&EPA
United States Office of Air Quality EPA-451/R-93-006
Environmental Protection Planning and Standards April 1993
Agency Research Triangle Park, NC 27711
Air/Superfund
AIR/SUPERFUND
NATIONAL TECHNICAL GUIDANCE
STUDY SERIES
ESTIMATION OF AIR IMPACTS FOR
SOLIDIFICATION AND STABILIZATION
PROCESSES USED AT SUPERFUND SITES
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EPA 451/R-93-006
ESTIMATION OF AIR IMPACTS
FOR SOLIDIFICATION AND STABILIZATION
PROCESSES USED AT SUPERFUND SITES
Report ASF - 34
Prepared for:
Office of Air Quality and Standards
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12tn Moor
Chicago, IL 60604-3590
April 1993
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DISCLAIMER
This report has been reviewed by the
Office of Air Quality Planning and Standards,
U.S. Environmental Protection Agency, and has
been -approved for publication as received from
the contractor. The contents reflect the
views and policies of the Agency, but any
mention of trade names or commercial products
does not constitute endorsement or
recommendation for use.
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TABLE OF CONTENTS
Page
INTRODUCTION 1
PROCESS DESCRIPTION 1
ESTIMATION OF VOC AIR EMISSIONS 5
Average Long-Term VOC Emission Rate 6
Short-Term VOC Emission Rate 6
ESTIMATION OF PARTICULATE MATTER AIR EMISSIONS 8
ESTIMATION OF AMBIENT AIR CONCENTRATIONS 12
ESTIMATION OF HEALTH EFFECTS 17
Cancer Effects Due to Long-Term Exposure 17
Non-Cancer Effects Due to Long-Term Exposure 29
Short-Term Exposure 30
EXAMPLE 31
CONCLUSIONS 35
REFERENCES 36
APPENDDC A PHYSICAL PROPERTY DATA FOR SELECTED ORGANIC
COMPOUNDS
APPENDIX B PHYSICAL PROPERTY DATA FOR SELECTED SEMI-VOLATILE
ORGANIC COMPOUNDS
11
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LIST OF FIGURES
Page
Process Flow Diagram for Ex-Site Stabilization and
Solidification 3
One-Hour Average Downwind Dispersion Factor Versus Distance
for Excavation With No Air Emission Controls 16
LIST OF TABLES
1 Default Values for Estimating Emissions from Solidification/Stabilization . . 9
2 Default Values for Estimating PM Emissions from S/S Processes 11
3 Metal Concentration and Enrichment Data (Z) 13
4 Example Scenarios for Stabilization or Solidification 14
5 Long-Term and Short-Term Health-Based Action Levels for Organic
Compounds in Ambient Air 18
6 Long-Term and Short-Term Health-Based Action Levels for Semi-Volatile
Organic Compounds in Air 26
7 Long-Term and Short-Term Health-Based Action Levels for Metals
in Ambient Air 28
8 Estimated Emission Rates and Ambient Air Concentrations . 35
9 Action Level Concentrations 35
111
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INTRODUCTION
The U.S. Environmental Protection Agency's Office of Air Quality Planning and
Standards and the Regional Air Offices have been given the responsibility to evaluate air
impacts from Superfund sites. An important part of this program is the analysis of air
impacts from various alternatives for cleaning up Superfund sites. Since these analyses
are frequently required for planning purposes prior to actual cleanup, they depend on
estimated emissions and ambient concentrations rather than on field measurements.
This report provides procedures for roughly estimating the ambient air
concentrations associated with the solidification/stabilization of contaminated soil or
sludge. These procedures are analogous to procedures for air strippers, soil vapor
extraction systems, and excavation that have previously been published1*2^.
Solidification/stabilization processes are used to immobilize toxic and hazardous
constituents in contaminated soil or sludge. Procedures are given to evaluate the effect
of treatment rate and contaminant concentration on the emission rates and on the
ambient air concentrations at selected distances from the treatment area.
Health-based ambient air action levels are also provided for comparison to the
estimated ambient concentrations. Many of the health levels have not been verified by
EPA or are based on extrapolations of oral exposures or occupational exposures. Their
use could either under or over estimate the potential health effects. The use of action
levels that are neither EPA-verified nor EPA-approved should be considered on a case-
by-case basis. The statements and conclusions presented in this report are those of the
authors and do not reflect U.S. EPA policy.
PROCESS DESCRIPTION
Information related to air emissions from solidification/stabilization (S/S)
processes is very limited. The following discussion is adapted from a recent compilation
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models4. Additional general information about S/S processes is contained in Cullinane,
etal.5.
