Methods of control of natural objects and environmental monitoring: educational-methodological handbook. 9786010410961

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AL-FARABI KAZAKH NATIONAL UNIVERSITY ________________________________________________________

O. I. Ponomarenko, M. A. Botvinkina, I. V. Matveyeva

METHODS OF CONTROL OF NATURAL OBJECTS AND ENVIRONMENTAL MONITORING Educational-methodological handbook

Almaty «Qazag university» 2015

UDC 502/504(075.8) LBC 20.1873 P 82 It is recommended for publication by the Academic Council of the Faculty of Chemistry and Chemical technology and RISO of al-Farabi Kazakh National University (Protocol 39 16 January 2015)

Reviewer: PhD on speciality Radiological Ecology, Radiation Biology, Radiation Chemistry Abishev T.B.

P 82

Ponomarenko O.I. Methods of control of natural objects and environmental monitoring: educational-methodological handbook / O.I. Ponomarenko, M.A. Botvinkina, I.V. Matveyeva – Almaty: Kazakh Universitity, 2014. – 165 p. ISBN 978-601-04-1096-1 There is the information on environmental monitoring in the educational-methodological handbook. The principles of environmental normalization of pollutants, i.e. their income into the environment and the content in the air, water, soil and food, are presented. Educational-methodological handbook includes practical works on monitoring of air, surface water, soil and food, as well as methods of analysis of natural environments. In addition to the theoretical material, very important in practical work of the environmental monitoring data and reference standards, i.e. maximum allowable concentration of pollutants in air, water and soil; sources of air pollution; requirements for drinking water; maximum permissible concentrations of heavy metals in food raw materials and products, are given. It is recommended for students enrolled on chemical specialties, as well as experts in the field of ecology.   -     

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UDC 502/504(075.8) LBC 20.1873

ISBN 978-601-04-1096-1

© Ponomarenko O.I., Botvinkina M.A., Matveyeva I.V. 2015 © Al-Farabi KazNU, 2015

CONTENT INTRODUCTION..................................................................................................................5 1. Monitoring of environment........................................................................... 7 1.1 Concepts of substances-pollutants of the environment. Toxicity...............................7 1.2 Quality of the environment and its standards.............................................................8 1.3 Heavy metals as the major pollutants of natural environments.................................10 1.4 Classification and system of monitoring....................................................................12 1.5 Designing of monitoring systems as the basis of their effective functioning............18 1.6 Fundamentals of chemical monitoring....................................................................... 20 1.7 Organization of monitoring system............................................................................22 1.7.1 Sampling and organization of the network of monitoring of the pollution of air, soil and natural waters.................................................23 1.7.2 Plan (map) of monitoring objects....................................................................28 1.7.3 Environmental assessment of the study area, the environment and the objects of anthropogenic impact................................................................ 28 2. METHODS OF CONTROL OF NATURAL OBJECTS...............................................33 2.1 Contact Methods of Environmental Monitoring.......................................................... 33 2.1.1 Chemical methods of analysis.........................................................................36 2.1.2 Methods of molecular spectroscopy................................................................37 2.1.3 Methods of Atomic Spectroscopy...................................................................40 2.2 Distance methods of environmental control..............................................................41 2.3 Biological methods of environmental control............................................................43 3. MONITORING OF ATMOSPHERE..............................................................................46 3.1 Assessment of atmospheric air pollution...................................................................46 Laboratory work #1. Determination of dust content of air........................................50 Laboratory work #2. Measurement of the deposition of pollutants from the air.......52 Laboratory work #3. The investigation of natural rainfall.........................................53 Laboratory work #4. Analysis of snow cover............................................................ 55 Laboratory work #5. Determination of heavy metals in atmospheric precipitations.............................................................................................................. 55 Laboratory work #6. Express methods of determining of carbon dioxide in indoor air................................................................................................................56 Laboratory work #7. Determination of sulfur dioxide in the laboratory air.............59 Laboratory work #8. Determination of sulfur content in coal...................................60 Laboratory work #9. Effect of acid rain on living organisms.................................... 61 Laboratory work #10. The estimated amount of emissions into the air from motor vehicles............................................................................................................62 Laboratory work #11. Determination of lead content in the leaves of the trees growing in different areas of the city......................................................68 4. MONITORING OF SOIL................................................................................................ 70 4.1 Assessment of soil contamination..............................................................................70 4.2. Sampling and preparation of soil samples for analysis..............................................72 Laboratory work #12. Determination of physical properties of soils........................74 Laboratory work #13. Determination of soil acidity.................................................76 Laboratory work #14. Determination of the biological activity of soils...................78 Laboratory work #15. Determination of chemical composition of soil.....................80 5. MONITORING OF WATER OBJECTS........................................................................ 84 5.1 Evaluation of surface water pollution........................................................................85 5.2 Sampling of water and sample preparation for analysis............................................88

5.3 Organoleptic characteristics of natural water samples...............................................89 Laboratory work #16. Identification of the main organoleptic characteristics..........89 5.4 Chemical properties of natural water samples...........................................................93 Laboratory work #17. Determination of the pH value.............................................. 93 Laboratory work #18. Determination of the dry residue........................................... 95 Laboratory work #19. Determination of water hardness...........................................96 Laboratory work #20. Determination of dissolved oxygen.......................................99 Laboratory work #21. Determination of water oxidability........................................ 101 Laboratory work #22. Quantitative determination of nitrates...................................105 Laboratory work #23. Determination of chlorides.................................................... 106 Laboratory work #24. Determination of sulfate........................................................ 107 Laboratory work #25. Determination of the taste and aftertaste of water................. 110 Laboratory work #26. Determination of sediment....................................................110 Laboratory work #27. Determination of surface-active substances (surfactants).....110 5.5 Biochemical processes in the aquatic environment................................................... 112 Laboratory work #28. Evaluation of the eutrophic status of water bodies and watercourses on the basis of chlorophyll A...............................113 Laboratory work #29. Evaluation of the eutrophic state of water reservoirs and watercourses by content of phosphorus in them..................115 5.6 Heavy metals in natural waters and their sorption on sediments...............................116 Laboratory work #30. The study of migration of heavy metals in model systems «water – sediment».............................................117 Laboratory work #31. Determination of different forms of heavy metals in sediments.....................................................................................117 Laboratory work #32. Determination of oils in sediments of natural water reservoirs.........................................................................................118 6. MONITORING OF FOOD..............................................................................................120 6.1 Assessment of Food Contamination.......................................................................... 120 6.2 Legislative regulation of food quality........................................................................124 6.2.1 Requirements for the quality and safety of food products.............................. 124 6.3 General recommendations on sampling of food and their preparation for analysis..126 Laboratory work #33. Determination of the content of iron in the food................... 127 Laboratory work #34. Determination of dyes (containing sulfur) in drinks..............129 Laboratory work #35. Determination of vitamin C in drinks....................................129 Laboratory work #36. Determination of sulfitated reagents......................................131 Laboratory work #37. Determination of heavy metals in food.................................132 Laboratory work #39. Influence of salts on the properties of the protein..................133 Laboratory work #40. Influence of acidity on the properties of the protein..............134 Laboratory work #41. Effect of ethanol on the properties of the protein..................135 Laboratory work #42. Determination of hazardous substances (solanine) in potatoes..................................................................................................................135 Laboratory work #43. Determination of foreign matter (starch) in sour cream........ 136 Laboratory work #44. Determination of caffeine and tannin in tea...........................136 7. Data Processing and Presentation of the results........................... 138 7.1 Data processing and obtaining of statistical estimates...............................................138 7.1.1 Estimation of the mean value and its uncertainty...........................................138 7.1.2 Assessment of the reliability of the differences of mean values.....................140 7.2 Ecological mapping of microdistrict.......................................................................... 140

References....................................................................................................................... 145 appendix............................................................................................................................. 146

INTRODUCTION Ecology, environmental pollution, environmental monitoring, environmental chemistry are common words and their combinations, expressing a general concern for the state of environment in our time. First cause of the problem is detection of intense and disturbing changes caused by human activities, man-made changes in environmental systems, especially in the biosphere. Environmental factors can have a different nature and can have harmful effect on the organism. These are physical factors, such as temperature, pressure, fluctuations of the medium (sound, vibration etc.) which are at a sufficient impact force can damage the organism. To the chemical factors the presence of substances in the environment that effect on living organisms by chemical and physical-chemical interactions with molecules and atoms which are part of living substance can be referred. Constitution of the Republic of Kazakhstan establishes the right of every citizen to a healthy environment, reliable information about its condition and compensation for a damage caused to his health or property by ecological offenses. For radical improvement of the environment, targeted and thoughtful actions will need. Responsible and effective policy in relation to the environment will be possible only if we accumulate reliable data on the current state of the environment, evidence-based knowledge about the interaction of the important environmental factors. The Environmental Code of the Republic of Kazakhstan (Article 39) describes the types of effects to be taken into account in the assessment of influence on the environment. 1. The procedure of impact assessment on the environment shall be accounted for: 1) direct effects, i.e. impacts which are directly provided by the main and related types of planned activities in the area of the object; 2) indirect effects, i.e. impacts on the environment, which are caused by indirect (secondary) factors, arising as a result of the realization of the project; 3) cumulative effects, i.e. impacts, resulting from the ever-increasing changes, caused by past, present or reasonably foreseeable actions that accompany the implementation of the project. 2. In the procedure of impact assessment on the environment shall be carried out the assessment on: 1) air; 2) surface water and groundwater; 3) the bottom surface of the water reservoirs; 4) landscapes; 5) land and soil cover; 6) flora; 7) fauna; 8) condition of ecological systems; 9) state of health of the population; 10) social services (employment, education, transport infrastructure). This teaching manual is devoted to the consideration of methods of integrated assessment of ecological state of water objects, atmosphere, soil and foods. In this regard, the manual describes the most common phenomena and patterns observed in natural objects. Great attention is paid to issues of organization of observations, carrying out of sampling, as well as methods and tools for environmental monitoring. 5

The questions of organization, functioning and performance of monitoring systems are described. This educational-methodical handbook considers environmental quality standards, the basic characteristics of pollutants of natural objects and foods, their standardization, methods of control of the state of natural ecosystems for monitoring at different levels. The manual gives a classification of modern methods of environmental control. The attention is focused on the methods of analysis of pollution of air, water, soil and food, which are used in the performance of the listed practical work. The manual contains 42 practical works, which differ significantly from traditional activities on various sections of chemistry. The specificity is in their integrative character. These works suggest the presence not only of fundamental chemical knowledge, but sufficiently broad concepts of the areas of general ecology, hydrochemistry, atmospheric chemistry, pedology, toxicology etc. It is based on an integrated approach, i.e. practical work includes the study of real natural objects. Carrying out of such works contributes to: – development of skills of students to organize a system of monitoring of the state of the environment and detect trends; – familiarizing of students to specific environmental activities through the solution of practical problems; – formation of the modern scientific worldview, including an evaluation of possible adverse effects of human activities on the biosphere and humanity. All chapters in the manual are completed by checklists. In addition, the guide contains the applications containing reference information and guidelines, which are very important in practical work: MPC of harmful substances in natural water, air, food raw materials and products; parameters, which are obligatory in monitoring program; methods of preservation, features of the sampling and storage of samples etc. Teaching manual is designed for teachers and students of environmental, chemical, and biological specialties, as well as experts in the field of environmental protection.

1. MONITORING OF ENVIRONMENT 1.1 Concepts of substances-pollutants of the environment. Toxicity Anthropogenic impacts are the activities related to the realization of economic, military, recreational, cultural and other interests of humans making physical, chemical, biological and other changes in the environment. By nature, depth and area of distribution, time of action and nature of applications they may be different: focused and spontaneous, direct and indirect, long-term and short-term, point and area and so on. Anthropogenic impacts on the biosphere by their environmental effects are divided into positive and negative. The positive effects include the reproduction of natural resources, restoration of groundwater resources, field-protective forest planting, land reclamation in places of mining of mineral resources etc. Negative effects on the biosphere include all types of impacts made by human and oppressive nature. Unprecedented on capacity and variety of negative anthropogenic impacts particularly sharply began to appear in the second half of XX century. Under their influence, the natural biota of ecosystems ceased to be a guarantor of the stability of the biosphere, as it was observed earlier, for billions of years. Negative effect manifests itself in the most diverse and ambitious actions: the exhaustion of natural resources, deforestation of large areas, salinization and desertification of lands, reducing the number and species of animals and plants etc. The main factors of global destabilization of the environment include: – increasing of consumption of natural resources when they are reducing; – increasing of the world population when reducing the habitable areas; – degradation of the main components of the biosphere, reducing of the ability of nature for self-maintenance; – potential climate change and the depletion of the ozone layer; – reducing of the biodiversity; – increasing of environmental damage from natural disasters and man-made disasters; – inadequate coordination of the international community in environmental protection problems. The main and most common type of negative human impact on the biosphere is pollution. Pollution is inflow into natural environment of any solid, liquid or gaseous substances, microorganisms or energy (in the form of sounds, noise, radiation) in amounts harmful to health of human, animals, plants and ecosystems. By objects of pollution it is distinguished pollution of surface or groundwater, air pollution, soil pollution etc. Recently problems associated with contamination of near-Earth space have become urgent. Sources of pollution can be natural (dust storms, volcanic activity, landslides etc.) and anthropogenic. The most dangerous anthropogenic pollution sources for the populations of all organisms are industries (chemical, metallurgical, cellulose-paper, building materials etc.), heat power engineering, transportation, agriculture, and other technologies. There are the following types of pollution: chemical, physical and biological. 7

The types of pollution are any adverse anthropogenic changes to ecosystems: ingredient (mineral and organic) pollution as a set of substances foreign to the natural biogeocenosis (e.g., domestic sewage, pesticides, products of combustion in internal combustion engines etc.); parametric pollution is changes in the quality parameters of the environment (heat, noise, radiation, electromagnetic); biocenotic pollution disturbs the composition and structure of populations (overexploitation, deliberate introduction and acclimatization of species etc.); fixed-destruction pollution associated with impaired and the transformation of landscapes and ecosystems in the course of nature (damming of streams, urbanization, felling etc.). In general form, we can determine the toxicity, as a property (ability) of chemicals acting on biological systems by non-mechanical, cause their damage or destruction, or, in the context of the human body, the ability to cause abnormal function, disease or death. Substance, that has a toxic effect, is called toxicant, and the process of effecting of toxicant on the body is toxication (on the ecosystem – toxification). By N.S. Stroganov, toxicity of the substance to the individual organism is defined as the inverse value of the median lethal concentration: # = 1/LC50. Substances differ greatly in toxicity. With lower amount of substance is capable of causing to damage the organism, it is more toxic. Quantitative measures of toxicity for living organisms are a measure of acute toxicity NOEC, LC0, LC50, LC100, established for a «pure» substance during laboratory research. Indicators are not universal values and are established for each test object individually. NOEC (no observed effect concentration) is maximum inactive concentration of substance; LC0 is the minimum sensitivity threshold at which specific test reactions or mortality of the test object is observed; LC50 is a standard measure of toxicity, which shows the concentration of substance that possible to cause death in 50% of test organisms within a set time (24, 48, or 96 h); LC100 is the highest lethal threshold for all animals or test culture of seaweed used in the experiment. 1.2 Quality of the environment and its standards The quality of the environment is the degree of compliance of its characteristics to people's needs and technological requirements. All environmental protection activities are based on the principle of normalization of environmental quality. This term means the establishment of standards (indicators) of allowable human impact on the environment. Environmental quality standards are a set of common requirements for the state of natural and industrial facilities. They provide measures to ensure the optimal state of the environment, the quality of which consist of technical, economical, organizational norms that determine the quality parameters of the environment. 8

