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

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
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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
xii Contents
Chapter 14 Aquatic Toxicity of Cyanide 251
Robert W. Gensemer, David K. DeForest, Angela J. Stenhouse,
Cortney J. Higgins, and Rick D. Cardwell
Chapter 15 Toxicity of Cyanide to Aquatic-Dependent Wildlife 285
Jeremy M. Clark, Rick D. Cardwell, and Robert W. Gensemer
Chapter 16 Human Health Risk Assessment of Cyanide in Water and Soil 309
Barbara D. Beck, Mara Seeley, Rajat S. Ghosh, Peter J. Drivas, and
Neil S. Shifrin

Chapter 17 Ecological Risk Assessment of Cyanide in Water and Soil 331
Roman P. Lanno and Charles A. Menzie
Chapter 18 Regulation of Cyanide in Water and Soil 351
David V. Nakles, David A. Dzombak, Rajat S. Ghosh, George M. Wong-Chong,
and Thomas L. Theis
Chapter 19 Cyanide Treatment Technology: Overview 387
George M. Wong-Chong, Rajat S. Ghosh, and David A. Dzombak
Chapter 20 Ambient Temperature Oxidation Technologies for Treatment of Cyanide 393
Rajat S. Ghosh, Thomas L. Theis, John R. Smith,
and George M. Wong-Chong
Chapter 21 Separation Technologies for Treatment of Cyanide 413
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
Cyanide 439
Rajat S. Ghosh, John R. Smith, and George M. Wong-Chong
Chapter 23 Microbiological Technologies for Treatment of Cyanide 459
George M. Wong-Chong and Jeanne M. VanBriesen
Chapter 24 Cyanide Phytoremediation 479
Stephen D. Ebbs, Joseph T. Bushey, Brice S. Bond, Rajat S. Ghosh, and
David A. Dzombak
Chapter 25 Management of Cyanide in Municipal Wastewaters 501
David A. Dzombak, Anping Zheng, Michael C. Kavanaugh,
Todd L. Anderson, Rula A. Deeb, and George M. Wong-Chong
Chapter 26 Management of Cyanide in Industrial Process Wastewaters 517
George M. Wong-Chong, David V. Nakles, and David A. Dzombak
Chapter 27 Cyanide Management in Groundwater and Soil 571
Rajat S. Ghosh, David V. Nakles, David A. Dzombak, and
George M. Wong-Chong
© 2006 by Taylor & Francis Group, LLC

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 inwater and soilare generallyvery 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 22 µg/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
© 2006 by Taylor & Francis Group, LLC
2 Cyanide in Water and Soil
contamination in water and soil. This book presents current scientific understanding and engineering
approaches for managing water and soil contamination with cyanide.
1.1 CYANIDE IN HISTORY
Cyanide is a chemical well known to the public as a highly toxic agent [4]. For many, the word
“cyanide” evokes emotions of death. This perception is prevalent in the history of cyanide dating
back to antiquity, long before any understanding of the chemistry of this family of compounds
was known. Traitorous Egyptian priests of Memphis and Thebes were poisoned using the pits of
peaches [5]. In the 20th century, HCN gas was used in gas chambers in the World War II Holocaust,
in prisons for execution of criminals with death sentences, and also as a chemical warfare agent.
In 1782, the Swedish chemist Carl WilhelmScheele discovered a flammable, water-soluble acidic
gas, later identified as HCN, when he heated the cyanide-bearing solid Prussian Blue in an aqueous
sulfuric acid solution [6–8]. The name given to the evolved gas was Prussian Blue Acid, also referred
to as prussic acid or blue acid [7]. This same gas caused Scheele’s death four years later [8]. The
words “cyanine” and “cyanide,” derived from the Greek word “kyanos” for blue, soon came into use

