Water challenges and solutions on a global scale 9780841231061, 0841231060, 9780841231054

Table of contents :
Content: 1. Overview of Global Water Challenges and Solutions2. Raising Awareness of Water Issues: The Education Connection, the Educational Potential3. The Effects of Climate Change on Water Resources of Small Developing Countries DS A Case Study of the Republic of Macedonia 4. Drinking Water and Sanitation in Central America: Challenges, Perspectives, and Alternative Water Treatment Irwing M. Ramirez-Sanchez, Susan Doll, and Erick R. Bandala5. Water Challenges and Solutions for Brazil and South America 6. Critical Water Issues in Africa 7. Organochlorine Pesticide Contamination in the Kaveri (Cauvery) River, India: A Review on Distribution Profile, Status, and Trends 8. Ganges River Contamination: A Review9. Water Challenges in India and Their Technological Solutions 10. Water Resources, Water Scarcity Challenges, and Perspectives 11. Contamination Profiles of Perfluorinated Chemicals in the Inland and Coastal Waters of Japan Following the Use of Fire-Fighting Foams 12. Overcoming the Water Treatment Challenges and Barriers in Small, Rural, and Impoverished Communities in Developing Countries 13. Building a Sustainable Water Management System in the Republic of Serbia: Challenges and Issues 14. Sustainable Water Cleaning System for Point-of-Use Household Application in Developing Countries To Remove Contaminants from Drinking Water 15. Potential Uses of Immobilized Bacteria, Fungi, Algae, and Their Aggregates for Treatment of Organic and Inorganic Pollutants in Wastewater 16. Improving the Water Holding Capacity of Soils of Northeast Brazil by Biochar Augmentation 17. Reclaimed Water Systems: Biodiversity Friend or Foe? 18. Nanotechnology Solutions for Global Water Challenges 19. Sustaining Water Resources: A Global Imperative

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Publication Date (Web): December 3, 2015 | doi: 10.1021/bk-2015-1206.fw001

Water Challenges and Solutions on a Global Scale

In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

Publication Date (Web): December 3, 2015 | doi: 10.1021/bk-2015-1206.fw001

In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

ACS SYMPOSIUM SERIES 1206

Publication Date (Web): December 3, 2015 | doi: 10.1021/bk-2015-1206.fw001

Water Challenges and Solutions on a Global Scale Satinder Ahuja, Editor Ahuja Consulting, Calabash, North Carolina

Jailson B. de Andrade, Editor Institute of Chemistry, Salvador-BA, Brazil

Dionysios D. Dionysiou, Editor University of Cincinnati, Cincinnati, Ohio

Kiril D. Hristovski, Editor Arizona State University, Tempe, Arizona

Bommanna G. Loganathan, Editor Murray State University, Murray, Kentucky

Sponsored by the ACS Division of Environmental Chemistry, Inc.

American Chemical Society, Washington, DC Distributed in print by Oxford University Press

In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

Publication Date (Web): December 3, 2015 | doi: 10.1021/bk-2015-1206.fw001

Library of Congress Cataloging-in-Publication Data Names: Ahuja, Satinder, 1933- editor. | American Chemical Society. Division of Environmental Chemistry. Title: Water challenges and solutions on a global scale / Satinder Ahuja, editor, Ahuja Consulting, Calabash, North Carolina [and four others] ; sponsored by the ACS Division of Environmental Chemistry. Description: Washington, DC : American Chemical Society, [2015] | Series: ACS symposium series ; 1206 | Includes bibliographical references and index. Identifiers: LCCN 2015042000| ISBN 9780841231061 | ISBN 9780841231054 Subjects: LCSH: Water-supply. | Water-supply, Rural. | Drinking water. | Water--Pollution. | Water reuse. | Water quality management. Classification: LCC TD345 .W26154 2015 | DDC 628.1--dc23 LC record available at http://lccn.loc.gov/2015042000

The paper used in this publication meets the minimum requirements of American National Standard for Information Sciences—Permanence of Paper for Printed Library Materials, ANSI Z39.48n1984. Copyright © 2015 American Chemical Society Distributed in print by Oxford University Press All Rights Reserved. Reprographic copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Act is allowed for internal use only, provided that a per-chapter fee of $40.25 plus $0.75 per page is paid to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. Republication or reproduction for sale of pages in this book is permitted only under license from ACS. Direct these and other permission requests to ACS Copyright Office, Publications Division, 1155 16th Street, N.W., Washington, DC 20036. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN THE UNITED STATES OF AMERICA In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

Publication Date (Web): December 3, 2015 | doi: 10.1021/bk-2015-1206.fw001

Foreword The ACS Symposium Series was first published in 1974 to provide a mechanism for publishing symposia quickly in book form. The purpose of the series is to publish timely, comprehensive books developed from the ACS sponsored symposia based on current scientific research. Occasionally, books are developed from symposia sponsored by other organizations when the topic is of keen interest to the chemistry audience. Before agreeing to publish a book, the proposed table of contents is reviewed for appropriate and comprehensive coverage and for interest to the audience. Some papers may be excluded to better focus the book; others may be added to provide comprehensiveness. When appropriate, overview or introductory chapters are added. Drafts of chapters are peer-reviewed prior to final acceptance or rejection, and manuscripts are prepared in camera-ready format. As a rule, only original research papers and original review papers are included in the volumes. Verbatim reproductions of previous published papers are not accepted.

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In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

Editors’ Biographies

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Satinder Ahuja Satinder Ahuja (Ph.D., University of the Sciences in Philadelphia) rose to the position of Senior Research Fellow at Novartis Corporation while simultaneously serving as Adjunct Professor at several universities. As President of Ahuja Consulting, he assures drugs and water quality. He helps solve the problem of arsenic contamination of groundwater worldwide and encourages water quality research at Ahuja Academy of Water Quality. His latest books from Elsevier are Comprehensive Water Quality and Purification, Volumes 1−4 (2014); Water Reclamation and Sustainability (2014); Food, Energy, and Water: The Chemistry Connection (2014); and Monitoring Water Quality: Pollution Assessment, Analysis, and Remediation (2013).

Kiril D. Hristovski Kiril D. Hristovski (Ph.D., Civil and Environmental Engineering at Arizona State University) is an Associate Professor in the Engineering and Environmental & Resource Management Programs at the Polytechnic School within the Fulton Schools of Engineering and is a Senior Sustainability Scientist with the Global Institute of Sustainability at Arizona State University. His research focuses on environmental implications and applications of nanomaterials and developing simple and novel water treatment technologies with special emphasis on their use in developing countries. Since 2007, he has produced over 60 peer-reviewed research articles. Dr. Hristovski is a recipient of a Fulbright Specialist Program Fellowship.

Bommanna Loganathan Bommanna Loganathan is a Professor in the Department of Chemistry and Watershed Studies Institute at Murray State University. His research interests include distribution and temporal trends of persistent, bioaccumulative, and toxic chemicals in the environment and biota. He has published over 85 peer-reviewed articles and 35 papers in international conference proceedings. Dr. Loganathan is a recipient of several teaching and research awards, including the 2013 Max Carman Outstanding Teacher Award, the 2012 Karl Hussung Professorship in Chemistry, the 2010 Presidential Research Fellowship, the Sandra Flynn Professor of the Year Award, the 2007 MSU Distinguished Researcher Award, and the Elsevier’s 2007-2011 Top Cited Author Award. He is also a fellow of the American Chemical Society. © 2015 American Chemical Society In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Dionysios (Dion) Dionysiou Dionysios (Dion) Dionysiou is currently a Professor of Environmental Engineering and Science at the University of Cincinnati. He teaches courses and performs research in the areas of drinking water quality and treatment, advanced oxidation technologies and nanotechnologies, and physical-chemical processes for water quality control. He is currently an Editor of the Chemical Engineering Journal and the Journal of Advanced Oxidation Technologies, a Special Issue Editor of the Journal of Environmental Engineering (ASCE), and an editorial board member of several other journals. Dr. Dionysiou is the author or co-author of over 350 refereed journal publications, conference proceedings, book chapter publications, and editorials. He is currently co-editing three books on water reuse, harmful algal blooms, and photocatalysis.

Jailson Bittencourt de Andrade Jailson Bittencourt de Andrade is a full Professor in the Department of General and Inorganic Chemistry, Institute of Chemistry, of the Universidade Federal da Bahia – UFBA and Member of the Brazilian Academy of Sciences. His work in scientific research includes analytical, environmental, and inorganic chemistry. Currently, he is the National Secretary of the Secretariat of Policies and Programs in Research and Development at Ministry of Science, Technology and Innovation, Associate Editor of the Annals of the Brazilian Academy of Science and the Analytical Methods and member of the Editorial Board of the Microchemical Journal.

436 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Preface Water is the most crucial material for human survival, after air. Without water, life would not be possible. It is important to know how much water is available to us and how much water is polluted. We need to monitor pollutants vigorously, both at point and nonpoint sources, using advanced analytical techniques that can monitor ultratrace amounts of contaminants. Water reclamation is an absolute necessity today because we have contaminated our surface water, and even groundwater in some cases, to a point that it is not clean enough for drinking or cooking. Most importantly, we have to use water judiciously and reclaim water that is contaminated. This book provides information on various global water challenges and solutions. We face many water challenges in terms of availability, quality, and sustainability (Chapter 1). There is an urgent need to find ways to make water more sustainable. To achieve this objective, we will have to address scientific, technical, economic, and social issues. Chapters 2 and 3 raise our awareness of water issues, as well as the impact of climate change. Water challenges, including sanitation issues in Central America, South America, and Africa, are covered in Chapters 4, 5, and 6. Water pollution in various rivers in India is encompassed in Chapters 7, 8, and 9. The currently implemented solutions are discussed in some detail. Water scarcity in the Middle East provides an interesting study in that part of the world (Chapter 10). The impact of firefighting foams on water in Japan is discussed at some length in Chapter 11. Overcoming the water treatment challenges in various European countries is covered in Chapters 12, 13, and 14. Chapter 15 discusses the role of immobilized microorganisms and aggregates in wastewater treatment. Reducing the effect of drought on soil in northeast Brazil is covered in Chapter 16. Promoting biodiversity through the maintenance of healthy wetlands can provide beneficial and sustainable ecosystems; however, it can also have adverse consequences on human health (see Chapter 17 for a study in Australia). Nanotechnology solutions to global water challenges are provided in Chapter 18. As a result of their exceptional adsorptive capacity for water contaminants, graphemebased nanomaterials have emerged as a subject of significant importance in the area of membrane filtration and water treatment. Global fresh water is finite, and its supply is severely strained by competing forces of an expanding world population on the one hand, and alterations in the water cycle as a result of climate change on the other (Chapter 19). I would like to thank the authors for their interesting contributions and coeditors for their help in preparation of this manuscript. I am sure this book will be found useful by many scientists, chemical engineers, educators, and administrators who are involved worldwide in water challenges and solutions.

ix In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Satinder (Sut) Ahuja Ahuja Consulting 1061 Rutledge Court Calabash, North Carolina, 28467, U.S.A.

x In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

Chapter 1

Overview of Global Water Challenges and Solutions Publication Date (Web): December 3, 2015 | doi: 10.1021/bk-2015-1206.ch001

Satinder (Sut) Ahuja* Ahuja Consulting, 1061 Rutledge Court, Calabash, North Carolina 28467 *E-mail: [email protected].

Even though Earth is a water planet, we have a very limited quantity of fresh water available to us. Increasing human population, lifestyle and activities not only place high demand on the amount of usable water, but also diminish the quality of water. This chapter discusses water availability, quality, remediation, and sustainability. It also provides a broad overview of global water challenges and solutions. The solutions may be applicable in both developing and developed countries.

Introduction Water is the most crucial material for human survival, after air. Without water, life would not be possible. To detect potential life on other planets, our space program is constantly looking for water on various planets. Here on Earth, we need to know how much water is available to us and how much of it is polluted. We need to monitor pollutants vigorously, both at point and nonpoint sources, and purify water for drinking. Water reclamation (the act or process of recovering) is an absolute necessity because we have polluted our surface water, and even groundwater in some cases, to a point that water needs to be purified for drinking (see Chapter 1 in reference 1). The limited water availability issues discussed in this chapter also dictate the need for water reclamation. Most important, we have to use water judiciously and reclaim contaminated water. We need to find ways to make water more sustainable, i.e., water sustainability is an absolute necessity (1–7). The word sustainability is made up of two words—sustain (to provide what is needed for something or someone to exist) and ability (the power or skill to do something). To achieve sustainability, we © 2015 American Chemical Society In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

must ensure that we meet our needs and avoid compromising the ability of future generations to meet their needs (8). We have to address scientific, technical, economic, and social issues (4) to attain this objective. Globally, we face many water challenges in terms of availability, quality, and sustainability. This book provides information on various global water challenges and solutions.

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Global Water Resources and Use Patterns The data on water consumption in the world are available from the United Nations (UN/UNESCO). Worldwide water consumption is estimated to be around 914,546 billion liters/year. Agriculture accounts for 70% of all water consumption, industrial usage accounts for 20%, and domestic usage is 10%. In highly industrialized countries, however, manufacturing consumes more than half of the available water. In Belgium, for example, industries use up to 80% of the available water. Here is some important information about the availability and quality of our worldwide water supplies: • • • • •

Freshwater comprises only 3% of the total water available to us. However, only 0.06% is easily available. More than 80 countries in the world have water shortages. According to the UN, 2.7 billion people will face a water shortage by 2025. Almost 1.2 billion people drink unclean water today. Five million to ten million people around the world are killed by waterrelated disease yearly, mostly children.

Over the last 50 years, freshwater withdrawals have tripled. The demand for freshwater is increasing by 64 billion cubic meters per year (1 cubic meter = 1,000 liters) because of the following reasons: • • • •

The world’s population is growing by roughly 80 million each year. Changes in lifestyles and eating habits in recent years require more water consumption per capita. Water demand is rapidly increasing because of accelerated energy demand. The manufacture of energy from alternate sources such as biofuels has a major impact on water demand because 1,000 to 4,000 liters of water are needed to produce just one liter of biofuel.

Nearly 85% of the world population live in the dry part of our planet. This problem is further compounded because almost 2.5 billion people do not have access to adequate sanitation, and poor sanitation affects water quality. As a result, nearly 80% of diseases in developing countries are associated with water. Global population growth projections to around 3 billion people over the next 40 years, along with changing diets, will cause an increase in food demand 2 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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by over 70% by 2050. It is estimated that water consumption will increase by about 19% by 2050. And that number will be even greater if there is no technological progress or policy intervention. One of the greatest pressures on freshwater resources is the impact of water usage for irrigation and food production. As mentioned before, agriculture accounts for approximately 70% of global freshwater withdrawals (up to 90% in some fast-growing economies). Water availability is predicted to decrease in many regions, and future global agricultural needs are growing. Water is obviously not confined to political borders. Nearly 46% of the globe’s (terrestrial) surface is covered by trans-boundary river basins. An estimated 148 states have international basins within their territory, and 21 countries lie entirely within them. There are 276 across-border river basins in the world (64 transboundary river basins in Africa, 60 in Asia, 68 in Europe, 46 in North America, and 38 in South America). Of the 276 trans-boundary river basins, 185 are shared by two countries. And 256 out of 276 are shared by 2, 3, or 4 countries (92.7%), and 20 of 276 are shared by 5 or more countries. Interestingly, 18 nations share the Danube River basin. Nearly all Arab countries suffer from water scarcity. An estimated 66% of the Arab region’s available surface freshwater originates outside the region. About 66% of the African land mass is arid or semiarid, and more than 300 million of the 800 million people in sub-Saharan Africa live in water-scarce environments; i.e., they have fewer than 1,000 m3 per capita (9). The process by which land turns desert-like is not restricted to African countries, where the Sahara is stealthily growing southward by about 48 square kilometers a year. The major causes of desertification are climate change and poor soil conservation, which degrade the soil. The overuse of chemical fertilizers, failure to rotate crops, and irresponsible irrigation all rob the earth of its nutrients, and there is swift depletion of plant life and loss of topsoil. According to China’s State Forestry Administration, more than 27% of the country has undergone desertification. Inner Mongolia, in northern China, has experienced one of the worst cases. Desertification has hit 18 provinces and impacts more than 400 million people. The root causes are climate change and poor soil conservation, seriously degrading the soil. The overuse of chemical fertilizers, failure to rotate crops, and irresponsible irrigation rob the soil of its nutrients. Eventually, the land gives way to sand. While China loses arable land, the government is reclaiming land. About 20 years ago, the government began planting millions of trees, constructing terraces and small-scale dams. It also has banned grazing from some areas. Loess plateau, in central and northern China, for instance, covers more than 620,000 square kilometers and is highly prone to erosion because of silt. It is believed that many centuries ago the plateau was fertile and easy to farm, but deforestation and overgrazing turned it into a desert. It is one of the most severely eroded lands in China. A large part of the loess plateau has been reclaimed. According to Professor Charles Jia, University of Toronto, Canada, the other big problem is that China simply doesn’t have enough water. Large-scale industrialization has overwhelmed scarce supplies, and drinking water has become the biggest casualty. China has about 7% of the world’s freshwater but sustains more than 20% of the 3 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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population (by comparison, the Great Lakes contain 21% of the world’s freshwater supply). The other big problem is that China simply doesn’t have enough water. Large-scale industrialization has overwhelmed scarce supplies, and drinking water has become the biggest casualty. Advanced countries like the US are not immune to water shortages. A severe drought in California is now approaching four years. It has depleted snow packs, rivers, and lakes; and groundwater use has soared to make up the shortfall. The Sierra Nevada snowpack, which Californians rely on heavily during the dry summer months for their water needs, continued to disappoint in the winter of 2014—15. A recent manual survey by the Department of Water Resources (DWR) at the Phillips snow course in the mountains 90 miles east of Sacramento found 0.9 inches of water content in the snow, just 5% of the March 3 (2015) historical average for that site. Recent electronic readings by the DWR indicate the water content of the northern Sierra snowpack is 4.4 inches, 16% of the average for the date. The central and southern Sierra readings were 5.5 inches (20% of average) and 5 inches (22%), respectively. A recent report from Stanford University asserts that nearly 60% of the state’s water needs are now met by groundwater, up from 40% in years when there are normal amounts of rainfall and snowfall. Relying on groundwater to make up for the shrinking surface water supplies comes at a rising price, and this hidden water found in California’s Central Valley aquifers is the focus of what amounts to a new gold rush. Well-drillers are working overtime, and farmers and homeowners short of water now must wait in line more than a year for their new wells. In most years, aquifers recharge as rainfall and stream flow seep into unpaved ground. But during droughts the water table—the depth at which water is found below the surface—drops as water is pumped from the ground faster than it can recharge. Central Valley wells that till now struck water at 500 feet must now be drilled down 1,000 feet or more, at a cost of more than $300,000 for a single well. And as aquifers are depleted, the land begins to shrink. Groundwater comes from aquifers—spongelike gravel- and sand-filled underground reservoirs—and we see this water only when it flows from springs and wells. In the United States, we rely on this hidden and shrinking water supply to meet our needs; and as droughts shrink surface water in lakes, rivers, and reservoirs, we rely even more on groundwater from aquifers. Some shallow aquifers recharge from surface water, but deeper aquifers contain ancient water locked in the earth by changes in geology thousands of years ago. These aquifers typically cannot recharge, and once this "fossil" water is gone, it is gone forever—potentially changing how and where we can live and grow food, among other effects (10). California has pushed harder than any other state to adapt to a changing climate, but scientists warn that improving its management of precious groundwater supplies will shape whether it can continue to supply more than half of the nation’s fruits and vegetables on an imminent hotter planet. As a drilling frenzy unfolds across the Central Valley, California’s agricultural heartland, the consequences of the overuse of groundwater are becoming very clear. In some places, water tables have dropped 50 feet or more in just a few years. With less underground water to buoy it, the land surface is sinking as much as a foot a year in spots, causing roads to buckle and bridges to crack. Shallow wells have run dry, depriving some poor communities of water. Some of the underground 4 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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water-storing formations so critical to California’s future—typically, saturated layers of sand or clay—are being permanently damaged by the excess pumping, and will never again store as much water as farmers are withdrawing. In normal times, agriculture consumes roughly 80% of the surface water available for human use in California, and experts say the state’s water crisis will not be solved without major involvement with farmers. California’s greatest resource in dry times is not its surface reservoirs, but its groundwater. Scientists say it is obvious that drought has made apparent the need for better controls. While courts have taken charge in a few areas and imposed pumping limits, groundwater in most of the state has been a resource anyone could grab. The land devoted to almond orchards in California has doubled in 20 years, to 860,000 acres. The industry has been working hard to improve its efficiency, but growing a single almond can still require as much as a gallon of California’s precious water. The expansion of almond, walnut, and other water-guzzling trees and vine crops has come under sharp criticism from some urban Californians. The groves make agriculture less flexible because the land cannot be idled in a drought without killing the trees. Putting strict limits in place is expected to take years. The new law, which took effect January 1, 2015, does not call for reaching sustainability until the 2040s. Worldwide Water Quality Developing and developed countries have different, yet similar, problems with water quality. These water quality issues in China and the US are discussed in some detail below, as they represent a fast developing country and a very developed country.

Developing Countries People need to be prudent when they drink water in Africa, Asia, and Latin America. The rivers in these areas are frequently considered the most polluted in the world. They have 3 times as many bacteria from human waste as the global average, and 20 times more lead than rivers in developed countries. In 2004, water from half of the tested sections of China’s seven major rivers was found to be undrinkable because of pollution. The Yangtze, China’s longest river, is “cancerous” with pollution. The pollution from untreated agricultural and industrial waste could turn the Yangtze into a “dead river” within a short time. This would make it impossible to sustain marine life or provide drinking water to the booming cities along its banks. Almost half of China’s water sources are polluted. Wells and aquifers are contaminated with fertilizers and pesticide residues and heavy metals such as arsenic and manganese from mining, the petrochemical industry, and domestic and industrial waste. More than three-fourths (76.8%) of 800 wells monitored in nine provinces and autonomous regions and municipalities, including Beijing, Shanghai and Guangzhou, failed to meet standards for groundwater in a 2011 national evaluation (11). 5 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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China, like many other countries, has failed to keep up with demand for clean water (12, 13). It is well known that decades of reckless pollution had spawned a string of “cancer villages.” These are communities near chemical, pharmaceutical, or power plants with unusually high death rates. Environmentalists, NGOs, and academics long argued that contaminated water that villagers rely on for drinking, cooking and washing, was the prime suspect. Nearly 450 cancer villages were identified in the late 1990s. The belated recognition appeared in a recent environment government ministry’s five-year plan for tackling pollution. The document said: “In recent years, toxic and hazardous chemical pollution has caused many environmental disasters, cutting off drinking water supplies, and even leading to severe health and social problems such as cancer villages.” China is the world’s largest grain producer. It has also become the world’s largest producer and consumer of fertilizers and pesticides. Its fields are a bigger source of water contamination than factory effluents, the Chinese government said in its first pollution census in 2010. More than half of China’s water pollution comes from fertilizers, pesticides, and livestock waste that are carried into lakes, rivers, wetlands, coastal waters, and underground aquifers by rainfall and snowmelt. Pig and poultry farms are also major polluters of water.

Developed Countries Nearly 40% of the rivers in the US are too polluted for fishing, swimming, or aquatic life. The Mississippi River drains nearly 40% of the soil and water of continental United States, including its central farmlands, and it carries an estimated 1.5 million metric tons of nitrogen pollution into the Gulf of Mexico every year. Nearly 1.2 trillion gallons of untreated sewage, storm water, and industrial waste are discharged into US waters annually. Lakes are even worse—46% of them are extremely polluted. Two-thirds of US estuaries and bays are either moderately or severely degraded from eutrophication (nitrogen and phosphorus pollution). Even the most advanced country, like the US, is facing a water crisis. Most experts agree that the US water policy is in chaos. Decision making about allocation, repair, infrastructure, and pollution is spread across hundreds of federal, state, and local agencies. • • •

Over 700 different chemicals have been found in US drinking water as it comes out of the tap! The EPA classifies 129 of these different chemicals as being particularly dangerous. The EPA sets standards for approximately 90 contaminants in drinking water.

The quality of water in Europe’s rivers and lakes worsened between 2004 and 2005. Almost one-third of Ireland’s rivers are polluted with sewage or fertilizer. The Sarno River in Italy is the most polluted river in all of Europe, featuring a mix of sewage, untreated agricultural waste, industrial waste, and chemicals. The Rhine, which flows through many European countries, is regarded by many as the 6 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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dirtiest large river; almost one-fifth of all the chemical production in the world takes place along its banks. The King River is Australia’s most polluted river, suffering from a severe acidic condition related to mining operations. Canadian rivers are also polluted. The failure of safety measures relating to production, utilization, and disposal of a large number of inorganic/organic compounds from arsenic to zinc can cause contamination of our water supplies (7). The discussion below briefly covers various contamination problems with water. Arsenic contamination affects almost 200 million people worldwide, even in developed countries such as the US. The most polluted area in the world, Bangladesh, has arsenic-contaminated groundwater over 85% of its total land area. Naturally occurring arsenic contaminates millions of wells that were installed to eliminate microbial contamination. After years of drinking this water, residents face arsenicosis, which can lead to a slow and agonizing, painful disease, resulting in death. In searching for a possible solution, the author organized workshops in Bangladesh and India. Then several symposia were planned by him at the American Chemical Society, UNESCO, and International Union of Pure and Applied Chemistry meetings. Detailed discussion on how groundwater is contaminated with arsenic, desirable methods for monitoring arsenic contamination at ultratrace levels (below one part per million), and the best alternatives for reclamation are available in a text entitled Arsenic Contamination of Groundwater (2). Over 80% of used water worldwide is not collected or treated. The need for groundwater recharge may ultimately limit how much water farmers can have from surface irrigation systems, even in flush years—the same way that credit card limits determine how many fancy dinners one can eat. Yet in a state where irrigation rights have been zealously guarded for generations, such limitations may not go down easily. The treatment of wastewater requires significant amounts of energy, and demand for power to do so is expected to increase globally by 44% between 2006 and 2030 (14), especially in countries not covered by the Organization of Economic Cooperation and Development where wastewater currently receives little or no treatment. Pollution knows no borders either. Up to 90% of wastewater in developing countries flows untreated into rivers, lakes and highly productive coastal zones, threatening health, food security, and access to safe drinking water and bathing water. Sources of Contamination Drinking water comes mainly from the following sources: rivers, lakes, wells, and natural springs. These sources are exposed to a variety of conditions that can cause contamination of water. Some of the sources of contamination are listed alphabetically below. • • •

Combustion products of coal/oil (gasoline) Detergents Disinfectants 7 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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• • • • • • • •

Drugs (pharmaceuticals and illicit drugs) Fertilizers Gasoline and its additives Herbicides Insecticides Pesticides Phthalates Volatile and semi-volatile compounds

About 12,500 tons of antimicrobials and antibiotics are administered to healthy animals on US farms each year. A 2002 US Geological Survey found pharmaceuticals (hormones and other drugs) in 80% of the streams sampled in 30 states. These contaminants are suspected in the increase of fish cancer, deformities, and feminization of male fish. The world’s seas are inundated by a variety of water pollution problems. The Baltic Sea, Yellow Sea, Bohol Sea, Congo Basin and Victoria Lake are affected severely by eutophication. The primary problem with the Gulf of Mexico is microbiological contamination, and the Aral Sea contains a variety of pollutants. Solid waste and radionuclides are the primary pollutants around the Pacific Islands and the Benguela Current (West Coast of Africa). The Caribbean Sea has problems with suspended solids and spills. The extensive use of plastics and their careless disposal has led to pollution of various water bodies. Large parts of the Pacific Ocean are referred to as “plastic oceans,” where enormous gyres, about the size of Texas, are covered with plastic debris. The Pacific is the largest ocean realm on our planet, approximately the size of Africa—over 10 million square miles—and it is the home of two very large gyres. The Atlantic Ocean contains two more gyres, and other plastic oceans exist in other bodies of water. Volatile organic contaminants (VOCs) may enter directly into our water resources from various spills, by improper disposal, or from the atmosphere in the form of rain, hail, and snow. In general, VOCs have high vapor pressures, low-to-medium water solubilities, and low molecular weights. These properties allow them to move freely between water and air. Many volatile organic contaminants find their way to our drinking water (4).

