United States
EnvironrnontBl Protoctlon
Agency
Office of Water
Regulations and Standards
Washington. DC 20460
June, IMS
Environmental Profiles
and Hazard Indices
for Constituents
of Municipal Sludge:
Cyanide
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PREFACE
This document is one of a series of prelimin.. •/ assessments dealing
with chemicals of potential concern in municipal sewage sludge. The
purpose of these documents is to: (a) summarize the available data for
the constituents of potential concern, (b) identify the key environ-
mental pathways for each constituent related to a reuse and disposal
option (based on hazard indices), and (c) evaluate the conditions under
which such a pollutant may pose a hazard. Each document provides a sci-
entific basis for making an initial determination of whether a pollu-
tant, at levels currently observed in sludges, poses a likely hazard to
human health or the environment when sludge is disposed of by any of
several methods. These methods include lands reading on food chain or
nonfood chain crops, distribution and marketing programs, landfilling,
incineration and ocean disposal.
These documents are intended to serve as a rapid screening tool to
narrow an initial list of pollutants to those of concern. If* a signifi-
cant hazard is indicated by this preliminary analysis, a more detailed
assessment will be undertaken to better quantify the risk from this
chemical and to derive criteria if warranted. If a hazard is shown to
be unlikely, no further assessment will be conducted at this time; how-
ever, a reassessment will be conducted after initial regulations are
finalized. In no case, however, will criteria be derived solely on the
basis of information presented in this document.
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TABLE OP CONTENTS
Page
PREFACE i
1. INTRODUCTION 1-1
2. PRELIMINARY CONCLUSIONS FOR CYANIDE IN MUNICIPAL SEWAGE
SLUDGE 2-1
Landspreading and Distribution-and-Marketing 2-1
Landfilling 2-1
Incineration 2-1
Ocean Di sposal 2-1
3. PRELIMINARY HAZARD INDICES FOR CYANIDE IN MUNICIPAL SEWAGE
SLUDGE 3-1
Landspreading and Distribution-and-Marketing 3-1
Landfilling 3-1
Index of groundwater concentration resulting
from landfilled sludge (Index 1) 3-1
Index of human tpxicity resulting from
groundwater contamination (Index 2) 3-8
Incineration 3-10
Ocean Disposal 3-10
A. PRELIMINARY DATA PROFILE FOR CYANIDE IN MUNICIPAL SEWAGE
SLUDGE 4-1
Occurrence 4-1
Sludge 4-1
Soil - Unpolluted 4-1
Water - Unpolluted 4-2
Air 4-2
Food 4-2
Human Effects 4-3
Ingestion 4-3
Inhalation 4-4
11
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TABLE OF CONTENTS
(Continued)
Page
Plant Effects 4-4
Phytotozicity 4-4
Uptake 4-5
Domestic Animal and Wildlife Effects 4-5
Toxicity 4-5
Uptake 4-5
Aquatic Life Effects 4-6
Toxicity 4-6
Uptake 4-6
Soil Biota Effects 4-6
Toxicity 4-6
Uptake 4-7
Physicochemical Data for Estimating Fate and Transport 4-7
5. REFERENCES 5-1
APPENDIX. PRELIMINARY HAZARD INDEX CALCULATIONS FOR
CYANIDE IN MUNICIPAL SEWAGE SLUDGE A-l
in
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SECTION 1
INTRODUCTION
This preliminary data profile is one of a series of profiles
dealing with chemical pollutants potentially of concern in municipal
sewage sludges. Cyanide was initially identified as being of potential
concern when sludge is placed in a landfill.* This profile is a
compilation of information that may be useful in determining whether
cyanide poses an actual hazard to human health or the environment when
sludge is disposed of by this method.
The focus of this document is the calculation of "preliminary
hazard ind.-.es" for selected potential exposure pathways, as shown in
Section 3. Each index illustrates the hazard that could result from
movement of a pollutant by a given pathway to cause a given effect
(e.g., sludge •» groundwater •» human toxicity). The values and assump-
tions employed in these calculations tend to represent a reasonable
"worst case"; analysis of error or uncertainty has been conducted to a
limited degree. The resulting value in most cases is indexed to unity;
i.e., values >1 may indicate a potential hazard, depending upon the
assumptions of the calculation.
The data used for index calculation have been selected or estimated
based on information presented in the "preliminary data profile",
Section 4. Information in the profile is based on a compilation of the
recent literature. An attempt has been made to fill out the profile
outline to the greatest extent possible. However, since this is a pre-
liminary analysis, the literature has not been exhaustively perused.
The "preliminary conclusions" drawn from each index in Section 3
are summarized in Section 2. The preliminary hazard indices will be
used as a screening tool to determine which pollutants and pathways may
pose a hazard. Where a potential hazard is indicated by interpretation
of these indices, further analysis will include a more detailed exami-
nation of potential risks as well as an examination of site-specific
factors. These more rigorous evaluations may change the preliminary
conclusions presented in Section 2, which are based on a reasonable
"worst case" analysis.
The preliminary hazard indices for selected exposure routes
pertinent to landfilling are included in this profile. The calculation
formulae for these indices are shown in the Appendix. The indices are
rounded to two significant figures.
Listings were determined by a series of expert workshops convened
during March-May, 1984 by the Office of Water Regulations and
Standards (OWRS) to discuss landspreading, landfilling, incineration,
and ocean disposal, respectively, of municipal sewage sludge.
