1992-06-30 PB92228600 Amoco Yorktown - EPA Pollution Prevention Project Volume II - Air Quality Data

PB92228600
1111111111111111111111111111111
Amoco - U.S. EPA

Pollution Prevention Project
Yorktown, Virginia
Air Quality Data

Volume II
&EPA
REPRODUCED BY, NJJI

u.s. Department of Commerce
National Technical Information Service
Springfield, Virginia 22161
Form Approved
REPORT DOCUMENTATION PAGE OM8 No. 0704-0788
Pt'~I,,:, ~~""~:-"'I.4 ~q,den for this cOllectiOn of InfOfl'!'latlon 1\ e-stlmated to a"era9~ 1 hour l)e'r response, Including the' tlm~ for reYIe-wlng Instructlon~. !loearct"ung eXisting data sourc~.
.... n9 Ihe (Oliectlon of InformatiOn. Send comments r~arding thi, burden ~llmale or any otller a_ct at th"
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' ~(,.,. ,""',lIlalnlng Ih~ data ne~~. and C()mpletJn9 ana rey.~
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2• REPORT DATE
June 30, 1992
13• REPORT TYPE
Final
AND DATES COVERED
March 25, 1991 - June, 1992
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Amoco/EPA Pollution Prevention Project
Air Quality Data Volume II
6. AUTHOR(S)
D.N. Blewitt)
J.W. Keating) Amoco Corporation
J.F. Yohn )
7. PERfORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION
Amoco Corporation - Environmental Affairs and Safety Dept REPORT NUMBER
200 E. Randolph Drive
Chicago, IL 60601
9. SPONSORING I MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORING I MONITORING

United States Environmental Protection Agency AGENCY REPORT NUMBER
401 M Street, SW ~vashington DC 25460
Amoco Corporation
200 E. Randolph Dr., Chicago, IL 60601
11. SUPPLEMENTARY NOTES
Part of multi-volume set documenting Amoco/USEPA Pollution Prevention Project
12a. DISTRIBUTION I AVAILABILITY STATEMENT 12b. DISTRIBUTION CODE
13. ABSTRACT (MaxImum 100 words)

~s part of the Amoco/USEPA Pollution Prevention Project, on air quality evaluation of
Amoco Oil Company's Yorktown Virginia Refinery was conducted. This document defines
~aseline air quality in terms of air emissions and ambient air quality. This baseline
~as used to eVciluate potential impact of different pollution prevention options.
~hree objects of this study were to: 1) Quantify current air emissions from the
facility; 2) Quantify ambient air quality impacts of these emissions; and 3) identify
Ibenefits of implementing pollution prevention alternatives or additional control
measures.
Extensive computer modeling of the airshmimmediately around the Refinery was con-
ducted using the ISC Short Term model with approximately 80 on-site emission sources
and 8700 hourly meteorological data points.
14. SUBJECT TERMS 15. NUMBER OF PAGES

Pollution Prevention, Oil REfining, Yorktmm, Air pollution,
Air Quality, Air emissions (industrial), computer modeling, 16. PRICE CODE
Amoco.
17. SECURITY CLASSIFICATION ,18. SECURITY CLASSIFICATION 19. SECURITY CLASSIFICATION 20. LIMITATION OF ABSTRACT
OF REPORT OF THIS PAGE OF ABSTRACT
Unclassified _" Unclassified Unclassified SAR
I -
NSN 7540-01·280-5500 Standard Form 298 (Rev. 2-89)
Prescrobed by ... NSI Std. l39·18
298·102
AN AIR QUALIT1i EVALUATION OF THE AMOCO YORKTOWN REFINERY
AS PART OF TH]~ AMOCO--USEPA POLLUTION PREVENTION PROJECT
Amoco corporation
Environment, Health and Safety Department
Prepared by:
D. N. Blewitt, J. W. Keating and J. F. John
July 30, 1992

Table of contents
PAGE
List of Figures iii

List of ~rables v
Foreword viii
Executive Summary x
1.0 INTRODuc'rION 1
2.0 SOURCE SAMPLING 3

2.1 API Separator Measurements 5
2.2 Coker Pond Measurement 14
2.3 Landfarm Measurements 19
2.4 Sewer Vent Measurements 24
3.0 AMBIENT MEASUREMENTS 30
3.1 Description of the Air Quality 32
Monitoring Program
3.1.1 Charcoal Tube Sampling 32
3.1. 2 Evacuated Canister Sampling 36
3.2 Monitoring Results 37
3.2,1 Charcoal Samplers 37
3 •.2.2 Monitoring Results from Wind 58
Direction TO-14 Samplers
3.3 Quality 1\ssurance 62
3.4 Meteorological Monitoring 65
3.5 Tracer Experiments 68
4.0 EMISSION INVENTORY 69

4.1 Hydrocarbon Air Toxics Emission Inventory 69
4.1.1 API Separator 71
4.1.2 Barge Loading 73
4.1.3 Blowdown Stacks 73
4.1.4 Coker Pond 75
4.1.5 Cooling Tower 77
4.1.6 Inactive Landfarm 78
4.1.7 Loading Rack 78
4.1. 8 Proc:ess Fugitives 78
4 . 1. 9 SewE~r Vents 83
4.1.10 Tanks 85
4.1.11 Wastewater Tank 86
4.1.12 Summary of VOC Emissions 86
4.2 Emissions of Criteria Pollutants 92
5.0 ACCURACY OF THE EMISSION INVENTORY FOR BTEX 94

5.1 Modeling Methodology 95
5.1.1 Process Fugitives 95
5.1. 2 Storage Tanks 99
5.1. 3 API Separator, Coker Pond and Landfarm 99
5.1.4 Point Sources 101
i
Table of contents cont.
5.2 Methodology Used to Compare Measured and 103

Predicted Concentrations
5.3 Discussion of Results 110
5.3.1 site A1 110
5.3.2 site A2 119
5.3.3 sites A3 and A4 126
5.3.4 sites A5 and A6 136
5.4 Conclusions Regarding Accuracy of the 146
Inventory for BTEX
6.0 EXPOSURE MODELING 155

6.1 Exposure Modeling for BTEX 156
6.1.1 Methodology 156
6.1. 2 Results 158
6.2 Impacts from Other SARA Chemicals 181
6.2.2 Results 182
6.3 Modeling of criteria Pollutants 194
6.3.2 Results 198
6.4 Modeling of Other Chemicals 202
6.4.2 Results 203
7.0 CONCLUSIONS 205

7.1 Emission Inventory Development 205
7.2 Ambient Sampling Program 206
7.3 Accuracy of the Emission Inventory 206
7.4 Ambient Air Quality 207
8.0 REFERENClllS 209
APPENDICES
Appendix A Analyses of Tracer Data

Appendix B* ISCST Modeling of BTEX Monitoring Data
Appendix c* Summary of Modeling and Monitoring comparisons
Appendix D* Annual Modeling Analyses for BTEX
Appendix E* Culpability Analyses for BTEX
Appendix F* Annual Modeling Analyses for SARA Chemicals
Appendix G* Culpability Analyses for SARA Chemicals
Appendix II* Modeling Analyses for criteria Pollutants
Appendix I Summary of Wind Persistence
Appendix ~r Responses to USEPA Comments
*Appendix included in a separate document.
ii
List of Figures
PAGE
1 Comparison of VOC Emissions Determined from xii

this S1:udy to the Previous Inventory
2-1 Cutaway Diagram of Flux Chamber and Support 7
Equipment
2-2 Sampling Approach for API Separator 8
2-3 Emissions; from the API Separator 13
2-4 Sampling Arrangement Used to Monitor the Coker 15
Quenching Pond Inlet
2-5 Emissions from Coker Blowdown Pond 20
2-6 Emissions from the Inactive Landfarm 23
2-7 Sampling Design for the Sewer Vent Direct 25
Measurements
3-1 Sampling Location 35
3-2 Benzene 50
3-3 Toluene 51
3-4 Ethy lben2: ene 52
3-5 Xylene 53
4-1 VOC Emissions from this study 89
4-2 VOC Emissions from SARA Inventory 89
5-1 Receptor Grid Used in Comparing Modeled 106

to Observed Impacts
5-2 Comparison of Predicted and Observed 111
Concentrations for BTEX at Site A1
Concentrations for BTEX at site A2
Concent.rations for BTEX at Site A3
5-5 comparison of Predicted and Observed 128
Concentrations for BTEX at site A4
5-7 comparison of Predicted and Observed 139
5-8 Histogram of Benzene Emissions 149
5-9 Histogram of Toluene Emissions 150
5-10 Histogram of Ethylbenzene Emissions 152
5-11 Histogram of Xylene Emissions 153
6-1 Coarse Grid 159
6-2 Fine Grid 160
6-3 Benzene Annual Average Concentrations 162
6-4 Toluene Annual Average Concentrations 163
iii
List of Figures Cont.
6-5 Ethylben:z:ene Annual Average Concentrations 164
6-6 Xylene Annual Average Concentrations 165
6-7 Source Culpability for Benzene 168
6-8 Source Culpability for Toluene 170
6-9 Source Culpability for Ethylbenzene 172
6-10 Source Culpability for Xylene 174
6-11 Histogram of Benzene for sensitivity Analysis 178
6-12 Annual Average Benzene Concentrations for the 179
Emission Inventory Sensitivity Cases
6-13 Source Culpability for Butadiene 185
6-14 Source Culpability for Cyclohexane 187
6-15 Source Culpability for Naphthalene 188
6-16 Source Culpability for Trimethylbenzene 190
6-17 Source Culpability for MTBE 192
6-18 Source Culpability for Propylene 193
6-19 Source Culpability for Ethylene
iv
List of Tables
PAGE
2-1 Speciatec:i Hydrocarbon Emissions from the 10-11

API Separator
2-2 speciated Emissions from Coker Quench Pond 16
(Quench Area)
2-3 speciated Emissions from Coker Quench Pond 17-18
(Overflow Area)
2-4 speciated Emissions from the Landfarm 22
2-5 Summary of Emissions Measurements 27
from Sewer Vents
2-6 Summary (:>f Sewer Vent Emissions from the 28
Yorktown Refinery
3-1 Summary of Net BTEX Concentrations 38-40
for Sampling Day 1
for Sampling Day 2
3-3 Summary of Net BTEX Concentrations 43
for Sampling Day 3
for Sampling Day 4
3-5 Summary ()f Net BTEX Concentrations 46
for Sampling Day 5
3-6 Summary ()f Net Concentration Measurements 60-61
Using USEPA TO-14 Sampling Method
3-7 Ratio of Ambient Measurements to Toluene 63-64
3-8 Accuracy and Precision Estimates for the 66
2-Hour Charcoal Tube Sampling
3-9 Accuracy and Precision Estimates for TO-14 67
Sampling
4-1 Basis of Emission Estimates 70
4-2 Emissions from Barge Loading 74
4-3 composition Breakdown of BTEX and Non-BTEX VOC 76
Emissions from the Blowdown Stacks
4-4 Emissions from Cooling Tower 79
4-5 Emissions from Product Loading Rack 80
4-6 Emissions from Process Fugitives 82
4-7 VOC Emissions for Storage Tanks 87-87a
4-8 Emissionsl from wastewater Tank 88
4-9 Summary of Air Emissions in Region Near the 91
Yorktown Refinery
4-10 Summary of Criteria Pollutant Emissions (TPY) 93
5-1 ISCST Control Switch Initialization 96

5-2 Fugitive Volume Sources 98
5-3 Tank Area Sources 100
5-4 Ground-Based Area Sources 102
5-5 Point SOUlrces 104
v
List of Tables cont.
PAGE
5-6 Summary of Comparisons of Predicted and 113

Observed Concentrations for site A1
5-7 Average Modeled Contribution for Site A1 115
5-8 Average Modeled Concentrations, Measured 116
Concentrations, and Cp/Co Ratios During
Periods of Coker Pond, Blowdown Stack and
Sewer Vent Impacts at Site A1
5-9 Summary of Comparison of Predicted and 121
Observed Concentrations for Site A2
5-10 Average Modeled Source Contribution for 123
Site A2
Periods of Sewers, Blowdown Stack and Tank
Impacts at Site A2
5-12 Summary of Comparison of Predicted and Observed 129
Concentrations for Site A3 and A4
5-13 Averaged Modeled Source Contribution for 132
Site A3
Site A4
Periods of Sewers, Blowdown Stack and Tank
Impacts at site A3
5-16 Average lModeled Concentrations, Measured 135
Concen'trations, and Cp/Co Ratios During
Periods of Tank Impacts at site A4
5-17 summary lof Comparison of Predicted and Observed 140
Concen'trations for Sites A5 and A6
Site A5
5-19 Averaged Modeled Source contribution for 143
site A6
Concentrations, and Cp/Co Ratios During API
Separator and water Tank at site A5
5-21 Average Modeled concentrations, Measured 145
concentrations, and Cp/Co Ratios During API
Separa1:or and Sewer Impacts at site A6
6-1 Maximum l~nnual Average Predicted Concentrations 166
for the Yorktown Refinery for BTEX Chemicals
6-2 Comparis()n of Annual Average Predicted Impacts 176
to Typical Measured Concentrations for
Different Types of Environments for BTEX
Chemicclls
vi
List of Tables cont.
6-3 Area contained within the Benzene 0.12 and 1.2 180
ug/m**3 Isopleth
6-4 Maximum Jlmnual Average Predicted Concentrations 183
for the Yorktown Refinery SARA Chemicals
6-5 Comparison of Annual Average Predicted Impacts 196
to Typical Measured Concentrations for
Different types of Environments for SARA
Chemicals
6-6 Criteria Pollution Source Emission Parameters 199
for the Yorktown Refinery
6-7 Criteria Pollutant Emission Rates from the 200
Yorktown Refinery
6-8 Comparisons of Maximum Predicted Impacts of 201
criteri.a Pollutants to NAAQS
6-9 Maximum Annual Average Predicted Concentrations 204
for other Chemicals
vii
:roreword
This is the second volume of air quality sampling and analysis

work completed at Amoco oil Company's Yorktown, Virginia
Refinery. This work is part of a multi-media, joint AMOCOjUSEPA
Pollution Prevention Project. Overall goals of the Project were
to (1) inventory releases of all pollutants to the environment
from the Refinery; (2) develop, evaluate and rank process,
maintenance, and operating alternatives that reduce these
releases; and (3) identify barriers and incentives to
implementing the alternatives identified. Other volumes in this
study document sampling and analysis work in other media, peer
review, workshops, public opinion surveys, ecological impacts,
economic analysis, etc.
The multi-media sampling and analysis program showed that at this

facility, nearly 90 percent of the releases to the environment
were airborne. Consequently, many of the release reduction
options and subsequent analyses focussed on airborne materials,
primarily hydrocarbons.
As in any experimental program, there is uncertainty: in the

sampling methods, the analytical measurement techniques, and the
interpre'tation of results. In general, there are few standard
methods defined for this kind of work. Computer analysis tools
for studying pollutant dispersion are not exact. We have
attempted to use ithe best scientific tools available and
appropriate for the study at hand. Appendix J of this volume
provides an extensive summary of comments, questions, and
viii
proposals exchangred between Amoco and the EPA Off ice of Air
Quality Planning and standards regarding this material. The
reader is referred to this material to understand the complexity,
and diverse views which this type of study can engender. While
opinions may differ over the value of certain experimental
techniques, the interpretation of dispersion models, etc. there
is no doubt that the air emissions inventory for -this Refinery
has improved dramatically as a result of this study.
Howard Klee, Jr. Mahesh Podar

Amoco Corporation USEPA
ix
Executive Summary
As part of the AmocojUSEPA Pollution Prevention project, an
air quality evaluation of Amoco Oil Company's Yorktown
Refinery was conducted. The purpose of this portion of that
analyses was to define baseline air quality in terms of air
emissions and ambient air quality. This baseline was used
to evaluate potential impacts of different pollution
prevention options.
The estimation of baseline emissions was performed using
engineering calculations, USEPA emission factors and source
testing. Emissions were quantified for:
1) Benzene, toluene, ethylbenzene and xylene (BTEX)
2) Other SAF~ reported hydrocarbons (methanol,
ethylene, propylene, l,2,4-trimethylbenzene, MTBE,
cyclohexane, naphthalene, 1,3-butadiene)
3) Criteria pollutants
It was found t.hat the refinery's total non-methane
hydrocarbon emissions are approximately 7,900 tons per year,
and benzene emissions were estimated to be 67 tons per year.
Source testing' performed on the API separator, sewer vents
and the coker pond provided realistic estimates of volatile
organic compound (VOC) emissions. One limitation of this
x
study was that: no information was developed on the
variability of voe emissions with time. This is a
limit:ation of all short-term emission measurements.
However, since the source testing was performed during warm
ambient temperatures, and since the refinery was operating
near or at maximum capacity, the emission estimates should
be conservatively biased.
Figure 1 presents a summary of voe emission estimates as a
result of this study. Also, presented in Figure 1 are the
previous emission estimates that would have been assumed
without this field project. As indicated by comparison of
these two figures, without the improved revised emission
measurement inventory data, the benefits of pollution
prevention options could not have been accurately
quantified.
The accuracy of the emission inventory for BTEX was tested
by comparing modeling predictions to ambient air
measurements. Because the design of the ambient sampling
enabled identification of specific source impacts under
steady meteorological conditions, a comparison could be made
of model predictions, using the emission inventory, to the
observed ambient measurements. This comparison indicated
that the model predictions and the observed concentrations
generally agre~ed wi thin a factor of two. However, there was
a great deal of scatter in that data. As a result of this
xi
FIGURE 1. COMPARISON OF VOC EMISSIONS
DETERMINED FROM THIS STUDY TO THE PREVIOUS INVENTORY
II
~
Z I-
o Z
l::- LU
(J) o
z a:
o LU
a..
(J)
(J)
~
w
TOWER
BLOWDOWN BARGE COKER LAND FARM
EMISSION SOURCE
I0 EMISSIONS ~ PERCENT
VOC EMISSIONS FROM SARA INVENTORY
II
~
(J)
Z I-
o Z
l::- W
(J) o
z a:
o w
a..
(J)
(J)
~
W
FARM
BLOWDOWN WASTEWATER FUGITlVES COOUNG TOWER
EMISSION SOURCE
IO·EMISSIONS ~ PERCENT
xii
comparison, the project concluded that there was not a
significant bias in the emission inventory.
The emission inventory developed for the refinery was used
to predict annual average concentrations of BTEX, SARA
reported hydrocarbons and criteria pollutants. This was
done using one year of meteorological data. For benzene,
the maximum annual average concentration beyond the
fenceline was 6.2 ug/m3 • This concentration was predicted
in the river near the barge loading transfer point. At this
location, the majority of the predicted impacts were from
barge operations. The maximum annual average benzene
concentration on land was 1.3 ug/m3 • About 45 percent of
the predicted impacts were from barge operations. At a
nearby residence the maximum estimated modeled annual
average benzene concentration was 0.64 ug/m3 • Barge
operations were responsible for approximately 50 percent of
the projected impacts.
Similar analyses were conducted for the TEX and the other
SARA reported chemicals.
An important aspect of these analyses is the concept of
developing sit.e specific exposure criteria. The benzene
impact assessment for this refinery uniquely provides
insight on control strategies/options and allows for a
determination of the relative risk reduction. The concept
xiii
of relative risk reduction tends to better focus control
strat.egy selection criteria and optimize the monies spent on
emissions reductions.
No risk assessment was performed as part of this analysis,
although exposure assessment provides a site-specific,
speciated hydrocarbon data-base by source (both spatially
and temporally) to allow a relative benzene risk reduction
assessment for various control options.
Modeling was also performed for criteria pollutants (802'
N0 2, PM-10 and CO). These model predictions were then
compared to USEPA significant "levels and applicable national
ambient air quality standards (NAAQ8). The results of this
analysis indicated that for all criteria pollutants, except
802' predicted concentrations were less than the U8EPA
significant levels. For 802' the maximum contribution to
the 24-hour N~~Q8 of 365 ug/m3 was 50 ug/m3 (about
14 percent of the NAAQ8) .
xiv
1.0 Introductiott
As part of the Amoco/USEPA Pollution Prevention Program, an air
quality evaluation of the Amoco oil Company Yorktown Refinery was
conducted. This evaluation focused on determining baseline
conditions for the refinery in terms of air emissions and ambient
air quality. Three specific objectives of this study were
identified:
1) Quantify current air emissions from the facility;
2) Quantify ambient air quality impacts of these emissions;
and,
3) Identify emission reduction and ambient air quality benefits
of implementing pollution prevention alternatives or
additional control measures.
This rE!port present:s the results of the first two objectives
which utilized data from the air quality field sampling program
conduct:ed as part of this proj ect by Amoco and Radian corporation
. during September 2!:i through October 1, 1990. The field program
focused on both source emissions sampling and ambient monitoring.
Source emissions sampling was conducted on several different
source types where there was a large uncertainty in previous
emission estimates. The ambient air sampling program was
conduc·t:ed to identify the impacts from individual sources or
groups of sources and was used in subsequent air quality impact
1
analyses to confirm or verify the accuracy of the emission
invento~ (i.e., both magnitude and speciation of individual
chemicals). Results of the third objective are presented in a
report which describes the benefits of various pollution
prevention options for the facility (Klee, et aI, 1991).
The scope of these analyses was to estimate air quality impacts
from all air emissions emitted directly from the refinery.
Secondary effects of those emissions, such as ozone formation
from VOC and NO x ' were not considered in this study.
In this report, section 2.0 discusses the source sampling program
and methodology. section 3.0 presents the results obtained from
the ambient air quality sampling program. In Section 4.0, the
emission inventory for the refinery is presented. Section 5.0
contains the analysis performed to test the accuracy of the
Benzene., Toluene, Ethylbenzene and Xylene (BTEX) portion of the
inventory. Section 6.0 presents the results of a dispersion
modeling analysis VJ'hich translated the emissions from the
facility into ambie:nt air quality impacts at and beyond the
refinery fenceline. Conclusions and references are presented in
section 7.0 and 8.0, respectively.
2
2.0 Source sampling
Prior t:o the initiation of the field sampling program, a review
of facility sources, estimated emissions, and the quality of the
data used in developing these emission estimates was made. The
review indicated that previous emission estimates for the API
separat:or, sewer vEmts, inactive landfarm, blowdown stacks and
the coker blowdown pond were questionable and uncertain, at best.
For example, the past emission estimates for the API separator
were based on an emission factor of 5 pounds per 1,000 gallons of
water from refinery wastewater treatment facilities (AP-42, USEPA
1985). site-specific speciated emission estimates were then
developed from this factor based on the proportion of various
chemical constituents found in the effluent water. This emission
factor (i.e., 5 poundsjl,OOO gallons of water) was also utilized
to estimate emissions from sewer vents. Review of the reference
used to develop this factor revealed that it was based on a
single measurement from an API separator conducted in 1960.
Similarly, little data existed on emission factors for speciated
hydrocarbon emissions from an inactive landfarm or a coker
blowdo~m pond. All of these emission sources are "fugitive" in
nature (i.e., they do not originate from a stack, do not have
buoyancy or momentum, and cannot be easily sampled to obtain a
mass emission rate) and are likely to be very site specific.
This section of thE~ report presents an overview of the source
sampling that was performed on these fugitive sources. For more
3
detailed information on this sampling, the reader is referred to
Measurements of Hydrocarbon Emissions and Ambient Air
Concentrations at the Amoco Yorktown Refinery, Volume I (Radian
1991) •
This study was desiqned to provide an estimate of emissions at a
single point in time. Since the refinery was operating at or
near maximum capacit.y, and sampling was conducted in the summer,
emissions should approximate maximum/peak facility emission
ra"tes. Annual emissions were estimated by assuming that
maximum/peak emissions were constant for all hours of the year.
While this assumption is simplistic, it is also conservative,
given the time when the sampling program was conducted and the
operational status of the refinery. This approach does not
account for schedultad shutdowns, routine maintenance or unit
downtimta. This emission estimate technique is also consistent
with thta assumptions used in the exposure modeling (Le. I annual
average concentrations that are contained in Section 6).
It should be noted "that the problems of spatial and temporal
representation of emissions are not unique to this study. The
same problems exist if emission factors or models are used to
characberize emissitons. In the case of emission factors,
emissions are measured for a short time period and the
measurements are normalized to some form of process conditions.
These factors are then applied to the entire population of
4
sources. Clearly, there is a great deal of uncertainty in this
method of attempting to quantify emissions.
In the case of using models to estimate emissions from water
impoundments, the models have been compared to some very limited
measurE~ment data. Comparison of model predictions and actual
measurements used 1:0 validate the model indicates a large amount
of scatter in the model predictions with a general trend of
substantial model overprediction. In applying such a model to
estimate annual aVE~rage emissions, one must address the issue of
tefuporal and spatial variation in data to initialize the model
("Emission models use average influent and effluent
concentrations to estimate annual emission, ... " USEPA 1989).
Emission model estimates are further complicated by requiring the
use of average meteorological conditions for an entire year.
Clearly, this is a question which must be addressed for all types
of procedures for estimating emissions and is not limited to this
s'tudy. One recommendation which results from this observation is
that this is an an~a where additional research is needed.
2.1 API Separator l~easurements
Becausle of the larq'e surface area of the API oil-water separator
(26,000 square feet) at the Yorktown Refinery, it was not
possible to make direct emission measurements from the total
unit. Instead, it was necessary to make a flux measurement from
5
a portion of the surface area. This was performed using an
isolation flux chamber which was suspended over the surface of
the water. The isolation flux chamber was developed for
estimating the emission rates from surface impoundments
(Keinbush, et al 1988 and Radian 1985). Specific details on the
sampling of this source are presented in (Radian 1991). The
following section provides an overview of that sampling.
Figures 2-1 and 2-2 present a schematic of the isolation flux
chamber as well as how it was applied to sampling the API
separator. The principle of the chamber is that the emissions
from the surface are isolated from the atmosphere using an inert
chamber of known surface area. The chamber is then purged with a
known amount of ultra-high purity air. The outlet concentration
from the chamber is then measured, using a total hydrocarbon
analyzer, to determine when equilibrium conditions are achieved.
After equilibrium conditions are obtained, a whole air sample is
collected using an evacuated Suma canister (USEPA Method TO-14,
USEPA 1989). Thus, from the concentration measurements, the
purge gas rate and the surface area of the chamber, a flux rate
(grams per second per square meter) can be estimated (Radian
1991) .
During the method development of the flux chamber, it was found
that the range of relative accuracy for this method has been
estimated to be between 77 and 124 percent (Keinbush et al 1988).
6
THERMOCOUPLE
SYRINGE/CANISTER
SAMPLING PORT
~_~IN~LE~T,-----.,
REAL TIME
ANALYZER
CARRIER STAINLESS STEEL

GAS OR PLEXIGLAS
'"
r §
....~
~
l-----~.--J
CUT AWAY TO St-I')W
ONE OF THREE SWEEP AIR INLE~ LiNE
ADJUSTABLE,SUPPORT AND THE OUllE-, LINE
FLOATATIONS
FIGURE 2-1. CUTAWAY DIAGRAM OF FLUX CHAMBER AND SUPPORT EQUIPMENT.

co
Liquid Surface
FIGURE 2-2. SAMPLING APPROACH FOR API SEPARATOR.

This was estimated by determining the recovery of 40 different
compounds. The ave~rage recovery was 103 percent (Keinbush et al
1988). As part of the original evaluation of the method
performed by Radian, it was found that single chamber precision
was approximately ±7 percent at an emission rate of 5,000 ug/m2-
min (Keinbush, et al 1988). One limitation of this method may be
that it: does not rE~plicate the wind speed near the ground
(probably overestimates velocity). Therefore, because emissions
from these sources are mass transfer limited, it is possible that
there is a positive bias (i.e., overestimate) in these measured
emission rates.
Two replicate measurements of concentration were made on the API
separator. The replicate samples were taken at opposite ends of
the separator box. These replicate samples were taken within
2 hours of each other. The results from these samples are
present:ed in Table 2-1. As indicated in this table, there is a
very large variation in concentration between the two samples.
This difference probably reflects the spatial and temporal
variability in emissions from this source. The results from the
two replicate samples were averaged and these values were used in
subse~lent analyses. It is believed that using a mean of the two
replicate samples represents actual emissions at the time
sampling was performed. To estimate annual emissions, we assumed
that the hourly emissions would be constant at this rate over the
entire year (i.e., summation of this rate over 8,760 hours). As
9
TABLE 2-1. SPECIATED HYDROCARBON EMISSIONS FROM THE API SEPARATOR
API API AVE EMISSION SURFACE EMISSION EMISSION PERCENT' I

SAS SA7 CONC RATE AREA RATE RATE OF I
COMPOUND NAME (UG/M"3) (UG/M"3) (UG/M"3) (UG/MIN-M"2) (M*'2) (G/SEC) rrONS/YR) TOTAL
ISOBUTANE 1230 5480 3355 129.27 24D0 0.01 0.18 0.31

ISOBUTENE + I-BUTENE 474 1850 1162 44.77 24D0 0.00 0.06 0.1 I
N·BUTANE 1710 8190 4950 190.73 24D0 0.Q1 0.27 0.4
T·2·BUTENE 307 1810 1059 4D.79 2400 0.00 0.06 0.1 1
C·2·BUTENE 177 958 568 21.87 24D0 0.00 0.03 0.0
ISOPENTANE 1510 74D0 4455 171.66 24D0 0.01 0.24 0.4
TRICHLOROFLUOROMETHANE 13 20 17 0.64 24D0 0.00 0.00 0.0
2·METHYL-1-BUTENE 268 4D8 338 13.02 24D0 0.00 0.02 0.0
N·PENTANE 154D 2590 2065 79.57 24D0 0.00 0.11 0.2
T-2·PENTENE 977 6330 3654 14D.77 24D0 0.01 0.20 0.3
C-2-PENTENE 598 3220 1908 73.52 24D0 0.00 0.10 0.2
2-METHYL-2-BUTENE 805 3110 1958 75.42 24D0 0.00 0.10 0.2
2,3·DIMETHYLBUTANE 0 4Dl0 2005 77.26 24D0 0.00 0.11 0.2
ISOHEXANE 4070 6530 5300 204.22 24D0 0.01 0.28 0.5
I-' 3-METHYLPENTANE 2680 0 134D 51.63 24D0 0.00 0.07 0.1
o N-HEXANE 3360 15800 9580 369.13 24D0 0.01 0.51 0.8
CHLOROFORM 18 28 23 0.90 24D0 0.00 0.00 0.0
T·2·HEXENE 0 4830 2315 89.20 24D0 0.00 0.12 0.2
C·2·HEXENE 0 1610 805 31.02 24D0 0.00 0.04 0.1
METHYLCYCLOPENTANE 3850 18100 10975 422.88 24D0 0.02 0.59 1.0
2,4-DIMETHYLPENTANE 1060 5150 3105 119.64 24D0 0.00 0.17 0.3
l,l,l-TRICHLOROETHANE 8 9 9 0.33 24D0 0.00 0.00 0.0
BENZENE 11300 27300 19300 743.65 24D0 0.03 1.03 1.7
CYCLOHEXANE 2650 9720 6185 238.32 24D0 0.01 0.33 0.5
ISOHEPTANE + 2,3-DIMETHYLPENTANE 5450 24D00 14725 567.37 24D0 0.02 0.79 1.3
3·METHYLHEXANE 2860 12600 7730 297.85 24D0 0.01 0.41 0.7
2,2,4-TRIMETHYLPENTANE 1420 17000 9210 354.87 24D0 0.01 0.49 0.8
N·HEPTANE 4190 18200 11195 431.36 24D0 0.02 0.60 1.0
METHYLCYCLOHEXANE 5470 2670 4D70 156.82 24D0 0.01 0.22 0.4
2,5-DIMETHYLHEXANE 810 2480 1645 63.38 2400 0.00 0.09 0.1
2,2,3·TRIMETHYLPENTANE 690 2880 1785 68.78 24D0 0.00 0.10 0.2
TOLUENE 64700 162000 113350 4367.52 24D0 0.17 6.07 10.0
3·METHYLHEPTANE 3630 14800 9215 355.07 24D0 0.01 0.49 0.8
N-OCTANE 4910 19600 12255 472.20 24D0 0.02 0.66 1.1
ETHYLBENZENE 16900 56300 36600 1410.24 24D0 0.06 1.98 3.2
P-XYLENE + M-XYLENE 53800 176000 114900 4427.24 24D0 0.18 6.16 10.1
O-XYLENE 23400 68300 45850 1766.66 24D0 0.07 2.48 4.0
N·NONANE 8410 23200 15805 608.99 24D0 0.02 0.85 1.4
ISOPROPYLBENZENE 0 6830 3415 131.58 24D0 0.01 0.18 0.3
N-PROPYLBENZENE 744D 27800 17620 678.92 24D0 0.03 0.94 1.5
M·ETHYLTOLUENE 26300 98700 62500 24D8.21 2400 0.10 3.35 5.5
l,3,5·TRIMETHYLBENZENE 11300 38300 24900 955.58 24D0 0.04 1.33 2.2
TABLE 2-1. SPECIATED HYDROCARBON EMISSIONS FROM THE API SEPARATOR
API API AVE EMISSION SURFACE EMISSION EMISSION PERCENT

SA6 SA7 CONC RATE AREA RATE RATE OF
COMPOUND NAME (UG/M·*3) (UG/M**3) (UG/M"3) (UG/MIN-M·*2) (M·*2) (G/SEC) (TONSIYR) TOTAL
O-ETHYLTOLUENE 10200 37000 23600 909.34 2400 0.04 1.26 2.1

T-BUTYLBENZENE 30600 96700 63650 2452.52 2400 0.10 3.41 5.6
N~DECANE 8650 18100 13375 515.36 2400 0.02 0.72 1.2
P-ISOPROPYLTOLUENE 1850 2890 2370 91.32 2400 0.00 0.13 0.2
INDAN 3180 0 1590 61.26 2400 0.00 0.09 0.1
INDENE 2800 0 1400 53.94 2400 0.00 0.08 0.1
M-DIETHYLBENZENE 5540 16300 10920 420.76 2400 0.02 0.59 1.0
N-BUTYLBENZENE 5970 16600 11285 434.63 2400 0.02 0.60 1.0
P-DIETHYLBENZENE 5430 16500 10965 422.50 2400 0.02 0.59 1.0
N-UNDECANE 792 1560 1176 45.31 2400 0.00 0.06 0.1
UNIDENTIFIED VOC 197000 604000 400500 15431.76 2400 0.62 21.46 35.2
UNIDENTIFIED HALOGENATED VOC 29 22 25 0.97 2400 0.00 0.00 0.0
TNMHC -----
"---___~5~000 ____ !7~ 1137500
--~~--~
43829.33 2400 1.75 60.95 100.0
......
......
previously discussed, we feel that this estimate is conservative
since the refinery 1N'aS operating at or near maximum capacity
during 'the sampling. As indicated by Table 2-1, the total VOC
emission rate is approximately 61 tons per year. Emissions of
BTEX cOlmpounds are 1, 6, 2, and 9 tons per year, respectively.
(See Radian 1991 for computational solutions). Table 2-1
presents a summary IOf those compounds for which emissions from
the API separator w,ere above the analytical detection limits of
the TO-14 Method. It should be noted that approximately
35 perc,ent of the botal emissions were not identifiable by this
method. This large fraction is a result of many small peaks
which could not be identified from the chromatogram (see Radian
1991 for additional details).
Figure 2-3 compares the results of this sampling program to the
emission estimates previously made for this source. As indicated
in this figure, total VOC emissions are estimated, based on this
sampling, to be 61 tons per year (based on the average of the
2 measurements and assuming that emissions are constant during
the entire year) compared to 1,277 tons per year based on the
AP-42 emission factor. For all species of interest, the flux
chamber measurements result in a lower emission rate estimate.
An attempt to perform a collaborative estimate of emissions from
this source using CHEMDAT7 (USEPA 1989) was unsuccessful because
not all of the data necessary to run the model were available.
12
FIGURE 2-3
EMISSIONS FROM THE API SEPERATOR
a:
-~
~
z
I-'
W o
t::-
en
z
o
(f)
(f)
~
w
1.0
BENZENE
2.2 coker Pond Measurements
MeasurE~ments of emissions from the coker pond were also made
using 1:he isolation flux chamber. Coker pond emission sampling
was conducted in both the quench section and the overflow
section. sampling in the quench section was conducted over the
entire 18-hour coking cycle, with samples obtained every 6 hours
during the 18-hour period. Thus, an attempt was made to
integrate the sample with respect to time in order to account for
the variability in emissions as a result of changes in process
conditions. The overflow section pond was sampled in an
analogous manner to the API separator. Replicate samples were
collected from both sections of the coker.
Figure 2-4 represents a schematic of the sampling approach used
for this source. Tables 2-2 and 2-3 present the results for flux
chamber measurements from both sections of the pond. From this
pond, 1:otal emissions were estimated by summing these two tables.
As indicated by these data, total VOC emissions from this source
are approximately 261 tons per year. These tables indicate
emissions of the identified chemicals which were above the
analytical detection limits using the Method TO-14. Speciated
emissions for BTEX are 1.4, 2.9, 1.0, and 6.0 tons per year,
respec1:i vely • Annual estimates of emissions from this source are
based on the assumption that emissions are constant at the
14
Support line
I-'
VI
Siabilazalion Line
FIGURE 2-4. SAMPLING ARRANGEMENT USED TO MONITOR THE COKER QUENCHING POND INLET.
TABLE 2-2. SPECIATED EMISSIONS FROM COKER QUENCH POND (QUENCH AREA)
CONC CONC AVG EMISSION SURFACE EMISSION EMISSION PERCENT
COMPOUND NAME SA-ll SA-16 CONC RATE AREA RATE RATE OF
(UG/M**3) (UG/M**3) (UG/M'*3) IUG/MIN-M**2) (M**2) IG/SEC) (TONS/YR) TOTAL
1';>UtlUIANt: lUOUUU IOUUUU IO~UUU 1410<' U.Ub ~.U u.o
"4!l."~
N-BUTANE 710000 751000 730500 56294 248.25 0.23 8.1 3.1
T·2·BUTENE 48086 58614 53350 4111 248.25 0.02 0.6 0.2
C-2-8UTENE 34877 43929 39403 3036 248.25 0.01 u.~ u.£
CHLOROETHANE 10269 23 5146 397 248.25 0.00 0.1 0.0

ISOPENTANE 228210 216247 222229 17126 248.25 0.07 2.5 0.9
TRICHLOROFLUOROMETHANE 134671 44 67308 5187 248.25 0.02 0.7 0.3
2-METHYL+BUTENE 29286 55622 42464 3272 248.25 0.01 0.5 0.2
N-PENTANE 547186 455014 501100 38616 248.25 0.16 5.6 2.1
T-2-PENTENE 53601 72669 63135 4865 248.25 0.02 0.7 0.3
C-2-PENTENE 16751 53150 34951 2693 248.25 0.Q1 0.4 0.1
METHYLENE CHLORIDE 233295 23 116659 8990 248.25 0.04 1.3 0.5
2·METHYL-2-BUTENE 59625 83317 71471 5508 248.25 0.02 0.8 0.3
ISOHEXANE 119609 111047 115328 8887 248.25 0.04 1.3 0.5
3-METHYLPENTANE 57673 29 28851 2223 248.25 0.01 0.3 0.1
N-HEXANE 577310 642255 609783 46991 246.25 0.19 6.8 2.6
CHLOROFORM 243060 82 121571 9369 248.25 0.04 1.3 0.5
T-2-HEXENE 54602 113016 83759 6455 246.25 0.03 0.9 0.4
2-METHYL-2-PENTENE 47810 402 24106 1858 246.25 0.01 0.3 0.1
C-2-HEXENE 25633 31872 28752 2216 246.25 0.01 0.3 0.1
METHYLCYCLOPENTANE 254260 272714 263467 20305 246.25 0.08 2.9 1.1
2,4-DIMETHYLPENTANE 19710 20417 20063 1546 246.25 0.01 0.2 0.1
BENZENE 10.5970 149645 127808 9849 246.25 0.04 1.4 0.5
CYCLOHEXANE 71870 97513 84692 6527 246.25 0.03 0.9 0.4
ISOHEPTANE + 205770 227291 216530 16686 248.25 0.07 2.4 0.9
2,3 DIMETHYLPTANE
3-METHYLHEXANE 152400 158572 155466 11982 248.25 0.05 1.7 0.7
i-'
a- 2,2,4-TRIMETHYLPENTANE 26246 30750 28488 2196 246.25 0.01 0.3 0.1
N-HEPTANE 704850 810150 757550 58379 248.25 0.24 8.4 3.2
METHYLCYCLOHEXANE 208040 241620 224830 17326 248.25 0.07 2.5 1.0
2,2,3-TRIMETHYLPENTANE 47090 42100 44695 3437 248.25 0.01 0.5 0.2
2,3,4-TRIMETHYLPENTANE 115760 23198 69479 5354 248.25 0.02 0.8 0.3
TOLUENE 169980 360789 265375 20450 248.25 0.08 2.9 1.1
3-METHYLHEPTANE 161680 164748 163213 12578 248.25 0.05 1.8 0.7
N-OCTANE 947700 939524 943612 72717 248.25 0.30 10.5 4.0
ETHYLBENZENE 58530 121172 89851 6924 248.25 0.03 1.0 0.4
P-XYLENE + M-XYLENE 248650 487435 368543 28401 248.25 0.12 4.1 1.6
STYRENE 204530 426 102478 7897 248.25 0.03 1.1 0.4
O-XYLENE 126100 207932 167016 12871 248.25 0.05 1.9 0.7
N-NONANE 884170 1010630 947400 73009 248.25 0.30 10.5 4.0
ISOPROPYLBENZENE 27960 34359 31159 2401 248.25 0.01 0.3 0.1
N-PROPYLBENZENE 534000 134077 334038 25742 248.25 0.11 3.7 1.4
M-ETHYLTOLUENE 821000 260329 540665 41665 248.25 0.17 6.0 2.3
1,3,5-TRIMETHYLBENZENE 32700 108000 70350 5421 248.25 0.02 0.8 0.3
O-ETHYLTOLUENE 118000 164000 141000 10866 248.25 0.04 1.6 0.6
T-BUTYLBENZENE 76600 176000 126300 9733 248.25 0.04 1.4 0.5
N-DECANE 556000 690000 623000 48010 248.25 0.20 6.9 2.7
1,2,3-TRIMETHYLBENZENE 15500 0 7750 597 248.25 0.00 0.1 0.0
M-DIETHYLBENZENE 29900 67000 48450 3734 248.25 0.02 0.5 0.2
N-BUTYLBENZENE 79700 141000 110350 8504 248.25 0.04 1.2 0.5
P-DIETHYLBENZENE 39700 99000 69350 5344 248.25 0.02 0.8 0.3
N-UNDECANE 36900 713000 374950 26895 248.25 0.12 4.2 1.6
UNIDENTIFIED VOC 7160000 10300000 8730000 672756 248.25 2.78 96.8 37.3
UNIDENTIFIED
HALOGENATED VOC 0 12400 6200 478 248.25 0.00 0.1 0.0
TNMHC 21300000 25500000 23400000 1803264 248.25 7.46 259.4 100.0
TABLE 2-3, SPECIATEDEMISSIONS FROM COKER QUENCH POND (OVERFLOW AREA)
COMPOUND NAME SA-20 SA-21 CONC RATE AREA RATE RATE OF
(UG/M**3) (UG/M*'3) (UG/M**3) (UG/MIN-M'*2) (M*'2) (G/SEC) (TONSNR) TOTAL
ISOBUTANE 0.00 4.50 2.25 0.17 95 0.0000 0.000 0.8

ISOBUTENE + 1-BUTENE 186.00 1.20 93.60 7.21 95 0.0000 0.000 0.7
N-BUTANE 377.00 16.20 196.60 15.14 95 0.0000 0.001 3.1
METHANOL 0.00 58.40 29.20 2.25 95 0.0000 0.000 3.1
T-2-BUTENE 0.00 0.00 0.00 0.00 95 0.0000 0.000 0.2
C-2-BUTENE 0.00 0.00 0.00 0.00 95 0.0000 0.000 0.2
CHLOROETHANE 0.00 0.20 0.10 0.01 95 0.0000 0.000 0.0
ETHANOL 0.00 163.00 81.50 6.28 95 0.0000 0.000 0.0
ACETONE 0.00 24.30 12.15 0.94 95 0.0000 0.000 0.0
ISOPENTANE 299.00 0.00 149.50 11.51 95 0.0000 0.001 1.0
TRICHLOROFLUOROMETHANE 3210.00 0.70 1605.35 123.61 95 0.0002 0.007 0.3
2-METHYL-l-BUTENE 0.00 2.60 1.30 0.10 95 0.0000 0.000 0.2
N-PENTANE 571.00 8.90 289.95 22.33 95 0.0000 0.001 2.1
T-2-PENTENE 0.00 0.00 0.00 0.00 95 0.0000 0.000 0.3
t-' C-2-PENTENE 0.00 0.00 0.00 0.00 95 0.0000 0.000 0.2
-..J METHYLENE CHLORIDE 0.00 215.00 107.50 8.28 95 0.0000 0.000 0.5
2-METHYL-2-BUTENE 0.00 1.10 0.55 0.04 95 0.0000 0.000 0.3
1,1-DICHLOROETHANE 0.00 5.00 2.50 0.19 95 0.0000 0.000 0.3
NEOHEXANE 0.00 0.60 0.30 0.02 95 0.0000 0.000 0.3
ISOHEXANE 286.00 13.80 149.90 11.54 95 0.0000 0.001 0.5
3-METHYLPENTANE 186.00 0.00 93.00 7.16 95 0.0000 0.000 0.1
N-HEXANE 901.00 8.00 454.50 35.00 95 0.0001 0.002 2.7
CHLOROFORM 0.00 164.00 82.00 6.31 95 0.0000 0.000 0.5
T-2-HEXENE 0.00 0.00 0.00 0.00 95 0.0000 0.000 0.4
2-METHYL-2-PENTENE 0.00 0.00 0.00 0.00 95 0.0000 . 0.000 0.1
G-2-HEXENE 0.00 0.00 0.00 0.00 95 0.0000 0.000 0.1
METHYLCYCLOPENTANE 651.00 2.50 326.75 25.18 95 0.0000 0.001 1.2
1,2-DICHLOROETHANE 0.00 2.00 1.00 0.08 95 0.0000 0.000 1.2
1,1,1-TRICHLOROETHANE 0.00 344.00 172.00 13.24 95 0.0000 0.001 1.2
2,4-DIMETHYLPENTANE 0.00 0.70 0.35 0.03 95 0.0000 0.000 0.1
CARBON TETRACHLORIDE 0.00 3.10 1.55 0.12 95 0.0000 0.000 0.1
BENZENE 295.00 4.70 149.85 11.54 95 0.0000 0.001 0.6
1-BUTANOL 0.00 26.20 13.10 1.01 95 0.0000 0.000 0.6
CYCLOHEXANE 225.00 0.00 112.50 8.66 95 0.0000 0.000 0.4
ISOHEPTANE + 2,3-DIMETHYLPENTANE 609.00 3.50 306.25 23.58 95 0.0000 0.001 1.0
3-METHYLHEXANE 373.00 2.30 187.65 14.45 95 0.0000 0.001 O.B
TRICHLOROETHANE 0.00 47.80 23.90 1.B4 95 0.0000 0.000 O.B
1,2-DICHLOROPROPANE 0.00 6.80 3.40 0.26 95 0.0000 0.000 0.8
2,2,4-TRIMETHYLPENTANE 0.00 4.60 2.30 0.18 95 0.0000 0.000 0.1
N-HEPTANE 3310.00 1.50 1655.75 127.49 95 0.0002 0.007 3.3
METHYLCYCLOHEXANE 1060.00 0.90 530.45 40.84 95 0.0001 0.002 1.0
TOLUENE 5210.00 21.60 2615.80 201.42 95 0.0003 0.011 1.2
3-METHYLHEPTANE 933.00 0.60 466.80 35.94 95 0.0001 0.002 0.8
TABLE 2-3, SPECIATED EMISSIONS FROM COKER QUENCH POND (OVERFLOW AREA)
COMPOUND NAME SA-2O SA-21 CONC RATE AREA RATE RATE OF
(UG/M**3) (UG/M**3) (UG/M**3) (UG/MIN-M**2) (M**2) (G/SEC) (TONSIYR) TOTAL
TETRACHLOROETHANE 0,00 541,00 270,50 20,83 95 0,0000 0,001 0,8

HEXANAL 0,00 4,60 2,30 0,18 95 0,0000 0,000 0,8
CHLOROBENZENE 9,10 4,55 0,35 95 0,0000 0,000 0,8
N-OCTANE 9260,00 0,00 4630,00 356,51 95 0,0006 0,020 6,5
ETHYLBENZENE 2810,00 2,70 1406,35 108,29 95 0,0002 0,006 0.4
P-XYLENE + M-XYLENE 8370,00 9,00 4189,50 322,59 95 0,0005 Om8 1,7
STYRENE 2770,00 0,00 1385,00 106,65 95 0,0002 0,006 0,5
O-XYLENE 3770,00 3,30 1886,65 145,27 95 0,0002 0,006 0,8
N-NONANE 20400,00 0,60 10200,30 785.42 95 0,0012 0,043 4.4
ISOPROPYLBENZENE 646,00 0,00 323,00 24,87 95 0,0000 0,001 0,1
N-PROPYLBENZENE 1950,00 0,90 975,45 75,11 95 0,0001 0,004 8,5 I
I
M-ETHYLTOLUENE 8040,00 3,10 4021,55 309,66 95 0,0005 0,017 18,7
I
l,3,5-TRIMETHYLBENZENE 5190,00 1,50 2595,75 199,87 95 0,0003 0,011 0,3
O-ETHYLTOLUENE 7760,00 1,40 3880,70 298,81 95 0,0005 0,016 0,6
N-DECANE 5870,00 3,20 2936,60 226.12 95 0,0004 0,012 2,7
P-ISOPROPYLTOLUE 5650,00 3,20 2826,60 217,65 95 0,0003 0,012 2,7
l,2,3-TRIMETHYLBENZENE 2230,00 6,40 1118,20 86,10 95 0,0001 0,005 0,0
M-DIETHYLBENZENE 5530,00 0,00 2765,00 212,91 95 0,0003 0,012 0,2
t-'
00 N-BUTYLBENZENE 12100,00 0,00 6050,00 465,85 95 0,0007 0,026 0,5
P-DIETHYLBENZENE 8170,00 0,00 4085,00 314,55 95 0,0005 0,017 0,3
N-UNDECANE 3360,00 11,90 1685,95 129,82 95 0,0002 0,007 1.6 I
UNIDENTIFIED VOC 485000,00 1120,00 243060,00 18715,62 95 0,0296 1.030 37,3
i
UNIDENTIFIED HALOGENATED VOC 0,00 94,60 47,30 3,64 95 0,0000 0,000 0,0
TNMHC 692000,00 2990,00 347495,00 26757,12 95 0,0424 1.473 100,0 i
measur~=d rate over a complete year. The conservative results and
implications of this methodology have been previously discussed.
As indicated by thle replicate sampling, there was a large
variation in measured flux between samples. This variation was
typically less than a factor of 2. The sampling on the coker
pond was conducted near the point of water discharge, thus, this
should represent the location of maximum emissions.
As in the case of the API separator, a large fraction
(approximately 30 percent) of the voe emissions were not
identifiable. Onc,e again, these unidentified compounds were a
result of many small chromatogram peaks. (See Radian 1991 for
more details.) Figure 2-5 summarizes the results for BTEX and
total voe emissions.
2.3 La:ndfarm. Measurements
One flux chamber m,easurement was made in the center of the
inactive landfarrn. The surface of the soil had been recently
tilled, which should have enhanced emissions on a temporary
basis.
In reviewing the emission measurements, several things should be
kept in mind. First, the emission estimate reflects only one
sampling or datapoint. Thus, no attempt was made to spatially
average or integra·te emissions over the entire surface area of
the landfarrn (16.5 acres) or to describe emissions as a function
19
U
to I
ci ~
ItO
(\J Z
f-
0
Z
0
CL
Z w
S zW
0 ....J
0 x>-
S
Oi
....J
!!'len
~a: W
Z
ILI
W W
~~ N
DO Z
w
80 CDI
~~ W
0
a:
u..
C/) w
Z
z
w
;:)
0 ....J
C/) 0
f-
C/)
~
W
w
z
W
N
Z
W
CD
,... ,...
b::lV'3A/SNO.u SNOISSIv.J3
20
of time. Surface conditions (e.g., moisture, etc.) of the
soilcould greatly a.ffect the emission rate. Second, the flux
measurements were only slightly above those measured in the
sample blank. At t:hese low concentration levels, the accuracy
and precision of the measurements could greatly affect the
extrapolation of the limited flux data over the entire surface of
the landfarm, sincE~ the total area of the landfarm was large in
proport:ion to the area of the flux chamber.
For this source, annual emissions were estimated by assuming that
the single measurement of flux from the inactive landfarm is
representative of emissions over the entire surface area and for
all hours of the yE~ar. We acknowledge that this assumption is
overly simplistic given the data but it provides an indication of
the importance of t:his source compared to the other refinery
sources. It should be noted that prior to this measurement, no
data was available to estimate emissions from this source.
Table 2-4 and Figure 2-6 present a summary of these emission
data. As indicated in these data, total voe emissions are
estimated at approximately 53 tons per year.
Emissions from BTEX compounds were found to be 0.0, 0.5, 0.6, and
3.4 tons per year, respectively. As with the other two source
types for which thi.s sampling approach was used, a very large
fraction of the spe~ciated emission data were not identifiable
21
TABLE 2-4, SPECIATED EMISSIONS FROM THE LANDFARM
CONC:I\TION I BLI\.NK NET FLUX EMISSION EMISSION PERCENT

