Perchlorate; Environmental Occurrence, Interactions and Treatment

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

 Chapter 13. The Biochemistry and Genetics of Microbial Perchlorate Reduction

Laurie A. Achenbach, Kelly S. Bender, Yvonne Sun, and John D. Coates

    Introduction.............................................................................. 297
    Chlorite Dismutase Gene........................................................... 298
    Hybridization Analysis with a cld Gene Probe............................. 301
    Perchlorate Reductase Operon.................................................. 303
    Perchlorate Reductase Protein Subunits..................................... 304
    Gene Organization of cld and pcr Genes.................................... 306
    Conclusion................................................................................ 308
    References............................................................................... 309

Chapter 14. Field Demonstration of In Situ Perchlorate Bioremediation in Groundwater

P. B. Hatzinger, J. Diebold, C. A. Yates and R. J. Cramer

    Introduction.............................................................................. 311
    Site History and Characterization............................................... 312
    Demonstration System Design................................................... 324
    Demonstration Results and Discussion....................................... 328
    Demonstration Summary and Conclusions.................................. 338
    Credits..................................................................................... 340
    References............................................................................... 340

 Chapter 15. Perchlorate Removal by Modified Activated Carbon

Robert Parette and Fred S. Cannon

    Introduction.............................................................................. 343
    Materials and Methods.............................................................. 344
    Perchlorate Asorption by Virgin GAC........................................ 347
    Iron Pre-loaded and Ammonia Tailored GAC............................. 352
    Cationic Polymer Pre-loaded GAC............................................. 352
    Cationic Surfactant Pre-loaded GAC.......................................... 354
    Desorption of Surfactants from GAC......................................... 360
    Coadsorption of Organics.......................................................... 363
    Thermal Reactivation of Exhausted Tailored GAC...................... 366
    Conclusions.............................................................................. 368
    References............................................................................... 370

  Chapter 16. Titanium Catalyzed Perchlorate Reduction and Applications

Baohua Gu, Peter V. Bonnesen, Frederick V. Sloop, and Gilbert M. Brown

    Introduction.............................................................................. 373
    Perchlorate Reduction Kinetics by Ti(III)................................... 374
    Electrochemical Reduction of Perchlorate and Resin Regeneration 378
    Studies with 36Cl Radio-Labeled Perchlorate............................... 383
    Summary and Implications......................................................... 386
    References............................................................................... 386

  Chapter 17.Membrane and Other Treatment Technologies – Pros and Cons

Ping Zhou, Gilbert M. Brown, and Baohua Gu

    Introduction.............................................................................. 389
    Reverse Osmosis...................................................................... 390
    Nanofiltration and Ultrafiltration................................................. 392
    Electrodialysis........................................................................... 394
    Comparisons of Treatment Technologies.................................... 397
    References............................................................................... 403

Index.................................................................................................. 405

List of Contributors........................................................................... 409