1-1
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SECTION 2
PRELIMINARY CONCLUSIONS FOR CYANIDE IN MUNICIPAL SEWAGE SLUDGE
The following preliminary conclusions have been derived from the
calculation of "preliminary hazard indices", which represent conserva-
tive or "worst case" analyses of hazard. The indices and their basis
and interpretation are explained in Section 3. Their calculation
formulae are shown in the Appendix.
I. LAHDSPREADING AND DISTRIBUTION-AND-MARKETING
Based on the recommendations of the experts at the OWRS meeting
(April-May, 1984), an assessment of this reuse/disposal option is
not being conducted at this time. The U.S. EPA reserves the right
to conduct such an assessment for this option in the future.
II. LANDFILLING
The landfill disposal of municipal sewage sludge is expected to
result in a substantial increase in cyanide concentrations in
groundwater, especially when worst-site parameters are present in
the saturated zone or when the cumulative worst case is evaluated
(see Index 1). In most cases, cyanide may pose a slight human
health hazard as a result of drinking groundwater contaminated by
municipal sewage sludge landfills. However, a moderate health
hazard may be associated with the cumulative worst-case landfill
scenario (see Index 2).
III. INCINERATION
Based on the recommendations of the experts at the OURS meetings
(April-May, 1984), an assessment of this reuse/disposal option is
not being conducted at this time. The U.S. EPA reserves the right
to conduct such an assessment for this option in the future.
IV. OCEAN DISPOSAL
Based on the recommendations of the experts at the OWRS meetings
(April-May, 1984), an assessment of this reuse/disposal option is
not being conducted at this time. The U.S. EPA reserves the right
to conduct such an assessment for this option in the future.
2-1
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SECTION 3
PRELIMir\HY HAZARD INDICES FOR CYNANIDE
IH "JHICIPAL SEWAGE SLUDGE
I. LANDSFREADING AND DISTRIBUTION-AND-HARKETING
Based on the recommendations of the experts at the OWRS meetings
(April-May, 1984), an assessment of this reuse/disposal option is
not being conducted at this time. The U.S. EPA reserves the right
to conduct such an assessment for this option in the future.
II. LANDPILLING
A. Index of Groundwater Concentration Resulting from Landfilled
Sludge (Index 1)
1. Explanation - Calculates groundwater contamination which
could occur in a potable aquifer in the landfill vicin-
ity. Uses U.S. EPA's Exposure Assessment Group (EAG)
model, "Rapid Assessment of Potential Groundwater Contam-
ination Under Emergency Response Conditions" (U.S. EPA,
1983). Treats landfill leachate as a pulse input, i.e.,
the application of a constant source concentration for a
short time period relative to the time frame of the anal-
ysis. In order to predict pollutant movement in soils
and groundwater, parameters regarding transport and fate,
and boundary or source conditions are evaluated. Trans-
port parameters include the interstitial pore water
velocity and dispersion coefficient. Pollutant fate
parameters include the degradation/decay coefficient and
retardation factor. Retardation is primarily a function
of the adsorption process, which is characterized by a
linear, equilibrium partition coefficient representing
the ratio of adsorbed and solution pollutant concentra-
tions. This partition coefficient, along with soil bulk
density and volumetric water content, are used to calcu-
late the retardation factor. A computer program (in
FORTRAN) was developed to facilitate computation of the
analytical solution. The program predicts pollutant con-
centration as a function of time and location in both the
unsaturated and saturated zone. Separate computations
and parameter estimates are required for each zone. The
prediction requires evaluations of four dimensionless
input values and subsequent evaluation of the result,
through use of the computer program.
2. Assumptions/Limitations - Conservatively assumes that the
pollutant is 100 percent mobilized in the leachate and
that all leachate leaks out of the landfill in a finite
period and undiluted by precipitation. Assumes that all
soil and aquifer properties are homogeneous and isotropic
throughout each zone; steady, uniform flow occurs only in
3-1
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the vertical direction throughout the unsaturated zone,
and only in the horizontal (longitudinal) plane in the
saturated zone; pollutant movement is considered only in
direction of groundwater flow for the saturated zone; all
pollutants exist in concentrations that do not signifi-
cantly affect water movement; for organic chemicals, the
background concentration in the soil profile or aquifer
prior to release from the source is assumed to be zero;
the pollutant source is a pulse input; no dilution of the
plume occurs by recharge from outside the source area;
the leachate is undiluted by aquifer flow within the
saturated zone; concentration in the saturated zone is
attenuated only by dispersion.
3. Data Used and Rationale
a. Unsaturated zone
i. Soil type and characteristics
(a) Soil type
Typical Sandy loam
Worst Sandy
These two soil types were used by Gerritse et
al. (1982) to measure partitioning of elements
between soil and a sewage sludge solution
phase. They are used here since these parti-
tioning measurements (i.e., K
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estimated by infiltration or net recharge. The
volumetric wa'war content is used in calculating
the water n. Cement through the unsaturated zone
(pore water velocity) and the retardation
coefficient. Values obtained from COM, 1984.
(d) Fraction of organic carbon (foc)
Typical 0.005 (unitless)
Worst 0.0001 (unitless)
Organic content of soils is described in terms
of percent organic carbon, which is required in
the estinu.-'ion of partition coefficient, Kj.
