United States
 Environmental Protection
 Agency
 Hazardous Waste Engineering
 Research Laboratory
 Cincinnati OH 45268
 Research and Development
EPA/600/S2-85/057 July 1985
l\\
Project  Summary
Evaluation  of  Air Emissions
from  Hazardous  Waste  Treat-
ment  Storage,  and  Disposal
Facilities
W. D. Balfour, R. G. Wetherold, and D. L. Lewis
  This study examines the fugitive air
emissions from landfills, surface im-
poundments, storage tanks, containers
(drums), solvent recovery processes,
and land treatment technologies at
Hazardous Waste Disposal Facilities
(HWDFs). The main objective was to de-
velop and demonstrate techniques for
determining air emissions from the
above sources. Various predictive mod-
els for estimating air emissions exist for
some of these sources. These models
have been identified and  evaluated for
applicability to  select HWDFs.  Sam-
pling approaches have been identified
for measuring the air emissions from
these different operations. Procedures
for the collection and  qualitative and
quantitative analysis of the air samples
and the liquid and solid samples taken
in conjunction with the air samples
have also been developed. The result-
ing analytical data have provided gen-
eral information on the level of air emis-
sions from the sources studied. This
document summarizes  the findings
from each of four HWDFs tested, com-
paring and contrasting the measured
and predicted emission results and the
experiences gained in using the various
sampling approaches.

  This Project Summary was devel-
oped by EPA's Hazardous Waste Engi-
neering Research Laboratory, Cincin-
nati, OH, to announce  key findings of
the research project that  is fully docu-
mented in a separate report of the same
title (see Project Report ordering infor-
mation at back).
Introduction

  The Office of Solid Waste (OSW) is
required, under Executive Order 12291,
to conduct a Regulatory Impact Analy-
sis (RIA) that will examine costs and
benefits for various alternatives to con-
trol air emissions from the treatment,
storage, and disposal operations at haz-
ardous  waste disposal  facilities
(HWDFs). This study has examined the
fugitive air emissions from landfills,
surface impoundments, storage tanks,
containers (drums), solvent recovery
processes, and land treatment tech-
nologies at HWDFs.
  The main objective of this study was
to develop and demonstrate techniques
for determining air emissions from the
above HWDF technologies (sources).
Various predictive models for estimat-
ing air emissions exist for some of these
sources. These models have been iden-
tified and evaluated for applicability to
select HWDFs. Sampling approaches
have  been identified for measuring the
air emissions from these treatment,
storage, and disposal operations. Pro-
cedures for the collection and qualita-
tive and quantitative analysis of the air
samples and the liquid and solid sam-
ples taken in conjunction with the air
samples have  been developed. The
resulting analytical data have provided
general information on the level of air
emissions from the sources studied.
Specific information  has been pre-
sented in  separate Data Volumes for
each of the four sites tested. This docu-
ment summarizes the findings from

-------
each of these sites, comparing and con-
trasting the measured and  predicted
emission results and the  experiences
gained in using the  various sampling
approaches.

Predictive Models for Compari-
son to Air Emission Measure-
ments
  Reviews of models for estimating air
emissions from hazardous waste treat-
ment, storage, and disposal facilities
have been  provided to EPA  by Radian
and GCA. GCA has recommended those
models shown in Table 1 for use in pre-
dicting emissions from various  treat-
ment, storage, and disposal facilities.
Data were collected at the sites for input
to the models. Where possible, mea-
sured values were used as input. Where
measured values were not possible, in-
put values were obtained from records,
literature  values, engineering esti-
mates, etc.

Sampling Approaches for Mea-
suring Air Emissions
  The sampling approaches for mea-
suring air  emissions from treatment,
storage, and disposal facilities (TSDFs)
include:
  • emission isolation flux chamber,
  • vent sampling,
  • concentration-profile,
  • transect technique, and
  • mass balance.
Table 2  presents the sampling ap-
proaches identified as applicable to var-
ious treatment, storage,  and disposal
facilities.

