1

Appendix 4: 

Analysis of data on short-term emission rates 

relative to long-term emission rates 
2

Analysis of data on short-term emission rates 

relative to long-term emission rates 

Ted Palma 

Roy Smith 

EPA/OAQPS/SBAG 

1. Introduction 

1.1. The problem 

The process of listing hazardous air pollutants (HAPs) provided by the Clean Air Act (CAA, 

section 112(b)(2)) explicitly includes acute toxicity as a listing criterion. For this reason, in 

addition to chronic exposures, EPA considers acute exposures in risk-based decision-making for 

the HAP regulatory program. Estimating acute exposures via dispersion modeling requires input 

data on hourly meteorological conditions (available for most areas of the US) and short-term 

emission rates of individual facilities (almost universally absent from the National Emissions 

Inventory (NEI), the Toxic Release Inventory (TRI), and state emission databases). 

Lacking short-term emission rates, we must estimate peak short-term rates based on annual 

average rates, which are available. For Risk and Technology Review (RTR) rulemakings, we 

have assumed that the 1-hour emission rate for each facility could exceed the annual average 

hourly emission rate by as much as tenfold, and further assumed that this tenfold emission spike 

could coincide with worst-case meteorological conditions and the presence of a human receptor 

at the facility boundary, as a means of screening for potentially significant acute exposures. 

In a consultation on the “RTR Assessment Plan”, a panel of the EPA’s Science Advisory Board 

(SAB), several reviewers questioned the appropriateness of the factor of ten; some even 

suggested that this tenfold assumption may underestimate actual maximum short-term emissions 

for some facilities, and thereby also underestimate maximum acute risks. The SAB 

recommended an analysis of available short-term emissions data for HAP to test this assumption. 

This analysis responds to that SAB recommendation and attempts to test the protectiveness of the 

tenfold assumption using a database of “event emissions” collected from facilities in the 

Houston-Galveston area, to compare events representative of HAP releases to long-term release 

rates. We welcome comments from the public on the methods used and the conclusions reached 

by this analysis. 

2. Methods 

2.1. Texas Commission on Environmental Quality event emissions database 

The Texas Commission on Environmental Quality (TCEQ) collects emissions data using online 

reporting required of any facility releasing 100 pounds or more of a listed chemical (primarily 

ozone-forming VOCs) during a non-routine event. The TCEQ data are intended to improve the 

state’s knowledge of how short-term releases affect tropospheric ozone levels in that area. The 

database we utilized in our analysis was a subset of the TCEQ data covering emission events that 
3

occurred in an eight-county area in eastern Texas during a 756-day period between January 31, 

2003 and February 25, 2005. 

The complete emissions event data were obtained in April 2007 from Cynthia Folsom Murphy, a 

research scientists with the University of Texas at Austin (UTA) Center for Energy and 

Environmental Resources. The data were provided in four Excel spreadsheets generated from an 

original MS Access file. We used these Excel files to reconstruct a MS Access database in order 

to facilitate selection of a representative subset of records for this analysis. 

Although some of the released substances were HAPs, this was incidental to the database’s 

primary purpose of enhancing the TCEQ’s knowledge of photochemical activity. Thus, more 

than 80% of the released mass was ethene and propene, neither of which are HAPs. The 

database included release events caused by accidents, equipment failures, maintenance, startup, 

and shutdown. It also contained facility names, information on amounts of individual 

compounds released. To provide a basis for comparing the event releases with “typical” 

emissions, the UTA staff included total VOC emissions data for each facility for calendar year 

2004, obtained from the EPA Toxic Release Inventory (TRI). The database did not contain any 

records for facilities that did not experience any reportable events during this period. 

2.2. Data filtering 

Because the event release data were intended for modeling short-term releases of ozoneproducing VOCs, the database includes releases from accidents (which are regulated under 

section 112(r) of the CAA and are therefore not considered in residual risk assessments) and 

releases of light hydrocarbon compounds that are not HAPs and are much more volatile than 

most HAPs. This intent of this analysis, on the other hand, was to evaluate short-term releases of 

HAPs due to normal process variability or scheduled startups, shutdowns, and maintenance, 

relative to long-term release rates. Because the full emission events database was not 

representative of likely HAP emissions normally considered under the residual risk program, we 

filtered the release data as follows in an attempt to improve its representativeness: 

1. Hydrocarbons of C5 or less were dropped, except that all HAPs (including non-VOCs) 

were retained regardless of molecular structure; 

2. Accidental releases were dropped, but all others (including startup, shutdown, and 

maintenance) were retained; 

3. Only facilities whose long-term VOC releases exceeded 0.068 tons per day (25 tons per 

year) were retained, to approximate the population of facilities likely to be subject to 

residual risk standards (i.e., major facilities); 

4. A few release records had to be dropped because their facility numbers did not link to any 

facility in the database; 

5. A few facilities had to be dropped because the database did not include their 2004 TRI 

VOC release information. 

