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4.5.6 Leaks and Spills on Soil
SEAMS Model (Fresh Spills)--
The SEAMS manual presents the following model for estimating volatile
releases from spills or leaks where a contaminant pool is visible on the soil
surface (41).
E. - Ki6 C* A (Eq. 52)
where ^Et - emission rate of component i (g/sec);
Kig- gas phase mass transfer coefficient of component i
(cm/sec);
C. - vapor concentraiton of chemical i (g/cm3); and
A - contaminated surface area (cm2).
Guidance on methods for estimating K.g and C. is presented in the SEAMS
iicability--
This model can be used for estimating air emissions of volatile species
from contaminant pools on soil surfaces.
The model does not consider the soil phase mass transfer resistance,
therefore it is not appropriate for use when spilled contaminants have seeped
into surface soils. Also, since the model does not consider the liquid phase
resistance, it is only useful for estimating releases of pure compounds.
SEAMS Model (Old Spills)--
The SEAMS manual recommends the use of the SEAMS land treatment model in
cases where past spills, leaks or intentional disposal directly onto surface
soils have resulted in contaminated surface soils with liquids in the pore
spaces. This model is described in Section 4.5.5.
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4.5.7 Emission Models for Fugitive Dust
Fugitive dust at hazardous waste sites (airborne wastes or contaminated
soils) most commonly results from wind erosion of the wastes or vehicular
travel over unpaved contaminated roads. The U.S. EPA has developed equations
to estimate fugitive dust emissions arising from vehicle travel on unpaved
roads (AP-42). The U.S. Soil Conservation Service (SCS), and Cowherd and
Gillette have developed models for predicting fugitive dust emissions
resulting from wind erosion from soil surfaces.
SCS Model--
The SCS model (71) takes into account such factors as surface soil
moisture content, roughness, and cloddiness, type and amount of vegetative
cover, wind velocity and the amount of soil surface exposed to the eroding
wind force. The SCS equation can be expressed as:
E - f(I-,CMC',L',V) - (Eq. 53)
where E - potential annual average wind erosion soil loss;
I* « soil credibility index;
C* • climatic factor;
K* - soil ridge roughness factor;
I" - field length along the prevailing wind direction; and
V - vegetative cover factor.
For the sake of brevity, the details of the calculation method are not
presented in this document. The reader is directed to the Skidmore and
Woodruff (59) source document and the SEAMS Manual (41) for further guidance.
Vehicular Traffic-
The US EPA has developed the following equations which can be used to
estimate fugitive dust emissions resulting from vehicular travel on
contaminated unpaved roads (54);
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EVJ - k(5.9) (fg)
or In metric form:
-} Q 5 f " p) (Eo. 55)
' * ' l q' '
365
where EVT - emission factor for vehicular traffic (Ib/vehicle mile
traveled, kg/vehicle kilometer traveled);
k - 0.45 * particle size multiplier for particles <10 urn (i.e.,
particles that may remain suspended once they become airborne
and which can be inhaled into the respiratory system);
s - silt content of raod surface material (percent);
Sp - mean vehicle speed (mph, kph);
W - mean vehicle weight (tons, Mg);
w - mean number of wheels; and
D » number of days with at least 0.254 mm (0.01 inch) of
precipitation per year.
The SCS wind equation computes total fugitive dust emissions due to wind
erosion which result from the combination of surface creep, saltation, and
suspension. If only the fraction of soil loss that is suspendable and trans-
portable over significant distances by wind is desired, the wind equation must
be adjusted (reduced) to reflect emissions from only this phenomenon.
Applicability --
The SCS model is applicable to wind-blown dust.
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Limitations --
The SCS model is designed to estimate annual erosion losses and is not
reliable when altered to estimate short term emissions (e.g., 24-hour
emissions).
Cowherd Model --
Cowherd (55) has developed a predictive equation for estimated respirable
particulate emissions from soils of "limited erodibility." The annual average
nti of respirable particulate emissions is a function of surface and climatic
factors represented by the following equation:
E10 - 0.83 f (1-V) P(UJ (50/PE)2 (Eq. 56)
where E10 - Annual average PM10 emission factor (mg/m2 - hr).
f » Frequency of disturbance per month.
U+ - Fastest mile of wind for the period between disturbances
(m/sec).
P(lT) - Erosion potential, i.e., quantity on the surface prior to
the onset of wind erosion (g/mz)
V * Fraction of contaminated surface area covered by
continuous vegetative cover.
PE - Thornthwaite's Precipitation Evaporation Index.
Soils of limited erodibility are nonhomogeneous surfaces impregnated with
nonerodible elements (stones, clumps of vegetation, etc) and contain a finite
reservoir of erodible material. In contrast, bare surfaces of finely divided
material are characterized by an "unlimited reservoir" of erodible particles.
Guidelines for characterizing the wind erosion potential of a surface and for
evaluating the terms in the Cowherd model are presented in the EPA manual
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entitled Rapid Assessment of Exposure to Participate Emissions from Surface
Contamination Sites (55).
Applicability --
The Cowherd model is applicable for estimating the emission rate of
respirable (less than 10 microns in diameter) wind-blown dust from surfaces of
limited erodibility.
Limitations --
The model is designed for estimated an annual average emission rate. It
is not designed to estimate short-term emissions.
Gillette Model --
Gillette (55) has developed the following model for estimating annual
respirable particulate emissions from wind erosion of surfaces with an
"unlimited reservoir" of erodible particles:
E10 - 0.036 (1-V)
JL
U
t
F(x) (Eq. 57)
where E10 * Annual average PM10 emission rate (g/m2 -hr).
V * Fraction of contaminated surface vegetative cover.
U * Mean annual wind speed (m/sec).
Ut * Threshold value of wind speed at 7m (m/sec).
x - 0.886 Ut/U (dimension less ratio).
F(x) * Empirical function.
Soil moisture is not taken into account in this equation because highly
arodible soils do not readily retain moisture. Gillette modified equation 55
slightly to obtain the following expression for estimating worst-case 24-hour
average emission rates:
E10 - 0.036 (1-V) (U. -2)3 (Eq. 58)
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where E1Q - 24-hour average PM10 emission rate (g/m2 -hr).
V * Fraction of contaminated surface area covered by
vegetation.
V
U+ * Mean annual fastest mile of wind (m/sec).
It should be noted, however, that the 24-hour average emission rate
predicted by this equation is based on annual average parameter values for U+.
Guidelines for evaluating the terms in the Gillette equations are presented in
the EPA manual entitled Rapid Assessment of Exposure to Particulate Emissions
from Surface Contamination Sites (55). The reader is referred to this
document for a more detailed discussion of the models.
Applicability --
The Gillette models are applicable for wind-blown dust emissions from
highly erodible surfaces. Both annual and short-term emissions can be
estimated.
Limitations --
The short-term model is based on annual average parameter values and may
overestimate the 24-hour average emission rate.
Vehicular Traffic-
The U.S. EPA has developed the following equations which can be used to
estimate fugitive dust emissions resulting from vehicular travel on
contaminated unpaved roads (54):
r t/c qi ,_ii ,Sj>> ,W, 0.7 ,w. 0.5 r365-DD~| (Eq. 59)
tyy - Kp.sj 112> ^30J 13; ^4^ [__ 355 _J
or in metric form:
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0=3
365-Dp
365 J
where Eyj* emission factor for vehicular traffic (Tib/vehicle mile
traveled, kg/vehicle kilometer traveled);
k - 0.45 « particle size multiplier for particles <10um (i.e*,
particles that may remain suspended once they become airborne
and which can be inhaled into the respiratory system);
s - silt content of road surface material (percent);
Sp - mean vehicle speed (mph,kph);
W • mean vehicle weight (tonssMg);
w - mean number of wheels; and
Dp - number of days with at least 0.254mm (0.01 inch) of
precipitation per year.
To estimate fugitive emissions due to vehicle travel for a given time
period, the emission factor, EVT defined above, is multiplied by the vehicle
miles traveled during that time period. Maximum release conditions may be
estimated by using a small value of Dp in the model to reflect assumed
drought conditions. Average emissions can be estimated by using annual
average value for Dp. Whenever possible, values for climatic and soil
parameters should be obtained for the particular site in question. Cowherd
et.al. (55) provides default values for model parameters that can be used when
site-specific data are not available.
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Applicabillty--
The AP-42 dust model is only applicable to dust resulting from vehicular
traffic.
4.5.8 Additional Models
Additional models identified but not included here are: Hwang's
modification of Farmer, (52,60) RTI Open Dump Model, (44) Hartley Method,
(37,61) Hamaker Method, (61) and Dow Method (61). The latter three equations
were developed for volatilization of pesticides applied to soil.
4.5.9 Non-Aerated Lagoons
Mackay and Leinonen Dynamic Two-Film Model —
This dynamic model (56,57) best serves those instances involving isolated
disposal of a given quantity of waste, as opposed to the steady-state scenario
offered by the other models. Laboratory validation of this model was reported
(57).
This model assumes that nearly stagnant films of well mixed bulk air and
water systems occur on both sides of the liquid/air interface.
NI " KiL (Ct - PiA) (Eq. 61)
C, - P,/H, + (C10 - P/H,) exp (-K1L t/L)
where N, - mass flux rate (mol/m2->
K1L - overall mass transfer coefficient (m/hr);
C1 * concentration of i at time t (mol/m3);
P, » equilibrium partial pressure of i in the vapor (atm);
H, - Henry's Law constant for i (atm-m3/mol);
Cio • initial concentration of i at t - 0 (mol/m3);
t - time (hr); and
L - depth of lagoon (m).
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icability--
The model offers an alternative to the steady-state scenario. However,
Wetherold (37) reports that despite its theoretical validity, the model is
difficult to apply to the "real world." The input parameters are difficult to
determine or" find in available literature. And, this modal best applies to
the emissions of single compounds.
Limitations--
The model fails to provide for white caps, thermoclines, eddy diffusion
and other similar phenomena, tending to under-predict emissions when these
conditions occur at the lagoon.
Thibodeaux, Parker and Heck Model--
This model (53)s which can be applied to both non-aerated and aerated
lagoons, evolved from basic accepted theories of mass transport. It is used
to determine emission rates of individual compounds, assuming that the
concentration of each compound remains constant in the aqueous phase (it does
not interact with the other compounds present}., It also assumes that the
influx of the compound is steady, that its bi©degradation rate is steady, and
that the lagoon surface can be clearly separated into either quiescent (non-
aerated) or turbulent (aerated) zones.
To use the equation, four mass transfer coefficients must be determined
from impartial relationships.
q, - M,^, (X, - X,*) (Eq. 62)
For each volatile component i:
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(Eq-65)
where q^ » flux of component i from the lagoon surface (g/cm2-sec);
Mt » molecular weight of component i (g/g-mol);
K^* overall liquid-phase mass transfer coefficient for component i
(mol/cm2-s);
X1 * mole fraction of component i in the aqueous phase (this must be
measured); and
X,*- mole fraction of component i in equilibrium with the mole
fraction of i in air, Y1 (if Yt is assumed to be negligible,
X,* can equal 0);
Kp kj * overall liquid-phase mass transfer coefficient for
aerated non-aerated zones of a lagoon, respectively (mol/cm2-
A^., A,, » surface areas of aerated and unierated zones, respectively
(cm);
1C, kj - individual liquid phase mass transfer coefficients for
the aerated and unaerated zones, respectively (mol/cm-s);
K*, K" - individual gas phase mass transfer coefficients for the
aerated and unaerated zones, respectively (mol/cm-s); and
H • Henry's Law constant in mole fraction form (y * Hx).
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Applicability--
The Thibodeaux, Parker, and Heck model is applicable to aerated, non-
aerated, and combined lagoons. The model assumes steady-state conditions and,
therefore, is applicable to undisturbed lagoons. The model is probably not
applicable to disturbed (disturbed sludge) conditions.
The accuracy of this model has not been verified as of 1982. Wetherold
(37) expressed some skepticism regarding the accuracy or availability of some
parameters necessary for the calculation of the mass transfer coefficients.
Also, the model requires additional development to satisfy the need for a
predictive model capable of predicting total VOC emissions from a lagoon
containing a complex mixture of compounds (37)»
way to deal with this, as suggested by DeWolf (53), is to sum up the
emissions estimated for several classes of compounds by selecting a
representative compound from each class. Acknowledging this selection as
"arbitrary", DeWolf provides some suggestions, noting that some compounds are
more likely to be encountered and those in mid-molecular weight range of 4 to
8 carbons are "likely to dominate in frequency of occurrence". He suggests:
Compound
Olefins
Aromatics Toluene
Haloganated hydrocarbons Methylene chloride
Oxygenated hydrocarbons Acetone
Smith, Bomberger, and Haynes Model--
The Smith et al. model (37) is applicable to emissions prediction for
highly volatile compounds in a lagoon setting. The model is not applicable to
low and intermediate volatility compounds. Also, liquid phase resistance
should be the controlling resistance.
The volatilization rate is expressed as a first-order kinetic equation.
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E - (Ka)env (c) (Eq. 66)
Ka (Eq. 67)
env
where E • mass emission rate per unit volume (Ibs/gal-day);
(Ka)env * volatilization rate constant for compound a in the environment
(day'1);
c » concentration of compound a (Ibs/gal);
Ka » ratio of volatilization constants of compounds a and oxygen as
K*
L*b K lab measured in laboratory (dimensionless); and
(K')env - oxygen reaeration rate in the environment (day"1).
Applicability-
The model is applicable to volatilization of high volatility compounds
from non-aerated waste disposal lagoons.
The model is limited in that it is designed to predict emission rates of
highly volatile individual compounds and it may be difficult to apply to
complex multicomponent wastes. The model is not appropriate for estimating
emissions of low or intermediate volatility compounds. Also, Wetherold (1982)
notes that determining the ratio of volatilization constants of a compound
(K*/K*) is expensive in the laboratory; attempts to estimate this ratio simply
using diffusion coefficient values increase the model's overall uncertainty.
Shen Model--
The Shen Model (48,58) presents an empirical equation for determining
volatile emissions from lagoons. The Shen Model is (48):
ERP1 - 18 x 10'6 KL1 AC, (Eq. 68)
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where ERpi - emission rate potential of compound i (g/sec);
A » lagoon surface area (cm2);
Cf » concentration of compound i in lagoon (mg/1); and
KL1 - liquid-phase mass transfer coefficient of compound i (g-mol/
KL1 - 4.45 x 10'3 (M^T0-5 (1.024)t'20 (U) °'67 (H)'0'85 (fq. 69)
where M, * molecular weight of compound i (g/mole);
t • lagoon surface temperature (oc);
U » surface velocity - 0.035 wind speed (cm/sec); and
H » average liquid depth of the lagoon (meter).
Applicability--
The Shen Model is applicable as a screening technology to estimate
volatile emission rates from lagoons. It appears, from Shen's discussion,
that the model assumes the lagoon is a dilute water solution, although this is
not explicitly stated. Shen indicates that the model should only be used when
"emission rates and risks are clearly acceptable or unacceptable.'
The model should be limited to use as a screening technology.
RTI Model--
The RTI Model is a simple volatile constituent mass transfer model (44):
E, * K,A C, (Eq. 70)
where E, - air emissions for component i from the liquid surface (g/sec);
K, - overall mass transfer coefficient for component i (m/sec);
A - liquid surface area (m2); and
C, - concentration of component i in the liquid phase (g/m3).
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The calculation of the mass transfer coefficient (K,) will depend on
whether the lagoon is quiescent, turbulent, a combination of quiescent and
turbulent, or has an oil film. In addition, the equation can be adjusted to
account for losses due to biodegradation. Several methods for calculation of
KL are given«in the listed reference as well as examples for applying the
model to specific site types.
Applicability—
The RTI Model is applicable to assessing volatile emissions from aerated
and non-aerated lagoons. The model is applicable to quiescent and turbulent
lagoons and can be adjusted to include biodegradation, although the toxic
nature of most waste lagoons will limit biological activity. The model is
applicable to both undisturbed and disturbed site conditions.
Limitations--
The model is not applicable to lagoons with a surface crust. While the
calculation of the mass transfer coefficient includes wind speed for quiescent
lagoons, the turbulent lagoon calculations appear to consider wind speed to
have negligible iffect on the emission rate.
4o5.10 Aerated Lagoons
Thibodeaux, Parker, and Heck Model--
This model is described in 4.5.9.
RTI Model--
This model is described in 4,5.9, and can be adjusted for aeration.
Chemdat 6--
EPA has published a number of models for RCRA sites, including models for
aerated lagoons (75). This same model is also available in a more user-
friendly version known as the Surface Impoundment Modeling System (SIMS).
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4.5.11 Sources of Model Input Data
The models presented in the previous sections require a wide variety of
input parameters. Table 17 provides a list of references which contain
tabulated data for some af the common chemical and soil property parameters;
hwoever, many of the models require additional input data such is mass
transfer coefficient, soil vapor concentration, etc. In these cases, the
reader is referred to the source document for each model. The authors
generally provide guidance on methods for estimating speicific model
parameters.
In addition, a number of existing data bases may be useful for supplying
the data requirements of the emission model. Data bases that contain landfill
facility data, chemical property data, geophysical data, and meteorological
data are described below. Hore detailed information regarding the data bases
is contained in Appendix D. Physical and chemical properties for compounds
frequently encountered at Superfund sites are given in Appendices F and G.
Landfill Data Bases
Five data bases have been identified that may provide the landfill
facility data required to estimate emissions using available techniques.
« Solid waste landfill survey;
« National Survey of Hazardous Waste Treatment, Storage, Disposal, and
Recycling Facilities;
« National Survey of Hazardous Waste Generators;
* Industrial Subtitle D Facility Study - Mail Questionnaire;
• Industrial Subtitle D Facility Study - Telephone Survey,
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Chemical Property Data Bases
* EPA Chemical Properties Data Base; and
© National Library of Medicine Online Service (HSDB)
« EPA GEMS Database
Geophysical Data Bases
* GEMS Geoecology Data Base; and
Soil Temperature Data Base.
Meteorological Data Bases
« STAR Data Base; and
« ' NCDC Data Bases.
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TABLE 17, DATA SOURCES FOR SELECTED MODEL PARAMETERS
Model Parameters Reference Number
Henry's Law Constant (H) 44, 51, §6, 62
Diffusion Coefficient (D) 41, 44, 53, 63
Soil Porosity (Pt,P8) 41, 64
Vapor Pressure (P*) 44, 51, 53, 56, 63
Methane Generation Rate Constant (k) 73, 74
Potential Methane Generation of Refuse (tT0) 73, 74
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SECTION 5
CASE STUDIES
Section 5 is a collection of five case studies that demonstrate the
protocol described in this manual for developing BEEs. The purpose of this
section is to document different experiences regarding site investigation and
characterization and to demonstrate the protocol for developing BEEs as
applied to these case studies. The sites selected represent different regions
of the country, different types and distributions of waste, varying levels of
air emissions potential, and varying levels of historical air pathway analyses
(APA) performed in support of the Remedial Investigation/Feasibility Study
(RI/FS) process.
Only the first case study demonstrates application of the complete
protocol. The protocol was implemented only partially at the other sites.
The assessment techniques used (or not used) in these case studies do not
necessarily represent the best or most technically suitable assessment
techniques. Many factors influenced the decision-making process concerning
the development of BEEs leading to air pathway evaluations. Also, the work at
these sites was conducted without the benefit of a formalized protocol for
designing APA programs and developing BEEs.
5.1 CASE STUDY 1: PETROLEUM WASTE LANDFILL/LAGOON
Case Study 1 is a disposal area for wastes from a defunct refinery.
5.1.1 Site History
The petroleum waste site resulted from years of dumping bottom sludge
from refinery vessels and tanks at a disposal area located adjacent to the
refinery. The on-site disposal activity was performed as general refinery
upkeep and was typical of the oil industry at that time.
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This small refinery was located in Southern California between the
foothills of a mountain range and a small community. The refinery dumped its
wastes on site from about 1930 to 1950. In 1952, the refinery was dismantled
except for an old garage and several tanks. Since 1953, the site has been a
crude oil pumping station. No known dumping has resulted from the pumping
station operation; therefore, all waste dates back over 35 years. At present,
the property is separated from an elementary school and a number of residences
by a fence and a drainage channel. The site is shown in Figure 22,
The refinery dumped most of its sludge in a landfill on the western edge
of the property. The landfill covered approximately one acre of surface area
and was bermed at the middli at some unknown time, thereby separating the
landfill at the north end from a lagoon at the south end. The landfill is
bilieved to have resulted from dumping soil into the landfill to solidify the
liquid waste. Investigations of the site disclosed that the entire
landfill/lagoon contained roughly 11,100 cubic yards of waste to a depth of
about 6 feet. The waste was an oily sludge, with an odor and appearance
typical of refinery wastes.
The site is subject to hot summers and mild winters. Precipitation is
approximately 20 inches per year, occurring predominantly during the winter
months. During site work, winds generally were light and easterly or
northeasterly during cooler periods. During warmer periods, onshore sea
bfiizts yielded moderate breezes from the west and southwest. The residential
neighborhood was downwind of the lagoon and landfill most of the time.
5.L2 Objectives
The objectives of the site work, from an air pathway perspective, were
several-fold: provide estimates of the undisturbed and disturbed site
emissions; to use BEEs to develop a litigation plan; and to conduct ambient
monitoring during the remedial investigation and mitigation to ensure worker
and community protection through the setting of appropriate action levels.
Table 18 summarizes the activities conducted at the site to address the air
pathway. These activities are described below.
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N
30-foot M«t«orologieai Tower
1 0-foot Meteorological Toww
Suspcatd Disposal Areas. 1-8
0 '00 200 300 <00 JOB
Figure 22. Location of suspected disposal areas.
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TABLE 18. APA ACTIVITIES CONDUCTED AT THE SITE
APA Objectives
Determine the baseline and disturbed emissions for the site using direct
emission measurement techniques. Protect on-site workers and the public from
air emissions during the investigation by using air monitoring and action
levels to stop site work.
Scoping
The lagoon and landfill were determined to contain petroleum waste that had a
moderately high volatile organic air emissions potential. Particulate
emission potential from the sludge/tar-like solid waste was considered to be
low.
Screening Measurements
The site was surveyed using real-time instruments (indirect technique) for
indicator compounds on a grid system. Soil samples were collected for head
space analyses to assess air emissions potential (direct technique}. These
data were used to design the in-depth measurement strategy.
In°Depth Measurements
The in-depth emission measurements included:
t Undisturbed baseline emission measurements using the surface
• Disturbed baseline emission measurements using the downhole emission
chamber; and
• Air monitoring for worker and public protection.
These data were used to develop undisturbed and disturbed site BEEs.
Mitigation
Undisturbed and disturbed BEEs were used to develop a remedial alternative
that included excavation and removal of the waste and air emissions control
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5.1o3 Scoping
In late 1980, the owner sought regulatory agency approval to remove the
waste and apply it to site roads. California's Regional Water Quality Control
Board denied,the request after two sets of samples, sent to two independent
laboratories, disclosed high lead concentrations in the waste. The owner then
sought a more thorough environmental evaluation of the site and
recommendations for remediation.
The initial task in completing the scoping phase of the site
characterization was a review of existing data. Information was collected
from the owner's site files, from files at a similarly operated refinery, from
public agencies, and from available references. The collected data were
reviewed to provide a working knowledge of the site history, conditions, and
environmental setting. Essentially no activities had been conducted to
determine waste volume, environmental impacts, emissions characteristics, or
waste existence and type in other suspected disposal areas.
The site investigation was initiated by a site inspection. The
inspection served to familiarize the crew with the site, to locate special
features, and to assist in the development of appropriate sampling methods.
This undertaking identified two types of wastes: a tar-like waste and a
granular waste that gave off fumes and white vapors when it came in contact
with water. The granular waste caused eye irritation and hindered breathing.
Based on this site scoping, the potential for volatile air emissions during
site mitigation was deemed to be high and further site characterization
activities were initiated.
5.1.4 Overview of Fieldwork for Site Characterization
An undisturbed emission survey (see 5.1.5) was completed to assess the
atmospheric impacts of volatilized compounds under prevailing site conditions.
The emission survey used indirect real-time instrument measurement techniques.
Knowledge of the type of waste indicated that total hydrocarbons and benzene,
as representative of aromatic species, were good indicator compounds for
volatile emissions from the petroleum waste. It was also possible that sulfur
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dioxide (S02) could be an air contaminant from the waste. Thus, total
hydrocarbons, benzene, and S02 were selected as the indicator compounds.
Other compounds may have been equally well suited for use as indicators, but
the compounds selected proved to be adequate. Testing for these compounds
showed low emissions (less than three times background levels) of total
hydrocarbons, benzene, and S0r This result was obtained by comparing on-site
emission rate data to background or off-site data. It was concluded that no
significant atmospheric impacts existed on or off site for undisturbed site
conditions.
To assess the potential impacts of air emissions of the combined site
during remediation and to provide adequate monitoring for on-site personnel
and nearby residences, a monitoring program was conducted that included:
constant meteorological monitoring at two stations; monitoring for emissions
from waste disturbance activities at the property boundary between the waste
and the nearby residences; and surveying of corehole borings.
Two meteorological towers (see Figure 22) were used to collect continuous
data. A 33-foot tower equipped with meteorological instrumentation collected
the primary meteorological site data during the field activity. In addition,
a 10-foot tower provided micro-meteorological wind speed and wind direction
data. The towers were positioned upwind and downwind of the landfill and
lagoon. Meteorological data were used in receptor modeling, in conjunction
with the measured emission rate data, for planning remedial options.
Additional waste characterization efforts were performed. Five core
holes were drilled through the waste and into the soils below the waste to
permit sampling of the waste and soils and examination of waste and soil
stratification and physical properties. They also provided a means for
measuring volatile species emissions as a function of depth in the waste.
Wastes were found to be only 5 or 6 feet deep over the §0,000 square-foot pit
area, for a total of approximately 11,100 cubic yards of wastes in the
landfill and ligoon. Wastes were generally soft and semi-fluid in the lagoon
and hard or soil/waste mixtures in the landfill. The waste had a pH below -
2.0, contained varying levels of trace metals (including high concentrations
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of lead in some samples), and had a very high percentage of organic material.
Soils below the wastes were predominantly alluvial gravels mixed with sand and
silt. The soils rapidly buffered acidic waste leachate. Trace metals were
found in varying concentrations and no apparent trend existed with depth. The
underlying soils had been impacted by low levels of hydrocarbons originating
in the waste pit.
In addition to the air-related work described above, extensive work was
undertaken to assess the impact of the site on local ground water. Also,
eight small areas suspected of being former waste disposal areas were
investigated.
The site inspection data were reviewed and a subsequent site
investigation plan was developed. This Included an undisturbed emission
survey, air monitoring on-site and at the fenceline during drilling and
sampling of wastes in the landfill and lagoon, and an emissions survey under
disturbed conditions to estimate the potential for emissions during possible
future disturbance of the wastes during an excavation activity.
S.I.5 Undisturbed Emissions Survey
Both screening and in-depth measurements were performed.
Screening Measurements--
A survey of the undisturbed surface emissions was conducted. First, the
main waste pit disposal area was surveyed and a map was prepared with a grid
system overlying the waste area to provide location reference. An emissions
survey was performed which consisted of a real-time instrument survey (an
indirect measurement screening technique) for indicator species at randomly
selected grid points mapped over the landfill and lagoon. This survey
provided general data on the level of gas concentrations from the landfill and
lagoon, identified potential areas of higher concentrations, documented
background conditions (i.e., gas species concentration background levels), and
provided input into the safety program, ensuring adequate worker/operator
protection. This screening technique was selected because it was a quick and
177
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inexpensive way to survey the site for areas of high air emissions potential.
These data could then be used to design the in-depth measurement approach.
During the emission screening, portable, ret!-time monitors were used to
determine sulfur dioxidi (S02), total hydrocarbon compounds (THC), and
aromatic compounds (benzene). THC measurements were made with an organic
vapor analyzer (OVA). S02 measurements were made with an electrochemical cell
instrument. The HNU analyzer was used to detect aromatic species reported as
benzene. S02, THC, and benzene, as well as surface and air temperature, were
measured at 27 grid node points under quiescent conditions. The portable
analyzers provided rapid feedback, but could not differentiate between various
hydrocarbon or sulfur species.
For.this site, benzene, S02,. and THC were used as indicators of air
emissions. Benzene is a carcinogenic contaminant representative of aromatic
compounds. Sulfur dioxide was a possible inorganic air contaminant on site.
Total hydrocarbons were monitored for an indication of total organic air
emissions.
In-Depth Measurements--
After completion of the screening measurements, in-depth measurements
were conducted te quantitite th@ gas emissions from the undisturbed site for
risk assessment purposes and to aid in siting drilling locations. The need
for this type of sampling was determined before any screening measurements
were performed, based on the waste type and the proximity of receptors (i.e.,
the suspected large volume of highly volatile wastes was considered likely to
cause significant air impacts during any remedial waste removal or disturbance
activities). Direct emission measurements were performed using an emission
isolation flux chamber. This in-depth technique was selected because it is
ideally suited to obtain emission rates from homogenous area sources. The
flux chamber is relatively easy to use and multiple measurements (i.e., 8 to
10) can be obtained in one day. Gas samples collected from the flux chamber
outlet line were analyzed using real-time analyzers. Samples also were
collected in gas canisters for detailed hydrocarbon speciation in an off-site
laboratory.