Monitoring Water Contaminants Our civilization has managed to pollute our waters to the point where we must disinfect water for drinking. To assure water purity, we need to monitor contaminants from arsenic to zinc (7). In the 1978 Metrochem meeting, the author emphasized the need to analyze very low levels of various contaminants, in a paper entitled “In Search of Femtogram” (a femtogram is 10−15g, or one part per quadrillion), to fully understand their impact on animals. For example, dioxin (2,3,7,8-tetrachloro-dibenzodioxin) can cause abortions in monkeys at the 200 parts-per-trillion (ppt) level (15). PCBs (polychloro biphenyls) at the 0.43 ppb 8 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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(parts-per-billion) level can weaken the backbones of trout (16). This suggests that ultratrace analysis is necessary to monitor materials like PCBs and dioxin (17–19). We have known for some time now that water that we call potable may actually contain many trace and ultratrace contaminants, as exemplified by an analysis of Ottawa drinking water (20). It contained insecticides like α-BHC (an isomer of lindane), lindane, and aldrin, at ppt levels. In addition, it contained phthalates at significantly higher concentrations. In 2010, a UN resolution declared the human right to “safe and clean drinking water and sanitation.” A simple definition of potable water is “any water that is clean and safe to drink. National primary drinking water regulations control water quality in the US, in response to public concern about degraded water quality and the widespread view that pollution of our rivers and lakes was unacceptable. The Clean Water Act (CWA) became law in 1972. Control of point-source contamination, traced to specific “end of pipe” points of discharge or outfalls, such as factories and combined sewers, was the primary focus of the CWA. Other nations adopted similar measures and have seen improvement in point-source contamination as well. In the US, potable water must be cleaner than the maximum contaminant level mandated by local, state, and federal guidelines (USEPA national primary drinking water regulations). Water is a clear liquid, though a layperson might describe water’s color as white or blue. The fact is that many colors that have been ascribed to water relate to the materials that may be present in it (see below). For example, blue water generally refers to ocean water, which gets its color from the reflection of the color of the sky; and we have seas that are described by various other colors because of their appearance: Red Sea, Yellow Sea, Black Sea, and White Sea. Water generated from activities such as laundry, dishwashing, and bathing is called gray water, and water which has come into contact with fecal matter is called black water. Frequently, municipal water may have an odor at times, and that odor relates to the chlorination of water. A musty odor in drinking water may be the result of by-products of blue-green algae. The tests commonly carried out on drinking water are turbidity, total organic carbon, chlorite, chlorine dioxide, fluoride, sulfate, and orthophosphate (21). Some unregulated substances are also investigated. Surprisingly, testing of arsenic is not performed regularly. The impact on water quality of a variety of contaminants has been discussed earlier (22).

Water Reclamation Over 80% of the used water worldwide is not collected or treated. This situation has to change, as we don’t have an unlimited supply of safe water for our needs; and water reclamation is absolutely necessary (22). Some examples of wastewater reclamation are discussed below. According to a 2012 Ministry of Water Resources of the People’s Republic of China, China Water Resources Bulletin 2011 (China Water & Power Press, 2012), a closer look at how water is used reveals that this problem is tractable. Almost two-thirds of municipal water is used by industry, agriculture, and construction. 9 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Households consume the remaining one-third (365 million people used 15.3 billion tons of water in 2011). Of that, laundry, bathing, and dishwashing take up the most (together more than 80%). Cooking and drinking use just over 2% (1.1 billion tons). In other words, most household water does not need to be drinkable. Bringing a large developing country such as China up to the same standards as a developed country will require more intensive water treatment. This has environmental consequences. In Jiangsu province, for example, carbon dioxide emissions increased by 28% in 2012 when a type of water filtration called ozone–biological activated carbon treatment was extended to one-quarter of the provinces’ supply (5.3 million tons per day). China and other underdeveloped countries need cheap, energy-efficient methods of water purification that minimize chemical use. Water purification systems that improve drinking water at the point of use are a good fit in many areas. In Kenya, Bolivia, and Zambia, water purifiers have been shown to reduce diarrheal disease by 30–40%. Fewer than 5% of Chinese homes currently have these purifiers, despite a unit’s low cost of only around 1,500 to 2,000 renminbi. China’s water-purification industry is growing by about 40% a year—fewer people are buying water dispensers and barreled water. But water-purification devices are unregulated. Incomplete after-sales service leads to improper maintenance, and delays in changing filter cartridges can introduce microorganisms. Filters and units made from toxic materials such as nonfoodgrade plastic are ineffective. Treated gray water (wastewater from showers and baths) and black water (from toilets) are increasingly used in China for industrial and irrigation purposes, and for flushing toilets in new residences. But this type of recycling is impractical for most existing households because of the high cost and the disruption in the home while installing the necessary plumbing. It has been suggested that by using cheap, low-carbon water purifiers in all homes, China can avoid the technology “lock-in” that leads developed countries to waste potable water, and China can leapfrog to a sustainable supply system. In the long term, the improvement of water sources will ensure that most people have safe drinking water.

Producing Drinking Water from Rivers River water is frequently used for drinking, after purification. An example from India is provided here. Water for drinking is obtained from the Yamuna River before it is subjected to local contamination in Delhi. The recently constructed Sonia Vihar Water Treatment Plant helps meet the great demand of more water for the 15 million residents of Delhi. Various steps involved in the purification of water are shown in Figure 1. Water from the Ganges River can also be utilized with this same process.

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Producing Drinking Water from the Ocean

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It is necessary to desalinate ocean water before using it for drinking or cooking. Desalination removes some amount of salt and other minerals from salt water. The principal process uses membranes to desalinate water by reverse osmosis. This process uses semipermeable membranes and pressure to separate salts from water. This system uses less energy than does thermal distillation, leading to a reduction in overall desalination expenses over the past decade. Desalination continues to be energy-intensive, however, and future costs will continue to rely on the price of both energy and desalination technology.

Figure 1. Water purification process at the Sonia Vihar Plant. Various desalination methods are listed below: • • • •

Mechanical vapor compression Multi-effect distillation Multistage flash distillation Reverse osmosis

Reverse osmosis uses the least amount of energy, compared to the other methods shown above. Energy consumption of seawater desalination can be as low as 3 kWh/m3 including pre-filtering and ancillaries; this far exceeds 0.2 kWh/m3 or less required for freshwater supplies from local sources. All desalination processes generate large quantities of a concentrate that may have residues of pretreatment and cleaning chemicals, their reaction by-products, and heavy metals because of corrosion. Chemical pretreatment and cleaning are a necessity in the majority of desalination plants, typically including treatment against biofouling, scaling, foaming, and corrosion in thermal plants, and against biofouling, suspended solids, and scale deposits in membrane plants. Some methods of desalination, in combination with evaporation ponds, solar stills, and condensation traps, do not discharge brine. They don’t use chemicals in their processes, nor do they burn fossil fuels. Membranes or other critical parts, 11 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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such as components that include heavy metals, are not utilized; thus they do not cause toxic waste (or high maintenance). There is a new approach that works like a solar still, but is on the scale of industrial evaporation ponds. It is called “full desalination” because it converts the entire amount of saltwater intake into distilled water. One of the unique advantages of this type of solar-powered desalination is the feasibility of inland operation. Other advantages include no air pollution from desalination power plants and no temperature increase of endangered natural water bodies from power plant cooling-water discharge. Another important advantage is the production of sea salt for industrial and other uses.

Producing Drinking Water from Poisoned Wells Arsenic contamination of groundwater has been reported in a large number of countries in the world; Bangladesh and Bengal (India) suffer most. Almost one-hundred million people in Bangladesh are at risk, as they consume arseniccontaminated water at levels of 10 ppb or greater. Inorganic arsenic above the 10 ppb level can increase the risk of lung, skin, bladder, liver, kidney, and prostate cancers.

Sources of Arsenic Contamination Water contamination in Bangladesh and India has been attributed to the geology in parts of those countries. Microbially mediated reduction of assemblages comprising arsenic sorbed to ferric oxyhydroxides is gaining consensus as the chief mechanism for the mobilization of arsenic into groundwater. A recent microcosm-based study has provided the first direct evidence for the role of indigenous metal-reducing bacteria in the creation of toxic, mobile As(III) in sediments from the Ganges delta (2). Arsenic contamination from other sources is possible anyplace in the world because arsenic compounds are used commercially for the following applications: • • • • •

Pesticides: monosodium methyl arsonate, disodium methyl arsonate Insecticide: dimethylarsenic acid Aquatic weed control and sheep and cattle dip: sodium arsenite Defoliating cotton bolls: arsenic acid, arsenic pentoxide Some pharmaceuticals and decolorizing glass: arsenic trioxide

Large areas in the west, midwest, and northeast US have high arsenic concentrations. For example, in North Carolina, arsenic was found in 960 wells statewide in January 2000. According to the Wilmington Star News of August 18, 2003, half of the state’s population depends on groundwater. The state toxicologist, Ken Rudo said “for new wells, arsenic test is pretty much not done.”

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Monitoring Arsenic at Ultratrace Levels

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A number of methods can be used for analyzing arsenic in water at 10 ppb or an even lower level (2). The speciation of arsenic requires separations based on solvent extraction, chromatography, and selective hydride generation. Detection limits for arsenic down to 0.0006 µg/L can be obtained with inductively coupled plasma mass spectrometry (ICP-MS -I). HPLC CP-MS is currently the best technique available for determination of inorganic and organic species of arsenic. The main problem is the high cost. Using hydride generation (HG), arsenic can be determined by a relatively inexpensive atomic absorption spectrometer or atomic fluorescence spectrometer (AFS) at single-digit µg/L. For developing countries, there is a need for low-cost, reliable instrumentation and dependable field test kits.

Remediation The following methods can be used for remediation of arsenic contamination of water: • • • • • • • • • • • •

Coagulation with ferric chloride or alum Sorption on activated alumina Sorption on iron oxide–coated sand particles Granulated iron oxide particles Polymeric ligand exchange Nanomagnetite particles Hybrid cation exchange resins Hybrid anion exchange resins Polymeric anion exchange Reverse osmosis Nanomagnetite particles Sand with zero valent iron

Two filters that stand out in terms of their usefulness for serving a small family or a community are briefly described below.

Single Family Systems These systems are based on solid sorbents. Special emphasis has been placed on iron-based filters because they appear to be chemically most suitable for arsenic removal, they are easy to develop, and they are environmentally benign. Arsenic removal mechanisms for a SONO filter are based on surface complexation reactions, sorption dynamics, and kinetics (see details in Chapter 12 in reference (2)). This is one of the four filters approved by the Bangladesh government for public use. The manufacturer claims that the filtered water meets Bangladesh standards (50 ppb of arsenic vs 10 ppb standard in the US), has no 13 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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breakthrough, works without producing toxic wastes. These figures are based on EPA guidelines (3). The filter costs about $40, lasts for five years, and produces 20–30 L/hour for daily drinking and cooking needs of one or two families. A large number of these filters have been used all over Bangladesh and continue to provide more than a billion liters of safe drinking water. This innovation was recognized by the National Academy of Engineering Grainger Challenge Prize for Sustainability, with the highest award for its affordability, reliability, ease of maintenance, social acceptability, and environmental friendliness. It should be noted that the flow rate may decrease 20–30% per year if the groundwater has high iron levels (>5 mg/L), because of formation and deposition of natural HFO in sand layers. The sand layer (about one-inch thick) then has to be removed, washed and reused, or replaced with new sand. A protocol for elimination of pathogenic bacteria should be used once a week in areas where coliform counts are high. It should be noted that, as with all commercial filters, the consumer needs to be alert to manufacturing defects, and mishandling during transportation.

Community-Based Filters A community filter can serve about 200 households and requires no chemical addition, pH adjustment, or electricity (see Chapter 13 in reference (2)). A large number of these filters have been installed since 1997, and have the following characteristics: • •

Utilize activated alumina as an adsorbent media that can be regenerated Purify Influent arsenic solutions ranging from 100 μg/L to 500 μg/L, containing both As(III) and As(V) species

When the filter is exhausted, the media can be replaced and the spent media is then taken to a central regeneration facility for further reuse. An arsenic-laden spent regenerant form is converted to a small volume of sludge that can be contained in an aerated, coarse sand filter. The process is claimed to be environmentally sustainable because the treatment residues are not toxic under normal environmental conditions. It is also economically sustainable, as the villagers collectively maintain the units by paying a monthly water tariff of about $0.40.

Recycling Wastewater to Groundwater The Orange County Water District (OWCD) in California treats and injects 70 mM gallons/day into groundwater. It takes treated sewer water that would otherwise be discharged into the ocean, purifies it to near distilled quality and then recharges it into the groundwater basin. OCWD ensures the Orange County 14 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

groundwater basin is free of contamination and that usage is sustainable. It uses microfiltration, reverse osmosis, and ultraviolet (UV) to purify wastewater. Microfiltration removes bacteria and protozoa, and also particles and suspended solids. Reverse osmosis removes viruses, bacteria, and chemical contaminants such as dissolved salts, metals, organic compounds, including endocrine disruptors and other pharmaceuticals. UVlight inactivates microbes and prevents replication; UV with hydrogen peroxide is used to destroy small organics.

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Recycling Wastewater to Surface Water A preliminary treatment process used by NEWater in Singapore removes debris and sandy materials from used water. The primary treatment process allows the solid pollutants in suspension (primary sludge) to settle to the bottom of the tanks and lighter materials like scum or greasy materials to float to the surface of the tank. The secondary treatment takes the upper layer of water and puts it into the aeration tank that is a bioreactor and final clarifier. The used water is mixed with a culture of microorganisms, known as activated sludge, in the aeration tank. The microorganisms absorb and break down the organic pollutants. The clear supernatant water at the top of the tank is collected and discharged from the tanks as the final effluent. The sludge is allowed to remain in the digesters for 20–30 days. Anaerobic digestion of the organic matter in sludge produces biogas, which contains 60—70% methane.

Reclaiming Wastewater for Drinking Singapore gets 30% of its water requirements via the purification process developed by NEWater. To produce drinking water, the following treatment steps are used in addition to those listed above: • • • •

Membrane filtration Reverse osmosis Elimination of bacterial impact Capture of nutrient value

The amount of testing done to reclaimed water should relate to how it is going to be recycled. For example, if it is recycled into a surface water supply, its quality after purification should match or exceed the requirements of the surface water to which it is being added. Similar rules may be followed for mixing with groundwater. Recycled wastewater for drinking must meet potable water requirements, with the added assurance by ultratrace analysis that no toxic contaminants are present (4). A variety of global challenges to water and solutions are covered below. 15 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Raising Awareness of Water Issues: The Education Connection, the Educational Potential The challenges posed by finite amounts of clean, potable water and a continuously growing human population are still not well understood by a significant portion of the population (Chapter 2). An increased awareness of water concerns, specifically of wastewater treatment technologies and sanitation practices, can be attained if these issues are addressed thoroughly and repeatedly in general chemistry classes at both high school and college levels, and in upper level undergraduate chemistry curriculum courses such as industrial chemistry and environmental chemistry. Engineering classes should include courses related to water problems. This chapter presents a detailed approach to raising the awareness of current water topics by repeated exposure in college chemistry classes in several different courses.

The Effects of Climate Change on Water Resources of Small Developing Countries – A Case Study of the Republic of Macedonia In the absence of high-resolution climate-change model predictions, employing empirical data collected over a long period may be the only viable option to predict the climate change impact on small and developing countries where the socioeconomic structure is strongly rooted in water- dependent sectors such as agriculture or energy production (Chapter 3). The overarching goal of this study is to demonstrate the suitability and significance of employing empirically obtained historical data in predicting the impact of future global climate change trends in a small country like the Republic of Macedonia. The climate change effects on the national surface water resources of Macedonia were assessed by examining temperature trends and other descriptors of global warming spanning over 50 years, by testing three data-driven hypotheses. The analysis extended over 50 years of historical records, and three data-driven hypotheses were tested. The records describe statistically significant trends: increase in national average temperatures, surface water resources depletion, and fluctuations in the magnitude of precipitation. These grim scenarios indicate substantial socioeconomic and environmental challenges for the Republic of Macedonia for fear that adequate mitigation measures are not implemented.

Drinking Water and Sanitation in Central America: Challenges, Perspectives, and Alternative Water Treatment Chapter 4 analyzes plausible alternatives for water treatment and wastewater sanitation aimed to improve the population’s health by assuring their access to safe drinking water in countries in Central America. Water treatment alternatives for the region are proposed as centralized and non-centralized systems. Challenges 16 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

and perspectives for the region are considered on the basis of intervention of low-cost water technologies, education about safety practices, and awareness for governments in implementing water management strategies.

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Water Challenges and Solutions for Brazil and South America Freshwater is unevenly and temporally distributed across the planet or is located in places that are difficult to access. South America is relatively well-endowed with freshwater, although millions of people suffer from restrictions on potable water and proper sanitation systems, because of longer drought periods, as well as the lack of an adequate infrastructure and proper governance (Chapter 5). It is estimated that 60—80% of water is used in agricultural irrigation in developing countries in South America. As for energy, South America has one of the greenest energy mixes, when the large contribution of hydropower, wind power, and biofuels are taken into account. The water demand for power generation from different sources focuses our attention on water-energy nexus in South America.

Critical Water Issues in Africa Water scarcity, purity, and delivery have become major challenges of humanity, especially in Africa (Chapter 6). On that continent, 325 million people lack access to safe water. The majority of those who lack water live in rural areas. Africa is second to Australia in dryness, but it is home to 15% of the global human population and has only 9% of global renewable water resources. Most of Africa’s surface water has become polluted by human activities, and its wells are rapidly becoming dry. Impacts of climate change and climate variability are making water scarcity even more stressful. Technologies used for water harnessing are outmoded and inefficient. African countries need to modernize water purification technology; it is essential that these countries adopt new methods like roof, pavement, and urban water catchment to recharge its declining groundwater level. Provision of safe drinking water policy needs to change from piped water in every home to appropriate water-use technology in every home. Some potential new technologies still require further research. Chapter 6 highlights some recent developments of nanomaterials that give promise to future water purification trends. Similarly, small-scale water harnessing technologies are outlined for groundwater recharge and drinking water purification. The design of water education in African nations is reviewed, and specific steps for improvement are also given in this chapter.

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Organochlorine Pesticide Contamination in the Kaveri (Cauvery) River, India: A Review on Distribution Profile, Status, and Trends Water sources such as rivers are often reported to contain various organochlorine pesticides (OCPs) because of their tremendous usage in agriculture and vector control activities (Chapter 7). Monitoring studies on rivers in India are limited, and the presently reviewed Kaveri River is one such river in southern India that has served as a lifeline (agriculture, drinking water, and industry) for centuries. The frequently reported OCPs in this river include hexachloro-cyclohexane (HCH), dichloro-diphenyl-trichloroethane (DDT), endosulfan, aldrin, dieldrin, and heptachlor epoxide. The concentrations of HCH, DDT, and endosulfan residues in Kaveri’s water were detected at levels up to 2300 ng/L, 3600 ng/L and 15400 ng/L, respectively. While in sediment, HCHs and DDTs were reported with maximum concentration of 158 ng/g dw and 9.15 ng/g dw, respectively. Even biota (fish, shrimp) samples collected in the river were found to contain significant levels of HCH (228 ng/g) and DDT (2805 ng/g) residues. The levels of some of the OCPs in the Kaveri River exceeded safety guideline values; therefore, these waters are considered a threat to the population because continuous exposure cannot be ruled out.

Ganges River Contamination: A Review Persistent organic pollutants (POPs), pesticides, organotin compounds, perfluorinated compounds, heavy metals, and other emerging contaminants like pharmaceuticals, personal care products, steroids, hormones, phthalates, plasticizers, etc., have been used in a wide range of agricultural, sanitation, and industrial commodities in the Ganges River basin, resulting in vigorous deterioration of the river (Chapter 8). India has recently prepared the National Implementation Plan (NIP) of the Stockholm Convention. The Ganges is believed to be highly polluted with POPs and other contaminants; however, no systematic study and analysis of POPs and other toxics have been conducted. This chapter aims to examine the present status, spatial and temporal distribution pattern of POPs and other chemicals in multi-compartment Ganges River surroundings. This review leads to the conclusion that the Ganges River is highly contaminated with DDT, HCHs, and heavy metals, etc. However, the scarcity of data on other POPs and emerging contaminants makes it challenging to assess their exposure in the entire length of the river. No evidence of a general decline in DDT and HCH residues in the river and its biota were found in this study.

Water Challenges in India and Their Technological Solutions Problems associated with water can be broadly grouped as (a) inadequate availability of water, (b) poor quality of water for its intended use, and (c) indiscriminate use of this valuable natural resource (Chapter 9). The technological approaches for solving the problems may therefore emanate from (a) recovering 18 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

water from sustainable resources, (b) augmentation of quality of water from available and accessible sources, and (c) renovation for recycling. Technology missions on reclamation, augmentation, and renovation for water was initiated in 2009 to address the water challenges following three-pronged technological approaches stated by the Union Ministry of Science and Technology. The mission shaped several research-led solutions through nationally coordinated approaches.

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Water Resources, Water Scarcity Challenges, and Perspectives The continuously growing global water scarcity and the evidence for climatic changes require a refocus on reliable and sustainable water supplies, especially in arid and semiarid regions, as they are the most water-deprived regions in the world (Chapter 10). Population growth, urbanization, and increasing water demands intensify the pressure on many water resources, causing rapid depletion of supply and quality degradation to a degree that part of the resources may not be safe to use and can cause health and environmental risks. Such adverse development is strongly apparent in the Middle East and other places where global warming impacts are already apparent, leading to a situation in which available water resources are depleted, deteriorated, and unable to satisfy basic needs. To provide an integrated picture of water challenges and possible solutions at global and regional scales, a drivers-pressures-state-impacts-responses (DPSIR) framework is applied to give details regarding the water shortage issue and mitigation measures, with examples from the Middle East, California, India, and other regions facing these challenges. Reversing the trend of growing water shortages, while securing basic water needs for all, is a challenging and ambitious task, but an achievable one provided that comprehensive and consolidated water management strategies are implemented. A comprehensive and integrated water management policy combining advanced management and conservation as well as the harnessing of nonconventional water resources (water reuse and desalination), together with trans-boundary cooperation on shared water resources can provide a sound solution to the challenges posed by water scarcity are discussed in this chapter.

Contaminated Profiles of Perfluorinated Chemicals in the Inland and Coastal Waters of Japan Following the Use of Fire-Fighting Foams This chapter deals with the impact of two natural disasters (earthquake followed by tsunami) and consequent human activities on the quality of inland and coastal waters of Japan (Chapter 11). Two cases of accidental petrochemical fires in Japan that involved the use of aqueous film-forming foam (AFFF) have been investigated as potential sources of perfluoroalkly substances (PFASs) in inland and coastal waters of Japan. PFASs were identified and quantified in seawater, lake water, snow, runoff, and surface soil samples. Concentrations of individual PFASs were measured in water samples employing the use of high-performance liquid chromatography with electrospray tandem mass spectrometry. The 19 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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total concentrations of the sum of PFASs in seawater and lake water samples from Tomakomai ranged from 0.32 to 405 ng/L. The greatest concentration of perfluorooctane sulfonate (PFOS) was found at T19 (311 ng/L) of December 2003. Total fluorine (TF), inorganic fluorine (IF) and extractable organic fluorine (EOF) were also measured in the samples, using a newly developed method, namely combustion ion chromatography for fluorine (CIC-F). The results revealed that IF was the major contributor to TF in water samples. However, the major portion of organofluorine fraction still remains unknown, suggesting the occurrence of other unknown fluorinated organic compounds, in addition to known individual PFASs such as PFOS, PFOA, and perfluorononanoic acid. Additionally, composition and profiles of PFASs in two locations impacted by AFFF were different. This suggests different sources of organic fluorine released from AFFF. In Tomakomai, the release of AFFF is expected to be a major source of PFASs; while in Kashima, other sources such as the fluorochemical industry appears to contribute to a major source of contamination.

Overcoming the Water Treatment Challenges and Barriers in Small, Rural, And Impoverished Communities in Developing Countries Many developing countries face unique water treatment challenges and barriers because the communities do not have a well-established socioeconomic, educational, and technological infrastructure that is capable of supporting conventional water treatment solutions (Chapter 12). It is not uncommon for many proposed and implemented water treatment solutions to fail in developing countries, especially in small, needy, and rural communities. This chapter examines underlying factors that contribute to water treatment challenges and barriers in developing world communities and proposes a systems approach for developing a sustainable water treatment solution in these communities. Five different categories of challenges and barriers to water treatment solutions in developing countries are identified and examined: economics-driven factors; knowledge-based factors; sociocultural implications; adequacy of supporting infrastructure; and environmental specifics. A systems approach, which stems from the need to resolve these challenges, is elucidated in an attempt to minimize the failure rate of implementing inadequate water treatment solutions in little rustic deprived communities of the developing world.

