## UNITED STATES ENVIRONMEN TAL PROTECTION AGENCY

NATIONAL VEHICLE AND FUEL EMISSIONS LABORATORY

2000 TRAVERWOOD DRIVE

ANN ARBOR, MI 48105-2498

OFFICE OF

AIR AND RADIATION



## Date: September 13, 2012

MEMORANDUM

SUBJECT: Hydrocarbon Composition of Gasoline Va por Emissions from Enclosed Fuel Tanks

FROM: Catherine Yanca, Assessment and Standards Division

TO: EPA Docket EPA-HQ-OAR-2010-0799

The following materials were used by EPA duri ng the rulemaking. EPA inadvertantly failed to

physically include them in the docket before sign ature of the final rule. These materials were

prepared before the rule was signed, and were no t altered, edited, or otherwise amended in any

way after signature.

# Hydrocarbon Composition of Gasoline

Vapor Emissions from Enclosed Fuel Tanks

Draft

### EPA-420-R-11-018

December 2011 

## Assessment and Standards Division

Office of Transportation and Air Quality

and

Human Exposure & Atmospheric Sciences Division

Office of Research and Development

U.S. Environmental Protection Agency 

# Hydrocarbon Composition of Gasoline

Vapor Emissions from Enclosed Fuel Tanks

Draft

NOTICE

This technical report does not necessarily represent final EPA decisions or

positions. It is intended to present technical analysis of issues using data

that are currently available. The purpose in the release of such reports is to

facilitate the exchange of technical information and to inform the public of

technical developments.

## 1 Introduction

The purpose of this report is for EPA OTAQ (Office of Transportation and Air Qual ity) to give a

summary of EPA ORD (Office of Research and Development) work on the composition of

hydrocarbon emissions from gasoline, specifically the head space components above gasoline in

an enclosed fuel tank. These profiles were used in EPA’s proposed Tier 3 rule and antibacksliding study. The profiles were used to speciate hydrocarbon emissions from onroad

vehicle and nonroad engine gasoline refueling, portable fuel container emissions, and vapor

losses during storage and transport.

Overview and Prior Work

Headspace vapors are those hydrocarbon compounds in gaseous form above a gasoline s ample in

an enclosed space such as a vehicle fuel tank or frequently a fuel storage tank used in the

distribution for gasoline

. Some of these vapors are emitted to the atm osphere in transport,

storage, and utilization of gas oline. The numerous hydrocarbo n compounds (about 120

individual hydrocarbons) represent the more volatile and lower molecular weight components of

the gasoline.

For EPA’s RFS2 rule, EPA ORD measured headspace emissions for an E0 base gasoline and an

E10 sample splash-blended from the E0 gasoline For EPA’s RFS2 rule, EPA ORD measured

headspace emissions for an E0 base gasoline and an E10 sample splash-blended from the E0

gasoline. 1



## However, the anti-backsliding and Tier3 analyses also required modeling an E15 blend, since in

Januar y, 2011, EPA granted partial waivers that allow the introduction into commerce of

gasoline that contains greater than 10 volume percent (vol%) ethanol and up to 15 vol% ethanol

(E15) for use in model year (MY) 2001 and newer light-duty motor vehicles, subj ect to certain

conditions. 2 

## On October 13, 2010, EPA granted the first partial waiver for E15 for use in

MY2007 and newer light-duty motor vehicles (i.e., cars, light-duty trucks and medium-duty

passenger vehicles). On January 21, 2011, EPA granted the second partial waiver for E15 for use

in MY2001-2006 light-duty motor vehicles. These decisions were based on test results provided

by the U.S. Department of Energy (DOE) and other test data and information regarding the

potential effect of E15 on vehicle em issions.

In order to ensure consistency between headspace profiles for E0, E10 and E15 fuels, new

profiles were developed using fuel samples from the EPAct test program. 3

1 

### U. S. EPA. 2009. Hydrocarbon Composition of Gasoline Vapor Emissions from Enclosed Fuel Tanks. Office of

Transportation and Air Quality, Ann Arbor, MI, and Office of Research and Development, RTP, NC. EPA

- 420 -D10

- 011, January 2010. 

## Properties of the six

fuels tested are summarized in Table 1. Fuels 13 and 14 are E0 fuels, fuels 6 and 10 are E10, and

2 

### Federal R egister. 2011. Partial Grant of Clean Air Act Waiver Application Submitted by Growth Energy to

Increase the Allowable Ethanol Content of Gasoline to 15 Percent; Decision of the Admininstrator. 76(17):4662

-

4683.

3 

### Add reference: Phase 3 EPAct/V2?E

- 89 Test Program.

## 2 fuels 27 and 28 are E15. One fuel in each pair is low in aromatics (15-17 volume percent) and

one is high in aromatics (about 34-35 percent). Olefin levels range from 6 -9 percent, and

volatiliti es are similar, with DVPEs of about 7 percent.

Sample Preparation

The 6 gasoline samples tested for headspace and whole composition were received from

Southwest Research Institute in amber -tinted quart bottles via FedEx shipment. To prepare for

testing, these bottles were placed in large cooler containing ice. After a 20 – 30 min period 25 ml

aliquots were withdrawn using Pasteur pipettes and put into 50 ml Erlenmeyer flasks then placed

into a constant water

- temperature bath maintained at 25 o 

## C. Similar 2 5 ml aliquots of each

sample were placed into 20 x 150 mm Pyrex culture bottles, capped and stored in the ice bath.

Triple distilled water (70 μl) was injected into recently cleaned and vacuum evacuated six liter

SUMMA canisters to condition the canister surface. This small volume o f water vaporizes to

coat the internal surfaces of the canister wi th a monolayer of water vapot. This deactivate s and

conditions active surface sites , allowing the storage of the VOC vapors obtained from the

gasoline and gasol ine head space injections at 25 °C. Without this deactivation, si gnificant losses

of these compounds from benzene to the higher molecular weight hydrocarbons would be

observed during the sample storage period.

. After a 20 min equilibration time, 100 μL a liquots of the headspace vapors were taken from the

Erlenmeyer flask and injected into the SUMMA canisters. The canisters were then filled with

UHP helium to 40 psig. The prepared canisters were allowed to equilibrate for a 12 to 15 h

period before perfor ming both GC/FID and GC/MS analyses. Whole fuel samples were prepared

by injecting 0.02 μL aliquots of the cooled liquid into the 6

- L canisters, then filled with UHP

helium to 40 psig. More details of these procedures are published elsewhere. Likewise mor e

detail concerning the GC/FID and GC/MS methodology are published elsewhere. 4



## The results obtained for two each E0, E10, and E15 fuels sent to RTP for headspace an alysis are

provided in the attached tables . Results for both the headspace at 25 ° C and whole f uel analyses

of E0, E10 and E15 gasolines are included . About 140 compound peaks are presented from the

more than 200 compound peaks observed representing approximately 98% of total VOC

concentration. Compound name, VOC type (paraffin, olefin, aromatic, oxygenate, unknown),

and RTINDEX 5

4 

### Harley, R.A., S.A. McKeen, M.O. Rodgers, and W.A. Lonneman, Analysis of motor vehicle emissions during the

Nashville/Middle Tennessee Ozone Study, J. Geophys. Res., 106, 3559

- 3567, 2001 

## for each compound are provided in the first 3 columns to the left.

5 

### RTINDEX is a technique used to place the elution order and/or location of various VOCs on the GC column. The

most common approach is to determine the retention time of a mixture of the C 2 

### -C 15 

### normal paraffins (i.e., ethane

through pentadecane) then place other VOCs by retention time w h ere these compounds elute in reference to the

normal paraffins. For example

, the retention time of benzene on an EPA GC column with an RTINDEX value of

651.21 is about half way between the centerary retention times of the C 6 

### and C 7 

### nornal alkanes – n- hexane being

defined with an RTINDEX value of 600.00 and n

- heptane with a defi ned RTINDEX value of 700.00.