2.3. Analysis 
4

Annual VOC emissions and emission event release data were both converted to lb/hr. In order to 

conform to our atmospheric dispersion models, which estimate ambient concentrations for 

periods of 1 hour or more, amounts released during events shorter than 1 hour were assigned to 

the whole hour. For example, a release of 100 lb in ten minutes was converted to 100 lb/hr. 

Events longer than 1 hour were converted normally, e.g., a release of 100 lb in 120 minutes was 

converted to 50 lb/hr. The event release rates for individual compounds were summed, yielding 

a total release rate for each event. This total release rate for each event was divided by the 

annual VOC release rate for the facility to derive the ratio of peak-to-mean emission rate for the 

event. 

3. Results and Discussion 

3.1. Database filtering 

The original database contained 505 individual contaminants, including multiple redundancies. 

These redundancies did not affect this analysis, so we did not resolve them. After filtering out 

light, non-HAP, VOCs, 317 contaminants remained (Table 1). 

The database contained release records for 150 unique facilities. Of these, 48 facilities (Table 2) 

were major VOC emitters that reported releases of at least one of the contaminants in Table 1. 

The database contained 3641 individual release events reported by the original 150 facilities. Of 

these, 319 events involved a Table 1 contaminant released by a Table 2 facility during startup, 

shutdown, or maintenance. For evaluating short-term releases for residual risk assessments, 

these 319 events comprise the most representative subset of the full database. 

3.2. Descriptive statistics 

For this subset of emission events, ratios of event release rate to long-term release rate varied 

from 0.00000004 to 74. Distribution statistics appear in Tables 3 and 4. The 99th percentile ratio 

was 9 (i.e., an event release rate nine times the long-term average). Only 3 ratios exceeded our 

default assumption of 10, and of these only one exceeded 11. The full cumulative probability 

density of the ratios is shown in Figure 1. 

Figure 2 shows the relationship between ratio and event duration. As expected, the ratio 

declined as duration increased. Only 18 events lasted less than 2 hours, but these events 

produced the three highest ratios. Figure 3 is a similar ratio vs. duration plot, but with duration 

as a percentage of total time. Only 35 events exceeded 1% of the total period covered by the 

database. Figure 4 shows the relationship between ratio and total amount released, and suggests 

that the highest ratios were produced by facilities whose routine VOC emissions were relatively 

small. Thus, the events themselves also tended to be relatively small in absolute terms. 

3.3. Discussion 

These results suggest that the tenfold ratio assumption for short-term releases is protective, and 

that the facilities for which it may underestimate event releases may tend to be smaller emitters. 

However, this analysis is limited in the following ways by the nature of the database and the 

filtering that we applied: 
5

1. The only long-term release data available from the database were total VOC emissions 

for 2004. Ideally, we would have preferred to have routine release rates for each 

individual contaminant. However, retrieving these data from other sources and linking 

them to this database was not feasible. 

2. Removing VOCs that are not representative of HAPs, and comparing the releases against 

all VOCs, would tend to underestimate the true ratios. This effect could be quantitatively 

large. 

3. Retaining HAPs that are not VOCs (such as toxic metals), and including them in the total 

to be compared against all VOCs, would tend to overestimate the true ratios. The size of 

this effect is not known, but seems likely to be less than for (2) above. 

4. The database contains only facilities that had at least one release event during the 

reporting period. The number of facilities in the statistical population that did not 

experience an event is not known. The lack of data for these facilities (whose ratios in 

this analysis would have been zero) would cause the descriptive statistics to be skewed 

toward an overestimate. The size of this effect is unknown. 

Table 1. Event emissions in the Houston-Galveston area. 

Representative contaminants included in the analysis, selected because 

they are either HAPs or VOCs with more than 5 carbon atoms. (These 

data were retrieved directly from the original database, which included 

multiple redundancies that did not affect the analysis and were left 

intact.) 

Contaminant HAP CAS SAROAD 

2-Methyloctane No 3221-61-2 90008 

2-Methylpentane No 107-83-5 43229 

2-methylhexane No 591-76-4 43263 

2-Methylpentane No 107-83-5 43229 

2,2,3-Trimethylpentane No 564-02-3

2,2,4-Trimethylpentane Yes 540-84-1 43250 

dimethyl butane No 75-83-2 43291 

2,3-Dimethylbutane No 79-29-8 43276 

2,3,4-Trimethylpentane No 565-75-3 43252 

2,3-Dimethylbutane No 79-29-8 43276 

2,4-Dimethylpentane No 108-08-7 43247 

2-methylheptane No 592-27-8 43296 

2-methylhexane No 591-76-4 43263 

2-Methylpentane No 107-83-5 43229 

3-Methylhexane No 589-34-4 43295 

3-Methylpentane No 96-14-0 43230 

3-Methylhexane No 589-34-4 43295 

3-Methylpentane No 96-14-0 43230 

3-Methylheptane No 589-81-1 43253 

3-Methylhexane No 589-34-4 43295 

3-Methylpentane No 96-14-0 43230 
6

Table 1. Event emissions in the Houston-Galveston area. 