Stabilization and solidification technologies are gaining increased use as Superfund
site remediation methods. The goal of these processes is to immobilize the toxic and
hazardous constituents in the waste, usually contaminated soil or sludge. This can be
accomplished by several means:
1) Changing the constituents into an immobile (insoluble) form;
2) Binding them in an immobile, insoluble matrix; or
3) Binding them in a matrix which minimizes the material surface exposed to
solvents (groundwater) which could leach the hazardous constituents.
A few S/S processes involve in-situ treatment, however, most generally require
excavation and other soil handling activities. Nearly all the commercially available
stabilization and solidification technologies are proprietary. S/S processes may be considered
to be point sources of VOC emissions if the process is enclosed or has an air collection
system.
Solidification and stabilization processes are usually batch operations, but may be
continuous. All ex-situ S/S processes follow the same basic steps shown in Figure 1.
Wastes are first loaded into the mix bin (wastes are sometimes dried before addition to the
bin), and other materials for the solidification or stabilization are added. The contents of the
bin are then thoroughly mixed. After a sufficient residence time, the treated waste is
removed from the bin. The amount of fixative added may be equal to the mass of the
contaminated material. The solidified material is usually formed into blocks and allowed to
cure for up to several days. The blocks can then be placed in lined excavations on-site.
This description does not apply, however, to in-situ treatment methods, which use a variety
of techniques (from applied high voltage to injection of stabilizing agents) to immobilize the
contaminated waste in-place without excavation or soils handling.
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Excavation of Contaminated
Soil or Sludge
Addition of Binding
or Stabilizing Agent
(Typical materials used
include Fly Ash, Portland
Cement, Cement Kiln Dust,
and LJme Kiln Oust)
Treated Soil or Sludge
Waste Returned to Ground
Where Mixture Hardens and Traps
Contaminants
Figure 1. Process Row Diagram for Ex-Situ Stabilization and Solidification
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Typical raw materials used in stabilization processes include fly ash, portland
cement, cement kiln dust, lime kiln dust, or hydrated lime. Other additives that may be
used to solidify or encapsulate wastes include asphalt, paraffin, polyethylene, or
polypropylene.
During the solidification/stabilization soil remediation process, there are
numerous possible VOC and PM emission sources, including fugitive emissions before
treatment, emissions during excavation and soil handling, during the preparation of the
mixing agent, during the treatment of the contaminated soil, and, finally, emissions from
the treated soil after remediation.
The primary source of VOC emissions from stabilization and solidification
processes is volatilization of organic contaminants in the material to be treated.
Volatilization can occur during waste handling activities such as soil excavation and
transport or during the process of mixing the binding agents with the waste. Also, some
evaporative emissions will occur from waste even after stabilization, especially during the
curing period immediately after the blocks are formed. Lab studies, though, have shown
that the largest fraction of volatile loss occurs during the mixing phase because heat may
be required to assist mixing or may be generated by exothermic stabilization reactions.
In general, VOC emissions from stabilization and solidification processes will
depend on the type and concentration of the VOCs in the waste, the duration and
thoroughness of the mixing, the amount of heat generated in the .process, and the
average batch size processed. The longer or more energetic the mixing and processing,
the greater likelihood that organic compounds will volatilize. The volatile losses will also
increase as the temperature of the waste/binder mixture increases. Binding agents 'vith
high lime contents generally cause highly exothermic reactions. The batch size influences
volatilization by affecting the mean distance a volatilized molecule has. to travel to reach
the air/solid interface at the surface of the stabilized waste. The larger the block of
material, the lower the rate of volatilization.
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Factors influencing the (uncontrolled) VOC emission rate also include the soil
permeability before and after remediation, the exact treatment process and how the mixing is
accomplished, and the composition of the mixing agent. Indeed, the latter may be
specifically designed to control one certain class of contaminants, and may not be effective
for any others. The impermeability of the treated soil will also determine the amount of
emissions (and leachate) that escape.
Emissions of particulate matter (PM) from S/S processes also can be significant. The
PM emission potential will depend on the moisture content and particle size distribution of
the material to be treated. Process design and operating factors such as the duration and
thoroughness of the mixing and the degree to which the process is enclosed also will affect
the PM emission rate. Additional PM emissions may result from material handling
operations associated with the stabilization agent or other raw materials (e.g., fly ash, kiln
dust).
ESTIMATION OF VOC AIR EMISSIONS
Little information exists about the fate of volatile contaminants in wastes treated by
stabilization and solidification methods. A literature search found no available field data on
air emissions at Superfund sites using this type of remediation technology. Laboratory
studies, however, have estimated that 70-90% of the volatile contaminants in the treated
waste eventually evaporate. Experiments also show that most of the loss occurs within 60
minutes of mixing the waste with binding agents.