Sampling Sites
  Six sites were investigated during an
initial pretest  site survey. The survey
was designed to select those sites that
had TSDFs most suitable for testing.
The recommendations for field testing
and  results from the initial sampling
and analytical  efforts are found  in the
pretest site survey report. Four of these
six sites were tested, including Sites 2,
4, 5, and 6.

Testing Program
   The field testing conducted at the
sites is shown in Table 3. The field test-
ing was performed during the following
periods during the Fall of 1983.
   • Site 5 - September 30 - October 11,
   • Site 4 - October 11 and 12,
   • Site 6 - October 24-28, and
   • Site 2 - November 14-18.
A systems and performance audit of the
Table 1.    Recommended Air Emissions Models for Hazardous Waste Disposal Facilities

      Source                                     Model(s)
Landfill
Landtreatment
Surface Impoundment
Open Tank
Storage Pile


Fixed Roof Tanks



Floating Roof Tanks
Farmer, et al (1978) - for Covered Landfills
Thibodeaux (1980) - Landfill Equation-without internal
  gas generation
Thibodeaux (1981) - Landfill Equation-with internal
  gas generation

Hartley Model (1969)
Thibodeaux-Hwang (1982)

Mackay and Leinonen (1975) - Unsteady-State Predic-
  tive Model for Nonaerated Surface Impoundments
Thibodeaux, Parker, and Heck (1981) - Steady-State
  Predictive Model for Nonaerated and Aerated Sur-
  face Impoundments

Thibodeaux (1980) - Aerated Surface Impoundment
  (ASI) Model
Hwang (1970) - Activated Sludge Surface Aeration
  (ASSA) Model
Freeman (1980) - Diffused Air Activated Sludge (DASS)
  Model

Midwest Research Institute Emission Factor Equations
  for Storage Piles

API (1962), modified by TRW/EPA, Fixed Roof Tank
  Breathing Losses
API (1962) - Fixed Roof Tank Working Losses

API (1980) - Evaporation Loss from External Floating
  Roof Tanks
EPA/API (1981) - Standing Storage Losses from Exter-
  nal Floating Roof Tanks
EPA/API (1981) - Standing Storage Losses from Inter-
  nal Floating Roof Tanks
on-site sampling and analytical  activi-
ties was conducted by Radian's Quality
Assurance Coordinator on October 5-7.

Conclusions
  The field testing performed in this
program has provided data on the air
emission rates from a  variety of sources
within hazardous waste treatment, stor-
age, and disposal facilities (TSDFs). Air
emission  rates  were  measured using
various approaches and predicted using
existing models. Neither the measure-
ment approaches nor the  predictive
models have been validated, and as
such, this program represents a demon-
stration of these approaches for mea-
suring/modeling erpissions from  TSDF
sources. The measured and predicted
emission rates  have been  compared
throughout this report as a relative com-
parison only. The accuracy of the mea-
sured and the predictive procedures are
not established. The  experiences
gained during  this program should,
however, provide a basis for future field
testing of TSDFs.
  A summary of the results of the emis-
         sion rate measurements from the vari-
         ous TSDFs tested is given  in Table 4.
         Only the total nonmethane hydrocar-
         bon (TNMHC) emissions are included in
         this table. Results are provided for both
         the entire surface area (kg-C/day) and
         per unit area (kg-C/hectare-day). The
         emission rates presented in the table
         represent an average of all the measure-
         ments for a given source. The measure-
         ments were made over a relatively short
         period  of time and  under specific pro-
         cess operating and meteorological con-
         ditions.  For these reasons, caution
         should be used in attempting to extrap-
         olate these data to sources at  other
         TSDFs, or for longer time periods (i.e.,
         annual averages).
           The highest emissions measured at
         an active landfill were encountered dur-
         ing active dumping of the waste (23.1
         kg-C/day). Emission rates were  lower
         (1-10 kg-C/day) in areas of the landfills
         which did not have active dumping con-
         current with the measurements. All but
         one  of the  landfills tested were very
         large with multiple cells. Because of the
         large exposed surface areas, the emis-

