Sustainable Water Purification 9781119651147, 111965114X

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Sustainable Water Purification

Scrivener Publishing 100 Cummings Center, Suite 541J Beverly, MA 01915-6106 Publishers at Scrivener Martin Scrivener ([email protected]) Phillip Carmical ([email protected])

Sustainable Water Purification

M. Safiur Rahman and

M.R. Islam

This edition first published 2020 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA and Scrivener Publishing LLC, 100 Cummings Center, Suite 541J, Beverly, MA 01915, USA © 2020 Scrivener Publishing LLC For more information about Scrivener publications please visit www.scrivenerpublishing.com. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, except as permitted by law. Advice on how to obtain permission to reuse material from this title is available at http://www.wiley.com/go/permissions. Wiley Global Headquarters 111 River Street, Hoboken, NJ 07030, USA For details of our global editorial offices, customer services, and more information about Wiley products visit us at www.wiley.com. Limit of Liability/Disclaimer of Warranty While the publisher and authors have used their best efforts in preparing this work, they make no rep­ resentations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of merchant-­ ability or fitness for a particular purpose. No warranty may be created or extended by sales representa­ tives, written sales materials, or promotional statements for this work. The fact that an organization, website, or product is referred to in this work as a citation and/or potential source of further informa­ tion does not mean that the publisher and authors endorse the information or services the organiza­ tion, website, or product may provide or recommendations it may make. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for your situation. You should consult with a specialist where appropriate. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read. Library of Congress Cataloging-in-Publication Data ISBN 9781119650997 Cover image: Water background - Anna1311 | Dreamstime.com, Surf with clouds - Penguinpete | Dreamstime.com, Mountains with Rain - Jan Baars | Dreamstime.com Cover design by Kris Hackerott Set in size of 11pt and Minion Pro by Manila Typesetting Company, Makati, Philippines Printed in the USA 10 9 8 7 6 5 4 3 2 1

Contents Prefacexi 1 Introduction 1.1 Opening Remarks 1.2 Climate-Water-Food Nexus 1.3 Background 1.4 Insufficiency in Water Purification Processes 1.5 Introduction to Zero Waste Engineering 1.6 Scope of the Book 1.7 Organization and Introduction of the Chapters

1 5 8 9 11 12 12

2 Water Science 2.1 Introduction 2.2 Unique Features of Water 2.3 Natural State of Matter 2.4 Source of Water and Its Role in Sustaining Life 2.4.1 Inorganic Minerals 2.4.2 Organic Contaminants 2.4.3 Radioactive Minerals 2.4.4 Biological

15 16 31 37 38 49 49 50

3 Sustainability of Current Water Purification Technologies 3.1 Introduction 3.2 Sustainability Criteria 3.3 Sustainability in the Information Age and Environmental Insult 3.3.1 Agriculture and Development 3.3.2 Desertification 3.3.3 Ecosystem Change 3.3.4 Fisheries 3.3.5 Deforestation 3.3.6 Marine Litter 3.3.7 Water Resources

59 68 69 71 72 72 72 73 74 75 vii

viii  Contents 3.4 Biological Processes 3.4.1 Sulfate Reducing Bacteria 3.5 Chemical Precipitation 3.6 Membrane Separation 3.6.1 Microfiltration 3.6.2 Ultrafiltration 3.6.3 Nanofiltration 3.6.4 Reverse Osmosis 3.7 Ion Exchange 3.8 Ozonation 3.9 UV Radiation 3.10 Adsorption 3.10.1 Existing Sorbents 3.10.2 Agricultural Waste 3.10.3 Industrial By-Products 3.10.4 Natural Materials 4 Sustainable Drinking Water Purification Techniques 4.1 Introduction 4.2 Natural Lifestyle 4.2.1 Environmental Awareness 4.2.2 Corporatization and Healthcare 4.2.3 Death and Lifestyle 4.2.4 Role of Water in Bodily Functions 4.2.5 A Relevant Anecdote 4.3 Natural Minerals 4.3.1 Filters 4.3.2 Ground Water Recharge 4.3.3 Aeration 4.3.4 Brick, Clay and Others 4.4 Solar UV Treatment 4.5 Natural Ozonation 5 Sustainable Purification Techniques for Agricultural Waters 5.1 Introduction 5.2 Organic vs. Chemical Agricultural Practices 5.2.1 Denaturing for a Profit 5.2.2 The Consequences 5.2.3 The Sugar Culture and Beyond 5.3 Removal of Heavy Metals 5.3.1 Application of Wood Sawdust for Removal of Heavy Metals

77 80 82 85 88 90 92 95 97 99 104 107 108 109 114 118 123 126 131 134 135 140 147 148 149 150 150 150 151 152 155 161 169 170 171 179 181

Contents  ix 5.3.1.1 Composition, Structure and Morphology of Wood 182 5.3.1.2 Structure and Morphology of Wood 183 5.3.1.3 Removal of Heavy Metals Using Wood Saw Dust 191 5.3.1.4 Conclusion 206 5.4 Removal of Heavy Metals Using Fish Scale 208 5.4.1 Fish Scale Collection and Treatment 208 5.4.2 Experimental Setup and Procedure 209 5.4.2.1 Static Method 209 5.4.2.2 Dynamic Method 211 5.4.3 Conclusions 215 5.5 Solar UV Treatment 216 5.5.1 Effects of UV-Radiation 217 5.5.2 Effects of Temperature (Infrared Radiation) 218 5.5.3 Advantages of Solar Water Disinfection (SoDis) 218 5.5.4 Limitations of Solar Water Disinfection 219 5.6 Bioremediation for Sustainable Purification of Water 219 6 Sustainable Purification Techniques for Industrial Wastes 6.1 Removal of Radionuclides 6.2 Removal of Heavy Metals Precious Metals 6.2.1 Precious Metals and Heavy Metals Recovery 6.3 Industry Lifestyle Change 6.3.1 Mercury 6.3.2 Sal Ammoniac 6.3.3 Sulphur 6.3.4 Arsenic Sulphide 6.3.5 Refining Techniques 6.4 The Energy/Water Crisis 6.4.1 Are Natural Resources Finite and Human Needs Infinite? 6.4.2 The Finite/Infinite Conundrum 6.5 Certain Sustainable Technologies 6.5.1 Direct Use of Solar Energy 6.5.2 Effective Separation of Solid from Liquid 6.5.3 Effective Separation of Liquid from Liquid 6.5.4 Agricultural Waste for Water Purification and Value Addition 6.5.4.1 Orange Peel 6.5.4.2 Pomelo Peel

221 224 225 231 237 244 246 251 256 258 258 269 270 270 274 275 276 277 277

x  Contents 6.5.4.3 Grapefruit Peel 6.5.4.4 Lemon Peel 6.5.4.5 Banana Peel 6.5.4.6 Cassava Peel 6.5.4.7 Jackfruit Peel 6.5.4.8 Pomegranate Peel 6.5.4.9 Garlic Peel 6.5.5 A Novel Desalination Technique 6.5.6 A Novel Separation Technique

278 278 279 280 281 281 282 283 296

7 Summary and Conclusions 7.1 Summary 299 7.2 Conclusions 300 7.2.1 Chapter 1: Introduction 300 7.2.2 Chapter 2: Water Science 300 7.2.3 Chapter 3: Sustainability of Current Water Purification Techniques 301 7.2.4 Chapter 4: Sustainable Drinking Water Purification Techniques 301 7.2.5 Chapter 5: Sustainable Purification Techniques for Agricultural Wastes 302 7.2.6 Chapter 6: Sustainable Purification Techniques for Industrial Wastes 302

References and Bibliography 303 Index325

Preface Every civilization in human history recognized the importance of water and understood the importance of water and air in their natural state for the sustenance of life. This all changed during the plastic era. For over a century, the current civilization has been synonymous with synthetic chemicals. All such processes undergo deliberate ‘denaturing’, starting with removing innate water, which is ubiquitous in nature. At present, between 25,000 to 84,000 synthetic chemicals are used to drive modern corporate culture, the hallmark of Capitalism. The number of synthetic chemicals has multiplied 25 times since 1970, with a rise in economic dividend from $171 billion to over $4 trillion today. As these chemicals have created numerous problems in all aspects of civilization, another line of industry has cropped up – the so-called waste management and cleanup industry, which ironically has introduced a new line of synthetic chemicals to ‘purify’ the current contamination. In this scheme, water is the most important yet most hapless victim. There are numerous techniques available today to purify water – the most potent purifier on Earth. Ironically, all techniques use chemicals to replace the contaminants of the water under treatment. These chemicals are all toxic to the environment, despite being ‘certified’ by the same establishment that upholds the plastic culture, which is responsible for the current toxic shock. It should come as no surprise that all techniques used for water purification today are unsustainable. This dichotomy arises from the fact that today’s civilization is driven by science that is incapable of identifying the causes, let alone remedying them of the inherent unsustainability of purification techniques. In this book, the source of contaminations is identified as synthetic chemicals, which should not have entered the ecosystem to begin with. Any purification technique must use sustainable techniques. Sustainability lies within the adoption of a zero-waste scheme, rather than struggling to ‘minimize’ waste. In this book, sustainable purification techniques are presented that are applicable to municipal, agricultural and industrial sectors. xi

xii  Preface They range from organic contaminants to radioactive wastes. For each technique, it is shown how value addition and conversion of waste into value-added products can turn a zero-waste process into an economically successful endeavor. This book shows that any paradigm shift to turn this toxic culture into a healthy one starts with water – the first ‘element’ of the universe. M. Safiur Rahman M.R. Islam

1 Introduction 1.1 Opening Remarks Water is synonymous with life. This has been the case since the pre-historic time to modern era (Tsiaras et al., 2019). While the indispensability of water for sustaining life is well known, water being the first creation and as such the ubiquitous phase on earth as well as the cosmos is little known in the modern era. This is a typical problem related to New Science, which disconnected modern knowledge from the previous annals of science. In the pre-Socratic cosmogony of Thales, considered to be the first ‘element.’* This was more than a poetic gesture, it was rather an attempt to answer the question: “What is the common stuff from which everything is composed?” This notion of water being the first creation permeated through Christianity. In Genesis 1:1-2, it is stated, “And the Spirit of God was hovering over the face of the waters”. Quran (11:7) points to the existence of water before any other creation, the exact word being: “and His (creator’s) throne/dominion extends on the water - that He might manifest to you, which of you is best in action....” (Qur’an 11:7). This throne is similar to the notion of ‘lotus’ in ancient India (Tresdder, 1997). This, in addition to indispensability of water for sustainability of humans (67:30; 24:54) as well as overall origin of every life on earth (24:45). Islam (2014) presented the scientific justification of water as both the first matter of cosmos as well as the first material of life. As such, Islam (2014) characterized water as the ubiquitous phase. It follows that the purity of water is pivotal to global sustainability. For human health, water is the vehicle for carrying nutrients to all cells in our body and oxygen to our brain. Water allows the body to absorb and assimilate minerals, vitamins, amino acids, glucose and other substances. Water flushes out toxins and waste. Water helps to regulate body temperature and maintains the overall metabolism for sustaining life. * This term does not relate to modern scientific term, which emerges from atomic theory. Rather, it refers to a material in its natural state. M. Safiur Rahman and M.R. Islam. Sustainable Water Purification, (1–14) © 2020 Scrivener Publishing LLC

1

2  Sustainable Water Purification As such, humanity, civilization, the environment, and the cosmos are all connected seamlessly (depicted in Picture 1.1). Modern investigation in material science has been marred with the first premise, which is inherent to the Big Bang theory. The fundamental

Picture 1.1  Humanity, civilization, environment and the cosmos are all connected through ubiquitous water and ‘vital force’ (Photo: Rola Iceton, published with permission).

Introduction  3 premise is: creation is made in two stages, namely 1) fundamental element is created out of nothing; 2) all other elements evolve from fundamental element. This theory considers hydrogen atoms as the first material in existence, thus creating paradoxical depiction of mass and matter. In the past decade, observations from space and the ground have found water to be the most abundant molecular species, after hydrogen, in the atmospheres of hot, gaseous extrasolar planets (Tsiaras, 2019). However, as early as 2011, evidence surfaced that the existence of hydrogen molecules is not factual and comes from the assumption that hydrogen is the first ‘element’ to come to existence. Khan and Islam (2016) point to the fact that scientists actually look for water molecules even in outer galaxy to consolidate the claim that the assumption that hydrogen, which is not the most abundant molecule in universe. With the premise that water is the first ‘element’ in existence, the existence of ‘energy’ and its natural state can be properly retooled. Islam (2014) introduced the concept of characteristic time to assure sustainability. It involves identifying natural state of a matter, which is dictated by the time function. Table 1.1 shows fundamental properties of tangible (e.g. matter) and intangible (e.g. energy). The tangible-intangible duo can be regarded as a yin-yang. In ancient Chinese, as well as ancient Indian culture, water and fire are considered to be the original yin yang. The term ‘fire’ represents energy (Qi in Chinese, often translated as ‘vital force’, “material energy”, “life force” or “energy flow” in figurative sense and ‘air’ in literal sense). Table 1.1 shows the yin yang nature of energy and matter. The yin yang shows contrast as well as interdependence. For instance, no matter is Table 1.1  The tangible and intangible nature of yin and yang (From Islam, 2014). Yin (tangible), water

Yang (intangible), ‘energy’ (Qi)

Produces form

Produces energy

Grows

Generates

Substantial

Non-Substantial

Matter

Energy

Contraction

Expansion

Descending

Ascending

Below

Above

Water

Fire

4  Sustainable Water Purification produced without energy and no energy is produced without matter. Water is needed for plant, which is then needed for fire. This logic also shows nothing is natural (hence sustainable) unless it is part of the positive negative cycle. For instance, fire without water is not real. That would explain why diamond cannot be set on fire even though it is made out of carbon. Similarly, the presence of mass would indicate the presence of energy. This would make the existence of zero energy and infinite mass an absurd concept, even though new cosmic physicists routinely tout that notion (Krauss, 2012). Figure 1.1 depicts a water-fire yin yang. It shows how yin and yang encircle each other alternating as a continuous function of time. As time progresses, yin becomes yang and vice versa. This progression confirms the existence of characteristic time function for every object at every scale. Within the limitations of natural traits that is finite, the following picture depicts the role of two counteracting entities being held in harmony by the ‘mother’, the one that dictates the universal order (Islam, 2014). This most important takeaway of this discussion is that water and energy form the foundational yin yang pattern and sustainability is making sure they are at their natural state. As we will see in Chapter 2, this gives a new and scientifically accurate starting point for discussion of sustainability. With this definition, all other descriptions in physics and chemistry have to be retooled. For instance, even the term ‘gravity’ bars an implicit assumption that the force between two objects is uniquely related to their

Figure 1.1  Water-fire yin yang, showing how without one the other is meaningless.

Introduction  5 masses, independent of other factors, such as history, or current state of motion. Scientifically, if two objects are in natural state, the force between them would be different from that prevailing if at least one of them is not.

1.2 Climate-Water-Food Nexus Climate-Water-Food nexus epitomizes current civilization that depends on energy as the driver. As such it is one of the most popular themes used in both sustainability and climate change research (Hellegers et al., 2008; Bazilian et al., 2011). Table 1.2 shows key elements of the water component of the nexus. The primary energy source of the Earth is the sun. The sunlight is essential to photosynthesis that requires CO2 and water as well as the presence of a plant biomass. As such, CO2 is integral to the Energy-Water-Food nexus (Figure 1.2). In this process, any pollutant added to the process that produces CO2 can alter the quality of food, which then can alter the entire water cycle, thus forming a ‘spiraling down’ mode in the overall ecosystem. In an agricultural process, any artificial chemical added to the water or soil system will affect the quality of food. Equally impactful is the overall composition of the atmosphere and the temperature, because each of the oxidation reactions is a sensitive function of temperature and composition. Even Table 1.2  Synergies between water and sustainable growth (modified from UN Water, 2013). Characteristics of sustainable growth

Characteristics of water security

Effective use of natural resources

Meet social and economic development need of water

Valuing ecosystem

Supply of adequate water for maintaining ecosystems

Inter-generational economic policies

Sustainable water availability for future generations

Protection of vital assets from climate-related disasters

Balance the intrinsic value of water with its uses for human survival and well being

Reduce waste of resources

Harness the productive power of water, maintain water quality, and avoid pollution and degradation.

6  Sustainable Water Purification

ed eed is n od ter w fo Wa gro to s ort nsp ater tra od l) w Fo irtua (v

W to ater ge ne is ne rat ed e e ed ne rgy En e rg to y sup is n e ply ed wa ed ter

Water

Energy is needed to produce food

Energy

(Sunlight)

Food can be used to produce energy

Food CO2

Figure 1.2  The Water-Food-Energy Nexus (Modified from Lal, 2013).

a small amount of toxins can alter the natural pathway irreversibly through catalytic actions. In connection with environmental resource management, the term nexus was introduced for the first time during the 1980s, notably in a project by the UN University (Food-Energy Nexus programme, as pointed out by Sachs and Silk, 1990). However, the Nexus Approach only gained prominence in international academia and policy circles in the lead-up to the Bonn Conference (2011) on the “Water, Energy and Food Security Nexus”. The well-known definition of ‘nexus’ was reinforced in this conference to delineate “management and governance across sectors and scales”, reducing trade-offs, and building synergies, overall promoting sustainability and a transition to green economy (Hoff, 2011). When looking at the before mentioned nexus of water, energy, and food security, the question arises as to which environmental resources have to be managed in an integrated way to achieve the sought integrated and sustainable management. Considering the fact that nature is continuous, meaning there is no barrier to either mass or energy transport, not a single particle of mass (thus energy) can be isolated, any point is inflicted with toxicity will have an impact on the rest of the ecosystem. In this regard, it is important to recognize the science used to study this process. Scientists cannot determine the cause of global warming with the science that assumes all molecules are identical, thereby making it impossible to distinguish between organic CO2 and industrial CO2. In the mean time, the environmental resources to be studied are: water, soil, and atmosphere. In modern society, waste, instead of atmosphere is made into an integral part of this nexus (Figure 1.2). It is because the modern age is synonymous with wasting habits. Such wasting habits are systemic and integral part of technology development. Such a tendency comes from the fact that in today’s

Introduction  7 society everything is denatured and the artificial version is constructed and promoted as the ideal version. In Chemical Engineering, an entire subject is dedicated to denaturing materials and then sold in medicine/medical industry - which itself is 100% artificial and harmful to humans. Such a process is inherently unsustainable (Khan and Islam, 2007). Figure 1.3 depicts how any of the waste forms its own cycle and never assimilates with the ecosystem. As an example, if one considers CO2 that is generated from industrial activities or exhausts of combustion engines, any such CO2 would end up being rejected by the ecosystem. In contrast, any CO2 produced through organic activities (such as breathing of plants and animals) will be readily absorbed by the plants that will transform it into carbohydrates. Thus, from the same activity (oxidation or breathing), either waste (CO2 from exhaust) or a beneficial product (CO2 from breathing) is generated. In this process, waste accumulates within a system separate from the ecosystem and grow into a cancer-like entity within the overall global system. The remedy to this accumulation of waste and its inherent unsustainability is in making the use of fuel and mass wholly zero-waste, which can happen only when any product that is the outcome of an engineering process is entirely usable by some other process, which in turn would result in products that are suitable as inputs to the process. A perfect system is 100% recyclable and, therefore, zero waste. Such a process remains zero waste as long as each component of the overall process also operates at zero waste.

Water

Soil Waste

Atmosphere

Figure 1.3  The water-soil-atmosphere nexus.

8  Sustainable Water Purification The production of food relies on water, soil, and atmosphere. There is no waste generated if all nutrients and all pesticides are wholly organic. This not be the case for last 100 years or so (ever since the plastic culture has dominated current civilization), significant amount of waste is generated. This waste thus ends up creating further pollution of soil, water, and atmosphere and propagate through the food chain creating long-term insult to the environment. Equally important is the role of energy sources.

1.3 Background Water is a transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth’s hydrosphere, and the fluids of most living organisms. It is vital for all known forms of life, even though it provides no calorie organic nutrients. Its chemical formula is H2O, meaning that each of its molecules contains one oxygen and two hydrogen atoms, connected by covalent bonds. Water is the name of the liquid state of H2O at standard ambient temperature and pressure. It forms precipitation in the form of rain and aerosols in the form of fog. Clouds are formed from suspended droplets of water and ice, its solid state. When finely divided, crystalline ice may precipitate in the form of snow. The gaseous state of water is steam or water vapor. Water moves continually through the water cycle of evaporation, transpiration (evapotranspiration), condensation, precipitation, and runoff, usually reaching the sea. The distribution of water on the Earth’s surface is extremely uneven. Only 3% of water on the surface is fresh; the remaining 97% resides in the ocean. Of freshwater, 69% resides in glaciers, 30% underground, and less than 1% is located in lakes, rivers, and swamps. Looked at another way, only one percent of the water on the Earth’s surface is usable by humans, and 99% of the usable quantity is situated underground. Due to different types of natural and anthropogenic activities surface and ground water become contaminated. Water pollution by toxic pollutions (inorganic and organic) has become a subject of interest especially since the establishment of the EPA (Environmental Protection Agency) in 1970. The problem of water quality degradation of both surface and sub-surface streams has been evident for a long time. Achieving an acceptable quality of surface water focuses on reducing emissions of known pollutants to within safe industrial and drinking standards. In developing nations, many of today’s industrial projects are environmentally hostile. The quality of drinking water is an important factor in determining human welfare. It has been noted that polluted drinking water is the cause

Introduction  9 for waterborne diseases which wiped out the entire populations of cities. The major sources of water pollution are domestic waste from urban and rural areas, and industrial wastes which are discharged into natural water bodies. The rivers and lakes near urban centres emit disgusting odours and fish are being killed in millions along the sea coasts. Extensive studies of the subject of water pollution by toxic pollutions (inorganic and organic) have been developed during the recent years. In today’s world, the study and research of pollutants should not be confined to their more removal or relocation. Economic feasibility, one of the key factors in any engineering project, must be addressed. Many of today’s engineering works are environmental friendly but that criterion is no longer sufficient. Time has come to make environmental works appealing rather than friendly. Islam and Wellington (2001) gave much stress on the development of environmentally appealing research projects mentioning introduction of novel methods in the areas of engineering research.

1.4 Insufficiency in Water Purification Processes Vast majority of water contamination is due to industrial waste, which contain synthetic (uunatural) chemicals, which emerge from the industrial applications. The contaminated water, which contain synthetic chemical, biological, organic waste and other contaminants, suspended solids, and gases are treated in order to remove the undesired components in the water stream. It is routine that water is first disinfected in order to remove bacteria and organic organisms, algae, etc. Although most water is purified for human consumption, the purification agents are invariably synthetic chemicals, which are toxic to the environment and to humans. In addition, water is subject to chlorination, fluoridisation, and others with the pretext of maintaining levels of chemicals under certain pre-determined values. Even for commercial applications, synthetic chemicals are added in order to make the water usable. For medical and pharmaceutical purposes, the purity of water is increased by exposing water to rigorous purification processes, which invariably use one or more of the following techniques: –– –– –– –– ––

filtration sedimentation distillation chemical processes electromagnetic and other form of irradiation (such as ultraviolet light)

10  Sustainable Water Purification Although the above processes reduce the concentration of suspended particles, parasites, bacteria, algae, viruses, and fungi as well as reduce the concentration of a range of dissolved and particulate matters, the water stream picks of parts of the chemicals used to purify and as long as the concentration is smaller than the regulatory body’s requirement there remains no way to determine their long-term impact. Jaspal and Malvya (2020) reviewed major water purification composites. The use of such composites is considered to be the latest technology in water purification. The use of different types of composites ranges from nanocomposites, activated charcoal composites, polymer composites, oxide-based composites, hybrid composites, and biosorbent composites, etc. Water purification takes place via adsorption process. These composites have been explored for treating or elimination of various hazardous substances like heavy metal species, different classes of colored contaminants (dyes), several organic and inorganic pollutants from wastewater. The most significant advantage of the use of composites is the combination of properties of two materials into one for specific applications. In the current scenario, composites have gained popularity in various fields such as constructional, aeronautical, vehicular, biomedical, industrial etc. (Mahajan and Aher, 2012). The use of the said materials in wastewater treatment is becoming a research focus

Dyes

Polluted Water Heavy Metals

Pesticides

Synthetic Chemicals

Phenolic Compounds etc.

Water + Toxins

Figure 1.4  Water purification process.

Introduction  11 for many. The properties offered by composites include specific strength, processability, and design flexibility. While these composites successfully eliminated Zn2+, Ni2+, Cu2+, Pb2+, Hg, etc., each ion is replaced with another component from the adsorbing chemicals that are used in the process. Each of these composites would be considered unsustainable if environmental sustainability were considered (Khan and Islam, 2016). Figure 1.4 shows how chemicals are removed from the contaminated water only to be replaced with toxins, which arise from the purification process. The above purification process does not include the impact of using unnatural radiation (e.g. ultraviolet). Although conventional analysis makes it impossible to identify the impact, let alone quantify it, Islam and Khan (2019) Islam et al. (2016) have shown that the effluent water would carry the signature of each unnatural process (energy or mass) used during the purification cycle.

1.5 Introduction to Zero Waste Engineering Natural additives have been used for the longest time, dating back to the regime of the Pharaohs of Egypt and the Hans of China (Gove, 1965). However, the renaissance in Europe has given rise to industrial revolution that became the pivotal point for the emergence of numerous artificial chemicals. Today, thousands of artificial chemicals are being used in everyday products, ranging from health care products to transportation vehicles. With renewed awareness of the environmental consequences and more in-depth knowledge of science, we are discovering that such ubiquitous use of artificial chemicals is not sustainable (Khan and Islam, 2016). If the pathways of various artificial chemicals are investigated, it becomes clear that such chemicals cannot be assimilated in nature, making an irreparable footprint that can be the source of many other ecological imbalances (Chhetri and Islam, 2008). Most persistent and bioaccumulative chemicals eventually find their way into our bodies via the food chain. Chemical industries mass produce artificial additives and, therefore, gain the advantage due to the economy of scale, in line with modernization since the industrial revolution. Federal regulators have determined that about 4,000 chemicals used for decades in Canada pose enough of a threat to human health or the environment that they need to be subjected to safety assessments (The Globe and Mail, 2006). These artificial additives are either synthetic themselves or derived through an extraction process that uses synthetic products. Even when the source is natural, it may have been contaminated through

12  Sustainable Water Purification artificial agents, such as chemical fertilizer, pesticide, etc. These artificial chemicals have a number of hidden adverse side effects. Furthermore, once artificial additives are disposed into the environment, they remain in nature for a very long time. These synthetic products never degrade biologically; they are either pulverized (hence become invisible) or oxidized to produce toxins (Khan and Islam, 2016). On the other hand, natural additives are naturally occurring substances that are considered valuable in their natural form. Most of the natural materials are readily biodegradable, so they have zero waste and they have no long term negative impact. Natural materials are inherently superior to synthetic materials with regard to efficacy and safety in matters related to human health. Any attempt to improve current engineering practices should investigate the possibility of replacing artificial additives with natural ones that are environment friendly and truly sustainable (Khan and Islam, 2007).

1.6 Scope of the Book This book takes a holistic approach for water purification. All existing technologies are reviewed and evaluated against a sustainability criterion. Based on the shortcoming of existing technoloigies and overall lifestyle, new line of technologies are proposed. These technologies are all wholly sustainable, meaning they simultaneously meet environmental, economical, and technological challenges. Such technologies are presented for three categories, namely, drinking water, agricultural use, and industrial waste management. It is shown that each of the proposed technologies has the potential to turn waste into asset, thus creating double dividend.

1.7 Organization and Introduction of the Chapters The introduction chapter (Chapter 1) introduces the readership such concepts as zero waste engineering, sustainability and others. This is followed by Chapter 2, which discusses water science. With a truly scientific approach, this chapter offers a delinearized history of water science and delineates the role of water in all aspect of life all through history. Chapter 3 (Sustainability of Current Water Purification Techniques) presents a detailed account of all major water purification techniques. Each technique is tested for its sustainability. Chapter 4 (Sustainable Drinking Water Purification Techniques) presents a discussion on what needs to be done in terms of lifestyle adjustment.

Introduction  13 This is following by the presentation of an array of sustainable technologies, all suitable for drinking water. Recommendations are made for the best options for drinking water. Chapter 5 (Sustainable Purification Techniques for Agricultural Wastes) presents a number of options for purifying agricultural waste. The possibility of deriving double dividend by adding value to the waste or by extracting minerals from the waste stream is discussed. Chapter 6 (Sustainable Purification Techniques for Industrial Wastes) presents a discussion on how to reset the current ‘technological disaster’ to a sustainable mode. It then presents several options for complete sustainability during industrial waste water treatment. A number of emerging technologies, each having tremendous commercial potentials, are presented. Chapter 7 (Summary and Conclusions) lists a summary and key conclusions from each chapters. Chapter 8 is a comprehensive bibliography and a list of references.

2 Water Science 2.1 Introduction Scientifically, water represents the most natural state of the entire universe. It is the epitome of balance between two opposites, namely, hydrogen and oxygen. In philosophical terms, water represents the balanced yin-yang state of harmony between oxygen and hydrogen. It also carries all signatures of the history of a person or an entity. This is recognized in Chinese traditional medicine, which uses the water element to track history, including the genetic makeup of a human (Dong, 2013). At the same time, water represents the ideal state of ‘calm energy’, which is reflected in its resilience, lucidity, and robustness simultaneously. Figure 2.1 shows such as representation. The perfect circle containing oxygen and hydrogen elements represent natural state of water. It is no surprise that today, the most abundant element in the universe is considered to be hydrogen while the most abundant element on earth crust is oxygen. Meanwhile, 71% of Earth’s surface is covered with water. Water also exists in the atmosphere, in glaciers, and the Earth’s core (see Islam, 2020 for details). Investigating true science behind water with New Science has been a difficult preposition. It is because New Science is based on theories and ‘laws’ that are inherently spurious. Even then, numerous observations made by New Science physicists have unearthed trends that support the truly scientific background of nature, including water. For instance, water is considered to be the main carrier of oxygen, and as such designated to be a tracer of the origin and the evolution mechanisms of cosmic entities. Today, for temperate, terrestrial planets, the presence of water is considered to be of great importance as an indicator of habitable conditions (Tsiaras et al., 2019). On the other hand, describing water properties or attempting to characterize water with New Science has created great chaos. With ‘laws’ governing any other fluids, water comes across as an anomaly to every rule. Everything about water is so unique it is perceived as chaotic or ‘weird’ M. Safiur Rahman and M.R. Islam. Sustainable Water Purification, (15–58) © 2020 Scrivener Publishing LLC

15

16  Sustainable Water Purification

Energy Water

Oxygen Hydrogen

Figure 2.1  Sustainability implies natural balance between water and energy as well as unaltered state of water.

by scientists (Jha, 2015). Islam et al. (2010) deconstructed currently used density and viscosity models and showed that the none of these models is suitable for describing water properties. Khan and Islam (2016) showed that quantum theories that have long been trusted to describe all material properties are inherently flawed and by nom means any improvement over Newtonian models. The inadequacy of existing models in capturing water properties goes far beyond semantic. If any of these properties that deviate starkly from conventional fluids were missing, the entire no life on earth would survive. Grand design or not, water is uniquely suited for sustenance of life on earth. Water defines the natural state of matter and as such any material that doesn’t have water as the starting point is considered to be artificial and as such become a threat to environmental integrity.

2.2 Unique Features of Water Both philosophically and scientifically water is the most unique material on earth and arguably in the universe. There can be no life without water. Even in bulk form, more than half of every biological cell is water. Table 2.1 show various unique features of water. One important distinction of these features is that each of them makes water uniquely

Water Science  17 Table 2.1  H2O is more cohesive than H2S, despite their similar structures, because water forms hydrogen bonds. Property

H2O

H2S

molar mass [g mol–1]

18.015

34.081

boiling pointa [K]

373.12

212.85

melting pointa [K]

273.15

187.45

enthalpy of vaporizationb [kJ mol–1]

40.657

18.622

entropy of vaporizationb [J mol–1 K–1]

108.95

87.9

critical temperature [K]

647.1

373.2

critical pressure [MPa]

22.06

8.94

critical molar volume [cm3 mol–1]

55.9

98.5

critical density [kg m–3]

322

347

critical compressibility

0.229

0.284

specific heat capacityc (CV) [J mol–1 K–1]

74.539

26

specific heat capacityc (Cp) [J mol–1 K–1]

75.3

34.6

At 101.3 kPa. At boiling. c At 25 °C and 101.3 kPa. a

b

suitable for sustaining life and in fact human lives. Water has extreme qualities as a solvent, reactant, product, catalyst, chaperone, messenger, and controller (Brini et al., 2017). With those pivotal roles, each item of water uniqueness qualities (see Table 2.2) is pivotal to forming the biomolecular structure and driving all functions of a living system. They are dominant forces in the folding of proteins and nucleic acids, the partitioning of solutes across membranes, and the binding of metabolites and drugs to biomolecules. Specific water molecules often play critical roles in biological mechanisms. Modeling such a convoluted system has been a daunting task and modern tools have proven to be largely inadequate, even when the most sophisticated tools are used (Habershon et al. 2009). Life depends on the solubility of gases in water. Humanity depends on sea life for food, and they require conditions under which oxygen

Other fluids

Monotonous relationship

Always higher than liquid phase

Phase behavior congruent with their molecular weight

Cold liquid freezes faster than hot liquid

Property/ functions

Densitytemperature

Solid phase density

Phase behavior

Phase change

Table 2.2  Unique properties of water.

Hot water freezes faster than cold water

Anomalously linked to molecular weight, which is very light

Always lower than liquid phase

Parabolic, with optimum at 4C

Water

(Continued)

Any other matter would vaporize entirely. For instance, Hydrogen sulphide (H2S) is a gas, even though it is twice the molecular weight of water. Other similar-sized molecules, such as, ammonia (NH3) are also gases.

Key to ice floating on water, otherwise life could not be sustained

Essential feature for sustaining aquatic lives. This also helps water to seep through cracks under cycles of freeze and thaw

Comment

18  Sustainable Water Purification

moderate

Limited reactivity

Surface tension

Reaction

Longest memory cycle

Memory

Geologic time, ice age, hot spill, flood

Necessary for sustaining life under both arid and arctic conditions

All phases unusual, ice conductivity order of magnitude higher than corresponding polymer, more so for ice nanotubes

Thermal conductivity

Limited memory effect

Describes natural state and state of purity, depending on

Necessary for capillary action for plants

Unique combination of fire water yin yang in solid ‘ice’ form

Ideal carrier

Comment

Reacts with every material, although not all are detectable with New Science

Very high

Hydrate in abundance

Absent

Gas solid crystal

Water Ubiquitous solvent

Other fluids

Solubility

Property/ functions

Table 2.2  Unique properties of water. (Continued)

Water Science  19

20  Sustainable Water Purification (O2) has sufficient solubility in water. Marine plants require carbon dioxide (CO2), which must be dissolved in water, in order for photosynthesis to produce carbohydrates, which releases oxygen. Gas solubility in water depends on temperature, pressure, and salinity. Here the role of carbon is essential and complimentary, justifying the water carbon yin-yang structure (Figure 2.2). Note that this representation cannot be sustained with atomic representation of elements, because atomic theory imposes artificial boundary around ‘atoms’. In reality, no such structure exits. As a result, Islam (2014) represented with the galaxy model, which offers continuity among all ‘particles’ within a matter. As such, this figure is a scientific representation of two entities with opposite but complimentary properties. This goes beyond carbon and spills into the realm of hydrocarbon or oil, characterized as ‘hydrophobes’. This point has to be elaborated. A longstanding mixing rule is: “like dissolves like”. In general, when two species A and B are combined in a mixture, the AA and BB attractions tend to be stronger than the AB attractions. The fact that oil and water often do not mix is consistent with this rule. However, here again, the uniqueness of water comes into play. In systems other than water/oil, immiscibility is attributed to energies. For oil and water, the thermodynamic signature of the immiscibility (at room temperature) is entropic. This is manifested in the different temperature dependences of solvation, as manifested in Figure 2.3. This figure shows how the entropy, enthalpy, and free energy depend on temperature when dissolving toluene in water. Interestingly, even though the entropy and enthalpy of aqueous solvation of nonpolar solutes change substantially with temperature, the solvation free energy is relatively independent of temperature. This in itself is a unique feature of water. Dissolving oil is entropically favorable in hot water, but entropically unfavorable in cold water. For toluene in water. The solvation free energy

Carbon Water

Figure 2.2  Water carbon yin-yang.

Water Science  21

E / kJ mol–1

0 ∆G

–15

T∆S

–30 ∆H

–45 0

40

T/ °C

80

120

Figure 2.3  Energy at various temperatures.

depends little on temperature. The enthalpy and entropy depend more strongly on temperature, and they compensate. In cold water, the solute induces more ordering than in bulk waters, and the cages have good H-bond and solute interactions. In hot water, insertion of oil breaks potential water–water hydrogen bonds, leading to both higher entropies and higher enthalpies. More will be discussed in the next section. Water structure and explanation of aqueous solvation have caused intrigue for centuries. Atomic theory views liquid water as an ensemble of cage-like structures, not a single ice-like structure. Cold water has more population of open-cage states. Introducing a small hydrophobic particle shifts the equilibrium further toward these more open and ordered states, and water has slower dynamics in the first few solvation shells. Hotter water has less cage-like organization. Therefore, introducing a solute into hot water acts more like conventional “like-dissolveslike” situations, for which the solute insertion into water is unfavorable for energetic reasons. The solubilities of nonpolar molecules depend on their sizes. Consider a series of nonpolar solutes in water, having increasing radii. They will induce first-shell water structuring that differs depending on the solute size; see Figure 2.4. Such assumptions are not necessary if one uses the galaxy model, proposed by Islam (2014). This model describes this process as equivalent to merger of two galaxies in which each of them has numerous components with respective natural frequencies. However, after the merger occurs

22  Sustainable Water Purification

Figure 2.4  A small solute is compatible with water’s natural cages. A large solute does not fit in a cage. In cold water, small solutes can fit in the available cavities with minimal perturbation of the water structure. This process is favored by enthalpy and opposed by entropy. However, in cold water, big solutes do not fit in preexisting cavities. First, shell solvating water molecules around large nonpolar solutes are more disordered. Dissolving large solutes in cold water is opposed by enthalpy (breaks hydrogen bonds) and favored by entropy.

Number of particles

Proton Higgs Boson quark electron proton dust specks boulders moons

planets

Sun

Galaxy

Particle size

Figure 2.5  Number of particles vs particle size.

Water Science  23

Figure 2.6  Colors and wave lengths of visible light.

Radio waves

Infrared

700 Nm Red

550 Nm Yellow

400 Nm to 700 Nm

Long Wavelengths

Visible Light Spectrum

500 Nm Green

450 Nm Blue

400 NM Violet

X Rays

100-800 NmUltraViolet

Gamma Rays

Cosmic Rays

Short Wavelengths

(physical or chemical), the resulting products have a frequency that is different from previous ones. If each particle is tagged, this model can help track a natural process apart from an artificial process. Figure 2.5 shows how this model casts the number of particles with their respective numbers in a natural system. Here, no distinction is made between light particle and mass particle as imposing such a distinction is contrary to natural order and renders the model aphenomenal. This depiction is equally valid in describing energy balance as well as mass balance, as the boundary between mass fundamental particle and energy ‘particles’ is removed. As such Figure 2.5 can also represent any natural flame will have a smooth spectrum as shown in the spectrum of the sunlight. Any alteration of light source would create a spectrum that is not natural, hence harmful. Figure 2.5 also indicates that photon emission is similar to any other radiation from a body of mass. This emission within the visible wavelengths is related to the existence of a flame. Even though a flame is typical of visible light emission, most recent theories indicate the presence of continuous emission throughout the entire spectrum. Light in the blue spectrum may also be a little stronger to allow the carotenes and xanthophylls to absorb more light as well. Figure 2.6 shows the existence of these wavelengths in visible light. Of importance in the above graph, Figure 2.7 is the notion that artificial rays are harmful at all times. As the exposure is increased, the harm is accentuated. For the short-term, artificial light visible light is less harmful than artificial non-visible rays (e.g. gamma ray, X-ray, etc.) on both sides of the spectrum (both long wavelengths and short ones). The reason for such behavior has been discussed by Khan and Islam (2016) and will be discussed later in this section. The above graph follows the same broad form as the wavelength spectrum of visible sunlight (Figure 2.8). Figure 2.9 recasts visible colors on intensity of solar radiation for the visible light section. This figure confirms that green vegetation should be the

24  Sustainable Water Purification Degree of benefit/necessity

Blue violet

Green

Ultraviolet

Yellow Orange Bright red Dark red Infra red microwave radio wave

X-ray Gamma ray

1/frequency of characteristic wavelength Blue violet

Green

Ultraviolet

Yellow Orange Bright red Dark red Infra red microwave radio wave

X-ray Gamma ray

Degree of harm/vulnerability

Figure 2.7  Artificial and natural lights affect natural material differently. (From Islam et al., 2015).

4500

Intensity (counts)

4000 3500 3000 2500 2000 1500 1000 500 0 400

450

500

550

600

650

700

750

Wavelength (nm)

Figure 2.8  Wavelength spectrum of visible part of sunlight. (From Islam et al., 2015).

Intensity (counts)

Water Science  25 4500 4000 3500 3000 2500 2000 1500 1000 500 0 400

450

500

550

600

650

700

750

Wavelength (nm)

Figure 2.9  Visible natural colors as a function of various wavelengths and intensity of sunlight. (From Islam et al., 2015).

most abundant color on earth for which the sun is the only natural source of energy. This figure also shows the area under the intensity-wavelength curve is the greatest for green materials. Red has longer wavelength but their intensity in sunlight is much smaller than green lights. If sunlight represents the original and the most beneficial energy source, any natural process emerging from sunlight will become beneficial. Such energy system is in harmony with water in its natural state. New science defines the potential of mean force (PMF) as the free energy of bringing two particles together in a solvent from a large original distance apart. Figure 2.10 shows the PMF of two hydrophobic (in this case oil) spheres in water. This curve manifests oscillatory behavior. The first minimum represents the free energy of the two particles brought into direct contact. This configuration is favorable because the direct-contact state minimizes the total water-accessible surface of the two hydrophobes, w(r) r

Figure 2.10  Water is structured differently around two hydrophobes at different separations. The PMF is the reversible work spent to bring two hydrophobic particles from infinite distance to the distance r. (Redrawn from Brini et al., 2017).

26  Sustainable Water Purification relative to all other separations. Under such conditions, this can onset follow up events, with subsequent minima forming ‘cells’ within water’s caging structure. The unique aspect of water here is its ability to form cage structures, causing the solvent-separated state to be relatively stable for some hydrophobes. The tetrahedral hydrogen bonding organization of water itself is considered to be a unique feature of water. In classical terms, the collective interactions between water molecules can be represented by (i) a radial dispersion attraction with steric repulsion at short-range and (ii) electrostatic interactions between spatially localized groupings of charge. In this way, hydrogen bonding is a consequence of these localized electrostatic interactions leading to nearly tetrahedral arrangement of surrounding water molecules. While this description itself has a number of assumptions imbedded to it, such description begins to show how water is unique. This explains the difficulty encountered throughout history to describe water behaviour with a comprehensive model. Also important for biology are water’s surface tension and capillary action. As stated in Table 2.2, surface tension is yet another unique feature of water. Attributed to the relatively high attraction of water molecules to each other through a web of hydrogen bonds, water has a higher surface tension (72.8 mN/m at 20 °C) than most other liquids. Surface tension is an important factor in the phenomenon of capillarity. Because most solids are water-wet, meaning the contact angle is less than 90o, leads to high capillary pressure. The heights and branching of trees depends on water’s capillary action. Due to an interplay of the forces of adhesion and surface tension, water exhibits capillary action whereby water rises into a narrow tube against the force of gravity. Adhesion is another unique feature of water. Water adheres to the inside wall of the tube and surface tension tends to straighten the surface causing a surface rise and more water is imbibed up through cohesion. The process continues as the water flows up the tube until there is enough water such that gravity balances the adhesive force. For example, when water is carried through xylem up stems in plants, the strong intermolecular attractions (cohesion) hold the water column together and adhesive properties maintain the water attachment to the xylem and prevent tension rupture caused by transpiration pull. This is instrumental for proper functioning of trees. In solid form, it is less dense still, which is why standard ice floats on water. That is one reason why life on Earth has flourished—if ice were denser than water, lakes and oceans would freeze from the bottom

Water Science  27 up, almost certainly preventing the kind of chemistry that makes life possible. Liquid water tends to be a more cohesive than other simple liquids. This is typically explained by stating that water–water attractions arise from hydrogen bonding in addition to van der Waals interactions that are typical in simpler liquids. For example, a higher temperature is required to melt ice than to melt solids of simple liquids. And, a higher temperature is required to boil liquid water than to boil other simpler liquids. In addition, water has a relatively high surface tension, of 72.8 mN m–1 at room temperature, due to its high cohesion, the highest of the common nonionic, nonmetallic liquids. Brini et al. (2017) presented an interesting comparison between water and hydrogen sulphide (H2S). Atomic theory tells us that these two have have similar atomic structures. Both have sp3 hybridized orbitals, with bond angles (of HOH and HSH) being 104.45° and 92.1°, respectively. Oxygen and sulfur belong to the same group of the periodic table. However, because sulfur has twice as many electrons as oxygen, it is larger and less electronegative. Therefore, the O–H bond is much more polar than the S–H bond. Even though H2S has almost twice the molar mass of H2O, it is a gas at room temperature and pressure, while H2O is a liquid, indicating greater cohesion in water. Water has a higher melting point, boiling point, and heat of vaporization, as well as a higher heat capacity (which reflects the higher capability for storing thermal energy through these additional types of bonds). While these features are attributed to hydrogen bonding, they speak of unique nature of water. The unique aspects of water properties cannot be captured with tangible qualities. In order to capture the properties as well as water-energy nexus, the term ‘water energetics’ has been introduced (Vassiliev et al., 2012). Brini et al. (2017) presented a useful way to compare the energetics of water and other materials is with an energy ladder. It is shown in Figure 2.11. The left figure shows the ladder for other materials whereas the figure to the right shows that of water. The lowest-energy state of a conventional material is the solid. Introducing energy (e.g. by raising temperature) melts the solid, leading to fewer weaker, more disordered van der Waals interactions in the liquid state. Introducing even more energy breaks the remaining van der Waals contacts, boiling the liquid. The right figure of Figure 2.11 shows that the melting temperature of water is higher than that for the liquid on the left. This in part is explained by the existence of tetrahedral hydrogen bonds. On the other hand the higher boiling point of water is explained by higher

28  Sustainable Water Purification Energy Energy

Steam

Gas Hot water Liquid Cold water Solid Simple Material

Ice Water

Figure 2.11  Energy–volume relationship of water, vs simpler materials. (left) Simple materials (cold) achieve low energies by tight-binding into solids, (warmer) achieve higher energies by forming looser liquid states, and (hot) achieve the highest energies when most bonds are broken in the gas phase. The black bars indicate transitions: heating melts the solid, then boils the liquid. (right) Water (very cold, ice) achieves its lowest energies through open low-density hydrogen bonded structures, (cold liquid water) achieves intermediate energies through some breakage of cages, leading to increased density, (hot liquid water) achieves higher energies by breakage of more bonds, leading to looser liquid, and (hot) achieves its highest energies, like simpler materials, by breaking most bonds, to reach the low-density gas phase. (Redrawn from Brini et al., 2017).

cohesion of water. This figure also shows the nature of the two states of liquid water: that cold water tends to retain a little more cage-like, icelike structure and hot water tends to retain less of it. Water shows further ‘anomalies’ compared to other matter. The so-called Mpemba effect is the observation that warm water freezes more quickly than cold water. The effect has been measured on many occasions with many explanations put forward. One idea is that warm containers make better thermal contact with a refrigerator and so conduct heat more efficiently. Hence the faster freezing. Another is that warm water evaporates rapidly and since this is an endothermic process, it cools the water making it freeze more quickly. Others have attempted to the Mpemba ‘paradox’ with unique properties of the different bonds that hold water together. However, none of these explanations are entirely convincing. Lasanta, A. et al. (2017) analyzed a simplified version of the bulk property evaluation of the Mpemba effect. In this experiment, the particles in the liquid are miniscule spheres that lose a tiny bit of energy each time they collide with one another. The conventional wisdom is that the time it takes for each beaker of water to freeze depends only on its initial temperature.

Water Science  29 Particles in the hotter water move faster, which means they have more slowing to do – so the hotter the liquid, the longer it should take. They discovered that the Mpemba effect is present in granular fluids, both in uniformly heated and in freely cooling systems. In both cases, the system remains homogeneous, and no phase transition is present. Analytical quantitative predictions are given for how differently the system must be initially prepared to observe the Mpemba effect. They followed up with developing models that use both molecular dynamics and Monte Carlo simulation. The Mpemba effect is demonstrated in Figure 2.12. The Leidenfrost effect is yet another unique feature of water. This effect can make beads of liquid float above a hot surface (Shirota et al., 2016). This phenomenon is known as the Leidenfrost effect, after the 18th-­century German doctor who first described it. The bottom layer of the droplet that touches the hot surface does indeed evaporate, but then it forms a thin cushion of vapour that temporarily protects the rest of the droplet from the extreme heat. This keeps the rest from becoming vapour and lets the droplet move around the hot plate with ease. When a liquid droplet impacts a hot solid surface, enough vapor may be generated under it as to prevent its contact with the solid. The minimum solid temperature for this so-called Leidenfrost effect to occur is termed the Leidenfrost temperature, or the dynamic Leidenfrost temperature when the droplet velocity is non-­negligible. Shirota et al. (2016) observed the wetting/drying and the levitation dynamics of the droplet impacting on an (isothermal) smooth sapphire surface using high speed total internal reflection imaging, which enabled them to observe the droplet base up to about 100 nm above the substrate surface. By this method they were able to reveal the processes responsible for the transitional regime between the fully wetting and the fully levitated droplet as the solid temperature increases, thus shedding light on the characteristic time- and lengthscales setting the dynamic Leidenfrost temperature for droplet impact on an isothermal substrate. Heat conductivity sets water apart from other matters, in all three phases. This effect is further accentuated for nanotubes and ice. Guo et  al. (2010) compared the calculated thermal conductivity values of Ice-NTs with the experimental ones of ices Ih and XI, both of which have the highest thermal conductivity values among the bulk ices in the simulation temperature region. As one can see in Figure 2.13, a distinctly larger thermal conductivity of IceNTs than that of the bulk ices was observed. Their results show the unusually high thermal conductivity of Ice-NTs, which was attributed to their unique 1D proton-ordered structures and thus the phonon dispersions.

30  Sustainable Water Purification 20

*

Gas present

Time of freezing, min

* 15

*

No gas

* *

10

* * *

5 0 290

*

* *

310 330 350 Start temperature, K

370

Figure 2.12  Paradoxical behavior of water (from Woijciechowski et al.). 21

ice XI, exp28,29 ice lh, exp28,29 (6,0) Ice-NT (5,0) Ice-NT (4,0) Ice-NT

18

K(W/mk)

15 12 9 6 3 40

60

80

100 120 140 160

Temperature(K)

Figure 2.13  Temperature dependence of thermal conductivity of isolated (4, 0), (5, 0), and (6, 0) Ice-NTs in comparison to experimental results of ices Ih and XI. The thermal conductivity of the Ice-NTs is sensitive to the temperature and tube diameter, but insensitive to the polarization. The Ice-NTs have distinctly higher thermal conductivity than that of the bulk ices.

Figure 2.13 shows the temperature dependence of thermal conductivity of (4, 0), (5, 0), and (6, 0) Ice-NTs with infinite length (from 50 to 150 K). Tables 2.3 and 2.4 show various thermal properties of water. Note specific thermal properties that are unique for water.