## 3 Table 1. Properties of EPAct fuels tested.

PROPERTY UNIT TEST METHOD EPAct Phase 3 Fuel

6 10 13 14 27 28

Density, 60 o 

### F g/cm 3 

### D4052 0.7342 0.7644 0.7540 0.7223 0.7434 0.7699

API Gravity,

60 o 

### F o 

### API D4052 61.1 53.4 56.0 64.2 58.6 52.1

Ethanol vol. % D5599 10.56 9.82 <0.10 <0.10 14.91 14.98

Total Content

of Oxygenates

Other Than

Ethanol vol. % D5599 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10

Distillation

IBP oF

D86 ( OptiDist or

equivalent for E10,

E15 and E20 fuels) 106.7 104.7 96.6 100.4 104.8 103.9

5% evap oF 130.4 130.0 127.0 126.5 135.3 136.3

10% evap oF 135.9 136.3 139.8 135.5 142.3 144.2

20% evap oF 142.6 144.3 158.7 147.3 152.0 154.0

30% evap oF 148.3 151.0 178.2 160.0 158.0 160.2

40% evap oF 153.4 161.6 199.9 175.1 163.8 165.8

50% evap oF 188.5 217.1 222.5 192.8 221.5 216.6

60% evap oF 228.2 261.5 245.2 212.0 265.1 240.2

70% evap oF 267.7 290.4 269.8 237.3 274.9 251.6

80% evap oF 310.1 317.5 303.5 280.1 311.3 268.4

90% evap oF 340.4 340.2 337.9 338.5 340.3 298.8

95% evap oF 352.7 354.3 354.4 354.5 351.9 327.3

FBP oF 369.2 372.4 377.5 377.5 372.2 363.2

DVPE (EPA

equation) psi D5191 7.24 7.11 6.92 7.14 6.97 6.87

Aromatics vol. % D1319 15.0 34.0 34.1 16.9 14.9 34.5

Olefins vol. % D1319 8.8 6.1 6.3 8.5 7.4 7.0

Saturates vol. % 100

- D1319Aromatics

- D1319Olefins

-

D5599Ethanol 65.6 50.1 59.6 74.6 62.9 43.5

Benzene vol. % D3606 0.68 0.52 0.51 0.52 0.56 0.59

S mg/kg D5453 23 25 23 24 26 24

RON

- D2699 96.3 98.5 95.8 91.5 100.8 102.7

MON

- D2700 86.6 87.2 85.8 84.6 89.2 89.4

(RON+MON)/2

- - 91.5 92.9 90.8 88.1 95.0 96.1

C mass % D5291 mod. 81.52 83.47 86.76 85.28 80.27 81.78

H mass % D5291 mod. 14.21 12.83 13.15 14.29 14.01 12.62

O mass % D5599 4.0 3.6 <0.1 <0.1 5.5 5.4

Net Heat of

Combustion MJ/kg D4809 41.785 41.210 43.171 43.519 41.062 40.383

Water mass % E

- 1064 0.073 0.067 0.014 0.015 0.090 0.091

Lead g/l D3237

- <0.003 <0.001 <0.001 <0.003 <0.003

Copper Strip

Corrosion - D130 1A 1A 1A 1A 1A 1A

Solvent Washed

Gum Content mg/100ml D381 <0.5 <0.5 1.5 <0.5 0.5 <0.5

Oxidation

Stability min. D525 >240 >240 >240 >240 >240 >240

## The columns labeled HS and Whole provide the fraction that the observed peak concentration

obtained as parts

- per

- billion carbon (ppbC) is to the sum of all observed peaks obtained as ppbC.

At the bottom of the spreadsheet column is the ratio that the sum of listed peaks is of all the

observed peaks. This value is typically 98 – 99%. Also included are tables with the percent sum

of t he various compound groups to the total VOC. The concentration of e thanol was corrected

for the reduced FID response due to the presence of an oxygen atom. For e thanol, the carbon

atom attached to the hydroxyl ( OH ) group has about 50% reduced response wi th the FID

compared to the other carbon in the compound. Consequently the correction for the 2 carbons in

ethanol is given as 2/1.5 or 1.33.

Precision and Accuracy of Results

In past analyses of whole gasoline and gasoline headspace samples at 25 °C, ORD has measured

both precision and accuracy for these analyses. Repeat analysi s for instrumental precision is

more commonly performed with repeatability of 5% or better.

National Instit ute of Standards and Technology/ Standard Reference Material

(NIST/SRM) propane in air standard cylinder is used to determine accuracy. The assumption is

made (as it is in EPA measurements of motor vehicle exhaust) that all hydrocarbons respond in

the flame ionization detector (FID) with a uniform per carbon response. However, ethanol, as

well as any other oxygenated hydrocarbons in gasoline, does not respond in this way. As

discussed earlier, an adjustment was made for the presence of oxygen in the FID response.

4

## Table 2

. Headspace (HS) and whole fuel composition of Fuel 13. Compound type: p = paraffin,

o = olefin, a = aromatic, ox = oxygenate, u = unknown.