SA-8 CONCENTRATION RATE AREA RATE RATE OF
COMPOUND NAME (UG/M"3) (UG/M"3) (UG/M"3) (UG/sEC-M"2) (M"2) (GISEC) (TONSIYR) TOTAL
I
N-BUTANE 28.8 32.1 <LLD 0.000 6.68E+04 0.000 0.000 0.00
TRICHLOROFLUOROMETHANE 11.5 0 11.5 0.007 6.68E+04 0.000 0.017 0.03
N-PENTANE 26.8 30.7 <LLD 0.000 6.68E+04 0.000 0.000 0.00
METHYLENE CHLORIDE 7.4 0 7.4 0.005 6.68E+04 0.000 0.011 0.02
ISOHEXANE 40.9 17 23.9 0.015 6.68E+04 0.001 0.036 0.07
3-METHYLPENTANE 21.7 11.2 10.5 0.007 6.68E+04 0.000 0.016 0.03
N-HID'..ANE 52.7 37.8 14.9 0.010 6.68E+04 O'()ol 0.022 0.04
I
METHYLCYCLOPENTANE 54.2 26.6 27.6 0.018 6.68E+04 0.001 0.041 0.08 I
BENZENE 26.2 35.7 <LLD 0.000 6.68E+04 0.000 0.000 0.00 !
CYCLOHEXANE 51.4 11.8 39.6 0.025 6.68E+04 0.002 0.059 0.11
ISOHEPTANE + 2,3-DlME1HYLPENTANE 76.3 32.9 43.4 0.028 6.68E+04 0.002 0.065 0.12
3-METHYLHEXANE 50.3 18.9 31.4 0.020 6.68E+04 0.001 0.047 0.09
N-HEPTANE 150.0 52.6 97.4 0.062 6.68E+04 0.004 0.145 0.27
METHYLCYCLOHEXANE 111.0 28.5 82.5 0.053 6.68E+04 0.004 0.123 0.23
TOLUENE 505.0 195 310 0.199 6.68E+04 0.013 0.461 0.87
3-ME1HYLHEPTANE 63.9 20.9 43 0.028 6.68E+04 0.002 0.064 0.12 !
N-OCTANE 150.0 47.3 102.7 0.066 6.68E+04 0.004 0.153 0.29

ETHYLBENZENE 477.0 63.3 413.7 0.265 6.68E+04 0.Q18 0.616 1.17
[:::5 P-XYLENE + M-XYLENE 1740.0 197 1543 0.989 6.68E+04 0.066 2.296 4.35
STYRENE 74.6 0 74.6 0.048 6.68E+04 0.003 0.111 0.21
O-XYLENE 836.0 79.6 756.4 0.485 6.68E+04 0.032 1.125 2.13
N-NONANE 355.0 37.6 317.4 0.203 6.68E+04 0.014 0.472 0.89
ISOPROPYLBENZENE 103.0 6.3 96.7 0.1)62 6.68E+04 0.004 0.144 0.27
N-PROPYLBENZENE 633.0 28 605 0.388 6.68E+04 0.026 0.900 1.71
M-ETHYLTOLUENE 1770.0 96.2 1673.8 1.073 6.68E+04 0.072 2.490 4.72
P-ETHYLTOLUENE 875.0 0 875 0.561 6.68E+04 0.037 1.302 2.47
1,3,5-TRIME1HYLBENZENE 1080.0 35.5 1044.5 0.670 6.68E+04 0.045 1.554 2.94
O-ETHYLTOLUENE 905.0 33.4 871.6 0.559 6.68E+04 0.037 1.297 2.46
T-BUTYLBENZENE 3560.0 101 3459 2.217 6.68E+04 0.148 5.147 9.75
N-DECANE 691.0 23.1 667.9 0.428 6.68E+04 0.029 0.994 1.88
P-ISOPROPYLTOLUENE 462.0 11.6 450.4 0.289 6.68E+04 0.019 0.670 1.27
M-DlE1HYLBENZENE 997.0 18 979 0.628 6.68E+04 0.042 1.457 2.76
N-BUTYLBENZENE 959.0 18.7 940.3 0.603 6.68E+04 0.040 1.399 2.65
P-DlE1HYLBENZENE 1080.0 19.3 1060.7 0.680 6.68E+04 0.045 1.578 2.99
N-UNDECANE 970.0 11.4 958.6 0.614 6.68E+04 0.041 1.426 2.70
UNIDENTIFIED VOC 18900.0 801 18099 11.602 6.68E+04 0.775 26.929 51.01
TNMHC 37900.0 2420 35480 22.744 6.68E+04 1.519 52.790 100.00
FIGURE 2-6
EMISSIONS FROM THE INACTIVE LAND FARM
/~I---------------------'--------------'---------------'-------------~-----------------
52.88
t.)
~
z
g
CJ)
z
o
CiCJ)5
~
w
BENZENE TOLUENE ETHYLBENZENE XYLENE TNMHC

(51 percent). This: large fraction was a result of many
smallchromatogram peaks which could not be resolved (see Radian
1991 for more details).
2.4 Sewer Vellt Measlurements
Emission from sewer vents originated from a square grate
approximately 3 to 4 feet on a side. Emissions were estimated
from these sources by first covering the grate with an air-tight
plastic tarp and installing a 7-inch diameter pseudo stack 8-
inches tall in the center of the plastic. Thus, all of the
vapors escaping from this section of the sewer passed through the
pseudo stack. Figure 2-7 presents a schematic of the sampling
approach used. (See Radian 1991 for more details.)
The concentration of the vapor was determined by sampling with a
charcoal tube sampler (NIOSH Method 1501, NIOSH, 1984). These
samples were integrated over a 30-minute period. In order to
calculate the mass emission rate, the volume flow rate was
determined. This was performed by measuring the stack exit
veloci t:y using a hot-wire anemometer. The volume flow was then
compute~d using the velocity and the cross-sectional area of the
pseudo stack.
Emission measurements were made from three different sewer vent
locations along the~ main sewer trunkline (near the coking unit,
the cooling tower and the tank farm). At the sewer vent near the
24
Sewer Emissions
N
V1
.,
FIGURE 2-7. SAMPLING DESIGN FOR THE SEWER VENT DIRECT MEASUREMENTS.
cooling tower (AF-2), it was not possible to divert all of
thevent gas through the sampling stack. Consequently, this
measurement may und,~rstate the emission rate from the process
sewer VE~nts and has not been included in the total emission
es-timatE=s.
Table 2--5 presents a summary of the results of the sewer vent

samplinq-. As indicated by the data contained in this table,
speciatE=d emissions were very consistent between sampling points
AF-l and AF-3. Emi::;sions from other sewer vents were estimated
from these data (T~ble 2-6). As indicated from this table, total
voe emissions for all sewer vents are approximately 117 tons per
year. 'rhe estimate of total voe emissions was made by
multiplying toluene emissions measured from the sewer by the
ratio of total non-lillethane hydrocarbon (TNMHC) to toluene
measured at the API separator. The resulting speciated emissions
for BTEX are 2, 12, 4, and 15 tons per year, respectively.
Annual ,emissions were computed by assuming that these measured
emission rates were constant over the entire year.
Several points can be made regarding the sampling approach

employed in the sewer sampling and possible bias in the resulting
emissions. First, -the sampling approach only reduced the area of
the total sewer vent openings by about 1 percent. As a result of
this, there should be little pressure drop on the system and air
could s-till sweep through the sewers in an unaltered manner. It
26
TABLE 2-5, SUMMARY OF EMISSIONS MEASURMENTS FROM SEWER VENTS
:SbWER VbNT VbNT J-i.MISSI()N J-<:MISS IN
VENT CONC FLOW RATE RATE THC
NUMBER COMPOUND (UG/M3) (M3/MIN) (G/SEC) (TONSIYR) . (PPM)
AFI BENZENE 5.30E+05 1.50 0.01325 0.5 2000

TOLUENE 2.10E+06 1.50 0.05250 1.8
ETHYLBENZENE 6.30E+05 1.50 0.01575 0.5
XYLENE 2.30E+06 1.50 0.05750 2.0
C4 1.70E+05 1.50 0.00425 0.1
C5 3.50E+05 1.50 0.00875 0.3
C6 6.70E+04 1.50 0.00168 0.1
C7 7.10E+05 1.50 0.01775 0.6
cs+ 5.50E+05 1.50 0.01375 0.5
AF2 BENZENE 1.40E+04 1.20 0.00028 0.01

TOLUENE 1.90E+04 1.20 0.00038 0.01
ETHYLBENZENE 3.70E+03 1.20 0.00007 0.00
XYLENE 2.10E+04 1.20 0.00042 0.01
C4 9.40E+03 1.20 0.00019 0.01
C5 1.20E+04 1.20 0.00024 0.01
C6 4.00E+04 1.20 0.00080 0.03
C7 4.00E+04 1.20 0.00080 0.03
cs+ 3.20E+04 1.20 0.00064 0.02
AF3 BENZENE 1.30E+05 1.90 0.00412 0.1 1000

TOLUENE 1.00E+06 1.90 0.03167 1.1
ETHYLBENZENE 4.00E+05 1.90. 0.01267 0.4
XYLENE 1.60E+06 1.90 0.05067 1.8
C4 2.50E+04 1.90 0.00079 0.0
C5 3.00E+04 1.90 0.00095 0.0
C6 3.00E+04 1.90 0.00095 0.0
C7 7.70E+05 1.90 0.02438 0.8
C8+ 4.60E+06 1.90 0.14567 5.1
NOTES: 1)30-MINUTE INTEGRATED SAMPLE

2)AF1 SEWER BOX ADJACENT TO COKER
3)AF2 SEWER BOX NEAR THE COOLING TOWER LOWER BOUND
3)AF3 ADJACENT TO TI-IE API SEPERATOR
27
TABLE 2-6, SUMMARY OF SEWER VENT EMISSIONS FROM THE YORKTOWN REFINERY
SEWER BENZENE TOLUENE E-BENZENE XYLENE C4 C5 C6 C7 C8+
VENT EMISSIONS EMISSIONS EMISSIONS EMISSIONS EMISSIONS EMISSIONS EMISSIONS EMISSIONS EMISSIONS
NUMBER (fONS/YR) (fONS/YR) (fONS/YR) (fONS/YR) (fONS/YR) (fONS/YR) (fONS/YR) (fONS/YR) (fONS/YR)
woo 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
AF3 0.46 1.81 0.55 2.00 0.14 0.31 0.07 0.63 0.49
S31 0.46 1.81 0.55 2.00 0.14 0.31 0.07 0.63 0.49
S35 0.30 1.45 0.49 1.88 0.09 0.17 0.05 0.73 0.66
AF3 0.30 1.45 0.49 1.88 0.09 0.17 0.05 0.73 0.66
W84 0.30 1.45 0.49 1.88 0.09 0.17 0.05 0.73 0.66
AF2 0.14 1.10 0.44 1.97 0.03 0.03 0.03 0.83 5.08
W05 0.14 1.10 0.44 1.97 0.03 0.03 0.03 0.83 5.08
W12 0.30 1.45 0.49 1.88 0.09 0.17 0.05 0.73 0.66
TOTAL 2.42 11.63 3.95 15.46 0.70 1.39 0.42 5.84 13.77
TOTAL 117
N
00
should be kept in TIlind that the temperature in the sewers
wasabout 100 F.
0
SE~cond, any ambient wind flow would enhance flow
from the stack compared to the normal sewer grate. In summary,
there should not be significant bias in these data.
29
3.0 Ambient Measurements
The primary goal of the ambient air quality sampling program was
to provide additional verification of the BTEX emission inventory
by comparing the measured concentrations to the predicted
concentrations using the Industrial Source Complex (ISCST)
dispersion model. The ambient monitoring program provided both
speciation data and quantitative impact measurements paired in
time and space. For this analysis, the emission inventory
developed in section 4 and actual on-site meteorology were used
as input to the model. Predicted concentrations were then
compared to observed concentration measurements. It is possible
to quantitatively evaluate the quality of emission estimates (for
speciated hydrocarbon emissions) used in developing the emission
inventory. This verification process is discussed in section 5.
Ambient air monitoring sites were located with the objective to
quantify short-term net air quality impacts associated with
specific refinery process units.
It was not the intent of this ambient monitoring program to
estimate long-term air quality impacts, nor was it a goal to
conduct the ambient monitoring program across the full spectrum
of possible meteorological conditions.
After verification of the emissions inventory, additional
modeling was conducted, using all possible meteorological
conditions, to estimate' the long-term air quality impact
30
(Section 6). The following reasons have been presented why it is
preferable to use a model to estimate long-term impacts as
opposed to attempting to estimate impacts from a long-term
monitoring program.
1) Models can provide estimated concentrations over a wider
geographical region than could be practically done using
mcmitors.
2) Models ensure that the maximum ground-level concentration is
identified.
3) Models help identify which sources or groups of sources are
rE!sponsible for the estimated impacts.
4) Models take into account the full range of possible
meteorological conditions.
5) Models enable forecasting potential benefits from the
application of controls or changes in operations, in terms
of environment:al impacts.
This last point is critical for evaluating the effectiveness of
changes in refinery operation on potential community exposure.
The following SUbsections provide an overview of the sampling
31
methodc)logy used, a summary of the monitoring results,
concluslions regarding the monitoring program and an overview of
the quality assurance program implemented as part of the field
sampling program. A detailed discussion of the ambient
monitoring program, samplers, and analytical protocols is
provided in an accompanying report (Radian 1991).
3.1 Description of the Air Quality Monitoring Program

Ambien1: monitoring for hydrocarbon species was conducted using
two different sampling methodologies. The first approach
utilizE:d a charcoal tube sampler developed by Amoco for
determining BTEX concentrations. This sampler was patterned
after NIOSH sampling Method 1502 (NIOSH 1984). The second
sampling method used evacuated stainless steel canisters to
collect a whole air sample (USEPA Method TO-14) which could be
analyzed for up to 150 hydrocarbon compounds (EPA 1988).
The TO'-14 samplers used a wind-direction sampling vane which

enabled samples to be collected only when the wind direction was
within a selected range. The sampling strategy for both the
charcoal tubes and evacuated canisters was to obtain data for
specific and persistent wind directions in order to characterize
the concentrations both upwind and downwind of refinery sources.
3.1.1 !Charcoal Tube Sampling

The charcoal samplers used a charcoal ampule as a sampling media.
32
Air was drawn into the sampler at a known rate and passed through
the ampule where the organics were sorbed onto the charcoal.
These samplers were equipped with 12 charcoal tubes, solenoid
valves, and a timer which channeled air flow through a different
tube every 2 hours. Thus, with these samplers, it was possible
to obtain 2-hour discrete samples for a 24-hour period with
unattended operation. The 2-hour integration of time is very
important in this sampling strategy. By sampling over this
relatively short period of time, it is possible to collect a
sample under relatively constant meteorological conditions (wind
speed and direction). Thus, using this sampling technique,
specific source impacts can be observed.
After t:he air sample was collected, the charcoal ampule was sent
to a laboratory for chemical analyses. This sampling focused on
BTEX compounds with an analytical detection limit of 0.5 ppb for
each compound. Quantification of chemicals other than BTEX would
have required analytical method development not possible within
the schedule for this project and, therefore, was not included in
this sampling protocol.
During the sampling[ program, 10 charcoal ampule samplers were
used. The location of the samplers was chosen based on
meteorological data which indicated a predominant northeast and
southwe~st flow. This flow regime was dominated by a land and sea
breeze, caused by t:he York River and nearby Chesapeake Bay. The
33
monitoring locations were further refined by modeling benzene
impacts using the SARA 313 emission inventory. The exact monitor
locations were chosen based on maximum predicted impacts for the
2 predominant flow regimes. The sampling locations are indicated
in Figure 3-1 and are labeled A1 through A10. Thus, for a
southwest wind, site A1 would measure impacts from the delayed
coker unit, site A2 would measure the impacts from the Combo and
Ultraformer Units, sites A3 and A4 would be downwind of the
product storage tanks, and site A5 would measure the impacts from
the wastewater treatment area. sites A6, A7, AS, A9, and AID
would measure background concentrations. For other wind
directions, similar source receptor patterns were developed.
Prior b:':> deploying the samplers, the physical location of each
site was reviewed to ensure that no air flow obstructions were
present~.
In employing this sampling strategy, not all samples were
analyzed. A sample~ was selected for analysis if the following
2 criteria were satisfied:
1) The wind speed, direction and stability class as measured on
site, were reasonably constant for the 2-hour period; and
2) Samplers were upwind and downwind of an identified source.
34
...
•
•
,. .J
\\
,_....:!
3.1. 2 ;e:vaouated ca:nister sampling
The second sampling approach utilized a Xonetech Model 9llA
sampler equipped with a wind direction sampling vane. The
sampling media for this sampler was a TO-l4 canister. This
sampler allowed air to be collected by the evacuated canister if
the wind direction was within a predetermined sector. Samples
were collected over a 24-hour period. These samplers were
generally located at sites A2, A3, AS and AlD. Sites A2 and A3
were downwind locations and AS and AlD were upwind locations.
The sampling vanes were orientated so that samples were collected
for a southwest flow with a ±45°-sector. Source identification
with this sampling method is not as precise as with the charcoal
samplers with the 2-hour integration period.
Depending on the day and the sampling location, these samples
were analyzed for BTEX. Two samples per day were also analyzed
for l50 organic compounds using USEPA Method TO-l4. Thus, with
these samplers, it was possible to examine impacts of other
chemicals in addition to BTEX.
It: is useful to compare the advantages of both these sampling
methods. The analytical detection limit of both methods are
similar, approximately 0.5 ppb for BTEX compounds. The precision
of measurements using the charcoal tubes is better than that
found for the TO-l4 Method. For benzene, the precision (based on
field duplicate samples) of the charcoal sampler was found to be
36
±3 percent while that of the TO-14 Method was ±18 percent. The
canister method, however, provides one with the ability to
identify compounds other than BTEX. Finally, because of the
discre'te 2-hour sampling period used with the charcoal samplers,
it is easier to correlate measured results with meteorological
events and, therefore, to identify specific source impacts.
While 2-hour samples could be collected with TO-14 canisters, the
samplers would havl= required a modification to allow automated 2-
hour sample collections over a 24-hour period. The lack of an
automated sampler plus increased analytical costs made such
sampling prohibitive.
3.2 Monitoring Results
3.2.1 pharcoal SamJ)lers
Tables 3-1 through 3-5 present a summary of BTEX concentrations
obtainE~d from the charcoal samplers. Not all of the samples were
analyzE~d (see sample selection criteria in Section 3.1.1). Two
blocks of data are presented for each sampling period analyzed.
The first block lists the day samples were taken, the date,
sample sequence number (i.e., 1-12), time of day and the average
meteorological conditions observed during the 2-hour period. The
second block lists monitoring observations and monitoring data
for sit:es that best: fit the data selection criteria. The column
labeled upwind or downwind indicates that the sampler was either
upwind (U) or dowmdnd (D) of a source. Upwind sources are
identified in the s,econd column of the second block of data. The
37
TABL.E 3-1, SUMMARY OF NET BTEX CONCENTRATIONS FOR SAMPLING DAY 1
DAY SEC~ ws
NO. NO. TIME (MPH) WD STAB.
16:00 7.2 237 o
SITE UPWIND UPWIND' NET NET NET NET

NO. OR SOURCES BENZENE BENZENE TOLUENE TOLUENE E·BENZENE E·BENZENE XYlENES XYlENE
DOWNWIND (UGIM"3) (UGIM"3) (UGIM"3) (UGIM"3) (UGIM"J) (UGIM"3) (UGIM"3) (UGIM"3)
1 0 ,'-'UI\tot' '''..... '''.'0 10.'0
59.33
'U.,~ <LLU U.UU O.b;l 0.""
2 D ULTRA 27.46 26.78 54.31 13.62 13.62 52.48 52.48
3 D PTANKS 23.06 22.38 32.53 27.50 5.99 5.99 26.27 26.27
4 D PTANKS 26.61 25.93 27.73 22.70 5.53 5.53 17.86 17.86
5 D PTANKS 10.58 9.91 39.75 34.72 12.67 12.67 49.75 49.75
6 D P TANKS OFI API 15.01 14.33 45.42 40.40 12.02 12.02 46.28 46.28
7 U O.2~j 4.95 <LlD <LlD
8 U 1.51 4.48 <LlD <LlD
9 U 0.27' 5.65 <LlD <LlD
AVG 0.68 AVG 5.03 AVG 0.00 0.00
~
SEQ, WS
NO. DATE NO. TIME (MPH) WD STAB.
I 0!l725 2 nl:oo S.2 :m 0
SITE UPWIND UPWIND NET NET NET NET

NO. OR SOURCES BENZENE BENZENE TOLUENE TOLUENE E·BENZENE E·BENZENE XYLENES XYLENE
DOWNWIND (UGIM"3) (UGIM"3) . (UGIM"3) (UGIM"3) (UGIM"3) (UGIM"3) (UGIM"3) (UGIM"3t
1 U l'-'UI\toH lU."" ~.;;O 1;;.01
13.63
b.1U ~.8a ~.sa .r" D.""
2 D ULTRA 2.64 1.25 6.42 <LlD 0.00 7.67 6.23
3 D PTANKS 35.46 33.87 51.68 44.26 16.93 16.93 62.23 60.79
4 D PTANKS 13.27' 11.68 17.61 10.21 <LlD 0.00 6.00 4.56
5 0 RET POND 21.32' 19.73 89.51 82.10 30.37 30.37 136.21 134.77
6 U 4.85 16.86 0.48 5.77
7 U 0.01 4.64 <LlD <LlD
8 U 0.86 4.07 <LlD <LlD
9 U 0.63 3.85 <LlD <LLD
AVG 1.59 AVG 7.41 AVG 0.00 AVG 1.44
~
SEa WS
--,-- I 0!l725 ~ 22:00 3.1 ,SB E

DOWNWIND (UGIM"'3l (UGIM"3) JUGIM"3) (UGIM"3) (UGIM"3) (UGIM"3) (UGIM"3) (UGIM"3)
1 U ,1'-'UI\to,. "".IU ,..,..." ......... '".rt> !I."" !I."" "' ..... "".;;Ij
2 0 ' PS 20.16 18.41 34.51 27.43 <LlD 0.00 12.78 10.70
3 0 PTANKS 110.98 109.23 80.93 73.75 12.33 12.33 115.32 113.24
4 0 PTANKS 105.07 103.32 274.07 268.99 63.45 63.45 271.66 269.58
5 0 RET POND 0.82 0.00 2.08 0.00 <LlD 0.00 2.40 0.32
6 U 1.48 7.69 <LlD 0.18
7 U 2.20 7.72 <LlD 3.04
8 U 4.23 9.60 <LlD 4.48
9 U 3.67 8.32 <LlD 0.28
AVG 1.75 AVG 7.08 AVG 0.00 AVG 2.08
~
DAY
NO.
; UPWIND
DATE
01l7::!S
SEQ
NO.
5
TIME
00:00
ws
(MPH)
3.5
WD
,!l3
STAB.
0
\ SITE UPWIND NET NET NET NET

J NO. OR SOURCES BENZENI: BENZENE TOLUENE TOLUENE E·BENZENE E·BENZENE XYlENES XYLENE
DOWNWIND (UGIM"3) (UGIM"3) (UGIM"3) (UGIM"3) (UGIM"3) (UGIM"3j (UGIM"3) (UGIM"3)
LJ COKER
~".'" "b. HI ..... '>0 ;;0.;;1 a.f4 a.f4 ;;0.:>4 .,.,...
2 0 PS 4.14 1.42 14,60 6.51 1.18 1.18 5.33 2.60
3 0 PTANKS 81.18 78.43 82.77 74.68 11.55 11.55 70.74 68.01
4 D PTANKS 164.42 161.68 501.OS 493.00 129.A2 129.92 451.42 448.68
5 0 RET POND 0.77 0.00 2.04 0.00 <LlD 6.00 0.44 0.00
8 U 1.37 5.58 <LlD 1.60
7 U 1.57 7.12 <LlD 2.97
8 U 3.87 9.08 <LlD 4.64
1.49
9 U 4.10
- 2.72
10.58
AVG 8.OS
<LlD
AVG 0.00 AVG 2.73
NOTE: THE AVG REFERS ~ro THE AVERAGE OF THE UPWIND SAMPLES.
38
TABLE 3-1, SUMMARY OF NET BTEX CONCENTRATIONS FOR SAMPLING DAY 1
ws
~
OAY sl:a
NO. DATE N'D. TIME (MPH) WD STAS.
'====~==·=T===9M~R.~!6==~====~II===T==~o~z~:oo~=r===4~.a~~F=~2~~~=T=====D~==~

NO. OR SOURCES BENZENE BENZENE TOWENE TOWENE E-BENZENE E-BENZENE XYlENES XYlENE
DOWNWIND (UGnlf"3) (UGM"3) (UGnIf"3) (UGnIf"3) (UGnIf"3) (UGnIf"3) (UGnIf"3J JUGnIf"3)
u LUl\t;t ~~.4'
28.43
...,..." ..4.""
32.94
...,..." a.w a.B8 , ....>I
'4.~'
2 D PS 25.22 29.08 <llD 0.00 9.04 9.04
3 D PTANKS 103.90 102.70 100.10 96.23 11.43 11.43 50.19 50.19
4 D PTANKS 17.58 16.37 52.08 48.22 12.00 12.00 49.00 49.00
5 D RET POND 8.l!6 5.65 28.13 24.27 8.74 8.74 33.41 33.41
6 U <LLD 4.84 <llD <llD
7 U <ULD 3.00 <llD <llD
8 U 2.116 4.11 <llD <llD
9 U 1.!18 3.50 <llD <llD
AVG 1.21 AVG 3.86 AVG 0.00 AVG 0.00
~
DAY SEa WS
o~!l 04:00 B.l m D

NO. OR SOURCES BENZENE BENZENE TOLUENE TOLUENE E-BENZENE E-BENZENE XYlENES XYLENE
DOWNWIND (UG/M"3) (UGnIf"3) (UGnIf"3) (UGnIf"3) (UGnIf"3) (UGnIf"3J (UGnIf"3) (UGnIf"3)
u ILUl\t::t
"".' "l.~ ";>.b~ "'U., .. ;>.1" 3.111 14.UI 14.UI
2 D ULTRA 10.23 9.25 26.61 23.14 <llD 0.00 23.10 23.10
3 D PTANKS 120.38 119.40 125.28 121.79 13.82 13.82 52.58 52.58
4 D PTANKS 10.:16 9.38 17.91 14.45 <llD 0.00 6.22 6.22
5 D RET POND 25.:12 24.34 107.75 104.28 33.73 33.73 134.71 134.71
6 U LAACK 0.10 4.01 <llD <llD
7 U <UD 3.49 <llD <LLD
8 U 2.55 3.86 <llD <LLD
9 U 1.27 2.49 <LLD <LLD
AVG 0.98 AVG 3.46 AVG 0.00 AVG 0.00
ws
~
SECl
1 09126 a 00:00 4.6 m D

NO. OR SOURCES BENZE:NE BENZENE TOLUENE TOLUENE E-BENZENE E-BENZENE XYLENES XYLENE
DOWNWIND (UGnIf"3) (UGnIf"3) (UGnIf"3) (UGnIf"3) (UGnIf"3) (UGnIf"3) (UGnIf"3) (UGnIf"3)
2
0
D
i~Ul\t::H
ULTRA
",U... '
25.57
1".:>11
23.95
1".1"
56.23
1...1"
50.19
;>.""
11.89
a.a..
11.38
"...
46.07
".f;>
42.49
3 D PTANKS n,37 75.74 99.24 93.21 13.45 13.14 51.99 48.41
4 D PTANKS 43.67 42.04 67.75 61.71 10.03 9.73 38.50 34.92
5 D RET POND 32.1-4 30.51 131.44 125.41 44.39 44.09 183.06 179.48
6 U 3.1SI 16.42 1.21 14.32
7 U <ill) 4.04 <llD <llD
8 U 3.3C1 1.79 <llD <llD
9 U 0.031 1.88 <llD <llD
AVG 1.63 AVG 6.03 AVG 0.30 AVG 3.58
g; NO.
I
DATE
09i2B
seal
NO.
9
TIME
08:00
WS
(MPH)
5.6
WD
222
STAB.
D

NO. OR SOURCES BENZENE BENZENE TOWENE TOLUENE E-BENZENE E-BENZENE XYlENES XYLENE
DOWNWIND (UGnIf"'3J l!1GnIf"3) J:UGnIf":l). J:UGnIf"n (UGnIf"31 roGM"31 (UGnIf"31 (UGnIf"3J
1 u LUI\t;H ...,. ".,.toO ...,..... .....
"<llD ....
"- "u..... '"'u.....
2 D ULTRA ""'''''
7.10 5.22 18.54 13.99 0.00 12.82 12.62
3 D PTANKS SO.lEI 78.30 92.72 88.18 11.40 11.40 40.09 40.09
4 D PTANKS 4.50 2.82 10.99 6.43 1.03 1.03 0.29 0.29
5 D RET POND 10.38 8.SO 40.24 35.88 13.82 13.82 50.65 SO.65
6 U 0.14 3.65 <LLD <llD
7 U 1.81 6.57 <llD 0.84
9 U 3.82 5.46 <llD <llD
AVG 1.89 AVG 4.56 AVG 0.00 AVG 0.00
NOTE: THE AVG REFERS TO THE AVERAGE OF THE UPWIND SAMPLES,

39

NO. OR SOURCES BEN~E BENzeNE TOLUENE TOLUENE E-BENZENE E-BENZENE XYLENES XYLENE
DOWNWIND (UG/M"3) (UG/M"3) (UG/M"31 (UG/M"3) __(tJG/M"3) (UG/M"3) (UG/M"3) (UG/M"3)
0 !,",UI\t:t '0.' '''.00 .00 '''.'>0 ".'"'u ".;,::u ".4' 9.34
2 D ULTRA 29.EI6 29.40 61.56 57.37 14.45 14.45 58.09 58.02
3 D PTANKS 4O.'~7 39.90 55.21 51.02 11.17 11.17 37.37 37.30
4 D PTANKS 28.~i5 27.98 25.68 21.48 7.58 7.58 29.51 29.44
5 D RET POND 11.)'8 11.21 49.33 45.14 15.04 15.04 80.57 60.50
6 D LRACK 6.39 5.81 20.74 16.54 1.91 1.91 17.07 17.00
7 U 1.13 4.58 <LLD 0.14
9 U <LLD 3.81 <LLD <LLD
AVG 0.57 AVG 4.19 AVG 0.00 AVG 0.07
~
SEC) WS
NO. DATE NO. nME (MPH) WD STAB.
1 01l12S n 12:rnl B.2 2:15 0

NO. OR SOURCES BENZENE BENZENE TOLUENE TOLUENE E-BENZENE E-BENZENE XYLENES XYLENE
DOWNWIND (UG/M"3) (UG/M"3) (UG/M"3) _(UG/M"3) ~UG/M"31 ~UG/M"3) (UG/M"3) (UG/M"3)
U lvul\t:r 42.32 ~.2:> 14.0.. '''.'0 0 ..... 0 •..., .>.I.;;;; 33.33
2 D ULTRA 17.1,8 17.11 101.32 98.83 39.76 39.76 159.39 159.39
3 0 PTANKS 16.95 16.87 99.89 97.40 39.10 39.10 156.05 156.05
4 D 1.1E1 1.11 7.52 5.02 <LLD 0.00 4.31 4.31
5 0 1.Zi! 1.15 8.72 6.23 <LLD 0.00 4.60 4.60
6 D O.lel 2.89 <LLD <LLD
7 U 0.10 2.68 <LLD <LLD
9 U 0.01 2.11 <LLD <LLD
9 U O.OS 2.09 <LLD <LLD
Ava 0.07 Ava 2.49 AVG 0.00 Ava 0.00
ws
b
DAY SEa
NO. DATE NO. nME (MPH) we STAB.
oro:!s 12 l~:rnl !l.S 22~ 0

NO. OR SOURCES BENZSNE BENZENE TOLUENE TOLUENE E-BENZENE E-BENZENE XYLENES XYLENE
DOWNWIND (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3)
4 -u IP IANI<;S 18.:>4 111.41 ;J;,::.oo ':1..,0 .:."., .:."., 1 r."" r.3a
5 D RET POND 5.56 5.44 31.16 26.07 13.01 13.01 84.20 53.71
6 U 0.25 7.23 <LLD 0.97
7 U <LLCI 4.56 <LLD <LLD
9 U <LLCI 2.95 <LLD <LLD
NOTES: Ava 0.12 Ava 5.09 AVG 0.00 Ava 0.48
l)PS= POWER STA'nON
2)L RACK= LOADING RACK
3)RET POND= STORM WATER RElrENnON POND
4)ULTFIA= ULTRAFORMER
5)COKER= DELAYED COKER UNIT
6)API= API SEPERATOR
NOTE: THE AVG REFERS TO THE AVERAGE OF THE UPWIND SAMPLES.

FIGURE 3-2, SUMMARtY OF NET BTEX CONCENTRATIONS FOR SAMPLING DAY 2

NO. OR SOURCES BENZENE BENZENE TOLUENE TOLUENE B-BENZENE B-BENZENE XYLENES XYLENE
DOWNWIND (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) ~UG/M"3) . (UG/M"3) (UG/M"3)
0 b lKJ:>lI'VNU iU.b~ IIJ.M lI5.~y 1I.1I L.Y~, li.Y~
7 D COKER 9.35 9.35 10.14 9.03 """"

<Ul)
,,"'lO
0.00 5.91 5.91

2 U <Ul) 1.31 <Ul) <Ul)
5 U <LLD 0.92 <Ul) <LLD
AVG 0.00 AVG 1.11 AVG 0.00 AVG 0.00
SEQ WS
NO. NO. 11ME (MPH) WD STAB.
03:15 5.1 334 0

NO. OR SOURCES BENZENE BENZENE TOLUENE TOLUENE B-BENZENE E-BENZENE XYLENES XYLENE
DOWNWIND (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3J. ,CUG/M"3) ~UG/M"3) (UG/M"3)
"Z u KJ:>lI'VNU
<Ul)
I;./) 1;./) "'.H H>.(» 11.0> v.ro 111./V LU.iV
U 3.79 <Ul) <Ul)
5 U <LLD 3.14 <Ul) <Ul)
AVG 0.00 AVG 3.46 AVG 0.00 AVG 0.00
SEQ ws
05:15 6:2 346 o
DOWNWIND (UG/M"'3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UGIM"3) (UG/M"~,
6 D RET POND 12.84 11.&5 25.79 22.42 1.26 1.26 14.22 14.22
2 U 1.97 6.75 <Ul) <LLD
5 U <LLD <LLD <Ul) <LLD
AVG 0.98 AVG 3.38 AVG 0.00 AVG 0.00
SEQ WS
2 uJ:B 6.0 342 o
UPWIND UPWIND NET NET NET NET
OR SOURCES BENZENE BENZENE TOLUENE TOLUENE B-BENZENE E-BENZENE XYLENES XYLENE
DOWNWIND (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3)
0 ItsAK""" •• )1 I;.V, 0."" 1.W <u..u IJ.W <u..u V.W
D RET POND 11.74 10.30 25.23 19.75 1.35 1.35 14.11 14.11
D COKER 8.15 6.71 10.&5 5.38 <Ul) 0.00 4.65 4.65
U 1.44 5.47 <LLD <LLD
AVG 1.44 AVG 5.47 AVG 0.00 AVG 0.00
SEQ ws
2 g #.15 ).6 341 o
"7
DOWNWIND
U
D
I t<.Cl
COKER
~V!HJ
(UG/M"'3)
o.J,
6.57
(UG/M"3)
J •. ,
5.lS
(UG/M"3)
10.11
8.39
(UG/M"3)
.,~
3.02
(UG/M"~
<u..u
<Ul)
jI.lG/M··3)
u.w
0.00
.....,
(UG/M"~
1.18
.....,
(UG/M"3)
1.18
2 U 1.58 5.25 <Ul) <Ul)
5 U 1.28 5.49 <Ul) 0.00 <Ul)
AVG 1.43 AVG 5.37 AVG o AVG o
41
FIGURE 3-2, SUMMARY OF NET BTEX CONCENTRATIONS FOR SAMPLING DAY 2
SEQ ws
2 10 0:15 1.2 324 D

NO. OR SOURCES BENZENE BENZENE TOLUENE TOLUENE E-BENZENE E-BENZENE XYLENES XYLENE
DOWNWIND (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UGIM"3) (UGIM"3) (UG/M"3) (UG/M"3)
. b D """. rv"u \J.lIl 0$ 1.)1 0.39 <LI.J:J 11.00 <I..LV u.w
7 D COKER 7.78 7.78 9.84 8.72 0.91 0.91 6.39 6.39
8 U <WD 0.62 <WD <WD
10 U <WD 0.60 <WD <WD
2 U <LU) 192 <Lill <Lill
4 U <W) 181 <LLD <Lill
5 U <LLD 0.70 <LLD <LLD
AVG 0.00 AVG 1.12 AVG 0.00 AVG 0.00
SEQ WS
NO. NO.
11
TIME
15:15
NET
(MPH)
6:9
WI)
328
NET
STAB.
D I NET NET
SITE UPWIND UPWIND
NO, OR SOURCES BENZENE BENZENE TOLUENE TOLUENE E-BENZENE E-BENZENE XYLENES XYLENE
DOWNWIND (UG/M"3) (UGIM"3) (UG/M"3) (UG/M"3) (UGIM"3) (UG/M") (UGIM"3) (UGIM")
6 D lKJ:.lI'UNU <I..LV 0.00 \J.bl U,lY <I..I..U 1J.00 <LLU V.W
7 D COKER 12.18 12.18 13.81 13.39 125 1.25 11.18 IllS

2 U <WD 0.73 <WD <Lill
5 U <LLD 0.10 <WD <Lill
AVG 0.00 AVG 0.42 AVG 0.00 AVG 0.00
NOTES:
I)RET POND= RETENTION POND
2)COKER=DELAYED COKER UNIT
3)BARGE=BARGE I..oADING
.47

DOWNWIND (UG/M·*3) (UG/M'*3) (UG/M"3) (UG/M*'3) (UG/M'*3) (UG/M'*3) (UG/M*'3) (UG/M**3)
IU u IAN" l;j.bI! 1;j.tIl; l~.;j;j l~.;j;j .,..,.. ".00 ;.~" ..."
5 U 0.01 <LLD <LLD <LLD
AVG 0.01 AVG 0.00 AVG 0.00 AVG 0.00
[±
SEC! WS
DATE NO. TIME (MPH) WD STAB.
3 I Og72S 5 OS:!lll 1.7 2SIl I:l

DOWNWIND (UG/M*'3) (UG/M"3) (UG/M**3) (UG/M*'3) (UG/M*'3) (UG/M'*3) (UG/M'*3) (UG/W*3)
~ u )l.oU"l:H bb."" b4.b" 0".44 bU."" l;j.W l;j.W bO"''' 02.18
3 D COMBOIULTRA 160.09 156.23 230.53 221.61 45.72 45.72 239.42 236.12
4 D PTANKS 75.41' 71.60 115.56 106.64 21.21 21.21 86.69 83.39
5 D PTANKS 87.5<1 83.67 213.39 204.48 70.67 70.67 306.96 303.66
6 D API 77.1~1 73.27 115.81 106.90 12.09 12.09 56.75 53.45
9 U 3.77 9.56 <LLD 4.06
10 U 3.96 8.27 <LLD 2.55
~IVG 3.86 AVG 8.92 AVG 0.00 AVG 3.30
~
SEa ws
I Og72S S oa:ljO 1.2 27tl F

DOWNWIND (UG/M*·3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3)
I:l ~UNU U.Ul <u.u u.u <u.u V.Vl <u.u u.u·
"6 D API 4.60
U.U
4.60 10.76 4.60 <LLD 4.60 4.27 4.80
7 U 6.71 8.03 <LLD 1.86
AVG 6.71 AVG 6.71 AVG 6.71 AVG 6.71
ws
~
SEa
NO. ~==~D~A~TE?===r===N~OF'===r==~TI~M~EF=~==(~M~PH?)==r=~WD~==~====ST~AFB='==~
I M72S S 12m 3.0 324 B

DOWNWIND (UG/M**3) (UG/M**3) (UG/M**3) (UG/M'*3) (UG/M**3) (UG/M*'3) (UG/M**3) (UG/M**3)
~ u 'UNU U.W <:.10 u..... <u.u U.UU <u.u U.UU
5 U 3.00 2.06 <LLD <LLD '

10 U 3.00 1.23 <LLD <LLD
AIIG 3.00 AVG 1.65 AVG 0.00 AVG 0.00
~
SEa ws
1111729 111 lS:!lll :1.7 12!l B

DOWNWIND (UG/M**:i) (UG/M*'3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3)
U IANI\,:S u.tie U.tiO ".bf .{tI <LLU U.W <I.W u.w
2 D PTANKS 2.67 2.83 4.96 4.07 <LLD 0.00 <LLD 0.00
3 U 0.01 <LLD <LLD 0.00 <LLD
7 U 0.06 1.78 <LLD <LLD
AVG 0.04 AVG 0.89 AVG 0.00 AVG 0.00
NOTES:
l)P TANKS PRODUCT= STORAGE TANKS
2)COKEA=DELAYED COKER UNIT
3)COMBOIULTRA= COMBO UNIT AND ULTRAFOAME'R UNIT
4jR POND=RETENnON POND
5)API=API SEPERATOR
NOTE: THE AVG REFERS ~ro THE AVERAGE OF THE UPWIND SAMPLES *
43
TABLE 3-4. SUMMARY OF NET BTEX CONCENTRATIONS FOR SAMPLING DAY 4
~F==~D~A~TE~==T===N~OF·===r==~TI~M~EF=~==(9~1~P.d~F=~==~W~DF==r====s9TAS~'===9
~. 09/29 ~ 02:00 223 0
SITE UNWIND UPWIND NET NET NET NET

NO. OR SOURCES BENZENE BENZENE TOLUENE TOLUENE E-BENZENE E-BENZENE XYLENE XYLENE
OOWNWIN (UG/M o03) (UG/Mo03) (UG/M o03) (UG/M o0 3) (UG/Mo*3) (UG/M*o3) (UG/M o03) (UG/Mo*3)
'" u ' c;ul\t:r ~4.tiO
89.83
,,1.U1
86.19
44.~o
128.78
"".i"
119.25
0."" O.U..
,,~.'''' 24:06·
3 D I ULTRA/COM 19.86 19.86 130.04 125.28
4 D PTANKS 17.13 13.49 n.41 67.86 19.05 19.05 86.00 83.24
5 D RPONDS 4.87 1.23 13.02 3.50 2.96 2.96 15.18 10.42
6 U 2.93 8.68 <LLD 4.04
7 U 1.35 3.43 <LLD <LLD
8 U 2.99 6.73 <LLD <LLD
9 U 4.34 10.38 <LLD 5.49
AIIG 3.64 AVG 9.53 AVG 0.00 AVG 4.76
~
WS
DATE NO. TIME (MP~ WD STAB.
Oro:19 :1 O~:OO 1.9 212 0

NO. OR SOURCES BENZENIE BENZENE TOLUENE TOLUENE E-BENZENE E-BENZENE XYLENE XYLENE
DOWNWIN (UG/Moo:l) (UG/M o0 3) (UG/Mo03) (UG/M o0 3) (UG/M o03) (UG/Mo03) (UG/M o0 3) (UG/M o0 3)
2 D COKER 40.,4 '>b.'.> ou."'" 4:<.19 0."" 0."" ,"~.1" 20.04
3 D ULTRA/COMBO 68.30 64.79 101.49 93.73 15.99 15.99 143.53 140.94
4 D PTANKS 3.30 0.00 9.60 1.86 <LLD 0.00 6.81 4.22
5 D RET POND 5.28 1.77 10.35 2.62 <LLD 0.00 6.45 3.86
6 U 3.12 7.02 <LLD 2.85
7 U 2.38 5.70 <LLD 0.70
8 U 3.44 7.87 <LLD 1.45
9 U 5.10 10.36 <LLD 5.35
AVG 3.51 AVG 7.73 AVG 0.00 AVG 2.59
~
WS
NO. DATE NO. TIME (MP~ WO STAB.
~ OroZ9 3 06:00 1.4 z15 0

NO. OR iSOURCES BENZENE, BENZENE TOLUENE TOLUENE E-BENZENE E-BENZENE XYLENE XYLENE
DOWNWIN (UG/Mo03) (UG/M o03) (UG/Mo*3) (UG/Mo03) (UG/MOOS) (UG/M o03) (UG/Mo03) (UG/Mo*3)
:< u ";UI\t:, 04.82 ~.03 1UO.~5
"i."" ' ' ' '3 D."" 'OO.vo.: "9.9"
3 D IJLTRA/COMBO 86.30 82.11 128.03 118.40 22.48 21.99 157.01 150.97
4 D PTANKS 26.53 22.34 60.04 50.41 18.84 18.38 73.93 67.69
5 D I~ETPOND 3.67 0.00 9.03 0.00 <un 0.00 9.03 2.99
6 U 5.46 14.46 1.92 12.76
7 U 3.35 5.95 <un 2.89
8 U 3.19 7.38 <un 2.17
9 U 4.79 10.73 <un 6.32
-
AVC, 4.20 AVG 9.83 AVG 0.48 AVG 6.04
~
WS
NO DATE NO. TIME (MPH) WD STAB.
~. L'==~0~9~/Z~9=='=9r===9~====r=~O~8:~OO~=P===#0.~~===P==~21~8F==T====~F====~

DOWNWIN (UG/MoOS) (UG/Mo0 3) (UG/Mo0 3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/Mo03) (UG/Mo*3)
:< u LiUl\t:t SO.at> ~.W (~.UO ~.rl ~.:<:> b.ll ;J4.W . JO:03
3 D LlLTRA/COM80 231.40 226.97 294.86 286.37 28.25 28.11 197.86 193.01
4 0 PTANKS 82.44 78.00 120.01 111.72 19.94 19.80 107.03 102.15
5 D FlPOND 81.58 57.13 159.81 151.52 48.35 48.21 210.89 208.02
6 0(1) 30.01 25.58 76.83 86.54 22.85 22.51 105.27 100.40
7 IJ 5.00 9.53 0.42 8.26
8 U 3.39 5.65 <un 1.47
9 U 4.91 9.68 <un 6.87
AVG 4.43 AVG 8.29 AVG 0.14 AVG 4.87
l)UGHT AN[) VARRIBLE WINDS IMPOSSIBLE TO CLEARLY DEFINE UPWIND OR DOWNWIND CONDmONS
NOTE: THE AVG REFERS iTO THE AVERAGE OF THE UPWIND SAMPLES.
44
TABLE 3-4. SU!vlMARY OF NET BTEX CONCENTRATIONS FOR SAMPLING DAY 4

NO. OA SOURCES BENZEIllE BENZENE TOLUENE TOWENE E-BENZENE E-BENZENE XYLENE XYLENE
OOWNWIN (UG/M"*3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M·*3)
LJ IAN"" V.V U.W <LUI U.UO <u.u V.UU <U.U 0.00
2 0 PTANKS 12.3E1 10.36 22.37 20.24 3.63 3.63 18.51 18.51
3 0 LA 1.88 0.00 5.40 3.28 <LLD 0.00 6.40 6.40
9 U 1.66 0.64 <LLD <LLD
10 U 4.33 5.53 <LLD <LLD
AVG 2.00 AVG 2.12 AVG 0.00 AVG 0.00
~
WS
I 09J29 10 20:00 3.3 151 0

DOWNWIN (UG/M*·3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3)
2
D
0
11-'::;ILJLlHA
PTANKS
'''.1''
18.67
12.
18.66
15.98
29.37
15.98
29.37
<UJJ
4.66
U.W
4.88
0.0,
28.43
o.Of
28.43
3 0 LA 18.27 16.26 33.42 33.42 8.64 8.64 50.93 SO.93
4 0 LA 1.64 1.63 7.59 7.59 1.42 1.42 11.73 11.73
AVG 0.01 AVG 0.00 AVG 0.00 AVG 0.00
NOTES:
l)COKER=DELAYED COKER UNIT
2)COMBOIULTRA=COMBINATION AND ULTRAFORMER UNITS
3)P TANKS=PRODUCT STORAGE TANKS
4)R POND= RETEN"nON POND
5)PS POWER STATION
6)LA=LOADING RACK
45
TABLE 3-4. SUMMARY OF NET BTEX CONCENTRATIONS FOR SAMPLING DAY 5
NO. DATE NO. WSnME STAB. we
b UPWIND
(MPH)
__~5__~I____~09~/~30~.__~__~__ .~~~oa~:00~__L -__~3.~6__~__~20~a~-L____~D~__~
NET NET
SITE UPWIND NET NET
NO. OA SOURCES BENZENE BENZENE TOLUENE TOLUENE E-BENZENE E-BENZENE XYLENE XYLENE
DOWNWIND (UG/M**3) (UG/M**3) (UG/M*'3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3)
1 u l,-uI\t:r ~/./~ 34.81 ~".o .. "U.UI <u.u V.W 10."0 1".1"
2 D COMBOiULTRA 170.74 167.82 263.32 257.68 7.99 7.63 31.46 29.23
3 D PTANKS 46.59 45.67 74.67 69.04 13.64 13.27 97.01 94.78
5 D A POND 2.23 0.00 5.45 -0.18 <LLD 0.00 1.16 0.00
6 U 1.31 2.80 <LLD 1.09
7 U 2.35 5.22 <LLD 1.03
8 U 2.28 3.94 <LLD <LLD
9 U 5.75 10.57 1.45 6.79
AVG 2.92 AVG 5.63 AVG 0.36 AVG 2.23
b;
DATE NO. nME WS WD STAB.
{MP~
097:10 Z Ol'!:oo Z. lilt! 0

DOWNWIND (UG/M**3) (UG/M**3) (UG/M**3) (UG/M"3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3)
u COKEA 1.1;4 4.{" 11.0<0 0.00 <u..u U.W ".,it. .1i4
2 D COMBOiULTRA 40.05 36.93 53.77 47.91 <LLD 0.00 10.18 8.30
3 D PTANKS 52.79 49.67 68.09 82.23 18.98 18.64 130.06 128.17
5 D RPOND 0.79 0.00 2.68 0.00 <LLD 0.00 <LLD 0.00
6 U 1.47 3.70 <LLD <LLD
7 U 1.67 3.85 <LLD <LLD
8 U 3.56 5.63 <LLD 0.90
9 U 5.79 10.27 1.33 6.62
~
AVI" 3.12 AVG 5.86 AVG 0.33 AVG 1.86
O. ===~D~A~T~E====F===N~OF'==:=r==~n~M~E~=r==~WS~==T===~W~DF==T====ST~A~B=.==~
~ O!l7:1O 3 10:00
NET
(MPH)
2.6 :204 C
SITE UPWIND IJPWIND NET NET NET

DOWNWIND (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3)
1 u . ~.;ul\t:11 .IV Q.04 ....., "1.39
..... <u.u U.W . 4.11 ( 4.U2
2 D COMBOiULTRA 3.69 1.53 5.43 <LLD 0.00 <LLD 0.00
3 D F'TANKS 76.88 74.72 78.05 74.01 12.24 12.24 70.56 68.70
5 D FlPOND 1.32 0.00 3.39 0.00 <LLD 0.00 1.04 0.19
6 U FlPOND 0.32 1.41 <LLD <LLD
7 U 0.46 2.01 <LLD <LLD
8 U 2.02 2.99 <LLD <LLD
·9 U 3.86 6.07 <LLD 1.71
AVG, 2.16 AVG 4.04 AVG 0.00 AVG 0.86
we
~
NO. DATE NO. nME WS STAa·
5 J 09730 4 12:00 ~~
.2 225 C

DOWNWIND (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3)
1 u ,-OKEA 14.~" IU.'" ".00 0."" <u.u -II."'" ".;;oU -II. '"
2 D COMBOiULTRA 35.80 31.33 64.67 51.31 8.77 8.45 39.04 35.55
3 D PTANKS 20.82 18.55 23.81 20.25 0.99 0.67 10.87 8.19
5 D RPOND 7.57 3.30 9.27 5.90 1.68 1.34 9.21 8.73
8 D 15.43 12.63 1.28 9.95
8 U 1.63 0.63 <LLD <LLD
9 U O.Dl <LLD <LLD <LLD
AVG 4.27 AVG 3.37 AVG 0.32 AVG 2.49
NOTE: THE AVG REFERS 'TO THE AVERAGE OF THE UPWIND SAMPLES.
46 .
TABLE 3-5. SUM[MARY OF NET BTEX CONCENTRATIONS FOR SAMPLING DAY 5
NO. DATE NO. TIME ws WD STAB.
(MPH)
g 08/30 6 16:00 4.B 230 6

DOWNWIND (UG/M**3) (UGIM**3) (UGIM**3) (UGIM**3) (UGIM**3) (UGIM**3) (UGIM**3) (UGIM**3)
u .,v,,'" 1.10 .f4 O.!m O.!m <LUJ U.OO <LW u.uv
2 0 GOMBONLTRA 12.87 12.88 4.39 4.39 <llD 0.00 <llD 0.00
3 0 PTANKS 75.69 75.88 80.97 80.97 10.70 10.70 46.10 46.10
8 D API 10.53 10.52 <llD 0.00 <llD 0.00 <llD 0.00
5 0 nPOND 925.18 925.17 55.94 55.94 0.80 0.80 1.88 1.88
7 U 0.01 <llD <llD <llD
AVG, 0.01 AVG 0.00 AVG 0.00 AVG 0.00
~
DATE NO. TIME WS WD STAB.
(MP!:!)
08/30 19:00 3.& :!lB C

NO. OR SiOURCES BENZENE BENZENE TOLUENE TOLUENE E-BENZENE E-BENZENE XYLENE XYLENE
DOWNWIND (UG/M**3) (UGIM**3) (UG/M**3) (UGIM**3) (UGIM**3) (UGIM**3) (UG/M**3) (UGIM**3)
u ) "uREA "'U. ",U.1U ,.~.
.bl U.40 U.40 .BI .~,
2 0 C:OMBONLTRA 7.36 6.75 15.60 15.37 <llD 0.00 7.36 7.36

3 D PTANKS 105.84 105.24 97.67 97.44 12.34 12.34 53.56 53.56
5 D RPOND 738.90 738.30 80.97 80.73 4.05 4.05 16.77 16.77
6 U 2.39 0.30 <llD <llD
9 U 0.01 0.64 <llD <llD
AVG 0.61 AVG 0.24 AVG 0.00 AVG 0.00
~
DATE NO. TIME WS WD STAB.
(MPH)
5 I og7!lo 6 ~O:OO ~.B :no [l

