Impact, Monitoring and Management of Environmental Pollution [1 ed.] 9781613247778, 9781608764877

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Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved. Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved. Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

POLLUTION SCIENCE, TECHNOLOGY AND ABATEMENT

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

IMPACT, MONITORING AND MANAGEMENT OF ENVIRONMENTAL POLLUTION

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POLLUTION SCIENCE, TECHNOLOGY AND ABATEMENT

IMPACT, MONITORING AND MANAGEMENT OF ENVIRONMENTAL POLLUTION

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

AHMED EL NEMR EDITOR

Nova Science Publishers, Inc. New York

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Copyright © 2010 by Nova Science Publishers, Inc. All rights reserved. No part of this book may be reproduced, stored in a retrieval system or transmitted in any form or by any means: electronic, electrostatic, magnetic, tape, mechanical photocopying, recording or otherwise without the written permission of the Publisher. For permission to use material from this book please contact us: Telephone 631-231-7269; Fax 631-231-8175 Web Site: http://www.novapublishers.com NOTICE TO THE READER The Publisher has taken reasonable care in the preparation of this book, but makes no expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No liability is assumed for incidental or consequential damages in connection with or arising out of information contained in this book. The Publisher shall not be liable for any special, consequential, or exemplary damages resulting, in whole or in part, from the readers’ use of, or reliance upon, this material. Any parts of this book based on government reports are so indicated and copyright is claimed for those parts to the extent applicable to compilations of such works.

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Independent verification should be sought for any data, advice or recommendations contained in this book. In addition, no responsibility is assumed by the publisher for any injury and/or damage to persons or property arising from any methods, products, instructions, ideas or otherwise contained in this publication. This publication is designed to provide accurate and authoritative information with regard to the subject matter covered herein. It is sold with the clear understanding that the Publisher is not engaged in rendering legal or any other professional services. If legal or any other expert assistance is required, the services of a competent person should be sought. FROM A DECLARATION OF PARTICIPANTS JOINTLY ADOPTED BY A COMMITTEE OF THE AMERICAN BAR ASSOCIATION AND A COMMITTEE OF PUBLISHERS. Additional color graphics may be available in the e-book version of this book. LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA Impact, monitoring, and management of environmental pollution / editor, Ahmed El Nemr. p. cm. Includes index. ISBN HERRN 1. Civil engineering--Environmental aspects. 2. Construction industry--Environmental aspects. 3. Pollution--Measurement. I. El-Nemr, Ahmed, 1962TD195.C54I47 2009 628.5--dc22 2009040471

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CONTENTS   Preface

ix 

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The Editot

xxi

Chapter 1

Impact of Environmental Pollution Yuanzhi Zhang and Yufei Wang

Chapter 2

Environmental Aspects and Impacts of Construction Industry Nik Norulaini Nik Ab Rahman, Fatehah Mohd Omar and Mohd Omar Ab Kadir

41     

Chapter 3

Radiation in the Environment: Sources, Impacts and Uses Amidu O. Mustapha

61   

Chapter 4

Freshwater Cyanobacterial (Blue-Green Algae) Blooms: Causes, Consequences and Control NK Sharma, KK Choudhary, Rakhi Bajpai and AK Rai  

73 

Chapter 5

Avian Immunotoxicology: Current Trends and Future Directions Michael J. Quinn, Jr.

97   

Chapter 6

Unplanned Urbanization and Associated Risk on Human Exposure and Sustainable Development: A Case Study Md. Jahir Bin Alam

115   

Toxic Effects of Lead and Cadmium as Industrial Pollutants on the Chromosome Structure in Model Mammalian Species M. Topashka-Ancheva and S. E. Teodorova

133   

Chapter 8

Marine Pollution in Water, Sediment and Biota Qing Xu, Hongyan Xi and Yuanzhi Zhang

157   

Chapter 9

Heavy Metal Pollution in Aquatic Environments Ayse Bahar Yilmaz

193   

Chapter 10

Heavy Metal Contaminations in Mediterranean Sediments Amany El-Sikaily, Azza Khaled and Ahmed El Nemr

223   

Chapter 7

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1   

vi Chapter 11

Cadmium and Organotin Pollution in an Estuarine Environment from Argentina: An Overview S. Botté , F. Delucchi , R.H. Freije , and J.E. Marcovecchio

263   

Antimony in Urban Roadside Surface Soils: Concentration, Source and Mode of Occurrence Xue Song Wang

285   

Organochlorine Pesticides, Polychlorinated Biphenyls and Polybrominated Diphenyl Ethers in Fresh Water Fish Species Özlem Turgay

293   

Atmospheric Pollution by Airborne Particle Dynamics in the Brussels Urban Environment Z.Y. Offer, D. Carati, L.Brenig, P.Vanderstraeten, Y. Lénelle, and A. Meurrens

315     

A Cadmium Standard Regression Line: A Possible New Index for Biological Monitoring Mariko Mochizuki, Makoto Mori, Ryo Hondo, and Fukiko Ueda

331     

Ecological Monitoring of Coastal Marine Environment at Kalpakkam, Southeast Coast of India K.K. Satpathy , A.K. Mohanty, Gouri Sahu1, M.V.R. Prasad, S. K. Sarkar, S. Biswas and M. Selvanayagam

339     

The Use ofBiomarkers in Bivalve Molluscs for the Evaluation of Marine Environment Pollution Juan Fernández-Tajes, Blanca Laffon and Josefina Méndez

409   

Chapter 18

Biomarkers Overview and Environmental Applications Vincent Leignel and Justine Marchand

431   

Chapter 19

Bioaccumulation of Some Heavy Metals in Freshwater Crayfish Utku Güner

479   

Chapter 20

Bioaccumulation of Heavy Metal by Microbes Nermeen A. El-Sersy, Gehan A. Abou-Elela and Hanan M. Abd- Elnaby

495     

Chapter 21

The Aromatic Hydrocarbon Receptor Mediated Cytochrome P450 1a Induction in Aquatic Animals: Biomonitoring of Organic Pollution in an Aquatic Environment S. Arun

517   

Chapter 12

Chapter 13

Chapter 14

Chapter 15

Chapter 16

Chapter 17

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Contents

Chapter 22

Heuristics Approach: Towards Sustainable Control of Environmental Pollution Nik Norulaini Nik Ab Rahman, Anees Ahmad, Fatehah Mohd Omar, and Mohd Omar Ab Kadir

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537 

 

Contents Chapter 23

vii

Application of Bioreactor Landfill Technology to Municipal Solid Waste Management: Asian Perspective Chart Chiemchaisri, Ruwini Weerasekara, Kurian Joseph, Sunil Kumar and Chettiyappan Visvanathan

553     

Chapter 24

A New Theoretical Basis for Description of Living Matter Svetla E. Teodorova

569   

Chapter 25

Modelling Local and Regional Boundary Conditions of the Geographical Distribution of Mosses and their Metal Loads in Germany Roland Pesch and Winfried Schröder

581   

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Index

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597 

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PREFACE In the 21st century, the fate of the environment has become a critical issue in both developed and developing countries throughout the world. The environment is considered the surroundings in which an organism operates, including air, water, land, natural resources, flora, fauna, humans and their interrelation. Water pollution, poor air quality, global warming, acid rain, ozonosphere hole, etc., these issues are featured regularly in our newspapers, news reports and TV programs. Pollution has been used quite freely for many years without a clear definition, and it is generally accepted that environmental pollution can be defined as the contamination of air, water, or soil in such a manner as to cause real or potential harm to human health or well-being, or to damage or harm nonhuman nature without justification. Pollution can take many forms, the air we breathe, the water we drink, the soil where we grow our food, and even the increasing noise we hear every day, all contribute to health problems and a lower quality of life. The result of human activities is the main cause of environmental pollution; most people have witnessed pollution in the form of an open garbage dump or an automobile pouring out black smoke. However, pollution can also be invisible, odorless, and tasteless. Some kinds of pollution do not actually dirty the land, air, or water, but they reduce the quality of life for people and other living things, for example, noise from traffic and machinery. We have become much more aware of how vulnerable it is to destruct our world by the human activities. Population increases and technological advances are creating a burden on society by requiring continued expansion and concomitant resource use. Substantial evidence exists showing that such development has led to detrimental impacts on the environment. We know that increased societal activities and demands are changing soil, water, air, climate, and resources in unexpected ways. This in turn has led to a renewed interest in protecting the environment and has focused attention on the concept of environmental monitoring and site characterization, including an evaluation of the physical, chemical, and biological factors that impact the environment. This information is necessary for researchers, decision-makers, and the community as a whole, to implement social changes needed to preserve and sustain a healthy environment for future generations. We also know that the environment exists as a continuum of biosystems and physio-chemical processes that help sustain life on earth. Therefore environmental monitoring should ideally consist of examining the integrative nature of these processes.

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Ahmed El Nemr

The purpose of this review book is to document the latest research in this field which is vital for everyone. As reported in chapter 1, environmental pollution includes any substance that may adversely impact our possessions or lives. It may be in the form of particulate solids, liquids, gases or vapors. Pollutants are created artificially by various industrial processes, accidents, and from some in house activities and materials. But some arise from natural processes, some of which are sudden and dramatic, such as lightning, volcanoes and forest fires, whilst others derive from slow continuous processes such as the decay of animal and vegetable matter. Thus, the effects of pollution would cause harm or discomfort to humans or other living organisms, or damage the environment. In chapter 2, given the international focus on sustainability in recent years, there is a dire need to evaluate the aspects and impacts in the construction industry and identify methods and techniques that would facilitate sustainability and impact assessment and decision making at the various project level interfaces. The construction activities are being kept under rigid analysis and control due to its intimacy and direct association with the outdoor (external) environment. Any construction, irrespective of size, type and location will cause impacts onto the environment arising from the construction activities, for as long as the construction goes on until the commissioning stage. These environmental impacts are typically classified as air pollution, land contamination and degradation, noise pollution and water pollution. Construction activities impart significant impacts on the environment across a broad spectrum whether it is off-site, on-site and operational activities. Off site activities comprehend office management, documentation, policy, and planning, engineering and architectural drawings. On site construction activities relate to the pre-construction and the actual construction of a physical facility, resulting in air pollution, water pollution, traffic problems and the generation of construction wastes. Activities in the construction industry are complex, highly dispersed and resource demanding. Radiation is transport of energy in the form of electromagnetic waves or energetic particles through space or material. Although all forms of radiation are important, the main concern in this chapter is the ionizing radiation, i.e. those that can cause ionization in the medium through which they traverse. The environment is permeated by ionizing radiation from diverse artificial and natural sources. Ionization can disrupt normal biological processes in living tissues; therefore it may be harmful to living organisms in the environment, including human beings. But as a natural component of the environment, ionizing radiation is not always detrimental to life; rather it is compatible with life. A complete elimination of ionizing radiation from the environment is therefore neither possible (because some of the sources are not amenable to control) nor desirable since it has many important beneficial applications. Indeed there are clear evidences that the authors present and emerging lifestyles will not be sustainable without applications of radiation technologies, e.g., in health, agriculture, energy, environmental studies, etc. There are many authoritative books and reviews on various aspects of radiation and radioactivity in the environment. Therefore chapter 3 will focus mainly on the impacts of radiation in the environment: on one hand as an environmental contaminant or pollutant arising partly from both natural phenomena and human activities, and on the other hand as a tool for studying and conserving the environment. An overview of the various natural and artificial sources of environmental radiation is first presented, followed by a presentation of the environmental and radiological impacts of the various sources. The latter includes reviews of the developments in radiation

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dose assessment and radioactivity measurement techniques, as well as a brief description of the beneficial uses of radiation particularly in environmental studies. As reported in chapter 4, the harmful algal blooms (HABs) are natural phenomena however, due to human activities and interventions incidences of HABs have increased globally. Onset, development and proliferation of blooms are closely associated with nutrient enrichment of water bodies (eutrophication) and climatic changes; and their possible interaction. Cyanobacteria are amongst the most successful bloom forming algae. They can convert and use different form of C, N, P, and S that help them in occupying almost all kind of aquatic habitats. Moreover, they grow well in shaded light, show resistance against grazing pressure and release allelochemicals to out-compete co-occurring organisms. Presence of gasvacuoles facilitates their migration in water column to ensure enough light and nutrient availability. Cyanobacterial blooms adversely affect water quality, structure and composition of biological communities and a range of ecological services. Many of the bloom forming cyanobacteria produce toxins responsible for mass mortality of aquatic and exposed vertebrate populations. Chapter 2 describes the causes and consequences of cyanobacterial blooms and a few measures adopted to control bloom formation proliferation. Impact of climatic change on cyanobacterial bloom formation has also been discussed. Immunotoxicology is a relatively recent subdiscipline of the larger field of toxicology with the majority of its studies focused on mammalian systems. Immunotoxicological studies that concentrate on avian species have steadily increased over the past two decades. Birds occupy a wide variety of ecological niches and are good representatives of many different trophic levels, making them good indicators for environmental health assessments. Chapter 5 describes current methods that are commonly used to assess immune status in birds and suggests directions for future efforts. The usefulness of measures that assess the effects of environmental contaminant exposure on immunological structure will be compared to those that test function. Particular attention is paid to emerging issues in the field, such as developmental immunotoxicology (DIT) and the use of cytokine measures in immunotoxicity evaluations, and how they are being, or should be, addressed in avian species. In chapter 6, some emergency planning policies in Sylhet urban area are taken by Government. It is seen that a considerable part of the concerned area is under high-risk zone and some parts come under very high-risk zone. It is also found that about half of the population (55.22%) comes under very high-risk zone and it constitutes about 51.29% of total area. Again, 44.78% of population is living in the rest area having high-risk exposure due to existing surface water quality. The author concluded that if the surface water of Sylhet Municipality is being used as the source of water supply system it should be treated under high degree of treatment. Detail study will help to take a sustainable urban planning and also the way to improve the situation. A survey on ecologo-toxicological experiments exploring the karyotype responses of small mammalian species to heavy metal load is proposed in chapter 7. The animals used were laboratory mice Mus musculus alba inbreed line BALB/c and wild Guenther’s vole Microtus guentheri, adapted to laboratory conditions. Industrial mixture containing lead and cadmium in high concentrations was applied as representative of emission to the environment. The polymetal dust was mixed with conventional animal food at 1% concentration. The metal quantities in animals’ diet were about 780 mg/kg lead and 64 mg/kg cadmium. The type of chromosomal aberrations and chromosomal aberration frequency in bone marrow cells as well as the changes in the nuclear proteins in liver and kidney tissues

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were studied. The presented mathematical model describes successfully the time course of chromosomal aberration frequency in female BALB/c mice. The responses of both species were compared and the high relevance of their use in ecotoxicology and zoomonitoring was confirmed. The frequencies of the chromosomal aberrations in the exposed Guenther’s vole and BALB/c mice differed insignificantly. The most frequently encountered aberrations were chromatide breaks and centromere-centromeric fusions (c/c). In Guenther’s vole, significant damages of the chromosomal protein were found on day 60 after exposure. In BALB/c mice changes in the electrophoretic profiles were recorded yet on day 15. No trend of continued increase of the chromosomal aberration frequency in both rodents was established during the exposure. This fact suggests a relative high resistance of genetic apparatus to heavy metals as a component of the anthropogenic pollution. In chapter 8, many potentially toxic chemical adhere to tiny particles which are then taken up by plankton and benthos animals. Most of them are either deposit or filter feeders, concentrating upward within ocean food-chains. In addition, since most animal feeds contain high fish meal and fish oil content, toxins could be found a few weeks later in commonly consumed food items derived from livestock and animal husbandry. As rivers are the common entrance of contaminants to the marine environment, many particles combine chemically in a manner highly depletive of oxygen, leading to estuaries to become anoxic. Chapter 9: Metals which in their standard state have a specific gravity (density) of more than about 5 g cm-3 are described as ‘heavy metals’. Some of them such as copper, iron, chromium, zinc and nickel are essential in very low concentrations for the survival of all forms of life. These are described as essential trace elements. Only when present in greater quantities, these can cause metabolic anomalies like the heavy metals lead, cadmium, arsenic and mercury which are already toxic in very low concentrations. Heavy metals are produced from a variety of natural and anthropogenic sources. Human beings release a high anthropogenic emission of heavy metals into the biosphere. Waste (i.e. emission, wastewater and waste solid) is the origin of heavy metal pollution to water, soil and plants. In aquatic environments, metal pollution can arise from direct atmospheric deposition, geological weathering or through discharge of agricultural, municipal, residential or industrial waste. Under certain environmental conditions, heavy metals may accumulate to a level of toxic concentration causing ecological damage. As a result, living things inhabited in contaminated waters may show rather high metal concentrations. In addition, metal bioaccumulation causes biochemical or pathological effects on fish resulting in decrease of growth, fecundity and survival. The members from the upper level of the food chain may carry a critical level of metals and are hence more explanatory than observing water or sediments. Therefore, numerous reports describe metal residues in aquatic organisms such as mussels, shrimps and wild fish from marine and freshwater species. Such studies have been carried out to determine the levels of some heavy metals in some tissues of aquatic organisms from marine and inland waters. Liver, spleen and kidney tissues are known to have high metabolic activities and thus have been used to observe the level of absorbed metals. Gonads, which can be attributed to the reproductive cycle of fish, have also accumulated high amount of heavy metals. Metal concentrations in the skin and gill have reflected the concentration of metals in waters. Although it is well known that muscle is not an active tissue in accumulating heavy metals, muscle tissue accumulation levels were also studied because of their consume by humans.

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Metal uptake by aquatic organisms from contaminated water may differ depending on its ecological needs and metabolism, as well as other factors such as salinity, temperature, contamination gradients of water, food, sediment and interacting agents. Two main objectives prevail in aquatic pollution monitoring programs: (1) determining contaminant concentrations in consumed part of organisms considering the health risk for humans, and (2) using organisms as an environmental indicator of aquatic ecosystems quality. The Mediterranean Region, embracing parts of two continents as diverse as Europe and Africa, is a complex geographic, ecological, cultural and socio-political set-up based around the Mediterranean Sea basin. The Mediterranean climate, with mild wet winters and hot dry summers, has been used as a model for many other regions around the world. Its landscape and monuments continues to be the greatest tourist destination in the entire world. As a consequence, urbanization has been particularly growing along the coastal strip, to accommodate both permanent and temporal population, with the result of a substantial modification of the coast itself and adverse effects on the quality of the environment. The highly developed industrial countries in the North stand in stark contrast to the countries in the South. These differences have significant implications when addressing environmental issues and particularly those related with the management of persistent toxic substances (PTSs). The description of the contamination of Mediterranean coast sediment with heavy metals is summarized in this review. The concentrations of Fe, Mn, Ni, Hg, Cd, Pb, Zn, etc. in sediment collected from Mediterranean coast of eight countries were presented in chapter 10. Most of the published articles about the contamination of sediment of Mediterranean with heavy metals have been discussed in this work. The total heavy metal concentrations have been monitored for almost thirty years, while organotin compounds have only been evaluated in the last few years. Inter-tidal as well as subtidal surface sediments were fully analyzed and the corresponding results are included in chapter 11. Cadmium contents within sediments were slightly higher close to the area where the industrial effluents are discharged, as well as near the harbor zones during the study period. The analysis revealed that with the exception of the last analyzed period-cadmium is at background concentrations within the study system. A permanent monitoring program within the inner zone of the estuary has demonstrated that cadmium concentrations slightly increased during the study period, indicating a regular input of these metals into the system. In addition, recent studies have shown similar contents of cadmium on both tidal flats and sub-tidal sediments within the estuary. Organotin compounds (DBT and TBT) were found in sediments of the entire studied area. Their concentrations ranged from very low values within low impacted areas to higher ones next to the most active harbor facilities. The highest amounts of both DBT and TBT were recorded in the neighborhood of dry docks where careenage of ships may be the main source. These results throw light upon the process of accumulation of cadmium and organotin compounds within the analyzed sediments, allowing the author to conclude that the inner area of the Bahía Blanca estuary could be considered an intermediate polluted system. Antimony (Sb) is one of the elements of increasing environmental significance. In chapter 12, concentrations of Sb were measured on 21 roadside surface soil samples collected from a medium-size city, Xuzhou (China), in order to assess the magnitude of contamination and to identify the possible contamination sources. The mode of occurrence of Sb and the effect of particle size fractions on Sb concentration distributions were also investigated from

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two specific soil samples. Median of Sb concentrations of the investigated urban surface soils is 0.96 mg/kg. This value is a little higher compared to the regional background value. The Sb in the Xuzhou surface soils is mainly attributed to the inputs of coal combustion and almost independent of the particle size fractions. The most common mode of occurrence of Sb is in association with Fe-Mn oxides. In chapter 13, the production and intensive agricultural or industrial use of persistent organohalogenated pollutants (POPs), such as organochlorine pesticides (OCPs) or polychlorinated biphenyls (PCBs), have led to the widespread contamination of the environment. Polybrominated diphenyl ethers (PBDEs) have come into extensive use as flame retardant additives to plastics, textiles, electronics and paints. Persistent organic pollutants (POPs) have been found in food since the 1960s. Fish is a suitable indicator for the environmental pollution monitoring because they concentrate pollutants in their tissues directly from water, but also through their diet, thus enabling the assessment of transfer of pollutants through the trophic web. Data on the presence and distribution of organohalogenated contaminants in fish and especially edible fish species is therefore important not only from ecological, but also human health perspective. As reported in chapter 14, wind erosion, airborne particle production, their transport, deposition and accumulation on different natural and anthropic surfaces have always given rise to inconvenience for many people. During the last decades this phenomenon has become a very important international problem. A major effect of the atmospheric particles corresponds to the broad term of air pollution. Air pollution is essentially caused by the presence of what is called “fugitive dust emissions”. The latter term denotes dust that is injected into the atmosphere by the combined effects of man’s activity and the action of the wind, especially over farms, unpaved roads and other ground surfaces, industrial activity and re-suspension of particles by traffic flow. Wind-blown dust is also an efficient way to spread pathogens that are harmful to people, animals and plants. Particles less than 2 μm in diameter are retained in the human lungs. Some of these particles are pathogenic and may have a considerable negative impact on health. The field measurements (PM10 and PM2.5 concentrations), the laboratory analysis (particle size distribution, micromorphology, mineralogy, and chemistry) and the study of the data and the correlations with the atmospheric dynamics, lead to the following general conclusion: the majority of the airborne particle concentrations measured in Brussels belongs to sources located out of the urban area. A smaller percentage of the particles originate from local sources. They are caused by different human activities: road traffic, domestic heating, building industry, general industrial activities, etc… Under dry weather conditions, wind and local activities may lead to the resuspension of the coarser particles (between PM2.5 and PM10) formerly deposited on different urban surfaces. The formation of secondary aerosols (e.g. ammonium salts), under conditions with mild temperature and a relative high humidity range, seems to be an important contributor to the PM2.5 concentration. Recent EC directives on the allowed concentrations of PM10, PM2.5 and, especially, smaller particles in urban and rural areas imposes further investigations in order to determine with enough accuracy their origin, shape and chemical composition.

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As the recent outbreak of Saharan dust storm over the Brussels region has shown, the constant field monitoring, laboratory analysis and data study of extreme events involving airborne particles are an important part of our research program. The methods of biological monitoring for estimating environmental contamination, a solution to the problems of environmental monitoring using wildlife and the using of the CSRL for data obtained from wildlife are reported in chapter 15. In chapter 16, a detailed account of the hydrographic features including nutrient distribution in the coastal waters of Kalpakkam is discussed. Keeping this view in the backdrop, recent results of studies (2006-2008) on i) qualitative and quantitative abundance of phytoplankton, ii) seasonal variations in phytoplankton community organization and iii) the influence of environmental variables on phytoplankton species assemblage in the Kalpakkam coastal waters, southeast coast of India are also discussed in chapter 16. Notwithstanding the interest driven by either, the three important parameters for practical use undoubtedly are a) type of benthos, b) their growth rate and c) their seasonal variations. Therefore, monthly and seasonal status of benthic community in the southeast coast of India is discussed in this chapter as part of ecological studies. The impact of the presence of such a high density of fouling organisms residing inside the tunnel on the adjacent coastal environment is also discussed. The degradation of the habitat, together with the overexploitation of natural resources, the invasion by alien species as well as pollution, represent the major problems jeopardizing coastal regions. Human activities are the main cause of marine pollution, including recurrent spills of toxic agents both in open sea and in estuarine areas. Besides, natural disasters such as landslides and flash floods also contribute significantly to the increase of marine pollution. Over the last decades, the use of biomarkers for biomonitoring the impact of several contaminants has been increased. A biomarker can be defined as measure at a molecular, cellular or whole organism level, of the exposure to contaminants (exposure biomarkers) or of the organism response to the pollutants (effects biomarkers). Genotoxicity biomonitoring is one of the most important features to evaluate the environmental stress and the pollution impact on marine organisms. In this sense, the development of suitable and sensitive biomarkers, such as those for the assessment of DNA damage, is required. The aim of chapter 17 is to provide an overview of the practical use of genotoxicity biomarkers in marine bivalve molluscs to evaluate the extent and consequences of environmental contamination in these organisms. This review illustrates the results obtained during the development and application of exposure/effect biomarkers for biomonitoring purposes in several sentinel species. In chapter 18, some ecotoxicological investigations are presented to illustrate the common use of the biomarkers and the biomarkers more recently developed. Anthropogenic inputs of pollutants such as heavy metals into the marine environment have increased their levels to large extents within past few decades. The available literature on heavy metal bioaccumulation by freshwater crayfish has been analysed. A very uneven data distribution was found, Orconectes, Cambarus Procambarus and Astacus are the most commonly investigated orders of crayfish. Furthermore, Zn, Cu, Pb and Cd are the most intensively researched heavy metals, and only infrequent investigations of other metals are documented. At some conditions bioaccumulation levels of some heavy metals were as follows Mn> Zn >Cu>Ni>Cr>Pb>Cd. Accumulated metal concentrations are interpreted in terms of different trace metal accumulation patterns, dividing accumulated metals into two

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components - metabolically available metal and stored detoxified metal. Chapter 19 will focus on bioaccumulation of some heavy metals on freshwater crayfish. In chapter 20, marine environment is considered to be as one of the most important habitats that must be protected from pollution worldwide. In recent years marine pollution has increased, due to increase in ship traffic and the uncontrollable dumping of toxic materials and wastes to the seas. Heavy metals have received considerable attention in recent years with regard to toxicity to aquatic life. Chapter 20 deals with sources, distribution and fate of heavy metals in the sea water. Heavy metals accumulation by microorganisms is regarded as an attractive alternative to the physical and chemical methods applied for the treatment of heavy metals contamination. Bacillus Staphylcoccus, Corynebacterium, Enterobacter, Escherichia, Aeromonas, Pseudomonas, Klebsiella, Vibrio, Arthrobacter, Brevibacterium, Deinococcus, Erwinia, Micrococcus, Nacardia, Sarratia, Tthiobacillus, and Zoogloea are the most important bacterial species that used in the bioaccumulation processes. Chapter 20 also reviews bacteria-metals interactions and mechanisms of metal cations accumulation by bacteria. Moreover minimal inhibitory concentrations (MICs) of most heavy metals to E. coli, resistance mechanism to copper, zinc and arsenic and finally, the accumulation of metal inside the bacterial cell and change in cell morphology were also reviewed. In chapter 21, the molecular mechanism of AhR mediated CYP1A induction in aquatic organisms is described and the way it could be applied as a suitable biomarker for the early detection of organic pollution in aquatic environment is explained. The control of environmental pollution is a multi facet management system which encompasses the role of individuals, industries, states, nations as well as international agencies. Its success demands a great vision and zeal for the sustainable developments and requires great care at the topmost hierarchy of environmental management system followed by the economy of the industries. The first step in this process is the knowledge of impact of pollutants. In order to understand the impact of different types of environmental pollution and to establish ways and means to address the issues, we need to look at the inevitable trade-off situation that characterizes all pollution-control activities. An effort made in reducing the generation of hazardous wastes or the release of emissions and effluents would require the industry to seek change to some part of processing and management of the industry and this might be procured from intense research and development. Absence of such effort will inadvertently increase the damages incurred onto the environmental. The management of hazardous wastes by industries is done through ‘command-and-control’ approach through governing laws which is based on various types of standards to bring about improvements in environmental quality. However managing hazardous wastes via complying with standards alone is not sufficient. The increasing cost in end of the pipe hazardous waste management in addition to mainstreaming and operating efficient pollution control equipment has led many industries to find better ways to delay with the hazardous wastes handling and disposal. Chapter 22 presents a set of heuristics to stimulate an investigation aimed at clearing the doubts and complexities pertaining to the requirements of pollution-control specifically for multi-product plants and initiate the implementation of improved pollution-prevention and pollution-control solutions. In recent years, due to the advance in knowledge of landfill behavior and decomposition processes of municipal solid wastes (MSW), there has been a strong thrust to upgrade existing landfill technology from a storage/containment concept to a process-based approach, in other words, as a bioreactor landfill. Operating landfills as bioreactors and hence enhancing the

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stabilization of wastes is one such option that has been elaborately investigated and already been in practice in the U.S. and European countries. As compared to many developed countries, the concept of leachate recirculation is still relatively new to Asia. Nevertheless, there are laboratory scale and pilot scale researches including few full-scale implementation of this technology in Asia. Research and development activities relating to aspects of landfill bioreactor are keeping the interest of scientists and engineers alive and enriching the literatures. Findings of bioreactor landfill research have resulted in generation of enormous data and their publication in variety of journals and books. Collating data from such diverse sources would help understand the bioreactor landfill concept, benefits to be derived, design and operational issues, possible solutions to many of these issues, ongoing researches, etc. Chapter 23 is an attempt to present an overview in this direction in Asian perspective. As reported in chapter 24, in the context of environmental pollution, it is of prime importance to study the organism's overall response to harmful environments. This could be carried out if there were suitable dynamic variables, describing the state of a living system. In this respect, a new approach to life phenomena is needed because in phenomenological aspect, the biological objects in their entirety could be not adequately described in the terms of other science fields. The main features of the living system are its integrity and selfregulation. Energy dissipation runs in the living systems but there the more substantial property is the increase of the energy worth. Here a new theoretical basis and new science field, biodynamics, is suggested. A new state variable vitality as integral characteristic of a biological object is stated. It is impossible to deduce the macro-characteristics of a living system based on the processes on molecular level. Vitality could be a phenomenological characteristic uniquely determining the status of the living object. Quantities biological energy and synergy are introduced. The synergy is assumed as a measure of self-regulation quality. Biological principle for maximum synergy is stated. The conception proposed is illustrated on the case of recovery process of some biological object after some transitory disturbance. Based on variational principle of Hamilton type an equation describing the recovery process is obtained. If a quantity as vitality could be measured this could provide a great benefit for biology, medicine, and ecology. The UNECE Heavy Metals in Mosses Surveys measure environmental concentrations of metals in mosses throughout Europe for ecotoxicological risk assessments. The metal loads depend on the deposition rate as well as on local and regional boundary conditions. In chapter 25 the most important boundary conditions are identified with help of the German moss survey data 1990, 1995, and 2000 using tree based models: moss species, precipitation, slope direction, and landuse. The knowledge of their influence on the metal accumulation is essential for the interpretation of the biomonitoring data and is of importance for designing the monitoring nets of succeeding monitoring campaigns. A shift of the geographical distribution of mosses could be observed by means of Classification and Regression Trees (CART). Based on the model, a predictive map was calculated in a GIS environment. Alexandria in 15 April, 2010

Ahmed El Nemr

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The Editor

Professor Ahmed El Nemr was born 1962 in El Behera, Egypt. He received his BSc degree in chemistry in 1984 with a general grade of excellent and his MSc degree in organic chemistry from Alexandria University under the supervision of Professor E. S. H. El Ashry, after which he was awarded his PhD in Engineering in Applied Chemistry by Keio University, Yokohama, Japan. He worked from 1991 to 1997 (six years) as a researcher at the Institute of Bioorganic Chemistry, Kawasaki, Japan with Professor Tsutomu Tsuchiya. He is now working as Professor at the Environmental Division, National Institute of Oceanography and Fisheries, Egypt. He is the head of Egypt National Oceanography data center (ENODC) and the national coordinator of Egypt at IODE-IOC-UNESCO. Professor El Nemr has over 124 published research papers in international journals and author of two books published by Blackwell and Nova Science publishers as well as he is Editor to one book in corrosion published by research sign post publishers. He is Editor of two web sites. His research interest is devoted to explore novel approaches for synthetic methodologies in carbohydrate chemistry and the synthesis of natural compounds. Syntheses of deuterated carbohydrates using different methods are one of his main works. Syntheses of carbohydrates in the form of their nitrogen derivatives as raw materials for the synthesis of other classes of organic compounds and heterocyclic compounds were also of his great interest. Isolation of some natural compound from marine algae as well as isolation of chitin and chitosan and their chemical modification study. Corrosion inhibition and its prediction for selected organic compounds using Quantum chemical calculations. New activated carbons development from agriculture wastes is also of his great interest. Removal of textile dyes, organic pollutants and heavy metals from water using macro algae, activated carbons and agriculture wastes as well as water treatment and wastewater purification. The distribution of petroleum hydrocarbon, pesticides, polycyclic aromatic hydrocarbons, polychlorinated biphenyls and heavy metals in the Mediterranean, Red Sea and inland waters (Egypt) was investigated and correlated with pollution and environmental aspects. Oil spill and Machine oil treatment technologies.

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Chapter 1

IMPACT OF ENVIRONMENTAL POLLUTION Yuanzhi Zhang1 and Yufei Wang Institute of Space and Earth Information Science, The Chinese University of Hong Kong, Shatin, NT, Hong Kong, China

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ABSTRACT Environmental pollution includes any substance that may adversely impact our possessions or lives. It may be in the form of particulate solids, liquids, gases or vapors. Pollutants are created artificially by various industrial processes, accidents, and from some in-house activities and materials. But some arise from natural processes, some of which are sudden and dramatic, such as lightning, volcanoes and forest fires, whilst others derive from slow continuous processes such as the decay of animal and vegetable matter. Thus, the effects of pollution could cause harm or discomfort to humans or other living organisms, or damage the environment.

1. INTRODUCTION Water pollution, poor air quality, global warming, acid rain, ozonosphere hole, etc.; these issues are featured regularly in our newspapers, news reports and on TV programmes. We have become much more aware of how vulnerable it is to destruct our world by human activity.

What is Environmental Pollution? Pollution has been used quite freely for many years without a clear definition, and it is generally accepted that environmental pollution can be defined as the contamination of air,

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water, or soil in such a manner as to cause real or potential harm to human health or wellbeing, or to damage or harm non-human nature without justification. Pollution can take many forms, the air we breathe, the water we drink, the soil where we grow our food, and even the increasing noise we hear every day; these all contribute to health problems and a lower quality of life. The following words list the major forms of pollution, Traditional forms of pollution include: Air pollution is caused by the release of chemicals, particulate matter, or biological materials into the atmosphere by human activities that tend to interfere with human comfort, health and cause environmental damage. Common air pollutants include carbon monoxide, sulfur dioxide, and nitrogen oxides produced by industry and motor vehicles. Air pollution causes acid rain, ozone depletion, photochemical smog, and other such phenomenon. Water pollution is the contamination of water bodies such as lakes, rivers, oceans, and groundwater caused by human activities, and refers to the addition of foreign substances to a water source. These impurities have a detrimental effect on water quality, and can be harmful to living organisms and aquatic life. Soil pollution refers to the pollution of soil with toxic compounds, chemicals, salts, and radioactive materials, which have adverse effects on plant growth and animal health. Radioactive pollution is the result of the 20th century’s activities in atomic physics, such as nuclear power generation and nuclear weapons research, manufacturing and deployment. Modern pollution forms include: Noise pollution occurs when continuous noise is loud enough to be annoying or physically harmful, which encompasses roadway noise, aircraft noise, industrial noise as well as high-intensity sonar. - Light pollution, light from cities and towns at night that interferes with astronomical observations is known as light pollution, it can also disturb natural rhythms of growth in plants and other organisms. - Thermal pollution is a temperature change in natural water bodies caused by human influence, such as heat from hot water that is discharged from a factory into a river or lake, where it can kill or endanger aquatic life. - Visual pollution can refer to the presence of unattractive or unnatural visual elements of a landscape or any other thing that a person might not want to look at. Commonly cited examples are advertisements, skywriting, houses, automobiles, traffic signs, roadways, litter, graffiti, overhead powerlines and buildings.

Environmental Pollution Causes Pollution can occur naturally, for example through volcanic eruptions, when a volcano erupts, spewing out huge quantities of ash, chlorine, sulfur dioxide, and other chemicals. But the result of human activities is the main cause of environmental pollution; most people have witnessed pollution in the form of an open garbage dump or an automobile pouring out black smoke. However, pollution can also be invisible, odorless, and tasteless. Some kinds of pollution do not actually dirty the land, air, or water, but they reduce the quality of life for people and other living things, for example, noise from traffic and machinery.

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Motor vehicles, small industries and businesses are some of the major factors responsible for poor air quality. The number of vehicles and small businesses have increased with population growth. With economic growth also comes an increasing demand for industry and agriculture, which can both greatly impact on our air quality. Energy use and greenhouse gas emissions can also impact air quality. Greenhouse gas emissions act like a blanket surrounding the earth, trapping the heat of the sun in the atmosphere, warming the planet; and humans contribute to this enhanced greenhouse effect by burning fossil fuels such as coal to generate electricity and by driving petrol fueled cars. There are many different chemical substances that contribute to air pollution, and the major air pollutants are nitrogen oxides, carbon monoxides, and organic compounds that can evaporate and enter the atmosphere. Air pollution results from a variety of causes, not all of which are within human control. Dust storms in desert areas and smoke from forest fires and grass fires contribute to chemical and particulate pollution of the air. The source of pollution may be in one country but the impact of pollution may be felt elsewhere. The discovery of pesticides in Antarctica, where they have never been used, suggests the extent to which aerial transport can carry pollutants from one place to another, and as a result, poses threat to the health of people and ecosystems. Though some pollution comes from these natural sources, most pollution is the result of human activity. The biggest causes are the operation of fossil fuel-burning power plants and automobiles that combust fuel. In the United States, these two sources are responsible for about 90% of all air pollution. Water pollution is largely caused by human activity and has a major impact on our local waterways and their ability to be healthy and function naturally. Water pollution occurs when a body of water is adversely affected due to the addition of large amounts of materials to the water. There are many causes for water pollution but two general types exist: direct pollution and indirect pollution. Direct pollution occur when harmful substances are emitted directly into a body of water. Oil spills, effluent outfalls from factories, refineries and waste treatment plants best illustrates the direct pollution. Today, many people dump their garbage into streams, lakes, rivers, and seas directly, thus making water bodies the final resting place of cans, bottles, plastics, and other household products. Indirect pollution means delivering pollutants indirectly through environmental changes. An example of this type of water pollution is when fertilizers or pesticides from a field are carried into a stream by rain. Soil pollution typically arises from the rupture of underground storage tanks, application of pesticides, percolation of contaminated surface water to subsurface strata, oil and fuel dumping, the leaching of wastes from landfills or direct discharge of industrial wastes to the soil. The most common chemicals involved are petroleum hydrocarbons, solvents, pesticides, lead and other heavy metals [1]. Soil pollution can lead to water pollution if toxic chemicals leach into groundwater, or if contaminated runoff reaches streams, lakes, or oceans. Soil also naturally contributes to air pollution by releasing volatile compounds into the atmosphere. The decomposition of organic materials in soil can release sulfur dioxide and other sulfur compounds, causing acid rain. Heavy metals and other potentially toxic elements are the most serious soil pollutants in sewage. Sewage sludge contains heavy metals and, if applied repeatedly or in large amounts, the treated soil may accumulate heavy metals and consequently become unable to even support plant life.

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The natural environment contains many sources of noise: wind, volcanoes, oceans, and animal sounds are all familiar intrusions accepted at various levels. Man-made noises are generated from machines, automobiles, trains, planes, explosives and firecrackers. Both kinds of noise affect sleep, hearing, communication, as well as mental and physical health.

Environmental Pollution Effects The amount of pollution that has entered our environment has been greatly increased by human activity and can have a negative impact on human quality of life and the health of the environment.

Ecosystem Effect

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The naturally occurring effect of air pollution is known as the greenhouse effect. Humans contribute to this enhanced greenhouse effect by burning fossil fuels such as coal to generate electricity and by driving petrol fueled cars, so that more heat is being trapped and the earth is warming up at an accelerated rate. This can change the Earth's climate. Predicted climate changes include hotter weather, more brushfires and storms, loss of some plants and animals, rising sea levels and a loss of biodiversity. Pollutants like oil, detergents, nitrogen and phosphate from fertilizers and lead can have a tremendous impact on the ecosystem, especially if the water gets polluted. In a lake, for example, it can wreak havoc on the ecological balance by stimulating plant growth and causing the death of fish due to suffocation resulting from lack of oxygen. The oxygen cycle will stop, and the polluted water will also affect the animals dependant on the lake water.

Human Health Effects Many studies in people have demonstrated an association between environmental exposure and certain diseases or other health problems. Pollutants are known to be a factor in many illnesses and diseases including cancer, immune diseases, allergies and asthma. Some illnesses are discussed in relation with certain pollutants: for example, Minamata disease, which is caused by mercury compounds. A recent research project concluded that pollution deserves a place alongside heart disease and cancer on the list of leading causes of death worldwide. Contamination of water, air and soil leads to 40 percent of the planet’s death toll, according to a study conducted by Prof. David Pimentel. “In the United States alone, 76,000 people are in the hospital each year, with 5,000 deaths, just due to pollution of air, food or water. Cancers are increasing in the U.S., and AIDS is on the rise,” Pimentel said. Noise pollution, for example, noise is inescapable in the industrial environment, which is increasing with advances in industrialization and urbanization. Noise not only causes irritation or annoyance but also constricts the arteries, and increases the flow of adrenaline and forces the heart to work faster. Health experts are of the opinion that excessive noise can also lead to neurosis and nervous breakdown.

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Economic Effects The effects of environmental pollution on human health and the environment have involved the economic impact. The World Bank has warned that air pollution is costing China 3.8 percent of its gross domestic product, causing more diseases and claiming more lives, while it has put the combined health and non-health cost of outdoor air and water pollution for China's economy at around US$100 billion a year, or about 5.8 percent of the country's GDP. According to the Healthy People 2000 report, each year in the United States: • • •

The health costs of human exposure to outdoor air pollutants range from $40 to $50 billion. An estimated 50,000 to 120,000 premature deaths are associated with exposure to air pollutants. People with asthma experience more than 100 million days of restricted activity, costs for asthma exceed $4 billion, and about 4,000 people die of asthma.

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Soil pollution leads contaminates an estimated 12 million tonnes of grain with heavy metals every year, causing direct losses of 20 billion yuan (US$2.57 billion). Harmful substances accumulate in crops and, via the food chain, find their way into our bodies, where they can cause a variety of illnesses. The Environmental Defense Fund article, “Why is it Better to Buy Green Electricity?” states that acid rain causes $6 billion a year in damage to crops, forests, lakes, and buildings. The potential economic impact of global warming is estimated to be in the billions of dollars. While green sources of electricity may cost more, they do not incur the external costs of traditional fossil fuel-based generation. The EDF article states that: “Increasing reliance on green sources reduces financial risks such as future regulations, taxes on greenhouse gases, and price fluctuations associated with fossil fuels. Green resources increase U.S. energy self sufficiency, and thus economic security, by reducing reliance on fossil fuel imports. They also help reduce current rapid depletion of natural resources. Green resources are a good source of jobs and income because they rely on local labor, land, and resources. Rural communities would probably benefit the most from renewable energy development, as wind and biomass energy production is likely to take place in rural areas.”

2. ENVIRONMENTAL POLLUTANTS AND THEIR IMPACTS What Substances are Pollutants? The United States Environmental Protection agency (EPA) defines a pollutant as any substance introduced into the environment that adversely affects the usefulness of a resource. Almost any chemical, any substance, any material, whether generated by human beings or nature can pollute, but synthetic and other industrial chemicals most concern people.

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Chemicals pollutants are more easily understood if you first understand the chemicals of which they are composed. There are two major categories of chemicals, organic chemicals and inorganic chemicals. Organic chemicals: To say that a chemical is organic simply means that it contains at least one carbon atom and, typically, more. Organic chemicals contain other elements, if the chemical contains only carbon and hydrogen it is called a hydrocarbon. Other organic chemicals often also contain additional elements, such as oxygen, nitrogen, and sulfur, but carbonates and simple oxides of carbon are not considered organic chemicals. If a carbon atom is bonded to a metal, the chemical is an organometallic; an example is methylmercury, a common water pollutant. An organic chemical can be simple, such as the methane found in natural gas, or it may be more complicated such as a vitamin. Sucrose and acetic acid are examples of common organic chemicals produced in nature, and they can also be synthesized by humans. People start with the natural organic chemicals found in petroleum, coal, or wood to make plastics, drugs, pesticides and other chemicals. The organic chemicals made in living organisms are called biochemicals; the well known biochemicals are proteins, fats, and carbohydrates. Inorganic chemicals: Inorganic chemicals can be formally defined with reference to why they are not organic chemicals. Organic chemicals are those which contain carbon, although some carbon-containing compounds are traditionally considered inorganic, for example, carbon monoxide, carbon dioxide, carbonates, cyanides, cyanates, carbides, and thyocyanates. Inorganic chemicals may contain almost any element in the periodic table from nitrogen and sulfur to lead. Traditionally, inorganic chemicals are considered to be of mineral, not biological, origin. Comparatively, most organic chemicals are traditionally viewed as being of biological origin. Differentiating chemicals from one another on the basis of whether a particular chemical is organic or inorganic is not difficult. Do not be confused by the term organic as commonly used to refer to what is “natural.” When we state that a chemical is organic what we are stating is that it contains at least one carbon atom. The term natural comes into play when speaking about organic chemicals simply because they are synthesized naturally by animals, microorganisms, and plants [2]. When the term pollutant is mentioned, certain images often form in people’s mind, depending upon their experiences. Figure 1 shows the pollution categories; the categories here are fairly logical, but others can be devised. Organic Pollutants: Examples of organic pollutants consist of Polychlorinated Biphenyls (PCBs), pesticides, hydrocarbons and aromatic amines. PCBs are one of the dangerous organic chemicals. PCBs have notable features, such as heat resistance, insulation, and chemical stability, however, PCB production was banned in the 1970s due to its high toxicity. Many pesticides are also organic pollutants, such as the once heavily used pesticide DDT and the carbamate pesticides. Oil enclosed within a tanker is not a pollutant. Spilled into the environment, however, it becomes a pollutant. A small oil spill may go unnoticed, but a large one can be disastrous. Inorganic Pollutants: Examples of inorganic pollutants consist of salt, nitrate or metals, and metals may exist as organometallic pollutants; for example, methylmercury. A common category of inorganic pollutants is the synthetic plant nutrients found in fertilizers. Nitrate, a component of fertilizers, is one example.

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The nitrogen and sulfur acids found in acid rain are also inorganic pollutants; salts are another example, including sodium chloride, which is common table salt. Rain or snow melt runoff from salt piles or roads treated with salt may contaminate well water to an extent that it becomes undrinkable. Metal emissions often are produced by industrial operations, but naturally occurring metals can also present problems. Arsenic is a natural component of bedrock in areas with granite and is sometimes found in drinking water at levels high enough to raise concern for human health. Mercury is found naturally in marine waters and some fresh waters, but it is also often the result of human activities. When electric power plants and other facilities burn coal, oil, or wastes that contain mercury, the volatile mercury escapes into the atmosphere and later settles onto land and water. In water, microorganisms can convert mercury into methylmercury, an organometallic chemical that is much more toxic than elemental mercury itself. Cadmium and lead are other metals released by these facilities [3].

Figure 1. Sources of water pollution.

Acid pollutants: The best known acid pollutants, sulfuric acid and nitric acid, have been mentioned as the inorganic pollutants found in acid rain. Acids are also found in runoff from coal mining and metal mining sites. Drainage form mines can severely acidify nearby water bodies. Physical pollutant: Physical pollutants consist primarily of solid materials found in inappropriate locations. For example, soil, carried in rainwater runoff from agricultural fields and construction sites, or the trash sitting in a vacant lot, are all physical pollutants. Another different physical pollutant is high-temperature water released from electric power plants. Radiological pollutants: Radiological pollutants are found naturally in rocks, water and soil. Two of the better known radioactive elements are radon and radium. One anthropogenic

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(man-made) source of radioactive pollutants are the hazardous waste sites in locations formerly operated for military purposes. Biological pollutants: Biological pollutants consist of pathogenic microorganisms, such as viruses, protozoa and infectious bacteria. Microorganisms are always naturally present in soil, water, air, and food, as well as on and within our bodies and those of all animals and plants. Both these microbes and those found in sewage or animal wastes can pose problems. The broader term biological pollutant includes dead and living microorganisms and fragments of insects and other organisms that can contaminate air, water or food.5 “I am, therefore I pollute.” That applies to any process, and the following words list several pollutant sources.6 • • • • • • • • • • • • • •

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•

Motor vehicles including cars, buses, airplanes, ships, and off-road vehicles. Chemical and petroleum refineries. Manufacturing facilities. Commercial operations such as dry cleaners, bakeries, and garages. Plants that generate electric power by burning coal, oil, or natural gas. Agricultural operations growing crops or raising animals. Food processing operations. Mining operations. Construction operations. Military operations. Forestry operations. Construction and road building. Consumer product use. Municipal operations including drinking-water and wastewater treatment, and road maintenance. All activities occurring in commercial and municipal buildings, and in private dwellings.

So the pollutant sources are various and they can reach the environment in many ways. The pollutant does not just stay in one place, it can move through air, water or soil, and change its form as it travels. In an accident that happened in a Swiss facility, large quantities of chemicals washed into the Rhine River; the chemicals flowed downstream into France and Germany and killed fish and other aquatic life along the way, which is the example of the water movement of pollutants. Sulfur dioxide and nitrogen oxides emitted to the atmosphere from sources burning fossil fuels can be blown many hundreds of miles. Converted to acidic substances as they travel, the result is acid deposition settling onto water and land over a whole region [4]. “Grasshopper Effect” is a special case of pollutant movement (Figure 2). Persistent and volatile pollutants, including certain pesticides, industrial chemicals and heavy metals, evaporate out of the soil in warmer regions, and travel in the atmosphere toward cooler areas, condensing out again when the temperature drops. The process of multiple cycles of evaporation and condensation, repeated in “hops,” is sometimes called the “grasshopper effect.”

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Figure 2. The Grasshopper Effect or global distillation [22].

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The Classification of Environmental Pollutants Environmental pollution includes any substance that may adversely impact our possessions or lives. There are different kinds of pollutants, each of which comes from different sources. Pollutants can be created artificially by various industrial processes, accidents, or from some indoor activities and materials. But some arise from natural processes, some of which are sudden and dramatic, such as lightning, volcanoes, earthquakes and forest fires, whilst others derive from slow continuous processes such as the decay of animal and vegetable matter. It is essential to identify the sources of pollution, in order to be able to formulate a policy to eliminate it altogether. Many approaches for pollutants classification have been used in the pollution literatures. For example, air pollutants can be divided into natural pollutants and anthropogenic pollutants. Natural pollutants are those that are found in nature. For example, volcanic activity produces sulfur dioxide, and particulate pollutants derive from forest fires. Anthropogenic pollutants are those that are produced by human activities. For example, sulfur dioxide is produced by fossil fuel combustion and particulate matter comes from diesel engines. Air pollutants can also be classified as direct or indirect. Direct pollutants are emitted directly into the atmosphere from an identifiable source, such as carbon monoxide and sulfur dioxide. Indirect pollutants are those that are produced in the atmosphere by chemical and

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physical processes from direct pollutants and natural constituents. For example, ozone is produced by hydrocarbons and oxides of nitrogen in the presence of sunlight. Different products, processes and activities of our industrialized world together have formed different environmental pollutants, but all the pollutants must come in the form of solid, liquid or are gaseous. On the basis of this fact, in this book, the pollutants are divided into four categories, solid pollutant, liquid pollutant, gaseous pollutant and other pollutant.

2.1. Solid Pollutants 2.1.1. Solid Waste Solid waste is a generic term used to describe the things we throw away. It includes all garbage, refuse, trash and other discarded solid materials resulting from residential, commercial, agriculture and other human activities. The U.S. EPA regulatory definition is broader in scope. It includes any discarded item; things destined for reuse, recycle, or reclamation; sludges; and hazardous wastes. The regulatory definition specifically excludes radioactive wastes and in situ mining wastes. In this section, we have limited the discussion to solid wastes generated from residential and commercial sources. Sludge, hazardous and radioactive waste will be discussed in the following sections.

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Characteristics of Solid Waste Massive mountains of solid wastes are disposed each day by our consumer society. It is estimated that about 10 billion tonnes of solid wastes are produced every year in the world and are dumped into their surroundings. Solid waste disposal creates a problem primarily in highly populated areas. The more concentrated the population, the greater the problem becomes. Various estimates have been made of the quantity of solid waste generated and collected per person per day. In 1998, the U.S. EPA estimated that the nation average rate of solid waste generated was 2.02 kg／capita · day, up from 1.2 kg／capita · day in 1960 [5]. On this basis, in 1998, the United States produced 200 teragrams (Tg, one Tg is equivalent to 1×1012 grams, or 1×109 kilograms (Kg), or 1×106 megagrams (Mg)) of solid waste. We may not notice our contributions to air pollution; we may likewise casually send the contaminated water we produce down drains and toilets. It is somewhat more difficult to ignore the solid waste that we produce. Trash was the bane of many cities, as people dumped anything. Households are one contributor to Municipal Solid Waste (MSW, residential and commercial trash or garbage generated by a particular municipal area), and household waste contains anything that we choose to discard, which includes waste food, papers and newspapers, packaging, bottles, metal cans, batteries, grass clippings and other yard waste, clothing, furniture and appliances, paint and other discarded household chemicals. Households are only one contributor to solid waste. Others generating solid waste are institutions such as hospitals, government offices, schools, and prisons. Commercial businesses including restaurants, grocery stores, and offices are large generators too.

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Industries also generate solid waste. Table 1 shows the sources of solid waste within a community.

The Impacts of Solid Waste Almost any garbage has unpleasant odors. Uncollected solid waste increases risk of injury, diapers and other sanitary items contain microorganisms, sometimes infectious, so do rotting food and yard wastes. Table 1. Sources of solid waste within a community [23] Source Residential

Commercial

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Institutional Construction and demolition Municipal services (Excluding treatment facilities) Treatment plant sites; Municipal incinerators Municipal solid waste Industrial

Agricultural

Typical Facilities, Activities, or Locations Where Wastes Are Generated Single family and multifamily detached dwellings, low-, medium-, and high-rise apartments, etc.

Stores, restaurants, markets, office buildings, hotels, motels, print shops, service stations, auto repair shops, etc. Schools, hospitals, prisons, governmental centers New construction sites, road repair⁄renovation sites, razing of building, broken pavement Street Cleaning, landscaping, catch basin cleaning, parks and beaches, other recreational areas

Types of Solid Wastes Food wastes, paper, cardboard, plastics, textiles, leather, yard wastes, wood, glass, tin cans, aluminum, other metals, ashes, street leaves, special wastes(including bulky items, consumer electronics, white goods, yard wastes collected separately, batteries, oil, and tires), household hazardous wastes Paper, cardboard, plastics, wood, food waste, glass, metals, special wastes(see above), hazardous wastes, etc. As above in commercial Wood, steel, concrete, dirt, etc.

Special wastes, rubbish, street sweeping, landscape and tree trimmings, catch basin debris, general wastes from parks, beaches, and recreational areas

Water, wastewater, and industrial treatment processes, etc.

Treatment plant wastes, principally composed of residual sludges

All of the above

All of the above

Construction, fabrication, light and heavy manufacturing, refineries, chemical plants, power plants, demolition, etc.

Industrial process wastes, scrap materials, etc. Nonindustrial wastes including food wastes, rubbish, ashes, demolition and construction wastes, special wastes, hazardous wastes

Field and row crops, orchards, vineyards, dairies, feedlots, farms, etc.

Spoiled food wastes, agricultural wastes, rubbish, hazardous wastes.

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The group at risk from the unscientific disposal of solid waste include the population in areas where there is no proper waste disposal method, especially the preschool children, waste workers, and workers in facilities producing toxic and infectious material. Other high-risk groups include the population living close to a waste dump and those whose water supply has become contaminated either due to waste dumping or leakage from landfill sites. Waste dumped near a water source causes contamination of the water body or the ground water source, and uncollected solid waste can also obstruct storm water runoff, resulting in the forming of stagnant water bodies that become breeding grounds of disease. Over the last few years, the consumer market has grown rapidly, leading to products being packed in cans, aluminium foils, plastics, and other such non-biodegradable items that cause incalculable harm to the environment. The unhygienic use and disposal of plastics and its effects on human health has become a matter of concern. Coloured plastics are harmful as their pigment contains heavy metals that are highly toxic. Some of the harmful metals found in plastics are copper, lead, chromium, cobalt, selenium, and cadmium. Solid wastes need not be hazardous to present problems; the large amount of trash generated presents concerns: How do we handle it and where should it go? Consider packaging, generated in large quantities. The composition of packaging may make it very difficult to recycle, or prevent it from biodegrading. If it contains hazardous metals, expensive controls are necessary to prevent metal emissions if it is incinerated. Or, if disposed of in a landfill, much of this waste can last indefinitely. Even when dumped in the open environment where there is sunlight, heat, and water, many items are long lasting. Table 2 shows the type of litter we generate and the approximate time it takes to degenerate.

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Table 2. The type of litter we generate and the approximate time it takes to degenerate Type of litter Organic waste such as vegetable and fruit peels, leftover foodstuff, etc. Paper Cotton cloth Wood Woolen items Tin, aluminium, and other metal items such as cans Plastic bags Glass bottles

Time needed to degrade One or two weeks 10-30 days 2-5 months 10-15 years One year 100-500 years May be one million years Undetermined

The United States alone, with its 100 million households, generated 232 million tons of municipal solid waste in 2000. Handling waste is expensive whether it is incinerated or landfilled, or recycled. Americans pay about $30 billion per year for waste management, second or third only to the amount communities spend on education and police protection.

2.1.2. Hazardous Waste Introduction to Hazardous Waste Hazardous waste is waste with properties that make it dangerous or potentially harmful to human health or the environment. As with municipal solid waste, hazardous waste is also a

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small percentage of total wastes, but hazardous waste has been abandoned at many thousands of sites around the world. At these sites, hazardous substances evaporate into the air, contaminate soil, seep into groundwater or run off into nearby water. Hazardous waste is not a specific chemical. As defined by the US Resource Conservation and Recovery Act (RCRA), it is a legal term given to waste that has one or more of the following characteristics – ignitability, corrosivity, reactivity, or toxicity. Ignitable wastes can create fires under certain conditions, are spontaneously combustible. Ignitable waste is a fire hazard. Petroleum distillates and many organic solvents are ignitable. Corrosive wastes can cause grievous injury at the point of contact: the skin, eyes, lungs, or the mouth. Strong acids and alkalis are corrosive, and so are chlorine and hydrogen peroxide. Corrosive wastes are capable of corroding metal containers, such as storage tanks and barrels. Reactive wastes are unstable under “normal” conditions. They can cause explosions, toxic fumes, gases, or vapors when heated, compressed, or mixed with water. More familiar reactive substances are dynamite, gun ammunition, and firecrackers. Toxic wastes are harmful or fatal when ingested or absorbed. Examples are arsenic and cyanide, pesticides and many metals. Hazardous waste is considered solid waste under the RCRA, but the universe of hazardous wastes is large and diverse. Hazardous wastes can be solids, liquids, contained gases, or sludges. They can be the by-products of manufacturing processes or simply discarded commercial products, like cleaning fluids or pesticides.

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Sources of Hazardous Waste Hazardous waste is produced both on a huge scale by major industries and on a relatively tiny scale by individuals. No matter where it comes from, waste can be dangerous. Most hazardous waste is generated by large facilities that manufacture chemicals, petroleum, metal, plastic, and textile products. Large petroleum refineries and chemical manufacturers generated up to 90% of the approximately 270 million tons of hazardous waste that the United States produced in 1998. Manufacturers of metal products are another large generator, producing wastewater with high-enough concentrations of metals to be hazardous. Military operations also generate large quantities of hazardous waste. Small businesses, such as gas stations, auto repair shops, photographic developers, and dry cleaners, produce many toxic waste products. These by-products include sulfuric acids, heavy metals found in batteries, and silver-bearing waste, which comes from photo finishers, printers, dentists, doctors, and veterinarians. Heavy metals, solvents, and contaminated wastewater result from paint manufacturing. Photo processing also creates organic chemicals, chromium compounds, phosphates, and ammonium compounds. Even cyanide can be a byproduct, resulting from electroplating and other surface-treatment processes. Hospital waste contaminated by chemicals used in hospitals is considered hazardous. These chemicals include formaldehyde and phenols, which are used as disinfectants, and mercury, which is used in thermometers or equipment that measure blood pressure. Hospital wastes also include swabs, bandages, human excreta, and discarded medicines. It has been roughly estimated that of the 4 kg of waste generated in a hospital at least 1 kg would be infected. This waste is highly infectious and can be a serious threat to human health if not managed in a scientific manner.

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If you think industry is the only source of hazardous waste, you may be surprised. There is hazardous household waste as well. Some examples of household hazardous waste are old batteries, shoe polish, old medicines and medicine bottles; oil-based paints and thinners, furniture strippers; automotive products, such as gasoline, antifreeze, lubricants, car wax, brake fluid, and batteries; poor chemicals, fertilizers, pesticides, herbicides; and other household cleaning products. These products can be harmful to the environment if they are not disposed of properly, which means they should not be dumped down the drain, and empty or partially empty hazardous waste containers should not be thrown in the garbage.

Impact of Hazardous Waste

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One of the main causes of the abundance of hazardous waste is that people do not realize how large a problem it is. Because it can be simply removed and sent to a landfill, it is often assumed that the problem ends there. Industries have often displayed an unwillingness to find ways to deal with hazardous waste because of the expenses associated with it, many industries and governments create crude landfills to store waste, and often just dump waste chemicals into nearby bodies of water. Sadly, it is often only after someone has died or become seriously ill that governments will intervene and reduce levels of dumped hazardous waste. Increasing amounts of hazardous waste have caused increasing health problems. Health problems occur because of the chemical and physical nature of the waste, and its concentration and quantity; the impact also depends on the duration of exposure. Adverse effects on humans range from minor temporary physical irritation, dizziness, headaches, and nausea to long-term disorders, cancer or death. Table 3 shows the potential effects of selected hazardous substances. Table 3. Health effects of selected hazardous substances [24] Chemical Pesticides DDT BHC Petrochemicals BENZENE VINYL CHLORIDE

Source

Health Effects

Insecticides Insecticides

Cancer; damage to liver, embryos, bird eggs Cancer, embryo damage

Solvents, pharmaceuticals and detergents Plastics

Headaches, nausea, loss of muscle coordination, leukemia, damage to bone marrow Lung and liver cancer, depression of central nervous system, suspected embryotoxin

Other Organic Chemicals DIOXIN Herbicides, waste incineration PCBs Electronics, hydraulic fluid, fluorescent lights Heavy Metals LEAD Paint, gasoline

CADMIUM

Zinc, batteries, fertilizer

Cancer, birth defects, skin disease Skin damage, possible gastro-intestinal damage, possibly cancer-causing Neurotoxic; causes headaches, irritability, mental impairment in children, brain, liver, and kidney damage Cancer in animals, damage to liver and kidneys

Hazardous waste can also cause environmental contamination. Dangerous chemicals often migrate from uncontrolled sites, percolating from holding ponds and pits into

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underlying groundwater, then flowing into lakes, streams, and wetlands. Produce and livestock in turn become contaminated, and then enter the food chain. Hazardous chemicals then build up, when plants, animals, and people consume contaminated food and water. There are many case histories that epitomize our concern with hazardous wastes. That which is common practice today may be the seed of disaster for tomorrow.

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2.1.3. Radioactive Waste Sources of Radioactivity in the Environment Pollution of the natural environment by radioactive substances is of concern because of the considerable potential that ionizing radiation has for damaging biological material and because of the very long half-lives of some radionuclides [6]. Radioactivity is defined as the property possessed by some elements with spontaneously emitting alpha particles (α), beta particles (β), or sometimes gamma rays (γ) by the disintegration of the nuclei of atoms. It is a naturally occurring phenomenon, and can not be stopped. The process of unstable nuclei giving off energy to reach a stable condition is called radioactive decay. This process produces nuclear radiation, and the emitting isotopes are called radionuclides (radio isotopes). All decay processes result from energy changes that eventually result in the formation of a stable nucleus. All radioisotopes follow the same law of decay: a fixed fraction of the atoms present will decay in a unit of time. That is, for each isotope there is a period of time during which half of the atoms initially present will decay. Each radioactive element can be characterized by the time it takes for half of the element to decay; this is called half-life of the element. Some elements decay in seconds while others take thousands of years. Since the rate of radioactive decay is not dependent on physical variables such as temperature or pressure, the half-life of each radioisotope is constant. Radioactivity in the environment comes from natural and man-made sources. Although natural radioactivity is the most likely to be encountered in the environment due to its widespread dispersal, man-made radioactivity poses the greatest environmental risk. Natural radioactivity harnessed by man and not properly disposed of is also a potential threat to the environment. There are five basic sources of radioactivity in the environment: the nuclear fuel cycle, mining activities, medical and laboratory facilities, nuclear weapons testing and seepage from natural deposits [7]. Nuclear fuel cycle: The nuclear fuel cycle is defined as the activities carried out to produce energy from nuclear fuel. These activities include, but are not limited to, the mining of uranium-containing ores, enrichment of uranium to fuel grade specifications, fabrication and use of fuel rods, and isolation and storage of waste produced from power plants. A current concern in the nuclear power field is the safe disposal and isolation of either spent fuel from reactors or, if the reprocessing option is used, wastes from reprocessing plants. This waste will remain radioactive for many thousands of years; they must be isolated from the biosphere until the radioactivity contained in them has diminished to a safe level. Mining activities: Mining, processing, and the use of coal, natural gas, phosphate rock, and rare earth deposits result in the concentration and release or disposal of large amounts of low-level radioactive material. Medical and laboratory facilities: Radioisotopes are used extensively in medical facilities and biomedical research laboratories. Clinical use of radioisotopes is expanding rapidly in

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such areas as cancer treatment and diagnostic testing. Although most of these isotopes are strong emitters of gamma radiation, they have short half lives. Nuclear weapons testing: The use of nuclear devices in weapons is the primary cause of radioactive fallout. Tritium and several isotopes of iodine, cesium and strontium are found in the environment largely because of nuclear testing. In the United States, a large percent of radioactive waste results from defense department activities. Natural deposits: The majority of radioactivity in groundwater is due to seepage from natural deposits of uranium and thorium (Table 4), and natural radioactivity is common in the rocks and soil that makes up our planet. Natural sources of radioactivity also include radon gas, which is colorless, odorless, inert and emitted from beneath the ground. In the United States, people are typically exposed to about 350 millirems of ionizing radiation per year, and the major natural source of radiation is radon gas, which accounts for about 55% of the total radiation dose.

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Table 4. Average soil and rock concentration of uranium and thorium [25]

Rocks Igneous Silica (granites) Intermediate (diorites) Mafic (basalt) Ultramafic (dunites) Sedimentary Limestones Carbonates Sandstones Shales (Mean value in earth’s crust) Soils Typical range World average Average specific activity (pCi／kg)

Uranium (mg／kg)

Thorium (mg／kg)

4.7 1.8 0.9 0.03

20.0 8.0 2.7 6.0

2.2 2.1 1.5 3.5 3.0

1.7 1.9 3.0 11.0 11.4

1-4 2 670

2 - 12 6.7 650

Biological Effects of Radioactivity Since even a small amount of radiation exposure can have serious (and cumulative) biological consequences, and since many radioactive wastes remain toxic for centuries, radioactive pollution is a serious environmental concern even though natural sources of radioactivity far exceed artificial ones at present. The problem of radioactive pollution is compounded by the difficulty in assessing its effects. Radioactive waste may spread over a broad area quite rapidly and irregularly, and may not fully show its effects upon humans and organisms for decades in the form of cancer or other chronic diseases. Radioactivity is toxic because it forms ions when it reacts with biological molecules. These ions can form free radicals, which damage proteins, membranes, and nucleic acids. The range of effects include cataracts, gastrointestinal disorders, blood disorders including

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leukaemia, damage to the central nervous system, cancer, genetic damage and changes to chromosomes producing mutations in later generations. The biological effect of radiation is measured in units called rems. The permissible level for occupational radiation exposure is five rems per year to the whole body. It is believed that this level can be absorbed for a working lifetime without any sign of biological damage. The first case of human injury was reported in the literature just a few months following Roentgen’s original paper in 1895 announcing the discovery of x-rays. As early as 1902, the first case of x-ray induced cancer was reported in literature. The long-term biological significance of small, chronic doses of radiation, however, was not widely appreciated until the 1950s, and most of our current knowledge of the biological effects radiation has been accumulated since World War II. One of the most informative studies of the harmful effects of radiation is a long-term investigation of the survivors of the 1945 atomic blasts at Hiroshima and Nagasaki by James Neel and his colleagues. The survivors of these explosions had abnormally high rates of cancer, leukemia, and other diseases. However, there seemed to be no detectable effect on the occurrence of genetic defects in children of the survivors. Radioactive pollution is an important environmental problem. It could become much worse if extreme vigilance is not utilized in the handling and use of radioactive materials, and in the design and operation of nuclear power fields.

2.2.Liquid Pollutants

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2.2.1. Wastewater Source of Wastewater Do you know what happens to the water when you pull the plug, flush the toilet or drain the washing machine? This so-called “wastewater” is not only a vital resource but, after treatment, will be released to our land, waterways or the ocean. Wastewater is any water that has been adversely affected in quality by anthropogenic influence. It comprises liquid waste discharged by domestic residences, commercial properties, industry, and/or agriculture and can encompass a wide range of potential contaminants and concentrations [8]. Wastewater comes from a variety of sources; every building with running water generates some sort of wastewater: Domestic wastewater: used in toilets, showers, baths, kitchen sinks and laundries in homes and offices is domestic wastewater. Industrial wastewater: Wastewater from manufacturing and industrial operations such as food processing, metal refining or mining operation. This includes liquid waste from any process, such as the water used to cool machinery or clean plant and equipment. Agricultural wastewater: generated from a variety of farm activities including animal feeding operations and the processing of agricultural products. Stormwater: A form of wastewater is runoff that flows from agricultural and urban areas such as roofs, parks, gardens, roads, paths and gutters into stormwater drains after rain. Wastewater pollution has always been a major problem throughout the world. Wastewater may contain contaminants such as oil, dirt, human waste, and chemicals, if it is

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not treated before being discharged into waterways, serious pollution is the result. Unless properly treated, wastewater can harm public health and the environment. The water we use never really goes away. In fact, there never will be any more or any less water on Earth than there is right now, which means that all of the wastewater generated by our communities each day from homes, farms, businesses, and factories eventually returns to the environment to be used again. So, when wastewater receives inadequate treatment, the overall quality of the world’s water supply suffers.

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What is in Wastewater? Wastewater is mostly water by weight. Other materials make up only a small portion of wastewater, but can be present in large enough quantities to endanger public health and the environment. Anything can be flushed down a toilet, drain, or sewer; even household sewage contains many potential pollutants. The wastewater components that should be of most concern to homeowners and communities are those that have the potential to cause disease or detrimental environmental effects. Organisms: Many different types of organisms live in wastewater and some are essential contributors to treatment. A variety of bacteria, protozoa, and worms work to break down certain organic pollutants in wastewater by consuming them. Through this process, organisms turn wastes into carbon dioxide, water, or new cell growth. Bacteria and other microorganisms are particularly plentiful in wastewater and accomplish most of the treatment. Most wastewater treatment systems are designed to rely in large part on biological processes. Pathogens: Many disease-causing viruses, parasites, and bacteria also are present in wastewater and enter from almost anywhere in the community. These pathogens often originate from people and animals that are infected with or are carriers of a disease. The likely sources in communities include hospitals, schools, farms, and food processing plants. The important wastewater-related diseases, such as gastroenteritis, hepatitis A, typhoid, cholera, and dysentery, can result from a variety of pathogens in wastewater. Outbreaks of these diseases can occur as a result of drinking water from wells polluted by wastewater. Even municipal drinking water sources are not completely immune to health risks from wastewater pathogens. Drinking water treatment efforts can become overwhelmed when water resources are heavily polluted by wastewater. For this reason, wastewater treatment is as important to public health as drinking water treatment. Organic Matter: Organic materials in wastewater originate from plants, animals, or synthetic organic compounds, and enter wastewater in human wastes, paper products, detergents, cosmetics, and foods. Many organics are proteins, carbohydrates, or fats and are biodegradable, which means they can be consumed and broken down by organisms. However, even biodegradable materials can cause pollution. Large amounts of biodegradable materials are dangerous to lakes, streams, and oceans, because organisms use dissolved oxygen in the water to break down the wastes. This can reduce or deplete the supply of oxygen in the water needed by aquatic life, resulting in fish deaths, odors, and overall degradation of water quality. The amount of oxygen organisms need to break down wastes in wastewater is referred to as the biochemical oxygen demand (BOD5) and is one of the measurements used to assess overall wastewater strength. Some organic compounds are more stable than others and cannot be quickly broken down by organisms, posing an additional

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challenge for treatment. This is true of many synthetic organic compounds developed for agriculture and industry. In addition, certain synthetic organics are highly toxic. Pesticides and herbicides are toxic to humans, fish, and aquatic plants and often are disposed of improperly in drains or carried in stormwater. Inorganic Matter: Inorganic minerals, metals, and compounds, such as sodium, potassium, calcium, magnesium, cadmium, copper, lead, nickel, and zinc are common in wastewater. They can originate from industrial and commercial sources, stormwater, and inflow and infiltration from cracked pipes and leaky manhole covers. Most inorganic substances are relatively stable, and cannot be broken down easily in wastewater. Large amounts of inorganic substances can contaminate soil and water; some are toxic to animals and humans and may accumulate in the environment. Nutrients: Wastewater often contains large amounts of the nutrients nitrogen and phosphorus in the form of nitrate and phosphate, which promote plant growth. Organisms only require small amounts of nutrients in biological treatment, so there normally is an excess available in treated wastewater. In severe cases, excessive nutrients in receiving waters cause algae and other plants to grow quickly depleting oxygen in the water. Nutrients from wastewater have also linked to ocean “red tides” that poison fish and cause illness in humans. Solids: Solids in wastewater must be reduced by treatment, because they can increase BOD5 when discharged to receiving waters and provide places for microorganisms to escape disinfection. Settleable solids such as sand, grit, heavier organic and inorganic materials will settle out from the wastewater stream during the preliminary stages of wastewater treatment, and the solid organic material makes up a biologically active layer of sludge on the bottom of settling tanks. Suspended solids which resist settling may remain suspended in wastewater, suspended solids in wastewater must be treated, because they will clog soil absorption systems or reduce the effectiveness of disinfection systems. Dissolved solids can dissolve like salt in water, and some dissolved materials are consumed by microorganisms in wastewater, but others, such as heavy metals, are difficult to remove by conventional treatment. Excessive amounts of dissolved solids in wastewater can have adverse effects on the environment. Oil and Grease: Fatty organic materials from animals, vegetables, and petroleum are not quickly broken down by bacteria and can cause pollution in receiving waters. When large amounts of oils and greases are discharged to receiving waters, they increase BOD and trap trash, plants, and other materials, causing foul odors, attracting flies and mosquitoes and other disease vectors. Petroleum-based waste oils used for motors and industry are considered hazardous waste and should be collected and disposed of separately from wastewater. Gases: Such as hydrogen sulfide, carbon dioxide and methane. Gases in wastewater can cause odors, or are potentially dangerous. Methane gas, for example, is highly combustible. The gases hydrogen sulfide and ammonia can be toxic and pose asphyxiation hazards. Both gases emit odors, which can be a serious nuisance.

Domestic Wastewater Domestic households produce an average of 200- 300L of wastewater per person every day! Much of the wastewater we produce has been changed in a way that means it cannot be used again unless it is treated.

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Many household products are potentially hazardous to people and the environment and never should be flushed down drains, toilets, or storm sewers. Some examples of hazardous household materials include motor oil, transmission fluid, antifreeze, paint, paint thinner, varnish, polish, wax, solvents, pesticides, rat poison, oven cleaner, and battery fluid. Treatment plant workers can be injured and wastewater systems can be damaged as a result of improper disposal of hazardous materials. The disposal of fats, oils and grease down sinks and drains, and the incorrect disposal of items such as cotton buds and nappies down the toilet are significant causes of sewer blockages and flooding. In addition, there are thousands of chemicals in domestic wastewater resulting from the use of cleaning, pharmaceutical, and hygiene products that cannot be removed or treated in wastewater treatment systems, and may reach local drinking water sources. Table 5 shows the typical major pollutant of untreated domestic wastewater.

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Table 5. Typical Major Pollutants of Untreated Domestic Wastewater 8 Physical Volatile Suspended Solids Fixed Suspended Solids Total Suspended Solids (TSS) Volatile Dissolved Solids Fixed Dissolved Solids Total Dissolved Solids (TDS) Chemical Biochemical Oxygen Demand (BOD5) Chemical Oxygen Demand (COD) Total Organic Carbon (TOC) Organic N Free Ammonia N Total Nitrogen Organic P Inorganic P Total Phosphorus Fats, oil and grease Fecal Coliforms Non-fecal Coliforms Total Coliforms Total Viruses

Concentrate (mg/L) 240 60 300 175 265 440 250 500 160 15 25 40 4 5 9 100 107-108 MPN/L 9×107-9×108 MPN/L 108-109 MPN/L 1,000-10,0000 infectious units/L

Construction of public underground sewerage systems is the key to minimizing domestic water pollution. Several advanced nations have considered the construction of public underground sewerage systems as an indicator of national competitiveness. But change in our behavior would be more efficient to reduce the pollutant load of domestic wastewater and sewer blockages, and therefore reduce damage to the environment and risk to our valued water resources.

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Industrial Wastewater The main industrial polluters include chemical, food, and pulp and paper industries, the wastewater from such plants significantly raise the levels of heavy metals and organic or inorganic pollutants in the water system. Table 6. Examples of Industrial Wastewater Concentrations for BOD5 and TSS [26]

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Industry Ammunition Fermentation Slaughterhouse Pulp and paper Tannery

BOD5 (mg/L) 50-300 4500 400-2500 100-350 700-7000

TSS (mg/L) 70-1700 10,000 400-1000 75-300 4000-20,000

The immediate environmental impacts of the inadequate wastewater treatment include water pollution, groundwater and soil contamination, and the reduced availability of clean water. Other longer-term impacts can include the depletion of natural resources, landscape degradation, reductions in biodiversity, and health risks. The problems associated by industrial activities are caused by discharges of wastewater into the sewerage systems without pre-treatment and by inadequate treatment facilities. Extra treatment steps are essential to remove inorganic materials from industrial wastewater sources. For example, heavy metals, which are discharged with many types of industrial wastewaters, are difficult to remove by conventional treatment methods. Although acute poisonings from heavy metals in drinking water are rare, potential long-term health effects of ingesting small amounts of some inorganic substances over an extended period of time are possible. Industrial wastewater also contains pesticides, which can contaminate the groundwater, and the mass consumption of unhealthy water can be severe to the population’s health. Mining operations, both underground and open pit, generate large volumes of wastewater. In China, the discharge of wastewater in the process of ore separation amounted to 3.6 billion tons annually, and little wastewater met the standard of industrial wastewater drainage. Much wastewater contained harmful metallic ions, and the concentration of solid suspended substances is far beyond the standards. Wastewater discharged without any treatment can contaminate surface and groundwater water, surrounding crops and farmlands. In Jiangxi province, the acidic wastewater discharged from a polymetallic mine, has led to the serious river water pollution —fishes vanished in this river which is 25 km long, plants perished, and the river water could not be used for drinking any more.

Agricultural Wastewater It is well known that agriculture is the single largest user of freshwater resources, using a global average of 70% of all surface water supplies. However, agriculture is a cause of water pollution. As the FAO (Food and Agriculture Organization of the United Nations) makes quite clear, “Appropriate steps must be taken to ensure that agricultural activities do not adversely affect water quality so that subsequent uses of water for different purposes are not

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impaired.” Agriculture wastewater can come from the animal feedlots, farm irrigation, dairy farming and orchards, and may contain phosphorus, nitrogen, metals, artificial fertilizer residues, insecticides, herbicides, pesticides, pathogens or salt; all of which are potentially very harmful. Pesticide-containing wastewaters from agriculture that enter the environment can give rise to severe and long-lasting ecological damage. Many of the farmlands requires the uses of some type of pesticide to maintain their cropland, effluent wastes containing pesticides pouring into the streams, lakes, and rivers eventually seeps into the groundwater. However, water is neither produced nor destroyed and the amount of vital usable water is quite limited. As you may know, there is a water shortage taking place right now in the urban, industrial, and agricultural sectors within China. To help alleviate the water shortage, wastewater treatment plants will help increase the supply of usable water, improve the environment, and reduce water pollution. Pesticides and herbicides are toxic to humans, fish, and aquatic plants and often are disposed of improperly in drains or carried in stormwater. In receiving waters, they kill or contaminate fish, making them unfit to eat. They also can damage processes in treatment plants. Benzene and toluene are two toxic organic compounds found in some solvents, pesticides, and other products. Additionally, the excessive application of fertilizers in agriculture causes the nutrient pollution in ditches, rivers and lakes. Phytoplankton and algae thrive in the nutrient-rich water. However, excessive algae can discolour the water, give an unpleasant smell and rob the water of valuable oxygen as bacteria work overtime feeding on dead algae remains. Blue-green algae can also produce toxins, which kill wildlife, cause skin rashes, and cause pains and stomach upsets. Milk spillage, silage liquor, and cattle and pig slurry are all examples of pollution sources in the agricultural wastewater. Accidental milk spillage from dairies is a serious contaminant. Cattle and pig slurry contain elevated levels of copper that can be toxic in the natural environment, and ascarid worms are also common and can infect humans if wastewater treatment is ineffective. Silage liquor is even stronger than slurry, with a low pH value, silage liquor can be highly corrosive; it can attack synthetic materials, causing damage to storage equipment, and can lead to accidental spillage.

Stormwater Stormwater is water from precipitation that flows across the ground and pavement when it rains or when snow and ice melt. The water seeps into the ground or drains into what we call storm sewers. Stromwater is a concern to us because of two main issues: one related to its volume, the other related to the pollutants it carries. As stormwater travels over the land, it picks up all kinds of chemicals and sediments that are not naturally found in our waterways, such as heavy metals, bacteria, pesticides, suspended solids, nutrients, and floating materials. In the United States, stormwater runoff from residential, commercial, and industrial areas is responsible for 21% of impaired lakes and 45% of impaired estuaries [9]. The impacts from stormwater are caused not only by the pollutants in the runoff, but also by its volume. As the water flows over land it can erode soil and then redeposit that soil in streams, causing muddy water and degrading aquatic habitats.

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The main pollutants in the stormwater can be divided into three categories: natural pollutant, such as leaves, garden clippings and animal droppings; chemical pollutant, such as detergents, coolant, oil, grease, fertilizers and paint; and litter pollutant, such as plastic bags, cigarette butts, paper and cans. The pollutant in stormwater ends up discharging into waterways as sediment, sludge and solids. These can be caught in stormwater treatment measures, but the most effective way to reduce this problem is to prevent pollution entering the stormwater system in the first place. The traps don't catch all the silt or litter, and they don't stop chemicals. Table 7 shows the environmental impacts of stormwater pollution. Table 7. Environmental Impacts of Stormwater Pollution [27] Issue Animal and human waste

Dissolved solids (salinity)

Heavy metals(e.g. cadmium, chromium, copper, zinc and lead)

High runoff rates

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Litter

Nutrients (nitrogen and phosphorous)

Oil and grease

Sediment (e.g. soil, sand, clay, and dust)

Probable Sources Leaking septic tanks, run-off from animal holding yards, and dog droppings. Primarily groundwater. Possibly also from air-conditioning and cooling systems Runoff from roads and carparks, deterioration of building surfaces (e.g. roofs), swimming pool water, air conditioning coolants, pesticides, batteries and electroplating. Impervious surfaces (e.g. roads, roofs, paved areas, and footpaths) directly connected to the stormwater system. Littering (e.g. bottles, cigarette butts, and plastic bags), overflowing rubbish bins, tree litter and vegetation, uncovered truck and trailer loads. Decaying vegetation (e.g. leaves and lawn clippings), treated wastewater, excess fertilizers, biodegradable detergents, animal droppings, washdown water from cars, leaky sewage systems and irrigated lawns. Runoff from roadways or carparks, poor storage and/or illegal dumping of waste lubricating oils. Erosion from building sites and bare earth (e.g. unsealed roads), soil stockpiles on footpaths, roads and driveways, washing cars in the street.

Environmental Impacts Increased nutrient levels in stormwater which lead to an increase in toxic algal blooms. Alters the chemical balance of our waterways, which may kill some aquatic plants and animals. Have toxic effects on aquatic plants and animals. Can build up in aquatic species, such as mussels, and have a dangerous impact on the food chain. Increased pollution of waterways, erosion of creek banks, lowering of water levels in wetlands which affects aquatic flora and fauna, increased flow disturbance which can reduce the diversity of aquatic life. Visual pollution. Toxins in the litter can kill fish, dolphins, and birds. Decaying litter can reduce water oxygen levels and kill aquatic animals and plants. Promotes toxic and non-toxic algal blooms which reduce the amount of light and oxygen in the water, disadvantaging other plants and animals. Also promotes unwanted weed growth. Form a film over water and makes it difficult for aquatic animals and plants to breath. Can be toxic to plants and animals. Smothering of plants and animals that live on the bottom of rivers, creeks, and the sea. Increase in sedimentation of the water. Heavy metals and other pollutants attach to the sediment particles, which transport them through waterways and harm water quality.

2.2.2. Sludge Problems When the wastewater is treated and discharged to a watercourse, the job is not over. Left behind are the solids, suspended in water, commonly called sludge. The sludge is made of

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materials settled from the raw wastewater and of solids generated in the wastewater treatment process (Figure 3).

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Figure 3. Wastewater treatment process [4].

Large quantities of sludge is a result of wastewater treatment. Initially, the sand, broken glass, small stones, and other dense material that is collected in the grit chamber is not true sludge in the sense that it is not fluid. However, it still requires disposal.Grit can be drained of water easily and is relatively stable to biological activity. In the primary treatment, primary sludge from the bottom of the primary clarifiers contains 3-8% solids (1% solids=1 g solids／100mL sludge volume), which is approximately 70% organic. This sludge rapidly becomes anaerobic and is highly odiferous. And secondary sludge consists of microorganisms and inert material that have been wasted form the secondary treatment processes. Thus, the solids are about 90% organic. When the supply of air is removed, this sludge also becomes anaerobic, creating noxious conditions if not treated before disposal. In the past sludge was dumped at sea, landfilled or incinerated. Dumping at sea is prohibited in the United States and a number of other countries. Landfills are costly and limited in capacity. Europeans are increasingly incinerate the sludge, but then they must still deal with the ash, and incineration has its owm staggering costs and complexities. Sludge contains nutrients, chemicals which help plants to grow, so sludge can be used to replace other kinds of fertilizers. One problem with spreading sludge on land is that some sludge contain chemicals that are toxic; that means they can injure our health if they get into the food we eat or the water we drink. Land application is running into resistance and regulatory issues. Bad operation of the wastes treatment plants, inadequate treatment and disposal of the sludge, and lack of the standards for sludge management are all problems associated to the current treatment systems. Sludge is one major source of polluting in urban areas. It can enter open water in a mumber of ways including: discharge form water pollution control plants, sewage system malfunctions and storm water runoff. Microorganisms derived from sludge, including bacteria viruses, and parasites can infect humans at beaches as well as the living organisms in oceans.

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Various nutrients in the waste products contained in sludge, including nitrogen and phosphate based fertilizing agents, cause oceans to undergo eutrophication. When this occurs, the ocean water becomes enriched by inorganic nutrients used by phytoplankton. This, in turn, leads to excessive bacterial growth, and algal bloom. After the algae die off, decomposers use up all of the available oxygen during cellular respiration. The result is a massive fish kill, and a depletion of fish populations.

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2.2.3 Oil Pollution Oil Pollution Sources Oil is a general term used to denote petroleum products which mainly consist of hydrocarbons. Crude oils are made up of a wide spectrum of hydrocarbons ranging from very volatile, light materials such as propane and benzene to more complex heavy compounds such as bitumens, asphaltenes, resins and waxes. Refined products such as petrol or fuel oil are composed of smaller and more specific ranges of these hydrocarbons. Oil pollution is simply the spilling of crude or refined petroleum product into the environment. The major oil pollution sources include: Oil release on land: Oil release on land happens every day all over the world. Since many humans rely heavily on petroleum products such as plastic, fuel, and lubricating oil, oil spills are an unfortunate byproduct of the human way of life. Oil spill also occurs when filling, emptying and cleaning tanks or pipes, or in the everyday running of factories, pipelines, or oil wells on land, which may result from technical failure, negligence, vandalism, accidents or armed conflict. After a spill, the majority of the product evaporates and the rest is biodegraded during its journey as run-off or through the sewer or drainage system. Other more persistent substances may flow into the sewer system and end up in the sea. Oil tanker accidents: Oil tanker accidents, such as explosion, grounding and collision, release large volumes of oil into the ocean at once, posing a serious threat to marine animals and seabirds. According to insurer’s statistics, 80% of oil tanker accidents which cause oil spills at sea are a result of human errors [10]. Analysis of significant spills shows that a high proportion of spills are due to groundings and collisions. Collisions are generally due to manoeuvring errors, especially in poor visibility or busy shipping traffic areas. Groundings are also often a result of manoeuvring errors, often made worse by high winds, challenging currents and bad weather. Operational discharge: Marine transportation has increased enormously in recent years. A significant amount of oil comes into the sea from operational discharges. Operational discharge means the release of wastewaters(including ballast and bilge waters) containing a certain quantity of hydrocarbons at sea form oil-tanks and non-tanks. Operational discharges are mostly deliberate and “routine,” and can be effectively controlled and avoided. Natural seepage: Oil spills can also be caused by natural seepage, such as release from the ocean bottom and eroding sedimentary rocks. Natural seepage from the rocks beneath the sea floor accounts for about half of oil entry into oceans, that which occurs over widespread areas of the sea floor and does not result from human activity. Natural seepage can also be accelerated through human activity, such as drilling.