Fuel # 13 Headspace@25C and Whole Fuel Composition

Compound Type RTINDEX 

### HS Whole

Propane p 300.00 0.029 0.025

Isobutane p 361.88 0.355 0.060

Butene

- 1 o 389.97 0.147 0.055

Isobutylene o 390.92 0.167 0.000

n

- Butane p 400.00 9.555 1.906

t

- Butene

- 2 o 411.64 0.729 0.155

2,2

- Dimethylpropane* p 413.35 0.075 0.073

c

- Butene

- 2 o 425.94 0.551 0.128

3

- Methyl

- 1

- Butene o 457.43 0.249 0.070

Ethanol ox 461.50 0.000 0.000

Isopentane p 474.54 21.286 8.590

Pentene

- 1 o 489.36 0.873 0.356

2

- Methyl

- 1

- Butene o 496.17 1.361 0.630

n

- Pentane p 500.00 6.190 3.070

Isoprene o 504.19 0.024 0.011

trans

- 2

- Pentene o 508.72 1.950 1.000

Unknown u 513.67 0.015 0.012

cis

- 2

- Pentene o 516.35 1.045 0.547

2

- Methyl

- 2

- Butene o 521.04 2.276 1.255

2,2

- Dimethylbutane p 535.47 0.336 0.213

Cyclopentene o 551.84 0.343 0.221

3

- Methyl

- 1

- pentene o 557.98 0.195 0.138

Cyclopentane p 562.82 0.500 0.340

2,3

- Dimethylbutane p 565.46 1.917 1.450

2

- Methylpentane p 570.09 4.769 3.764

3

- Methylpentane p 583.52 3.376 2.807

2

- Methyl

- 1

- Pentene o 588.52 0.322 0.271

Hexene

- 1 o 589.36 0.186 0.147

n

- Hexane p 600.00 5.275 4.786

trans

- 3

- Hexene o 602.80 0.348 0.320

trans

- 2

- Hexene o 604.98 0.488 0.451

2

- Methyl

- 2

- Pentene o 607.37 0.458 0.429

Unknown u 608.87 0.135 0.112

cis

- 3

- Hexene o 610.49 0.281 0.262

4

- Methylcyclopentene* o 612.17 0.069 0.062

cis

- 2

- Hexene o 614.50 0.258 0.238

cis

- 3

- Methyl

- 2

- pentene* o 620.74 0.386 0.376

2,2

- DiMethylpentane p 625.13 0.191 0.201

Methylcyclopentane p 627.20 2.443 2.342

2,4

- Dimethylpentane p 631.38 0.992 1.051

2,2,3

- TriMethylbutane p 637.00 0.103 0.105

2,4

- DiMethyl

- 1

- Pentene o 647.79 0.014 0.015

1

- Methylcyclopentene o 651.00 0.309 0.331

Benzene a 651.21 0.784 0.842

3,3

- DiMethylpentane p 657.00 0.093 0.120

Cyclohexane p 660.96 1.783 1.891

4

- Me

- 1

- Hexene o 665.23 0.003 0.017

2

- Methylhexane p 668.68 0.788 0.952

2,3

- Dimethylpentane p 670.80 0.557 0.666

1,1

- DiMeCyclopentane p 674.11 0.066 0.082

3

- Methylhexane p 677.22 0.599 0.746

5

- Methyl

- 2

- hexene* o 680.55 0.008 0.010

c

- 1,3

- DiMeCyclopentane p 684.41 0.133 0.160

t

- 1,3,

- DiMeCyclopentane p 687.12 0.149 0.188



## 5

## 6 2,2,4

- TriMethylpentane p 690.72 4.010 5.261

3

- Methyl

- 3

- hexene o 695.08 0.005 0.011

trans

- 3

- Heptene o 697.82 0.007 0.011

n

- Heptane p 700.00 0.370 0.508

3

- Me

- cis

- 3

- Hexene o 701.44 0.032 0.000

2,4,4

- TriMethyl

- 1

- Pentene o 712.30 0.008 0.011

MethylCyclohexane p 724.30 0.671 0.947

2,5

- DiMethylhexane p 733.56 0.452 0.758

2,4

- DiMethylhexane + EthylCyclopentane p 735.91 0.613 1.021

3,3

- DiMethylhexane + 1,2,4

- TriMeCyclopentane p 743.87 0.018 0.031

ctc

- 1,2,3

- TriMeCyclopentane p 751.44 0.007 0.013

2,3,4

- TriMethylpentane p 753.56 1.203 2.127

Toluene a 758.58 10.681 18.840

2,3

- DiMethylhexane p 762.98 0.243 0.632

2

- Methyl

- 3

- Ethylpentane p 765.00 0.000 0.000

2

- Methylheptane p 767.55 0.049 0.123

4

- Methylheptane p 769.28 0.015 0.038

3,4

- DiMethylhexane p 772.50 0.048 0.101

3

- Methylheptane p 775.34 0.047 0.122

ctc

- 1,2,4

