## MEMORANDUM

DATE: January 9, 2013

TO: Docket EPA-HQ-OAR-2011-0135

FROM: Catherine Yanca, Office of Transportation and Air Quality/Assessment and Standards Division

SUBJECT: Mobile Source Hydrocarbon Speciati on Profiles for the Tier 3 Rule NPRM and Anti-backsliding Study AQ Modeling

Mobile Source Speciation Profile s used in the Tier 3 NPRM

To model the air quality impact of air pollutant emissions using photochemical models, speciation profiles are used to distribute total volatile organic compound (VOC) mass into emission estimates for individual species. Mobile source emission profiles used in the analysis of the proposed Tier 3 standards are listed below in Table 1. Additional information on the use of these profiles in air quality modeling, such as applicable source categories, can be found in the Emissions Inventory Technical Support Document. The EPA maintains a database of VOC and particulate matter (PM) speciation profiles for various emission sources including mobile sources. This database, called SPECIATE, maintains the record of each profile including its referenced source, testing methods, a subjective rating of the quality of the data, and other detailed data that allow researchers to decide which profile is most suitable for model input. Many of the profiles used are available in the SPECIATE version 4.3 database at: http://www.epa.gov/ttn/chief/software/speciate/index.html. Several profiles have been submitted for inclusion in the next version of SPECIATE and since this is not yet publically available, these profiles are included in this memorandum.

Table 1 lists the VOC speciation profiles used in Tier 3 NPRM air quality modeling Profile ID Profile Name Source

8750 Gasoline Exhaust - Reformulated gasoline (pre-Tier 2) SPECIATE v. 4.3 8751 Gasoline Exhaust - E10 ethanol gasoline (pre-Tier 2) SPECIATE v. 4.3 8756 Gasoline Exhaust - Tier 2 light-duty vehicles using 0% Ethanol - Composite Profile SPECIATE v. 4.3

8757 Gasoline Exhaust - Tier 2 light-duty vehicles using 10% Ethanol - Composite Profile SPECIATE v. 4.3

8758 Gasoline Exhaust - Tier 2 light-duty vehicles using 15% Ethanol - Composite Profile SPECIATE v. 4.3

8753 Gasoline Vehicle - Evaporative emission - Reformulated gasoline SPECIATE v. 4.3

8754 Gasoline Vehicle - Evaporative emission - E10 ethanol gasoline SPECIATE v. 4.3

8872 Gasoline Vehicle - Evaporative emission - E15 ethanol gasoline - Calculated Submitted to SPECIATE. Included in this document. 8766 Diurnal Permeation Evaporative Emissions from Gasoline Vehicles using 0% Ethanol - Combined - Composite Profile SPECIATE v. 4.3

8769 Diurnal Permeation Evaporative Emissions from Gasoline SPECIATE v. 4.3

### Vehicles using 10% Ethanol - Combined - Composite Profile 8770 Diurnal Permeation Evaporative Emissions from Gasoline Vehicles using 15% Ethanol - Combined SPECIATE v. 4.3

8869 Gasoline Headspace Vapor - 0% Ethanol (E0) Combined - EPAct/V2/E-89 Program Submitted to SPECIATE. Included in this document. 8870 Gasoline Headspace Va por - 10% Ethanol (E10) Combined - EPAct/V2/E-89 Program Submitted to SPECIATE. Included in this document. 8871 Gasoline Headspace Va por - 15% Ethanol (E15) Combined - EPAct/V2/E-89 Program Submitted to SPECIATE. Included in this document. 8774 Diesel Exhaust Emissions from Pre-2007 Model Year Heavy-Duty Diesel Trucks SPECIATE v. 4.3

8775 Diesel Exhaust Emissions from 2007 Model Year HeavyDuty Diesel Engines with Controls SPECIATE v. 4.3

4547 Gasoline Headspace Vapor - Ci rcle K Diesel - adjusted for oxygenates SPECIATE v. 4.3

5565 Aircraft Exhaust SPECIATE v. 4.3 2480 Industrial Cluster, Ship Channel, Downwind Sample - 1993 SPECIATE v. 4.3



## Profile 8872:

Profile 8872 “Gasoline Vehicle - Evaporative emission - E15 ethanol gasoline – Calculated” is a composite profile calculated by adjusting the ex isting profile 8754 1 