-------
sions for the total source were similar in
magnitude  to the surface  impound-
ments. No measurable emissions were
detected through the cover of the inac-
tive landfills tested. Both inactive land-
fills did however have vents from which
emissions were detected (<0.01 kg-
                           C/day). Emissions from the vents were
                           not constant, rather they occurred as
                           puffs with no specific frequency of oc-
                           currence.
                             A  variety of surface impoundments
                           were tested,  including small  surface
                           area receiving ponds (high  liquid con-
                                 centrations) and large surface area pol-
                                 ishing  ponds (now liquid concentra-
                                 tions). As expected, the emissions from
                                 the receiving ponds were higher (order
                                 of magnitude) than the polishing ponds
                                 on a  per surface area basis. Emissions
                                 from the total sources were more simi-
Table 2.  Summary of Emission Measurement Approaches for Selected Activities within a Hazardous Waste Disposal Facility


                                                                                                   Comments
Activity
Emission Measurement
     Approach3
Treatment Plants
1)  Physical, biological and/or chemical
    treatment units, including continuous
    mixing in open tanks
2)  Spraying/aeration and spray irrigation
3)  Distillation and cracking/refining

Storage
4)  Open tanks
5)  Surface impoundments
6)  Evaporation ponds or tanks
    (unheated and heated)
7)  Drum recycling operations
8)   Spent drum storage

Disposal Facilities
9)   Landfills (active and inactive)
W) Landtreatment
Fugitive Sources
71)  Vacuum pumps used on tank trucks
                                Emission isolation flux chamber

                                Mass balance

                                Transect technique
                                Vent sampling
                                Transect technique
                                Vent sampling
                                See 1) above
                                Concentration-profile technique

                                Transect technique
                                Emission isolation flux chamber

                                Mass balance

                                See 1) above

                                Transect technique

                                Emission isolation flux chamber
                                See 7) above


                                Transect technique

                                Emission isolation flux chamber
                                Vent sampling
                                Emission isolation flux chamber
                                Mass balance

                                Transect technique
                                Vent sampling
                                Transect technique
                                   Open tanks; little or no surface disturb-
                                   ance
                                   Batch process or steady-state operation/
                                   process
                                   Requires minimal interferences from other
                                   emission sources; applicable when
                                   surface is highly agitated
                                   Closed tanks
                                   Requires minimal interferences from other
                                   sources; must consider aerosal vs. vapor
                                   during sampling collection
                                  Must meet criteria for the micro-
                                  meteorological model
                                  Requires minimal interferences from other
                                  emission sources; not applicable to large
                                  impoundments
                                  Small surface impoundments and/or
                                  minimal surface disturbances
                                  Batch process or steady-state operation/
                                  process
                                  Requires minimal interferences from other
                                  emission sources
                                  Bagging of single drums only
                                  Requires minimal interferences from other
                                  emission sources
                                  Covered landfill only
                                  Covered landfill with gas collection system

                                  Requires some knowledge of biodegrada-
                                  tion rate
                                  Requires minimal interferences from other
                                  emission sources
                                                                                     Requires minimal interferences from other
                                                                                     emission sources
3Description of emission measurement approaches:
  Emission isolation flux chamber - direct emission measurement, no interference from other emission sources.
  Mass balance - indirect emission measurement based upon difference in bulk component concentrations.
  Transect technique - indirect emission measurement based upon ambient concentrations downwind from source, other emission sources
                               can interfere with measurements.
  Vent sampling - direct emission measurement, no interferences from other emission sources.
  Concentration-profile technique - indirect emission measurement based upon ambient concentrations immediately above surface,
                               minimal interference from other emission sources as long as a concentration profile can be measured.

