CYANIDE in WATER and SOIL: Chemistry, Risk, and Management - Chapter 1 ppt

The chemistry of cyanide is both complex and diverse, and there are many different chemicalforms of cyanide, including solid, gaseous, and aqueous species, and both inorganic and organic

CYANIDE in

Chemistry, Risk, and Management

A CRC title, part of the Taylor & Francis imprint, a member of the Taylor & Francis Group, the academic division of T&F Informa plc.

David A Dzombak Rajat S Ghosh George M Wong-Chong

Chemistry, Risk, and Management

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“Cyanide” is a chemical with a long and fascinating history of respectful and productive use bymankind The fundamental cyanide species, the cyanide ion CN−, is a highly versatile and strongbinder of metals in aqueous solution, a property that has been exploited in ingenious ways forcommercial processes that have benefited society The best known and largest volume uses of cyanideare in the gold mining and electroplating industries In hydrometallurgical gold mining, aqueoussolutions 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 solidmetals are dipped and coated with the metal from solution The deposition of the metal from solutiononto the solid metal is governed by the electrochemical gradient induced in the system, and by themetal–cyanide solution chemistry Cyanide is also produced incidentally in significant quantities in anumber 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 cyanidereleases in the form of gases, solids, and liquids The substantial use of cyanide compounds incommerce coupled with the substantial incidental production of cyanide compounds means thatsignificant amounts of cyanide are introduced into the environment on a continuous basis Cyanidespecies 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 fargreater 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 chemicalforms 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 chemicalforms of cyanide, including solid, gaseous, and aqueous species, and both inorganic and organicspecies 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 ofthe cyanide

In our careers in environmental engineering and science, we have encountered many differentproblems involving cyanide in water and soil Cyanide has been a focus in engineering and researchprojects that we have performed related to industrial and municipal wastewater treatment, ground-water treatment, industrial waste management, site remediation and restoration, and water qualityassessment These projects have been sponsored by a wide range of companies, industrial researchorganizations, and regional and federal government agencies There is widespread interest in cyanidemanagement for environmental and human health protection We have learned much about cyanideuse, management, emissions, and behavior in the environment in the course of these projects Oureducation has been aided by useful knowledge and information acquired from many different sourcesand people

We undertook the preparation of this book to bring together in one place some of the currentknowledge and information about cyanide release to, and behavior in, the environment, and means

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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 the gold miningindustry 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 orientationtoward advancement of hydrometallurgical gold mining There is much to be learned from theextensive knowledge about cyanide that has been gained in the gold mining industry, but there is abroader range of cyanide challenges in environmental engineering and science Our book takes onthis 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, bothanthropogenic and natural We have tried to develop an appropriate balance of depth and scope ofcoverage There have been compromises made on depth of coverage in some topical areas, but in allareas we have endeavored to provide good and current references to enable the reader to learn moreabout topics of particular interest

We developed this book to serve as a useful reference tool for engineers and scientists, ing both practitioners and researchers, in academia, industrial organizations, government, andengineering and science consulting firms We hope we have succeeded in our goal

includ-Effective management and remediation approaches for cyanide in the environment require sideration of issues spanning many different fields In this context, we have collaborated with a widerange of individuals possessing a wide range of expertise in our cyanide-related projects To addressthe range of topics that we wanted to examine in this book, we engaged a number of our formerand 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

con-We are also grateful to Alcoa, Inc and Niagara Mohawk Power Corporation for financial supportthat helped make this book project possible; and USFilter Corporation, the RETEC Group, Inc andthe Carnegie Mellon University Department of Civil and Environmental Engineering for providingassistance with preparation of graphics and the manuscript We owe special thanks to JacquelineZiemianski, Donna Silverman, and Kacey Ebbitt of the RETEC Group, Inc for their good work withpreparation of graphics and securing permissions for use of copyrighted material, and to NicholeDwyer of Carnegie Mellon University for her careful work in helping us with revising and formattingthe text, with completing and formatting references, and with permissions Finally, we thank ourfamilies for their understanding as we used many hours of family time to work on this book