According to environmental law, compliance with environmental regulations, i.e. standards that define the quality of the environment, provides: – environmental safety of the population; – preservation of genetic fund of humans, plants and animals; – rational usage and reproduction of natural resources in the context of sustainable development. Decreasing the limit value of environmental standards, the quality of the environment is increasing. In case of increasing of the level of development of society, environmental quality standards tend to tighten, i.e. decreasing of the limit value. The main environmental quality standards and the impact on the environment are the following: sanitation and hygiene: – the maximum permissible concentration (MPC) of hazardous substances; – acceptable level of physical impacts (noise, vibration, ionizing radiation etc.); production and business: $ permitted emission of harmful substances; $ permitted discharges of hazardous substances; $ permissible removal of environmental components; $ norm of waste production and consumption; composite indicators: – permissible anthropogenic stress on the environment. – It is impossible to eliminate harmful substances from entering to the environment due to economical and technological reasons, so standards of maximum permissible concentration (MPC) of hazardous substances should be used. All existing MPC represent a compromise between acceptable and really existing level of pollution of the atmosphere, hydrosphere and lithosphere. Normative parameters, used in monitoring, are divided into two main groups: – sanitation and hygiene; – ecological. Sanitation and hygiene indicators are established based on the requirements of ecological safety of the population, but they do not take into account the reactions of other organisms to pollution. So to assess the state of the environment ecological criteria, which are considered as a measure of human impact on ecosystems and landscapes, are also used. They include indicators of state of air, water, soil and biogeocenotic cover in general, as well as an important place is occupied by biological indicators. The combination of a variety of criteria makes it possible to obtain a comprehensive assessment of the environmental situation. There are many approaches for solving of this problem, but generally the search of complex environmental indicators is complex and not completely solved problem. Maximum permissible concentration (MPC) is the amount of contaminant in the soil, air or water medium, which at permanent or temporary effects on humans has no effect on his health and does not cause adverse effects to its progeny, as well as minimize environmental damage to natural communities. There are more than 1,900 MAC of harmful chemicals for water basins, more than 500 – for air and more than 130 - for soils in our country. MACs are established 9

on the basis of comprehensive research and constantly monitored authorities of the State Committee on Sanitary Epidemiological Supervision. MPC periodically reviewed and adjusted. Following the approval of norm becomes legally obligatory. For atmospheric air there are two norms of MPC: one-time and daily average. Maximum single maximum permissible concentration (MPC m.s.) should not cause reflex reactions in the human body (sense of smell, change of the light sensitivity of the eyes etc.) at the inhalation of air during 30 minutes. The daily average maximum permissible concentration (MPC d.a.) should not affect a person directly or indirectly harmful interference indefinitely long (years) exposure. If there are few pollutants with synergistic effect (such as dioxides of sulfur and nitrogen; ozone, nitrogen dioxide and formaldehyde) in the composition of the air, the sum of ratios of concentrations (C, mg/m3) to the MPC (mg/m3) should not exceed 1 in calculations: &1/ MPC1 + &2/ MPC2 + ....+ &n/ MPC n < 1. The maximum permissible concentration of harmful substances in the soil (MPC, mg/kg) should not directly or indirectly affect to the environment, disrupt the natural purification capacity of the soil and adversely affect human health. MPC of pollutants in the water is such a concentration, above which it becomes unusable for one or more types of usages. MPCaq is the maximum permissible concentration of pollutants in different types of water reservoirs of utility and drinking, cultural and community, fishery purposes (mg/l). The permissible level of radiation and other physical effects on the environment is a level which is not harmful for health of human, animals, plants and their genetic fund. The permissible level of radiation exposure is determined by the radiation safety standards. Acceptable levels of exposure to noise, vibration, magnetic fields etc. are also established. Permissible emission or discharge is the maximum amount of pollutants per unit of time, which allowed throwing by this particular company in the atmosphere or discharging to the water reservoir, without causing excess MPC of pollutants and adverse environmental impacts in them. 1.3 Heavy metals as the major pollutants of natural environments Heavy metals belong to the most prevalence of pollutants of water, soil and air. Heavy metals are included in the food chain through cycling, concentrating in microorganisms, plants, animals, and thus affect people. Water-soluble and dispersed forms of presence of metals in water and soil are distinguished. Heavy metals include metals with a specific weight greater than 4.5 g/cm3. First of all, metals, with the most widely used in large volumes in industrial activity and in result of accumulation in the environment represent a serious danger in terms of their biological activity and toxic properties, are the most interesting. Among them are lead, mercury, cadmium, zinc, bismuth, cobalt, nickel, copper, tin, antimony, vanadium, manganese, chromium, molybdenum and arsenic. Heavy metals are related to non-conservative metals, i.e. their content in water, soil, active and digested sludge depends of temperature, salinity, presence of 10

inorganic and organic complexing agents, biological activity, time of year and the value of pH. Currently, emissions of heavy metals as a result of human activities became comparable with the magnitude of the natural emissions of these elements. Moreover, industrial intake of a number of elements significantly exceeds natural intake, resulting in a change in the natural cycles of metals, the direction and pace of their migration and accumulation. Calculations of estimates of relative income of metals into the biosphere from anthropogenic sources, cited in various studies, are highly variable (Table 1). Table 1 Intensity of metal input into the atmosphere, 103 tons / year Metal

Cobalt

Natural sources

Anthropogenic sources

removal from the ocean

volcanic eruptions

weathering of the lithosphere

combustion of fuel

others

0.2

0.1

7

0.9

2

Copper Iron Manganese Lead Yttrium Zinc Mercury

5 50 7 8 10 8 4

6 300 9 0.4 0.7 10 0.004

10 10000 200 3 30 80 0.24

2 2000 8 4 20 80 -

50 4000 400 400 2 200 0.11

Cadmium

-

0.17

0.4

-

0.055

Only as a result of the metallurgical plants on the Earth surface annually enters (thousand tons): copper – not less than 154.7, zinc - 121.5, lead – 89, Ni – 12, cobalt – 0.765, molybdenum – 1.5, mercury – 0.031; because of burning of coal and oil (thousand tons): lead – 3.6, mercury – 1.6, copper – 2.1, zinc – 7, nickel – 3.7. Heavy metals leak into surface and water from the atmosphere or by dumping of untreated sewage. Mining and processing are not the most powerful source of environmental pollution of metals. The process of coal combustion is the main source of many metals in the biosphere. All metals are presented in coal and oil. There are toxic chemicals, including heavy metals, considerably larger than in the soil, in the ash of power plants, industrial and household furnaces. The amount of mercury, cadmium, cobalt, arsenic in atmospheric emissions from fuel combustion is 3-8 times higher than the amount of extracted metals. Metals relatively quickly accumulate in the soil and are extremely slow derived from it: the half removal of zinc is up to 500 years, cadmium – up to 1,100 years, copper – up to 1,500 years, lead – up to several thousand years. 11

Significant source of contamination of soil metals is application of fertilizer from sludge obtained from industrial and sewage treatment plants. The content of heavy metals in sewage sludge and industrial waste varies depending on the type, location and method of their producing. It is generally accepted that the greatest amount of heavy metals are in phosphorus fertilizers. The smallest amounts of metals contain nitrogen fertilizers; potash fertilizers are close to nitrogen, but with larger concentration of lead (about 20 times). Based on concentrations in nitrogen and potassium fertilizers heavy metals form similar decreasing series: for calurea – Fe> Ni> Zn> Mn> Pb> Cu> Cd; for potassium chloride – Fe> Ni> Mn> Pb> Zn> Cu> Cd. The metal content in lime, generally, is less than their concentrations in the phosphate fertilizers. Organic fertilizers are usually characterized by low concentrations of most heavy metals. Aerosol pollution entering the atmosphere, are removed from it by the natural self-purification processes. An important role is played by atmospheric precipitation. As a result, industrial emissions to air, wastewater discharges create the prerequisites for entering of heavy metals in soil, groundwater and open water, plants, sediments and animals. To understand the factors that regulate the concentration of metal in natural waters, their chemical reactivity, bioavailability and toxicity, it is necessary to know not only the total content, and the proportion of free and bound forms of the metal. Thus, the chelate forms of Cu, Cd, Hg are less toxic than the free ions. Transition of metals in the aquatic environment in the form of metal complex has three consequences: 1) it can be increasing of the total concentration of metal ions by passing it into solution from sediment; 2) the membrane permeability of complex ions may differ significantly from the permeability of hydrated ions; 3) the toxicity of the metal as a result of complexation can vary greatly. Generally, the effects of anthropogenic pollution of the environment by heavy metals can be divided into four groups: – changing in concentration of metals within the individual components of the biosphere; – changing in the species and types of metal compounds within the individual components of the biosphere; – appearance of compounds of metals in some areas in large quantities, not specific for these natural conditions; – mechanical movement of considerable masses of metals without significantly changing of their species. 1.4 Classification and system of monitoring The term «monitoring» first appeared in the recommendations of the special commission of SCOPE (Scientific Committee on Problems of the Environment) of UNESCO in 1971, and in 1972 there were first proposals to the Global Environment Monitoring System (UN Stockholm Conference on the Environment). The term 12

«monitoring» (from the Latin monitor, meaning supervising) means a system of repetitive targeted observations of one or more elements of the environment in space and time. The ancient philosophers believed that everything in the world is connected to everything that careless interference with even seemingly minor importance can lead to irreversible changes in the world. Observing nature, we evaluated its long time with the townsfolk positions, not thinking about the appropriateness of the value of our observations, that we are dealing with the most complex and self-organizing and selfstructured system, that man is the only particle of the system. And if in the time of Newton humanity admired the integrity of this world, it is now one of the strategic thoughts of humanity is a violation of the integrity, inevitably arising from the commercial attitude to nature and the underestimation of the globalism of these violations. Man changes the landscape, creates artificial biosphere, organizes agrotechnonatural and fully technogenic biocomplexes, reconstructs the dynamics of rivers and oceans and changes in climate processes. Moving in this way, he paid to harm of nature, and ultimately himself, all his scientific and technical capabilities until recently. Negative feedback of wildlife are increasingly resisting the onslaught of the man, everything is more pronounced discrepancy goals of man and nature. And now we are witnessing a crisis point approaching which the genus Homo sapiens cannot exist. In this sense, the monitoring system is the mechanism that helps to prevent slipping of humanity to disaster. Companion of human activity is increasing of power of disaster. Natural disasters always occur. They are one of the elements of the evolution of the biosphere. Storms, floods, earthquakes, tsunamis, forest fires etc. annually bring enormous material damage, absorb human lives. Simultaneously more and more anthropogenic causes of many accidents are gaining strength. Regular oil tanker accidents, the accident at Chernobyl, explosions at factories and stores with emissions of toxic substances and other non-predictable disaster are the reality of our time. The growth of the number and capacity of accidents demonstrates the helplessness of man in the face of impending ecological disaster. Only prompt largescale introduction of monitoring systems can push it. The modern term «monitoring» refers to regularly performed for a given program of observation of natural objects, natural resources, flora and fauna, allowing them to allocate state and processes occurring in them under the influence of human activities (Figure 1). MONITORING

OBSERVATIONS of the state of the environment and of the factors affecting on it

ASSESSMENT of the actual state of the environment

Fig. 1. Components of the monitoring 13

PREDICTION of state of the environment and assessment of projected

To achieve these goals, environmental monitoring solves the following problems: $ selection of the object of observation; $ providing of the collection, processing, storage, complete, reliable and comparable information on the state of surveillance; $ timely making available data of monitoring to interested consumers; $ harmonized methodological and metrological support of conducting various kinds of environmental monitoring. According to methods of observation monitoring can be divided into several classes: physical, biological, chemical, environmental, ecobiochemical, complex. Physical monitoring system is based on the observation of the influence of physical processes and phenomena on the environment (floods, earthquakes, tsunamis, volcanic eruptions, erosion etc.). Biological monitoring is monitoring by using bioindicators (organisms, presence, status and behavior of which are judged on the changes in the environment). Chemical monitoring is system of observations of the chemical composition (natural and anthropogenic) of atmosphere, precipitations, surface and ground waters, waters of the oceans and seas, soils, sediments, vegetation, animals and control of the dynamics of the distribution of chemical pollutants. Global task of chemical monitoring is to determine the actual level of environmental contamination of highly toxic substances. The environmental monitoring is organized monitoring of the environment in which: firstly, there is continuous assessment of environmental conditions of the human environment and biological objects (plants, animals, microorganisms etc.), and the assessment and the functional value of ecosystems; secondly, there is creating of the conditions for determining of corrective actions in cases where the targets of environmental conditions are not achieved. Ecobiochemical monitoring is monitoring, based on an evaluation of the two components of the environment (chemical and biological). There are different approaches to the classification of monitoring (by the nature of tasks, by levels of organization, by natural media for monitoring). Figure 2 shows the classification covering the entire block of environmental monitoring, observing the changing of abiotic components of the biosphere and response of ecosystem to these changes. Thus, monitoring of the environment includes both the geophysical and biological aspects that defines a wide range of research methods and techniques used in its implementation. The monitoring system In accordance with this definition and assigned to system functions in the monitoring system should include the following basic procedures: $ selection (definition) of the object of observation; $ examination of the selected object of observation; $ preparation of the information model for the observed object; $ planning of measurements; 14

$ $ $

assessment of the state of the object of observation and identification of its information model; prediction of changes in the state of the object of observation; presenting of information in a user friendly form and bring it to the consumer.