Building a Sustainable Water Management System in the Republic of Serbia: Challenges and Issues The Republic of Serbia is an example of a developing country with a water management system that has not adequately transitioned to address the need of the new socioeconomic paradigm (Chapter 13). The goal of this study is to identify and evaluate the existing barriers that hinder the development and implementation of an integrated national water resources management system and find ways to mitigate the upcoming effects of climate change and successfully manage the 20 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

water resources for the next generations. To achieve this goal, the water resources management system in Serbia is examined through the prism of regulations, management, engineering, and education, which represent principal pillars of every national socioeconomic system. The key findings and the outcome of this study reveal that an in-depth analysis of the existing situation and identification of barriers represent the initial steps in the process of developing and implementing an integrated national water management system.

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Sustainable Water Cleaning System for Point-of-Use Household Applications in Developing Countries to Remove Contaminants from Drinking Water A point-of-use (POU) water treatment system that is based on pyrolysis of banana peels (PBP) adsorption was evaluated with synthesized and real water samples (Chapter 14). PBP resulted in the formation of a large porous surface area adsorbent with strongly negative surface charges. Batch and continuous flow studies were conducted to determine the adsorption capacity and the rate of removal of pollutants.

Potential Uses of Immobilized Bacteria, Fungi, Algae and Their Aggregates for Treatment of Organic and Inorganic Pollutants in Wastewater Bioremediation of wastewater using microorganisms and their aggregates is recognized as an efficient green treatment (biological origin) with a relatively low cost compared to conventional physical and chemical treatment processes (Chapter 15). Heterotrophic microorganisms such as bacteria, fungi and often microalgae are used for removal of targeted pollutants from wastewater. Microorganism can be used in the following ways • •

Direct mixing of free microorganisms with waste water; there is no separation between microorganisms and treated water. Microorganisms immobilized in bedding materials or encapsulated within a matrix; there is a distinct separation between microorganisms and the treated water.

However, immobilized or encapsulated cells are considered more efficient than free cells as they have better metabolic activity, less vulnerability to toxic substances, and greater plasmid stability. Lignocellulosic biomasses, ceramics, polymers from both natural and synthetic origin are commonly used as bedding materials or for entrapment of microorganisms within it. These immobilized cells show immense potential to clean up a wide range of pollutants including phenolic compounds, hydrocarbons, propionitrile, organic and inorganic dyes, N,N-dimethylformamide, pyridine, benzene, toluene, xylene, heavy metals, and unwanted amount of nutrients such as nitrogen and phosphorus from 21 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

the wastewater streams. Integrated process of assimilation, adsorption and biodegradation is the sole responsible mechanism behind wastewater remediation by immobilized microorganisms.

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Improving the Water Holding Capacity of Soils of Northeast Brazil by Biochar Augmentation The northeast area of Brazil, a semiarid region, frequently experiences severe drought (Chapter 16). Despite rainfall during two or three months of the year, the presence of soils with low water retention capacity, together with intense insulation, results in infiltration of water to deeper soil layers, rapid evaporation, and deficiency of water during the remainder of the year. In this work, the authors propose that the use of soil conditioners derived from agricultural and industrial wastes improves soil water supply. Five biochars, prepared by slow pyrolysis, were produced from green coconut shells, orange peels, palm oil bunch (PO), sugarcane bagasse (SB), and water hyacinth (WH) plants. Charcoal fines obtained from the metallurgy industry were also used. The soils investigated were two quartzarenic neosols denoted QN1 and QN2. After mixing with 5% (m/m) of biochar, both soils showed an increased water-retention capacity, compared to the original samples. The biochars that provided the best water retention were PO and SB (absolute increases of 5.5% and 6.5%, respectively) for soil QN1, SB, and WH (absolute increases of 7% and 8%, respectively) for soil QN2. These results could be explained by the polarity of the biochars, as shown by their hydrophilicity, measured by 13C NMR spectroscopy, as well as by the increased presence of micropores that could physically retain water (revealed by scanning electron microscopic analyses).

Reclaimed Water Systems: Biodiversity Friend or Foe Surface-flow type constructed wetlands are commonly prescribed by local authorities for stormwater and wastewater treatment in many parts of Australia and elsewhere (Chapter 17). Despite the fact that little is known about the biodiversity in constructed wetlands up to now, artificial wetlands can potentially develop and become complex ecosystems with a variety of fauna and flora, including macroinvertebrate communities. Such communities could play an important role in the ecological functioning of healthy aquatic ecosystems because they process detritus and algae and also provide food to other aquatic animals. In the meantime, nuisance macro-invertebrate species including chironomid midges and mosquitoes associated with man-made systems could raise significant health concerns as disease vectors. Water quality conditions such as dissolved oxygen, temperature, nutrients, pH, heavy metal, and organic contaminants are the key determinants of macroinvertebrate populations in man-made reclaimed water systems. Therefore, the potential impact of different reclaimed water quality parameters on aquatic macroinvertebrate assemblage has been reviewed systematically. This chapter underscores the importance of promoting biodiversity 22 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

through the maintenance of healthy wetlands, i.e., water-quality monitoring and control aspects, and beneficial and sustainable ecosystem services that have consequences for human health, i.e., disease vector regulations.

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Nanotechnology Solutions for Global Water Challenges The rapid and continued growth in the area of nanomaterial-based devices offers significant promise for addressing future water quality challenges (Chapter 18). Meager availability of clean and safe drinking water is responsible for more deaths than war, terrorism, and weapons of mass destruction combined. This suggests that contaminated water poses a significant threat to human health and welfare. Additionally, standard water disinfection approaches such as sedimentation, filtration, and chemical or biological degradation are not fully capable of destroying emerging contaminants (e.g., pesticides and pharmaceutical waste products) or certain types of bacteria (e.g., Cryptosporidium parvum). Nanomaterials and nanotechnology-based devices can potentially be employed to solve the challenges posed by various contaminants and microorganisms. Nanomaterials of different shapes, namely nanoparticles, nanotubes, nanowires and fibers, have the ability to function as adsorbents and catalysts. They have an expansive array of physicochemical characteristics, making them highly attractive for the production of reactive media for water membrane filtration, a vital step in the production of potable water. As a result of their exceptional adsorptive capacity for water contaminants, grapheme-based nanomaterials have emerged as a subject of significant importance in the area of membrane filtration and water treatment. Also, advanced oxidation processes, with or without sources of light irradiation or ultrasound, have been found to be a promising option for water treatment at near ambient temperatures and pressures. Furthermore, the uses of visible light-active titanium dioxide photocatalysts and photo-Fenton processes have shown a significant potential for water purification. A wide variety of nanomaterial- based sensors for monitoring water quality are also reviewed in detail.

Sustaining Water Resources: A Global Imperative Global freshwater is finite, and its supply is severely strained by competing forces of an expanding world population on the one hand and alterations in the water cycle as a result of climate change on the other (Chapter 19). A range of regional concerns regarding freshwater use have been identified and must be addressed in order to maintain the sustainability of this precious resource. Rigorous conservation methods constitute an essential approach, whether this involves farm use, electric power generation, all related emerging energy technologies, or domestic use. Innovative technologies such as water reuse, desalination, and additional water storage infrastructure to replenish groundwater supplies are effective in providing restorative measures to augment world water 23 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

supplies. But water is unevenly distributed globally, resulting in water-deprived regions with no available safe water. As demand for water intensifies, regional integration will provide benefits of enhanced security of supply, improved public health, more reliable food supply, and better economic efficiency.

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Conclusions A variety of water challenges are faced by various countries globally. Some of the challenges and solutions have been highlighted here. It is important to remember that water pollution in our modern society is inevitable. We need to improve monitoring of point and nonpoint source pollution. Furthermore, it is important to use effective safety measures that can prevent further pollution. Rain and snow are nature’s way of recycling water; however, rain and snow are now usually contaminated with various pollutants that we have added to the atmosphere. It is still desirable to collect rainwater and use it for a variety of purposes. To achieve water sustainability, water must be used judiciously, and production of wastewater should be minimized. Some water reclamation methods are covered here. Diverse solutions are essential for different countries; recognition of various solutions that have been found can help both developing and developed countries.

References 1. 2. 3.

4. 5.

6.

7.

8. 9.

Ahuja, S. Handbook of Water Purity and Quality; Elsevier: Amsterdam, 2009. Ahuja, S. Arsenic Contamination of Groundwater; Mechanism, Analysis, and Remediation; Wiley: New York, 2008. Novel Solutions to Water Pollution; Ahuja, S., Hristovski, K., Eds.; ACS Symposium Series 1123; American Chemical Society: Washington, DC, 2013. Ahuja, S. Monitoring Water Quality: Pollution Assessment, Analysis, and Remediation; Elsevier: Waltham, MA, 2013. Comprehensive Water Quality and Purification; Cruse, R. M., Wing, E., Lee, S., Chen, X., Ahuja, S., Eds.;Elsevier: Kidlington, Oxford, U.K., 2014; Vol. 4, pp 41−56. Ahuja, S. Environmental Perspectives in Water Sustainabilty. In Teaching and Learning about Sustainability; ACS Symposium Series 1205; American Chemical Society, Washington, DC, 2015. Ahuja, S. Assuring Water Purity by Monitoring Water Contaminants from Arsenic to Zinc; American Chemical Society Meeting, Atlanta, March 26−30, 2006. Brundtland, G. H. Our Common Future, The World Commission on Environment and Development; United Nations, 1987. New Partnership for Africa’s Development; 2006, www.un.org/en/ africarenewal///subjindx/nepad.html. 24 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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10. Groundwater Depletion; available at http://water.usgs.gov/edu/ gwdepletion.html (August 28, 2015) 11. China City Statistics, Urban Water Supply Statistics Yearbook; 2012. 12. Tao, T.; Yin, K., Nature 2014, 511, 527; July 31, 2014. 13. Qiu, J. Nature http://dx.doi.org/10.1038/news.2009.111; 2009. 14. Scott, J.; Carter, R.; Drury, A. IR; Cengage Learning, 2014 15. Chem. Eng. News 1978 August7. 16. Chem. Eng. News 1978 Sept.25. 17. McNeil, E. E.; Otson, R.; Miles, W. F.; Rajabalee, F. J. M. J. Chromatogr. 1977, 132, 277–285. 18. Ahuja, S. Water Sustainability and Reclamation; American Chemical Society Meeting, San Diego, March 25−29, 2012. 19. Ahuja, S. Water Reclamation and Sustainability, Elsevier, Amsterdam, 2014. 20. Ahuja, S. CHEMTECH 1980, 11, 702. 21. Ahuja, S. Ultratrace Analysis of Pharmaceuticals and Other Compounds of Interest; Wiley: New York, 1986. 22. Ahuja, S. Trace and Ultratrace Analysis by HPLC; Wiley: New York, 1992.

25 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

Chapter 2

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Raising Awareness of Water Issues: The Education Connection, the Educational Potential Shelby Maurice and Mark A. Benvenuto* Department of Chemistry and Biochemistry, University of Detroit Mercy, 4001 W. McNichols Road, Detroit, Michigan 48221-3038 *E-mail: [email protected].

The challenges posed by finite amounts of clean, potable water and a continuously growing human population are still not well understood by a significant portion of that population. An increased awareness of water issues, specifically of waste water treatment technologies and sanitation practices, can be attained if these issues are addressed thoroughly and repeatedly in general chemistry classes at both high school and college level, and in upper level undergraduate chemistry curriculum courses such as industrial chemistry and environmental chemistry, as well as engineering classes. This chapter presents a detailed, mapped approach to raising the awareness of current water issues by repeated exposure in college chemistry classes in several different courses.

Introduction Water may be the single most important chemical for the propagation of life, if one considers all aquatic life, including deep sea organisms – although one might argue air is equally so – and it is certainly the material that humankind has chosen to live next to for all of known history. Living near salt water as well as fresh water has provided humans with food, with drinking water in the case of freshwater lakes, rivers, and streams, and with a means of moving ourselves and heavy objects, once we had discovered how to build boats. The human population explosion that has occurred in the twentieth century though has put strains on water supplies that have not occurred at any other time in history (1, 2). The sheer number of people living © 2015 American Chemical Society In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

on or near water, and the construction of numerous dams across major and minor rivers mean that existing water resources are stressed more severely than they have been at any other time (3). In this environment it becomes imperative for an educated citizenry to understand water issues, and how those issues affect themselves, their local community, and the greater global community. What can be called ‘water education’ can be built into the chemistry curriculum at several levels (4–13).

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The Issues: Water Treatment Technologies There are several well-established means of purifying water of soluble, slightly soluble, and insoluble contaminants. It is generally agreed that desalination, waste water treatment, and conservation are the three categories into which all water purification falls, with desalination being the most expensive, waste water treatment such as sewage clean-up second, and conservation efforts the least expensive of the three (3, 4). Desalination There are several different methods of desalination of sea water or brackish water. A partial, but non-exhaustive list of them includes: i. Reverse osmosis ii. Multi-stage flash distilling – roughly 75% of operations iii. Membrane distillation iv. Electrodialysis reversal v. Nano-filtration vi. Ion exchange vii. Solar desalination viii. Freezing desalination By far the most common is multi-stage flash distilling in which some amount of saline or brackish water is heated rapidly – flashed – and the condensate collected, resulting in pure water. By repeating the flashing process numerous times, large amounts of clean water can be collected, while the more saline fraction of the water is returned to the source. Desalination efforts can be performed on a small scale, such as in the rescue and emergency kits of recreational boaters. But enormous amounts of water are desalinated through industrial-scale plants in various countries, or off their coasts. Israel, Singapore, and Venezuela all have large desalination plants that serve their populations. Sewage – Waste Treatment Waste water treatment and sewage treatment often mean exactly the same thing in terms of chemical purification and re-concentration of water. While the 28 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

steps in any reclamation process differ based on the starting aqueous mixture, there are several common, broad steps that all waste water must undergo for treatment and clean-up. i.

ii.

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iii.

iv.

v.

vi.

vii.

Pre-treatment: This is the removal of macroscopic wastes from an incoming water stream. This includes yard waste in many municipal areas, as well as pieces of litter and other objects. Primary treatment – settling: This involves allowing smaller particulate matter to settle to the bottom of tanks, thus clearing the water further, usually at very low cost. Fat and oil removal, if necessary: This is simply the removal of non-aqueous liquid material, either through mechanical means such as skimming, or through chemical means such as encapsulation by surfactants. Secondary beds – microbial digestion: This step involves the removal of microscopic and in some cases such microscopic materials by beneficial microbes. Chemical addition, chlorine: The addition of chlorine to reclaimed water is imperative when the water will be re-used by people. The chlorine serves as a thorough and yet inexpensive anti-bacterial shock. Settling beds/ponds: This step can occur before the addition of chlorine, but is designed to be a final physical separation of any foreign materials from the water. Discharge to local waters

Importantly, any combination of these steps is usually less expensive than the desalination of sea water. This is a matter of the cost of the energy involved in desalination, in pumps to force water through membranes, in the cost of the membranes, and in the cost of the electricity to run such operations. While there are some costs involved in sewage and waste-water treatment, the uses of settling ponds and microbial digestion often mean cost savings in comparison (5, 14, 15). Water Conservation The third of the three broad categories when it comes to water purification and use – conservation – is by any and all measures the least expensive. This is because it essentially involves doing nothing but maintenance on already existing systems. Being aware of and fixing leaks in the system, from water mains all the way to the consumer and home tap leaks is much more a matter of improving the behavior of users than it is a matter of the chemistry that is involved in separating water from salts or other pollutants. In areas where population density is high, and there is the belief that people will not change voluntarily, systems of tax incentives as well as punishments have been used effectively to conserve water. This often means lowering taxes on consumers and businesses that show less water use in monthly summaries, as well as police actually fining residents for wasting water, such as watering suburban lawns on what have been designated ozone alert days (which now occurs in several municipalities in the United States). 29 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Remaining Materials – Organics, Such as Pharmaceuticals One current issue with water chemistry and purification, one that is gaining a certain amount of notice, even in the common press (3–5, 15–20), is that of pharmaceuticals that remain in water even after treatment in water and sewage treatment plants. Essentially, pharmaceuticals are active organic molecules that are designed to be relatively stable in water – since humans and animals that ingest such materials are themselves mostly water – and sewage treatment plants have never been designed to neutralize such materials. The end result is that pharmaceuticals which have been urinated or excreted into toilets, passed through animals and into their waste materials, or that have been disposed of in toilets on purpose, as a way to keep them from garbage cans and the supposedly prying hands on small children, enter our waterways and our larger environment, essentially untouched and still active. While a chemical solution to this problem does not yet exist, this issue is certainly one that can be brought into the classroom for discussion and for raising awareness.

Water in the Curriculum General Chemistry Content The content of general chemistry textbooks has not changed markedly for the past several decades (21–24). Numerous textbooks cover the following subjects, and when they are aimed at students who are science and engineering majors, usually treat these topics in considerable detail: a. b.

Salts, nomenclature, ionic materials Reactions in solution, in water i. The basis of stoichiometry ii. The basis of redox and electrochemistry iii. Applications: from human health to battery-powered automobiles

c. d.

Heat capacity, water versus other liquids, and versus metals Solutions, concentrations, molarity i. Water as solvent, water as solute ii. The light-hearted, water as a component in mixed drinks

e. f. g. h.

Molecular structure, polarity, hydrogen bonding and water Colligative properties, including the vant Hoff factor Chemical equilibria, water as organic by-product Acid – base chemistry, pH and such measurements in water

In each of the above topics, it is not particularly difficult to focus on how the water can be the main theme behind the concept. In several of these cases, the chemistry involved is utterly dependent on water. 30 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Choosing just one example from the above list, “molecular structure, polarity, and hydrogen bonding,” a very simple experiment that can easily be run in the first semester freshmen chemistry laboratory is the mixing of several different amounts of an alcohol such as ethyl alcohol and water, and graphing the resultant volumes. It should be obvious that 50 mL of one liquid or the other is 50 mL. However, when the proportions are changed – 45 mL ethanol added to 5 mL water, then 40 mL ethanol added to 10 mL water, and so on, until a mixture of 25 mL of each is combined, the sum volume is never 50 mL. The largest deviation that students find tends to be the 25:25 mL mixture, which combines to form a 47.5 mL total volume of solution (within reasonable error, using standard graduated cylinders for measurement). This is an easy example of a means to show how hydrogen bonding affects a macroscopic measurement, volume. Likewise, numerous reactions in the first year of a general chemistry course involve the production of water. Indeed, understanding solubility and insolubility often includes the discussion of acid and base combinations that produce water, and note that it is the production of water that drives the reaction, by removing ions from solution. As well, the basic understanding of molarity and molality can be one in which the amount of materials, usually solids, dissolved in water is the main topic of discussion. Numerous teachers have asked students to compute the molarity of seawater, or have provided data so that the concentration of some material in water, often pollutants, can be computed. In short, every item listed above has some equally straightforward experiment that can utilize water, and thus raise student awareness of water chemistry.

Environmental Chemistry Content The technologies we have already discussed: desalination, sewage clean-up, and conservation are almost impossible to omit from an environmental chemistry class. Such classes usually discuss water pollution in considerable detail. For example, the processes for water desalination that were just listed indicate that multi-stage flash distilling is the major means by which water is desalinated. This is also an energy intensive operation, and this point can be the beginning of an in-class discussion on energy as part of a chemical equation. Such a discussion can also focus on the fact that it is energetically and economically more favorable to clean up once-used water, also called grey water, with settling ponds and microbes than it is to desalinate sea water. Thus, this example can serve to initiate a discussion and increase understanding for students in an environmental chemistry class. But this could also be applicable in a basic biochemistry class should microbial clean-up of water be the focus of the discussion. Additionally, this point can be used in first semester physical chemistry classes when energy is the aspect of water purification being examined. An easy off-shoot of the larger subject of water in an environmental chemistry class is the water cycle in local areas. This is both straightforward and easy to use to bring home for students the importance of water and water chemistry, since it affects them and their families (19). 31 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

Industrial Chemistry Content

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The production of water, discussed above, is a subject often covered in industrial chemistry classes, simply because clean water is required for numerous large-scale chemical processes (25). Water use in the following processes is all performed daily on a massive basis: The Chlor-Alkali Process. This produces sodium hydroxide, elemental chlorine, and elemental hydrogen according to the following reaction:

All three products are used profitably, and water is a reactant as well as the solvent for the process. The Solvay Process. While Na2CO3 production is the main product, and the reaction chemistry can be shown simply as follows:

The process is much more complex and intricate, and importantly it requires water again as both reactant and solvent. The Frasch Process. Elemental sulfur is still extracted from underground deposits in some parts of the world using s triple tube assembly that forces superheated water into the sulfur deposit to force it to the surface. While there is no reaction chemistry to accompany this, water is essential to the process. The Contact Process. This method of sulfuric acid production requires water once again both as reactant and solvent. It can be outlined in five reactions.

It can be noted when discussing this chemistry that simply trying to “stop” the process at the third step and attempt direct addition of sulfur trioxide to water is never done on a large scale because it produces a corrosive aerosol mist. The Ostwald process. The production of nitric acid is another absolutely huge piece of chemistry, one that is probably taught in all industrial chemistry courses. The three general reactions that define it again require water. They are:

Here we see that water is both a product and at a later step a reactant. Additionally, the use of water in the final step produces more nitrogen monoxide, which is used to perpetuate the reaction. 32 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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The Washoe Process. This method of producing silver is not one that lends itself easily to reaction chemistry, but steam is required to heat the ore – mercury amalgam, and ultimately to isolate silver metal. Pulp and paper production. This is another example in which an industrial process utterly depends on water. Almost every step of the pulp and paper making process requires large amounts of clean water, and even though it is not possible to present chemical equations that show neatly how it is used, the production can not be accomplished without it. Mining operations and water. The term “mining” implies digging holes in the ground and putting men and machinery into them to extract some material. However, this has become something of a misnomer, as solution mining is now used for several water-soluble materials, such as the just mentioned sulfur, and especially for potash. In such solution mining operations, hot water is injected into the mine, the potash is solvated, and the brine solution is extracted. This is an example of a very large-scale water use for western Canada, where such mines are located. Oil refining and fracking. The discussion of what get called “fracking fluids” has become part of what is reported in the national and local news, usually in relation to some odd or exotic chemical used in the mix. But an understanding of fracking fluids means the awareness that most of any fluid mix is water. This means a great deal of water is needed for such operations, and also means that some way needs to be found to separate the water from the other materials whenever it is returned to the surface above the fracking site.

Incorporation into the Curriculum In General Chemistry In any general chemistry class, several opportunities can be taken to emphasize water at every point of discussion. Water can be the thread or theme that connects numerous concepts throughout the entire course. As well, general chemistry is taken by a relatively large number of students, certainly of science and engineering students. Three examples that utilize water extensively follow. Scaling up. Reaction chemistry examples do not have to be in grams or milligrams. They continue to be at this scale for no reason other than this is the general range of balances in teaching laboratories, to which many general chemistry classes are connected. But it is quite easy to scale up a problem in which some reaction is run in water and a product is formed (silver nitrate, for example) from grams to tons, and to determine how much water would then be needed. Emphasis on human health. A large number of students enter colleges and universities with the plan to graduate and then attend a medical, dental, veterinary, or some other health profession-related school. Tying together the idea of access to clean water, its consumption, and its use brings the chemistry being taught to life by making it immediately relevant. The subject matter is no longer simply material to be memorized. It is information and knowledge that these students will need and will use in their next educational undertaking. 33 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

Water and current quality of life. It is not difficult to make connections between chemical products that are made today, and the water that isolates or produces them. The fields in which medicines, refined metals, plastics, and fertilizers will be used may seem wide (and scattered) to students, but water in one substance that connects them all. This can be a very useful “hook” as a teaching tool.

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In Organic Chemistry In the traditional curriculum, organic chemistry remains the major chemistry course of the sophomore year, although numerous colleges and universities have in the past decade moved to a model in which some organic chemistry is taught in the first year, while subjects such as equilibrium, entropy, and kinetics are moved to the second year. But wherever it falls, the organic chemistry course can serve as a course of study in which one can emphasize where water works as a solvent, and where it does not. Additionally, in this class the instructor can discuss points of water production, meaning often as by-product. These condensation reactions are numerous. A non-exhaustive list includes: a. b. c. d. e. f. g. h. i. j.

Aldol condensation Claisen – Schmidt condensation Darzens condensation Dieckmann condensation Guareschi – Thorpe condensation Knoevenagel condensation Michael condensation Pechmann condensation Schiff’s Base condensation Ziegler condensation

Using just the Schiff’s Base condensation as an example, as shown here, it can be explained that not only is water the reaction by-product, but its formation is the energetic driving force.

The Schiff’s base condensation is a very “forgiving” reaction, in that it can run in numerous organic solvents. But it cannot be run in water or in alcohols that still contain a small percentage of water (such as 96% ethanol). It is the formation of water that drives the reaction to completion, and thus using it as or in a solvent will drive the equilibrium back to the reactants’ side. In Industrial and Environmental Chemistry We have already discussed the numerous large scale processes that require water either as a reactant or as a solvent, or both. In addition to this, past and present incidents can be discussed throughout such a class. This does not need 34 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

to be an eternal litany of spills. On the contrary, such negative incidents can be counterbalanced by examples of processes where a secondary product finds a positive use. Additionally, the improvements that processes undergo over the course of time deserve to be noted. An example of this might be how the HCl produced in an organic synthesis, which in past decades might have been discarded, is now captured in water and used in some other process (the pickling of steel and other metals accounts for slightly more than half of all HCl produced today).

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Conclusions This chapter has outlined several points where water can be used in the chemistry curriculum to prove some learning point. Water is not only a common material, it can serve as a common example in general chemistry, organic chemistry, environmental chemistry, and industrial chemistry classes. Its structure, properties, and reactivity can be an educational focus at several points in each of these classes. Constant reinforcement of water chemistry and its many uses develops awareness of water’s abilities and limitations in students. All the points that have been discussed are quite easy to incorporate in the classes mentioned, which can make water a recurring, and oftentimes central topic in the curriculum.

References 1. 2. 3. 4.

5. 6.

7. 8. 9.

