CYANIDE in WATER and SOIL Chemistry, Risk, and Management © 2006 by Taylor & Francis Group, LLC A CRC title, part of the Taylor & Francis imprint, a member of the Taylor & Francis Group, the academic division of T&F Informa plc. CYANIDE in WATER and SOIL David A. Dzombak Rajat S. Ghosh George M. Wong-Chong Chemistry, Risk, and Management Boca Raton London New York © 2006 by Taylor & Francis Group, LLC Published in 2006 by CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2006 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10987654321 International Standard Book Number-10: 1-56670-666-1 (Hardcover) International Standard Book Number-13: 978-1-56670-666-7 (Hardcover) This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. No part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Catalog record is available from the Library of Congress Visit the Taylor & Francis Web site at and the CRC Press Web site at Taylor & Francis Group is the Academic Division of Informa plc. L1666_Discl.fm Page 1 Friday, October 21, 2005 4:20 PM (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC) 222 Rosewood Drive, Danvers, MA http://www.taylorandfrancis.com http://www.crcpress.com © 2006 by Taylor & Francis Group, LLC For permission to photocopy or use material electronically from this work, please access www.copyright.com Preface “Cyanide” is a chemical with a long and fascinating history of respectful and productive use by mankind. The fundamental cyanide species, the cyanide ion CN − , is a highly versatile and strong binder of metals in aqueous solution, a property that has been exploited in ingenious ways for commercial processes thathave benefited society. The best known and largest volume uses of cyanide are in the gold mining and electroplating industries. In hydrometallurgical gold mining, aqueous solutions of CN − are used to extract and concentrate gold from ores containing very small amounts of gold. In electroplating, solutions of metal–CN species are used as the baths into which solid metals are dipped and coated with the metal from solution. The deposition of the metal from solution onto the solid metal is governed by the electrochemical gradient induced in the system, and by the metal–cyanide solution chemistry. Cyanide is also produced incidentally in significant quantities in a number of industrial processes, including coal coking and gasification, iron and steel manufacturing, aluminum manufacturing, and petroleum refining. This results in the need for control of cyanide releases in the form of gases, solids, and liquids. The substantial use of cyanide compounds in commerce coupled with the substantial incidental production of cyanide compounds means that significant amounts of cyanide are introduced into the environment on a continuous basis. Cyanide species are frequently occurring contaminants in water and soil. There are also natural sources of cyanide, such as black cherry and cassava plants. Indeed, there is a natural cycle of cyanide. However, anthropogenic inputs of cyanide to the environment are far greater in amount than natural inputs. Of course, “cyanide” is also widely known, and perhaps best known, as a potent human toxin. The most toxic form of cyanide is hydrogen cyanide, HCN, which is as toxic, and often even more so, to wildlife, especially aquatic life. There is great fear of “cyanide” in society, but some chemical forms of cyanide are nontoxic and in fact used regularly in food and cosmetic products. An example is the solid Prussian Blue, or ferric ferrocyanide, which is used as a blue pigment for use in inks, dyes, cosmetics, and other products. The chemistry of cyanide is both complex and diverse, and there are many different chemical forms of cyanide, including solid, gaseous, and aqueous species, and both inorganic and organic species. The particular chemical forms of cyanide that exist in a system, referred to as the speciation of the chemical, are all important in determining the environmental fate, transport, and toxicity of the cyanide. In our careers in environmental engineering and science, we have encountered many different problems involving cyanide in water and soil. Cyanide has been a focus in engineering and research projects that we have performed related to industrial and municipal wastewater treatment, ground- water treatment, industrial waste management, site remediation and restoration, and water quality assessment. These projects have been sponsored by a wide range of companies, industrial research organizations, and regional