Water Science  31 Table 2.3  Thermal properties of ice (Website 1). Thermal conductivity - k (W/mK) other units

Specific heat - cp (kJ/kgK)

Temperature -t(oC)

Density -ρ(kg/m3)

0.01 (Water)

999.8

0

916.2

2.22

2.050

-5

917.5

2.25

2.027

-10

918.9

2.30

2.000

-15

919.4

2.34

1.972

-20

919.4

2.39

1.943

-25

919.6

2.45

1.913

-30

920.0

2.50

1.882

-35

920.4

2.57

1.851

-40

920.8

2.63

1.818

-50

921.6

2.76

1.751

-60

922.4

2.90

1.681

-70

923.3

3.05

1.609

-80

924.1

3.19

1.536

-90

924.9

3.34

1.463

-100

925.7

3.48

1.389

Officially water at 0 °C is ice.

2.3 Natural State of Matter This series of work outlines fundamental features of nature and shows there can be only two options: natural (true) or artificial (false). They show that Aristotle’s logic of anything being ‘either A or not-A’ is useful only to discern between true (real) and false (artificial). In order to ensure the end being real, they introduce the recently developed criterion of Khan

2.06 10-37 3.31 10-24 9 10-10

-150

Vapour pressure (Pa abs)

-200

-220

Temperature (oC)

Table 2.4  Vapour pressure ice. -90

-80

-70

-60

0.0014 0.0097 0.055 0.261 1.08

-100 3.94

-50

-30

12.84 38

-40

-10

-5

-0.01 103.2 259.9 401.7 611.7

-20

32  Sustainable Water Purification

Water Science  33 (2006) and Khan and Islam (2007a). If something is convergent when time is extended to infinity, the end is assured to be real. In fact, if this criterion is used, one can be spared of questioning the ‘intention’ of an action. If any doubt, one should simply investigate where the activity will end up if time, t goes to infinity. The inclusion of real (phenomenal) pathway would ensure the process is sustainable or inherently phenomenal. Khan and Islam (2007a) described the characteristic features of Nature. This is listed in modified form in Table 2.5. This table lists the inherent nature of natural and artificial products. It is important to note that the left hand side statements are true – not in the tangible sense of being “verifiable”, but because there is no counter-example of those statements. The left hand side of Table 2.5 shows the characteristic features of Nature. These are true features and are not based on perception. Each is true insofar as no example of the opposite has been sustained. It is important to note that the following table describes everything in existence as part of universal order and applies to everything internal, including time, and human thought material (HTM). However, the source of HTM, i.e., intention, forms no part of these features. At the same time, all the properties stated on the right-hand side, which assert the first premise of all “engineered products”, are aphenomenal, they are only true for a time period approaching zero, resulting in being “verifiable” only when the standard itself is fabricated. In other words, every statement on the right-hand side only refers to something that does not exist. For instance, honey molecules are considered to be extremely complex. They are complex because they have components that are not present in other products, such as sugar, which is identified as made up of “simple” molecules. Why are sugar molecules simple? Because, by definition, they are made of the known structures of carbon and hydrogen. This process is further obscured by yet another post-Renaissance misconception, “whatever cannot be seen, does not exist” (Islam et al., 2012), which is similar to the principle of “dilution is the solution to pollution” that has governed both regulatory agencies and other environmental industries in the post-Renaissance world. A further review of Table 2.5 now will indicate how every item on the right-hand side is actually a matter of definition and a false premise. If one considers the features of artificial products in Table 2.5 with those of Table 2.6, it becomes clear that any science that would “prove” the features (based on a false premise) in Table 2.5 is inherently spurious. However, the science of tangibles does exactly that and discards all natural processes as “pseudoscience”, “conspiracy theory”, etc. This also shows that

34  Sustainable Water Purification Table 2.5  Typical features of natural processes as compared to the claims of artificial processes (from Islam et al., 2015). Feature no.

Feature of natural

Feature of artificial

1

Complex

Simple

2

Chaotic

Ordered

3

Unpredictable

Predictable

4

Unique (every component is different), i.e., forms may appear similar or even “self-similar”, but their contents alter with passage of time

Normal

5

Productive

Reproductive

6

Non-symmetric, i.e., forms may appear similar or even “self-similar”, but their contents alter with passage of time

Symmetric

7

Non-uniform, i.e., forms may appear similar or even “self-similar”, but their contents alter with passage of time

Uniform

8

Heterogeneous, diverse, i.e., forms may appear similar or even “self-similar”, but their contents alter with passage of time

Homogeneous

9

Internal

External

10

Anisotropic

Isotropic

11

Bottom-up

Top-down

12

Multifunctional

Unifunctional

13

Dynamic

Static

14

Irreversible

Reversible

15

Open system

Closed system

16

True

Artificial

17

Self healing

Self destructive

18

Nonlinear

Linear (Continued)

Water Science  35 Table 2.5  Typical features of natural processes as compared to the claims of artificial processes (from Islam et al., 2015). (Continued) Feature no.

Feature of natural

Feature of artificial

19

Multi-dimensional

Uni-dimentional

20

Zero degree of freedom*

Finite degree of freedom

21

Non-trainable

Trainable

22

Continuous function of space, without boundary

Discrete

23

Intangible

Tangible

24

Open

Closed

25

Flexible

Rigid

26

Continuous function of time

Discrete function of time

27

Balanced

Inherently unstable

*With the exception of humans that have freedom of intention (Islam et al., 2014).

Table 2.6  True difference between sustainable and unsustainable processes. Sustainable (Natural)

Unsustainable (Artificial)

Progressive/youth measured by the rate of change Non-progressive/ resists change

Conservative/youth measured by departure from natural state

Unlimited adaptability and flexibility

Zero-adaptability and inflexible

Increasingly self evident with time

Increasingly difficult to cover up aphenomenal source

100% efficient

Efficiency approaches zero as processing is increased

Can never be proven to be unsustainable

Unsustainability unravels itself with time

36  Sustainable Water Purification the current engineering practices that rely on false premises are inherently unsustainable. The case in point can be derived from any theories or “laws” advanced by Bernoulli, Newton (regarding gravity, calculus, motion, viscosity), Dalton, Boyle, Charles, Lavoisier, Kelvin, Poiseuille, Gibbs, Helmholz, Planck and others who served as the pioneers of modern science. Each of their theories and laws had in common the first assumption that would not exist in nature, either in content (tangible) or in process (intangible). At this point, it is appropriate to familiarize the readership of Table 2.7 that lists the fundamental features of the external entity. The existence of Table 2.7  Features of external entity (from Islam, 2014). Feature no.

Feature

1

Absolutely external (to everything else)

2

All encompassing

3

No beginning

4

No end

5

Constant (independent of everything else)

6

Uniform

7

Alive

8

Infinity

9

Absolutely True

10

Continuous

11

All pervasive in space

12

All pervasive in time

13

Infinite degree of freedom

14

Unique

15

Open system

16

Dissimilar to everything else

17

Absolute Time that control time that controls mass

18

Absolute mass (pure light)

Water Science  37 an external entity is necessary condition in order to eliminate the notion of void that had been inherited from Atomism philosophy and was carried forward by first Thomas Aquinas and then by subsequent scientists, without exception (Islam, 2014). This external entity was first recognized as God (from the ancient Greek philosophers to Avicenna and Averroes of the Islamic golden era), then conflated as plenum and aether (Islam et al., 2013; 2014). While the existence of such entities has been denied and sometime ‘proven’ to be non-­ existent, the traits of this external entity have been included in all forms of ‘fundamental’ particles, ranging from photon to the Higgs boson. In addition, such features have also been invoked in galactic models in the form of various entities, ranging from “dark matter”, “black hole” to “absolute void”. Newton introduced this as ‘external’ force and defined it as the originator of differential motion. The original Averroes concept, as supported by the Qur’an was that such originator of motion is the Creator, whose traits are all different from the traits of creation. With the first premise of ‘Nature is perfect’, any technology that conflicts with natural traits will not be sustainable.

2.4 Source of Water and Its Role in Sustaining Life Water covers 71% of the Earth’s surface, mostly in seas and oceans. Small portions of water occur as groundwater (1.7%), in the glaciers and the ice caps of Antarctica and Greenland (1.7%), and in the air as vapor, clouds (formed of ice and liquid water suspended in air), and precipitation (0.001%) (Gleick, 1993). Water plays an important role in the world economy. Approximately 70% of the freshwater used by humans goes to agriculture (Baroni et al., 2007). Fishing in salt and fresh water bodies is a major source of food for many parts of the world. Much of long-distance trade of commodities (such as oil and natural gas) and manufactured products is transported by boats through seas, rivers, lakes, and canals. Large quantities of water, ice, and steam are used for cooling and heating, in industry and homes. Water is an excellent solvent for a wide variety of substances both mineral and organic; as such it is widely used in industrial processes, and in cooking and washing. Water is also central to many sports and other forms of entertainment, such as swimming, pleasure boating, boat racing, surfing, sport fishing, diving, ice skating and skiing. Water is one of the most of the ingredient for a sustainable life process. For instance: (1) approximately 65% of our body mass is made up of fluid,

38  Sustainable Water Purification including skin, tissues, cells and the organs, (2) water avoids dehydration (dehydration is a condition where the body does not have enough water to guide many functions), (3) water helps to remove some ingredients from the body like toxins and waste items from the body, via cleansing it, (4) water generally an important term that proceeds all the nutrients and we eat and carry the digest nutrients into the cells by circulating with from the lymphatic systems, (5) water can help to overcome several health problems: constipation, asthma, allergy, hypertension, migraine and many more.

2.4.1 Inorganic Minerals This group of contaminants includes the minerals and toxic metals. Some of these contaminants, like calcium and magnesium are naturally occurring. Others like copper and lead usually get into the water from pipes. Some of these contaminants such as lead and arsenic can be quite dangerous. However, this types of contaminant enter the water system via one certain, identifiable source, such as a pipe or a ditch. This type of contamination source includes municipal sewage systems and industrial and construction sites. Table 2.8 lists various contaminants and their pathways. Following is a discussion of various contaminants. Arsenic: Arsenic is notorious as a toxic element. Its toxicity, however, depends on the chemical (valency) and physical form of the compound, the route by which it enters the body, the dose and duration of exposure and several other biological parameters. It is recommended that, when water is found to contain arsenic at levels of 0.05 ppm, an attempt should be made to ascertain the valency and chemical forms of the element. Arsenic is commonly associated as an alloying additive with lead solder, lead shot, battery grids, cable sheaths and boiler piping. Nowadays, most arsenic originates from paints or pharmaceuticals and is commonly found in sewage. The concentration of arsenic in sea water is around 0.002 ppm. The primary concerns are carcinogenicity and mutagenicity. Silver: Silver occurs naturally in elemental form and as various ores. It is also associated with lead, copper and zinc ores. Because some metals such as lead and zinc are used in distribution systems and also because in some countries silver oxide is used to disinfect water supplies, silver levels in tap water may sometimes be elevated. The levels of silver in drinking water should not exceed 1 ppb. In industry, silver is used in the manufacture of silver nitrate, silver bromide and other photographic chemicals, water distillation equipment, mirrors, silver plating equipment, special batteries, table cutlery, jewe­ lry, dental medical and scientific equipment including amalgams.

Water Science  39 Cadmium: Cadmium is widely distributed in the Earth’s crust, but is particularly associated with zinc and copper and is produced commercially only as a by-product of zinc smelting. Cadmium shows no signs of being an essential trace element in biological processes; on the contrary, it is highly toxic to the human organism. Like mercury, cadmium and its compounds enter the environment only from geological or human activities (metal mining, smelting and fossil fuel combustion). Cadmium and its compounds are black-listed materials, which by international agreement may not be discharged or dumped into the environment. Cadmium is a cumulative poison and a maximum level of 0.005 ppm is permitted for drinking water. Chromium: Most rocks and soils contain small amounts of chromium. Chromium in its naturally occurring state is in a highly insoluble form; however, most of the more common soluble forms found in soils are mainly the result of contamination by industrial emissions. The major uses of chromium are for chrome alloys, chrome plating, oxidising agents, corrosion inhibitors, pigments for the textile glass and ceramic industries as well as in photography. Hexavalent chromium compounds (soluble) are carcinogenic and the guideline value is 0.05 ppm. Lead: Lead is not only the most abundant of heavy metals occurring in nature, it was also one of the first metals used on a large scale by man. Although it is not a nutritionally essential element, its monitoring is important because of its toxicity to human health. Lead is a cumulative poison. Most of the lead produced in metallic form, in batteries, cable sheathing, sheets and pipes, etc., is recovered and recycled, but most lead used in compound form, like paints and petrol additives is lost to the environment, eventually ending up in the aquatic environment. Lead compounds, similar to the ones used in petrol additives are reportedly being used in the production of mercurial fungicides. The presence of lead in drinking water is limited to 0.01 ppm. Mercury: Although a comparatively rare element, mercury is ubiquitous in the environment, the result of natural geological activity and man-made pollution. Mercury from natural sources can enter the aquatic environment via weathering, dissolution and biological processes. Although extremely useful to man, mercury is also highly toxic to the human organism, especially in the form of methyl mercury, because it cannot be excreted and therefore acts as a cumulative poison. The potential for long-term human health hazards from ingesting mercurycontaminated fish has led several nations to establish regulations and guidelines for allowable sea-food mercury levels. Nearly all levels above

40  Sustainable Water Purification 1 ppb in water are due to industrial effluents connected with chlorine and caustic soda production, pharmaceuticals, mirror coatings, mercury lamps and certain fungicides. Nickel: Nickel is ubiquitous in the environment. Nickel is almost certainly essential for animal nutrition, and consequently it is probably essential to man. Nickel is a relatively non-toxic element; however, certain nickel compounds have been shown to be carcinogenic in animal experiments. Tin: Tin and its compounds are significant and controversial chemicals in the environment. As is the case with other elements, not all chemical forms of tin are equally biologically active. In contrast to the low toxicity of inorganic tin (derived from eating canned foods), some organic tin compounds, also known as organotins, are toxic. Tributyltin and Triphenyltin, constituents of anti-fouling paints, are highly toxic and their presence in harbour waters is limited generally to 0.002 and 0.008 ppb respectively. In many countries, organotin anti-fouling paints are not allowed on vessels less than 25 metres long, and the start of a fishing season generally sees an increase of this compound in the water as freshly painted vessels are launched back into the water. Copper: The presence of Copper in the water supply, although not constituting a hazard to health, may interfere with the intended domestic uses of water. Copper enhances corrosion of aluminium and zinc fittings, stains clothes and plumbing fixtures. Copper is used in alloys, as a catalyst, in anti-fouling paints and as a wood preservative. Urban sewage contains substantial amounts of copper. The human taste threshold for copper is low, 5.0 - 7.0 ppm, and the taste is repulsive. The limit for drinking water is 1.0 ppm. Iron: The presence of Iron in drinking water is objectionable for a number of reasons unrelated to health. Under the pH conditions existing in drinking water supplies, ferrous salts are unstable and precipitate as insoluble ferric hydroxide, which settles out as rusty silt. Such water tastes unpalatable, promotes the growth of “iron bacteria” and the silt gradually reduces the flow of water in the piping. The recommended guideline level of iron in water is 0.3 ppm. Manganese: Anaerobic groundwater often contains elevated levels of dissolved manganese. The presence of Manganese in drinking water is objectionable for a number of reasons unrelated to health. At concentrations exceeding 0.15 ppm Manganese imparts an undesirable taste to beverages and stains plumbing fixtures. The recommended value is 0.1 ppm.

Occurs naturally in some rocks and drainage from mines.

Enters environment from natural weathering, industrial production, municipal waste disposal, and manufacturing of flame retardants, ceramics, glass, batteries, fireworks, and explosives.

Enters environment from natural processes, industrial activities, pesticides, and industrial waste, smelting of copper, lead, and zinc ore.

Occurs naturally in some limestones, sandstones, and soils in the eastern United States.

Aluminum

Antimony

Arsenic

Barium

Can cause a variety of cardiac, gastrointestinal, and neuromuscular effects. Associated with hypertension and cardiotoxicity in animals.

Causes acute and chronic toxicity, liver and kidney damage; decreases blood hemoglobin. A carcinogen.

Decreases longevity, alters blood levels of glucose and cholesterol in laboratory animals exposed at high levels over their lifetime.

Can precipitate out of water after treatment, causing increased turbidity or discolored water.

Potential health and other effects

(Continued)

Sources to groundwater

Contaminant

Inorganic contaminants found in groundwater

Table 2.8  Inorganic contaminants found in groundwater.

Water Science  41

Occurs naturally in soils, groundwater, and surface water. Often used in electrical industry equipment and components, nuclear power and space industry. Enters the environment from mining operations, processing plants, and improper waste disposal. Found in low concentrations in rocks, coal, and petroleum and enters the ground and

Found in low concentrations in rocks, coal, and petroleum and enters the groundwater and surface water when dissolved by acidic waters. May enter the environment from industrial discharge, mining waste, metal plating, water pipes, batteries, paints and pigments, plastic stabilizers, and landfill leachate.

May be associated with the presence of sodium in drinking water when present in high concentrations. Often from saltwater intrusion, mineral dissolution, industrial and domestic waste.

Beryllium

Cadmium

Chloride

Deteriorates plumbing, water heaters, and municipal water-works equipment at high levels. Above secondary maximum contaminant level, taste becomes noticeable.

Replaces zinc biochemically in the body and causes high blood pressure, liver and kidney damage, and anemia. Destroys testicular tissue and red blood cells. Toxic to aquatic biota.

Causes acute and chronic toxicity; can cause damage to lungs and bones. Possible carcinogen.

Potential health and other effects

(Continued)

Sources to groundwater

Contaminant

Inorganic contaminants found in groundwater

Table 2.8  Inorganic contaminants found in groundwater. (Continued)

42  Sustainable Water Purification

Enters environment from old mining operations runoff and leaching into groundwater, fossil-fuel combustion, cement-plant emissions, mineral leaching, and waste incineration. Used in metal plating and as a cooling-tower water additive.

Enters environment from metal plating, industrial and domestic waste, mining, and mineral leaching.

Often used in electroplating, steel processing, plastics, synthetic fabrics, and fertilizer production; also from improper waste disposal.

Occur naturally but also enters environment from man-made sources such as landfill leachate, feedlots, or sewage. A measure of the dissolved “salts” or minerals in the water. May also include some dissolved organic compounds.

Chromium

Copper

Cyanide

Dissolved solids

May have an influence on the acceptability of water in general. May be indicative of the presence of excess concentrations of specific substances not included in the Safe Water Drinking Act, which would make water objectionable. High concentrations of dissolved solids shorten the life of hot water heaters.

Poisoning is the result of damage to spleen, brain, and liver.

Can cause stomach and intestinal distress, liver and kidney damage, anemia in high doses. Imparts an adverse taste and significant staining to clothes and fixtures. Essential trace element but toxic to plants and algae at moderate levels.

Chromium III is a nutritionally essential element. Chromium VI is much more toxic than Chromium III and causes liver and kidney damage, internal hemorrhaging, respiratory damage, dermatitis, and ulcers on the skin at high concentrations.

Potential health and other effects

(Continued)

Sources to groundwater

Contaminant

Inorganic contaminants found in groundwater

Table 2.8  Inorganic contaminants found in groundwater. (Continued)

Water Science  43

Occurs naturally or as an additive to municipal water supplies; widely used in industry.

Result of metallic ions dissolved in the water; reported as concentration of calcium carbonate. Calcium carbonate is derived from dissolved limestone or discharges from operating or abandoned mines.

Occurs naturally as a mineral from sediment and rocks or from mining, industrial waste, and corroding metal.

Enters environment from industry, mining, plumbing, gasoline, coal, and as a water additive.

Fluoride

Hardness

Iron

Lead

Affects red blood cell chemistry; delays normal physical and mental development in babies and young children. Causes slight deficits in attention span, hearing, and learning in children. Can cause slight increase in blood pressure in some adults. Probable carcinogen.

Imparts a bitter astringent taste to water and a brownish color to laundered clothing and plumbing fixtures.

Decreases the lather formation of soap and increases scale formation in hot-water heaters and lowpressure boilers at high levels.

Decreases incidence of tooth decay but high levels can stain or mottle teeth. Causes crippling bone disorder (calcification of the bones and joints) at very high levels.

Potential health and other effects

(Continued)

Sources to groundwater

Contaminant

Inorganic contaminants found in groundwater

Table 2.8  Inorganic contaminants found in groundwater. (Continued)

44  Sustainable Water Purification

Damages the heart and liver of laboratory animals exposed to large amounts over their lifetime. Toxicity results from the body’s natural breakdown of nitrate to nitrite. Causes “bluebaby disease,” or methemoglobinemia, which threatens oxygencarrying capacity of the blood.

Occurs as an inorganic salt and as organic mercury compounds. Enters the environment from industrial waste, mining, pesticides, coal, electrical equipment (batteries, lamps, switches), smelting, and fossil-fuel combustion.

Occurs naturally in soils, groundwater, and surface water. Often used in electroplating, stainless steel and alloy products, mining, and refining.

Occurs naturally in mineral deposits, soils, seawater, freshwater systems, the atmosphere, and biota. More stable form of combined nitrogen in oxygenated water. Found in the highest levels in groundwater under extensively developed areas. Enters the environment from fertilizer, feedlots, and sewage.

Mercury

Nickel

Nitrate (as nitrogen)

(Continued)

Causes acute and chronic toxicity. Targets the kidneys and can cause nervous system disorders.

Causes aesthetic and economic damage, and imparts brownish stains to laundry. Affects taste of water, and causes dark brown or black stains on plumbing fixtures. Relatively non-toxic to animals but toxic to plants at high levels.

Occurs naturally as a mineral from sediment and rocks or from mining and industrial waste.

Manganese

Potential health and other effects

Sources to groundwater

Contaminant

Inorganic contaminants found in groundwater

Table 2.8  Inorganic contaminants found in groundwater. (Continued)

Water Science  45

Enters environment from fertilizer, sewage, and human or farm-animal waste.

Enters environment from naturally occurring geologic sources, sulfur, and coal.

Enters environment from ore mining and processing, product fabrication, and disposal. Often used in photography, electric and electronic equipment, sterling and electroplating, alloy, and solder. Because of great economic value of silver, recovery practices are typically used to minimize loss.

Derived geologically from leaching of surface and underground deposits of salt and decomposition of various minerals. Human activities contribute through de-icing and washing products.

Nitrite (combined nitrate/nitrite)

Selenium

Silver

Sodium

Can be a health risk factor for those individuals on a low-sodium diet.

Can cause argyria, a blue-gray coloration of the skin, mucous membranes, eyes, and organs in humans and animals with chronic exposure.

Causes acute and chronic toxic effects in animals-”blind staggers” in cattle. Nutritionally essential element at low doses but toxic at high doses.

Toxicity results from the body’s natural breakdown of nitrate to nitrite. Causes “bluebaby disease,” or methemoglobinemia, which threatens oxygencarrying capacity of the blood.

Potential health and other effects

(Continued)

Sources to groundwater

Contaminant

Inorganic contaminants found in groundwater

Table 2.8  Inorganic contaminants found in groundwater. (Continued)

46  Sustainable Water Purification

Sources to groundwater

Elevated concentrations may result from saltwater intrusion, mineral dissolution, and domestic or industrial waste.

Enters environment from soils; used in electronics, pharmaceuticals manufacturing, glass, and alloys.

Found naturally in water, most frequently in areas where it is mined. Enters environment from industrial waste, metal plating, and plumbing, and is a major component of sludge.

Contaminant

Sulfate

Thallium

Zinc

Inorganic contaminants found in groundwater

Table 2.8  Inorganic contaminants found in groundwater. (Continued)

Aids in the healing of wounds. Causes no ill health effects except in very high doses. Imparts an undesirable taste to water. Toxic to plants at high levels.  

Damages kidneys, liver, brain, and intestines in laboratory animals when given in high doses over their lifetime.

Forms hard scales on boilers and heat exchangers; can change the taste of water, and has a laxative effect in high doses.

Potential health and other effects

Water Science  47

Cause poisoning, headaches, dizziness, gastrointestinal disturbance, numbness, weakness, and cancer. Destroys nervous system, thyroid, reproductive system, liver, and kidneys. Cause cancer. Damages nervous and reproductive systems, kidney, stomach, and liver.

Enter environment as herbicides, insecticides, fungicides, rodenticides, and algicides.

Used as sealants, linings, solvents, pesticides, plasticizers, components of gasoline, disinfectant, and wood preservative. Enters the environment from improper waste disposal, leaching runoff, leaking storage tank, and industrial runoff.

Pesticides

Plasticizers, chlorinated solvents, benzo[a] pyrene, and dioxin

Can cause cancer and liver damage, anemia, gastrointestinal disorder, skin irritation, blurred vision, exhaustion, weight loss, damage to the nervous system, and respiratory tract irritation.

Enter environment when used to make plastics, dyes, rubbers, polishes, solvents, crude oil, insecticides, inks, varnishes, paints, disinfectants, gasoline products, pharmaceuticals, preservatives, spot removers, paint removers, degreasers, and many more.

Volatile organic compounds

Potential health and other effects

Sources to groundwater

Contaminant

Table 2.9  Organic contaminants found in groundwater.

48  Sustainable Water Purification

Water Science  49 Zinc: The concentration of zinc in tap water can be considerably higher than that in surface water owing to the leaching action of zinc from galvanised pipes, brass and other zinc alloys. Zinc imparts to water an undesirable astringent taste and in concentrations in excess of 5 ppm. The water may appear opalescent and develop a greasy film on boiling. Levels of zinc should be kept well below this value.

2.4.2 Organic Contaminants The term organic implies that these contaminants are carbon-based, which usually means that they are derived from petroleum. As such, the term should not be conflated with organic as in natural excretion from living organisms. New Science doesn’t distinguish between the two types and they must be treated differently as the synthetic form is inherently toxic to the environment. Because they are carbon-based, they can easily bind with human tissue, making them extremely toxic even in small fractions. To put this in perspective, inorganic contaminants are usually measured in parts per million or parts per billion, but Dioxin and PCBs for example are dangerous in parts per quintillion! Table 2.9 lists the organic chemicals, commonly found in groundwater, affected by either agricultural or industrial waste. Also shown are sources, pathways, and potential health hazards.

2.4.3 Radioactive Minerals This radioactive elemental group is really a subset of the first group and can include uranium, plutonium and radium. The dangers of these contaminants are obvious. Radioactive minerals occur irregularly in the bedrock, similar to other minerals such as iron, arsenic and quartz. Radionuclides dissolve easily in water. The U.S. Environmental Protection Agency (EPA) sets drinking water standards and has determined that certain radioactive minerals as specified above are a health concern. Exposure to radioactivity increases one’s risk of various cancers. Other sources of radioactivity in the environment include x rays, radiation from the sun, foods from plants that concentrate radioactivity as they grow, fluorescent watch dials, and many other sources. At lower exposures, the risk of cancer is reduced. The principal health concerns associated with regulated radionuclides in water include: radon gas increases the risk of lung cancer; uranium increases toxicity risk to the kidneys; and radium increases one’s risk of bone cancer. However, the standards for the permissible amount of radioactivity in drinking water are called maximum contaminant levels (MCLs). EPA finalized new health standards for radioactivity in drinking water for public water systems in

50  Sustainable Water Purification 2000. Additional revisions to these MCLs may be proposed by 2005-2006. The following is a summary of the current mineral radionuclide MCLs. Test name

Radiation type

EPA Standards

Radon

Alpha

Proposed 300/4, 000 pCi/L (CGR 11/99)

Compliance Gross Alpha*

Alpha

15 pCi/L **

Uranium

Alpha

30 ug/L (approximately 20 pCi/L)***

{Radium 226

Alpha

}

{Radium 228

Beta

} Total of 226 & 228 = 5 pCi/L

Beta

Beta

4 milirems per year

*Compliance gross alpha equals the concentration of analytical gross alpha (in pCi/L) minus the concentration of uranium (in pCi/L) **pCi/L (picocuries per liter) ***micrograms per liter (ug/L) can be converted to pCi/L by multiplying the U (ug/L) by 0.67. CFR = Code of Federal Regulations (proposed rule)

2.4.4 Biological Bacteria and parasitic microorganisms are what most people think of when they talk about water contamination. If the right municipal treatment process is not in place there can be very dangerous outbreaks. The most common and widespread danger associated with drinking water is contamination, either directly or indirectly, by sewage, by other wastes, or by human or animal excrement. If such contamination is recent, and if among the contributors there are carriers of communicable enteric diseases, some of the living causal agents may be present. The drinking of water so contaminated or its use in the preparation of certain foods may result in further cases of infection. Natural and treated waters vary in microbiological quality. Ideally, drinking water should not contain any microorganisms known to be pathogenic to man. In practice, this means that it should not be possible to demonstrate the presence of any coliform organism in any sample of 100 ml. Pathogenic organisms found in contaminated water may be discharged by human beings who are infected with disease or who are carriers of a particular disease. The principal categories of pathogenic organisms are, as shown in Table 2.10, bacteria, viruses, protozoa and helminths.

Water Science  51 Table 2.10  List of infectious agents potentially present in drinking water contaminated by sewage. Organism

Disease

Remarks

Escherichia coli (enteropathogenic)

Gastroenteritis

Diarrhoea

Legionella pneumophila

Legionellosis

Acute respiratory illness

Leptospira (150 spp.)

Leptospirosis

Jaundice, fever

Salmonella typhi

Typhoid fever

High fever, diarrhoea

Salmonella (~1700 spp.)

Salmonellosis

Food poisoning

Shigella (4 spp.)

Shigellosis

Bacillary dysentery

Vibrio cholerae

Cholera

Extremely heavy diarrhoea, dehydration

Yersinia enterocolitica

Yersinosis

Diarrhoea

Bacteria

Viruses Adenovirus (31 types)

Respiratory disease

Enteroviruses (67 types, e.g., polio, echo, and Coxsackie viruses)

Gastroenteritis, heart anomalies, meningitis

Hepatitis A

Infectious hepatitis

Jaundice, fever

Norwalk agent

Gastroenteritis

Vomiting

Reovirus

Gastroenteritis

Rotavirus

Gastroenteritis

Protozoa Balantidium coli

Balantidiasis

Diarrhoea, dysentery

Cryptosporidium

Cryptosporidiosis

Diarrhoea

Entamoeba histolytica

Amoebic dysentery

Prolonged diarrhoea with bleeding (Continued)

52  Sustainable Water Purification Table 2.10  List of infectious agents potentially present in drinking water contaminated by sewage. (Continued) Organism

Disease

Remarks

Giardia lamblia

Giardiasis

Mild to severe diarrhoea, nausea

Fasciola hepatica

Fasciolasis

Sheep liver fluke

Dracunculus medinensis

Dracunculosis

Guinea worm

Ascaris lumbricoides

Ascariasis

Roundworm

Enterobius vericularis

Enterobiasis

Pinworm

Hymenolepis nana

Hymenolepiasis

Dwarf tapeworm

Taenia saginata

Taeniasis

Beef tapeworm

Taenia solium

Taeniasis

Pork tapeworm

Trichuris Trichiura

Trichuriasis

Whipworm

Helminths

Bacteria Faecal pollution of drinking water may introduce a variety of intestinal pathogens - bacterial, viral, and parasitic - their presence being related to microbial diseases and carriers present at that moment in the community. Intestinal bacterial pathogens are widely distributed throughout the world. Those known to have occurred in contaminated drinking water include strains of Salmonella, Shigella, enterotoxigenic Escherichia coli, Vibrio cholerae, Yersinia enterocolitica, and Campylobacter fetus. These organisms may cause diseases that vary in severity from mild gastro-enteritis to severe and sometimes fatal dysentery, cholera, or typhoid. The modes of transmission of bacterial pathogens include ingestion of contaminated water and food. The significance of the water route in the spread of intestinal bacterial infections varies considerably, both with the disease and with local circumstances. Among the various waterborne pathogens, there exists a wide range of minimum infectious dose levels necessary to cause a human infection. With Salmonella typhi, ingestion of relatively few organisms can cause disease; with Shigella flexneri, several hundred cells may be needed, whereas many millions of cells of Salmonella serotypes are usually required to cause gastroenteritis. Similarly, with

Water Science  53 toxigenic organisms such as enteropathogenic E. coli and V. cholerae as many as 108 organisms may be necessary to cause illness. The size of the infective dose also varies in different persons with age, nutritional status, and general health at the time of exposure. Surveillance of the bacterial quality of water is also important, not only in the assessment of the degree of pollution, but also in the choice of the best source and the treatment needed. Bacteriological examination offers the most sensitive test for the detection of recent and therefore potentially dangerous faecal pollution, thereby providing a hygienic assessment of water quality with a sensitivity and specificity that is absent from routine chemical analysis. It is essential that water is examined regularly and frequently as contamination may be intermittent and may not be detected by the examination of a single sample. For this reason, it is important that drinking water is examined frequently by a simple test rather than infrequently by a more complicated test or series of tests.

Viruses Viruses of major concern in relation to waterborne transmission of infectious disease are essentially those that multiply in the intestine and are excreted in large numbers in the faeces of infected individuals. Concentrations as high as 108 viral units per gram of faeces have been reported. Even though replication does not occur outside living hosts, enteric viruses have considerable ability to survive in the aquatic environment and may remain viable for days or months. Viruses enter the water environment primarily by way of sewage discharges. With the methods at present available, wide fluctuations in the number of viruses in sewage have been found. On any given day, many of the 100 or so known enteric viruses can be isolated from sewage, the specific types being those prevalent in the community at that time. Procedures for the isolation of every virus type that may be present in sewage are not yet available. As sewage comes into contact with drinking water, viruses are carried on and remain viable for varying periods of time depending upon temperature and a number of other less well-defined factors. It is generally believed that the primary route of exposure to enteric viruses is by direct contact with infected persons or by contact with faecally contaminated objects. However, because of the ability of viruses to survive and because of the low infective dose, exposure and consequent infections may occur by less obvious means, including ingestion of contaminated water. Explosive outbreaks of viral hepatitis and gastroenteritis resulting from sewage contamination of water supplies have been well documented epidemiologically. In contrast, the transmission of low levels

54  Sustainable Water Purification of virus through drinking water of potable quality, although suspected of contributing to the maintenance of endemic enteric viral disease within communities, has not yet been demonstrated. In some developing areas, water sources may be heavily polluted and the water-treatment processes may be less sophisticated and reliable. Because of these factors, as well as the large number of persons at risk, drinking water must be regarded as having a very significant potential as a vehicle for the environmental transmission of enteric viruses. As with other microbial infections, enteric viruses may also be transmitted by contaminated food. Enteric viruses are capable of producing a wide variety of syndromes, including rashes, fever, gastroenteritis, myocarditis, meningitis, respiratory disease, and hepatitis. In general, asymptomatic infections are common and the more serious manifestations are rare. However, when drinking water is contaminated with sewage, two diseases may occur in epidemic proportions - gastro-enteritis and infectious hepatitis. Apart from these infections, there is little, if any, epidemiological evidence to show that adequately treated drinking-water is concerned in the transmission of virus infections. Gastroenteritis of viral origin may be associated with a variety of agents. Many of these have been identified only recently occurring as small particles with a diameter of 270-350 microns in stools of infected individuals with diarrhea. Viral gastroenteritis, usually of 24-72 hours’ duration with nausea, vomiting and diarrhea, occurs in susceptible individuals of all ages. It is most serious in the very young or very old where dehydration and electrolyte imbalance can occur rapidly and threaten life if not corrected without delay. Hepatitis, if mild, may require only rest and restricted activities for a week or two, but when severe it may cause death from liver failure, or may result in chronic disease of the liver. Severe hepatitis is tolerated less well with increasing age and the fatality rate increases sharply beyond middle age. The mortality rate is higher among those with pre-existing malignancy and cirrhosis.

Protozoa Protozoa are single-celled eucaryotic micro-organisms without cell walls. The majority of protozoa are aerobic. Protozoa feed on bacteria and other microscopic microorganisms. Of the intestinal protozoa pathogenic for man, three may be transmitted by drinking water: Entamoeba histolytica, Giardia spp., and Balantidium coli. These organisms are the etiological agents of amoebic dysentery, giardiasis and balantidiasis, respectively, and have all been associated with drinking water outbreaks. All three have

Benzene and other petrochemicals can be cancer causing even at low exposure Linked to reproductive disorders and some cancers

Fertilizer runoff; mature from livestock operations, septic systems

Underground petroleum storage tanks.

Effluents from metals and plastics degreasing, fabric cleaning, electronics and aircraft manufacture

Nitrate

Petro-chemicals

Chlorinated Solvents

Western United States, Industrial zones in East Asia

United States, United Kingdom, parts of former Soviet Union.

Midwestern and mid-Atlantic United States, North China Plain, Western Europe, Northern India

United States, Eastern Europe, China, India

Principal regions affected

(Continued)

Restricts amount of oxygen reaching brain, which can cause death in infants, linked to digestive tract cancers.

Organochlorines linked to reproductive and endocrine damage in wildlife; organophosphates and carbonates linked to nervous systems

Runoff from farms, backyards, golf courses, landfill leaks

Pesticides

Health and ecosystem effects at high concentrations

Sources

Threat

Table 2.11  Some major threats to groundwater*.

Water Science  55

Naturally occurring, possibly exacerbated by over-pumping aquifers and by phosphorus from fertilizers

Mining waste and tailings, landfills, hazardous waste dumps

Seawater intrusion, de-icing salt for roads

Arsenic

Other Heavy metals

Salts

Freshwater unusable for dinking or irrigation

Nervous system and kidney damage; metabolic disruption

Nervous systems and liver damage, skin cancers

Health and ecosystem effects at high concentrations

*Major sources: European Environmental Agency, USGS, British Geological Survey.

Sources

Threat

Table 2.11  Some major threats to groundwater*. (Continued)

Coastal China and India, Gulf coasts of Mexico and Florida, Australia, Philippines

United States, Central America and northeastern South America, Eastern Europe

Bangladesh, Eastern India, Nepal, Taiwan

Principal regions affected

56  Sustainable Water Purification

Water Science  57 worldwide distribution. As a group, the intestinal pathogenic protozoa occur in large numbers in the faeces of infected individuals in man and a wide variety of domestic and wild animals. Coliform organisms do not appear to be a good indicator of Giardia or E. histolytica in treated water because of the increased resistance of these protozoans to inactivation by disinfection. Table 2.11 shows major threats to groundwater.

3 Sustainability of Current Water Purification Technologies 3.1 Introduction Water is the most valuable resource. It is also the most abundant. Yet, water conflicts or wars have been the predominant theme (Gleick, 1993). One out of 10 of world population does not have access to safe drinking water. Over 80% of the disease in developing countries is related to poor drinking water and sanitation. Globally, 4,500 children die every day from preventable diseases related to a lack of access to clean water, adequate sanitation and hygiene. Medical research has reported many cases of lasting damage to women’s health in consequence to carrying heavy jugs of water, like chronic fatigue, spinal and pelvic disfigurements, and effects on reproductive health such as spontaneous miscarriages. The west has an entirely different set of problems. The entire urban system that takes pride in water purification through a central water management company routinely ‘purifies’ waste water by removing solids, then a series of chemical treatments that turn water into a chemical potion with long-term impacts on both human health and the environment. This water contains practically all synthetic chemicals that are consumed as prescription drugs and other means. While studies are cropping up showing how every disease relates to the water quality, which is deemed ‘clean’ by all acceptable standards, little has been done to correct the overall water purification scheme. It is commonly acknowledged that Education is essential for short and long-term economic progress. No country has succeeded in rapid and sustaining economic growth without at least 40% of literate adults. Not having access to clean water and sanitation systems lowers school attendance rates and increases risk of disease and death, meaning GDP also decreases. This entire argument is built on the notion that today’s education system is indeed sustainable. In reality, this is a false premise that has become the biggest impediment to identifying the real cause behind most spectacular

M. Safiur Rahman and M.R. Islam. Sustainable Water Purification, (59–122) © 2020 Scrivener Publishing LLC

59

60  Sustainable Water Purification breakdown of today’s technology development mode, aptly denominated as ‘technological disaster’ by Nobel laureate Chemist, Robert Curl. There is no shortage of patronizing comments like: “No other single intervention is more likely to have a significant impact on global poverty than the provision of safe water” (Schuster-Wallace et al., 2008). In a world of real science, these hollow statements have no place and bear no relevance to the real problem involving water management. While it has become fashionable to talk about Africa and about how more than a quarter of the population spends more than 30 minutes, sometimes up to 6 hours, walking 3.75 miles just to collect enough water for the day, the focus should be on what quality of water we drink in the west. The west, which spends tremendous amount of money on ‘purifying’ water only to drink less than 5% of it, while squandering the rest while simultaneously relying on bottled water to drink is certainly not in a position to set guidelines for water sustainability. As usual, the water problem is linearized and the solution proposed is reduced into a dollar figure. The UN estimates it would cost an additional $30 billion to provide access to safe water to the entire planet. That is a third of what the world spends in a year on bottled water. Sustainability in water is also featured prominently in economic development consideration. In order to maintain economic development and minimize future regional and international conflicts, the United States has set up strategies for sustainable supplies of high-quality fresh water (NRC, 2014). The principal considerations are: –– –– –– ––

demand management, improved water storage capacity, water quality protection, and advancements in supply-enhancing water treatment technologies.

There is another resource, which is dependent on technologies. Because less than 3% of world water resource has salinity below potable value, desalination offers an alternative. There are an estimated between 15,000–20,000 desalination plants that produce more than 20,000 m3/day. Desalination technologies can create new sources of freshwater from otherwise impaired waters, such as seawater or brackish water. However, like nearly all new fresh water sources, desalinated water comes at substantially higher costs than today’s existing water sources, keeping these technologies out of the reach of many communities.

Sustainability of Current Water Purifcation Technologies  61 According to the World Health Organization (WHO, 1984), total dissolved solids (TDS) should be less than 1,000 mg/L in drinking water based on taste considerations, and the EPA has set a secondary standard for TDS in drinking water of 500 mg/L (EPA, 2002). By comparison, seawater has an average TDS of about 35,000 mg/L. Table 3.1 shows various sources of water and their corresponding TDS values. According to Envisioning the Agenda for Water Resources Research in the Twenty First Century (NRC, 2001b), both in the United States and worldwide, “the principal water problem in the early twenty-first century will be one of inadequate and uncertain supplies….” Finite quantities of developed water supplies exist, and growing demand has outstripped supply in many regions of the world, including parts of the United States. This shortage arises from the fact that none of the existing water purification technologies is sustainable (Khan and Islam, 2016). Traditional solutions to water scarcity have focused on developing additional supplies (e.g., drilling wells, building dams to store water that would otherwise become irretrievable). However, even when options are available for developing new supplies or transferring water from other areas where supplies are more plentiful, water development can be extremely expensive (AMTA, 2001a). Awareness has also grown over the past few decades about the negative environmental consequences of expanding water development, such as stream degradation and aquifer depletion (Gleick, 2003). Past efforts have focused on safety and short-term reaction to drinking water. Recently, a report by the World Health Organisation/Unicef Joint Monitoring Programme collected data on drinking water from the previous 17 years to give a detailed view of the state of access to drinking water Table 3.1  Classification of source water, according to quantity of dissolved solids. Water source total dissolved solids (milligrams per liter) potable water (NRC, 2014). Water source

Total dissolved solids (milligrams per liter)

Potable water

Pb(II) > Zn(II) > Cr(II) (Ajmal et al., 2000). The extent of removal of Ni(II) was found to be dependent on sorbent dose, initial concentration, pH and temperature. The adsorption follows first-order kinetics. The process is endothermic showing monolayer adsorption of Ni(II), with a maximum adsorption of 96% at 50°C for an initial concentration of 50 mg/l at pH 6. As similar study was undertaken by Annadurai et al. (2002) but Tonni et al. (2005) reported that the result obtained by Ajmal et al. (2000) when the initial concentration of Ni(II) was 1000 ppm, was significantly higher than that of a similar study undertaken by Annadurai et al. (2002) when the initial concentration of Ni(II) was 25ppm. Tonni et al. (2005) suggested that the adsorption capacity of an adsorbent depends on the initial concentration of adsorbate. Coconut shell: Coconut shell is an agricultural waste from coconut industry. Babel and Kurniawan (2004b) studied the of coconut shell charcoal (CSC) modified with oxidizing agents and/or chitosan for Cr(VI) removal from wastewater (Figure 3.30). To make Cr removal by CSC more economical, Kurniawan (2002) studied the regeneration of the spent adsorbent and reported that desorption and regeneration of CSC with NaOH and HNO3 still enabled the same column for multiple uses in subsequent cycle with a regeneration efficiency of more than 95% (Kurniawan, 2002). Babel and Kurniawan (2004b) found that CSC oxidized with nitric acid had higher Cr adsorption capacities (10.88 mg/g) than that oxidized with sulfuric acid (4.05 mg/g) or coated with chitosan (3.65 mg/g). The results

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Figure 3.30  Coconut based best activated carbon.

suggest that surface modification of CSC with a strong oxidizing agent generated more adsorption sites on its solid surface for metal adsorption. Hazelnut shell: Cimino et al. (2000) investigated the removal of cadmium, zinc and chromium ions from aqueous solutions using hazelnut shell as biosorbent substrate (Figure 3.31). Batch equilibrium tests showed that

Figure 3.31  Hazelnut shell.

Sustainability of Current Water Purifcation Technologies  113 the maximum removal of Cd2+, Cr3+ and Zn2+ ions was observed only into a specific pH range from 4 to 6. Cimino et al. (2000) reported that that the metal ion sorption obeyed both the Langmuir and Freundlich isotherms and more Cr3+ ions were removed than both Cd2+ and Zn2+ ions. Ni(II) removal from simulated solution using hazelnut shell activated carbon was studied by Demirbas et al. (2002). They found that metal adsorption improved with an increasing temperature, suggesting that the adsorption was endothermic. The optimum Ni(II) removal took place at pH 3.0 with metal adsorption capacity of 10.11 mg/g, when the initial metal concentration was 15 mg/L. (Kobya et al., 2004) investigated the Cr(VI) adsorption capacity using hazelnut shell with an initial Cr(VI) concentration of 1000 mg/L. About 70 mg/g of Cr(VI) capacity occurred at pH 1.0. The results indicate that the adsorption capacity of individual adsorbent depends on the initial metal concentration. Peanut Husk: Peanut husk carbon prepared from peanut husks (PHC, Figure 3.32) has been used for the adsorption of Pb2+, Zn2+, Ni2+ and Cd2+, over a range of initial metal ion concentration (0.15 mM). The results show that Pb2+ has best affinity to PHC than Cd2+, Ni2+, Zn2+ (Ricordel et al., 2001). From the FTIR study it was reported that PHC contained polar functional groups such as aldehydes, ketones, acids and phenols and these groups could be involved in chemical bonding and would be responsible for the adsorption capacity of the PHC (Ricordel et al., 2001). Functional identification on the basis of IR spectrum were referred to the IR spectra of carbons of other works (Bautista-Toledo et al., 1994; Fanning and Vannice, 1993). Periasamy and Namasivayam (1995) studied the peanut hulls as an adsorbent for Ni(II) removal from synthetic solution and it was observed that the maximum Ni(II) removal from synthetic solution

Figure 3.32  Peanut husk.

114  Sustainable Water Purification using peanut hull was observed at pH ranging from 4–5 in batch test. But in column studies the maximum Cu(II) removal (65.57 mg/g) occurred at pH ranging from 6–10. This result is significantly higher than that of Brown et al. (2000), who also employed peanut hulls in batch studies for Cu(II) removal with an adsorption capacity of 10.17 mg/g. This phenomenon could be due to the inherent difference in the nature of both studies. In batch experiments, the concentration gradient decreased with increasing contact time; while in column operation, the adsorbent continuously had physicochemical contact with fresh feeding solution at the interface of the adsorption zone, as the adsorbate solution passed through the column. Consequently, Rao et al. (2002) studied the metal removal by peanut hull in column studies and it was reported that the removal capacity was more in column studies rather than that in batch studies.

3.10.3 Industrial By-Products A wide variety of industrial by-products such as chitin, fly ash, waste iron metallic iron, hydrous titanium oxide, red mud, etc were investigated as adsorbents for heavy metals removal. Several studies have been conducted on the potentiality of industrial by-products for metal removal and it has been reported that industrial byproducts might be used as cost-effective adsorbents. Maximum industrial by-products are inexpensive and abundantly available that can be obtained from industrial processing only. They can be chemically modified to improve their removal performance. The remainder of the section will briefly describe some of these industrial by-products that might be used as adsorbents. Chitin and Chitosan: Chitosan can be produced chemically from chitin and the chemical production of chitosan is not very costly. It is also found naturally in some fungal cell walls. Both chitin and chitosan are inexpensive and abundant. Both have highly adsorbent capacity to remove heavy metal from aqueous solution (Rahman et al., 2004). Berkeley (1979) and Rorrer et al. (1993) reported that chitin is second only to cellulose in terms of abundance in nature and is found in the exoskeletons of crabs and other arthropods and in the cell walls of some fungi. Chitin is also a waste product of the crab meat canning industry. Metal adsorption capacity of chitosan is five to six times greater than of chitin due to the free amino groups exposed during deacetylation (Yang and Zall, 1984). Bailey et al. (1999) mentioned some factors such as crystallinity, percent deacetylation, and amino group content that affect adsorption. Bailey et al. (1999) also appreciated the necessity of loose cross-linking with glutaraldehyde as suggested by Kurita et al. (1986) to ensure most effective

Sustainability of Current Water Purifcation Technologies  115 adsorption and stability, but they also did mention some of the limitations of chitosan. It is soluble in acidic solution and it is nonporous and that again necessitates the technique of acylation to increase porosity (Hsien, 1995). Moreover, improvement in sorption is obtained by grafting functional groups such as amino acid esters, pyridil etc. Bailey et al. (1999) is associated with great complexity that may limit the use of chitosan. The adsorption capacity of chitosan could be improved by the substitution of various functional groups, such as organic acids, onto the chitosan backbone. Some functional groups grafted to chitosan to improve adsorption capacity are pyridyl (Baba and Hirakawa, 1992), amino acid esters (Ishii et al., 1995; Rahman et al., 2003), oxo-2-glutaric acid (Guibal et al., 1994), and polyethyle-nimine (Kawamura et al., 1993) substituted pyridine rings (Tong et al., 1991). Fly ash: Bailey et al. (1999) reported that fly ash consists of carbon and oxides of silica, alumina and iron (Figure 3.33). Grover and Narayanaswamy (1982) observed that fly ash, a waste product from thermal power plants, has some adsorption capabilities for Cr (VI). At pH 2.0 the Cr (VI) adsorption capacity was observed 4.250 mg/g. Bayat (2002) studied the fly ash of thermal power plans and found that the adsorption capacity of the Seyitomer and Afsin–Elbistain fly ash for Ni(II) and Cu(II) was 0.93 mg/g and 1.35 mg/g respectively when the initial concentration was 25 mg/L for both metals. As indicated by the applicability of the Langmuir isotherm for the equilibrium data of both metals, monolayer adsorption might occur on the surface of the adsorbent. Kapoor and Viraraghavan (1996) noted that the properties of fly ash are extremely variable and the adsorption capacity varies with the lime content. Banerjee et al. (1997) presents information

Figure 3.33  Fly ash.