to describe the gas [7]. In 1811, Guy Lussac determined the composition of the gas as consisting of
one molecule each of carbon, hydrogen, and nitrogen [6]. He referred to the HCN gas as hydrocyanic
acid, or hydrogen cyanide.
1.2 CYANIDE CHEMICAL STRUCTURE
Cyanide compounds contain the cyano-moiety, which consists of the carbon atom triply bonded to
the nitrogen atom (−C≡N). The most basic, and most toxic, of these compounds is hydrogen cyanide
(H−C≡N), hydrocyanic acid. HCN is a gas at ambient temperature, and is freely soluble in water.
In water, HCN dissociates at high pH (pK
a
= 9.24 at 25
◦
C) to form the cyanide anion, CN
−
.
There are many different inorganic and organic cyanide compounds. Inorganic compounds
include simple salts of cyanide with various metals such as sodium cyanide, NaCN(s), potassium
cyanide, KCN(s), and more complex solids such as ferric ferrocyanide, Fe
4
(Fe(CN)
6
)
3
(s), alsoknown
as Prussian Blue. The simple salts are highly soluble in water. The aqueous solubility of Prussian
Blue and other similar complex cyanide solids are functions of pH and redox potential. There are
also many organocyanide compounds, such as acetonitrile (CH
3
CN), acrylonitrile (CH
2
CHCN), and

cyanogenic glycosides.
1.3 CYANIDE AND THE ORIGIN OF LIFE
1.3.1 R
OLE OF HYDROGEN CYANIDE IN THE PRODUCTION OF
AMINO ACIDS
In the Precambrian or prebiotic period, about 4.6 billion years ago, primary components of the
earth’s atmosphere were carbon monoxide, methane, hydrogen, nitrogen, ammonia, and water [9].
The German biologist E. Pfluger hypothesized that as the earth’s surface slowly cooled from an
incandescent mass, HCN was formed by the chemical union of carbon and nitrogen, and that this
compound had time to transform and polymerize to form proteins which constitute living matter [10].
of HCN and formaldehyde (another compound formed from the reaction of the constituents in the
primitive earth’s atmosphere) to form glycine. These two compounds allow the synthesis of many
amino compounds. Oro and Kimball [11,12] demonstrated the synthesis of adenine, a nucleic acid,
and other purine intermediates from HCN under possible primitive earth conditions. These abiotically
synthesized proteins were important stepping-stones to life, as we know it today.
© 2006 by Taylor & Francis Group, LLC
Figure 1.1 and Figure 1.2 illustrate the polymerization of HCN, to form adenine, and the reaction
Introduction 3
N
+HCN
Hydrogen
cyanide
N
N
N
N
N
+HCN
+HCN
N

N
N
N
Diaminomaleonitrile (HCN)
4
Adenine (HCN)
5
Hydrogen Carbon Nitrogen
(HCN)
2
(HCN)
3
+HCN
N
N
N
N
N
N
FIGURE 1.1 Polymerization of hydrogen cyanideto form adenine. (Source: Barbieri, M., The Organic Codes:
An Introduction of Semantic Biology, Cambridge University Press, Cambridge, MA, 2002. With permission.)
1.3.2 STANLEY MILLER’S EXPERIMENT
In 1953, Stanley Miller demonstrated that HCN and certain organic compounds, including aldehydes
and amino acids, can be formed from the constituents of the prebiotic earth atmosphere, that is,
methane, ammonia, hydrogen, and water [9]. The experiments, which earned Miller a Nobel Prize,
was claimed to be a crude model of the primitive earth’s atmosphere, was charged with water and
air was evacuated; then, a mixture of ammonia, methane and hydrogen was added. The water in the
small flask was boiled to initiate a circulation of gases and water vapor into the reaction flask, in
which an electric spark was generated. The spark initiated the reaction of the ammonia, hydrogen,
© 2006 by Taylor & Francis Group, LLC

were performed in a spark-discharge reaction apparatus as shown in Figure 1.3. The apparatus, which
4 Cyanide in Water and Soil
Formaldehyde Ammonia
Hydrogen
cyanide
Ammonitrile Water Ammonia Glycine
+
+
Ammonitrile Water
+
+
+
Hydrogen Carbon Nitrogen
N
N
N
N
N
N
N
N
N
Oxygen
FIGURE 1.2 Reaction of hydrogen cyanide and formaldehyde to form glycine. (Source: Barbieri, M., The
Organic Codes: An Introduction of Semantic Biology, Cambridge University Press, Cambridge, MA, 2002.
With permission.)
spark discharge
Electrodes
Gases
Water out