Monitoring of sources of exposure

Sources of exposure

Monitoring Factors of influence of factors -----------------------------------------------------------------------------------------of -------influence Physical Biological Chemical Natural environment Monitoring -----------------------------------------------------------------------------------------of state of -------the biosphere Atmosphere Ocean The surface of the Biota land with rivers and lakes, groundwater

Geophysical monitoring

Biological monitoring

Fig. 2. Classification of environmental monitoring

It should be noted that the monitoring system itself does not include quality control activities of the medium, but it is a source of information necessary for making important decisions. The main purpose of monitoring is to ensure environmental management systems and environmental safety of timely and reliable information to enable: $ evaluate the indicators of status and functional integrity of ecosystems and human environment; $ identify the causes of changes in these parameters and to assess the impact of such changes, and to identify corrective measures in cases where the targets of environmental conditions are not achieved; $ create the conditions for determining the corrective measures arising negative situations before they will be harmed. Based on these three main objectives, environmental monitoring should be focused on a number of indicators of three general types: compliance, diagnosis and early warning. 15

The most universal approach to defining the structure of the system of monitoring of anthropogenic environmental changes is its division into blocks (Figure 3). Besides the above main objectives, environmental monitoring can be focused on the achievement of specific program objectives related to ensuring the necessary information organizational and other measures for the implementation of specific nature protection activities, projects, international agreements and obligations of states in their respective fields.

Fig. 3. Block diagram of the monitoring system

Environmental monitoring system can be developed at the level of an industrial facility, city, district, region, republic etc. Today The Observation Network for sources of exposure and the Biosphere state already covers the entire globe. The Global Environment Monitoring System (GEMS) was established jointly by the international community. The first priority was recognized organization of monitoring of environmental pollution and it’s causing factors of influence. The monitoring system is characterized at several levels, which correspond to specially developed programs:  impact monitoring (I) is a study of the strong impacts on a local scale;  regional monitoring (R) is a manifestation of migration and transformation of pollutants, joint impact of various factors specific to the region's economy;  background monitoring (B) is on the basis of Biosphere Reserves, which excluded any economic activity. The character and mechanism of synthesis of information on the environmental situation during its motion through the hierarchies of monitoring system are defined 16

set of graphical representation of spatially distributed data characterizing the environment in a certain territory, together with the blank maps of the area. The resolution of information portrait depends on the scale of used blank maps. Resolution of information portrait depends on the scale of used blank maps. At movement of environmental information from the local level (city, district, zone of influence industrial design etc.) to the national scale, blank maps, on which this information is applied, increases, hence changing the resolution of the information portraits of ecological conditions in different hierarchical levels of monitoring. So, at the local level of monitoring, all emission sources (industrial ventilation tubes, wastewater discharge etc.) must attend in information portraits. At the regional level, closely spaced sources of exposure «combine» into one multicast source. As a result, the regional information portrait of small town with dozens of emission appears as a local source, the parameters of which are determined by monitoring data sources. At the national level of monitoring is observed even greater synthesis of spatially distributed information. Industrial areas, large enough territorial units may play a role of local sources of emissions at this level. At transition from one hierarchical level to another, not only information about the sources of emissions, but other data characterizing the environment are generalized. In developing of a monitoring system following information is required: $ sources of pollutants in the environment, i.e. emissions of air pollutants from industry, energy, transport and other facilities; wastewater discharges into water bodies; surface runoff of pollutants and nutrients in the surface water of land and sea; inclusion to the earth's surface and (or) in the soil layer of pollutants and nutrients with fertilizers and pesticides during agricultural activities; place of burial and storage of industrial and municipal waste; technological accidents, resulting to the release of hazardous substances into the atmosphere and (or) the spills of liquid pollutants and hazardous substances etc.; $ transfers of pollutants, i.e. atmospheric transport processes; migration and transport processes in an aqueous medium; $ landscape-geochemical processes of redistribution of pollutants, i.e. migration of contaminants in the soil profile to the groundwater level; migration of contaminants on the landscape-geochemical pairings based on geochemical barriers and biochemical cycles; biochemical cycle etc.; $ data on the state of anthropogenic emission sources, i.e. capacity of source of emission and its location, the hydrodynamic conditions of entering of emission into the environment. In the zone of influence of emission sources systematic observation of the following objects and the parameters of the environment is organized. 1. Atmosphere: chemical and radionuclide composition of the gas and particlephase air-sphere; solid and liquid precipitation (snow, rain) and their chemical and radionuclide composition; thermal and humid air pollution. 2. Hydrosphere: chemical and radionuclide composition of the medium of surface waters (rivers, lakes, reservoirs etc.), groundwater, suspensions and 17

sediment in natural drains and water bodies; thermal pollution of surface and groundwater. 3. Soil: chemical and radionuclide composition of the active layer of the soil. 4. Biota: chemical and radioactive contamination of agricultural land, vegetation cover, soil zoocenoses, terrestrial communities, domestic and wild animals, birds, insects, aquatic plants, plankton and fish. 5. Urban environment: chemical and radiation background of the air environment of human settlements; chemical and radionuclide composition of food, drinking water etc. 6. Population: characteristic demographic parameters (number and density of population, fertility and mortality rates, age structure, morbidity rate, birth defects and anomalies); socio-economic factors. Monitoring systems of natural environments and ecosystems include monitoring tools of environmental air quality, ecological state of surface waters and aquatic ecosystems, ecological condition of the geological environment and terrestrial ecosystems. Programs of observations are formed according to the principle of priority of choice (for priority determination) of pollutants and integral characteristics (reflecting the group of phenomena, processes or substances). 1.5 Designing of monitoring systems as the basis of their effective functioning It is noted in recent publications the importance of the stage of design (or planning) for the effective work of the monitoring system. It is emphasized that the proposed scheme or structure of design is relatively easy to apply for simple, local monitoring systems, but with the design of the national monitoring systems is facing great difficulties associated with their complex and contradictory. The essence of the design of the monitoring system should be to create a functional model or to plan the entire process chain for obtaining of information. As all stages of obtaining of information are closely linked, lack of attention to the development of any stage will inevitably lead to a sharp decrease in the value of all the information received. Based on the analysis of creating of national systems, the basic requirements for the design of such systems were formulated. These requirements should include the following five basic steps: 1) identification of tasks of monitoring and requirements for information needed for their realization; 2) establishment of the organizational structure and development of a network of observation of the principles of their realization; 3) formation of monitoring network; 4) development of a system for obtaining of data/information and the presentation of information to consumers; 5) establishment of a system of checking of the information received on the compliance to original requirements and review, and if necessary, the monitoring system. In the design of monitoring systems should be remembered that the results largely depend on the volume and quality of the original information. It should 18

include as much detail information about the spatio-temporal variability in the quality of natural objects, should contain detailed information about the kinds and amounts of economic activity, including data on the sources of pollution. It is also needed to rely on all legislative acts relating to the control and management of the environment, to take into account the financial capacity, the total physical and geographical situation, the basic methods of quality management and other information. 1. Definition of the tasks of monitoring systems of natural objects and requirements for information necessary for their realization. The role of the first stage is currently undervalued, that is the cause of many of the above-mentioned defects. To determine the requirements for information for the quality of natural objects requires more detail and linkage between objectives. As an example, water quality monitoring program developed in Canada can be noted. An important role is played formulation of as possible better understanding of water quality and methods to evaluate it. On the basis of clearly defined objectives, as well as the previously collected data of water quality, the information requirements, including the type, form and timing of its presentation to consumers, as well as suitability for water quality management should be determined. At the first stage of design, basic statistical methods of data processing should be selected, as from them the frequency and timing of observations, as well as requirements for the accuracy of the values largely depends. 2. Creating of the organizational structure of a network of observation and the development of the principles of their realization. This is the main and most difficult step in which, taking into account the objectives and the existing experience of the functioning of the system of monitoring, the structural main units of observation of networks, including central and regional (and/or problematic), with indication of their main tasks are defined. Actions to comply with the optimum ratio between the types of observational networks, including observations at fixed sites, operating a relatively long time on constant program, regional short tests to detect the spatial aspects of pollution, as well as intense local observations in areas of greatest interest are provided. At this stage it is decided the appropriateness and the scale of usage of automated, remote and other subsystems of monitoring. In the second stage general principles of observation are also developed. They may be presented in the form of guidelines or manuals for a number of activities: – the organization of spatial aspects of observations (choosing of the location of control points, their category according to the importance of the object and its conditions, determine the location of observing alignments, verticals, horizons etc.); – compilation of the program of observations (indicators, terms and frequency to observe are planned, while provides recommendations for physical, chemical and biological parameters for typical situations); – organization of the system of control of correctness of work and accuracy of the results obtained at all stages. It is assumed that there are uniform guidelines for the selection and conservation of samples of water, soil, air, guidance on their chemical analysis etc. 19

3. Construction of the monitoring network. This step provides realization based on the proposed organizational structure of the network previously developed principles of observation, taking into account specific local (regional) conditions. The relations of types of observation networks are refined, the locations of the points in the stationary network are set, areas of intensive observations are highlighted, frequency of observations of natural objects for a possible revision of the observation network is planned. A concrete program for each item and the type of observation are provided, which regulatory the list of studied parameters, frequency and timing of their observations. In the presence of automated and/or distant observations for environmental quality, their programs of work are refined. 4. Development of a system to obtain data/information and the presentation of information to consumers. At this stage the features of the hierarchical structure of obtaining and collecting of information (observation points – regional information centers – a national information center) are determined. Development of databases on the quality of natural objects is planned and the types and conditions of presentation of information services, performed with them, are defined. A detailed description of the main forms of information published in the form of papers, reports, reviews, and describing the state of the natural objects in the country for a certain period of time is presented. The procedure for checking the precision and accuracy of obtaining data at all stages of work are also provided. 5. Establishment of a system of checking of the information received on the compliance to original requirements and review, and if necessary, to the monitoring system. After creating of a system of monitoring and beginning of its functioning there is a need to verify whether the information meets to its original requirements, whether it is possible to manage effectively the quality of natural objects on the basis of this information? If the information obtained corresponds to requirements imposed on it, the monitoring system can be left unchanged. If these requirements are not met, as well as new problems appear, the monitoring system needs to be revised. Legal security services of the environment and human health from the effects of pollutants is realized by various branches of legislation: constitutional, civil, criminal, administrative, health, nature protection, natural resource, as well as regulatory and legal acts, international conventions and agreements. 1.6 Fundamentals of chemical monitoring Solution of complex tasks of environmental protection and environmental safety is associated with chemical monitoring. Chemical monitoring is one of the most important cross-cutting fundamental problems of modern science for the following reasons: – the specificity and complexity of the various physical-chemical composition of the object of analysis, which introduces limitations on potential methods of analysis and makes it impossible to achieve the transfer of analytical and physical chemistry of the natural environment without additional research; – absence of suitable methods to identify compounds present in the ion, nondissociated, colloid, suspension and other physical-chemical conditions in multicomponent mixtures with unpredictable composition; 20

– necessity of quantitative determination of pollutants from the many impurities of variable composition, and the limit of detection of methods and instruments that are often associated with multiple concentration; – problem of the adequacy of the formulation of analytical tasks; – necessity of development of research methodologies that allow to study the conditions of the components in the environment, to assess the toxicity of the forms and their transformation in ecosystems, with many physical and chemical processes occurring in the real world, cannot be adequate modeling. Reliable and sufficient information on the normalized and normalized ecotoxicants needed for decision-making system can be obtained by chemical monitoring and cost-effective control only in the case of clearly defined criteria of environmental safety (regulations), the goals of ecological and chemical monitoring (control), choice of determined indicators and choices of analysis (scheme of control). All this is inextricably linked to the specifics of the investigated object, which is manifested in a variety of forms of existence of the components, which are of varying in lability and can transform not only in changes of natural conditions, but also under the influence of conditions of analysis. The necessity of new methodological approaches to chemical environmental monitoring and the development of new indicators is associated with the unsatisfactory state of the problem in our country and abroad, as the idea of an environment based on the hygiene principle of normalization (system of MAC) and by component analysis of the total contents of standardized compounds are insufficient. Speaking about the aquatic environment, various forms of co-existence of elements have different toxicity to aquatic biota and mammals, a transformation in the processes of interaction with inanimate nature and in the technological cycle of water treatment (co-precipitation, flotation, adsorption, extraction, complexation etc.) undergoes. To understand the behavior of toxicants in the biosphere it is necessary to know the species in the environment and the mechanisms of migration in food chains. The joint presence of toxicants affects their toxicological properties and the ability to accumulate in the metabolic transformation of living organisms. These effects are almost do not take into account existing standards. The main criteria for the formulation of analytical tasks must act importance, completeness and accuracy of the information received. In our opinion, the information is complete, which allow not only to evaluate the quality of the environment in a particular place and time interval on the basis of compliance of the current system of standardized indicators, but also answer (if non-compliance) to the questions: what exactly is bad; what is the reason; what are the implications for the biota; what to do; who is guilty? System-integrated studies of natural environments provide the opportunity to develop the principles, diagnostic algorithms of physical-chemical methods, test parameters, which allow quantifying the quality of the natural objects and predicting changes of this state. Some known and new indicators are below: 21

$ content of fat-soluble compounds and forms of metals; $ quantitative determination of ionic forms in a wide pH gradient and the dynamics of changes in the concentrations of these forms of real-time, determined on the basis of physiological parameters of digestion and absorption; $ the ability to concentrate the compounds in media with different degrees of hydrophilicity/hydrophobicity in static and dynamic conditions; $ complexing ability of natural waters relative to heavy metals; $ ability of natural waters to bind ligands-complexing agents, differing in their ability to form complexes, and the kinetics of complexation; $ dynamics of selective dissection of connected and inert forms of metals (complexes with humic substances, colloidal form, particulate etc.) defined by a set of chemical reagents in the fields of different physical nature (microwave, US and electrical). Chemical monitoring (e.g., of natural waters) using the proposed indicators, depending on the purpose should provide the following types of information: $ the amount of toxic forms of the elements and their compounds, and the level of toxicity of natural waters for the biota, and an assessment of these factors should be considered separately for humans and mammals, and for aquatic biota. It is necessary to consider the type of water consumption (periodic in the first case or continuous in the second) and the main diet, typical for this species and the region; $ the nature and mechanism of the effects of pollutants on the environment (animate and inanimate nature): instant, sustained, cumulative, catalytic, specific, integral etc.; $ the adequacy and effectiveness of the methods used for cleaning of natural and waste waters, depending on the type of natural waters and the environment in a given period of time; $ the ability of natural waters to self-cleanse and buffer capacity of reservoirs relative to pollution in a given time; $ the source of contamination and its geographical location. Efficiency of obtaining the degree of informativeness and accuracy of chemical monitoring of the results determine the content and effectiveness of environmental activities, methods, and intensity of natural resources, conditions and prognosis of conservation of biota in the conditions of technogenic civilization development. 1.7 Organization of monitoring system The effectiveness of monitoring depends crucially on its proper organization. Development of monitoring program. $ Goals and objectives. The main goal of any monitoring program is informational. The result should be to get information, to eliminate a particular uncertainty or, alternatively, to identify lack of information. Tasks are the specific actions or steps necessary to achieve the goal. $ The choice of priorities: the objects of observation and defined parameters. 22