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The site was divided into zones of high and low emissions potential based
on plotted results from the real-time instrument survey. Locations for in-
depth measurements were randomly selected from grid cells in these different
zones. Based on the results of the real-time instrument survey., nine flux
chamber measurements were performed to assess the undisturbed emission from
the main landfill/lagoon. The flux chamber was constructed and operated as
described in Section 4. Measurements at a given grid point were typically
made over a 40-minute time period.
Chemical measurements performed on the air leaving the emission chamber
included:
t Continuous determination of S02 (InterScan);
• Continuous determination of THC (OVA);
• Continuous determination of benzene (HNU); and
« Grab sampling for organic speciation (Photovac 1010).
Undisturbed Emission Survey Results--
A total of 27 grid nodes were sampled, including sampling at five
background locations (upwind of each block), five duplicate sample points, and
sampling at one control point location at three different times of the day
(morning, noon, and afternoon). The control point was one of the grid points
that wis regularly sampled to establish an estimate of the temporal
variability in emissions at the site.
Very low gas concentrations were observed over the exposed waste. Most
of the screening measurements showed background levels at the locations
sampled for S02, THC, and benzene as shown in Table 19. Moderately low levels
of undisturbed emissions were observed over exposed waste in the lagoon and
the landfill. Table 20 provides undisturbed site emissions data.
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TABLE 19. SUMMARY OF SCREENING MEASUREMENTS OF UNDISTURBED WASTE
Range of Values
Number of SO* (pptn) THC fppm) Benzene (ppm)
Average Peak Average Peak
41 OoOOS 0.005 2-4a 2-4fi 0.01-0.80b 0.01-0.70b
a Differences probably due to instrument drift.
b Background levels only detected at 30 of 41 points.
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TABLE 20. CASE STUDY 1: SUMMARY OF UNDISTURBED SITE EMISSIONS DATA
Lagoon S02 THC* Benzeneb
Location
(Surface) (mg/m2, min"1) (ug/nr, min"1) (ug/m2, min'1)
»
#1 0.14 1.8 4.7
n 0=14 120 470
#3 0.14 7.3 43
14 0.14 44 1.8
IS 5.6 7.3 11
8 As determined by portable FID (OVA)
b As determined by portable PID (HNu),
Average 1.2 36 98
Landfill
Location
#1
n
Average
0.14
UL.
0.77
7.3
££_
18
3.6
3^6
3.6
181
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The results of the screening and in-depth emissions testing showed that:
• The emissions were highest in the landfill and lagoon where wastes
were exposed (especially where natural disturbances occurred; i.e.,
cracking of surface, waste seeps, etc.);
• Control point sampling at various times of the day (same location)
indicated a large temporal variation in emissions due primarily to
solar surface heating;
f Areas surrounding the combined site or in overburden on top of the
waste material showed background levels of emission; and
s Volatile emission rates from the combined site (landfill and lagoon)
were low for S02 and benzene under undisturbed conditions. For
steady-state conditions: S02 amission rates ranged from background
to 5.6 ug/m2 minute"1; THC emission rates ranged from background to
120 ug/m2s minute'1; and benzene from background to 470 ug/m2,
minute'1. Emissions did show a high dependence on diurnal
temperature fluctuations with more emissions observed during the
hottest periods, as expected. The field photovac analytical
capability provided limited hydrocarbon speciation data that helped
direct more detailed hydrocarbon sampling and analysis. The
photovac data were not used to determine emission estimates.
5ol.6 Disturbed Emissions Survey
Both screening and in-depth measurements were performed.
Screening Measurements--
Samples of soil/waste were collected during drilling at each sampling
point as part of the screening survey. Screening for volatile organic
compounds (VOCs) in these samples was performed at the field site with a
Photovac 1010 portable photoionization gas chromatograph (GC). This GC has
part-per-billion (ppb) level sensitivity for milliliter volumes of air. Soil
182
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and waste samples were collected (2 to 3 grams) and stored In 40 ml VOA vials
with Teflon\ SEPA. The vials were equilibrated In a 30'C water bath for 30
minutes prior to the head space analysis for VOCs. This sampling procedure Is
considered a direct measurement screening-technique.
»
During disturbance activities, fenceline monitoring for S02 and benzene
was conducted using portable real-time instruments. Also meteorological
conditions were monitored during all work disturbing the site. Action levels
were established to require cessation of site activities if exceedances were
noted (none occurred) to protect the local community.
Downwind and border monitoring consisted of three activities:
• S02 and THC were monitored immediately downwind of the disturbance
activity;
• S02 and THC were monitored at a mobile unit approximately 40 feet
downwind of the initial disturbance activities; and
• S02 and benzene were monitored at a mobile unit at the downwind
fenceline between the drilling operation and the nearby residences.
Standard monitoring procedures (see Volume IV of this series of manuals) were
used in operating the border and downwind stations. Air analyzers were
operated according to written quality control protocols and continuous data
printouts were collected using strip chart recorders. The monitoring stations
were positioned each day based on wind direction data from the meteorological
stations.
In-Depth Measurements--
Downhole emission measurements at various depths in the waste were
conducted during drilling activities to determine an emissions "profile" in
the waste. These data were used to characterize the waste properties and to
predict potential gas emission from the wastes if they were excavated.
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Downhole emissions measurements were performed using the direct emissions
measurement technique (i.e. downhole flux chamber). This technique is
considered an in-depth measurement technique and was applicable for the
landfill and the lagoon. The plexiglas chamber had an exposed surface area of
0.00318 m2. 'The chamber input and output lines were 40 feet long,
facilitating flux measurement to 30 feet below land surface.
Five locations for drilling were selected as part of the solid waste
investigation. They are shown in Figure 23. They were representative of
waste bodies and were equally spaced across the waste areas. Hydrocarbon
samples were collected in 2.8-liter stainless steel canisters. After
collection, the canisters were shipped to an off-site laboratory for analysis.
A total of 18 downhole emission measurements were performed and realtime
data for S02, THC, and benzene were collected at each point using the real-
time analyzers. Canister samples were collected at six locations (at various
depths within the five core holes) for speciation analyses. Canister samples
were not collected at all sampling locations in an effort to conserve project
resources. The indicator compounds were used to represent air emissions
potential in the absence of the canister samples.
184
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RADIAN
§
I
•Q
Q
€
14.
CONCaETE
PAD
N
'CO
Figure 23. Location of waste soil coreholes.
185
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Disturbed Emission Survey Results--
The results of air monitoring conducted during drilling are summarized in
Table 21. The results of border and immediate downwind monitoring for
disturbed site activities indicated no significant impact from fugitive
emissions downwind from the site (northeast) boring activities. Even though
the disturbed waste had a high emissions potential, small amounts of waste
were exposed in the drilling operations following the conservative operating
procedure. The border station was positioned on the west border to assess
neighborhood safety. This location also provided valuable onsite safety
information for site operations personnel.
The results of the downhole emissions survey included peak and steady-
state emissions for S02 and THC at the given depth. Benzene data were not
collected due to the lack of an extractive pump in that analyzer that could
pull the sample through the long sampling lines. The steady-state values are
more representative of the level of emissions expected involving a disturbance
of the waste (i.e., removal). Data results are presented in Table 22 to
illustrate the S02 and THC emissions observed as a function of the type of
waste/soil. This format illustrates the relative emissions characteristics of
S02 and THC per depth in the cores as well as the emission tendencies of the
waste/soil. A comparison of peak to steady-state emission values is used to
identify emission sources in the waste pit (i.e., limit of vertical
contamination).
Volatile emission rates from the site under disturbed conditions were
higher than the undisturbed site and demonstrated potential for volatile
emissions during waste disturbance activities. The S02 emission rates under
disturbed conditions ranged from background (1.6 EE4 ug/m2, minute"1) to 1.1.
EE6 ug/m2, minute"1, and the THC emission rates ranged from 3.8 EE3 ug/m2,
minute"1 to 3.8 EE6 ug/m2, minute"1. The results of the hydrocarbon speciation
analyses indicated the following hydrocarbon composition:
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TABLE 21. DOWNWIND/BORDER MONITORING RESULTS
Location
»
West Border
(Fence)
Core S-l
Downwind
40 m
Core S-2
West Border
(Fence)
Core S-2
West Border
(Fence)
Core S-3
West Border
(Fence)
Core N-l
West Border
(Fence)
Core N-2
Date
08/02/83
08/02/83
08/02/83
08/03/83
08/03/83
08/03/83
08/05/83
08/05/83
08/08/83
08/08/83
08/09/83
08/09/83
Species
Benzene*
S02b
Benzene
S02
Benzene
S02
Benzene
S02
Benzene
S02
High Leveld
(ppmv)
0.12C
Background
Background
Background
Background
Background
0.35
0.12
0.12C
Background
0.16C
Background
Duration
Elevated
Background
<5 minutes
a Benzene instrument (HNU) background typically 0.1 ppmv.
b S02 instrument (InterScan Analyzer) background typically 0.05 ppmv.
c Reading attributed to instrument drift.
d Background refers to instrument reading in "clean" air.
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TABLE 22. SUMMARY OF DOWNHOLE EMISSIONS DATA
SO. (ua/m2 min"1)
Core
S-l
Average
S-2
Average
S-3
Average
N-l
Average
N-2
Average
Depth
(ft)
5
7-1/2
15
2-1/2
4-1/2
15
20a
20
5
10
15
20
30
5
10
15
25
10
20
Peak
<1.9E4
>1.1E4
2.2E3
1.1E4
6.0E3
2.5E3
>1.1E4
4.0E3
1.6E2
4.6E2
7.6E2
3.0E2
6.0E2
LIE3
1.7E3
9.7E2
LIE3
1.6E3
6.7E2
Steady"
State
7.2E3
3.8E3
<8.3E2
3.9E3
5.4E3
1.9E3
1.7E3
>1.1E4
2.9E3
4.6E3
1.6E2
4.6E2
4.6E2
1.6E2
1.6E2
2.3E2
1.6E2
1.7E3
7.6E2
7.6E2
8.5E2
1.3E3
6.8E2
9.9E2
THC (ua/m2min~M
Peak
1.6E2
1.3E4
>3.8E4
1.9E3
8.3E3
>3.8E4
>3.8E4
>3.8E4
4.6E2
>3.8E4
1.6E4
>3.8E4
>3.8E4
>3.8E4
LIE4
2.3E4
>3.8E4
>3.8E4
>3.8E4
Steadyb
State
3.8E1
6.8E3
6.8E1
2.3E3
3.831
3.8E1
9.5E1
>3.8E4
3.8E2
9.3E5
7.6E1
>3.8E4
7.6E3
2.3E2
6.0E2
9.3E5
3.8E2
8.8E2
2.0E2
2.9E2
4.4E2
5.6E3
2.6E2
2.9E2
'Range of emissions, two measurements were conducted.
Steady-state values were averaged by core by operable unit to determine BEEs
E - Exponential Notation (7.2E3 = 7.2 x 103 = 7200).
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Hydrocarbon Class Average % _Ranqe %a
Alkanes 79.0 68-87
Alkenes 15.0 0.87 - 21
Aromatics 4.2 2.4 - 8.1
Oxygenates 0.62 0.15-1.5
Halogenated 1.2 0.091-3.3
Sulfonated ND ND
Unidentified 2.0 0.42 - 6.6
a5 cores, 6 canister samples
These data show that most of the air emissions were alkane species and of no
significant concern regarding toxicity. The aromatic fraction was, as
expected, around 5 percent, and was composed of numerous compounds.
5.1.7 Development of BEEs
Calculation of baseline emission estimates (BEEs) can be developed from
either ambient concentration data (indirect techniques) or from emission rate
measurement data (direct techniques). BEEs can be calculated for each
contaminant species detected or for a group of contaminant species. BEEs
obtained from direct measurement techniques which provide rate data (i.e.,
mass per unit time per given surface area) are preferable. The BEE is
normalized for the area of the source and has units of mass of contaminant or
group of contaminants per time.
BEEs can be calculated from individual emission sources and summed for
sites containing multiple emission sources (operable units), such as a lagoon
and a landfill with each source characterized by different air emission rates
and contaminant species.
The calculation of an undisturbed emission estimate for this site
included the following considerations. The site consisted of a waste area
containing a landfill in the northern portion and a lagoon in the southern
portion, separated by a berm. Each portion of the site was evaluated
separately. Undisturbed emission factors for each of the two operable units
were calculated separately and then averaged to provide an overall site
189
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emission estimate. The undisturbed emission rates for the lagoon and the
landfill, and the combined site emission estimate calculations are presented
below.
The undisturbed BEE for the lagoon (average) was calculated for S02 and
THC. The surface emission isolation flux chamber survey results from five
single measurements were averaged by species and multiplied by the lagoon
surface area to determine the unit BEE.
2 2 3
Lagoon BEEcn = (1.2ug/m-min)(6860 m) = 8.2 x 10 ug/min of SO,
MJ2
THC
Lagoon BEETHC » (36 ug/m2-min)(6860 m2) = 2.5 x 105 ug/min of THC
Similarly, the BEE for the landfill operable unit (average) was calculated for
S02 and THC. The emission isolation flux chamber survey results were averaged
for each species and multiplied by the surface area of the landfill to
determine the unit's BEE.
Landfill BEE$() - (0.77 ug/m2-min)(7240 m2) = 5.6 x 103 ug/min of SO
Landfill BEETHC - (18 ug/m2-min)(7240 m2) = 1.3 x 10s ug/min of THC
The overall site BEE (for S02 and THC) can be obtained by summing the
respective unit BEEs by species.
Calculation of emission estimates for disturbed site conditions can be
performed from either air monitoring data (concentration measurements) during
waste disturbances or from direct emission rate measurement data.
Concentration values can be expressed as a concentration (ppm-v) for each
species, as a ratio of the species concentration to the total concentration
from all species, or as a percentage value for the species of interest over
the total concentration contributed from all other species. The disturbed
site emission flux data has the units of mass per time per unit area.
190
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The emission estimate is calculated by multiplying the average measured
emission rate by the total surface area of disturbed material. This results
in a single value of mass per unit time which provides a relative estimate of
the rate of air emissions from the source. Emission estimates can be
calculated for a site with either individual sources or with multiple sources.
, These operable units often are investigated and remediated independently.
Emission estimates for a combined site can be calculated by using the highest
disturbed emission estimates for each source and summing the emission per time
for each source.
Summaries of the average disturbed emissions flux for both units of the
Case Study 1 site are presented below:
Landfill
S02 - 9.2 x 102 (ug/m2-min)
THC - 1.7 x 103 (ug/m2-min)
Lagoon
S02 - 2.9 x 103 (ug/m2-min)
THC - 6.4 x 103 (ug/m2-min)
These data can be used in conjunction with estimates of exposed disturbed
waste to predict air impacts from various waste disturbance and treatment
techniques.
Example
Excavation of the landfill would typically expose 50 m2 of waste at a
time. The estimate of THC air emissions from the site activity would be:
THC (landfill) = 1.7 x 103 (ug/m2, minute'1) x 50m2
- 8.5 x 10s (ug/min)
Depth-specific information could be used to provide area and depth-specific
emission estimates as needed.
191
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5.1.8 Summary
The Case Study 1 investigation was generally a thorough, well documented
study that fully addressed the air pathway for volatile contaminants. The
study followed closely the steps outlined in this manual's protocol and all
objectives were met. Furthermore, site personnel report that the knowledge of
the potential for emissions, ultimately resulted in a safer and more cost-
effective remediation of the site. BEEs were used in risk assessment and in
designing removal plans. Air emission control techniques were selected based
on the BEEs.
5.2 CASE STUDY 2: BRUIN LAGOON
Case Study 2 is a disposal lagoon that received various wastes from a
mineral oil refinery. This site was under remediation in 1984 when subsurface
gases were unexpectedly released during cleanup. Work was halted and the
remedial design was reassessed. A second Remedial Investigation/Feasibility
Study (RI/FS) was then performed. This case study focuses on the APA
conducted during this second RI/FS (see Table 23).
5.2.1 Site History
Bruin Lagoon is located about 45 miles north of Pittsburgh, in Bruin
Borough of Butler County, Pennsylvania. The 4-acre site is situated along the
western bank of Bear Creek's South Branch, approximately 7 miles upstream of
the creek's confluence with the Allegheny River. Part of the site lies within
the creek's 100-year floodplain. To the west, the site is bordered by private
homes and State Route 268. Bruin Borough's main residential and commercial
areas are within five blocks of the site and more than 30 residences are
within 500 feet of the lagoon. To the south is an abandoned refinery, which
is the source of the wastes deposited in the lagoon. Also, adjacent to the
site are two ponds and a small stream that drain into Bear Creek.
192
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TABLE 23. APA ACTIVITIES CONDUCTED AT THE CASE STUDY #2 SITE
APA Objectives
Assess the extent and composition of subsurface gas pockets. Monitor the
ambient air for health and safety reasons.
Scoping
Initially, the lagoon was determined to contain wastes that had minimal
potential for volatile or particulate matter emissions (first RI/FS). The
second RI/FS did assume that volatile emissions from subsurface gas pockets
were likely.
Screening Measurements
A variety of portable, real-time analyzers and detector tubes were used to
monitor the ambient air during drilling activities. Monitoring took place at
the site perimeter and in the ambient breathing zone near the drill rig. Soil
samples were collected and the emissions from the samples were scanned. The
screening data were used to design the in-depth measurement strategy.
In-Depth Measurements
The in-depth emission measurements involved collecting and analyzing grab
samples of gas from boring/wells whenever the ambient breathing zone
monitoring showed elevated concentrations significantly over background
levels. However, these data were not used to develop undisturbed and disturbed
site BEEs.
Mitigation
The disturbed waste emissions data were used in the development of the
remedial action plan. Although disturbed emission rates were not calculated,
knowledge of areas considered to be "hot spots" were used to conduct site
operations in a way that prevented major releases of air toxics to the air.
The remedial alternative included gas monitoring during on-site stabilization
and neutralization of the unstabilized sludge and collecting, venting, and
treating as necessary.
193
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Currently in remediation, Bruin Lagoon is an unlined earthen diked lagoon
that has been partially covered with 9300 cubic yards of stabilized soil/
sludge mixture treated during the first attempt at remediation. Beneath this
material is approximately 17,200 cubic yards of unstabilized sludge/tar, with
up-welling of the waste in a number of areas. The sludge/tar contains
sulfuric acid and heavy metals, along with other contaminants. The lagoon
area of the site is generally level and lacks vegetation. A cross-sectional
view of the site is shown in Figure 24.
Bruin Oil Company, producer of white (mineral) oil, began disposing of
its wastes at the lagoon in the 1930s. This continued for more than 40 years.
Materials discarded there included:
• Residues scraped from crude oil storage tanks;
• Used bauxite, charcoal filtering agents, and bone powder;
• Oils not meeting specification;
t Coal fines;
• Lime;
• Spent alkali; and
• Boiler house coal and ashes.
The lagoon attracted national attention in 1968 when about 3,000 gallons
of acidic sludge spilled into the South Branch of Bear Creek through a breach
in the dike. In the Allegheny River, roughly 4 million fish died and many
downstream communities temporarily lost their water supplies. The spill was
addressed, but the remedial investigation of the site didn't begin until 1981.
The abandoned refinery and the lagoon were owned by AH & RS Coal Company,
which underwent bankruptcy proceeding in 1986.
194
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Existing
Lagoon
Clean
SoKF*
<-v'
' < v' '• *'? V
• -'
Top ol Bediock
Walat Table
Aquilur
0
5
LEGEND:
Indicalus Flow OiiocUon
NOT TO SCALE
Figure 24. Generalized flow regime of perched zone and bedrock aquifer.
-------
5.2.2 Objectives
The objectives of the site work, from an air pathway perspective, were
two-fold: to monitor the ambient air for health and safety reasons; and to
assess the extent and composition of subsurface gas pockets. To meet the
latter objective, sampling and analysis of vapors contained in the shallow
wells were performed to: identify the composition and extent of gases trapped
under the site; determine their regeneration rates; and assess the potential
for their release into the atmosphere during remedial construction work.
5.2.3 Scoping
The existing data were reviewed to provide a working knowledge of the
site history, conditions, and environmental setting. Based on this review, no
specific potential emission characterization was called for in the first
RI/FS. After unexpected emissions were encountered when drilling through the
bottom of the lagoon during remediation, the second RI/FS did address the air
pathway to a greater extent.
5.2.4 Overview of Fieldwork For Site Characterization
EPA contractors began what would become the first RI/FS at Bruin Lagoon
in July 1981. Air monitoring during this remedial investigation failed to
find detectable levels of organics, sulfur dioxide (S02), hydrogen sulfide
(H2S), hydrogen chloride (HC1), or hydrogen cyanide (HCN) in ambient air at
the site. Although one well boring showed organic vapors during drilling
operations, the levels were not detectable at the ambient breathing zone.
Significantly, no borings through the open lagoon were performed in this
initial effort.
With the RI/FS completion in January 1982, EPA and the Pennsylvania
Department of Environmental Resources (PADER) selected a remedial alternative
that included sludge stabilization, dike reinforcement, debris removal, and
construction of a multi-layer cap to cover the lagoon. Design kicked off in
September 1982 and cleanup actually started in August 1983.
196
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The project proceeded until May 4, 1984, when hazardous gas and acid mist
escaped from an unanticipated crust, thought to be the bottom of the lagoon,
that was broken during mitigation. These organic vapors and sulfur dioxide or
hydrogen sulfide reached the ambient breathing zone but were not detectable at
the site perimeter. Gas sampling was performed for worker and public
protection. Gas samples from beneath the crust revealed high concentrations
of carbon dioxide, hydrogen sulfide, and sulfuric acid mist. Consequently,
EPA suspended cleanup activities and immediately launched in emergency
response, which included some removal, covering the lagoon with stabilized
sludge, installing 13 shallow gas monitoring wells, and collecting and
analyzing additional sludge and soil samples.
The site remained in the emergency mode until September 1984. The second
RI/FS was initiated the following January. Air monitoring conducted
throughout this RI included:
• Health and safety;
• Site perimeter;
t Ambient breathing zone;
• Downhole concentration sampling and analysis; and
• Sample screening.
Conclusions drawn from a review of all of these activities (the two RI/FS
endeavors and the emergency action) included identification of a "hot spot" in
the unstabilized portion of the lagoon that contained carbon dioxide, hydrogen
sulfide, sulfur dioxide and methane at levels deserving attention during
remediation. The RI/FS concluded, however, that subsurface gases were not
present throughout the site. To address the "hot spot" the remedial
alternative selected in September 1986 included gas monitoring, venting, and
treating during excavation, followed by post-closure monitoring.
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5.2.5 Undisturbed Emissions Survey
Based on the available documentation, no screening or in-depth mea-
surements were made to assess the undisturbed emission at the site. Since the
site contains heavy metals and is unvegetated, an evaluation of the entrained
particulate matter from the site would have been advisable, and some screening
measurements for particulates and inorganic gases may have been warranted.
Some air monitoring was performed immediately prior to site disturbances.
These limited data do address undisturbed emissions.
5.2.6 Disturbed Emissions Survey
Both screening (air monitoring and sample headspace) and in-depth (soil
vapor well) measurement techniques were used to assess the emissions during
site disturbances such as drilling. The following discussions are largely
taken from the second RI/FS prepared for the Bruin Lagoon site (65).
Screening Measurements--
The following air monitoring equipment was available on site during all
drilling activities:
• HMD photoionization detector (PID) with 11.7 and 10.2 eV probes;
• OVA (organic vapor analyzer) flame ionization detector (FID);
• H2S portable gas monitor;
• S02 portable gas monitor;
• H2S monitor alarms;
• Explosimeter/oxygen monitor; and
• Detector tubes S02, H2S, H2S04, 02, C02, natural gas.
Based on gases detected in past site work, portable direct reading real-
time instrumentation was primarily used for gas characterization and health
and safety purposes. Detector tubes were used for screening of possible
instrumentation interferences, confirmation of direct reading concentrations,
and analysis of gases not detected on available instrumentation.
198
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The direct reading monitoring instruments determined to be most effective
for monitoring drilling operations were the HNU PID (11.7 eV), H2S portable
gas monitor, H2S monitor alarms, and S02 portable gas monitor. The HNU PID
was selected over the OVA FID due to the sensitivity of this instrument to
hydrogen sulfide gas. The HNU PID could detect both hydrogen sulfide gas and
organic vapors. This selection was made because of past historical data
demonstrating possible H2S gas release.
Periodic monitoring of ambient air at the site perimeter was routinely
performed during drilling operations. Also, if ambient breathing zone
concentrations indicated possible gas releases, perimeter monitoring was
immediately initiated. Seventeen monitoring locations were established along
the site fence line at intervals of approximately 150 feet and marked with
stakes. Figure 25 shows the perimeter monitoring locations. Perimeter
monitoring was conducted with the H2S and S02 portable gas monitors and the
HNU PID.
During all drilling operations, the H2S and S02 portable gas monitor, H2S
monitor alarms, explosimeter/oxygen monitors, and HNU PID were used for
characterization of the ambient breathing zone. Background levels were
determined prior to starting the drilling.
Portable instrument readings provided continuous, real-time monitoring of
each split spoon and drilling depth to determine at what depth, if any, gas
releases occurred. Each split spoon and core sample was scanned with Figure
25 all direct reading instrumentation immediately after collection. Samples
showing positive readings were usually selected for chemical analysis.
In-Depth Measurements--
If ambient breathing zone monitoring showed elevated concentrations
significantly above background levels, a grab sample of the gas present in the
boring/well was collected for analysis. These grab samples were analyzed to
characterize the emitted gases. Grab samples were collected from a point
approximately 3 feet below the ground surface by inserting tubing into the
199
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Btluntu* t Ohu HR
LEGEND:
_4. Sueam
—*r— Fonce
Piopoi ty Lino
• Bodiock WuH
A Shallow Wtil
© SodBonog
• Pufhnolof An
Momloiing Location
NOTE: AW4 was not in&tuNud
050 100
Seal* In F»«i
:o
;5
:z
Figure 25. Monitor well and soil boring locations at the Bruin Lagoon site.
-------
boring/well and pumping the gas into an air bag collector. The bag sample was
then sealed and analyzed on-site using available instrumentation and detector
tubes.
Disturbed Emission Survey Results--
The following results are taken from the second RI/FS prepared for the
Bruin Lagoon site (65).
Air monitoring conducted during the 1981 remedial investigation of Bruin
Lagoon revealed no detectable levels of organics, S02, H2S, HC1, or HCN in the
ambient air at the site. Organic vapors were detected within one well boring
during drilling operations; however, no detectable levels were found in the
ambient breathing zone at this location. It should be noted that no borings
were constructed through the open lagoon during the initial RI and, as a
result, the gases trapped below the crust were not encountered.
Background air monitoring performed during field work in June 1984 showed
no detectable levels of H2S or methane. Air samples collected from the soil
boring indicated the presence of H2S, C02, methane, and aromatic hydrocarbons.
S02 was not detected in the downhole samples. H2S was present in the soil gas
on the average at about 300 to 400 ppm; initial concentrations were greater by
an order of magnitude or more.
Low levels of organic vapors, sulfur dioxide and hydrogen sulfide were
released into the ambient breathing zone when the subsurface of the site was
disturbed by drilling operations. S02 concentrations were observed as high as
50 ppmv but typically were found at 0.5 to 18 ppmv in the breathing zone
during drilling operations. H2S concentrations were lower with high
concentrations observed at 14 ppmv with typical concentrations of 1 to 10
ppmv. However, concentrations of these gases were not detectable at the site
perimeter.
The analytical results for the subsurface gas samples collected from the
13 shallow wells installed during the 1984 emergency action showed various
concentrations of volatile organics, S02, H2S04, and methane in the wells.
201
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Methane was observed in all the wells ranging from 2.6 to 4,400 ppm. These
concentrations showed good correlation with the organic CH4 levels measured in
the field by the OVA. Analysis of carbon tube samples collected for each well
showed no detectable volatile organic compounds. Sulfur dioxide was found to
be present iri 11 of the 13 wells, with four wells having S02 concentrations
greater than 100 ppm.
The results of the 1984 sampling of subsurface gases at the Bruin Lagoon
site showed elevated levels of S02. The presence of H2S04 mist was limited to
three wells (A-8, A-10, and A-13). Additionally, reactions and gas releases
occurred during the installation of each of these wells. Elevated levels of
S02 also were detected in well A-2. These wells are all located within 50
feet of one another, and, as a result, the data suggest that this area of the
site is a "hot spot" with respect to potentially harmful trapped subsurface
gases. Additional sampling one year later confirmed the presence of a "hot
spot" area located in the central part of the site.
5.2.7 Development of BEEs
No baseline emission estimates or disturbed emission estimates were
generated. It was noted, however, that remediation may result in the release
of pockets of hazardous gases trapped below a crust at the bottom of the
lagoon. BEEs would allow performance of risk assessments for various release
and meteorological scenarios at receptor points of interest.