116  Sustainable Water Purification on the adsorption kinetics of organic compounds and reports increasing capacity with increasing carbon content. The surface area of fly ash is reported as 1-6 m2/g. A potential advantage of fly ash is that it could easily be solidified after the metals are adsorbed because it contains pozzolanic particles that react with lime in the presence of water, forming cementitious calcium-silicate hydrates. Raoa et al. (2002) explored the adsorption capacity of bagasse and fly ash and reported that efficiencies of adsorbent materials for the removal of Cr(VI) and Ni(II) were found to be between 56.2 to 96.2% and 83.6 to 100%, respectively. These results were obtained at the optimized conditions of pH, contact time, sorbent dose, sorbate concentration of 100 mg/l and with the variation of adsorbent particles size between 0.075 and 4.75 mm. The order of selectivity is powdered activated carbon >bagasse > fly ash for Cr(VI) removal and powdered activated carbon >fly ash > bagasse for Ni(II) removal. Gupta et al. (2003) studied bagasse fly ash for Cd(II) and Ni(II) removal from synthetic solution and reported that about 90% of 14 mg/L of Cd(II) and 12 mg/L of Ni(II) were removed at pH ranging from 6.0 to 6.5. The metal removal improved with an increasing temperature, suggesting an endothermic reaction. Raoa et al. (2002) reported that the sorption data has been correlated with Langmuir and Freundlich adsorption models. Coffee residue: Coffee residues (Figure 3.34) are solid wastes discarded from the extraction process of instant coffee manufacturing and a huge amount of these wastes are currently disposed of by burning as fuel or mixed with fertilizer. Boonamnuayvitaya et al. (2004) investigated the utilization of coffee residues binding with clay as adsorbent (hereafter called CC-adsorbent) for the removal of heavy metal ions in aqueous solutions. The adsorption capacities of the CC-adsorbent for Cd2+, Cu2+, Pb2+, Zn2+ and Ni2+ were determined by the Langmuir isotherm model. The adsorption increased in the order of Cd2+ >Cu2+ >Pb2+ >Zn2+ >Ni2+. Since coffee residues hold several functional groups, they have high potential for heavy metal adsorption. Boonamnuayvitaya et al. (2004) also studied the functional group in coffee residue using FTIR indicated that the O–H, C=O and C–N groups were found in all samples where O–H was maximum. This group should play a major role in heavy metal adsorption as mentioned in lead adsorption by active cokes from lignite using mild oxidation (Finqueneisel et al., 1998). Kapoor and Viraraghavan (1995) reported these functional groups in the study of biosorption mechanism of fungi. Boonamnuayvitaya et al. (2004) studied the electrical potential and zeta potential measurement indicated that a negatively charge ions present in CC adsorbent resulting in the electrostatic interaction between active sites and metal ions.

Sustainability of Current Water Purifcation Technologies  117

Figure 3.34  Coffee beans and residue (simulated).

Bark: Bark is a solid waste product of the timber industry from mechanical wood processing and is effective because of its high tannin content (Figure 3.35). The polyhydroxy polyphenol groups of tannin are thought to be the active species in the adsorption process (Bailey et al., 1999). As metal cations displace adjacent phenolic hydroxyl groups, ion exchange takes place and forms a chelate (Randall et al., 1974; Vazquez et al., 1994).

Figure 3.35  Pine bark chips.

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Figure 3.36  Lignin.

The major problem with tannin containing materials is the discoloration of water from soluble phenols. Alves et al. (1993) and Vazquez et al. (1994) pointed out that the application of pre-treatments such as acidified formaldehyde eliminates the bleeding of colored compounds without appreciable reduction in capacity. The pre-treatment, again, increase costs. Randall et al. (1974) compared bark adsorption to that of peanut skins, walnut expeller meal and coconut husks. A study with peanut skins was found effective to remove lead, mercury, copper and cadmium (Randall et al., 1978). Though this was successful in withstanding disintegration in contact with water and discoloration, the cost of adsorbent polymerization with formaldehyde is noticeable. Lignin: Lignin, an extract from the waste product (black liquor) of the paper industry, showed very good adsorptive capacity for lead (Figure 3.36). Srivastava et al. (1994) reported that this capacity might reach up to 1865 mg/gm. Moreover, the authors also reported removal of zinc; capacity being 95 mg/gm. Polyhydric phenols and several functional groups on the surface are thought to be responsible for high adsorption on lignin. The functional groups include ketones, aldehydes, acids, alcohols etc. and they take part in exchanging cations.

3.10.4 Natural Materials Like as agricultural wastes and industrial by product, natural materials can be used as low-cost adsorbents for heavy metal removal from aqueous

Sustainability of Current Water Purifcation Technologies  119 streams. It was reported in literature by several authors (Trgo et al., 2003; Peric et al., 2004; Kurniawan et al., 2005) reported that many natural materials available in certain regions were used for the removal of heavy metal from contaminated water due to its metal binding capacity. Bailey et al. (1999); Babel and Kurniawan (2003b) reported that after additional processing may improve the adsorption capacity of natural materials for the removal of heavy metal from an aqueous solution. Zeolites: Zeolites are alumina silicates and because of their crystalline structure, their net surface charge is negative which helps to adsorb the positive charged metal ions. Kurniawan et al. (2005) reported that zeolite appears as one of the most promising for metal purification among minerals that possess sorbent properties. In many countries, zeolites have been used as a low-cost adsorbent for the treatment of metalcontaminated wastewater. The adsorption behavior of natural (clinoptilolite) zeolites (Figure 3.37) in order to consider its application to purity metal finishing wastewaters. The batch method was employed, using metal concentrations in solution ranging from 100 to 400 mg/l of Co2+, Cu2+, Zn2+, and Mn2+. The sorption isotherms of binary solute systems could be fitted by the competitive Langmuir model and the result showed that natural zeolite can be used effectively for the removal of metal cations from wastewater. Peric et al. (2004) studied the uptake of zinc (II), copper (II), and lead (II) from aqueous solutions by ion exchange on natural zeolitic and it was reported that the efficiency of removal was higher for Pb(II) and Cu(II) than for Zn(II)

Figure 3.37  Zeolite.

120  Sustainable Water Purification ions. The metal removal by zeolites was a complex process, involving ion exchange and adsorption. Zeolites belong to the class of minerals known as “tectosilicates.” Most common natural zeolites are formed by alteration of glass-rich volcanic rocks (tuff) with fresh water in lakes or by seawater. Zeolites are naturally occurring hydrated aluminosilicate minerals (Badillo-Almaraz et al., 2003). The presence of more than 40 zeolite species in nature has often inspired several researchers to use it as an adsorbent. Leppert (1990) reported that the adsorption of lead on zeolite is significant (155.4 mg/ gm). The study also demonstrated a moderate removal of chromium (II), 26 mg/gm. Although the amount of lead removal is significant, chromium removal is not. Leppert (1990) also mentioned that the capacity might vary for different species. Desborough (1995) illustrated that the clinoptilolite-rich rocks (CRRs) could be used for lead removal from wastewater. Moreover, the alteration of zeolites is sometimes necessary for the removal of metals such as chromium (VI) to increase sorption. Santiago et  al. (1992). They recommended the use of complex organic cations, which are high in cost. Babel and Kurniawan (2003b) studied Cr(VI) uptake from simulated wastewater using natural zeolite and treated by sodium chloride. NaCl treated zeolite had better removal capabilities (3.23 mg/ g) for Cr(VI) ions than as-received zeolite (1.79 mg/g) at an initial Cr concentration of 20 mg/L. NaCl was suitable to reuse zeolite with regeneration efficiency of more than 90% (Kurniawan, 2002). These results suggest that the Cr adsorption capacities of zeolite varied, depending on the extent of chemical treatment (Wingenfelder et al., 2005) and due to ion exchange between Na(I) of zeolite and Cr(III) ions in the solution (Kurniawan, 2002). Clay: Clay has high adsorption capacity like as zeolite to remove heavy metal from contaminated water (Figure 3.38). There are three types of clay, i.e., montmorillonite, bentonite and kaolinite. Montmorillonite has the highest adsorption capacity out of the three and it is twenty-times cheaper than that of activated carbon (Virta, 2002). Two properties of clay assist in the sorption of heavy metals. Firstly, the negative charge on the surface and secondly, the large surface area (up to 800 m2/g). Several researchers studied different types of clay as adsorbents. Sharma et al. (1990) used wollastonite and Viraraghavan and Kapoor (1995) employed bentonite to remove heavy metals from wastewater. In fact, presence of montmorillonite, a major component in bentonite attracts heavy metals because of its largest surface area and highest cation exchange capacity. Ulmanu et al. (2002), studied Cu(II) and Cd(II) removal from synthetic solution using bentonite and higher adsorption capacities was found for both ions (Cu(II): 18.16 mg/g; Cd(II): 9.34 mg/g).

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Figure 3.38  Clay.

Chromium (III) removal from simulated solution was examined by bentonite and an expanded perlite. Kinetics studies showed that the Cr(III) uptake by bentonite was faster than that by perlite and Cr(III) removal by bentonite (96%) was remarkably higher than that by perlite (40%) at the same Cr concentration of 20 mg/L (Chakir et al., 2002). Kaya and Oren (2005) have reported that bentonite consists of clay, silt and sand; and this material is valuable for its tendency to absorb water in the interlayer site. One of the materials from clay minerals is kaolinite which has a tetrahedral (Si center) and octahedral (Al center) structure. It was reported that kaolinite had the highest adsorption capacities of Cu(II) compared to other metals i.e Ni(II), Mn(II) and Co(II) due to their small ionic radius and the metal sorption on kaolinite followed the Langmuir isotherm (Arias et al., 2002; Yavuz et al., 2003). To increase the sorption capacity of clay, Cadena et al. (1990) suggested tailoring or modifying the natural exchangeable cation of clay with an organophilic cation; tetramethyl ammonium ion (TMA+). This complex modification demonstrated a lead uptake of 58 mg/gm. China clay has been reported to adsorb only 0.29 mg/gm of lead (Yadava et al., 1991). Abollino et al. (2003) studied the adsorption of Cd(II), Cr(III), Cu(II), Ni(II) and Zn(II) ions on Na-montmorillonite using column operations and it was reported that Cu(II) was the least adsorbed of the cations, while Cd(II) ion was the most adsorbed due to its high charge density. Lin and Juang (2002) reported that the modified montmorrilonite using sodium dodecyl

122  Sustainable Water Purification sulfate (SDS) significantly improve its removal for Cu(II) and Zn(II). The pretreatment of clay with hydorchloric (HCl) acid significantly improved the removal of Ni(II), Cu(II) and Zn(II) from simulated wastewater and the  maximum adsorption capacities for the cations in the solution were in the order: Cu(II) > Ni(II) > Zn(II) (Vengris et al., 2001). Vengris et al. (2001) reported that acid treatment changed the chemical composition and mineralogical structure of clay that enhancing its uptake capacity.

4 Sustainable Drinking Water Purification Techniques 4.1 Introduction The water quality has severely deteriorated globally in last few decades, mainly due to the anthropogenic activities, urbanization, industrialization and the western lifestyle’s utilization of natural water resources. The main source of water pollution is synthetic chemicals arising from domestic waste, agricultural waste, toxic industrial wastes. In recent years, various toxic chemicals (e.g., micropollutants, personal care products, endocrine disrupting compounds, pesticides, inorganic anions, and countless others) have been detected at dangerous levels in drinking waters in many parts of the world and a variety of health risks to human beings due to water pollution have been reported in literature. While the world focuses on the detectable level and ‘safety’, any sustainable development must focus on the source of the real toxicity. The urgency should be in developing robust, economically appealing and environmentally friendly processes, which may be readily implemented indigenously. Numerous treatment technologies are available with varying degree of success to control/minimize water contamination, all claiming some sort of sustainability. However, as we have seen in Chapter 3, none of the current commercial systems fall under the category of true sustainability. Nevertheless, the formal shortcomings are listed as: –– high operational and maintenance costs –– generation of toxic sludge –– complicated procedures involved in the treatment. In general, adsorption processes have gained more popularity in water treatment due to convenience, ease of operation and simplicity of design (Faust and Aly, 1987). For drinking water purification, activated carbon is considered a universal adsorbent. However, we seen in Chapter 3 that M. Safiur Rahman and M.R. Islam. Sustainable Water Purification, (123–154) © 2020 Scrivener Publishing LLC

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124  Sustainable Water Purification activated carbon, as prepared today, is not sustainable, and it being costly makes it even less appealing. However, its widespread use in wastewater treatment is sometimes restricted due to its higher cost. A large variety of low-cost adsorbents (LCA) have been examined for their ability to remove various types of pollutants from water and wastewater and have been reviewed extensively. Natural materials or the wastes/by-products of industries are more appealing than synthetic ones from just economic perspective. However, from sustainability considerations, natural materials are most attractive. A protocol based on the numerous studies for the development, utilization and application of low-cost adsorbents generally adopted by researchers was suggested by Gupta et al. (2009). The LCAs as reported in literature are usually called substitutes for activated carbons because of their similar wide use; however, in a broad and clearer way they are essentially substitutes for all expensive adsorbents. Figure 4.1 shows Gupta et al.’s protocol. They presented a protocol for the development, utilization, and application of LCA. It is worthwhile noting here that these materials are usually called substitutes for activated carbons because of their wide use and especially for their application in treating wastewater. The general notion is to replace with another material, which is less costly. These low-cost alternative adsorbents are classified in two ways (Gupta et al., 2009): –– on basis of their availability (i.e., natural materials such as wood, peat, coal, lignite, etc.; –– industrial/agricultural/domestic wastes or byproducts such as slag, sludge, fly ash, bagasse fly ash, red mud, etc.; and synthesized products) or depending on their nature (i.e., inorganic and organic). In view of what we have seen in Chapter 3, this classification does not conform to the sustainability requirement. For a purification technique to be sustainable, all levels of intervention have to be natural. Before discussing purification of drinking water, it is important to note that the standard of drinking water is groundwater. Ground water from the oldest rock is the most balanced and most nourishing. The lowest quality is the one from shallow reservoirs, which are vulnerable to contamination with synthetic chemicals, arising from waste water, both from domestic sources as well as industrial or agricultural sources. Some of this research has become a sensitive issue. For instance, when Lina Nikoleris discovered in her doctoral work (Lund University in Sweden) that showed that hormones found in birth control pills alter the genes in fish, which can cause

Sustainable Drinking Water Purification Techniques  125 Industrial, agricultural, and domestic activities

Organic precursors

Inorganic precursors

Physical activation

Chemical activation

Carbonization

Mixing precursor with chemical

Activation

Chemical treatment

Activation

Washing and drying

Washing and drying

Sieving and storage

Sieving and storage

Washing and drying

Sieving and storage

Characterization of adsorbent

adsorption and testing of adsorbent batch process

Removal of pollutants by small scale column

Removal of pollutants by large scale column

Figure 4.1  Protocol for development of low-cost adsorbents and their utilization for wastewater treatment.

changes in their behavior, other agencies quickly moved to marginalize the effect. The work showed that the hormone ethinyl-estradiol (EE2) is an active substance in many birth control pills which affects aquatic organisms when released as waste into the water. In her thesis, Nikoleris studied how fish are affected by EE2 (Nikoleris and Hansson, 2015). The thesis studied three different fish species: salmon, trout and roach, which are economically important fish that live in both sea and freshwater. Even at low concentrations of EE2, fish were found to be affected. In particular,

126  Sustainable Water Purification a change in the genetic balance in fish as well as difficulty in catching food were noticed. Previous studies have shown that the fish also develop problems with procreation (Kim et al., 2010). This chapter focuses on restoring real science to offer a guideline for sustainable drinking water purification.

4.2 Natural Lifestyle Our civilization is defined by the way our human needs are planned. If we start off with the premise that ‘nature is good’, we can measure the worth of any civilization by its proximity to natural thinking and usage of natural resources, water being the most valuable resource. In today’s world, led by profiteers, water has become the most important target for denaturing. To the extent that considerations of profitability overrule every other consideration in the Information age, “profit” has become an obscenity. In an era of maximizing profit and minimizing value, Big Pharma is widely alleged to push its wares by deceiving the public—even offering to pay doctors for prescribing their products—as well as bribing politicians. All this creates a vicious cycle of the health industry and government getting richer, feeding the oldest scheme of Trinity formed through Government, Church, and Corporations. The scheme extends even onto the black market, where drugs are sold illegally, people become addicted and need to spend money for their fix. In countries where health care is free of charge, this frequently implicates the judicial order by dragging the prison system drags the government, along with other government-sponsored corporations (e.g. prison system) in the most sinister form. We continuously hear about the threats to human existence that loom on us because of the process that we have followed as a human race. In this process, modern society has become an expression of contradictions, as depicted in Figure 4.2. We claim to have progressed as a human race, yet we have increased our per capita energy consumption, personal stress, and per capital waste while intangibles, such as state of the environment, quality of natural resources, quality of personal and social life, have diminished. Meanwhile profit of big corporations has skyrocketed, along with disparity between the rich and the poor. Oxfam’s 2019 report acknowledged, the richest 147 billionaires in the world control about 1 percent of global wealth (Matthews, 2019). Figure 4.3 shows clearly how a small (in global perspective) number of millionaires control a shocking share of the world’s wealth. As the figure shows, 42 million people, or 0.8 percent of the world’s population, have net worth in excess of $1 million. That group—roughly the

Sustainable Drinking Water Purification Techniques  127 Population Per capita energy consumption Environment pollution Stress, waste

State of environment Natural resources Quality of life Social integration Before industrial age

Industrial age

Figure 4.2  Modern civilization is full of contradictions and paradoxes.

42 m (0.8%) > USD 1 million USD 100,000 to 1 million USD 10,000 to 100,000

USD 142.0 trn (44.8%) 436 m (8.7%)

1,335 m (26.6%)

USD 124.7 trn (39.3%)

USD 44.2 trn (13.9%)

< USD 10,000

USD 6.2 trn (1.9%) 3,211 m (63.9%)

Wealth range

Total wealth (%of world)

Number of adults (percent of world adults)

Figure 4.3  The global wealth pyramid.

global 1 percent—controls 44.8 percent of the world’s wealth. The more shocking part of the 2019 Oxfam report is that the bottom half ’s wealth fell by 11 percent, whereas a few thousand billionaires saw their wealth increase by 12 percent. In order to appease the Establishment, economists have often resorting to distort data to portray a positive image of the global economic extremis. As shown in Figure 4.4, they plot extreme poverty for various geographic locations. Extreme poverty is defined as living with per capita household consumption below 1.90 international dollars per day. These data are based on household surveys, which take years to collect. Nevertheless, economic growth in India, China, and even sub-Saharan African is taken as a sign

128  Sustainable Water Purification 60% 50% Sub-Saharan Africa

40% 30% 20%

South Asia Wold Latin America and the Caribbean East Asia and Pacific Europe and Central Asia Middle East and North Africa

10% 0% 1987

1990

1995

2000

2005

2010 2013

Share of the population living in extreme poverty, by world region

Extreme poverty is defined as living with per capita household consumption below 1.90 international dollars per day (in 2011 PPP prices). International dollars are adjusted for inflation and for price differences across coutries.

Figure 4.4  Share of the population living in extreme poverty, by world region.

that the progress continued through to the present day. The fact that is being hidden is that countries that used to have natural lifestyle are the hardest hit. For instance, sub-Saharan Africa shows more than twice the extreme poverty rate than the next region (South Asia). The fact that there are 16 billionaires in sub-Saharan Africa living alongside the 358 million people living in extreme poverty is rarely mentioned (Oxfam, 2020). This aspect is further covered in Chapter 5.

Real income growth per adult (%)

250%

Bottom 50% captured 12% of total growth

200%

Top 1 captured 27% of total growth

Prosperity of the global 1%

150%

100% Rise of emerging countries

Squeezed bottom 90% in the US & Westerm Europe

50%

0% 10

20

30

40

50

60

70

80

Income group (percentile)

90

99

99.9

99.99 99.999

Sustainable Drinking Water Purification Techniques  129 The clearest evidence of the real inequality comes from the so-called “Loch Ness” graph produced early 2018 by a team of economists—led by Facundo Alvaredo, Lucas Chancel, and the famous inequality research trio Thomas Piketty, Emmanuel Saez, and Gabriel Zucman (Matthews, 2019). The chart shows how each percentile of the global income distribution saw its incomes increase from 1980 to 2016. There’s a bulge at the left, with people in poor emerging market economies seeing their incomes rise by 100 to 125 percent over those 36 years, modest income growth in the middle (including the poor and middle class in the US and Western Europe), and then skyrocketing growth for the global 1 percent, and especially the global 0.001 percent and global 0.0001 percent. WEF (2020) pointed out, the world’s 2,153 billionaires have more wealth than the 4.6 billion people who make up 60 percent of the planet’s population. So, what is driving this inequality? Oxfam’s report, ‘Time to Care’, puts the blame on ‘sexist economies’ that are ‘fuelling the inequality crisis—enabling a wealthy elite to accumulate vast fortunes at the expense of ordinary people and particularly poor women and girls’. What gender equity has to do with such economic extremism? Oxfam clarifies: The 22 richest men in the world have more wealth than all the women in Africa. The tragedy of inequality is being exploited with sinister agendas. First of all, it is reduced to promote liberal agenda of so-called gender equality. The conclusion? “Governments around the world can, and must, build a human economy that is feminist and benefits the 99%, not only the 1%.” (Whiting, 2020). Then, the effect is being connected to climate emergency, the solution of which is reduced to universal carbon tax (Islam and Khan, 2019). The ‘generous’ ones are also promoting taxing the rich. Mathews (2019) made the case for such tax as: “The rich really are getting preposterously rich. And there’s a real argument to be made—the political argument that Oxfam’s statistic is meant to make—that making taxes more progressive and directing the funds to, say, cash payments to poor households would lead to faster poverty reduction than has occurred under the current system. One analysis suggests that up to 50 percent of global extreme poverty could be ended if developing countries adopted higher top tax rates.”

According to Oxfam’s 2016 report, the top 1% of the world controls more wealth than the rest of the world combined. The average wealth for the top 1% was worth, on average, $1.7 billion while the average wealth of the bottom 90% was around $5,000. The report states: “Power and privilege is being

130  Sustainable Water Purification used to skew the economic system to increase the gap between the richest and the rest…The fight against poverty will not be won until the inequality crisis is tackled.” The trend in Figure 4.5 worsened in 2019. Oxfam (2020) reports far worsening scenario, particularly regarding women and girls. Women and girls put in 12.5 billion hours of unpaid care work each and every day—a contribution to the global economy of at least $10.8 trillion a year, more than three times the size of the global tech industry. This income difference is associated with higher rates of health and social problems, and lower rates of social goods, a lower level of economic utility in society from resources devoted on high-end consumption, and even a lower wealth of bottom 50%

$2.5 $2.0 $1.5 $1.0

Wealth of richest 62 people

$0.5 $0.0

2000 2001 2002 2003 2004 2005 2006 20072008 2009 2010 2011 2012 2013 2014 2015

Figure 4.5  History of wealth accumulation (in trillion).

Worse Index of health and social problems

USA

Better

Portugal United Kingdom Greece New Zealand Ireland France Australia Austria Canada Italy Denmark Germany Spain Finland Belgium Switzerland Netherlands Norway Sweden Japan High

Low Income inequality (Gini)

Figure 4.6  Health and social problems are worse in more unequal countries (from Oxfam, 2020).

Sustainable Drinking Water Purification Techniques  131 level of economic growth when human capital is neglected for high-end consumption. Oxfam (2020) states that the most crucial aspect of the crisis is income inequality itself. It is true in personal level as well as national and global levels. Crucially, inequality, not the overall wealth of a country, appears to be the most influential factor. Highly unequal rich countries are just as prone to these ills as highly unequal poor countries. As Figure 4.6 demonstrates, the USA pays a high price for having such high-income inequality. Overall, only topic that has not been discussed is to return to natural lifestyle. Sadly, that’s where true sustainability lies.

4.2.1 Environmental Awareness The past few decades have witnessed a fundamental shift in public awareness of and concern about the threats to water resources and surrounding ecosystems. But when it comes to policy, little has changed. Most decisions about the management of water resources remain the product of economic criteria and politically charged reasoning – regardless of whether they concern a town, a region, a country or even several countries. Despite repeated calls from world experts, we continue to move in a wrong direction. Water pollution today is justified through ‘water management’. This has an overwhelming impact on the ecosystem, even more acute than what DDT and GMO has on the environment. The factors are considered to be the most important ones affecting water resources: –– population growth, particularly in water-short regions; –– movement of large numbers of people from the countryside to towns and cities; –– demands for greater food security and higher living standards; –– increased competition between different uses of water resources; and –– pollution from factories, cities, and farmlands. Climate change and natural variability in the distribution and occurrence of water further complicate the sustainable development of our water resources. Once again, environmental insult began with commercialization of the insult. In a paper published in 1894, it was formally proposed to add chloride to water to render it “germ-free.” Two other investigators confirmed this proposal and published it in many other papers in 1895. Early attempts at implementing water chlorination at a water treatment plant were made in 1893 in Hamburg, Germany, and in 1897 the town of

132  Sustainable Water Purification Maidstone, England was the first to have entire water supply treated with chlorine. Permanent water chlorination began in 1905, when a faulty slow sand filter and a contaminated water supply led to a serious typhoid fever epidemic in Lincoln, England. Ever since chlorination has become a symbol of civilization. This event is synonymous with the ‘plastic culture’. Ever since, ozonation is used by many European countries and also in a few municipalities in the United States and Canada. Disinfection with chloramine is also becoming increasingly common. The issue of undesirable by-products is less serious with chloramine than chlorine (gas or hypochlorite). Unlike chlorine, chloramine has a longer half-life in the distribution system and still maintains effective protection against pathogens. The reason chloramines persist in the distribution is due to the relatively lower redox potential in comparison to free chlorine. Chloramine is formed by the addition of ammonia into drinking water to form monochloramine and/or dichloramine. Whereas Helicobacter pylori can be many times more resistant to chlorine than Escherichia coli, both organisms are about equally susceptible to the disinfecting effect of chloramine UV radiation to disinfect offers a new genre of contamination that essentially moves from chemical pollution to energy pollution. Because New Science has already disconnected energy from mass, it becomes impossible to compare the environmental impact caused by chlorine and UV (Khan and Islam, 2012). The next series of planned water pollution is through water fluoridation. The pretext here is that fluoride will prevent dental cavities, leading to savings in dental care (Islam et al., 2015). Typically, a fluoridated compound is added to drinking water, a process that in the U.S. costs an average of about $1.02 per person-year. Defluoridation is needed when the naturally occurring fluoride level exceeds recommended limits. A 1994 World Health Organization expert committee suggested a level of fluoride from 0.5 to 1.0 mg/L (milligrams per litre), depending on climate. Bottled water typically has unknown fluoride levels, and some domestic water filters remove some or all fluoride. In Europe, only Ireland (73%), Poland (1%), Serbia (3%), Spain (11%), and the U.K. (11%) fluoridate any of their water. Most developed countries, including Japan and 97% of the western European population, do not consume fluoridated water. In the U.S., about 70% of public water supplies are fluoridated. This equates to approximately 185 million people, which is over half the number of people drinking artificially fluoridated water worldwide. In terms of planned contamination of water, aspirin would come next. The popularity of aspirin declined after the market releases of paracetamol (acetaminophen) in 1956 and ibuprofen in 1969. In the 1960s and 1970s, John Vane and others discovered the basic mechanism of aspirin’s effects, while clinical trials and other studies from the 1960s to the

Sustainable Drinking Water Purification Techniques  133 1980s established aspirin’s efficacy as an anticlotting agent that reduces the risk of clotting diseases. This followed revival of Aspirin sales well into the 21st century. The scheme has become so successful that today, the following question is a serious one: “Should governments add low doses of aspirin to water supplies to save billions in healthcare costs? Or give free pills away?” Then there are numerous sources of pollution that are unplanned. One such source, namely, birth control pills and other medications have been making headlines over the last decade. It is well known that trace amounts of birth control and other medications—as well as household and industrial chemicals of every stripe—are present in many urban and suburban water supplies around the world as long as there is a water treatment plant or the ground water is in communication with the surface water. While this would cause alarm because no medication is naturally degradable, the debate revolved around whether their levels are high enough to warrant concern. For instance, in 2008 the U.S. Geological Survey (USGS) tested water in nine states across the country and found that 85 man-made chemicals, including some medications, were commonly slipping through municipal treatment systems and ending up in our tap water. Another report by the Associated Press found trace amounts of dozens of pharmaceuticals in the drinking water supplies of some 46 million Americans. However, according to USGS, such chemicals and medications are so diluted—at levels equal to a thimble full of water in an Olympic-sized swimming pool—that they do not pose a health threat. Scientific investigation, however, suggests that even extremely diluted concentrations of drug residues harm fish, frogs and other aquatic species, and have been shown to labs to impair human cell function. This effect cannot be tracked with conventional engineering analysis that relies heavily on fundamental premises that are based on misconceptions (Islam et al., 2010; Khan and Islam, 2012). One of the common culprits is estrogen, much of which is inadvertently released into sewers through the urine of women taking birth control. Studies have shown that estrogen can wreak reproductive havoc on some fish, which spawn infertile offspring sporting a mixture of male and female parts. Researchers at the University of Pittsburgh found that human breast cancer cells grew twice as fast when exposed to estrogen taken from catfish caught near untreated sewage overflows. Today’s science does not allow us to identify, let alone quantify risks associated to such artificial chemicals. What we know for fact is the number of breast cancer has skyrocketed in countries that use estrogen the most. Even though USA showed some decline in cancer rate, it is thought to be because of reduced usage of Hormone Replacement Therapy (HRT).

134  Sustainable Water Purification Climate Change Climate change is considered to be the equivalent of global obesity (Islam and Khan, 2016) that captures the overall environmental insult caused by the modern day practices. In the late decades of the 20th Century, the term global warming became in vogue and substantial government funding became available for research in this area. As an interesting note, substantial government funding was available for global cooling in the preceding decades to the global warming phenomenon. At the time, living in Northern Alberta, Canada (which is still subject to cold winters) there were cries of beware, danger in the streets from those scientists who continually advocated the coming of the glaciers – another Ice Age was about to arrive. Within the recent decades, the cause of global cooling has been diminished and the term global warming took over. However, as late as 2010, Chilingar et al. (2010) claimed that we are well within a cycle of global cooling. Global warming has been a subject of discussion since the late 1970s. It is thought that the accumulation of carbon dioxide in the atmosphere causes global warming, resulting in irreversible climate change. Even though carbon dioxide has been blamed as the sole cause for global warming, there is no scientific evidence that all carbon dioxides are responsible for global warming. Precisely to address this critical gap, this chapter includes a detailed analysis of greenhouse gas emissions from the Pre-industrial Age to the (for some) “Golden Era” of petroleum. A new theory has been developed, which shows that not all carbon dioxides contribute to global warming (Islam and Khan, 2019). The climate of the Earth can be affected by natural factors that are external to the climate system, such as changes in volcanic activity, solar output, and the variance of the orbit of the Earth around the Sun. Of these, the two factors relevant on time scales of contemporary climate change are changes in volcanic activity and changes in solar radiation. In terms of the energy balance of the Earth, these factors primarily influence the amount of incoming energy. Volcanic eruptions are episodic and have relatively short-term effects on climate. Changes in solar irradiance have contributed to climate trends over the past century but since the Industrial Revolution, the effect of additions of greenhouse gases to the atmosphere has also been recognized. However, as Islam and Khan (2019) recently pointed out, one must understand what is the most damning trait of modern-day technology development for one to discern major causes of climate change.

4.2.2 Corporatization and Healthcare The golden era of plastic and artificial chemicals is synonymous with spending money on medicines before even discovering the cause of the

Sustainable Drinking Water Purification Techniques  135 25%

Actual

Projected

20%

15%

10%

5%

0% 1961

1967

1973

1979

1985

1991

1997

2003

2009

2015

2021

2027

Figure 4.7  Healthcare expenditure in USA during 1961-2027.

disease. The United States has one of the highest costs of healthcare in the world. In 1902 governments in the United States spent 0.25 percent of GDP on health care programs. In the early 21st century, governments spent over 7 percent of GDP on health care programs. Health care spending increased rapidly during the second half of the 20th century, most of which related to medicine and diagnostic tools. In 2017, the U.S. spent about $3.5 trillion on healthcare, which averages to about $11,000 per person. Relative to the size of the economy, healthcare costs have increased dramatically over the past few decades, from five percent of GDP in 1960 to 18 percent in 2017. The Center for Medicare and Medicaid Services (CMS) projects that such costs will climb to $6 trillion, or about $17,000 per person, and will represent about 19 percent of GDP by 2027. Figure 4.7 shows percentage of GDP spent on healthcare throughout 1960 through 2020 (predicted for 2018-2020). Health care spending started out at the beginning of the 20th century at 0.25 percent of Gross Domestic Product (GDP). It increased slowly during the first half of the century, peaking at one percent of GDP in 1933 and then declining to 0.38 percent of GDP in World War II. In 1965 Congress passed Medicare, the federal health care program for Americans over 65 years old, and Medicaid, the joint federal-state health care program for the poor, and ever since health care spending has consistently grown much faster than GDP.

4.2.3 Death and Lifestyle Figure 4.8 shows top 10 leading causes of death in USA. Throughout last few decades, the 10 leading causes of death involved heart disease, cancer, chronic lower respiratory diseases, stroke, unintentional injuries, Alzheimer’s disease, diabetes, influenza and pneumonia, kidney disease, and

136  Sustainable Water Purification Heart disease Cancer Unintentional injuries Chronic lower respiratory diseases Stroke Alzheimer’s disease

2016

Diabetes Influenza and pneumonia Kidney disease

2017

Suicide 0

120 160 40 80 Deaths per 100,000 U.S. population (age adjusted)

Figure 4.8  Death rate for major causes of death in USA (SOURCE: CDC/NCHS, National Vital Statistics System, Mortality).

suicide. In 2011, they accounted for 73.8% of all deaths in the United States (Islam et al., 2015). From 2011 to 2012, age-adjusted death rates declined significantly for 8 of 10 leading causes of death. The rate decreased 1.8% for heart disease, 1.5% for cancer, 2.4% for chronic lower respiratory diseases, 2.6% for stroke, 3.6% for Alzheimer’s disease, 1.9% for diabetes, 8.3% for influenza and pneumonia, and 2.2% for kidney disease. The rate for suicide increased 2.4%. The rate for unintentional injuries remained the same. Heart disease and cancer remain the 1st and 2nd leading causes of death, respectively, over the 80-year period. A 80-year perspective points to both stability and change in the leading causes of death: stability because three causes (heart disease, cancer, and stroke) remained among the five leading causes each year between 1935 and 2010; and change because other causes moved into or dropped out of the five leading causes at different points over the past 80 years. There were also changes in the proportion of all deaths that were due to each of the leading causes. For example, heart disease and cancer were the leading causes of death from 1935 to 2010, but it was in 1983 that these two conditions accounted for the highest percent (60 percent) of all deaths. In 2010, they constituted 47 percent of all deaths. According to the CDC, the 10 leading causes of death together account for about three quarters of United States deaths. Cancer caused nearly as many deaths as heart disease – 152.5 per 100,000. This represented a significant decrease from the 155.8 cancer deaths per 100,000 seen in 2016. The remaining top 10 causes of death, in decreasing order, were unintentional injuries, chronic lower respiratory diseases, influenza and pneumonia, kidney disease, and suicide.

Sustainable Drinking Water Purification Techniques  137 Though life expectancy at birth decreased to 78.6 years in 2017, down from 78.7 years in 2016, that change was driven primarily by suicide and drug overdose. However, heart disease remains the leading cause of death in the United States, at 165 deaths per 100,000 individuals in 2017. This represents a slight, statistically non-significant, decrease from the 165.5 deaths per 100,000 caused by heart disease in the previous year. Other diseases related to cardiometabolic health saw increases. Stroke and diabetes each caused a small but significant increase in deaths in 2017, which saw a 1-year increase to 37.6 from 37.3 stroke deaths per 100,000 people. Diabetes deaths increased to 21.5 from 21 per 100,000 the previous year. Stroke was the fifth and diabetes the seventh most common cause of death, according to the data brief published by the CDC’s National Center for Health Statistics (NCHS). Alzheimer’s disease deaths also increased significantly, from 30.3 per 100,000 in 2016 to 31 per 100,000 in 2017. Although Alzheimer’s exact etiology remains under study, cardiovascular disease factors and Alzheimer’s disease share many risk factors and are often comorbid. Infant deaths from congenital malformations decreased from 2016 to 2017, from 122.1 to 118.8 deaths per 100,000 live births. The age-adjusted death rate for the total population decreased 1.1% from 731.9 deaths per 100,000 standard population in 2017 to 723.6 in 2018 (Figure 4.9).

721.9

All causes

1723.6

165.0

Heart disease

1163.6

2017 2018

152.5

Cancer 49.4 148.0 40.9 139.7 37.6 137.1 31.0 130.5 21.5 21.4 14.3 214.9 13.0 12.9 14.0 214.2

Unitentional injuries Chronic lower respiratory diseases Stoke Alzheimer disease Diabetes Influenza and pneumonia Kidney disease Suicide 0

1149.1

200

400

600

800

Deaths per 100,000 U.S. standard population

Figure 4.9  Age-adjusted death rates for all causes and the 10 leading causes of death in 2018: United States, 2017 and 2018.

138  Sustainable Water Purification In 2018, the 10 leading causes of death (heart disease, cancer, unintentional injuries, chronic lower respiratory diseases, stroke, Alzheimer disease, diabetes, influenza and pneumonia, kidney disease, and suicide) remained the same as in 2017. Causes of death are ranked according to number of deaths. The 10 leading causes accounted for 73.8% of all deaths in the United States in 2018. From 2017 to 2018, age-adjusted death rates decreased for 6 of 10 leading causes of death and increased for 2. The rate decreased 0.8% for heart disease (from 165.0 in 2017 to 163.6 in 2018), 2.2% for cancer (152.5 to 149.1), 2.8% for unintentional injuries (49.4 to 48.0), 2.9% for chronic lower respiratory diseases (40.9 to 39.7), 1.3% for stroke (37.6 to 37.1), and 1.6% for Alzheimer disease (31.0 to 30.5). The rate increased 4.2% for influenza and pneumonia (14.3 to 14.9) and 1.4% for suicide (14.0 to 14.2). Rates for diabetes and kidney disease did not change significantly. Other conditions have all occupied spots within the five leading causes for some but not all years between 1935 and 2019. Specifically, chronic lower respiratory diseases entered the five leading causes of death in 1979; certain diseases of early infancy was among the five leading causes only from 1949 to 1962 and 1964; accidents entered the five leading causes of death in 1946; kidney disease was among the five leading causes only from 1935 to 1948; and influenza and pneumonia was among the five leading causes between 1935 and 1945, again in 1963, and between 1965 and 1978. For all but the oldest age group (85 years and over), mortality risk fell more than 50 percent between 1935 and 2010 (Figure 4.10). The greatest reduction was among persons 1–4 years of age where the death rate Age in years

Pecentage change

0

Under 1

1-4

5-14

15-24

25-34

35-44

45-54 55-64 65-74

75-84

85 and over

–20 –40 –60 –80

–100

Figure 4.10  Percentage change in death rates by age: United States, 1935–2010. NOTE: 2010 data are preliminary. SOURCE: CDC/NCHS, National Vital Statistics System, Mortality.

Sustainable Drinking Water Purification Techniques  139 declined from 440.9 to 26.6 deaths per 100,000 population, a decrease of 94 percent. Declining death rates were seen among the over 65 population, although not of the same magnitude as among the younger ages. For example, for persons 65–74 years of age, death rates declined by 62 percent, while death rates decreased by 58 percent for those 75–84 years of age, and declined 38 percent for persons 85 years or more. In 2018, life expectancy at birth was 78.7 years for the total U.S. population—an increase of 0.1 year from 78.6 years in 2017 (Figure 4.11). For males, life expectancy changed from 76.1 in 2017 to 76.2 in 2018—an increase of 0.1 year. For females, life expectancy increased 0.1 year from 81.1 years in 2017 to 81.2 in 2018. Life expectancy for females was consistently higher than it was for males. In 2018, the difference in life expectancy between females and males was 5.0 years, the same as in 2017. In 2018, life expectancy at age 65 for the total population was 19.5 years, an increase of 0.1 year from 2017. For males, life expectancy at age 65 increased 0.1 year from 18.0 in 2017 to 18.1 in 2018. For females, life expectancy at age 65 increased 0.1 year from 20.6 years in 2017 to 20.7 in 2018. The difference in life expectancy at age 65 between females and males was 2.6 years remains unchanged from 2017.

At birth 78.6 78.7

Both sexes

2017 2018

76.1

Male

76.2 81.1 81.2

Female At age 65 19.4

Both sexes

19.5 18.0 18.1

Male

20.6 20.7

Female

0

20

40 60 Life expectancy (years)

80

Figure 4.11  Life expectancy at selected ages, by sex: United States, 2017 and 2018.

100

140  Sustainable Water Purification

4.2.4 Role of Water in Bodily Functions One of the biggest problems in describing the role of natural elements in affecting human physiology is, New Science has focused on tangible thereby disconnected the natural sequence in research (Islam et al., 2017). Only recently, it is being recognized as a major issue (Liu, 2017). Any discussion of sustainability must take a holistic approach and as such, this section is opens with a discussion of traditional Chinese medicine and New Science. As we have seen in Chapter 2, the science of water uses a holistic approach and that approach is now connected to various diseases that have origins in various vital organs. It is interesting that the most frequent cause of death in USA is heart disease. There is a general acknowledgement in all civilizations that the heart is the most important organ in the human body. In ancient medical classics from Babylon, Egypt, Greece, Rome, and China, it is generally described as being the center of a system of vessels supplying the various parts of the body (Acierno, 1994). In Islamic medicine, heart is where conscience lies and governs the overall consciousness of a person (Islam et al., 2017). Although western medicine considers the heart as a vital organ, only eastern medicinal practices (traditional Chinese medicine, TCM, Ayurveda, Islamic medicine, etc.) retained the original role of the heart. Europe has reduced it into tangible aspects. That focus has removed heart (or any other vital organ) from its fundamental role in working in concert with the whole body. Traditional Chinese medicine (TCM) retained the original role of the heart (called the monarch organ) and its relationship between the heart and exterior things. In TCM, the physiological functions of the heart are governing blood and vessels, controlling the mind, opening into the tongue, manifesting on the face, and so on. Only the tangible aspects of these functions are covered in modern Western medicine through anatomical structure, spatial connection, and micromechanical character of the organ. TCM and Western medicine have their separate diagnostic and management systems that are very different from each other. Figure 4.12 shows an integrative view of the heart in traditional Chinese medicine (left half) and Western medicine (right half). This figure clearly shows how western medicine has disconnected vital connection of the heart with other organs by neglecting intangibles. Based on this fundamental truth, Chinese medicine and Western medicine have formed their own knowledge systems and have developed respective theories for the diagnosis and management of heart diseases.

Sustainable Drinking Water Purification Techniques  141 Traditional Chinese Medicine

Western Medicine hide Brain anterior insular spirits penaquedutal gray matter

Fire

X-Ray

anterior cingulate cortex

Emotion Joy

5-element

Amygdale

parabrachial

Lung

nucleus

BNP

Season

Summer

Manifest Collaterals in Blood Face Meridians

Direction South

Color Red

MRI

Hypothalamus

Zong QI

DCG Gas (O2, CO2)

Heart

ECG

Nervous Sys.

Ions

Lung Pulmonary circulation

ANP

open to Tongue

interior exterior

Circulatory Sys. Shao Yin vessel

Small Intestine Flavor Bitter

Lab Exam.

Kidneys

n io lat u c Coronary cir ic m angiography e st Sy Ultrasonic Doppler

Figure 4.12  Integrative comparison of TCM and western medicinal description of heart and other vital organs.

The heart is regarded as the monarch of all organs in TCM, and “Shen ) is what defines the purpose of life and primary job descripMing” ( tion assigned to every human. The closest translation of this word would be khalīfah (viceroy, Quran 2:30 defines that to be the principal function of each human) in Arabic and avatar in Sanskrit). In TCM, one thinks with the heart. This is in line with Islamic narrative of heart functions. The responsibility of the heart is to be the emperor of all organs, even of the brain, for the commander-in-chief achieved dominion over the whole body by governing blood and vessels. Furthermore, at a higher level, the heart is seen as the center of the mind and consciousness for its storing spirit (Flaws et al., 2008). Normal mental activity depends on regular cardiac function, for example, people will lose their mind when the heart is in disorder. As can be seen from Figure 4.12, for western medicine, the heart is like a mechanical pump that generates pressure to transport blood through the body. Besides its role as the dynamic source of circulation, the heart is also seen as the engine (another mechanical role) of the body because it

142  Sustainable Water Purification propels the blood flow. The exact structure of the heart was not clear until the Renaissance period when it was discovered that the heart is made up of four separate chambers. Further anatomical studies revealed that the heart has a blood supply system of its own and a conducting system that consists of specialized cardiac muscles found in the sinoatrial node and in the atrioventricular node and bundle (Moore et al., 2014). There is nothing in common between TCM approach and the western approach. Yet, numerous modern TCM researchers as well as alternate medicine practitioners have rushed to find similarities and often recommended that the two be combined in order to complete a treatment. Liu (2017) summed up the difference in the following statement: “Systematic descriptions of the heart by TCM terms can be found in ancient Chinese medical classics, which were recompiled in 200 BC. From then on, TCM theories have been guiding the clinical practice steadily for more than 2,000 years. In comparison, Western medicine, originating from the “Corpus Hippocraticum,” has continuously been updating its theories with new discoveries. It looks as if these 2 types of medicine have been running on 2 different rails starting from the same station but going into different directions.”

That phrase ‘same station’ happens to be very mechanical description of the most tangible functions of the heart. A holistic consideration must involve both tangible and intangible aspects of any process. The combination of five element theory and Zang Fu theory shows that there is a continuation connection through various “energy” levels. The five elements each has a spirit (intangible) aspect of it. Figure 4.13 shows how different spirits connect with Shen, the umbrella ‘spirit’ belonging to the creator. Creator

SHEN HUN

ZHI

YI

PO

Figure 4.13  The existence of 5 spirits, the heart being the dominant one and creator being connected to the heart.

Sustainable Drinking Water Purification Techniques  143 It is the heart that controls all other organs, both physically and spiritually. In this process, hun relates to the wood element, Yi to the earth element, Po to the metal element and Zhi to the water element. Liao et al. (2017) shows how these elements are connected to both Zang and Fu organs, along with the emotions that trigger imbalances in the respective organs (Figure 4.14). The 5 Zang organs include heart, lung, liver, spleen, and kidney. The theory does not only describe the physiological functions of the 5 Zang organs but also shows their relationships between the organs and the body, the organs and the orifices, and also describes the relationship between the 5 Zang organs and the 5 constituents, the 5 Zang organs, and the focal external manifestations. Table 4.1. Completes the description and inserts Islamic description of intangible qualities attributed to various organs. This is derived from the following Hadith. ‘Iyād Ibn Khalīfa heard ‘Alī say at Siffīn, “The intellect (Aql) is located in the heart. Mercy (rahma) is located in the liver, Compassion (rafa) is located in the spleen. The self or characteristic wind (nafs) is located in the lungs” (Al-Albani, Book 30, Hadith no. 10)

The next cause of death is cancer, which relates to practically all vital organs. Although new science focuses on the organ or location, where the fu organ Small intestine

Large intestine

Gallbladder

Stomach

Bladder

zang organ

Heart

Lung

Liver

Spleen

Kidney

Governing

Vessels

Skin

Tendons

Four limbs

Bones

Opens

Tongue

Nose

Eyes

Mouth

Ears,external genitals and anus

Face

Hair

Nails

Lips

External manifestation

Hair

Figure 4.14  The Five Zang organs, its constituents, and its orifices (From Liao et al., 2017).

Sour Qi (Nafs)

Small intestine

Heart

Vessels, sex glands

tongue

Face

Intuition Joy Peace

Moodiness

Bitter

Aql

Fu organ

Zang organ

Governing

Opens

External manifestation

Trait

Mental part

Taste

Islamic/Ibn Sina

Sensitivity

Sadness

Hair

Nose

Skin

Lung

Large intestine

Po

Shen

Intangible element

Metal

Fire

Tangible element

Empathy (Rahma)

Spicy

Mental activity

Anger

Nails

Eyes

Tendon

Liver

Gall bladder

Hun

Wood

Table 4.1  Complete description of the 5-element theory as applied in human physiology.

Pity (Rafa)

Sweet

Pondering

Worry

Lips

Mouth

Four limbs

Spleen

Stomach

Yi

Earth

Salty

Will power

Fear

Hair

Ears, external genitals and anus

Bones

Kidney

Bladder

Zhi

Water

144  Sustainable Water Purification

Sustainable Drinking Water Purification Techniques  145 cancer manifests itself, holistic analysis (such as TCM) would reveal something different. For instance, skin cancer is a matter of skin in New Science but it is a matter of lung in TCM. Brain cancer is a matter of brain in New Science, TCM says it is a matter of kidney, spleen, and heart, which collectively governs all emotions and tangible brain and bone marrow activities (Sakatani, 2007). The holistic approach stems from the simple principle that there is no discontinuity between mass and energy or tangible and intangible. Everything that makes up a human being, mind-body-spirit, correlates at an energetic level to something tangible in nature. This principle of interconnectedness also applies between different physical aspects of our bodies. For example, the Kidney organ correlates with the tissue of bone/teeth, the sensory taste of salt, the sensory organ of the ear, and the areas of the lower back, knees, and the heels/feet. Liver Health: According to TCM, the Liver is the organ that is most affected by excess stress or emotions. In Islamic medicine, empathy resides with liver. As such, any imbalance will cause a person to lose empathy, depriving him of the essence of humanity. At that point, the body gets launched into a spiralling down mode. While New Science does not recognize this process of the progression of a disease, it does recognize the connection between alcoholism, cigarette addiction with aggressive behaviour, then back to liver damage. Heart Health: True cardiovascular health is not about physical fitness of the heart, it’s rather about deep contentment with one’s life and destiny. TCM recognizes the role of contentment and love are often associated with the heart representing a state of peacefulness. Ancient Chinese culture recognized the need for the heart to be in tune with Dao (Highest consciousness) for it to reach statement of good health. In Islamic heart is where conscience and intention resides – intention being the only freedom a human has. Islamic philosophy dictates that act on empathy, conscience and long-term objectives make a heart peaceful and give rise to any fruitful decision. Spleem Health: Chronic stress, worry, and anxiety can damage Spleen and related stomach functions very quickly. Without the proper functioning of the Stomach and its partner organ the Spleen, you can easily begin to suffer from poor digestive health and low metabolism function. Lung Health: Too much sadness and grieving can harm the Lung and its partner, the Large Intestine. While new science focuses on smoking to cause lung cancer, it ignores the intangible aspects. For instance, a person confined in an office, in absence of sunlight will develop lung cancer, as evidenced in many cases, but New Science fails to explain such occurrences.

Immune system is important, and as such both water element and lung play a role Includes genetic vulnerability and water quality

Water, wood Metal Water Fire, Earth, wood

Lung, Heart, Kidney, Spleen

Lung, heart

Heart, lung, Kidney

N/A

Spleen, Kidney

Kidney, Liver

Lung

Kidney

Heart, Spleen, Liver

Chronic lower respiratory diseases

Stroke

Unintentional injuries

Alzheimer’s disease

Diabetes

Influenza and pneumonia

Kidney disease

Suicide

Earth, Water

N/A

Fire, metal, Water

Metal, fire

Metal, water, Earth

Unless schizophrenia, it is a combination of several factors

Genetic one is related to Kidney but Non-genetic one is combination of heart, spleen, lung and kidney

Food quality, water quality as well as energy quality (e.g. artificial light, energy sources) will affect

N/A

Water quality as well as genetic vulnerability will play a role

Most sensitive to air quality, including the one due to air conditioning

Cancer is the overall failure of the immune system that succumbs to repeated insult with artificial material.

Heart diseases are often linked to lung and overall immune system, affected by artificial thinking; affected by artificial light and other energy sources

Cancer

Fire

Heart

Comments

Heart disease

Elements

Vital organs involved

Disease

Table 4.2  Various leading causes of death to vital organs that govern the related function.

146  Sustainable Water Purification

Sustainable Drinking Water Purification Techniques  147 According to TCM, lung is connected to large intestine and govern skins. New Science rarely looks at skin or intestine cancer’s link to the lungs. Kidney Health: The Kidney is the “reserve generator” of energy in the body, supplying extra vital energy to all the organs when necessary. Its corresponding emotion of fear can be a red flag that these powerhouses of the body are themselves low on immunity and working too hard. The kidney has water as the primary element and it thus contains all genetic information of a person. While New Science recognizes the role of genetics, it confines to negative aspects and does not include the role of environment in shaping water ‘energy’. This, in turns, makes it impossible to trace the root cause of any disease. The next most death-causing disease is lower respiratory disease. In TCM, this disease is connected to both lung and heart (Zhen et al., 2018). As such, lifestyle, air quality and water quality will feature prominently. Stroke is the next most fatal disease. Stroke in TCM, relates to the heart, lung, as well as spleen and kidney (Zhang and Yang, 2012). Alzheimer’s disease is New Science is most about brain and nervous system. In TCM, it is connected to Kidney as well as Spleen (Sun et al., 2013). As such water quality as well as genetic factors feature prominently. Also important is to maintain organic food habits. New science connected refined fuel with Alzheimer only recently (Helou and Jacker, 2013). Similarly, all other deadly diseases relate to some form lifestyle and water quality issues. They are listed in Table 4.2.