DOWNWIND (UG/M**3) (UGIM**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UGIM'*3)
u l;U"I::H ;Z.bf .fo Z.l9 2.00 <LW O.W <~ U.UU
2 0 COM80!UTlRA 0.01 0.00 1.23 0.49 <llD 0.00 <llD 0.00
3 0 PTANKS 104.55 103.62 110.80 110.06 13.88 13.88 54.36 54.38
6 0 U~ 0.01 0.00 <llD 0.00 <llD 0.00 <llD 0.00
5 0 RPOND 2194.9 2193.95 215.98 215.24 17.34 17.34 65.76 65.76
8 U 1.94 1.18 <llD <llD
9 U 0.82 1.05 <llD <llD
AVG 0.92 AVG 0.74 AVG 0.00 AVG 0.00
~NO_ DATE NO. TIME WS

(MPH)
WD STAB.
5 [ 08/30 9 22:00 4.2 ~2' [l
SITE UPWIND UfWlND NET NET NET NET

DOWNWIND (UG/M**3) (UG/M**3\ (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3)
U ) ",'REA 0.U1 0.00 <LW 0.00 <lIU o;w <ll.D U.UU
2 0 C()M80NLTRA 49.73 48.11 94.68 93.52 18.10 18.10 73.44 73.44
3 0 PTANKS 48.93 47.21 87.22 66.06 8.72 8.72 36.69 38.69
5 0 RPOND 1109.1 1107.47 131.38 130.22 9.73 9.73 36.15 36.15
6 U 4.69 2.88 <llD <llD
7 U 0.93 1.22 <llD <llD
8 U 0.86 <LlD <llD <llD
9 U 0.01 0.53 <llD <llD
AVG 1.62 AVG 1.16 AVG 0.00 AVG 0.00
NOTE: THE AVG REFERS ~W THE AVERAGE OF THE UPWIND SAMPLES.
47
TABLE 3-5. SU~1MARY OF NET BTEX CONCENTRATIONS FOR SAMPLING DAY 5

DOWNWIND (UG/M.**3) (UG/M**3) (UG/M**3) (UG/M**3)
3 D IAN"'; .,..,,, e."" 10.40 10.40
(UG/M**3)
,(0
(UG/M**3)
1,(0
(UG/M**3)
".uo
(UG/M**3)
".uo
6 D RPOND 704.66 694.32 81.48 74.29 6.83 6.83 28.14 24.63
5 D RPOND 26.21 23.11 20.34 18.03 <LLD 0.00 8.85 8.60·
2 U 7.53 5.93 <LLD <LLD
7 U 5.96 5.15 <LLD 1.24
B U 1.99 0.50 <LLD <LLD
9 U 0.01 <LLD <LLD <LlD
- 3.10 AVG 2.32 AVG 0.00 AVG 0.25
O. -===D~AffiT~E====r===N90~'=='=r==~TT-IM~E~=r==~W~S~=r===W~D===r===S=T"A=B'===9
~ _
10/01 12 04:00
(MPH)
9.2 5.6 0

DOWNWIND (UGIM**3) (UG/M**3) (UGIM**3) (UG/M**3) (UGIM**~ J.UGIM**3) (UGIM**3) (UGIM**3)
1J I c;OKEHlCOMBU 10.25 10.'14 .19 r.19 <LW U.UV ".~ 3.0
B D ULTRA 0.01 0.00 <LLD 0.00 <LlD 0.00 <LLD 0.00
9 D COKER 0.01 0.00 <LLD 0.00 <LLD 0.00 <LlD 0.00
10 D COKER 0.91 0.90 <LLD 0.00 <LlD 0.00 <LlD 0.00
2 U 0.01 <LLD <LLD <LlD
AV(, 0.01 AVG 0.00 AVG 0.00 AVG 0.00
NOTES:
1)COKER~DELAYEO COKER UNIT
2)COMBOIULTRA=COMBINATION UNIT ULTRAFORMER UNIT
3)R POND=RETENTION POND
4)API=API SEPERATOR
5)P TANKS=PRODUGT STORAGE TANKS
NOTE: THE AVG REFERS TO THE AVERAGE OF THE UPWIND SAMPLES *
48
concentrations in micrograms per cubic meter (ug/m3) for each
compound are listed under each compound's name. Net impacts were
estimated as follows:
1) The concentrations at the upwind samplers were averaged;
then
2) This average 'was subtracted from the downwind sampler's
concentration.
In Table 3-1, for ,example, on sampling day 1, hour 02:00 at
site 1, the average benzene concentration is 23.47 ug/m3. The
upwind concentration average is 1.21 ug/~ (from [0.00, 0.00,
2.96, 1.88] for sites A6, A7, A8 andA9, respectively), making
the net benzene for site 1, 22.26 ug/~ (since 23.47 - 1.21 =
22.26). The resulting benzene concentration at this site is
primarily attributable to the delayed coking unit.
In Figures 3-2 through 3-5, the BTEX monitoring results are
plotted as a function of wind direction and overlaid on a
refinery plot plan. The concentration scale on these plots is
logari1t:hmic (1. e., 10, 100, 1,000 ug/m3). From these figures, it
is possible to correlate the monitoring data to the responsible
sources.
The aVE:rage 2-hour background concentration for BTEX over the
49
'\
w
~
Ii
-- I
.... +-
I . ...,i
I
9 19
AI«7CD an.. COMPANY

YD~D'VN MF"lN£RY
YQliCTD\{H.VA.
• I'CLLlJTtDH PKV£HTXIt ~D..IEtT
!tbJlbenzene measurements •• • SAMPLE lDCA TlDNS
function of wind direction
AIo'DCO alRPCRAT~
GRtl.IHD'w'ATEJi: ~T SECTIDN
Rina 1 1 U8/m3
Rin, 2 10 U8/.3
Rinc 3 100 ua/m 3 WG. HC,
... .11
' TlOlOZ01AS
J.IIItAVH JY' ..
D. L UTCHFltLD SOILI: DI rEEl'
i 10-D-'O
.
Figure 3- 4. Et~ylbenzene
•
~IVER •
\
'.
ala
Xylene Me&8Urement • • • •
function of wind direction At«lCll IXJRPORATJOII
Ring 1 u,/~3 GRWNDYATtR NANA:&MEHT SECTIDN
Ring 2 10 ug/.)
Ring 3 100 ug/m 3 D"G. NO.
'Mll2O!AS ... ...
l)RA\iN IYI ....
J). L LITOi'1Q..II SOOU,"=r
i 10·!3-'O
---.
Figure 3-5. Xylene
53
5-day sampling program was 2.4, 4.8, 0.04, and 1 ug/m3,
respectively.
Charcoal samplers were used inside the refinery fenceline.
However, because of the 2-hour averaging time, these data cannot
be compared directly to any applicable air quality standards
which are typically for longer averaging periods.
Discussion of Monitoring Results

The highest net benzene concentrations were measured at site A5.
At this site, the maximum 2-hour benzene concentration was
2,195 ug/m3, which occurred on day 5 at hour 20:00. At this
location on this day, several other elevated concentrations of
benzene were observed (1,107 ug/m3 at 22:00, 925 ug/m3 at 1,600
and 739 ug/m3 at 18:00). Based on an analysis of these data,
elevated concentrations resulted from emissions at an earthen
surface impoundment~ used as an equalization basin, and located
upwind of this sampler. Several days prior to the field sampling
program, the equalization basin was permanently removed from
service and drained prior to cleanup. Because the basin was
removed from service (to meet a compliance deadline for land use
restrictions on characteristically hazardous streams), it has not
been possible to quantify emissions. The following provides a
summary of the analysis that was conducted.
Based on our analysis, there are three reasons why the drained
54
equalization basin and not the API separator was responsible for
the elevated concentrations at site 5.
The first reason for this conclusion is based on the observed
meteorological data. The high benzene measurements at site 5 are
summarized in the following table, along with the reported wind
direction.
Net Mean
Benzene WD
(ug/m3 ) (Deg)
16 925 230
18 738 218
20 2194 210
22 1107 221
The orientation between the API separator and the sampler at
site 5 was about 190°. As indicated by the wind direction data,
mean flow was a minimum of 20° away from the orientation of the
API separator and sampler, and ranged to a maximum of 40°. Winds
during these sample periods were light but not calm. Ideally,
one would like more separation between sources to aid in source
culpability analysis. However, these data strongly suggest the
emissions from the .API separator were not the dominant source.
The second reason that these measurements are not a result of
emissions from the .API separator was made by examining the ratio
of: toluene to benzene; ethylbenzene to benzene; and xylene to
55
benzene for the concentration measurements at site 5 and the
emission measurements at the API separator.
At site 5, the ratio of toluene to benzene ambient air
measurements was 0.097. The ratio of ethylbenzene to benzene was
0.006 and the ratio of xylene to benzene was 0.022. By
comparison, the rat:io of toluene to benzene emissions from the
API separator was approximately 6. For ethylbenzene and benzene,
the ratio of emissions was 2 while for xylene and benzene the
ratio was 8.6. Thus, the source characteristics of the API
separator are very different than the profile of ambient
concentrations observed at Site 5 during these times.
The third reason supporting the premise that the API separator is
not the culpable source, is that strong hydrocarbon odors were
detected during thE~ sampling program emanating from these basins.
Thus, a sUbstantial portion of the anomalous impacts may be
explained by these temporary sources. The preceding analysis and
observation provides a strong indication that the API separator
was not responsible for these large impacts.
At Site A6, an elevated concentration of about 700 ug/m3 was
observed on day 5 at 00:00. During this period, wind direction
was variable as indicated by the large sigma theta. During the
above referenced time periods, TEX concentrations were
56
considerably lower than the measured benzene concentrations.
Based on the analysis done for the elevated concentrations at
site 5, we feel that the drained equalization basins were
responsible for this concentration. At site A6 when the benzene
concentration was approximately 700 ug/m3 , toluene, ethylbenzene
and xylene concentrations were 81, 7 and 28 ug/m3 , respectively.
An estimated worker exposure assessment was performed using a
crude approximation using a power law relationship (USEPA 1987)
to convert 2-hour benzene concentration measurements into an 8-
hour exposure for comparison to the 1 ppm (3200 ug/m3 ) OSHA
standard. At site A5, where the highest benzene concentrations
were measured, the extrapolated maximum 8-hour exposure is
slightly below 0.5 ppm (1600 ug/m3 ) . At site A6, where the
700 ug/m3 concentration was recorded, the extrapolated maximum 8-
hour exposure is approximately 0.15 ppm (480 ug/m3 ) .
Analyzing the monitoring data provides an estimate of the short-
term air quality impacts of selected refinery sources. The
following discussion presents monitoring results for various
sources.
Tanks
The impacts of the product storage tanks emissions were clearly
identified at sites A3 and A4. The maximum 2-hour benzene impact
from these sources was 160 ug/m3 • The maximum 2-hour toluene
57
impact was 493 ug/m3 • For ethylbenzene, the maximum 2-hour
impact was 130 ug/m3. The product storage tanks contributed a
maximum xylene (combined) impact of 448 ug/m3. These maximum 2-
hour impacts occurred at the same time.
Coker
The impact:s of emissions from the delayed coker unit were
observed at site Al. The maximum 2-hour impacts for BTEX from
this unit were 90, 80, 13 and 62 ug/m 3 , respectively. The peak
benzene, t:oluene, ethylbenzene and xylene (total) impacts all
occurred on day 3, hour 06:00.
Coker/Ultraformer
The maximum 2-hour impacts for BTEX from the Combo and
Ultra former unit emissions as observed at site A2 were 227, 286,
46 and 236 ug/m 3 , respectively.
Loading Rack
At site AS, the impacts from the product loading rack emissions
were observed resulting in a maximum 2-hour benzene impact of
18 ug/m 3 • The maximum toluene impact for this source was
33 ug/m3 • Similarly, the maximum ethylbenzene concentration was
9 ug/m 3 and the maximum xylene concentration was 51 ug/m3 •
3.2.2 Monitoring Results From Wind Direction TO-14 Samplers
The results from the 150-compound analyses using the wind
58
direction TO-14 samplers are presented in Table 3-6. This table
summarizes the net increase in impacts (upwind subtracted from
downwind impacts) for those 84 chemicals where at least one
downwind sample concentration exceeded the upwind sample
concentration during the sampling period. If an increase was not
observed, then the chemical was not listed in this table. The
reader is referred to the Radian report (Radian 1991) for a list
of all 150 chemicals included in this portion of the analysis.
For sampling day 1, the upwind sampler did not collect a
sufficient volume to permit analyses of the canister. Therefore,
the upwind data from the other sampling days were averaged and
used as upwind concentrations for sampling day 1.
While it is difficult to determine explicitly the source of
emissions from these data, these data provide a semi-quantitative
indicator of emissions from the facility. Since refinery
emission rates for -the BTEX compounds have been defined with a
reasonable degree of confidence, it should be possible to get a
rough estimate of the refinery emissions for those 84 compounds
measured with the TO-14 canisters. This can be done by rationing
the measur,ed concen"tration of one of the BTEX compounds to the
measured concentrations of the other 84 compounds and then
multiplying that ratio by the emission for the BTEX compound.
Since toluene has one of the highest estimated emission of the
BTEX compounds and it also had the largest downwind impacts for
59
TABLE 3-6. SUMMARY OF NET CONCENTRATION MEASURMENTS USING USEPA
TO-14 SAMPLING METHOD
DAY 1 DAYS 4,5&6 DAY 1 DAY 4 DAY 4 DAYS DAYS DAYS DAYS DAY 6 DAY 6
SITEA3 AVERAGE SITEA3 SITEA3 AVERAGE SITEA3 SITEA2 SITEA3 DAYS SITEA2 SITEA3 SITEA2 SITEAZ
DOWNWIND UPWIND NET DOWNWIND UPWIND NET DOWNWINJ: DOWNWIND AVERAGE NET NET DOWNWIND NET
COMPOUND NAME (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) UPWIND (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3)
1,1, I-TRICHLOROImiANE 0.80 3.37 NO 4.70 2.70 2.00 0.90 1.00 1.70 NO NO 10.20 3.50
1,2,3-TRIMETHYLBENZENE NO 0.47 ND 18.40 1.75 16.65 4.20 5.80 0.70 ND 5.10 ND ND
1,2,4-TRIMETHYLBENZENE ND 1.30 ND ND 0.00 0.00 1.50 ND 1.95 ND ND NO NO
l,3,5-TRIMETHYLBENZENE 6.70 1.57 5.13 22.00 1.45 20.55 6.90 6.20 1.75 3.38 4.45 3.00 1.80
1-0CTENE NO 0.00 0.00 2.40 0.00 2.40 NO NO 0.00 0.00 ND NO NO
2,2,3-TRIMETHYLPENTANE 2.30 0.00 2.30 12.30 0.75 11.55 NO NO 0.00 2.30 NO NO NO
2,2,4-TRIMETHYLPENTANE 7.80 2.07 5.73 38.30 3.50 34.80 5.10 10.10 1.95 3.78 8.15 NO NO
2,2,S-TRIMETHYLHEXANE 1.90 0.00 1.90 3.70 0.00 3.70 NO NO 0.00 1.90 NO NO NO
2,3,4-TRIMETHYLPENTANE NO 0.20 NO 20.20 1.30 18.90 0.60 2.50 0.30 NO 2.20 NO NO
2,3-0IMETHYLBUTANE 11.30 0.83 10.47 43.30 1.00 42.30 12.70 26.60 0.45 10.02 26.15 NO NO
2,4-DIMETHYLPENTANE 2.20 0.20 2.00 12.50 0.70 11.80 ND ND 0.30 1.70 NO NO NO
2,S-OIMETHYLHEXANE 2.60 0.00 2.60 8.20 0.35 7.85 ND NO 0.00 2.60 NO ND ND
2-BUTANONE NO 1.00 NO NO 0.00 0.00 NO NO 0.00 0.00 ND NO ND
2-METHYL-I-BUTENE 6.90 1.33 S.57 22.40 0.45 21.95 10.30 37.60 0.00 5.57 37.60 NO NO
2-METHYL-I-PENTENE 2.10 0.00 2.10 15.80 0.00 15.80 14.40 17.40 0.00 2.10 17.40 NO NO
2-METHYL-2·BUTENE 15.50 2.30 13.20 48.40 0.30 48.10 17.60 80.00 0.00 13.20 80.00 NO NO
2-METHYL-2-PENTENE 4.30 0.00 4.30 10.10 0.00 10.10 6.30 21.00 0.00 4.30 21.00 NO ND
3-METHYLHEPTANE 4.40 0.57 3.83 14.30 0.40 13.90 5.90 5.00 0.85 2.98 4.15 ND ND
3-METHYLHEXANE 9.60 2.03 7.57 40.00 2.00 38.00 12.80 20.80 0.70 6.87 20.10 ND NO
3·METHYLPENTANE 23.40 2.80 20.60 86.40 2.65 83.75 37.40 55.10 2.25 18.35 52.85 NO NO
A·PINENE ND 3.07 NO NO 7.15 NO ND ND 4.60 ND ND NO NO
ACETONE 16.80 18.60 ND 13.50 3.20 10.30 13.10 33.50 18.95 NO 14.55 ND NO
'"o B·PINENE NO 0.77 ND NO 3.35 ND NO NO 1.15 NO NO NO NO
BENZENE 20.80 3.30 17.50 119.00 4.45 114.55 33.00 70.30 2.20 15.30 68.10 NO NO
C2-BUTENE 12.90 1.83 11.07 11.70 0.00 11.70 15.70 31.30 0.00 11.07 31.30 NO NO
C2-HEXENE ND 0.00 0.00 6.50 0.00 6.50 3.40 6.50 0.00 0.00 6.50 ND NO
C2-PENTENE 5.00 0.93 4.07 10.30 0.00 10.30 6.50 26.20 0.00 4.07 26.20 ND NO
C3-HEXENE 2.00 0.00 2.00 3.50 0.00 3.50 2.80 8.90 0.00 2.00 8.90 ND ND
CARBON TEl'RACHLORIDE NO 0.47 NO 0.40 0.65 ND 0.60 0.60 0.60 NO NO NO NO
CHLOROFORM NO 0.05 NO NO 0.15 NO 0.10 NO 0.07 NO ND NO NO
CHLOROMImiANE ND 0.53 ND 0.50 0.85 NO 0.70 1.00 0.80 NO 0.20 NO NO
CYCLOHEXANE 7.10 2.20 4.90 15.60 0.95 14.65 11.00 16.90 1.35 3.55 15.55 NO NO
CYCLOPENTANE 8.30 1.30 7.00 24.40 0.30 24.10 23.60 20.00 0.35 6.65 19.65 NO NO
DICHLORODIFLUOROMETHANE 3.70 3.23 0.47 4.30 3.30 1.00 2.30 3.00 3.20 NO NO 2.70 NO
ETHANE 151.00 51.33 99.67 29.80 14.40 15.40 200.00 4.40 10.50 89.17 NO 6.50 NO
ETHYLBENZENE 9.10 1.77 7.33 37.20 2.40 34.80 15.10 20.80 2.10 5.23 18.70 NO NO
ETHYLENE + ACETYLENE 30.60 13.03 17.57 7.50 5.40 2.10 4.30 2.10 4.20 13.37 ND ND NO
HEPTANAL ND 1.43 NO NO 2.45 NO 2.40 8.30 2.15 NO 6.15 ND NO
HEXANAL 2.60 2.37 0.23 19.80 1.95 17.85 3.50 8.00 0.55 ND 7.45 NO ND
INOAN ND 0.00 0.00 ND 0.40 ND NO ND 0.00 NO ND NO ND
ISOBUTANE 247.00 12.30 234.70 121.00 5.95 115.05 179.00 195.00 4.35 230.35 190.65 3.50 NO
ISOBUTENE + I-BUTENE 21.20 5.77 15.43 15.40 0.65 14.75 ND 23.20 0.00 15.43 23.20 ND NO
ISOHEPTANE + 13.00 2.87 10.13 58.60 2.15 56.45 15.50 29.80 1.65 8.48 28.15 ND NO
2,3-DIMETHYLPENTANE
ISOHEXANE 44.70 4.67 40.03 154.00 4.10 149.90 62.90 104.00 2.85 37.18 101.15 NO NO
ISOPENTANE 152.00 16.57 135.43 NO 13.50 NO 287.00 296.00 8.95 126.48 287.05 NO ND
ISOPRENE NO 0.70 NO NO 0.25 NO NO 3.50 1.05 NO 2.45 NO NO
L1MONENE ND 0.67 NO NO 3.30 NO NO NO 1.00 NO NO NO NO
M-OIETHYLBENZENE NO 1.03 NO 11.30 1.25 10.05 2.30 5.60 1.55 NO 4.05 NO NO
TABLE 3-6. SUMMARY OF NET CONCENTRATION MEASURMENTS USING USEPA
TO-14 SAMPLING METHOD (CONTINUED)
DAY 1 DAYS 4,5&6 DAY 1 DAY 4 DAY 4 DAYS DAYS DAY 5 DAYS DAY 6 DAY 6
SITEA3 AVERAGE SITEA3 SITEA3 AVERAGE SITEA3 SITEA2 SlTEA3 DAYS SITEA2 SITEA3 SITEA2 SITEA2
DOWNWINI UPWIND NET DOWNWINI: UPWIND NET DOWNWIN[ DOWNWIND AVERAGE NET NET DOWNWINI: NET
COMPOUND NAME (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3) UPWIND (UG/M"3) (UG/M"3) (UG/M"3) (UG/M"3)
M·EYHYi.TOLUENE 9.10 3.00 6.10 40.30 2.85 37.45 10.10 13.10 3.80 2.30 9.30 10.90 9.50
ME1HANOL 53.00 0.00 53.00 ND 0.00 0.00 NO ND 0.00 53.00 ND NO ND
METHYLCYCLOHEXANE 8.00 3.60 4.40 24.90 1.30 23.60 11.70 9.30 2.45 1.95 6.85 NO ND
METHYLCYCLOPENTANE 12.70 2.80 9.90 39.40 1.60 37.80 ND 36.80 1.05 8.85 35.75 ND ND
METHYLENE CHLORIDE ND 0.47 ND 0.60 1.55 ND 0.30 0.30 0.60 NO ND 0.50 NO
N·BUTANE 185.00 13.90 171.10 116.00 11.10 104.90 331.00 208.00 3.05 168.05 204.95 NO ND
N·BUTYLBENZENE 3.30 0.27 3.03 19.90 1.25 18.65 3.80 9.10 0.40 2.63 8.70 NO ND
N-DECANE 5.40 3.53 1.87 7.10 0.75 6.35 4.00 1.10 3.15 ND ND 8.80 4.50
N-HEPTA"l8 12.10 1.73 10.37 29.70 1.40 28.30 16.80 14.10 0.70 9.67 13.40 NO ND
N·HEXANE 24.90 3.07 21.83 67.70 2.80 64.90 55.10 60.80 2.45 19.38 58.35 ND ND
N-NONANE 3.70 2.67 1.03 6.20 0.75 5.45 8.70 1.20 2.30 ND ND NO ND
N-OCTANE 5.40 1.73 3.67 12.30 1.15 11.15 10.70 3.20 0.95 2.72 2.25 ND ND
N·PENTANE 69.80 13.73 56.07 155.00 6.30 148.70 241.00 160.00 5.20 50.87 154.80 ND ND
N·PROPYLBENZENE 2.70 1.53 1.17 10.60 0.95 9.65 6.90 5.10 1.75 ND 3.35 NO ND
N·UNDECANE 5.60 3.23 2.37 9.30 1.05 8.25 2.50 1.90 2.55 NO ND 11.10 6.50
NEOHEXANE 17.80 0.00 17.80 90.50 0.35 90.15 7.70 0.70 0.00 17.80 0.70 ND ND
O-ETHYLTOLUENE 3.60 0.30 3.30 17.00 1.25 15.75 4.50 5.10 0.45 2.85 4.65 NO ND
O-XYLENE 12.00 2.13 9.87 64.40 2.85 61.55 16.80 22.00 2.30 7.57 19.70 2.80 1.00
P·DIETHYLBENZENE ND 0.40 NO 2.70 0.00 2.70 0.70 2.50 0.60 ND 1.90 NO ND
P-ETHYLTOLUENE 5.80 0.00 5.80 19.20 1.50 17.70 6.80 6.20 0.00 5.80 6.20 ND ND
P·ISOPROPYLTOLUENE NO 0.00 0.00 ND 0.30 ND ND NO 0.00 NO ND ND ND
P·XYLENE + M·XYLENE 28.60 4.40 24.20 153.00 7.65 145.35 42.90 63.50 3.90 20.30 59.60 8.00 2.60
'";-' PROPANE 138.00 32.37 105.63 98.80 15.65 83.15 358.00 17.70 13.50 92.13 4.20 5.70 ND
PROPYLENE 18.00 10.17 7.83 13.50 2.65 10.85 34.90 2.50 0.30 7.53 2.20 ND NO
T-2-BUTENE 32.70 1.63 31.07 16.20 0.00 16.20 22.50 43.30 0.00 31.07 43.30 NO NO
T·2-HEXENE 2.40 0.00 2.40 5.30 0.00 5.30 4.10 13.70 0.00 2.40 13.70 NO ND
T·2-PENTENE 14.50 5.57 8.93 30.20 0.95 29.25 14.70 45.30 0.00 8.93 45.30 ND NO
T-BUTYLBENZENE 13.20 2.00 11.20 NO 4.05 ND 14.00 6.50 3.00 8.20 3.50 ND NO
TETRACHLOROETHYLENE NO 0.05 NO ND 0.25 ND ND ND 0.08 NO ND NO ND
TOLUENE 84.90 6.30 78.60 257.00 12.65 244.35 65.40 116.00 5.40 73.20 110.60 3.80 NO
TRICHLOROFLUOROMETHANE 1.40 2.17 ND 2.50 5.50 ND 1.30 1.40 2.50 ND ND 1.20 NO
UNIDENTIFIED 3.00 0.17 2.83 0.10 0.45 NO 0.10 0.20 0.20 2.63 ND 0.50 0.40
HALOGENATED VOC
UNIDENTIFIED VOC 81.90 71.83 10.07 629.00 39.30 589.70 239.00 352.00 69.10 NO 282.90 127.00 49.70
TNMHC 1710.00 367.67 1342.33 3030.00 233.50 2796.50 2560.00 2430.00 221.00 1121.33 2.209.00 206.00 NO
ND=NOT DETECTED
BTEX compound, it has been selected as the surrogate chemical to
obtain data for the remaining compounds. This technique should
provide a "ballpark" estimate if the premise that the
source/receptor relationship is identical for toluene and the
other 83 chemicals. This technique was used to prepare
Table 3-7. In Table 3-7, the annual emission rate for toluene
developed in section 5 was used as a basis for this rationing.
The last column on this table provides rough approximation of the
annual emissions for those 84 chemicals ranked from highest
emission to the lowest.
Also included in Table 3-7 is an estimate of the standard
deviation of the ratio of the various chemicals to toluene.
3.3 Quality Assurance
A quality assurance program was included as part of the sampling
protocol. The quality assurance program included sample blanks
and replicate (co-located) samples. From these latter samples,
an estimate of sampling precision was made. For the charcoal
samplers, a total of 32 duplicate samples were collected
(approximately 5 percent of the total samples collected).
Replicate samples were collected in several different ways. In
some cases, an Amoco sampler was moved to another location and
co-located with another Amoco sampler. Thus, identical co-
located samplers could be examined for precision. In other
cases, replicate samples were collected with portable samplers.
62
TABLE 3-7. RATIO OF AMBIENT MEASUREMENTS TO TOLUENE
DAY 1 DAY 4 DAY 5 DAY 5 MEAN SIGMA ORDEROFMAGNiTODE

SITE 3 RATIO SITE 3 RATIO SITE 2 RATIO SITE 3 RATIO RATIO RA110 ESTIMATE OF
NET TO NET m NET TO NET TO TO m EMISSIONS
COMPOUND NAME (UG/M""3) mLUENE (UG/M""3) TOLUENE (UG/M"31 TOLUENE (UG/M"3l TOLUENE TOLUENE TOLUENE (TONSIYEAR)
TNMHC 1342.3 17.078 2796.5 11.445 1121.3 15.319 2209 19.973 15.95 3.09 2904
lSOBUTANE 234.7 2.986 115.1 0.471 230.4 3.147 190.65 1.724 2.08 1.08 379
N-BUTANE 171.1 2.177 104.9 0.429 168.1 2.296 204.95 1.853 1.69 0.74 307
ISOPENTANE 135.4 1.723 ND 0.000 126.5 1.728 287.05 2.595 1.51 0.94 275
UNIDENTIFIED VOC 10.1 0.128 589.7 2.413 ND 0.000 282.9 2.558 1.27 1.21 232
mLUENE 78.6 1.000 244.4 1.000 73.2 1.000 110.6 1.000 1.00 0.00
N-PENTANE 56.1 0.713 148.7 0.609 50.9 0.695 154.8 1.400 0.85 0.32 155
PROPANE 105.6 1.344 83.2 0.340 92.1 1.259 4.2 0.038 0.75 0.57 136
ETHANE 99.7 1.268 15.4 0.063 89.2 1.218 ND 0.000 0.64 0.61 116
ISOHEXANE 40.0 0.509 149.9 0.613 37.2 0.508 101.15 0.915 0.64 0.17 116
P-XYLENE + M-XYLENE 24.2 0.308 145.4 0.595 20.3 0.277 59.6 0.539 0.43 0.14 78
BENZENE 17.5 0.223 114.6 0.469 15.3 0.209 68.1 0.616 0.38 0.17 69
METHANOL 53.0 0.674 0.0 0.000 53.0 0.724 ND 0.000 0.35 0.35 64
N-HEXANE 21.8 0.278 64.9 0.266 19.4 0.265 58.35 0.528 0.33 0.11 61
3-METHYLPENTANE 20.6 0.262 83.8 0.343 18.4 0.251 52.85 0,478 0.33 0.09 61
T-2-BUTENE 31.1 0.395 16.2 0.066 31.1 0.424 43.3 0.392 0.32 0.15 58
2-METHYL-2-BUTENE 13.2 0.168 48.1 0.197 13.2 0.180 80 0.723 0.32 0.23 58
NEOHEXANE 17.8 0.226 90.2 0.369 17.8 0.243 0.7 0.006 0.21 0.13 38
T-2-PENTENE 8.9 0.114 29.3 0.120 8.9 0.122 45.3 0,410 0.19 0.13 35
2,3-D1METHYLPENTANE
ISOHEPTANE + 10.1 0.129 56.5 0.231 8.5 0.116 28.15 0.255 0.18 0.06 33
METHYLCYCLOPENTANE 9.9 0.126 37.8 0.155 8.8 0.121 35.75 0.323 0.18 0.08 33
2,3-D1METHYLBUTANE 10.5 0.133 42.3 0.173 10.0 0.137 26.15 0.236 0.17 0.04 31
ISOBUTENE + I-BUTENE 15.4 0.196 14.8 0.060 15.4 0.211 23.2 0.210 0.17 0.06 31
0- O-XYLENE 9.9 0.126 61.6 0.252 7.6 0.103 19.7 0.178 0.16 0.06 30
W C-2-BUTENE 11.1 0.141 11.7 0.048 11.1 0.151 31.3 0.283 0.16 0.08 28
2-METHYL-I-BUTENE 5.6 0.071 22.0 0.090 5.6 0.076 37.6 0.340 0.14 0.11 26
3-METHYLHEXANE 7.6 0.096 38.0 0.156 6.9 0.094 20.1 0.182 0.13 0.04 24
N-HEPTANE 10,4 0.132 28.3 0.116 9.7 0.132 13.4 0.121 0.13 om 23
ETHYLBENZENE 7.3 0.093 34.8 0.142 5.2 0.071 18.7 0.169 0.12 0.04 22
CYCLOPENTANE 7.0 0.089 24.1 0.099 6.7 0.091 19.65 0.178 0.11 0.04 21
ETHYLENE + ACETYLENE 17.6 0.223 2.1 0.009 13.4 0.183 ND 0.000 0.10 0.10 19
C-2-PENTENE 4.1 0.052 10.3 0.042 4.1 0.056 26.2 0.237 0.10 0.08 18
M-ETHYLmLUENE 6.1 0.078 37.5 0.153 2.3 0.031 9.3 0.084 0.09 0.04 16
2-METHYL-2-PENTENE 4.3 0.055 10.1 0.041 4.3 0.059 21 0.190 0.09 0.06 16
2,2,4-TRIMETHYLPENTANE 5.7 0.073 34.8 0.142 3.8 0.052 8.15 0.074 0.09 0.03 16
CYCLOHEXANE 4.9 0.062 14.7 0.060 3.5 0.048 15.55 0.141. 0.08 0.04 14
T-BUTYLBENZENE 11.2 0.142 ND 0.000 8.2 0.112 3.5 0.032 0.07 0.06 13
p-ETHYLmWENE 5.8 0.074 17.7 0.072 5.8 0.079 6.2 0.056 0.07 0.01 13
2-METHYL-I-PENTENE 2.1 0.027 15.8 0.065 2.1 0.029 17,4 0.157 0.07 0.05 13
PROPYLENE 7.8 0.100 10.9 0.044 7.5 0.103 2.2 0.020 0.07 0.04 12
METHYLCYCLOHEXANE 4.4 0.056 23.6 0.097 2.0 0.027 6.85 0.062 0.06 0.02 11
1,3,5-TRIMETHYLBENZENE 5.1 0.065 20.6 0.084 3.4 0.046 4.45 0.040 0.06 0.02 11
N-BUTYLBENZENE 3.0 0.039 18.7 0.076 2.6 0.036 8.7 0.079 0.06 0.02 10
T-2-HEXENE 2.4 0.031 5.3 0.022 2.4 0.033 13.7 0.124 0.05 0.04 10
O-ETHYLmWENE 3.3 0.042 15.8 0.064 2.9 0.039 4.65 0.042 0.05 0.&1 9
3-METHYLHEPTANE 3.8 0.049 13.9 0.057 3.0 0.041 4.15 0.038 0.05 0.01 8
ACETONE ND 0.000 10.3 0.042 ND 0.000 14.55 0.132 0.04 0.05 8
N-OCTANE 3.7 0.047 11.2 0.046 2.7 0.037 2.25 0.020 0.04 0.01 7
C-3-HEXENE 2.0 0.025 3.5 0.014 2.0 0.027 8.9 0.080 0.04 0.03 7
TABLE 3-7. RATIO OF AMBIENT MEASUREMENTS TO TOLUENE (CONTUNED)
DAY 1 DAY 4 DAYS DAY 5 MEAN SIGMA ORDEROFMAGNfIUDE

SITE 3 RATIO SITE 3 RATIO SITE 2 RATIO SITE 3 RATIO RATIO RATIO ESTIMATE OF
NET TO NET TO NET TO NET TO TO TO EMISSIONS
COMPOUND NAME (UGIM"3) TOLUENE (UG/M"3) TOLUENE (UG/M"3) TOLUENE (UG/M"3) TOLUENE TOLUENE TOLUENE (TO~S/yEAR)
HEXANAL 0.2 0.003 17.9 0.073 ND 0.000 7.45 0.067 0.04 0.03 7
1,2,3·TRIME1HYLBENZENE ND 0.000 16.7 0.068 ND 0.000 5.1 0.046 0.03 0.03 5
2,2,3-TRIME1HYLPENTANE 2.3 0.029 11.6 0.047 2.3 0.031 ND 0.000 0.03 0.02 5
2,5-DlME1HYLHEXANE 2.6 0.033 7.9 0.032 2.6 0.036 ND 0.000 0.03 0.01 5
2,3,4-TRIME1HYLPENTANE ND 0.000 18.9 0.077 ND 0.000 2.2 0.020 0.02 0.03 4
2,4-DlME1HYLPENTANE 2.0 0.025 11.8 0.048 1.7 0.023 ND 0.000 0.02 0.02 4
C2-HEXENE 0.0 0.000 6.5 0.027 0.0 0.000 6.5 0.059 0.02 0.02 4
N-PROPYLBENZENE 1.2 0.015 9.7 0.039 ND 0.000 3.35 0.030 0.02 0.02 4
M-DIE1HYLBENZENE ND 0.000 10.1 0.041 ND 0.000 4.05 0.037 0.02 0.02 4
UNiDENtiFIED 2.8 0.036 ND 0.000 2.6 0.036 ND 0.000 0.02 0.02 3
HALOGENATED VOC
2,2,5-TRIMETHYLHEXANE 1.9 0.024 3.7 0.015 1.9 0.026 ND 0.000 0.02 0.01 3
N-UNDECANE 2.4 0.030 8.3 0.034 ND 0.000 ND 0.000 0.02 0.02 3
HEPTANAL ND 0.000 ND 0.000 ND 0.000 6.15 0.056 O.oJ 0.02 3
N-DECANE 1.9 0.024 6.4 0.026 ND 0.000 ND 0.000 O.oJ 0.01 2
N-NONANE 1.0 0.013 5.5 0.022 ND 0.000 ND 0.000 O.oJ 0.01 2
P-DIE1HYLBENZENE ND 0.000 2.7 0.011 ND 0.000 1.9 0.017 0.01 0.01 1
ISOPRENE ND 0.000 ND 0.000 ND 0.000 2.45 0.022 O.oJ 0.01 1
DlCHLORODIFLUOROMETHA 0.5 0.006 1.0 0.004 ND 0.000 ND 0.000 0.00 0.00 0
l-OCTENE 0.0 0.000 2.4 0.010 0.0 0.000 ND 0.000 0.00 0.00 0
t,l,t-TRICHLOROETHANE ND 0.000 2.0 0.008 ND 0.000 ND 0.000 0.00 0.00 0
CHLOROMETHANE ND 0.000 ND 0.000 ND 0.000 0.2 0.002 0.00 0.00 0
0- t,2,4-TRIME1HYLBENZENE ND 0.000 0.0 0.000 ND 0.000 ND 0.000 0.00 0.00 0
~ 2-BUTANONE ND 0.000 0.0 0.000 0.0 0.000 ND 0.000 0.00 0.00 0
TETRACHLOROETHYLENE ND 0.000 ND 0.000 ND 0.000 ND 0.000 0.00 0.00 0
TRICHLOROFLUOROMETHAN ND 0.000 ND 0.000 ND 0.000 ND 0.000 0.00 0.00 0
INDAN 0.0 0.000 ND 0.000 ND 0.000 ND 0.000 0.00 0.00 0
ME1HYLENE CHLORIDE ND 0.000 ND 0.000 ND 0.000 ND 0.000 0.00 0.00 0
LlMONENE ND 0.000 ND 0.000 ND 0.000 ND 0.000 0.00 0.00 0
P-ISOPROPYLTOLUENE 0.0 0.000 ND 0.000 ND 0.000 ND 0.000 0.00 0.00 0
B-PINENE ND 0.000 ND 0.000 ND 0.000 ND 0.000 0.00 0.00 0
A-PINENE ND 0.000 ND 0.000 ND 0.000 ND 0.000 0.00 0.00 0
CHLOROFORM ND 0.000 ND 0.000 ND 0.000 ND 0.000 0.00 0.00 0
CARBON TETRACHLORIDE ND 0.000 ---
ND 0.000 -- ------
ND 0.000_ _ "---__ I<D 0.000 0.00 0.00 0
ND=NOT DETECTED
For a portion of these samples, the sampling rate was varied to
determine if the sampling rate would effect the resulting
concentration. ThE~ overall precision using the charcoal samplers
for BTEX was ±3, 13, 17 and 3 percent, respectively. Table 3-8
summarizes the quality assurance data for the charcoal samplers.
Analyses were also conducted to determine if breakthrough was
occurring in the charcoal tubes. The results of these analyses
indicated that the maximum amount of benzene and toluene found in
the back section of the charcoal tubes was 6 and 3 ug/m3 ,
respectively. As a result of these low concentrations found in
the back section, significant breakthrough did not occur. (See
Radian 1991 for more details.)
Duplicate samples were collected using the TO-14 canister. These
data are summarized in Table 3-9. As indicated by these data,
the precision (from replicate samples) and accuracy for benzene
are ±18 and ±5.7 percent, respectively. (See Radian 1991 for
more details.)
3.4 Meteorological Monitoring
As part of the sampling program, a meteorological tower was
installed at the refinery. This system measured wind speed, wind
direction, temperature, and sigma theta (standard deviation of
horizontal wind direction). These measurements were made at a
height of 18 meters. This elevation was chosen to avoid
65
TABLE 3-8. ACCURACY AND PRECISION ESTIMATES
FOR THE 2-HOUR CHARCOAL TUBE SAMPLING
NIOSllL EXPERIENCE FOR BIAS AND PRECISION FOR BTEX

MEASURED BY METHOD 1501
Accuracy Overall
ChemictlL1 Bias
(%)
Benzene 0.8
-8.1
Toluene 3.8
Xylene -2.1
PRECISION ESTIMATES FOR TWO-HOUR CHARCOAL TUBE SAMPLES
Precision (%}
Compound N* Total Analytical
Benzene 14 28 3
Toluene 17 35 3
Ethylbenzene 5 22 17
Xylene 7 20 3
3
*Number of duplica.te sets with .concentration greater than 1 ugjm
SUMMARY OF FRONT/BACK SECTION ANALYSIS RESULTS
Front Section Back Section Ratio: FrontLBack

Compound N* Max Conc N* Max Conc Min (%} Max (%)
3 3
Benzene 38 699 ugjm 3 6 ugjm 1.3 6.0
Toluene 37 294 9 3 0.3 137
Ethylbenzene 22 71 0 <U.D
Xylene 26 307 0 <LLD
*Number of samples above detection limit
66
TABLE 3-9
ACCURACY AND PRECISION ESTIMATES FOR TO-14 SAMPLING
TO-14 PERFORMft.NCE EVALUATION RESULTS FOR MARCH 1990

AUSVOC LABORATORY - AUSTIN, TEXAS
Theoretical Reported
Value Result Accuracy
Paramet:er (ppbv) (ppbv) (%)
Benzene 2.09 1. 97 -5.7
Toluene 4.10 4.36 6.3
O-xylene 3.606 3.57 -0.8
Mean = -6.0
Std. Dev = 11.1
n = 26
DUPLICATE CANISTER RES0LTS
Duplicate A-16 Samples A-17 Precision

Sample No. (ppmv) (ppmv) (%)
Benzene 46.8 56.3 18
Toluene 95.7 137.0 35
Ethylbenzene 27.8 12.8 89
Xylene 159.7 348.0 74
Note: Duplicate samples collected on the Coker Pond
67
influences from an adjacent building/structures.
This monitoring equipment met or exceeded the accuracy and
precision requirements established by USEPA.
A PC-based data acquisition system was used to collect the
meteorological data. The computer would scan each measurement
channel at a rate of 10 channels per second. The computer would
then average the data to compute 5, 15, and 60-minute averages.
Atmospheric stability was determined from the sigma theta data
using procedures developed by USEPA (USEPA 1987c).
3.5 Tracer Experiments
Unfortunately, because of a limited sampling array and the
meteorological conditions, the Ultraformer unit could not be
distinctively identified as an isolated source. These data did
not satisfy the study objectives. As a result of these problems,
these data could not be used to test the accuracy of the volume
source algorithm in the dispersion model, nor estimate fugitive
emissions by comparing the ratio of pollutant to SF6 • Appendix A
discusses analyses of these data.
68
4.0 Emission Inventory
One of the preliminary goals of the first phase of this project
was to develop and verify an air quality emission inventory for
the Yorktown RefinE!ry. One of the requirements of this inventory
was that emissions be quantified for each individual source.
Further, the invent:ory for each source had to describe individual
hydrocarbon species. In addition to quantifying emissions, the
inventory needed to provide data on source location and source
characteristics (eg. exit diameter, exit temperature, release
height, type of source, etc.) so that emissions could be
translated into exp6sure through dispersion modeling.
In developing the emission inventory for the Yorktown Refinery,
many different approaches were used. This section outlines those
approaches and is broken into two categories: 1) speciated
hydrocarbon emissions and 2} criteria pollutant emissions (i.e.,
S02' N0 2 , CO, PM-10). An estimate of the overall accuracy of the
inventory (primarily BTEX) is presented in section 5.
4.1 Hydrocarbon Air Toxies Emission Inventory
Table 4-1 summarizE!s the basis for estimating the emission
inventory for the various source categories. The following
provides an overviE!w 9f the assumptions used in developing these
estimates. In reviewing these data, the time scale of the
emission estimates should be noted. For some sources, the time
scale is integrated over the sampling time while for other
69
TABLE 4-1. BASIS OF EMISSION ESTIMATES
SOURCE TYPE BASIS OF EMISSION ESTIMATE SPECIATED EMISSIONS
API SEPARATOR DIRECT MEASUREMENT DIRECT MEASUREMENT

BARGE LOADING AP-42 RATIO OF TOTAL EMISSIONS USING COMPONENT FRACTION
BLOWDOWN STACKS AP-42 AND SPECIATION AP-42 AND DIRECT MEASUREMENT
COKER POND DIRECT MEASUREMENT DIRECT MEASUREMENT
COOLING TOWER WATER SAMPLING MASS BALANCE DIRECT MEASUREMENT
INACTIVE LANDFARM DIRECT MEASUREMENT DIRECT MEASUREMENT
LOADING RACK AP-42 RATIO OF TOTAL EMISSIONS USING VAPOR OR LIQUID FRACTION
-...J PROCESS FUGITIVE AP-42 DEFAULT COMPONENTS RATIO OF TOTAL EMISSIONS USING VAPOR OR LIQUID FRACTION
o
SEWER VENT DIRECT MEASUREMENT DIRECT MEASUREMENT
TANKS AP-42 ~ .~.
RATIO OF TOTAL EMISSIONS USING VAPOR OR LIQUID FRACTION
sources the time scale for the emissions is based on a generic
emission factor which incorporates annual process throughput.
Where possible, speculation on how well the inventory can be
scaled with respect: to time has been provided. It should be
noted that the issue of time scale for emission inventories is
not unique to this project or the source measurements made as
part of this study. In fact, many published emission factors
suffer from the same problem. Typically, emission measurements
are made over a short time period. These measurements are then
scaled or adjusted to reflect normalized process conditions and
then assumptions are made regarding how these emissions scale
with time.
4.1.1 API Separato~
Emissions from the API separator were estimated by direct
measurement using a flux chamber. This sampling resulted in an
estimation of speciated hydrocarbon emissions, as discussed in
Section 2.1.
Several assumptions were made in extrapolating these measurements
to estimate annual emissions. First, it was assumed that the
flux rate was uniform over the area of the API separator (the
area of the separator included the forebay portion of the
separator). Second, it was assumed that these emissions would be
constant with respect to time. Review of the replicate
measurement data indicate a large variability in the measured
71
flux between the replicate data (approximately a factor of 2 in
some cases). Thesei replicate samples were collected at opposite
ends of the separator. As a result of this variability, the
assumption of uniform emissions over the entire area of the
surface is overly simplistic. However, the mean of the two
samples probably represents a reasonable average for the entire
pond.
Regarding the variability of emissions with time for this source,
one of the major factors which can affect emissions is the wind
speed at the interface of the water and the air. The location of
this unit is slight~ly below grade and, therefore, the wind speed
at the surface of t~he water will, in general, be quite low and
relatively constant. By contrast, the flux chamber by design
creates an artificial velocity over the surface of the water.
Therefore, it is likely that these measurements represent an
upper-bound estimate on emissions. At the time of sampling, the
ambient temperature was approximately 80°F which should result in
high evaporation rate. Therefore, scaling these measurements
linearly ",rith respEict to time represents a conservative estimate
of annual emissions.
other methods of estimating annual emissions contain the same
inherent limitations as do these measurements. For example, if
emissions were to be estimated using a model such as CHEMDAT7,
annualized estimatEis of the amount of oil contained in the water
72
would be required. Thus, one would have to estimate the annual
average (in space and time) oil content of the water.
4.1.2 Barge Loading
Emissions from barsre loading were estimated using the emission
factor from AP-42 (784 tons per year). Speciated emissions were
then determined by ratioing total VOC emissions by the
composition of separate products loaded. These emission
estimates are summarized in Table 4-2. Although this is a
reasonable estimate! of annual emissions, no estimate of short-
term emissions was made.
4.1.3 Blowdown stac:ks
Emissions from blowdown stacks were estimated using a combination
of methods. A field sampling program was initiated in May of
1991 to sample emissions from these sources. This sampling
showed sUbstantial VOC emissions, however, the QA/QC of the
samples indicated probable errors in the data. These sources
were re-tested. However, this sampling was not completed on
schedule or within the timeframe of this portion of project. The
results of the blowrdown stack sampling are discussed in
Appendix I. As a result of the sampling problems, VOC emissions
were estimated using the AP-42 emission factor for uncontrolled
blowdown stacks.
As part of this analysis, "Amoco performed a literature review to
73
TABLE 4-2
EMISSIONS FROM BARGE LOADING
Compound Emissions (T/Yr)
VOC 784.0
Benzene 16.3
Toluene 76.3
Ethylbenzene 5.7
Xylene 36.9
Cyclohexane 2.4
styrene 3.4
1, 2, 4 Trimethylbenzene 22.0
Naphthalene 5.1
MTBE 8.8
74 .
identify the basis for this emission factor. It was found that
no experimental data was used to derive this factor. Because of
the lack of any other data to estimate emissions from these
sources, the AP-42 factor was used. Emissions for specific
blowdown stacks were estimated by multiplying estimated emissions
using AP-42 for the refinery by the ratio of unit capacity to
refinery capacity. Speciated hydrocarbon emissions were obtained
by assuming that the relative fraction of hydrocarbon species
obtained in the first Radian sampling was correct and this
fraction was then used to apportion hydrocarbon emissions. In
the modeling analysis, the exit velocity and temperature were
conservatively set to minimize plume rise for these sources.
Table 4-3 presents the fraction of the total emissions estimated
for the S1!ffiA report~ed chemicals. It should be noted that this
analysis assumed voe emissions from the blowdown stacks were

5,200 tons per year, however, based on limited source testing, it
is believed that actual voe emi?sions are approximately

3,900 tons per year.
4.1.4 Coker Pond
Section'2.2 discusses the sampling methodology and results for
the coker blowdown pond. Measurements were made at two
locations: the quench area and the overflow area. Two replicate
samples were collected in each area.
75
TABLE 4-3. COMPOSITION BREAKDOWN OF BTEX AND NON-BTEX VOC EMISSIONS FROM THE BLOWDOWN STACKS
COKER BLOWDOWN ULTRAFORMER BLOWDOWN COMBO BLOWDOWN

STACK STACK STACK TOTAL
%OF EMISSIONS %OF EMISSIONS %OF EMISSIONS EMISSIONS
COMPOUND TOTALVOC (t/yr) TOTALVOC (t/yr) TOTALVOC (t/yr) (t/yr)
BENZENE 0.20 4.4 1.90 8.8 0.40 9.2 22.4
TOLUENE 0.80 19.7 7.50 35.0 0.40 10.1 64.8
ETHYLBENZENE 0.70 16.7 1.60 7.4 0.10 17.4 41.5
XYLENE 3.50 84.1 6.20 28.9 0.40 8.6 121.6
MTBE 0.00 0.0 0.00 0.0 0.00 0.0 0
ETHYLENE 0.40 8.9 3.30 15.4 0.70 16.3 40.6
NAPTHALENE 0.00 0.0 0.00 0.0 0.00 0.0 0
...... CYCLOHEXANE 3.00 7.6 0.60 3.0 0.90 20.5 31.1
0'\
TRIMETHYLBENZENE 1.60 38.0 0.40 2.0 0.10 21.0 61
PROPYLENE 0.60 14.7 1.30 6.2 1.90 43.4 64.3
BUTADIENE 0.00 0.0 0.00 0.0 0.01 0.2 0.2
TNMHC 100.00 2444.0 100.00 468.0 100.00 2288.0 5200
NOTE: SUBSEQUENT MEASURMENTS INDICATE VOC EMISSIONS ARE APPROXIMATELY 3900 tJyr
In the quench area, the samples were collected near the point of
discharge and samples were integrated over the entire process
cycle (18 hours). Thus, there was an attempt to account for the
periodic changes in process conditions through sample
integration. Also, the samples were collected near the point of
discharge and, therefore, should represent the maximum emission
rate. Comparison of the replicate samples indicates that there
was some variability between the replicate samples.
since this pond was located within a process unit, the wind flow
across the surface of the pond will be dramatically reduced due
to obstructions from process equipment. Thus, changes in wind
speed are not likely to influence estimates of annual emissions
greatly. Also, the sampling methodology (flux chamber) created
an artificial boundary layer which may represent an upper bound
on emissions. Therefore, it was assumed that the average of
these 2 replicate measurements can be used to estimate annual
emissions.
Annual emissions were estimated for the overflow section of the
coker pond in the same way as the quench area of the pond.
4.1.5 cooling Tower
Estimating emissions from the cooling tower involved using the
AP-42 emission factor for cooling towers and collecting water
samples (BTEX) going to the cooling tower. Speciated emissions
77
were computed by ratioing the total voe estimate by the water
component fraction. It was further assumed that emissions were
constant at this rate over the entire year. Table 4-4 summarizes
emissions from this source.
4.1.6 Inactive Landfarm
One flux chamber measurement was made in the center of the
inactive landfarm. The surface of the soil had been recently
tilled which should have temporarily enhanced emissions. Because
of the limited data collected, the emission estimates for this
source was assumed to be constant over the entire surface area
with time. Given the fact that the surface was recently
disturbed and the sampling occurred during warm weather, this
approach should be quite conservative. The emission estimates
are summarized in section 2.3.
4.1.7 Loading Rack
Emissions from the loading rack were estimated using the USEPA-42
emission factor (USEPA 1985). Speciated emissions were
determined by ratioing the total voe emissions by the various
components in the products. The emissions are summarized in
Table 4-5.
4.1.8 Process Fugitive
Process fugitive emissions and total voe emissions were estimated
by using the component default assumptions contained in the
78
TABLE 4-4
EMISSIONS FROM COOLING TOWER
Compound Emissions (T!Yr)
VOC 1. 81
Benzene 0.12
Toluene 0.43
Ethylbenzene 0.73
Xylene 0.34
79
TABLE 4-5
EMISSIONS FROM PRODUCT LOADING RACK
Species Emissions (T!yr)
VOC 53.0
Benzene 1.1
Toluene 4.9
Ethylbenzene 0.5
Xylene 2.7
1,2,4 Trimethylbenzene 1.6
80
process fugitive emission factors (Radian 1985). Speciated
emissions were then estimated using the average stream components
derived for a generic refinery. Table 4-6 summarizes these
emission estimates for each unit by chemical species. These
emission estimates contain a great deal of uncertainty as a
result of the emission factors; the exact count of the number of
components, and the uncertainty and variability in hydrocarbon
stream composition.
The monitoring/modE~ling analysis was designed to provide a check
on all of these assumptions. In reality, the impacts measured
downwind of a process source are a result of actual emissions
from within that portion of the unit (i.e., pump, flange valves,
sewers). These measured concentrations were compared to model
predictions using an emission inventory based on generalized
emission factors, default component and generic stream
compositions, as a means of confirming the estimated emissions.
Based on the results presented in section 5, reasonable agreement
was found between t:he two sets of concentrations. Thus, the
project concluded t:hat the emission inventory is representative
of total actual emissions (within the limit of uncertainty in our
analysis) and significant benzene sources have not been omitted.
A sensitivity analysis was performed to examine what additional
amount of benzene e~missions would result from process sewers. In
81
TABLE 4-6, EMISSIONS FROM PROCESS FUGITIVES
l,3-SlITA- CYCL.O· ETHYL· MElliYL-