Values, obtained from R. Griffin (1984) are
representative values for subsurface soils.
ii. Site parameters
(a) Landfill leaching time (LT) = 5 years
Sikora et al. (1982) monitored several sludge
entrenchment sites throughout the United States
and estimated time of landfill leaching to be 4
or 5 years. Other types of landfills may leach
for longer periods of time; however, the use of
a value for entrenchment sites is conservative
because it results in a higher leachate
generation rate.
(b) Leachate generation rate (Q)
Typical 0.8 m/year
Worst 1.6 m/year
It is conservatively assumed that sludge
leachate enters the unsaturated zone undiluted
by precipitation or other recharge, that the
total volume of liquid in the sludge leaches
out of the landfill, and that leaching is com-
plete in 5 years. Landfilled sludge is assumed
to be 20 percent solids by volume, and depth of
sludge in the landfill is 5 m in the typical
case and 10 m in the worst case. Thus, the
initial depth of liquid is 4 and 8 m, and
average yearly leachate generation is 0.8 and
1.6 m, respectively.
(c) Depth to groundwater (h)
Typical 5 m
Worst 0 m
3-3
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Eight landfills were monitored throughout the
United States and depths to groundwater below
them were listed. A typical depth to ground-
water of 5 m was observed (U.S. EPA, 1977).
For the worst case, a value of 0 m is used to
represent the situation where the bottom of the
landfill is occasionally or regularly below the
water table. The depth to groundwater must be
estimated in order to evaluate the likelihood
that pollutants moving through the unsaturated
soil will reach the groundwater.
(d) Dispersivity coefficient (a)
Typical 0.5 m
Worst Not applicable
The dispersion process is exceedingly complex
and difficult to quantify, especially for the
unsaturated zone. It is sometimes ignored in
the unsaturated zone, with the reasoning that
pore water velocities are usually large enough
so that pollutant transport by convection,
i.e., water movement, is paramount. As a rule
of thumb, dispersivity may be set equal to
10 percent of the distance measurement of the
analysis (Gelhar and Axness, 1981). Thus,
based on depth to groundwater listed above, the
value for the typical case is O.S and that for
the worst case does not apply since leachate
moves directly to the unsaturated zone.
iii. Chemical-specific parameters
(a) Sludge concentration of pollutant (SC)
Typical 476.2 mg/kg DW
Worst 2686.6 mg/kg DW
The typical and worst sludge concentrations are
the median and 95th percentile values,
respectively, statistically derived from sludge
concentration data from a survey of 40 publicly
owned treatment works (POTWs) (U.S. EPA, 1982).
(See Section 4, p. 4-1).
(b) Soil half-life of pollutant (t^) - Data not
immediately available.
(c) Degradation rate (y) = 0.0 day'1
The unsaturated zone can serve as an effective
medium for reducing pollutant concentration
through a variety of chemical and biological
3-4
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decay mechanisms which transform or attenuate
the pollutant. While these decay processes are
usually complex, they ai approximated here by
a first-order rate constai*. The degradation
rate is calculated using the following formula:
Since half-life data are not immediately
available, it is conservatively assumed that
U = 0.0 day'1.
„'•
(d) Organic carbon partition coefficient (Koc) =
0.0 mL/g
The organic carbon partition coefficient is
multiplied by the percent organic carbon
content of soil (foc) to derive a partition
coefficient (Kd), which represents the ratio of
absorbed pollutant concentration to the
dissolved (or solution) concentration. The
equation (Koc x foc) assumes that organic
carbon in the soil is the primary means of
adsorbing organic compounds onto soils. This
concept serves to reduce much of the variation
in Kd values for different soil types. Since
data are not immediately available, it is
conservatively assumed that Koc = 0.0 mL/g.
b. Saturated zone
i. Soil type and characteristics
(a) Soil type
Typical Silty sand
Worst Sand
A silty sand having the values of aquifer por-
osity and hydraulic conductivity defined below
represents a typical aquifer material. A more
conductive medium such as sand transports the
plume more readily and with less dispersion and
therefore represents a reasonable worst case.
(b) Aquifer porosity (0)
Typical 0.44 (unitless)
Worst 0.389 (unitless)
Porosity is that portion of the total volume of
soil that is made up of voids (air) and water.
Values corresponding to the above soil types
3-5
-------
are from Pettyjohn et al. (1982) as presented
in U.S. EPA (1983).
(c) Hydraulic conductivity of the aquifer (K)
Typical 0.86 m/day
Worst 4.04 m/day
The hydraulic conductivity (or permeability) of
the aquifer is needed to estimate flow velocity
based on Darcy's Equation. It is a measure of
the volume of liquid that can flow through a
unit area or media with time; values can range
over nine orders of magnitude depending on the
nature of the media. Heterogenous conditions
produce large spatial variation in hydraulic
conductivity, making estimation of a single
effective value extremely difficult. Values
used are from Freeze and Cherry (1979) as
presented in U.S. EPA (1983).
(d) Fraction of organic carbon (foc) =
0.0 (unitless)
Organic carbon content, and therefore adsorp-
tion, is assumed to be 0 in the saturated zone.
ii. Site parameters
(a) Average hydraulic gradient between landfill and
well (i)
Typical 0.001 (unitless) !
Worst 0.02 (unitless)
The hydraulic gradient is the slope of the
water table in an unconfined aquifer, or the
piezometric surface for a confined aquifer.
The hydraulic gradient must be known to
determine the magnitude and direction of
groundwater flow. As gradient increases, dis-
persion is reduced. Estimates of typical and
high gradient values were provided by Donigian
(1985).
