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to gross effects such as death. The effects of greatest concern are the
ones that are irreversible and impair the normal functioning of the indi-
vidual. Some of these effects include respiratory toxicity, developmental
and reproductive toxicity, central nervous system effects, and other
systemic effects such as liver and kidney toxicity, cardiovascular toxic-
ity, and immunotoxicity.
E.2.1 Health Benchmark Levels •;•
For chemicals that give rise to toxic endpoints other than cancer and
gene mutations, there appears to be a level of exposure below which adverse
health effects usually do not occur. This threshold-of-effect concept
maintains that an organism can tolerate a range of exposures from zero to
some finite v^lue without risk of experiencing a toxic effect. Above this
threshold, toxicity is observed as the organism's homeostatic, compensat-
ing, and adaptive mechanisms are overcome. To provide protection against
adverse health effects in even the most sensitive individuals in a popula-
tion, regulatory efforts are generally made to prevent exposures from
exceeding a health "benchmark" level that is below the lowest of the
thresholds of the individuals within a population.
Benchmark levels, termed reference doses (RfDs), are operationally
derived from an experimentally obtained no-observed-effect level or a
lowest-observed-effect level by consistent application of generally order-
of-magnitude uncertainty factors that reflect various types of data used to
estimate the RfD. The RfD is an estimate (with uncertainty spanning
perhaps an order of magnitude or greater) of daily exposure to the human
population (including sensitive subpopulations) that is likely to be with-
out an appreciable risk of deleterious effect.
The Agency has developed verified oral RfD for a large number of
chemicals, but has only recently established an internal work group to
begin the process for establishing inhalation RfDs. Agency-verified
inhalation reference doses for acute and chronic exposures will be used in
this analysis when they become available. Unverified inhalation reference
doses that have been developed by the Agency may be used on an interim
basis after careful review of the supporting data base.
E-28
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E.2.2 Noncarcinogenic Chemicals of Concern
A preliminary list of 179 TSDF chemicals of concern for the noncancer
health assessment is shown in Table E-8. Constituents were drawn from the
Agency's final rule on the identification and listing of hazardous waste
(Appendix VIII)14 and from the Industry Studies Data Base, a hazardous
waste data base developed by EPA's Office of Solid Waste.15 To be selected
from these sources, the chemical must have had either an Agency-verified
oral reference dose (as of September 30, 1987),16 or a Reference Air
Concentration (RAC) found in the Agency's proposed rule on the burning of
hazardous waste in boilers and industrial furnaces.17 Additional chemicals
were added to Table E-8 based on knowledge of a high toxicity associated
with that substance.
E.3 EXPOSURE ASSESSMENT
Three models were used to assess exposure, and ultimately risks, for
air emissions from TSDF. The Humari Exposure Model (HEM) was used to calcu-
late the number of people exposed to predicted ambient concentrations of
total volatile organics (VO) at each of about 2,300 TSDF in the United
States. The results of these analyses were used to quantify annual cancer
incidence. To determine the maximum lifetime cancer risk, the Industrial
Source Complex Long-Term (ISCLT) model was used to estimate the highest
ambient concentrations of VO in the vicinity of two TSDF. In addition,
this model was used in the evaluation of chronic noncancer health effects.
Finally, the Industrial Source Complex Short-Term (ISCST) model was used to
estimate ambient concentrations of individual chemicals of concern for the
acute noncancer health effects assessment and as a preliminary screen for
the chronic noncancer health effects assessment. Each of these is briefly
described below.
E.3.1 Human Exposure Model
In addition to the composite unit risk estimate, a numerical expres-
sion of public exposure to the pollutant is needed to produce quantitative
expressions of cancer incidence. The numerical expression of public
exposure is based on two estimates: (1) an estimate of the magnitude and
location of long-term average air concentrations of the pollutant in the
vicinity of emitting sources based on air dispersion modeling; and (2) an
E-29
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TABLE E-8. TSDF CHEMICALS - NONCANCER HEALTH EFFECTS ASSESSMENT
Chemical
Chemical
acetone (67-64-1)
acetaldehyde3 (75-07-0)
acetonitrile (75-05-8)
acetophenone (98-86-2)
acetyl chloride (75-36-5)
l-acetyl-2-thiourea (591-08-2)
acrolein3 (107-02-8)
acrylic acid (79-10-7)
acrylonitrilea (107-13-1)
aldicarb (116-06-3)
aldrin3 (309-00-2)
allyl alcohol (107-18-6)
ally! chloride3 (107-05-1)
aluminum phosphide (20859-73-8)
5-aminomethyl-3-i soxazol ol
(2763-96-4)
4-aminopyridine (504-24-5)
ammonia (7664-41-7)
ammonium vanadate (7803-55-6)
antimony (7440-36-0)
arsenic9 (7440-38-2)
barium (7440-39-3)
barium cyanide (542-62-1)
benzidine3 (92-87-5)
benzoic acid (65-85-0)
beryllium3 (7440-41-7)
1,1-biphenyl (92-52-4)
bi s(2-ethy1hexyl)phthalate3
(117-81-7)
bromodichloromethane (75-27-4)
bromoform (75-25-2)
butanol (71-36-3)
cadmium3 (7440-43-9)
calcium chromate3 (13765-19-0)
calcium cyanide (592-01-8)
carbon disulfide (75-15-0)
carbon oxyfluoride (353-50-4)
carbon tetrachloride3 (56-23-5)
chlordane3 (12789-03-6)
chlorine (7782-50-5)
chloroacetaldehyde (107-20-0)
2-chloro-l,3-butadiene
(126-99-8)
chloroform3 (67-66-3)
chloromethane3 (74-87-3)
3-chloropropionitrile (542-76-7)
chromium III (7440-47-3)
chromium VI (7440-47-3)
copper cyanide (544-92-3)
cresols3 (1319-77-3)
crotonaldehyde (4170-30-3)
cumene (98-82-8)
cyanide (57-12-5)
cyanogen (460-19-5)
cyanogen bromide3 (506-68-3)
cyanogen chloride (506-77-4)
cyclohexanone (108-94-1)
2,4 D (dichlorophenoxyacetic
acid) (94-75-7)
DDT3 (50-29-3)
(continued)
E-30
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TABLE E-8 (continued)
Chemical
Chemical
decabromodiphenyl oxide (1163-19-5)
di-n-butyl phthalate (84-74-2)
1,2-dichlorobenzene (95-50-1)
1,4-dichlorobenzene3 (106-46-7)
dichlorodifluoromethane (75-71-8)
1,1-dichloroethane3 (75-34-3)
1,1-dichloroethylene3 (75-35-4)
2,4-dichlorophenol (120-83-2)
l,3-dichloropropenea (542-75-6)
dieldrin3 (60-57-1)
diethyl phthalate (84-66-2)
dimethoate (60-51-5)
dimethyl amine (124-40-3)
dimethyl aniline (121-69-7)
(alpha, alpha) dimethyl
phenethylamine (122-09-8)
dimethylterephthalate (120-61-6)
2,4-dinitrophenol (51-28-5)
dinoseb (88-85-7)
diphenyl amine (122-39-4)
disulfoton (298-04-4)
endosulfan (115-29-7)
endothall (129-67-9)
endrin (72-20-8)
epichlorohydrina (chloro-2,3-
epoxy-propane) (106-89-8)
ethyl acetate (141-78-6)
ethyl benzene (100-41-4)
ethylene glycol (107-21-1)
ethylene oxidea (75-21-8)
ethylene thiourea3 (96-45-7)
fluoracetic acid, sodium salt
(62-74-8)
fluoride (16984-48-8)
fluorine (7782-41-4)
formaldehyde3 (50-00-0)
formic acid (64-18-6)
freon 113 (76-13-1) ,
furan (110-00-9)
gamma-hexachlorocyclohexane
(lindane) (58-89-9)
heptachlor3 (76-44-8)
heptachlor epoxide3 (1024-57-3)
hexachlorobutadiene3 (87-68-3)
hexachlorocyclopentadiene (77-47-4)
hexachloroethane3 (67-72-1)
hydrogen chloride (7647-01-0)
hydrogen cyanide (74-90-8)
hydrogen sulfide (7783-06-4)
isobutyl alcohol (78-83-1)
lead (7439-92-1)
maleic hydrazide3 (123-33-1)
malononitrile (109-77-3)
mercury (7439-97-6)
methacrylonitrile (126-98-7)
methomyl (16752-77-5)
methoxyclor (72-43-5)
methyl bromide (bromomethane)
(74-83-9)
(continued)
E-31
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TABLE E-8 (continued)
Chemical
Chemical
methyl chloroform (1,1,1-
trichloroethane) (71-55-6)
methylene chloride9 (75-09-2)
methyl ethyl ketone (78-93-3)
methyl iodide9 (74-88-4)
methyl isobutyl ketone (108-10-1)
methyl isocyanate (624-83-9)
2-methyl lactonitrile (75-86-5)
methyl parathion (298-00-0)
nickel carbonyl9 (13463-39-3)
nickel cyanide (557-19-7)
nickel refinery dusta (7440-02-2)
nitric oxide (10102-43-9)
nitrobenzene9 (98-95-3)
4-nitroquinoline-l-oxide (56-57-5)
osmium tetroxide (20816-12-0)
pentachlorobenzene9 (608-93-5)
pentachloroethane9 (76-01-7)
pentachloronitrobenzene (82-68-8)
pentachlorophenol9 (87-86-5)
phenol (108-95-2)
m-pheny1enediamine9 (25265-76-3)
phenylmercuric acetate (62-38-4)
phosgene (75-44-5)
phosphine (7803-51-2)
potassium cyanide (151-50-8)
potassium silver cyanide (506-61-6)
pronamide9 (23950-58-5)
propanenitrile (107-12-0)
n-propylamine (107-10-8)
2-propyn-l-ol (107-19-7)
pyridine (110-86-1)
selenious acid (selenium dioxide)
(7783-00-8)
selenourea (630-10-4)
silver (7440-2.2-4)
silver cyanide (506-64-9)
si 1 vex (93-72-1)
sodium azide (26628-22-8)
sodium cyanide (143-33-9)
styrene9 (100-42-5)
strychnine (57-24-9)
1,2,4,5-tetrach1orobenzene
(95-94-3)
1,1,1,2-tetrach1oroethane9
(630-20-6)
tetrachloroethylene9 (127-18-4)
2,3,4,6-tetrachlorophenol
(58-90-2)
tetraethyl dithiopyrophosphate
(3689-24-5)
tetraethyl lead (78-00-2)
thallic oxide (1314-32-5)
thallium (7440-28-0)
thallium (1) acetate (563-68-8)
thallium (1) carbonate (6533-73-9)
thallium (1) chloride (7791-12-0)
thallium (1) nitrate (10102-45-1)
thallium (1) selenite (12039-52-0)
thallium (1) sulfate (10031-59-1)
thiomethanol (methyl mercaptan)
(74-93-1)
thiosemicarbazide (79-19-6)
(continued)
E-32
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TABLE E-8 (continued)
Chemical
Chemical
thiram (137-26-8)
toluene (108-88-3)
1,2,4-trichlorobenzene (120-82-1)
l,l,2-trichloroethanea (79-00-5)
tri chloromonof1uoromethane
(75-69-4)
2,4,5-trich1orophenola (95-95-4)
1,2,3-trichloropropane (96-18-4)
vanadium pentoxide (1314-62-1)
warfarin (81-81-2)
xylene(s) (1330-20-7)
zinc cyanide (557-21-1)
zinc phosphide (12037-79-5)
zineb* (12122-67-7)
( ) = Chemical Abstracts Service (CAS) Number.
aCarcinogen.
E-33
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estimate of the number of people living in the vicinity of emitting
sources.
The EPA uses the Human Exposure Model (HEM) to make these quantitative
estimates of public exposure and risk associated with a pollutant. The HEM
uses an atmospheric dispersion model that includes meteorological data and
a population distribution estimate based on 1980 Bureau of Census data to
calculate public exposure.18
The dispersion model in HEM used data for a model plant that was
placed at each TSDF location (initially about 5,000 sites). The location
of each TSDF was obtained from the TSDF Industry Profile (see Appendix D,.
Section D.2.1). Inputs to the initial run included a unit cancer potency
estimate (1.0) and a unit emission rate (10,000 kg VOC/yr). In addition,
an exit velocity and an effluent outgas temperature of 0.1 m/s and 293 K
were assumed. These inputs were used to estimate the concentration and
distribution of the pollutant at distances of 200 m to 50 km from the
source. The population distribution estimates for people residing near the
source are based on Bureau of Census data contained in the 1980 Master Area
Reference File (MARF) data base.19 The data base is broken down into
enumeration district/block group (ED/BG) values. The MARF contains the
population centroid coordinates (latitude and longitude) and the 1980
population of each ED/BG (approximately 300,000) in the United States. By
knowing the geographic location of the plant (latitude and longitude), the
model can identify the ED/BG that fall within the 50-km radius used by HEM.
The HEM multiplies the concentration of the pollutant at ground level
at each of the 160 receptors around the plant by the number of people
exposed to that concentration to produce the exposure estimates. The total
exposure, as calculated by HEM, is illustrated by the following equation:
N
Total exposure = E (P,)(C.) ,
1=1 1 1
E - summation over all grid points where exposure is calculated
P-J = population associated with grid point i
(E-2)
E-34
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Ci = long-term average pollutant concentration at grid point i
N = number of grid points.
The HEM assumes that: (1) people stay at the same location (residence) and
are exposed to the same concentrations of the pollutant for 70 years; (2)
the terrain around the plant is flat; and (3) concentrations of the pollut-
ant are the same inside and outside the residence.
E.3.2 ISCLT Model
As noted above, the ISCLT model was used to estimate ambient concen-
trations of VO for estimating maximum lifetime risk for the cancer health
effects assessment and the chronic noncancer effects study. The ISCLT
model is a steady-state, Gaussian plume, atmospheric dispersion model that
is applicable to multiple point, area, and volume emission sources. It is
designed specifically to estimate long-term ambient concentrations of
pollutants in the vicinity of industrial source complexes. The model was
applied to two TSDF to estimate the highest concentrations of VO and
individual chemicals at the fence!ine, or beyond, of two TSDF. As
described later in Section E.4, the highest ambient VO concentrations are
used with the composite unit risk estimate to calculate maximum lifetime
risk. A detailed discussion of the model and its application to the two
TSDF is contained in Appendix J.
E.3.3 ISCST Model
The ISCST model was used to estimate ambient concentrations of indi-
vidual hazardous waste constituents for purposes of evaluating acute,
noncancer health risks. It was also used as a screening tool to identify
which of the chemicals of concern in Table E-8 should be further evaluated
with the ISCLT (see also Appendix J). The ISCST is similar in nature to
the ISCLT, except that it is suitable for estimating short-term ambient
concentrations (e.g., concentrations averaged over 1 h, 3 h, 8 h, 24 h,
etc.) as well as long-term averages. ISCST was applied to two TSDF to
estimate the highest constituent concentrations for variable averaging
times at the fendine or beyond. A detailed description of this model and
its application are also contained in Appendix J.
E-35
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E.4 RISK ASSESSMENT
E.4.1 Cancer Risk Measurements
Three pieces of information are needed to assess the cancer risks of
exposure to TSDF air emissions: (1) an estimate of the carcinogenic
potency, or unit risk estimate, of the pollutants in TSDF air emissions;
(2) an estimate of the ambient concentration of the pollutants from a TSDF
that an individual or group of people breathe; and (3) an estimate of the
number of people who are exposed to those concentrations.
Multiplying the composite unit risk estimate by (1) the numerical
expressions of public exposure obtained from HEM and (2) the maximum
concentration predicted by ISCLT gives two types of cancer risk measures:
(1) annual incidence, a measure of population or aggregate risk, and (2)
individual risk or maximum lifetime risk. The definition and calculation
of annual incidence are discussed in the next section. Maximum lifetime
risks are discussed in Section E.4.1.2.
E.4.1.1 Annual Cancer Incidence. One expression of risk is annual
cancer incidence, a measure of aggregate risk. Aggregate risk is the
summation of all the risks to people estimated to be living within the
vicinity (usually within 50 km) of a source. It is calculated by
multiplying the estimated concentrations of the pollutants by the unit risk
estimate by the number of people exposed to different concentrations. This
estimate reflects the number of excess cancers among the total population
after 70 years of exposure. For statistical convenience, the aggregate
risk is divided by 70 and expressed as cancer incidence per year.20
A unit cancer potency estimate of 1.0 and a unit emission rate of
10,000 g/yr were used as input data for HEM. Annual incidence, attributed
to each TSDF, as calculated by using HEM, is proportional to the cancer
potency estimate and emissions. Thus, another model was used to scale the
annual incidence for each TSDF by the estimated composite unit risk esti-
mate and by the estimated VO emission that were attributed to each TSDF:
Annual incidence = HEM annual incidence x
Composite
unit risk
estimate
ITS
VO emissions
for TSDF XX
10,000 kg
(E-3)
E-36
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The annual incidences were then summed over all TSDF. This scaling and \
final aggregation was performed with the Source Assessment Model (SAM) (see
Appendix D).
E.4.1.2 Maximum Lifetime Risk. Maximum lifetime risk or individual
risk refers to the person or persons estimated to live in the area of high-
est ambient air concentrations of the pollutant(s) as determined by the
detailed facility modeling. The maximum lifetime risk reflects the proba-
bility of an individual developing cancer as a result of continuous
exposure to the estimated maximum ambient air concentration for 70 years.
The use of the word "maximum" in maximum lifetime risk does not mean the
greatest possible risk of cancer to the public. It is based only on the
maximum exposure estimated by the procedure used,21 and it does not incor-
porate uncertainties in the exposure estimate or the unit risk estimate.
Maximum lifetime risk is calculated by multiplying the highest ambient
air concentration by the composite unit risk estimate. The product is the
probability of developing cancer for those individuals assumed to be
exposed to the highest concentration for their lifetimes. Thus,
Maximum lifetime risk = [Composite unit risk]
[estimate at 1 /jg/m J
E.4.2 Noncancer Health Effects
Highest ]
ambient air
.concentration]
(E-4)
E.4.2.1 Chronic Exposures. The assessment of noncancer health
effects associated with chronic exposures to TSDF chemicals of concern is
based on a comparison of the chemical-specific health benchmark levels (as
discussed in Section E.2.1) to estimated ambient concentrations at various
receptor locations around a facility. Inhalation exposure limits are com-
pared to the highest annual average ambient concentration for each chemical
at the selected facilities. These annual concentrations represent an
estimation of the highest average daily ambient concentration experienced
over a year. Ambient concentrations that are less than the RfO are not
likely to be associated with health risks. The probability that adverse
effects may be observed in a human population increases as the frequency of
exposures exceeding the RfD increases and as the size of the excess
increases.
E-37
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Because Agency-verified RfD were not available, an interim screening
approach was used. The likelihood of adverse noncancer health effects was
determined by comparing modeled ambient concentrations of individual
constituents to the available health data. These health data were obtained
from various sources, including EPA reports and documents, data used to
support occupational exposure recommendations and standards (e.g., American
Conference of Governmental Industrial Hygienists, Documentation of the
Threshold Limit Values), and other published information. An assessment of
the potential for adverse noncancer health effects was made case-by-case,
considering: (1) the magnitude of the differences between the exposure
concentration and the lowest-observed-adverse-effect level or the no-
observed-adverse-effect level, and (2) the quality of the health effects
data base. The modeled ambient concentrations in Appendix J, Tables J-18
and J-19, were compared to the information in health effects documentation
for noncancer chemicals.22 the modeled concentrations were, in most cases,
three orders of magnitude below health effects levels of concern. The
probability that such effects will occur increases with increasing exposure
concentrations. This screening effort was used only to give a preliminary
indication of the potential for noncancer health effects, and will be
replaced by an analysis that uses inhalation reference doses as they become
available.
E.4.2.2 Acute Exposures. An assessment of the potential for non-
cancer health effects associated with short-term (acute) exposure to TSDF
chemicals of concern at selected facilities was conducted as a screening
effort to provide additional qualitative support to the overall noncancer
health effects analysis. In addition to the lack of short-term inhalation
health benchmark levels at this time, acute inhalation data are limited for
many of the TSDF chemicals of concern. The assessment was conducted by
comparing maximum modeled ambient concentrations for averaging times of
15 min, 1 h, 8 h, and 24 h to available short-term health data matched to
the appropriate averaging time. A determination of the risk of adverse
health effects associated with estimated short-term exposures was based on
a consideration of the quality of the available health data and the proxim-
ity of the exposure concentration to the health effect level. The modeled
E-38
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ambient concentrations in Appendix J, Tables J-18 and J-19, were compared
to the information in health effects documentation for noncancer chemi-
cals. 23 The modeled concentrations were, in most cases, three orders of
magnitude below health effects levels of concern.
E.5 ANALYTICAL UNCERTAINTIES APPLICABLE TO CALCULATIONS OF PUBLIC HEALTH
RISKS IN THIS APPENDIX
E.5.1 Unit Risk Estimate
The procedure generally used to develop unit risk estimates is fully
described in Reference 1, using nickel as an example. The low-dose extrap-
olation model used and its application to epidemiological and animal data
have been the subjects of substantial comment by health scientists. The
uncertainties are too complex to be summarized in this appendix. Readers
who wish to go beyond the information presented in the reference should see
the following Federal Register notices: (1) EPA's "Guidelines for
Carcinogenic Risk Assessment," 51 FR 33972 (September 24, 1986), and (2)
EPA's "Chemical Carcinogens; A Review of the Science and Its Associated
Principles," 50 FR 10372 (March 14, 1985), February 1985.
Significant uncertainties associated with the cancer unit risk esti-
mates include: (1) selection of dose-response model, (2) selection of
study used to estimate the unit risk estimate, and (3) presence or absence
of a threshold. Uncertainties related to the composite risk estimate
include the assumption of additivity of carcinogenic risk. According to
the EPA "Guidelines for the Health Risk Assessment of Mixtures," a number
of factors such as data on similar mixtures and the interactions among
chemicals must be considered before additivity can be assumed.24 Because
of the sheer number of chemicals emitted from TSDF and the lack of specific
information on particular compounds, EPA assumed additivity.
E.5.2 Public Exposure
E.5.2.1 General. The basic assumptions implicit in the methodology
are that all exposure occurs at people's residences, that people stay at
the same location for 70 years, that the ambient air concentrations and the
emissions that cause these concentrations persist for 70 years, and that
the concentrations are the same inside and outside the residences. From
E-39
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this it can be seen that public exposure is based &n a hypothetical rather
than a realistic premise. It is not known whether this results in an over-
estimation or an underestimation of public exposure.
E.5.2.2 The Public. The following are relevant to the public as
dealt with in this analysis:
• Studies show that all people are not equally susceptible to
cancer. There is no numerical recognition of the "most
susceptible" subset of the population exposed.
• Studies indicate that whether, or not exposure to a particu-
lar carcinogen results in cancer may be affected by the
person's exposure to other substances. The public's expo-
sure to other substances is not numerically considered.
• Some members of the public included in this analysis are
likely to be exposed to compounds in the air in the work-
place, and workplace air concentrations of a pollutant are
customarily much higher than the concentrations found in the
ambient or public air. Workplace exposures are not numeri-
cally approximated.
• Studies show that there is normally a long latency period
between exposure and the onset of cancer. This has not been
numerically recognized.
• The people dealt with in the analysis are not located by
actual residences. As explained previously, they are
"located" in the Bureau of Census data for 1980 by popula-
tion centroids of census districts.
• Many people dealt with in this analysis are subject to
exposure to ambient air concentrations of potentially toxic
pollutants where they travel and shop (as in downtown areas
and suburban shopping centers), where they congregate (as in
public parks, sports stadiums, and school yards), and where
they work outside (as mailmen, milkmen, and construction
workers). These types of exposures are not dealt with
numerically.
E.5.2.3 Ambient Air Concentrations. The following are relevant to
the estimated ambient air concentrations used in this analysis:
• Flat terrain was assumed in the dispersion model. Concen-
trations much higher than those estimated would result if
emissions impact on elevated terrain or tall building near a
plant.
• The estimated concentrations do not account for the additive
impact of emissions from plants located close to one another.
E-40
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• Meteorological data specific to plant sites are not used in
the dispersion model. As explained, meteorological data from
a National Weather Service station nearest the plant site are
used. Site-specific meteorological data could result in
significantly different estimates, e.g., the estimates of
where the higher concentrations occur.
• With few exceptions, the emission rates are based on assump-
tions and on limited emission tests. See the Background
Information Document for details on each source.
E.6 REFERENCES
1. U.S. Environmental Protection Agency. Health Assessment Document for
Nickel and Nickel Compounds. Publication No. EPA-600/8-83-012FF.
Office of Health and Environmental Assessment, Washington, DC. 1986.
p. 8-156.
2. Reference 1, p. 8-156.
3. U.S. Environmental Protection Agency. Carcinogen Assessment of Coke
Oven Emissions. Publication No. EPA-600/6-82-003F. Office of Health
and Environmental Assessment. Washington, DC. 1984. p. 147.
4. Reference 1, p. 8-161.
5. Reference 1, p. 8-179.
6. Reference 1, p. 8-162.
7. Reference 1, p. 8-179.
8. U.S. Environmental Protection Agency. Health Assessment Document for
Carbon Tetrachloride. Publication No. EPA-600/8-82-001F. Environ-
mental Criteria and Assessment Office, Cincinnati, OH. September
1984. p. 12-10.
9. U.S. Environmental Protection Agency. Hazardous Waste Management
System; Identification and Listing of Hazardous Waste; Final Rule.
51 FR 28296. August 6, 1986.
10. Memorandum from Lisa Ratcliff, EPA, to Bob Scarberry and Debra
Dobkowski, EPA. June 29, 1987. Inhalation exposure limits.
11. Reference 10.
12. Memorandum from Branscome, M., RTI, to Docket. September 28, 1988.
Calculation of composite unit risk estimates.
13. U.S. Environmental Protection Agency. Guidelines for Carcinogen Risk
Assessment. 51 FR 33992. September 24, 1986.
E-41
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14. Reference 9.
15.
16.
Memorandum from Coy, Dave, RTI, to McDonald, Randy, EPA/OAQPS. May 2,
1986. Listing of waste constituents prioritized by quantity.
U.S. Environmental Protection Agency. Status Report of the RfD Work
Group. Environmental Criteria and Assessment office, Cincinnati, OH.
1987.
17. U.S. Environmental Protection Agency. Burning of Hazardous Waste in
Boilers and Industrial Furnaces; Preamble Correction. 52 FR 25612.
July 8, 1987.
18. U.S. Environmental Protection Agency. User's Manual for the Human
Exposure Model (HEM). Office of Air Quality Planning and Standards,
Research Triangle park, NC. Publication No. EPA/450/5-86-001. 1986.
19. Department of Commerce. Local Climatological Data. Annual Summaries
with Comparative Data. 1967.
20. U.S. Environmental Protection Agency. Inorganic Arsenic NESHAPs:
Response to Public Comments on Health, Risk Assessment, and Risk
Management. Publication No. EPA/450-5-85-001. Office of Air Quality,
Planning, and Standards, Research Triangle Park, NC. April 1985.
p. 4-13.
21. Reference 20, p. 4-18.
22. Alliance Technologies Corporation. Estimation of Human Health Risks
from Exposure to Air Emissions from Treatment, Storage, and Disposal
Facilities. Prepared for U.S. Environmental Protection Agency, Office
of Air Quality Planning and Standards. Research Triangle Park, NC.
July 22, 1988. 107 p.