and federal government agencies. There is widespread interest in cyanide management for environmental and human health protection. We have learned much about cyanide use, management, emissions, and behavior in the environment in the course of these projects. Our education has been aided by useful knowledge and information acquired from many different sources and people. We undertook the preparation of this book to bring together in one place some of the current knowledge and information about cyanide release to, and behavior in, the environment, and means v © 2006 by Taylor & Francis Group, LLC vi Preface of controlling or remediating these releases. No other broad-based examination of this topic exists. While there has been much good research and engineering development performed in thegold mining industry on cyanide management and control of environmental releases, most notably the work of Dr Terry Mudder and colleagues, this work has been focused on the industry with an orientation toward advancement of hydrometallurgical gold mining. There is much to be learned from the extensive knowledge about cyanide that has been gained in the gold mining industry, but there is a broader range of cyanide challenges in environmental engineering and science. Our book takes on this broader scope. This book tries to address the full range of issues pertaining to cyanide fate, transport, treatment, and toxicity in water and soil. We examine the sources of cyanide released to the environment, both anthropogenic and natural. We have tried to develop an appropriate balance of depth and scope of coverage. There have been compromises made on depth of coverage in some topical areas, but in all areas we have endeavored to provide good and current references to enable the reader to learn more about topics of particular interest. We developed this book to serve as a useful reference tool for engineers and scientists, includ- ing both practitioners and researchers, in academia, industrial organizations, government, and engineering and science consulting firms. We hope we have succeeded in our goal. Effective management and remediation approaches for cyanide in the environment require con- sideration of issues spanning many different fields. In this context, we have collaborated with a wide range of individuals possessing a wide range of expertise in our cyanide-related projects. To address the range of topics that we wanted to examine in this book, we engaged a number of our former and current collaborators to help us with the book. We are most grateful to the contributing authors, listed following this preface and in the header for each chapter. We are also grateful to Alcoa, Inc. and Niagara Mohawk Power Corporation for financial support that helped make this book project possible; and USFilter Corporation, the RETEC Group, Inc. and the Carnegie Mellon University Department of Civil and Environmental Engineering for providing assistance with preparation of graphics and the manuscript. We owe special thanks to Jacqueline Ziemianski, Donna Silverman, and Kacey Ebbitt of the RETEC Group, Inc. for their good work with preparation of graphics and securing permissions for use of copyrighted material, and to Nichole Dwyer of Carnegie Mellon University for her careful work in helping us with revising and formatting the text, with completing and formatting references, and with permissions. Finally, we thank our families for their understanding as we used many hours of family time to work on this book. David A. Dzombak Rajat S. Ghosh George M. Wong-Chong © 2006 by Taylor & Francis Group, LLC Editors David Dzombak, Ph.D., P.E., DEE, is a professor in the Department of Civil and Environmental Engineering at Carnegie Mellon. Dr Dzombak’s research and professional interests include aquatic chemistry; fate and transport of chemicals in surface and subsurface waters; water and wastewater treatment; in situ and ex situ soil treatment; hazardous waste site remediation; abandoned mine drainage remediation; and river andwatershed restoration. He has over 70 peer-reviewed publications and is the joint holder of three patents related to water and soil treatment. He has extensive research and consulting experience with cyanide management and treatment in soils, wastewaters, and process residuals. He has served as a member of the U.S. Environmental Protection Agency Science Advisory Board and is involved with numerous other professional service activities. Dr Dzombak received his Ph.D. in Civil-Environmental Engineering