## for E10 evaporative emissions using the ratio of E10 to E15 fuel speciation profiles from EPAct/V2/E-89 Program Phase 3. 2 

## Six fuels from the EPAct/V2/E-89 Program Phase 3 were used: three E10 fuels (fuels 6, 10, 12) and three E15 (fuels 26, 27, 28). We aver aged the E10 fuel speciation profiles and the E15 fuel speciation profiles, then created an E10/E15 ratio for each compound using the averaged profiles. The E10/E15 per compound ra tio was then applied to the compounds in profile 8754 and renormalized to sum to 100 percent.

SPECIES_ID CAS SPECIES_NAME WT_PER 25 526-73-8 1,2,3-trim ethylbenzene 0.0530 30 95-63-6 1,2,4-trimethylbenzene 0.6144 36 135-01-3 1,2-diethylbenzene 0.0543 44 108-67-8 1,3,5-trim ethylbenzene 0.1324 48 542-92-7 1,3-cyclopentadiene 0.0006 59 105-05-5 1,4-diethylbenzene 0.0088 64 106-98-9 1-butene 0.0007 75 637-92-3 1-ethylter tbutylether 0.0258 78 592-41-6 1-hexene 0.0006 80 611-14-3 1-Methyl-2-ethylbenzene 0.0146 89 620-14-4 1-Methyl-3-ethylbenzene 0.7274 94 622-96-8 1-Methyl-4-ethylbenzene 0.1665 106 124-11-8 1-nonene 0.0044 107 111-66-0 1-octene 0.0016