23. Reference 22.
24. U.S. Environmental Protection Agency. Guidelines for the Health Risk
Assessment of Chemical Mixtures. 51 FR 34014. September 24, 1986.
25. Chemical Manufacturers Association. Comments of the Chemical Manufac-
turers Association on the Environmental Protection Agency Document,
"Hazardous Waste TSDF - Background Information for Proposed RCRA Air
Emission Standards - Volumes I and II." Washington, D.C. July 11,
1988. 105 p.
E-42
-------
APPENDIX F
TEST DATA
-------
-------
APPENDIX F
TEST DATA
An ongoing test program is being conducted to develop an air emission
data base in support of standards to control emissions from hazardous waste
treatment, storage, and disposal facilities (TSDF).
The purposes of the test program are to:
• Provide an indication of air emission levels from TSDF
• Evaluate effectiveness of emission controls
• Evaluate measurement techniques for determining air emis-
sions from hazardous waste TSDF
• Evaluate modeling techniques for estimating air emissions
from hazardous waste TSDF.
Source testing has been conducted at TSDF covering five categories:
• Surface impoundments
• Wastewater treatment (WWT) systems
• Active and inactive landfills
• Land treatment facilities
• Transfer, storage, and handling operations.
In addition, data are available from petroleum transfer, storage, and
handling operations and from fugitive sources at petroleum refineries and
synthetic organic chemical manufacturing industries (SOCMI) facilities that
are applicable to TSDF fugitive emission sources.
The types of controls that have been tested are add-on controls for
the suppression of emissions, capture and containment devices to control
vented off-gases, and volatile organic (VO) removal processes such as steam
F-3
-------
strippers and thin-film evaporators. These sources have been tested for
their effectiveness as well as any emissions they produce.
The subsequent sections of this appendix summarize the available test
data by TSDF emission source category and control type. For each source
category, descriptions of the facility and types of wastes managed per
facility are presented, along with air emission sources tested, objectives
of tests, sampling locations, sampling and analytical techniques used, and
tabular summaries of test results. (Note: The use of "VO" in the
presentation of test results does not refer to test results from the VO
test method described in Appendix G.)
Tables F-l through F-9 present summaries of tests. There are two
summary tables for surface impoundments, two for WWT systems, and two for
landfills. The first of each pair of tables presents general information
including test site identification number, test site location, test
description, test year, test sponsor, and test duration. The second table
of each pair presents measured emission data. Summaries of testing and
test results for land treatment; transfer, storage, and handling opera-
tions; and controls are each presented in one table. Each table includes
site identification number, test site location, test year, test sponsor,
test description, test duration, test procedure, source tested or control
tested, and summary of test results.
F.I TEST DATA AT EMISSION SOURCES
F.I.I Surface Impoundments
F.I.1.1 Site I.1 Site 1 is a RCRA-permitted commercial hazardous
waste TSDF. The facility includes four general waste management processes:
surface impoundments (ponds), landfills, wastewater treatment unit, and
solvent recovery. Ponds 2, 6, and 8 are currently being used as surface
impoundments. Pond 2 acts as the receiving basin. An oil film covers much
of its surface, and floating solid debris is visible on the pond's surface
as well. Pond 2 has a capacity of approximately 5,700 m3. Each of the
surface impoundments is operated with approximately 1.5 m of freeboard; the
dimensions of each of the surface impoundments are given in Table F-10.
From Pond 2, the aqueous waste is pumped to Pond 6. Caustic is added
to the wastewater at Pond 6 to raise the pH to approximately 11, and poly-
mer is added to promote solids settling. Pond 6 has a capacity of about
9,500 m3.
F-4
-------
TABLE F-l. SUMMARY OF TSDF SURFACE IMPOUNDMENT TESTING3
Site
No.
Test site
location
Test Test Test Test
description year sponsor duration
1 Oklahoma
commercial TSDF
2 California
commercial TSDF
3 Louisiana
refinery/lubricating
'oil plant
4 Texas
chemical manufacturing
plant
Mississippi
chemical manufacturing
plant
California
commercial TSDF
7 New York
commercial TSDF
Field test
(3 impoundments)
• Liquid samples
• Biological
activity testing
Field test
(4 impoundments)
» Liquid samples
• Biological
activity testing
Field test
(1 impoundment)
• Liquid samples
• Biological
activity testing
Field test
(1 impoundment)
• Liquid samples
« Biological
activity testing
Field test
(1 impoundment)
• Flux chamber
» Liquid samples
• Sludge samples
Field test
(1 impoundment)
• Flux chamber
« Liquid samples
Field test
(3 impoundments)
• Flux chamber
• Liquid samples
1987 EPA/ORD
1 day
1986 EPA/ORD
1986 EPA/ORD
1986 EPA/ORD
1983 EPA/ORD
1 day
1 day
1 day
1985 EPA/OAQPS 3 days
1984 EPA/OAQPS 2 days
1 week
TSDF = Treatment, storage, and disposal facility.
ORD = Office of Research and Development.
OAQPS = Office of Air Quality Planning and Standards.
aThis table presents a summary of the air emission, liquid concentration, and
biological activity testing conducted at TSDF surface impoundments.
F-5
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F-6
-------
TABLE F-3. SUMMARY OF TSDF WASTEWATER TREATMENT SYSTEM TESTING9
Site
No.
Test site
location
Test Test Test .Test
description year sponsor duration
8 East Coast
petroleum refinery
East Coast
synthetic organic
chemical manufacturer
10 East Coast
synthetic organic
chemical manufacturer
11 Florida
acrylic fiber
manufacturer
12 Connecticut
specialty chemical
manufacturer
13 Louisiana
organic chemical
manufacturer
Field test
(submerged aerated)
• Flux chamber
• Liquid samples
• Biological
activity testing
Field test
(surface aerated)
• Liquid samples
• Biological
activity testing
Field test
(surface aerated)
• Flux chamber
• Liquid samples
• Biological
activity testing
Field test
(surface aerated)
• Liquid samples
• Biological
activity testing
Field test
(covered surface
aerated)
• Liquid samples
• Vent samples
Field test
(wastewater treat-
ment plant)
• Liquid samples
• Ambient air
samples
1987 EPA/ORD
1 week
1986 EPA/ORD
1 week
1986 EPA/ORD
1 week
1986
EPA
Region IV
2 days
1984 EPA/ORD
1 week
1983
EPA/ORD/
Union
Carbide
26 days
TSDF = Treatment, storage, and disposal facility.
ORD = Office of Research and Development.
aThis table presents a summary of the air emission, liquid concentration, and
biological activity testing conducted at TSDF wastewater treatment systems.
F-7
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-------
TABLE F-5. SUMMARY OF TSDF LANDFILL TESTING9
Site
No.
Test site
location
Test
description
Test
year
Test
sponsor
Test
duration
14 California
commercial TSDF
California
commercial TSDF
15 Gulf Coast
commercial TSDF
16 Northeastern
commercial TSDF
Northeastern
commercial TSDF
Field test
(1 landfill)
• Flux chamber
• Soil samples
Field test
(2 landfills)
• Flux chamber
• Soil samples
Field test
(1 landfill)
• Flux chamber
• Soil samples
Field test
(2 landfills)
• Flux chamber
• Vent samples
• Soil samples
Field test
(2 landfills)
• Flux chamber
• Vent samples
• Soil samples
1984 EPA/OAQPS 2 days
1984 EPA/OAQPS 2 days
1983 EPA/OSW 3 days
1983 EPA/OSW 2 days
1983 EPA/OSW 1 week
TSDF = Treatment, storage, and disposal facility.
OAQPS = Office of Air Quality Planning and Standards.
OSW = Office of Solid Waste.
aThis table presents a summary" of the air emission and soil concentration
testing conducted at TSDF landfills.
F-9
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F-22
-------
TABLE F-10. SURFACE IMPOUNDMENT DIMENSIONS AT TSDF SITE 1
Impoundments
Dimensions, ma
Pitch (hor:vert)
2
6
8
36 x 30 x 4.6
61 x 33 x 4.6
71 x 72 x 5.2
2:1
2:1
1:1
TSDF = Treatment, storage, and disposal facility.
aLength and width dimensions refer to the bottom of the ponds.
F-23
-------
Treated wastewater from Pond 6 is then pumped to Pond 8. Pond 8,
which has a capacity of approximately 26,000 m3, acts as a holding pond
prior to the aerated WWT unit. Effluent from the WWT system is then pumped
back to Pond 8 so that the only route for aqueous removal is evaporation.
Grab samples of wastewater for chemical analysis were collected on
April 7, 1987, in 1-L amber glass bottles with Teflon-lined screw caps and
in 40-mL zero-headspace, Teflon-lined, septum volatile organic analysis
(VOA) vials. Because no "anaerobic zones" were identified in Ponds 2 or 6
(i.e., no dissolved oxygen [DO] < 1.0 mg/L were measured), only one set of
grab samples was collected from these impoundments. Samples were taken
from two different locations within Pond 8: one in the aerobic zone near
the surface of the wastewater, and one in the anaerobic zone near the bot-
tom of the lagoon.
The samples were analyzed for purgeable organics according to EPA
Method 6242 and for base/neutral and acid extractables according to EPA
Method 625.3 Data for the purgeable organics identified in the samples are
presented in Table F-ll.
The extractable organic analysis included 56 compounds. The data for
the compounds present in the wastewater samples are presented in Table
F-12.
In addition to the chemical analysis samples, samples were obtained at
each of the sampling points for biological activity testing. Due to the
extremes in pH found in Ponds 2 and 6 (0.5 and 11.5, respectively), the
samples from these ponds were not expected to be biologically active. Only
a limited amount of wastewater was collected from these ponds to document
the presence or absence of biological activity. At Pond 2, approximately
3.8 L of wastewater was collected in a 9.5-L plastic container. At Pond 6,
two 1-L amber glass bottles were filled using the residual wastewater left
in the bucket after filling the chemical analysis sample containers. Sam-
ples for biological testing were collected from near the surface and from
near the bottom of Pond 8. The biological testing samples were 9.5 L in
volume and were collected in 9.5-L plastic containers.
Microscopy studies were employed to confirm the presence of micro-
organisms in the wastewater. Both wet drop slides and gram-stained slides
F-24
-------
TABLE F-ll. ANALYSES OF SAMPLES TAKEN AT SITE 1 SURFACE
IMPOUNDMENTS: PUREGEABLE ORGANICS9
Concentration, pg/L
Pond 2
aerobic
Constituent sample
Methyl ene chloride 1
Chloroform
1,1,1-Trichloroethane 16
Tetrachloroethene
1,1,2, 2-Tetrachl oroethane
Benzene
Toluene 2
Ethyl benzene
Chlorobenzene
Acetone0 35
Isopropanol0 156
l-Butanolb.c 71
Thiobismethane0
Freon 113C
Methyl ethyl ketonec 27
Total xylenes0 1
,850
880b
,000
<50
<50
<50
,070
<50
42b
,000
,000
,300
<50
<50
,000
,140
Pond 6
aerobic
sample
46b
22b •
30b
<50
15b
gb
33b
llb
7b
5,450
8,400
510
<50
<50
210
<50
Pond 8
duplicate
aerobic samples
47b
2.3b
<50
22b
<50
<50
43b
12b
2b
4,500
4,200
<50
1,300
40b
510
47b
36b
2.5b
<50
24b
<50
<50
46b
15b .
3b
4,200
3,200
<50
1,300
23b
490
49b
Pond 8
anaerobic
sample
44b
<50
<50
<50
<50
<50
47b
<50
3b
4,100
3,200
<50
1,500
49b
620
<50
TSDF = Treatment, storage, and disposal facility.
Determined by EPA Method 624.
blndicates concentration is below the reportable quantitation limit.
These compounds were positively identified, but the accuracy of
quantitation is not guaranteed within 30 percent.
clndicates compounds identified that are not Method 624 target analytes.
These compounds are not quantitated according to Method 624; their
absolute accuracy is not guaranteed. However, the relative concentra-
tions for any one compound should be consistent (i.e., should show
correct relative trends).
F-25
-------
TABLE F-12. ANALYSES OF SAMPLES TAKEN AT SITE 1 SURFACE
IMPOUNDMENTS: EXTRACTABLE ORGANICS9
Concentration, /*g/L
Constituent
Bis (2-chloroisopropyl)
ether
Bis (2-ethylhexyl)
phthalate
Isophorone
2-Nitrophenol
N-Nitrosodiphenylamine
Pond 2
aerobic
sample
17,600
6,560
72,800
<1,000
<4,000
Pond 6
aerobic
sample
76b
78b
5,600
660
35b
Pond 8
duplicate
aerobic samples
68b
43b
34b
670
35b
<200
<200
75b
490
40b
Pond 8
anaerobic
sample
148b
<200
160b
800
137b
TSDF = Treatment, storage, and disposal facility.
aDetermined by EPA Method 625.
blndicates concentration is below the reportable quantisation limit.
These compounds were detected, but the accuracy of quantitation is not
guaranteed within 30 percent.
F-26
-------
were employed. No motile organisms were observed using the wet drop
slides; a few stalks of algae were observed in the samples collected from
Ponds 6 and 8. Numerous bacteria were observed in all the wastewater sam-
ples using gram-stained slides. The bacteria observed were predominantly
gram-negative, with scattered gram-positive bacteria visible.
From the microscopy studies, all wastewater samples apparently
contained microorganisms. Pond 8 appeared to be the most heavily popu-
lated, and Pond 6 appeared to be the least populated. No other studies
were performed to further identify the microorganisms.
The presence of aerobic biological activity was determined by the
ability of the microorganisms to remove oxygen from the wastewater. Two
experiments were employed to measure the oxygen consumption rate of the
microorganisms.
The first experiment performed was the dissolved oxygen (DO) depletion
experiment. The procedure employed was as follows. A wide-mouth, amber
glass, 0.5-L bottle was filled with the wastewater sample and allowed to
come to thermal equilibrium. Air was then bubbled through the sample for
approximately 5 min to raise the initial DO concentration. A magnetic stir
bar was added to the sample bottle. The lid, fitted with a DO probe, was
secured allowing the wastewater to overflow in order to ensure zero
headspace within the bottle. The sample was stirred using a magnetic
stirrer, and the DO concentration was recorded with time. The DO depletion
experiments were approximately 1 day in duration. A parallel DO depletion
experiment was performed on each of the wastewater samples by adding 0.5 g
of biocide (mercuric acetate) to the 500-mL sample prior to testing. The
parallel samples (denoted as killed) were used to distinguish between bio-
logical oxygen consumption and chemical oxygen consumption.
The second oxygen uptake rate experiment employed a manometric
biochemical oxygen demand (BOD) apparatus and was consequently termed the
BOD-type experiment. The procedure employed was as follows. To a 0.5-L
amber glass respirometry bottle, 350 to 400 ml of sample was quantitatively
added. The bottle was then placed on a magnetic stirring plate and slowly
agitated. The respirometry bottle lid has a tube fitting to allow the
bottle to be connected to a mercury manometer and a sealing nipple that
F-27
-------
houses lithium hydroxide. During biodegradation, the lithium hydroxide
absorbs the carbon dioxide produced so that the consumption of oxygen
results in a decrease in the total pressure of the system according to the
ideal gas law. The pressure drop resulting from aerobic (oxygen consuming)
biological activity was measured with the mercury manometer as a function
of time. The rate of oxygen consumption in these experiments was suffi-
ciently slow so that the oxygen transfer rate was not limiting. The BOD-
type experiments were longer in duration than the^DO depletion experiment
and were performed over a 1- to 2-week period.
There was negligible oxygen consumption in the poisoned wastewater
samples collected from Ponds 6 and 8, indicating that the oxygen consump-
tion observed by these samples was biological in nature. The oxygen con-
sumption of the poisoned sample from Pond 2, on the other hand, was nearly
identical to the oxygen consumption of the sample with no biocide added.
This indicated that the oxygen consumption exhibited by this sample was
chemical in nature, as would be expected by the biologically prohibitive pH
(pH - 0.5) measured in Pond 2. Plant personnel stated that this low pH was
not indicative of normal operating conditions for Pond 2.
The component-specific rate determinations were designed to permit
organic removal due to biodegradation while limiting their removal by air
stripping. The calculated rate constants are summarized in Table F-13. In
general, the first-order rate constants typically fit the data better than
the zero-order rate constants as judged by the correlation coefficient of
the regression analysis. This is probably a consequence of the low initial
concentrations for most of the volatile organics studied. The rate con-
stants for a single compound, as calculated for the two different ponds,
are in fair agreement because they are within a factor of 2 or 3. Each
zero-order rate constant is at least two orders of magnitude less than the
biodegradation rate constants typically reported from laboratory experi-
ments employing single-component systems. The low concentrations, and the
presence of the multiple, potentially competing substrates, are among the
reasons for the low zero-order biodegradation rates observed.
F.I.1.2 Site 2.4 Site 2 is primarily engaged in the treatment and
disposal of dilute (less than 10 percent organic) aqueous wastes generated
F-28
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TABLE F-13. SUMMARY OF CONSTITUENT-SPECIFIC BIODEGRADATION RATES
IN SAMPLES TAKEN AT SITE 1 SURFACE IMPOUNDMENTS
Zero-order bi orates,3
x 103 mq/q-h
Constituent
Chloroform
Methylene chloride
Toluene
Acetone
Isopropanol
Benzene
Ethyl benzene
Methyl ethyl ketone
1,1, 1-Tri chl oroethane
Trichloroethene
Pond 6
2.65
3.34
3.74
684
532
0.89
1.43
22.4
137
1.63
Pond 8
0.19
2.04
4.21
318
222
38.7
First-order
x 103
Pond 6
5.77
1.73
4.44
22.8
10.9
22.9
1.38
0.20
1.92
3.06
9.86
3.73
13.7
6.57
bi orates,
L/h
Pond 8
2.46
0.88
4.42
2.10
2.29
1.50
1.20
1.83
1.00
2.34
TSDF = Treatment, storage, and disposal.
aThe zero-order biodegradation rate constants were normalized for the
biomass concentration as measured by the volatile suspended solids
content. The rate constants reported for Pond 6 were based on the
biomass concentration measured in Pond 8 (i.e. 16 mg/L).
F-29
-------
by industry and commercial TSDF. The organics in these streams are either
unsuitable for recycling or are too low in concentration to make recovery
economically attractive. A number of treatment technologies are employed
at Site 2, including neutralization, distillation, air stripping, chemical
oxidation, incineration, and solar evaporation. The overall processing
objective is to reduce the VO concentration in the aqueous streams to a
level that is acceptable for final disposal of the waste in evaporation
ponds.
Approximately 227 million L of wastewater is pumped to the evaporation
ponds for disposal each year. At the time of the site visit, the B-Pond
was the receiving pond. From the B-Pond, the wastewater was pumped to the
C-Pond. The B- and C-Ponds each cover approximately 81,000 m2 and have a
depth of 1.2 to 1.8 m. Appropriate piping is in place to allow the trans-
fer of liquid between any two ponds at the disposal site to ensure adequate
freeboard and to maximize the surface area for evaporation. There is no
discharge from the site; each pond is dredged once a year to remove accumu-
lated solids.
Two samples were taken at different places in the B-Pond on Septem-
ber 23, 1986. One sample each was taken from Ponds C, D, and E. The
samples were analyzed for purgeable organic priority pollutants by EPA
Method 624 and extractable organic priority pollutants by EPA Method 625.
Concentration data are presented in Table F-14 for purgeable organics. No
extractable organic priority pollutants were found in any of the samples.
In addition to the chemical analysis samples, samples were obtained at
each of the sampling points for biological activity testing. These samples
were collected in 9.5-L plastic containers.
Microscopy studies were initially employed to confirm the presence of
microorganisms in the wastewater. There were no motile microorganisms
observed using wet drop slides. Pond B(W) and B(SE) samples appeared to
have agglomerations of coccoid blue-green algae. The abundance of inor-
ganic solids, however, especially in the D-Pond sample, hindered the wet
drop slide studies. Both filamentous and nonfilamentous bacteria were
observed using gram-stained slides of Pond B(W), B(SE), C, and D samples.
Both gram-positive bacteria (stained purple) and gram-negative bacteria
F-30
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TABLE F-14. PURGEABLE ORGANICS ANALYSES3 FOR WASTE SAMPLES
TAKEN AT SITE 2 SURFACE IMPOUNDMENTS
Concentration, /*g/L
Constituent
Acetoneb
Methylene chloride
Chloroform
1,2-Dichloroethane
1,1, 1-Trichl oroethane
Tetrachloroethane
Freon 113b
Toluene
Ethyl benzene
Total xylenesb
Benzene
B-Pond
(SE corner)
1,700
35C
BQLd
BQLd
BQLd
BQLd
BQLd
35C
BQLd
56C
BQLd
B-Pond
(W side)
1,600
56C
BQLd
BQLd
BQLd
BQLd
BQLd
40C
BQLd
7QC
BQLd
C-Pond
54
BQLe
BQLe
BQLe
BQLe
BQLe
BQLe
7.5C
BQLe
BQLe
BQLe
D-Pond
2,800
11,000
110
120
1,300
130
550
890
170
820
60C
E-Pond
16,000
12,000
BQLC
BQLC
760
640C
370
3,000
100
430
69C
TSDF = Treatment, storage, and disposal facility.
Determined by EPA Method 624.
^Indicates nontarget compounds quantitated using a response factor from
a single-point calibration.
cCompound identified below strict quantisation limit; accuracy of
reported concentration not ensured to be within 30 percent.
dBelow method quantisation limit of 100 /tg/L.
eBelow method quantisation limit of 10 pg/L.
F-31
-------
(stained red) were observed. No cell cultures were grown to characterize
the bacteria further.
The presence of aerobic biological activity was determined by the
ability of the microorganisms to remove oxygen from the wastewater. Two
experiments were performed to measure the oxygen consumption rate of the
microorganisms.
The first oxygen uptake experiment performed was the DO depletion
experiment. The general procedure employed was as follows. Two wide-
mouth, amber glass, 0.5-L bottles were filled with the wastewater sample
being tested. To one of these bottles, approximately 0.5 g of mercuric
acetate was added to arrest all biological activity. Both samples were
left at room temperature (23 °C) for several hours to ensure that thermal
equilibrium of both samples had been reached and that effective poisoning
of the "killed" sample had been accomplished. Before testing, a magnetic
stir bar was added to the sample bottle, and air was bubbled through the
wastewater for several minutes to raise the initial DO concentration. The
bottle lid, which was fitted with a DO probe, was then secured to the
bottle allowing the wastewater to overflow to ensure zero headspace within
the bottle. To test, the sample was stirred using a magnetic stirrer, and
the DO concentration was recorded with time. The DO uptake experiments
were typically short in duration (less than 1 hour) and provided an esti-
mate of the initial oxygen utilization rate.
The second oxygen uptake rate experiment performed was similar to a
BOD determination. To a 0.5-L amber glass respirometry bottle, 250 ml of
sample was added. The respirometry bottle lid has a tube fitting to allow
the bottle to be connected to a mercury manometer. A T-connector was
inserted in the manometer tubing; lithium hydroxide was poured in the side
tube to absorb produced carbon dioxide, and the side tube was sealed. The
bottle was then clamped in a wrist-action shaker and sufficiently agitated
to ensure that oxygen transfer was not rate limiting. The pressure drop
resulting from aerobic (oxygen-consuming) biological activity was measured
with the mercury manometer as a function of time. Duplicate runs were
performed. The BOD-type experiments were typically long term in nature (on
the order of days) and provided an estimate of the average potential oxygen
utilization rate.
F-32
-------
A summary of oxygen utilization rates for samples from Ponds B, C, and
D is given in Table F-15.
F.I.1.3 Site 3.5 Site 3 operates two separate manufacturing
facilities, a petroleum refinery and a lubricating oil plant on the Gulf
Coast. The refinery produces various grades of gasoline and fuel oils.
The lubricating oil plant refines crude oil fractions from the refinery to
the lubricating oil base, which is blended into lubricating oil at other
sites. The two facilities have separate WWT systems and discharge through
separate outfalls to rivers.
Process wastewater enters the refinery WWT system at a flow rate of
approximately 18,900 L/min. The WWT system consists of neutralization,
equalization, flocculation, dissolved air flotation (the float is pumped to
a sludge tank), aeration, and clarification (the bulk of the underflow is
recycled to the aeration basin, excess sludge is pumped to an aerobic
digester, and the overflow passes to the refinery polishing pond).
The lube oil plant's process wastewater stream flows intermittently to
a retention/neutralization basin. The neutralized wastewater along with
another "oily water" stream and cooling water flows to an American
Petroleum Institute (API) separator. The flow from the API separator is
approximately 7,600 L/min and passes to dissolved air flotation, equaliza-
tion, aeration, and clarification. The clarifier overflow then flows
through an open channel to the polishing pond, which also receives storm
water runoff from a holding basin. ,
Preliminary sampling of the polishing ponds was performed on
August 27, 1986, to determine the wastewater composition and to evaluate
the potential for biodegradation and air emissions. The refinery polishing
pond has a depth of 1.2 to 3 m, a flow rate of 27 million L/d, and a reten-
tion time of 1.7 d. The lube oil polishing pond has a depth of approxi-
mately 1.2 to 1.5 m, a flow rate of 11 million L/d, and a retention time of
4 d. Both polishing pond's discharge to rivers.
Two samples, one near the bottom and the second approximately 7.6 cm
below the surface at the same point, were collected, from each polishing
pond for chemical analysis. Each sample was pumped through tygon tubing
into an amber glass bottle with Teflon-lined cap. The refinery polishing
F-33
-------
TABLE F-15. SUMMARY OF RESULTS FOR ALL OXYGEN UPTAKE EXPERIMENTS
PERFORMED WITH SAMPLES TAKEN AT SITE 2 SURFACE IMPOUNDMENTS3
Pond sample
Experimental oxygen uptake rate,
aiiu pi coci —
vation status
B(W) (normal)
B(W) (killed)
B(SE) (normal)
B(SE) (killed)
C (normal)
C (killed)
D (normal)
D (killed)
DO depletion
7.19
0.227
12.1
0.504
2.85
0.242
38C
38C
BOD-type
34.9
33.8
5.75
143
TSDF s Treatment, storage, and disposal facility.
DO s Dissolved oxygen.
BOD s Biochemical oxygen demand.
aThe purpose of this table is to demonstrate noncompound-specific
oxygen uptake rates determined by two methods and to demonstrate
the biological (as compared with chemical) nature of the oxygen
demand.
^Oxygen uptake rates were determined by using a least squares
linear regression on the data.
cThe DO depletion experiment was modified as explained in the text.
F-34
-------
pond sampling point was at the edge of the pond opposite the inlet and
about halfway along the length. The lube oil plant polishing pond samples
were collected at a point 1.8 m from the edge of a small pier near the
inlet end of the pond. In addition, a sample was obtained from each pond
at the same sampling point for biodegradation rate studies. These were
pumped into Nalgene containers.
The chemical analysis for purgeable organics was done in accordance
with EPA Method 624. The analysis involved a gas chromatography-mass
spectrometry (GC-MS) search for 31 specific organic priority pollutants.
None of these compounds was found in any of the four chemical analysis
samples above a minimum detection limit of 10 /*g/L. The samples also were
analyzed for acid, base, and neutral extractable compounds by EPA
Method 625. This analysis involved a search for 81 specific organic
compounds, none of which was found at concentrations above the minimum
detection level.