Given the available data, the best method for determining BEEs for this
site would be to take the existing ambient air monitoring data and back-
calculate an emission rate using an air dispersion model. This is done by
setting up the model's run conditions to match those at the site as closely as
possible, and then varying the source term to find an emission rate that
produces downwind concentrations equal to those actually measured. Using the
respective air monitoring data sets, this procedure could be used for both
undisturbed and disturbed conditions. However, the accuracy of this procedure
is limited by the amount and representativeness of the available air
monitoring data.
202
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5.2.8 Summary
The Case Study 2 investigation points up the need to consider potential
emissions from the disturbed site before any remedial actions are undertaken.
Here, no soil borings through the open lagoon were performed during the first
RI/FS. The initial failure to do so, or to even consider potential air
emissions at this site, resulted in the need for a second RI/FS and associated
schedule delays and extra expenses. The study did not closely conform to the
steps outlined in the protocol of this manual. No undisturbed emission
measurements were performed (beyond some background air monitoring) and no
emission rate data were collected.
The best technique for screening particulate matter (PM) emissions at
this site would have been to collect upwind/downwind samples on filters using
high-volume sampling pumps (hi-vols). The total particulate matter present in
the air would be determined by dividing the filter weight gain by the volume
of air sampled. Analysis of the filter catch for selected metal species would
assist in assessing the health impacts from undisturbed emissions. A less
acceptable alternative would have been to measure the ambient particulate
matter loadings using a portable particulate matter analyzer. The activities
conducted, however, provided valuable data that were very useful in the
design, selection, and implementation of the remedial alternative.
5.3 CASE STUDY 3: LOWRY LANDFILL
Case Study 3 is an active municipal landfill that formerly also accepted
liquid and solid industrial wastes and domestic sewage sludge. This case
study focuses on APA activities conducted at the site (see Table 24).
5.3.1 Site History
The Lowry Landfill is co-owned by the City and County of Denver,
Colorado. It opened for business as a municipal landfill in 1965. The site
is located about 20 miles southeast of Denver and two miles east of the City
203
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TABLE 24. APA ACTIVITIES CONDUCTED AT THE CASE STUDY #3 SITE
APA Objectives
A soil gis study was conducted to locate waste pits, determine the extent of
off-site subsurface gas migration, and determine the waste pit contribution to
such migration. An air monitoring program was conducted to measure ambient
air pollutants during installation of monitoring wells in the waste pits.
Scoping
The landfill was determined to contain both hazardous and municipal wastes.
The generation of off-gases from the wastes was considered to be a hgih
probability.
Screening Measurements
The ambient air was monitored upwind and downwind of the site during
monitoring well installation. Samples were collected using a variety of
adsorption media. Soil samples were collected and the emissions from the
samples were scanned.
In-Depth Measurements
The in-depth emission measurements involved collection of soil gas samples at
a large number of points using vapor monitoring wells for deep samplign and
ground probes for shallow sampling. However, these data were not used to
develop undisturbed and disturbed site BEEs.
Mitigation
Migration plans have not yet been prepared. The site is currently under study
to further understand the air emissions potential from the site. These study
activites include air monitoring at nearby receptors of concern (e.g.,
community school).
204
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of Aurora, in Arapahoe County. The site covers approximately 480 acres. The
surrounding area was mostly undeveloped when the landfill was established, but
is growing rapidly today. (Proximity of the closest residence was not given
in the Remedial Investigation (RI) report.
*
From 1965 until the advent of the Resource Conservation and Recovery Act
(RCRA) in 1980, the facility accepted municipal refuse, liquid and solid
industrial waste (some of which was hazardous), and domestic sewage sludge.
The landfill handled these wastes by excavating pits, filling them three-
quarters with liquids and then covering the waste with refuse until a mound
several feet above the land surface was created. Landfills were dug
repeatedly, sometimes into old, filled landfills. The landfills at the south
end of the facility were covered with as much as 30 to 60 feet of refuse.
In 1975, Continental Oil Company contracted with site owners to set up
and run an oil sludge disposal operation in the southeastern portion of the
site. This operation and the acceptance of industrial waste stopped with RCRA
in 1980. At that time, the City and County of Denver hired a private firm to
manage the site as a municipal waste facility only. This contractor, Waste
Management, Inc., formed a subsidiary which opened a hazardous waste disposal
facility just north of Lowry. This facility was closed in 1982.
In the early 1980s, Lowry Landfill began to be closely scrutinized by a
number of public agencies due to odor problems and other concerns. These
first cursory looks focused primarily on the groundwater contamination
pathway, studying only shallow groundwater. Not all landfills were located or
confirmed. Initial investigations disclosed that records of types and
locations of waste were incomplete and inaccurate. Also, no measures had been
taken to prevent leachate or seepage from these pits.
Among the 60 pits identified through aerial photographs, it was estimated
that roughly 100 million gallons of liquid wastes were disposed on-site over
15 years. Wastes identified include: acid and alkaline sludges; caustics and
solids; brines, including plating wastes and other water-based sludges;
organics, both natural and synthetic, such as petroleum-based oils, grease,
and chlorinated solvents and sludges; watersoluble oils; municipal sewage
205
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sludge; low-level radioactive wastes; pesticide wastes; asbestos; and metallic
wastes.
EPA did not become intimately involved at the site until about 1981 when
Lowry was first considered as a candidate for the NPL. In 1984, Lowry was
placed on the NPL and formal investigations were initiated.
5.3.2 Objectives
At the Lowry site, a soil gas study and an air quality investigation were
performed as part of the RI. The soil gas study was conducted to help locate
the waste pits, to determine the extent of any off-site subsurface migration,
and to determine the waste pit contribution to such migration. The air
quality investigation was conducted to measure contaminants in the ambient air
during installation of monitoring wells in the waste pits.
5.3.3 Scoping
Existing data were collected and reviewed to provide a working knowledge
of the site history, conditions, and environmental setting. A topographic map
of the site and its environs was developed from aerial photos. Surveying was
performed to map sampling locations and determine the relative coordinates and
elevation of each location.
5.3.4 Overview of Fieldwork For Site Characterization
The purpose of the first phase, of a two-phase remedial investigation,
was to characterize the site geology and climate; identify the location and
contents of all landfills; characterize the extent of contamination, including
air and soil gas; and identify data gaps to be filled in during rememdial
investigation Phase II.
Investigatory work into some of the landfills was thwarted by three piles
of vehicle tires, two piles of roughly 2 million tires each and one pile of up
to 8 million tires. Findings disclosed that soil gas, air, groundwater,
surface water, and soil all were contaminated and that some migration was
206
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occurring. To detect air contamination, contractors sampled upwind and
downwind of the site, and.50 feet downwind from the five waste pit wells
shortly after installation (to demonstrate a worst-case emissions scenario).
The results showed that air quality was degraded as it crossed the site from
south to north (the direction of the prevailing wind). Volatile organic
compounds (VOCs) were detected at 0.020 to 16 parts per billion (ppb) higher
in the downwind samples relative to the upwind samples.
Separately, samples for soil gas emissions were taken from the landfills,
from gas well points and probes, and from 10 gas sampling wells installed
around the site perimeter by the contracted facility operator in 1981. The
results disclosed 19 VOCs, found in ranges of 37 to 160,000 ppb, and verified
that contaminated soil gas was migrating off-site in the vicinity of one of
the perimeter wells.
A complete meteorological monitoring station has been operating at Lowry
since April 21, 1985. It measures wind speed and direction, temperature,
relative humidity, barometric pressure, and precipitation on a 10-meter tower.
Measurements are taken by a Climatronics Electronic Weather Station (EWS)
connected to a Campbell Scientific CR21 data logger. The data are read
periodically into a mainframe DEC-10 computer.
5.3.5 Undisturbed Emissions Survey
No screening or in-depth measurements were made to assess the undisturbed
emissions at the site. However, the Phase I RI report (66) does recommend
that ambient air and meteorological monitoring be performed in the planned
Phase II work to collect background data. Based on the types of waste present
and the presence of contaminated soil gas, screening measurements (at a
minimum) would have been warranted for this site during Phase I activities.
5.3.6 Disturbed Emissions Survey
Both screening (headspace sampling and upwind/downwind air monitoring)
and in-depth (soil vapor wells) measurement techniques were used to assess the
air pathway.
207
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Screening Measurements--
Split spoon samples collected during drilling activities were retrieved
and opened, then the air space above the samples was scanned using an HNU
portable organic vapor analyzer.
*
The ambient air was monitored over a 12-day period during installation of
monitoring wells in the waste pits. The monitoring took place in November and
December of 1985 during which there was some snow cover; therefore, the
results do not equal a worst-case scenario. Samples were collected upwind and
downwind of the site and 50 feet downwind of the waste pit well installations.
A controlled release of waste pit well gas was permitted to help predict
ambient air impacts associated with remediation of the waste pits. Samples
were collected by concentrating air on carbon molecular sieves (CMS),
polyurethane foam, Tenax, and glass fiber filters. The sampling methods are
listed in Table 25.
In-Depth Measurements--
Soil gas samples were collected from a number of locations, including 10
existing soil vapor wells around the perimeter of the facility and wells
installed at four locations in suspected waste pits. The wells at the waste
pits were drilled to within 2 feet of the water table. Ground probes also
were driven into the waste pits at the same four locations to measure the gas
emanating from the waste pits and municipal refuse and reaching the near-
surface. Three more ground probes were installed at areas without underlying
waste pits.
Samples were collected from all locations using a pump to transfer gas to
a tedlar bag within a rigid-wall container. Sample gas was extracted at
roughly 1 L/min for 4 to 5 minutes. The perimeter soil vapor wells required
purging (three well volumes) before sample collection; the other sampling
points had free-flowing gas.
Samples were analyzed for priority pollutants by GC/MS using EPA Method
624 at an off-site location.
208
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TABLE 25. SUMMARY OF AIR MONITORING AT LOWRY LANDFILL
Collection
Media
Tenax
Carbon
Molecular
Sieve
Glass Fiber
Filters
Polyurethane
Foam (PUF)
N/A
Equipment Number of
Description Samples
Gillian HFS 52
personal pumps
Gillian HFS 52
personal pumps
Sierra Accu-Vol 20
high-volume
samplers
GMW Model PS-1 26
high-volume
samplers
Climatronics Continued
Wind Mark III
Analytes
Highly Volatile
Organic Compounds
VOCs
TSPa, Metals
Sem1-volatiles and
Pest1c1des/PCBs
Met Data
Duration of
Sampling
(Hours)
8-12
8-12
8-12
8-12
N/A
Method of Analysis
4
GC/MS
(Method TO-1)
GC/MS
(Method TO-2)
EPA Reference
Methods
GC/MS (Method 625
and Method TO-4)
N/A
Total suspended particulate matter.
-------
Disturbed Emission Survey Results--
A large data base was developed during this program and is summarized
here.
The upwind/downwind sampling indicated that the site is a VOC emissions
source. Total VOCs on-site were 54 ppb higher than upwind values, and
downwind concentrations were 25 ppb higher than upwind values. Downwind
concentrations of acetone, carbon disulfide, and toluene were 3 to 10 times
the upwind values. During the controlled release, these compounds were found
at 8 to 100 times the upwind values. Other compounds, such as 1,1,1-
trichloroethane, benzene, and TCE also were found at elevated (4 to 20 times)
levels downwind. These emissions could be expected to be greatly higher
during non-winter weather conditions.
The upwind/downwind sampling showed particulate matter emissions to be a
problem at the site. The upwind values averaged 187 ug/m3 and the downwind
samples averaged 325 ug/m3 with a range of 112 to 643 ug/m3. The average
downwind total solid particulates (TSP) exceeded the Primary TSP National
Ambient Air Quality Standard of 260 ug/m3.
Nineteen hazardous volatile organic compounds were detected in soil gas
samples emanating from waste pit liquid. These compounds were similar to
those found in the liquid samples. Concentrations ranged from 460 to 291,000
ppb. Nineteen volatile organic compounds were found in the refuse gas
samples, in ranges of 37 to 160,000 ppb. Compounds were nearly identical to
those found in gas samples above waste pit liquids except that the
concentration of compounds above these liquids was two to five times greater
than in the overlying refuse and six times greater than in refuse with no
underlying pits. It is reasonable to conclude that the liquids and refuse are
contributing to gas contamination.
210
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The results of perimeter well gas sampling indicate that subsurface
contaminant migration has occurred at Well GPM-3 and possibly at GPM-7.
Thirteen hazardous substances were detected in gases at Well GMP-3, near waste
pits and refuse disposal areas. Substances included volatile organics at
ranges of 9-to 1,200 ppb.
5.3.7 Development of BEEs
No baseline emission estimates for either the undisturbed or disturbed
wastes were generated, though sufficient data exist to estimate a disturbed
BEE. Given the available data, the best method for determining BEEs for this
site would be to take the existing ambient air monitoring data and back-
calculate an emission rate using an air dispersion model. This is done by
setting up the model's run conditions to match those at the site as closely as
possible, and then varying the source term to find an emission rate that
produces downwind concentrations equal to those actually measured. Using the
respective air monitoring data sets, this procedure could be applied to both
undisturbed and disturbed conditions.
5.3.8 Summary
The Case Study 3 investigation did not closely conform to the protocol
steps outlined in this manual. No undisturbed emission measurements were
performed and no emission rate data were collected. While substantial data
were collected, scheduling the air monitoring during cold temperatures and
snow cover conditions limited the data's applicability.
The best technique for screening undisturbed emissions at this site would
be to: 1) perform ambient air monitoring around the perimeter of the facility
to determine the magnitude of baseline emissions from the site and to verify
if any adverse health or safety risks are present; and 2) survey the site
using a portable analyzer and windscreen to delineate any localized emission
"hot spots." The results of these screening studies would need to be
interpreted to determine if any further undisturbed emission measurements were
warranted.
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5.4 CASE STUDY 4: WESTERN PROCESSING LANDFILL
Case Study 4 is a former industrial waste processing and recycling
facility.
5.4.1 Site History
The 13-acre Western Processing site is situated in the Green River Valley
between Seattle and Tacoma, five miles inland from Puget Sound. The site was
used for agricultural purposes until 1951 when it was leased to the Department
of Defense. An anti-aircraft artillery base operated there until the lease
expired in 1960. The owner opted for a cash settlement and left in place the
installation's buildings and on-site drainage system that linked its
facilities to a septic tank, a tile subsurface drain field, a 500-gallon
chlorination tank and a ditch leading to Mill Creek which runs along the
site's western border.
Western Processing, a waste recycling operation, purchased the site in
1960 and claimed to have reclaimed or recycled millions of gallons of liquid
waste and thousands of tons of solid waste before it was shut down in 1982.
The wastes handled included: animal blood, brewer's yeast, chrome baths,
corrosive liquids, crank case oil, flue dust, lead, pickle liquor, plating
bath solutions, solvents and paints, and zinc skimmings. These wastes were
handled, stored, or disposed of in storage lagoons (acid/caustic/cyanide
wastes), a fertilizer plant, a solvent recovery plant, bulk storage tanks,
cooling water lagoons, a chlorine gas tank storage house, a laboratory,
naphtha storage tanks, a 55-gallon drum storage area, and piles of flue dust.
By the late 1970s, the below-ground surface impoundments had been filled and
were being used to store waste material.
The site is located in an industrial area. A barbed wire fence separates
the site from a bicycle and jogging trail, which follows a railroad right-of-
way. This is the nearest community exposure to the site. Trail users
reported seeing hoses draped over the fence discharging into a ditch along the
railroad tracks that feeds into Mill Creek, prior to the closure of the
recycling plant (67). The site is shown in Figure 26.
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5.4.2 Ob.iectives
The Remedial Investigation/Feasibility Study (RI/FS) process did not
address the air pathway for contaminant transport to any meaningful extent.
Therefore, no objectives were set or met.
5.4.3 Overview of Fieldwork for Site Characterization
State and local inspections of Western Processing or its vicinity date
back to 1977. These were initially concerned about the quality of water in
Mill Creek. In 1982, EPA determined that the company's management practices
were resulting in the release of priority pollutants and other contaminants to
the environment.
A remedial investigation initiated in the fall of 1982 led to emergency
and interim remedial site activities in April 1983. These included removal of
some liquids, solids, and drums, and reorganization of concrete blocks from
five surface impoundments to create a large diked area where excavated
materials were then placed. The excavated materials contained solvents, paint
sludge, and some heavy metals. Also, buried storage tanks and drums were
encountered during this activity. Later in the fall, the state of Washington
led an effort to prevent storm water infiltration and runoff, which included
further excavation and berming as well as paving of the reaction pond.
A Phase I^surface cleanup, funded by the potentially responsible parties,
started with release of a remedial action plan (68) in July 1984. In that
plan, it was clear that air emissions work had been limited. The report noted
the northerly direction of winds would primarily deposit any contaminants
stirred up or blown off waste piles in or near Puget Sound. The report cited
a 1982 air analysis that showed only trace amounts of trichloroethene,
toluene, xylene, and tetrachloroethene. The low levels and high volatility of
these compounds, coupled with wide atmospheric dispersal, were thought to
create only limited effects on receptors during .past operations. "Although
past releases into the atmosphere may have been greater than observed in the
1982 samples and undoubtedly included particulate matter and contaminants.
213
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RADIAN
SANITARY
CHAIN FIEUO
DISCHARGE LINE
WESTERN PROCESSING
Figure 26. Western processing site.
-------
Other than volatile organics, this pathway is not believed to have been
significant."
That the air pathway was overlooked to some extent during the RI/FS stage
is apparent.. However, Phase II remediation work began in 1987 to remove
shallow wastes at the site, and a comprehensive air monitoring program was
initiated. This program is outlined below (as described in Lepic and Foster
(69).)
An air monitoring program was implemented to ensure adequate protection of
both the field team and the surrounding community. Work area monitoring was
conducted to identify action levels where personnel protection levels must be
upgraded. Continuous upwind and downwind perimeter monitoring was conducted.
Direct reading, real-time instruments were used to determine total gases
and vapors, cyanide, gamma radiation and combustible gas; particulate
concentrations also were measured. The field instrumentation used at Western
Processing included:
t OVA 128: total organic vapors;
• HNU PI 101: total organic vapors;
• Hand-held aerosol monitor (HAM): total particulates;
• Gastech CGI: combustible gases;
t Ludlum 19: gamma radiation;
t Monitox Compur 4100: cyanide;
• Draeger pump and colorimetric detector tubes: cyanide and methane;
• Hi-volume air samplers: suspended particulates; and
• Recording meteorological station: wind direction and speed.
Air was monitored regularly at 16 fixed locations around the site perimeter
to detect any possible off-site migration of airborne contaminants. In
addition, monitoring was conducted at each sample location to determine
adequate protection levels and to ensure worker safety. These monitoring
procedures are described below:
215
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• Borehole and excavation site monitoring: an OVA, HNU and HAM were used
to monitor the breathing zone at the drill rig and backhoe during the
subsurface exploration and sampling activities. A cyanide detector
and combustible gas indicator were used regularly; and
•»
• Drum, tank and utility monitoring: an OVA and HNU, radiation detector,
combustible gas indicator and cyanide monitor were used to test the
atmosphere within containers for flammable vapors.
5.4.4 Scoping
Collection and review of the existing data were performed. Based on this
data review, no need for an air pathway analysis was perceived.
5.4.5 Undisturbed Emissions Survey
No screening or in-depth measurements were made to assess the undisturbed
emissions at the site. Table 26 lists some of the contamination found at the
site. Based on the very high concentrations of heavy metals (e.g., lead at
31,000 ppm) found in the surface soil, an evaluation of the entrained
particulate matter from the site would have been advisable, and some screening
measurements were warranted.
5.4.6 Disturbed Emissions Survey
No screening or in-depth measurements were made to assess the disturbed
emissions at the site. Based on the very high concentrations of organic
compounds in the subsoil, an evaluation of the emission potential would have
been advisable.
216
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TABLE 26. MAXIMUM AND AVERAGE CONCENTRATIONS IN SOIL FOR SELECTED CONTAMINANTS
Contaminant
*
Chromi urn
Zinc
Arsenic
Antimony
Lead
Cyanide
Phenol
Aldrin
Dieldrin
PCB-1248
Hexachloroethane
Phenanthrene
Pyrene
1,1,1 -Tri chl oroethane
Methyl ene Chloride
Toluene
Trichloroethene
Maximum
Surface
5,300
81,000
38
98
31,000
15
19.0
0
0.145
3.30
5,090
20,000
16,000
0
0.130
0
0.037
Cone, (com)
Subsurface
7,600
40,500
102
130
141,000
179
65.0
2.86
3.34
19.6
1,80
62.4
11.0
174
49
394
580
Average3
Cone, (ppm)
594
2,580
3.28
8.59
5,450
11.2
1.65
0.006
0.007
0.341
0.0192
720
184
2.87
1.49
6.44
19.3
Based on geometric averaging approach.
217
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5.4.7 Development of BEEs
No baseline emission estimates for either the undisturbed or disturbed
wastes were generated. Given the available data, the best method for
determining BEEs for this site would be to take the existing ambient air
monitoring data (discussed below) and back-calculate an emission rate using an
air dispersion model. This is done by setting up the model's run conditions
to match those at the site as closely as possible, and then varying the source
term to find an emission rate that produces downwind concentrations equal to
those actually measured. Using the respective air monitoring data sets, this
procedure could be applied to both undisturbed and disturbed conditions.
5.4.8 Summary
The best technique for screening undisturbed particulate matter emissions
at this site would have been to collect upwind/downwind samples on filters
using high-volume sampling pumps (hi-vols). The total particulate matter
present in the air would be determined by dividing the filter weight gain by
the volume of air sampled. Analysis of the filter catch for selected metal
species would assist in assessing the health impacts from undisturbed
emissions. A less acceptable alternative would have been to measure the
ambient particulate matter loadings using a portable particulate matter
analyzer.
Screening VOC emissions also would have been advisable, based on the
waste composition data. The best technique for screening undisturbed VOC
emissions at this site would have been to: 1) perform ambient air monitoring
around the perimeter of the facility to determine the magnitude of baseline
emissions from the site and to verify if any adverse health or safety risks
were present; and 2) survey the site using a portable analyzer and windscreen
to delineate any localized emission "hot spots." The results of these
screening studies would need to be interpreted to determine if further
undisturbed emission measurements were warranted.
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The best technique for assessing disturbed VOC emissions would have been
to expose representative areas of waste using a backhoe (or drill rig), and to
measure emission rates using the flux chamber technique. The best technique
for assessing particulate matter emissions would have been to use hi-vol
samplers arrayed downwind (i.e., transect technique) to capture emissions
during site disturbances.
5.5 CASE STUDY 5: OUTBOARD MARINE CORP. LAGOON/LANDFILL
Case Study 5 is a manufacturing site where harbor sediments and nearby
land are contaminated with PCBs.
5.5.1 Site History
Outboard Marine Corp. (OMC) sits on the west shore of Lake Michigan, 37
miles north of Chicago and 10 miles south of the Wisconsin border. This
hazardous waste site evolved from an outboard motor manufacturer that used
PCBs in die cast machines from the early 1950s to the early 1970s.
Over the years, the facility discharge created three areas of contami-
nation (see Figure 27). The first is Waukegan Harbor, a 37-acre irregularly
shaped harbor feeding into Lake Michigan. The operation also led to
contamination of "North Ditch," a small tributary that drains surface water
runoff into Lake Michigan. A nine-acre parking lot north of the plant was
identified as another area, of significant PCB contamination.
Concerns about possible receptors of site contamination included the
harbor's biological community and fish in Lake Michigan. The City of
Waukegan, population 67,653 in 1980, is nearby, but the harbor area is zoned
industrial. The 15 businesses in the immediate harbor area that employ about
3,500 people were the immediate concern. Also, the local Port Harbor received
heavy recreational use and long-term plans included development of the Upper
Harbor. Potentially, people in a variety of locations could be exposed to the
contamination via direct contact, fish consumption or possible drinking water
contamination.
219
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RADIAN
EAST-WEST PORTION
OF NORTH DITCH
NORTH SHORE
SANITARY
DISTRICT
OUTBOARD MARINE CORP.
JOHNSON OUTBOAROS OIV.
PLANT NO. 2
NEW
DIE
CAST
COMPLEX
OMC CORPORATE
HEADQUARTERS
OFFICES
OMC OUTFALL
JOHNSON OUTBOAROS
PLANT NO. 1
Figure 27. Map of Case Study 5 site.
-------
OMC purchased roughly 9 million pounds of PCBs from Monsanto Co. over a
20-year period beginning in the early 1950s. OMC used the PCBs as hydraulic
fluids in die casting machines and related equipment. This equipment leaked
routinely and the fluids ran from the plant floor into floor drains that
discharged into Waukegan Harbor and North Ditch. EPA estimated that as much
as 20 percent of the PCBs purchased could have been discharged.
It was not until 1975 that the Illinois Environmental Protection Agency
(IEPA) discovered the high levels of PCBs in soils and harbor sediments near
CMC's plant. This discovery was triggered by a 1971 EPA study that showed PCB
concentrations in Lake Michigan fish. In 1976, the EPA began to regulate PCB
disposal. At that time, OMC began to sample its outfalls and then sealed two
outfalls leading to North Ditch, pursuant to a joint Administrative
Enforcement Order by EPA and IEPA (70). OMC later declined to immediately
remove sediments contaminated with PCBs, as demanded by EPA. When clean-up
negotiations among EPA, IEPA, and OMC failed, legal actions were filed. These
legal actions were still pending in early 1988. Superfund money for this site
became available in 1983.
5.5.2 Ob.iectives
The objective of the APA for this site was to model the exposure of
downwind receptors to PCBs during baseline conditions.
5.5.3 Scoping
Existing data were collected and reviewed to provide a working knowledge
of the site history, conditions, and environmental setting. No information
was uncovered that indicated a need to modify the air pathway analysis
objectives.
221
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5.5.4 Overview of Fieldwork for Site Characterization
Discovery steps through site characterization led to the conclusion that
PCB concentrations were significant and that PCB release to the surrounding
environment could follow a number of pathways.
Waukegan Harbor--
EPA contractors estimated that in Slip Number 3 in the harbor about 7,200
cubic yards of-muck, varying in thickness from 2 to 5 feet, was contaminated
by about 167,200 pounds of PCBs. Concentrations typically exceeded 500 ppm.
Another 3,700 cubic yards of sand and silt (about 7 feet thick) were
contaminated by about 138,000 pounds of PCBs. In one localized area near a
former OMC outfall, concentrations exceeded 10,000 ppm.
In the upper harbor about 35,700 cubic yards of muck, 1 to 5 feet thick,
were contaminated with approximately 5,000 pounds of PCBs. Concentrations
here typically were 50 to 500 ppm.
North Ditch--
Contractors broke the North Ditch into three areas for study. In the
"crescent ditch," about 28,900 cubic yards of soil, roughly 25 feet thick,
were contaminated by about 403,700 pounds of PCBs, creating concentrations
ranging from 5,000 to 38,000 ppm. Another 2,300 cubic yards of soil 3 feet
thick north of the die storage area were contaminated by an estimated 200
pounds of PCBs. Concentrations here typically were about 200 ppm.
The "oval lagoon," about 27 feet deep, contained about 14,600 cubic yards
of soil contaminated by about 85,500 pounds of PCBs in the top 5 feet.
Concentrations within those 5 feet were about 26,000 ppm; no data were
available for below 5 feet.
In the main part of North Ditch, about 25,000 cubic yards of soil about
25 feet thick were contaminated by at least 4,300 pounds of PCBs.
Concentrations in 200 feet of the ditch's western portion were typically above
5,000 ppm PCBs and another 1,000 feet of the central/western portion of the
ditch showed concentrations of 500 to 5,000-ppm.
222
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Parking Lot--
The parking lot also showed significant contamination in contractor
studies. Approximately 278,000 pounds of PCBs were found in 105,000 cubic
yards of soil. Volatilization was thought to be slight because of soil cover
and partial pavement. Air emission estimates were not made.
5.5.5 Undisturbed Emissions Survey
No air monitoring for the presence of PCBs was conducted at the site.
Dispersion modeling was used to estimate rates of PCB volatilization. The PCB
concentration expected in solution at the sediment/water interface was
estimated by mixing contaminated sediment with water, decanting the mixture,
and measuring the PCB concentration in the water. This concentration number
was plugged into transport rate equations. Contractors assumed a
volatilization rate of 3.8 mg/m2/hour from a saturated solution, based on data
provided by General Electric Corporation. Assuming volatilization to be
proportional to the PCB concentration in the solution, calculations showed
that roughly 3.3 pounds of PCB were leaving the harbor portion of the OMC site
through the atmosphere per month. The rate would vary positively with
temperature. EPA estimated that 12 to 40 pounds of PCBs were volatilizing
from the harbor each year. In addition, the North Ditch was estimated to be
contributing another 15 pounds of PCBs to the atmosphere per year.