Representative contaminants included in the analysis, selected because 

they are either HAPs or VOCs with more than 5 carbon atoms. (These 

data were retrieved directly from the original database, which included 

multiple redundancies that did not affect the analysis and were left 

intact.) 

Contaminant HAP CAS SAROAD 

Acetaldehyde Yes 75-07-0 43503 

Acetic Acid No 64-19-7 43404 

Acetonitrile Yes 75-05-8 70016 

Acetophenone Yes 98-86-2

Acrolein Yes 107-02-8 43505 

Acrylic acid Yes 79-10-7 43407 

Acrylonitrile Yes 107-13-1 43704 

alkylphenol No none

Benzene Yes 71-43-2 45201 

Benzo[a]anthracene Yes 56-55-3 46716 

Benzo[a]pyrene Yes 50-32-8 46719 

Benzo[b]fluoranthene Yes 205-99-2 46717 

Biphenyl Yes 92-52-4 45226 

Butanol No 35296-72-1

Butyl Acrylate No 141-32-2 43440 

t-Butyl Alcohol No 75-65-0 43309 

butylcyclohexane No 1678-93-9 90101 

Butyraldehyde No 123-72-8 43510 

C9 Aromatics No none

Naphthalene Yes 91-20-3 46701 

Nonane No 111-84-2 43235 

C9+ No none

Carbon tetrachloride Yes 56-23-5 43804 

Carbonyl Sulfide Yes 463-58-1 43933 

Chloral No 75-87-6

Trichloromethane Yes 67-66-3 43803 

Chlorothalonil No 1897-45-6

Petroleum No 8002-05-9

Petroleum No 8002-05-9

Cumene Yes 98-82-8 45210 

Cyclohexane No 110-82-7 43248 

Cyclohexanol No 108-93-0 43317 

Cyclohexanone No 108-94-1 43561 

Cyclohexanone No 108-94-1 43561 

Decane No 124-18-5 43238 

Decane No 124-18-5 43238 

1,2-Dichloroethane No 107-06-2 43815 

Diethylbenzene (mixture) No 25340-17-4 45106 

Methyl Ether No 115-10-6 43350 

Dimethylcyclohexane No 27195-67-1 98059 

Dimethylcyclopentane No 28729-52-4 90064 
7

Table 1. Event emissions in the Houston-Galveston area. 

Representative contaminants included in the analysis, selected because 

they are either HAPs or VOCs with more than 5 carbon atoms. (These 

data were retrieved directly from the original database, which included 

multiple redundancies that did not affect the analysis and were left 

intact.) 

Contaminant HAP CAS SAROAD 

Dimethylcyclopentane No 28729-52-4 90064 

Dimethyl formamide Yes 68-12-2 43450 

Dimethylhexane No 28777-67-5 90067 

Dimethyl pentane No 38815-29-1 90063 

Epichlorohydrin Yes 106-89-8 43863 

Ethyl Alcohol No 64-17-5 43302 

Ethyl Acrylate Yes 140-88-5 43438 

Ethyl Alcohol No 64-17-5 43302 

Ethyl Benzene Yes 100-41-4 45203 

Ethyl Chloride Yes 75-00-3 43812 

Ethylcyclohexane No 1678-91-7 43288 

ethylacetylene No 107-00-6 43281 

Ethyl Benzene Yes 100-41-4 45203 

Ethylene Oxide Yes 75-21-8 43601 

ethylmethylbenzene No 25550-14-5 45104 

formaldehyde Yes 50-00-0 43502 

Furfural No 98-01-1 45503 

straight-run middle distillate No 64741-44-2

Gasoline No 86290-81-5

Gasoline No 86290-81-5

Heavy Olefins No none

n-Heptane No 142-82-5 43232 

n-Heptane No 142-82-5 43232 

Heptylene No 25339-56-4

hexane Yes 110-54-3 43231 

hexane Yes 110-54-3 43231 

2-Methylpentane No 107-83-5 43229 

hexane Yes 110-54-3 43231 

Hexene No 25264-93-1 43289 

Indeno[1,2,3-cd]pyrene Yes 193-39-5 46720 

Isobutyraldehyde No 78-84-2 43511 

2-Methyl-1-propanol No 78-83-1 43306 

2-Methyl-1-propanol No 78-83-1 43306 

Isobutyraldehyde No 78-84-2 43511 

Isoheptanes (mixture) No 31394-54-4 43106 

2-Methylpentane No 107-83-5 43229 

2,2,4-Trimethylpentane No 540-84-1 43250 

2,2,4-Trimethylpentane No 540-84-1 43250 

Isopar E No 

Isoprene No 78-79-5 43243 

2-Propanol No 67-63-0 43304 
8

Table 1. Event emissions in the Houston-Galveston area. 