4.2.5 A Relevant Anecdote A relevant anecdote, which highlights the role of lifestyle and particularly water quality, exists from Ecuador. The village of Vilcabambawas identified as the “valley of longevity” by a Harvard Medicine professor (Leaf, 1973). French studies had shown that the diet and lifestyle of the inhabitants may have been a factor. Nobel Laureate Chemist, Richard Laurence Millington Synge, the man who discovered amino acids, claimed that there are remarkable medicinal qualities to be found in the plant life in certain places near the Ecuador in the proximity of the valley of Vilcabamba. Thanks to scientific chemical assay techniques, analysis has now shown that the fruit, roots and herbs of this particular equatorial subarea offer some of the strongest anti-oxidant protection in the world. In 1981, the Ecuadorian government hired medical journalist Dr. Morton Walker to study these people in depth. In his book, “The Secret to a Youthful Long Life”, Walker reported that his research showed the mineral rich water that the Vilcabambans drank was key to their long lives and health. Laboratory analysis of the Vilcabamba

148  Sustainable Water Purification water determined that the unique balance of enriched colloidal minerals in the local drinking water was ideal for promoting optimum human health. In 1991, businessman Craig Keeland traveled to Vilcabamba to study the anti-oxidants. He developed and marketed a whole fruit puree made from Vilcabamba fruits and vegetables and sold it through his former company, Youngevity, which he sold in 2005. In July 2003, Keeland formed a new company that developed a whole food puree product called ViaViente which is now sold globally in over 26 countries and territories. Keeland founded the Andes Children’s Foundation in 2003 to support the education of children in Vilcabamba. Furthermore, medical researchers had confirmed that the retinas of 100 year-old residents are often comparable with those of 45 year-old city-dwellers. The same village now forms the core of another epidemiological study. It has the highest rate of stomach cancer in the world (over 50 for 100,000 inhabitants). How is such drastic switch possible? The answer, of course, lies within consideration of each health practices that has changed in that community (Islam et al., 2015). Such practices may include, water purification, usage of European toilet, processed food, smoking cigarettes, and numerous other artificial changes that are made in name of civilization. Natural processes have been replaced with new processes that increased the profitability and created a paradigm shift.

4.3 Natural Minerals Any water purification technique can be physical, chemical or biological. Sustainability considerations require that each of these use natural material or process. Physical processes include factors, such as dilution, adsorption, sedimentation, evaporation, advection and mixing. Each of these can be enhanced with natural materials. Chemical processes are include factors, such as, hydrolysis, photochemical reactions, photolysis, oxidation, reduction, and ridding of free radicals. Biological processes can include microorganism-dependent oxidations, reductions, biotransformation, accumulation by organisms, filtration of water by suspension-feeding organisms, excretion of molecules which are instrumental in increasing the rate of some chemical processes of degradation of pollutants, production of oxygen that is involved in chemical oxidation of pollutants, transpiration, regulation of biological processes of water purification by other organisms (Ostroumov, 2006).

Sustainable Drinking Water Purification Techniques  149

4.3.1 Filters As stated earlier, freshly withdrawn ground water is the best for drinking. If water has to be stored (say for lack of natural source), it should be stored in glass containers. More importantly, it should be recognized that chlorine infested water or water, which is recycled from sewage is not acceptable for human consumption. Today, water filtration has become necessary in most parts of the world due to pollution. We have sophisticated technology to filter water, but none of them is sustainable because each uses chemical resins or others to ‘purify’ the water. There are natural options that have been used for hundreds and thousands of years before man-made alternatives were invented and promoted as a sign of sophistry and civilized lifestyle. Sand: The use of sand for water filtration dates back thousands of years. The Greeks and Romans used sand to remove sediment from the water in their pools and bathhouses. Sand can filter out particles as small as 25 microns and leave no harmful residuals in the water. Also, sand is excellent for removing bacteria, eliminating the possibility of secondary contamination. Oysters: Oysters naturally filter toxins when they feed. The water passing through the oysters is purified enough to drink. In some parts of the world, natural oyster reefs are still the preferred method for water filtration. One adult oyster can filter more than 60 gallons of water per day. In Chapter 5, details are given on the use of fish scale and other biological materials, which are more suitable for agricultural applications. Plants: Plants are a natural choice for water filtration, especially in wetland areas. Plants automatically filter the water in which they live by adding oxygen and removing carbon dioxide. Some plants also remove heavy metals and toxins while stimulating the growth of beneficial bacteria. Water lettuce and water hyacinth are so effective that they are sometimes incorporated into the first step of wastewater purification. Charcoal: Charcoal is a slow, but effective, water filter. The carbon in charcoal helps remove toxins. Charcoal filters out particles larger than a micron, including nitrogen oxide, lead and sulfur oxide. Coconut: Coconut filters water by absorbing it through layers of fiber. Coconut milk is second only to water in purity. Commercial water filters often use coconut carbon filters to remove toxins and particles. The coconut husks can trap most particles, toxins and parasites, including cryptosporidium and giardia.

150  Sustainable Water Purification Zeolite, Limestone, etc: These are natural rocks that can act as a filter as well as enricher of minerals in the drinking water. Unlike chemical filters, they do not need recharging or cleaning with toxic chemicals.

4.3.2 Ground Water Recharge In many cases, groundwater is in shallow or over-exploited. The infiltration surface can be constructed to preserve and enhance the capability of the soil to pass flows from the basin into the groundwater. Also using the planted surface, rather than crushed stone or sand surface can help improve the groundwater rechargement quality because it prevent of runoff flowing. Also, the water undergoes natural filtration and mineralization as long as synthetic fertilizer or pesticide are used. This process can be practiced especially in river valleys and sedimentary plains by infiltrating river or lake water into shallow sand and gravel layers. The infiltration technique is chosen according to the hydrogeological conditions, the available ground space, the water need, the composition of the infiltrated water, and the degree of purification to be achieved (Balke et al., 2000).

4.3.3 Aeration Increase in air can increase the population of aerobic bacteria and the death of harmful anaerobic bacteria. Reduced oxygen in water decreases water quality and finally eutrophycation occurs. Eutrophication is when the environment becomes enriched with nutrients. This can be a problem in marine habitats such as lakes as it can cause algal blooms. Some algae even produce toxins that are harmful to higher forms of life. This can cause problems along the food chain and affect any animal that feeds on them.

4.3.4 Brick, Clay and Others Clay minerals are well known for their ability to remove heavy metals from water (Jiang et al., 2010; Chaalal and Islam, 2000). Recently brick, made out of natural clayey soil, has been found to be effective in filtering water while removing metals from it. In fact, the sorption characteristics of brick were found to be better than those of sand (Arias et al., 2006; Boujelben et al., 2009) and to increase with the quantity of oxides and/or hydroxides of iron, aluminum and manganese associated with the material (Boujelben et al., 2008). Furthermore, the adsorption performance of crushed bricks for a wide variety of salts was found to be comparable with that of activated

Sustainable Drinking Water Purification Techniques  151 charcoal (Selvaraju and Pushpavannam, 2009; Yadav et al., 2006). Dehou et  al. (2012) reported works on crushed bricks, showing excellent data about their capacity to remove dissolved iron(II) from ground waters which were sampled in Bangui-region wells in Central African Republic.

4.4 Solar UV Treatment With the plastic era came the era of artificial energy and artificial water cleaning techniques. Over a century ago, advanced oxidation processes (AOPs) were described as chemical degradation reactions which involve hydroxyl radical (• OH) in the primary step (Mihaela, 2017). It was the beginning of chemical treatment for purifying water. The first study on the degradation of organic compounds through a process which at that time was not known as proceeding through hydroxyl radical reactions was published by Fenton (Fenton, 1894). Fenton observed that tartaric and racemic acids are degraded in solutions in the presence of trace amounts of ferrous (Fe2+) salts and hydrogen peroxide but he did not investigate the mechanism of this reaction. Haber and Weiss (1932) were the first to propose that Fe2+ reduces H2O2 with formation of hydroxyl radicals. Although the photochemical decomposition of H2O2 was extensively investigated from the early 1900’s through the 1950’s, the first study on OH production via H2O2 photolysis for the purpose of organic contaminant destruction in aqueous waste streams was reported in 1975 (Koubeck, 1975). The UV/H2O2 process is also the most commercially implemented AOP. The first UV system using the UV/H2O2 process was installed in 1992 in Gloucester (ON, Canada) to treat 1,4-dioxane (pump & treat with aquifer recharge application). The first UV/H2O2 process was first time implemented to water treatment for public consumption in 1998 in Salt Lake City, UT, to remove tetrachloroethene (PCE) from contaminated groundwater. Currently, numerous full-scale UV/H2O2-based systems are installed at water utilities around the world to treat micropollutants in contaminated surface waters, groundwater, and wastewater tertiary effluents for water reuse. In 1990s, the negative effects of this process started to surface. In 2000, Al-Maghrebi et al. (2000) showed that all benefits of the process could be achieved, without the sideeffects by using solar UV directly. Chaalal and Islam (2000) showed that such process can be coupled with novel natural membrane systems in order to remove even radioactive compound from the water stream.

152  Sustainable Water Purification

4.5 Natural Ozonation Ozonation is an old water purification technique. In recent years, catalytic ozonation has received considerable attention due to its high oxidation capacity on organic matters in the wastewater. The direct catalytic oxidation seems to be relatively slow and selective (Sui et al., 2010), so different catalytic ozonation processes are combined to overcome these limitations and enhance the treatment efficiency (Dai et al., 2014). Recently, catalytic ozonation with solid catalysts has received wide attention, which exhibits relatively high degradation efficiency for organic pollutants in wastewater (Qi et al., 2012; Zhang et al., 2017). The solid catalysts mainly include carbon materials,  metal oxides  and metal oxides on supports. In particular, the Fe-based catalysts are most widely applied to catalytic ozonation since (1) they are widespread and abundant in nature and can be easily synthesized and obtained; (2) they almost have no toxicity; (3) some Fe-based catalysts show a high catalytic activity in catalytic ozonation system (Wang and Bai, 2017). The Natural mackinawite (NM), as a non-toxic mineral, is a precursor with great abundance to the more stable iron sulfide minerals (e.g., greigite and pyrite) (Gong et al., 2016). NM is mainly composed of iron sulfide (FeS) and has long-term stability in anoxic sediments (Jeong et al., 2007). Several studies have attempted to investigate NM to facilitate the removal of chromium, heavy metals and radionuclide from solutions or soils including hexavalent chromium (Mullet et al., 2004), dichlorodiphenyltrichloroethane (Pirnie et al., 2006), carbon tetrachloride, and 1,1,1-trichloroethane (Choi et al., 2009), tetrachloroethylene and trichloroethylene (Jeong and Hayes, 2007), hexachloroethane (Butler and Hayes, 1998), Cu2+, Cd2+ and Pd2+ (Ozverdi and Erdem, 2006), technetium (Tc), etc (Fan et al., 2014). Peng et al. (2018) used NM for catalytic  ozonation  for DMAC degradation. Their analysis of catalyst characterization suggests that NM had a favorable active species for catalytic ozonation. They optiimized several operating parameters to obtain the maximum degradation of DMAC (i.e., NM = 3.5 g/L, ozone flow rate = 300 ml/min and initial pH = 6.8, the DMAC degradation = 96.6%). Furthermore, NM could effectively catalyze ozone for the degradation of DMAC in comparison with application of ZVI/O3  and FeS/O3  (synthetic FeS) under the same conditions. In addition, degradation intermediates and pathways of DMAC were proposed. Meanwhile, the activated sludge inhibition experiment was carried out to prove the decreasing biotoxicity of the  degradation products  of DMAC

Sustainable Drinking Water Purification Techniques  153 were reduced via NM/O3 process. In addition, through control experiments (i.e., O3 alone, NM alone, Fe2+/O3 and Na2S/O3 system), NM was proved to have an irreplaceable activity to catalyze ozonation for DMAC degradation, meanwhile the S2− species could play an important role in promoting the Fe(II)/Fe(III) cycle. Besides, the reaction mechanisms involved ROS (HO•, H2O2 and O2•−) were investigated, the results show that the extraordinary efficiency for DMAC degradation was mainly caused by generation of HO• in NM/O3 system. NM/O3 process can be a great potential technology for treating the high concentration of the toxic and refractory pollutants in  industrial wastewater  due to NM with abundant, widespread source, low-cost and safety performances, moreover NM had an excellent catalytic activity to enhance the treatment efficiency. To-date, no one has reported ozonation without resorting to synthesis from oxygen, which is subjected to high voltage or UV irradiation. This is one area of research that should be expanded.

5 Sustainable Purification Techniques for Agricultural Waters 5.1 Introduction The water treatment issues confronting the agriculture market today include an ever-increasing demand for irrigation water, compromised water quality, declining availability, and expanded government regulations. As globalization takes hold, the world is moving toward more agricultural practices of the west. These practices are not sustainable and therefore very taxing on the global environmental health. Land and water resources are central to agriculture and rural development, and are intrinsically linked to global challenges of food insecurity and poverty, climate change adaptation and mitigation, as well as degradation and depletion of natural resources that affect the livelihoods of millions of rural people across the world (FAO, 2011). FAO predicts that world population will increase to 9.1 billion by 2050. In addition, economic progress, notably in the emerging countries, translates into increased demand for food and diversified diets. World food demand will surge as a result, and it is projected that food production will increase by 70 percent in the world and by 100 percent in the developing countries. Yet both land and water resources, the basis of our food production, are finite and already under heavy stress, and future agricultural production will need to be more productive and more sustainable at the same time (FAO, 2011). This builds up the hype that an apocalyptic crisis is imminent. This is the same model that has driven energy policy and virtually all aspects of modern economy (Islam et al., 2018). In economics, the notion of there being infinite need and finite resources is a fundamental premise that is asserted with dogmatic fervor in contemporary economics. In the context of water or petroleum resources, this notion has to help foment fear that is actually the driver of contemporary economics. This model starts off with the premise that needs must grow continually in order for the economy to thrive. Then, it implies, without

M. Safiur Rahman and M.R. Islam. Sustainable Water Purification, (155–220) © 2020 Scrivener Publishing LLC

155

156  Sustainable Water Purification looking at the validity of that premise, that there has to be an endless supply of resource to sustain the greed. Because such endless supply contradicts the other premise that natural sources are finite, there arises an inherent contradiction. One such article is written by Mason (2017), who poses this wrong-headed question: “But what happens to that equation when the net amount of energy we extract from the earth is shrinking? How, then, does an economy grow exponentially forever if the one element it needs more than anything to flourish is contracting with time?”

Then, he primes the audience with the need of a paradigm shift, that would involve challenging all orthodoxies involving the economy, as if to propose a revolution. Next, he creates a prophet out of a neuroscientist, Chris Martenson, who in recent years has turned his attention to the economy, particularly as it relates to dwindling energy resources and growing debt. Note how the premise of ‘dwindling energy resources’ is imbedded in this ‘revolutionary’ concept. How revolutionary is it? He writes: “He also got rid of most any equity stocks and put his money in gold and silver. He has been labelled a prophet of doom and a survivalist, by some. But more recently, his views have been receiving wider and more serious attention. He has been to Canada to talk to oil and gas investors, of all people. That’s incongruous given his view that we’re pillaging the Earth of its energy resources in the most inefficient and wasteful ways possible.”

Intuitively, it sounds simple – if I use up a certain amount of a finite quantity each year, it will eventually run out. But that tells you that you cannot have constant or increasing resource extraction from a finite resource, it does not tell you anything about what you do with the resources you extract, how productive they are, or whether or not they enable continued economic growth. It is certainly possible to sustain exponential growth infinitely with finite resources, as long as the usage is confined to sustainable or zero-waste operations. Similarly, all solutions end up proposing to minimize waste and maximize profit – an economic euphemism for Utilitarianism that has been preaching ‘maximizing pleasure and minimizing pain’ at a personal level. There has always been plenty of discussion in economics discourse about manipulating the interest rate, but never about eliminating it. There are plenty of suggestions regarding how to minimize waste, but one never proposes a solution to achieve zero-waste. There are even talks about

Sustainable Purifcation Techniques for Agricultural Waters  157 continuously increasing productivity, but never talk about the fundamental assumption of infinite need and finite resource. Nature is infinite – in the sense of being all-encompassing – within a closed system that nevertheless lacks any boundaries. Somewhat paradoxically, nature as a system is closed in the sense of being self-closing. This self-closure property has two aspects. First, everything in a natural environment is used. Absent anthropogenic interventions, conditions of net waste or net surplus would not persist for any meaningful period of time. Secondly, nature’s closed system operates without benefit of, or dependence upon, any internal or external boundaries. Because of this infinite dimension, we may deem nature – considered in net terms as a system overall – to be perfectly balanced. Of course, within any arbitrarily selected finite time period, any part of a natural system may appear out of balance. However, to look at nature’s system without acknowledging all the subtle dependencies that operate at any given moment introduces a bias that distorts any conclusion that is asserted on the basis of such a narrow approach. From where do the imbalance and unsustainability that seem so ubiquitous in the atmosphere, the soil, and the oceans actually originate? As the “most intelligent creation of nature,” men were expected to at least stay out of the natural ecosystem. Einstein might have had doubts about human intelligence or the infinite nature of the Universe, but human history tells us that human beings have always managed to rely on the infinite nature of nature. From Central American Mayans to Egyptian Pharaohs, from Chinese Huns to the Manichaeans of Persia, and from the Edomites of the Petra Valley to the Indus Valley civilization of the Asian subcontinent, all managed to remain in harmony with nature. They were not necessarily free from practices that we no longer consider (Pharaohs sacrificed humans to accompany the dead royal for the resurrection day), but they did not produce a single gram of an inherently anti-nature product, such as DDT. In modern times, we have managed to give a Nobel Prize (in medicine) for that invention. Islam et al. (2010, 2012) and Khan and Islam (2016) have presented detailed accounts of how our ancestors dealt with energy and water needs and the knowledge they possessed that is absent in today’s world. Regardless of the technology these ancient civilizations lacked that many might look for today, our ancestors were concerned with not developing technologies that might undo or otherwise threaten the perceived balance of nature that, today, seems desirable and worth emulating. Nature remains and will remain truly sustainable. By contrast, the western nations, who control the UN agenda, the focus is in selling western technology, train the indigenous population and then

158  Sustainable Water Purification throw them in deep despair that all efforts of salvaging them has been futile. If that is tot enough, further guilt is imparted and other experts show up to lecture them about demographics, changing consumption patterns, biofuel production and climate change impacts. The UN reports identify geographic zones with high population densities, where rainfed and irrigated crop production systems are under increasing pressure and are at heightened risk of reaching limits to increased production and productivities. These ‘systems at risk’ are drawn to the attention of the global community for concerted and timely remedial intervention, including through investments and international cooperation, not only on a global scale but locally, where the consequences of lack of action on agricultural livelihoods are likely to be greatest. The global land area is 13.2 billion ha. Of this, 12 percent (1.6 billion ha) is currently in use for cultivation of agricultural crops, 28 percent (3.7 billion ha) is under forest, and 35 percent (4.6 billion ha) comprises grasslands and woodland ecosystems (FAO, 2011). Low-income countries cover about 22 percent of the land area. Land use varies with climatic and soil conditions and human influences (Figure 5.1). Deserts prevail across much of the lower northern latitudes of Africa and Asia. Dense forests predominate in the heartlands of South America, along the seaboards of North America, and across Canada, Northern Europe and much of Russia, as well as in the tropical belts of Central Africa and Southeast Asia. Cultivated land is 12 to 15 percent of total land in each category. Grasslands and woodlands (33 to 39 percent) and forest land (20 to 33 percent) dominate land use and cover in all three country income categories.

>75% forest 50–75% forest >75% grass/shrub 50–75% grass/shrub >75% crops 50–75% crops Mixed >50% non-vegetable >50% bulb-up

Figure 5.1  Map showing global land use.

Sustainable Purifcation Techniques for Agricultural Waters  159 Cultivated land is a leading land use (a fifth or more of the land area) in South and Southeast Asia, Western and Central Europe, and Central America and the Caribbean, but is less important in sub-Saharan and Northern Africa, where cultivation covers less than a tenth of the area. Recall from Chapter 3 that this region is subject to most denigration in matters of drinking water use and sanitation. Table 5.1 shows land use for different income groups. The global area of cultivated land has grown by a net 159 Mha since 1961 (Figure 5.2). This increase, however, includes a larger area of land newly brought into cultivation, while over the same period previously cultivated lands have come out of production. The entire net increase in cultivated areas over the last 50 years is attributable to a net increase in irrigated cropping, with land under rainfed systems showing a very slight decline. Irrigated area more than doubled over the period, and the number of hectares needed to feed one person has reduced dramatically from 0.45 to 0.22 ha per person (FAO, 2010b). Missing from this description is the degradation of land quality due to the use of chemical fertilizers. Many recent studies have reported continuous degradation of soil with chemical fertilizers whereas continuous nourishment with organic fertilizer (e.g., Lin et al., 2019; Gregory et al., 2015). This is key feature of water sustainability that has been ignored by government bodies and international agencies. Lin, W. et al., 2019, The effects of chemical and organic fertilizer usage on rhizosphere soil in tea orchards, PLoS One, 14(5): e0217018. Gregory, A.S. et al., 2015, A review of the impacts of degradation threats on soil properties in the UK, Soil Use and Management, 12 October. Instead of looking at the global scenario, FAO takes a narrow view of sustainability concludes that a decline of about 135 Mha (3.3 percent) in forested area between 1990 and 2010 suggests that the expansion in the cultivated area and the replacement of degraded arable land with new cultivated land have been partly achieved through conversion of previously forested areas (FAO, 2010d). Globally, about 0.23 ha of land is cultivated per head of the world’s population. High-income countries cultivate more than twice the area per capita (0.37 ha) than low-income (0.17 ha) countries, while middle-income countries cultivate 0.23 ha per capita (Table 5.2). Assuming well-adapted production systems are used (meaning conforming to western standards), currently cultivated land is mostly of prime (28 percent of the total) or good quality (53 percent). The highest regional proportion of prime land currently cultivated is found in Central America and the Caribbean (42 percent), followed by Western and Central Europe (38 percent) and North America (37 percent). For

38

47

15

Low22 income

Middle53 income

High25 income

380

735

441

12

11

15

Global share of Share of global land, % population, % Mha %

Country category

20

880

27

2285 33

564

Mha %

Cultivated Forest land land

Table 5.1  Land use for various income growth.

1299

2266

1020

Mha

39

33

36

%

Grassland and woodland ecosystems

592

1422

744

Mha

18

21

26

%

31

69

52

Mha

1

1

1.8

%

Sparsely vegetated and barren Settlement and land infrastructure

123

79

41

4

1

1.4

Mha %

Inland water bodies

160  Sustainable Water Purification

Sustainable Purifcation Techniques for Agricultural Waters  161 Irrigated

Cropland per person

1600

0.50

1400

0.45

1200

0.40

1000

0.35

800

0.30

600

0.25

Hectare/person

Million hectares

Rainfed

0.20

400 1961 1965 1970 1975 1980 1985 1990 1995 2000 2005 2008

Figure 5.2  Evolution of land (From FAO, 2011).

high-income countries as a whole, the share of prime land in currently cultivated land is 32 percent (Table 5.2). In low-income countries, soils are often poorer and only 28 percent of total cultivated land is classed as prime. FAO, 2011, The state of the world’s land and water resources for food and agriculture (SOLAW) – Managing systems at risk. Food and Agriculture, Organization of the United Nations, Rome and Earthscan, London. In this chapter, guidelines are provided for sustainable water purification techniques applicable to the agricultural industry.

5.2 Organic vs. Chemical Agricultural Practices Conventionally, water sources used for agricultural applications include groundwater, surface water, treated municipal and industrial wastewaters, as well as liquid manures stored in lagoons onsite at large dairy and swine operations. Dairy and CAFO manure storage, treatment, and handling regulation compliance are major issues confronting these segments of the agricultural producer market. There are also water treatment issues and regulations confronting the vegetable and fruit processor’s segment of the market that involve vegetable/fruit washing and wastewater recycling that must be addressed. All plants require different set of nutrients such as the macro and micro nutrients for good and healthy growth (Tucker, 1999). The external features of plants do not show the impact of organic and non-organic agricultural practices differently. This is similar to external features of a human on

735

380

1556

Middle-income countries

High-Income countries

Total

Source: adapted from Fischer et al. (2010).

441

Low-income countries

6905

1031

3223

2651

Cultivated land Population (Mha) (million)

Regions

Table 5.2  Land use for various country classifications.

0.23

0.37

0.23

0.17

Cultivated land per capita (ha)

29

32

27

28

Prime land

52

50

55

50

19

19

18

22

Good land Marginal land

Rainfed crops (%)

162  Sustainable Water Purification

Sustainable Purifcation Techniques for Agricultural Waters  163 healthy diet or steroid. Each soil needs fertilizers to compensate for the nutrients taken by the plant. Before the so-called Green Revolution that made chemical fertilizer ubiquitous, the practice of applying partially decomposed animal waste in plants were the norm. natural and old process of returning the lost nutrients back into the soil. Today, the natural process of nourishing the soil is no longer the norm. During the Green Revolution, chemical fertilizer as well as synthetic pesticide were introduced with the promise of unprecedented growth in yield. The story of English wheat is typical. It took nearly 1,000 years for wheat yields to increase from 0.5 to 2 metric tons per hectare, but only 40 years to climb from 2 to 6 metric tons per hectare. Modern plant breeding, improved agronomy, and the development of inorganic fertilizers and modern pesticides fueled these advances (IFPRI, 2000). A superficial sustainability was quickly reached in the industrial countries and the threat of starvation was eliminated. These ‘advances’ were much slower in reaching developing countries. The colonial powers invested little in the food production systems of these countries, and by independence, their populations were growing at historically high rates. By the mid-1960s, hunger and malnutrition were widespread, especially in Asia, which increasingly depended on food aid from the west. Back-toback droughts in India during the mid-1960s made the already precarious situation worse, and a 1967 report of the U.S. President’s Science Advisory Committee concluded that “the scale, severity and duration of the world food problem are so great that a massive, long-range, innovative effort unprecedented in human history will be required to master it.” The plot thickened. Soon, the Rockefeller and Ford foundations took the lead in establishing an international agricultural research system to help transfer and adapt scientific advances to the conditions in developing countries. The first investments were in research on rice and wheat, two of the staple food crops for developing countries. The breeding of improved varieties, combined with the expanded use of fertilizers, other chemical inputs, and irrigation, led to dramatic yield increases in Asia and Latin America, beginning in the late 1960s. In 1968, U.S. Agency for International Development (USAID) Administrator William S. Gaud coined the term “Green Revolution” to describe this phenomenal growth in agriculture. To achieve higher yields for rice and wheat, scientists needed to develop plants that were more responsive to plant nutrients and that had shorter, stiffer straw to support the weight of heavier heads of grain. They also needed to develop varieties that could mature quicker and grow at any time of the

164  Sustainable Water Purification year, thereby permitting farmers to grow more crops each year on the same land. This was, in essence, putting the crops on steroid or growth hormone. New varieties also needed to be resistant to major pests and diseases, which flourish under intensive farming conditions, and to retain desirable cooking and consumption traits. Borrowing from rice-breeding work undertaken in China, Japan, and Taiwan, the International Rice Research Institute (IRRI) in the Philippines developed semi-dwarf varieties that met most of these requirements. Similar achievements were made for wheat after Norman Borlaug (later awarded the Nobel Peace Prize for his work) crossed Japanese semi-dwarf varieties with Mexican wheats at what is now known as the International Center for Maize and Wheat Improvement (CIMMYT) in Mexico. It was the first form of GMO and the culture of vaccine and antibiotic (Islam et al., 2015). Within years, the term Green Revolution, which originally described developments for rice and wheat, became synonymous with high-yielding varieties (HYVs) other major food crops, important to developing countries, including sorghum, millet, maize, cassava, and beans. Today, a full-fledged system of international agricultural research centers now works on practically all aspects of developing-country agriculture (the Future Harvest Centers that make up the Consultative Group on International Agricultural Research). The adoption of HYVs occurred quickly. By 1970, about 20 percent of the wheat area and 30 percent of the rice area in developing countries were planted to HYVs, and by 1990, the share had increased to about 70 percent for both crops. Yields of rice and wheat virtually doubled. Higher yields and profitability also led farmers to increase the area of rice and wheat they grew at the expense of other crops. Furthermore, with faster-growing varieties and irrigation, they grew more crops on their land each year. These changes more than doubled cereal production in Asia between 1970 and 1995, while population increased by 60 percent. Instead of widespread famine, cereal and calorie availability per person increased by nearly 30 percent, and wheat and rice became cheaper. Latin America experienced significant gains as well, but the impact in Sub-Saharan Africa was much more modest. Poor infrastructure, high transport costs, limited investment in irrigation, and pricing and marketing policies that penalized farmers made the Green Revolution technologies too expensive or inappropriate for much of Africa. It was thee beginning of a culture that would later be outed to have created the biggest scientific fraud in human history. External features were all looking attractive. For instance, The Green Revolution led to sizable increases in returns to land, and hence raised farmers’ incomes. Moreover, with greater income to spend, new needs for

Sustainable Purifcation Techniques for Agricultural Waters  165 farm inputs, and milling and marketing services, farm families led to a general increase in demand for goods and services. This stimulated the rural nonfarm economy, which in turn grew and generated significant new income and employment of its own. Real per capita incomes almost doubled in Asia between 1970 and 1995, and poverty declined from nearly three out of every five Asians in 1975 to less than one in three by 1995. The absolute number of poor people fell from 1.15 billion in 1975 to 825 million in 1995 despite a 60 percent increase in population. In India, the percentage of the rural population living below the poverty line fluctuated between 50 and 65 percent before the mid-1960s but then declined steadily to about one-third of the rural population by 1993. What was not accounted for in this rosy picture is the overall decline in quality of food and the increasing control of big banks that controlled all farmers, who became ever more dependent for paying for the western technology and agricultural products. The Green Revolution also created a façade of good nutrition. Without regards to the quality of food, meaning organic food and chemically grown food, food values were reduced to a linear number counted with calories. Everything artificial replaced everything natural, ranging from refined oil to all crops and livestock. As the transition from natural to artificial was completed, the profit margin of the western corporations skyrocketed. With the degradation of quality of food, followed the environmental degradation and increased income inequality, inequitable asset distribution, and worsened absolute poverty. Also, it became clear that owners of large farms were the main adopters of the new technologies because of their better access to irrigation water, fertilizers, seeds, and credit. Small farmers were either unaffected or harmed because the Green Revolution resulted in lower product prices, higher input prices, and efforts by landlords to increase rents or force tenants off the land. The Green Revolution encouraged unnecessary mechanization, thereby pushing down rural wages and employment. The crisis has hit Indian farmers so hard that Farmers’ suicide in India became synonymous with any social status of India. This national catastrophe of farmers committing suicide began in the 1990s, often by drinking pesticides, due to their inability to repay loans mostly taken from landlords and banks. As of 2014, in Maharashtra alone, more than 60,000 suicides had taken place, with an average of 10 suicides every day (Website 2). Figure 5.3 shows a total of nearly 300,000 Indian farmers had committed suicide since 1995. Of these, 60,750 farmer suicides were in the state of Maharashtra since 1995, with the remainder spread out in Odisha,

166  Sustainable Water Purification

Suicides Reported as per NCRB

Farmer suicides from 1995 to 2015

2015

2014

2013

2012

2011

2010

2009

2008

2007

2006

2005

2004

2003

2002

2001

2000

1999

1998

1997

1996

1995

20000 19000 18000 17000 16000 15000 14000 13000 12000 11000 10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0

Year

Figure 5.3  Suicide rate among farmers in India.

Telangana, Andhra Pradesh, Madhya Pradesh, Gujarat and Chhattisgarh, all states with loose financial and entry regulations. A number of social activist groups and studies proposed a link between expensive genetically modified crops and farmer suicides (Gruère and Sengupta, 2011). Bt cotton (Bacillus thuringiensis cotton) was claimed to be responsible for farmer suicides. The Bt cotton seeds cost nearly twice as much as ordinary ones. The higher costs forced many farmers into taking ever larger loans, often from private moneylenders charging exorbitant interest rates (60% a year). The moneylenders force farmers to sell their cotton to them at a price lower than it fetches on the market. According to activists and studies, this created a source of debt and economic stress, ultimately suicides, among farmers. Increasing costs in farming associated with decreasing yields even with use of BT cotton seeds are often quoted cause of distress among farmers in central India. A 2015 study in Environmental Sciences Europe found that farmer suicide rates in India’s rainfed areas were “directly related to increases in Bt cotton adoption.” Factors leading to suicide included “high costs of BT cotton” and “ecological disruption and crop loss after the introduction of Bt cotton.” (Gutierrez et al., 2011). Overall, agricultural processes have been turned on their heads at the expense of food quality and the overall environmental and

Sustainable Purifcation Techniques for Agricultural Waters  167 socio-economical integrity. A popular anecdote drives this point of socio-economic extremism. Consider the following 1. A healthy baby is born in a hospital after epidural treatment.* 2. A few days later, the baby is not responsive and feeling very lethargic. 3. The baby is rushed to the emergency, everything is considered other than the effect of epidural. Many blood tests and others are performed to check for infection. The baby goes home, ‘untreated’. 4. The mother takes the baby to a doctor. 5. The doctor gives the baby vaccines. 6. The child develops serious symptoms and is prescribed Tylenol. 7. A few days later, the child is back to doctor with symptoms of infections, and is prescribed antibiotic by the doctor. 8. The child continues to develop symptoms and more antibiotics follow, and Tylenol becomes a routine ‘home remedy’ 9. Child develops symptoms of asthma and ADHD. 10. Doctor prescribes steroids and Ritalin. 11. Mom thanks doctor for helping her child. In this particular anecdote, each activity is an economic activity with profound impact on the overall health of the child. Yet, during the same process, corporate profit skyrockets all at the expense of denaturing the child’s health (Figure 5.4). As Figure 5.4 depicts, this degeneration of the natural order is a mirror image of natural progression. They both reach an equilibrium, albeit the one at the bottom being the fictitious one. In modern economics, this fictitious equilibrium is anticipated and all measures are taken to introduce another process of denaturing which is more toxic than the previous one. That brings in the concept of Honey Sugar Saccharine® Aspartame®, denoted as HSS®A®N degradation by our research group (starting with Zatzman and Islam, 2007). The HSS®A®N pathway is a metaphor representing many other phenomena and chinks of phenomena that originate from in some natural form but become subsequently engineered through many intermediate stages into “new products”, ultimately * A solution of local anesthetic (freezing) and often a narcotic as well as is then given through this catheter inserted near the spinal cord. Also, added infusion of oxytocin or other synthetic hormone to induce early delivery.

168  Sustainable Water Purification Natural

Natural Healthcare

Activities 1 2

3

4

5

6

Region of exponential profiteering

7 8 9 10

Artificial

Corporate ‘Healthcare’

Figure 5.4  Economic activities have become synonymous with corporate profiteering and denaturing of the society.

transforming into nothing, for which the profit margin approaches infinity. These “new products” include materials, technology, and thought processes. This paper identifies the HSS®A®N pathway in theories of physics as discussed by all major scientists and philosophers. Since 2007, the authors have striven to popularize this Honey → Sugar → Saccharin®→Aspartame® pattern as a kind of shorthand reference to a particularly critical insight, often overlooked or only tangentially acknowledged, into the essence of the transformation of natural into artificial. This is a pattern so characteristic and widespread across every department of modern industrialized commodity production as to have become invisible. HSS®A® represents an entire class of other processes of degradation of a gift of Nature by its commodification as a byproduct of industrial-scale organic chemistry. In follow up papers, the works of Newton, Maxwell, Einstein, Feynman, and Hawking are reviewed and their fundamental premises deconstructed. Once identified, it becomes clear how disinformation works in the current system in the context of laws and theories of physics. One can then figure out a way to reverse the process by avoiding aphenomenal schemes that lead to ignorance packaged with arrogance. This mode of economics drives the waste-based technology, which is inherently anti-nature. By taking the short-term approach of maximizing quarterly profit, mechanisms have been created that make the world environment continuously worse. Figure 5.5 elaborates this aspect for technology development. It shows how cost to customers, which is indicative of

Sustainable Purifcation Techniques for Agricultural Waters  169

Quality of food

Honey Sap Natural juice Molasses

Cost to customers

Brown sugar Sugar Refined food/oil Instant mix/TV dinner Nutrient powder, energy drinks

Chemical refining/Denaturing

Figure 5.5  The outcome of short-term profit-driven economics model.

corporate profit, goes up exponentially as the quality of food goes down. This figure may be readily extrapolated to other aspects of social development, including politics and education.

5.2.1 Denaturing for a Profit Almost two decades ago, the author’s research group uncovered this progression from honey to sugar to saccharin to Aspartame®, labeling it the HSSA Syndrome. Numerous titles among its publications elaborate on the repeated appearance of the degenerative results of this cycle as a metaphor for many other phenomena in which engineered interventions degrade the quality and effectiveness of existing naturally-sourced chemicals and processes. The discovery and elaboration of the HSSA pattern has rich implications for the very notion of sustainability. Our research has yet to find a single corporate-controlled chemically-engineered process today that did not invent, and-or indefinitely extend a future for itself, either by adding anti-nature elements to a natural source or by completely replacing the natural source with a chemically-engineered substitute. Indeed: this describes the essence of the “plastics revolution” of our own time. Today, containers of literally every description as well as function-critical components all kinds of engines and other machines have been or are being replaced with chemically-engineered substitutes. These generally replace sources that were non-toxic or of relatively neutral impact when disposed of as waste in the environment. All that is really being sustained, then, is an artificially low cost-price to the consumer and maximum profit for the corporate sector. The problem here is neither one of growth or of development as things

170  Sustainable Water Purification in themselves, but of how these are actually carried out, that is to say: their pathways. As processing is done, the quality of the product is decreased (along the HSSA syndrome). Yet, this process is called value addition in the economic sense. The price, which should be proportional to the value, in fact, goes up inversely proportional to the real value (opposite to the perceived value, as promoted through advertisements). Here, the value is fabricated, similar to what is done in the aphenomenal models used in economics (Chapter 3). The fabricated value is made synonymous with real value or quality (as proclaimed by advertisements), without any further discussion of what constitutes quality. This perverts the entire value addition concept and falsifies the true economics of commodity (Zatzman and Islam, 2007). Logically, before certifying a process or system as ‘sustainable’, the conformity of the process with nature must be demonstrated. Instead, exactly the opposite criterion is used, that is to say, unless a mess has been made out of natural order a patent is not granted.

5.2.2 The Consequences At present, numerous debates break out in favor and against any study that appears in the mainstream literature. Both sides use New Science to make their points, without questioning the validity of the “laws” and theories of New Science. In this book, the premises behind all of these laws and theories are challenged. Just like what happened in global warming for which each party calls the other party ‘the flat-earth theorist’ or ‘conspiracy theorist’, debates rage on as to every point of modern medical and chemical industries. Ironically, scientists all believe in the “chemicals are chemicals” or “energy is energy” mantra debate over why organic food and wood stove are better than their toxic alternatives but they all agree that it’s carbon or heat that cause cancer. Just like the global warming debate, for which no one asks ‘how could carbon dioxide be the enemy when we need carbon dioxide for producing life-sustaining plants,’ no one wonders how high temperature or carbon can give cancer when carbon is the essence of life and clay ovens produced healthy breads for thousands of years – all at high temperatures. No amount of doctrinal sermon can explain these contradictions, particularly as the same group, which promotes nuclear as “clean” energy, considers genetically modified, chemical fertilizers and pesticide infested crops derivatives processed through toxic means as “renewable”. This same group also proclaims that electricity collected with toxic silicon photovoltaics and stored with even more toxic batteries – all to be

Sustainable Purifcation Techniques for Agricultural Waters  171 utilized through the most toxic “white light” – as sustainable. In the past, the same logic has been used in the “I can’t believe it’s not butter” culture that saw the dominance of artificial fat (transfat) over real fat (saturated fat) as geared toward creating a similar crisis involving water (CBC, Dec. 19, 2008; Icenhower, 2006). Classical dynamics as represented by Newton’s laws of motion, emphasizes fixed and unique initial conditions, stability, and the equilibrium of a body in motion (Islam et al., 2010). However, it is not possible with the ‘laws’ and theories to make a distinction between the natural products and their corresponding artificial substitutes (Table 5.3). Consequently, the same theories that formed the basis of engineering the artificial products cannot be called upon to make the reversal. The above transitions embody the main bulk of modern technological developments that have been characterized by Nobel laureate chemist, Robert Curl as a ‘technological disaster’. This process has affected the water resources the most, followed by petroleum – the 2nd most abundant liquid on Earth. The most toxic chemical that has emerged from this process is plastic materials that have revolutionized modern era, aptly called the ‘plastic era’ for over a century. Plastic waste has in turn polluted everything on the earth crust. Most notable of the affected natural chemical is the salt (sodium chloride) – the most important chemical of a human blood system – is contaminated by plastic around the world. A recent study (Genza, 2017) shows that sea salt around the world has been contaminated by plastic pollution, adding to experts’ fears that microplastics are becoming ubiquitous in the environment and finding their way into the food chain via the salt in our diets. New studies have shown that tiny particles have been found in sea salt in the UK, France and Spain, as well as China and now the US. Up to 12.7m tonnes of plastic enters the world’s oceans every year, equivalent to dumping one garbage truck of plastic per minute into the world’s oceans, according to the United Nations. This represents the symptom of the ‘plastic addiction’, which is synonymous with the plastic era of over 100 years right up to the Information Age.

5.2.3 The Sugar Culture and Beyond In the HSSA degradation process of turning natural into artificial, the most important transition has been from honey to sugar. This transition has become iconic to the overall technology development process. The invention of sugar correlates strongly with the most meaningful degradation in overall health and lifestyle in human society during recorded

172  Sustainable Water Purification Table 5.3  Transitions from natural to processed. Wood

plastic

Glass

PVC polyester

Cotton

Natural fiber Clay

synthetic fiber

cement

Molasses Sugar

Sugar Sugar-free sweeteners

Fermented flower extract

perfume

Water filter (Hubble bubble) Graphite, clay Chalk

cigarette filter

chalk

marker

Vegetable paint

plastic paint

Natural marble

artificial marble

Clay tile

ceramic tile

Ceramic tile Wool silk Bone

vinyl and plastic

polyester synthetic hard plastic

Organic fertilizer Adaptation

chemical fertilizer

bioengineering

history. While molasses were being manufactured without introducing any health hazards, artificial sugar meant the introduction of numerous toxic chemicals that are simply not suitable for human consumption. However, this was introduced as a symbol of civilization. Sugar is white, and it is sweeter than molasses, and far more profitable than honey. Today, the world consumes some 110 million tones of sugar annually. Yet, sugar is prepared following a process that has never existed in nature. If one starts with the premise that unnatural is not sustainable, the

Sustainable Purifcation Techniques for Agricultural Waters  173 production of sugar would mark a clear divergence from sustainable technology. If one has any confusion as to the existence of sugar as a natural process, one should be reminded of the process involved in manufacturing sugar. For instance, it involves crushing sugar cane, following by ‘cleaning’ with calcium hydroxide, a synthetic chemical that is not used by natural processes for anything of benefit, let alone for cleansing. At a later stage, brown sugar is ‘refined’ with chemical bleach, a potent toxin that oxidizes useful nutrients to render sugar ‘white’. Then a series of other ‘refining’ material, such as, chalk, granulated carbon, etc. may be introduced. While this color is appealing to the public that would consume sugar unconsciously, what does it say about the long-term sustainability of the food that just got reduced into a toxin? Indeed, anyone with conscious and minimum knowledge about how food is processed in a human body would have prevented engineers from employing such a technique. This intervention did not happen. Instead the entire engineering discipline focused on how quickly more sugar can be manufactured, while marketing agencies went out and found new markets to sell the product. Two questions arise here. First, why did an enlightened group of people resort to using toxins to process food? Were they that much intellectually bankrupt that they could not find a technique that nature has already in place? After all, what can be cleaner or whiter than milk? Why did the goodness of milk have to be compromised in nature? It is often understood, it is because denaturing leads to increasing the profit margin. Natural processes can never be fully “cost-effectively engineered” in the sense of “subjected to command and control regimes consistent with maximizing profit in the shortest possible time”. They are not amenable to the principle desideratum of mass production, which is profit based on minimum input costs. Minimizing input costs is not possible in a mass production context without sacrificing quality—usually through conversion of the real/natural into something artificial. If a reality index† were associated with pricing, the corrected profit would invariably always be negative. In reality, nothing is cheaper than natural products as long as sunshine and mother’s milk are still available “for free”, i.e., at no charge or at no cost to one’s capital outlay. How does this obvious logic elude modern-day academics? If the focus is so short-term that long-term benefits and short-falls are entirely disregarded in all economic †

We’ll see in subsequent chapters that in scientifically correct pricing, there should be a penalty in turning natural (real) to artificial. With the current technology development mode, turning from natural to artificial actually increases the profit margin – so much so that a scientific pricing would create a paradigm shift in economic developments.

174  Sustainable Water Purification calculations (Zatzman and Islam, 2007), it will indeed elude the powers of conventional observation. Conventionally, long-term costs, including costs of damaging the quality of a product or polluting the environment are disregarded, leaving the general public to pick up the remedial costs much later. This much about immediate practice is almost trivially obvious. In the absence of an economic theory that includes long-term elements, however, any engineered product can be marketed as anything else, covering the economic bottom line. This is far from obvious and the perfect cover for a system that is entirely artificial from root to surface. In this process, engineers have been playing a robotic role. They had no option to look into the natural order for solutions. This robotization starts early in the education system, and pervades all disciplines. It did not take humanity long to detect the effects of the sugar culture. For nearly a century, it has been known that sugar is responsible for non-genetic diabetes. Any reasonable consideration and rational reaction of this superflux of diabetes would lead to health warnings against sugar and to minimizing its consumption. Yet, the exact opposite happened. Sugar consumption skyrocketed as more and more processed food and fast food hit the marketplace. Sugar was introduced even as the first drink a newborn gets, displacing the age-old practice of giving honey to a newborn. Based on flawed analysis, honey was in fact banned from pediatric sections of the hospital and labels slapped on honey containers, warning people that honey can cause b ­ otulism – an utterly aphenomenal conclusion‡. Today, sugar or similar sweeteners are ubiquitous, some food containing 75% sugar (Gillespie, 2010). Over time, more ‘side effects’ of this sweet poison have emerged. For example, addiction to refined sugar is more problematic than addiction to cocaine, and is associated with obesity, cancer, and diabetes (Goldwert, 2012). Chemical engineering research has focused on several fronts, all maximizing short-term economic benefits. For instance, the notion that ‘chemicals are chemicals’ irrespective of their natural or artificial origin and components was used to sell the general public in the idea that natural sugar is the same as refined sugar, therefore, refined, i.e. artificial, sugar should be preferred because it’s cheaper. After all, if honey has just as many calories as sugar but costs twice as much, the immediate practical reason to opt for honey disappears. Once this dogma of refinement trumps natural availability entrenched itself, research could focus—and indeed has focused—on developing cheaper and more effective forms of sweetener.

‡

Botulism is a rare paralytic illness caused by a toxin which is very poisonous to humans. As late as August 3, 2013 headline reads “New Zealand recalls dairy products over botulism fears”.

Sustainable Purifcation Techniques for Agricultural Waters  175 Biomedical engineering research revealed the addictive nature of sugar. As research began to reveal addictive nature of sugar, it was taken as a boon. It causes a euphoric effect that triggers dopamine, the chemical that controls pleasure in the brain. This should have triggered in a conscientious mind that natural sugar which produces natural glucose—the only food for the brain—cannot possibly be the same as artificial sugar that intoxicates the brain. The received message instead was: adding sugar to any product would make it addictive and sales will skyrocket! Recently, Munro (2015) presented how such epidemic of addiction is turned into a huge profit making industry, thus completing the loop between food companies and pharmaceutical companies. For alcohol addiction, Munro quoted, Harvard Graduate, addiction expert, and author, Dr. Lance Dodes: “I became the Director of the Alcoholism Treatment Unit at Harvard’s McLean Hospital. I’ve probably treated a couple of thousand people who have one addiction or another. Almost all residential treatment programs in the United States are 12 Step based, so their effectiveness will depend entirely on whether 12 Step programs work and the statistics for AA are not good. It is helpful for 5‒10% and that’s a good thing. That’s 5‒10% of people who are being helped by A.A. ‒ it’s a lot better than zero percent ‒ but it shouldn’t be thought of as the standard of treatment because it fails for most people ‒ for the vast majority of people.”

Add to it the fact that scientists are beginning to discover that sugar may actually be more addictive than cocaine (for instance, Sullum, 2013 some of the scholarly articles that opened up the debate. While it is known that sugar causes many ailments, it is little known that the fact sugar is addictive is a motivating factor for the food industry, who then colludes with the pharmaceutical industry while the academic community remain totally preoccupied with advancing ever growing number of paradoxical theories (Satel and Lilienfeld, 2014). The mindset of drug dealers is the moral equivalent of such a marketing policy. Medical research groups focused on ‘fighting’ symptoms of sugar. Because sugar consumption led to non-genetic diabetes, the immediate replacement of natural insulin with artificial insulin became the focus. Anyone with common sense and good conscience would be able to see this ‘remedy’ to diabetes as devastating as attaching an artificial limb because the limb had a cut that would otherwise heal naturally. Medical professionals, however, put diabetes patients on permanent insulin. Considering that insulin must be produced internally for it to have natural hold of the sugar burning process in an organic environment, how scientific is this?

176  Sustainable Water Purification A different campaign involved engineering the fabrication of poisons in order to fight bacteria that thrive under sugary conditions. It became a common practice to use toxic chemicals, such as sodium nitrate, sorbic acid, sulfur dioxide, benzoate, and others to fight off bacterial growth. Magically, these toxins not only restored the original longevity of food (before adding sugar), they also increased shelf life! This was considered to be great technological progress in the eyes of modern corporations and corporatizers. The obsession to alter natural properties in order to ‘fight’ bacteria or natural decay was so intense that, by the 1960s, use of gamma-rays to kill bacteria became a common practice. It was assumed that the process of irradiation itself would not affect food. It was nothing but a publicity stunt as anyone with logical thinking should have known natural fat is necessary for sustenance of life. The biggest accomplishment of Margarine-producing companies, the first artificial fat, which was derived from animal fat in the Napoleon era, was to render non-edible vegetable oil into artificial butter. Before, the fraud of trans fatty acid was detected, and a huge campaign that started in 1970s culminated in 1990s when USA Health department actively campaigned in favor of artificial fat and calories against natural fat and natural sugar (as in fruits, etc.). The Food pyramid was replaced with a dart board that placed artificial food at the centre, and ‘fat-free’ became the sign of good health. The sugar peddlers soon discovered “if you take fat out of food, it tastes like cardboard;” therefore, fat was replaced with sugar. The sugar consumption saw an unprecedented growth. See Figure 5.6. Increased sugar consumption is likely to be concentrated in developing countries (Figure 5.7). Asia and Africa will show the most growth, with growth in Asia attributable to population growth rates, economic 200 150 100 50 0 60

65

70

75

80

85 90 Years

95

00

05

10

12 est.

Figure 5.6  Millions of tons of sugar produced globally over the years (from Islam et al., 2018).