1 

### SPECIATE v. 4.3 at http://www.epa.gov /ttn/chief/software/speciate/index.html 2 

### U.S. EPA. Assessing the Effect of Five Gasoline Properties on Exhaust Emissions from Light-Duty Vehicles certified to Tier-2 Standards: Part I - Study Design and Execution (EPAct/V2/E-89 Test Program Final Report). August, 2011.SPECIES_ID CAS SPECIES_NAME WT_PER 108 109-67-1 1-pentene 0.1630 112 464-06-2 2,2,3-trim ethylbutane 0.0006 118 540-84-1 2,2,4-trim ethylpentane 5.2912 121 3522-94-9 2,2,5-tr imethylhexane 0.2387 122 75-83-2 2,2-dimethylbutane 0.5331 124 590-73-8 2,2-dimethylhexane 0.0006 126 590-35-2 2,2-dimethylpentane 0.0011 127 463-82-1 2,2-dimethylpropane 0.0037 130 565-75-3 2,3,4-trim ethylpentane 4.7827 136 79-29-8 2,3-dimethylbutane 1.0996 138 584-94-1 2,3-dimethylhexane 0.1831 140 565-59-3 2,3-dimethylpentane 1.6933 141 107-39-1 2,4,4-trimet hyl-1-pentene 0.0010 149 589-43-5 2,4-dimethylhexane 0.6121 151 4032-94-4 2,4-dimethyloctane 0.0205 152 108-08-7 2,4-dimethylpentane 1.3621 156 592-13-2 2,5-dimethylhexane 0.0907 181 563-46-2 2-methyl-1-butene 0.4322 184 763-29-1 2-methyl-1-pentene 0.0138 185 513-35-9 2-methyl-2-butene 0.8444 186 2738-19-4 2-methyl-2-hexene 0.0031 187 625-27-4 2-methyl-2-pentene 0.0175 193 592-27-8 2-methylheptane 0.0465 194 591-76-4 2-methylhexane 0.3190 199 107-83-5 2-methylpentane (isohexane) 2.0374 203 558-37-2 3,3-dimethyl-1-butene 0.0004 206 563-16-6 3,3-dimethylhexane 0.0016 208 562-49-2 3,3-dimethylpentane 0.0014 215 926-82-9 3,5-dimethylheptane 0.0398 230 563-45-1 3-methyl-1-butene 0.0179 239 616-12-6 3-methyl-trans-2-pentene 0.0301 242 1120-62-3 3-methylcyclopentene 0.4963 244 589-81-1 3-methylheptane 0.0810 245 589-34-4 3-methylhexane 0.2801 247 2216-33-3 3-methyloctane 0.0011 248 96-14-0 3-methylpentane 0.7169 258 691-37-2 4-methyl-1-pentene 0.0032 262 674-76-0 4-methyl-trans-2-pentene 0.0272 264 589-53-7 4-methylheptane 0.0044 267 2216-34-4 4-methyloctane 0.0006 302 71-43-2 Benzene 2.7466 352 638-04-0 Cis-1,3-dimethylcyclohexane 0.0007 353 2532-58-3 Cis-1,3-dimethylcyclopentane 0.0110 367 590-18-1 Cis-2-butene 0.0357 368 6443-92-1 Cis-2-heptene 0.0011 369 7688-21-3 Cis-2-hexene 0.0073 371 627-20-3 Cis-2-pentene 0.2403 385 110-82-7 Cyclohexane 0.0070 388 110-83-8 Cyclohexene 0.0006SPECIES_ID CAS SPECIES_NAME WT_PER 390 287-92-3 Cyclopentane 0.2032 391 142-29-0 Cyclopentene 0.0236 442 64-17-5 Ethyl alcohol 19.2668 449 100-41-4 Ethylbenzene 1.6549 491 75-28-5 Isobutane 0.6888 497 115-11-7 Isobutylene (isobutene) 0.0006 508 78-78-4 Isopentane (2-Methylbutane) 7.5862 511 78-79-5 Isoprene (2-methyl-1,3-butadiene) 0.0012 522 108-38-3; 106-42-3 M & p-xylene 4.5116 548 1634-04-4 Methyl t-butyl ether (MTBE) 0.2813 550 108-87-2 Methylcyclohexane 0.0201 551 96-37-7 Methylcyclopentane 0.3148 592 106-97-8 N-butane 17.2315 596 104-51-8 N-butylbenzene 0.0242 599 112-40-3 N-dodecane 0.0481 600 142-82-5 N-heptane 0.2691 601 110-54-3 N-hexane 0.7447 604 111-65-9 N-octane 0.0569 605 109-66-0 N-pentane 3.8661 608 103-65-1 N-propylbenzene 0.0713 620 95-47-6 O-xylene 1.6083 671 74-98-6 Propane 0.3644 717 108-88-3 Toluene 14.0058 725 822-50-4 Trans-1,2-dimethylcyclopentane 0.0142 737 624-64-6 Trans-2-butene 0.0138 739 14686-13-6 Trans-2-heptene 0.0010 740 4050-45-7 Trans-2-hexene 0.0181 741 13389-42-9 Trans-2-octene 0.0004 742 646-04-8 Trans-2-pentene 0.7540 743 14686-14-7 Trans-3-heptene 0.0013 744 13269-52-8 Trans-3-hexene 0.0040 746 14850-23-8 Trans-4-octene 0.0009 1649 162071-36-5 3-Ethylpentene 0.0006

