Key Concepts inEnvironmental

Chemistry

Grady Hanrahan

AMSTERDAM l BOSTON l HEIDELBERG l LONDON

NEW YORK l OXFORD l PARIS l SAN DIEGO

SAN FRANCISCO l SINGAPORE l SYDNEY l TOKYOAcademic Press is an Imprint of Elsevier

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Library of Congress Cataloging-in-Publication Data

Hanrahan, Grady.

Key concepts in environmental chemistry / Grady Hanrahan.

p. cm.

ISBN 978-0-12-374993-2

1. Environmental chemistry. 2. Environmental toxicology. I. Title.

TD193.H36 2012

628–dc23

2011019245

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.

For information on all Academic Press publications visit our

website at www.elsevierdirect.com

Printed in the United States of America

11 12 13 14 9 8 7 6 5 4 3 2 1

Contents

Preface to Faculty ixPreface to Students xiiiAcknowledgments xvAbout the Author xvii

1. Introduction to Environmental Chemistry 3

1.1. Overview and Importance of Environmental Chemistry 41.2. Ecosystem Considerations 51.3. Review of Energy and Thermodynamic Concepts 71.4. Review of Chemical Kinetics and Chemical Equilibrium 81.5. Global Water and Element Cycles 12

1.5.1. The Global Water Cycle 131.5.2. The Global Carbon Cycle 161.5.3. The Global Nitrogen Cycle 201.5.4. The Global Phosphorus Cycle 24

1.6. An Introduction to Environmental Data Analysis 271.7. End of Chapter Problems 281.8. References 30

2. Environmental Statistical Analysis and SamplingConsiderations 33

2.1. Introduction to Environmental Statistics 342.2. Sample Collection 34

2.2.1. The Sampling Process 362.3. The Distribution and Transformation of Data 38

2.3.1. Normal Distribution and Log-Normal Distributions 392.4. Inferential Statistics and Hypothesis Testing 442.5. Outlying Results 472.6. Analysis of Variance 482.7. Graphical Data Analysis 51

2.7.1. The Use of the Scatterplot in Environmental DataAnalysis 52

2.7.2. Standard Addition and Internal Standard Methods 562.8. Multivariate Data Analysis: A Brief Introduction 57

2.8.1. Multivariate Correlation Analysis 57

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2.8.2. Pattern Recognition Techniques 592.8.3. Data Reduction 622.8.4. Multivariate Calibration Techniques 66

2.9. End of Chapter Problems 672.10. References 70

3. Aqueous Chemistry 73

3.1. Chemical Composition and Properties of Water 743.1.1. Atomic Structure and Hydrogen Bonding 743.1.2. Surface Tension and Heat Capacity 763.1.3. Water Density 77

3.2. Acid-Base Phenomena 793.2.1. The Carbonate System in Aquatic Systems 823.2.2. Carbonate Species Distribution 84

3.3. Oxidation-Reduction in Natural Waters 863.3.1. Redox Variables 873.3.2. Aqueous Nitrogen Species 883.3.3. Reduced Phosphorus Species Reconsidered 903.3.4. Trace Metals in Natural Waters 95

3.4. Dissolution and Precipitation in Aquatic Environments 973.5. Adsorption in Aquatic Environments 1003.6. The Bjerrum Plot: Construction from Excel Spreadsheets 1043.7. End of Chapter Problems 1043.8. References 106

4. Surface/Groundwater Quality and Monitoring 109

4.1. Surface and Groundwater Relationships 1094.1.1. Flow in Groundwater Systems 1104.1.2. Contaminant Retention and Release 1124.1.3. Contaminant Transport Processes and Plume

Behavior 1134.2. Water Quality Units and Concentration Considerations 115

4.2.1. SI Units of Measure and Conversions 1154.2.2. Chemical Concentrations 116

4.3. Water Quality Parameters and Criteria Guidelines 1204.3.1. Drinking Water Standards 1204.3.2. Inorganic and Organometallic Compounds 121

4.4. Physico-Chemical Water Quality Indicators 1334.4.1. Electrical Conductivity (EC) 1344.4.2. Dissolved Oxygen (DO) 136

4.5. Developmental Toxicants 1374.6. Biological Assessements 1384.7. Water Quality Monitoring 140

4.7.1. Water Quality Monitoring Design 141

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4.7.2. Sample Preservation and Storage for SubsequentLaboratory Analysis 142