from the Massachusetts Institute of Technology in 1986. He also holds an M.S. in Civil-Environmental Engineering and a B.S. in Civil Engineering from Carnegie Mellon University, and a B.A. in Mathematics from Saint Vincent College. He is a registered Professional Engineer in Pennsylvania, and a Diplomate of the American Academy of Environmental Engineers. Dr Dzombak was elected a Fellow of the American Society of Civil Engineers in 2002. Other awards include the Professional Research Award from the Pennsylvania Water Environment Association (2002); Jack Edward McKee Medal from the Water Environment Federation (2000); Aldo Leopold Leadership Program Fellowship from the Ecological Society of America (2000); Distinguished Service Award from the Association of Environmental Engineering and Science Professors (1999); Walter L. Huber Civil Engineering Research Prize from the American Society of Civil Engineers (1997); Harrison Prescott Eddy Medal from the Water Environment Federation (1993); and National Science Foundation Presidential Young Investigator Award (1991). Rajat S. Ghosh, Ph.D., P.E., is a Program Manager with the EHS Science and Technology Group of Alcoa, Inc., theworld’s largestproducer ofaluminum. He formerly was a SeniorTechnicalConsultant in the Pittsburgh office of The RETEC Group, Inc., a U.S. environmental engineering and consulting company. Dr Ghosh’s research and professional interests are in geochemistry, transport and treatment of inorganic compounds (especially cyanide and heavy metals) in the subsurface; analytical method development for various inorganic and organic compounds; and subsurface multiphase flow and chemistry of organic compounds including coal tar, DNAPLs, and petroleum hydrocarbons. Dr Ghosh has extensive research and consulting experience with the electric power, natural gas, and aluminum industries in the United States in relation to cyanide management and treatment issues in soil and groundwater. In addition, Dr Ghosh serves as a senior technical reviewer for the U.S. Department of Defense basic environmental science and technology development program for site remediation under the auspices of the Strategic Environmental Research and Development Program (SERDP) and Environmental Security and Technology Certification Program (ESTCP). Dr Ghosh received his Ph.D. in Civil-Environmental Engineering from the Carnegie Mellon University in 1998. He also holds an M.S. in Chemical Engineering from University of Wyoming and a B.S. in Chemical Engineering from Jadavpur University, India. He is a registered Professional Engineer in Pennsylvania. He has over 20 professional publications in the open literature and is a joint holder of a U.S. patent on cyanide treatment technology. Dr Ghosh serves as a member of ASTM’s D-19 Committee on Water. Dr Ghosh was elected as a member of the Sigma Xi Honor Society. Other vii © 2006 by Taylor & Francis Group, LLC viii Preface awards include the Jack Edward McKee Medal from the Water Environment Federation (2000) and the Graduate Student Award from American Chemical Society (1998). George M. Wong-Chong, Ph.D., P.E., DEE, retired director of process wastewater research at USFilter Corporation (Engineering and Construction), has over 35 years of experience in techno- logy development, design, construction, operation, research and teaching of the management and treatment of contaminated groundwater, wastewaters, and solid hazardous waste. Dr Wong-Chong’s experience spans a range of industries including iron and steel, coal tar refining, organic chemicals, petroleum refining, munitions, aluminum manufacturing, coal gasification, live stock agriculture, and municipal wastewater. His experience in the iron and steel industry, where cyanide is a major concern, is internationally recognized; for coke plant wastewaters he developed a patented process, NITE/DENITE™, for the direct biological treatment of flushing liquor, which can contain very high concentrations of ammonia, cyanide, phenols, and thiocyanate. He also holds a patent for the physical/chemical treatment of municipal and industrial wastewaters. Dr Wong-Chong received his Ph.D. in Agricultural Engineering from Cornell University in 1974. He also holds an M.S. in Envir- onmental Engineering from the University of Western Ontario, Canada, and a B.S. in Chemical Engineering from McGill University, Canada. He is a registered Professional Engineer in 10 states, and a Diplomate of the American Academy of Environmental Engineers. In 1999, Dr Wong-Chong received the