CYANIDE in WATER and SOIL: Chemistry, Risk, and Management - Chapter 18 pot

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
CONTENTS
18.1 U.S. Regulations, Guidelines and Criteria for Cyanide in Water 352
18.1.1 Drinking Water 355
18.1.2 Surface Water and Groundwater 359
18.1.3 Federal Wastewater Discharge Standards 360
18.1.3.1 Effluent Guidelines and Standards 360
18.1.3.2 Specific Characteristics of Guidelines/Standards 361
18.1.4 Groundwater (RCRA and CERCLA) 362
18.1.4.1 Groundwater (RCRA) 371
18.1.4.2 Groundwater (CERCLA) 372
18.2 U.S. Regulations, Guidelines, and Criteria for Soil,
Sediment, and Process Residuals 372
18.2.1 Soil and Process Residuals 372
18.2.1.1 Listed Wastes 373
18.2.1.2 Characteristic Wastes 373
18.2.2 Sediment 373
18.3 International Regulatory Standards and Guidelines for Cyanide in Water and Soil 375
18.3.1 Water 376
18.3.1.1 Drinking Water 376
18.3.1.2 Surface Water 376
18.3.1.3 Groundwater 377
18.3.2 Soil 378
18.3.3 Sediment 378
18.4 Technical/Regulatory Issues 380
18.4.1 Lack of Consistency: Analytical Methods and Regulations 380
18.4.2 Cyanide Transformation in the Environment 381

18.4.3 Cyanide Toxicological Database 381
18.4.4 Cyanide as a CERCLA Hazardous Substance 382
18.5 Summary and Conclusions 382
References 383
Various forms of cyanide in water and soil have been regulated in the United States and elsewhere for
many years, dating back to the beginning of the environmental era of the early 1970s. The primary
driver for regulating cyanide, of all forms, is the acute human and ecological toxicity associated with
hydrogen cyanide. The toxicological effects of this compound on humans and animals have been
351
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extensively examined and are well understood (see Chapters 13–15). However, it is also understood
352 Cyanide in Water and Soil
that cyanide may exist in a number of different chemical forms, none of which are as toxic as
hydrogen cyanide. In fact, several forms of cyanide are known to exist naturally in the environment
or approved for regulatory use relatively recently.
These circumstances have led to fairly conservative cyanide regulations for soil and water that are
in many cases based on the concentration of total cyanide. That is, many regulations do not discrim-
inate among the various forms of cyanide that may be present. This was a reasonable approach for
regulating cyanide-impacted media in the 1970s, given the previous state of the analytical methods
and the potential for specific nontoxic forms of cyanide to release hydrogen cyanide under certain
environmental conditions. However, as the science for the detection of cyanide species and the under-
standing of the fate of these species in the environment has evolved, modifications to the regulatory
framework have begun to be implemented at both the state and Federal levels in the United States,
and in other countries as well.
This chapter presents a summary of the U.S. environmental regulations that address the forms
of cyanide that may be present in a soil or water matrix. A brief examination of some water and soil
regulations for cyanide in other countries is also provided.
At the Federal level in the United States, cyanide in water and soil is regulated under the Clean
Water Act (CWA), the Safe Drinking Water Act (SDWA), and the Resource Conservation and Recov-
ery Act (RCRA). The regulations promulgated under these acts by the U.S. Environmental Protection

Agency (USEPA) havesetforthspecific standards and criteria for cyanide in receiving water, drinking
water, wastewaters, soil, and various wastes. Spills of regulated hazardous substances that contain
cyanide may also invoke the requirements of Superfund, that is, the Comprehensive Environmental
Response and Liability Act, or CERCLA. At the same time, there are number of state regulations
that address cyanide, most of which have been derived from the existing Federal legislation.
In addition to summarizing the regulations, this chapter also discusses a number of technical
issues that can, and often do, complicate the strict application of the regulations. These issues
can be grouped under the topics of cyanide speciation, cyanide analytical methods, environmental
transformation of cyanide, and cyanide toxicology. Each of these topics is also discussed in more
detail in other chapters of this book.
18.1 U.S. REGULATIONS, GUIDELINES AND CRITERIA
FOR CYANIDE IN WATER
Water quality-related standards and guidelines for cyanide in the United States are voluminous
authority (national or state), regulatory focus (surface water, drinking water, wastewater), health
effects target (human or aquatic life), cyanide form (total, free, complexed, amenable), if specified,
summarizes such categories as they are defined by selected states. A complete listing of all health-
related cyanide standards as of 1997 can be found in the U.S. Department of Health and Human
Services report on the Toxicological Profile for Cyanide [1].
A review of the information contained in Tables 18.1–18.4 reveals several features of interest.
First, criteria for cyanide vary significantly depending on the designated use for the water. These
criteria also reflect the large differential toxicities that cyanide compounds can exhibit among tar-
get organisms. For instance, numerical standards related to human consumption and exposure are
generally considerably higher than those for sensitive aquatic organisms. Further, the most sensitive
organism can vary depending on the specific aquatic environment (e.g., marine vs. fresh waters,
or cold vs. warm waters). Second, in recognition of the toxicity differences among cyanide spe-
cies (regardless of target organism), many criteria attempt to differentiate among chemical forms
© 2006 by Taylor & Francis Group, LLC
and to serve as a source of nitrogen in the natural life cycle of plants and other organisms (Chapters 3
and 12). Analytical methods for the detection of these different forms of cyanide have been developed
and complex. Tables 18.1–18.4 present a summary of this information according to the governing

and water usage or origin. State criteria are often assigned based on water usage category. Table 18.5
Regulation of Cyanide in Water and Soil 353
TABLE 18.1
National USEPA Guidelines for Cyanide
Description Limit (µg/l) Designation
1-Day Health Advisory
Child 220 Cyanide
10-Day Health Advisory
Child 220 Cyanide
Lifetime Health Advisory
Adult 200 Cyanide
Longer-term Health Advisory
Child 200 Cyanide
Adult 800 Cyanide
Maximum contaminant level
Copper cyanide, cyanide, potassium silver cyanide,
sodium cyanide
200
Maximum contaminant level goal
Cyanide, potassium silver cyanide, sodium cyanide,
potassium cyanide
200
Copper cyanide 1300
Ambient water quality criteria for human health
Potassium silver cyanide, sodium cyanide,
potassium cyanide, copper cyanide (water and fish)
200
Ambient water quality criteria for aquatic
organisms
Sodium cyanide, potassium cyanide

Freshwater acute 22
Freshwater chronic 5.2
Marine acute 1
Copper cyanide
Freshwater acute 9.2
Freshwater chronic 6.5
Marine acute 2.9
Proposed rule: Great Lakes system water quality
standards
Acute water quality criteria for protection of
aquatic life
22 Free cyanide
Chronic water quality criteria for protection of
aquatic life
5.2 Free cyanide
Source: Information from ATSDR, Toxicological profile for cyanide (update), U.S.
Department of Health and Human Services, Public Health Service, Agency for Toxic
Substances and Disease Registry, Atlanta, GA, 1997.
of cyanide, sometimes by specifically listing them (e.g., free cyanide, copper cyanide, potassium
cyanide), or by specifying an operational class of cyanide compounds as measurable by an analytical
procedure (e.g., cyanide amenable to chlorination). Third, and perhaps most critically, the degree
of specificity among cyanide compounds and chemical forms listed among the various standards,
when viewed collectively across national and state criteria, is inconsistent with available approved
analytical methodologies; that is, many more chemical forms are recognized as being of importance
than current approved analytical methods can accommodate.
© 2006 by Taylor & Francis Group, LLC
354 Cyanide in Water and Soil
TABLE 18.2
State Human Health Standards for Cyanide
State Description Limit (µg/l) Designation

Arizona Drinking water guideline 220
Domestic water source (DWS) 140 Total cyanide
Fish consumption (FC) 210,000 Total cyanide
Full body contact (FBC) 3,100 Total cyanide
Partial body contact (PBC) 3,100 Total cyanide
Colorado 200
Connecticut Degree of treatment
Disinfection and chemical 10
Complete 200
Maximum permissible level 200
District of Columbia Class C 3
Class D 200
Florida Domestic/drinking 200
MCL (Maximum contaminant level) 200
Criteria for surface waters, Class I–V 5.0
Iowa MCL
Class B waters 5
Class C waters 20
Illinois MCL 200
Idaho MCL 200
Indiana Continuous (4-day average) Point of water intake 200
Kansas Drinking water guideline 154
Kentucky MCL: domestic water supply 200 Free cyanide
Massachusetts Drinking water guideline 140
Maine Drinking water guideline 154
Michigan Domestic/drinking 150 Free cyanide
Minnesota Drinking water guideline 154
Class A and B waters 10 (CN)
Class D waters 200 (CN)
New Hampshire Drinking water guideline 154