- TriMeCyclopentane p 781.70 0.037 0.082

t

- 1,4

- DiMeCyclohexane p 783.92 0.017 0.034

2,2,5

- Trimethylhexane p 785.98 0.418 0.909

1,1

- DiMethylCyclohexane p 790.50 0.008 0.017

2,2,4

- TriMethylhexane p 794.85 0.004 0.023

n

- Octane p 800.00 0.051 0.153

cis

- 2

- Octene o 812.37 0.010 0.021

2,3,5

- TriMethylhexane p 819.44 0.063 0.142

2,4

- DiMethylheptane p 825.88 0.015 0.023

2,6

- DiMethylheptane p 831.77 0.016 0.029

1c2

- DiMethylcyclohexane n

- Propylcyclopentane p 834.70 0.000 0.005

2,5

- DiMeHeptane p 838.60 0.036 0.091

Ethylbenzene a 855.40 0.479 1.765

ctt

- 1,2,4

- TriMeCyclohexane p 860.26 0.012 0.036

m

- & p

- Xylene a 863.65 1.654 6.945

3

- Methyloctane p 873.73 0.004 0.017

ctc

- 1,2,4

- TriMeCyclohexane p 881.42 0.037 0.113

o

- Xylene a 887.56 0.319 1.582

Nonene

- 1 o 889.31 0.000 0.000

Nonane p 900.00 0.007 0.024

trans

- 2

- Nonene o 902.49 0.017 0.047

cis

- 2

- Nonene o 912.37 0.006 0.008

Isopropylbenzene a 920.34 0.026 0.071

3,5

- DiMethyloctane p 927.97 0.007 0.010

2,6

- DiMethyloctane p 937.70 0.022 0.029

n

- Propylbenzene a 950.95 0.041 0.313

m

- Ethyltoluene a 957.45 0.163 1.364

p

- Ethyltoluene a 960.02 0.106 0.702

1,3,5

- TriMethylbenzene a 964.32 0.094 0.934

3

- Methylnonane p 973.55 0.003 0.016

o

- Ethyltoluene a 976.97 0.069 0.561

Unknown u 986.65 0.037 0.033

Unknown u 988.06 0.000 0.000

1,2,4

- TriMethylbenzene a 991.48 0.250 2.578

n

- Decane p 1000.00 0.036 0.117

Isobutylbenzene + 1

- Me

- 2

- Propylcyclohexane a 1008.16 0.013 0.065

sec

- Butylbenzene a 1010.39 0.012 0.055

m

- Cymene a 1018.22 0.013 0.066

1,2,3

- TriMethylbenzene a 1022.13 0.117 0.619

Unknown u 1031.59 0.094 0.428

Indane n 1036.98 0.017 0.138

Unknown u 1040.81 0.040 0.164

## 7 Unknown u 1048.17 0.129 0.772

n

- Butylbenzene + p

- Diethylbenzene a 1054.69 0.000 0.271

1

- Me

- 4

- isoPropylbenzene a 1059.44 0.020 0.042

Unknown u 1062.68 0.009 0.109

1

- Me

- 2

- n

- Propylbenzene a 1067.27 0.020 0.423

1,4

- DiMe

- 2

- Ethylbenzene a 1075.98 0.081 0.134

Unknown u 1078.46 0.017 0.175

1,2

- DiMe

- 4

- Ethylbenzene a 1084.27 0.021 0.289

Unknown u 1086.66 0.000 0.339

1,3

- DiMe

- 2

- Ethylbenzene a 1092.85 0.087 0.050

Unknown u 1094.62 0.017 0.038

n

- Undecane p 1100.00 0.004 0.072

1,2

- DiMe

- 3

- Ethylbenzene a 1107.49 0.010 0.126

1,2,4,5

- Tetra

- Me

- Benzene a 1119.01 0.016 0.220

Unknown u 1123.00 0.026 0.326

t

- 1

- But

- 2

- MeBenzene a 1139.52 0.056 0.027

Unknown u 1144.96 0.005 0.143

Methylindane n 1156.53 0.019 0.142

n

- Pentylbenzene + t

- 1

- Me

- 2

- (4MP)cyclohexane a 1158.21 0.017 0.069

t

- 1

- But

- 3,5

- DiMeBenzene a 1174.77 0.000 0.030

Unknown u 1175.94 0.079 0.000

t

- 1

- But

- 4

- Ethylbenzene a 1183.89 0.000 0.023

Naphthalene n 1189.56 0.000 0.000

n

- Dodecane p 1200.00 0.000 0.000

% Listed Peaks are of Total VOC 99.02 98.25

## 8 Table 3

. Summary statistics for the hydrocarbon composition of Fuel 13.



# Summary Statistics for Fuel #13

HS Whole



# %Ethanol 0.000 0.00

%Paraff ins 70.10 48.96

%Olefins 13.12 7.57

%Aromatics 15.15 38.81

%Unknowns 0.60 2.64

%Fused Rings 0.04 0.28

## 9 Table 4

. Headspace and whole fuel composition of Fuel 14.