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Oil Pollution Impacts The exact nature and duration of any impacts from an oil spill depend on a number of factors. These include the type and amount of oil and its behaviour once spilled; the physical characteristics of the affected area; weather conditions and season; the type and effectiveness of the clean-up response; the biological and economic characteristics of the area and their sensitivity to oil pollution [11]. Oil spills may result in widespread death of wildlife and fish. Physical contact, ingestion, and destruction of food resources are all different ways that oil spill can kill organism. The effects of spilled oil can spread through food chains to disturb species that depend on each other for sustenance. You may always see some picutres and videos of wildlife covered in black, sticky oil after an oil spill, and these pictures are usually of oiled birds. Other marine life such as marine mammals can also suffer from the effects of an oil spill. Even small spills can severely affect marine wildlife. The effects of oil spill on birds include the external effets associated with oiling of plumage and the internal effects associated with the pathological effects of ingested oil [12]. The life of a bird depends on regular contact with the water surface in the case of finding food or having rest between flights. Oil destroys the waterproofing and insulating properties of the plumage. The bird will suffer from chilling and it is often unable to fly or remain afloat in the water. The bird has difficulty in obtaining food or escaping predators. Whales, dolphins and seals in the open sea do not appear to be particularly at risk from oil spills. Marine mammals such as seals and otters that breed on shorelines are, however, more likely to encounter oil. Species which rely on fur to regulate their body temperature are the most vulnerable since, if the fur becomes matted with oil, the animals may die from hypothermia or overheating. Oil spills in the open sea also affect the surface layers of plankton, which is the first element in the food chain, as large marine mammals feed on them. Other threats to wildlife are the risks of direct ingestion, irritation of the eyes and nostrils, inhalation of toxic vapours, suffocation by coating with oil as well as longer term toxic effects impairing the organism’s metabolism. Shorelines, more than any other part of the marine environment, are exposed to the effects of oil as this is where it naturally tends to accumulate. The algae, fish and shellfish which live in coastal pools, on the rocks and in the sand or mud, are inevitably affected. Marine birds and mammals, such as numerous species of birds feeding on the foreshore at low tide and nesting on the seafront, or marine mammals resting on the shore, are also obvious victims. Depending on the type of shoreline, the impact can range from being relatively limited to extremely serious. Rocky and sandy shores exposed to wave action and the scouring effects of tidal currents suffer relatively little from oil spill as they usually selfclean quite rapidly. The arrival of oil at the shoreline can be detrimental to many human activities. Swimming in the sea, recreational fishing, diving, surfing, and sailing all become impossible amongst oil slicks, causing economic and social consequences which can be very significant in popular tourist regions. Industries which require a constant seawater supply for their normal operation can also be adversely affected by oil spills, such as desalination stations, electric power stations, thalassotherapy centres, and marine aquariums. If the impact is mild and transient, it may generate only a slight inconvenience. If it is more serious, it can paralyse activities until clean-up is complete, or impose the destruction of stocks destined for future production.

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2.3. Gaseous Pollutants A different mix of vapors and gaseous pollutants can be found in outdoor and indoor environments. Outdoor gaseous pollutants primarily come from the combustion of fossil fuels in power plants, various industrial processes, and motor vehicles. Indoor gaseous pollutants come from cigarette smoking, the use of certain construction materials, cleaning products, and home furnishings. Each of these pollutants, in their gaseous form, can cause harm to human health and the environment. Table 8 lists some common gaseous pollutants in the air. Sulfur dioxide (SO2), carbon monoxide (CO), and nitrogen oxides (NOx) as well as ozone (O3) are always recognized as being major pollutants of concern.

2.3.1. Sulfur Dioxide Sources of Sulfur Dioxide Sulfur dioxide accounts for about 18% of all air pollution, making it second to CO as the most common urban air pollutant.

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Table 8. Common Gaseous Pollutants Pollutants Sulfur dioxide(SO2)

Characteristics Colorless gas, with a sharp irritating odor

Sulfur trioxide(SO3)

Soluble in water to form H2SO4

Hydrogen sulfide(H2S) Nitrous oxide(N2O)

Rotten egg odor at low concentrations, odorless at high concentrations Colorless; used as aerosol carrier gas

Nitric oxide(NO)

Colorless; sometimes used as anaesthetic

Nitrogen dioxide(NO2)

Brown or orange gas

Carbon monoxide(CO)

Colorless, odorless and flammable

Carbon dioxide(CO2)

Colorless and odorless

Ozone(O3)

Very reactive

Hydrocarbons(CxHy) Hydrogen fluoride(HF)

Many different compounds Colorless, acrid, very reactive

Gaseous Pollutants Impacts Damage to vegetation, building materials, respiratory system; forms acid rain as sulfurous acid Highly corrosive, forms acid rain as sulfuric acid Extremely toxic Relatively inert; not a combustion product Produced during combustion and hightemperature oxidation; oxidized in air to NO2; it is a part of photochemical smog and acid rain Component of photochemical smog formation; toxic at high concentration Product of incomplete combustion; toxic at high concentration Product of complete combustion of organic compounds; implicated in global climate change; contributes to photochemical smog Damage to vegetation and materials; produces in photochemical smog Emitted from automobile emissions Product of aluminum smelting; causes reactive fluorosis in cattle; toxic

In the United States and the developed nations of the world, the largest single anthropogenic source of sulfur dioxide is the combustion of sulfur-containing fossil fuel, for both electric power generation and process heat. Sulfur dioxide emission sources include:

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Industry sources: Many industrial processes emit sulfur dioxide in significant quantities. Some important industrial emitters, in addition to fossil fuel combustion for power generation, are nonferrous smelters, oil refining, pulp and paper manufactures. Small textile bleaching and food preserving facilities and wineries, as well as fumigation activities, all emit sulfur dioxide to air. Transport sources: Vehicle exhaust. Consumer products that may contain sulfur dioxide: Some solvents, dechlorination agents, bleaches and fumigation products. Natural sources: Although most SO2 comes from human activities, there are many natural sources. Some geothermal activities produce SO2, including hot springs and volcanic activity; the natural decay of vegetation on land, in wetlands and in oceans all emit sulfur dioxide to air.

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Impacts of Sulfur Dioxide Sulfur dioxide is a common pollutant to which we are exposed at very low levels every day by breathing air in cities and some industrial environments. Higher exposure levels are more likely to be found in the workplace where it is produced as a by-product, such as in smelting and the combustion of coal or oil. Exposure can also happen from the manufacture of fumigants, food preservatives, bleaches and wine making. Sulfur dioxide will enter our body and affect human health when it is breathed in. It irritates the nose, throat and lung, can cause coughing, wheezing, shortness of breath, or a tight feeling around the chest. Sulfur dioxide can also enter our bodies when we eat or drink food or beverages which contain sulfur dioxide as a preservative. The effects of sulfur dioxide are felt very quickly and most people would feel the worst symptoms in 10 or 15 minutes after breathing it in. Direct exposure to SO2 gas can trigger allergic-type reactions and asthma in sensitive individuals, and can also aggravate pre-existing respiratory or heart disease. Exposure of the eyes to liquid sulfur dioxide can cause severe burns, resulting in the loss of vision. One effect of sulfur oxide environmental pollution is the formation of acid rain, which results when sulfur dioxide (as well as other gases such as nitrogen dioxide) reacts with water and atmospheric oxygen to produce sulfuric acid, the main constituent of acid rain. Uncontaminated rain has a pH of about 5.6, but acid rain can be as acidic as pH 2. Acid rain damages forests and crops, changes the makeup of soil, and makes lakes and streams acidic and unsuitable for fish. Continued exposure over a long time changes the natural variety of plants and animals in an ecosystem.

2.3.2. Nitrogen Oxides Nitrogen oxides (NOx, pronounced “knocks”), is the generic term for a group of highly reactive gases, all of which contain nitrogen and oxygen in varying amounts. Many of the nitrogen oxides are colorless and odorless. However, one common pollutant, nitrogen dioxide (NO2) along with particles in the air can often be seen as a reddish-brown layer over many urban areas.

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Sources of Nitrogen Oxides Nitrogen oxides are emitted almost anywhere that combustion occurs, especially when fuel is burned at high temperatures. Motor vehicles are the major source of nitrogen oxides, including off-road vehicles such as construction equipment. Motor vehicles account for more than 50% of NOx emissions overall, and a greater percentage in urban areas. Other primary manmade sources of NOx are electric utilities, and industrial, commercial, and residential sources that burn fuels. NOx can also be formed naturally. Scientists estimate that nature produces between 20 and 90 million tonnes of nitrogen oxides on Earth each year. Natural sources include volcanoes, oceans, biological decay and lightning strikes.

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Impacts of Nitrogen Oxides NOx causes a wide variety of health and environmental impacts, because of various compounds and derivatives in the family of nitrogen oxides, including nitrogen dioxide, nitric acid, nitrous oxide, nitrates, and nitric oxide. Direct exposure to NOx gases irritates the lungs, aggravates asthma, and lowers resistance to infection. Long-term exposure to nitrogen oxides makes animals more susceptible to respiratory infections. Nitrogen dioxide exposure lowers the resistance of animals to such diseases as pneumonia and influenza. Humans exposed to high concentrations suffer lung irritation and potentially lung damage. Nitrogen dioxide is poisonous to vegetation, can fade and discolor fabrics, cause leaves to fall and reduce the growth rate. NOx contributes to formation of haze, which cause visibility impairment most noticeable in national parks. Nitrogen oxide also helps form acid rain. NOx and sulfur dioxide react with other substances in the air to form acids which fall to earth as rain, fog, snow or dry particles, some may be carried by wind for hundreds of miles. Increased nitrogen loading in water bodies, particularly coastal estuaries, upsets the chemical balance of nutrients used by aquatic plants and animals and accelerates eutrophication. In the stratosphere, nitrogen oxides play a crucial role in maintaining the level of ozone. Ozone is formed through the photochemical reaction of nitrogen dioxide and oxygen. However, too little nitrogen dioxide results in too little ozone being formed. On the other hand, too much nitric oxide reduces the level of ozone because of an increase in the reaction of ozone to convert nitric oxide to nitrogen dioxide. In the lower atmosphere, nitrogen oxides play a major role in the formation of photochemical smog in a complex set of reactions that lead to the formation of a variety of nitrated organic compounds (from volatile organic matter) and excessive levels of ozone. One member of NOx gases, nitrous oxide or N2O, is a greenhouse gas. It accumulates in the atmosphere with other greenhouse gasses causing a gradual rise in the earth temperature. In the air, NOx can react readily with common organic chemicals and even ozone, to form a wide variety of toxic products, some of which may cause biological mutations.

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2.3.3. Ozone Ozone (O3) is a gas composed of three oxygen atoms. Photochemically formed organic oxidants, classified as ozone, are a secondary gaseous pollutant. That is, ozone is not emitted directly into the air, but is the result of chemical reactions in the ambient air. Ozone is created by a chemical reaction between nitrogen oxides and volatile organic compounds (VOC) in the presence of sunlight at ground-level. Ozone has the same chemical structure whether it occurs miles above the earth or at ground-level. Ozone can be “good” or “bad”, depending on its location in the atmosphere. Groundlevel ozone is considered “bad.” Motor vehicle exhaust and industrial emissions, gasoline vapors, and chemical solvents as well as natural sources emit NOx and VOC that help form ozone. Ground-level ozone is the primary constituent of smog. Sunlight and hot weather cause ground-level ozone to form in harmful concentrations in the air. As a result, it is known as a summertime air pollutant. Many urban areas tend to have high levels of “bad” ozone, but even rural areas are subject to increased ozone levels because wind carries ozone and pollutants that form it hundreds of miles away from their original sources. “Good” ozone occurs naturally in the stratosphere approximately 10 to 30 miles above the earth’s surface and forms a layer that protects life on earth from the sun’s harmful rays.

Sources of Ozone O3 is not a primary pollutant, that is, it is formed from precursors. The sources of ozone are actually the sources of the precursors. •

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•

• •

Motor vehicles associated with cars, trucks, buses are a major source of the O3 precursors, NOx and VOCs. Fuel combustion from off-road engines in aircraft, trains, construction equipment, agricultural operations, and lawn and garden equipment also contributes the emission of precursors. O3 precursors also include facilities that burn fossil fuels and emit NOx and VOCs, especially coal-burning electric power plants and industrial facilities. Organic compound evaporation from consumer products such as paints, cleaners, and solvents is also a source of O3 precursors.

Impacts of Ozone Ozone pollution is really an increase in the concentration of ozone in the air at ground level. Because sunlight has a critical role in its formation, ozone pollution is principally a daytime problem in the summer months. Urban areas with heavy traffic and large industrialized communities are the primary areas with ozone problems. When temperatures are high and there is little wind, ground-level ozone can reach levels that are dangerous to health. Ozone can inflame and irritate the respiratory tract, causing breathing difficulty, coughing, and throat irritation. Exposure to ozone can also increase the lungs’ susceptibility to infections, allergens, and other air pollutants. Some people are at

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especially high risk for health problems associated with O3. These include children, who normally spend a lot of time outdoors in the summer months when ozone is highest; active adults who exercise or work vigorously outdoors; and people with asthma or other respiratory problems. Often people who are affected by ozone will experience symptoms. But that’s not always the case. Some damage can occur without any noticeable signs, and lung damage can continue to occur even after symptoms go away. High levels of ozone also reduce crop and timber yields, damage native plants, and damage materials such as rubber, plastic, paint and fabrics. 2.3.4. Carbon Monoxide Carbon monoxide (CO) is a product of the incomplete combustion of carbon-containing compounds, and toxic at small doses. Carbon dioxide (CO2) is a complete product of combustion, and is much less toxic. Only under ideal conditions, with an excess of oxygen and optimal burning conditions, is carbon completely oxidized to carbon dioxide.

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Sources of Carbon Monoxide Carbon monoxide is pervasive; hundreds of millions of tons are emitted yearly. Although we can not see or smell carbon monoxide, this poisonous gas is the major gaseous pollutant. Most of the CO in the ambient air comes from vehicle exhaust. In urban areas, up to 80 or 90% of CO is emitted by motor vehicles. High levels are possible near large parking lots, traffic jams, or crowded city streets, where large numbers of slow-moving cars accumulate. Carbon monoxide is also produced by common home appliances, such as gas or oil furnaces, gas refrigerators, gas clothes dryers, gas ranges, gas water heaters or space heaters, fireplaces, charcoal grills, and wood burning stoves. Cigarette smoke contains CO too. Individuals with CO exposure at work, and who also smoke, increase their risk of adverse effects. The chemical transformation of methane, a gas emitted from decaying plants in swamps and marshlands, is also another source of carbon monoxide. The major natural source of carbon monoxide is the combustion of wood and coal. Huge quantities of carbon monoxide are produced, for example, during a forest fire or a volcanic eruption. The amount of carbon monoxide produced in such reactions depends on the availability of oxygen and the combustion temperature. Lower levels of oxygen and lower temperatures result in the formation of higher percentages of carbon monoxide in the combustion mixture. Carbon monoxide from natural sources usually dissipates quickly over a large area, posing no threat to human health.

Impacts of Carbon Monoxide Carbon monoxide (CO) is a colorless, odorless deadly gas. Because you can’t see, taste, or smell it, carbon monoxide can kill you before you know it is there. The great danger of carbon monoxide is its attraction to hemoglobin in the blood stream. When inhaled, carbon monoxide enters the blood stream by combining with hemoglobin, the substance that carries oxygen to the cells. This combination occurs 200 times more readily with carbon monoxide than with oxygen, reducing the amount of oxygen distributed throughout the body by the

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blood stream. When CO is present in the air, it rapidly accumulates in the blood, causing symptoms similar to the flu, such as headaches, fatigue, nausea, dizzy spells, confusion, and irritability. As levels increase, vomiting, loss of consciousness, and eventually brain damage or death can result. Everyone is at risk for carbon monoxide poisoning. However, individuals with greater oxygen requirements, such as unborn babies, infants, children, senior citizens, and people with coronary or respiratory problems are at greater risk. People especially susceptible to CO also include those exposed to carbon monoxide for long periods of time, such as traffic officers, and cigarette smokers. Smoking while driving in heavy traffic may result in increased exposure to CO, which is formed by the mixture of cigarette smoke and engine exhaust.

2.3.5. Indoor Gaseous Pollutants Between working, playing, eating, and sleeping, most of us spend about 90% of our time indoors. Since healthy lungs thrive on unpolluted air, keeping the air clean in your home and workplace is essential for good health. This is especially important for people with allergies or a lung disease such as asthma, bronchitis, or emphysema. Concentrations of gaseous pollutants with adverse health effects have these effects indoors as well as out of doors. Indeed, the limited volume of air inside a building, especially one with poor air circulation, causes pollutant concentrations to increase rapidly [13]. Carbon Monoxide: Carbon Monoxide is one of the most import indoor gaseous pollutants and continues to kill many people a year through accidental poisoning. Improperly vented gas appliances, wood-burning stoves, kerosene heaters, and tobacco smoke raise carbon monoxide levels indoors. Carbon monoxide also can enter your house when a vehicle is idling in an attached garage or near the house. At moderate levels, carbon monoxide can cause headaches and irregular heart beats. At higher levels, it can cause loss of consciousness, coma and death. Many fatal cases of carbon monoxide poisoning result from the accidental blockage of flues, but leakage of combustion products into the room air and misuse of fuel burning appliances are also important causes. Environmental Tobacco smoke: It is the smoke yon inhale from someone else’s cigarette, pipe or cigar and is another very significant indoor gaseous pollutant (Second-hand Smoke). It contains tar droplets and a cocktail of various other toxic chemicals including carbon monoxide, nitric oxide, ammonia, hydrogen cyanide and acrolein, together with proven animal carcinogens such as N-nitrosamines, polycyclic aromatic hydrocarbons and benzene. Environment tobacco smoke can irritate the eye, nose and throat. Exposed babies and children are more prone to chest, ear, nose and throat infections. Women exposed during pregnancy tend to have lower birth weight babies, and asthmatics may be adversely affected by acute exposures. The causal links have been established between environmental tobacco smoke exposure and heart disease, lung cancer in adults, and sudden infant death syndrome, asthma and middle ear disease in children. Nitrogen Dioxide: NO2 is generated indoors by gas, oil and solid fuel appliances. The main sources are unflued appliances such as gas cookers, gas wall heaters and kerosene heaters. Exposure to high levels typically occurs in the kitchen during gas cooking. Nitrogen dioxide can impair breathing, irritate the eye and lead to chronic bronchitis and emphysema. Nitrogen oxides may also have behavioral and psychological effects, such as lengthening reaction times or causing depression.

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Formaldehyde: Formaldehyde is a colorless gas with a pungent odour that is given off from various furnishings and fittings found in the home. One of the most important sources is pressed wood products (hardwood, plywood, particleboard and fiberboard), made using bonding materials containing urea-formaldehyde resin, which has become increasingly used in buildings and furniture over the last few decades. Another source is urea-formaldehyde foam insulation installed in wall cavities. Formaldehyde is also released by combustion appliances, cigarettes, paper products, floor covering, textiles, disinfectants, toothpastes, shampoos, cosmetics, and some medicines. Studies have shown that indoor concentrations often exceed 1.0 ppm. At levels ranging upwards from 0.05, formaldehyde exposure can lead to rashes, irritation of respiratory tract, nausea, headaches, dizziness, and aggravation of bronchial asthma. All of these effects appear at lower concentrations in people who have been exposed to the substance for long periods of time. Radon Gas: Indoor radon problems generally result from the entry of radon gas released as a result of the radioactive decay of uranium found in soil around the house and in the geological formation under the foundation, through cracks, drains, sumps, or other house openings. Building materials such as granite, clay, bricks, rocks, sandstone, and concrete containing alum shale may also be major sources of radon, depending on their uranium content. Exposure to radon has been linked to an increased risk of lung cancer.

2.4. Other Pollutants and their Impacts

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2.4.1. Noise Pollution What is Noise Pollution? No one on earth can escape the sounds of noise: an unwanted, disturbing sound. Noise is probably the most frequently forgotten of the environmental pollutants, yet its effects can be many and far-reaching. The word noise is derived from the Latin term “nausea,” referring originally to nuisance noise. Noise pollution is unwanted sound or environmental noise, which can not only be physically harmful and painful, but can also decrease concentration, productivity, and peace of mind. Even though noise only stays in the air for a short time, its effects are cumulative in terms of temporary or permanent hearing loss. Noise intensity is measured in decibel (dB) units; increased distance diminishes the decibel level that reaches the ear. The zero on a decibel scale is at the threshold of hearing, the lowest sound pressure that can be heard; 20 dB is whisper, 60 dB is normal conversation, and 80 dB is the level at which sound becomes physically painful. What is a truly safe level of noise is controversial; levels of between 55 and 65 dB have been used for planning purposes in the USA and have been called “acceptable.” In the past several decades, noises in all areas, especially in urban areas, have been increasing rapidly. Perhaps 150 million US citizens live in areas where the daily average noise levels exceed the US Environmental Protection Agency’s safe noise level of an average of 55 decibels. In Hong Kong, over a million people live in even noisier environments [14]. Slowly, insensibly, we seem to accept noise and the physiological and psychological deterioration that accompanies it as an inevitable part of our lives. Although we attempt to set

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standards for some of the most major sources of noise, we often are unable to monitor them [15]. Although most developed nations have government agencies responsible for the protection of the environment, no nation has a single body that regulates noise pollution. In the United States, Canada, Europe, and most other developed parts of the world, different types of noise are managed by agencies responsible for the source of the noise. Transportation noise is usually regulated by the relevant transportation ministry, health-related work noise is often regulated by health ministries and worker’s unions, and entertainment noise such as loud music is a criminal offense in many areas. As the bodies responsible for noise pollution reduction usually view noise as an annoyance rather than a problem, and reducing that noise often hurts industry financially, little is currently being done to reduce noise pollution in developed countries.

Noise Pollution Sources Transportation vehicles are the most significant sources of noise pollution, with aircraft, railroad stock, trucks, buses, automobiles, and motorcycles all producing excessive noise. Construction equipment, like jackhammers and bulldozers, also produce substantial noise pollution. Office equipment, factory machinery, appliances, power tools, hum from lighting fixtures, and audio entertainment systems are other common sources of noise pollution. The sources of noise pollution will be investigated in some detail in the following paragraphs. Transportation Noise: the source of most noise worldwide is transportation systems, including road traffic noise, aircraft noise and railroad noise.

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•

•

•

Road Traffic Noise: Road accounts for approximately 70% of total noise emissions by transportation. The main sources of noise come from the engine and the friction of the wheels over the road surface. Furthermore, travel speed and the intensity of traffic are directly linked with its intensity of noise. Road traffic is the most widespread source of noise in all countries and the most prevalent cause of annoyance and interference. Therefore, traffic noise reduction measures should have the highest priority. Aircraft Noise: Air transportation accounts for 20% of total noise emissions by transportation. As air transportation took a growing importance in intercity transportation, noise emissions have increased significantly to the point of becoming a major concern near airports. Aircraft noise comes from the jet engine, the aerodynamic friction and ground craft operations. Railroad Noise: Railroad accounts for 10% of total noise emissions by transportation. Noise comes from the engine (mostly diesel), the friction of wheels over the rails, and whistle blowing. Furthermore, when trains are moving at high speed, areoacoustic noise becomes more important than other sources. The most important noise impacts of railroad operations are in urban areas where the majority of transshipment functions are performed. Furthermore, railroad terminals are often located in central and high density areas of cities.

Construction Noise: The noise from the construction of highways, city streets, and buildings is a major contributor to the urban scene, and most construction workers lose a lot of their hearing. Construction noise sources include pneumatic hammers, air compressors,

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bulldozers, loaders, dump trucks, and pavement breakers. Most construction noise comes from equipment. These decibel levels have been measured in Table 10. The noise levels can change. The noise from an earthmover is 94 decibels from 10 feet away, only 82 decibels if you are 70 feet away. A crane lifting a load can make 96 decibels of noise; at rest, it may make less than 80 decibels. Industry Noise: In most developing countries, industry noise levels are higher than those in developed countries. Industrial noise is usually considered mainly from the point of view of environmental health and safety, rather than nuisance, as sustained exposure can cause permanent hearing damage. Industry noise has been a hazard linked to heavy industries such as ship-building. Table 8. Construction Equipment Decibels

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Equipment Pneumatic hammer Jackhammer Concrete joint cutter Portable saw Stud welder Bulldozer Earth Tamper Crane Earthmover Front-end loader Backhoe

Decibels 103-113 102-111 99-102 88-102 101 93-96 90-96 90-96 87-94 86-94 84-93

Airborne noise from industrial facilities is hazardous to the long-term health of employees; one method to control industry and construction noise is providing workers with hearing protection devices; these devices must have enough noise attenuation to protect against the anticipated exposures, but must not interfere with the ability to hear human speech and warning signals in the workplace. Noise in Home: Private dwellings are getting noisier because of internally produced sound as well as an external community sound. Certain household equipment, such as vacuum cleaners, fans, air conditioners and some kitchen appliances have been and continue to be noisemakers, although their contribution to the daily noise dose is usually not very large. External noise from emergency vehicles, traffic, refuse collection, and other city noises is also a problem for urban residents, especially when windows are open or insufficiently glazed. Neighbor noise is also a contributor to the noise in home, such as ear-splitting music, slamming doors, barking dogs, late night parties and deafening drilling- all of which can greatly impact people’s daily lives.

Impacts of Noise Human Health Effects: Exposure to noise will cause a number of physiological and psychological responses. •

Hearing loss: Approximately 10% of the population in industrialized societies suffers from significant hearing loss. Exposure to noise pollution exceeding 75 decibels for more than eight hours daily for a long period of time can cause loss of hearing. The

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•

•

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•

hazards increase with the intensity of the noise and the period of exposure. And hearing loss is usually irreversible. The sound produced by a bursting cracker, exceeding 150 decibels, can cause a ringing sensation called “tinnitus” and can impair hearing permanently. It is now accepted that aging alone is not the principal cause of hearing loss, but that it is rather due to cumulative long-term exposure to environmental and occupational noise. Annoyance and stress: Annoyance by noise is a response to auditory experience. Annoyance has its base in the unpleasant nature of some sounds, in the activities that are disturbed or disrupted by noise, in the physiological reactions to noise, and in the responses to the meaning of “message” carried by the noise [16]. Annoyance caused by noise varies depending on the source, time of day, frequency of occurrence and from person to person. Annoyance causes physiological effects demonstrated by stress indicators, such as hormone release and increased blood pressure. The longterm effects of elevated stress levels can be very serious for cardio-vascular health. Annoyance and stress lead to difficulty concentrating, irritability and increases in aggressive behavior; motor vehicle and aircraft noise are the most important sources of sound levels which give rise to these effects. Sleep disturbance: Almost all of us have been awakened or kept from falling asleep by loud, strange, frightening, or annoying sounds. Sleep disturbance is one of the most serious effects of environmental noise. WHO guidelines say that for good sleep, the sound level should not exceed 30 dB for continuous background noise, and individual noises events exceeding 45 dB should be avoided. Sleep disturbance is clearly detrimental to well being, and longer term disturbances are damaging to physical and mental health. Tiredness also reduces concentration spans, which decreases productivity and performance at work or school and increases the risk of accidents. Cardiovascular disease: Exposure to loud noise can cause blood vessels to constrict. This makes the heart work harder to pump the same amount of blood. Through the years, this may contribute to heart disease. The link between noise and heart disease has been investigated since the 1960s. Over recent years, results from many epidemiological studies have been collated to show that there is a causal link between noise and serious health problems including high blood pressure and heart disease. A study by the German Federal Environment Agency has recently carried out research firmly establishing the causal link between road traffic noise and heart disease.

Environmental Effects: Noise can have a detrimental effect on animals. An impact of noise on animal life is the reduction of usable habitat that noisy areas may cause, which in the case of endangered species may be part of the path to extinction. One of the best known cases of damage caused by noise pollution is the death of certain species of beached whales, brought on by the loud sound of military sonar. Now, it is well known to all that plants are similar to human beings; they are also as sensitive as man. There should be a peaceful environment for their better growth. Noise pollution causes poor quality of crops in a pleasant atmosphere. Loud noise is also very dangerous to buildings, bridges and monuments. It creates waves which could strike the walls and put the building into a dangerous condition.

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2.4.2 Natural Disasters and their Pollution Although most instances of pollution result from the activities of humans, pollution can occur naturally. In many cases, natural pollution can cause an intensity of ecological damage that is as severe as anything caused by anthropogenic pollution. Volcanic Eruptions Pollution can be caused both by human and natural sources. Volcanic eruptions are an example of natural sources of pollution. When a volcano explodes, it releases huge quantities of ash, sulfur dioxide, carbon monoxide, solid particles, and other chemical materials into the air at a much greater rate than is normally the case. Plants, animals, and humans may be killed or injured by these materials. A massive volcanic eruption can blast huge clouds of ash and gases into the atmosphere. Millions of tonnes of sulfur dioxide gas may reach the upper atmosphere (the stratosphere). Locally, sulfur dioxide gas can lead to acid rain and air pollution downwind from a volcano. Globally, the sulfur dioxide transforms into tiny particles of sulfuric acid, known as aerosol, which can lead to lower surface temperature. The particles reflect energy from the sun back into space, preventing some of the sun’s rays from heating the Earth. Conversion of the sulfur dioxide to sulfuric acid aerosol in the stratosphere takes some months, so maximum cooling occurs up to a year after the eruption. It may take as long as seven years before the cooling influence of the volcanic aerosol disappears completely. Large eruptions, such as the Mount Pinatubo in the Philippines which occurred in 1991, can bring about a short but noticeable global cooling of up to 0.3°C. Volcanic eruptions can enhance global warming by adding CO2 to the atmosphere. However, a far greater amount of CO2 is contributed to the atmosphere by human activities each year than by volcanic eruptions. The small amount of global warming caused by eruption-generated greenhouse gases is offset by the far greater amount of global cooling caused by eruption-generated particles in the stratosphere. A few historic eruptions have released sufficient fluorine-compounds to deform or kill animals that grazed on vegetation coated with volcanic ash; fluorine compounds tend to become concentrated on fine-grained ash particles, which can be ingested by animals. Coal Fire Coal fire means the spontaneous combustion of coal, which is a global natural disaster that destroys resources and the environment. As a natural hazard, coal fire can occur in many places where coal is available in a great amount, especially in coal producing countries such as China, India, Indonesia and other developing countries. Underground and surface coal fires are serious and are a widespread problem [17]. In China’s coalfields, coal fires are spread over the northern part of the country. The factors causing coal fires are manifold, but they all can be attributed to the coals ability to react with oxygen. Spontaneous combustion is thereby one of the main coal fire causes. Underground coal fires are relentlessly incinerating millions of tons of coal around the world. The blazes spew out huge amounts of air pollutants, force residents to flee their homes, send toxic runoff flowing into waterways, and leave the land as scarred as a battlefield [18]. Coal fires induce considerable economic and environmental problems. The economic problem comprises in particular the loss of large amounts of the unrenewable fossil fuel. It is

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not only the burned coal that becomes useless for economic purpose but the access to remaining reserves is often made difficult or impossible by fires, and thus coal production suffers. Environmental effects caused by the coal fires can be noticed at local and global levels. Heat and noxious gases affect the immediate surroundings of active coal fires. The pollution turns it into an unpleasant place to live. Plants in the area are killed. The land surface is cracked or slumped, and as the burned coal turns to ash, often the rocks are overburdened and can no longer be supported. Extensive damage to infrastructure like buildings, roads and railways could be the consequence. The local population is not only plagued by the unpleasant environment but the rates of cancer, lungs and gastrointestinal diseases are higher than in other areas. The main problem affecting the global environment is that coal fires produce vast quantities of carbon dioxide, the main “greenhouse” gas. At present, Chinese coal fires produce 2-3% of the world’s total annual output of CO2 caused by fossil fuels.

Earthquake On May 12, 2008, an 8.0-magnitude earthquake hit the Sichuan Province in Western China, which was China’s most damaging earthquake since the 1976 Tangshan Earthquake disaster. More than 70,000 people died in the quake, including many schoolchildren who were killed when their schools collapsed. Of the more than 15 million people living in this area, more than 300,000 were injured during the quake and at least one third of the population was left homeless. The most immediate concerns after such a disaster are human casualties, injury, and property destruction. However, earthquakes and other natural disasters wreak substantial environmental damage, with consequences for human health and economy as well as biodiversity and resource availability [19]. Not only had people’s lives, homes, schools and other facilities been destroyed after the earthquake disaster, the ecological environment had also been severely challenged. More than one month after the Sichuan earthquake, the clean-up and reconstruction continue amid public fears of disease, chemical and radioactive contamination and unsafe food and drinking water. One of the biggest environmental issues in the immediate weeks after an earthquake is contaminated drinking water. Mountains of corpses and hazardous material spill from ruptured tanks and pipes of factories have the potential to leak into the water system, which may lead to water contamination as well as the spread of infectious diseases. After the Sichuan earthquake, landslides filled in portions of rivers, creating “quake lakes”- huge pools of backed-up water. These quake lakes are a lingering threat to residents, potentially endangering the lives of millions of people if the water builds up and then barriers break. Earthquake also causes ecosystem and habitat loss. Sichuan houses the primary reserves for China’s endangered icon, the giant panda. Forty-nine panda reserves suffered damage in the earthquake. It has been estimated that 80% of the panda habitat in Sichuan was damaged in the earthquake, though there are some panda casualties that have been difficult to verify because the area is still largely inaccessible. The irrigation system has also been damaged and will need a long time to repair. In addition, agricultural land is vulnerable as reconstruction begins, since this land may be taken over by temporary settlements or repurposed for rebuilding towns.

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3. CONCLUSION Between one-third and one-half of the land surface has been transformed by human action; more than half of all accessible surface fresh water is put to use by humanity; and about one-quarter of the bird species on Earth have been driven to extinction [20]. “We do not inherit the earth form our ancestors, we borrow it from our children.” This is a simple and old Native American saying, attributed to Professor W. A. Turmeau, and it expresses the key reason why we must stop polluting our planet. Concern about the state of our environment is now one of the main issues in people’s minds, even higher up the list than war, unemployment and their health [21]. More and more countries have realized the serious results of environmental pollution; most of them have enacted laws to prevent the environment from being further polluted and have also set up special Environment Ministries to facilitate the enforcement of these laws and regulations. We only have one earth, so we need to take care of her. On the first Earth Day in 1970, US senator Gaylord Nelson said, “The economy is a wholly owned subsidiary of the environment. All economic activity is dependent upon that environment with its underlying resource base.”

REFERENCES [1] [2] [3]

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[4] [5]

[6] [7] [8] [9] [10] [11] [12] [13]

Soil contamination. Available from: http://en.wikipedia.org/wiki/Soil_pollution Spellman, F. R. (1999). The Science of Environmental Pollution. Lancaster: Pa. Technomic Publishing. Hill, M. K. (1997). Understanding Environmental Pollution. Cambridge: Cambridge University Press. Hill, M. K. (2004). Understanding Environmental Pollution (2nd Edition). Cambridge: Cambridge University Press. U.S. Environmental Protection Agency (2000). Municipal Solid Waste Generation, Recycling, and Disposal in the United States: Facts and Figures for 1998, EPA 530-F00-024. Harrison, R. M. (2001). Pollution Causes, Effects, and Control (4th Edition). Cambridge: The Royal Society of Chemistry. David H.F. Liu, and Béla G. Lipták (2000). Hazardous Waste and Solid Waste. Lewis Publishers. Wastewater. Available from: http://en.wikipedia.org/wiki/Wastewater Stormwater. Available from: http://www.epa.gov/reg3wapd/stormwater Causes of Black Tides accidents. Available from: http://www.blacktides.com/uk/source/oil-tanker-accidents/causes-accidents.php Environmental impact of Oil Spills. Available from: http://www.itopf.com/marinespills/effects/environmental-impact/ Doerffer, J. W. (1992). Oil Spill Response in the Marine Environment. Pergamon Press. Peirce, J. J., Weiner, R. F., and Vesilind P. A. (1998). Environmental Pollution and Control (4th Edition). Butterworth-Heinemann.

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[14] Noise Pollution. Available from: http://www.karmayog.org /noisepollution /noisepollution_74.htm [15] Cause and Effects of Noise Pollution. Available from: http://www.karmayog.org /noisepollution/57.htm [16] Miller, J. D. (1974). Effects of Noise on People. Acoustical Society of America, Volume 56, pp. 729-764. [17] Coal Fire Overview. Available from: http://www.itc.nl/~coalfire/problem /overview.html [18] Michael Woods. Underground coal fire called a catastrophe. 2003, February, 15. Available from: http://www.post-gazette.com/healthscience/ 20030215coalenviro4p4. asp [19] He, G. Environmental Challenges after China’s Sichuan Earthquake. 2008, June, 24. Available from: http://earthtrends.wri.org/updates/node/316 [20] Vitousek, P. M., Mooney, H. A., Lubchenco, J., and Melilli, J. M. (1997). Human domination of Earth’s ecosystems. Science, Volume 277, pp. 494-499. [21] Gerry Best (1999). Environmental Pollution Studies. Liverpool: Liverpool University Press. [22] Air Quality in the North. Available from: http://www.ec.gc.ca/cleanairairpur/Regional_Clean_Air_Online/Prairie_and_Northern_Region/Air_Quality_in_the_ North-WSC812DD6E-1_En.htm [23] Tschobanoglous, G., Theisen, H., and Vigil, S. (1993). Integrated Solid Waste Management. New York: McGraw-Hill. [24] World Resources Institute and International Institute for Environment and Development. (1987). World Resources 1987. New York: Basic Books. [25] Boyle, M. (1988). Radon testing of soils. Environmental Science Technology, Volume 22, pp. 1397-1399. [26] Davis, M. L., and Masten, S. J. (2004). Principles of Environmental Engineering and Science. New York: McGraw-Hill. [27] Stormwater Pollution. Available from: www.epa.sa.gov.au/pdfs/water_general.pdf

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Chapter 2

ENVIRONMENTAL ASPECTS AND IMPACTS OF CONSTRUCTION INDUSTRY Nik Norulaini Nik Ab Rahman1, Fatehah Mohd Omar and Mohd Omar Ab Kadir School for off Campus, University Sains Malaysia USM, 11800, Penang, Malaysia

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ABSTRACT Given the international focus on sustainability in recent years, there is a dire need to evaluate the aspects and impacts in the construction industry and identify methods and techniques that would facilitate sustainability and impact assessment and decision making at the various project level interfaces. The construction activities are being kept under rigid analysis and control due to its intimacy and direct association with the outdoor (external) environment. Any construction, irrespective of size, type and location will cause impacts on the environment, arising from the construction activities, for as long as the construction goes on until the commissioning stage. These environmental impacts are typically classified as air pollution, land contamination and degradation, noise pollution and water pollution. Construction activities impart significant impact on the environment across a broad spectrum: whether it is off-site, on-site or operational activities. Off-site activities include office management, documentation, policy, planning, engineering and architectural drawings. On-site construction activities relate to the pre-construction and the actual construction of a physical facility, resulting in air pollution, water pollution, traffic problems and the generation of construction wastes. Activities in the construction industry are complex, highly dispersed and resource demanding.

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1. INTRODUCTION The construction industry can be defined as the industry that concerns construction works, and that includes construction extension, installation, repair, maintenance, renewal, removal, renovation, alteration, dismantling or demolition of: a) any building, erection, edifice, structure, wall, fence or chimney, whether constructed wholly or partly or below ground level; b) any road, harbour, railway, cable way, canal or aerodrome; c) any drainage, irrigation or river control works; d) any electrical, mechanical, water gas, petrochemical or telecommunication works or; any bridge, viaducts, dam, reservoir, earthworks, pipeline, aqueduct, culvert, driveshaft, tunnel or reclamation works Construction is not an inherently environmentally friendly industry and evidence has shown that construction is a major contributor to environmental disruption and pollution. The main reasons that have been identified include:

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1) Uniqueness of the construction industry- separated designs, construction, and multilayered contracting systems. 2) High degree of fragmentation - numerous participants pursuing singular interests on a project by project basis. Inhibits addressing environmental protection issues 3) Impact on environment- Ecological breakdown (flora and fauna); Pollutions: water, air, noise, vibration, socio-economic impact 4) The need to balancie environmental values with development- prevalence of imbalance towards development and the inadvertent environmental negligence The construction industry is one of the major contributors to the environmental impacts, which are typically classified as air pollution, waste pollution, noise pollution and water pollution. These impacts on the environment cut across a broad spectrum of off-site, on-site and operational activities. Off-site activities concern the mining and manufacturing of materials and components, land acquisition and project design. On site construction activities relate to the construction of a physical facility, resulting in air pollution, water pollution, traffic problems and the generation of construction wastage. In general the environmental impacts can be put under the categories of ecology, landscape, traffic, water, energy, timber consumption, noise, dust, sewage and health and safety hazards.

2. CONSTRUCTION PLAYERS AND THEIR ROLES, COMMITMENT AND RESPONSIBILITIES The key players in any project development are the owner, the designer or design professional and the constructor or contractor. Other entities, such as the authorities or regulators, subcontractors, material vendors and so forth are important supporting players in the development process; the major development of the project revolves around these three

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major players [1]. Table 1 gives a list of players who are involved at different stages of project development.

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Table 1. Construction players and their involvement in the various phases of construction development

Phases

Main Process

Main Players

Planning

The process of project identification, feasibility study, project appraisal and project master plan

Design

The process of translating business/social needs to products

Procurement

The process of securing the best process for transforming the product to built environment

Construction

The process of transforming the product to a built environment

Operation and maintenance

The process of utilizing the built environment to meet the business /social needs

Developer/Client Planner Architect Engineer Environmental Officer Financier Local Authority Regulator Developer/Client Architect Engineer Quantity surveyor Regulatory authorities Developer/client Architect Engineer Quantity Surveyor Main Contractor Architect Engineer Quantity Surveyor Regulatory authorities Project Manager Main Contractor Skilled and unskilled workers Suppliers Plant operators Financiers Developer/Client Management Corporation Regulatory Authorities Consensus

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Construction has to be a sustainable industry, which requires the creation of buildings and infrastructure to shape communities in a way that sustains the environment, generates wealth over the long term and enhances the quality of life of people without harming the future generation. The economic, social and environmental benefits which can flow from a more efficient and sustainable construction industry are potentially immense. Reducing consumption of materials and land, minimizing waste generation, using recycled materials, embracing energy efficiency and managing site operations to avoid pollution are good for business as well as the environment [2]. Achieving long term sustainability in the construction industry requires analysis and changes to what is built, where it is built, how it is built and the operation of the built facility [3]. The evolution of land use involves the transformation from natural vegetation to agriculture and then in some cases urban development. Urban development plays an important economic role. According to Chen and Hong [4] the construction industry holds fast to three main objectives, which are time, cost and quality. However, no emphasis has been put upon the environment and the level of degradation it has undergone caused by construction. These findings are reinforced with Dissertation [5] study that the four major obstacles to implementing a proper management system are: lack of governmental pressure, lack of client requirement/support, expensive implementation cost and sub-contracting systems. Every level of the industry should be made aware of the importance of environmental care since this will ensure mitigating measures will be practiced. The effectiveness of environmental protective measures can only be realized if all construction professionals participate in applying them as supported by Faith-Elle [6]. They also agreed that regulatory enforcement is ineffectual and this is largely due to lack of authority and consultants. However, despite the concerns raised the group, they did acknowledge that based on current practices, the importance of profit overtakes environmental management and care. Construction activities and practices that fail to control its impacts and the environment can cause damage to rivers, lakes and environmentally sensitive ecosystems, kill fish and aquatic life, upset ecological systems and wildlife habitats, and result in contamination of land and groundwater. The impact on the environment is particularly high when work is done on highland, on slopes, near coastal areas, rivers and lakes. Brown and Jacobs [7] had pointed out that when construction occurs near built-up areas, poor practices may result in noise and air pollution which may cause a nuisance and affect the health of neighboring communities. Large projects usually involve extensive land disturbance involving the removal of vegetation and reshaping the topography. Such activities make the soil vulnerable to erosion. The biological environment includes non-human animal and plant life, the distribution and abundance of the various species and the habitats of communities. Species forming a community are often interdependent so that a direct environmental effect on one species is likely to have indirect effects on another species [8]. Solid wastes can be either hazardous or non-hazardous. Construction projects generally generate more non-hazardous waste than hazardous wastes. Some of the types of wastes found at a typical construction site are construction waste, domestic waste and scheduled waste. Water quality is important for economic, ecological, aesthetic and recreational purposes. Changes in water quality may affect water treatment costs or even deny some the use of water. The potential for soil erosion and impacts on water quality are greatest during construction when removal of vegetation for initial clearing and grading activities exposes

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soil and makes it susceptible to erosion. The impacts are greatest during the rainy season where extensive land clearing has been carried out. Activities or major concerns for air quality are the burning of waste, the emission of dust and smoke, and the emission of chemical impurities such as heavy metals, acid and other toxic bases. Principle effects are on human health, aesthetic values (sight and smell) adjacent land uses, temperature modification and humidity changes. Air quality impacts from construction include increased dust and airborne particulates caused by grading, filling, removals and other construction activities. Air quality impacts may also result from the emissions of construction equipment and vehicles. The sector contributes to the loss of important natural assets and imposes severe stress on the environment. Agricultural land is often lost through urbanization and extraction of raw materials. Forest timber is harvested for construction and building materials faster than it can be replaced by planting new trees or by natural growth. Noise and vibration would be generated by various activities and equipment used in the construction project. Noise and vibration levels due to construction activities in the project area would vary depending on the types of equipment used, the location of the equipment and the operating mode.

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3. IMPACTS OF CONSTRUCTION ACTIVITIES ON THE ENVIRONMENT Activities in the construction industry are complex, highly dispersed and resource demanding. The industry contributes to the loss of important natural assets and imposes severe impacts and stress on the environment. Construction activities and practices that fail to control its impacts and the environment can cause damage to rivers, lakes and environmentally sensitive ecosystems, kill fish and aquatic life, upset ecological systems and wildlife habitats, and result in contamination of land and groundwater. The impact on the environment is particularly high when work is done on highlands, on slopes, near coastal areas, rivers and near lakes. When construction occurs near built-up areas, poor practice may result in noise and air pollution which may cause a nuisance and affect the health of neighboring communities. However, Woods et al. [3] had judiciously highlighted that the assessment of the environmental impacts must be done diligently and these must be verified during the actual construction activities.

4. LAND DEGRADATION Large projects usually involve extensive land disturbance involving the removal of vegetation and reshaping of the topography (Figure 1). Such activities make the soil vulnerable to erosion. Soil removed by erosion may become airborne and create a dust problem or be carried by water into natural waterways and pollute them. Due to the soil erosion of the exposed and loose earth, there will be a deterioration of water quality in the surrounding water bodies due to siltation and sedimentation. Siltation and sedimentation in the water bodies can result in mud floods and flash floods in the downstream area during heavy downpours.

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Landslides and slope failure can occur at unstable slopes or when slopes are saturated with water during heavy rainfalls [9]. Measures to address the impact of land disturbance on the environment should be included in the planning and design phase of the project before any land is cleared. The extent of exposure of bare surfaces to rainfall needs to be limited. Exposed surfaces need to be covered with turfing and plastic sheets as soon as possible.

Figure 1. Land clearing during site preparation for construction.

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5. LOSS OF FLORA AND FAUNA The biological environment includes non-human, animal and plant life, and the distribution and abundance of the various species and the habitats of communities. Species forming a community are often interdependent so that a direct environmental effect on one species is likely to have indirect effects on another species. Unfortunately, the loss of flora and fauna is imminent in any development. Planning is essential to ensure minimal losses during the implementation stages and steps must be taken later to ensure that the losses are “replenished.” This is essential, especially when development is within the vicinity of either a mountain range, a densely forested area or catchment areas. At the Planning stage, if the environmental considerations are described in detail and allowances made for implementation during the construction stages, then, the losses would be minimised and better protection could be put in place for the conservation of the flora and fauna [8].

6. SOLID WASTES Solid waste can be either hazardous or non-hazardous. Construction projects generally generate more non-hazardous waste than hazardous wastes. Some of the types of wastes found at a typical construction site are construction waste (Figure 2), domestic waste and scheduled waste. Construction waste are solid inert waste which usually consists of building

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rubble, but may also include demolition material, concrete, bricks, timber, plastic, glass, metals, bitumen, trees and shredded tires. Such wastes should be reused, recycled, or disposed of to an approved landfill. Disposal methods adopted depend on the nature of the material. Improper disposal can lead to the outbreak of diseases such as malaria, dengue and schistosomiasis, which is transmitted by mosquitoes and snails. Domestic waste can be found at construction sites which have nearby basecamps for the workers. Domestic wastes need to be properly disposed to avoid the infestation of rodents, roaches and other pests. These pests bring with them vector borne diseases such as cholera and rabies. The contractor is also responsible for the proper handling, storing, transporting and/or disposing of scheduled wastes. Examples of scheduled or hazardous wastes are used oil, hydraulic fluid, diesel fuel, soil contaminated with toxic or hazardous pollutants, waste paints, varnish, solvents, sealers, thinners, resins, roofing cement and more. The responsibility covers the proper handling, storing, transporting and disposal of these wastes.

Figure 2. Construction wastes.

7. WATER POLLUTION Water quality is important for economic, ecological, aesthetic and recreational purposes. Changes in water quality may affect water treatment costs or even deny some the use of water. The potential for soil erosion and impacts on water quality are greatest during

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construction when removal of vegetation for initial clearing and grading activities exposes soil and makes it susceptible to erosion. The impacts are greatest during rainy seasons where extensive land clearing has been carried out [10]. Figure 3 below shows the stream that had silt discharged into it from land clearing carried out nearby.

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Figure 3. Land clearing exposes soil that can be washed into water courses casuing siltation.

8. AIR POLLUTION Activities or major concerns for air quality are the burning of waste, the emission of dust and smoke, and the emission of chemical impurities such as heavy metals, acid and other toxic bases. Principle effects are on human health, aesthetic values (sight and smell) adjacent land uses, temperature modification and humidity changes. Air quality impacts from construction include increased dust and airborne particulates caused by grading, filling, removals and other construction activities. Air quality impacts may also result from the emissions of construction equipment and moving vehicles [11].

9. DEPLETION OF RESOURCES Activities in the construction sector are complex, highly dispersed and resource demanding. The sector contributes to the loss of important natural assets and imposes severe stress on the environment. Agricultural land is often lost through urbanization and the extraction of raw materials. Forest timber is harvested for construction and building materials faster than it can be replaced, by planting new trees or by natural growth.

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Many raw materials used in construction are limited resources. For example, the reserves of some metals will be gone in less than 30 years, if the current rate of exploitation continues. The consumption of fossil fuels contributes to increased air pollution and emissions of greenhouse gases [12].

10. NOISE AND VIBRATION Noise and vibration may be generated by various activities and equipment used during the construction project, such as the hydraulic drill. Noise and vibration levels due to construction activities in the project area vary depending on the types of equipment used, the location of the equipment and the operating mode. During a typical work cycle, construction equipment may be idling, preparing to perform tasks, or operating under a full load. Equipment may be congregated in a specific location or spread out over a large area. Adverse impacts resulting from construction noise and vibration are expected to be limited to areas adjacent to the project and temporary in nature. The construction noise and vibration impacts would be localized near the area where construction is taking place [11].

11. LAND CONTAMINATION

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Although it may be necessary to store chemicals and fuel on project sites, this inevitably creates an environmental risk. Spills such as used oil can severely pollute land (Figure 4) and be carried away with surface runoffs into nearby water courses. Reducing the quantities of chemicals and fuel stored on-site to minimum practicable levels is desirable.

Figure 4. Land contamination from reckless management of used oil.

12. ENVIRONMENTAL ASPECTS The first thing an organization in the construction industry has to do is to determine the environmental issues that must be managed. Environmental issues are those issues that are associated directly and indirectly with the construction activities.

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Environmental aspects are elements of an organizations’ activities that can interact with the environment. An environmental impact is any change to the environment, whether adverse or beneficial, wholly or partially resulting from organizations’ environmental aspects [13]. Examples of adverse impacts include pollution of air, and depletion of natural resources. Examples of beneficial impacts include job opportunities, availability of properties for sale, property enhancement, improved infrastructure and provisions of amenities. A project can have a number of environmental aspects related to their activities. Some will be directly within their control (e.g. direct aspects such as air emissions and water discharges) and some will be spawned indirectly (e.g. indirect aspects such as activities of raw material suppliers). As both types can lead to significant environmental impacts, both should be assessed for significance. The key to a successful management of environmental impacts is to accurately determine the industry’s environmental aspects and to arrive at the most significant aspects and impacts that require the most attention. Two definitions should be reviewed at this point which are ‘environmental aspect’ which is the element of the construction activities, that can interact with the environment. A significant environmental aspect is an environmental aspect that has or can have a significant environmental impact. Whereas an environmental impact is any change to the environment, whether adverse or beneficial, wholly or partially resulting from the construction. A construction project can have a number of environmental aspects related to their activities. Some will be directly within their control (e.g. direct aspects) and some will be of a nature that can only be indirectly influenced (e.g. indirect aspects). As both types can lead to significant environmental impacts, both should be assessed for significance. Construction industry will need to identify the aspects of their activities and determine their significance. Having evaluated environmental aspects for significance it is possible to prioritize actions that address issues relating to the construction operations [13]. There are three distinct requirements. •

• •

First, the construction industry shall identify the environmental aspects of its activities. In other words the industry must understand how it interacts with the environment. Second, the industry shall identify the specific environmental aspects that can be controlled, and over which it can be expected to have influence. Third, arrive at a list of significant environmental aspects based upon the individual environmental impact of each environmental aspect.

The importance of this third step cannot be underestimated. The final list of significant environmental aspects will provide the basis for the environmental policy statement, and the environmental objective(s) and targets. In other words, the list of significant environmental aspects drives the entire content and scope of the operational portion of the management of the environmental aspects and impacts effectively. One of the best ways to identify the environmental aspects is by recognizing associated impacts related to the construction industry activities, new or modified projects undertaken, any potential and actual emergency situations in the organization. The next course of action is

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to select an approach and establish and maintain a procedure for the assessment of significant aspects and associated impacts that had been identified; and evaluate its significance, including collection of additional information where required. Using the established significant procedure, significant aspects and associated impacts on which the organization is going to focus are determined [14]. The following questions will need to be answered in order to determine whether the environmental aspects meets the intent of managing the impacts well [15]: -

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-

Has the industry developed a procedure(s) to identify the environmental aspects of its activities that it can control and over which it can be expected to have an influence? Does the industry include the evaluation of non-routine conditions? Does the industry utilize and improve this procedure(s)? Has the industry utilized the procedure(s) to determine which of its environmental aspects have, or can have, significant impacts on the environment? Is the information relative to the environmental aspects kept up to date?

Such impacts may be local, regional or global, short or long term, with varying levels of frequency and likelihood of happening. These factors are normally considered in assigning a level of significance of each impact. Those involved in the construction industry should understand the activities that fall within the scope of its environmental management system, and may find it useful to group them to facilitate identification and evaluation of environmental aspects. The relationship between aspects and impacts is one of cause and effect. Figure 5 below shows the relationship of the construction activity, vis a vis, land clearing with the consequent aspects and impacts. The inputs of land clearing include machinery, fuel, and human resources. Land clearing requires earthworks that level the land, cutting down trees and the uprooting of shrubberies to accommodate the erection of new buildings. Along with this process, there will be aspects of land clearing that are coupled with environmental issues and aspects (Table 2). Other impacts associated with construction activities are depicted in Table 3. Loss of terrestrial habitat, loss of biodiversity Removal of v e ge t a t i on

Air pollution Emission to air

Loss of land fertility, erosion Removal of topsoil

Resources, fuel, machinery, l a n d a re a , vegetation, topsoil

Cleared l a nd

Generation of waste Land degradation, loss of aesthetic values

Surface runoff Erosion, siltation, flash floods

Figure 5. Examples of Environmental Aspects and Impacts from Land Clearing. Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

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Nik Norulaini Nik Ab Rahman, Fatehah Mohd Omar and Mohd Omar Ab Kadir

Table 2. Examples of associated environmental aspects and impacts from land clearing activities Construction activity or process Land Clearing

Environmental Aspects

Environmental Impacts

removal of existing vegetation

biomass incineration mulching of biomass exposed soil surface

Beneficial

Adverse

-revenue from sale of marketable trees or plants -use of tree trunks for temporary erosion control

loss of tree cover reduced aesthetics blocked waterways causing flooding loss of terrestrial habitat air pollution

-reuse in landscaping erosion and siltation water pollution flash floods Landslides air pollution land contamination air pollution vibration noise pollution risk to public safety

slope instability vehicular emissions vehicular movement

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Table 3. Examples of Environmental aspects and impacts during construction OUTPUT/IMPACT ASPECTS/INPUT Land clearing denude vehicular movement tree felling

Construction piling premix vehicular movement blasting drilling chemicals skid tanks scheduled wastes

Workers base camps public amenities

Air

Vibration

Noise

Dusty Fumes Heat

Annoyance

Annoyance

Annoyance

Annoyance Annoyance Annoyance

Annoyance Annoyance

Annoyance Annoyance

Dust Dust/fumes Dust/gases Dust VOCs

Water Silting High BOD Low DO Less suitable for aquatic life

Soil Surface runoffs Muddy Weakening of slopes

Spillage Spillage Spillage/ contaminant

Spillage Spillage Spillage/ contaminant

Sullage

Domestic wastes

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Aspect No

Yes

Legal Requirement No

Activities and Environmental Consequences

Yes

Yes

No

SIGNIFICANT ENVIRONMENTAL ASPECT (SEA)

Yes

Use of Materials No

Corporate Concern No

NOT SIGNIFICANT

Figure 6. Workflow for the evaluation of the significance of environmental aspects.

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13. HOW TO IDENTIFY ENVIRONMENTAL ASPECTS AND SIGNIFICANT IMPACTS The general flow of evaluating the significance of the environmental impacts is represented in Figure 6. In a more detailed approach, the first step in identifying environmental aspects and significant impacts of the construction is to develop a map of the processes and activities. First, categorize the activities into areas or steps in the process, so that it can be reviewed one by one. Some typical areas to consider might include: land clearing, mobilization of heavy machinery, building an access road, constructing earth drain, earth works, and piling. Next is to select a related construction activity followed by identifying as many as possible environmental aspects associated with the chosen activity, taking into account that environmental aspects can be positive (e.g. recycling waste) and negative (e.g. generation of toxic waste). Aspects rising from normal and abnormal operating conditions as well as potential emergency situations should also be considered [14.15]. The method statement of each operation can be used as a reference to identify environmental aspects. Keep in mind that the relationship between environmental aspects and environmental impacts is one of cause and effect. Then, evaluate the significance of the aspects and associated impacts by using a set of criteria appropriate to the construction sector. Among the criteria which are widely used are frequency, severity, probability, duration, legal requirements, environmental consequence, corporate concerns, resource depletion, human health effects etc. Application of the methodology and evaluation criteria should be consistent

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throughout the process. Lastly, develop a register, listing out all activities which have significant environmental aspects and their associated impacts. At the end of the identifying process, when all activities under the scope have been adequately covered as in Table 4, documented procedures for identification of aspect and impacts are prepared. In these documents, the methodology and criteria are clearly defined and the records of identified aspects and impacts for verification will be obtained. A prioritized list of significant aspects and impacts and the basis used to determine prioritization will also be kept in record. Accordingly, the most significant shall be addressed and managed first [15]. Table 4. Construction activities, examples and the sequence to establish significant aspects EXAMPLES Construction activities:

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Environmental aspects:

Environmental impacts:

Land clearing Mobilization of heavy machinery Building access road Constructing earth drain Earth works Piling Transportation of raw materials into site Transportation of from site Consumption of natural resources. Removal of vegetation Removal of top soil. Discharge of waste water, waste oil, building waste etc. Consumption of electricity. Emission of dust and other particulates Noise and dust Depletion of Natural Resources. Loss of soil fertility. Loss of flora and fauna. Loss of habitat Soil erosion Visual impact/ intrusion Water pollution – waste, siltation Air pollution –dust and particulate Global warming Noise pollution Flash floods The link between aspects and impacts is similar to “cause and effect”

SEQUENCE TO THE ESTABLISHMENT OF SIGNIFICANT ASPECTS Use an established methodology and evaluation criteria appropriate to the construction sector. The methodology can be qualitative, quantitative and semi-quantitative The evaluation team shall have common understanding on the methodology and application of the criteria. Application of the methodology and evaluation criteria should be consistent through out the process. From the evaluation process a list of significant aspects register shall be produced. The list leads to the following: a. The activities that are needed to be managed in order to reduce the environmental impacts from our organization b. Which activities are covered under legal and other requirements? c. What type of works that require competent people in order to prevent environmental impacts and compliance to the environmental policy? d. Which type of staff would require environmental related training? From the list it is critical to prioritize to ease the management process. Basis shall be its significance to the environment and legal compliance. The final list will guide the industry in setting its environmental policy and the environmental objectives.

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14. MONITORING AND MEASUREMENT Measuring and monitoring are required to ensure that the construction environmental objectives and targets are being achieved. Hickie and Wade [14] advocated the monitoring of environmental parameters as essential to ensure compliance to the regulation as well as maintaining the effectiveness of mitigating measures taken up. Examples of environmental issues that need to be measured and monitored:

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i)

Water quality (all affected rivers - 10 m upstream and downstream). The water quality at all river crossings should be monitored prior to construction to determine the baseline water quality by taking and analyzing water samples for the following parameters: Dissolved oxygen (DO), electrical conductivity, temperature, pH, biological oxygen demand (BOD), chemical oxygen demand (COD), ammoniacal nitrogen (NH3-N), nitrate (NO3-N), phosphate (PO4-P), oil and grease, turbidity, total suspended solids (TSS), total dissolved solids, total solids). For subsequent sampling parameters : pH, temperature, DO, BOD, COD, TSS, ammoniacal nitrogen, and oil and grease ii) Air quality (dust, air particulate at residential areas and at project site boundaries) iii) Noise (residential areas and forest reserves and at project site boundaries) iv) Erosion risks (erosion sensitive areas; temporary cover to control erosion and permanent erosion control – drainage, surface protection, gabions, riprap) v) Slope stability /protection (erosion sensitive areas; immediate revegetation, protect slope from concentrated surface runoff, hard plugs) vi) Solid and hazardous waste handling and disposal vii) Archaeological heritage sites viii) Waterway crossings (waterways must not be hindered; crossings shall be adequate to permit heavy storm water flow, embankments stability/protection) ix) River bank protection ( riprap, gabion) x) Flora and fauna xi) Health and safety xii) Sediment/silt trap (location, trap size, embankment, excavation, trap clean out, outlet, clearing, fill material, sedimentation, inspection after each rain and repairs, construction operations to minimize water pollution) xiii) Conservation of agricultural land - protected from any deterioration and impact (every month) xiv) Hydrology–drainage system-maintenance, drainage channels, flumes (pipes to channel water across the right of way, berms and berm spacing and conditions) xv) Compliance with government regulations – permits

Monitoring and measurements can serve many purposes in an environmental management system, such as tracking progress on meeting the environmental policy, achieving objectives and target, and continual improvement [16]. These will lead to, developing information to identify significant environmental aspects, monitoring emissions and discharges to meet applicable legal requirements or other requirements to which the organisation subscribes, monitoring consumption of water, energy or raw materials to meet

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objectives and targets. Russell [17] had suggested that monitoring also provides data to support or evaluate operational controls, organisation’s environmental performance and the performance of the environmental management system. Faith-Elle et al. [6] added that monitoring data can also be used to evaluate environmental performance, analyze root causes of problems, assess compliance with legal requirements, identify areas requiring corrective action, improve performance and increase efficiency. There are several procedures a contractor is advised to chart. The first would be to monitor key characteristics of operations and activities that can have significant environmental impacts and/or compliance consequences. This would be an indicator of where problems may be occurring in the process. The next is to track performance including progress in achieving objectives and targets. If special equipment is used to measure environmental performance, it is important to maintain and calibrate the equipment on a regular schedule and designate this task to a responsible staff with appropriate training. Throughout internal audits, one should also periodically evaluate compliance with applicable laws and regulations. To achieve these purposes, Meretsky et al., [8] recommended the contractor should plan what will be measured, where and when it should be measured, and what methods should be used. To focus resources on the most important measurements, the contractor should identify the key characteristics of processes and activities that can be measured and that provide the most useful information

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15. HOW TO CONDUCT MEASUREMENT Measurements should be conducted under controlled conditions with appropriate processes for assuring the validity of results, such as adequate calibration or verification of monitoring and measurement equipment, use of qualified personnel, and use of suitable quality control methods [18]. When necessary to ensure valid results, measuring equipment should be calibrated or verified at specific intervals, or prior to use, against standards traceable to international or national measurement standards. If no such standards exist, the basis used for calibration should be recorded. Written procedures for conducting measurement and monitoring can help to provide consistency in measurements and enhance the reliability of data produced. The measurement and monitoring results should be analyzed and used to identify both successes and areas requiring correction or improvement [10].

16. MANAGING ENVIRONMENTAL ASPECTS AND IMPACTS The concerted effort to provide economic boost and lifestyle improvement has failed to conserve the fragile natural resources. In recent times, we have encountered problems of encroachment of development into agricultural and forestry areas, degradation of the natural habitats through air pollution, disturbance of land and water contamination through soil runoff and erosion [8].

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Table 5. An example of summarized monitoring requirements for road construction Environmental issue Air quality and noise

Person responsible Environmental officer

Parameters

Frequency

Total suspended particulates

Construction phase: once a week during land clearing and earthworks Once a fortnight during other construction works Operational phase: none required: Construction phase: Standard C: 0.4 g/Nm3

Solid particles – all fuel burning equipment and asphalt plant Noise – border of construction area Soil erosion

Project Engineer

Sedimentation rates – silt traps

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Slope stability

Water quality

Environmental officer

Identified locations

Wildlife

Department of Wildlife

No of locations – every kilometer: Physical surveys and observations. Ground mammals

Solid waste

Environmental officer

Base camp and along kilometer stretch of the construction site.

Construction phase: once a fortnight Construction phase: twice a week during land clearing and earthworks. Once a fortnight during other construction works. Operational phase: none required. Construction phase: once a week Operational phase: Once a fortnight. Construction phase: Twice a week during land clearing and earthworks between month 1-20. Once a week during month 21 – 30 Operational phase: once fortnight Construction phases: BOD, E.coli at sewage discharge. All parameters to comply with regulations continuously throughout construction and operational phases. Construction phase: once a week during land clearing and earthworks to detect and relocate displaced animals. Post construction phase: patrol area once a month. Construction phase: once a week. Post construction phase: once a month.

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One of the most effective way to ensure that environmental issues are given proper considerations throughout the whole development process is to incorporate a form of environmental management. The term environmental management means the management of the impacts of human activities on the environment [19]. In Malaysia, environmental management has very much evolved from the first introduction of Environmental Impact Assessment (EIA) on new development to the current, environmental management in the construction industry which includes environmental management plan (EMP), environmental monitoring (EM) and environmental auditing (EA) [20]. Improvements in environmental performance are often seen as a cost burden to the operator, which they must either absorb to maintain their competitive edge or pass onto the customers if they are to maintain their profit margin. There are many benefits in pursuing better environmental performance not only for the environment directly but also for the industry financially. For example, in the area of waste minimization and pollution prevention, these include a reduction in operating costs and lower overall costs with comparison to competitors. The further financial motivator of having an environmental management system is the imperative of legislation usually backed by various financial penalties. Raising awareness of the ecological and environmental issues to a level where these issues are ranked as priority factors is a precursor for an enhanced environmentally benign construction. In many cases the industry is required to recognize long term interest in favor of short term gains. Chen et al., [5] had laid emphasis that with the environmental management system properly in place, the perception of ecologically sound construction is to be aimed for and valued and should be popularized rather than considered as unusual or unachievable. The environmental management system will be the conveyance of the message on the value of ecological and environmentally friendly construction. The environmental management system is to be promoted as a vehicle to develop environmentally friendly practices in the construction industry [6]. The system provides a standard framework that includes environmental policy, planning, implementation and operation, checking and corrective action and measurement review and improvement. It can be developed to assist the industry to improve their environmental performance on a voluntary basis through coherent allocation of resources, assignment of responsibilities and the continuing evaluation of practice. Benefits of having an environmental management system in the construction industry include: • • • • •

To project the environmental issues that might arise from the construction To prevent unwanted environmental problems To minimize environmental risks associated with construction To comply to laws and regulations To improve the overall environmental performance of the construction industry of Malaysia

Improvement of the construction industry environmental performance will be on a voluntary basis through coherent allocation or resources, assignment of responsibilities and the continuing evaluation of practice. This fosters self–organization and self regulation, which

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represent the groundwork from which it is hoped that continuous improvement of environmental performance can be sustained. Apart from the employment of EIA, EMP, EM and EA in development projects, other environmental management tools can also be incorporated such as the Environmental Management System, Environmental Performance Indicators, Life Cycle Analysis and Environmental Labeling [3]. The environmental management system is a part of the overall management system which includes organizational structure, planning activities, responsibilities, practices, procedures, processes and resources for developing, implementing, achieving, reviewing and maintaining the environmental policy (MS ISO 14001, 2004). It is a widely used tool for managing environmental impacts of the development process and for promoting sustainable development [21]. This system is best seen as a systematic framework that is continually monitored and intermittently reviewed. The system starts off by implementing a policy that mirrors the commitment of the organization toward environmental care, establishing the objectives and processes necessary to deliver results in accordance to the policy, implement the processes, monitor and measure processes against environmental policy, objectives, targets, legal and other requirements, and report the results, and finally to take actions to continually improve performance of the environmental management system.

17. CONCLUSIONS

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There are many approaches to identifying and prioritizing environmental aspects and impacts and the key is finding an approach that works for that particular organization. It is important to identify the most significant issues, but not to go into excessive details. An Environmental Management System, if implemented properly, can improve communications, establish responsibilities, training, and methods to address environmental issues and ultimately achieve environmental goals and sustainable construction.

REFERENCES: [1] [2] [3]

Al-Reshaid, K.; Kartam, N. Inter J. Project Management. 2005, 23. 309-320. Mendoza, G.A.; Prahbu, R. Forest Ecology and Management. 2000, 131, 107-126. Woods, C.; Dipper W.; Jones, C. J. Env. Planning and Management, 2000, 43(1), 2347. [4] Nik Norulaini N.A.; Mohd Omar, A.K. Environmental Management Plan for the construction of Benta Jerantut Highway, Department of Irrigation and Drainage, Malaysia, 2001 [5] Chen Z.; Heng L.; Hong J. Automation in Construction. 2004, 13, 621-628. [6] Faith-Elle, C.; Balfors, B.; Folkeson, L. J. Cleaner Production. 2006, 14, 163-171. [7] Brown, D.; Jacobs, P. Habitat Intl. 1996, 20, 493-507. [8] Meretsky, V.J.; Wegner, D.L.; Stevens, L.E. J. Env. Management. 2000, 25, 579-586. [9] Harbor, J., J. Geomorphology. 1999, 31, 247-263. [10] Dipper, B.; Jones, C.; Wood, C. J. Env Planning and Management. 1998, 41(6), 731747.

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60 [11] [12] [13] [14] [15]

[16] [17] [18]

Wood, G. J. Env. Planning and Management, 1999, 42, 671-689. Muttamara, S. J. Resources, Conservation and Recycling. 1996, 16, 335-349. Lahdelma, R.; Salminen, P.; Hokkanen, J. J. Env. Management. 2000, 26, 595-605. Hickie, D.; Wade, M. EIA Procedure. 1998, 18, 267-287. Zobel, T.; Burman, J.O. Factors of Importance in Identification and Assessment of Environmental Aspects in an EMS Context: Experiences in Swedish Organizations. 2004, 12, 13-27 Walker, G.; Bayliss, D. J. Env. Planning and Management, 1995, 38, 134-159. Russel, C.S. Reg Environ Change. 2001, 2, 73-76. Sanvicens, G.D.E.; Baldwin, P.J. J. Env. Planning and Management. 1996, 39, 429440. Selih, J., (2007). J. Civil Eng and Management. 2007, 13, 217-226. Morrison-Saunders, A.; Bailey, B. J. Env. Management. 1999, 24, 281-295. Ball, J. Building and Env. . 2002, 37, 421-428.

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[19] [20] [21]

Nik Norulaini Nik Ab Rahman, Fatehah Mohd Omar and Mohd Omar Ab Kadir

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In: Impact, Monitoring and Management… Editors : Ahmed El Nemr

ISBN 978-1-60876-487-7 © 2010 Nova Science Publishers, Inc.

Chapter 3

RADIATION IN THE ENVIRONMENT: SOURCES, IMPACTS AND USES Amidu O. Mustapha1 Department of Physics University of Agriculture, Abeokuta, Nigeria

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1. INTRODUCTION Radiation is the transport of energy in the form of electromagnetic waves or energetic particles through space or material. Although all forms of radiation are important, the main concern in this chapter is the ionizing radiation, i.e. those that can cause ionization in the medium through which they traverse. The environment is permeated by ionizing radiation from diverse artificial and natural sources. Ionization can disrupt normal biological processes in living tissues, therefore it may be harmful to living organisms in the environment, including human beings. But as a natural component of the environment, ionizing radiation is not always detrimental to life, rather it is compatible with life. A complete elimination of ionizing radiation from the environment is therefore neither possible (because some of the sources are not amenable to control) nor desirable since it has many important beneficial applications. Indeed, there is clear evidence that our present and emerging lifestyles will not be sustainable without applications of radiation technologies, e.g., in health, agriculture, energy, environmental studies, etc. There are many authoritative books and reviews on various aspects of radiation and radioactivity in the environment, e.g. see Eisenbud [1] and UNSCEAR [2]. Therefore this chapter will focus mainly on the impacts of radiation in the environment: on one hand as an environmental contaminant or pollutant arising partly from both natural phenomena and human activities, and on the other hand as a tool for studying and conserving the environment. An overview of the various natural and artificial sources of environmental radiation is first presented, followed by a presentation of the environmental and radiological impacts of the various sources. The latter includes reviews of the

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developments in radiation dose assessment and radioactivity measurement techniques, as well as a brief description of the beneficial uses of radiation particularly in environmental studies.

2. SOURCES OF ENVIRONMENTAL RADIATION The ultimate origin of radiation is the atom, the basic building block of matter. Most atoms are stable, but some are unstable. Instability in atoms may occur naturally, but it can also be induced artificially. An unstable atom has ‘excess’ internal energy, with the result that the nucleus can undergo a spontaneous change towards a more stable form. This is called 'radioactive decay' and the atom is said to be ‘radioactive.’ When an atom decays, it gives off some of its ‘excess’ energy as nuclear radiation in the form of gamma rays or energetic particles. This is the inseparable link between (nuclear) radiation and radioactivity. The internal energy of an unstable atom may also be given off as x-rays. Historically, it was William Rontgen’s discovery of the X-ray (atomic radiation) in 1895 that preceded and paved the way for the discovery of radioactivity (and hence nuclear radiation). The following year (1896), while investigating the fluorescence associated with x-rays, Henri Becquerel also discovered radioactivity and thus established the existence of a naturally occurring radiation emitting (or radioactive) element, subsequently called uranium. In 1898, two new radioactive elements were discovered and named polonium and radium by Pierre and Marie Curie. Therefore all the sources of radiation in the environment are either natural or manmade.

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2.1. Natural Sources of Radiation The two main components of natural sources are the emissions reaching the earth’s atmosphere from cosmic and solar activities, and the primordial radionuclides believed to have remained in measurable quantities since the elements which make up the earth were synthesized about 5 billion years ago. The primordial radionuclides and their radioactive decay products are distributed in rock, soil, building materials, water, air, foodstuffs, and in all the remaining living and non-living components of the environment.

(I). Cosmic or Extraterrestrial Sources of Radiation Cosmic radiations originate from outer space and penetrate earth’s geomagnetic shielding before reaching the earth’s atmosphere. Primary cosmic radiation comprises three components according to their origin. These include [2,3] solar radiation, which is produced in the sun; galactic radiation, generally believed to be produced and accelerated as a consequence of stellar flares, supernova explosions, pulsar acceleration, or explosion of galactic nuclei [4]; and the so-called Van Allen radiation, composed of charged particles trapped in the earth’s geomagnetic field, forming radiation belts. Primary Cosmic Rays The primary cosmic radiation consists mainly of highly energetic protons, some electrons, neutrinos, alphas and heavy ions. Primary cosmic rays only make direct

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contribution to the radiation exposure of human beings during flights at high altitudes or during space missions.

Secondary Cosmic Rays and Cosmogenic Radionuclides While penetrating the earth’s atmosphere, the primary cosmic radiation interacts with atoms in the earth’s atmosphere and produce secondary particles and photons (secondary cosmic radiation), and radionuclides (cosmogenic radionuclides). Secondary cosmic radiation consists mainly of neutrons, protons, kaons, electrons and muons. The most important cosmogenic radionuclides are 3H, 7Be, 14C and 22Na which are found in significant concentrations in body tissues [2,5]. At the ground level, human doses result mainly from secondary cosmic radiation. (Ii). Primordial Radionuclides or Terrestrial Sources of Radiation It has been reasoned [6,7] that, following its formation, the young earth probably contained a larger number of radioactive elements than there are at present. The short-lived radioactive elements decayed, leaving only those with half-lives comparable to the estimated age of the earth (4.6 billion years) [6]. The most important of these primordial radionuclides are 40K (half-life = 1.28 109 y), 87Rb (half-life = 4.7 1010 y), 232Th (half-life = 1.41 1010 y), and 238U (half-life = 4.47 109 y). Many more naturally occurring radioactive elements are formed along the decay series of 238U, 237Np, 235U, and 232Th. The primordial radionuclides and their radioactive decay products are therefore ubiquitous in the natural environment. They are found in the soil, rocks, building materials, water, food, air, and even in our bodies, since we are what we eat! Global reviews of values of various naturally occurring radionuclides in the environment are presented in the UNSCEAR reports [e.g., 2,8].

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2.2. Artificial Sources of Radiation Many test explosions were carried out in the 1950s and 1960s, which released radioactive products into the atmosphere. Nuclear weapons tests are the largest source of artificial radioactivity released into the environment [9]. The fallouts elements, e.g. 90Sr, 137Cs, etc, were transported around the world and eventually deposited in various environmental media. Anthropogenic radiation and radionuclides are also released into the environment during routine operations of nuclear reactors and supporting facilities such as uranium mines, mills and fuel fabrication plants; and from other non-nuclear establishments that use radioactive materials in their operations, e.g., hospitals and research institutions. Another important source of anthropogenic radionuclides in the environment is nuclear accident. Notable accidents in history are the Three Mile Island and Chernobyl nuclear accidents. Radionuclides are also released into the environment from stored and disposed radioactive wastes. Many radioactive materials have been manufactured as sealed sources of radiation for various uses. These, and many other electric operated machines, also generate radiation into the environment inadvertently through uses in medical procedures, industries, in agriculture, in engineering construction, in luggage checks at the ports, in radiography of motor and airplane parts, etc. There are also many consumer products in the market, which contain

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radioactive materials or/and emit radiation, e.g., television sets (which emit soft x-rays), radioluminescent time pieces, smoke detectors, gas mantle containing thorium, etc.

2.3. Technologically Enhanced Natural Sources of Radiation All the materials containing naturally occurring radioactive radionuclides, particularly K and those in the decay series of 238U and 232Th are called Naturally Occurring Radioactive Materials (NORM). There is no doubt about the distinction between the natural and the artificial sources of radiation, But the distinction between “unmodified natural radiation” and the “modified natural radiation” sources or the “technologically enhanced natural radiation sources” are sometimes not obvious. The latter has been defined [9] as truly natural sources of radiation exposures to which exposures could not occur without (or is increased by) some technological activities not originally designed to produce radiation. For example, nuclear and conventional (non-nuclear) mining operations often result in extraction and pilling of large quantities NORM. Extractions of these minerals, although not originally designed to produce radiation, may inadvertently result in the enhancement of the natural radiation background around the mining areas. This is one of the cases of human activities enhancing the natural radiation level. In another example, radionuclides such as 210Po and 226Ra are released into the atmosphere from coal-fired power stations. Other examples of technologically enhanced natural sources of radiation are: production and application of phosphate fertilizer, high altitude flight and space travel, etc.

40

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3.1. Historical and Contemporary Perspectives on the Impact of Radiation In the early days of X-rays and radioactivity, it was generally believed that ionizing radiation had numerous beneficial effects. The successful separation of radium (from its minerals) by the Curies was particularly followed by an explosion of interest in its use in medicine and industry. This paved way to commercial production and world-wide exploration and exploitation of its ore (uranium ore). By the 1930s, the world market for uranium ore had been fully developed, with major supplies from the Democratic Republic of Congo (then known as Belgian Congo), Canada and the USA. People visited spas to drink mineral water containing radium and inhale steam containing radon gas. But as the exploration and exploitation of uranium ore (for radium) continues, so do the growing concerns over the reported cases of health hazards associated with the use of radium. This, and earlier concerns over the safety of x-ray, led to the formation of the International committee on X Ray and Radium Protection in 1925. This committee was the forerunner of the present day International Commission on Radiological Protection (ICRP). Before the world could come to terms with the hazardous effects associated with the applications of radium in medicine and industry, another significant discovery had been made which further increased the exploration and exploitation of uranium. In 1938, Hahn and Strassman’s discovery of nuclear fission established a bigger use for natural terrestrial

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radioactivity. As a result of the requirement of the nuclear technology, attention was shifted from radium to uranium as the main product of uranium ore and radium was reduced to a byproduct [11] and an environmental pollutant. But the positive interests in radiation persisted through until the end of World War II. Public opinion about radiation changed after the war and following the development of nuclear weapons through out the cold-war era and subsequent increase in the use of nuclear power. The public has since become radio-phobia, raising objections to all levels of radiation in the environment. In contemporary times, the most important source of man-made radiation exposure to the majority of the people is from (beneficial) medical procedures, such as diagnostic X-rays, nuclear medicine, and radiation therapy. Some of the major radioisotopes used in these medical procedures are 131I, 99mTc, 60Co, 192Ir, 137Cs, etc. Many of us benefit from a multitude of products and services made possible by the careful use of such artificially produced radiation and radionuclides. However, most members of the public are also exposed, inadvertently, to radiation from consumer products, such as tobacco (thorium), building materials, combustible fuels (gas, coal, etc.), televisions, luminous watches and dials (tritium), airport X-ray systems, smoke detectors (americium), road construction materials, electron tubes, lantern mantles (thorium), etc. with no direct benefits. Members of the general public receive less radiation exposures from nuclear fuel cycle, which includes the entire sequence from mining and milling of uranium to the actual production of power at nuclear power plants, shipment of radioactive materials and residual fallout from nuclear weapons testing and even accidents, such as Chernobyl.

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3.2. Developments in the Assessment and Control of Radiological Impacts Human beings and the biota have always lived in a background of radiation from natural sources and it is only about a century ago that artificial sources of radiation became additional sources of exposures. But it is these additional exposures that generate more concerns and more responses in terms of limitation and control [12]. It was concern over the effects of fallout from nuclear weapon tests that initiated the establishment of UNSCEAR, in 1955, by the General Assembly [13,14]. Until recently, the common understanding is that natural exposures are mainly from sources that were generally not amenable to human control, such as cosmic rays, 40K in the body, and radionuclides in the earth’s crust [10]. However, three decades later there has been noticeable increase in awareness of the significance of natural exposures and the need to control the important components [12-16]. According to early assessments by the UNSCEAR, the world average dose from natural radiation was less than 1.0 mSv per annum prior to 1977 and only around 1.0 mSv per annum in 1977 [13]. Following the introduction of the concept of effective dose equivalent in 1977 [12], which implies that doses received in different organs are added to obtain the total dose, and the doubling of the quality factor of alpha particles, the world average annual dose rose to 2.0 mSv in the 1982 UNSCEAR Report. This value increased to 2.4 mSv in 1988 but it has remained so in the subsequent assessments [2]. This trend demonstrates an improvement in the understanding of the significance of exposures to natural sources of radiation and also in the assessment procedures.

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The problems associated with control of exposures to natural sources of radiation have still not been completely resolved. In 1977, the ICRP [12] approach was to distinguish between normal levels of exposure and enhanced levels. The primary dose limits recommended by the ICRP in the control of artificial sources of radiation do not apply to normal levels of natural exposure [12]. Seven years later, following many reports of unexpectedly high doses from natural sources of radiation, the commission [15] concluded that the distinction between normal and enhanced levels was unhelpful and difficult to establish. New guidelines were provided [15], based on the approach in which the emphasis is on the extent to which the exposure to the source is controllable. Exposures to natural sources were then classified into existing and new situations [15]. The new or future situations were considered easier to control than existing situations. In existing situations the exposures can be altered only by taking remedial actions and are likely to be more objectionable than the limitations for future situations which are implemented at the stage of decision and planning [15,16]. But there are cases when the borderline between the two situations will be ill-defined and the choice may seem arbitrary [15]. Approaches later shifted to distinguishing between intervention and practice, and between occupational and non-occupational exposures [16,17]. Previous and current approaches to assessments of radiation exposure [2] and establishing radiation protection standards [16] are focused only on protecting the human population with the assumptions that by protecting human beings the rest of the living environment are adequately protected. But there are ongoing efforts that are revealing a better understanding of the impacts of radiation on the non-human component of the living environment, and there are indications of dose limits specifically recommended to control radiation exposures of specific non-human populations. For example, 10 mGy/h, is the recommended dose limit [18] to prevent mortality increase in a population of aquatic organisms. It is also envisaged that the next ICRP recommendation will provide a framework for the protection of the non-human species and the environment. This paradigm shift will, however, require development of new nomenclature, data sets, reference dose models, etc. (e.g., see [19]).

3.3. Transport of Radionuclides in the Environment Radionuclides released into specific locations in the environment have the potential of being transferred to other parts through various routes by various transfer mechanisms. The likely routes for specific radionuclides and the concentrations at various compartments along the route depend on many factors. They include the mode of release, the physical characteristics of the sources or release points, physical and chemical properties of the radioactive materials, and a host of other environmental factors. Once released in the air, radioactive materials may be transported great distances by local and large-scale air movements. ‘The time periods that the materials remain airborne depend on the latitude, time of year and the height of injection into the atmosphere. The depletion processes include gravitational settlement and dry impaction, wet deposition (i.e. incorporation into rain drops and washout by falling precipitation). The physical and chemical characteristics of the materials themselves, e.g. particle size and chemical and physical forms, may also influence removal rates’ [2].

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The ratio of the concentrations in any two adjacent compartments along the transfer route is called the transfer factor. This is a very important parameter in dose assessments [2] and the accuracy of calculated doses depends on the transfer factors adopted. As a result of its importance, there are ongoing efforts to develop a better understanding of the behaviour and transport of radionuclides in the environment, e.g. using models. For example, see the book ‘Modeling Radioactivity in the Environment’ edited by Scott [20].

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3.4. Exposure of the General Public to Natural Background Radiation Exposure to the natural background radiation is inescapable for all human beings and other biota although it differs from place to place, depending on geology, latitude, and altitude of human settlements. Human beings are exposed to sources of radiation outside their bodies (external exposure), mainly from cosmic rays and radionuclides in the air, ground and in walls of buildings. Also, radionuclides are inadvertently incorporated into the living tissues by ingesting food and water and inhaling air. The circumscribed parts of the body are irradiated by emissions, mainly of low penetrating α- and β-particles, from the ingested or inhaled radionuclides and also from 40K in the body, leading to internal exposure. Assessments of human exposures to different components of natural sources of radiation have been carried out in many parts of the world. A breakdown of contributions from various components of the natural radiation sources indicates that radon is by far the greatest contributor to the world population-weighted annual effective dose equivalent in areas of normal background [2]. Table 1 shows a summary of worldwide averages and ranges of human exposures to natural background radiation. The typical background radiation levels in most parts of the world are not of any radiological significance. But there are a few areas in different parts of the world where significantly higher radiation levels have been recorded mainly due to the presence of enhanced concentrations of radioactive elements in the geologies of these areas. Such cases have been reported [2] in Brazil (e.g., Guarapari), China (Yangjiang), Egypt, India (e.g., Kerala), Iran (e.g., Ramsar), and Kenya [22]. Table 1. Ionizing radiation exposure of the general public from natural sources alone [2,21] World Average doses Source

Effective dose (mSv per year)

Typical range (mSv per year)

External Exposure - Cosmic rays - Gamma rays (terrestrial)

0.4 0.5

0.3 – 1.0 0.3 – 0.6

Internal Exposure - Inhalation (mainly radon) - Ingestion (40K, U and Th series) Total

1.2 0.3 2.4

0.2 – 10 0.2 – 0.8 1 – 10

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3.5. Comparing Human Exposures to Natural and Artificial Sources The general public perception is that artificially produced radiation is detrimental to human health and the living environment. But scientific evidence shows that natural sources of radiation contribute more to the collective radiation exposure of the world’s population than do all artificial sources [2]. About five decades of releases of artificially produced radionuclides into the environment has not resulted in obvious detriments to the global environment nor significantly increased the collective dose to the word’s population, in contrary to the public perception [9]. One of the significance of studying the natural component of environmental radiation is that it provides the benchmark for us to understand the radiological significance of the practices that generate artificial sources of radiation. This is depicted by the following two tables (2 and 3). Table 2 shows that about 80% of the collective dose received by human beings around the world is due to natural radiation exposures. Similarly, Table 3 shows that atmospheric nuclear weapon tests are the most important artificial source of radiation in the environment but they are comparatively insignificant to natural sources. One year’s collective dose (11 Million man Sv) from natural sources is more than double all the previous practices of test explosions (5 Million man Sv).