MCL 10 (CN)
Municipal/domestic 200
New Jersey Domestic/drinking 200
Groundwater quality: 200
New Mexico Groundwater 200 (CN)
New York Domestic/drinking 100
Groundwater Effluent Standards: maximum allowable
concentration
400
Surface waters and groundwater
A, A-S, AA, AA-S 100
GA 100
North Carolina Class GSA groundwater 154
Ohio 30-day average 200
Oklahoma Maximum allowable levels 200
Oregon Domestic/drinking 200
Rhode Island Drinking water guideline 150
Tennessee Domestic/drinking 200
Utah MCL 200 Free cyanide
Virginia Groundwater 5
© 2006 by Taylor & Francis Group, LLC
Regulation of Cyanide in Water and Soil 355
TABLE 18.2
Continued
State Description Limit (µg/l) Designation
Vermont Drinking water standard 154
Class A or B waters 200
Wyoming MCL — groundwaters 200
Wisconsin Public water supplier
Warmwater sport fish communities 600 Total cyanide

Cold water communities 600 Total cyanide
Great Lakes communities 600 Total cyanide
Nonpublic water supplier
Warmwater sport fish communities 40,000 Total cyanide
Cold water communities 40,000 Total cyanide
Warmwater forage and limited forage 120,000 Total cyanide
Groundwater
Enforcement standard 200
Prevention action limit 40
West Virginia Water quality criteria
Warm water fishery streams 5 Free cyanide
Trout waters 5 Free cyanide
Small nonfishable streams 5 Free cyanide
Water contact, recreation 5 Free cyanide
Water supply, public 5 Free cyanide
Source: Information from ATSDR, Toxicological profile for cyanide (update), U.S. Department of Health and
Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry, Atlanta, GA, 1987.
18.1.1 DRINKING WATER
The national water quality criterion for the protection of human health, that is, the maximum con-
taminant level or MCL, developed by the USEPA, is 200 micrograms per liter (µg/l), measured
also designated the maximum contaminant level goal, or MCLG, for cyanide in drinking water.
The concentration limit was derived based on the assumption that an adult can ingest 0.02 mg of
cyanide per kilogram of body weight per day without causing an unacceptable adverse health effect.
This acceptable dose was determined based on a study in which 10 female and 10 male rates were
provided a range of cyanide doses (delivered as sodium cyanide) in drinking water for 13 weeks [1].
Note that copper cyanide has an MCLG (1300 µg/l) that is much higher than that of free cyanide.
This elevated MCLG is indicative of the difference in toxicity between this form of cyanide and
those typically included as part of the free cyanide, that is, hydrogen cyanide, potassium cyanide,
potassium silver cyanide, and sodium cyanide.
Table 18.1 also lists other health-related cyanide standards, all of which were abstracted from

the U.S. Department of Health and Human Services report on the Toxicological Profile for Cyanide
explicitly designated as applicable to either children or adults; however, none of these advisories
designate the specific formofthecyanide to which they apply. The health advisories for children range
from 200 (Longer-term Health Advisory) to 220 µg/l (1- and 10-day health advisories) of cyanide;
only a Longer-term Health Advisory of 800 µg/l and a Lifetime Health Advisory of 200 µg/l are
specified for adults.
© 2006 by Taylor & Francis Group, LLC
as free cyanide (see Table 18.1). This value was developed under the SDWA; the same value is
(Table 7.1, [1]). These standards are referenced as Health Advisories and include levels that are
356 Cyanide in Water and Soil
TABLE 18.3
State Aquatic Life Standards for Cyanide
State Description Limit (µg/l) Designation
Alabama Freshwater:acute 22.0
Freshwater: chronic 5.2
Marine: acute 1.0
Marine: chronic —
Arizona Acute criteria for aquatic & wildlife
Cold water fishery (A&Wc) 22.0 T (total recoverable)
Warm water fishery (A&Ws) 41.0 T
Effluent dominated water (A&Wedw) 41.0 T
Ephemeral (A&We) 84.0 T
Chronic criteria for aquatic & wildlife
A&Wc 5.2 T
A&Ws 9.7 T
A&Wedw 9.7 T
A&We 19.0 T
Florida Criteria for surface water, Class I-V 5.0
Hawaii Freshwater: acute (ecological standard) 22
Freshwater: chronic (ecological standard) 5.2

Saltwater: acute (ecological standard) 1.0
Saltwater: chronic (ecological standard) 1.0
Indiana Acute aquatic criterion 22.0
Continuous (4-day average) outside of mixing zone: chronic
aquatic criterion
5.2
Kentucky Maximum allowable instream conc
Chronic (ecological standard) 5 Free cyanide
Acute (ecological standard) 22 Free cyanide
Maryland Ambient surface waters
Freshwater: acute 22.0
Freshwater: chronic 5.2
Estuarine: acute —
Estuarine:chronic —
Saltwater: acute 1.0
Saltwater: chronic —
Minnesota Class A, B, C waters 20.0 (CN)
Mississippi Freshwater: acute 22.0
Freshwater: chronic 5.2
Saltwater: acute 1.0
Saltwater: chronic 1.0
Missouri Chronic toxicity 5.0 Amenable to
chlorination
Acute toxicity 22.0 Amenable to
chlorination
Nevada Single value 52.0
24-h average 3.5
Propagation of wildlife 5.0
New York Surface waters & groundwaters
A, A-S, AA, AA-S, B, C 5.2

D 22.0
SA, SB, SC 1.0
SD 1.0
North Dakota Class I streams 5.0 Total cyanides
North Carolina Freshwater 5.0
© 2006 by Taylor & Francis Group, LLC
Regulation of Cyanide in Water and Soil 357
TABLE 18.3
Continued
State Description Limit (µg/l) Designation
Puerto Rico Coastal estuarine waters 20.0
Surface waters 20.0
Oklahoma Acute 45.93
Chronic 10.72
Ohio Outside mixing zone (maximum)
Cold water 46.0 Free cyanide
Limited resource warm water 22.0 Free cyanide
30-day average cold water 5.2 Free cyanide
Inside mixing zone (maximum)
Cold water 45.0
Limited resource warm water 92.0
Virginia Freshwater 5.2 Total cyanide
Saltwater 1.0 Total cyanide
Vermont Acute 22.0
Chronic 5.2
Wyoming Special A waters 5.0
Wisconsin Great Lakes 22.4 Free cyanide
Cold water 22.4 Free cyanide
Warm water sport fish 46.2 Free cyanide
All others 46.2 Free cyanide

Source: Information from ATSDR, Toxicological profile for cyanide (update), U.S. Department of Health and Human
Services, Public Health Service, Agency for Toxic Substances and Disease Registry, Atlanta, GA, 1997.
TABLE 18.4
Miscellaneous State Standards for Cyanide
State Description Limit (µg/l) Designation
Water quality:
agricultural
uses
Arizona Agricultural
irrigation (AgI)
No numerical
standard
Livestock
watering (Ag L)
200 Total recoverable
Nevada Ag L 200
Hazardous
constituents
Indiana Allowable
concentration
using leaching
test method:
Class IV 200
Class III 2000
Class II 5000
Source: Information from ATSDR, Toxicological profile for cyanide (update), U.S.
Department of Health and Human Services, Public Health Service, Agency for Toxic
Substances and Disease Registry, Atlanta, GA, 1997.
© 2006 by Taylor & Francis Group, LLC
358 Cyanide in Water and Soil

TABLE 18.5
Selected State Water Classifications
Florida
Class I — Potable water supplies
Class II — Shellfish propagation or harvesting
Class III — Recreation, propagating, and maintenance of healthy, well-balanced population of fish and wildlife
Class IV — Agricultural water supplies
ClassV—Navigation, utility, and industrial use
Minnesota
Class 1 — Domestic consumption
Class 2 — Aquatic life and recreation
New Jersey
GW1 — Ground water of special ecological significance
GW2 — Ground water for potable water supply
GW3 — Ground water with uses other than potable water supply
New York
Class N — fresh surface waters
Class A, AA, Special (AA-S) — fresh surface waters (drinking)
Class B — fresh surface waters (primary and secondary contact)
Class C, D — fresh surface waters (fishing)
Class SA — saline surface waters (fish propagation and survival)
Class SB — saline surface waters (primary and secondary contact)
Class SC — saline surface waters (fishing)
Class I — saline surface waters (secondary contact recreation)
Class SD — saline surface waters (fish survival)
Class GA — fresh groundwaters (drinking)
Class GSA — saline groundwaters (potable mineral waters)
Class GSB — saline groundwaters (receiving waters)
North Carolina
Class GA — groundwaters (drinking water)