UNIT VOC ETIiYLENE PROPYLEN DIENE HEXANE BENZENE TOLUENE BENZENE XYLENE BENZENE NAPTI\ALEN PHENOL CRESOL MTBE I
(fONSIYR) (fONSIYR) (fONSIYR) (fONSfYR) (fONSIYR) (fONSIYR) (fONSIYR) (fONSIYR) (fONSfYR) (fONSIYR) (fONSfYR) (fONSIYR) (TONSfYR) crONSIYR)
CRUDE 109.60 6.00 6.00 6.00 6.19 0..17 6.64 0..57 0..69 0..00 8.00 0..00 6.00 6.00
REFOR~ER 120..80 8.00 0.00 6.00 0..61 1.82 2.26 6.33 1.55 -t.90 O.lS G.OO 0.00 0.00
FCU 136.80 &13 16.43 0.61 0..00 6.31 1.S2 0..38 2.09 6.76 8.15 8.00 0..00 6.00
COKER 88.56 0..60 1.16 0..00 0..00 0..06 0..57 0..00 \.28 8.00 0..00 8.00 6.00 6.00
VRU 49.16 8.00 6.00 0..00 0.00 6.00 6.00 8.00 0..00 6.00 6.00 0..00 6.00 0..00
NAP HYDRO 33.56 8.00 0.00 6.00 0..51 6.21 0..69 6.\8 8.75 6.00 0..00 6.00 6.00 0..00
DlSTHYDRO 33.60 6.00 0..00 6.00 8.00 6.00 6.00 6.00 0..00 6.00 6.00 6.00 6.00 6.00
SRU 3.80 0..00 0.00 6.00 6.00 6.00 0..00 6.00 6.00 6.00 6.00 6.00 6.00 6.00
TREATING 43.80 0..00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 0..00
PROD BLENDING 47.90 0..00 0..00 6.00 0..0.2 0..90 4.92 0..35 1.35 1.63 0..08 0..00 0..00 0..00
co
N
POWER STATION 6.50. 6.00 0.00 0..00 0..00 0..00 0..00 6.00 0..00 0..00 0..00 0..00 0..00 0..00
POLY/MTBE 121.60 8.00 0..00 6.00 0..00 0..00 6.00 6.00 6.00 6.00 0..00 0..00 8.00 8.52
TOTAL 79550. 8.73 17.59 0..81 1.33 2.66 10..58 1.81 7.71 7.29 6,42 0..00 6.00 6.52
' - - - - . - L- ---.. -
this analysis, we estimated the area of sewer that was open to
the atmosphere and used the flux measurements from the sewers to
estimate emissions. As a result of this analysis, the sewers
within the process area are estimated to contribute an additional
2 to 4 tons per year of benzene. This is within the uncertainty
limits of our analYf;is and emissions of this magnitude are
addressed in the benzene sensitivity modeling.
One other issue that needs to be addressed is fugitive leak
monitoring that was conducted on the Ultra former unit. No direct
measurement of leak rates were made. such work requires
"bagging" individual components in statistically significant
numbers and was beyc:md the scope of this project. Rather, leak
monitoring was done to identify the fraction of leaking
components and determine if they could be repaired easily. That
sampling indicated that a larger than expected fraction of the
components had leak concentrations in excess of 10,000 ppm. The
Ultraformer and Pol:rmer Gasoline unit were selected for this
monitoring because they contained many "light ends" at high
pressure and would lbe expected to have easily detectable "leaks."
In both units, valves tested did not include a statistical
distribution of component sizes and services. This information
cannot be used to assess facility-wide fugitive emissions. The
data did show a high number of leaking components which could be
quickly repaired using simple tools. Hence, a leak detection and
repair program (LDAR) would be a reasonably cost-effective way to
83
reduce emissions from these sources.
Thus, while voe emissions may have been larger than estimated
using normal emission factors, benzene emissions were not
necessarily higher.
4.1.9 Sewer vents
Emissions from sewer vents were estimated through direct
measurement as discussed in section 2.
Given that the refinery was operating at maximum capacity, it is
assumed that linear extrapolation, as discussed in section 2, of
these measurements is a conservative estimate of annual
emissions.
During the course o,f this study, Amoco conducted a measurement
program to quantify emissions from 30 sewer vents at another
refinery. At this refinery, sewer vents are equipped with a vent
pipe as opposed to a grate at grade as found at the Yorktown
Refinery. This second set of measurements used a positive
displacement method to measure the flow rate. Both total voe

emissions and benzene compounds were measured. The result of
this measurement program estimated voe emissions (based on an
hourly measurement linearly extrapolated over the entire year) at
10 tons per year.
84
However, 6.5 tons per year were estimated from one vent and
lesser amounts from the other vents (it should be noted that
22 vents had less than 1 pound per day of emissions).
For benzene, total emissions from sewer vents were estimated
1.1 tons per year and 0.9 tons per year from the vent that had
the highest voe emissions.
It is useful to contrast these data to the measurements taken at
the Yorktown Refinery. At Yorktown, total voe emissions along
the main sewer trunkline were estimated at 117 tons per year or
about 13 tons per year per vent. This average is consistent with
the maximum emission rate measured at the other refinery (13 tons
per year at Yorktown vs. 6.5 tons per year at another refinery).
These other measurements are also consistent for benzene. At
Yorktown, total benzene emissions are approximately 2.4 tons per
year (approximately 0.3 tons per year per vent) compared to a
maximum of 0.9 tons per year at another refinery.
In summary, these data collaborate the measurements that were
made at the Yorktown Refinery and indicate that the measurement
technique did not significantly bias the results.
4.1.10 Tanks
Emission estimates for total voe emissions were based on AP-42
emission factors. speciated emissions were estimated by ratioing
85
the total voe emissions with the stream mixture. Table 4-7
summarizes these emissions.
4.1.11 wastewater Tank
Emissions from the wastewater tanks were estimated using a water
mass balance (inlet vs. outlet concentrations). These emissions
are summarized in Table 4-8.
4.1.12 Summary of voe Emissions
Figure 4-1 summarizes the results of the emission inventory
developed for total voe's for the Yorktown Facility. In this
figure, we have combined sewer vent emissions and the API
separator. As indicated by this figure, the largest emissions
are from the blowdown stacks, 5200 tons per year (65 percent) .
Process fugitives were the second largest emission source and
resulted in 796 tons per year (10 percent). Barge loading
emissions were 784 tons per year (10 percent). storage tanks and
the coker blowdown pond were the next largest voe emission
sources at 633 tons per year (8 percent) and 261 tons per year
(3 percent), respectively.
It is useful to contrast the results of the current inventory
development to original SARA inventory. Figure 4-2 presents the
same data as Figure 4-1 except the original SARA inventory was
used. It should be noted that the SARA inventory did not include
barge loading emissions because these are excluded by EPA
86
TAB LE 4-7. VOC EMISSIONS FOR STORAGE TANKS
ETHYL- NAPTH· l,2,4-TRI· TOTAL
CYCLOHEXA BENZENE TOLUENE XYLENE BENZENE ALENE METHYL- MTBE NMHC
TANK (TONS/YR) (TONS/YR) (TONSfl'R) (TONS/YR) (TONSIYR) (TONS/YR) BENZENE (TONSIYR) (TONS/YR)
(TONSIYR)
A 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0219

B 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0219
C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0219
0 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0219
E 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0219
DAYTK 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0219
100 0.0858 0.0420 0.1077 0.1935 0.0000 0.0000 0.0000 0.0000 5.9258
101 0.0858 0.0420 0.1077 0.1935 0.0000 0.0000 0.0000 0.0000 5.9258
102 0.0858 0.0420 0.1077 0.1935 0.0000 0.0000 0.0000 0.0000 5.9258
103 0.0858 0.0420 0.1077 0.1935 0.0000 0.0000 0.0000 0.0000 5.9258
104 0.0858 0.0420 0.1077 0.1935 0.0000 0.0000 0.0000 0.0000 5.9258
105 0.085& 0.0420 0.1077 0.1935 0.0000 0.0000 0.0000 0.0000 5.9258
106 0.0858 0.0420 0.1077 0.1935 0.0000 0.0000 0.0000 0.0000 5.9258
107 0.0858 0.0420 0.1077 0.1935 0.0000 0.0000 0.0000 0.0000 5.9258
108 0.0894 0.0438 0.111.3 0.1989 0.0000 0.0000 0.0000 0.0000 6.1411
109 0.0894 0.0438 0.111.3 0.1989 0.0000 0.0000 0.0000 0.0000 6.1411
110 0.1113 0.0548 0.1405 0.2519 0.0000 0.0000 0.0000 0.0000 7.7309
200 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9125
201 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9125
202 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9125
203 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9125
300 0.0566 0.0584 0.2281 0.2227 0.2227 0.0000 0.0000 0.0000 4.9202
301 0.0566 0.0584 0.2281 0.2227 0.2227 0.0000 0.0000 0.0000 4.9202
400 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0621
401 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0621
402 0.0000 0.0000 0.0000 0.0000 0.0000 0.0219 0.0000 0.0000 1.9436
403 0.0000 0.0000 0.0000 0.0000 0.0000 0.0219 0.0000 0.0000 1.9436
404 0.0000 0.0000 0.0000 0.0018 0.0000 0.0000 0.0000 0.0000 0.0657
405 0.0037 0.0018 0.0037 0.0073 0.0000 0.0000 0.0000 0.0000 0.2026
406 0.0000 0.0000 0.0000 0.0000 0.0000 0.0037 0.0000 0.0000 0.2500
409 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0438
500 0.0000 0.0000 0.0000 0.0000 0.0000 0.0219 0.0000 0.0000 0.0438
501 0.0000 0.0000 0.0000 0.0000 0.0000 0.0219 0.0000 0.0000 1.9436
502 0.0000 0.0000 0.0000 0.0000 0.0000 0.0018 0.0000 0.0000 0.1606
600 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0438
601 0.1058 1.5677 3.5223 0.2537 0.1515 0.0000 0.0000 0.0000 17.1800
602 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 4.9312 12.3300
604 0.2081 0.6278 0.4325 0.0000 0.0000 0.0000 0.0000 0.0000 28.0594
605 0.2081 0.6278 0.4325 0.0000 0.0000 0.0000 0.0000 0.0000 28.0594
606 0.0000 0.0712 0.7300 1.2775 0.2884 0.0602 0.3760 0.0000 4.3964
607 0.0000 0.0712 0.7300 1.2775 0.2884 0.0602 0.3760 0.0000 4.3964
608 0.0767 0.5603 1.7739 1.5221 0.2957 0.1533 0.5676 0.8322 34.8466
609 0.0000 0.7209 1.9108 1.8268 0.3486 0.1807 0.6552 0.4782 34.8685
610 0.0000 0.7209 1.9108 1.8268 0.3486 0.1807 0.6552 0.4782 34.8685
611 0.0000 0.7209 1.9108 1.8268 0.3486 0.1807 0.6552 0.4782 34.8685
612 0.0767 0.5603 1.7739 1.5221 0.2957 0.1533 0.5676 0.8322 34.8466
614 0.0913 0.5895 2.9620 4.8764 1.1406 0.3066 1.5020 0.0000 34.8557
615 0.0913 0.5895 2.9620 4.8764 1.1406 0.3066 1.5020 0.0000 34.8557
616 0.0000 0.3614 0.9545 0.9125 0.1734 0.0913 0.3267 0.2391 17.4196
617 0.0383 0.2811 0.8870 0.7610 0.1478 0.0767 0.2847 0.4161 17.4123
618 0.0073 0.0329 0.2610 0.4855 0.0858 0.0420 0.1752 0.0000 4.5351
622 0.2993 0.5439 0.3650 0.2628 0.0639 . 0.0000 0.0767 0.0000 21.0478
620 0.0274 0.1716 0.8651 1.4235 0.3322 0.0894 0.4380 0.0000 10.1817
700 0.0000 0.0475 0.5676 0.7866 0.1825 0.0000 0.3322 0.0000 17.1892
701 0.0420 0.0438 0.1734 0.1697 0.1697 0.0000 0.0000 0.0000 3.7413
87
TAB LE 4-7. VOC EMISSIONS FOR STORAGE TANKS
ETHYL- NAPTH· 1,2,4-TRI· TOTAL
CYCLOHEXA BENZENE TOLUENE XYLENE BENZENE ALENE METHYL- MTBE NMHC
TANK (fONSIYR) (fONSiYR) (fONS'YR) (fONSIYR) (fONSiYR) (fONSiYR) BENZENE (fONSiYR) (fONSiYR)
(fONSIYR)
702 0.0000 0.0402 0.4745 0.6588 0.1533 0.0000 0.2774 0.0000 14.4011
900 0.0000 0.1004 1.1899 1.6535 0.3833 0.0000 0.6972 0.0000 36.0839
901 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
902 0.0000 0.0073 0.0767 0.1058 0.0237 0.0000 0.0438 0.0000 2.3086
903 0.0000 0.0237 0.2884 0.3997 0.0931 0.0000 0.1679 0.0000 8.7472
905 0.0000 0.0055 0.0548 0.0748 0.0183 0.0000 0.0310 0.0000 1.6370
10 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
613 0.0913 0.5895 2.9748 4.8764 1.1406 0.3066 1.5020 0.0000 34.8557
619 0.0073 0.0329 0.2610 0.4855 0.0858 0.0420 0.1752 0.0000 4.5351
621 0.0256 0.1716 0.8651 1.4235 0.3322 0.0894 0.4380 0.0000 4.5351
87a
TABLE 4-8
EMISSIONS FROM WASTEWATER TANK
Compound Emissions (TlYrl
Total 19.0
Benzlene 0.5
Toluene 1.9
Ethylbenzene 0.4
Xylene 1.5
88
FIGURE 4-1.
VOC EMISSIONS FROM THIS STUDY
~
~
z
o ~
C w
en u
z a:
o w
a.
en
en
~
w
TOWER
SLOWDOWN BARGE COKER LAND FARM
EMISSION SOURCE
ID EMISSIONS ~ PERCENT
FIGURE 4-2.
VOC EMISSIONS FROM SARA INVENTORY
ct"
~
z
o I-
Z
C IJJ
en U
a:
z
o IJJ
0..
en
en
~
w
T01rAL TANKS COKER LAND FARM

SLOWDOWN WASTE WATER FUGITlVES COOUNG TOWER
EMISSION SOURCE
ID EMISSIONS ~ PERCENT
89
------------------------------------ --------
reporting rules. Comparison of these 2 figures indicate that
emission estimates ,yere relatively constant between the
2 inventories for process fugitives and storage tanks. However,
for sewers and the API separator, coker blowdown pond, and the
blowdown stack large differences exist between the 2 inventories
as a resul't of developing a more accurate emission inventory.
A comparison was made by Cohen, et aI, (1991) between speciated
emissions from the Yorktown Refinery and other VOC emission
sources in the vicinity (Table 4-9). This table summarizes total
regional emissions by 3 categories: Yorktown Refinery; VEPCO
(power plant) and mobile sources. For example, approximately
one-half of the benzene emissions in the region originate from
the refinery (67 tons per year) and the remainder come from
mobile sources (71 -tons per year). Similarly, for butadiene,
mobile sources are culpable for the majority of the emissions
(2.2 tons per year) while the refinery only emits 0.2 tons per
year. Based on total VOC's, however, the refinery contributes
nearly 80 percent to the immediate area, based on values reported
by the Vir<ginia Department of Air Pollution Control for auto
traffic and VEPCO.
4.2 Emissions of criteria Pollutants
As part of quantifying emission from the facility, emission
estimates 'were developed for criteria pollutants (S02' N0 2, CO
and PM-IO). Althou<gh ozone is a criteria pollutant, this
90
TABLE 4-9. SUMMARY OF AIR EMISSIONS IN REGION NEAR THE YORKTOWN REFINERY
REFINERY EMISSIONS VEPCO EMISSIONS AUTOMOTIVE EMISSIONS TOTAL

COMPOUND (TO NSNR) (%) (TONSNR) (%) (TONSNR) (%) (TONSNR)
BENZENE 67.2 48.4 0.6 0.0 71 51.2 138.8
BUTADIENE 0.2 8.8 0.0 0.0 2.2 91.2 2.4
ETHYLBENZENE 77.6 78.7 0.0 0.0 21 21.3 98.6
ETHYLENE 49.3 35.2 0.0 0.0 91 64.8 140.3
METHANOL 3.3 100.0 i
0.0 0.0 0 0.0 3.3
MTBE 16.6 100.0 0.0 0.0 0 0.0 16.6
NAPTHALENE 7.8 97.3 0.2 0.0 0.015 0.2 8.0
PROPYLENE 95.5 71.5 0.0 0.0 38 28.5 133.5
TOLUENE 181.8 54.9 0.6 0.0 149 45.0 331.4 I
\0 TRIMETHYLBENZENE 91.8 98.7 0.0 0.0 1.2 1.3 93.0
....
XYLENE (TOTAL) 276.5 67.9 0.6 0.0 130 31.9 407.1
VOC - -----
7905
------------- ----
77.8
-- -
55 0.0 2206 21.7 10166.0
SOURCE: VIRGINIA DEPARTMENT OF AIR POLLUTION CONTROL, 1988 (VEPCO AND AUTOMOTIVE) AND THIS STUDY
FOR AMOCO
pollutant is not emitted directly but is formed in the atmosphere
as a result of chemical reactions. This project will not address
ozone formation resulting from hydrocarbon and NO x emissions.
There are currently no emissions of lead from the facility,
therefore, this criteria pollutant will not be addressed.
Except for voe's, emissions of criteria pollutants usually tend
to originate from fuel fired refinery processes. The emissions
from these sources 'were estimated using USEPA emission factors
(USEPA 1985). No source testing was performed because it was
assumed that the confidence levels of accuracy of these factors
was adequate for the purpose of this study. Table 4-10 presents
a summary of these emissions.
92
TABLE 4-10. SUMMARY OF CRITERIA POLLUTANT EMISSIONS (TPY)
SOURCE S02 NOX PM-IO VOC* CO i
I
I
COKER 10.5 27.4 1.1 1.1 13.8
I
!
DESULFURIZATION/ULTRAFORMER 24.6 115.4 7.9 1.6 17.7
FCU/CRUDE 1814.8 115.4 509.3 1.7 17.4
POWER STATION 144.5 136.0 13.2 1.8 20.4
COKE HANDLING 28.0
SRU INCINERATOR 641.2 3.7 - - 431.0
FLARE 1169.0 3.7 - - 56.6
*DOES NOT INCLUDE THE VOC'S ESTIMATED IN THE PREVIOUS SECTIONS
'-0
W
5.0 Accuracy of the Emission Inventory for BTEX
This section describes the air dispersion modeling approach that
was used to confirm the accuracy of the BTEX emission inventory.
The accuracy assessment of the inventory was done by comparing
the ambient air monitoring data (discussed in section 3) and air
dispersion modeling concentration estimates. The input to the
model was the emission inventory along with meteorological
conditions observed during each ambient air monitoring sampling
period. It should be recalled that the monitoring program
focused on measuring impacts from specific units under persistent
meteorological conditions. A comparison was then made between
the observed concentrations and the model predictions. Based on
the results of this comparison, it was possible to draw
conclusions regarding the accuracy of the inventory. Admittedly,
this methodology is limited since dispersion models and
measurements are not completely accurate. However, this approach
does provide an opportunity to verify the inventory within the
limits of accuracy of the dispersion models. Typically, model
results within a factor of two of the actual measurements are
considered reasonable.
section 5.1 describes the modeling methodology used in this
analyses. section 5.2 discusses the methodology used to compare
the predicted and observed concentrations. The results of the
comparison are contained in section 5.3 Conclusions regarding
the inventory are presented in section 5.4.
94
5.1 Modeling Methodology
The USEPA Industrial Source Complex - Short-Term (ISCST)
dispersion model (USEPA 1987, version 3.4 dated 90346) was used
to estimate the observed concentrations at offsite locations
surrounding the refinery. This model is USEPA approved for
regulatory applicat.ions for multiple source industrial settings
such as rE~finery complexes. The model is capable of simulating
point area and volume sources. For point sources, the model
incorporat:es the effects of aerodynamic downwash on the
dispersion of the plume.
Table 5-1 presents a listing of how the model was initialized for
this analysis. Because the area surrounding the refinery was
determined to be the rural, the rural dispersion coefficients
were used. In modE~ling of BTEX compounds, it was assumed that
these chemicals would not undergo any chemical reactions or
transformation. This is a reasonable assumption since the travel
time to the monitors was quite short and, therefore, there is
little opportunity for chemical reactions or transformation to
occur.
The following sUbsections describe how each type of source was
modeled.
5.1.1 Process Fugitives
Process fugitives were simulated in ISCST by using the volume
95
TABLE 5-1. ISCST CONTROL SIJITCH INITIALIZATION
CALCULATE (CONCENTRATION=1,DEPOSITION=2) ISIJ(1) = 1

RECEPTOR GRID SYSTEM (RECTANGULAR=1 OR 3, POLAR=2 OR 4) ISIJ(2) = 1
DISCRETE RECEP10R SYSTEM (RECTANGULAR=1,POLAR=2) ISIJ(3) = 1
TERRAIN ELEVATliONS ARE READ (YES=1,NO=0) ISIJ(4) 0
CALCULATIONS ARE IJRITTEN TO TAPE (YES=1,NO=0) ISIJ(5) = 1
LIST ALL INPUT DATA (NO=0,YES=1,MET DATA ALSO=2) ISIJ(6) = 2
COMPUTE AVERAGE CONCENTRATION (OR TOTAL DEPOSITION)
IJITH THE FOLL~IING TIME PERIODS:
HOURLY (YES=~,NO=O) ISIJ(7) = 0
2-HOUR (YES=1,NO=O) ISIJ(8) 1
3-HOUR (YES=1,NO=0) ISIJ(9) 0
4-HOUR (YES=1,NO=0) ISIJ(10) = 0
6-HOUR (YES=1,NO=0) ISIJ(11) = 0
a-HOUR (YES=1,NO=0) ISIJ(12) = 0
12-HOUR (YES=1,NO=0) ISIJ(13) = 0
24-HOUR CYES::1,NO=0) ISIJ(14) = 0
PRINT 'N'-DAY TABLE(S) (YES=1,NO=0) ISIJ(15) = 0
PRINT THE FOLLOWING TYPES OF TABLES IJHOSE TIME PERIODS ARE
SPECIFIED BY 151.1(7) THROUGH ISIJ(14):
DAILY TABLES (YES=1,NO=0) ISIJ(16) 0
HIGHEST & SECOND HIGHEST TABLES (YES=1,NO=0) ISIJ(17) = 0
MAXIMUM 50 TABLES (YES=1,NO=0) ISIJ(18) 1
METEOROLOGICAL DATA INPUT METHOD (PRE-PROCESSED=1,CARD=2) ISIJ(19) = 2
RURAL-URBAN OPTION (RU.=O,UR. MODE 1=1,UR. MODE 2=2,UR. MODE 3=3) ISIJ(20) = 0
IJIND PROFILE EXPONENT VALUES (DEFAULTS=1,USER ENTERS=2,3) ISIJ(21) = 1
VERTICAL POT. TEMP. GRADIENT VALUES (DEFAULTS=1,USER ENTERS=2,3) ISIJ(22) = 1
SCALE EMISSION RATES FOR ALL SOURCES (NO=O,YES>O) ISIJ(23) = 0
PROGRAM CALCULATES FINAL PLUME RISE ONLY (YES=1,NO=2) ISIJ(24) = 1
PROGRAM ADJUSTS ALL STACK HEIGHTS FOR DOIJNIJASH (YES=2,NO=1) ISIJ(25) = 1
PROGRAM USES BUOYANCY INDUCED DISPERSION (YES=1,NO=2) ISIJ(26) = 1
CONCENTRATIONS DURING CALM PERIODS SET = 0 .(YES=1,NO=2) ISIJ(27) = 2
REG. DEFAULT OPTION CHOSEN (YES=1,NO=2) ISIJ(28) = 2
TYPE OF POLLUTANT TO BE MODELLED (1=S02,2=OTHER) ISIJ(29) = 1
DEBUG OPTION CHOSEN (YES=1,NO=2) ISW(30) = 2
.ABOVE GROUND (FLAGPOLE) RECEPTORS USED (YES= 1, NO=O) ISW(31) = 1
NUMBER OF INPUT SOURCES NSOURC = 67
NUMBER OF SOURCE GROUPS (=O,ALL SOURCES) NGROUP = 18
TIME PERIOD INTERVAL TO BE PRINTED (=O,ALL INTERVALS) IPERD =' 0
NUMBER OF X (RANGE) GRID VALUES NXPNTS = 0
NUMBER OF Y (THETA) GRID VALUES NYPNTS = 0
NUMBER OF DISCRETE RECEPTORS NXWYPT = 18
NUMBER OF HOURS PER DAY IN MET~OLOGICAL DATA NHOURS = 2
NUMBER OF DAYS OF METEOROLOGI1.1it DATA NDAYS = 27
SOURCE EMISSION RATE UNITS CONVERSION FACTOR TK =.10000E+07
HEIGHT ABOVE GRIOUND AT IJHICH IJIND SPEED IJAS MEASURED ZR = 18.00 METERS
lOGICAL UNIT NUMBER OF METEOROLOGICAL DATA IMET = 7
lOGICAL UNIT OF CALCULATION 'SAVE' TAPE ITAP = 3
J'LLOCATED DATA STORAGE LIMIT = 90000 WORDS
I~EQUIRED DATA STORAGE FOR THIS PROBLEM RUN MIMIT = 23261 IJORDS
•
96
source algorithm. The model requires that initial horizontal and
vertical dimensions (known as sigma 'y' and sigma 'z'

c ,
respectively) of each volume source be specified. These values
were dete:rmined based on the physical size of the process unit
(length, width, height and release height within the unit) .
Following USEPA guidelines, the initial sigma 'y' was calculated
by dividing the width of the unit by 2.15. Similarly, the height
of the uni.t was divided by 2.15 to estimate the initial sigma 'z'
(USEPA 1986). Table 5-2 indicates which process unit fugitives
were simulated as volume sources in the model. This table also
provides a listing of the ISC source numbers as well as the
initial sigma valuE~s.
In performing this analysis, sensitivity calculations were
conducted on the volume source algorithm to determine if a
process unit fugiti.ve source is best represented by a single
volume source of equal dimensions to the process unit or best
represented by subdividing the process unit into multiple volume
sources of smaller dimensions whose total dimension equals the
process unit size. These calculations entailed subdividing a
volume source into 4 and 9 equal sub-divisions and comparing
predicted concentrations for these alternate source descriptions
to the concentrations predicted by a single source. The results
of this analysis indicate that subdivision of these sources would
change the predicte~d concentrations by only a few percent. As a
result, fugitive emissions from each refinery process unit were
97
TABLE 5-2. FUGITIVE VOLUME SOURCES
RELEASE INITIAL INITIAL

ISCSOURCE HEIGHT SIGMAZ SIGMA Y
UNIT NUMBER (METER) (METER) (METER)
CRUDE FUGITIVES 1 6.096 2.835 13.488
REFORMER FUGITIVES 2 6.096 2.835 15.349
FCU FUGITIVES 3 6.096 2.835 7.442
COKER FUGITIVES 4 6.096 2.835 10.93
NAP HYDRO FUGITIVES 5 6.096 2.835 4.65
TREATING FUGITIVES 6 6.096 2.835 8.605
I.D
00 COMBO FUGITIVES 7 11.28 2.835 15.349
PRODUCT LOADING 8 9.144 4.253 7.209
modeled as a singl_= volume source in order to reduce required
computer resources.
5.1.2 storage Tanks
storage tanks were simulated in the model as elevated area
sources. The size of the area source used as input into the
model was a square of an equivalent cross-sectional area to the
round storage tank. The height of the tank was input into the
model as the height of the area source. The mass emission rate
was divided by the cross-sectional area of the source and this
flux (i.e., grams per second per square meter) was input into the
model.
Table 5-3 summarizes the tanks which were simulated as elevated
area sources. Also, contained in this table are the equivalent
size of the source" release height and ISC source number.
5.1.3 API Separator, Coker Pond·and Landfarm
The API separator, the coker pond and the two inactive landfarms
were simulated as three separate ground-level area sources. The
larger of the two inactive landfarms was subdivided into two area
sources of equal area. The remaining ground-level area sources
were modeled as a single area source. The length and width
dimensions of the area sources used in the model were a square of
equivalent size to the actual source.
99
TABLE 5-3. TANK AREA SOURCES
INITIAL RELEASE SOURCE

ISCSOURCE SIGMA Y HEIGHT AREA
TANKID# NUMBER (METER) (METER) (METER) **2
100 20 40.52 13.72 1641.71
101 21 40.52 13.72 1641.71
102 22 40.52 13.72 1641.71
103 23 40.52 13.72 1641.71
104 24 40.52 13.72 1641.71
105 25 40.52 13.72 1641.71
106 26 40.52 13.72 1641.71
107 27 43.28 13.72 1873.16
108 28 32.42 11.13 1096.01
109 29 32.42 11.13 1050.80
110 30 54.03 14.63 2918.81
300 35 24.31 11.28 591.02
301 36 24.31 11.28 591.02
601 49 19.8 11.28 392.04
606 53 32.42 11.28 1050.80
607 54 32.42 11.28 1050.80
608 55 32.42 11.28 1050.80
609 56 32.42 11.28 1050.80
610 57 32.42 11.28 1050.80
611 58 32.42 11.28 1050.80
612 59 32.42 11.28 1050.80
614 60 32.42 11.28 1050.80
615 61 32.42 11.28 1050.80
616 62 16.21 11.28 262.63
617 63 16.21 11.28 262.63
700 67 23.63 11.28 558.57
701 68 19.8 11.28 392.04
702 69 19.8 11.28 392.04
900 70 32.42 11.89 1050.80
903 73 9.05 9.449 81.90
905 74 4.05 7.315 16.41
604 83 32.4 11.3 1049.76
605 84 32.4 11.3 1049.76
618 85 32.4 11.3 1049.76
622 86 24.3 11.3 590.49
620 87 9.5 8.7 90.25
902 88 5:7 4.7 32.49
613 89 32.4 11.3 1049.76
619 90 32.4 11.3 1049.76
621 91 9.5 8.7 90.25
100
As in the case of the volume sources, a sensitivity analysis was
performed on the area source algorithm to determine if each area
source (the API separator, coker pond and landfarm) is best
represented by a single area source of equal dimensions to the
actual source or best represented by subdividing each source into
multiple area sources of smaller dimensions whose total dimension
equals the actual source dimension. For example, is it better to
characterize an area source of 10,000 m2 in size as single-area
source with a 100-meter side length or as 16 separate area
sources each having a 25-meter side length?
This analysis showed that when one source is repressed by
multiple area sources of reduced size, the model predictions are
slightly lower near the source. However, subdivision does not
have an effect at further downwind distances. As a result, each
of these sources would be modeled as a single area source to
conserve computer resources.
Table 5-4 presents a summary of the sources modeled as ground-
based area sources. This table lists the ISC source number,
emission flux rate and area source size.
5.1.4 Point Souroes
The sewer vents, blowdown stacks, and barge loading were
simulated as point sources.
101
TABLE 5-4. GROUND-BASED AREA SOURCES
SOURCE ISCSOURCE SOURCE

NUMBER AREA
(M**2)
API SEPERATOR 80 2400.02

COKER PONDS 101 342.25
LAND FARM 221 25344.64
* LANDFARM 222 33966.49
* LANDFARM 223 33966.49
* for modeling purposes, one IOf the land farms was subdivided into two area sources
102
For the blowdown st.acks, the actual stack height and measured
stack temperature was used. There were no nearby solid
structures. that would cause downwash for the blowdown stacks.
The releas.e height for barge loading was 3 meters and the release
height for sewer vents was at ground-level. For these sources, a
diameter of 1 meter and an exit velocity of 0.1 meter per second
was used. These stack parameters were selected to simulate zero
plume rise (i.e., no buoyancy or momentum induced dispersion).
Table 5-5 presents a summary of the point sources information.
5.2 Methodology Used to Compare Measured and Predicted

Concentrations
This sUbsection outlines the approach that was used in making the
comparison between the predicted and the observed concentrations.
The first step in this analysis was to identify a subset of the
BTEX measurements to be used for analysis. This subset consisted
of periods of persistent meteorological conditions and reasonable
source-receptor relations (i.e., alignment of source and receptor
for a given wind direction which persisted for approximately a 2-
hour period) existed. These 2-hour periods were then modeled
using the BTEX emission inventories and the observed (on-site)
meteorological conditions. Concentrations were then estimated at
each of the monitor locations. In order to account for
103
TABLE 5-5. POINT SOURCES
STACK STACK
SOURCE ISCSOURCE RELEASE EXIT EXIT STACK
NUMBER HEIGHT TEMPERATURE VELOCITY DIAMETER
(METER) (K) (METER/SEC) (METER)
MARINE BARGE LOADING 82 3.00 280.00 0.10 1.00

SEWER VENT 201 0.00 280.00 0.10 1.00
SEWER VENT 202 0.00 280.00 0.10 1.00
SEWER VENT 203 0.00 280.00 0.10 1.00
SEWER VENT 204 0.00 280.00 0.10 1.00
SEWER VENT 205 0.00 280.00 0.10 1.00
SEWER VENT 206 0.00 280.00 0.10 1.00
b SEWER VENT 207 0.00 280.00 0.10 1.00
+='
SEWER VENT 208 0.00 280.00 0.10 1.00
SEWER VENT 230 14.94 290.00 0.09 1.00
COKER BLOWDOWN STK 241 37.10 328.70 0.27 0.91
COMBOBLOWDOWNSTK 242 30.45 317.60 0.24 0.59
ULTRA FORMER BLOWDOWN STK 243 36.58 334.30 0.24 0.76
uncertainty in the measurement of wind direction, a fine receptor
grid was placed around the monitor location. This receptor grid
extended 150 meters on either side of the monitor location and
had a resolution of 50 meters. Comparisons were then made by
pairing the predictions and observations in time and space (with
spacial pairing being relaxed over this small receptor grid) .
This comparison is analogous to the techniques that have been
used to validate the USEPA dispersion models, except the
requirement for pairing was maintained. The receptor height was
set at 1.2 meters, which corresponded to the height of the
sampler inlet.
A post-processor program was written taking the ISCST binary
output file that contained the concentration, and importing it
into a summary spreadsheet. This spreadsheet contained the 2-
hour average measured and predicted concentrations, the model
estimated source contribution and the ratio of predicted-to-
observed (CpjCo) concentrations. These spreadsheets were
produced for each monitoring site and each chemical. Modeling
results are presented in Appendix B and the summary spreadsheets
are contained in Appendix C.
Figure 5-1 presents the fine receptor grid used, the location of
each monitor and source locations. After the modeling was
completed, the loca'tions of the predicted concentrations were
examined in relationship to the monitors. If model predictions
105
FIGURE 5-1 RECEPTOR GRID USED IN COMPARING MODELED TO OBSERVED IMPACTS
370396 370896 371396 371896 372396
4120888 I .to i i 4120888
4120388 4120388
o MONITOR
• RECEPTOR
b. SOURCE
en
w
I--:
~ 4119888 4119888
Q •• ..• •-A&
• • ••
c:::
o
o A
~ (.)
A
A1 _. -A.o. -•• -A4 0 •• _ •••
• • •a 0 • • .. -AQ. • •• 0 "0 " ... 0 • 0 0 -A-& 0
~ A • • • • • •• • • • • • • • • -. • • • • • A.
••••••
A ....... """. 0 0 6. 0 0 • • •
~ 4119388 .11..11..11. A Air 4119388
~
•
Az. A
. ... .
A e A A A A A ...... .
A 4.11. A
~ A
I- A~ A A
::::> A A
6. A
A 6
A A 6. A /j.
A .all.
A
A
4118888 4118888
A A
A A A
A A A
4118388 l. II 4118388
3703ge 3708ge 371396 371896 3723gS
UTM EAST COORDINATES
exhibited a large concentration gradient across the model
receptor grid, or if the maximum predicted occurred at the edge
of the grid, these time periods were eliminated from further
analysis. This criteria was imposed because the observance of
these conditions in the predicted concentrations indicated our
experimental design was inadequate to draw further conclusions
from these data.
Because the distance from the source to the monitors was
relatively small (typically about 200 meters), pairing in time
and space is appropriate and should somewhat reduce the poor
correlation typically observed when model verifications are
performed in this manner. Further,. because of the limited size
of the database, not pairing the data in time and space would
lead to inconclusive results.
The first technique used in making these comparisons was to plot
predicted and observed concentrations as a scatter plot. These
were produced for each site with a separate plot for each
compound. A general trend in the performance of the model
inventory can be observed from these plots for each chemical.
The second analytical technique used was to examine the ratio of
the average predicted concentration at a given site to the
average observed concentration at the same site (CpjCo). This
was done for each site and for each pollutant (i.e., calculation
107
of the mean predicted concentration at a given site and divided
it by the mean observed concentration at the same site). This
statistic provides an estimate of bias in the predictions. A
ratio of 1 implies a perfect agreement between model predictions
and the observed data. A ratio of less than 1 indicates that the
model underpredicts, while a ratio greater than 1 implies model
overprediction.
The third technique used was to compare the modeling and
monitoring data to determine what percent of the predicted
concentrations were within a factor of 2 of the observations.
Typically, this is the accuracy assigned to a dispersion model
such as ISCST.
In performing this analysis, it was found that for periods when
the monitored concentrations were near the analytical detection
limit, the model overpredicted the observations by a very large
amount. These data unrealistically skewed the overall model
statistics. There is a large uncertainty associated with
sampling and analyses of these low concentration levels.
Therefore, a second estimate of model bias was computed excluding
these time periods.
These statistics were used in the final analysis of the BTEX
inventory (i.e., scatter plots, bias calculations and percent of
the model predictions within a factor of 2 of the measurements) .
108
The next step was to allow the ISCST model to estimate source
culpability (i.e., individual source contribution to each
receptor location). Thus, for each 2-hour model prediction,
ISCST calculated the contribution from each source. A subset of
data was created using the ISCST estimates of source culpability
to further examine the comparison of model predictions and
observations to see if any additional conclusions could be drawn
regarding the accuracy of the emission inventory. In making
these comparisons, we looked for periods when the ISCST model
calculated a dominant source for a 2-hour period. We then
combined the data for the dominant source groups (i.e., process
fugitives, blowdown stack, tanks) and compared the model
performance to the observations. For example, for periods when
ISCST computed that: process fugitives were the dominant source,
statistics were computed comparing the model predictions to the
observations. The criteria chosen for identifying a dominant
source in this analysis was set at 50 percent of the total
impact.
A Cp/Co was calculated for those cases using the average
predicted concentrations and the average measured concentrations.
In this way, the accuracy of source specific BTEX emissions could
be estimated.
If the model predictions for a specific compound were within a
factor 2 of the measured concentrations, it was concluded that
109
the accuracy of the inventory was within the limits of
uncertainty of the dispersion model. Specifically, this was
determined by examining the overall mean bias (CpjCo) for a given
monitoring site. Thus, for a given site if Cp/Co was within the
range of 0.5 to 2.0, it was concluded that the inventory was
accurate for those sources which were influencing a specific
monitor. For situations where the bias exceeded a factor of 2,
it was concluded that the inventory might be inaccurate.
For those conditions where it was concluded that a possible
emission rate bias might exist, the emission data were reviewed
to determine if there was sound justification to adjust the
emission rate. In reviewing all the data, no sound justification
was found ,to make any adj ustments to the inventory. The
following section discusses analyses conducted to support this
conclusion.
5.3 Discussion of Results
This sUbsection presents the results of the model and monitoring
comparisons. These comparisons are presented by sampling site.
5.3.1 Site A1
Figure 5-2 presents the scatter plots for site A1. A separate
plot is presented for each chemical. On each plot, the perfect
correlation between predicted concentrations and observations is
indicated by a solid line'. The data points on each figure
110
FIGURE 5-2. COMPARISON OF PREDICTED AND OBSERVED
CONCENTRATIONS FOR BTEX AT SITE A1
150 A 400 f A
360
A 125 M
~ -
i300
...~ 100 §260
~ 76
e I~
~ 160
60
1 ~ 100 Legend:
26
8 50
1) Line indicates a
.•
8 00
01<°'\.0°0 perfect agreement
o 1", 'IV I' iii I Iii iii I i I" i i Iii r I I II i i IJ
I-' o 25 50 75 100 125 150 '" "'III"
50 100 150 200 250 300 350 400 between modeled
I-' PREDICTED CXN:ENTR,t,TION (UGA"It-3) PREDICTED CON:ENTRAl1ON (UG/M. . 3l
l~
and measured
SITE A1 BENZENE S HE AI TOLUEI>E
concentrations.
2) Data points above

100 450 I A the line indicate
model/inventory is
90 400 underestimating the
fI M
·80 observations.
~350
g
~ 70 3) Data points below
§300
~
the line indicate
model/inventory is
overstating the
u observations.
I: 150
30 1
!!l100
I:1
20
10-1 / - 50
0
00
0
0
0.1<
o iii 'i lii;O 0 i i 0I I I
1'1 i i I i i i i )1 i I') I I I i 7. iii I Iii i .1
10 20 30 40 50 60 70 80 90 100 50 100 1 b0 200 250 300 350 400 450
PREDICTED CCN:ENTRATI()II (UG/Ma-3) PREDICTED CON:ENTR"Tl()ll (UG/MO-3)
SITE Al ETHYLBENZEI>E SHE Al XYl..E/'£

indicate the actual points of comparison. A comparison of these
BTEX scatter plots for site A1 suggest several conclusions. For
all compounds, there is a tendency for the model to overpredict
the BTEX concentrations. Observed concentrations of ethylbenzene
and xylene are slightly lower than those of benzene and toluene.
This figure also indicates that there is a larger scatter in the
benzene observed and modeled data than there is for TEX.
Table 5-6 presents a summary of model statistics for this site
for each chemical. As indicated by this table, the mean bias for
the benzene model predictions was 1.9, indicating that the model
was overpredicting the observations. Examination of the data
indicates that the calculated bias-for benzene was affected by
periods when the monitored data were near the analytical
detection limit. When these were removed, the mean bias (CP/Co)
is 1.7. In addition, 44 percent of the benzene predictions are
within a factor of 2 of the observations.
The mean bias for the toluene model predictions is 6.5. When the
measured concentrations of toluene near the detection limit were
excluded, the ratio becomes 6.2. It was found that 7 percent of
the toluene predictions were within a factor of 2 of the
observations.
The mean Cp/Co ratio for ethylbenzene is 12.6, including periods
near the detection limit, and 8.0 excluding these periods. For
112
TABLE 5-6. SUMMARY OF COMPARISON OF PREDICTED AND OBSERVED
CONCENTRATIONS FOR SITE AI.
%
Cp/Co Cp/Co FACTOR
CHEMICAL ALL EXCLUDING MDL (a) OF 2 (b)
tlbNL.~,Nb 1.~ 1.1 44.4
TOLUENE 6.5 6.2 7.1
ETHYLBENZENE 12.6 8.0 12.5
XYLENE l3.1 12.0 0.0
a) Excluding periods when the measurments were at or near the analytical detection limit.
b)Percent of the predictions within at factor of two of the observations.
113
xylene, the mean Cp/Co ratio, including periods near the
detection limit, was 13.1 and 12.0, excluding these periods. For
ethylbenzene, 13 percent of the observations were within a factor
of 2 and for xylene, none of the data were within a factor of 2.
The poor correlation between model predictions and measured
concentrations for xylene may by a result of uncertainties in
xylene stream composition.
Table 5-7 provides information on the average source
culpabilities produced by the model for this site. This table
was prepared by averaging all source culpabilities for all data
collected at this site. It shows that three sources were largely
responsible for the measured BTEX concentrations at this site,
the process sewers, coker pond and coker blowdown stack.
Table 5-8 shows the average Cp/Co ratios for those periods when
either the sewers, the coker pond, or the blowdown stack had the
major influence on the predicted concentrations. "Major
influence" was defined as an impact for a 2-hour sampling period
of 50 percent or more by one source and contributions from other
sources were evenly distributed. For periods when the model
indicated that sewers were the major source, there was a
substantial overprediction which is probably a result of
uncertainties in wind directions and local turbulence. Both of
these factors will have a pronounced effect on a ground-level,
114
TABLE 5-7. AVERJllGE MODELED CONTRffiUTION FOR SITE Al
BENZENE TOLUENE
AVERAGE AVERAGE
PERCENT PERCENT
UNIT CONTRIBUTION UNIT CONTRIBUTION
1 LKUUD t<UlJllLVD 0.:.1. 1 LKUUD t'UlJlllVD V.I>
2 REFORMER FUGITIVE 0.0 2 REFORMER FUGITIVE 1.2
3 FCU FUGITl\IE 0.0 3 FCU FUGITIVE 0.1
4 COKER FUGITIVE 1.0 4 COKER FUGITIVE 2.8
5 NAP HYDRO FUGITIVE 0.0 5 NAP HYDRO FUGITIVE 0.7
6 TREATING FUGITIVE 0.0 6 TREATING FUGITIVE 0.0
7 PRO BLEND FUGITIVE 0.0 7 PRO BLEND FUGITIVE 0.0
8 PRODUCT LOADING 0.0 8 PRODUCT LOADING 0.0
9 TANKS 1.5 9 TANKS 2.1
10 API 0.0 10 API 0.0
11 WASTE H20 TANK 0.0 11 WASTE H20 TANK 0.0
12 BARGE LOADING 0.0 12 BARGE LOADING 0.0
13 COKER POND 47.7 13 COKER POND 32.6
14 SEWER 37.9 14 SEWER 51.6
15 LAND FARM 0.0 15 LAND FARM 0.0
16 COOLING TOWER 0.0 16 COOLING TOWER 0.0
17 BLOW DOWN STKS 11.8 17 BLOW DOWN STKS 8.2
ETHYLBENZENE XYLENE
AVERAGE AVERAGE
PERCENT PERCENT
UNlIT CONTRIBUTION UNIT CONTRIBUTION
1 LKUUht<UVITIVh 1.1 1 LKUUnt<UVlTIVh 0.1
3 FCU FUGITIVE 0.1 3 FCU FUGITIVE 0.3
10 API 0.0 10 API 0.0
14 SEWER 43.7 14 SEWER 35.7
115
TABLE 5-8. AVERAGE MODELED CONCENTRATIONS,
MEASURED CONCENTRATIONS, AND Cp/Co RATIOS DURING
PERIODS OF COKER POND, BLOWDOWN STACK
AND SEWERS IMPACTS AT SITE Al
Avg Modeled Avg Measured
Dominant Cone. Cone. Number
Source Chemical (ug/m3) (ug/m3) of Samples ~
Coker Pond Benzene 29.0 17.2 4 l.7
Toluene 194.5 79.8 1 2.4
Ethylbenzene 64.4 9.9 1 6.5
Xylene 233.7 19.0 6 12.3
Coker Blowdown Benzene 9.3 17.1 2 0.5
Stack Toluene 20.2 10.7 1 l.9
Ethylbenzene 14.5 8.4 1 l.7
Xylene 65.7 18.8 2 3.5
Sewer Benzene 68.0 13.9 2 4.9
Toluene 144.4 2l.1 5 6.8
Xylene 258.3 17.0 4 15.2
116
fugitive point source such as a sewer grate.
For benzene, when the sewer had the major impact, the mean bias
(CpjCo) was 4.9. When the coker pond had the major influence,
the mean bias (CpjCo) was 1.7. When the coker blowdown stack had
the major source contribution, the mean bias for benzene was 0.5.
Since the mean bias in the predicted benzene impacts for the
blowdown stacks was within a factor of 2 of the observations, it
was assumed that the emission rate used in the modeling was
accurate to within a factor of 2 of the actual emission rate.
For toluene, during periods when sewers were impacting the
monitor, the average CpjCo was 6.8. For periods when the coker
blowdown stack was the dominant source, the ratio of CpjCo was
1.9. Thus, predictions for the blowdown stack were within a
factor of 2 and it is assumed that the emission rates used in the
modeling are accurate within the prescribed margin. When the
coker pond was the dominant source, the ratio of Cp/Co was 2.4.
However, this calculation is based on only one sample.
For ethylbenzene and xylene, the ratio of CpjCo was 7.2 and 15.2,
respectively, during periods when sewers were largely responsible
for impacts. For ethylbenzene, when the coker blowdown stack was
affecting the monitor, the mean bias was 1.7. The ratio was 6.5
when the coker pond was affecting the monitor. The ratio of
CpjCo for xylene for the coker blowdown stack was 3.5 (based on
117
only two samples) and 12.3 for the coker pond.
Comparison of the ratio of Cp/Co for sewers indicates that a
significant bias exists in the BTEX data. For sources like a
sewer grate, it is not surprising that the model is not
replicating the observed data. For these events, small
uncertainties in wind direction could have a pronounced effect on
modeling results. Also, because of the high roughness in the
immediate vicinity of these sources, additional localized
dilution may have occurred. For these reasons, it was assumed
that the bias is a function of the modeling of near field affects
and not inaccuracies in the inventory. Therefore, the
measurements conducted on these sources were used in the emission
inventory.
Intercomparison of the ratio of Cp/Co for the coker pond
influence for all 4 chemicals indicate that, except for xylene,
the ratio of Cp/Co are similar (range of 1.7 to 6.5). These
results illustrate that a significant bias exists in the ground-
level area source algorithm in the ISCST model instead of with
the measured emission rate from the coker pond. This has been
documented previously in the literature.
For the coker blowdown stack, benzene, toluene, and ethylbenzene
model predictions w'ere wi thin a factor of 2 of the observations.
For xylene~, the deviation was greater than a factor of 2. This
118
larger deviation in xylene data may be a result of uncertainties
in estimat;ing the xylene content of the hydrocarbon streams
within the coker area.
5.3.2 site A2
Scatter plots for BTEX for site A2 are presented in Figure 5-3.
As indicated by this figure, the modeled predictions and the
observations agree quite well for benzene, while there is
significant bias toward model/inventory overprediction of the
observations for the other chemicals.
Table 5-9 presents summary statistics for these chemicals for
site A2. For benzene, the ratio of Cp/Co was 0.8. There were no
periods when samples at or near the analytical detection limit
affected this statistic. For this chemical, 56 percent of the
predictions were within a factor of 2 of the observations.
For toluene, the mean ratio of Cp/Co was 1.3 with 26 percent of
the predictions within a factor of 2 of the observations. Like
benzene, there were no periods when samples at or near the
detection limit affected this statistic.
For ethylbenzene, the ratio of Cp/Co, including periods when the
sampler concentrations were near the analytical detection limit,
was 5.2. When these periods were eliminated, this ratio became
3.8. In this case, approximately 30 percent of the predictions
119
200 350 I A
175
A <;1300
.
~ 150 ~
2 250
~125 is
~200
1,00 ~ 150
I 75 ;0 ~
~ 100
50 Legend:
o .0
50
25 1) Line indicates a
~
perfect agreement
e1< °00 ~o
0~;~111111111111111111111'111111111,,1 o Iii Iii between modeled
25 50 75 100 125 150 175 200 50 100 150 200 250 300 350
PREDICTED caaNTRATI<l'j (00..1'1.. 3) PREDICTED CON:ENTRATI<l'j (OO/M. . 3l and measured
SITE A2 EENZENE SITE A2 TOLUEI'£ concentrations.
:.--l
N
0 2) Data points above
the line indicate
100 ~I A
model/inventory is
90 underestimating the
350
A A observations.
. 80
~ 70
~300 3) Data points below
~
.... is 250 the line indicate
60
model/inventory is
50
i~200 overstating the
observations.
40
I 30
~16e
I ~100
20 , 0
00
50
10-=1 / 0 0
0 o 0
0
10 20 30 40 50 60 70 80 90 100 50 100
. _.
150 200 250 300 350 400
PREDICTED CONCENTRATI<l'j (OO/M"3) PREDICTED CON:ENTRATlON (00/110-3)
SITE A2 ETHYLBENZENE SITE A2 XYLENE