David A DzombakRajat S GhoshGeorge M Wong-Chong

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 aquaticchemistry; 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 and watershed restoration He has over 70 peer-reviewed publicationsand is the joint holder of three patents related to water and soil treatment He has extensive researchand consulting experience with cyanide management and treatment in soils, wastewaters, and processresiduals He has served as a member of the U.S Environmental Protection Agency Science AdvisoryBoard and is involved with numerous other professional service activities Dr Dzombak receivedhis 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 Engineeringfrom 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 CivilEngineers in 2002 Other awards include the Professional Research Award from the PennsylvaniaWater Environment Association (2002); Jack Edward McKee Medal from the Water EnvironmentFederation (2000); Aldo Leopold Leadership Program Fellowship from the Ecological Society ofAmerica (2000); Distinguished Service Award from the Association of Environmental Engineeringand Science Professors (1999); Walter L Huber Civil Engineering Research Prize from the AmericanSociety of Civil Engineers (1997); Harrison Prescott Eddy Medal from the Water EnvironmentFederation (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., the world’s largest producer of aluminum He formerly was a Senior Technical Consultant

in the Pittsburgh office of The RETEC Group, Inc., a U.S environmental engineering and consultingcompany 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 methoddevelopment for various inorganic and organic compounds; and subsurface multiphase flow andchemistry of organic compounds including coal tar, DNAPLs, and petroleum hydrocarbons DrGhosh has extensive research and consulting experience with the electric power, natural gas, andaluminum 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 siteremediation under the auspices of the Strategic Environmental Research and Development Program(SERDP) and Environmental Security and Technology Certification Program (ESTCP) Dr Ghoshreceived 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 inChemical Engineering from Jadavpur University, India He is a registered Professional Engineer inPennsylvania 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-19Committee on Water Dr Ghosh was elected as a member of the Sigma Xi Honor Society Other

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viii Preface

awards include the Jack Edward McKee Medal from the Water Environment Federation (2000) andthe 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 logy development, design, construction, operation, research and teaching of the management andtreatment of contaminated groundwater, wastewaters, and solid hazardous waste Dr Wong-Chong’sexperience 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 majorconcern, 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 veryhigh concentrations of ammonia, cyanide, phenols, and thiocyanate He also holds a patent for thephysical/chemical treatment of municipal and industrial wastewaters Dr Wong-Chong received hisPh.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 ChemicalEngineering 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-Chongreceived the Pennsylvania Water Environment Association Professional Research Award and theAmerican Institute of Chemical Engineers Pittsburgh Section Award for Outstanding ProfessionalAccomplishments 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 technologydevelopment

Todd L Anderson, P.E.

Malcolm Pirnie, Inc

Emeryville, CA

Barbara D Beck, Ph.D., DABT

DABT, Gradient Corp

David A Dzombak, Ph.D., P.E., DEE

Carnegie Mellon UniversityPittsburgh, PA

Michael C Kavanaugh, Ph.D., PE, DEE

Malcolm Pirnie, Inc

ix

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

Mara Seeley, Ph.D., DABT

DABT, Gradient Corp

Thomas L Theis, Ph.D., P.E., DEE

Univ of Illinois at ChicagoChicago, IL

Thomas C Young, Ph.D.

Clarkson UniversityPotsdam, NY

George M Wong-Chong, David A Dzombak, and Rajat S Ghosh

Rajat S Ghosh, David A Dzombak, and George M Wong-Chong

George M Wong-Chong, Rajat S Ghosh, Joseph T Bushey, Stephen D Ebbs, and Edward F Neuhauser

George M Wong-Chong, David V Nakles, and Richard G Luthy

David A Dzombak, Rajat S Ghosh, and Thomas C Young

Stephen D Ebbs, George M Wong-Chong, Brice S Bond, Joseph T Bushey,

and Edward F Neuhauser

Rajat S Ghosh, David A Dzombak, Sharon M Drop, and Anping Zheng

David A Dzombak, Joseph T Bushey, Sharon M Drop, and Rajat S Ghosh

Thomas C Young, Xiuying Zhao, and Thomas L Theis

Rajat S Ghosh, Johannes C.L Meeussen, David A Dzombak, and

David V Nakles

David A Dzombak, Sujoy B Roy, Todd L Anderson, Michael C Kavanaugh, and Rula A Deeb