Because no priority pollutants were found in the chemical analysis
samples above the minimum detection limit, no compound-specific biodegrada-
tion rates were obtained. However, the presence of aerobic biological
activity was determined by the ability of the microorganisms to remove
oxygen from the wastewater. A wide-mouth, amber glass, 0.5-L bottle was
filled with wastewater from each biodegradation rate sample and allowed to
come to thermal equilibrium. Air then was bubbled through the sample for
approximately 5 min to raise the initial DO concentration. A magnetic stir
bar was added to the sample bottle. The lid, fitted with a DO probe, was
secured allowing the wastewater to overflow in order to ensure zero head-
space within the bottle. The sample was stirred using a magnetic stirrer,
and the DO concentration was recorded with time. Figures F-l and F-2
present the results of the DO depletion experiments on the samples obtained
near the surfaces of the refinery polishing pond and the lube oil plant
polishing pond, respectively. In addition, on the basis of the measured
oxygen uptake rate, the amount of biomass was estimated to be 0.0031 g/L in
the refinery polishing pond and 0.0014 g/L in the lube oil polishing pond.
F.I.1.4 Site 4.8 Site 4 is a chemical plant located in a south-
western State. The plant produces aldehydes, glycols, glycol ethers,
F-35
-------
1 5
-------
Regression Output:
y-intercept = 0.204 mg/L
slope = 0.171 mg/L-h
R2 = 0.9882
a Experimental DO uptake
Linear regression DO uptake
Figure F-2. TSDF Site 3 lube oil plant polishing pond dissolved oxygen uptake curve.7
F-37
-------
nitriles, esters, and numerous other products. Manufacturing wastewater is
treated in a series of seven oxidation basins.
Wastewater and runoff are collected at different points within the
manufacturing area of the plant. The wastewater flows through four small
basins for settling and skimming to the series of seven oxidation basins.
Six of these basins contain mechanical aerators; one is unaerated. The
discharge from the unaerated basin is pumped either to the last aerated
basin or to a series of four large unlined facultative (facultative means
both aerobic and anaerobic activity are present) basins. The wastewater
effluent averages 11.7 million L/d and is discharged from either the last
aerated basin or the last large facultative basin to surface water.
The discharge permit application for the plant included the informa-
tion presented in Table F-16 about organic priority pollutants found at
detectable levels in the effluent.
Preliminary sampling was performed on August 26, 1986, from the first
facultative lagoon to determine the composition of wastewater in the lagoon
and the potential for biodegradation and air emissions. The lagoon is
243,000 m^ in area, and the depth ranges from 0.6 to 1.5 m. The lagoon was
not well mixed.
Two samples, one near the bottom and one near the surface of the
lagoon, were collected for chemical analysis. Each sample was pumped
through tygon tubing into an amber glass bottle with Teflon-lined cap. The
sampling point was 1.8 m from the north edge of the lagoon. In addition,
samples were pumped into Nalgene containers from the same sampling point
for biodegradation rate studies.
The chemical analysis for purgeable organics was done in accordance
with EPA Method 624. The analysis involved a GC-MS search for 31 specific
organic priority pollutants. None of these compounds was found in either
sample above a minimum detection limit of 10 /
-------
TABLE F-16. ORGANIC PRIORITY POLLUTANTS FOUND AT DETECTABLE
LEVELS IN TSDF SITE 4 WASTEWATER EFFLUENT3
Methyl ene chloride
AcenaphthyLene
Bis(2-ethyl hexyl) phthalate
Naphthalene
Maximum
30-day value,
30
10
71
12
Long-term
average value,
18
10
24
4
TSDF = Treatment, storage, and disposal facility.
aThis table presents information obtained from the Site 4 discharge
permit application.
F-39
-------
Two experiments were performed to measure the oxygen consumption rate
of the microorganisms in the wastewater. The first was the DO depletion
experiment. A wide-mouth, amber glass, 0.5-L bottle was filled with
wastewater from the biodegradation rate sample and allowed to come to
thermal equilibrium. Air then was bubbled through the sample for approxi-
mately 5 min to raise the initial DO concentration. A magnetic stir bar
was added to the sample bottle. The lid, fitted with a DO probe, was
secured allowing the wastewater to overflow in order to ensure zero head-
space within the bottle. The sample was stirred, and the DO concentration
was recorded with time. Figure F-3 presents the results of the DO deple-
tion experiment. In addition, on the basis of the measured oxygen uptake
rate, the amount of biomass at this facultative lagoon was estimated to be
0.044 g/L.
The second oxygen uptake rate experiment performed was similar to a
BOD determination. A 300-mL sample was added to a 0.5-L amber glass
respirometry bottle. The respirometry bottle lid has a tube fitting that
allows the bottle to be connected to a mercury manometer. A T-connector
was inserted in the manometer tubing, lithium hydroxide was poured in the
side tube to absorb carbon dioxide, and the side tube was sealed. The
bottle then was clamped in a wrist-action shaker and sufficiently agitated
to ensure that oxygen transfer was not rate limiting. The pressure drop
resulting from aerobic biological activity was measured with the mercury
manometer as a function of time. The results of the BOD oxygen consumption
experiment are presented in Figure F-4.
The presence of anaerobic biological activity was determined by the
ability of the wastewater sample to produce gas in the absence of oxygen.
In the test procedure, nitrogen was bubbled through the liquid sample to
purge any oxygen that may have been introduced during sample collection or
transfer. The sample container was then sealed with a lid modified with a
small tubing connection to a quantitative gas collection system. Two dif-
ferent gas collection systems were used. One system consisted of a water-
filled inverted graduated cylinder that collected gas by water displace-
ment. The second gas collection system consisted of a horizontal syringe
whose free-moving plunger provided a quantitative measure of the volume of
F-40
-------
4.0
3.5
3.0
Regression Output:
y-intereept = 0.315 mg/L
slope = 2.40 mg/L-hr
R2 = 0.9745
a Experimental DO uptake
Linear regression OO uptake
20
10
Time (min)
60
80
Figure F-3. TSDF Site 4 dissolved oxygen uptake curve/
F-41
-------
"3b
D
8
Regression Output:
/•intercept = 2.06 mg/L
slope = 1.57 mg/L-hr
R2 = 0.9924
Q Experimental BOO
Linear regression BOD
I— 1
Rgure F-4. TSDF Site 4 biochemical oxygen demand curve.10
F-42
-------
gas produced. Direct exposure of the sample to light was limited by
employing amber glass sample containers or cardboard box shields. Anaero-
bic gas generation in the sample from the first facultative lagoon at
Site 4 was measured to be 0.022 mL/L-h.
F.I.1.5 Site 5.11 site 5 is a chemical manufacturing plant that
produces primarily nitrated aromatics and aromatic amines. The raw materi-
als for this process include benzene, toluene, and nitric and sulfuric
acid. A field study program was conducted during a 3-day period from
November 18 to November 20, 1985. The lagoon studied during the testing
program was the wastewater holding pond for the WWT system at the plant.
The WWT system includes two decant tanks, a steam stripper, a carbon
adsorption system, and final pH-adjustment tank prior to the discharge of
the wastewater stream into surface water.
The goals of the lagoon field study were to:
• Evaluate the three-dimensional variation of organic chemical
concentrations in the Site 5 wastewater holding lagoon
• Measure lagoon air emissions using emission isolation flux
chambers.
Additional testing was performed on the Site 5 steam stripper (refer to
Section F.2.3.1.3) and carbon adsorption system (refer to Section F.2.2.2).
Two wastewater streams that enter the process at the beginning are
distillation bottoms from aniline production (Resource Conservation and
Recovery Act [RCRA] waste code K083) and the nitrobenzene production waste-
water (RCRA waste code K104). These two wastewater streams flow into,a
holding tank, called the "red" tank, due to the color of the wastewater
streams. As the tank is filled, the overflow passes through a submerged
outlet into the wastewater holding lagoon. The.third process stream that
enters the lagoon is the plant sump wastewater. This stream is intermit-
tent and occurs primarily during periods of heavy rain. Two sump pumps are
activated when needed, both of which pump into the lagoon. The organic
sump pump is normally the only one in operation and pumps directly into the
steam-stripper feed tank.
The lagoon where the test program was conducted is 105 m by 36 m by
3 m (the depth is measured from the plant roadway elevation rather than
F-43
-------
from the top of the berm). It is surrounded by a cement wall and a plant
roadway on the east or plant side. The wall extends 0.3 m above the road
surface. The berm on the other three sides is 1.7 m wide, consists of
ground seashells, and extends to approximately the same height above the
lagoon contents as the cement wall. The lagoon is lined with packed clay.
During the test period, the liquid level in the lagoon ranged from 1.2 m to
2.1 m in depth, with about 40.6 cm of freeboard (measured down from the
level of the plant roadway) above the liquid surface. The remaining depth
was comprised of a bottom sludge layer, the thickness of which was never
measured directly. By subtraction, this layer varied from about 0.6 m to
1.5 m deep. Retention time in the lagoon is 20.8 days.
Sampling locations were selected using a systematic approach. The
lagoon was divided into 15 grids of equal area; each was approximately 12 m
by 21 m or 250 m^. Four of the grids (A, B, E, and F) were chosen for
liquid and air emission sampling. Two liquid grab samples were collected
from the impoundment surface at each sampling location just prior to plac-
ing the flux chamber in position. Duplicate gas canister samples were
collected at each flux chamber location. An additional location near the
southwest corner of the lagoon was sampled to examine the effect of a
sludge layer on the emission processes. Sludge layer emissions were meas-
ured, and two liquid and one sludge sample also were collected. After the
flux chamber samples were collected, liquid samples were collected at 0.3-m
increments of depth, and a sediment sample was collected from the bottom at
each of four of the sampling locations (A, B, E, and F) for the stratifica-
tion study. Sampling spanned 2 days; Locations A and B were sampled on
November 19, 1985, and Locations E and F and the southwest corner on Novem-
ber 20, 1985.
Gas samples were collected in evacuated stainless-steel canisters.
Liquid grab samples from the impoundment surface were collected in clean,
glass VOA vials fitted with Teflon capliners. A Bacon Bomb sampler,
designed for collecting samples from storage tank bottoms, was used to
collect liquid grab samples from specified depths for the stratification
study. This sampler consists of a nickel-plated brass container with a
protruding plunger. A cord was attached to the upper end of the plunger to
F-44
-------
open the bomb, which closed when tension on the cord was released. A Ponar
grab sampler (clamshell-type scoop) was used to sample sediment and sludge
to a depth of several centimeters at the bottom of the lagoon. Offsite
analyses of gas, liquid, and sludge samples were performed on a Varian
Model 3700 GC with flame ionization detector/photoionization detector/Hall
electrolytic conductivity detector (FID/PID/HECD).
Table F-17 presents the results of the direct emission measurement
program. Results of the stratification analyses are summarized in Table
F-18. The results for each grid point provide fairly conclusive evidence
of stratification between the liquid and sludge layers, but not in the
liquid layer itself. The sludge layer ranged up to several hundredfold
more concentrated than the liquid layer. Table F-19 provides the results
of a comparison of the liquid and sludge organic contents using an average
concentration for each of the four primary lagoon organic components
(nitrobenzene, 2,4-dinitrophenol, 4,6-dinitro-o-cresol, and benzene)
reported in the liquid and sludge layers.
F.I.1.6 Site 6.15 Site 6 is a commercial hazardous waste TSDF. The
site began operation in 1972 and was acquired by the current owner in 1979
and upgraded to accept hazardous wastes. Before a waste is accepted for
disposal at the facility, samples must be analyzed to determine compat-
ibility with the facility processes. Water-reactive, explosive, radio-
active, or pathogenic wastes are not accepted. Hazardous wastes are
received from the petroleum, agricultural products, electronics, wood and
paper, and chemical industries.
Emission measurements-were performed for 2 days during the period from
June 18 through 23, 1984, on a surface impoundment at Site 6. Source
testing of inactive and active landfills at Site 6 is described in Section
F.I.3.2. Section F.I.5.1 presents the results of the Site 6 drum storage
and handling area testing.
The surface impoundment is used for volume reduction via solar evapor-
ation. There is daily activity at most of the Site 6 surface impoundments.
Wastes are transported to the impoundments by tank truck. During the first
day of testing at the impoundment, a liquid-phase material balance was made
over an 8.5-h period. According to company records, 58,000 L of waste were
dumped into this impoundment during this 8.5-h period.
F-45
-------
TABLE F-17. SOURCE TESTING RESULTS FOR TSDF SITE 5,
WASTEWATER HOLDING LAGOON12
Constituent
Cyclohexane
Tetrachl oroethy 1 ene
Toluene
Benzene
n-Undecane
Methylchloride
Total NMHCd
Emission
rate,3
x 103 Mg/yr
1.8
0.7
2,800
7,600
3.7
120
15,000
Liquid
concentration,**
x 103 mg/L
38
58
2,600
17,000
150
29
75,000
Mass transfer
coefficient,0
x 106 m/s
' 0.4
0.1
9.0
3.7
0.2
35
1.7
TSDF s Treatment, storage, and disposal facility.
NMHC - Nonmethane hydrocarbon.
aAverage of emission rates measured with a flux chamber at Grid Points A, B,
E, F, and the SW corner.
^Average of concentrations measured from liquid samples taken at Grid Points
A, B, E, F, and the SW corner.
cCalculated from measured emission rates and liquid concentrations.
NMHC totals do not represent column sums because only constituents
detected in gas and liquid samples are presented.
F-46
-------
TABLE F-18.
STRATIFICATION STUDY RESULTS9 FOR TSDF SITE 5,
WASTEWATER HOLDING LAGOON13
Constituent concentrationc
Sample
location^
A-l
B-l
E-l
F-l
A-2
B-2
E-2
F-2
A-3
E-3
F-3
A-4
A-5
B-5
E-5
F-5
Sample
type
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
Sludge
Sludge
Sludge
Sludge
Sample
depth, m
0-0.3
0-0.3
0-0.3
0-0.3
0.9
0.9
0.9
0.9
1.2
1.2
1.2
1.5
1.8
1.2
1.5
1.5
Nitro-
benzene
440
630
390
670
560
880
420
460
480
380
350
1,100
87,000
130,000
14,000
120,000
2,4-Dinitro-
phenol
1 , 400
160
130
470
250
320
<20
3,000
210
260
110
210
4,600
18,000
9,300
5,200
4,6-Dinitro-
o-cresol
32
38
25
63
28
45
15
82
45
<10
30
56
2,300
7,700
3,300
2,600
Benzene
12
15
17
16
13
23
21
30
9.4
32
59
23,000d
1,000
1,000
372
2,400
TSDF = Treatment, storage, and disposal facility.
aThis table presents the results of the analysis of three-dimensional
variation of organic chemical concentrations in the TSDF Site 5 wastewater
holding lagoon. Liquid samples were collected at 0.3-m increments of depth
and a sediment sample was collected from the bottom at each of four sampling
locations.
^Sampling grid (A, B, E, and F) and sample number at each depth within the
grid (1, 2, 3, 4, and 5).
Concentration results are gas chromatography-flame ionization detector
analyses, in mg/L for liquids and mg/kg for sludges.
dSample contaminated with sludge.
F-47
-------
TABLE F-19. SLUDGE:LIQUID ORGANIC CONTENT COMPARISON
FOR TSDF SITE 5, WASTEWATER HOLDING LAGOON14
Liquid data Sludge data
Weight ratio
sludge: liquid
Estimated waste volume
Average waste constituent
concentrations3
Nitrobenzene
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
Benzene
Estimated weight of
waste constituent
4,400 m3 4,100
560 mg/L
460 mg/L
38 mg/L
22 mg/L
88,000 mg/kg
9,300 mg/kg
4,000 mg/kg
1,200 mg/kg
Nitrobenzene
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
Benzene
2,500 kg
2,000 kg
170 kg
100 kg
360,000 kg
38,000 kg
16,000 kg
4,900 kg
Average
144
19
94
49
= 77
TSDF s Treatment, storage, and disposal facility.
aAverage concentrations calculated using all liquid values greater than detec-
tion limits.
F-48
-------
The objectives of the testing program at the surface impoundment were:
• To obtain emission rate data using the emission isolation
flux chamber approach
• To obtain emission rate data using a mass balance approach
• To obtain data on the concentration of VO for comparison to
compounds identified during emission measurements and as
future input to predictive models.
The surface impoundment is a rectangular pond with nominal dimensions
of 137 m by 46 m. The entire surface of the pond was gridded (24 equal
grids). Emission measurements using the flux chamber and liquid samples
were collected on June 20 and June 22, 1984. Six sampling locations
(grids) were randomly selected for the flux chamber measurements. However,
only three different locations could be sampled (one sample per location)
on the first day and four different locations (one sample each at two loca-
tions and duplicate samples at two locations) on the second day because of
time constraints. Liquid samples were taken corresponding to each emission
measurement at each sampling location.
Air emission measurements were made using the emission isolation flux
chamber. It should be noted that during the flux chamber measurements, an
additional 30.5 m of sampling line was required to reach the sampling loca-
tions from the shore. Under normal conditions, the flux chamber is oper-
ated with 3.1 m of sampling line. In addition, during collection of the
canister samples on June 20 at two sampling locations, the chamber differ-
ential pressure was higher than normal. This abnormality may have affected
those canister results on June 20.
Air samples were collected in evacuated stainless-steel canisters and
analyzed offsite by a Varian Model 3700 GC-FID/PID/HECD. Liquid samples
were collected in glass vials with Teflon-lined caps following the guide-
lines outlined in American Society of Testing and Materials (ASTM) D33701,
"Standard Practices for Sampling Water."16 Liquid samples also were
analyzed offsite by the Varian Model 3700 GC-FID/PID/HECD. Table F-20
summarizes the test results for the Site 6 surface impoundment.
F.I.1.7 Site 7.17'18 Site 7 is a commerical hazardous waste
management facility located in the northeastern United States. The site
was developed for hazardous waste operations in the early 1970s.
F-49
-------
TABLE F-20. SOURCE TESTING RESULTS3 FOR TSDF SITE 6, SURFACE IMPOUNDMENT
Constituent
Mean
emission rate,
Mg/yr
Mean
liquid concentration,
mg/L
Mass transfer
coefficient,*3
xlO6 m/s
June 20, 1984, resu1tsc
Toluene 0.4
Ethyl benzene 0.2
Methylene chloride 2.4
1,1,1-Trichloroethane 4.9
Chloroform 0.2
p-Dichlorobenzene 0.1
Total NMHCd 16
June 22, 1984, results
9.0
4.9
18
28
1.0
1.8
320
0,
0,
0.7
1.2
0.9
0.3
0.2
Toluene
Ethyl benzene
Methyl ene chloride
1,1, 1-Tri chl oroethane
Chloroform
p-Dichl orobenzene
Total NMHCd
2.0
1.1
6.8
9.3
0.5
0.1
61
4.3
5.4
4.2
19
0.2
2.0
280
2.4
1.0
8.4
2.6
12
0.4
1.1
TSDF s Treatment, storage, and disposal facility.
NMHC s Nonmethane hydrocarbon.
aAir emissions were sampled with a flux chamber and liquid concentrations were
determined from grab samples.
^Calculated from measured emission rates and liquid concentrations.
cDuring collection of the canister samples on June 20 at two sampling points,
the chamber differential pressure was higher than normal. This abnormality
may have affected those canister results on June 20.
"The NMHC totals do not represent column sums because only major constituents
(in terms of relative concentrations) are presented.
F-50
-------
The site's aqueous WWT system has a throughput of 545,000 L/d with
typical discharges ranging from 330,000 to 382,000 L/d. At the time of the
tests, wastes accepted into the WWT system included washwaters, pickle
liquors, and leachates from other facilities within the WWT system. The
WWT process at Site 7 includes chemical, physical, and biological treat-
ment. A holding pond, a reducing lagoon, and an oxidizing lagoon of the
WWT system were tested for emissions during the first week of October 1983.
Testing of an active and a closed landfill at Site 7 is described in
Section F.I.3.5. Section F.I.5.3 discusses testing of emissions from the
Site 7 drum storage building.
The holding pond is an 18,000-m3 aerated (pump aerator) Hypalon-lined
lagoon that receives the aqueous phase from the salts area of the WWT sys-
tem. The aqueous phase includes organics that are soluble or suspendible
at a pH greater than 11.5. Dimensions of the pond are nominally 135 by 36
by 3.1 m. Freeboard ranges from 0.6 to 1.5 m. Filling and discharge of
the holding pond are conducted monthly. The field test took place several
days after draining. At the time of the test, the pond had a nominal 0.3
to 0.5 m of liquid waste and several meters of sludge present. Because of
the low liquid level, the pump aerator was not operational.
The reducing lagoon is a 3,900-m3 Hypalon-lined lagoon that receives
incoming wastes to the WWT system that are classified as reducing agents.
The pH is typically less than 2. Dimensions of the lagoon are nominally 34
by 33 by 3.9 m. The freeboard ranges from 0.6 to 1.5 m. Liquid waste is
received via tank truck and discharged through a flexible hose into the
lagoon. Localized discharges into the corners of the lagoon have created a
zone of bulk solids, precipitation products, and construction debris. The
surface of the lagoon was coated with an oil film. The frequency of waste
unloading observed during the field test was nominally four to five tank
trucks per day. The frequency is not regular. The WWT system is operated
on a batch basis, making the residence time (throughput) dependent upon the
volume of waste received into the system.
The oxidizing lagoon is a 3,900-m3 Hypalon-lined lagoon that receives
incoming wastes to the WWT system"that are oxidizing agents. The wastes
include halogens and organics compounds (total organic carbon less than
F-51
-------
2 percent) and have a pH less than 2. Dimensions of the lagoon are
nominally 35 by 35 by 4.1 m. The freeboard ranges from 0.6 to 1.5 m.
Liquid waste is received via tank truck and discharged through flexible
hose into the lagoon. Localized discharges into the north corner of the
lagoon have created a prominent "delta" of bulk solids, precipitation
products, and construction debris. The surface of the lagoon was coated
with an oil film. The frequency of waste unloading observed during the
field test appeared somewhat greater for the oxidizing lagoon than for the
reducing lagoon (four to five truckloads per day). As with the reducing
lagoon, the oxidizing lagoon is a batch operation, making the residence
time (throughput) dependent on the volume of waste received.
The objective of the testing program at Site 7 surface impoundments
was to develop and verify techniques for estimating air emissions from
these sources. The reducing lagoon and oxidizing lagoon were each gridded,
and air emission measurements were made within certain grids using the flux
chamber technique. Liquid samples were obtained concurrent with flux cham-
ber testing. Concurrent samples were collected from two grids at each
lagoon. Duplicate flux chamber measurements and concurrent liquid samples
were taken at a single location in the holding pond.
Air sample collection was made by evacuated stainless-steel canisters,
and analysis was conducted offsite using a Varian Model 3700 GC-FID/PID/
HECD. Liquid samples were collected in glass containers in a manner that
would minimize any headspace and analyzed offsite by the Varian Model
3700 GC-FID/PID/HECD. Tables F-21 through F-23 summarize the test results
from the holding pond, reducing lagoon, and oxidizing lagoon, respectively.
F.I.2 Wastewater Treatment
F.I.2.1 Site 8.19,20
Site 8 is a petroleum refinery located on the East Coast with a
capacity of 180,000 barrels per day. Limited quantities of benzene,
toluene, and cumene are also produced. Most of the operations are
continuous (as opposed to batch) processes. Rainwater collected in the
process area is treated as process wastewater.
The plant has two separate primary treatment trains that treat waste-
water from different process areas. The more concentrated wastewater
F-52
-------
TABLE F-21. SOURCE TESTING RESULTS3 FOR TSDF SITE 7, HOLDING POND
Constituent
Mean
emission rate,
x 106 Mg/yr
Mean liquid
concentration,
x 103 mg/L
Mass transfer
coefficient,'3
x 109 m/s
Benzene
Toluene
Ethyl benzene
Naphthalene
Methyl ene chloride
Chloroform
1,1, 1-Trichl oroethane
Chlorobenzene
p-Dichlorobenzene
Acetaldehyde
Total NMHCC
7,900
81,000
15,000
500
240,000
3,400
18,000
<370
6,000
11,000
1,200,000
19
230
37
2
500
10
30
62
9
21
2,600
2,700
2,300
2,600
1,600
3,100
2,200
3,900
<39
4,300
3 , 400
3,000
TSDF = Treatment, storage, and disposal facility.
NMHC = Nonmethane hydrocarbon.
aAir emissions were sampled with a flux chamber and liquid concentrations
were determined from grab samples.
^Calculated from measured emission rates and liquid concentrations.
cThe NMHC totals do not represent column sums because only major constituents
(in terms of relative concentrations) are presented.
F-53
-------
TABLE F-22. SOURCE TESTING RESULTS3 FOR TSDF SITE 7, REDUCING LAGOON
Constituent
Mean
emission rate,
x 106 Mg/yr
Mean liquid
concentration,
x 103 mg/L
Mass transfer
coefficient,'5
x 106 m/s
Benzene
Toluene
Ethyl benzene
Styrene
Naphthalene
Methyl ene chloride
Chloroform
1,1, 1-Tri chl oroethane
Carbon tetrachloride
p-Dichlorobenzene
Total NMHCC
1,600
160,000
2,700
2,000
500
12,000
1,000
35,000
12,000
38,000
640,000
9.2
910
14
10
5.4
29
5.0
130
31
420
3,600
4.9
5.0
5.5
5.7
2.6
12
5.7
7.6
11
2.6
5.0
TSDF s Treatment, storage, and disposal facility.
NMHC - Nonmethane hydrocarbon.
aAir emissions were sampled with a flux chamber and liquid concentrations
were determined from grab samples.
^Calculated from measured emission rates and liquid concentration.
cThe NMHC totals do not represent column sums because only major constituents
(in terms of relative concentrations) are presented.
F-54
-------
TABLE F-23. SOURCE TESTING RESULTS3 FOR TSDF SITE 7, OXIDIZING LAGOON
Constituent
Mean
emission rate,
x 103 Mg/yr
Waste
concentration,'3
Mass transfer
coefficient,0
x 109 m/s
Toluene
Ethyl benzene
1, 1 , 1-Trichloroethane
Total NMKCd
170
43
2,000
7,600
7.8
20
1.0
1,400
380
37
35,000
94
TSDF = Treatment, storage, and disposal facility.
NMHC = Nonmethane hydrocarbon.
aThis table presents the results of analyses of air and waste oil and solids
mixture samples collected during source testing at the TSDF Site 7 oxidizing
lagoon. Air emissions were sampled with a flux chamber and waste concentra-
tions were determined from grab samples.
lagoon surface contained oils and solids; therefore, the grab sample of
waste from the pond was a sludge and was analyzed as a soil sample.
cCalculated from measured emission rates and waste concentration.
NMHC totals do not represent column sums because only major constituents
(in terms of relative concentrations) are presented.
F-55
-------
stream (containing most of the petrochemical plant wastewater and some of
the refinery wastewater), typically 5,700 to 7,600 L/min, flows to a skim
and surge tank that is operated for hydraulic equalization (i.e., the tank
level rises and falls while wastewater is pumped out at a relatively
constant rate). The water flows to an API separator. Effluent from this
separator is mixed with a small volume of "desalter water" and then passes
through two parallel roughing filters. The roughing filter effluent is
combined and then divided between two parallel 18 m diameter by 2.4 m deep
primary clarifiers. The underflow from the primary clarifiers is pumped to
two thickeners. The primary clarifier overflow is combined and split
between the two parallel 37 m diameter by 5.5 m deep oxidation tanks.
These tanks have approximately 0.6 m of freeboard and hold 5.7 million L
each.
The second wastewater stream enters a skim and surge tank that is
operated for hydraulic equalization and is gravity fed at a relatively
constant rate (typically 9,500 to 11,000 L/min) to a second API separator.