(b) Distance from well to landfill (Al)
Typical 100 m
Worst 50 m
This distance is the distance between a
landfill and any functioning public or private
water supply or livestock water supply.
3-6
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(c) Dispersivity coefficient (a)
Typical 10 m
Worst 5 m
These values are 10 percent of the distance
from well to landfill (AH), which is 100 and
SO m, respectively, for typical and worst
conditions.
(d) Minimum thickness of saturated zone (B) = 2 m
The minimum aquifer thickness represents the
assumed thickness due to preexisting flow;
i.e., in the absence of leachate. It is termed
the minimum thickness because in the vicinity
of the site it may be increased by leachate
infiltration from the site. A value of 2 m
represents a worst case assumption that
preexisting flow is very limited and therefore
dilution of the plume entering the saturated
zone is negligible.
(e) Width of landfill (W) = 112.8 m
The landfill is arbitrarily assumed to be
circular with an area of 10,000 m2.
iii. Chemical-specific parameters
(a) Degradation rate (y) = 0 day'1
Degradation is assumed not to occur in the
saturated zone.
(b) Background concentration of pollutant in
groundwater (BC) = 0 Ug/L
It is assumed that no pollutant exists in the
soil profile or aquifer prior to release from
the source.
4. Index Values - See Table 3-1.
S. Value Interpretation - Value equals the maximum expected
groundwater concentration of pollutant, in Ug/L, at the
well.
6. Preliminary Conclusion - The landfill disposal of
municipal sewage sludge is expected to result in a
substantial increase in cyanide concentrations in
groundwater, especially when worst-site parameters are
present in the saturated zone or when the cumulative
worst case is evaluated.
3-7
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B. Index of Human Toxicity Resulting from Groundwater
Contain"nation (Index 2)
1. t_-?lanation - Calculates human exposure which could
result from groundwater contamination. Compares exposure
with acceptable daily intake (ADI) of pollutant.
2. Assumptions/Limitations - Assumes long-term exposure to
maximum concentration at well at a rate of 2 L/day.
3. Data Used and Rationale
a. Index of groundwater concentration resulting from
landfilled sludge (Index 1)
See Section 3, p. 3-9.
b. Average human consumption of drinking water (AC) =
2 L/day
The value of 2 L/day is a standard value used by
U.S. EPA in most risk assessment studies.
c. Average daily human dietary intake of pollutant
(DI) - Data not immediately available.
d. Acceptable daily intake of pollutant (ADI) =
7560 Ug/day
The reported ADI value is based on the no-
observable-adverse-effect-level (NOAEL) in mammals
(10.8 mg/kg/day) for the inhibition of cytochrome
oxidase activity in rats (U.S. EPA, 1984). (See
Section 4, p. 4-3.)
4. Index 2 Values - See Table 3-1.
5. Value Interpretation - Value equals factor due only to
groundwater contamination by landfill by which expected
intake exceeds ADI. The value does not account for the
possible increase resulting from daily dietary intake of
pollutant since DI data were not immediately available.
6. Preliminary Conclusion - In most cases, cyanide may pose
a slight human health hazard as a result of drinking
groundwater contaminated by municipal sewage sludge
landfills. However, a moderate health hazard may be
associated with the cumulative worst-case landfill
scenario.
3-8
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TABLE 3-1. INDEX OP CROUNDUATER CONCENTRATION RESULTING FROM LANDFILLED SLUDGE (INDEX 1) AND
INDEX OF HUMAN TOXICITY RESULTING FROM GROUNDUATER CONTAMINATION (INDEX 2)
Site Characteristics
Sludge concentration
Unsaturated Zone
Soil type and charac-
teristics^
Site parameters6
Saturated Zone
Soil type and charac-
teristics^
Site parameters^
Index 1 Value (pg/L)
Index 2 Value
1
T
T
T
T
T
13
3.4xlO-3
2
W
T
T
T
T
73
1.9xlO-2
3
T
W
T
T
T
13
3.4x10-3
Condition of
4
T
NA
U
T
T
13
3.4x10-3
Analysisa»b»c
5
T
T
T
U
T
69
1.8xlO-2
6
T
T
T
T
W
520
0.14
7
W
NA
U
U
W
16000
4.1
8
N
N
N
N
N
0
0
aT = Typical values used; W = worst-case values used; N = null condition, where no landfill exists, used as
basis for comparison; NA = not applicable for this condition.
Index values for combinations other than those shown may be calculated using the formulae in the Appendix.
*-See Table A-l in Appendix for parameter values used.
Dry bulk density (Pdry), volumetric water content (8), and fraction of organic carbon (foc).
^Leachate generation rate (Q), depth to groundwater (h), and dispersivity coefficient (o).
*Aquifer porosity (0) and hydraulic conductivity of the aquifer (K).
SHydraulic gradient (i), distance from well to landfill (AH), and dispersivity coefficient (a).
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III. INCINERATION
Based on the recommrndaiions of the experts at the OWR5 meetings
(April-May, 1984), an Assessment of this reuse/disposal option is
not being conducted at tnis time. The U.S. EPA reserves the right
to conduct such an assessment for this option in the future.
IV. OCEAN DISPOSAL
Based on the recommendations of the experts at the OWRS meetings
(April-May, 1984), an assessment of this reuse/disposal option is
not being conducted at this time. The U.S. EPA reserves the right
to conduct .such an assessment for this option in the future.