Class GSA — groundwaters; usage and occurrence (potable mineral waters)
Class GC — groundwaters; usage and occurrence (nondrinking uses)
Vermont
Class A(1) — Ecological waters
Class A(2) — Public water supplies
Class B — Cold and warm water fish habitats
Wyoming
Special A waters — Suitable for fish and aquatic life
Source: Information from ATSDR, Toxicological profile for cyanide (update), U.S. Department of Health and
Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry, Atlanta, GA, 1997.
a greater degree of variability in the concentrations of cyanide that are acceptable in drinking water.
An examination of all 50 states reveals that most states do adopt, in some manner, the national
MCL of 200 µg/l free cyanide. However, there are often variations from this value based on a
specific classification of the water that is being consumed. For example, Arizona has a drinking
water guideline of 220 µg/l free cyanide but also has a standard of 140 µg/l of total cyanide for
domestic water sources (DWS). Similarly, Massachusetts and Maine have drinking water guidelines
© 2006 by Taylor & Francis Group, LLC
A review of the human health standards and guidelines for various states (Table 18.2) indicates
Regulation of Cyanide in Water and Soil 359
of 140 and 154 µg/l, respectively, although they do not indicate the form of cyanide that should
be measured. New Hampshire has a similar drinking water guideline (i.e., 154 µg/l) but also has
its own MCL of 10 µg/l, measured as [CN]. This value represents the lowest human-health water
quality standard for cyanide that exists among all of the 50 states.
18.1.2 SURFACE WATER AND GROUNDWATER
Section 304(a)(1) of the Clean Water Act requires USEPA to develop and publish ambient water
quality criteria for selected pollutants, of which cyanide is one. Ambient surface water quality criteria
for aquatic organisms are provided to protect against both chronic and acute toxicological effects.
Simply stated, acute toxicity is toxicity that occurs very rapidly, for example, minutes to hours,
after exposure whereas chronic toxicity occurs only after exposure over long periods of time, for
example, days to years. The chronic and acute ambient water criteria for cyanide in freshwater are

5.2 and 22 µg/l, respectively, expressed as free cyanide (as CN). These criteria were developed
criteria. However, the same is not true for saltwater criteria, which are 1.0 µg/l for both chronic
and acute toxicity. These criteria are at or below the detection limit for available analytical meth-
the saltwater criteria, Cancer irroratus, is uncommon and atypically sensitive [2]. This issue is
examined in detail in Chapter 14, where the aquatic toxicity database underlying the national ambi-
ent water quality criteria for cyanide is summarized and critiqued. Surface water quality criteria
are also defined specifically for copper cyanide with values of 9.2, 6.5, and 2.9 µg/l respect-
ively, for acute and chronic effects in freshwater and both acute and chronic effects in saltwater
The Clean Water Act also directs USEPA to develop ambient water quality criteria for protection
of human health, especially for exposure through consumption of fish and also including incidental
water consumption, for example, through recreation activities. The criteria are developed using a
methodology that incorporates a set of standard data and approaches for evaluating exposure and
health risk [3]. The human health water quality criteria for cyanide were revised in 2003 [4]. The
criterion for both “consumption of water and organism” and “consumption of organism only” is
140 µg/l total cyanide. It is noted in the USEPA criteria document [3] that the recommended
water quality criterion is expressed as total cyanide even though the Integrated Risk Information
System (IRIS) reference dose used to derive the criterion is based on free cyanide. USEPA notes
that “if a substantial fraction of the cyanide present in a water body is present in complexed form
(e.g., Fe
4
[Fe(CN)
6
]
3
), this recommended criterion may be overly conservative.”
Typical examples of these categories include potable water supplies, recreational use, agricultural
water supplies, groundwater, saline/fresh surface water, and cold/warm water fish habitats, to name
a few. A review of the state aquatic life protection criteria in Table 18.3 reveals a range of concentra-
tions for total cyanide and total recoverable cyanide (1.0 µg/l [saltwater/acute and chronic effects
(several states); New York: selected freshwater effects] to 84 µg/l [Arizona]); cyanide amenable to

chlorination (Several states: 5 µg/l [chronic toxicity] to 22 µg/l [acute toxicity]), and free cyanide
(5.2 µg/l [Ohio: 30-day average cold water] to 46.2 µg/l [Wisconsin: warm water sport fish and all
others]).
Cyanide water quality criteria for groundwater are not common. Those that do exist usually treat
the groundwater as either a potential drinking water or as a potential source to an adjacent surface
water. In the former instance, the criteria are usually based onthe MCL or 200 µg/l of freecyanide. In
the latter case, the criteria approach those concentrations that will be protective of aquatic organisms,
that is, approximately 5 µg/l (Virginia). New York is an exception and has a maximum allowable
concentration of 400 µg/l of cyanide (unspecified form) as a groundwater effluent standard. Many
© 2006 by Taylor & Francis Group, LLC
based on trout toxicity data (Chapter 14). There is little debate about the validity of these freshwater
ods (Chapter 7). Further, some have suggested that the test organism used by the USEPA to derive
(see Table 18.1).
State surface water criteria are often assigned based on water usage categories (Tables 18.3–18.5).
360 Cyanide in Water and Soil
states have developed groundwater quality guidelines for cyanide in the context of contaminated site
remediation, however, as discussed in subsequent sections on RCRA and CERCLA.
18.1.3 FEDERAL WASTEWATER DISCHARGE STANDARDS
The ambient water quality criteria provide guidance to states in adopting water quality standards,
which ultimately provide a basisforcontrollingdischarges or releases of pollutants intothewaterways
of the nation. The limits associated with these discharges or releases are set in the National Pollution
Discharge Elimination System (NPDES) permits established under the authority of the Clean Water
Act. Ambient water quality criteria that are derived to address site-specific situations are not included
as part of this Federal regulation.
18.1.3.1 Effluent Guidelines and Standards
Cyanide has been regulated inindustrial wastewater discharges for many years. Under the direction of
the Clean Water Act, the USEPA has developed effluent guidelines and standards for a large number
of specific industries. These guidelines and standards are technology-based, that is, they are based
on a projection of the effluent quality that will be produced by applying the best available treatment
(BAT) technology to the typical wastewater that is generated by the specified industrial category.

(Another category of treatment technologies is the best practical treatment or BPT. BPT differs from
BAT in that the former gives some consideration to the cost of treatment.) These discharge standards
have been developed for a total of 56 industry categories and are presented in the U.S. Code of Federal
Regulations (40 CFR, Subchapter N, Parts 400 to 471). The discharge of some chemical form of
evaluations for the industrial categories listed in Table 18.6 are implemented as part of the NPDES
permit system, which requires a permit for all discharges to the surface waters of thenation. Permitted
discharges must comply with the discharge limits that are prescribed for the appropriate industrial
categories. State environmental agencies usually administer the NPDES program for the USEPA. In
issuing a discharge permit, a state has the authority to stipulate either BAT limits or more stringent
water quality limits, depending on the classification of the receiving water body.
There is another set of discharge standards for these industrial categories which applies when
the treated effluent is discharged to a publicly owned treatment facility, or POTW, prior to the
discharge to a surface water body. These standards are known as pretreatment standards and were
developed taking into consideration that some degree of treatment of the regulated contaminants
would occur in the POTW. Two sets of standards exist for discharges to POTWs: (1) Pretreatment
standards for new sources (PSNS) and (2) Pretreatment standards for existing sources (PSES). The
differences in these standards reflect the assumption that new sources of wastewater are expected to
generate reduced loads of contaminants as a result of improved or more efficient upstream process
operations. Generally, these standards are essentially the same as BAT limits. For discharges to
POTWs, pretreatment discharge limits may be based on PSES or PSNS limits or more stringent
water quality limits, as dictated by NPDES requirements for the POTW.
The Pollution Prevention Act, passed in 1990, is aimed at helping industry reduce or prevent pol-
lution at the source, with one benefit being improved compliance with wastewater effluent guidelines
and limits. USEPA was directed to provide technical assistance to businesses and to promote source
reduction with industry. In response, USEPA developed initiatives with many different industries.
In the context of reducing the volume and environmental impact of industrial wastewater discharges,
the Agency initiated collaborations, for example, with the electroplating and metals manufacturing
industries. Efforts of these industries in source reduction have yielded progress. In the years ahead
there will be increasing focus on modification of manufacturing processes as part of wastewater
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cyanide is regulated in 13 of these industrial categories, listed in Table 18.6. Treatment technology
Regulation of Cyanide in Water and Soil 361
TABLE 18.6
USEPA Industrial Wastewater Discharge Categories
that Include Effluent Standards for Cyanide
Electroplating
Organic chemicals, plastics, and synthetic fibers
Inorganic chemicals manufacturing
Iron and steel manufacturing
Nonferrous metals manufacturing
Steam electric power generation
Ferroalloy manufacturing
Pharmaceutical manufacturing
Photographic processing point sources
Battery manufacturing
Coil coating point sources
Aluminum forming
Nonferrous metals forming and metal powders point sources
Note: Information from 40 CFR Chapter N Effluent Guidelines and
Standards 400–471.
management strategies. The Pollution Prevention Act, and the assistance it makes available to com-
panies through the USEPA, provides the framework for new directions in effluent limit compliance
approaches.
18.1.3.2 Specific Characteristics of Guidelines/Standards
18.1.3.2.1 Specified cyanide analytical methods
Part 136 of Title 40 (Guidelines Establishing Test Procedures for the Analysis of Pollutants) of
the Code of Federal Regulations describes the analytical methods that should be used to determine
compliance with the effluent guidelines and standards. Specifically, Table IB of Part 136 presents a
list of approved inorganic test procedures. The test procedures that are specified for cyanide are:
1. Total cyanide: Manual distillation (Standard Methods 4500 CN C [5] and ASTM