On the basis of the objective should be to identify priorities: monitoring objects and parameters are defined. Objects are considered both manmade and natural. For example, if the objective of the program is related to the state of the river, the choice of the object may appear as the definition of a company or particular runoff, which will focus its actions of monitoring. If the problem is the state of the environment in polluted urban area, prioritization can start with choosing of the environment to monitor (air, water, soil, snow cover). $ Feedback. During the monitoring it must necessarily be implemented a feedback mechanism that allows to adjust the program, identify its weaknesses. Thus, taking into account the specific methods and equipment, interpretation of the results of the first measurements can be revised priorities of the program. After some time, materials accumulate for re-evaluation of program objectives, its compliance with the available resources. Prerequisite of effective work of a feedback mechanism is to control the quality of data and its correct and competent interpretation. For specific purposes or to identify the significance of the observed changes, to attract experts from outside may be useful. At this stage, much attention should be paid to the methods of processing and storage of primary data. The final stage is to spread the information obtained on the basis of carried out control programs, and make recommendations to all interested groups and organizations. In general, the program should: $ be scientifically based; $ be sufficiently flexible to allow revision of objectives and approaches on the basis of the results obtained; $ provide significant results, i.e. results carrying meaningful information that can be interpreted; $ be cost-effective, fully managed and controlled in terms of financial and time constraints. The general sequence of development and implementation of the monitoring scheme is presented in Figure 4. 1.7.1 Sampling and organization of the network of monitoring of the pollution of air, soil and natural waters When the controlled parameters are selected, it is necessary to determine the number and location of sampling sites (observations) and temporal sampling mode (observation). A place for the initial assessment or sampling is selected according the purposes of analysis and on the basis of careful consideration of all available prior information, as well as full-scale study area, or the controlled object, and must take into account all the conditions that could have an impact on the composition of the sample or the result of primary assessment of the presence and level of contamination. Point of observations is the place in which complex works to obtain data on the quality of the natural environment are realized. 23

Sampling is the most important part of the analytical procedure in monitoring of environmental quality by contact methods of observation. The sampling error is much higher than the error of sample preparation, and the error of sample preparation, in turn, is larger than the error of the method of analysis. That is why properly selected sample is the key to obtain reliable results. Representative sample statistically correctly reflects the state of the object of analysis and its qualitative and quantitative composition in a given time and in a given place, contains enough material for analysis, provides the conditions of preservation of the material composition of the medium during all time until the result of the analysis. Samples can be simple (single) and mixed. Sampling of a simple sample is single sampling in a single point of space of the total volume of material, which is necessary for analysis. Composite sample (averaged, combined, composite) is prepared by combining of several simple samples taken by a certain program at different points of space at the same time or in a selected single point in space at specific time intervals. During the monitoring of air pollution three categories of observation stations (stationary, route and mobile (undertorch)) are established. Stationary station is designed to provide continuous recording of concentrations of pollutants or regular air sampling for following analysis.Route station is designed for regular air sampling at a fixed location for observations, which is carried out using mobile equipment. Mobile station is designed for sampling under the plume in order to identify the source. The number of stations and their location is determined by population size, area of the settlement and the terrain, the development of industry and the network of highways. The number of stationary stations is set as follows (at least): 1 post – up to 50,000 inhabitants, 2 posts – 100,000 inhabitants, 2-3 post – 100,000-200,000 inhabitants, 3-5 posts – 200,000-500,000 inhabitants, 5-10 posts – more than 500,000 inhabitants, 10-20 posts (stationary and route) – more than 1 million inhabitants. Observations on the stations are held by one of the four programs: full, partial, shortened, daily. The full program is designed to obtain information about the single and average daily concentrations. Observations by the full program are performed daily by recording with automatic devices at regular intervals at least four times with a mandatory selection at 1:00 am, 7:00 am, 13:00 pm, 19:00 pm. It is allowed to perform observation on a rolling basis: 7:00 am, 10:00 am, 13:00 pm – on Tuesday, Thursday and Saturday; 16:00 pm, 19:00 pm, 22:00 pm – on Monday, Wednesday and Friday. Observations by partial program are allowed to carry out in order to obtain information about the single concentrations daily at 7:00 am, 13:00 pm, 19:00 pm. By shortened program observations are realized to obtain information about the single concentrations daily at 7:00 am and 13:00 pm. Observations by this program may be carried out at a temperature below – 45 °C and in places where the average monthly concentrations is below 1/20 of a single MAC. 24

Fig. 4. The general sequence of development and implementation of monitoring schemes 25

Daily program of sampling is designed to obtain information about the daily average concentration. Observations by this program are held by continuous daily sampling (1:00 am, 7:00 am, 13:00 pm, and 19:00 pm). The properties of substances and hazard class by establishing of the following frequency of sampling and analysis often take into consideration: $ for the first class – at least once per 10 days; $ for the second class – at least once per month; $ for the third and the fourth classes – at least once per quarter. In monitoring of surface water quality is carried out: $ monitoring of the level of pollution of surface water by physical, chemical, hydrological and hydrobiological indicators in control areas; $ observations, designed to solve specific problems. For the monitoring of surface waters are organized: $ stationary network of observation stations for the natural composition and surface water pollution; $ specialized network of stations for solving research problems; $ temporary expeditionary network of stations. Network of hydrochemical observations should include: in space: – as possible the water objects located in the territory of the studied basin; – all length of the watercourse with the definition of the influence of its major tributaries and wastewater into it; – all area of the reservoir with a definite influence on it most major tributaries and effluents in waste water; in time: – all the phases of the hydrological regime (spring floods, summer low water, summer and autumn rain floods etc.); – various water yield years (high water, medium, and low water); – daily changes of chemical content of water; – catastrophic wastewater discharges into water objects. All stations of observation of water quality of reservoirs and streams are divided into four categories – depending on the frequency and detailing observation programs. Purpose and location of control stations are determined by the rules of observations of water quality of ponds and streams. The stations of the first category are placed on medium and large water bodies and streams that are important for the national economy: $ in areas of cities with a population higher than 1 million of inhabitants; $ in spawning and wintering areas of the most valuable commercial fish species; $ in areas of repeated accidental discharges of pollutants; $ in areas of controlled discharges of wastewater, resulting in observed high water pollution. The stations of the second category are placed on water bodies and streams within the following areas: $ in areas of cities with a population from 0.5 to 1 million of inhabitants; $ in the spawning and wintering of valuable commercial fish species; 26

$ in important for fisheries areas before the dams of rivers; $ in areas of organized discharges of waste water of drainage from irrigated areas and industrial wastewater; $ at the areas of intersection of the rivers by the state border; $ in areas with average water pollution. The stations of the third category are placed on the water bodies and streams: $ in areas of cities with populations of less than 0.5 million of inhabitants; $ on the closing areas of large and medium rivers; $ in the mouths of polluted tributaries of large rivers and reservoirs; $ in areas of controlled discharges of wastewater, resulting lower water pollution. The stations of the fourth category are placed: $ in uncontaminated areas of water bodies and watercourses; $ in areas of controlled discharges of wastewater, resulting lower water pollution. Parameters, determination of which is provided by the mandatory program of observations of the quality of surface water by hydrochemical and hydrobiological indicators, are given in the appendix. In assessment of the level of soil contamination, due to the extremely high laboriousness and cost of the work, does not always need a continuous investigation of contaminated soils. Appropriateness and cost-effective way is to track their air and water pollution, by analyzing the combined soil samples collected at the so-called key areas, which are located in sectors-radius of prevailing air currents. The control of the levels of contamination of soil is based on three main parameters: $ size (area) of the elementary area from which the mixed soil sample is taken, showing the level of soil contamination; $ number of samples required for preparing of the representative sample of the mixed soil sample; $ key area is smallest geomorphological unit of landscape adequately showing the genesis and soil properties. The key area usually has a size of 1-10 m and more. The main share of key areas for monitoring of soil pollution should be located in the direction of two extreme rays (compass points) of wind rose. With unclear marked wind rose areas should characterize the territory evenly towards all points of the compass of wind rose. In the key area elementary areas whose sizes depend on the distance from the source are allocated. Within a certain elementary section selects operation (test) platform from which samples were taken for the preparation of the mixed soil sample. If the size of the elementary area is quite large and soil cover is complex, then within the area a number of test work sites are identified. The size and configuration of the sample areas are selected individually, depending on the contouring of soil cover, topography, vegetation etc. Key areas of the same biogeocenoses allow to compare different areas on the degree of human impact on the natural environment. Some key areas (experimental) are located in areas with environmental stresses (in the settlements at the industrial site, in areas of intensive exploitation of natural resources) and the others (control) – in clean, «background» areas of the natural environment. 27

When selecting the key areas, features of terrain should to be taken in consideration. In each pair of key areas (experimental and control) both regions must be as much as possible in the same conditions of the accumulation of contaminants in the soil. Each of them is put on the plan of area. Categories of each area correspond to the sign of a certain form (for example, the triangle indicates the experimental areas, squares – control areas). Inside the sign number of the key area is placed. 1.7.2 Plan (map) of monitoring objects For getting of the cartographic basis of the study area it is necessary to record the visual areas, represent field plans and make topographical drawing according to them at a scale of 1:5000-1:25000, which will be the basis for mapping of the phenomena studied. Copies of topographic maps can be used. If the study area is located in the countryside, then the plan must identify all settlements; note waterways of microregion (rivers, streams, springs); specify the lakes, ponds and swamps; put roads and other transport routes crossing territory of microregion. In urban areas quarterly grid of microregion is put in the plan. Special characters must identify the types of buildings within its limits (low-rise, high-rise, high-rise buildings, especially stone and wood), since this affects the microclimate conditions. In any case, whether urban or countryside, in a plan (map) are put: – areas of natural vegetation, and other crops; – permanent sources of environmental pollution (areal, line, point), industrial plants, landfills and industrial solid and domestic waste, highways, railway lines, the storage of fuels and lubricants etc.; – directions of migration of pollution (air – wind rose, water – by the direction of streams). In the plan also key areas for various applications, where observations carried out annually (monitoring of the natural environment) are marked. Site plan with a natural, industrial and agricultural facilities, settlements, road network and key sites, is replicated and serves as the main working document for environmental monitoring. It is recommended to make an electronic map or series of maps (electronic atlas) stored together with all data (data bank) in the computer's memory. These cards are very comfortable, as they can be stored in computer memory, at the necessary moment to show in the screen with variable zoom ratios, edit, and add in them data about occurring changes. E-cards are particularly valuable for monitoring tasks, as using them it is convenient to compare the environmental situation in the past and present. In recent years, special program – «Geographic Information Systems» (GIS), that produce computer processing, mapping, and allow to realize a dialogue with the map (ask a question and receive an answer) have been widely spread. 1.7.3 Environmental assessment of the study area, the environment and the objects of anthropogenic impact The most important factor affecting the state of the natural object is human activity. Therefore, the general characteristic of human factors, described by a set of parameters, is presented. It is necessary to take into consideration the number of 28

people per unit of area, the presence of factories (and their types), boiler, drinking water sources (and their quality), sewerage, transport network, landfill sites (including the unresolved), high voltage power lines, chimneys of thermal power plants and manufactories of factories (and characteristics of the discharge of them), water reservoirs (and their conditions). In addition, it is required air quality assessment, the definition of places of strong gas pollution, noise pollution and radioactivity. The task of monitoring is annual monitoring of the condition of the territory. Based on these results it can be estimated the value of the disturbance of ecosystems. Monitoring provides data for several years, which makes it possible to make estimates of the rate of changes in the area of disturbance zones. Such approaches have been developed in detail by a famous russian scientist B.V. Vinogradov, who proposed for indicating of the disturbance of ecosystems and natural environment of the territory two groups of features: $ features of dysfunctional state (static characteristics); $ features of adverse changes in the territories (dynamic characteristics). Research program of environmental monitoring provided assessments of ecological state of territory by static and dynamic methods. Anthropogenic factors those determine technogenic impact on natural objects, manifested through the transformation of the landscape through settlements closeness of industrial zones, the presence of logging areas, agrocenoses, mining, transport networks (roads, railways, oil and gas pipelines). Territories, where such factors are presented, are considered to some extent disadvantaged. This estimation of dysfunctional territories consists of many parameters, among them are botanical and soil, territorial static and dynamic, natural and anthropogenic. In each region, these parameters are closely related to each other, dependent from each other and can therefore be expressed by one general indicator. The methodology of the work. On the plan of the territory it should be applied boundaries of disturbed, retired from land management and lands occupied by settlements. By imposing of mosaic (mesh), to measure their area, calculate the proportion of the area in percentage of: $ zones of dysfunction of forest biocenosis from the total area of forest biocenosis; $ zones of dysfunction of meadows from the total area of grassland habitats; $ lands retired from land management, from the total area of land-use; $ lands occupied by the settlements from the total studied land area. Environmental assessment on the static characteristics. The proportion (percentage) of the total area disturbed is a generalized environmental assessment of the territory by static features. Environmental assessment is done by four classes of ecological dysfunction of lands: a) the total area of dysfunctional lands is less than 5%, it is ecological norms; b) the total area of dysfunctional lands is from 5 to 20%, it is environmental risk; c) total area of dysfunctional lands is from 20 to 50%, it is environmental crisis; 29

g) the total area of dysfunctional lands is more than 50%, it is ecological disaster. The percentage of disturbed and lands taken out of land management are included in the appropriate section of the ecological passport. Environmental assessment on dynamic characteristics. Generalized environmental assessment of the territory by static characteristics shows «environmental portrait» of a certain year. Systematic annual observations allow to track the changes of dysfunctional areas and lands taken out from land management, to evaluate the rate of increase of adverse changes. Changing of the dysfunctional area per year (in percentage) is a generalized ecological assessment of area by dynamic characteristics. This environmental assessment of lands by rate of increasing of adverse processes also can be attributed to one territory of four classes: a) rate of increasing is less than 0.5% per year, it is ecological norms; b) rate of increasing is from 0.5 to 2%, it is environmental risk; c) rate of increasing is from 2 to 4%, it is environmental crisis; g) rate of increasing is more than 4%, it is ecological disaster. The rate of increasing of dysfunctional areas in the study area per year is recorded in the ecological passport. The general conclusion of the degree of dysfunction of ecological state of the territory should be on the basis of both overall evaluations – statical and dynamical. Quantitative results of individual studies cannot be made reliable estimates of the natural environment and to identify trends in its changes. For example, a one-time sampling at different points in the region and their analysis cannot give a reliable assessment of the territory, if it is not supported by repeated studies. Only long-term observations of the same objects on used techniques allow to accumulate data that will make more reliable estimates of changes in the environment in comparison with non-systemic single studies. Therefore, the most interesting results are obtained in the case where they are used for comparison of samples taken at different locations (e.g., on the background areas and at the site exposed by anthropogenic activity) or in the same place at different times. Studies on the environmental monitoring program include biota, natural environment and sources of anthropogenic impact. It should be noted the difference of main objects of monitoring carried out in rural and urban areas. If for rural areas the main focus of research is the monitoring of biota, for the urban is monitoring of environments and objects of technogenic influence. Monitoring of biota includes assessment of biodiversity of plants and animals, the vitality of species, abundance, occurrence and changes in the amount of instances of species in their habitats; definition of phenophase of plants; terms of appearance and disappearance of butterflies, other insects, birds; phenotypic studies, such as white clover, in populated areas and in natural landscapes. At selecting of bioindicators that react to changes in environmental conditions by changing their indicators, emphasis is placed on the number of species, especially rare, adapted to living in certain limits of external influences. In addition, an important 30