The effluent from the separator is evenly split between the two oxidation
tanks. This wastewater enters the oxidation tanks as a separate stream
from the other treatment train.
Air is supplied to the oxidation tank from one of three available 600
horsepower compressers. The air is approximately evenly divided between
the two tanks and enters through a distributor system of 2,000 diffusers
per tank. The dissolved oxygen in the tanks is typically maintained
between 1.5 and 2.0 mg/L. The oxidation tanks are typically operated at
1,800 to 2,300 mg/L of mixed liquor volatile suspended solids. Based on a
combined wastewater flow of 19,000 L/min, the residence time in the
oxidation tanks is approximately 10 to 11 hours.
The overflow from the two aeration tanks is' combined and then split
between two parallel secondary clarifiers. The clarifiers are 43 m in
diameter and 2.7 m deep. The overflow from the clarifiers is combined and
passed through a final sand filter before discharge to the river. About
1/3 of the flow to the secondary clarifiers is pumped from the bottom and
returned to the aeration tanks. These streams are not combined (the east
secondary clarifier returns sludge to the east oxidation tank; the west
F-56
-------
secondary clarifier returns sludge to the west oxidation tank). When
necessary to limit the mixed liquor suspended solids (MLSS) to the desired
range of 1,800 to 2,300 mg/L, sludge is wasted from the return lines. The
oxidation tank in the east was 2,300 mg/L during the test, based on
analyses conducted by the plant. No sludge was being wasted at the time of
the site visit. Waste-activated sludge is pumped to the thickeners where
it is combined with primary sludge. The thickened sludge is centrifuged
and the solids are incinerated.
A field test to measure air emissions from one of the two parallel
oxidation tanks (using a mass emissions flux chamber) and biodegradation
rates was conducted in August 1987. For flux chamber sampling, the oxida-
tion tank was divided into five concentric rings, each having an equal
area. Emissions were first measured along a diameter at the midpoint of
each ring. In addition to these 10 points, the tank's centroid and three
other points were also sampled. The three additional points lay on two
transverse lines 25° and 43° off the original transect line.
Air samples were taken in evacuated canisters and analyzed by GC-
FID/PID/HECD. Using sample concentrations and. airflow rates as measured
with the flux chamber, average emissions were calculated for the tank
surface. The emissions data are tabulated by compound in Table F-24. Note
that these emissions are given for a single aeration tank and should be
doubled to approximate the total emissions from the activated sludge units
at the refinery.
Biodegradation rate tests were conducted with mixtures of aeration
tank influent and recycled-sludge. The more concentrated of the two
aeration tank influent streams was used. This resulted in higher, and thus
easier to detect, concentrations of benzene, toluene, and xylene than the
average concentration of the combined tank influents.
In order to distinguish between removal of organics from mixed liquor
due to biodegradation and removal due to mass transfer into the air,
experiments were conducted that permitted biodegradation to take place
while limiting air stripping. The samples of aeration tank feed and
recycled sludge were mixed in proportions that reflected the actual ratio
of aeration tank feed and recycle sludge at the time they were taken.
F-57
-------
TABLE F-24. SOURCE TESTING RESULTS9 FOR TSDF SITE 8,
AERATION TANK
Compound
Emission rate,
x 103 Mg/yr
Liquid
concentration,
Mass transfer
coefficient,'5
x 106 m/s
Methane
C-3 VOC
n-Heptane
n-Octane
n-Nonane
n-Decane
n-Undecane
3-Methyl heptane
Methyl -cycl ohexane
Toluene
Cyclopentane
Isoheptane
Benzene
p,m-Xylene
o-Xylene
Ethyl benzene
TNMHCC
510
17
28
53
68
57
34
23
19
26
1.2
11
1.7
5.1
3.9
1.4
1,200
NA
NA
NA
NA
NA
NA
NA
NA
NA
<2.7
NA
NA
<1.1
<1.1
<1.1
NA
NA
NC
NC
NC
NC
NC
NC
NC
NC
NC
>280
NC
NC
>47
>140
>100
NC
NC
NA = Not analyzed.
NC s Not calculated.
TNMHC s Total nonmethane hydrocarbons.
aAir emission data estimated from flux measurements made at different
points on the surface of a submerged aeration activated sludge tank.
Liquid composition estimated from average of eight samples of aeration
tank effluent taken over an 8-day period. Note that the test was con-
ducted on, and data were reported for, one of two identical aeration
tanks at the refinery.
^Calculated from measured emission rates and average effluent concen-
tration. Tank area = 1,080 m2.
cThe TNMHC emission rate is based on a chromatographic trace that
includes unidentified hydrocarbons not listed in this table.
F-58
-------
The gross sample was divided using a 2-L NalgeneR graduated cylinder
as follows: seven 1-L bottles were partially filled with 500 cm^ of
mixture, and two SOO-cm^ bottles were completely filled with mixture. The
filled bottles were designated for volatile suspended solids analysis and
immediately stored on ice. One of the partially filled 1-L bottles was
immediately preserved with 10 ml of saturated copper sulfate solution and
agitated gently to ensure that the copper sulfate solution was distributed.
Approximately 100 ml was then poured from the bottle into a disposable
polypropylene beaker. The beaker was then used to fill two pre-acidified
40-cm3 septum vials. The two 40-cm3 bottles were stored on ice immediately
thereafter.
The partially filled 1-L bottles and the partially filled 500-mL
bottle were then mounted on a wrist action shaker and continuously
agitated. As time progressed, bottles were removed from the shaker, one by
one, and preserved with copper sulfate using the same procedure as for the
initial sample. The test was conducted over a period of approximately two
oxidation tank residence times. Similarly, 40-cm3 vials of acidified
sample were filled for purgeable organics analysis. The temperature of the
test mixture at T=0 was 35 °C. The ambient temperature where the test was
conducted varied between 23 and 27 °C. Biodegradation rate test samples
were analyzed for benzene, toluene, and xylenes by EPA Method 602. A total
of three tests were conducted, one each on August 4, 5, and 6, 1987.
An attempt was made to simultaneously measure total oxygen uptake of
the mixture by a respirometric technique. This proved unsuccessful,
possibly because of interferences from dissolved gases in the mixture. The
test was, however, conducted under conditions in which an excess of oxygen
was always available.
Upon analysis of the preserved samples, it was found that essentially
all of the benzene, toluene, and xylene present in the mixture was biode-
graded between the T=0 sample and the next sample (taken at approximately
2 hours). Thus, only lower bounds on biodegradation rates could be calcu-
lated. Rates determined for the three tests are presented in Table F-25.
Because of the higher than expected removal rates, lower bounds on
compound-specific zero order biodegradation rates were based on the removal
F-59
-------
TABLE F-25. BIODEGRADATION RATES3 DETERMINED BY
SHAKER TESTS AT SITE 8
Compound
Benzene
Toluene
p-Xylene
m-Xylene
o-Xylene
Biodegradation
Test 1
>3.5
>4.3
>0.60
>1.7
>1.3
rates, /ig/min-gbiomass
Test 2
>1.4
>1.8
>0.15
>0.84
>0.46
Test 3
>0.40
>0.58
. >0.17
>0.47
>0.34
Total xylenes
>3.5
>1.44
>0.94
aThese rates reflect the essentially complete disappearance of the com-
pounds present at the beginning of the test over a reaction time of
110 to 120 minutes. The rates have been normalized by the biomass con-
centration as determined from a parallel analysis. The difference in
rates between tests is caused by changes in the composition of the
aeration tank influent on successive days.
F-60
-------
rate observed in the first reaction time interval normalized by the inde-
pendently determined volatile suspended solids concentration:
K =
t B
where:
K = lower bound on biodegradation rate, pg compound/(min-gbiomass)
C0 = concentration of compound in bottle preserved at t = 0, /jg/L
Ct = concentration of compound in bottle preserved next, /tg/L
t = reaction time, minutes
B = volatile suspended solids concentration in bottles, g/L.
For two of the three tests, Ct was below detection level for all of the
compounds of interest. The lack of intermediate data precludes the calcula-
tion of first order rate constants or constants of the more complicated
Monod kinetic models.
F.I.2.2 Site 9.2* Site 9 is a synthetic organic chemical production
plant. Plant wastewater is treated in a system that includes two parallel,
mechanically aerated, activated sludge units that discharge to a UNOX-
activated sludge system. A field test was conducted in November 1986 to
determine biodegradation rates for methanol and formaldehyde. Biodegra-
dation rates were determined for the mechanically aerated systems by test-
ing a sample composed of aeration tank feed and recycled sludge mixed in
proportions to actual unit flows.
Each sample was divided using a 2-L plastic graduated cylinder as
follows: up to seven 1-L bottles were partially filled with 500 ml of
mixture, one 1-L bottle was completely filled with the mixture, and one
specially prepared 500-mL bottle was partially filled with 250 ml of the
mixture. The filled bottle was designated for volatile suspended solids
analysis and immediately stored on ice. One of the partially filled 1-L
bottles was immediately preserved with 10 mL of saturated copper sulfate
solution and agitated gently to ensure that the copper sulfate solution was
distributed. This bottle was then used to fill two 40-mL septum vials.
F-61
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The 1-L bottle and the two 40-mL bottles were stored on ice immediately
thereafter for shipment to a laboratory for organic compound analysis.
The specially prepared 500-mL bottle had a plastic tubing stub fitted
into and protruding through the cap. Polyvinyl chloride (PVC) tubing was
connected to the stub leading to a plastic T-connector. One side of the
T-connector was attached to a short length of tubing filled with lithium
hydroxide. The other side of the T-connector was connected to a mercury
manometer. This bottle was used to monitor oxygen uptake over time.
The partially filled 1-L bottle and the partially filled 500-mL bottle
were then mounted on a wrist-action shaker and continuously agitated. Over
a period of up to 24 h, bottles were removed from the shaker one by one and
preserved with copper sulfate using the same procedure as for the initial
sample. Similarly, 40-mL vials were filled for purgeable organics analy-
sis.
Biodegradation rate test samples were analyzed for purgeable organics
by EPA Method 624 (formaldehyde by an MS technique,22 and methanol by
direct-injection GC).
Based on the decrease in methanol and formaldehyde with increasing
reaction times, zero-order biodegradation rates were calculated. These
rates were then normalized by dividing by the biomass present (as indicated
by volatile suspended solids) in the bottles. Biodegradation rates for
methanol and formaldehyde were determined to be 0.53 and 0.082 /jg/
(g»biomass-h), respectively.
F.I.2.3 Svte_10.23.24 site 10 is a synthetic organic chemical
production plant. Wastewater is collected at various points in the
manufacturing area of the plant and pumped intermittently to a sump in the
WWT area. Wastewater is pumped intermittently from this sump to an
equalization tank with a residence time of approximately 90 h. The
equalization tank is not completely mixed and is operated primarily to
accommodate hydraulic surges.
Wastewater is then pumped to a splitter box where it is mixed with
recycled sludge and divided between two identical and parallel, above-
ground, concrete aeration tanks providing approximately 6 days of residence
time. Air is supplied through static mixers in each tank. Approximately
F-62
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5 cm of foam was present on the surface of the tanks except in the areas
directly above the mixers. The aeration tanks contained 2,500 mg/L of
mixed-liquor suspended solids during the test. The water level is main-
tained by an overflow weir.
The wastewater from the two tanks overflows to a splitter box where it
is recombined and then divided evenly between two clarifiers. Sludge is
returned to the aeration tanks at the influent splitter box in an amount
sufficient to maintain the desired volatile suspended solids content of the
mixed liquor.
One tank was divided into 27 2.44 m x 2.44 m grids. An enclosure
device, the isolation emission flux chamber, was used to measure the off-
gas flow rate from the different parts of a grid. A slipstream of the
sample gas was collected for hydrocarbon analysis.
A field test to measure air emissions (with a mass emissions flux
chamber) and biodegradation rates was conducted in September 1986.
Compound-specific air emissions integrated over the tank surface are given
in Table F-26 along with liquid concentration data obtained from analyses
of mixed-liquor samples taken at the same points at which the flux chamber
measurements were made. Gas and liquid analyses were conducted by GC-
FID/PID/HECD.
Samples of a mixture of aeration tank feed and recycled sludge were
dipped from the influent splitter box at the upstream end of the aeration
tank. Each sample was divided using a 2-L plastic graduated cylinder as
follows. Up to seven 1-L bottles were partially filled with 500 ml of
mixture; one 1-L bottle was' completely filled with mixture; and one
specially prepared 500-mL bottle was partially filled with 250 ml of
mixture. The filled bottle was designated for volatile suspended solids
analysis and immediately stored on ice. One of the partially filled 1-L
bottles was immediately preserved with 10 mL of saturated copper sulfate
solution and agitated gently to ensure that the copper sulfate solution was
distributed. This bottle was then used to fill two 40-mL septum vials.
The 1-L bottle and the two 40-mL bottles were stored on ice immediately
thereafter for shipment to a laboratory for organic compound analysis.
F-63
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TABLE F-26. AIR EMISSIONS AND MIXED-LIQUID COMPOSITION IN THE
AERATION TANK AT SITE 10a
Constituent
Emission rate,
x 103 Mg/yr
Liquid
concentration,
Mass transfer
coefficient,'3
x 106 m/s
Methane
C-2 VOCC
Cyclopentane
Isobutene + 1-Butene
t-4-Methyl -2-pentene
Toluene
Methyl ene chloride
1,1, 1-Trichl oroethane
Acetaldehyde
Dimethyl sul fide
Acetone
170
1.1
.93
.12
.11
2.9
.13
.70
5.6
.13
°d
0.0
15.8
0.5
0.0
0.0
1.6
8.3
6.0
170
4.9
70
NM
6.9
180
NM
NM
180
1.6
12
3.3
2.6
0
NM s Not meaningful.
VOC = Volatile organic compound.
aAir emission data estimated from flux measurements made at different
points on the surface of a submerged aeration activated sludge tank
and the average composition of the mixed liquor present in the tank.
^Calculated from measured emission rates and liquid concentration.
cVolatile organic compounds containing two carbons, e.g., ethane.
^Acetone measurements from the tank surface did not exceed blank
concentration levels.
F-64
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The specially prepared 500-mL bottle had a plastic tubing stub fitted
into and protruding through the cap. Tygon tubing was connected to the
stub leading to a plastic T-connector. One side of the T-connector was
attached to a short length of tubing filled with lithium hydroxide. The
other side of the T-connector was connected to a mercury manometer. This
bottle was used to monitor oxygen uptake over time.
The partially filled 1-L bottle and the partially filled 500-mL bottle
were then mounted on a wrist-action shaker and continuously agitated. Over
a period of about 19 h, bottles were removed from the shaker one by one and
preserved with copper sulfate using the same procedure as for the initial
sample. Similarly, 40-mL vials were filled for purgeable organics analy-
sis.
Biodegradation rate test samples were analyzed for purgeable organics
by EPA Method 624, acid extractable organics by EPA Method 625, and
methanol by direct injection GC.
The slope of the linear regression line through the data points
represents the best estimate of the compound-specific biodegradation rate.
Concentrations would be expected to decline monotonically in the absence of
chemical analysis errors. This slope was then normalized for the biomass
concentration. Selected biodegradation rate constants are given in Table
F-27. Multiple rates for the same compound reflect data obtained during
different tests. Taking the rate constant for phenol, as an example, as
0.25 /jg/min-g biomass, would imply that a tank with mixed-liquor volatile
suspended solids of 2,500 mg/L could effectively biodegrade 5,400 fig/L of,
phenol. The actual difference between phenol in the influent and the
effluent of the aeration tank during the study period averaged 6,200 /*g/L
(based on a weighted average of aeration tank feed concentration and
recycled sludge vs. aeration tank effluent); the effluent and recycle
streams were below the detection limit of 250 /tg/L.
F.I.2.4 Site II.25 The Site 11 facility produces acrylic fibers by
the continuous polymerization of acrylonitrile with methyl methacrylate.
Wastewater from this process is discharged to an aerated equalization basin
and then treated by flocculation before being disposed of by deep-well
injection. Tests were conducted on the discharge trough and equalization
basin on May 20 and 21, 1986.
F-65
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TABLE F-27. BIODEGRADATION RATE CONSTANTS OBSERVED IN
SHAKER TESTS CONDUCTED AT SITE 10 AERATION TANK9
Constituent
Rate constant,
/;g/(min-g biomass)
Methanol
Phenol
2,4,6-Trichlorophenol
Styrene
Oxirane
1,1,1-Trichloroethane
12.8
5.7
0.087
0.25
0.29
0.037
0.0011
0.38
0.59
0
TSDF = Treatment, storage, and disposal facility.
aThis table presents zero-order biodegradation rate constants
determined from analyses of shaker test samples at Site 10.
Where more than one rate is presented, data were obtained
from different tests conducted during a 1-week period.
F-66
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The process wastewater containing acrylonitrile is discharged into an
open trough where it cascades downhill the length of the freeboard into the
equalization basin. The trough is constructed of stainless steel and is
approximately 30 cm wide with a total length of 8.2 m. The surface area of
the basin is approximately 4,000 m2. During the testing program, the
trough length above the equalization basin water!ine was approximately
6.4 m; the depth of the equalization basin was approximately 2.7 m. The
estimated daily loading rate for acrylonitrile entering the equalization
basin over the 2 days of the testing program was 115 kg/d, based on a mean
discharge concentration of 56.8 ppm at 2 million L/d.
The objectives of the testing program at Site 11 were to determine:
• Acrylonitrile emissions from the discharge trough prior to
the equalization basin
• Biological activity of the equalization basin
• Concentration of acrylonitrile in the equalization basin
with respect to time.
To determine acrylonitrile emissions from the discharge trough, grab
samples were collected at the trough influent and effluent. A beaker was
dipped into the flow, and each sample was transferred into triplicate VGA
vials. Samples were collected three times daily at approximately 4-h
intervals. Initial readings for temperature and pH were recorded, and
duplicate analyses using GC-FID were performed to determine the acryloni-
trile concentration of each sample. Flow rate measurements were not
performed because of the short period of time (less than 2 s) that the
discharged wastewater resided in the trough. In addition, the flow rate in
the discharge trough was highly variable, which led to alteration of the
sampling protocol for the final four sampling events to allow for simultan-
eous collection of influent and effluent samples. Because of the short
residence time in the trough and the change in sampling protocol, results
of testing acrylonitrile emissions from the discharge trough prior to the
equalization basin were inconclusive.
To quantify the biological activity of the equalization basin, BOD
analyses were conducted on a representative sample of the basin. The sam-
ple was collected by compositing grab samples from four different points
F-67
-------
about the perimeter of the basin with a glass container. Two separate BOD
analyses were then prepared and run in triplicate. Dilutions of 0.5, 0.67,
1.33, and 1.67 percent were used, and the aliquots were left unseeded.
Because BOD analyses also can measure the oxygen depletion used to oxidize
reduced forms of nitrogen (nitrogenous demand), an inhibitor (2-chloro-6
[trichloromethyl]pyridine) was added to one set in order to better quantify
the carbonaceous oxygen demand (COD) of the system. All analyses were
performed in accordance with Standard Methods for the Examination of Water
and Wastewater (16th Edition).26 Table F-28 summarizes the results of the
BOD analyses and shows essentially no change in mean BOD with addition of
the inhibitor. This indicates that the oxygen demand on the system is not
due to the oxidation of nitrogenous compounds and implies that oxygen
demand is related to the biochemical degradation of organic material and
the oxidation of inorganic materials such as sulfides.
To determine the acrylonitrile concentration in the" equalization basin
with respect to time, a total of three different composite grab samples was
collected as described previously for the BOD analyses. After each collec-
tion, portions of the composite sample were allocated to eight VOA vials.
Two of these were analyzed immediately to determine the initial acryloni-
trile concentration of the basin. Three of the VOA vials then were set
aside under ambient conditions to be analyzed after their respective hold-
ing time had elapsed. The remaining three were spiked with 5 /*L of stock
acrylonitrile and were analyzed to determine their initial acrylonitrile
concentration; then they were set aside under ambient conditions to be
reanalyzed after their respective holding time had .elapsed. All of the
acrylonitrile concentration determinations were conducted using a Hewlett-
Packard 5840 GC-FID. The acrylonitrile concentrations of the basin compos-
ites were below the detection limit of 5 ppm. Table F-29 presents the
acrylonitrile concentrations of the equalization basin spiked samples.
In addition to the eight VOA vials, three aliquots of each composite
were placed in standard BOD bottles. The DO concentration then was meas-
ured with a YSI 5720A BOD DO probe. The ground-glass stoppers then were
placed in the bottles, and a water seal was placed around the rim. The
bottles were set aside under ambient conditions and were reanalyzed for DO
F-68
-------
TABLE F-28. BIOCHEMICAL OXYGEN DEMAND RESULTS3 FROM EQUALIZATION
BASIN AT TSDF SITE II2?
Sample Time
date sampled
5/20/86 1000
5/20/86 1000
5/20/86 1000
5/20/86 1000
Method blank
Method blank
Percent
of aliquot
analyzed
0.5
0.67
0.5
0.67
NA
NA
TSDF = Treatment, storage, and
DO = Dissolved oxygen.
BOD = Biological oxygen demand
NA = Not applicable.
Initial
DO,
ppm
8.2
8.2
8.2
8.2
8.2
8.2
disposal
Final
DO, Mean BOD,b
ppm ppm
4.5
675
4.0
4.6
685
4.0
8.0
8.0
facility.
Analysis
comments
Total BOD
Inhibited BOD
300 mL of dilution
water
aGrab samples from four different points about the perimeter of the basin
were composited and two separate BOD analyses were prepared and run in
triplicate. An inhibitor (2-chloro-6[trichloromethyl]- pyridine) was added
to one set in order to better quantify the chemical oxygen demand of the
system.
bBOD is calculated as follows: BOD = [(Initial DO - Final D0)/Aliquot %] x
100.
F-69
-------
TABLE F-29.
ACRYLONITRILE CONCENTRATIONS OF THE EQUALIZATION BASIN
SPIKED SAMPLES3 AT TSDF SITE
Sample
date
5/20/86
5/20/86
5/21/86
pH
7.0
6.7
3.2
Mean initial
concentration,
mg/L
93
97
99
Mean final
concentration,
mg/L
52
45
105
Percent
reduction
44
54
NA
Mean total
holding
time, h
34.4
28.5
6.8
TSDF - Treatment, storage, and disposal facility.
NA - Not applicable.
aGrab samples from four different points about the perimeter of the basin
were composited a total of three different times. After each collec-
tion, portions of the composite sample were allocated to eight volatile
organic analysis vials, three of which were spiked with 5 fiL of stock
acrylonitrile. This table presents the results of the analyses of the
three sets of spiked samples.
F-70
-------
when their respective holding time had elapsed. Table F-30 presents the
results of the DO analyses.
F.I.2.5 Site 12.30 The Site 12 plant produces specialty chemicals in
a number of separate batch operations. Wastewater originates from water
used during the reaction process, water produced by the reaction, water
used"in rinsing the final products, and water used in cleaning operations.
The wastewater is treated in a series of processes (neutralization, primary
clarification, and activated sludge) prior to being discharged. Testing
was conducted during the week of August 13 through 19, 1984.
The site was chosen because of the emission control system used to
minimize odor from the aerated lagoon that is part of the activated sludge
system. Therefore, the test program was focused on the lagoon enclosure.
Specifically, the primary objectives of the lagoon enclosure testing were
to:
• Measure the control efficiency of the activated carbon beds
that were used in the treatment of the off-gases from the
lagoon
• Measure the overall effectiveness of the dome and carbon
adsorption systems
• Determine the validity of Thibodeaux's model for predicting
emission rates from aerated impoundments.
In addition, the effectiveness of 0.21-m3 drums of carbon used to control
breathing and working losses from the neutralizer tanks was evaluated.
Results of the analysis of the effectiveness of the dome are presented
in Section F.2.1.1. Effectiveness of the vapor-phase carbon adsorption is
discussed in Section F.2.2.1.2.
!
The aerated lagoon at Site 12 is approximately 46 by 130 m. The
lagoon aeration is performed by two large 56-kW (75-hp) aerators and 25
smaller 5.6-kW (7.5-hp) aerators. At least one of the large aerators and
an average of 16 of the smaller aerators are operated at all times. The
depth of the lagoon is generally held near 1.5 m. During the test period,
the level was substantially lower at 0.55 m. The lagoon is covered with a
PVC-coated polyester dome structure. The dome is an air-tight inflated
bubble structure, approximately 9 m tall at the highest point. The dome is
F-71
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TABLE F-30. DISSOLVED OXYGEN DATA FOR EQUALIZATION
BASIN SAMPLES9 AT TSDF SITE Il29
Sample
date
5/20/86
5/20/86
5/21/86
PH
7.0
6.7
3.2
Mean
initial DO,
mg/L
6.8
6.3
8.4
Mean
final DO,
mg/L
0.3
0.2
6.8
Mean
percent
reduction
96
97
19
Mean total
holding
time, h
29.5
25.6
9.4
TSDF = Treatment, storage, and disposal facility.
DO s Dissolved oxygen.
aGrab samples from four different points about the perimeter of the basin
were composited a total of three different times. After each collec-
tion, three aliquots of the composited sample were placed in standard
biochemical oxygen demand bottles for DO concentration analysis.
F-72
-------
pressurized by a main blower and equipped with an emergency fan, a propane-
powered auxiliary blower (for use during power failures), and a propane
heater (for winter operation). The air in the dome structure is purged
continuously through a fixed two-bed carbon adsorption system. The beds
are alternately regenerated every 24 h. The carbon adsorption system is
designed to remove odorous compounds (primarily orthochlorophenol, which is
not a VO) from the exhaust gases.
The wastewater from the batch reactors flows into two neutralizer
tanks for pH adjustment. At the time of the tests, the plant estimated
that the wastewater flow rate averaged 20.8 L/s. The capacity of each tank
is approximately 75,000 L. In the neutralizer tanks, caustic or acid is
added to maintain the pH in a range of 5 to 9. To reduce odors and VO
emissions, two 0.21-m3 (55-gal) drums of activated carbon are used to
capture vented hydrocarbon losses from these covered neutralizer tanks.
Liquid and slurry samples were collected at various locations around
the WWT facility at Site 12 to characterize inlets to and outlets from the
system. In addition, the vapor stream entering the carbon adsorption
system (representing air emissions from the aerated lagoon controlled by
the dome) was sampled. The liquid and sludge samples were collected in
glass containers with Teflon-lined caps. The sample bottles were filled to
minimize any headspace. Gas volumetric flow rate was determined by
procedures described in EPA Reference Method 2.31 Average gas velocity was
determined following procedures outlined in Reference Method 1.32 gas sam-
ples were collected from the carbon adsorption system inlet and outlet two
to three times daily in evacuated gas canisters.
Offsite analyses of air samples were performed on a Varian Model
3700 GC-FID/PID/HECD. Liquid samples were prepared in a purge-and-trap
manner and then analyzed by GC-FID/PID/HECD.
Table F-31 summarizes the test results from the covered aerated lagoon
used to evaluate the validity of Thibodeaux's model for predicting emission
rates from aerated impoundments.
F.I.2.6 Site 13.33»34 Site 13 is a large, continuously operated
organic chemical complex. A test program was conducted during August 1983
on the biological WWT system at this site. It has a large flow of 14.3 x
F-73
-------
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F-74
-------
1C)6 L/d from 16 production units. The majority of the process units dis-
charge continuously.