Saline Water Conversion; ACS Advances in Chemistry Series 27; American Chemical Society: Washington, DC, 1960. Saline Water Conservation – II; Gould, R. F., Ed.; ACS Advances in Chemistry Series 38; American Chemical Society: Washington, DC, 1963. Letter Report Assessing the USGS National Water Quality Assessment Program’s Science Plan; National Academies Press: Washington, DC, 2011. Letter Report Assessing the USGS National Water Quality Assessment Program’s Science Framework; National Academies Press: Washington, DC, 2010. Urban Stormwater Management in the United States; National Academies Press: Washington, DC, 2009. Nutrient Control Actions for Improving Water Quality in the Mississippi River Basin and Northern Gulf of Mexico; National Academies Press: Washington, DC, 2009. Water Contamination Emergencies: Can We Cope? Thompson, K. C., Gray, J., Eds.; Royal Society of Chemistry: London, 2004. Water Contamination Emergencies: Enhancing Our Response; Thompson, K. C., Gray, J., Eds.; Royal Society of Chemistry: London, 2006. Water: The Power, Promise, and Turmoil of North America’s Fresh Water. National Geographic 1993 November. 35 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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10. Gorbachev, M. Water: The Globe’s Most Precious Resource, the World’s Most Pressing Problem. Civilization, A Special Section 2000 October/November. 11. Water: Our Thirsty World. National Geographic 2010 AprilA Special Issue. 12. Troubled Waters: Are We Emptying the Oceans? Virginia Quarterly Review 2011 Summer, 87 (3). 13. The Future of Fish. Time 2011 July18, 28–36. 14. Particulates in Water: Characterization, Fate, Effects, and Removal; Kavanaugh, M. C., Leckie, J. O., Eds.; ACS Advances in Chemistry Series 189; American Chemical Society: Washington, DC, 1980. 15. Environmental Chemistry of Lakes and Reservoirs; Baker, A., Ed.; ACS Advances in Chemistry Series 237; American Chemical Society: Washington, DC, 1994. 16. Harvard Medical Advisor, Pharmaceutical and Personal Care Products. The Detroit Free Press 2011 July3, D4. 17. Utah Waterways Test Positive for Prescription Drugs. KSL TV (accessed 29 April 2015) http://www.ksl.com/?nid=148&sid=3959442. 18. Area Tap Water Has Traces of Medicines. The Washington Post 2008 March10, B01. 19. Detroit Water Dept. Must Reorganize to Survive. DBusiness, Annual 2014 (accessed 29 April 2015) http://www.dbusiness.com/Blogs/Annual-2014/ Detroit-Water-Dept-Must-Reorganize-to-Survive/. 20. It’s All in the Water: Studies of Materials and Conditions in Fresh and Salt Water Bodies, Benvenuto, M. A., Roberts-Kirchhoff, E. S., Murray, M. N., and Garshott, D. M., Eds.; ACS Symposium Series 1086; American Chemical Society: Washington, DC, 2011. 21. Partington, J. R. Text-Book of Inorganic Chemistry; MacMillan & Co., Ltd.: London, 1933. 22. Brown, T. L.; LeMay, H. E., Jr. Chemistry: The Central Science; PrenticeHall: New Jersey, 1977. 23. Masterson, W. L.; Slowinski, E. S. Chemical Principles, 4th ed.; W.B. Saunders Company: London, 1977. 24. Brady, J. E.; Senese, F. Chemistry: Matter and Its Changes, 5th ed.; John Wiley & Sons, Inc.: New Jersey, 2009. 25. Benvenuto. M. A. Industrial Chemistry; DeGruyter: Berlin, 2014.

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Chapter 3

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The Effects of Climate Change on Water Resources of Small Developing Countries – A Case Study of the Republic of Macedonia Trajče Mitev,1 Tomas Custodio,2 Kiril D. Hristovski,*,2 and Jon W. Ulrich3 1Faculty of Natural and Technical Sciences, University “Goce Delčev”– Štip, 2000, Republic of Macedonia 2The Polytechnic School, Ira A. Fulton Schools of Engineering, Arizona State University, Mesa, Arizona, 85212, United States 3Applied Sciences and Mathematics, College of Letters and Sciences, Arizona State University, Mesa, Arizona, 85212, United States *E-mail: [email protected]. Tel: + 1 480 727 1291.

In absence of high-resolution climate-change model predictions, employing empirical data collected over a long period may be the only viable option to predict the climate change implications affecting small and developing countries where the socio-economic structure is strongly rooted in water dependent sectors such as agriculture or energy production. The overarching goal of this study is to demonstrate the suitability and significance of employing empirically obtained historical data in predicting the impact of future global climate change trends in a small country like the Republic of Macedonia. The climate change effects on the national surface water resources of Macedonia were assessed by (1) examining temperature trends and other descriptors of global warming spanning over 50 years; and (2) testing three data-driven hypotheses. The 50-year historical records describe statistically significant trends: increase in national average temperatures, surface water resources depletion, and fluctuations in the magnitude of precipitation. Realizations of such grim scenarios could create

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substantial socio-economic and environmental challenges for the Republic of Macedonia if adequate mitigative measures are not implemented.

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Introduction Concerns of climate change—enabled extreme weather events have risen over the last decade (1–3). Arguments against the greenhouse gas induced climate shifts are slowly and steadily being silenced by the overwhelming evidence, which steadily emerges as the number of record temperatures continue to increase (4–8). These trends offer nothing more than grim projections of future scenarios (9–12). Published predictions from climate change models generally project increase in temperatures and changes in precipitation and surface water hydrology on a regional scale; however, for small countries, which may encompass only a small portion of a larger region, the resolution of even high resolution climate change models generates a high-level of uncertainty on a local or national scale (13–17). As such, these global models are often rendered unsuitable for predicting climate changes or developing national or local mitigation strategies that would enable enhanced socio-economic and ecological resilience of small countries. Alterations in temperature, precipitation, surface hydrology, and subsequent impacts on the quality and quantity of national water resources could have multifaceted environmental, socio-economic, and political implications, and be one of the main factors determining the level of seriousness of these climate change consequences (15, 18–23). Specifically, climate change consequences can prove to be quite significant for small and especially developing countries where the socio-economic structure is strongly rooted in water dependent sectors such as agriculture or energy production (24–27). In such small countries, employing empirical data collected over a long period may be the only viable option to ascertain the validity of global climate model projections on a local or regional scale. The Republic of Macedonia, located in the southeastern corner of Europe, could be considered a model of a small developing country with fragile socioeconomic and ecological systems, for which the global climate models predict increase in temperatures and water scarcity indices (16, 24, 25, 28–35). However, these models do not provide specific predictions on a local level, and as such are impractical in addressing the impacts of climate change on the smaller regions of this small country. The overarching goal of this study is to demonstrate the suitability and significance of employing empirically obtained historical data in predicting the impact of future global climate change trends in a small country or its region. To address this goal, the climate change impacts on the national surface water resources of Macedonia were assessed by using temperature trends and other descriptors of global warming. Specifically, a set of three hypotheses were addressed:

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(1) H1: The average temperature on national level has exhibited an increasing trend over the last 50 year period; (2) H2: Surface water hydrology has exhibited a declining trend over the last 50 year period; (3) H3: There is statistically significant correlation between the average temperatures and the average surface water hydrology.

Extensive temperature, surface water flow rate, and precipitation data were obtained from the National Hydro-Meteorological and the State Statistical Offices of the Republic of Macedonia for the period 1961-2012. A set of regression analyses were conducted to test the hypotheses and examine whether statistically significant correlation patterns exist among the different environmental determinants.

Methodology Data Collection A dataset for the period 1961 – 2010 was obtained from National Hydrometeorological Office of the Republic of Macedonia by transcribing the official log books. Data from the period 2011-2012 was obtained from the State Statistical Office of the Republic of Macedonia (36, 37). Data from 2013 was not available during the time this study was conducted, and as such, it was not included in the analysis. Temporal demographics estimates were also obtained from the French National Institute for Demographic Studies (INED) (38, 39). The dataset encompassed (1) temperature data from 10 locations across the country; (2) flow rate data from 14 measuring stations located on the rivers across the 7 watersheds; and (3) precipitation data 12 rain gage stations dispersed in each watershed. Figure 1 provides a map of the Republic of Macedonia, and shows the locations from which data was obtained. Each watershed was characterized by at least one dataset containing temperature, flow rate, and precipitation data. Considering that Macedonia is relatively small in population (~ 2 million) and territory (~25,000 km2), the national averages, estimated from the extensive data sets, were considered to be representative of the entire country (31, 37, 40).

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40 Figure 1. Watershed map of the Republic of Macedonia with data collection locations for temperature, river flow rates, and precipitation.

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Data Analysis and Hypotheses Testing To address the goal of this study, three hypothesis-driven aspects of the obtained data were examined: (1) temporal changes in national average temperature were evaluated by testing hypothesis H1; (2) temporal changes in surface water hydrology were evaluated by testing hypothesis H2; and (3) correlation between temperature and surface water hydrology was examined by testing hypothesis H3. Additionally, a regression analysis matrix, which is presented in Table 1, was generated to (1) examine the correlation between two climate variables; (2) provide additional evidence in support of the three hypotheses; and (3) determine the existence of any statistically significant patterns that could be used as a basis for future prediction. Patterns characterized by statistical significance of p ≤ 0.05 were identified as statistically significant correlations. Patterns characterized by statistical significance of p > 0.10 were rendered statistically insignificant, while patterns for which 0.05 < p < 0.10 were characterized as potentially significant. Normal distribution analyses were used to identify any outliers, which may have occurred as a result of atypical extreme events (e.g. 100-year floods). To determine the effects of climate change on precipitation intensity, the changes in magnitude of annual precipitation were also examined by correlating them to the temperature and time variables. For adequate comparison and where needed, each dataset was normalized against a 30-year average comprised of the period between 1961 and 1991.

Table 1. Regression Analysis Matrix and Employed in Support of the Hypotheses Testing and Obtained p Values

41 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

Results and Discussion

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Temporal Changes in Average National Temperatures Figure 2 illustrates the temporal changes in the average national temperature over the period 1961-2012. The statistically significant correlation (p < 1.7 x 10-4) clearly indicates a global warming trend and unmistakably supports hypothesis H1. The linear model Summarized in Table 2 projects an increase of 0.02 0C/year in the average national temperature although some regions may experience greater or lesser changes. These projections suggest that the average national temperature will reach about 12 0C by year 2060, which is an increase of about 1.7 0C when compared to the 30-year national average based on the period between 1961 and 1991.

Figure 2. Statistically significant increase in national average temperature for the period 1961-2012 (n = 514; p < 1.7 x 10–4). The error bars represent standard deviation.

Temporal Changes in National Surface Water Resources It is inevitable that these temperature increases will have deleterious effects on the national surface water resources in the Republic of Macedonia. Figure 3 illustrates a statistically significant trend (p < 7.5 x 10–4) in support of H3, and demonstrates a decrease of national average surface water resources with the rise of average temperatures. This pattern correlates well with the statistically significant trend in Figure 4, which describes a decrease in the national average surface water flow rates for the period 1961–2012 and supports hypothesis 42 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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H2 (p < 0.026). Although the surface water trend does not consider the two outliers resulting from extreme flooding events, a subsequent regression analysis, conducted with inclusion of these outliers, suggests there is a trend that indicates statistical significance (p < 0.06). Further, a detailed pattern analysis of the data suggests that the 15-year period between 1980 and 1995 has witnessed three-fold decrease trend (p < 1.2 x 10–4) in the surface water hydrology as characterized by a threefold decrease in the average river flow rates (Figure 5). This decrease was mirrored by a statistically significant decrease in the average annual precipitation on national level during the 1979 – 1994 period (p < 7.5 x 10-5) as illustrated in Figure 5. This is not surprising considering that the surface water hydrology in the Republic of Macedonia is directly related to the annual precipitation as illustrated in Figure 6 (p < 1.52 x 10–8).

Figure 3. Statistically significant decrease in national average flow rates with increase in average temperatures for the period 1961-2012 (n = 1,216; p < 7.5 x 10–4). The error bars represent standard deviation. One could argue that this decreasing trend in surface water resources could be attributed to population and economic growth, rather than to climate change. However, the validity of these conjectures can be easily negated by three arguments. First, during the period between 1975 and 2003, there was no construction of major water reservoirs, which could have caused significant impact on the national surface hydrology (41), yet there was a significant decrease in surface water resources. Second, during the same period, the Macedonian economy was affected by a crippling economic recession, which negates the conjecture that the decrease of surface water resources could have been affected by a positive economic growth (32, 42, 43). Third, as illustrated in Figure 7, surface water resources show improvement water with growth in population during the period 1988 – 2010, negating the conjecture that suggests the decrease in water resources is primarily related to population growth. Consequently, it 43 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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is evident that climate change, as manifested by increase in average national temperature, have been the major contributor to the diminishing surface water resources in the Republic of Macedonia.

Figure 4. Statistically significant decrease in national average river flow rates for the period 1961-2012 (n = 702; p < 0.026). The circled data points represent outliers. The error bars represent 95% confidence intervals.

Figure 5. Statistically significant decrease in national average precipitation (solid line and diamonds) for the period 1979-1994 (n = 180; p < 1.2 x 10–4) mirrored by a decreasing trend (dashed line and squares) of the average river flow rates for the period (n = 210; p < 7.5 x 10–5). The error bars represent 95% confidence intervals. 44 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Figure 6. Statistically significant correlation (n = 1,300; p < 1.52 x 10–8) between average flow rates and precipitation on national level demonstrating the strong dependence of surface water resources on annual precipitation in the Republic of Macedonia. The error bars represent standard deviation.

Table 2. Summary of the Linear Models Obtained from the Statistically Significant Trends (SST); t Represents the Modeled Year

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Figure 7. Increase of surface water resources with growth in population during the period 1988 – 2010 negates the conjecture that the decrease in water resources is primarily due to population growth.

Effects of Climate Change on Precipitation Intensity Figure 8 illustrates the increasing trend resulting from the annual changes in average precipitation (▵ precipitation/year) during the period of 1962 to 2012. As illustrated by the trend line, the magnitude of these precipitation fluctuations has been slowly increasing over the last 50 years. This statistically significant trend (p < 0.007) is indicative of future extreme weather conditions characterized by significant changes in precipitation between years or seasons. This trend typically may not change the overall average hydrological picture of the country because it may be restricted to small regions. For example, one small region of the country may be affected by intensive rainfall during one year, while another small region may be affected with such rainfall the following year. However, the effects of this growing trend are becoming more evident by the increasing number of short-term floods in small town and rural areas across the country (44–48). The regression linear model suggests an increase in average precipitation fluctuations on national level of up to 50 mm/year by 2060, potentially characterized by short rapid rainfall periods during spring and summer seasons and dry winters with limited snowfall. 46 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Figure 8. Statistically significant (n = 600; p < 0.007) trend of increasing magnitudes in annual average precipitation changes (▵ precipitation/year) during the period of 1962 to 2012.

The Implications of Climate Changes on Macedonian Water Resources, Economy, and Society The statistically significant trends of increasing temperatures, surface water resources depletion, and fluctuations in the magnitude of precipitation predict grim scenarios. The arrival of water shortages and increases in the number of extreme weather events is inevitable and it should be anticipated. These implications have the potential to significantly affect Macedonian agriculture and food production, both as a result of loss of irrigable agricultural land and flooding. The harbingers of these grim scenarios are already emerging as exemplified by the increased number of local and regional floods, some of which exhibit never-before recorded magnitudes (49, 50). As hinted by the recent flood damages in neighboring Serbia, the consequences of such scenarios could cause devastating effects on the fragile economies, with possible tangible costs exceeding 20% of the national budgets (51, 52). However, when the intangible damages stemming from eco-system degradation and loss of biodiversity are considered, these costs have a potential to exacerbate the impacts of climate changes on the Macedonian water resources, economy, and society (2, 34). Additionally, considering the interconnectedness of surface hydrology and groundwater resources, it is realistic to postulate that groundwater resources will also be adversely affected because of aquifer depletion and contamination (35, 53). This environmental implication of climate change is especially somber because the majority of Macedonian population depends on groundwater as potable water 47 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

source (54). Catalyzed by the increase in temperatures in the future, demands for both surface and groundwater are expected to increase in Macedonia (55, 56). In turn, this increase could cause new or intensify the existing water restrictions, which have become a regular occurrence over the last couple of decades (47, 57, 58).

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Conclusions The analysis of a half-century historical record of climate change indicators in the Republic Macedonia support the overarching low-resolution predictions of global scale models and generate statistically significant trends applicable to smaller regions. These trends predict significant impacts on the hydrological prospects of Macedonia, which could create substantial socio-economic and environmental challenges for the country. They necessitate development of an adequate national water resource management strategies that incorporate (1) a high-detail threat assessment of current and future water deficiencies; (2) an evolving platform comprised of specific and evolving action plans to foresee and address local and national water needs and opportunities, with emphasis on highest risks and priorities; and (3) a national integrated water resource management system run by administration capable of mitigating the effects of the imminent grim scenarios. Development and implementation of such strategies and system, however, is not possible without creating the next generation of homegrown water professionals, who would have the expertise and skills to address this complex issue of national importance.

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35. Eturk, A.; Ekdal, A.; Gurel, M.; Karakaya, N.; Guzel, C.; Gonenc, E. Evaluating the impact of climate change on groundwater resources in a small Mediterranean watershed. Sci. Total Environ. 2014, 499, 437–447. 36. State Statistical Office of the Republic of Macedonia. Macedonia in figures 2012; 2013 [cited 2014 Sept 12] [about 11 p.]; available from: http://www.stat.gov.mk/Publikacii/Mak_Brojki_2012_A.pdf. 37. State Statistical Office of the Republic of Macedonia. Macedonia in figures 2013; 2014 [cited 2014 Sept 12] [about 11 p.]; available from: http://www.stat.gov.mk/Publikacii/MK_Brojki_2013_a.pdf. 38. Avdeev, A.; Eremenko, T.; Festy, P.; Gaymu, J.; Le Bouteillec, N.; Springer, S. Populations et tendances démographiques des pays européens (1980-2010). Population 2011, 66, 9–133 French. 39. INED. All about population/Data; 2014 [cited 2014 Sept 5]; available from: http://www.ined.fr/en. 40. Hristovski, K. D.; Hild, N. R.; Young-Hristovski, J. E. The environmental management system in the Republic of Macedonia – problems, issues and challenges. Commun. Post-Commun. Stud .2010, 43, 115–124. 41. Hydrobiological Office Ohrid. Fishing basis for Kozjak accumulation for period 2009-2014; Ministry of Agriculture, Forestry and Water Economy of the Republic of Macedonia: Macedonia, 2008. 42. Rajsic P. The Economy of Tito’s Yugoslavia: Delaying the Inevitable Collapse - Ludwig von Mises Institute Canada; 2014 Mar [cited 2014 Dec 15] [about 1 p.]; available from: http://mises.ca/posts/articles/the-economyof-titos-yugoslavia-delaying-the-inevitable-collapse/. 43. International Monetary Fund (IMF). Report for Selected Countries and Subjects. World Economic Outlook Database; 2011 Apr [cited 2014 Oct 15] [about 1 p.]; available from: http://www.imf.org/external/pubs/ft/weo/2011/01/weodata/ weorept.aspx?pr.x=60&pr.y=10&sy=1991&ey=2016&scsm=1&ssd=1&sort=country&ds=.&br=1&c=962&s=NGDP_RPCH%2CNGDPD%2CNGDPDPC%2CPPPGDP%2CPPPPC&grp=0&a=. 44. Macedonian Information Agency. [Possible evacuation. Flow accumulation & Quot; Put & Quot]; 2012 Mar [cited 2014 Dec 15] [about 1 p.]; available from http://vecer.mk/makedonija/mozhna-evakuacija-na-naselenieto Macedonian. 45. Radio Free Europe. [Floods in Strumica and Valandovsko]; 2010 Sep [cited 2014 Dec 15] [about 1 p.]; available from http://www.makdenes.org/archive/ news/20100926/428/428.html?id=2168565 Macedonian. 46. Radio Free Europe. [Macedonia. Flood Evacuations].; 2013 Feb [cited 2014 Dec 15] [about 1 p.]; available from http://www.slobodnaevropa.org/archive/ news/20140514/500/500.html?id=24911158 Macedonian. 47. Dnevnik [Restrictions of drinking water in Kavadarci]; Macedonian 2011 Jun [cited 2014 Dec 15] [about 1 p.]; available from:http://www.dnevnik.mk/ default.asp?ItemID=5415BDEE4C6D4B4687D949272B1B1455 Macedonian.

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48. Krstevski. Poplavi Vo Kumanovo 8 Juni 2011; 2011 Jun [cited 2014 Dec 15] [about 1 p.]; available from http://wn.com/ poplavi_vo_kumanovo_8_juni_2011 Macedonian. 49. Reuters. [Macedonia at risk of flooding]; 2010 Feb [cited 2014 Dec 15] [about 1 p.]; available from http://www.b92.net/info/vesti/ index.php?yyyy=2010&mm=02&dd=19&nav_id=412493 Macedonian 50. Radio Televizija Srbije. [Macedonia, two dams affected by floods]; 2013 Feb [cited 2014 Dec 15] [about 1 p.]; available from http://www.rts.rs/page/stories/sr/story/11/Region/1274552/ Makedonija,+dve+brane+ugro%C5%BEene+zbog+poplava+.html. 51. Filipovic, G. Srbia Adopts 2014 Budget With Europe’s Highest Fiscal Deficit; Bloomberg 2013 Dec 13 [cited 2014 Oct 12] [about 1 p.]; available from http://www.bloomberg.com/news/2013-12-13/serbia-adopts-2014budget-with-europe-s-highest-fiscal-deficit.html. 52. Tanjug. [EBRD: Flood damages in Serbia 1.5 to two billion euro]; Politika Online 2014 May [cited 2014 Aug 15] [about 1 p.]; available from: http://www.politika.rs/vesti/najnovije-vesti/EBRD-Steta-od-poplava-uSrbiji-15-do-dve milijarde-evra.sr.html. 53. Klove, B.; Ala-Aho, P.; Bertrand, G.; Gurdak, J. J.; Kupfersberger, H.; Kværner, J.; Muotka, T.; Mykrä, H.; Preda, E.; Rossi, P.; Bertacchi Uvo, C.; Velasco, E.; Pulido-Velazquez, M. Climate change impacts on groundwater and dependent ecosystems. J. Hydrol. 2014, 518, 250–266. 54. Novak, J.; Kodre, N.; Terpin Savnik, S.; Repnik Mah, P.; Sisko Novak, S.; Dolinar, D.; Pipus, G.; Pivec, N.; Invanc, A.; Dodic, J.; Erzen, P.; Panovski, Z. National Strategy for Water for republic of Macedonia (2011-2041); Hidroinzinering doo: Ljubljana, Slovenia, 2011. 55. Ten Brink, P.; Avramovski, L.; Vermoote, S.; Bassi, S.; Callebaut, K.; Lust, A.; Hunt, A. Task 2 Benefits for the former Yugoslav Republic of Macedonia and other countries of SEE of compliance with the environmental acquis; Final report – Part II: Country; The European Commission – DG Environment: Brussels, Belgium, 2007. 56. Srna. [Floods in Macedonia]; 2010 Feb [cited 2014 Dec 15] [about 1 p.]; available from http://www.blic.rs/Vesti/Svet/177690/Poplave-u-Makedoniji Macedonian. 57. Municipality of Prilep. Water management; 2014 [cited 2014 Dec 15] [about 1 p.]; available from http://www.prilep.gov.mk/informacii/en/watermanagement/. 58. Kumanovo. [It improves the PE “water”]; 2012 Sep [cited 2014 Dec 15] [about 1 p.]; available from tri.kumanovonews.com/vesti/se-podobruvarabotata-na-jp-vodovod Macedonian.

52 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

Chapter 4

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Drinking Water and Sanitation in Central America: Challenges, Perspectives, and Alternative Water Treatment Irwing M. Ramírez-Sánchez,1 Susan Doll,2 and Erick R. Bandala*,1 1Grupo de Investigación en Energía y Ambiente, Posgrado en Ciencias del Agua, Universidad de las Américas Puebla, Sta. Catarina Mártir, Cholula, Puebla, 72810, Mexico 2Department of Sustainable Technology and the Built Environmental, Appalachian State University, Boone, North Carolina, 28608, U.S.A. *E-mail: [email protected]. Tel: +52 222 2292652.

Although the Central America region has no widespread water shortage, water resources are uneven or inadequately distributed and despite the current lack of data for the region, it is estimated that 2.1 million urban and 13.2 million rural inhabitants have no access to safe drinking water. In addition, the use of pit latrines, septic tanks and direct discharges to water bodies are frequent practices. In some countries of Central America, the money spent by the government on treating diarrheal disease is four times the amount of money required to monitoring water quality and improve water sanitation systems. For this reason, this chapter analyzes plausible alternatives for water treatment and wastewater sanitation aimed to improve population’s health by assuring access to safe drinking water. Water treatment alternatives considered for the Central America region are centralized and non-centralized systems. Finally, challenges and perspectives for the region are addressed based on interventions of low-cost water technologies, education about safety practices and proposals for Governments in implementing water management strategies.