5.5.6 Disturbed Emissions Survey
No field measurements or modeling estimates were made to assess the
emissions during site disturbances. It would be advisable to conduct a
laboratory or field study to determine the degree to which volatilization will
increase during dredging or other site remediation work. The emission
estimates could then be used as inputs to dispersion models to assess the
impact on downwind receptors.
223
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5.5.7 Development of BEEs
As discussed above, undisturbed (baseline) emission estimates were
developed for two of the three operable units at tht site. These estimates
were 12 to 40 Ib. PCB/year and 15 Ib. PCB/year. No disturbed emission
estimates were developed. If emission rate data were available for waste in
the disturbed state (e.g., flux chamber test data), then disturbed emission
estimates should have been developed using the same modeling approach used to
develop the BEEs.
5.5.8 Summary
The air pathway for contaminant transport was assessed at this site for
undisturbed conditions using modeling techniques. This was a valid, cost-
effective option, given the logistical problems of making direct field
measurements at this site and the low probability of detecting PCBs in the
ambient air downwind of the site.
The best technique for assessing the disturbed PCB emissions would have
been to dredge up representative contaminated material and directly measure
emissions with a flux chamber. As an alternative, this approach could be
modified to perform the work in a laboratory setting.
224
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SECTION 6
REFERENCES
•
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28. Kerfoot, H.B. Soil-Gas Measurement for Detection of Groundwater
Contamination by Volatile Organic Compounds. Environmental Science and
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29. Schmidt, C.E., R. Vandervort, and W.D. Balfour. Technical Approach and
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32. EPA Reference Methods, Environment Reporter, December 5, 1980.
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1983. 26 pp.
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34. National Institute for Occupational Safety and Health (NIOSH). NIOSH
Manual of Analytical Methods. 1985.
35. L.J. Thibodeaux, D.G. Parker, and H.H. Heck. Measurement of Volatile
Chemical Emissions from Uastewater Basins. U.S. EPA, Hazardous Waste
EngineerinResearch Laboratory, EPA/600/5-2-82/095. Cincinnati, OH 1982
36. C.Cowherd, K.Axetell, C.M. Guenther, and G.A. Jutze. Development of
Emission Factors for Fugitive Dust Sources. EPA 450/3-74-037. U.S.
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37. Wetherold, R.G., and D.A. Dubose. A Review of Selected Theoretical
Models for Estimating and Describing Atmospheric Emissions from Waste
Disposal Operations. EPA Contract 68-03-3038, U.S. Environmental
Protection Agency, Office of Research and Development, Industrial
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38. Esplin, G.J. Boundary Layer Emission Monitoring. JAPCA Vol. 38, No. 9,
1158-1161 September 1988.
39. U.S. Environmental Protection Agency. Guideline on Air Quality Models
(Revised). Office of Air Quality Planning and Standards, PB86-245248.
Research Triangle Park, NC July 1986.
40. Baker, L.W., and K.P. MacKay. Screening Models for Estimating Toxic Air
Pollution Near a Hazardous Waste Landfill. Journal of the Air Pollution
Control Association, 35(11):1190-1195, 1985.
41. U.S. Environmental Protection Agency. Superfund Exposure Assessment
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42. Farmer, W.J., M.S. Yang, J. Letey, W.F. Spencer, and M.H. Roulier. Land
Disposal of Hexachlorobenzene Wastes: Controlling Vapor Movement in
Soils. In: Land Disposal of Hazardous Wastes. Proceedings of the Fourth
Annual Research Symposium, U.S. Environmental Protection Agency,
Municipal Environmental Research Laboratory, San Antonio, TX, March 6, 7,
and 8, 1978. pp. 182-190.
43. Farmer, W.J., M.S. Yang, J. Letey, and W.F. Spencer. Land Disposal of
Hexachlorobenzene Wastes: Controlling Vapor Movement in Soil.
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Research and Development, Municipal Environmental Research Laboratory,
Cincinnati, OH, 1980. 69 pp.
44. U.S. Environmental Protection Agency. Hazardous Waste, Treatment,
Storage and Disposal Facilities (TSDF) -- Air Emission Models. Draft
Report, Office of Air Quality Planning and Standards, Research Triangle
Park, NC, 1987. pp. 6-1 to 6-50.
45. Radian Corporation. Survey and Assessment of Air Emission Modeling
Techniques for Landfills. Draft Final Report. EPA Contract 68-01-7287,
U.S. Environmental Protection Agency, Washington, D.C., 1988. 115 pp.
46. Shen, T.T. Estimating Hazardous Air Emissions from Disposal Sites.
Pollution Engineering, 13(8):31-34, 1981.
47. Shen, T.T. Air Quality Assessment for Land Disposal of Industrial
Wastes. Environmental Management, 6(4):297-305, 1982.South Coast Air
Quality Management District. Landfill Gas Emissions: Report of the Task
Force, El Monte, CA, 1982.
48. Shen, T.T., and G.H. Sewell. Air Pollution Problems of Uncontrolled
Hazardous Waste Sites. Civil Engineering for Practicing and Design
Engineers, 3(3):241-252, 1984.
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49. Farino, W., P. Spawn, M. Jasinski, and B. Murphy. Review of Landfill
AERR Models. In: Evaluation and Selection of Models for Estimating Air
Emissions from Hazardous Waste Treatment, Storage, and Disposal
Facilities. Revised Draft Final Report. Contract No. 68-02-3168, U.S.
Environmental Agency, Office of Solid Waste, Land Disposal Branch, 1983.
pp. 5-1 - 5-13.
50. Shen, T.T. Air Pollution Assessment of Toxic Emissions from Hazardous
Waste Lagoons and Landfills. Environment International, ll(l):71-76,
1985.
51. Thibodeaux, L.J., and S.T. Hwang. Landfarming of Petroleum Wastes -
Modeling the Air Emission Problem. Environmental Progress, l(l):42-46,
1982.
52. Hwang, S.T. Toxic Emissions from Land Disposal Facilities. Environmental
Progress, l(l):46-52, 1982.
53. DeWolf, G.B., and R.G. Wetherold. Protocols for Calculating VOC
Emissions from Land Applications Using Emission Models. Radian
Corporation, Austin, TX, EPA Contract No. 68-02-3850, U.S. Environmental
Protection Agency, Research Triangle Park, NC, 1984. 28 pp.
54. U.S. EPA AP-42: Compilation of Air Pollutant Emission Factors, Fourth
Edition. USEPA/OAQPS RTP, NC September 1985.
55. Cowherd, C., 6.E. Muleski, P.J. Englehart, and D.A. Gillette. Rapid
Assessment of Exposure to Particulate Emissions From Surface
Contamination Sites. EPA/600/8-85/002. Prepared for U.S. Environmental
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February 1985.
56. Mackay, D., and P.J. Leinonen. Rate of Evaporation of Low-Solubility
Contaminants from Water Bodies to Atmosphere. Environmental Science and
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58. Shen, TIT. Hazardous Air Emissions from Industrial Waste Treatment
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63. Perry, R.H. and C.H. Chilton. Chemical Engineer's Handbook. Sixth
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64. Brady, N.C. The Nature and Properties of Soils. Eighth Edition,
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II. EPA No 38.8L08.3 Milwaukee, WI. September 2, 1986.
67. CH2M Hill. Final Remedial Investigation Data Report: Western
Processing. RA-WA-37-OL16-1, Kent, WA. December 17, 1984.
68. Dames and Moore and Landau Associates Western Processing Technical Basis
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69. Lepic, K.A. and A.R. Foster. Superfund 1987: Proceedings of the Eighth
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70. U.S. Environmental Protection Agency. Superfund Record of Decision:
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71. Skidmore, E.L. and N.P. Woodruff. Wind Erosion Forces in the United
States and Their Use in Predicting Soil Loss. Agriculture Handbook No.
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Research Service, 1968.
72. Emcon Associates. Methane Generation and Recovery from Landfills. Ann
Arbor Science Publishers, Inc. 1982.
73. U.S. EPA. Air Emissions from Municipal Solid Waste Landfills.
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74. McGuinn, Y.C., Radian Corporation. Use of landfill Gas Generation Model
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233
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APPENDIX A
ANNOTATED BILIOGRAPHY
-------
APPENDIX A
ANNOTATED BIBLIOGRAPHY
*
I. Adams, D.F. Sulfur Gas Emissions from Flue Gas Desulfurization
Sludge Ponds. Journal of the A1r Pollution Control Association,
29(9):963963, 1979.
This article describes an enclosure used to measure natural
sulfur species emissions. This article was used to assist in
the development of the Radian surface flux chamber.
II. Aim, R.R., C.P. Hanauska, K.A. Olson, and M.T. P1ke. The Use of
Stabilized Aqueous Foams to Suppress Hazardous Vapors -- A Study of
Factors Influencing Performance. In: Superfund '87: Proceedings of
the 8th National Conference, The Hazardous Materials Control
Research Institute, Washington, D.C., November 16-18, 1987. pp. 480-
484.
This article presents results from laboratory and field testing
of 3M vapor suppression foams. Field testing was performed on
excavated material using a direct emissions approach: surface
emissions Isolation flux chamber.
III. Aim, R.R., K.A. Olson, and R.C. Peterson. Using Foam to Maintain Air
Quality During Remediation of Hazardous Waste Sites. Presented at
the Air Pollution Control Association's 80th Annual Meeting and
Exhibition, New York, NY, June 21-26, 1987. 17 pp.
This paper is not useful for determining emission measurements
or estimating techniques. It also is not useful as a case
study. It provides some data on the effectiveness of foams
from laboratory tests and Radian testing of 3M foam, using a
surface isolation flux chamber.
IV. Aim, R.R., K.A. Olson, and E.A. Reiner. Stabilized Foam: A New
Technology for Vapor Suppression of Hazardous Materials. Presented
at the International Congress on Hazardous Materials Management,
Chattanooga, TN, June 8-12, 1987. 13 pp.
This paper is not useful for determining methods of emission
measurement or estimating, or as a case study. It provides
data on the effectiveness of vapor suppression foam from
laboratory tests using a "Radian-style" flux chamber and GC.
The paper Includes few details and references Radian field
testing of 3M foams.
-------
V. Asolan, M.F., and M.J. Barboza. A Practical Methodology for
Designing and Conducting Ambient Air Monitoring at Hazardous Waste
Facilities. For Presentation at the 79th Annual Meeting of the Air
Pollution Control Association, Minneapolis, MN, 1986, 16 pp.
• This paper presents an approach for designing ambient tir
monitoring programs, including a decision tree. The emphasis
1s placed on establishing program objectives, including why
sampling 1s performed, for who, and what 1s to be sampled. The
approach is intended for use for project planning rather than
project execution.
VI. Astle, A.O., R.A. Ouffee, and A.R. Stankunas. Estimating Vapor and
Odor Emission Rates from Hazardous Waste Sites. In: National
Conference on Management of Uncontrolled Hazardous Waste Sites, U.S.
Environmental Protection Agency, et al., Washington, D»C., 1982.
pp. 326-330.
This article discusses sampling and evaluation of emissions for
odor. The sampling tunnel may have some usefulness for
investigating volatile emission rates versus wind speed;
however, the technique would require development and testing.
VII. Baker, L.W., and K.P. Mackay. Screening Models for Estimating Toxic
A1r Pollution Near a Hazardous Waste Landfill. Journal of the Air
Pollution Control Association, 35(11):1190-1195, 1985.
Baker and Mackay evaluate performance of four air dispersion
models to calculate the ambient air concentration of vinyl
chloride versus measured concentration downwind of a landfill.
The vinyl chloride emission rate was calculated using Shen's
modification of Fanner's gas migration equation. The air
dispersion models used are a ground level point source model,
two virtual point source mdoels, and a simple box model.
VIII. Balfour, W.D., R.G. Wetherold, and D.L. Lewis. Evaluation of Air
Emissions from Hazardous Waste Treatment, Storage, and Disposal
Facilities. EPA 600/2-85/057, U.S. Environmental Protection Agency.
Cincinnati, OH, 1984. 2 vol.
Emission rates based on direct and indirect emission
measurements were compared to emission rates calculated from
predictive models. Emission rate measurement techniques were
also compared against each other. Emission measurement
techniques include surface isolation flux chamber, vent
sampling, concentration profile, transect, and mass balance.
Predictive models include the Thibodeaux, Parker, and Heck
^Models (non-aerated surface impound), the Thibodeaux-Hwang
'Model (land treatment), and an API model (tanks). Details for
each measurement technique and model are provided.
-------
IX. Balfour, U.O., C.E. Schmidt, and 8.M. Eklund. Sampling Approaches
for the Measurement of Volatile Compounds at Hazardous Waste Sites.
Radian Corporation, Austin, TX, no date. 29 pp.
Sampling techniques for measuring volatile emission rates and
for measuring soil gas concentrations are discussed. Emission
rate techniques Included are emission Isolation flux chamber,
vent sampling, concentration profile, transect, and mass
balance. Soil gas concentration techniques are headspace
analysis of soil cores, soil gas probes (ground probe), and
passive samplers.
Each approach 1s described, and the applicable equations are
presented.
X. Balfour, W.D., and C.E. Schmidt. Sampling Approaches for Measuring
Emission Rates from Hazardous Waste Disposal Facilities. Radian
Corporation, Austin, TX, 1984. 13 pp.
Balfour and Schmidt present five sampling approaches for
measuring volatile emissions: surface emission isolation flux
chamber, vent sampling, concentration-profile, transect
technique, and mass balance. A comparison of the applicability
of each technique to various TSOF sites or units is given.
XI. Balfour, W.O., B.M. Eklund, and S.J. Williamson. Measurement of
Volatile Organic Emissions from Subsurface Contaminants. Radian
Corporation, Austin, IX, 1985. 20 pp.
This paper presents results of field measurement performed with
the surface emission isolation flux chamber. It also evaluates
the effect of six operating variables on measured emission rate
and appropriateness of statistical sampling procedure for area
.sources, and provides an analysis of variability in the method.
XII. Banerjee, P., and O.H. Homer. The Impacts of Using Assumed Versus
Site-Specific Values in Determining Fate and Transport. In:
Superfund'87: Proceedings of the 8th National Conference, The
Hazardous Control Research Institute, Washington, O.C., November 16-
18, 1987. pp. 126-128.
This article does not discuss emission rate measurement;
rather, 1t emphasizes the Importance of the need to obtain
site-specific data rather then assumed or literature-derived
values as inputs to risk assessment.
XIII. Berrafato, L.R., and R.A. Wadden. Predicted vs. Measured Air
Emissions of Volatile Organics from a Simulated Hazardous Waste
Lagoon. In: Toxic Hazardous Wastes, Proceedings of the 18th Mid-
Atlantic Hazardous Waste Conference, Chera. Ind. Inst. Toxicol.,
Research Triangle Park, NC, 1986. pp. 515-525.
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Evaporation of toluene and chlorobenzene from a simulated
lagoon was measured based on the liquid concentration of these
chemicals 1n the lagoon. The evaporation rate was compared to
a predictive node! similar to the Mackay-leinonen Model. The
rtsults showed the model may be useful for order of magnitude
. estimates.
XIV Bilslcy, I.L. Air Pollution Aspects of Hazardous Waste Disposal in
Texas. Environmental Progress, 5(2):123-129, 1986.
This article examines the Texas administrative review process
-for proposed hazardous waste disposal facilities. A case study
of a waste disposal facility application is reviewed.
XV. Blasko, M.J., B.F. Cockroft, W.C. Smith, and P.P. O'Hara. Design of
Remedial Measures and Waste Removal Program, Laekawanna Refuse
Superfund Site. In: Superfund '87: Proceedings of the 8th National
Conference, The Hazardous Control Research Institute, Washington,
D.C., November 16-18, 1987. pp. 367-370.
This article discusses the development of the design and con-
struction bid package for the remedial measures and removal
program. No information on emissions data is given. The RI
report would have to be reviewed directly to see if a case
study exists.
XVI. Breton, M., T. Nunno, P. Spawn, W. Farino, and R. Mclnnes.
Evaluation and Selection of Models for Estimating Air Emissions from
Hazardous Waste Treatment, Storage, and Disposal Facilities. EPA-
450/8-34-020, U.S. Environmental Protection Agency, Office of Air
Quality Planning and Standards, Emission Standards and Engineering
Division, Research Triangle Park, NC, 1984. 157 pp.
Mathematical models describing the release rate of volatile air
emissions from hazardous waste treatment, storage, and disposal
facilities were compiled and reviewed. Mathematical modeling
techniques which predict volatile air emission release rates
from landfills, landfarms, surface impoundments, storage tanks,
wastewater treatment processes, and drum handling and storage
facilities were assessed. Existing field test validation
efforts were also reviewed. Models reviewed include: landfill
-- Fanner Model, Shen modification of Fanner Model, Thibodeaux
a Model, Thibodeaux Convective "Add On" Model, Thibodeaux b
Model, and Shen's Open Dump Model; land treatment --
Thibodeaux-Hwang Model and Hartley Model; lagoons -- Mackay and
Leinonen Model, Mackay and Wolkoff Model, Thibodeaux, Parker
and Heck model, Shen Model, Smith Model, and McCord Model.
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XVII. Caputo, Jr., K., and R.L. Blttle. Case History: A Superfund
Cleanup In Central Pennsylvania. In: Hazardous and Toxic Wastes:
Technology, Management and Health Effects, S.K. Majumdar and E.W.
Miller, eds. Pennsylvania Academy of Science, Easton, PA, 1984.
pp. 228-241.
This chapter 1s not relevant to the current project; no
emission measurements are reported. Caputo and EHttle describe
the general details of an emergency cleanup at an Industrial
site.
XVIII. Caravanos, J., and T.T. Shen. The Effect of Wind Speed on the
Emission Rates of Volatile Chemicals from Open Hazardous Waste Dump
Sites. Source unknown.
This article presents a modified diffusion equation (Shen
Model), which includes wind speed as a variable. Experimental
data are presented for benzene, carbon tetrachloride, and
trichloroethylene applied to soil, which approximate a spill.
The equation also could be applied to waste exposed at surface.
XIX. Cassis, J.A., E.P. Kunce, and T.A. Pederson. Remedial Action at
Uncontrolled Hazardous Waste Sites: Problems and Solutions. In:
Hazardous Waste Management for the 1980s, T.L. Sweeney, H.G. Bhatt,
R.M. Sykes, and O.J. Sproul, eds. Ann Arbor Science, Ann Arbor, MI,
1982. pp.241-264.
This chapter is not relevant to this program. The authors
describe a remedial action plan for the Pollution Abatement
Services Oswego Site in Oswego, New York.
XX. Clraorelli, A.J. Palraerton Zinc National Priorities List Site:
Atmospheric Deposition Analysis of Cadmium, Zinc, Lead and Copper in
the Vicinity of the New Jersey Zinc Palmerton Facility. U.S.
Environmental Protection Agency Region III Air Management Division,
1986. 93 pp.
Cimorelli discusses heavy metal deposition from stack
emissions. Meteorological data are used to identify areas of
high deposition, to design a soil sampling program.
XXI. Countess, R.J., R. Brewer, and R.J. Gordon. Sampling Airborne Toxic
Organics by Remote Control. Presented at the 78th Annual Meeting of
the A1r Pollution Control Association, Detroit, MI, 1985. 16 pp.
This paper describes a radio-controlled air sampler, which
> would be useful as a sampling method.
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XXII. Cowherd, C. Measurement of Part1culate Emissions from Hazardous
Waste Disposal Sites. For presentation at: 78th Annual Meeting, Air
Pollution Control Association, Detroit, MI, June 16-21, 1985.
Article describes the MRI wind tunnel and exposure profiling
• techniques for partieulate emissions rite measurement. The MRI
wind tunnel is a portable wind tunnel which can be used for
direct emissions measurement. The exposure profiling technique
is used for indirect emissions measurement and is similar to
the transect technique.
XXIII. Cox,'R.D., K.J. Baughman, and R.F. Earp. A Generalized Screening
and Analysis Procedure for Organic Emissions from Hazardous Waste
Disposal Sites. In: Proceedings of the 3rd National Conference and
Exhibition on Management of Uncontrolled Waste Sites, Washington,
D.C., 1982.
The authors describe a technique developed by Radian
Corporation for analysis of gas, liquid, and solid
environmental samples. The technique uses gas chromatography
with flame ionization, photoionization and Hall electrolytic
conductivity detectors, as well as mass spectrometry.
XXIV. DeWolf, G.B., and R.G. Wetherold. Protocols for Calculating VOC
Emissions from Surface Impoundments Using Emission Models:
Technical Note. Radian Corporation, Austin, TX, EPA Contract No.
68-02-3850, U.S. Environmental Protection Agency, Research Triangle
Park, NC, 1984. 34 pp.
OeWolf and Wttherold present the Thibodeaux models for aerated
and rsonaeratad steady-state impounds and the Mackay and
Liinonen Model for unsteady-state impounds. Input variables
are defined, sources of these variables are suggested, and
approximate precision levels for the variables are given.
Physical property inputs are discussed and methods for their
estimation are given, along with selected values for some
materials.
XXV. OeWolf, G.B., and R.G. Wetherold. Protocols for Calculating VOC
Emissions fro«> Land Applications Using Emission Models. Radian
Corporation, Austin, TX, EPA Contract No, 68-02-3850, U.S.
Environmental Protection Agency, Research Triangle Park, NC, 1984.
28 pp.
The authors present the Thibodeaux-Hwang Model for land
treatment and the Fanner Model for landfills. Input variables
are defined, sources of the variables are suggested, and
-approximate precision levels for the variables are given.
Physical property inputs are discussed and methods for their
estimation are given, along with selected values for some
materials.
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XXVI. Dupont, R.R. A Flux Chamber/Solid Sorbent Monitoring System for Use
In Hazardous Organic Emission Measurements from Land Treatment
Facilities. Presented at the 79th Annual Meeting of the Air
Pollution Control Association, Minneapolis, MN, 1986. 15 pp.
This paper reports on testing of the emission Isolation flux
chamber with Tenax\ tubes as the sampling media.
XXVII. Dupont, R.R. A Flux Chamber/Sorbent Tube Monitoring System for
Hazardous Organic Emission Measurements from Land Treatment
Facilities. In: 192nd National Meeting, American Chemical Society,
Division of Environmental Chemistry, 26(2):394-397, 1986.
This 1s not useful for a case study; the technology 1s already
known. The article reports that testing of the emission isola-
tion flux chamber with Tenax\ tubes for sample collection was
effective for measuring specific volatile species under both
laboratory and field conditions.
XXVIII. Dupont, R.R. Measurement of Volatile Hazardous Organic Emissions.
Journal of the A1r Pollution Control Association, 37(3):168-176,
1987.
An emissions isolation flux chamber was laboratory tested In
combination with Tenax\ and charcoal tube sampling to determine
the recovery efficiencies for selected organics. The testing
validates the use of a "Radian-style" flux chamber. Testing
included the use of flow rates significantly below the standard
protocol.
XXIX. Elclund, B.M., W.D. Balfour, and C.E. Schmidt. Measurement of
Fugitive Volatile Organic Emission Rates. Environmental Progress,
4(3):199202, 1985.
This article describes the design and operation of a "Radian-
style" emission isolation flux chamber. It also provides
limited data from several projects, which can be used as
emission measurement case studies.
XXX. Elclund, B. Detection of Hydrocarbons in Groundwater by Analysis of
Shallow Soil Gas/Vapor. Radian Corporation, Austin, TX, 1985. 78
pp.
This report describes five method.s of measuring soil vapor
concentrations: surface flux chamber, soil probe, downhole
flux chamber, accumulator, and soil coring. All five methods
, s/aiou1d be useful for data collection for direct measurement
and/or predictive modeling.
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XXXI. EJclund, B.M., W.O. Balfour, and C.E. Schmidt. Measurement of
Fugitive Volatile Organic Compound Emission Rates with an Emission
Isolation Flux Chamber. For presentation at: AIChE Summer National
Meeting, Philadelphia, PA, 1984. 8 pp.
. The authors present the procedures for using the surface
emission Isolation flux chamber for direct emission rate
measurement. Also presented are the results of measurements at
two spill sites, three landfills, several surface impounds, a
landfarn, and a remedial action.
XXXII. EJclund, B.M., M.R. Klenbusch, D. Ranum, and T. Harrison.
Development of a Sampling Method for Measuring VOC Emissions from
Surface Impoundments. Radian Corporation, Austin, TX, no date. 7
pp.
This paper describes the development program for evaluating and
modifying the design and operation of the surface isolation
flux chamber for use on surface impounds.
XXXIII. Enfield, C.G., R.F- Carsel, S.Z. Cohen, T. Phan, and D.M. Walters.
Approximating Pollutant Transport to Ground Water. Ground Water,
20(6): 711-722, 1982.
This article does not provide information on emission rate
determination. It present three transport models for
evaluating the movement of organic chemicals through the soil
to the groundwater. The models include losses due to
degradation and sorption. Field data are compared to the
models.
XXXIV. Engineering Science, Inc. Determination of Air Toxic Emissions from
Non-Traditional Sources in the Puget Sound Region. EPA 910/9-86-
148, U.S. Environmental Protection Agency, Region X and Puget Sound
A1r Pollution Control Agency, Seattle, WA, 1986. 108 pp.
This report develops emission estimates for several selected
sources in the Puget Sound Region including POTWs, industrial
wastewater treatment plants, Superfund sites, municipal land-
fills, and TSDFs. Emissions are based on theoretical
equations. The report contains some useful examples of
theoretical equation applications. The report may also provide
case study site information.
XXXV. Farino, W., P. Spawn, M. Jasinski, and B. Murphy. Review of
Landfill AERR Models. In: Evaluation and Selection of Models for
Estimating Air Emissions from Hazardous Waste Treatment, Storage,
and Disposal Facilities. Revised Draft Final Report. Contract No.
68-02-3168, U.S. Environmental Agency, Office of Solid Waste, Land
Disposal Branch, 1983. pp. 5-1 - 5-13.
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This section describes six predictive models that estimate
volatile emissions: Fanner, Shen's modification of Farmer,
TMbodeaux (three variations), and Shen's Open Dump. The first
five models are based primarily on gas diffusion through the
landfill cover.
XXXVI. Fanner, U.J., M.S. Yang, J. Letey, W.F. Spencer, and H.H. Roulier.
Land Disposal of Hexachlorobenzene Wastes: Controlling Vapor
Movement In Soils. In: Land Disposal of Hazardous Wastes.
Proceedings of the Fourth Annual Research Symposium, U.S.
Environmental Protection Agency, Municipal Environmental Research
Laboratory, San Antonio, TX, March 6, 7, and 8, 1978. pp. 182-190,
Fanner presents a predictive equation for determining
hexachlorobenzene vapor diffusion through a soil cover.
Volatilization through soil, water, and polyethylene film was
studied in laboratory simulations. The predictive equation
should be applicable to other waste types.
XXXVII. Fanner, W.J., M.S. Yang, J. Letey, and W.F. Spencer. Land Disposal
of Hexachlorobenzene Wastes: Controlling Vapor Movement in Soil.
EPA-600/280-119, U.S. Environmental Protection Agency, Office of
Research and Development, Municipal Environmental Research
Laboratory, Cincinnati, OH, 1980. 69 pp.
The volatilization fluxes of hexachlorobenzene through a
covering of soil, water, and polyethylene film were simulated
1n the laboratory. Volatilization through soil was directly
related to soil porosity. Fanner develops a diffusion equation
for determining flux rates through the soil covering.
XXXVIII. Glllespie, D.P., F.J. Schauf, and J.J. Walsh. Remedial Actions at
Uncontrolled Hazardous Waste Sites, Survey and Case Study Investiga-
tion. In: Proceedings of the Second National Symposium on Aquifer
Restoration and Ground Water Monitoring, National Water Well
Association, Worthington, OH, 1982. pp. 369-374.
This paper 1s not useful. It discusses how nearly half of all
remedial actions completed by 1980 were ineffective at cleaning
up the sites.
XXXIX. Gravitz, N. Derivation and Implementation of Air Criteria During
Hazardous Waste Site Cleanups. Journal of the Air Pollution Control
Association, 35(7):753-758, 1985.
This article presents an approach for developing fenceline air
^monitoring criteria to protect community health. The approach
is dependent on developing acceptable community exposure
levels, and back calculating the fenceline concentration by
assuming Gaussian wind dispersion. The method does not require
emissions measurement.
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XL Greenberg, M. A Review of: 1) A Technical Approach for Sampling and
Analysis of VOCs at Hazardous Waste Sites and 2) Some Case Studies
in New Hampshire. Presented before the Fall Meeting, Air Pollution
Centre! Association New England Section, Conference on Air Toxics,
Worcester, MA, October 6-7, 1986. 30 pp.
This document contains overhead slides for a conference
presentation on sampling VOCs in ambient air at landfills.
Case studies are not worked up as emission estimates.
XLI. Hani sen, R.C., and M.A. McOevltt. Protocols for Sampling and
Analysis of Surface Impoundments and Land Treatment/Disposal Sites
for VOCs. EPA Contract No. 68-02-3850, U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards,
Research Triangle Park, NC, 1984. 88 pp.