Representative contaminants included in the analysis, selected because 

they are either HAPs or VOCs with more than 5 carbon atoms. (These 

data were retrieved directly from the original database, which included 

multiple redundancies that did not affect the analysis and were left 

intact.) 

Contaminant HAP CAS SAROAD 

2-Propanol No 67-63-0 43304 

Cumene Yes 98-82-8 45210 

Isopropylcyclohexane No 696-29-7 90128 

Diisopropyl ether No 108-20-3 85005 

Kerosene No 64742-81-0

Methyl ethyl ketone No 78-93-3 43552 

Methyl isobutenyl ketone Yes 141-79-7

Methanol Yes 67-56-1 43301 

Methyl Acetylene No 74-99-7 43209 

Cresol Yes 1319-77-3 45605 

Methyl Chloride Yes 74-87-3 43801 

methyl cyclohexane No 108-87-2 43261 

Methyl ethyl ketone No 78-93-3 43552 

Iodomethane No 74-88-4 86025 

Methyl Mercaptan No 74-93-1 43901 

methyl cyclohexane No 108-87-2 43261 

Methylcyclopentane No 96-37-7 43262 

2-Methyldecane No 6975-98-0 98155 

Methylheptane No 50985-84-7 90045 

2-methylheptane No 592-27-8 43296 

2-Methyl nonane No 871-83-0 90047 

Tert-butyl methyl ether No 1634-04-4 43376 

meta-xylene No 108-38-3 45205 

Nonane No 111-84-2 43235 

Naphtha No 8030-30-6 45101 

Naphthalene Yes 91-20-3 46701 

Naphtha No 8030-30-6 45101 

Naphthalene No 91-20-3 46701 

Butyl acetate No 123-86-4 43435 

Butyraldehyde No 123-72-8 43510 

Nonane No 111-84-2 43235 

Nonane No 111-84-2 43235 

Octadecene No 27070-58-2

n-Octane No 111-65-9 43233 

Octene (mixed isomers) No 25377-83-7

ortho-xylene No 95-47-6 45204 

Parathion Yes 56-38-2

4-Aminohippuric Acid No 61-78-9

Phenol Yes 108-95-2 45300 

Silicone No 63148-62-9

Naphtha No 8030-30-6 45101 
9

Table 1. Event emissions in the Houston-Galveston area. 

Representative contaminants included in the analysis, selected because 

they are either HAPs or VOCs with more than 5 carbon atoms. (These 

data were retrieved directly from the original database, which included 

multiple redundancies that did not affect the analysis and were left 

intact.) 

Contaminant HAP CAS SAROAD 

Naphtha No 8030-30-6 45101 

Polyethylene No 9002-88-4

Poly(Isobutylene) No 9003-27-4

Chloromethyl pivalate No 18997-19-8

Process fuel gas No none

Propionic Acid No 79-09-4 43405 

Propylene oxide No 75-56-9 43602 

para-xylene No 106-42-3 45206 

Styrene Yes 100-42-5 45220 

Sulfolane No 126-33-0

t-Butyl Alcohol No 75-65-0 43309 

t-Butyl Alcohol No 75-65-0 43309 

tert-butyl hydroperoxide No 75-91-2

Toluene Yes 108-88-3 45202 

Aqualyte(TM), LSC cocktail No 25551-13-7 45107 

1,3,4-Trimethylbenzene No 95-63-6 45208 

trimethylcyclopentane No 30498-64-7 98058 

trimethylpentane No 29222-48-8 90092 

Undecane No 1120-21-4 43241 

Vinyl acetate Yes 108-05-4 43453 

Vinyl acetate Yes 108-05-4 43453 

Vinyl chloride Yes 75-01-4 43860 

vinyl resin No none

Vinylcyclohexane No 695-12-5

xylenes Yes 1330-20-7 45102 

xylenes Yes 1330-20-7 45102 

meta-xylene Yes 108-38-3 45205 

ortho-xylene Yes 95-47-6 45204 

para-xylene Yes 106-42-3 45206 

Mineral spirits No 64475-85-0 43118 

Propylene glycol No 57-55-6 43369 

Vinyl chloride Yes 75-01-4 43860 

1-Decene No 872-05-9 90014 

2-Ethyl-1-hexanol No 104-76-7 43318 

2-Pyrrolidone No 616-45-5

Aromatic No none

Decene No 25339-53-1 90014 

2-N,N-Dibutylaminoethanol No 102-81-8 86007 

Diisopropanolamine No 110-97-4 86004 

N,N-Dimethylethanolamine No 108-01-0 84004 

trifluoroethane No 27987-06-0
10

Table 1. Event emissions in the Houston-Galveston area. 

Representative contaminants included in the analysis, selected because 

they are either HAPs or VOCs with more than 5 carbon atoms. (These 

data were retrieved directly from the original database, which included 

multiple redundancies that did not affect the analysis and were left 

intact.) 