© 2015 American Chemical Society In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Introduction Water is one of the most important elements for public health. A target of the Millennium Development Goals is to reduce by half the proportion of the population without sustainable access to safe drinking water and basic sanitation. While the United Nations has recognized the human right to safe water and sanitation, water supply depends on the amount of available water, the legal, economic and social framework, and the engineered distribution system (1). Central America is the geopolitical region that connects North America and South America and includes Belize, Costa Rica, El Salvador, Guatemala, Honduras, Nicaragua, and Panama. The settlement patterns in Central America have changed from historically predominantly rural to now nearly equal urban as shown in Table 1. The overall population is 46.5 million habitants (2) and shows differential increasing rates across countries. The demographic changes have modified the economic structure of the countries within the region, producing effects on social and environmental-related issues, i.e. the lower importance of agriculture’s contribution to gross domestic product (GDP) or imbalance between water supply and water demand (3). The main runoff in Central America is to the Pacific coast (c.a. 30 % of total water) being this region where the most intensive economic development and over 70 % of population occur (3) giving water resources unevenly between rural and urban areas, as also showing in Table 1. As shown in Table 1, urban access to drinking water is uniformly greater then 86% with rural access considerably lower in all countries, especially El Salvador and Nicaragua. Overall, 2.1 million urban and 13.2 million in rural areas of Central America have no access to drinking water. Similarly, with the exception of Costa Rica, access to adequate sanitation is significantly lower in rural areas particularly in Belize. Total affected populations are 1.1 million and 8.7 million in urban and rural areas, respectively. In order to avoid the undesirable consequences of the lack of access to safe drinking water, poor and marginalized groups in the countries of the region may pay more than 25% of their monthly-earned incomes to get drinking water from independent suppliers. The low level of water supply service is usually correlated with the regions with extreme poverty, whereas wealthy regions usually have access to high-quality water services (9). The water stress at the household and community levels can be compared using the Water Poverty Index (WPI) (10), that links household welfare with water availability and indicates the degree of impact on human populations due to water scarcity. The lower the WPI value, the higher the impact of water scarcity on human populations. The WPI values for countries in Central America are also shown in Table 1 (5). In agreement with the index values included, El Salvador shows the highest water stress and Costa Rica has the lowest degree of water scarcity. Water quantity, however, is not the only complex topic in the region. In Central America, most countries do not have water quality monitoring systems or regulations to forbid the use of dangerous chemicals such as pesticides, or to reduce the pollution due to agricultural practices, industry activities, or services sector (3). As a result, the impact of the presence of undesirable toxic chemicals in drinking water is poorly understood or completely unknown. 54 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Table 1. Central America Population Distribution, Access to Drinking Water and Sanitation, and Water Poverty Index Value (WPI). Data source: references (4) and (5). Population, %

Drinking water, %

Sanitation, %

Country

Urban

Rural

Urban

Rural

Urban

Rural

WPI

Belize

50.36

49.64

99.60

62.70

70.90

25.30

66.3

Guatemala

34.98

65.02

87.34

47.91

94.72

70.31

59.3

El Salvador

50.75

49.25

86.30

16.70

85.76

50.38

55.9

Honduras

46.55

53.45

89.00

63.20

93.98

49.50

60.2

Nicaragua

53.62

46.38

88.26

14.43

93.00

56.00

58.2

Costa Rica

43.11

56.89

99.47

81.44

88.76

97.13

66.8

Panama

55.21

44.79

86.75

76.15

98.65

86.54

66.5

Even though rarely differentiated in official drinking water data, Halder et al. (6) have proposed two different source types to be considered in water supply services: improved or unimproved drinking water. Improved drinking water sources includes the use of household connections, public standpipes, boreholes, protected dug wells, protected springs, and rainwater collection. Unimproved drinking water sources include unprotected wells, unprotected springs, rivers or ponds, vendor-provided water, bottled water (due to potential limitations in quantity), and tanker truck water. The global ratio of inhabitants using improved drinking water is 83%, whereas in Latin America this value drops to 40 % (6). Inadequate or poor drinking water quality is highly correlated with diarrheic illnesses. In Central America, the population sector with the highest mortality rate, related to diarrheic diseases associated with poor water quality, is children aged one to four years old. The mortality rate per 1000 inhabitants varies for the different countries in the region and has been reported as high as 1.9 in Costa Rica, 2.4 in El Salvador, 4.1 in Nicaragua, 5.3 in Honduras and 8.6 in Guatemala (7). These numbers are two orders of magnitude higher when compared with other developing countries in Latin America where the mortality rate per 100,000 inhabitants are 1.1 in Chile and Cuba and 3.1 in Mexico. Due to the lack of access to water sources with the proper water quality in the different countries within the region, women and children spend several hours daily collecting water from polluted sources that in many cases are far away from their communities and/or in hard to access locations. The time wasted in collecting water reduces the time that could otherwise be invested in activities such as household chores, child care, education, farming or any other productive activities. As usually happens in poor and developing countries (8), women and girls are responsible for assuring the supply and treating water for household consumption (9). 55 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

The aim of this chapter is to analyze the situation in the Central American region related to drinking water quality and wastewater sanitation in order to identify the main challenges, suggest some perspectives, and propose cost-effective alternatives for the management and enhancement of water quality that may help the sustainable development of the region.

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Drinking Water and Sanitation in Central American Countries Available data for drinking water and sanitation are summarized below for all the countries included within the Central American region. The information was classified and organized to provide a complete set of information for understanding the problem complexity occurring in the study area. Belize Surface and groundwater resources in the country are adequate to avoid further water supply shortages. However, despite the water availability, water quality is becoming a major concern. Even though 97% of the population has access to drinking water, only 11% of inhabitants in urban areas have accesses to sewerage service. In the rural sector, 87% of the population has access to only rudimentary water facilities, i.e. pit latrines, and septic tanks, as the most common forms of sanitation infrastructure (11). As a result of this situation, the risk of surface and underground water being polluted by the poorly treated or completely untreated sewage water increases as the wastewater discharges increase. The urgency of implementing cost-effective wastewater treatment processes is clear in the case of Belize to maintain the viability of its sustainable growth and improve the quality of life of inhabitants. Guatemala Although the available per capita water resources in Guatemala is higher than 9.7 x 1010 m3 per year, the entire country lacks access to safe drinking water because of pollution and rain seasonality in the country. The actual water infrastructure reaches only 1.5 % of the available water (12). According to Guatemala’s Statistical Institute, drinking water and sanitation coverage in the country are 73.5 and 55.96 % respectively. Significant reductions when comparing data before and after the damage caused by hydro-meteorological events, combined with the lack of investment in public infrastructure, indicate that improvement in public services has fallen behind population growth. Based on official data, coliform bacteria are found in more than 90% of surface water in the country, and only 15% and 25 % of the water supplied is treated for disinfection (improved water source) in rural and urban areas, respectively (9). The amount of municipal wastewater discharge is nearly 668 million cubic meters (Mm3) but only 6% is treated. This situation significantly contributes to the frequency of waterborne diarrheic diseases, lack of nutrition and high mortality within the population sector younger than five years old. 56 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

El Salvador

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Almost no information is available related to water quality, water pollution, wastewater discharge, or treatment. Surface water quality monitoring in 55 rivers across the country has shown that the entire country does not have any water source with excellent water quality, and that only 12% of the surface water is considered good, 50% is considered as regular, 31 % is bad and 7% is indexed as terrible (13). As shown, significant improvement are required in El Salvador not only to generate basic information on the surface water quality but also related to underground water quality, wastewater quality and quantity, as well as wastewater production and treatment. Honduras In Honduras, the reported population coverage for drinking water in urban areas is 82% and 72% for sanitation. For rural areas, these data become 68% and 64%, respectively. Drinking water disinfected by chlorine in rural areas covers only 32% of the population (14), and only 52% of individuals living in rural Honduras use improved water sources. As a result, the country has a mean of 18.6 episodes of diarrhea per child-year in children less than five years old (6). Nicaragua Information about water quality, wastewater generation, and treatment in Nicaragua is also almost nonexistent. Nevertheless, diarrheic diseases are reported commonly present all around the country where household sanitation is not in common use. In some areas, mortality due to diarrheic diseases accounts for 7.3% of the overall mortality every year. There is no sanitation infrastructure and it has been proposed by some authors (15) that simple and low-cost interventions such as improve microbiological water quality by chlorination and latrine infrastructure development to reduce wastewater effluents may reduce the prevalence of diarrheic diseases in isolated regions of Nicaragua. Costa Rica In Costa Rica, 98.3 % of the population receives drinking water, but only 82% receives it from improved water sources (16). Drinking water from improved sources frequently includes disinfection by filtration or settling when needed (1). Another problem of drinking water services is the disruption of water supply resulting in the need for bringing the water by truck. It is estimated that approximately 800 thousand inhabitants receive water from unimproved water sources (1). Pathogen contamination from untreated or improperly treated sewage is the major form of surface water contamination. Despite 67% of households in the country possessing septic systems only human sewage goes into the septic tank, with wastewater effluents from personal hygiene, cooking or washing clothes being discharged into natural streams without any further treatment (1). 57 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Natural streams are not the preferred source of domestic water supply due to potential water contamination, mostly from untreated sewage, sediment, and agricultural chemicals. Increasing episodes of water supply sources contamination by hydrocarbons, pathogens, gasoline, nitrates, herbicides (i.e. bromacil and diuron), and insecticide (i.e. terbufos) have been documented recently (1). Based on the high amount of microbiological contamination and the high incidence of waterborne diseases reported across the country, it is estimated that the amount of money spent on treating diarrheal disease in Costa Rica in 2002 was four times the potential cost of monitoring water and sanitation systems in the same period (1).

Panama Surface water in Panama is mainly represented by 150-350 rivers of mean length in the range between 56 and 350 km. However, the country has no water storage/control infrastructure. The national household coverage of drinking water and sanitation are 92.9% and 94.5%, respectively. However, there are communities with 50% or less of coverage of drinking water. From the total sanitation coverage, 33.1% of household are connected to sewage, 30% possess a septic tank, and 31.4% uses a latrine as the only sewage service (17).

Alternative Water Treatment and Sanitation Even though Central America precipitation and water resources may appear at glance to be a regional wealth of water, there are social, economic, legal, and political impediments to the efficient use and the protection of such abundant water resources. To supplying drinking water and sanitation, municipalities and operating agencies use expensive conventional water technology in spite of successful experiences in the region using low-cost technologies (8). The number of surface water sources reported as contaminated due to excess in agricultural practices has increased in Central America as a result of the massive use of herbicides, pesticides and fertilizers and untreated sewage. Fewtrell et al. (18) summarize the reduction in diarrheal disease morbidity due to improvements in one or more components of water and sanitation in less developed countries. Some of these interventions are point-of-use water treatment (hypochlorite chlorination, solar disinfection, boiling, pasteurization, and simple filtration), source improvements (safe household storage, tube well construction), sanitation (hand pump and latrine installation, pit latrine), and hygiene and health education. The reduction in diarrheal disease was 33% through improvement in hygiene, 36% related to sanitation, 19% associated with the improvement of water supply, and 12% related to multiple interventions. To improve drinking water and sanitation, local governments, NGO´s and citizens also should recognize the need to consider that the approach of centralized water treatment systems is as valuable as non-centralized water treatment systems when the necessary resources for implementation are available. 58 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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The approach of centralized water treatment systems is based on treatment plants with conventional treatment processes such as coagulation, flocculation, sedimentation, rapid or pressure sand filtration or, even ultrafiltration systems (19). It is well known that these treatment processes provide reasonably safe drinking water with few occurrences of coliform, and a very rare presence of E. coli, in the drinking water in zones that lack drinking water services (19). On the other hand, many communities in Central America do not have enough residents to warrant further development of centralized water treatment systems and the government will not invest in such systems for sparsely populated areas. For these cases, non-centralized water treatment systems have emerged in the last decade as an interesting cost-effective, on-site alternative for low-income, isolated rural, or peri-urban zones (20). Non-centralized water treatment systems are broadly divided in two categories described below: non-centralized drinking water systems and non-centralized sanitation systems.

Non-Centralized Drinking Water Systems In Central America, boiling water is one of the most common point-of-use water treatments for households. Even though the practice of boiling improves the microbiological quality of water, reducing thermo-tolerant coliforms by 86.2%, it does not fully remove the potential risk of waterborne pathogens. Furthermore, boiling water practices have the associated problems of requiring fuel and potential negative effect on indoor air quality (21). To avoid the potential limitations of water boiling procedures, other non-centralized drinking water treatment alternatives may be adopted such as filtration, solar disinfection, or chlorination. Among the most interesting non-centralized water treatment systems alternatives for Central America are: 1) Gravity-fed Ultrafiltration (GFU), 2) Solar Water Distillation, 3) Solar Water Disinfection, 4) Point-of-Entry/Use Chlorination, 5) Countertop UV Disinfection, and 6) Ceramic Filters for Point-of-Use. These systems are discussed in more detail in the following sections as proposed methodologies for the different areas in the region. 1) Gravity-fed Ultrafiltration (GFU). This system is useful for household applications, especially for low-income residents (22). It is a fully integrated, gravity-fed, point-of-use microbial water treatment system. To meet the needs of the most vulnerable populations, it was designed to operate without electricity or any other power input, and without a piped-in water supply. The process is designed to treat water of unknown microbiological quality and meet internationally recognized levels for microbiological water purifiers, as well as heavier levels of turbidity that may characterize water in such settings, especially during rainy seasons. The microbiological barrier consists of a 26-cm-long × 3-cm-wide plastic cylindrical cartridge containing some hollow fibers with a 20 nm pore size. Source water is introduced into the system by dipping the 2.5 L receptacle into an open vessel or pouring water into it whenit is hanging or mounted on a wall. The water passes through a cleanable 27-μm textile pre-filter mounted in the removal plastic 59 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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basket inside the receptacle, and then through a 1-m length of 12-mm diameter plastic tubing filling the cartridge. A slow-eluting solid chlorine tablet can be installed in the halogen chamber located at the receptacle to help prevent biofilm. When the side tap is opened, water passes through the walls of a hollow fiber membrane bundle that mechanically removes microbes and other suspended solids greater than 20 nm in size, as it flows out the tap,. The textile pre-filter is cleaned by removing its basket from the receptacle and rinsing it with water. The microbial cartridge (plastic tubing cartridge) must also be cleaned from time to time by backwashing it. Gravity-fed ultrafiltration is usually designed to produce ~150 mL of product water/minute (9 L/hour) and to last for at least 18,000 L. As it relies on mechanical filtration and not disinfection or adsorption, there is no need for a means of measuring volume of water treated or end of useful life; as long as the device remains intact, water from the tap will be effectively treated. When the flow from the unit cannot be restored to an acceptable rate by pre-filter cleaning and cartridge backwashing, the entire unit should be replaced, as intended. Assuming a household of five persons, the unit is capable of providing 2 L of safe drinking water per person per day for almost five years without any part replacement. In larger quantities, the manufacturer sells this configuration for about two dollars. Using the previous assumptions, this works out to less than $1 per person per year. The cost per liter of treated water would be $ 0.001. The device was tested through 20,000 L (~110% of design life) at moderate turbidity (15 NTU), achieving a 6.9 log reduction of E. coli, 4.7-log reduction for MS2 coliphage (proxy for enteric pathogenic viruses), and 3.6 log reduction for Cryptosporidium oocysts. This exceeded levels established for microbiological water purifiers. With periodic cleaning and backwashing, the GFU unit produced treated water at an average rate of 143 mL/min (8.6 L/hour) (range 293 to 80 mL/min) over the course of six months of evaluation (22). 2) Solar Water Distillation. Since the early 1990s, there has been a continuous effort to develop solar water distillation technology to meet drinking water requirements in poor water regions (24). It has been demonstrated that solar distillation effectively eliminates salts (i.e., arsenic), heavy metals, bacteria, and microbes from contaminated water sources as well as some pesticides and volatile organic compounds (23). It is also able to provide cost-effective, reliable, and safe water. A solar distiller uses the basic principles of evaporation and condensation for cleaning water. The contaminated feed water enters into the distiller, and the solar radiation penetrates a glass surface, causing the water to heat up through the greenhouse effect and subsequently evaporate. It has been determined that about 0.5 m2 of solar water distiller area is needed per person to meet their potable water needs consistently throughout the year (23). When the water evaporates inside the still, the purified water condenses on the underside of the glass, runs into a collection trough, and then to a collection container. During the process, the salts and microbes in the raw water remain in the original feed water and are left behind. The additional water fed into the still flushes out concentrated waste from the basin to avoid excessive salt build-up from the evaporated salts. Solar distilled water production rate is a function of the amount of solar energy and ambient temperature. Typical production efficiencies 60 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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for single-basin solar stills have been determined to be up to 60 percent in the summer and 50 percent during the colder winter, with typical production of about 0.8 liters per sun-hour per square meter. The effectiveness of distillation for producing safe drinking water is well established and long recognized (20, 24). Distillation is the only stand-alone point-of-use (POU) technology with NSF (National Sanitation Foundation) certification for arsenic removal. Solar distillation removes all salts and heavy metals, as well as biological contaminants (i.e. Cryptosporidium parvum, E. coli) (23). Although initially, lack of interest by the population for owning a solar distiller was reported, solar water distillation technology has gradually improved over the past decades. Over time, some households started to reconsider the idea of using alternative, clean energy to achieve their water requirements. In the survey carried out by Hanson et al. (23), a very important percentage of the population showed enthusiasm about the economic benefits of using solar distillation for safe drinking water production. They found that paying a relatively low price for a solar distiller was a favorable alternative to having to buy water on a regular basis. Others valued the independence and fascination they experienced from being involved in the production of their purified water. In many cases, residents were concerned about the color or odor of the local water supply, while the overwhelming characteristic that gains the residents’ attention is poor taste. Survey results showed that one of the reasons residents looked for a water purification system was to improve the taste of their local water. Since many of the local water supplies are high in salts and minerals (e.g., iron or sulfur), they often have a marginal or poor taste. 3) Solar Water Disinfection. Solar water disinfection (SODIS) is an environmentally friendly and low-cost point-of-use treatment technology for drinking water purification (25). SODIS takes advantage of the bacteriostatic capability of the UV-A portion (wavelength 320–400 nm) of solar radiation combined with the dissolved oxygen to inactivate pathogens in water through the production of reactive oxygen species (ROS). Typically, SODIS uses UV-A-transparent polyethylene terephthalate (PET) bottles filled to three-fourths of their capacity with water; agitated to increase the water’s dissolved oxygen content; and exposed to sunlight for six hours. According to the Swiss Federal Institute of Aquatic Science and Technology (26, 27), the best bacteria inactivation effect is reached when heat and UV radiation combine synergistically (28, 29). SODIS has been widely tested for application in rural communities in Mexico where water is scarce. Removal up to 100 percent of the pathogenic microorganisms in water has been achieved by direct exposure to solar radiation using plastic bottles of commercial beverages. The technological approach has been identified as cost-effective for application in marginal communities (25, 30). Different studies have been performed to determine energy requirements and doses to achieve pathogen inactivation to a certain level. Some of them have shown thermal inactivation of Escherichia coli is important only when water reaches temperatures over 45 °C when a strong synergy with the effect of radiation is observed. It is concluded that disinfection using solar energy is a low cost and effective method to improve the microbiological quality of water in places with high ambient temperatures and solar radiation (31). However, bacterial regrowth after short storage (24 hours) of SODIS-treated water has been observed (32, 33). 61 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Seeking improvements in SODIS performance, research has focused on a reduction in irradiation time. Prevention of bacterial regrowth and advanced oxidation processes (AOPs) have been found to be important contributors in SODIS enhancement. AOPs generate hydroxyl radicals (•OH) via titanium dioxide (TiO2) photocatalysis, Fenton reagent (ferrous iron and hydrogen peroxide), UV/hydrogen peroxide, UV/ozone, electron beam excitation, sonolysis, and gamma irradiation. Among various AOPs, photocatalytic processes have been found to be very attractive for the mineralization (conversion into carbon dioxide, water, and other mineral species) of aqueous pollutants and inactivation of pathogenic microorganisms (31, 34–36). Recently, Sharma et al. (37) demonstrated that ferrates based technologies are highly promising and environmentally friendly and exhibit high oxidation capacity of persistent organic pollutants, inactivation of viruses and bacteria, and removal by coagulation of heavy metals and arsenic. Application of these technologies to water disinfection using solar radiation, coined as Enhanced Photocatalytic Solar Disinfection (ENPHOSODIS), has allowed the efficient inactivation of highly resistant microorganisms (31, 38, 39). Several different improvements have been developed for ENPHOSODIS processes to achieve higher disinfection rates using shorter irradiation times, or using not only the UV part of the solar radiation but also taking advantage of the solar visible spectrum (34, 38). Other mechanical improvements have been attempted, such as the immobilization of the semiconductor photocatalyst (i.e., titanium dioxide) on inert and transparent solid matrixes to avoid the solids removals step after the water treatment (32, 40). All these technological improvements focused on the generation of safe drinking water are currently under review, and no experimental results are reported for its field application as point-of-use water treatment processes. However, laboratory-scale results have been good enough to generate high expectations related to the application of ENPHOSODIS-type methodologies to remove chemicals and biological contaminants from drinking water (31, 38). 4) Point-of-Entry/Use Chlorination. An important concern related to water quality is the possibility of microbial contamination during collection, transport, and storage. Therefore, chlorination at the point-of-use or point-of-entry could be a low-cost (less than $1 per day/person) way to purify water. However, chlorine is known to be ineffective against important pathogens such as Cryptosporidium parvum and Giardia lamblia and the potential formation of harmful disinfection byproducts in waters containing low organic content (31, 41). 5) Countertop UV Disinfection. UV disinfection uses wavelength radiation between 100 and 280 nm (UV) being highly germicidal. UV disinfection has shown satisfactory results in removing total coliform, E. coli, and an indicator virus, bacteriophage MS2. Also, it is known to be highly effective for Cryptosporidium and Giardia strains (31). However, this method is not practical for low income households as it requires access to and ability to pay for electricity. 6) Ceramic Filters for Point-of-Use. Filters are constructed with clay and sawdust collected from available materials near to the communities. In this processes, size exclusion and sorption are the main mechanisms for bacteria removal. It has been demonstrated that the reduction in total coliforms and E. coli 62 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

can be as high as 87% and 92%, respectively (42). These results suggest that this point-of-use technology can effectively improve water quality in the developing world. To improve performance of ceramic filters it has investigated the effect of percent sawdust and impregnation with silver nanoparticles to reduce the viable counts in the effluent (42). The strengths and weakness of centralized water supply and these non-centralized water treatment technologies are summarized in Table 2

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Non-Centralized Sanitation Systems Given the developing political and economic environment of Central America, centralized sewage management systems are not a realistic solution in the short to medium term (43). Small communities or tourism-based businesses will require decentralized wastewater management systems (DWMS) or non-centralized sanitation systems. The advantage of non-centralized sanitation systems over centralized systems is that smaller units can often be designed, installed, operated, and maintained using local materials and labor, and often without any mechanization or power requirements. They can be effectively used for various point sources of wastewater, such as schools, housing blocks, and tourist facilities. The following two non-centralized sanitation processes may be adequate for implementation in Central American to improve the quality of the wastewater being discharged into natural streams. 1) Coco peat based biofilter. Coco peat forms a low-cost biofilter that treats the polluted discharges from septic tanks (43) in areas where coconut production is locally important (i.e. El Salvador). Coco peat filter technology is a proven cost-effective, sustainable alternative to other secondary wastewater treatment technologies, showing removal efficiency of 90% of organic matter, suspended solids, and pathogenic bacteria (44). 2) Constructed wetlands. Constructed wetlands are well suited to some rural and developing areas. It has been shown that vertical flow constructed wetlands using Chrysopogon zizanioides and Cymbopogon flexuosus are useful to reuse domestic greywater with removal efficiencies in the range of 98% for turbidity, 80% of total suspend solids, 79% of chemical oxygen demand, 87% biochemical oxygen demand, 71% nitrates, and 52% phosphates (45). To improve performance of a constructed wetland, hybrid wetland systems have been also investigated showing significant improvements in the removal of ammonia (52%), 54 % of nitrate, 78% of biochemical oxygen demand, and 56% of chemical oxygen demand for effluents with chemical oxygen demand loading as high as 690 g m-2 d-1 (46).

63 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Table 2. Review of the Strengthens and Weakens of the Point of Use, Point of Entry Technologies Proposed for the Central American Region Technology

Main reported advantages

Main estimated disadvantages

Sites/areas to be implemented

Main challenges for implementing

Not always applicable for scattered populations, fails with the removal of non-conventional pollutants (i.e. pesticides, emerging) in water; requires highly specialized operation

Urban locations with medium to high economical incomes

Investment, operational and maintenance costs; proper operation and efficient prices establishment

Centralized water supply system Includes well known/ conventional water treatment processes; able to generate the required amount/quality of water; initial and operative costs well understood Non-centralized water treatment 1) GFU

Designed for household use especially with low income; no power inputs required; able to meet international standards for microbiological quality

No replacement cost reported; may need periodical major maintenance; no information on the minimum water quality required is available; field tests must be carried out to assess its performance

Small settlements with dispersed population; low-income settlements lacking access to basic services (i.e. electricity, piped water)

Can affect water taste or odor; may need continuous water feeding to generate the required amount of water; process efficiency may decay for water with high load of suspended or dissolved solids

2) Solar distillation

Widely tested in field work along the US-Mexico border; able to remove not only microorganisms but other organic and inorganic pollutants (i.e. heavy metals, VOCs); provides cost-effective safe water

Requires significant amount of solar radiation; depending on the design it may have considerably low efficiency

Reported as highly applicable to the US-Mexico border strip; small settlements with high amount of solar radiation

Initial unwillingness of people to use the technology; investment and maintenance cost may be high, depending on source water quality

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Main reported advantages

Main estimated disadvantages

Sites/areas to be implemented

Main challenges for implementing

3) Solar disinfection

Highly cost-effective; widely tested in field work; many different approaches reported

Requires significant levels of solar UV radiation; microorganism re-growth may occur if nor properly applied; use of recommended PET bottles may produce cross-contamination

Point-of-use technology; it may be applied in both rural or urban communities; tested in field work for many different conditions

Initial unwillingness of people to use the technology; difficult to determine the end point of the process during cloudy days; health risks related to cross-contamination

4) Chlorination

Highly cost effective, relatively easy to monitor, field tested

Ineffective against certain pathogens, overdosage is common and may lead to taste and odor and disinfection byproducts

Small settlements with spread population; low-income settlements lacking access to basic services (i.e. electricity, piped water)

Storage and dosing of chlorine; in the case of large storage tanks, difficulty in climbing the tank to monitor chlorine residual and addition of chlorine

5) Countertop UV disinfection

Designed for household use, highly effective against a wide spectrum of microbial pathogens, easy to operate, no formation of known disinfection by-products (DBPs), field tested

Moderate to high cost, requires electricity, maintenance of the UV lamp required.

Urban or rural communities with access to electricity

Initial investment of the device, periodic cleaning of the UV lamp

6) Ceramic Filters for Point-of-Use

Percent reduction of total coliform bacteria of 87.11% and E. coli bacteria of 92.82%, as well as turbidity

Cost of equipment and energy to produce filters

Nicaragua, Guatemala, Peru, Vietnam, Cambodia, Ghana, Yemen, and Myanmar

Optimizing the filter composition and manufacture and use procedures

65

Technology

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Conclusions The available data for the Central America region shows an important lack of understanding of the volume, use and quality of surface and underground water. As an example, a survey developed in Guatemala suggests a significant misinformation about the causes of diarrhea. The survey suggested that people attribute diarrheic diseases to dirty food (28%), to dirty water (44%), to flies/insects (3%), to poor hygiene/environment (12.5%), cold weather (16%), and to carrying heavy items (3%) (42). Consequently, any water intervention projects in the region should be coupled with educational initiatives as well as considering an ethnographic point of view (47) and anthropological tools (48) to improve public acceptability for the adoption of new technologies. In the region, water problems are closely related to waterborne diseases, pollution, gender equality, and infrastructure. This situation often results in country Governments reacting to the effects of contaminated domestic water rather than preventing water contamination that is the root cause of the problems. It has been pointed out that local authorities spend more than four times the cost of monitoring water and sanitation systems for treating water-borne diseases. Judicious use of funds to implement low-cost non-centralized drinking and water sanitation systems could significantly improve diarrheal diseases and lower treatment costs. Non-centralized drinking and sanitation water systems should be considered for local water legislation. Feasible drinking water treatment alternatives such as Gravity-fed Ultrafiltration, Solar Water Distillation, Solar Water Disinfection, Ceramic Filters for Point-of-Use and sanitation alternatives such as Biofilter or Constructed wetlands could become valuable tools for the improvement of the quality of life for the region’s inhabitants. For monitoring implementation of human right to water in rural and peri-urban areas a regional methodology should be developed and standardized. Flores et al. (49) propose consideration of availability, accessibility, affordability, quality, participation and access to information, and non-discrimination. Trevett et al., (50) provided evidence that water quality deterioration occurs between the points of supply and consumption. Showing that safe household storage is also very important. Finally, Governmental efforts should be aimed to 1) hygiene and health education, 2) non-centralized drinking water and sanitation interventions, 3) standardization of measurements of implementation of human right, and 4) consider anthropological variables to improve adoption and appropriation of practices and technologies.