The report gives detailed description for analysis of volatile
organics by Radian gas chromatography with multiple detectors
(GC/MD) system and gas chromatography with mass spectrometry
(OS/MS) system. The report gives a brief discussion of predic-
tive emission models and lists inputs to models, but does not
present models. A description of a statistical approach to
cellecting sufficient samples for representativeness is
included.
XLIL Helslng, L.O., M.P. Morningstar, J.B. Berkowitz, and T.T. Shen. Risk
Analysis of Pollutants at Hazardous Waste Sites: Integration Across
Media is the Key. Ins Superfund '87: Proceedings of the 8th
National Conference, The Hazardous Control Research Institute,
Washington, D.C., November 16-18, 1987. pp. 471-475.
This paper describes the types of pollutants frequently found
at hazardous waste sites and how they can be transferred from
one media to another. This paper describes how all media need
to be taken into account when performing risk analysis. No
information on emission rate determination is provided.
XLIII. Hwang, S.T. Measuring Rates of Volatile Emissions from Non-Point
Source Hazardous Waste Facilities. Presented at the 75th Annual
Meeting of the Air Pollution Control Association, New Orleans, LA,
1982. 22 pp.
This paper presents Concentration Profile, Plume Mapping (tran-
sect), and Upwind/Downwind models for indirectly measuring
emission rates.
XLIV. Hwang, S.T. Toxic Emissions from Land Disposal Facilities. Environ-
mental Progress, l(l):46-52, 1982.
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Hwang gives theoretical equations for emission rate estimates
from surface Impoundments (natural surface and aerated), land-
fills (based on soil diffusion), and land treatment (oily
wastes). The equations require knowledge of waste and site
characteristics to determine variables and coefficients. All
equations would be difficult to apply for a complex waste,
requiring computer calculation. The equations can be applied
more easily to a single component waste, or Its primary compo-
nents.
XLV. Hwang, S.T. Comparison of Model Predicted Volatile Emission Rates
Versus Results of Field Measurements at Hazardous Waste Sites.
Presented at: American Institute of Chemical Engineers, National
Meeting, Summer 1984. American Institute of Chemical Engineers, New
York, NY. 18 pp.
Paper presents a comparison of measured and estimated emission
rates based on field sampling results and theoretical models.
Measurements were performed at landfills, surface Impounds, and
land treatment facilities. Field sampling techniques used were
concentration profile, transect, and surface emission Isolation
flux chamber. The predicted emission rates were generally
within the confidence Intervals of the measured emission rates,
although the author indicates that more study is required to
validate the models. The specific models used are referenced
but not discussed.
XLVI. Hwang, S.T. Estimating and Field-Validating Hazardous Air Emissions
from Land Disposal Facilities. In: Third Pacific Chemical
Engineering Conference, Seoul, Korea, 1983. pp. 338-343.
Models for estimating volatile emissions are reviewed,
Including Shen's modification of Farmer's equation (landfill),
the Thlbodeaux-Hwang equation (land treatment) and surface
'impound equation. Predicted versus measured emissions
(concentration profile and upwind/downwind techniques) are
compared, but limited data are given.
XLVII. Hwang, S.T. Model Prediction of Volatile Emissions. Environmental
Progress 4(2):141-144, 1985.
Hwang presents a comparison of measured and predicted emission
rates. Measurement techniques Include transect and
concentration profile techniques. Isolation flux chambers and
upwind/downwind are also discussed. The article contains
limited data from potential case studies.
XLVIII. ICF, Incorporated. The RCRA Risk-Cost Analysis Model Phase III
Report Appendices. Submitted to the Office of Solid Waste, Economic
Analysis Branch, U.S. Environmental Protection Agency, 1982.
Appendix E, 31 pp.
-------
Appendix E describes natural chemical, physical, and biological
processes that reduce the concentration of chemicals in the
environment. These processes are the basis for deriving
surfaci and groundwater decay rates for the chemicals included
. 1n the RCRA Risk-Cost Analysis Model. Important for baseline
emission rate estimates 1s the discussion on volatilization
from water.
XLIX. Jubach, R.W., R.R. Stoner, T.F- laccarino, and D.R. Smiley. An
Atmospheric Field Program Conducted at a Hazardous Waste Site.
Presented at the 78th Annual Meeting of the Air Pollution Control
Association, Detroit, MI, 1985. 14 pp.
This study characterizes the atmospheric dispersion at a
hazardous waste site from ground level release. The study
consists of releasing a tracer gas and measuring the concentra-
tion with two sampling arrays (i.e., transect techniques).
Measuring the of actual waste releases are not included.
Downwind data could be useful as a theoretical case study.
L. Kaplin, E.J., A.J. Kurtz, and M. Rahirai. VOC Sampling for Emission
Rate Determination and Ambient Air Quality on an Inactive Landfill.
Presented at New England Section, Air Pollution Control Association,
Fall 1986 Conference, Worcester, MA, October 6-7, 1986. 27 pp.
This paper describes sampling performed at an inactive landfill
in New York (a municipal waste landfill containing industrial
waste). Sampling included ambient air, emission flux chamber
(crude), crevices, and vent, sampled with Tenax, PUF/GFF, mylar
bags, impingers, and high volume samplers with GFF. Flux
measurements included both covered and uncovered areas. Data
are somewhat limited, but this study may be useful as a case
study.
LI. Karably, L.S., and K.B. Babcock. Effects of Environmental Variables
on Soil Gas Surveys. In: Superfund '87: Proceedings of the 8th
National Conference, The Hazardous Control Research Institute,
Washington, D.C., November 16-18, 1987. pp. 97-100.
This may be useful as a case study if sufficient soil data are
available. Soil gas was measured at 40 locations and over time
at a fire fighting training area. This paper reports how
environmental conditions (principally weather) affected
results. Limited analytical data are presented.
LII. Karirai, A.A., W.J. Fanner, and M.M. Cliath. Vapor-phase Diffusion
of Benzene in Soil. Journal of Environmental Quality, 16(l):38-43,
1987.
-------
The authors use Farmer's diffusion model and laboratory testing
method to determine benzene emission rates through soil (I.e.,
landfill emissions). The effects of soil bulk density and
moisture content are Investigated.
LIU. Kelnbusch, N.R. Measurement of Gaseous Emission Rates from Land
Surfaces using an Emission Flux Chamber: Users Guide, EPA Contract
68-02-3889, Radian Corporation, Austin, TX, 1986.
This document Includes a detailed description for using the
emission Isolation flux chamber, Including design of sampling
sprogram, QA/QC, data reduction, and examples.
LIV. Kerfoot, H.B. Soil-Gas Measurement for Detection of Groundwater
Contamination by Volatile Organic Compounds. Environmental Science
and Technology, 21(10):1022-1024, 1987.
This article describes sampling using a ground probe system for
soil gas. Soil gas data are correlated with groundwater data
showing good correlation. Soil gas data are correlated with
soil probe depth below ground surface, also showing good
correlation. Ground water was at shallow depth in this study
(3-4m). Data could be used as a case study If additional soil
characteristics data are available.
LV. Kerfoot, H.B., and P.B. Durgin. Soil-Gas Surveying for Subsurface
Organic Contamination: Active and Passive Techniques. In: Superfund
'87: Proceedings of the 8th National Conference, The Hazardous
Control Research Institute, Washington, O.C., November 16-18, 1987.
pp. 523-524.
This article provides an overview of considerations in
designing a soil-gas survey. It does not provide information
on sampling techniques for air pathway assessment.
LVI. Leplc, K.A., and A.R. Foster. Remediation at a Major Superfund
Site: Western Processing -- Kent, Washington. In: Superfund '87:
Proceedings of the 8th National Conference, The Hazardous Control
Research Institute, Washington, O.C., November 16-18, 1987. pp. 78-
84.
This article summarizes a remedial Investigation conducted at a
Western Processing site. Continuous upwind and downwind air
monitoring was conducted, as well as some location-specific
sampling. It may be useful as a case study. No data on air
monitoring are presented; the author would have to be
contacted.
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LVII. Liwis, R.G., B.E. Martin, D.L. Sgontz, and J.E. Howes. Measurement
of Fugitive Atmospheric Emissions of Polychlorinated Blphenyls from
Hazardous Waste Landfills. Environmental Science and Technology,
19(10):986-991, 1985.
. This article describes tir sampling for PCBs at three
uncontrolled landfills and one controlled landfill. Emission
rates were not calculated. The data set may be usable for
calculating emission rates. Sampling was performed using low-
volume and high-volume samplers and PDF cartridges.
LVIII. Mackay,- D.M., P.V. Roberts, and J.A. Cherry. Transport of Organic
Contaminants in Groundwater. Environmental Science and Technology,
19(5): 384-392, 1986.
This article describes the mechanisms involved in the transport
of organic chemical contaminants in ground water, including
advection, dispersion, sorption and transformation.
LIX. Mackay, 0., and P.J. Leinonen. Rate of Evaporation of Low-
Solubility Contaminants from Water Bodies to Atmosphere.
Environmental Science and Technology, 9(13): 1178-1180, 1975..
The authors present predict models (Mackay and Leinonen) for
emission rates from aqueous systems. Equations are presented
for both steady and unsteady state systems.
LXo Mackay, D., and A.T.K. Yeun. Mass Transfer Coefficient Correlations
for Volatilization of Organic Solutes from Water. Environmental
Science and Technology, 17(4):211-217, 1983.
Volatilization rates of organic compounds in water were
measured in a wind-wave tank for compounds of varying Henry's
'Law Constants. The data yielded correlations for liquid and
vapro-phase transfer coefficients as a function of windspeed,
and showed that interactions did not occur when mixtures of
compounds volatilized simultaneously.
LXI. Marquardt, G.O. Toxic Air Quality Investigation at a Hazardous
Waste Site. In: Superfund '87: Proceedings of the 8th National
Conference, The Hazardous Control Research Institute, Washington,
O.C., November 16-18, 1987. pp. 284-295.
This article does not provide data for baseline conditions.
However, it may be useful as a case study. Sampling was per-
formed upwind, on site, and downwind during field investigation
(drilling) and during a controlled release from a gas well.
Sampling techniques could be used for indirect measurement of
baseline emissions; techniques include Tenax\, carbon molecular
sieve, high-volume particulate sampler, and PDF.
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LXII. Meegoda, N.J., and P. Ratnaweera. A New Method to Characterize
Contaminated Soils. In: Superfund '37: Proceedings of the 8th
National Conference, The Hazardous Control Research Institute,
Washington, D.C., November 16-18, 1987. pp. 385-389.
This paper 1s not related to emission rate determination; it
presents an electrical method to determine engineering
characteristics of soil.
LXIII. Miller, G.C., V.R. Herbert, and R.G. Zepp. Chemistry and
Photochemistry of Low-Volatility Organic Chemicals on Environmental
Surfaces. Environmental Science and Technology, 21(12):1164-1167,
1987.
This article discusses factors affecting the transformation,
mobility, and fate of xenobiotic chemicals (specifically
dioxins and PAHs). Emphasis is placed on discussing effects on
and near the soil surface and factors that affect the rate of
photolysis.
LXIV. Panaro, J.M. Air Monitoring and Data Interpretation During Remedial
Action at a Hazardous Waste Site. In: Hazardous Wastes and
Environmental Emergencies: Management, Prevention, Cleanup, Control,
Hazardous Materials Control Research Institute, Houston, TX, 1984.
pp.160-164.
Panaro describes the air monitoring program employed during
Initial remedial measures at a chemical recycling plant. He
does not address emission estimates.
LXV. Polcyn, A.J., and H.E. Hesketh. A Review of Current Sampling and
Analytical Methods for Assessing Toxic and Hazardous Organic
Emissions from Stationary Sources. Journal of the Air Pollution
Control Association, 35(1):54-60, 1985.
This article is a brief review of sampling methods (i.e.,
sample collection media) and analytical methods. The methods
are summarized in tables, and give references for detailed
descriptions. The article does not discuss measurement
techniques (I.e., sampling design) or modeling.
UCVI. Qulmby, J.M., R.W. Cibulskis, and M. Gruenfeld. Evaluation and Use
of a Portable Gas Chromatograph for Monitoring Hazardous Waste
Sites. Source unknown.
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This paper evaluates the use of the Century Systems Organic
Vapor Analyzer Model OVA-128 which 1s a portable gas
chrofflttograph with a fume ionization detector (GC-FID). The
piper addresses instrument operating performance, QA/QC
consideration, operational difficulties and recommended field
uses. Instruments can be used to perform field screening of
ambient air, as well as other uses.
LXVII. Radian Corporation. Review of Soil Gas Sampling Techniques.
Austin, TX, 1983. 26 pp.
^Report presents the results of a literature review to identify
techniques applicable to soil gas sampling and measurement.
LXVIII. Radian Corporation. 3M Foam Evaluation for Vapor Mitigation:
Technical Memorandum. Sacramento, CA, 1986. 9S pp.
The effectiveness of temporary and stabilized foam for control-
ling VOC emissions from petroleum refinery waste was tested.
Testing was performed using the surface emission isolation flux
chamber.
LXIX. Radian Corporation. A1r Quality Engineering Manual for Hazardous
Waste Site Mitigation Activities, Revision No. 2. Sacramento, CA,
1987. 291 pp.
This guidance document provides general information for
designing and reviewing air monitoring programs for hazardous
waste site remedial programs. An overview of New Jersey's
agency involvement in the remedial process is given. Sampling
and analysis methods are discussed in detail.
LXX. Radian Corporation. Ambient Air Monitoring at Hazardous Waste and
Superfund Sites, Revision No. 2. Sacramento, CA, 1987. 389 pp.
This guidance document provides information for reviewing air
quality engineering activities for hazardous waste site
remediation programs. It also provides an overview of the
phases of the hrzardous site remediation process and the role
of New Jersey's agencies 1n the process. Descriptions are
given for types of waste sites, potential air contaminants, and
basic remedial processes.
IXXI. Radian Corporation. Survey and Assessment of Air Emission Modeling
Techniques for Landfills. Draft Final Report. EPA Contract 68-01-
7287, U.S. Environmental Protection Agency, Washington, D.C., 1988.
115 pp.
-------
Article reviews theoretical models for landfill air emissions
Including: Farmer Model* Shen Model, Thibodeaux a Model,
Thibodeaux Logrithnric Gradient Model, RTI Closed Landfill
Model, Thibodeaux Convective "Add On* Model, Thibodeaux b
Model, Thibodeaux Exact Model, Arnold's Open Landfill Model,
. Shen's Open Landfill Model, and RTI Open Landfill Model.
LXXII. Saeger, M.L., and E.E. Rlckman, Jr. Final Report: Ambient Air
Monitoring at Hazardous Waste Treatment, Storage, and Disposal
Facilities, Phase I. EPA Project Number 68-02-4326, U.S.
Environmental Protection Agency, Emissions Standards and Engineering
Division, Office of Air Quality Planning and Standards, Research
Triangle Park, NC, 1968.
The authors contacted several state and federal regulatory
agencies and treatment, storage and disposal facilities (TSOFs)
to determine the air monitoring requirements for TSOFs. Few of
the states contacted had established requirements, and there
was no consistency among states. The program was of a limited
scope and was Intended to determine if a study should be
conducted to assess the feasibility of conducting air
monitoring programs at TSOFs.
LXXIII. Schmidt, C.E., and D.L. Gordy. Designing Air Monitoring Programs
for Remediation at Hazardous Waste Sites. Presented at the Annual
Conference of the Air Pollution Control Association, San Francisco,
CA, 1985. 14 pp.
This paper presents a methodology for developing site-specific
air monitoring programs for hazardous waste site remediation.
The Information presented focuses on fugitive gas phase air
contaminants.
LXXIY. Schmidt, C.E., and J.K. Meyer-Schmidt. Assessment, Monitoring, and
Modeling From a Superfund Site Remedial Action. Presented at the
Air Pollution Control Association Annual Conference, San Francisco,
CA, 1985. 20 pp.
This paper gives a brief overview of RI/FS activities performed
at the McColl waste site in Fullerton, California.
Measurements included surfaces screening survey, surface flux,
ground probes, and downhole flux. Indirect measurements were
performed by ambient air sampling. Modeling was used to
predict downwind concentrations from direct measurement. Data
can be used directly as a case study for both direct and
Indirect emission estimates. Data can also be used with
predictive models.
LXXV. Schmidt, C.E., R. Stephens, and G.A. Turl. Case Study: Control and
Monitoring of A1r Contaminants During Site Mitigation. Radian
Corporation, Sacramento, CA, 1987. 8 pp.
-------
This article presents an RI/FS/RM case study where an air
pathways assessment was performed at a hazardous waste site.
Both baseline and disturbed site air emissions were measured
and reported.
UCXVI. Schmidt, C.E., and M.W. Eltgroth. Off-Site Assessment of A1r
Emissions from Hazardous Waste Disposal Facilities. Reprinted from:
Management of Uncontrolled Hazardous Waste Sites, Hazardous
Materials Control Research Institute, Silver Spring, MD, 1983.14 pp.
»F1eld data and modeling (tugrangian model) were used to
estimate downwind air concentrations of contaminants using
measured disturbed site emissions data. Modeled data were
compared to measured data.
UCCVIL Schmidt, C.E., and W.D. Balfour. Direct Sas Emission Measurement
Techniques and the Utilization of Emissions Data from Hazardous
Waste Sites. Reprinted from: National Conference on Environmental
Engineering Proceedings, Environmental Engineering Division, ASCE,
1983. 8 pp.
This article -describes direct emissions measurement techniques
and discusses various applications of these techniques to waste
management. Techniques included are surface and downhole
Isolation flux chambers, ground probes, and soil vapor
monitoring wells.
IXXVIIL Schmidt, C.E., Re Vandervort, and W.D. Balfour. Technical Approach
and Sampling Techniques Used to Detect and Map Subsurface
Hydrocarbon Contamination. For presentation at the 79th Annual
Meeting, Air Pollution Control Association, Minneapolis, MN, 1986.
31 pp.
This paper presents a case study where several direct air emis-
sions measurement techniques were used to detect emissions from
a gasoline plume on groundwater about 90 feet below the land
surface.
LXXIX. Shen, T.T., and T, J. Tofflemlre. Air Pollution Aspects of Land
Disposal of Toxic Waste. Ini National Conference on Hazardous
Material Risk Assessment, Disposal and Management, Miami Beach, FL,
April 25-27, 1979. pp. 153-159.
This paper provides a general discussion of the air pollution
dangers inherent in landfill ing industrial waste, especially
co-disposal with municipal waste. Volatilization processes are
discussed. Also discussed are methods for reducing the rate of
volatile loss.
-------
LXXX. Shen, T.T. Estimating Hazardous Air Emissions from Disposal Sites.
Pollution Engineering, 13(8):31-34, 1981.
This article presents Shen's modification of Fanner's equation
for the diffusion of volatile* from a landfill, and Ziegler's
modification of Arnold's equation for open dumps (also referred
' to as Shen's open dump equation). A table of diffusion
coefficients for selected compounds 1s given. Two example
calculations for PCS emission are also given.
LXXXI. Shen, T.T., and G.H. Sewell. Air Pollution Problems of Uncontrolled
Hazardous Waste Sites. Civil Engineering for Practicing and Design
Engineers, 3(3):241-252, 1984.
Shen and Sewell provide three theoretical equations for
predicting emission rates (Shen landfill model, Shen landfarm
model, Shen lagoon model) for volatlles and one for dust. The
equations require some field data about soil, waste
characteristics, site size, etc., but no direct or indirect
measurement of emissions. The equations should be used with
caution, and some spedesspecifie coefficients may be difficult
to determine or infer.
LXXXII. Shen, T.T. Air Pollution Assessment of Toxic Emissions from
Hazardous Waste Lagoons and Landfills. Environment International,
ll(l):71-76, 1985.
Shen briefly discusses the available methods for determining
emission rates and their drawbacks. He does not provide
technical detail for the use of methods, but includes isolation
flux chamber, transect, concentration profile, and predictive
models.
LXXXIII. Shen, T.T. A1r Quality Assessment for Land Disposal of Industrial
Wastes. Environmental Management, 6(4):297-305, 1982.
Shen presents a models for predicting emission rates from land-
fills (Shen modification of Farmer), dumps (Arnold Model) and
lagoons based on the diffusion theory. Shen also presents data
on the comparison of predicted versus measured ambient concen-
tration of PCBs at a Niw York landfill. This article may be
useful as a case study.
LXXXIV. Shen, T.T. Hazardous Air Emissions from Industrial Waste Treatment
Facilities. In: Industrial Waste: Proceedings of the Fourteenth
Mid-Atlantic Conference, June 27-29, 1982, J.E. Alleman and J.T.
Kavanagh, eds., Ann Arbor Science, Ann Arbor, MI, 1982. pp. 361-
372,,
Shen presents predictive models for dust and volatile organics
emissions from lagoons (Shen Model), and discusses the fate of
volatile emissions in the environment in general terms.
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LXXXV. Sherman, S., W. Dickens, and H. Cele. Analysis Methods and Quality
Assurance Documentation of Certain Volatile Organic Compounds at
Lower Detection Limits, In: Superfund '87: Proceedings of the 8th
National Conference, The Hazardous Control Research Institute,
Washington, D.C., November 16-18, 1987. pp. 280-283.
This paper 1s not useful. It discusses modification of EPA
Method 624 to allow lower detection limits for groundwater
analysis.
LXXXVI. Skipa, K.J., D.F. Ellas, and J.O. Gram. Monitoring and Evaluating
Multiple Source Emissions at Hazardous Waste Sites. Presented at
the 78th Annual Meeting of the Air Pollution Control Association,
Detroit, MI, 1985. 11 pp.
This paper discusses, in a generic form, the issues to be con-
sidered 1n selecting monitoring and modeling approaches to
assess the air impacts from a hazardous waste site.
LXXXVII. Smith, P.G., and S.L. Jensen. Assessing the Validity of Field
Screening of Soil Samples for Preliminary Determination of
Hydrocarbon Contamination. In: Superfund '87: Proceedings of the
8th National Conference, The Hazardous Control Research Institute,
Washington, O.C., November 16-18, 1987. pp. 101-103.
This paper compares results from vapor screening of samples in
tht field using portable analyzers" (FID and PID) to results
frera laboratory TPH analyses. Comparison of the results shewed
peer comlation indicating the field screening of vapors
should not be used as the sole criteria for selecting samples
for analysis.
LXXXVIII. South Coast Air Quality Management District. Landfill Gas
Emissions: Report of the Task Force, El Monte, CA, 1982.
This report describes task force activities, including sampling
of emissions at several landfills in the South Coast Air
Quality Management District. Data presented are very limited;
sampling methods were headspace over landfill, shallow ground
probe, and vent sampling. Site-specific sampling results could
possibly be worked up as a case study.
LXXXIX. Springer, C., K.T. Valsaraj, and L.J. Thibodeaux. In Situ Methods
to Control Emissions from Surface Impoundments and Landfills.
Journal of the Air Pollution Control Association, 36(12):1371-1374,
1986.
-------
This article discusses various control measures to reduce air
emissions from landfills and lagoons. Included are air-
supported structures, floating objects, shape modification,
aerodynamic redesign, of! and surfactant covers, and synthetic
membrane covers. The effectiveness and other considerations
for use of each method are discussed in general.
•*
XC. St. Clalr, A.E., and K.T. Ajraera. Remedial Action at Uncontrolled
;, Hazardous Waste Sites. Environmental Progress, 3(3): 188-193, 1984.
This paper describes the feasibility study approach used to
develop and select a cost-effective remedial action alternative
for the McColl Superfund site 1n Fullerton, California. Data
from the McColl remedial Investigation, not presented in this
paper, can be used as a case study of baseline emission rate
determination.
XCI. Thibodeaux, L.J., and S.T. Hwang. Landfarming of Petroleum Wastes -
- Modeling the A1r Emission Problem. Environmental Progress,
l(l):42-46, 1982.
This article reviews volatilization from land fanning of
petroleum wastes, discusses distribution of oil waste in the
soil, and presents a gradient!ess diffusion model for
estimating emissions (Thibodeaux-Hwang Model). The article
also gives predicted versus measured emission rates for
Oeldrin.
XCII. Thomas, R.G. Volatilization from Soil. In: Handbook of Chemical
Property Estimation Methods, W.J. Lyraan, W.F. Reehl, and D.H. Rosen-
blatt, eds. McGraw-Hill, New York, NY, 1982. pp. 16.1 - 16.50.
This chapter presents a discussion of the theory of volatiliza-
tion of organics from soil. Thomas presents five models for
calculating volatile loss from the soil. The models are:
Hartley Model; Hamaker Model; Meyer, Letey, and Fanner Model;
Jury, Grover, Spencer, and Fanner Model; and Dow Methods. This
work 1s based on pesticides applied to soiT. A decision tree
Indicating which models apply for varying conditions is
included. The models could be applied to sites with known
contaminants.
XCIII. Thomas, R.G. Volatilization from Water. In: Handbook of Chemical
Property Estimation Methods: Environmental Behavior of Organic Com-
pounds, W.J. Lyman, W.F. Reehl, and O.H. Rosenblatt, eds., McGraw-
Hill, New York, NY, 1982. pp. 15-1 to 15-34.
"Chapter describes the volatilization process from water.
Various methods for estimating volatilization rates are
discussed. The Mackay and Leinonen model and others are
presented.
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XCIV. Thorntloe, S. Summary of Reports Prepared for the Development of
Air Emission Stindirds fer Hazardous Wasti Treatment, Storage, and
Disposal Facilities* U-.S. Environmental Protection Agency, Office of
A1r Quality Planning and Standards, Emission Standards and
Engineering Division, Chemicals and Petroleum Branch, Research
Triangle Park, NC, 1987.
This report contains annotated bibliographies and contacts for
several studies and reports. Most are directly applicable to
treatment, storage, and disposal facilities, but some may
•provide sampling techniques applicable to uncontrolled sites.
XCV. Tucker, W.A., and L.H. Nelken. Diffusion Coefficients in Air and
Hater. In? Handbook of Chemical Property Estimation Methods:
Environmental Behavior of Organic Compounds, W.J. Lyman, W.F. Reehl,
and D.H. Rosenblatt, eds. McGraw-Hill, NY, 1982. pp. 17-1 to 17-25.
Chapter discusses molecular diffusion in air and water.
Methods are not useful for estimating dispersion in air.
Methods may be relevant to uncontrolled sites (i.e., within
lagoon or landfill), however, factors such as wind mixing
(lagoons) or soil gas flow (landfills) may outweigh molecular
diffusion.
XCVI. U.S. Environmental Protection Agency. Letter from J.R. Farmer,
Director, Emission Standards and Engineering Division, to D. Kolar,
Environmental Counsel9 Browning Ferris Industries, dated October 30,
1987, regarding EPA's investigation of techniques for controlling
air emissions from municipal landfill facilities.
The U.S. EPA sent a questionnaire to Browning Ferris Industries
requesting Information on their landfills. The results, des-
cribed in this memorandum, do not provide information for base-
line emissions.
XCVII. U.S. Environmental Protection Agency. Material on RCRA Facility
Investigation Guidance (RFI) provided by the U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards, to
Radian Corporation, Sacramento, CA, December 1987=
The material provided includes a Section 12 on Air, Case Study
14: Use of Air Monitoring Data and Dispersion Modeling to
Determine Contaminant Concentrations Down-Wind of a Land
Disposal Facility, and Case Study 15: Use of Meteorological
(Data to Design an Air Monitoring Network. This material
"provides a recommended strategy for characterizing releases to
the air. Air monitoring and modeling are discussed in general
form. The Field Methods section provides considerable
information on available sampling media and appropriate soecies
applications.
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XCVIII. U.S. Environmental Protection Agency. RCRA Facility Investigation
(RFI) Guidance, Volume III, Section 12, A1r and Surface Water
Releases. OSWER Directive 9502.00-6C, Office of Solid Waste, 1987.
' Provide recommended strategy for characterizing releases to
air, which Includes characterizing the source and the
environmental setting for removal actions at RCRA facilities.
XCIX. U.S. Environmental Protection Agency. Superfund Exposure Assessment
Manual. OSWER Directive 9285.5-1, Office of Solid Waste and
Emergency Response, Washington, O.C.
Section 2.3 of this manual presents eight equations for
predicting short-term and long-term emission rates for
landfills with and without internal gas generation, lagoons,
landfarms, spills and leaks. Both particulates and volatile
emissions are discussed. Equations and discussions are given
for determining input variables.
C. U.S. Environmental Protection Agency. Hazardous Waste Treatment,
Storage and Disposal Facilities (TSDF) -- Air Emission Models. EPA-
450/3-87-026, Office of Air and Radiation, Office of Air Quality
Planning and Standards, Research Triangle Park, NC, 1987.
Analytical models are presented for estimating air emissions
from hazardous waste treatment, storage, and disposal
facilities (TSDF). Air emission models have been developed for
aerated and nonaerated surface impoundments, land treatment
facilities, landfills, and wastepiles (RTI models). Emission
model predictions are compared to available field data. This
report also Includes emission factors for transfer, storage,
and handling operations at TSDFs. The models have been
assembled into a spreadsheet that is included in this report as
floppy diskette for use on a microcomputer. Appendices include
a list of physical-chemical properties for approximately 700
compounds and a comprehensive source list of pertinent
literature in addition to that cited in the report.