At the WWT system, the wastewater passes through a flowmeter and
discharges into a two-stage agitated pH adjustment system where sulfuric
acid or caustic is added to adjust the pH and renders the waste amenable
for subsequent biological treatment. The retention time within this system
averages 30 min.
After pH adjustment, the wastewater drops 0.91 m into a splitter box
and gravity-flows to two of three primary clarifiers. The clarifiers
remove any floating materials or organic layers from the quiescent liquid
surface as well as any settleable solids. The floating materials are
directed to a completely closed 114,000-L horizontal decanter. The
decanted water is intermittently pumped back to the pH adjustment system.
The accumulated organics in the decanter were quantitatively characterized
at the end of the study. The underflow from the clarifier is pumped con-
tinuously to the primary solids settling basin (PSSB) where the solids are
settled out and the supernatant is gravity-transferred to the aerated sta-
bilization basins for further treatment. The retention time of the waste-
water in the primary clarifiers averaged 2.7 h during this study.
The clarified wastewater from the primary system flows by gravity to
an equalization basin. This basin is well mixed by recirculation pumps
with submerged suction and discharge lines and serves to "equalize" peak
loads. An oil mop located at one end of the basin may be used to reduce or
eliminate floating organics not removed in the clarifiers. Although float-
ing organics were present- on the basin during this study, the oil mop was
not used. At the southeast corner of the basin, the wastewater passes over
an overflow weir and drops 0.6 m from a discharge pipe into a waste trans-
fer ditch that leads to the secondary treatment area. The wastewater
remains in this basin for approximately 50 h.
The wastewater is pumped from the ditch into one of two parallel
aerated stabilization basins, each containing 15 aerators (3.7 to 56 kW and
7.5 to 75 kW [5 to 75 hp and 10 to 100 hp]). Approximately half of the
aerators were in operation during this study. Within these basins, a
microbial population capable of degrading the organics present in the waste
F-75
-------
is maintained. The concentration of this population, measured as mixed
liquor suspended solids (MLSS), was 1,000 to 2,200 mg/L. To maintain a
viable biological population, both phosphorus and nitrogen are added as
nutrients to the waste transfer ditch or feed line ahead of the aerated
stabilization system as required. The liquid retention time in these
basins was 250 hours (10.5 days).
The effluent from the aerated stabilization basins is pumped to a UNOX
biological system. This system consists of four trains in parallel. Each
train contains three completely enclosed reactors in series. The MLSS
concentration in these reactors was on the order of 6,000 mg/L during this
study, and the liquid retention time was about 27 hours.
Some key physical parameters of each WWT process unit are presented in
Table F-32. The wastewater remained within this treatment facility for a
total of approximately 330 hours before being discharged to the receiving
water. The duration of this study represented 1.7 retention times of the
wastewater within the facility.
The objective of this study was to develop a mass balance for selected
organic compounds in an industrial biological WWT facility at a typical
organic chemical production complex. Eight chemicals were monitored in
this study, including four of high volatility (benzene, toluene,
1,2-dichloroethane, and ethyl benzene) and four of low volatility
(tetralin, 2 ethyl hexanol, 2 ethyl hexyl aerylate, and naphthalene).
Sampling was conducted between August 1 and 23, 1983. Twenty-four-
hour composite samples of the wastewater were collected from the influent
to the treatment plant, the effluent from the primary system, the effluent
from the equalization basin, the effluent from the aerated stabilization
basin, and the final effluent from the treatment plant. The samples were
analyzed onsite within 12 h of collection by GC. On each day of the study,
total VO concentrations were measured by an organic vapor analyzer (OVA) in
the ambient air upwind and downwind of each unit in the treatment facility.
Air samples around the aerated stabilization basins also were collected
daily on Tenax sorbent cartridges for subsequent analysis by GC-FID or
GC-MS.
F-76
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TABLE F-32. PHYSICAL PARAMETERS OF PROCESS UNITS AT TSDF
SITE 13, WASTEWATER TREATMENT SYSTEM35
Inlet box & pH adjustment tanks
Splitter box
Primary clarifiers
Equalization basin
Waste transfer ditch
Aerated stabilization basin
UNOX reactors
Two 61-m3 uncovered tanks
4.6 m diameter, 3.7 m high
Each mixed with 7.5-kW (10-hp), 45-rpm
agitator 0.91 m wide, 3.7 m long
Open top, rectangular, water drops
1.4 m
Three in parallel—two usually in
operation, 13.7 m diameter, 2.4 m deep
3.6-Mg basin (3.1-Mg effective volume)
Approximately 3.4 m deep
122 m long, open ditch, 0.6 to 1.5 m
deep, 1.2 to 3 m wide
Two basins in parallel--each holds
11 Mg, 3.7 m deep (MLSS 1,500 to 3,000
mg/L)
Aerators—3.7 to 5.2 kW (5 to 7 hp)
7.5 to 75 kW (10 to 100 hp)
12 reactors in 4 parallel trains of 3
reactors each
Each reactor 9.4 m diameter by 8.5 m
deep
TSDF = Treatment, storage, and disposal facility.
MLSS = Mixed liquor suspended solids.
F-77
-------
Tables F-33, F-34, and F-35 summarize the test results from the
primary clarifiers, equalization basin, and aerated stabilization basins,
respectively.
F.I.3 Landfills
F.I.3.1 Site 14.36 site 14 is a commercial hazardous waste
management facility located northeast of San Francisco, CA. The current
owners took over the site in 1975. The site accepts a variety of wastes.
Emission measurements were performed on the active landfill at Site 14
on October 11 and 23, 1983. The open landfill covered approximately
19,970 m2 and was contained within the confines of the natural topography
and an earthen embankment. No liner was used because of the low permeabil-
ity of the natural soil (clay). The landfill did not include any type of .
leachate collection system, nor any gas ventilation. This landfill had
been worked for approximately 4 years. One more lift was planned for the
landfill before closing it. The landfill accepted only hazardous waste,
primarily inorganic pigments, solids such as organic-contaminated soils,
and organic sludges. No liquids were accepted into the landfill, and no
fixation was performed. Any drums received were crushed prior to placement
into the landfill.
Material was unloaded in the north corner and spread over the surface
by bulldozers. Compactors then went over the waste surface prior to addi-
tional waste being spread. Periodically, dirt was brought in to be mixed
with the waste being spread, but no attempt was made to cover the landfill
on a daily basis. Activity at the landfill was on an as-needed basis.
The objectives of the testing program were to obtain:
• Emission rate data at the active landfill using the emission
isolation flux chamber approach
• Data on the concentration of VO compounds in the landfill
soil/waste for comparison to compounds identified during
emission measurements and as future input to predictive
models.
The sampling grid was established over the eastern side of the
landfill and included approximately 93 percent of the total exposed area.
The western side of the landfill was only sampled at one, nonrandomly
selected point (one air canister sample and corresponding soil sample)
F-78
-------
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F-81
-------
because of the extremely moist sampling surface and the relatively small
surface area of this side. Sampling points within the grid were randomly
selected. Points were chosen in 6 out of 20 grids. Duplicate air canister
samples and corresponding duplicate core samples were collected at two
locations; single air canister samples and corresponding core samples were
collected at four locations. The area appeared to be homogeneous. The
sampling locations were thought to be representative of the landfill as a
whole.
The emission isolation flux chamber was used for the air emission
testing. Air samples were collected in stainless-steel canisters. Soil
samples were collected with a thin-wall, brass core sampler. Air and soil
samples were analyzed offsite using a Varian Model 3700 GC-FID/PID/HECD.
Table F-36 presents a summary of the source testing results.
F.I.3.2 Site 6.37 Site 6 is a commercial hazardous waste TSDF. The
site began operation in 1972 and was acquired by the current owner in 1979
and upgraded to accept hazardous wastes. Before a waste is accepted for
disposal at the facility, samples must be analyzed to determine compatibil-
ity with the facility processes. Water-reactive, explosive, radioactive,
or pathogenic wastes are not accepted. Hazardous wastes are received from
the petroleum, agricultural products, electronics, wood and paper, and
chemical industries.
Emission measurements were performed on the inactive landfill June 19,
1984, and on the active landfill June 21, 1984, at Site 6. Source testing
was also conducted on a Site 6 surface impoundment (refer to Section
F.I.1.6) and the Site 6 drum storage and handling area (refer to Section
F.I.5.1).
Free liquids were not accepted for disposal, to the active landfills.
Any containers containing free liquids were solidified prior to disposal.
The landfills accepted bulk waste solids and containerized solids. Empty
drums were crushed prior to burial.
Containerized solid wastes were transported to the facility in sealed
containers and unloaded directly into the assigned burial area. Containers
of previously examined and tested compatible wastes were placed upright in
the landfill disposal areas and covered with soil. Bulk solid wastes were
F-82
-------
TABLE F-36. SOURCE TESTING RESULTS3 FOR TSDF SITE 14, ACTIVE LANDFILL
Constituent
Tetrachloroethylene
Total xylene
Toluene
1,1,1-Trichloroethane
Ethyl benzene
Total NMHCC
Mean
emission rate,
Mg/yr
3.3
3.8
2.2
1.8
1.0
54
Mean soil
concentration,
x 10~3 /ig/m3
130
16
25
260
.78
1,400
Emission
flux rate,b
x 106 g/m2«s
5.2
6.0
3.5
2.9
1.6
86
TSDF = Treatment, storage, and disposal facility.
NMHC = Nonmethane hydrocarbon.
aAir emissions were sampled with a flux chamber and soil concentrations were
determined from samples collected with a thin-wall, brass core sampler.
bThe emission flux rate is the emission rate converted to grams/second divided
by the exposed surface area (19,970 m2) of the landfill.
cThe NMHC totals do not represent column sums because only major constituents
(in terms of relative concentrations) are presented.
F-83
-------
placed in layers in the landfill, compacted, and covered daily with soil.
Subsequent layers of solid wastes and soil cover, sloped for drainage, were
added until the final landfill configuration was achieved.
At the time of testing, none of the landfills had been closed.
Completed landfills had a 0.91-m native clay cover. Active landfills had
approximately 0.3 m of native clay between lifts and 15.2 cm of loose cover
applied daily. The landfill areas had no leachate collection systems and
no gas ventilation systems.
Landfill activities at the site involved operations at three different
landfills. The expansion of one landfill was operational and encompassed
approximately 153,800 m2. This active landfill was used to dispose of bulk
solids, empty containers, containerized reactive and high pH materials,
hydroxide filter cake, and contaminated soil. It was covered daily with
0.61 or 0.91 m of soil. The inactive landfill was completed in 1982 and
has a surface area of approximately 12,140 m2. The waste types disposed of
at this site included containerized waste solvents, sludges, and toxics.
The objectives of the testing program at the Site 6 landfills were to
obtain:
• Emission rate data at the inactive landfill using the emis-
sion isolation flux chamber approach
• Data on the concentration of VO in the inactive landfill
soil for comparison to compounds identified during emission
measurements
• Emission rate data at the active landfill using the emission
isolation flux chamber approach
• Data on the concentrations of VO compounds in the active
landfill soil for comparison to compounds identified during
emission measurements.
The inactive landfill was an elliptical area of nominally 2,370 m2.
The area was divided into 25 equal grids. Sampling locations were selected
randomly and were thought to be representative of the overall landfill.
Air emission measurements were made at two grid points (one air canister
sample at each point), and a single soil core sample was collected at a
different point. Therefore, the soil sample did not correspond to the air
emission samples.
F-84
-------
The active landfill was relatively homogeneous, but for sampling
purposes it was divided into two areas. The temporary storage area had not
received fresh waste in 1 to 2 days. The surface area of the temporary
storage area was 1,490 m2. It was divided into eight equal grids, from
which three were randomly selected for air emission measurements (single
air canister samples at each grid). Corresponding single soil cores were
obtained at each of the three grid points. The active working area had a
surface area of 670 m2. Corresponding single air emission measurements and
soil sampling were conducted at one location selected by visual inspection
due to time limitations.
The emission isolation flux chamber approach was used in testing air
emissions. Gas samples were collected in evacuated stainless-steel canis-
ters. Soil samples were collected with a thin-wall, brass core sampler.
Gas and soil samples were analyzed offsite using a Varian Model 3700 GC-
FID/PID/HECD. Table F-37 summarizes the source testing results for the
inactive landfill. Tables F-38 and F-39 summarize the source testing
results for areas 1 and 2, respectively, of the active landfill.
F.I.3.3 Site 15.38,39 site 15 is a commercial waste disposal
operation that services four industrial clients exclusively. The site is
located in the Gulf Coast area and includes both a land treatment area and
a landfill. It has been in operation since 1980. Tests were conducted on
the land treatment area and the landfill during the week of November 14,
1983. The land treatment source testing is discussed in Section F.I.4.5.
The landfill that was tested at Site 15 consists of multiple cells
with overall dimensions of 549 by 152 by 4.6 m deep.
At the time of the tests, the active cells in the landfill included:
• A = centrifuge filter cake
• B = polymerization catalysts
• C = reduced metal catalysts
• D = miscellaneous.
Cell A consists of a rectangular pit with nominal dimensions of 15.2
by 12.2 by 3.0 m deep. Wastes disposed of in cell A were expected to
F-85
-------
TABLE F-37. SOURCE TESTING RESULTS3 FOR TSDF SITE 6,
INACTIVE LANDFILL
Constituent
Methylene chloride
1,1,1-Trichloroethane
Total NMHCC
Mean emission
rate, x 103 Mg/yr
10
5.3
56
Emission flux rate
x 109 g/m2«s
130
71
750
b
i
TSDF = Treatment, storage, and disposal facility.
NMHC = Nonmethane hydrocarbon.
aAir emissions were sampled with a flux chamber.
bThe emission flux rate is the emission'rate converted to grams/second
divided by the surface area (2,370 m2) of the inactive landfill.
GThe NMHC totals do not represent column sums because only major
constituents (in terms of relative concentrations) are presented.
F-86
-------
TABLE F-38. SOURCE TESTING RESULTS9 FOR TSDF SITE 6,
ACTIVE LANDFILL, TEMPORARY STORAGE AREA
Constituent
Toluene
Ethyl benzene
Total xylene
Methylene chloride
Chloroform
1,1, 1-Trichl oroethane
Tet rach 1 oroethy 1 ene
Total NMHCC
Mean
emission rate,
x 103 Mg/yr
3.4
5.9
30
20
2.6
120
30
660
Mean soil
concentration,
/tg/m3
ND
NO
ND
1,200
ND
ND
0.65
18,000
Emission
flux rate,b
x 109 g/m2«s
73
130
650
430
56
2,600
650
14,000
TSDF = Treatment, storage, and disposal facility.
ND = Not detected.
NMHC = Nonmethane hydrocarbon.
aAir emissions were sampled with a flux chamber and soil concentrations were
determined from samples collected with a thin-wall, brass core sampler.
bThe emission flux rate is the emission rate converted to grams/second divided
by the surface area (1,470 m2) of the active landfill temporary storage area.
cThe NMHC totals do not represent column sums because only major constituents
(in terms of relative concentrations) are presented.
F-87
-------
TABLE F-39. SOURCE TESTING RESULTS9 FOR TSDF SITE 6
ACTIVE LANDFILL, ACTIVE WORKING AREA
Emission
flux rate,b
Constituent
Vinyl chloride
Methyl ene chloride
Chloroform
1 , 1 , 1-Trichloroethane
1,2-Dichloropropane
Tetrachl oroethyl ene
Total NMHCC
x 103 Mg/yr
19
200
34
680
3.8
270
1,400
^ V I I V*V/I l\~\*l 1 1* I Ut»
/*g/m3
ND
ND
ND
ND
ND
ND
31,000
x 109 g/m2«s
900
9,500
1,600
32,000
180
13,000
66,000
TSDF = Treatment, storage, and disposal facility.
ND = Not detected.
NMHC = Nonmethane hydrocarbon.
aAir emissions were sampled with a flux chamber and soil concentrations were
determined from samples collected with a thin-wall, brass core sampler.
bThe emission flux rate is the emission rate converted to grams/second divided
by the surface area (670 m?) of the active landfill active working area.
cThe NMHC totals do not represent column sums because only major constituents
(in terms of relative concentrations) are presented.
F-88
-------
include solids from acrylonitrile, acetone cyanohydrin, lactic acid, terti-
ary butylamine, and iminodiacetic acid production activities. Waste is
typically unloaded with cell A four to eight times per month. During the
test period, a single truckload of waste was unloaded. The waste covered
approximately 25 percent of the floor of the cell and was left uncovered.
The objectives of the test program at cell A were to provide data to
evaluate both measurement and modeling techniques for determining air emis-
sions from hazardous waste landfills and to provide an indication of the
air emission levels from cell A. Gas-phase sampling was performed by the
emission isolation flux chamber method, and solid grab samples were col-
lected. For the flux chamber sampling, cell A was divided into 20 equal
grids, and samples (single air canister samples) were collected from two of
the grids. Nine solid grab samples were collected, of which two were
selected for detailed analysis. Only one of the solid samples selected for
detailed analysis corresponded to a flux chamber measurement.
Gas samples were collected in evacuated stainless-steel canisters.
Solid samples were collected in glass VOA vials with Teflon-lined caps and
filled with material so that no headspace was present. Gas and solid
sample offsite analysis was done using a Varian Model 3700 GC-FID/PID/HECD.
Table F-40 presents the source testing results from cell A of the Site 15
landfill.
F.I.3.4 Site 16.40«41 Site 16 is a commercial hazardous waste
management facility located in the northeastern United States. The site
includes four chemical landfills with provisions for a fifth. Landfills M,
N, and 0 were closed in 1978, 1980, and 1982, respectively. Landfill P was
opened in February 1982. At the time of the test, the categories of waste
placed in landfill P included:
• Flammables--paint waste, etc. (flashpoints from 27 to 60 °C)
• Pseudo metals—cyanide, arsenic, etc. (no longer an active
cell)
• Toxics—polychlorinated biphenyls (PCB), pesticides, etc.
• General organics—flashpoints greater than 60 °C
• Heavy metals—oxidizers, WWT sludge.
F-89
-------
TABLE F-40.
SOURCE TESTING RESULTS3 FOR TSDF SITE 15,
ACTIVE LANDFILL, CELL A
Constituent
Emission rate,
x 106 Mg/yr
Soil
concentration,
Emission
flux rate,b
x 109 g/m2.s
Acrylonitrile
Benzene
Toluene
Ethyl benzene
All xylene
Styrene
Isopropylbenzene
n-Propyl benzene
Naphthalene
Chlorobenzene
Acetaldehyde
Total NMHCC
<370
540
<370
<370
<740
<370
<370
<370
ND
<370
1,100
4,800
1.5
0.21
0.69
0.29
1.9
0.67
0.73
0.32
0.51
ND
ND
31
<63
93
<63
<63
<130
<63
<63
<63
ND
<63
190
820
TSDF = Treatment, storage, and disposal facility.
ND = Not detected.
NMHC s Nonmethane hydrocarbon.
aAir emissions were sampled with a flux chamber and soil concentrations were
determined from a sample collected in a glass VOA vial.
bThe emission flux rate is the emission rate converted to grams/second divided
by the surface area (185 m2) of cell A.
cThe NMHC totals do not represent column sums because only major constituents
(in terms of relative concentrations) are presented.
F-90
-------
Liquids were not accepted in landfill P. The waste material was limited to
5 percent free fluid, which included air (previous value had been 10 per-
cent). Liquid wastes were solidified prior to disposal. Municipal wastes
were kept separate from the chemical waste and disposed of in the sanitary
landfill.
Testing was performed at landfills P and 0 on October 11 and 12, 1983.
At the time of testing, landfill P was 240 by 160 by 8.5 m deep at grade
and had a volume of 3.3 x 10^ m^. The landfill has a 3.2-ha bottom and was
4 ha at the top of the berm. Major categories of waste were disposed of in
distinct subcells. The area allocated for each type of waste in landfill P
was nominally:
• Heavy metalS--35 percent
• General organics--35 percent
• Flammables--20 percent
• Toxics—10 percent.
A 15.2-cm cover was placed over the disposed waste daily to minimize
exposure to the atmosphere. The cover could consist of soils, ashes, lime,
hydrated carbon, or low-level contaminated soils.
Chemical landfill 0 is typical of the inactive landfills at Site 16.
Landfill 0 was closed in 1982 and occupies approximately 2 ha. Wastes were
segregated into subcells for general waste categories as described for
landfill P. The final cap of the landfill includes 0.9 m of compacted
clay, a 0.2-cm high-density polyethylene (HOPE) liner, 0.5 m of loose clay,
and 15.2 cm of topsoil and vegetation. The design permeability of the cap
is 1 x 10~7 cm/s.
Closed landfills at Site 16 include both standpipes for leachate
collection and gas vents. There are two standpipes in each of the five
subcells, for a total of 10. The standpipes are 61 cm diameter and open to
the atmosphere. There are two gas vents per subcell, for a total of 10.
The gas vents are valved shut, with provisions for gas release through
carbon canisters if the gas pressure builds up within the subcells.
The objectives of the test program at landfills 0 and P were to
provide data to evaluate both measurement and modeling techniques for
F-91
-------
determining air emissions from inactive and active hazardous waste
landfills and to provide an indication of the air emission levels from
landfills 0 and P.
Emission measurements were made at the inactive chemical landfill 0
using the flux chamber and vent sampling techniques. No emissions were
detected as measured by the flux chamber with continuous total hydrocarbon
(THC) monitor; therefore, no syringe or canister samples were taken. Six-
teen vents were sampled, at least one vent from each cell. Fifteen samples
by real-time hydrocarbon analyzer and one canister and two syringe samples
were collected. No solid samples were collected.
Emission sampling at the active chemical landfill P was limited to two
flux chamber measurements in the flammable cell only. One canister and two
syringe samples were collected. No solid samples were collected. No
attempt was made to grid the area. The nominal surface area of the active
landfill was 38,000 m2.
Canister samples were analyzed offsite using a Varian Model 3700 GC-
FID/PID/HECD. Syringe samples were analyzed onsite by GC-FID. Table F-41
presents the results of the canister sample collected from a standpipe in
the general organic cell of landfill 0. Table F-42 presents the results of
the canister sample collected from the flux chamber over the flammable cell
of landfill P. The nonmethane hydrocarbon (NMHC) totals represent averages
of the canister and syringe samples.
F.I.3.5 Site 7.42,43,44 site 7 is a commercial hazardous waste
management facility located in the northeastern United States. The site
was developed for hazardous waste operations in the early 1970s. Site 7
has a total of nine chemical landfills. Seven are closed, one is under
construction, and one is active (landfill B). Tests were conducted at
landfill B and one of the closed landfills (landfill A) during the first
week of October 1983. Also at Site 7, tests were conducted on three
surface impoundments in the WWT system (refer to Section F.I.1.7) and on
the drum storage building (refer to Section F.I.5.3).
When the tests were conducted, landfill B covered an estimated 2.5 ha,
with dimensions of 128 by 168 by 10.4 m at completion. The waste was
segregated into subcells according to the general category of the waste.
F-92
-------
TABLE F-41. SOURCE TESTING RESULTS9 FOR
TSDF SITE 16, INACTIVE LANDFILL 0
Constituent
Emission rate,
x 103 Mg/yr
Benzene
Toluene
Ethyl benzene
Total xylene
Styrene
n-Propyl benzene
Methylene chloride
Chloroform
1,1, 1-Tri chl oroethane
Total NMHCb
3.3
230
9.7
28
3.9
3.0
220
7.4
3.4.
930
TSDF = Treatment, storage, and disposal facility.
NMHC = Nonmethane hydrocarbon.
aThis table presents the results of the analysis of
a single canister sample collected from a stand-
pipe in the general organic cell.
bThe NMHC totals do not represent column sums
because only major constituents (in terms of
relative concentrations) are presented.
F-93
-------
TABLE F-42. SOURCE TESTING RESULTS9 FOR TSDF SITE 16,
ACTIVE LANDFILL P, FLAMMABLE WASTE CELL
Constituent
Emission rate,
x 103 Mg/yr
Emission flux rate,b
- x 109 g/m2«s
Toluene
Total xylene
Methyl ene chloride
1,1, 1-Trichloroethane
Tetrach 1 oroethy 1 ene
Total NMHCC
100
190
380
51
250
1,900
420
790
1,600
210
1,000
7,900
TSDF = Treatment, storage, and disposal facility.
NMHC = Nonmethane hydrocarbon.
aAir emissions were sampled with a flux chamber. One air canister
sample was collected from the flammable waste cell. No soil samples
were collected.
"The emission flux rate is the emission rate converted to grams/second
divided by the surface area (7,600 m2) of the flammable waste cell.
cThe NMHC totals do not represent column sums because only major
constitutents (in terms of relative concentrations) are presented.
F-94
-------
Table F-43 lists the subcells' percent of area occupied, types of wastes
accepted, and cover material at the time of the testing. The waste
accepted included both drums and bulk fill. Municipal waste was not
accepted. Waste was being disposed of at landfill B at a rate of
6,900 m3/mo.
All cells of landfill B were active during the sampling at Site 7.
The activity in the landfill and type and form of waste disposal (bulk vs.
drum) was dependent on the waste received. Drums were unloaded from semi-
trailers via towmotor with drum grabbers and positioned in the suitable
cell for disposal. The drums were used in alternating layers (drum layer,
bulk waste layer), giving the cell structural integrity. Some drums were
crushed in place after delivery using earth-moving equipment. Layers of
waste were covered with 15.2 cm of clay or low-level contaminated soils on
a daily basis, leaving little waste exposed to the atmosphere. The inter-
nal berms of landfill B were being increased (in height) allowing for fill-
ing at different rates.
Chemical landfill A is one of seven inactive landfills at Site 7.
Landfill A was built in September 1978, covers 2.6 ha of surface area, and
contains 371,000 m3 of waste. The landfill has subcells for general waste
categories as previously described for landfill B. The final cap of the
landfill includes 0.9 m of compacted clay, a 5.1-/tm PVC liner, 0.46 m of
uncompacted clay, and 15.2 cm of topsoil/sod. The design permeability of
this cap is 1 x 10'7 cm/s. During the field test, a new cap was being
installed. The capping process was essentially complete, with the topsoil
being finished off.
Closed landfills at Site 7 include a gas collection system with open
vents and a leachate collection system. The gas collection system has a
total of 18 vents, with each subcell vented individually. The vents are
15.2-cm schedule 40 PVC pipe. The leachate collection system has one well
for each subcell for a total of seven. Leachate is pumped directly to the
WWT system. Table F-44 lists the purgeable organics (as measured by EPA
Method No. 624) reported by Site 7 in the leachate from chemical land-
fill A.
F-95
-------
TABLE F-43. DESCRIPTION^ OF TSDF SITE 7,' DESCRIPTION OF SUBCELLS
IN ACTIVE LANDFILL
Percent of General
area waste
Subcell occupied category
Waste description
Composition
of cover
No. 1
No. 2
No. 3
40
10
25
Heavy metals
Pseudo metals
Cadmium, chromium, copper,
cobalt, iron, lead,
manganese, mercury, nickel,
tin, etc.
Antimony, arsenic, beryl-
lium, bismuth, phosphorus,
selenium, tellenium
General wastes Nonhalogenated aromatics,
hydroxyl and amine deriva-
tives, acid aldehydes,
ketones, flashpoint
greater than 54 °C
65% soil
35% neutral'
ized salts
Soils with
calcium
carbonate
waste solids
65% soil
35% neutral-
ized salts
No. 4 15
No. 5 10
Halogenated
wastes
Flammable
wastes
Controlled organics with
flashpoint greater than
54 °C not suitable for
fuel, PCB-contaminated
soils
Organics with flashpoints
greater than 27 °C and less
than 54 °C not suitable
for fuel
65% soil
35% neutral-
ized salts
65% soil
35% neutral-
ized salts
TSDF = Treatment, storage, and disposal facility.