-------
Table 3.
Site
2




4




5

Summary of Field Testing
Source
Landfill (active)


Landtreatment

Chemical Landfill D
(active)
Chemical Landfill C
(inactive)

Wastewater treatment.
Reducing Lagoon 1
Wastewater treatment,
Oxiriirinn 1 aannn 2
Performed
Sampling Approach
Transect technique and
Emission isolation flux
chamber
Emission isolation flux
chamber and
Concentration-profile
technioue

Flux chamber

Flux chamber


Flux chamber
Flux chamber
Model
No specific model
applicable

Thibodeaux-Hwang
(1982), Hartley
(1969)

No specific model
applicable
No specific model
applicable

Thibodeaux, Parker
and Heck (1983)
Thibodeaux, Parker
anri Her.k /IflR.lt
ity control procedures were readily per-
formed. The statistical sampling ap-
proach appears suited to the sampled
ponds, landfarm, and some landfills.
However, certain of the landfills were
quite large and heterogeneous in na-
ture, making the overall representative-
ness of the limited data obtained sus-
pect in these cases. In general, very
good correlations were observed be-
tween all components detected from
the chamber and the volatile compo-
nents in the corresponding liquids and
solids (waste). The variability in the
emission rates determined using the
flux chamber was typically much less
than the transect, concentration-profile,
or predicted emission rates.
        Wastewater treatment,
        Holding Pond 6
        Hazardous, non-hazardous
        drum storage building
        Chemical Landfill 10
        (active)

        Chemical Landfill 7
        (inactive)

        Distillation Process

        Closed Tanks (vented)
        Drum Storage and
        Handling3
        Spray Evaporation Pondb
Concentration-profile
Flux chamber
Vent sampling

Transect technique
Flux chamber

Flux chamber
Vent sampling

Mass balance

Vent sampling
Transect technique

Transect technique
Thibodeaux, Parker
and Heck (1983)
No specific model
applicable
Individual cells,
Farmer, et al (1978)
Thibodeaux (1980)
No specific model
applicable

No specific model
applicable
API/EPA (1962)
No specific model
applicable
No specific model
applicable
3Testing scheduled, but not performed due to meteorological conditions; qualitative data
 obtained.
bLimited testing performed due to meteorological conditions.
lar due to the differences in size of the
ponds, with the receiving ponds (1-7 kg-
C/day) being somewhat higher than the
polishing ponds (0.4-1.4 kg-C/day).
  The highest  emissions measured
were for the land  treatment of oily
wastes. Depending on the approach
used for making the measurement and
the time that the measurement was
made after initial  spreading of the
waste, the emission rates ranged from
3-60 kg-C/day. The waste  was surface
spread and included daily tilling. Emis-
sions tended to decrease rapidly follow-
ing the initial application and to in-
crease slightly with each day's tilling.
  Emissions  during solvent recovery
operations for 1,1,1-trichloroethane and
methylethylketone (MEK) were at nomi-
nally 1% of the throughput for the distil-
lation process. Losses (emissions) dur-
ing washing of the 1,1,1-trichloroethane
were substantially greater (16.7%).
Emissions from a drum storage build-
ing were measured at 0.2 kg-C/day. Sur-
veys around outside drum storage
    areas showed measurable TNMHC con-
    centrations, but no emission rates were
    determined.  Measurements  of  the
    breathing losses (emissions) from
    fixed-roof storage tanks were at-
    tempted, but no measurable flow from
    the vents could be detected.
      A number of field sampling tech-
    niques were used  in this study includ-
    ing:
      • emission isolation flux chamber
      • transect technique
      • concentration-profile technique
      • vent sampling
      • mass balance
    As a result of the experience gained in
    using these techniques, several general
    statements on the use and limitations of
    each of the approaches can be made.
      The emission isolation flux chamber
    technique was  simple and  straight-
    forward to execute in the field. No spe-
    cific  meteorological conditions pre-
    vented sampling, with the exception of
    high winds during tethered operation at
    some ponds. Field calibration and qual-
  The transect technique required more
instrumentation and was more labor in-
tensive than the emission isolation flux
chamber. The transect technique is very
dependent upon and very vulnerable to
ambient meteorological conditions, the
physical surroundings about the mea-
sured source, and the configuration of
the source itself. During the testing peri-
ods, testing was often prevented due to
unacceptable atmospheric stabilities,
high/low wind speeds, variable wind di-
rection, and wrong wind direction.
Transect testing was precluded at some
sites because of the proximity of obsta-
cles that produced  air turbulence and
prevented proper  plume formation.
These experiences  emphasize the  ex-
tent  to  which meteorological depen-
dence can escalate the cost and ability
of obtaining emission data  using  the
transect technique.  In general, the  un-
certainty associated with the  emission
rates  estimated  by the  transect tech-
nique are greater than those measured
by other methods.
  The concentration-profile  technique
required the most instrumentation and
was the most labor intensive of  the
three sampling approaches. It too is de-
pendent on ambient meteorological
conditions and physical  configuration
of the source. During the field testing,
unsatisfactory meteorological  condi-
tions resulted in several days'  delay
and, in some  cases,  samples  of
questionable  validity. Both the
concentration-profile and transect tech-
niques require analysis of air samples
which are at least an order of magnitude
more dilute than corresponding flux
chamber samples. This fact impacts the
analytical  procedures which can  be
used  with these approaches and  the
level of compounds which may be de-

