About this book


Perchlorate anion is a widespread, environmentally persistent contaminant recently discovered in U.S. groundwater and drinking water supplies. This book summarizes the most current knowledge and understandings of the extent and potential sources of perchlorate contamination, its behavior, exposure pathways in the environment, toxicology and risk assessment, and recent advances in treatment technologies for removing perchlorate from contaminated soil and water.  Its natural occurrence and its unique isotopic signature (between natural and anthropogenic sources) and novel detection techniques are discussed in this comprehensive reference for environmental professionals, regulators, policy makers, scientists, engineers, and others interested in issues associated with perchlorate in the environment.

This book provides a detailed description of the perchlorate chemistry, microbiology, biochemistry, genetics, geochemical occurrences and environmental forensics, toxicology and risk assessment to engineering solutions and policy.  Presented in this book also include innovative remediation technologies and monitoring tools for cleaning up contaminated sites including bioremediation, selective and regenerable ion-exchange, modified granular activated carbon, and catalyzed destruction.

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PREFACE

Perchlorate (ClO4-) has been detected recently in groundwater, surface water, and soils and, more ominously, in plants, food products and human breast milk in many areas of the United States and the world. Because of its potential health affect on thyroid function by interfering with iodide uptake, the widespread occurrence of perchlorate in the environment has generated considerable interest in its contamination source, environmental interactions, toxicology, risk assessment, and remediation technologies. Most perchlorate is manufactured for use as a primary ingredient of solid rocket propellant and explosives. However, perchlorate is also used in pyrotechnic devices, such as fireworks, highway flares, gun powder, and air bags, and in a wide variety of industrial applications such as tanning and leather finishing, rubber manufacturing, and paint and enamel production. Naturally-occurring perchlorate is also known to exist, particularly in the hyperarid Atacama Desert in Chile . The widespread use and the presence of both natural and anthropogenic perchlorate thus have resulted in intense public debate and far-reaching ramifications, ranging from public health issues to liabilities that could be imposed by environmental cleanup needs.

The goal of this book is to provide the current state of science and technology with respect to the occurrences and potential sources of perchlorate contamination, its behavior, exposure pathways, and detection in the environment, toxicology and risk assessment, and recent advances in treatment technologies for removing perchlorate from contaminated soil and water. To this end, internationally recognized experts in each respective field of perchlorate research have contributed to this text to render a complete inter-disciplinary overview of the state of the science. The book is intended to serve as a comprehensive reference for environmental professionals, regulators, policy makers, scientists, engineers, and others interested in issues associated with perchlorate in the environment. The book consists of 17 chapters covering diverse subjects. The first six chapters describe the challenges and various sources of perchlorate contamination, its chemistry and detection in the environment, its natural occurrence and unique isotopic signatures that may be used for environmental forensics. Chapters 7 to 9 summarize our current understanding of perchlorate toxicology, risk assessment, and exposure pathways. The remaining chapters address recent advances in innovative treatment technologies for remediating perchlorate contaminated soil and water. In particular, significant advances in selective ion exchange and its regeneration technologies enable the treatment of large volumes of contaminated water with reduced costs. Furthermore, rapid advances in our understanding of the microbiology, biochemistry and genetics of perchlorate-reducing microorganisms offer great hope for eliminating perchlorate from contaminated environments in the future. Presented in this book several chapters are also devoted to field demonstration and case studies involving the use of highly-selective, regenerable ion exchange processes, in situ bioremediation strategies, and modified activated carbon technologies for perchlorate removal. Further attention is given to other treatment technologies, such as titanium-catalyzed reduction and membrane filtration, and to the pros and cons of various remedial options.

We wish to thank the authors for their contributions and for their cooperation during the preparation of this book. Special thanks are expressed to Juske Horita and Denise Parker for their expert review and editorial support. Finally, this book would not have been possible without the support of the U.S. Department of Energy, Department of Defense’s Strategic Environmental Research and Development Program (SERDP) and the Environmental Security Technology Certification Program (ESTCP), and the Laboratory Directed Research and Development Fund of the Oak Ridge National Laboratory. 

Baohua Gu, Oak Ridge, Tennessee

John D. Coates, Berkeley, California

 

TABLE OF CONTENTS

 

Preface................................................................................................... iii

Contents.................................................................................................. v

 Chapter 1. Perchlorate:  Challenges and Lessons

S. E. Cunniff, R. J. Cramer and H. E. Maupin

How Perchlorate Became an Issue............................................ .... 1

Facing the Challenge of Emerging Contaminants............................ 7

Perchlorate Environmental Science and Technology Development... 9

Outreach.................................................................................... 11

Lessons Learned........................................................................ 11

Conclusions................................................................................ 13

References................................................................................ 14

Chapter 2. The Chemistry of Perchlorate in the Environment

Gilbert M. Brown and Baohua Gu

Introduction................................................................................ 17

Redox Properties of Chlorine Compounds.................................... 18

General Physical and Chemical Properties of Perchloric Acid
and the Perchlorate Anion........................................................... 22