D2036-98(A) [6]) followed by titrimetric (Standard Methods 4500 CN D [5]) or spec-
trophotometric analysis, manual (USEPA Method 335.2 [7]; Standard Methods 4500 CN
E [5]; ASTM 2036-98(A) [6], and USGS Method I-3300-85 [8]) or automated analysis
(USEPA Method 335.3 [9] and USGS Method I-4302-85 [10]) of the distillation offgas
absorber liquid;
2. Cyanide amenable to chlorination: Manual distillation with and without chlorination
(USEPA Method 335.1 [11]; Standard Methods 4500 CN G [5]; and ASTM D2036-98(B)
[12]) followed by titrimetric or spectrophotometric (manual or automated) analysis of the
distillation offgas absorber liquid; and
3. Available cyanide: Flowinjectionandligandexchange, followedbyamperometry(USEPA
Method OIA-1677 [13]).
Based on these prescribed analytical methods, it is evident that the guidelines and standards are
regulating industrial discharges on some combination of total, amenable, and available cyanide.
egories that have specific discharge limits for cyanide. The specific discharge limits for each of the
© 2006 by Taylor & Francis Group, LLC
Table 18.7 identifies those methods that have been prescribed for each of the 13 industrial subcat-
362 Cyanide in Water and Soil
total cyanide is the predominant form of cyanide that is used for determining compliance, having
been identified explicitly in 11 of the 13 industrial subcategories. For the other two industrial subcat-
egories, no form of cyanide is specified. In many cases, amenable cyanide is also specified; however,
it is used in tandem with the use of total cyanide.
18.1.3.2.2 Range of cyanide discharge limits
The discharge limits for the 13 industrial categories that are presented in Table 18.7 are based
on one of two criteria: (1) concentration-based criteria, that is, the cyanide concentration that is
achievable in the effluent discharge after the application of a specific treatment, or (2) normalized
mass criteria, that is, the mass of cyanide in the effluent discharge normalized per pound of product
or related by-product. These different discharge criteria are also presented in terms of maximum
values averaged over different time periods, typically one day, 4 days, or 30 days or monthly.
Examples of the type and range of the concentration criteria shown in Table 18.7 are provided
below:

1-day maximum:
• Total cyanide: 1200 µg/l (organic chemicals, plastics, and synthetic fibers) —
33,500 µg/l (pharmaceutical manufacturing).
• Amenable cyanide: 860 µg/l (metal finishing) — 5000 µg/l (electroplating
national pretreatment standards for existing sources [<38, 000 l/day]).
4-day maximum averages:
• Total cyanide: 1000 µg/l (electroplating national pretreatment standards for
existing sources [>38, 000 l/day]).
• Amenable cyanide: 2700 µg/l (electroplating national pretreatment standards
for existing sources [<38, 000 l/day]).
30-day (monthly) maximum averages:
• Total cyanide: 420 µg/l (organic chemicals, plastics, and synthetic fibers) —
9400 µg/l (pharmaceutical manufacturing).
• Amenable cyanide: 320 µg/l (metal finishing).
The normalized mass criteria in Table 18.7 cannot be easily summarized because of the different
bases that were used for the normalization. For example, in the steam electric power generating
subcategory, the allowable cyanide discharge is normalized per megawatt hour; in the precious metals
subcategory, the discharge is normalized per troy ounce; while in several of the other categories, it is
per million pounds of material production.
18.1.4 GROUNDWATER (RCRA AND CERCLA)
Two primary pieces of U.S. legislation that govern the management of residuals containing cyanide,
and groundwater contacted by these residuals, are the Resource Conservation and Recovery Act
(RCRA) and the Comprehensive Environmental Response, Compensation, and Liability Act (CER-
CLA). Congress enacted RCRA in 1976 (RCRA Public Law 94-580) and CERCLA in 1980 (later
amended and reauthorized in 1986, Public Law 99-499). RCRA established a system for managing
hazardous wastes from the point of origin to the final disposal, that is, cradle to grave, while CERCLA
addresses legacy sites where hazardous substances have been released to the environment.
18.1.4.1 Groundwater (RCRA)
Under RCRA, wastes may be classified as hazardous wastes or solid (nonhazardous wastes). A solid
waste under RCRA is hazardous if it is not excluded from the hazardous waste regulations and (1) it

© 2006 by Taylor & Francis Group, LLC
various categories are also presented in this table. Based upon a review of Table 18.7, it is clear that
Regulation of Cyanide in Water and Soil 363
TABLE 18.7
Technology Performance Standards for Selected Industrial Categories
a
Standard
b
Industrial subcategory Cyanide form NSPS PSES PSNS BPT BAT
Electroplating
(1) <38,000 l/day Amenable cyanide
5.0 mg/l (1-day max)
2.7 mg/l (4-day average
max)
(2) ≥38,000 l/day Total cyanide
1.9 mg/l (1-day max)
1.0 mg/l (4-day average
max)
Organic chemicals,
plastics, and synthetic
fibers (with and
without end-of-pipe
biological treatment)
Total cyanide 1200 µg/l (1-day
maximum)
420 µg/l (max monthly
average)
1200 µg/l (1-day
maximum)
420 µg/l (max monthly

average)
1200 µg/l (1-day
maximum)
420 µg/l (max monthly
average)
Inorganic chemicals
manufacturing
(1) Hydrogen peroxide
production (electrolytic
process)
Amenable cyanide
0.0004 lbs/1000 lbs of
product (1-day max)
0.0002 lbs/1000 lbs of
product (30-day
average)
(2) Hydrogen cyanide
production
Amenable cyanide 0.10 lbs/1000 lbs of
product (1-day max)
0.021 lbs/1000 lbs of
product (30-day
average)
1700 µg/l (1-day max);
360 µg/l (30-day
average)
0.10 lbs/1000 lbs of
product (1-day max)
0.021 lbs/1000 lbs of
product (30-day

average)
0.10 lbs/1000 lbs of
product (1-day max)
0.021 lbs/1000 lbs of
product (30-day
average)
Total cyanide
c
0.65 lbs/1000 lbs of
product (1-day max)
0.23 lbs/1000 lbs of
product (30-day
average)
11,000 µg/l (1-day
max)
4000 µg/l (30-day
average)
0.65 lbs/1000 lbs of
product (1-day max)
0.23 lbs/1000 lbs of
product (30-day
average)
0.65 lbs/1000 lbs of
product (1-day max)
0.23 lbs/1000 lbs of
product (30-day
average)
© 2006 by Taylor & Francis Group, LLC
364 Cyanide in Water and Soil
TABLE 18.7

Continued
Standard,
b
Industrial subcategory Cyanide form NSPS PSES PSNS BPT BAT
Iron/steel
manufacturing
d
(1) By-product coke
making (iron and steel)
Total cyanide 0.00297 lbs/1000 lbs of
product (1-day max)
0.00208 lbs/1000 lbs of
product (max monthly
average)
0.00724 lbs/1000 lbs of
product (1-day max)
0.00506 lbs/1000 lbs of
product (max monthly
average)
0.00297 lbs/1000 lbs of
product (1-day max)
0.00208 lbs/1000 lbs of
product (max monthly
average)
0.0657 lbs/1000 lbs of
product (1-day max)
0.0219 lbs/1000 lbs of
product (max monthly
average)
0.00297 lbs/1000 lbs of

product (1-day max)
0.00208 lbs/1000 lbs of
product (max monthly
average)
(2) Sintering (NSPS,
PSES, and PSNS apply
only when sintering
wastewater is cotreated
with iron making
wastewater)
Total cyanide 0.00100 lbs/1000 lbs of
product (1-day max)
0.000501 lbs/1000 lbs of
product (max monthly
average)
0.00300 lbs/1000 lbs of
product (1-day max)
0.00150 lbs/1000 lbs of
product (max monthly
average)
0.00100 lbs/1000 lbs of
product (1-day max)
0.000501 lbs/1000 lbs of
product (max monthly
average)
Cyanide limits not
specified
0.00300 lbs/1000 lbs of
product (1-day max)
0.00150 lbs/1000 lbs of

product (max monthly
average)
(3) Ironmaking (iron
blast furnace)
Total cyanide 0.000584 lbs/1000 lbs of
product (1-day
average)
0.000292 lbs/1000 lbs of
product (30-day
average)
0.00175 lbs/1000 lbs of
product (1-day
average)
0.000876 lbs/1000 lbs of
product (30-day
average)
0.000584 lbs/1000 lbs of
product (1-day
average)
0.000292 lbs/1000 lbs of
product (30-day
average)
0.0234 lbs/1000 lbs of
product (1-day
average)
0.00782 lbs/1000 lbs of
product (30-day
average)
0.00175 lbs/1000 lbs of
product (1-day

average)
0.000876 lbs/1000 lbs
of product (30-day
average)
Salt bath descaling
(Reducing)
(a) Batch Total cyanide 0.00102 lbs/1000 lbs of
product (1-day max)
0.000339 lbs/1000 lbs of
product (30-day
average)
0.00102 lbs/1000 lbs of
product (1-day max)
0.000339 lbs/1000 lbs of
product (30-day
average)
0.00102 lbs/1000 lbs of
product (1-day max)
0.000339 lbs/1000 lbs of
product (30-day
average)
0.00102 lbs/1000 lbs of
product (1-day max)
0.000339 lbs/1000 lbs of
product (30-day
average)
0.00102 lbs/1000 lbs of
product (1-day max)
0.000339 lbs/1000 lbs
of product (30-day

average)
(b) Continuous Total cyanide 0.00569 lbs/1000 lbs of
product (1-day max)
0.00190 lbs/1000 lbs of
product (30-day
average)
0.00569 lbs/1000 lbs of
product (1-day max)
0.00190 lbs/1000 lbs of
product (30-day
average)
0.00569 lbs/1000 lbs of
product (1-day max)
0.00190 lbs/1000 lbs of
product (30-day
average)
0.00569 lbs/1000 lbs of
product (1-day max)
0.00190 lbs/1000 lbs of
product (30-day
average)
0.00569 lbs/1000 lbs of
product (1-day max)
0.00190 lbs/1000 lbs of
product (30-day
average)
© 2006 by Taylor & Francis Group, LLC
Regulation of Cyanide in Water and Soil 365
Nonferrous metals
manufacturing