Fuel # 14 Headspace@25C and Whole Fuel Composition

Compound Type RTINDEX HS Whole

Propane p 300.00 0.006 0.02

Isobutane p 361.88 0.139 0.05

Butene

- 1 o 389.97 0.090 0.00

Isobutylene o 390.92 0.111 0.03

n

- Butane p 400.00 1.329 0.39

t

- Butene

- 2 o 411.64 0.386 0.15

2,2

- Dimethylpropane* p 413.35 0.127 0.09

c

- Butene

- 2 o 425.94 0.439 0.12

3

- Methyl

- 1

- Butene o 457.43 0.242 0.07

Ethanol ox 461.50 0.000 0.00

Isopentane p 474.54 27.892 10.72

Pentene

- 1 o 489.36 0.987 0.35

2

- Methyl

- 1

- Butene o 496.17 1.513 0.62

n

- Pentane p 500.00 6.924 3.03

Isoprene o 504.19 0.027 0.01

trans

- 2

- Pentene o 508.72 2.296 1.00

Unknown u 513.67 0.020 0.01

cis

- 2

- Pentene o 516.35 1.247 0.54

2

- Methyl

- 2

- Butene o 521.04 2.739 1.28

2,2

- Dimethylbutane p 535.47 1.142 0.65

Cyclopentene o 551.84 0.442 0.22

3

- Methyl

- 1

- pentene o 557.98 0.246 0.15

Cyclopentane p 562.82 2.766 1.65

2,3

- Dimethylbutane p 565.46 1.313 0.93

2

- Methylpentane p 570.09 5.353 4.11

3

- Methylpentane p 583.52 4.147 3.51

2

- Methyl

- 1

- Pentene o 588.52 0.375 0.30

Hexene

- 1 o 589.36 0.200 0.15

n

- Hexane p 600.00 6.840 6.87

trans

- 3

- Hexene o 602.80 0.354 0.36

trans

- 2

- Hexene o 604.98 0.503 0.49

2

- Methyl

- 2

- Pentene o 607.37 0.462 0.46

Unknown u 608.87 0.154 0.13

cis

- 3

- Hexene o 610.49 0.281 0.28

4

- Methylcyclopentene* o 612.17 0.073 0.06

cis

- 2

- Hexene o 614.50 0.268 0.25

cis

- 3

- Methyl

- 2

- pentene* o 620.74 0.379 0.41

2,2

- DiMethylpentane p 625.13 0.181 0.22

Methylcyclopentane p 627.20 2.741 3.00

2,4

- Dimethylpentane p 631.38 0.490 0.67

2,2,3

- TriMethylbutane p 637.00 0.055 0.08

2,4

- DiMethyl

- 1

- Pentene o 647.79 0.012 0.02

1

- Methylcyclopentene o 651.00 0.290 0.39

Benzene a 651.21 0.760 0.86

3,3

- DiMethylpentane p 657.00 0.077 0.12

Cyclohexane p 660.96 2.520 3.46

4

- Me

- 1

- Hexene o 665.23 0.023 0.00

2

- Methylhexane p 668.68 0.581 1.04

2,3

- Dimethylpentane p 670.80 0.639 1.13

1,1

- DiMeCyclopentane p 674.11 0.049 0.07

3

- Methylhexane p 677.22 0.466 0.86

5

- Methyl

- 2

- hexene* o 680.55 0.007 0.01

c

- 1,3

- DiMeCyclopentane p 684.41 0.093 0.17

t

- 1,3,

- DiMeCyclopentane p 687.12 0.109 0.21

2,2,4

- TriMethylpentane p 690.72 7.510 15.87

3

- Methyl

- 3

- hexene o 695.08 0.004 0.01

trans

- 3

- Heptene o 697.82 0.006 0.01

n

- Heptane p 700.00 0.275 0.65

3

- Me

- cis

- 3

- Hexene o 701.44 0.024 0.00

2,4,4

- TriMethyl

- 1

- Pentene o 712.30 0.190 0.41

MethylCyclohexane p 724.30 0.423 0.95

2,5

- DiMethylhexane p 733.56 0.328 0.84

## 10 2,4

- DiMethylhexane + EthylCyclopentane p 735.91 0.411 1.06

3,3

- DiMethylhexane + 1,2,4

- TriMeCyclopentane p 743.87 0.012 0.03

ctc

- 1,2,3

- TriMeCyclopentane p 751.44 0.005 0.01

2,3,4

- TriMethylpentane p 753.56 0.529 1.43

Toluene a 758.58 3.049 7.86

2,3

- DiMethylhexane p 762.98 0.119 0.35

2

- Methyl

- 3

- Ethylpentane p 765.00 0.008 0.00

2

- Methylheptane p 767.55 0.041 0.10

4

- Methylheptane p 769.28 0.015 0.03

3,4

- DiMethylhexane p 772.50 0.020 0.05

3

- Methylheptane p 775.34 0.038 0.10

ctc

- 1,2,4

- TriMeCyclopentane p 781.70 0.029 0.08

t

- 1,4

- DiMeCyclohexane p 783.92 0.012 0.04

2,2,5

- Trimethylhexane p 785.98 0.108 0.33

1,1

- DiMethylCyclohexane p 790.50 0.007 0.02

2,2,4

- TriMethylhexane p 794.85 0.004 0.02

n

- Octane p 800.00 0.044 0.16

cis

- 2

- Octene o 812.37 0.004 0.01

2,3,5

- TriMethylhexane p 819.44 0.016 0.06

2,4

- DiMethylheptane p 825.88 0.005 0.02

2,6

- DiMethylheptane p 831.77 0.006 0.02

1c2

- DiMethylcyclohexane n

- Propylcyclopentane p 834.70 0.003 0.01

2,5

- DiMeHeptane p 838.60 0.021 0.05

Ethylbenzene a 855.40 0.359 1.15

ctt

- 1,2,4

- TriMeCyclohexane p 860.26 0.007 0.02

m

- & p

- Xylene a 863.65 1.229 4.01

3

- Methyloctane p 873.73 0.005 0.02

ctc

- 1,2,4

- TriMeCyclohexane p 881.42 0.010 0.04

o

- Xylene a 887.56 0.270 0.88

Nonene

- 1 o 889.31 0.000 0.00

Nonane p 900.00 0.009 0.03

trans

- 2

- Nonene o 902.49 0.008 0.03

cis

- 2

- Nonene o 912.37 0.002 0.00

Isopropylbenzene a 920.34 0.024 0.09

3,5

- DiMethyloctane p 927.97 0.006 0.02

2,6

- DiMethyloctane p 937.70 0.026 0.08

n

- Propylbenzene a 950.95 0.063 0.20

m

- Ethyltoluene a 957.45 0.241 0.75

p

- Ethyltoluene a 960.02 0.133 0.37

1,3,5

- TriMethylbenzene a 964.32 0.147 0.45

3

- Methylnonane p 973.55 0.004 0.01

o

- Ethyltoluene a 976.97 0.110 0.35

Unknown u 986.65 0.024 0.07

Unknown u 988.06 0.000 0.00

1,2,4

- TriMethylbenzene a 991.48 0.409 1.33

n

- Decane p 1000.00 0.061 0.19

Isobutylbenzene + 1

- Me

- 2

- Propylcyclohexane a 1008.16 0.021 0.07

sec

- Butylbenzene a 1010.39 0.015 0.05

m

- Cymene a 1018.22 0.020 0.06

1,2,3

- TriMethylbenzene a 1022.13 0.156 0.41

Unknown u 1031.59 0.196 0.57

Indane n 1036.98 0.022 0.07

Unknown u 1040.81 0.075 0.22

Unknown u 1048.17 0.284 0.87

n

- Butylbenzene + p

- Diethylbenzene a 1054.69 0.000 0.18

1

- Me

- 4

- isoPropylbenzene a 1059.44 0.067 0.05

Unknown u 1062.68 0.022 0.13

1

- Me

- 2

- n

- Propylbenzene a 1067.27 0.048 0.49

1,4

- DiMe

- 2

- Ethylbenzene a 1075.98 0.168 0.10

Unknown u 1078.46 0.033 0.15

1,2

- DiMe

- 4

- Ethylbenzene a 1084.27 0.047 0.19

Unknown u 1086.66 0.064 0.32

1,3

- DiMe

- 2

- Ethylbenzene a 1092.85 0.123 0.03

Unknown u 1094.62 0.023 0.04

n

- Undecane p 1100.00 0.019 0.07

1,2

- DiMe

- 3

- Ethylbenzene a 1107.49 0.031 0.06

1,2,4,5

- Tetra

- Me

- Benzene a 1119.01 0.023 0.14

Unknown u 1123.00 0.042 0.20

## 11 t

- 1

- But

- 2

- MeBenzene a 1139.52 0.060 0.02

Unknown u 1144.96 0.005 0.09

Methylindane n 1156.53 0.027 0.08

n

- Pentylbenzene + t

- 1

- Me

- 2

- (4MP)cyclohexane a 1158.21 0.025 0.05

t

- 1

- But

- 3,5

- DiMeBenzene a 1174.77 0.011 0.09

Unknown u 1175.94 0.005 0.00

t

- 1

- But

- 4

- Ethylbenzene a 1183.89 0.000 0.05

Naphthalene n 1189.56 0.000 0.00

n

- Dodecane p 1200.00 0.000 0.00

% Listed Peaks are of Total VOC 98.95 97.27

## 12 Table 5

. Summary statistics for the hydrocarbon composition of Fuel 14.



# Summary Statistics for Fuel #14

HS Whole



# Ethanol 0.000 0.000

%Paraffins 76.11 65.81

%Olefins 14.23 8.17

%Aromatics 7.61 20.35

%Unknowns 0.95 2.79

%Fused Rings 0.05 0.15

## 13 Table 6

. Headspace and whole fuel composition of Fuel 6.