Water in
Water droplets
Liquid water in trap conaining
organic compounds
Boiling
water
To a
vacuum
pump
Condenser
FIGURE 1.3 Apparatus for experiment by Stanley Miller that demonstrated formation of hydrogen cyanide
from constituents of the prebiotic Earth atmosphere. (Source: Miller, S.L. and Orgel, L.E., The Origins of Life
on Earth, Prentice-Hall, Englewood Cliffs, NJ, 1974. With permission.)
methane, and water to form HCN and aldehydes. A typical experiment entailed operating of the spark
the reaction profiles for ammonia (charged material), and amino acids, HCN and aldehydes (reaction
products). Miller’s data clearly demonstrated a mechanism for abiotic production of HCN in the
atmosphere, one that also exists today during electrical discharges associated with thunderstorms [9].
© 2006 by Taylor & Francis Group, LLC
continuously for about 1 week with regular analysis of samples from the system. Figure 1.4 shows
Introduction 5
Molar concentration
Time (h)
Aldehydes (×10
3
)
HCN
(×10
2
)
Amino acids(×10

3
)
NH
3
(×10)
8
7
6
5
4
3
2
1
25 50 75 100 125 150
FIGURE 1.4 Reactant and product concentrations in the experiment by Stanley Miller. (Source: Miller, S.L.
and Orgel, L.E., The Origins of Life on the Earth, Prentice-Hall, Englewood Cliffs, NJ, 1974. With permission.)
The findings of Miller are further substantiated by the discovery of the presence of CO, HCN, OH
•
,
formaldehyde and methanol in outer space [13].
1.4 UBIQUITY OF CYANIDE COMPOUNDS
IN NATURE
Cyanide compounds occur commonly in nature. HCN is present in outer space, in the earth’s atmo-
sphere, in plants, animals, microbes, and fungi. Cyanide can be produced by certain plants, bacteria,
rence, role, and environmental impact of cyanide in plants, animals, microbes, and fungi. The natural
1.4.1 CYANIDE IN OUTER SPACE
Hydrogen cyanide has been detected at a number of locations in outer space. For example, it is a
trace constituent in the nitrogenous atmosphere of Titan, the largest moon of Saturn [14], and in the
coma of the Hale–Bopp comet [15]. Polymerization products of HCN are the dominant components
of dust grains sampled from the tail of Comet 81P/Wild2 in 2004 [16]. This presence of HCN in

space is now being used to study the birth of massive stars [17]. The detection of large amounts of
HCN toward the center of a protostar (an evolving star) means that it has already started to warm up;
from this information it is possible to determine the degree of evolution and the age of the star [17].
1.4.2 H
YDROGEN CYANIDE IN EARTH’S ATMOSPHERE
Hydrogen cyanide is detectable in the troposphere and stratosphere of the earth. Its concentra-
tion in the nonurban troposphere of the northern hemisphere has been reported as approximately
160 pptv [18]. In the tropical upper troposphere, a range of HCN concentrations from 200 to 900 pptv
© 2006 by Taylor & Francis Group, LLC
fungi, and algae. Chapter 3, which examines natural sources of cyanide, discusses in detail the occur-
cycle of cyanide in the environment is the focus of Chapter 12.
6 Cyanide in Water and Soil
has been reported [19]. From field measurements and modeling it has been established that biomass
burning is a major global source of HCN emissions [19,20]. Estimates of the total release of HCN
to the atmosphere from biomass burning range from 1.4 to 2.9 × 10
12
g (as N) per year [19]. The
residence time of HCN in the atmosphere is approximately two to four months [19]. The oceans of
the world provide a sink for the atmospheric releases of HCN and other compounds from biomass
1.5 CYANIDE IN INDUSTRY
most cyanide compounds are manufactured starting with HCN, which is synthesized by the platinum-
catalyzed reaction of ammonia and methane [3]. HCN is a basic chemical feed stock used in the
manufacture of sodium cyanide for gold mining and electroplating; adiponitrile for nylon; methyl
methacrylate for clear plastic; triazines for agricultural herbicides; methionine for animal food
supplement; and chelating agents (e.g., nitrilotriacetate) for water and wastewater treatment [3].
Worldwide annual production and manufacturing capacity of HCN in 1992 were estimated to be
0.95 million tons and 1.32 million tons, respectively [3]. A 2001 estimate of worldwide cyanide
production was 2.60 million tons [7]. In 2001, 0.75 million tons of HCN were produced in the U.S.
sodium cyanide [3,21,22], much of which is used in hydrometallurgical gold mining. The production
and use of cyanide is growing, as indicated by the chronological tabulation of HCN production in