CI. Vandervort, R., C.E. Schmidt, and W.D. Balfour. Surface and Subsur-
face Gas/Vapor Monitoring Techniques Applied to Environmental
Contamination Caused by Petroleum Products and Processing Wastes.
Radian Corporation, Sacramento, CA. 12 pp.
This paper discusses the application of surface and subsurface
emission rates and vapor concentration measurements for
; investigating petroleum leaks and hazardous waste site
investigations.
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CII. Vaught, C.C. A Basic Programming Technique for the Estimation of VOC
Emissions from Hazardous Waste Treatment, Storage, and Disposal
Facilities. Presented at the 78th Annual Meeting of the Air
Pollution Control Association, Ditreit, MI, June 16-21, 1985. 9 p.
. This paptr describes a BASIC program for use on microcomputer.
The program uses unspecified predictive models to estimate
emission rates for surface impounds, landfills, land treatment,
and storage tanks. The program includes a chemical library of
required model variables which are accessed by use of CAS num-
bers, as well as estimation programs for filling data gaps, and
adjustments for site- specific temperature conditions. The
^program was developed in 1985 and may have been updated.
CIII. Vogel, G.A. Air Emission Control at Hazardous Waste Management
Facilities. Journal of the Air Pollution Control Association, 35(5):
558-566, 1985.
This article is not related to emissions measurement. It
identifies a method to control toxic air emissions from tanks,
lagoons, landfills, land treatment facilities, and waste piles.
Control cost information is also included.
CIV. Walker, K.A. Air Emissions from Hazardous Waste Treatment, Storage
and Disposal. Presented at the 77th Annual Meeting of the Air
Pollution Control Association, San Francisco,. CA, 1984. 14 pp.
Summarizes OSW's work which is presented in detail by Balfour,
Wttherold, and Lewis (1984) included elsewhere is this biblio-
gnphy. Volatile air emissions it TSDFs were compared for
measured versus predictive models.
CY. Weston, R.F. Performance of Remedial Response Activities at Uncon-
trolled Hazardous Waste Sites (REMII): Draft Remedial
Investigation/ Feasibility Study Report for the Bruin Lagoon Site,
Bruin Borough, Pennsylvania. IKS. EPA Contract No. 68-01-6939, U.S.
Environmental Protection Agency, 1986.
This report presents the results of the remedial investigation
performed at a refinery waste lagoon locatei 45 miles north of
Pittsburg in Bruin Borough, Butler County, Pennsylvania. Air
pathway analysts were performed for determining the health and
safety requirements for workers and nearby residences during
excavation of the lagoon. Also, sampling and analysis of sub-
surface soil gas from wells located in the lagoon were
performed to determine the soil gas composition, regeneration
rates, extent of trapped soil gas within the lagoon and to
assist in the assessment of the potential for the release of
soil gas into the atmosphere during future excavation.
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CVI. Wetherold, R.G., and O.A. Oubose. A Review of Selected Theoretical
Models for Estimating and Describing Atmospheric Emissions from
Waste Disposal Operations. EPA Contract 68-03-3038, U.S.
Environmental Protection Agency, Office of Research and Development,
Industrial Environmental Research Laboratory, Cincinnati, OH, 1982.
73 pp.
This report presents models for determining emissions from
landfills, land treatment, lagoons, waste piles, and tanks.
Models Include both predictive models and Indirect measurement
techniques. Estimates of model precision and accuracy, and
potential sources for model variables are included* Models
Included are: Hartley Model; Th1 bodeaux-Hwang Model; Farmer
Model; Smith, Bomberger, Haynes Model, Mackay and Leinonen
Model; Thlbodeaux Concentration Profile; and Thibodeaux,
Parker, and Heck Model.
CVII. Wetherold, R.G., 8.M. Eklund, and T.P. Nelson. A Case Study of
Direct Control of Emissions from a Surface Impoundment. In:
Proceedings of the llth Annual Research Symposium on Incineration
and Treatment of Hazardous Waste, Annual Solid Waste Research
Symposium, U.S. Environmental Protection Agency, Cincinnati, OH,
1985. pp. 85-92.
Testing was performed to determine the effectiveness of an
Inflated flexible dome enclosure in controlling VOC emissions
from an aerated wastewater lagoon. Effectiveness was investi-
gated by performing a mass balance of VOCs around the system.
The article is not directly applicable to baseline emission
estimates.
Wood, J.A., and M.L. Porter. Hazardous Pollutants in Class II Land-
fills. South Coast Air Quality Management District, El Monte, CA,
1986.
This report describes sampling for air toxics at several Class
II landfills. Landfill gas sampling was performed at 20 sites
from vents (when present) and headspace over the site. Ambient
air sampling was performed at five sites'. Air toxics were
detected even though the species cannot be legally disposed of
at Class II landfills.
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APPENDIX B
CHEMICAL AND PHYSICAL PROPERTIES
AFFECTING BASELINE EMISSION ESTIMATES
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CHEMICAL AND PHYSICAL PROPERTIES OF THE WASTE MATERIAL AFFECTING EMISSIONS
Property
Effect
Saturation Concentration
Diffusion Coefficient
Molecular Weight
Partial Pressure of
Constituents
Weight Fraction
Combination of Constituents
Concentration of Waste
Henry's Law Constant
The waste will tend to reach equilibrium with
the soil vapor. If sufficient waste is
present, the equilibrium concentration within
the air-filled voids of the soil matrix will
reach saturation. Because the rate of
emission to the atmosphere is directly
proportional to the soil vapor concentration,
the emission rate will increase as saturation
concentration increases.
Compounds with high overall diffusion
coefficients will be emitted at higher rates
than those with lower diffusion coefficients
via increased transport, on a relative basis.
The overall diffusion coefficient may be
comprised of diffusion through the soil-water
interface, soil-air interface, soil, water,
air, and soil vapor.
Lower molecular weight compounds typically
have higher volatilization and diffusion
coefficients. Other compound characteristics
may predominate. Molecular weight is used to
determine diffusion rates in some predictive
models.
High partial pressure increases the emission
rate of a species by increasing its soil
vapor concentration.
An effect similar to partial pressure, it is
used as an input to some predictive models.
Not as important as Henry's Law constant.
This increases the complexity of the
emissions process and determines the emission
rate. It may change over time as more
volatile species are lost.
Increasing waste concentration increases the
emission rate for dilute wastes by increasing
the vapor pressure and, therefore, vapor
concentration.
This is used to determine diffusion
coefficients. A high Henry's Law constant
produces a higher diffusion rate.
(Continued)
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Property
Effect
Porosity
Adsorption/Absorption
Properties of Soil
Soil Moisture
Wick Effect
Particle Size Distribution
Organic Content of Soil
Microbial Activity
One of the controlling factors for diffusion
through the soil. Emission rates typically
increase with increasing soil porosity.
Total porosity, i.e., dry soil, may represent
worst-case conditions for predictive models.
Air-filled porosity may be more a realistic
parameter for many sites.
Soil with high sorption properties will
reduce the vapor density of the sorped
compounds and, therefore, the emission rate.
The effect may be minimal where high waste
concentrations saturate the sorption sites.
The effect may be reversed causing increased
emissions.
Its effect varies. High moisture will reduce
the air-filled porosity, with pores being
filled under worst-case conditions and,
therefore, should reduce the emission rate.
Moisture may be preferentially adsorped by
the soil, releasing volatiles and increasing
the emission rate. Drying of soil may
increase available sorption sites. Moisture
is required for the wick effect.
Sell moisture may draw waste constituents to
the surface through the soil pores. This
process can increase the concentration of the
constituents at the surface and, therefore,
increase the emission rate.
This affects the total soil porosity and soil
pore continuity. Increased soil pore
continuity increases the emission rate. A
higher percent of fines will typically
increase particulate emissions.
High organic content will increase the
sorptive characteristics of the soil and
reduce the emission rate. High organic
content also will increase microbial action.
Its effect varies. It may reduce the
emission rate by biological reduction of the
waste present. It also may increase the
emission rate due to gas formation which
carries volatile species to surface.
(Continual)
-------
Property
Effect
Depth of Landfill Cover
Compaction of Landfill Cover
Ground Cover
Size of Landfill/Lagoon
Amount of Exposed Waste
Water Depth in Lagoon
Aeration of Lagoons
Temperature
Wind
Emission rates decrease with increasing depth
(thickness) of cover as the diffusion path
increases. For an open dump or landfill, the
cover thickness is zero.
Increasing compaction reduces the soil
porosity and disrupts continuity of the soil
pores, thereby, reducing the emission rate.
Soil cover, typically vegetation, will reduce
particulate emissions by reducing the
erodability of the soil. It also will help
hold soil moisture, which reduces the air-
filled porosity and reduces volatile
emissions.
The emission rate is directly proportional to
the size of the landfill or lagoon.
Emission will increase when waste is exposed
at the surface, both due to volatilization
and wind erosion.
Water overlying waste will act as a cover.
Diffusion through water may control the
emission rate.
Aeration increases emission of volatile and
particulates with increasing volume of air
used and/or agitation. The effect is due to
air stripping of volatiles and bulk transport
of liquid particles.
Increasing temperature increases the
volatilization rate for organic.species and,
therefore, the emission rate. Increasing
temperature reduces soil moisture, increasing
air-filled porosity and the emission rate.
Wind removes the volatilized compound
concentration in the boundary layer over the
site, maintaining the driving force for
volatilization. Increasing wind speed
reduces the boundary layer over the site.
Wind causes turbulence within the boundary
layer, providing the driving force for
surface soil/waste erosion and increasing
particulate emission rate.
(Continued)
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Property Effect
Cloud Cover • Increased cloud cover reduces solar heating
of the surface and, therefore, the
volatilization rate from surface. It also
affects wind stability.
Precipitation Emissions are reduced by reducing the air-
filled soil porosity. It may increase
landfill emission by displacing soil vapor
from soil voids. It may increase surface
water and air emissions by floating waste
constituents to the surface. Precipitation
increases agitation of the lagoon surface,
potentially increasing emissions, but it also
increases water depth over waste in the
lagoon.
Humidity Increasing partial pressure of water vapor in
air reduces the capacity for some types of
volatilized material. It may reduce air-
filled soil porosity.
Barometric Pressure Changing barometric pressures cause bulk flow
of soil vapor into/out of soil. The overall
net effect is to increase the emission rate.
The effect increases with frequency and scale
of barometric changes.
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APPENDIX C
ESTIMATION OF AN OVERALL SOURCE EMISSION RATE
USING EMISSION FLUX MEASUREMENTS
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C.O ESTIMATION OF AN OVERALL SOURCE EMISSION RATE USING EMISSION FLUX
MEASUREMENTS
This appendix provides guidance on how measured emission fluxes can
be used to estimate an overall emission rate for an area source. The
•*
information applies to any of the direct emission measurement technologies
which are designed to measure an emission flux at a specific point on the
emitting surface. A statistical sampling strategy and computation techniques
are discussed, and an example calculation is provided.
C.I Statistical Sampling Strategy
To obtain an overall emission rate for a source, a statistically
valid sampling strategy must be developed before samples are collected.
Development of this strategy involves the following:
0 Division of the total area into zones;
• Subdivision of the zones into smaller units of equivalent area;
t Determination of the number and location of units to be sampled
per zone;
t Measurement of emission fluxes from the predetermined grid
points; and
• Calculation of an overall emission rate based on the average
flux for each zone.
Sampling strategies can be designed to obtain data that will satisfy
different statistical criteria. The strategy described below provides an
estimated average emission rate within 20 percent of the true mean with 95
percent confidence.
C-l
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C.I.I Zones
Based on area source records and/or preliminary screening data (e.g.
real-time instrument survey of surface emissions), subdivide the total area
source into zones where heterogeneous chemical distribution is exhibited, i.e.
areas expected to exhibit comparable emission rates. The zones should be
arranged to maximize the between-zone variability and minimize within-zone
variability.
C.I.2 Grids
Divide each zone into an imaginary grid with unit areas that depend
on zone area size (Z) as follows:
i Z <500 m2, divide the zone into units with areas equal to five
percent of the total zone area;
• 500 m2 < Z <4,000 m2, divide the zone area into units of 25 m2;
• 4,000 m2 < Z <32,000 m2, divide the zone area into 160 units;
• Z > 32,000 m2, divide the zone area into units with area equal
to 200 m2.
Assign a series of consecutive numbers to the units in each zone.
C.I.3 Sample Size
The number of units to be sampled for the Kth zone (nK) is
calculated based on the area of the zone as follows:
nK = 6 + 0-15Leaof zoneK(m2
C-2
-------
C.I.4
Sample Localions
The nK units to be sampled in each zone are selected using a table
of random numbers. A unit is selected for measurement only once. Emission
flux measurements are then obtained for each randomly selected unit using one
of the direct emission measurement techniques.
C.I.5
Zone Emission Rates
After all the unit emission rates are determined, a preliminary mean
emission rate for each zone is calculated as follows:
(Eq. C-2)
where: EK - mean emission rate for zone K;
n« - number of units sampled in zone K;
measured emission rate for the ith unit in zone K
In addition, the variance ($£) and coefficient of variation (CVK) are
calculated for each zone using the following relationships:
(Eq. C-3)
CVL
(100)(SK)
L
(Eq. C-4)
C-3
-------
Before calculating an overall emission rate that represents all the
zones measured, the data for each zone must be tested for level of confidence.
That is, for the calculated coefficient of variance (CVK) of zone K, the zone
sample size (nK) must be equal to or greater than the sample size required
(n«) to estimate the overall emission rate within 20 percent of the overall
emission rate with 95 percent confidence. The total number of samples (nK) to
be collected for different confidence levels can be calculated as follows:
t2 CV2
n,/ > <* K (Eq. C-5)
t
where a study requires 100 (l=2a) percent confidence that the emission rate
estimates will be within p percent of the true mean. The parameter ta is the
(1-a) percentage point of a student's t-distribution with NK degrees of
freedom. Tabulated t-values can be found in any book on standard statistical
techniques. Recommended values for ta are listed in Table C-l. The sample
sizes required for 95 percent confidence and a 20 percent confidence interval
(a - 0.025, p - 20) are listed in Table C-2.
For each zone, the calculated coefficient of variation (CVK) is used
to determine the required sample size (nK). If NK > nK, then (NK - nK)
additional units must be sampled in zone K. Additional units are identified
using a random numbers table. If additional samples are required to meet the
specified confidence limits, then the mean zone emission rate (£„), variance
2
(S^), and of coefficient of variation (CV.,) be recalculated using equations
C-l, C-2, and C-3. NK samples are used instead of nK in the recalculations.
If NK is significantly larger than nK (i.e., emission rates from
units within the zone are very different), it may be most effective to rezone
the entire area using the preliminary measured emission rates as a guide. The
new zones will need to be gridded as discussed previously.
C-4
-------
TABLE C-l. TABULATED VALUES OF STUDENT'S "t"
Degrees of
Freedom*
*
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Tabulated
"t" Value**
12.706
4.303
3.182
2.776
2.571
2.477
2.365
2.306
2.262
2.228
2.201
2.179
2.160
2.145
2.131
2.120
2.110
2.101
2.093
2.086
Degrees of
Freedom*
21
22
23
24
25
26
27
28
29
30
40
60
120
CO
Tabulated
"t" Value**
2.080
2.074
2.069
2.064
2.060
2.056
2.052
2.048
2.045
2.042
2.021
2.000
1.980
* Degrees of freedom (df) are equal to the number of samples collected less
one.
** Tabulated "t" values are for a two-tailed confidence interval and a
probability of 0.05 (the same values are applicable to a one-tailed
confidence interval and a probability of 0.025).
C-5
-------
TABLE C-2. TOTAL SAMPLE SIZE REQUIRED BASED ON THE PRELIMINARY SAMPLE
COEFFICIENT OF VARIATION ESTIMATE*
Coefficient of Number of Samples
Variation - CV (%)** Required (NK) per Zone K
0 -
19.2 -
21.7 -
24.1 -
26.1 -
28.1 -
29.8 -
31.6 -
33.2 -
34.7 -
36,3 -
37.7 -
1 39.0 -
40.3 -
41.6 -
42.9 -
44.0 -
45.2 -
46.3 -
47.4 -
48.5 -
49.6 -
50. 8 -
51.7 -
52.4 -
19.1
21.6
24.0
26.0
28.0
29.7
31.5
33.1
34.6
36.2
37.6
38.9
40.2
41.5
42.8
43.9
45.1
46.2
47.3
48.4
49.5
50.7
51.6
52.3
53.4
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
* Value given is the sample size required to estimate the average emission
rate with 95 percent confidence that the estimate will be within 20 percent
of the true mean.
** For CVs greater than 53.4, the same size required is greater or equal to
CV2/100.
C-6
-------
C.I.6 Overall Area Emission Rate
i
Once the zone emission rates have been determined within the
specified confidence limits, the overall area source mean emission rate (E) is
calculated as follows:
E - 2 WK • EK (Eq. C-6)
where: EK - mean emission rate for zone K;
WK - fraction of the site area covered by zone K (zone area/site
area); and
7 - total number of zones sampled.
C.2 Example Calculations
The following example calculations are presented for a hypothetical
site contaminated by a spill of JP-4 aviation fuel. The total contaminated
area is 1,000 m2. Other pertinent data and calculations are summarized in
Table C-3.
Results from a preliminary emission survey performed with a portable
real-time analyzer (organic vapor analyzer) were used to divide the area
source into emission zones. The survey indicated that two zones of
contamination were present; a small zone with a high concentration of
contaminant (250 m2) and a larger zone with low level contamination (750 m2).
C-7
-------
TABLE C-3. HYPOTHETICAL SITE DATA AND EXAMPLE CALCULATIONS
Site Data ====================
Total Site Area = 1,000 nr
Number of Zones * 2
of Zone I - 250 m2
Area of Zone 2 « 750 m2
Zone 1
Total number of units - 20 (12.5 nr)
Number of units to be sampled:
nK = 6 + 0.15 ^area(m2)
J3.. = 6 + 0.15 V250 m2
Measured Emission Flux from Randomly
Selected Units EK1 /*g/iii2«min
Unit 4
Unit 6
Unit 8
Unit 13
Unit 14
Unit IK
unit is
Unit 19
Unit 23
Unit 25
14.4
12.6
19,6
14.9
10.0
1 S. £
10 = 0
10.7
11.5
11.4
- K
Mean Emission Rate - EK - — y^
121.7
I - 13
C=8
-------
TABLE C-3. (Continued)
Variance =
= —i-j f (*JJ - nK E*
* = -^- [1724.5 - (9) (13. 5) 2]
= 10.5
= 3.2
(100) (Sr)
Coefficient of Variation = CVK = -——
(100) (3.2)
CVi = 23.7
NK (from Table C-2) = 8
NK < nK (8 < 9)
Zone 2
Total number of units - 30 (25 m2)
Number of units to be sampled:
nK - 6 + 0.15 /750 m2
nr = 10
C-9
-------
TABLE C-3. (Continued)
Measured Emission
Flux from Randomly
Selected Units
Unit 2
Unit 4
Unit 7
Unit 12
Unit 13
Unit 17
Unit 22
Unit 23
Unit 25
Unit 29
EK<
/id/in «min
0.10
0.25
0.30
0.17
0.18
0,25
0.20
0.21
0.15
0.30
Mean Emission Rate » E2 = 0.211 /tg/m2»min
Variance « S^ - j^y |o.4829 - (10)(0.211)M
- 4.19 x 10"3
0.0647
Coefficient of Variation - CV, - (100)(0-0647)
* 0.211
CV., = 30.7
NK (from Table C-2) = 12
N > n (12 > 10)
(Continued)
C-10
-------
TABLE C-3. (Continued)
Emission Rates for 2 additional units:
Additional Units K., ng/mz • min
Unit 3 OJ
Unit 10 0.15
— 2
Recalculated Mean Emission Rate = E2 - 0.205 m
Recalculated Variance « S
2 __L_
2 ~ 12-1
71
0.5454 - (12)(0.205)2
- 3.74 x 10"3
S2 = 0.0611
Recalculated Coefficient of Variation = CV£ =
CV2 = 29.8
NK (from Table C-2) - 12
Overall Source Mean Emission Rate
1
' WK'EK
K-l
7- 2
_ 2
Zone 1: E, - 13.5 /Kj/m • min
u 250 m
1 1,000 nT
C-ll
—I
(Continued)
-------
TABLE C-3. (Continued)
Zone 2: E^ - 0.205 /ig/ffl • min
«. - -^
1,000
E - (0.25)(13.5) + (0.75)(0.205)
- 2
E = 3.5 /jg/m • min
O12
-------
To obtain an overall emission rate for the total area, the zones
were divided into units according to the criteria specified in Section C.I.2
and assigned consecutive numbers. The number of units to be sampled in each
zone was calculated using Equation C-l. This calculation and hypothetical
emission rates for each randomly selected unit are summarized in Table C-3.
The mean, variance and coefficient of variation were calculated for each zone
using Equations C-2, C-3, and C-4.
For zone 1 the level of confidence check indicates that a sufficient
number of samples were collected since NK < nK (8 < 9). No additional samples
were required from this zone. The coefficient of variation (CVK) for Zone 2
indicates that two additional samples were required (CV2 - 30.7, NK « 12 from
Table C-2). The two new zones were sampled and a new mean, variance, and
coefficient of variation were calculated using the new sample size (nK = 12).
The level of confidence check then indicated that a sufficient sample size (nk
= 12) had been collected.
The overall area mean emission rate were then calculated using
Equation C-6, as shown in Table C-3. The final result was an overall emission
rate of 3.5 /jg/m2«min.
C-13
-------
APPENDIX D
DESCRIPTION OF SOURCES OF MODEL INPUT DATA
D-l
-------
Solid Waste Landfill Survey
The Solid Waste Landfill Survey was initiated by the U.S. Environmental
Protection Agency in 1986. Detailed questionnaires were sent to a total of
1,200 municipal landfills; 98 percent responded. The information provided in
these responses was complied into a SAS data file by Development Planning and
Research Associates, Inc. (DPRA). The information included in this
computerized data base includes:
Operations Information
t Owner and operator
• Location
§ Number of other municipal landfills in the vicinity
• Shortest distance from the property line/landfill to a residence
• Total area
t Total design capacity
t Total remaining capacity
• Landfill method
t Waste processing techniques
• Quantity of waste from transfer stations
t Quantity of waste from resource recovery stations
• Ratio of waste to cover
• Operational hours
Hvdroqeological Information
• Terrain
• Soil type beneath landfill
t Landfill relation to the water table
• Distance from bottom of landfill to bedrock
D-2
-------
• Average permeability, porosity, and hydraulic gradient
of uppermost aquifer
§ Average groundwater flowrati
Waste Composition Information
• Average annual quantity of waste
• Percent of wastes by category (including industrial waste
characterization)
• Percent accepting liquids
§ Acceptance of liquid solvents
• Segregation of waste types
Design Information—for Closed. Active and Planned Units
• Date opened
t Date last received waste
§ Total volume
• Total area
• Maximum height above original grade
• Maximum height below original grade
• Average number of lifts
• Average lift height
• Liner type, thickness, and permeability
• Final cover material, thickness, and permeability
• Type of leachate collecting system
• Volume of leachate collected
• Method of leachate disposal
• Run-on/run-off systems
-------
Monitoring Information
§ Gas monitoring and recovery systems
• A1r emissions monitoring
Nationa> Survey of Hazardous Waste Treatment. Storage. Disposal, and
Recycling Facilities -- The National Survey of Hazardous Waste Treatment,
Storage, Disposal, and Recycling Facilities was initiated in 1987. The
database includes the following type of information:
• Permit data
• Commercial status of landfill
• Operating status
t Expected closure date
• Total capacity
• Surface area
• Liner data
• Quantity of hazardous waste received and generated
• Quantity of non-hazardous waste
• Remaining capacity
• Lab pack waste data
• Expected physical changes to be made
• Waste segregation
t Air pollution controls
• Air emission monitoring systems
• Cover type planned
• Waste restrictions
• Waste composition
National Survey Of Hazardous Waste Generators -- The U.S. Environmental
Protection Agency sent this questionaire to a number of hazardous waste
generators 1n 1987. Information requested in the questionnaire included the
following.
D-4
-------
Operational Information
« Ownership
§ Total land area
• Lofigitude and latitude of facility
Waste Composition Information
t NPDES Permit
§ Waste water quantity
§ Destination of hazardous waste
• Quantity of hazardous waste
• Management and quantity of gaseous hazardous waste
t Quantity and management of reactive materials
• Quantity and management of radioactive waste
t Waste minimization programs
Hazardous Waste Management Unit Information
• Any present onsite
• Terrain
• Soil type
• Relation to water table
• Average permeability, porosity, and hydraulic gradient of the
uppermost aquifer
t Groundwater flowrate
• Shortest distance of waste management unit to property boundary
D-5
-------
Solid Waste Management Unit Information
• Presence of SWMU's
« Number receiving hazardous waste
t Number receiving non-hazardous waste
• Type of unit
• Annual quantity of waste received
• Active or closed
• Start-up date and completion date
• Total quantity waste
• Waste types
t Groundwater monitoring
• Releases of hazardous waste from SWMU
• Waste piles
t Drummed hazardous waste in temporary accumulation areas
Hazardous Waste Information
t Types of waste
• Sources and processes producing waste
• Waste quantity generated per year
• Physical form of waste
• - Liquids
• Characteristics
Industrial Subtitle D Survey
The Industrial Subtitle D Survey was initiated by the U.S. EPA and sent
to facilities in January 1988. The results of the survey will be used to aid
the U.S. Environmental Protection Agency in developing strategies for the
management of Subtitle D waste. The information included in this data base is
listed below.
D-6
-------
Facility Information
• Location
• Total area
• Waste minimization
• Wastes generated and managed
t Physical and chemical characteristics of waste
§ Waste constituents
• Small quantity generator hazardous waste
Active and Closed Landfill Information -- (Also impoundments, land
application units, waste piles)
• Total area
• Total design capacity
• Maximum height above original grade
• Maximum height below original grade
• Average number of lifts
t Average height of lifts
e Liner type and thickness
e Year opened
• Years till closure
• Amount of waste disposed of in landfill
• Wastes present in landfill
• Time spent adding, covering, and compacting waste
• Waste processing
• Landfill method
• Ratio of waste-to-cover
t Percent capacity used
f Leachate collection systems
• Volume of leachate collected
• Management of leachate
t Run-on/run-off systems
D-7
-------
Other Waste Management Practices Information
§ Incineration: design parameters, control devices, feed compositions
and residual management
• Energy Recovery: design parameters, control devices, feed
composition, and residual management
• Storage/Treatment tanks: design, process, amount treated, feed
composition, and residual management
• Wastewater treatment system: design, process, waste quantity, and
composition;
• Recycling refuse: types, quantity, and residual management;
• Offsite management: quantity;
• Underground injection: waste quantity and composition.
Monitoring Information
• Gas systems
• Air emissions
t Soils
§ Groundwater
• Surface Water
Hvdroqeological Information
• Terrain
• Soil type
• Relation to water table
• Permeability, porosity, and hydraulic gradient of uppermost aquifer
• Average groundwater flowrate
D-8
-------
Industrial Subtitle D Telephone Survey -- The Industrial Subtitle D
Telephone Survey was also designed to gather information which would aid the
U.S. Environmental Protection Agency in developing strategies for the
management of Subtitle D waste. The survey began in 1986 and includes the
following information:
• Number of active landfills at a facility
• Total area
t Total waste quantity in 1985
• Remaining design capacity
• Number receiving offsite waste
• Is offsite waste household waste?
• Also, similar set of questions for surface impoundments, land
ication units, and waste piles
t Is the facility a small quantity hazardous waste generator (SQG)?
• Does the facility dispose of SQG waste?
• Does the waste management unit receive solvents or metals?
CHEMICAL PROPERTY DATA BASES
EPA Chemical Properties Data Base -- This chemical properties data base
is presented in Appendix D of a Office of Air Quality Planning and Standards
(OAQPS) report (44). This data base was developed for the use of calculating
emission rates from hazardous waste, treatment, storage, and disposal
operations with theoretical and empirical models. This data base is available
D-9
-------
in LOTUS format on a floppy disk and contains data on about 760 chemical
compounds. The data provided in this data base are:
e Chemical name
•*
t CAS number
t Molecular weight
« Vapor pressure at 2S*C
t Solubility
• Henry's law constant
• Diffusion coefficient in water
• Diffusion Coefficient in air
• Boiling point
• Coefficients for the Antoine equation for estimating vapor pressure
at temperatures other than 25*C
• Cancer unit risk value
§ Allowable daily intake in air
• Ratio of biochemical oxygen demand to chemical oxygen demand
The major limitations of this data base are: (1) the physical property
data is not complete for all compounds and (2) the properties data provided in
the data base represent a mixture of cited values and estimated values.