TABLE 5-9. SUMMARY OF CONIPARISON OF PREDICTED AND OBSERVED
CONCENTRATIONS FOR SITE A2.
%
Cp/Co Cp/Co FACTOR
CIffiMICAL ALL EXCLUDING MDL (a) OF2 (b)
Jj~l~L.~l~~ u.~ u.~ )).)
TOLUENE 1.3 1.3 26.1
XYLENE 4.2 4.0 14.3
b)Percent of the predictions within a factor of two of the observations.
121
were within a factor of 2 of the observations.
In the case of xylene, the overall ratio of Cp/Co was 4.2,
including periods \~hen the measured concentration was near the
analytical detection limit. When these periods were ,excluded,
this ratio dropped to 4.0. In this case, only 14 percent of the
predictions were within a factor of 2 of the observations.
Table 5-10 shows the average source culpabilities produced by the
model for this site. As indicated in the table, the combo unit
blowdown stack, se~lers, and tanks were primarily culpable for
BTEX impacts.
Table 5-11 shows the average Cp/Co ratios for those periods when
the model indicated that a single source was the primary
contributor to a significant predicted concentration (dominant
source was defined as 50 percent of total contribution for a
single event) .
As shown in this table for benzene, when the combo unit blowdown
stack was the dominant source, the average ratio of Cp/Co was
0.7. Similarly, for sewers, the average ratio of Cp/Co was 1.0.
When the t.anks were the dominant source, the average Cp/Co was
0.5.
As shown in the table, the impacts for the combo blowdownstack
122
TABLE 5-10. AVERAGE MODELED SOURCE CONTRIBUTION FOR SITE A2
BENZENE TOLUENE
AVERAGE AVERAGE
PERCENT PERCENT
1 Cl{UlJb FUvlTIVb U.5 1 Cl{UUh J:<UvITIYh U.3
6 TREATING FUG ITIVE 0.0 6 TREATING FUGITIVE 0.8
8 PRODUCT LOADING 0.0 8 COMBO FUGITIVE 0.0
10 API 0.0 lOAPI 0.0
12 BARGE LOAD ING 0.0 12 BARGE LOADING 0.0
14 SEWER 38.9 14 SEWER 58.2
ETHYLBENZENE XYLENE
AVERAGE AVERAGE
PERCENT PERCENT
1 Cl{UUbJ:<UvI11Yh U.5 1 Cl{UUh J:<UvITIYh U.S
7 PRO BLEND FUGITIVE 03 7 PRO BLEND FUGITIVE 0.3
8 PRODUCT LOADING 0.0 8 COMBO FUGITIVE 3.3
10 API 0.0 10 API 0.0
14 SEWER 56.4 14 SEWER 55.4
123
MEASURED CONCENTRATIONS AND Cp/Co RATIOS
DURING PE:RIODS OF SEWERS, BLOWDOWN STACK, AND TANK IMPACTS
AT SITE A2
Source Chemical (ug/m3) (ug/m3) of Samples .QtiQQ

Sewers Benzene 31. 8 33.2 6 1.0
Toluene 138.6 54.3 16 2.6
Xylene 168.7 25.5 14 l3.5
Combo Unit Benzene 15.2 21. 8 4 0.7
Blowdown Stack Toluene 42.8 68.5 3 0.6
Xylene 70.2 76.6 4 0.9
Tanks Benzene 11.8 25.7 3 0.5
Toluene 46.7 28.3 3 1.7
Xylene 46.8 40.8 2 1.1
124
for toluene exhibited an average ratio of 0.6. When the toluene
emissions for the sewers were the major impact, the average ratio
was 2.6. When the tanks were impacting, the ratio was 1.7.
For ethylbenzene, t.he mean ratio for Cp/Co for periods whem the
combo blowdown stack was affecting the monitor was 1.3, 9.1 for
the sewers, and 1.3 for the tanks. In the case of the xylene
emissions from the blowdown stack, the model was on average
replicating the observations within a factor of 2, (Cp/Co of
0.9). Thet ratio was 13.5 for the sewer xylene emissions and
1 . 1 from t.he tanks.
Intercompa.rison of these data indicate several important trends.
First, for the sewe.rs, benzene impacts were generally within a
factor of 2. Toluene impacts were slightly overstated, and for
ethylbenzene and xylene a large positive bias was observed. It
should be recalled that those impacts originate from measured
source emi.ssions data. This variation in impacts may result from
actual variations in emission rate over time. Comparison of
these data. to sewer impacts from Site A1 indicate a similar bias
for ethylbenzene and xylene, but large differences for benzene
and toluene.
Second, for the combo blowdown stack and storage tanks,
comparison of the data indicate that the emission rate used in
the modeling is representative of actual emissions within the
125
limits of uncertainty of this analyses.
5.3.3 sites A3 and A4
The results from sites A3 and A4 will be presented together since
both of these moni t.oring locations were generally downwind of the
storage tanks.
Figures §-4 and 5-5 present the BTEX scatter plots for sites A3
and A4, respectively.
As indicated by the benzene scatter plots for site A3, the
predicted concentrations are slightly underestimating the
observed concentrat.ions. For toluene, ethylbenzene and xylene,
the plots show reasonable agreement between the modeled and
measured concentrations, although there is considerable scatter
in the toluene data.
At site A4, in general, the model reproduces the observed data
for all chemicals. However, for ethylbenzene and xylene, there
is a tendency for the model to overpredict the highest measured
concentrations while for benzene, the model may be
underpredicting the highest observed concentrations. As noted at
the other sites, there is considerably more scatter in the
toluene data than w'ith the other chemicals.
Table 5-12 presents a summary of modeled/measured concentration
126
~0J A
225 o _300J
A M250
" 200
~ ~ J
/1
_ .
~ 175
§200
~ o
I:: 1,5,
O(j
co
~ 100
\ ~ 100 Legend:
00 "
I 75 • ~
. .0 '"
60 1) Line indicates a
504 / '"
25 perfect agreement
between modeled
o l'i i Ii I Ii I I I Ii i i II iii I I I I i i i i i i i i i I i i i i i i i i /I I I I i I rt o f'"
o 25 50 75 100 125 150 175 200 225 250 50 100 150 200 250 300 and measured
PREDICTED ca-cENTRATIa-I (UGA1.. 31 '" PREDICTED CON:ENTRATIa-I (UG/M"31 concentrations.
SITE A3 EENZENE SITE A3 TOLUEN::
~
N the line indicate
'I
model/inventory is
l00ji------------------------~A 275
underestimating the
90 250 observations.
j 0
A ~225
"80
~ ~ 3) Data points below
g200 the line indicate
~ 70
model/inventory is
- 175
8
overstating the
observations.
125
I'se
u
30
roo
i;!;j 75
0
I:1
20 o 0
50 .'0 ••
o
10 25
1 /0 .0
10 20 30 40 50 6121 70 80 90 100 25 50 75 1 00 125 1 50 1 75 200 225 250 275
PREDICTED CCNCENTRATIa-I (UGA1o-31 PREDICTED CON:ENTRATION (UG//1M-31
SITE A3 ETHYLBENZEN:: SITE A3 XYLENE

150 A 150 f JI
A 125 ., 125
~ ~
~ 100 § 100
...
o
o 175
I~ u
50 ! 50 Legend:
1 [IS
o 1) Line indicates a
25 ° 25 'II
00 perfect agreement
o
between modeled
o V, and measured
25 50 75 100 125 150 , 25 50 75 100 125 150
PREDICTED CXN:ENTRATIet! (UO/MI. 3) PREDICTED CON:ENTRATIet! (UO/M"3l concentrations.
SITE A4 BENZENE SITE A4 TOLUEI'£
I-' the line indicate
N
00 model/inventory is
J----------------------------- A 350 A
100 1 underestimating the
90 observations.
.,"80 .,300
~ 3) Data points below

~ 70 ~250 the line indicate
~ model/inventory is
~ 60 overstating the
;200 observations.
I: ~150
30
~
~100
1 20
50
10 o
o
iii I i Iii II I II i i i i i Iii iii Iii i ,,,,,,,,,,1 (3 y; ,0, ~

0r"o""", I o .
10 20 30 '10 50 60 70 80 90 100 50 100 150 200 250 300 350
PREDICTED CON:ENTRATIet! (UO/MI.3) PREDICTED CON:ENTRATlON (UO/t!o-J)
SITE A4 ETHYLBENZEI'£ SITE A4 XYLENE

TABLE 5-12. SUMMARY OF COMPARISON OF PREDICTED AND OBSERVED
CONCENTRATIONS FOR SITES A3 AND A4.
SITE A3
%
Cp/Co Cp/Co FACTOR
tlhNLhNh V.4 V.4 )4.L
TOLUENE 1.2 1.1 79.1
XYLENE 1.4 1.4 72.7
SITEA4
%
Cp/Co Cp/Co FACTOR
tltl"lL.tI'IIJ:'.. V.b u.o bU.U
TOLUENE 1.2 1.2 90.0
XYLENE 1.6 1.6 54.5
b)Percent of the predictions within a factor of two of the observations.
129
statistics for these sites. For benzene, the ratio of Cp/Co was
0.4 at Site A3 and 0.6 at Site A4. Fifty-four percent of the
predicted concentrations were within a factor of 2 at site A3 and
60 percent at site A4.
The ratio of Cp/Co for toluene was 1.1 at site A3. For this
case, 79 percent of the predictions are within a factor of 2 of
the observations. .At Site A4, the ratio of Cp/Co was 1.2 with
90 percent of the predictions within a factor of 2 of the
observations.
For ethylbenzene at Site A3, the ratio of Cp/Co was 1.9 with no
measurements being near the analytical detection limit. At
site A4, the ratio of Cp/Co for all periods was 1.8; this value
dropped to 1.6 when concentrations above the detection limit were
included. At site j~3, 55 percent of the ethylbenzene predictions
were within a factor of 2 of the observations. At Site A4,
67 percent of the predictions were within a factor of 2 of the
observations.
At both sites, xylene concentrations were always over the
detection limit and were overestimated slightly with a Cp/Co at
site A3 of 1.4 and Cp/Co at site A4 was 1.6. At Site A3,
73 percent of the observations were within a factor of 2 and at
site A4, 55 percent of the observations were within a factor
of 2.
130
As shown by Tables 5-13 and 5-14, the average culpable BTEX
sources at sites A3 and A4 are the storage tanks, although at
site A3 there were some periods when other source impacts were
dominant.
Tables 5-15 and 5-16 present data on the ratio of Cp/Co when the
model indicated that a single source was responsible for the
observed impacts for sites A3 and A4, respectively.
At site A3 for tank impacts, the ratio of Cp/Co for benzene was
0.4, indicating the~ impacts from these sources were being
underpredi.cted. However, for the other chemicals, the ratio of
Cp/Co was 1.1, 1.6 and 1.5 for TEX, respectively, indicating an
excellent agreement. between the model predictions and
observations.
At this si.te, on two occasions the combination of the model
predictions and the monitor data indicate that the ultra former
blowdown stack was the dominant source. During these time
periods, the model and the monitoring data agreed (Cp/Co was
equal to 1).
Also at this site, ethylbenzene and xylene impacts were observed
from the sewers. For these data, predictions and observations
agreed within a factor of 2.
131
TABLE 5-13. AVERAGE MODELED SOURCE CONTRffiUTION FOR SITE A3
BENZENE TOLUENE
AVERAGE AVERAGE
PERCENT PERCENT
1 CKUUt rUUIlWt U.U 1 CKUUt rUUUIVt U.U
10 API 0.0 10 API 0.0
14 SEWER 4.7 14 SEWER 16.3
ETHYLBENZENE XYLENE
AVERAGE AVERAGE
PERCENT PERCENT
1 LKUU!H'UVLl1V~ 0.2 1 CKUUtrUVll1V~ U.O
10 API 0.0 10 API 0.0
11 WASTE H20 TANK 0.0 11 WASTE H2O TANK 0.0
14 SEWER 23.3 14 SEWER 25.4
132
TABLE 5-14. AVERAGE MODELED SOURCE CONTRIBUTION FOR SITE A4
BENZENE TOLUENE
AVERAGE AVERAGE
PERCENT PERCENT
1 CKUUl::'- t'UULlIVl::'- U.U 1 CKUUl::'- t'UUllIVl::'- U.UU
6 TREATING FUG ITIVE 0.0 6 TREATING FUGITIVE 0.00
8 COMBO FUGITIVE 0.0 8 COMBO FUGITIVE 0.00
9 TANKS 93.1 9 TANKS 93.60
10 API 0.0 lOAPI 0.00
14 SEWER 1.2 14 SEWER 0.80
17 BLOW DOWI"f STKS 3.2 17 BLOW DOWN STKS 1.90
ETHYLBENZENE XYLENE
AVERAGE AVERAGE
PERCENT PERCENT
1 CKUUl::'- t'UUITIVl::'- U.Uj 1 CKUUl::'-l'UUUIVl::'- U.Ul
9 TANKS 92.47 9 TANKS 93.90
10 API 0.00 10 API 0.00
14 SEWER 2.48 14 SEWER 2.50
133
PERIODS OF TANKS, BLOWDOWN STACK
AND SEWERS IMPACTS AT SITE A3
Source Chemical Cug/m3) Cug/m3) of Samples QPLQ.Q

Toluene 102.3 89.6 24 1.1
Ethy1benzene 25.4 15.9 15 1.6
Xylene 110.7 72.4 18 1.5
Ultraformer Ethy1benzene 20.9 20.1 2 1.0
BlowdoWIl
Stack
Sewers Ethy1benzene 16.7 17.2 2 1.0
Xylene 141.9 158.4 2 0.9
134
PERIODS OF TANK IMPACTS
AT SITE A4
Source Chemical (ug/m3) (ug/m3) of Samples guQQ
Toluene 60.7 50.1 11 l.2
Ethy1benzene 60.7 50.1 8 l.2
Xylene 74.5 45.6 11 l.6
135
At site A4, tanks were the dominate sources. All model data were
within a factor of 2 of the observations.
The conclusion reached regarding these data is that benzene
impacts are underpredicted but are close to being within a factor
of 2 of the measurements at Site A3 and are within a factor of 2
at site A4. Toluene, ethylbenzene, and xylene impacts show very
little bias between predictions and measurements. For these
data, it can be concluded that the inventories for benzene,
toluene, ethylbenzene and xylene are accurate within the limits
of uncertainty of the dispersion model.
5.3.4 sites AS and A6
The results from sites A5 and A6 will be discussed together since
they are both related to impacts from the wastewater treatment
area.
Figure 5-6 shows a reasonable agreement between the model and the
measurements for benzene at Site A5. In this plot, measurements
were excluded when ·the inactive retention basin was affecting the
monitor (see section 3) . For toluene and xylene, there is
considerable scatter in the data. For ethylbenzene, reasonable
agreement is seen between the predictions and the observations.
However, a·t. the highest observed concentrations, some
overprediction by the model was found.
136
FIGURE 5-6. COMPARISON.OF PREDICTED AND OBSERVED
150 A ~J *
225
A
~ 125
200
~
~ gt 175
~ 100 ~
S150
I!:
175 ~ 125
~ 100
50 I$!
I 75
1 Legend:
50
25
1) Line indicates a
25
perfect agreement
between modeled
25 50 75 100 125 150 25 50 75 100 125 150 175 200 225 250 and measured
PREDICTED CONCENTRATION (UG/M"3) PREDICTED CONCENTRATION (UG/M--3)
'-l
"'"
-- concentrations.
SITE A5 BENZENE SITE A5 TOLUENE
100 350 the line indicate
model/inventory is
90 underestimating the
A 1'1 300
. observations .
: B0
1:
, ~
g 70 g250
3) Data points below
~ § the line indicate
:: 60 I-
~200 model/inventory is
I-
z overstating the
I.. ~ 150 observations.
40
~
0:
30
~ 100
1 20
50j ..
10
o V' i i i I I~
10 20 30 40 50 60 70 80 90 100 o 50 100 150 200 250 300 350
PREDICTED CONCENTRATION (UGA1"3) PREDICTED CONCENTRATION (UG/M"3)

At site A6, substantial overprediction by the model was observed
for all chemicals as seen in Figure 5-7.
As shown on Table 5-17, the calculated bias (CpjCo) for benzene
at site A5 was 37.1 and 0.8 for site A6 for all periods. When
the concentrations near the detection limit are not included, the
Cp/Co is 1.0 for site A5 and 0.7 for site A6. The fraction of
the model predictions within a factor of 2 was 55 percent at
site A5 and 25 percent at site A6. It should be noted that the
bias statistics for site A6 for benzene are skewed by one
datapoint. If this outlyer is removed, Cp/Co for all periods is
3.7, and 3.4 for those above the detection limit.
For toluene, the ratio of Cp/Co was 1~6 at site A5 and 8.1 at
site A6 (both of these values have excluded the periods when the
measured concentrat.ions were near the detection limit). At
site A5, 75 percent of the predictions were within a factor of 2
of the observations, and at site A6, only 5 percent of the
observations were vd thin a factor of 2.
At Site AS and A6, the mean ethylbenzene values of Cp/Co was 1.4
and 24.1, respectively, (excluding periods near the analytical
detection limit). At site A5, 62 percent of the observations
were withi.n a factor of 2. Only 4 percent of the predictions
were withi.n a factor of 2 for Site A6.
138
FIGURE 5-7. COMPARISON OF PREDICTED. AND OBSERVED
800 , :A
70121
1;]
f
i:l /1 g600
§ 125 §S00
i g
~ 1121121 m400
§
~ 75 ~30e Legend:
~
~ 5121 @l200 1) Line indicates a
perfect agreement
25 11210
. between modeled
o 00 0
o o. 0 0 I and measured
o Ii IIII r III II' i I j II II i 1111, i i l l •
25 5121
a ar", """" """"",
75 100
"",~""""", I
125 150 175 200 o 10121 2121121 30121 40121 50121 60121 71210 800 concentratl.ons.
PREDICTED ca-lCENTRATICN (00,11.. 3) PREDICTED CONCENTRATION (00,11"3)
SITE A6 BENZENE SITE A6 TOLUENE 2) Data points above

w"
\.0 the line indicate
model/inventory is
300 A underestimating the
900 , A
observations.
81210
A 25121 A 3) Data points below
~70121 the line indicate
~ g
~200 model/inventory is
3600 overstating the
~500 observations.
aJ
I'~ ~41210
o
11121121 ~3121121
Bl
8 200
5121
1121121
a !' ,., ~ ,'p , '1 , .,

5121 1 00 15121 200 250 3121121 1121121 2121121 3121121 400 5121121 600 700 800 9121121
PREDICTED CON:ENTRATION (00/11"3) PREDICTED CON:ENTRATION (UG/11"3)

TABLE S-17. SUM~,fARY OF COMPARISON OF PREDICTED AND OBSERVED
CONCENTRATIONS FOR SITES AS AND A6.
SITE AS
%
Cp/Co Cp/Co FACTOR
CHEMICAL ALL EXCLUDING MDL (a) OF2 (b)
BENZENE 37.1 1.0 -54])
TOLUENE 1.S 1.6 7S.0
ETHYLBENZENE 2.2 1.2 61.S
XYLENE 2.3 1.3 37.S
SITEA6
%
Cp/Co Cp/Co FACTOR
CHEMICAL ALL EXCLUDING MDL (a) OF2 (b)
BENZENE (c) 0.8 0.7 25.0
TOLUENE 11.0 8.1 4.8
ETHYLBENZENE 31.S 24.1 4.0
XYLENE 2S.2 21.1 0.0
a)Exc1uding periods when the measurments were at or near the analytical detection limit.
b)Percent of the predictions wihtin a factor of two of the observations.
c) Statistic influenced by an outlyer if this is removed, Cp/Co IS 3.68 and 3.42 when data above the detection linit are used.
140
For xylene, the ratio Cp/Co was 2.3 for Site AS for all
observations and 1.3 when the measured concentrations are near
the detection limit. At site A6, the xylene Cp/Co ratio was 2S.2
for all observations and 21.1 when the observations near the
detection limit are removed. For Site AS, 38 percent of the
observations were within a factor of 2 and at site A6, none of
the observations were within a factor of 2.
As shown on Tables 5-18 and 5-19, the API separator is the most
significant BTEX source impacting Sites AS and A6. The
wastewater tank impacted these locations a few hours.
In examining these data, it is apparent that the averaged
predictions are within a factor of 2 of the averaged observed
data.
Tables S-20 and 5-21 present the average predicted and observed
concentrations and resulting bias when one source had the
majority of the impact for Sites AS and A6.
For site A5, the API separator and the water tank were the
dominant sources. For the API separator, model predictions were
within a factor of 2 for all chemicals. For the wastewater tank,
impacts were within a factor of 2 for benzene and toluene but for
ethylbenzene and xylene, impacts were underpredicted slightly,
however, this was based on"only one sample.
141
TABLE 5-18. AVERAGE MODELED SOURCE CONTRIBUTION FOR SITE AS
BENZENE TOLUENE
AVERAGE AVERAGE
PERCENT PERCENT
1 CKUUbrUUrUVb 0.0 1 CKUUbrUUUIVb 0.0
10 API 49.7 10API 53.0
14 SEWER 2.0 14 SEWER 2.4
ISLAND FARM 0.0 15 LAND FARM 2.1
ETHYLBENZENE XYLENE
AVERAGE AVERAGE
PERCENT PERCENT
1 CKUUb rUUfu v n 0.1 1 CKUUbrUUlTIVb 0.0
10 API 59.8 10 API 59.5
14 SEWER 2.3 14 SEWER 2.2
ISLAND FARM 9.7 15 LAND FARM 135
142
TABLE 5-19. AVERAGE MODELED SOURCE CONTRmUTION FOR SITE A6
BENZENE TOLUENE
AVERAGE AVERAGE
PERCENT PERCENT
UNIT CONTRffiUTION UNIT CONTRffiUTION
1 CKUUb J:<UUUIYb U.U 1 CKUUbJ:<UUUIYb O.1l
2 REFORMER RJGITIVE 0.3 2 REFORMER FUGITIVE 0.0
10 API 56.1 10 API 68.3
14 SEWER 35.0 14 SEWER 25.9
ETHYLBENZENE XYLENE
AVERAGE AVERAGE
PERCENT PERCENT
UNIT CONTRffiUTION UNIT CONTRffiUTION
1 CKUUb J:<UUlllYb U.1l 1 CKUUbJ:<UUlTIYb U.U
5 NAP HYDRO RJGITIVE 0.0 5 NAP HYDRO FUGITIVE 0.0
10 API 63.4 10 API 63.2
14 SEWER 30.1 14 SEWER 29.9
143
API SEPARATOR AND WATER TANK IMPACTS
AT SITE AS
Source Chemical (ug/m3) (ug/m3) of Samples .QpLgQ
API Benz,ene 40.8 104.0 9 0.4
Toluene 265.7 36.3 11 7.3
Ethylbenzene 96 .5 5.6 6 17.0
Xylene 360.0 20.7 8 17.4
Watertank Benzene 58.2 7.3 4 8.5
Toluene 172.2 11.3 3 15.2
Ethylbenzene 158.5 l.5 2 101.9
Xylene 604.7 15.7 2 38.6
144
API SEPARATOR AND SEWER IMPACTS
AT SITE A6
Source Chemical (ug/m3) (ug/m3) of Samples ~
API Benzene 40.8 104.0 9 0.4a
Toluene 265.7 36.3 11 7.3
Xylene 360.0 20.7 8 17.4
Sewers Benzene 58.2 7.3 4 8.5
Toluene 172.2 11.3 3 15.2
Ethylbenzene 158.5 l.5 2 101.9
Xylene 604.7 15.7 2 38.6
aInf1uenced by outlyer if removed Cp/Co 2.1
145
At site A6, the API separator and the sewers were the dominant
sources. For cases when the separator was the dominant source at
site A6, the benzene Cp/Co was 0.4. This statistic is strongly
influenced by one measurement.
During this time period, concentrations of TEX were very low.
This elevated benzene concentration may be a result of the surge
basins which had been removed from service and were undergoing
remediation. If this datapoint is excluded, then Cp/Co becomes
2.1. For TEX, the ratio of Cp/Co for the API separator was 7.3,
17.0 and 17.4, respectively. Since the emission rate from this
source. was measured, it is assumed that the observed
overprediction is a result of bias in the area source algorithm
and not bias in the emission inventory.
The model estimates at Site A5 were slightly closer to the
observations than at Site 6. This may be because this monitoring
site was further from the source than site A6.
5.4 conclusions Regarding the Accuracy of the Inventory for BTEX

As a result of this analysis, a number of conclusions can be
reached regarding the accuracy of the emission inventory for
BTEX. First, it was found that, in general, actual emissions
from BTEX sources are well characterized by the inventory
developed as a result of this study. Recall that the monitor
data reflects actual emissions of BTEX and these data were
146
compared t.o estimated concentrations using a hypothesized
emission inventory. This comparison, therefore, provides a means
of confirming the accuracy of both the magnitude and speciation
of emissions. Based on the results of this analysis and
recognizing the limits of uncertainty of this analysis, total
refinery emissions are being accurately represented by this
inventory. The results of this analysis indicate that all
significant emission sources have been accounted for in this
inventory. Thus, this inventory represents a realistic baseline
from which pollution prevention options for air emissions can be
studied.
Second, comparison of this inventory with the original SARA
inventory shows that there are two significant source types
(barge loading and the blowdown stacks) not included in the SARA
inventory. It should be noted that barge loading is not included
in the SARi\ reporting requirements. The use of only the SARA
inventory to identify prevention options would have given
erroneous results.
Summau
The following presents a summary of the results of this analysis
by chemical.
Benzene
Based on the results of these analyses, it can be concluded that
147
the benzene inventory is accurate to within the limits of
uncertainty of the ISC model. This conclusion was reached for a
wide range of source types.
In addition, it is useful to compare the distribution of benzene
emissions using the original SARA emission estimate and the
estimated emissions that resulted from this study. This
information is presented in Figure 5-8. As indicated by this
figure, the original SARA emissions for benzene were 18 tons per
year. The estimated emissions as a result of this analysis,
excluding barge loading, were 52.1 tons per year, primarily
because of an estimated 32 tons from the blowdown stacks which
was not part of the SARA inventory .. When barge loading is
included, the total benzene emissions were 67.2 tons per year.
In Figure 5-8 under the category of wastewater treatment,
emissions from the API separator, sewer vents, and other sources
associated with thE~ wastewater treatment portion of the refinery
have been combined.
Toluene
In general, toluene emissions were found to be accurately
represented within the uncertainty limits of the dispersion
model.
Figure 5-9 presents; a histogram plot of toluene emissions using
148
FIGURE 5-8.
HISTOGRAM OF BENZENE EMISSIONS
~
Ltl
~
Z
1--', 0
~ l:::-
(/)
z
o
(/)
(/)
:a:
LlJ
BLOWDOWN STACKS BARGE LOADING COKER POND
EMISSION SOURCE
f.--ACTUAL EMISSIONS _ SARA )

[I ______________._ n _ _. __. _ _ _ _ _ _ • _ _ _ _ . _ _ _ _ _ _ _ _ _ • ___ _
FIGURE 5-9.
HISTOGRAM OF TOLUENE EMISSIONS
cc
L1j
~
21
g
W 1
~ ~
c:
2
o
(/)
(/)
:E
W
WASTEWATER TREA
SLOWDOWN STACKS SARGE LOADING
EMISSION SOURCE
r~~~?TUA~_~~ISSIONS - SARA REPORT l

the SARA inventory and the inventory resulting from this
analysis. Similar to the benzene inventory, changes in the
toluene emissions were observed.
For toluene, the SARA inventory estimated 91.4 tons per year of
emissions. As a result of this study, toluene emissions were
estimated to be 129.1 tons per year, excluding barge loading.
Including barge loading, toluene emissions are estimated to be
181.9 tons per year, with the blowdown stacks contributing
56.5 tons per year to these totals.
Ethy1benzene
In general, ethylbenzene emissions were estimated within the
limits of uncertainty of the analytical tools.
The distribution of ethylbenzene emissions from the original SARA
inventory and this analysis are contained in Figure 5-10. Total
ethylbenzene emissions estimated in the SARA inventory were
24.4 tons per year. As a result of this study, emissions were
63.6 tons per year excluding barge loading and 77.6 tons per year
including barge loading, with the blowdown stacks contributing
45 tons to these totals.
Xylene
Figure 5-11 presents the distribution of xylene emissions for the
SARA estimates and as a result of this study. The SARA inventory
151
FIGURE 5-10
HISTOGRAM FOR ETHYLBENZENE EMISSIONS
C?
L5
......
~
z
lJ1
N g
(fJ
Z
o
(fJ
(fJ
~
w

EMISSION SOURCE
I~ ACTUAL EMISSIONS ItB SARA ~

FIGURE 5-11.
HISTOGRAM OF XYLENE EMISSIONS
~
~
~
z
o
t-' /::::..1
~ (f)
Z
o
(f)
(f)
::a:
w
EMISSION SOURCE
, _ ACTUAL EMISSIONS _ SARA

L~ __~________~___ __
for xylene was 107.5 tons per year. As a result of this study,
the estimated emissions were 207.3 tons per year excluding barge
loading and 276.5 tons per year including barge loading, with the
blowdown stacks contributing 121.6 tons to these totals.
Except for the sewer and coker pond xylene sources (which are
measured emission rates) the xylene emissions were generally
found to result in model predictions within a factor of 2 of the
measured concentrations. The only exception to this was the
coker blowdown stack xylene emissions. However, that exception
was based on only two datapoints which are insufficient for
drawing any conclusions.
154
6.0 ExpoSu.re Modeling
In this section, the em~ssion inventory that was developed in
previous sections is translated into ambient air concentrations
(or exposure) beyond the refinery fenceline. Dispersion modeling
was used to perform this task. A follow-up report (Klee et al
1991) will also use dispersion modeling to determine what
benefits can be derived, in terms of exposure, from the
implementation of pollution prevention options. For example, the
question can be asked, "What are the changes in exposure (or
risks) of various pollution prevention options and will these
changes significantly reduce exposure?" The results of these
analyses can be compared to the benefits that would be derived if
pollution prevention practices were-ranked using other criteria,
such as mass emission rates. The intercomparison of pollution
prevention options will be addressed as a part of the ranking
criteria for this project.
An important aspect of these analyses is the concept of
developing site-specific exposure criteria. The benzene impact
assessment for this refinery uniquely provides insight on control
strategies/options and allows for a determination of incremental
risk. The concept IJf incremental risk tends to better focus the
ideal selection of control strategies and optimizes the monies
spent on emission reductions.
No risk assessment was performed as part of this analysis,
155
although the exposure assessment provides a site-specific,
speciated hydrocarbon database by source (spatially and
temporarily adjusted) to allow an incremental benzene risk
assessment.
Exposure estimates were developed for four types of chemicals:
1) BTEX; 2) other SARA reported chemicals; 3) criteria pollutants
(S02' N0 2, PM-10 and CO); and 4) other chemicals. The modeling
methodology that was used for these four groups of chemicals was
similar.
The following sUbsections present the modeling methodology used
and results for each group of chemicals. section 6.1 presents
the modeling performed for BTEX chemicals. In section 6.2, the
modeling for the other SARA chemicals is presented and
Section 6.3 contains the information for the criteria pollutants.
section 6.4 presents data for chemicals which appear on the SARA
list, but are not elmitted in quantities which require reporting.
6.1 Exposure Modeling for BTEX
6.1.1 Methodology
The modeling of the impacts for BTEX chemicals was performed
using the USEPA ISCST dispersion model. This is the same' model
used in section 5 to test the accuracy of the emission inventory
for BTEX. For this analysis, the model was executed with 1-year
156
of sequential hourly meteorological data so that an assessment of
annual average impacts could be made.
The meteorological data used in this analysis were 1987 surface
observations collected by the National Weather Service (NWS) at
Norfolk, v'irginia, and upper air data, from Wallops Island,
Virginia, for 1987. Norfolk is about 80 kilometers from the
refinery and both locations experience the same land and sea
breeze conditions. Therefore, these data are representative of
meteorological conditions at the refinery. In compiling the
historical data for this analysis, it was found that this was the
only data set readily avail~ble. Ideally, it would be desirable
to perform an analysis using more than I-year of meteorological
data. However, annual impacts should be consistent from year to
year and we were more concerned with the intercomparison of
scenarios or relative change in exposure than maximum impacts.
For BTEX chemicals, the emission inventory developed in Section 5
was used as input to the ISCST model. Concentrations were
predicted at a total of 859 receptors. The receptor grid was
composed of a coarse grid and a fine grid. The coarse grid
extended 10 kilometers from the refinery center. The resolution
of the coarse grid 'was 1 kilometer. The fine grid extended
0.5 kilometers from the refinery center and had a resolution of
250 meters. The fine grid included receptors within the refinery
fenceline. This was done so that modeling results could be
157
displayed as concentration isopleths. As a result of this, care
should be exercised in analyzing the computer listings from the
ISCST model (contained in Appendix 0). Also, receptors were
excluded from an area surrounding the barge loading area because
of the inability of dispersion models to correctly assess the
impact when a receptor is located on top of or adjacent to an
emission source. Figures 6-1 and 6-2 present plots of the two
receptor srrids.
In performing the modeling, both 24-hour and annual averages were
computed, however, only the annual results will be presented
here.
6.1.2 Results
The modeling results are summarized in several different ways.
First, the results are presented as concentration isopleths.
These figures are overlayed onto a USGS topographic map
containing the Yorktown Refinery.
Second, maximum predicted concentrations for various receptor
classifications were calculated as follows: 1) beyond the
fenceline in the York River; 2) beyond the fenceline on land; and
3) at a nearby residence. These locations were identified by
overlaying predicted concentrations onto a USGS topographic map.
158
FIGURE 6-1 COARSE GRID
360198 362198 364198 36619B 368198 370198 372198 374198 376198 378198 380198 38219B
4130213 4130213
4128213 4128213
4126213 • • -I 4126213
t •
en ..124213 [ • • • • • + ~ 4124213
W
I- .
~
Z ..122213 I- ~ 4122213
0
0::::
t-- ~ 4120213
U"I o0 4120213 I-
1.0
U
:r:
I- 4118213 l- ~ 4118213
n::: l-
0 •
Z
4118213 I- ~ 4116213
~
I-
:::::>
4114213 I- ~ 4114213
4112213 • • 4112213
•
4110213 4110213
4108213 4108213
360198 362198 364198 36619B 368198 370198 372198 374198 376198 378198 380198 38219B
FIGURE 6-2 FINE GRID
367698 368698 369698 370698 371698 372698 373698 374698 375698
<123713 ~ l4'2J7'J
4122713 I- -I 4122713
4121713 I- --I 4121713
(f) l-
W •
~ • •
~ 4120713 L -I 4120713
0
0::: I- ..
~O
°0
U 4119713 • -I 4119713
•
:c e
l-
~
t
~ 4118713 I- -I 4118713
~
I-
:::::>
4117713 I- -I 4117713
4116713 4116713
4115713 4115713
367698 368696 369696 370696 371696 372696 373698 374698 375698
The third approach was to perform additional modeling to examine
source culpability for the maximum concentrations at the three
receptor classifications beyond the refinery fenceline.
The fourth approach compared modeled concentrations and typical

annual average concentrations measured in pristine, rural and
urban areas, as reported in the literature.
Figures 6-3, 6-4, 6-5 and 6-6 present concentration isopleths for
each of the BTEX chemicals, respectively. As indicated by these
figures, isopleths are orientated in a northeast/southwest
direction. These directions coincide with the prevailing wind
conditions observed at the refinery.
Maximum Predicted concentrations

Table 6-1 presents the maximum predicted annual average
concentrations at e~ach of the four receptor classifications for
BTEX. For benzene, the maximum annual average concentration, the
maximum concentration in the York River was 6.2 ug/m3, the
maximum concentration on land beyond the refinery fenceline was
1.3 ug/m3 and the maximum concentration at a nearby residential
receptor was 0.6 ug/m3• Table 6-1 also provides the UTM
coordinates for each of these receptors. It should be noted that
the maximum estimated benzene concentration occurred in the river
as a result of the proximity of the receptors to the barge
transfer point.
161
nGURE 6-3. BENZENE ANNUAL AVERAGE CONCENTRATIONS (UG/M**3)
377000
4121~OO -~-}.;'" 4121500
4120500 ~~~ ;;o& "<;l!0if. 4 ~~

_ ~~~ I ,~~
. _.. 4120500 ~ ._ :'f . _ ~ .
(f)
W
~
Z
o 4119500 Ihrl!i....~ Ml~ r:~,..{l' J:~_iWl'f<l:::,i!"J_<i I ~ -~~-: M J -- ' J''t[ll<~~~ \- lUI'~ , ""I 4119500
a-
.... 00::
N
0
I 0
I 4118500 ~ , ~"'I(6~- ,"X:Ii'I""_ = I~ tmA" ·2'~~:! II;\.. ,MB _,~JtJ.JY=-"_~~~~·\'v ~ 4118500
f-
0::
0
Z
~ 4117500 ~')JK.~ /'X'~~A~ 8 jl/~,,1.!.1 ''':~~,.:.li L t'?fA"""-' --';/ 1 \ : ' ~~~ 4117500
f-
:::::>
4116500 ~..J.2>XL~~:U~< ~ M' I ~l,. , L _ _-~l!;"'JR~ U 'Im"mIlIJT. F ~ - \ •~ L' ~ ) -.l 4116500
4115500 W Ujl!~·~~ ~~.Mr¥3;:;!ti~iJrN-?r~~>¥r l \) 7~il 4115500

-?J 0 .. ~
367000 368000 369000 370000 371000 372000 373000 374000 375000 376000 377000
FIGURE 6-4. TOLUENE ANNUAL AVERAGE CONCENTRATIONS (UG/M**3)
3870(10,
~
4111* 4121500
·m0500 ~~~~c;q; e~it· j P5iE--f\liiIf~:/~~ IS.:.-t~ . ~~~ 4120500

if)
W
~
Z
,... o 4119500 ~'\l\~AI' .~· j{:M\.b· F"I:¥i*~· 1-. tt J ·'~ · J;Wil. ·~""' -i',~ _ i· ~ · ~ 4119500
a.
w er
0
0
U
I 4118500 ~~~~~I::114~mM R§jlJ.;;ke:l,f~:]1711"," fli'J'fr: .·"tgr~. . .~~~~~·1r.I 4118500
f-
er
0
z ~. I "
4117500 ~~A . ,II/A _
PrJ:),, UI ~
,.;.r-"v . ,......~.
. . .. . L ~}({-:v ~ \)~ .A I 4117500
~ . . ··
f-
:::>
4116500 r~~\l -"'<>:t7~ ( : ..!If I~ ...P- I... : ~!li'jfh. ..~~ l.I;;ra\-"l~ ·l·' ~ . \ ~0 I' ·... 'IJ ) ...! 4116500
4115500 r -- ' <""' '3'" p ~/:fW''' - f= - - ~~~iJfl)1Pf("'~.d'~f'%ii!O \) ~~ if1 D ~1 4115500