the United States in Table 1.1.
In addition to use of cyanide compounds in gold mining, electroplating, and chemical produc-
tion, cyanide compounds are also used in some applications that involve direct distribution to the
environment. Sodium ferrocyanide, Na
4
(Fe(CN)
6
) and ferric ferrocyanide, Fe
4
(Fe(CN)
6
)
3
(s) are
used as an anticaking agent in road salt [23]. It is the presence of ferric ferrocyanide that gives
a blue color to salt in which it is used. These compounds can dissolve in water after placement on
road surfaces. Sodium ferrocyanide is also used in some forest fire retardants [24].
1.6 CYANIDE RELEASES TO WATER AND SOIL
Most cyanide that occurs in water and soil is anthropogenic, derived from industrial processes, but
there arenatural sources of cyanide as noted above. The combination of widespread industrial sources
and natural sources leads to detectable concentrations of cyanide in many natural waters, though con-
centrations are usually low. In a 1981 evaluation of monitoring data in the USEPA STORET database,
it was determined that the mean concentration of total cyanide in surface waters of the United States
did not exceed 3.5 µg/l, but in 37 of 50 states there were sampling locations where total cyanide con-
centrations in excess of this level were reported [25]. Sample results from a number of industrialized
areas had total cyanide concentrations greater than 200 µg/l. Total cyanide concentrations in U.S.
drinking water intake supplies are usually very low (<10 µg/l) to nondetectable [26,27]. Analyses
of six Canadian surface waters for a performance comparison of analytical techniques yielded total
cyanide concentrations less than 12 µg/l for the three streams sampled, but in the range of 19 to
The major sources of cyanide in water and soil are discharges and wastes from metal mining

processes, metal manufacturing and finishing processes, chemical production, and petroleum refin-
ing [4,28,29]. Cyanide contamination of water and soil from industrial sources can be recent, from
ongoing operations, or may be from wastes disposed long ago. For example, cyanide occurs in soil
and groundwater inthe vicinity of old spent potlining landfillsat aluminum smelting facilities [30,31],
and in old disposal areas for oxide box wastes at former manufactured gas plant sites [31–33].
© 2006 by Taylor & Francis Group, LLC
burning [19], as discussed in Chapter 11.
Substantial quantities of cyanide compounds are used and produced in commerce (Chapter 4). Today
(Table 1.1). A significant fraction, estimated to range from 8 to 20%, of HCN is used to produce
49 µg/l for the three lakes sampled (Table 1.2).
Introduction 7
TABLE 1.1
Production of Hydrogen Cyanide in
the United States, 1983–2001
Production,
Year 10
3
tons/yr
2001 750
2000 765
1999 745
1998 725
1997 710
1996 695
1995 675
1994 645
1993 600
1992 570
1991 565
1990 585

1989 565
1988 500
1987 470
1986 430
1985 365
1984 365
1983 330
Sources: Production estimates for 1983–1988:
Data from Pesce, L.D., Kirk-Othmer Encyclope-
dia of Chemical Technology, Vol. 7, John Wiley
& Sons, New York, 1993. Production estimates
for 1989–2001: 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 4378
Stream 2 6 4 10 12
Stream 3 4 4 11 12
Lake 1 5 6 21 19
Lake 2 10 12 25 27
Lake 3 17 19 48 49
Source: Reprinted from Water Res., 104, Sekerka, I. and Lechner,
J.F. Potentiometric determination of low levels of simple and total
cyanides, 479, copyright (1976), with permission from Elsevier.
© 2006 by Taylor & Francis Group, LLC
8 Cyanide in Water and Soil