Pennsylvania Water Environment Association Professional Research Award and the American Institute of Chemical Engineers Pittsburgh Section Award for Outstanding Professional Accomplishments in the Field of Consulting Engineering. Dr Wong-Chong has over 50 publica- tions and presentations to his credit and remains very interested in waste water treatment technology development. © 2006 by Taylor & Francis Group, LLC Contributors Todd L. Anderson, P.E. Malcolm Pirnie, Inc. Emeryville, CA Barbara D. Beck, Ph.D., DABT DABT, Gradient Corp. Cambridge, MA Brice S. Bond, M.S. Southern Illinois University Carbondale, IL Joseph L. Borowitz, Ph.D. Purdue University West Lafayette, IN Joseph T. Bushey, Ph.D. Syracuse University Syracuse, NY Rick D. Cardwell, Ph.D. Parametrix, Inc. Albany, OR Jeremy M. Clark Parametrix, Inc. Albany, OR Rula A. Deeb, Ph.D. Malcolm Pirnie, Inc. Emeryville, CA David K. DeForest Parametrix, Inc. Bellevue, WA Peter J. Drivas, Ph.D. Gradient Corp. Cambridge, MA Sharon M. Drop, M.S. Alcoa, Inc. Pittsburgh, PA David A. Dzombak, Ph.D., P.E., DEE Carnegie Mellon University Pittsburgh, PA Stephen D. Ebbs, Ph.D. Southern Illinois University Carbondale, IL Robert W. Gensemer, Ph.D. Parametrix, Inc. Albany, OR Rajat S. Ghosh, Ph.D., P.E. Alcoa, Inc. Pittsburgh, PA Cortney J. Higgins, M.S. Carnegie Mellon University Pittsburgh, PA Gary E. Isom, Ph.D. Purdue University West Lafayette, IN Michael C. Kavanaugh, Ph.D., PE, DEE Malcolm Pirnie, Inc. Emeryville, CA Roman P. Lanno, Ph.D. Ohio State University Columbus, OH Richard G. Luthy, Ph.D., P.E., DEE Stanford University Stanford, CA ix © 2006 by Taylor & Francis Group, LLC x Contributors Johannes C.L. Meeussen, Ph.D. Energy Research Centre of the Netherlands Petten, The Netherlands Charles A. Menzie, Ph.D. Menzie-Cura and Associates Winchester, MA David V. Nakles, Ph.D., P.E. The RETEC Group Pittsburgh, PA Edward F. Neuhauser, Ph.D. Niagara Mohawk Power Co. Syracuse, NY Sujoy B. Roy, Ph.D. Tetra Tech, Inc. Lafayette, CA Mara Seeley, Ph.D., DABT DABT, Gradient Corp. Cambridge, MA Neil S. Shifrin, Ph.D. Gradient Corp. Cambridge, MA John R. Smith, Ph.D., P.E. Alcoa, Inc. Pittsburgh, PA Angela J. Stenhouse, M.S. Parametrix, Inc. Bellevue, WA Thomas L. Theis, Ph.D., P.E., DEE Univ. of Illinois at Chicago Chicago, IL Jeanne M. VanBriesen, Ph.D. Carnegie Mellon University Pittsburgh, PA George M. Wong-Chong, Ph.D., P.E., DEE USFilter Corporation Pittsburgh, PA Thomas C. Young, Ph.D. Clarkson University Potsdam, NY Anping Zheng, Ph.D. URS Corp. Wayne, NJ Xiuying Zhao, Ph.D. Clarkson University Potsdam, NY © 2006 by Taylor & Francis Group, LLC Contents Chapter 1 Introduction 1 George M. Wong-Chong, David A. Dzombak, and Rajat S. Ghosh Chapter 2 Physical and Chemical Forms of Cyanide 15 Rajat S. Ghosh, David A. Dzombak, and George M. Wong-Chong Chapter 3 Natural Sources of Cyanide 25 George M. Wong-Chong, Rajat S. Ghosh, Joseph T. Bushey, Stephen D. Ebbs, and Edward F. Neuhauser Chapter 4 Manufacture and the Use of Cyanide 41 George M. Wong-Chong, David V. Nakles, and Richard G. Luthy Chapter 5 Physical–Chemical Properties and Reactivity of Cyanide in Water and Soil 57 David A. Dzombak, Rajat S. Ghosh, and Thomas C. Young Chapter 6 Biological Transformation of Cyanide in Water and Soil 93 Stephen D. Ebbs, George M. Wong-Chong, Brice S. Bond, Joseph T. Bushey, and Edward F. Neuhauser Chapter 7 Analysis of Cyanide in Water 123 Rajat S. Ghosh, David A. Dzombak, Sharon M. Drop, and Anping Zheng Chapter 8 Analysis of Cyanide in Solids and Semi-Solids 155 David A. Dzombak, Joseph T. Bushey, Sharon M. Drop, and Rajat S. Ghosh Chapter 9 Fate and Transport of Anthropogenic Cyanide in Surface Water 171 Thomas C. Young, Xiuying Zhao, and Thomas L. Theis Chapter 10 Fate and Transport of Anthropogenic Cyanide in Soil and Groundwater 191 Rajat S. Ghosh, Johannes C.L. Meeussen, David A. Dzombak, and David V. Nakles Chapter 11 Anthropogenic Cyanide in the Marine Environment 209 David A. Dzombak, Sujoy B. Roy, Todd L. Anderson, Michael C. Kavanaugh, and Rula A. Deeb Chapter 12 Cyanide Cycle in Nature 225 Rajat S. Ghosh, Stephen D. Ebbs, Joseph T. Bushey, Edward F. Neuhauser, and George M. Wong-Chong Chapter 13 Human Toxicology of Cyanide 237 Joseph L. Borowitz, Gary E. Isom, and David V. Nakles xi © 2006 by Taylor & Francis Group, LLC [...]