Industrial Preparation of Perchlorate............................................ 25

Chemical Reduction of Perchlorate.............................................. 27

Electrochemical Reduction of Perchlorate.................................... 32

Formation of Perchlorate in the Environment................................ 34

Fate of Perchlorate in the Environment........................................ 39

Conclusions................................................................................ 42

References................................................................................ 42

 Chapter 3. Occurrence and Formation of Non-Anthropogenic Perchlorate

W. Andrew Jackson, Todd Anderson, Greg Harvey, Greta Orris, Srinath Rajagopalan, and Namgoo Kang

Introduction................................................................................ 49

Occurrences.............................................................................. 50

Potential Mechanism of Formation............................................... 60

Conclusions................................................................................ 64

References................................................................................ 66

 Chapter 4. Alternative Causes of Wide-Spread, Low Concentration Perchlorate Impacts to Groundwater

Carol Aziz, Robert Borch , Paul Nicholson, and Evan Cox

Introduction................................................................................ 71

Chilean Nitrate Fertilizers............................................................ 72

Fireworks................................................................................... 76

Safety Flares.............................................................................. 80

Blasting Agents.......................................................................... 82

Electrochemically-Produced Chlorine Products............................. 84

Conclusions................................................................................ 87

References................................................................................ 88

 Chapter 5. Stable Isotopic Composition of Chlorine and Oxygen in Synthetic and Natural Perchlorate

Neil C. Sturchio , J. K. Böhlke, Baohua Gu, Juske Horita, Gilbert M. Brown, Abelardo D. Beloso, Jr., Leslie J. Patterson,
Paul B. Hatzinger, W. Andrew Jackson, and Jacimaria Batista

Introduction................................................................................ 93

Previous Isotopic Studies of Perchlorate....................................... 95

Materials and Methods................................................................ 97

Results and Discussion.............................................................. 101

Summary and Conclusion.......................................................... 105

References............................................................................... 107

 Chapter 6. Recent Developments in Perchlorate Detection

Pamela A. Mosier-Boss

Introduction.............................................................................. 111

Source of Perchlorate Contamination – Man-made or  Natural.... 113

Gravimetry and Other Ion Pairing Methods................................. 115

Electrochemical Methods.......................................................... 117

Separation Methods: IC and CE................................................. 123

Spectroscopic Methods............................................................. 135

References............................................................................... 148

 Chapter 7. The Ecotoxicology of Perchlorate in the Environment

Philip N. Smith

Introduction.............................................................................. 153

Ecological Exposure.................................................................. 153

Effects in Ecological Receptors................................................. 156

Conclusions.............................................................................. 163

References............................................................................... 164

Chapter 8. Perchlorate Toxicity and Risk Assessment

David R. Mattie, Joan Strawson, and Jay Zhao

Perchlorate Occurrence and Exposure....................................... 169

Perchlorate Health Effects........................................................ 170

Perchlorate Risk Assessment.................................................... 177

Summary and Implications......................................................... 191

References............................................................................... 191

Chapter 9. Using Biomonitoring to Assess Human Exposure to Perchlorate

Benjamin C. Blount and Liza Valentín-Blasini

Introduction.............................................................................. 197

Assessing Human Exposure to Perchlorate................................. 198

Attributes of Effective Biomonitoring Methods............................ 200

Biomonitoring Applications........................................................ 203

Conclusions.............................................................................. 205

References............................................................................... 205

 Chapter 10. Recent Advances in Ion Exchange for Perchlorate Treatment, Recovery and Destruction

Baohua Gu and Gilbert M. Brown

Introduction.............................................................................. 209

Nature of Ion Exchange............................................................ 210

Selective and Non-Selective Resins............................................ 217

Column Flow-Through Operations.............................................. 219

Resin Regeneration and Reuse.................................................. 224

Other Novel Regeneration Techniques....................................... 232

Perchlorate Destruction and Regenerant Recycling..................... 235

Ion-Exchange Selection Issues and Cost Analysis....................... 239

References............................................................................... 249

  Chapter 11. Field Demonstration using Highly Selective, Regenerable Ion Exchange and Perchlorate Destruction Technologies for Water Treatment

Baohua Gu and Gilbert M. Brown

Introduction.............................................................................. 253

Case Study 1............................................................................ 254

Case Study 2 – Edwards AFB Site............................................ 264

Field Performance Evaluation.................................................... 267

Perchlorate Destruction and Regenerant Recycling..................... 274

Conclusions.............................................................................. 276

References............................................................................... 277

 Chapter 12. The Microbiology of Perchlorate Reduction and its Bioremediative Application

John D. Coates and Laurie A. Achenbach

Introduction.............................................................................. 279

The microbiology of Perchlorate Reduction................................. 280

General Characteristics of DPRB.............................................. 281

Phylogeny of DPRB................................................................. 282

Environmental Factors Controlling DPRB Activity...................... 284

The Microbiology of Biofouling During Perchlorate   Bioremediation 286

Conclusions.............................................................................. 290

Acknowledgements................................................................... 290

References............................................................................... 291