3-10
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SECTION 4
PRELIMINARY DATA PROFILE FOR CYANIDE IN MUNICIPAL SEWAGE SLUDGE
I. OCCURRENCE
A. Sludge
1. Frequency of Detection
Detected in 992 of 432 samples from
40 POTWs
Detected in 72Z of 72 samples from
10 POTWs
2. Concentration
36 to 286,000 yg/L in 40 POTWs
10 to 4,000 pg/L in 10 POTWs
SOth percentile = 476.2 Ug/g DW
Mean = 835.6 Ug/g DW
95th percencile = 2686.6 iig/g DW
B. Soil - Unpolluted
1. Frequency of Detection
Data not immediately available.
2. Concentrat ion
Cyanides are not: absorbed or retained
within soils. Microbial metabolism
rapidly degrades cyanide and thus
minimizes soil accumulation.
Cyanide is not a natural constituent of
soil. Plants can synthesize quite large
amounts of cyanide in tissues under
certain climatic conditions. Incor-
poration of cyanide-containing plant
materials into soils usually results in
the transformation of cyanide into
harmless nitrogen gas or into nitrate by
microbial oxidation.
U.S. EPA, 1982
(p. 41)
U.S. EPA, 1982
(p. 49)
U.S. EPA, 1982
(p. 41)
U.S. EPA, 1982
(p. 49)
Statistically
derived from
U.S. EPA, 1982
U.S. EPA, 1978
(p. 2)
Fuller, 1977
(p. 70)
4-1
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C. Hater - Unpolluted
1. Frequency of Detection
Despite numerous potential sources of U.S. EPA, 1980
pollution, cyanide is relatively (p. C-2)
uncommon in U.S. water supplies.
2. Concentration
a. Freshwater
Data not immediately available.
b. Seavater
Data not immediately available.
c. Drinking water
8 llg/L maximum concentration U.S. EPA, 1982
0.09 llg/L average for 2,595 water (p. C-4)
samples
D. Air
1. Frequency of Detection
Cyanides are uncommon in air. U.S. EPA, 1980
(p. C-l)
Cyanides are usually not found in air. U.S. EPA, 1978
(p. 9)
2. Concentration
Data not immediately available.
E. Food
1. Frequency of Detection
Except for certain naturally occurring U.S. EPA, 1982
organonitrites in plants, it is uncommon (p. C-5)
to find cyanide in foods in the United
States. Additionally, there are no data
indicating bioconcentration of cyanide.
The bioconcentration factor will be very
close to zero.
4-2
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2. Concentration
Data not immediately available.
II. HUMAN EFFECTS
A. Ingestion
1. Carcinogenic!ty
a. Qualitative Assessment
There have been no detailed studies U.S. EPA, 1978
to implicate cyanide as a carcino- (p. 183)
genie agent.
b. Potency
Data not immediately available.
c. Effects
There is no evidence that chronic U.S. EPA, 1980
exposure to cyanide results in (p. C-23)
carcinogenic effects.
2. Chronic Tozicity
a. ADI
7.56 mg/day. The ADI for man has U.S. EPA, 1984
been derived by taking the NOAEL in (p. 17)
mammals (10.8 mg/kg/day) multiplied
by the weight of the average man
(70 kg) and dividing by a safety
factor of 100. This is based on
data for the inhibition of cyto-
chrome oxidase activity in rats.
b. Effects
The chronic effects of long term U.S. EPA, 1978
exposure to low cyanide levels are (p. 139)
not well understood.
Cyanide ingested by humans at quanti- U.S. EPA, 1976
ties of 10 mg or less per day is not (p. 67)
toxic and is biotransferred to the
less toxic thiocyanate.
4-3
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3. Absorption Factor
The percentage of a given dose absorbed U.S. EPA, 1978
is a factor of dose size and absorption 'p. 128)
rate: death may intervene before
absorption is complete.
4. Existing Regulations
Water quality criterion for drinking U.S. EPA, 1980
water = 200 Ug/L (p. c-24)
B. Inhalation
1. Carcinogenic!ty
Data not immediately available.
2. Chronic Toxicity
a. Inhalation Threshold or NPIH
No data immediately available for
cyanide.
b. Effects
Inhalation of cyanogen or halogenated U.S. EPA, 1978
cyanogens causes respiratory irrita- (p. 129)
tion with possible hemorrhage and
pulmonary edema. Inhalation of HCN
vapor can be fatal.
Inhalation of 270 ppra HCN vapor U.S. EPA, 1978
brings death immediately; 135 ppm (p. 129)
is fatal after 30 minutes.
3. Absorption Factor
Data not immediately available.
A. Existing Regulations
Threshold limit values on the basis of ACGIH, 1982
time-weighted average for cyanogen is
20 mg/m3 or 10 ppm.
III. PLANT EFFECTS
A. Phytotoxicity
Cyanide is toxic to plants inhibiting U.S. EPA, 1978
electron transport in photosynthetic and (p. 100)
respiratory functions.
4-4
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Cyanides are found in many plants and animals U.S. EPA, 1976
as metabolic intermediates which are (p. 65)
generally not stored for long periods of
time.
Cyanide is naturally produced by some fungi. Fuller, 1977
at least one bacterium, and many vascular (p. 145)
plants.
Cyanide is utilized as an energy source and/
or source of nitrogen by plants and
microorganisms.
Cyanide and related compounds have long been
regarded as potential fertilizers. Cyanamide
serves as a fertilizer because it forms
ammonia readily in soils.