(1) Primary aluminum
smelting
(a) Cathode
reprocessing with dry
potline scrubbing
Total cyanide 157.6 lbs/million lbs of
cryolite recovered
(1-day max)
70.06 lbs/million lbs of
cryolite recovered
(max monthly average)
157.6 lbs/million lbs of
cryolite recovered
(1-day max)
70.06 lbs/million lbs of
cryolite recovered
(max monthly average)
157.6 lbs/million lbs of
cryolite recovered
(1-day max)
70.06 lbs/million lbs of
cryolite recovered
(max monthly average)
(b) Cathode
reprocessing operated
with wet potline
scrubbing
Total cyanide
0.00 (1-day max and
max monthly average)

(c) Potline wet air
pollution control
operated with cathode
reprocessing
Total cyanide
3.771 lbs/million lbs of
aluminum produced
(1-day max)
1.676 lbs/million lbs of
aluminum produced
(30-day average)
(2) Primary beryllium Total cyanide 0.00 to
449.2 lbs/million lbs of
beryllium carbonate
produced (1-day max)
0.0 to
179.7 lbs/million lbs of
beryllium carbonate
produced (max
monthly average)
0.00 to
449.2 lbs/million lbs of
beryllium carbonate
produced (1-day max)
0.0 to
179.7 lbs/million lbs of
beryllium carbonate
produced (max
monthly average)
0.00 to

651.3 lbs/million lbs of
beryllium carbonate
produced (1-day max)
0.0 to
269.5 lbs/million lbs of
beryllium carbonate
produced (max
monthly average)
0.00 to 449.2 lbs/million
lbs of beryllium
carbonate produced
(1-day max)
0.0 to
179.7 lbs/million lbs of
beryllium carbonate
produced (max
monthly average)
(3) Secondary precious
metals
Total cyanide 0.00 to 10.0 mg/troy oz.
(1-day max)
0.00 to 4.0 mg/troy oz.
(max monthly average)
0.00 to 10.0 mg/troy oz.
(1-day max)
0.00 to 4.0 mg/ troy oz.
(max monthly average)
0.00 to 10.0 mg/troy oz.
(1-day max)
0.00 to 4.0mg/troy oz.

(max monthly average)
0.00 to 20.82 mg/
troy oz. (1-day max)
0.00 to 8.616 mg/
troy oz. (max monthly
average)
0.00 to 10.0 mg/troy oz.
(1-day max)
0.00 to 4.0 mg/ troy oz.
(max monthly average)
© 2006 by Taylor & Francis Group, LLC
366 Cyanide in Water and Soil
TABLE 18.7
Continued
Standard
b
Industrial subcategory Cyanide form NSPS PSES PSNS BPT BAT
(4) Secondary tin Total cyanide 0.007 to 23.0 mg/kg
(1-day max)
0.003 to 9.2 mg/kg (max
monthly average)
0.007 to 23.0 mg/kg
(1-day max)
0.003 to 9.2 mg/kg (max
monthly average)
0.007 to 23.0 mg/kg
(1-day max)
0.003 to 9.2 mg/kg (max
monthly average)
0.010 to 33.35 mg/kg

(1-day max)
0.004 to 13.8 mg/kg
(max monthly average)
0.007 to 23.0 mg/kg
(1-day max)
0.003 to 9.2 mg/kg
(max monthly
average)
(5) Primary zirconium
and hafnium
Total cyanide 0.00 to 8.694 mg/kg
(1-day max)
0.00 to 3.478 mg/kg
(max monthly average)
0.00 to 8.694 mg/kg
(1-day max)
0.00 to 3.478 mg/kg
(max monthly average)
0.00 to 12.610 mg/kg
(1-day max)
0.00 to 5.216 mg/kg
(max monthly average)
0.00 to 8.694 mg/kg
(1-day max)
0.00 to 3.478 mg/kg
(max monthly
average)
Steam electric power
generation
Total cyanide Nondetect in chemicals

Added for cooling tower
maintenance
Nondetect in chemicals
Added for cooling tower
maintenance
Nondetect in chemicals
Added for cooling tower
maintenance
Nondetect in chemicals
Added for cooling
tower maintenance
Ferroalloy
manufacturing
(1) Covered electric
furnace
Total cyanide 0.0005 kg/Mwh (1-day
average)
0.0003 kg/Mwh (30-day
average)
0.004 kg/Mwh (1 day
max)
0.002 kg/Mwh (30-day
average)
0.0005 kg/Mwh (1-day
average)
0.0003 kg/Mwh
(30-day average)
(2) Covered calcium
carbide furnace
Total cyanide

0.0056 lbs/million lbs
(1-day max)
0.0028 lbs/million lbs
(30-day average)
0.0056 lbs/million lbs
(1-day max)
0.0028 lbs/million lbs
(30-day average)
(3) Metal finishing Total cyanide
1.20 mg/l (1-day max)
0.65 mg/l (30-day
average)
1.20 mg/l (1-day max)
0.65 mg/l (30-day
average)
1.20 mg/l (1-day max)
0.65 mg/l (30-day
average)
1.20 mg/l (1-day max)
0.65 mg/l (30-day
average)
Amenable cyanide 0.86 mg/l (1-day max)
0.32 mg/l (30-day
average)
0.86 mg/l (1-day max)
0.32 mg/l (30-day
average)
0.86 mg/l (1-day max)
0.32 mg/l (30-day
average)

0.86 mg/l (1-day max)
0.32 mg/l (30-day
average)
© 2006 by Taylor & Francis Group, LLC
Regulation of Cyanide in Water and Soil 367
Pharmaceutical
manufacturing
Total cyanide 33.5 mg/l (1-day max)
9.4 mg/l (30-day
average)
33.5 mg/l (1-day max)
9.4 mg/l (30-day
average)
33.5 mg/l (1-day max)
9.4 mg/l (30-day
average)
33.5 mg/l (1-day max)
9.4 mg/l (30-day
average)
33.5 mg/l (1-day max)
9.4 mg/l (30-day
average)
Photographic
processing
d
Not specified
0.038lb/1000 ft
2
of
product (91-day max)

0.019lb/1000 ft
2
of
product (max monthly
average)
Battery
manufacturing: zinc
subcategory
Total cyanide 0.039 mg/kg (1-day
max)
0.016 mg/kg (30-day
average)
0.38 mg/kg (1-day max)
0.16 mg/kg (30-day
average)
0.039 mg/kg (1-day
max)
0.016 mg/kg (30-day
average)
2.54 mg/kg (1-day max)
1.05 mg/kg (30-day
average)
0.38 mg/kg (1-day max)
0.16 mg/kg (30-day
average)
Coil coating
(1) Steel basis material Not specified 0.063 mg/m
2
of area
processed (1-day max)

0.025 mg/m
2
of area
processed (max
monthly average)
0.34 mg/m
2
of area
processed (1-day max)
0.14 mg/m
2
of area
processed (max
monthly average)
0.063 mg/m
2
of area
processed (1-day max)
0.025 mg/m
2
of area
processed (max
monthly average)
0.80 mg/m
2
of area
processed (1-day max)
0.33mg/m
2
of area

processed (max
monthly average)
0.34mg/m
2
of area
processed (1-day max)
0.14mg/m
2
of area
processed (max
monthly average)
(2) Galvanized basis
material
Not specified 0.07 mg/m
2
of area
processed (1-day max)
0.028 mg/m
2
of area
processed (max
monthly average)
0.26 mg/m
2
of area
processed (1-day max)
0.11 mg/m
2
of area
processed (max

monthly average)
0.07 mg/m
2
of area
processed (1-day max)
0.028mg/m
2
of area
processed (max
monthly average)
0.76 mg/m
2
of area
processed (1-day max)
0.32 mg/m
2
of area
processed (max
monthly average)
0.26 mg/m
2
of area
processed (1-day max)
0.11 mg/m
2
of area
processed (max
monthly average)
(3) Aluminum basis
material