TABLE 1.3
Examples of Discharges from Gold Mine Heap Leaching Operations
Location Release date/period Release scenario Reference
Baia Mare, Romania January 30–February 2, 2000 100,000 m
3
(26 million gallons) of
cyanide-bearing tailings released due to
tailings dam failure
[34]
Gold Quarry Mine, Nevada, USA June 6, 1997 245,000 gallons cyanide solution leakage
from heap leach pad; discharge to two
nearby creeks
[44]
Omai, Guyana August 19–24, 1995 4.2 million m
3
(1.1 billion gallons) of
cyanide-bearing tailings water released
due to tailings dam failure
[45]
USMX Mine, Utah, USA March 11–14, 1995 7 million gallons treated leach solution
containing 0.2 ppm cyanide, released
from storage ponds to East Fork of
Beaver Dam Wash
[46]
Summitville, Colorado, USA 1986–1992 Sustained cyanide solution leaks from
heap leach pad, from transfer pipes, and
from tailings pond; discharge to Alamosa
River
[47,48]
The most dramatic releases of cyanide to water and soil have occurred in the failure of or

substantial leakage from heap leaching pads or tailings ponds associated with gold mining operations.
Table 1.3 lists some large-volume discharges that have occurred since 1992. The failure of the tailings
pond dam at a gold mine near Baia Mare, Romania, in January 2000 provides an example of the
large scale of impact that can result from such discharges. Due to heavy precipitation coupled with
a rapid snowmelt, a gold mine tailings pond near Baia Mare filled to capacity and overflowed,
resulting in washout of a section of the earthen containment dam for the pond. Approximately
100,000 cubic meters of tailings water containing free cyanide, metal–cyanide complexes, metals,
and suspended solids were discharged from January 30 to February 2, 2000 [34]. Based on cyanide
concentrations in the tailings pond and the approximate spill volume, it is estimated that 50 to 100
River, which subsequently joins with the Lapus River, and then the Somes River. The Somes flows
into Hungary, and there it discharges into the Tisza River, which flows through Hungary and into
Serbia (formerly, Yugoslavia). Just north of Belgrade the Tisza discharges into the Danube, which
returns to Romania and eventually discharges into the Black Sea. It took the plume of contamination
about 14 days to reach the Danube, which is approximately 800 km in river distance from the spill
location. The plume then traveled an additional 1,200 km in the Danube. Total cyanide concentrations
as high as 32.6 mg/l were measured in the Somes River at the Hungarian–Romanian border. The
maximum cyanide concentration observed in the Tisza River at the Hungarian–Yugoslavian border
was 1.5 mg/l, and in the Danube River near the Yugoslavian–Romanian border was 0.34 mg/l. These
concentrations, while demonstrating the dilution, biodegradation, and volatilization of the cyanide
during riverine transport to the Black Sea, nevertheless were 15 to 1,500 times greater than water
quality criteria to protect freshwater aquatic life to acute exposures. As a result, massive fish kills
in the Hungarian portion of the Tisza River as a result of the spill was 1,240 tons [34]. There were
also substantial but unquantified fish kills in the Tisza River in Yugoslavia.
Smaller in scale but more widespread are the many continuing releases of cyanide from solid
wastes disposed on land in the past and from ongoing wastewater discharges. Cyanide-bearing oxide
© 2006 by Taylor & Francis Group, LLC
tons of cyanide were released. As shown in the map on Figure 1.5, the spill entered the Sasar
were experienced due to the cyanide plume from Baia Mare (Figure 1.6). An estimate of dead fish
Introduction 9
SLOVAKIA

HUNGARY
Budapest
Miskoic
Szeged
UKRAINE
Baia Mare
Bucharest
Sasar
ROMANIA
MOLDOVA
Black
sea
BUICARIA
YUGOSLAVIA
Belgrade
1
2
4
5
6
7
8
9
3
Timisoara
Tiza
FIGURE 1.5 Map showing the river transport route for the cyanide plume from the spill at Baia
FIGURE 1.6 Worker removing dead fish killed by a cyanide spill in Hungary’s Tisza River, at Kiskore on
February 9, 2000. Photo by Laszlo Balogh. © Reuters 2000. Used with permission.
© 2006 by Taylor & Francis Group, LLC