Cyanide added to soils in modest amounts (up
to 200 Ug/g NaCN) is slightly less effective
as a N-fertilizer for some crops.
B. Uptake
Free cyanide is not found in plants. U.S. EPA, 1978
(p. 4)
Cyanide producing plants can have up to U.S. EPA, 1978
378 Ug/g CN in tissues. (p. 87)
IV. DOMESTIC ANIMAL AND WILDLIFE EFFECTS
A. Tozicity
See Table 4-1.
Cyanide has an unusually low degree of U.S. EPA, 1980
chronic toxicity. It does not appear to be (p. C-2)
mutagenic, teratogenic, or carcinogenic.
B. Uptake
Cyanide has a low degree of persistence in U.S. EPA, 1980
the environment and it is not accumulated or (p. C-l)
stored in any mammalian species that has been
studied.
There is no data available indicating biocon- U.S. EPA, 1980
centration of cyanide. The U.S. EPA Duluth (p. C-5)
laboratory states that the bioconcentration
factor will be very close to zero.
4-5
-------
Cyanides are found in many plants and animals
as metabolic intermediates which are
generally not stored for long periods of
time.
V. AQUATIC LIFE EFFECTS
A. Toxicity
1. Freshwater
Freshwater aquatic organisms and their U.S. EPA, 1985
uses should not be affected unaccep-
tably if the four-day average concen-
tration of free cyanide (the sum of
cyanide present as HCN and CN~*,
expressed as CN) does not exceed
5.2 Ug/L more than once every three
years on the average and if the one-
hour average concentration does not
exceed 22 Ug/L more than once every
three years on the average.
2. Saltwater
Saltwater aquatic organisms and their U.S. EPA, 1985
uses should not be affected unaccep-
tably if the one-hour average concen-
tration of free cyanide (the sum of
cyanide present as HCN and CN~*,
expressed as CN) does not exceed
1.0 ug/L more than once every three
years on the average.
B. Uptake
Data not immediately available.
VI. SOIL BIOTA EFFECTS
A. Toxicity
See Table 4-2.
A wide variety of microorganisms are able U.S. EPA, 1978
to metabolize cyanide. These organisms may (p. 3)
play a role in the treatment of cyanide
wastes. If a mixed population in a sludge
sample has not been exposed to cyanide
concentration, small cyanide concentration
(200 ppm) can be toxic. However, the popula-
tion can be acclimated to cyanide after which
higher concentrations can be metabolized.
4-6
-------
B. Uptake
Data not immediately available.
VII. PHYSICOCHEMICAL DATA FOR ESTIMATING PATE AND TRANSPORT
Molecular weight: HCN 27
26
Physical form at standard temperature and
pressure: colorless liquid
Solution in water: soluble in all proportions
Vapor pressure:
-178°C 100 torr
7°C 380 torr
21.9°C 658.7 torr
26.7°C (b.p.) 760 torr
Cyanide commonly occurs in water as hydro- U.S. EPA, 1980
cyanic acid (HCN), the cyanide ion (CN~*),
simple cyanides, metallocyanide complexes, or
as simple chain and complex ring organic com-
pounds. "Free cyanide" is defined as the sum
of the cyanide present as HCN and as CN~^.
The alkali metal salts such as potassium
cyanide (KCN) and sodium cyanide (NaCN) are
very soluble in aqueous solutions and the
resulting cyanide ions readily hydrolyze with
water to form HCN. The extent of HCN forma-
tion is mainly dependent upon water tempera-
ture and pH. At 20°C and a pH of 8 or
below, the fraction of free cyanide existing
as HCN is at least 0.96.
Cyanide ions form complexes with a variety of
metals, especially those of the transition
series. The stabilities of these complexes
are highly variable. Zinc and cadmium cyanide
complexes, when diluted with water, are known
to dissociate rapidly and nearly completely
to form HCN. Some of the other metallocyanide
anions, such as those formed with copper,
nickel, and iron, demonstrate varying degrees
of stability.
4-7
-------
TABLE 4-1. TOXICITV OP CYANIDE TO DOMESTIC ANIMALS AND WILDLIFE
Peed
Chemical Porn Concentration
Species Ped (|ig/g)
Dog NaCN NR«
-is
00
Dog. beagle NaCN ISO
Rat HCN 100-300
fumigated
into feed
Water Daily
Concentration Intake Duration
(ng/L) (mg/kg) of Study Effects
NR 0.5-2.0 IS months Administered once or
twice per day producing
toxic signs but recovery
within 1/2 hour I no long-
tern effects
NK NR 30 days No effect
NR NR 2 years No effect
References
U.S. EPA, 1980 (p. C-18)
.
U.S. EPA. 1980 (p. C-19)
U.S. EPA, 1980 (p. C-19)
• NR - Not reported.
-------
TABLE 4-2. TOXICITY Of CYANIDE TO SOIL BIOTA
Experimental Experimental Experimental
Tissue Soil Application
Chemical Porm Soil Concentration Concentration Rate
Species Applied Type (kg/ha)
Nitrifying bacteria Cyanide Calcareous NR* 100 of N NR
Nitrifying bacteria Cyanide Calcareous NR 200 of N NR
Nitrifying bacteria CN NR NR <200 NR
Tissue
Concentration
(pg/g) Effects
NR No effect on rate of
nitrogen conversion
SOX reduction in
nitrogen conversion
NR Readily transformed
or degraded depend-
ing on oxidation/
reduction conditions
References
Puller, 1977 (p.