Sustainable Purifcation Techniques for Agricultural Waters  177 60

Million tons

50 1983

40

1988

30

1993 1996

20

2003

10 0 Europe

North and Central America

South America

Asia

Africa

Oceania

Figure 5.7  Sugar production history by region (From Islam et al., 2015).

development and changing tastes and preferences. In Africa the effect of population growth is expected to surpass the decline in per capita sugar consumption. Central America, South America and the Caribbean have shown a steady increase in consumption, mainly as a result of an increase in population as well as globalization. Sugar consumption in industrial countries will decline, although this fall should be more than offset by growth in Asia and Africa alone. In North America and the EU, consumption is stagnant: the population is only growing slowly and the effect of rising incomes on expenditure on sugar and sugar-containing products is minimal. In the USA, High Fructose Corn Syrup (HFCS/in Europe called HFS or High Fructose Syrup), is displacing evermore sugar, though at a slower growth rate than in the past. In Central Europe and the Former Soviet Union (FSU), consumption has decreased significantly as economic transformation takes place, however seems to be increased again. The three largest sugar consumers are India, the EU 15 and the Former Soviet Union (see Table 5.4). Consumption in the FSU and the USA has fallen sharply, but has risen significantly in India, China and Pakistan. The highest per capita consumption occurs in Brazil, with Mexico in second place. China has the lowest per capita consumption. However, China is the place that leads in saccharine production. These will all correlate with diabetes, cancer, and other ailments that are considered to be driven by genetics. The three largest sugar consumers are India, the EU 15 and the Former Soviet Union (see Table 5.4). Consumption in the FSU and the USA has fallen sharply, but has risen significantly in India, China and Pakistan.

10,50

12,40

8,93

6,55

4,30

3,23

0,89

1,73

2,70

56,84

EU

FSU*

USA

Brazil

China

Mexiko

Pakistan

Indonesia

Japan

Total

*FSU= Former Soviet Union.

5,60

1980

71,32

2,83

2,65

2,29

4,43

7,13

6,62

7,85

13,40

13,067

11,07

1990

78,12

2,60

3,25

2,93

4,25

8,50

8,30

8,73

10,27

14,525

14,75

1996

89,1

2,4

3,2

3,6

5,0

10,2

9,8

9,5

10,5

14,6

20,0

2001

Total sugar consumption (in million tons)

India

Country

64,5

1,7

2,3

2,8

3,6

7,4

7,1

5,4

7,6

10,6

14,5

% of world consumption

Table 5.4  Sugar consumption for various regions/countries (from Islam et al., 2015).

–

23,1

11.8

10.7

46.5

4.3

54.

39.2

46.7

31.1

8.3

1980

–

22.9

14.8

20.4

54.5

6.2

44.

31.4

46.2

38.1

13.4

1990

–

19,0

15,8

24,5

46,7

6,3

53,1

29,0

37,0

34,5

15,7

2001

Per capita consumption in kg

178  Sustainable Water Purification

Sustainable Purifcation Techniques for Agricultural Waters  179 CH2OH H

C

C

H

OH

O

H

H

C

C

C

OH

OH

OH

H

Figure 5.8  Sugar structure (note how all catalysts disappear).

The highest per capita consumption occurs in Brazil, with Mexico in second place. China has the lowest per capita consumption. However, China is the place that leads in saccharine production. These will all correlate with diabetes, cancer, and other ailments that are considered to be driven by genetics. The consumption of sugar has been increasing in Asia due to lower prices and freer availability. In the last 20 years, sugar consumption sugar consumption in Asia increased by 26 Million tons. 38% of world sugar consumption belongs to Asia. Figure 5.8 shows the chemical structure of a typical sugar molecule. Note how no information pertaining to catalysts and numerous chemicals is attached to the molecular structure. As more and more people got addicted to sugar, an entire generation became afflicted with sugar-induced health problems. This crisis, along with the mantra that fat is evil, led to the development of alternative sweeteners that are “sugar-free”. A new index started to surface: the measuring of everything in terms of calories, indicative of unhealthiness. So, an entire line of artificial products was manufactured, all focusing on maximizing sweetness and minimizing cost. It meant the introduction of Saccharin®. Chemical Fertilizer has been determined to be the second cause of Soil Degradation after soil erosion (Tetteh, 2015). The over use of Chemical fertilizer has resulted to Hardened soil, Decreased in Fertility, low soil quality, increased used of Pesticide and Herbicide, Polluted air and water, and also produces Greenhouse Gasses. It also contains salt as well as other acidic materials which is one of the most critical characteristics of chemical Fertilizer and is expected to damage the soil in the long run.

5.3 Removal of Heavy Metals Determination of various treatment processes for wastewater depends on the compounds constituting the waste. Metals exist in wastewaters in many forms such as soluble, insoluble, inorganic, metal organic, free metal, reduced, oxidized, adsorbed, precipitated, and complexed. Toxic heavy

180  Sustainable Water Purification metals of particular concern treatment of industrial wastewaters include copper, zinc, cadmium, lead, nickel, silver, mercury, chromium, and iron. The metal processing, plating, and metal finishing industries are sources of such metal wastes (Peters and Ku, 1985). Organic wastes also play a significant role as water micro pollutants since some of them are industrially used widely as pesticides, resin components, disinfect ants, preservatives, bactericide, and synthetic reagents etc. (Shin et al., 1996). However, minimization of the heavy metals emission into the environment is necessary to protect natural waters and thus preserve the good quality of water. There are different methods available to remove these heavy metals from the streams, such as, chemical precipitation, electrodeposition, electro-coagulation, reverse osmosis, membrane filtration, solvent extraction, ion exchange, adsorption and biosorption (Patterson, 1989). However, many technologies are extremely expensive (Meunier et al., 2003). Apart from being expensive, these technologies have several disadvantages, such as: need for continuous input of chemicals, the production of toxic sludge, or inefficient in reducing metal ion levels in treated wastewater to the permissible concentrations, which are required by government legislation. The prime factors to be considered in choosing one of these methods are the economic considerations, availability of the raw materials, and regulatory requirements. Islam and Wellington (2001) gave much stress on the development of environmentally appealing research projects. Moreover, they mentioned the introduction of novel methods in the areas of engineering research. Any novel method carries tremendous impetus in making green technologies. This has encouraged our research group into discovering materials and methods for the removal of heavy metals that are efficient, economically attractive, and environmentally appealing. The adsorption process is an attractive option for the removal of heavy metals from wastewater. Activated carbon is a commonly used adsorbent for the removal of organic and inorganic compounds present in water and wastewater treatment but its high cost renders it economically not competitive. An economical and easily available adsorbent would certainly make an adsorbent-based process a viable alternative for the removal of heavy metal from wastewater. In recent years, the search for low-cost adsorbents that have metal-binding capacities has intensified. Materials locally available in large quantities, such as, natural materials, agricultural waste or industrial byproducts can be utilized as low-cost adsorbents. Some of these materials can be used as adsorbents with little processing (Rahman and Islam, 2009a and b; Rahman et al., 2013).

Sustainable Purifcation Techniques for Agricultural Waters  181

5.3.1 Application of Wood Sawdust for Removal of Heavy Metals It has been reported in the existing literature that lignocellulosic materials present in biomasses have an excellent capacity for binding heavy metal ions due to different types of functional groups present in its structure (Dore, 1919; Burba and Willmer, 1983; Aoyama et al., 1993; Srivastava et al., 1994; Marshall and Champagne, 1995; Saeed et al., 2002). As wood sawdust contains a significant amount of lignocellulosic materials, therefore, wood saw dust has been studied so often and detailed as an adsorbent of heavy metals from waste water. On the other hand, wood saw dust is abundant byproduct. For instance, in Canada 4,175,000 km² land out of a total of 10 million square kilometers is covered by forest. It has been reported that Canada is the world’s biggest exporter of timer (90%) (WRI, 2007). Every year a huge amount of wood plants are using to different sectors such as wood furniture industries, thermal power plant, paper mill, home heating (Figure 5.9). Wood sawdust is a byproduct of wood furniture industries

Plants

Good CO2 Power plant

Alkaline soln extraction

Wood ash

Paper mill

Wastewater treatment

Home heating

A s h Cement & Ceramic Ind.

Bio-diesel plant-ash use as catalyst

Wastewater treatment

Fertilizer

Wood sawdust

Green Field Agric. Field

Wood sawdust

Forest

Wood chips Bark

Soil Nutrients Plants

Byproducts

Wood

Figure 5.9  Possibilities for a sustainable utilization of wood sawdust.

182  Sustainable Water Purification Aqueous streams (Synthetic wastewater)

Natural Adsorbent (wood sawdust)

Function group studies (NMR, FTIR)

Characterization of sawdust (SEM-DX)

Different Parameters (pH, Temp, contact time, initial conc) effect on adsorption

Batch isotherm studies

The Langmuir isotherm modeling

The Freundlich isotherm modeling

Maple sawdust as an adsorbent material

Figure 5.10  Organization of the study on metal adsorption process using maple wood sawdust sample.

and it might be used for industrial wastewater treatment. Characterization of wood sawdust and their application for heavy metal removal process have been schematically shown Figure 5.10.

5.3.1.1 Composition, Structure and Morphology of Wood Wood is primarily composed of hollow, elongate, spindle-shaped cells that are arranged parallel to each other along the trunk of a tree. When lumber and other products are cut from the tree, the characteristics of these fibrous cells and their arrangement affect such properties as strength and shrinkage as well as the grain pattern of the wood. Wood is primarily composed

Sustainable Purifcation Techniques for Agricultural Waters  183 H

OH

C

C

OH

H

C H

H C CH2OH

CH2OH C H

H

C

C O

O

O O

H OH

H

C

C

H

OH

C H

Figure 5.11  Chemical structure of cellulose in wood sample (WSE, 2007).

of cellulose, lignin, hemicelluloses, celluloses, and minor amounts (5% to 10%) of extraneous materials (Browning, 1975; Rowell, 1984). Cellulose: Cellulose, the major component, constitutes approximately 50% of wood substance by weight. It is a high-molecular-weight linear polymer consisting of chains of 1 to more than 4 b-linked glucose monomers. During growth of the trees, the cellulose molecules are arranged into ordered strands called fibrils, which in turn are organized into the larger structural elements that make up the cell wall of wood fibers (Figure 5.11). Most of the cell wall cellulose is crystalline. Lignin: Lignin constitutes 23% to 33% of the wood substance in softwoods and 16% to 25% in hardwoods. Although lignin occurs in wood throughout the cell wall, it is concentrated toward the outside of the cells and between cells. Lignin is often called the cementing agent that binds individual cells together. Lignin is a three-dimensional phenylpropanol polymer (Figure 5.12), and its structure and distribution in wood are still not fully understood. Hemicelluloses: The hemicelluloses are associated with cellulose and are branched, low-molecular-weight polymers composed of several different kinds of pentose and hexose sugar monomers. The relative amounts of these sugars vary markedly with species. Hemicelluloses play an important role in fiber-to-fiber bonding in the papermaking process. The component sugars of hemicellulose are of potential interest for conversion into chemical products.

5.3.1.2 Structure and Morphology of Wood Structure: The microscopic cellular structure of wood, including annual rings and rays, produces the characteristic grain patterns in different species of trees (Figure 5.13). The grain pattern is also determined by the plane in which the logs are cut at the saw mill. In transverse or cross sections, the

184  Sustainable Water Purification H2COH CH CO H2COH CH CO

5’ H3CO

H2COH CH CH 6’ O

H2COH O HC HC

OCH3

O

0,4

CH2 CH HC

H2COH HC CO

CHO CH CH

H2COH 25 HC OCH3 O HC

H2COH 5 15 H2COH HC 6 OCH3 H3CO OCH3 24 HC O O H3CO HC OCH3 H3CO 3 CH O O OH H3CO OCH 3 H2COH O H2COH 14 OCH3 OCH3 HC 12 O O CH 4 OCH H CO 3 3 H COH 2 2 HC O OCH3 HCOH OCH3 22 O OCH3 HC H3CO 13 11 O CHO O H2COH H2COH CH H2C OCH3 H3CO OCH3 H2COH O CH HC CH O HC 8 O HC CH CO HOCH2 CH CO CH2 HC O CH OCH3 OCH OCH3 H2COH 2 9 10 21 CH2OH 19 O CH C 7 H3CO OCH3 H CO CH O O HC 3 O CH H3CO OCH3 OH CO HOCH2 CH CHO 18 20 H2COH 16 O OCH3 H3CO H2C CH2 H2COH O HC O H3CO HC CH CH HC O HOCH2 CH CHO CH2 CH2 HC 17 9’ 10’ 24’ OCH3 H3CO OH H3CO OCH3 H3CO OCH3 O O O 0,5 1

H2COH HC CH

OCH3

CH2OH CH CH 23 OH

OCH3

H2COH CH HC 25’ OH

Figure 5.12  Chemical structure of lignin in beech (Fagus sylvatica) (Gaballah and Kilbertus, 1998).

Thin pits Horizontal plane

Annual ring

Pore

Crossbars Wood rays

Vertical plane

Wood rays

Vertical plane

Figure 5.13  Cell structure of poplar wood (Adopted from USDAFS, 1980).

OCH3 0,1

Sustainable Purifcation Techniques for Agricultural Waters  185 annual rings appear like concentric bands, with rays extending outward like the spokes of a wheel. The annual rings can be counted to age-date the tree (Armstrong, 2007). New wood cells are formed on the inside of the cambium and new bark cells on the outside. Thus, new wood is laid down to the outside of old wood and the diameter of the woody trunk increases. In most species, the existing bark is pushed outward by the formation of new bark, and the outer bark layers become stretched, cracked, and ridged and are finally sloughed off (Hoadley, 1990). The woods have specialized structures called vessels for conducting sap vertically, which on the end grain appear as holes or pores. The vessels are made up of relatively large cells with open ends set one above the other and continuing as open passages or tubes for relatively long distances. The pores of woods vary considerably in size, being visible without a magnifying glass in some species but not in others. In most woods the ends of the individual cells of the vessels are entirely open, whereas in others, the opening has crossbars on the radial surface. Most of the smaller cells are spindle shaped cells usually having small cavities and relatively thick walls (Core et al., 1979). Many species of wood have unique chemical and physical or structural properties. Scanning electron microscopy is the best known and most widely-used of the surface analytical techniques. SEM, accompanied by X-ray analysis, is considered a relatively rapid, inexpensive, and basically non-destructive approach to surface analysis and elemental analysis of samples (Thipse et al., 2002). In recent years, CP/MAS NMR (Nuclear Magnetic Resonance) and FTIR (Fourier Transform Infrared) spectroscopy have been using as a very valuable tool for studying the chemical composition of wood, as well as for analyzing the chemical changes that occur various processes, including weathering, decay and chemical treatment (Gil and Neto, 1999; Moore and Owen, 2001; Baldock and Smernik, 2002). Morphology: Scanning electron microscopy (SEM) is the best known and most widely-used of the surface analytical techniques. SEM, accompanied by X-ray analysis, is considered a relatively rapid, inexpensive, and basically non-destructive approach to surface analysis (Thipse et al., 2002). Due to the manner in which the image is created, SEM images have a characteristic three-dimensional appearance and are useful for judging the surface structure of the sample. It is often used to survey surface analytical problems before proceeding to techniques that are more surface-sensitive and more specialized. EDX (Energy-dispersive X-ray). Spectrometry coupled with SEM (Scanning Electron Microscope) was used to characterize maple wood sawdust samples. The electron microphotographs of

186  Sustainable Water Purification the particles of maple wood sawdust samples before adsorption and after adsorption are shown in Figures 5.14 and 5.15. The change of the micrographs of the cell materials in the maple wood sawdust particle may have been influenced by the metal ions. It could be assumed that the dense areas might be contained most of the sorbed metals ions. Most the researchers who studied the areas of metal sorption on microbial biomass observed

S-4700 20.0 kV 11.9 mm ×2.00k SE(U)

20.0 um

Figure 5.14  SEM microphotograph of particle of the untreated maple sawdust sample.

S-4700 3.0 kV 13.1 mm ×2.50k SE(U)

20.0 um

Figure 5.15  SEM microphotograph of particle of the treated maple sawdust sample.

Sustainable Purifcation Techniques for Agricultural Waters  187 that heavy metals were deposited on cell walls (Mullen et al., 1989, 1992; Tsezos and Volesky, 1982 a, b; Shuttleworth and Unz, 1993). To confirm the existence of the metals ions on cell walls of the maple sawdust particles, Energy-dispersive X-ray (EDX) microanalysis was carried out in this study. The EDX spectra for the untreated and treated particles of the maple wood sawdust using metal ions solution are shown in Figures 5.16 and 5.17. When the microprobe was focused on the dense areas of the surface of the maple sawdust it was noticed clearly the presence of metals ions. The EDX spectra analysis revealed the metal ions signal on the surface of the treated maple sawdust with metal ions (II) in Spectrum 1

C

O

Au

Au Pd Pd

Au

0 1 2 3 4 5 6 Full Scale 221 cts Cursor: –0.157 keV (0 cts)

Au

7

8

Au

9

10

Au

11

12

13

Au 14

15

16

17

18

19

20 keV

Figure 5.16  Corresponding EDAX coupled with SEM spectrum of the particle of untreated maple sawdust sample. Spectrum 2

C

O

Au Pb

Au Pb

Au

Pd Cd Pd Cd Cd

0 1 2 3 4 5 6 7 Full Scale 384 cts Cursor: –0.033 keV (1058 cts)

Au 8

Pb

9

Pb Au 10

11

Pb Pb

12

13

Au

Pb 14

15

16

17

18

19

Figure 5.17  Corresponding EDX coupled with SEM spectrum of maple sawdust after treated by lead and cadmium ions solution.

20 keV

188  Sustainable Water Purification solution (Figure 5.17), which was not present before adsorption of metal ions on the surface of the sawdust (Figure 5.16). It was noticed in EDX spectra (Figure 5.17) that the intensity of lead (II) ions were higher than that of cadmium (II) ions. This might be an indication that the uptake of lead ions is higher than that of cadmium ions. Also, it can be inferred that ion exchange with lead ions is more significant than with cadmium (II). The presence of gold and palladium peaks in all spectra results from the gold and palladium purposely settled to increase the electric conduction and to improve the quality of the micrographs. It is also observed in the SEM-EDX spectra on the surface of wood sawdust that there is a significant difference between the oxygen peaks before (Figure 5.16) and after (Figure 5.17) metals ions adsorption. The atomic concentration of oxygen decreased after metal ions biosorption was decreased. This might be due to the fact that the metal ions biosorption was accompanied by a change in oxygen, providing evidence that the oxygen of carboxylic group took part in the metal biosorption. For different metal ions with different types of adsorbents, similar results were also reported by Kuyucak and Volesky (1989). Functional groups: Fourier Transform Infrared (FTIR) spectroscopy has been used as a very valuable tool for studying the chemical composition of wood, as well as for analyzing the chemical changes that occur various processes, including weathering, decay and chemical treatment (Moore and Owen, 2001; Baldock and Smernik, 2002). Rahman (2007) used FTIR Spectrometer to detect vibration frequency changes for each functional group presented in maple wood sawdust during the metal adsorption process. The spectra are collected by a spectrometer using KBr pellets. In each case, 1.0 mg of maple wood sawdust sample and 100 mg of KBr (potassium bromide) were homogenized using mortar and pestle thereafter pressed into a transparent tablet at 200 kgf/cm2 for 5 min. The pellets were analyzed with an infrared spectrometer-VECTOR 22, Bruker Co, Germany in the transmittance (%) mode with a resolution of 4 cm-1 in the range 4600–500 cm-1. The background obtained from the scan of pure KBr is automatically subtracted from the sample spectra. All spectra are plotted using the same scale on the transmittance axis. It is very important to know the chemical structure of used carbon in adsorbent for understanding the adsorption capacity. The metals adsorption capacity is strongly influenced by the surface structures of carbon-oxygen (functional groups) and surface behavior of carbon (Ricordel et al., 2001). Functional groups in maple wood sawdust were determined by Fourier Transform Infrared (FTIR) Spectroscopy. The spectrum assignments were made based on the model spectrums and the types of functional

Sustainable Purifcation Techniques for Agricultural Waters  189

30

Transmittance [%] 40 50 60 70

80

90

100

groups found in different literatures (Colthup et al., 1990; Silverstein and Webster, 1998; Field et al., 2002). The transmittance FTIR spectra between 4000 to 500 cm-1 of the maple wood sawdust and of maple wood sawdust with metals adsorbed are shown in Figures 5.18 and 5.19 respectively. The maple wood sawdust FTIR spectrum showed six intense bands, around 3385, 2904, 2427, 1735, 1384 and 1056 cm-1. The broad band around 3385 cm-1 is attributed to the surface of hydroxyl groups and chemisorbed water (Baldocka and Smernik, 2002; Boonamnuayvitaya et al., 2004; Montanher et al., 2005; Coskun et al., 2006). The peaks at around 2904 cm-1 represented C-H stretching vibrations and -CH3 wagging (Montanher et al., 2005; Ozmen et al., 2006). The FTIR spectra at around 2427 cm-1 is characteristic of the carboxyl acid groups referring to the IR spectra of carbons of other workers (Toledo et al., 1990; Fanning and Vannice, 1993). The band around 1735 cm-1 might be assigned to the carbonyl (C=O) stretching vibration (Wu et al., 2004; Ozmen et al., 2006). The peaks at 1647 cm-1 and 1596 cm-1 in maple wood sawdust spectrum were caused by the stretching band of carboxyl groups. A narrow band spectrum was observed at around 1384 cm-1 and was attributed to the aromatic CH and carboxyl-carbonate structures (Tsai and Chang, 1995). In addition, the intensity of the band at 1241 cm-1, related to C–O stretching vibration of the acetate function (Ozmen et al., 2006) was observed. The strong peaks at 1115-1056 cm-1 represented C-OH stretching vibration.

4000

3500

3000

2000 2500 Wavenumber cm–1

1500

1000

Figure 5.18  FTIR spectrum on the surface of untreated maple wood sawdust.

500

30

Transmittance [%] 40 50 60 70

80

90

100

190  Sustainable Water Purification

4000

3500

3000

2500 2000 Wavenumber cm–1

1500

1000

500

Figure 5.19  FTIR spectrum on the surface of treated maple sawdust by metals solution.

The FTIR spectrum after metal binding is shown in Figure 5.19. The spectral analysis before and after metal binding indicated the difference on the transmittance of the peaks at 3385, 2427, 1735, 1364, and 1056 cm-1 for maple wood sawdust with Cu(II), Cd(II) and Pb(II) adsorbed and for the native maple wood sawdust. It was observed in Figure 5.19 that the main adsorption bands centered at around 1000 cm-1 and at 3400 cm-1 had largely diminished while the adsorption band at around 2427 cm-1 had almost disappeared. It was observed that the adsorption band around 1735 cm-1 for the carbonyl (C=O) in chelating group shifted to higher frequencies (1757 cm-1) with the intensity of the peak decreasing. This observation was supported by the presence of metal ions bondings with carboxylate group, as shown in Figure 5.19. An increase in the absorption frequency for the -COO- group corresponds to an increase in the covalent character of the metal-carboxylate bond (Hebeish et al., 1998). Many additional absorbances derived from contributions of the various vibration modes of C originating from carbohydrates and lignin were observed in the 1800– 500 cm-1 spectral region (Shafizadeh, 1984; Pandey, 1999; Villaescusa et al., 2004). In an aqueous solution, two hydrogen atoms are released for each divalent metal cations by sorbent. FTIR studies reveal that several functional groups, which are able to bind with heavy metal ions, are present in the maple wood sawdust. It is likely that the carboxyl and hydroxyl groups

Sustainable Purifcation Techniques for Agricultural Waters  191 presented in maple wood sawdust might be participating in the divalent metal adsorption.

5.3.1.3 Removal of Heavy Metals Using Wood Saw Dust Wood sawdust is a solid waste product obtained from different types of wood processing industries. It is mainly composed of plant fibers that contain cellulose, hemicellulose, lignin, etc. It has been reported in literature that lignocellulosic materials present in biomasses have the capacity for binding heavy metal ions due to different types of functional groups present in its structure (Dore, 1919; Burba and Willmer, 1983; Aoyama et al., 1993; Srivastava et al., 1994; Marshall and Champagne, 1995; Saeed et al., 2005). Several biomass materials are now being used as low cost adsorbents for heavy metal removal from aqueous solutions. However, maple wood sawdust as an adsorbent has not been studied thoroughly. A sample element “Copper (Cu)” has been experimentally used to show the heavy metals removal efficiency from contaminated water following different experimental condition along with adsorption isotherm modeling. The effect of contact time on the adsorption process



Sorption(%) =

(C0 − Ce ) X100 C0

(5.1)

where, Co = Initial concentration (mg/L) of the metal solution and Ce = Equilibrium concentration (mg/L) of the metal solution The effect of maple sawdust dose on the adsorption process The effect of maple wood sawdust concentration on the adsorption process was studied at a room temperature of 23 ºC and at constant pH value of 5.0. Copper solution samples of 100 ml each were placed in five Erlenmeyer flasks and different amount of maple sawdust ranging form 1 g/L to 30 g/L were placed in the flasks. Initial concentration of copper solutions were 5mg/L, 10 mg/L, 25 mg/L, 50 mg/L and 100 mg/L. The concentration of copper solutions before adsorption and after adsorption was measured by atomic absorption spectrophotometer and the percentage of metal adsorption was calculated using Equation 5.1 and the results are shown in Figures 5.20 through 5.22. It was observed that the equilibrium concentration was decreased quickly with the increasing weight of maple wood

192  Sustainable Water Purification 100 Adsorption percentage (%)

90 80 70 60 50 40

Experiment 1 Experiment 2 Experiment 3 Average value

30 20 10 0 0

50

100

150

200

250

300

350

400

Contact time (min)

Figure 5.20  Effect of contact time on removal of copper ions (II) by maple sawdust (Experimental data are plotted showing the points and trend line with points shows the mean value of the triplicate analysis).

sawdust for different concentrations of the copper solution (Figure 5.21). The copper ions were already adsorbed well (82.53%) by 10 g/L of maple sawdust. After that, copper ions removal percentage was not improved significantly with the increasing adsorbent concentration, as shown in Figure 5.21. It was revealed that the copper removal percentage was higher for the 100

Adsorption percentage (%)

90 80 70 60 50 40

Initial Conc = 5mg/L Initial Conc = 10mg/L Initial Conc = 25mg/L Initial Conc = 50mg/L Initial Conc = 100mg/L

30 20 10 0 0

5

10 15 20 25 Maple sawdust concentration (g/L)

30

35

Figure 5.21  The effect of sawdust concentration on copper removal percentage (%) using different concentrations of copper ions solutions (mean values of the triplicate analysis are used to draw the figure).

Sustainable Purifcation Techniques for Agricultural Waters  193

Equilibrium concentration (mg/L)

120 Initial Conc = 5mg/L Initial Conc = 10mg/L Initial Conc = 25mg/L Initial Conc = 50mg/L Initial Conc = 100mg/L

100 80 60 40 20 0 0

5

10

15

20

25

30

35

Maple wood sawdust dosage (g/L)

Figure 5.22  The effect of maple wood sawdust dosage on copper ions adsorption process (mean values of the triplicate analysis for the different concentration of copper ions solutions are used to generate the figure).

lowest concentration of copper solution (5 mg/L) with the constant amount of the adsorbent. This can be explained by the observation that when metal concentration is lower, all copper ions present in the solution can interact with the binding sites of a fixed amount of adsorbent. Consequently, when metal concentration is increased the binding sites of the fixed amount of adsorbent can be occupied by preference and, as a result, less amount of copper is adsorbed. The effect of initial concentration on the adsorption process The metal uptake is particularly dependent on initial heavy metal concentration. At low concentration values, metals are adsorbed by specific sites, while with increasing metal concentrations the specific sites are saturated and exchange sites are filled. Different concentrations of copper ions solutions i.e. 5, 10, 25, 50 and 100 mg/L were used and the experiments were carried out triplicate with the same condition. From the experimental studies, it was shown that the percentage of copper adsorption decreased from 83.61% to 58.27% with the increment of the initial copper ions concentration (Figure 5.23). Several researchers have also studied the effect of initial sorbate concentration on sorption of heavy metals by using different biomass and found similar results with this study (Al-Asheh et al., 1996; Hasan et al., 2004; Chuah et al., 2005). At the beginning of initial concentrations (5 mg/L), the copper removal percentage was higher due

194  Sustainable Water Purification 100

Adsorption percentage (%)

90 80 70 60 50 40

Sawdust = 5(g/L) Sawdust =10(g/L) Sawdust = 20(g/L) Sawdust = 30(g/L)

30 20 10 0 0

10

20

30

40

50

60

70

80

90

100

110

Initial Cu(II) ions concentration (mg/L)

Figure 5.23  The effect of initial concentration of metal on copper adsorption using maple wood sawdust samples (mean values of the triplicate analysis for the different concentration of copper ions solutions are used to draw the graph).

to a larger surface area of the maple wood sawdust being available for the adsorption of copper ions. When the concentration of the metal ions solution became higher, the copper removal percentage was lower because the available sites of adsorption became less. As can be seen from Figure 5.23, the copper adsorption percentage is 78.26% to 83.61% at sorbate concentrations of 5 mg/L, whereas the metal adsorption percentage was 58.19% to 67.44% at higher sorbate concentrations of 100 mg/L for the different amount of maple sawdust concentration ranging from 5 g/L to 30 g/L. At a higher initial concentration, the ratio of initial number of moles of copper (II) to the available adsorption surface area was higher, and as a result adsorption percentage was less. This might be the major mechanism of the effect of the initial metal ions concentration in aqueous solution on the adsorption process. The effect of pH on the adsorption process The pH value of the aqueous solution is an important controlling parameter in the adsorption process. These pH values affect the surface charge of adsorbent, the degree of ionization and speciation of adsorbate during adsorption. Thus the effect of pH (H+ ion concentration) in the solutions on the copper removal efficiency was studied at different pH ranging from 2.0 to 8.0 as shown in Figure 5.24. The experiment was performed triplicate with an initial copper concentration of 25 mg/L, temperature of 23ºC with a constant agitation using a laboratory made shaker. The heavy metal ions

Sustainable Purifcation Techniques for Agricultural Waters  195 100

Adsorption percentage (%)

90 80 70 60 50 Experiment 1 Experiment 2 Experiment 3 Average value

40 30 20 10 0

0

1

2

3

4

5

6

7

8

9

pH value of Cu(II) ions solution

Figure 5.24  The effect of pH values (2.0, 4.0, 5.0, 6.0, 7.0 and 8.0) on the adsorption of copper for 25mg/L metal solution and 10 g/L maple wood sawdust sample (experimental results are plotted showing only points and the mean values for the triplicate analysis are used to draw the trend line).

are completely released under circumstances of extreme acidic conditions. It was observed that the biosorption was very little (28.66%) at an initial pH value of 2.0. A sharp increase in the biosorption of copper ions from 28.66% to 83.25% occurred in the pH range of 3-4. It is observed that the adsorption capacity is very low at strong acidic medium and the adsorption capacity increases with increasing pH values, until a certain pH value is reached. This can be explained on the basis of decrease in competition between positively charged H+, H3O+ and Cu2+ for the same functional groups. As the pH value is increased, more ligands are exposed and the number of negatively charged groups on the adsorbent matrix probably increased, enhancing the removal cationic species (Chang et al., 1997; Reddad et al., 2002). It was observed that the optimum copper (II) ions removal occurred between the pH values of 5.0 to 6.0. It was also observed that the adsorption capacity was increased again at pH value from 6-7, which might be due to onset of precipitation of copper ions as insoluble Cu(OH)2 and not due to adsorption. As a result, the maximum adsorption was observed at pH of 7.0 and it might be due to interaction of the species of Cu(II) ions i.e Cu2+, Cu(OH)+, Cu(OH)2 with the surface functional groups present in maple wood sawdust. The metal uptake depends on the active sites of the adsorbent as well on the nature of the metal ions in solution. At a pH value of 6.0 there are three species of Cu(II) ions present in solution as suggested by several

196  Sustainable Water Purification authors (Leckie and James, 1974; Baes Jr., and Mesmer, 1976). Cu(OH)+ and Cu(OH)2 in large quantities and Cu2+ is small in quantity. These species were adsorbed at the surface of the maple wood sawdust either by ion exchange mechanism or by hydrogen bonding for the adsorption process due to the –COOH groups and –OH groups present in the most adsorbent (Jeon et al., 2001; Zacaria et al., 2002).



(-ROH) + Cu2+ → (RO)Cu + H+

[Ion exchange]



(-RCOOH) + Cu2+ → (RCOO)Cu + H+

[Ion exchange]



-ROH + CuOH+ → (-RO)CuOH + H+

[Ion exchange]



-RCOOH + CuOH+ → (-RCOO)CuOH + H+

[Ion exchange]



(ROH) + Cu(OH)2 → (-ROH)2Cu(OH)2

[H – bonding]



(RCOOH) + Cu(OH)2 → (-RCOOH)2Cu(OH)2

[H – bonding]

(where, -R represents the matrix of sawdust). In Rahman (2007)’s study, the maximum copper ions adsorption was found in pH value of 7.0, however a pH value of 6.0 was chosen as being the optimum for further experiment to avoid the precipitation of Cu(OH)2+ as Cu2+ precipitates above pH 6.5 in the form of Cu(OH)2. At this pH, the Cu(II) ions species present in the solution exist in two forms, Cu2+ being the major component and Cu(OH)+ the minor one. Several researchers have also investigated the effect of pH on biosorption of heavy metals by using different biomass and found similar results with this study. Saeed et al. (2005) investigated the biosorption of heavy metals by black gram husk and determined the optimum pH 5.0 for Cu(II) sorption. Qin et al. (2006) reported the optimum pH value for Cu(II) adsorption on peat was 4.0. The reported optimum pH value for Cu(II) ions on waste brewery biomass was 4.0 (Marques et al., 2000), sugar beet pulp was 5.5 (Reddad et al., 2002). Montanher et al. (2005) studied rice bran using different pH values in solutions for the removal of Pb(II), Cu(II), Cd(II) and Zn(II) and the maximum heavy metals removal efficiency was achieved at pH values around 5-6. Analysis of the maximum adsorption capacity using isotherms The adsorption isotherm study is fundamental and the maximum adsorption capacity on adsorbent may be mathematically determined by the

Sustainable Purifcation Techniques for Agricultural Waters  197 isotherms. The adsorption isotherm is based on the assumption that every adsorption site is equivalent and independent of whether or not adjacent site are occupied. Isotherms show the relationship between metal concentration in solution and amount of metal adsorbed on a specific sorbent at a constant temperature. Isotherm studies were conducted in a series of 250 ml Erlenmeyer Flasks. Each flask was filled with 100 ml of different initial concentration of Cu(II) ions solution (5 mg/L, 10 mg/L, 25 mg/L, 50 mg/L and 100 mg/L). A fixed amount of maple wood sawdust (10 g/L) was taken in each flask and the experiment was conducted at room temperature (23 ºC). After equilibration, the solution was separated using Whatman-40 filter paper and the metal ions concentration in solution before and after adsorption was measured by AAS. The equilibrium adsorption capacity was calculated using the following expression (Goel et al., 2005).



qe (mg / g ) =

(C0 − Ce )V m

(5.2)

where, qe = Equilibrium adsorption capacity (mg/g) Co = Initial concentration (mg/L) of copper ions in solution, Ce =  Equilibrium concentration (mg/L) of copper ions in  solution V = Volume of aqueous solution (ml) and m = Dry weight of the adsorbent (g/L). Akinbiyi (2000) presented a graphical representation of several form of isotherms, as shown in Figure 5.25. When equilibrium solid phase concentration of an adsorbate increases sharply from a low to a high equilibrium concentration, the adsorption is said to be favorable and results in a ­convex-shaped isotherm (also called, Type I isotherm). Isotherms of concave shape indicate an unfavorable adsorption process and are called Type III isotherms. When equilibrium solid phase concentration of an adsorbate increases linearly with equilibrium concentration of an adsorbate in the liquid phase, the isotherm obtained is called a linear or a Type II isotherm. The amount of copper ions adsorbed per specific amount of adsorbent (qe) was calculated according to Equation (5.2). The dependence of the metal uptake data (qe) on the equilibrium concentration of copper (Ce) in aqueous solutions for different pH values is shown in Figure 5.26. It is observed that the pH has a significant effect on adsorption equilibrium.

198  Sustainable Water Purification Irreversible

Equilibrium concentration of adsorbate on adsorbent

Favorable

Linear

Unfavorable

Equilibrium concentration of adsorbate in liquid phase

Figure 5.25  Plots of various kinds of isotherms (adapted from Akinbiyi, 2000).

Metal Adsorbed (qe) mg/g adsorbent

8 pH 2 pH 4 pH 6 pH 8

7 6 5 4 3 2 1 0

0

10

20

30

40

50

60

70

80

Equilibrium concentration (Ce) mg/L

Figure 5.26  Equilibrium concentration (mg/L) vs metal adsorption capacity mg/g maple wood sawdust (mean values of the triplicate analysis for different pH values are used).

In order to establish the maximum metal sorption capacity, adsorption studies were performed at different pH values. The Langmuir and the Freundlich isotherms are the most widely used isotherm and these two isotherms were applied by Rahman (2007). Figure 5.26 indicates that the metal adsorption increased sharply followed the isotherm type-I as the pH was increased from 4.0 to 6.0. It reveals that the adsorption isotherms were favorable at pH value 4.0 and 6.0. However, adsorption isotherms were unfavorable at pH value 2.0 and 8.0 for this study.

Sustainable Purifcation Techniques for Agricultural Waters  199 A.  Langmuir isotherm An American chemist, Irving Langmuir, developed a theoretical equilibrium isotherm relating the amount of solute sorbed on a surface to the concentration of solute (Langmuir, 1916). This equation is derived from simple mass action kinetics, assuming chemisorption. The Langmuir adsorption isotherm has found wide range of applications, including water treatment. Its advantages include simplicity, having some physical basis, and its ability to fit a broad range of experimental data. The Langmuir model assumes that the uptakes of metal ions occur on a homogenous surface by monolayer adsorption without any interaction between adsorbed ions. The Langmuir model can be described as the following



qe =

qm K LCe 1 + K L Ce

(5.3)

The Langmuir adsorption isotherm equation can be linearized as given below



Ce 1 1 = + Ce qe K L ⋅ qm qm

(5.4)

where, qe = Amount of metal adsorbed per specific amount of    adsorbent (mg/g) qm = Amount of metal ions required to form a monolayer   (mg/g) KL =   Langmuir equilibrium constant, and Ce =   Equilibrium concentration of the solution (mg/L) The equilibrium data were analyzed using the linearized form of Langmuir adsorption isotherm Equation (5.4). The Langmuir constants, KL and monolayer sorption capacity, qm were calculated from the slope and intercept of the plot between Ce/qe and Ce (Figure 5.27). The Langmuir adsorption isotherm was determined at different pH values ranging from 2.0 to 8.0 for a concentration range of 5-100 mg/L. All solutions contain a fixed specific mass of sawdust (10 g/L). The isotherm constants were calculated from the isotherm equations for the different pH values are presented in Table 5.5.

200  Sustainable Water Purification 12 y = 0.182x + 6.8269 R2 = 0.5474

10

y = 0.1213x + 2.8565 R2 = 0.9205

Ceq /qeq

8 6

y = 0.1088x + 2.4646 R2 = 0.9294

4 2 0

pH 4

0

10

pH 6

20 30 40 Equilibrium conc (Ce) mg/L

pH 8

50

60

Figure 5.27  The Langmuir isotherms plots for the adsorption of copper ions onto maple sawdust sample at different pH values (4.0, 6.0 and 8.0) for each copper ions solution (5, 10, 25, 50 and 100 mg/L).

The linear plot of Ceq/qeq and Ce demonstrates that the experimental data fit Langmuir isotherms reasonably well over the whole copper concentration range studied. The regression coefficient values (r2) in the case of Langmuir isotherms for different pH values were varied from 0.54 to 0.92. The r2 value near unity indicates an excellent fit to the isotherm equation and near zero indicates a very poor fit. Therefore, the equation that gives maximum coefficient of correlation is the best fit equation and this equation is used to determine the amount of metal ions required to form a monolayer on adsorbent (qm) and the Langmuir equilibrium constant (KL) (Utgikar et al., 2000; Figueira et al., 2000; Brown et al., 2000; An et al., 2001; Say et al., 2001). The values of both Langmuir isotherm parameters are calculated from linearized equation and the results are presented in Table 5.5. It is observed that the maximum metal adsorption capacity varied with the change of pH value and the maximum metal adsorption was found to be at a pH of 6.0. Sing and Yu (1998) have been reported that the higher value of KL, the higher is the affinity of adsorbent for the metal biosorbed. It is evident from the values of KL for various pH values (Table 5.5) that the affinity of maple sawdust to biosorb copper ions is greater at a pH value of 6.0 than that the pH values of 4.0 and 8.0. From the Table 5.5, it can be seen that the value of qe is smaller than qm for all pH values. This indicates that the adsorption of copper ions onto sawdust is of a monolayer type, with still unsaturated surface of the maple wood sawdust (Ozer et al.,

qe (mg/g)

5.6

6.1

5.4

pH value

4

6

8

5.494

9.191

8.244

qm (mg/g)

0.026

0.044

0.043

KL (L/mg)

The Langmuir isotherm constants

0.5474

0.9294

0.9205

r2

0.885

0.819

0.823

RL

qe =

qe =

qe =

0.142Ce 1 + 0.026Ce

0.404Ce 1 + 0.044Ce

0.354Ce 1 + 0.043Ce

Equation

Table 5.5  The Langmuir adsorption isotherm parameters and equation for adsorption of copper (II) on maple sawdust.

Sustainable Purifcation Techniques for Agricultural Waters  201

202  Sustainable Water Purification 2006). The variation of Langmuir isotherm constant KL according to pH values indicates the fact that the affinity of metal ions onto sawdust is pH dependent. Hall et al. (1966) showed that the main characteristic of the Langmuir isotherm was its dimensionless constant separation factor (equilibrium parameter), RL. This separation factor (RL) can be calculated using the following equation:

RL =



1 1 + K L Co

(5.5)

where, KL is the Langmuir constant and Co is the initial concentration of metal ion. The value of separation parameter RL provides important information about the nature of adsorption (Table 5.6). The values of the Langmuir separation parameter, RL was calculated using Equation (5.5) at different pH value and was shown in Figure 5.28. The values of RL between 0 to 1.0, indicating more favorable sorption of copper ions on maple sawdust for the pH values of 4.0 and 6.0. However the Langmuir separation parameter RL is dependent on concentration and according to McKay et al. (1982), this indicates that the sorption of copper onto sawdust is also feasible at the concentrations studied. B.  Freundlich isotherm An empirical sorption isotherm was presented by a German physical chemist Herbert Max Finley Freundlich (Freundlich, 1926). This isotherm assumes that the metal ions uptakes occur on a heterogeneous surfaces by multilayer adsorption and the amount of adsorbate adsorbed increases Table 5.6  Use of separation parameter, RL in getting information about the nature of adsorption (Hall et al., 1966). Serial no.

Value of RL

Information about the adsorption

1.

RL >1

Unfavorable

2.

RL = 1

Linear

3.

O< RL 4.0 and < 8.0. The adsorption coefficients (KF, 1/n) agreed well with the conditions of favorable adsorption. On the basis of linear regression correlation coefficient (r2) value, the sorption data were somewhat better fitted by the Langmuir isotherm model as compared to Freundlich isotherm model for the adsorption of Cu(II), Cd(II) and Pb(II) from the aqueous solutions. • At equilibrium, the maximum metal adsorption capacity qmax (mg/g) of the maple sawdust samples was in order of lead (9.52 mg/g) > copper (9.19 mg/g) > cadmium (7.429 mg/g). It might be due to the metals ions properties i.e. ionic size of metal, the nature and distribution of active groups on the biosorbent, and the mode of interaction between the metal ions and the biosorbent. • The maximum metal adsorption capacity qe (experimental value) was smaller than qmax (model value) for the adsorption of lead, copper, cadmium ions. This indicated that the adsorption of the metals ions onto the maple sawdust samples was a monolayer type one that did not fully cover the surface of the sawdust. • It can be concluded that the use of maple sawdust as an effective and environmentally friendly adsorbent may be an alternative to more costly materials such as activated carbon for the removal of heavy metals from aqueous solution.

208  Sustainable Water Purification The main advantage of use this adsorbent is that it does not mix with and can be very easily separated from water.

5.4 Removal of Heavy Metals Using Fish Scale A variety of treatment technologies are available with different degree of success to control and minimize water pollution. However, the shortcomings of most of these methods are high operational and maintenance costs, generation of toxic sludge and complicated procedure involved in the treatment. Comparatively, adsorption process is considered a better alternative in water and wastewater treatment because of convenience, ease of operation and simplicity of design. In wastewater treatment plants (WWTPs), adsorption processes are applied for the removal of dissolved pollutants that remain from the subsequent biological phases or after chemical oxidation treatments. A large variety of low-cost adsorbents have been examined for their ability to remove various types of pollutants from water and wastewater. Generally, the goal is to replace activated carbons – representing the stateof-the-art – by means of a by-products coming from various activities such as agriculture and industry. These by-products currently pose a variety of disposal problems due to their bulk volume, toxicity or physical nature (i.e., petroleum wastes, scrap tyres). If these wastes could be used as lowcost adsorbents, it will provide a two-fold advantage to environmental pollution. A recent study done by Mustafiz et al. (2003) suggested that fish scales of Atlantic cod, Gadus morhua Linnaeus, be a better alternative to reduce the level of lead, arsenic and chromium in water. Following Mustafiz et al. (2003), several researchers have investigated the sorption capabilities of fish scales for the uptake of heavy metals in water. The uptake abilities of scales from different fish species should be similar because most fish scales contain significant portions of organic protein (collagen), and the structure of collagen shows that it contains the possible functional groups, such as phosphate, carboxyl, amine and amide, that are involved in the biosorption of heavy metals (Mustafiz et al., 2003).

5.4.1 Fish Scale Collection and Treatment Atlantic cod scales were collected from a local fish market in Halifax, Nova Scotia for the heavy metals removal study. The grain size tests were performed in both acidic and alkaline environment and the size of the grains

Sustainable Purifcation Techniques for Agricultural Waters  209 varied less than 50 microns. The scales are rinsed with distilled water to remove the sodium ions and then dried at temperature of 65 °C (Cole, 2001) for 12 hours. The drying was complete after 12 hours. The following chemicals are used for the treatment of fish scale before using for heavy metal removal. 1. 2. 3. 4. 5.

Water Hydrochloric acid (5% concentration) Acetone Soap Sodium hydroxide (5% concentration)

The treatment of the fish scales with each of the reagents (1 through 5) mentioned above included allowing the bio-adsorbent to be in contact with the reagents for 5 hours. The adsorbent was then rinsed with deionized water until a stable pH value of the leachate was observed. The sample was completely dried in a baking oven at a temperature of 65 °C for 16 hours. The fish scale collected from the market was oven dried (after washing with deionized water repetitively) for two days at 65 °C. This dried scales were then grounded in laboratory by pulverize to produce powdered mass of size in the range of 5-50 µm.

5.4.2 Experimental Setup and Procedure 5.4.2.1 Static Method Atlantic cod (Gadus Morhua) fish scale was collected from the Fishermen’s Market located in Bedford, Halifax, Canada. The sample was then oven dried at 110 °C for 48 h. The scales were pulverized to the finest size (37 micron). Lead solutions were prepared for 3 different concentrations, 25 ppm, 12.5 ppm, and 6.25 ppm. This was followed by the addition of 10 g of fish scales in each solution. The beakers were kept covered in order to avoid evaporation. The solutions were kept for several hours and samples were collected into test tubes from each beaker. Concentrations of lead ions were measured by the atomic absorption (AA) technique.

5.4.2.1.1 Effect of Time

The adsorption behavior of 12.5 ppm lead solution with time is displayed in Figure 5.31. The lead concentration decreased from 12.5 ppm to 0.48 ppm in 120 h. However, fluctuations in the concentrations of the lead solution were observed. This was perhaps due to the local desorption coefficient

210  Sustainable Water Purification 30

Concentration (ppm)

25 20 25 ppm

15

12.5 ppm

10

6.25 ppm 5 0 0

20

40

80 60 Time (hours)

100

120

140

Figure 5.31  Concentration of lead with time.

dominating the sorption process (between an 8–16 h and 24–52  h time period). Desorptive behavior of the cations has a significant role, as observed with the intermediate increases in concentrations of the solutions in the case of the 12.5 ppm and 6.25 ppm solutions. It is likely that with a sharp decrease in the concentration of the solutions, the lead ions adsorbed on the fish scales tend to diffuse back to the bulk solutions. This is followed by an increase in adsorption in later time intervals. Borwankar and Wasan (1986) reported a kinetic-diffusion model that could predict the surface concentration at specific influent concentrations (provided other physical parameters are available). This model showed that a sharp decline in the potential energy of the solution could be possible. Moreover, after reaching the equilibrium point, if the exothermic energy of adsorption overcomes the desorption energy barrier, a diffusion process between adsorbed and bulk phase is established. A similar kinetic-diffusion model based on the concept of adsorption and diffusion may be applied to describe the behavior of the solution at 12.5 ppm. Overall, the static equilibrium was reached after a relatively longer time period when compared to dynamic equilibrium. The delay is partly attributed to the fact that unlike in dynamic equilibrium, the sorption effect in the case of static equilibrium is initially localized to the first few layers of the adsorbent.

5.4.2.1.2 Effect of Environmental pH

The fish scales when treated with caustic soda (5%) and left in a solution of cobalt under shaking condition for 24 h yielded maximum adsorptivity. In

Sustainable Purifcation Techniques for Agricultural Waters  211

(a)

(b)

(c)

Figure 5.32  (a) Magnified image (100 times) of dried and pulverized fish scale before adsorption. (b) Magnified image (100 times) of fish scale after adsorption (but not dried). (c) Magnified image (100 times) of fish scale after adsorption (after drying).

other words, an increase in pH enhances the adsorptivity of the fish scales. But the acidic solution performed poorly in adsorbing the heavy metals. Figures 5.32a–c show microstructures of fish scales. Images of cod fish scales were taken by a computer image analyzer. This device has been proven to be effective for observing microstructures of biological materials (Chaalal and Islam, 2001). In Figure 5.32a, the white color signifies the surface of the scale, while the black spots are the voids. The variation in color shows that the surface is uneven at particular sites. In Figure 5.32b, some distinct black spots are observed. This gives the impression that there are still vacant sites where more adosorption is possible. The rest of the area looks more stable. Figure 5.32c shows the image that was taken after the scale had been dried at room temperature after adsorption. A brownish-grey color was observed in this case, which could be seen around the black areas. This was an indication of the presence of some foreign species, which was likely to be the metal cations.

5.4.2.2 Dynamic Method The experimental setup used for the dynamic test is shown in Figure 5.33. The column used for the study of cobalt alone in the dynamic system (continuous system) was made of plastic and was 30 cm long and 10 mm in diameter. The column was filled with the scales of a fish scales washed with liquid soap and rinsed. The height of the material was 22 cm. The flow was downward in this study and the inlet concentration was also changed. To study the mixture of cobalt chloride (CoCl2), zinc nitrate hexahydrate (Zn(NO3)2.6H2O), strontium nitrate (SrNO3), and lead nitrate

212  Sustainable Water Purification

Solution Tank

Atomic Absorption

Adsorption Column

Pump

Figure 5.33  Schematic of the dynamic system.

(Pb(NO3)2) solutions a new column was used. Fifty ppm of each compound was mixed. A mixture of 200 ppm metals was flown through the new column containing 4 g of fish scales treated with 5% sodium hydroxide (NaOH). This glass column had an interior diameter of 11 mm and a height of 12 cm. The upward flow was controlled with a small pump (at a flow rate of 2 ml/min). Concentrations of lead ions were measured by the atomic absorption (AA) technique. From Figures 5.34a and b it is observed that an increase in the flow rate from 1 ml/min to 7 ml/min resulted in a decrease in the breakthrough time period. This is obvious because saturation was achieved earlier with a faster flow rate. Figures 5.35 to 5.38 7–10 represent the outlet concentration as a function of time for each metal. The feed is a mixture of strontium, cobalt, zinc, and lead (50 ppm each). From Figures 5.35 it is observed that in the case of strontium ions in the mixture, breakthrough did not take place for the first 12 min the influent was adsorbed by the scale. This might be due to the fact that strontium was competing with lead and zinc and both showed tremendous affinity for the adsorbent. As a result, there might develop a concentration gradient between the feed and the solution already present. So strontium ions with the least electron affinity among the 4 species diffused back into the bulk solution (Lide, 1991). The energy barrier required for desorption was provided by the heat of adsorption of all the species. But eventually this resulted in an increase of vacant sorption sites. An increase in site concentration resulted in a proportionate increase in strontium ion adsorption

Sustainable Purifcation Techniques for Agricultural Waters  213 60 50 40 30 20 10 0 0.00

5.00

10.00

15.00 Time (hours) (a)

20.00

15

20 25 Time (hours) (b)

30

30

25.00

30.00

Concentration (ppm)

25 20 15 10 5 0 0

5

10

35

45

40

Figure 5.34  (a) Adsorption of cobalt in a continuous system (breakthrough); concentration = 50 ppm and flow = 1 ml/min. (b) Adsorption of cobalt in a continuous system (breakthrough); concentration = 100 ppm and flow = 7 ml/min.