4.7.3. Field Sampling and Analysis 1424.7.4. Data Analysis and Method Validation 1464.7.5. Dissemination of Results and Decision Making 146

4.8. Introduction to Environmental Modeling: A WaterQuality Perspective 147

4.9. End of Chapter Problems 1494.10. References 150

5. Water Treatment and Related Technologies 155

5.1. Municipal Wastewater Treatment 1565.2. The Treatment of Municipal Sewage and Water 156

5.2.1. Primary Treatment 1575.2.2. Secondary Treatment 1595.2.3. Tertiary Treatment 160

5.3. Disinfection 1645.3.1. Chlorination 1645.3.2. Ozonation and Ultraviolet Radiation 166

5.4. Use and Disposal of Biosolids 1685.5. Point-of-Entry and Point-of-Use Technologies 170

5.5.1. Activated Carbon 1705.5.2. Reverse Osmosis 1715.5.3. Ion Exchange 172

5.6. End of Chapter Problems 1745.7. References 176

6. The Atmosphere and Associated Processes 179

6.1. Introduction 1806.2. The Layers of the Atmosphere 180

6.2.1. The Boundary Layer 1816.3. Atmospheric Radiation and Photochemical Reactions 182

6.3.1. Energy of a Photon: UnderstandingBasic Photochemistry 183

6.4. Pressure and Temperature Considerations 1886.5. Biosphere-Atmosphere Interactions 190

6.5.1. Biogenic Emissions 1906.5.2. Anthropogenic Sources of Emission 193

6.6. Transport, Transformation, and Deposition Processes:A Brief Introduction 1956.6.1. Atmospheric Removal Processes 1986.6.2. Example Deposition Processes 198

6.7. Global Climate Change: A Primer 2056.8. End of Chapter Problems 2076.9. References 209

vContents

7. Air Pollutants and Associated Chemicaland Photochemical Processes 215

7.1. Introduction 2167.1.1. Indoor Air Pollution: A Primer 216

7.2. Ambient Particulate Matter: Primary and SecondaryContributions and Formation 220

7.3. Photochemical Mechanism of Ozone (O3) Formation:The Role of VOCS and NOx 223

7.4. Peroxyacetyl Nitrate (PAN) Formation and NOx Transport 2287.5. Photochemical Smog: Formation Conditions and

Health Effects 2297.6. Aldehydes in the Atmosphere 2317.7. Heterogeneous Atmospheric Reactions 233

7.7.1. The Role of Transition Metals and OtherAtmospheric Species in Catalyzed and UncatalyzedOxidation of Sulfur(IV) Oxides 235

7.8. Example Predictive Atmospheric Models 2377.9. End of Chapter Problems 239

7.10. References 241

8. Soil Chemistry 245

8.1. Introduction to Soil Chemistry 2468.2. Soil Formation, Composition, and Structure 2468.3. Soil Organic Matter and Biochemical Aspects 249

8.3.1. An Introduction to Humic Substances 2508.4. Sorption of Metals and Hydrophobic Organic

Compounds in Soils 2518.4.1. Metal Adsorption in Soils 2538.4.2. The Role of Weak Organic Acids 256

8.5. Pesticide Adsorption in Soils 2578.6. Acid and Base Characteristics 2598.7. End of Chapter Questions 2608.8. References 261

9. Environmental Toxicology and Hazardous WasteCharacterization 265

9.1. Introduction to Environmental Toxicology 2659.2. Evaluating Exposure Pathways and Mechanisms of Action 268

9.2.1. Toxic Effects and Factors Influencing Toxicity 2699.2.2. Toxicity Testing 2709.2.3. Xenobiotic Metabolism: Biotransformation 274

9.3. Hazardous Waste Identification, Characterization,and Minimization 2809.3.1. Hazardous Waste Identification and Characterization 2809.3.2. Hazardous Waste Minimization 283

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9.4. Risk Assessment 2859.4.1. Calculating Statistically-Estimated Risk Associated

with Exposure 2889.5. End of Chapter Problems 2909.6. References 292

10. Green Chemistry and SustainableChemical Processes 297

10.1. Principles of Green Chemistry 29810.2. Life of the Manufactured Chemical Product 30210.3. Sustainable Chemical and Related Processes 307