Contaminant HAP CAS SAROAD 

2,2'-Oxybisethanol No 111-46-6 43367 

Hydrocarbons No none

Methyl Formate No 107-31-3 43430 

Isopropylamine No 75-31-0 86014 

n-Butanol No 71-36-3 43305 

Polypropylene glycol ether No 

N-Vinyl-2-Pyrrolidinone No 88-12-0

1,1-Di(t-Amylperoxy) 

Cyclohexane No 15667-10-4

1,2,3-Trimethyl-4-ethylbenzene No none

2-Methyldecane No 6975-98-0 98155 

2-methylheptane No 592-27-8 43296 

2-Methyl nonane No 871-83-0 90047 

2,5-Dimethylhexane-2,5-

dihydroperoxide No 3025-88-5

Butyl ether No 142-96-1 43372 

1,2-Dichloroethane Yes 107-06-2 43815 

Hydrindene No 496-11-7 98044 

Methylheptane No 50985-84-7 90045 

methyl methacrylate No 80-62-6 43441 

Naphtha No 8030-30-6 45101 

hexane Yes 110-54-3 43231 

tert-amyl hydroperoxide No 3425-61-4

1,3,4-Trimethylbenzene No 95-63-6 45208 

n-Butanol No 71-36-3 43305 

2-Butoxy ethanol Yes 111-76-2 43308 

hexane Yes 110-54-3 43231 

cycloheptane No 291-64-5 43115 

n-Heptane No 142-82-5 43232 

n-Octane No 111-65-9 43233 

Hexyl Carbitol No 112-59-4

Nonene No 27215-95-8

Silane, ethenyltrimethoxy No 2768-02-7

tetrahydrofuran No 109-99-9 70014 

Vinyl chloride Yes 75-01-4 43860 

Methyl Formate No 107-31-3 43430 

Phenyl ether No 101-84-8

phosgene Yes 75-44-5

1,2-Dichloroethane No 107-06-2 43815 

2-Butoxy ethanol Yes 111-76-2 43308 

Gasoline No 86290-81-5

1-Tridecanol No 112-70-9
11

Table 1. Event emissions in the Houston-Galveston area. 

Representative contaminants included in the analysis, selected because 

they are either HAPs or VOCs with more than 5 carbon atoms. (These 

data were retrieved directly from the original database, which included 

multiple redundancies that did not affect the analysis and were left 

intact.) 

Contaminant HAP CAS SAROAD 

1,2,4-Trichlorobenzene Yes 120-82-1 45208 

2-(2-Butoxyethoxy)ethanol Yes 112-34-5 43312 

2,3,4-trihydroxybenzophenone 

Ester No 1143-72-2

Methyl n-amyl ketone No 110-43-0 43562 

4,4-Cyclohexylidenebis[phenol] No 843-55-0

Anisole No 100-66-3

2-Butoxy ethanol Yes 111-76-2 43308 

Cresol-Formaldehyde novolac 

Resin No proprietary

Decane No 124-18-5 43238 

gamma-Butyrolactone No 96-48-0

Dimethyl pentane No 38815-29-1 90063 

Dodecyl Benzenesulfonic Acid No 27176-87-0

Ethanol Amine No 141-43-5 43777 

ethyl lactate No 687-47-8

Hexamethyldisilazane No 999-97-3

Methyl ethyl ketone No 78-93-3 43552 

Cresol Yes 1319-77-3 45605 

Naphthalene Sulfonic Acid Resin No 

Naphthalene Sulfonic Acid Resin No 

n-Butanol No 71-36-3 43305 

Decane No 124-18-5 43238 

1-Methyl-2-pyrrolidinone No 872-50-4 70008 

Pentyl Ester Acetic Acid No 

Phenol Formaldehyde Resin, 

Novolac No 

Phenol Formaldehyde Resin, 

Novolac No 

Propylene Glycol Monomethyl 

Ether No 107-98-2 70011 

Pyrocatechol No 120-80-9

Carbon Disulfide Yes 75-15-0 43934 

Hexene No 592-41-6 43245 

VOC No none

Methacrylic acid No 79-41-4 84009 

Methyl 3-hydroxybutyrate No 1487-49-6

t-Butyl Alcohol No 75-65-0 43309 

methyl valeraldehyde No 123-15-9

Butyl Methacrylate No 97-88-1 85008 

dipropyl ether No 111-43-3

n-Propanol No 71-23-8 43303 

Propyl propionate No 106-36-5 86052 
12

Table 1. Event emissions in the Houston-Galveston area. 

Representative contaminants included in the analysis, selected because 

they are either HAPs or VOCs with more than 5 carbon atoms. (These 

data were retrieved directly from the original database, which included 

multiple redundancies that did not affect the analysis and were left 

intact.) 