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Table 2. Collective dose committed to the world population by a 50-year period of operation for continuing practices or by single events from 1945 to 1992 [3] Source

Basis of commitment

Collective effective dose (million man Sv)

Natural sources

Current rate for 50 years

650

Medical exposure Diagnosis Treatment

Current rate for 50 years

Atmospheric nuclear weapon tests

Completed practice

30

Nuclear power

Total practice to date Current rate for 50 years

0.4 2

Severe accidents

Events to date

0.6

Occupational exposure Medical Nuclear power Industrial uses Defence activities Non-uranium mining

Current rate for 50 years

Total (all occupations)

90 75

0.05 0.12 0.03 0.01 0.4 0.6

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Table 3. Summary of world estimates of effective dose equivalent [8]

Source or practice

Present annual individual doses (mSv) Per caput Typical (World (Exposed population) individuals)

ANNUAL Natural Background

2.4

Collective dose commitments Million Equivalent man Sv years of background PER YEAR OF PRACTICE

1–5

0.4 – 1

0.1 - 10

2–5

0.2 – 0.5

0.002

0.5 - 5

0.01

0.001

Nuclear power production SINGLE

0.0002

0.001 – 0.1

0.001 (0.3)a

0.0001 (0.004)a

PER TOTAL PRACTICE 0.01

0.01

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1

Medical exposure (diagnostic) Occupatio nal exposure

All test explosions together

a

11

5 (26)a

0.5 (2.4)a

0.6

: The additional long-term collective dose commitments from radon and carbon-14 for nuclear power production and carbon-14 for test explosions are given in parentheses.

Tables 2 and 3 deal with exposures of the general public. Some people will receive additional radiation exposure due to special needs, e.g., medical needs (medical exposures), bearing in mind the requirements of justification, optimization and dose limitation according to the ICRP Recommendation. Another group (fewer) of people receive extra amount due to the nature of their jobs (Occupational exposure). Occupational exposures that are related to naturally occurring sources of radiation are also comparatively higher than those related to artificial sources as shown in Table 4.

3.6. Beneficial Uses of Radiation in the Environment As contaminants, the radiological impact of radiation and radioactivity in the environment have been stressed in the previous sections. Some of their beneficial uses will also be mentioned in this section. In basic researches, radiation is being used as a convenient tool to study fundamental processes. For example, scientists are studying cosmic radiation to

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explain the primeval changes that took place billions of years ago as well as the ongoing transformations and developments taking place in the universe based on the association of such changes with the natural radiation. Radiation and radioactivity is also playing very important role in our day to day lives. It has several applications in Agriculture, industry and health. Many radionuclides, both naturally occurring and artificially produced, are being used in environmental studies. The most common naturally occurring radionuclides include 234Th, 222 Rn, 210Pb, 14C, 7Be, 3H, etc. While 137Cs, 90Sr, 14C, and 3H are among the anthropogenic radionuclides that are mostly applied in environmental studies. Table 4. Occupational radiation exposures [21]

Radiation sources

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MAN-MADE SOURCES Nuclear fuel cycle Other industry Defense activities Medicine Education/veterinary TOTAL ENHANCED NATURAL SOURCES Mining (excluding coal) Coal mining Aircrew Mineral processing Radon in Workplaces (above ground) TOTAL

Average doses to workers Number of monitored Effective dose Workers (mSv per year) 800,000 700,000 420,000 2,320,000 360,000 4,600,000

1.8 0.5 0.2 0.3 0.1 0.6

760,000 3,910,000 250,000 300,000 1,250,000 6,500,000

2.7 0.7 3.0 1.0 4.8 1.8

The simplicity of the decay law and the occurrence of decay series, i.e. transmutation from one radioactive specie (parent) to another radioactive specie (daughter) are two of the traits that illustrate the uniqueness of radioactivity, which attract interests to its study and applications [23]. Many applications also take advantage of the specificity of radioactivity and the sensitivity with which it can be detected to quantify specific isotopes in the environment, even at very low concentrations. Some examples of applications of radionuclides in radio-tracing and radiometric dating are given below.

Radio-Tracing In radiotracer techniques, a small amount of radioactive isotope is mixed with a substance containing a large amount of other stable isotopes of the element. The element is said to be tagged, and it is now monitored through various chemical, biological, and physical processes. This tracer technique is widely employed in many fields including medicine, biology, agriculture, metallurgy, hydrology, etc. It has been used to solve otherwise technologically intractable problems in medical diagnosis, criminology, pollution, leakage, etc. 3H is also a tracer for the world hydrological cycle, and 14C is used for tracing global carbon cycle [2]. The ability to trace groundwater using these radionuclides has provided a valuable tool for

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groundwater exploitation. The measurements of radionuclides transfer processes from past releases have also been used to study and infer large-scale atmospheric and hydrological movements on the earth [2]. Similarly, fallout radonuclides, e.g. 90Sr and 137Cs, have been used to infer material removal or renewal times (residence times) in the environment. Kirk and Masque [24] review many uses of natural radionuclides in quantifying the rates of coastal ocean processes. For example, 234Th, 210Pb, 14C, and 7Be are used to study the rates of scavenging, sediment mixing and accumulation, while 222Rn and 226Ra are used to study rate of groundwater inflow [24].

Radiometric Dating One of the earliest uses of radioactivity is radiometric dating. It is generally based on the decay law: N (t ) = N (t = 0) exp(−λt ) , where N (t ) is the number of nuclei present in the sample at time t, N (t = 0) is the number at t = 0 , and

λ is the probability per unit time that

a decay will occur, also called decay constant. There are a number of dating schemes depending on the age range of interest. For example, ages in the million to billion years age range such as the age of the earth are determined from the ratio of uranium (238U) to lead (210Pb), e.g. in rock samples. Ages down to thousands of years are determined using radiocarbons (14C) dating, while ages of the order of few years, e.g. age of water in aquifers, are determined using tritium (3H).

REFERENCES

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[1]

[2] [3] [4]

[5] [6]

[7] [8]

Eisenbud, M. (1987) Environmental Radioactivity, 3rd Ed. Academic Press Inc., London. IAEA (1992) Analytical Techniques in Uranium Exploration and Ore Processing. Technical Report, International Atomic Energy Agency, Series No. 341, 8199, IAEA, Vienna. UNSCEAR (2000) Sources of ionising radiation, United Nations Scientific Committee on Effects of Atomic Radiation, Report, United Nations; New York. UNSCEAR (1993) Sources of ionising radiation, United Nations Scientific Committee on Effects of Atomic Radiation, Report, United Nations; New York. O’Brien, K., Friedberg, W., Duke, F. E., Snyder, L., Darden Jr., E. B., and Sauer, H. H. (1992) The Exposure of Aircraft Crews to Radiation of Extraterrestrial Origin. Radiat. Prot. Dosim. 45(1-4), 145-162. Bouville, A. and Lowder, W. M. (1988) Human population Exposure to Cosmic Radiation, Radiat. Prot. Dosim. 24, 293-299. AGI/NAGT (1990) American Geological Institute and The National Association of Geology Teachers. Laboratory Manual in Physical Geology, Second Ed., Merrill Publishing Co., London. Cox, P. A. (1995) The Elements on Earth - Inorganic Chemistry in the Environment, Oxford University Press, New York. UNSCEAR (1988) Sources of ionising radiation, United Nations Scientific Committee on the Effects of Atomic Radiation, 1988 Report, United Nations; New York.

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[10] [11]

[12]

[13]

[14] [15]

[16]

[17]

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[18]

[19]

[20] [21] [22]

[23]

[24]

Amidu O. Mustapha Hamilton, T.F. (2004) Linking legacies of the cold war to arrival of anthropogenic radionuclides in the oceans through the 20th century, In: Hugh D. Livingston ed., Marine radioactivity Elsevier Ltd London. Steinhausler, F. (1992) The Natural Radiation Environment: Future Perspective, Radiat. Prot. Dosim. 45(1-4), 19-23. Molinari, J. and Snodgrass, W. J. (1990) The Chemistry and Radiochemistry of Radium and the Other Elements of the Uranium and Thorium Natural Decay Series, In: The Environmental Behaviour of Radium. Technical Report 310, Vol. 1, 3-10, IAEA, Vienna. ICRP (1977) Recommendations of the International Commission on Radiological Protection, International Commission on Radiological Protection Publication 26, Annals of the ICRP, 1( 3). UNSCEAR (1982) Sources of ionising radiation, United Nations Scientific Committee on Effects of Atomic Radiation, 1982 Report to the General Assembly, United Nations; New York. IAEA (1988) Facts about Low-Level Radiation, International Atomic Energy Agency, IAEA/P1/A 14E 85-06482, IAEA, Vienna. ICRP (1984) Principles for Limiting Exposure of the Public to Natural Sources of Radiation, International Commission on Radiological Protection Publication 39, Annals of the ICRP, 14 ( 1). ICRP (1991) Annual Limits on Intake of Radionuclides by Workers Based on the 1990 Recommendations, International Commission on Radiological Protection Publication 61, Annals of the ICRP 21(4). ICRP (1993) Protection Against Radon-222 at Home and at Work, International Commission on Radiological Protection Publication 65, Annals of the ICRP 23(2). IAEA (1988) Assessing the impact of deep sea disposal of low level radioactive wastes on living marine resources. Technical Report, International Atomic Energy Agency, Series No.288, IAEA, Vienna. Volkle H. (2006) Radiation Protection of the environment under the light of the new concept of radiation protection of Non-Human species. ICRP Second European Congress May 15-19 2000 Paris. Scott, E.M. (2003) Modeling Radioactivity in the Environment Elsevier Ltd. London Gentner N. (2004) Protecting against natural radiation. 11th International Radiation Protection Association (IRPA) May 23-28, 2004 Madrid, Spain. Mustapha, A.O., Patel, J.P. Kalambuka, H.A. Acholla O., Maina, D. (2008) Outdoor external doses in the high background radiation area of Lambwe east location south western Kenya. Proc. 12th International Congress of the International Radiation Protection Association 19-24 October 2008 Buenos Aires Argentina. Alexander W.R., Smith, P.A., McKinley, I.G. (2003) Modeling radionuclide transport in the geological environment: a case study from the field of radioactive waste disposal In: Scott, E.M. (ed.) Modeling Radioactivity in the Environment Elsevier Ltd. London Kirk, C.J. and Masque, P. (2004) Natural radionuclides applied to coastal zone processes In: Hugh D. Livingsto (ed.) Marine Radioactivity, Elsevier Ltd. London.

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In: Impact, Monitoring and Management… Editors : Ahmed El Nemr

ISBN 978-1-60876-487-7 © 2010 Nova Science Publishers, Inc.

Chapter 4

FRESHWATER CYANOBACTERIAL (BLUE-GREEN ALGAE) BLOOMS: CAUSES, CONSEQUENCES AND CONTROL NK Sharma1, KK Choudhary 2, Rakhi Bajpai 2 and AK Rai1 2, * 1

Department of Botany, Postgraduate College, Ghazipur (UP) -233001, India 2 Department of Botany, Banaras Hindu University, Varanasi (UP) -221005, India

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ABSTRACT Harmful algal blooms (HABs) are a natural phenomena however, due to human activities and interventions, incidences of HABs have increased globally. Onset, development and proliferation of blooms are closely associated with the nutrient enrichment of water bodies (eutrophication) and climatic changes; and their possible interaction. Cyanobacteria are amongst the most successful bloom forming algae. They can convert and use different forms of C, N, P, and S that help them in occupying almost all kinds of aquatic habitats. Moreover, they grow well in shaded light, show resistance against grazing pressure and release allelochemicals to out-compete co-occurring organisms. Presence of gas-vacuoles facilitates their migration in the water column to ensure enough light and nutrient availability. Cyanobacterial blooms adversely affect water quality, structure and composition of biological communities and a range of ecological services. Many of the bloom forming cyanobacteria produce toxins responsible for mass mortality of aquatic and exposed vertebrate populations. This chapter describes the causes and consequences of cyanobacterial blooms and a few measures adopted to control bloom formation and proliferation. The impact of climatic change on cyanobacterial bloom formation has also been discussed.

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INTRODUCTION Phytoplankton production is important in supporting the productivity of aquatic ecosystems. Biomass produced by the phytoplankton provides the energy and materials for the use of other organisms in aquatic food webs. The size of phytoplankton assemblages depends upon the balance between “bottom-up” and “top-down” controls. Bottom-up control operates through level of light and nutrients, which determines the rate of biomass production of a particular water body. However, grazers consume this newly produced biomass and exert ‘top-down” control [1]. Due to rapid industrialization and other socio-economic factors various types of organic and inorganic pollutants are released into water bodies bringing a change in their nutrient status, pH, turbidity and temperature. Consequently, accelerating the bottom-up effect weakens the top-down control, resulting in massive phytoplankton growth i.e., the bloom. “In late June 2008, the waters and shores at the Qingdao venue hosting the Olympic sailing regatta experienced a massive green tide covering about 600 sq km. Lasting over two weeks, it took more than 10,000 people to clean up, removing over one million tonnes of green mass from the beach and coast” [2]. Organisms mainly responsible for such changes are algae. For instance, in the above case it was the green alga Enteromorpha prolifera. Luxuriant growth of algae makes water colored and turbid. A condition often termed as blooming of water bodies. A bloomed water body (chlorophyll-a ≈300µg/L) has algal biomass higher than that of oligotrophic (≈1.5 to 10.5µg/L) waters [3]. It has a minimum cell concentration of approximately 20,000 cells mL-1 [4]. Blooms are not static communities, rather they show variation in space and time. They exhibit a succession of dominance; diatoms and green algae dominate in the winter and spring; green algae dominate in late spring and summer, and cyanobacteria dominate in late summer fall. There are a number of taxonomically unrelated algal species that form blooms, which are identified by the dominant group/species e.g. cyanobacterial bloom or Microcystis bloom [4]. Eutrophic (nutrient rich, highly productive system) and hypertrophied (extreme eutrophy) conditions favor as well as extend the period of cyanobacterial (blue-green algae) dominance in an ecosystem [3]. Cyanobacteria are the most notorious bloom formers [1]. They infest almost every type of waters (with the possible exception of acidic waters) but, freshwater cyanobacterial bloom especially; waters used for drinking and recreational purposes are of the greatest concern. Since a number of surface bloom forming cyanobacteria produce toxins, there are hazardous effects on co-occurring aquatic biota as well as exposed human and animal populations [5].

1. CYANOBACTERIAL BLOOMS Cyanobacteria constitute a group of prokaryotic photoautotrophs with an oxygenic mode of photosynthesis. They are supposed to have originated and evolved in the “proterozoic era” in nutrient limiting conditions; and subsequently distributed into a wide range of habitats [6]. They show morphological, reproductive and physiological adaptations in order to occupying different ecological habitats. Cyanobacteria form symbiotic associations with other microbes,

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higher plants and animals and produce different kind of resting spores. Some genera are able to fix dinitrogen (N2) in adverse nitrogen-limiting condition. Cyanobacteria possess certain unique adaptations that make them a successful competitor in a bloom environment. These include, their ability to grow in warm waters, capture reduced photosynthetic flux densities, utilize low TN: TP ratio and, to access low dissolved CO2 concentration (in form of bicarbonate). In addition, bloom forming cyanobacteria may undergo organizational changes during different stages of bloom development. For example, filamentous forms such as straight, spiral or twisted chains of cells may achieve secondary structures due to aggregation or enlargement of filaments [7, 8]. Similarly, globular colonies change to loose aggregation of separate colonies [9]. Ability to reorganize thallus structure according to environmental conditions helps cyanobacteria in buoyancy regulation, which is an active process in which gas vacuoles inflate and deflate in an effort to regulate the cells at an optimum depth for nutrient and light availability. Vertical migration also helps in formation of blooms at the surfaces. Cyanobacteria commonly inhabiting eutrophic freshwater bodies are species of Microcystis, Oscillatoria, Spirulina, Anabaena, Anabaenopsis, Aphanizomenon, Nodularia, Cylindrospermum, Tolypothrix, Calothrix, Mastigocladus, Scytonema, Nostoc, Rivularia and Gloeotrichia [10].

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1.1. Temporal and Spatial Dynamics of Cyanobacterial Blooms In a bloomed aquatic ecosystem, population size, species composition and cell densities of cyanobacteria show temporal and spatial variation. Some freshwater bodies may have seasonal blooms that start in summers and last into autumn. A few have persistent blooms, while in many cases blooms occur as extreme peaks and crashes lasting a few days or weeks [11]. Seasonality of blooms in a particular water body is subject to the extent to which different environmental factors influence bloom dynamics [11]. In temperate regions blooms generally occur during the warm, windless days of late summer (possibly due to increased light intensities and temperature). Havens [11] reported that in deep temperate eutrophic lakes with stable summer stratification, phytoplankton progresses through the dominance of diatoms in spring, followed by clear water; cyanobacteria dominate in mid to late summer with water temperature >200C, depletion of inorganic nitrogen and free CO2. In tropics, cyanobacterial blooms may appear at any time as temperature remains relatively constant throughout the year. If winters are not too cold, cyanobacterial blooms may occur throughout the year [12, 13]. In such conditions, diversity and dominance of species are determined by the thermocline establishment brought about by meteorological changes. Depression in the thermocline increases diatoms populations and decreases cyanobacterial populations. Reestablishment of thermocline again makes cyanobacteria abundant. Reynolds [14] found that succession of algal species in eutrophic water bodies is determined by stratification and nutrient availability. In general, in eutrophic water bodies following successional sequence has been observed: diatoms → cyanobacteria → green algae → dinoflagellates, depending upon light and nutrient availability [15]. Eutrophy favors the growth of diatoms and cryptomonads but cyanobacteria can maintain their dominance even under reduced nutrients [15]. Cyanobacterial blooms may develop within (metalimnatic bloom) or onto the surface (surface bloom) of the water bodies. However, based on perceived threat to human, surface

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blooms are of greater concern compared to metalimnetic blooms [1]. Although appearance of surface blooms is a seasonal event, persistent surface blooms have now become common in many eutrophic water bodies. This may be because of the loss of buoyancy regulation and senescence [16], which supports the cyanobacterial dominance at the surface [17, 18]; or due to the presence of underlying colonies that often blocks the downward movement of cyanobacteria [16, 19]. For instance, in eutrophic water bodies metalimnion is dominated by diatoms and prevent the downward migration of cyanobacteria. Many planktonic cyanobacteria contain gas vacuoles that help cyanobacteria in buoyancy regulation [20]. A gas-filled vesicle has a density of about one tenth that of water making the cell lighter than water [21]. Gas-vacuoles remain under dynamic state (i.e., vacuole formation ↔ vacuole collapse) depending upon environmental changes. Buoyancy regulation enables cells/colonies to acquire light and nutrients in water column therefore, provides a competitive edge over other phytoplankton. In aquatic systems, when buoyancy is reduced, small-sized cyanobacteria dominates while, large-sized are prevalent at enhanced buoyancy. Turbulence is another factor facilitating the quick appearance of surface bloom due to upward migration of an existing dispersed phytoplankton communities present in metalimnion [22]. There are some cyanobacteria inhabiting both surfaces as well as metalilimnionic waters. For example, cyanobacteria Aphanizomemon flos-aquae and Oscillatoria agardhii form surface bloom but, are also reported from metalimnion of eutrophic lake [23]. Both these species occur as single filaments in metalimnion but as aggregates in an epilimnetic zone [23]. Likewise, within a genus, species may show variation in their spatial distribution. For example, Oscillatoria rubescens occurs in the metalimnetic zone while, O. agardhii may occur in metalimnetic zone [24, 25, 26] as well as in mixed layers [27]. In general, cyanobacterial population gradually decreases with water depth but, diatom population increases with increase in water depth. This contrasting depth distribution helps cyanobacterial population to remain in epilimnion.

1.2. Factors Affecting Cyanobacterial Bloom Formation and Proliferation The exact mechanism behind the development of cyanobacterial blooms is still to be fully resolved. Factors such as environmental (nutrient enrichment, light intensity and duration, temperature, alkalinity), biotic (zooplankton grazing, viral lysis, allelopathic interactions) and water body characteristics (physical structure, residence time, water turbulence) are supposed to be involved in the development and expansion of freshwater algal blooms [4]. Paerl [10] opined that physical factors are mainly responsible for the development of cyanobacterial bloom in marine ecosystems, while trophic status is more important for freshwater ecosystems. Based on trophic state (nutrient status and productivity), natural aquatic bodies are categorized as oligotrophic, mesotrophic and eutrophic. Oligotrophy symbolizes a nutrient poor state of the water body while; mesotrophy is nutrients rich state providing optimal conditions for growth and development of species. Eutrophy (excessive nutrients) is a temporary state released with the utilization of nutrients by phytoplankton, and leads to increased productivity of the water body. Due to increased surface: volume ratio, algae utilize nutrients more efficiently than that of other phytoplankton groups leading to exuberant population growth in nutrient enriched conditions [7]. However, behavior of different cyanobacteria in natural ecosystems is not similar, and is dependent upon their

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ecophysiological properties. Cyanobacteria with similar eco-physiological characteristics (ecostrategists) are grouped together; different ecostrategists occupy different ecosystems as well as different niches of an aquatic ecosystem. Knowledge about the factors (Table 1) responsible for cyanobacterial bloom development is important in developing control measures. Table 1. Physico-chemical conditions favoring surface cyanobacterial bloom formation Factors Nutrient input Water temperature Water column Flushing Dissolved carbon N:P ratio Light Salinity pH

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Vertical mixing

Conditions Excessive P loading High (>25OC) temperature Persistent and stable water column; depends upon size and volume of the system and wind velocity Long water retention time/ slow flushing Low dissolve inorganic carbon support cyanobacteria growth Low (8) Large-scale vertical mixing prevents surface accumulation of blooms, favors eukaryotic taxa Shears (small-scale turbulence) inhibit cyanobacterial bloom formation

1.2.1. Nutrient Enrichment Eutrophication is a natural aging process of aquatic ecosystems resulting from hundreds or thousands of years of human activities that added nutrients to them [28]. Nixon [29] defined eutrophication as “the process of increased organic enrichment of an ecosystem generally through increased nutrients inputs.” In general, eutrophication favors cyanobacterial bloom formation however, after a certain point eukaryotic algae replace the cyanobacteria [11, 30]. Concentration of individual nutrients, their modifications and relative ratios have long been held responsible for the development of cyanobacterial blooms [31]. Amongst various nutrients, nitrogen (N) and phosphorous (P) have mainly been implicated in cyanobacterial blooming of water bodies. Other nutrients include potassium, sodium, and magnesium salts; depending upon the requirement of individual species/groups. Provasoli [32] considered monovalent ions as absolutely essential for algal growth and development. Industrialization as well as intensive agricultural practices has led to the substantial increase in the concentration of such nutrients in waters (i.e., allochthonous sources, Table 2). Besides these outside sources, nutrient content of an ecosystem can also increase due to internal recycling of nutrients (i.e., autochthonous source). Rate of water renewal plays a critical role in nutrient loading and subsequent eutrophication. Stagnant waters are more sensitive to eutrophication than running waters, since such waters collect excessive nutrients from other sources than replenished waters. Multiple cloudy days and intense rainfall which increases flushing rate reduces the bloom development [11]. The drying of wetlands also increases nutrient concentration leading to eutrophication [33]. Photosynthetic depletion of free CO2 from waters favors cyanobacterial dominance in blooms. Since cyanobacteria have low Ks for

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CO2 and can use bicarbonate as carbon source [34]. It also allows cyanobacteria to form surface bloom as they move to the air-water interface where CO2 is available in plenty. Below, we have discussed the importance of nitrogen and phosphorus in cyanobacterial bloom formation. Table 2. Allochthanous sources of nutrient enrichment and their importance Type

Characteristics

Example

Importance

Point sources

When nutrients enter into water bodies directly from their source of origin;

Industrial and domestic wastes;

Point sources are less important and contribute a little in eutrophication because they may be controlled and regulated with little efforts They are difficult to regulate and vary with season, precipitation and other irregular events. For N and P, nonpoint sources act as a major input in many water estuaries [29, 109].

Wastewater treatment plants Storm water drains

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Non-point sources

Nutrients are gathered at one site and carried away to the water bodies by other means

Soil Retention (Excess application of chemical fertilizer to agricultural fields often accumulates in soils and eventually makes its way along with rain water to water bodies causing eutrophication) Runoff to surface water and leaching to groundwater (Excess nutrients move either horizontly into other surface waters i.e., runoff or vertically downwards to ground waters i.e., percolation or leachate) Atmospheric deposition (Due to combustion of fossil fuels different compounds are released into the atmosphere and deposited onto water bodies e.g., nitrogen is released into air due to volatilization of ammonia and nitrous oxide production, which eventually moves into water bodies along with rain i.e., acid rain).

Sharpley et al. [110] reported that in many water bodies amount of phosphorus lost to surface waters increased linearly with the amount of phosphorus in the soil.

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1.2.1.1. Nitrogen Cyanobacterial blooms occur mainly in eutrophic waters. Therefore, it was assumed that they require high phosphorous and nitrogen [35]. Amongst the various nutrients affecting the growth rate of cyanobacteria induced eutrophication; nitrogen has been the most limiting in water bodies [36]. In natural ecosystems, nitrogen is available in different inorganic forms viz. NO3-, NO2--, NH4+ and organic forms like amino acids, organo-nitrates and urea [37, 38]. Concentration and available forms of nitrogen regulate the species composition and relative size distribution of the phytoplankton cells in communities [39]. In oligotrophic lakes, N2fixing cyanobacteria appear first and colonize the system, while in eutrophic water bodies, species deficient in nitrogen will appear first and utilize nitrogen with enhanced biomass production [40]. Large-size species will have maximum accumulation leading to their abundance [41, 42]. Similarly, NH4+ rich waters are generally dominated by small species as they have greater affinity for NH4+ over NO3- than large species [43]. 1.2.1.2. Phosphorus In freshwater bodies, availability of phosphorous (P) is the most crucial factor determining the growth of cyanobacteria. Cyanobacteria take P in orthophosphate form (PO43 ), and are bestowed with an ability to convert other phosphate (non-usable, non-available) forms into usable orthophosphate form. High concentration (30-100µg L-1) of total phosphorous promotes cyanobacterial bloom formation [44]. Moreover because of their high affinity (i.e., growth under P-limited condition) for P, they can store substantial amount of P during P-sufficient condition to continue for a few generation (cell division). Alternatively, excess P-loading in the water body may facilitates the growth of other phytoplankton leading to increased turbidity (low light availability), which favors cyanobacterial growth [35]. Besides alone, phosphorous in combination with other nutrients may regulate cyanobacterial dominance in bloom environment. Ratio of nitrogen and phosphorous (N:P ratio) is another measure regulating cyanobacterial bloom formation. Redfield ratio (i.e., 16N:1P) is a measure of an appropriate N: P ratio for the sustainable development of aquatic ecosystems. Eutrophic water bodies with low TN: TP ratios favor cyanobacterial dominance [31, 45]. High N: P ratio is an indicative of phosphorus limitation and vice-versa [46]. However, Reynolds [47] questions the tenability of resource ratio hypothesis and discounts this as coincidental. According to Downing et al. [44], TP is better predictor of cyanobacterial dominance than TN: TP ratios. Further, P is limiting nutrients in freshwaters while, N is in estuarine and marine waters [1, 48]. 1.2.2. Environmental Factors Environmental factors such as light, temperature, water column stability and pH are important determinants of cyanobacteria bloom development [11, 34]. In aquatic ecosystems, the zone in which photosynthesis occurs is known as euphotic zone (Zeu). It extends from the surface to the depth which receives 1% of the surface light intensity. It may be deeper or shallower than the mixed upper zone of a thermally stratified water body (i.e., the epilemnion, Zm). Photosynthesis driven high biomass production often results in turbidity of the water. Consequently, the eutrophic zone becomes more shallow than the epilimnion of the water body (Zeu/Zm ratio is 180µE m-2 s-1) to extended period inhibited the growth of Oscillatoria agardhii (now Planktothrix). Under low intensity light conditions cyanobacteria out-grow other phytoplankton species. For instance, Van Liere and Mur [51] observed that in a similar but low-light condition, cyanobacterium Oscillatoria agardhii out-competed the green alga Scenedesmus protuberance (requires high intensity light). Surface-blooms forming cyanobacteria are more tolerant to high light intensities than their sub-surface dwelling counterparts. Possibly, because of high production of carotenoids which protects the cells from photoinhibition [52]. Cyanobacteria have low maintenance cost in terms of energy. At low light intensity their growth rate is higher compared to other phytoplankton species. This provides for them a competitive edge in turbid water bodies. Kallqvist [53] reported that in a eutrophic lake, at one meter depth, diatom such as Asterionella, Synedra and Diatoma grew faster than the cyanobacterium (Planktothrix). However, at intermediate depth (2 m) growth rate was similar for all the species. While, in deep waters, (3 m) only Planktothrix grew. High pH favors cyanobacterial bloom formation [11]. Likewise, they attain maximal growth at temperatures range 25-30°C [54]. This temperature is high enough for the growth of green algae and diatoms: a possible explanation as to why cyanobacterial bloom occurs during summer in temperate and boreal water bodies. Zhang and Prepas [55] argued that thermal stratification of the water column is important for the formation of cyanobacterial blooms. Further, stochastic processes such as wind velocity and rainfall affect water column stability. Low wind velocity and absence of rainfall facilitates cyanobacterial bloom formation. The effects of artificial mixing (water column stability) on phytoplankton have been investigated by several groups. Visser et al. [56] reported that artificial mixing prevents blooms of Microcystis sp.

1.2.3. Biotic Interactions In bloom, cyanobacterial populations are relatively stable. As such, they show resistance against well known zooplankton grazers (except, some ciliates and rhizopods) but are susceptible to viral, bacterial and actinomycete attack. However, the significance of such grazing to cyanobacterial population breakdown is not very well understood [35]. Moreover, buoyancy regulation further lowers the sedimentation of cyanobacterial populations. Hence, once a population is established, it shows high prevalence [35]. Cyanobacteria produce various kinds of secondary metabolites that may have allelopathic properties. Allelopathy refers to the inhibitory or stimulatory effect of organisms through the production and release of diverse kind of organic compounds. This phenomenon is closely related with the competition for limiting nutrient resources. Allelochemicals are usually produced under nutrient limited condition [57]. Arguably, under cultural eutrophication, availability and altered nutrient ratios can stimulate production of allellochemicals [57]. Suikkanen et al. [58] believed that allelochemicals produced by Microcystis aerugenosa may be responsible for their dominance (suppression of other phytoplankton) in blooms. Cyanotoxins such as microcystins may affect the structure, composition, succession and

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pattern of species dominance in a phytoplankton community [59, 60]. For instance, researchers believe that persistent bloom of Cylindrospermopsis raciborskii in Lagoa Santa Lake (Brazil) could be because of the allaelochenmical produced by the species [61, 62]. Suikkanen et al. [63] found that cell-free extract of Aphanizomenon and Nodularia stimulated the growth of the cyanobacterial community.

1.2.4. Water Body Characteristics In shallow lakes (mean depth 3m) water bodies. Blooms of many species remain homogenously dispersed throughout the epilimnion (i.e., homogenously dispersed ecostrategists). They are extremely sensitive to high light intensity and show weak buoyancy regulation. Such types of ecostrategists are found in eutrophic and hypertrophic shallow lakes forming monoculture but persistent blooms. In addition, a few cyanobacteria form blooms in metalimnion (i.e., stratifying ecostrategists). The phycoerythrin pigment of such species allows them to absorb the green light that penetrates up to this depth. Most metalimnetic blooms are found at light intensities of 1-5% of the surface irradiance (Zeu/Zm = 0.7-1.2) [35]. The cyanobacterial bloom of ecosystems that are low in inorganic nitrogen but receive enough light is dominated by N2-fixing species (i.e., N2-fixing ecostrategists) [10]. Restorative strategies that reduce nitrogen concentration in water bodies increase the probability of N2-fixing cyanobacteria to dominate in the subsequent bloom.

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Cyanobacteria may also form mats on the bottom sediment of shallow but clear (allow light to reach to the sediment bottom) water bodies. Table 3. Cyanobacterial ecostrategists; Mur et al. [35]. Type Scum-formers

Habitat Characteristics Calm, buoyancy regulation is operational

Genera/species Microcystis, Anabaena, Aphanizomenon

Homogeneously dispersed

Vertical mixing less frequent, shallow, nutrient enriched

Planktothrix agardhii, Limnothrix redekei

Stratified

Metalimnion of thermally stratified lakes

Planktothrix rubescens, and other Planktothrix spp.

N2-fixers

well–stratified eutrophic lakes, low inorganic nitrogen, but well lit, intermediate stages of lakes undergone nutrient regulation Small, intermittently flushed lakes Very shallow water bodies

Anabaena, Aphanizomenon, Cylindrospermopsis, Nodularia, Nostoc spp.

Small colony formers Benthic

Aphanothece sp. Oscillatoria limosa

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2. CLIMATIC CHANGE AND CYANOBACTERIAL BLOOMS During the last century, human activities such as fossil fuel burning, changed land use patterns and deforestation have substantially increased the atmospheric CO2 level. According to the estimate of an intergovernmental panel on climatic change, the atmospheric CO2 level is estimated to be more than double by 2100 [70]. Little is known about the way these climatic changes will affect the formation and proliferation of cyanobacterial blooms. Studies indicate that global warming and worldwide proliferation of harmful cyanobacterial blooms are positively linked [71]. Frequency of cultural eutrophication has increased substantially in recent decades [72]. However, cultural eutrophication is not the only but one amongst multiple anthropogenic factors responsible for the global expansion of cyanobacterial bloom [71]. Other factors such as elevated CO2 level and rising temperature may also affect the development and proliferation of cyanobacterial blooms. There are a few studies that had investigated the impact of CO2 enrichment on bloom development [73, 74]. The majority of these deals with the impact of CO2 enrichment on marine phytoplankton; only a few on freshwater algal blooms [75]. Most water bodies are supersaturated with CO2 owing to inputs of carbon from deposited sediments (recycling) as well as fresh input from the catchments [76]. Normally, in natural freshwater bodies, dissolved inorganic carbon (DIC) concentration remains high enough (1.5-2.2 mmol/L) to that required for normal cynobacterial growth [77]. However, water bodies experiencing intense cyanobacterial bloom may suffer from carbon limitation even under high concentration of DIC [75]. Change in CO2 availability may affect physiology, nutrient cycling and interactions among major phytoplankton groups [78, 79]. The doubling of the CO2 level

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may increase CO2 dissolution resulting in lowering of the pH values. Concentration and form of DIC (CO2, H2CO3, HCO3- and CO3 2- ) is strongly linked to the pH value [75]. Efficiency of RuBisCO differs between different phytoplankton groups [80]. Cyanobacterial RuBisCO shows low affinity for CO2 (Kc value 200-300 µmol/L) [77]. But, cyanobacteria possess effective CO2-concentrating mechanism (CCM) that elevates CO2 level near the enzyme [81]. Induction of CCMs is regulated by the external concentration of DIC. And, high CO2 concentration of water is likely to repress the CCM. Cyanobacteria grow better at higher temperatures (>250C) than do diatoms and green algae [82, 83]. Therefore, rising temperature may provide them competitive advantage over other planktonic groups [83, 84]. Further, the warming of surface waters strengthens the vertical stratification and reduces vertical mixing in water bodies [71]. It also lengthens the optimal growth period (due to global warming lakes stratify earlier in spring and de-stratify later in autumn). Presence of gas vesicles in many cyanobacteria helps them to exploit stratified conditions. The dynamic nature of gas vesicles keeps cyanobacteria mobile in the water column assisting them in getting light and nutrients. They accumulate cyanobacteria at the surface even when mixing is weak [71, 82, 85, 86]. Also, dense cyanobacterial surface blooms may even locally increase water temperatures through the intense absorption of light [87, 88] that could provide additional competitive advantage to cyanobacteria over nonbuoyant phytoplankton [71]. Rising temperature is likely to affect the pattern of precipitation and drought that could further enhance cyanobacterial dominance [71]. Freshwater discharge prevents blooms through flushing however, as the discharge recedes and water residence time increases, nutrient loads will increase, eventually promoting blooms [71]. Excess withdrawal of freshwater for agricultural use is likely to increase the salinity of freshwater bodies. However, little is known about the impact of increasing salinity on cyanobacterial bloom development. Marine and brackish cyanobacteria are more salt-tolerant than freshwater phytoplankton species, [89] as evidenced by increasing reports of toxic cyanobacterial blooms in brackish waters [90]. Climatic changes have forced some species to expand their geographical range, and are now reported from previously unknown territories [86, 91]. Therefore, it is argued that high nutrient loading, rising temperature, enhanced stratification, increased residence time, and salinazation all favor cyanobacterial dominance in many aquatic ecosystems [71]. Paerl and Huisman [92] have provided an extensive review of the effect of climatic chage on global expansion of cyanobacterial blooms.

3. ECOLOGICAL CONSEQUENCES OF CYANOBACTERIAL BLOOMS Cyanobacterial blooms are responsible for a number of socio-economic as well as ecological problems (Figure 1). They interfere in the process of sedimentation and often clog the sand filters used in water treatment plants. Also, they corrode concrete and metallic walls of the pipes and boilers by secreting acids (carbonic and oxalic acids). Blooms change the pH and hardness of water by consuming dissolved CO2 hence, rendering it unfit for drinking purposes. Furthermore, cyanobacterial mucous encourages the growth of pathogenic organisms such as amoeba and bacteria. Cyanobactrial bloom may affect ecosystems directly (toxic effect on fish and other aquatic fauna) or indirectly (shading, oxygen depletion etc). Some of the effects are discussed below.

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Figure 1. A summary of socio-ecological responses and impacts associated with freshwater cyanobacterial blooms (redrawn from Havens [11]).

3.1. Decreased Water Transparency Dense surface cyanobacterial blooms causes a decrease in water transparency. In addition, a regular deposition of particulate matters (nutrient loading) in water bodies together with metalimniotic cyanobacterial blooms also decreases transparency of the waters (increase the turbidity). Resultantly, light traveling to the different strata of water bodies filtered out affecting the growth, and development of aquatic populations. For instance, shading affects the photosynthesis of the metalimnetic populations responsible for maintaining oxygen in deep waters. Massive surface blooms also decrease the level of turbulence in water bodies which, doesn’t allow mixing of different strata. Consequently, the oxygen level of

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metalimnion and benthic zone declines. This affects the internal cycling of nutrients and may cause nutrient deprivation to surface populations.

3.2. Increased Productivity and Decreased Biodiversity of the Water Body Blooming in a water body increases its productivity. Nutrient enrichment releases the nutrient-stressed condition prevailing in the oligotrophic water body (P-limitation in case of cyanobacteria) that facilitates the growth of cyanobacteria. This also triggers the competition for efficient utilization of nutrient(s) hence, decrease in the biodiversity of the system. Further, a dense and long-lasting bloom suppresses the growth of submerged epiphytes through shading (light limitation) [83].

3.3. Decreased Biomass of Benthic Flora

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Dense cyanobacterial surface blooms hamper the penetration of light into waters. This causes death and subsequent settling of cells resulting in the increase of organic carbon deposition to the bottom of water bodies. Increase organic carbon availability along with empouring of sewage wastes promotes microbial activity, which create hypoxia (1mgL-1) and TN (>5mgL-1) small green algae can outcompete cyanobacteria [30]. Importance of reducing anthropogenic N and P loading in ecosystem for the control of cyanobacterial bloom formation has long been recognized [102, 103]. N and P are key limiting nutrients in most aquatic and terrestrial ecosystems [104]. However, increased industrialization, agricultural run off containing unused fertilizers, municipal wastewater and fossil fuel burning has overloaded ecosystems with these nutrients. N-only reduction has substantially reduced the bloom of non-heterocystous cyanobacteria but not of heterocystous from. Also, this does not apply in case of brackish and saline waters [104]. Similarly, in many cases, P-only reduction strategies were unfruitful [104], as P is rapidly recycled between sediments and waters. Moreover, species like Microcystis can vertically migrate (buoyancy regulation) to consume phosphorous at the sediment–water interface. Studies indicate that no single factor, rather interaction between many factors is responsible for bloom development [104, 105] (Figure 3). Controlling P input to freshwater may increase the concentration of N in downstream estuarine and costal waters [104, 106, 107]. Therefore, unless there is clear evidence, control measures focusing exclusively on P or N reduction would not work [104, 108]. Another major drawback associated with nutrient control measures is high cost. The use of chemicals is an effective mean of bloom control. For instance, algicides such as copper sulphate, sodium penta-chlorophenate, tetra-chlorobenzoquionone, chlorophenyl dimethyle urea, phenazene1-carboxylic acid, potassium permanganate, 2,3-dichloronapthaphenol, dichloropene and chlorine have effectively been used in bloom control. The exact dose of these algicides depends on pH and other characteristics of water and water body, and concentration of cyanobacteria. However, efficacy of these chemicals is often short lived and some of them can have adverse side effects. A suitable algicide should be inexpensive, potent and specific to the target (i.e., non-toxic to other organisms). Biological means of bloom control include modification of food web by introducing suitable organisms that could eat blooms and eaten up by other aquatic organisms such as fish. Use of cyanophages (LPP-1and 2, SM-1, N-1, AS-1) may help in selective removal of bloom forming species. The introduction of floating angiosperms such as Lemna, which shade the water body hence, inhibit the bloom formation. Chrysophytes such as Ochromonas danica engulf and digest the cells of Microcystis aeruginosa, may also prove fruitful.

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Figure 2. Approaches commonly used for control of blooms.

The Metropolitan Water Board of London has found that artificial circulation of water in reservoirs is an effective method of reducing bloom development. Manual harvesting (by nets) of cyanobacterial cells is another method however, small unicels can not be removed by this method. For them, electrical flocculation method (use of positive current) followed by routine mechanical removal has been found effective. 30

1000

Nitrate-N Nitrite-N Ammonium-N

15 400 10

20

15

10 200

B 

14

Nitrogen (mg.L-1)

600

Carbohydrate (μg.L-1)

20

Protein (mg.L-1)

Chlorophyll a (μg.L-1)

18

25

800

5

12 10 8 6 4 2

5

0

0

0 Feb

Mar

Apr

May

Jun

Jul

Aug Sep

Oct

0 Jan

Nov Dec

Feb

Mar

Apr

May Jun

Jul

Aug Sep

Oct

Nov

Dec

Month

Month

0.8

32

C 

PO4

8.4

12

8.2

11

28

8.0

26

7.8

24

7.6

22

7.4

20

7.2

18

7.0

16

6.8

5

6.6

4

10

o

Temperature (O C)

0.6

D 

30

other phosphorus

-1

0.7

0.4 0.3 0.2 0.1 0.0

8

14

Jan

Feb March Apr

May

Jun

Jul

Month

Aug

Sep

Oct

Nov

Dec

9

pH

0.5

Dissolved oxygen (mg.L )

Jan

P (mg.L-1)

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30

16

A 

25

Jan

Feb

Mar

Apr

May Jun

Jul

Aug Sep

Oct

7 6

Nov Dec

Month

Figure 3. Seasonal variation in cyanobacterial biomass in relation to environmental and nutritional factors (Durgakund Pond, Varanasi, India); biomass (A), nitrogen (B), phosphorous (C), temperature and dissolved oxygen (D); Sharma et al. [104].

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CONCLUDING REMARKS Our understanding of freshwater cyanobacterial blooms has improved substantially in recent times. However, there are many areas still unresolved and require further research. Some of them are: 1. Impact of nutrient enrichment and climate changes (alone as well as their interaction) on bloom dynamics (rare ↔ abundance species). 2. Impact of hydrological and watershed modifications (e.g., dams and sluices) that increase residence time on cyanobacterial bloom formation. 3. Analysis of the factors that could be manipulated to control the bloom, even when environmental conditions are favorable for their development. 4. Interaction/competition between toxic and non-toxic strains and its impact on cyanobacterial bloom. 5. Impact of physical, chemical and biological factors on the level of toxins. 6. There is a need to understand the effects of cyanobacterial blooms on community structure and composition rather, than on a particular species.

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[100] Francis, G. (1878). Poisonous Australian Lake. Nature, 18: 11-12. [101] Boyer, G.L.; Sullivan, J.J.; Andersen, R.J.; Harrison, P.J.; Taylor, F.J.R. (1987). Effects of nutrient limitation on toxin production and composition in the marine dinoflagellate Protogonyaulax tamarensis. Mar. Biol., 96: 123–128. [102] Schindler, D.W. (1974). Eutrophication and Recovery in Experimental Lakes: Implications for Lake Management. Science, 184: 897-899. [103] Schindler, D.W.; Hecky, R.E.; Findlay, D.L.; Stainton, M.P.; Parker, B.R.; Paterson, M.J.; Beaty, K.G.; Lyng, M.; Kasian, S.E.M. (2008). Eutrophication of lakes cannot be controlled by reducing nitrogen input: Results of a 37-year whole-ecosystem experiment. Proc. Natl. Acad. Sci. USA., 105:11254–11258. [104] Conley, D.J.; Paerl, H.W.; Howarth, R.W.; Boesch, D.F.; Seitzinger, S.P.; Havens, K.E.; Lancelot, C.; Likens, G.E. (2009). Controlling Eutrophication: Nitrogen and Phosphorus. Science, 323; 1014-1015. [105] Sharma, N.K.; Mohan, D.; Rai, A.K. (2009). Predicting Phytoplankton Growth and Dynamics in Relation to Physico-chemical Characteristics of Water Body. Water Air Soil Pollut., DOI 10.1007/s11270-009-9979-x [106] National Research Council (2000). Clean Coastal Waters. National Academies Press, Washington, DC. [107] Paerl, H.W.; Valdes, L.M.; Joyner, A.R.; Piehler, M.F.; Lebo, M.E. (2004). Solving problems resulting from solutions: The evolution of a dual nutrient management strategy for the eutrophying Neuse River Estuary, North Carolina, USA. Environ. Sci. Technol., 38: 3068-3073. [108] Conley, D.J. (2000). Biogeochemical nutrient cycles and nutrient management strategies. Hydrobiologia, 410: 87-96. [109] Carpenter, S.W.; Caraco, N.F.; Smith, V.H. (1998). Non-point pollution of surface waters with phosphorus and nitrogen. Ecol. Appl., 8: 559-568. [110] Sharpley, A.N.; Daniel, T.C.; Sims, J.T.; Pote, D.H. (1996). Determining environmentally sound soil phosphorus levels. J. Soil Water Conserv., 51: 160-166.

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Chapter 5

AVIAN IMMUNOTOXICOLOGY: CURRENT TRENDS AND FUTURE DIRECTIONS Michael J. Quinn1, Jr. U.S. Army Center for Health Promotion and Preventive Medicine Directorate of Toxicology Health Effects Research Program United States of America

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ABSTRACT Immunotoxicology is a relatively recent subdiscipline of the larger field of toxicology with the majority of its studies focused on mammalian systems. Immunotoxicological studies that concentrate on avian species have steadily increased over the past two decades. Birds occupy a wide variety of ecological niches and are good representatives of many different trophic levels, making them good indicators for environmental health assessments. This review describes current methods that are commonly used to assess immune status in birds and suggests directions for future efforts. The usefulness of measures that assess the effects of environmental contaminant exposure on immunological structure will be compared to those that test function. Particular attention is paid to emerging issues in the field, such as developmental immunotoxicology (DIT) and the use of cytokine measures in immunotoxicity evaluations, and how they are being, or should be, addressed in avian species.

1. INTRODUCTION Immunotoxicology is a relatively recent subdiscipline of the larger field of toxicology that can be succinctly defined as, the results of chemical exposure on the form and function of the immune system. Numerous laboratory studies have demonstrated immunoreactive or immunosuppressive effects following acute or chronic exposures to chemicals, metals, drugs, or environmental contaminants. In addition, many observational studies have shown 1 E-mail: [email protected]. Edgewood Area, Bldg. E-2100, Aberdeen Proving Ground, MD 21010.

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correlations between exposure to environmental toxins and effects on physiological and functional aspects of the immune system. Although most research in this field has been conducted with mammalian species, there is a steadily growing body of literature that demonstrates similar effects in birds. Birds perform many ecological functions that help maintain an ecosystem’s integrity, and they comprise a large percent of many biomes’ biomass. Birds also occupy many levels of the food web, making them excellent indicators for environmental health and risk assessments. Although traditionally overlooked in favor of basic data on mortality and reproduction, measures of immune effects in birds are a necessary compliment to the overall assessment of the risk to health associated with environmental chemical exposure in these species. Birds have played an important and contributing role in the basic understandings of the immune system. The main function of B cells was first discovered, in part, due to a fortuitous experiment in the laboratory with chicks (Gallus gallus; [1]). Bursectomization within the first phase of growth, followed by a humoral challenge to Salmonella pullorum, resulted in an unexpected absence of antibody production. Although mammalian B cell maturation occurs in bone marrow and not the bursa of Fabricius, this initial work in an avian species is credited for the development of the T cell and B cell concept for vertebrates [2]. Interestingly, the “B” in “B cells” refers to the avian “bursa” and not the mammalian “bone” marrow. Current methods used to assess avian immunocompetence for ecological risk assessment and poultry management [3] are often derived from rodent protocols [4,5]. Due to the unique features of the avian immune system, and an emphasis on human health over environmental health concerns, progress in avian immunology and the effects of environmental contaminants have been comparably slower than efforts made at understanding mammalian systems. Also, much of the current information available on avian immune system development and function have come from studies that used poultry, therefore a basic assumption of similarities in immune systems between altricial and precocial birds is often made. This chapter will begin with descriptions of the current methodologies used to assess contaminant effects on the avian immune system, focusing on measurements that assess effects on form (structure) and function. A summary of the current ideas and methods employed in the broader field of immunotoxicology will follow, with emphasis on how these may be adopted for use in an avian paradigm.

2. MEASURES OF FORM Mass, histology, and cellularity are the more commonly used measures in avian immunotoxicity tests. Benefits of these measures include the ease of data collection and the relative abundance of control data available for comparisons between study and non-study animals. An obvious disadvantage to the information gained from these measures is the limitation of not being able to fully predict functional effects of environmental chemical exposure, although altered immune organ size or histology are often associated with alterations in lymphoid function. Immune organ masses are most often expressed as percentages of body mass, although organ weight:brain weight ratios or other indices, such as [organ weight / (body weight - organ weight)] x 100, are also used. Histological measures are often descriptive and qualitative, although recent studies have used more quantitative

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measures, which allow for statistical analyses (i.e. area of bursal follicles, area of thymal cortex, number of vacuoles per tissue area) to be made. It should be realized, however, that histological measures have been demonstrated to be insensitive indicators of immunotoxic potential [6]. Factors such as age, sex, strain of subjects, housing conditions, and nutritional status, can further confound the interpretation of histological analyses of this already dynamic set of tissues. Because the avian thymus is the only primary lymphoid organ that is analogous to that of mammals, it remains one of the more studied immune structures in birds. The thymus is the site of T cell differentiation, and as such, chemical effects experienced by this organ early in embryogenesis have the potential to lead to effects on cell mediated responses and immune response modulation throughout adulthood. The most detailed histological assessment of the avian thymus (as well as the other lymphoid organs) can be found in Bishop et al. [7]; this includes thickness of cortex, relative amounts of tangible body macrophages in the cortex and medulla, cortical lymphocyte density, presence of heterophils, and degree of thymic involution (atrophy). Thymic lymphocyte differentiation in birds had been initially difficult to assess due to the scarcity of T cell markers [8], however thymocyte surface marker expression had been incorporated into ecotoxicological studies little more than twenty years later [9]. The development of avian-specific (chicken) monoclonal antibodies have allowed for the measure of the following lymphocyte phenotypes: CD4-CD8-, CD4+CD8+, CD4+CD8-, CD4CD8+, TCRαβ+, and TCRλδ+. The number of available monoclonal antibodies for wild species has been a long standing challenge to avian and other non-mammalian studies. Although more useful antibodies are available through academic and commercial resources, the lack of cross reactivity often limits immune measures that make use of them in domestic fowl. The early discovery of the bursa of Fabricius’ exquisite sensitivity to androgens and its role in B cell maturation gained this organ quite a bit of attention in the laboratory despite it being a structure unique to birds. The bursa is a bird’s second and final primary lymphoid organ that regresses into a smaller, non-functional remnant organ by adulthood in many species, or remains as a secondary lymphoid organ in others [10]. Early descriptions of histological alterations of the bursa observed in response to exposure to exogenous steroids had been mostly qualitative. Degree of plicae (fold) development, vacuolization, and thickening or wrinkling of epithelia are often observed effects of androgens’ effects on a developing bursa of Fabricius [11,12]. Although these descriptions may be useful markers of exposure, qualitative descriptions of effects do not allow for the rigor of statistical analyses that more quantitative measures would provide. Quinn et al. [13,14] were the first to describe quantitative measures of the bursa of Fabricius in response to exposure to androgen active endocrine disrupting chemicals (EDCs) which included: number of follicles, size of follicles, and cellular area vs. non-cellular area. The measures focused on the follicles since these were the sites of B cell maturation. Desirable measures for future studies may include average width of the epithelial layers that surround the plicae, since alterations in this area of the bursa have been known to cause inhibitory effects on the ability of embryonic stem cells to penetrate the bursa from their splenic migration [11]. While structural measures of the thymus and bursa of Fabricius are normally more suggestive of developmental effects and may be indicative of effects on the immune system throughout adulthood, toxic actions of chemicals on the spleen may cause more immediate effects on immunological function. As a secondary lymphoid organ, much less attention has

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been paid to basic research on the avian spleen, leading it to be labeled as the “neglected organ” [15]. Current studies of splenic structure, however, have revealed it as a highly dynamic organ, suggesting promising future research on the avian immune system to include the spleen. In adult birds, the spleen serves as the major source of antibody production. Numbers of germinal centers, intensely basophilic cells, and red pulp area are areas of the spleen that experience great seasonal changes and are closely associated with timing of increased stress on the immune system [16], and would therefore likely be appropriate for use in immunotoxicity studies. Two components of the intestinal immune system, the gut-associated lymphoid tissues (GALT) and the mucosa-associated lymphoid tissues (MALT), are also rarely studied. The GALT is part of the MALT, and includes the bronchial, salivary, nasopharyngeal, and genitourinary immune tissues [17]. Of these, the Peyer’s patches are the major inductive sites for immunoglobulin (Ig) A responses in the gastrointestinal tract. T lymphocyte and IgA precursor B cell activation occurs in the Peyer’s patches, and these cells then migrate to effector sites for the conduction of antigen-specific secretory IgA antibody responses [18]. No ecotoxicological studies that used measures of any avian GALT or MALT structure could be located in the current body of avian literature. Total and differential white blood cell counts are the most commonly used cellular measures of immune effects of environmental chemical exposure in birds. Decreased numbers of total and individual cell types can be often indicative of an immunosuppressive effect, while an increase is typically associated with an elevated immune response. Avian leukocytes are composed of: eosinophils, basophils, heterophils, lymphocytes, and monocytes. Eosinophils and basophils are granulocytes that respond to parasites and mediate inflammation, respectively. Heterophils and lymphocytes (B, T, and natural killer, or NK, cells) are the most common of the circulating immune cells. The B and T lymphocytes mediate specific immune responses, while the NK cells nonspecific. Heterophils, or neutrophils, are granulocytes that play an important role in responses against bacteria. Heterophil and lymphocyte counts are often expressed as heterophil to lymphocyte, or H:L, ratios, which is often used as a general measure of stress [19]. Monocytes are phagocytic leukocytes that mature into macrophages. Total leukocyte counts can be easily determined with a hemacytometer, the eosinphil unopette method, or by the less known rapid “pin head” estimation method [20]. Differential leukocyte counts are often manually done under a light microscope at 1000x, which require some practice to be certain of individual cell identifications. Cell counts from lymphoid tissue can be made by separating immune cells from connective tissue, and counting under a hemacytometer. As is often the case with gross measures of immune organs, a multitude of possible confounding factors other than toxicants may affect immune cell concentrations. Additionally, since leukocyte counts have been shown to be less sensitive markers of immunosuppression in rodents [21], this may also be true for birds. Although these basic measures are not the most informative of the available methods to assess immune status, they remain some of the most often used due to ease of collection and frequent applicability in veterinary medicine. Their values increase when used in conjunction with other, more informative in vivo or in vitro response tests. Measurement of circulating levels of general immunoglobulins are not as commonly used as leukocyte counts, but can be a good and simple measure to include in immunotoxicity tests, especially those that focus on changes in the immune system that have resulted from

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developmental exposure to chemicals. In Japanese quail (Coturnix japonica), all circulating immunoglobulins in day old chicks come from only two possible sources: deposition by the hen as the egg was being formed in the oviduct, or from production by the chick itself. All antibodies that are produced by the chick on day one originate only from B cells that matured in the bursa, whereas after hatch, B cell maturation can occur in other lymphoid organs, such as the spleen and intestinal mucosa. In studies where hens remain untreated and in ovo exposure occurs through egg injections, one may assume that any differences in Ig levels are due to the chemical exposure if maternal Ig deposition remains similar across exposure levels. Testosterone has been shown to have a negative effect on IgG production and has been demonstrated to increase levels of circulating IgM in hatchling chickens [22]. The inhibition of affinity maturation by testosterone may prevent normal isotype switch from IgM production to IgG production by lymphocytes. The overall amount of antibodies produced in response to foreign antigens may not significantly decrease under testosterone treatments, however, the quality of the antibodies produced may be altered. As such, immunotoxicity studies involving androgen-active compounds or EDCs that disrupt the normal estrogen/androgen ratio may consider inclusion of a basic measure of circulating immunoglobulin isotypes.

3. MEASURES OF FUNCTION

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3.1. In Vivo Two in vivo tests of immune function that test both arms of the specific immune system, the cell-mediated and humoral response systems, most frequently encountered in current avian immunotoxicity articles are the phytohemagglutinin (PHA) skin test and the foreign red blood cell challenge. PHA is a lectin from the bean plant, Phaseolus vulgaris, that acts as a mitogen. As a mitogen, PHA is able to stimulate most T cells, contrasted with specific antigens, such as tuberculin, which are only able to stimulate T cells with surface receptors specific to them. The measure of the in vivo response to PHA incorporates aspects of T cell activation, proliferation, differentiation, and cytokine production, which results in an influx of additional leukocytes and fluid at the site of injection. Injection sites for birds typically include non-feathered fleshy structures, such as the patagial web (wing web), wattle, dewlap, or interdigitary skin. The resulting inflammation is quantified using a stimulation index that is often determined by subtracting the thickness of the PHA injection site from the thickness of a control injection site approximately 24 h post injection. Many studies have reported the repeatability of consecutive measurements of the same swelling site of a PHA injected wing-web to be high [23,24]. Granbom et al. [25], however, found spatial and temporal repeatability of PHA responses to be low. Spatial differences were found by comparing right and left patagia of starlings (Sturnus vulgaris) injected with identical amounts of PHA. Slight variations in the exact locations of the injections was offered as a likely reason for the observed lack of repeatability. Temporal repeatability was assessed by comparing swellings produced in starlings that received a first injection of PHA at 50 days of age, then a second injection 46 days later. Although little can be done to overcome differences in swellings by location in individuals, especially with smaller species

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and injection sites, Granbom et al. [25] suggest that studies report an estimate of spatial repeatability, at least until the reasons for these differences are better understood. This study concluded by further suggesting that both wings be injected with PHA for this test, and that calculations be made on the mean response in both wings. Phosphate buffered saline (PBS) is most often used as the vehicle for PHA and is the normal control treatment for this test. Although the method proposed by Granbom et al. [25] would disallow use of a control treatment, Smits et al. [24] had demonstrated no swelling effect of PBS injections alone. Grasman [26], however, reported that the difference between the PHA and PBS responses often gives greater statistical power than that of PBS alone. Once the potential for spatial and temporal variation is taken into account, and the calculated or estimated variability is reported, the PHA skin test remains a reliable and minimally invasive test of T cell function. As mentioned, immune tests that use specific antigens such as tuberculin differ from mitogens in their ability to stimulate only lymphocytes with surface receptors specific to them. These delayed type hypersensitivity (DTH) skin tests have an advantage in their ability to test the action of memory T cells. This advantage comes at a price, however, in that the test requires an additional immunization for the stimulation of these memory cells. This occurs during an inflammatory response resulting from a second immunization given several weeks after the first. While the PHA skin test is difficult to perform with wild-caught species, the DTH skin test is considerably more involved with the need to capture and restrain birds for the measurement of the resulting inflammation a third time. Although it has been demonstrated to be an effective site for testing cell mediated responses, the feather has remained relatively obscure in current immunotoxicity tests. In fact, the use of feathers in this context appears to have been confined to studies investigating vitiligo, an autoimmune disease characterized by the destruction of pigment cells in feathers, in Smyth line chickens. Use of the feather as an in vivo “test tube” has the advantage over the wing web response test in that cellular activities are able to be directly assessed [27]. Growing feathers with approximately 5-10 mm of living pulp can be collected as soon as 6 hours following injections of PHA or bacterial lipopolysaccharide (LPS). Basic histological observations are able to reveal infiltration of heterophils, macrophages, and lymphocytes into the pulp. For assessment of an antigen-specific cell mediated response, developing feathers can also be injected with Mycobacterium butyricum [28]. Leukocyte infiltration profiles from feathers collected 4, 24, 48, and 72 hours post-injection have been shown to be identical to those demonstrated in wattle and wing web tissues, making feather analysis particularly attractive as a less invasive method. As noted, the feather has benefits as an immunotoxicity test site: injections and removal are minimally invasive, and repeated sampling over the period of an immune response is easily accomplished. Additionally, feathers can be stored safely frozen for later use in assays. Frozen sections and suspensions of developing feathers have been labeled to determine B cell and CD4/CD8 T cell profiles [29,30]. Terminal deoxynucleotide transferase-mediated fluorescein-dUTP nick end labeling (TUNEL) has also been used with frozen feather pulp to detect in situ cell apoptosis [31]. The above described studies are usually published in immunology-specific journals and, therefore, may have been obscured from many wildlifefocused researchers who tend to publish more commonly in the avian or toxicology-focused journals. Clearly, these relatively new immune testing techniques developed using feathers

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have great promise for use in avian immunotoxicity tests and would be an important complement to the more widely used methods. The foreign red blood cell challenge is the most common test used in avian species to measure antibody responses by B cells. Foreign red blood cells are useful in this test because they are often easy to acquire and are non-infectious. Tests using erythrocyte inoculations can give strong antibody responses without excessively challenging the overall health of the test organisms. Measurement of the antibody titers in avian species is normally accomplished through hemagglutination assays. Hemagglutination assays are easily adaptable to wild species, contrasted with ELISAs (enzyme-linked immunosorbent assays) that require speciesspecific antibodies. In addition, because the agglutination assay can be seen with the naked eye or through a magnifying glass, no complex equipment other than an incubator is required. The basic hemagglutination assay method closely approximates the total agglutinating activity of IgM and IgG [19]. An initial incubation with 2-mercaptoethanol dissociates IgM disulfide bonds which results in a titer produced by IgG-antigen interactions; IgM activity can be approximated by subtracting the values derived from IgG activity from that of the total immunoglobulin activity. Measurement of both isotypes following a secondary red blood cell challenge incorporates an assessment of the humoral arm’s memory function. The most common species erythrocyte type used in this type of humoral response measurement is sheep. Because maximum titers are reached approximately six days post immunization, this measurement is easily performed in the laboratory. The two species that have been used most often for this test are Japanese quail (Coturnix japonica) and the northern bobwhite (Colinus virginianus). Japanese quail have been shown to be minimally sensitive to sheep, human, chicken, turkey, and duck erythrocytes and do not produce immunoglobulins to human, bovine, and mouse albumins [32,33]. The Japanese quail does, however, mount a very strong antibody response to chukar partridge (Alectoris chukar) erythrocytes. Although partridge red blood cells can easily be collected from donors at game farms, this bird may be only seasonally available in many areas. Determination of a strongly antigenic and commercially available red blood cell type is highly desirable for use in Japanese quail since it is one of the most often used species in avian toxicity tests. The northern bobwhite responds adequately to immunizations using sheep red blood cells, however, little work has been done to assess this species’ sensitivities to other foreign red blood cells. A recent study tested northern bobwhite antibody responses to injections of sheep, rat, rabbit, cow, and chicken red blood cells to determine relative sensitivities to commercially available foreign red blood cells (Quinn, unpublished data). Identification of the most appropriate antigen to elicit a humoral response in specific species will help to optimize the ability to detect effects on the immune system by exposure to environmental chemicals. Although northern bobwhite appeared to respond strongly to rat red blood cells, high variability in responses were observed among individuals. Chicken red blood cells elicited the poorest responses for both primary and secondary challenges. Sheep and cow cells were adequate antigens for this test in bobwhites; however, rabbit erythrocytes elicited the strongest responses with the least amount of variability among individuals. Of these foreign cell types, rabbit erythrocytes, appear to be the ideal antigen for this test of the humoral response in the northern bobwhite. Bovine serum albumin (BSA) and bacterial LPS are also used to measure antibody responses in birds. The main difference among these more commonly used antigens is that the foreign red blood cells and BSA challenges result in a more integrated response since they

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require the use of helper T cells. The response to bacterial LPS does not require helper T cells, and is, therefore, a more specific measure of B cell function alone. Additionally, an in vivo test of macrophage phagocytic activity has been performed in mallards via India ink clearance [34], however, no study has yet linked this in vivo test to immunosuppression in an avian species.

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3.2. In Vitro A small number of in vitro immune assays are currently used in avian systems. Although recent screening protocols have recommended fewer in vitro tests (reviewed in Fairbrother et al. [35], others argue that they should be a requirement in complement with in vivo tests because of the inherent complexity of the immune system. The argument is made that in vitro testing allows for isolation of “the specific cellular and humoral components to determine function, signal transduction, and a possible role of these constituents without the complexity and redundancy of immunity in intact animals” [36]. The use of avian in vitro immunotoxicity assays should increase as new methodologies are developed and as more tests with wild species are validated. Mitogen-induced lymphocyte proliferation is one of the more common immune assays used in avian systems. Following activation of lymphocytes, cell proliferation occurs early in the immune response. This increase in B and T cell numbers can be induced separately or in unison through exposure to the appropriate mitogen (bacterial lipopolysaccharide is B cellspecific, PHA is T cell-specific, pokeweed mitogen activates both cell lines). The 3Hthymidine incorporation assay has been generally used to measure lymphocyte proliferation in poultry, however bromodeoxyuridine incorporation is also used. Because cells used in the Alamar blue assay do not need to be lysed, this method is sometimes preferred to the titrated thymidine assay when further analyses of the cells are required. Additionally, this assay is nontoxic and requires less time to complete while the being as accurate as the titrated thymidine assay [37]. Flow cytometry is used in a few in vitro immunotoxicity tests. Macrophages or monocytes are incubated with fluorescent latex microbeads post in vitro or in vivo chemical exposure. The number of cells and the number of beads phagocytized are then evaluated using flow cytometry. Respiratory, or oxidative, burst by macrophages and monocytes can also be measured by flow cytometry. This is a measure of reactive oxide species production (superoxide radical and hydrogen peroxide) by these cells in an attempt to destroy bacteria or fungi. Although still early in development, the field of toxicogenomics is rapidly growing. The release of the full chicken genome sequence has accelerated the identification of genes involved in the immune response. Genes related to toll-like receptors and cytokines have already been indentified [38]. Pathogen control in the poultry industry is the major drive in the advancement of avian genomics [39], however the imminent characterization of the genomes of the northern bobwhite and Japanese quail will soon follow that of the chicken, which may be more applicable to ecotoxicological situations (Gust and Quinn, unpublished data). Rapidly developing advances in proteomic (the study of proteins expressed by a genome) and metabonomic (the study of metabolic responses to chemical exposure)

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techniques and methodologies, as well as new methods for data analysis for these subdisciplines and genomics, show great promise for use in avian immunotoxicity studies.

4. DEVELOPMENTAL IMMUNOTOXICITY

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4.1. Avian Studies The number of studies demonstrating correlations between sub-adult environmental toxicant exposures and altered immune responses or the development of certain diseases has steadily risen over the past decade. Increases in the incidence of asthma, allergies, and autoimmune diseases have caused researchers in the human health field to focus more attention on what toxicologists had known for quite some time: developing systems, including the immune system, are more sensitive to chemical exposure than established adult systems. Rodent studies have shown immunosuppression resulting from embryonic exposure to toxicants at levels as low as 10 times lower than those that illicit similar responses in adults [40]. Interest in developmental immunotoxicity (DIT) has further increased as more studies have shown evidence for immune dysfunction in adults stemming from embryonic, fetal, and neonatal exposures to toxins [41]. Although studies have examined the relationship between environmental toxin exposure and immune system development and function in avian species, studies specifically labeled as DIT tests have been limited to mammalian systems. DIT has been defined as “the study of adverse effects on the developing organism that may result from exposure prior to conception (either parent), during prenatal development, or postnatally to the time of sexual maturation” [42]. The diseases that have been associated with DIT to date have been mostly chronic in nature [43]. Similar DIT related diseases in avian species are sure to exist, but may go overlooked with the current methods used to assess immunotoxicity in birds. In wild species, DIT related diseases may also occur completely unnoticed as weaker individuals suffering from the effects of DIT alterations may succumb to death by predation or parasitism earlier than unaffected individuals. Diseases that are often correlated with DIT effects in mammals include those of reproductive and neurological (behavioral) natures, which could have potential population effects in a wild setting. Surely, similar effects in birds would be of interest to ecologists and farmers. For example, one study demonstrated suppression of childhood responses to vaccines due to DIT effects from early exposure to polychlorinated biphenyls (PCBs; Heilmann et al. [44]); PCBs are a group of common environmental contaminants frequently encountered by wild and agricultural avian species. Although avian DIT studies do exist, most have not examined adult responses in subadult toxicant exposed individuals. Incidentally, only one publication could be located that even used the phrase “avian developmental immunotoxicity” [45]; very few avian DIT studies could be located in the current literature. Embryonic exposure to PCB 126 in white leghorns caused a decrease in thymus and bursa of Fabricius cellularity, and PCBs 77 and 126 suppressed antibody titers to sheep red blood cells twofold at 28 days post hatch, however no effects on lymphocyte proliferation or PHA skin response were observed in this study [46]. Chicks from white leghorn hens given feed treated with PCB Aroclors 1232, 1242, 1248, and 1254 had smaller spleens and bursas at 1 and 21 days post-hatch [47]. Although chicks from hens fed Aroclor 1248 had reduced bursa weights at week 11, no differences in antibody

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production from primary and secondary challenges with Brucella abortus given at weeks 8 and 10, respectively, were observed [47]. Bunn et al. [48] observed altered levels of antibodies following challenges of bovine serum albumin given at six and eight weeks of age to chickens that were embryonically exposed to lead acetate. Bursal development has also been shown to be altered in chickens following embryonic exposure to triamcinolone acetonide [49]; in ovo injections at embryonic days 5 or 9 resulted in reduced size and number of bursal follicles and the number of lymphocytes in these follicles. Although these studies have added much needed information to the body of available avian DIT, none had performed adult immune assessments of structural or functional alterations in sub-adult contaminantexposed individuals. Because the effects of the endocrine system on the development of the immune system are well known, most efforts at determining DIT in birds have been with exogenous steroids or estrogen and androgen active EDCs. Androgens are famously immunosuppressive across taxa, including birds [50], although there is one report of exogenous testosterone enhancing antibody titers in response to sheep red blood cells in black-headed gull (Larus ridibundus) chicks [51]. During development, the bursa of Fabricius is exquisitely sensitive to testosterone [52] with its natural regression coinciding with the initiation of androgen production by the maturing gonads. The other primary lymphoid organs of birds, namely the spleen and thymus, appear to be quite unresponsive to androgens [53]. Many different androgens, such as androsterone, androstene-3, 17-dione, methylandrostene diol, 5αdihydrotestosterone (5α-DHT), testosterone propionate (TP), and 19-nortestosterone have been observed to reduce bursal weight and alter bursal morphology [54]. The effects of inhibition of development and regression are so marked that exogenous androgens are commonly used for chemical bursectomization. Androgen-active toxins (androgenic and antiandrogenic) have been shown to illicit effects similar to those of endogenous androgens. Trenbolone acetate, a synthetic androgen, injected into Japanese quail eggs at day 4 of incubation disrupted bursal development as indicated by lower mass and smaller and fewer follicles at day 1 of hatch [14]. Morphological differences in the bursas persisted throughout adulthood, although no differences in measures of the humoral and cell-mediated responses, as measured by antibody production in response to a challenge of chukar partridge red blood cells and the PHA wing web test, were observed. An anti-androgenic chemical, DDE (ethylene, 1,1-dichloro-2,2-bis(p-chlorophenyl), injected into Japanese quail eggs at day 1 of incubation also resulted in reduced numbers of bursal follicles and increased vacuolization within follicles in bursas collected from day old chicks [13]. However, these alterations disappeared as the birds reached adulthood, with the DDE-treated bursas appearing identical to those of controls. Again, neither test of humoral nor cell-mediated responses were different in adult quail embryonically exposed to DDE compared to controls. Taken together, it was suggested that the bursa of Fabricius might be quite resilient in its ability to overcome embryonic insults provided that contaminant exposure did not continue post hatch [13,14]. It was further suggested that functional differences might have been observed if the functional challenges were administered earlier (i.e. chick or juvenile stages) while the immune system was still developing. Little research has been done on the effects of estrogen on the avian immune system in general; however, a few current published reports are beginning to shed more light on its role in its development. Estradiol is a well-known enhancer of the humoral response in mammals [55], and recent studies have been finding this to be true in developing birds as well. Chicks

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embryonically exposed to estradiol at day 4 of incubation were observed to have enhanced antibody titers in response to goat red blood cells and killed Brucella abortus, while antibody responses to Brucella were significantly reduced when estradiol exposure occurred at day 14 of incubation [56]. As might be expected, embryonic day 14 estrogen treatment also caused a corresponding decrease in bursa weight. Estradiol 3-benzoate injected intramuscularly into two day old chicks enhanced antibody responses to Escheria coli and sheep red blood cell challenges at 14 days of age, and similar injections of antiestrogenic tamoxifen suppressed these responses [57]. Other studies have shown exogenous estrogen to have inhibitory effects on bursal development similar to that of androgens. The growth and differentiation of the oviduct and the appearance of progesterone receptors in the bursa correlate with the natural regression of the bursa, suggesting a role of estradiol similar to that of androgens. However, this is unlikely as endogenous estrogens are unable to induce bursal progesterone receptors [58]. Exogenous estrogens and estrogenic compounds appear to be consistently bursitic. Embryonic exposure to levels of estrogen as low as 0.1 ng/g resulted in cyst formation, increased connective tissue, reduced numbers of lymphoid cells, and flattened development of plicae in the bursa, in addition to reduced numbers of thymic lymphocytes in Japanese quail chicks aged 4 to 7 weeks [59,60]. Nonylphenol, an estrogenic chemical, also caused a decrease in the amount of lymphoid cells, increased vacuolization and connective tissue in the bursa, and altered the appearance of the thymus [59,60]. Yolk injections of estradiol in Japanese quail eggs at day four of incubation resulted in reduced follicle size and numbers in hatchling bursas with distorted plicae and thicker epithelial layers surrounding the plicae [61]. Bursas from a subgroup of adult birds from the same study were significantly larger than controls, suggesting an inhibition of natural bursal regression. Broiler chicks fed estradiol for 50 days had significantly smaller bursas than controls as well as a reduced number of total leukocytes and lymphocytes [53]. The studies mentioned in this section provide evidence that more functional tests of the immune system should be incorporated with structural ones when conducting avian developmental toxicity studies. Many examples demonstrate that immune organs are sensitive to structural changes from embryonic chemical exposure, but few show how function is altered. Additionally, many focus only on one life stage, often completely omitting investigation of how embryonic changes affect adult immunocompetence. Finally, the immune function of wild birds is practically unknown [62]; most of the current avian DIT studies use chickens and Japanese quail as model species. Basic difficulties of field studies vs. laboratory studies, current methodology limitations (i.e. unavailability of wild speciesspecific monoclonal antibodies), and subtle differences in windows of exposure and measurement of effects are challenges to carrying out a thorough DIT study with avian species. It should be realized that the unique sensitivity of the developing immune system with potential for persistent effects throughout adulthood makes this type of study critical in the assessment of immunotoxicity.

4.2. Cytokines Recent workshops and discussions have suggested that cytokine measurements should be included in DIT methodologies, however many factors continue to limit their current

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usefulness [41]. Cytokines are regulatory proteins that are released by immune cells and act as intercellular mediators in the generation of immune responses. To correctly interpret the implications of altered cytokine levels, cytokine profiles and interactions must be understood, as correct interpretation is possible only by considering the levels of other synergistic cytokines, cytokine inhibitors, and receptors [63]. Unfortunately, the same limitations that beset the use of cytokine measures in human DIT studies apply in avian studies, but to an even greater extent. The following must occur before cytokine measures can be used to evaluate or determine mechanisms for immunotoxicity: (1) better understanding of baseline cytokine levels in the bloodstream and lymphoid tissues and organs during different stages of development; (2) greater standardization for cytokine measurement techniques; and (3) better understanding of how environmental contaminants affect cytokine levels temporally and spatially (reviewed in Burns-Naas et al. [41]). Although interpretation of results that follow altered levels of avian cytokines are limited due to the state of the science, current DIT studies should include this information whenever possible to add to the body of literature on avian cytokines so that their basic functions and interactions may be learned. Currently, the Avian Cytokine Group (http://www.geel.li.csiro.au/aviancytokines) provides an open-access web site to share information on the function and methods used to detect avian cytokines. Much of the current research on avian cytokines is being done by the poultry industry for the development of immunotherapeutics and vaccine adjuvants [64]. Cytokine therapy is being explored as a possible alternative in the field of disease control in livestock because of an overuse of antibiotics in feed and the potential for development of antibiotic resistant bacteria. No studies could be located in the current literature that measured cytokines in the assessment of immunotoxicity in birds, although this measurement is being used increasingly in mammalian immunotoxicity studies. Evidence for cytokine-hormone crosstalk in birds further supports the notion so often emphasized by DIT proponents that immune and reproductive measures should occur simultaneously during a single study. Interleukin (IL)-6, IL-8, macrophage inflammatory protein (MIP)-1beta, and interferon (IFN)-gamma mRNA expression in the ovary, and IL1beta, IL-6, IL-8, MIP-1beta, IFN-gamma, and transforming growth factor (TGF)-beta2 mRNA expression in the oviduct of chickens were observed to be up-regulated during molting, suggesting a role for cytokines in gonadal regression [65]. Relationships between cytokine release and levels of hormones such as estrogen, progesterone, and corticosterone further demonstrate the interconnectedness of the endocrine and immune systems [65,66]. One of the first neuroendocrine immune interactions to be detailed in an avian species involves the initiation of the humoral response in chickens [66]. Chicken macrophages release IL-1 after antigen exposure, which stimulates corticotropin releasing factor (CRF) by the hypothalamus and other leukocytes. Adrenocorticotropic hormone (ACTH) release is then stimulated by CRF, which also enhances splenic lymphocyte activities. The ACTH causes corticosteroid production which causes lymphocytes to migrate from circulation to the secondary lymphoid organs for antigen processing and antibody production. The corticosteroids and ACTH help to down-regulate the humoral response by inhibiting antibody production and reducing lymphocyte responsiveness to stimuli. Mammalian studies are attempting to develop cytokine profiles to be used as biomarkers in molecular epidemiology of children’s health [67]. One of the main challenges in developing such a profile is that of obtaining distribution data for different ages and ethnic

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groups of healthy children. This would be especially difficult in birds with the additional need to gather the same abundance of data for many different species. If a model species with a cytokine profile that is representative of many different species could be found, not only could biomarkers for birds be developed, but mechanisms behind chemical induced immunosuppression and general avian immune function could be better understood.

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5. CONCLUSION There are relatively few available in vivo and in vitro tests used to assess immune status for avian species compared with those used in mammalian systems. The development of novel techniques and species-specific antibodies for birds compared to those for humans and for rodents used in extrapolation to human health criteria is reflective of the relative emphasis placed on human health versus wildlife health. Although avian immunotoxicity studies may appear to be far behind mammalian work, some evidence suggests that the thinking behind the design of the studies, if not the specific measures or technology, is quite similar between the two. The mammalian DIT experimental design that appears to be most appropriate and feasible for use in avian studies involves a multigenerational design that incorporates immune measures with those of reproduction and neurotoxicity [68]. A one-generation design that incorporates aspects of all three types of measures has already been done in young and adult Japanese quail that were embryonically exposed to androgen active compounds [69]. The U.S. Environmental Protection Agency is currently testing the usefulness of a two-generation toxicity test for EDCs in Japanese quail that employs measures of reproduction, development, behavior, and immune responses (Quinn, study in progress). More of the principles and techniques that are being used in human/mammalian DIT studies should be applied to those using birds. The traditional use of adult-only data is unlikely to be fully predictive of life stages that are experiencing immune system development. Toxicity tests that include the more sensitive life stages would be more likely to be inclusive of individuals at greatest risk. Although immunotoxicology is a relatively recent subdiscipline, increased interest and newly developing techniques and technology will likely stimulate further progress with work that includes avian species. While the field of immunotoxicology is still early in its development, and as methods are being developed, the potential for their use in wild species should continue to be emphasized because so little of the basic functioning of this system remains to be understood in these species.

REFERENCES [1] [2] [3]

Glick, B., T.S. Chang, R.G. Jaap. 1956. The bursa of Fabricius and antibody production in the domestic fowl. Poultry Sci., 35: 224-225. Silverstein, A.M. 1989. A History of Immunology. Academic Press, Inc., New York, NY. Dietert, R.R. and S.J. Lamont. 1994. Avian immunology: from fundamental immune mechanisms to the integrative management of poultry. Poultry Sci., 73: 975-978.

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Michael J. Quinn Luster, M.I., A.E. Munson, P.T. Thomas, M.P. Holsapple, J.D. Fenters, K.L. White, L.D. Lauer, D.R. Germolec, G.J. Rosenthal, J.H. Dean. 1988. Development of a testing battery to assess chemical-induced immunotoxicity. National Toxicology Program’s Guidelines for immunotoxicity evaluation in mice. Fund. Appl. Toxicol., 21: 71-82. ICICIS Group Investors. 1998. Report of validation of assessment of direct immunotoxicity in the rat. Toxicol., 125: 183-201. Schuurman, H.J., C.F. Kuper, J.G. Vos. 1994. Histopathology of the immune system as a tool to assess immunotoxicity. Toxicol., 86: 187-212. Bishop, C.A., H.J. Boermans, P. Ng, G.D. Campbell, and J. Struger. 1998. Health of tree swallows (Tachycineta bicolor) nesting in pesticide-sprayed apple orchards in Ontario, Canada. I. Immunological parameters. J. Toxicol. Environ. Health, Part A, 55: 531-559. Seto, F. 1981. Early development of the avian immune system. Poult. Sci., 60: 19811995. Grasman, K.A. and L.L. Whitacre. 2001. Effects of PCB 126 on thymocyte surface marker expression and immune organ development in chicken embryos. J. Toxicol. Environ. Health, Part A, 62: 191-206. Pasanen, S., T. Ylikomi, E. Paloki, H. Syvala, M. Pelto-Huikko, P. Touhimaa, P. 1998. Progesterone receptor in chicken bursa of Fabricius and thymus: Evidence for expression in B-lymphocytes. Mol. Cell Endocrinol., 141:119–128. Olah, I., B. Glick, I. Toro. 1986. Bursal development in normal and testosterone-treated chick embryos. Poult. Sci., 65: 574-588. Mase, Y. and T. Oishi. 1991. Effects of castration and testosterone treatment on the development and involution of the bursa of Fabricius and the thymus in the Japanese quail. Gen. Comp. Endocrinol., 84: 426-433. Quinn, M.J., Jr., C.L. Summitt, M.A. Ottinger. 2006. The effects of androgen disruption by DDE on the development and function of the immune system in Japanese quail. Immunotoxicol. Immunopharacol., 28: 535-544. Quinn, M.J., Jr., M. McKernan, E.T. Lavoie, M.A. Ottinger. 2007. Immunotoxicity of trenbolone acetate in Japanese quail. J. Toxicol. Environ. Health, Part A, 70: 88-93. John, J.L. 1994. The avian spleen: a neglected organ. Quart. Rev. Biol., 69: 327-351. Silverin, B., R. Fange, P.A. Viebke, J. Westin. 1999. Seasonal changes in mass and histology of the spleen in willow tits Parus montanus. J. Avian Biol., 30: 255-262. Lillehoj, H.S. 1991. Cell-mediated immunity in parasitic and bacterial diseases, in J.M. Sharma (ed.), Avian Cellular Immunology, 155-191. CRC Press, Inc., Boca Raton, FL, USA. Lillehoj, H.S., and J.M. Trout. 1996. Avian gut-associated lymphoid tissues and intestinal immune responses to Eimeria parasites. Clin. Microbiol. Rev., 9: 349-360. Gross, W.B. and P.B. Siegel. 1980. Effects of early environmental stresses on chicken body weight, antibody responses to RBC antigens, feeding efficiency, and reseponse to fasting. Avian Dis., 24: 569-579. Benjamin, N.R. 1958. A rapid method for the estimation of the total leukocyte count. Blood, 13: 677-683. Luster, M.I., C. Portier, D.G. Pait, K.L. White, Jr., C. Gennings, A.E. Munson, G.J. Rosenthal. 1992. Risk assessment in immunotoxicology. I. Sensitivity and predictability of immune tests. Fundam. Appl. Toxicol., 18: 200-210.

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[22] Deyhim, F., R.E. Moreng, E.W. Kienholz. 1992. The effect of testosterone propionate on growth of broiler chickens. Poult. Sci., 71: 1921-1926. [23] Alonso-Alvarez, C., and J.L. Tella. 2001. Effects of experimental food restriction and body-mass changes on the avian T-cell-mediated immune response. Can. J. Zool., 79: 101-105. [24] Smits, J.E., G.R. Bortolotti, and J.L. Tella. 1999. Simplifying the phytohaemagglutinin skin-testing technique of avian immunocompetence. Funct. Ecol., 13: 567-572. [25] Granbom, M., L. Raberg, and H.G. Smith. 2005. The spatial and temporal repeatability of PHA-responses. Behav. Ecol., 16: 497-498. [26] Grasman, K.A. 2002. Assessing immunological function in toxicological studies of avian wildlife. Integ. Comp. Biol., 42: 34-42. [27] Erf, G.F., B. Lockhart, K. Bateman, R. Finley, O.T. Bowen. 2007a. The feather as an in vivo test tube for tissue immune responses. Poult. Sci. Suppl. 1, 86: 143. [28] Erf, G.F., B. Lockhart, O.T. Bowen, K. Bateman, R.C. Finley. 2007b. Using the chicken feather as a window into cell-mediated tissue responses. J. Immunol., 178: 99. [29] Erf, G.F., A.V. Trejo-Skalli, J.R. Smyth, Jr. 1995. T cells in regenerating feathers of Smyth line chickens with vitiligo. Clinical Immunol. Immunopathol., 76: 120-126. [30] Shresta, S., J.R. Smyth, G.F. Erf. 1997. Profiles of pulp infiltrating lymphocytes at various times throughout feather regeneration in Smyth line chickens with vitiligo. Autoimmunity, 25: 193-201. [31] Wang, X. and G.F. Erf. 2004. Apoptosis in feathers of Smyth line chickens with autoimmune vitiligo. J. Autoimmunity, 22: 21-30. [32] Benton, E.H., G.W. Morgan, and P. Thaxton. 1977. Antibody responses to xenogenic red blood cell challenge in the Japanese quail. Immunol. Commun., 6: 259-265. [33] Pardue, S.L., J.P. Thaxton, and G.W. Morgan. 1981. Humoral immunity in Japanese quail following surgical bursectomy at various ages. Poult. Sci., 60: 2713-2719. [34] Fairbrother, A. and J. Fowles. 1990. Subchronic effects of sodium selenite and selenomethionine on several immune-functions in mallards. Arch. Environ. Contam. Toxicol., 19: 836-844. [35] Fairbrother, A., J. Smits, K. Grasman. 2004. Avian immunotoxicology. J. Toxicol. Environ. Health, B. 7: 105-137. [36] Silliman, C.C. and M. Wang. 2006. The merits of in vitro versus in vivo modeling in investigation of the immune system. Environ. Toxicol. Pharmacol., 21: 123-134 [37] Gogal, R.M., Jr., S. Ansar Ahmed, C. T. Larsen. 1997. Analysis of avian lymphocyte proliferation by a new, simple, nonradioactive assay (lympho-pro). Avian Diseases, 41: 714-725 [38] Jenkins, K.A., A.G.D. Bean, J.W. Lowenthal. 2007. Avian genomics and the innate immune response to viruses. Cytogenet Genome Res., 117: 207-212. [39] Burgess, S.C. 2004. Proteomics in the chicken: tools for understanding immune responses to avian diseases. Poult. Sci., 83: 552-573 [40] Luebke, R.W., D.H. Chen, R.R. Dietert, Y. Yang, M. King, M.I. Luster. 2006. The comparative immunotoxicity of five selected compounds following developmental or adult exposure. J. Toxicol. Environ. Health B Crit. Rev., 9: 1-26. [41] Burns-Naas, L.A., K.L. Hastings, G.S. Ladics, S.L. Makris, G.A. Parker, M.P. Holsapple. 2008. What’s so special about the developing immune system? Int. J. Toxicol., 27: 233-254.