Fuel # 6 Headspace@25C and Whole Fuel Composition

Compound Type RTINDEX HS Whole

Propane p 300.00 0.009 0.02

Isobutane p 361.88 0.126 0.06

Butene

- 1 o 389.97 0.076 0.00

Isobutylene o 390.92 0.085 0.03

n

- Butane p 400.00 4.886 1.34

t

- Butene

- 2 o 411.64 0.371 0.10

2,2

- Dimethylpropane* p 413.35 0.026 0.17

c

- Butene

- 2 o 425.94 0.376 0.09

3

- Methyl

- 1

- Butene o 457.43 0.247 0.07

Ethanol ox 461.50 6.487 8.76

Isopentane p 474.54 11.796 4.37

Pentene

- 1 o 489.36 1.071 0.37

2

- Methyl

- 1

- Butene o 496.17 1.602 0.63

n

- Pentane p 500.00 2.463 1.02

Isoprene o 504.19 0.032 0.01

trans

- 2

- Pentene o 508.72 2.477 1.03

Unknown u 513.67 0.018 0.01

cis

- 2

- Pentene o 516.35 1.347 0.57

2

- Methyl

- 2

- Butene o 521.04 2.910 1.30

2,2

- Dimethylbutane p 535.47 0.250 0.12

Cyclopentene o 551.84 0.507 0.25

3

- Methyl

- 1

- pentene o 557.98 0.260 0.15

Cyclopentane p 562.82 0.345 0.17

2,3

- Dimethylbutane p 565.46 2.701 1.81

2

- Methylpentane p 570.09 10.877 7.81

3

- Methylpentane p 583.52 7.087 5.65

2

- Methyl

- 1

- Pentene o 588.52 0.268 0.24

Hexene

- 1 o 589.36 2.287 1.91

n

- Hexane p 600.00 5.932 5.27

trans

- 3

- Hexene o 602.80 0.367 0.35

trans

- 2

- Hexene o 604.98 0.523 0.48

2

- Methyl

- 2

- Pentene o 607.37 0.471 0.44

Unknown u 608.87 0.159 0.13

cis

- 3

- Hexene o 610.49 0.293 0.28

4

- Methylcyclopentene* o 612.17 0.078 0.07

cis

- 2

- Hexene o 614.50 0.281 0.26

cis

- 3

- Methyl

- 2

- pentene* o 620.74 0.387 0.40

2,2

- DiMethylpentane p 625.13 0.162 0.18

Methylcyclopentane p 627.20 2.043 1.89

2,4

- Dimethylpentane p 631.38 0.763 1.03

2,2,3

- TriMethylbutane p 637.00 0.074 0.09

2,4

- DiMethyl

- 1

- Pentene o 647.79 0.013 0.02

1

- Methylcyclopentene o 651.00 0.316 0.39

Benzene a 651.21 0.949 1.15

3,3

- DiMethylpentane p 657.00 0.073 0.09

Cyclohexane p 660.96 1.597 1.32

4

- Me

- 1

- Hexene o 665.23 0.016 0.00

2

- Methylhexane p 668.68 0.655 0.93

2,3

- Dimethylpentane p 670.80 0.611 0.70

1,1

- DiMeCyclopentane p 674.11 0.032 0.03

3

- Methylhexane p 677.22 0.519 0.70

5

- Methyl

- 2

- hexene* o 680.55 0.010 0.02

c

- 1,3

- DiMeCyclopentane p 684.41 0.095 0.12

t

- 1,3,

- DiMeCyclopentane p 687.12 0.117 0.16

2,2,4

- TriMethylpentane p 690.72 7.197 6.82

3

- Methyl

- 3

- hexene o 695.08 0.007 0.01

trans

- 3

- Heptene o 697.82 0.013 0.03

n

- Heptane p 700.00 0.279 0.28

3

- Me

- cis

- 3

- Hexene o 701.44 0.045 0.11

2,4,4

- TriMethyl

- 1

- Pentene o 712.30 0.145 0.02

MethylCyclohexane p 724.30 0.356 0.12

2,5

- DiMethylhexane p 733.56 0.441 0.82

## 14 2,4

- DiMethylhexane + EthylCyclopentane p 735.91 0.582 1.19

3,3

- DiMethylhexane + 1,2,4

- TriMeCyclopentane p 743.87 0.011 0.01

ctc

- 1,2,3

- TriMeCyclopentane p 751.44 0.004 0.00

2,3,4

- TriMethylpentane p 753.56 0.973 2.92

Toluene a 758.58 4.071 9.04

2,3

- DiMethylhexane p 762.98 0.235 0.82

2

- Methyl

- 3

- Ethylpentane p 765.00 0.012 0.00

2

- Methylheptane p 767.55 0.045 0.05

4

- Methylheptane p 769.28 0.016 0.02

3,4

- DiMethylhexane p 772.50 0.040 0.14

3

- Methylheptane p 775.34 0.043 0.06

ctc

- 1,2,4

- TriMeCyclopentane p 781.70 0.027 0.01

t

- 1,4

- DiMeCyclohexane p 783.92 0.011 0.00

2,2,5

- Trimethylhexane p 785.98 0.279 1.19

1,1

- DiMethylCyclohexane p 790.50 0.007 0.00

2,2,4

- TriMethylhexane p 794.85 0.008 0.02

n

- Octane p 800.00 0.049 0.03

cis

- 2

- Octene o 812.37 0.007 0.03

2,3,5

- TriMethylhexane p 819.44 0.038 0.19

2,4

- DiMethylheptane p 825.88 0.008 0.04

2,6

- DiMethylheptane p 831.77 0.008 0.03

1c2

- DiMethylcyclohexane n

- Propylcyclopentane p 834.70 0.001 0.00

2,5

- DiMeHeptane p 838.60 0.026 0.08

Ethylbenzene a 855.40 0.415 0.98

ctt

- 1,2,4

- TriMeCyclohexane p 860.26 0.015 0.04

m

- & p

- Xylene a 863.65 1.430 3.53

3

- Methyloctane p 873.73 0.005 0.01

ctc

- 1,2,4

- TriMeCyclohexane p 881.42 0.034 0.15

o

- Xylene a 887.56 0.327 0.75

Nonene

- 1 o 889.31 0.000 0.10

Nonane p 900.00 0.008 0.01

trans

- 2

- Nonene o 902.49 0.020 0.09

cis

- 2

- Nonene o 912.37 0.003 0.01

Isopropylbenzene a 920.34 0.051 0.16

3,5

- DiMethyloctane p 927.97 0.015 0.06

2,6

- DiMethyloctane p 937.70 0.062 0.24

n

- Propylbenzene a 950.95 0.084 0.23

m

- Ethyltoluene a 957.45 0.324 0.86

p

- Ethyltoluene a 960.02 0.174 0.41

1,3,5

- TriMethylbenzene a 964.32 0.187 0.47

3

- Methylnonane p 973.55 0.004 0.01

o

- Ethyltoluene a 976.97 0.165 0.46

Unknown u 986.65 0.049 0.16

Unknown u 988.06 0.000 0.00

1,2,4

- TriMethylbenzene a 991.48 0.529 1.27

n

- Decane p 1000.00 0.115 0.40

Isobutylbenzene + 1

- Me

- 2

- Propylcyclohexane a 1008.16 0.035 0.11

sec

- Butylbenzene a 1010.39 0.023 0.06

m

- Cymene a 1018.22 0.029 0.08

1,2,3

- TriMethylbenzene a 1022.13 0.219 0.45

Unknown u 1031.59 0.288 0.89

Indane n 1036.98 0.022 0.03

Unknown u 1040.81 0.100 0.30

Unknown u 1048.17 0.368 1.10

n

- Butylbenzene + p

- Diethylbenzene a 1054.69 0.000 0.15

1

- Me

- 4

- isoPropylbenzene a 1059.44 0.039 0.06

Unknown u 1062.68 0.018 0.16

1

- Me

- 2

- n

- Propylbenzene a 1067.27 0.054 0.57

1,4

- DiMe

- 2

- Ethylbenzene a 1075.98 0.212 0.08

Unknown u 1078.46 0.033 0.11

1,2

- DiMe

- 4

- Ethylbenzene a 1084.27 0.046 0.13

Unknown u 1086.66 0.051 0.34

1,3

- DiMe

- 2

- Ethylbenzene a 1092.85 0.135 0.04

Unknown u 1094.62 0.018 0.05

n

- Undecane p 1100.00 0.015 0.08

1,2

- DiMe

- 3

- Ethylbenzene a 1107.49 0.022 0.05

1,2,4,5

- Tetra

- Me

- Benzene a 1119.01 0.016 0.12

Unknown u 1123.00 0.033 0.18

## 15 t

- 1

- But

- 2

- MeBenzene a 1139.52 0.047 0.02

Unknown u 1144.96 0.004 0.06

Methylindane n 1156.53 0.018 0.06

n

- Pentylbenzene + t

- 1

- Me

- 2

- (4MP)cyclohexane a 1158.21 0.019 0.04

t

- 1

- But

- 3,5

- DiMeBenzene a 1174.77 0.009 0.06

Unknown u 1175.94 0.001 0.00

t

- 1

- But

- 4

- Ethylbenzene a 1183.89 0.000 0.03

Naphthalene n 1189.56 0.000 0.00

n

- Dodecane p 1200.00 0.000 0.00



### % Listed Peaks are of Total VOC 98.40 94.49

## 16 Table 7

. Summary statistics for the hydrocarbon composition of Fuel 6.



# Summary Statistics for Fuel # 6

HS Whole



# %Ethanol 6.49 8.76

%Paraffins 64.21 50.90

%Olefins 16.91 9.87

%Aromatics 9.61 21.36

%Unknowns 1.14 3.51

%Fused Rings 0.04 0.09

## 17 Table 8

. Headspace and whole fuel composition of Fuel No 10.