SUM 100.0000



## Profiles 8869-8871:

Profiles 8869, 8870 and 8871 are h 

## eadspace vapor profiles for 0% ethanol fuel (gasoline), 10% ethanol fuel and 15% ethanol fuel, respectivel y. Headspace profiles were developed for two fuels of each blend (E0, E10, and E15), and the average of the two profiles was calculated to create the combined profile fo r each blend. Individual fuel profiles and a more detailed methodology for collection of the headspace vapor can be found in the following document in Docket EPA-HQ-OAR-2011-0135: U.S. EPA, Hydrocarbon Composition of Gasoline Vapor Emissions from Enclosed Fuel Tanks, Draft Report No. 420-R-11-018. December 2011.SPECIES_ID CAS SPECIES_NAME E0_WT_PER E10_WT_PER E15_WT_PER 3 538-93-2 (2-methylpropyl)benzene 0.0087 0.0248 0.0114 19 590-66-9 1,1-DIMETHYLCYCL OHEXANE 0.0079 0.0073 0.0016 20 1638-26-2 1,1-DIMETHYLCYCL OPENTANE 0.0577 0.0347 0.0117 25 526-73-8 1,2,3-TRIMETHYL BENZENE 0.1364 0.3033 0.0000 27 2815-57-8 1,2,3-TRIMETHYLCYC LOPENTANE 0.0057 0.0050 0.0000 28 95-93-2 1,2,4,5-TETRAMETHY LBENZENE 0.0191 0.0822 0.0106 30 95-63-6 1,2,4-TRIMETHYL BENZENE 0.3296 0.9187 0.3380 31 2815-58-9 1,2,4-TRIMETHYLCYC LOPENTANE 0.0404 0.0391 0.0117 37 933-98-2 1,2-DIMETHYL-3-ETH YLBENZENE 0.0207 0.0586 0.0153 39 934-80-5 1,2-DIMETHYL-4-ETH YLBENZENE 0.0343 0.0983 0.0208 44 108-67-8 1,3,5-TRIMETHYL BENZENE 0.1201 0.3256 0.1332 52 2870-04-4 1,3-DIMETHYL-2-ETH YLBENZENE 0.1047 0.2274 0.0826 60 1758-88-9 1,4-DIMETHYL-2-ETH YLBENZENE 0.1247 0.3558 0.1165 63 98-19-1 1-(1,1-dimethylethyl)-3,5-dimethylbenzene 0.0056 0.0328 0.0050 64 106-98-9 1-BUTENE 0.1184 0.0652 0.0636 78 592-41-6 1-HEXENE 0.1930 1.2885 0.2487 84 1074-17-5 1-Methyl-2-n-propylbenzene 0.0343 0.0980 0.0331 100 1074-55-1 1-METHYL-4-N-PROPYLBENZENE 0.0431 0.1264 0.0373 103 693-89-0 1-METHYLCYCLOPEN TENE 0.2992 0.3416 0.4363 106 124-11-8 1-NONENE 0.0000 0.0000 0.0594 108 109-67-1 1-PENTENE 0.9301 0.9164 0.8408 112 464-06-2 2,2,3-TRIMETHYLB UTANE 0.0794 0.0681 0.0748 117 16747-26-5 2,2,4-TRIMETHY LHEXANE 0.0038 0.0088 0.0112 118 540-84-1 2,2,4-TRIMETHYL PENTANE 5.7602 5.3981 4.7909 121 3522-94-9 2,2,5-TRIMETHY LHEXANE 0.2630 0.2941 0.9060 122 75-83-2 2,2-DIMETHYLBU TANE 0.7390 0.4343 0.0587 126 590-35-2 2,2-DIMETHYLPEN TANE 0.1858 0.1856 0.0622 127 463-82-1 2,2-DIMETHYLPR OPANE 0.1009 0.0364 0.0268 130 565-75-3 2,3,4-TRIMETHYL PENTANE 0.8664 0.9429 2.4487 132 1069-53-0 2,3,5-TRIMETHY LHEXANE 0.0391 0.0435 0.1196 136 79-29-8 2,3-DIMETHYLBU TANE 1.6153 2.3822 1.8352 138 584-94-1 2,3-DIMETHYLHE XANE 0.1809 0.2415 0.5755 140 565-59-3 2,3-DIMETHYLPEN TANE 0.5981 0.4636 0.5223 141 107-39-1 2,4,4-TRIMETHYL-1- PENTENE 0.0989 0.1259 0.0257 146 2213-32-3 2,4-DIMETHYL-1- PENTENE 0.0127 0.0132 0.0175 148 2213-23-2 2,4-DIMETHYLH EPTANE 0.0097 