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[42] Dietert, R.R. 2005. New developments in the assessment of developmental immunotoxicology. J. Immunotoxicol., 2: 185-190. [43] Dietert, R.R. and J.M. Dietert. 2007. Early-life immune insult and developmental immunotoxicity (DIT)-associated diseases: potential of herbal- and fungal-derived medicinals. Cur. Med. Chem., 14: 1075-1085. [44] Heilmann, C., P. Grandjean, P. Weihe, F. Nielsen, E. Budtz-Jorgensen. 2006. Plos Med., 3: e311, doi:10.1371/journal.pmed.0030311. [45] Dietert, R.R. 2007. Risk factors for avian developmental immunotoxicity (DIT): potential role of sex, hormone status, and age. J. Anim. Sci. 85: 143. [46] Lavoie, E.T. and K.A. Grasman. 2007. Effects of in ovo exposure to PCBs 126 and 77 on mortality, deformities, and post-hatch immune function in chickens. J. Toxicol. Ecol. Health A., 70: 547-558. [47] Harris, S.J., H.C. Cecil, J. Bitman, R.J. Lillie. 1976. Antibody response and reduction in bursa of Fabricius and spleen weights of progeny of chickens fed PCBs. Poult. Sci., 55: 1933-1940. [48] Bunn, T.L., J.A. Marsh, R.R. Dietert. 2000. Gender differences in developmental immunotoxicity to lead in the chicken: analysis following a single early low-level exposure in ovo. J. Toxicol. Environ. Health A., 61: 677-93. [49] Fisher, C.J. and R.H. Sawyer. 2005. The effect of triamcinolone on the development of the bursa of Fabricius in chick embryos. Teratol., 22: 7-12. [50] Deviche, P. and L. Cortez. 2005. Androgen control of immunocompetence in the male house finch, Carpodacus mexicanus Müller. J. Exper. Biol., 208: 1287-1295 [51] Ros, A.F., T.G.G. Groothuis, V. Apanius. 1997. The relation among gonadal steroids, immunocompetence, body mass, and behavior in young black-headed gulls (Larus ridibundus). Am. Nat., 150: 201-219. [52] Glick, B. 1983. Bursa of Fabricius, in Avian Biology, V. VIII. Academic Press, Inc. New York, D.S. Farner, J.R. King, and K.C. Parkes, ed. [53] Al-Afaleq, A.I. and A.M. Homeida. 1998. Effects of low doses of oestradiol, testosterone, and dihydrotestosterone on the immune response of broiler chicks. Immunopharmacol. Immunotoxicol., 20: 315-327. [54] Glick, B. 1980. The thymus and bursa of Fabricius: endocrine organs? in Avian Endocrinology, Academic Press, New York, A. Epple and M.H. Stetson ed. [55] Erbach, G.T. and J.M. Bahr. 1991. Enhancement of in vivo humoral immunity by estrogen: permissive effect of a thymic factor. Endocrinol., 128: 1352-1358. [56] Kondo, Y., C. Goto, A. Abe. 2004. Effects of estrogen treatment during the embryonic period on chick antibody production. J. Poult. Sci., 41: 85-93. [57] Leitner, G., T. Landsman, O. Blum, N. Zaltsmann, E.D. Heller. 1996. Effects of gonadal steroids and their antagonists on the humoral immune response of immuneselected broiler chicks. Poult. Sci., 75: 1373-1382. [58] Ylikomi, T. and P. Tuohimaa. 1989. Sex steroid sensitivity of developing bursa of Fabricius. Int. J. Dev. Biol., 33: 135-140. [59] Razia, S., K. Soda, K. Yasuda, S. Tamotsu, T. Oishi. 2005. Effects of estrogen (17 betaestradiol) and p-nonylphenol on the development of immune organs in male Japanese quail. Environ. Sci., 12: 99-110.

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[60] Razia, S., Y. Maegawa, S. Tamotsu, T. Oishi. 2006. Histological changes in immune and endocrine organs of quail embryos: exposure to estrogen and nonylphenol. Ecotoxicol. Environ. Saf., 65: 364-371. [61] Quinn, M.J., Jr., M. McKernan, E.T. Lavoie, M.A. Ottinger. 2008. Effects of estradiol on the development of the bursa of Fabricius in Japanese quail. J. Avian Biol., in review. [62] Muñoz, F.J. and M. De la Fuente. 2004. Effect of migratory cycle and 17B-estradiol on splenic leukocyte functions in female black-headed gulls. Pflugers Arch. Euro. J. Physiol., 445: 659-664. [63] Burger, D. and J-M. Dayer. 2002. Cytokines, acute phase proteins, and hormones. Annals of the New York Academy of Sciences, 966: 464-473. [64] Hilton, L.S., A.G.D. Bean, J.W. Lowenthal. 2002. The emerging role of avian cytokines as immunotherapeutics and vaccine adjuvants. Veterinary Immunol. Immunopathol., 85: 119-128 [65] Sundaresan, N.R., D. Anish, K.V. Sastry, V.K. Mohan, K.A. Ahmed. 2007. Cytokines in reproductive remodeling of molting white leghorn hens. J. Reprod. Immunol., 73: 3950. [66] Mashaly, M.M., J.M. Trout, G. Hendricks III, L.M. Al-Dokhi, and A. Gehad. 1998. The role of neuroendocrine immune interactions in the initiation of humoral immunity in chickens. Domestic Animal Endocrinol., 15: 409-422. [67] Duramad, P., I.B. Tager, N.T. Holland. 2007. Cytokines and other immunological biomarkers in children's environmental health studies. Toxicol. Lett., 172: 48-59. [68] Luster, M.I., J.H. Dean, D.R. Germolec. 2003. Consensus workshop on methods to evaluate developmental immunotoxicity. Environ. Health Perspect., 111: 579-83. [69] Quinn, M.J., Jr. 2005. Effects of Embryonic Exposure to Androgen-Active Chemicals in Japanese Quail. Doctoral Dissertation, University of Maryland, College Park, MD, USA.

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Chapter 6

UNPLANNED URBANIZATION AND ASSOCIATED RISK ON HUMAN EXPOSURE AND SUSTAINABLE DEVELOPMENT: A CASE STUDY Md. Jahir Bin Alam1 Civil and Environmental Engineering Department Shahjalal University of Science and Engineering Sylhet, Bangladesh

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ABSTRACT Unplanned urbanization leads to environmental degradation. Some emergency planning policies in the Sylhet urban area have been taken by the government. It is seen that a considerable part of the concerned area is classified as a high-risk zone and some parts are classified as very high-risk zones. It is also found that about half of the population (55.22%) is considered a very high-risk zone and this constitutes about 51.29% of total area. Again, 44.78% of population is living in the rest area (48.71%) having high-risk exposure due to existing surface water quality. It can be concluded that if the surface water of the Sylhet Municipality is being used as the source of the water supply system then it should be treated to a high degree of treatment. Detailed study will help in making a sustainable urban plan and will also pave the way to improving the situation.

1. INTRODUCTION Sylhet became a Municipality in 1878, covers an area of 5.82 square kilometers and is situated on the north bank of the Surma River. It is one of the many rapidly growing metropolitan areas located in the northeast region of Bangladesh, and is situated at 28.850 latitude and 98.800 longitude. According to the census of 1872, the population of the Sylhet Municipality was 16,846 [1]. Although the Sylhet Municipality was established almost 127 1 E-mail: [email protected].

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years ago, the actual expansion of the municipal area started in 1971. The 1971 war of liberation accelerated the rate of migration from rural to urban areas, and this large exodus led to rapid urbanization [2, 3]. In addition, Sylhet is also a home of several thousand expatriate workers who leave Sylhet to work abroad, leaving behind their children and spouses. For the sake of children’s education and also to avail urban amenities, many of the migrants’ families moved to the municipal areas of Sylhet which has further enhanced the urban population. At present, the Sylhet City Corporation has an area of 26.5 square kilometers, with an estimated population of around 500,000. But the city has been developed in an unplanned and haphazard way. Serious problems of environmental degradation have been realized and the aim of this study is to figure out which problems are related with the unplanned urbanization of Sylhet city.

2. METHODOLOGY A questionnaire was prepared which asked citizens their feelings about air pollution in Sylhet City. Data was collected from different hospital, clinics, households etc. Then random sampling was done. Every 30th shop’s or household’s family chief and hospital’s doctor, in every ward, was interviewed based on this questionnaire. The distribution of the respondents was as follows, by number of households (Table 1):

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Table 1: Ward wise household sampling Wards Zone wise

No. of Households

1, 2,3,4,5

17

6,7, 8

34

9,10, 11,12

24

13,14,15, 16

24

17,18

29

19, 20,21

29

22,23

29

24, 25

24

26,27

24

Total

234

Using a face-to-face technique, empirical data was collected for the study by sample survey method with the total containing 200 experts’ opinions.

2.1. Sampling Program The most important task of water quality analysis is sampling. One of the common causes of error in water quality analysis is improper sampling. So, the sampling of water should be accomplished with proper precautions meant to secure a representative sample. The sample

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must also be kept in such a manner that the concentration of the species to be analyzed remains unchanged during handling, transportation and possible storage. Meaningful and reliable sampling assures the validity of analytical findings. The goal of sampling is to obtain, for analysis, a portion of the main body of water that is fully representative. The critical factors are• • • •

Sampling point Sampling time Sampling frequency Maintenance of integrity of sample prior to analysis.

2.2. Sampling Procedure Applied The grabbing of samples procedure is applied in the sampling of water from the Sylhet Municipality. • •

•

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• •

Volume of samples: 2 liters of each sample in each location. Point of sampling: In this study, the surface water sources used are ponds and the Surma River. Thirteen sampling points were selected across the entire municipality area. The points were selected on the basis of ponds available. Those that were chosen are shown in figure 1. The feasibility of the ponds and Surma River as an alternative source were tested. The ponds were chosen as a community based water supply source. Preparation of sample containers: Plastic containers of capacity greater than 2 liters were used and prepared as mentioned before. Sample collection: The sample is collected according to the standard procedure as described before. Sampling Frequency: The sampling frequency of this study is taken at 3.

2.3. Analysis of Samples for the Study Area Assessment of water quality involves a lot of data and the problem intensifies when the area in question is considerably large. The Sylhet Municipality town, which is our area of interest, covers about 11 sq km and hence, water samples were collected from different parts of the area so that they could represent the true picture of the surface water. Water samples were analyzed for five environmental parameters-DO, pH, BOD5, As and Fe according to the procedure applied in APHA.

2.4. Developing SWQI Program Water has a variety of different uses such as: supplying public drinking water, crop irrigation, recreation, and maintenance of fish and wildlife habitats etc. Water quality requirements vary, depending on the intended use.

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Figure 1. Sampling locations of Sylhet Municipality.

The most significant problem facing the creation of surface water quality indices is that the uses for water are manifold and the quality of water demanded for each purpose varies tremendously. A high value of a certain parameter may be desirable in one instance and irrelevant or even detrimental in another. For example, high dissolved oxygen concentration is essential if good fishing is to be found in a body of water, but is only of marginal value in a drinking water supply, while it is highly undesirable in boiler-feed water. Therefore, the method, for calculating surface water quality index which has been adopted here, is based on the assumption that water quality is a general attribute of surface water, irrespective of the use to which the water is put. This will henceforth be called the general surface water quality index.

2.5. Method Adopting for Developing SWQI The method adopted for calculating the water quality index is known as the National Sanitation Foundation Water Quality Index (NSF WQI). The NSF WQI was developed using a formal procedure based on the Rand Corporation’s Delphi approach, using a panel of 142 people from throughout the United States, all with expertise in various aspects of water quality management.

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The following, table 2, shows the professions of NSF WQI panel participants: Table 2. Professions of NSF WQI panel participants [4]

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Regulatory officials (federal, interstate, state, territorial, regional) Managers of local public utilities Consulting engineers Academics Others (industrial waste control engineers and representatives of professional organization) Total

101 5 6 26 4 142

Members of the panel were polled by mail using three questionnaires. A brief description of the questionnaires is given below: Questionnaire-1: The respondents were asked to consider 35 water pollutant variables for possible inclusion in a water quality index. They were asked to designate each variable as follows: “do not include,” “undecided,” or “include.” Respondents were also asked to rate each “include” variable according to its significance to overall water quality. This rating was done on a scale of 1 (highest relative significance) to 5 (lowest relative significance). Questionnaire-2: Tabulated result of questionnaire-1 returned to the respondents for their further consideration along with questionnaire-2. In this, each member was asked to review their original ratings and to modify the response if desired. Each member was instructed to note his or her replies for each variable and to compare them with those of the entire group. Questionnaire-3: The respondents were asked to develop a rating curve for each of the included variables [5]. This was accomplished by providing blank graphs to each respondent. Levels of water quality from 0 to 100 were indicated on the ordinate of each graph, while various levels (or strengths) of the particular variable were arranged along the abscissa. Each respondent was asked to draw a curve on each graph, which, in their judgment, represented the variation of water quality produced, by the various quantities of each pollutant variable. The resultant relationships are called functional relationships or functional curves. The NSF WQI developers felt that such a procedure helped minimize problems associated with the arbitrary judgment incorporated into other indices. The investigators subsequently averaged the curves from the respondents to produce a set of average curves one for each pollutant variable. The resulting curves are shown in Figure 2 to Figure 6. In each figure, the solid line represents the arithmetic mean of all respondents’ curves, while the dotted lines bounding the area represent the 80 percent confidence limits. This was the approximate percent of the respondents’ curves which lie within the zone. A narrow band of shading denotes greater agreement among respondents than does a wide band. The investigators sought to derive a set of weights for the index which would add up to 1.0 but would reflect the significance ratings assigned to the variables by the panelists. The arithmetic means of the significant ratings were calculated for all variables rated in the questionnaires. Temporary weights then were derived by dividing the significance rating of each variable into the rating for the highest significance rating (rating of DO). Finally, each temporary weight was divided by the sum of the temporary weights, giving the subindex weights. The weights have a public health focus based on using the water for human consumption.

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Figure 2. Subindex Function for DO in the NSF WQI (For DO>140%, I1=50)(Ott, 1978).

Figure 3. Subindex Function for pH in the NSF WQI (Ott, 1978). Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

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Figure 4. Subindex Function for BOD5 in the NSF WQI (Ott, 1978).

Figure 5: Subindex Function for As in the SWQI . Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

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Figure 6. Subindex Function for Fe in the SWQI.

In this study, five environmental parameters have been considered for which the weights have been shown in Table 3. Table 3. Significance Ratings and Weights for Five Pollutant Variables

Environmental parameter DO PH BOD5 As Fe Sum

Mean of all significance rating 1.85 2.10 2.31 2.56 3.08

Temporary weight 1.0 0.88 0.80 0.72 0.60 4.0

Final weight 0.25 0.22 0.20 0.18 0.15 1.0

2.6. Development of Surface Water Quality Index (SWQI) Program in C The method mentioned in the previous section of this chapter for calculating the SWQI has nonlinear implicit functions in the form of curves for calculating the subindices. Since

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these subindices’ functions cannot be represented by equations and also involve rigorous brainstorming, it is quite difficult and time consuming to calculate SWQI manually. To overcome the above problem a well documented general purpose computer program has been written in the “Turbo C” language. In this computer program, the curves have been divided into small segments that are entered into the program as data and linear interpolation has been undertaken between the points. With the help of the computer program in “C,” the Surface Water Quality Index (SWQI) of all the areas has been calculated. The raw data has been fed in the program and the output of the program gave the index value with the input data in a separate output file [6]. Data was collected from laboratory tests [7, 8, 9, 10, 11] A sample calculation has been shown in Table 4. Table 4. Location name: Bhatalia

Environmental Parameter Do (% Saturation) PH BOD5 (mg/1) As Fe

Value 185.02 9.2 525 0.007 2.2

2.7. Calculation of Exposure Index

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For the assessment of risk exposure to the population, population density, population growth rate and area of wards or zones of the Sylhet Municipality are required and these are obtained from Statistical Bureau of Sylhet [12, 13].

2.8. Development of GIS for the Study Area For the development of GIS for the study area, six geo-coordinates of the Sylhet Municipality were taken by a GPS. A GIS for the study area has been developed using ARC/INFO GIS and ARC VIEW GIS software at the GIS Unit situated in Local Government Engineering Department (LGED) Head Office, Agargaon, Dhaka. The Sylhet Municipality area map has been digitized using a digitizer. Using ARC/INFO software, a TIC coverage has been created taking raster image as a background. This way the real world coordinates i.e. (latitude and longitude) of the study area have been established. Municipal Map Coverage: Raster image of Sylhet Municipality area overlaid with TIC coverage gave the areal coverage of the study area. Municipal Ward Coverage: The municipal area has been divided into five different zones. These have been digitized as a separate coverage using Mouse and Areal coverage as a background.

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The polygon attribute table for municipal coverage has been created using Build command. This table contains zone-id for each of the five zones along with perimeter and area.

2.9. Assessment of Surface Water Quality Using GIS The following procedures have been adopted for assessing the water quality of Sylhet Municipality area using the GIS developed already. i)

The SWQI calculated from the computer program have been given the attribute of surface water quality by adding a new field named “SWQI” into that attribute table in ARC View. ii) The quality of surface water of different zones has been described by five different categories based on the value of index lying in different ranges by selecting a graduated color option in the legend editor in Arc View. Five different categories of surface water quality based on the value of index lying in different ranges are given in table 5. Table 5. Different Category of Water Based on SWQI Value

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Descriptor Water quality Very Bad Bad Medium Good Excellent

Numerical Range of Index 0-10 11-23 24-70 71-90 91-100

The final result has been shown on the Areal map with different categories of water quality in different colors to help distinguish with ease. Assessment of Risk Exposure Using GIS: The following procedures have been adopted for assessing the risk exposure using GIS in the Sylhet Municipality area. 1) The Exposure Index (EI) calculated from Surface Water Load Index (SWLI), Population Density Index (PDI) and Growth Rate Index (GRI) described in the previous chapter have been given the attribute of risk assessment by adding a new field named “Exposure Index” into that attribute table in ARC View. 2) The risk exposure of different zones has been described by five different categories based on the value of exposure index lying in different ranges by selecting graduated color option in legend editor in Arc View. 3) Creating risk zones on the basis of Table 6 has qualitatively assessed the risk exposure. 4) The result consists of an Areal map with different risk zones distinguished by different colors shown on photograph in the next chapter.

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Table 6. Risk Zones Lying in Different Ranges of Exposure Index (EI) Risk-Zones Low Moderately Low Moderately High High Very High

Numerical Range Of Exposure Index 0-100 101-175 176-250 251-275 276-300

3. RESULTS AND DISCUSSIONS

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3.1. Solid Waste Disposal and Garbage Problem The City Corporation authority has set up only 160 concrete made bins for waste disposal in some places of the city area. About 240 tonnes of solid waste are produced everyday from domestic, commercial and clinical sources. Everyday, the City Corporation dumps about 135 tonnes of waste manually from main and other roads and the remaining (44%) is consumed by the city [14]. The solid wastes accumulated in the areas of Sylhet City are derived from various sources. A town of Sylhet's size is normally expected to generate waste of about 0.3kg/cap/day. On this basis, the waste generated in Sylhet town is 23.5 tonnes per day. It was found from the survey work that the generation rate was about 0.36 kg/cap/day. This rate is less than the generation rate of Comilla (0.46 kg/cap/day) and Chittagong (0.66 kg/cap/day) [15, 16]. Household waste disposal is one of the main problems across the city. Among the different options of waste disposal, 50 (21.4%) respondents generally throw their wastes into nearby ponds. 56 (23.9%) respondents generally dump their waste into nearby drains. From this present study, it was found that about 14.5% of the sampled households discard their wastes in their respective compound, while 12% used bins supplied by the Urban City. About 10.7% households throw their garbage on the roadsides. It was also found that either the Urban City or the local people improperly handle the open waste collection points. There was no house-to-house waste collection system in Sylhet. Therefore, the disposal of household waste has become a breeding ground for diseases. In addition, it was observed that solid waste was indiscriminately dumped into roads sides and open drains, leading to serious health risks and degradation of living environment for the people of town. The dumping of domestic wastes in the home and roadside arenas was found to be a potential source of pollution in the localities. In other words, garbage pollution is a serious environmental concern in Sylhet. About 63% households were found to have their own drainage system (internal), while 39% of households have their internal drainage systems directly connected with the city’s drainage system. In contrast, according to the majority of the respondents (63.4%) existing drainage facilities maintained by the Urban City were not satisfactory or sufficient. The most serious health threat is expected to come from pathogens. The corrosive and flammable nature of unprocessed solid wastes (broken glass, metal edges, chips, battery etc.) pose risks to workers and scavengers. On the other hand, the off-site nuisance and health hazards are due to the odorous gases emanating from solid waste disposal sites. Offensive

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odors may be generated during the active stage of composting. Formaldehyde is a common gas emitting from solid waste disposal site. Others are hydrogen, sulfides, ammonia, etc. A rough indicative estimate of maximum distances of health and odor impact was computed using the Gaussian Distribution Model for area sources with wind speed of 3 m/sec at a temperature in the range of 240-350C. The maximum missing height has been assumed to be 1500m and minimum mixing height as 450m. Formaldehyde is a common emitting gas from solid waste disposal sites. Other such gases include hydrogen, sulphide, and ammonia. Since formaldehyde has lowest value of TLV and odour threshold [13], safe distances in terms of health impact and odour impact have been computed. Considering formaldehyde emission of 0.2 g/sec-m2 [13] for 1000 MT solid waste occupying an open area of 0.1km2; the safe distance has been computed and is shown in table 1. It has been calculated based on future urban plan of Sylhet Municipality (200MT) [16; 17].

3.2. Water Logging Due to Unplanned Urbanization

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Water logging is a very common physico-hydrological phenomenon in the city of Sylhet. Even after a minor downpour the city of Sylhet experiences much disturbing water logging very frequently. The main reason of water logging in the city is attributed to the drainage congestion in the city due to unplanned structural growth. One decade ago there were about 17 ponds in Sylhet city. These ponds used to carry a huge amount of rainwater. But now many of these have been filled for various purposes such as Dhopadighi (for the construction of “Osmani Children Park”), Laldighi (for the construction of Hawkers market) [18]. Formerly, this canals and ponds used to carry a huge amount of surface run-off and daily wastewater and these were ultimately drained into the Surma River. Their effectiveness has now been greatly reduced.

3.3. Increase of Traffic Noise Levels in Sylhet City due to Unplanned Urbanization This study aims at studying the level of noise pollution in Sylhet City and analyzing its level of severity. Moreover, as most of the schools and hospitals, which are particularly vulnerable, are located near the roads, noise levels at these places at different distances have been determined in order to evaluate safe distances. Time-weighted average noise levels have been measured at the roadside as well as at distances away from the roadside. This was done to analyze the effects of distance and existing roadside barriers on the reduction of noise levels. The traffic noise index was also calculated to measure annoyance responses to motor vehicle noise using the following formula: TNI (dBA) = 4(L10 - L90) + (L90 - 30) (dBA) where, L10 and L90 are the A-weighted decibel levels exceeded 10% and 90% of the time respectively (i.e. the peak and ambient levels respectively). In order to determine safe distances for schools and hospitals, noise levels at different locations at different times were measured. From data, it is observed that the noise level

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remains almost constant during the sixteen hours of measurement. During this time traffic composition also remains similar. From analysis, it is observed that even in residential areas, the level of noise pollution is very severe for households located near the roadside. Most of the schools and hospitals, which are particularly vulnerable, are located near roads. Noise level reduces linearly with distance unless any noise-reducing barrier is used. The following model is calibrated to estimate the effect of distance on noise reduction. Using this model, desirable positions for locating the vulnerable institutions can be obtained [11, 19]. Noise level (dBA) = 84.314 -0.3886Dm where, Dm is the distance from roadside in meter.

(1)

3.4. Groundwater Fluctuation in Sylhet City Urban areas generally generate more run-off, but they increase the area of impervious surface thereby reducing the infiltration of rainfall and lowering the water tables. It is clear from analysis that the water level has declined with time. It is evident from analysis that groundwater recharge responded linearly with the rainfall and the recharge pattern of Sylhet can be expressed by the equation [11] GWR = 7076.1 – 0.9034 (TRF) (R2 = 0.0338)

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It is observed from analysis that although the amount of rainfall is increasing, it cannot replenish ground water because the urban areas are now becoming impervious thereby preventing rainwater to enter through the soil. As a result, ground water levels in urban areas is lowering day by day.

3.5. Seismicity and Urbanization Soil Stability Factor for sandy and clay soil are 4 and 5 respectively [20]. The earthquake Damage Index (EDI) can be calculated using the following formula EDI = Earthquake Risk Factor* {1+ (10-soil stability factor)/10} Earthquake Risk factor = S/(0.1+ d1.1), where S= severity index; d = distance from the fault in feet. Based on these factors, along with the population density of a given zone in Sylhet city, hazard maps were constructed [11].

3.5.1. Surface Water Assessment The study of the quality of water for the Sylhet Municipality was conducted in March 2002. Laboratory tests were performed for determining the DO, pH, BOD5, As and Fe content of sample waters. Map showing the areas classified in different water quality categories on the basis of Surface Water Quality Index (SWQI) are shown in Figure 7.

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Figure 7. Sylhet Municipality areas classified in different water quality categories on the basis of Surface Water Quality Index (SWQI).

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Map showing the potential risk zones, which gives qualitative assessment of risk exposure to the inhabitants of the area of interest shown in Figure 8.

Figure 8. Sylhet Municipality area classified in different risk zones based on Exposure Index .

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Percentage of area and population coming under diferent risk zones shown in Figure 9 and 10.

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Figure 9. Percentage of area lying under different categories of risk zone.

Figure 10. Percentage of population lying under different categories of risk zone.

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Following are the salient features of the results presented above: i)

ii)

iii)

iv)

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v)

We found that the DO [%saturation] of all samples were significant, the pH value of all samples were tolerable, and the BOD5 value of all samples were high. As content of all samples were much lower than the Bangladesh standard value and the Fe content of all the samples were higher than the Bangladesh standard level. It is clear from analysis that no area has surface water of excellent quality and at the same time some areas viz. Taltola, Zindabazar, Amborkhana, Hawa para, Mazumdari have very bad quality of surface water. Some areas viz. Baruth Khana, Jharnarpar, Mirabazar have a bad quality of surface water. Some areas viz. Dargah Mahallah, Kajal Shah, Subid bazar, Bhatalia, Sekhghat have a medium quality of surface water. Analysis shows that about half of the population (47.02%) falls under the very bad quality of surface water and it constitutes about 47.28% of total area. Only 30.12% of population is living in the area (31.75%) having medium quality of surface water. Again 22.86% of population is living in the area (20.97%) having bad quality of surface water. Figure 8 shows that a considerable part of the concerned area viz. Dargah Mahallah, Kajal Shah, Subid bazar, Bhatalia, Sekhghat, Taltola, Zindabazar is under high-risk zone and some parts viz. Baruth Khana, Jharnarpar, Mirabazar, Amborkhana, Hawa para, Mazumdari come under very high-risk zone. Figure 9 and 10 shows that about half of the population (55.22%) comes under very high-risk zone and it constitutes about 51.29% of total area. Again, 44.78% of population is living in the area (48.71%) having high-risk exposure due to existing surface water quality.

4. CONCLUSION Unplanned urbanization gave rise to severe environmental problems in the city area. Some emergency planning policies can be suggested for the development of Sylhet City such as area development policies which include development of new areas like Upashahar, Korer Para Housing Estate, Bagbari Housing Estate, Tilagor, Surma residential area, etc. each with infrastructure service and urban facilities to reduce the pressure at their urban center, which will help with accelerating the rate of development in the designated areas of urban fringe like Tilagor, Akhalia, Kadamtoli, etc., land resource optimization, gradual dispersion to satellite town like Upashahar, Khadimnagar, South Surma, etc. and also infrastructure development policies like incremental road network development, development of bypass roads to relieve the pressure on existing urban network, preservation and maintenance of the low lying lands, ponds, depressions, etc. and for flood retention as a better means of solution to the existing water logging situation. It is seen that a considerable part of the concerned area is under highrisk zone and some parts come under very high-risk zone. It is also found that about half of the population (55.22%) comes under very high-risk zone and it constitutes about 51.29% of total area. Again, 44.78% of population is living in the rest area (48.71%) having high-risk exposure due to existing surface water quality. It can be concluded that if the surface water of Sylhet Municipality is being used as the source of water supply system it should be treated to

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a high degree of treatment. However, detailed study, if possible, should be carried out to establish a more generic picture of this city, its problems, and potential ways to improve the situation.

REFERENCES [1] [2]

[3] [4] [5] [6] [7] [8]

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[9]

[10] [11] [12] [13] [14] [15] [16] [17]

Hunter, W.W. A statistical account of Assam. Vol-II, Trubner and Co., London,1879. Rahman, H. and Nag, M. Traffic contribution to noise and air pollution in Sylhet city. B. Sc Engineering Thesis, Shahjalal University of Science and Technology, Sylhet, 2005. Rahman, M.S. Bangladesh Pourashava Statistics. National Institute of Local Government, Dhaka,1990. Canter, L.W. Environmental Impact Assessment. 2nd edition, McGraw-Hill Inc. Singapore, 1996. Ott, W. R. Environmental Indices: Theory and Practice. Ann Arbor Science Publishers Inc, 1978. Kelley Al. and Pohl lra. A Book on C, Programming in C. Second edition, The Benjamin/Cummings Publishing Company Inc, 1990. Uddin, M.M., Mondal, S. A case study of existing water supply system of Sylhet Municipality. 2002. Hossain, A. Evaluation of Surface water Quality: A case study on Surma River. B.Sc Engineering Thesis, Civil and Environmental Engineering Department, Shahjalal University, 2001. Muyan, Z. and Mamun ,M. Predication of pollution status of the Surma River by Simulation. B.Sc Engineering Thesis, Civil and Environmental Engineering Department, Shahjalal University, 2003. Shiddiky, M. J. A. A study on the water quality parameters of the Surma River, M.Sc thesis, Chemistry Department, Shahjalal University of Science and Technology, 2002. Khan, S. K. Problems of Sylhet city due to unplanned urbanization. B. Sc Engineering Thesis, Shahjalal University of Science and Technology, Sylhet, 2005. Bangladesh Bureau of Statistics (BBS). Statistical year book of Bangladesh, 19th edition, 1998. Department of Environment, Bangladesh 2000. Annual report-2002. Dhaka, Bangladesh. Salam, A. Analysis and design of solid waste management system for residential zone of Dhaka city. M.Sc Thesis, Department of Civil Engineering, BUET, Dhaka,2000. Alam, J. B. and Hasan Bhakt, A. S. Baseline survey of Sylhet and Habiganj. report submitted in World Health Organization, 2003. Sheblii S. Solid Waste Collection and Transport System in Sylhet Pouroshava. B. Sc Engineering Thesis, 2001. Ibney, F and Ali. , M. A (2005). A study on solid waste management system of Dhaka city corporation: effect of composting and landfill locations. UAP journal of Civil and Environmental Engineering, 1(1): 18-26.

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[18] Haque M.S. Study of the Traffic Facilities on Amberkhana to Bondor under Sylhet City Corporation. B. Sc Engineering Thesis, Shahjalal University of Science and Technology, Sylhet, 2005. [19] Ahmed K. A Study on Noise Pollution in Dhaka City. Department of Environment, Bangladesh, 1998. [20] Ansari M. Seismic Risk of Sylhet. paper presented in seminar in SUST, 2005.

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In: Impact, Monitoring and Management… Editors : Ahmed El Nemr

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Chapter 7

TOXIC EFFECTS OF LEAD AND CADMIUM AS INDUSTRIAL POLLUTANTS ON THE CHROMOSOME STRUCTURE IN MODEL MAMMALIAN SPECIES M. Topashka-Ancheva 1 and S. E. Teodorova2 1

Institute of Zoology, Bulgarian Academy of Sciences, Bd. Tzar Osvoboditel 1, 1000 Sofia, Bulgaria 2 Institute for Nuclear Research and Nuclear Energy, Bulgarian Academy of Sciences, 72 Tzarigradsko chaussee, 1784 Sofia, Bulgaria

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ABSTRACT A survey on ecologo-toxicological experiments exploring the karyotype responses of small mammalian species to heavy metal load is proposed. The animals used were laboratory mouse (Mus musculus alba) inbreed line BALB/c and wild Guenther’s vole (Microtus guentheri), adapted to laboratory conditions. An industrial mixture containing lead and cadmium in high concentrations was applied as a representative of emission to the environment. The polymetal dust was mixed with conventional animal food at a 1% concentration. The metal quantities in the animals’ diet were about 780 mg/kg lead and 64 mg/kg cadmium. Chromosomal aberration frequency and the type of chromosomal aberrations in bone marrow cells as well as the changes in the nuclear proteins in liver and kidney tissues were studied. Samples for analyses were taken on days 15, 40, 60, and 90. The presented mathematical model describes successfully the time course of the chromosomal aberration frequency in female BALB/c mice. The responses of both species were compared and the high relevance of their use in ecotoxicology and zoomonitoring was confirmed. The frequencies of the chromosomal aberrations in the exposed Guenther’s vole and BALB/c mice differed insignificantly. The most frequently encountered aberrations were chromatide breaks and centromere-centromeric fusions (c/c). In Guenther’s vole, significant damage to the chromosomal protein were found on the sixtieth day after exposure. In BALB/c mice, changes in the electrophoretic profiles were recorded on day 15. No trend of continued increase of the chromosomal aberration frequency in both rodents was established during the exposure. This fact suggests a

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M. Topashka-Ancheva and S. E. Teodorova relative high resistance of genetic apparatus to heavy metals as a component of the anthropogenic pollution.

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1. INTRODUCTION The effect of the environmental pollutant – polymetal industrial dust, on chromatin structure of small mammals in ecotoxicological experiments was tested. The study of the model mammalian species organisms' response to heavy metal exposure is of prime importance in the context of the effect that these metals could have in humans. Small mammals, and especially rodents, are preferred in experiments for the reason of their basic position in the food chain, fast reaching of maturity, high total metabolism and specific biological reactions (substantial increase of chromosome aberrations frequency, changes of hematological indices etc.) to environmental pollution. Industrial pollutants settle on soil and plants and thus penetrate the food chain, including humans. Toxicological experiments using samples collected from the waste products of an industrial operator allow assessment of the harmful effects of the pollutants on the populations inhabiting the respective region. Of particular interest is the study of heavy metal mixtures. Because such mixtures are widespread industrial pollutants, it is important to estimate the bioaccumulation and toxicity of these metals in combination. Lead, cadmium and mercury are the most toxic heavy metals, affecting genetic status, hemopoesis, blood parameters, different physiological functions, and body weight. We focused our attention on lead and cadmium due to the presence of these metals in the mixture used in our experiment. ’s. The toxic action of heavy metals has been studied at the cellular and sub-cellular levels [1]. Ershev and Pleteneva [2] have published on the distribution, lethal doses, toxicokinetics, and toxicity mechanisms of metals and other inorganic compounds. In addition, Goyer [3] has presented a detailed view on the toxicokinetics, toxicity, and pathological effects of the metals. Chromosomal aberrations (CA), involving gross alterations of genetic material, have been considered as a sensitive endpoint for detecting genotoxic effects induced by heavy metal and toxic chemicals. The study of cytogenetical alterations is considered highly relevant in the human context (International Commission for Protection [4], World Health Organization [5] ). Lead has long been recognized as a potential hazard to human health [6-9]. A significant ecotoxicological risk to a wild population of bank voles, associated with high Pb tissue concentration has been estimated [10]. Lead affects a wide range of physiological systems and organs, including the central nervous system, hematopoetic system, cardiovascular system, kidneys, and gastrointestinal tract [11]. Lead also produces an excessive amount of reactive oxygen species resulting in oxidative stress, thereby resulting in hypertension that leads to renal dysfunction and chronic kidney disease [12]. Lead also has multiple hematological effects. Microcytosis and hypohromy of red blood cells appear because of disturbed heme synthesis [3]. Reticulocytosis has been observed in adult amphibians exposed to inorganic Pb [13]. Significant decreases in red blood cells and mean corpuscular hemoglobin and significant increase in the frequency of micronucleated polychromatic bone marrow erythrocytes were found in Algerian mice (Mus spretus) exposed to Pb [14]. Lead is

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known to damage the chromosomal structure in mammalian cells [15-17]. Mutagenicity and carcinogenicity of Pb have been reported [18-20]. At toxic doses, lead acetate and lead nitrate have induced DNA breaks determined by nick translation [18]. Bilban and Jakopin [21] found that the incidence of structural CA in workers in a lead-zinc mine is probably more strongly influenced by heavy metals than by radon. Cadmium exposure is a chronic problem resulting in a gradual accumulation of Cd in target organs – the liver and kidneys. Tissue concentrations of Cd in wild species and critical tissue concentrations of this metal, leading to different dysfunctions, were discussed by Cooke and Johnson [22]. Tubular necrosis and renal dysfunction have been noted as the most characteristic features of Cd nephrotoxicity [22-24]. Chronic pulmonary disease, disturbance of calcium metabolism, hypertension, and cardiovascular effects could also occur because of Cd intake [3]. However, Cd bound to metallothionein is nontoxic under the critical concentration [2,3]. Carciniogenic activity of Cd was established [25-27]. Generation of DNA single-strand breaks and CA has been found only at considerably very high Cd concentrations [28]. In addition, other authors consider that a direct induction of CA by cadmium compounds is ambiguous [29]. Involvement of reactive oxygen species induced by Cd has been shown to generate DNA single strand breaks and CA [30]. Both lead and cadmium could exert pronounced indirect genotoxic effects, interacting with DNA repair processes [28]. The inhibition of DNA repair could play a role in the accumulation and stability of DNA damage, resulting in the initiation of carcinogenic processes. The heavy metal and toxic element influence on small mammals, chosen as zoomonitors, was studied in our three-year (1994, 1995, and 1996) biomonitoring of a few polluted regions in Bulgaria. The zoomonitors used were from the order Rodentia, families Muridae (three species) and Cricetidae (five species) and from the order Insectivora, family Soricidae (two species). A comparative evaluation of heavy metal loads in the different species was made using data for liver and body bioaccumulation [31]. Chromosome aberrations, micronuclei (Howell-Jolly bodies) and basophilic granulations had been found in the rodents inhabiting the polluted regions [32,33]. To explore the toxic effect of lead and cadmium in conditions of a chronic exposure, we carried out ecologo-toxicological experiments using an industrial pollutant, polymetal dust, which is a waste product from KCM-Plovdiv, a lead-zinc facility near Plovdiv and Asenovgrad in Bulgaria. Wild Guenther’s vole Microtus guentheri and laboratory mouse Mus musculus alba inbreed line BALB/c were examined in two experiments, respectively. Bioaccumulations of Zn, Cu, Pb, and Cd in body and organs of Guenther’s vole were studied and clastogenic effect of the dust on the animals was recorded in a 60-day experiment [3437]. Bioaccumulations of the same metals, structural and numerical chromosome changes, and blood pathology (decrease in hemoglobin, significant reticulocytosis, microcytosis, hypohromy, and basophilic erythrocytic granulation) were investigated in BALB/c mice during the 90-day experiment [38,39]. In addition, electrophoretic profiles of the chromosomal proteins from the liver and kidney in both rodents were examined [36,38]. The influence of Pb and Cd contamination on the resting metabolism and body temperature in the context of thermoregulation was studied in BALB/c mice [40]. A mathematical model for zinc and cadmium bioaccumulations in BALB/c mice was proposed [41]. Data for the chronic exposed female BALB/c mice suggested some regularity in the time course of the structural CA and we found grounds to construct a mathematical model trying to

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explain the kinetics of chromosomal aberrations frequency (CAF), observed in bone marrow cells. The model was based on modeling Pb bioaccumulation in bones [42]. The present chapter deals with the results concerning quantitative (frequency) and qualitative (type of aberrations) characteristics of the structural chromosome changes and chromosomal protein changes observed in Guenther’s vole and BALB/c mice during chronic ecologo-toxicological experiments. The survey proposed compares the responses of both species in order to make a reliable assessment of their sensibility with a view to their further use in ecotoxicology and zoomonitoring.

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2. EXPERIMENTAL ANIMALS Mammalian species from the order Rodentia – Guenther’s voles Microtus guentheri (Arvicolidae), males and females, and white mice Mus musculus alba inbred line BALB/c (Muridae)- both males and female were used in two ecologo-toxicological experiments (the first experiment with Guenther’s voles and the second experiment with white mice). The wild Guenther’s voles were adapted to laboratory conditions. The white mouse and Guenther’s vole are species accepted as bioindicators in the Global biological monitoring system [43]. Being phytophaguses, voles and mice represent a basic step in the trophic chain. One hundred and twenty Guenther’s voles (60 males and 60 females), adapted to laboratory conditions, and one hundred and eighty white mice (BALB/c), 8–10 weeks of age, were divided into control and experimental groups. Guenther’s voles were distributed as follows: a control group of 30 and an experimental group of 90 animals. BALB/c mice were distributed into a control group of 50 and an experimental group of 130 animals. The mean start weights were –Guenther’s voles: 52.96 ± 1.58 g; BALB/c mice: 20 ± 1.5 g. The experimental rodents, both Guenther’s voles and white mice, were exposed to polymetal industrial dust from the electrofilters of the lead-zinc plant “KCM-Plovdiv,” mechanically mixed to a 1 % concentration with conventional, balanced animal food. The polymetal samples collected from electrofilters represented airborne contaminants in the working zone of the plant. The quantities of the metals (mg/kg) in the diet were as listed in Table 1. Table 1. Quantities ( mg/ kg ± SD) of the heavy metals in the rodents’ diet Elements Zn Cu Pb Cd

Guenther’s vole and BALB/c mice Control Experimental 90.9 ± 25.9 1945.0 ± 429.2 11.3 ± 1.1 20.9 ± 7.3 61.8 ± 20.9 784 ± 243.6 3.5 ± 1.9 64.1 ± 10.5

Control and experimental animals were reared in a vivarium and housed in cages constructed of solid plastic sides with stainless steel grid ceilings and floors in a room with a controlled temperature (approximately 20o), humidity (45-75%) and light cycle (12 h light, 12 h dark). All animals were allowed access to food and water ad libitum. All of the animal

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experiments were conducted according to approved protocols, and in compliance with the requirements of the European Convention for Protection of Vertebrate Animals used for experimental and other Specific Purposes and the current Bulgarian laws and regulations. The concentrations of Zn, Cu, Pb and Cd in the whole body and in different organs and tissues (liver, kidney, spleen, and bones) of the control and experimental animals were determined on days 15, 40, and 60 of exposure in the experiment with Guenther’s voles and on days 15, 40, 60, 90 and 120 of exposure in the experiment with BALB/c mice. The animals were euthanased, and after the removal of the alimentary tract, the tissues were dried at 600C to a constant weight. The dried tissues were dissolved in a mixture of concentrated nitric–perhloric acid (4:1) [44]. Analyses of the metals were carried out by atomic absorption spectrometry using a Perkin-Elmer (Polo Alto, CA) 2380 instrument. At the same time points, samples for cytogenetical analyses as well as for electrophoretic separation were taken.

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3. CHROMOSOMAL ABERRATIONS The karyotype of the South European Guenther’s vole (Microtus guentheri) used in the first experiment contains 54 acrocentric chromosomes (2n = 54) [45]. The fact that the chromosomes are acrocentric facilitates the cytogenetical studies on chromosome structure alterations caused by various agents. Here chromosome aberrations in mitotic chromosomes of bone marrow cells were analyzed. All subspecies of Mus musculus (domesticus, musculus, castaneus, and bactrianus) as well as the laboratory lines have a karyotype with 20 pairs of chromosomes (2n = 40), including 19 autosomal pairs and the X and Y sex chromosomes. All of the 19 autosomes as well as the X chromosome are of acrocentric type. In both experiments, the cytogenetical analysis was performed as described by Preston et al. [46]. Mitomycin C (3.5 mg/kg, in saline solution; ip injected) was used as a positive control. The other animals were injected with only 0.2 mL 0.9% NaCl. Bone marrow chromosomal aberration assays were performed on groups of animals, each one (control and experimental) consisting of 5 males and 5 females. The animals were injected ip with colchicine at a dose of 0.4 mg/kg, 1 h before isolation of the bone marrow cells. Bone marrow cells were flushed from the femur with 0.075 M KCl at 37°C over 20 min. Thereafter the cells were fixed in methanol-acetic acid (3:1), dropped onto cold slides and air dried. To examine chromosome aberrations the slides were stained with a 5% Giemsa solution. At least 100 well-spread metaphases were analyzed per animal at random. The frequencies of chromosome aberrations were determined for each animal. The mean ±SD for each group was calculated and the data was statistically evaluated for their significance by analysis of variance using the Student t test. Comparisons between the experimental and control groups were made using ANOVA-SPISS 7.5. The CAF in the analyzed metaphases of bone marrow cells of both Guenter’s voles and BALB/c mice are presented in Figure 1. In the same figure the CAF in male and female mice are presented separately. The percentages of aberrant metaphases in the control groups were within the range of spontaneous frequencies. The differences between control and experimental groups for both voles and mice were statistically significant (Table 2).

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Table 2. P values of a comparison of the chromosome aberration frequency in Guenter’s vole and BALB/c mice: control (c) and experimental (15; 40; 60; 90); and in the different time points for the experimental groups P

Chromosome aberration frequency

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Guenther’s voles

BALB/c mice

Pc 15

< 0.001

< 0.001

< 0.01

MalesFemales Control P15 < 0.02

Pc 40

< 0.001

< 0.001

< 0.001

P40 < 0.02

P40 > 0.1

P40 < 0.02

P40 > 0.1

Pc 60 Pc 90 P15 40 P15 60 P15 90 P40 60 P40 90 P60 90

< 0.001

< 0.001 < 0.001 < 0.05 < 0.02 > 0.1 < 0.01 < 0.1 > 0.1

< 0.001 < 0.01 < 0.001 < 0.01 < 0.05 < 0.1 < 0.01 < 0.02

P60 > 0.1 P90 < 0.05

P60 < 0.001 P90 < 0.001

P60 < 0.02

P60 > 0.1

< 0.05 > 0.1 > 0.1

Males

Females

Guenther’s voles to BALB/c mice Control Experimental

MalesFemales Experimental P15 < 0.001

P15 < 0.02

P15 > 0.1

Figure 1. Frequency of the chromosomal aberrations in bone marrow cells of Guenther’s voles (Microtus guentheri) and BALB/c mice (Mus musculus alba) exposed to industrial heavy metal mixture.

There was a statistically significant difference between the control groups in Guenter’s voles and BALB/c mice, averaged by gender (P < 0.02), and this result was expected. The

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spontaneous CAs in BALB/c mice are relatively higher compared to those in Guenter’s voles due to the specific character of the mouse karyotype. We found that among the spontaneous CAs in mice centromere-centromeric fusions (c/c fusions) predominate. This type of CAs, mainly referred to the whole arm translocations, has been given the name “Robertsonian translocations.” The simple fusion of events, resulting in the attachment of two standard chromosomes at their centromeres, have formed the non-standard karyotype of Mus musculus. The rate of exchanges between non-homologous chromosomes in the mouse is particularly high [47]. This is facilitated by the acrocentric nature of mouse’s chromosomes. The acrocentric chromosomes in genus Mus are prone to spontaneous c/c fusions because of the specific structure of the centromeric regions. Robertsonian translocations cause structure forms as meta- and submeta-centric chromosomes through centric exchanges of two acrocentrics. This phenomenon is due to single strand’s breaks in the minor SAT DNA located in the centromeric regions of mice chromosomes [47]. No statistically significant difference was observed, however, between CAF in Guenter’s voles and BALB/c mice, regarding the experimental groups (P > 0.1). One could state that both studied species showed similar patterns in their responses to the applied industrial mixture. The distribution of the different types CA is displayed in Figure 2. Chromatide breaks predominated in both Guenter’s voles and BALB/c mice. In BALB/c mice there were also many centromeric fusions (c/c) although c/c were less compared to the breaks. The following ratios were calculated for the experimental animals: breaksG.vole/c/cG.vole = 7.3 and

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breaksBALB/c/cBALB = 1.77. In BALB/c mice took place the ratios: breaksmales/breaksfemales = 1.7 and c/cmales/c/cfemales = 1.6. Telomere-telomeric fusions (t/t) were detected at lower frequency: bellow 1% in Guenter’s voles and maximum 3.5% in BALB/c mice. It is known that Pb induces terminal deletions in mice chromosomes [16]. We supposed that a formation of "sticky telomeres" linking each other is possible. Centromere-telomeric fusions (c/t) and ring chromosomes were found below 1% in both rodents. The scarce presence of t/t and c/t shows that Pb and Cd have a weak effect on DNA component of telomeres. Fragments in Guenter’s voles were found of maximum 2.7% and in BALB/c mice bellow 0.5%. An important finding could help to explain the high level of CAF in the experimental animal groups. Demarque et al. [48] established that the Pb concentration in bone marrow is proportional to that in bones. Lead is well known as a bone-seeking element [49] and in our experiment with BALB/c mice, in mice bones a Pb concentration of 1625 ± 42 mg/kg was measured on day 90 [42]. Therefore, it was reasonable to expect a high Pb concentration in bone marrow which led to significant increase of CAF. As mentioned above, Pb is known to damage the chromosomal structure in mammalian cells. An influence of Cd from the polymetal dust does not appear to be related to chromosomal damage because of the specific distribution of Cd in cells. A small quantity of Cd is found in the nucleus and mitochondria, and the greater part is in cytosol, where Cd is bound to metallothionein [2]. The Cd concentrations in mice bone observed during the experiment were not high (20 mg/kg on day 90) although very high Cd levels in the liver (479.1 + 28.9 mg/kg) and kidney (465.7 + 11.1 mg/kg) on the same day were found [39,42]. Explorations of other authors indicated that no relationship has been observed between genetic damages, and liver and kidney Cd concentrations [50,51]. An effect of copper is possible, since clastogenetic effects of copper sulfate on bone marrow chromosomes have been noted by Agarval et al. [52].

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Figure 2. Distribution of the types chromosomal aberrations revealed in Guenther’s vole (Microtus guentheri) and BALB/c mice (Mus musculus alba).

According to recent considerations, copper and iron ions are not direct genotoxic factors, but they are factors inducing genesis of genotoxic oxygen species [53]. However, the maximum Cu concentration we found in bones was 12.6 ± 1.9 mg/kg. The bone Zn was much higher: 468.6 ± 37.8 mg/kg on day 60 but Zn is not known to damage severely DNA. Thus, it is reasonable to consider that in our experiments Pb bioaccumulation was the main factor generating CA in bone marrow cells. Different genetic reactions were observed in experimental male and female BALB/c mice. The CAF in males was higher than the CAF in females (Figure 1, Table 2). The highest CAF in male mice was 23% (day 60) and the highest CAF in female mice was 15.77% (day 40). The CAF in males were 2.6, 1.64, and 1.9 times higher when compared to females on days 15, 60, and 90, respectively (P < 0.001). The CAF in males and females did not differ significantly only on day 40 (P > 0.1). After day 60, a significant decrease of the CAF (by 25%) was observed in the females (Table 2). The scientific literature lacks studies targeted to the elucidation of the differences between the genetic reaction to toxic agents in male and female individuals. The most investigations of genotoxicity have been carried out on male specimens and thus there are not many results providing comparative analyses. Dubinin [54] suggested, in the context of experiments studying the influence of the dose rate on mutations in mouse oocytes, that the mutation rate in females is lower than that in males because of more effective repair in females. Recently Scheirs et al. [51], investigating effects of environmental pollution on wood mice (Apodemus sylvaticus), reported that the genetic damage was higher in male mice

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than in female ones at the most polluted site, but not at the other areas. Probably, significant differences in genetic responses in both sexes are visible at relatively more severe assaults. Our results regarding CAF levels in male (CAFM) and female (CAFF) mice obtained in severe conditions (high doses of two toxic metals, especially lead) indicated clearly a more sensitive genetic apparatus in males and a more effective repair in females. The greater susceptibility in males was expressed by the sharp increase of CAFM after the beginning of the exposure (day 15) when CAF = 20%. On day 90 CAFM was the same as CAFM on day 15. This fact suggests a lower repair in males compared to females. The bone Pb increased 4 times (Figure 3) and CAFF increased 2 times (Figure 1, Table 2) in the interval 15 – 40 days. After day 40 Pb slightly increased but CAFF decreased. These results once more confirm the good repair ability in females. Structural CA may be induced mainly by direct DNA breakage, by replication on a damaged DNA template, and by inhibition of DNA synthesis [55,56]. They can be divided into two main classes: chromosome-type aberrations (CSA) involving both chromatids of one or multiple chromosomes and chromatid-type aberrations (CTA) involving only one of the two chromatids [56,57]. Metaphase analysis provides information on the timing of DNA lesions relative to DNA replication [58]. CSA result from double-strand breaks (DSB), incompletely- or non-repaired, formed in G0/G1 phase of the cell cycle or from DSB generated before replication in early S phase. In such cases in metaphase there are chromosome-type breaks, dicentric and ring chromosomes, and fragments. DSB generated in postreplicative DNA in later S phase and in G2 phase give rise to CTA (chromatid type breaks and exchanges) [57]. CTA may arise also, in response to single-strand breaks (SSB) induced in early S phase. CTA are usually generated by S-phase-dependent clastogens (e.g. chemicals) [59]. SSB resulting from Cd and Pb influence were reported by Privezentsev et al. [60], Valverde et al. [61], and Shaik et al. [62]. Chromatide breaks observed in metaphase would result from incomplete or failed repair [63]. In our experiment with BALB/c mice isochromatide breaks (chromosome-type breaks), dicentric and ring chromosomes, occurred infrequently ( Figure 2). Fragments, occurring in Guenter’s voles, suggest some percentage of CSA. The high presence of chromatide breaks and Robertsonian translocations in the examined rodents suggests an essential prevalence of CTA. Thus, the data of our experiments, compared with the data of other authors, provide evidence that Pb and Cd are mainly S-phasedependent clastogens.

4. NUCLEAR PROTEINS It is of importance to explore also the chromosomal protein in animals chronically exposed to heavy metals. Most probably, the toxic metals bind to the proteins [64]. Structural alterations and chemical modulations of DNA and histones induced by genotoxic agents and mainly the degree of DNA damage repair in the nuclear chromatin are the crucial events leading to cell death or cancerogenesis [65]. As far as the chromatin complex has been considered as a target of the heavy metal action [66, 67] some detectable changes in its protein moiety could be expected. Some of the more interesting and novel theories of Pb toxicity have focused on lead–protein interactions. The interaction with proteins [68] and DNA–protamine complex [69] has been intensively studied. In the cell nucleus, chromatin

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consists of repeating subunits – nucleosomes. Each nucleosome core includes 147 bp of DNA wrapped around a histone octamer. The core histones are arranged in a tripartite manner. One molecule of histone H1 binds to the DNA linking adjacent nucleosomes [70]. Non-histone chromosomal proteins rather than histones are responsible for the differences in chromatin template activity during the S-phase and mitosis and it was proposed that non-histone proteins may modify gene expression during the cell cycle by mediating the binding of histones to DNA [71]. Non-histone proteins activate regions of repressed DNA by their association with histones [72]. In parallel with the chromosomal changes in rapidly proliferating bone marrow, we also investigated the nuclear protein patterns in liver and kidney cells from Guenter’s voles and BALB/c mice, exposed to the same industrial mixture. The electrophoretic profiles of chromosomal proteins in these tissues were explored. Chromatin was isolated from the vole’s and mouse’s livers and kidneys by the method of Djondjurov et al. [73] using Nonidet P-40 washed nuclei, which were extracted with increasing concentrations of NaCl/EDTA, pH 8.1 (0.075/0,025 M and 0.037/0.0125 M) and deionized water. Electrophoretic separation was carried out in SDS-slab polyacliamide gels containing 15% acrylamide according to Laemli [74]. Slabs were 0.1 cm thick, 10 cm long and were run at a constant voltage of 5 V/cm. Molecular weight markers: phosphorilase B, bovine serum albumin, carbonic anhydrase, and egg albumin (Serva) were run in parallel. Protein samples, containing about 80–100 g protein, were dissolved in a sample buffer and applied on the gel. Gels were stained with 0.1% Serva Blue R 250 and scanned with a laser densitometer LKB Bromma at 472 nm. Quantitative measurements were made by gravimetric estimation of the peak areas of the densitometric tracings. Protein concentration was measured by the method using bovine serum albumin as a standard [75]. The comparative analysis of the electrophoretic profiles in Guenter’s voles on days 15 and 40 revealed a similarity in liver and kidney tissues. Specific differences in the chromosomal protein profiles between the exposed and control animals were found in the pattern of liver and kidney proteins on the sixtieth day of exposure. In each one a prominent band for each tissue was found. There were increases of high molecular weight fractions of non-histone proteins, different for each tissue. In addition, distinct changes in the bands representing the group of lysine-rich histone proteins were observed. The fact that significant differences were observed only at the end of the experiment could suggest a non-pronounced direct influence of the heavy metals on the content of the chromosomal proteins in Guenter’s vole. The comparative analysis of the electrophoretic profiles in BALB/c mice revealed significant changes in the non-histone proteins yet on day 15. A decrease or loss of two high molecular weight fractions in the kidney and an increase of three high molecular weight fractions in the liver were observed. These differences between the exposed and control animals persisted up to day 90 in the kidney, but only up to day 60 in the liver. On day 90, a relative similarity was established between the preparations of liver tissue from the exposed and control mice. To some degree, this fact correlates with the result indicating no aggravation regarding CAF in bone marrow cells from day 60 up to day 90. In the histone fraction of the exposed in BALB/c mice no specific changes were found. While regarding CAs in bone marrow cells, we could consider that the main toxic effect is exerted by Pb, in the case of the electrophoretic profiles of chromosomal proteins in liver and kidney it seems most likely that Cd plays a decisive role. An essential mechanism of Cd

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poisoning pathogenesis is related to the interaction of this metal with high-molecular proteins, especially enzymes containing thiol groups [2,76]. The concentrations of Cd we determined on day 60 in liver and kidney in Guenter’s voles were: 172.7 ± 10.58 mg/kg and 159 ± 7.35 mg/kg, respectively [36]. The concentrations of Cd on day 90 in livers and kidneys in BALB/c mice were 479.1 ± 28.9 mg/kg and 465.7 ± 11.1 mg/kg, respectively [39]. The lower levels of Cd in Guenter’s voles’ tissues compared to that in BALB/c mice’ tissues could explain the quite different responses both rodents reflected in their nuclear protein patterns. Although both species were exposed to heavy metals via equal food composition, containing the same metal concentrations, we should take into account the different body mass of the rodents. The mean body weight of Guenter’s voles was 2.5 times higher than that of BALB/c mice. Respectively, less tissue concentrations of heavy metals could be expected in Guenter’s voles, hence the lower effects of Cd poisoning. Lead ions Pb2+ bind SH-groups in active centers of many enzymes and thus reduce their activity [2]. However, the Pb concentrations in the livers and kidneys of the studied rodents at the end of the experiments were as follows: in Guenter’s voles – 10.5 ± 0.89 mg/kg and 45.2 ± 7.3 mg/kg; in BALB/c mice – 9.8 ± 0.7 mg/kg and 10.56 ± 2.1 mg/kg, respectively. These concentrations were much less compared to Cd concentrations and it is clear that liver and kidney chromosomal proteins could be predominantly damaged by Cd influence. In administration of Cd alone, (3 mg CdCl2/kg) Klimova and Mišòrova [65] have found no quantitative changes of histones extracted from the testes of rats with the exception of transient increase in the H1t subtype in H1 histone fraction. The finding of RabbaniChadegani et al. [77] is of interest. They have observed that in rat liver chromatin, in the presence of lead, the histone bands become weak and finally disappear at an increase of Pb concentration. These authors conclude that Pb affects chromatin structure attaching preferentially to histone proteins. Thiesen and Bach [78] consider that toxic metals ions either bind to the free thiol and other functional groups of the proteins or replace zinc and other essential metal ions in metal-dependent proteins. However, the molecular mechanism of leadchromatin interaction, especially the binding sites of histone proteins and the nature of cross links between the histone proteins themselves or histones and DNA remain unknown and need further investigation.

5. MATHEMATICAL MODEL FOR CAF TIME COURSE In our experiment with BALB/c mice, the Pb concentration in bones was 80 times higher than that of the bone Cd. It was already noted that Pb concentration in bone marrow is proportional to that in bones [79]. A confirmation of this finding is the establishment of Valverde et al. [80] that among the different analyzed organs of CD-1 mice, exposed to inhaled Pb, bone marrow and the brain have shown the highest DNA damage. Thus, we found grounds to assume that in our experiments, CA induction may be due predominantly to Pb toxic effect [42]. We considered CAF as a result from three main factors: 1) induction of DNA damage by the toxic agent; 2) biological self-regulation in the form of DNA repair; and 3) inhibition of DNA repair. The mathematical model of CAF kinetics we proposed was based on a simple model for Pb bioaccumulation in mouse bones.

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Three compartments of Pb movement were considered: gastrointestinal tract, blood, and bones. It may be assumed that Pb is distributed evenly into compartments, which allows the use of differential equation for its kinetics. After entering into the gastrointestinal tract, Pb moves to the blood and then to the bones. Thus, one can write the following system of ordinary differential equations:

dx = −b1 x dt

(1)

dy = b1 x − b2 y dt

(2)

dz = b2 y dt

(3)

under initial conditions:

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t0 = 0, x(t0) = x0 = B, y(t0) = 0, z(t0) = z0

(4)

where x, y, and z are the concentrations [mg/kg] of lead in gastrointestinal tract, blood, and bones, respectively; t is time [days]; t0 is the moment of the start of the experiment; b1 ([b1] = [day-1]) and b2 ([b2] = [day-1]) are rate constants of Pb accumulation in blood and bones, respectively; dx/dt, dy/dt, and dz/dt are the rates of change of Pb levels in the three compartments, respectively. We considered the change of CAF with the time as result of DNA damage induced by bone Pb and of DNA repair during the experiment. Thus, the following ordinary differential equation may be written for CAF kinetics:

dq = az (t ) − k (t ) q dt

(5)

under initial condition: t0 = 0, q(t0) = q0

(6)

where q is CAF (in percentages), dq/dt is the rate of change of CAF with time, z(t) is Pb concentration in bones during the experiment, a ([a] = [(mg/kg)-1day-1]) is a constant of induction of CA by Pb (induction constant), and k(t) ([k] = [day-1]) represents the rate of CA elimination. We considered q0 as the average level of the spontaneous CA recorded in the control group. The coefficient k(t) may be assumed as an integral characteristic of DNA repair (repair parameter). In fact, it is not constant. We supposed that k increases (at least during some time period) because the increase of CA activates DNA damage response

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pathway and thus accelerates DNA repair. We proposed the following ordinary differential equation for the parameter k(t):

dk = r − ck dt

(7)

under initial condition: t0 = 0,

k (t0) = k0

(8)

where r ([r] = [day-2]) is a genetically determined parameter characterizing repair potential (repair potential constant). Through the second term in the right side we take into account the third factor playing a role in CA accumulation, DNA repair inhibition, due to the toxicant. The constant c ([c] = [day-1]) may be considered as an inhibition constant. The modeling results were as follows. The analytical solution of equation (3) representing the bioaccumulation of Pb in bones under conditions (4) was

z (t ) = z 0 + B(1 −

b2 b1 e −b1t + e −b2t ) b2 − b1 b2 − b1

(9)

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This solution is represented in Figure 3. The experimentally determined values of bone Pb are displayed in the same figure. The constant B = x0 ([B] = [mg/kg]) is the concentration of the absorbed Pb in the mouse’s gastrointestinal mucosa during the experiment.

Figure 3. Change with time of the concentration of lead in bones of BALB/c mice during the ecotoxicological experiment (experimental points and model solution). The time point “0” corresponds to Pb concentration in the control group.

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M. Topashka-Ancheva and S. E. Teodorova The analytical solution of equation (7) was

r k (t ) = k 0 e −ct + (1 − e −ct ) c

(10)

Taking into account (9) and (10) the differential equation (5) can be written in the form:

b2 b1 dq r e −b1t + = az 0 + a[ B (1 − e −b2t )] − [k 0 e −ct + (1 − e −ct )]q (11) dt b2 − b1 b2 − b1 c Equation (11) cannot be solved analytically. Its numerical solution is displayed in Figure 4.

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The solutions (9) and (10), and the numerical solution of (11) were calculated as the initial conditions (4) and (6) were determined on the base of the experimental data: z0 = 7 mg/kg (lead concentration in bones of control mice), and q0 = 3.3% (the mean value of CAF in control females). Lead concentration in the food of the experimental animals was 784 mg/kg (Table 1). The daily food consumption per animal was about 6g. Thus, the entire ingested Pb quantity during the experiment might be L = 423 mg. According to data of Ershov and Pleteneva [2] the coefficient of gastrointestinal absorption of Pb is about 10%; i. e. η = 0.1. The absorption coefficient η is a dimensionless coefficient (0 ≤η ≤1). Therefore, the quantity of Pb available for entering in blood was B = ηL = 42.3 mg. Converted to concentration in mg/kg, taking into account that the mean mouse weight was 25 g, B = x(t0) = 1700 mg/kg. The parameters were fitted by minimization of χ2 by the use of an iterative Gauss-Newton procedure [81,82]. Thus the following values were obtained: b1 = 0.05 day-1, b2 = 0.08 day-1, a = 0.0057 (mg/kg)-1day-1, k0 = 0.027 day-1 r = 0.011 day-2, c = 0.0025 day-1.

Figure 4. Time course of the chromosomal aberration frequency (CAF) in the analyzed metaphases of bone marrow cells in the female BALB/c mice (experimental points and model solution). The time point “0” corresponds to CAF in the control group.

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The fate of the cell is finally determined by whether or not the various lesions inflicted on the genome are repaired or eliminated by apoptosis [79]. Cells bearing unstable aberrations such as dicentrics, rings, and chromosome fragments can be eliminated by apoptosis. Stable aberrations may have deleterious consequences for the organism since they are much less effective in causing apoptotic cell death [59]. In our case, unstable aberrations occurred infrequently and therefore, the apoptosis, as a regulating mechanism has not played a role. Thus, the parameter k(t), characterizing the elimination of CA can be considered as responsible only for repair. Of course, behind of the parameter k(t), presumed as an integral characteristic of DNA repair, lies a quite sophisticated complex of processes. The DNA damage response pathway is comprised of three general sets of factors, some with overlapping functions: sensors that recognize damaged DNA, transducers that amplify the damage signal, and effectors that induce a cellular response for repair [58]. The repair processes involve DNA polymerases and repair proteins. Nucleotide excision repair or base excision repair removes a variety of helix-distorting lesions caused by chemicals [83,84]. We assumed that the rate of elimination of CA (the rate of CAF decrease) is proportional to CAF level (the second term to the right side of equation (5)). This suggestion seems to be reasonable because an increase of CA involves more sensors, transducers and effectors of the DNA damage response pathway. The repair parameter k(t) is considered as depending on two parameters: r (an integral characteristics of the genetic repair potential) and c (an integral characteristics of DNA repair inhibition). The presence of CA is determined not only by induction of DNA damage but also by disturbance of DNA repair mechanisms. Hartwig [28] noted that for compounds of both Pb and Cd indirect genotoxic effects might be predominant at biologically relevant doses. He reported that an inhibition of DNA polymerize β as well as a decrease in the fidelity of DNA polymerization has been observed. Data of Karakaya et al. [85] suggest that Pb exposure may cause reduction in DNA repair capacity and that this could explain why Pb exposed workers were observed as more prone to DNA damage. Beyersmann and Hechtenberg [86] established an inhibition of DNA repairs process by Cd. Hartman and Hartwig [87] indicated that Cd blocks DNA repair disturbing protein interactions involved in DNA damage recognition. An inhibition of DNA repair and decrease of antioxidants following Cd exposure was reported by Waisberg et al. [88]. The animal age is another factor influencing DNA repair. An increasing failure of the DNA repair system with increasing age has been established by Walter et al. [89]. In our kinetic model the summary inhibition effect on DNA repair is represented by the inhibition constant c. The condition for steady state for the repair parameter k(t) (i. e. k = const and therefore, dk/dt = 0) follows from equation (7):

dk = 0 = r − ck dt Hence:

k=

r c

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(12)

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Taken into account the values of parameters r and c we obtained from (12) the asymptotic value of k(t) k = 4.4 day-1. From (10) we calculated for day 90: k (90) = 0.9 day-1. Therefore, it is clear that during the experiment k(t) is in its linear phase of change. In conditions of much higher concentrations of toxic metals or much more prolonged exposure the parameters r and c should probably not remain constant over time and k(t) would soon reach saturation at lower levels. But the resolution of this issue requires more complex consideration and further experiments. CAF level may depend not only on repair but also on to what extent DNA is susceptible to metal impact. Oxidative stress is known as a course of indirect DNA-metal interaction. Induction of lipid peroxidation and an increase in free radicals in mice exposed to Pb and Cd result in DNA injury [80] and it is clear that endogenous antioxidant levels may be a factor decreasing the organism’s susceptibility to genetic damages. Really, a positive influence of antioxidant levels in Pb intoxication was reported [61,90]. We could assume that in our model the induction constant a in equation (5) is a measure of the extent of susceptibility to DNA damage. Obviously the value of a will be lower in higher presence of endogenous antioxidants. Further experiments combining an exposure of animals to toxic metals and an antioxidant supplementation could help to find some relation between the antioxidant level and induction constant values. A more detailed quantitatively description of CAF dynamics requires a quite complicated kinetic model. The aim of this model was to indicate only the main tendencies of change in CAF on phenomenological level. The good agreement of the experimental data displaying the time course of CAF during the exposure with the model solution (Figure 4 ) suggests that the mathematical model here proposed, though simplified, well describes the balance between the CA bearing stimulated by the toxic agent, repair, and repair inhibition.

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6. CONCLUSION The effect of environmental pollution on structures and functions of the living organisms, including the integrity of hereditary apparatus, reproductive abilities etc., has been intensively studied. In this context during the past years, we investigated the effect of heavy metals from a polymetal industrial dust on the chromosomal structure and electrophoretic profile of nuclear proteins in small mammalian species (Guenther’s vole and white mice inbreed line BALB/c) in ecotoxicological experiments. Although the experiments were carried out using metal mixture but not metal compounds alone we could consider that the main genotoxic effect causing chromosome aberrations was exerted by Pb. Lead, a bone-seeking element, reached in our experiments a very high bone concentration. Lead concentration in bone marrow is proportional to that in bones. Lead is well known to damage the chromosomal structure in mammalian cells. The effect of Cd on chromosome DNA has been found only at high concentrations. The Cd concentrations in animal bones in our experiments were much less compared to those of Pb. Essential effects of copper and zinc could not be expected because of the low Cu concentration in bones and nonreported events of DNA damages by Zn. In contrast, it is quite reasonable to regard the observed toxic effect of heavy metal mixture on the nuclear proteins as dependent mainly on Cd concentration, which was significant in liver and kidney tissues of the experimental

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rodents. Changes in the non-histone and histone fraction of chromatin proteins may reflect the appearance of adaptive proteins and/or an early damage of the studied tissues. Taking into account that metaphase analysis provides information on the timing of DNA lesions relative to DNA replication, our observation on the distribution of the different types of structural chromosome aberrations allows concluding that Pb and Cd are mainly S-phasedependent clastogens. Intensive further investigations are needed to explain the detailed mechanisms of heavy metals action. Male and female BALB/c mice were explored separately. Significantly lower CAF levels were found in females compared to males and this could be explained assuming higher sensibility of male and a more effective DNA repair in female animals. The results obtained from the metaphase analysis in our experiments revealed a lack of correlation between the exposure duration and the total percentage of metaphases with chromosomal aberrations. This suggests a relative high resistance of chromosomal structure to anthropogenic pollutants such as heavy metals. The fact that the harvested aberrations did not increase incessantly with time in the rapidly proliferating bone marrow cell population could be due to a relative equilibrium between the processes of induction of aberrations by the mutagene (heavy metal) and DNA repair. Thus, our observations demonstrate that the chromosome apparatus responds quickly and at the same time, it remains relatively stable with good repair potential. There were no significant differences between CAF levels in both rodent species. Thus, our studies convincingly suggest that the species Guenther’s vole is also susceptible to genotoxic influences and along with BALB/c mice can be considered as a suitable model for monitoring of heavy metals impact on mammals. The experimental data regarding CAF time course support the rightness of our theoretical supposition that the rate of CA elimination is proportional to CA induction. The maximum value of CAF in females about day 40 (Figure 4) indicates a certain inertness in the defense reaction because of the travel of the DNA damage to the response pathway. However, after that the DNA repair managed to compensate and even diminish CAF. Though simplified, the mathematical model presents the basic trend in CAF development reflecting the balance of the processes of DNA damage, DNA repair, and DNA repair inhibition. The model allows determining some characteristic phenomenological parameters of CAF kinetics in the female BALB/c. Such a model could be used for the prediction of the kinetics of structural chromosomal changes in small mammals exposed to lead at different concentrations and in prolonged exposures. The present data concerning the clastogenic effects of heavy metals, especially lead and cadmium, on tissues of model mammalian species are valuable for the biological monitoring. The administration of heavy metals using a procedure of supplementation of the conventional animal food by industrial metal mixture affords to simulate toxicity, which might result from environmental pollution through contaminated food. The metal concentrations applied were enhanced compared to those occurring in the environment but this was chosen as means to assess the maximum hazard levels for the mammalian organism. Chromosome aberrations have been regarded as a very sensitive endpoint for detecting genotoxic effects induced by chemicals and hence such investigations can be considered as highly relevant in human context.

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[47] Kipling, D; Wilson, HE; Mitchell, AR; Teylor, BA; Cooke, HJ (1994) Mouse centromeric mapping using oligonucleotide probe that detect variants of the minor satellite. Chromosoma, 103, 46-55. [48] Demarque, D; Jouanny, J; Poitevin, B; Saint Jean, Y (1995) Pharmacologie et Matiere Medicale Homeopathique. France: Boiron- C.E.D.H. [49] O’Flaherty, E (1993) Physiologically based models for bone-seeking elements. IV. Kinetics of lead disposition in humans. Toxicol. Appl. Pharmacol. 118, 16-29. [50] Ieradi, LA; Cristaldi, M; Mascanzoni, D; Cardarelli, E; Grossi, R; Campanella, L (1996). Genetic damage in urban mice exposed to traffic pollution. Environ. Pollut. 92, 323-328. [51] Scheirs, J; De Coen, A; Covaci, A; Beernaert, J; Kayawe, VM; Caturla, M; De Wolf, H; Baert, P; Van Oostveldt, P; Verhagen, R; Blust, R; De Coen, W (2006) Genotoxicity in wood mice (Apodemus sylvaticus) along a polluted gradient: exposure- age-, and gender-related effects. Environ. Toxicol. Chem. 25 (8), 2154-2162. [52] Agarval, K; Sharma, A; Talukder, G. (1990) Clastogenetic effects of copper sulphate on the bone marrow chromosomes of mice in vivo. Mutation Res. 243, 1 - 6. [53] Botev, B. and Topashka-Ancheva, M. (2008) Tumors as a General Biological Problem. Sofia-Moscow: Pensoft. (In Bulgarian). [54] Dubinin, NP (1986). General Genetics. Moscow: Naouka Publ. House. (In Russian). [55] Sorsa, M; Wilbourn, J; Vainio, H (1992) Human cytogenetic damage as a predictor of cancer risk. In: Vainio H, Magee PH, McGregor DB, McMichael AJ editors. Mechanisms of Carcinogenesis in Risk Identification (pp. 543-554). Lyons and International Agency for Research on Cancer. [56] Albertini, RJ; Anderson, D; Douglas, GR; Hagmar, L; Hemmimki, K; Merlo, F; Natarajan, AT; Norppa, H; Shuker, DE; Tice, R; Waters, MD; Aitio, A (2000). IPCS guidelines for the monitoring of genotoxic effects of carcinogens in humans. International Programme on Chemical Safety. Mutation Res. 463, 111-172. [57] Hagmar, L; Stromberg, U; Bonassi, S; Hansteen, I-L; Knudsen, LE; Lindholm, C; Norppa, H (2004). Impact of types of lymphocyte chromosomal aberrations on human cancer risk: results from Nordic and Italian cohorts. Cancer Res. 64, 2258-2263. [58] Franco, S; Alt, FW; Manis, JP (2006) Pathways that suppress programmed DNA breaks from progressing to chromosomal breaks and translocations. DNA Repair 5, 1030-1041. [59] Mateuca, R; Lombaert, N; Aka, PV; Decordier, I; Kirsch-Volders, M (2006) Chromosomal changes: induction, detection methods and applicability in human monitoring. Biochimie 88, 1515-1531. [60] Privezentsev, KV; Sirota, NP; Gaziev AJ (1996). The genotoxic of cadmium studied in vivo. Tsitologia i genetika 30 (3), 45-51. [61] Valverde, M; Fortoul, TI; Diaz-Barriga, F; Mejia, J; del Castillo, ER (2002) Genotoxicity induced in CD-1 mice by inhaled lead: differential organ response. Mutagenesis 17 (1), 55-61. [62] Shaik, AP; Sankar, S; Ready, SC; Das, PG; Jamil, K (2006). Lead-induced genotoxicity in lymphocytes from peripheral blood samples of humans: in vitro studies. Drug and Chemical Toxicology 29 (1), 111-124. [63] Pfeiffer, P; Goedecke, W; Obe, G (2000). Mechanisms of DNA double-strand repair and their potential to induce chromosomal aberrations. Mutagenesis 15, 289-302.

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[64] Fraisio da Silva, J. J. R. and Williams, R. J. P. (1993) The Biological Chemistry of the Elements: the Inorganic Chemistry of Life. Oxford: Clarendon Press. [65] Klimova, Š. and Mišòrova, E. (2004) Effects of cadmium and ionizing radiation on histones in rat testes. Acta Vet. Brno 73, 483-489. [66] Popenoe, E. A. and Schmaeler, M. A. (1979) Interaction of human DNA polymerize beta with ions of copper, lead, and cadmium. Arch. Biochem. Biophys. 196 (1), 109120. [67] Borochov, N; Ausio, J; Eisenberg, H (1984) Interaction and conformational changes of chromatin with divalent ions. Nucl. Acids Res. 12, 3089-3096. [68] Goering, PL (1993) Lead–protein interactions as a basis for lead toxicity. Neurotoxicology 14, 45–60. [69] Quintanilla-Vega, B; Hoover, D; Bal, W; Silbergeld, EK; Waalkes, MP; Anderson, LD (2000) Lead effects on protamine-DNA binding. Am. J. Ind. Med. 38, 324–329. [70] Bradbury, EM (2004) Chromatin structure and dynamics: State of the Art. Molecular cell 10 (1), 13-19. [71] Stein, G; Hunter, G; Lavie, L (1974) Non-histone chromosomal proteins. Evidence for their role in mediating the binding of histones to deoxyribonucleic acid during the cell cycle. Biochem. J. 139 (1), 71–76. [72] Stein, GS; Stein, JL; Kleinsmith, L (1975) Chromosomal proteins and gene regulation. J. Scient. Am. 4, 47–57. [73] Djondjurov, L; Ivanova, E; Tsanev, R (1979) Two chromatin fractions with different metabolic properties of non-histone proteins and of newly synthesized RNA. Eur. J. Biochem. 97(1), 133-139. [74] Laemmli, UK (1970) Cleavage of structural proteins during the assembly of the head of bacteriophage T4. Nature 227, 680-685. [75] Angelova, A; Stambolova, M; Tsanev, R (1984) Distribution and metabolic behaviour of "tightly bound" acid-soluble non-histone chromosomal proteins in developing rat brain cells. Int. J. Biochem. 16 (7), 763-771. [76] Klaasen CD (1980) Heavy metals and heavy metal antagonists. In: Glimman AY, editor. The Pharmacological Basis of Therapeutics (pp. 1615-1637). New York. [77] Rabbani-Chadegani, A; Abdosamadi, S; Fani, N; Mohammadian, S ( 2009) A comparison of the effect of lead nitrate on rat liver chromatin, DNA and histone proteins in solution. Arch. Toxicol. 83 (6), 565-570. [78] Thiesen, H. J. and Bach, C. (1991) Transition metals modulate DNA–protein interactions of SP1 zinc Wnger domains with its cognate target site. Biochem. Biophys. Res. Commun. 176, 551–557. [79] Decordier, I; Dillen, L; Cundari, M; Kirsch-Volders, M (2002) Elimination of micronucleated cells by apoptosis after treatment with inhibitors of microtubules. Mutagenesis 17, 337-344. [80] Valverde, M; Trejo, C; Rojas, E (2005) Is the capacity of lead acetate and cadmium chloride to induce genotoxic damage due to direct DNA-metal interaction? Toxicology and Industrial Health 21 (10), 243-248. [81] Alexandrov, L (1971) Regularized computerizing processes of Newton-Kantarovich type. JVM i MF 2 (1), 31-41. (In Russian). [82] Alexandrov, L; Drenska, M; Karadjov, D (1984) Program System REGN for solution of nonlinear system of equations PRS-165/REGN RSIC. Tennesee: Ooak Ridge.

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[83] Wood, RD (1996) DNA repair in eukaryotes. Annual Rev. Biochem. 65, 135-167. [84] Lindahl, T. and Wood, R. D. (1999) Quality control by DNA repair. Science 286, 18971905. [85] Karakaya, AE; Ozcagli, E; Ertas, N; Sardas, S (2005). Assessment of abnormal DNA repair responses and genotoxic effects in lead exposed workers. Am. J. Ind. Med. 47 (4), 358-363. [86] Beyersmann, D. and Hechtenberg, S. (1997) Cadmium, gene regulatory and cellular signaling in mammalian cells. Toxicol. Appl. Pharmacol. 144, 247-261. [87] Hartman, M. and Hartwig, A. (1998) Disturbance of DNA damage recognition after UV-radiation by nickel(II) and cadmium(II) in mammalian cells. Carcinogenesis 19, 617-621. [88] Waisberg, M; Joseph, P; Hale, B; Beyersmann, D (2003) Molecular and cellular mechanisms of cadmium carcinogenesis. Toxicology 192, 95-117. [89] Walter, CA; Intano, GW; McCarrey, JR; McMahan, CA; Walter, RB (1998) Mutation frequency declines during spermatogenesis in young mice but increases in old mice. Proc. Nat. Acad. Sci. USA 95, 10015-10019. [90] Gochfeld, M (1997) Factors influencing susceptibility to metals. Environ. Health Perspect. 105 (suppl. 4), 817-822.

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In: Impact, Monitoring and Management… Editors : Ahmed El Nemr

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Chapter 8

MARINE POLLUTION IN WATER, SEDIMENT AND BIOTA Qing Xu, Hongyan Xi and Yuanzhi Zhang1 Institute of Space and Earth Information Science, The Chinese University of Hong Kong, Shatin, NT, Hong Kong, China

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ABSTRACT Usually, marine pollution is the harmful effect caused by the entry into the ocean of chemicals or particles. A possibly related issue is that many potentially toxic chemicals adhere to tiny particles which are then taken up by plankton and benthos animals. Most of them are either deposit or filter feeders, concentrating upward within ocean food-chains. In addition, since most animal feeds contain high fish meal and fish oil content, toxins could be found a few weeks later in commonly consumed food items derived from livestock and animal husbandry. As rivers are the common entrance of contaminants to the marine environment, many particles combine chemically in a manner highly depletive of oxygen, leading to estuaries to become anoxic.

1. WHAT IS MARINE POLLUTION? Humans began polluting the Earth’s seas the first time we threw wastes into the sea like fruit peels, half-gnawed bones etc., but at that early time there was no obvious effect to the sea. The impact of human activity on the balance of the oceans began with the rise of agriculture and industry during the earliest civilizations. After settled communities replaced nomadic tribes, more human and animal waste was found concentrated in the nearest body of water, either as runoff or as sewage. Undoubtedly, along these waters discharged into coastal waters and oceans, nutrient levels in the sea increased and initially improved the plankton productivity. In addition, humans also poured sufficient sewage into the sea to increase fishery production. However, when there were no obvious negative consequences happening, so no one considered this to be “pollution” [1]. 1 Email: [email protected].

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Until 1967, the term “marine pollution” had only been used when the tanker Torrey Canyon wrecked and spilled more than 36 million gallons of crude oil just 20 miles off the western coast of Cornwall, England, which caused an environmental disaster. The United nations Joint Group of Experts on the Scientific Aspects of Marine Pollution (GESAMP) defined marine pollution in 1972 as “the introduction by man, directly or indirectly, of substances or energy to the marine environment resulting in deleterious effects such as: hazards to human health; hindrance of marine activities, including fishing; impairment of the quality for the use of seawater, and reduction of amenities.” Wastes from human activities entering the sea include degradable wastes (rapidly diluted to a harmless level), conservative wastes (metals and halogenated hydrocarbons not subject to a bacterial attack, and therefore essentially permanent additions to the sea), and solid wastes (plastics, dredging spoil, mine tailings, etc.) [2]. However, most inputs are not as simple in their constitution, but quite complex due to their various sources. Usually, similar complexities exist in particular geographical sites. Industrialized estuaries often have a multiplicity of inputs from the surrounding industries as well as from the urban populations. As far as the sources of input are concerned, they can be categorized into several aspects, as follows [2]:

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A. Direct Outfalls Estuaries, coastal towns, coastal industry are the main sources of direct discharged waste. Historically, most ports grew up on estuaries; they became centers of population and industries. Before humans realized marine pollution was an issue and the severe consequences it brought, the urban and wastes were let out directly into the estuaries without any treatment. On the other hand, coastal industries were developed with demands for more interest and sufficient supplies, such as mariculture installations, which were responsible for part of the direct input of unconsumed food and pesticides to inshore waters.

B. River Inputs Obviously, rivers flow via estuaries into the sea, carrying potential pollutants from the entire catchment area. All land wastes, like organic wastes, pesticides, fertilizers and oils washed off by rainfall, or directly discharged, enter rivers and streams, then flow into the sea.

C. Shipping Usually, ships carry many toxic substances: industrial chemicals, liquid gases, oil and so on. If accidents like shipwrecks happen at sea, these substances will be released into the water. The larger the vessel capability, the worse damage the accident will result in. A wreck of large tankers can induce a severe tragedy to both human lives and the marine environment.

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D. Offshore Inputs Much waste is dumped at sea by humans to reduce the pressure of the environment on the land or inshore area. These wastes always have a high organic content and are also contaminated with heavy metals, oils and other substances; sewage sludge is one example. Offshore industrial activities also result in kinds of inputs in to sea, including mining, oil exploration and extraction, sand and gravel extraction, and so on.

E. Atmospheric Inputs

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Particulates in nature, dusts in the air returned to the land or the sea by rainfall; some of the atmospheric deposition on land is carried to the sea via rivers. Ocean-atmospheric interaction can dissolve some gaseous wastes near the surface. Many unknown factors for atmospheric inputs to the sea exist and need to be estimated, but their contributions to the pollution can not be ignored.

Figure 1. Wastes reach the marine environment from a large variety of sources, including but not restricted to the following. 1. Oil spills; 2. Lost or dumped munitions; 3. Garbage and waste from ships; 4. Dumped nuclear and industrial waste; 5. Lost or dumped vessels, their cargoes and power plants; 6. Oiled drill cuttings; 7. Washout of atmospheric pollutants including heavy metals and hydrocarbons; 8. Industrial wastes; 9. Urban wastes and street drainage; 10. Sewage effluent; 11. Traffic exhaust(via the atmosphere); 12. Agricultural fertilizers and pesticides; 13. Cooling water (waste heat) (Credit: Clark, 2001 [2]).

Some of the inputs mentioned above are man-made, but most of the substances exist naturally in the sea, such as oil from natural seepage, particulate from erosion, organic material forming bacterial degradation, and so on. Whether these natural inputs which may be

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more polluting should be referred to as “pollution” still remains a question. However, the marine pollutants brought by these substances have been divided into several large categories: sewage, marine debris, toxic chemicals, heavy metals, oil, and radioactive materials. Figure 1 gives a general concept of the waste inputs.

2. MARINE POLLUTANTS 2.1. Sewage

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Sewage is human waste. It is organic and biodegradable, meaning it comes from living organisms and is decomposes by bacteria. Besides, wastes from animal excretions and plant matter rot where they land, and reach the sea as runoff following rains. Sewage is the mainly liquid waste which contains some solids produced by humans. It is one type of waste water, which typically consists of washing water, faeces, urine, laundry waste and other material that goes down drains and toilets from households and industry. Sewage can be discharged into the ocean intentionally or unintentionally. Pipes often carry it to a river or directly into the sea, while in an unintentional way it often happens when the capacity of a sewage system is overloaded and exceeded during heavy rainfalls. Once this occurs, sewage can enter the water without any treatment [3].