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disinfection of Escherichia coli using Nitrogen-doped TiO2. J. Surf. Interface Mater. 2014, 2, 1–9. Molina, J.; Sanchez-Salas, J. L.; Zuñiga, C.; Mendoza, E.; Cuahtecontzi, R.; García-Perez, G.; Gutierrez, E.; Bandala, E. R. Low temperature processing of thin films based on rutile TiO2 nanoparticles for UV photocatalysis and bacteria inactivation. J. Mater. Sci. 2014, 49, 786–793. Jimenez-Gonzalez, A.; Gelover, S. Structural and optoelectronic characterization of TiO2 films prepared using the sol-gel technique. Semicond. Sci. Technol. 2007, 22, 709–716. Castillo-Ledezma, J. H.; Pelaez, M. A.; Sanchez-Salas, J. L.; Dionysiou, D. D.; Bandala, E. R. Solar water disinfection using NF-TiO2: Estimation of scaling-up parameters. Int. J. Chem. React. Eng. 2013, 11, 1–8. Kallman, E. N.; Oyanedel-Craver, V. A.; Smith, J. A. Ceramic Filters Impregnated with Silver Nanoparticles for Point-of-Use Water Treatment in Rural Guatemala. J. Environ. Sci. 2011, 407–515. Robbins, D. Guidance for Improving Sanitation in El Salvador’s Tourism Areas Though Decentralized Wastewater Management Systems. Policy Brief 2013, 1–4. Robbins, D. Cocoa peat Effluent Water Filtration Systems in the Philippines: A Comparative Evaluation of Alternative Implementation Models. Research Triangle Institute (RTI) International 2014, 25, 50. Pillai, J. S; Vijayan, N. Decentralized Greywater Treatment for Non potable Reuse in a Vertical Flow Constructed Wetland. Int. Conf. Green Technol. 2012, 58–63. Saeed, T.; Afrin, R.; Muyeed, A. A; Sun, G. Treatment of tannery wastewater in a pilot-scale hybrid constructed wetland system in Bangladesh. Chemosphere 2012, 88, 1065–1073. Wells, E. C.; Zarger, R. K.; Whiteford, L. M.; Mihelcic, J. R.; Koenig, E. S.; Cairns, M. R. The impacts of tourism development on perceptions and practices of sustainable wastewater management on the Placencia Peninsula, Belize. J. Cleaner Prod. 2014, 1–12. Deal, J. Health Impact of Community-Based Water Treatment Systems in Honduras. J. Anthropol. 2011, 1–5. Flores, Ó.; Jiménez, A.; Pérez-Foguet, A. Monitoring access to water in rural areas based on the human right to water framework: a local level case study in Nicaragua. Int. J. Water Resour. Dev. 2013, 29, 605–621. Trevett, A. F.; Carter, R. C.; Tyrrel, S. F. Water quality deterioration: A study of household drinking water quality in rural Honduras. Int. J. Environ. Health Res. 2004, 14, 273–283.

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Chapter 5

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Water Challenges and Solutions for Brazil and South America Gisele O. da Rocha,1,2,3 Jeancarlo P. dos Anjos,1 and Jailson B. de Andrade*,1,2,3 1Institute

of Chemistry, Universidade Federal da Bahia – UFBA, Av. Barão de Geremoabo 147, 40170-290, Salvador-BA, Brazil 2INCT for Energy and Environment, Av. Barão de Geremoabo S/N, 40170-115, Salvador-BA, Brazil 3Centro Interdisciplinar de Energia e Ambiente – CIEnAm - UFBA, Av. Barão de Geremoabo S/N, 40170-115, Salvador-BA, Brazil *E-mail: [email protected].

Although the earth is considered to be well served in terms of bodies of water, freshwater constitutes only 3 % of the total. However, freshwater is unevenly and temporally distributed across the planet or is located in places that are difficult to access. South America is relatively well-endowed with freshwater, although millions of people suffer from restrictions on potable water and proper sanitation systems because of long periods of drought as well as a lack of adequate infrastructure and proper governance. In analyzing the human use of water, it is estimated that 60-80 % is used in agricultural irrigation in developing countries such as those of South America. With regards to the energy matrix, South America has one of the greenest energy mix if the large contributions of hydropower, wind power and biofuels are taken into account. Therefore, the water demand required and produced for power generation by using different sources is discussed throughout this chapter, with a focus on the water-energy nexus in South America.

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Introduction Even though there are approximately 1,386,000,000 km3 of water on Earth, when considering all the source types and all the physical states of this water, 97 % is saline water. Of the remaining 3% that is freshwater, about 99.7 % is trapped in ice caps or found in the ground, which requires energy to be made available (1, 2). The actual, readily available amount of freshwater (4,158,000 km3) is unevenly distributed across the planet. Nowadays, there are 43 countries across the world that face low to severe water stress (a total of 700 million people) because of more frequent and longer drought periods, and others are suffering from intense floods because of climate change (2–4). This number will be even higher by 2025. By 2025, approximately 60% of the global population may suffer from physical water scarcity (2, 5). Freshwater is a very valuable and unique natural and renewable resource for humankind. The world’s civilization as we know it today depends on clean, welldistributed and readily available freshwater sources. However, sufficient energy for supporting every aspect of modern life is also highly necessary for reaching a pleasant quality of life. Water and energy are the two fundamental resources for mankind that are completely cross-linked, because it is necessary to spend considerable amounts of water for energy production, and energy is also required for water consumption (2). In fact, human use of freshwater reserves over the last 50 years has tripled (4). Considering the population projections by the United Nations, the world population will exceed 9.5 billion people by 2050 (6). A complete rethinking and a change of paradigms about water use towards energy efficiency and water security will likely be necessary to avoid the collapse of water and energy resources, and even to guarantee basic necessities for the next generations. South America (SA) is located in the Southern Hemisphere and comprises 13 countries that are distributed over 17.8 million km2 (7). In 2013, South America had a population of 406.5 million inhabitants and 4.37 trillion US dollars in GDP (8). SA is relatively well-endowed with freshwater, although its water bodies are spatially and temporally distributed in an uneven fashion, and millions of people suffer from restrictions on potable water and proper sanitation systems because of a lack of adequate infrastructure and proper governance (9). The actual average total for renewable water resources in South America is 19.5 billion km3 y-1, with a range from 99 million km3 y-1 (for Suriname) to 8647 million km3 y-1 (for Brazil) (7). Although Brazil possesses nearly 44.3 % of the total renewable water resources of South America, some places, such as the states of São Paulo, Rio de Janeiro and Minas Gerais, which are the most industrialized and populated areas, have experienced severe water restrictions in the last ten years. However, the Amazonian Region, which possesses less than 20 % of the Brazilian population, has plenty of water and has been suffering recent flood events. Accordingly, there are reports of water scarcity in Peru, Uruguay, Ecuador, Bolivia and Colombia (10–13).

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Water Use The water cycle begins with the production or extraction of water from different natural sources, such as groundwater, aquifers, lakes, rivers, and oceans. After this process, freshwater usually requires treatment to remove suspended solids and microorganisms in addition to the removal of some undesired organic compounds, dissolved gases or dissolved ions (only in the case of groundwater). Thus, treated water can be used in different ways by many consumers in residential, commercial, industrial, and agricultural areas. However, treated water may be contaminated during its use in different sectors, which may then require proper treatment before it is discharged or reused. The level of water pollution differs with the sector and type of application, as do the treatment requirements (14). When considering water use, three different and important sectors should be taken into account, namely agriculture, industry and residential areas. The water demand in South America in relation to all the Americas (North America, Central America and Caribbean and South America) by sector is found in Figure 1. The total water withdrawal in South America was 130, 22 and 42 km3 y-1 for the agricultural, industrial and domestic sectors, respectively (Figure 1) (15). This distribution represented approximately 32 %, 8 %, and 31 % for the agricultural, industrial and domestic sectors, respectively, in South America in relation to the total withdrawals within the three Americas. The water use expression as the percentage of total renewable water resources (TRWR) is a good indicator of the pressure on water resources. The pressure on water resources is considered to be high when the value is above 25 %. Therefore, the use of industrial water is especially important in Brazil (18 %), Chile (11 %), El Salvador (20 %), Guatemala (17 %), and Venezuela (7 %). Contamination from domestic and industrial wastewater, mining residues and diffuse agricultural pollution (pesticides, fertilizers, etc), is a regional problem, with special emphasis on areas that are suffering from major water resource pressures (15). Water is essential to the residential sector, and the World Health Organization defined the average water requirement for human survival as close to 0.0025 m3 per capita per day (16, 17). However, residential water use rates in South American countries are far beyond the minimum required for basic human survival, and treated water wastage rates may be contributing to these high indices (14). Brazilian cities such as São Paulo and Brasilia consume average amounts that are larger than those of some Brazilian states (for instance, Santa Catarina and Minas Gerais) and other capitals in South America, such as Bogota (Colombia) and Santiago (Chile) (Figure 2). On average, approximately 2 to 3 % of global energy consumption is used to pump and treat water for urban residents and industries. However, in some countries, it is estimated that approximately 10-30 % of pumped water is likely lost through leaks (18).

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Figure 1. Water withdrawal by different sectors for South America in relation to the Americas. Data from Ref. (15).

Figure 2. Average residential water use (m3 per capita/day) in some South American locations. Reproduced/adapted with permission from Ref. (14). Copyright (2012) from Elsevier. In addition to its use in agricultural, industrial and domestic areas, freshwater has a diversified use in the power generation sector. However, it is important to gauge the use of water in this sector because thermal power plants use large amounts of water for cooling, and significant amounts of water can be lost in the process by evaporation (19). Power plants also use significant amounts of land area and would therefore interfere with the existing water flow in these locations (20). 74 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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In considering the use of water for human activities, it is estimated that 60-80 % is used in agricultural irrigation in the developing countries of South America (21, 22). Thus, irrigation is an important component of food security because irrigated agriculture contributes 40 % of all produced food (15). Agriculture has become increasingly specialized in some countries, such as Brazil, Uruguay, Argentina and Chile, in response to global political and economic pressures to meet the expanding demands of the food sector. However, skilled agricultural systems may result in cumulative negative effects to the environment through the following factors: (i) water contamination with excess nutrients, pesticides, and pathogens, (ii) sinking groundwater levels from high demand and competition from a variety of stakeholders, including specialized crop production, (iii) rising greenhouse gas concentrations from soils depleted of inorganic matter, (iv) dysfunctional soils that have become exhausted from excessive tillage, salt accumulation, and pesticide inputs, and (v) the loss of family farms and rural infrastructure (23, 24). Because of the scarcity of drinking water and its waste by different sectors (agricultural, industrial, and domestic), some alternatives have been adopted to meet the demand brought on by global population growth. Thus, desalination processes have been used to obtain freshwater from salt water. During these processes, saline water is heated to vaporization, causing freshwater to evaporate, leaving behind a highly concentrated saline solution called brine. Desalination is performed by using thermal processes, such as multi-stage flash (MSF) and multi-effect distillation (MED), or electrically driven processes, such as reverse osmosis (RO). However, these processes are still costly because they require more stringent processing steps to remove ions that are present at higher concentrations than those of water drawn from wells, rivers or other water bodies. Desalination also brings another problem, namely high amounts of brine, which does not have any direct use and may accumulate in the environment. Even so, it is estimated that water desalination will reach up to 15 million m3 freshwater per day in some countries by 2030 (14, 22, 25).

Energy Generation in South America The energy matrix from South America will be discussed here by considering two primary divisions, that is (i) the power sector, which describes electricity production that is performed in different ways, as represented by hydropower, wind power, nuclear power, and thermoelectric power (which uses natural gas, oil, coal, or biofuels); and (ii) the transportation sector, which describes energy generation from renewable and non-renewable liquid fuels, such as fossil fuels (natural gas, oil, and coal) and biofuels (ethanol and biodiesel). In comparison with other continents, South America has one of the greenest energy matrices if the high share of renewable energy derived from hydropower plants, wind power, and biofuels is considered.

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Power Sector The power sector is represented by a complex network of power plants for electricity generation and thousands of kilometers of transmission lines for energy distribution per millions of people. The gross domestic product (GDP), electricity prices, population growth, proportion of the population with access to the electricity supply, and standards of living are factors that influence the continuous growth of the electricity demand (26). The power plant type will be chosen on the basis of the types of available resources in a given country and on affordable operational costs. In the Latin America region, electrical energy is primarily produced by hydropower (given the high availability of freshwater), thermal power plants (which run with fossil fuels or biofuels), wind power, and nuclear power. Although other forms of energy generation, such as geothermal power, solar photovoltaics (solar PV), marine, and concentrated solar power are potentially favorable for the region, they do not have significant current use, nor are they projected to have significant use by 2035, as shown in Figures 3 and 4.

Figure 3. Estimates of Electricity generation (TWh) for Latin America, according to the New Policies Scenario from EIA. The values on top of each bar are the totals for electricity generation (TWh) for the given years. Data taken from Ref. (26). 76 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Figure 3 shows the gradual increment of electricity generation (in TWh) in the Latin America region from 1990 to 2035 according to the New Policies Scenario (NPS) from the Energy Information Agency (26). The total electricity generation from 1990 (489 TWh) to 2011 (1109 TWh) has increased more than twice because of the economic growth experienced by Latin American countries. Projections to 2035 (2045 TWh) show that this amount would duplicate again. This projection shows the demand for electric energy production in the region to meet by 2035 to guarantee economic and social growth. These points show the urgent need for planning by Latin American leaders and policymakers. In Figure 4, the negligible share from geothermal power, solar photovoltaics (solar PV), marine, and concentrated solar power are also shown, and all of them together will only account for approximately 3 % of the electric energy mix in 2035. The major contributors will be hydropower plants, oil/natural gas/coal from thermopower plants as well as nuclear power. Each of the major forms of electricity production will be discussed with regards to their economic, social, and environmental impacts as well as the water-energy nexus for South American societies. Fossil fuels and biofuels will we discussed in terms of energy production through liquid fuels in the transportation sector.

Figure 4. Electricity generation shares among different types of energy sources for 2011 and 2035 in Latin America, according to the New Policies Scenario from the EIA. Data taken from Ref. (26).

Hydropower In a global context, hydropower is a significant source of electricity. Hydroelectricity is an alternative source of electricity that employs the hydraulic potential of a certain portion of a river by building a dam. It is a proven, mature, predicable, low-carbon emitter and cost-competitive technology, and it relies on a renewable energy source (2, 27, 28). Hydropower is a very efficient technology for energy production because approximately 96 % of water movement inside turbines is converted into electric energy (27). Electricity generation in South America comes mostly from hydropower stations. In all South American countries, electricity comes primarily from large plants, which feed national electricity grids. In spite of its widespread use, there 77 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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are many adverse impacts from installing large hydropower stations that should not be neglected. This subject includes complex issues with both social and environmental impacts. The expropriation of large urban and rural areas could be regarded as a negative social impact, which would move a large number of people to new areas and causes great distress and tension in the affected population. From an environmental point of view, the disruption of sediment transportation, fish migration, downstream flows and estuaries, and a lack of environmental integrity in the affected aquatic system can be observed (2, 27, 29). Both social and environmental concerns tend to be exacerbated over time. Another alternative for obtaining the advantages of hydroelectricity as well as minimizing its disadvantages is to replace large-scale setups with small-scale hydroelectric power. Small-scale hydropower stations seem to be sources of clean and renewable energy, which would please many ecologists and environmental activists, and these stations would not provoke the same social issues (29, 30). Additionally, small, decentralized hydropower stations would be good alternatives for the electrification of small towns, small villages, and remote and rural areas that are not connected to the primary electrical grids. However, they have not been developed to their full potential. South American electricity is a centralized system that is primarily derived from large hydropower stations, as in Paraguay (96 %), Brazil (87 %), Venezuela (70 %), and Colombia (75-76 %) (30). Nevertheless, some countries such as Peru, Argentina and Brazil also had installed capacities of 69.4, 15, and 21 MW from small hydropower stations in 2013 (30). However, these stations contribute a small amount of the total electricity produced by hydropower stations in their respective countries. Hydroelectricity has been noted for having a large water footprint from a global average standpoint (31); the larger the reservoir, the higher the water loss via evaporation. Until recently, there have been no comprehensive estimates about the water footprints of hydropower plants (HPP). The water budget for hydropower plants is still unclear. However, Mekonnen and Hoekstra (32) have calculated the water footprint from 35 hydropower plants (HPP) around the world (with 15 HPP from South America) (Table 1), and the average blue water footprint of the selected HPP is 59.3 Gm3 yr-1. However, this number may vary greatly from one place to another, as noted in Table 1, according to the reservoir surface and climate characteristics. When considering the amount of stored water in hydropower reservoirs, this amount would also be regarded as a huge amount of stored energy. When one reservoir loses a certain amount of water by evaporation and the water vapor migrates to distant regions, energy is also being lost. The amount of water, and also the embodied quantity of energy in the water, can be transported from a water-rich to a water-poor region that would then become enriched in both water and energy or vice-versa. This water/energy availability or scarcity would likely be exacerbated over time because of climate changes, as evidenced by IPCC reports and their scenario projections to 2050 or 2100 (3, 27). In theory, this movement of energy and water could reach transboundary regions and could even raise ethical and diplomatic issues when considering geopolitically stressed places, or when one freshwater reservoir is shared by two or more countries and at least one of them uses more freshwater or pollutes it more than others. 78 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

Table 1. Water Footprint of Electricity for Selected Hydropower Plants in South America*

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Hydropower plant

*

Reservoir area (ha)

Country

Installed capacity (MW)

Evaporation (mm yr-1)

Water footprint (m3 GJ-1)

Chivor

Colombia

1200

1008

1607

1.7

El Chocon

Argentina

81600

1200

2089

131

Estreito

Brazil

45600

1050

2285

70.6

Guri

Venezuela

426000

10300

2787

71.7

Itaipu

Brazil-Paraguay

135000

14000

1808

7.6

Itumbiara

Brazil

76000

2082

2239

52.5

Jaguari

Brazil

7001

460

1782

14.4

Marimbondo

Brazil

43800

1400

2330

38.3

Pehuenche

Chile

200

500

1884

0.4

Playas

Colombia

1100

204

1663

3.6

San Carlos

Colombia

300

1145

1726

0.3

São Simão

Brazil

67400

1635

2229

40.8

Sobradinho

Brazil

421400

1050

2841

399

Tucurui

Brazil

243000

8400

2378

49.5

Yacyreta

Argentina-Paraguay

172000

2700

1907

79.6

Reproduced/adapted with permission from Ref. (32). Copyright (2012) European Geosciences Union, from Mesfin M. Mekonnen and Arjen Y. Hoekstra.

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The volume of stored water energy has been declining in relation to the overall size of South America in the last 30 years (26). Projections from the Energy International Agency (EIA) in its New Policy Scenario (NPS) on Latin America for hydropower-based electricity generation ranges from 715 TWh in 2011 to 1186 TWh in 2035. The electrical capacity is projected to be 258 GW in 2035 compared with 143 GW in 2011 (26). However, it is unknown if Latin America will fulfill these projections by 2035 because this region of the world is suffering from restrictions on water, which is unequally available throughout the region. In addition, climate changes may contribute to a dramatic reduction in the water supply of this region. Therefore, HPP is subject to freshwater availability and might suffer some drawbacks in the next 20-30 years. Although Brazil is very famous for having plenty of freshwater, this water is primarily located in the Amazon (where less than 20 % of the Brazilian population lives). In the southern, southeastern and northeastern regions of Brazil (where more than 80 % of the Brazilian population lives), there is much less water available, and there are even some places that are facing water scarcity from climate changes. The São Paulo metropolitan area, which is the most populated and industrialized region in Brazil, has been experiencing water scarcity in recent times from an abnormal decline in water levels in the Cantareira basin, from insufficient rainfall (2). There have also been reports of water scarcity in Peru, Uruguay, Ecuador, Bolivia and Colombia, at least since 2000 (10–13). Those regions are likely facing long drought periods, and they eventually may not have an adequate energy supply. To prevent suffering from energy shortages and to depend less on climatic conditions that directly affect electric energy from hydroelectrics, each country uses other energy resources, depending on their own characteristics. For example, Colombia and Peru, which are the only South American countries with coal reserves, use coal for energy generation via thermopower plants. Bolivia possesses good reserves of natural gas and also uses this resource in thermopower stations. Despite having the biggest freshwater reserves in the continent, Brazil has also used a small amount of electricity as generated by either biodiesel, fossil diesel or burning natural gas in thermopower stations. The share from hydropower and other forms of electric energy generation for South America from now until 2035 and thereafter will depend on the abundance of the water supply. When this resource is abundant, hydropower is the most competitive and affordable form of electricity generation. Wind Power The use of wind energy implies that the kinetic energy of moving air will be converted into useful energy, such as electricity. As a result, the ease and the benefits of using wind to supply electricity are highly dependent on local wind conditions as well as the ability of wind turbines to reliably extract energy over a wide range of typical wind speeds (27). The global generating capacity of electrical energy from wind power was 318 GW by the end of 2013 (33). New Policies Scenario (NPS) projections from EIA estimates that the wind power-generating capacity of electricity will be 1130 GW in 2035 (26). 80 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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After hydropower, wind is the largest producer of renewable power in Latin America. Electricity generation from wind power in Latin America was 4 TWh in 2011 and it will be 103 TWh in 2035, according to the NPS. Thus, the wind power electrical capacity, which was 2 GW in 2011, will be 29 GW in 2035 (26). In the South American region, Brazil, Chile and Argentina are the primary countries that are investing in wind farms. At the end of 2013, the production capacities were 3.399 MW, 355 MW, and 217 MW for Brazil, Chile and Argentina, respectively. In the rest of South America, wind power is very small and incipient, with a total of 143 MW for Colombia, Ecuador, Guyana, Peru, Uruguay, and Venezuela altogether (34). Brazil leads the wind power sector in Latin America by far because of its more extensive experience in using this technology, its favorable areas close to the Atlantic coastline with strong winds (7 m s-1 wind velocity), and governmental commitment in recent years (35). In 2014, Brazil had 128 wind farms onshore. Wind power use in Chile remains modest but is increasing quickly. At the end of 2010, its installed capacity was 172 MW; however, this capacity had risen to 355 MW by the end of 2013. In August 2014, Chile inaugurated its largest wind farm, called El Arrayan, which is located on a coastal hillside 400 km north from the capital of Santiago. This farm consists of 50 giant turbines with an installed capacity of 115 MW and is going to feed part of the electricity grid for the copper mining industry (36). Argentina is the South American country with the highest wind power potential because it has plenty of sites distributed around its territory (75 % of the total area) that receive strong winds (7-9 m s-1 wind velocity) as well as a high level of technology and experience in the wind power industry, with one homegrown wind turbine manufacturer. However, at 217 MW of installed capacity, Argentina is far below its wind power potential (27, 35). The use of wind energy is gaining importance because of its environmental benefits and possible contributions to the provision of domestic energy. Wind energy is convenient when the water footprint is considered, because wind power’s direct water consumption is essentially negligible. The life cycle of water consumption by wind power (both direct and indirect consumption) is 0.64 L kWh-1 (2, 37). In comparison with thermo-power stations, which burn coal, natural gas or diesel for energy production and emit large amounts of greenhouse gases (GHG), which contribute to the intensification of climate changes, wind power emits very low levels of GHG (8-20 g CO2/kWh) and would help with climate change mitigation. Therefore, the more wind power is used, the less fossil fuels are used for energy generation. Additionally, the energy used and the GHG emissions produced in the direct manufacture, transport, installation, operation and decommissioning of wind turbines is small, if accounting for the energy generated and the emissions avoided during the lifespan of wind farms (and their costs are recovered after 3.4-8.5 months of wind farm function) (27). Wind power has been gaining significant progress since 2009 and exhibits versatility because it can be adjusted to have more benefits from turbine movements beyond electricity generation. During the production of electric energy, the wind power turbine movement could also be used for pumping freshwater from difficult access locations to cause desalinization, providing 81 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

the necessary energy for water to pass through membrane systems (27). Thus, wind power would be valuable to help areas with freshwater restrictions and to improve energy and water interdependence. However, interruptions in wind power should also be considered, together with the necessary investment in R&D to make it a mature technology. For these reasons, wind power requires additional backup reserves of energy from other sources, which are usually non-renewable, high-carbon emitters (2, 38).