367000 368000 369000 370000 371000 372000 J73000 374000 375000 376000 377000
FIGURE 6-5. ETHYLBENZENE ANNUAL AVERAGE CONCENTRATIONS (UG/M**3)
367000 35eooo 369000 370000 371000 372000 373000 374000 375000 376000 377000
4121500 4121500
4120500 ;j;;I_\':::' ~ ~ ', lao: . . , ' ' ~ ~"" J~~ _~:V ~ . .; . -l 4120500
(f)
W
~
Z
..... 0 4119500 ~"R\~~,...(" :;A~ }f~5i'" 7J~_. "q ~'\ I ':_I!'J' J J:~ ';~K' r ,'" s:.::.....
~ 4119500
'"
~ 0et::
o
o J"(""';-__~-1?)(l/.i~~~ --c ~IJ/~~ ~";11·· '1' ~""'".... ~ ~. ~--
,,!II. . \. "
I 4118500 "" _ 'ti;.~~"IIi.,, _-A ;k'; _ _"'.4;; c.. ·t~ :;t~y. ,- ~~.!.,..'~ ":, - ~~',l1\\l'f:---_ .......,, , ~7;II' - ~~tl... r\'l 4118500
I-
et::
o
Z
~ 4117500 fis.
~~~J1~r.lll ~- L '·~I~,!\.</ , \ ~~\\ \\lrl 4117500
I-
:::)
• -- -
I . -;:~
- ' ..
- .//.~ '-...J 0 ~
(tt' - -~ jjV(/O~O~ . . '. . ~~
o· "'_ ., ,r . ~ n: '. ,:~
... -,;: . . \1-\ : . ~J
I 't
4116500 ~ --. _ ,~:_"::oft· - _< 1" c..1 '...• -. : ~ _1>/ t-,: ;L . , ; : , ~ ~\ ' ~
-r.: 0 ' \. L ~- 4116500
41 15500 t!'m\'[>~ <o f"~ ~~~~'~F~4&':\~J'$U \\ . N,'1;1 -;, j Q4j 4115500

367000 368000 369000 370000 371000 372000 373000 374000 375000 376000 377000
FIGURE 6-6 . XYLENE ANNUAL AVERAGE CONCENTRATIONS (UG/M**3)
367000 366000 369000 370000 371000 372000 373000 37<1000 375000 376000 377000
4121500 4121500
4120500 W\ '! ~ <--..r» . if' t::: IS §i r _~~~V ~ - . ; • . ...t 4120500

(/)
W
~
Z
04119500 1."td._~~.-r:r:;;;a~;iIlM.i 1=e'~, . (1iA~' :;r·f J ··' ~:~ )~~ .·· r,; .r-·-"" ~~~ 4119500
.... n:::
B; 0
o
U
I 4118500 \. ;Tfl i~, _ ~~lllt1;-...=-:::;~ 4118500
l-
n:::
o
z
~ 4117500 .., ~_~ /..d.?a~ ...";!\(~'YJb L C· .I~'<...-:/ . \- ~~ \llJ 4117500
I- .• ( -~~,~O
:::>
I '.. . C/ 0 ." "\., .... . . : , 'l..,... \
~ . rj
:;:
"flO ''" ~.r/ b O~O'~ .~"., .~.,-: . . . . ~: ..
~: "• . r; "
4116500 1?~
~. - 'C,. I . .' Sf:? J~' ~£ .\ : ~ ~o . o~,.. ~: . 4116500
vl,\~~ ~":~/-<{""t{llW~'~~ \ ') . !$iC' 1 . I U~ I

4115500 ~ I ' L d \ '- "'''1 I{ 4115500
w - IUl:'~'<;)- ~~ " . rl ~ . ....::r~~ iW
367000 368000 369000 370000 371000 372000 373000 374000 375000 376000 3nooo
TABLE 6-1. MAXIMUM ANNUAL AVERAGE PREDICTED CONCENTRATIONS
FOR THE YORKTOWN REFINERY FOR BTEX CHEMICALS
OUTSIDE THE PLANT FENCELINE IN YORK RIVER OUTSIDE THE PLANT FENCELINE ON LAND OUTSIDE THE PLANT FENCELINE AT A NEARBY RESIDENCE
CONC. LOCATION (M) CONC. LOCATION (M) CONC. LOCATION (M)
CHEMICAL (UG/M**3) E. N. (UG/M**3) E. N. (UG/M"3) E. N.
BENZENE 6.2 372698 4121213 1.3 372698 4119963 0.64 373448 4120213
TOLUENE 21.9 372698 4121213 5.4 372698 4119963 2.37 373448 4120213
ETHYLBENZENE 5.9 372698 4121213 1.6 372698 373448 4120213
XYLENE 28.7 372698 4121213 7.2 372698 ::::: 1____ : : _____ --

373448
----------------------------
4120213
----------------------- ---------
I-'
0'\
0'\
For toluene, the ma.ximum annual concentration in the York River
was 21.9 ug/m3 , the maximum concentration beyond the fenceline on
land was 5,.4 ug/m3 and the maximum concentration at the nearest
residence was 2.4 u.g/m3 •
For ethylbenzene and total xylene, the maximum predicted average
concentration in the York River was 5.9 and 29 ug/m3 ,
respectively. The maximum predicted annual average concentration
on land beyond the refinery fenceline was 1.6 ug/m3 for
ethylbenzene and 7.2 ug/m3 for xylene. At a nearby residential
receptor, the maximum concentration for ethylbenzene was
0.72 ug(m3 and 3.1 ug/m3 for xylene.
Source cu1pabi1ities
Figure 6-7 presents annual average source culpabilities for the
receptors where the maximum benzene concentrations were predicted
in the river, on land beyond the fenceline and at a nearby
residence. As indicated from this figure, for the receptor
located in the river, 93 percent (5.8 ug/m3) of the impacts are
from barge transfer operations. The remainder of the impacts are
from tanks (3 percent or 0.20 ug/~) and blowdown stacks
(2 percent or 0.10 ug/m3).
For the maximum onshore impacts beyond fenceline, 41 percent
(0.53 ug/m3) are from barge loading. The large impact from barge
loading results from this receptor being located near the shore
167
FIGURE 6-7. SOURCE CULPABILITY FOR BENZENE
IN YORK RIVER
-
( \')
i<
i< 7.00 100 Z
0
-
::E
(!) 6.00
~
90
80
i=
::::l
-
::J
Z
0
5.00
4.00
'" 70
60
SO
aJ
a:
l-
Z
0
~
a:
3.00 40 0
30 I-
I- 2.00 Z
Z ~
% 20 W
W
- 0
1.00
0
Z 0.00
~ 10
0
a:
w
0 FUGITIVES API SARGE SEWER COOLING TOTAL a..
0 TANKS H20 TANK COKER LAND SLOWDOWN
SOURCE
I~ CONCENTRATION EtW PERCENT OF TOTAL
AT FENCELINE ON LAND
cr;-
... 1 . 4 n - . - r - - · - - - - - - - - - - - - - - - - _ , . . - - · . . , . .100 Z
... 90 0
~ 1.2 80
i=
::::l
2. 1.00..J~------------------_I: I+U--"i-70 aJ
a:
oZ O.
60
50
I-
Z
0
~ 0.6 40 U
I-
Z 0.4·n.JI----------VAm----------I' :mt--f30 Z
20 W
W U
U 0.2'n.JI-----YA+U-----YAl-1tI--------,--t:l.H.ft---i
10 a::
oZ
U
O•. oo-iJ--.i:4:ll~=w,.ra=.u.-_,.IGd!:lI&,od-,.c.GI;l:IIp.-..,......,.I(4;!¥:I::W.--r-0
API RG SEWER COOLING OTAL
W
a..
H20 TANK COKER LAND SLOWDOWN
SOURCE
I~ CONCENTRATION m PERCENT OF TOTAL I
AT A NEARBY RESIDENCE
cr;-
... o.7u 100 Z
... 90 0
:iE 6uo i=
G o. f-:80 ::::l
2. o. 5u 70 aJ
oz O. 4u-
60 ~
i= ;!'; ~ 50
oZ
c{ o. 3u- 40 U
g:Z ~ 30 I-
o. 2u Z
w .-.r"I'ft ~ 20
U
W
U o. 1u- a::
9~~ ~
10
oZ o. -"""'" a~ o ~
U FUGITIVES API BARGE SEWER COOLING TOTAL
TANKS H20 TANK COKER LAND SLOWDOWN
SOURCE
1m CONCENTRATION m PERCENT OF TOTAL I
168
of the York River. In addition, at this location, product
storage tanks are responsible for 24 percent of the total
estimated impact (0.,32 ug/m3 ). The API separator contribution at
this location was 11 percent (0.14 ug/m3 ). Blowdown stacks and
process fugitives accounted for 8 percent (0.11 ug/m3 ) and
9 percent (0.11 ug/m3 ), respectively, while sewers contributed
5 percent of the to1:al contribution (0.065 ug/m3 ) .
Barge operations are responsible for 53 percent of the total
predicted maximum concentration at the nearby residential
receptor (0.34 ug/m3:). The storage tanks contribution was
19 percent (0.12 ug/m3 ) . The process fugitive contribution was
7 percent (0.046 ug/m3 ), and the blowdown stacks resulted in
10 percent of the total predicted concentration (0.065 ug/m3 ).
From these model predictions, it can be seen that impacts from
barge operations represent a large percentage of the total
impacts at all three receptor categories. For onshore impacts,
storage tanks have the largest impact, however, their impact in
the river is quite small. Impacts from process fugitives and the
blowdown stacks are similar for the maximum onshore receptors.
Figure 6-8 presents source culpabilities for toluene. As
indicated by this figure, source culpabilities for toluene are
similar to those developed for benzene. This is not surprising
since BTEX emissions originate from the same sources.
169
FIGURE 6-8. SOURCE CULPABILITY FOR TOLUENE
IN YORK RIVER
M 25.00 100
iI
iI
Z
0
--2-
:E
C!) 20.00
~
90
80
i=
:::l
~ ~ 70 CO
Z 15.00 60
a:
~
0 Z
~ 50
~
0
10.00 ~ 40 ()
~ ~ 30 ~
Z ~ Z
W
W
()
5.00
~ 20 ()
~
Z
0
()
0.00
FUGITIVES
- API
1%
SARGE SEWER COOLING TOTAL
10
0
a:
w
a.
SOURCE
I~ CONCENTRATION ffEl PERCENT OF TOTAL
..:E.
M 6.00 100 Z
90 0
--2-
C!) 5.00 F
80 =>
70 CO
Z
4.00
60
a:
~
0 Z
3.00 50
~
0
40 ()
~ 2.00 ~
30 Z
Z W
W 20
() 1.00 ()
Z 10 a:
W
0 0.00 0 a.
()
H20 TANK
....
M
2.50 100 Z
0
:E
~ 2.00
~ 90
80
i=
:::l
2- t% CO
Z 1.50
70
60
a:
~
0 Z
50
~ ~ 0
()
~
1.00 40
30 ~
~
Z Z
0.50 20 W
W
~m~_ ~~
() ()
10
Z ~ a:
w
0
()
0.00
-
FUGmVES
TANKS
API BARGE
H2O TANK COKER
SEWER
lAND
COOUNG TOTAL
SLOWDOWN
0
a.
SOURCE
ImCONCENTRATION ElBPERCENTOFTOTAL I
170
In the river, 93 percent (20 ug/m3 ) of the maximum predicted
annual average impacts resulted from the barge operations.
For the maximum onshore impacts beyond the refinery fenceline,
barge loading was responsible for 34 percent (1.9 ug/m3 ) of the
total impact. Product storage tanks contributed 19 percent
(1.0 ugjm 3 ), the API separator impact was 15 percent
(0.81 ugjm3 ). Process fugitives contributed 9 percent
(0.051 ugjm3 ). The wastewater tank contribution was 8 percent
(0.45 ugjm3 ) , sewers contributed 6 percent (0.34 ugjm3 ) , and
blowdown stack contribution was 6 percent of the total impact
(0.31 ugjm 3 ).
For the maximum concentration at a residential receptor, the
largest toluene contribution was from barge loading, 50 percent
(1.2 ugjm3 ) . storage tanks contributed 18 percent (0.39 ugjm3 ).
Blowdown stacks and process fugitives had similar impacts on an
annual basis at 9 percent (0.21 ugjm3 ), and 8 percent
(0.18 ugjm3 ), respectively.
The culpability results for ethylbenzene are summarized in
Figure 6-9. For the maximum concentration, located in the river,
the majority of the predicted impacts for ethylbenzene were from
barge operations, 90 percent (5.4 ugjm3 ).
For the receptor showing the maximum onshore impacts, sewers had
171
FIGURE 6-9. SOURCE CULPABLITY FOR ETHYLBENZENE
IN YORK RIVER
,
....
(i). 00
z
~
~
f-oo o
~.
~ f-.o §
~
::::::l
~
z
. 10
~
CD
o ~ f-.o
Z
~ "'" ~
o
3
~ f-.o o
t-
t- ""'" '" Z
Z ill
ill ~ o
0' ",.
a:
~
Z
-
'0
o -. ill
0..
o " Fll<lTNES
TN«S
SEWER TOTAL
SOURCE
-( ' ) , ..,.
-It
-It
, 00
z
o
-
---
::::iE' i=
(!), .~
:::>
:::> 10 CO
Z
, ...., a:I-
0' Z
~ f-;n
oo
~" - .
1-".., ~
I-
Z '" ZW
W".0-
ra> o
o
z c:
8"
0
~mI~
FUO~ N"I
m BNKE ~
~
COOLNG
m TOTAL
'0
W
a.
TAhKS H2O TAN< COKER LNCl fl..O'I\{)()WN
SOURCE
I~ CONCENTRATION E!E PERCENT OF TOTAL I
, 00
M
-It z
1-.0
-It o
~ ,..,. OIl i=
:::>
-z ·
(!)
o
"
:::> 10
reo
CO
a:
I-
Z
... o
i="
~
I-
Z
. ''''
~
~
~
o
I-
Z
W
W
o
''''
~ 1-00 oc:
m~
I
_m~ ~ m_ 10
ooZ •• W
a.
I'UGIllIS N'I
SOURCE
I~ CONCENTRATION lIm PERCENT OF TOTAL
172
the largest single contribution at 38 percent (0.65 ug/m3 ).
Emissions from storage tanks, the API separator and the blowdown
stacks had similar Eathylbenzene impacts; 13 percent (0.23 ug/m3 ),
11 percent ( 0 . 19 ug/m3 ) and 13 percent ( 0 • 21 ug/m3 ),
respectively.
For ethylbenzene at a nearby residence, barge operations were
responsible for the majority of the impacts; 43 percent
(0.31 ug/m3 ) of the total impact.
The culpability results for xylene are presented in Figure 6-10.
For xylene at the receptor where maximum impacts were predicted
in the river, barge loading contributed 93 percent (27 ug/m3 ).
For maximum onshore impacts beyond the refinery fenceline, sewers
had the largest contribution, 40 percent (2.8 ug/m3 ) . The
remainder of the impacts were from product storage tanks,
14 percent (1. 0 ug/m3 ), the API separator, 12 percent (0.8 ug/m3 )
and barge operations, 15 percent (1.1 ug/m3 ).
At a nearby residence, barge loading had the largest
contribution, 51 percent (1.6 ug/m3 ). Similar impacts were
predicted for the API separator, barge operations and sewers at
approximately 9 percent (0.3 ug/m3 ) each. The impact from the
blowdown stacks was 12 percent (0.4 ug/m3 ).
173
FIGURE 6-10. SOURCE CULPABILITY FOR XYLENE
IN YORK RIVER
-....
t ') :lQ ~
~
,00
z
...., o
~
:J
.. ~
'"
~ ~
~
1=
rs> :J
10 co
~ :n .~
...., ~
~
Z
o Z
~ ,.
~
~
o
o
~ '" l-
~
~
l- '0
Z '" Z
W
o • ~ 20
W
o
~
a:
z
oo 0
FUGrTIllES - API BARGE SEWER COCl..NG
~
TOTAl
'0
w
a..
TAN(5 H2O TN« COKER UYfJ Bl...OWOCIW!"I
SOURCE

,
....
cry. ~
~
00
z
o
::::lE' ~
a2- . ~
~ 1=
roo :J
CD
I
70
a:
oz • rs' l-
z
~ < 8l-
'"
l-
~ ~ "" ZW
odi • rz, o
~ ~~ a:
~
z'
8 0
~MS
mm1l APt
m
BMGE SE'WER
~
COOI.Nl TOTAL
10
w
a..
TN«S H:i!O TNt< COKEA LNiJ EILCJ!M)()ytfoI
SOURCE

8iC 3.50 100 Z
iC
90 0
--::: 3.00
80 i=
::::>
-
(!)
::::> 2.50 70 OJ
if
Z 2.00 ~ 60 I-
0 ~~ 50
Z
0
~
I-
1.50
1.00
~
40
30
0
I-
Z
Z
W ~~ 20 0
W
m~~
0 0.50 a:
Z
0
0
0.00
FUGITIVES API
HImSARGE SEWER COOLING TOTAL
~"""""
10
0
w
a.
SOURCE
I~ CONCENTRATION m PERCENT OF TOTAL
174
comparison of '~orktown Impacts with "Typical" Ambient Air
It is useful to place the results of this modeling into the
perspective of ambi,ent measurements. Table 6-2 contains a
summary of modeling results for BTEX and a summary of ambient
measurements of BTEX for remote, rural and urban sites. These
monitoring data were obtained from the EPA database (Shah and
Heyerdahl 1988). All of these data represent annual average
concentrations.
For benzene, refinery impacts at the refinery fenceline are
similar to concentrations observed in a rural environment. At
the nearby residence, predicted benzene impacts due to the
refinery are similar to concentrations observed in a remote
setting. It should be noted that actual benzene concentrations
at these locations will be larger than just the refinery impact
as a result of other background sources (eg. automotive).
The toluene impacts from the refinery at the fencelirie and at the
nearby residence receptor fall in between the measurements made
in a rural and urban environment.
For ethylbenzene, the maximum fenceline receptor is less than a
typical urban concentration, while at the nearby residence,
refinery impact is the same as a typical rural measurement.
No data were available for xylene.
175
TABLE 6-2. COMPARISON OF ANNUAL AVERAGE PREDICTED IMPACTS TO TYPICAL
MEASURED CONCENTRATIONS FOR DIFFERENT TYPES OF ENVIRONMENTS FOR BTEX CHEMICALS
MAXIMUM PREDICTED MAXIMUM PREDICTED
CONCENTRATION CONCENTRATION TYPICAL REMOTE TYPICAL RURAL TYPICAL URBAN
AT THE FENCELINE (a) AT A NEARBY RESIDENCE CONCENTRATION CONCENTRATION CONCENTRATION
CHEMICAL (UG/M**3) (UG/M**3) (UG/M*·3) (UG/M**3) (UG/M**3)
BENZENE 1.3 0.6 0.51 1.5 5.7
TOLUENE 5.4 2.4 0.19 1.3 7.7-12.0

!
ETIIYLBENZENE 1.6 0.7 0.06 0.7 2.7 I
t-' a) Predicted on land

o...J
()"\
Benzene Emission Inventory sensitivity Modeling
As part of the exposure modeling that was conducted for benzene,
several sensitivity model simulations were conducted to examine
the effect of uncertainties in the emission inventory for benzene
on population exposure. In this analysis, upper and lower bounds
estimates of benzene emissions were made. Figure 6-11 presents a
summary of the emission rates for the various source categories
used in this analysis. For the upper-bound case, the emission
rate of benzene from API separator and the sewers was doubled,
process fugitive emissions were doubled and emissions from
product storage tanks were doubled. This upper-bound case
resulted in estimated benzene emissions of 86.6 tons per year.
In the lower-bound case, estimates of emissions were reduced for
wastewater treatment, process fugitives and the storage tanks.
For this case, refinery benzene emissions were set at 62.0 tons
per year.
These two cases were then modeled using the ISCST model and the
resulting concentrations isopleths are presented in Figure 6-12.
As indicated by this figure, there is some difference between the
isopleths for the u.pper case inventory and the base case
inventory. These modeling results were further analyzed by
computing the areas contained within the 0.12 and 1.2 ug/m3
isopleths (Table 6-3). As indicated, the difference in area
inscribed within th.e 0.12 ug/m3 isopleth for the baseline
inventory and the area for the upper-limit inventory estimate
177
FIGURE 6-11. HISTOGRAM OF BENZENE
FOR SENSITIVITY ANALYSIS
a:
-US
.~
CJ)
z
o
I-'
C
...... CJ)
00
z
o
CJ)
CJ)
:E
w
EMISSION SOURCE
r- UPPER LIMIT -.BASELINE ~ LOWERUM-IT]

FIGURE 6-12. ANNUAL AVERAGE BENZENE CONCENTRATIONS FOR THE
EMISSION INVENTORY SENSITIVITY CASES

.....
- 37_ 371000 372BOO 313eee 37"""'" 3/seee 376000 377000
,~ ~-
~ :iQI Ii! ~
. " - I L,L ,J " p~
C -. ~j
<4121S1e <4121500
I. . _: • <4121l1500
<4121l1500 hl~~(:&!" "",;::;;-.,~
~;;'~.' -~ 2Z1GJ~~ ~ ~~~
~
~
~ <4119600 ~""'~B''''5 ~~»...r'J~I'i IiiCP 1-:.:J ' l~1f·::1Wr·- : \ B.\Tl\::~ 1. ~'\..~ ~ <4119500
. ~
...
<D
~
0
U
~ '"tS600 ~·~I.~~~.ii3~~~' ?:j,QI.L:C2JJJ\"('~II/ (fULQ L3¥.i!k::~,'\'~~ ... IS ·
§
~ <4117500 ~§'(. ~J~;-I..4/J rTJ , -
•. ~ ' "?5 . , ~~~\---
. . :-/ ~ . xf'.
_ 'l,. " ~. .~ 4tt7Se8t
<4, 16500 ~';:V~-=:().1'l'~ < ' . \;). I ~c. ~\ti,i(YbItQJ ~ .. r.s.r:~ .H.-Z -l~. f,.~. ?o 'l' ~ <4116500
l~ \ 'm't~¥ C;] JV...A!i , . , \ \1 . ll'K(,' • -(1 { Il -., JI

n_ <4116600
r_ :,.1111 36geee 37HU 371000 3j)aBa
LARO£ OAIM lNVENTORY ~ L.IMIT

SOL.ID fIII8I!l..lNE INVENTCRt
SMAl.L DASH L.QIa L.IMIT INY!NTClRl'
TABLE 6-3. AREA CONTAINED WITHIN THE BENZENE 0.12 AND
1.2 UG/M**3 ISOPLETHS
AREA I AREA
WITHIN WITHIN
EMISSION
I I
I .12 UG/M**3 PERCENT 1.2 UG/M**3 PERCENT
CASE (M**2) CHANGE (M**2) CHANGE
BASE CASE 8.56E+07 5.73E+06
UPPER BOUND 1.53E+08 78.81 8.26E+06 44.32

t-'
00
o LOWER BOUND 8.34E+07 -2.54 4.67E+06 -18.38
increasled by 6,740 square kilometers. At the 1.2 ug/m3
concentration level, the area within this concentration isopleth
increases by 253 square kilometers.
Based on the results of this analysis, we feel that the exposure
modeling for benzene is representative of actual refinery
impacts.
6.2 Impacts from Other SARA Chemicals
6.2.1 Methodology
Dispersion modeling was also conducted for the non-BTEX voe

compounds which are emitted at the refinery and reported under
SARA 313. These chE:micals are: butadiene, cyclohexane,
naphthalene, trimethylbenzene, MTBE, ethylene propylene and
methanol.
For this group of chemicals, modeling was conducted in an
analogous manner to BTEX (i.e., the same meteorological data and
receptor grids were used). For these chemicals, however, there
were noi: sufficient ambient air quality measurements to perform
the verification of the inventory that was done for BTEX
compound.s. The accuracy of the inventory for these chemicals
should be similar to BTEX, since emissions from both groups of
chemicals come from the same sources. Thus, it can be assumed
that if the composit:ion of the hydrocarbon stream is known, then
the emissions of the~ other compounds can be accurately
181
determined. This is the procedure that was taken for process
fugitives, storage itanks, barge operations and product loading.
For the sewer vents, the measurement methodology did not allow
direct quantification of emissions for these chemicals.
Emissions from this source type were estimated by first computing
the ratio of toluen'~ to the chemical of interest in the API
separator. Then this ratio was multiplied by measured emission
rate measurements for toluene in the sewers to estimate emissions
for the other chemicals.
The emissions of th,~se chemicals from the cooling tower could not
be quanitified. Since impacts from this source were small for
BTEX ch'~micals, the omission of this source from the modeling
will not be significant.
6.2 .2 Rt:!sul ts
Table 6·-4 summarizes the modeling results for the SARA reported
chemicals and Appendix E contains the output listings from the
ISCST model. In this table, the maximum predicted concentration
is pres'~nted for receptors located beyond the fenceline in the
York River (adjacenit to the barge operations), beyond the
fenceline but onshore, and at a nearby residence.
For the receptors located in the river, MTBE impacts were the
highest (3.5 ug/m3 ) and impacts from butadiene were the lowest
182
TABLE 6-4. MAXIMUM ANNUAL AVERAGE PREDICTED CONCENTRATIONS
FOR THE YORKTOWN REFINERY FOR SARA CHEMICALS
OUTSIDE THE PLANT OUTSIDE THE PLANT AT A NEARBY

IN YORK RIVER ON LAND RESIDENCE
("1"'\,.1("
VVI'IV. CONC. CONC.
CHEMICAL (UG/M**3) (UG/M**3) (UG/M**3) I
CYCLOHEXANE 1.19 0.08 0.34
NAPTHELENE 2.31 0.27 0.15

I-'
00
w
TRIMETHYLBENZENE 9.16 2.23 1.12
MTBE 3.50 0.51 0.27
ETHYLENE 0.93 1.03 0.44
PROPYLENE 2.39 1.87 1.02
BUTADIENE 0.05 0.00 0.00
METHANOL 0.29
~--- - _.. --
0.30 0.07
It sh.ould be noted that butadiene was not detected
in any of the TO-14 canister data. For all of these chemicals,
maximum impacts occurred in the vicinity o~ the barge operations.
For the receptors beyond the refinery fenceline and on land, the
highest predicted impacts occurred as a result of
trimethylbenzene emissions (2.2 ug/m3 ). This impact occurred
along the northeast boundary of the refinery. The smallest
maximum predicted concentrations were from butadiene emissions
(0.00036 ug/m3 ). This impact was predicted to occur along the
northwest boundary CJf the refinery.
The maximum residen1tial impacts were greatest from

trimethylbenzene and propylene (1.1 and 1.0 ug/m3 , respectively)
and butadiene impacts were the smallest (0.0020 ug/m3 ).
Annual average source culpabilities for butadiene are presented

in Figure 6-13. As indicated by this figure, only two source
groups contributed 1:0 the butadiene impacts; process fug i ti ves
and the blowdown stacks. The distribution of impacts between
these two source gr()ups was relatively constant for the receptors
considered. ,/\bout 35 percent of the impacts were from process
fugi ti VE~S and the rE~mainder came from the blowdown stacks.
Impacts for this chE~mical are very small and are below the
analytical detection limit.
184
FIGURE 6-13. SOURCE CULPABLITY FOR BUTADIENE
IN YORK RIVER
(Y)
-II 0.01 100 Z
-
-II
~
(.!)
2-
z
0.00
0.00
0.00
90
80
70
60
0
i=
:::l
CO
a:
l-
0.00
0 SO Z
0.00
~
0
0.00 40 ()
I- 30 I-
0.00 Z
Z W
W 0.00 20
()
()
Z 0.00 10 a:
0 0
w
0.00 c....
() FUGITIVES API BARGE SEWER COOLING TOTAL
SOURCE
(Y)
-II 0.00 100 Z
-II
- 90 0
~ 0.00 i=
(.!) ~ 80 :::l
0.00 CO
2- ~ 70
a:
z 0.00 60 l-
0 SO Z
0.00
~
0
40 ()
0.00 I-
I- 30 Z
Z 0.00 I - - W
W 20
()
()
Z
0.00 10 a:
0 0
w
0.00 c....
SOURCE
I~ CONCENTRATION 1m PERCENT OF TOTAL
(Y)
-II 0.00 100 Z
-II
~ 90 0
a-2- 0.00 80
70
i=
:::l
CO
z 0.00 60
a:
I-
0 ~ 50
Z
~
0
0.00 40 ()
I- 30 I-
Z Z
iii! 20 W
W 0.00
~
()
()
Z 10 a:
w
0 0.00 0 c....
() FUGITIVES API SARGE SEWER COOLING TOTAL
SOURCE
185
Figure 6-14 presents annual average source culpabilities for
cyclohexane for the three receptors. For the receptor located in
the York River, barge operations contributed the majority of the
impacts, 77 percent (0.92 ug/m3 ). Fifteen percent of the total
predicted impact was from the blowdown stacks (0.18 ug/m3 ).
At the fenceline receptor located on land, 52 percent of the

impact 'was from blo'wdown stacks (0.83 ug/m3 ). In addition,
22 perc,ent of the impact at this receptor came from the coker
pond (0.18 ug/m3 ). The remaining impacts were from process

fugitiv1es, 7 percent (0.55 ug/m3 ) and storage tanks, 13 percent
(0. 11 Ui~/m3).
At a nearby residence, the largest source contribution was from

the blmvdown stacks; 70 percent (0.24 ug/m3 ). storage tanks had
the second largest contribution, 13 percent (0.045 ug/m3 ).
Process fugitives, barge loading, the coker pond and the sewers
contributed in the range of 2 to 5 percent (0.007-0.018 ug/m3 ) of
the total impact.
Figure 6-15 presents annual average culpability listings of

source impacts for the maximum receptors (i.e., beyond the
fenceline in the river, beyond the fenceline on land and the
residence) for naph1:halene. For the receptor located in the
. river, 1:he largest source contribution was from barge operations,
97 percent (2.2 ug/m3 ). At this location, product storage tanks
186
FIGURE 6-14. SOUfRCE CULPABLITY FOR CYCLOHEXANE
IN YORK RIVER
M
iI 1.20 100 Z
iI
::a 90 0
""- 1.00 80
i=
C!) ::J
2- ~ 70 CD
Z
0.80
:% 60
a:
I-
0 50 Z
0.60
~
0
40 ()
I- 0.40 30 I-
Z Z
20 W
m
W 0.20 ()
-
()
Z
10 a::
w
0 0.00 0 a..
() FUGITIVES API SARG SEWER COOLING TOTAL
SOURCE
AT FENCELINE ON u\ND
M
iI 0.90 100 Z
iI
::a 0.80 90 0
i=
a2- 0.70 ~
~
80
70
::J
CD
Z
0.60 ~~ 60
a:
I-
0 0.50 Z
~ 50
~ 0.40
0
()
~
~ 40
0.30 I-
~
I- 30 Z
Z 0.20 W
20
W
()
0.10
~ ~ :%
10
()
a::
Z
0 0.00
~'!'Irnt~ -J@l- ~ ~ 0
w
a..
SOURCE
~ o. 35 100 Z
iI
90 0
~ o. 30 80
i=
::J
2- o. 25 70 CD
~ a:
oz o.20 ~~
60
50
I-
Z
0
~ o. 15 ~ ~
40 ()
I-
~ o. 10 ~ 30 Z
w ~ ~ 20 W
() o. 05
z
8 o.- ,,,,,,,m.
FUGilTIVES API
-"""'"
BARGE SEWER COOLING
~
~TAL
10
0
()
a::
w
a..
SOURCE
I~ CONCENTRATION !HB PERCENT OF TOTAL ]
187
FIGURE 6-15. SOURCE CULPABLITY FOR NAPTHALENE
IN YORK RIVER
ro-
-Ie 2.50 100 Z
-Ie
0
--2- ~
:E 90
2.00 80
i=
CJ ::J
70 aJ
Z 1.50 60
a:
I-
0 50 Z
~
0
1.00 40 ()
~
I
I- 30 I-
Z Z
20 W
~
W 0.50 ()
()
Z
0
()
0.00 -
FUGITIVES
TANKS
API MRG
H20 TANK
SEWER
COKER
COOLING
LAND
OTAL
SLOWDOWN
10
0
a:
W
a..
SOURCE
I~ CONCENTRATION m PERCENTOFTOTAL
ro-
..
..
:E
0.30 100 Z
90 0
.Ii'!
a2- 0.25 80
i=
::J
aJ
Z
0.20
70
60
a:
I-
0 ~ Z
0.15 50
~
0
~~ 40 ()
I- 0.10 30 I-
Z
Z
W 0.05
~ 20 W
()
()
Z
0 0.00
._] 10
0
a:
w
a..
() FUGITIVES API BARG SEWER COOLING TOTAL
SOURCE
ro-
... 0.16 100 Z
-Ie
0
--2-
:E 0.14
CJ 0.12
90
80
i=
::J
aJ
Z 0.10
70
60
a:
I-
0 50
Z
0.08
~
0
40 ()
0.06
I- 30 I-
Z 0.04 Z
~ 20 W
W
()
,;tt1 ~ ()
0.02 a:
~
10
Z
0
~_1?1lI ~ w
()
0.00
SEWER COOLING
0 a..
FUGITIVES API SARG TOTAL
TANKS H2O TANK COKER LAND SLOWDOWN
SOURCE
188
had a small contribution to the total impact, 3 percent
(0.07 ug/m3). For the maximum receptor onshore, the major
contribution was still from barge operations, 68 percent
(0.18 ug/m3). However, product storage tanks, 30 percent
(0.08 Ui~/m3) and process fugitives, 2 percent (0.006 ug/m3)
contributed to the overall impact. At a nearby residence, source
contributions were similar to the maximum receptor on land: barge
operations contributed 78 percent, product storage tanks
contributed 21 percent and process fugitives contributed
2 percent. However, for this receptor, concentrations were about
a factor of 1.8 smaller than those predicted at the maximum
receptor on land.
A summary of the distribution of source culpabilities for

trimethylbenzene arIa shown in Figure 6-16. Again, barge
operations had the maximum impact in the York River, contributing
92 percent (8.4 ug/m3). However, small contributions were
observed from process fugitives, product storage tanks and the
blowdown stacks. For the process fugitives, the contribution was
1 percent (0.13 ug/m3), for the product storage tanks and the
blowdown stacks the contribution was approximately 2 percent
(0.2 ug/m3). At thE~ receptor where the maximum impact was
predictEad on land, barge operations had the largest impact,
35 percEant (0.78 ug/m3). At this receptor, contributions were
also predicted from:: product storage tanks, 18 percent
(0.40 ug/m3); from t:he landfarms, 16 percent (0.35 ug/m3); and
189
FIGURE 6-16. SOURCE CULPABLITY FOR TRIMETHYLBENZENE
IN YORK RIVER
-
C')
iC
,~
'"
,00
z
o
~ a
~ i=
a-'
~~
,~
::J
CO
2-' 70
z •
,~
~
o z
i=
~
~
.,
.~
,w-
~
~~
'"oo
8I-
Z
ill
ill
o
2
~ ,. o
a:
Z
oo
'w-
0 FLOll'ut:S
-
TNoI<S
API
Hi!O TN«
8.tYtGE
c:acm
SE\IER
1.»0
COD...NG
-~
EUJ¥«JCMIN
TOTAL
ill
0..
SOURCE

M
iC 2.50 100 Z
90 0
iC
--2-
~
(!) 2.00 80
70
i=
::J
CO
a:
Z 1.50 60 I-
0 50
Z
0
~
I-
1.00 40
30
0
I-
Z
Z 20 ill
ill 0.50 0
0 10 a:
Z ill
0 0.00 0 0..
0
M
iC .80 100 Z
it
~ .60 90 0
i=
a-2- .40 80
70
::J
CO
z .20
60
a:
I-
01 .IJU' Z
50
~
0
0.80 40 0
I- 0.60 ~ 30 I-
Z
ffi 0.40 ~ 20 ill
-m ~
.~
0
oz 0.20 10 a:
~m1m- I'JfCI1 ~ ~t;: ill
8 0.00 FUGIITIVES API BARGE SEWER COOLING TOTAL
0 0..
TANKS H20 TANK COKER LAND BLOWDOWN

SOURCE
. 190
process fugitives, 10 percent (0.22 ug/m3 ). At a nearby
residence, the largest source contribution was from product
storage tanks. These sources contributed 18 percent of the total
impact (0.30 ug/m3)" Barge operations had the second highest
impact, 16 percent (0.27 ug/m3 ). The remaining impacts resulted
from process fugitives, 9 percent (0.14 ug/m3 ), the API
separator, 5 percent (0.10 ug/m3), sewers, 7 percent
(0.12 U9/m3), the inactive landfarms, 6 percent (0.09 ug/m3) and
the blo'Wdown stacks, 9 percent (0.15 ug/m3).
The annual average culpability results for MTBE are presented in

Fi9ure 6-17. As indicated in this figure at all three receptor
locations, barge operations are responsible for the largest
source contribution, 97 percent (3.4 ug/m3) in the river,
61 perc1ent (0.31 ug/m3) at the fenceline on land and 41 percent
(0.11 w:r/m3) at the residence. Process fugitives and product

storage tanks also contributed to the overall impact. In the
river, these sources contributed approximately 2 percent
(approximately 0.1 ug/m3) of the total contribution. At the
residence, the impact from process fugitives was 23 percent
(0.06 U9/m3) and from storage tanks the contribution was
37 percjent (0.098 u9/m3).
Annual average culpability results for propylene are presented in

Figure 6-18. As indicated by this figure, process fugitives and
blowdown stacks are the only sources which contribute to the
191
FIG"URE 6-17. SO'URCE CULPABLITY FOR MTBE
IN YORK RIVER
(i)
...... 3.50 100 Z
~ 0
--
::E
CJ
2-
3.00
2.50 ~~
90
80
70
F=
::J
co
Z 60
a:t-
0 2.00 Z
~ 50
~t-
0
1.50 ~~ 40 (J
30 t-
Z 1.00 Z
W 20 W
(J
(J 0.50
Z 10 cc
w
0
(J
0.00 ~
FUblTIVES API BARGE SEWER COOLING TOTAL
0 a..
SOURCE
M
... 0.60 100
... Z
0
--2-
::E
CJ 0.50
90
F=
~
80 ::J
70 co
Z
0.40
60
a:t-
0 50
Z
0.30
~
f;: 0
40 (J
t- 0.20 30 t-
Z Z
W ...A 20 W
0.10 (J
Im~
(J
Z 10 cc
0
w
(J
0.00
BARG SEWER COOLING TOTAL
0 a..
FUGITIVES API
SOURCE
I ~ CONCENTRATION 1m PERCENT OF TOTAL
M
... 0.30 100
... Z
::E 90 0
a2- 0.25 80
70
F=
::J
co
Z
0.20
60
a:t-
0 50
Z
0.15
~
0
40 (J
t- 0.10 ~ t-
~
30 Z
Z
ill J~ ~ 20 W
(J
0.05
JII ~
(J
Z ~ 10 cc
w
0 0.00 0 a..
(J FUGITIV S API BARG SEWER COOLING TOTAl
SOURCE
I~CONCENTRATION ImPERCENTOFTOTAl I
192
FIGURE 6-18. SOURCE CULPABLITY FOR PROPYLENE
IN YORK RIVER
(Y)
2.50 100 Z
""
~ 90 0
--2-
:E
(!) 2.00
~
80
i=
::J
ID
Z 1.50
70
60
a:l-
-!~
0 SO
Z
~I-
0
1.00 40 ()
30 I-
Z Z
0.50 20 W
W ()
()
~
10 CC
Z W
0 0.00 0 c..
() FU(,IT1VES API BARGE SEWER COOLING TOTAL
SOURCE

(Y)
2.00 100 Z
"
" 0
~
90
--2-
:E
(!)
1.80
1.60 80
70
i=
::J
ID
Z
1.40
1.20 60
a:
l-
0 SO Z
1.00
~ ~~
0
0.80 40 ()
r~~~ ~
I- 0.60 30 I-
Z Z
W 0.40 20 W
~
()
()
0.20 10 CC
Z :~ W
0 0.00 0 c..
() FUGITIV:S API BARGE S EWER COOLING TOTAL
SOURCE
(Y), ,
"" z
-9Il
o
~, co- .... i=
~
(!) ::J
2- .., ro ID
z
oi= ..,.
~
~
~
Q
f-.o 8
I-
~
. ~
Q
Z
W
()
~ ~
w
()
cc
Z
o
() . ~
TANKS
~ '0
w
c..
SOURCE
193
propylene impacts. For the process fugitives, source impacts
ranged from 60 perc.ent (1. 4 ug/m3 ) in the river to 53 percent
(0.54 ug/m3 ) at a nearby residential receptor.
Figure 6-19 presents the culpability results for ethylene.
Results are similar to propylene. Culpable sources are process
fugitives and the blowdown stacks. Source culpabilities for
process fugitives range from 65 percent (0.63 ug/m3 ) of the total
at the residence to 42 percent for the receptor located on land
beyond the fenceline.
Table 6-5 presents a summary of the modeled concentrations
compared to annual average measurements for remote, rural and
urban locations for cyclohexane, naphthalene, trimethylbenzene
and butadiene (Shah and Heyerdahl 1988).
As indicated by this table for cyclohexane and trimethylbenzene,
refinery impacts are similar to concentrations measured in an
urban environment. For naphthalene and butadiene, refinery
impacts reflect rural concentrations.
6.3 Modeling of criteria Pollutants
6.3.1 Methodology
The mod1eling of the impacts for criteria pollutants was performed
using the USEPA ISCST model, the same model which was used for
the BTEX and SARA analyses. For this analysis, the model was
194
FIGURE 6-19. SOURCE CULPABLITY FOR ETHYLENE
IN YORK RIVER
M 10.00 100
iC
iC
Z
0
--
~ 9.00 90
~ 1=
C!J 8.00 80 :::l
~ OJ
2- 7.00 70
Z 6.00 ~ 60
0:
l-
0 SO Z
5.00 0
~
I-
4.00
3.00
40
30
0
I-
Z
Z ~ W
W 2.00 20
0 ~ 0
a:
Z
0
0
1.00
0.00 -
FUGITIVES API
~
BARGE SEWER COOLING
-
TOTAL
10
0
w
a..
SOURCE
I~ CONCENTRATION [±II PERCENT OF TOTAL
M
iC 1.00 100 Z
iC
0.90 90 a
E. 0.80 60
1=
:::l
CJ
OJ
2. 0.70 70
0:
Z
0
0.60
0.50
aa 60
so
l-
Z
a0
~
I-
0.40
0.30
~ ~
~
40
30 I-
Z
Z i% ~ ~
20 W
W
0
Z
0
0.20
0.10
i%
i% a
~
~
~
10
0
a:
w
0.00 0 a..
0 FUGITIVES API BARGE SEWER COOLING TOTAL
SOURCE
M 100
iC .20 Z
iC
~ 90 a
a2- 1.00 80
70
1=
:::l
OJ
z 01 .80 I:': 0:
60 l-
o f')
SO Z
~
.uv a0
I-
01
01 .40
~ 40
30 I-
~
Z Z
20 W
~ 01.20
10
0
a:
Z w
oo 0>.00
FUGITIVES API BARGE SEWER COOLING TOTAL
0 a..
SOURCE
Ifm CONCENTRATION tI±I1 PERCENT OF TOTAL I
195
TABLE 6-5. COMPARISON OF ANNUAL AVERAGE PREDICTED IMPACTS TO TYPICAL
MEASURED CONCENTRATiONS FOR DiFFERENT TyPES OF ENViRONMENTS FOR SARA CHEMiCALS
MAXIMUM PREDICfED MAXIMUM PREDICfED

CONCENTRATION CONCENTRATION TYPICAL REMOTE TYPICAL RURAL TYPICAL URBAN
AT TIlE FENCELINE (a) AT A NEARBY RESIDENCE CONCENTRATION CONCENTRATION CONCENTRATION
CHEMICAL (UG/M**3) (UG/M**3) (UG/M**3) (UG/M**3) (UG/M··3)
CYCLOHRXANE 0.83 0.34 0.00 0.09 1.03-1.72
NAPTHALENE 0.27 0.15 0.00 0.00 1.20
TRlMETHYLBENZENE 2.30 1.10 0.21 0.83 1.10
BUTADIENE 0.00 0.00 0.00 0.22 .64-.32 j

I-'
'.0
0\
a) PREDICTED ON LAND
executed with one year of meteorological data so that annual and
other appropriate averaging period impact estimates could be
made. A description of the meteorological data is presented in
section 6.1. The criteria pollutants modeled were S02, CO, PM-10
and N0 2 ,.
The emission parameters used for the fired refinery process
sources were based on engineering calculations and AP-42 emission
factors. For NO x emissions, it was conservatively assumed that
all NO x emissions WE~re emitted as N0 2 • Flare emissions were based
on typical stream compositions of the gas going to the flare.
The PM-10 emissions from the coke pile were computed using AP-42
emission factors. This source was modeled as two ground-based
area sources. Emissions from the FCU were based on AP-42
emission factors.
The impacts from fli~re was modeled using the approach developed
by the Texas Air control Board (TACB). This approach assumes
that the plume rise from a flare can be accurately modeled using
the buoyant plume rise algorithm contained in the ISCST model
provided the buoyancy flux is conserved. This is achieved by
assuminq an exit velocity of 20 mls and a stack temperature of
1000°C. A pSleudo s1:ack diameter is calculated so that the
buoyant flux is equivalent to that of a comparable point source
of equal sensible hE~at. The amount of heat loss from the flare
is computed as a function of molecular weight. A study conducted
197
by API showed that this approach showed reasonable agreement with
available experimental data (API 1989).
Table 6-6 presents the inventory parameters and Table 6-7 lists
the modeled emission rates for each source. Building downwash
parameters were included in the criteria pollutant modeling
analysis.
concentrations were estimated at a total of 916 receptors. The
receptor grid was composed of two parts, a coarse grid and a fine
grid. The coarse grid extended 10 kilometers from the refinery
center with a resolution of 1 kilometer. The fine grid extended
1 kilometer from the refinery boundary and had a resolution of
250 meters. In addition, concentration estimates were also made
along the plant property boundary at 100-meter intervals. It
should be noted that although this grid is similar to the grid
used for the BTEX and SARA inventory modeling, differences do
exist in the fine grid areas, since the criteria pollutant fine
grid excludes receptors located within the refinery fenceline.
6.3 .2 Resul ts.
The criteria pollutant modeling results are summarized in
Table 6-8. Maximum predicted concentrations for the applicable
averaging periods are presented in comparison with National
Ambient Air Quality Standards (NAAQS) and Prevention of
Significant Deterioration (PSD) significant impact
198
TABLE 6-6. CRITERIA POLLUTION SOURCE EMISSION PARAMETERS FOR THE YORKTOWN REFINERY
UTM COORDINATES EXIT EXIT STK

STKHEIGHT TEMPERATURE VELOCITY DIAMETER
EASTING NORTHING (m) (K) (m/s) (m)
SOURCE (m) (m)
.
POWER STATION 371368.0 4119230.0 45.72 555.4 7.00 1.81
PACKAGE BOILER 371316.0 4119198.0 8.23 580.4 11.92 1.07
COKER 370916.0 4119198.0 39.01 584.8 9.18 1.98
t--' ULTRA FORMER 371233.0 4119212.0 42.82 505.4 12.95 2.49
1.0
1.0
FCU 371037.0 4119231.0 64.62 593.7 7.96 3.96
SRU INCINERATOR 371446.0 4119330.0 30.48 894.3 7.40 1.37
FLARE 371313.0 4119317.0 60.96 1273.2 20.00 0.85
COKER PILE 370748.0 4113053.0 1.83 * 142.25
* side length of a 20234.5 m**2 area source

TABLE 6-7. CRITERIA POLLUTION EMISSION RATES FROM THE YORKTOWN REFINERY
PM-lO S02 co NOx
SOURCE (ton/yr) (ton!yr) (ton/yr) (ton!yr) I
!puw bK ~Tf\.nlJl'1 O.~ 0/.1 :>.1 :>4.j
POWER STATION 6.2 67.1 5.1 54.3 I
PACKAGE BOILER 0.9 7.8 10.2 39.7
COKER 1.1 10.5 13.8 27.4
ULTRA FORMER 7.9 24.6 17.7 115.4
FCU 509.3 1814.8 17.4 486.2
SRU INCINERATOR -- 641.2 431.0 3.7
FLARE -- 1169.0 56.6 3.7
N
COKER PILE * 30.0 -- -- --
o
o
* 20234.5 m**2 area source
TABLE 6-8. COMPARISON OF MAXIMUM PREDICTED IMPACTS OF CRITERIA POLLUTANTS TO NAAQS
I~- --
MAX PSD
AVERAGING PREDICTED PERCENT OF SIGNIFICANT
POLLUTANT PERIOD CONe. NAAQS NAAQS IMPACTS
(ug/m**3) (ug/m**3) (ug/m**3)
S02 ANNUAL 5.6 80 7 1

N 3 HOUR 165.6 1300 13 25
o
......
24 HOUR 49.7 365 14 5
CO 1 HOUR 101.3 40000 <1 2000
8 HOUR 40.7 10000 <1 500
PM-10 ANNUAL 0.3 50 1 1
24 HOUR 2.9 150 2 5
N02 ANNUAL 1.0 100 1
-~--
_._--
1
* These are the PSD significant levels for TSP since PM-10 significant levels are undefined
concent:rations.
Maximum predicted impacts beyond the refinery fenceline from CO,
PM-10 and N0 2 are below PSD significant impact concentrations.
S02 maximum predicted impact was greater than the PSD significant
concehtrations for the annual, 3-hour and 24-hour averaging
periods but still only a small percent of the NAAQS; 7 percent,
13 percent and 14 percent, respectively. Although all of the
criteria pollution sources in the area of the Yorktown Refinery
were not accounted for in the criteria modeling, impacts from the
Yorktown Refinery are relatively small and well below the
prescribed NAAQS values.
6.4 Modeling of Other Chemicals

6.4.1 !![ethodoloqy
Modeling was also conducted for chemicals on the SARA listing but
which are released in small enough quantities that they are not
reported under SARA..
These c:hemicals were carbon tetrachloride, PNA compounds, nickel
and vanadium ..
Carbon tetrachloride emissions were estimated to be 0.0025 tons
per year based on material usage. Emissions of PNA compounds
were based on PNA source measurements made at the coker pond
(Radian 1991). Nickel and vanadium emissions are associated with
202
particulate emissions at the fluidized catalytic unit (FCU).
These WE;re estimated based on the content of these metals
containE;d on the caicalyst used in the FCU.
6.4.2 Results
Modeling results for these chemicals are presented in Table 6-9.

As indicated by these data, impacts from these emissions are
extremely low.
203
TABLE 6-9. MAXIMUM ANNUAL AVERAGE PREDICTED CONCENTRATIONS FOR OTHER CHEMICALS
OUTSIDE PLANT FENCELINE IN YORK RIVER I OUTSIDE PLANT FENCELINE ON LAND OUTSIDE PLANT FENCELINE AT A RESIDENCE
COMPOUND
CONe. CONe. CONe.
~m··3) (ug/m**3) (ug/m··3)
_~i.!JJjiit._£.%l
NAPTI-IALENE 2.1E-03 5.JE-03 l.3E-03
ACENAPHTHALENE 6.4E-03 1.5E-02 4.0E-03
ACENAPHTHENE 1.4E-02 3.2E-02 8.4E-03
FLUORENE 7.9E-03 1.9E-02 4.9E-03
N 4.0E-05 5.0E-05 2.0E-05

o
.p.
VANADiUM 1.8E-04 2.3E-04 2.2E-04
_~!lt.'£ilt.$gl·
CARBONTETRACHLORIDE .... 2.2E-04 2.3E-04 5.0E-05
7. () Conclusion
As a result of this study, a number of conclusions can be reached
regarding air emissions from the Amoco oil Company Yorktown
Refinery: data was compiled on air emissions for a wide range of
compounds; the accuracy of the emission estimates was tested for
BTEX compounds using modeling and monitoring data; and, the long-
term ambient air quality impacts beyond the refinery fenceline
were estimated using a dispersion model.
The following sUbsections summarize the findings for each of

these areas.
7.1 Emission Invent()ry Development

As a result of this study, air emissions were quantified for the
facility. Emission estimates were made for total VOCs, BTEX,
other SARA reported chemicals and criteria pollutants. For voe
compounds (which includes BTEX and other SARA compounds)
emissions were quant:ified using source testing, engineering
calculat:ions and USEPA emission factors. For criteria
pollutants, USEPA emission factors were used.
For voe emissions, it was found that refinery emissions are

approxi]rrately 7,900 tons per year and benzene emissions were
estimatE~d to be 67 t:ons per year. Source testing performed on
the API separator, s;ewer vents and coker pond provided realistic
estimatE~s of VOC emissions.· One limitation of this study was
205
that no information was developed on the variability of VOC
emi.ssions or speciat.ed hydrocarbon emissions with time. This,
however, is a limita.tion of all emission inventories. We believe
that since the source testing was performed during warm ambient
temperatures and whe,n the refinery was operating near or at
maximum capacity, emission estimates should be conservative.
This is clearly an area where additional research is needed.
7.2 Ambient sampling Program

An ambient air sampling program was conducted as part of this
study. The purpose of this study was not to document long-term
air quality impacts nor was it to measure refinery impacts during
all types of meteorological conditions, but rather it was
designed to me~asure impacts from specific process units under
persistent meteorological conditions. The results from this
sampling were used to test the accuracy of the emission
inventory.
7.3 Accuracy of the Emission Inventory

The accuracy of the emission inventory for BTEX was tested by
comparing modeling predictions to ambient air measurements.
Because the design of the sampling enabled identification of
specific source impacts under steady meteorological conditions,
this allowed comparison of model predictions to the observed
ambient measurements. This comparison indicated that the model
predictions and the observed concentrations generally agreed
206
within a factor of 2, however, there was a great deal of ~catter
in the data. As a result of this comparison, it was concluded
that thlere was not a significant bias in the emission inventory
and that no sUbstantial emissions have been omitted.
7.4 Ambient Air Quality
The emission inventory developed for the refinery was used to
predict concentrations of BTEX, SARA reported chemicals and
criteria pollutants. This was done using one year of
meteorological data. For benzene, the maximum annual average
concentration beyond the fenceline was 6.2 ug/~. This
concentration was predicted in the river near the barge loading
transfer point. At this location, th~ majority of the predicted
impacts were from barge operations. The maximum annual average
benzene concentration on land was 1.3 ug/m3 • About 45 percent of
the predicted impacts was from barge operations. At a nearby
residence, the maximum benzene value was 0.64 ug/m 3 • Barge
operations were responsible for approximately 50 percent of the
projected impacts.
Similar analyses were conducted for the TEX and the other SARA
reported chemicals.
Modeling was also performed for criteria pollutants (S02' N0 2,
PM-IO and CO)" These model predictions were then compared to
USEPA significant levels and applicable NAAQS. The results of
207
this analysis indicated that for all criteria pollutants, except
S021 predicted concentrations were less than the USEPA
significant levels. For S021 the maximum contribution to the 24-
hour NAAQS of 365 ug/m3 was 50 ug/m3 (about 14 percent of the
NAAQS) .
208
8.0 References
Cohen, Y. and D.T. Allen, "Multi-Media Assessment of
Emissions (MAE) from the Amoco oil Company Yorktown Refinery
(Amoco/EPA Pollution Prevention project)" National Center for
Intermedia Transport Research UCLA.
Keinbush, M.R., D. Runum, and B. Ekland, "Evaluation of Flux

Chamber Method for Measuring Air Emissions from Surface
Impoundments" Radio corporation 1988.
Klee, H., C.E. DeLuca, D.N. Blewitt, J. Cummings Saxton 1992,

"Projects, Evaluation and Ranking" Amoco EPA Pollution
Prevention Project.
NIOSH 1984, "NIOSH Manual of Analytical Methods 3rd Edition

u.s. Dept. of HHS, PHS, CDC, NIOSH Division of Sciences and
Engineering".
Radian 1985, "Measurements of Gaseous Emission Rates from

Land Surfaces using an Emission Flux Chamber". User's Guide.
EMSL/EPA.
Radian 1985 b , "Model Evaluation of Refinery and Synfuels VOC

(Volatile Organic Compounds) Emissions Data."
Radian 1991, "Measurements of Hydrocarbon Emissions and

Ambient Air Concentrations at The Amoco Yorktown Refinery."
Shah, Jitendra J. and Emily K. Heyerdahl, 1988, "National

Ambient Volatile Organic Compounds (VOC) Data Base Update"
EPA.
USEPA 1987, "Guideline for Air Quality Maintenance and

Planning and Analysis. Volume 10 (Revised): Procedures for
Evaluating Air Quality Impact of New Stationary Sources"
OAQPS.
USEPA 1987 b , "Industrial Source Term Complex (ISC) Dispersion

Model User's Guide--Second Edition (Revised)" OAQPS.
USEPA 1986, "Guideline on Air Quality Models (Revised)"

OAQPS.
USEPA 1988, "Compendium Method TO-14. Determination of

Volatile Organic Compounds (VOe's) in Ambient Air Using Summa
Passivated canister Sampling and Gas Chromatographic
Analyses." EMSL.
USEPA 1985, "Compilation of Air Pollutant Emission Factors"

OAQPS.
USEPA 1989, "Hazardous waste Treatment, storage, and Disposal

Facilities (TSDF') - Air Emission Models" November 1989 Review
Draft.
209
USEPA 1987, "On-site Meteorological Program Guidance for
Regulatory Modeling Applications" OAQPS.
210
Appendix A
Analyses of Tracer Data

1.0 Introduction
As part of the air quality field sampling program that was conducted
at the Amoco oil Company Yorktown Refinery, a series of tracer
experiments were conducted. The purpose of these experiments was to
first attempt to evaluate the accuracy of the volume source
algorithm in the industrial source complex model (ISCST) and
secondly, attempt to use the tracer data in conjunction with the
ambient measurements of BTEX to aid in estimating process fugitive
emissions for these chemicals.
In these experiments sulfur hexafluoride (SF 6 ) was released from the
center of the Ultraformer unit. The tracer was released as a series
of four point sources (line source) at an elevation of approximately
6 meters above grade. The release points covered a distance of
approximately 36 meters long with a 12 meter separation between
release points. The design of the tracer release attempted to
simulate process fugitives by uniformly releasing tracer within a
portion of the unit. The release rate of SF 6 was measured on an
hourly basis and thei ambient concentration of tracer was measured
downwind of the releiase point. Complete details of "these
experiments are provided in Radian 1991.
The followi.ng sections provide: 1) a comparison of model
predictions made by the ISCST model to the experimental data and 2)
an analysis of the data which attempted to use the tracer data and
the ambient BTEX measurements to aid in estimating process fugitive
emissions. Because of the limited amount of downwind ambient
measurements, it is impossible to draw firm conclusions from these
analyses.
A-l
2.0 comparison of SF 6 Tracer Data to ISCST Model Predictions
An analysis was performed using the tracer data to evaluate the
performance of the volume source algorithm in the ISCST model.
This is the algorithm which is used to simulate process fugitive
emissions. This portion of the model has not been previously
evaluated for this type of source.
This limited evaluation was performed by executing the ISCST model
using the hourly SF 6 emission rates and the corresponding on-site
meteorological data. The resulting model predictions were then
compared to the measured SF 6 concentrations. Because of the limited
number of samplers available for this study, and because of light
and variable meteorological conditions, all but six hours of tracer
data were eliminated from further analyses (Table 1).
2.1 Methodology and Results
In performing this analysis, six different modeling approaches were
used. The first three modeling approaches simulated the tracer
release as a volume source and the remaining three model runs
simulated the tracer release as point sources.
The first modeling approach was to model the tracer release as a
single volume sourc,e. For this case the dimensions of the
processing portion of the Ultraformer unit were used (30.48 meters
by 7.6 meters). The release height of the tracer release was used
(6.1 meters). The ISCST model was run in the rural mode for the 6
hours of tracer data.
A-2
TABLE 1
CASE-HOUR DATA DESCRIPTIONS
MAXIMUM
OBSERVED TRACER
WIND SPEED FLOW VECTOR TEMPERATURE CONCENTRATION
HOUR (MIS) (DEGREES) STABILITY ( K) (UG/M·* *3)
300 2.5 159.2 4 292.2 /.79

400 2.8 166.0 4 292.1 0.89
500 2.7 166.7 4 291.7 1.00
600 3.0 163.0 4 291.5 0.75
700 2.4 161.6 4 2<) 1.3 1.21
------
800 2.3 159.7 ---~--
3
~----------~ ---
2<) 1.0
- - - - - - - - - - - - - - ..- - - - - - --------- ---------
0.83
----- - - i
~
w
The second modeling approach was to use equal adjacent volume
sources. The rational for this case was to examine the effect of
increasing the initial dispersion by using multiple volume sources.
For this case, the model was also run in the rural mode.
The third modeling approach incorporated subdivide volume sources as

in Case 2, except the initial dispersion was increased by using the
urban dispersion curves. It should be noted that this case is not
applicable to estimating concentrations beyond the refinery
fenceline since the initial dilution caused by the processing unit
is a very localized effect (Petersen 1989).
The remaining three approaches simulated the tracer releases as

point sources.
The fourth approach explicitly modeled the tracer release using the
downwash algorithm contained in the ISCST model. For this case,
dimensions of the Ultra former unit were used as input to the model.
The fifth approach was the same as Case 4, except downwash was not
used. This case was not physically realistic in its simulation of
the experiment.
The sixth approach treated the tracer release as point sources with
downwash, but utilized the urban dispersion curves.
Table 2 summarizes the results for the volume source simulation.

The table presents the maximum observed concentration, the maximum
A-4
predicted concentration, the ratio of predicted to observed
concentration and the mean ratio of predicted to observed
concentration. As indicated by these data, the ISCST model, in
general, overpredicted the observed concentrations by a large
margin. While the simulation of the tracer data using the urban
dispersion curves provides the best overall model performance, the
enhanced dispersion caused by the process unit is a very localized
effect and such enhancements in dispersion would not be
representative of atmospheric dispersion at the Yorktown Refinery
beyond the processing unit area. Therefore, we do not believe that
this isa realistic approach for modeling refinery impacts beyond
the fenceline.
Table 3 presents a comparison of the modeling and monitoring data
for the si][ulations that utilized point source releases. As in the
case of the volume source simulations, the model is overstating the
observations by a lclrge margin. The best overall model performance
was achieved for point source simulations without incorporating any
enhanced dilution from the roughness of the unit. This is a very
unrealistic simulation and we feel that such a treatment cannot be
accurately applied to simulate effects.
2.2 Summary
As a result of this limited analysis, several conclusions can be
drawn.
1) In the near field, the.ISCST model may be overstating the
observed concentrations by a large margin.
A-5
TABLE 2
VOLUME SOUI~CE MODELING RESULTS SCENAH I () 1 THRU 3
SCENARIO I SCENARIO 2 ~l SCENARIO 3

SINGLE VOLUME SOURCE 9 VOLUME SOl ~RCE 9 VOLUME SOURCE,JJRBAN
MAXIMUM I MAXIMUM MAXIMUM 1 MAXIMUM
OBSERVED PREDICfED PRED!CfED PREDICTED
CONCENTRATION CONCENTRATION
I RATIO
I CONCENTRATION RA TlO I CONCENTRATION
CASE-HOUR I ,UG/M·u3) (UG/M*u3) (C /CD {lJG/I\1·"3L
300 1.79 6 .... 9 30.2 7-1.1 ... \.5 1~.9 J(l.()

400 0.89 77.7 87.1 82.4 92.4 22.2 24.9
500 1.00 68.0 67.8 72.3 72.1 1<).2 1<).1
600 0.75 57.3 76.5 5<).8 7<).8 18.1 24.2
700 1.21 52.6 43.7 5(i.7 47.1 15.6 12.9
SilO O.IB :\5.1 42.7 3().2 47 .... 10.1 12.2
:t>
I
0\
MEAN I. 'ifffMS9.l0MtiH MEAN ·,.,• • ·,·)Q3i4ihtfl MEAN
TABLE 3
POINT SOURCE SENSITIVITY MODELING RESULTS SCENARIOS 4 THRU 6
SCENARIO 4 SCENARIOS
4-POINTSOURCE WITH 4-POINT SOURCE WITHOUT
DOWNWASH DOWNWASII
MAXIMUM MAXIMUM MAXIMUM
OBSERVED PREDlCfED PREDICffiD I PREDICIED
CONCENTRATION CONCENTRATION RATIO CONeENTR_ATION RATIO CONCENTRATION RATIO
(UG/M··3) (UG/M··3) (Cp/Co) (UG/M"3) (ep/Co) (UG/M··3) (el
300 1.79 75.7 42.3 21.8 12.2 99.1 55.4

400 0.89 68.2 76.6 21.2 23.8 89.9 101.0
500 1.00 73.7 73.7 22.3 22.3 97.1 97.1
600 0.75 50.9 67.9 17.4 23.2 64.9 86.5
700 1.21 68.1 56.3 21.0 17.4 86.9 71.8
800 0.83 44.0 53.0 11.7 13.6 50.7 61.1
:>
I
MEAN ltlt.~mlI6..: MEAN @WfmifsjijMt% MEAN
"
2) This overprediction could be caused by many things; one
possibility is that it is due to the inability of the model to
account for the enhancement entrainment resulting from the
process unit structure. This effect is likely a near field
effect and its importance i diminished in further distances
from the source.
3) It was concluded that this tracer study did not provide

sufficient scientifically sound information on how best to
model this source.
4) Additional experimental datasets are needed to provide more

complete evaluation of model performance for this type of
source.
A-8
3.0 Use of the Trac:er Data to Aid in Estimating Process Fugi ti ve
Emissions
The second goal of these experiments was to use the tracer data
in conjunction with ambient measurements of BTEX to aid in
estimation process fugitives. This can be done, for example, by
examining the ratio of measured benzene concentration to measured
SF 6 concentrations. since the emission rate of SF6 is known, the
emission rate of benzene can be calculated from these ratios.
This technique has been successfully used for isolated sourcesJ
The limitation of this technique is that emissions of the
chemical of interest and the tracer have to be emitted in a
similar location. If this is not the case, then both chemicals
will not be exposed to the same dispersive forces and, therefore,
will not experience the same amount of dilution.
Table 4 summarizes the available concurrent SF6 and benzene
measurements. As indicated by the concurrent meteorological
data, winds were variable during this sampling. This allowed
sources other than the Ul traformer to impact the monitors. Thes.e
additional impacts bias the BTEX monitoring results and prevent
the Ul tra:Eormer from being considered an isolated source. As a
result of this analysis, no conclusions regarding BTEX emissions
can be drawn from 1:hese data.
A-9
TABLE 4. SUMMARY OF THE CONCURRENT SF6 AND BTEX MEASURMENTS
SF6 BENZENE
DILUTION FACTOR CONC WS
SAMPLING DAY TIME SITE (M3/SEC) (UG/M3) WD (MIS) COMMENTS
1 20 1 1.06 -- -- -- SITE 1 NOT IN A PREVAILING DOWNWIND
21 0 9.4 211 2.8 DIRECTION. WINDS WERE VARIABLE

23 6.562 90.35 198 1.4 DIRECTION. WINDS WERE VARIABLE

5 0 21.43 224 2.8 DIRECTION. WINDS WERE VARIABLE

17 0.437 0.65 129 1.7 DIRECTION. WINDS WERE VARIABLE
:r..... 4 6 2 0.871 -- -- -- CALM WINDS. COMBO AND COKER WILL

o 7 2.463 80.6 215 0.6 INFLUENCE BTEX MEASURMENTS
4 8 2 2.22
9 2.463 80.93 218 CALM NOT APPROPRIATE FOR ANALYSIS
4 16 1 0.49 NO BTEX MEASURED FOR COMPARISON

17 0 0 125 1.6 -----
4.0 References
Radian 1991, "Measurements of Hydrocarbon Emissions and Ambient
Air Concentrations at the Amoco Yorktown Refinery."
Petersen 1989, "Effect of Homogeneous and Heterogeneous Surface
Roughness on Heavier Than - Air Gas Dispersion." API.

Appendix B
ISCST Modeling Results of BTEX Monitoring Data
(Appendix included in a separate document)

Appendix C
Summary of Modeling and Monitoring Comparisons

Appendix D
Annual Modeling for BTEX

Appendix E
Culpability Analyses for BTEX

Appendix F
Annual Modeling Analyses for SARA Chemicals

Appendix G
Culpability Analyses for SARA Chemicals

Appendix H
Modeling Analyses for criteria Pollutants

Appendix I
Summary of Wind Persistence
Appendix I - Summary of Wind Persistence
DAY DATE HOUR SEQ WD WS SIGMA
1 9/25 16 1 237 7.2 18

18 2 211 6.2 9
22 4 198 3.1 12
0 5 193 3.5 11
9/26 2 6 202 4.6 13
4 7 224 6.1 13
6 8 224 4.6 10
8 9 222 5.6 14
10 10 225 6.3 17
12 11 235 8.2 21
14 12 224 9.6 18
2 9/27 1 4 338 4.5 15

3 5 334 5.1 13
5 6 346 6.2 15
7 7 342 6 14
9 8 341 5.6 15
13 10 324 7.2 15
15 11 328 6.9 17
3 9/28 22 1 84 4.5 9
6 5 269 1.7 25
8 6 270 1.2 31
12 8 324 3 26
16 10 129 3.7 24
4 9/29 2 1 223 1.6 8

4 2 212 1.9 8
6 3 215 1.4 24
8 4 218 0.4 22
16 8 125 3.5 24
20 10 151 3.3 20
5 9/30 6 1 203 3.6 14

8 2 190 2.7 14
10 3 204 2.6 15
16 6 230 4.8 15
18 7 218 3.8 13
20 8 210 4.6 12
22 9 221 4.2 11
10/1 0 10 245 4.2 20
4 12 5.8 9.2 18
Appendix J
Responses to USEPA Comments

APPENDIX J
Table of Contents
1.0 Response to General Comments by Dr. David Guinnip 1-1

on Ail: Quality Data, Volume II, dated October 24, 1991
2.0 Attacl~ent 1, Comments by OAQPSjUSEPA on Ambient 2-1

Dispersion!Measurement Program, dated November 25, 1991
2.1 Response to Attac~ent 1 2-3
3.0 Attacl~ent 2, Comments by OAQPSjUSEPA on Measurements of 3-1

Emissions from Open Wastewater Sources
4.0 Attacl~ent 3, Comments by OAQPSjUSEPA on Refinery Organic 4-1

Air Emission Sources
5.0 Memorandum from K.C. Hustvedt, OAQPSjUSEPA, to Ann Bailey, 5-1

OARjUSEPA, regarding Concerns with the Amoco/EPA Yorktown
Refinery Study, dated June 1, 1992
5.1 Discussion of Memorandum 5-12
SUBJECT INDEX
Responses to General Comments
from Dr. D. Guinnip

October 24, 1991
PAGE SUBJECT
1 Tracer Data; BTEX Emissions
2-4 spatial and Temporal Coverage; Replicate Sampling
5-6 Emission Measuring Techniques-Standard? non-standard?
6 Flux Chamber Sampling (API Sep. & Coker Pond)
7 Benzene Measurements at API Sep.
8-9 BTEX Meas. - Prediction of
10 Wind Direction Persistence During Intensive Meas.·
11 BTEX & TNMHC Emissions - Consistency of Measurement
11-12 Blowdown Stacks Emissions - Methods/Meas. Problems
12-13 VOC Emissions from Blowdown Stks-Methods/Meas. Prob.
14 Meas. of Speciated HC's from Bldwn. Stks.-Problems ...
14-15 Model Predictions vs. Actual Meas. Emissi.ons
16 Tracer Test - Validity of
16-17 Meas. of Sewer Vent Emissions
17 Meteorological stability
18 Area Classification (Rural) ; Sensitivity Tests
19 Emission Figures - Accuracy and Reasonableness of
20 NMHC Emissions
21-23 Elevated Benzene Concentration - Validity/Cause of
23 BTEX Emiss. - Model Prediction vs. Actual Measurement
24 Toluene, Xylene, Ethylbenzene - Model Pred. vs Meas.
25-26 Community Air Quality Monitoring
26 Toluene, Benzene, Ethylbenzene Emmis, - Impacts, Rural
vs. Urban
1-1
Responses to comments from Dr. David Guinnip dated
October 24, 1991 regarding the Amoco/USEPA Pollution Prevention
Air Quality Analys:ls Report, Volume II.
General Comments:
1) Inconsistencies of tracer data and other measurements.
As explained in Appendix A of the report (attached), we feel that

the data provided by the tracer experiments was not of sufficient
quality to draw any conclusions regarding BTEX emissions from the
Ultraformer. Our analysis of these data indicate the following.
There were only a limited number of samples where an overlap of

SF 6 measurements and BTEX measurements occurred. Examination of
meteorological data from these periods indicate that the
Ultraformer was never well isolated from other refinery process
sources. This criteria is essential if this technique is to be
used to estimate emissions using this procedure. This is because
emissions of BTEX from other sources in the vicinity of the
Ultra former unit will not experience the same amount of dilution
at the monitoring location as emissions from the Ultraformer
itself. In retrospect, we are no longer sure that the method
that was used to release Tracer within the unit represented
emissions throughout the unit. Thus, it is not possible to
simply ta};:e the rat:io of SF6 to BTEX and compare it to the SF6
emission rate to infer an emission rate of BTEX. We feel that,
based on the limitations in these data, no conclusions can be
1-2
drawn. We have included a table in Appendix A of the report
which summarizes these data. We have also conducted a benzene
sensitivity analysis to address the uncertainties in benzene
emissions. This analysis is also discussed in the report.
2 and 3) Insufficient replicate sample measurements and

insufficient spatial and temporal coverage.
The question of sanlple replicates and adequate spatial and

temporal coverage always becomes a problem in attempting to
estimate emissions (especially for emission sources that are
difficult to measure) .
The study was designed to address spatial distribution of

emissions by collecting a limited number of replicate samples.
For the emission measurements that were made for the API
separator and the coker pond, two replicate measurements were
made. The replicate measurements were made in a sequential mode
(i.e., one measurement made after another). For the active
portion of the coker pond integrated, replicate samples were
collected over the entire l8-hour coking cycle. For the sewer
samples, a 3D-minute average sample was collected. We feel that
by use of these replicate samples and inter-comparisons of the
data, we have addressed the issue of spatial representation of
the data.
1-3
One can always argue that additional data are needed to address
the issue of spatial representation. In the case of the sewers,
we found that emission measurements made at the upstream portion
and downstream portions of the sewers were reasonably consistent.
(See Table 2-5 in the report). The sampling on the coker pond
was conducted near the point of water discharge. Thus, this
should represent the location of maximum emissions. For the API
separator, the replicate samples were collected at opposite ends
of the separator box and, thus, a mean should reflect the
emissions over the entire separator.
The major question regarding this study is the question of
temporal variations in emissions. This study was not designed to
address this problem and, as such, the estimated emissions
reflect a "snap shot" in time. We feel that since the refinery
was operating at or near maximum capacity and sampling was
conducted in the late summer, emissions should reflect peak
emission rates. Annual emissions were estimated by assuming that
emissions were constant at this rate for all hours of the year.
While this assumption is very simplistic, we feel that it is
conservative, given the time when the sampling program was
conducted and the operational status of the refinery.
It should be noted that the problem of temporal representation of
emissions is not unique to this study. The same problems exist
if emission factors (such as AP-42) or models (such as CHEMDAT7)
1-4
are used to characterize emissions. In the case of emission
factors, emissions are measured for a short time period and the
measurements are normalized to some form of process conditions.
These factors are then applied to the entire population of
sources. Clearly, there is a great deal of uncertainty in this
method of attempting to quantify emissions.
In the case of models to estimate emissions from water
impoundments, the models have been compared to some very limited
measurement data. Agreement between the model predictions and
the measurements used to validate the model indicates a large
amount of scatter in the model predictions with a general trend
of sUbstantial model overprediction. In applying such a model to
estimate annual average emissions, one must address the issue of
temporal and spatial variation in data to initialize the model
("Emission models use average influent and effluent
concentrat.ions to estimate annual emissions, .•. " USEPA 1989).
The model estimates are further complicated by requiring the use
of average meteorological conditions.
Clearly, this is a question which must be addressed for all types
of procedures for estimating emissions and is not limited to this
study. one recommendation which results from this is that this
USEPA 1989 "Hazardous Waste Treatment, storage and Disposal

Facilities (TSDF) - Air Emission Models." OAQPS
1-5
is an area where additional research is needed.