Puller, 1977 (p.
Puller, 1977 (p.
14S)
145)
146)
NR • Not reported.
-------
SECTION 5
REFERENCES
Abramowitz, M., and I. A. Stegun. 1972. Handbook of Mathematical
Functions. Dover Publications, New York, NY.
American Conference of Governmental Industrial Hygienists. 1982.
Threshold Limit Values for Chemical Substances and Physical Agents
in the Working Environment with Intended Changes for 1983-84.
Cincinnati, OH.
Camp D. esser and McKee, Inc. 1984. Development of Methodologies for
Evaluating Permissible Contaminant Levels in Municipal Wastewater
Sludges. Draft. Office of Water Regulations and Standards, U.S.
Environmental Protection Agency, Washington, D.C.
Donigian, A. S. 1985. Personal Communication. Anderson-Nichols & Co.,
Inc., Palo Alto, CA. May.
Freeze, R. A., and J. A. Cherry. 1979. Groundwater. Prentice-Hall,
Inc., Englewood Cliffs, NJ.
Fuller, W. H. 1977. Movement of Selected Metals, Asbestos, and Cyanide
in Soil. Application to Waste Disposal Problems. EPA-600/2-77-
020. U.S. Environmental Protection Agency, Cincinnati, OH.
Gelhar, L. W., and G. J. Axness. 1981. Stochastic Analysis of
Macrodispersion in 3-Dimensionally Heterogeneous Aquifers. Report
No. H-8. Hydrologic Research Program, New Mexico Institute of
Mining and Technology, Soccorro, MM.
Gerritse, R. G., R. Vrieaema, J. W. Dalenberg and H. P. DeRoos. 1982.
Effect of Sewage Sludge on Trace Element Mobility in Soils. J.
Environ. Qual. 2:359-363.
Griffin, R. A. 1984. Personal Communication to U.S. Environmental
Protection Agency, ECAO - Cincinnati, OH. Illinois State
Geological Survey.
Pettyjohn, W. A., D. C. Kent, T. A. Prickett, H. E. LeGrand, and F. E.
Witz. 1982. Methods for the Prediction of Leachate Plume
Migration and Mixng. U.S. EPA Municipal Environmental Research
Laboratory, Cincinnati, OH.
Sikora, L. J., W. D. Burge and J. E. Jones. 1982. Monitoring of a
Municipal Sludge Entrenchment Site. J. Environ. Qual.
2(2):321-325.
U.S. Environmental Protection Agency. 1976. Quality Criteria for
Water. U.S. Environmental Protection Agency, Washington, D.C.
5-1
-------
U.S. Environmental Protection Agency. 1977. Environmental Assessment
of Subsurface Disposal of Municipal Wastewater Sludge: Interim
Report. EPA/530/SW-547. Municipal Environmental Reseo.-ch
Laboratory, Cincinnati, OH.
U.S. Environmental Protection Agency. 1978. Reviews of the
Environmental Effects of Pollutants: V. Cyanide. EPA 600/1-78-
027. U.S. Environmental Protection Agency, Cincinnati, OH.
U.S. Environmental Protection Agency. 1980. Ambient Water Quality
Criteria for Cyanides. EPA/440/5-80-037. U.S. Environmental
Protection Agency, Washington, D.C.
U.S. Environmental Protection Agency. 1982. Fate of Priv -ity
Pollutants in Publicly-Owned Treatment Works. EPA/440/1-82/333.
U.S. Environmental Protection Agency, Washington, D.C.
U.S. Environmental Protection Agency. 1983. Rapid Assessment of
Potential Groundwater Contamination Under Emergency Response
Conditions. EPA 600/8-83-030.
U.S. Environmental Protection Agency. 1984. Health Effects Assessment
for Cyanide. Final Draft. ECAO-CIM-H011. Cincinnati, OH.
September.
U.S. Environmental Protection Agency. 1985. Ambient Water Quality
Criteria for Cyanide. Unpublished.