Fuel # 10 Headspace@25C and Whole Fuel Composition

Compound Type RTINDEX HS Whole

Propane p 300.00 0.008 0.01

Isobutane p 361.88 0.076 0.02

Butene

- 1 o 389.97 0.055 0.00

Isobutylene o 390.92 0.058 0.04

n

- Butane p 400.00 4.024 1.32

t

- Butene

- 2 o 411.64 0.269 0.10

2,2

- Dimethylpropane* p 413.35 0.047 0.07

c

- Butene

- 2 o 425.94 0.266 0.09

3

- Methyl

- 1

- Butene o 457.43 0.170 0.07

Ethanol ox 461.50 6.406 7.74

Isopentane p 474.54 8.787 4.06

Pentene

- 1 o 489.36 0.762 0.36

2

- Methyl

- 1

- Butene o 496.17 1.140 0.58

n

- Pentane p 500.00 3.817 1.94

Isoprene o 504.19 0.022 0.01

trans

- 2

- Pentene o 508.72 1.823 0.95

Unknown u 513.67 0.016 0.01

cis

- 2

- Pentene o 516.35 0.991 0.52

2

- Methyl

- 2

- Butene o 521.04 2.197 1.18

2,2

- Dimethylbutane p 535.47 0.618 0.35

Cyclopentene o 551.84 0.396 0.24

3

- Methyl

- 1

- pentene o 557.98 0.229 0.13

Cyclopentane p 562.82 0.601 0.37

2,3

- Dimethylbutane p 565.46 2.063 1.32

2

- Methylpentane p 570.09 11.190 7.62

3

- Methylpentane p 583.52 6.106 4.35

2

- Methyl

- 1

- Pentene o 588.52 0.364 0.27

Hexene

- 1 o 589.36 0.290 0.16

n

- Hexane p 600.00 6.388 5.22

trans

- 3

- Hexene o 602.80 0.384 0.31

trans

- 2

- Hexene o 604.98 0.549 0.45

2

- Methyl

- 2

- Pentene o 607.37 0.498 0.41

Unknown u 608.87 0.159 0.12

cis

- 3

- Hexene o 610.49 0.306 0.25

4

- Methylcyclopentene* o 612.17 0.082 0.05

cis

- 2

- Hexene o 614.50 0.297 0.24

cis

- 3

- Methyl

- 2

- pentene* o 620.74 0.414 0.38

2,2

- DiMethylpentane p 625.13 0.209 0.22

Methylcyclopentane p 627.20 2.235 2.04

2,4

- Dimethylpentane p 631.38 0.449 0.41

2,2,3

- TriMethylbutane p 637.00 0.062 0.06

2,4

- DiMethyl

- 1

- Pentene o 647.79 0.014 0.02

1

- Methylcyclopentene o 651.00 0.367 0.38

Benzene a 651.21 0.793 0.95

3,3

- DiMethylpentane p 657.00 0.081 0.10

Cyclohexane p 660.96 1.548 1.66

4

- Me

- 1

- Hexene o 665.23 0.018 0.03

2

- Methylhexane p 668.68 0.712 0.93

2,3

- Dimethylpentane p 670.80 0.316 0.24

1,1

- DiMeCyclopentane p 674.11 0.037 0.05

3

- Methylhexane p 677.22 0.547 0.72

5

- Methyl

- 2

- hexene* o 680.55 0.012 0.02

c

- 1,3

- DiMeCyclopentane p 684.41 0.110 0.15

t

- 1,3,

- DiMeCyclopentane p 687.12 0.135 0.19

2,2,4

- TriMethylpentane p 690.72 3.599 0.20

3

- Methyl

- 3

- hexene o 695.08 0.009 0.02

## 18 trans

- 3

- Heptene o 697.82 0.018 0.03

n

- Heptane p 700.00 0.300 0.39

3

- Me

- cis

- 3

- Hexene o 701.44 0.061 0.12

2,4,4

- TriMethyl

- 1

- Pentene o 712.30 0.107 0.02

MethylCyclohexane p 724.30 0.363 0.39

2,5

- DiMethylhexane p 733.56 0.368 0.16

2,4

- DiMethylhexane + EthylCyclopentane p 735.91 0.489 0.27

3,3

- DiMethylhexane + 1,2,4

- TriMeCyclopentane p 743.87 0.014 0.02

ctc

- 1,2,3

- TriMeCyclopentane p 751.44 0.006 0.01

2,3,4

- TriMethylpentane p 753.56 0.913 0.98

Toluene a 758.58 6.355 15.10

2,3

- DiMethylhexane p 762.98 0.248 0.35

2

- Methyl

- 3

- Ethylpentane p 765.00 0.000 0.00

2

- Methylheptane p 767.55 0.064 0.07

4

- Methylheptane p 769.28 0.022 0.03

3,4

- DiMethylhexane p 772.50 0.043 0.06

3

- Methylheptane p 775.34 0.062 0.06

ctc

- 1,2,4

- TriMeCyclopentane p 781.70 0.039 0.03

t

- 1,4

- DiMeCyclohexane p 783.92 0.017 0.01

2,2,5

- Trimethylhexane p 785.98 0.309 0.60

1,1

- DiMethylCyclohexane p 790.50 0.007 0.01

2,2,4

- TriMethylhexane p 794.85 0.010 0.02

n

- Octane p 800.00 0.078 0.07

cis

- 2

- Octene o 812.37 0.009 0.02

2,3,5

- TriMethylhexane p 819.44 0.049 0.11

2,4

- DiMethylheptane p 825.88 0.011 0.03

2,6

- DiMethylheptane p 831.77 0.014 0.02

1c2

- DiMethylcyclohexane n

- Propylcyclopentane p 834.70 0.003 0.00

2,5

- DiMeHeptane p 838.60 0.044 0.06

Ethylbenzene a 855.40 0.958 2.36

ctt

- 1,2,4

- TriMeCyclohexane p 860.26 0.020 0.04

m

- & p

- Xylene a 863.65 3.423 8.48

3

- Methyloctane p 873.73 0.011 0.01

ctc

- 1,2,4

- TriMeCyclohexane p 881.42 0.043 0.11

o

- Xylene a 887.56 0.731 1.54

Nonene

- 1 o 889.31 0.000 0.00

Nonane p 900.00 0.019 0.01

trans

- 2

- Nonene o 902.49 0.025 0.05

cis

- 2

- Nonene o 912.37 0.000 0.00

Isopropylbenzene a 920.34 0.067 0.11

3,5

- DiMethyloctane p 927.97 0.017 0.04

2,6

- DiMethyloctane p 937.70 0.080 0.15

n

- Propylbenzene a 950.95 0.191 0.41

m

- Ethyltoluene a 957.45 0.751 1.66

p

- Ethyltoluene a 960.02 0.367 0.88

1,3,5

- TriMethylbenzene a 964.32 0.464 0.99

3

- Methylnonane p 973.55 0.009 0.02

o

- Ethyltoluene a 976.97 0.348 0.70

Unknown u 986.65 0.066 0.13

Unknown u 988.06 0.000 0.00

1,2,4

- TriMethylbenzene a 991.48 1.308 2.70

n

- Decane p 1000.00 0.187 0.27

Isobutylbenzene + 1

- Me

- 2

- Propylcyclohexane a 1008.16 0.064 0.10

sec

- Butylbenzene a 1010.39 0.043 0.07

m

- Cymene a 1018.22 0.061 0.09

1,2,3

- TriMethylbenzene a 1022.13 0.387 0.74

Unknown u 1031.59 0.590 0.65

Indane n 1036.98 0.064 0.14

Unknown u 1040.81 0.218 0.23

Unknown u 1048.17 0.840 1.01

n

- Butylbenzene + p

- Diethylbenzene a 1054.69 0.000 0.26

## 19 1

- Me

- 4

- isoPropylbenzene a 1059.44 0.214 0.05

Unknown u 1062.68 0.053 0.12

1

- Me

- 2

- n

- Propylbenzene a 1067.27 0.142 0.52

1,4

- DiMe

- 2

- Ethylbenzene a 1075.98 0.500 0.14

Unknown u 1078.46 0.109 0.17

1,2

- DiMe

- 4

- Ethylbenzene a 1084.27 0.151 0.29

Unknown u 1086.66 0.212 0.31

1,3

- DiMe

- 2

- Ethylbenzene a 1092.85 0.319 0.07

Unknown u 1094.62 0.045 0.04

n

- Undecane p 1100.00 0.056 0.07

1,2

- DiMe

- 3

- Ethylbenzene a 1107.49 0.095 0.12

1,2,4,5

- Tetra

- Me

- Benzene a 1119.01 0.149 0.21

Unknown u 1123.00 0.148 0.29

t

- 1

- But

- 2

- MeBenzene a 1139.52 0.210 0.03

Unknown u 1144.96 0.022 0.15

Methylindane n 1156.53 0.094 0.13

n

- Pentylbenzene + t

- 1

- Me

- 2

- (4MP)cyclohexane a 1158.21 0.089 0.08

t

- 1

- But

- 3,5

- DiMeBenzene a 1174.77 0.057 0.05

Unknown u 1175.94 0.000 0.00

t

- 1

- But

- 4

- Ethylbenzene a 1183.89 0.024 0.02

Naphthalene n 1189.56 0.020 0.00

n

- Dodecane p 1200.00 0.000 0.00

% Listed Peaks are of TotalVOC 97.21 95.52

## 20 Table 9

. Summary statistics for the hydrocarbon composition of Fuel 10.