Not specified 0.095 mg/m
2
of area
processed (1-day max)
0.038 mg/m
2
of area
processed (max
monthly average)
0.29 mg/m
2
of area
processed (1-day max)
0.12 mg/m
2
of area
processed (max
monthly average)
0.095 mg/m
2
of area
processed (1-day max)
0.038 mg/m
2
of area
processed (max
monthly average)
0.98mg/m
2
of area

processed (1-day max)
0.41mg/m
2
of area
processed (max
monthly average)
0.29mg/m
2
of area
processed (1-day max)
0.12mg/m
2
of area
processed (max
monthly average)
Aluminum forming
(1) Rolling with neat oil Total cyanide 0.00039 to 0.41 lbs/
million lbs of
aluminum rolled
(1-day average)
0.00016 to 0.17 lbs/
million lbs of
aluminum rolled (max
monthly average)
0.00057 to 0.59 lbs/
million lbs of
aluminum rolled
(1-day average)
0.00024 to 0.25 lbs/
million lbs of

aluminum rolled (max
monthly average)
0.00039 to 0.41 lbs/
million lbs of
aluminum rolled
(1-day average)
0.00016 to 0.17 lbs/
million lbs of
aluminum rolled (max
monthly average)
0.00057 to 4.61 lbs/
million lbs of
aluminum rolled
(1-day average)
0.00024 to 1.91 lbs/
million lbs of
aluminum rolled (max
monthly average)
0.00057 to 4.04 lbs/
million lbs of
aluminum rolled
(1-day average)
0.00024 to 1.67 lbs/
million lbs of
aluminum rolled (max
monthly average)
© 2006 by Taylor & Francis Group, LLC
368 Cyanide in Water and Soil
TABLE 18.7
Continued

Standard
b
Industrial subcategory Cyanide form NSPS PSES PSNS BPT BAT
(2) Rolling with
emulsions
Total cyanide 0.026 to 0.41 lbs/million
lbs of aluminum rolled
(1-day average)
0.011 to 0.16 lbs/million
lbs of aluminum rolled
(max monthly average)
0.038 to 0.59 lbs/million
lbs of aluminum rolled
(1-day average)
0.016 to 0.25 lbs/million
lbs of aluminum rolled
(max monthly average)
0.026 to 0.41 lbs/million
lbs of aluminum rolled
(1-day average)
0.011 to 0.16 lbs/million
lbs of aluminum rolled
(max monthly average)
0.038 to 4.61 lbs/million
lbs of aluminum rolled
(1-day average)
0.016 to 1.91 lbs/million
lbs of aluminum rolled
(max monthly average)
0.038 to 0.59 lbs/

million lbs of
aluminum rolled
(1-day average)
0.016 to
0.25 lbs/million lbs of
aluminum rolled (max
monthly average)
(3) Extrusion Total cyanide 0.036 to 0.41 lbs/million
lbs of aluminum
extruded (1-day max)
0.024 to 0.17 lbs/million
lbs of aluminum
extruded (max monthly
average)
0.052 to 1.2 lbs/million
lbs of aluminum
extruded (1-day max)
0.022 to 0.5 lbs/million
lbs of aluminum
extruded (max monthly
average)
0.036 to 0.41 lbs/million
lbs of aluminum
extruded (1-day max)
0.015 to 0.17 lbs/million
lbs of aluminum
extruded (max monthly
average)
0.052 to 4.61 lbs/million
lbs of aluminum

extruded (1-day max)
0.022 to 1.91 lbs/million
lbs of aluminum
extruded (max monthly
average)
0.052 to 1.2 lbs/million
lbs of aluminum
extruded (1-day max)
0.022 to 0.5 lbs/million
lbs of aluminum
extruded (max
monthly average)
(4) Forging Total cyanide 0.010 to 0.41 lbs/million
lbs of aluminum forged
(1-day average)
0.004 to
0.163 lbs/million lbs of
aluminum forged
0.015 to 1.2 lbs/million
lbs of aluminum forged
(1-day average)
0.006 to 0.5 lbs/million
lbs of aluminum forged
0.010 to 0.41 lbs/million
lbs of aluminum forged
(1-day average)
0.004 to
0.163 lbs/million lbs of
aluminum forged
(5) Drawing with

neat oil
Total cyanide 0.0004 to 0.408 lbs/
million lbs of
aluminum drawn
(1-day average)
0.0002 to 0.163 lbs/
million lbs of
aluminum drawn (max
monthly average)
0.0006 to 0.591 lbs/
million lbs of
aluminum drawn
(1-day average)
0.0003 to 0.245 lbs/
million lbs of
aluminum drawn (max
monthly average)
0.0004 to 0.408/
million lbs of
aluminum drawn
(1-day average)
0.0002 to 0.163 lbs/
million lbs of
aluminum drawn (max
monthly average)
0.00057 to 4.61 lbs/
million lbs of
aluminum drawn
(1-day average)
0.00024 to 1.91 lbs/

million lbs of
aluminum drawn (max
monthly average)
0.0006 to 0.591 lbs/
million lbs of
aluminum drawn
(1-day average)
0.0002 to 0.245 lbs/
million lbs of
aluminum drawn (max
monthly average)
© 2006 by Taylor & Francis Group, LLC
Regulation of Cyanide in Water and Soil 369
(6) Drawing with
emulsions of soap
Total cyanide 0.0004 to 0.408 lbs/
million lbs of
aluminum drawn
(1-day average)
0.0002 to 0.16 lbs/
million lbs of
aluminum drawn (max
monthly average)
0.0006 to 0.591 lbs/
million lbs of
aluminum drawn
(1-day average)
0.0003 to 0.25 lbs/
million lbs of
aluminum drawn (max

monthly average)
0.0004 to 0.408 lbs/
million lbs of
aluminum drawn
(1-day average)
0.0002 to 0.16 lbs/
million lbs of
aluminum drawn (max
monthly average)
0.0006 to 4.61 lbs/
million lbs of
aluminum drawn
(1-day average)
0.0003 to 1.91 lbs/
million lbs of
aluminum drawn (max
monthly average)
0.0006 to 0.591 lbs/
million lbs of
aluminum drawn
(1-day average)
0.0003 to 0.25 lbs/
million lbs of
aluminum drawn (max
monthly average)
Nonferrous metals
forming and metal
powders point sources
(1) Precious metal
forming

Not specified 0.0009 to 1.94 lbs/
million lbs of metal
formed (1-day average)
0.0004 to 0.802 lbs/
million lbs of metal
formed (max monthly
average)
0.0009 to 1.94 lbs/
million lbs of metal
formed (1-day average)
0.0004 to 0.802 lbs/
million lbs of metal
formed (max monthly
average)
0.0009 to 1.94 lbs/
million lbs of metal
formed (1-day average)
0.0004 to 0.802 lbs/
million lbs of metal
formed (max monthly
average)
0.0009 to 3.51 lbs/
million lbs of metal
formed (1-day average)
0.0004 to 1.45 lbs/
million lbs of metal
formed (max monthly
average)
0.0009 to 1.94 lbs/
million lbs of metal

formed (1-day average)
0.0004 to 0.802 lbs/
million lbs of metal
formed (max monthly
average)
(2) Titanium forming Not specified 0.010 to 0.84 lbs/million
lbs of titanium formed
(1-day average)
0.005 to 0.351 lbs/
million lbs of titanium
formed (max monthly
average)
0.010 to 0.84 lbs/million
lbs of titanium formed
(1-day average)
0.005 to 0.351 lbs/
million lbs of titanium
formed (max monthly
average)
0.010 to 0.84 lbs/million
lbs of titanium formed
(1-day average)
0.005 to 0.351 lbs/
million lbs of titanium
formed (max monthly
average)
0.010 to 8.47 lbs/million
lbs of titanium formed
(1-day average)
0.004 to 3.51 lbs/million

lbs of titanium formed
(max monthly average)
0.010 to 0.84 lbs/million
lbs of titanium formed
(1-day average)
0.005 to 0.351 lbs/
million lbs of titanium
formed (max monthly
average)
(3) Zinc forming Not specified 0.0003 to
0.338 lbs/million lbs of
zinc formed (1-day
average)
0.0001 to
0.135 lbs/million lbs of
zinc formed (max
monthly average)
0.0003 to 0.338 lbs/
million lbs of zinc
formed (1-day average)
0.0001 to 0.135 lbs/
million lbs of zinc
formed (max monthly
average)
0.0004 to 1.04 lbs/
million lbs of zinc
formed (1-day average)
0.0002 to 0.430 lbs/
million lbs of zinc
formed (max monthly

average)
0.0003 to
0.338 lbs/million lbs of
zinc formed (1-day
average)
0.0001 to 0.135 lbs/
million lbs of zinc
formed (max monthly
average)
© 2006 by Taylor & Francis Group, LLC
370 Cyanide in Water and Soil
TABLE 18.7
Continued
Standard
b
Industrial subcategory Cyanide form NSPS PSES PSNS BPT BAT
(4) Zirconium–hafnium
forming
Not specified 0.005 to 9.11 lbs/million
lbs of metal formed
(1-day average)
0.002 to 3.77 lbs/million
lbs of
zirconium-hafnium
formed (max monthly
average)
0.005 to 9.11 lbs/million
lbs of metal formed
(1-day average)
0.002 to 3.77 lbs/million

lbs of
zirconium-hafnium
formed (max monthly
average)
0.005 to 9.11 lbs/million
lbs of metal formed
(1-day average)
0.002 to 3.77 lbs/million
lbs of
zirconium-hafnium
formed (max monthly
average)
0.005 to 9.11 lbs/million
lbs of metal formed
(1-day average)
0.002 to 3.77 lbs/million
lbs of
zirconium-hafnium
formed (max monthly
average)
0.005 to
9.11 lbs/million lbs of
metal formed (1-day
average)
0.002 to
3.77 lbs/million lbs of
zirconium-hafnium
formed (max monthly
average)
(5) Metals powder Not specified 0.004 to 2.29 lbs/million

lbs of powder atomized
(1-day average)
0.002 to 0.948 lbs/
million lbs of powder
atomized (max
monthly average)
0.004 to 2.55 lbs/million
lbs of powder atomized
(1-day average)
0.002 to 1.06 lbs/million
lbs of powder atomized
(max monthly average)
0.004 to 2.29 lbs/million
lbs of powder atomized
(1-day average)
0.002 to
0.948 lbs/million lbs of
powder atomized (max
monthly average)
0.004 to 2.55 lbs/million
lbs of powder atomized
(1-day average)
0.002 to 1.06 lbs/million
lbs of powder atomized
(max monthly average)
0.004 to
2.55 lbs/million lbs of
powder atomized
(1-day average)
0.002 to