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Nuclear Energy Nuclear power is a type of heavily concentrated energy. For instance, the energy density of reactor-grade uranium is 3.7 x 106 MJ kg-1 in comparison with 55.6, 45.8, and 21.5 MJ kg-1 for natural gas, diesel, and coal, respectively (2). Supporters of nuclear power would note that it is a promising solution to meet increasing energy demands by providing cheap and reliable energy as well as helping to reduce CO2 emissions and mitigate climate changes. A complete and well-organized nuclear fuel cycle system would help in transitioning the global energy system from non-renewable to renewable and sustainable power generation (39). However, there are many negative aspects of nuclear power. Concerns about hazards, nuclear accidents, the depletion of uranium reserves, and unfavorable economic aspects have effectively slowed down the growth of nuclear energy in many western countries since the 1980s. However, nuclear power remains important and has somewhat expanded in some countries such as the USA, China, Russia, and India (40). If nuclear power has a favorable carbon footprint, according to Schneider et al. (41) and also as recently reviewed by da Rocha et al. (2), the same cannot be said about its water and land uses. The steps in the nuclear fuel cycle that are considered for these estimates are (for water use, land use) as follows: uranium extraction (6.3 x 10 6 L, 362 m2), conversion (1.1 x 10 6 L, 8.7 m2), enrichment (3.1 x 10 4 L, 6.17 m2), fuel fabrication (1.68 x 10 4 L, 0.63 m2), and depleted uranium management (1.1 x 10 4 L, 9.1 m2) per ton of uranium. This activity requires 7.46 x 106 L water use and 387 m2 land use per ton of uranium (41). Therefore, nuclear-based electricity uses of water and land can be easily observed, and they should be taken into account when planning a new nuclear plant. The global nuclear electricity yield was 2359 TWh from 31 countries and Taiwan in 2013 (42), and the NPS projection of nuclear power with regard to electric energy production through 2035 is 4294 TWh, with a 12 % share of the energy mix. Indeed, nuclear power is a very important form of energy generation in the USA and the EU because their nuclear electricity production in 2013 was 790.2 TWh and 847.5 TWh, respectively. In South America, there are three nuclear power plants in Argentina and two others in Brazil, which has a third one under construction (42–44). Argentina and Brazil are the only South American countries with operational nuclear reactors. In 2013, the total nuclear electric energy produced was 19.5 TWh. The projection from the EIA in the NPS for 2035 for the electricity generated from nuclear power in Latin America is 53 TWh, which is 2.7 times higher than the 2013 level (26). 82 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Although the nuclear power program in Brazil is being phased out, Argentina has just finished negotiations with China for the construction of two new nuclear power plants (in February 2015). In 2014, Bolivia announced its intention to start a nuclear program and contacted France for help with viability studies and also to acquire the associated know-how (45–47). Chile, which is subject to tsunamis and earthquakes just like Japan, abandoned its then-serious considerations of nuclear power after the Fukushima nuclear accident. Venezuela and Uruguay also abandoned their nuclear power plans. At this moment, nuclear power plays only a small role in the electric energy mix of Brazil, with a share of only 3 % (43). The current generation capacity comes from two nuclear power reactors, namely Angra I (640 MW, operational in 1985) and Angra II (1.35 GW, operational in 2000), which have been operating at Angra dos Reis, a region close to Rio de Janeiro (2). The preliminary work on a third reactor known as Angra III (1.35 GW) has been ongoing since 1980, but it was suspended after the Chernobyl disaster (in 1986) and re-started only in 2010. The construction of Angra III was then delayed again after the 2011 Fukushima accident (26). Nuclear-based electricity in Argentina supplies approximately 10 % of its electric energy. The power generation capacity comes from three nuclear reactors, namely Atucha 1/Peron (335 MWe, operational in 1974) and Atucha 2/Kirchner (692 MWe, operational in June 2014), both of which are 100 km away from Buenos Aires, along with Embalse (600 MWe, operational in 1983) in Cordoba, which produces 1927 MWe. Argentina has already announced the construction of its two next nuclear reactors by the China National Nuclear Corporation (44). Transportation Sector The transportation sector is fueled by fossil fuels and biofuels. With respect to fossil fuels, the primary energy sources are oil, coal, and natural gas from conventional and unconventional sources. Biofuels generate energy from biodiesel and ethanol. Fossil Fuels Coal, petroleum, and natural gas are generally regarded as non-renewable fossil fuels. They have been widely used by humankind for energy production. The energy density for natural gas is 55.6 MJ kg-1, and it is 45.8, 45, 44.2, and 21.5 MJ kg-1 for diesel, gasoline, crude oil, and coal, respectively (2). These fuels are used for energy production in buildings, industries and in the transportation sector. At the end of 2013, the Americas (which includes North, Central and South Americas as well as the Caribbean) had one-third of the known worldwide reserves of crude oil (536 billion barrels), and one-tenth of known natural gas reserves (688 trillion cubic feet (Tcf)) as well as immense recoverable resources of oil and gas, including tight oil and shale gas reservoirs. In 2012, the Americas produced 29 % of the world’s liquid fuel supply, at almost 26 million barrels per day (bbl/d), and they consumed one-third of the world’s liquid fuels, at close to 30 million 83 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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bbl/d. In the same year, the Americas produced and consumed approximately 31 % of the world’s natural gas use, at 37 Tcf, and they accounted for 20% of the global natural gas trade in imports and exports, both at 6 Tcf. More than 80 % of natural gas imports and exports in the Americas were transported via pipeline to neighboring countries, and the remainder was traded within the region as liquefied natural gas (LNG) (48). Latin America has the second-largest conventional oil reserves outside the Middle East. However, this region’s natural gas and coal reserves are not as large. Indeed, fossil fuels are not equally distributed in Latin America. Oil and gas reserves are concentrated in Venezuela (both) and Bolivia (natural gas only), and most coal reserves are located in Colombia and Peru. For this reason, coal-fired thermoelectric plants generate nearly 40 % of the total electricity in the latter countries. Chile, which does not possess large amounts of coal, oil or natural gas, imports liquefied natural gas (LNG) from Asia, principally after Bolivia stopped natural gas exports (as well as for other South American countries, such as Brazil, Argentina and Peru). Unlike the rest of the countries in South America, diesel and other hydrocarbon fuel derivatives in Brazil are only used in the transportation sector (49). South America and the Caribbean have approximately 126 billion barrels of oil resources, approximately 44% of which are offshore from Brazil (50). Brazil is the world’s leader in oil exploration in deep and ultra-deep waters and has one of the largest Pre-Salt proven reserves. Unconventional oil and gas from shale wells have been mentioned in Brazil as well as in Argentina (which has the second largest shale gas reserve in the world, only after China) (2, 51). Figure 5 shows the total primary energy demand (TPED) (in megatons of oil equivalent, or Mtoe) in Latin America from 1990 with projections until 2035, according to the NPS from the Energy International Agency (26). The TPED shows an increasing trend in the region from 1990 (331 Mtoe) to 2035 (941 Mtoe), which represents an increase of 610 Mtoe (or approximately 3 times) between the two periods. In Figure 6, the TPED share is shown (%) between 2011 and 2035 in the energy matrix in Latin America among nuclear power, fossil fuels, and renewables. Shale gas is released from impermeable rocks through a process called hydraulic fracturing, or fracking. This process requires large amounts of water and also produces huge amounts of wastewater from fracking fluids, which raises major concerns in relation to ecosystem and human health hazards. Water is the primary component of fracking fluids (95 %). Most of the remaining 5 % consists of sand or other proppants as well as biocides, gelling agents, scale inhibitors and lubricants. These toxic chemicals are used to hold open the fractures that are initiated by high pressure injections of water into the rock and to make shale gas extraction possible (52, 53). In a recently published review by da Rocha et al. (2) (and references therein), some estimates of the water footprint of fossil fuel exploitation are reported. Shale gas extraction demands 50-100 times more water than the extraction of conventional natural gas. For instance, the drilling step for Marcellus shale requires 296 thousand liters of water, and the fracking step requires 140,600 thousand liters of water per well. Surprisingly, although shale gas consumes more water than conventional gas, it consumes less water than coal. For comparison 84 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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purposes, coal extraction consumes 11-53 L water per MWh (L MWh-1), and shale gas extraction consumes 29.4 L MWh-1. Instead, the water requirement for conventional natural gas extraction is negligible.

Figure 5. Total primary energy demand (Mtoe) between 1990 and 2035 for Latin America, according to New Policies Scenarios from the Energy International Agency. Data taken from Ref. (26).

Figure 6. Total primary energy demand share (%) for Latin America in 2011 and 2035, according to New Policies Scenarios from the Energy International Agency. Data taken from Ref. (26). The water demand for traditional oil production is 28-73 L GJ-1, the demand for enhanced oil recovery is 75-9,065 L GJ-1, and the demand for oil sands is 70-1,800 L GJ-1. The water requirements for on-site consumptive water use by shale oil production are 629-703 L of water per barrel for surface production, and 159-322 L of water per barrel for in situ production (1, 2, 54). 85 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Biomass An important argument in favor of biofuel production is the reduction in greenhouse gas emissions, in comparison with fossil fuels (55). Renewable fuels primarily originate from agricultural products such as sugar cane, maize, vegetable oils, and forest biomass, among others. The primary biofuels produced are biodiesel and ethanol, which can be used alone or mixed with fossil fuels (56). South America possesses a diverse set of renewable energy sources, which can contribute significantly to the future demand in the global energy supply (57). Figure 7 shows that South and Central America have a prominent position in the global production of biodiesel, coming right after Europe. The primary biofuel producer in South America is Brazil, which has used biofuel since the 1970s when the oil crisis was the basis for the creation of the proalcohol program. The emergence of this program allowed for targeted sugarcane production to obtain energy. This initiative has allowed the use of sugarcane juice for producing sugar and ethanol in the same industrial plant. Other countries that stand out in terms of biofuel production in South America are Argentina, Chile, Colombia, Paraguay, Peru, Uruguay and Venezuela (58–60). Figure 8 shows that the production of the primary raw materials used in the production of biodiesel (soybean) and ethanol (sugarcane) is concentrated in the Americas, between the years 2005 and 2013. South America plays an important role in the production of raw materials for biodiesel production. A total of 839,270,836 tons of sugarcane and 145,853,460 tons of soybeans were produced by this continent in 2013. Of this total, the largest producers of sugarcane for that year were Brazil, Colombia and Argentina, corresponding to 88 %, 4.1 % and 2.8 % of the total production, respectively. Similarly, the largest soybean producers were Brazil, Argentina and Paraguay, corresponding to 56 %, 34 % and 6.2 %, respectively (61). It is estimated that these numbers will tend to increase significantly in the coming years through government incentives for biofuel production in South America.

Figure 7. Contributions to the production of biodiesel in 2010. Reproduced/adapted with permission from Ref. (59). Copyright (2015) from Elsevier. 86 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Figure 8. Distribution of sugarcane and soybean production by continent, between the years 2005 and 2013. Data taken from Ref. (61).

Some authors criticize biofuels because of their need for large amounts of water for feedstock production, and this need could cause large-scale water scarcity (62–64). In Brazil, which is the largest sugarcane producer in South America, the total water consumption by ethanol production is primarily distributed over the industrial process, such as sugar cane washing (5,330 L), extracting/grinding (400 L), juice concentration (30 L), electrical power generation (70 L), fermentation (4,000 L), distilling (4,000 L) and others (800 L), when considering the total water consumption for each stage per metric ton of sugar cane (1). In biodiesel production from soybean oil, it is estimated that approximately 14 and 321 L of water are used per liter of resulting fuel. This estimate is the average consumption, when considering different steps of biodiesel production, such as 0.5 L water with allocation, 120 L with crop irrigation, 11 L with farm inputs, 0.05 L with biodiesel plant construction, 1 L with biodiesel production and 1.3 L with distribution and marketing (65). To ensure the increased production of raw materials that are used in the production of biofuels, South American countries have made intensive use of pesticides and fertilizers to protect crops against pest attacks and ensure successful harvests (Table 2) (66). Given the large amount of pesticides and fertilizers that have been used in different fields, the increasing contamination of various water sources close to the production regions becomes worrisome because it could bring harm to human health and the environment (67–69). In addition to the problems caused by the excessive use of fertilizers, the intensive use of pesticides on areas close to rivers and lakes is one of the primary problems that cause the contamination of water resources. Pesticides that are applied to crops can persist in the soil for several years, and they may reach the surface water and groundwater. Thus, drinking water can be an important form of human exposure to contamination from pesticides that are transported and dissolved in water (68, 69). 87 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

Table 2. Production of the Primary Raw Materials for Biofuel Production (Biodiesel and Ethanol) and the Amounts of Pesticides and Fertilizers Used in Some South American Countries. Data taken from Ref. (61). Country

Sugarcanea

Soybeansa

Fertilizersb, c

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(tons)

Pesticidesb, d

(tons/1000 ha)

Argentina

23,700,000

49,306,201

38.25

not available

Bolivia

8,065,889

2,347,282

7.8

8.10

Brazil

739,267,042

81,699,787

80.59

not available

Colombia

34,876,332

85,442

215.56

14.50

Paraguay

5,544,797

9,086,000

55.74

not available

Peru

10,992,240

2,709

69.31

3.49

Data production for the year 2013; Data on the consumption in 2010; Nitrogen + phosphate fertilizers; d Active ingredient use in arable land and permanent crops.

a

b

c

Figure 9. Estimated production of vehicles in South America and light vehicle sales in South American countries by 2019. Reproduced/adapted with permission from Ref. (71) CARCON Automotive. Studies on the impact of biofuel production on water quality have shown that this activity leads to the eutrophication (increased concentration of nutrients, especially nitrogen and phosphorus) of water bodies. Eutrophication can cause excessive plant growth and the decay of aquatic systems, leading to an increase in phytoplankton, decreased dissolved oxygen, increased turbidity, a loss of 88 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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biodiversity, a reduction in commercially important fishes, and other undesirable ecological effects (70). Thus, the production of raw materials (sugar cane and soybeans) for biofuel production has shown significant growth in recent years because of the increased sales of ethanol and biodiesel, which are encouraged by a significant increase in the South American fleet. Projections indicate an increase in the production and sale of vehicles in the coming years to countries such as Brazil and Argentina, which are important players in the biofuel production scenario in South America (Figure 9) (71). Considering the alternatives to fossil fuels, it is necessary to understand not only the costs and impacts of carbon emissions but also their potential impacts on land use, natural resources and other environmental impacts for which the production of alternative (bio)fuels may result in the pollution of water resources (65) as well as in air pollution when biofuel is burned.

Conclusions South America is a region of the globe with a diversified energy matrix and good reserves of freshwater. However, because this water is not equally available throughout the continent, many places face water scarcity. Additionally, many South American countries have suffered from intense droughts since 2000. This scarcity directly impacts not only well-being but also the power generation of the population. The worsening of the population’s well-being includes restrictions on drinking water, improper sanitation or water treatment processes as well as insufficient water for any activities needed by a given person to survive. In turn, restrictions on power generation could bring economic restrictions to the continuous development of the region. The primary challenges for South America regarding the water-energy nexus are as follows: • •

•

•

• •

the development of sufficient infrastructure (which is missing in parts of South America); political and economic stability (which some countries do not possess in the moment because they are developing countries or are suffering from recent corruption scandals); large domestic and international investments for the development or improved production of (conventional and unconventional) fossil fuels and biofuels; anticipated planning of alternative actions by the governments to suppress possible drawbacks in water availability and energy production from climate changes; governmental planning for the next 30-40 years for the water-energy nexus through food security and environmental sustainability; and finding a convenient balance regarding the contribution of biofuels and fossil fuels to the energy mix to meet energy demands, population growth, and international environmental agreements, such as the Copenhagen Accord and the Kyoto Protocol. 89 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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64. Chavez-Rodriguez, M. F.; Mosqueira-Salazar, K. J.; Ensinas, A. V.; Nebra, S. A. Water reuse and recycling according to stream qualities in sugar-ethanol plants. Energy Sustainable Dev. 2013, 17, 546–554. 65. Harto, C.; Meyers, R.; Williams, E. Life cycle water use of low-carbon transport fuels. Energy Policy 2010, 38, 4933–4944. 66. Zarbin, P. H. G.; Rodrigues, M. A. C. M.; Lima, E. R. Feromônios de insetos: tecnologia e desafios para uma agricultura competitiva no Brasil. Quím. Nova 2009, 32, 722–731. 67. FAO - Food and Agriculture Organization of the United Nations. Biodiversity for Food and Agriculture. Contributing to food security and sustainability in a changing world; FAO: Rome, 2010; 66 p. 68. Menezes Filho, A.; Santos, F. N.; Pereira, P. A. P. Development, validation and application of a method based on DI-SPME and GC-MS for determination of pesticides of different chemical groups in surface and groundwater samples. Microchem. J. 2010, 96, 139–145. 69. Azizullah, A.; Khattak, M. N. K.; Richter, P.; Häder, D. P. Water pollution in Pakistan and its impact on public health - A review. Environ. Int. 2011, 37, 479–497. 70. Delucchi, M. A. Impacts of biofuels on climate change, water use, and land use. Ann. NY Acad. Sci. 2010, 1195, 28–45. 71. CARCON Automotive. Visão do mercado automotivo; http://automotivebusiness.anankecdn.net.br/pdf/pdf_302.pdf, accessed 16th February 2015.

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Chapter 6

Critical Water Issues in Africa

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Shem O. Wandiga* Department of Chemistry, College of Biological and Physical Sciences, School of Physical Sciences, P.O. Box 30197-00100 Nairobi, Kenya *E-mail: [email protected].

Water scarcity, purity and delivery have become major challenges of humanity especially in Africa. Globally 748 million and in Africa 325 million people lack access to safe water. Water diseases kill 842,000 people annually. The majority of those who lack water live in rural areas. Africa is second to Australia in dryness but is home to 15% of global human population and has only nine percent of global renewable water resources. Most of Africa’s surface water has become polluted by human activities and its wells are becoming dry. Impacts of climate change and climate variability are making water scarcity more stressful. Technologies used for water harnessing are outmoded and inefficient. Africa needs to modernize its water purification technology; it requires adopting new methods like roof, pavement and urban water catchment to recharge its declining ground water level. Provision of safe drinking water policy need to change from piped water to every home to supply of point of use technologies at every home. There exist some potential new technologies that still require further research. The chapter highlights some recent development of nanoscience materials in water treatment that give promise to future trends. Similarly, small scale water harnessing technologies are outlined for ground water recharge and drinking water purification. Design of water education in Africa is reviewed and specific steps for improvement given.

© 2015 American Chemical Society In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Introduction Safe drinking water and sanitation are the major challenges in Africa. Water is essential for life but in Africa it is also the major challenge for safe living. Substantial amount of resources is spent to find it in space and to establish that life can exist in other planets besides our earth. Unfortunately, when we have it we take it for granted; abuse it by polluting it or using it extravagantly. Access to safe water is one of the leading global challenges in this century. Globally 748 million people lack access to it, it kills 842,000 people every year and 82% of those who lack it live in the rural areas of the world with only 18% living in urban areas. In Africa 325 million people lack access to safe water (1, 2). Today, most sources of water in Africa have high loads of soil sediments, human wastes and chemical pollutants. The sources of water in the continent is mainly from its 63 shared water basins, six major aquifers and more than 160 inland lakes (2) larger than 27km (2). The surface water sources supply 173 million people with their daily water needs. However, Africa has large areas of desert, arid and semi arid lands. It is second to Australia in dryness, it has 15 percent of global population and only 9 percent of global renewable water resources (1). In the dry areas water sources are mainly from ground water, sand beds of perennial rivers, springs, and manmade dams and pans. Source of potable water is mainly boreholes (24 percent) in rural areas that are increasingly becoming unreachable and piped water (39 percent) in urban areas serving mainly the middle and upper class dwellers. About 37 percent use untreated water for drinking that cause diarrheal diseases and other water born diseases (2). Examples of sources of water are shown in Figures 1-6 below:

Figure 1. Water pan in Bondo Sub-county, Kenya showing shared water usage. Photo taken by Prof. Shem Wandiga. 96 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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The continent’s water availability is unevenly distributed and follows more closely the ecological zones and some international boundaries. For example equatorial Central Africa tropical zone has 50.66 percent of available water while Northern Africa has only 2.99 percent (3). Climate variability and climate change has contributed significantly to water scarcity and non-availability. Africa therefore relies heavily on its ground water that represent only 15 percent of total renewable water resources that supplies about 75 percent of its population with drinking water (3). The impacts of climate change and climate variability combined with fast increasing human population projects a diminishing supply of safe water in the future. For example, it is projected that 25 African countries will be water stressed by 2025 compared to 13 in 1995 (3). Inadequate financial resources and institutional arrangements portray a situation that will continue to get worse in the coming years. The big gap in technological knowledge between African states and developed nations and low political will to prioritize water challenges are not likely to make the improvement of water quality, improved sanitation, reduced industrial and irrigation applications any better at present or in future Africa.

Figure 2. Kowuor Water Pan, Nyangoma Division Bondo Sub-county, Kenya. Photo taken by Prof. Shem Wandiga.

Economic losses caused by water in the continent are large. Africa’s GDP is suppressed by 5% due to lack of sanitation infrastructure, 2% due to power outages, between 5%-25% due to drought and floods whose figure may go higher when future impacts of climate change and climate variability are taken into account (3). Investment potential in water services is huge as amount needed to improve Africa water situation is US $50 billion per annum for the period from 2010 to 2030 and US$ 30 billion for the following 30 years (3). 97 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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This chapter examines the critical water issues in the continent along the Millennium Development Goals (MDG) water targets: soil and water conservation and management, improved water harvesting technologies, improving drinking water purification technologies, new technological innovations for sanitation, mobilization of communities in improvement of health and hygiene and framework for the design for education in water.

Figure 3. River Yala: Jaramogi Oginga Odinga University of Science and Technology abstraction Point. Photo taken by Prof. Shem Wandiga.

Figure 4. Shallow well point of water. Photo taken by Prof. Shem Wandiga. 98 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Figure 5. Nairobi River, showing human waste pollution. Photo taken by Prof. Shem Wandiga.

Figure 6. Settled pond water separated from particulates for multipurpose use. Photo taken by Prof. Shem Wandiga.

The Millennium Development Goals (MDG) Water Challenges A. Water Targets Sub-Sahara Africa has made small progress in achieving the improved drinking water MDG target. Since access to piped water in every home has stagnated at about 16 percent between 1990 and 2012 (2) it is unlikely that it will change much post 2015 unless we adopt new technologies. Two out of five people in Sub-Sahara Africa lack access to improved drinking water sources (2). Increasing population combined with declining surface water sources due to 99 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

climate change and climate variability require a change of approach in catchment, storage and purification technologies for supply of safe drinking water. It is most unlikely that piped water with concomitant high engineering costs will yield the desired outcome in the second phase of development. Other water harvesting, storage and purification technologies need to be promoted given the fact that the amount of rainfall has not changed and will remain the same. However, the pattern of rainfall and duration of rainfall has changed and will continue to change.

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B. Soil and Water Conservation and Management Water catchment technologies that capture roof water and storm run-offs and store it have been implemented in other countries and need to be adopted and improved in Africa to safely use such water for drinking, irrigation and household chores. Presently these technologies are ignored and not used enough in many of the African communities. Catchment of roof and storm water and storing it in large tanks above ground or underground offer many advantages such as no mineral additives in the water, ease of delivery and allow recharge of water aquifers so that ground water table rises as opposed to its rapid decline (4–6). Secondly, ground water filtration improves quality by eliminating impurities. The construction of shallow wells and deep wells with high recharge rate enhance community’s access to drinking water (7). Three technologies exist for water catchment. The first is the installation of roof water tanks beside the built environment (5, 6). One square meter of roof harvests one liter of water for every one millimeter of rainfall. A simple roof of a house can thus fill a tank of 225,000 cubic meters every season. Harvesting similar amount twice a year is possible. The harvested amount can see the average household of 7 through the dry seasons (4). The second technology is the building of sand dams along perennial rivers to slow down the rate of river flow and allow the water to percolate through the sand into ground water on the upper side of the sand dam (5, 6), and the third technology that is least preferred is the building of earthen dams to form reservoirs or ponds that can collect surface water from hills. Such dams are used by both animals and human (see Figure 1 above). They can be sources of zoonotic diseases transfer. Secondly they accumulate dirt, have high evaporation rate and become sites for algal and broad weeds habitat (5). Urban water collection has great potential for ecological system improvement and ground water recharge. Run-offs from roads or pavement areas can be channeled into reservoirs or underground storage ponds that will improve plant growth and ensure seasonal pastures for animals. Building plastic ponds of 120 meter cubed made of plastic and ropes enable small scale irrigation of crops. Lastly improved rainwater/soil conservation technologies like Zai or tassa and stone rows and half moon allow soil to retain water for crop growth (7–9). The choice of the technology is dependent on government policy for community support as initial investment is needed for the poor communities. Technology works best where there is strong community participatory approaches to farming, depends on the nature of the innovation being promoted and the topology and soil type. Construction of large dams works best when done between 100 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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hills. However construction of stone rows (7) can be done on plains or slopes. Stone walls are placed at distances of 0-10 cm, 10-20 cm and 20-40cm depths along the slope and may be arranged in rows or half-moon configuration. Water together with nutrients are retained upstream of the stone wall. Zai or tassa (7) is the technology of digging planting pits in the farm area, mixing the soil with manure or fertilizer (use of farm yard manure is preferred) and planting seeds in the pit. Watering is done using sprinkler as one would do in flat row planting (9–11). Widespread use and government support of soil and water conservation and management will improve soil carbon content, crop yields, resilience to drought and reduce undernutrion. Some of the above technologies are widely practiced in Ethiopia, Bukina Faso, Mali, Senegal and Niger in Africa and Nicaragua and Brazil in South America for example. However, government policies are lagging behind the efforts of researchers and NGOs workers’ efforts (11, 12).