Mare, Romania, January–February 2000. (Source: Data from: UNEP, />CyanideSpill/ENGCyanide.pdf, 2000.)
10 Cyanide in Water and Soil
box wastes at thousands of former manufactured gas plant (MGP) sites throughout the United States
and Europe are an example of a widely distributed industrial legacy waste. These wastes, which
contain the iron cyanide solid Prussian Blue, were disposed in onsite landfills at many MGP sites.
Dissolved cyanide is generated by contact of these solids with groundwater, resulting in under-
ground plumes of contamination that can move significant distances, depending on subsurface
conditions [31,35,36]. At a former MGP site in Wisconsin, it was demonstrated that dissolved
cyanide moved with the groundwater through the sand and gravel aquifer beneath the site, toward a
municipal drinking water supply well located 500 m from the site [31]. In another area of Wisconsin,
oxide box wastes from an MGP operation were placed as landfill material in three-foot thick
layers along an electric transmission line corridor, amounting in just one section of the corridor to
26,000 tons of fill material [37]. Remediation efforts involving removal of the material commenced
in the 1990s. 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 can be very challenging because of the
complexity of the chemistry and toxicology of cyanide, the risk it poses in different environmental
contexts, and stringent regulatory requirements to be satisfied [32,40,41]. Many different chemical
forms of cyanide occur in water and soil, including dissolved free cyanide (HCN, CN
−
), metal-
cyanide complexes (e.g., Ni(CN)
2−
4
, Fe(CN)
4−
6
), and organocyanide (e.g., acetonitrile, CH

3
CN)
species, as well as metal-cyanide solids (e.g., ferric ferrocyanide, Fe
4
(Fe(CN)
6
)
3
(s)). In addition,
HCN in water can volatilize, forming HCN(g). The different chemical forms of cyanide and their
affected by different chemical reactions, and each has different physical, chemical, and toxicological
properties. For example, the toxicological significance of each individual metal–cyanide complex
is determined by its ability to release free cyanide (CN
−
or HCN), the target species of concern,
under pertinent exposure conditions. The chemical dissociative properties of each complex thus
control the release of free cyanide and hence toxicity. Thus, the differences in properties mean that
the various cyanide species vary in their toxicity to animals and plants, in their fate and transport
Until recently, regulation and management of cyanide in water and soil have been focused on total
of a long-standing, simple, robust technique for measuring total inorganic cyanide content: strong
acid digestion to transform all inorganic cyanide compounds to HCN followed by distillation to
volatilize and capture the HCN(g). While such total cyanide measurements are useful and indeed
continue to be the predominant means of monitoring cyanide, they provide no direct information
about cyanide speciation. The focus on total cyanide content has made regulations of cyanide in
water and soil confusing and inconsistent, and has led to management and treatment approaches of
varying effectiveness.
Knowledgeof cyanidespeciation is critical to technically and economically effectivemanagement
of cyanide in water and soil. This is now fairly well recognized in the engineering, science, and
regulatory professional communities, but measurements, regulations, treatment technologies, and
site management plans with a species-specific focus are still evolving for cyanide. We are in the

midst of transitioning to species-specific approaches with respect to cyanide, similar to the transition
that occurred through the 1980s for management of metal contaminants in water and soil. This book
is intended to help with and to accelerate that transition.
© 2006 by Taylor & Francis Group, LLC
reactivity and properties are discussed in Chapters 2, 5, and 6. Each of these species is formed and
in the environment (Chapters 9–11), and in their treatability by physical, chemical, and biological
treatment technologies (Chapters 19–24).
(inorganic) cyanide content (Chapter 18). This focus has been driven in large part by the availability
Introduction 11
1.8 CYANIDE REGULATIONS
Cyanide aqueous discharge regulations in the United Statesare based on effluent discharge limitations
for categorical industries (e.g., iron and steel, organic chemicals manufacturing, and electroplating)
and receiving water quality criteria. Effluent limits for categorical industries are largely based on the
performance of Best Available Technology Economically Achievable (BAT) and are contained in
the U.S. Code of Federal Regulations (40CFR, Parts 425–471). Thirteen major industry categories
are identified in the federal regulations, including 43 subcategories with cyanide discharge limits
discharger, is not included in these industry categories.
Receiving water quality criteria, which are based on aquatic toxicity studies and aimed at pro-
tection of aquatic life, are significantly more stringent than BAT discharge limits. For discharges to
water bodies in which the designated use mandates protection of aquatic life, cyanide effluent limits
are usually developed with the objective of not exceeding water quality criteria. Discharge limits
based on consideration of water quality criteria tend to be very stringent, and can be at or below detec-
tion limits achieved in routine commercial analyses. For example, effluent limits for shallow-water
marine discharges in the United States are often set at the marine water quality criterion of 1 µg/l
free cyanide. The detection limit for free cyanide with standard analytical methods often exceeds
with measuring cyanide in water, wastewater, soil and sludges, and the very troublesome issues of
detection, practical quantitation limits, and measurement precision. In addition, water quality cri-
teria reflect toxicity to very sensitive aquatic species that may not be present in a particular receiving
water.
Soil cleanup standards for cyanide have been established by some states in the United States