There are several alternative approaches for estimating the emissions from S/S
processes. The best method is to directly measure the emissions during full-scale or pilot-
scale operation. The next best method is to estimate the emissions using predictive equations
with site-specific inputs. If site-specific inputs are not available, a conservative estimate can
be made using default values for the input parameters. Equations are given below for
estimating an average long-term emission rate (Equation 1) and a short-term emission rate
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(Equation 2). Equation 2 is the recommended equation for estimating VOC emissions;
Equation 1 can be used as a gross check of total emissions.
Average Long-Term VOC ftmfosioa Rate (Worst Case)
A simple check of the total emissions potential for the site should be made by
dividing the total mass of a given contaminant to be removed by the expected duration of the
clean-up:
ER * (SV)(C)OS)(1) / tR (Eq. 1)
where ER = Average worst case emission rate (g/sec);
Sv = Volume of contaminated soil to be treated (m3);
C = Average contaminant concentration 0*g/g);
0 = Bulk density of soil (g/cm3);
1 = Constant (g/10Vg * 10*cm3/m3); and
tR = Duration of remediation (sec).
The volume of contaminated soil and the total mass of each contaminant of concern present
are typically determined during the remedial investigation (RI) of the site, while the fraction
of contaminated soil that must be treated is typically determined during the feasibility study
(FS) of the site. Final clean-up criteria should also be considered when calculating the
volume of soil to be treated. The duration of the clean-up will usually be limited by the
operational rate of the treatment process. For Equation 1, a typical default value for bulk
density of uncompacted soil is 1.5 g/cm3. The following section contains an empirical
equation for estimating a short-term emission rate.
Short-Term VOC Emission Rate
VOC emissions from stabilization and solidification processes can be estimated using
a mass-balance approach. The following equation is applicable to ex-situ
solidification/stabilization processes:
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ER = C Q (2.78 x 10-7)(V/100) (Eq. 2)
where ER = Emission rate of contaminant i (g/sec);
C = Concentration of contaminant i in soil 0*g/g);
Q = Treatment (feed) rate of soil (kg/hr);
2.78 x 10"7 = Conversion factor (g/kg • g/jtg • hr/sec); and
V = Fraction of contaminant i volatilized (%).
The same equation can be used for in-situ processes, if the treatment rate, Q, is
calculated as follows:
Q = Q' 0 1000 (Eq. 3)
where Q' = Treatment (feed) rate of soil (nrVhr);
j8 = Bulk density of soil (g/cm3); and
1000 = Conversion factor (kg/g • cm3/m3).
Site-specific field data must be collected (e.g., during the RI/FS) to provide the input
data necessary to generate reasonably accurate estimates of air emissions. The only field
data required is knowledge of the specific contaminants present in the soil or waste to be
stabilized or solidified and the average contaminant concentration. The treatment rate of the
unit can be obtained from the vendor or estimated from design documents and the results of
any feasibility study. The fraction of VOCs that will be stripped during the process will be
highly dependent on the system design and operating procedures. Field test data should be
obtained to estimate this parameter. The concentration of contaminant in the soil or sludge
to be treated should be available from remedial investigation studies.
The major limitation of these equations is the lack of air emissions data available for
developing default values for the term in the model for the percent of VOCs lost from the
process. Only one field study5 and two laboratory studies7-8-9 of air emissions- from these
processes have been identified, though a third study10 does provide some useful performance
data. These studies show that from 40 to 100% of the VOCs present in the waste are lost
during the mixing step of the processes. Essentially all of the VOCs are lost to the
atmosphere by the end of the curing step.
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Table 1 gives default values to be used in Equations 1, 2, and 3. Feed rates vary
widely; values of 5 to 130 tons/hr have been published for ex-situ processes and 25 to 100
tons/hr for in-situ processes. Information is given in Table 1 for estimating emissions of
semi-volatile organic compounds (SVOCs). Organic compounds can be divided based on
vapor pressure at 25°C.
VOCs = Vapor Pressure S1 mm Hg; and
SVOCs = Vapor Pressure < 1 mm Hg.
Vapor pressure data for organic compounds can be found in Appendices A and B.
ESTIMATION OF PARTICULATE MATTER AIR EMISSIONS
The emissions of PM from stabilization and solidification have been found to be over
1 kg/hr for full-scale operations6. No models, however, are available for estimating PM
emissions from the processing step of stabilization and solidification operations. An emission
factor has been published that can be converted into an emission estimation equation13:
ER = (0.05)(Q)(2.78xl04) . (Eq. 4)
where ER = Emissions (g/sec);
0.05 = Emission factor (g/kg);
Q = Treatment rate (kg/hr); and
2.78x10"* = Conversion factor (hr/sec).
Emissions from materials handling operations such as excavation, storage, and reagent
transfer also should be considered when addressing air impacts from the total site operations.