... States, 19 83–20 01 Year Production, 10 3 tons/yr 20 01 2000 19 99 19 98 19 97 19 96 19 95 19 94 19 93 19 92 19 91 1990 19 89 19 88 19 87 19 86 19 85 19 84 19 83 750 765 745 725 710 695 675 645 600 570 565 585 565 500 470 430 365 365 330 Sources: Production estimates for 19 83 19 88: Data from Pesce, L.D., Kirk-Othmer Encyclopedia of Chemical Technology, Vol 7, John Wiley & Sons, New York, 19 93 Production estimates for 19 89–20 01: ... Drivas, and Neil S Shifrin 309 Chapter 17 Ecological Risk Assessment of Cyanide in Water and Soil Roman P Lanno and Charles A Menzie 3 31 Chapter 18 Regulation of Cyanide in Water and Soil David V Nakles, David A Dzombak, Rajat S Ghosh, George M Wong-Chong, and Thomas L Theis 3 51 Chapter 19 Cyanide Treatment Technology: Overview George M Wong-Chong, Rajat S Ghosh, and David A Dzombak 387 Chapter 20 Ambient... plants, in their fate and transport in the environment (Chapters 9 11 ), and in their treatability by physical, chemical, and biological treatment technologies (Chapters 19 –24) Until recently, regulation and management of cyanide in water and soil have been focused on total (inorganic) cyanide content (Chapter 18 ) This focus has been driven in large part by the availability of a long-standing, simple, robust... of cyanide in water and soil confusing and inconsistent, and has led to management and treatment approaches of varying effectiveness • We are in the midst of transitioning to species-specific approaches with respect to cyanide, similar to the transition that occurred for management of metal contaminants in water and soil REFERENCES 1 MPC, The last American dinosaur: The 18 72 Mining Law, Mineral Policy... 2000 10 0,000 m3 (26 million gallons) of [34] Gold Quarry Mine, Nevada, USA June 6, 19 97 Omai, Guyana August 19 –24, 19 95 USMX Mine, Utah, USA March 11 14 , 19 95 Summitville, Colorado, USA 19 86 19 92 cyanide- bearing tailings released due to tailings dam failure 245,000 gallons cyanide solution leakage from heap leach pad; discharge to two nearby creeks 4.2 million m3 (1. 1 billion gallons) of cyanide- bearing... efforts involving removal of the material commenced in the 19 90s Related legal actions eventually resulted in settlements totaling $ 21. 8 million against the responsible company [38,39] Thus, even localized cyanide contamination problems can have significant technical, regulatory, and legal implications 1. 7 CYANIDE: CHEMISTRY, RISK, AND MANAGEMENT The management and regulation of cyanide in water and soil... Cyanide in Industrial Process Wastewaters George M Wong-Chong, David V Nakles, and David A Dzombak 517 Chapter 27 Cyanide Management in Groundwater and Soil Rajat S Ghosh, David V Nakles, David A Dzombak, and George M Wong-Chong 5 71 © 2006 by Taylor & Francis Group, LLC 1 Introduction George M Wong-Chong, David A Dzombak, and Rajat S Ghosh CONTENTS 1. 1 1. 2 1. 3 Cyanide in History ... Achievable (BAT) and are contained in the U.S Code of Federal Regulations (40CFR, Parts 425–4 71) Thirteen major industry categories are identified in the federal regulations, including 43 subcategories with cyanide discharge limits (see Chapter 18 ) It is interesting to note that the gold mining industry, a major cyanide user and discharger, is not included in these industry categories Receiving water quality... and algae • Background concentrations of cyanide in water and soil are very low Most cyanide found in water and soil is the result of anthropogenic contamination from industrial sources • The major sources of cyanide in water and soil are discharges and wastes from metal mining processes, metal manufacturing and finishing processes, chemical production, coal conversion processes, and petroleum refining... 19 89–20 01: Data from Myers, E., American Chemistry Council, Washington, DC, personal communication, 2002 TABLE 1. 2 Concentrations of Free Cyanide and Total Cyanide in Six Surface Water Samples from Across Canada Free cyanide (µg/l) Total cyanide (µg/l) Sample Electrode Colorimetry Electrode Colorimetry Stream 1 Stream 2 Stream 3 Lake 1 Lake 2 Lake 3 4 6 4 5 10 17 3 4 4 6 12 19 7 10 11 21 25 48 8 12 12 19 . Atmosphere 5 1. 5 Cyanide in Industry 6 1. 6 Cyanide Releases to Water and Soil 6 1. 7 Cyanide: Chemistry, Risk, and Management 10 1. 8 Cyanide Regulations 11 1. 9 Cyanide Treatment Technology 11 1. 10 Summary. to original U.S. Government works Printed in the United States of America on acid-free paper 10 9876543 21 International Standard Book Number -1 0 : 1- 5 667 0-6 6 6 -1 (Hardcover) International Standard. (Table 1. 2). Introduction 7 TABLE 1. 1 Production of Hydrogen Cyanide in the United States, 19 83–20 01 Production, Year 10 3 tons/yr 20 01 750 2000 765 19 99 745 19 98 725 19 97 710 19 96 695 19 95 675 19 94