Rajat S Ghosh, Stephen D Ebbs, Joseph T Bushey, Edward F Neuhauser,

and George M Wong-Chong

Joseph L Borowitz, Gary E Isom, and David V Nakles

xi

xii Contents

Robert W Gensemer, David K DeForest, Angela J Stenhouse,

Cortney J Higgins, and Rick D Cardwell

Jeremy M Clark, Rick D Cardwell, and Robert W Gensemer

Barbara D Beck, Mara Seeley, Rajat S Ghosh, Peter J Drivas, and

Neil S Shifrin

Roman P Lanno and Charles A Menzie

David V Nakles, David A Dzombak, Rajat S Ghosh, George M Wong-Chong, and Thomas L Theis

George M Wong-Chong, Rajat S Ghosh, and David A Dzombak

Rajat S Ghosh, Thomas L Theis, John R Smith,

and George M Wong-Chong

David A Dzombak, Rajat S Ghosh, George M Wong-Chong,

and John R Smith

Chapter 22 Thermal and High Temperature Oxidation Technologies for Treatment of

Rajat S Ghosh, John R Smith, and George M Wong-Chong

George M Wong-Chong and Jeanne M VanBriesen

Stephen D Ebbs, Joseph T Bushey, Brice S Bond, Rajat S Ghosh, and

David A Dzombak

David A Dzombak, Anping Zheng, Michael C Kavanaugh,

Todd L Anderson, Rula A Deeb, and George M Wong-Chong

George M Wong-Chong, David V Nakles, and David A Dzombak

Rajat S Ghosh, David V Nakles, David A Dzombak, and

George M Wong-Chong

1 Introduction

George M Wong-Chong, David A Dzombak, and

Rajat S Ghosh

CONTENTS

1.1 Cyanide in History 2

1.2 Cyanide Chemical Structure 2

1.3 Cyanide and the Origin of Life 2

1.3.1 Role of Hydrogen Cyanide in the Production of Amino Acids 2

1.3.2 Stanley Miller’s Experiment 3

1.4 Ubiquity of Cyanide Compounds in Nature 5

1.4.1 Cyanide in Outer Space 5

1.4.2 Hydrogen Cyanide in Earth’s 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 and Conclusions 12

References 12

Cyanide compounds are produced and used in commerce in large quantities In the United States, for example, approximately 200 million pounds of sodium cyanide are used annually just in heap leaching extraction of gold from ore [1], with much of this use taking place in one state, Nevada, which accounts for about 70% of U.S gold production [2] Large amounts of sodium cyanide are also used in electroplating [3] Cyanide compounds are also produced incidentally in many processes, such as in aluminum and steel production, and are associated with wastewaters, solid wastes, and air emissions from these processes In addition, cyanide compounds are present in legacy wastes disposed onsite at numerous manufactured gas plant sites in the United States and Europe As a result, cyanide is a commonly encountered contaminant in water and soil

Because of the high degree of toxicity in certain forms of cyanide, primarily hydrogen cyanide (HCN), acceptable levels of cyanide compounds in water and soil are generally very low For example, the U.S drinking water maximum contaminant level for free cyanide (HCN and CN−) is 0.2 mg/l, while the U.S ambient water quality criterion for acute exposures in freshwater systems is 22µg/l.

As this thousandfold difference indicates, some aquatic organisms are significantly more sensitive

to cyanide than are humans

Addressing problems of cyanide contamination in water and soil can be very challenging Complicating factors include the complex chemistry and speciation of cyanide; the analytical challenges of measuring cyanide species in water and soil; the differential toxicity, reactivity, and treatability of the various cyanide species; overlapping and sometimes inconsistent regulations pertaining to cyanide; and the widespread public fear of cyanide, regardless of its form and location Knowledge in all these areas is needed to develop effective strategies to remedy or manage cyanide

1