indicator is the percentage of different species: in some cases it is more reliable indicator of pollution by chemicals than the change in the number of one species. Biodiagnostics of environment is performed at key sites of the area by sparing technique. a) Description of phytocenosis (frequency is once per year): – layering of vegetation; – number of plant species, in percentage; – an abundance of plant species, in scales per 5 points; – phenophase of plants; – viability of the species, in the scales per 1-3 points. b) Description of the fauna: – number of types of soil or near soil fauna (2-3 times per summer season); – number of hollow-nesting birds (1 time per summer season). Monitoring of environments and objects of technogenic influence provides assessment of the following definition of and indicators. Assessment of the level of air pollution (once per year): – by the results of lichen diagnosis; – by morphological and anatomical changes of pine needles (crowns without conifers, damage, drying of conifers, and the average increase in life expectancy of conifers, pine tree state of the generative organs); – by characterization of movement of transport; – by chemical composition of the snow cover, the acidity of atmospheric precipitation; – by dust content (the rate of deposition of dust per day). Assessment of the level of soil pollution (once per year): – estimation of soil properties by plants-indicator (fertility, moisture and soil acidity); – determination of the phenotypic structure of populations of white clover; – determination of soil properties by species of invertebrate animals – indicators of soil conditions; – microbiological activity of soils (the characterization of soil respiration, the decomposition rate of cellulose, 2-3 times per summer season); – determination of the quality of the pollen grains of various plants (tomatoes, crops, wild plants – weeds, different trees). Assessment of the level of contamination of water (1-3 times per year): – by physical, chemical properties of water, vegetation indicators, biotic index, analysis of sediments; – by the density of populations of species – bioindicators of water reservoirs with an estimations of abundance, in points. Questions for control: 1. 2. 3. 4.

What is environmental monitoring? What objects are the subjects of its observations? What is the basis of the monitoring of the environment? List the tasks of monitoring of anthropogenic changes in the biosphere. What are the types of monitoring? By what signs are they differed? 31

5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20.

List the basic principles of monitoring systems. What levels of monitoring systems are differed? What is the principle of difference? What is the purpose of the national environmental monitoring system? What tasks are designed to solve global environmental monitoring? List types of sources of pollution. What means «toxic»? Give examples of toxicants and xenobiotics. What is the maximum permissible concentration? What is the MPC in the air of exposure zone? What is the quantitative difference MPCwt and MPCwf? What MPC of main pollutants do you know? What industries are the most dangerous for the environment? What pollutants are priorities? Why? Sources of heavy metals in the environment. What areas become contaminated with heavy metals more frequently? What are the most harmful substances which may pollute the environment?

2. METHODS OF CONTROL OF NATURAL OBJECTS To obtain objective information on the state and level of contamination of various environmental objects must have reliable means and methods of control. Improving the efficiency of monitoring of the conditions of the environment can be achieved by increasing of productivity, efficiency and regularity of measurements, increasing the scale of coverage simultaneous control; automation and optimization of technical devices of controls and the process itself. Tools of environmental monitoring and control are divided into contact, noncontact (distance) and biological. 2.1 Contact Methods of Environmental Monitoring Contact methods of control of the environment are represented as classical methods of chemical analysis, as well as modern methods of instrumental analysis. Classification of contact control methods is shown in Figure 5.

CONTACT METHODS OF ANALYSIS

CHEMICAL

PHYSICAL PHYSICAL AND CHEMICAL

Gravimetric

Titrimetric

Spectral

Magnetic spectrosc opy Electrochemical

Mass spectro metry

X-ray

Chromato -graphic

Fig. 5. Structure of the contact methods of the monitoring and control of the environment

Many physical-chemical properties of solutions, such as light-absorption, angle of rotation of the plane of polarization, conductivity, and others are dependent on the concentration of the substance. Thus, by measuring of these values, we can determine the amount of substance in the sample solution. All these methods are called physical-chemical methods of analysis. Physical-chemical methods of analysis mainly have less accuracy than chemical methods, especially gravimetry. Accuracy of most physical-chemical methods is ± 5%. 3

The main methods of physical-chemical analysis are photometric, electrochemical, chromatographic methods. Electrochemical methods of analysis (Figure 6) are based on measuring of various electrical characteristics of substances (change in electroconductivity, electric potential, current value). Methods of chromatographic analysis (Figure 7) are based on the difference in adsorptivity of substances, in the constants of ion exchange, precipitation and solubility etc. Spectral methods of analysis (Figure 8) is a set of qualitative and quantitative methods of determining the composition of the object, based on the study of the spectra of the interaction of matter with radiation, including the spectrum of electromagnetic radiation, acoustic waves on the distribution of mass and energy of elementary particles and others. Depending on the purpose of analysis and types of spectra identify several methods of spectral analysis. Atomic and molecular spectral analyses allow to determine the elemental and molecular composition of matter, respectively. In the emission and absorption methods composition is determined by the emission and absorption spectra. Mass spectrometric analysis is carried out by the mass spectrum of atomic or molecular ions and allows to determine the isotopic composition of the object.

ELECTROCHEMICAL METHODS OF ANALYSIS

Methods without electrode reactions

Direct conductometric measurements

Conductometric titration

Methods based on electrode reactions

In the absence of current

Potentiometric methods

Electrochemical sensors

In the presence of

Voltammetric methods

Fig. 6. Electrochemical methods

34

Amperometric titration

Coulometric methods

CHROMATOGRAPHIC METHODS OF ANALYSIS

Mobile phase is liquid

Mobile phase is gas (vapor)

Gas chromatography

Gas Liquid Chromatography

High performance liquid chromatography

Normalphase

Thin-layer chromatography

Reversedphase

Gas chromatography mass spectroscopy

Fig. 7. Chromatographic methods of analysis of pollutants SPECTRAL METHODS OF ANALYSIS

Atomic spectroscopy

Hard radiation

Molecular spectroscopy

UV-visible spectroscopy

Photometry

Fluorescence analysis

Fluorescent methods

Chemiluminescence analysis

Radio wave spectroscopy

Electron paramagnetic resonance Fig. 8. Spectral methods of analysis of pollutants 35

Methods of structural analysis

IRspectroscopy

Nuclear magnetic resonance

2.1.1 Chemical methods of analysis Gravimetric, titrimetric (volume) and visual colorimetry are the most readily available from the quantitative chemical methods of analysis. Gravimetric method The essence of the method is the determination of the mass and the percentage of content of element, ion or chemical compound, which present in the test sample. The required fraction is isolated either in pure form or in the form of a compound of known composition. The content of a number of heavy metals, anions, dry matter in fruits and vegetables, fiber, «raw» ash in the plant material are determined gravimetri-cally. Furthermore, this method determines the crystallization water in salts, the total and hygroscopic moisture content of the soil etc. Gravimetric analysis is performed by the following steps: $ selection of average sample and its preparation for analysis; $ taking of sample; $ sample dissolution; $ choice of precipitator and precipitation of the element being determined (with the sample to be complete precipitation); $ filtering; $ washing of the precipitate (with the sample to be complete washing); $ drying and calcining of the precipitate; $ weighing; $ calculation of the results of the analysis. Analytical practice found that during gravimetric analysis the most convenient sample is from 0.5 to 2.0 g. Weighed sample of the substance should be taken out of the calculation, after calcination to obtain gravimetric form weight of about 0.1-0.3 g for amorphous precipitate and weight of about 0.5 grams for crystalline. Titration (volumetric) method This method has several advantages over the gravimetric method (speed of analysis, the relative simplicity of operations and sufficient accuracy), that is why, it is widely used in laboratory practice. In this kind of analysis is replaced by measuring the volume weighting as the analyte and reagents used in this definition. In this type of analysis weighting is replaced by measuring of volumes of analyte and reagents used in this definition. If it is necessary to analyze dry matter by volume method, then it is accurately weighed (0.1÷0.2 g), dissolved in flask, stirred, a known volume of the resulting solution it taken by pipette, if it is necessary, the buffer mixture, indicator etc. are added and the titration is carried out. Methods of the titrimetric analysis are divided into 4 groups. Methods of acid-base titration. The basis of these methods is the neutralization reactions. The equivalence point is fixed by using of indicators which change their color depending on the medium of reaction (pH value). These methods determine the concentrations of acids, alkalis and salts hydrolyzed in aqueous solutions. As working solutions titrated solution of acids and strong bases are used. Methods of precipitation. By precipitation titration method elements, which interacting with a titrated solution may be deposited in the form of sparingly soluble 36

compounds, are determined; wherein the properties of the medium change, that allows to establish equivalence point. Methods of oxidation-reduction. These methods are based on redox reactions, which occur between the analyzing substance and the substance of the working solution (permanganatometry, iodometry, chromatometry etc.). They are used for the detection of various reducing (Fe2+, C2O2-4, NO2- etc.) or oxidizing agents (Cr2O72-, MnO-4, ClO3-, Fe3+ etc.). The equivalence point is determined by the change of color of solution or redox indicator. Methods of complexation. These methods provide the ability to define a variety of cations (*g2+, &2+, Zn2+, Hg2+, A13+ etc.) and anions (CN-, F-, &1-), which have the ability to form hardly dissociated complex ions. Special interest is Trilon B, which is widely used in the quantitative analysis. Equivalence point is most often established by the disappearance of the analyzed cation in the solution using of socalled metal-indicators. As an indicator to determine the total content of calcium and magnesium, Eriochrome Black T and chrome dark blue can be taken, to determine calcium – murexide, iron – ammonium thiocyanate in the sulfanilic acid etc. 2.1.2 Methods of molecular spectroscopy In absorption spectroscopy the absorption of electromagnetic radiation in the UV, visible (traditionally called spectrophotometry) and infrared spectrum (IRspectroscopy) are used. Photometric methods of analysis Methods of photometric analysis based on the absorption in the visible spectral range, i.e. in the wavelength range of 400÷760 nm, are most widely used. The photon energy spectrum in those areas is sufficient for transitions of the electrons in a molecule from one energy level to another. The main contribution to the change of energy of the molecule contributes electronic transition, but purely electronic transition of the molecule is not feasible, it is accompanied by changes in the vibrational and rotational energies. Therefore, the molecular absorption spectrum consists of a plurality of spectral lines. Photometric methods of analysis are based on measurement of the absorption transmission and scattering of light by the analyte. Some colorless or weakly colored ions can interact with other ions or organic compounds to give colored compounds. Such reactions are called color reaction. For example, Fe3+ ions are weakly colored, but in reaction with thiocyanate SCN- ions, they form dark red complex ions. Blue copper ions with ammonia molecules form bright blue copper-ammonia complex ions. Colorless manganese ions *n2+ can be oxidized to bright crimson *n@4- ions. It is clear that the amount of received colored ions (or molecules), is equivalent to the amount of determined ions. Therefore, the colored reaction formed the basis of the photometric determinations. Color reactions used in photometry, should satisfy the following conditions: 1. The reaction of obtaining of the colored solution should occur with high speed. 2. The obtained colored compound should have enough intense color; as it is intensive, method of analysis is more sensitive. 37

3. Colouring should be stable in time and insensitive to light. Color intensity should not vary with changes in temperature and pH. If pH of solution has a significant influence on the intensity of color, carrying out of color reaction should occur at strictly defined pH. 4. The color intensity should be directly proportional to the concentration of the colored compound. The solution of the colored compound must obey the LambertBeer law. To reduce the deviation from the Lambert-Beer law, it is necessary to operate in optimum conditions, choosing optimal reagent, and a method of preparing of colored subject and standard solutions. In the preparation of colored solutions must adhere to the following rules: 1. To the standard and test solutions the same reagents in the same sequence and in the same quantities should be added. 2. Colored solution of the standard and the test should be prepared simultaneously, as it is often that the color intensity changes in time. 3. Colored solutions of the standard and the test should be prepared in equal volume in order to the intensity of the color was independent of dilution. Therefore colored solutions are prepared in a volumetric flasks or graduated tubes. 4. Coloring of the test and standard solutions are compared in similar vessels at the same lighting. To prepare the colored solution of known concentration so-called standard solutions are used. The standard solution contains a precisely known amount of analyte. Typically, the concentration of the standard solution is expressed in milligrams of substance per milliliter of solution (mg/ml). Weight of substance necessary for such solutions is calculated by the formula: m

M 1QV , M 21000

where: M1 is molar mass of dissolved substance, g/mol; M2 is molar mass of analyte, g/mol; Q is mass of the analyte, which corresponds to 1 liter of standard solution, g; V is given volume, ml. Example. It should be prepared a standard solution for the photometric determination of ammonia. Solutions should be prepared from ammonium chloride NH4Cl with an ammonia content of 1 mg/ml. Calculate the weight of salt to make 1 liter of solution: m

M NH 4 Cl QV M NH 3 1000

53,49 ˜ 1 ˜ 1000 17,032 ˜ 1000

3,1409 g

If difficultly soluble compound forms in the reaction, it remains in suspension in small quantities. Turbidity degree of the solution will be directly proportional to the 38

amount of analyte. Therefore, in photometric methods not only the color reactions but reactions with the formation of difficultly soluble substances are used. A measure of light absorption are values called transmission and optical density. Transmission: I I T 100% , or T I0 I0 where: I is intensity of the transmitted light; I0 is the intensity of the incident light. Optical density:

A

lg

1 T

lg

I0 . I

If the sample solution does not absorb the light, the transmittance is 100% and the optical density is zero. If the light transmittance is zero, the optical density is infinity. The main parameters to be considered when selecting the optimal conditions photometric determinations are the wavelength, optical density, the thickness of the light absorbing layer and the concentration of the colored substance. Conditions and sequence of photometric determination of substance are the following: 1. Selection of photometric form of substance, i.e. a compound, which is converted into a substance to measure optical density, based on the molar absorption coefficient at a given wavelength and the presence of other components in the test object. 2. Measurement of absorption spectrum and choice of optimal wavelength, usually it is the maximum of absorption. However, if the impurity is absorbed at this wavelength, it is better to choose a different range of the spectrum. 3. Investigation of the influence of external substances on optical density. 4. Establishment of a range of concentrations with conformity of the Beer– Lambert–Bouguer law. For this purpose, standard solutions of different concentrations of the analyte are used, the photometric reaction is carried out and simultaneously the blank solution (containing no analyte) is prepared. The cell is selected so that the optical density of the solution with the lowest concentration is not less than 0.05÷0.1 and the highest is not more than 0.8÷1.0, and the thickness of absorbing layer is less than 5 cm. 5. The optical density of all solutions is measured and calibration graph is built in the axes «optical density – concentration» (standard solutions). By measuring of the optical density of the sample solution, its concentration is found from the graph. 6. Carrying out of calculations to determine the concentration of substances in solution. There are several methods of photoelectric measurements, among them are the calibration curve method; the method of the molar absorption coefficient; addition 39

method; method of differential photometry; the spectrophotometric titration method. Most commonly used is the calibration curve method. 7. Checking of the result of analysis, the assessment of its reproducibility and issue of the final result with the metrological evaluation. There are different photometric methods: spectrophotometry, photoelectroncolorimeter, nephelometry, fluorometry. Photoelectrocolorimeter is determination of matter by the absorption of light by colored solution passed through the filter and measured by photocell. Photoelectrocolorimetric method is more objective than the visual colorimetry and gives more accurate results. For determination photoelectrocolorimeter (FEC) of different brands are used. Principle of the FEC is following. The light flux passing through the colored liquid is partially absorbed. The remaining part of the light falls on the solar cell, in which an electric current, is recorded by the ammeter. The greater is the concentration of the solution, the greater is its optical density and the greater is the level of light absorption, and consequently, the less force is photocurrent. Nephelometry is a visual definition of the content of substance by turbidity of the solution. Nephelometric determination can be carried out instrumentally. In this case concentration is determined by the intensity of the light scattered by suspended particles of suspension and measured by photocell. 2.1.3 Methods of Atomic Spectroscopy Atomic Emission Spectrometry. The principle of the method is the following: the atom got energy usually by collisions with high-temperature atoms and molecules in the source, where the atomization and excitation, which is reduced to electronic transitions within the atom with lower levels to higher. The resulting excited atom can lose purchased energy in the radiation process and return to the original state. Besides this transition, there are other possible transitions from a higher energy level to a lower, which results in a series of emission lines of a single element. For isolation or separation of atomic lines and measuring their intensities spectrographs and spectrometers (optical devices of the same type, differing only in the methods of registration and measurement of the radiation source) are used. Devices consist of a dispersing device (monochromator), designed for the separation of different emission line by wavelength, and the radiation detector of any type. Quantitative determination of the content of the element is carried out by the calibration curve, showing the dependence of the measured intensity of lines of elements (standards) on the concentrations of elements that emit these lines. Atomic absorption spectrometry is an analytical method for the determination of elements, based on the absorption of radiation, which is the characteristic radiation of free (unexcited) atoms. During determination the part of the analyzed sample is transferred to the atomic vapor (aerosol) and it is measured the absorbance of this steam emission characteristic for the element being determined. An atomic vapor is obtained by spraying a solution of an analyte in a flame. Unexcited atoms of elements, found in the plasma in a free state, absorb characteristic resonance radiation certain wavelength for each element. Consequently, the optical electron of the atom moves to 40

a higher energy level and simultaneously passed through the plasma radiation weakens. Usage of resonance radiation makes this process highly selective. The method has a sufficient sensitivity (detection limit reaches 10-3 g/cm3). The error of this method does not exceed 1-4%. Installations for the atomic absorption spectrometry always contain a discharge tube (i.e., hollow cathode lamps made of the element being determined), a burneratomizer, a monochromator, a photomultiplier, an amplifier of alternating current and output meter. The schematic scheme of installation of atomic absorption analysis is shown in Figure 9. The light from the discharge tube 1, emitting line spectrum of the element being determined, is passed through the flame of the burner 2, in which a thin aerosol of analyte is injected. Spectral range, corresponding to the position of the measured resonance line, is isolated by monochromator 3. Then emission of leased line comes to a photomultiplier or photocell 4. The output current is amplified in unit 5 and is registered in measuring device 6. 3

1 2 7 6 5

4

Fig. 9. Installation for atomic absorption analysis 1 - discharge tube (a source of resonance radiation); 2 - burner-atomizer; 3 - monochromator; 4 – photocell (photomultiplier); 5 - amplifier; 6 - meter; 7 - modulator

The intensity of the resonance radiation is measured twice: before spraying a test sample in the flame and in the time of spraying. The difference between these counts is a measure of absorption, and hence a measure of the concentration of the element. 2.2 Distance methods of environmental control Contact methods of observation and monitoring of the natural environment are complemented by non-contact (distance) based on the usage of two properties of probing fields (electromagnetic, acoustic, gravity) to interact with the controlled object and transfer the information to the sensor. Probing fields have a wide range of 41

informative features and a variety of effects of interaction with the substance of the object of control. The principles of functioning of the non-contact control are conventionally divided into passive and active. In the first case it is registering of probing field coming from the object of control, in the second it is realized the registration of reflected, past or reemitted probing fields generated by the source. Non-contact methods of monitoring and control are presented by two main groups of methods: aerospace and geophysical. The main types of aerospace research methods are optical photography, television, infrared, radio thermal, radiolocation, radar and multispectral photography. Initially, the radio waves were used to analyze the state of the ionosphere (using reflected and refracted waves), latter centimeter waves started to be used in studying of rainfalls, clouds, atmospheric turbulence. Area of usage of radio acoustic methods is limited by relatively local amounts of air pollution (about 1-2 km in radius) and allows their functioning on the ground and on board aircraft. One of the reasons of the appearance of the reflected acoustic signal are small scale temperature inhomogeneities, which allows to control the temperature changes, the profiles of wind speed, the upper limit of the fog. The principle of lidar (laser) probing is that the laser beam is scattered by molecules, particles, inhomogeneities of air; absorbed, modifies its own frequency, pulse shape, whereby the fluorescence occurs, which allows qualitatively or quantitatively judge the air environment parameters such as pressure, density, temperature, humidity, concentration of gases, aerosols, wind parameters. The advantage of lidar sensing is monochromaticity, coherence and the possibility to modify the spectrum, which allows selective control of individual parameters of air environment. The main disadvantage is the limited height of sensing of the atmosphere from the Earth because of influence of clouds. The main methods of non-contact control of natural waters are radiobrightness, radar, fluorescent. Radiobrightness method uses a range of probing waves from visible to meter for the simultaneous control of agitation, temperature, and salinity. Radar (active) method is to receive and process (amplitude, power, frequency, phase, polarization, spatial and temporal) of the signal reflected from a excited surface. For distance control of parameters of oil pollution of the water environment (surface coverage, thickness, the approximate chemical composition) laser reflective, laser fluorescence methods and photographing in polarized light are used. Fluorescent method is based on absorption of optical waves by oil and on the difference of emission spectra of light and heavy oil fractions. The optimal choice of the length of the exciting wave allows to identify the types of petroleum products according to the amplitude and shape of the fluorescence spectra. Geophysical research methods are used to study the composition, structure and condition of rocks, within which can develop different hazardous geological processes. Among them are magnetic prospecting, electromagnetics, thermal intelligence, visual surveys (photo, television), nuclear geophysics, seismic and geoacoustic and other methods. The main type of direct study of dangerous geological processes and phenomena is a complex engineering-geological survey 42

(EGS). Methodology of complex EGS is enough well developed. Methods of preparation of engineering geological information during shooting are well designed and include a complex of preliminary, field and laboratory studies. During GCI a field study is based on the traditional routes of geological, topographic and geodetic and landscape-indicator research, mining and drilling exploration work, field testing of rocks, dynamic and static sounding etc. In this complex of works includes special aerospace, geophysical, mathematical, surveying, hydrological observations. Images from satellites are transmitted to Earth in real time in a range of 1700 MHz. The possibility of free receiving of satellite information by ground stations is provided by the World Meteorological Organization, according to the concept of «Open Sky». At the ground station of receiving of satellite information is performed receiving, demodulation, primary processing and preparation of satellite data for input into a personal computer of station. Satellite data of distance sensing allows to solve the following problems of control of the environment: $ determination of meteorological characteristics: vertical profiles of temperature, integral characteristics of humidity, the nature of cloud cover; $ control of the dynamics of atmospheric fronts, hurricanes, obtaining of maps of major disasters; $ determination of the temperature of the underlying surface, operational control and classification of the pollution of soil and the water surface; $ detection of major or permanent industrial emissions; $ control of technogenic impact on the conditions of forest park zones; $ detection of large fires and isolation of fire-risk zones in the forests; $ detection of thermal anomalies and the thermal emission of large manufactures and thermoelectric plant in metropolitan areas; $ registration of smoke plumes from pipes; $ monitoring and prognosis of seasonal floods and river overflows; $ detection and assessment of the level of zones of major floods; $ control of the dynamics of snow cover and snow cover pollution in the areas of influence of the industrial enterprises. 2.3 Biological methods of environmental control It is evident that the evaluation of the environmental situation in the territory during the formation of an effective monitoring system is impossible without the usage of methods of biodiagnostics of environmental quality. To assess the quality of the environment, the level of favorability for mankind is necessary first of all, in order to: $ determine the state of natural resources; $ development of strategies of management in the region; $ determination of the maximum permissible capacity for each region; $ decision of future development of areas of intensive industrial and agricultural usage, contaminated areas etc.; $ decision on the construction, start-up or stop of certain company; 43

$

evaluating of the effectiveness of environmental protection measures, the introduction of treatment facilities, modernization of production etc.; $ introduction of new chemicals and equipment; $ creation of recreational and conservation areas. None of these questions cannot be objectively resolved only at the level of consideration of formal parameters, and requires a special multifaceted evaluation of habitat quality, i.e. requires an integral characteristic of its condition, biological assessment. Direct (integral) methods of evaluation of ecological conditions, in turn, can also be divided into two groups – bioindication and bioassay (the last one is also called toxicological methods). The object of study of bioindication are organisms or communities of organisms-bioindicators observed in their natural habitat. Bioindicators are plant and animal organisms, the presence, quantity and condition of which serve as indicators of changes in the quality of their environment. The level of bioindication can vary from simple visual diagnostics of plants to study of immune and genetic changes in the body of indicators. The second group of methods is studying of reaction of test objects - the organism placed in the test medium. They involve an assessment of the toxic properties of pollutants using the model of living systems (test objects). Assessment of toxicity is usually performed in laboratory conditions. Methods of bioindication are based on observations of individual organisms, populations or communities of organisms in their natural habitat in order to determine the quality of the environment by their reactions (changes). In agriculture, methods of bioindication for the diagnosis of feeding of crops are widely used. This method of visual bioindication is based on studying of external features of phyto- and biocoenoses which reflect the quality of habitat change. As features of the visual bioindication, outward of plants is used. There are a lot of such features associated with malnutrition of plants, among them are slowing growth of stems, branches and roots; yellowing; browning; bending of leaves; «edge burns»; formation of rot; lignification of stems etc. For the purposes of bioindication of environmental quality, population and ecosystem criteria, which are characterized by parameters of the number and biomass of individual species; ratio in communities of different species, their distribution and abundance etc., can be used. To get more reliable, long-term prognosis, along with the species-indicators, changes, occurring in populations of resistant species that can withstand significant perturbing effects (effects of environmentally adverse factors) for a long time, are tracked. More precise methods of biodiagnostics are immunological and genetic methods. Immunological methods are based on measurements of immune system under influence of external disturbing factors. As a result of any kind of adverse effects on the immune system of living organisms, primarily changes the functional state of immune cells, i.e. splenocytes and lymphocytes. When adding of special substances – 44

standard mutagens (lipopolysaccharides et al.) into body cells, depending on the kind of effects the inhibition of the reaction may be indicative of inappropriate immunological status of the organism. Genetic methods allow to analyze genetic changes, arising from adverse external influences. The appearance of these changes characterize mutagenic activity of environment, and may be saved in cell populations reflects the effectiveness of the immune potency of the organism. The distinctive simplicity of methods for assessing of the ecological situation of bioindication methods, no need of special tool maintenance are their indisputable advantages. Bioassay as a method of integral evaluation of toxic pollution have long been used in the monitoring of environmental quality abroad and become applicable in our country. Arguments in favor of the usefulness of bioassay approaches of the quality of the environment are their versatility, speed, and simplicity, availability and cheapness. The high sensitivity of the test-organisms to the action of pollutants even has led some experts to the idea of the possibility of a complete replacement of all hygienic standards to only criterion qualitative assessment of the environment on the basis of bioassay. It identified necessity of studying the effectiveness of bioassay. In particular, to identify volley discharges of pollutants into water bodies and especially to detect abrupt changes in the quality of drinking water, bioassay is important as a signal indicator of the express control, allowing in one hour to get data of the integral assessment of the toxicity of the water and make the necessary measures to protect the population, while the organoleptic properties of water may remain unchanged, and it is require several hours or even days for identification of substances, received in water, by chemical methods. Currently special attention is paid to toxicological bioassay techniques, i.e. usage of biological objects in controlled conditions as a means of identifying of the total water toxicity. In the «Rules of the protection of surface waters» biological testing is required by the analysis of the quality of natural and waste waters. Any combination of traditional analytical instruments is not able to provide a specific biological effect identified in the controlling of toxicity as integral indicator. Questions for control: 1. 2. 3. 4. 5. 6.

Similarity and difference of methods of bioindication and bioassay. Give examples. What is the difference between spectrophotometric method and photometric analysis? The structure of the of physical-chemical methods of analysis used in the analysis of natural objects. The structure of the contact methods of observation used in environmental monitoring. Method of bioindication, the area of its application. Give examples. Chemical and analytical methods for the determination of contaminants in the environment.