35

Concentration (ppm)

30 25 20 15 10 5 0

0

20

40

60 80 Time (minutes)

Figure 5.35  Strontium breakthrough in the mixture.

100

120

140

214  Sustainable Water Purification

Concentration (ppm)

until steady-state equilibrium was achieved. Further, note that all the zinc and lead ions were being adsorbed during that time. Figure 5.36 shows that in the case of cobalt ions, the equilibrium time interval was reached after 200 min. The adsorption rate was slower in comparison to the strontium ions. However, Lide (1991) reported that cobalt ions exhibit higher electron affinity than strontium ions. This behavior is illustrated by the fact that after 50 min the vacant adsorption sites were still being preferentially filled first by the cobalt ions. Figure 5.37 shows the breakthrough of lead ions in the mixture. In this figure, the process of adsorption reached its first phase after 75 min. The larger size of the lead ions leads to a lower mobility and higher surface contact with the adsorbent. Figure 5.38 shows the breakthrough of zinc in the mixture. For the zinc solution, the electron affinity is unstable. Since the ionic radii of zinc ions are smaller than those of lead ions, it is assumed that the affinity will be larger in comparison to the lead ions. Consequently, even though the mobility of zinc ions is higher than that of lead ions, the

50 40 30 20 10 0 0

50

100

150 Time (minutes)

200

250

300

250

300

Figure 5.36  Cobalt breakthrough in the mixture.

Concentration (ppm)

0.12 0.1 0.08 0.06 0.04 0.02 0 0

50

100

150 Time (minutes)

Figure 5.37  Lead breakthrough in the mixture.

200

Concentration (ppm)

Sustainable Purifcation Techniques for Agricultural Waters  215 8 6 4 2 0 0

50

100

150

200

250

300

Time (minutes)

Figure 5.38  Zinc breakthrough in the mixture.

zinc ions are adsorbed for higher time intervals because there are still vacant sites available.

5.4.3 Conclusions The novel technique of using fish scales as adsorbents proposed can eliminate nearly 95% of lead ions in the influent. Experiments have also been conducted with cobalt, zinc, and strontium ions. They also showed a marked decrease of metal concentrations in their respective effluent solutions. It is expected in the future that the technique of using fish scales as an adsorbent will be developed into a patent to aid in the removal of heavy metals from waste water. Based on these experiments, the following conclusions can be reached: (1) The presence of maxima was observed in the adsorbed amount versus the concentration curve of lead ions, (2) for lead ions, breakthrough is more distinct in comparison to breakthrough of strontium or zinc ions because desorption effects are minimal, (3) the metal ions appeared in the effluent solution in the following order: (a) strontium after 15 min, (b) cobalt after 25 min, (c) lead after 1 h, and (d) zinc after 2.5 h, (4) in competitive adsorption, the mobility and electron affinity of each cation plays a vital role in its respective adsorption behavior. The availability of adsorption sites determines whether the mobility or the electron affinity will dominate. In general, industries spend considerable resources in wastewater treatment. This novel technique can result in energy savings of significant amounts from a more efficient wastewater treatment system operating for fewer hours. Chemicals such as chromic acid, nickel sulfate, and zinc cyanide are used by the electroplating industry to produce “decorative and protective finishes” on metal and plastic products. An average plating shop produces huge amounts of “waste rinse water” per year that requires

216  Sustainable Water Purification treatment for the removal of toxic metal ions and organics. Disposal in land falls (burial of metal sludge or solidified metal sludge) results in the loss of valuable metals and energy resources. The evaluation of this proposed novel method has the potential to separate toxic metal ions from wastewater. Moreover, there is the scope of finding the adsorbed metals on the surface of fish scales as a major source of new biopolymers. This will save enormous handling costs of energy that requires replacement of the discharged wastewater. It will ultimately lead to the improvement of electroplating economics. Also, formation of less viscous new biopolymers (study is underway) from the “adsorbed scale” can reduce pumping and drilling costs and the costs of pipeline corrosion, which will certainly benefit the petroleum industry.

5.5 Solar UV Treatment Solar water distillation is the process of using the energy from sunlight to separate freshwater from salts or other contaminants. The untreated water is placed into a still basin which absorbs heat, eventually reaching high temperatures, causing the water to evaporate, cool and condense into vapour, leaving the contaminants in the underlying basin. The vapour forms as drops on an overlying cover (usually glass) that are channeled and collected in a separate basin as freshwater. Solar water distillers are simple and relatively cheap technologies that provide alternative sources of freshwater in water stressed areas. Saltwater or soft water (surface water with few ions) can be used to produce safe drinking water, while more heavily polluted water such as waste water should only be used for non-drinking purposes such as industrial water reuse, unless additionally treated. Small and simple solar water distillers are usually built for single households, though larger systems can also be set up for shared use. It is well documented that solar energy can be an effective means of cleaning contaminated water. This is because ultraviolet (UV) light destroys the formation of DNA linkages in microorganisms, thereby preventing them from reproducing and thus rendering them harmless. The World Health Organization  lists solar disinfection in clear bottles by the combined action of UV radiation, as well as thermal disinfection (pasteurization) in opaque vessels with sunlight from solar cookers or reflectors and combination systems employing chemical coagulation-flocculation as some of the most promising and accessible technologies for household water treatment.

Sustainable Purifcation Techniques for Agricultural Waters  217 There are various products available on the market for water purification using solar energy. One method for solar water disinfection (also called SoDis) uses solar energy to make water contaminated with bacteria, viruses, protozoa and worms safe to drink. Water contaminated with non-biological agents such as toxic chemicals or heavy metals require additional steps to make the water safe to drink. It is a simple water treatment method using solar radiation (UV-A light and temperature) to destroy pathogenic bacteria and viruses present in the water. Its efficiency to kill Protozoa is dependent on the water temperature reached during solar exposure and on the climatic and weather conditions. Microbiologically contaminated water is filled into transparent containers and exposed to full sunlight during 6 hours. SODIS uses two components of the sunlight for the water disinfection. The first, UV-A radiation has a germicidal effect. The second component, infrared radiation, raises the water temperature and is known as pasteurisation when the water temperature is raised to 70°C–75°C. The combined use of both UV-A radiation and heat produce a synergetic effect enhancing the efficiency of the process.

5.5.1 Effects of UV-Radiation Solar radiation can be divided into three ranges of wavelength: UV radiation, visible light and infrared radiation. UV radiation cannot be perceived by the human eye. It is a very aggressive radiation that can cause severe damage to the skin and eyes and destroys living cells. Luckily most of the UV-C and UV-B light in the range of 200 to 320 nm is absorbed by the ozone (O3) layer in the atmosphere which protects the earth from radiation coming from space. Only a higher fraction of UV-A radiation in the wavelength range of 320 nm to 400 nm, near the visible violet light, reaches the surface of the earth. UV-A light has a lethal effect on human pathogens present in water. These pathogens are not well adapted to aggressive environmental conditions as they find their specific living conditions in the human gastrointestinal tract. Therefore, they are more sensitive to sunlight than organisms commonly abundant in the environment. UV-A radiation directly interacts with the DNA, nucleic acids and enzymes of the living cells, changes the molecular structure and leads to cell death. UV radiation also reacts with oxygen dissolved in the water and produces highly reactive forms of oxygen (oxygen free radicals and hydrogen peroxides). These reactive molecules also interfere with cell structures and kill the pathogens.

218  Sustainable Water Purification

5.5.2 Effects of Temperature (Infrared Radiation) Another aspect of the sunlight is the long-wave radiation called infrared. Also this radiation cannot be seen by the human eye, but we can feel the heat produced by light of the wavelength beyond 700 nm. The infrared radiation absorbed by the water is responsible for heating it up. Microorganisms are sensitive to heat. The following table lists the temperature and exposure time required to eliminate microorganisms. It can be seen that water does not have to be boiled in order to kill 99.9% of the microorganisms. Heating up the water to 50 to 60 °C for one hour has the same effect.

5.5.3 Advantages of Solar Water Disinfection (SoDis) Solar water distillers are typically used in remote areas where there is limited access to freshwater and centralized distribution systems. Technical experts may be required to introduce the system and train direct users in use and maintenance. The systems require siting on flat and open areas with access to water and sunlight. The “roof ” of the system is installed with a transparent cover (often glass), placed at an angle to receive maximum sunlight. The sun penetrates through the cover and into the underlying still basin. The untreated water is collected in the still basin and heated up by the sun, eventually evaporating and separating from the contaminants. It is important that the material used for the still basin can absorb heat, for example a leather sheet, silicon, reinforced plastic, or steel plate. The slanted cover funnels the thin layer of condensed water from its underside into a channel (pipe, tube), which leads to a separate water storage container so it can be used for domestic purposes or drinking water. The remaining contaminants in the still basin should be appropriately disposed. The specific objectives of solar water disinfection (SoDis) are given below: • SoDis improves the microbiological quality of drinking water. • SoDis improves the family health.   • SoDis can serve as an entry point for health and hygiene education. • Public water supply systems in developing countries often fail to provide water safe for consumption. SoDis provides individual users a simple method that can be applied at household level under their own control and responsibility. • SoDis is easy to understand.

Sustainable Purifcation Techniques for Agricultural Waters  219 • Everybody can afford SoDis, as the only resources required are sunlight, which is cost free and plastic bottles. • SoDis does not require a large and costly infrastructure and therefore easily is replicable in self-help projects. • SoDis reduces the need for traditional energy sources such as firewood and kerosene/gas. • Consequently the use of SoDis reduces deforestation, a major environmental problem in most developing countries, and SoDis decreases air pollution created by burning conventional energy sources. • Women and children often spend much of their time and energy collecting firewood. SoDis reduces this workload as less firewood needs to be collected. • Financial advantages: Household expenditures can be reduced when the user’s family health is improved: less financial resources are required for medical care. In addition, expenses for traditional energy sources such as gas, kerosene and firewood are reduced. Only limited resources are required for the procurement of transparent plastic bottles. Therefore even the poorest can afford SoDis.

5.5.4 Limitations of Solar Water Disinfection • SoDis requires sufficient solar radiation. Therefore it depends on the weather and climatic conditions. • SoDis requires clear water. • SoDis does not change the chemical water quality. • SoDis is not useful to treat large volumes of water.

5.6 Bioremediation for Sustainable Purification of Water Microbial bioremediation is the use of prokaryotes (or microbial metabolism) to remove pollutants. The oldest example, and the most successful, is sewage treatment, which has been used in one form or another, for thousands of years. However, the connection between disease and contaminated water was only made in the late 1800s.  Whether the sewage is buried below an outhouse, in septic tanks or processed in modern wastewater treatment plants, bioremediation of the water is largely, if not

220  Sustainable Water Purification entirely, based on microbial degradation of the organics to inorganics. Bioremediation happens naturally in the environment, but has also been used to remove agricultural chemicals (e.g., pesticides, fertilizers) that leach from soil into groundwater and the subsurface. Certain toxic metals and oxides, such as selenium and arsenic compounds, can also be removed from water by bioremediation. The reduction of SeO4-2 to SeO3-2 and to Se0 (metallic selenium) removes selenium ions from water and is catalyzed by bacteria and archaea using the selenium ions are terminal electron acceptors in anaerobic respiration. As an active ingredient of some pesticides, mercury is used in industry, and is also a by-product of certain processes such as battery production. Methyl mercury is usually present in very low concentrations in natural environments, but it is highly toxic because it accumulates in living tissues. Several species of bacteria can carry out the biotransformation of toxic mercury into nontoxic forms. Bacteria such as Pseudomonas aeruginosa can convert Hg+2 into the less toxic Hg0 through anaerobic respiration.

6 Sustainable Purification Techniques for Industrial Wastes 6.1 Removal of Radionuclides The formation of radioactive isotopes of cesium and strontium is considered to be one of the most difficult long-term problems associated to nuclear reactors. Commonly proposed methods, used for removal of cesium and strontium, are adsorption on zeolites, clay minerals, and synthetic exchangers (Amphelett, 1964). In a similar way, phosphate, arsenate, tungstate, and molybdate salts of zirconium, thorium, titanium, and other metals have also been considered for CsC removal. Each of these methods has its shortcomings (Komarneni and Roy, 1986). For instance, zeolites tend to decompose at high pH, clays cannot sustain selectivity at high sodium concentrations, organic materials undergo radiolysis in the presence of large amounts of 137CsC, and others (Mercer and Ames, 1978). The use of biomass as an effective adsorbent has been gaining popularity since 1990s. Avery and Tobin (1992) reported the use of Saccharomyces cerevisiae in order to adsorb divalent metal cations in dilute solutions onto the cell walls, both alive or denatured. They reported particularly high selectivity for Sr2C atoms. In a similar approach, living sunflower stalks have been found to reduce Sr2C concentration within hours of implementation in a hydroponic pond (Anon., 1997). The study by AlMarzouqi and Islam (1999) reveals more about the adsorptive properties of both denatured and live sunflower stalks. Their study found that sunflower stalks are not reliable in adsorbing strontium when other contaminants are present in the liquid stream. Similar use of organic materials has gained popularity in developing technologies or removal for heavy metal from wastewater streams (Shiskowski and Viraraghavan, 1993; Viraraghavan and Dronamraju, 1993). Until 2001. No research reported the ability to remove these two elements to level acceptable by regulatory agency. For the first time, Chaalal and Islam (2001)

M. Safiur Rahman and M.R. Islam. Sustainable Water Purification, (221–298) © 2020 Scrivener Publishing LLC

221

222  Sustainable Water Purification introduced a novel combination of some of the well-known adsorption techniques are introduced in order to develop a comprehensive technique that reduces strontium concentration to a low level and has the potential of being an effective wastewater treatment process. The schematic of the Chaalal Islam process is presented in Figure 6.1. It contains an algae-packed column. This column constitutes the first filtration column of the process. The permeability of the packed column was high enough to allow continuous flow with only hydrostatic pressure of the line connected to the source trough. In addition to Sr2+ ions, these algae are known to adsorb most of Mg2+ and Ca2+ commonly found in water contaminated with strontium. However, the selectivity to Sr2C ions is usually significantly higher than that of the other ions. In case adsorption of Mg2C and Ca2C is a problem, these ions can be removed with Na3PO4 prior to this treatment step (Avery and Tobin, 1992). The packed column was connected to the air-curtain driven fluidized bed/membrane system. The Fluidized bed/membrane reactor is a very successful air curtain driven fluidized bed reactor (Backhurst et al., 1988), coupled with a membrane system (see Figure 6.1). The membrane system was an addition to the design of Backhurst et al. (1988). Compressed air is injected into the reactor through a series of perforations in a transverse tube in order to create fluid circulation with an air curtain. This process provides very efficient

Contaminated water tank

Algae-packed column (φ = 40 mm)

Compressed cotton membrane

Fluidized bed/membrane reactor

Fluidized bed with resins (φ = 45 mm) Compressed air

Air bubbles

Figure 6.1  The Chaalal set-up for removing radionucleiods (from Chaalal and Islam, 2001).

Purification Techniques for Industrial Waste  223 and rapid mass transfer in the liquid phase (Chaalal, 1990). Even though this technique has been employed in mixing mechanically sensitive materials (e.g. filamentous bacteria or larvae) with great success, the application of such a process in remediating contaminated water is new. Air was supplied to the reactor through a transverse tube with equally spaced 16 perforations of 1Ð6 mm diameters, placed in a single row. The tube was placed centrally (wall in the left and membrane to the right) across the narrow width of the bottom of the tank. A pre-specified amount of API bentonite powder was suspended in the reactor. This bentonite was of API grade and was supplied by the local water and electricity department. The bentonite particles were aimed at adsorbing the bulk of the contaminants. The membrane was installed in order to separate the bentonite from the suspensions. The same membrane, however, can be designed to separate some of the residual contaminants from the suspension. Water exited the apparatus via a 7-mm thick compressed cotton filter (membrane) enclosed in a perforated plexiglas box which retained the bentonite particles and adsorbed contaminants. Turbidity measurements of the effluent showed non-detectable loss of bentonite. The filter did not appear to become plugged with bentonite for the duration of the laboratory test. Besides, bentonite was primarily maintained in suspension by the air curtain. Effluent from the fluidized bed/membrane reactor was passed through a fluidized ion-exchange reactor. One gram of resin (Amberlite IR-120Na) was added to the fluidized bed of a relatively small diameter of 45 mm (see Figure 6.1). A single source of air bubbles was added to the bottom of the fluidized bed. Air bubbles were injected at a rate of 75 bubbles a minute, which was found to be adequate to keep the resins in suspension. Finally, bio-encapsulation followed by bioseparation was performed. Bacterial growth curves show that the bacteria (mesophilic and thermophilic strains) can survive and thrive in concentrations as high as 100 mg/l. Beyond this concentration, bacteria do not survive and are destroyed within 24 h. It is anticipated that the best use of bio-concentration is at a concen­ tration lower than 10 mg/l. Besides, bacterial growth rates being higher at lower concentration, it is most efficient to use the bio-concentration method for low concentrations of strontium. This process was later optimized for thermophilic bacteria, which were selected from the UAE, where harsh climate conditions prevail (Chaalal et al., 2015). They discovered that the use of thermophilic bacteria enhances the purification process but total recovery remains the same (meaning time required is reduced).

224  Sustainable Water Purification

6.2 Removal of Heavy Metals Precious Metals The industrial development is synonymous with the contamination of valuable surface and groundwater resources with toxic contaminants, such as heavy metals, dyes, nutrient ions (nitrogen and phosphate), and precious metals (PMs) (Won et al., 2014; Abdi and Kazemi, 2015; Shakoor et al., 2015). Out of all these, heavy metals in general poses the biggest threat as they are ubiquitous. Several conventional techniques (e.g., chemical precipitation, chemical coagulation, ion exchange, electrochemical technology, membrane process, ultrafiltration) have been used to achieve effective and rapid removal of these environmental contaminants, particularly metal ions, because of their toxic nature, and high production cost, and the limited or decreasing availability of metal deposits (Das, 2010; Lin et al., 2015; Dodson et al., 2015). However, as discussed in Chapter 3, none of these techniques are sustainable. In addition, they are high cost operations. Most importantly, they only transfer toxicity from one level to another, with superficial camouflaging the apparent toxicity to barely meet the regulatory requirement, which is always trailing the science of sustainability. Recently, sorption using biosorbents and biochars has seen significant advancements and is considered a promising technology for immobilizing (anionic/cationic) PMs and heavy metals, with subsequent recovery from water and wastewaters. This is attributed to the low cost and high efficiency, the negligible production of chemical or biological sludge, regenerability and reusability, and recovery of metals by the desorption process (Vijayaraghavan and Yun, 2008). A wide variety of biomaterials have been identified and examined to generate low-cost sorbents for the purification of water and wastewater, such as fungi, algae, and biowastes from agricultural and industrial by-products (Vijayaraghavan and Yun, 2008; Park et al., 2010). In the past few decades, biosorption of heavy metals, PMs, and ionic dyes has been widely and successfully studied for their removal from water and wastewater using agricultural and food industry biowastes: for example, peels of various fruits and vegetables, wheat straw, rice husk, and sugarcane bagasse (Shakoor et al., 2015; Abid et al., 2016). In addition to biosorbents, studies revealed significant advancements in the production of biochar from biowastes which differ in their physicochemical properties from carbonized materials (i.e., activated carbons) (Khare et al., 2013). Heavy metals such as zinc (Zn), nickel (Ni), iron (Fe), chromium (Cr), lead (Pb), manganese (Mn), copper (Cu), and cadmium (Cd) have been used in different industrial manufacturing/catalytic processes and released

Purification Techniques for Industrial Waste  225 into the environment through wastewater discharges or from their solid waste resources (Ghaly et al., 2014). In addition to heavy metals, PMs such as platinum group metals (PGMs) (ruthenium [Ru], rhodium [Rh], palladium [Pd], osmium [Os], iridium [Ir], and platinum [Pt]) are widely used in a variety of “hi-tech” industries owing to their unique physical and chemical properties (details on heavy metals and PMs have been provided in the following sections). The increasing demand of these heavy and PMs is in direct contrast to their reduced availability, particularly of PMs, and this has led to great rises or fluctuations in their prices, as well as efforts to explore new deposits. This prompted the need to remove and recover these metals from the water or wastewater and their secondary resources. Some researchers have tried to use various biomasses to recover PMs, in particular Au, Pt, Pd, and Ru. Table 6.1 shows the various types of biomaterials used to prepare biosorbents and biochars to recover heavy metals and PMs.

6.2.1 Precious Metals and Heavy Metals Recovery Precious metals, such as, gold (Au), silver (Ag), Pt, Pd, and Rb are used in various manufacturing fields including jewelry, electronics, dental industries, and the textile industry (Ghaly et al., 2014). The demand for PMs has increased, especially in the emerging economies of the world (McGlone, 2015). However, acquiring these PMs is difficult economically and technologically owing to their restricted supply by specific producing countries or their uneven distribution in production areas (Kawamoto, 2008). Heavy metals are described as metals which in their standard state have a specific gravity of more than 5 and atomic weight of 63.546-200.590 (Aslam, 2011). Heavy metals are responsible for many toxic effects on human health, such as lead poisoning (Pb), immune depression and skin diseases (Zn and Cu), cancer (Cr, Cd), neurological disorders (Mn), and blood disorders (Fe) (Abdalla et al., 2013). There is growing anxiety about securing a stable supply of these elements; therefore, the development of recycling technologies is important for using heavy metals and PMs resources efficiently, thus reducing their environmental burden through sustainable processes (Umeda et al., 2011). The following sources of precious metals and heavy metals are identified by Niazi et al. (2016): –– Municipal Wastewater and Storm Water –– Farm Wastewater Effluent of varying composition from farms

Source

Solid waste

Solid waste

Solid waste

Solid waste

Solid waste

Liquid waste

Liquid waste

Liquid waste

Liquid waste

Liquid waste

Precious metals/ heavy metals

Au, Ag, Pt, Rh, Ru

Au, Ag, Pt, Pd

Ag, Au, Pt

Au, Ag Pt, Ir

Ru, Ir, Pd

Soluble form of various PMs

Dissolved PMs

Ru, Ir, Rh

Au, Ag Pt, Pd

Au, Pt

Table 6.1  Sources of metals and heavy metals.

Municipal sewage

Hospital wastes jewelry-processing/making industry wastewater

Spent homogenous catalyst

Waste solutions from hydrometallurgy

Spent electroplating and other solutions

Heterogonous catalytic waste

Waste electrical and electronic equipment

Bottom ash fractions of incinerated MSW

Incineration bottom ash of MSW

Municipal Solid Waste (MSW)

Origin

(Continued)

Hartman and Schuster (2013)

Umeda et al. (2011)

Kwak et al. 2013

Won et al. (2014)

Cui and Zhang (2008)

Paul (2009), Won et al. (2014)

Cui and Zhang (2008), Park and Fray (2009)

Bakker et al. (2007)

Muchova et al. (2009)

Morf et al. (2013)

References

226  Sustainable Water Purification

Fumes or dust Oil spillage

Atmospheric air

Solid waste

Atmospheric air

Liquid waste

Agricultural soils

Atmospheric air

Atmospheric air

Oil polluted soil

Au, Ag, Cu

Zn, Cu

Cu, Pb Zn

Cu, Hg, Pb, Cd, Ni,

As, Cd Cu

Cd

Ni

Ni, Cu, Pb

Tobacco making

Wastewater irrigation industrial production, fertilizer and pesticide abuse, fossil fuel combustion

Aqueous wastes from industries of metal-plating, mining operations,tanneries, smelting, alloy industries, storage battery manufacture

Motor vehicle emissions, drips of crankcase oil, vehicle tire wear, asphalt road surfaces

Plastic, paper, ash, kitchen waste from MSW

Volcanic eruptions ashes

Incineration of PM vapors

Atmospheric air

Pt, Ir

Automotive catalyst exhaust

Origin

Atmospheric air

Source

Platinum group metals

Precious metals/ heavy metals

Table 6.1  Sources of metals and heavy metals. (Continued)

(Continued)

Osuji and Onajake (2004)

Kasprzak et al. (2003)

Järup (2003)

Du et al. (2015)

Kadirvelu et al. (2001)

Brow and Peake (2006)

Long et al. (2011)

Scher et al. (2013)

Gimeno-Gabra et al. (2003)

Bardi and Stefano (2014)

References

Purification Techniques for Industrial Waste  227

Households bleach, acid caustic chemicals, dental amalgam, ink and paper coatings, etc. Rice husks, olive pomace, orange wastes, compost Peanut, canola, soybean, straw biochars

Alamo switchgrass biochar Sugar beet tailing biochar Soybean stalk-based biochar Anaerobically digested dairy waste residue

Livestock manure

Agrochemicals

Domestic waste

Biochar

Biochar

Biochar

Biochar

Biochar

Biochar

Biochar

Biochar

Cu, Zn

Hg, As

Hg

Cu2+

Cu2+

Cu2+, Zn2+, Cd2+, Pb2+ removal

Cu2+, Cd2+

Cd2+, Pb2+

Cr6+

Hg2+

PB2+

Buffalo weed biochars

Pig and cow manure biochar

Sprayed as pesticides or fungicides

Provided to animals as dietary supplements

Sewage sludge

Liquid waste

Cu, Zn

Origin

Source

Precious metals/ heavy metals

Table 6.1  Sources of metals and heavy metals. (Continued)

Inyang et al. (2012)

Kong et al. (2011)

Dong et al. (2011)

Regmi et al. (2012)

(Continued)

Yakkala et al. (2013)

Kolodyńska et al. (2012)

Tong et al. (2011)

Pellera et al. (2012)

Tangahu and Warmadewanthi (2001)

Nicholson et al. (2003)

Nicholson et al. (2003)

Nicholson et al. (2003)

References

228  Sustainable Water Purification

Empty fruit branches Aerobically composted swine manure Bioproduct chars from pine, wood, pine bark, oak wood, oak bark Sugarcane pulp residue biochar Brewery waste yeast Rice husk carbon Grapefruit peel Tangerine peel Corn style Plantanus orientalis leaf Powder Pinus brutia leaf prawn carapace Modified rice husk Activated carbon Bamboo charcoal

Biochar

Biochar

Biochar

Biochar

Biochar

Biochar

Biochar

Biochar

Cu2+

PB2+, Cd2+, As3+

CR3+

Ag

Au

Ce

La

Zn

Origin

Source

2+

Precious metals/ heavy metals

Table 6.1  Sources of metals and heavy metals. (Continued)

(Continued)

Dodson et al. (2015)

Dodson et al. (2015)

Dodson et al. (2015)

Dodson et al. (2015)

Yang et al. (2013)

Mohan et al. (2007)

Meng et al. (2013)

Mubarak et al. (2013)

References

Purification Techniques for Industrial Waste  229

Won et al. (2014) Won et al. (2014)

Seaweed Hen eggshell membrane PEI-modified C. glutamicum biomass Decarboxylated PEI-Modified C. glutamicum biomass

Biochar

Biochar

Biochar

Biochar

AU(I)

AU(III)

Pd(II)

Ru

Won et al. (2014)

Won et al. (2014)

Won et al. (2014)

Polyethyleneimine (PEI)-grafted chitosan beads

Biochar

Ir

Activated carbon Polyethyleneimine (PEI)-grafted chitosan Beads Seaweed

Biochar

References

Nd

Origin

Source

Precious metals/ heavy metals

Table 6.1  Sources of metals and heavy metals. (Continued)

230  Sustainable Water Purification

Purification Techniques for Industrial Waste  231 –– Industrial Wastewater –– Electrical and Electronic Equipment –– Heterogeneous Catalytic Wastes (from motor vehicles) Aqueous wastes Bioremoval of PMs through biosorbents and biochar can be applied directly to recover elements from fluid or aqueous phases. The most available aqueous wastes that contain PMs are summarized next. Used in electroplating and other aqueous solutions used in the electroplating industry, metal objects are coated with a thin layer of different metals. The used or spent aqueous solutions from electroplating are produced as a result of washing and batch dumps containing dissolved forms of various precious as well as base metals themselves. PMs in electronic industries are used as crucial materials in connectors, switches, relay contacts, connecting wires, and strips (Cui and Zhang, 2008). The wastewater or aqueous solutions of these wastes contain various PMs that require recycling after removal from water systems. For example, aqueous waste from the semiconductor electronic industry is a main source of PMs in surface water streams. Hydrometallurgy Waste: Various hydrometallurgical methods have been exploited for the recovery of PMs from ores and secondary sources after leaching from solution waste. Hydrometallurgical techniques involve ion exchange, solvent extraction, reduction, and co-precipitation (Das, 2010). As a result of these processes, a huge amount of secondary waste is produced with low concentrations of dissolved PMs. These PMs need to be immobilized from their aqueous phases and recovered for future use in the relevant industries. Waste Homogeneous Catalysts Solution: In contrast to heterogeneous catalysts, homogeneous catalysts act in the same phase as the reactants. Because they are difficult to isolate from the reaction media, they are frequently detected in the product and waste solution (wastewater) streams. For example, preparation of acetic acid on a large or industrial scale in industries involves the use of PMs as a catalyst (Ru, Ir, or Rh). Figure 6.2 shows the blown up version of the sorption of biomass.

6.3 Industry Lifestyle Change Ancient practices right up to the era of industrial revolution were all sustainable (Khan and Islam, 2012). The technological marvels ranging from

232  Sustainable Water Purification Natural biomass modification

BIOSORBENTS Desorption/ Recovery of metals

Sorption of metals

BIOWASTES

ion exchange

Electrostatic attraction

sorption on biomass

Surface precipitation Micro-precipitations

Co-precipitation Surface complexation Physical sorption (inner sphere) Exchangeable metal ions Metal ions in aqueous soln. Metal ions bound to desorption & biochar Mineral components in biomass

Pyrolysis

Sorption Biochar of metals

Desorption/ Recovery of metals

Figure 6.2  Process involved at the surface of the biomass during biosorption and biochar recovery. (Modified from Bhatnagar et al., 2015).

pyramids and mummies to curving houses out of rock were all based on sustainable developments. It is the modern era that introduced unsustainable technologies through an array of ‘refining’ and processing tools, starting with coal and oil refining. Ever since chemicals extracted from these technologies have been used across the entire spectrum of today’s lifestyle. This resulted in the largest accumulation of waste within waterbodies all across the globe. Ever since, the world’s water resources have been under increasing threat from the impacts of energy production and utilization and ubiquitous existence of synthetic chemicals, all derived from petroleum products. As the global population grows, a persistent challenge is how to access enough water to meet humanity’s needs while also preserving the integrity of aquatic ecosystems. There is no moving forward unless there is a fundamental shift in energy utilization and collective lifestyle change. Perhaps the most lucrative value addition done is in the pharmaceutical industry. It is a very broad field, dealing with both synthetic, biological and natural medicines as well as cosmetics and food ingredients. Even when biological and natural medicines are used, they are either denatured or added to synthetic products.

Purification Techniques for Industrial Waste  233 Ion exchange Electrostatic attraction (Inner-sphere)

M M–

pH < pHPZC (anionic metal attraction)

M

M

M– M–

pH < pHPZC (cationic metal attraction)

O O C

M

O R

O M O O C H2+ O R H2+ O M Sorption on biomass (biosorbent and biochar) O M+ O C R O M M+ O O C R M+ M O O O H M H H M H2+

M

Surface complexation (Inner-sphere)

M

Surface precipitation/ micro-precipitation M O

M

H

M CO32– + M2+ SiO42– + M2+ 2PO42– + 3M2+

MCO3 ↓ MSiO4 ↓ M3(PO4)

Co-precipitation

Outer-sphere complexation (Physical sorption)

Exchangeable metal ions (Ca2+, Mg2+, Na+, K+) M

Metal ions (M+/M–) in aqueous solution

M

Metal ions (M+/M–) bound to biosorbent and biochar Mineral components in biomass (PO43–, CO32–)

Figure 6.2a  Metal removal mechanisms at the surface of biosorbents and biochars through sorption process.

In the ancient era, all the way up to the pre-industrial revolution age, both energy and pharmaceutical sectors were using natural ingredients. The knowledge of how beneficial oil could be was widespread all across the ancient world and people from all continents used oil for a number of purposes. These practices were also extremely effective and produced far more durable products than what are available today, without adding toxic chemicals. In terms of petroleum use, pre-industrial age era used natural products in their raw form. For instance, for millennia tar, a naturally deposited petroleum product, was used as a sealant for roofing shingles, brick bonding, the hulls of ships and boats (Daintith, 2008). The desired quality of tar was its ability to be waterproof. Tar was also used us a general disinfectant. Often tar would be mixed with other natural oil, such as balsam turpentine, linseed oil or Chinese tung oil, to obtain the desired properties.

234  Sustainable Water Purification One important direct use of petroleum products (e.g. tar) was medicinal (Barnes and Grieve, 2017). Since most oils that had seeped to the surface would mostly evaporate and leave behind bitumen - the tarry component of the mixture of hydrocarbons from which it is composed, this tarry material was the most in use. Even in Ancient Europe, tar once had the reputation of being a panacea. Pine tar, a carbonized distilled form of pine, is reported to be in use for over 2000 years as a medicine for skin conditions because of its soothing and antiseptic properties (Barnes and Grieve, 2017). Although pine tar is considered to be distinct from coal tar or naturally occurring petroleum tar, they all have medicinal values for a wide range of applications because of its antipruritic, anti‐inflammatory, antibacterial and antifungal nature (Muller, 1984). In addition to its keratolytic action, pine tar has been shown to be antipruritic (Braun‐Falco, 1991), anti‐inflammatory, antiseptic (Dawber, 1994), astringent, keratoplastic, cytostatic, antibacterial (Veijola and Mustakallio, 1964) and antifungal (Ishida et al., 1992). This is no surprise because it is well known that tar from natural sources have all of the natural chemicals (including heavy metals) that can serve as a medicine. After all, the pharmaceutical industry indeed uses the synthetic version of the same chemicals. Similarly, crude oil is known to have been used since the ancient era. Even today, some parts of the globe use crude oil for medicinal (Dienye et  al., 2012) and therapeutical (Hoke, 2015) purposes. However, in the modern era, use of crude oil or petroleum products in their native form is not promoted as a valid material source for any application and invariably all petroleum resources undergo refining. In terms of refining petroleum products, there is evidence that even during medieval era, refining techniques were present. However, those days, refining was not done in an unsustainable manner (Islam et al., 2010). There is evidence that both distillation and expression were common during the medieval era. In the perfume industry, as early as during early Islamic era (7th century onward), distillation in the form of hydrodistillation and production of absolute, mainly through Enfleurage and fermentation was common (Katz, 2012). The distillation process for refining oil appears to have been practiced through­out ancient times. Recent discovery of a 5000-year-old earthenware distillation apparatus, used for steam distillation tells us that our ancestors were well versed on developing sustainable technologies (Shnaubelt, 2002). Khan and Islam (2016) demonstrated how an earthenware distillation apparatus is sustainable. The ancient and middle age practices were mainly focused on medicinal applications. It was the case in ancient Orient and ancient Greece and Rome, as well as the Americas the oils used for medicinal purposes.

Purification Techniques for Industrial Waste  235 However, as reported by Islam et al. (2010), Medieval era scientists were also refining oil for producing shoot-free light. During the fifth century AD, the famed writer, Zosimus of Panopolis, refers to the distilling of a divine water and panacea. Throughout the early Middle Ages and beyond, a basic form of distillation was known and was used primarily to prepare floral waters or distilled aromatic waters. These appear to have been used in perfumery, as digestive tonics, in cooking, and for trading. Over 1000 years ago, Al-Rāzī (865-923), a Persian Muslim alchemist, wrote a book titled: Kitāb al-Asrār (Book of Secrets), in which he outlined a series of refining and material processing technologies (See Taylor, 2015 for the translation). Al-Rāzī developed a perfectly functioning distillation process. In this distillation process, he used naturally occurring chemicals. His stockroom was enriched with products of Persian mining and manufacturing, even with sal ammoniac, a Chinese discovery. These were all additives that he was using similar to the way catalysts are used today. His approach was fitting for his time, but way ahead of today’s concept of technology development. He avoided the ‘intellectual approach’ (what has become known as mechanical approach ever since Newtonian era or New Science) in favour of causal or essential approach (what Khan and Islam, 2016, called the ‘science of intangibles’). Table 6.2 shows that the 389 Table 6.2  Classification of the procedures use by Al-Razi in book of secrets. Type of procedure

Purpose

Count

Percent

Example

Primary

Produces a substance that transforms metals into gold or silver

175

45

Sublimation of mercury

Intermediate

Prepares materials required for primary procedures

127

33

Calcination of silver through burning

Reagent

Produces a chemical used in other procedures

51

13

Liquids that dissolve or create colours

Preparation

Instructions for a method used in other procedures

36

9

Mixing through pulverizing and roasting

389

100

Total

236  Sustainable Water Purification procedures by Al-Rāzī can be divided into four basic types: primary, intermediate, reagent, and preparation methods. The 175 “primary” procedures involve transformation of metals into gold or silver. It is worth noting here that bulk of Newton’s unpublished work also involved transformation of metals into gold (Zatzman and Islam, 2007). The 127 preparatory procedures involve softening and calcination. Today, equivalent processes are called denaturing, in which the natural features of materials are rendered artificial. Al-Rāzī then adds 51 procedures for reagent preparations. The reagents are solvents and tinctures, which usually contain trace amount of heavy metals. It is similar to what is used today except that Al-Rāzī used natural sources. Table 6.2 further shows 36 instructions for commonly needed processes such as mixing or dissolving. The procedure types include sublimation, calcination, softening whereas major sources are all natural (such as, quicksilver, sulfur, metals, stones). The calcination, sublimation and calcination themselves are also done through natural processes. The dominant theme was all source materials are derived from plants, animals and minerals and used in their natural state. The knowledge of seven alchemical procedures and techniques involved: sublimation and condensation of mercury, precipitation of sulphur, and arsenic calcination of minerals (gold, silver, copper, lead, and iron), salts, glass, talc, shells, and waxing. In addition, the source of heat was fire. Al-Rāzī gave methods and procedures of coloring a silver object to imitate gold (gold leafing) and the reverse technique of removing its color back to silver. Also described was gilding and silvering of other metals (alum, calcium salts, iron, copper, and tutty, all being processed in a furnace with real fire), as well as how colors will last for years without tarnishing or changing. Al-Rāzī classified naturally occurring earthly minerals into six divisions (Rashed, 1996): Four spirits (Al-Arwāh, the plural of the Arabic word Rūh, which is best described in the Qur’an as an order of Allah): 1. 2. 3. 4.

mercury sal ammoniac, NH4Cl sulfur arsenic sulphide (orpiment, As2S3 and realgar, As4S4 or AsS)

Even though this classification has been often referred to as ‘ghosts that roam around the earth’, this translation is ill-conceived and defies Qur’anic logic. Correct meaning is these materials are the source materials as in

Purification Techniques for Industrial Waste  237 essence. In our previous work, we have called it the ‘intangible’ (Zatzman and Islam, 2007; Khan and Islam, 2012; Islam et al., 2010; Islam et al., 2015). The above list is meaningful. Each of these materials bears some significance in terms of sustainability and human health. In today’s society, mercury is known to be a toxic material with adverse effects on the body and unanimously portrayed as a toxic chemical with long-term implication, it is one of those rare metals that had time-honoured applications even in the ancient society (Iqbal and Asmat, 2012). This unique heavy metal, which is less toxic in its elemental form than in its compound form, has enjoyed both industrial and medicinal applications throughout history (Wong, 2001).

6.3.1 Mercury From ancient times, the history of mercury has been connected with that of the medicine and chemistry (Block, 2001). Both sulphur and mercury are known to have been used in early civilizations in China, India and Egypt. Mercury has particular relevance to the history of science of both medicine and alchemy (Norn et al., 2008). Both sulphur and mercury have been used as disinfectants. In post Roman Catholic Church (RCC) Europe, mercury was first introduced by Muslim physicians and it was first mentioned in European literature in 1140 by Matthaeus Platearius, who recommended its use for treatment of syphilis as well as for treatment of wound and others (Block, 2001). On the medicinal side, mercury, in both its elemental and compound forms, has been used throughout history as a microbiocide (Weber and Rutala, 2001). However, ancient times had used only natural processes for extracting mercury. In this context, Figure 6.3 summarizes Beneficial Optimal Limiting

Harmful

Unnatural metals

Natural metals

Metal ion concentration

Figure 6.3  The usefulness of metal depends on its concentration as well as source (Figure adapted from Islam et al., 2016 and Weber and Rutala, 2001).

238  Sustainable Water Purification how metals act within human bodies. This figure is adapted from Islam et al. (2016), who used the bifurcation to demonstrate that natural chemicals act the opposite way from unnatural chemicals, and Weber and Rutala (2001), who did not distinguish between natural processing and unnatural processing, settling instead for ‘essential’ and ‘non-essential’ varieties. Islam et al. (2015) as well as Islam (2014) contended that every naturally occurring chemical is beneficial at some concentration, beyond which it becomes toxic (see the top graph in Figure 6.3) On the other hand, what is perceived as non-essential (as per Weber and Rutala, 2001, most heavy metals are non-essential although there is almost yearly discovery that these metals are also essential, albeit at a very small concentrations. The concept that unnatural metals, i.e., the ones processed through non-sustainable techniques is inherently toxic to the organism is new but it answers all the question regarding how toxicity functions within an organic body. As discussed by Islam and Khan (2018), the presence of artificially processed metal is akin to introducing a cancer cell that continues to wreck havoc to the organism. In ancient times, only the upper graph of Figure 6.3 existed because all processes were sustainable from both mass and energy perspectives (Khan and Islam, 2016). Today, it has become a common practice to lump chemicals that had been in use since the ancient time with those discovered in later era, for which there is no longer a natural processing technique available. For instance, many clinical studies have lumped cadmium, lead, mercury, thallium, bismuth, arsenic, antimony and tin in the same vein. Yet, cadmium was discovered in 1872 (just before the invention of electricity in 1979), thallium was discovered in 1861 whereas other metals were either used in their natural form (ore) or processed through natural means (e.g. open fire, natural additives). The first metal to be smelted in the ancient Middle East was probably copper (by 5000 BCE), followed by tin, lead, and silver. To achieve the high temperatures required for smelting, furnaces with forced-air draft were developed; for iron, temperatures even higher were required. Smelting thus represented a major technological achievement. Charcoal was the universal fuel until coke was introduced in 18th-century England (Islam et al., 2010). Many forms of mercury exist in nature, including elemental mercury, inorganic mercury, and organic mercury (Weber and Rutala, 2001). From ancient times onward, organic mercury* compounds have been used as antiseptics, antibacterials, fungicides and other disinfectants. These are * Organic mercury compounds, sometimes called organomercurials, are those containing covalent bonds between carbon and mercury. Examples are methylmercury, dimethylmercury and methylmercury chloride (methylmercuric chloride).

Purification Techniques for Industrial Waste  239 highly toxic beyond very low concentration. It means their optimal concentration (Figure 6.3) is quite low. Beyond the optimal concentration, organic mercury can produce toxicity through skin absorption, ingestion, or inhalation. They are also associated with gastrointestinal, renal, and neurologic toxicity. Thimerosal (merthiolate; 2(9-ethylmerucrio-thio) benzoic acid sodium salt has been widely used as a bactericide at concentrations of 0.001% to 0.1%. It has also been used as preservatives in pharmaceuticals and cosmetics, including in vaccines, eyedrops, contact lens cleaning and storage solutions, cosmetic creams, toothpaste, mouthwash, etc. (Van’t Veen and Joost, 1994). While this is widely recognized, few are aware of the fact that the chemicals that are used in modern industry are not chemicals that are naturally occurring, they are instead synthetic. Therefore, they are toxic even below the optimal concentration, meaning the lower graph of Figure 6.3 should be consulted. This same principle also applies to mercury vapour. For instance, today’s mercury vapor lamps use an arc through vaporized mercury in a high-pressure tube to create very waves (of various wavelengths) directly from its own arc. This is different from fluorescent lightbulbs, which use the mercury vapor arc to create a weaker light that mainly creates UV light to excite the phosphors. This usage is just one of many alterations of original usage of mercury. In Figure 6.4, relative output spectra of low- and medium pressure mercury arc lamps are shown. The ‘medium pressure’ refers to lamps for which

500 400 Relative Irradiance

300 200 100 0

E

D

C Medium B Pressure Lamp type

A

320 300 280 260 240 Wavelength 230 (nm) Low 200 Pressure

Figure 6.4  Relative output spectra of low- and medium pressure mercury arc lamps in the germicidal UV range. A=2 kW, 100 W/in; B=3.5 kW, 150 W/in; C=5 kW, 150 W/in; D= 6.4 kW, 150 W/in; E=7 kW, 200 W/in (from Blachley III and Peel, 2001).

240  Sustainable Water Purification the internal pressures are in the range of 2 to 5 bar and that operate at temperatures ranging from 700-900 C. The important aspect of the figure is the fact that UV output is a strong function of internal pressure of the lamp generate characteristic wavelengths of a broad spectrum. With conventional mass and energy balance treatment that disconnects the transition between mass and energy such dependence of relative irradiance on pressure cannot be quantified or predicted qualitatively. However, the technique (using the ‘galaxy’ model) proposed by Islam (2014) and later used by Khan and Islam (2016) makes it possible to account for alteration in the subatomic level to be coupled with tangible expression, such as light intensity. The next feature of this figure is the fact that different irradiance level of UV will kill different types of bacteria. Once again, such anti-bacterial effects can be described with the galaxy model that allows for different wavelengths to destroy different types of bacteria (based on their characteristic length).† Knowledge of cinnabar (HgS) is traced back to ancient Assyria and Egypt, but also to China (Wang, 2015). It had value for both medicinal and alchemy applications. In traditional Chinese medicine (TCM), cinnabar has been a high value medicinal component. Wang (2015) pointed out Shennong’s Classic of Materia Medica claims that cinnabar can treat practically all ailments involving the five yang organs‡, namely, heart, liver, spleen, lung and kidney. Cinnabar reportedly has calming and revitalizing effects, which help build one’s strength and improve vision, and kill “evil spirits”. The term “evil spirit” has been known to imply inexplicable ailments, including mental illness (Islam et al., 2017). There have been reports of improvement of lungs and hearts owing to ‘moistening actions’ of cinnabar while consumed orally or even applied externally. Most significantly, cinnabar was known to be a cure of convulsion and epilepsy, as well as fetal toxicity and pox virus. It was also considered to prevent malaria (Wang, 2015). One such compound is mercury sulphide (cinnabar), which is known ), Greek and Arabic (called zinjafar in ancient Chinese (called zhūshā, ) culture with universal use in medicine as well as general alchemy. Cinnabar has been used in traditional Chinese medicine as a sedative for more than 2000 years (Huanga et al., 2007). In addition to being used for insomnia, cinnabar is thought to be effective for cold sores, sore throat, and some skin infections. † ‡

For details of the galaxy model, see Islam (2014). On the yang side of the yin-yang are six organs, namely, gall bladder, stomach, small intestine, large intestine, bladder and triple burner.

Purification Techniques for Industrial Waste  241 Cinnabar is generally found in a massive, granular or earthy form and is bright scarlet to brick-red in color, has the highest refractive index of any mineral (King, 2002). It turns out that mercury compounds continued to be used in Europe during 15th through 20th century. In the era before synthetic antibiotics, sexually-transmitted diseases were of great concern. In search for a cure, various forms of mercury were tried. As such, mercury was the remedy of choice for syphilis in Protestant Europe. Paracelsus (1493-1541) formulated mercury as an ointment because he recognized the toxicity and risk of poisoning when administrating mercury as an elixir. Mercury was already being used in Western Europe to treat skin diseases. The dominating medical use of Hg, (in metallic form and as calomel, Hg2Cl2), in Sweden in the second half of the 19th century indicates that some persons were highly exposed to Hg, mainly for treatment of syphilis, and 0.3-1% of the population of 3.5-5 millions were treated for venereal diseases (10,000-50,000 patients). Sublimate (HgCl2 ) is in certain countries still used as an antiseptic for wounds. It was used in large quantities during the World Wars, triggered by the largely increased use of Hg in explosives. Sublimate was also used for preserving wood. In the 1830’s, dental restorative material, called ‘amalgam’ was introduced to the United States. This amalgam was developed in England and France and contained silver, tin, copper, zinc and mercury. The amalgam fillings were not openly embraced by organized dentistry in America, and in 1840, members of the American Society of Dental Surgeons were required to sign pledges not to use mercury fillings. By this time, the current methods of refining metals (including mercury) have been in place. Mercury and its compounds used in dental practice may be responsible for release of mercury into the oral cavity. Compounds of mercury tend to be much more toxic than the element itself, and organic compounds of mercury (e.g., dimethyl-mercury) are often extremely toxic and may be responsible in causing brain and liver damage. Recently, Wang et al. (2013) conducted an interesting study. They orally administered various doses of cinnabar for 10 consecutive days, then studied the mercury levels. They discovered that the mercury level in serum and tissues are significantly higher than that of vehicle control (Table 6.3). The serum mercury levels in the cinnabar groups were increased in a dose‐ dependent manner. However, the serum mercury content for the cinnabar group was only about 1/100 of that of the HgCl2 group at the same dose. The mercury levels in the brain tissue of the cinnabar group were raised slowly with the increasing dose and were about 1/19 of HgCl2 group at the same

Serum (ng/ml)

1.39 ± 0.05

401.94 ± 30.3

4.10 ± 0.47

14.63 ± 0.59

26.75 ± 6.98

75.30 ± 9.24

Group

Vehicle

HgCl2 0.01 g/kg

Cinnabar 0.01 g/kg

Cinnabar 0.05 g/kg

Cinnabar 0.1 g/kg

Cinnabar 1 g/kg

13.27 ± 2.22

12.20 ± 1.44

11.07 ± 2.10

10.63 ± 2.53*

190.25 ± 11.8

2.96 ± 1.24

Brain (ng/g)

89.47 ± 10.02

84.75 ± 9.47

32.73 ± 6.96

25.58 ± 5.97

5571.91 ± 1211

11.19 ± 4.31

Liver (ng/g)

Table 6.3  Mercury contents after cinnabar and HgCl2 administration for 10 days (From Wang et al., 2013).

455.88 ± 76.93

271.10 ± 49.25

82.69 ± 20.02

70.00 ± 18.02

23592.40 ± 446

14.24 ± 2.97

Kidney (ng/g)

242  Sustainable Water Purification

Serum (ng/ml)

1.52 ± 0.02

24.62 ± 1.55

27.44 ± 3.29

Group

Vehicle

Cinnabar 0.1 g/kg

HgS 0.1 g/kg

8.03 ± 1.98

12.12 ± 1.19

1.83 ± 0.49

Brain (ng/g)

41.39 ± 9.78

77.57 ± 10.17

5.71 ± 1.69

Liver (ng/g)

454.56 ± 70.68

206.21 ± 33.76

16.29 ± 1.19

Kidney (ng/g)

Table 6.4  Mercury contents after cinnabar and HgS administration for 10 days (From Wang et al., 2013).

Purification Techniques for Industrial Waste  243

244  Sustainable Water Purification dose. Similar to the pattern of the HgCl2 group, mercury accrued more in kidney than in liver. However, in the HgCl2 group, mercury accumulation was about 330 times higher than that of the cinnabar group. Meanwhile, there were no significant differences in the tissue distribution patterns between the cinnabar and pure HgS groups (Table 6.4) except that the pure HgS group accumulated mercury in the kidney ~2 times higher than that of the cinnabar group. This study indicates that cinnabar is remarkably different from HgCl2 in mercury absorption and tissue distribution. This finding is profound because up until recently synthetic chemicals were considered to be the same as natural chemicals (Khan and Islam, 2016). As will be discussed in latter chapters, this marks a bifurcation point in terms of natural chemicals following a different pathway from artificial chemicals.