1.06 lbs/million lbs of
powder atomized
(max monthly
average)
a
Information from ASTDR, Toxicological profile for cyanide (update), U.S. Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease
Registry, Atlanta, GA, 1997.
b
NSPS = New source performance standards. PSES = Pretreatment standards for existing sources. PSNS = Pretreatment standards for few sources. BPT = Best practical treatment
technology. BAT = Best available treatment technology.
c
40 CFR Subchapter N Part 415.422–415.426.
d
Information from USFDA, 40 CFR Part 420, Effluent limitations guidelines, pretreatment standards and new source performance standards for the iron and steel manufacturing point source
category; Final rule, U.S. Environmental Protection Agency, Washington, DC, 2002.
© 2006 by Taylor & Francis Group, LLC
Regulation of Cyanide in Water and Soil 371
TABLE 18.8
Land Disposal Treatment Standards for Cyanide in Water
Waste description under RCRA Cyanide form Standard (mg/l)
D003 Amenable cyanide 0.86
Total cyanide Reserved
F006, F019 Total cyanide 1.20
Amenable cyanide 0.86
F007, F008, F009 Total cyanide 1.90
Amenable cyanide 0.100
F010 Total cyanide 1.90
Amenable cyanide 0.100
F011, F012, P013, P021, P029,
P030, P063, P074, P098, P099,

P104, P106, P121
Total cyanide 1.90
Amenable cyanide 0.100
F037, K048, K049, K050, K051,
K052
Total cyanide 0.028
K005, K007 Total cyanide 0.740
K011, K013, K014 Total cyanide 21.0
K060 Total cyanide 1.90
K086 Total cyanide 1.90
Source: Information from ATSDR, Toxicological profile for Cyanide (update),
U.S. Department of Health and Human Services, Public Health Service, Agency
for Toxic Substances and Disease Registry, Atlanta, GA, 1997.
is a listed waste (i.e., listed in one of three lists [“F” List — Nonspecific source waste; “K” List —
specific source list; or “P” or “U” Lists — Commercial chemical products] developed by USEPA
and contained in the Code of Federal Regulations (CFR) at 40 CFR 261.31-33), or (2) exhibits one
or more of four characteristics; ignitability, corrosivity, reactivity, and toxicity (40 CFR 261.21.24).
If an environmental medium, such as groundwater, becomes contaminated (i.e., mixed) with
a hazardous waste, in accordance with the USEPA “contained in” policy, it will be regulated as a
hazardous waste until such time as the medium is treated to remove the contaminant. This policy
results in the potential applicability of the Land Disposal Restrictions (LDR) to contaminated media
during environmental remediation activities. The LDRs specify concentration levels for contaminants
that must be achieved before the impacted material can be placed in a landfill, surface impoundment,
waste pile, injection well, land treatment facility, salt dome formation, underground mine or cave,
or concrete bunker or vault. (LDRs do not apply to wastes that are discharged to surface waters,
where NPDES requirements apply, or to Publicly Owned Treatment Works, where pretreatment
requirements apply.)
There are several land disposal treatment standards that would be applicable to impacted ground-
water should it become mixed with specific listed or characteristic hazardous wastes that contain
cyanide. These concentration limits and the form of cyanide to which they apply are summarized in

Table 18.8.
Many states have been active in developing guidelines and standards for groundwater remedi-
ation under RCRA and CERCLA. A wide range of approaches has been used in establishing these
guidelines and standards. As cyanide is a frequently occurring subsurface contaminant [14], it is
frequently included in state lists of guidelines and standards. These lists are available via the Inter-
net; an excellent compendium is available at cleanuplevels.com [15]. In Pennsylvania, for example,
© 2006 by Taylor & Francis Group, LLC
372 Cyanide in Water and Soil
groundwater “medium specific concentrations” (MSCs) have been developed for free cyanide. The
free cyanide MSC is 200 µg/l for usedaquifers with total dissolved solids (TDS) less than2,500 mg/l;
20,000 µg/l for used aquifers with TDS greater than 2,500 mg/l; and 200,000 µg/l for nonuse
aquifers. Wisconsin has developed state public health groundwater quality standards for use in
remediation planning. The “enforcement standard” for cyanide (presumably free cyanide, but form
not specified) is 200 µg/l, while the “preventive action limit” is 40 µg/l. As is evident from these
two examples, many of the guidelines or standards are tied to the USEPA drinking water MCL of
200 µg/l.
18.1.4.2 Groundwater (CERCLA)
Section 121(d) of the Comprehensive Environmental Response, Compensation, and Liability Act
(CERCLA), as amended by the 1986 Superfund Amendments and Reauthorization Act (SARA),
requires that onsite remedial actions must attain or waive Federal or more stringent State applicable
or relevant and appropriate requirements (ARARs) upon completion of the remedial action. There
are three types of ARARs: (1) chemical specific, for example, total cyanide concentration in soil
<50 mg/kg; (2) action specific, for example, if an onsite landfill is proposed, it should meet con-
temporary landfill standards; and (3) location specific, for example, prohibition of land disposal in
a flood plain. Where ARARs do not exist for important chemicals at a site, or where the USEPA
determines an environmental regulation is not appropriate to determine clean-up levels, such levels
may be set through the use of quantitative risk assessment. More specifically for impacted ground-
water at a CERCLA site, maximum contaminant levels (MCLs) and maximum contaminant level
goals (MCLGs) under the Safe Drinking Water Act and water quality criteria under the Clean Water
Act represent potential chemical-specific ARARs. At the McAdoo Associates Superfund Site in

Pennsylvania, for example, the USEPA acute-exposure ambient water quality criterion for free cyan-
ide of 22 µg/l was adopted as the groundwater quality to be achieved at a downgradient point of
exposure [16]. Location-specific ARARs might include limits on activities in wetlands as prescribed
under Sections 401 and 404 of the Clean Water Act. Lastly, action-specific ARARs are usually
technology or activity-based requirements or limitations on actions or conditions involving specific
substances such as the application of existing BPT or BAT to cyanide-impacted groundwater. Stated
differently, nearly all of the water-related regulatory requirements that are discussed within this
chapter may be applicable, under some set of circumstances, to a groundwater on a CERCLA site
that has been impacted by some form of cyanide.
As noted in the previous discussion on RCRA, states have been very active in developing
guidelines and standards for groundwater remediation. As cyanide is a frequently occurring sub-
surface contaminant [14], it is frequently included in state lists of guidelines and standards. These
lists are available at cleanuplevels.com [15].
18.2 U.S. REGULATIONS, GUIDELINES, AND
CRITERIA FOR SOIL, SEDIMENT, AND PROCESS
RESIDUALS
18.2.1 S
OIL AND PROCESS RESIDUALS
As previously mentioned, wastes may be classified as hazardous wastes or solid (nonhazardous)
wastes. A solid waste under RCRA is hazardous if it is not excluded from the hazardous waste
regulations and (1) it is a listed waste (i.e., listed in one of three lists [“F” List, “K” List, or the “P” or
“U” Lists]), or (2) exhibits one or more of four characteristics, ignitability, corrosivity, reactivity, and
toxicity. Similar to groundwater, if soil becomes contaminated (i.e., mixed) with a hazardous waste,
in accordance with the USEPA “contained in” policy, it will be regulated as a hazardous waste until
© 2006 by Taylor & Francis Group, LLC
Regulation of Cyanide in Water and Soil 373
such time as it is treated to remove the contaminant. This policy results in the potential applicability
of the Land Disposal Restrictions (LDR) to contaminated media during environmental remediation
activities. The LDRs specify concentration levels for contaminants that must be achieved before the
impacted soil can be placed in a landfill, waste pile, land treatment facility, concrete bunker, or vault.