45

3. MONITORING OF ATMOSPHERE The role of atmosphere in natural processes is enormous. Presence around the globe of atmosphere determines the overall thermal regime of surface of our planet, protecting it from harmful cosmic and ultraviolet radiation. The circulation of the atmosphere effects on the local climatic conditions, and through them - on the regime of rivers, land cover and on the processes of relief formation. Clean air is essential for life of human, plants and animals. Atmospheric pollution has a negative impact on living organisms, leading to a reduction in the population, species diversity of plants and animals, diseases of human... The main components of air are divided into three groups: fixed, variable and random. The first group includes oxygen (21% by volume), nitrogen (about 78%) and noble gases (about 1%). The second group includes carbon dioxide (0.02-0.04%) and water vapor. The third group includes random components that change the natural composition of the atmosphere, get into the air from various sources (mainly anthropogenic origin) and are classified as pollutants. Thus, near the metallurgical plants air often contains sulfur dioxide, technological impurities of heavy metals; in places where there is the decomposition of organic residues - ammonia and other gaseous and liquid substances. Air quality assessment can be done using both climate and pollution monitoring. The main parameters of meteorological research include air temperature (maximum, minimum, daily, daily average); wind characteristics (speed and direction); air humidity; atmospheric phenomena (types of clouds, liquid and solid fallout); condition of the underlying surface in a radius of 100 m from the observation point (grass is green or yellowing; soil is dry and dusty, dry and non-dusty, moist, wet, snow etc.). Usually climate monitoring is carried out at the meteorological site. Some parameters are determined visually, and for some of them special instruments are required, among them are thermometers, anemometers to determine wind speed, a psychrometer to determine air humidity. 3.1 Assessment of atmospheric air pollution Man pollutes the atmosphere for thousands of years, however, the consequences of the use of fire, which he used all this period, were insignificant. This initial air pollution was not a problem because at that time people lived in small groups, taking immeasurably vast untouched natural environment. And even large concentration of people in a relatively small area, as it was in the classical antiquity, was not accompanied by serious consequences. It was so until the early nineteenth century. Only last hundred years of development of the industry have led to such consequences, which at first people could not even imagine. Basically there are three main sources of air pollution: industrial, domestic boilers, transport. The proportion of each of these sources in the total air pollution varies greatly depending on location. Now it is generally accepted that the most heavily pollute the 46

air of industrial production. Sources of pollution are power plants, which together with the smoke emit in the air sulfur and carbon dioxides; steel plants, particularly non-ferrous metals, which emit in the air nitrogen oxides, hydrogen sulfide, chlorine, fluorine, ammonia, phosphorus compounds, particles and compounds of mercury and arsenic; chemical and cement plants. Harmful gases released into the air from burning of fuel for industry, domestic heating, transport work, burning and recycling of household and industrial waste. Depending on the source and mechanism of the formation distinguish primary and secondary air pollutants. Primary are chemical substances entering directly into the atmosphere from stationary or mobile sources. Secondary are formed by reacting of the primary pollutants with each other and with the substances present in the air (oxygen, ozone, ammonia, water) under the influence of ultraviolet radiation. Frequently secondary pollutants are much more toxic than the primary air pollutants. Thus, air entering sulfur dioxide is oxidized to sulfur trioxide, which reacts with water vapor to form sulfuric acid droplets. When sulfur trioxide reacts with the ammonia, crystals of ammonium sulfate are formed. Similarly, as a result of chemical, photochemical, physical-chemical reactions between pollutants and atmospheric components other secondary features are formed. Taking into account toxicity and potential dangers of pollutants, their prevalence and emission sources, they were conditionally divided into several groups: 1. Main (criterial) atmospheric pollutants (CO, SO2, nitrogen oxides, hydrocarbons, solid particles). 2. Polycyclic aromatic hydrocarbons (PAHs). 3. The trace elements (mainly metals). 4. Permanent gases (CO2, fluorochloromethane etc.). 5. Pesticides. 6. Abrasive solid particles (quartz, asbestos etc.). 7. Variety contaminants, which have multifaceted effect on the body (nitrosamines, ozone, sulfates, nitrates, ketones, aldehydes and others.). Carbon monoxide is obtained by incomplete combustion of carbonaceous materials. In the air it enters from the burning of solid waste, with the exhaust gases and industrial emissions. Annually, this gas enters the atmosphere at least 1,250 million tons. Carbon monoxide is a compound, actively reacting with components of the atmosphere, and contributes to raising the temperature of the planet and the greenhouse effect. Sulfur dioxide is released during the combustion of sulfur containing fuel or processing of sulphurous ores (up to 170 million tonnes per year). Part of the sulfur compounds are released during the combustion of organic residues in the mining dumps. Sulfur trioxide is formed by the oxidation of sulfur dioxide. The final reaction product is an aerosol or solution of sulfuric acid in rainwater, which acidifies the soil, exacerbates respiratory diseases of human. Fall of sulfuric acid aerosol from plumes of chemical plants is observed at low cloud cover and high humidity. The leaf blades of plants growing at the distance of less than 11 km from such companies are usually thickly dotted with small necrotic spots formed in areas of settling of drops of 47

sulfuric acid. Pyrometallurgical companies of non-ferrous and ferrous metals, as well as TPP annually emit tens of millions of tons of sulfur trioxide. Hydrogen sulfide and carbon disulfide enter the atmosphere, separately or together with other sulfur compounds. The main sources of emissions are the enterprise for manufacturing of artificial fiber, sugar, coke, oil, and oil fields. In an atmosphere, interacting with other contaminants, they are exposed slow oxidation to sulfur trioxide. Nitrogen oxides are formed mainly at high-temperature fixation of nitrogen and oxygen in power plants and internal combustion engines at electric discharges in the atmosphere. The main sources of emissions are the companies that produce nitrogen fertilizers, nitric acid and nitrates, aniline colorants, nitrocompounds, viscose silk, celluloid. The amount of nitrogen oxides released into the atmosphere is 20 million tons per year. Fluorine compounds. Pollution sources are the production of aluminum, enamel, glass, ceramic, steel, phosphate fertilizers. Fluorinated substances enter the atmosphere in the form of gaseous compounds, i.e. hydrogen fluoride or dust of sodium and calcium fluorides. Compounds are characterized by the toxic effect. Fluorine derivatives are strong insecticides. Chlorine compounds are released into the atmosphere from chemical companies producing hydrochloric acid, chlorinated pesticides, organic colorants, hydrolyzed alcohol, bleach, soda. In the atmosphere molecule of chlorine and hydrochloric acid vapor occur as an impurity. Toxicity of chlorine is determined by the type of compounds and their concentration. In the metallurgical industry for iron smelting and its refining to steel, various heavy metals and toxic gases are released into the atmosphere. Thus, based on 1 ton of cast iron, 12.7 kg of sulfur dioxide and 14.5 kg of dust particles, determining the amount of compounds of arsenic, phosphorus, antimony, lead, mercury vapor and rare metals, resin substances, and hydrogen cyanide release. Aerosol pollution of the atmosphere. Aerosols are solid or liquid particles in suspension in the air. The solid components of aerosols in some cases especially dangerous for organisms and humans cause specific diseases. In the atmosphere aerosol pollution accepted as smoke, fog, mist or haze. Much of the aerosols are formed in the atmosphere by reacting of solid and liquid particles among themselves or with steam. The average size of the aerosol particles is 1-5 microns. In the Earth's atmosphere annually receives about 1 km3 of dust particles of artificial origin. A large number of dust particles are also formed during the production activities of people. The main sources of artificial aerosol air pollution are TPP, which consume high ash coal, enrichment plants, steel, cement, magnesite and soot plants. Aerosol particles from these sources have very diverse chemical composition. Most often the compounds of silicon, calcium and carbon are found in their composition, less are found metal oxides, among them are iron, magnesium, manganese, zinc, copper, nickel, lead, antimony, bismuth, selenium, arsenic, beryllium, cadmium, chromium, cobalt, molybdenum, and asbestos. More variety is characteristic for organic dust consisting aliphatic and aromatic hydrocarbons, salts of acids. It is formed by the combustion of residual oils in the pyrolysis process of petroleum, petrochemical 48

plants and other similar facilities. Constant sources of aerosol pollution are industrial waste dumps, i.e. artificial mound of redeposited material, preferably overburden formed during mining or waste of processing enterprises, TPP. The source of dust and poisonous gases is massive blasting. Thus, as a result of one, medium by mass, explosion (250-300 tons of explosives) in the atmosphere about 2 thousand m3 of nominal carbon monoxide and more than 150 tons of dusts are released. Production of cement and other building materials is also a source of air pollution by dust. Main technological processes of production are grinding and chemical treatment of charge, semifinished products and the products obtained in the flow of hot gases, which are always accompanied by the emission of dust and other harmful substances into the atmosphere. Atmospheric pollutants include saturated and unsaturated hydrocarbons, comprising from 1 to 13 carbon atoms. They undergo various transformations, such as oxidation, polymerization, interacting with other atmospheric pollutants after excitation by solar radiation. As a result of these reactions peroxides, free radicals, hydrocarbon compounds with oxides of nitrogen and sulfur, frequently in the form of aerosol particles are formed. At certain weather conditions particularly large concentrations of harmful gases and aerosol can form in the surface air layer. This usually occurs in those cases when air layer immediately above the source of gas and dust emissions inversion exists, i.e. disposing a layer of cold air over the warm, which prevents air masses and prevents upward migration of impurities. As a result, harmful emissions concentrate at the inversion layer, their content near earth surface increase dramatically, which becomes one of the causes of the previously unknown in nature photochemical fog. Photochemical fog (smog). Photochemical fog is a multicomponent mixture of gases and aerosol particles of primary and secondary origin. The composition of the main components of smog includes ozone, oxides of nitrogen and sulfur, and numerous organic compounds of peroxide nature collectively called photo-oxidants. Photochemical smog occurs as a result of photochemical reactions under certain conditions: the presence of high concentration of nitrogen oxides, hydrocarbons and other pollutants in the atmosphere, intense solar radiation and no wind or very low air exchange in the surface layer at a powerful and long (at least one day) increased inversion. Stable windless weather, usually accompanied by inversions, required to create a high concentration of the reactants. Such conditions are usually from June till September and less often in winter. For continuous fine weather solar radiation causes the splitting of molecules of nitrogen dioxide to form nitric oxide and atomic oxygen. The atomic oxygen and molecular oxygen produce ozone. It would seem that ozone oxidizing nitric oxide, should again be converted into molecular oxygen and nitrogen oxide - into nitrogen dioxide. But it does not happen. Nitrogen oxide reacts with olefins of exhaust gases which then split by a double bond to form fragments of molecules and an excess of ozone. As a result of the continued dissociation, new masses of nitrogen dioxide split and give an additional amount of ozone. Cycling reaction appears, as a result of which in the atmosphere ozone is gradually accumulated. This process stops during the night. In turn, ozone reacts with olefins. In the atmosphere various peroxides concentrate, which together form characteristic 49

oxidants for photochemical fog. They are the source of so-called free radicals with strong reactivity. By their physiological effects on the human body, they are extremely dangerous for the respiratory and circulatory systems, and are often the cause of premature death of urban residents with poor health. Contained in the atmosphere solid particles are dust, sand, ash, soot, volcanic dust and organic (macromolecular compounds) and inorganic aerosols. Frequently toxicity of solids is due to adsorption on their surface of hazardous compounds such as PAHs or nitrosamines. Polycyclic aromatic hydrocarbons (PAHs) may be both primary and secondary atmospheric pollutants, and generally they are adsorbed on solid particles. Many of PAHs differ by marked carcinogenic, mutagenic and teratogenic effect and represent a serious threat to humans. The main sources of emissions of PAHs are CHP plants operating on oil or coal, as well as an enterprise of the petrochemical industry and transport. Trace amounts of chemical elements are represented in the atmosphere such highly toxic pollutants as arsenic, beryllium, cadmium, magnesium and chromium. They are generally present in air in the form of inorganic salts adsorbed on solid particles. About 60 metals are identified in the products of coal combustion. In the flue gas of CHP heavy metals are found. Accumulating in the atmosphere, pollutants react with each other, hydrolyze and oxidize under the influence of moisture and atmospheric oxygen as well as change their composition under the influence of radiation. Consequently, the duration of residence of toxic impurities in the atmosphere is closely related to their chemical properties. Large duration of residence in the air of inactive compounds of following group of toxicity, i.e. permanent gases (freons and carbon dioxide). Among pesticides, which usually are sprayed from airplanes, especially toxic are organophosphorus pesticides, in presence of which in atmosphere the products formed are more toxic than the parent compound. Laboratory work #1. Determination of dust content of air Dust content of air is the most important environmental factor that accompanies us everywhere. Dust is any solid particle suspended in the air. Harmless dust doesn’t exist. Environmental hazard of dusts for human is determined by nature and the concentration in the air. Dust can be divided into two large groups. 1. The fine dust, which consists of light and moving particle size of up to several tens or hundreds of microns (1 micron is equal to 10-3 mm). This dust can stay in the air for a long time – «soar». It enters with the air into the lungs during breathing, may accumulate in the body. 2. The coarsely dust, consisting of heavy and slow-moving particles. Such dust quickly fall out of the air with no wind, forming dust deposits (e.g., on cabinet). Dust deposits are sources of secondary air pollution. In one cm3 of indoor air it can be up to 106 grains of different size, nature and severity. Dust can contain organic matter (particles of biogenic origin – plant, animal and human) and inorganic matter (particles of soil, building materials, detergents, 50

various chemicals etc.). Dust particles can content harmful microorganisms adsorbed even finer particles of harmful substances (e.g., heavy metals, organic compounds). The most toxic is dust, containing complex protein molecules and elementary organisms (live and dead), for example, the dust of protein-vitamin concentrate, dust of chitinous cover of dead household insects, such as flies, cockroaches, ants etc. Such dust cause allergic diseases by inhalation and by contact with skin. Certain types of dust can create an explosive mixture with the air (wood, cotton, flour etc.). It is important to be able to assess air quality on the content of dust in it, knowing its diversity and submitting an environmental hazard. Study of dust content of air pollution by contamination of leaves is important because green plantings in urban areas play an important role of air purifier, precipitating on the surface up to 60% of the dust. Progress of work: Method #1. Per 5 trees of the same species are selected near the road and far away from it (for control). Per 10 leaves are teared at a height of 1-1.5 m from each tree at the road site and they are put into a clean glass bank with cover. In other bank in the same way leaves from control trees growing away from the road are sampled. Sampling points are marked in the map of microdistrict. Leaves in banks are poured with distilled water, then thoroughly wash the dust from the surface of each leaf. Water is filtered and the precipitate is weighed after drying. This result gives a mass of dust on the washed surface. To determine the surface of washed leaves, 5 leafs are taken (different size is better), wiped them from the water and encircle each of them on paper. Then it is necessary to cut along the contour and weigh the projection of leaves. From the same paper square 10x10 cm is cut and weighed. Calculate surface of washed leaves by the following formula: S

M1 N1 (dm2), 5M 2

where: M 1 is mass of paper, cut along the contour of 5 leaves; 2 M 2 is mass of 1 dm of paper; N1 is number of washed leaves. Thereafter, it is possible to determine how much of dust is deposited on 1 m3 of surface of leaves, and knowing the exact time of accumulation of dust (from the last heavy rain before the research), it is possible to calculate the average rate of deposition of dust per day (g/m2·day):

v

m100 , St 51

where: m is mass of dust, g; S is the surface of washed leaves, dm2; t is the time of deposition of dust, days. Having carried out similar studies in different parts of the district, it is possible to create a map of dust content of air in the area. Method #2. Sample the leaves from the trees in different parts of the study area (near the road, close to houses, in the green zone) and, if possible, at different heights, specifying the location and height of the leaves. Attach to the surface of the leaves sticky tape (scotch tape). Remove the film from the leaves with a layer of dust and glue it onto a sheet of white paper, signing the location of the plants and height of the leaves. Evaluate the level of dust content by the scale: The level of dust content