-------
tected.  The method is also  limited to
flat, relatively large area sources. The
variability in the emission rates deter-
mined  using the concentration-profile
technique  was  typically greater than
with the flux chamber, but better than
the transect technique.
   It is generally expected that the flux
chamber will result in lower  measured
emission  rate than the  concentration-
profile technique, due to the absence of
wind effects in the flux chamber. In
              comparing the emission rates  deter-
              mined by both methods at the landtreat-
              ment area. Site 2,  the  concentration-
              profile values were  indeed higher than
              the flux chamber values. The difference,
              however, may have also been due  in
              part to  the time dependence of the
              emission rates from the  landtreatment
              area and the fact that the concentration-
              profile measurements were made fol-
              lowing tilling (which is expected to tem-
              porarily  increase the emission  rate).
 Table 4.   Emission Rates of Total Nonmethane Hydrocarbons from TSDF
          Sources Measured Using Various Sampling Approaches
                                                         Emission Rate
      TSDF Source
 Sampling Approach     (Kg-C/hectare-day)    (Kg-C/day)
Active Landfill
Site 5-Landfill 10
Site 4-Landfill D

Site 2-Landfill Q
Inactive Landfill
Site 5-Landfill 7
Site 4-Landfill C
Surface Impoundments
Site 5-Lagoon 1

Site 5-Lagoon 2

Site 5-Pond 6


Site 6-Pond 3

Solvent Recovery
Site 6-1,1,1-Trichloroethane
Site 6-MEK

Landtreatment
Site 2-Landtreatment
Drum Storage Building
Site 5

Storage Tanks
Site 6
Transect Technique         3.8, 9.2a
Emission Isolation Flux      4.5b, 13b
Chamber
Emission Isolation Flux      4.1b
Chamber
Emission Isolation Flux      0.8b
Chamber
Emission Isolation Flux
Chamber
Vent Sampling
Emission Isolation Flux
Chamber
Vent Sampling
Emission Isolation Flux      10
Chamber
Emission Isolation Flux      49
Chamber
Emission Isolation Flux      2.7
Chamber
Concentration-Profile        0.8
Transect Technique         54d
Mass Balance
Mass Balance
                             e, 16.7%f
                          Emission Isolation Flux     626-539
                          Chamber
                          Concentration-Profile       1080-831h
Vent Sampling


Vent Sampling
                                          9.5, 23.1
                                          1.1b,8.2b

                                           1.6b

                                           0.015b
                                           <0.01

                                           <0.001



                                           1.4

                                           7.1

                                           1.4

                                           0.4
                                           2.7d
                                           35-38

                                         60.5-46.5"