In the context of RCRA and CERCLA, the states have been very active in developing guidelines
and standards for soil remediation. A wide range of approaches has been used in establishing these
guidelines and standards. As cyanide is a frequently occurring subsurface contaminant [14], it is
frequently included in state lists of guidelines and standards. These lists are available at cleanup-
levels.com [15]. As an example, Pennsylvania has established “medium specific concentrations”
(MSCs) for cyanide in soil for use in direct contact risk evaluations, and also for soil-to-groundwater
evaluations. The direct contact MSCs for free cyanide are 4,400 mg/kg for surface soil at residential
sites (0 to 15 ft depth); 56,000 mg/kg for surface soil at nonresidential sites (0 to 2 ft depth); and
190,000 mg/kg for subsurface soil at nonresidential sites (2 to 15 ft depth). The free cyanide MSCs
for the soil-to-groundwater scenario are 200 mg/kg for both residential and nonresidential sites when
impacts on a used aquifer with TDS <2, 500 mg/l are relevant; 2,000 mg/kg for both residential
and nonresidential sites when impacts on a used aquifer with TDS >2,500 mg/l are relevant; and
190,000 mg/kg for both residential and nonresidential sites when impacts on a nonuse aquifer are rel-
evant. Other states have established their own kinds of classifications considering the unique nature
and uses of their soils and groundwaters.
18.2.1.1 Listed Wastes
There are several listed wastes that contain cyanide and for which land disposal treatment standards
have been specified. The same land disposal restrictions apply to soil that has been mixed with
cyanide that must be achieved before they, or a mixture of the waste with soil, can be managed in
one of the above-noted land disposal units.
The data provided in Table 18.9 indicate that concentrations of amenable cyanide between 9 and
30 mg/kg can be placed in a land disposal facility while total cyanide concentrations in a land disposal
facility are limited to between 1.2 and 590 mg/kg.
18.2.1.2 Characteristic Wastes
Reactivity is one of the four “characteristics” defined in RCRA that must be satisfied for a solid
waste to be considered a “characteristic” hazardous waste. Until recently, one of the categories of
wastes defined in the regulations in 40CFR 261.23 as a reactive waste had the following properties:
cyanide-bearing waste, which generate toxic fumes when exposed to mild acidic or basic conditions.
However, in 2004 this regulation was revised by withdrawing the category of reactive cyanide. This
withdrawal of the reactive cyanide was prompted by the fact that the specified test conditions, that is,

exposure to a strong acid, would rarely, if ever, yield toxic cyanide fumes because of the extremely
18.2.2 SEDIMENT
Sediments in freshwater, estuarine, and coastal systems can become contaminated as a result of
interactions with the overlying water and from deposition of material already contaminated. The
presence of chemical contaminants in sediments is a concern with respect to potential effects on
benthic organisms living in sediments, and on the broadercommunityofaquaticorganisms, especially
those that feed on benthic organisms and their food chain relatives. Since contaminated sediments
serve as a reservoir of chemical mass that can be released to the water column over time, the entire
© 2006 by Taylor & Francis Group, LLC
low solubility of the common solid forms of cyanide, such as ferric ferrocyanide (see Chapters 2
and 5), in water at pH values in the range 2.0 to 5.0.
these wastes. Table 18.9 provides a list of these cyanide-containing wastes and the concentrations of
374 Cyanide in Water and Soil
TABLE 18.9
Land Disposal Treatment Standards for Cyanide in Soil/Wastes
Waste description under RCRA Cyanide form Standard (mg/kg)
D003 Amenable cyanide 30
Total cyanide 590
F006, F007, F008, F009, F019 Amenable cyanide 30
Total cyanide 590
F010 Total cyanide 1.5
Amenable cyanide Not applicable
F011, F012, P013, P021, P029,
P030, P063, P074, P098, P099,
P104, P106, P121
Total cyanide 110
Amenable cyanide 9.1
F037, K048, K049, K050, K051,
K052
Total cyanide 1.8

K005, K007 Total cyanide Reserved
K011, K013, K014 Total cyanide 57
K060 Total cyanide 1.2
K086 Total cyanide 1.5
Source: Information from ATSDR, Toxicological profile for cyanide (update),
U.S. Department of Health and Human Services, Public Health Service, Agency
for Toxic Substances and Disease Registry, Atlanta, GA, 1997.
aquatic community of plants and animals is potentially impacted by the presence of contaminants in
sediments.
Chemical quality standards or guidelines for sediments are most relevant in three primary con-
texts in the United States: (1) management of sediment from navigational dredging; (2) cleanup
actions under CERCLA in which sediments have been identified as a contaminated site or part of a
contaminated site; and (3) development of total maximum daily load (TMDL) plans for protection of
aquatic systems under the Clean Water Act. For dredging operations and contaminated site remedi-
ation, quality objectives are established on a site-specific basis, using state or U.S. quality guidelines
or site-specific risk assessment. These assessments make use of existing water quality and sediment
quality criteria established for the protection of aquatic life. Thus, sediment management or cleanup
objectives are related to the same analyses performed to identify chemical levels that are protective
of benthic and aquatic life.
Efforts to plan for and develop U.S. sediment quality criteria have been underway since the
1970s. In addition to the scientific complexities involved, the development of sediment quality
criteria has been administratively challenging in that more than ten Federal statutes provide authority
to USEPA to address contaminated sediment [17]. Under Section 304(a) of the Clean Water Act,
the USEPA is specifically charged with the development and implementation of sediment quality
criteria. Implementation of this charge, however, requires coordination with regulations developed
under other statutes that pertain to dredging, contaminated site remediation, and other areas. USEPA
has developed a Contaminated Sediment Management Strategy to address the coordination issue
and to establish the framework for development of sediment quality criteria and approaches to
management of contaminated sediment [17].
The USEPA is developing sediment quality criteria for the protection of benthic organisms, to

be applied in cases where the sediment total organic carbon exceeds 0.2% dry weight, the primary
route of exposure is in direct contact with the sediment, and the sediments are continually submerged
© 2006 by Taylor & Francis Group, LLC
Regulation of Cyanide in Water and Soil 375
or there is information indicating that equilibrium has been established between the water and the
sediments. Sediment quality criteria have been developed for several nonionic organic compounds,
and are in development for additional organic compounds and selected metals. No sediment quality
criteria have been established by the USEPA for any cyanide species.
As part of the Contaminated Sediment Management Strategy, USEPA is conducting a National
Sediment Inventory [18] for the purpose of assessing the quality of U.S. freshwater, estuarine,
and coastal sediments, and for building the scientific foundation upon which national sediment
quality criteria can be established. Sediment quality screening levels have been established for some
contaminants by the USEPA, for the purpose of interpreting the NSI data [18]. These screening levels
are for selected metals and persistent organic compounds. No screening levels have been established
yet for any cyanide species.
It is not theintentionoftheUSEPA thatsedimentqualitycriteriaorscreeninglevelsshouldbeused
as mandatory cleanup levels for remediation or decision levels for dredged material management
[17]. Decisions about what constitutes desired or acceptable sediment quality in those situations
should be based on analysis of potential effects for different levels and types of contaminants in
particular situations. This is the governing principle of the U.S. Army Corps of Engineers in their
management of dredged material [19].
A number of states, for example, Florida and Washington, have developed sediment quality
criteria. It appears that no state sediment quality criteria have been established yet for any cyanide
species. As is the case for the USEPA sediment quality screening levels, the state sediment quality
criteria that have been established are focused primarily on some metals and persistent organic
compounds.
Some cyanide sediment quality guidelines have been developed and reported in the United States
Region 5 developed some guidelines for cyanide concentrations in nonpolluted, moderately-polluted,
and heavily-polluted sediments [20]. The sediment quality guidelines reported in Table 18.10, while
not developed in the current framework for establishment of U.S. sediment quality criteria, suggest

that concentrations below 0.1 mg/kg will be protective of benthic life in freshwater systems. For
the guidelines summarized in Table 18.10, the particular form of cyanide was not specified in the
original reports. A conservative approach would be to consider these values to refer to total cyanide,
though the toxic form of interest will usually be free cyanide.
Cyanide contamination in sediments is not often a driver in sediment management regulation
and decision-making because dissolved free cyanide (HCN, CN
−
), the most toxic form of cyanide,
sediments. Other dissolvedforms of cyanide, most notably metal–cyanide complexes, can be retained
longer in sediments butarelesstoxic. In addition, cyanidespecieshave lowbioaccumulationpotential
concentrations and total amounts, such as will be the case for sediments contaminated from a former
waste disposal activity or spill. Development of a sediment quality goal for cyanide at a particular
site, if desired, will require a site-specific risk assessment. If such an assessment is undertaken, the
information in Chapter 5 on cyanide species reactivity, especially solid–water partitioning, will be
useful.
18.3 INTERNATIONAL REGULATORY STANDARDS
AND GUIDELINES FOR CYANIDE IN WATER AND SOIL
Regulations paralleling those of the United States have been developed in most other industrial-
ized countries for managing discharges of contaminants to water and land, for establishing acceptable
concentrations of contaminants in drinking water and surface water, and for guiding cleanup of
© 2006 by Taylor & Francis Group, LLC
is highly soluble and biodegradable (see Chapters 5 and 6) and thus usually has a short half-life in
(Chapter 14; and [4]). Cyanide in sediments may become a concern when present in significant mass
for specific applications. These are summarized in Table 18.10. For example, in the 1970s USEPA