PCB = Polychlorinated biphenyls.
aCharacteristies of the active landfill B subcells at the time source testing was
conducted. y
F-96
-------
TABLE F-44. PURGEABLE ORGANICS3 REPORTED
IN LEACHATE FROM CHEMICAL LANDFILL A
AT TSDF SITE 746
Compound
Mean
concentrations,
Chloromethane
Bromomethane
Vinyl chloride
Chloroethane
Methyl ene chloride
Tri chl orof 1 uoromethane
1,1-Dichloroethene
1,1-Dichloroethane
Trans-l,2-Dichloroethene
Chloroform
1,2-Dichloroethane
1,1,1-Trichloroethane
Carbon tetrachloride
Bromodi ch 1 oromethane
1,2-Dichloropropane
Trans-l,3-Dichloropropene
Trichloroethene
Cis-l,3-Dichloropropene
1,12-Tri chloroethane
Benzene
2-Chloroethyl vinyl ether
Bromoform
Tetrachloroethene
1,1,2, 2-Tetrachl oroethane
Toluene
Chlorobenzene
Ethyl benzene
<10
<10
<10
<10
25,295
189
55
944
4,061
2,193
7,596
502
64
50
89
50
2,493
150
90
1,842
<10
50
941
3,357
4,378
559
1,427
TSDF = Treatment, storage, and disposal facility.
Measured by EPA Method 624.
F-97
-------
The major compounds found were methylene chloride, trans-l,2-dichloro-
•ethene, chloroform, 1,2-dichloroethane, trichloroethane, benzene, 1,1,2,2-
tetra-chloroethane, and toluene. In the wastes disposed of in the
landfill, these compounds were typically present in higher concentrations
than the other purgeable organics.
The objectives of the test program at landfills A and B were to
provide data to evaluate both measurement and modeling techniques for
determining air emissions from inactive and active hazardous waste land-
fills and to provide an indication of the air emission levels from land-
fills A and B.
Emission measurements were made at the inactive chemical landfill A
using both vent sampling and flux chamber techniques. Each of the 18 vents
was surveyed using a real-time hydrocarbon analyzer and syringe, and single
canister samples were collected from two vents in the general organic cell.
Single-flux chamber measurements were made in the toxic and general organic
cells. No emissions were detected by the flux chamber measurements. No
solid samples were collected.
Emission measurements were made at active landfill B using flux
chamber techniques. The flammable and general organic cells were gridded,
and single canister samples were taken in one of four grids in the flam-
mable cell and in two of nine grids in the general organic cell. Single
soil samples also were collected in glass VOA vials during the flux chamber
measurements. The exposed surface area of the flammable cell was 2,100 m2
and of the general organic cell 4,200 m2.
No emissions through the cap of inactive landfill A were detected
using the flux chamber technique. The canister samples were taken from two
vents and were analyzed offsite using Varian Model 3700 GC-FID/PID/HECD.
Table F-45 presents the results of the analyses.
The canister and soil samples from the flux chamber testing at active
landfill B were analyzed using Varian Model 3700 GC-FID/PID/HECD. Tables
F-46 and F-47 present the results of the analyses for the flammable and
general organic cells, respectively.
F-98
-------
TABLE F-45.
SOURCE TESTING RESULTS3 FOR TSDF SITE 7,
INACTIVE LANDFILL A
Constituent
Benzene
Toluene
Total xylene
1,1-Dichloroethylene
Methylene chloride
Chloroform
1,1, 1-Trichloroethane
Tetrach 1 oroethy 1 ene
1,1-Dichloroethane
Acetaldehyde
Total NMHCb
Vent 2A emission
rate, x 105 Mg/yr
730
280
130
140
11,000
3,100
3,100
1,100
1,200
58
44,000
Vent 3-2 emission
rate, x 109 Mg/yr
840
2,800
3,600
ND
27,000
1,200
550
620
ND
ND
220,000
TSDF = Treatment, storage, and disposal facility.
ND = Not detected.
NMHC = Nonmethane hydrocarbon.
aThis table presents the results of the analysis of vent samples collected
during source testing at the TSDF Site 7 inactive landfill A. Single
canister samples were collected from two vents in the general organic
cell.
bThe NMHC totals do not represent column sums because only major
constituents (in terms of relative concentrations) are presented.
F-99
-------
TABLE F-46. SOURCE TESTING RESULTS9 FOR TSDF SITE 7,
ACTIVE LANDFILL B, FLAMMABLE WASTE CELL
Compound
Toluene
Ethyl benzene
Total xylene
Styrene
Isopropyl benzene
n-Propyl benzene
Naphthalene
Methyl ene chloride
1,1, 1-Trichloroethane
Tetrach 1 oroethy 1 ene
Total NMHCC
Emission rate,
x 106 Mg/yr
62,000
17,000
57,000
13,000
3,700
5,300
600
5,900
110,000
170,000
700,000
Soil
concentration,
x 103 /tg/g
ND
,220
11,000
ND
430
1,400
1,000
ND
97
12,000
220,000
Emission
flux rate.b
x 109 g/m2«s
940
260
860
200
56
80
9.1
89
1,700
2,600
11,000
TSDF = Treatment, storage, and disposal facility.
ND = Not detected.
NMHC = Nonmethane hydrocarbon.
aAir emissions were sampled with a flux chamber and soil concentrations were
determined from samples collected in glass volatile organic analysis vials.
"The emission flux rate is the emission rate converted to grams/second divided
by the surface area (2,100 m2) of the flammable waste cell.
cThe NMHC totals do not represent column sums because only major constituents
(in terms of relative concentrations) are presented.
F-100
-------
TABLE F-47. SOURCE TESTING RESULTS3 FOR TSDF SITE 7,
ACTIVE LANDFILL B, GENERAL ORGANIC WASTE CELL
Compound
Mean
emission rate,
x 103 Mg/yr
Mean soil
concentration,
Mean emission
flux rate,b
x 109 g/m2»s
Benzene
Toluene
Ethyl benzene
Total xylene
Styrene
Isopropylbenzene
n-Propyl benzene
Naphthalene
Methylene chloride
1 , 1 , 1-Trichloroethane
Tetrachl oroethy 1 ene
Total NMHCC
8.4
490
890
4,300
1,800
48
100
4.4
97
59
1.5
9,600
ND
10
39
200
87
4.4
8.2
14.
1.0
ND
• 1.6
1,200
63
3,700
6,700
32,000
14,000
360
760 "
33
730
450
11
72,000
TSDF = Treatment, storage, and disposal facility.
ND = Not detected.
NMHC = Nonmethane hydrocarbon.
aAir emissions were sampled with a flux chamber and soil concentrations were
determined from samples collected in glass volatile organic analysis vials.
emission flux rate is the emission rate converted to grams/second divided
by the surface area (4,200 m2) of the general organic cell.
cThe NMHC totals do not represent column sums because only major constituents
(in terms of relative concentrations) are presented.
F-101
-------
F.I.4 Land Treatment
F.I.4.1 Site 17.47 A study from 1986 to 1987 by a corporate research
facility consisted of a bench-scale laboratory simulation of a land
treatment operation. The goals of that simulation were to measure air
emissions that result from current land treatment practices, to determine
the effectiveness of land treatment as a means of biologically degrading
refinery sludges, and to measure the effectiveness of potential emission
control strategies, including centrifugation and thin-film evaporation
(TFE). The test setup consisted of two soil boxes, each with a surface
area of approximately 0.46 m2. Soil and waste from a company-owned land
treatment operation were placed in the soil boxes for testing. For each
test, ambient air that was treated to remove carbon dioxide (C02) and
hydrocarbons was circulated over the soil boxes at regulated conditions.
Installed instrumentation was used to monitor air flow and temperature
profiles in the boxes and to obtain samples of the air both upstream and
downstream of the soil boxes. The air samples were analyzed for
hydrocarbons using GC-FID and for C02 using gas chromatograph-thermal
conductivity detector (GC-TCD). Prior to application of waste to the soil
surface, the waste was analyzed by the modified oven drying technique^
(MOOT) to determine the oil, water, and solids content and by gravimetric
purge and trap to determine the VO content.
For the first test, only one soil box was used, and API separator
sludge (RCRA waste code K051) was applied using subsurface injection, which
is the normal method of waste application by the company. For the second
test, two soil boxes were used. API separator sludge was applied to one
box, and API separator sludge treated in a laboratory to simulate a centri-
fuge and drying operation was applied to the other box. In a third test,
emissions were measured from samples of an oily waste that had been
processed by TFE in a previous study of TFE (described in Section
F.2.3.3.1). Two samples of TFE-processed waste were evaluated: one that
was generated under operating conditions of high feed rate and low
temperature, and one generated under conditions of low feed rate and high
temperature. The first test was continued for about 2-1/2 months, the
second was continued for 22 days, and the third was continued for 26 days.
F-102
-------
The results of the sludge analyses for the test runs are presented in
Table F-48. Table F-49 presents the cumulative emissions over the test
period and the weight fraction of applied oil emitted over the test period.
F.I.4.2 Site 18.49 In 1986, bench-scale laboratory experiments were
set up to simulate a land treatment operation. The objectives of the study
were to:
• Measure air emissions of total and specific VO from land-
treated refinery sludges
• Correlate the measured emissions with the total and specific
VO
• Document the presence of bioactivity in the soil/sludge
mixture.
The simulation was carried out using four identical soil boxes that
were enclosed and instrumented to control and monitor experimental condi-
tions. Airflow over the soil, temperature, and humidity were controlled to
preselected values. The concentration of VO in the air downstream of the
soil boxes was monitored and used to estimate total VO emissions. In one
test run, samples of the air downstream of the soil boxes were collected in
canisters and analyzed for specific VO constituents. Measured emissions
were correlated with results of analyses of the applied waste.
Two different test runs were made using soil and sludge from two
different land treatment operations. In each test, land treatment soil was
placed in each of the four soil boxes, and sludge was applied to three of
the soil boxes. Two of the boxes with sludge applied served as duplicate
tests, and the third was treated with mercuric chloride to eliminate (or
reduce) bioactivity in the soil. The fourth box had no sludge applied and
was used as a control box.
Each test was continued for 31 days, during which time emission rates
were measured on a semicontinuous basis using THC analyzers. After sludge
was applied to a soil box, it remained on top of the soil for 24 hours and
then was mixed into the soil to simulate tilling. Additional "tillings"
were carried out at 8 and 15 days after waste application. Analyses of the
raw sludge were made using several different analytical methods, and the
results were compared with measured VO emissions over the entire test
F-103
-------
TABLE F-48. WASTE ANALYSES3 OF PETROLEUM REFINERY SLUDGES
USED IN LAND TREATMENT TESTS AT SITE 17
Percent composition,
Waste
constituent
Oil
Water
Solids
VO
Test 1
API separator
sludge
6.8
71.3
21.9
2.4
Test
API separator
sludge
8.8
78.4
13.2
2.5
wt %
2
Centrifuged
waste*3
10.9
0.9
88.4
0.2
TFE-
processed
waste0
17.4
80.5
2.2
NA
Test 3
TFE-
processed
wasted
67.3
17.8
15.2
NA
Note: Test numbers do not correspond to those used in the test report.
VO - Volatile organic.
TFE = Thin film evaporator.
NA - Not analyzed.
aThe oil, water, and solids content was determined using the modified oven
drying technique. The volatile organic content was determined using
gravimetric purge and trap technique.
bAPI separator sludge, treated to simulate a centrifuge and drying operation,
was used.
C0ily waste processed by TFE under conditions of high feed rate and low
temperature.
dOily waste processed by TFE under conditions of low feed rate and high
temperature.
F-104
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TABLE F-49. MEASURED AIR EMISSIONS3 FROM LAND TREATMENT
LABORATORY SIMULATION AT SITE 17
Test
Test 1,
sludge
Test 2,
sludge
Test 2,
wasted
Test 3,
waste6
Test 3,
wastef
No.
API separator
API separator
centrifuged
TFE-processed
TFE-processed
Test
duration,
d
69
22
22
26
26
Emissions
Wt
Cumulative, kgb appl
0.38
0.06
0.005
0.005
0.01
% of
ied oilc
40
11
1
1
2
Note: Test numbers do not correspond to those used in the test report.
aLaboratory simulation of land treatment operation using subsurface
injection.
bAir samples analyzed for hydrocarbons by gas chromatograph-flame
ionization detector and for C02 by gas chromatograph-thermal
conductivity detector.
cWeight fraction of applied oil emitted over test period.
dAPI separator sludge, centrifuged and dried before testing.
eOily waste processed by TFE under conditions of high feed rate and
low temperature.
y waste processed by TFE under conditions of low feed rate and
high temperature.
F-105
-------
period. In the second test run, GC'MS analyses were made of both the raw
sludge and the air downstream of the soil beds to determine the fraction of
VO in the applied waste that is emitted during the test.
Table F-50 shows the makeup of the waste used in each of the test runs
as determined by the modified oven drying technique. For Run 1, the waste
was an API separator sludge; for Run 2, the waste was an induced air
flotation (IAF) sludge.
Table F-51 summarizes the results of the two test runs. For each
test, the table presents the oil (organic) loading on each soil box as
determined from the modified oven drying technique sludge analysis, the
cumulative emissions from each soil box over the test period, and the
percent of applied oil emitted from each box over the test period.
F.I.4.3 Site 19.50 From June 25 through July 5, 1985, field
experiments were conducted at Site 18, an active midwestern refinery that
has a crude-oil-processing capacity of approximately 14.3 million L/d
(90,000 bbl/d). Operations conducted at the facility include atmospheric
distillation, vacuum distillation, delayed coking, fluid catalytic
cracking, catalytic reforming, aromatic isomerization, lube oil processing,
and asphalt processing.
The field study used a test plot that has been used routinely in the
past for land treatment of oily refinery sludges. Most of the sludge
applied to the site in the last 3 years has been an oily WWT sludge com-
posed of API separator and dissolved air flotation (DAF) bottom sludges
with an average composition of 71 percent water, 22 percent oil, and 7 per-
cent solids. The field test plot also receives biological sludge from an
onsite activated sludge plant two to three times a year. Single monthly
sludge applications of 3,180 to 3,980 L (20 to 25 bbl) of oil per plot, or
approximately 39,300 L/ha (100 bbl/acre), are normal during warm periods.
This is equivalent to 11,900 L of sludge per plot (75 bbl of sludge per
plot). In cold weather, loadings are routinely half these rates. Plots
are generally tilled within a few days of surface waste application. A
second tilling is usually carried out 2 to 3 weeks later. A 4-week treat-
ment period from the first tilling event is generally used before waste is
reapplied in a given location.
F-106
-------
TABLE F-50. WASTE ANALYSES9 OF PETROLEUM REFINERY SLUDGES
USED IN LAND TREATMENT LABORATORY SIMULATION AT SITE 18
Waste
constituent
Percent composition, wt %
Run lb Run 2C
Oil
Water
Solids
29.5
65.0
5.5
21.3
69.7
9.0
aThe oil, water, and solids content was determined using the
modified oxygen drying technique.
^American Petroleum Institute separator sludge was used.,
clnduced air flotation float was used.
F-107
-------
TABLE F-51. TOTAL VO EMISSIONS AT 740 HOURS AFTER APPLICATION OF
PETROLEUM REFINERY SLUDGES TO LAND TREATMENT SOIL BOXES, SITE 18
Test
Test run/ duration, 011 1oadin96
soil box3 h kg oil/m2
Percent of Percent of
Total VO total oil total VO
emissions at applied applied
740 h,c kg emitted emitted
Run id 740
Box 1
Box 2
Box 3
Box 4
9.58
No sludge
applied
9.47
9.7ie
0.14
Negligible
0.17
0.20
5.2
NA
6.5
7.46
19
NA
27
33
Run 2d
Box 1
740
5.68
0.29
18
41
Box 2
Box 3
Box 4
No sludge
applied
5.57
5.32
0.05
0.29
0.32
NA
19
22
NA
56
49
VO = Volatile organics.
NA = Not applicable.
aFor Run 1, American Petroleum Institute (API) separator sludge was
surface-applied. For Run 2, induced air flotation sludge was surface-
applied.
bAs measured using the modified oven drying technique (MOOT).
cBased on emissions associated with the sludge only (i.e., VO emissions
from Box 1, 3, or 4 minus the VO emissions from control Box 2). VO
concentrations were measured using two Byron Instrument Analyzers.
During the first 24 h after sludge application, a real-time total hydro-
carbon analyzer (Byron 401 analyzer) measured emissions once per minute.
Long term monitoring was done using a Byron 301 analyzer, with an average
total hydrocarbon measurement made approximately once per hour. (An
average measurement consisted of the average of five individual measure-
ments taken during that period.)
dSludge applied to Box 1 and Box 3 as duplicate tests; sludge treated
with mercuric chloride to eliminate (or reduce) bioactivity applied to
Box 4 and no sludge applied to Box 2.
eAverage MOOT results used rather than MOOT results for Box 4.
F-108
-------
The specific objectives of the project were to:
• Evaluate a type of flux chamber for measuring air emissions
at hazardous waste land treatment facilities in conjunction
with emission source testing, compliance monitoring, and
model validation activities
• For seven waste constituents, evaluate the Thibodeaux-Hwang
air emission model in field studies using actual hazardous
wastes to determine its applicability and limitations rela-
tive to the prediction of full-scale hazardous air emissions
from land treatment facilities.
The test plot was approximately 6 m by 182 m and was divided in half
lengthwise with three emission measurement locations per half to conform
with waste application methods normally used by the refinery. Waste
applications were made independently to each side of the field plot using
gravity feed from a tank truck equipped with a slotted application pipe
approximately 3 m in length and 8 cm in diameter. Each side of the
application area received a full truckload of waste corresponding to
approximately 3,330 L as reported by the tank truck operator.
Tilling was conducted approximately 24 h after waste application and
again approximately 155 h after waste application due to rainfall that had
occurred following the first tilling. Tiller depth ranged from approxi-
mately 17 cm to approximately 23 cm.
The application area was subdivided into six subsections, with each
subsection further subdivided into 396 grid locations of 0.69 m by 0.69 m.
Six sampling flux chambers were used for sample collection at randomly
chosen grid locations. The same sample locations were used throughout the
test program to preserve spatial continuity of the data collected. Four
distinct sampling phases were conducted:
• Background sampling of the test site prior to tillage
• Background sampling of the test site following tillage and
prior to waste application
• Specific constituent emission sampling following waste
addition
• Specific constituent emission sampling following each of two
tilling operations.
F-109
-------
Tenax sorbent tubes were used to collect the air emission samples to be
used for quantifying seven constituents. The constituents that were quan-
tified are identified in Table F-52.
In addition to the flux chamber sampling of air emissions, soil
samples and samples of the waste applied during field testing were col-
lected for analysis. The soil samples were analyzed for particle size
.distribution, particle density, oil and grease, and specific constituents.
Air emission and waste samples were analyzed by GC-FID.
Table F-52 presents the concentration of specific organic constituents
in the hazardous waste applied during field testing. The values represent
averages of 10 waste samples. Figure F-5 presents measured emission flux
data over time for one test plot over one testing period. Data for other
tests show similar trends. Table F-53 presents cumulative emissions for
each constituent monitored and shows the weight fraction emitted for each
constituent over the test period. These test results show wide variations
among the different measurement locations in the weight fraction of applied
constituents emitted to the air. In a few instances, values of measured
emissions of a constituent are greater than measured values of the amount
applied. This anomaly exists for ethylbenzene at all sampling locations
and for benzene at three sampling locations. No clear reason for these
anomalies are evident in the test report. Oil in the soil prior to the
application of waste for the test would contribute to measured emission
values and could account for part of the reported results. Emission data
for the test show most of the measured emissions occurred during the first
24 hours of the test before the waste was tilled into the soil.
F.I.4.4 Site 20.52 jn 1984/ field tests of land treatment emissions
were conducted at Site 20, a West Coast commercial crude oil refinery
producing a variety of hydrocarbon products. Refinery wastewater treatment
sludges, some of which are RCRA-listed hazardous wastes, are applied to an
onsite land treatment plot using subsurface injection.
The applied waste is typically 50 to 75 percent DAF/API float, 20 to
30 percent separator cleanings, and about 5 percent miscellaneous oily
waste. The sludge composition- is typically about 76 percent water, 12 per-
cent solids, and 12 percent oil (boiling curves usually start about
F-110
-------
TABLE F-52. WASTE ANALYSIS, CONCENTRATION OF
VOLATILE ORGANIC CONSTITUENTS IN PETROLEUM
REFINERY SLUDGES3 APPLIED IN LAND TREATMENT
FIELD EXPERIMENTS AT TSDF SITE 1951
Constituent^
Concentration,
waste0
Benzene
Toluene
Ethyl benzene
p-Xylene
m-Xylene
o-Xylene
Naphthalene
249
631
22
33
181
56
124
TSDF = Treatment, storage, and disposal facility.
aWaste was a combination of American Petroleum
Institute separator sludge and dissolved air
flotation sludge.
bConstituent analysis done using gas chromatograph-
flame ionization detector.
cEach concentration is the average of 10 waste
samples.
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-------
177 °C). Annual sludge disposed of ranges from about 5.4 to 9.1 x 106
kg/yr, and a typical application rate is about 16 L/m? (50 bbl/1/8 acre).
The objectives of the test program at the Site 20 land treatment
facility included the following:
• To determine the amount of organics volatilized relative to
the applied purgeable organics and of the applied oil
• To estimate the emissions of applied VO from the test plots
for the 5-week testing period and annually for the entire
land treatment facility
To determine the effectiveness of subsurface injection in
reducing VO emissions from land treatment by comparing the
measured emission rates from the two application methods
To determine the extent of oil degradation and/or measurable
biological activity
To determine the effects of various environmental and opera-
tional parameters on emission rates and emission rate meas-
urements, including those due to the emission measurement
procedure
• To compare the measured emission rates to those calculated
using the Thibodeaux-Hwang air emission model.
Three adjacent plots were selected for the emission tests; each plot
was 27.7 m long and 15.2 m wide. A portion of the land treatment area was
recovering from oil overloading, but the test plots were selected in an
area that had not experienced oil overloading. The center plot of the
three was used as a "control plot," i.e., no waste was applied, and sludge
was applied to the other two test plots using normal refinery procedures.
Each plot was tilled two to three times per week (in addition to tilling
immediately following sludge application) during the test period. (This
was the typical practice at this refinery.) The waste loading was
1.40 x 104 kg of sludge per plot.
Two flux chambers were used simultaneously throughout the testing
program to measure emissions. Eight measurements were made daily on each
test plot and two on the control plot. Each plot was marked into 21 grids.
Both random and semi continuous sampling techniques were employed. Of the
eight measurements made on each test plot, four measurements were made on
F-114
-------
random grids, while the remaining four measurements were made (two each) on
two control grids. This procedure was designed to reduce both random and
systematic error associated with the estimate of the mean emission rate.
In addition to the flux chamber sampling of air emissions, numerous other
parameters were analyzed.
Sampling was performed for 4 days during three separate sampling
periods that were approximately 7 to 10 days apart. Testing began
October 9, 1984, and concluded on November 2, 1984. During this time,
tilling occurred approximately three times per week for a total of 16
episodes.
Canister air samples, sludge samples, and liquid samples were analyzed
by GC-FID/PID/HECD. The determination of water, oil, and solids content in
the sludge was done according to the tetrahydrofuran (THF) protocol sup-
plied by the land treatment operator. The percent of oil and grease in
soil grab samples was determined by EPA Method 413.I.53 Soil physical
properties were determined by standard methods from undisturbed soil cores.
Results of an analysis of a single sludge sample by the THF method showed
71.6 percent water, 19.8 percent oil, and 8.6 percent solids. Figure F-6
shows the trend over the first 12 days in half-day average emission flux
rates of total VO as calculated from the combined Byron (onsite, syringe
samples) and Varian (offsite, canister samples) GC analytical results.
Table F-54 shows estimated total cumulative emissions of selected individ-
ual compounds and total VO over the entire test schedule.
F.I.4.5 Site 15.55 From November 14 through November 17, 1983, field
tests of land treatment emissions were conducted at Site 15, a commercial
waste disposal operation that services four industrial clients exclusively.
The site is located in the Gulf Coast area and includes both a land
treatment area and a landfill. Tests of landfill emissions are discussed
in Section F.I.3.3. Waste in the form of an oil-water emulsion is disposed
of as it is received because there is no onsite storage. Liquid waste is
received via tank truck and discharged through flexible hose onto the
surface (at ambient temperature) and spread with a toothed harrow (teeth
up). For the field test, the dimensions of the application area were
nominally 30 m by 18.3 m.
F-115
-------
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-------
TABLE F-54. ESTIMATED CUMULATIVE EMISSIONS OF SELECTED ORGANIC
CONSTITUENTS AND TOTAL VO FROM CRUDE OIL REFINERY WASTE LAND
TREATMENT FIELD TESTS AT TSDF SITE 2054
Cumulative emissions, b
wt % of applied material0
Constituent9
n-Heptane
Methyl cyclohexane
3-Methyl -heptane
n-Nonane
1-Methy 1 cycl ohexene
1-Octene
/J-Pinene
Limonene
Toluene
p-, m-Xylene
1,3, 5-Trimethyl benzene
o-Ethyl -toluene
Total 'V0d
Total oil
Surface Subsurface
application injection
60
61
52
56
49
50
17
22
37
35
21
32
30
1.2
94
88
77
80
76
74
21
26
56
48
27
42
36
1.4
TSDF = Treatment, storage, and disposal facility.
VO = Volatile organics.
^Air samples for chemical specification were collected in canisters using
a flux chamber.
^Test duration was 5 weeks.
cWaste oil consists of 50 to 75 percent dissolved air flotation/American
Petroleum Institute (API) float, 20 to 30 percent API separator clean-
ings, and about 5 percent miscellaneous oily wastes.
^Determined using a purge-and-trap technique and analyzed using a Varian
Model 3700 GC-FID/PID/HECD.
F-117
-------
A single truckload of waste totaling 20,060 L was offloaded during the
testing period. The calculated application rate was 34,720 g/m2; however,
observations indicated the waste was not spread evenly, and daily tilling
did not appear to even out the waste during testing. In addition, the
waste was reported to have been aged for about 1 year. Table F-55 lists
waste and land application characteristics.
The objective of the test program at the Site 15 land treatment plot
was to provide data to evaluate both measurement and modeling techniques
for determining air emissions from hazardous waste land treatment technolo-
gies. Because the test,was conducted using aged waste, results are not
expected to be representative of the level of air emissions from other land
treatment operations.
For measurement purposes, the surface of the land treatment plot was
divided into six equal grids. Air emission measurements were made over a
3-day period using the flux chamber technique. Flux chamber sampling
locations were selected at random, with the control point providing a
common position for sampling each day. Canister samples were collected
from two grids in addition to the control point. Soil samples also were
collected from two grids in addition to the control point, though only two
of the soil samples (control point and grid 5) corresponded to flux chamber
measurements. Gas and soil sample analysis was done offsite using a Varian
Model 3700 GC-FID/PID/HECD. Figure F-7 presents the emission flux rates
over time as calculated from the flux chamber measurements. Table F-56
shows cumulative measured total VO emissions and cumulative benzene emis-
sions.