A. How Does Sewage Pollute? Sewage can decompose so that it has a relatively short lifespan. Microscopic organisms like bacteria and fungi satisfy their needs for energy by consuming dead organic substances, a process called biodegradation. However, these microorganisms consume oxygen in their respiration process. If the biological oxygen demand (BOD) is low, meaning there is too little oxygen in the water to sustain these biodegraders, they will die and so do all the plankton that depend on them. This process is called eutrophication [1]. Eutrophication is an increase in chemical nutrients -- typically compounds containing nitrogen or phosphorus -- in an ecosystem. It may occur on land or in water. The term is often used to mean the resultant increase in the ecosystem's primary productivity (excessive plant growth and decay), and further effects including lack of oxygen and severe reductions in water quality, fish, and other animal populations. Once the nutrient-rich sewage enters the sea, a series of consequences happen, such as extreme overgrowth of phytoplankton, dead zooplankton, water discoloration etc., which are all related to an event called red tide. Red tide usually happens in estuary, marine, or fresh water. Some red tides are associated with the production of natural toxins, depletion of dissolved oxygen or other harmful impacts, and are generally described as harmful algal blooms (HABs). The most conspicuous effects of red tides are the associated wildlife mortalities among marine and coastal species of fish, birds, marine mammals and other organisms. Moreover, in industrialized regions, sewage that reaches the sea usually contains industrial waste, including heavy metals and toxic chemicals. For example, agricultural runoff which reaches the sea usually contains toxic pesticides. These inorganic matters will mix with organic wastes in sewage which often results in more severe damage to the sea.

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B. Sewage Services Sewage services exist to manage sewage through the collection, treatment and recycling of safe disposal into the environment. A system of sewer pipes (sewers) collects sewage and takes it for treatment or disposal. The system of sewers is called sewerage, sewerage system, or a sewage system. In places where a main sewage system has not been provided, sewage may be collected from homes by pipes into septic tanks or cesspits. There, it may be treated or collected in vehicles and taken for treatment or disposal [3]. Sewage treatment is a form of waste management which removes the contaminants from sewage to produce liquid and solid (sludge) suitable for discharge to the environment or for reuse [3]. A septic tank or other on-site wastewater treatment system such as biofilters can be used to treat sewage close to where it is created. In developed countries sewage collection and treatment is typically subject to local, state and federal regulations and standards. Much of the world’s sewage is piped directly into the sea without any treatment. Once sewage enters the ocean there is no way to remove or clean up it. The damage is done and the eco-balance of that area is no longer the same [1]. Thus, great measures have to be taken on how to monitor and deal with sewage efficiently.

2.2 Marine Debris

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Marine debris are the materials, such as plastic, glass, and metal, that decompose extremely slowly or do not decompose at all. It is also known as marine plastic litter, which refers to human-created waste that has found itself floating in a lake, sea, ocean or waterway and is particularly hazardous. Unlike metal and glass, oceanic debris floats on the water surface. It also tends to accumulate at the centre of gyres and coastlines frequently washing aground where it is known as beach litter [4].

A. Types of Marine Debris Some forms of marine debris such as harmless driftwood occur naturally. Although human activities have been adding similar material into the oceans for thousands of years, only recently, with the advent of plastic, has our influence become an issue because many types of plastic marine debris do not biodegrade [5]. The seabed is littered with undetonated bombs, abandoned offshore oil rigs, outdated rocket engines, drums of toxic chemicals and radioactive waste, sunken ships, automobiles, pop cans, soda bottles, pieces of wood, and other items. Waterborne plastic is both unsightly and dangerous. It poses a serious threat to navigation, fishing nets, boats, coastal habitations, as well as to seabirds, fish, marine reptiles, and marine mammals. Ocean dumping, accidental container spillages and wind-blown landfill waste are all contributing to this growing problem. Actually, plastics have only existed for less than 150 years. They were developed during the 1860s. After that, a wide variety of plastics and plastic products welled up for all sorts of reasons. There are two main types of plastic debris found in the ocean; one is plastic resin pellets and the other manufactured products. Plastic resin pellets are “raw” plastic that can be melted down and molded into many types of manufactured goods. Once they are poured into the ocean accidentally, they are easily blown away by the wind because of their light weight.

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Manufactured plastic products that become marine debris include fishing gear, shipping and packaging materials and household plastics. Due to the stable physical and chemical property of the plastics, it will usually take as long as 500 years for many of them to decompose. The long durability and high strength of plastics make them a persistent pollution problem [1]. But how does the marine debris enter the sea?

B. Source of Debris Originally, it was thought that oceanic waste stemmed directly from ocean dumping or indirectly via run-off from rivers and streams; but now it is thought that the majority comes from rubbish blown seaward from landfills. There are several ways through which marine debris can enter the sea. They are intentional dumping from ships, as part of sewage, from polluted rivers and streams, in runoff from beaches littered with trash, being swept from land by wind or storms, accidental discharge from ships or garbage barges on their way to offshore landfills, and so on.

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C. Environmental Impacts Plastic marine debris often floats, which makes it hazardous to animals that live on or in the sea. Since it looks similar to natural prey of these animals, once it is eaten by mistake, plastic debris, when bulky or tangled, is difficult to pass, and may become permanently lodged in the digestive tracts of these animals, blocking the passage of food and causing death through starvation or infection [6]. Tiny floating particles also resemble zooplankton, which can lead filter feeders to consume them and cause them to enter the ocean food chain. More recently, reports have shown that there may now be, by weight, 30 times more plastic than plankton in the North Pacific “garbage patch,” the most abundant form of life in the ocean [7]. Marine debris also interferes with navigation, beaches and coastal waters, which makes the coastal scenes unsightly.

Figure 2. This turtle was trapped in a ghost net, an abandoned fishing net. Sea turtles breathe at the surface, so if they get entangled and cannot escape, they will drown (Source of the image: http://www.noaanews.noaa.gov/stories2005/s2429.htm).

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Many toxins can be found in plastic materials. One of the most harmful among them is polychlorinated biphenyl (PCB), which can leach into the surrounding waters. Though safety standards are increasing (PCBs were banned in the 1970s), all the plastics produced in the years prior are still circulating in the world's oceans. Moreover, Ghost nets, which are fishing nets that have been left or lost in the ocean by fishermen, can also entangle and kill fish, dolphins, sea turtles (Figure 2), sharks, dugongs, crocodiles, penguins and various seabirds, crabs and other creatures, including the occasional human diver [8]. However, not all marine debris in the ocean does harm. Those which sink such as iron, concrete and the like, do little damage to the environment as they are immobile and inert. Actually, they can even attract fish and can be used to build artificial reefs, and thus increase the biodiversity of a coastal region.

D. Monitoring and Studies on Marine Debris Researches on monitoring and resolving marine debris issue have been developed in recent decades on the international coverage. The National Oceanic and Atmospheric Administration (NOAA) Marine Debris Program (MDP) is such a representative. The NOAA MDP was launched in 2005 after the NOAA National Ocean Service's Office of Response and Restoration received a budget line titled “Marine Debris” for $5 million. On December 22, 2006, the Marine Debris Research, Prevention, and Reduction Act was signed into law, which legally established the NOAA Marine Debris Program. To date, the program serves as a centralized marine debris capability within NOAA in order to coordinate, strengthen, and increase the visibility of marine debris issues and efforts within the agency, its partners, and the public. This Program is undertaking a national and international effort focusing on identifying, reducing, and preventing debris in the marine environment [9].

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2.3. Toxic Chemicals Thousands of chemical compounds are developed for various purposes by human beings. We use them to kill insects, remove dirt, dissolve paint and do a lot of other important things. Unfortunately, most of these chemicals are toxic and harmful to humans, animals and plants. The most harmful chemicals are PCBs, Dichloro-Diphenyl-Trichloroethane (DDTs) and dioxins. DDT is the most harmful insecticide, while PCBs and dioxins are primarily byproducts of manufacturing processes. All of them are part of family of toxins known as chlorinated hydrocarbons, kinds of industrial and agricultural chemicals that do not break down easily in the environment [1]. PCBs are chlorinated hydrocarbons with the chemical formula C12H10-xClx.. They were used as coolants and insulating fluids for transformers and capacitors, pesticide extenders, cutting oils, adhesives, wood floor finishes, paints, de-dusting agents, and in carbonless copy paper [10]. PCBs are classified as persistent organic pollutants which bio-accumulate in animals. In the 1970s, PCB production was banned due to the high toxicity of most PCB congeners and mixtures. DDT is one of the best known synthetic pesticides. It has a long, unique, and controversial history. First synthesized in 1874, DDT’s insecticidal properties were not discovered until 1939. In the early years of World War II, DDT was used with great effect to control mosquitoes spreading malaria, typhus, and other insect-borne diseases among both

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military and civilian populations. After the war, DDT was made available for use as an agricultural insecticide, and soon its production and use expanded [11]. Dioxins contain a large amount of chlorinated aromatic hydrocarbons that are all toxic. Dioxin is a general term that describes a group of hundreds of chemicals that are highly persistent in the environment. The most toxic compound is 2,3,7,8-Tetrachlorodibenzo- pDioxin (TCDD). The toxicity of other dioxins and chemicals like PCBs that act like dioxin are measured in relation to TCDD. Dioxin is formed as an unintentional by-product of many industrial processes involving chlorine such as waste incineration, chemical and pesticide manufacturing and pulp and paper bleaching. High levels of dioxins usually can be found downstream of almost every paper mill in the world.

A. How Do Toxic Chemicals Enter the Ocean? All kinds of chemicals, including toxic ones, enter the ocean in numerous ways. Due to the chemical stability of PCBs, they are widely used in the industrial fields. They enter the environment via paint, plastic, adhesive and manufacturing processes, then their compounds can be found in the rivers or streams as industrial waste, which make their way to the ocean. PCBs are more persistent than many other chemical residues. This means they can remain in the ecosystem for at least 500 years after entering the ocean. Since DDT is usually used to kill insect pests as an exterminator, it can enter the ocean via rivers and agriculture runoffs. However, more DDT is taken up by the wind during the aerial spraying of crops and forests. Thus, it will be in the atmosphere and enter the sea with precipitation. As far as the dioxins are concerned, most of them in the ocean environment come from untreated waste water that was discharged by paper mills into rivers and streams. Dioxins also enter the sea via the atmosphere, intentional dumping and so forth. Moreover, marine incineration is another way that all these chlorinated hydrocarbons and other toxic chemicals enter the ocean [1]. Chemicals also enter the sea from land-based activities. They can escape into water, soil, and air during their manufacture, use, or disposal, as well as from accidental leaks or fires in products containing these chemicals. Once in the environment, they can travel for long distances in air and water, including in ocean currents. B. Impacts on Living Organisms Almost every marine organism, from the tiniest plankton to whales and polar bears, is contaminated with man-made chemicals. These chemicals (toxic or non-toxic) are first absorbed by phytoplankton, zooplankton and other microorganisms that live in the surface waters after they enter the sea, which can prevent these organisms from developing, and decrease the entire plankton population. Tiny animals at the bottom of the food chain absorb the chemicals as they feed. Because they do not break down easily, the chemicals accumulate in these organisms, becoming much more concentrated in their bodies than in the surrounding water or soil. These organisms are eaten by small animals, and the concentration rises again. These small animals are in turn eaten by larger animals, which can travel large distances with their even further increased chemical load. This process is called “bioaccumulation.” Animals higher up the food chain, such as seals, can have contamination levels millions of times higher than the water in which they live. And polar bears, which feed on seals, can have contamination levels up to 3 billion times higher than their environment. People become contaminated either directly from household products or by eating contaminated seafood and animal fats.

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People once assumed that the ocean was so large that all pollutants would be diluted and dispersed to safe levels. But in reality, they have not disappeared - and some toxic man-made chemicals have even become more concentrated as they have entered the food chain. Evidence is mounting that a number of man-made chemicals can cause serious health problems - including cancer, damage to the immune system, behavioral problems, and reduced fertility.

C. Human Reactions on Toxic Chemicals and Solutions For centuries, the oceans have been a convenient dumping ground for waste generated on land. This continued until the 1970s, with dumping into sea the accepted practice for disposal of nearly everything, including toxic material such as pesticides, chemical weapons, and radioactive waste. Dumping of the most toxic materials was banned by the London Dumping Convention in 1972, and an amended treaty in 1996 (the London Convention) further restricted what could be dumped at sea. However, there are still the problems of alreadydumped toxic materials, and even the disposal of permitted substances at sea can be a substantial environmental hazard. In 1962, a book named “Silent Spring” [12] catalogued the environmental impacts of the indiscriminate spraying of DDT in the US and questioned the logic of releasing large amounts of chemicals into the environment without fully understanding their effects on ecology or human health. The book suggested that DDT and other pesticides may cause cancer and that their agricultural use was a threat to wildlife, particularly birds. Its publication was one of the signature events in the birth of the environmental movement. “Silent Spring” resulted in a large public outcry that eventually led to most uses of DDT being banned in the US in 1972 [13]. DDT was subsequently banned for agricultural use worldwide under the Stockholm Convention, but its limited use in disease vector control continues to this day in certain parts of the world and remains controversial. However, concerning toxins that already exist in the ocean, currently there are not very much effective ways to clear away the persistent chemical toxins in the marine environment. Also, industrial processes that can generate these toxic chemicals are far more difficult to alter or stop from producing these harmful byproducts. Nevertheless, lowering the demand for the products related to them, or establishing and installing some efficient equipments for containment and treatment of all contaminated wastewater, can certainly help reduce the toxic chemical pollution.

2.4. Heavy Metals By today’s definition, heavy metals are not just dense elements. A heavy metal is a member of an ill-defined subset of elements that exhibit metallic properties, which would mainly include the transition metals, some metalloids, lanthanides, and actinides. Many different definitions have been proposed, some based on density, some on atomic number or atomic weight, and some on chemical properties or toxicity [14]. The term heavy metal has been called “meaningless and misleading” in an International Union of Pure and Applied Chemistry (IUPAC) technical report due to the contradictory definitions and its lack of a “coherent scientific basis.” As discussed below, depending on context, heavy metals can include elements lighter than carbon and can exclude some of the heaviest metals. One

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dictionary defines heavy metal as “common transition metals, such as copper, lead, and zinc. These metals are a cause of environmental pollution (heavy-metal pollution) from a number of sources, including lead in petrol, industrial effluents, and leaching of metal ions from the soil into lakes and rivers by acid rain” [15]. Actually, many heavy metals are essential for life, but only extremely small quantities are needed. Anything over this small amount can be very toxic. Nowadays, heavy metals in industrial waste have enlarged the normal original contents that the ocean has, which leads to unnaturally high levels of these toxic metals and their compounds in sea water. Living marine organisms are suffering from serious illness caused by the toxic heavy metals. Heavy metal pollution can arise from many sources but most commonly arises from the purification of metals, e.g., the smelting of ores and the preparation of nuclear fuels. Electroplating is the primary source of chromium and cadmium. Through precipitation of their compounds or by ion exchange into soils and muds, heavy metal pollutants can localize and lay dormant. Unlike organic pollutants, heavy metals do not decay and thus pose a different kind of challenge for remediation [16].

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A. How Do Heavy Metals Enter the Ocean? There are two sources of marine heavy metals. The first one is the natural origin. A large amount of heavy metals from the earth crust weathering, seabed volcano eruption and land water discharge enter the ocean directly or via rivers, streams and atmosphere. In this way, they make up the natural amount of marine heavy metals. Human activity is now the other main source of heavy metal pollution in the ocean. Heavy metals can be from industrial waste or mine waste water discharge, and loss of heavy metal pesticide. Heavy metals can also be released into the atmosphere from coal or oil burning, and then transported to the ocean by wind and precipitation. According to the gross estimation, more than 3,000 tons of mercury released from mineral burning enters the sea every year in the world. Besides, scoria and mineral slurry that contain mercury also can transport the mercury to the ocean. Therefore, every year about 10,000 tons of mercury produced by human activity enters the ocean all over the world, which is equivalent to the total year output of mercury in the world. Moreover, lead concentration in the atmosphere has been increasing sharply year by year since 1924. Atmospheric transportation of heavy metals is one of the main ways to pollute the ocean though it is hard to measure the amount. But the total amount of lead, zinc, cadmium, mercury and selenium that are transported to the ocean via aerosols is much more than that of from land transportation. Airborne particles of heavy metals compounds settle in the ocean via precipitation and they contribute to the high levels of heavy metals found in the coastal waters of industrial areas. Additionally, some metals are dumped into the sea intentionally, for example, nerve gas rockets and copper sulfate were dumped into the ocean after World War II.

B. Impacts on Living Organisms Living organisms require various amounts of heavy metals such as iron, cobalt, copper, manganese, molybdenum and zinc; but excessive levels can be detrimental to the organism. Other heavy metals such as mercury, plutonium, and lead are toxic metals that have no known vital or beneficial effect on organisms, and their accumulation over time in the bodies of living organisms can cause serious illness. For certain organisms or under certain conditions, certain elements that are normally toxic are beneficial. Examples include vanadium, tungsten,

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and even cadmium [17]. The impacts of some typical heavy metals on living organisms, lead, mercury, cadmium and copper, are listed as follows. Lead: Although lead may initially disperse when it enters the ocean, marine organisms easily concentrate it. This bioaccumulation can end up making fish toxic for human consumption. It will be very harmful once lead enters the food chain. It is a poisonous metal that can damage nervous connections (especially in young children) and cause blood and brain disorders. Long term exposure to lead or its salts can cause nephropathy, and colic-like abdominal pains. High blood levels are associated with delayed puberty in girls [18] Symptoms of lead poisoning also include learning abilities, mental retardation and so on. Mercury: Mercury occurs in deposits throughout the world and is harmless in an insoluble form, such as mercuric sulfide. However, it is poisonous in soluble forms. Mercury poisoning (also known as mercurialism, hydrargyria, Hunter-Russell syndrome, or acrodynia when affecting children) is a disease caused by exposure to mercury or its toxic compounds. Mercury is a cumulative heavy metal poison which occurs in its elemental form, inorganically as salts, or organically as organomercury compounds. The three groups vary in effects due to differences in their absorption and metabolism, among other factors [19]. However, with sufficient exposure all mercury-based toxic compounds damage the central nervous system and other organs or organ systems such as the liver or gastrointestinal tract. Symptoms typically include sensory impairment (vision, hearing, speech), disturbed sensation and a lack of coordination. The type and degree of symptoms exhibited depend upon the individual toxin, the dose, and the method and duration of exposure. A well documented environmental disaster associated with heavy metals is the Minamata disease caused by mercury pollution. Due to its toxicity, there have been campaigns in many countries to ban mercury altogether. Cadmium: Cadmium has no constructive purpose in the human body. It and its compounds are extremely toxic even in low concentrations, and will bioaccumulate in organisms and ecosystems. In humans, cadmium gravitates first to the liver and kidneys but eventually ends up replacing calcium (to which it is chemically similar) in bones. Severe cases of cadmium poisoning, called Itai-itai, make the bones of some victims so brittle that mere coughing can cause fractures. Cadmium can also cause high blood pressure. Copper: As one of the first metals ever mined, copper is also an essential trace element required for the survival of plants and animals. But in large doses, copper is highly toxic. Chronic copper depletion leads to abnormalities in metabolism of fats, high triglycerides, fatty or cirrhosis liver, stunted growth, and poor melanin etc..

C. Monitoring and Cleaning Up of Heavy Metals Now it is possible to measure the amounts of most of these metals in the sea. This work has been performed in many countries and regions all over the world, while in some other parts of the world, no regular measurements have been taken. Many agencies keep track of heavy metal levels in fishing areas and in waters used for recreation. In some cases they are still ignored and heavy metal measurements are not taken until people get sick or local citizens complain. Totally cleaning up the extra levels of heavy metals that have been contributed, by human activities, into the ocean still remains an unsolvable issue unless we realize what level of each heavy metal is safe for marine life and human beings. However, many laws and regulations have been executed to decrease or ban the utilization of those products which let off compounds of harmful metals.

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2.5. Oil

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The “oil” we mentioned here is actually petroleum which is a naturally occurring, flammable liquid found in rock formations in the Earth consisting of a complex mixture of hydrocarbons of various molecular weights, plus other organic compounds. The proportion of hydrocarbons in the mixture is highly variable and ranges from as much as 97% by weight in the lighter oils to as little as 50% in the heavier oils and bitumens. Most geologists view crude oil and natural gas as the product of compression and heating of ancient organic materials over geological time. Oil is formed from the preserved remains of prehistoric zooplankton and algae which have been settled to the sea (or lake) bottom in large quantities under anoxic conditions. Crude oil varies greatly in appearance depending on its composition. It is usually black or dark brown (although it may be yellowish or even greenish). Petroleum is used mostly, by volume, for producing fuel oil and gasoline (petrol), both of which are important "primary energy" sources. By volume, 84% of the hydrocarbons present in petroleum is converted into energy-rich fuels (petroleum-based fuels), including gasoline, diesel, jet, heating, other fuel oils, and liquefied petroleum gas [20]. Due to its high energy density, easy transportability and relative abundance, petroleum has become the world's most important source of energy since the mid-1950s. It is also the raw material for many chemical products, including pharmaceuticals, solvents, fertilizers, pesticides, and plastics. The remaining 16% not used for energy production is converted into these other materials. Oil pollution is the most obvious kind of marine pollution which attracts great public attention because the oil spills are visible. Many people may encounter it in different ways and its damage to the land and ocean habitats also remains enormous.

A. How Do Oils Enter the Ocean? Oils can reach the sea and ocean from a variety of sources such as oil extraction and transport, as well as from urban sources. Most inputs have been substantially reduced, but evaporation from oil cargoes, previously ignored, appears to make a major contribution which returns to sea by rain out. Tanker accidents attract much publicity, but are not an important source, except locally. Natural inputs from oil seeps occur in several parts of the world [2]. Nearly more than half of the oil in the ocean arrives there naturally through seepage from the ocean floor (Figure 3). The other is contributed by oil tankers, offshore oil facilities, runoff from roads and factories, and via the atmosphere. Offshore oil platforms can have many times of major, medium and small oil spills over its period of production. A significant amount of oil also leaks daily into the sea from these installations. When extreme pressure explodes an offshore oil rig, the blowouts may lead to very large spills. The blowouts cause an uncontrolled release of oil from the well. Although great precautions have been taken to prevent them, accidents happen occasionally. Ships introduce oil into the marine environment in several kinds of ways. Substandard and poor maintained ships, human error and adverse weather conditions, which may result in ship accidents, can cause oil spills. Usually, major shipping disasters involving oil tankers make the oil spill more frequent and intense. Coastal oil refineries, and urban and river run-off are the main sources that oil enters the ocean from land. Oil and petrol that are let by factories, houses and vehicles can be seen on the roads. This is washed down drains and into water courses and eventually reaches the sea.

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The atmosphere also contributes the unburned portion of heating oil, gasoline and other petroleum products. These then fall with rain into the ocean. But these incomplete combustion hydrocarbons never take up the whole atmospheric input source. It can not be ignored that the loss of petroleum hydrocarbons to the atmosphere by evaporation from cargoes of oil tankers and other containers, takes up a main amount of the atmospheric inputs.

Figure 3. Relative contribution of average, annual releases (1990-1999) of petroleum hydrocarbons (in kilotonnes) from natural seeps and activities associated with the extraction, transportation, and consumption of crude oil or refined products to the marine environment. (Figure from: Oil in the Sea III: Inputs, Fates, and Effects (2003) [21]).

B. Impacts on the Environment and Living Organisms Shores and coastal areas: Shores and coastal lines are high-energy beaches usually with more sheltered areas and rocks. Once oil reaches there, it is hard to remove it by wind blowing or wave action. A considerable variety of animals and the more sensitive red and green algae are killed by exposure to fresh oil. But much of the oil reaching beaches is bunker fuel or crude oil that has been at sea for several days that has lost most of its toxic constituents, so it poisons few organisms. However, the weathered oil may still cause damage because of its physical properties [2].

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Plankton: Plankton, especially the neuston, which lives in the top few centimeters of the sea, might be supposed to be particularly at risk because it is exposed to the highest concentration of water-soluble constituents leaching from floating oil, which are toxic to a wide range of planktonic organisms. Fixed vegetation also suffers from the oil destruction in salt marshes, sea grass beds and mangrove swamps which are low-energy areas likely to trap oil. Seabirds: The loss of sea birds due to oil pollution attracts the greatest public concern. It is difficult to give a precise estimate, but it is quite possible that tens or even hundreds of thousands of seabirds are oiled in the north-east Atlantic every year [2]. Seabirds are strongly affected by oil spills. The oil penetrates and opens up the structure of the plumage of birds, reducing its insulating ability, and so making the birds more vulnerable to temperature fluctuations and much less buoyant in the water. It also impairs birds' flight abilities, making it difficult or impossible to forage and escape from predators. As they attempt to preen, birds typically ingest oil that coats their feathers, causing kidney damage, altered liver function, and digestive tract irritation. This and the limited foraging ability quickly cause dehydration and metabolic imbalances. Most birds affected by an oil spill die unless there is human intervention [22]. Marine mammals: Marine mammals exposed to oil spills are affected in similar ways as seabirds. Oil coats the fur of Sea otters and seals, reducing their insulation abilities and leading to body temperature fluctuations and hypothermia. Ingestion of the oil causes dehydration and impaired digestion. Once an oil slick begins to weather or breaks up or disappears, the damage won’t stop accordingly. On the contrary, this is another beginning of a longer cycle of destruction. As oil droplets descend to the bottom of the ocean, they can clog the gills of fish and poison other sea life. If they sink into the sediment on the ocean floor, they may remain there for decades, centuries, and even longer, which will disturb the deep marine ecosystem or even slow down the whole evolutionary process. Moreover, public health also risks from oil pollution, so do commercial activities like fisheries, tainting and tourisms.

C. Monitoring and Control of Oil Pollution The monitoring and control of oil spills may be most widely studied compared to any other marine pollutant. While oil spills occur and remain on the surface of a sea, it usually can be monitored by aircraft and remote imaging devices (Figure 4). But once the slick begins to break up, it becomes much harder to track. Moreover, the impact of oil spill on coastlines, marine wildlife and fisheries must be monitored. Various countries and academic marine science departments all over the world are dedicated to the task of monitoring and cleaning up the oil spills. The Global Marine Oil Pollution Information Gateway compiled and presented by people all around the world will guide people to facts on oils (hydrocarbons) and marine oil pollution [24]. Information will be found on the efforts made by the international community to address the problem and find ways to take preventive action on the global, regional and national level. A slick is usually dispersed but not cleaned up with detergents which make oil settle to the bottom. Oils that are denser than water, such as PCBs, can be more difficult to clean as they make the seabed toxic. Much has been learned about how to best clean up oil spills since

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the Exxon Valdez. For example, some cleaning methods used after the Valdez spill inadvertently caused additional damage; the high pressure, hot water washing of the rocky shore removed both sediments and nutrients that could have aided in the recovery of the ecosystem [25]. Many other methods, such as controlled burning and dispersants for cleaning up oil spills, will be introduced in detail in Section 2.4. As for the prevention of oil pollution, the most important measures are those that prevent them in the first place. To do so, a variety of international, national or local conventions or laws on prevention of oil spills have been developed and entered intor force which will also be described in Section 2.4. Besides, finding alternative, renewable sources of energy is the best long-term solution to the oil pollution.

Figure 4. Oil spills (dark areas) detected by synthetic aperture radar (SAR) in a sea area with a busy shipping lane off the coast of Malaysia (near Kuantan). This ERS-2 SAR image was acquired on 4 April 1997 at 0325 UTC over the South China Sea. The imaged area is 100 km * 100 km. @ESA 1997. (Image from Alpers and Espedal, 2003 [23]) \

2.6. Radioactive Materials In 1986, French physicist Henri Becquerel discovered radioactivity when he was working with compounds containing the element uranium, shortly after the discovery of X rays. Radioactive materials are the most dangerous, longest-lasting pollutants that humans are adding to our environment, which includes the oceans. Their danger does not only contain the damage to living organisms, but also lie in the long-lasting and the continual emission of dangerous levels of radiation for thousands of years or even longer.

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Radioactivity is the spontaneous disintegration of atomic nuclei. The nucleus emits alpha particles, beta particles, or gamma rays during this process. Materials such as uranium, actinium and thorium that emit this kind of radiation are said to be radioactive and to be undergoing radioactive decay. Thus, radioactive materials are substances whose atoms are decaying—breaking down—into other atoms [1]. According to the penetrating abilities of the radiations, they are categorized into three types: alpha, beta, and gamma radiation. The alpha radiation can be stopped by a sheet of paper. Beta particles were later identified as high speed electrons. Six millimeters of aluminum are needed to stop most beta particles. Several millimeters of lead are needed to stop gamma rays, which have been proven to be high energy photons. Alpha particles and gamma rays are emitted with a specific energy that depends on the radioactive isotope. Beta particles, however, are emitted with a continuous range of energies from zero up to the maximum allowed for by the particular isotope. Of the three types of radiation gamma rays are the most dangerous. The time required for half of the atoms in any given quantity of a radioactive isotope to decay is the half-life of that isotope. Each particular isotope has its own half-life. For example, the half-life of 238U is 4.5 billion years. That is, in 4.5 billion years, half of the 238U on Earth will have decayed into other elements. In another 4.5 billion years, half of the remaining 238U will have decayed. One fourth of the original material will remain on Earth after 9 billion years. The half-life of 14C is 5730 years, thus it is useful for dating archaeological material. Nuclear half-lives range from tiny fractions of a second to many, many times the age of the universe [26]. Therefore, the harm that radioactive materials bring on is incredibly tremendous.

A. How Do Radioactive Materials Enter the Ocean? Natural part: Sea water is slightly radioactive. It contains a small but significant amount of radioactive elements that undergo spontaneous radioactive decay and produce energy, subatomic particles, and a remainder, or daughter nucleus, smaller than the original. Nearly all of the radioactive materials in the ocean are natural. The natural radioactive elements in the ocean are radioisotopes of potassium, rubidium, thorium, uranium etc. They reach the oceans mostly as a result of run-off from weathered rock or, in case of their disintegration products, by decay of the primordial substances in the water itself. Other radioactive substances, such as 3H and 14C, originate in the atmosphere through the interaction of cosmic radiation from outer space and the constituents of the air, and can also be produced in the course of human activities (GESAMP, 1991). Both of these two categories of radioactive substances are then distributed through the water column by physical, chemical and biological processes, and subsequently deposited in the ocean sediments. Table 1 lists some of the radioactive materials found in the ocean, along with their mass and activity [27]. Radioactivity is often expressed as decays per second, a unit referred to as a Becquerel (Bq). Sea water has a radioactivity of about 12.6 Bq [2]. Human activities: Since the 1940s, the latest stage of World War II with the explosion of the first nuclear weapons, pollution of the marine environment by radioactive materials generated by humans has increased the ocean’s radiation beyond its natural. Nuclear weapons tests had introduced artificial radionuclides into the environment until the signing of the test ban treaty between the USA, the former USSR, and the UK in 1963. From then until 1974 atmospheric tests were conducted by France in the Pacific Ocean, and by the People’s Republic of China, which made relatively minor contributions. From that time, all tests are

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believed to have been carried out underground with no discharge to the atmosphere [2]. Radioactive fallout was generated during the explosions of nuclear weapons. Then radiation from the explosions contaminates dust and other particles in the air, which eventually reach the surface of the earth. The radiation also contaminates the ground where the bomb was detonated. The contaminated soil can then washes into the sea, and contaminated dust blown into the air settles over the ocean eventually [1].

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Table 1 Some radioactive materials found in the ocean Nuclide

Total Mass

Total Activity

Uranium

90 μg

1.1 Bq

Thorium

30 μg

0.11 Bq

Potassium

17 mg

4,400 Bq

Radium

31 pg

1.1 Bq

Tritium

0.06 pg

23 Bq

Polonium

0.2 pg

37 Bq

Carbon

1.8 μg

15,000 Bq

Nuclear power plants sometimes discharge radioactive water into nearby waterways, and the gases are discharged from the smokestacks and emitted from tailings left over from the milling of uranium fuel. Nuclear power plants also produce radioactive waste, or radwaste. The first radwaste was released into the sea in 1944. Nuclear-powered vehicles, nucleararmed devices and nuclear weapons factories are other sources of radioactive pollution. Beside intentional inputs, radioactive pollutants can be released to the ocean by accidents which may also be fatal.

B. Impacts on Living Organisms It is difficult to identify the ecological impacts of radioactivity in the sea, since toxicity tests on marine organisms are not very informative. But the health hazard was fully recognized 40 years after the discovery of radioactivity. The radioactive isotopes, or radionuclides, contained in fallout that lands in the sea eventually end up in concentrated form in the bodies of marine plants and animals, and accumulate at the top the food chain. Since human beings are among the most radiosensitive of all living organisms, this problem is exacerbated. In contrast, many organisms near the bottom of the food chain, such as insects, can tolerate much higher levels of radiation than humans can, so they can survive and pass radionuclides in more concentrated form up to the food chain. The natural environment appears to be little affected by present levels of radioactivity, but there is naturally more concern about risks to the human population. About 78% of human exposure is from natural sources, but varies widely. Medical treatment (largely X rays)

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accounts for about 14%. Other man-made sources account for less 1%. Exposure to radiation may result in cancers or genetic damage. Chronic exposure to ionizing radiation may produce somatic effects, most importantly leukaemia and cancer of the bone, lungs, or breast; or genetic damage manifested in some abnormalities or defects in the next generation. Different radionuclides present different kinds of health hazard, depending on their chemistry [2]. However, radioactive substances have therapeutic uses. Extremely small doses are used to diagnose illness and higher doses are used to treat cancer, for instance. But any living organisms can be killed by radiation if given a large enough dose. The effects of exposure to abnormally high levels of radiation can take years and even decades to develop [1].

C. Monitoring and Disposal of Radioactive Materials A variety of authorities and agencies have been established to do series of existing radiation monitoring and detecting works. The International Committee on Radiological Units ICRU (originally known as the International X-Ray Unit Committe) was conceived at the First International Congress of Radiology (ICR) in London in 1925 and officially came into being at the ICR-2 in Stockholm in 1928. The primary objective was to propose an internationally agreed upon unit for measurement of radiation as applied to medicine. From 1950 on, the ICRU expanded its role significantly to embrace a wider field. The ICRU has as its principal objective the development of internationally accepted recommendations regarding: (1) quantities and units of radiation and radioactivity; (2) procedures suitable for the measurement and application of these quantities in diagnostic radiology, radiation therapy, radiation biology, nuclear medicine, radiation protection and industrial and environmental activities; (3) physical data needed in the application of these procedures, the use of which assures uniformity in reporting [28]. The U.S. Environmental Protection Agency (EPA) established RadNet (previously known as ERAMS) by consolidating a number of existing radiation monitoring networks. The RadNet program was initially responsible for monitoring radiation associated with nuclear weapons testing, but the program was later expanded to include monitoring radiation emergencies, following trends in environmental radioactivity levels, and providing data for dose calculations. Since it began, RadNet has developed an important environmental radiation database containing almost thirty years of data. This data has been studied to provide information about releases of radioactivity to the environment, from weapons tests and nuclear accidents to natural releases such as fires around a DOE site [29]. Once the radioactive waste enters the ocean, it is nearly impossible to remove or clean up, but methods and regulations on disposing radwaste have been carried on to help reduce the damage. Radioactive waste is categorized as either high level or low level. High-level radioactive waste is stored temporarily in spent fuel pools and in dry cask storage facilities. In 1997, in the 20 countries which account for most of the world's nuclear power generation, spent fuel storage capacity at the reactors was 148,000 tonnes, with 59% of this utilized. Away-fromreactor storage capacity was 78,000 tonnes, with 44% utilized. With annual additions of about 12,000 tonnes, issues for final disposal are not urgent. While the low-level radioactive waste deposal is concerned, it depends on who “owns” the waste. The handling and disposal are regulated differently. All nuclear facilities, whether they are a utility or a disposal site, have to comply with Nuclear Regulatory Commission (NRC) regulations. The three low-level waste

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facilities in the U.S. are Barnwell, South Carolina, Richland, Washington, and Clive, Utah [30, 31]. Moreover, the deposal methods must be developed further. Reprocessing, a procedure that could eliminate the majority of radioactive waste, must be perfected. We should continue making an effort to ban all nuclear testing, the use of nuclear weapons and nuclear-powered vehicles globally.

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3. MARINE POLLUTION IN WATER, SEDIMENT AND BIOTA Any material discharged into the sea inevitably causes some changes in the marine environment. The change may be great or small, long-lasting or transient, widespread or extremely localized. If the change can be detected and is regarded as damaging, it constitutes pollution. Much effort has been devoted to measuring levels of contamination of water, sediments and organisms. However, to determine whether the observed level of contamination will cause pollution generally requires a study of its biological effects [2]. Due to the wide diversity of pathways of contaminants entering the marine environment, their impacts are various and non-regular. The inputs to the oceans need to be controlled, but the attention should also be paid to the processes and status of the ocean under the effect of contaminants. Therefore, the values, assessments and distributions of them are needed for further schemes. The Group of Experts on the Scientific Aspects of Marine Pollution (GESAMP) is an advisory body consisting of specialized experts nominated by the Sponsoring Agencies (IMO, FAO, UNESCO, WMO, WHO etc.). Its principle task is to provide authoritative, independent, interdisciplinary scientific advice to organizations and member Governments to support the protection and sustainable use of the marine environment [32]. Since the first GESAMP review, as a result both of large-scale international scale surveys and of more restricted national exercises, a large amount of additional and more reliable information has become available on the concentration and distribution of contaminants from many parts of the world. Also, as indicated below, there have been improvements in the sampling and analytical techniques and in data quality controlling and modeling generally. This section focuses on the most critical potential pollutants within each category whose measurements are globally or locally available. Coastal and open ocean zones are separated where this appears to be useful, and examples will be selected from species of economic importance or bioindicator value.

3.1. Contaminants in Water 3.1.1. Contaminants in Coastal Waters It is obvious that contaminants are more concentrated in coastal waters, since they are largely associated with discharges to estuaries where most of the contaminants from land accumulate. But the variability is very high and dependent on the fluctuating physical and chemical conditions found in inshore waters. In that case, concentrations of contaminants may be very different both from spatial and temporal scales. It is hard to get all the information of

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coastal waters all over the world, but some typical regions are concerned in this section, from which some general characters can be learned and also suitable to other coastal regions. Historical records showed that mercury concentrations varied between 10~90 ng l-1 at hot spots, but may be only 1.0 ng l-1 or less close by, owing not only to the pattern of discharge, but also to the rapid formation and sedimentation of particulates forms of mercury. Cadmium outside the influence of industrialized areas may concentrate at 1~100 ng l-1, while lead concentration is highest in the immediate vicinity of industrial activity and river inputs. In southern Californian Bight lead concentrations are from 25~150ng l-1. Chlorinated hydrocarbons in coastal waters have their highest levels in industrialized zones, PCBs may range from 1 to 10 ng l-1, while DDT residues are generally below 5 ng l-1 in coastal waters though much higher levels were reported near sources [2]. Concentrations of nutrients nitrogen, phosphorus and dissolved and particulate carbon are also increasing, which may cause blooms of algae called red tides or harmful algal blooms. During the past 30 years, it is believed that countless red tides occurred in many coastal regions all over the world, but perfect solutions are still under development now. However, outstanding effects have been achieved along with great efforts that have been carried out in these several decades. Based on the NOAA reports released in May 2008, coastal waters show a decline trend in contaminants [33]. Based on two decades (1986-2005) of study, the report shows that environmental laws enacted in the 1970s are having a positive effect on reducing overall contaminant levels in coastal waters of the U.S. However, the report points to continuing concerns with elevated levels of metals and organic contaminants found near urban and industrial areas of the coasts. It is noted that pesticides, such as DDT, and industrial chemicals, such as PCBs, show significant decreasing trends around the nation, but similar trends were not found for trace metals. Moreover, what is of concern is that there are contaminants that continue to be problematic, including oil-related compounds from motor vehicles and shipping activities. The findings are the result of monitoring and analysis of 140 different chemicals in U.S. coastal and estuarine areas, including the Great Lakes. Significant findings from this report include: 1) Nationally decreasing trends of the pesticide DDT are documented with a majority of the sites monitored along the Southern California coast. 2) Decreasing trends were also found for the industrial chemicals PCBs. The Hudson-Raritan Estuary, one area of the country where some of the highest concentrations of these chemicals were found, now shows 80 percent of monitored sites with significantly decreasing trends for this pollutant. 3) Tributyl-tin, a biocide used as a compound to reduce or restrict the growth of marine organisms on boat hulls, was found to have greater than anticipated consequences as it affected not only the targeted organisms, but also other marine and fresh water life as well. First regulated in the 1980s, this compound is now decreasing nationally [33]. However, two major groups of contaminants raise great concerns: 1) Oil related compounds (Polycyclic aromatic hydrocabons, i.e., PAHs) from motor vehicles and shipping activities continue to flow into coastal waters daily. 2) Flame retardants known as PBDEs are a new class of contaminants currently being evaluated by NOAA to determine whether they are increasing in coastal waters and what effects they may have on both marine and human health. NOAA plans to issue a report on flame retardants in coastal waters later this year.

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3.1.2. Contaminants in Open Ocean Waters Since most of the contaminants are produced during human activities on land, obviously contaminants’ concentrations in open ocean waters should be lower than that in coastal waters. Among the metals selected for review by GESAMP, mercury does not display any distinctive depth distribution in the oceans, at least on the basis of data available. Measured concentrations in ocean waters range from 0.37 to 7.0 ng l-1, although representative levels tend to be around 1 ng l-1. In the north-west Atlantic, concentrations are about twice those of the north-east Pacific, while in the western Pacific there is some evidence that mercury decreases along a north-south gradient, possibly as a result of atmospheric transport from the continents and deposition via rain. For cadmium, reported concentrations in surface waters are more variable, from 0.2 to 200 ng l-1. The lowest concentrations (up to 10 ng l-1) are found in the open ocean, particularly in the sub-tropical and central gyres, with higher levels (up to 200 ng l-1) in enclosed seas, such as the Baltic and the North Sea, enhanced by river inputs. Unlike mercury, cadmium shows a nutrient-like distribution, being low in surface waters and increasing with depth. Lead concentrations in the open north Atlantic and north Pacific oceans range from 5 to 50 ng l-1 in surface samples. Arsenic is present in sea water principally as dissolved arsenate but also as arsenite in anoxic conditions. Concentrations in open waters surrounding the UK are around 2.6 μg l-1. Lower values, 1.3 to 1.7 μg l-1, are found in the Atlantic and 1.4 to 1.8 μg l-1 in the Pacific. Selenium in ocean waters is about 0.1 μg l-1, and higher in coastal waters [32]. Chlorinated hydrocarbon levels in the open ocean are around a few ng l-1 and are fairly uniformly distributed at all depths, but the highest concentrations occur in surface microlayers naturally enriched in lipid compounds. Levels of PCBs in the surface waters of the temperate zone of the northern hemisphere where there are more industrial activities are higher than those in the tropics, which presents a contrast to DDT [32]. According to a new study, a notorious class of environmental contaminants appears to be increasing in the open ocean despite regulations [34]. Researchers say the trend is threatening endangered bird species and potentially humans as well. The 1963 Clean Air Act and 1972 Clean Water Act restricted the use of PCBs and DDT in U.S., and some studies have reported declines of contaminants in marine predators that live in estuaries and coastal areas near shore. But PCB and DDT levels have also dropped in larger expanses of open oceanic zones. Researchers at the University of California did a series of experiments and measurements on two species of albatross to assess the contaminants level in the open waters. Results showed that PCB and DDT levels were twice as high as they were 10 years ago [34]. Also, it has significant implication on pollutants in organisms, which will be discussed in detail in the following subsection.

3.2. Contaminants in Sediments Contaminant distributions and concentrations in sediments reflect both local mineralogy and the nature and origin of the sediments like grain size, clay, organic content and so on. Sediment heterogeneity and the large variations in measurements of contaminant concentrations in sediments make data interpretation difficult. Deep sea sediments have more sparse information due to the considerable range. For instance, in the deep north Atlantic, lead has the highest concentrations, which range from 3 to 60 parts per million (ppm,

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equivalent to mg l-1), while cadmium in deep sea sediments is usually less than 0.05; mercury is from 0.01 to 0.6 ppm. Arsenic concentrations in the Pacific reach 20 ppm, with the highest values closest to active volcano ridges. Due to the limited samples taken during the series of cruises, the data for chlorinated hydrocarbons in deep open ocean sediments are exiguous [32]. However, data on sediments in coastal waters are more extensive but even more variable, so it is quite difficult to describe the definite ranges of different part of oceans all over the world. In that case, several main regions from the north to south hemisphere including the tropic belts will be concerned respectively. Research on these areas shows the latest information on the sediment contamination. Arsenic (As), trace metals and organic micro contaminants in sediments from the Pechora Sea in Russia have been determined for grab and core samples. Most of the organic matter appears to be of marine origin, but a terrestrial origin for organic contaminants is indicated for the coastal areas in the vicinity of the Pechora estuary. All organic micro-contaminant concentrations, except lindane, were low. Lithium normalization of Cd, Cr, Cu, Hg, Ni, Pb, V, and Zn concentrations indicates that they are at or near natural levels as a result of natural granular and mineralogical variability in the sediments. High levels of As, however, occur in fine grained surface and subsurface sediments. The As enrichment is most likely due to the deposition and post-depositional modification of As-rich radioactive particulate material dispersed into the Pechora Sea by underwater nuclear explosions in Guba Chernaya on the southwest coast of Novaya Zemlya during the 1950s and 1960s. All PCB congeners were at or below the detection limit of 0.1 ng g-1 (dry weight basis, same as follows). These values are comparable to northern North Sea and Barents Sea concentrations. This was also the case for the DDTs and HCBs. However, relatively high concentrations of lindane were found in the sediment from Guba Chernaya and in an adjacent trough that are approximately an order of magnitude higher than those found in the northern North Sea and Norwegian Trench [35]. Analysis and experiments have also been performed in different bays in Korea. During the research on trace organic contaminants in sediment, pore water and water samples from Onsan Bay in Korea in 2002, persistent organic pollutants and alkylphenols (APs) were determined in sediment and water samples, by using instrumental analysis and in vitro gene expression cell bioassay [36]. Results showed that PAHs were the predominant compounds in sediments with concentrations as great as 573 ng g-1. The PAH concentrations were elevated in sediment from inland rivers that flow through Onsan City (mean: 116 ng g-1) and discharge into Onsan Bay. Concentrations of polychlorinated biphenyls (PCBs) in sediments ranged from 1.0 to 56.2 ng g-1. Among different analyzed organochlorine (OC) pesticides (hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), chlordane compounds (CHLs), and DDTs), DDT concentrations were the greatest, ranging from 0.01 to 7.58 ng/g. The spatial gradient of contaminant concentrations suggested that streams and rivers were the major sources of PCBs, PAHs, and APs to the bay. Maximum concentrations of nonylphenol, octylphenol, and bisphenol A in sediments were 860, 11, and 204 ng g-1, respectively. Based on a mass balance analysis, PAHs apparently accounted for only a small portion of dioxinlike responses elicited by sediment extracts. Contamination by persistent OCs, such as DDTs, HCHs, CHLs, HCB and PCBs were examined in sediments, soils, fishes, crustaceans, birds, and aquaculture feed from Lake Tai, Hangzhou Bay, and in the vicinity of Shanghai city in China during 2000 and 2001. OCs were detected in all samples analyzed, and DDT and its metabolites were the predominant contaminants in most sediments, soils and biota. Concentrations of DDT and ratio of DDT to

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total DDTs were significantly higher in marine fish than those in freshwater fish. While the use of DDTs has been officially banned in China since 1983, these results indicate a recent input of technical DDTs into the marine environment around Hangzhou Bay. Comparison of OC concentrations in fish collected from Lake Tai and Hangzhou Bay suggests the presence of local sources of HCHs, CHLs and PCBs at Lake Tai. Higher proportions of penta- and hexa-PCB congeners in fish at Lake Tai may suggest the use of a highly chlorinated PCB product, such as PCB5, around this lake. This is a comprehensive study to examine the present status of OC contamination in various environmental media, such as sediments, soils and wildlife, in China [37]. In the United States, temporal and spatial distributions of contaminants in sediments of Santa Monica Bay (SMB) in California in 2003 were examined and analyzed [38]. SMB is located adjacent to the greater metropolitan Los Angeles area. It is an important ecological and economic resource for the area’s population of more than 10 million people and has been subjected to numerous stresses as a result of rapid urbanization and industrialization. Contaminant sources include, but are not limited to, municipal wastewater, urban runoff, industrial facilities, direct waste dumping, oil spills, natural oil seeps, and atmospheric deposition. The contaminant contributions to SMB from these sources have changed dramatically over time, a combination of increased inputs due to population growth and reductions resulting from improved waste treatment procedures, enhanced source control efforts, changed waste disposal practices, and increased public awareness, among others. Contaminant inputs from wastewater discharge, a major source of contamination to SMB, have declined drastically during the last three decades as a result of improved treatment processes and better source control. To assess the concomitant temporal changes in the SMB sediments, a study was initiated in June 1997, in which 25 box cores were collected using a stratified random sampling design. Five sediment strata corresponding to the time intervals of 1890-1920, 1932-1963, 1965-1979, 1979-1989, and 1989-1997 were identified using 210Pb dating techniques. Samples from each stratum were analyzed for metals, 1,1,1-Trichloro- 2,2bis(p-chlorophenyl)ethane (DDT) and its metabolites (DDTs), PCBs, and total organic carbon (TOC). Samples from the 1965-1979, 1979-1989, and 1989-1997 strata were also analyzed for PAHs and linear alkylbenzenes (LABs). Sediment metal concentrations increased from 1890-1979 and were similar during the time intervals of 1965-1979, 1979-1989, and 19891997, although the mass emissions of trace metals from sewage inputs declined substantially during the same time period. Trace organic contamination in SMB was generally highest in sediments corresponding to deposition during the years of 1965-1979 or 1979-1989 and showed a decline in concentration in the 1989-1997 stratum. Temporal trends of contamination were greatest in sediments collected from areas near the Hyperion Treatment Plant (HTP) outfall system and on the slope of Redondo Canyon. The highest contaminant concentrations were present in sediments near the HTP 7-mile outfall in the 1965-1979 stratum. Elevated trace metal and organic concentrations were still present in the 1989-1997 stratum of most stations, suggesting that sediment contaminants have moved vertically in the sediment column since sludge discharges from the 7-mile outfall (a dominant source of contamination to the bay) ceased in 1987. The widespread distributions of DDTs and PCBs in SMB and highly confined distribution of LABs around the HTP outfall system were indicative of a dispersal mechanism remobilizing historically deposited contaminants to areas relatively remote from the point of discharge.

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In the past years, a variety of methods for releasing or remediating the contamination in sediments have been developed in many countries and regions. In Germany, remobilization and demobilization of contaminants in sediments of the Mulde reservoir Saxony were studied [39]. Several sediment cores were analyzed for heavy metals and organic chemicals such as chlorobenzenes and DDTs. The comparison between anoxic and oxidized sediment cores showed the potential danger for heavy metal (Zn and Cd) remobilization from sediment due to bioturbation or resuspension by flooding. Chemical sequential extraction was used to describe the partitioning of heavy metals among different mineralogical components in the sediments. Results showed remobilization of Zn and Cd from the sediments. The stable fraction organic sulfidic bound of Zn and Cd was much decreased. Simultaneously, the carbonate fraction for Cd and Zn increased. Furthermore, the simulation of the diffusion of organic pollutants showed remobilization of 1,4-dichlorobenzene. The results confirmed the necessity of sediment remediation in the reservoir. Capping seems to be a promising approach for a low-cost remediation.

Figure 5. Major processes influencing the long term fate of sediment contaminant deposits (Figure from S tull, 1989 [40]).

In another study, the history, effects and future of contaminants in sediments of a reservoir on the Palos Verdes Shelf near a major marine outfall were investigated [40]. On the Palos Verdes Shelf, a reservoir of historically discharged wastewater constituents lies partly buried beneath progressively less contaminated sediments. Highest surface sediment concentrations are focused at an offshore of the ocean outfalls. Near the discharge, core stratigraphy reflects the mass emission history of trace contaminants, and peak concentrations are buried 20-40 cm below the sediment surface. Despite the removal of the world's largest manufacturer of DDT from the Los Angeles County Sanitation Districts' sewer system in 1971, a large amount of DDT on the order of 200 metric tons still remain in shelf deposits.

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Fish continue to bioaccumulate DDT, and some are reproductively impaired. Improvements in wastewater treatment have progressively decreased effluent solids discharges since the mid-1980s. Particulate inputs from the other major source, the Portuguese Bend landslide, have also declined rapidly. The declining solids raised the concern that historic contaminant deposits could be re-exposed, particularly (1) by physical forces, producing net erosion in the near shore, and (2) by burrowing benthic organisms. Therefore, studies of trace constituent distributions, benthic biological activity, and sediment dynamics are needed for a better understanding of the transport and fate of particulates and contaminants (Figure 5) which is necessary for sound management decisions.

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3.3. Contaminants in Organisms Based on the statistics in GESAMP, mercury and cadmium have been measured extensively in mixed zooplankton samples from the Mediterranean, where concentrations are around 0.1 and 2 ppb (Parts per billion), respectively. So far there is no evidence that the mercury found in deep-sea fish is related to human activities. Arsenic is present in marine algae, typically at 10 to 100 ppm, about three orders of magnitude above levels in sea water. Since arsenic is transferred via the food chain to mollusks and shrimp and eventually to man, (there is little data found in marine bird and mammals) the values are so low that it cannot imply the biomagnifications through the food chain. Data on chlorinated hydrocarbons in open ocean plankton are sparse, but research showed clearly that they have reached the deep ocean, demonstrating a transfer through the food chain [32]. Levels of contaminants in nearshore organisms are of great relevance to pollution impact because they are more directly exposed to land-based sources and to higher water concentrations. Out of great concern about human health, the worldwide review of measurement in marine biota became necessary. Analysis of PCB, DDT, and CHL contamination in selected finfish and shellfish species from estuarine and coastal marine waters of New Jersey (US) indicates that consistently the highest organochlorine contaminant levels in samples from the north and northeast regions of the state are in proximity to industrialized sites. A major conclusion of this study is that some commercially and recreationally important finfish and shellfish species in New Jersey waters, especially those which are lipidrich, have continued to accumulate PCBs, DDTs and CHL from the environment long after restrictive regulations were first placed on their use in the United States during the 1970s [41]. The greatest impact of OC contamination is nearby urban centers, most notably Newark and New York City. The marine ecosystem of the Pearl River Delta, located on the southern coast of China, has been heavily exploited following the rapid economic growth that has occurred since the 1980s. An investigation was carried on which aimed to elucidate trace organic contamination in marine biota inhabiting the Pearl River Delta area [42]. Biota samples, including greenlipped mussels (Perna viridis), oysters (Crassostrea rivularis) and shrimp (Penaeus orientalis) were sampled from 16 stations fringing the estuary. Elevated concentrations (on a dry weight basis) of polycyclic aromatic hydrocarbons (27.8-1041.0 ng g-1), petroleum hydrocarbons (PHs) (1.7-2345.4 ng g-1), PBCs (2.1-108.8 ng g-1), DDTs (1.9-79.0 ng g-1), and HCHs (n.d.– 38.4 ng g-1) were recorded. A human health risk assessment was conducted to estimate the risk to local residents associated with the consumption of biota collected from the Pearl River

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Estuary. The results indicated that PCBs were at levels that may cause deleterious health effects in populations that consume large amounts of seafood. However, it would be instructive to establish health criteria for trace organic contaminants that are specific to the local populations, in order to derive a more accurate and relevant health risk assessment. The composition and spatial distribution of aliphatic and PAHs were investigated in biota and coastal sediments from four countries surrounding the Gulf (Bahrain, Qatar, United Arab Emirates and Oman) [43]. The levels of total PHs (TPHs), aliphatic unresolved mixture and PAHs in sediments and biota were relatively low compared to world-wide locations reported to be chronically contaminated by oil. Only in the case of the sediments collected near the BAPCO oil refinery in Bahrain, having concentrations of 779 μg g-1 TPH equivalents and 6.6 μg g-1 PAHs, can they be categorized as chronically contaminated. Some evidence of oil contamination was also apparent in sediments and bivalves around Akkah Head and Abu Dhabi in the UAE, and near Mirbat in Oman. Contaminant patterns in sediments and biota indicated that the PAHs were mainly from fossil sources, with the exception of the high PAH concentrations in sediments near the BAPCO refinery that contained substantial concentrations of carcinogenic PAH combustion products. The current state of knowledge of levels, spatial and temporal trends of contaminants in the Arctic marine ecosystem varies greatly among pollutants and among environmental compartments. Levels of PCBs, OC pesticides and some heavy metals such as mercury and lead, in Arctic marine mammals and fish are relatively well documented because of the need for comparisons with biota in more polluted environments and interest in the contamination of native diets. Levels of heavy metals, alkanes, PAH and OCs in the Arctic Ocean are comparable to uncontaminated ocean waters in the mid-latitudes. But concentrations of alphaand gamma- HCHs are higher in northern waters far removed from local sources, possibly because lower water temperature reduces transfer to the atmosphere. Bioaccumulation of OCs and heavy metals in Arctic marine food chains begins with epontic ice algae or phytoplankton in surface waters. Polychlorinated camphenes (PCCs), PCB, DDT and CHL-related compounds are the major OCs in marine fish, mammals and seabirds. Mean concentrations of most PCBs and OC pesticides in the ringed seal (Phoca hispida) and polar bear (Ursus maritimus) populations in the Canadian Arctic are quite similar indicating a uniform geographic distribution of contamination, although alpha-HCH showed a distinct latitudinal gradient in bears due to higher levels in zones influenced by continental runoff. Ringed seals from Spitzbergen have higher levels of PCBs, total DDT and polychlorinated dioxins/furans (PCDD/PCDFs). In contrast to other OCs, PCDD/PCDFs in Canadian Arctic ringed seals and polar bears were higher in the east/central Arctic than at more southerly locations. Remarkably high cadmium levels are found in the kidney and liver of the narwhal (Monodons monoceros) from western Baffin Bay (mean of 63.5 μg g-1) and western Greenland waters (mean of 39.5μg g-1). Mercury concentrations in the muscle of ringed seals and cetaceans frequently exceed 0.5μg g-1 especially in older animals. Cadmium concentrations in polar bear livers increased from west to east, while mercury levels were higher in ringed seals from the western Canadian Arctic, which suggests that natural sources of these metals predominate. Studies of temporal trends in OCs in ringed seals and seabirds in the Canadian Arctic indicate PCB and DDT levels declined significantly from the early 1970s to the 1980s [44]. There is a lack of temporal trend data for other OC pesticides as well as for heavy metals and hydrocarbons.

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3.4. Trends and Conclusions Due to the fact that so many intrinsic and external factors can affect measured concentrations, reliable geographical trends are extremely difficult to detect, but more and more comprehensive and long-term studies carried out all over the world have proved useful, at least in connection with local sources of pollution. However, time trends are quite difficult to establish because reliable records are not available for sufficient long periods, or the same species have not been sampled consistently. Marine organisms are still useful to pinpoint land-based sources of OC pesticides and PCBs, though data on PCBs and total DDT residue levels in mussels from different regions shows that the variability is large. Usually the highest DDT and PCBs levels are found in marine organisms from areas with dense industrial and agricultural inputs, and the lowest in organisms from less contaminated coastal areas and the open ocean. However, long after the establishments of restrictions and laws in many countries and districts, these contaminants are controlled and treated more powerfully. Maybe decline trends of contamination levels will appear in those specifically areas, such as PCB levels declining due to the ban on the manufacture of these compounds in the early 1970s. Contaminants’ relative concentrations and distributions in different ecological compartments (water, sediments, biota) are valuable in developing models of transfer from source to target, in establishing spatial and temporal trends and possibly in identifying a mechanism for toxic action. Data sampling and analyses are often be used to monitor the contaminated environment and signal the possibly potential hazardous events. Also, data sets can be used in the estimation of temporal trends in coastal areas and doing long-term analyses of organisms and marine sediments. However, in some cases, data may be misleading. For instance, discharges of nutrients may be quickly taken up by plankton, and thus seen as increased production, not as higher concentrations in water. Again, some toxic substances may operate at low concentrations by triggering an effect, without being degraded or bound up in the process, so that measurements of data may not provide a true indication of their impact. Monitoring contaminant trends can be realized via tracing them in sea water, sediments and organisms, but inherent difficulties in achieving reliable results from analyzing contaminants in sea water severely limits the use of sea water. While sediments and organisms, as good integrators of contaminant inputs, are easier to analyze for trace contaminants and offer the best way at present to establish spatial and temporal trends in contaminant distribution. Moreover, international programs have been carried on which can provide a good basis for the analysis of geographic and temporal trends such as the Mussel Watch, UNEP Regional Seas program and so on [32].

4. PREVENTION AND CONTROL OF MARINE POLLUTION 4.1. Methodology The ocean has the ability of self-purification. This may make people overestimate its pollutant carrying capacity. But the fact tells us the marine self-purification ability is limited. For a specific area, the total quantity of pollutants it can accommodate is more limited. Once the quantity exceeds the largest load, the control on the marine pollution will become much

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more difficult than the control on land or atmospheric pollution. This is because marine pollution control needs a longer period of time, more complex technology and more investment. Take the oil spills as an example. The oil may be crude oil, refined petroleum products (such as gasoline or diesel fuel) or by-products, ships' bunkers, oily refuse or oil mixed in waste or released from natural geologic seeps on the sea floor. These oil spills are harmful to aquatic plants and wildlife, including fish, birds and humans. Controlling these potentially dangerous spills is critical to the integrity of our waterways. So far, a variety of techniques have been developed to stop the spread of oil in the ocean or coastal waters once the oil has spilled. Theses techniques include 1) Bioremediation: use of microorganisms [45] or biological agents [46] to break down or remove oil. 2) Dredging: for oils dispersed with detergents and other oils denser than water. 3) Skimming: requires calm waters. 4) Dispersants: they act as detergents which cluster around oil globules and allow them to be carried away in the water. But the dispersed oil droplets infiltrate into deeper water and can lethally contaminate corals [47]. 5) Controlled burning: can effectively reduce the amount of oil in water, if done properly. But it can only be done in low wind, and can cause air pollution [48]. 6) Solidifying: solidifiers make the oil stay retained in the solid mass allowing for easy removal [49]. During the cleaning up the oil spills, the equipments used in different ways include booms which are large floating barriers that round up oil and lift the oil off the water, skimmers which are boats that skim spilled oil from the water surface, sorbents which are large sponges absorbing oil, chemical dispersants and biological agents which break down the oil into its chemical constituents, high-pressure or low-pressure hoses which wash oil off beaches, vacuum trucks, which vacuum spilled oil off of beaches or the water surface, shovels and other road equipments which are typically used to clean up oil on beaches [50] and solidifiers which react with oil and form a cohesive mass that floats on water for quick removal [49]. Oil spills are not the only pressure on marine habitats; chronic urban and industrial contamination or the exploitation of the resources they provide are also serious threats. Although different methods have been developed and can be adopted once marine pollution occurs, it is not easy to achieve the desired results. In order to prevent and control marine pollution, we must treat the root cause, not symptoms. Therefore, great measures must be taken first on the control of sources of pollution. Among them, the conventions or laws on prevention of marine pollution have been proven to be the most effective measures. In the past several centuries, a variety of international conventions (agreements among nations or by international organizations on behalf of participating nations) or laws as well as many national or local laws have been developed. In the next section, we will focus on the international conventions on marine environmental protection.

4.2. Conventions on Protection of Marine Environment In this section, some key international conventions (agreements among nations or by international organizations on behalf of participating nations) or laws concerning marine pollutions will be introduced.

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The first known international agreement is the simple ‘Law of the Sea.’ It was formulated by the lawyer Grotius in the seventeenth century, who said that “Mare Liberum…The sea is free” [51]. In the following century, this absolute freedom of passage was eliminated within territorial waters. The intention of this eighteenth-century agreement was simply to allow nations to protect themselves against invaders. The law of the sea remained essentially unchanged for next 200 years. In the eighteenth and nineteenth centuries, the industrial revolution and the upsurge in international commerce which followed resulted in the adoption of a number of international treaties related to shipping, including safety. The subjects covered included tonnage measurement, the prevention of collisions, signaling and others [52]. By the end of the nineteenth century suggestions had been made for the creation of a permanent international maritime body to deal with these and future measures. Although the plan was not put into effect, international co-operation continued in the twentieth century, with the adoption of still more internationally-developed treaties. Among them the first known international treaty that contained provisions for marine pollution prevention was signed in 1942 and put into force on September 22 in the same year. The treaty said ‘Each of the High Contraction Parties shall take all practical measures to prevent the exploitation of any submarine areas claimed or occupied by him in the Gulf from causing the pollution of the territorial waters of the other oil, mud or any other fluid or substance liable to contaminate the navigable waters or the foreshore and shall concert with the other to make said measures as effective as possible [51]. The first significant, multinational effort to prevent marine pollution was an accord signed in London in 1954 that focused almost exclusively on oil pollution from tankers. Although the International Convention for the Prevention of Pollution of the Sea by Oil was heavily amended over the years and has been superseded by the International Convention for the Prevention of Pollution form Ships (MARPOL, 1973), it remains a landmark convention. In 1958, the International Maritime Organization (IMO) came into existence. The IMO was made responsible for ensuring that the majority of these international conventions were kept up to date. It was also responsible for developing new conventions as and when the need arose. As a result, numerous international conventions as well as protocols and amendments to protect the oceans have been formulated since 1950s. We summarize the most important of these in Table 1. In Table 2, the international conventions concerning marine safety and liability and compensation were also listed. This is because marine accidents or incidents can lead to pollution of the marine environment. Thus safe management is very important. In addition, pollution will never be totally eliminated; compensation for pollution damage is an important form of protection. Compensation is necessary for environmental restoration, but it also functions as a deterrent, and thus, has a preventive effect. Among these conventions, the MARPOL Convention is the main international convention covering prevention of pollution of the marine environment by ships from operational or accidental causes. MARPOL was adopted on 2 November 1973 at IMO and covered pollution by oil, chemicals, and harmful substances in packaged form, sewage and garbage. As the 1973 MARPOL Convention had not yet entered into force, the 1978 MARPOL Protocol absorbed the parent Convention. The combined instrument is referred to as the International Convention for the Prevention of Marine Pollution from Ships, 1973, as modified by the Protocol of 1978 relating thereto (MARPOL 73/78). It entered into force on 2

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October 1983. The convention includes regulations aimed at preventing and minimizing pollution from ships - both accidental pollution and that from routine operations (see [52] for more details of different conventions). Through the variety of international conventions, international efforts have been devoted to protecting and preserving the marine environment. The conventions have also contributed to the development of international laws on the marine environment protection and preservation. Based on the conventions, practical measures can be taken by governments and private and public entities (a) to prevent accidents to ships at sea; (b) to ensure safe management so as to prevent accidents or incidents that can lead to marine pollution; and (c) to prepare and equip themselves to be able to take necessary and appropriate measures to prevent, mitigate or minimize pollution when accidents occur [53]. Table 2. List of IMO conventions Abbreviation

Title

Maritime safety LL

International Convention on Load Lines, 1966

STP

Special Trade Passenger Ships Agreement, 1971

CSC

Convention on the International Regulations for Preventing Collisions at Sea, 1972 International Convention for Safe Containers, 1972

SOLAS

International Convention for the Safety of Life at Sea, 1974

INMARSAT

Convention on the International Maritime Satellite Organization, 1976

SFV

The Torremolinos International Convention for the Safety of Fishing Vessels, 1977

STCW

International Convention on Standards of Training, Certification and Watch keeping for Seafarers, 1978

STCW-F

International Convention on Standards of Training, Certification and Watch keeping for Fishing Vessel Personnel, 1995

SAR

International Convention on Maritime Search and Rescue, 1979

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COLREG

Marine pollution OILPOL 1954

International Convention for the Prevention of Pollution of the Sea by Oil, 1954, as amended

INTERVENTION 1969

International Convention relating to Intervention on the High Seas in Cases of Oil Pollution Casualties, 1969

INTERVENTION PROT 1973

Protocol relating to Intervention on the High Seas in Cases of Pollution by Substances other than Oil, 1973, as amended

MARPOL, 1973

International Convention for the Prevention of Pollution from Ships, 1973

MARPOL PROT

Protocol of 1978 relating to the International Convention for the Prevention of Pollution from ships, 1973, as amended

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Abbreviation

Title

MARPOL PROT 1997

Protocol of 1997 to amend the International Convention for the Prevention of Pollution from Ships, 1973, as modified by the Protocol of 1978 relating thereto (Annex VI on the prevention of air pollution from ships)

LC 1972

Convention on the Prevention of Marine Pollution by Dumping of Wastes and Other Matter, 1972, as amended

LC PROT 1996 OPRC 1990 HNS-OPRC AFS 2001 BWM 2004

Protocol of 1996 to the Convention on the Prevention of Marine Pollution by Dumping of Wastes and other matter, 1972 International Convention on Oil Pollution Preparedness, Response and Cooperation, 1990 Protocol on Preparedness, Response and Co-operation to Pollution Incidents by Hazardous and Noxious Substances, 2000 International Convention on the Control of Harmful Anti-Fouling Systems, 2001 (ANTI-FOULING) International Convention for the Control and Management of Ships' Ballast Water and Sediments, 2004

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Liability and compensation CLC 1969

International Convention on Civil Liability for Oil Pollution Damage, 1969

FUND 1971

International Convention on the Establishment of an International Fund for Compensation for Oil Pollution Damage, 1971

NUCLEAR 1971

Convention relating to Civil Liability in the Field of Maritime Carriage of Nuclear Material, 1971

PAL 1974

Athens Convention relating to the Carriage of Passengers and their Luggage by Sea, 1974

LLMC 1976

Convention on Limitation of Liability for Maritime Claims, 1976

HNS 1996 BUNKERS 2001

International Convention on Liability and Compensation for Damage in connection with the Carriage of Hazardous and Noxious Substances by Sea, 1996 International Convention on Civil Liability for Bunker Oil Pollution Damage, 2001 (Bunkers Convention)

5. SUMMARY During the last twenty years, there has been an increasing number of conflicts arising from different claims to use the marine environment. The increased use of maritime space for various potentially conflicting purposes leads to the over-exploitation of the oceans and seas, accompanied by marine pollution. The direct victim of marine pollution is primarily marine life. For example, the spread of oil spills not only blocks the sun radiation, affecting the photosynthesis of marine plants, but hinders air-sea exchange, leading to large areas of hypoxia of sea water, thereby endangering the marine life. Frequent algal blooms also do great harm to aquaculture production by reducing the yield significantly. Sometimes humans themselves will become the direct

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victims of marine pollution. For example, the oil spills will pollute the beach and thus trigger allergic dermatitis or other diseases. The indirect victims of marine pollution are of course human beings themselves. The sharp drop in aquaculture production often causes great economic losses. Eating aquatic products with high concentration of pollutants will absolutely harm the human body and even cause incidents such as poisoning and infection. The enrichment of some carcinogens via the food chain can cause more serious harm to the human beings. In the future, the use of marine resources will intensify, which will lead to the deterioration of the marine environment. Scientists’ warnings of a long-term deterioration have started to arouse the concerns of the public and governments. Some necessary measures have been taken into effect to reduce the harmful effects of marine pollution. Numerous conventions on marine environmental protection have also been adopted. However, more needs to be done in political and legal arenas. In a word, the prevention and controlling of marine pollution is a long-term and arduous task. There is a long way to go. Persistent efforts are needed to protect the marine environment.

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[48] Barry, C. (2007). Slick Death: Oil-spill treatment kills coral. Science News, 172, 67-67. [49] Delaune, R. D., Lindau, C. W., and Jugsujinda A. (1999). Effectiveness of ‘Nochar’ solidifier polymer in removing oil from open water in coastal wetlands. Spill-Science and Technology Bulletin, 5, 357-359. [50] Emergency Response: Responding to Oil Spills. Office of Response and Restoration, NOAA. [51] Ruster, B., and Simma B. (1975). International protection of the environment: Treaties and related documents, Vol. 1. Dobbs Ferry. NY: Oceana Publications Inc. [52] IMO Conventions [online]. 2002 [cited 2008 July 18]. Available from: http://www.imo.org/ [53] Basedow, J., and Magnus, U. (2007). Pollution of the Sea – Prevention and Compensation, NY: Springer Berlin Heidelberg.

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In: Impact, Monitoring and Management… Editors : Ahmed El Nemr

ISBN 978-1-60876-487-7 © 2010 Nova Science Publishers, Inc.

Chapter 9

HEAVY METAL POLLUTION IN AQUATIC ENVIRONMENTS Ayse Bahar Yilmaz1 Faculty of Fisheries, Mustafa Kemal University 31200 Iskenderun-Hatay, Turkey

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ABSTRACT Metals which in their standard state have a specific gravity (density) of more than about 5 g cm-3 are described as ‘heavy metals’. Some of them, such as copper, iron, chromium, zinc and nickel are essential in very low concentrations for the survival of all forms of life. These are described as essential trace elements. Only when present in greater quantities, these can cause metabolic anomalies like the heavy metals lead, cadmium, arsenic and mercury which are already toxic in very low concentrations. Heavy metals are produced from a variety of natural and anthropogenic sources. Human beings release a high anthropogenic emission of heavy metals into the biosphere. Waste (i.e. emission, wastewater and waste solid) is the origin of heavy metal pollution to water, soil and plants. In aquatic environments, metal pollution can arise from direct atmospheric deposition, geological weathering or through discharge of agricultural, municipal, residential or industrial waste. Under certain environmental conditions, heavy metals may accumulate to a level of toxic concentration causing ecological damage. As a result, living things inhabited contaminated waters may show rather high metal concentrations. In addition, metal bioaccumulation causes biochemical or pathological effects on fish resulting in decrease of growth, fecundity and survival. The members from the upper level of the food chain may carry a critical level of metals and are hence more explanatory than observing water or sediments. Therefore, numerous reports describe metal residues in aquatic organisms such as mussels, shrimp and wild fish from marine and freshwater species. Such studies have been carried out to determine the levels of some heavy metals in some tissues of aquatic organisms from marine and inland waters. Liver, spleen and kidney tissues are known to have high metabolic activities and thus have been used to observe the level of absorbed metals. 1 E-mail: [email protected]. Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

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Ayse Bahar Yilmaz Gonads, which can be attributed to the reproductive cycle of fish, have also accumulated high amounts of heavy metals. Metal concentrations in the skin and gills have reflected the concentration of metals in waters. Although it is well known that muscle is not an active tissue in accumulating heavy metals, muscle tissue accumulation levels were also studied because of their consumption by humans. Metal uptake by aquatic organisms from contaminated water may differ depending on its ecological needs and metabolism, as well as other factors such as salinity, temperature, contamination gradients of water, food, sediment and interacting agents. Two main objectives prevail in aquatic pollution monitoring programs: (1) determining contaminant concentrations in consumed part of organisms considering the health risk for humans, and (2) using organisms as an environmental indicator of aquatic ecosystem’s quality.

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1. INTRODUCTION It has been well documented that there are numerous industrial chemicals in use and continually, new ones enter the market place. These chemicals are found in anthropogenically altered aquatic environments. Fortunately, only a very small percentage of those chemicals enter waterways, but the possibility for uptake of chemicals by aquatic organisms are immense. The discharge of large volumes of treated water (industrial or domestic effluents) to coastal and offshore waters may result in an increase in the concentrations in the receiving waters. This is due to the chemicals that are present in wastewater at concentrations much higher than those in the ambient seawater. The major classes of toxic chemicals of concern for fish are metals, chlorine, cyanides, ammonia, detergents, acids, pesticides, polychlorinated biphenyls, petroleum hydrocarbons and other miscellaneous chemicals [1]. These chemicals may be taken up into the tissues of marine organisms living near the treated water discharge. The extent of this bioaccumulation depends on the concentration and physical form of the chemicals in the ambient water and sediments near the discharge [2]. The conditions producing a low dissolved oxygen concentration and toxic chemicals are the most important types of water pollution affecting fish. All heavy metals are potentially harmful to most organisms at some level of exposure and absorption. Their presence in the environment has increased in certain areas to critical levels, which threaten the health of aquatic and terrestrial organisms, man included. Therefore, numerous reports describe metal residues in wild fish from marine species [3-12]. These studies are mostly based on accumulating high levels of trace metals in different tissues of fish, such as liver, gonads, gills, and muscle.

2. WHAT IS “HEAVY METAL”? The clearest distinction among the elements is their classification as metals, non-metals, or metalloids. The “staircase” line that runs from the top of group 3A (13) to the bottom of Group 6A (16) on the periodic table is the dividing line for this classification [13]. The metals

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appear in the large lower-left portion of the periodic table. About three-quarters of the elements are metals including many main-group elements (1A, 2A) and all the transition and inner transition elements. They are generally shiny solids at room temperature (mercury is the only liquid) that conduct heat and electricity well and can be tooled into sheets (malleable) and wires (ductile). There has been a tendency in the literature on water pollution to speak of nearly all metals as “heavy metals,” although some have tried to avoid this designation [14]. Lying at the staircase line, metalloids (also called semi-metals) show properties between those of metals and nonmetals. Metaloids such as selenium and arsenic are included within metals in many references. The “Borderline” and “Class B” metal and metalloid ions are often referred to as “heavy metals” in general nomenclature. They comprise As3+, Cd2+, Co2+, Cr3+, Cu2+, Fe2+, Ga3+, In3+, Mn2+, Ni2+, Pb2+, Sb3+, Sn2+, Sn4+, Ti2+, and V2+ as borderline ions; and Ag+, Au+, Bi3+, Cu+, Hg2+, Pb4+, Pd2+, Pt2+, and Tl3+ as Class B ions [14].

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2.1. Essential Elements -Trace Metals Many essential macro and micro nutrients are known to have biochemical or physiological functions in animals. All marine organisms contain metals as normal constituents of their tissues. Several metals are essential trace nutrients required for various physiological or biochemical functions in marine organisms. Some metals such as sodium, potassium, magnesium and calcium are called major essential elements. The expression “trace metals” is often used instead of the word “metal” alone for biological activities. This reflects the important fact that many metals are required for normal physiological function in animals but only at trace concentrations, and these concentrations vary considerably among different species. Important trace metals include copper, iron, zinc, manganese, cobalt, selenium, tin and chromium. Altered physiological functions are observed when one or more of these reach sufficently high concentrations in cells [1].

2.2. The Solubilty of Heavy Metals and their Compounds in Aquatic Systems When metals are relaesed into the environment via a wide spectrum of natural and anthropogenic sources (i.e. wide variety of industrial effluents and old mines), they are also transferred to aquatic systems by natural activities. Chemical speciation of metals in aquatic systems is dependent on the specific physical, chemical and physochemical factors that prevail in local environments. Factors such as salinity, dissolved oxygen, pH, hardness, and sedimentary load all influence the prevailing chemicals forms of metals in aquatic systems [15]. Acid precipitation also causes the leaching of metals from surroundig soils [16]. Metals tend to complex with organic and inorganic chemicals and this may reduce their bioavailability to resident organisms [17]. These, in turn, influence metal bioavailability and toxicity [15]. Metals in the form of pure metal, precipitates, or heavy minerals are not bioavailable to marine organisms [18]. If metals oxidize and their oxides are soluble, they may become available. Dissolved metals in seawater tend to form complexes with inorganic and organic ligands. Metal complexes vary substantially in bioavailabilty to marine organisms [2]. F1–,

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Cl1–, SO42–, OH1–; and HCO31–, CO32– and HPO42– create inorganic, anionic ligands in natural waters. Some trace metals may also be important for oxic natural waters. In anoxic waters S and N exist in forms of HS1–, S2– and NH31– [19,20]. The bioavailability of a metal in dissolved in seawater depends on the fraction of the total metal’s activity. Most metals are available in forms of free ion and aqua ions, (e.g., M[OH]2 and M[OH]1–) [19].

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3. BIOAVAILABILITY OF HEAVY METALS When metals enter natural waters, there are several things that may happen to greatly affect their bioavailability [1]. Soluble chemical forms include simple aquated metal ions, metal ion complexes with inorganic anions, and metal ion complexes with organic ligands such as amino, fulvic, and humic acids [21]. Environmental conditions that cause a shift of the dominant metal from one form to another not only affect the bioavailability of the metal but can also affect the direct uptake to different pathways [15]. For dissolved metals, there is considerable evidence for the view that the ionic form in solution is the major bioavailable form in aquatic environments [22]. If there is a considerable amount of organic material or suspended solids, the actual amount of dissolved metal available to be absorbed by the fish will be greatly reduced. This tendency to form complexes with organic and inorganic ligands (primarily chloride, carbonate, and hydroxide) varies with the metal [23]. For example, copper binds to organics far more readily than either cadmium or silver does [24]. Many studies in which free metal ion concentrations have been controlled with chelating agents or measured with electrochemical procedures implicate the free metal ion concentration rather than the total metal concentration as the major determinant of metal accumulation or toxicity [15]. Dissolved Cu, Cd and Zn, (e.g., the ionic form or analytically labile form) in some cases, correlates best with metal accumulation or toxicity [25]. The relative importance of the bioavailability of other chemical forms of dissolved metals, particularly organically chelated forms, is not as clearly understood [26]. Consequently, it is important that the dissolved metal is measured rather than just the total concentration in the water, in order to assess the amount of metal actually available for absorption by the fish [1].

3.1. Bioaccumulation-Bioconcentration-Biomagnification-Uptake A word about terminology: the expressions “bioaccumulation” and “bioconcentration” are used rather synonymously in the literature. They refer to the process of fish’s acquiring a body burden of some chemical that is at a higher concentration than that in the water [1]. Veith and Kosian [27] suggest the term bioconcentration to be limited to the accumulation of a chemical directly from water and exclude that obtained via food while bioaccumulation would refer to the accumulation from both food and water. According to Neff [2], bioconcentration is a special case of bioaccumulation. Bioconcentration is defined as uptake and retention of a chemical from water alone. Uptake from other sources is not considered. Bioaccumulation is the uptake and retention of a bioavailable chemical from any one of, or all possible external sources (water, food, substrate, air). For bioaccmulation to occur, the rate of

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uptake from all sources must be greater than the rate of loss of the chemical from the tissues of the organism. Many higly soluble chemicals, such as ammonia and some inorganic ions are bioavailable and rapidly penetrate permeable tissues of marine organisms. However, they are not retained and are lost just as rapidly from the tissues by diffusion, metabolic transformation, or active transport. Their concentrations in tissues are equal to or lower than their concentrations in the ambient medium or they are regulated by the organism at a particular level independent of concentrations in ambient medium. Some other bioavailable chemicals are taken up rapidly, but are transformed and/or excreted rapidly by metabolic processes of the organism and are not bioaccumulated [2]. Bioaccumulation of metals by marine organisms is more complex than bioaccumulation of other chemicals (non-polar organics and inorganics) and involves interactions between aqueous speciation of the metal and the biochemistry of the organism [19]. Bioaccumulation of chemicals from food is called trophic transfer. Biomagnification is the process whereby a chemical, as it is passed through a food chain or food web by trophic transfer, reaches increasingly higher concentrations in the tissues of animals at higher trophic levels. Trophic transfer of contaminants in marine food webs involves many of the same physical and chemical processes that are involved in the accumulation of contaminants from water [2]. Fish may accumulate both bioconcentration directly from water and biomagnification from feeding itself with creatures in the lower level of the food chain. Generally, the term “uptake” is referred to by several researchers for the accumulation of pollutants in the fish. This term describes the processes better, because the pollutants are actually taken into the body of the fish. The amount of uptake depends on a number of parameters such as the uptake rate, metabolism of the chemical, form of the chemical and the phychemical parameters of seawater.

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3.2. Biological Concentration Factor (BFC) The magnitude of bioconcentration is measured with the bioconcentration factor (BCF). BCF describes the extent to which something accumulates in an aquatic organism. The BCF is the ratio at equilibrium of the concentration of a chemical in the tissues of the organism to the concentration of the chemical solution in the water to which the organism was exposed [2]. BCF = Ct / Cw = k1/ k2

(1)

where, Ct and Cw are the concentration of the chemical in tissue and water, respectively, at equilibrium, k1 is the uptake clearance, and k2 is the release rate constant. BCF is a unitless value obtained by dividing the concentration in one or more of the tissues by the average concentration in the water. Uptake clearance has units of unit mass of chemical/unit mass of tissue/ unit time, which translates to time–1 [28]. The release rate constant also has units of time–1 ; therefore, BCF is unitless.’

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4. IMPORTANCE OF HEAVY METALS IN THE MARINE ORGANISMS’ ENVIRONMENT Unlike most organic contaminants, metals are important natural components of the marine organism environment. All metals with the potential of becoming pollutants are present at trace or ultratrace concentrations in seawater and all are present at higher concentrations in uncontaminated sediments and tissues of marine organisms than in seawater (Table 1).

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Table 1. Typical concentrations [µgl -1 (ppb)] of selected metals in seawater and ocean water

Metal

Seawater*

Arsenic (As) Barium (Ba) Cadmium (Cd) Chromium (Cr) Copper (Cu) Iron (Fe) Lead (Pb) Manganese (Mn) Mercury (Hg) Molybdenum (Mo) Nickel (Ni) Vanadium (V) Zinc (Zn)

1–3 3 – 34 0.001 – 0.1 0.1 - 0.55 0.03 - 0.35 0.008 – 2.0 0.001 – 0.1 0.003 – 1.0 0.00007 – 0.006 8 – 13 0.1 – 1.0 1.9 0.006 – 0.12

Clean open-ocean water* 0.5 – 3 3 – 34 1 – 100 0.1.10-3 – 0.55.10-3 0.05 – 0.35 0.002 – 0.2 0.07.10-3 – 6.10-3

0.006 – 0.523

* Data from Neff [2].

Seventeen trace nutrients are required by some terrestrial and marine organisms, such as zinc, iron, chromium, manganese, cobalt, nickel, copper and selenium. Many of the trace nutrients are components of bioactive proteins or enzyme cofactors. Some of the trace nutrients; vanadium-arsenic-tin are essential to only a few species of marine organisms [2]. Several of the essential trace nutrient metals are considered to be important environmental contaminants because of their toxicity and potential to be mobilized by man’s activities [29]. These include vanadium, chromium, nickel, copper, zinc, arsenic, tin, and selenium. Because they are essential micronutrients, marine organisms have evolved mechanisms for accumulating them from water and food and for regulating their forms, distribution, and concentrations in tissues and body fluids [30]. Some marine organisms accumulate apparently nonessential metals in their tissues to high concentrations or essential metals at concentrations much higher than required. In most cases, the reasons for the bioaccumulation are not known [2].

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4.1. The Routes for a Substance to Enter a Fish There are four possible routes for a substance to enter a fish: gill, drinking water, skin, and food. For dissolved metals, there is considerable evidence for the view that ionic form in solution is the major bioavailable form in the aquatic environment [22]. The gill tissue (which is the main point of entry for dissolved substances) will be exposed to a far greater amount of selected pollutants than terrestrial animal breathing air. A fish must breathe roughly 20 times more of its respiratory medium (i.e., water) than a terrestrial animal in order to obtain an equivalent amount of oxygen [1]. For example, a 250-g trout at rest will pass approximately 48 l of water over its gills each hour [31]. Gills possess a counter current blood/water flow system, very thin epithelial membranes, and large surface areas, which facilitates the uptake of materials from the water and their transfer to blood [1]. As for the issue of drinking water, it is different for fish from mammals. Also, different fish types’, like saltwater and freshwater fish, behaviors are actually contrasting. Saltwater fish have to drink water, because the water in their environment is saltier than the liquids in their bodies. Osmosis causes water from their body tissues to be released into their environment. Saltwater fish have to constantly drink large quantities of water to replace what they lose through osmosis. Diffisuon then releases the excess salts and minerals taken in and not needed. The salts and minerals exit through special cells at the base of their gills back into the saltwater. Saltwater fish urinate very little because of these processes. On the other hand, freshwater fish do not actively drink water, but absorb the water through their skin and gills. So freswater fish urinate in large quantities to prevent their tissues from taking on too much water. Fish need osmosis and the diffusion process to keep their tissues and organs working properly. An interesting example for fish is the salmon that lives in both fresh and salt water, and consequently, they have the characteristics of both types of fish [32, 33]. The importance of skin relies on the size of the fish and the type of toxicant. While large fish account for less than 10% of the total absorbed dose (chlorethanes), small fish skin, due to the large surface to volume ratio, can account for up to one half of the absorbed dose [34]. Food, another possible route for a substance to enter a fish, varies greatly as route of exposure and depends mostly on the availability of the substance.

4.2. Mechanisms of Metal Uptake Most metals are absorbed by fish in the ionic form since the outer surface of a gill epithelial cells has a negative charge attracting metallic ions. But recently it has been found that not all metals bind to the surface equally well. The affinity of the gill for metals is determined by the microenvironment of the gill surface which is complex, because it includes the epithelial membranes as well as the mucus layer with its mixture of glycoproteins, mucopolysaccharides, several low molecular weight compounds, and water [1]. Contrary to what might first be expected, the absorption of a metal into cells of the gill is inversely proportional to the surface-binding affinity. For example copper, which has a low affinity, is absorbed into the cells much more readily than either calcium or cadmium [31]. The mechanism of metal uptake through the gill has been assumed to be simple diffusion, and mucus on the surface of the gill has a considerable influence on the accumulation by the gills

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of metals [35]. The rate of metal uptake into the gill tissue correlates with the weight-specific metabolic rate, thus small fish accumulate it more rapidly than large ones, because the higher flow rate of water over the gills of small fish apparently results in greater uptake. Metals and some of their aqueous ligands may move through cell membranes of gills, gut epithelia, and other permeable body surfaces by lipid permeation of charged species, complex permeation of metal-ligand complexes, carrier-mediated transport, diffusion of hydrated ions through ions channels, ion-exchange pumps, endocytosis of precipitated species, and solvent drag with water influx in dilute media [19]. Biological membranes of the general body surface and gills of marine organisms transfer most metal ions by simple passive diffusion and carrier molecules. All essential trace elements probably have specific carrier molecules in gill and gut epithelia. Many metal ions readily bind to organic molecules, including essential organic nutrients, and may be absorbed through the gut wall bound to the organic nutrients. Unionized forms of metals may more easily penetrate into biological membranes than polar, ionic forms [36].