C. Improved Drinking Water Purification Technologies Provision of safe drinking water in the African household has proven to be intractable using the prevailing technologies of water supply. In many instances there is not sufficient water for pumping. Where water exists in abundance there is lack of resources or appropriate technology to distribute it to every home. Maintenance is a major bottleneck in many communities where water has been supplied. Many efforts have been expended in sinking and development of boreholes in rural Africa. Most of the boreholes are abandoned because of lack of knowledge, maintenance resources or spare parts and lack of ownership. The many boreholes built and uncontrolled water withdrawals have succeeded in lowering the water table to an extent that reaching water table has become expensive. Therefore there is need for a paradigm shift from providing piped water to every home in the rural areas to providing technology for water purification at the point of use. For us to realize success in this area the technology needs to meet the following criteria: be cost effective, acceptable and affordable, must meet the agreed standards, provide sufficient output, and comply with health concerns, social concerns and scalable and link up with industry. Every consumer must be empowered with the capacity to measure water quality at the point of use. Assessing water quality at various levels is important for water security. Today, there is no dearth of new technologies in the market. Across the world, companies have researched on and introduced various technologies in the areas ranging from water monitoring to water treatment. However, a lot of these technologies are either too cost prohibitive in the African scenario or do not cater to the nuances of the African market. These technologies require a testing ground to review both the relevance and the efficacy of the solution. Also it has to go beyond the technical or technological aspects and address the social aspects of adoption of such innovations. There is need to identify barriers to the uptake of the technology specifically in terms of contextual determinants and which are a central reason for low adoption 101 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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rates of beneficial health technologies in developing countries. For instance, the impact of technology and treatment interventions for safe drinking water in homes intrinsically depends upon household decision -making, specifically, how women’s preferences, welfare and opportunity cost of time are captured in the decisions. For example, differences in men’s and women’s costs and preferences related to a lack of access to safe drinking water can affect household choices depending on women’s “say” or power over household decisions. Social innovation and applied research is required in the following areas: First, develop affordable and safe drinking water solutions at the household level. The emphasis is on affordability, which is the primary reason why many of the available technologies are not acceptable. Several Grand Challenges have to be taken up in the years to come to get solutions around the African continent such that every citizen is empowered with clean water, conforming to standards. As input water in various parts of the country (12) varies, technologies offered must be adaptable to those regional requirements. The role of advanced materials and nanotechnology enabled solutions cannot be over emphasized in this context. Second, real time water quality monitoring at various levels, linked through wireless networks is an urgent need. While several sensors exist currently, they are either expensive or do not cover all parameters of importance or do not work at concentrations of relevance. Third, quality of drinking water sources must be known online, at least to enforcement agencies, nationally. These sensors, especially for micro-organisms, and toxins such as arsenic and fluoride, must be deployable at schools, community facilities and large dwellings, besides large water sources. Affordable sensors for essential water quality parameters are expected to become part of water purifiers in the years to come. At the same time, colorimetric test strips for quality parameters could be made available for consumers. The mission of this exercise is to empower everyone the right to know his/her water quality. Nanotechnology research is moving very fast. Candidate materials most commonly mentioned involved nanofiltration, the germicidal efficiency of nanosilver and the photo catalytic degradation power of nanotitanium. In our research we recently published (13) the results of Titanium (IV) oxide Tungsten (VI) oxide composite. “The research findings appeared on world’s prestigious International Journal of Photo catalysis. This work focused on synthesis of Titanium (IV) Oxide and Tungsten (VI) Oxide composite and testing the composite as a photo catalyst in deactivation of Escherichia coli in water. Modified wet chemistry method was used and the synthesized nanoparticles calcined at 575° C, taken through X-Ray fluorescence and X-Ray diffraction. The result showed a particle size diameter of 18.99nm. The nanoparticles photo catalytic inactivation efficacy of Escherichia coli in water was tested. 3M Petri films from 3M Microbiology Products, U.S.A., were used for Escherichia coli colony forming units’ counts. ATUV 8W G8 T5 lamp from PHILIPS emitting between 350-600nm was used as energy source. The catalyst reduced Escherichia coli count by log 3.415 at an optimum catalyst amount of 0.75 g/L at pH 7.3 using the Chick-Watson model for disinfection kinetics. This work proved that photo catalysis is a promising technology in water purification with possible and practical opportunities existing especially for small-scale point-of-use water purification 102 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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units where potable water could be treated for disinfection of pathogens or trace priority pollutants remaining in water distribution network after conventional treatment methods. This work proved that nano particles can provide solutions in treatment of drinking water especially for poor communities living in the tropics. Although a lot has been done on photo catalytic decomposition of pollutants in water, this work went further to explore the potential of simple composite synthesized using locally available and abundant (TiO2) resource in Kenya. The composite was synthesized using fairly mild conditions and later tested for water purification applications using Escherichia coli in natural water samples collected from the environment as opposed to lab cultured strains. The experiments proved that the titanium (IV) oxide- Tungsten (VI) oxide composite can be effectively used in the removal of microbial pollutants from water. The results indicated a negligible Escherichia coli reduction rate variation to acid conditions. From the data obtained significant disinfection was not observed for the dark control (photo catalyst only with no UV), UVA irradiation alone (in the absence of photo catalyst) or with the sample stirred in the presence of photo catalyst. Process taking place during dark control was explained as adsorption-desorption of the Escherichia coli from the surface of the photo catalyst. Photo catalysis is a promising technology in water purification with possible and practical opportunities existing for small-scale point-of-use water purification units where potable water could be treated for disinfection of pathogens or trace priority pollutants remaining in (or entering) the water distribution network following conventional treatment; for example, chlorine-resistant pathogens, endocrine-disrupting chemicals (EDCs) or pharmaceuticals and personal care products (PPCPs). Our earlier work (unpublished) showed that our photo catalyst composite was effective in removal of heavy metals and organochlorine pesticides which are some of the pollutants that are not removed by chlorination. The green reactions of photo catalysis are ideal in energy saving and emission reductions. This work focused on exploring the potential of nanoparticle photo catalysis in use for water purification. Escherichia coli was used as model bacteria to explore disinfection kinetics of the nanocomposites used and the optimum working conditions of pH, initial catalyst amount and time factors. The findings can be applied to point-of-use water purification especially for poor communities living in the tropics where solar energy can be harvested and harnessed to effect pathogen removal. The major limitation in this work was the subsequent requirement to filter the nanoparticles after each test. This is due to the fact that the tests were performed with dispersed and stirred nanoparticles in water. Anchoring procedure for the nanoparticles on immobilized support will be undertaken later. From the findings of this research work, it is recommended that policy makers take into consideration the potential contributions of scientific research into policy implementation in water purification processes. In Kenya, the right to clean drinking water is embedded in the constitution as a right to every citizen. This can only be realized if clean and energy efficient technologies are adopted and incorporated into policies that guide water purification and distribution. The relevant Kenya Government research funding bodies should work with research institutions through funding water purification research, and coordinate the implementation of research findings to target communities. 103 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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D. New Technological Innovations for Sanitation Integrated water management requires use of surface, ground, grey and storm water in a well planned system. The planning starts with the mobilization of the community to agree to work and plan their residential areas or urban centers such that there are specifically designated areas for residence, farming, animals, water reservoirs, playground and other infrastructures like roads and energy generation. The waste from each designated area is integrally used in the generation of safe water and energy through biogas system or solar energy generation system. Well designed drainage system does not allow blockage during rainy season, but provides conduits for free flow of storm and grey water to its storage tank, similarly river water is channeled to its storage tank. With well recharged aquifer, ground water can be added from a well to the surface and storm water tanks. The roof catchment water is filtered through sand and charcoal and stored in a separate storage tank (9, 12). The grey water is used for energy production, storm, surface and ground water is for agriculture and rain water is for drinking. A schematic of a possible integrated water supply and sanitation system for a future development of Arua, Uganda is given in the report (9) on storm water reference (9) page 8. Small homesteads can use the same planning principle to develop a safe sanitary system. However, for rural Africa the digging of pit latrines will continue to play a major role in providing safe sanitation (9). I describe below one of our studies (12) in a typical rural community in Kenya: The purpose of the study (14–16) was to establish the relationship between the water quality challenges, community health and water rights conditions. Health challenges have been linked to water quality and household income. About 69% of the households have no access to treated water. Whereas 92% of the respondents appear to be aware that treatment of water prevents water borne diseases, the lowest income group and children share a high burden of water borne diseases requiring hospitalization and causing mortality. Open defecation (12.3%) in these areas contributes to high incidence of water borne diseases, especially in the rainy season. The community’s constitutional rights to quality water in adequate quantities are most infringed. Increased investment in water provision across studied sites, improved sanitation and availability of affordable point of use water purification systems will have major positive impact on the health and economic well being of the community. Water quality still presents a serious problem to Lake Victoria riparian communities. Since several initiatives put in place are not having the desired impact of and saving lives, there is a need for all stakeholders to rethink the approaches that have been used in water quality management at the point of use. Most desirable would be initiatives that work through community sensitization and capacity building. The overall objective of this project was to mobilize and train the local communities on water quality at the point of use and sensitize individuals on their water rights as provided for in the Kenya Constitution, 2010. The awareness created is expected to improve well being, create income generation opportunities and reduce poverty of the people. 104 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Water rights of the people living in the area under study have not been met is a fact. However, under the new constitutional dispensation, the responsibility for this state of affairs and the solutions lie with the National Government, the County government and the community themselves. The study was conducted in Bondo sub-county, Siaya District, Kenya. It was stratified as follows: Lake region (up to 10 km inwards from the lake shore), River Yala region (up to 10 km south of the river), and Middle region (area between Lake and River regions above). Results indicated that the major sources of potable water in the area under study are: Lake Region, - lake water at 55.3%, River Yala region tap water at 47.4% and Middle region, tap water at 29.2%. A total of 30.6% in all the three regions is connected to tap water with the other 69.4% sourcing their water from alternative sources. The first ranked issue of concern to the residents of the River Yala region is availability of water. The region is predominantly supplied by reticulated water from Siaya and Bondo Water and Sanitation Co. Ltd. (SIBO), and it is clear from the importance attached to this issue by the respondents that the piped water supply is inadequate. Besides availability, quality and affordability are also issues in this region. In the Lake region water quality is the major issue followed by availability, access, and affordability which are also made worse by household distance from the lake. Meeting the right to quality water in adequate quantities as enshrined in the constitution is a serious challenge as the legislative framework as outlined in the Constitution makes water and sanitation a shared function between the County Governments and the National Government. Clear demarcation of duties and functions is being prepared and anticipated in the revised Water Act yet to be tabled in Parliament. Provision of the necessary legislation and policy to guide the distribution and use of water is the responsibility of the National government. The study found that the source of water is not a significant determinant of water borne diseases (16). This implies that all sources have low water quality. The lowest income group and children share a high burden of water borne disease. 64% of the hospitalized cases are from those earning between US$ 0 and US$2.5 as constitute 60% of those who lost their lives. 82% of those affected were children between the ages of 5 and 15. This is a serious challenge as water borne diseases are known to cause nutrition imbalances and mental retardation. The community can play a pivotal role in reversing this situation by improving knowledge and awareness about diseases related to water quality, availability and management. Actions that should be taken include, volunteering to attend training and sensitization meetings and workshops, taking their children to school and implementing recommendations from the various trainings meetings. Analysis of data shows that over 69% of the households have no access to treated water. The water drawn for community use in general may require some form of treatment to eliminate the disease causing microorganisms. Significant differences were found in the number of deaths between the group that often treats water and the group that never treats water. Stringent measures and awareness campaigns need to be put in place to improve sanitation in the district and eliminate negative practices such as open defecation. 105 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Improvement of water quality will have a major and positive impact on the poor. The WHO report (17) (2008) clearly demonstrates that poor water quality, sanitation and hygiene cause more deaths in Kenya than malaria and other Millennium Development Goal (MDG) diseases (17). An increased investment in water will serve the interest of all as well as meet the constitutional requirement for rights to water and sanitation. The existing situation can be improved through further engagement of communities in the area in capacity building for service providers, community health workers and the community itself. Other measures addressing the public health dynamics, such as creating awareness on the importance of hygienic practices through notice boards in public places communicating about diseases and general health ensuring access to hand washing facilities will also go far in ensuring the community ownership of water and sanitation issues in the Sub-County. Based on the findings of this study and the conclusions made, it was noted that improvement of water quality will have a major positive socio-economic and health impact on the poor. In order to make this a reality, the following recommendations are proposed: Reticulated tap water supply along the river region by SIBO be enhanced and extended to the middle region to improve availability, affordability, access and quality; given the fact that the Lake Victoria region will require extra unavailable financial resources to develop new and maintain existing reticulated supplies for household water, it is critical that in the meantime a new policy be instituted to encourage and establish point of use water purification systems; The County government provides improved sanitation systems in the Sub-County to cover all users and awareness and education campaigns is needed to sensitize the community on the dangers of untreated water and poor sanitation, to create ownership of the infrastructure that supplies water to the community and to build the capacity of the community members empowering them in the management of the existing water resources.

Framework for the Design of Education and Outreach Programs In the recent times many institutions have focused attention on what needs to be done to improve the water challenges in Africa. Several Science-Policy Interface Conferences/Workshops have been held over the past decade in Africa. The scope and reach of such activities have ranged from continental, sub-regional, national and sub-national in scale. The participants have included policy and decision maker, scientists, civil society, media and end users. Consequently, the African water Science Agenda has been well cross-pollinated and articulated to address real needs. Some of the key topical issues that have been considered include scientific assessment of Africa’s water resources and systems; research and technology to assess and monitor water related disasters (with emphasis on floods) and knowledge and technology to improve water quality, quantity and availability. At the Africa Union-NEPAD 2007 conference (18) the following 106 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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research and development topics were considered: flood control: acquire, modify and apply the technologies; develop technologies for improving quality; develop technologies to increase the supply of water to African households; research on and development of desalination technologies, with emphasis on small modular units that use low and renewable energy; research on and related technology development for treating and supplying drinking water from aquifers; research and application of knowledge on eutrophication - develop new technologies to address eutrophication related problems. Similarly the below outreach challenges were highlighted at the Scientific Conference (19) on Water Management Issues in Africa, 28-31 March 2012: Providing safe drinking water; ensure access to adequate sanitation; provide water for food security; prevent land degradation and water pollution; meeting growing water demand; manage water under global climate change; develop hydropower to enhance energy security; and enhance capacity to address water challenges. The outreach scales considered have included: LARGE SCALE: Regional and sub-regional systems (e.g. trans-boundary rivers and aquifers) and large scale supply/sanitation systems and infrastructures (cities, cross-border transfers, large dams, large scale irrigation); INTERMEDIATE SCALE: Sub-national or small trans-boundary systems (e.g. in-country large river/lake basins, water towers) and smaller supply/sanitation systems and infrastructure (e.g. towns, medium-sized dams, medium scale irrigation) and SMALL SCALE: local systems (e.g. small river/lake basins, localized groundwater aquifers) and local supply/sanitation systems and infrastructures (e.g. rural water supplies, small dams, small-scale irrigation).

Extending Technologies through Outreach (Improving Water Availability) Micro-agricultural Water Management (Micro-AWM) (20) refers to the large set of small-scale technologies and practices such as low-cost water lifting technologies (for example treadle pumps), low-cost water application technologies (e.g., drip irrigation kits), technologies to capture and store rainwater either in small reservoirs or in the root zone (rainwater harvesting), and conservation tillage and other soil nutrient and water conservation technologies. These technologies have great potential, and there are also disappointing cautionary cases; but no examples of adoption on a sufficiently large scale as to make a significant national impact in Africa as in contrast to South Asia. Examples of local success stories are KickStart’s programs for manufacturing and marketing treadle pumps in Kenya and Tanzania – some 45,000 treadle pumps were sold by 2006 in what may be the best example of scaling up; positive impacts of treadle pumps in reducing poverty in Malawi and Ghana. “Low-cost irrigation pumps increase farmer’s net farm income by nearly 10 times (20).”

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Extending Technologies through Outreach (Promoting Water Security and Data Acquisition) SMART WATER SYSTEMS (SWS). Smart water metering (21) refers to a system that measures water consumption or abstraction and communicates that information in an automated fashion for monitoring and billing purposes. It presents a new approach to promote water security with uncertain but significant future risks from population growth, hydrological variability and extreme events, and intensifying water allocation demands across water supply, agriculture, industry and ecosystems. Having launched M-PESA in 2007, the Kenyan mobile network operator Safaricom is the global mobile-banking leader, with more than 13 million users and 22,000 retail agents. By coupling mobile banking and smart water metering, SWS can create a secure, transparent and low-cost flow of funds and information between consumer, water service provider and delivery system. Such technological innovations measure water use on daily time-steps and relay packets of data to a central database to alert water point failure and trigger response, integrate into mobile-payment/billing models, establish and monitor new Service Level Agreements and performance based contracts with private-sector Rural Water Service Providers, and provide a national database of water points, volumetric use and performance metrics to improve sector transparency and accountability. If developed will greatly improve water delivery and trade.

Extending Technologies through Outreach (Sand Dams) Small-scale Sand dams (5–7) (Figure 7) at the household or village level—offer considerable potential for mitigating drought. The SASOL Foundation (6) has constructed in excess of 500 sand dams in Kitui District in Kenya. These illustrate elegant micro-technologies at its simplest. With low maintenance costs and a lifetime of 50 years, the potential of sand dams for improving livelihoods is proven and the technology is entirely domestic. Sand dams are especially suited to crystalline basement rocks, which cover much of Kenya, and are a sound climate change adaptation strategy in arid and semi-arid areas. The assessment of WASH technologies (22) that have been tried and the level of their success shows that very few of them have been successful. It is obvious that not all have met the criteria for judgment. Additional work still remains to be done. The challenges that face the African communities in providing safe drinking water and sanitation are compounded by the loss of its trained manpower. Loss of university academics to industry due to comparatively low academic salaries - “one lecturer has the potential to graduate 50 to 70 students” continues to deny the continent the potential to make breakthrough in new innovations. Unlike the United Kingdom and other countries, much of South Africa’s leading water-related expertise (including its research capacity) lies outside of the public sector, which includes semi-public institutions. It is concentrated in private sector consultancies, as the state and its affiliates contract a considerable amount of work out to the private sector. Because these data and reports are seen as saleable assets, the 108 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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consultancies are less likely to make them freely available to other researchers and organizations, in contrast to the practice by government departments or the national research councils. Private consultancies are also smaller than research institutions, which contributes to the problem of critical mass.

Figure 7. Sand dam under construction in Sakai, Makueni, Kenya. Photo taken by Prof. Dan Olago.

Other challenges facing Africa include variable monitoring and evaluation (M&E) systems that may be classified as: strong, intermediate and weak (23). Typically, the weak countries have systems that are project-based and fragmented, have little capacity to gather, analyze and report, lack national frameworks for M&E, and suffer from a paucity of demand for the information they offer. Intermediate M&E systems have substantial weaknesses that are recognized as such and are being upgraded over time. Even within those few countries considered to have strong M&E systems, however, there are failings that undermine monitoring and the use of information in sector planning and management. Generally there is the lack of demand for information by management that is typically inexperienced in the use of management information systems (MIS). As a result, water resources information in these countries is typically fragmented, unreliable and out-of-date. In a single country it is common to see a variety of indicators and methods of data collection used to measure the same parameter, which renders comparative analysis impossible. No country has been identified as having a functional central sector-wide database and/or MIS, although Senegal is building one and Uganda is rehabilitating its own (22). Low “water awareness” amongst the communities, lack of adequate finance to roll out programs and lack of adequate finance and skills to support maintenance of existing water systems is common features in most countries. 109 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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What Can Be Done To Promote Education? To promote water knowledge: the Africa Water Facility (24) 2012-2016 Strategic Plan allocates 15% of its budget to the design and implementation of information systems or "monitoring and evaluation" systems to serve the needs of the water sector and to the development of knowledge products, for wiser use and management of water resources and better decision making at national, regional and trans-boundary levels. If skilled and talented people are not attracted to the water sector, then technological innovation cannot happen. Institutions should be orientated so that practical innovations and participatory design and implementation of programs are nurtured and encouraged. The regulatory and policy framework in the continent and respective countries needs to be clear and unambiguous with respect to innovation and community involvement in the sector. The countries should build and harmonize solutions-oriented databases. Partnering with industry – joint projects, student attachments; partnering with Civil Society, NGOs and Community Based Organizations, recognition of actions required at different scales and setting up of coordinated networks and institutions to address the issues at appropriate scales, building and harmonizing solutions-oriented databases and provision of adequate funding through Public-Private Partnerships (PPPs) will make some marked difference.

Conclusions Water is quintessential resource that must be given highest priority by governments, communities and private sector in Africa and the rest of the world bodies. Challenges facing safe water and sanitation provisions in Africa are enormous and will not be solved by governments. Multi faceted approach is required. Development of new and emerging technologies that include nanoscience and nanotechnologies may contribute to water purification at point of use. Coupling such technologies with Information and Computing Technologies will produce real time data that can be used by decision and policy makers for individual and community safety. The challenges caused by climate change and climate variability require that Africa adopts rain catchment and rain harvesting technologies as urgently as possible. Application of ecosystem based approaches for adaptation to climate change is highly recommended. Cooperation at national, inter river basin and regional levels is the most appropriate approach to solving water basin wide issues. Such issues include water pollution, resource use, legalization and harmonization of legal frameworks. Cooperation between countries and counties will help solve water challenges. Lastly, provision of quality training of young people in all areas of required expertise at different levels of education and incetivization of trained personnel is a must for the continent.

110 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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University, 2011; available at: http://washtechafrica.wordpress.com (accessed March 28, 2015). 23. Hope, R.; Foster, T.; Money, A.; Rouse, M.; Money, N. and Thomas, M. 2011. Smart Water Systems; Project report to UK DFID, April 2011; Oxford University: Oxford. 24. The Africa Water Facility 2012-2016 Strategic Plan; http:// www.africanwaterfacility.org/fileadmin/uploads/awf/Publications/AWFStrategy-2012-2016.pdf (accessed March 28, 2015).

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Chapter 7

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Organochlorine Pesticide Contamination in the Kaveri (Cauvery) River, India: A Review on Distribution Profile, Status, and Trends Nikhil Nishikant Patil, Krishna Kumar Selvaraj, Vimalkumar Krishnamoorthy, Arun Elaiyaraja, and Babu Rajendran Ramaswamy* Department of Environmental Biotechnology, Bharathidasan University, Tiruchirappalli - 620024, Tamil Nadu, India *E-mail: [email protected].

Numerous studies have reported organochlorine pesticides (OCPs) in water resources such as rivers and lakes, etc. Agricultural and vector control activities contribute significantly to the contamination of persistent OCPs in rivers. In India, monitoring studies on rivers are limited. This chapter deals with OCPs contamination profile, status and trends in the Kaveri River, which is one of the longest rivers in southern India that serves as a water source for agriculture, drinking water and industrial purposes for centuries. The reported OCPs in this river includes hexachlorocyclohexane (HCH), dichloro-diphenyltrichloroethane (DDT), endosulfan, aldrin, dieldrin, heptachlor epoxide etc. The concentrations of HCHs, DDTs and endosulfan residues in Kaveri River water were observed up to 2,300 ng/L, 3,600 ng/L and 15,400 ng/L, respectively, while in sediment, HCHs and DDTs were reported with the maximum concentration of 158 ng/g dw and 9.15 ng/g dw, respectively. Biota (fish, shrimp) samples collected from the river were found to contain significant levels of HCHs (228 ng/g) and DDTs (2,805 ng/g). The levels of some OCPs in the Kaveri River environment exceeded safety guideline values, therefore we cannot rule out the threat to resident organisms

© 2015 American Chemical Society In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

because of continuous exposure. Future monitoring studies are warranted to understand the contamination status, effects on biota, and to design control measures to protect the Kaveri River ecosystem.

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Introduction Indiscriminate usage of pesticides in agriculture and public health purposes to meet the demand for food and to prevent insect borne diseases in many countries has resulted in ubiquitous occurrence of the pesticide residues in abiotic and biotic components globally (1). Despite the remarkable economic benefits (enhanced agricultural productivity and the control of vector-borne diseases), some of the pesticides may cause environmental contamination that lead to adverse health effects in wildlife and on the human population, including cancer, endocrine disruption, developmental deformities, etc. (2, 3) Among various synthetic organic chemicals, organochlorine pesticides (OCPs) were highly used in the last century and are still used sparingly in developing countries. Persistent, bioaccumulative and toxic properties of organochlorines prompted researchers for continuous monitoring of OCPs in the environment and ecotoxicological evaluation even in post-usage era. The tropical climate in India is favorable for breeding of various types of pests and thereby frequent use of pesticides in agricultural and malarial vector control practices is inevitable. At present, India ranks second in pesticide production among the Asian countries and fourth globally (4, 5). In 1985, the Indian government banned the use of pesticides listed in the Stockholm Convention dirty dozen, with an exception of DDT, which is still used to control malaria (6). The pesticide consumption has increased a few orders of magnitude, from 154 MT (metric tonnes) in 1954 to 41,822 MT in 2009-2010. In India, 67% of pesticides are consumed in agriculture and horticulture (7), whereas about 8.5% is utilized for public health (8). Among the pesticides in India, insecticide usage (80%) is much higher than herbicide (15%) and fungicide (2%) unlike the global scenario where herbicide (47.5%) and fungicide (17.5%) usage predominates (9). In terms of volume, OCPs still constitute a major fraction (40%) of pesticide used in India, followed by organophosphates (30%), carbamates (15%), synthetic pyrethroids (10%) and others (5%) (Figure 1) (2, 10). Therefore, monitoring of OCPs is still considered important. In India, information on OCPs occurrence in environmental matrices such as air, water, soil is limited. Especially in southern India, only few reports were available pertaining to riverine ecosystem to date. Among the states in southern India, Tamil Nadu, with an area of 1,30,000 km2, uses a higher proportion (12,500 MT) of pesticides annually than other Indian states (11). In fact, the Kaveri River delta region has the highest rate of pesticide consumption for rice (29%), followed by cotton (27%), vegetables (9%) and pulses (9%). This chapter deals with the Kaveri River basin (Figure 2), a major river basin in Tamil Nadu state for assessing the fate of OCPs. 116 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Figure 1. Pattern of pesticides usage in India.

Figure 2. Map showing the Kaveri River and its tributaries, south India. indicates major sampling locations. 117 In Water Challenges and Solutions on a Global Scale; Loganathan, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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Among the twenty peninsular rivers in India, Kaveri is one of the longest rivers flowing in southern India. Rising in Karnataka state at Talacauvery (11°9’N, 79°52’E) in the Western Ghats, it flows 800 kilometers southeast and exits in the Bay of Bengal (Figure 2). The river covers a basin of about 72,000 km2 in Karnataka and Tamil Nadu state. The tributaries of the Kaveri includes Shimsha, Hemavati, Arkavati, Honnuhole, Lakshmana Tirtha, Kabini, Bhavani, Lokapavani, Noyyal and Amaravati Rivers. The Kaveri River delta is one of the most developed and populated regions (350 people/km2) supporting agriculture for centuries and serves as lifeline for southern India. The river receives a multitude of pollutants through the release of untreated wastewater and agricultural runoff (12). Although, the river has many tributaries, studies on pesticide residue are limited to the main river.

OCPs in River Water The agricultural drainage, urban and rural runoff form a major source of pesticides in rivers. Babu Rajendran and Subramanian (13) first reported OCPs residues in Kaveri River (Manikaranai - 11°06′N; 79°42′E and Melaiyur - 11°07′N; 79°45′E) and its tributary Coleroon (Kollidam - 11°21′N; 79°50′E). Water samples were analysed using GC-ECD and the results showed ubiquitous presence of HCHs and DDTs with higher levels of HCHs (3.2-182 ng/L) in pre-monsoon (July to September) and monsoon seasons (October to December). Among HCH isomers, α, β, and γ-HCH were reported up to 101.3, 79.3 and 73 ng/L, respectively. Increased HCH levels during pre-monsoon and monsoon seasons than post-monsoon season indicates the use of HCH (10% BHC dust) for rice, pulses and cotton in the Kaveri delta region. In the case of DDT and its metabolites, they did not observe any clear differences with respect to seasons. The reported levels of DDTs were (0.75-4.17 ng/L) one order of magnitude lower than HCHs and this may be due to continuing use in only vector control. Further, Babu Rajendran and Subramanian (13) reported that DDT levels were below Eurpean Commision (Council Directive 98/83/EC) maximum acceptable concentration (100-500 ng/L) and lower than USA water quality guidelines (2,000 ng/L). Begum et al. (14) reported pesticide (HCHs, DDTs and endosulfan) residues in upper reaches of the Kaveri River in Karnataka state and found at least one of the OCPs in all the locations. The HCHs (50-2,430 ng/L) and DDTs (50-1,750 ng/L) concentrations were higher than reported in an earlier study by Babu Rajendran and Subramanian (13) (Table 1) from the lower reaches of the river. Although HCHs were forbidden for agricultural use in 1997, the Indian government has allowed the use of the γ-isomer (lindane) for some crops in addition for use in the health sector (15, 16). Other than HCHs and DDTs, endosulfan was reported in the Kaveri river for the first time up to 840 ng/L by Begum et al. (14)

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Table 1. Concentration of OCPs in Water, Sediment, and Biota Samples from Kaveri River and Other Indian Rivers OCPs

River

ΣDDT

Σ3HCH

Heptachlor

Heptachlor epoxide

Endosulfan

Reference

Water (ng/L) Kaveri

3.2-182

0.75-4.17

-

-

-

(13)

Kaveri

50-2,430

50-1,750

-

-

< 10-840

(14)

Kaveri

ND-47.4

ND-49

260

-

-

(17)

Kaveri

2300

3600

-

-

15,400

(18)

Kabini*

BDL-7.2

BDL-0.4

BDL-0.75

BDL-2.4

-

(19)

Tamiraparani