F.I.4.6 Site 21.58 Over a period of 7 months in 1983, an independent
research organization conducted a laboratory study of land treatment
emissions by setting up a laboratory simulation of the land treatment of
oily refinery sludges. The simulation used both soil and sludges from
refineries that use land treatment routinely to dispose of their hazardous
waste.
The objectives of the study were to:
• Obtain detailed information and samples of sludges and soils
from refineries that use land treatment to dispose of oilv
sludges
F-118
-------
TABLE F-55. TSDF SITE 15 WASTE AND LAND TREATMENT
FACILITY3 CHARACTERISTICS56
Characteristic
Measure
Area of land treatment site (m2)
Waste volume applied (L)
Oil in waste (wt %)
Average density of applied waste (g/cm^)
Average depth of oil penetration (cm)
Approximate elapsed time from waste
application
First tilling (h)
Second tilling (h)
TSDF = Treatment, storage, and disposal facility.
aSite 15 is a commercial waste disposal operation that services four
industrial clients exclusively. During the testing period at the land
treatment site, a single truckload of waste with the characteristics
listed was offloaded.
520
20,060
23.4
0.9
19.6
19
47
F-119
-------
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F-120
-------
TABLE F-56. MEASURED CUMULATIVE LAND TREATMENT
EMISSIONS9 AT TSDF SITE 1557
Constituent
Total VOC
Elapsed time,
h
69
Measured emissions,!3
wt %
0.77 (wt % of
Benzene
69
applied oil)
3.9 (wt % of
applied benzene)
TSDF = Treatment, storage, and disposal facility.
VO = Volatile organics.
aAir emissions sampled with a flux chamber.
^Test was conducted using surface-applied waste reported to
have been aged about 1 year. As a result, the volatiles are
expected to have been emitted to the atmosphere prior to the
test.
C0etermined using purge-and-trap technique and analyzed using
a Varian Model 3700 gas chromatograph-flame ionization
detector/photoionization detector/Hall electrolytic
conductivity detector.
F-121
-------
Characterize sludge and soil samples by both chemical and
physical properties
• Identify sludge and soil samples that represent a broad
range of typical land treatment operations
• Measure volatility during an 8-hour test using different
combinations of sludge and soil types in controlled
laboratory simulations of land treatment operations.
Actual soil and sludge samples were obtained from eight refineries.
Soil samples were analyzed to determine pH (Method 21 from Agriculture
Handbook No. 60).59 specific gravity (ASTM D854-54),60 moisture content
(using weight loss after 16 h at 50 °C), particle size distribution (ASTM
D422),61 soil classification (ASTM D2487>,62 oil and grease content (EPA
Method No. 413.1), organic carbon by heating (ASTM D2974),63 and organic
carbon by titration. Sludge samples were analyzed to determine oil, water,
and solids content (by centrifugation), oil and grease content (EPA Methods
413.1 and 413.2),64 ancj volatility (using procedures developed in an
earlier phase of study).
The results of the soil and sludge analyses were used to select three
soils and three sludges to represent a wide range of field conditions.
Soils were selected to represent sand, silt, and clay soil types and
sludges were selected to represent high, medium, and low volatility
sludges. A series of tests was conducted using different combinations of
the selected soils and sludge samples. The tests were conducted in
enclosed soil boxes with a surface area of 0.093 m2. Oil loading of the
soil was varied over a wide range in the tests.
During each test, THC emissions were monitored continuously using a
Byron 401 analyzer. During each test, air flow over the soil box, humid-
ity, soil and air temperatures, and background levels of hydrocarbons were
periodically monitored and regulated as necessary.
Figure F-8 presents the average emission flux rate for all tests over
time. These values were calculated in.a separate study65 from the test
report. The average cumulative emissions over time for all tests that were
run for the entire 8-hour test period are presented in Table F-57.
F-122
-------
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F-123
-------
TABLE F-57. AVERAGE CUMULATIVE EMISSIONS FROM A
LABORATORY SIMULATION OF PETROLEUM REFINERY
WASTE LAND TREATMENT3 AT SITE
Run
number
18
21
24
27
28
32
33
34
35
36
37
40
41
44
45
46
47
48
49
50
51
Type of
wasteb
SL-14
SL-11
SL-14
SL-11
SL-14
SL-11
SL-11
SL-14
SL-12
SL-11
SL-14
SL-12
SL-11
SL-13
SL-13
SL-13
SL-13
SL-13
SL-13
SL-13
SL-13
Cumulative emissions,0
wt % of applied oil
9.1
4.4
0.02
0.6
0.1
3.0
2.6
0.01
0.9
78.8
9.9
0.7
2.8
4.9
49.9
7.7
6.9
5.0
9.7
1.1
0.47
Independent research Laboratory simulation of land treat-
ment activities. Total hydrocarbon emissions monitored
using a Byron 401 analyzer.
^Sludge type (surface applied):
SL-11 = Emulsions from wastewater holding pond
SL-12 = Dissolved air flotation (DAF) sludge
SL-13 = Mixture of American Petroleum Institute (API)
separator bottoms, DAF froth, and biological
oxidation sludge
SL-14 = API separator sludge.
cTest duration for each run was 8 h.
F-124
-------
F.I.4.7 Site 22.67 In 1979, field tests were conducted at a land
treatment facility at Site 22, a Midwestern petroleum refinery. The
refinery had a capacity of 19.7 million L/d (124,000 bbl/d) and produced a
typical fuels product mix.
In the spring of 1976, three 2.4 m by 46 m test plots, designated A,
B, and C, were laid out side by side on a flat grassy area near a tank farm
on refinery property. During 1976, 1977, and 1978, the plots were used for
land treating oily refinery wastes. Over this 3-year period, Plot A
received a centrifuge sludge and Plot B an API separator sludge. Plot C
was used as a control and received no waste applications. The final waste
applications were carried out on November 10 and 14, 1978, on Plots A and
B, respectively, and the final tilling on December 4. All three plots were
rototilled on May 10, 1979, in preparation for the emission study that
began May 22. Tests were concluded October 9, 1979.
The objective of the field tests conducted at Site 22 was to attempt
to quantify VO emissions from the land treatment of two refinery wastes
(API separator sludge and a centrifuge sludge). The API separator sludge
was applied at a rate of 29.9 L/m2 (760 bbl/acre) and contained 1.7 kg/m2
(15,000 Ib/acre [5.2 weight percent]) organic fraction. Centrifuge sludge
from a refinery sludge and wastewater treatment dewatering operation was
applied at a rate of 35.4 L/m2 (900 bbl/acre) and contained 3.2 kg/m2
(28,300 Ib/acre [8.1 weight percent]) organic fraction. Table F-58 sum-
marizes the waste loading on Plots A and B of the test site and presents
properties of the applied sludges.
The API separator sludge was obtained from the primary WWT separators,
sampled, and, prior to being applied to the test plot, was weathered for 14
days in open 18.9-L buckets in an outdoor open shelter. The centrifuge
sludge was derived from centrifuge dewatering of an oily sludge mix stem-
ming from normal refinery operations and wastewater treating, including the
API separator sludge.
The sludges were analyzed using a modified extraction technique for
phase separation to determine the amount of organics, water, and minerals
in the sludge. However, because of the temperatures involved, some loss of
light organics may have occurred. Soil sampling was attempted, but diffi-
culties with obtaining a representative soil sample and uneven waste
spreading made organic balance determinations of little significance.
F-125
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TABLE F-58. WASTE CHARACTERISTICS AND APPLICATION RATES FOR
FIELD EXPERIMENTS ON PETROLEUM REFINERY WASTE LAND
TREATMENT, TSDF SITE 22&8
Test information
Sludge type
Total sludge applied (kg/m2)
Total oil applied (kg/m2)
Incorporation depth (cm)
Final oil concentration in soil
Sludge composition3
Oil (wt %)
Water
Solids
Test location
A
Centrifuge sludge
39.0
3.2
20.3
(wt %) 4.3
8.1
72.1
19.8
Test location
B
API separator
sludge
33.0
1.7
20.3
3.0
5.2
85.2
9.6
TSDF - Treatment, storage, and disposal facility.
API = American Petroleum Institute.
aAnalyzed using a modified extraction technique for phase separation.
Because of temperature involved, some loss of light organics may have
occurred.
F-126
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A flux chamber with a surface area of 0.093 m2 was inverted over the
area of the test plot to be studied and served to collect total emissions
from the plot soil beneath it. The box was continuously purged with a
stream of fresh air that was carried from the box through sample lines into
an adjacent trailer where a Mine Safety Appliances Company Model 11-2 con-
tinuous hydrocarbon/methane analyzer was used to measure VO as methane and
total NMHC. There was no identification of specific organic emissions.
The experimental program was carried out in three phases:
• Phase I - Background Tests 1, 2, and 3 on the three test
locations.
• Phase II - Emission Tests 4, 5, and 6 on the centrifuge
sludge applied to test location A.
Test 4 data were not included.
Test 5 was conducted at a new location with new waste
applied.
Test 6 followed rototilling at the end of run 5 on the
same ground area.
Phase III - Emission Tests 7, 8, and 9 on the API separator
sludge applied to test location B.
Test 7 was conducted at a new location with new waste
applied.
Test 8 was conducted at a new location with new waste
applied.
Test 9 followed rototilling at the end of run 8 on the
same ground area.-
Table F-59 summarizes the Site 22 data providing the fraction of
applied oil emitted during the test. These results were calculated using
the measured emission flux rates and the amount of oil applied during waste
application. Figure F-9 shows derived tabular values of total VO emission
flux versus time at Site 22.
F.I.5 Transfer, Storage, and Handling Operations
F.I.5.1 Site 6.70 Site 6 is a commercial hazardous waste TSDF. The
site began operation in 1972 and was acquired by the current owner in 1979
and upgraded to accept hazardous wastes. Before a waste is accepted for
F-127
-------
TABLE F-59. FRACTION OF APPLIED OIL EMITTED BY LAND TREATMENT TEST
AT TSDF SITE 22^9
Waste
type Test No.a
Centrifuge
sludge
API separator
sludge^
5
6
7
8
9
Test duration,
d/h
0.83/19.9
12.8/307
25.8/619
5.1/122
21.7/520 .
Wt % of applied
oil emitted
0.1
1.8
10.9
3.3
10.4
TSDF = Treatment, storage, and disposal facility.
API - American Petroleum Institute.
aAir emissions sampled with flux chamber. Waste was surface-applied.
bWeathered for 14 d in open 18.9-L buckets in an outdoor open shelter
prior to application.
F-128
-------
g
CO
.CD
-------
disposal at the facility, samples must be analyzed to determine compatibil-
ity with the facility processes. Water-reactive, explosive, radioactive,
or pathogenic wastes are not accepted. Hazardous wastes are received from
the petroleum, agricultural products, electronics, wood and paper, and
chemical industries.
All wastes that are stored at the facility are received in bulk
0.21-m3 drums, 18.9-L pails, or carboys. Wastes are stored in drums or
tanks. Typical wastes stored at the facility include pesticides, PCB, wood
preservatives, and miscellaneous organics.
The drum marshalling area is situated near the waste processing area.
Bermed embankments surround the staging area. All drums are offloaded into
this area. Here, they are opened and sampled to determine the proper proc-
essing. The drums containing free liquids are then selected for decanting.
Pumpable organics are sent to the surge tanks and separation tanks for
physical separation of phases. Chlorinated organics are solidified and
then landfilled. Supplemental fuels are sent to the fuel tanks for storage
and testing prior to being hauled offsite. Nonchlorinated, nonignitible
aqueous organic wastes are sent to the aqueous organic tank. Sludges from
the decanting operation are solidified with the non-RCRA kiln dust and
landfilled. During the site visit, the drum handling area contained 220
open drums. Turnaround time for the drum handling area is approximately
3 days.
The objective of the drum storage and handling area testing was to
survey ambient concentrations at and immediately downwind of the drum stor-
age and handling area. Section F.I.1.6 discusses source testing of a
Site 6 surface impoundment; Section F.I.3.2 describes the emission measure-
ments made on inactive and active Site 6 landfills.
A survey was made during the morning of June 22, 1984, of the various
drum storage areas, including the tank storage area, an outside drum stor-
age area, a building for PCB drum storage, and a drum transfer area. Dur-
ing the survey, no specific activity was taking place in the area. Ambient
hydrocarbon measurements were made in the immediate vicinity of the storage
areas using a portable OVA. Table F-60 presents the results of the survey.
F-130
-------
TABLE F-60. SUMMARY OF DRUM STORAGE AND HANDLING AREA SURVEY
OF AMBIENT HYDROCARBON CONCENTRATIONS,9 SITE 671
Sampling
location
Concentration of
THC, ppm
Comments
Vicinity of tank
storage
Drum storage area
Drum transfer area
PCB building
0.2
0.0
0.0
0.1
220 empty drums; all open;
in good condition
600 empty drums; all open;
in good condition
No decantation in progress
70 drums; 32 empty; all in
good condition
THC = Total hydrocarbon.
PCB = Polychlorinated biphenyl.
aAmbient hydrocarbon measurements were made in the immediate vicinity of
the storage areas with a portable organic vapor analyzer.
F-131
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F.I.5.2 5Mte_23.72,73 site 23 is a commercial chemical conversions
and reclaiming facility located in the eastern United States. Solvents are
recycled at the facility.
The objectives of the testing program at Site 23 were to develop and
verify techniques for determining air emissions from drum storage areas and
storage tanks. The field testing was conducted during the week of
October 24, 1983.
A large number of drums were located in the various drum storage areas
at Site 23. Site personnel provided a drum inventory taken in July 1982.
The total inventory of drums amounted to almost 28,000, with approximately
3,000 of those being empty, used drums. Test personnel did not do a com-
plete drum inventory during the test period, but they estimated that the
number of drums in storage in three areas was approximately 35 percent less
than had been inventoried in July 1982. Additionally, the number of empty,
used drums in storage appeared to be significantly less than the 3,000
inventoried by plant personnel.
The drums in the three major storage areas were, for the most part,
stacked four drums high. One of the areas was partially submerged in
approximately 0.3 to 0.6 m of water. This area served as an emergency
retention area during periods of excessive rainfall and was enclosed with
an earthen dike. None of the drum storage areas was covered.
During the test period, several types of drum handling activities were
being performed. The basic operations were:
• Emptying old drums filled with waste and distillation
residues
• Removing the tops of empty, used drums in preparation for
removing these drums from the plant site
• Emptying drums of spent solvent for purification
• Filling drums with the reclaimed solvent and/or bottoms from
the solvent distillation/purification process.
Emissions were examined using real-time gas analyzers. The measure-
ments were made at a distance of approximately 2.4 m from the drums on all
four sides of the drum pile. The wind during this examination was from the
F-132
-------
southwest and had a speed of 1.2 km/h. Between the two drum storage areas
was a drum transfer area that contained a number of open drums. This area
contributed to the emissions measured on the adjoining sides of the two
storage areas. The measured gas concentrations are presented in Table
F-61.
Storage tanks at Site 23 range in size from 1,290 to 71,900 L.
Feedstocks, products, and wastes are all stored in aboveground tanks. In
addition, three underground storage tanks are used to store boiler fuel.
All of the tanks are vented directly to the atmosphere. Pressure-relief
valves are not present in the vent lines.
Sampling was attempted on five storage tank vents. The sampling
equipment consisted of a hot wire anemometer for velocity measurements and
a variety of gas monitoring/collection devices. Portable FID and/or PID
analyzers were used to obtain real-time continuous total hydrocarbon con-
centration measurements in excess of 10,000 ppmv at the exits of these
vents. When the hot wire anemometer proved to be insufficiently sensitive,
a dry-gas meter and a 10-mL bubble meter were used to measure gas flows.
These meters also failed to register any gas flows, so no further examina-
tion of vent emissions was undertaken.
F.I.5.3 Site 7.75 Site 7 is a commercial hazardous waste management
facility located in the northeastern United States. The site was developed
for hazardous waste operations in the early 1970s. Source testing was
conducted at a drum storage building during the first week of October 1983.
Section F.I.1.7 discusses source testing on three surface impoundments in
the Site 7 WWT system and Section F.I.3.5 presents source testing results
from Site 7 active and closed landfills.
Drum storage at Site 7 takes place in two buildings. One building is
used for storage of drums containing PCB, and another building (different
location) houses hazardous and nonhazardous drums. Field measurements were
made at the hazardous and nonhazardous drum storage building only. The
building dimensions are nominally 33.5 by 48.8 by 4.9 m, with a 12:1 roof
slope. The building is ventilated by two manually operated fans nominally
rated at 0.75 kW (1 hp)— 5.8 m3/s at 0.245 standard pressure (S.P.).
Makeup air enters through two vents at the end of the building opposite the
F-133
-------
TABLE F-61.
RESULTS OF EMISSION SURVEY^ AT DRUM STORAGE AREA,
SITE 2374
Sampling location
Distance of
measurement from
drums, m
Concentration of
THC, ppm
OVA
PID
Upper drum storage area
East side
East side
South side
West side
North side
Lower drum storage area
East side
South side
West side
North side
0.3
6.1
2.4
2.4
1.5
2.4
2.4
2.4
2.4
60
7
5
5-7
10-20
10-20
20-30
5
7
9
0.5
0.1
0.1
5-10
0-2
5-15
0.1
0-0.2
THC = Total hydrocarbon.
OVA = Organic vapor analyzer.
PID = Photoionization detector.
aReal-time gas analyzer measurements were made on all four sides of the
drum pile. The wind was from the southwest at 1.2 km/h. A drum
transfer area containing a number of open drums between the two drum
storage areas contributed to the emissions measured on the adjoining
sides of the two storage areas.
F-134
-------
fans and through a 27.4-m roof vent. The design ventilation rate for the
drum storage building and adjoining office is six air changes per hour.
Four emergency fans nominally rated at 1.1 kW (1-1/2 hp)--6.9 m^/s at
0.286 S.P.--are available. An explosive-level monitor provides an alarm
warning at 35 percent and activates the emergency fans at 60 percent.
The drum storage building is designed to process 1,000 drums/day.
This translates to 10 to 11 trucks/day. Total design storage capacity is
2,000 drums. Drums are filled, labeled, sealed, inventoried, and stored in
cordoned areas by material type. The stored drums typically are comprised
of 40 to 50 percent landfill waste, 35 to 50 percent fuels, 1 to 5 percent
chlorinated solvents for recycling, 5 to 10 percent aqueous waste, and
1 percent other. During the field test, it was estimated that the storage
area had 1,500 drums. The drum types included 95 percent standard 0.16-m3
steel drums, 2 to 5 percent overpack, and 1 percent 0.11-m3 fiber drums.
No leakage was observed.
The objective of the tests on the drum storage building was to develop
and verify techniques for determining air emissions from drum storage
facilities. A vent was fabricated at the exit of the ventilation fans.
Velocity traverses and real-time THC measurements were made at a total of
48 points within the vent. The hydrocarbon measurements were all 4 ppmv by
OVA and 0 ppmv by PID. In addition, a single canister sample was collected
from the exhaust air and analyzed offsite using a Varian Model 3700
GC-FID/PID/HECD. The emission rate from the vent was calculated as the
product of the concentration and flow rate. Table F-62 lists the measured
emission rates.
F.2 TEST DATA ON CONTROLS
The controls considered for TSDF emission sources serve either to
suppress air emissions by capture, containment, or destruction of VO (e.g.,
by using enclosures or covers for surface impoundments and tanks or combus-
tion devices for vents) or to remove VO from hazardous waste streams (e.g.,
by steam stripping or distillation) to avert air emissions from downstream
treatment or disposal operations. This section presents the results of
field tests conducted to evaluate the efficiency of controls to suppress
air emissions or remove VO from hazardous waste streams.
F-135
-------
TABLE F-62. SOURCE TESTING RESULTS3 FOR TSDF
SITE 7 DRUM STORAGE BUILDING76
Constituent
Toluene
Total xylene
Naphthalene
Methyl ene chloride
1,1, 1-Tri chl oroethane
Carbon tetrachloride
Tetrachl oroethy 1 ene
Total NMHCb
Emission rate,
x 106 Mg/yr
2,300
1,000
560
80,000
4,500
3,500
45,000
150,000
TSDF = Treatment, storage, and disposal facility.
NMHC = Nonmethane hydrocarbon.
aVent emission rate calculated as the product of the
concentration and flow rate. Concentration deter-
mined from a single canister sample of the exhaust
air and flow rate determined from velocity traverses
made at a total of 48 points within the vent.
bThe NMHC total does not represent a column sum
because only major constituents (in terms of
relative concentrations) are presented.
F-136
-------
F.2.1 Capture and Containment
F.2.1.1 Air-Supported Structures—Site 12.77 Section F.I.2.5 con-
tains a description of the testing program conducted during the week of
August 13 through 19, 1984, at the Site 12 WWT system. One of the objec-
tives of the testing program was to measure the control efficiency of the
dome and carbon adsorption system designed to control odors and emissions
from the aerated lagoon serving as part of the activated sludge system.
The control effectiveness of the dome structure is a measure of the
dome's ability to contain gas-phase NMHC emissions from the aerated lagoon.
During the test, the control effectiveness could not be quantified. The
plant indicated the dome had a relatively good seal and estimated the total
leakage at 0.14 m3/s. Test personnel performed a crude leak check of.the
dome by surveying the perimeter with a portable hydrocarbon analyzer. The
measured total hydrocarbon concentration ranged from 2 to 3 ppmv near the
carbon adsorber to 30 to 40 ppm at the escape hatch. Personnel also used
water to roughly quantify any detected leak by spraying the liquid along
the dome seal and observing any bubbles. Relatively few small leaks were
found, indicating that the leak rate may be much less than 0.14 m3/s.
F.2.2 Add-on Control Devices
F.2.2.1 Gas-Phase Carbon Adsorption.
F.2.2.1.1 Site 24.78 A test program was conducted for 4 days during
May 1985 on the air-stripping system used to treat leachate at Site 24.
Site 24 is on the National Priority List (NPL—Superfund) currently managed
by EPA under the Comprehensive Environmental Response, Compensation, and
Liability Act (CERCLA). One of the objectives of the test program was to
assess the performance of the existing gas-phase, fixed-bed carbon
adsorption system used to treat the air effluent from the air stripper.
The air-stripping' process is described in Section F.2.3.2.1.
Air samples of the stripper exhaust and carbon adsorber exhaust were
taken at a variety of water and air flow rates. No information was docu-
mented concerning sampling equipment, but sample analysis was performed
using GC-MS. Process data collected included all stripper influent and
effluent temperatures and both air and water influent rates to the air
stripper.
F-137
-------
Material balances and stream flow and concentration data were used to
characterize the carbon adsorber system influent and effluent. Air meas-
urements were taken under the test conditions yielding the highest VO
removal from the water. This was obtained when the influent water rate was
throttled down to 1,140 kg/h, and the air flow correspondingly increased to
4.8 m3/min, giving the highest airrwater ratio observed during testing.
Table F-63 presents the source testing results.
F.2.2.1.2 Site 12.79 Section F.I.2.5 contains a description of the
WWT system at Site 12, including the activated carbon fixed beds used to
treat the off-gases from the aerated lagoon and the carbon canisters used
to control breathing and working losses from the neutralizer tanks.
To measure the effectiveness of the gas-phase fixed-bed carbon
adsorption control devices, the inlet to and exhaust from the carbon
adsorption system and the inlet to and exhaust from the disposable carbon
drums were sampled during the week of August 13 through 19, 1984.
Gas volumetric flow rate was determined by procedures described in EPA
Reference Method 2. Average gas velocity was determined following proced-
ures outlined in EPA Reference Method 1. Gas samples were collected from
the carbon adsorption system inlet and outlet two to three times daily in
evacuated gas canisters. Evacuated gas canisters fitted with flow control-
lers were used to collect the carbon drum inlet and outlet samples inte-
grated over a 16-h period. Offsite analyses of these samples permitted
calculation of the removal efficiency of each vent emission control device.
In addition, a small canister of clean, activated charcoal was placed in
line upstream bypassing each 0.21-m3 (55-gal) drum to collect all VO being
vented over a known time interval. The carbon was extracted offsite to
yield the mass/unit time of VO reaching the control devices. This informa-
tion was combined with the removal efficiency data to allow calculation of
the average emissions to the atmosphere from each control device as well as
the efficiency of the carbon drums. Offsite analyses of air samples were
performed on a Varian Model 3700 GC-FID/PID/HECD. Table F-64 presents the
carbon adsorption fixed-bed system removal efficiency for specific species.
Table F-65 presents the neutralizer vent carbon drum removal efficiency
results.
F-138
-------
TABLE F-63. SOURCE TESTING RESULTS3 FOR TSDF SITE 24, AIR STRIPPER
EMISSIONS WITH GAS-PHASE, FIXED-BED CARBON ADSORPTION SYSTEM APPLIED
Exhaust from Exhaust from
air stripper carbon adsorber
Constituent
1,2,3-Trichloropropane
(o.m)-Xylene
p-Xylene
Toluene
Aniline
Phenol
2-Methyl phenol
4-Methyl phenol
Ethyl benzene
1 , 2-Di ch 1 orobenzene
1 , 2 , 4-Tri chl orobenzene
Other V0d
Total V0e
Mass flow
rate,
x 103
kg/h
13
5.2
1.7
2.8
NA
NA
NA
NA
0.75
0.097
NA
0.48
24
Mass flow
rate ,
Cone.,
ng/L
44,000
18,000
6,000
9,800
NA
NA
NA
NA
2,600
340b
NA
1,700
82,400
x 106
kg/h
0.14
2.6
1.7
1.6
NA
NA
NA
NA
0.43
0.14
NA
0.58
7.3
Carbon
adsorber
system
organic
removal
Cone., efficiency,
ng/L wt. %
<1.0
9.0
5.7
6.0
NA
NA
NA
NA
1.5
<1.0b'c
NA
2.0
25.0
99.999
99.95
99.9
99.9
NA
NA
NA
NA
99.9
99.9
99.9
99.97
TSDF = Treatment, storage, and disposal facility.
NA = Not available.
VO = Volatile organics.
aThis tables demonstrates the effectiveness of activated carbon as an
adsorbent for VO in gas streams.
^Concentration reported for all isomers of dichlorobenzene, not just
1,2-dichlorobenzene.
cConstituent concentration below detection limit.
dlncludes 4-methyl-2-pentanone, chlorobenzene, tetrachloroethylene, and
dichlorocyclohexane isomers.
elncludes all speciated organics.
F-139
-------
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F-141
-------
As the results in Table F-64 indicate, the carbon beds were not
removing the major species in the dome exhaust gas stream. This was not
unexpected for at least two reasons. First, the beds were not originally
designed for bulk removal of NMHC from the air stream. Rather, the beds
were designed for odor control (for which they appeared to be effective)
and specifically for removal of orthochlorophenol. Second, the extremely
high (saturated) water vapor content in the exhaust gas stream interfered
with the removal capabilities of the activated carbon. Generally, acti-
vated carbons are used only on gas streams with a relative humidity of
50 percent or less. The carbon drums were achieving a high degree of
removal for specific components (i.e., 1-2 dichloroethane, benzene,
toluene, chlorobenzene, and chloroform) and a relatively high degree of
removal for specific compound groups (except halogens).
F.2.2.2 Liquid-Phase Carbon Adsorption—Site 5.82 Tests were
conducted on November 20, 1985, to evaluate the effectiveness of liquid-
phase carbon adsorption used to treat steam-stripped wastewater at Site 5.