Procedures for estimating these emissions can be found in Reference 4.
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Table 1
Default Values for Estimating Emissions From Solidification/Stabilization
Parameter
Feedrate
Bulk density of
soil
% Volatilized
(VOCs)
% Volatilized
(Semi-Volatiles)
Symbol
Q
fl
V
V
Units
kg/hr
g/cm3
%
%
Default
Value
45,000
1.5
80"
100b
5a
Expected Range
4,500-120,000 (ex-situ)
23,000-91,000 (in-situ)
1.0 - 2.0
40-100*
100"
0-5
Reference
10
11
12
9
9
Author's
Estimate0
•
"During mixing
"After 40 days of curing
'Based on very limited data adapted from Reference 6
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PM emissions from the transfer of the stabilized waste can be estimated as14:
f \« ^ 5)
0.000561 — 1 (M)
E = Hi?"1
where E = Emissions (g);
0.00056 = Empirical factor (g/kg);
U = Wind speed (m/sec);
2.2 = Empirical factor (m/sec);
M = Mass of material handled (kg);
XIQO = Moisture fraction (%); and
2 = Empirical factor (%).
The output from Equation S can be converted into an emission rate by dividing by the
expected duration of the transfer operations. The minimum Meld data required to estimate
emissions using Equation 5 are the soil moisture content and the mass of material handled.
Default values for use with equations 4 and 5 are given in Table 2.
If the dust is contaminated, the PM emissions from Equation 4 or 5 may be translated
to emission rates of the contaminant as follows:
E, = X, E (Eq. 6)
where EI = Emissions of contaminant i (g); and
Xj = Fraction of contaminant i in paniculate matter (unitless).
In general, the dust and silt at a site will contain a higher fraction of the metal species than
the bulk soil at the site; i.e. the paniculate matter is enriched with the metals13.
10
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Table 2.
Default Values for Estimating PM Emissions from S/S Processes
Parameter
Treatment rate
Wind speed
Moisture fraction
Symbol
Q
U
XffiO
Units
kg/hr
m/sec
%
Default Value
45,000
4,4
2
Expected Range
4,500 - 120,000 (ex-situ)
23,000 -91, 000 (in-situ)
0.6 - 6.7
0.25 - 4.8
Reference
10
11
14
14
11
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Therefore, Xj is equal to:
Xj = C Z 10^ (Eq. 7)
where C = Concentration of metal in the bulk soil (ug/g);
Z = Enrichment factor (unitless); and
10"* = Conversion factor (g/ftg).
Table 3 contains default values of metal enrichment factors for use in Equation 7. The
minimum data needed from RI/FS or other site investigations is the identity and average
concentration of metal species in the soil or sludge. In addition to metals, paniculate
matter also may contain SVOCs. Equation 6 is applicable for SVOCs as well as metals.
The equations presented in this section are all empirically based and drawn from
measurements at actual sites; they are meant to predict the behavior of average sites. If
a particular site has unusual meteorological conditions, nibble, debris, or soils with high
silt content, etc., the accuracy of these models may be affected. It is prudent to always
monitor actual field emissions, at least from some test location, to verify the model
predictions.
ESTIMATION OF AMBIENT AIR CONCENTRATIONS
Estimates of short-term, worst-case ambient concentrations should be obtained by
using site specific release parameters in the EPA's TSCREEN model15. Estimates of
long term concentrations should be obtained by using EPA's Industrial Source Complex
(ISCLT) model. Here, for simplicity, the annual average estimates are derived by
multiplying the short term estimate obtained from the TSCREEN model, by a conversion
factor to account for variations of wind direction over time. This approach results in a
higher estimate of the annual average concentration than if the ISCLT model with site
specific data, is used.
Table 4 presents three remediation scenarios that address both ex-siru and in-situ
processes. The scenarios were developed based on a review of the existing literature.
12
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Table 3.
Metal Concentration and Enrichment Data (Z)
CAAA* Metals
Antimony (Sb)
Arsenic (As)
Beryllium (Be)
Cadmium (Cd)
Chromium (Cr)
Cobalt (Co)
Lead (Pb)
Manganese (Mn)
Mercury (Hg)
Nickel (Ni)
Selenium (Se)
Other Metals
Barium (Ba)
Silver (Ag)
Median Enrichment Factor (Z)
-
1.28
—
1.31
4.72
—
734
—
3.00
~
2.00
1.85
1.00
Source: Reference 14
'CAAA = Clean Air Act Amendments of 1990
13
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Table 4.
Example Scenarios for Stabilization or Solidification
Parameter
Ex-Situ Prpcesse?