6.3.2 Sal Ammoniac Sal ammoniac is a naturally occurring substance, mainly containing NH4Cl. It is the best known of the ammonium-bearing minerals. It forms in natural fumaroles, where gas vents from underground from volcanic activity. It also forms from the process of the burning of coal in coal deposits. The formation of Sal ammoniac is unique, as it is created from sublimation, meaning it crystallizes directly from gaseous fumes and bypasses a liquid phase. Sal ammoniac is highly soluble in water. It is known for its utility in many applications, ranging from fertilizer, to colouring agent to medical usage. Sal ammoniac (naturally occurring Ammonium Chloride) has reported to be first found in the wastelands of Central Asia, from which it was used by Muslim Alchemists of the medieval age, primarily for distillation of organic materials (Multhauf, 1965). In later centuries, there is evidence that Sal ammoniac was being produced through solar distillation of camel urine and other organic products, in proportion of five parts urine, one part common salt, and one-half part soot, which was also derived from natural products (Malthauf, 1965). Soot in general is a common source of heavy metals. Whenever soot is formed, they contain heavy metals that act as the nucleation site within the powdery soot. It is also reported that soot collected from the chimney of camel dung furnaces in Egypt contained natural ammonium chloride. This is expected as any herbivorous animal would have natural supply of salt in its diet. The concept of combining ammonia (then known as volatile alkali) and hydrochloric acid (then known as ‘spirit of salt’) was not invented until late 18th century (Malthauf, 1965). The now well-known synthesis process was:

Purification Techniques for Industrial Waste  245

NH3 + HCl

NH4Cl

(6.1)

This synthesis process was deemed to be cheaper than the ‘decomposition, which used decomposition of soot (including organic material), sulfuric acid and salt. By the mid-nineteenth century the synthetic process had superseded all others for the manufacture of sal ammoniac, and it was accomplished with utter simplicity through the addition of hydrochloric acid to the “ammonia liquor”, which was a residue from coal distillation. Later on, another process evolved. It involved double decomposition of ammonium sulfate and sodium chloride:

(NH4)2CO3 + CuSO4

CuCO3↓ + (NH4)2S04

(6.2)

(NH4)2S04+ 2NaCl

Na2SO4+ 2NH4C1

(6.3)

Ammonium carbonate refers to smelling salts, also known as ammonia inhalants, spirit of hartshorn or sal volatile. Today, this chemical is known as baker’s ammonia – the source of gaseous ammonia. It is also the form taken by ammonia when distilled from carbonaceous material without drying. Similarly, copper sulfate can be derived from naturally occurring blue vitriol, other sulfates, such as calcium sulfate (gypsum in its natural state). In Equation 6.2, the requirement is that an insoluble carbonate be formed, permitting the separation of the ammonium sulfate. The separation of the sal ammoniac in the second reaction was accomplished either by its sublimation or by differential crystallization. Even later, came the double decomposition of ammonium carbonate and magnesium chloride (bittern), following the reaction:

(NH4)2CO3 + MgCl2

MgCO3 + 2NH4Cl

(6.4)

This involved one step less than the preceding process and moreover utilized as a source of magnesium chloride the waste mother liquor, “bittern,” which is the waste of brine after production of common salt and is rich in magnesium chlorides, sulfates, bromides, iodides, and other chemicals present in the original sea water. This process was introduced commercially by the well-known hydrometer inventor, Antoine Baume, only a year after the establishment of the Gravenhorst factory, and we have a circumstantial account of his works written in 1776, while it was still in operation.

246  Sustainable Water Purification

6.3.3 Sulphur As per New Science, sulfur is the tenth most abundant element in the universe, has been known since ancient times. Table 6.5 shows abundance numbers for various elements in the universal scale. On earth, this scenario changes. Table 6.5 lists the most abundant elements found within the earth’s crust. Wexler (2014) points out that the use of sulphur has been popular since the ancient Greek period in production of chemical ‘weapon’. As early as 420 BC, toxic aerosol was created with natural pitch and sulphur powder. This tradition was continued by the Romans, who often added other natural chemicals to increase the deadly effect of the toxic cloud. Similarly, both ancient Chinese and Indian cultures used sulphur for warfare. They, however, added combustible chemicals, such as explosive saltpeter or nitrate salts, and/or a variety of plant, animal, or mineral poisons, such as arsenic and lead, in making smoke and fire bombs. In even the new world and in India, the seeds of toxic plants and hot peppers have been in use to rout attackers (Wexler, 2014). When it comes to using sulphur for material processing or medicinal needs, Muslim scientists of the medieval era are the pioneers (Islam et al., 2010). As pointed out by Norris (2006), the Sulfur–Mercury theory of metal composition by these scientists is paramount to understanding sustainable material processing. This theory is in the core of the so-called exhalation theory that includes continuous transition between solid and gaseous

Table 6.5  Abundance number for various elements present in the universe (from Heiserman, 1992 and Croswell, 1996). Element

Atomic number

Mass fraction, ppm

Abundance (relative to silicon)

Hydrogen

1

739,000

40,000

Helium

2

240,000

3,100

Oxygen

8

10,400

22

Neon

10

4,600

8.6

Nitrogen

7

960

6.6

Carbon

6

1,090

3.5

Silicon

14

650

1

Magnesium

12

580

0.91

Iron

26

10,900

0.6

Sulfur

16

440

0.38

Purification Techniques for Industrial Waste  247 phases. Norris (2006) identified the main strengths of the mineral exhalation theory as compositional flexibility and upward mobility: the mixing of protometallic vapours, which could vary compositionally and react with other mineral matter during their movement through subterranean regions, seemed sufficient for producing a plurality of metals and ores. The Muslim scientists considered metals to be of composite material. Among their most important conceptual advances in this field is the idea that metals, and many minerals, are composed of compositional principles likened to sulfur and mercury. In this theory, the Sulfur generally corresponds to the dry and solid qualities of a metal, while the Mercury provides the moisture and metallic character. It has been suggested that the Sulfur–Mercury theory may have been derived by generalising the process by which cinnabar congeals when sulfur and mercury are combined under appropriate conditions (Principe, 1998). These substances, often referred to as “sophic” or “philosophic” sulfur and mercury in later literature, were hypothetical materials qualitatively. This term is no longer in use. In the New Science era, the focus has been on tangible aspects and materials are characterized based on their tangible features, irrespective of the source of the material (Islam, 2014). Khan and Islam (2012) introduced the Avalanche theory that leaves room for counting all entities in a material. Islam (2014) extended that theory and introduced the galaxy theory that includes the entire history of the individual ‘particles’ within any material body. It was a restoration of original theory developed by Muslim scholars of the medieval era and a departure from the ‘science of tangibles’ that has dominated the New science, which emerged from sixteenth and seventeenth centuries. Another possible physical analogue would seem to be the process of smelting sulphide ores, with the consequent generation of sulfurous fumes and earthy dross, and a molten metal considered as a type of mercury. Avicenna (Ibn Sīnā) held a similar view as we know from his work that he considered metallic mercury being “solidified by sulfur vapour”. During his epoch materials were considered to be whole and the elemental consideration was unfathomable. The general theme was material is inherently a composition of various matters and cannot be reconstituted from ‘refined’ materials. The mercury-sulphur theory added to this context the notion that every component nature, irrespective of its physical or external appearance, pays a role in the nature of the final product (Norris, 2006). This principle also applies to Avicenna’s work that theorize the production of precious metals by combining base metals with various “solidifications” of mercury treated with one or more kinds of sulphur (Newman, 2014). Remarkably, none of the Muslim scholars of that era believed that a scheme outside of natural processes can be initiated, let alone sustained.

248  Sustainable Water Purification Newman (2014) points to another important point. That is material processing and refining were routine except that at no time artificial or synthetic material was used. These processes may appear to be crude or unsanitary in today’s standard, but they were nevertheless wholly organic. For instance, he mentions about the use of vinegar, and sour milk, and goats’ whey, and water of chickpeas and boys’ urine during boiling and sublimation. Avicenna was known to recognize water as the mother material whereas earth materials were today’s equivalent of catalysts. For instance, quicksilver is considered to be composed of a watery moisture united with a subtle earth. Avicenna had described this inherent earth within mercury as being “sulphurous.” As discussed in previous sections, this characterization amounts to the intangible designation, the term ‘intangible’ covering trace elements as well as vapour phase. When this principle is applied to say, heating cinnabar in a current of air and condensing the vapour, the following equation emerges in conventional sense. The equation for this extraction is



HgS + O2 + Hg + SO2 + Σ

(6.5)

In this equation, Σ contains information regarding intangibles (called ‘sulphurous’ by Avicenna) In true scientific form, this equation should be written as

Cinnabar + air + natural additives ---------- Natural Healing

quicksilver + Σ (6.6)

In this format, any process can be described with its sustainability considerations intact. It also implicitly recognizes the role of water as the mother substance (ubiquitous), thus “humidity” being an intrinsic property of matter. This process was the hallmark of Medieval Muslim scientists, such as Avicenna and and Al-Rāzī. For instance, Al-Rāzī’s Kitāb al-Asrār is filled with similar recipes for refining a host of mineral products ranging from sal ammoniac and orpiment to boraxes and alkalis (Newman, 2014). Islam (2014) recognized this process as the tangible-intangible yin-yang – a form that was later used by Islam et al. (2018) to formulate a new characterization technique for crude oil. Norris (2006) saw it as mercury and sulphur combination, thought to be equivalent to water-oil version for minerals. In later centuries, the theory of double unctuosity§ was introduced in order recognize the existence of intrinsic contents within bulk material. §

‘Intangible’ would be the closest meaning of this word.

Purification Techniques for Industrial Waste  249 Unlike Muslim scientists, none of these scientists recognized the existence of water as the mother material, whose concentration cannot be reduced to nil irrespective of the refining process carried out. Nevertheless, European scientists went ahead and used the concept of a double humidity, one of which is flammable, with a common reference to distillation of ethanol from wine. The logic here is: just as wine contains a highly volatile, combustible material that can be distilled off (ethanol), and a less volatile component that is not combustible, so too does the metallic intangible, sulphur. These scientists saw normal sulphur as having a burning unctuosity that blackens and burns metals when it is fused and dropped on them. For this reason, Albert adds, alchemists Eventually, this principle would lead to modern refining techniques with the addition of synthetic chemicals as the catalysts (one type of intangibles or unctuous material). For quicksilver, they accepted Avicenna’s claim that it contains a liquid component along with a ‘subtle earth’. However, Avicenna described the ‘subtle, unctuous, humidity’ as ‘water’, whereas European scientists envisioned the ‘moist’ component as mercury. Furthermore, the likes of Albertus Magnus have introduced three forms of intangibles, rather than two. The Wyckoff (1967) translation offers the following quote: We know, therefore, that the ability of metals to be burnt is [due to] the Sulphur, and not to the Quicksilver by itself. Furthermore, we also know that in anything that contains very unctuous moisture mixed with earthiness, the moisture is of three kinds. One of these is extremely airy and fiery, adhering to the surface, as a consequence of the [upward] motion of those elements [Fire and Air], so that they always rise to the surface of things in which they are mixed and combined. The second, close beneath this, contains more wateriness floating about among the parts of the thing. The third has its moisture firmly rooted and immersed in the parts and bounded in the combination; and therefore this is the only one that is not easily separated from the combination, unless the thing is totally destroyed. And therefore this must be the nature of Sulphur (p. 197-198).

Here we can see that Albertus Magnus has divided the extrinsic moisture into two types while retaining the unitary character of the third, intrinsic humidity. His goal in making this new bifurcation probably lay in the desire to have both a flammable and a non-flammable type of unfixed humidity. Thus, the first extrinsic moisture is fiery and airy, hence combustible, while the second is not, being composed of “wateriness” (Newman, 2014). Whatever the intention of Albertus was, this point about distinguishing ‘fiery’ element from others is of profound implication. In later

250  Sustainable Water Purification Being Tangible

Intangible Passive

Quantity

Active Quality

Figure 6.5  Scientific pathway of a chemical reaction Modified from Kalbarczyk (2018).

centuries, this formed the basis of considering energy as a form, discrete from mass, thereby creating opacity in maintaining natural energy sources. The original form of the mass energy transformation theory of Avicenna is depicted in Figure 6.5. This figure shows how any matter will have tangible and intangible components, the intangible component being the driver for so-called chemical reactions. For instance, the intangible component will include energy source as well as the presence of trace elements, including catalysts. Just like components of energy source are not traceable, components of catalysts are considered to be insignificant in determining final mass of various reaction products. New Science, in essence, focuses on the tangibles and adds the effect of intangibles through tangible expressions. For instance, heating is evaluated through the temperature and catalysts are measured by the mere presence and for both cases no determination is made as to how the pathway changes in presence of two sources of temperature (or catalytic reaction) that are different while have the same external expression (for instance, temperature or mass of catalyst). Another important aspect of Islamic scholars was the recognition of water as the mother and ubiquitous phase. Islam (2014) recognized this observation and reconstituted the material balance equations to develop new characterization of materials as well as energy. Tichy et al. (2017) discussed an interesting aspect of water content and sustainability. They studied the role of humidity on the behavior of insects. Optimal functionality is a direct function of humidity optimization within an organic body. This optimization is necessary for metabolic activities, as well as overall survival abilities. From an evolutionary perspective, this need of optimum humidity can explain the existence of hygroreceptors very likely. Interestingly, these hygroreceptors are associated in antagonistic pairs of a moist and a dry cell in the same sensillum with a thermoreceptive cold cell. Although the mechanism by which humidity stimulates the moist and dry cells is little known, it is clear that the duality that Avicenna envisioned persists in all levels of natural functions.

Purification Techniques for Industrial Waste  251 Also of significance is the fact that the moist cell and the dry cell appear to be bimodal in that their responses to humidity strongly depend on temperature. Either modality can be changed independently of the other, but both are related in some way to the amount of moisture in the air and to its influence upon evaporation (Tichy et al., 2017). This scientific model was altered by subsequent European scholars, who recognized the natural refining process through the ‘theory of three humidities’ (Newman, 2014).

6.3.4 Arsenic Sulphide Arsenic sulphide, in its natural form has been in use for longest time. Similar to any other natural products, Arsenic trisulfide had a wide range of industrial use, including tanning agent, often with with indigo dye. Orpiment is found in volcanic environments, often together with other arsenic sulfides, mainly realgar (“ruby sulphur” or “ruby of arsenic”). Similar to mercury, this naturally occurring chemical was used throughout history as a potent poison or a medicine (Frith, 2013). Arsenic was used in traditional Chinese as well as Indian medicine. In addition, it was popular as a cosmetic product in eye shadow in the Roman era. In traditional Chinese medicine, preparations can be obtained in the form of coated or uncoated pills, powder or syrups. Different studies have shown that the majority of traditional Chinese medicines, such as Chinese herbal balls, show high doses of as varying between 0.1 and 36.6 mg per tablet, causing patients to get intoxicated by the high As dose and Indian ayurvedic herbal medicine products are also known to cause lead, mercury and As intoxication. Avicenna recommended arsenic with the gum of pine for asthma. He also prescribed arsenic in honey water, for a wide range of remedies, including for herpes esthiomenos of the nose (Aegineta, 1847). Avicenna discussed the use of white, red, and yellow arsenic, all being used in their natural state. It was much later that ‘refined’ arsenic emerged. For instance, arsenic was known as early as the fourth century B.C., when Aristotle referred to one of its sulfides as “sandarach,” or red lead (now known as As4S4). It was only in 1250 that Albertus Magnus, a German philosopher and alchemist that isolated the element. Of course, the word arsenic comes from the Persian word “zarnikh,” which means “yellow orpiment,” which the Greeks adopted as “arsenikon”. This is commonly denominated as Arsenic trisulfide (As2S3), although natural state contains other chemicals that are in perfect balance with the molecular form. Of course, the more common form is crystalline oxides, As2O3 (white arsenic). The most common form, however, is the Arsenopyrite (FeAsS), an iron arsenic sulfide, also called mispickel.

252  Sustainable Water Purification Nowadays, the therapeutic use of As is making a comeback in modern medicine. Arsenic-trioxide, for instance, is used in treating patients with relapsed acute promyelocytic leukemia (APL). However, the notion of natural state of arsenic being different from synthetic one’s is absent. Long before being hailed as “the arsenic that saved” in early 20th century (Vahidnia et al., 2007), Muslim scholars considered Arsenic sulphide as a chemical of crucial pharmaceutical value. The word arsenic is derived from the Persian zarnikh and Syriac zarniqa, later incorporated into ancient Greek as arsenikon, which meant “masculine” or “potent” and referred primarily to orpiment, or yellow arsenic. The word became arsenicum in Latin and arsenic in old French, from which the current English term is derived (Vahidnia et al., 2007). In post-Renaissance Europe, the use of arsenic as a poisoning agent became common. Its application in getting rid of wealthy people became so popular that by the 17th century France, white arsenic became known as poudre de succession, the ‘inheritance powder’ (Vahidnia et al., 2007). In the 19th century, the same tactic was used to commit insurance fraud. During that era, one of the most infamous case was that of Goeie Mie (‘Good Mary’) of Leiden, The Netherlands, who poisoned at least 102 friends and relatives between 1867 and 1884, distributing arsenic-trioxide (ATO) in hot milk to her victims after opening life insurance policies in their names. Of the 102 people poisoned, 45 persons became seriously ill, often with neurological symptoms and 27 persons died; 16 of whom were her own relatives (De Wolff and Edelbroek, 1994). Research during that period led to the development of post-mortem detection of poison, followed by decrease in incidents of poisoning with arsenic. During the 19th century, European women applied arsenic powder to whiten their faces as well as to their hair and scalp to destroy vermin. It was also thought that arsenic consumption by women gave “beauty and freshness” to the skin. For the first time in Europe, medicinal applications of arsenic are found in late 18th century, when various chronic disorders were being treated with arsenic (Bentley and Chasteen, 2002). Arsenic continued to be used in cosmetics well into the early twentieth century and this was a common source of accidental poisoning. When arsenic is heated, it oxidizes and releases an odor similar to that of garlic. Striking various arsenic-containing minerals with a hammer might also release the characteristic odor. At ordinary pressure, arsenic, like carbon dioxide, does not melt but sublimes directly into vapor. Liquid arsenic only forms under high pressure. Curiously, alchemists gave emphasis on characterizing material in terms of mercury and arsenic. Mercury, lead and arsenic are effective mitotic

Purification Techniques for Industrial Waste  253 poisons (turbagens) at particular concentrations, due to their known affinity for thiol groups and induce various types of spindle disturbances. New Science classifies these clastogenic effects to be S-dependent. The availability of cations affects the number of aberrations produced quantitatively. Plants, following lower exposure, regain normalcy on being allowed to recover (Patra et al., 2004). However, as usual New Science does not distinguish between natural arsenic and processed arsenic, thereby obscuring any usefulness of the research findings. Historically, New Scientists¶ have focused on medicinal effects of arsenic when it comes to finding any positive aspect of arsenic. Citations of medicinal applications range from Ancient China to Ancient Greece through Ancient India (Doyle, 2009). Hippocrates (469–377 BC) recommended arseniko as a tonic whilst Dioscorides (c. 54–68AD) recommended it for asthma. A Greek surgeon‐herbalist working in Nero’s army, he made extensive observations on asthma, including the use of realgar mixed with resin, inhaled as a smoke for the relief of cough or taken as a potion for asthma. The Roman Pliny secundus (23ade extensive observations and Nero (37–68 AD) using it to kill Britanicus in 55AD. Egyptologists claim that ancient Egyptians used arsenic to harden copper at least 3000 years ago. This was confirmed by Islam et al. (2010), who reviewed ancient technologies and found them to be totally sustainable because they used no artificial mass or energy source. They also discussed the fact that such chemicals were added in the embalming fluid during processing of mummies. Of course, the Medieval Islamic golden era saw numerous applications through alchemy. However, the role of arsenic in material processing has drawn little attention from New Scientists. In Europe, during the New Science era, the use of arsenic is synonymous with processed derivatives of arsenic, rather than naturally occurring version. Graeme and Pollack (1998) described how artificial processing of arsenic can render both mercury and arsenic into toxic agents. They pointed out that Greeks and Romans continued to use natural arsenic throughout the Medieval era for various medical purposes. Even during the 1800s, arsenic remained in use for medical purposes in treating leukemia, psoriasis, and asthma. Of interest is the fact that the Fowler’s solution was not withdrawn from the US market until the 1950s. Meanwhile, Erlich and Bertheim produced nearly 1000 compounds of arsenic to be used in the treatment of syphilis; the use of such compounds ¶

This term is applied to Newton and scientists of the post-Newtonian era that are believers of New Science, which is premised on the ‘infallibility’ of Newtonian description of mass and energy.

254  Sustainable Water Purification was not curtailed until after the advent of penicillin in 1943. The arsenic-containing drug melarsoprol (Mel B) is still the drug of choice for treating African trypanosomiasis at the meningoencephalitic stage 1, 2, 3, 4. Note that commercial use of electricity began in 1870s. Although it is unknown among New scientists, the use of electricity for thermal alteration renders a process unsustainable. In the meantime, while natural penicillin was discovered in 1928 by Alexander Fleming, Professor of Bacteriology at St. Mary’s Hospital in London, mass production was possible only after synthetic version of penicillin was created. This transformation from natural penicillin to Benzylpenicillin (C16H18N2O4S) first took place in 1942 (Fischer and Ganellin, 2006). This transition from natural to artificial is symbolic of what has happened in sustainability considerations, natural being sustainable while artificial (or synthetic) being unsustainable. Arsenic may occur in an inorganic or an organic form. The inorganic arsenic compounds include the arsenites, the arsenates, and elemental arsenic. The organic arsenic compounds include arsine and its organic derivatives. In modern era, synthetic or inorganic arsenic has been the only one used for commercial applications. In all these applications, arsenic is never in its natural form and all the byproducts are inherently toxic to the environment. For instance, arsenic is a byproduct of the smelting process for many metal ores such as, cobalt, gold, lead, nickel, and zinc. The natural form of arsenic was used in ancient and medieval era for similar applications. It seems even in modern Europe as late as 19th century arsenic was used in paints and dyes for clothes, paper, and wallpaper (Meharg 2003). Even then, arsenic for the production of green pigments following the synthesis in the late eighteenth century of copper arsenite was in its toxic form. These pigments were widely used in wallpapers. In damp rooms, fungi living on the wallpaper paste turned the arsenic salts into highly toxic trimethylarsine. Arsenic pigments were responsible for untold numbers of cases of chronic illness and many deaths (Meharg, 2003). The source of both organic and inorganic arsenicals are naturally occurring minerals, such as, arsenopyrite (FeAsS), realgar (As4S4) and orpiment (As2S3). As these erode, they react with moisture and oxygen to form arsenites and arsenates that are water soluble and consequently end up in both surface and groundwater. Some of these chemical forms and oxidation states cause acute and chronic adverse health effects, including cancer (Hughes, 2002). The metabolism involves reduction to a trivalent state and oxidative methylation to a pentavalent state. The trivalent arsenicals, including those methylated, have more potent toxic properties than the pentavalent arsenicals. The exact mechanism of the action of arsenic is

Purification Techniques for Industrial Waste  255 not known, but several hypotheses have been proposed. What is missing in this analysis is the role of artificial chemicals. At a biochemical level, inorganic arsenic in the pentavalent state may replace phosphate in several reactions. In the trivalent state, inorganic and organic (methylated) arsenic may react with critical thiols in proteins and inhibit their activity. However, this ‘organic’ in New Science doesn not mean that an artificial state has been avoided. As such, potential mechanisms include genotoxi­ city, altered DNA methylation, oxidative stress, altered cell proliferation, co-carcinogenesis, and tumor promotion cannot be tracked to artificial chemicals. A better understanding of the mechanism(s) of action of arsenic will make a more confident determination of the risks associated with exposure to this chemical. In surface waters, these chemicals can be absorbed by algae that then convert them to arsenosugars, arsinolipids and arsenobetaine. In surface waters, these can be absorbed by algae that then convert them to arsenosugars, arsinolipids and arsenobetaine. Fish and other forms of marine life feed on these algae and concentrate the arsenic compounds. When the same arsenic compounds are absorbed by plants, similar but less complex reactions take place and further dilution occurs when they are passed on to grains. Figure 6.6 shows the pathway followed by the original naturally occurring ore, containing arsenic. Most arsenic in the terrestrial environment is found in rocks and soils. Arsenic in surface and ground water is mostly a mixture of arsenite and arsenate. Although New Science designates various components in molecular form, in reality molecules are

Bio concentration

arsenosugar, arsinolipids, arsenobetaine

O–

As

O–

Surface water

O– Naturally occurring ore

Air Moisture

(Absorbed by algae) Arsenites and Arsenates

arsenopyrite (FeAsS), realgar (As4S4), orpiment (As2S3)

Groud water

O– –O

As

O–

O–

Figure 6.6  Pathway followed by arsenic chemicals.

Filtration

256  Sustainable Water Purification fictitious and never exist in isolation. During the pre-New Science era chemical equations were not written in molecular or atomic form, hence the words, such as ‘air’ (instead of Oxygen), ‘moisture’ (instead of H2O) and chosen. This figure shows that in order for arsenic to travel natural pathway, the entire chain of air and moisture has to be free of synthetic chemicals. In the post-industrial revolution, major sources of arsenic include the combustion of coal, nonferrous metal smelting, and the burning of agricultural wastes. These are inherently toxic to the environment. Similarly, each chemical containing arsenic that has been widely used as herbicides, fungicides, wood preservatives, desiccants, cattle and sheep dips, and dyestuffs is necessarily synthetic or artificially processed. Today, arsenic continues to be widely used in agriculture, in glass and ceramics, as a metal alloy, and in semiconductors and other electronic devices – all causing irreparable harm to the environment. It is no surprise that the entire branch of toxicology deals with only artificial type of arsenic products (Hughes, 2002).

6.3.5 Refining Techniques In terms of processing of petroleum crude, Al-Rāzī’s work is likely the oldest complete reference available today. In his Kitāb al-Asār, Al-Rāzī described two methods for the production of kerosene, termed naft abyad (white

Picture 6.1  The refining technique used by the Alchemists.

Purification Techniques for Industrial Waste  257 petroleum), using an apparatus called an alembic. Picture 2.1 shows this device. The complete distilling apparatus consists of three parts (Bearman et al., 2012): 1. the “cucurbit” (Arabic, qar‘; Greek, βίκος, bikos), the still pot containing the liquid to be distilled 2. The “head” or “cap” (Arabic, al-anbīq; from Greek ἄμβιξ, ambix, meaning `cup, beaker`) fits over the mouth of the cucurbit to receive the vapors, 3. A downward-sloping “tube” (Greek σωλήν, sōlēn), leading to the “receiver” (Arabic, kābīlā, Greek ἄγγος, angos, or φιάλη, phialē) container. This set up is often reduced to one retort, used for distillation. This setup, however, uses open fire and the material used in different parts is entirely sustainable, it has no artificial material in it. The original process was used to prepare rose water. Picture 6.1 shows a schematic of the original distillation system. One method used clay as an absorbent, whereas the other method used ammonium chloride (sal ammoniac). The distillation process was repeated until most of the volatile hydrocarbon fractions had been removed and the final product was perfectly clear and safe to burn. It is not clear from the literature what was the most used source for producing kerosene, but the word naft implies a petroleum source. However, it is conceivable similar technique was used to refine olive oil, which would in fact produce gases that are beneficial to human health (Islam et al., 2010). During the same period, kerosene was also produced during the same period from oil shale and bitumen by heating the rock to extract the oil, which was then distilled. Similarly, Avicenna wrote volumes on plants and their uses. His instruction manual also contained refining processes. His improvement of the cooling system within the distillation apparatus is most noteworthy (Waines, 2010). Today, such distillation processes are all be eliminated. Perhaps the closest to retaining the original sustainable refining technologies is the perfume industry, for which extracting essential oils from plants is the biggest technological challenge. The advantage of distillation is that the volatile components can be distilled at temperatures lower than the boiling points of their individual constituents and are easily separated from the condensed water. For the perfume industry, the use of water is desirable as water is the most ubiquitous material and does not alter the original aroma. Such fascination for water is absent in the chemical industry, particularly the ones dealing with petroleum fluids. In fact, in considering petroleum waste disposal, water is considered to be an undesirable by-product of the

258  Sustainable Water Purification petroleum operation that need to be removed in order to ensure proper functioning of the refining process. Similarly, the process of expression, also referred to as cold pressing, is popular in the perfume industry. Numerous essential oils are routinely extracted through cold pressing. In particular, citrus essential oils, such as tangerine, lemon, bergamot, sweet orange, and lime employ the process of expression. In older times, expression was done in the form of sponge pressing. The zest or rind of the citrus would first be soaked in warm water to make the rind more receptive to the pressing process. A sponge would then be used to press the rind, thus breaking the essential oil cavities, and absorb the essential oil. Once the sponge was filled with the extraction, it would then be pressed over a collecting container, and there it would stand to allow for the separation of the essential oil and water/juice. The essential oil would finally be siphoned off. Centuries ago, less labor-intensive processes have been employed. One such process, termed the Écuelle à piquer, involves a prodding, pricking, sticking action to release the essential oil. During this process, the rind of the fruit is placed in a container having spikes that will puncture the peel while the device is rotated. The puncturing of the rind will release the essential oil that is then collected in a small area below the container. While it is not commonly understood, the material used in those puncturing spikes would affect both the quality of the essential oil and the sustainability of the process (Khan and Islam, 2016). Today, the majority of modern expression techniques are accomplished by using machines using centrifugal force. The spinning in a centrifuge separates the majority of essential oil from the fruit juice.

6.4 The Energy/Water Crisis The energy crisis was scientifically fomented through the advancement of so-called Peak Oil theory that became the driver of many other theories with great impact on economic polices. Peak oil is one of the concept that promotes the notion that global oil reserve is limited and at some point will start to run out, leading to sharp rise in oil price (Speight and Islam, 2016). These fears are based on premises that are not scientific.

6.4.1 Are Natural Resources Finite and Human Needs Infinite? In economics, the notion of there being infinite need and finite resources is a fundamental premise that is asserted with dogmatic fervor in

Purification Techniques for Industrial Waste  259 contemporary economics. In the context of petroleum resources, this notion has to help foment fear that is actually the driver of contemporary economics. This model starts off with the premise that needs must grow continually in order for the economy to thrive. Then, it implies, without looking at the validity of that premise, that there has to be an endless supply of energy to feed it. Because such endless supply contradicts the other premise that natural sources are finite, there arises an inherent contradiction. One such article is written by Mason (2017), who poses this wrong-headed question: “But what happens to that equation when the net amount of energy we extract from the earth is shrinking? How, then, does an economy grow exponentially forever if the one element it needs more than anything to flourish is contracting with time?”

Then, he primes the audience with the need of a paradigm shift, that would involve challenging all orthodoxies involving the economy, as if to propose a revolution. Next, he creates a prophet out of a neuroscientist, Chris Martenson, who in recent years has turned his attention to the economy, particularly as it relates to dwindling energy resources and growing debt. Note how the premise of ‘dwindling energy resources’ is imbedded in this ‘revolutionary’ concept. How revolutionary is it? He writes: “He also got rid of most any equity stocks and put his money in gold and silver. He has been labelled a prophet of doom and a survivalist, by some. But more recently, his views have been receiving wider and more serious attention. He has been to Canada to talk to oil and gas investors, of all people. That’s incongruous given his view that we’re pillaging the Earth of its energy resources in the most inefficient and wasteful ways possible.”

Intuitively, it sounds simple – if I use up a certain amount of a finite quantity each year, it will eventually run out. But that tells you that you cannot have constant or increasing resource extraction from a finite resource, it does not tell you anything about what you do with the resources you extract, how productive they are, or whether or not they enable continued economic growth. It is certainly possible to sustain exponential growth infinitely with finite resources, as long as the usage is confined to sustainable or zero-waste operations. Similarly, all solutions end up proposing to minimize waste and maximize profit – an economic euphemism for Utilitarianism that has been preaching ‘maximizing pleasure and minimizing pain’ at a personal level.

260  Sustainable Water Purification There has always been plenty of discussion in economics discourse about manipulating the interest rate, but never about eliminating it. There are plenty of suggestions regarding how to minimize waste, but one never proposes a solution to achieve zero-waste. There are even talks about continuously increasing productivity, but never talk about the fundamental assumption of infinite need and finite resource. The notion of ‘The Infinite’ has intrigued humanity for a long time. In ancient civilizations, infinity was not a ‘large number’. It was something external to creation. In other words, only a Creator was considered to be infinite, along with many other traits that could not be part of Creation. However, this ‘infinity’ has nothing to do with the unbounded-ness of nature that has no boundary. Even though the ancient Greeks had a similar concept of infinitude, post-Aquinas Europe developed an entirely different take on infinitude, one highlighted recently by Khan and Islam (2016). In a study published nearly 2 decades ago, Lawrence Lerner, Professor Emeritus in Physics and Astronomy at the University of Chicago, was asked to evaluate how Darwin’s theory of evolution was being taught in each state of the United States (Lerner 2000). In addition to his attempt to find a standard in K-12 teaching, Lerner made some startling revelations. His recommendations created controversy, with many suggesting he was promoting “bad science” in name of “good science.” However, no one singled out another aspect of his finding. He observed that “some Native American tribes consider that their ancestors have lived in the traditional tribal territories forever.” He then equated “forever” with “infinity” and continued his comment stating, “Just as the fundamentalist creationists underestimate the age of the earth by a factor of a million or so, the Black Muslims overestimate by a thousand-fold and the Indians are off by a factor of infinity” (Lerner 2005). This confusion between “forever” and “infinity” is not new in modern European culture. In the words of Albert Einstein, “There are two things that are infinite, human stupidity and the Universe, and I am not so sure about the Universe.” Even though the word “infinity” emerges from a Latin word, infinitas, meaning “unbounded-ness,” for centuries this word has been applied in situations in which it promotes absurd concepts. In Arabic, the equivalent word (la nihāyah) means “never-ending.” In Sanskrit, similar words exist (Aseem, meaning ‘no end’) and those words are never used in mathematical terms as a number. This use of infinity to enumerate something (e.g., infinite number of solutions) is considered to be absurd in other cultures. Nature is infinite – in the sense of being all-encompassing – within a closed system that nevertheless lacks any boundaries. Somewhat

Purification Techniques for Industrial Waste  261 paradoxically, nature as a system is closed in the sense of being self-closing. This self-closure property has two aspects. First, everything in a natural environment is used. Absent anthropogenic interventions, conditions of net waste or net surplus would not persist for any meaningful period of time. Secondly, nature’s closed system operates without benefit of, or dependence upon, any internal or external boundaries. Because of this infinite dimension, we may deem nature – considered in net terms as a system overall – to be perfectly balanced. Of course, within any arbitrarily selected finite time period, any part of a natural system may appear out of balance. However, to look at nature’s system without acknowledging all the subtle dependencies that operate at any given moment introduces a bias that distorts any conclusion that is asserted on the basis of such a narrow approach. Figure 6.7 shows how the population in more developed countries reached a plateau while that of less-developed countries continued to grow, albeit with a slowed rate. In terms global energy need, this figure presents an interesting divide. In average, the energy consumption per capita of the ‘less-developed countries’ is an order of magnitude less than that of ‘more-developed countries’. In mathematical terms, it means the world has a capacity of sustaining energy needs of the majority of the population even if the population is increased 10-fold. In practical terms, it means that if we could contain the per capita energy consumption, we would have no worries about natural population growth. Indeed, the energy consumption of the ‘more developed countries’ has been contained. In last 20 years, the most populous ‘developed country’, the USA has shown practically 10 9 8 7 6 5 4 3

Less-developed countries

2 1 0 1950

More-developed countries 1970

1990

2010

2030

2050

Figure 6.7  There are different trends in population growth depending on the state of the economy.

262  Sustainable Water Purification constant per capita energy consumption. The USA is an important case as this country personifies global trend in terms of energy consumption. Historically, the USA has set standards for all aspects of technology development and other tangible aspects of civilization for a duration that has been synonymous with petroleum golden era – i.e., whatever it does today is emulated by the rest of the world in years to come. Table 6.6 shows per capita energy consumption (in tons of oil equivalent per year) of the USA in the last few decades, along with predictions for 2015. In this, Canada represents an interesting case. Canada follows the USA’s trend closely in matters of per capita energy consumption but falls far behind in matters of population growth, expenditure in research and development (particularly in energy and environment), expenditure in defense and pharmaceutical industries, and other long-term economic stimuli. Japan, on the other hand represents other extremity of the energy consciousness spectrum. As can be seen in Table 6.6, Japan maintains steady per capita energy consumption at almost half the value of that of Canada. At the same time, Japan has maintained very high relative investment in education and research and development. However, Japan’s population has been dropping, or keeping pace with Europe and unlike the USA. Canada’s population growth has been a mix of Europe/Japan (decline) and USA (mild growth). The difficulty involved in maintaining a balance Table 6.6  Per capita energy consumption (in TOE) for certain countries (From Islam et al., 2018). Countries

1990

1995

2000

2005

2010

2015

USA

7.7

7.8

8.2

7.9

7.3

7.3

Canada

7.5

7.9

8.1

8.4

7.6

7.6

Japan

3.6

4.0

4.1

4.1

3.7

3.9

Germany

4.4

4.1

4.1

4.1

4.0

3.8

Russia

5.9

4.3

4.2

4.5

4.8

5.5

Saudi Arabia

3.9

4.8

5.1

6.0

6.6

7.7

China

0.8

0.9

0.9

1.3

1.8

2.2

India

0.4

0.4

0.5

0.5

0.6

0.7

Indonesia

0.6

0.7

0.7

0.8

0.9

1.2

Sri Lanka

0.3

0.3

0.4

0.5

0.5

0.6

Purification Techniques for Industrial Waste  263 between urbanization and per capita energy consumption is most sternly manifested in the case of Saudi Arabia. Both Germany and Russia show mild per capita energy consumption, signaling prudent usage of energy sources and high energy efficiency. Saudi Arabia is a ‘developing country’ in all measures except that it is projected to be the most energy-consuming country in the world by 2015. In as early as 1995, it exceeded the per capita energy consumption of Russia and Germany and is slated to exceed that of USA by 2015. Saudi Arabia represents the global trend by ‘developing countries’ to emulate the wasteful habits of the USA while shunning positive aspects of USA in the areas of economic growth, education or research and development. This trend of Saudi Arabia is alarming and is a trademark of global obsession with wasteful energy habits. Saudi Arabia is just an example of this obsession that is all pervasive in the developing countries as can be seen in Figure 6.7. Figure 6.8 shows the growth in per capita energy consumption for some key countries that are not characterized as ‘more developed countries’. These countries all had very modest per capita energy needs in 1990. However, they all show exponential growth in energy needs in the last two decades. China leads the pack with the highest growth in energy needs. It nearly triples the energy need in 25 years. This trend shows that China could have dealt with its ‘population crisis’ by keeping the per capita energy consumption in check. This would have avoided many shortcomings of the one-child policy that China has imposed on its population for decades. Similar growth is shown by Indonesia – another country that

2.2

per capita energy, TOE

2.1 1.9

China

1.7 1.5 Indonesia

1.3 1.1 0.9

India

0.7 0.5 0.3 1990

Sri Lanka 1995

2000

2005

2010

Figure 6.8  Per capita energy consumption growth for certain countries.

2015

264  Sustainable Water Purification attempted to decrease its population rather while increasing per capita energy needs. Over the two decades, Indonesia has doubled its per capita energy consumption. India has shown restraints in per capita energy consumption. While this is the case, its per capita energy consumption has doubled during the decades of concern. Sri Lanka has been the lowest energy consuming country (from the list of countries) but still maintains growth very similar to India and Indonesia. It has been recognized for some time that there is a strong correlation between per capita energy need and GNP (as well as GDP). Over the last 30 years, the average consumption of the global ‘South’ has been nearly an order-of-magnitude less than that of the ‘West’ (Goldemberg et al., 1985; Khan and Islam, 2012). As the West has been trying to boost its population and contain its per capita energy consumption, while increasing its GNP, the ‘south’ has been trying to contain its population while increasing the per capita energy consumption as well as GNP. These contradictory measures have created confusions in both the west and the ‘south’. This is most visible in the definition of GNP and GDP that reward an economy for increasing wasteful habits (e.g. per capita energy consumption). This contradiction has been discussed by Khan and Islam (2007), who introduced new techniques for measuring economic growth that could take account of true sustainability. They showed that true sustainability would increase GNP by increasing efficiency (rather than increasing per capita energy consumption). Figure 6.9 shows how energy consumption has become synonymous with the concept of societal welfare, as expressed as tangible expression of the ‘quality of life.’ Goldenberg et al. (1985) correlated per capita energy

Tangible index 100 80 60 40 20 0

0

0.5 1.0 1.5 2.0 2.5 Energy consumption per-capita (kW)

Figure 6.9  A strong correlation between a tangible index and per capita energy consumption has been at the core of economic development (from Goldenberg, 1985).

Purification Techniques for Industrial Waste  265 consumption with a Physical Quality of Life Index (PQLI), which is an attempt to measure the quality of life or well-being of a country. The value is the average of three statistical data sets: basic literacy rate, infant mortality, and life expectancy at age one, all equally weighted on a 0 to 100 scale. It was developed for the Overseas Development Council in the mid-1970s by Morris David Morris, as one of a number of measures created due to dissatisfaction with the use of GNP as an indicator of development. PQLI is best described as the measure of tangible features of the society, not unlike GDP (Khan and Islam, 2007). Ever since, numerous other indices have been proposed, including more recently developed Happiness index, but they all suffer from similar short-comings, i.e., focus on tangibles, as outlined by Khan and Islam (2012 and Zatzman, 2012, 2013). The following steps are used to calculate Physical Quality of Life: 1) Find the percentage of the population that is literate (literacy rate). 2) Find the infant mortality rate (out of 1000 births). INDEXED Infant Mortality Rate = (166 - infant mortality) × 0.625 3) Find the Life Expectancy. INDEXED Life Expectancy = (Life expectancy - 42) × 2.7 4) Physical Quality of Life = (Literacy Rate + INDEXED Infant Mortality Rate + INDEXED Life Expectancy)/3. This trend goes back to the earliest times of the Industrial Revolution more than two-and-a-half centuries ago. Khan and Islam (2012) discussed the mindset that promoted such wasteful habits in all disciplines. Figure 6.10 summarizes the dilemma. At the dawn of the industrial age, Per capita energy consumption of developed countries Population Per capita energy consumption of developing countries

TIME SINCE INDUSTRIAL REVOLUTION

Figure 6.10  While population growth has been tagged as the source of economic crisis, wasteful habits have been promoted in name of emulating the west.

266  Sustainable Water Purification civilization began to be defined by consumption and wasteful habits. As the population grew, the energy consumption per capita should have been decreased in order compensate for the increasing energy demand. This would be in line with the claim that industrialization had increased human efficiency. The opposite happened in the developed countries. For centuries, the per capita energy consumption increased, along with dependence on mechanization. It only stabilized in 1990s. By then, the population growth in the west has been arrested and have been declining in most part (the exception being USA). This population and energy paradox was further accentuated by encouraging the developing countries to emulate the west in wasteful habits. In every country, consumption per capita increased with time as a direct result of colonialism and imposed culture that is obsessed with externals and short-term gains. As a result, a very sharp increase in per capita energy consumption took place in the developing countries. As can be seen from Table 6.6, even with such increase, the “south” has not caught up with the “west”, with the exception of some petroleum-rich countries. A major case in point here is China. For the last two decades, it attempted to curtail its population growth with a one-child per family law. The current Chinese government at the behest of the latest congress of the Communist 1.4

2.0

1.3

1.8

1.2

1.6 Population growth

1.1

1.4 Per capita energy

1

1.2

0.9

1.0

0.8

0.8

0.7 0.6 1961

1965

1970

1975

1980

1985

1990

1995

2000

2005

Figure 6.11  Population and energy paradox for China (From Speight and Islam, 2016).

Purification Techniques for Industrial Waste  267 Party of China has now repudiated this policy as practically unenforceable. Furthermore and even more interesting, however is that Figure 6.11 shows that the population growth has in fact been dwarfed by the increase in per capita energy consumption. A similar conclusion emerges from the comparable statistical profile for the Indian subcontinent, where infanticide and female-selective abortion is in order to boost male population in favor of female population that is considered to be a drain to the economy. This finding is meaningful considering India and China hold one third of the world population and can effectively change the global energy outlook either in favor or against sustainability. In order to change the above trend, and address the population and energy paradox, several indices have been introduced. These indices measure happiness in holistic terms. Comparing one person’s level of happiness to another’s is problematic, given how, by its very nature, reported happiness is subjective. Comparing happiness across cultures is even more complicated. Researchers in the field of “happiness economics” have been exploring possible methods of measuring happiness both individually and across cultures and have found that cross-sections of large data samples across nations and time demonstrate “patterns” in the determinants of happiness. The New Economics Foundation was the first one to introduce the term “Happiness index” in mid 2000’s (Khan and Islam, 2007; White, 2007). In first ever ranking, Bangladesh, one of the poorest nations of the time was found to be the happiest among some 150 countries surveyed. At that time, Bangladesh was among the lowest GDP countries along with very low per capita energy consumption. This study demonstrated that happiness is in fact inversely proportional to per capita energy consumption or GDP. Before, this study would set any trend globally in terms of energy policies, a number of similar happiness indices were introduced in succession, all showing a direct, albeit broad, correlation between GDP and happiness. One such index is the Happy Planet Index (HPI) that ranks 151 countries across the globe on the basis of how many long, happy and sustainable lives they provide for the people that live in them per unit of environmental output. It represents the efficiency with which countries convert the earth’s finite resources into well being experienced by their citizens. The Global HPI incorporates three separate indicators: a) ecological footprint: the amount of land needed to provide for all their resource requirements plus the amount of vegetated land needed to absorb all their CO2 emissions and the CO2 emissions embodied in the products they consume;

268  Sustainable Water Purification b) life satisfaction: health as well as “subjective well-being” components, such as a sense of individual vitality, opportunities to undertake meaningful, engaging activities, inner resources that help one cope when things go wrong, close relationships with friends and family, and belonging to a wider community; c) life expectancy: included is the child death, but not death at birth or abortions. The first item couples CO2 emission levels with the carbon footprint measure. This emission relates only to fossil fuel usage, and does not take in account the fact that CO2 that is emitted from refined oil is inherently tainted with catalysts that are added during the refining process. This creates bias against fossil fuels and obscures the possibility of finding any remedy to the energy crisis. The Organization for Economic Co-operation and Development (OECD) introduced the Better Life Index. It includes 11 topics that the OECD has identified as essential to wellbeing in terms of material living conditions (housing, income, jobs) and the quality of life (community, education, environment, governance, health, life satisfaction, safety and work-life balance). It then allows users to interact with the findings and rate the topics against each other to construct different rankings of wellbeing depending on which topic is weighted more heavily. For the purpose of this analysis, what matters is the Life Satisfaction survey. Life satisfaction is a measure of how people evaluate the entirety of their life and not simply their feelings at the time of the survey. The OECD study asks people to rate their own life satisfaction on a scale of 0 to 10. The ranking covers the organization’s 34 member countries plus Brazil and Russia. The Happy Planet Index ranked Costa Rica as the happiest country in 2012. The particularly high score relates to high life expectancy and overall wellbeing. Vietnam and Colombia follow in second and third place. Of the top ten countries, nine are from Latin America and the Caribbean. Countries from Africa and the Middle East dominate the bottom of the ranking instead. Botswana is last after Bahrain, Mali, the Central African Republic, Qatar and Chad. Developed nations such as the United States and the European Union member countries tend to score high on life expectancy, medium-to-high in wellbeing, but rather low on their ecological footprint, which puts them in the ranking’s second-tier.

Purification Techniques for Industrial Waste  269

6.4.2 The Finite/Infinite Conundrum The next assumption introduced in energy management is that oil (or fossil fuel) reserve is finite. The theory first assumes the ultimate recoverable reserve, then expresses cumulative oil production as a function of the ultimate recoverable reserve. Cavallo (2004) defines the Hubbert curve used to predict the U.S. peak as the derivative of:



Q(t ) =

Qmax 1 + ae −bt

(6.7)

Where Q(t) is the cumulative oil production and Qmax is the maximum producible reserve and a and b are constants. The year of maximum annual production (peak) then back is calculated as:



1 t max = ln(a) b

(6.8)

The fixation of Qmax is in the core of the Hubbert curve. Theoretically, the recoverable reserve increases for two reasons: 1) the boundary of resource; 2) the technology. As discussed in earlier sections, the boundary of resource is continuously moving. The recent surge in unconventional oil and gas reserve makes an excellent point to this regard. In fact, the following section makes the argument that this boundary is fictitious and for a sustainable recovery scheme, this boundary should not exist. The second reason for the reserve to grow is the technology that becomes applicable to a broader resource base. There is a general misconception that Hubbert was concerned with “easy” oil, “easy” metals, and so forth that could be recovered without greatly advanced mining efforts and how to time the necessity of such resource acquisition advancements or substitutions by knowing an “easy” resource’s probable peak. The difficulty of Hubbert curve is not its assumption that easy oil recovery is constant, it is rather the notion that a resource that turns into reserve with time is finite. As shown in previous sections, accessing greater resource bases is not a matter of ‘more difficult’ technology, it is rather a matter of producing with sustainable techniques.

270  Sustainable Water Purification

6.5 Certain Sustainable Technologies 6.5.1 Direct Use of Solar Energy Much has been talked about solar energy but all involving creation of solar panels, then storage of electricity through a series of very toxic devices, which make the process extremely environment hostile and utterly inefficient (See Chhetri and Islam, 2008 for detailed analysis). The same solar energy has tremendous potential if used directly. Islam (2020) discussed the use of solar-assisted steam injection projects in some of the most demanding enhanced oil recovery schemes. With renewed focus on environmental impacts, companies are turning to solar energy, especially in places, where the sunlight is plentiful. For any solar high-temperature system, a solar contractor is necessary. Such collector will have much higher efficiency than conversion to electricity if used directly. Figure 6.12 shows a widely used steam power plant, which transforms heat energy to electrical energy. The solar collector efficiency indicates the fraction of solar energy that can be transferred to the thermal fluid in the receiver. The parabolic solar collector efficiency varies much on the fluid temperature. Eck et al. (2005) reported that the collector efficiency shows higher at low temperature ranges (Figure 6.13).

Heat Loss Flue Gas S t a c k

Fuel

Transmission line

Q

Q

Transformer

Q Steam Generator Turbine

Cooled Water

Fire

Oxygen

Pump Furnace Water

Figure 6.12  Typical steam power plant.

Q

Cooling Tower

Warm Water Q

Purification Techniques for Industrial Waste  271 80

Collector Efficiency [%]

70 60 DNI = 1000 W/m2 DNI = 800 W/m2 DNI = 600 W/m2 DNI = 400 W/m2

50 40 30 20

0

50

100 150 200 250 300 350 400 450 500 T – Ta [K]

Figure 6.13  Collector efficiency at different direct normal irradiance (DNI) as a function of fluid temperatures above the ambient temperatures (Redrawn from Eck et al., 2005).

At low fluid temperatures, the thermal loss is minimal, as shown in Figure 6.14. From the figure, it is found that at a fluid temperature of 100°C (78 C above ambient temperature), the efficiency of solar collector is 75%. The solar transmission efficiency is dependent on the heat transfer loss from the thermal fluid to the fluid in the generator and the bubble pump. An efficient system will have more than 90% efficiency of transmission. Heat Receiver

Tracking Mechanism

Concentractor Reflective Surface

Figure 6.14  The thermal loss of the collector with respect to fluid temperature above the above the ambient temperature (Redrawn from Odeh et al., 1998).

272  Sustainable Water Purification If the efficiency of the solar system is calculated from the solar energy on the parabolic surface to the heat transfers to the heating fluid, the overall efficiency will be:



Overall energy transfer efficiency = Collector efficiency (75%) × Transmission efficiency (90%).