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4.3. Accumulation of Heavy Metals in Different Organs Particle-bound metals are often ingested by aquatic organisms in association with food. In vertebrates, the lowered pH of the stomach helps to solubilize metals, which are then absorbed in the intestine under alkaline conditions [15]. Insoluble metal compounds and complexes can be accumulated in the tissues of marine animals by pinocytosis, endocytosis, and phagocytosis in the gut and some permeable outer epithelia. Direct uptake of particles of insoluble metal compounds, probably via gut, into tissues of marine organisms may remain as insoluble concentrations in vacuoles or intercellular spaces. Although these insoluble metals have been accumulated, they have not been assimilated. They usually remain biologically inert and are not readily accumulated from food by predators [37]. According to some researchers, some of the accumulated metals may be sequestered more or less permanently as granules in intracellular vacuoles; the remainder may desorb from binding sites and diffuse to the external, ambient medium when ambient concentrations of the metal decrease. Specific metal-binding proteins, such as metallothionein, may contribute to the control of intracellular concentrations and turnover of some metals [38,39]. Concentrations of some metals continue to increase in some tissues (particularly the kidney and liver or hepatopancreas) of some species of marine animals, resulting in an increase in body burdens of metals with increasing weight, length, and age [1]. In most cases, metals accumulate in the kidney and liver in solid concentrations that are biologically inert and not bioavailable to consumers of the marine organisms [40]. Various studies suggest that growth may partially or completely change the net accumulation of metals over time; and metal concentrations in tissues may decrease gradually during longterm exposure to metals under natural environmental conditions [41,42]. Tissue burdens of metals tend to vary widely on a seasonal basis due to differences in growth rate, body composition, sexual condition, nutrition, salinity, pH, hardness and temperature [3,43,44].

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5. TOXICITY OF SOME ESSENTIAL AND NONESSENTIAL ELEMENTS As explained in secion 4, it is impossible to discuss all heavy metal bioaccumulation values for each metal type, compounds and its ligands, which is also dependent on a number of physicochemical parameters during the creation of their forms, in a single chapter. Hence, studies on metals that are accepted as essential by several researchers, i.e. zinc, copper and chromium, and metals accepted as inessential for any concentration i.e. lead, cadmium and arsenic, will be discussed in this paper including their compounds and forms in seawater, and bioaccumulation values in different tissues of marine organisms. Inland seas face the risk of industrial waste from many industrialized and developing countries lying at their coastlines. Besides the anthropogenic waste coming via rivers and the atmosphere, heavy sea traffic increases pollution. These inland seas house a significant marine population. Hence, the “heavy metal” tables in the following chapter given for the discussion are based on some researches on marine organisms (e.g. fish, mollusks, cephalopods, crustaceans) in the inland seas.

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5.1. Zinc Zinc entering the oceans is derived from air and rivers, flux rates of zinc from the atmosphere and rivers vary widely in different geographic regions in the oceans. Zinc concentrations in estuaries and coastal waters frequently are much higher than those in the ocean (Table 1), with concentrations often as high as 4 µg l–1 and occasionally as high as 25 µg l–1 [45]. Zinc concentrations in surface waters of the oceans are nearly four times as low as deep sea [46]. Higher concentrations of zinc in marine waters are derived from upwelling of zinc-rich deep-ocean water. Zinc forms a variety of inorganic complexes in seawater, the relative proportion of different complexes depending on seawater salinity and pH. Uncomplexed zinc (Zn2+), the most bioavailable form, may represent 17 to 46 percent of the total dissolved zinc at the pH of seawater. The quantitatively most important dissolved or microparticulate zinc complexes or compounds in seawater at a pH of 8.1 are Zn(OH)2, ZnCl+, ZnCl2, and ZnCO3. Complexes with S2– or HS1– and microparticulate ZnS also may be present in anoxic waters [20]. Being a cofactor in nearly 300 enzymes, zinc is an essential micronutrient in all marine organisms, [47]. Because it is an essential micronutrient, numerous species of marine animals appear to be able to regulate tissue zinc at concentrations in seawater and sediments from normal ambient levels to incipient lethal levels [48,49]. Table 2 shows some results of studies from several countries at the Mediterranean coastline observing zinc accumulation in tissues of different species. In wild marine fish, zinc concentrations in some organ tissues may be very high, gill, hepatopancreas, liver and gonads, in particular, may contain several times zinc than edible tissues. Muscles contain much lower zinc concentrations than skin. This distribution of zinc in fish tissues undoubtedly reflects the distribution of requirements for zinc as a cofactor in several important enzymes. Much of the zinc in organ tissues of fish appears to be bound to metallothionein [50,51].

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The Risk-Based Concentrations (RBC) for zinc in edible tissues of marine animals consumed by man is 811 µg/g wet wt (4055 µg/g dry wt; dry wt was converted from wet wt by multiplying by a dry/wet ratio of 5) [1]. It is not possible to estimate a concentration of zinc in tissues of marine fish that would be expected to be associated with adverse effects in the animal themselves or their consumers, including man.

Table2.Typical Concentrations of Zinca(Zn) in different tissues of marine fish Species Mugil auratus* Mugil labrosus * Mugil capito*

Sparus auratus Atherina hepsetus Mugil cephalus Trigla cuculus Sardina pilchardus Scomberesox saurus

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Siganus rivulatus* Sargus sargus* Pelagic Sardinella aurita Trachurus trachurus Scomber japonicus Benthic Serranus scriba Epinephelus costae Cephalopholis nigri P. prayensis Pagellus acarne* Liza saliens* Sarpa salpa* Peaenus japonicus Sardina pilchardus

P. semisulcatus*

Mugil cephalus*

Zn in some tissues (µg/g dry weight) Gill Liver Muscle 33.58±18.0 53.19±21.30 6.59±1.14 5 54.93±14.06 6.90±0.16 33.06±17.3 49.20±20.72 6.53±1.34 2 36.96±19.4 6 Muscle Liver Gill 26.66±7.62 76.47±17.41 63.10±9.10 24.34±5.30 70.18±24.87 85.51±11.3 37.39±6.88 71.21±14.24 6 24.89±6.46 108.64±32.18 110.03±34. 34.58±8.64 73.22±19.84 58 16.48±2.83 68.99±14.95 89.36±55.9 8 101.85±11. 97 80.82±11.1 7 Muscle Liver Gill 9.93±3.03 182.6±76.43 33.19±14.6 5.03±1.22 88.02±21.89 16.15±5.94 Muscle 23 42 32

Liver -

Gill -

16-20 13-19 13 11-16 Muscle 5.557±1.37 27.77±2.43 26.160±3.60 Tail Muscle 24.7±3.47 Muscle 42.4±7.84

117-166 507 100 103-134 Liver 16.63±1.99 55.78±2.44 49.66±3.68 Hepatopancrea s 123.5±31.5 Liver 82.8±27.4 Hepatopancrea s Male 234–266 Female 185–284

45-88 83 120 79-97

Ref. Skin 72.69±14.42 60.65±14.94 65.87±14.88

[7]

[5]

[52]

[11]

Muscle Male 6.0–10.2 Female 4.3–10.3 Muscle 38.23±14.78

[4] Gill 137.4±47.9 [9] 51.9±14.9 Gonad Male 51.1–110 Female 41.8–116

Gill Male 167–241 Female 142–181 Skin 100.56±28.1

Gonad 281.56±91.

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[3]

[8]

Heavy Metal Pollution in Aquatic Environments Species T. mediterraneus*

Pagellus erythrinus* Sparus auratus* Mullus barbatus* P. caeruleostictus* S. undosquamis* S. chrysotaenia* T. mediterraneus Boops boops Mullus barbatus Alosa caspia E. encrasicholus Trachurus trachurus Sarda sarda Clupea sprattus Phycis phycis Argyrosomos regius Diplodus sargus Pagellus acarne Pagellus bogaraveo Pagrus pagrus H. dactylopterus Solea vulgaris Lophius piscatorius Octopus vulgaris Siganus rivulatus* Sargus sargus*

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E. microdon*

Zn in some tissues (µg/g dry weight) 19.55±10.78

Muscle 8.15±6.13 3.93±2.93 4.17±0.91 3.81±2.03 3.65±2.21 17.96±14.71 15.2±9.75 Muscle 24±13 18±7 Muscle 20.41±1.75 17.38±2.01 12.05±2.30 11.20±1.44 9.50±0.60 Muscle 14-17 15-16 14-19 15-25 15-20 12-20 17-20 19-24 19-24 61-85 Muscle 6.80-9.10 4.70-5.17 Kidney 47.73±13.26

203 Ref.

8 60.79±16.42 Skin 30.9±7.10 38.2±12.8 3.56±4.32 15.6±7.71 4.01±1.87 6.20±1.87 45.5±30.7

05 38.44±14.2 9 Gonad 130±144 24.5±21.1 24±8.60 29.4±24.3 51.5±38.6

Gill 94±36 68±24

[53]

[54]

[55]

[56]

[57] Heart 34.53±9.96

[58]

aConcentrations are in µg/g dry weight except the cases are denoted with asteriks(*) which are in µg/g wet weight References: (1) Mediterranean Sea, Italy, Storelli et al. (2006) [7]. (2) Northern East Mediterranean Sea, Iskenderun Bay, Turkey, Canli and Atli (2003) [5]. (3) El-Mex Bay, Egypt, Masoud et al. (2007) [51]. (4) Mauritania coast, France, Roméo et al. (1999) [11]. (5) Khomse Coast, Libya, Metwally and Fouad (2008) [4]. (6) North-east Mediterrenean Sea, Canli et al (2001) [9]. (7) Northern East Mediterranean Sea, Iskenderun Bay, Turkey, Yılmaz and Yılmaz (2007) [3]. (8) Northern East Mediterranean Sea, Iskenderun Bay, Turkey, Yılmaz (2003) [8]. (9) Northern East Mediterranean Sea, Iskenderun Bay, Turkey, Yılmaz and Ismen (2003) [53]. (10) Aegean and Ionian Seas, Catsiki and Strogyloudi (1999) [54], (11) Middle Black Sea (Samsun, Turkey), Tüzen (2003) [55]. (12) Portuguese coast, Carvalho et al. (2005) [56]. (13) El-Mex Bay and Eastern Harbour, Alexandria, Egypt, Khaled (2004) [57]. (14) The Arabian Gulf, Eastern province of Saudi Arabia, Ashraf (2005) [58].

5.2. Copper Estuaries and coastal waters have higher concentrations of dissolved copper than the open ocean (Table 1), the highest concentrations occuring in the low salinity regions of estuaries

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and decreasing with higher salinity [59]. Copper concentrations may be much higher in heavily industrialized coastal water. Copper can occur in seawater in several forms such as; copper-chloride complexes, copper hydroxide, copper carbonate, inorganic complexes of copper. Free cupric copper ion (Cu2+) usually represents less than 5 percent of the total dissolved inorganic copper in sea water, at a seawater pH (8.2) nearly 80 percent of the copper in seawater that is not complexed to dissolved organic ligands is complexed to carbonate (a less toxic species) (Sadiq, 1992). Monovalent copper (Cu1+) is restricted to anoxic environments. Although free copper ion and hydroxides are the most toxic species to aquatic fauna, Cowan et al. [36] showed that copper hydroxide species (Cu[OH]2 and Cu[OH]1– ) are more toxic and, by implication, more bioavailable than free copper ion (Cu2+). Table 3. Typical Concentrations of Coppera (Cu) in different tissues of marine fish Species Mugil auratus* Mugil labrosus * Mugil capito* Sparus auratus Atherina hepsetus Mugil cephalus Trigla cuculus Sardina pilchardus S. saurus

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Siganus rivulatus* Sargus sargus* Pelagic Sardinella aurita Trachurus trachurus Scomber japonicus Benthic Serranus scriba Epinephelus costae Cephalopholis nigri P. prayensis Limanda limanda Platichthys flesus P. platessa Gadus morua Boops boops Mullus barbatus

P. erythrinus* Sparus auratus* Mullus barbatus* P. caeruleostictus* S. undosquamis* S. chrysotaenia* T. mediterraneus* Lophius piscatorius* Aphanopus carbo* Molva dypterygia*

Cu in some tissues (µg/g dry weight)

Ref.

Muscle 0.93±0.14 0.84±0.17 0.88±0.06 Muscle 2.84±0.43 4.00±0.56 4.41±1.67 2.19±0.83 4.17±0.58 2.34±0.45 Muscle 2.34±0.7 1.64±0.4

Liver 154.63±24.31 169.32±13.38 177.78±10.45 Liver 33.37±16.24 54.17±35.38 202.80±265.8 26.09±8.14 29.26±13.19 18.18±6.96 Liver 31.9±8.9 16.9±5.06

Gill 2.41±0.28 2.17±0.48 2.43±0.44 Gill 5.02±0.83 14.64±3.64 13.48±7.34 10.92±5.96 8.99±1.49 11.01±2.05 Gill 8.5±3.46 3.45±1.9

Muscle 2.8 1.6 1.7

Liver -

Gill -

0.3-0.9 1.0-1.2 0.6 0.9-1.6 Muscle 0.83-0.97 0.78-1.8 1.2-2.2 0.9-1.6 Muscle 1.9±1.6 1.8±1.1

8.1-12.8 49.1 14.9 13.8-18.0 Liver 4.1-20.8 25.6-52.2 9.1-11.7 8.6-9.5

1.4-2.3 1.4 1.7 1.6-3.1

Skin 1.09±0.12 0.92±0.17 1.14±0.31

[7]

[5]

[52]

[11]

Muscle 1.75±0.28 1.70±0.31 4.01±0.21 2.08±0.12 4.18±4.62 2.72±0.69 2.06±0.18 Muscle 0.15±0.03 0.12±0.05 0.15±0.08

[61]

Gill 3.8±2.7 5.1±4.6

[54] Skin 6.32±0.40 8.24±1.13 13.7±3.34 9.09±2.96 7.01±1.98 2.13±0.41 9.12±2.63

Liver 6.53±9.00 11.87±8.53 3.95±1.73

Gill 0.57±0.12 0.88±0.18 -

Gonads 21.3±9.1 59.6±30.9 1.94±0.21 10.9±5.89 9.79±8.29 Gonads 0.56±0.64 -

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[53]

[62]

Heavy Metal Pollution in Aquatic Environments M. poutassou* M. merluccius*

0.29±0.09 0.27±0.10 Muscle 1.45±0.65 1.29±0.71

3.47±2.21 6.50±4.89

Hepatopancreas Male 24.2-101 Female 51.5-64.1 Hepatopancreas 585.7±84.3 Liver 24.74±7.75

Siganus rivulatus* Sargus sargus*

Muscle Male 17.2-41.0 Female 14.9-42.4 Tail Muscle 22.59±6.77 Muscle 14.53±6.44 Muscle 2.93±0.18 1.94±0.10 1.52±0.35 1.28±0.14 1.79±0.62 Muscle 0.7-1.6 0.7-1.3 0.9-1.4 0.9-1.3 0.7-1.3 0.7-3.0 0.7-2.3 0.7-1.2 0.7-1.9 7-16 Muscle 1.372-1.804 0.906-1.075

E. microdon*

Kidney 4.26±1.32

Heart 3.96±0.98

Mugil cephalus* T. mediterraneus*

P. semisulcatus*

Peaenus japonicus Sardina pilchardus Alosa caspia E. encrasicholus Trachurus trachurus Sarda sarda Clupea sprattus

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Phycis phycis Argyrosomos regius Diplodus sargus Pagellus acarne Pagellus bogaraveo Pagrus pagrus H. dactylopterus Solea vulgaris Lophius piscatorius Octopus vulgaris

Skin 5.36±3.43 3.33±2.61

Gill Male 32.1-44.3 Female 27.9-48.8 Gill 321.4±117.2

205 Gonads 35.37±23. 53 11.37±7.6 6 Gonad Male 55.9-114 Female 22.9-65.1

[8]

[3]

[9]

9.54±3.43

[55]

[56]

[57]

[58]

aConcentrations are in µg/g dry weight except the cases are denoted with asteriks(*) which are in µg/g wet weight References: (1) Mediterranean Sea,Italy, Storelli et al. (2006) [7], (2) Northern East Mediterranean Sea, Iskenderun Bay, Turkey, Canli and Atli (2003) [5], (3) El-Mex Bay, Egypt, Masoud et al. (2007) [52], (4) Mauritania coast, France, Roméo et al. (1999) [11], (5) The Eastern English Channel and the Southern Bight of the North Sea, Henry et al. (2004) [61], (6) Aegean and Ionian Seas, Catsiki and Strogyloudi (1999) [54], (7) Northern East Mediterranean Sea, Iskenderun Bay, Turkey, Yılmaz and Ismen (2003) [53], (8) Rockall Trough west of Scotland, Mormede and Davies (2001) [62], (9) Northern East Mediterranean Sea, Iskenderun Bay, Turkey, Yılmaz (2003) [8], (10) Northern East Mediterranean Sea, Iskenderun Bay, Turkey, Yılmaz and Yılmaz (2007) [3], (11) North-east Mediterrenean Sea, Canli et al (2001) [9], (12) Middle Black Sea (Samsun), Turkey, Tüzen (2003) [55], (13) Portuguese coast, Carvalho et al. (2005) [56], (14) El-Mex Bay and Eastern Harbour, Alexandria, Egypt, Khaled (2004) [57], (15) The Arabian Gulf, Eastern province of Saudi Arabia, Ashraf (2005) [58].

While low molecular weight lipophilic copper-organic complexes are bioaccumulated rapidly by the coastal marine diatoms, higher molecular weight organic complexes of copper are bioaccumulated inefficiently by marine animals. Because copper is an essential trace nutrient like zinc, most marine organisms have evolved mechanisms to control concentrations of the free ion in tissues in the presence of variable concentrations in ambient water,

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sediments, and foods. Above natural environment concentrations of copper, the ability to regulate copper breaks down and copper accumulates in the metallothionein. Metallothionein and very low molecular weight ligands (e.g. glutathione) in the cytoplasm of cells bind excess copper, maintaining intracellular concentrations of free copper ion at nontoxic levels. Only when the binding capacity of the intracellular ligands is exceeded and free copper accumulates in the cell, does copper become toxic [2]. Observing the samples from Mediterrenean Sea, marine fish usually contain very low concentrations of copper in muscle and skin and the highest concentrations usually are in the liver and gonads (Table 3). Although copper accumulation levels in the skin and gills depend on the fish type, accumulation in gills are in most cases higher than accumulation in skin (Table 3, ref. 5). According to RBC, copper in edible tissues of marine animals consumed by man is 100 µg/g wet wt (500 µg/g dry wt; dry wt was converted from wet wt by multiplying by a dry/wet ratio of 5) [2]. These health standards concentrations for copper in fishery products consumed by man vary from one country to another and range from 10 to 100 µg/g wet wt [60]. Muscles of several studied species (except liver) of fish and shrimps from Mediterranean frequently contain concentrations of copper lower than the RBC. The highest concentrations were in the liver with 203 and 178 µg/g wet wt in Mugil cephalus collected from İskenderun Bay, Turkey, and in Mugil capito collected from Mauritania coast, Italy, respectively. Other species usually contain lower concentrations of copper, nearly always below the RBC value (Table 3).

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5.3. Chromium Several essential trace nutrient metals including chromium are considered important environmental contaminants because of their toxicity and potential to be mobilized by man’s activities [29]. In nature, although chromium can occur nine oxidation states between 2- and 6+ [63], it primarily has two valency states in the ocean; particle-active trivalent chromium, Cr3+, and more soluble hexavalent chromium, Cr6+, [64]. In the natural pH of seawater, most of the chromium in oceanic surface waters is in fact hexavalent. In contrast, in nearshore and estuarine waters and hypoxic ocean waters, the dissolved Cr6+ /Cr3+ratio usually ranges from 1 to 20 and appears to be controlled by biological activity [65]. The concentration of total dissolved chromium in open-ocean surface waters is about 0.1 to 0.55 µg l–1 and usually decreases with depth. Cr3+ tends to bind to suspended particles or creates complexes with low molecular weight dissolved organics, because it has a low solubility in seawater. More soluble Cr6+ can be reduced readily to Cr3+ by marine organisms, dissolved organic material, and possibly by reactive ferrous iron Fe2+ [66]. In contrast, oxidation of Cr3+ to Cr6+ by dissolved oxygen is very slow at the pH of seawater and is influenced by several ions in seawater. Dominant species of Cr3+ in seawater are hydroxide ions [Cr(OH)2+, Cr(OH)21+, and Cr(OH)3] both of which have a very low solubility rate in seawater [67]. Chromium may have little effect on enzyme of energy metabolism. This element did inhibit the enzyme Na, K ATPase in the kidney and intestines, but not in gills or the liver. Na, K ATPase is critical for the function of the so-called “sodium pump” located in cellular membranes. From these results, one could predict that chromium would cause loss of sodium in the urine of freshwater fish and a

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reduction in the uptake of sodium from the water, thereby producing an altered electrolyte homeostasis [1]. Table 4. Typical Concentrations of Chromiuma (Cr) in different tissues of marine fish Species Mugil auratus* Mugil labrosus * Mugil capito* Sparus auratus Atherina hepsetus Mugil cephalus Trigla cuculus Sardina pilchardus Scomberesox saurus Siganus rivulatus* Sargus sargus* P. semisulcatus*

Mugil cephalus* T. mediterraneus* Boops boops Mullus barbatus Peaenus japonicus

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Sardina pilchardus Phycis phycis Argyrosomos regius Diplodus sargus Pagellus acarne Pagellus bogaraveo Pagrus pagrus H. dactylopterus Solea vulgaris Lophius piscatorius Octopus vulgaris Saurida undosquamis Mullus barbatus Sparus aurata

Cr in some tissues (µg/g dry weight)

Ref.

Muscle 0.15±0.06 0.16±0.05 0.15±0.06 Muscle 1.24±0.46 2.21±1.09 1.56±0.30 2.42±0.47 2.22±0.54 1.70±0.42 Muscle 0.86±0.46 0.45±0.23

Liver 0.68±0.29 0.64±0.35 0.90±0.31 Liver 1.66±0.33 3.69±2.77 4.58±3.45 8.77±4.69 17.16±9.57 5.01±2.10 Liver 2.69±2.06 1.87±0.68

Gill 0.35±0.14 0.32±0.18 0.32±0.06 Gill 3.31±0.71 14.74±6.00 4.85±1.41 10.28±4.69 7.58±1.01 14.62±9.42 Gill 1.84±1.02 0.79±0.36

Muscle Male 6.8-13.1 Female 5.9-9.3 Muscle 1.46±0.53 1.28±0.42 Muscle 1.4±1.2 1.6±1.4 Tail Muscle 1.30±0.40 Muscle 2.15±0.45 Muscle 0.7-1.3 0.8-1.0 0.4-1.3 0.16-0.99 0.6-1.7 0.58-1.07 0.93-1.1 0.91-1.3 0.03-2.1 1.1-2.1 Muscle 1.142-2.215 2.107-3.289 1.158-1.437

Hepatopancreas Male 23.1-46.1 Female 22.4-54.1

Gill Male 57.6-78.2 Female 47.0-61.7

Skin 0.20±0.07 0.21±0.05 0.23±0.07

[5]

[52]

Skin 3.22±1.28 10.90±2.29

Hepatopancreas 5.75±3.01 Liver 4.73±1.65

[7]

Gonad Male 8.0-23.2 Female 2.2-13.8 Gonad 10.06±3.59 10.60±1.95

Gill 5.0±4.3 5.1±4.7 Gill 26.63±13.50

[3]

[8]

[54]

[9]

17.76±10.14

[56]

[6]

aConcentrations are in µg/g dry weight except the cases are denoted with asteriks(*) which are in µg/g wet weight References: (1) Mediterranean Sea,Italy, Storelli et al. (2006) [7]. (2) Northern East Mediterranean Sea, Iskenderun Bay, Turkey, Canli and Atli (2003) [5]. (3) El-Mex Bay, Egypt, Masoud et al. (2007) [52]. (4) Northern East Mediterranean Sea, Iskenderun Bay, Turkey, Yılmaz and Yılmaz (2007) [3]. (5) Northern East Mediterranean Sea, Iskenderun Bay, Turkey, Yılmaz (2003) [8]. (6) Aegean and Ionian Seas, Catsiki and Strogyloudi (1999) [54]. (7) North-east Mediterrenean Sea, Canli et al. (2001) [9]. (8) Portuguese coast, Carvalho et al. (2005) [56]. (9) Northern East Mediterranean Sea, Iskenderun Bay, Turkey, Türkmen et al. (2005) [6].

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Organ tissues of fish usually do not contain significantly higher concentrations of chromium than muscle tissue does (Table 4). Gill and liver tissues of some fish from Iskenderun Bay, Mediterranean (ref. 2 and 7) contain high concentrations of chromium. The chromium accumulation for shrimp (Penaeus semisulcatus) differs depending on the sex samples from male shrimps show a declining level of chromium accumulation at gill, gonads, hepatopancreas and muscles, respectively, while chromium level in the hepatopancreas is higher than in gonads by females [3]. Because chromium is also an essential micronutrient, marine organisms have evolved mechanisms for accumulating it from the water and food and for regulating its forms, distribution, and concentrations in tissues and body fluids. However, there is relatively little published information on the bioaccumulation of chromium by marine organisms. The RBC for chromate chromium (Cr6+, CrO42–) in edible tissue of marine animals consumed by man is 8.1 µg/g wet wt (40.5µg/g dry wet). This concentration (as total chromium) is rarely exceeded in edible tissues of marine invertebrates and fish consumed by man, and most of the chromium in edible tissues is trivalent. Therefore, hexavalent chromium usually does not to pose a health risk to consumers of fishery products [2].

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5.4. Lead The concentrations of lead in clean open-ocean water are in the range of 0.002 to about 0.2 µg l–1 (Table 1), but its concentrations may increase nearly to 10 µg l–1 in some industrialized estuaries. There is an inverse relationship between salinity and dissolved lead concentration in estuaries [2]. The anthropogenic lead entering the ocean is derived mostly from burning leaded gasoline and from metal smelters. Since leaded gasoline is still in broad use, most of the lead comes from vehicular exhaust and resuspension of lead deposited on roadways. Much of this atmospheric lead finds its way into the surface waters [68]. Leaded gasolines often contain more than 500 mg l–1. As a result of the removal of alkyllead from gasoline in North America and its continuing phase-out in the rest of the world, concentrations of lead in the atmosphere and in surface waters of the ocean have decreased dramatically in recent years [69]. Inorganic lead is available in more than seven forms in seawater; including carbonate (PbCO3), chloride complexes (PbCln), hydroxide complexes (PbOHn) as the most significant ones. These are the most abundant at the normal pH and salinity of seawater [70]. Dissolved lead in estuarine and coastal waters is complexed with dissolved and colloidal organic ligands. Dissolved leads bound to sulfides and oxides, and dissolved organic matter are in a non-labile form for marine organisms. Usually less than 5 percent of the inorganic lead in seawater is in the free ionic form (Pb2+) which is considered as the most bioavailable, toxic form of inorganic lead [71]. Although inorganic lead is moderately toxic to marine organisms, alkyllead compounds usually are considered to be more toxic than inorganic lead to marine organisms. Lead apparently exerts its toxic effects by binding to cellular binding sites and biomolecules such as enzymes and hormones [72].

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Table 5. Typical Concentrations of Leada (Pb) in different tissues of marine fish Pb in some tissues (µg/g dry weight)

Siganus rivulatus* Sargus sargus*

Muscle 0.04±0.02 0.04±0.02 0.05±0.02 Muscle 5.54±0.74 6.12±1.25 5.32±2.33 4.27±1.03 5.57±1.03 2.98±0.03 Muscle 1.69±0.6 1.17±0.2

Liver 0.30±0.14 0.30±0.19 0.18±0.06 Liver 8.87±2.13 41.24±46.27 12.59±5.80 23.01±10.87 39.43±17.91 17.54±7.89 Liver 6.81±2.0 3.95±2.7

M.merluccius* Mullus Barbatus*

Muscle 49.10-3-141.10-3 39.10-3-298.10-3

Liver 57.10-3-158.10-3 99.10-3.970.10-3

Muscle 0.036±0.01 0.012±0.006 0.010±0.007 Muscle 0.001-0.12 0.008-0.04 0.01-0.10 0.001-0.07 Muscle 0.05±0.01 0.10±0.03

Liver 1.94±0.21 1.88±0.16 1.82±0.13 Liver 0.04-0.18 0.08-0.26 0.09-0.38 0.21±0.007 Liver 0.09±0.01 0.21±0.11

Muscle Male 0.3-0.6 Female 0.2-0.6 Tail Muscle 5.40±1.04 Muscle 7.67±1.73 Muscle 7.45±3.44 1.03±0.49

Hepatopancreas Male 1.1-1.3 Female 0.4-0.9 Hepatopancreas 14.70±2.30 Liver 19.99±9.98

Mugil auratus* Mugil labrosus * Mugil capito* Sparus auratus Atherina hepsetus Mugil cephalus Trigla cuculus Sardina pilchardus Scomberesox saurus

Pagellus acarne* Liza saliens* Sarpa salpa* Limanda limanda Platichthys flesus Pleuronectes platessa Gadus morua Xiphias gladius* Thunnus thynnus*

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P. semisulcatus*

Peaenus japonicus Sardina pilchardus Mugil cephalus* T. mediterraneus* Pagellus erythrinus* Sparus auratus* Mullus barbatus* P. caeruleostictus* S. undosquamis* S. chrysotaenia* T. mediterraneus Lophius piscatorius* Aphanopus carbo* Molva dypterygia* M. poutassou* M. merluccius*

Muscle 1.13±0.33 2.16±0.35 2.24±0.27 2.24±0.38 2.47±4.24 1.41±0.58 1.00±0.18 Muscle 0.002±0.007 0.009±0.012 0.003±0.002 0.008±0.007 0.008±0.016

Liver 0.05±0.018 0.05±0.071 0.05±0.080 0.05±0.018 0.05±0.042

Ref. Gill 2.33±0.32 2.49±0.40 2.48±0.44 Gill 13.31±2.87 12.37±4.76 8.95±3.07 12.81±4.74 8.99±2.48 16.25±4.52 Gill 8.83±2.4 6.6±2.6

Skin 0.10±0.06 0.17±0.05 0.28±0.17

[2]

[5]

[52]

[77]

[4]

[61]

[78] Gonad Male 0.9-3.0 Female 0.1-1.1

Gill Male 0.6-0.9 Female 0.7-1.7 Gill 93.63±20.78

[3]

[8]

20.65±9.69

Gill 0.006±0.046 0.013±0.074 -

Skin 37.39±18.44 4.78±1.98

Gonad 62.33±26.17 8.41±2.69

Skin 4.12±0.45 11.7±2.61 16.2±3.50 12.1±1.37 8.85±2.31 1.17±0.45 5.15±1.62

Gonad 12.5±4.81 87±46.5 1.85±0.54 8.57±3.17 5.42±3.68 Gonads 0.005±0.012 -

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[9]

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Table 5. (Continued) Alosa caspia E. encrasicholus Trachurus trachurus Sarda sarda Clupea sprattus

Muscle 0.52±0.16 0.38±0.02 0.85±0.16 0.22±0.04 0.74±0.11

Phycis phycis Argyrosomos regius Diplodus sargus Pagellus acarne Pagellus bogaraveo Pagrus pagrus H. dactylopterus Solea vulgaris Lophius piscatorius Octopus vulgaris

Muscle 90%) and poor in sand [122].

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Location Northern inner shelf of Sea Marmara Erdek Bay Gulf of Izmit Golden Horn Estuary Gulf of Gemlik Northern shelf Istanbul Metroplitan offshore The Sea of Marmara Northern inner shelf of Marmara Sea Gulf of Izmit Average Shale

Table 5. The mean concentration of metals in sediments along Marmara Sea Coast Heavy metals concentrations μg/g Cd Cu Co 19.8

0.2 μg/g) in the northern part of Haifa Bay extends approximately 3 km to the north and south of the chlor-alkali plant outfall, and about 1 km offshore to a water depth of 12 m. The sediments in this area are composed mostly of fine-grained quartz sand (the dominant mode (>65%) is 125-150 μm with less than 3% silt and clay particles) derived from the Nile Delta [159,160]. As mentioned by Krom et al. [161], the levels of mercury even at the most contaminated stations are moderate compared to those found in sediments adjacent to other chlor-alkali plants.

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Heavy Metal Contaminations in Mediterranean Sediments

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Table 7. Concentration of metals in sediment of Mediterranean coast of Israel Heavy metals concentrations (μg/g)

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

Location Kishon river estuary (1988-1992) Opposite Kfar Galim Opposite Tira (19901992) Opposite Zikhron Yaakov (1988-1992) Taninim river estuary (1989-1992) Hadera river estuary Alexander river estuary Poleg river estuary (1989-1992 Opposite Tel-Aviv (1988-1990) Yarkon river estuary Soreq river estuary Avteach r. estuary (1988-1989) Haifa Bay (1984-1987)

Hg 0.046-0.070

Cd 0.10-0.19

Cu 233-4.21

Fe 2050-3230

Pb 9.29-10.90

Zn 11.20-20.40

ND-0.007

0.08-0.31

1.52-2.05

1054-2192

4.98-7.50

3.75-6.13

0.004-0.006

0.07-0.09

1.47-1.52

1436-1353

5.03-6.57

3.80-5.98

ND-0.011

0.06-0.11

1.26-1.51

1360-2137

4.85-6.77

3.69-5.81

ND.-0.006

0.05-0.09

1.28-1.44

1060-1545

4.61-6.15

3.35-5.46

ND-0.011

0.06-0.10

1.23-1.63

1350-2215

3.59-6.61

3.15-6.95

ND-0.005

0.014-0.09

1.15-1.56

1009-2021

4.10-6.04

2.62-10.70

ND-0.008

0.07-0.09

1.30-1.42

1640-1704

4.32-5.52

3.37-5.27

ND-0.054

0.0110.032

3.48-8.57

1998-3290

5.91-10.80

10.20-28.40

ND-0.020

0.07-0.18

2.78-5.00

1896-5896

5.24-10.30

6.52-18.80

ND-0.009

0.05-011

1.20-1.50

2060-3413

4.25-5.04

4.50-6.38

ND

0.10-0.11

1.53-1.75

2430-3963

5.25-5.50

6.68-8.40

0.03-0.78

0.13-1.25

1.7-40.3

0.11%-0.66

5.8-29.9

8.06-108.7

Referenc es [141]

[151]

Marine sediments inside Haifa Bay have a relatively high amount of carbonates, which consist mainly of mollusk shell debris, but outside Haifa Bay, different composition and structure where sediment consists mainly of coarse sand (fraction 0-5-1-0 mm) and medium sand (fraction 0.25-0.50 mm). The Kishon river system, which is the only point trace metal pollution source in southern Haifa Bay [144], does not affect the sediments in the outer part of Haifa Bay [162]. There is also evidence that there is no trace metal pollutant transfer perpendicular to the shore direction from inner to outer Haifa Bay. The mercury contamination of the sediments in these areas was found to be logically decreased with increase of distance from the plant [163]. Data recorded by [162] showed that sediments of core in the outer part are practically free of excess mercury. Thus neither dissolved mercury nor the polluted fine-grained

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sediment fractions were transferred from the inner part of Haifa Bay over Foxhound Reef and Akko Ledge in the outer Bay direction. This indicates that all the mercury which has been reaching sediments in the north inner part of Haifa Bay [151] are from the Chlor-alkali plant situated on the shore.

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8. EGYPT Alexandria is the main summer resort in Egypt (about 4 million citizen and two million summer visitors). About 40% of the nation’s industry surrounds the city [164]. The area of the study covers the coastal strip along Alexandria city from Agami in the west to Maamoura in the east. The area is covered with well-sorted sand that differs locally in the origin, type of sediments and texture [165]. More than 18 x 106 m3 of untreated sewage and wastewater were discharged annually from a large numbers of outlets into Alexandria coastal water through the local sewerage system [166]. Pollutants are produced from industrial, anthropogenic and agricultural activities [164]. The direct discharge of raw sewage and industrial wastewater causes high rate of pollution to the coastal waters off Alexandria [164]. El-Sayed et al. [167] recorded that mercury concentration fluctuated from 8.02 to 15.5 μg/g in the beach sands from the polluted area beyond the Chlorine-Alkali plant at El-Mex area, west. The inner shelf sediments off Alexandria showed a slight tendency to decrease in mercury concentration with increased distance from the effluent pipe of the plant and ranged from 0.14 to 1.4 μg/g. The Western Harbor, Alexandria is characterized by high mercury concentration in the fine, organically rich sediments covering this sheltered area. Patches of high mercury associated with fine sediments covering the inner shelf was also observed. It is presumed that the elemental mercury discharged the area beyond Alexandria is converted to Chloro-complexes as HgCl-- or HgCl0, due to the large amounts of the chlorinated byproducts discharged from the plant through the same effluent pipe. Aboul-Naga et al. [168] studied the distribution of total and leachable fraction of Pb, Ni and Cd in surface sediments of Abu Qir Bay, east of Alexandria which receives effluents of many industrial activities, domestic and agricultural drainage (about 2×106 m3day, Said [169]). Total metal concentrations ranged between 23.7 and 125.9 μg/g (average 65.5±21.1) for lead, 27.7 to 162.9 μg/g (average 91.0±35.5) for nickel and 1.58 to 7.20 μg/g (average 4.86±1.28) for cadmium, the highest concentrations were measured in the vicinity of points recognized as potential sources pollution. Concentrations in the leachable fraction were relatively low and averages for Pb, Ni and Cd were 2.3, 32.0 and 0.10 μg/g, respectively. They reported that Ni was the most mobile among the three studied metals as it fluctuated between 26 and 49% from its total concentration. More than 97% of Pb and Cd are present in less mobile forms. Variations of the residual concentrations of Pb and Ni appeared as mostly related to the mud and organic matter content which means that this fraction is tightly held in the crystal lattice and/or present as sulphide and organic complexes. Organic matter and mud contents explain most of the variability of the leachable Pb, which agrees with the high adsorption capacity of the fine fraction. Only the leachable Ni was found to be related to the carbonate content, which explains the relative higher mobility of this element. The distribution, enrichment and accumulation of Cd, Cu, Zn, Cr, Pb and Al in the surficial sediments of the Eastern Harbor, Alexandria City were studied by Abdallah [170].

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The concentrations of the five metals ranged from 83.4 to 3168.7, 23.0-117.1, not detected39.0, 0.08-3.11 and 37.0-154.0 for Zn, Cu, Cr, Cd and Pb, respectively. Chromium falls in the group of elements without enrichment (EF < 1) in the study area. According to calculations of enrichment factors, Pb and Cd are of moderately severe enrichment, while Zn has the highest level of enrichment (severe enrichment). Regarding other elements, Cr is at back-ground levels and Cu is of minor enrichment. The distribution of the concentration of metals gives information about sources of pollution in the area; Al displays a distribution differing from pollution derived elements. Furthermore, a similar pattern of distribution shared by Cr and Cu indicates that mixed sewage wastes affect the area. Finally, similar distribution patterns for Cd, Zn and Pb with high EF point to the operation of numerous shipyards (construction and paint) in the same area. A sequential extraction procedure was applied to identify forms of Mn, Cu, Cd, Cr, Zn and Fe in El-Mex Bay, West of Alexandria [171]. The concentrations of trace metals were found to be (μg/g) for Mn: 1930.2, Cu: 165.3, Cd: 60.9, Cr: 386.3, Zn: 2351.3 and Fe: 10895. Most of elements were found in reducible fractions, except Fe found in acid soluble residue, characterizing stable compounds in sediments. Labile (non-residual) fractions of trace elements (sum of the first four fractions) were analyzed because they are more bioavailable than the residual amount. Correlation analysis was used to understand and visualize the associations between the labile fractions of trace metals and certain forms, since Fe-and Mnoxides play an important role in trace metals sorption within aquatic systems, especially within El-Mex Bay sediments that characterized by varying metal bioavailability. The total and leachable concentrations of Co, Zn, Mn, and Sr were studied by ElSammak and Aboul-Kassim [172] along the Alexandria coastal area from Agami in the west to Maamoura in the east where Pollutants are produced from industrial, anthropogenic and agricultural activities [164]. The total average concentrations of Co, Ni, Zn, Mn, Mg, Fe, Si were 50.24±19.5 μg/g, 85.7±34.1 μg/g, 101.8±43.9 μg/g, and 1105.4±443.3 μg/g, 1.149±0.757%, 10.36±4.13%, and 16.1±8.65%, respectively. The calculated contamination factors are found to fall in the following sequence: Co>Ni>Fe>Sr>Mn>Zn. Pollution Load Index (PLI) is used to find out the mutual pollution effect at different stations by the different metals in this area, which varies between 0.151 and 1.77 with an average of 1.279 ± 0.417 μg/g. In general, there is an increase of PLI toward the western side. The Eastern Harbor and Mex bay are said to the most polluted areas at Alexandria beach [173]. Khalil et al. [174] reported that the concentrations of Fe, Mn, Zn, Cu, Ni, Co, Cd and Pb fluctuated from 2685 to 3072, 56.27-64.69, 7.89-21.63, 2.67-7.48, 2.92-14.75, 1.42-4.22, 0.75-1.40, and 4.51-8.51μg/g, respectively, in sediment samples in front of Lake Brullus. The distribution of vanadium along the coastal area of the Egyptian Mediterranean Sea was reported by El-Moselhy [175]. The concentration of vanadium fluctuated between 3.76 and 168.0 μg/g with an average value 40.58 μg/g. The highest value was recorded in front of Lake Manzala sector due to the huge amount of wastewater effluents from the lake, as well as the effect of waiting area for ships passing through the Suez Canal to the Red Sea. A relatively higher value was observed at Port Said Station (103.9 μg/g) which suffers from pollution through different sources such as industrial and shipping activity, fishing port, ship waiting area, and effluents from Lake Manzala. The lowest value was recorded in front of ElArish city, representing a relatively clean area. El-Dabaa and Marsa Matruh sectors recorded

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relatively low values of vanadium which ranged from 4.49 to 8.41 μg/g which are far away from the pollution sources. Total and leachable concentrations of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn in sand and mud fractions in surficial sediments from Sidi-Krir (west of Alexandia) to Rashid (east of Alexandria) along the Mediterranean Sea were reported by El Nemr et al. [176]. The mean concentration of total heavy metals in sandy sediment fractions represented the next decreasing order Fe > Mn > Cu > Pb > Zn > Ni > Cr > Co > Cd and the mean concentrations of leachable heavy metals decreased in the order Fe > Mn > Pb > Ni > Zn > Co > Cu > Cr > Cd. Cadmium, cobalt and chromium showed the lowest concentrations for both total and leachable fractions at most studied locations. The mean concentration of the total heavy metals in muddy sediments fractions represented the next decreasing order Fe > Mn > Cr > Zn > Pb > Ni > Cu > Co > Cd and the mean concentrations of leachable heavy metals decreased in the next order Fe > Mn > Zn > Pb > Cu > Ni > Co > Cr > Cd. Cadmium and cobalt showed the lowest concentrations for both total and leachable fractions at most studied locations. The study showed that the heavy metal concentrations in sediments were varied significantly within sediment samples and locations. The mean concentrations of total heavy metals were in mud and sand fractions were 6.95 and 11.83 for Cd, 40.17 and 39.20 for Co, 110.80 and 58.25 for Cr, 70.44 and 41.71 for Cu, 118230.0 and 9314.5 for Fe, 814.87 and 469.19 for Mn, 72.92 and 71.20 for Ni, 78.72 and 92.93 for Pb, 79.87 and 75.31 for Zn, respectively. In addition, this investigation has clearly shown that the Egyptian coast along Mediterranean Sea received heavy inputs of heavy metals. Several metals (Cd, Cu, Ni and Pb) exhibited concentrations that are sufficiently high exceed sediment quality guidelines. The metals contamination in sediment of studied locations may be of anthropogenic origin with the exception of some local anomalies. The difference in concentrations of heavy metals between mud and sand in the same location is reasonable, due to the difference in capability of mud and sand to adsorb heavy metals from the water column. The PCA shows that the sediment samples could be classified into six groups according to their metal concentrations in total fractions for both sand and mud. On the other hand, the PCA for metals exhibited that the nine heavy metals studied could be classified into four groups according to their median metal concentrations in both sandy and muddy sediment samples. The application of different statistical methods is an efficient tool in achieving better understanding of the state of the environment. El Sikaily [177] reported the contamination of heavy metals (Al, Co, Cr, Cu, Ni, Pb, Cd, Cu and Zn) in ten surface sediment samples collected from Egyptian Mediterranean coast. The concentration fluctuated between 0.385-16.465, 0.473-1.068, 9.208-33.399, 3.50023.180, 20.672-63.024, 7.500-39.315, 22.734-122.921 μg/g dry weight for Al, Cd, Co, Cr, Cu, Ni, Pb, and Zn, respectively. El Sikaily [177] applied different normalizing methods to the data such as surface/background ratio, index of geoaccumulation (Geo-Index), reference metal normalization, to compensate the influence of the natural variability in sediment mineralogy and granulometry and to assess whether the concentrations observed in surface sediments represent a background or contaminated levels. El Sikaily [177] reported that the two methods of calculations (Cf and Igeo) were useful and successful but Igeo was more specific to determine the degree of contamination than the contamination factor which was attributed to the wide scale of contamination factor. The concentrations of certain heavy metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pd and Zn) in the total and labile fractions of muddy sediment samples collected from eleven sites in Lake

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Burullus in 2003 were reported by El Nemr [178] to evaluate the pollution status of the lake. The average concentrations of the heavy metals analyzed in total sediment fractions exhibited the following decreasing order: Fe (12755-45869 mg/kg) > Mn (1311-4008 mg/kg) > Cu (32.27-167.1 mg/kg) > Ni (64.2-115.7 mg/kg) > Zn (44.83-141.37 mg/kg) > Cr (50.81-81.98 mg/kg) > Pb (46.18-80.35 mg/kg) > Co (35.05-76.9 mg/kg) > Cd (7.4-12.34 mg/kg), while the average concentrations of the heavy metals analyzed in the labile fraction followed the order: Fe (2.303-8.997 mg/kg) > Mn (1144-3588 mg/kg) > Cu (28.25-109.75 mg/kg) > Ni (48.0-68.0 mg/kg) > Pb (31.70-69.85 mg/kg) > Zn (30.53-84.69 mg/kg) > Co (26.37-59.15 mg/kg) > Cr (15.09-48.15 mg/kg) > Cd (5.05-8.33 mg/kg). The concentrations of all studied heavy metals ranged between the Effect Range-Low (ERL) and the Effect Range-Median (ERM) for most studied locations in the lake. Metal pollution index (MPI) showed very high values for both total and labile fractions at all the examined locations. El Nemr [178] reported that the field observation revealed that Lake Burullus received industrial, agricultural and domestic sewage and suggested that the anthropogenic input was the main source of heavy metal contamination. El Nemr [178] also reported the health hazard calculations for the contaminated sediments and exhibited that there is a possibility of health risk due to longterm exposure of the human to the polluted sediments of Lake Burullus.

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9. ALGERIA Sediments in Algiers Bay have a high capacity to concentrate and retain toxic trace elements due to the fine fraction ( Zn > Pb > Cu > Cr and recorded that the concentration fluctuated between 199-370, 60-356, 16-93, 23-79, 15-63 μg/g, respectively. Benamar et al. [183] reported that the distribution of Cr, Cu, Zn and Pb in surficial sediment was irregular and depended on the bay morphology. The level of pollution by heavy metals of the bottom sediments in Algiers Bay has been shown to be significant compared with that of Surkouf area, considered to be a region with low anthropogenic activity. The central and western sectors of the bay, near the main emission of waste water and of Algiers harbor, have the highest concentrations of copper and lead. In contrast, the sector in front of the mouth of El-Harrach River has low concentrations of copper. This is due to the low content of organic carbon and clay minerals [179]. This trend is not seen for lead. The enrichment in the western sector of these elements could be explained by the absorbability of

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these elements for organic matter. It was pointed out that the sediments of the western sector of the bay are rich in organic matter [179]. The geographical distribution of lead and copper seems to be dependent on sedimentary facies where they recorded high levels in fine sediment as previously reported by Arnoux et al. [184] who pointed out

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that lead and copper contents increase in the fine fraction ( coarse for all the metals. The average total extractable metal concentrations for Cd, Cr, Cu, Fe, Ni, Pb, and Zn were 1.1, 8.8, 4.7, 1,291.3, 13.9, 5.7 and 20.4 μg/g, respectively. The northeastern shelf had the lowest metal levels while the highest were in northwestern part mainly due to the significant tourism activities in the northwestern part. Comparison of our results to the Earth’s crust values and to previous studies points out that our samples were relatively unpolluted with respect to the heavy metals investigated; most of the metals are not from anthropogenic sources. Enrichment factors as the criteria for examining the impact of the anthropogenic sources of heavy metals were calculated, and it was observed that the investigated samples were not contaminated with Cr, Cu, and Fe, moderately contaminated with Ni, Pb, and Cd, and contaminated with Cd in some sites.

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[34] Long, E., Macdonald, D., Smith, S., and Calder, F. (1995). Incidence of adverse biological effects within ranges of chemical concentrations in marine and estuarine sediments. Environ. Manag., 19(1), 81-97. [35] Giusti, L, and Hao Z.H. (2002). Heavy metals and arsenic in sediments, mussels and marinewater from Murano (Venice, Italy) Environ. Geochem. Heal., 24, 47-65. [36] Romano, E., Ausili, A., Zharova, N., Magno, M.C., Pavoni, B. and Gabellini, M. (2004). Marine sediment contamination of an industrial site at Port of Bagnoli, Gulf of Naples, Southern Italy. Mar. Pollut. Bull., 49, 487-495. [37] Adamo, P., Arienzo, M., Imperato, M., Naimo, D., Nardi, G. and Stanzione, D. (2005). Distribution and partition of heavy metals in surface and sub-surface sediments of Naples city port. Chemosphere, 61, 800-80. [38] Buccolieri, A., Buccolieri, G., Cardellicchio, N., Dell’Atti, A.., Di Leo, A. and Maci, A. (2006). Heavy metals in marine sediments of Taranto Gulf (Ionian Sea, Southern Italy). Mar. Chem., 99, 227–235. [39] Sprovieri, M., Feo, M.L., Prevedello, L., Manta, D.S., Sammartino, S., Tamburrino, S. and Marsella, E. (2007). Heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in surface sediments of the Naples harbour (southern Italy). Chemosphere, 67, 998-1009. [40] Celico, F., Esposito, L. and Mancuso, M. (2001) Complessita idrodinamice idrochimica dellarea urbana di Napoli: scenari interpretative (Hydrodynamic and hydrochemical complexity of Naples urban area: some interpretation). Geol. Tecn. Ambientale, 2, 3554. [41] Damiani, V., Baudo, R., De Rosa, S., De Simone, R., Ferretti, O., Izzo, G. and Serena, F. (1987). A case study: Bay of Pozzuoli (Gulf of Naples, Italy). Hydrobiol., 149, 201211. [42] Leodaris, S., Maroukian, X., Dassenakis, M., Poulos, S., Paulopoulos, K. and Kloukiniotou, M. (1994). Environmental Study in the Avlida Coastal Zone (South Euvoikos Gulf). Depart. of Geology, Univ. Athens, pp. 16–24. [43] Dassenakis, M., Andrianos, H., Depiazi, G., Konstantas, A., Karabela, M., Sakellari, A. and Scoullos, M. (2003). The use of various methods for the study of metal pollution in marine sediments, the case of Euvoikos Gulf, Greece. Appl. Geochem., 18, 781-794. [44] Dassenakis, M. and Kloukiniotou, M. (1994). Cu and Zn in sediments of southern Euripos straits, Greece. In: Proc. 6th Internat. Conf. Environmental Contamination, Delphi, Greece, pp. 368–370. [45] Dassenakis, M., Degaita, A. and Scoullos, M. (1995). Trace metals in sediments of a Mediterranean estuary affected by human activities: Acheloos river estuary, Greece. Sci. Total Environ., 168, 19-31. [46] Salomons, W. and Forstner, U. (1984). Metals in the Hydrocycle. Springer-Verlag, Berlin. [47] Kaberi, H. and Scoullos, M. (1996). The role of the green algae Ulva sp. in the cycling of copper in marine coastal ecosystems. MAP/UNEP Tech. Rep. Ser., 104, 83–96. [48] Leal, M.F.C., Vaconcelos, M.T.S.D. and Van der Berg, C.M.G. (1999). Copper induced release of complexing ligands similar to thiols by Emiliana puxlegi in seawater cultures. Limnol. Oceanog., 44, 1750-1762.

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[168] Aboul-Naga, W.M., El Sayed, M.A. and Deghedy, E.M. (2002). Leachable and Residual Pb, Ni and Cd in the sediments of Abu-Qir Bay, Alexandria. Egypt. Bull. Nat. Inst. Oceanogr. Fish., A.R.E., 28, 307-317. [169] Said, M.A., Ennet, P., Kokkila, T., Sarkkula, J. (1995). Modelling of transport process in Abu-Qir Bay, Egypt. Proceeding of the second International Conference on the Mediterranean Coastal Environmental. MEDCOAST 95. [170] Abdallah, M.A.M. (2007). Accumulation and distribution of heavy metals in surface sediments of a semi-enclosed basin in the southeastern Mediterranean Sea, Egypt. Med. Mar. Sci., 8, 31-40. [171] Abdallah M.A.M. (2009). Speciation of Trace Metals in Coastal Sediments of El-Mex Bay South Mediterranean Sea–West of Alexandria (Egypt). Environ. Monit. Assess., DOI10.1007/s10661-006-9507-Z. [172] El-Sammak. A.A. and Aboul-Kassim T.A. (1999). Metal Pollution in the Sediments of Alexandria Region, Southeastern Mediterranean, Egypt. Bull. Environ. Contam. Toxicol., 63, 263-270. [173] El-Sammak, A.A. and Aboul-Kassim, T.A. (1998). Copper and lead concentrations in the sediments of Alexandria Region Southesatern Mediterranean, Egypt. Fresenius Environ. Bull., 7(3-4), 126-133. [174] Khalil, M.Kh., Radwan, A.M. and El-Moselhy, Kh.M. (2007). Distribution of phosphorus fractions and some of heavy metals in surface sediments of Brullus Lagoon and adjacent Mediterranean Sea. Egypt. J. Aquat. Res., 33(1), 277-289. [175] El-Moselhy, Kh.M. (2006). Distribution of vanadium in bottom sediments from the marine coastal area of the Egyptian Seas. Egypt. J. Aquat. Res., 32(1), 12-21. [176] El Nemr, A., El-Sikaily, A. and Khaled, A. (2007). Total and leachable heavy metals in muddy and sandy sediments of Egyptian coast along Mediterranean sea. Environ.Monit.Assess., 129,151-168. [177] El-Sikaily, A. (2008): Assessment of some heavy metals pollution in the sediments along the Egyptian Mediterranean coast. Egypt. J. Aquat. Res., 34(3), 58-71. [178] El Nemr, A. (2003): Assessment of heavy metal pollution in surface muddy sediments of Lake Burullus, southeastern Mediterranean, Egypt. Egypt. J. Aquat. Biol and Fish, VoI.7, No.4: 67-90 [179] Maouche, S. (1987). Mecanismes hydrosedimentaires en baie d'Alger (Algerie). Doctorat thesis, Perpignan University, p.213. [180] Leclaire, L. (1972). La sêdimentation holoceÂne sur le versant mêridional du bassin Algéro-Baleares. Thése d'Etat, Faculté des sciences de Paris, p. 382. [181] Chouikhi, A., Boulahdid, M., Sellali, B., Boudjellal, Y. and Et Azzouz, M. (1991). Distribution des sels nutritifs des eaux interstitielles et des mêtaux lourds dans les sêdiments marins superficiels du Golf d'Arzewet de la baie d'Alger. Symposium International sur la pollution des eaux marines. Casablanca, p. 10. [182] Boudjellal, B., Sellali, B., Benoud, D. and Et Mallem, M.T. (1992). Mêtaux lourds dans les sédiments superficiels de la baie d'Alger. Résultats du workshop sur la circulation des eaux et pollution des cotes mêditerraniéennes du Maghreb. Rabat, 153-156. [183] Benamara, M.A., Toumerta, I., Tobbechea, S., Tchantchane, A. and Chalabi, A. (1999). Assessment of the state of pollution by heavy metals in the surficial sediments of Algiers Bay. Appl. Rad. Isotopes, 50, 975-980.

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[184] Arnoux, A., Monod, A.J.L., Tatossian, J., Blanc, A. and Oppetit, F. (1980). La pollution chimique des fonds du Golfe de Fos. C.I.E.S.M. VI. J. Etud. Pollut., Cagliari. [185] Lambert, C.E. (1981). Le cycle interne du Fer et du Manganese et leurs interactions avec la matieÁre organique dans l'oceÂan. Doctorat thesis, de Picardie University, p. 235. [186] Chester, R., Stoner, J.M. (1985). Trace elements in total particulate material from surface sea-water. Nature, 255, 50-51. [187] Faguet, D. (1982). Influence des substances humiques sur les formes dissoutes et particulaires de quelques meÂtaux (Zn, Fe, Co, Mn) dans les milieux marins et lagunaires. Doctorat thesis, Perpignan University, p. 129. [188] Alomary, A. A.; Belhadj, S. (2007). Determination of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) by ICP-OES and their speciation in Algerian Mediterranean Sea sediments after a five-stage sequential extraction procedure. Environ. Monit. Assess 135, 265-280.

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Chapter 11

CADMIUM AND ORGANOTIN POLLUTION IN AN ESTUARINE ENVIRONMENT FROM ARGENTINA: AN OVERVIEW S. Botté1 (1), F. Delucchi (1), R.H. Freije2 (2), and J.E. Marcovecchio (1) 1. Área de Oceanografía Química, Instituto Argentino de Oceanografía (IADO).CCTCONICET-Bahía Blanca. Florida 7000, Edificio E-1. CC 804, B8000FWB Bahía Blanca, Argentina 2. Química Ambiental, Departamento de Química, Universidad Nacional del Sur (UNS). Av.Alem 1252, 8000 Bahía Blanca, Argentina

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Total heavy metal concentrations have been monitored for almost thirty years, while organotin compounds have only been evaluated for the last few years. Intertidal as well as subtidal surface sediments were fully analyzed and the corresponding results are included in this review. Cadmium contents within sediments were slightly higher close to the area where industrial effluents are discharged, as well as near the harbour zones during the study period. The analysis revealed that –with the exception of the last analyzed period- cadmium is at background concentrations within the study system. A permanent monitoring programme within the inner zone of the estuary has demonstrated that cadmium concentrations slightly increased during the study period, indicating a regular input of these metals into the system. In addition, recent studies have shown similar contents of cadmium on both tidal flats and sub-tidal sediments within the estuary. Organotin compounds (DBT and TBT) were found in the sediments of the entire studied area. Their concentrations ranged from very low values within low impacted areas to higher ones next to the most active harbour facilities. The highest amounts of both DBT and TBT were recorded in the neighbourhood of dry docks where careenage of ships may be the main source. These results throw light upon the process of accumulation of cadmium and organotin compounds within the analyzed sediments, allowing us to 1

E-mail: [email protected], [email protected], [email protected]. Fax: (54-291) 4861112/1519 2 E-mail: [email protected]. Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

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S. Botté, F. Delucchi , R.H. Freije et al. conclude that the inner area of the Bahía Blanca estuary could be considered an intermediately polluted system.

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1. INTRODUCTION Coastal zones present great dynamism and are submitted to constant changes depending on several factors such as climatic conditions, tides and the input of freshwater and sediments from the continent. The tide function is essential to drive a number of processes such as erosion, sediment circulation and deposition, which play an important role in settling down environmental morphology and sediment distribution. Most processes occurring within an estuary are related to the input, output, transport and distribution of sediments. The biota-sediment interactions are always present and vary with both the environmental and geomorphological conditions. Some artificial processes such as dredging alter the channels and outline maximum turbidity areas, increasing the sediment deposition [1]. Moreover, most biological and chemical pollutants are closely related to the fine suspended particle matter, SPM [2]. The geomorphology of the analysed coastal zone may determine hydrodynamic conditions which foster the deposition of particles (with the adsorbed pollutants), leading to a possible alteration of the benthonic communities [1]. Estuaries are zones of harbour, industrial and recreational development and essential from the environmental point of view. They usually become sediment sinks as well as pollutant deposits. Both the settlement of ports in low flushing areas and the deposition of sediments in estuaries turn these environments into ideal areas to study the input, circulation and accumulation of pollutants [3]. The use of TBT was internationally banned for vessels lesser than 25 m in length in the late 1980s [4] and in Argentina in 1998 [5], due to its high toxicity in different marine organisms. However, there are only a few studies about organotin pollution in the coastal zones of Argentina [6-9]. In Argentina there are only guide levels of Cd for soil qualities but not for marine sediments or seawater, which regulate maximum levels of Cd in soils destined to agricultural (3 µg g-1), residential (5 µg g-1) and industrial uses (20 µg g-1), respectively [10]. In addition, it must be considered that background concentrations of cadmium in the shale/clays and sediments were opportunely described between 0.2 and 0.3 µg g-1 [11]. Although cadmium concentrations generally range from 0.1-10.0 µg g-1 dry wt in estuarine sediments, its concentrations in contaminated coastal sediments may exceed 200 µg g-1 dry wt [12]. However, this kind of information is scarcely available within Bahía Blanca estuarine biota [13-18]. In tidal flat estuaries, as the case of Bahía Blanca, sediments may remain in motion for a long time as pollutant traps [19] depending on their hydrodynamics. Many pollutants, such as heavy metals and organotin compounds, enter the aquatic system as consequence of several anthropic processes and generally accumulate in coastal sediments, and eventually may be transferred to the biota [20,21]. Besides, the potentially deleterious effects of toxic elements on marine and estuarine organisms have been fully recognized [22]. This chapter refers to only two pollutants: cadmium and organotin compounds (DBT and TBT) for several reasons, both are extremely toxic at low concentrations, the area is strongly influenced by traffic of

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vessels, and both are included in different kinds of coating pigment (for corrosion resistance, corrosion prevention, antifoulant). The impact of urban sewage, harbour activities and industrial waste on metal distribution (Cd) as well as on organotin pollution (DBT and TBT) in estuarine sediments were fully studied within different areas of the Bahía Blanca estuary in Argentina. The obtained results are a good starting point to assess the environmental condition of this system, and is an essential step to develop an Integrated Management Programme directed to preserve the natural resources within this estuary.

2. HEAVY METAL POLLUTION WITHIN ESTUARIES

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2.1. Composition and Sources Estuaries include large amounts of human activity which are responsible for most pollutant inputs. Both the industrialized societies and the urban settlements have significantly increased heavy metal accumulation within the marine environment. In addition, heavy metals not only deserve special attention but are also the focus of numerous environmental investigations due to their high toxicity, extreme persistence, non-degradability, and a strong tendency to be bioaccumulated [12,23,24,25,26]. In order to understand their potential risk and to study their environmental behaviour, heavy metals can be grouped into two categories: (i) Transitional Metals (e.g. copper, cobalt, iron), and (ii) Metalloids (e.g. arsenic, cadmium, lead, mercury, and tin). The first group includes those elements which are essential for the metabolic function of marine organisms when in small amounts, but which can become toxic for biota at high concentrations. In contrast, the elements of the second group do not have any biological role, and can be toxic at extremely low concentrations. Moreover, organometal pollutants (e.g., tributyl tin -TBT-, alkylated lead, or methylmecury) are particularly toxic compounds which affect marine organisms, damaging not only the structure but also the functioning of the estuarine biota, being in the end potentially deleterious to man [12,20,27]. Estuarine waters can receive heavy metals from two kinds of sources: Natural Processes (including erosion and weathering of rocks, leaching of soils, volcanic activities, emissions of deep-sea hydrothermal vents, or forest fires); and Anthropogenic ones, by means of atmospheric deposition, rivers inflow, direct discharges or dumping (e.g., mining, smelting, refining, electroplating, and other industrial operations) [12]. Those human activities are usually greater in estuarine and coastal waters as well as in fluvial watersheds, mainly in those located near urban or industrialized centres [24]. Since heavy metals are generally particle-reactive and rapidly adsorb onto suspended sediments and other particle matter, the sea bottom and particularly estuarine sediments. They act as a reservoir, trap and repository for a large amount of contaminants [28,29]. Moreover, a change in the environmental conditions may cause a remobilization of the accumulated pollutants (heavy metals, organometallic compounds) [11,12]. On the other hand, degradation of alkyltins is much slower in sediments where the halflives are estimated to be of several years. The great stability of the TBT adsorbed onto sediments shows the long-term storage capacity of this compartment [30]. Microbial

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degradation and UV photolysis of TBT conduce to dibutyltin (DBT) and monobutyltin (MBT), and can take days to weeks in water, and several years to decades in anoxic sediments [31].

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2.2. Metal Toxicity Metal toxicity varies largely within estuarine and marine organisms related to different processes and conditions which regulate them. Likewise, the capacity of the organisms to intake, store, remove, or detoxify heavy metals considerably differs [12]. In addition, many intrinsic (i.e. surface impermeability, nutritional state) and extrinsic (i.e. dissolved metal concentration, temperature) factors influence heavy metal uptake, as well as the accessibility of metals to organisms (i.e. metal bioavailability) [32,33]. Environmental studies have demonstrated that organotin compounds persist in sediments and affect non-target organisms such as oysters and gastropods. The first deleterious effects on non-fouling organisms were evidenced in Arcachon Bay (France) where the oyster Crassostrea gigas suffered severe shell malformations and reduced reproduction [30]. Moreover, there is vast literature about the impact of heavy metals and organotin compounds on estuarine and marine organisms [12]. TBT induces imposex in gastropods, a false penis in female specimens, since this compound is known to be an endocrine disruptor [34]. Trace amounts of TBT were found in tissues from fishes, seabirds and dolphins from the Baltic Sea [20]; and in sharks, dolphins and tuna from coastal waters of Italy [35]. The most commonly documented effect of butyltins in marine mammals was immune suppression. The resistance of fishes against bacteria decreased even at very low TBT concentrations. Greater accumulation of butyltin compounds may have also contributed to the immune dysfunction in dolphins. Butyltin compounds are potent inhibitors of energy production in cells. They damage plasma membranes and inhibit ion pumps leading to the alteration of calcium homeostasis and apoptosis of thymocytes resulting in immunotoxicity [36]. Marine organisms present different contents of Cadmium. Kennish [12] gave some examples: mussels (Mytilus spp.) in coastal regions present mean levels of 1-5 µg g-1 dry wt, while the gastropods Nucella lapillus and Patella vulgate inhabiting the Bristol ChannelSevern estuary contain values of 144 and 277 µg g-1 dry wt. In addition, it has been reported for some crab species that cadmium accumulates mainly in the exoskeleton, and residues of this metal have also been detected in soft tissues (such as the ovary) but at much lower magnitudes. In spite of this low concentration one has demonstrated that the cadmium produces significant inhibition of ovarian growth during the reproductive period. This inhibition in the eyestalkless Chasmagnathus granulata crab is caused by inhibiting the secretion and/or mode of action of extra-eyestalk hormones that stimulate ovarian growth. This is has received strong support from the in vitro experiments, at least with respect to the mode of action of extra-eyestalk hormones. Cadmium completely inhibited the stimulating effect of both 17-hydroxyprogesterone and methyl farnesoate when it was added to the incubation medium [37]. On the other hand, and since many species of crustaceans inhabit estuaries, numerous studies have aimed to examine the bioaccumulation and effects of various toxicants in these animals [38]. Acute lethal toxicity bioassays are useful both to provide a measurement of the relative toxicity of substances, measuring the sensitivity of the species’ different stages of life

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to a particular substance, and to determine concentrations of chronic toxicity so as to assess water quality criteria. Several studies have been carried out in order to examine the bioaccumulation and effects of various toxicants in crustaceans inhabiting the Bahía Blanca estuary. Therefore, the response of the crab Chasmagnathus granulata from the Bahía Blanca estuary to metal toxicity was studied tending to identify the deleterious effects on this organism, which is considered a key species within the mentioned estuary, acknowledged as a man-impacted system in the marine coastal system of Argentina [16]. Cadmium presented the highest acute toxicity in this study, even the corresponding LC50 obtained values were higher than the corresponding metal concentrations measured within the Bahía Blanca environment. Moreover, cadmium displayed a significantly higher acute toxicity than lead (21 times) towards Chasmagnathus granulata zoeae I at the end of 96h of exposure [14]. In addition, cadmium levels in the Bahía Blanca estuary were significantly lower than the endpoints calculated by Andrade et al. [13] for Thalassiosira curviseriata from this environment. Taking into account that the chronic value (57 µg Cd dm−3) was significantly (p60 mg Mo/l and on growth at >1,000 mg Mo/l Bioconcentration factors were low, but depending on initial dose, measured residues (mg/kg fresh weight) were as high as 16 in amphipods, and were 3 in clams, 18 in crayfish muscle, and 32 in crayfish carapace [59-61].

ACKNOWLEDGMENTS I thank Dr. Volkan AKSOY for his careful reading of, and helpful comments on, an earlier version of this manuscript.

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[56] Underwood, E J. (1971). Trace elements in human and animal nutrition. Academic Press, New York: 116-140. [57] Chappell, W. R., and K. K. Petersen (eds.). (1976). Molybdenum in the environment. Vol. 1. The biology of molybdenum. Marcel Dekker, New York: 1-315. [58] Friberg, L. and J. Lener., (1986). Handbook of the toxicology of metals. Vol. II: specific metals. Elsevier Science Publ., New York. [59] Chappell, W. R., R. R. Meglen, R. Moure-Eraso, C. C. Solomons, T. A. Tsongas, P. A. Walravens, and P. W. Winston. (1979). Human health effects of molybdenum in drinking water. U. S. Environ. Protection Agency Rep. 600/1-79-006. 101 pp. [60] Friberg, L., and J. Lener. (1986). Molybdenum. Pages 446-461 in L. Friberg, G. F. Nordberg, and V. B. Vouk (eds.). Handbook of the toxicology of metals. Vol. II: specific metals. Elsevier Science Publ., New York. [61] Goyer, R. A. (1986). Toxic effects of metals. Pages 582-635 in C. D. Klaassen, M. O. Amdur, and J. Doull (eds.). Casarett and Doull's toxicology. Third edition. Macmillan Publ., New York.

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Chapter 20

BIOACCUMULATION OF HEAVY METAL BY MICROBES Nermeen A. El-Sersy1, Gehan A. Abou-Elela and Hanan M. Abd- Elnaby National Institute of Oceanography and Fisheries, Kayet Bey, El-Anfoushy, Alexandria, Egypt

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ABSTRACT Marine environment is considered to be as one of the most important habitats that must be protected from pollution worldwide. In recent years marine pollution has increased, due to increase in ship traffic and the uncontrollable dumping of toxic materials and wastes to the seas. Heavy metals have received considerable attention in recent years with regard to toxicity to aquatic life. This chapter deals with sources, distribution and fate of heavy metals in the sea water. Heavy metals accumulation by microorganisms is regarded as an attractive alternative to the physical and chemical methods applied for the treatment of heavy metals contamination. Bacillus, Staphylcoccus, Corynebacterium, Enterobacter, Pseudomonas, Klebsiella, Vibrio, Arthrobacter, Escherichia, Aeromonas, Brevibacterium, Deinococcus, Erwinia, Micrococcus, Nocardia, Sarratia, Thiobacillus, and Zoogloea are the most important bacterial species that used in the bioaccumulation processes . This chapter also reviews bacteria-metals interactions and mechanisms of metal cations accumulation by bacteria. Moreover minimal inhibitory concentrations (MICs) of most heavy metals to E.coli, resistance mechanism to copper, zinc and arsenic and finally, the accumulation of metal inside the bacterial cell and change in cell morphology were also reviewed.

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1. HEAVY METALS POLLUTION Approximately 71 percent of the earth’s surface is covered with water, nearly 99 percent of which is sea water. Marine environment is considered to be as one of the most important habitats that must be protected from pollution worldwide. Marine pollution is the introduction by man, directly or indirectly, of substances or energy to the marine environment resulting in deleterious effects such as, hazards to human health, hindrance of marine activities, including fishing, impairment of the quality for the use of sea water and reduction of amenities. In recent years marine pollution has increased, due to increase in ship traffic and the uncontrollable dumping of toxic materials and wastes to the seas. Marine pollution can be divided into a number of categories. thermal, oil or petroleum hydrocarbons, microbiological, radiation contamination, nutrients, heavy metals, particulate organic and inorganic substances, persisting solids plastic or any other pollutants. Heavy metals have received considerable attention in recent years with regard to toxicity to aquatic life. Heavy metals pollution can be defined as an increase in the level of these metals relative to the natural occurrence in any component of the environment. Heavy metals entering the marine environment from discharge of waste water especially the industrial and agriculture effluents. Although some heavy metals are essential for microbial growth at low concentration they can exert toxic effects at high levels. Microorganisms have the ability to accumulate heavy metals to different extents depending on their species and the interaction with physicochemical factors in the surrounding environment, this phenomenon called bioaccumulation.

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1.1. Ecology and Sources of Heavy Metals Of the 90 naturally occurring elements [1] there are approximately 65 elements that exhibit metallic properties, which may be termed “heavy metals” [2]. It is reported that heavy metals are metals with a density of above 5 g/cm3. Not all of the heavy metals have a good or bad biological function. This is simply because some heavy metals are not available to the living cell in the usual ecosystem [1]. In biological contexts, the principal chemical species are cations. Thus, heavy metal cations play an important role as “trace elements” in sophisticated biochemical reactions. It is generally accepted that heavy metals will interact with chemical and biological processes and cause changes within the biota. The major reasons for the particular sensitivity of aquatic systems to heavy metals pollution may be in the structure of their food chain, compared with land systems, the relatively small biomass in aquatic environments generally occurs in greater variety of trophic levels whereby accumulation of xenobiotic and poisonous substances can be enhanced [3,4]. Abed et al. [5] found that, in recent years, heavy metals have received great attention because of their release into the environment from different sources.

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1.1.1. Natural Sources The processes by which metals are supplied to the sea under natural conditions can be placed in three categories; • • •

Coastal supply, which includes input from rivers and from erosion by wave action. Deep sea supply, which includes metals released by deep sea volcanoes and those released from particles or sediments by chemical processes. Supply which by-passes the near-shore environment and includes metals transported in the atmosphere as dust particles and also materials which is produced by glacial erosion [6].

1.1.2. Man-Made Sources • •

• •

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•

Heavy metals are prevalent in municipal and industrial effluents, they modify the structure and productivity of aquatic ecosystems [7,8]. Irrigated agriculture and industrial pollution caused by factories, which lack the ability to control and safely dispose their wastes are important sources of pollutants [9]. Many processes involved in mining, smelting and refining release a variety of metals into water ways [6]. Waters such as leaks, [10] and sewage sludge are often dumped at sea, sometimes contain high concentrations of heavy metals. Atmospheric inputs of heavy metals to the sea where the contamination of the atmosphere has resulted from burning of fossil fuels, the smelting and refining of metals and from the use of metallic products such as arsenical pesticides in agriculture and leaded petrol in motor vehicles [6].

1.2. Distribution and Fates of Heavy Metals in the Sea Metals are introduced into the environment from various sources. The natural recycling of some metals, that generally occurred in biogeochemical cycles, had been disrupted as a result of the large quantities of metals and pollutants that are currently entering the environment from various sources [11]. Generally the total amounts of heavy metals in the oceans are thought to be constant as a result of a geochemical balance between the rates at which they are introduced and those at which they are removed by incorporation into the sediment. The ranges of some heavy metals in sea water are e.g. Ni, Zn, Pb, Cd and Cu are (0.13-43), (0.2-48), (0.03-13), ( 0, in organism growth and development as well as in recovery and training processes. In the aging processes, in severe and chronic diseases G decreases, i. e. dG < 0. In mature, healthy BO the synergy G could be assumed almost constant i. e. dG = 0. The following equation for the balance of biological energy B could be written: dB = dU + dZ – dR

(3)

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Here U = UW + UV

(4)

is the genome energy; UW is potential genome energy and UV is recovery energy. UW = const is characteristic for a given species. The recovery energy UV, should be proportional to the difference W – V(t), i. e. UV = K (W – V). UV should be positive function and the simplest such expression is the positive determined quadratic form:

UV =

1 K (W − V ) 2 2

(5)

K ([K] = [kg m2 b–2 s–2]) is the homeostatic inductivity, representing the feedback control strength. U has minimum at V(t) = W, when U = UW . We assume that the power of immune response P, expressed on a phenomenological level, should be proportional to the rate of change of the vitality, i. e. P = MV , where M ([M] = [kg m2 b–2 s–1]) is immune memory impulse. To be a positive function P should be constructed as follows:

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P = MV 2

(6)

The immune response has a cumulative effect. The state of a BO at a given moment depends not on the immune synthesis at that moment but on the summary effect of immune response in all prior moments. Therefore the immune response energy Z in the recovery process should have the form: t

t

t0

t0

Z (t ) = ∫ P( τ)dτ = ∫ MV ( τ) 2 dτ

(7)

Because BO behavior is considered on a phenomenological level, we are interested in the total effect of immune response and do not differentiate cell and humoral immunity. During the recovery process the biological energy B decreases to some extent at the expense of the energy R, spent for surmounting the metabolic “resistance” due to waste products of metabolism (non-fully oxidized substances, macromolecules damaged by free radicals etc.) and toxicants (heavy metals, bacterial and virus toxins etc.) occurring in the cell and decreasing the efficiency of the metabolic processes and hence of the self-regulation. It is reasonable to define R as follows:

R=

1 2 AV 2

(8)

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where A ([A] = [kg m2 b–2]) is resistance coefficient. The time derivative of G in (2) taking into account (3) and (4) could be written in the form:

G = WB = W (U V + Z − R )

(9)

Taking into account (5), (7) and (8) one obtains from (9):

G = W [ − K (W − V ) + MV − AV)V = WΦ V

(10)

where

Φ U = − K (W − V )

(11)

is biological force of homeostatically orchestrated feedback control ;

Φ Z = MV is biological force of immune reactivity;

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A New Theoretical Basis for Description of Living Matter

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Φ R = AV

(13)

is biological force of metabolic resistance.

Φ = ΦU + Φ Z − Φ R

(14)

is biological recovery force. Their dimension is: [ΦU] = [ΦZ] = [ΦR] = [Φ] = [kg m2 b–1 s–2]. We postulate the following principle for biological systems: G(W) = max G(V, V )

(15)

It means that the synergy G of BO in its normal, undisturbed state has maximum. G(W) corresponds to excellent health. After disturbance BO goes to recovery, to irreversible damage, or to death: 1) Recovery: dV > 0 , V ↑; then it follows from (15), (10) and (14) that dG > 0,

G (V) → G(W) and

ΦU + Φ Z − Φ R > 0

2) Destruction: dV < 0 , V ↓; then we have:

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dG < 0,

G (V) → G(Vunstable)

and

ΦU + Φ Z − Φ R > 0

but Φ < Φcrucial

3) Death: V = 0; therefore V = 0 and from (10) it follows: dG = 0,

G = const = 0

and

Φ=0

In training processes in the living organism with followed improvement of the vital parameters and health dW > 0 and W → W*, where W* > W; then: dG > 0,

G (V) → G(W*)

This means that in a training process the optimal vitality increases due to the genetical reserve being determined by the potential genome energy UW. The synergy of such an organism increases respectively. One of the most profound concepts in theoretical physics is that the equations of motion in different fields can be obtained based of integral variational principles. The variational principle of Hamilton allows a common treatment of dynamic problems in mechanics, electrodynamics, optics, thermodynamics, quantum mechanics etc. By means of appropriately chosen Lagrangeans the basic equations in physics can be introduced. This approach has a great heuristic concern. The presence of variational principles in all fields of physics clearly

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shows that a basic nature law exists. This promises validity of a variational principle of Hamilton type in fields, where there are no other approaches to some problems. We propose the following integral principle: T

Γ = ∫ (U + Z − R )dt = max

(16)

t0

choosing the Lagrangean:

L = L (V (t), V (t), t) = U + Z –R,

where U, Z and R are determined by the equations (4), (5), (7) and (8). After variation of (16)

Γ′(ε ) ε =0 = 0

(17)

where ε is an arbitrary parameter, the biodynamic equation is obtained:

V +

K 2M KW V + V= A − 2 M (T − t ) A − 2 M (T − t ) A − 2 M (T − t )

(18)

under initial conditions:

V (t0 ) = V0 and

V (t0 ) = V0

(19)

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V0 is the state of the disturbed BO from where the recovery process starts and V0 is the start rate of time change of V. T is the time period of the recovery process. Equation (18) has physical sense and aperiodic solution under the conditions:

A > 2 MT

(20)

M 2 > K ( A − 2 MT )

(21)

It is clear from (20) that the recovery period T is so much longer as higher is the contamination of the organism expressed by the coefficient A. When the immune memory impulse M has a higher value, T is shorter. If (21) is not valid and K >

M2 (that A − 2 MT

could be a situation most often in younger organisms) an over-shoot time course of the recovery process takes place. However, in such cases the following condition should be satisfactory:

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M2 < K < K crucial A − 2 MT

577

(22)

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At K > Kcrucial an over-regulation takes place, an oscillatory regime is generated and BO fails in an unstable regime. Many targeted investigations and empirical datum are needed to determine the real value of W for different species and different ages. If T and one of the parameters K, M, and A were known the areas of the two others parameters could be determined using (20) and (21). When all constants were known the BO state might be calculated at each moment and the recovery course would be predicted. In Figure 1 two possible time courses of recovery processes are presented at different values of the parameters. The experimentally measurements of many biological characteristics (changes in metabolite concentrations, biopotentials etc.) often indicate very similar time courses. The curves displayed in Figure 1 are numerical solutions of equation (18).

Figure 1. Time courses of the quantity vitality V during recovery processes. In exemplification a recovery period T = 20 days and a value of 100 bions for the optimal vitality W were chosen. The initial conditions were supposed V0 = 60 b and V = 1.8 b/day. The displayed curves were calculated at two sets of different values of the characteristic constants: A = 9, M = 0.2, K = 0.03; A = 8, M = 0.19, K = 0.18 (the over-shoot curve).

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3. CONCLUSION The proposed theoretical approach (presuming development of a new science field: biodynamics) is of great theoretical importance. The biological self-regulation and integrity provide a new quality of matter. Therefore, it is quite reasonable to evaluate the state of living systems in terms of a specific energy form. It is impossible to deduce the macrocharacteristics of a biological system based on the processes on a molecular level because of invincible mathematical difficulties. Thus, a new phenomenological theory for living matter should be founded. Biodynamics will be also very important for practical purposes as a new step in the exploration of living systems in the context of several disturbances and environmental changes, such as global change and environmental pollution. The designing of a new device that will measure quantity “vitality” would revolutionize biology and medicine. It could provide a quick and easy assessment of the health status of BO, particularly a human, and would allow for the study of the organism's overall response to harmful environments as well as the ability to provide a prognosis of the recovery processes. The optimal vitality W at respective age, and synergy G could be added as important integral biomarkers in patient’s files alongside their other data. Although the work is heuristic at this stage, a further development of the idea here proposed is quite realistic.

REFERENCES

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[1]

Bohr, N (1938). Biology and Atomic Physics. “Congressi di fisica, radiologia e biologia sperimentale. Bologna, 1937. (Celebrazione del secondo centenario dell nascita di Luigi Galvani)”. Bologna, pp.6-15. [2] Bohr, N (1957). Die Physik und das Problem des Lebens København: Atomfysik og menneskelig erkendelse. [3] Shrödinger, E (1944). What is Life? Cambridge: University Press. [4] Goodwin, BC (1963). Temporal Organization in Cells. London: Academic Press Inc. Ltd. [5] Rosen, R (1967). Optimality Principles in Biology. London: Butterworths. [6] Szent-Györgyi, A (1968). Bioelectronics. A Study in Cellular Regulation, Defense, and Cancer. New York London: Academic press. [7] Nicolis, G., and Prigogine, I. (1978). Self-organization in Nonequilibrium Systems. From Dissipative Structures to Order through Fluctuations. New York London Sydney Toronto: John Wiley and Sons. [8] Davidov, A (1979). Biology and Quantum Mechanics. Kiev: Naukova Dumka Publishing House. (In Russian). [9] Di Cera, E (ed.) (2001). Thermodynamics in Biology. Oxford New York: Oxford University Press. [10] Kurzynski, M (2005). The Thrrmodynamic Machinery of Life. Berlin Heiderlberg New York: Springer.

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[11] Bljumenfeld, LA (1967). Preface to the Russian edition. In: H. Quastler. The emergence of biological organization, pp. 5-6. Moscow: Mir Publishing house. (In Russian). [12] Quastler, H (1964). The Emergence of Biological Organization. New Haven and London: Yale University Press. [13] Eigen, M (1971). Molekulare Selbstorganistion und Evolution (Self organization of matter and the evolution of biological macro molecules). Naturwisswnschaften, 58(10), 465-523. [14] Volkenstein, MV (1994). Physical Approaches to Biological Evolution. Berlin Heidelberg: Springer Verlag. [15] Sheldrake, R. (1981). A new science of life. The hypothesis of formative causation. London: Blond & Briggs. [16] Waterman TH (1961). Comparative physiology. In: Waterman TH, editor The Physiology of Crustacea, vol II. New York: Academic; pp. 521-593. [17] Waterman TH (1965). The Problem. In: Waterman TH, Morowitz HJ editors. Theoretical and Mathematical Biology. New York Toronto London: Blaisdell Publishing Company; pp. 11-33. [18] Presman, AS (1968). Electromagnetic fields and living nature. Moscow: Naouka Publishing House. (In Russian). [19] Elizarov, AA (1997). Instrumental methods for investigating physical fields of biological objects. Measurement Techniques, 40(7), 700-707. [20] Gyarmati, I (1970). Non-equilibrium thermodynamics: Field theory and variational principles. Berlin Heidelberg New York: Springer-Verlag. [21] Prigogine, I., and Defay, R. (1954). Chemical thermodynamics. London New York Toronto: Longmans Green and Co. [22] Haase, R (1963). Thermodynamik der Irreversiblen Prozesse. Darmstadt: Dr. Dietrich Steinkopff Verlag.

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Chapter 25

MODELLING LOCAL AND REGIONAL BOUNDARY CONDITIONS OF THE GEOGRAPHICAL DISTRIBUTION OF MOSSES AND THEIR METAL LOADS IN GERMANY Roland Pesch1 and Winfried Schröder Chair of Landscape Ecology, University of Vechta, Vechta, Germany

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ABSTRACT The UNECE Heavy Metals in Mosses Surveys measure environmental concentrations of metals in mosses throughout Europe for ecotoxicological risk assessments. The metal loads depend on the depostion rate as well as on local and regional boundary conditions. In this chapter the most important boundary conditions are identified with help of the German moss survey data 1990, 1995, and 2000 using tree based models: moss species, precipitation, slope direction, and landuse. The knowledge of their influence on the metal accumulation is essential for the interpretation of the biomonitoring data and is of importance for designing the monitoring nets of succeeding monitoring campaigns. A shift of the geographical distribution of mosses could be observed by means of Classification and Regression Trees (CART). Based on the model, a predictive map was calculated in a GIS environment.

Keywords: Biomonitoring, classification and regression trees (CART), CARTography, GIS, metal accumulation, predictive mapping.

1. INTRODUCTION Metals emitted into the atmosphere come down to earth by wet and dry deposition. Subsequently the metals accumulate in soils and in biomass. Monitoring the bioaccumulation of metals by means of mosses is particularly suitable for exposure analysis [1], i.e. measuring 1 E-mail: [email protected].

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and predicting the environmental concentration of contaminants (Predicted Environmental Concentrations - PEC). For ecotoxicological risk assessments, PEC values have to be related to Predicted No Effect Concentrations (PNEC values) [2]. Metal accumulation surveys have been performed in, at least, 21 European states every five years since 1990 [3]. Germany participated in all the three surveys. Based on the results of these surveys, two working hypotheses are to be investigated in the paper at hand. The first one assumes that aside from depositions further interacting boundary conditions influence the metal loads in mosses. It should be examined statistically which of these conditions are likely to be the most important ones. Such an identification of significant impact factors of the metal bioaccumulation is, on the one hand, essential for the interpretation of the survey data. On the other hand, it helps to redesign the monitoring net throughout time in case of geographical shifts of the incidence of the moss species to be sampled. A predictive mapping of mosses may therefore support the spatial adjustment of the monitoring network. Thus, the second hypothesis assumes that a spatial shift of moss species can be predicted from one monitoring campaign to the other.