10.3.1. Design of Sustainable Technology 30710.3.2. Emerging Environmental Technologies 30810.3.3. Sustainability Metrics 311

10.4. Pollution Prevention and Waste Minimization 31310.5. Sustainable Materials and Application Areas 314

10.5.1. Agricultural Practices 31410.6. End of Chapter Problems 31710.7. References 318

Appendix I 321Appendix II 323Appendix III 325Appendix IV 327Appendix V 329Index 333

viiContents

Preface to Faculty

PHILOSOPHICAL APPROACH

New instrumental and data analysis capabilities have led to fresh insights intothe field of environmental chemistry and questions regarding the future of thisrapidly evolving area of scientific study. As teachers and scholars, we have theability to influence the curious minds of students, simultaneously guiding themthrough the path of knowledge and truth. And when considering the dynamicnature of environmental systems, varying both spatially and temporally acrossa wide range of matrices, there is an increasing need for training on tools thatcan account for complexity, variability, scale, and purpose.

Key Concepts in Environmental Chemistry provides a modern and conciseintroduction to environmental chemistry principles and the dynamic nature ofenvironmental systems. It offers an intense, one-semester examination offundamental chemical concepts encountered in this field of study and providesintegrated data analysis and research tools to help elucidate complex chemicalproblems of environmental significance. Principles typically covered in morecomprehensive textbooks are well integrated into general chapter topics andapplication areas. Unique to this book is its integrated approachda distinctiveblend of theoretical and practical material from all aspects of environmentalchemistry including statistical analysis and modeling concepts not covered (orlimited coverage) in current textbooks. By presenting basic principles togetherwith research-based applications and methods in the field of environmentalchemistry, students will fully comprehend the power of such tools in explainingcomplex chemical problems of environmental importance.

PURPOSE AND ORGANIZATION

The purpose of this textbook is to provide students with an indispensableresource for learning the basic concepts of environmental chemistry from aneasy to follow, condensed, application and inquiry-based perspective. Addi-tional statistical, sampling, modeling, and data analysis concepts and exercisesare introduced for greater understanding of the underlying processes ofcomplex environmental systems and fundamental chemical principles. Eachchapter houses problem-oriented exercises that stress the central conceptscovered. Research applications and case studies from experts in the field aredirectly tied to theoretical background offered in each chapter. This textbook

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opens with a broad definition and overview of the field of environmentalchemistry. It provides detailed understanding of chemical, physical, and bio-logical processes that will shape the foundation of material covered in subse-quent chapters. In addition, in-depth examination of the hydrologic cycle willbe beneficial in understanding surface and groundwater concepts and theinteractions that occur within such systems. Chapter 2 deals with theoreticaland applied statistical concepts useful in solving real-world environmentalproblems. The basic methodology presenteddsuch as sample collection, datadistribution, hypothesis testing, analysis of variance (ANOVA), and multivariateanalysisdprovides necessary background to study and characterize complexchemical data sets and the myriad of physical measurements accompanyingextensive environmental analyses.

Chapters 3 and 4 examine the chemical processes affecting the distributionof chemical compounds in natural waters. Chapter 3 begins by reviewing thechemical composition and physical properties of water, including the role ofhydrogen bonding, density, salinity, and temperature in governing aqueoussystems. The focus of the chapter then shifts to the study of the carbonatesystem, oxidation/reduction reactions, acid/base chemistry, adsorption pro-cesses, and chemical precipitation. In Chapter 4, detailed understanding of thehydrologic cycle presented in Chapter 1 is beneficial in grasping surface andgroundwater concepts and the chemical/physical interactions that occur withinsuch systems. A review of typical concentration units encountered in aqueouschemistry is presented, followed by information on drinking water standards,physico-chemical indicators, and selected environmental regulations relative tochemical, biological, and physical contaminants.

Chapter 5 presents a solid overview of wastewater treatment processes andrelated technologies including activated carbon, reverse osmosis, and ionexchange processes as applied to real-world situations. The next two chaptersexamine atmospheric chemical and physical processes and the impact ofnatural and anthropogenic pollutant releases. Chapter 6 provides an introduc-tion to atmospheric layers, a review of basic photochemistry, and informationon transport, transformation, and exchange processes between the biosphereand the atmosphere. Chapter 7 provides a more detailed investigation ofatmospheric pollutants including the identification of primary sources andsecondary precursor compounds. Particular importance is given to the mech-anism of ozone formation and information on heterogeneous atmosphericreactions.