Site 5 is a chemical manufacturing plant; the wastewater streams that are
produced are predominantly water-soluble. The two major waste streams are
redwater and Whitewater. The waste streams pass through decanters where
the oils are separated from the aqueous phase. A surface impoundment
(lagoon) is used as a large storage vessel to provide a stable flow to the
steam-stripping unit. The field testing of the Site 5 wastewater holding
lagoon is described in Section F.I.1.5. The steam stripper removes organic
compounds and water from the waste stream. Section F.2.3.1.3 describes the
field testing of the steam stripper. The organics separate and are trans-
ferred to an organic slopsump. The water that separates from the steam-
stripper condensate is recycled to the wastewater stream. Effluent from
the steam stripper is passed through a liquid-phase carbon adsorption unit
to recover any residual organics in the stream. The effluent is then pH-
adjusted and discharged to surface water.
Sampling was conducted over a 2.5-h period with an average of four
samples collected from each sampling point. Liquid grab samples were
collected from the carbon adsorber influent and effluent streams in 40-mL
VOA bottles. In addition, the temperatures of the influent and effluent
F-142
-------
streams were measured. The VO in the liquid samples were speciated and
quantified using a Varian Model 3700 GC-FID/PID/HECD. Material and energy
balances and stream flow and concentration data were used to characterize
the process streams around the carbon adsorption unit.
The flow rate of the stream leaving the carbon adsorption unit was
31,500 kg/h. The influent stream flow rate should have been virtually
identical. Table F-66 presents the source testing results for the TSDF
Site 5 liquid-phase carbon adsorption system.
F.2.2.3 Condensation.
F.2.2.3.1 Site 25.83 Tests were performed on September 24 and 25,
1986, to evaluate the performance of the condenser system used to recover
VO stripped from wastewater at Site 25. The system consisted of a water-
cooled primary condenser, a decanter, and a water-cooled vent condenser.
The steam stripping process is described in Section F.2.3.1.1.
The overhead vapors from the stripper pass through a condenser cooled
with cooling tower water. The condensate enters a decanter that separates
the heavier organic layer from water. The entire water layer is returned
to the steam stripper, and the organic layer is drained periodically by the
operator to a small collection tank for recycle back to the process. The
collection tank is open-topped and has a layer of water and sludge floating
on top of the organic layer.
The condenser is vented through the decanter to a vent condenser
(cooled with cooling tower water). The vent condenser receives vapors from
the initial water/organics/solids decanters and the steam stripper con-
denser/decanter. The initial decanters and storage tank are fixed-roof
tanks and have conservation vents that open as necessary to prevent pres-
sure buildup.
Samples of the vapor and liquid condensate condensed in the primary
condenser were taken, and flow rates at these points were measured. The
samples were analyzed by direct-injection GC after the compounds were iden-
tified using GC-MS.
Table F-67 presents the source testing results including mass flow
rates of four specific volatile organics into and out of the Site 25
primary condenser. Condenser organic removal efficiencies are reported
F-143
-------
TABLE F-66. SOURCE TESTING RESULTS9 FOR TSDF SITE 5, STEAM STRIPPER
WASTEWATER TREATED BY A LIQUID-PHASE CARBON ADSORPTION SYSTEM
Influent to
carbon adsorber
Constituent
Nitrobenzene
2-Nitrotoluene
4-Nitrotoluene
Total
Water
Mass flow
rate,
kg/h
1.29
0.076
0.139
1.51C
31,500d
Cone . ,
ppmw
40
2.4
4.4
47
NA
Effluent
from carbon
adsorber
Mass flow
rate,
kg/h
<0.025
<0.025
<0.025
<0.075C
31,500d
Cone.,
ppmw
<0.8
<0.8
<0.8
<2.4
NA
Carbon
adsorber
organic
removal
efficiency,^
wt %
>98
>67
>82
>95
NA
TSDF « Treatment, storage, and disposal facility.
NA = Not applicable.
aThis table presents the effectiveness of carbon adsorption as a wastewater
treatment technology for dilute nitroaromatic-containing streams.
bValues represent minimum removal efficiencies resulting from constituent
concentrations below analytical detection limits.
GCalculated as the total of the three detected compounds.
dBalance after accounting for three quantitated organics.
F-144
-------
TABLE F-67. SOURCE TESTING RESULTS3 FOR TSDF SITE 25, STEAM STRIPPER
OVERHEAD TREATED BY PRIMARY WATER-COOLED CONDENSER84
Constituent
Chloromethane
Methyl ene chloride
Chloroform
Carbon tetrachloride
Total V0d
Vapor
75
10,500
2,940
136
13,700
Mass flow rate,
ink Liquid outc
.7 67.1
9,420
2,780
122
12,400
q/h
Vapor out
8.6
1,050
160
14
1,230
Condenser
organic
removal
efficiency,
%
88.6
90.0
94.4
89.6
90.9
TSDF = Treatment, storage, and! disposal facility.
VO = Volatile organics.
aThis table presents mass flow rates by constituent into and out of the
primary water-cooled condenser associated with the steam stripper at
TSDF Site 25. Under operating conditions at the time of the test, no
additional removal was observed in the secondary condenser.
mass balance around stripper.
cBy difference between inlet and outlet vapor flows.
^Total of four quantified organics.
F-145
-------
based on effluent data. The condenser influent data presented are based on
a mass balance.
F.2.2.3.2 Site 26.85 Tests were performed on July 22 and 23, 1986,
to evaluate the performance of the condenser system used to recover VO
steam stripped from wastewater at the Site 26 plant. The system consisted
of a primary condenser cooled with cooling tower water in series with a
secondary condenser cooled with glycol. The steam-stripping process is
described in Section F.2.3.1.2.
Samples of the condensate and vapor leaving the secondary condenser
vent were analyzed, and the flow rates at each point were measured. The
vapor flow rate (noncondensibles) leaving the condenser vent was measured
by the tracer gas dilution technique with propane as the tracer because
this is a closed system operated at a pressure of 28 kPa. Although the
condenser was vented to an incinerator, these data were obtained to assess
condenser vent rates because many steam strippers have the overhead stream
vented to the atmosphere. The average condenser vent flow rate was 3.1 L/s
reported at 101 kPa of pressure and 25 °C.
Condenser system efficiency was evaluated from the organic loading
(organics entering the primary condenser with the vapor) and the quantity
of organics leaving through the secondary condenser vent. The difference
between the mass rates of organics entering with the feed and the mass
rates of organics leaving the stripper with the bottoms represents the
organic loading on the condenser. The 1,2-dichloroethane was by far the
major organic constituent entering the condenser.
The mass rate of organics leaving the condenser vent was determined
from the measurement of the vent flow rate and concentration. Table F-68
presents the source testing results for the Site 26 condenser system.
The condenser system removal efficiency for the major component
(1,2-dichloroethane) was consistently above 99 percent. However, as the .
vapor-phase concentration decreases and the volatility of individual
constituents increases, the condenser efficiency drops. Solubility of the
vapor constituents in the condensate also may affect condenser efficiency.
The overall mass flow rates from the condenser vent average about
20 Mg/yr of VO for this system. These rates represent emissions from the
F-146
-------
TABLE F-68.
SOURCE TESTING RESULTS9 FOR TSDF SITE 2(
OVERHEAD TREATED BY CONDENSER SYSTEM^
STEAM STRIPPER
Constituent
Vinyl chloride
Chloroethane
1,1-Dichloroethene
1, 1-Dichloroethane
1,2-Dichloroethene
Chloroform
1,2-Dichloroethane
Total VO, g/s (Mg/yr)
Average
vent mass
flow rate,
g/s
0.084
0.043
0.031
0.013
0.0098
0.11
0.34
0.63 (20)
Average
condenser
system
organic
removal
efficiency,"
%
6
47
15
88
84
96
99.5
Condenser
system
organic
removal
efficiency
range,
%
(0-15)
(32-65)
(0-53)
(83-94)
(73-94)
(93-99)
(99.2-99.8)
TSDF = Treatment, storage, and disposal facility.
VO = Volatile organics.
aThis table describes the TSDF Site 26 condenser system efficiency as
evaluated from the mass flow rates of constituents entering the water-cooled
primary condenser and leaving the glycol-cooled secondary condenser vent.
bBased on the propane tracer measurement of vapor flow rate.
F-147
-------
secondary condenser cooled with glycol at about 2 °C. The emission rates
would be expected to be higher for condensers cooled only with cooling
tower water at ambient temperatures (e.g., 25 °C).
The overall condenser removal efficiency for total VO is high because
the removal is dominated by the high loading of a single constituent (1,2-
dichloroethane). An average VO loading of 68 g/s is reduced to an average
vent rate of 0.63 g/s and represents a VO control efficiency of 99.1
percent.
F.2.3 Volatile Organic Removal Processes
F.2.3.1 Steam Stripping.
F.2.3.1.1 Site 27. Tests were performed on the Site 27 steam
stripper on January 13 and 14, 1988. The Site 27 plant produces linear
alkyl benzenes for use in detergent manufacturing by catalytic reaction of
ClO~Cl4 parafins with benzene. The feed to the stripper generally contains
between 1,500 and 2,000 ppm benzene. The treated wastewater contains
approximately 1 ppm benzene and is discharged to an aerated lagoon for
further treatment. An overhead stream is produced that is 3 to 6 percent
benzene.
Wastewater streams are generated from raw benzene purification,
catalyst regeneration, off-specification products, storm water, and
laboratory and maintenance operations. These streams are combined and
collected in a 1,100 m3, floating-roof, benzene-contaminated wastewater
storage tank. This tank serves to equalize any variation in flow rate or
concentration. The tank uses a floating roof to contain emissions. A
skimming system removes any hydrocarbon layer that may develop on top of
the water layer and transfers this to a drag tank.
The stripper feed is pumped from the storage tank through a preheat
exchanger and then enters near the top of the steam stripper at a maximum
mass flow rate of 3,600 kg/h. Steam is injected at the bottom of the
column at a maximum mass flow rate of 442 kg/h and flows countercurrent to
the feed. The steam stripping tower contains two, 3.7 m, packed sections
and has a diameter of 36 cm. The overall length of the column is 13 m.
The steam stripper remains idle until the liquid level of the holding
tank reaches 50 to 60 percent full. This process normally takes 1 to 2
F-148
-------
days. The steam stripper is operated somewhere between 10 percent and 20
percent of the time.
The treated or "stripped" effluent exiting the bottom of the column
flows through a preheat exchanger (serves to preheat the incoming waste)
and ultimately to an aerated wastewater lagoon at an adjoining facility.
The overhead vapors emanating from the top of the packed tower are
liquified in a water-cooled condenser and collected in a baffled, overhead
collection vessel. The aqueous phase is recycled to the top of the
stripping column while the organic-rich phase is collected in a dedicated
storage tank. The overhead collection vessel is under a nitrogen purge and
vents to1the flare system.
The primary objective of the test was to obtain data on the
effectiveness of steam stripping on removing volatile and semi volatile
organics from aqueous wastes. Additional objectives included assessment of
the effectiveness of the overhead condenser and characterization of the
treated and untreated waste. Liquid samples of feed, bottoms, aqueous
condensate, and recovered organic condensate were collected. Bottoms
samples (treated wastewater) were taken five times over a 16-h period. The
other liquid streams were sampled two to three times in the same period.
Condenser vent (gaseous) samples were taken three times in the course of
the test. Process data, including feed and steam flow rates, feed overhead
vapor and overhead condensate temperatures, and steam and column pressure
were collected throughout the test period. The efficiency of the condenser
could not be evaluated, as flow rates were unavailable for the organic
condensate and the condenser vent gas. Condensed vent gas was routed to a
flare system to control atmospheric emissions.
Liquid samples were analyzed for volatile and semi volatile organics
using EPA Methods 824087 and 8270.88 Vent gas samples were collected on
charcoal tubes, extracted and analyzed by NIOSH Method 127.89 Source
testing results based on averages of two sets of complete samples are given
in Table F-69. Note that total VO data in this table is the sum of the
four listed chemical constituents.
F.2.3.1.2 Site 25.90 Tests were performed on the Site 25 steam
stripper on September 24 and 25, 1986. The Site 25 plant produces one-
carbon chlorinated solvents such as methylene chloride, chloroform, and
F-149
-------
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F-150
-------
carbon tetrachloride. The steam stripper is used to recover solvents and
to treat the plant's wastewater. The major contaminants that are recovered
and monitored by the plant include methylene chloride, carbon tetrachlor-
ide, and chloroform with National Pollutant Discharge Elimination System
(NPDES) discharge limits of 50, 55, and 75 ppb, respectively. Plant analy-
ses showed variable concentrations in the feed stream to the steam strip-
per, ranging from hundreds of parts per million to saturation of the water
phase with organics and concentrations in the effluent generally on the
order of 50 to 75 percent of the NPDES discharge limits.
The wastewater at this plant consists of reactor rinse water and
rainfall collected from diked areas around the plant; consequently, the
flow rate and composition of the wastewater is cyclical and dependent on
the amount of rain. Plant personnel indicated that the steam stripper
operated roughly 75 percent of the time with accumulation in storage when
the stripper is not operating. Once the stripper is started, it operates
in an essentially continuous mode until the wastewater in storage has been
steam-stripped.
Site 25 wastewater enters one of two decanters (each approximately
76 m3) where it is processed as a batch. Sodium hydroxide solution
(caustic) is added to the decanter to adjust the pH, and flocculants are
added to aid in solids removal. The mixture is recirculated and mixed in
the decanter and allowed to settle. The wastewater (upper layer) is sent
to the stripper feed (or storage) tank (approximately 470 m3). The organic
layer (on the bottom) is removed periodically from the decanter and sent to
a surge or collection tank, and solids are removed periodically with a
vacuum truck for disposal. The cycle time for a batch of wastewater in the
decanter is about 1 day.
The steam stripper feed passes through a heat exchanger for preheating
by the effluent from the stripper. The stripper column is packed with
2.5-cm saddles and processes about 0.8 L/s. The stripper effluent, after
cooling by the heat exchanger, enters one of two open-topped holding tanks
(about 19 m3) where the pH is adjusted and analyzed for comparison with the
discharge limits. If the analysis is satisfactory, the water is pumped to
a surge tank for final discharge to the river under the NPDES permit. The
F-151
-------
overhead vapors from the stripper pass through the condenser system
described in Section F.2.2.3.1.
The primary objective of the field test of the steam-stripping process
at Site 25 was to determine how efficiently it removes VO from the waste-
water. Liquid samples were taken from the stripper feed, bottoms, and
condensate five times at approximately 2-h intervals during the day shift
for each of the 2 days of testing. The samples were taken in 40-mL glass
VOA vials with septa and no headspace. Vapor samples were taken three
times each test day-from the primary condenser vent, secondary or tank
condenser vent, and the vent of the stripper's feed (storage) tank. Vapor
samples also were collected over the open organic collection tank and from
the decanter vent prior to the vent condenser. The vapor samples were
taken in evacuated electropolished stainless steel canisters. Process data
were collected throughout the test. Process data included the feed flow
rate and temperature, steam flow rate and temperature, cooling water
temperature, column pressure drop, heat exchanger temperature, and outage
measurements for the holding tanks.
Samples for VO initially were analyzed by GC-MS using EPA Method 624.
After the individual components were identified by GC-MS, the compounds
were quantified by EPA Method 601.91 Method 601 is a purge-and-trap
procedure that is used for analysis of purgeable halocarbons by GC. The
Method 601 results are reported for aqueous samples. The level of VO in
the organic phase was determined by direct-injection GC. All of the vapor
samples were analyzed by GC with calibration standards for the components
of interest. Source testing results for the Site 25 steam stripper are
given in Table F-70.
F.2.3.1.3 Site 26.92 Tests were performed on the Site 26 steam
stripper on July 22 and 23, 1986. The Site 26 plant produces 1,2-dichloro-
ethane (ethylene dichloride [EDC]) and vinyl chloride monomer. Wastewaters
from the production processes and from other parts of the plant, including
stormwater runoff, are collected in a feed tank from which the waste is
pumped into the steam-stripper column. The organics are stripped from the
waste and condensed overhead in a series of two condensers described in
Section F.2.2.3.2. Approximately 2,400 Mg/yr of VO are removed from the
F-152
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F-153
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waste stream. The entire condensate, both aqueous and organic phases, is
recycled to the production process. The effluent stream from the stripper
column is sent through a heat exchanger to help preheat the feed stream and
then is sent to a WWT facility.
No design information is available for the tray steam-stripper column.
Typically, the feed rate is about 850 L/min to the column operating at
136 kPa. Steam is fed at 446 kPa and at 146 °C at a rate of about
1,700 kg/h.
The objective of the field test of the steam-stripping process at
Site 26 was to determine how efficiently it removes VO from hazardous waste
streams. Liquid samples were taken from the stripper influent and effluent
and from the overhead condensate aqueous and organic streams. Air emis-
sions from the condenser vent also were sampled. Sampling was conducted
over 2 days with samples taken five times at 2-h intervals on each day.
Liquid grab samples were collected in 40-mL VOA vials. Gas vent samples
were collected in evacuated stainless steel canisters. Process data were
collected at half-hour intervals throughout the testing. Process operation
data collected included feed, effluent, condensate, and steam flow rates;
temperatures of the feed, effluent, and condensate; and the steam pressure.
The VO in the water samples were analyzed by a purge-and-trap
procedure with separation and quantification performed by GC-MS analysis
(EPA Method 624). The organic phase in the condensate was analyzed by
direct-injection GC. The vent gas analysis procedures are detailed in the
site-specific test and quality assurance plan dated July 7, 1986, but were
not presented in the report.
Stream flow and concentration data were used to characterize all
process streams around the steam stripper. Table F-71 presents the source
testing results including average stream mass flow and composition data for
each stream entering and leaving the Site 26 steam stripper as well as
organic removal efficiencies. The organic removal efficiency for the steam
stripper was calculated on the basis of influent and effluent flows'from
the stripper. The composition data available for the condensate are pre-
sented in Table F-71 but are not used to calculate removal efficiencies.
This is done because of the need to see the actual amount of organic
F-154
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F-155'
-------
removed from the wastewater and because of the incompleteness of the
condensate data.
F.2.3.1.4 Site 5.93 Field evaluations were performed on November 20,
1985, of the steam-stripping system at Site 5. Section F.2.2.2 contains a
description of Site 5 and an evaluation of the liquid-phase carbon
adsorption system at the facility. The following paragraphs describe the
steam-stripping system at Site 5.
Wastewater from a feed tank is pumped to the steam-stripping column
where the organics are steam-stripped in the column and condensed from the
overhead stream. The stripped organics are separated from the condensed
steam in the organic condensate tank. The aqueous layer is recycled from
the organic condensate tank to the feed tank. The organic phase is sent to
a vented storage tank. From there, the organics are transferred to tank
trucks and taken bffsite for resale as fuel.
The steam-stripping column is 19.2 m high with an internal diameter of
0.46 m. The column is' packed with 3.17 m3 of 2.5-cm diameter stainless
steel rings. The steam stripper operates with a gas-to-liquid ratio rang-
ing from 55 m3/m3 at the bottom of the column to 24 m3/m3 at the top of the
column. Steam is fed to the column at approximately 130 °C and 365 kPa
pressure at a feed-to-steam ratio of 14.7 kg/kg.
The objective of the field test of the steam-stripping process at
Site 5 was to determine how efficiently it removes VO from hazardous waste
streams. Liquid and gas samples were collected and process parameters
measured at various points in the steam-stripping system. Liquid samples
were collected from the steam-stripper influent and effluent and from the
overhead aqueous and organic condensates. Emissions from the condensate
tank vent were sampled. Sampling was conducted over a 2.5-h period with an
average of four samples collected from each sampling point. Liquid grab
samples were collected in 40-mL VOA bottles. Gas vent samples were col-
lected in evacuated stainless steel canisters. Process operating data were
collected over a 4.5-h period to ensure that the process was operating at
steady state. Process data collected included feed, steam, and vent gas
flow rates, temperatures, and pressures.
F-156
-------
Vent gas was analyzed using GC-FID; identifications were confirmed
with GC-MS. The VO in the liquid samples were speciated and quantified
using a Varian Model 3700 GC. Material and energy balances and stream flow
and concentration data were used to characterize all process streams around
the steam stripper. Table F-72 presents the Site 5 steam stripper source
testing results.
' The steam-stripper organic removal efficiency was calculated based on
the influent and effluent flows for the stripper. The composition data for
the overhead streams are presented but are not used to calculate removal
efficiencies. This is done to show the actual removal of organics from the
waste stream. It also minimizes any background interference effects for
the wastewater. By looking at the same bulk stream of liquid, the same
liquid background is present, allowing for consistency between samples.
F.2.3.1.5 Site 28.94 Source testing was conducted from December 3
through 5, 1984, on the Site 28 steam stripper. Site 28 is engaged in the
reclamation of organic solvents for recycle and sale. The live steam-
stripping process is used for organic solvent reclamation. This system is
located inside a building that also contains three 3.8-m3 waste solvent
storage tanks and three 3.8-m3 product storage tanks. The building also is
used for drum storage. There are five 38-m3 outside storage tanks that are
used primarily for contaminated solvent and residue storage. An oil/gas-
fired boiler system is used for process steam generation. An analytical
laboratory is maintained in the building that houses company offices.
The contaminated organics processed by Site 28 are generated mostly by
the chemical, paint, pharmaceutical, plastics, and heavy manufacturing
industries. The types of chemicals recovered include the following VO:
ketones, aromatic hydrocarbons, chlorinated solvents, freons, and petroleum
naphthas. The recovered products may be recycled back to the generator or
marketed to suitable end users. Generally, 50 to 70 percent solvent recov-
ery from the waste stream is expected. Residues from the stripping process
are solidified by mixing with sorbents and shipped offsite to be land-
filled.
Contaminated organic solvents are charged to the stripper tank in a
batch operation. Steam is injected through spargers into the tank. The
F-157
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F-158
-------
stripper volume is circulated and pumped into the steam line for enhanced
contact between the steam and the stripper liquid. The stripped organics
and steam leaving the tank are directly condensed overhead and enter a
decanter. The decanter then contains two immiscible phases and, upon com-
pletion of the batch stripping, the organic phase is decanted to a storage
tank and the aqueous phase enters a miscible solvent tank. The aqueous
residual currently is being landfilled. The recovered solvents are
recycled or sold.
The horizontal stripping tank has a volume of 1.9 m3 with a steam
sparger running lengthwise along the bottom of the tank. Steam is usually
supplied at 240 kPa and at unknown temperature at a rate of about 250 kg/h.
The objective of the field test of the steam-stripping process at
Site 28 was to determine how efficiently it removes volatiles from hazard-
ous waste streams. Liquid and gas samples were collected and process
parameters measured at various points in the steam-stripping process.
Liquid samples were collected from the steam-stripper influent, condensate,
miscible solvent tank, and recovered VO storage tank. Gas samples were
collected from the condenser, miscible solvent tank, and recovered VO stor-
age tank vents. In addition, the volumes of liquid in the steam stripper,
miscible solvent tank, and recovered VO storage tank were monitored.
Four batch tests were performed with the steam-stripper system. The
four batch charges contained: (1) aqueous xylene, (2) 1,1,1-trichloro-
ethane/oil, (3) aqueous 1,1,1-trichloroethane, and (4) aqueous mixed
solvents. Each batch was sampled and monitored in the same fashion. The
liquid stripper contents were sampled at the beginning and end of each
batch test, with two intermediate samples taken. Liquid distillate samples
were taken at the end of the process, and gas vents were tested near the
midpoint of the process. Liquid grab samples were collected in 40-mL VOA
bottles. Gas vent samples were collected in evacuated stainless steel
canisters. Process data were collected periodically for the distillate
rate, overhead vapor temperature, and steam pressure and rate, and all
other process data were gathered at the start or finish of the operation.
Vent gas was analyzed by headspace GC-analysis method. The VO in the
liquid samples were speciated and quantified by direct-injection GC and
F-159
-------
headspace GC. Material and energy balances and process volume and concen-
tration data were used to characterize the batch stripping process.
Site 28 steam stripper source testing results are presented in Table F-73.
The organic removal efficiency was calculated on the basis of initial and
final mass of a constituent in the stripper tank. The composition data for
the overhead streams are presented but are not used to calculate removal
efficiencies. This is done because of difficulties in measuring the batch
volumes in combination with high organic removal efficiencies obtained.
Removing small, final amounts of a constituent from the stripper tank would
change the organic removal efficiency but would not significantly change
the volume in the condensate receiving tanks. By looking at the same bulk
volume of material, the actual amount of organic removed from the waste is
determined. This also removes the effect of any receiver tank contamina-
tion, volume reading bias for the stripper tank, or background interference
in the liquid.
F.2.3.1.6 Site 29.95 Tests were performed August 18 and 19, 1984, on
the Site 29 steam stripper. The steam stripper at Site 29 is used to
remove VO, especially methylene chloride, from aqueous streams. The steam
stripper removes 38.6 Mg/yr VO from the waste streams.
A process waste stream consisting of methylene chloride, water, salt,
and organic residue is fed to the steam stripper in which much of the VO is
stripped and taken overhead. The overhead vapor is condensed, with the
aqueous phase being recycled to the column and the organic phase stored for
reuse. The bottoms stream is used to preheat the incoming waste. Then it
is either sent to a publicly owned treatment works or sent back into a tank
for the feed stream, depending on whether the effluent meets discharge
limits. If the midpoint temperature of the stripping column is above a
given setpoint, the effluent meets limitations and is sent to the treatment
facility.
The stripping column contains 3.0 m of 1.6-cm pall rings and has a
diameter of 0.20 m. The waste stream feed rate is approximately 19 L/min
with an overhead organic product rate of about 0.28 L/min. Steam was fed
at a pressure range of 190 to 320 kPa, although the temperature and rate
were unspecified.
F-160
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The objective of the field test of the steam-stripping process at
Site 29 was to determine how efficiently it removes volatiles from hazard-
ous waste streams. Liquid samples were collected from the process waste
feed, stripper effluent, and organic overhead condensate. Air emissions
from the product receiver tank vent also were sampled. Sampling of the
influent and effluent was conducted approximately hourly for 5 h on the
first day and 12 h on the second, although a shutdown and restart delay of
6 h occurred on the second day because of instrument difficulties. Liquid
grab samples were collected in either a glass or stainless steel beaker and
then distributed into individual glass bottles for analysis. A composite
sample of the organic product was collected in glass bottles after comple-
tion- of the test. Gas vent samples were collected in evacuated glass
sampling bulbs. Process data collected included feed flow rate; column,
feed, effluent, and vent temperatures; and steam pressure.
Vent gas was analyzed using GC-FID (Method 18).96 The VO in the
liquid samples were analyzed by GC-MS (Method 8240).97 Material and energy
balances and stream flow and concentration data were used to characterize
all process streams around the steam stripper. Table F-74 presents the
source testing results.
F.2.3.2 Air Stripping.
F.2.3.2.1 Site 24.98 A test program was conducted for 4 days during
May 1985 on the Site 24 air stripping system. Site 24 is an NPL Superfund
site currently managed by EPA under CERCLA. It is a 1.6-ha abandoned waste
disposal facility that operated from 1962 to 1970. Several lagoons were
used to dispose of various liquids and sludges during operation of this
dump.
In response to citizen complaints received in early 1983, EPA
installed monitoring wells, a security fence, and a soil cap and regraded
portions of the site during these initial actions. A leachate collection
and treatment system also was installed by EPA at this time. The treatment
system consisted of an induced-draft air stripper. Air is drawn counter-
currently to the water flow, and, upon leaving the column, the air passes
through granular-activated carbon before entering the atmosphere. The
effectiveness of the gas-phase carbon adsorption system is discussed in
F-163
-------
F-164
-------