0.0097 0.0161 149 589-43-5 2,4-DIMETHYLHE XANE 0.2560 0.2679 0.4621 152 108-08-7 2,4-DIMETHYLPEN TANE 0.7413 0.6059 0.9913 155 2216-30-0 2,5-DIMETHYLH EPTANE 0.0288 0.0351 0.0485 156 592-13-2 2,5-DIMETHYLHE XANE 0.3899 0.4047 0.6588 160 1072-05-5 2,6-DIMETHYLH EPTANE 0.0113 0.0111 0.0214 162 2051-30-1 2,6-DIMETHYLOC TANE 0.0236 0.0710 0.0498 181 563-46-2 2-METHYL-1-BUTENE 1.4371 1.3708 1.2674 184 763-29-1 2-METHYL-1-PENTENE 0.3483 0.3158 0.4104SPECIES_ID CAS SPECIES_NAME E0_WT_PER E10_WT_PER E15_WT_PER 185 513-35-9 2-METHYL-2-BUTENE 2.5076 2.5533 2.3767 187 625-27-4 2-METHYL-2-PENTENE 0.4601 0.4848 0.5577 189 609-26-7 2-METHYL-3-ETHYLPENTANE 0.0039 0.0058 0.0208 193 592-27-8 2-METHYLHEPTANE 0.0446 0.0545 0.0382 194 591-76-4 2-METHYLHEXANE 0.6847 0.6833 0.5462 199 107-83-5 2-METHYLPENTANE 5.0613 11.0338 3.3747 206 563-16-6 3,3-DIMETHYLHE XANE 0.0075 0.0062 0.0023 208 562-49-2 3,3-DIMETHYLPEN TANE 0.0850 0.0768 0.0317 212 583-48-2 3,4-DIMETHYLHE XANE 0.0338 0.0416 0.1099 217 15869-93-9 3,5-DIMETHYL OCTANE 0.0064 0.0163 0.0156 230 563-45-1 3-METHYL-1-BUTENE 0.2457 0.2085 0.1935 232 760-20-3 3-METHYL-1-PENTENE 0.2208 0.2444 0.2442 237 4914-89-0 CIS-3-METHYL-3 -HEXENE 0.0323 0.0616 0.0966 244 589-81-1 3-METHYLHEPTANE 0.0421 0.0525 0.0419 245 589-34-4 3-METHYLHEXANE 0.5324 0.5328 0.4237 246 5911-04-6 3-METHYLNONA NE 0.0033 0.0067 0.0085 247 2216-33-3 3-METHYLOCTANE 0.0047 0.0081 0.0076 248 96-14-0 3-METHYLPENTANE 3.7615 6.5965 2.1229 257 3769-23-1 4-METHYL-1-HEXENE 0.0132 0.0172 0.0285 264 589-53-7 4-METHYLHEPTANE 0.0147 0.0188 0.0146 271 7385-82-2 TRANS-5-METHYL-2-HEXENE 0.0076 0.0113 0.0148 302 71-43-2 BENZENE 0.7720 0.8709 1.0846 350 7667-60-9 Cis,trans-1,2,4-trimethylcyclohexane 0.0331 0.0561 0.1149 351 2207-01-4 Cis-1,2-dimethylc yclohexane 0.0007 0.0010 0.0000 353 2532-58-3 CIS-1,3-DIMETHYLCY CLOPENTANE 0.1128 0.1025 0.0929 367 590-18-1 CIS-2-BUTENE 0.4947 0.3211 0.3213 369 7688-21-3 CIS-2-HEXE NE 0.2632 0.2891 0.3364 370 7642-04-8 Cis-2-OCTENE 0.0070 0.0081 0.0227 371 627-20-3 CIS-2-PENTENE 1.1462 1.1693 1.0818 372 7642-09-3 CIS-3-HEXE NE 0.2812 0.2993 0.3391 385 110-82-7 CYCLOHEXANE 2.1515 1.5724 0.4900 390 287-92-3 CYCLOPENTANE 1.6332 0.4730 0.1955 391 142-29-0 CYCLOPENTENE 0.3921 0.4516 0.4372 442 64-17-5 ETHANOL 0.0000 6.4467 27.1853 449 100-41-4 ETHYLBENZENE 0.4186 0.6864 0.6007 451 1640-89-7 ETHYLCYCLOPENTANE 0.2560 0.2679 0.4621 464 25550-14-5 Ethyltoluenes (meth ylethylbenzenes) 0.4108 1.0645 0.4660 485 496-11-7 INDAN 0.0195 0.0432 0.0182 491 75-28-5 ISOBUTANE 0.2472 0.1008 0.0983 497 115-11-7 2-METHYLPROPENE (ISO BUTYLENE) 0.1388 0.0714 0.0799 508 78-78-4 2-METHYLBUTANE (ISO PENTANE) 24.5893 10.2913 8.9647 511 78-79-5 ISOPRENE 0.0257 0.0270 0.0267 514 98-82-8 ISOPROPYLBENZENE (CUMENE) 0.0250 0.0591 0.0404