Chapter 8 presents a condensed view of soil chemistry including soilformation, composition, and structural concepts. The role of pH and organicmatter is critically examined to help explain the adsorption and transportationof selected contaminants. The final chapters survey environmental toxicologyconcepts and green chemistry and sustainable chemical processes. Chapter 9provides an overview of environmental toxicology and hazardous waste char-acterization including toxicity testing and examination of dose-response

x Preface to Faculty

relationships. Finally, Chapter 10 presents material related to the burgeoningarea of green chemistry. It starts with coverage of the 12 Principles of GreenChemistry and their relation to chemical and industrial processes. Lastly,information on example sustainable chemical and related processes is pre-sented, including emerging environmental technologies and sustainabilitymetrics.

xiPreface to Faculty

Preface to Students

You are enrolled in a course that has considerable relevance to today’s globalsocietydthis is true not only for human health and well-being, but also for thefragile ecosystems in which we live, work, and play. When it comes to safe-guarding global natural resources; air, soil, and water quality; human health;and social and political systems, we as educated citizens have the ability tomake important decisions that affect these vital considerations. Key Concepts inEnvironmental Chemistry has been written to provide a condensed examinationof key environmental concepts and the development of analytical skills.Numerous tools are provided to help you succeed in both. It is essential torecognize that those concepts and skills will help foster learning and provideyou with the ability to examine and interpret environmental data as they relateto real-world problems.

I encourage you to master both theoretical and application-based contentpresented within this textbook. Provided are worked example problems, casestudies, and research applications to complement the learning process. As youwork through the end of chapter problems, go back and reflect upon infor-mation gathered and learned in relevant chapters. Admittedly, this text will notprovide you with information on all aspects of environmental chemistry.However, it does present a concise and detailed look at key concepts of envi-ronmental chemistry in which you will likely encounter along your academicand work-related career path. You are encouraged to explore the externalsources of information recommended in this textbook. Finally, I encourage youto further develop your analytical skills through hands-on, practical-basedlaboratory exercises that accompany the lecture course. With practice andpatience, you will be sure to contribute significantly to furthering the knowl-edge base of environmental topics for years to come.

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Acknowledgments

The author is grateful to many of those who supported this effort. First andforemost, I wish to thank Piyawan and my family for their continued patienceand support of my academic pursuits. To Kanjana Patcharaprasertsook for themeticulous illustrations housed in this book. To Professor Greg Santillan forstimulating conversations and helpful comments regarding the Lake Nyosinformation presented in Chapter 1. I thank all of the reviewers for theirvaluable comments and constructive criticism during the early stages of thisbook, and all of the publishers who have granted permission for use of externalmaterial housed in this book. I thank Elsevier and Academic Press for believingin the concept of this book. In particular, I would like to acknowledge LindaVersteeg, Anita Koch, Lisa Lamenzo, Emily McCloskey, and the supportingeditorial staff. To Vicki Wright and Jennifer Arceo for their help with scanningand formatting of chapter material. Finally, to my colleagues Drs. KrishnaFoster, Haco Hoang, Mehdi Jalali-Heravi, Nate Carlson, and Crist Khachikianfor their continued research collaboration in the environmental field.

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About the Author

Grady Hanrahan received his Ph.D. in Environmental Analytical Chemistryfrom the University of Plymouth, UK, in 2001. With experience in directingundergraduate and graduate research, he has taught in the fields of AnalyticalChemistry and Environmental Chemistry at California State University, LosAngeles (CSULA), and California Lutheran University (CLU). He is currentlythe John Stauffer Endowed Professor of Analytical Chemistry and AssistantDean of the College of Arts and Sciences at CLU. He has considerable expe-rience in environmental analysis and modeling, particularly in areas of low-income and underrepresented populations. He was a major participant ina National Institutes of Health (NIH) grant award studying the correlationbetween the chemical composition of air pollutants in the East Los Angelesregion and the potential impact of long-term exposure to these chemicals onhuman health. Dr. Hanrahan has recently completed work on a U.S. EPA-funded project where he developed an integrated modeling approach to assessthe health of aquatic systems in Southern California watersheds. He continuesto be active in the field and is the author of five books and 45 peer-reviewed,scientific papers.

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