Point 5 4 3 2 1

Very high High Medium Low Minor

According to the results of observations complete the table: The level of dust of air of the investigated territory Place

The height from the surface of the soil

The level of dust of air

Close to road Living area

Laboratory work #2. Measurement of the deposition of pollutants from the air One of the reasons that air pollution causes common concern is a toxic dust and particles that enter the body by inhalation and can cause various diseases. Particles in air are usually divided into two categories: fine and coarse. Fine aerosol particles are composed of substances such as compounds of carbon, lead, sulfur and nitrogen, entering into the atmosphere as a result of human activity. Coarse particles consist of natural substances which are formed due to natural erosion and during various operations for crushing of stone. The most common of coarse particles include gypsum, limestone, marble, calcium carbonate (chalk), silicon and silicon carbide (carbide used for welding). Primary fine impurities (soot, fly ash, metal particles and vapor) are released into the atmosphere as a result of physical or chemical processes. Secondary fine impurities formed due to the reactions between different gases in the atmosphere. Secondary impurities are performed from sixty to eighty percent of all fine particles detected in the cities. The human nose is natural filter from large dust particles, but does not prevent fine particles, so such materials as sulfuric acid, arsenic, beryllium, or nickel, can get 52

into the lungs. Some substances (benzo[a]pyrene, benzanthracene-supertoxicants, metal compounds) that enter the body by inhalation, are carcinogenic. Specialists consider that these substances sharpen respiratory diseases, i.e. asthma, chronic bronchitis, pulmonary emphysema, and cause irregular breathing and eye irritation. Furthermore, in the air in relatively small amounts of mineral glass fiber asbestos are presented. Asbestos causes cancer of the lungs and pleura. Nickel, arsenic, chromium, and talc associated with the formation of cancerous tumors. Progress of work: 1. Take two wide mouth vessels with volume of 100-200 ml, and wash them carefully. 2. Pour into vessels the mixture of distilled water and alcohol (50:50) upto a height of 1.5-2.5 cm. 3. Put one vessel near the highway, or other sources of pollution, the other – in a few meters away from it. 4. Leave vessels for 4 weeks. During the evaporation of the liquid, add to them the solution. If the vessels are overflowing, as a result of precipitation, finish the experiment. 5. At the end of sampling of the material, evaporate the solution in clean weighed beaker. Then weight the glass again, and determine the amount of sediment. 6. Based on the area of the opening of the vessel, calculate the amount of material deposited per 1 m2. Laboratory work #3. The investigation of natural rainfall Monitoring of the atmospheric precipitation and investigation of method of sampling is of interest both in terms of meteorological estimates of the amount of precipitation, and from the point of view of further analysis of samples for the determination of various air pollutants, such as heavy metals, nitrates, chlorides, sulfates, acidity etc. Samples of wet precipitation (rain and snow) are extremely sensitive to contamination that may occur in the sample using not enough clean glassware, contact of foreign (non-atmospheric origin) and other particles. It is believed that wet precipitation samples should not be taken near sources of significant pollution of the atmosphere, such as boilers or CHP, open storage of materials and fertilizers, transport junctions and others. In such cases, the precipitation samples would be significantly affected by these local sources of anthropogenic contamination. Progress of work: Samples of precipitation should be collected into special containers made from neutral materials. Rainwater is collected by using a funnel (diameter is not less than 20 cm) in a graduated cylinder (or directly into the bucket) and stored there until analysis (Figure 10). 53

Fig. 10. A device for sampling of liquid precipitation (rain gauge): a – funnel; b – graduated cylinder

Calculation of rainfall (h) in mm is carried out using the formula:

h

4V SD 2

d2 H, D2

where: V is volume of sample of precipitation, ml; D is diameter of the funnel, cm; d is diameter of the graduated cylinder, cm;  is the height of column of sampled liquid. Sampling of snow is usually carried out by cutting the cores to the full depth (to the ground), and to do this it is advisable at the end of a heavy snowfall (in early March). The volume of snow in terms of water can also be calculated according to the above formula, where D is diameter of the core. Methodology: 1. Put a graduated cylinder under the open sky. 2. After each rainfall drain the excess water and measure its pH and amount of precipitation in milliliters. 3. Carry out this work within one month. 4. Create a histogram of acid precipitation by the model below.

54

Laboratory work #4. Analysis of snow cover Snow cover accumulates in its structure almost all substances entering the atmosphere. In connection with this, snow can be regarded as a specific indicator of clean air. Depending on the source of contamination the composition of the snow cover changes. Thus, near the boiler, rail networks, serving locomotives on fuel oil, a large flow of transport, operating on diesel sulfur-containing fuel, as well as a number of specific industries should expect high content of sulfur compounds. Anthropogenic sources of nitrogen compounds content are vehicles, power system, industrial enterprises. Informative parameter is the pH of snow water. In normal (unpolluted) state, it varies from 5.5 to 5.8. Near steelworks, around CHP, boiler usually has a pH values of snow is higher, i.e. represents a weakly alkaline or alkaline medium, due, apparently, to deposition of ash particles, containing compounds of hydrocarbons of potassium, calcium, magnesium, raising the pH of snow water. Along the highway, in places of industrial emissions of combustion products with a predominance of oxides of sulfur, nitrogen, carbon, pH of snow cover decreases, indicating the acidity of precipitation. Progress of work: Analysis of snow cover should be made once at the end of the winter season. Snow must be taken throughout the depth of its deposition in glass bottles (the best is three-liter). Immediately after the melting of the sample, when the temperature of melt water reaches room, its analysis is carried out. For chemical analysis of snow cover, territory of the campus should be divided into squares, take a sample of snow in each of them, with mass not less than 3 kg. After temperature of the melt water reached room temperature, the analysis on the following components is carried out: compounds of nitrogen, sulfates, some heavy metals, by methods described below in the section on analysis of the physical-chemical properties of water. Furthermore, it is necessary to determine the total concentration of salt, the presence of insoluble substances and snow water acidity. Total salt content of meltwater is found by adding of 5 ml of 10% hydrochloric acid to 500 ml of the filtered melt water, followed by evaporation to dryness and weighing the residue. The presence of insoluble substances is determined by filtration, drying of the precipitate on the filter and weighing. Laboratory work #5. Determination of heavy metals in atmospheric precipitations One of the ways of human impact on the natural environment is the release of a variety of toxic substances into the atmosphere with the subsequent transfer of these pollutants of air masses and precipitation on the elements of the underlying surface. It is known that up to 30% of toxic substances come in the aqueous medium with precipitation that accumulate and change the natural properties of water and the conditions of existence of aquatic organisms. 55

As noted earlier, the difference between the heavy metals from other toxicants is their inability to biodegradation. Once released into the water body, they become permanent components of the ecosystem. According to the degree of enrichment of atmospheric precipitation metals are arranged in the following order: Zn> Pb> Cd> Ni. In precipitations these elements are present in soluble (salts, complex ions), and slightly soluble forms. So mercury compounds in atmospheric precipitations are represented in two groups: the first group is element form and organic compounds, and the second is inorganic derivatives. The main quantity of mercury contained in the precipitations is in the form of organometallic compounds. The lead content of precipitation can vary from 0.05 to 7.3 \g/l. Background content of this element in the atmospheric precipitations is 0.3-4.4 \g/l. Background natural sources are responsible for the receipt of about 17 thousand tons of lead. The maximum number of heavy metals, including lead in precipitation, contains in winter, which is determined by a higher level of air pollution from fuel combustion. In the cold period the content of zinc and cadmium in atmospheric precipitations is increased due to frost formation process. Progress of work: 1. Sample fresh, or old snow (during spring thaw), or rain water in the area where you live. 2. Carry out sampling of snow on an open site with the help of plastic trowels in clean plastic bags. 3. Sample rainwater in a clean plastic ware during the day. 4. Thaw snow samples at room temperature, without heating. 5. Select 250 ml of sample of precipitation in a heat-resistant glass. 6. Evaporate sample on a water bath. The final volume should be 25-50 ml. 7. If there is an insoluble precipitate, filter the solution. 8. Exactly measure the prepared volume and add 1 ml of concentrated hydrochloric acid. 9. Give a flask to laboratory assistant to measure the concentrations of heavy metals by atomic absorption spectroscopy. 10. According to obtained diagram, create calibration curve for each metal, evaluate metal content in the test solution. 11. Express the content of each heavy metal per unit of volume of the test samples of atmospheric precipitation. Laboratory work #6. Express methods of determining of carbon dioxide in indoor air It has long been known that carbon dioxide is directly related to global warming, but as it turned out, the carbon dioxide can be directly related to our health. Man is the primary source of carbon dioxide in the room, since we breathe out from 18 to 25 liters of gas per hour. 56

Elevated levels of carbon dioxide levels can be observed in all areas where there are people, i.e. in the classroom and college auditoriums, conference rooms and office space, in bedrooms and children's rooms. That fact that we do not have enough oxygen in a stuffy room is a myth. Calculations show that, contrary to the existing stereotype, headache, weakness and other symptoms occur at the person in the room is not from lack of oxygen, namely from an excess of carbon dioxide. Man begins to feel uncomfortable, a shortage of fresh air much earlier than the level of oxygen in the room falls to a critical level. Only recently in the European countries and the US level of carbon dioxide in the room was measured only in order to check the quality of ventilation, and it was assumed that CO2 is dangerous to humans only in high concentrations. Studies on the effect of the same carbon dioxide on the human body in a concentration of about 0.1% appeared recently. Few people know that the clean air of the city contains about 0.04% of carbon dioxide, and as closer the content of CO2 in the room to this number, the better the person feels. According to research carried out in the UK by the largest accounting firm KPMG, a high level of CO2 in the air of office space can be a cause of morbidity of employees and can reduce the concentration of their attention on third. Elevated carbon dioxide levels may be the cause of the headache, inflammation of the eye, nose and throat, as well as cause tiredness of staff. As a result of research, carried out by Indian scientists among residents of Kolkata, it was found that even low concentrations of carbon dioxide were a potentially toxic gas. Scientists concluded that carbon dioxide on the toxicity is similar to nitrogen dioxide, taking into account its effect on cell membranes and biochemical changes occurring in human blood, such as acidosis. Prolonged acidosis, in turn, leads to diseases of the cardiovascular system, hypertension, fatigue and other adverse consequences to the human body. Method #1. The method is based on the reaction of carbon dioxide with a solution of soda. Progress of work: In a syringe of 100 ml, full 20 ml of 0.005% soda solution with phenolphthalein having a pink color, and then 80 ml of air is aspirated and shaken for 1 min. If there is no decolorization of the solution, gently squeeze the air from the syringe, leaving therein the solution, aspirate new portion of air and shake it for 1 minute. This operation is repeated 3-4 times, followed by the addition of the air in small portions per 10-20 ml, each time shaking the contents for 1 minute until colorless of the solution. Calculating of the total volume of air passed through the syringe, determine the concentration of CO2 in the air according to the data of the Table 2. Method #2. The method is based on neutralizing of weakly ammoniacal solution by carbon dioxide in the presence of phenolphthalein indicator. Later it is performed a comparative study of investigating air and air of open atmosphere where the CO2 is kept at 0.04% in the city and 0.03% in rural areas. 57

Table 2 The dependence of the CO2 content in the air from the air volume, decolorizing of 20ml of 0.005% sodium carbonate solution Volume of air, ml 80 160 200 240 260 280 300 320

Concentration of 2, % 0.32 0.208 0.182 0.156 0.144 0.136 0.128 0.120

Volume of air, ml 330 340 350 360 370 380 390 400

Concentration of 2, % 0.116 0.112 0.108 0.104 0.100 0.096 0.092 0.088

Volume of air, ml 410 420 430 440 450 460 470 480

Concentration of 2, % 0.084 0.080 0.076 0.070 0.066 0.060 0.056 0.052

Progress of work: The tube is poured by 10 ml of the absorbing solution (for 500 ml of distilled water is added 0.04 ml of a solution of ammonia and 1 ~ 2 drops of 1% phenolphthalein solution), and is closed by a rubber cap which have been pierced in advance from the syringe needle. First, the study is carried out with an open air atmosphere. For this, the air is taken by syringe till 20 ml mark and under pressure is added through the needle into the vial with ammonia solution. Without releasing the plunger, tube is vigorously shaken to absorb CO2 from the air. These manipulations are performed to complete bleaching of the absorption solution. Record the number of times (number of needles) have to enter air from the syringe into the vial so that the solution became colorless. Thereafter, the tube is freed from the used solution, washed with distilled water, filled with 10 ml of fresh absorbing solution and similarly the test with investigated air is carried out. Again, write down the number of syringes necessary for bleaching of the solution. As a rule, in the second case to neutralize the ammonia solution requires less air syringes. The concentration of carbon (IV) oxide in air is determined by the following formula: ͲǤͲͶ݊ ‫ݓ‬ሺΨሻ ൌ ݊ଵ where:  is the amount of syringes of air of open atmosphere; n1 is the amount of syringes of investigated air. Method #3. Analysis is based on the reaction of CO2 with calcium hydroxide. Progress of work: 1. Prepare a saturated solution of calcium hydroxide. At 20° C in a saturated solution, mass fraction of the Ca(OH)2 is 0.1647%. The density of this solution is 1.001 g/ml. 58

2. Determine the capacity of the compressor (l/min). For this purpose it should be measured water displaced by volume of air injected for 1 min in inverted cylinder with water. 3. Analyze the air in the laboratory, and in another room of the department. For this purpose pour the cylinder by 200 ml of distilled water. Measure by pipette and put there: 2 ml of a saturated solution of calcium hydroxide. Add 10 drops of 1% phenolphthalein solution. The gas outlet tube placed in the cylinder of the compressor so that the sprayer reaches the cylinder bottom. Turn on compressor in electricity and determine by stopwatch the time required to complete bleaching of solution. 4. Write the equation for the reaction of occurring processes. Calculate the volume fraction of CO2 in the air. ܻൌ

ሺʠʝଶ ሻ ൉ ͳͲͲΨ ሺƒ‹”ሻ

Compare with the maximum permissible content of CO2 (the norm is Y 100

75

5-20

5-50

100

-

0.01-0.03

0.03-0.25

>0.25

-

5-80

80-500

500-1500

-

30-40

25-30

15-25

12-15

0.01-0.015

0.15-0.60

>0.06

-

0.01-0.020

0.2-0.3

>0.03

-

Concentration of carbonate, mgC/l | during summer rH of silt BOD5, mg@/l

2-7 6.9-7.2 25-30 2.3-3.3

7-20 7.2-8 15-25 3.3-5.5

15-20 8-9.5 7-17 >5.5

-

Concentration of dissolved oxygen, % of saturation

95-105

50-155