                                           0.2


                                           
-------
between predicted and measured emis-
sion rates in half of the cases examined
for Lagoon  1. In all other cases, the pre-
dicted rate  was greater than the mea-
sured rate for Lagoon 1. For Lagoon 2,
the predicted rate was orders of magni-
tude greater than the measured  rate in
all cases. This discrepancy is attributed
to problems in modeling the sludge/oil/
aqueous  surface encountered for this
lagoon.  Predicted emissions were
compared to emission  rates for Hold-
ing Pond  6 measured using both
concentration-profile and flux  chamber
techniques. In general, the predicted
rates are statistically greater than those
measured by the concentration-profile
technique  and  less than  those mea-
sured by the flux chamber.
  The Thibodeaux, Parker, and Heck air
emission model was also used to pre-
dict emissions from the spray  evapora-
tion pond at Site 6 due to vaporization
of the liquid surface. The  model does
not include emissions due to vaporiza-
tion from the spray nozzles and  would
therefore be expected to predict lower
emission rates than would  be mea-
sured. This was not the case, however.
Due to the  poor quality of the transect
data, the measured data are perceived
to have underestimated the true emis-
sion rate. However, it should  be noted
that both the predicted and measured
emission rates had very broad confi-
dence intervals, which both  included
the corresponding  mean values and a
zero emission  rate. The imprecision of
the predicted values is attributed to the
wide variability in the concentrations of
compounds found in the pond  samples.
  The Thibodeaux-Hwang  air  emission
model was used to predict emissions
from the landfarm. The  predicted emis-
sions show a time dependence, with the
emission rate decreasing exponentially.
The effect of retilling the area is to in-
crease emissions initially; however, the
emission rate quickly  returns  to the
range of values predicted if no tilling
had occurred.  The predicted emission
rates were compared with the emission
rates measured using the flux  chamber
and concentration-profile techniques. In
general, the predicted emissions agreed
with the measured emissions for  spe-
cific compounds, but did not agree with
the compound  classes  and total non-
methane  hydrocarbon emission rates.
In all cases, the predicted emission rates
were significantly greater than  the mea-
sured emission rates for the compound
classes and total nonmethane hydrocar-
bons. This discrepancy may be caused,
at least in part, by the composite param-
eters which were  used for the com-
pound classes. The Thibodeaux-Hwang
model was developed for single compo-
nents. To apply the model to multicom-
ponent compound groups or classes, a
set  of parameters  was developed  for
each group by averaging the parameter
values of the more  prominent com-
pounds contained within the group. A
more sophisticated approach may be
needed to extend the model to multi-
component systems.
  Existing predictive  models were  not
used to estimate emissions from the in-
active chemical landfills in light of  the
heterogeneous nature of the waste and
inability of the  existing  models to  ac-
count for vented emissions.
  The API imperical model  for breath-
ing  losses was used to predict breathing
losses from four of the fixed-roof tanks
at Site 6. The annual emission rates pre-
dicted by the API model were then used
to calculate  flow rates  through the
vents. Additionally, vent flow rates were
calculated based upon  vapor displace-
ment calculations. The flow rates calcu-
lated by each method are quite similar,
and  all were at or below  the detection
limits for the flow measurement tech-
niques used on site. The field observa-
tions and predicted emission rates from
the fixed-roof tanks are therefore con-
sistent with each other.
  In summary, the Thibodeaux, Parker,
and  Heck surface impoundment model
appears to be generally  applicable to in-
dividual compounds in  impoundments
having no oil on the surface and/or no
mechanical  sprays. The  Thibodeaux-
Hwang landtreatment mode! appears to
adequately describe the  emissions of
single compounds. However, it  was not
found to be satisfactory for compound
classes or total  NMHC emissions.
   W. D. Balfour, R. G. Wetherold, and D. L Lewis are with Radian Corporation,
  Austin, TX 78766.
  Paul dePercin is the EPA Project Officer (see below).
   The complete report, entitled "Evaluation of A ir Emissions from Hazardous Waste
    Treatment, Storage, and Disposal Facilities," (Order No. PB 85-203 792/AS;
    Cost: $11.50, subject to change) will be available only from:
          National Technical Information Service
          5285 Port Royal Road
          Springfield, VA 22161
          Telephone: 703-487-4650
   The EPA Project Officer can be contacted at:
          Hazardous Waste Engineering Research Laboratory
          U.S. Environmental Protection Agency
          Cincinnati, OH 45268
                                                                           U. S. GOVERNMENT PRINTING OFFICE: 1985/559-111/20624

-------
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
     BULK RATE
POSTAGE & FEES PAID
        EPA
   PERMIT No. G-35
Official Business
Penalty for Private Use S300
EPA/600/S2-85/057

-------