4) Use of non-standard and poorly documented emission measurement

techniques.
The first topic that should be addressed with respect to this

question is that measurement of emissions from non-point sources
is very difficult and there are no standard measurement
techniques that can be routinely applied to quantify emissions.
In developing the field program, there was insufficient time and
funding to underta]ce a major method development and verification
program. Consequently, we employed methods that had been
previously applied to such sources. Method development for
measurement of emissions from such sources is clearly an area
where additional research needs to be conducted.
Emissions from the API separator and the coker pond were measured
with a flux chamber. This device was developed by Radian
Corporation for USEPA to estimate emission fluxes and emissions
from such sources. Radian also developed procedures for the
implementation of 1:his method and estimated the associated
accuracy and precision of the method. Further, Radian, in its
role as the contractor for conducting the field program,
developed a sampling protocol for· the program prior to taking any
samples. This protocol was reviewed by USEPA and comments
received were incorporated into the protocol prior to conducting
1-6
the field sampling program. It should be noted that no comments
were received regarding the source sampling measurements prior to
the sampling program. In retrospect, additional work could have
been done with respect to the sewer samples to address the
current concerns of USEPA, had we received comments prior to the
start of the sampling program.
In summary, we feel that the emission estimates developed as part
of this project reflect an accurate estimate of emissions, within
the limits of uncertainty of our analysis techniques. From this
analysis, we have <;rained an understanding of what sources are
important with regard to speciated hydrocarbon emissions.
We acknowledge your comments regarding the limits of this study
and will include comments regarding these limitations.
specific comments
1) Discuss the differences between the replicates in more
detail - What are possible causes? They were averaged for
analysis. state. this up front. Is this approach conservative or
not (especially where samples differ so greatly)?
I am assuming that this question refers to the sampling that was
performed using the flux chamber (i.e., the API separator and the
coker pond). In the analysis of these data, replicate samples
were averaged for further analyses. This will be stated up front
1-7
in the final report.
For benzene measurements at the API separator, the difference
between the replicate samples was slightly greater than a factor
of 2. It should be noted that the measurements were taken at
opposite ends of the separator box. We feel the use of a mean of
these measurements is a representative measure of emissions, to
examine annual average benzene exposure. If the maximum emission
rate would have been used, then estimated annual emissions of
benzene from this source would have been 1.5 tons per year
instead of 1.0 tons per year. Similar trends were observed for
other chemicals for this source. Replicate samples on the coker
were generally within a factor of 2 from each other.
It is our belief, because of the nature of these sources, that
emissions will be variable and that the estimation of actual
annual emissions will be difficult. We feel that the estimated
emissions reflect emissions during a time period when maximum
emissions would be expected (the refinery was operating at
maximum capacity).
We feel that an important area of future research should be to
develop better measurement methods and tools to extend these
measurements to ob'tain more accurate estimates of long-term

emissions.
1-8
We believe that the benzene exposure modeling and the sensitivity
analysis address the uncertainty in emissions.
2) Discuss more in detail how predicted concentrations values

were derived for di.rect comparison with measurements. Why expect
the maximum predicted concentration to occur at the monitor?
Shouldn't this comparison always result in the prediction being
higher than the measurement? Shouldn't the measurement of any
values higher than the predictions immediately send up a red
flag? I see it as indicating the possibility of underestimated
benzene .missions for some of the sources - e.g., wastewater
treatment, storage tanks.
The following discussion presents an overview of the method that

was used to make the model data comparisons and clarifies the
discussion in the report. A subset of the BTEX measurements were
identified for analysis. This subset consisted of periods when
meteorological conditions were persistent and good source-
receptor relations existed. These 2-hour periods were then
modeled using the BTEX emission inventories and the observed (on-
site) meteorological conditions. Concentrations were then
predicted at the monitor locations. In order to account for
uncertainty in the measurement of wind direction, a fine receptor
grid was placed around the monitor location (see Figure 5-1 in
the report). This receptor grid extended 150 meters on either
side of the monitor. Comparisons were then made by pairing the
1-9
predictions and observations in time and space (with spacial
paring being relaxed over this small receptor grid). This
comparison is analogous to the techniques that have been used to
validate the USEPA dispersion models, except we maintained the
requirement for pairing.
Given this method of analysis, there is no reason to expect
predictions to be higher than the observation. If a receptor
grid was placed around an entire unit, then this would be true.
Consequently, we fE~el that this is a reasonable approach to
confirm emissions and does not lead us to the conclusion that
benzene emissions for the wastewater treatment unit were
underestimated. There may be a slight underestimate in benzene
emissions from storage tanks but the data are within the limits
of uncertainty of our analysis.
The surprising result of this analysis is how well the ISCST
model replicates the data, considering the stringent limits that
were placed on the comparison of the data.
3) If there was a significant gradient in predicted

concentrations within the array surrounding the monitor, state
this and discuss the implications. How was this dealt with?
If model predictions exhibited a sharp concentration gradient
across the model receptor grid or if the maximum predicted
1-10
occurred a.t the edge of the grid, these time periods were
eliminated from further analysis. We imposed this criteria
because if these co,ndi tions were observed in the predicted
concentrations, then our experimental design was inadequate to
draw further conclusions from the data. This topic will be
better addressed in the report.
4) Does the available met data allow for some quantification of
wind direction persistence during the intensive measurement
periods? If so, discuss results and their implications.
We can get an estimate of wind persistence during the intensive
measurement period by using sigma theta (standard deviation of
wind direction) as an indicator. The larger the value of sigma
theta, the less persistence. Sigma theta was computed from on-
site meteorological data according to USEPA guidelines (USEPA
1986). Persistence was already inferred in the draft report
where atmospheric stability class was reported. We will amend
Tables 3-1 through 3-5 to include sigma theta data and will
discuss these results. The raw meteorological data does contain
enough information to examine persistence in alternate ways,
however, we do not have the resources to pursue this topic
further.
USEPA 1986 "Guideline on Air Quality Models Revised" OAQPS.
1-11
5) Some of the information concerning "before" and "after"
emission inventories is confusing. For example, page 10 and page
126 do not appear at first glance to be consistent" and the
consistency of these with the figures on page iii is also not
apparent. Please correct and discuss.
Page 10 presents average emission estimates for BTEX and TNMHC
for the API separa·tor. On page 126, a figure summarizing our
best estimate of the distribution of benzene (only) emissions for
the entire refinery is presented. In this figure, we have
coml::>ined several emission sources into the single category of
wastewater treatment. These include the API separator sewer
vents and other emissions associated with this port.ion of the
refinery. The figure on page iii presents a distribution of
refinery TNMHC emissions. In this case, the wastewater category
has been combined as in the figure on page 126. Thus, these
figures are not inconsistent, but present different emission
data. We will clarify this further in the final report.
6) Discuss status of "better information on blowdown stacks", as
we discussed at OUJ~ meeting.
The results from the investigation on blowdown stacks will be
documented in a supplementary report. We used AP-42 emission
factors and calculated total emissions of 5,200 tons/year for the
refinery modeling studies. As discussed below, after much
1-12
effort, sampling results showed we had about 3,900 tons/year.
Model runs were not redone with the lower value.
The following provides an overview of the issues relating to
emissions from these sources. Prior to this project, it was
assumed that VOC emissions from these sources were negligible.
It was initially believed that we could obtain water samples from
these sources and use a mass balance approach to estimate
emissions. Upon careful review of the system, it was concluded
that the system was too complicated to estimate emissions in this
manner. As a result of this, source sampling was undertaken by
Radian Corporation" An initial set of samples were collected in
May of 1991. Results of this sampling were obtained in June and
review of that data indicated that, if the stack sampling results
were representative of actual long term emissions, then an
unrealistic amount of hydrocarbons (product) were being emitted.
It was further concluded that if these data truly reflect actual
emissions, the entire refinery mass balance is suspect. Review
of the data indicated concerns regarding: the water vapor content
in the stack; molecular weight of the material in the stack; the
accuracy of canister dilutions that occurred; and poor precision
in the replicate data. As a result of those and other
uncertainties, Radian agreed to conduct a second round of
sampling at their own expense. This was conducted in September,
1991.
1-13
The sampling approach for the second round of data was redesigned
to address the uncertainties that arose during the first
sampling. Analyses were performed to measure the moisture in the
stack, samples werle collected to better define the non-VOe
content of the stack, sample dilutions were preformed prior to
filling canisters and replicate samples were collected on all
stacks.
The first result of the second sampling was that stack flows were
greatly reduced from the first set of samples. In fact, flows
were reduced to the point that accurate flow rate measurements
were not attainable using conventional EPA recommended flow
measurement and sampling techniques.
The second problem that occurred was that for one stack at the
combo unit where the molecular weight of the effluent was
sufficiently different from air, that the calibration of the flow
rate measurements (sample dilution and moisture content) were
affected. Recalibration was done in Radian's laboratories using
reference gases. Finally, Radian made an unrealistic assumption
about the sample mloisture content to close the material balance
around this one stack.
In order to comple"te the air quality analysis, it was concluded
that we would estimate emissions from the blowdown stacks using
the uncontrolled emission factor contained in AP-42. This factor
1-14
is not based on any actual source measurements. Emissions for
specific blowdown stacks were estimated by multiplying estimated
emissions using AP-42 for the refinery by the ratio of unit
capacity to refinery capacity. Speciated hydrocarbon emissions
were obtained by assuming that the relative fraction of
hydrocarbon species obtained in the first Radian sampling was
correct and this fraction was used to apportion hydrocarbon
emissions. In the modeling analysis, the exit velocity and
temperature were set to minimize plume rise, a conservative
assumption for impact analysis.
In conclusion, we believe that emissions from these sources are
not insignificant as originally believed and the emissions are
variable. Further, the quantification of the emissions from
these sources are very difficult and not amenable to conventional
source sampling methods. Amoco has filed an amended TRI report
for Yorktown as a result of this work. As a result of this,
Amoco is also undertaking a concentrated study to better
understand emissions from these sources at other facilities.
7) Discuss criteria for isolating which sources are contributing
to which measurements. (I heard the figure of 50 percent tossed
around).
The first step in conducting the comparisons between the model
predictions and the measurements was to compare all .available
1-15
data. From this analysis, we computed statistical information
regarding the level of agreement .. The next step was to allow the
ISCST model to estimate source culpability. Thus, for each 2-
hour model prediction, ISCST computed the contribution from each
source. We created a subset of data using the ISCST estimates of
source culpability to further examine the comparison of model
predictions and observations, to see if any additional
conclusions could be drawn regarding the accuracy of the emission
inventory. In making these comparisons, we looked for periods
when ISCST model computed a dominant source for a 2-hour period.
We then combined the data for the dominant source groups (i.e.,
process fugitives, blowdown stacks, tanks) and compared the model
performance to the observations. For example, for periods when
ISCST computed that process fugitives were dominant, we computed
statistics comparing the model predictions to the observations
(see Table 5-8). 'I~he criteria chosen for identifying a dominant
source in this analysis was set at 50 percent of the total
impact.
We feel that by subdividing the data in this manner that we have
gained further insi.ght into the accuracy of the emission
inventory.
8) After seeing the documentation on the tracer study, it appears
difficult to justify discounting these data and still using the
same methods to corroborate emission estimates in the main
1-16
report. Please include some discussion and/or just.ification.
The validity of the tracer test to estimate process fugitive

emissions has previously been discussed. I do not believe that
the method that was used to confirm emissions is the same method
used in the tracer test. We attempted to verify emissions by
identifying meteorological conditions when the various process
units were isolated. Unfortunately, we did not have these
conditions when the SF6 was released. These events were then
modeled using estimated emissions and a comparison of
observations and predictions was made. We will amplify this
point further in Appendix A.
9) More concern was expressed about measuring sewer emissions

using the "stack" method and the conservativity (or not) of such
an approach.
We feel that attempting to estimate emissions from sewers vents

is a very complex task. The sampling approach we employed
provided a practical method of attempting to quantify emissions
from such sources. It is our belief that this method did not
appreciably bias the results. In reviewing these data, we found
that the surface area of the sewer open to the atmosphere was
reduced by only 1 percent by placing the stack over the sewer
grate. As a result of this, there should be little pressure drop
on the system and air could still sweep through the sewers in an
1-17
unaltered manner. It should be kept in mind that the temperature
in the sewers was about 100°F or more. Thus, there should be a
natural flow out of the vents. Second, any ambient wind flow
would enhance the 1:low from the stack compared to the normal
sewer grate. In summary, we feel that there should not be a
significant bias in these data. Mr. Hustvedt commented that the
measured emission vvas higher than his model would predict. In
retrospect, I believe that there are further experiments that
could be done to better address this question, however, we do not
have the resources to pursue this any further.
10) Is D stability appropriate for these calculations? Is rural
dispersion appropriate? Were sensitivity studies done (for BTEX
measurements as well as tracer) to address ranges of results if
characterization oj~ ISC input parameters is imprecise?
First the stability class that was used in the analysis was the
class measured on-site during the sampling program. Stability
Class D was not always used. Stability class was measured using
a on-site meteorological tower according to USEPA Guidelines.
During our meeting to discuss this matter, it was suggested that
a differential temperature measurement should have been used. It
should be pointed out that in order to make this measurement, so
that it is useful in describing the atmospheric stability class,
a great deal of care must be used. This is part of the reason
why this approach is not currently allowed to estimate stability
1-18
class by USEPA (USE:PA 1986).
Second, the area around the refinery would be classified as rural
according to the Auer land use criteria. Impacts from the low
level sources would have been reduced by about a factor of 3 if
the urban dispersion curves had been used in the ISCST model. A
question that could be raised is "does the heat energy that is
released from the refinery as well as the obstructions of the
process units increase dispersion (at least in the vertical
dimension)?" I believe that these factors can and do influence
localized dispersion, however, the influence of such factors is
only applicable near the source, while further downwind such
effects become less important.
Third, sensitivity tests were conducted as part of the modeling
of the tracer releases and the BTEX analysis. As a result of
these tests, some i.nferences were drawn as to the sensitivity of
the ISCST model to the analysis of the BTEX data.
In the report we wi.ll address the issue of model sensitivity
tests.
Responses to Comments from Bob Faoro dated October 3, 1991
Regarding the Amoco USEPA Pollution Prevention Air Quality
USEPA 1986 "Guideline on Air QU'ality Models (Revised)." OAQPS.
1-19
Analysis Report
1) Do the final emlssion figures, both the total and from the
individual sources, look reasonable? Do the individual facility
sources rank as expected? Do the emission figures agree with
comparable estimates, if available, from other plants?
First, based on the results of this analysis, we believe that the
emission estimates provide a reasonable estimate of emissions at
the time sampling \i\TaS conducted. As with any estimate of this
type, there is an uncertainty associated with these estimates.
Based on the typiccLl uncertainty associated with the tools used
in this analysis, I would place the uncertainty in emissions at a
factor of 2. Realistically, it may not be possible to estimate
emissions from a facility such as a refinery with more accuracy
than this.
Second, the ranking of sources was not as expected. See the
figure on page iii of the report. This figure presents a
histogram of estimated voe emissions prior to and as a result of
this study. As indicated by this figure, the distribution of
emissions among source groups is very different as a result of
this study, highlighting the benefits of site-specific analysis
in defining emission problems and solutions.
Third, Amoco currently does not have accurate data against which
1-20
such comparisons can be made at other facilities. Most
refineries estimate rather than measure emissioris for reasons
outlined in the project summary.
2) It appears that only a small fraction of the total NMHC
emissions from the plant are BTEX. The question is what major
compounds are in the non-BTEX portion and are in sUfficient
quantities to be of concern?
Please refer to Tables 3-6 and 3-7 in the report for specific
information on other He emissions. The data presented in this
table shows the net difference between upwind and downwind TO-14
samplers equipped with directional sampling heads. These were
set to sample only during periods when the samplers were either
upwind or downwind of the refinery. From these data, we were
able to estimate net impacts. A crude estimate of emissions was
made from these measurements.
Modeling was conducted on many of these chemicals and is
presented in the report. Based on a review of these results by
Dr. Mark Klan, a toxicologist with Amoco, the projected ambient
concentrations beyond the fenceline are not of concern for human
health.
3) The highest net benzene concentration measured (2195 ug/m3 )
was reported at site 5 on day 5 at 20:00 hours. It appears that
1-21
this value was explained away because ot a "temporary" earthened
equalization basin and thus was not used to verity emissions.
There were other potential sources upwind ot site 5, e.g. the API
separator l , besides the basin, so how can you be so sure that this
was the sole predominate cause? It looks suspect that these
potentially valuable data (there were other high benzene
concentrations reported at this site on day 5) were ignored it
lim interpreting the tirst paragraph on page 45 correctly.
There were three rElasons why we felt that culpability for

elevated benzene concentrations at Site 5 could not be assigned
to sources other than the unearthened pits.
1) Our conclusion was based on the observed meteorological

data. The high benzene measurements at site 5 are
summarized in the following table along with the reported
wind direction.
Net Mean
Benzene WD
HOUl:: (ug/m3 ) (Deg)
16 925 230
18 738 218
20 2194 210
22 1107 221
1-22
The orientation between the API separator and the sampler at
site 5 was about 190°. As indicated by the wind direction data,
mean flow was a minimum of 20° away from the orientation of the
API separator and t.he sampler, and ranged to a maximum of 40°.
Winds duri.ng these sample periods were light but no·t calm.
Ideally, one would like more separation between sources to aid in
source culpability analysis, however, these data strongly suggest
the emissi.ons from the API separator were not the dominate
source.
2) These measurements are not a result of emissions from the
API separator based on looking at the ratio of: toluene to
benzene; ethylbenzene to benzene; and xylene to benzene for
both the measurements at site 5 and from emission
measurements at the API separator.
At site 5, the ratio of toluene to benzene ambient air
measurements was 0.097. The ratio of ethylbenzene to benzene was
0.006 and the ratio of xylene to benzene was 0.022. By
comparison, the ratio of toluene to benzene emissions from the
API separator was approximately 6. For ethylbenzene and benzene
the ratio of emissions was 2, while for xylene and benzene the
ratio was 8.6. Thus, the source characteristics of the API
separator are very different than the profile of ambient
concentrations observed at site 5 during these times.
1-23
3) The API separator is not the culpable source benzene, we
observed during the sampling program that strong hydrocarbon
odors were coming from these basins. Thus, we feel that
large impacts could have resulted from these temporary
sources.
We feel that the sum of these arguments provide strong but

indirect evidence that the API separator was not responsible for
these impacts. This discussion will be expanded in the report.
4) Do you mean by t~he statement at the bottom of page 90 "In

reviewing the data no sound justification was found to make any
adjustments to the inventory", that air monitoring data was never
used to make any adjustments to the inventory? If this was true
then how can you e)[plain the large percentage of the time when
the predicted and observed pairs differed by more that a factor
of 2?
Based on our analysis we concluded that the emission inventory is

representative of actual BTEX emissions within the limits of
uncertainty our analysis techniques. I feel that the comparisons
between model predictions and the measurements indicate good
agreement. While there is a large amount of scatter in the data,
the correlation between predicted and observed agreement is quite
good. Typical comparisons performed to validate air quality
models generally show more scatter and the criteria for
1-24
comparisons are generally less stringent than we imposed in this
study. If one examines the model performance for benzene for
sites 1-4, the average ratio of predicted to observed was found
to be 0.88 (a ratio of 1 would imply a perfect fit) and
54 percent of the predictions were within a factor of 2 of the
observations. Model performance at sites 5 and 6 was not
considered here because poor model performance was observed as a
result of the area source algorithm in the ISCST model. The fact
is well documented in the literature. In general, the ratio of
Cp to Co for benzene was within a factor of 2 at all sampling
sites (1-4). For t:oluene, the mean ratio of Cp to Co was 2.5
with 51 percent of the predictions within a factor of 2 of the
observations. This mean ratio is strongly influenced by
sUbstantial model over prediction at site 1. For the remaining
sites, the mean rat:io of Cp to Co is 1. 2 with 65 percent of the
predic.tions wi thin a factor of 2 of the observations.
For ethylbenzene and xylene, comparison between model predictions
and the measurement:s indicate over-estimation of the measurements
at Sites 1 and 2. However, at sites 3 and 4, agreement was quite
good.
Overall, my conclusion of these comparisons is that model
comparisons with the observed data is generally better than is
typically observed in this type of analysis.
1-25
6) It sure would have helped to confirm your conclusions about
the plant's impact beyond the fenceline to have done BTEX
monitoring at the nearest residential location closest to the
maximum impact.
We made a number of requests to OAR personnel to join us in this

sampling program, including a specific request to monitor air
quality in the community. We were advised that resources were
not available for ambient monitoring. While I believe that long-
term monitoring studies, such as those suggested in this comment,
can be valuable in assisting in managing air quality resources, I
feel that, in this case, such a study would not provide useful
information to confirm the conclusions that were drawn from this
study.
The first issue that must be addressed is the issue of source

culpability. When ambient monitoring is performed for air
toxics, it is very difficult to assign source culpability over a
long averaging period (annual period in this case). While
methods exist to aid in identifying culpable sources for short-
time peric)ds, these are not completely accurate and become
impractical when extrapolating to annual average concentrations.
Also, benzene emissions from sources other than the refinery in
the region around the refinery are approximately equal to
refinery benzene emissions.
1-26
The second issue that should be kept in mind is that at the level
of concern one is interested in for benzene (i.e., 0.12 to
1.2 ug/m3 ), current analytical methods may be incapable of
accurate and precise measurements.
7. In terms of thel comparison of the modelled results with the

typical ambient measurements taken in remote, rural and urban
locations (see page 150); are the pollutant impacts what you
would expect, i.e., toluene the highest, with benzene and
ethylbenzene about the same?
Given that the emissions of toluene are greater than benzene or

ethylbenzene, it should be expected that toluene impacts should
be greater than benzene or ethylbenzene. This is consistent with
measurements in urban settings, as indicated on the table on page
150. In the urban setting the sources are probably in close
proximity to the point where the measurements were made. Thus,
there is little opportunity for photochemical transformation.
This may not be the case for the rural or remote monitoring data.
1-27
ATTACHMENT 1
AMBIEN'!' DISPERSIOHIMEhSTJRElHEN'l' PROGRAM
.1. Discuss more in detail how predicted concentration

val ues were deri VE!d. for direct I;ompari:!on wi th measurement~. Why
expect the maximum predicted concentration to occur at the
monitor? Shouldn't this comparison always result in the
prediction beinqhigher than th~ m~~surement? Shouldn/~ th9
measurement of ~ values higher than predictions immediat~li
send up a red flag? I see it as indicating the possibility of
underestimated benzene emissions for som~ of the sourco~ - e.g.,
wastewater treatment, storage tanks.
2. If there was a significant gradient. 1n predicted
thl!=l and discuss the implications. HOW was this dealt with?
3. Does the available met data allow some quantification of
periods? If so, discuss results and tneir implications.
4. Di scuss c:r:iteria for isolating which sources are
contributing to which measurements. (I heard the figure o£ 50
percent tossed around)
s. After see:i.ng the documentation on the tracer study, it
appears difficult to justify discounting these data and still
using the sa1'!le methods to corroborate emissions estimates in the
main report. Please include additional discussion or
justifications. There was a heavy reliance on dispersion
mod.eling of the lonq-t.erm. air quality impact. These models and
methodologies were proven inaccurate using tracer testing at
Yorktown. There is i concern that good and useful concentration
data is boing rajectad because of inappropriate use of the
dispersion models. Incorrect selection of stability classes can
cause the predicted concentration of tracer to be an order of
ruaqnitude too high. NQutral stability was predicted from wind
direction changes, even in the afternoon when the atmosphere was
expected to be highly unstable (from the results of planetary
boundaJ.""Y la.yer calc.'Ulations:). Oneef the advantages of usinq a
tracer is that the true dispersion characteristics of the wind
can be measured. These dispersion characteristics can then be
useu to interpret ooncentration data and evaluate the air
emission predictions. If the dispersion models are determined to
be inappropriate for the tracer release (paqe A-6) , there is
little b~$is for olaiminq that thA same dispersion models and
methodology are appropriate for other releases of volatiles (page
ii). The text should be revised for consistency. EPA
recommendations for' at.l1lospheric stability determination should be
carefully followed. If the actual tracer data indicates that the
2-1
EPA recommendations are inaccurate, ttlls is significant and
should be reported.
6. There is an apparent discrepancy oetween tho air
concentrations predicted by the dispersion modeling and the
measured ~i.r concentrations. The maximum concentration in the
predicted benzene concentration is a taw ml~ro9ram5 of benzenQ
per cubic meter, while the measured benzene concentrations in the
a. b." ara substantially hiqher in most cases. If dispersion models
are to be used for determining air quality, the~e modelS_3hould
appear tOI be consistent with the me.asured data.
7. Is D stal:)ility appropriate for these calculations? Is

L'ural'dispcrsion apprnpriate for estimates within a processing
facility? Were sensitivity studies done (for B'l'EX mea~urements
as well as tracer) to address ranges of results if
j nput parameters is imprecise?
cha.t'dcterizClt.ion of ISC
2-2
SOBJECT INDEX
RESPONSES TO ATTACHMENT 1
PAGE SUBJECT
2-3 Tracer Release Data
3-4 ISCS'r Model and Results; Fugitive Emission Meas.
5 Dispersion Models-Accuracy of; stability Classes
7-8 Dispersion Models vs. Meas. of Air Concentration
2-3
Responses to Attachment 1
Ambient Dispersion/Measurement program
(Note: Original questions from memo and attachments are repeated
in bold. Response is in normal type.)
1. Discuss more i:n detail how predicted concentration values were
derived for direct comparison with measurements. Why expect the
-maximum predicted Iconcentration to occur at the monitor?
Shouldn't this comparison always result in the prediction being
higher than measurement? Shouldn't the measurement of any values
higher than predictions send up a red flag? I see it as an
indicating the possibility of underestimating benzene emissions
for some of the sources - e.g. wastewater treatment, product
storage tanks.
Answered in response 2 to Dr. David Guinnip's Question #2, dated
October 24, 1991.
2. If there was a significant gradient in predicted
this and discuss tlle results and implications. How was this
dealt with?
Answered in response 3 to Dr. David Guinnip's dated October 24,
1991.
3. Does the available met data allow for some quantification of
2-4
periods? If so, discuss results and their implications? Answered
in response to Dr. David Guinnip's Question #4, dated October 24,
1991.
4. Discuss criteria for isolating which sources are contributing
to which measurements. (I heard a figure of 50 % tossed around).
Answered in response to Dr. David Guinnip's Question #7, dated
October 24, 1991.
Sa. After seeing 'the documentation on the tracer study, it
appears difficult to justify discounting these data and still
using the same methods to corroborate emissions in the main
report. Please in~clude additional discussion or justifications.
Based on our analysis of the tracer data in Appendix A we are
convinced that the data are (unfortunately) of insufficient
quality to draw any firm conclusions. In the case of testing the
volume source algorithm in the ISCST dispersion model, only 6-
hours of limited data exist against which any model versus monitor
comparisons can be made. Because of the limited number of
downwind SF6 samplers used in this experiment, it is not possible
to test this aspect of the dispersion model adequately. This is
clearly an area where a well designed and comprehensive field
program and model validation program should be conducted. Perhaps
EPA would consider co-funding a joint measurement program with the
2-5
American Petroleuml Institute or Chemical Manufacturers Association
to help improve source measurement methods and results?
with respect to the use of the ISCST model to aid in the
confirmation of emissions, process fugitives make up only a
fraction of total hydrocarbon emissions (approximately 10% VOC and
3% benzene). Thus, even if the tracer tests had provided a
comprehensive evaluation of the volume source algorithm, there are
many other sources that contribute to the observed impacts that
would be missing in such an analysis (i.e., blowdown stacks, barge
loading, etc.). We concluded that, within the limits of
uncertainty, the model replicates the observed data quite well. If
the model had a significant overall bias, then model performance
for BTEX chemicals should be consistent between chemicals (we saw
this at site A-6) because the sources of BTEX are generally the
same. However, for storage tank impacts, for example, model
performance varied by chemical. For toluene, the model (using
storage tanks modeled as elevated area sources) showed no bias
(the ratio of predicted to observed results, Cp/Co, was 1.15
paired in time and space) with 85 % of the predictions within a
factor of two of the observations. For perfect agreement we would
expect Cp/Co = 1.0. For xylene and ethylbenzene, there was a
slight bias toward over-prediction but many of the predictions
were within a factor of two (61% ethylbenzene and 64% for xylene).
By contrast, benzene impacts were slightly under-predicted when
compared to the observations, but approximately 58% of the data
are within a factor of two. The general impression that one is
2-6
left with is that the stream composition of benzene may be
slightly under-stated and therefore emissions may be slightly
understated for these sources. The bias in the benzene data,
however, are within the uncertainty limits of the analysis.
This modeling analysis has provided valuable insight into
quantifying the accuracy of the emissions. Before this analysis
was conducted, no data existed on the accuracy of actual refinery
emissions. We concur with EPA that this is an area where
additional research is needed. One specific research topic that
needs to be addressed, is the extrapolation of a "snapshot" point
in time emission estimate into an annual emission rate. Some EPA
models--CHEMDAT7, for example--share this same problem.
5b. These models and methodologies were proven inaccurate using
the tracer testing at Yorktown. There is a concern that good and
useful concentration data is being rejected because of
inappropriate use of the dispersion models.
As previously stated we believe that the models and methodologies
used in this analysis were not proven inaccurate by the tracer
test. We further believe that the modeling was used as a tool to
provide better understanding air quality issues at the refinery.
The use of a model in this manner does not seem inappropriate to
us.
5c. incorrect selection of stability classes can cause the
predicted concentrations of tracer to be an order of magnitude to
2-7
high. Neutral stability was predicted from wind direction
changes, even in the afternoon when the atmosphere was expected
to be unstable (from the results of planetary boundary
calculations).
stability classes 'were computed according to USEPA guidelines (see
section 3.4). The tracer data analysis that we preformed
(presented in Appendix A) considered 6-hours of data. That was
the only data that met any minimum criteria of acceptability. All
of these data were collected during the nighttime or early morning
(5-hours of D and 1-hour of C stability were recorded). See Table
1 in Appendix A.
5d. One of the advantages of using a tracer is that the true
dispersion characteristics of the wind can be measured. These
dispersion characteristics can then be used to interpret the
concentration data and evaluate emission predictions.
The statement is true, provided that enough high quality data
exist to make this comparison, and that basic similarities between
the emission sources and the tracer release exist. (See response
Dr. David Guinnip's Question #1, dated October 24, 1991.) Table
4 in Appendix A pr1esents the concurrent SF6 data and benzene
measurements. As indicated by these data, only 7 concurrent
samples exist. Unfortunately, during these time periods the
samplers 'were either not in a prevailing downwind direction or
variable meteorolo9ical conditions existed. We were unable to
draw conclusions regarding emissions from these limited data.
2-8
Se. If the dispersion models are determined to be inappropriate
for the tracer release (page A-6), there is little basis for
claiming that the same dispersion models and methodology are
appropriate for other releases of volatile (page ii). The text
should be revised for consistency.
The first statement has been rephrased to state that the tracer
test data were inappropriate to test the dispersion model here.
These statements are not necessarily inconsistent. The tracer
test was designed to test only one portion of the model (volume
source). The tracer test indicates that there is not enough data
in this data set to preform such an analysis.
Sf. EPA recommendations for atmospheric stability determinations
should be carefully followed.
EPA recommendations were followed. See section 3.4 of the report.
Sg. If the actual tracer data indicates that the EPA
recommendations aria inaccurate, this is significant and should be
reported.
Amoco does not believe that the tracer data is of sufficient

quality to suggest that the EPA recommendations are inaccurate;
however,_ we have reported our findings in the document. EPA may
wish to draw its o'r,m conclusions from these data. Experimental
field programs to levaluate regulatory models from industrial
settings is a research program that needs to be pursued.
2-9
6. There is an apparent discrepancy between the air
concentrations predicted by the dispersion model and the measured
air concentrations. The maximum concentration in the predicted
benzene concentrations is a few micrograms of benzene per cubic
meter, while the measured benzene concentrations in the air are
substantially higher in most cases. If dispersion models are to
be used for determining air quality, these models should appear
consistent with the measured data.
It appears that the author is confusing measured concentrations
from 2-hr or 24-hr samples with calculated annual average
concentrations calculated by dispersion modeling. We would expect
the short term results to be higher than the annual average values
calculated. When compared on the same time-frame ]:)asis, the
results match fairly closely.
We believe that as one examines the data provided in the report it
can be seen that the maximum predicted concentrations at each site
r~plicates the maximum observed concentration generally within a
factor of 2. This shows that the model actually replicates the
observed data quite well. Note that all of the BTEX sources are
the same for a given site.
7. Is D stability appropriate for these calculations? Is rural
dispersion appropriate? Were sensitivity studies done (for BTEX
measurements as well as tracer) to address ranges of results if
characterization of ISC input parameters is imprecise?
2-10
Answered in response to Dr. David Guinnip's Question #10, dated
October 24, 1991.
2-11
ATTAl:HMENT 2
MEASlffiEMBHT OF EMISSIONS FROM OPEN WAST~WATER SQURCES
There are three key steps to the determination of air
emicsions from op,en wastewater sources. First, the amount of
organics entering the system must be mea~ured or ostimated.
Next, the release rate (fraction emitted)" must be estimated. The
relcasQ rate can be estimated using either Chemdat7 or the flux
chamber. The flux chamber must be used appr('lF;-:~iC':te 1y, hOW@VAT,
as described below. Finally, the effect of comr;eting mechanisms
to air emissions, such as removal from the system in an oil layer
or through destruction by biodegradation or photolysis, mus~ be
estimated. It is critical that all possible emission sources be
id~ntified and their ~elease rates estimated to obtain a valid
emission estimate. Sources such as drains and junotion boxes can
be significant emission sources if there are "sweep gasses passing
tJu"uugh them ana li¥eirs i.n clarifiers can be major sources because
of the aeration alrld stripping that occurs
This approach has heen used by EPA to estimate annual
organic air emissions from open wastewater sources in setting air
emission standards. The EPA first determines the average
concentr~tion of I;;;pecific organic compounds entering the system.
Then this value, along with model physical and meteoroloyical
parameters for a system, is used in the appropriate Chemdat7
emission ~stimAtion model. The biological treatment portion of
the model is used, as appropriate, to account for this competing
mechanism.
The flux chalwer is a useful tool for determining the
"standardized" flux of specific compounds from the surface of an
open area ~Qurce as an altQrnative to the Chemdat emission model.
To determine the flu~, measurements of the concentrations ot
specific compounds in the wastewater under the chamber are taken
at tne same tlme the emission ratA for the surface under the flux
chamber is measured. The ratio of these values is the emission
flux for that point on the surface at that time. The measurement
is "standardized" because tho area under the chamber is effected
by the standardized winds under the chamber rather than the
ambient winds tha1~ are effecting the rest of the surface.
The flux chamber can be used to estimate the instantaneous
emission rate froDI a surface, but it is hiqhly uncertain to
extrapolate the emission rate measured from testinq one point to
other areas of the surface or to other points in time because ot
large spatial and temporal variations that occur in this type
system. Incomplete mixinq and losses due to air emissions would
cause spatial variations at a given time and process (inlet
orqanics) or meteclroloqical (wind speed and temperature) chanqes
would cause the average concentration to increase or decrease
which would cause temporal variations.
3-1
SUBJECT INDEX
RESPONSES TO ATTACHMENT 2
PAGE SUBJECT
9-15 Measurement of Emissions from Open wastewater

Sources
9-10 Measurements
11 Model Accuracy; Wind Speed Effects
12 Input: Data Availability
14 Annual Emissions; Peer Review
3-2
Response to Attachment 2
Measurement of Emissions From open wastewater Sources
uncertainties will exist with any type of emission estimating
method one chooses for an open wastewater source--both measurement
and modeling.
Measurements. In the case of measurements, estimating mass
emission rates is difficult. If this were an easy measurement
then there would be little need for discussion on this point. One
may be able to estimate short-term emissions through measurements,
but extrapolating to a long-term annual rate is uncertain. At
Yorktown, measurements were made during warm weather when the
facility was operating near maximum capacity. We would expect
higher than "average" emissions under these conditions.
Nevertheless, annual emissions were calculated by simple linear
extrapolation from the "snapshot" values. This may bias the
emissions used in this study on the high side.
Further, measurement techniques such as a flux chamber alter the
environment from which the measurement is made. Arguments can be
made that the flux chamber results in measurements which are
either higher ~ lower than the actual emissions. The precision
and accuracy of the flux chamber was addressed by Radian
Corporation when they developed this technique under contract to
EPA.
3-3
Attempts 1:0 develop and validate a new measurement method to
estimate E~missions from such sources would be a maj or research
program. Prior to the measurements at Yorktown, we were not aware
of any measurements to quantify actual emissions from an open API
separator. The Ap··42 emission factor commonly used for this
source is 30+ years old and was based on surveys rather than
measurements. EPA has given this emission factor a "0" quality
rating. Because we did not have the resources to conduct a major
research program on sampling methodologies, we chose to use a
previously developed sampling technique. We felt that possible
limitations of the sampling method were less significant than the
lack of any quantitative emission measurements for this source
type. For more discussion on the implementation of the sampling
methods, please refer to our responses to the general comments
raised by Dr. David Guinnip dated October 24, 1991.
Models. Models also have limitations when used to estimate

emissions from sources such as these.
Model accuracy. TOI be considered useful as a predictive tool,

models must replica.te experimental measurements with a reasonable
degree of accuracy. EPA has published some comparisons between
model predlictions for wastewater sources and observed mass
transfer coefficients. Figures 1 and 2 summarize the range of
model predictions of mass transfer coefficients versus measured
mass transfer coefficients. These data were taken from the
CHEMDAT7 model evaluation (USEPA, 1989). As indicated by these
3-4
Figures, t.he CHEMDA.T7 model exhibits a significant and consistent
bias toward over-estimating transfer rates by factors of 10-20 or
more. The performance of the model is further complicated because
data have not been developed to compare model predicted estimates
of emissions to actual measured emission rates.
Thus, only a small portion of the model has been evaluated and the
model has not been tested in its entirety for the problem it is
attemptingr to simulate.
wind speed effects. The formulation of the CHEMDAT7 7 model is

based on limited data obtained under ideal conditions. For
example, the question can be asked do the wind speed correlations
used in developing this model apply to a pond located in the
center of a process unit or to a pond slightly below grade (i.e.,
does the air flow across the pond surface correlate with the
assumptions in the model of a 10-meter/sec wind speed in the open
atmosphere)?
Input data availability. Representative water samples and

analyses must be obtained to initialize and use the CHEMDAT7
model. Th.is model is used to estimate annual emissions. One must
then address the spatial and temporal issues related to obtaining
representative water samples. For example, for a given open
source, how does one determine the number of samples necessary and
how does one determine the appropriate sampling interval.
3-5
other sampling problems such as determining the amount of free oil
on the surface of the water must also be addressed. EPA
documentation (USEPA, 1990) cites benzene levels of 1-10% in
various petroleum "'7aste oil streams. The source of this
information is unclear. However, these values are significantly
higher than values measured at Yorktown, and would lead to
correspondingly higher calculated emissions.
This same EPA documentation lists the following benzene

concentrations for various aqueous waste streams. These were
calculated based on assumptions about benzene concentrations in
crude oil" free oil levels in wastewater, and benzene partitioning
between oil and water. Measured values from the Yorktown Project
are shown for comparison.
comparison of Calc~llated and Measured Benzene concentrations in

Wastewater streams
ppm ppm
Process Source Benzene Benzene
Calculated Measured
1. Crude storage 8-43 0.37
2. Catalytic Re~forming 500-630 0.:88
3. Coking 13-320 0.9
4. Gasoline Stclrage 13-320 1.9
5. Catalytic Cracking 13-320 0.37
In each case, the llIleasured concentration is 10 to 1000 times less

than the calculated value. These higher estimated concentrations
would be expected t,o show correspondingly higher emission rates.
3-6
All of these factors--higher than measured mass transfer
coefficients, higheir than measured benzene content in oil streams,
higher than measureid benzene content in wastewater streams, and
higher than measureid wind veloci ties--are used by the CHEMDAT7
model. This apparent compounding of errors emphasizes the
critical importancei of field measurements in evaluating emission
sources and matching model estimates with those measurements.
Annual emissions. Another issue related to the use of such a

model to E~stimate annual emissions is the use of average
meteorology. CHEMDAT7 uses an average meteorology ·to calculate
annual emissions, based on a single input water concentration. A
more accurate approach would model a range of meteorological
conditions (and wat.er concentrations), and then the average
emission rate would be computed as a weighted average for the
conditions which prevail for different time periods.
Peer Review. Models used for national regulatory analysis, policy

decisions, and compliance determinations deserve to be of the
highest technical and scientific quality. Peer review of proposed
models is an essent.ial step in the quality assurance process. EPA
has developed a number of these tools over the years, which are
now standard method.s of choice. The CHEMDAT7 model has not yet
been peer reviewed. A number of model assumptions are unproven,
and appear overly simplistic for calculating emissions from real
wastewater sources. Among these, CHEMDAT7 does not quantify (1)
the large impact of a separate oil phase on evaporative losses in
3-7
petroleum processing wastewater systems, (2) the impacts of solid
absorbent materials on emission levels, (3) the impact of surface
active agents in enhancing or inhibiting evaporative losses, and
(4) the actual level of oil present in aqueous systems.
Development of emission models is an important research area

worthy of greater USEPA attention and resources. Models clearly
have a place in attempting to estimate emissions. They are
essential tools for evaluating complex alternatives. However,
they should be based on sound science, evaluated rigorously
against representative data, and should undergo peer review as
part of a formal submittal following the USEPA Modeling Guideline.
3-8
Emissions Modeled vs. Measured
us EPA Chemdat 7 Model
Figure 1
Mass Transfer Coefficient
25 -
20 -
15 -
W
I
ID 10 -
5- . ~
o ---t--=
Site 5-1 (B) Site 5-1 (T) Site 5-6 (B) Site 5-6 (T) Site 5-2 (T)
Test Locations
D Model Estimates B Measured

8 • benzene, T • Toluene
Source: USEPA Hazardous Waste Treatment
Storage & Disposal Air Emission Models
1989 Review Draft
Emissions Modeled vs. Measured
us EPA Chemdat 7 Model
Figure 2
Mass Transfer Coefficient
35· ~
30
25
20
w 15
....oI
10
5
o~·----~----------~----------~-----------~----------~----~
Toluene Benzene Ethylbenzene TCE MeCI

Chemicals (multiple tests)
o Model Estimates -8- Avg. Measured
Source: USEPA Hazardous Waste Treatment

Storage & Disposal Air Emission Models
1989 Review Draft
ATTACHMENT 3
REFINERY ORGANIC AIR EMISSION SOURCES
The following .are observations and comments on the air

emission estimates in the YorKtown study along the lines of the
comments previously made in the note from KC Hustvedttc MQ.~3\
Joyce dated June 13, 1991, (Attach~ent 4) ana in the discus~ion
of October 8, 1991. The listing of sources is the same as was
presented in Table .2 of the note.
1. storagp. tanks
AP-4.2 was used to estimate emissions organic emissions from

tanks. This;~ state-of-the-art. The emissions were speciated
using estimated concentrations in the stored products and
temperatures. Clear documentation of this speciation is needed.
This approach appeaJr!l:t reasonable except. for the ratio of
predicted to observ~ad ambient concentrations when tanks were
targeted showed thai:: the benzene emissions may have been
understatad.
2. Equipment. leaks
AP-42 emission factors were used along with estimated
default equipment cc:mnts developed by Radian Corporation for EPA.
Tnie i5 a reaGonaQle approach where you hav~ no site-specific
information. We uncierstand t.hat the emissions were speciated
using estimated concentrations in the products. Again, clear
documentation of thio cpeciation is needad. SitA-~PQcifio
est.imates of equipment leak emissions could have easily been
derived for this major emission source by either counting all of
tllt:l equipment or by count.ing the actual numbar of pumps and
rat.ioing t.herest of the equipment.. There are also improved
methods of estimating emission rates through screening for site-
specitic l~~~ frequenCies. Overall, the lack of cit.e-speeific
informat.ion in the equipment leak emissions .introduces
significant uncertainty but not necessarily a high or low bias.
'l'ne leak trequency ~,! the 5mall sample of equipment. tested in
this program was hiqher than has been found elsewhere, indicating
emissions may be understated.
3• Coker pond
emissions from t.lle coker pond were directly measured.
Concerns with the measurement technique used are outlined in
Attachment 2.
4-1
4. Wa~t.t;!wdL£::!L· t;ullf:!t;tion and t,,"t=i:ltment Systf;!U
The key to est.imating emissions from a wastewater treatment

system 1s to determine the amount ot organics (or BT~X) that
enters the system. Because this was not done in the Yorktown
study, it is difficult to know what the emissions were. This is
an important omission nere, because, as discusse~. belOW, several
air emission sources in the wastewater system were not measured
or the measUrement technique appeared to have a negative bias.
In a separate sUbmi t:tal 'Co 'Cne Agency, estimates.:;' 6C 1:Ii.Q/yr ot
benzene in the system and about 30 Mq/yr benzene air emissions
were made for the Yorktown refinery. This compares to the
estimate of about 3 Mq/yr benzene air emissions in this study. A
discussion of emissions from. each of the source types appears
below.
Drains
Process unit d.rain emissions were included in the process
unit equipment leak emissions based on AP-42 factors and default
equipment counts. The AP-42 factors are base~ on testing that
consisted of baqgim;J the drain, which would be reasonable for a
drain with a water seal, but for open (unsealed) drains this
would qreatly restrict the air flow and would reduce predicted
emissions. If the .in-unit drains a Yorktown are not water
sealed, drain emissions may be severely understated.
In-unit junt::tion boxes
These units Well:'e not tested and their emissions are not
reflected .in the emission estimates.
In-unit wastewater separators
These units were'not tested and their emissions are not
rE!!flAntp.d jn th9 emission estimat9!t. The removal of oil from the
water with in·unit separators is likely part of the reason that
the API separator may have lower emissions than AP-42 would
predict.
Sewer systeJIl junction boxes

Three of the nine junction boxes were directly measured, but
it is unclear from the report how the measured emissions were .
used to estimate facility emissions. We understand that one of
the three tests was rejected because there was a nearby by-pass
vent stack that was not measured. If correct, this should be
clearly stated in the report and the other two junction boxe~
should also be checked to make sure they do not have similar
problems. Also, the measurement technique, covering the open
grated area and addinq a staok, would dofinitely effect the wind
flow in the sewer system and the emissions from the junction box
4-2
being measured. Although it is possiOle tna'C emission:.; were
eitner increased or decreased, it is more likely that covering
th~ grate decreased flow more than adding the stack increased
flow and therefore emissions are likely understate(1.
API separator forebay
This unit was not tested and its emissions are not reflected
in the emi ~sion est.imates. This introduces a large negative bias
in the emission estimates because a significant portion ot' the
emissions from the API separator w~uld occur from the forebay.
The forabay is the most turbulent area, promoting a high fraction
of volatiles emitted, and it is where the concentrations would be
at the greatest.
API separat.or
TWO direct maa.surements were made ~ General concerns with
the techniques used are discussed in Attachment 2. More
specifically for the API separator, the measurements did not take
into acoount that mora ia emitted where the concentrations in the
aqueous phase are highest (at the inlet to the separator bays)
and that many of the organics partition into the oil phase where
they are much more ca~ily emitted. Both of ~he factors would
indicate that the estimated emissions from the API separators is
understated.
Clarifiers
The:::u:! unit:::; were not tested and thGi~ emissions are not
reflected in the emission estimates.
Biological treatment tanh:
This lxnit was not tested and its emissions are not reflected
in tne emission estlmates.
Other wastewater treatment units
These units were not tested and their emissions are not
reflected in the emission estimates.
5. Slowdown drums and other process vents
It is unclear how ~lowdown arum ~missions will be estimated
in the final study. Several episodes of estimation and samplinq
have occurred, most of which have indicated that this is a major
source of air emissions. It there aru other process vents, suoh
as a vacuum system noncondensable qas vents or vents on other
accumulators that are not tiea into the blowdown or flare header
system, these emissions would. also lile misslng Cram the inventory.
4-3
6. Land tre~tment: unit
Emissions froln this unit were directly measured based on

only one mt!~:;$u.rf::!mliimt. I wUlJ.lu "yrt:le L.h~L these estimates are
likely overestimates and should be used with caution.
7. . cooling Tower
"Non-contact" water
It is unclear if any of these units exist, or if so, how
they were characteri2ed.
Pump gland water
The air quality report indicates that total emissions from
this cooling tower '~ere estimated using AP-42, which was
developed for non-contact cooling towers, and these emissions
were speciated by iJnlet sampling. The recently received overview
report indicates th~ese emissions were measured by mass balance,
however. This needs to be clarified. As. we discussed, previous
testing of non-contact cooling towers showed great uncertainty in
estimating emissionls based on a mass balance approach so these
data would also be I:liqhly uncertain.
8. Transfer operai~ions
AP-42 was used to estimate emissions organic emissions from

transfer operations. The emissions were speciated using estimated
concentrations in the products. This appears reasonable except
for the f~action of benzene in the emissions seems much lower
than the averaqe fr!lction of benzene in gasoline.
9. others (?)
None identi f:i eeL
4-4
SOBJECT INDEX
Responses to Attachment 3
PAGE SUBJECT
14 Tanks-Organic Emissions from
15-16 Equipment Leaks-Lack of site Specific Leak Freq.
16 Coker Pond Emiss.; Lack of Data Concerning Entering
Organic Emmis. Into Wastewater Treatment Systems
17 Organic Concentration of wastewater Streams
17-18 Benzene Emissions, NESHAP
18-21 unit Draining, In-Unit Junction Boxes, In-unit
wastewater Separators--Measurements, Lack of etc.
21 Sewer System Junction Boxes
22-23 API Separator Forebay Area; API sep--
Testing-lack of, Bias in Estimation etc.
23 Clarifiers--Lack of Testing; Biological Treatment
Tanks--Lack of Testing
24 Other Wastewater Treatment Units--Lack of Tests
24-25 Blowdown Drums & Other Process vents
25-26 Cooling Towers-Existence of
26 Pump Gland Water-Measurement Techniques
26-27 Transfer Operations-Benzene Fraction
4-5
Response to Attachment 3
Refinery Organic Air Emission Sources
(Note: Original questions and comments are repeated
in l60LD. Response is in normal type.)
The following are observations and comments on the air emission
estimates in the Yc)rktown study along the lines of the comments
previously made in the note from R.C. Hustvedt to Mark Joyce dated
June 13, 1991, (At1~achment 4) and in the discussion of
october 8, 1991. The listing of sources is the same as was
presented in Table 2 of the note (attached).
1. storage Tanks
AP-42 was used to 4!stimate organic emissions from tanks. This is
state-of-the-art. The emissions were speciated using estimated
concentrations in 1~he stored products and temperatures. Clear
documentation of this speciation is needed. This approach appears
reasonable except for the ratio of predicted to observed ambient
concentrations when tanks were targeted showed that the benzene
emissions may have been understated.
The method is discussed in detail in the Volume II document.

Speciation data was based on laboratory analysis of Yorktown
products in tankage. These will vary somewhat in day-to-day
operation since gasoline is blended for octane and vapor pressure
specifica1:ions, rather than for composition. Other products
would be expected to have less variability. The issue of ,possible
underestimation of benzene emissions was discussed in the response
to Attachment 1.
4-6
2. Equipment Leaks
AP-42 emission factors were used along with estimated default
equipment. counts developed by Radian corporation for EPA. This is