Contaminant HAP CAS SAROAD 

1,2-Epoxybutane Yes 106-88-7

Methylamine No 74-89-5

1,1-Dimethylcyclohexane No 590-66-9

1,1-Dimethylcyclopentane No 1638-26-2

2-Methylpentane No 107-83-5 43229 

dimethyl butane No 75-83-2 43291 

2,3,3-Trimethylpentane No 560-21-4

2,3-Dimethylhexane No 584-94-1

2,3-Dimethylpentane No 565-59-3

2,4-Dimethylhexane No 589-43-5

2,5-Dimethyl-hexane No 592-13-2

2-Butoxy ethanol Yes 111-76-2 43308 

2-mercaptoethanol No 60-24-2

Bisphenol A No 80-05-7

straight-run middle distillate No 64741-44-2

4-Vinylcyclohexene No 100-40-3

straight-run middle distillate No 64741-44-2

Allyl alcohol No 107-18-6

xylenes Yes 1330-20-7 45102 

Naphthalene Yes 91-20-3 46701 

3-Methylethylcyclohexane No 

VOC No none

Gasoline No 86290-81-5

Butyl ether No 142-96-1

dimethyl butane No 75-83-2

Dodecene No 25378-22-7

Styrene Yes 100-42-5 45220 

tetrahydrofuran No 109-99-9 70014 

hexane Yes 110-54-3 43231 

2-Propanol No 67-63-0 43304 

liquified petroleum gas No 68476-85-7

Methyl acetylene propadiene No 

methyl isobutyl ketone Yes 108-10-1

Methyl n-amyl ketone No 110-43-0 43562 

Methylpentane No 43133-95-5

Tert-butyl methyl ether Yes 1634-04-4 43376 

Toluene Yes 108-88-3 45202 

Mineral oil No 8012-95-1

Gasoline No 86290-81-5

2,2-Dimethylpropane No 463-82-1 43222 

n-propylbenzene No 103-65-1
13

Table 1. Event emissions in the Houston-Galveston area. 

Representative contaminants included in the analysis, selected because 

they are either HAPs or VOCs with more than 5 carbon atoms. (These 

data were retrieved directly from the original database, which included 

multiple redundancies that did not affect the analysis and were left 

intact.) 

Contaminant HAP CAS SAROAD 

propylcyclohexane No 1678-92-8

n-Octane No 111-65-9 43233 

ortho-xylene No 95-47-6 45204 

Gasoline No 86290-81-5

propylenimine No 75-55-8

Gasoline No 86290-81-5

Technical White Oil No 

Total Alkylate - non-speciated No 

Trichloroethylene Yes 79-01-6

Di(2-ethylhexyl) 

peroxydicarbonate No 16111-62-9

trimethylcyclopentane No 30498-64-7 98058 

Ultraformate No 

4-Vinylcyclohexene No 100-40-3
14

Table 2. Event emissions in the Houston-Galveston area. Major emitters 

reporting at least one release event of a representative substance. 

Company Name 

2004 VOC Emission 

Rate (lb/h) 