Treatment Unit:
Dimensions
Area
Release height
In-Situ Prpcesses
Treatment Area:
Dimensions
Area
Release Height
Units
m
m2
m
m
m2
m
Scenario
5x5x2
25
2
10x10
100
1
14
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Figure 2 can be used to estimate the maximum hourly ambient air concentration for an
emission rate of 1 gram per second at selected distances downwind from a treatment site. Of
the variables listed in Table 4, only the physical dimensions of the treatment area factors into
the estimated downwind dispersion. The curves were calculated according to the following
assumptions: 1) the combined emission rate is 1 gram per second; 2) a flat terrain without
any structures near the treatment site; 3) the emission plume is of low, positive buoyancy;
4) the only downwash structure is the ex-situ treatment unit; 5) the emissions are uniformly
distributed over the emitting area and constant over time; and 6) the receptors are at ground
level. The dispersion model used is not reliable for estimating air concentrations close-in to
area sources. Estimates should not be made for any downwind location that is closer to the
source than the side length of the source.
If a given source is larger than the example scenario, Figure 2 may still be used. The
dispersion factor, in micrograms/m3 per g/sec, obtained from Figure 2 can be substituted into
Equation 8 to estimate the maximum hourly ambient concentration and into Equation 9 to
estimate the annual average ambient air concentration for a given downwind distance. Since
TSCREEN provides maximum short-term estimates, the factor of 0.08 in Equation 9 is used
to convert the short-term estimate to an annual average estimate.
Cm = (ER)(F) (Eq. 8)
C, = (ER)(F)(0.08) (Eq. 9)
where Cm = Maximum hourly ambient air concentration(/ig/m3);
G, = Annual average ambient air concentration (/tg/m3);
ER — Emission rate (g/sec); and
F = Dispersion Factor from Figure 2 G*g/m3/g/sec).
The 0.08 factor in Equation 9 was developed by the U.S. EPA for point sources.
This factor has recently been revised and it is still under review by EPA and may be subject
to further change. There is no EPA policy for converting from hourly to annual estimates
for area sources. Various factors have been published that range up to 0.08." Factors up to
0.20 have been suggested for certain specific locations17. Graphical estimation tools in lieu
15
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of these factors also have been proposed.13-18 It is assumed that this point source factor can
be applied to area sources without greatly increasing the overall uncertainty of the air impact
estimate. As previously stated, the recommended approach is to use ISCLT to estimate long-
term concentrations.
ESTIMATION OF HEALTH EFFECTS
Cancer Effects Due to Long-Ten
Potential cancer effects resulting from long-term exposure to substances emitted to the
air can be evaluated using inhalation unit risk factors.' Inhalation unit risk factors are a
measure of the cancer risk for each /xg/m3 of concentration in the ambient air. They are
available on EPA's Integrated Risk Information System (IRIS), the Agency's preferred
source of toxicity information. User Support can be contacted at (513) 569-7254. The next
best source of inhalation unit risk factors is EPA's Health Effects Assessment Summary
Tables (HEAST) which are updated annually.19 Inhalation unit risk factors listed in IRIS as
of January 1993 or in HEAST (FY 1992) are given in Table 5 for 168 volatile and semi-
volatile organic compounds. This is an updated version of the same table contained in
References 2 and 3. Similar information is given in Tables 6 and 7 for selected semi- volatile
organic compounds and metals, respectively.
Equation 10 can be used to estimate the cancer risk at a specified distance downwind
of the excavation area. Cancer risk is a measure of the increased probability of developing
cancer in a lifetime as a result of the exposure in question. Equation 10 assumes continuous
exposure (24 hours/day, 365 days/year for 70 years) to the estimated annual average
concentration in air.
R = (CJ(IUR) (Eq. 10)
17
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R is the cancer risk from long-term exposure to a specific compound in air, (unitless);
Ca is the annual average ambient concentration estimated from Equation 9, 0*g/m3); IUR is
the inhalation unit risk factor, (/ig/m3)'1 obtained from Tables 5, 6, or 7.
If the source operates for less than 70 years, multiply C, by x/70, where x is the
expected operating time of the source in years before using Equation IT). If more than one
contaminant is present, the cancer risks for each contaminant can be summed to derive the
total cancer risk at a specified distance downwind of the source.
Non-Cancer Effects Due to Long-Term Exposure
Non-cancer effects can be evaluated by using chronic inhalation reference
concentrations (RfCs). An inhalation RfC is an estimate (with uncertainty spanning perhaps
an order of magnitude) of continuous exposure of the human population to contaminants in
the air that is likely to be without appreciable risk of deleterious effects during a lifetime.
During the past three years, the EPA has become increasingly active in the development of
chemical specific RfCs.