and by some countries in Europe (see Chapter 18). Many other government organizations have
established soil screening or action levels to define when additional remedial investigation or action
is needed. Soil cleanup standards or screening levels for cyanide vary widely. For example, soil
cleanup standards for free cyanide in residential surface soils, where direct human contact can occur,
have been set at 30, 160, 1,600, and4,400 mg/kg by Florida, Maryland, New Jersey, and Pennsylvania,
respectively. Free cyanide cleanup standards for nonresidential surface soils established by the same
four states are 39,000, 4,100, 56,000, and 23,000 mg/kg. By contrast, the Netherlands has set the
“intervention value” for free cyanide in soil at the low value of 20 mg/kg based on human health risk
considerations, and has established separate values for complexed cyanide at 50 mg/kg for soils with
pH ≥5 and at 650 mg/kg for soils with pH < 5 [42]. The Dutch soil “target values” for protection of
ecosystems are even lower: 1.0 mg/kg for free cyanide and 5.0 mg/kg for complexed cyanide [42].
Acceptable concentrations of free and complexed cyanide in water and soil are determined by
cyanide aqueous discharge limits and treatment/management objectives for soil and other cyanide-
contaminated media.
1.9 CYANIDE TREATMENT TECHNOLOGY
An array of technologies is available for the treatment of cyanide in surface water and ground-
water, wastewaters, and contaminated soils and sludges. These technologies, discussed in detail in
processing. Example applications of the technologies employed most commonly in municipal and
of cyanide contamination management is that commercial applications of the technologies in an
economical mode of operation may not yield treated water, soil, or sludge with cyanide concentra-
tions that meet specified regulatory limits. Careful evaluation of technology performance, including
treatability testing, is needed prior to application of technologies for cyanide management.
© 2006 by Taylor & Francis Group, LLC
(see Chapter 18). It is interesting to note that the gold mining industry, a major cyanide user and
this amount by factors of 2 to 5 or more. Chapters 7 and 8 discuss the analytical issues associated
risk assessment. Chapters 13 to 17 examine the toxicity and risk issues that drive the establishment of
Chapters 19–24, span the gamut of biological, chemical, electrolytic, physical, and thermal treatment
industrial settings are presented in Chapters 25–27. An important message from these examinations
12 Cyanide in Water and Soil
1.10 SUMMARY AND CONCLUSIONS

• Cyanide compounds are produced and used in commerce in large quantities.
• Many different chemical forms of cyanide can exist in water and soil, each of which has
different physical, chemical, and toxicological properties.
• Because of the high degree of toxicity of certain forms of cyanide, primarily hydrogen
cyanide (HCN), acceptable levels of cyanide compounds in water and soil can be very
low, for example, 1 µg/l for free cyanide in marine waters of the United States.
• Many aquatic organisms are significantly more sensitive to cyanide than are humans.
• Cyanide species can be formed in nature by both abiotic and biotic processes. Cyanide
can be produced by certain plants, bacteria, fungi, 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.
• The management and regulation of cyanide in water and soil can be very challenging
because of the complexity of the chemistry and toxicology of cyanide and, accordingly,
the risk it poses in different environmental contexts. A further complication is that there
is widespread public fear of cyanide, regardless of its form and location.
• The focus on total cyanide content has made regulations 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.
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14 Cyanide in Water and Soil
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