ATOFINA PETROCHEMICALS LA PORTE PLANT 47.88 

BALL METAL BEVERAGE CONTAINER CONROE 

FACILITY 

24.18 

BASF FREEPORT SITE 46.47 

BELVIEU ENVIRONMENTAL FUELS 112.3 

BOC GROUP CLEAR LAKE BOC GASES PLANT 9.52 

BP AMOCO CHEMICAL CHOCOLATE BAYOU PLANT 130.4 

BP AMOCO CHEMICAL PASADENA PLANT 36.92 

BP AMOCO POLYMERS 57.18 

BP PRODUCTS NORTH AMERICA TEXAS CITY 737.4 

BP TEXAS CITY CHEMICAL PLANT B 112.2 

CELANESE BAY CITY PLANT 17.12 

CELANESE CLEAR LAKE PLANT 53.11 

CELANESE PASADENA PLANT 5.934 

CHEVRON PHILLIPS CEDAR BAYOU PLANT 105.3 

CHEVRON PHILLIPS CHEMICAL SWEENY COMPLEX 106.7 

CHEVRON PHILLIPS HOUSTON CHEMICAL COMPLEX 215.7 

CROWN BEVERAGE PACKAGING 18.05 

CROWN CENTRAL PETROLEUM PASADENA PLANT 114.3 

CROWN CORK & SEAL 18.10 

DEER PARK LIQUID STORAGE TERMINAL 124.8 

DOW CHEMICAL LA PORTE SITE 5.902 

DOW TEXAS OPERATIONS FREEPORT 203.2 

E I DUPONT DE NEMOURS AND COMPANY - LA 

PORTE PLANT 

51.30 

EQUISTAR CHEMICALS CHANNELVIEW COMPLEX 275.4 

EQUISTAR CHEMICALS CHOCOLATE BAYOU 

COMPLEX 

84.87 

EQUISTAR CHEMICALS LA PORTE COMPLEX 90.97 

EXXON MOBIL CHEMICAL BAYTOWN OLEFINS PLANT 84.73 

EXXONMOBIL CHEMICAL BAYTOWN CHEMICAL 

PLANT 

313.7 

EXXONMOBIL CHEMICAL MONT BELVIEU PLASTICS 

PLANT 

40.64 

GOODYEAR HOUSTON CHEMICAL PLANT 85.68 

ISP TECHNOLOGIES TEXAS CITY PLANT 22.12 

KANEKA TEXAS CORPORATION 20.55 

KINDER MORGAN LIQUID TERMINALS PASADENA 913.9 

KINDER MORGAN LIQUIDS TERMINALS 132.7 

LBC HOUSTON BAYPORT TERMINAL 12.83 

LYONDELL CHEMICAL BAYPORT PLANT 30.04 

LYONDELL CHEMICAL CHANNELVIEW 74.15 

MARATHON ASHLAND PETROLEUM TEXAS CITY 

REFINERY 

111.8 

MOBIL CHEMICAL HOUSTON OLEFINS PLANT 26.29 

MORGANS POINT PLANT 31.03 

PASADENA PLANT 13.40 
15

Table 2. Event emissions in the Houston-Galveston area. Major emitters 

reporting at least one release event of a representative substance. 

Company Name 

2004 VOC Emission 

Rate (lb/h) 

SHELL OIL DEER PARK 405.2 

SOLUTIA CHOCOLATE BAYOU PLANT 53.09 

STOLTHAVEN HOUSTON TERMINAL 7.347 

SWEENY COMPLEX 157.1 

UNION CARBIDE TEXAS CITY OPERATIONS 174.4 

VALERO REFINING TEXAS CITY 260.1 

WHARTON GAS PLANT 7.552 

Table 3. Frequency distribution for ratio of event 

emission rate to long-term emission rate 

Bin Frequency 

Cumulative 

Frequency 

1.00E-08 0 0 

3.16E-08 0 0 

1.00E-07 2 2 

3.16E-07 1 3 

1.00E-06 0 3 

3.16E-06 2 5 

1.00E-05 1 6 

3.16E-05 2 8 

1.00E-04 5 13 

3.16E-04 9 22 

1.00E-03 15 37 

3.16E-03 28 65 

1.00E-02 33 98 

3.16E-02 41 139 

1.00E-01 59 198 

3.16E-01 38 236 

1.00E+00 33 269 

3.16E+00 31 300 

1.00E+01 16 316 

3.16E+01 2 318 

1.00E+02 1 319 

3.16E+02 0 319 
16

Table 4. Statistics for ratio of event emission 

rate to long-term emission rate 

Statistic for Ratio Value 

Median 0.043923 

75th %ile 0.342655 

90th %ile 2.204754 

95th %ile 3.344422 

96th %ile 3.400832 

97th %ile 3.8126 

98th %ile 4.790098 

99th %ile 8.973897 

Max 74.37138 

Average 0.815352 

Figure 1. Cumulative probability density for ratio of event to routine emission rates. 

Cumulative probability of event ratios

0

50

100

150

200

250

300

350

1.E-07 1.E-06 1.E-05 1.E-04 1.E-03 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04

Ratio of event emission rate to long-term emission rate

n
17

Figure 2. Relationship between ratio of event to duration emission rate and emission 

duration.

Event ratio vs. duration

1.E-08

1.E-07

1.E-06

1.E-05

1.E-04

1.E-03

1.E-02

1.E-01

1.E+00

1.E+01

1.E+02

1 10 100 1,000 10,000 100,000

Event duration (min)

Ratio -- event emission rate to long-term emission rate

Figure 3. Relationship between ratio of event to duration emission rate and emission duration, as 

percentage of total time. 

Event ratio vs. duration

1.E-08

1.E-07

1.E-06

1.E-05

1.E-04

1.E-03

1.E-02

1.E-01

1.E+00

1.E+01

1.E+02

0% 1% 2% 3% 4% 5% 6% 7% 8%

Event duration (as % of total time)

Ratio -- event emission rate to long-term emission rate
18

Figure 4. Relationship between ratio of event to duration emission rate and total amount emitted 

during the event. 

Event ratio vs. 2004 VOC releases -- by event

1.E-08

1.E-07

1.E-06

1.E-05

1.E-04

1.E-03

1.E-02

1.E-01

1.E+00

1.E+01

1.E+02

1 10 100 1,000

Long-term VOC releases (lb/hr)

Ratio -- event emission rate to long-term emission rate
Technical Memorandum

TO: EPA Docket No. EPA-HQ-OAR-2010-0682 

 

FROM: Brenda Shine, Environmental Engineer

Refining and Chemicals Group, SPPD (E143-01)

DATE: March 15, 2012

SUBJECT: Derivation of Hourly Emission Rates for Petroleum Refinery Emission Sources 

Used in the Acute Risk Analysis

I. Purpose:

This memorandum documents the assumptions used to derive the hourly emission rates used to 

estimate acute risks from emissions of petroleum refinery emission sources. In past Risk and 

Technology (RTR) rulemakings, when we have lacked hourly emissions data or other specific 

information about the source category processes, we assumed that the 1-hour emission rate for 

any emission point could be 10 times higher than its average hourly emissions, calculated by 

dividing annual emissions by 8760 hours per year. The basis for this assumption was derived 

from an analysis of short term release information collected from facilities in the HoustonGalveston area and a comparison against routine emission rates for an entire facility. The 

conclusions of this analysis were that the hourly emissions from any single release event to the 

average annual VOC release rate for an entire facility was seldom greater than a factor of 10. 