If inhalation RfCs were not available from either IRIS or HEAST, then chronic oral
reference dose (RfD) data (in mg/kg/day) were multiplied by 70 kg (average body weight of
an adult), then divided by 20 m3/day (average adult inhalation rate), and finally multiplied by
1000 /*g/mg to derive a value in ng/m3. This methodology was selected for this screening
document. The EPA, however, does not condone derivation of RfCs from data for other
routes of exposure on a chemical specific basis.
The EPA considers the minimum basis for the derivation of an RfC to be a properly
conducted inhalation study that examines portal of entry effects. Portal of entry effects are
particularly important with respect to inhalation. There are many known cases where
respiratory effects due to inhalation exposure are much more severe than effects resulting
from equivalent oral doses. Therefore, ambient air action levels based on extrapolated oral
29
-------
data should be used cautiously since there may be significant differences between the oral
and inhalation exposure pathways.
For compounds lacking RfC or RfD values, action levels were based on occupational
exposure levels recommended by the Occupational Safety and Health Administration
(OSHA)20 and the American Conference of Governmental Industrial Hygienists (ACGIH)21.
The action levels were estimated by using the lower of the OSHA Permissible Exposure
Limit-Time Weighted Average (PEL-TWA) level (or ceiling value) or the ACGIH Threshold
Limit Value-Time Weighted Average (TLV-TWA) level (or ceiling value). The lower value
was divided by 1000 to compensate for differences between occupational and residential
exposures. It should be noted that occupational exposure levels are not intended for
evaluation or control of community air pollution or in estimating the toxic potential of
continuous, uninterrupted exposures. Therefore, ambient air action levels based on
occupational exposure limits are not precise distinctions between safe and dangerous ambient
air concentrations, nor are they necessarily indices of toxicity.
Long-term ambient air action level concentrations for non-carcinogens based on RfCs,
extrapolated RfOs and occupational exposure levels are also listed in Tables 5, 6, and 7.
The action levels are in units of /tg/m3 to facilitate comparison to the ambient air
concentrations estimated from Equation 9.
Short-Term Exposure
The short-term (one hour) action levels, in /xg/m3, are presented in the last column of
Tables 5, 6, and 7. The listed values were obtained by dividing the lowest of (1) the OSHA
PEL-TWA or (2) the ACGIH TLV-TWA (or ceiling limits if 8-hour averages are not
available) by 100. Division by 100 accounts for variations in human sensitivity (occupational
levels are designed to protect healthy adult workers) and for uncertainties in using
occupational exposure levels to derive ambient air action levels.
30
-------
The occupational exposure levels on which the short-term action levels are based are
subject to change. To check the values in Tables 5, 6, and 7 (or to derive values for
compounds not listed in the tables), determine the current OSHA PEL-TWA values by con-
sulting 29 CFR Section 1910 and the most recent edition of the ACGffl publication entitled
Threshold limit Values and Biological Exposure Indices.
*
The short-term action levels listed in Tables 5, 6, and 7 can be compared directly
with the estimated maximum hourly ambient air concentrations obtained by using Equation 8
and Figure 2. Use of the short term action levels should consider that no EPA accepted
method exists to determine the short-term concentrations of airborne chemicals acceptable for
community exposure.
EXAMPLE
The following steps illustrate the use of the estimation procedures presented in this
document. The goal is to estimate the maximum hourly and annual average ambient air
concentrations at the nearest receptor to an S/S area and compare these values to the action
level concentrations listed in Tables 5, 6, and 7.
Step 1 First, collect all necessary information. For this example, assume a
site that has approximately 10,000 m3 of soil contaminated with 100
/ig/g of lead. The site also contains chloroform and 1,1,1-
trichloroethane at concentrations in the soil of 0.01 and 0.05 ug/g,
respectively. The material will be treated in-situ using a proprietary
stabilization process. The treatment rate has not yet been determined,
nor has the need for air emission controls, so a default rate of 45,000
kg/hour and no air emission controls are assumed. The S/S process is
expected to be in continual operation for 14 days (1.210 x 10* seconds).
The bulk density of the soil at the site averages about 1.5 g/cm3. The
nearest off-site downwind receptor is 400 meters away.
Step 2 Estimate the total emissions potential for the site. Using Equation 1,
the worst-case average long-term emission rate of chloroform would be:
31
-------
ER - aWW01X14Xl) - 1.24 x 10* g/sec
(1.21 x 106)
The average long-tenn emission rate for 1,1,1-trichloroethane is
6.20x10"* g/sec, and for lead it is 1.24 g/sec. All these rates assume
that 100% of the contaminant is lost to the atmosphere and that all
contaminated material is treated.
•
Step 3 Estimate the VOC emission rate of each compound from the S/S
operation. The appropriate data are used with Equations 2 and 3.