2. METHODS

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2.1. Sampling and Chemical Analysis The sampling and chemical analysis in the European Heavy Metals in Mosses Surveys was done according to a standard operation procedure [3,4]. Accordingly, the following sitespecific characteristics have to be considered which are significant for the investigation presented in this chapter: In vegetation stands the moss species samples should be collected at least 5 m afar from trees to avoid canopy drip. Further, the mosses should be collected 100 m afar from any ordinary road or single house, 300 m from settlements, primary roads and highways and 1000 m from industrial plants. The moss specie Pleurozium schreberi should be favoured and the concentration of, at least, As, Cd, Cu, Fe, Hg, Ni, Pb, V and Zn should be measured by means of convenient analytical methods. In Germany, the mosses were sampled at 592 (1990), 1026 (1995) and 1028 (2000) sites, respectively. In each of the samples in 1990 As*, Cd*, Cr, Cu, Fe, Ni, Pb, Ti, V and Zn (*not considered in the new federal states) were measured. In 19952 and 2000 Al, As, Ba, Ca, Cd, Cr, Cu, Fe, Hg, K, Na, Mg, Mn, Ni, Pb, Sb, V, Sr, Ti and Zn were analysed. The data from the 1990 and 1995 surveys and that from the 1995 and 2000 campaigns were assured to be comparable [5,6,7].

2.2. Multi-Metal Accumulation Index (MAI) To detect the spatial and temporal trends of the bioaccumulation of several metals as a whole, the metal-specific data were aggregated to metal-integrating indices. Complementarily to the nominal index computed by [8], an ordinally-scaled index was calculated by percentile statistics that aggregates the site-specific measurement data on Cr, Cu, Fe, Ni, Pb, Ti, V and Zn measured all over Germany in 1990, 1995 and 2000: All the site-specific measurements of 2

In 1995, further 20 elements were analysed [7]. These are not listed here.

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each of the three campaigns were ranked according to the absolute values of each of the eight metals and put into ten classes according to the 10th to the 90th percentile. Rank numbers were then assigned to each class for each of the metals: Measurement values below the 10th percentile were labelled 1, those lying inside the interval between the 10th and 20th percentile were labelled 2, and so on. To calculate the metal indices, the eight rank numbers were then averaged for each sampling site. In this way, each of the sites can be described by a multimetal accumulation index (MAI) ranging from 1 to 10 which integrates the sampling sitespecific measured bioaccumulation data. In this chapter these indices are used to correlate the metal accumulation with local and regional land characteristics.

2.3. Integration of Measurements and Data on Local and Regional Land Characteristics in a GIS Together with the measurement data and the MAI-values, data on the local and regional land characteristics were integrated with help of ArcGIS 9.0. Each sampling site was described with regard to those local boundary conditions that might influence the metal accumulation in mosses. The respective site-specific information was documented in a MS Access database, including: • • • •

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•

coordinates, date of sampling, administrative district, name of moss sampler, moss species, number of sub-samples (sampling points), altitude, inclination and slope direction, vegetation aspects (distance between the sampling points and trees, height of surrounding trees, dominant tree species, low canopy and herbaceous layer) as well as land use aspects (type of dominant land use, distance to roads, human settlements, industrial facilities and type of industry).

This sampling site-specific information was complemented by surface data from digital maps on other regional land characteristics that could influence the metal accumulation: altitude (UNEP Grid), monthly precipitation means from 1961-1990 (German Meteorological Service) and landcover (Corine Landcover). Because in Germany no complete inventory on georeferenced emission sources is accessible for research purposes, a 5 km buffer was set around each monitoring site and was intersected with the Corine landcover data. The percentage of those land use categories that can act as emission sources of metals was calculated and defined as an emission index. These categories include urban and industrial areas, streets, railways, airports, disposal and construction sites.

2.4. Identification of Significant Boundary Conditions of Metal Accumulation The statistical relations between the metal accumulation and local and regional land characteristics were modelled by classification and regression trees (CART) using SPSS

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Answer Tree 3.1. CART allows uncovering hidden structures in complex data matrices [9]. A major advantage of this technique is its ability to model non-additive and non-linear relationships among input variables, consisting of one dependent or target variable and a set of independent or predictor variables. In contrast to most of the classification techniques as, e.g. cluster analysis or classical regression analysis [8,10], CART handles very large sets of mixed, i.e. both categorical and parametric data without prior transformation of scale dignity sensu [11]. Thus, CART is very well applicable to environmental investigations [10, 12-32]. The classification results are, compared to classical regression methods, very easy to read and immediately indicate the variable that significantly discriminates between classes [33]: CART applies decision trees to display class memberships by recursively partitioning a heterogeneous data set into more homogeneous subsets (also called classes, groups, nodes) by means of a series of binary splits. Each split separates a parent node into two child nodes. CART calculates classes that are homogeneous with respect to the features of the dependent variable. Whether the target variable is of metric, ordinal or nominal scale dignity, different impurity measures exist. The Gini index is commonly used when the target variable is categorical, allthough other options are availible (entropy, twoing index) [34]. When the target variable is metric the LSD-measure (Least Squared Deviation) is used. In this way growing trees are processed until the maximum tree Tmax is reached depending on user specified restrictions, e.g. insufficient number of cases in a node or until further splitting is impossible (only one case or identical cases in the node). Smaller trees can be produced by pruning the maximum tree either automatically or interactively by expert judgements. Thus, CART dendrograms display a hierarchical system of decision rules that allow classifying objects (e.g. sampling sites) according to the features of the predictor variables. CART does not make any assumptions with regard to the distribution of the data. It can make repeated use of one explanatory variable so it can work with data that might have multiple interrelations. Further, CART is extremely robust with respect to special cases (outliers as, e.g., rare biotopes) because they will be separated as a class of its own. Thus, they will no longer affect the calculation of the rest of the decision tree. The most significant disadvantage of tree-based methods is the lack of a broadly accepted procedure for statistical inference [10]. To investigate the hypothesis on the boundary conditions of the metal accumulation, decision trees were computed using MAI 1990, 1995, and 2000, respectively, as the target variable. The following categorical and continuous data on local and regional boundary conditions were set as the predictor variables: land use, emission index, distance of the monitoring site to trees and shrubs, to unvegetated areas as well as to possible emission sources (industrial plants, roads and highways, human settlements), monthly precipitation means as well as altitude, slope gradient and slope direction.

2.5. Predictive Moss Mapping From 1990 to 2000 the geographical distribution of the moss species changed. The shifting of the occurence of moss species impedes the sampling significantly because, according to the survey guidelines (section 2.1), Pleurozium schreberi should be sampled by priority at the same sites in each survey. Thus, a probability based prediction of the geographical distribution of Pleurozium schreberi could help to restructure the monitoring net. Such predictive habitat mapping is based on a model of the relationship among

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environmental variables and the incidence of a moss species. This model may be applied to a geographic data base to predict the occurrence of Pleurozium schreberi where only data of biogeographic significant environmental characteristices are available [21, 35-39]. To this end, we combined site-specific data on the incidence of Pleurozium schreberi and surface data on precipitation, altitude and landcover by means of GIS-techniques and analysed the multiple statistical relations with help of CART-models.

3. RESULTS 3.1. Boundary Conditions of Metal Accumulation

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To investigate the first hypothesis on the boundary conditions of the metal accumulation one decision tree was computed each for the campaigns 1990, 1995 and 2000 (Figs. 1, 2, 3). Each dendrogram depicts the first three levels of binary splitting.

Figure 1. Decision tree on boundary conditions of metal accumulation 1990 (first three levels) Figure 1 depicts the decision tree calculated from the monitoring data 1990 plus surface data on altitude, precipitation and land use. The multi-metal index is taken as the target variable. The predictor variables are taken from the metadata (location describing information documented by the moss collectors) and the surface data (s. above) intersected with the monitoring data.

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Figure 2. Decision tree on boundary conditions of metal accumulation 1995 (first three levels) Figure 2 depicts the decision tree calculated from the monitoring data 1995 plus surface data on altitude, precipitation and land use. The multi-metal index is taken as the target variable. The predictor variables are taken from the metadata (location describing information documented by the moss collectors) and the surface data (s. above) intersected with the monitoring data.

By the example of the decision tree calculated from the survey data 1995 (Figure 2) it should be demonstrated how to read a decision tree. Decision trees are inverted trees with the root on the top and the leaves downwards. The elements of such trees are called nodes (classes, groups). The root is the parent node, the leaves are the child nodes, each being represented by a box which contains, amongst others, the following information: 1. node number, 2. arithmetic mean of the MAI-values from those sampling sites belonging to the respective node, 3. standard deviation of the MAI, 4. number of sampling sites in the respective node. The green bars represent the number of sampling sites belonging to one of ten MAI categories ranging form 0 to 1 (low metal accumulation, on the left) to 9 to 10 (high metal accumulation, on the right). For 1995 the CART calculations were performed with data on 1024 sites in Germany (Figure 2). The metal accumulation in terms of MAI approximates a Gaussian distribution with a mean of 5.5. The moss species is considered to be the most powerful predictor that devides the total sample into two subsets. The left one contains those sites where

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Scleropodium purum (S.p.) and Pleurozium schreberi (P.s.) were sampled. At these sites (n = 795) the mean MAI is roughly 5.2. But at those sites where Hypnum cupressiforme (H.C.), Hylocomium splendens (H.S.), Brachythecium rutabulatum (B.R.), Brachythecium albicans (B.A.), Rhytiadelphus squarrosus (R.S.), Rhytiadelphus triquetus (R.T.), Eurhynchium praelongum (E.P.), Plagiotheticum undulatum (P.U.), Abietinella abetina (A.A.) and Hypnum jutlandicum (H.J.) were sampled (n = 229) the MAI is about 6.6 and the statistical distribution of the MAI values is quite different. Node 13 is further split by the emission index: In cases the emission index exceeds 7.8 at sites with Scleropodium purum and Pleurozium schreberi, the MAI is roughly 6.1. If the emission index is below or equal 7.8 (node 16) the MAI is about 4.9 (node 15). Node 16 is further divided by the topography: In flat landscapes (node 21) there are more sampling sites with low metal accumulation than in hilly landscapes (node 22). In cases where other moss species than Scleropodium purum and Pleurozium schreberi were sampled, the precipitation in November (62.8 mm) and the emission index (8.2 %) were taken as splitting criteria.

Figure 3. Decision tree on boundary conditions of metal accumulation 2000 (first three levels) Figure 3 depicts the decision tree calculated from the monitoring data 2000 plus surface data on altitude, precipitation and land use. The multi-metal index is taken as the target variable. The predictor variables are taken from the metadata (location describing information documented by the moss collectors) and the surface data (s. above) intersected with the monitoring data.

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From all the three CART-models we can conclude that the metal accumulation in mosses is determined, aside from the metal deposition, by the following site-specific and regional boundary conditions: moss species, precipitation, slope direction, distance to unvegetated areas and landuse. In a further step of statistical analysis we tested if the the statistical association detected by means of CART could be corroborated by bivariate statistics. This was done with help of Spearman correlation analyses (for the metrically scaled variables) as well as contingency tables (Cramers-V and chi-square-statistics) (Table 1). The latter was done for the investigation of the association between the MAI-values and the moss species as well as the slope direction. In order to meet the assumptions for the chi-square-statistics the slope direction had to be classified as follows: 1 no particular direction; 2 N, NNW, NNE; 3 S, SSE, SSW; 4 W, NW, SW, WSW, WNW; 5 E, SE, NE, ESE, ENE. The moss species had to be grouped according to four categories: Pleurozium schreberi, Scleropodium purum, Hypnum cupressiforme and other moss species. The MAI-values were put into four classes according to the three quartiles. Table 1. Statistical associations between the MAI-values and the boundary conditions

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Boundary conditions precipitation Jan precipitation Aug altitutde em ission index slope direction Boundary conditions precipitation Nov em ission index dis tance to unveg. Areas m oss s pecies slope direction Boundary conditions precipitation Jan precipitation Aug altitutde em ission index m oss s pecies slope direction

1990 Spearm an corr. -0.30 -0.34 -0.16 0.17

Cramers-V

0.17 1995 Spearm an corr. -0,01* 0.26 0.28

Cramers-V

0.2 0,12* 2000 Spearm an corr. -0,01* -0,01* 0,05* 0.27

Cramers-V

0.23 0.13

* no signific ant correlation (0,01)

Table 1 depicts that not in all cases significant correlations could be found for the relationships between the MAI-values and the boundary conditions. In all three monitoring campaigns the first spliting variable (1990: precipitation in January; 1995 and 2000: moss species) show moderate but distinct significant relationships to the metal bioaccumulation. Other such associations can be observed for the emission index (in 1990, 1995, 2000), the

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slope direction (in 1990 and 2000) and the distance of the sampling site to unvegetated areas (in 1995). The monthly precipitation means (January and August) are only significantly correlated with the MAI-values in 1990, whereas in 1995 and 2000 no such observation can be made.

3.2. Predicting the Incidence of Pleurozium schreberi

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According to the second hypotheses and the methodology outlined in sections 1 and 2.5, respectively, a CART-model on the statistical relations between the occurence of Pleurozium schreberi in 1995 and regional land characteristics (altitude, land cover, monthly precipitation) was calculated. The statistical rules from this model were applied on the availible surface data to predict the occurrence of Pleurozium schreberi at sites where no mosses were sampled in 1995. This resulted in a prediction map depicting the spatial probability distribution of Pleurozium schreberi (Figure 4).

Figure 4. Prediction of Pleurozium schreberi from the 1995 incidences (Figure 4 shows the probability of finding P.s. in the territory of Germany for the campaign 2000. The map is calculated from a decision tree for the incidence of P.s. (target variable) from a set of predictor variables (altitude, land use and precipitation).)

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Figure 5. Validation of the Pleurozium schreberi prediction by incidence data from 2000 (Figure 5 shows how far the predivtive mapping of P.s. depicted in Figure 4 is equivalent to the found incidence of P.s. in the campaign 2000.)

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The probability map calculated from the occurence of Pleurozium schreberi 1995 (Figure 4) was validated by GIS-intersection with help of the moss monitoring data 2000. The result of validation is depicted in figure 5. As can be seen, the precision of the predicted incidence of Pleurozium schreberi is quite well: For 50 % of the German territory the precision is +/- 10 %. Predictions with a precision less that 30 % only occur on 12 % of the territory.

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4. DISCUSSION Amongst the countries which participate in the Metals in Mosses Survey it is only Germany that integrates measurement data from the campaigns 1990, 1995 and 2000 as well as sampling site-specific and regional surface data on land characteristics into a GIS. That is why a discussion of comparable investigations is hardly possible. [5] analysed the relations between the site-specific characteristics on the one hand and the metal-specific and the metalintegrating accumulation on the other hand by means of bivariate statistics. [40] used CART to relate metal accumulation data with site characteristics and data on ecoregions. Both investigations proved statistical dependencies between the metal accumulation in mosses and some sampling site-specific characteristics and landscapes. These findings could be corroborated and detailed by the investigation presented in the paper at hand. The UNECE Heavy Metals in Mosses Surveys revealed that local emission sources such as factories and densely populated areas with high traffic activities promote the accumulation of metals in mosses [3,41-43]. Based on the chemical analysis of 17 metals in Scleropodium purum and Hypnum cupressiforme at 75 sites in Galicia (NW Spain), [44] found that canopy drip did not influence the metal accumulation in mosses significantly. While in accordance to these findings [5] could not detect any distinct relationship between the accumulation of metals in mosses and the distance of the sampling location to the nearest tree by Spearman rank correlation, contingency tables analyses on the other hand show significant dependencies for almost all elements in 1995 and 2000. The latter findings are corroborated [40]. Accordingly, the topographical features altitude and inclination do not show any directional dependency from the metal accumulation in mosses in terms of the Spearman correlation coefficients. Again, the cross-tabulations revealed diverging results: Whereas no clear conclusions could be drawn for the slope direction and the slope inclination, respectively, the altitude was observed to significantly influence the metal accumulation. Altitude was the only sampling site character which was proved to be correlated with each metal species and the metal-integrating accumulation indices. Based on a small data set, the correlation between altitude and metal accumulation in mosses was already corrobarated for Pb, Cd, and Zn along transects on five mountain ranges within the northern and eastern Alps [45]. But no prove was given for such correlations over large areas as, e.g., the territory of a country as large as Germany. The moss-specific accumulation of metals was investigated on the basis of small samples: [6,7, 46-51]. Fernandez and Carballeira [45] among others compared the metal accumulation in several moss species, each sampled at the same location (co-located samples). By this, all potential impact factors others than the moss species could be assumed to be constant. The investigation in hand, too, confirms significant associations between the moss species from different sampling sites and the metal concentrations in mosses. But the moss species

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compared were taken at different sites. Further, it should be beared in mind, that the metal accumulation might vary within species. Siewers et al. [7] found that the mean variation between the metal loads of four to eight subsamples of Pleurozium schreberi taken at one of 49 sites in North Rhine-Westfalia (federal state of Germany) varied between 12 (Cu) and up to 29 % (As). There are no further investigations that quantify the intra- and interspecies variability by way of a statistically sound approach. Together with altitude and collected moss species, ecoregional dependencies can be observed in each of the moss surveys in Germany for almost all metal elements including the ordinal indices of metal accumulation [40]. In addition to Pesch and Schröder [40], the investigation presented in the paper at hand used the ecoregional characteristics disaggregated as single GIS-layers on precipitation, land use (emission index) and altitude. This should enable a more specific interpretation of the ecoregional boundary conditions of metal accumulation.

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5. CONCLUSION CART is a powerful tool to corroborate results from bivariate statistics and to uncover multivariate relations between the metal accumulation in mosses and sampling site-specific and regional land characteristics. Additionally, CART allows integrating nominal, ordinal and metric data in one model. The CART models presented in this paper correlate and rank the factors promoting the metal accumulation in mosses. First order factors are moss species and precipitation. Land use (emission index), precipitation, and altitude are proved to be second order factors. Third order promoters are: topography (flat / slope direction), precipitation, land use (emission index) and distance to unvegetated areas. The verification and the multivariate differentiation of the boundary conditions of metal accumulation in mosses presented in the paper at hand should induce further investigations. If different moss species accumulate metals differently, conversion factors for the moss species used in national and international PEC monitoring systems should be calculated. Since the site-specific and regional land characteristics are associated with the metal accumulation in the mosses, these conversion factors should be regionalized. The regional land characteristics should additionally be used for geostatistical surface estimations of the site-specific data on metal accumulation to optimise the mapping of temporal and spatial trends. A further support for the mapping of metal accumulation in mosses throughout Europe is expected from predictive mapping. As shown by the example of Germany, the changing incidence of moss species throughout time and space impedes the sampling significantly because certain moss species should be sampled by priority. Thus, a probability based prediction of the geographical distribution of moss species could help to adjust the monitoring net. The respective model presented in this paper detects the statistical rules that govern the relationship among environmental variables and the geographical pattern of Pleurozium schreberi. The model could be applied to predict the incidence of Pleurozium schreberi for those sites where Pleurozium schreberi has not been sampled yet. As validated by use of the incidence data of Pleurozium schreberi from the moss survey 2000, the precision of the predicted Pleurozium schreberi incidence calculated from the survey data 1995 is quite well.

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[19] Lawrence, R., and Labus, M. (2003). Early detection of douglas-fir beetle infestation with subcanopy resolution hyperspectral imagery. Western J. Appl. Forest, 18, 202-206. [20] McBratney, A.B., Odeh, I.O.A., Bishop, T.F.A., Dunbar, M.S., and Shatar, T.M. (2000). An overview of pedometric techniques for use in soil survey. Geoderma, 97, 293-327. [21] McBratney, A.B., Mendonca, M.L., and Minasny, B. (2003). On digital soil mapping. Geoderma, 117, 3-52. [22] Moisen, G.G., and Frescino, T.S. (2002). Comparing five modelling techniques for predicting forest characteristics. Ecol. Model, 157, 209-225 [23] Morrison, S.F., Forbes G.J., Young, S.J., and Lusk, S. (2003). Within-yard habitat use by white-tailed deer at varying winter severity. Forest Ecol. Manag, 172, 173-182. [24] Negron, J.F. (1998). Probability of infestation and extent of mortality associated with the douglas-fir beetle in the Colorado Front Range. Forest Ecol. Manag, 107, 71-85. [25] Negron, J.F., Wilson, J.L., and Anhold, J.A. (2000). Conditions associated with roundheaded pine beetle (Coleoptera: Scolytidae) infestations in Arizona and Utah. Environ. Entomol., 29, 20-27. [26] Nerini, D., Durbec, J.P., Mante, C., Garcia, F., and Ghattas, B. (2000). Forecasting physicochemical variables by a classification tree method. Application to the Berre Lagoon (South France). Acta Biotheor., 48, 181-196. [27] Nerini, D., Durbec, J.P., and Mante, C. (2000). Analysis of oxygen rate time series in a strongly polluted lagoon using regression tree method. Ecol Model, 133, 95-105. [28] Nigh, G.D., and Love, B.A. (2004). Predicting crown class in three western conifer species. Can. J .Forest Res., 34, 592-599. [29] Sá, A.C.L., Pereira, J.M.C., Vasconcelos, M.J.P., Silva, J.M.N., Ribeiro, N., and Awasse, A. (2003). Assessing the feasibility of sub-pixel burned area mapping in Miombo Woodlands of Northern Mozambique using MODIS imagery. Int. J. Remote Sens, 24, 1783-1796. [30] Thuiller, W. (2003). BIOMOD – Optimizing predictions of species distributions and projecting potential future shifts under global change. Glob. Change Biol., 9, 13531362. [31] Walmsley, J.L., Barthelmie, R.J., and Burrows, W.R. (2001). The statistical prediction of offshore winds from land-based data for wind-energy applications. Bound-Lay Meteorol, 101, 409-433. [32] Wösten, J.H.M., Pachepsky, Ya.A., and Rawls, W.J. (2001). Pedotransfer functions. Bridging the gap between available basic soil data and missing soil hydraulic characteristics. J. Hydrol., 251, 123-150. [33] Clark, L.A., and Pregibon, D. (1992). Tree-based models. In J.M. Chambers, and T.J. Hastie (Editors). Statistical Models in S. (377-419). New York: Chapman and Hall. [34] Steinberg, D., and Colla, P. (1995). CART. Tree-Structured Non-Parametric Data Analysis. San Diego, Ca: Salford Systems. [35] Estrada-Pena, A., and Santos-Silva, M.M. (2005). The distribution of ticks (Acari: Ixodiae) of domestic livestock in Portugal. Exp Appl Acarol, 36, 233-246. [36] Jackson, R.D., and Bartolome, J.W. (2002). A stae-transition approach to understanding nonequilibrium plant community dynamics in Californian grasslands. Plant. Ecol., 162, 49-65.

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[37] Vayssieres, M.P., Plant, R.E., Allen-Diaz, B.H. (2000). Classification trees. An alternative non-parametric approach for predicting species distributions. J. Veg. Sci., 11, 679-694. [38] White, D., and Sifneos, J.C. (2002). Regression tree cartography. J Comput Graph Stat, 11, 600-614. [39] Yen, P.P.W., Huettmann, F., and Cooke, F. (2004). A large-scale model for the at-sea distribution and abundance of Marbled Murrelets (Brachyramphus marmoratus) during the breeding season in coastal British Columbia, Canada. Ecol. Model., 171, 395-413. [40] Pesch, R., and Schröder, W. (2005). Integrative exposure assessment through classification and regression trees on bioaccumulation of metals, related sampling site characteristics and ecoregions. Ecol. Inf,. 1, 55-65. [41] Rühling, A., Rasmussen, L., Mäkinen, A., K. Pilegaard,, and Steinnes, E. (1987). Survey of Atmospheric Heavy Metal Deposition in the Nordic Countries in 1985 Monitored by Moss Analysis. Nord 21. [42] Rühling, A. (1994). Atmospheric Heavy Metal Deposition in Europe – Estimations Based on Moss Analysis. Nord 9. [43] Rühling, A., and Steinnes, E. (1998). Atmospheric Heavy Metal Deposition in Europe 1995 – 1996. Nord 15. [44] Fernandez, J.A., and Carballeira, A. (2002). Biomonitoring metal deposition in Galicia (NW Spain) with Mosses: Factors affecting bioconcentration. Chemosphere, 46, 535542. [45] Zechmeister, H. (1994): Biomonitoring der Schwermetalldepositionen mittels Moosen in Österreich, Monographien Umweltbundesamt, Wien. [46] Folkeson, L. (1979). Interspecies calibration of heavy-metal concentrations in nine mosses and lichens: Applicability to deposition measurements. Water Air Soil Poll., 11, 253-260. [47] Herpin, U., Lieth, H.,, and Markert, B. (1995). Monitoring der Schwermetallbelastung in der Bundesrepublik Deutschland mit Hilfe von Moosanalysen. UBA-Texte 31/95, Berlin. [48] Köhler, J., and Peichl, L. (1993). Vergleich verschiedener Moosarten als Bioindikatoren für Schwermetalle in Bayern (i.R. des ECE-Moosmonitoring 1991). Augsburg: Bayerisches Landesamt für Umweltschutz. [49] Ross, H.B. (1990). On the use of mosses (Hylocomium splendens and Pleurozium schreberi) for estimating atmospheric trace metal deposition. Water Air Soil Poll., 50, 63-76. [50] Thöni, L., Schneyder, N., and Krieg, F. (1996). Comparison of metal concentrations in three species of mosses and metal freights in bulk precipitations. Fresen J. Anal. Chem., 354, 703-708. [51] Wolterbeek, H.T., Kuik, P., Verburg, T.G., Herpin, U., Markert, B., and Thöni, L. (1995). Moss interspecies comparisons in trace element concentrations. Environ. Monit. Assess 35, 263-286.

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INDEX

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A  abdomen, 302, 307  abdominal, 167, 482  aberrant, 137, 333  abiotic, 461, 502  abnormalities, 167, 174, 189, 277, 414, 424, 425,  446  absorption, 19, 80, 83, 146, 167, 194, 196, 199, 270,  373, 412, 482, 521  absorption coefficient, 146  absorption spectroscopy, 270  Abu Dhabi, 182  academic, 99, 170, 341  acceptors, 503  access, 38, 53, 54, 75, 108, 136, 433, 434, 564  accessibility, 226, 266  accidental, 22, 32, 161, 162, 164, 185, 226, 302, 324,  328  accidents, xii, 1, 9, 25, 36, 39, 63, 65, 68, 69, 158,  168, 173, 174, 185, 186  acclimatization, 442, 485  accommodation, 559  accountability, 544, 545  accounting, 268, 540, 542, 543, 544, 552  accuracy, xvi, 67, 270, 287, 316, 317, 343  acetate, 106, 110, 135, 154, 288  acetic acid, 6, 137, 288  acetylcholine, 86  acetylcholinesterase, 426, 429, 440, 466  achievement, 562  acid, 1, 2, 3, 5, 7, 8, 27, 28, 29, 37, 45, 48, 78, 87,  137, 154, 166, 247, 270, 287, 288, 289, 291, 304,  312, 318, 415, 426, 436, 477, 480, 504, 515, 519,  548, 550, 551 

acidic, 8, 21, 28, 74, 226, 428, 546  acidification, 227  acidity, 226  acrocentric chromosome, 137, 139  actinomycetes, 499  activation, 100, 101, 104, 412, 445, 456, 461, 469,  470, 503, 517, 519  active centers, 143  active oxygen, 151  active site, 453, 520  active transport, 197, 504  acute, 21, 32, 97, 113, 211, 214, 219, 221, 267, 279,  296, 334, 418, 428, 456, 469, 480, 489, 491, 572  Adams, 475, 477  adaptability, 434  adaptation, 420, 442, 448, 453, 464, 473, 475, 502,  525, 570, 571  additives, xvi, 293, 294  adducts, 411, 414, 416, 422, 426, 427, 443, 444,  468, 469  adenomas, 295  adenosine, 572  adenylate kinase, 451  adhesives, 163, 301, 302, 304  adjustment, 556, 582  administration, 143, 149, 312, 457, 531  administrative, 583  adrenal cortex, 295  adrenaline, 4  adsorption, 237, 246, 278, 362, 363, 480, 489, 498,  503, 504, 512, 513, 515  adult, 100, 105, 106, 107, 109, 111, 134, 150, 306,  382, 384, 406, 412, 423, 472, 480, 481, 491, 529  adult population, 406  adulthood, 99, 106, 107 

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598

Index

adults, 31, 32, 105, 483  advertisements, 2  advisory body, 175  Aegean Sea, 233, 234, 236, 238, 241, 254, 255, 258,  426, 468  aerobic, 214, 296, 298, 439, 464, 512, 556, 557, 562,  563, 564, 568  aerosol, 27, 37, 302, 316, 317  aerosols, xvi, 166, 228, 316, 317, 320, 324  aesthetics, 52, 559  aetiology, 424  Africa, xv, 223, 224, 298, 309  afternoon, 320  agar, 505  age, 63, 71, 99, 101, 106, 107, 112, 136, 147, 153,  172, 200, 257, 273, 331, 333, 414, 428, 435, 437,  438, 447, 453, 454, 488, 490, 578, 593  agent, 143, 148, 217, 412, 425, 445, 491  agents, xv, xvii, 25, 28, 86, 137, 140, 141, 163, 184,  190, 194, 217, 318, 409, 410, 411, 412, 414, 418,  420, 437, 445, 543  agglutination, 103  aggregates, 76, 81, 324, 328, 582  aggregation, 75  aggressive behavior, 36  aging, 36, 77, 571, 573  aging process, 77, 571, 573  agricultural sector, 22  agriculture, 3, 10, 17, 19, 21, 22, 44, 61, 63, 70, 157,  164, 224, 237, 297, 298, 317, 318, 324, 403, 496,  497, 506  aid, 437, 518, 540, 560  air emissions, 50, 549  air pollutant, 2, 3, 5, 9, 27, 30, 37, 538, 548  air pollutants, 2, 3, 5, 9, 30, 37, 538, 548  air pollution, xii, xvi, 3, 4, 5, 10, 27, 37, 41, 42, 44,  45, 49, 52, 56, 116, 131, 184, 187, 315, 316, 544,  545  air quality, 1, 3, 45, 48  airborne particles, xvii, 316, 317, 318, 322, 324, 326,  328, 329  aircraft, 2, 30, 34, 36, 170  air‐dried, 286  airplanes, 8  airports, 34, 583  albinism, 450  albumin, 142  alcohols, 439, 546  aldehydes, 441, 546  aldrin, 294 

algal, 23, 25, 73, 74, 75, 76, 77, 81, 82, 89, 90, 92,  93, 160, 176, 187, 214, 358, 515  Algeria, 225, 249  alicyclic, 546  alien, xvii, 409  alien species, xvii, 409  alimentation, 435  alkali, 241, 244, 246, 416, 417  alkaline, 200, 411, 416, 417, 421, 422, 444, 543, 546  alkalinity, 76, 555  alkaloids, 86  alkanes, 182, 522  allele, 445, 449, 451, 452, 453  alleles, 449, 451, 452, 453  allergens, 30  allergic, 28, 188  alloys, 393  alpha, 15, 65, 172, 182, 435  Alps, 591  alternative, 108, 117, 171, 495, 498, 560, 564, 595  alters, 507  aluminium, 12, 298, 550  aluminum, 11, 27, 150, 172, 393  Aluminum, 505  ambient air, 30, 31  amendments, 185  American Association for the Advancement of  Science, 407  americium, 65  amine, 504  amines, 6, 411, 443, 522, 531  amino, 79, 91, 196, 406, 436, 441, 448, 449, 460,  519  amino acid, 79, 91, 406, 436, 448, 449, 519  amino acids, 79, 91, 436  amino groups, 441  ammonia, 19, 32, 78, 126, 194, 197, 340, 345, 348,  353, 356, 357, 362, 369, 390, 393, 395, 397, 406,  512, 548  ammonium, 13, 85, 91, 288, 316, 320, 402, 562  ammonium salts, xvi, 316, 320  amphibia, 150  amphibians, 134  amplitude, 272  Amsterdam, 90, 92, 150, 278, 279, 421, 424, 466,  492, 593  anaerobic, 24, 236, 296, 298, 299, 519, 556, 557,  562, 564  anaerobic bacteria, 519  analysis of variance, 137 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

Index analytical techniques, 175, 480  androgen, 99, 101, 106, 109, 110, 295  androgens, 99, 106, 107  Aneuploidies, 413  aneuploidy, 411, 413, 423, 424, 470  angiosperms, 87  anhydrase, 142, 482  animal feeding operations, 17  animal health, 2  animal husbandry, xiv, 157  animal models, 306  animal studies, 300, 473  animal tissues, 286, 304, 489  animal waste, 8, 157  anion, 438, 516  anions, 196, 480, 498, 500, 504, 515  anode, 417  anoxia, 85, 470  anoxic, 157, 168, 177, 180, 196, 201, 204, 226, 237,  266  antagonist, 435  antagonistic, 449  antagonists, 112, 154  Antarctic, 282, 338, 402, 454, 472  anthropic, 232, 264, 315, 316  antibiotic, 108, 453  antibiotics, 108  antibody, 98, 100, 103, 105, 106, 107, 108, 109, 110,  112, 471  antibonding, 520  antigen, 100, 102, 103, 108  antimony, 221, 286  antioxidant, 148, 418, 438, 439, 440, 464, 465, 467,  472, 477, 531  antioxidants, 147, 148, 440, 464, 465  antioxidative, 457  antitumor, 435  apoptosis, 102, 147, 154, 266, 418, 427  apoptotic, 147, 418  apoptotic cells, 418  application, 3, 22, 24, 54, 64, 78, 174, 248, 270, 409,  411, 421, 463, 466, 472, 473, 498, 513, 515, 539,  559, 562, 563, 565  aquaculture, 178, 187, 188, 296, 343  aquatic habitat, 22, 73  aquatic habitats, 22, 73  aquatic systems, 76, 87, 195, 247, 302, 348, 496,  518  aqueous solution, 500  aquifers, 71 

599

Arabian Gulf, 203, 205, 210, 213, 219  arabinoside, 471  Arctic, 182, 190, 300, 310  Arctic Ocean, 182  Argentina, 72, 263, 264, 265, 267, 268, 269, 274,  278, 279, 280, 281, 282, 283, 291, 399, 415  argument, 104  arid, 318, 454  Aristotle, 238  arithmetic, 119, 333, 586  Arizona, 594  Arkansas, 486  armed conflict, 25  Army, 97  aromatic, 6, 164, 176, 190, 298, 310, 411, 426, 436,  443, 447, 452, 522, 529, 531, 535, 546  aromatic compounds, 310  aromatic hydrocarbons, 164, 190, 447, 452, 529,  535, 546  Aromatic hydrocarbons, 517  aromatic rings, 522  aromatics, 547  arsenic, 13, 181, 193, 195, 198, 201, 214, 220, 221,  229, 253, 260, 265, 311, 462, 495, 506, 507, 508,  516  arsenite, 177, 214, 456, 507, 508  arsenobetaine, 214  arteries, 4  arthritis, 300  Arthropoda, 375, 524  artificial, 16, 22, 61, 63, 64, 65, 66, 68, 69, 80, 88,  163, 172, 229, 264, 452, 570  aryl hydrocarbon receptor, 532, 533, 534  asbestos, 229, 232, 252  Ascidians, 378, 382, 384  ash, 2, 24, 37, 38, 268, 488  Asia, xix, 239, 403, 411, 553, 554, 555, 558, 561,  562, 563, 564, 565  Asian, 296, 405, 529, 553, 554, 558, 561, 562, 563,  565  asphalt, 57  asphaltenes, 25  Assam, 131  assaults, 141  assessment procedures, 65  assets, 45, 48  assignment, 58, 519  assimilation, 354, 488  associations, 74, 247, 451, 588, 591  assumptions, 66, 584, 588 

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Index

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

600

asthma, 4, 5, 28, 29, 31, 32, 105  asymptotic, 148  Athens, 187, 237, 253, 254, 256, 260  Atlantic, 170, 177, 217, 218, 220, 224, 225, 227, 257,  278, 280, 418, 457, 465, 467, 469, 477  Atlantic Ocean, 224, 225, 227  Atlas, 94, 403, 512  atmospheric deposition, xiv, 159, 179, 193, 265  atmospheric particles, xvi, 315, 316, 325  atomic absorption spectrometry, 137, 219  atomic emission spectrometry, 337  atomic physics, 2  atoms, 15, 30, 62, 63, 172, 298, 301, 304, 572  atrophy, 99  attachment, 139  attention, 50, 65, 97, 99, 105, 134, 168, 175, 211,  265, 341, 412, 440, 495, 496, 522, 539, 550, 554,  558, 560, 561  audio, 34  Australia, 86, 90, 219, 252, 330, 411, 563, 566, 567  authority, 44, 125  autoimmune, 102, 105, 111  autoimmune disease, 102, 105  autoimmune diseases, 105  automobiles, 2, 3, 4, 34, 161  automotive, 14  Autonomous, 225  autopsy, 338  autoradiography, 433, 443  autosomes, 137  availability, 21, 31, 50, 73, 75, 79, 80, 82, 85, 91, 93,  199, 217, 282, 341, 357, 364, 383, 406, 419, 449,  484, 486, 492, 499, 540, 551  awareness, 58, 65, 540, 554 

B  B cell, 98, 99, 100, 101, 102, 103, 104  B cells, 98, 101, 103  babies, 32  Bacillus, xviii, 495, 499, 515  Bacillus subtilis, 515  background noise, 36  background radiation, 67, 72  backwaters, 342, 346, 348, 360, 363, 368, 396, 403,  404  bacteria, 8, 18, 19, 22, 24, 83, 100, 104, 108, 160,  214, 266, 390, 446, 495, 498, 499, 500, 504, 506,  507, 512, 513, 514, 515, 516 

bacterial, 25, 80, 102, 103, 104, 110, 158, 159, 411,  495, 498, 499, 500, 507, 508, 510, 512, 513, 514,  515, 516, 574  bacterial cells, 498, 513  bacterial strains, 499  bactericides, 286  bacteriophage, 154  bacterium, 461, 508, 513  Bahrain, 182  Balearic Islands, 464  ballast, 25, 81  Bangladesh, 115, 130, 131, 132  banks, 23, 234  Barents Sea, 178  barges, 162  barley, 298  barrier, 127, 504, 560  barriers, 38, 126, 184, 560  BAS, 151, 152  basic research, 69, 100  basophils, 100  baths, 17  batteries, 10, 11, 13, 14, 23  battery, 20, 110, 125, 420, 488  BD, 218, 219, 476, 490  beaches, 11, 24, 162, 169, 184, 260  Beagle Channel, 274, 282  behavior, 20, 76, 109, 112, 285, 347, 403, 454, 480,  553, 571, 574  behavioral change, 432  behavioral problems, 165  behaviours, 215  Belgium, 227, 304, 307, 308, 312, 313, 315, 319,  322, 403  beliefs, 549  benchmark, 68  beneficial effect, 64, 166, 448  benefits, 44, 58, 65, 102, 278, 550, 554, 557  Bengal, Bay of, 340, 346, 350, 367, 373, 398, 400,  401, 402, 403, 404, 405  benign, 58  benthos animals, xiv, 157  benzene, 25, 32, 541  benzo(a)pyrene, 422, 426, 427, 428, 436, 522  beta, 15, 108, 112, 154, 172, 455  beta particles, 15, 172  beverages, 28  bicarbonate, 75, 78  bile, 435, 520  bile acids, 435, 520 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

Index bilge, 25  bilirubin, 435  bioactive, 198  bioassay, 178  bioassays, 219, 266  bioassimilation, 480  bioavailability, 195, 196, 217, 247, 266, 280, 299,  307, 410, 421, 436, 437, 486  biochemical, 18, 152, 193, 195, 216, 221, 312, 410,  419, 432, 433, 442, 451, 453, 456, 459, 470, 472,  496, 502, 518, 528, 532, 561, 570, 572, 573  biochemistry, 197, 401, 462, 515, 518, 530  bioconcentration, 196, 197, 217, 425, 488, 595  biodegradable, 12, 18, 23, 160, 298, 554, 558  biodegradable materials, 18  biodegradation, 160, 296, 301, 512, 555, 556, 558,  561  biodiversity, 4, 21, 38, 85, 163, 364  biofilm formation, 498  biogas, 561  biogeochemical, 228, 279, 285, 402, 497  bioindicators, 136, 447  biological activity, 24, 181, 206, 561  biological consequences, 16  biological macromolecules, 518, 572  biological processes, xii, 18, 61, 172, 340, 496, 571  biological responses, 433  biological systems, 294, 481, 518, 572, 575  biologically, 19, 147, 200, 216, 354, 398, 410, 438,  487, 488, 507  biology, 70, 174, 339, 340, 406, 464, 477, 478, 493,  569, 570, 571, 578  biomarker, 409, 416, 419, 420, 426, 427, 428, 433,  434, 435, 436, 437, 438, 439, 440, 444, 446, 453,  454, 455, 458, 461, 462, 463, 464, 466, 471, 517,  519, 528, 529, 534  Biomarker, 425, 433, 528, 534  biomass, 5, 52, 74, 79, 88, 92, 98, 341, 364, 372,  373, 375, 381, 387, 388, 390, 399, 406, 496, 498,  500, 504, 513, 514, 515, 555, 581  biomedical, 15  biomolecules, 208  biomonitoring, 135, 308, 409, 412, 416, 418, 419,  420, 432, 437, 443, 454, 463, 466, 472, 473, 475,  581  biophysical, 570  biophysics, 571  Bioreactor, 553, 555, 556, 558, 559, 560, 561, 563,  564, 565, 566, 567, 568  bioreactors, 553, 556, 557, 563, 565, 567 

601

bioremediation, 190, 297, 500, 507  biosorption, 500, 504, 513, 514, 515  biosphere, xiv, 15, 193, 488  biosynthesis, 434  biota, 65, 67, 74, 178, 181, 182, 183, 190, 220, 264,  265, 276, 278, 305, 307, 480, 489, 496, 518, 569  biotic, 76, 318, 339, 461, 502  biotic factor, 502  biotransformation, 426, 434, 435, 445, 455, 457,  467, 468, 477, 518, 521, 529, 531, 534  Biotransformation, 434, 457, 532  birds, 23, 26, 97, 98, 99, 100, 101, 102, 103, 105,  106, 107, 108, 109, 160, 165, 170, 178, 184, 190,  279, 295, 296, 308, 309, 331, 332, 333, 334, 336,  337, 338, 432, 446, 450, 525  birth, 14, 32, 165, 413  birth weight, 32  births, 474  bisphenol, 178, 441, 467  bivalve, 211, 405, 409, 410, 411, 414, 415, 416, 417,  420, 437, 450, 471, 476, 492  black, xi, 2, 26, 39, 106, 112, 113, 168, 225, 317,  444, 455, 467  Black Sea, 203, 205, 210, 213, 219, 224, 239, 280  bladder, 302  bleaching, 28, 164  blocks, 76, 147, 187  blood, 13, 16, 31, 36, 103, 106, 107, 134, 135, 144,  146, 151, 167, 188, 199, 221, 305, 312, 313, 446,  486, 533, 534, 535  blood clot, 533, 534  blood plasma, 312  blood pressure, 13, 36  blood stream, 31  blood vessels, 36  bloodstream, 108  B‐lymphocytes, 110  boats, 161, 184, 229, 269  body composition, 200  body fluid, 198, 208  body size, 387  body temperature, 26, 135, 170  body weight, 98, 110, 134, 143, 212  Bohr, 578  boilers, 83  boils, 549  bomb, 173  bonding, 33, 520  bonds, 522 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

602

Index

bone, 14, 98, 133, 134, 136, 137, 138, 139, 140, 141,  142, 143, 144, 145, 146, 148, 149, 150, 151, 152,  153, 174, 300, 474, 533, 534  bone marrow, xiii, 14, 98, 133, 134, 136, 137, 138,  139, 140, 142, 143, 146, 148, 149, 150, 151, 152,  153  booms, 184  borderline, 66, 195  Boston, 216  bottleneck, 434, 448, 450  bottom‐up, 74  boundary conditions, xix, 581, 582, 583, 584, 585,  586, 587, 588, 592  bovine, 103, 106, 142  brain, 14, 32, 98, 143, 150, 154, 167, 440  brain damage, 32  brainstorming, 123  brass, 393  Brazil, 67, 81, 276, 282, 283, 296, 415, 473  Brazilian, 460  BrdU, 412  breakage rate, 419  breakdown, 4, 42, 67, 80, 295, 484  breast, 174, 295, 300  breast milk, 295, 300  breathing, 28, 30, 32, 199  breeding, 12, 125, 341, 380, 382, 383, 406, 476, 595  British, 595  British Columbia, 595  Brno, 154  broad spectrum, xii, 41, 42, 302, 435  brominated flame retardants, 308, 312  bromine, 304, 306  bromodeoxyuridine, 104  bronchial asthma, 33  bronchitis, 32  Brussels, 315, 316, 317, 318, 319, 320, 322, 323,  324, 328, 329  bubbles, 229  budget line, 163  Buenos Aires, 72, 267, 278, 279, 281, 291  buffer, 142, 318, 583  building blocks, 542  buildings, 2, 5, 8, 11, 33, 34, 36, 38, 43, 51, 67, 539  Bulgaria, 133, 135, 151, 234, 569  burn, 7, 29, 30, 305  burning, 3, 4, 8, 31, 32, 45, 48, 57, 82, 87, 166, 171,  184, 208, 286, 497, 555, 558, 563  burns, 28  bursa, 98, 99, 101, 105, 106, 107, 109, 110, 112, 113 

Burundi, 298, 309  buses, 8, 30, 34  business, 43, 44, 318, 540  bypass, 130  by‐products, 13, 163, 184, 246, 551 

C  caecum, 484  Caenorhabditis elegans, 439, 464  calcitonin, 466  calcium, 19, 135, 167, 195, 199, 221, 266, 338, 441,  466, 483  calcium channel blocker, 221  calcium channels, 221  calibration, 56, 420, 595  California, 89, 176, 177, 179, 220, 274, 282, 329,  330, 400, 405, 412, 470, 474  campaigns, 167, 269, 581, 582, 583, 585, 588, 591  Canada, 34, 64, 110, 309, 310, 311, 473, 474, 491,  492, 528, 567, 595  canals, 126, 229  cancer, 4, 14, 16, 17, 38, 153, 165, 174, 308, 413,  423, 424, 443, 450, 456, 465, 470, 477  Cancer, 14, 153, 295, 422, 424, 463, 469, 578  cancer treatment, 16  cancers, 174, 413, 444  capacity, 24, 92, 117, 147, 154, 160, 174, 183, 206,  211, 241, 246, 249, 260, 265, 266, 342, 345, 364,  411, 418, 419, 452, 498, 500, 524, 527, 538, 557,  559, 562, 566  capillary, 312  capital, 238, 519, 538, 549, 558  capital cost, 558  carapace, 482, 486, 489  carbides, 6  carbohydrate, 81, 93  carbohydrates, 6, 18, 81  carbon, 2, 3, 6, 9, 18, 19, 27, 31, 32, 37, 38, 69, 70,  77, 78, 82, 85, 93, 165, 176, 228, 249, 251, 298,  301, 306, 317, 339, 402, 520, 521, 522, 530  Carbon, 20, 27, 31, 32, 93, 173  carbon dioxide, 6, 18, 19, 31, 38, 339  carbon monoxide, 2, 3, 6, 9, 27, 31, 32, 37, 520, 521,  530  carbon paper, 301  carbonates, 6, 233, 238, 245  carboxyl, 504  carboxylic, 87  carcinogen, 151, 300, 427 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

Index carcinogenesis, 155, 421, 444, 468, 492  carcinogenic, 135, 151, 182, 214, 294, 295, 297, 421,  489, 522, 531, 543  carcinogenicity, 135, 300, 302, 306, 337, 432  carcinogens, 32, 153, 188, 295, 302, 435, 445, 469,  543  carcinoma, 472  carcinomas, 295  cardboard, 11  cardiovascular, 134, 135  Cardiovascular disease, 36  cardiovascular system, 134  cargo, 226, 269  carotene, 440  carotenoids, 80  carpets, 304  carrier, 27, 200, 453, 498  CAS, 541  case study, 72, 131, 188, 230, 253, 291, 292, 400,  477  Caspian, 447, 474  casting, 301  castration, 110  catabolic, 572  catabolism, 472  catalase, 433, 439  catalysis, 428, 439, 520  catalyst, 94  catalytic, 292, 435, 520, 522, 528, 529  catalytic activity, 528, 529  catchments, 82, 227, 235  catfish, 218, 441, 467, 470  cathode, 417  cation, 211, 516  cations, 495, 496, 504, 507, 513, 514  cats, 260  cattle, 22, 27, 151, 269  causation, 579  cavities, 33  cell adhesion, 530  cell culture, 414  cell cycle, 141, 142, 154, 412, 414, 424  cell death, 141, 147, 444, 471  cell division, 79, 417  cell growth, 18, 502  cell line, 104, 455, 458, 461, 530  cell membranes, 200, 507  cell metabolism, 570  cell surface, 500, 503, 504  cellular regulation, 484 

603

Cellular response, 472  cement, 47, 230, 233, 241  central nervous system, 14, 17, 134, 167  centralized, 163  centromere, xiv, 133, 139  centromeric, xiv, 133, 139, 153  cephalopods, 201  ceramic, 233  cesium, 16  changing environment, 226, 443  channels, 55, 86, 200, 211, 229, 237, 264, 441  chaperones, 462, 526  Chaperones, 463  charcoal, 31  charged particle, 62  chelates, 504  chelating agents, 196  chelators, 486  chemical agents, 417  chemical bonds, 573  chemical composition, xvi, 91, 235, 259, 316, 317,  319, 324  chemical interaction, 363  chemical properties, 66, 165, 298, 319, 328, 396  chemical reactions, 30, 572  chemical stability, 6, 164, 302  chemical structures, 436  chemical vapour, 544  chemical weapons, 165  chemistry, 91, 174, 217, 219, 220, 237, 243, 280,  315, 316, 317, 318, 398, 407, 421, 443, 480, 498,  514, 515, 543, 570  Chernobyl, 63, 65, 450, 476  Chernobyl accident, 476  chicken, 99, 103, 104, 110, 111, 112  chickens, 101, 102, 106, 107, 108, 111, 112, 113  chicks, 98, 101, 105, 106, 107, 112, 489  childhood, 105  children, 14, 17, 31, 32, 39, 108, 113, 116, 150, 167,  300, 483  China, 1, 5, 21, 22, 37, 38, 40, 67, 157, 171, 172,  178, 181, 190, 285, 286, 287, 291, 292, 296, 298,  303, 307, 309, 311, 506, 515  Chinese, 1, 38, 151, 157  chlordane, 178, 294, 302  chlordanes, 296  chloride, 7, 151, 154, 196, 204, 208, 211, 225, 298,  414, 425, 498, 551  chlorinated hydrocarbons, 163, 164, 178, 181, 294,  302, 470, 546 

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604

Index

chlorination, 302, 396, 400  chlorine, 2, 13, 87, 164, 194, 229, 241, 294, 298,  301, 302, 306, 393, 407  chlorobenzene, 295  chlorophenols, 447  chlorophyll, 74, 80, 259, 339, 342, 349, 363, 365,  372, 378, 396, 397, 398, 403  Chlorophyll‐a, 363, 372, 396  cholera, 18, 47  cholesterol, 520  cholinesterase, 454, 466  chromatid, 141, 412, 423, 445, 470  chromatin, 134, 141, 143, 149, 152, 154, 413  Chromatin, 142, 154  chromatography, 444  chromium, 13, 23, 166, 193, 195, 198, 201, 206, 208,  218, 219, 227, 234, 236, 248, 249, 282, 419, 422,  456, 515, 550  Chromium, 198, 206, 219, 220, 247, 470, 505, 506  chromosome, 134, 135, 136, 137, 138, 141, 147,  148, 149, 151, 152, 412, 413, 414, 424, 433  chromosomes, 17, 137, 139, 141, 153, 413, 423,  445, 470, 507  Chromosomes, 424  chronic, 16, 17, 32, 97, 105, 134, 135, 136, 150, 184,  211, 214, 219, 221, 267, 280, 295, 302, 333, 336,  338, 418, 428, 469, 473, 573  chronic disease, 16, 573  chronic diseases, 16, 573  chronic kidney disease, 134  Chronic pulmonary disease, 135  cigarette smoke, 32  cigarette smokers, 32  cigarette smoking, 27  cigarettes, 33  Cincinnati, 475, 567  circulation, 32, 88, 108, 232, 234, 235, 237, 255,  257, 261, 264, 328, 342, 401, 431, 557  cirrhosis, 167  cis, 302  citizens, 33, 116, 167  civilian, 164, 294  clams, 383, 414, 418, 469, 476, 488, 489, 529, 535  classes, xxi, 141, 194, 433, 435, 436, 461, 519, 546,  583, 584, 586, 588  classical, 432, 447, 584  classification, 9, 194, 216, 255, 306, 436, 480, 581,  583, 584, 593, 594, 595 

classified, xii, 9, 30, 41, 42, 66, 115, 127, 128, 163,  248, 291, 300, 302, 411, 413, 436, 437, 503, 519,  588  clay, 23, 33, 127, 177, 225, 228, 235, 244, 249, 267,  324, 363, 498  clays, 264, 289, 480  Clean Air Act, 177  Clean Water Act, 177  cleaning, 11, 13, 14, 20, 25, 27, 167, 170, 171, 184,  543, 546, 547, 549  cleanup, 545  clean‐up, 26, 38  cleavage, 522  climate change, 4, 89  Climatic change, 83  clinical, 125, 413, 489  clinics, 116  clone, 525  cloning, 455, 460, 462, 475, 525, 532, 534  closure, 556, 557, 558  clothing, 10  clouds, 37  cluster analysis, 345, 584  clusters, 436  coagulation, 237  coal, xvi, 3, 4, 6, 7, 8, 15, 28, 30, 31, 37, 38, 40, 64,  65, 70, 166, 232, 243, 285, 286, 289, 298, 488  coal‐burning, 30  coalfields, 37  coastal areas, 44, 45, 169, 177, 178, 183, 215, 224,  229, 239, 340, 373, 416  coastal communities, 237  coastal zone, 72, 190, 237, 264, 411  coatings, 238, 304, 543  cobalt, 12, 166, 195, 198, 248, 265, 439, 513, 514  coding, 448, 449, 450  codon, 476  cofactors, 198, 439  cold war, 72  Coleoptera, 594  colic, 167  collaboration, 278  collisions, 25, 185  colon, 472  colonization, 341, 382, 383, 384, 397  Colorado, 486, 594  colors, 124  Columbia, 492  coma, 32, 302  combined effect, xvi, 315 

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Index combustion, xvi, 9, 27, 28, 29, 30, 31, 32, 33, 37, 78,  182, 268, 285, 286, 289, 298, 306, 332, 520  combustion processes, 298  commerce, 185  commercial, 8, 10, 11, 13, 17, 19, 22, 29, 64, 99, 125,  170, 190, 219, 229, 230, 234, 241, 244, 276, 291,  297, 304, 305, 312, 319, 320, 443, 498  communication, 4, 322, 403  communities, 5, 12, 18, 30, 43, 44, 45, 46, 73, 74,  76, 79, 94, 157, 264, 294, 382, 389, 405, 406, 431,  432, 479, 512, 518  compaction, 557  comparative research, 465  compatibility, 302  compensation, 93, 185, 187  competition, 80, 85, 89, 379, 383, 389, 480, 500, 502  competitive advantage, 83  competitiveness, 20  competitor, 75  compilation, 271, 273  complement, 103, 104, 419  complementary, 326, 433, 442, 468, 570  complementary DNA, 468  complexity, 104, 253, 443, 459  compliance, 54, 55, 56, 137, 320, 545, 546  components, 18, 42, 62, 65, 67, 100, 104, 180, 198,  269, 298, 306, 317, 319, 340, 342, 400, 452, 479,  488, 503, 504, 520, 531, 541, 542, 543, 544, 555,  559, 564, 565  composition, 2, 73, 75, 79, 80, 89, 93, 95, 127, 143,  168, 182, 227, 230, 237, 245, 252, 255, 317, 319,  339, 367, 368, 370, 371, 372, 373, 375, 379, 382,  383, 384, 397, 404, 406, 416, 431, 460, 480, 504,  531, 551  compositions, 190, 309, 436  composting, 126, 131  compression, 168  computer, 123, 124, 286  computers, 304, 305, 306  concentrates, 296  conception, 105, 569, 572  concrete, 11, 33, 46, 83, 125, 163  Concrete, 35  condensation, 8  conditioning, 23  conduction, 100  conductivity, 559, 570  confidence, 119, 272, 273  confidence interval, 272, 273  configuration, 233, 556 

605

conformational, 154  conformity, 545  confusion, 32, 541  Congress, 72, 174, 216, 400, 514, 565  conifer, 594  conjugation, 299, 456, 457, 521  Connecticut, 260  connective tissue, 100, 107  consensus, 483, 540  consent, 552  conservation, 46, 476, 538, 539, 549  constraints, 258, 447, 563  construction, 7, 11, 20, 27, 29, 30, 34, 35, 41, 42, 43,  44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 57,  58, 59, 63, 65, 126, 227, 247, 559, 564, 583  Construction and demolition, 11  construction materials, 27, 65  construction sites, 7, 11, 47, 583  consultants, 44, 540  consumer electronics, 11  consumer goods, 306  consumers, 200, 202, 208, 211, 212, 214, 300  consumption, 21, 42, 44, 49, 55, 81, 119, 146, 167,  169, 181, 194, 214, 215, 294, 296, 390, 391, 396,  398, 442, 538  contaminant, 22, 52, 61, 97, 98, 106, 176, 177, 178,  179, 180, 181, 183, 189, 194, 225, 230, 280, 285,  291, 296, 299, 311, 410, 450, 451, 453, 461, 469,  478, 517, 518, 521, 538  contaminated food, 15, 149, 434, 440  contaminated soils, 297  continental shelf, 227, 228, 235, 238, 251, 259  contingency, 588, 591  continuing, 58, 68, 176, 208  continuity, 277  continuous data, 584  contraceptives, 441  control group, 136, 137, 138, 144, 145, 146  controlled, 25, 50, 56, 78, 95, 136, 171, 175, 183,  196, 206, 286, 304, 339, 348, 438, 454, 480, 505,  555, 556, 557, 562  convection, 328  convective, 325, 563  conversion, 521, 545, 556, 557, 592  conversion rate, 556  cooking, 32  cooling, 23, 37, 341, 342, 357, 389, 390, 391, 393,  396, 397, 400, 403, 405, 513  coordination, 14, 167, 218, 573  coral, 191, 406 

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606

Index

coral reefs, 406  correlation, 149, 234, 289, 317, 322, 326, 345, 348,  354, 356, 357, 358, 360, 363, 364, 372, 373, 415,  419, 434, 439, 444, 445, 446, 588, 591, 593  correlation coefficient, 289, 591  correlations, 98, 105, 289, 315, 316, 354, 451, 452,  588, 591  corrosion, 265, 393, 403, 506  corrosive, 13, 22, 27, 125, 545  corrosivity, 13  cortex, 99  cortical, 99  corticosteroids, 108  corticosterone, 108  corticotropin, 108  cortisol, 433  Corynebacterium, 495, 499  cosmetics, 18, 33  cosmic rays, 62, 65, 67  cost saving, 545  cost‐effective, 551  costs, 5, 24, 44, 47, 58, 278, 540, 543, 544, 545, 547,  548, 549, 551, 557, 558  costs of production, 549  cotton, 20  coughing, 28, 30, 167  coupling, 447, 448, 452, 498, 561  covalent, 416, 443, 469, 520  covalent bond, 416, 520  coverage, 123, 124, 163, 341, 373, 375, 377, 379,  381, 502  covering, 33, 74, 185, 239, 246, 548, 554  crab, 266, 267, 279, 280, 437, 439, 455, 461, 465,  486, 487, 523, 532  Crassostrea gigas, 266, 414, 424, 451, 470, 471, 476  Crete, 224, 233  criminology, 70  Croatia, 210, 213, 424, 426  crops, 5, 8, 11, 21, 28, 36, 164, 296, 298, 322  cross links, 143  crosstalk, 108  crude oil, 158, 168, 169, 184, 189, 229, 337, 419,  429, 450, 458, 531  crust, 16, 65, 166, 250, 251, 270, 286  crustaceans, 178, 190, 201, 211, 266, 267, 296, 309,  383, 410, 411, 436, 483, 484, 486, 487, 490, 523,  529  crystal, 246  crystal lattice, 246  crystalline, 294, 465, 483 

crystals, 484  C‐terminal, 525  cultural, xv, 80, 82, 223, 241  culture, 236, 405, 421, 423, 499, 500, 512  customers, 58, 545  cyanide, 13, 550  cyanobacteria, 73, 74, 75, 76, 77, 79, 80, 81, 83, 85,  86, 87, 89, 90, 91, 92, 93, 94, 367, 438, 464  Cyanobacteria, 73, 74, 75, 77, 79, 80, 81, 82, 83, 86,  89, 90, 91, 92  cyanobacterium, 80, 85, 92, 93, 94  cycles, 8, 95, 317, 377, 402, 412, 497, 512, 550  cycling, 85, 220, 253, 256, 340, 438, 489, 498  cyclohexane, 298  cyclophosphamide, 445  Cyprus, 224, 254  cyst, 107  cysteine, 435, 436, 484  cysteine residues, 484  cytochemistry, 472  cytochrome, 428, 451, 455, 457, 465, 469, 470, 506,  518, 520, 521, 524, 528, 530, 531, 532, 533, 534  cytogenetic, 151, 152, 153, 412, 413, 414, 416, 417,  423, 445  cytokine, 97, 101, 107, 108  cytokines, 104, 108, 113, 437  cytokinesis, 471  cytology, 490  cytometry, 104, 413  cytoplasm, 206, 413, 437, 525, 526  cytoplasmic membrane, 86, 507  cytosine, 471  cytosol, 139, 520, 532  cytosolic, 435, 441, 484  cytotoxic, 426  cytotoxicity, 472, 530  cytotoxins, 85 

D  D. melanogaster, 527  dairies, 11, 22  dairy, 22  danger, 31, 171, 180, 232, 329, 410  data analysis, 105  data base, 585  data collection, 98, 541  data distribution, xvii, 479  data set, 66, 183, 325, 584, 591  database, 174, 468, 583 

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Index dating, 70, 71, 172, 179  daughter cells, 445  Dead Sea, 516  death, 4, 14, 26, 32, 36, 85, 105, 162, 277, 302, 487,  518, 575  deaths, 4, 18, 486, 487  decay, 1, 9, 15, 28, 29, 33, 62, 63, 64, 70, 71, 160,  166, 172  decibel, 33, 35, 126  decision making, xii, 41  decision trees, 584  decisions, 181, 540, 546  decomposition, xviii, 3, 349, 356, 359, 553, 556, 557,  558, 566  deep‐sea, 181, 219, 265  deep‐sea hydrothermal vents, 265  defects, 14, 174, 413  defense, 16, 149, 458, 459, 518  defense mechanisms, 518  defenses, 478, 503  deficiency, 485, 502  definition, xi, 1, 10, 91, 165, 325, 433  deflate, 75  deflation, 329  deforestation, 82  deformities, 112, 446  degenerate, 12  degradation, 18, 21, 41, 44, 56, 125, 159, 265, 270,  296, 298, 299, 302, 348, 409, 472, 543, 555, 556,  557, 562  degradation process, 562  degradation rate, 298, 472  degrading, 22, 235, 431  degree,  42, 99, 115, 131, 141, 142, 167, 244, 248,  301, 302, 304, 332, 333, 334, 336, 420, 449, 500,  502, 546, 569, 573  dehydration, 170  delayed puberty, 167  delivery, 251, 456  Delphi, 118, 253, 474  delta, 220, 235, 241  Delta, 181, 244, 252, 257, 298, 330  demand, 3, 18, 55, 160, 165, 400, 546, 548, 549, 551  demobilization, 180, 190  Democratic Republic of Congo, 64  demographic, 224, 447, 448  denaturation, 502  denatured, 437  denaturing gradient gel electrophoresis, 449  dengue, 47 

607

Denmark, 318, 329, 419, 429  density, 34, 76, 99, 165, 193, 307, 326, 341, 342,  350, 357, 369, 370, 371, 374, 377, 379, 382, 383,  389, 397, 398, 446, 468, 496, 557, 558  dentists, 13  deoxynucleotide, 102  deoxyribonucleic acid, 154  dependant, 4, 437, 451, 458  dependent variable, 584  deposition, 8, 66, 78, 84, 85, 101, 177, 178, 179,  255, 264, 292, 301, 310, 315, 316, 317, 318, 325,  328, 329, 330, 477, 505, 508, 513, 581, 588, 595  deposition rate, xix  deposits, 15, 16, 167, 180, 227, 237, 238, 249, 251,  257, 264, 483  depression, 14, 32  deprivation, 85  derivatives, 29, 188, 310, 438, 521  dermal, 218  dermatitis, 188  dermatological, 300  desalination, 26, 342  desert, 3, 330  desire, 549  desorption, 237, 299, 362, 512  destruction, 26, 38, 102, 170, 551  detection, 153, 178, 267, 282, 283, 300, 320, 413,  421, 422, 423, 424, 426, 427, 428, 433, 442, 444,  445, 448, 467, 470, 471, 473, 517, 519, 527, 528,  529, 593, 594  detergents, 4, 14, 18, 23, 170, 184, 194, 417  determinism, 91  detoxification, 211, 434, 435, 436, 457, 482, 484,  490, 491, 501, 503, 504, 513, 514, 516, 520, 521,  522, 532  Detoxification, 484, 530  detoxifying, 446, 456, 466  detritus, 390  deuterium oxide, 463  devaluation, 572  developed countries, xix, 34, 35, 161, 553  developed nations, 27, 34  developing countries, xi, 35, 37, 201, 296, 554, 558,  561, 563, 567  deviation, 397  diagenesis, 252  diagnostic, 16, 65, 69, 174, 428, 442, 473  diatoms, 74, 75, 76, 80, 83, 92, 205, 363, 367, 368,  370, 399  dibenzofurans, 303, 313 

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608

Index

dibenzo‐p‐dioxins, 303, 311, 313  dicentric chromosome, 413  dielectric, 301, 302  dielectrics, 306  diesel, 9, 34, 47, 168, 184, 317, 318, 329, 532  diesel engines, 9  diesel fuel, 47, 184, 329  diet, 133, 136, 293, 294, 299, 300, 306, 331, 482,  486, 489  dietary, 150, 294, 312, 474, 486, 488, 492  diets, 182, 214, 294, 520  differentiation, 99, 101, 107, 448, 449, 502, 592  diffusion, 180, 197, 199, 505, 526, 570  diffusion process, 199  digestion, 170, 288, 413, 444  digestive tract, 162, 170  dignity, 584  dimeric, 435, 460  dimerization, 525, 533  dimethylsulphoxide, 418  dimorphism, 463  dinoflagellates, 75, 367, 368, 370  dioxin, 164, 311, 446, 457, 466, 525, 526, 533  dioxin receptor, 533  dioxins, 163, 164, 182, 306, 435  directives, xvi, 316, 317  disaster, 15, 37, 38, 158, 167  discharges, 21, 25, 50, 55, 175, 179, 181, 183, 230,  234, 235, 236, 244, 265, 269, 354, 540, 547  discomfort, 1, 318  discounts, 79  Discovery, 530  discrimination, 416, 449  discs, 286  diseases, 4, 5, 18, 29, 38, 47, 105, 163, 443  disinfection, 19  dispersion, 130, 233, 301, 497  displacement, 502  disposition, 152, 153, 312, 457  dissipative structure, 570  dissipative structures, 570  dissociation, 299  dissolved oxygen, 18, 88, 118, 160, 194, 195, 206,  339, 392, 502  distillates, 13  distillation, 9  distilled water, 270  distress, 446  disulfide, 103, 440  disulfide bonds, 103 

diurnal, 317  diuron, 424  diversity, 23, 75, 85, 86, 89, 175, 291, 341, 366, 370,  372, 373, 377, 388, 404, 432, 437, 475, 476, 477,  532, 533  diving, 26, 331, 336  division, 325, 411, 413, 540, 567  dizziness, 14, 33  DNA breakage, 141  DNA damage, 135, 141, 143, 144, 147, 148, 149,  155, 409, 410, 412, 414, 416, 417, 418, 419, 422,  423, 425, 426, 427, 428, 429, 433, 443, 445, 463,  465, 469, 470, 472  DNA strand breaks, 411, 414, 419, 427, 428, 444,  452, 469  doctor, 116  dogs, 35  dominance, 74, 75, 76, 77, 79, 80, 83, 90, 91, 92,  341, 367, 370, 379, 382, 384, 387, 388, 475  donors, 103, 428  doors, 32, 35  dosage, 538  double bonds, 522  drainage, 21, 25, 42, 55, 125, 126, 159, 211, 234,  238, 241, 246, 345, 355, 363, 364, 480, 559, 560,  563  drinking, 7, 8, 18, 20, 21, 38, 74, 83, 117, 118, 199,  295, 333, 425, 493, 538  drinking water, 7, 18, 20, 21, 38, 117, 118, 199, 295,  333, 425, 493  Drosophila, 459, 475, 525  drought, 83  drug metabolism, 530  drug resistance, 456  drugs, 6, 97, 435, 456, 520  drying, 77  dumping, 3, 12, 23, 125, 161, 162, 164, 165, 179,  238, 265, 268, 271, 429, 495, 496, 554, 555, 561  duodenum, 455  duplication, 423, 453, 520  durability, 162, 393, 551  duration, 14, 26, 53, 76, 149, 167, 341, 387, 389,  487  dust, 23, 42, 45, 48, 54, 55, 133, 134, 135, 136, 139,  148, 152, 173, 188, 233, 305, 315, 316, 317, 318,  324, 329, 330, 497, 544  dust storms, 318, 329, 330  dusts, 159, 431  dynamic theory, 571  dysplasia, 302 

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Index

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

E  E. coli, 506, 507, 508  early warning, 447  earth, 3, 4, 16, 23, 29, 30, 33, 39, 45, 53, 54, 62, 63,  65, 71, 166, 173, 286, 301, 317, 318, 356, 496,  581  earthquake, 38, 127, 257  earthworm, 432, 463  eating, 32, 164, 279, 296, 303, 446  echinoderms, 436  ecological damage, xiv, 22, 37, 193  ecological systems, 44, 45, 304  ecologists, 105  ecology, 42, 89, 90, 91, 92, 93, 165, 341, 399, 402,  404, 406, 421, 431, 476, 569  economic, 3, 5, 26, 37, 39, 42, 44, 47, 56, 74, 83,  175, 179, 181, 188, 410, 498, 551  economic activity, 39  economic growth, 3, 181  economic losses, 188  economic problem, 37  economic security, 5  economics, 545, 547  economy, 5, 38, 39, 537  ecosystem, 4, 28, 38, 74, 75, 77, 87, 95, 98, 160,  164, 170, 171, 181, 182, 190, 194, 229, 282, 295,  337, 339, 369, 398, 399, 406, 410, 411, 432, 453,  475, 478, 488, 496, 499, 512  ecotoxicological, 99, 100, 104, 134, 145, 148, 152,  310, 313, 410, 431, 433, 434, 435, 437, 438, 471,  474, 518, 581, 582  ecotoxicology, 133, 136, 433, 442, 443, 446, 449,  450, 451, 453, 475, 477, 478, 530, 593  education, 12, 116  Education, 70  Eel, 528  efficacy, 87  effluent, 3, 22, 159, 181, 234, 236, 243, 244, 246,  471, 474, 507, 528, 529, 535  effluents, 166, 194, 195, 229, 234, 235, 236, 237,  238, 244, 246, 247, 263, 268, 415, 440, 441, 444,  450, 466, 467, 480, 496, 497, 508, 514, 531, 534,  537, 538  efflux mechanisms, 507  efflux transporter, 458  efflux transporters, 458  egg, 27, 101, 142, 433, 447  eggs, 14, 106, 107, 295, 310, 447, 472 

609

Egypt, xxi, 67, 203, 205, 207, 210, 213, 219, 223,  225, 246, 260, 261, 300, 303, 495  Egyptian, 219, 247, 248, 261, 303  electric charge, 572  electric current, 570  electric power, 7, 8, 26, 27, 30  electric utilities, 29  electrical, 42, 55, 88, 301  electrical conductivity, 55  electrical resistance, 301  electricity, 3, 4, 5, 54, 195  electrochemical, 196  electrolyte, 207  electromagnetic, xii, 61, 431, 571  electromagnetic wave, xii, 61  electromagnetic waves, xii, 61  electron, 65, 503, 520, 522, 530  electron density, 520  electronic, v  electronics, xvi, 293, 294, 305, 306  electrons, 62, 63, 172, 520  electrophoresis, 417, 422, 427, 428, 442, 443, 444,  449  electroplating, 13, 23, 265, 488, 549, 550  electrostatic, v, 520  elongation, 326, 328, 469  embryo, 14, 413, 421, 424, 445, 452  embryogenesis, 99  embryonic, 99, 105, 106, 107, 112, 491  embryonic stem, 99  embryonic stem cells, 99  embryos, 14, 110, 112, 113, 424, 447, 450, 453, 457,  458, 476, 485, 533, 534  emergency planning, xiii, 115, 130  emerging issues, xiii, 97  emission, 27, 30, 45, 48, 126, 133, 151, 171, 180,  193, 249, 298, 318, 320, 324, 329, 330, 540, 563,  564, 583, 584, 587, 588, 591, 592  emission source, 27, 324, 583, 584, 591  emitters, 16, 28  emphysema, 32  employees, 35  employment, 59  encoding, 508, 518  endangered, 36, 38, 177, 476  Endangered Species Act, 283  endocrine, 99, 106, 108, 112, 113, 266, 280, 294,  308, 441, 466  endocrine system, 106, 441  endocrine‐disrupting chemicals, 466 

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610

Index

endocytosis, 200  endoderm, 482  endogenous, 106, 107, 148, 416, 428, 438, 439, 520,  522  endonuclease, 413, 417  endoplasmic reticulum, 520  energy consumption, 452, 545  energy density, 168  energy efficiency, 44  energy transfer, 572  engineering, v, xii, 41, 63, 538, 540, 565  engines, 30, 161  England, 158, 218, 491, 529, 534  English, 205, 210, 213, 219, 227, 254, 278, 337, 444,  469  Enhancement, 112, 514, 566  enlargement, 75, 300, 302, 472  entertainment, 34  enthusiasm, 551  entrapment, 498  entropy, 570, 572, 584  environmental audit, 58  environmental awareness, 552  environmental change, 3, 76, 367, 453, 525, 570,  578  environmental characteristics, 403  environmental chemicals, 103, 308, 473  environmental conditions, 75, 89, 193, 265, 277,  295, 341, 356, 362, 369, 410, 419, 554  environmental contaminants, 97, 98, 105, 108, 177,  198, 206, 294, 310, 410, 421, 423, 454, 456, 478,  519  environmental degradation, 115, 116, 306  environmental effects, 18  environmental factors, 66, 75, 341, 404, 416, 435,  437, 459, 487  environmental impact, 21, 23, 29, 41, 42, 45, 50, 53,  54, 56, 59, 165, 226, 543, 554, 557, 558  Environmental Impact Assessment, 58, 131  Environmental Impact Assessment (EIA), 58  environmental issues, 38, 49, 51, 55, 58, 59, 223,  539  environmental movement, 165  Environmental Performance Indicators, 59  environmental policy, 50, 54, 55, 58, 59  environmental protection, 42, 188  Environmental Protection Agency, 33, 39, 109, 174,  214, 221, 295, 298, 475, 552  environmental threats, 555  environmental tobacco, 32 

environmentalists, 480  enzymatic, 431, 433, 434, 438, 442, 451, 465, 503,  561  enzymatic activity, 442, 451  enzyme, 83, 103, 189, 198, 206, 211, 302, 419, 439,  440, 442, 453, 455, 457, 458, 464, 465, 467, 482,  485, 489, 502, 503, 528, 531, 532, 572  enzyme induction, 302, 455  enzyme‐linked immunosorbent assay, 103  enzymes, 143, 201, 208, 211, 218, 221, 295, 417,  426, 435, 438, 439, 440, 441, 442, 449, 455, 456,  457, 465, 466, 468, 477, 485, 502, 503, 506, 507,  518, 519, 520, 521, 529, 531, 534  eosinophils, 100  EPA, 5, 10, 39, 174, 214, 221, 243, 295, 298, 300,  303, 308, 309, 311, 492, 541, 550, 552, 567  epidemiological, 36, 331, 333  epidemiology, 108  epiphytes, 85  episodic, 227  epithelia, 99, 200  epithelial cell, 199  epithelial cells, 199  epoxides, 443, 522  epoxy, 373  equilibrium, 149, 197, 301, 333, 390, 485, 522, 579  equipment, xviii, 13, 17, 22, 29, 30, 34, 35, 45, 48,  49, 56, 57, 103, 319, 413, 537, 539, 541, 545, 546,  550, 558, 559, 560, 564  erosion, xvi, 23, 44, 45, 47, 52, 54, 55, 56, 57, 159,  181, 235, 249, 264, 265, 315, 316, 450, 497  erythrocyte, 103  erythrocytes, 103, 134, 425, 442, 444, 465, 470  Escherichia coli, 505, 510, 514, 516  estates, 234  esterase, 86, 440, 452  esters, 440, 546  estimating,  547, 595  estradiol, 107, 112, 113  estrogen, 101, 106, 107, 108, 112, 113, 463  estrogens, 107  estuaries, 22, 29, 78, 157, 158, 175, 177, 201, 203,  208, 211, 214, 221, 229, 235, 243, 258, 264, 266,  276, 278, 279, 283, 340, 401, 403, 421, 452, 467,  469, 476, 477, 492  estuarine, 79, 87, 90, 91, 94, 176, 181, 190, 206,  208, 214, 217, 224, 253, 259, 264, 265, 266, 268,  277, 280, 282, 291, 360, 368, 399, 403, 405, 409,  425, 429, 466, 473, 478, 490  estuarine systems, 399 

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Index ethane, 179  ethers, xvi, 293, 294, 304, 305, 308, 312, 313, 546  ethical, 539  ethnic groups, 109  ethylene, 106, 546  ethylene glycol, 546  EU, 283, 317, 320  eukaryotes, 155, 435, 437  eukaryotic, 77, 417, 444, 461  eukaryotic cell, 417, 444, 461  euphotic zone, 79, 81  Euro, 113  Europe, 34, 223, 227, 229, 239, 300, 324, 411, 564,  565, 581, 592, 595  European, 24, 72, 137, 251, 300, 302, 303, 318, 329,  420, 421, 427, 434, 455, 477, 550, 553, 582, 593  European Community, 420  European Union, 303  Europeans, 24  eutrophic, 75, 76, 79, 80, 81, 82, 87, 92  eutrophication, 25, 29, 73, 77, 78, 79, 80, 82, 87, 91,  92, 93, 94, 160, 254, 402  evaporation, 8, 30, 168, 169, 302  evidence, 42, 61, 68, 87, 89, 91, 105, 107, 109, 141,  151, 177, 181, 182, 196, 199, 237, 243, 245, 294,  295, 306, 349, 451, 453, 487, 488, 491, 534  evolution, 44, 89, 95, 317, 318, 330, 432, 434, 448,  459, 462, 468, 477, 507, 533, 570, 571, 579  evolutionary, 170, 447, 448, 475, 533  evolutionary process, 170  e‐waste, 313  exchange rate, 407  exchange rates, 407  excision, 147  excretion, 211, 312, 390, 393, 397, 406, 407, 482  exercise, 31, 543  exogenous, 99, 106, 107, 416, 438, 520  exons, 458  exoskeleton, 266, 482, 489  experimental condition, 453  experimental design, 109  expert, 469, 584  expertise, 118  experts, 4, 116, 175  exploitation, 48, 64, 71, 184, 185, 187, 234  explosions, 13, 17, 62, 63, 68, 69, 173, 178, 301, 302  explosive, 541, 545  explosives, 4  exponential, 442 

611

Exposure, 28, 30, 32, 33, 35, 36, 67, 71, 72, 113, 115,  123, 124, 125, 128, 174, 221, 295, 299, 301, 305,  306, 311, 338, 341, 485, 487, 492  external costs, 5  extinction, 36, 39, 448  extracellular, 354, 503, 504  extraction, 45, 48, 64, 159, 168, 169, 180, 226, 233,  241, 247, 250, 257, 262, 270, 288, 289, 291, 559  extraction process, 233  extrapolation, 109  Extraterrestrial, 62, 71  extrinsic, 266  Exxon, 171, 476  Exxon Valdez, 171, 476  eye, 32, 103  eyes, 13, 26, 28 

F  fabrication, 11, 15, 63  facies, 250  faecal, 390  failure, 25, 45, 147, 487, 545  false, 266  family, 11, 29, 116, 135, 163, 211, 219, 368, 456,  459, 460, 462, 519, 520, 523, 533  farm, 17, 22  farmers, 105  farming, 22, 317  farmland, 466  farmlands, 21, 22  farms, 11, 18, 103, 315, 343  Faroe Islands, 291  fasting, 110, 457  fat, 298  fatigue, 32  fats, 6, 18, 20, 164, 167, 294  fatty acid, 294, 441  fatty acids, 294, 441  fauna, 46, 55, 83, 204, 259, 260, 338, 341, 377, 405  fear, 550  fears, 38  February, 40, 269, 270, 275, 340, 342, 343, 345, 346,  348, 350, 356, 359, 364, 368, 370, 382, 388  fecal, 20, 489  feces, 305, 488  federal government, 563  feedback, 572, 573, 574  feed‐back, 540  feeding, 22, 26, 110, 197, 215, 397, 438, 563 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

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612

Index

feelings, 116  fees, 551  feet, 35, 127  feldspars, 237, 243  females, 136, 137, 140, 141, 146, 149, 208, 435  femur, 137  ferric oxide, 498  ferritin, 483, 484  ferrous metal, 487  fertility, 54, 165, 295, 398  fertilizer, 14, 22, 64, 78, 237, 360  fertilizers, 3, 4, 6, 14, 22, 23, 24, 87, 158, 159, 168,  228, 480  fetal, 105, 150, 306  fibrosis, 296  fidelity, 147  field theory, 570  film, 23  filter feeders, xiv, 157, 162, 396  filters, 83, 319, 324, 325, 326  financial resources, 447  finfish, 181, 190  fingerprinting, 449, 476  Finland, 528  fire, 13, 37, 40, 301, 306, 311, 313, 543  fire hazard, 13  fires, 3, 13, 37, 164, 174, 301, 558  first dimension, 443  fish meal, 157  fish oil, 157  fisheries, 170, 224, 244, 340, 403, 404  fishers, 483  fishing, 26, 118, 158, 161, 162, 163, 167, 188, 234,  236, 244, 247, 269, 496, 538  fission, 64  fitness, 431, 452, 453, 518  fixation, 93  flame, 176, 282, 283, 293, 294, 302, 304, 305, 306,  307, 308, 313, 438  flame retardants, 176, 302, 304, 306, 308, 313  flammability, 302, 541  flexibility, 562  flight, 64, 170  floating, 22, 87, 161, 162, 170, 184  flocculation, 88, 250  flood, 130, 251  flooding, 20, 52, 180, 280  flora, 23, 42, 46, 54, 367  flora and fauna, 23, 42, 46, 54  flotation, 234, 515 

flow, 4, 23, 25, 44, 53, 55, 104, 158, 176, 178, 199,  200, 227, 234, 236, 239, 243, 256, 391, 413, 448,  480, 540, 543, 549, 559, 560  flow rate, 200, 391, 543, 559  fluctuations, 5, 170, 325, 353, 369, 372, 485  flue gas, 299  fluid, 14, 20, 24, 47, 101, 185, 400, 486  fluorescence, 62, 417, 442  fluorescent light, 14, 301  fluoride, 27  fluorinated, 546  fluorine, 37, 229  fluorometric, 442  flushing, 77, 81, 83, 264, 566  fluvial, 237, 265  focusing, 87, 98, 163, 413, 443, 446  foils, 12  follicle, 107  follicles, 99, 106  follicular, 295  Food and Drug Administration, 483  food intake, 305  food production, 230  food safety, 215  foodstuffs, 62, 295, 298, 302  forest fire, 1, 3, 9, 31, 265  forest fires, 1, 3, 9, 265  forestry, 56, 297  Forestry, 8, 258  forests, 5, 28, 152, 164  formaldehyde, 13, 33, 126  fossil, 3, 4, 5, 8, 9, 27, 28, 30, 37, 49, 78, 82, 87, 182,  232, 268, 332, 497  fossil fuel, 3, 4, 5, 8, 9, 27, 28, 30, 37, 49, 78, 82, 87,  332, 497  fossil fuels, 3, 4, 5, 8, 27, 30, 38, 49, 78, 497  fouling, xvii, 266, 342, 389, 391, 393, 400, 405, 406,  407  fowl, 99, 109  Fox, 400, 427, 474  fractures, 167  fragility, 278  fragmentation, 42, 419  France, 8, 153, 172, 203, 205, 213, 219, 225, 227,  228, 229, 251, 266, 276, 313, 431, 470, 477, 528,  530, 534, 594  free radical, 16, 148, 428, 438, 443, 460, 465, 574  free radicals, 16, 148, 438, 443, 460, 465, 574  freedom, 185  frequency distribution, 273 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Index fresh water, 7, 39, 160, 176, 250, 296, 340, 345, 346,  359, 360, 363, 459, 480, 486, 514, 515, 549  friction, 34  Friday, 319  fuel, 3, 5, 15, 25, 29, 32, 49, 51, 57, 63, 65, 70, 168,  169, 173, 174, 189, 268, 286  fuel cycle, 15, 65, 70  fugitive, 315, 547  fumarate, 435, 457  fumigants, 28  fumigation, 28  functional analysis, 533  functional aspects, 98  fungal, 112, 298  fungi, 104, 160, 390, 404, 432, 436, 498, 499, 504,  514  fungicide, 298, 300, 457  fungus, 463  furnaces, 31  furniture, 10, 14, 33, 304, 306  fusion, 139 

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

G  galactic, 62  Gamma, 67  gamma radiation, 16, 172  gamma rays, 15, 62, 172  garbage,  2, 3, 10, 11, 14, 125, 162, 185, 271  gas chromatograph, 270, 282, 283, 312  gas exchange, 454  gas exploration, 480  gas phase, 301  gaseous waste, 159  gases, 1, 13, 19, 28, 29, 37, 38, 52, 125, 158, 173,  286  gasoline, 14, 30, 168, 169, 184, 208  gastric, 302  gastric mucosa, 302  gastroenteritis, 18  gastrointestinal, 16, 38, 86, 100, 134, 144, 145, 146,  167, 294  gastrointestinal tract, 86, 100, 134, 144, 167  Gaussian, 126, 586  gel, 142, 417, 422, 427, 428, 442, 443, 444, 468, 513  gels, 142  gemma, 524  GenBank, 533  gender, 138, 153 

613

gene, 142, 154, 155, 178, 190, 431, 433, 434, 436,  442, 443, 445, 448, 449, 450, 453, 455, 459, 460,  461, 462, 463, 464, 467, 468, 476, 507, 508, 516,  518, 519, 520, 525  gene expression, 142, 178, 190, 431, 433, 434, 436,  442, 443, 449, 453, 459, 460, 461, 464, 468, 518  gene pool, 448  generation, 2, 5, 27, 41, 42, 44, 53, 79, 108, 109,  125, 174, 270, 283, 382, 393, 438, 443, 452, 508,  522, 537, 538, 541, 543, 544, 545, 546, 549, 554,  555, 556, 557, 559, 562, 565  generators, 10, 551  genes, 104, 433, 439, 442, 443, 445, 448, 449, 450,  456, 458, 459, 460, 475, 505, 507, 515, 516, 518,  519, 526, 527, 530  genetic, 17, 134, 139, 140, 141, 147, 148, 152, 174,  410, 411, 412, 413, 414, 417, 418, 420, 423, 424,  433, 434, 442, 443, 445, 447, 448, 449, 450, 451,  452, 468, 470, 475, 476, 477, 502, 505, 519, 570  genetic control, 505  genetic defect, 17  genetic diversity, 447, 448, 449, 450, 475, 477  genetic drift, 434, 448  genetic information, 468  genetic marker, 470  genetic mutations, 476  genetics, 421, 475  Geneva, 150, 188, 310  genome, 104, 147, 448, 450, 573, 575  genomes, 104  genomic, 442, 458  genomics, 104, 111  genotoxic, 86, 134, 135, 140, 141, 147, 148, 149,  153, 154, 155, 410, 411, 412, 414, 416, 418, 419,  422, 423, 425, 427, 429, 443, 444, 450, 468, 469,  471  genotoxicology, 420  genotoxins, 421, 445, 470, 471, 475  genotype, 448, 451, 452, 477  genotypes, 448, 450, 451, 452, 453, 477  geochemical, 252, 254, 258, 271, 277, 497  geochemistry, 252, 258  geology, 67, 227  geomagnetic field, 62  geothermal, 28  Ger, 566  Germany, ix, 8, 94, 180, 227, 330, 475, 563, 566,  581, 582, 583, 586, 589, 591, 592, 593  germline mutations, 476  GH, 150, 151, 532 