For the petroleum refinery source category, we have additional knowledge of the emission point 

release characteristics that enable us to refine the default factor of 10 to something more realistic 

for this source category.

 

II. Acute Factors for the Petroleum Refinery Source Category:

Instead of using the default factor of 10 described above, we estimated variability of hourly 

emissions based on the operating characteristics of refinery emission sources in the following 

manner: 

a. For many sources that are associated with continuous operations and are essentially 

steady state, such as Fluid Catalytic Cracking Units (FCCU), and sulfur recovery plants 

(SRU), we would not expect significant variability in hourly emissions. Typical source 

test variablility is typically ±30 to 50%. We have applied an hourly multiplier of 2 to 

estimate maximum hourly rates as an upper range of the expected variability. This 

assumption was used for the following types of sources: FCCU, SRU, Chemical 

Processes, miscellaneous process vents, refinery processes (not specified) and 

incinerators.

b. For delayed cokers, we considered the average venting cycle time in calculating our 

hourly emission rate. The process cycle for delayed cokers is 1 day (24 hours), with the 
2 

depressurization vent having an average venting cycle time of, on average, 2 to 3 hours 

per cycle. Since the depressurization vent opens for 730 to 1,095 hours per year, a factor 

of 8 to 12 times the annual average emission rate could be used to account for this 

emission process. The emissions are expected to be somewhat variable, with higher 

emissions at the start of the venting cycle. We therefore applied an hourly multiplier of 

20 to estimate maximum hourly rates for delayed coker emissions. 

c. There are three types of catalytic reformers: Continuous, cyclic, and semi-regenerative. 

Continuous reformers (SCC 30601602) are expected to have stable operations (much like 

the FCCU and SRU), so a factor of 2 is appropriate for estimating the maximum hourly 

emissions rate. Cyclic reformers (SCC 30601603) typically vent for 2,000 to 4,000 hours 

per year, suggesting a factor of 2 to 4 for these units. However, their emissions over the 

venting period are expected to be somewhat variable, so a factor of 10 is applied as a 

conservative estimate. Semi-regenerative reformers (SCC 30601604) are expected to 

vent approximately 10-15 days per year, suggesting a factor of 30 or 40. The venting is 

not expected to be uniform over this period, so a factor of 60 is applied for these units. 

d. For evaporative loss sources such as wastewater, we expect moderate variability in 

maximum hourly emissions from annual average emissions. Emissions from wastewater 

are dependent on organic loading to the unit and on the mass transfer (volatilization) rate 

from the wastewater surface (which is dependent on the wastewater temperature and air 

wind speed). The loading rates are expected to vary by a factor of 2 during normal 

operations and the mass transfer rates are expected to vary by a factor of 2 due to 

seasonal/meterological variations. We therefore applied an hourly multiplier of 4 to 

estimate maximum hourly rates from wastewater sources. 

e. For fugitives from equipment leaks, we note that the current methods of estimating 

emissions make use of correlation equations in conjunction with Method 21 readings that 

ultimately provide an hourly emission rate for the monitoring period in question. The 

actual emission rates estimated based on the direct Method 21 readings are commonly 

divided by two to estimate the average emission rate between monitoring intervals (i.e., 

assuming the leak started mid-way between monitoring intervals as described in the 

emissions protocol). We expect the emission estimates from the direct Method 21 

readings to provide a direct measure of the maximum hourly emissions (as leak repair 

will be applied to reduce hourly emissions immediately after a monitoring cycle). 

Therefore, we applied an hourly multiplier of 2 to estimate maximum hourly rates from 

the annual average emission rates.

f. For storage vessels, higher hourly rates from loading operations can occur; however, the 

majority of tanks are floating roof tanks; emissions from these tanks are associated with 

wind-driven losses from fitting controls and clingage from exposure of external floating 

roof tank shells. These emissions would not be expected to vary as significantly as fixed 

roof tanks, but the emissions from floating roof tanks are expected to be dependent on 

temperature (seasonal variability) and, in the case of external floating roofs, wind speed. 
3 

There may also be variability in the crude oil processed or the intermediates and products 

stored in a given tank. As with wastewater sources, each of these factors is expected to 

cause a factor of 2 variability. We therefore applied an hourly multiplier of 4 to estimate 

maximum hourly rates from storage tanks.

g. For other transfer and loading operations, maximum hourly rates can be approximated 

from pumping rates; a factor of 2 for these sources would not adequately account for 

higher maximum hourly emissions in most cases. Considering the hours of actual 

product loading during the year (commonly 1,000 to 2,000 hours per year), we applied a 

factor of 10 to these emission sources.