For chloroform, the emission rate would be:
ER - (0.01)(45,000)(2.78xlO-7)(100/100) = \35\IV* g/sec
The VOC emission rate for 1,1,1-trichloroethane is 6.26x10"* g/sec.
Step 4 Estimate the PM and metal emissions. The paniculate matter
emissions will be the sum of PM emissions from mixing and transfer
operations. From Equation 4, the mixing emissions are:
ER = (0.05)(45,000)(2.78xlO-4) = 0.63 g/sec
From Equation 5, the transfer emissions for PM can be calculated.
The mass of material handled is 45,000 kg/hr or 12.5 kg/sec.
Assuming default values of 4.4 m/sec for wind speed and 2% for
moisture content:
/44V-3
0.00056— 12.5
= 0.0172 g/sec
The total emission rate for paniculate matter is the sum of the two
rates:
ERPM = 0.63 + 0.017 = 0.65 g/sec.
The fraction of this value that is lead can be determined using the
enrichment factor for lead of 7.34 from Table 3 and Equation 7:
Xlead = (100)(7.34)(10^) = 7J4X10"4
32
-------
This fraction can then be'used along with the total emission rate in
Equation 6:
Mead
(7.34xl04)(0.65) = 4.8x10-* g/sec
Step 5 Compare the estimated emission rates from Step 3 and 4 to those from
Step 2. The comparison is:
Compound
Chloroform
1,1, 1-Trichloroethane
Lead
Equation 1
Emission Rate
(g/sec)
1.24X10-4
6.20X104
1.24
Equation 2
Emission Rate
(g/sec)
1.25x10-*
6.26x10-*
4.8X1O4
Step 6
The VOC emission rates estimated using Equations 2 and 3 are
essentially the same as the total emissions potential for the site. This is
expected since the default value used for the percent of the contaminant
that is volatilized is 100%.
The estimated emissions of lead are far below the total amount of lead
present, which is as expected since far less than 100% of the lead
present would be expected to become airborne. The estimated VOC
and PM emission rates are used below to assess air impacts.
Estimate the downwind ambient air concentrations. From Figure 2, the
maximum hourly ambient air concentration at a distance of 400 meters
for an in-situ process with a treatment area of 100 m2 is approximately
3,000 ug/m3 per g/sec emission rate. This corresponds to an annual
average dispersion factor of 240 ug/m3 per g/s (3,000 x 0.08 = 240).
Using Equation 8, the hourly average ambient air concentration for
chloroform would be:
Cm * (1.25xl04)(3000) = 0.38 ug/m3
33
-------
Using Equation 9, the annual average air ambient concentration for
chloroform would be:
C. = (0.038)(0.08) = 0.030 ug/m3
The ambient air concentrations estimated from Equations 8 and 9 are
presented in Table 8.
Step 7 Compare the downwind concentrations to the action level ambient air
concentrations. The short-term and long-term action levels from Tables
5, 6, and 7 for the compounds of interest are presented in Table 9. Of
the estimated maximum hourly ambient concentrations, only lead is
within an order of magnitude of the applicable short-term action levels.
The annual average ambient concentrations are below the applicable
long-term action levels for the VOCs as is the estimated concentration
for lead.
Step 8 Document the results of the air pathway analysis and define a future
course of action. Based on these screening level results, a more
rigorous analysis of the air impacts is not necessary. The air impacts
should be re-examined, however, when site-specific input data are
available, if the inputs differ from the default values. Also, it would
still be adviseable to perform an ambient air monitoring program during
the remediation to document actual worker and community exposures.
CONCLUSIONS
The procedures presented here are not intended to negate the need for rigorous
analyses that consider site specific meteorological conditions and the health effects of the
specific compounds involved. Although the procedures are based on what is typical and
reasonable for cleaning up Superfund sites, the underlying assumptions need to be kept in
mind. For example, emission models assume typical operating conditions, dispersion models
assume Gaussian distribution of the plume and many of the health levels are not endorsed by
the Environmental Protection Agency. EPA's Regional Toxicologist should be contacted for
general lexicological information and technical guidance on evaluation of chemicals without
established toxicity values.
34
-------
Table 8.
Estimated Emission Rates and Ambient Air Concentrations
Chloroform
1,1, 1-Trichloroethane
Lead
Soil Concentration
For Example
Problem G»g/g)
0.01
0.05
100
Emission Rate
(g/s)
1.25 x 104
6.26 x 104
4.8 x 104
Ambient Concentrations
Oig/m3)
Maximum
Hourly
0.38
1.9
1.4
Annual Average
0.030
0.15
0.12
Table 9.
Action Level Concentrations
Chloroform
1,1, 1-Trichloroethane
Lead
Action Levels /tg/m3
Short-Term
98
19,000
1.5
Long-Term
0.0431
l.OOO2
0.15
'Based on 10"*, 70-year risk.