a reasonable approach where you have no site-specific information.
We understand that the emissions were speciated using estimated
concentra.tions in the products. Again, clear documentation of
this speciation is needed. site-specific estimates of equipment
leak emissions could have easily been derived for this major
emission source by either counting all of the equipment or by
counting the actual number of pumps and rationing ·the rest of the
equipment. There are also improved methods of estimating emission
rates through screening for site-specific leak frequencies.
Overall, the lack of site-specific information in the equipment
leak emissions introduces significant uncertainty but not
necessarily a high or low bias. The leak frequency of the small
sample of equipment tested in this program was higher than has
been found elsewhere, indicating emissions may be understated.
speciation of emissions was developed using stream compositions
from similar processes at another Amoco refinery. Approximately
150 internal and product streams were analyzed for chemical
constituents covered in the SARA 313 list. These compositions
were then used to estimate compositions of potential fugitive
emissions from equipment containing these streams.
What is suggested in this comment is a "bottom up" effort in
developing an emission inventory. This is certainly a preferred
approach. What this Project attempted was a "top down" approach
4-7
(i.e., an attempt to confirm our previous estimates in a holistic
manner). The issue of component leak frequency is addressed in
section 4.1.8.
3. Coker Pond
Emissions from the coker pond were directly measured. Concerns
with the measurement technique used are outlined in Attachment 2.
See response to Attachment 2 and responses 2, 3, and 4 to general

questions raised by Dr. David Guinnip.
4. wastewater Collection and Treatment System

The key to estimating emissions from a wastewater treatment system
is to determine the amount of organics (or BTEX) that enters the
system. Because this was not done in the Yorktown study, it is
difficult to know what the emissions were. This is an important
omission here, because, as discussed below, several air emission
sources in the wastewater system were not measured or the
measurement technique appeared to have a negative bias. In a
separate submittal to the Agency, estimates of 60 Mg/yr of benzene
in the system and about 30 Mg/yr benzene air emissions were made
for the Yorktown Refinery. This compares to the estimate of about
3 Mg/yr benzene air emissions in this study. A discussion of
emissions from each of the source types appears below.
We agree that emission estimates would require information about
the amount of organics in the wastewaters. contrary to the
author's statements, extensive surface water measurements were
made and reported in separate documentation, previously provided
4-8
to EPA which documented organic chemical loadings :in different
water streams. As discussed below, the measurements showed very
little organics present in many streams.
However, organic content information is not required to measure
emissions directly. Thus measurements from sewer vents, the API
Separator, and the Coker Pond were made directly at these sources.
The writer has referred to material submitted to EPA under the 90-
day notification program which followed release of the Benzene
Waste operations NESHAP rule in 1990. In that submittal,
approximately 60 Mg/year of benzene were reported as the total
annual benzene (TAB) at the Refinery. The intention and result of
the 90-day report established that the Yorktown Refinery would be
subject to provisi1ons of the NESHAP rule, since its TAB exceeded a
de minimus level of 10 Mg/year. The data was collected under a
tight time deadline and not subjected to rigorous quality control,
once the de minimus quantity was exceeded. In reviewing this
data, it is apparent that the information is not of high enough
quality to make a material balance for benzene at the Refinery.
The only conclusion we can draw from the report is that the
Refinery did exceed the 10 Mg/year de minimus level. Closer
inspection of the information showed the following:
60 Mg/year NESHAP Submittal
-17 Mg/year double counted at inlet to sewer system

and API separator outlet,
-42 Mg/year recovered oil from API separator
3 Mg/year emitted
4-9
It is interesting to compare the measured emissions value
(approximately 4 Mg/year) with values reported by EPA based on
modeling results and estimates (USEPA, 1990): these show a range
of emissions of 2.6 Mg/year to 32 Mg/year. The measurement
program at Yorktown and the rough material balance above both fall
within this range, albeit at the lower end.
- Drains
Process unit drain emissions were included in the process unit
equipment leak emi:ssions based on AP-42 factors and default
equipment counts. The AP-42 factors are based on testing that
consisted of baggi:ng the drain, which would be reasonable for a
drain with a water seal, but for open (unsealed) drains this
would greatly restrict the air flow and would reduce predicted
emissions. If the in-unit drains a Yorktown are not water sealed,
drain emissions ma:y be severely understated.
- In-unit jun1ction boxes

These units were not tested and their emissions are not reflected
in the emission es'timates.
- In-unit wastewater separators

in the emission estimates. The removal of oil from the water with
in-unit separators is likely part of the reason that the API
separator may have lower emissions than AP-42 would predict.
Not all of the emission components mentioned were specifically
4-10
addressed or measured individually in the development of the
inventory. Limited budget and manpower resources required careful
targeting of the testing program. OAQPS review and comments on
the sampling plan 'were solicited in April, 1990, but none were
given. Ambient monitoring and modeling analysis was designed to
provide a check on all emission sources. The ambient
concentrations (impacts) measured downwind of a process source are
the result of actual emissions from within that portion of the
unit from all sources such as pumps, flanges, valves, sewers, etc.
The measured impac"ts obtained from ambient sampling were compared
to model predictions which used an emission inventory derived as
described above from stream compositions, default component
counts, and generic emission factors.
The detailed comparison is discussed in section 5.0 of the
document. Reasonable agreement was found between the modeled and
monitored concentrations. Thus, we believe the emission inventory
presented represen1ts the total actual emissions wi thin the
uncertainty limits of the analysis. Significant benzene sources
have not been omitted.
We have performed a sensitivity analysis to examine what
additional benzene emissions would result from process sewers
using different assumptions about sewer size, etc. In this
analysis we estima1:ed the total area of the sewer that was open to
the atmosphere and used the flux measurements from the sewers to
estimate emissions.. Based on this analysis, we estimate the
4-11
sewers might contribute 2-4 tons per year of benzene. This is
within the uncertainty limits of the analysis. Details of the
sensitivity calculations are presented in Figure 6-11 and 6-12.
This analysis does not support the suggestion that unit separators
had large emissions which were excluded from measurement. As
noted earlier, we would be most interested in discussing whatever
measurements OAQPS might have to support their theory.
- Sewer system junction boxes

Three of the nine junction boxes were directly measured, but it is
unclear from the report how the measured emissions were used to
estimate facility lamissions.We understand that one of the three
tests was rejected because there was a nearby by-pass vent stack
that was not measul~ed. If correct, this should be clearly stated
in the report and 11:he other two junction boxes should also be
checked to make SUl~e they do not have similar problems. Also, the
measurement technicJUe, covering the open grated area and adding a
stack, would definitely effect the wind flow in the sewer system
and the emission fl~om the junction box being measured. Although
it is possible that emissions were either increased or decreased,
it is more likely 1;hat covering the grate decreased flow more than
adding the stack illcreased flow and therefore emissions are likely
understated.
Again, we would be interested in discussing whatever specific

measurements OAQPS has obtained on this issue. Amoco has obtained
an independent set of measurements from other sewer vents at
4-12
another Amoco refinery. These are discussed in section 4.1.9,
Volume II. comparison of theses two data sets indicates that the
results are similar. During discussions in Triangle Park on
October 8, 1991 we were told our measured emissions from sewers
were higher than would be calculated by EPA models. The statement
above suggesting emissions were understated appears inconsistent
with the previous (October 8, 1991) statement.
- API separator forebay

This unit was not 1tested and its emissions are not reflected in
the emission estimates. This introduces a large negative bias in
the emission estimates because a significant portion of the
emissions from the API separator would occur from the forebay.
The forebay is the most turbulent area, promoting a high fraction
of volatiles emitted, and it is where the concentrations would be
at the greatest.
- API separatc)r
Two direct measureillents were made. General concerns with the
techniques used artt discussed in Attachment 2. More specifically
for the API separa1;or, the measurements did not take into account
that more is emitted where the concentrations in the aqueous phase
are highest <at the inlet to the separator bays) and that many of
the organics partition into the oil phase ~here they are much more
easily emitted. Both of the factors would indicate that the
estimated emission!1 from the API separators is understated.
We included the forebay area of the separator in calculating

4-13
emissions for this source. We used the average flux rate
measurement over the entire separator area to compute total
emissions. Results from the monitoring program never observed
high concentrations from this source. We feel that the monitoring
results confirms that emissions from this source are not grossly
underestimated. We would be interested in discussing any relevant
measurements OAQPS may have available on this topic.
Sensitivity calculations considered the highest emissions measured
from the ;~PI separator instead of the average emissions. Even
though this increased separator emissions by 90%, there was no
significant change in modeled concentrations outside the facility
fenceline.
- Clarifiers
These units were nc)t tested and their emissions are not reflected
in the emission es1~imates.
Two clarifiers are present at the Refinery, located downstream of
the aeration basin in the biological treatment unit. One handles
separation of treated water from microorganisms; the second is
part of the aerobic sludge digester. In these locations, ~
benzene would be expected in the water entering these units.
Therefore no emissions would be expected from this source, and
hence, no measurements were made.
- Biological 1;reatment tank
This unit was not tested and its emissions are not reflected in
4-14
the emission estimates.
Water entering the biological treatment system contains no free

oil and less than 1 ppm benzene. This information was previously
reported as part of the Surface Water sampling program in this
Project. Since the benzene concentration is low, emissions from
this source would also be expected to be quite low, and within the
accuracy of the overall emission inventory. Hence, no
measurements were made.
- other wastewater treatment units

in the emission eS1t;imates.
These sources are included in the inventory to some extent under
the category of waste water tank. Emissions were included based
on a material balance around the tank on the inlet and outlet
water streams. Ambient air samples did not show the presence of
elevated impacts downwind of the wastewater treatment area.
s. Blowdown Drums and other Process vents

It is unclear how lolowdown drum emissions will be estimated in the
final study. SevelE."al episodes of estimation and sampling have
occurred, most of which have indicated that this is a major source
of air emissions. If there are other process vents, such as a
vacuum system noncondensable gas vents or vents on other
accumulators that are not tied into the blowdown or flare header
system, these emissions would also be missing from the inventory.
4-15
See Section 4.1.3 in the report and the response to question #6
raised by Dr. David Guinnip for a discussion of blowdown stack
emissions. AP-42 estimated emissions were used for purposes of
modeling the Refinery inventory. The AP-42 emission factor is not
based on any measurements. Measurement of Blowdown stack
emissions was finally completed in July, 1992. The results were
about 98% lower than the estimated values, a reduction of 5100
tons per year of VOC emissions.
The technique involved injecting SF6 into the base of the blowdown
stack. The concentration of SF6 was measured at a point midway up
the stack. The flow rate in the stack was then calculated based
on the amount of dilution of SF6 underwent in the stack. Also,
during the sampling, conventional EPA flow rate measurements were
taken and it was concluded that typical blowdown stack flow rate
is so slow. that conventional stack sampling methods would not
provide accurate data.
The previous modeling inventory was updated to reflect these data

and benzene impacts beyond the fenceline were determined.
Comparison of the location of the 0.12 ug/m3 isopleth, with the
original isopleth, indicates that to the east there is no change
in the lo,cation of the 0.12 isopleth for the original modeling and
this revision. However, for other directions, the location of the
0.12 ug/m3 isopleth is moved closer to the refinery by a distance
that ranges from 300 to 1000 meters. In addition, we calculated
4-16
the area within this concentration level and compared it to the
previous modeling. In this analysis we found that approximately
60 square kilometers were contained within the 0.12 ug/m3 isopleth
and for the original analysis the area contained in the 0.12 ug/m2
isopleth was approximately 89 square kilometers.
There are no other routine vents that are routed directly to the
atmosphere during normal operation. A flare system handles a
number of low pressure gas streams.
6. Land Treatment unit

Emissions from this unit were. directly measured based on only one
measurement. I would agree that these estimates are likely
overestimates and should be used with caution.
No comment
7. cooling Tower
- "Non-contac't" water
It is unclear if any of these units exist, or if so, how they were
characterized.
There are no cooling towers for non-contact cooling water. Most

process cooling is accomplished with once-through water from the
York River. Hence, no measurements were made.
- Pump gland 1water

The air quality report indicates that total emissions from this
cooling tower were estimated using AP-42, which was developed for
4-17
non-contact cooling towers, and these emissions were speciated by
inlet sampling. ~~he recently received overview report indicates
these emissions were measured by mass balance, however, This
needs to be clarified. As we discussed, previous testing of non-
contact cooling tc,wers showed great uncertainty in estimating
emissions based on a mass balance approach so these data would
also be hiqhly uncertain.
Emissions from the small cooling tower which handles pump gland
cooling water werE~ based on a mass balance approach: measuring
inlet and outlet concentrations of hydrocarbons in the water, and
attributing all differences to emissions from the tower.
8. Transfer opeJl:'ations
AP-42 was used to estimate emissions organic emissions from
transfer operations. The emissions were speciated using estimated
concentrations in the products. This appears reasonable except
for the fraction c)f benzene in the emissions seems much lower than
the average fraction of benzene in gasoline.
The benzene fraction was based on as-produced Yorktown gasoline
blends.
9. others
None identified.
No response is ne4:::essary.
4-18
References
1. USEPA, 1990. "Final NESHAP Standards for waste operations:
Basis for Impact Calculations," Office of Air Quality
Planning and Standards, Research Triangle Park, Table
2-5.
2. USEPA, 1989. "Hazardous Waste Treatment, Storage and Disposal
Facilities (TSDF) Air Emission Models," Office of Air
Quality Planning and Standards, Research Triangle Park
(EPA-450-3-87-026).
4-19
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Air Quality Planning and Standards
Flesearch Triangle Park, North Carolina 27711
June 1, 1992
MEMORANDUM
SUBJECT: Concerns with the Amoco/EPA Yorktown Refinery study
FROM: Kent C. austvedt, Chief
Petroleum Section, CPB (MD-13)
/C--C ~
TO: Ann Bailey, Special Assistant to the DM
Office of Air and Radiation (ANR-443)
I. Summary and Conclusions
The purpose for this memo is to document Agency concerns
with the interpretation of certain data developed during the
Amoco/EPA joint pollution prevention study conducted at the Amoco
Yorktown refinery (the study). The study is being interpreted to
conclude that benzene emissions from wastewater sources are a
minor contributor to overall refinery benzene emissions and that
control of benzene emissions, such as is required by the benzene
waste operations NESHAP, is the least cost effective means of
reducing benzene emissions.
As discussed in the following sections, there is a great
deal of uncertainty in the wastewater emission estimates reported
in the s'tudy and :L t is possible that the magnitude of benzene
emissions is substantially understated. The test program was of
limited scope, with potentially major sources of benzene
emissions not measured or estimated. Other information provided
to the Agency by Amoco indicate that benzene emissions would be
much greater than what the study suggests. In addition, the
control approach used to estimate the cost of the wastewater
controls is an integrated approach that will provide pollution
prevention and release reduction benefits to several media, which
were not accounted for in the study results. While the Agency
and the study conclusions support this multimedia integrated
compliance approach, it must be recognized that this is a more
expensive means of compliance than a narrow approach.
II. Background
Quantification of air releases from petroleum refineries is
a difficult task 'that involves a great deal of uncertainty. The
study characterizled refinery releases based on emission factors,
where they were believed to be reasonable, and on measured or
estimated emissions from other sources. Amoco is to be commended
5-1
for undertaking thi.s joint project with the Agency. I especially
appreciate their wi.llingness to discuss the study test program
and the concerns about the uncertainties in the use of the
resul ts of the test: program. Amoco has made several substantive
changes to the report as a result of our discussions. Many of
our concerns have been alleviated through these discussions.
Early coordination with appropriate parties is critical to
the success of this type project and Amoco did attempt to obtain
such involvement. It is unfortunate that the OAQPS Chemicals and
Petroleum Branch and Emissions Measurement Branch were
inadvertently not involved in the planning stages of the
measurement program to take advantage of experience gained in
refinery measurements programs, such as the ORD study,
"Assessment of Atmospheric Emissions from Petroleum Refining",
that was conducted in the late 1970's in coordination with OAQPS
and the American Petroleum Institute.
III. Concerns with Benzene Waste Operations NESHAP
GENERAL
In interpreting the results of the study with respect to the
benzene waste operations NESHAP, it is important to note that the
study was not designed to characterize benzene emissions from
NESHAP affected sources. Data were developed that can be
compared to certain portions of the wastewater standards, but, as
discussed below, most of the sources were not measured.
Moreover, it appears that some sources that the study does not
include in the comparisons of benzene emissions reduction and
cost effectiveness would be controlled under the NESHAP. In the
tables describing the controls, one of the reasons listed for
control of the blowdown system is ·the benzene NESHAP. Also,
control of the desalter and coker pond and at least portions of
the sample purge controls could be attributable to the NESHAP.
Control of these sources, as would be required under the benzene
NESHAP, would increase the amount of benzene emissions controlled
and improve the cost effectiveness of control.
AMOCO SUBMITTALS
In other submittals to the Agency, Amoco has provided
additional information that can be used to compare against the
study estimates. In earlier discussions on the benzene waste
operations NESHAP, Amoco presented to the Agency information on
the benefits of cluster compliance approaches. The presentation
included data on the cost and benzene emission reductions of
various control programs. In this presentation, it was reported
by Amoco that the Yorktown refinery had 31 Mg/yr of benzene
emission from their waste operations. Although the basis for
this estimate was not presented, it would indicate that the study
estimate of about 4 Mg/yr of benzene emissions could be
5-2
substantially understated.
Also, the Amoco Yorktown refinery "90-day" compliance report
submitted to the Agency for the benzene standard showed
information that would tend to indicate that the measurement
program understated emissions. In the 90~day report for the
standards, facilities are to identify their benzene in wastes at
the point. of generation, where they are first formed at the exit
to the production process. This identifies the maximum benzene
emission potential for aqueous wastes. The purpose of this
report is to compare against the 10 Mg/yr total annual benzene in
waste (TA.B) facili-::'y applicability trigger in the standards that
identifies facilities to be controlled.
Amoco reported 63.3 Mg/yr TAB in their report, although most
of it was not determined at the point of generation as required
in the rule. Many facilities reported TAB in a similar manner,
which is one of the reasons the Agency proposed clarifications to
the rule. Because Amoco found that they were over 10 Mg/yr and
subject· to the control requirements of the rule, they may not
have used normal quality control in their report, but the numbers
do indicate that benzene emissions could have been substan'tially
higher than was found in the study.
Of Amoco's total reported TAB, only about 4.2 Mg/yr TAB was
determined at the point of generation; the rest was for wastes
already in the management system. There were 21.4 Mg/yr TAB in
the oil recovered in the coker and combo unit oil/water
separators, which would include some amount of double accounting
for the small amount of TAB that was measured at the point of
generati()n. This benzene in recovered oil is the remaining
benzene after emissions within the process unit from the process
drains, junction boxes, and the oil/water separator.
Amoco also reported 20.4 Mg/yr TAB in oil and sludge
recovered from thE! API separator, which may also include a small
amount of double accounting from the 4.2 Mg/yr of TAB that was
determined at the point of generation, but does not double count
for the oil recovered in the in-unit oil/water separators. The
benzene in the API separator oil and sludge is what remains after
emissions from the process unit drains, junction boxes, and
oil/water separators, the sewer system junction boxes, and the
API separator. Finally Amoco reported 17.5 Mg/yr TAB in the
water leaving the API separator, which was substantially higher
than was found in the study and is likely overstated. From the
estimating techniques outlined in the background document for the
benzene NESHAP, it.would be estimated that 25 to 75 percent of
the TAB was emitted prior to the recovery of the oil that was the
basis for these measurements. This would indicate that benzene
emissions from the wastewater system could have been as high as
40 to 60 Mg/yr.
5-3
EMISSION ESTIMATES
Background - ']~he Air Quality Data Volume II of the study
final report addresses concerns on the overall air release
inventory previously articulated in a November 25, 1991, note
from KC Hustvedt, et al., to Mark Joyce. Appendix J of Volume II
contains Amoco responses to the questions raised in this note.
Several of these rE~sponses have also been incorporated into the
text. The purpose for this section is to clarify and elaborate
on these comments in light of Amoco's responses for the
wastewater processE~s regulated by the benzene waste operations
NESHAP.
The major uncertainty in the estimation of wastewater
emissions is the extrapolation from the measured results to
refinery emissions. A direct extrapolation can be done if
representative emissions are measured. If the emission
measurements are not representative of the entire system, a
technique for extrapolation based on system design with respect
to emission mechanisms and the "source term" must be developed.
The emission mechanisms depend on the source being evaluated, but
they generally are a function of system geometry, operation and
meteorological conditions. For air emissions from wastewater
sources, the source term is the loading of benzene, or the
wastewater flow and benzene concentration, at the point the
wastewater first enters the wastewater system.
In the previous comments on the study, the determination of
the representative nature of the measurements was characterized
in terms of identifying and accounting for spatial and temporal
variability. Amoco's response to the note shows that the
concerns with spatial and temporal variation were not clearly
stated. 'rhe main spatial concern involves the location where
samples were taken with respect to the degree of mixing in the
system and the definition of the source term, or the total amount
of benzene in wastewater when it first enters the wastewater
system (prior to losses due to emissions). Temporal variation
was meant to refer to changes in concentration with time, due
mainly to process changes, such as tank drawdowns, coker
blowdown, or maint4:mance acti vi ties, or to meteorological
conditions. Emissions per unit area (flux rate) and emissions
per component are highest where there is the highest
concentration of b49nzene. Generally, Amoco tested in the latter
stages of the wastewater management process, after most of the
benzene was emitted. The high ambient temperatures and full
capacity utilization during the test should result in accelerated
losses (exacerbate the problem) early in the system due to higher
ambient temperatures and wastewater temperatures.
Emission Sources of Concern - Benzene emissions occur from
three distinct areas in the refinery wastewater collection and
treatment system. These are the pFocess unit wastewater handling
5-4
system, which includes process drains, junction boxes, and
oil/water separators; the wastewater conveyance system from the
process unit to thl9 treatment system (the sewer system); and the
wastewater treatment system. The following sections describe the
study efforts to estimate emissions from each of these areas and
the uncertainties associated with them.
A. Process unit systems - The major concern with the study is
that the benzene emission estimates were not provided for the
process unit wastewater handling system, where a sUbstantial
portion of the emissions are expected to occur. Emissions were
not measured or es~imated from the process drains, junction
boxes, or oil/water separators in the process unit where the
waste was first generated. Previous EPA studies, including the
benzene NESHAP bac:kground document (Reference 1), the BACT/LAER
Document (Reference 2) and more recent sewer studies at several
facilities, such as the Shell oil emission test (Reference 3),
and the Rhom and Haas tracer study (Reference 4), have indicated
that about half of the benzene emitted from the wastewater system
would be emitted within the process unit.
B. Sewer systems - Emissions from sewer systems are a function
of many factors, including the system geometry (the existence of
covers and water seal especially), the quantity of oil and
specific organics entering the system, the degree of saturation
of the air in the sewer system, and the amount of airflow out of
the system.
Measurements were made on two of the nine sewer junction
boxes in the conveyance system. The average of the two measured
values was used to estimate emissions from six of the other
unmeasured junction boxes while one was assumed to have zero
emissions. While linear extrapolation could be a valid approach
for estimation if the sources are similar, Amoco could have done
corroborative studies to indicate their degree of similarity. An
example would be comparing the gas flow and benzene concentration
of vapors being emitted from the unmeasured junction boxes to the
measured ones to establish a basis for extrapolation.
There is not only a concern with the extrapolation from
these two measurements to long-term emissions, but also a
secondary concern with uncertainties in the junction box sampling
method, which likely affected the measured emissions. The method
used to measure emissions from junction boxes affected one of the
major emission mechanisms, air flow through that junction box,
and thus introduces uncertainty. The method involved covering
all but Cl 0.3 square foot area for a "pseudo-stack" in the
normally 12 squaret foot open top junction box and measuring the
flow and concentration in the stack.
Amoco's respolnse to concerns on this measurement technique
was that it reducEid the total open area in the sewer system by
5-5
only one percent so the free flow of air in the system should not
be inhibited. This response is difficult to follow because it
appears that durinq the testing one of the nine junction boxes
has been essentially completely covered, reducing the open area
of the system by over ten percent, rather than just one percent.
Moreover, the chanqe in open area of the junction box being
measured would appear to be the more appropriate comparison, and
it has been reduced by a factor of 40.
In another response to comments on the effect of covering
the junction box during the test, Amoco compared the results of
the Yorktown junction box test to tests they have performed at
another refinery that had all junction boxes inherently covered.
It is not surprising that these had lower measured emissions
because this would be a controlled, rather than an uncontrolled
system.
In the Appendix J response to comments, Amoco attributes a
statement to me that was actually made by Dr. Allen of Research
Triangle Institute. Based on a review of the report, he
concluded. that Amoco's measured sewer emission rates agreed with,
or, in fact, understated, benzene emissions compared to what-he
preqicted using the BACT/LAER models (Reference 2).
Unfortunately, Dr. Allen's conclusion was based on the erroneous
assumption that the mass of benzene in the sewer system could be
determined by the water sampling results found in the water
quality volume of the study report. When he compared the results
of the sewer testing to the amount of benzene in the waster
phase, he found the measured benzene emissions were greater than
the benzene content in the wastewater system, indicating well
over on half of th.e benzene was being emitted. Upon closer
inspection, however, it was determined that the water quality
volume did not report the oil layer that was present in the sewer
and thus did not include the quantity of benzene that was present
in the oil phase. The presence of unquantified oil containing
benzene in the se\<lrers makes it impossible to compare the measured
values to what we would estimate with our models.
C. wastewater tre~atment system - As suggested by Amoco and as
indicated by the benzene concentration in the API separator
effluent reported in the water sampling report, most of the
benzene emissions from the Yorktown refinery wastewater treatment
system likely come from the API separator system.
Two measurements of API separator emissions were made with
the flux chamber. No measurements were made in the forebay to
the API separator, where the highest concentrations of benzene
and the most turbulence should have lead to higher emissions than
in the separator. The two measured values were substantially
different, which would be expected because they were taken at
opposite ends of t:he separator. This highlights the importance
of charac:terizing or otherwise taking into account the spatial
5-6
variability.
The relative location of the oil layer in the separator to
the flux chamber is of great concern because of the large effect
the oil has on emissions. As compared to emissions with no oil
layer being present, emissions of benzene would be increas,ed if
there were a thin layer of oil and would be decreased if there
were a thick layer of oil. Generally, thickness of the oil layer
constantly changes as oil is periodically skimmed off the
surface. The study does not report the thickness of the oil
layer on average or during the test and does not identify if the
flux chamber was located on a representative thickness of oil.
Measurement of API separator emissions is difficult to do
for an individual facility and extremely difficult to generalize
from one facility to the next. There have been several tests of
API separators since AP-42 was published. In the Refinery
Assessment progra~~ in the late 70's, several API separators were
measured with limited success using a mass balance approach.
This led the Agency to initiate another program to measure
emissions with Engineering science. This program of ambient
testing and tracer studies also failed to produce useful results.
Shell Oil independently performed tests and developed emission
factors 'that were used by EPA in the 80's as the basis for a new
source performancE3 standard for refinery wastewater systems.
Fina~ly, Chemdat7 can be used to estimate emissions for
separators and was used, along with industry-supplied inputs, in
the benzene waste NESHAP development.
Ambient monitoring cross-checks - In Amoco's response to
comments on the potential underestimation of benzene emissions
from the wastewat~9r treatment system, they cite the ambient
testing program as indicative that their emission estimation
program did not miss any major sources of benzene emissions. The
major mechanism for these ambient monitoring cross-checks is the
comparison of predicted ambient concentrations from emission
models/measuremen'ts and dispersion models versus measured ambient
concentrations. Ratios of these values near one indicate good
agreement. Several concerns have been identified regarding
ability to conclude from the ambient monitoring study that
benzene emissions from waste operations are not understated as
discussed below.
The major concern is that at several sampling points the
ratio of predicted to measured benzene concentrations indicate
that emissions were understated, several times by as much as a
factor of two or more. This was especially true for the ambient
samples near the sewers and API separator. In addition, when
comparing the benzene ratios to the ratios for the other
aromatics tested, benzene was almost always a factor of two to
over ten times less. This would indicate that either the benzene
emissions were grossly understated or the other aromatics
5-7
emissions were grossly overstated. Interacting with this was the
methodology used to develop the ratios of measured versus
predicted values. The maximum predicted concentration for a
receptor grid around the monitoring location was used to compare
with the measured value ("spatial pairing was relaxed"). This
assumes that the monitor was placed at the point of maximum
ambient concentration. Even though the monitors were placed at
approximately the predicted point of maximum concentration, it is
unlikely this was the actual maximum during the test period.
This further indicates that the ratio of one should be the upper
limit and measurements less than that would indicate emissions
are greatly unders~ated. Finally, due to the nature of the
ambient sampling, it is impossible to definitively differentiate
the contributions -to benzene concentrations for individual source
types upwind of the monitor. Benzene emissions from different
sources within a process unit, such as equipment leaks, blowdown
drums, and wastewa'ter collection systems, quickly combine and are
measured as one value. Some of these sources were estimated to
be major sources of benzene emissions so their predicted
contributions could have actually been emissions from the
wastewater system.
COST ESTIMATES
There are several allowable control approaches under the
benzene waste operations NESHAP. These include treating
individual streams, retrofitting controls on the sewer system, or
replacing the s,ewer system (the integrated or "cluster"
approach). Treating individual streams with a steam stripper was
used as the cost basis for the rule. Clusters approaches would
generally cost more (they are generally not the least cost means
of compliance) but are attractive because, as discussed below,
they offer co-compliance with other rules and multimedia
protection.
Amoco initially considered and later rejected the second
approach, retrof i t,ting controls. The compliance approach
selected by Amoco and costed in this study involved replacing
their in-ground gravity sewer system with an above-ground
pressurized systelnl and replacing their API separator system with
an improved system that includes parallel plate interceptors and
an induced air floatation system.
The compliance approach selected by Amoco will not only
reduce exposure to benzene from waste operations, but also will
(1) improve effluent quality and ease compliance with future
revisions to the €iffluent guidelines, (2) separately manage the
process and stormwater from outside the process units, a
pollution prevention activity that would address future
stormwater rules, (3) eliminate the potential for future
groundwater contamination for the sewer system, (4) ease
compliance with RCRA toxicity characteristic, waste listings, and
5-8
minimum technology requirements, and (5) assist with future
compliance with ozone non-attainment requirements, new source
performance standards for refinery wastewater treatment systems,
and potential refinery MACT standards.
Finally, in the study cost analysis, Amoco used the same
costing techniques for all the sources but these techniques are
not completely consistent with the approach generally used by
EPA. The main cost difference identified is the use of a 5 year
project life for amortization of project costs rather than a 15
year life used in EPA analyses. This means the costs are
internally comparaole, but should be used with caution if they
are to be compared against EPA cost estimates.
V. other concerns
In responding to comments on the study, Amoco raised issues
not directly related to the study that require comments for the
record. The following responds to several of these issues.
Chemdat emission models - Amoco appears to be highly
critical of the use of the Chemdat7 emission models for standards
development. These models were developed for EPA's Office of
Research and Development in the early 80's. They have been peer
reviewed by academ.ia, industry, and government on several
occasions. These models are based on the emission mechanisms of
the source and use the key parameters as inputs, such as the
amount of benzene entering a system. The use of modelling in
standards development is a standard and well-accepted practice.
This is an especially good use of models because annual average
inputs can be used to estimate long-term emissions.
In criticizing Chemdat7, Amoco cites selected data from the
Chemdat7 background document (Reference 5) that indicate the
models overstate emissions. On balance, a review of all of the
data in the report~, rather than just selected data, shows that
Chemdat7 sometimes overpredicts and sometimes underpredicts
emissions as compared to measured emissions. There are, of
course, uncertainties in both the emission measurements and
emission estimates from Chemdat7 so on balance the models are
generally considered to be reasonable predictors of emissions.
Benzene concentration data - In addition, in the draft
report Amoco compares the benzene concentration data used in the
development of thE! benzene waste rule with measured data from the
study. Although the study final report has not been published,
these data have already been submitted to EPA as official
comments in response to the proposed clarifications to the
benzene NESHAP. Because the concentrations measured in the study
were significantly less than those used in the analysis of the
benzene rule, this comparison is being used in an attempt to
indicate that the Agency's data base for the standards is
5-9
insufficient and the standard should be reanalyzed. A detailed
comparison of the basis for these numbers, however, shows that
this comparison is not valid.
The benzene rule wastewater concentration data were
calculated values based on the concentration of benzene in
process fluids at ,equilibrium with wastewater at the point the
wastewater is generated. This would be prior to (1) losses of
benzene to atmosphere due to emissions from the collection system
drains, junction boxes, and manholes, (2) dilution of the
concentration of benzene due to mixing with other wastewaters
that do nc~ contain benzene, and (3) removal of benzene with the
recovered oil in the in-unit API separators. The Amoco data to
which these are compared were samples of the water phase in the
first junction box after the process unit, which is after
reductions in the benzene concentration due to the emissions,
dilution, and removal described above. In addition, Amoco's
samples represent only a portion of the wastewater stream; they
only measured the benzene content of the water phase and not of
any oil phase that may have been present. This is especially
significant because most of the benzene in the wastewater stream
would partition into the oil phase. The water quality volume
states that an oil phase was generally present in the wastewater
system.
Flux chamber testing - The flux chamber measures emissions
from an area source by covering an area and capturing the emitted
vapors for measurement. The flux chamber does a reasonably good
job of measuring the emission rate from individual points within
an area source under the standardized conditions that exist
within the chamber. Measurements made with the flux chamber need
to then be extrapolated to estimate emissions from an area
source.
In several places in the study report it is suggested that
the flux chamber w'ould overstate emissions. Many arguments could
be made for the uncertainty of estimating emissions through flux
chamber tests because the standardized conditions in the chamber
modify the actual emissions environment. certain factors could
increase emissions, such as the wind within the chamber exceeding
the ambient wind, or they could reduce emissions, such as the
buildup of vapors within the chamber suppressing further
emissions or the chamber isolating the wastewater under it from
the wind-induced bulk mixing of the liquid, which is the limiting
factor in volatile organic emissions. On balance, without
additional stUdies it would be difficult to conclude that flux
chamber measurements are biased high or low.
VI. References
1. Basis for Benzene Waste Impact Calculations, Docket item IV-
B-4, February 16, 1990.
5-10
2. Industrial Wastewater Volatile Organic Compound Emissions -
Background Information for BACT/LAER Determinations, EPA 450/3-
90-004, January 1990.
3. Emission Test Report, Shell Manufacturing Complex, EMB Report

No. 88-IWW-06, Sep'tember 1991.
4. Emission Test Report, Rohm and Haas Company, EMB Report No.
91-IWW-07, May 1992.
5. Hazardous Waste Treatment, storage, and Disposal Facilities

(TSDF) - Air Emission Models, Review Draft, EPA 450j3-87-026R,
November 1989.
cc: Bruce Jordan, ESD (MD-13)

Howard Klee, Amoco Corporation
Joe Padgett, OAQPS (MD-11)
Mahesh Podar, OPPE (PM-221)
John Seitz, OAQPS (MD-10)
Michael Shapiro, OAR (ANR-443)
Lydia Wegman, OAQPS (MD-10)
Jim Weigold, OAQPS (MD-10)
Susan Wyatt, CPB (MD-13)
5-11
Discussion of MemoJ~andum from Office of Air Quality Planning and
Standards Dated June 1, 1992 by K. C. Hustvedt
The referenced Memorandum is included preceding these notes.

Direct quotations or topical headings from the Memorandum are
provided in bold, followed by discussion.
1. NESHAP Issues
Many of Mr. Hustvedt's concerns relate to the Benzene Waste

Operations NESHAP regulation (abbreviated below as the Benzene
NESHAP or NESHAP), a rule to be finalized in late 1992. It is
worth noting that t:he Refinery is subj ect to hundreds of existing
and many proposed regulations. No specific legislation or
regulation was selected for particular study in this Project. The
Pollution Prevention Project began before formulation of the
NESHAP rule, with Cl primary focus on collecting data, particularly
where little existed, about refinery emission sources. Many of
the comments in this Memorandum have been previously discussed and
reviewed viith Mr. Hustvedt. See the preceding correspondence for
specific details.
Previous Submittals
Mr. Hustvedt discusses previous submittals made by ,~oco under

various regulatory requirements. Pages 2-3 of the Memorandum
again discuss Amoco's 90-day filing under the NESHAP rule. This
subject is discussed at length on pages 16-18 of the preceding
document and is not repeated here. In summary, the required 90-
day submittal was simply a way of determining if the Refinery
5-12
would or would not be covered by the proposed NESHAP regulation.
Since the Refinery's Total Annual Benzene Quantity (TAB) exceeded
the threshold level of 10 Mg/year, the Refinery is required to
meet requirement of the NESHAP rule. The data quality obtained
for this 90-day report was not sufficiently good to make
meaningful jUdgements about the absolute value of benzene
emissions from this facility. The 90-day report did not address
the subject of emissions, but rather simply cataloged wastewater
streams that contain benzene, following EPA specified procedures.
2. Emission Estimates
Pages 4-8 of the Memorandum discuss various aspects of emissions
estimates and measurements for wastewater systems. Once again,
this material was previously discussed with Mr. Hustvedt, as
documented in the preceding correspondence. It will not be
repeated here. The primary point of the many, many discussions
between OAQPS and j~oco, was to explain that a refinery has a
number of potential benzene emission sources. At Yorktown (and
other facilities--see below) benzene emissions from wastewater
sources are a small percentage of the total potential emissions.
The Agency has also been briefed by Sun Petroleum about benzene
emissions from many refinery sources (Sun, 1992). In Sun's case,
emissions were calculated using OAQPS approved modeling procedures
for wastewater sources (and estimated using AP-42 factors for
other sources) at 1:he Marcus Hook Refinery. No measurements were
made. The attached Figure 1 shows both the Sun (Marcus Hook) and
Amoco (Yorktown) emissions. The two refineries have different
5-13
capacities and configurations. Yet, from this figure it is clear
that wastewater sources are a relatively minor contributor to
total potential emissions.One significant difference between the
two facilities is 1:he number of API separators present: Marcus
Hook has 14, Yorktown has 1. This difference is reflected in
higher calculated emissions from Marcus Hook for this source
category. Both facilities have approximately the same emissions
on a per separator basis.
Mr. Hustvedt has frequently cited previous studies as the basis
for their current calculation methods for wastewater sources. We
appreciate OAQPS recently making copies of these studies available
to Amoco for study. One involved a study of Shell Oil Company's
Deer Park facility near Houston Texas (EPA, 1991). A second
involved a study of emissions from a Rohm and Haas chemical plant
(EPA, 1992).
Both Amoco and OAQPS recognize that emission measurements are
difficult. Like many experimental programs, such measurements
involve uncertainty. However, based on our review of these
documents both studies appear to have serious limitations, as
discussed below.
Shell Study
This report was part of work completed by Radian Corporation to
develop and test Method 25D--a method to determine potential
organic emissions from a wastewater sample. The goals of this
study were to:
5-14
(1) determine the analytical and sampling variability of method
25D.
(2) determine compounds present in waste water.
(3) compare quantities of compounds removed by the method to
the quantities of compounds present in the water stream.
(4) compare concentrations of compounds found in sewer
collection systems to concentrations found in the vapor
(head) space.
This last task, which is most relevant to the measurements made in
the present Amoco/EPA study, was performed by the Research
Triangle Institute (RTI) for EPA. It was not discussed in detail
in Radian's report" but included as an Appendix. The copy of the
report supplied by OAQPS was, unfortunately, missing the actual
sampling data from sewer measurements. Tables 2-9 through 2-21
which contain the results are not included in the document. Every
odd-numbered page in Appendix G is missing. RTI used two testing
devices to measure gas phase concentrations of organics in the
sewer system: a TIN sniffer and an HNu meter. The TLV device
showed 1200 ppm, and the HNu meter showed 80 ppm of benzene in the
sewer vapor space. A third measurement technique collected a
sample of the headspace gas in a canister and analyzed it
following EPA method 8240. The resulting benzene concentration
was 540 ppm. This wide variation in measurements is not discussed
in the report material we received. More troublesome, the
expected equilibrium concentration of organics should have been 15
5-15
ppm, based on measured liquid phase concentrations. All
measurements therefore appear to have exceeded equilibrium values-
-a thermodynamic impossibility.
Rohm and Haas
In this study conducted by Radian for EPA, emissions were measured
at four points in an underground sewer system located at a Roh~
and Haas chemical plant. Emission rates were calculated from gas
flow rates and gas phase concentrations, exactly the same method
used at Yorktown. The vapor flow rates were based on short term
tests, which showed a large range. It appears that only one gas
phase concentration sample was collected, during the last 8 hours
of the test program at sample point L/Vl.
A number of liquid phase samples were collected with the intention
of completing a material balance on the sewer system. The plan
was to cross-check measured air emissions with changes in liquid
phase concentrations. This was not successful, as stated in the
report: "total air emissions from the sewer system do not equal
the rate of volatile tracer compound mass lost from the water." In
one set of measurem,ents, a TeE tracer showed air emissions of 1055
mg/minute, while wa'ter concentration measurements showed a loss of
8320 mg/minute. In this case, the emissions estimates developed
by Radian appear no better, but possibly worse than the
measurements completed in the Amoco/EPA study. Radian also
assisted with the ~noco/EPA measurement program.
5-16
3. cost Estimates
compliance Approach
While we agree there are several possible approaches permitted

under the benzene 'waste operations NESHAP, only one appeared to be
acceptable from a combination of compliance, future regulatory
actions, minimizing waste generation, and safety. This was the
approach Amoco chose to use at Yorktown. Mr. Hustvedt correctly
points out that Amoco rejected simply installing carbon canisters
on each sewer vent as a control technique. This approach may
reduce capital cost, but has high operating costs and generates
SUbstantial quanti"ties of solid waste in the form of spent carbon.
In addition, regene~ation of the carbon generates other airborne
wastes, such as criteria pollutants, requires excessive waste
handling, and potential occupational exposure problems. While
these additional wastes generated are not considered under the
NESHAP rule, they are, nevertheless, direct byproducts of this
rule. Amoco chose an alternative because we did not believe it
prudent to solve an air pollution problem by generating solid
waste and other air pollutants.
In a similar way, using a steam stripper to remove benzene from

wastewater has a large operating cost and generates significant
criteria pollutants through the need for additional steam
generation. As explained by EPA, steam stripping did not
necessarily eliminate the need for direct emission controls on
sewer systems such as carbon canisters.
5-17
Economic Analysis
As Mr. Hustvedt observed, the cost methodology used in this
project differs from EPA on several points. The methodology used,
however, was agreed to by the joint Amoco/EPA Workgroup which
managed this Project. As to differences: first, Agency capital
estimates are typically based on open literature correlations for
capital equipment costs as a function of processing capacity.
Amoco has found thE~se to be of very poor quality, typically
underestimating capital costs by factors of 2-5. Most industrial
firms, including Arnoco, have developed their own cost information
based on many years of engineering and construction experience
with the types of equipment peculiar to their industry. steam
strippers are commonly used in petroleum processing, and there is
a great deal of good, albeit proprietary, cost data available.
Second, the Agency cost estimates for steam strippers cited by Mr.
Hustvedt as the basis for the NESHAP rulemaking use materials of
construction which are inappropriate for the streams being
treated. The materials of construction included in the cost
estimate are not of sufficient quality (primarily metallurgy) to
be serviceable with these streams for typical equipment lifetimes
(20 years or more) expected in refinery service. Using
appropriate metallurgy for this service would increase the capital
cost above EPA's estimate. Also, the Agency's cost values for
estimating the cost effectiveness of steam strippers was based on
1986 cost data. Industry typically uses current cost information,
or adjusts older data to account for inflation. such adjustments
5-18
were not made in determining the impact of the NESHAP rule on the
regulated community. All three factors--proper materials
selection, use of correct capital cost factors, and the effects of
inflation--were properly accounted for in the cost estimates
prepared for this Project.
Financial analysis of each option also used several features which
differ from normal EPA practice. Federal income taxes were
factored in all economic analyses. These are normally excluded
from EPA calculations, but must be paid by industrial concerns.
Tax consequences have a major impact on project economic
evaluations. Equipment costs were amortized according to current
IRS regulations which provide for a 10-year amortization period.
EPA typically uses a longer project time period.
4. Other Items
Models
Pages 14 of the "Response to General Comments" discusses the
subject of modeling at some length. This will not be repeated
here. However, several items in Mr. Hustvedt's Memorandum dated
June 1, 1992, deserve comment.
CHEMDAT7
Amoco recognizes the utility (and limitations) of mathematical
models. The CHEMDAT7 model is cited by Mr. Hustvedt as the basis
for estimated emissions from wastewater sources. The comparison
of field data and calculations shown in previous correspondence
show that this model consistently overpredicts emissions (EPA,
5-19
1989a). Data selected for comparison were chosen only where it
was possible to ma}~e side-by-side comparisons of measured and
estimated emissions. Unfortunately, there are relatively few
opportunities, because emission measurement data is limited. In
several places emission measurements were inferred rather than
"measured" based on material balances. In Amoco's experience,
material balance te~chniques are not sufficiently accurate to
provide a number for comparison. This conclusion appears to have
been confirmed by :Radian in the Rohm and Haas study cited above.
Amoco has offered to work with OAQPS, sharing data and techniques
developed in severa.l ongoing emission measurement programs now
underway at our facilities. To date, this offer has not been
accepted.
other orga.nizations have noted similar concerns about the

inaccuracy of CHEMDAT7 model predictions. The American Petroleum
Institute completed a research project to measure benzene,
toluene, ethylbenzene and xylene (BTEX) emissions from refinery
wastewater impoundments in 1990. The objective of the program was
to evaluate EPA's CHEMDAT7 model used to estimate emissions from
hazardous waste storage, treatment and disposal facilities.
Concurrent measurements of BTEX wastewater concentrations and BTEX
airborne emissions 'were made at a phenolic equalization basin and
retention basin at a refinery. Emissions were measured using a
conventional up-wind/down-wind technique along with simUltaneous
remote-sensing measurements. Good agreement was found between the
5-20
up-wind/down-wind and remote-sensing measurements. Comparison of
the measured emissions with the CHEMDAT7 modeled emissions showed
that the model oVerpredicted emissions by more than an order of
magnitude (API, 1990). These results were communicated to
Mr. Hustvedt some -time ago.
Peer Review
To the best of our knowledge, the CHEMDAT7 model has not been peer
reviewed as requested by the EPA Science Advisory Board
"Resolution on the Use of Mathematical Models" (EPA, 1989b). That
Resolution raises a number of issues regarding the use of models
in environmental decision-making which have not been observed in
the use of CHEMDAT7. We encourage OAQPS to undertake the kind of
peer review and field validation suggested by the Science Advisory
Board.
5-21
References
API, 1990. Indaco Air Quality Services and the University of

Denver, "Measurement of the BTEX Emission Fluxes from
Refinery wastewater Impoundments Using Atmospheric Tracer
Techniques," API Publication No. 4518, American Petroleum
Institute, Washington, D.C., December 1990.
EPA, 1989a. "Hazardous Waste Treatment, storage, and Disposal

Facilities (T~mF) - Air Emission Models, Review Draft," EPA
450/3-87-026R November, 1989.
j,
EPA, 1989b. "Report of the Environmental Engineering committee:

Resolution on Use of Mathematical Models by EPA for
Regulatory Assessment and Decision-Making," EPA-SAB-EEC-89-
012, January 1989.
EPA, 1991.. "Emission Test Report, Shell Manufacturing Complex,"

EMB Report 88--IWW-06, September 1991.
EPA, 1992. "Emission Test Report, Rohm and Haas Company," EMB
Report No. 91--IWW-07, May 1992 .
Sun, 1992. Private communication, Sun Co., June 1992.
5-22
Benzene Sources at Refineries
API Sep 1
Tanks 10.5
~
Fugitive 37
Fugitive 5.8
lI.-"!
f
~ .......... Sewers 8 Sewers 2.5
~J
(~) Tanks
Blowdown Stacks 32
Barge Load 22
Amoco - Yorktown
Sun .. Marcus Hook
Units are tons/year

1992-06-30 PB92228600 Amoco Yorktown - EPA Pollution Prevention Project Volume II - Air Quality Data

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1992-06-30 PB92228600 Amoco Yorktown - EPA Pollution Prevention Project Volume II - Air Quality Data

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PB92228600

Amoco - U.S. EPA

Air Quality Data

REPRODUCED BY, NJJI

9. SPONSORING I MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORING I MONITORING

12a. DISTRIBUTION I AVAILABILITY STATEMENT 12b. DISTRIBUTION CODE

13. ABSTRACT (MaxImum 100 words)

14. SUBJECT TERMS 15. NUMBER OF PAGES

D. N. Blewitt, J. W. Keating and J. F. John

July 30, 1992

List of Figures iii

2.0 SOURCE SAMPLING 3

4.0 EMISSION INVENTORY 69

5.0 ACCURACY OF THE EMISSION INVENTORY FOR BTEX 94

5.2 Methodology Used to Compare Measured and 103

6.0 EXPOSURE MODELING 155

7.0 CONCLUSIONS 205

8.0 REFERENClllS 209

Appendix A Analyses of Tracer Data

*Appendix included in a separate document.

1 Comparison of VOC Emissions Determined from xii

5-1 Receptor Grid Used in Comparing Modeled 106

2-1 Speciatec:i Hydrocarbon Emissions from the 10-11

5-1 ISCST Control Switch Initialization 96

5-6 Summary of Comparisons of Predicted and 113

This is the second volume of air quality sampling and analysis

The multi-media sampling and analysis program showed that at this

As in any experimental program, there is uncertainty: in the

Howard Klee, Jr. Mahesh Podar

air quality evaluation of Amoco Oil Company's Yorktown

Refinery was conducted. The purpose of this portion of that

analyses was to define baseline air quality in terms of air

emissions and ambient air quality. This baseline was used

to evaluate potential impacts of different pollution

The estimation of baseline emissions was performed using

engineering calculations, USEPA emission factors and source

testing. Emissions were quantified for:

1) Benzene, toluene, ethylbenzene and xylene (BTEX)

2) Other SAF~ reported hydrocarbons (methanol,

ethylene, propylene, l,2,4-trimethylbenzene, MTBE,

cyclohexane, naphthalene, 1,3-butadiene)

It was found t.hat the refinery's total non-methane

hydrocarbon emissions are approximately 7,900 tons per year,

and benzene emissions were estimated to be 67 tons per year.

Source testing' performed on the API separator, sewer vents

and the coker pond provided realistic estimates of volatile

organic compound (VOC) emissions. One limitation of this

variability of voe emissions with time. This is a

limit:ation of all short-term emission measurements.

However, since the source testing was performed during warm

ambient temperatures, and since the refinery was operating

near or at maximum capacity, the emission estimates should

Figure 1 presents a summary of voe emission estimates as a

result of this study. Also, presented in Figure 1 are the

previous emission estimates that would have been assumed

without this field project. As indicated by comparison of

these two figures, without the improved revised emission

measurement inventory data, the benefits of pollution

prevention options could not have been accurately

The accuracy of the emission inventory for BTEX was tested

by comparing modeling predictions to ambient air

measurements. Because the design of the ambient sampling

enabled identification of specific source impacts under

steady meteorological conditions, a comparison could be made