D-10
-------
National Library of Medicine Online Service =- The National Library of
Medicine maintains i Hazardous Substances Data Bank (HSDB) that contains data
on chemical properties. The HSDB data bank is derived from a core set of
standard texts and augmented with Information from government documents,
technical reports, and journal literature. The data file is maintained,
reviewed, and updated on the National Library of Medicine's (NLM) Toxicology
Data Network (TOXNET), where it is also searchable. The data bank is
organized by chemical, with over 4100 chemical substance records contained in
the file. Types of data available include:
• Substance name
• CAS number
• Boiling point
t Freezing point
• Specific gravity
• Critical temperature and pressure
• Dissociation constants
• Heat of combustion
• Heat of vaporization
• Octanol/water partition coefficient
• Solubilities
• Vapor density
• Vapor pressure
t Relative evaporation rate
• Viscosity
The HSDB also contains data in an environmental fate/exposure potential
file on the following:
t Biodegradation
t Abiotic degradation
• Bioconcentration
t Soil adsorption/mobility
• Volatilization from water/soil
D-ll
-------
Geophysical Data Bases
The GEMS Geoecology Data Base and the soil temperature data base,
available through the National Climatic Data Center (NCDC), can be used to
obtain geophysical data for a specific site.
GEMS Geoecology Data Base--
This data base contains county-level data on a variety of environmental
parameters including climatic and terrain data. The terrain data includes
county soil types from national atlantes, together with some physical and
chemical properties of general soil classes. The climatic parameters archived
include annual average and monthly maximum and minimum temperatures and
monthly precipitation dati.
NCDC Soil Temperature Data Base--
This data base is available on computer tape and provides data collected
over the period 1967-1982. The primary source of the archived data is daily
measurements taken by the Federal Government, State governemnt, and University
sponsored Agriculture Research and Experimentation station network. The data
are stored by State number, Station Index number, and Division number by daily
data, monthly extremes, and monthly average. Each record contains the daily
measurements for a particular depth. The major parameters that make up the
data file are:
t Depth of soil temperature measurement;
• Soil type; and
• Daily temperature.
Meteorological Data Bases
Meteorological Statistical Array (STAR) data bases and National Climatic
Data Center (NCDC) data bases may be useful sources of meteorological
information.
D-12
-------
STAR Data Base--
Two STAR data sets were identified, the data set created for the
Industrial Source Characterization - Long-term (ISCLT) model and the data set
created for the Human Exposure Modal (HEM). The STAR data set generated for
ISCLT is available through the GEMS data management system. This data set was
derived from NCDC data and contains data for 394 weather stations in the
continental United States. The ISCLT STAR data set provides the following
information for each STAR site:
• Frequency of occurrence for different combinations of wind speed,
stability class, and wind direction;
• Years of record;
• Annual average mixing height;
• Annual average precipitation;
t Annual average temperature; maximum and minimum temperatures;
t Average morning mixing height;
• Average afternoon mixing height;
• Stability classes and frequency of occurrence;
• Average weighted wind speed for each stability class;
• Average weighted wind direction for each wind speed;
• Average wind speed; and
• Representative wind speeds and frequency of occurrence.
D-13
-------
NCDC Data Bases--
The NCDC archives meteorological data collected from cooperative weather
stations. Daily and monthly average are available for:
t Maximum and minimum temperature;
• Precipitation;
• Snowfall and snow depth;
• Evaporation;
t Soil temperature;
t Relative humidity;
• Mixing height;
• Wind Speed;
§ Wind Direction; and
• Pressure tendency and pressure change.
D-14
-------
APPENDIX E
DESCRIPTION OF REMOTE SENSING TECHNIQUES
-------
REMOTE SENSING TECHNIQUES
FOR MEASURING TRACE GASES
IN THE AMBIENT AIR
DRAFT TECHNICAL NOTE
Prepared For:
Ms. Anne Pope
The U. S. Environmental Protection Agency
Non-Criteria Pollutants Programs Branch
MD-15
Research Triangle Park, NC 27711
Prepared By:
Radian Corporation
November 7, 1989
E-l
-------
TABLE OF CONTENTS
1.0 INTRODUCTION ......................... 1=1
2.0 REMOTE SENSING TECHNIQUES 2-1
2.1 Active Remote Sensing 2-4
2.2 Passive Remote Sensing 2-16
3.0 APPLICATION OF REMOTE SENSING TECHNIQUES ........... 3-1
3.1 Point Source Monitoring ...... ....3-2
3.2 Area Source Monitoring 3-8
3.3 Permiter Monitoring Applications 3-11
3.4 Advantages/Disadvantages of Remote Sensing Techniques . 3-12
LIST OF TABLES
2=1 Summary of Various Remote Sensing Techniques .........2-2
LIST OF FIGURES
2-1 Optical Configuration for Long Path FTIR ...........2-6
2-2 Differential bsorption Lidar Operated in A Range Resolved or
Topographical Refectance Mode ................ 2=11
2-3 Basic DIAL Lidar System Configuration ............ 2-12
2-4 Differential Absorption Lidar Using a Non-Laser Source ... 2-14
3-1 EPA Rose Infrared Spectrometer System ............. 3-4
E-2
-------
1.0 INTRODUCTION
The environmental impacts from the release of airborne toxic
chemicals is a topic of great interest among air pollution scientists. This
interest extends to all types of emission sources including stationary point
sources (e.g. incinerator stacks, ground water strippers) as well as area
source emissions (i.e., landfills and lagoons). It is important that
measurement methods be developed to accurately assess the impact of airborne
chemical emissions on the environment. Until now, traditional air sampling/
analytical techniques have been used to characterize emission impacts of
airborne toxic chemicals in the environment. While these techniques can
provide useful information, very often these methods are unable to provide
adequate temporal and spatial resolution due to inherent limitations (i.e.,
physical, manpower, capital cost, operating cost, etc.). One major limitation
is the significant time delay typically encountered between the start of
sample collection and the reporting of analytical results.
Significant advances have been made in recent years to develop
practical remote sensing methods for measuring trace gases in the ambient
environment. The development of cost-effective and very powerful
microcomputer technology and reliable medium to low powered gas and semi-
conductor lasers has made a possible the development of remote sensing
techniques which can be used to measure the emission impacts of toxic airborne
chemicals in the ambient environment. As a result, several promising remote
sensing technologies have emerged, and ultimately may provide scientists with
useful tools to conduct environmental assessment studies. Remote sensing
could, potentially, allow for rapid screening or in-depth studies of ambient
concentrations of airborne toxic compounds. This has obvious implications for
the Superfund Program, where there is a need for real-time concentration data
for specific analytes for both baseline conditions and during remediation.
Such data are essential for making on-site decisions that may affect the
health and safety of on-site workers and the surrounding community.
E-3
-------
This document briefly summarizes some of the more recent
developments in remote sensing technology as it applies to the
characterization of emission impacts both area and stationary point emission
sources. This document discusses some of the advantages and practical
limitations of selected remote sensing technologies. Finally, some general
comments and recommendations are provided regarding the future technological
development required to advance the development of remote sensing for
environmental applications.
E-4
-------
2.0 REMOTE SENSING TECHNIQUES
/
Remote sensing methods can be divided into two general categories.
These categories include active remote sensing and passive remote sensing
techniques. * Active remote sensing typically entails directing a focused beam
of energy (usually light energy from a controlled source) through the
atmosphere and then sensing the interaction of the beam of electromagnetic
energy with the constituent(s) of interest (1). This process usually involves
sensing the amount of reflected energy returned to the sensor, through the
process of atmospheric backscatter, or by measuring the amount of molecular
absorption or neutral absorption (attenuation) that occurs when the reflected
energy beam interacts with those constituents of interest.
Passive remote sensing involves two modes of detection (e.g.,
emission or absorbance). In the emission mode, the target compound(s) emit
electromagnetic energy which is sensed directly. In the absorbance mode the
target compound(s) react in a manner whereas to change the transmissivity of
natural light (e.g., direct sunlight, scenery light skylight, or thermally
emitted light). Because uncontrolled light sources are used in conjunction
with most passive remote sensing techniques, operational periods are generally
limited to periods of sufficient natural lighting.
There are a number of remote sensing techniques which deserve
serious consideration for environmental measurement applications. An
extensive review of remote sensing methods has been recently compiled by
Saeger et.al. (1) for the U. S. Environmental protection agency. A summary
listing of those remote sensing techniques which are in common use for
environmental measurement applications are given in Table 2-1. The table
includes both active and passive remote sensing technologies, which appear
suited for measuring trace concentrations of gas or vapors from a variety of
emission sources. A brief summary of these methods is provided.
E-5
-------
TABLE 2-1. SUMMARY OF VARIOUS REMOTE SENSIMG TECHNIQUES
Technique
Spectral
Region
Measurement
Heasurment
Application
Effective Range
(oatars)
Active Remote Sensing,
Long Path Interferometry
Fourier Transform IR (FTIR)
IR
Gases and Vapors
Fabry-Perot Intarferometry UV and Some gasae
VIS
Area, perimeter
Stack
8,3 to X kro
Undetsrmiuad
Most «pplie«tions
use * telescopic
traziacBittmr/
receives.
High resolution in
UV and visible
regions. Technique
has nofc been field
tested.
T
0\
Long Path Lidar
Atmospheric Backscatter
Lida
Differential Absorption
Lida (DIAL)
VIS and Opacity, aerosol
Hear IR cone,, aersol depth.
UV and Atmospheric gases
IR and organic vapors
Area and Stack
Area, stack, and
perimeter.
O.S te 15 km
0.1 to 8 km.
used
to measure Hie
aeatteeing Ceerosols
and fine dust
partieles).
DIAL sen be used in
ranging as
coneentsatiaii modes.
Technique is useful
in eliminating
atmoapheEie
interfesenees.
Raman Scattering Lidc UV and
VIS
Gas Imaging
Backscatter/Absorptlon Gas IR
Imaging (BAGI)
Atmospheric gases
and organic vapors
Plume ranging and
detection.
Area, stack, 0.1 to 1.0 km.
particle mattar.
smoke, temperature
profiles, and
tracking atmospheric
dyes and tracers.
Stacks, area, 0.1 to O.S km
perimeter.
'
Technique is
generally limited to
cleat sky. nighttime
applieati'ins . The
technique t>££#s»
limited sensitivity.
Employee DIAL
measurement
approach, Cursently
method eannot
measure
concentration.
(Continued)
-------
TABLE 2-1. (Continued)
T
Technique
Paaijv* Remote Sensing
Radiometers
Gaa Correlation Spectroscopy
Non-dispersive DCS
Mask correlation
Spectroscope
Inter ferometry
Spectral
Region
UV and
VIS
IR
UV and
IR
IR
Measurement Measurement
Parameter(s) Application
Opacity, velocity. Stack
and atiDoapheric
pollutants
Atmospheric Stack perimeter
pollutant*
Atmospheric Stack perimeter
Pollutants
gases and vapors Stack
Effective Range
(meters) Commits
0.1 to 1.0 km Technique* usas
wavelengths to
eliminate
atmospheric
intee£*;enc«a .
two
0.1 to 1.0 km Typically limited to
one compound
0.1 to 1.0 km Use* skylight ac
source>. Limited
daylight hours.
0.1 to 2.0 km Utilises Fourier
Transform IR
to
-------
2.1 Active Remote Sensing
Several promising aetlve remote sensing measurement techniques have
been developed for environmental measurement applications. Techniques which
appear promising for measuring the presence of trace levels of toxic gases and
vapors in the atmosphere include:
• Long Path Interferometry;
• Long Path Lidar; and
• Gas Imaging.
Lone; Path Interferometers
Long path (open path) interferometry can be used in both the active
and passive remote sensing modes. As such these devices are useful in
assessing the impacts of airborne chemical emissions from a variety of
emission sources. There are several types of interferometers used in
environmental remote sensing applications (1,2,3,4,5,6,7,8). The most common
types are the Michelson interferometer and the Fabry-Perot interferometer.
The Michelson interferometer has replaced most wavelength dispersive
spectrometers for applications in the infrared region. This device uses a
sophisticated optical arrangement to split incoming radiation into two paths.
The two beams are then recombined after introducing a path difference with a
moveable mirror. This results in the encoding of a multiplexed spectral
inteferogram. A microcomputer is used to perform digitized encoding of the
interferogram, and a Fourier transformation of the interferogram is then
performed to produce a spectrally resolved output. This technique results in
a substantial improvement in spectral resolution and throughput over
conventional grating spectrometers. The Fabry-Perot interferometer is used to
obtain high resolution and throughput in the ultraviolet and visible ranges.
Circular apetures are used instead of slits to improve throughput of these
devices.
E-8
-------
Long path (open path) interferometery can be used in either the
active or passive modes. In active remote sensing applications, the system
incorporates either a single ended or double ended telescopic
transmitter/receiver configured to measure the absorbance of features of those
constituents of interest. A coaxial telescope arrangement is used to direct a
line of site beam of infrared light across an area of concern. In a double
ended configuration, the light source is mounted on a tripod or some other
mounting device at some fixed path distance from the receiver
optics/interferometer as shown in Figure 2-1. This arrangement can be
modified by the addition of collimator optics such that the transmitter and
receiver are housed in the same unit, and corner cube retroflectors are then
used to reflect the transmitted IR beam back to the receiving telescope. The
latter design offers several advantages over the double ended design in that
the retrorefleetors are much more portable and easier to align. Both
arrangements can be configured to permit multiple reflectance targets to be
used to extend path coverage over a wider area.
Typically, long path Fourier Transform IR (FTIR) is used in the
absorbance mode to make horizontal measurements over distances of 0.01 to 2.0
km. These devices are used to gather path averaged concentration measurements
for a variety of gases and vapors that have moderate to strong absorbance
features in the infrared region. Because these systems employ an
interferometer and sophisticated signal processing computer hardware and
software, they can be programmed in either a spectral search mode or used to
selectively scan selected regions of the infrared spectrum if the absorbance
frequencies of the compounds of interest are known.
Long path FTIR is capable of measuring path integrated
concentrations in the low ppm-meter range. The ultimate sensitivity will
depend on the width the pollutant plume and distribution of the gas or vapor
molecules along the directed path. In most instances it is convenient to
relate the path integrated concentration measurements in terms of one meter
closed path cell. System calibrations can be performed in the field by
inserting closed gas cells in a specially designed mount and directing the
light source through the cell.
E-9
-------
VAN HALL
satinet, TELESCOPE
USHT
MWKf
Figure 2-1. Optical Configuration for Long Path FTIR.
E-10
-------
Long path FTIR. is quite versatile because it can be used to obtain
both qualitative and quantitative information regarding the presence of
compounds which exhibit strong absorbance features in the infrared spectrum.
Spectral libraries exist for a large number of gases and vapors, and software
programs designed to perform spectral matching for complex matricies are
available. This latter feature is very important if the system is being used
near emission sources which have not been previously characterized. However,
the technique is subject to atmospheric and chemical interferences (i.e.,
carbon dioxide, carbon monoxide, water vapor, etc.), and may not possess the
sensitivity or selectivity to accurately characterize extremely low
concentrations of gases and vapors. Spectral subtraction and data
manipulation techniques are used to minimize the effects of atmospheric and
chemical interferences (4). However, due to inherent limitations in the
sensor design, it may not be possible to completely eliminate atmospheric or
chemical interferencies using reference path and spectral subtraction
techniques.
Long path FTIR has been used to effectively characterize fugitive
emission sources from surface impoundments and landfarming operations.
Additionally, there are commercially available, open path FTIRs used in
perimeter monitoring applications. In the spectral search mode, long path
FTIR can be used to screen for the presence of infrared active species. Once
compounds of interest are detected, the system can then be placed in a scan
mode which will simultaneously scan for several compounds of choice.
Long Path Lidar
The development of laser technology has made possible the
development of long path Light Detection and Ranging (Lidar) techniques for
environmental and atmospheric measurement applications. Bordonali et.al. (2)
provide an excellent theoretical overview of Lidar based sensing techniques. A
number of Lidar methods have evolved. These include atmospheric (Mie)
backscatter, Differential Absorption Lidar (DIAL), fluorescence Lidar, Raman
backscatter Lidar, wedge Lidar, and Doppler Lidar. These methods have been
used in the following applications:
E-ll
-------
• Area and perimeter monitoring of airborne chemical emissions
from area sources;
•* Measurement of pipeline leaks and other stationary point
sources, and fugitive emissions;
• Monitoring of trace concentrations of vapors and gases which
-participate in photochemical reactions;
• Measurement of atmospheric parameters (i.e., temperature and
wind velocity); and
« Validation of pollutant transport models.
Of the Lidar methods cited, atmospheric backscatter and DIAL have
been demonstrated to be effective in assessing impacts of airborne chemical
emissions from area and stationary point sources. Depending on the particular
application, these types of measurement techniques offer the ability to
characterize the temporal and spatial impacts of air emission sources.
Atmospheric Backscatter Lidar
The most common and effective backscattering Lidar technique
involves the measurement of Mie scattering. In this application the
transmitter/receiver are collocated. The use of lasers permits the use of
intense monochromatic sources of light energy which are tunable and can be
emitted as continuous waves (CW) or in short duration pulses. The latter
permits useful range information to be obtained by measuring the time interval
over which backscattered light energy is returned to the receiver (2). When a
light beam is transmitted through the atmosphere a portion of the transmitted
light is scattered in many directions when it interacts with atmospheric
constitutents. A portion of the transmitted light energy is returned along
the axis of directed beam by a process known as backscatter.
E-12
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There are three scattering processes which occur. These are Mie,
Rayleigh, and Raman scattering. Hie scattering occurs when the parameters of
interest (i.e., aerosols, dust, water droplets, etc.) are the same size
(diameters) as the wavelengths of the incident light. Mie scattering is not
wavelength dependent, and untuned lasers can be used to measure aerosol
concentration, particulate emissions, and opacity. Sensors, which operate
based on the measurement of Mie scattering, employ lasers which operate in the
infrared and visible range (1). Pulsed Mie backscattering sensors are able to
determine both concentration, plume opacity and ranging information. For the
most part these types of devices have been used to characterize emissions from
power plant plumes. In these applications, the plume measurements are
referenced to clean air Lidar returns. These types of sensors are capable of
remotely measuring particle and aerosol concentrations at ranges of 0.1 to 15
km. However, these devices are not as sensitive as other remote sensors which
use optical reflectors to increase throughput of light energy from the
controlled source.
Differential Absorption Lidar (DIAU
Differential Absorption Lidar (DIAL) relies on the wavelength
dependence of those gases of interest to obtain quantitative concentration
data for specific analytes of interest. DIAL remote sensing systems typically
employ a laser(s) tuned to two different wavelengths. DIAL devices employ
either a single or double ended transmitter and receiver configurations. In
most cases, the single ended system is preferred due to the increased
sensitivity due to path doubling when reflectance targets are employed.
The DIAL technique involves tuning one laser to a wavelength for
which the compound of interest contains a strong spectral absorbance feature
(wavelength "on"), and the second laser tuned to a wavelength in a region of
low absorption (wavelength "off"). The technique of simultaneous one "on" and
one "off" sensing permits DIAL systems to be operated under a variety of
conditions and virtually free of other atmospheric interferences (aerosols,
water vapor, dust, fog, snow and water droplets). In some system designs, it
is possible to accomplish the same effect by tuning a single laser to two
E-13
-------
different wavelengths. Thus, by comparing the attenuation in the intensity of
the two signals (e.g. differential absorption) it is possible to detect the
presence of a particular compound ©f interest. This technique has been
particularly useful in measuring those gases and vapors which have strong
absorption features in the infrared and ultraviolet ranges.
The DIAL technique can be configured to measure the differential
absorbance of light returned to the receiver by the distributed reflectance of
aerosols and molecules. A modification of this technique involves using
topographical reflectors (hills, walls of buildings, etc.) to reflect the
light beam to the receiver. If the system is configured with pulsed lasers in
the UV visible range, it is possible t© not only obtain concentration data,
bue als© obtain ranging information t© determine the location and path width
of the plume. Typically, lasers in the infrared do not have sufficient power
to obtain effective ranging information. Figure 2-2 illustrates the use of
DIAL sensors in both the distributed reflectance and topographical reflectance
modes.
Figure 2-3 illustrates a DIAL system developed by TECAN REMOTE which
employs cornercube retroflectors in a topographical reflectance mode (4). In
this configuration the corner cube reflector acts as a man-made topagraphical
reflector with extremely high reflectance efficiency. This approach results
in greater signal reflectance than other natural or man made topographical
reflectors (i.e., walls, buildings, etc.). It is important to note that when
topographical"reflectors are used, the resulting measurement represents a path
averaged concentration measurement over the entire path, and ranging
measurements cannot be effectively obtained. The use of cornercube reflectors
permits lower powered lasers to be used with minimal degradation in sensor
performance. This is extremely important from the standpoint of eye safety.
Lasers operated in the IR range above 1.4 urn. and in the UV range below 0.4 urn
can present eye safety dangers, and may restrict their use in certain
E-14
-------
A . Ring* Resolved Measurmerrt
B • Integrated Mea*urment
B
Topographic
Reflector
Figure 2-2.
Differential Absorption Lidar Operated in A Range Resolved
or Topographical Refectance Mode
E-15
-------
R
=!=~~^
I LmerjJ
rv
BS
as
Receiver
Cube comer
No gas
present
^— Sign** 1
2
Low
quantity
of gas
present
—*J SfeuJ 1
High
quantity
of gas
present
Signal 1
Signal 2
BS « 8«am«plftt>r
M - Mirror
.Rj * UMT power mtartne* signal
Figure 2-3. Basic DIAL Lidar System Configuration.
E-16
-------
instances (i.e., populated areas, workplace area, etc.)- The effective path
range over which measurements can be made varies depending on system
configuration and application. Pulsed lasers can provide effective
measurements over a range of 5 km and continuous lasers can be used at
effective ranges up to 1 km.
Various types of lasers can be used to emit emission lines ranging
from 0.27 to 337 fan. There are four classes of lasers which are in widespread
use. They are distinguished based on the lasing medium, and include: gas
lasers, liquid lasers, semiconducting lasers, and dielectric crystals and
glasses (10). Those lasers which emit laser lines in the ultraviolet and
infrared spectrum are the most popular for use in remote sensing applications
involving the trace measurement of gases and vapors. One of the most
effective lasers used in commercial DIAL applications is the C02 laser. This
laser emits 60 emission lines between 9 and 12 /im.
It is important to note that differential absorption techniques can
also be used with a combination of blackbody radiation sources and narrow
bandpass filters (9) to obtain results which are functionally comparable to
conventional DIAL techniques which use laser sources. Figure 2-4 illustrates
an example of an infrared differential absorption system developed by TECAN
REMOTE. This double ended system, is limited in the effective range over
which measurements can measurements can be made (-200 meters). However, it
offers the ability to sequentially measure more than one compound using a
filter wheel and chopper arrangement to alternate between absorbing and
non-absorbing frequencies. This represents a practical advantage over
conventional DIAL systems which are typically designed to measure only one
compound at a time.
DIAL techniques are effective in characterizing chemical emissions
from stationary point sources, fugitive emissions from area sources. These
types of sensors offer reasonable effective ranges over which measurements can
be made, and are designed to minimize atmospheric interferences. These
systems can be configured for use in mobile labs or stationary shelters.
E-17
-------
THANSMTTTER
RECEIVER
• DIAL MONITORING PATH •
REFLECTING
CHOPTER
Figure 2=4. Differential Absorption Lidar Using A Non-Laser Source
E-18
-------
This permits both transient or semi-permanent/permanent monitoring to be
performed for both stationary and area monitoring source characterization
applications. While the systems are sensitive in the low to sub-part-per-
million meter range, the usefulness of these techniques as screening tools to
assess potential health hazards depends, to a large part, on the source
strength and other emission source characteristics. As such, these methods
may not be as sensitive as integrated point monitors in some applications.
The same also holds true for long path interferometery techniques.
Furthermore, it is important to note that it is possible to select wavelengths
where more than one compound will absorb, thus increasing the potential for
chemical interferences. In some cases the absorption characteristics of other
atmospheric or chemical interferents are such that either positive or negative
interferences can occur, thereby making data interpretation difficult.
Therefore, there may be times when the use of this technique may result in the
measurement of erroneous data. Physical obstructions (i.e., animals, man,
man-made objects, etc.) are easily detected and the measurement output can be
flagged accordingly.
Gas Imaging
A sensing technique which involves the use of Backscatter/
Absorption Gas Imaging produces a visible image of invisible gas plumes on
a video monitor (1). This technique measures the differential absorption of
backscattered radiation at the absorption wavelength of interest.
Sophisticated signal processing techniques are used to display a real time
image of the plume on a video monitor. A laser beam is directed to points
within the plume and outside of the plume to measure the amount of radiation
which is differentially absorbed by the gas species of interest. This system
has been used primarily in imaging gas plumes from stationary emission
sources, but can be used in other applications. Carbon dioxide gas lasers are
used as a laser source to produce emission lines in the infrared range. This
particular technique when coupled with other sophisticated data processing
techniques can be used to estimate plume volume, plume height, and plume
velocity. This particular technique has not been used to measure plume
concentration.
E-19
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2.2 Passive Remote Sensing
Several passive remote sensing techniques have been developed te
measure atmospherie parameters (i.e., temperature, water vapor, and
atmospheric 'gases), and chemical measurement parameters. In general these
devices have been used from satellite, aircraft and mobile ground based
platforms and for stationary stack measurement applications. These devices
include radiometers, gas correlation spectrometers, and interferometers. A
brief description of these types of remote sensing techniques follow.
Radiometers
Radiometers are n@n=dispersive measurement devices which have been
used over a wide spectral range including UV, visible and IR regions. These
devices are designed to measure electromagnetic radiation over a specified
spectral region (10). A series of interference filters can be use to isolate
the spectral regions of interest. Radiometers are low resolution devices.
The most common use of radiometers has been to measure temperature, opacity,
plume velocity, and gas concentration (in limited applications). As such,
these devices are rather limited in the ability to selectively monitor trace
gas concentration of airborne chemicals for environmental measurement
applications. However, they do have some application in obtaining infomration
(I.e, temperature, opacity) to track the transport of pollutants form specific
sources.
Gas Correlation Speetroscopy
Gas correlation spectroscopy simply measures the degree of
correlation between the spectrum of radiation emanating from the target gas
emissions compared to a known spectrum (1). This technique is extremely
sensitive and selective, and can be used to sense passive emissions from a
target gas over a large area. There are two basic types of gas correlation
spectrometers: non-dispersive and dispersive gas correlation techniques. Most
correlation spectrometers operate in the infrared spectrum.
E-20
-------
Non-dispersive gas correlation spectrometers use a gas cell filled
with the component of interest to mask the incoming radiation (1). In most
designs, the spectrometer consists of two cells (e.g. sample and reference).
The sample cell is filled with the gas constituent of interest. The reference
cell is either evacuated or filled with an inert gas. The incoming radiation
is alternated between the two cells (e.g., reference and sample cells). This
is accomplished typically by chopping the incoming radiation which is directed
through each cell. In the absorbent mode, the incoming radiation is
selectively absorbed by the target gas of interest. Due to differences in the
intensity of the incoming radiation and the absorption spectra of the gas in
the sample cell, there is an attenuation in the radiant energy passing through
the sample cell. Thus, the difference in the modulated signal is inversely
proportional to the gas concentration ©f the target constituent in the
atmosphere. In the emissions mode, the gas concentration is proportional to
the concentration of target gas concentration in the atmosphere.
In the dispersive mode, the incoming radiation is di-spersed into its
spectrum (typically using an optical grating). The dispersed radiation is
then superimposed on a machined mask positioned at the entrance to the
detector. The mask is machined such that the slits in the mask correspond to
the wavelength minima. The mask is specific to the spectrum of the target gas
of interest. The part of the incoming spectrum which matches the mask causes
an oscillation in the detector. The portion of spectrum of the incoming
radiation that does not match the mask causes a low amplitude variation in the
detector signal. The concentration of the target compound of interest is
proportional to the difference in the detector output (max vs. min) referenced
to the average.
Gas filter correlation techniques and mask correlation spectrometers
are typically designed to measure only one compound of interest. This limits
the overall utility of the method, unless the component of interest is an
atmospheric tracer which can be used to estimate the concentration of other
compounds of interest.
E-21
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Interferometrv
As previously mentioned, Fourier Transform interferometers can be
operated either as active of passive remote sensors. In the passive mode, the
infrared emissions can be detected using long path FTIR techniques. The
sensitivity in the emissions mode is typically on the order of a factor of lOx
less than when used in the absorbance mode. However, in most applications
involving the measurement of gas concentrations from stationary point source
plumes at elevated temperatures, it is necessary to determine the temperature
from the emission spectrum (7).
E-22
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3.0 APPLICATION OF REMOTE SENSING TECHNIQUES
Traditionally, direct source sampling techniques have been used to
estimate the emissions from stationary point sources (i.e., boiler stacks,
flares, tail gas treatment systems, incinerators, process vents, etc.). These
direct sampling techniques include a variety of integrated sampling and
continuous emissions monitoring devices (i.e. extractive and in-situ
monitors). Similarly, fugitive emissions from industrial sources, chemical
processes, and various types of treatment, storage, and disposal facilities
(i.e., landfills, surface impoundments, landfarms, aeration lagoons, etc.)
have been characterized using direct integrated sampling methods as well as
arrays of continuous measurement devices. While these devices are generally
effective in assessing air emission impacts, they can be quite costly in terms
of man-power, analytical costs, and/or routine operational costs.