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614

Index

Ghost, 163, 188  Gibbs, 491  Gibraltar, 224  gill, xiv, 199, 201, 208, 215, 221, 412, 414, 415, 416,  418, 419, 422, 424, 426, 429, 439, 445, 459, 465,  470, 486  gilthead seabream, 441  girls, 167  gland, 211, 418, 426, 428, 439, 457, 464, 468, 469,  472, 473  glass, 11, 24, 46, 103, 125, 161, 229, 230, 312  global climate change, 27  Global Positioning System, 343  global warming, xi, 1, 5, 37, 82, 83  glucose, 451  glutamine, 525  glutathione, 206, 299, 435, 439, 440, 456, 457, 458,  465, 485, 522  glutathione peroxidase, 439  glycerol, 438, 463  glycogen, 457  glycol, 546  glycoprotein, 436, 458  glycoproteins, 199  goals, 59, 551  gold, 506, 515  gonad, 429, 435  gonadal regression, 108  gonads, 106, 194, 201, 206, 208  government, v, 10, 14, 34, 55, 115, 186, 188, 551,  558  government policy, 551  gracilis, 375  grades, 232, 297  grading, 44, 45, 47, 48, 560  graffiti, 2  grain, 5, 177, 235, 237, 271, 289  gram negative, 515  gram‐negative bacteria, 507, 516  gram‐positive bacteria, 504  granites, 16  grants, 278  granules, 200, 460, 471, 483, 484  graph, 119, 333  graphite, 219  grass, 3, 10, 170, 298, 307, 477, 487  grasslands, 594  grazing, 73, 76, 80, 303, 383, 389  Great Lakes, 176, 217, 307, 313, 474 

Greece, 225, 229, 233, 234, 235, 236, 238, 253, 254,  255, 256, 257, 302, 311, 415, 426  greenhouse, 3, 4, 5, 29, 37, 38, 49, 563, 564  Greenhouse, 3  greenhouse gas, 3, 5, 29, 37, 49, 563, 564  Greenland, 182  gross domestic product, 5  ground water, 12, 78, 127, 554, 558  grounding, 25  groundwater, 2, 3, 13, 15, 16, 21, 22, 23, 44, 45, 70,  78, 127, 232, 539, 554  groups, 12, 76, 77, 80, 82, 83, 109, 136, 137, 138,  139, 143, 167, 176, 228, 239, 248, 294, 303, 304,  306, 325, 379, 384, 412, 414, 433, 434, 439, 443,  456, 485, 487, 502, 546, 584, 586  growth inhibition, 277  growth rate, xvii, 29, 79, 80, 92, 93, 200, 299, 341,  373, 375, 379, 380, 387, 447, 452  Guangdong, 307  guidance, 529  guidelines, 36, 66, 87, 153, 232, 248, 584  Gulf Coast, 280, 403  Gulf of Mexico, 220  Gulf of Oman, 190  gulls, 112, 113, 447, 455, 474, 476  gut, 100, 110, 200, 457, 482, 488 

H  habitat, 36, 38, 52, 54, 81, 409, 584, 594  habitation, 356  haemoglobin, 442, 457, 531  Haifa, 244, 245, 246, 259, 260  half‐life, 15, 63, 172, 299  halogen, 313  halogenated, 158, 535, 542, 543  handling, 17, 47, 55, 117, 174, 269, 537, 549, 552  hands, 333  harbour, 42, 251, 253, 263, 264, 265, 269, 271, 276,  279, 283, 375, 404, 405, 406, 419, 429, 445, 467,  474  hardness, 83, 195, 200  harm, 1, 2, 12, 18, 23, 27, 163, 172, 187, 188, 214  harmful, 2, 3, 12, 13, 14, 17, 21, 22, 30, 33, 61, 82,  94, 134, 157, 160, 163, 165, 167, 176, 184, 185,  188, 194, 214, 239, 244, 260, 295, 297, 315, 316,  433, 448, 503, 543, 569, 570, 578  harmful effects, 17, 134, 188, 214, 295, 570  Harvard, 334  harvest, 323, 324 

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Index harvesting, 88  hazardous materials, 20, 545  hazardous substance, 13, 14, 517, 538, 543  hazardous substances, 13, 14, 517, 538, 543  hazardous wastes, 10, 11, 13, 15, 44, 46, 47, 537,  538, 539, 541, 544, 551  hazards, 19, 36, 42, 64, 125, 158, 189, 496, 538  haze, 29, 328, 330  head, 100, 154, 269, 298, 558, 559, 562  health effects, 21, 32, 53, 94, 182, 303, 308, 328,  489, 493  health problems, 2, 4, 14, 31, 36, 165  health status, 218, 414, 578  hearing, 4, 33, 34, 35, 167  hearing loss, 33, 35  heart, 4, 28, 32, 36, 462  Heart, 203, 205, 210, 213, 219  heart disease, 4, 28, 32, 36  heat, 2, 3, 4, 6, 12, 27, 159, 195, 301, 302, 306, 342,  459, 461, 462, 463, 525, 546, 547, 572  heat shock protein, 459, 461, 462, 463, 525  heat transfer, 301  heating, xvi, 37, 94, 168, 169, 316, 317, 318, 320  heating oil, 169  heavy oil, 332  height, 66, 126, 583  helix, 147, 525, 533, 534  hematite, 290  hematological, 134, 151, 570  heme, 134, 434, 435, 519, 520  hemisphere, 177, 178, 411  hemoglobin, 31, 134, 135  hepatitis, 18  hepatocellular, 295  hepatocellular carcinoma, 295  hepatocyte, 421  hepatocytes, 211, 221, 464, 476  hepatoma, 455, 458  hepatotoxins, 85, 86  herbal, 112  herbicides, 14, 19, 22  Herbicides, 14  herbivorous, 267  heredity, 571  Hermes, 459  herring, 214, 447, 474, 476  heterodimer, 517, 519, 526  heterogeneity, 177, 251, 267, 454, 563  heterogeneous, 483, 584  heterotrophic, 514 

615

heterozygosity, 452  heuristic, 539, 540, 543, 544, 546, 547, 548, 575,  578  hexachlorobenzene, 178, 294, 296, 300, 304, 310  hexachlorocyclohexane, 294, 304, 309  hexachlorocyclohexanes, 178  hexane, 270  high blood pressure, 36, 167  high pressure, 171, 547  high risk, 31  high temperature, 29, 86, 270, 298, 305, 383, 555  higher quality, 550  highlands, 45, 188  high‐risk, 12, 115, 130  highways, 34, 582, 584  hip, 35  Hiroshima, 17  histidine, 436  histogram, 273, 274  histological, 99, 102, 277  Histological markers, 464  histology, 98, 110  histone, 142, 143, 149, 154  histopathology, 470  Holland, 113, 150, 424, 492  Holocene, 255  homeless, 38  homeostasis, 207, 211, 266, 440, 571, 572  homeowners, 18  homes, 17, 18, 37, 38, 161, 304  homogeneity, 273  homogeneous, 584  homogenous, 418  homolog, 516  homologous chromosomes, 139  homology, 436, 437  Honda, 338  honey, 432  Hong Kong, 1, 33, 157, 296, 298, 309, 415, 426  hormone, 36, 108, 112  hormones, 108, 113, 208, 266, 305, 306, 437, 438  hospital, 4, 13, 116  hospitals, 10, 11, 13, 18, 63, 126, 127  host, 66, 306, 414  hot spots, 176  hot spring, 28  hot water, 2, 171  hotels, 11  House, 150, 153, 578, 579 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

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616

Index

household, 3, 10, 11, 14, 18, 20, 35, 116, 125, 162,  164, 188, 239  household waste, 10, 14, 125, 239  households, 12, 19, 116, 125, 127, 160  housing, 99  human activity, 1, 3, 4, 25, 157, 166, 265, 267, 271,  318, 332  human exposure, 5, 67, 173  human milk, 311  human resources, 51, 540  humanity, 39  humic acid, 196, 480  humidity, xvi, 45, 48, 136, 311, 316, 320, 324, 328  humoral immunity, 112, 113, 574  humus, 302  hunting, 212  hybrid, 453, 559  hybridization, 468  hydraulic fluids, 301  hydride, 270, 283  hydrides, 270  hydro, 3, 6, 10, 25, 158, 159, 168, 169, 170, 176,  181, 182, 194, 258, 374, 411, 467, 469, 496, 521,  529, 542, 546  hydrocarbon, 6, 177, 258, 298, 426, 456, 512, 517,  519, 520, 526, 529, 531, 532, 533, 534  hydrocarbons, 3, 6, 10, 25, 158, 159, 168, 169, 170,  176, 181, 182, 194, 258, 411, 467, 469, 496, 529,  542, 546  hydrochemical, 253  hydrodynamic, 226, 264  hydrofluoric acid, 229  hydrogen, 6, 13, 19, 32, 104, 126, 418, 438, 439,  441, 480  hydrogen cyanide, 32  hydrogen peroxide, 13, 104, 418, 438, 439  hydrogen sulfide, 19  hydrolases, 440, 472  hydrologic, 560  hydrological, 70, 89, 126, 398, 401  hydrological cycle, 70  hydrology, 70, 255  hydrolysis, 507  hydroperoxides, 441  hydrophilic, 521  hydrophobic, 520  hydrostatic pressure, 437, 461  hydrothermal, 459  hydroxide, 196, 204, 206, 208, 520  hydroxides, 204, 290 

hydroxyl, 305, 438, 498, 504  hydroxyl groups, 504  hydroxylation, 522  hygiene, 20, 517  hypersensitivity, 102  hypertension, 134, 135, 150  hypertensive, 462  hypertrichosis, 300  hypothalamus, 108  hypothermia, 26, 170  hypothesis, 79, 349, 450, 452, 463, 579, 582, 584,  585  hypoxia, 85, 94, 187, 437, 446, 447, 453, 459  Hypoxia, 468  hypoxic, 206 

I  Iberian Peninsula, 225, 280  ice, 22, 182  identification, 43, 51, 54, 104, 366, 375, 413, 432,  461, 468, 541, 544, 582, 593  identity, 519  ignitability, 13  Illinois, 403  imagery, 594  images, 6, 94  imaging, 170, 326  imbalances, 170  immersion, 381  immobilization, 366, 498  immune cells, 100, 108  immune function, 101, 107, 109, 112  immune memory, 573, 576  immune response, 99, 100, 102, 104, 105, 108, 109,  110, 111, 112, 573, 574  immune system, 97, 98, 99, 100, 101, 103, 104, 105,  106, 107, 108, 109, 110, 111, 165, 446, 464, 473  immunity, 104, 110, 111, 447  immunization, 102, 103  immunocompetence, 98, 107, 111, 112  immunoglobulin, 100, 101, 103  immunological, 97, 99, 111, 113, 309, 433, 434, 436,  446  immunology, 98, 102, 109  immunosuppression, 100, 104, 105, 109, 474  immunosuppressive, 97, 100, 106, 302  impact assessment, 41  impairments, 441 

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Index implementation, 44, 46, 58, 538, 544, 547, 553, 557,  563, 564  imports, 5  impurities, 2, 45, 48, 442, 547  in situ, 10, 102, 328, 412, 444, 472, 475, 500  in vitro, 100, 104, 109, 111, 153, 178, 190, 221, 266,  412, 415, 418, 455, 457, 462, 470, 471, 532  in vivo, 100, 101, 102, 104, 109, 111, 112, 152, 153,  221, 306, 419, 422, 423, 424, 457, 470, 532  inactivation, 441, 502  inactive, 297  incentive, 551  incidence, 105, 135, 450, 582, 585, 589, 590, 591,  592  Incidents, 187  incineration, 24, 52, 164, 302, 539  inclusion, 101, 119  income, 5, 565  incomplete combustion, 27, 31, 169  increased competition, 480  incubation, 92, 103, 106, 107, 266  Indian, 340, 342, 346, 349, 368, 369, 372, 398, 399,  400, 401, 402, 403, 404, 405, 406, 561, 567, 568  Indian Ocean, 342, 346, 369, 400, 401, 402, 405, 406  indication, 183, 233, 489  indicators, 36, 97, 98, 99, 255, 258, 260, 306, 325,  341, 401, 410, 411, 420, 421, 422, 464, 465, 471,  475, 477, 479  indices, 98, 118, 119, 134, 151, 152, 366, 370, 372,  373, 378, 388, 432, 463, 467, 473, 582, 591, 592  indigenous, 422, 429, 512  indirect effect, 44, 46, 434, 448, 450  individual differences, 412  Indonesia, 37  industrial chemicals, 5, 8, 158, 176, 194, 308  industrial emissions, 30, 317  industrial location, 271, 414  industrial processing, 549  industrial revolution, 185  industrial wastes, 3, 229, 233, 236, 286, 507  industrialization, 4, 74, 87, 179, 236, 518  industrialized countries, 215  industrialized societies, 35, 265  inert, 16, 24, 27, 46, 163, 200, 305, 443  inertness, 149  infants, 32, 295  infection, 29, 162, 188  infections, 29, 30, 32, 446  infectious, 8, 11, 12, 13, 20, 38, 489  infectious disease, 38, 489 

617

infectious diseases, 38, 489  infertility, 413  infestations, 555, 558, 594  inflammation, 100, 101, 102  inflammatory, 102, 446  inflammatory response, 102  influenza, 29  information exchange, 570  infrastructure, 38, 43, 50, 130  ingest, 170  ingestion, 26, 150, 305  inhalation, 26, 302, 305  inherited, 228  inhibition, 101, 106, 107, 135, 141, 143, 145, 147,  148, 149, 151, 211, 221, 266, 277, 295, 414, 440,  444, 456, 466, 532  inhibitor, 86, 484  inhibitors, 108, 154, 266, 436, 439, 440, 500  inhibitory, 80, 99, 107, 418, 495, 505  inhibitory effect, 99, 107, 418  initiation, 106, 108, 113, 135, 444  injection, 66, 101, 102, 269, 559  injections, 101, 102, 103, 106, 107  injuries, 278, 413  injury, 11, 13, 17, 38, 148, 446, 467  innovation, 566  inoculation, 561  insecticide, 163, 164, 294, 296, 297, 450, 466, 478  insecticides, 22, 294, 438, 456, 463, 466  insects, 8, 163, 173, 436, 488, 555  insertion, 469  insight, 151  inspection, 55  inspections, 564  instability, 52, 433, 442, 446, 525, 558  institutions, 10, 63, 127  instruments, 318, 319  insulation, 6, 33, 170  insulators, 301  insults, 106  integration, 277, 559  integrity, 86, 98, 117, 148, 184, 342, 410, 412, 418,  429, 431, 434, 445, 452, 467, 473, 502, 538, 569,  570, 573, 578  intensity, 2, 33, 34, 36, 37, 76, 79, 80, 81, 319, 320,  328, 377, 379, 443, 546, 560, 570  interaction, 73, 87, 89, 141, 143, 148, 154, 159, 172,  359, 382, 471, 496, 500, 501, 503, 518, 525  Interaction, 89, 154, 243, 503, 514, 516, 530 

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618

Index

interactions, 76, 82, 90, 103, 108, 113, 141, 147,  154, 197, 218, 220, 262, 264, 329, 338, 434, 437,  445, 446, 450, 456, 464, 476, 495, 518, 533  interdisciplinary, 175, 518  interface, 78, 85, 87, 250, 402, 407  interference, 34, 442, 485, 500, 557  interferon, 108  interferon (IFN), 108  Intergovernmental Panel on Climate Change, 93  international, 41, 56, 163, 170, 171, 175, 183, 184,  185, 186, 315, 316, 337, 420, 512, 537, 592  International Agency for Research on Cancer, 153,  308, 313  International Atomic Energy Agency, 71, 72  international law, 186  interphase, 301  inter‐population, 449  interpretation, 99, 108, 177, 253, 428, 570, 581,  582, 592  interrelations, 584  interstate, 119  interval, 141, 341, 373, 572, 583  intervention, 66, 170  intestine, 86, 200, 486  intimacy, 41  intoxication, 148, 572  intramuscularly, 107  intrinsic, 183, 266, 502  introns, 449, 450  intrusions, 4  invasive, 94, 102, 460  inventories, 318, 329  inversion, 237  Investigations, 405  investment, 184  involution, 99, 110  iodine, 16, 365  ion transport, 503  ionic, 196, 199, 208, 211, 270, 484, 487, 500  ionization, 61  ionizing radiation, 15, 16, 61, 64, 154, 174  ions, 16, 21, 62, 77, 140, 143, 154, 195, 196, 197,  199, 206, 329, 436, 443, 460, 467, 480, 498, 500,  502, 503, 507, 513  irradiation, 417  irrigation, 22, 38, 42, 117, 559  irritability, 14, 32, 36  irritation, 4, 14, 26, 29, 30, 33, 170  island, 188, 229, 238, 303  isoenzymes, 435, 456, 520 

isoforms, 435, 441, 523  isolation, xxi, 15, 104, 137, 448, 458  isomers, 294, 297, 298, 302, 309  isopods, 462, 485, 486  isotope, 15, 70, 172  isotopes, 15, 16, 70, 220, 454  isozyme, 531  isozymes, 530  Israel, 225, 243, 244, 245, 259, 260, 315, 330  Italy, 203, 205, 206, 207, 210, 225, 227, 229, 230,  232, 252, 253, 256, 266, 274, 276, 291, 414, 415,  416, 420, 473, 565, 566, 567, 568 

J  January, 342, 346, 348, 350, 359, 362, 363, 364, 370,  379, 383, 588  Japan, 270, 331, 332, 337, 563, 564  Japanese, 101, 103, 104, 106, 107, 109, 110, 111,  112, 113, 337, 338, 563  Java, 340  Jerusalem, 259, 329  jewelry, 150  Jiangxi, 21  jobs, 5, 69  Jordan, 516  judgment, 119  Jun, 562, 568  Jung, 465  Jurassic, 227  justification, 2, 69  juveniles, 383, 440, 447 

K  kaolinite, 249  karyotype, xiii, 133, 137, 139  Kenya, 67, 72  kerosene, 32  ketones, 546  Keynes, 512  kidney, 14, 86, 133, 135, 137, 139, 142, 148, 150,  170, 182, 193, 200, 206, 218, 300, 306, 332, 333,  334, 337, 338, 455, 460, 467, 531  killing, 188, 472  kinetic energy, 572  kinetic model, 147, 148, 152  kinetics, 92, 136, 143, 144, 149, 220, 301, 503, 545,  570 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Index King, 111, 112, 217, 220, 260, 473  Korea, 178, 190, 303, 311  Korean, 338 

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

L  labeling, 102, 527, 532  labor, 5  laboratory studies, 97, 107, 414, 416, 418, 441, 535  lagoon, 229, 230, 252, 414, 439, 465, 473, 594  lakes, 2, 3, 5, 15, 18, 22, 28, 38, 44, 45, 75, 79, 81,  82, 83, 90, 91, 92, 93, 95, 166, 216, 300, 303, 311,  476, 479, 480, 487  land acquisition, 42  land disposal, 539  land use, 44, 45, 48, 82, 287, 583, 584, 585, 586,  587, 589, 592  landfill, 12, 14, 47, 131, 161, 268, 553, 554, 555,  556, 557, 558, 559, 560, 561, 562, 563, 564, 565,  566, 567, 568  landfill gas, 556, 566  landfill management, 555, 566  landfills, 3, 14, 162, 297, 554, 555, 556, 557, 558,  559, 560, 561, 562, 563, 564, 565, 566, 567  landscapes, 587, 591  land‐use, 554  language, 123  large‐scale, 66, 71, 175, 354, 498, 551, 565, 595  larva, 433, 452  larvae, 279, 383, 412, 423, 424, 447, 458, 460, 488,  529  larval, 341, 379, 382, 383, 387, 389, 413, 421, 445,  447, 491  laser, 142, 443  latency, 472  latex, 104  Latin America, 281, 282  laundry, 160  law, 15, 70, 71, 163, 185, 539, 572, 576  laws, 39, 56, 58, 137, 167, 171, 176, 183, 184, 537,  546, 570, 571, 572  leach, 3, 163  leachate, 78, 288, 553, 554, 555, 556, 557, 558, 559,  560, 561, 562, 563, 564, 565, 566, 567  leachate recirculation, xix, 553, 555, 557, 558, 561,  562, 563, 564, 566, 567  leachates, 268  leaching, 3, 78, 166, 170, 195, 237, 265, 292, 297,  513, 555  leakage, 12, 32, 70 

619

leaks, 164, 168, 497, 547  learning, 167  leather, 11, 230, 239, 268, 480  lectin, 101  legislation, 58  lesions, 86, 147, 296, 300, 411, 444, 474  leukaemia, 17, 174  leukemia, 14, 17, 425  leukocyte, 100, 110, 113, 296  Leukocyte, 102  leukocytes, 100, 101, 107, 108, 423, 473  liberation, 116, 431  Libya, 203, 210, 213, 216  life cycle, 483  Life Cycle Analysis, 59  life forms, 489  life‐cycle, 545  lifespan, 160, 572  lifestyle, 56  lifestyles, 61  lifetime, 17, 414, 487  ligand, 200, 518, 522, 525, 527, 529, 532, 534  ligands, 195, 196, 200, 201, 204, 206, 208, 220, 253,  445, 471, 484, 487, 500, 502, 504, 522  light conditions, 80  light cycle, 136  likelihood, 51  limitation, 65, 69, 79, 82, 85, 91, 93, 95, 98, 399, 539  limitations, 66, 107, 108, 468, 562  lindane, 178, 297, 303  linear, 123, 148, 179  links, 32, 573  lipid, 148, 177, 200, 294, 295, 296, 297, 298, 299,  304, 307, 425, 441, 465, 467, 472, 504, 520  Lipid, 299, 441, 467  lipid peroxidation, 148, 441, 465  lipids, 438, 441  lipofuscin, 441  lipophilic, 205, 294, 302, 521, 530  lipopolysaccharide, 102, 104  lipoprotein, 507  liquids, 1, 13, 199, 301, 556  liquor, 22  literacy, 189  literature, 17, 98, 100, 105, 108, 140, 195, 196, 225,  228, 266, 318, 341, 377, 413, 450, 453, 479  Lithium, 178  liver cancer, 14  liver cells, 302  liver disease, 300 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

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620

Index

liver enzymes, 295  liver transplant, 151  liver transplantation, 151  livestock, xiv, 15, 108, 157, 303, 594  living environment, 66, 68, 125  lobsters, 383, 486  localization, 525, 533  locus, 449, 451, 452, 453, 477, 520, 525  logging, 126, 130  logistics, 540  London, 71, 72, 88, 92, 131, 165, 174, 185, 189, 254,  398, 401, 402, 421, 422, 478, 492, 512, 515, 578,  579  long distance, 164, 318  long period, 32, 33, 35, 85, 183, 225, 277, 387  longevity, 387, 419, 432  long‐term, 14, 17, 21, 35, 36, 69, 151, 171, 183, 188,  200, 241, 249, 265, 278, 308, 318, 341, 373, 376,  384, 388, 397, 399, 465, 551, 556, 559, 563, 565  Los Angeles, 179, 180  loss of consciousness, 32  losses, 5, 46, 307, 557  low molecular weight, 199, 205, 206, 436, 484  low‐level, 15, 112, 174  low‐permeability, 560  lubricants, 14  lubricating oil, 23, 25  luggage, 63  lumen, 521  lung, 28, 29, 31, 32, 33, 86, 295  lung cancer, 32, 33  lung disease, 32  lungs, 13, 29, 30, 32, 38, 174, 315, 316  Luxembourg, 227  lying, 124, 129, 130, 201, 233, 583  lymph, 300  lymph node, 300  lymphoblast, 427  lymphocyte, 99, 100, 104, 105, 108, 111, 153, 428,  433, 474  lymphocytes, 100, 101, 102, 104, 106, 107, 108, 111,  153, 418, 424, 428, 471  lymphoid, 98, 99, 100, 101, 106, 107, 108, 110  lymphoid cells, 107  lymphoid organs, 99, 101, 106, 108  lymphoid tissue, 100, 108, 110  lymphomas, 295  lysimeter, 561, 562, 568  lysine, 142  lysis, 76, 417 

lysosomes, 445, 460, 471 

M  machinery, xi, 2, 17, 34, 51, 53, 54, 436, 539, 541,  545  machines, 4, 63, 462, 570  mackerel, 220, 257  macroalgae, 383, 406  macrobenthic, 377, 383, 390  macromolecules, 445, 452, 570, 572, 574  macronutrients, 90  macrophage, 104, 108  macrophage inflammatory protein, 108  macrophages, 99, 100, 102, 104, 108  magnesium, 19, 77, 195, 471, 483, 507  magnetic, v, 292  magnetite, 243  Maine, 431  maintenance, 8, 42, 43, 55, 80, 117, 130, 277, 546,  549, 554, 570, 572  Maintenance, 117, 557  malaria, 47, 163, 294, 297  Malaysia, 41, 58, 59, 171, 537, 563  males, 136, 137, 140, 141, 149  malondialdehyde, 433  Malta, 422  mammal, 483  Mammalian, 108, 133, 136, 152  mammalian cell, 135, 139, 148, 151, 155, 413, 417,  418, 422  mammalian cells, 135, 139, 148, 151, 155, 413, 417,  418, 422  mammals, 26, 57, 86, 99, 105, 106, 134, 149, 150,  170, 181, 182, 199, 211, 214, 299, 334, 337, 413,  436, 447, 454, 518, 521, 525, 527  manganese, 166, 195, 198, 227, 233, 238, 249, 250,  282, 439, 465, 483, 498, 505  Manganese, 198, 233, 250, 262, 506  manifold, 37, 118, 540  man‐made, 8, 15, 65, 159, 164, 165, 174, 228  mantle, 64  manufactured goods, 161  manufacturer, 180, 295, 542  manufacturing, 2, 11, 13, 17, 42, 163, 164, 241, 286,  297, 300, 313, 551, 552  manufacturing companies, 300  mapping, 153, 449, 581, 582, 584, 590, 592, 594  marine mammals, 26, 160, 161, 182, 266, 334, 446  maritime, 185, 187, 229, 291, 341 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

Index market, 12, 63, 64, 126, 194, 550  marketing, 540  markets, 11, 296, 309  marrow, 98, 137, 139, 143  marshes, 170, 229, 267, 268, 279, 281  Maryland, 113, 406  mass spectrometry, 270, 283, 287, 443  Massachusetts, 475  maternal, 101, 453  mathematical, xiv, 133, 135, 143, 148, 149, 152,  403, 578  matrix, 345, 352, 374, 504  maturation, 98, 99, 101, 105, 218, 435, 474  Mauritania, 203, 205, 206, 213, 216  measurement, 56, 58, 62, 102, 103, 107, 108, 127,  174, 181, 185, 260, 266, 288, 298, 343, 404, 427,  439, 469, 474, 559, 571, 582, 583, 591, 593  measures, 23, 34, 44, 55, 73, 77, 87, 97, 98, 99, 100,  106, 108, 109, 161, 171, 184, 185, 186, 188, 244,  287, 342, 398, 400, 411, 416, 432, 446, 545, 547,  550, 584  meat, 268, 295  mechanical, 42, 88, 288, 499, 547, 570, 572  mechanical energy, 572  mechanics, 564, 570, 571, 575  media, 63, 179, 200, 500, 502  median, 232, 248, 271, 274, 275, 288  mediators, 108  medicine, 14, 64, 65, 70, 174, 453, 464, 569, 578  Mediterranean climate, 223  Mediterranean countries, 229  medulla, 99  melanin, 167  melt, 7, 22  melting, 229, 417  meltwater, 300  membranes, 16, 199, 206, 211, 413, 437, 471, 485  memory, 102, 103  mental health, 36  mental impairment, 14  mental retardation, 167  mercury, 4, 7, 13, 134, 166, 167, 176, 177, 178, 181,  182, 189, 193, 195, 220, 221, 244, 245, 246, 255,  260, 265, 311, 338, 422, 439, 465, 477, 488, 492,  501, 502, 505  Mercury, 7, 167, 182, 198, 220, 221, 259, 260, 311,  488, 505  metabolic, 104, 152, 154, 170, 193, 197, 200, 212,  265, 297, 393, 411, 412, 454, 469, 484, 485, 488,  489, 490, 500, 502, 503, 504, 571, 574, 575 

621

metabolic disturbances, 152  metabolic dysfunction, 502  metabolic pathways, 297, 502  metabolic rate, 200  metabolite, 296, 416, 444, 521, 577  metabolites, 80, 92, 178, 179, 294, 297, 299, 302,  303, 305, 312, 410, 434, 438, 443, 502, 504, 521,  522, 523, 524  metabolizing, 457, 520, 522, 523, 531, 532  metal content, 226, 227, 234, 235, 236, 291, 482  metal ions, 143, 166, 196, 200, 216, 436, 480, 486,  498, 500, 501, 504, 505, 506, 507, 514, 515  metalloids, 165, 194, 195, 503  Metallothionein, 206, 338, 457, 459, 460  metallothioneins, 211, 433, 436, 459, 460, 461, 473,  484  Metallothioneins, 211, 436, 459, 471, 484, 491  metallurgy, 70, 230  metaphase, 141, 149, 411, 413, 445  meteorological, 75, 317, 318, 320  methane, 6, 19, 31, 445, 556, 557, 561  methanogenesis, 555, 556, 561  methanol, 137, 270  methylmercury, 6, 7, 492  Methylobacterium, 513  metric, 180, 584, 592  metropolitan area, 115, 226, 237  Miami, 401  mice, 110, 133, 134, 135, 136, 137, 138, 139, 140,  141, 142, 143, 145, 146, 148, 149, 150, 152, 153,  155, 295, 305, 312, 460  microalgae, 91  microarray, 443, 468  microarray technology, 443  microbes, 8, 74, 499, 503, 514, 555, 557  Microbes, 495, 503, 515  microbial, 85, 270, 299, 310, 359, 496, 498, 502,  503, 512, 554, 555, 556, 558, 561  Microbial, 265, 512, 513, 516, 555  microbial cells, 498, 502, 512  microcosm, 432  microenvironment, 199, 237  micronucleus, 151, 411, 413, 414, 424, 425, 426,  433, 470, 471  micronutrients, 198, 345, 501  microorganism, 561  microorganisms, 6, 7, 8, 11, 18, 19, 24, 93, 160, 164,  184, 280, 295, 296, 298, 487, 495, 498, 499, 502,  503, 504, 513, 515, 555  micro‐organisms, 432 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

622

Index

microsatellites, 449, 450  microscope, 100, 366, 417  microscopy, 326, 443  microsomes, 464, 520, 523, 527, 530, 531  microtubules, 154  microwave, 306  migrants, 116  migration, 73, 75, 76, 81, 99, 116, 331, 417, 448  migratory birds, 337  military, 8, 36, 164, 229, 276  milk, 22, 295  mine tailings, 158, 225, 234, 506, 515  mineral water, 64  mineralized, 297  mineralogy, 177, 237, 243, 248, 315, 316  minerals, 19, 64, 195, 199, 237, 243, 249, 363, 484,  498, 513  mines, 7, 63, 195, 234, 239, 487  mining, 7, 10, 15, 17, 42, 64, 65, 68, 70, 159, 211,  225, 226, 234, 239, 250, 265, 484, 497, 506, 565  minisatellites, 450  Ministry of Environment, 258  Minnesota, 90  misfolding, 437  misinterpretation, 447  misleading, 165, 183  missions, 63  Missouri, 492, 593  mitochondria, 139, 463  mitochondrial, 449, 464, 477  mitochondrial DNA, 449, 477  mitochondrial membrane, 464  mitogen, 101, 104  mitosis, 142  mitotic, 137, 411, 413, 445  mixing, 71, 77, 80, 82, 83, 84, 91, 92, 126, 243, 363,  369  mobility, 225, 226, 230, 246, 250, 251, 302, 449,  498, 557  modeling, 94, 111, 136, 145, 175, 218, 255, 329, 593  models, 66, 67, 153, 183, 217, 306, 325, 329, 421,  471, 476, 523, 581, 585, 588, 592, 594  modulation, 99, 456  moisture, 554, 555, 556, 557, 558, 559, 561, 562,  563  moisture content, 554, 555, 556, 557, 558, 561, 563  molecular biology, 456, 462  molecular markers, 448  molecular mechanisms, 150, 412  molecular weight, 142, 168, 205, 437, 443, 468 

molecules, 16, 200, 434, 436, 437, 441, 482, 485,  502, 504, 520, 526, 579  mollusks, 181, 201, 211, 341, 527, 529  molting, 108, 113, 486, 489  molybdenum, 166, 331, 337, 493  momentum, 540  monkeys, 333, 336  monoclonal, 99, 107, 527  monoclonal antibodies, 99, 107  monocytes, 100, 104  monomeric, 460  monoterpenes, 546  monsoon, 342, 345, 346, 348, 350, 354, 355, 356,  358, 359, 360, 362, 363, 364, 368, 369, 370, 371,  377, 378, 379, 382, 387, 388, 397, 401, 402, 403,  555  Montana, 593  Monte‐Carlo, 216  Moon, 303, 311, 465  morphogenesis, 571  morphological, 74, 296, 306  morphology, 85, 89, 106, 237, 239, 249, 264, 326,  495, 508, 511  mortality, 66, 73, 98, 112, 369, 397, 406, 410, 440,  447, 448, 450, 453, 593, 594  mortality rate, 447, 453  Moscow, 150, 153, 579  mosquitoes, 19, 47, 163  motels, 11  mothers, 492  motion, 264, 575  motorcycles, 34  motors, 19, 301  mountains, 10, 227  mouse, 103, 133, 135, 136, 139, 140, 142, 143, 145,  146, 150, 305, 312, 525, 532  mouth, 13, 249, 269  movement, 8, 52, 76, 144, 239, 558, 563  Mozambique, 594  mucosa, 100, 101, 145  mucosa‐associated lymphoid tissue, 100  mucus, 199  multidrug resistance, 458  multimedia, 301  multiple alleles, 449  multiplication, 340, 501  multiplicity, 158, 502, 519  multivariate, 258, 282, 592  municipal area, 10, 116, 123  municipal solid waste, 12, 553, 567 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Index muons, 63  muscle, 14, 182, 194, 206, 208, 212, 214, 215, 219,  220, 296, 302, 303, 304, 307, 407, 440, 486, 488,  489  muscle tissue, 194, 208, 215, 219, 440  muscles, 208, 214, 307, 482  music, 34, 35  mutagen, 489  mutagenesis, 470  mutagenic, 421, 422, 445, 448, 450  mutant, 443  mutants, 458  mutation, 140, 444, 448, 450, 475, 476, 502, 514  mutation rate, 140, 448, 450, 476  mutations, 17, 29, 140, 411, 434, 445, 448, 450, 453,  476  Mycobacterium, 102 

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

N  naming, 519  nanoparticles, 472  naphthalene, 467, 519  nation, 10, 34, 176, 246  national, 20, 29, 56, 163, 170, 171, 175, 184, 405,  420, 421, 592  National Academy of Sciences, 91  National Marine Fisheries Service, 469  National Oceanic and Atmospheric Administration,  163  National Oceanic and Atmospheric Administration  (NOAA), 163  national parks, 29  National Research Council, 95, 189  Native American, 39  native plant, 31  native species, 411  natural disasters, xvii, 38, 409  natural environment, 4, 15, 22, 63, 173, 200, 206,  412, 416, 447, 538  natural gas, 6, 8, 15, 168  natural habitats, 56, 379  natural killer, 100, 447, 474  natural killer cell, 447, 474  natural laws, 570  natural resources, 5, 21, 50, 54, 56, 265, 409, 538  natural selection, 448, 449  nausea, 14, 32, 33, 302  necrosis, 135, 296  negative consequences, 157, 410 

623

negligence, 25, 42  nematode, 464, 532, 593  nematodes, 436, 462, 522  neonatal, 105  nephropathy, 167  nephrotoxicity, 135  nerve, 166, 570  nerve gas, 166  nervous system, 294, 295  nesting, 26, 110  Netherlands, 89, 92, 94, 220, 276, 405, 406, 455  network, 130, 432, 582  neuroendocrine, 108, 113  neurotoxic, 86  neurotoxicity, 109  neurotoxins, 86  neutralization, 417, 548  neutrinos, 62  neutrons, 63  neutrophils, 100  Nevada, 329  New Jersey, 181, 190  New South Wales, 252  New Zealand, 93, 278  newspapers, 1, 10  Newton, 146, 154  next generation, 174, 557  nickel, 19, 155, 193, 198, 220, 227, 246, 332, 337,  439, 452, 464, 488, 491, 492, 501, 504, 513  nickel (Ni), 332  Niels Bohr, 570  Nielsen, 112  Nigeria, 61  Nile, 224, 227, 243, 244, 260, 303, 311, 439, 456  nitrate, 6, 19, 55, 135, 150, 154, 340, 342, 345, 348,  353, 354, 355, 356, 358, 361, 362, 363, 373, 378,  391, 392, 395, 397, 402, 437  nitrates, 29, 79  nitric acid, 7, 29, 270  nitric oxide, 29, 32  nitrification, 85  Nitrite, 350, 353  nitrogen compounds, 91, 393  nitrogen dioxide, 28, 29  nitrogen fixation, 356  nitrogen oxides, 2, 3, 8, 27, 28, 29, 30, 229  nitrosamines, 32  nitrous oxide, 29, 78  Nixon, 77, 91, 402  Nobel Prize, 294 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

624

Index

nodes, 584, 586  noise, 2, 4, 33, 34, 35, 36, 41, 42, 44, 45, 49, 52, 57,  126, 127, 131  non‐destructive, 458  non‐enzymatic, 438, 503  nonequilibrium, 570, 594  nonequilibrium systems, 570  non‐hazardous, 44, 46, 540  non‐human, 2, 44, 46, 66  non‐infectious, 103  nonlinear, 122, 154  non‐linear, 584  non‐metals, 194  non‐nuclear, 63, 64  non‐renewable, 189  nontoxic, 104, 135, 206, 214  normal, 13, 26, 33, 53, 61, 66, 67, 82, 101, 102, 110,  166, 195, 201, 208, 273, 277, 295, 320, 393, 422,  423, 428, 433, 444, 482, 485, 488, 505, 575  normal distribution, 273, 277  normalization, 178, 237, 248, 260, 325  North America, 208, 411, 478, 567  North Atlantic, 220  North Carolina, 95, 406  North Sea, 177, 178, 205, 210, 213, 219, 308, 415,  424, 425  Northeast, 218, 369, 469  Norway, 90, 221  nuclear material, 189  nuclear power, 2, 15, 17, 65, 69, 174, 342, 399, 400  nuclear power plant, 65, 342, 400  nuclear reactor, 63  nuclear receptors, 530  Nuclear Regulatory Commission, 174, 400, 491  nuclear technology, 65  nuclear weapons, 2, 15, 65, 172, 173, 174, 175  nuclei, 15, 62, 71, 142, 172, 417, 445  nucleic acid, 16, 438  nucleosome, 142  nucleosomes, 142  nucleotide sequence, 449, 507  nucleotides, 443, 444  nucleus, 15, 62, 139, 141, 172, 301, 413, 417, 437,  445, 503, 517, 518, 525, 526  nutrient cycling, 82, 498  nutrition, 91, 200, 489, 493  nuts, 549 

O  observations, 2, 57, 102, 149, 255, 272, 320, 329,  349, 350, 354, 356, 367, 368, 373, 379, 382, 383,  388, 390, 398, 400, 405, 426, 562  occupational, 17, 36, 66, 151  Oceania, 403  oceans, 2, 3, 4, 18, 24, 25, 28, 29, 72, 157, 161, 163,  165, 171, 172, 175, 177, 178, 185, 187, 201, 403,  497  odors, 11, 18, 19, 126, 558, 563  oestrogen, 441  offshore, 161, 162, 168, 180, 194, 228, 234, 237,  240, 244, 254, 340, 369, 397, 405, 594  offshore oil, 161, 168, 237  Ohio, 338  oil refineries, 168, 544  oil refining, 28  oil spill, 6, 25, 26, 168, 170, 171, 179, 184, 187, 189,  190, 416, 419, 426, 427, 429, 468, 469, 534, 535  oils, 19, 20, 25, 158, 159, 163, 168, 170, 184, 189,  301, 546  oligomeric, 520  Oman, 182  oncogene, 450, 451, 477  Oncogene, 445, 476  oncogenes, 445, 450  online, 188, 189, 190, 191, 225, 227, 233  oocytes, 140, 533  operator, 58, 134  operon, 506, 508, 516  optical, 443  optical density, 443  optics, 575  optimization, 69, 130, 444  oral, 295, 300, 302, 322, 455, 457, 522, 531  ordinary differential equations, 144  ores, 15, 166, 232, 234  organ, 6, 7, 98, 99, 110, 153, 167, 201, 265, 299,  437, 482, 486, 518  organelles, 434  organic chemicals, 6, 13, 29, 180, 447  organic compounds, xxi, 3, 18, 22, 27, 29, 30, 80,  168, 230, 311, 415, 546  organic matter, 29, 178, 208, 211, 227, 228, 237,  238, 246, 250, 299, 348, 349, 359, 480, 487, 554,  558  organic solvent, 13, 294, 541  organic solvents, 13, 294, 541  Organic wastes, 484 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

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Index organization,  49, 50, 54, 58, 59, 119, 341, 404, 433,  454, 475, 518, 570, 572, 578, 579  organizations, 50, 175, 184  organochlorinated, 302, 303, 308  organochlorine compounds, 313  organometallic, 6, 7, 265  organophosphates, 440, 466  organotin compounds, 263, 264, 266, 270, 276, 277,  279, 283  orientation, 298  osmolality, 490  osmosis, 199  osteoporosis, 300  Ottawa, 309  otters, 26, 170, 311  outliers, 584  ovarian, 266, 280  ovary, 108, 266, 458  overexploitation, xvii, 409  overload, 563  overproduction, 438  overtime, 22  oviduct, 101, 107, 108  oxalic, 83  oxalic acid, 83  oxidants, 30, 467  oxidation, 27, 91, 206, 220, 225, 296, 299, 302, 310,  353, 354, 357, 419, 429, 434, 439, 440, 442, 500,  503, 520, 547, 548  oxidation products, 302  oxidative, 104, 134, 418, 426, 427, 428, 435, 437,  438, 439, 440, 441, 456, 460, 464, 465, 467, 468,  472, 521, 522, 532  oxidative damage, 418, 438, 439, 464, 522  oxidative stress, 134, 426, 435, 437, 438, 439, 440,  456, 460, 464, 465, 467, 468  oxide, 27, 28, 29, 104, 230, 288, 289, 422, 423  oxides, xvi, 6, 10, 28, 29, 32, 195, 208, 225, 227, 229,  247, 285, 291, 317, 480, 522  Oxygen, 20, 348, 398  oxygenation, 348, 447, 459, 523  oyster, 266, 413, 424, 444, 451, 460, 469, 471, 476  oysters, 181, 266, 277, 376, 383, 384, 389, 397, 411,  414, 473  ozone, 2, 10, 27, 29, 30, 593  Ozone, 27, 29, 30 

625

P  Pacific, 162, 172, 177, 178, 188, 218, 332, 340, 411,  424, 476, 565, 593  packaging, 10, 12, 162  paints, xvi, 14, 30, 47, 163, 241, 276, 286, 293, 294,  302, 480, 491  paper, 11, 17, 18, 21, 23, 28, 33, 132, 163, 164, 172,  201, 241, 298, 345, 383, 466, 467, 528, 534, 542,  554, 567, 582, 591, 592  Paper, 11, 12, 463, 565  Paracentrotus lividus, 437  paradigm shift, 66  paramagnetic, 464  parameter, 67, 118, 122, 144, 145, 147, 277, 325,  328, 340, 413, 445, 576  Parasite, 454  parasites, 18, 24, 100, 110  parents, 453  Paris, 72, 261, 457, 530, 534, 567  particle morphology, 325  particle shape, 325  percolation, 3, 78, 560  performance, 36, 56, 58, 59, 342, 393, 540, 546,  549, 559, 560, 561  periodic, 6, 194, 389, 471  periodic table, 6, 194  periodicity, 90, 383  peripheral blood, 153, 423, 474  periplasm, 506  permeability, 225, 458, 486, 559, 560, 563  permeation, 200  permit, 55, 237, 436, 521  Perna perna, 415, 426  peroxidation, 441, 467  peroxide, 437, 439  perturbation, 433, 476  perturbations, 431, 433, 446, 471  pesticide, 6, 22, 110, 163, 164, 166, 176, 297, 309,  311, 435  pests, 47, 164, 297  petrochemical, 42, 268, 544  Petrochemicals, 14  petroleum, 3, 6, 8, 13, 19, 25, 168, 169, 181, 184,  194, 229, 230, 469, 473, 496, 512, 531, 534  Petroleum, 13, 19, 168  petroleum products, 25, 169, 184  Petrology, 330  P‐glycoprotein, 436, 458, 459  pH values, 83, 94, 345, 390 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

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626

Index

phagocytic, 100, 104  phagocytosis, 200  pharmaceutical, 20  pharmaceuticals, 14, 168, 480  pharmacology, 531  phenolic, 299, 546  phenotype, 442, 448, 451, 452  phenotypes, 99, 451  Philadelphia, 218, 477  Philippines, 37, 90  philosophy, 552  phobia, 65  phosphatases, 86  phosphate, 4, 15, 19, 25, 55, 64, 79, 85, 228, 340,  342, 345, 354, 359, 360, 361, 363, 373, 378, 391,  395, 397, 403, 437, 451, 471, 503, 504, 507, 548,  572  Phosphate, 102, 359, 360, 361, 364  phosphates, 13, 483  phospholipids, 504  phosphorous, 23, 77, 79, 85, 87, 88, 340, 360, 395,  396, 402, 403  phosphorus, 19, 22, 78, 79, 91, 95, 160, 176, 221,  261  Photocatalytic, 472  photochemical, 2, 27, 29  photodegradation, 402  photographs, 373  photolysis, 266, 296, 299  photons, 63, 172  photosensitivity, 300  photosynthesis, 74, 79, 81, 84, 90, 93, 187, 348  photosynthetic, 75, 92, 93, 94, 348, 349, 364  phototrophic, 461  phycoerythrin, 80, 81  physical environment, 377  physical factors, 76, 91  physical fields, 579  physical force, 181  physical health, 4  physical properties, 169  physicochemical, 201, 226, 389, 496, 594  physico‐chemical characteristics, 378, 499  physicochemical properties, 389  physico‐chemical properties, 340, 348  physico‐chemical properties, 431  physics, 571, 575  physio‐chemical, xi  physiological, 33, 35, 36, 74, 77, 86, 93, 98, 134, 152,  195, 296, 309, 339, 406, 410, 419, 421, 431, 432, 

433, 435, 437, 442, 448, 451, 452, 477, 482, 487,  502, 518, 570, 572  physiologists, 431  physiology, 82, 219, 421, 422, 462, 487, 491, 500,  502, 579  phytohaemagglutinin, 111  phytoplanktonic, 498  phytoremediation, 279  pig, 22, 530  pigments, 301, 542  pigs, 520, 547  pipelines, 25  pituitary, 211  placenta, 300  planar, 325  plankton, 26, 81, 92, 157, 160, 162, 164, 181, 183,  367, 398, 401, 402  planning, 33, 41, 46, 58, 59, 66, 549  plasma, 266, 287, 305, 312, 337, 441, 466  plasma membrane, 266  plasmid, 505, 506, 507, 508, 515, 516  plastic, 13, 23, 25, 31, 46, 136, 161, 162, 163, 164,  270, 302, 496, 560  plastic products, 161  plasticity, 447  plastics, 3, 6, 11, 12, 158, 161, 163, 168, 188, 286,  293, 294, 304, 305, 542  platforms, 168  platinum, 292  play, 6, 29, 100, 135, 238, 239, 243, 247, 264, 339,  364, 434, 435, 439, 479, 482, 496, 525, 564  plutonium, 166  pneumonia, 29  point mutation, 450, 453  poison, 19, 20, 167, 170, 489  poisoning, 32, 86, 143, 167, 188, 302, 333, 334, 336,  466, 489, 491  poisonous, 29, 31, 167, 496  poisons, 169, 437, 502  Poland, 152, 308, 338, 525, 532  polar bears, 164, 182  police, 12  policy makers, 554  political, 188, 223  polluters, 21  Pollution Prevention Act, 538  polonium, 62  polybrominated biphenyl ethers, 313  polybrominated diphenyl ethers, 304, 307, 312, 313,  415 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

Index polychlorinated biphenyls (PCBs), 178, 293, 302,  303, 305, 307, 308, 418  polycyclic aromatic hydrocarbon, 32, 181, 253, 411,  426, 427, 428, 435, 443, 446, 455, 465, 469, 472,  473, 521, 523, 529  polyethylene, 269  polymer, 191, 304  polymerase, 443, 449, 469  polymerase chain reaction, 443, 449  polymerization, 147  polymers, 306, 503, 504  polymorphism, 443, 449, 451, 465  polymorphisms, 424, 449  polypeptide, 520  polypeptides, 437, 504  polysaccharide, 502, 504, 513  polysaccharides, 504  polythene, 343, 365  polyunsaturated fat, 441  polyunsaturated fatty acid, 441  polyurethane, 304, 306, 313  polyurethane foam, 304, 306, 313  pond, 489  pools, 26, 38, 174, 555  poor, 1, 3, 14, 23, 25, 32, 36, 44, 45, 76, 167, 168,  239, 320, 354, 523, 529  population density, 123, 127, 368, 369, 371, 379,  397, 454  population growth, 3, 76, 123, 179, 447  population size, 75, 448  pore, 178, 190, 288, 560, 563  porous, 559  porphyria, 300  ports, 63, 158, 226, 230, 256, 264, 268, 405  Portugal, 225, 281, 439, 465, 594  positive correlation, 289, 348, 350, 354, 356, 357,  360, 363, 364, 373, 383, 415  potassium, 19, 77, 87, 172, 195, 418, 428  potato, 460  poultry, 98, 104, 108, 109  power, 3, 11, 15, 27, 28, 34, 64, 65, 68, 69, 102, 159,  173, 243, 342, 390, 391, 393, 399, 400, 404, 405,  406, 407, 508, 572, 573  power generation, 28  power plant, 3, 11, 15, 27, 159, 173, 342, 390, 391,  393, 399, 400, 404, 405, 406, 407  power plants, 3, 11, 15, 27, 159, 173, 342, 390, 391,  393, 400  power stations, 64 

627

precipitation, 22, 66, 78, 83, 91, 164, 166, 195, 225,  237, 250, 302, 318, 346, 363, 364, 377, 498, 561,  581, 583, 584, 585, 586, 587, 588, 589, 592  predators, 26, 170, 177, 200, 299  predictability, 110  prediction, 149, 333, 584, 589, 590, 592, 593, 594  predictor variables, 584, 585, 586, 587, 589  pre‐existing, 28, 289, 384, 541  pregnancy, 32  premature death, 5  preparation, 46, 166, 471  preschool, 12  preschool children, 12  present value, 363, 388  preservative, 28, 297  preservatives, 28  pressure, 15, 33, 44, 73, 93, 130, 159, 168, 184, 301,  302, 306, 342, 356, 379, 449, 451, 452, 548, 558,  559, 560, 563  prevention, 58, 171, 184, 185, 187, 188, 265, 400,  406, 533, 534, 538, 539, 540, 543, 544, 546, 547,  548, 549, 550, 552  preventive, 170, 185  priming, 428  printing, 302, 337, 542  priorities, 539  prisons, 10, 11  pristine, 433, 476  private, 8, 186  private dwellings, 8  proactive, 549, 550  probability, 53, 71, 81, 91, 94, 333, 334, 448, 545,  584, 589, 591, 592, 593  probability distribution, 589  probe, 153, 468  procedures, 54, 56, 59, 63, 65, 124, 174, 179, 196,  241, 540, 545, 547, 551  producers, 85, 298  productivity, 33, 36, 74, 76, 85, 92, 94, 157, 160,  339, 340, 358, 364, 377, 397, 398, 402, 403, 497  professions, 119  profit, 44, 58  profit margin, 58  profitability, 552  progeny, 112  progesterone, 107, 108  prognosis, 578  program, 123, 124, 163, 174, 183, 277, 316, 317,  410, 444, 540, 544, 563, 573  progressive, 230, 235, 341 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

628

Index

prokaryotes, 437  prokaryotic, 74  proliferation, 73, 82, 101, 104, 105, 111, 364, 368,  369, 372, 413, 417  promote, 19, 94, 243, 278, 556, 591  propagation, 256  propane, 25  property, 15, 38, 50, 162, 306, 508, 569  propylene, 546  protection, 12, 34, 35, 46, 55, 66, 72, 174, 175, 184,  185, 186, 191, 214, 437, 452, 458, 512, 538, 554  protective role, 465  protein kinase C, 86  protein sequence, 533  protein synthesis, 86, 463  Proteins, 141, 433, 437, 461  protocol, 218, 288, 414, 417  protocols, 98, 104, 137, 185, 444  protons, 62, 63  protooncogene, 151  protozoa, 8, 18  pruning, 584  pseudo, 390  Pseudomonas, xviii, 495, 499, 506, 513  Pseudomonas aeruginosa, 499  psychological, 32, 33, 35  pubertal development, 189  public, 18, 20, 38, 52, 65, 67, 68, 69, 117, 119, 163,  165, 168, 170, 179, 186, 188, 297, 320, 328, 427,  538, 545, 546, 554, 555, 564  public awareness, 179  public health, 18, 119, 170, 297, 328, 427, 538, 555  public safety, 52  publishers, xxi, 150, 151  pulp, 21, 28, 100, 102, 111, 164, 241, 298, 440, 466,  467, 474, 531, 534  pulp mill, 440, 466, 474  pumping, 562  pumps, 200, 266, 390, 503  pure water, 407  purification, xxi, 166, 183, 297, 457, 465, 498, 525,  566  purines, 417  PVC, 286, 567  pyrene, 412, 415, 424, 439, 445, 469, 470, 519, 524,  532, 534  pyrite, 225 

Q  Qatar, 182  QSAR, 530  quail, 101, 103, 104, 106, 107, 109, 110, 111, 112,  113  quality control, 56, 175, 545  quality of life, xi, 2, 4, 44  quantum, 340, 570, 575  quantum mechanics, 575  quartz, 237, 244, 480  Quebec, 310, 311, 474  questionnaire, 116, 119  questionnaires, 119  quinine, 457  quinones, 523 

R  radar, 171  radiation, 15, 16, 17, 61, 62, 63, 64, 65, 66, 67, 68,  69, 70, 71, 72, 171, 172, 173, 174, 187, 402, 422,  428, 437, 445, 496, 555  Radiation, 61, 62, 63, 64, 67, 69, 70, 71, 72, 189, 427  radiation therapy, 65, 174  radical, 104, 306, 438  radio, 15, 65, 70, 71  radioactive contamination, 38  radioactive isotopes, 173  radioactive waste, 10, 16, 63, 72, 161, 165, 173, 174,  175  radiography, 63  radioisotope, 15  radiological, 61, 67, 68, 69  radionuclides, 15, 62, 63, 64, 65, 66, 67, 68, 70, 72,  172, 173, 174, 419, 450, 451, 452, 475  radium, 7, 62, 64  radon, 7, 16, 33, 64, 67, 69, 135, 151, 407  rain, xi, 1, 2, 3, 5, 7, 17, 27, 28, 29, 37, 55, 66, 78,  166, 168, 169, 177, 296, 318, 347, 480, 554  rainfall, 46, 77, 80, 127, 158, 159, 225, 237, 340,  342, 377, 555  rainwater, 7, 126, 127, 564  Raman, 369, 404, 405  random, 116, 137, 179, 286, 448, 449, 476  random amplified polymorphic DNA, 476  randomly amplified polymorphic DNA, 449  RAPD, 434, 449, 451, 452, 476, 477  rape, 465 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

Index rare earth, 15, 252  rare earth elements, 252  ras, 450, 476  rat, 20, 103, 110, 143, 151, 154, 305, 310, 312, 336,  421, 456, 464, 468, 469, 492, 530, 558  ratings, 119  rats, 143, 151, 295, 305, 306, 312, 334, 455, 457,  492, 520  raw material, xxi, 45, 48, 50, 54, 55, 168, 232, 538,  541, 545, 547, 550, 551  raw materials, xxi, 45, 48, 54, 55, 232, 538, 541, 545,  547, 550, 551  reaction rate, 299  reaction time, 32  reactive oxygen, 134, 135, 438, 464  reactive oxygen species, 134, 135, 438, 464  reactivity, 13, 99, 301, 574  reading, 489  reagent, 287  reagents, 287, 461  reality, 165  real‐time, 442  receptor agonist, 457  receptors, 101, 102, 104, 107, 108, 518, 533  reclamation, 10, 42  Reclamation, 555  recognition, 147, 155, 526, 533  recombination, 445  reconstruction, 38  recovery, 171, 270, 416, 418, 419, 473, 498, 508,  531, 539, 569, 572, 573, 574, 575, 576, 577, 578  recovery processes, 577, 578  recreation, 117, 167, 243  recreational, 11, 26, 44, 47, 74, 264, 303, 483, 538  recreational areas, 11  recycling, 53, 77, 82, 161, 306, 497, 538, 539, 540,  546, 547, 550, 561  recycling plant, 306  recycling plants, 306  red blood cell, 101, 103, 105, 106, 107, 111, 134  red blood cells, 103, 105, 106, 107, 134  Red Sea, xxi, 224, 247, 424  redistribution, 218  redox, 226, 438, 480, 507, 555  Redox, 238, 480  redundancy, 104  reefs, 163  refineries, 3, 8, 11, 13, 230, 268  refining, 17, 265, 497  reflection, 412 

629

regeneration, 111, 340  regional, 51, 119, 170, 285, 288, 289, 318, 475, 581,  583, 584, 588, 589, 591, 592  Registry, 308, 309, 310, 483  regression, 106, 107, 333, 336, 581, 583, 584, 593,  594, 595  regression analysis, 584  regression line, 333, 336  regression method, 584  regular, 26, 56, 84, 167, 175, 232, 263, 269, 340,  364, 367, 432, 540  regulation, 55, 58, 75, 76, 80, 81, 82, 87, 90, 93, 154,  211, 218, 228, 283, 303, 435, 436, 446, 456, 457,  461, 463, 467, 468, 479, 485, 486, 490, 491, 518,  524, 533, 569, 570, 571, 577  regulations, 5, 39, 55, 56, 57, 58, 137, 161, 167, 174,  177, 181, 186, 541, 545, 546, 550, 551, 559, 563,  565  regulators, 42, 533, 554  rehabilitation, 555  relationship, 51, 53, 87, 105, 139, 208, 218, 219,  299, 334, 336, 341, 369, 382, 410, 413, 444, 486,  529, 584, 591, 592  relationships, 93, 119, 216, 312, 339, 453, 470, 584,  588  relative size, 79  relative toxicity, 266  relevance, 133, 181, 474  reliability, 56  remediation, 166, 180  remodeling, 113  remote sensing, 259  renal, 134, 135, 300  renal dysfunction, 134, 135  renewable energy, 5  reoxygenation, 437  repair, 11, 13, 38, 42, 135, 140, 141, 143, 144, 145,  147, 148, 149, 153, 417, 418, 420, 422, 423, 425,  427, 428, 518  repair system, 147, 518  reparation, 452  repeatability, 101, 111  repetitions, 288  replication, 141, 149, 412, 414, 444, 445, 448  reprocessing, 15  reproduction, 98, 109, 219, 266, 295, 339, 379, 388,  406, 433, 435, 438, 446, 447, 453, 466, 474, 489,  570  reproductive activity, 428  reptiles, 161 

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630

Index

research, 2, 4, 15, 36, 63, 89, 98, 100, 106, 108, 178,  181, 217, 278, 316, 317, 318, 329, 340, 366, 410,  443, 518, 524, 525, 537, 538, 540, 553, 561, 565,  566, 583  research and development, xviii, 537, 538, 540  researchers, xi, 81, 102, 105, 197, 200, 201, 342, 561  reserves, 38, 48, 55, 236  reservoir, 42, 90, 93, 180, 265  reservoirs, 88  residential, 10, 22, 29, 55, 127, 130, 131, 193, 264,  319  residues, 22, 164, 176, 193, 194, 225, 266, 269, 279,  297, 306, 309, 311, 411, 436, 443, 489, 557  resin, 33, 161  resins, 25, 47, 304  resistance, 6, 24, 29, 73, 80, 134, 149, 229, 265, 266,  435, 451, 452, 453, 458, 459, 477, 478, 489, 495,  502, 506, 507, 508, 512, 514, 515, 516, 550, 574,  575  resistence, 457  resolution, 148, 594  resource availability, 38  Resource Conservation and Recovery Act, 13  resources, 5, 21, 26, 37, 48, 56, 58, 59, 72, 80, 99,  184, 188, 383, 538  respiration, 25, 81, 92, 160, 397, 507  respiratory, 27, 28, 29, 30, 32, 33, 199, 339, 485,  503  respiratory problems, 31, 32  responsibilities, 58, 59  responsiveness, 108, 524  restaurants, 10, 11  restoration, 90, 185, 279, 346, 434  restriction enzyme, 449  retention, 77, 81, 130, 196, 426, 446, 472, 486, 488,  492, 515, 548  returns, 18, 168, 480  revenue, 52  Reynolds, 75, 79, 89, 90, 91, 93, 566  Rhode Island, 407  rhythms, 2  ribosomes, 485  ring chromosome, 139, 141  rings, 147, 301  Rio de Janeiro, 276, 283  risk assessment, xix, 98, 124, 181, 190, 219, 258,  297, 306, 422, 423, 432, 456, 459, 465, 470, 581,  582  risks, 5, 18, 21, 26, 55, 58, 125, 170, 173, 278, 301,  427, 453, 454, 483, 543, 546, 554, 558 

River Po, 307  river systems, 303, 311  RL, 220, 458, 474, 477  RNA, 154, 469  Robertsonian translocation, 139, 141  robotics, 443  rocky, 171, 406  rodent, 98, 149, 555  rodents, 47, 100, 109, 133, 134, 135, 136, 139, 141,  143, 149, 151, 152, 297, 300, 413  rods, 15  room temperature, 195, 288, 306  roughness, 325, 326, 328  Royal Society, 39, 189  rubber, 31  Rubber, 542  rubidium, 172  rural, 5, 30, 116, 316, 317, 450  rural areas, 5, 30, 316, 317  Russia, 178, 190  Russian, 150, 153, 154, 578, 579  Rutherford, 312  rutile, 228, 243  rye, 298 

S  S phase, 141  Saccharomyces cerevisiae, 513, 514, 515  safety, 35, 42, 55, 64, 163, 185, 186, 190, 337, 342,  400, 543, 558, 563  saline, 87, 102, 137, 334, 343, 346, 369, 377, 396  salmon, 199, 217, 218, 313, 450, 455, 467, 476  Salmonella, 98, 411, 422  salt, 6, 7, 19, 22, 83, 170, 199, 250, 267, 268, 279,  480, 510, 511  salts, 2, 7, 77, 167, 199, 211, 398, 417, 487  saltwater, 199  sample, 71, 116, 117, 123, 127, 142, 228, 276, 286,  287, 288, 289, 319, 332, 417, 442, 586  sample survey, 116  sand, 19, 23, 24, 26, 83, 159, 225, 227, 230, 233,  235, 239, 243, 244, 245, 246, 248, 267, 288, 343,  480, 487  satellite, 94, 130, 153  saturation, 130, 148  Saturday, 319  Saudi Arabia, 203, 205, 210, 213  savings, 550  scaling, 403 

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Index scanning electron microscopy, 329, 508  scarcity, 99  scavenger, 439, 555, 558  schema, 233  schistosomiasis, 47  school, 10, 18, 36, 38, 126, 127  science, 108, 170, 188, 189, 283, 569, 570, 571, 578,  579  science department, 170  scientific, 13, 68, 140, 165, 175, 340, 341, 349, 538,  540, 571  scientists, xix, 69, 367, 553  Scomber scombrus, 210, 213, 215  scrap, 11  sea floor, 25, 184  sea level, 4, 238  sea urchin, 419, 429, 436, 460  seabed, 161, 166, 170, 229, 233, 342, 389, 400  seabirds, 25, 161, 163, 170, 182, 188, 266, 332, 334,  337  seafood, 164, 182  seals, 26, 164, 170, 182, 338, 446, 457, 474, 547  search, 338, 571  searching, 571  seasonal factors, 444  seasonal variations, xvii, 267, 340, 341, 379, 416,  420, 555  seasonality, 446  Seattle, 283  second generation, 452  Second World, 232  Second World War, 232  secretion, 266  security, 564, 565  sedentary, 357, 376, 384, 388, 406, 432  sedimentation, 23, 45, 55, 80, 83, 176, 225, 229,  233, 255, 299, 366, 526  seed, 15  seeding, 323, 324, 512  seedlings, 465  seeds, 298, 300  seeps, 22, 168, 169, 179, 184, 190, 557, 558, 560  segregation, 560  selecting, 124  selectivity, 471, 545  selenium, 12, 166, 195, 198, 229, 260, 338, 422,  439, 465, 491  Self, 566, 578, 579  self‐organization, 570 

631

self‐regulation, xix, 143, 569, 570, 571, 572, 574,  578  semiarid, 454  semi‐arid, 250, 318  semi‐arid, 558  semiconductors, 286  senescence, 76, 460  senior citizens, 32  sensation, 36, 167  sensitivity, 26, 70, 94, 99, 107, 112, 266, 399, 417,  418, 428, 448, 451, 466, 491, 496, 514, 545  sensors, 147, 518, 533  separation, 21, 64, 137, 142, 443, 504  septic tank, 23, 161  series, 63, 64, 67, 70, 160, 174, 177, 178, 280, 325,  373, 390, 391, 461, 584  serine, 440  serum, 103, 106, 142, 221, 334  serum albumin, 103, 106, 142  services, v, xiii, 11, 65, 73, 161, 320  settlements, 38, 67, 582, 583, 584  settlers, 384  severe stress, 45, 48  severity, 53, 126, 127, 594  sex, 99, 112, 137, 208, 216, 331, 422, 435, 437, 438,  454, 461  sex chromosome, 137  shade, 87  Shanghai, 178, 190, 296, 309  shape, 43, 267, 316, 317, 325, 328, 389, 483  shares, 225, 525  shear, 400, 558  shear strength, 558  sheep, 103, 105, 106, 107  Sheep, 103  shellfish, 26, 181, 190, 211, 303, 341, 421, 427  shipping, 25, 162, 168, 171, 176, 185, 226, 230, 247,  268  shock, 437, 459, 461, 462, 463, 526  shoot, 576, 577  shores, 26, 74, 236, 406  short period, 379, 449  shortage, 22, 502  shortness of breath, 28  short‐term, 318, 373, 376, 383, 388, 448, 467, 487,  531  Short‐term, 150  shrimp, 181, 193, 208, 212, 215, 216, 218, 257, 477,  487, 491  shrubs, 584 

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632

Index

shuttles, 525  side effects, 87  sign, 17, 271  signal transduction, 104  signaling, 155, 185  signals, 35, 151, 443, 472, 525, 533  significance level, 374  signs, 2, 31  silica, 229  silicate, 288, 340, 342, 345, 362, 363, 364, 373, 378,  391, 395, 396, 397, 403  silicon, 340  silver, 13, 150, 196, 298, 307, 443, 457, 461, 487,  498, 513  Silver (Ag), 487  similarity, 142, 294, 317, 451, 510, 519  simulation, 180  simulations, 471  Singapore, 131, 340, 514  singular, 42  sister chromatid exchange, 411, 423, 444, 470  skeleton, 543  skin, 13, 14, 22, 101, 102, 105, 111, 194, 199, 201,  206, 295, 300, 302  slag, 238  sleep, 4, 36  sludge, 3, 19, 23, 24, 159, 161, 179, 226, 260, 306,  497, 514, 546, 549, 550, 562  small intestine, 211  small mammals, 134, 135, 149, 151  smelters, 28, 208, 299, 488  smelting, 27, 28, 166, 265, 497  smog, 2, 27, 29, 30  smoke, xi, 2, 3, 31, 32, 45, 48, 64, 65, 544  smoke exposure, 32  smokestacks, 173  smoothness, 326  social, 26, 43, 44, 91, 349, 565  social benefits, 565  social change, xi  society, xi, 10  sodium, 7, 19, 77, 86, 87, 111, 195, 206, 225, 270,  418, 441, 443, 461, 487  sodium hydroxide, 270  software, 123, 273  soil erosion, 44, 45, 47, 296, 318  soil particles, 289  soils, xvi, 40, 78, 166, 178, 190, 195, 243, 250, 264,  265, 285, 286, 289, 291, 292, 296, 299, 302, 309,  332, 337, 489, 581 

solar, 62, 555  solid phase, 283  solid waste, 10, 11, 12, 13, 125, 131, 158, 554, 559,  560, 561, 562, 564, 565, 566, 567  solidification, 417  solubility, 206, 294, 354, 498, 501  solutions, xviii, xix, 95, 146, 176, 288, 326, 402, 428,  538, 539, 549, 551, 554, 558, 565, 577  solvent, 200, 270, 412, 543, 547  solvents, 3, 13, 20, 22, 28, 30, 47, 168, 294, 541,  543, 546  soot, 317  sorbents, 184  sorption, 247, 302, 500  sorting, 225  sounds, 4, 33, 36  South America, 276, 281, 411  South Carolina, 175  South China XE "China"  Sea, 171  Southeast Asia, 555  space‐time, 426  Spain, 72, 220, 225, 226, 227, 250, 251, 260, 274,  276, 282, 300, 303, 310, 311, 409, 415, 456, 512,  528, 591, 595  spatial, 75, 76, 101, 102, 111, 175, 178, 179, 182,  183, 190, 254, 271, 280, 299, 313, 328, 405, 421,  582, 589, 592  spatial heterogeneity, 405  spawning, 383  specialists, 431  speciation, 195, 197, 218, 219, 220, 250, 262, 288,  291, 480  species richness, 366, 370, 371, 373, 388  specific gravity, 193  specific surface, 289, 560  specificity, 70, 370, 417, 449, 456, 462, 505, 507,  525, 533, 534  Spectrophotometer, 345  spectrophotometric, 345, 442  spectrophotometry, 345, 442  spectrum, 25, 195, 297, 520  speech, 35, 167  speed, 34, 126, 172, 320, 444  spermatogenesis, 155  S‐phase, 141, 142, 149  spills, 3, 25, 26, 39, 159, 168, 170, 171, 184, 188,  190, 226, 409  spin, 522  spindle, 413, 445  spleen, 86, 99, 101, 106, 110, 112, 137, 193 

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Index sponges, 184, 383, 436, 463, 521, 531  spontaneous abortion, 413  Sprague‐Dawley rats, 312  stability, 55, 57, 79, 80, 92, 127, 135, 225, 265, 307,  406, 426, 429, 436, 446, 452, 472, 473, 485, 499,  558, 560, 563  stabilization, xix, 461, 553, 555, 556, 557, 561, 562,  564, 565, 566, 568  stabilize, 556, 557  stages, 19, 42, 46, 75, 82, 106, 108, 109, 266, 279,  411, 413, 421, 447, 529, 545, 549, 561  stainless steel, 136, 269, 286  standard deviation, 272, 276, 288, 325, 586  standardization, 108, 420  standards, 21, 24, 34, 56, 66, 161, 163, 206, 537,  539, 555, 558  Standards, 186, 303, 539  Staphylococcus, 508, 514, 516  Staphylococcus aureus, 508, 514, 516  starfish, 535  starvation, 162, 446  state office, 551  statistical analysis, 588  statistical inference, 584  statistical mechanics, 570  statistics, 25, 181, 289, 582, 588, 591, 592  statutory, 545  steady state, 147, 486  steel, 11, 229, 232, 298, 373, 383  sterile, 225  steroid, 112, 520  steroid hormone, 520  steroid hormones, 520  steroids, 99, 106, 112, 434, 438, 520  stochastic, 80  stochastic processes, 80  stock, 34  stomach, 22, 200, 486  storage, 3, 13, 15, 22, 23, 117, 174, 211, 265, 437,  482, 539, 545, 553, 554, 556, 557, 559, 561  storms, 3, 4, 162  stormwater, 17, 19, 22, 23, 39, 548  stoves, 31, 32  strain, 99, 485, 513, 532  strains, 89, 294, 488, 499  Strait of Gibraltar, 224  S‐transferase (GST), 435  strategic, 283, 540, 555  strategic planning, 283 

633

strategies, 81, 87, 95, 278, 341, 490, 540, 544, 551,  566, 593  stratification, 75, 80, 83  stratosphere, 29, 30, 37, 299  streams, 3, 15, 18, 22, 28, 158, 162, 164, 166, 178,  235, 236, 268, 440, 447, 466, 474, 486, 543, 545,  548, 549  strength, 18, 162, 318, 500, 573  Streptomyces, 464  stress factors, 453  stress level, 36  stressors, 406, 473  stress‐related, 461, 464  strikes, 29  strong interaction, 480  strontium, 16  structural changes, 107  structural gene, 516  structural protein, 154  Student t test, 137  styrene, 472  sub‐cellular, 134  Subcellular, 513  subdomains, 525  subjective, 533  subsistence, 483  substitutes, 543  substitution, 444, 449, 502, 541, 543  substrates, 289, 435, 442, 505, 522, 555  subtraction, 441  suburbs, 319  sucrose, 526  sudden infant death syndrome, 32  suffering, 105, 166, 333  sugar, 323, 324  sulfate, 139, 166, 211, 443, 523  sulfur, 2, 3, 6, 7, 9, 27, 28, 29, 37, 332, 337, 546  sulfur dioxide, 2, 3, 9, 27, 28, 29, 37  sulfuric acid, 7, 13, 27, 28, 37  sulphate, 87, 153  sulphur, 229, 299, 329, 480, 483, 484  Sun, 313, 446, 472  Sunday, 317, 319, 320  sunlight, 10, 12, 30  supernatant, 288, 366  superoxide, 104, 438, 439, 441, 464, 467, 468  superoxide dismutase, 439, 441, 464, 467, 468  supervision, xxi  supervisors, 540  suppliers, 50 

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634

supply, 12, 18, 22, 24, 26, 91, 115, 117, 118, 130,  131, 389, 483, 497, 502, 538, 551, 562, 563, 564  suppression, 80, 93, 105, 266, 447  suppressor, 450, 476  surface area, 199, 227, 239, 241, 286, 357, 560  surface layer, 26, 228, 235  surfactants, 189  surfing, 26  surgical, 111  surplus, 548  surveillance, 466  survival, 167, 193, 389, 431, 442, 447, 448, 451, 452,  453, 487, 489, 490, 514  survivors, 17, 487  susceptibility, 30, 141, 148, 155, 453  suspensions, 102, 417, 444  sustainability, 41, 44, 448, 475, 557, 564  sustainable development, xviii, 59, 79, 337, 537  swamps, 31, 170  Sweden, 276, 563, 565  swelling, 101, 102  Switzerland, 227  symbiotic, 74  symptoms, 28, 31, 32, 167, 184, 302  synchronization, 573  syndrome, 167  synergistic, 108, 230, 449, 471  synergistic effect, 230  synthesis, xxi, 134, 141, 220, 435, 439, 441, 461,  463, 468, 513, 520, 572, 574  synthetic, 5, 6, 18, 22, 106, 163, 171, 414, 441  systematic, 59, 243, 291, 340, 375, 543 

T  T cell, 98, 99, 101, 102, 104, 111  T cells, 101, 102, 104, 111  T lymphocyte, 100  T lymphocytes, 100  Taiwan, 276, 280  tamoxifen, 107  tangible, 99  tankers, 158, 168, 169, 185, 269  tanks, 3, 13, 19, 25, 38, 52, 549, 556  tar, 32  target organs, 135  targets, 50, 55, 56, 59, 420, 453, 539, 540, 559  taste, 31, 301  tau, 444, 469  taxa, 77, 106, 367, 368, 370, 373, 375, 432 

taxes, 5  taxonomic, 234, 368  T‐cell, 111, 447  technological, xi, 64, 341, 559  technological developments, 559  technology, 109, 184, 269, 297, 544, 547, 549, 550,  553, 557, 561, 562, 563, 564  Tel Aviv, 243  telecommunication, 42  television, 64, 306  telomeres, 139  temperate zone, 177  temporal, 75, 101, 102, 111, 175, 179, 182, 183,  254, 300, 317, 322, 328, 354, 363, 375, 377, 383,  399, 407, 421, 438, 448, 475, 582, 592, 593  temporal distribution, 254, 328  teratogen, 489  teratogenic, 300, 302  terminals, 34, 268  territorial, 119, 185  territory, 589, 591  testes, 143, 154  testosterone, 101, 106, 110, 111, 112  Testosterone, 101  tetrachlorodibenzo‐p‐dioxin, 435, 447, 532  Texas, 403  textile, 13, 28, 233, 239, 241, 269, 298, 313, 471,  480  textile industry, 471  textiles, 11, 33, 293, 294, 304, 305  Thailand, 296, 309, 553, 563  Thailand XE "Thailand" , Gulf of, 296  thallium, 331  theoretical, 149, 304, 329, 569, 570, 571, 575, 578  theory, 403, 570, 571, 578, 579, 593  therapeutic, 174  therapy, 108, 456  thermal, 80, 404, 463, 472, 496, 548, 570  thermodynamic, 530, 570, 571  thermodynamic equilibrium, 570  thermodynamics, 570, 571, 572, 575, 579  Thessaloniki, 235, 236, 255  theta, 435  thinking, 109, 550  thioredoxin, 508  Thomson, 400  thorium, 16, 64, 65, 172  threat, 3, 13, 15, 25, 31, 38, 75, 125, 161, 165, 294,  410  threatening, 177 

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Index threats, 26, 184, 554  Three Mile Island, 63  threshold, 33, 126, 283, 303, 502, 541  threshold level, 541  throat, 28, 30, 32  thymidine, 104, 412, 423  thymocytes, 266  thymus, 99, 105, 106, 107, 110, 112  thyroid, 295, 300, 305, 306, 308, 489  thyroid cancer, 300  thyroid gland, 300  ticks, 594  tides, 19, 39, 160, 176, 230, 264, 404  tiger, 216  Tilapia, 218  timber, 31, 42, 45, 46, 48, 241  time consuming, 123  time periods, 66, 373, 502  time series, 593, 594  timing, 94, 100, 141, 149  tin, 11, 176, 195, 198, 229, 265, 282  tinnitus, 36  titanium, 446, 472  Titanium, 506  titanium dioxide, 446, 472  tobacco, 32, 65, 419, 429  tobacco smoke, 32  Tokyo, 258, 291, 331, 338, 533  tolerance, 296, 303, 442, 451, 452, 457, 464, 477,  502, 508, 512, 516  toll‐like, 104  toluene, 22  top management, 552  top‐down, 74  topsoil, 286  total energy, 85, 572  total organic carbon, 179  total organic carbon (TOC), 179  total product, 340  tourism, 224, 227, 229, 230, 243, 250  tourist, 26, 223, 230  toxic effect, 23, 26, 83, 135, 142, 143, 148, 208, 279,  467, 471, 480, 482, 496, 502, 507, 518  toxic metals, 141, 143, 148, 166, 504, 512, 514  toxic products, 29  toxic substances, xv, 158, 183, 223, 411  toxicological, 111, 133, 135, 136, 152, 295, 302, 305,  306, 310, 410, 411, 418, 438, 454, 471, 518  toxicology, 97, 102, 216, 221, 280, 312, 423, 433,  468, 472, 475, 493, 518, 532, 534 

635

toxin, 86, 87, 95, 105, 167, 415  toxins, 22, 73, 74, 85, 86, 89, 92, 94, 98, 105, 106,  157, 160, 163, 165, 438, 458, 574  trace elements, 193, 200, 217, 218, 230, 247, 249,  254, 258, 291, 496, 501, 502  tracers, 220  tracking, 55, 540, 542, 543, 552  trade, 229, 298, 453, 537, 538, 541, 551  trade‐off, 453, 537, 538  trading, 269  tradition, 294  traditional model, 534  traffic flow, 315  training, 54, 56, 59, 551, 572, 573, 575  traits, 70, 299, 442  trajectory, 410  trans, 197, 298, 302, 338, 522  transcript, 443  transcription, 433, 444, 469, 484, 518, 529, 532  transcription factor, 484, 518, 529, 532  transcription factors, 518  transcriptional, 442, 461, 533  transcripts, 439, 442, 469  transfer, 66, 67, 71, 181, 182, 183, 197, 199, 200,  218, 243, 245, 250, 293, 294, 301, 308, 490, 520,  522, 555, 556, 572  transference, 267, 269  transformation, 31, 44, 197, 306, 333, 424, 440, 521,  538, 584  transformations, 70, 310  transforming growth factor, 108  transition, 165, 195, 342, 369, 401, 594  transition elements, 195  transition metal, 165  transition period, 342, 369  translation, 135, 520  translational, 442  translocation, 507  translocations, 139, 153  transmission, 20, 570  Transmission Electron Microscopy, 508  Transmission Electron Microscopy (TEM), 508  transparency, 84, 339, 350, 372, 402  transplantation, 473  transportation, 25, 34, 117, 166, 169, 189, 318, 437,  545  transshipment, 34  traps, 23, 57, 264, 269  trauma, 572  travel, 8, 34, 64, 149, 164 

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636

Index

trawling, 235, 255  treaties, 185  treatment methods, 21  tree cover, 52  tree‐based, 584  trees, 45, 46, 48, 51, 52, 581, 582, 583, 584, 586,  593, 595  trend, 65, 133, 149, 176, 177, 182, 249, 271, 277,  307, 345, 347, 348, 349, 354, 356, 357, 358, 360,  363, 370, 372, 379, 382, 383, 389, 391, 414, 419,  421, 553, 563  trial, 544, 566  tribes, 157  trichloroethylene, 418, 543  Trichodesmium, 93, 367, 368, 370, 372, 397, 404,  405  triggers, 85  triglycerides, 167  trimmings, 11  tritium, 65, 71, 423, 425  tropical areas, 340  troposphere, 299  trout, 199, 217, 218, 303, 307, 421, 440, 441, 447,  455, 456, 457, 465, 466, 467, 471, 488, 492, 527,  528, 530, 531, 534  trucks, 30, 34, 35, 184  tsunami, 340, 343, 349, 354, 356, 362, 363, 364,  378, 397  Tsunami, 341, 349, 356, 402, 405  tubular, 300  tumor, 446, 450, 476  tumors, 476  tumour, 422  tumours, 300  tungsten, 166  turbulence, 76, 77, 84, 350  turbulent, 349, 350  turgor, 93  Turkey, 193, 203, 205, 206, 207, 210, 213, 216, 219,  225, 233, 239, 241, 242, 257, 258, 274, 298, 300,  308, 439, 457, 479  turnover, 200, 211  turtle, 162  turtles, 162, 163  Tuscany, 420  two‐dimensional, 443, 468  typhoid, 18  typhus, 163, 294  tyrosine, 520 

U  UAE, 182  ubiquitin, 437  ubiquitous, 63, 488, 517  UK, 93, 154, 172, 177, 216, 258, 274, 279, 282, 318,  407, 416, 462, 467, 472, 475, 490, 528, 535, 566,  593  Ukraine, 450  ulceration, 300  ultraviolet, 299, 445  ultraviolet light, 299, 445  unemployment, 39  uniform, 182, 268, 300, 355, 563  uniformity, 174, 562  unions, 34  United Arab Emirates, 182  United Kingdom, 189, 227, 338, 491, 563  United Nations, 21, 71, 72, 212, 483  United States, 3, 4, 5, 10, 12, 13, 16, 22, 24, 27, 34,  39, 97, 118, 179, 181, 221, 300, 313, 406, 475,  539  universe, 13, 70, 172  uranium, 15, 16, 33, 62, 63, 64, 65, 68, 71, 171, 172,  173, 451, 459, 514  urban areas, 17, 24, 28, 29, 30, 31, 33, 34, 116, 127,  324  urban centers, 181  urban population, 116, 158, 237  urban settlement, 265  urbanization, xv, 4, 45, 48, 115, 116, 130, 131, 179,  223, 518  urbanized, 307  urea, 33, 79, 87, 91  urine, 160, 206, 305, 435, 486 

V  vaccine, 108, 113  vaccines, 105  vacuole, 76  vacuum, 35, 184  Valdez, 171  validation, 94, 110, 318, 401, 426, 591  validity, 56, 117, 576  vanadium, 166, 198, 219, 247, 261, 331, 337  vandalism, 25  vapor, 306 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,

Copyright © 2010. Nova Science Publishers, Incorporated. All rights reserved.

Index variability, 90, 102, 103, 175, 178, 183, 227, 246,  248, 300, 325, 377, 412, 416, 418, 452, 466, 475,  488, 592  variable, 119, 168, 177, 178, 205, 227, 236, 318,  372, 412, 437, 438, 449, 452, 488, 551, 569, 584,  585, 586, 587, 588, 589  variables, 15, 119, 341, 370, 372, 388, 414, 435, 438,  454, 463, 562, 569, 584, 585, 588, 592, 594  vascular, 36  vasculature, 533, 534  vector, 47, 165, 328  vegetables, 19  vegetation, 23, 27, 28, 29, 37, 44, 45, 47, 52, 54,  170, 582, 583, 593  vehicles, 2, 3, 8, 27, 29, 30, 31, 34, 35, 45, 48, 161,  168, 173, 175, 176, 318, 497, 539, 564  vehicular, 52, 208  velocity, 77, 80, 81, 238, 390, 526  velvet, 331, 336  ventilation, 563, 564  venue, 74  verapamil, 436, 458  vertebrates, 98, 200, 432, 435, 440, 465, 490, 517,  519, 520, 524, 528, 531  vesicle, 76  vessels, 159, 232, 264, 265, 269, 271  veterinarians, 13  veterinary medicine, 100  VF, 461  vibration, 42, 45, 49, 52  victims, 26, 167, 188  video, 26  village, 269  vincristine, 414  viral, 76, 80  Virginia, 399, 469  virus, 447, 574  viruses, 8, 18, 24, 111  viscosity, 229  visible, 141, 168, 286, 367, 371, 397, 449  vision, xviii, 28, 167, 442, 537  visual, 2, 564  visualization, 417  vitamin C, 440  vitamin E, 418, 440  vitamins, 437, 520  vitiligo, 102, 111  voice, 188  volatility, 302  volatilization, 78, 296 

637

volcanic activity, 9, 28  voles, 134, 136, 137, 138, 139, 141, 142, 143  vomiting, 32, 302  vulnerability, 446, 448 

W  Wales, 416, 468  war, 39, 65, 116, 123, 164  Washington, 90, 91, 95, 175, 189, 217, 221, 308,  311, 313, 400, 467, 491, 492, 567  waste disposal, 10, 12, 125, 179, 239, 513, 554, 555,  558  waste disposal sites, 125  waste incineration, 14, 164  waste management, xviii, 12, 161, 232, 537, 539,  540, 541, 551, 564  waste products, 13, 25, 134, 229, 543, 574  waste treatment, 3, 179, 513, 545, 549  waste water, 54, 160, 164, 166, 226, 244, 249, 419,  496, 498, 514  wastewater treatment, 8, 18, 19, 20, 21, 22, 24, 161,  181, 227, 241, 545, 548, 557  Wastewater treatment, 24, 78  wastewaters, 21, 22, 25, 230, 415, 419  watches, 65  water heater, 31  water resources, 18, 20  water table, 127  watershed, 89, 227  watersheds, 265  water‐soluble, 170  waterways, 3, 17, 18, 22, 23, 37, 45, 52, 55, 173,  184, 194, 300  Watson, 91, 490, 566  waxes, 25  wealth, 43  weapons, 16, 63, 172, 174  weathering, 166, 193, 234, 238, 265, 318, 484  web, 87, 98, 101, 102, 106, 108, 197, 293, 294, 308  weight loss, 302  weight ratio, 98  well‐being, 2  wells, 18, 25, 556, 559  West Africa, 330  western blot, 442  Western countries, 529  wet, 66, 202, 203, 205, 206, 207, 208, 210, 211, 213,  214, 215, 223, 296, 301, 302, 303, 332, 333, 483,  555, 563, 581 

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638

Index

wetlands, 15, 23, 28, 77, 191, 280  wetting, 563  wheat, 298, 323, 324  wheezing, 28  white blood cell count, 100  wild ducks, 337  wildlife, 22, 26, 44, 45, 102, 109, 111, 117, 160, 165,  170, 179, 184, 299, 303, 304, 305, 308, 331, 333,  334, 335, 336, 440, 466, 474, 483, 487  wind, 4, 5, 29, 30, 77, 80, 81, 126, 161, 162, 164,  166, 169, 184, 225, 236, 237, 315, 316, 317, 318,  320, 330, 342, 350, 594  windows, 35, 107, 342, 468  wine, 28  winter, 74, 237, 267, 319, 321, 332, 340, 435, 444,  458, 469, 594  wires, 195  withdrawal, 83  women, 311  wood, 6, 11, 31, 32, 33, 140, 153, 161, 163, 188,  297, 299, 373  wood burning, 31  wood products, 33  wool, 269  workers, 12, 20, 34, 35, 43, 47, 70, 116, 125, 135,  147, 150, 151, 155, 295, 340, 341, 373, 522, 525,  527  workplace, 28, 32, 35  World Bank, 5, 565, 567  World Health Organisation, 310, 313  World Health Organization, 89, 131, 134, 150, 188,  220, 483  World Resources Institute, 40  World War, 17, 65, 163, 166, 172, 294 

worm, 423, 470  worms, 18, 22, 376, 383, 384, 410, 436  worry, 550  writing, 278 

X  X chromosome, 137  xenobiotic, 416, 420, 422, 456, 457, 464, 496, 518,  519, 520, 521, 522, 525, 527, 530, 531, 534  Xenobiotic, 433, 517, 519, 522, 526, 530  xenobiotics, 427, 433, 434, 435, 438, 441, 443, 446,  447, 455, 457, 458, 463, 467, 468, 522, 530, 531  x‐ray, 17, 62, 64 

Y  yeast, 436  yield, 187, 340, 543, 545, 557  yolk, 441  yuan, 5 

Z  zebrafish, 527, 533, 534  Zimbabwe, 300  Zinc, 14, 198, 201, 218, 234, 235, 236, 256, 485, 486,  490, 491, 505, 506, 507, 516  zooplankton, 76, 80, 160, 162, 164, 168, 181, 267,  280, 356, 366, 488, 492 

Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Incorporated, 2010. ProQuest Ebook Central,