2Based on reference dose concentrations (RfCs).
35
-------
ICES
1. Eklund, B., S. Smith, and M. Hunt. Estimation of Air Impacts For Air
Stripping of Contaminated Water. EPA-450/1-91-002. May 1991.
2. Eklund, B., S. Smith, P. Thompson, and A. Malik. Estimation of Air
Impacts For Soil Vapor Extraction (SVE) Systems. EPA Contract No. 68-D1-
0031, WA13. December 2, 1991.
3. Eklund, B., S. Smith, and A. Hendler. Estimation of Air Impacts for the
Excavation of Contaminated Soil. EPA-450/1-92-004. March 1992.
4. Eklund, B. and C. Albert. Models for Estimating Air Emission Rates From
•Superfund Remedial Actions. EPA-451/R-93-001. March 1993.
5. Cullinane, M. L. Jones, and P. Malone. Handbook for
Stabilization/Solidification of Hazardous Waste. EPA/540/2-86/001. June
1986.
6. Ponder, T.C. and D. Schmitt. Field Assessment of Air Emissions From
Hazardous Waste Stabilization Operations. In: Proceedings of the 17th Annual
Hazardous Waste Research Symposium, EPA/600/9-91/002. • April. 1991.
7. Weitzman, L., L. Hamel, P. dePercin, B. Blaney. Volatile Emissions from
Stabilized Waste. In: Proceedings of the Fifteenth Annual Research
Symposium. EPA-600/9-90/006. February 1990.
8. Weitzman, L., L. Hamel, and S. Cadmus. Volatile Emissions From Stabilized
Waste - Final Report. Report for EPA/RREL, Cincinnati under EPA Contract
No. 68-02-3993, WA32 and 37. May 1989.
9. Sykes, A.L., W.T. Preston, and D.A. Grosse. Volatile Emissions from
Stabilization/Solidification of Hazardous Waste. Presented at the 85th Annual
AWMA Meeting (Paper 98.07), Kansas City, MO, June 21-26, 1992.
10. Stinson, Mary K. EPA SITE Demonstration of the International Waste
Technologies/Geo-Con In Situ Stabilization/Solidification Process. Journal of
Air & Waste Management vol. 40, no. 11. November 1990.
11. U.S. EPA. HAZCON Solidification Process, Douglassville, PA - Applications
Analysis Report. EPA/540/45-89/001. May 1989.
12. U.S. EPA. Superfund Exposure Assessment Manual (SEAMs). EPA/540/1-
88/001. April 1988.
13. Eklund, B., et al. Air/Superfund National Technical Guidance Study Series,
Volume HI: Estimation of Air Emissions from Cleanup Activities at
Superfund Sites. Report No. EPA-450/1-89-003. NTIS PB89180061/AS.
January 1989.
36
-------
14. Cowherd, C., P. Englehart, G. Muleski, and J. Kinsey. Hazardous Waste
TSDF Fugitive Paniculate Matter Air Emissions Guidance Document. EPA
450/3-89-019. May 1989.
IS. U.S. EPA, A Workbook of Screening Techniques for Assessing Impacts of
Toxic Air Pollutants. EPA-450/4-88-009. September 1988.
16. Huey, N.A. and G J. Schewe. Empirical Factor Estimation of Air Toxic
Source Impacts. In: Proceedings of HMC/Superfund '92. Published by
Hazardous Materials Control Resources Institute, Greenbelt, Maryland. 1992.
17. Huey, N.A. (U.S. EPA, Region VII). Personal communication to Bart Eklund
(Radian Corporation). April 1993.
18. Guinnup, D.E. A Tiered Modeling Approach For Assessing the Risks Due to
Sources of Hazardous Air Pollutants. EPA-450/4-92-001. March 1992.
19. Health Effects Assessment Summary Tables (HEAST). U.S. Environmental
Protection Agency, Wash. D.C., OERR 9200.6-303(92-1), NTIS No.
PB91-92199, March 1992.
20. 29 CFR ch. XVII. Subpart Z. Section 1910.1000. July 1, 1990.
21. 1992-1993 Threshold Limit Values for Chemical Substances and Physical
Agents and Biological Indices, American Conference of Governmental
Industrial Hygienists, Cincinnati, Ohio, 1992.
37
-------
APPENDIX A
PHYSICAL PROPERTY DATA
FOR SELECTED ORGANIC COMPOUNDS
(For compounds in Table 5 of the report)
Source: Reference 4
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APPENDIX B
PHYSICAL PROPERTY DATA
FOR SELECTED SEMI-VOLATILE ORGANIC COMPOUNDS
(For compounds in Table 6 of the report)
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