Furthermore, the number of samples required to adequately characterize air
emission impacts may in some instances be cost prohibitive.
The use of remote sensing techniques may offer a more attractive
alternative for conducting both screening and routine surveillance monitoring.
This need is particularly critical around Superfund sites which are either in
the remedial investigation or remediation stages. Emissions of airborne toxic
chemicals from these sites pose a potential threat to both the workers on
site, and to local citizens who live and work in close proximity to these
sites. Additionally, the chemical manufacturing and petroleum refining
industries have shown interest in the applicability of remote sensing
technology to detect routine releases of airborne chemical emissions which are
reportable under SARA Title III. There is also interest in developing
perimeter and in-plant monitoring systems which can provide an early detection
of process malfunctions for emergency response purposes. This section
examines some practical applications of remote sensing technology in assessing
the emission impacts for a variety of trace gas constituents.
E-23
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For the purpose of this discussion, the examination of remote
sensing teehniques will be limited to those which are capable of measuring
trace levels of airborne ehemicals which might be emitted from a variety of
stationary point sources and area sources. A discussion of the practical
applications' of these technologies as well as the current limitations is
*
presented. These applications include the following:
« Point source monitoring (i.e., boiler stacks, flares,
incinerators, process vents, tailgas treatment systems, etc.);
« Screening of fugitive emissions from stationary area sources
(Io«., landfarms, surface impoundments, wastewater treatment
systems, landfills, etc.); and
• Routine Perimeter Surveillance Monitoring (i.e., chemical
plants, refineries, TSDF's, etc.).
3,1 Point Source Monitoring
A number of remote sensing techniques have been developed which are
designed to measure the concentration of various gases emitted from stationary
point sources (6,7) . To date these methods have been evaluated from sources
including: utility boilers, flares, cement plant kilns, etc. Both active and
passive remote sensing techniques have been used to characterize plume
temperature, opacity, particulate loading, and the concentration of combustion
gas products and other pollutants (i.e., N02, NO, CO, C02, HCL, NH3, HF, S02,
and H2CO. This technique is amenable to measuring a variety of organic and
inorganic compounds which exhibit strong absorbance features in the infrared
spectrum.
The most common remote measurement systems which have been used to
evaluate airborne chemical emissions from stationary point sources include:
• Long path FTIR operated in both the emissions, and absorbance
modes;
E-24
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« Gas filter and mask correlation spectroscopy; and
• Differential absorption Lidar,
«
The U. S. Environmental Protection Agency has conducted extensive
experiments to evaluate long path FTIR. The remote optical sensing emissions
(ROSE) system developed by EPA (3-8), is a good example of a mobile remote
sensing system based on the use of a commercially available Fourier Transform
infrared system. The ROSE system consisted of a Nicolet model 7199 FTIR which
was van mounted. The system was configured with a Dall Kirkham f/5 telescope.
A diagram of the system is shown in Figure 3-1. This system is capable of
measuring both in an emissions measurement mode (passive), or in an absorbance
mode (active) using cross stack sampling techniques.
In the cross stack mode, ports are installed in the stack, and a
collimated beam is aimed through the stack and reflected back to the receiver
located in the mobile van at the base of the stack. In the cross stack mode,
the system is capable of obtaining sensitivities on the order of 1 ppb. In
the emissions mode the receiver telescope is use to sense the IR emissions
signatures of pollutants of interest which exit the stack. The sensitivities
for most pollutants of interest is on the order of 1 ppm. In the emissions
mode, the FTIR system is particularly sensitive to plume temperature. Thus,
estimates of plume temperature are needed to correct the concentration
measurement data. Temperature measurements are estimated based on measuring
the spectral radiance of two different C02 lines. Of the two methods, the
cross stack measurement method is more sensitive and accurate than the
emission measurement mode. However, the logistics associated with the
emission measurement mode is more convenient, and yields acceptable accuracies
(+- 20X) when compared to extractive sampling techniques. Systems such as
this cost on the order of $200,000 to $300,000.
E-25
-------
VANWftil
INFRARED
S16NAI.
FROM
PtUME
DETECTOR . ,
Figure 3-1. EPA Rose Infrared Spectrometer System.
E-26
-------
Another useful tool which can be used to measure gas concentrations
from stationary point sources involves the use of gas filter correlation and
mask correlation spectrometers. These techniques have been previously
described in Section 2. The Barringer COSPEC is an example of a mask
correlation spectrometer (which can be used in either a passive or active or
passive mode. The COSPEC has been commercially developed to measure either
N02 or S02. In the active mode the system is reported to have sensitivities
of approximately 2 ppb over a range of 300 meters.
In the passive mode, the COSPEC system has been used in a variety of
plume tracking modes. In the look up mode, it is possible to track plumes
from stationary sources for long distances. The system is easy to use, it is
rugged, and can be operated by semi-skilled technicians. In the emissions
mode, the performance of the device is subject to drift based on the changes
in the source spectra (1). thus is limited to daylight use only. Furthermore,
these devices are also are sensitive to changes in the plume temperature. The
sensitivity in the passive mode is between 2-5 ppm-meters. The cost of the
COSPEC ranges from $30,000 to $50,000 depending on options. Gas filter
devices (which operate in a similar fashion) are also commercially available.
Differential Absorption Lidar can be used for measuring a variety of
gas species and can be operated in an emission or absorbance measurement mode.
These devices can be used to measure UV, VIS, and IR active species. Since
most DIAL systems employ the use of lasers, the specific compounds of interest
which can be detected will be dependent primarily on the emission lines of the
laser. These devices can be employed in a similar manner to the long path
FTIR, and can be used to perform range resolved, cross stack measurements, and
or used with topographical reflectors. Because the DIAL systems are active
remote sensing devices, these systems can be used both during the day and at
night, and have the ability to minimize atmospheric and chemical interferences
by use of differential absorption.
E-27
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While DIAL systems are very effective measurement tools, they do
have certain limitations. It must be noted that the current commercially
available systems are capable of measuring only one compound at a time, and
must be manually tuned for each compound of Interest. Furthermore, other
compounds wHich have absorption features at the designated absorption minima
of a compound of interest, can interfere (false negative)- and result in
erroneous measurement results.
Most commercially available DIAL systems have sensitivities and
selectivities which are comparable or better than long path FTIR's. The cost
of these systems are also generally comparable with that of FTIR's and range
from $100,000 to $200,000. These costs are dependent on the application
(stationary vs. mobile), and types ©f features dasired with regard effective
range, data processing capabilities, and data display.
Most remote sensing devices which measure the concentration of
^
pollutants emitted from stationary sources- are housed in mobile vans or on
lightweight tripods, and can easily be move to various vantage points to
conduct measurements. Some systems like the COSFEC device and other gas
correlation spectrometers can also be mounted in mobile platforms (i.e., vans,
airplanes, helicopters, etc.) and measurement results can be obtained while
the platform is in motion. This is particularly desirable for tracking plumes
from a point source, identifying "hot spots", or screening for gas leaks from
pipelines, etc.).
The applicability of using remote sensing techniques for measuring
emissions from stationary point sources will depend on a number of factors,
such as the characteristics of the source, site characteristics, meteorology,
and the limitations associated with the design and operation of the remote
sensor. Factors include:
E-28
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Source Characteristics
« Pollutant concentrations;
« Plume width;
« , Plume temperature;
• Plume exit velocity;
Site Characteristics
* Physical Obstructions which limit field of view;
« Objects which might interfere with plume dispersion (i.e.,
building wave effects);
• Accessibility of convenient vantage points to allow the set-up
and operation of remote sensing systems;
Meteorology
• Meteorological conditions that effect plume dispersion;
Limitations in Sensor Design
• Variations in measurement results for those devices which
require natural lighting;
• Field of view of the sensor;
• Selectivity and sensitivity;
• Number of compounds which can be measured;
E-29
-------
• Interferences (atmospheric or chemical);
« Logistics required to support measurements (available power,
need for eryogens to cool some detectors, physical space
requirements, etc.);
• The need for environmental enclosures required to filter out
vibration, and maintain constant temperature and humidity; and
« Overall complexity.
The methods described above have been shown to yield results comparable (+20%
t© 30%) to extractive point sampling techniques (i.e. long path FTIR,, gas
correlation, spectroseopy, and DIAL).
3.2 Area Source Monitoring
The use of remote sensing devices to assess impacts of emissions
from stationary and other area sources (i.e., chemical process units,
wastewater treatment systems, landfarms, landfills, waste handling facilities,
etc.) is an area of great interest. These devices offer the following
• Rapid assessment of toxic airborne chemicals over a wide area;
• Real-time assessment temporal and spacial variation of
emissions on ambient air quality; and
• Cost effective alternative to integrated point source
monitoring.
There are several remote sensing techniques which offer the ability"
to assess the ambient emission impacts from a variety of stationary and area
sources. Both active and passive sensing techniques have been used. They
include: long path interferometry, Lidar, DIAL and gas correlation
E-30
-------
spectrometers. These operation of these devices have previously been
described.
EPA has recently evaluated several types of remote sensing
techniques fer conducting pre-remedial air investigations near waste sites
(4). The purpose of these investigations was to assess the feasibility of
using remote sensing techniques to screen for air emissions from these sites.
In this preliminary investigation, three types of remote sensors were used.
They were long path FTIR, long path UV, and differential absorption Lidar.
The long path FTIR system consisted of Nicolet model 730 equipped
with a double ended Cassgrain receiver and transmitter. The energy source
consisted of a 100 watt halogen lamp and infrared globar source. A mercury-
cadmium-telluride liquid-nitrogen cooled detector was used to operate over a
range from 700 to 1400 cm-1. The system was equipped with a microcomputer
data system to process and display the measurement results from the sensor.
The receive.r optics and interferometer were located in a mobile van, and the
transmitter scope was tripod mounted at fixed distances from the
receiver/interferometer. The system was operated in the absorbance mode.
The UV system consisted of long path UV system designed and built by
the University of Denver. The system consisted on a single ended
transmitter/receiver. The system contained UV source (xenon arc lamp),
focusing mirror, retroreflectors, beam splitter, and photodiode array
monochromator. The system was used in both a qualitative and
semi-quantitative mode to measure a variety of aromatic and other compounds
with absorption features in the UV range.
The differential absorption Lidar system was manufactured by TECAN
REMOTE, and consisted of a dual C02 laser each capable of generating emission
lines over the range of 9 to 11 mircrometers. The LASERSAFE system contained
a photoconductive, mercury-cadmium-telluride detector, and lock-in amplifier
for signal processing, and optics were housed in a single ended transmitter/
receiver design. Retroreflectors positioned at a fixed distances from the
transmitter/receiver unit were used to reflect the infrared beams from the
E-31
-------
analytical and reference lasers tuned in a one "on" and one "off"
differential absorption mode.
Ix* EPA's limited evaluations studies, the IR and W systems have
been used to' monitor air emissions upwind, downwind, and cross wind of waste
sites. The purpose of these investigations was to assess air emission impacts
of toxic airborne chemicals emitted from hazardous waste sites. The Hazard
Ranking System (HRS) model was used to rank sites for possible inclusion on
the National Priorities List (NFL). The use of remote sensing offers the
potential for reducing the time and effort required to complete investigations
of this type. A total of 21 contaminants were designated for evaluation based
on previous investigations of the test sites.
The long path FTIR and UV systems were used in a qualitative mode to
first identify various volatile organic compounds emitted from each site, and
then the DIAL system was used to conduct quantitative assessments of those
contaminants in the DIAL library. The long path FTIR and UV systems were also
used in a semi-quantitative mode to determine path averaged concentrations of
toxic airborne chemicals at locations positioned both upwind, downwind, and
cross wind of the designated site areas. Because of shifting winds at the
test site, it was not always possible to position the equipment simultaneously
upwind and downwind of the designated facility.
The results of the limited evaluation suggest that remote sensing
can be used as an effective screening tool (at least in limited applications)
to screen for the presence of fugitive airborne toxic emissions from area
sources. However, it must be recognized that no comparative data was obtained
using alternative point sampling methods, and therefore no statement can be
made regarding precision and accuracy. Other techniques which are limited to
the number and quantity of contaminants which can be monitored (gas filter
correlation or mask filter correlation devices) may have limited applicability
in similar applications. However, Ohese types of devices are generally more
selective. Backscatter absorption gas imaging (BAGI) may have limited
application in identifying the presence of airborne toxic emission sources.
However, this method currently cannot yield quantitative data and lacks
sufficient sensitivity for certain types of fugitive sources.
E-32
-------
In investigations where the source of contamination is unknown, it
is desirable to use techniques such as the long path FTIR and UV systems to
identify possible contaminants of interest. Depending on site specific
factors (i.e., source type, source strength, the presence of background
contamination, meteorology, terrain considerations, etc.), these devices may
be subject to both chemical and atmospheric interferences which could mask the
measurement results. Therefore care must be taken to operate the systems in a
manner so as to minimize the effects of atmospheric inferences.
3.3 Perimeter Monitoring Applications
Remote sensing techniques offer a unique means of providing routine
continuous surveillance along the perimeter of waste sites under investigation
or along the perimeter of petroleum refining and petrochemical manufacturing
facilities. These measurements may be useful in detecting emissions of toxic
airborne chemicals emanating from stationary point or area sources. The
routine surveillance of these chemicals can provide data to assess both
community and worker exposure, and in estimating the magnitude of the release
of such materials. This type of information is useful in assessing the
effectiveness of control devices or the need to assess the effectiveness of
routine maintenance procedures aimed at minimizing the fugitive emissions from
various types of chemical processes, waste handling facilities, etc.
Furthermore, this type of monitoring can be used to warn of the presence of
dangerous releases of acutely toxic or flammable gases or vapors.
,"
Perimeter surveillance monitoring is usually performed for a limited
number of compounds where the sources are known. For applications such as
this, it is vital that the remote sensing device be capable of operating under
a variety of conditions (i.e., fog, rain, dust storms, etc.). Furthermore, it
is necessary that the device be capable of measuring those constituents of
interest both during the day and at night. Thus, active remote sensing
techniques are far more suited for this application than passive devices,
since these device employ controlled light sources. Differential absorption
Lidar (DIAL). long path FTIR, and UV systems offer the greatest potential for
conducting these types of measurements.
E-33
-------
These types of systems (e.g. DIAL, FTIR, and UV), can be easily
adapted for perimeter monitoring applications when operated in the absorption
mode. These devices can be used in single ended transmitter/ receiver
configuration in combination with strategically placed eornereube
retroreflectors. Some systems are configured with a separate transmitter and
receiver positioned apart (e.g., double ended design). In either case, these
devices can be equipped with rotating optical heads to direct a light beam to
a series of reflectance targets (e.g., multiple targeting configuration).
This reduces the number of remote sensing detectors required to conduct
continuous surveillance along the entire perimeter of a facility or site. In
addition, vertical reflector arrays can also be mounted to provide information
about plume dispersion characteristics. Micro-computers are used to control
the sequencing of the sensor head, and collect, process, and store path
averaged concentration measurements for one or more compounds of interest.
The remote sensing system can be wired to alarm systems, and the alarms can be
triggered when the processed signals from the sensor exceed pre-established
path-averaged concentration thresholds.
3.4 Advantages/Disadvantages of Remote Sensing Techniques
There are several obvious advantages to using remote sensing methods
over conventional point sampling and measurement techniques to conduct area
and perimeter surveillance. Remote sensing can yield a great deal of
information over the entire path of interest that could not be obtained
otherwise at a reasonable cost using conventional point source sampling and
measurement techniques. Furthermore, most remote sensing techniques can
provide virtual real-time measurements. This provides rapid feedback of
measurements data to allow the investigator to react to changing conditions in
the field, while avoiding the lengthy delays encountered by conventional
integrated sampling methods that depend on subsequent sophisticated analytical
steps. By measuring over longer path distances, it is possible to provide
surveillance over larger areas. This feature permits greater temporal and
spatial resolution to be obtained.
E-34
-------
Path averaged concentration measurements infer that the concen-
tration of the constituents of interest are uniformly distributed over the
entire path. Depending on the width of the plume and pathlength over which
measurements are made, the concentration of pollutants along a path may not be
uniform. Thus, the actual ambient concentrations measured at sensitive recep-
tors downwind of a source may be different. Thus remote sensing results which
yield path averaged measurements may not be ideal for estimating dose exposure
at discreet locations. Puff releases near the fenceline or other emission
"hot spots" may not be identified using remote sensing systems.
Remote sensing methods are generally effective for measuring a
variety gases and volatile vapors which have absorption features in the infra-
red or ultra-violet spectrum. However, depending on the type of source and
emission characteristics,, current remote sensing techniques may not possess
sufficent senstivity or resolution to identify trace concentrations of consti-
tuents of interest in extremely complex matrices. Thus, it may be necessary
to augment remote sensing methods with other sampling and analytical
techniques to confirm the identity of some gases and vapors.
The support systems for some remote sensing detectors may not be
amenable to routine continuous surveillance. Thus, the operational costs may
be prohibitive. This is particularly true of those systems which may require
liquid cryogens to cool the detector in order to achieve optimum system
performance.
Finally, it must be recognized that remote sensing systems are
currently not in widespread use. Thus, the capabilities and long term
operational effectiveness have yet to be determined. While these systems
offer tremendous potential for measuring trace gases from a variety of
sources, more effort is required at this time to assess the-most suitable
application of this technology. As with any application of measurement
technology, one must be carefully match the capability with overall program
goals. While remote sensing may offer the only practical alternative for some
environmental measurement applications, it may not be well suited for others.
Therefore, as with any well designed measurement program, the limitations of
any measurement methodology must be thoroughly understood and applied
correctly to achieve optimum results.
E-35
-------
APPENDIX F
PHYSICAL AND CHEMICAL PROPERTY DATA
(From ChemDat 7 Documentation)
-------
Tht following properties are given for each chemical (listed by name
and Chemical Abstract Source [CAS] number):
• Density
• Vapor pressure at 25 *C
• Solubility
• Henry's law constant
• Diffusion coefficient in water
• Diffusion coefficient in air
• Boiling point
• Coefficients for the Antoine equation for estimating vapor
pressure at temperatures other than 25 'C.
To estimate vapor pressures at temperatures other than 25 *C, the
Antoine equation coefficients are used with the following equation:
log/jQj Vapor Pressure (mm Hg) - A -
where
A, B, and C • the Antoine equation coefficient
T » temperature in *C.
Two approaches may be used to introduce a new compound and its
properties into CHEWJAT7. First, the data for one compound in
CHEMOAT7 may be replaced with data for the compound of interest in the
F-l
-------
Estimate the biodegradation rate constants using the following
methodology:
Approximate Kfnax fro* available data for %ax for eowpeynds
of siillif structure ind/or functional groups; and
Approximate Kj either by using the following correlation:
KjU/h/g) • 0.135 KQW 0.38
where K^ « octanol -water partitioning coefficient
or fay using the default (average) value for KI, which is
* 1 L/h/g, and then calculate Ks as: Ks
The following properties are given for each chemical (listed by n&m
and Chemical Abstract Source [CAS] number)?
• Density
• Vapor pressure at 25 *C
Solubility
« Henry's law constant
« Diffusion coefficient in water
« Diffusion coefficient in air
• Boiling point
• Coefficients for the Antoine equation for estimating vapor
pressure at temperatures other than 25 *C.
To estimate vapor pressures at temperatures other than 25 *C, the
Antoine equation coefficients are used with the following equation:
log HO) Vapor Pressure (mm Hg) « A - y ^ •
where
A, B, and C • the Antoine equation coefficient
T • temperature in *C.
Two approaches may be used to introduce a new compound and its
properties into CHEMOAT7. First, the data for one compound in
CHEMOAT7 may be replaced with data for the compound of interest in the
F-2
-------
columns specified above. With this approach, the list of compounds in
CHEMOAT7 remains constant at 62. The second approach involves append"
nig the new compound and its properties to the existing list of chemi-
cals in CHEMOAT7. All the equation!/calculations mist then be copied
from one of the existing rows via Lotus 1,2,3 into the appropriate
cells in the new row of the spreadsheet. As mentioned above, the
inclusion in CHEMOAT7 of all or a large part of the chemicals listed
in this appendix could result in increasing the time required to exer-
cise CHEMOAT7 and could prevent its use on some microcomputers.
The properties of interest listed above, with the exception of
the CAS number, ninic those in columns 8, 0-M, and Q of the CHEMOAT7
spreadsheet.
F-3
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.
-------
APPENDIX G
PHYSICAL AND CHEMICAL PROPERTY DATA
FOR 25 COMPOUNDS OF POTENTIAL
CONCERN AND FOR COMPOUND CLASSES
-------
APPENDIX G.
CHEMICAL AND PHYSICAL PROPERTIES FOR 25 COMPOUNDS OF POTENTIAL CONCERN
9MMM.
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Henry's Henry's Law log Kow
Law Henry's Law Constant (octanol -water
Constant Constant (atm) partition coeff
Compound (atm-m/mol) (atm-m3/gmol ) @20 C (9 25 C)
Acetone
Acrylonitrile
Benzene 0.00550
Carbon TetrachloMde 0.03020
Chlorobenzene 0.0039
Chloroform 0.0039
Diehlorobenzene,, e-
Di chlorobenzene. w-
01 chlorobenzene. p-
1.1 Dlchloroethane 0.0056
1.2 Dlchloroethane 0.0014
Ethyl benzene
Isopropy'l Alcohol
Methyl ene Chloride 0.0032
Methyl Ethyl Ketone
Methyl t-Butyl Ether
Napthalene
Phenol
Tetrachl oroethyl ene
Tol uene
1,1,2 Trichloroethane 0.0049
1.1.1 Trichloroethane
Tr1 chl oroethyl ene
Vinyl Chloride 0.19000
o-Xyl ene
m-Xyl ene
p-Xyl ene
2.
8.
5.
3.
3.
3.
1.
3.
1.
5.
1.
6.
1.
2.
4.
7.
1.
4.
2.
6.
7.
1.
9.
8.
5.
5.
5.
50E-05
80E-05
50E-03
OOE-02
93E-03
39E-03
94E-03
61E-03
60E-03
54E-03
20E-03
44E-03
50E-04
24E-03
35E-05
80E-04
18E-03
54E-07
90E-02
68E-03
40E-04
72E-02
10E-03
60E-02
27E-03
20E-03
27E-03
-0.
-0.
24
92
2.40E+02 2.13 8 20 C
1.29E+03 2.
83
2.84 8 20 C
1.70E-H32 1.97 9 20 C
3.
3.
1.90E+02 3.
1.
6.10E+01 1.
3.
38
38
39
79
48
15
-0.16/0.28 calc
1.
0.
1.74-t-O.
3.01/3,
1.
25
26
12
45
46
1.10E+03 2.60 8 20 C
3.40E+02 2.
4.30E+01 2.
4.00E+02 2
5.50E+02 2.
3.55E+05 1.
2.
3
3.
73
47
.5
29
38
77
.2
15
Flash
Point
(C)
-18
0
-11
non-flani
23
non-flam
66
63
65.5
-5
13
15
12
non-flamm@<
-3
-28
88
79
non-flam
4.4
non-flam
non-flam
non-flam
-78.9
17.1
29.4
27.2
Maximum V-L
Water Equil.
Vapor Solubility Constant
Density mg/L K
1
2
3
4
5
5
5
3
3
2
2
2
4
3
5
3
4
4
2
3
3
3
2
.83
.77
5.3
.88
.12
.05
.08
.08
.44
3.4
.66
.07
.93
.42
.42
.24
.83
.14
.63
4.6
.53
.15
.66
.66
.66
1000000
79000
1750
757.
466
8200
100
123
790
5500
8520
152
20000
268000
93000
150
535
4500
1500
1100
2670
175
130
198
6L9
313.1
40.8
49
71.3
17.1
49.8
48.7
2760.3
G-l
-------
APPENDIX G.
CHEMICAL AND PHYSICAL PROPERTIES FOR 25 COMPOUNDS OF POTENTIAL CONCERN
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Molecular
Compound We1 ght
Acetone
Acrylonitrile
Benzene
Carbon Tetrachlorid*
Chlorobenzene
Chloroform
Diehlorobenzene, o-
Dichlorobenzene. m-
Oi chlorobenzene, p-
1,1 Dlchloroethane
1,2 Oichloroethane
Ethyl benzene
Isopropyl Alcohol
Methyl ene Chloride
Methyl Ethyl Ketone
Methyl t-Butyl Ether
Napthalene
Phenol
Tetrachl oroethyl ene
To! uene
1.1.2 Triehloroethane
1,1.1 Trlchloroethane
Trichl oroethyl ene
Vinyl Chloride
o-Xylene
m-Xylene
p-Xyl ene
58
,,53
78
153
112
119
147
147
147
98
98
106
60
84
72
88
118
94
165
92
133
133
131
62
106
106
106
.08
.06
.12
.82
.56
.38
.00
.00
.00
.96
.96
.16
.09
.93
.11
.15
.19
.10
.83
.14
.41
.41
.40
.50
.20
.20
.20
Diffuslvity
Boiling Vapor in Water
Point Pressure (cm2/sec)
(C) (mti Hg) xlOE-05
56.2
77.4
80.1
76.7
131. S
61.2
17i.O
172.0
173.4
57.0
83.5
136.2
82.4
40.1
79.6
55.0
218.0
182.0
121.0
110.7
113.7
75.0
86.7
-13.9
144.0
138.8
138.5
266
114
95.2
113
11.8
208
1.5
2.28
1.2
234
80
10
42.8
400
100
245
0.023
0.0341
19
30
25
123
75
2660
7
8
9.5
1
1
0
0
0
1
0
0
0
0
0
0
1
1
0
0
0
0
0
0
0
0
0
1
1
0
.1400
.3400
.9940
.8840
.9000
.0600
.7900
.7860
.7900
.9880
.9880
.7800
.0400
.6600
.9800
.8026
.7500
.9000
.8200
.8600
.8800
.8800
.9100
.0400
.0000
.7800
roKSmaKSSKSS=333«X=3S3SSSS3SS3
Liquid Odor Oiffusivity
Density Threshold in Air
(g/cm3) (ppm) (cm2/sec)
0
0
0
1
1
1
1
1
1
1
1
0
0
1
0
0
1
1
1
0
1
1
1
0
0
0
0
.790
.810
.879
.595
.170
.489
.310
.290
.290
.256
.256
.870 0,
.790
.327
.820
.758
.140
.070
.624
.840
.320
.330
.400
.908
.880
.860
.860
100
21.4
0.84
21.4
0.21
675
2-4
0.02
15-30
120
3-100
,46-0.60
7.5
25-307
2
0.003
0.016
50
0.17
100
21.4
260
0.17
-1
-0.3
0.1240
0.1220
0.0932
0.0632
0.0730
0.0888
0.0690
0.0692
0.0690
0.0919
0.0907
0.0750
0.0980
0.1000
0.0808
0.0806
0.0590
0.0720
0.0870
0.0792
0.0780
0.0790
0.0900
0.0870
0.0700
G-2
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
EPA-450/l-89-002a
2.
3. RECIPIENT'S ACCESSION NO.
Air/Superfund National Technical Guidance
Study Series. Volume II - Estimation Of
Baseline Air Emissions. At Superfund Sites,
5. REPORT DATE
August 1990
». PERFORMING ORGANIZATION CODE
Bart Eklund and Charles Schmidt
8. PERFORMING ORGANIZATION REPORT NO.
FORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
8501 Mo-Pac Boulevard
Austin, Texas 78759
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-4392
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
OAR, OAQPS
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Interim Final
14. SPONSORING AGENCY CODE
IS. SUPPLEMENTARY NOTES
EPA Project Officers Anne A. Pope
S. ABSTRACT
This report presents available methods for estimating air
emissions at Superfund hazardous waste sites prior to any
remedial action. Methods described include direct emission
measurement techniques, indirect measurements and predictive
emissions modeling. Information is provided on selecting from
among the range of methods available given the associated range
of costs and uncertainties. This report revises and expands an
earlier report, Procedures For Conducting Air Pathway Analyses
For Superfund Activities. Volume II. Estimation Of -Baseline Air
Emissions At Superfund Sites. EPA^-450/1-89-002. It is one in a
series of reports that provide guidance on conducting air pathway
analysis at Superfund hazardous waste sites.
The purpose of this report is to assist EPA Air and Superfund
staff> State Air Superfund;program.staff, Federal and State
remedial and removal contractors, potentially responsible parties
and others in designing, conducting, and reviewing air pathway.
analyses at undisturbed hazardous waste sites.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lOENTIFIERS/OPEN ENOEO TERMS C. COSATI Field/Group
Superfund
Hazardous Waste Sites
Air Pathway Analysis
Emissions
8. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (TttteReportl
Unclassified
21. NO. OF PAGES
390
2O. SECURITY CLASS (Tliis pagel
Unclassified
22. PRICE
F«o« 2220-1 (R«». 4-77). i»«cviou» EDITION i* o«soucre
-------