5-2
-------
APPENDIX
PRELIMir
-------
where:
A, = X- [V* - (V*2 + 4D*
Al 2D*
_ Y - t (V*2 + 4D* x u*)*
2 ~ (4D* x t)*
BI = X— [V* + (V*2 + 4D* x
y + t (V*2 + 4D* x
B2 (4D* x t)*
and where for Che unsaturated zone:
C0 - SC x CF = Initial leachate concentration (yg/L)
SC = Sludge concentration of pollutant (mg/kg DW)
CF = 250 kg sludge solids/m3 Leachace =
PS x 103
PS = Percent solids (by weight) of landfilled sludge
20%
t = Time (years)
X = h = Depth to ground water (m)
D* = o x V* (m2/year)
a = Dispersivity coefficient (m)
V* = — 2 — (m/year)
0 x R
Q = Leachate generation rate (m/year)
6 = Volumetric water content (unitless)
R = 1 + J*££ x Kd = Retardation factor (unitless)
0
pdry = Dry bul-k density (g/mL)
Kd = foc x Koc (mL/g)
foc = Fraction of organic carbon (unitless)
Koc = Organic carbon partition coefficient (mL/g)
u* = ( ,-i
1
U = Degradation rate (day'1)
and where for the saturated zone:
C0 = Initial concentration of pollutant in aquifer as
determined by Equation 2 (ug/L)
t = Time (years)
X = AH = Distance from well to landfill (m)
D* = o x V* (m2/year)
a = Dispersivity coefficient (m)
A-2
-------
u* - K x i (m/year)
0 x R
K = Hydraulic conduct.'vity of Che aquifer (m/day)
i = Average hydrai'ic gradient between landfill and well
(unitless)
0 - Aquifer porosity (unitless)
R = 1 + £d£Z x Kd = Retardation factor = 1 (unitless)
0
since K Q.*"** - and B > 2
— K x i x 365 —
D. Equation 3. Pulse Assessment
C(Xt° = P(X,0 for 0 < t .< t0
co
= P(X,t) - P(X,t - t0) for t > t0
co
where:
to (for unsaturated zone) = LT = Landfill leaching time
(years)
t0 (for saturated zone) = Pulse duration at the water
table (x = h) as determined by the following equation:
t0 = [ o/08 c dt] * c
C( Y t)
P(X»t) = ft1 as determined by Equation 1
A-3
-------
B. Equation 4. Index of Groundvater Concentration Resulting
from Landfilled Sludge (Index 1)
1. Formula
Index 1 =
where:
Coax = Maximum concentration of pollutant at well =
maximum of C(Al,t) calculated in Equation 1
(Ug/U
2. Sample Calculation
12.9 Ug/L = 12.9 Ug/L
P. Equation 5. Index of Human Toxicity Resulting
from Groundwater Contamination (Index 2)
1. Formula
(II x AC) + DI
Index 2 =
where:
II = Index 1 = Index of groundwater concentration
resulting from landfiLled sludge (yg/L)
AC = Average human consumption of drinking water
(L/day}
DI = Average daily human dietary intake of pollutant
(Ug/day)
ADI = Acceptable daily intake of pollutant dig/day)
2. Sample Calculation
0.0034246095
A-4
-------
III. INCINERATION
Based on the recommendations of the experts at the OWRS meetings
(April-May, 1984), an assessment of this reuse/disposal option is
not being conducted at this time. The U.S. EPA reserves the right
to conduct such an assessment for this option in the future.
IV. OCEAN DISPOSAL
Based on the recommendations of the experts at the OURS meetings
(April-May, 1984), an assessment of this reuse/disposal option is
not being conducted at this time. The U.S. EPA reserves the right
to conduct such an assessment for this option in the future.
A-5
-------
TABLE A-l. INPUT DATA VARYING IN LANDFILL ANALYSIS AND RESULT FOR EACH CONDITION
>
Condition of Analysis
Input Data
Sludge concentration of pollutant, SC (Ug/g DW)
Unsaturated zone
Soil type and characteristics
Dry bulk density, f&Ty (g/aL)
Volumetric water content, 6 (unitless)
Fraction of organic carbon, foc (unitless)
Site parameters
Leachate generation rate, Q (in/year)
Depth to groundwater, h (m)
Dispersivity coefficient, a (m)
Saturated rone
Soil type and characteristics
Aquifer porosity, 0 (unitless)
Hydraulic conductivity of the aquifer,
K (a/day)
Site parameters
Hydraulic gradient, i (unitless)
Distance from well to landfill, A 4 (m)
Dispersivity coefficient, a (m)
1
476.2
1.53
0.195
0.005
0.8
5
0.5
0.389
4.04
0.02
100
10
2
2686.6
1.53
0.195
0.005
0.8
5
0.5
0.389
4.04
0.02
100
10
3
476.2
1.925
0.133
0.0001
0.8
5
0.5
0.389
4.04
0.02
100
10
4 5
476.2 476.2
NA° 1.5-
NA 0.195
NA 0.005
1.6 0.8
0 5
NA 0.5
0.389 0.371
4.04 3.29
0.02 0.02
100 100
10 10
6 7
476.2 2686.6
1.53 NA
0.195 NA
0.005 ' NA
0.8 1.6
5 0
0.5 NA
0.389 0.371
4.04 3.29
0.0005 0.0005
50 50
5 5
8
N«
N
N
V
N
N
N
N
N
N
N
N
-------
TABLE A-l. (continued)
>
Results
Unsaturated cone assessment (Equations 1 and 3)
Initial leachate concentration, Co (|ig/L)
Peak concentration, Cu (pg/L)
Pulse duration, to (years)
Linkage assessment (Equation 2)
Aquifer thickness, B (m)
Initial concentration in saturated cone, Co
fn»/l.i
1
119000
119000
5.00
126
119000
2
672000
672000
S.OO
126
672000
3
19000
19000
S.OO
126
119000
4
119000
119000
S.OO
253
119000
5
119000
119000
S.OO
23.8
119000
6
119000
119000
S.OO
6.32
119000
7
672000
672000
S.OO
2.38
672000
8
N
N
N
N
N
Saturated rone assessment (Equations 1 and 3)
Maximum well concentration, C^, (pg/L)
Index of groundwater concentration resulting
from landfilled sludge. Index 1 (ug/L)
(Equation 4)
Index of human toxicity resulting from
groundwater contamination, Index 2
(unitless) (Equation S)
12.9
12.9
73.0
73.0
12.9
12.9
12.9
12.9
68.8
68.8
S18
518
3.42x10-3 1.93x10-2 3.42xlO~3 3.42xlO'3 1.82xlO~2 0.137
15SOO
15500
4.11
aN •= Null condition, where no landfill exists; no value is used.
bHA = Not applicable for this condition.
------- |