Overall energy transfer efficiency = 67.5 %



(6.9)

It can be speculated that the extraction process of energy from different processes do not differ much. So the consideration of a solar system is beneficial as it has other benefits as discussed earlier. There are some existing efficient methods to concentrate the dispersed solar energy and transfer to the desired places. The most common method is the use of a parabolic trough (Figure 6.15) for the concentration of solar energy to obtain high temperatures without any serious degradations in the collector’s efficiency (Bakos et al., 2001; Geyer et al., 2002; and You et al., 2002). The parabolic trough collector consists of large curved mirror, which can concentrate the sunlight by a factor of 80 or more to a focal line depending upon the surface area of the trough. In the focal line of these is a metal absorber tube, which is usually embedded into an evacuated glass tube that reduces heat losses (Figure 6.16). A special high-temperature, resistive selective coating additionally reduces radiation heat losses. California power plants, known as solar electric generating systems have a total installed capacity of 354 MW (Kalogirou et al., 1997). These systems use thermo-oil as a heat transfer fluid, which can reach up to 400 C (Herrmann et al., 2004). The parabolic collector effectively produces heat at a temperature between 50°C and 400°C (Kalogirou, 2004).

Thermal loss W/m2

100 80 60 40 20 0

0 100 200 300 Fuel temperature above ambient temperature °C

Figure 6.15  Parabolic trough.

Purification Techniques for Industrial Waste  273 Convection loss Residual gas conduction loss Evacuated space

Radiation loss Glass tube Working fluid

Optical loss

Bream radiation

Absorber tube Reflector

Figure 6.16  Cross section of collector assembly (Redrawn from Odeh et al., 1998).

Khan and Islam (2016) reported the use of a parabolic trough has been constructed that is adjustable and moves along the direction of the sun so that maximum solar energy can be achieved anytime of the day (Figure 6.17). Each parabolic trough has a surface area of 4 m2 (2.25 m × 1.8 m) that can radiate almost 1.6 kW to 4 kW to the absorber, depending on the direct normal irradiance, which is again dependent on the geographical area. Taking 600 w/m2 as DNI (direct normal irradiance) and considering the energy transfer efficiency from solar surface to the heating point, it is found that one surface (4 m2) can supply 1.62 kW. A heating load of 10.47 kW will require 7 such parabolic collectors, which can supply necessary energy to run a refrigerator or an air cooler having a one ton cooling

Figure 6.17  Constructed parabolic trough.

274  Sustainable Water Purification

Nickel platting on copper metal surface Black painted aluminium surface incorporating outlet copper tube Inlet copper tube Outlet copper tube Ply wood surface

Solar pump

Oil storage tank

Steel frame supporting solar contractor

Figure 6.18  Experimental solar trough (from Khan and Islam, 2016).

load. The number of collectors will vary from place to place, depending on the DNI of any place and the climate of that place. The experimental data show that the parabolic collector can absorb 0.80  kW during early summer in a cold country when the environmental temperature is nearly 21 C. The thermal fluid used by Khan and Islam (2016) was vegetable oil. It is circulated by the solar pump and that is why no electricity is needed (Figure 6.18). The choice of waste vegetable oil itself is another step toward achieving true sustainability.

6.5.2 Effective Separation of Solid from Liquid Organic waste products such as, cattle manure, slaughter house waste, vegetable waste, fruit peels and pits, dried leaves and natural fibers, wood ash, natural rocks (limestone, zeolite, siltstone, etc.) are all viable options for the separation of fines and oil. In 1999, a patent was issued to Titanium Corporation for separation of oil from sand tailings (Allcock et al., 1999). However, this technique uses chemical systems, such as NaOH and H2O2, which are both expensive and environmentally hostile. Drilling wastes have been found to be beneficial in highway construction (Wasiuddin et al., 2002). Studies have shown that the tailings from oil sands are high in various mineral contents. To extract the minerals, usually the chemical treatment is used to modify the surface of minerals. Treatment with a solution derived from natural material has a great potential. Also, microwave

Purification Techniques for Industrial Waste  275 heating has the potential to enhance selective floatability of different particles. This aspect has been studied by Gunal and Islam (2000). Temperature can be a major factor in the reaction kinetics of a biological solvent with mineral surfaces. Various metals respond in a different manner under microwave condition, which can make significant change in floatability. The recovery process can be completed through transferring the microwave-treated fines to a flotation chamber (Henda et al., 2005). Application of bio membranes to separate solid from liquid has also given considerable attention recently (Kota, 2012). Even though, synthetic membranes are being used for some application, they are highly energy intensive to produce, toxic and costly.

6.5.3 Effective Separation of Liquid from Liquid The current practice involves separation of oil and water and the water is disposed as long as it has a hydrocarbon concentration below an allowable limit. However, it is expected that such practice cannot be sustained and further purification of water is necessary. Consequently, this task involves on both separation of oil and water and heavy metals removal from the water. The oil-water emulsion has been produced and it was found that the selected paper fibre material gives 98-99% recovery of oil without producing any water (Khan and Islam, 2006). An emulsion made up of varying ratios of oil and water was utilized in different sets of experiments. Almost all the oil-water ratios gave the same separation efficiency with the material used. The mentioned paper material, which is made of long fibrous wood pulp treated with water proofing material as filtering medium. Water proofing agent for paper used in these experiments is “Rosin Soap” (rosin solution treated with caustic soda). This soap is then treated with alum to keep the pH of the solution within a range of 4~5. Cellulose present in the paper reacts reversibly with rosin soap in presence of alum and forms chemical coating around the fibrous structure and acts as coating to prevent water to seep through it. This coating allows long chain oil molecules to pass making the paper a good conductor for oil stream. Because of the reversible reaction, it was also observed the performance of filter medium increases with the increased acidity of the emulsion and vice versa. As well, the filter medium is durable to make its continuous use for a long time keeping the cost of replacement and production cut-down. The material used as filtering medium is environmental friendly and useful for downhole conditions. Further, other paper-equivalent alternate materials, which are inexpensive and down-hole environment appealing, can be used for

276  Sustainable Water Purification oil-water separation. Human hair has been proven to be effective in separation of oil and water as well as heavy metal removal. Similarly, natural zeolites can also effectively function to separate liquidliquid from different solutions. Such zeolites can adsorb some liquid leaving others to separate depending on their molecular weight.

6.5.4 Agricultural Waste for Water Purification and Value Addition In modern era, agricultural waste peels have been seen as an ecological burden for the society. Ancient cultures valued any agricultural waste for other applications. Recently, waste peels, as lignocellulosic biomass-rich materials, have stimulated new gateways for the production of renewable, low cost and sustainable adsorbents for water treatment applications. Bhatnagar et al. (2015) reviewed the work conducted by various researchers over the last few decades on the use of various agricultural waste peels as adsorbents for the water and wastewater treatment. In this review, adsorption capacities for organic and inorganic pollutants by different peel-based adsorbents were summarized. Wherever applicable, different modification methods, which have been employed to develop modified peel-based adsorbents, have also been presented to highlight and discuss the key advancements on the preparation of novel adsorbents using agricultural waste peels. Adsorption mechanisms responsible for pollutants removal by peel-based adsorbents have also been discussed. In past few years, numerous approaches have been studied for the development of cheaper and more effective adsorbents containing natural biopolymers. These biopolymers represent an interesting and attractive alternative as adsorbents because of their particular structure, physicochemical characteristics, chemical stability, high reactivity and excellent selectivity toward aromatic compounds and metals, resulting from the presence of chemical reactive groups (hydroxyl, acetamido or amino functions) in polymer chains. Various bio-based/biopolymer materials have been examined for the removal of diverse type of pollutants from water. Agricultural by-products usually are composed of lignin and cellulose as major constituents and may also include other polar functional groups of lignin, which include alcohols, aldehydes, ketones, carboxylic, phenolic, and ether groups. These groups have ability to bind aquatic pollutants through different binding mechanisms. Among several agricultural wastes that have been studied as biosorbents for water treatment, “waste peels” from fruits and vegetables are of great importance since most of the peels are discarded as waste and find no application anywhere, which sometimes

Purification Techniques for Industrial Waste  277 pose serious disposal problems. Following is discussion on various fruit peels, considered to be waste.

6.5.4.1 Orange Peel The adsorption capacity of orange peels was found to be 7.75 (Pb2+), 6.02 (Ni2+), 5.25 (Zn2+). Table 6.7 Shows the composition of orange peels.

6.5.4.2 Pomelo Peel Pomelo has more peel and segment membrane than most other citrus fruits, generating a significant quantity of pomelo waste. Pomelo peel as biosorbent using the zinc chloride activating method was used in laboratory to Table 6.7  Chemical composition of orange peel adsorbent by X-ray fluorescence analysis. Characteristics

Values

CaO

1.42%

K2O

0.18%

SO3

0.14%

MgO

0.12%

Fe2O3

0.11%

SiO2

0.08%

P2O5

0.05%

BaO

0.02%

SrO

0.01%

Al2O3

0.01%

NiO

0.01%

WO3

Not detected

ZnO

Not detected

Mn

Not detected

Organic matter

97.83%

278  Sustainable Water Purification test its capability of removing Pb2+ from wastewater (Liu et al., 2012). The optimal conditions for the adsorption were found to be: 5.3–6.5 initial pH of the wastewater, 1.5 h of exposure duration, 10 g/L.

6.5.4.3 Grapefruit Peel Grapefruit is cultivated in all tropical and subtropical regions of the world, with approximately 4 million metric tons annual production. Thus, a lot of grapefruit peel (GFP) is available throughout the world. GFP contains several water soluble and insoluble monomers and polymers. The water soluble fraction contains glucose, fructose, sucrose and some xylose, while pectin, cellulose, hemicellulose and lignin constitute between 50% and 70% of the insoluble fraction. These polymers are rich in carboxyl and hydroxyl functional groups, which may bind pollutants in aqueous solution (Saeed et al., 2010).

6.5.4.4 Lemon Peel Lemon is of agronomic importance because the lemons are consumed as an ingredient in cooking, as garnish, and as juice in lemonade, carbonated beverages, and other drinks. To make better use of this cheap and abundant agricultural waste, lemon peel after juice extraction, can be utilized as an inexpensive adsorbent for aquatic pollutants. The adsorption potential of lemon peel was examined as an adsorbent for the removal of two anionic dyes, Methyl orange (MO) and Congo red (CR) from aqueous solutions (Bhatnagar et al., 2009). The adsorption capacities of lemon peel adsorbent for dyes were found to be 50.3 and 34.5 mg/g for MO and CR, respectively. Batch adsorption studies were conducted to remove cutting oil from wastewater using activated lemon peels (Tembhurkar and Deshpande, 2012). The effect of various important parameters, namely, pH, dose of adsorbent, contact time, mixing speed, and initial oil concentration, and their optimum conditions for maximum sorption efficiency were studied and results indicated that adsorbent dosage of 5 g/L, contact time of 70 min, mixing rate of 45–50 revolutions/min, and pH of 2 provided maximum oil removal efficiency. The feasibility of lemon peel waste was studied for the removal of cobalt ions from aqueous solutions (Bhatnagar et al., 2010). The maximum adsorption capacity of lemon peel adsorbent for cobalt removal was ca. 22 mg/g. Adsorption of Azure A dye in aqueous solution on commercial activated carbon (CAC) and indigenously prepared activated carbon from orange peel (OPC) and lemon peel (LPC) carbon have been studied (Meenakshisundaram et al., 2009).

Purification Techniques for Industrial Waste  279 Extent of dye removal increased with decrease in the initial concentration of the dye and particle size of the adsorbent and also increased with increase in contact time, amount of absorbent used and the initial pH of the solution. The biomass Citrus limetta fruit peels was examined for its potential for Pb2+ ions (Suryavanshi and Shukla, 2010).

6.5.4.5 Banana Peel Banana, Musa spp, is a worldwide consumed tropical fruit and comprises several varieties. Banana peel is the main residue, corresponding to 30–40% (w/w), and has been mainly used in composting, animal feeding, and the production of proteins, ethanol, methane, pectin, and enzymes. Cellulose, hemicellulose, pectin, chlorophyll, and other low molecular weight species are its main constituents. The banana peel presents a high adsorption capacity for metals and organic compounds, and this aspect is primarily due to the presence of the hydroxyl and carboxyl groups of the pectin. The adsorption of lead(II) and cadmium(II) on peels of banana has been studied in batch mode (Anwar et al., 2010). Maximum adsorption capacity of banana peels from Langmuir isotherm indicated that 1 g of banana peels can adsorb 5.71 mg of cadmium and 2.18 mg of lead. Untreated banana peels (UTBPs), alkali-hydrolyzed banana peels (AlBPs), acid-hydrolyzed banana peels (AcBPs), and bleached banana peels (BBPs) were used as adsorbents separately for the removal of Cr(VI) and Mn(II) from aqueous solution during batch experiments (Ali and Saeed, 2014). The maximum removal capacities for Cr(VI) were: UTBP (45%), AlBP (87%), AcBP, (67%) and BBP (40%). While for Mn(II), the maximum removal capacities of theses adsorbents were: UTBP (51%), AlBP (90%), AcBP (74%) and BBP (67%) at optimum conditions. The maximum removal of Cr(VI) and Mn(II) was obtained at initial concentration of 3 mg/L, adsorbent dose of 4 g/L, pH 6, and contact time of 60 min. It was noted that the metal ions removal capacity of these adsorbents was AlBP > AcBP > UTBP > BBP, which indicated that chemical treatment of banana peels enhanced the biosorption of metal ions. The adsorption of metals (Cu2+, Zn2+, Co2+, Ni2+, Pb2+) from synthetic solutions using the acid-, alkali-, and water-treated banana peels was investigated by Annadurai et al. (2003). The adsorption capacity was found to be 7.97 (Pb2+), 6.88 (Ni2+), 5.80 (Zn2+), 4.75 (Cu2+), and 2.55 mg/g (Co2+) using banana peel. Chemical and physical properties of banana peel are shown in Table 6.8. The banana peel showed a high adsorption capacity of phenolic compounds (689 mg/g). The adsorption process was very fast, and it reached equilibrium in 3 h of contact time. The equilibrium solid-phase concentration of phenols decreased with

280  Sustainable Water Purification Table 6.8  Chemical and physical properties of banana peel used in the experiments. (From Bhatnagar et al., 2015). Parameters

Data

Moisture content (%)

13.55

Volatile matter (%)

86.44

Ash (%)

3.85

C content (%)

31.79

O content (%)

42.87

K content (%)

14.86

Na content (%)

1.33

Si content (%)

1.48

Al content (%)

1.05

Cl content (%)

3.22

pH

6.60

increasing adsorbent (banana peel) concentration was mainly attributed to the unsaturation of the adsorption sites through the adsorption process. Desorption experiments showed chemisorptive interactions between the natural phenolic and the adsorption sites on the banana peel.

6.5.4.6 Cassava Peel Cassava is known as one of the most important agricultural commodities in many countries (e.g., Indonesia, Nigeria etc.). Cassava is used as raw material for the production of cassava starches and traditional foods and cakes. Its leaves can be utilized as vegetables or natural medicine since it contains high amounts of protein and other bioactive compounds, and its wood is often used as firewood for cooking. Cassava starch processing produces a large amount of solid wastes (cassava peels), and direct discharge of these solid wastes causes environmental problems. Utilization of cassava peels as precursor for activated carbon with a high surface area has been demonstrated by various researchers. Activated carbons were prepared from waste cassava peel by employing physical and chemical methods and their efficiency was tested in the removal of dyes and metal ions from aqueous

Purification Techniques for Industrial Waste  281 solution (Rajeshwarisivaraj et al., 2009). Both adsorbents were found efficient for dyes and metal ions, however, the material impregnated with H3PO4 showed higher efficiency than the heat treated materials. Sorption of arsenic from aqueous solution was carried out using polyvinyl pyrrolidone (PVP) K25 coated cassava peel carbon (PVPCC). In batch studies, the adsorption was dependent on initial As(V) concentration and adsorbent dosage. The adsorption was higher in batch mode when compared to the column mode studies. The IR studies confirmed the presence of PVP K25 and As(V) on the adsorbent. The XRD studies revealed that the nature of adsorbent was amorphous before and after the As(V) adsorption process.

6.5.4.7 Jackfruit Peel Jackfruit (Artocarpus heterophyllus L.) is specie of tree of the mulberry family (Moraceae) and is widely grown in Thailand, Indonesia, Myanmar, India, Philippines and Malaysia. Jackfruits usually reach 10–25 kg in weight at maturity however, the large sized jackfruits, sometimes, weight as much as 50 kg. Jackfruit peel wastes have no economic value and in fact often create a serious problem of disposal for local environments. Thus, utilizing jackfruit peel as a low-cost adsorbent would increase its economic value, will help to reduce the cost of waste disposal, besides this, the problem of environmental pollution also can be reduced considerably. Treatment of jackfruit peel with sulfuric acid produced a carbonaceous product (JPC) which was used to study its efficiency as an adsorbent for the removal of Cd(II) from aqueous solution (Inbaraj and Sulochana, 2004). Physical and chemical characteristics of JPC are summarized in Table 6.9.

6.5.4.8 Pomegranate Peel Punica granatum L. (Punicaceae), commonly called pomegranate, is one of the most popular fruits in the world due to its pleasant taste, high nutritional value, and many medical features. Pomegranate fruits are widely consumed fresh and in processed forms as juice, jams and wine. The pomegranate peel, a by-product from juice industry, constitutes 5% to 15% of its total weight. Pomegranate peel is composed of several constituents, including polyphenols, ellagic tannis and gallic and ellagic acids. Pomegranate peel is discarded as waste residue that can be used as a low cost and renewable source of biosorbent. Removal of lead(II) and copper(II) from aqueous solutions was studied using pomegranate peel (raw), activated carbon prepared from pomegranate peel (AC1) and activated carbon prepared from chemically treated pomegranate peel (AC2 and AC3) (El-Ashtoukhy et al., 2008).

282  Sustainable Water Purification Table 6.9  Physico-chemical characteristics of JPC. (From Bhatnagar et al., 2015). Parameters

Data

pH

7.24

Moisture content (%)

16.27

Bulk density (g/ml)

0.72

Ash content (%)

4.99

Water soluble matter (%)

1.32

Acid soluble matter (%)

9.30

Decolourising power, mg/g

46.50

Ion exchange capacity, meq./g

0.93

Surface area, m2/g

123.17

Iron content (%)

0.07

Ash analysis (%) SiO2

16.0

Na2O

4.03

K2O

0.72

MgO

33.8

CaO

16.6

6.5.4.9 Garlic Peel Garlic peel, an agricultural and easily available waste, could be an alternative for wastewater treatment processes. Due to the high consumption of garlic, massive amounts of peels are disposed, causing a severe problem in the community. The viability of garlic peel (GP) to remove Pb2+, Cu2+, and Ni2+ was evaluated. The results showed that the adsorption process could attain equilibrium within 20 min. GP had remarkable higher adsorption affinity for Pb2+ than Cu2+ and Ni2+ with the maximum adsorption capacity of 209 mg/g. The adsorption efficiency and uptake capacity of one metal ion were reduced by the presence of the other metal ion. The adsorption mechanism was supposed to be ion exchange between Ca2+ of GP with heavy metal ions

Purification Techniques for Industrial Waste  283 in the solution. Native garlic peel and mercerized garlic peel as adsorbents for the removal of Pb2+ has been studied. For determination of major components of native garlic peel and mercerized garlic peel, the elemental analysis was carried out, and the results are shown in Table 6.10. The adsorption capacity of garlic peel after mercerization was increased 2.1 times and up to 109.05 mg/g. FT-IR and scanning electron microscopy (SEM) results indicated that mercerized garlic peel offered more little pores acted as adsorption sites than native garlic peel and had lower polymerization and crystalline and more accessible functional hydroxyl groups, which resulted in higher adsorption capacity than native garlic peel. The FT-IR and X-ray photoelectron spectroscopy analyses of both garlic peels before and after loading with Pb2+ further illustrated that lead was adsorbed on the peels through chelation between Pb2+ and O atom that existed on the surface of garlic peels. The potential of garlic peel (GP) was also evaluated to remove methylene blue (MB) from aqueous solution in a batch process. Tables 6.11 through 6.13 show information about selected adsorbents.

6.5.5 A Novel Desalination Technique Desalination is a technique that has been used throughout history for production of sea salt. However, the use of desalination to produce drinking water is relatively new (Oren, 2008). Most of the techniques involved in this process are expensive and none of them is sustainable. Khan and Islam (2016) reported a novel desalination technique that can be characterized as totally environment-friendly process. This process uses no non-organic chemical (e.g. membrane, additives). This process relies on the following chemical reactions in four stages:

(1)saline water + CO2 + NH3 (2) precipitates (valuable chemicals) + desalinated water (3) plant growth in solar aquarium (4) further desalination Table 6.10  The percentages of main elements in garlic peels by element analysis. (From Bhatnagar et al., 2015). Material

C (%)

N (%)

O (%)

H (%)

S (%)

Native garlic peel

37.01

1.04

47.71

4.22

0.81

Mercerized garlic peel

36.01

1.47

48.79

4.11

1.02

284  Sustainable Water Purification Table 6.11  Uptake capacities of various peel-based adsorbents for metals removal. (From Bhatnagar et al., 2015). Peel/adsorbent type

Metal

Amount adsorbed

Citric acid modified orange peel

Cd(II)

0.90 mol/kg

Chemically modified orange peel

Cu(II)

289.0 mg/g

Mercapto-acetic acid modified orange peel

Cu(II)

70.67 mg/g

Mercapto-acetic acid modified orange peel

Cd(II)

136.05 mg/g

Mg2+ type orange peel adsorbent

Cu(II)

40.37 mg/g

K+ type orange peel adsorbent

Cu(II)

59.77 mg/g

KCl modified orange peel

Cd(II)

125.63 mg/g

KCl modified orange peel

Pb(II)

141.84 mg/g

KCl modified orange peel

Zn(II)

45.29 mg/g

KCl modified orange peel

Ni(II)

49.14 mg/g

Sulfured orange peel

Pb(II)

164 mg/g

Sulfured orange peel

Zn(II)

80 mg/g

Orange peel

As(III)

1.18 mg/g

Pomelo peel

Cu(II)

19.7 mg/g

Depectinated pomelo peel

Cu(II)

21.1 mg/g

ZnCl2 activated grapefruit peel

Pb(II)

12.73 mg/g

Grapefruit peel

Uranium(VI)

140.79 mg/g

Grapefruit peel

Uranium(VI)

104.1 mg/g

Banana peel

Cd(II)

5.71 mg/g

Banana peel

Pb(II)

2.18 mg/g

Activated carbon from cassava peels

Cu(II)

8.00 mg/g

Activated carbon from cassava peels

Pb(II)

5.80 mg/g

Pomegranate peel

Ni(II)

52 mg/g

Pomegranate peel carbon

Fe(II)

18.52 mg/g (Continued)

Purification Techniques for Industrial Waste  285 Tables 6.11  Uptake capacities of various peel-based adsorbents for metals removal. (From Bhatnagar et al., 2015). (Continued) Peel/adsorbent type

Metal

Amount adsorbed

Mercerized garlic peel

Pb(II)

109.05 mg/g

Egyptian mandarin peel (raw)

Hg(II)

19.01 mg/g

Egyptian mandarin peel (NaOH treated)

Hg(II)

23.26 mg/g

Egyptian mandarin peel (carbonised)

Hg(II)

34.84 mg/g

Potato peels

Cu(II)

0.3877 mg/g

Ponkan peel

Pb(II)

112.1 mg/g

Mosambi (Citrus limetta) peel

Cr(VI)

250 mg/g

Mango peel waste

Cu2+

46.09 mg/g

Mango peel waste

Ni2+

39.75 mg/g

Mango peel waste

Zn2+

28.21 mg/g

Litchi peel waste

Cr(VI)

101.10 mg/g

Modified Cucumis sativa peel

Cd(II)

58.14 mg/g

Zirconium loaded apple peels

AsO2−

15.64 mg/g

Zirconium loaded apple peels

AsO43−

15.68 mg/g

Zirconium loaded apple peels

Cr2O72−

25.28 mg/g

Muskmelon peel

Pb(II)

0.81 mol/kg

Ash gourd peel powder

Cr(VI)

18.7 mg/g

This process is a significant improvement over an existing US patent. The improvements are in the following areas: –– CO2 source is exhaust of a power plant (negative cost) –– NH3 source is sewage water (negative cost + the advantage of organic origin) –– Addition of plant growth in solar aquarium (emulating the world’s first and the biggest solar aquarium in New Brunswick, Canada).

286  Sustainable Water Purification Table 6.12  Uptake capacities of various peel-based adsorbents for organic pollutants removal. (From Bhatnagar et al., 2015). Peel/adsorbent type

Organic pollutants

Amount adsorbed

Orange peel

Congo red

22.4 mg/g

Orange peel

Procion orange

1.3 mg/g

Orange peel

Rhodamine-B

3.22 mg/g

Orange peel

Acid violet 17

19.88 mg/g

Orange peel

Direct Red 23

10.72 mg/g

Orange peel

Direct Red 80

21.05 mg/g

Activated carbon prepared from orange peel

Direct blue-86

33.78 mg/g

Activated carbon prepared from orange peel

Direct Yellow 12

75.76 mg/g

Activated carbon prepared from orange peel

Direct Navy Blue 106

107.53 mg/g

Orange peel waste

Toluidine blue

314.3 mg/g

Pomelo peel

Methylene blue

133 mg/g

Pomelo peel

Reactive Blue 114

16 mg/g

Activated carbon from pomelo peels

Malachite green

178.43 mg/g

Grapefruit peel

Crystal violet

254.16 mg/g

Activated banana peel

Methylene blue

19.671 mg/g

Natural banana peel

Methylene blue

18.647 mg/g

NaOH-activated cassava peels carbon

Methyl red

206.08 mg/g

Jackfruit peel

Methylene blue

285.713 mg/g

Garlic peel

Direct Red 12B

37.96 mg/g

Garlic peel

Phenol

14.49 mg/g (Continued)

Purification Techniques for Industrial Waste  287 Table 6.12  Uptake capacities of various peel-based adsorbents for organic pollutants removal. (From Bhatnagar et al., 2015). (Continued) Peel/adsorbent type

Organic pollutants

Amount adsorbed

Orange peel

Carbofuran

84.49 mg/g

Orange peel

Furadan

161.29 mg/g

Banana peel

Atrazine

14 mg/g

Banana peel

Phenolic compounds

689 mg/g

Jack fruit peel

Phenol

144.9 mg/g

Jack fruit peel

2-chlorophenol

243.9 mg/g

Jack fruit peel

4-chlorophenol

277.7 mg/g

Jack fruit peel

2,4-dichlorophenol

400.0 mg/g

Potato peels

Methylene blue

33.55 mg/g

Melon peel

Methylene blue

333.33 mg/g

Yellow passion fruit peel

Methylene blue

0.0068 mmol/g

Lychee peel waste

Acid Blue 25

200 mg/g

Cucumis sativa fruit peel

Malachite green

36.23 mg/g

Cucumber peel

Methylene blue

111.11 mg/g

Cucumis sativa peel

Crystal violet

32.24 mg/g

Unactivated guava fruit peel

Congo dye

61.12 mg/g

KOH + microwave heated guava fruit peel

Congo dye

120.62 mg/g

Breadnut skin chemically modified with NaOH

Malachite green

353.0 mg/g

Yam peels

Ultramarine blue dye

0.940 mg/g

Rambutan peel

Acid yellow 17

215.05 mg/g

Durian peel

Basic blue 3

49.50 mg/g

Adsorbate Cd(II) Cd(II) Cd(II) Cd(II) Cd(II) Cd(II) Cd(II) Cd(II) Cd(II) Cd(II) Cd(II) Cd(II) Zn(II)

Adsorbent

Crude orange peel (OP)

OP washed with iso-propyl alcohol

OP modified with citric acid

OP modified with alkali saponification

0.6SCA80 (Modified with citric acid after alkali saponification)

OP

SNa (modification after saponification with NaOH)

SAm

SCa

SCA

SOA (orange peel modified with oxalic acid after SNa)

SPA (orange peel modified with phosphoric acid after SNa)

OP

0.76 mol kg−1

0.91 mol kg−1

1.13 mol kg−1

1.00 mol kg−1

0.80 mol kg−1

0.81 mol kg−1

0.85 mol kg−1

0.49 mol kg−1

1.00 mol kg−1

0.85 mol kg−1

0.66 mol kg−1

0.64 mol kg−1

0.49 mol kg−1

qm

Langmuir constants

0.72

0.99

0.61

0.76

0.79

0.87

0.81

0.82

0.76

0.81

0.90

0.54

0.82

b or KL

(Continued)

Table 6.13  Adsorption isotherm studies of different pollutants onto agricultural waste peel-based sorbents. (From Bhatnagar et al., 2015).

288  Sustainable Water Purification

Adsorbate Zn(II) Zn(II) Zn(II) Zn(II) Zn(II) Zn(II) Ni(II) Ni(II) Ni(II) Ni(II) Ni(II) Ni(II) Ni(II)

Adsorbent

SNa

SAm

SCa

SCA

SOA

SPA

OP

SNa

SAm

SCa

SCA (orange peel modified with citric acid after SNa)

SOA (orange peel modified with oxalic acid after SNa)

SPA

2.01

1.28 mol kg

4.90 −1

4.34

1.09

1.48

6.89

0.62

0.89

0.83

1.00

1.13

1.49

0.65

b or KL

1.05 mol kg−1

1.11 mol kg−1

0.69 mol kg−1

0.70 mol kg−1

0.73 mol kg−1

0.46 mol kg−1

1.02 mol kg−1

1.05 mol kg−1

1.21 mol kg−1

0.96 mol kg−1

0.97 mol kg−1

1.17 mol kg−1

qm

Langmuir constants

(Continued)

Table 6.13  Adsorption isotherm studies of different pollutants onto agricultural waste peel-based sorbents. (From Bhatnagar et al., 2015). (Continued)

Purification Techniques for Industrial Waste  289

Adsorbate Co(II) Co(II) Co(II) Co(II) Co(II) Co(II) Co(II) Cu(II) Cu(II) Cu(II) Cu(II)

Adsorbent

OP

SNa

SAm

SCa

SCA

SOA

SPA

OP

OPAA

OP

MOP (sulfur modified orange peel)

−1

70.67 mg/g

50.94 mg/g

289.0 mg/g

44.28 mg/g

1.23 mol kg−1

0.80 mol kg−1

0.84 mol kg−1

0.78 mol kg−1

0.81 mol kg−1

0.82 mol kg−1

0.63 mol kg

qm

Langmuir constants

(Continued)

0.0549 L/mg

0.0161 L/mg

0.033 L/mg

0.019 L/mg

0.37

1.25

0.76

0.46

0.45

1.19

0.43

b or KL

Table 6.13  Adsorption isotherm studies of different pollutants onto agricultural waste peel-based sorbents. (From Bhatnagar et al., 2015). (Continued)

290  Sustainable Water Purification

Adsorbate Cd(II) Cd(II) Cu(II) Cu(II) Pb(II) Pb(II) Zn(II) Zn(II) Mo(VI) Mo(VI) Mo(VI) Mo(VI) Carbofuran

Adsorbent

OP

MOP

MgOP

KOP

MOP (Sulfur modified orange peel)

OP

MOP

OP

Zr(VI)-SOW

La(III)-SOW

Fe(III)-SOW

Ce(III)-SOW

OP

84.49 mg/g

0.99 mmol/g

1.10 mmol/g

1.22 mmol/g

1.35 mmol/g

25 mg/g

80 mg/g

90 mg/g

164 mg/g

59.77 mg/g

40.37 mg/g

136.05 mg/g

47.60 mg/g

qm

Langmuir constants

(Continued)

0.0124 L/mg

1.80 (m−3 kmol−1)

0.59 (m−3 kmol−1)

1.15 (m−3 kmol−1)

1.06 (m−3 kmol−1)

0.022 L/mg

0.010 L/mg

0.035 L/mg

0.066 L/mg

0.067 L/mg

0.095 L/mg

0.0742 L/mg

0.0126 L/mg

b or KL

Table 6.13  Adsorption isotherm studies of different pollutants onto agricultural waste peel-based sorbents. (From Bhatnagar et al., 2015). (Continued)

Purification Techniques for Industrial Waste  291

Adsorbate Fluoride Reactive Blue 114

Malachite green

Crystal violet Methyl orange

Congo red

Adsorbent

ZCOP (zirconium(IV)-loaded carboxylated orange peel)

Pomelo peel

PPAC

Grapefruit peel

Lemon peel

Lemon peel

178.43 mg/g

333 K

42.3 mg/g 27.1 mg/g

45 °C

42.0 mg/g

45 °C 25 °C

61.7 mg/g

25 °C

249.68 mg/g

164.91 mg/g

318 K

13.8 mg/g

323 K

145.78 mg/g

16.3 mg/g

303 K

303 K

14.6 mg/g

283 K

2.7020 mg/g

qm

Langmuir constants

(Continued)

7.9 × 103 (L mol−1)

9.2 × 103 (L mol−1)

7.8 × 103 (L mol−1)

8.1 × 103 (L mol−1)

0.131 L/mg

0.0068 L/mg

0.0062 L/mg

0.0056 L/mg

0.045 L/mg

0.166 L/mg

0.029 L/mg

1.555 L/mg

b or KL

Table 6.13  Adsorption isotherm studies of different pollutants onto agricultural waste peel-based sorbents. (From Bhatnagar et al., 2015). (Continued)

292  Sustainable Water Purification

Adsorbate Cobalt

Pb(II) Cd(II) Cr(VI) Cr(VI) Cr(VI) Cr(VI) Mn(II) Mn(II) Mn(II) Mn(II)

Adsorbent

Lemon peel

Banana peels

Banana peels

Untreated banana peels

Alkali-hydrolyzed banana peels

Acid-hydrolyzed banana peels

Bleached banana peels

Untreated banana peels

Alkali-hydrolyzed banana peels

Acid-hydrolyzed banana peels

Bleached banana peels

14.97 mg/g

45 °C

2.7359 mg/g

4.1516 mg/g

3.6010 mg/g

2.8636 mg/g

2.4644 mg/g

4.4889 mg/g

5.1098 mg/g

3.3557 mg/g

5.71 mg/g

2.18 mg/g

25.64 mg/g

25 °C

qm

Langmuir constants

(Continued)

0.9359 L/mg

0.9940 L/mg

0.9573 L/mg

0.9397 L/mg

0.7505 L/mg

0.9429 L/mg

0.9466 L/mg

0.8533 L/mg

0.04 L/mg

0.11 L/mg

3.90 × 103 (L mol−1)

6.68 × 104 (L mol−1)

b or KL

Table 6.13  Adsorption isotherm studies of different pollutants onto agricultural waste peel-based sorbents. (From Bhatnagar et al., 2015). (Continued)

Purification Techniques for Industrial Waste  293

285.713 mg/g 144.9 mg/g

Pb(II) Cu(II) Methylene blue Phenol 2-chlorophenol 4-chlorophenol 2,4-dichloro-phenol Ni(II)

2,4-di-chlorophenol

Cassava peels

Cassava peels

Jackfruit peel

Jackfruit peel carbon

Jackfruit peel carbon

Jackfruit peel carbon

Jackfruit peel carbon

Pomegranate peel

Pomegranate peel

75.8 mg/g 96.2 mg/g

45 °C

69.4 mg/g

45 °C 25 °C

51.8 mg/g

25 °C

400.0 mg/g

277.7 mg/g

243.9 mg/g

8.00 mg/g

5.80 mg/g

Adsorbate

Adsorbent

qm

Langmuir constants

(Continued)

8.3 × 103 L/mol

6.8 × 103 L/mol

24.0 × 103 L/mol

19.3 × 103 L/mol

0.0024 L/mg

0.0025 L/mg

0.0027 L/mg

0.0029 L/mg

0.0172 L/mg

0.34 L/mg

0.30 L/mg

b or KL

Table 6.13  Adsorption isotherm studies of different pollutants onto agricultural waste peel-based sorbents. (From Bhatnagar et al., 2015). (Continued)

294  Sustainable Water Purification

Adsorbate Pb(II) Cu(II) Ni(II) Pb(II) Pb(II) Methylene blue Mercury Mercury Mercury Cr(VI) Acid Blue 25 Malachite green Malachite green

Adsorbent

Garlic peel

Garlic peel

Garlic peel

Native garlic peel

Mercerized garlic peel

Garlic peel

Raw Egyptian mandarin peel

Chemically treated Egyptian mandarin peel

Carbonized Egyptian mandarin peel Mosambi peel Lychee peel Kemangsi skin (KS) Base-modified KS

34.84 166.66–250 mg/g 204.3 mg/g 177.4 mg/g 227.0 mg/g

23.26

19.01

82.64–142.86 mg/g

109.05 mg/g

51.73 mg/g

32 mg/g

37 mg/g

209 mg/g

qm

Langmuir constants

0.176 0.5–1 L/mg 1.57 × 103 L/mol 0.0036 L/mg 0.0333 L/mg

0.059

0.028

0.044–0.085 L/mg

0.2320 L/mg

0.1303 L/mg

0.564 L/mg

0.129 L/mg

0.112 L/mg

b or KL

Table 6.13  Adsorption isotherm studies of different pollutants onto agricultural waste peel-based sorbents. (From Bhatnagar et al., 2015). (Continued)

Purification Techniques for Industrial Waste  295

296  Sustainable Water Purification

Low/zero emission C

Reactor Recovered CO2

Fresh water

Irrigation water

Useful chemicals Ammonium chloride Sodum carbonate

Ammonia from sewage

Salt water

Figure 6.19  Desalination with maximum economic benefit.

A schematic of the process is shown in Figure 6.19. This process works very well for general desalination involving sea water. However, for produced water from petroleum formations, it is common to encounter salt concentration much higher than sea water. For this, water plant growth (Stage 3 above) is not possible because the salt concentration is too high for plant growth. In addition, even Stage 1 does not function properly because chemical reactions slow down at high salt concentrations. This process can be enhanced by adding an additional stage. The new process should function as:

(1)Saline water + ethyl alcohol (2) saline water + CO2 + NH3 (3) precipitates (valuable chemicals) + desalinated water (4) plant growth in solar aquarium (5) further desalination Care must be taken, however, to avoid using non-organic ethyl alcohol. Further value addition can be performed if the ethyl alcohol is extracted from fermented waste organic materials.

6.5.6 A Novel Separation Technique Chaalal and Islam (2001) developed a fully sustainable water purification technique that can be used to purify water from heavy metals, including

Purification Techniques for Industrial Waste  297 radioactive elements. The setup is shown in Figure 6.1. The technique involves treating the effluent in an algae-packed column. The permeability of the packed column is high enough to allow continuous flow with only hydrostatic pressure of the line connected to the source trough. The selection of algae depends on the type of contaminant to be removed. For instance, for the case of Strontium, C. vulgaris was chosen by Chaalal and Islam (2001). The packed column is connected to the air-curtain driven fluidized bed/membrane system. This reactor is a very successful air curtain driven fluidized bed reactor (Backhurst et al., 1988), coupled with a membrane system (see Figure 6.1). The membrane system was an addition to the design of Backhurst et al. (1988). Compressed air is injected into the reactor through a series of perforations in a transverse tube in order to create fluid circulation with an air curtain. The effluent then moves through to fluidized bed, packed with resins.

7 Summary and Conclusions 7.1 Summary For over a century of the plastic era, the current civilization has been synonymous with synthetic chemicals. At present, between 25,000 to 84,000 synthetic chemicals are used to drive corporate greed, which has become synonymous with capitalism. The number of synthetic chemicals has multiplied 25 times since 1970, with a rise in economic dividend from $171 billion to over $4 trillion today. As these chemicals have created numerous problems in all aspects of civilization, another line of industry has cropped up – the so-called waste management and cleanup industry, which ironically has introduced a new line of synthetic chemicals to ‘purify’ the current contamination. In this scheme, water is the most important victim. There are numerous techniques available today to purify water – the most potent purifier on Earth. Ironically, all techniques use chemicals to replace the contaminants of the water under treatment. These chemicals are all toxic to the environment although they are all certified to be used. It is no surprise that all techniques used for water purification today are unsustainable. This dichotomy arises from the fact that today’s civilization is driven by science that is in capable of identifying the causes, let alone remedying them, of inherent unsustainability of the purification techniques. In this book, the source of contaminations is identified as synthetic chemicals, which should not have entered the ecosystem to begin with. Any purification technique must use sustainable techniques. Sustainability lies within adoption of a zero-waste scheme, rather than struggling to minimize waste. This is establishes that the currently used technologies, which are claimed to be sustainable of varying degrees, are not sustainable. A sustainability analysis, performed on each of these technologies, shows that while each technology is suitable to some extent, none is wholly sustainable. When details of the health risks and overall environmental insults of today’s prevalent. This book finally presents a series of truly sustainable techniques that are environmentally appealing and economically attractive, often fetching M. Safiur Rahman and M.R. Islam. Sustainable Water Purification, (299–302) © 2020 Scrivener Publishing LLC

299

300  Sustainable Water Purification double dividends due to value addition to waste materials. In this book, sustainable purification techniques that are applicable to municipal, agricultural and industrial sectors are presented. The contaminants range from organic contaminants to radioactive waste. It is shown how value addition and conversion of waste can turn a zero-waste process into an economically successful endeavor. Specific recommendations are made for drinking, agricultural and industrial waste water.

7.2 Conclusions Based on the discussion presented in this book, the following conclusions can be made.

7.2.1 Chapter 1: Introduction • Current water purification techniques are deemed to be inadequate and counter-productive to the principle of water purification • Zero waste water management is the key to true sustainability • No existing technology can be declared acceptable, and to build a new one, a paradigm shift is needed

7.2.2 Chapter 2: Water Science • The role of water in sustaining life and proper functioning of all creations was well understood in every epoch outside the modern Eurocentric era • Water science cannot be understood with New Science, which focuses on tangible and short-term phenomena with a myopic approach • A comprehensive delinearized history unravels how environmental integrity is linked to water • A comprehensive purification scheme for water can lead to foundational change in environmental restoration • Every environmental insult with synthetic, unnatural chemicals ruptures the water cycle and creates obstacle to global environmental integrity • Even a slightest disturbance with unnatural chemicals can trigger a snowball effect making any technology environmentally unsustainable

Summary and Conclusions  301

7.2.3 Chapter 3: Sustainability of Current Water Purification Techniques • There are numerous technologies in place for water purification and all new technologies claim to have overcome the shortcoming of the previous ones • None of the currently used technologies is effective in truly purifying water • Each of the currently used technologies replace contaminants with equally if not worse chemicals, although each meet the regulatory requirement • The regularity requirements did not lead to positive change. Instead, more costly and less effective technologies have emerged • While some techniques are more effective than others, when sustainability criteria are considered, none meets the environmental or economical sustainability thresholds

7.2.4 Chapter 4: Sustainable Drinking Water Purification Techniques • The current superflux of unsustainable technologies is inspired by an overall lifestyle that focuses on tangible, external and corporate profiteering • Natural lifestyle must be restored before aspiring to purify water sustainably • Natural minerals were effective for water purification in every ancient civilization and that art should be restored • Each mineral application for water purification produces more effective, most cost-efficient than any currently used technique while being totally sustainable • Each purification technique can benefit from an addition of biological component • Natural sunlight for UV and natural catalysts for ozonation can result in a new array of sustainable water purification techniques • Overall, groundwater is the most suitable for drinking and all purification measures should come only if direct access to groundwater is not an option

302  Sustainable Water Purification

7.2.5 Chapter 5: Sustainable Purification Techniques for Agricultural Wastes • Many sustainable options for purifying agricultural waste are available • Wood dust and fish scales, along with farming waste can be used to purify agricultural waste • The use of biological material enhances the quality of water for agricultural applications • An overall zero waste scheme can be created if various water applications are considered holistically • Solar UV application is very attractive considering its appeal in developing countries, where sunlight is in abundance

7.2.6 Chapter 6: Sustainable Purification Techniques for Industrial Wastes • Sustainable purification technique is available even for most difficult to process radionuclides • Heavy metals and precious metals can be removed sustainably and minerals can be extracted to turn waste liability to asset, creating double dividend • A series of sustainable technologies for water purification are discussed each of which merits full considerations for commercial applications

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Index Absolute mass, 36 Absolute time, 36 Absolute void, 37 Absorption, 74, 101, 209, 211, 239, 244 Acetic acid, 231, 284 Acid violet, 286 Activated carbon, 96, 108, 109, 111, 112, 113, 115, 120, 123, 124, 180, 207, 208, 224, 229, 230 Adaptation, 155, 172 Additive, 11, 12, 38, 43, 44, 235, 238, 248, 283 Adsorption, 10, 67, 80, 81, 107, 117, 119, 121, 123 Adsorption capacity, 110, 111, 113, 114, 116, 119, 120, 121, 122, 188, 195–7, 200, 203, 205, 207, 276–9, 282, 283 Aerosol, 8, 246 Agricultural practice, 155, 161 Agricultural process, 5, 166 Agricultural soil, 227 Agricultural waste, 109, 111, 118, 122, 180, 256, 276, 278, 288 Algae, 9, 10, 43, 88, 110, 150, 222, 224, 255, 296 Amino acid, 1, 115, 147 Aphenomenal, 23, 33, 35, 68, 168, 170, 174 Aquinas, Thomas, 37, 260 Aristotle, 31, 75, 251 Atomic theory, 1, 21, 27 Atomic number, 246 Atomism, 37

Avalanche model/theory, 37 Avicenna, 144, 247 Biochemical, 42, 255 Biofuel, 158 Biological activity, 42, 80, 255 Biological mechanism, 17 Biological process, 39, 78–80, 148, 304 Biological solvent, 275 Biological treatment, 78, 79, 81 Biomass, 5, 79, 80, 86, 181, 186, 191, 193, 196, 221, 225, 230–3, 276, 279, 305, 308, 314, 320 Bones, 42, 44, 143, 144 Carbon, 115, 120, 123–5, 129, 149, 152, 170, 180, 188–90, 2006, 207, 224, 229, 230, 234, 238, 245, 247, 281, 286, 294 Carbon dioxide, 20, 74, 100, 103, 134, 149, 170, 252 Carbon footprint, 268 Carcinogen, 38–42, 44 Catalyst, 17, 40, 152, 179, 181, 226, 227, 231, 235, 248–50, 268, 301, 303 Catalytic ozonation/oxidation, 152 Catalytic process, 224 Catalytic reaction, 250 Charcoal, 10, 42, 111, 149, 151, 229, 232 Chloride, ammonium, 244, 257 cobalt, 217 magnesium, 245

325

326  Index sodium, 171, 245 zinc, 277 Cholesterol, 41 Chrystal violet, 286, 287, 292 Clean energy, 171 Climate change, 5, 73, 74, 76, 131, 134, 155, 158, 317 Coal, 44–46, 124, 234, 238, 244, 245, 256 Coal distillation, 245, 256 Coke, 71, 116, 238 Corrosion, 39, 40 Criteria, 131, 301 Crop, 74, 158, 162–6, 170, 318 Crude oil, 48, 234, 248, 306 Diffusion, 87, 95, 110, 210, 310 DNA, 106, 216, 217, 255 Efficiency, 79, 95, 99, 111, 119, 120, 152, 153, 191, 194, 196, 207, 224, 263, 264, 266, 267, 270–3, 279–2, 308 energy, 263 separation, 275 Einstein, Albert, 157, 168, 260 Electricity, 71, 170, 223, 238, 254, 270, 274 Electromagnetic, 9 Energy balance, 23, 134, 240 Energy consumption, 126, 127, 261–6 Energy demand, 20, 169, 185, 187, 266 Enhanced oil recovery, 270 Environmental impact, 68, 132, 270 Environmental integrity, 16, 300 Equilibrium, 21, 110–2, 115, 167, 171, 191, 193, 197–200, 202, 205, 206, 210, 214, 279, 282, 320 Eurocentric, 300 European union, 268 Fatty acid, 176 Fermentation, 234

Fertilizer, 12, 43, 46, 55, 56, 71, 79, 116, 150, 159, 163, 165, 170, 172, 179, 181, 220, 227, 244 Fluorescent, 49, 239 Freezing, 28, 30, 167 Gamma ray, 23, 24, 176 Gaseous, 3, 8, 9, 17, 18, 27, 28, 33, 37 Gas-solid crystal, 19 Gas solubility, 20 Gastroenteritis, 51–4 Galaxy model, 3, 20, 21, 240, 247 GDP, 59, 135, 264, 265, 267 GNP (Gross national product), 264, 265 Green revolution, 163–5, 311 Greenhouse gas, 134, 179 Groundwater, 37, 40–9, 55, 56, 62, 77, 86, 92, 124, 150, 151, 161, 220, 224, 254, 301, 308, 312 Health effect, 47, 254 Heart, 140–43, 145–7, 240, 314 Heart disease, 135–8, 140, 146, 305, 318 Heat loss, 272 Heat transfer, 271, 272, 314 Heavy metal, 275, 276, 282, 296, 302–307, 309, 310 Helium, 246 Holistic approach, 12, 140, 145 Honey→Sugar →Saccharine →Aspartame (HSSA) syndrome, 169–71 Hydrochloric acid, 209, 244, 245 Ibn Sina, 144, 247 Infra red, 24 Irreversible, 6, 34, 72, 77, 134, 198, 202 Intangibles, 3, 35, 36, 72, 126, 140, 142, 143, 145, 235, 237, 248, 249, 250 Intangible components/elements, 145

Index  327 Jackfruit, 287 Jaundice, 51 Jewelry, 38, 225, 226 Joints, 44 Judicial order, 126

OECD, 268 Oxidation, 57, 101, 103, 148, 151, 152, 208, 303 Ozone, 103, 104, 152, 217, 309, 313, 318

Kelvin, Lord, 36 Ketones, 110, 113, 118, 276

Pathway (natural), 6, 72, 256 Peak oil, 258 Permeability, 88, 222, 296 Porosity, 95, 108, 115

Life force, 4 Lifestyle, 12, 62, 63, 65, 123, 126, 128, 131, 135, 147, 149, 171, 231, 232, 301 Liquid phase, 18, 108, 197, 198, 223, 244 Liquid waste, 226–8 Mental, 44, 141, 144, 240, 312 Mesophilic, 223 Methylene, 110 Methylene blue, 283, 286, 287, 295 Monitoring, 39, 61, 66 Montmorillonite, 120, 121 Monte Carlo simulation, 29 Natural biomass, 232 Natural biopolymer, 276 Natural chemical, 171, 234, 238, 244, 246, 300 Natural decay, 176 Natural fat, 176 Natural frequency, 22 Natural gas, 37 Natural glucose, 175 Natural healing, 248 Natural insulin, 175 Natural light, 24 Natural order, 23, 167, 170, 174 Natural processing, 238 Newton, Sir Isaac, 168, 253 Newtonian, 16, 235, 253 Nobel laureate, 60, 147, 157, 164, 171 Nuclear, 42, 170 Nuclear Magnetic Resonance (NMR), 221

Quantum theory, 16 Radioactive, 49, 79, 151, 221, 296, 300, 306, 312 Radiation, 273 SEM (Electron scanning microscopy), 182, 185–8, 206, 283 Solar, 23, 134, 217, 219 Solar cooker, 216 Solar disinfection, 216–9 Solar electricity, 71 Solar radiation, 23, 134, 217, 219 Solar UV, 151, 216 Solar water distillation, 326, 328 Solid waste, 116, 117, 191, 225, 226, 280, 312 Steam, 8, 28, 37, 99, 100 Steam distillation, 234 Steam injection, 270 Steam power plant, 270 Subatomic, 240 Sustainable growth, 5 Sustainable technology, 13, 68–70, 74, 270, 312 Synthetic chemicals, 9, 10, 59, 76, 123, 124, 173, 232, 244, 249, 256, 299 Synthetic exchanger, 221 Titanium, 221, 274 Titanium oxide, 114

328  Index Thermal disinfection, 216 Thermal fluid, 270, 271, 274 Thermal loss, 271, 272

Vaccine, 164, 167, 211, 212, 214, 215, 239, 272, 273 Violet, 217

Ultraviolet (UV), 101, 102, 104–107, 132, 151, 153, 216, 217, 239, 240, 301, 302 Ultrasonic, 141 Unstable, 68–70, 238, 301 Uranium, 49, 50, 284, 320

Water quality, 5, 53, 59, 60, 65, 66, 91, 146, 147, 150, 155, 219, 316 Wetting, 29 X-ray, 23, 24, 141, 185, 187, 206, 277, 283 Yin-yang, 3, 4, 15, 19, 20, 241, 248