522 108-38-3; 106- 42-3 M & P-XYLENE 1.4418 2.4267 2.0123

550 108-87-2 METHYLCYCLOHEXANE 0.5468 0.3593 0.0755SPECIES_ID CAS SPECIES_NAME E0_WT_PER E10_WT_PER E15_WT_PER 551 96-37-7 METHYLCYCLOPENTANE 2.5916 2.1390 1.3982 592 106-97-8 N-BUTANE 5.4418 4.4550 5.7959 598 124-18-5 N-DECANE 0.0487 0.1506 0.0110 600 142-82-5 N-HEPTANE 0.3222 0.2895 0.1435 601 110-54-3 N-HEXANE 6.0574 6.1600 2.1815 603 111-84-2 N-NONANE 0.0081 0.0135 0.0175 604 111-65-9 N-OCTANE 0.0478 0.0635 0.0274 605 109-66-0 N-PENTANE 6.5570 3.1398 1.8924 606 538-68-1 N-PENTYLBENZENE 0.0105 0.0271 0.0060 608 103-65-1 N-PROPYLBENZENE 0.0519 0.1374 0.0602 610 1120-21-4 N-UNDECANE 0.0114 0.0354 0.0075 620 95-47-6 O-XYLENE 0.2945 0.5289 0.3449 671 74-98-6 PROPANE 0.0172 0.0082 0.0067 677 2040-96-2 Propylcyclopen tane 0.0007 0.0010 0.0000 717 108-88-3 TOLUENE 6.8651 5.2128 8.7886 727 1759-58-6 TRANS-1,3-DIMETHYLCY CLOPENTANE 0.1292 0.1258 0.1168 729 2207-04-7 Trans-1,4-dimethylc yclohexane 0.0145 0.0140 0.0029 737 624-64-6 TRANS-2-BUTENE 0.5578 0.3201 0.3191 740 4050-45-7 TRANS-2-HEXENE 0.4953 0.5359 0.6171 742 646-04-8 TRANS-2-PENTENE 2.1229 2.1503 1.9777 743 14686-14-7 TRANS-3-HEPTENE 0.0063 0.0151 0.0239 744 13269-52-8 TRANS-3-HEXENE 0.3508 0.3754 0.4226 981 68411-44-9 Butylbenzene 0.0135 0.0332 0.0150 1153 922-61-2 3-methyl-2-pentene 0.3826 0.4006 0.4819 1474 34522-19-5 trans-1-methyl-3-pr opylcyclohexane 0.0105 0.0271 0.0060 1652 27133-93-3 Methylindane 0.0228 0.0557 0.0132 1654 6434-77-1 CIS-2-NONE NE 0.0036 0.0015 0.0007 1655 1074-92-6 t-1-Butyl-2-Meth ylbenzene 0.0580 0.1283 0.0331 1879 1759-81-5 4-Methylcyclopentene 0.0711 0.0799 0.0906 2244 6434-78-2 TRANS-2-NONE NE 0.0126 0.0229 0.0357 2285 N/A UNKNOWN 1.8193 4.0992 2.4672

SUM 100.0000 100.0000 100.0000