# Summary Statistics for Fuel # 10

HS Whole



# %Ethanol 6.41 7.74

%Paraffins 57.68 38.07

%Olefins 12.20 7.51

%Aromatics 18.26 38.71

%Unknowns 2.48 3.22

%Fused Rings 0.18 0.26

## 21 Table 10. Headspace and whole fuel composition of Fuel No 27.

Fuel # 27 Headspace@25C and Whole Fuel Composition

**Compound** Type RTINDEX HS Whole

Propane p 300.00 0.004 0.04

Isobutane p 361.88 0.098 0.05

Butene

- 1 o 389.97 0.063 0.04

Isobutylene o 390.92 0.067 0.00

n

- Butane p 400.00 4.764 1.68

t

- Butene

- 2 o 411.64 0.319 0.11

2,2

- Dimethylpropane* p 413.35 0.029 0.27

c

- Butene

- 2 o 425.94 0.302 0.11

3

- Methyl

- 1

- Butene o 457.43 0.185 0.09

Ethanol ox 461.50 26.516 12.35

Isopentane p 474.54 9.620 5.05

Pentene

- 1 o 489.36 0.813 0.41

2

- Methyl

- 1

- Butene o 496.17 1.230 0.66

n

- Pentane p 500.00 1.834 1.05

Isoprene o 504.19 0.025 0.03

trans

- 2

- Pentene o 508.72 1.930 1.09

Unknown u 513.67 0.017 0.01

cis

- 2

- Pentene o 516.35 1.057 0.59

2

- Methyl

- 2

- Butene o 521.04 2.328 1.34

2,2

- Dimethylbutane p 535.47 0.058 0.04

Cyclopentene o 551.84 0.435 0.26

3

- Methyl

- 1

- pentene o 557.98 0.241 0.15

Cyclopentane p 562.82 0.193 0.13

2,3

- Dimethylbutane p 565.46 2.334 1.64

2

- Methylpentane p 570.09 3.356 2.27

3

- Methylpentane p 583.52 1.985 1.45

2

- Methyl

- 1

- Pentene o 588.52 0.419 0.29

Hexene

- 1 o 589.36 0.250 0.20

n

- Hexane p 600.00 1.639 1.26

trans

- 3

- Hexene o 602.80 0.429 0.34

trans

- 2

- Hexene o 604.98 0.627 0.50

2

- Methyl

- 2

- Pentene o 607.37 0.565 0.46

Unknown u 608.87 0.190 0.14

cis

- 3

- Hexene o 610.49 0.344 0.29

4

- Methylcyclopentene* o 612.17 0.092 0.07

cis

- 2

- Hexene o 614.50 0.342 0.28

cis

- 3

- Methyl

- 2

- pentene* o 620.74 0.492 0.41

2,2

- DiMethylpentane p 625.13 0.043 0.03

Methylcyclopentane p 627.20 1.317 1.10

2,4

- Dimethylpentane p 631.38 1.276 1.25

2,2,3

- TriMethylbutane p 637.00 0.093 0.09

2,4

- DiMethyl

- 1

- Pentene o 647.79 0.018 0.02

1

- Methylcyclopentene o 651.00 0.439 0.42

Benzene a 651.21 1.148 1.04

3,3

- DiMethylpentane p 657.00 0.003 0.05

Cyclohexane p 660.96 0.385 0.33

4

- Me

- 1

- Hexene o 665.23 0.027 0.03

2

- Methylhexane p 668.68 0.552 0.63

2,3

- Dimethylpentane p 670.80 0.678 0.81

1,1

- DiMeCyclopentane p 674.11 0.011 0.01

3

- Methylhexane p 677.22 0.435 0.50

5

- Methyl

- 2

- hexene* o 680.55 0.015 0.01

c

- 1,3

- DiMeCyclopentane p 684.41 0.096 0.11

t

- 1,3,

- DiMeCyclopentane p 687.12 0.122 0.14

2,2,4

- TriMethylpentane p 690.72 6.601 9.26

3

- Methyl

- 3

- hexene o 695.08 0.016 0.02

trans

- 3

- Heptene o 697.82 0.025 0.03

n

- Heptane p 700.00 0.154 0.18

3

- Me

- cis

- 3

- Hexene o 701.44 0.086 0.12

2,4,4

- TriMethyl

- 1

- Pentene o 712.30 0.033 0.03

MethylCyclohexane p 724.30 0.095 0.08

2,5

- DiMethylhexane p 733.56 0.756 1.42

## 22 2,4

- DiMethylhexane + EthylCyclopentane p 735.91 1.042 1.96

3,3

- DiMethylhexane + 1,2,4

- TriMeCyclopentane p 743.87 0.006 0.01

ctc

- 1,2,3

- TriMeCyclopentane p 751.44 0.000 0.00

2,3,4

- TriMethylpentane p 753.56 2.505 5.37

Toluene a 758.58 6.719 12.69

2,3

- DiMethylhexane p 762.98 0.570 1.34

2

- Methyl

- 3

- Ethylpentane p 765.00 0.017 0.06

2

- Methylheptane p 767.55 0.038 0.07

4

- Methylheptane p 769.28 0.013 0.02

3,4

- DiMethylhexane p 772.50 0.104 0.25

3

- Methylheptane p 775.34 0.043 0.08

ctc

- 1,2,4

- TriMeCyclopentane p 781.70 0.013 0.01

t

- 1,4

- DiMeCyclohexane p 783.92 0.004 0.00

2,2,5

- Trimethylhexane p 785.98 0.849 2.41

1,1

- DiMethylCyclohexane p 790.50 0.003 0.00

2,2,4

- TriMethylhexane p 794.85 0.010 0.03

n

- Octane p 800.00 0.037 0.03

cis

- 2

- Octene o 812.37 0.021 0.07

2,3,5

- TriMethylhexane p 819.44 0.112 0.38

2,4

- DiMethylheptane p 825.88 0.015 0.05

2,6

- DiMethylheptane p 831.77 0.019 0.07

1c2

- DiMethylcyclohexane n

- Propylcyclopentane p 834.70 0.000 0.00

2,5

- DiMeHeptane p 838.60 0.050 0.17

Ethylbenzene a 855.40 0.452 0.99

ctt

- 1,2,4

- TriMeCyclohexane p 860.26 0.027 0.08

m

- & p

- Xylene a 863.65 1.509 3.52

3

- Methyloctane p 873.73 0.010 0.03

ctc

- 1,2,4

- TriMeCyclohexane p 881.42 0.087 0.36

o

- Xylene a 887.56 0.288 0.73

Nonene

- 1 o 889.31 0.058 0.24

Nonane p 900.00 0.027 0.10

trans

- 2

- Nonene o 902.49 0.041 0.16

cis

- 2

- Nonene o 912.37 0.000 0.01

Isopropylbenzene a 920.34 0.062 0.23

3,5

- DiMethyloctane p 927.97 0.026 0.09

2,6

- DiMethyloctane p 937.70 0.084 0.30

n

- Propylbenzene a 950.95 0.074 0.21

m

- Ethyltoluene a 957.45 0.279 0.77

p

- Ethyltoluene a 960.02 0.173 0.38

1,3,5

- TriMethylbenzene a 964.32 0.176 0.50

3

- Methylnonane p 973.55 0.015 0.05

o

- Ethyltoluene a 976.97 0.154 0.44

Unknown u 986.65 0.058 0.15

Unknown u 988.06 0.000 0.00

1,2,4

- TriMethylbenzene a 991.48 0.441 1.16

n

- Decane p 1000.00 0.000 0.48

Isobutylbenzene + 1

- Me

- 2

- Propylcyclohexane a 1008.16 0.038 0.10

sec

- Butylbenzene a 1010.39 0.023 0.06

m

- Cymene a 1018.22 0.033 0.09

1,2,3

- TriMethylbenzene a 1022.13 0.000 0.26

Unknown u 1031.59 0.297 0.77

Indane n 1036.98 0.024 0.06

Unknown u 1040.81 0.105 0.26

Unknown u 1048.17 0.388 0.88

n

- Butylbenzene + p

- Diethylbenzene a 1054.69 0.000 0.06

1

- Me

- 4

- isoPropylbenzene a 1059.44 0.057 0.04

Unknown u 1062.68 0.031 0.13

1

- Me

- 2

- n

- Propylbenzene a 1067.27 0.056 0.45

1,4

- DiMe

- 2

- Ethylbenzene a 1075.98 0.195 0.05

Unknown u 1078.46 0.028 0.06

1,2

- DiMe

- 4

- Ethylbenzene a 1084.27 0.034 0.08

Unknown u 1086.66 0.036 0.22

1,3

- DiMe

- 2

- Ethylbenzene a 1092.85 0.145 0.02

Unknown u 1094.62 0.025 0.03

n

- Undecane p 1100.00 0.013 0.05

1,2

- DiMe

- 3

- Ethylbenzene a 1107.49 0.026 0.02

1,2,4,5

- Tetra

- Me

- Benzene a 1119.01 0.016 0.06

Unknown u 1123.00 0.033 0.10

## 23 t

- 1

- But

- 2

- MeBenzene a 1139.52 0.047 0.01

Unknown u 1144.96 0.004 0.03

Methylindane n 1156.53 0.022 0.04

n

- Pentylbenzene + t

- 1

- Me

- 2

- (4MP)cyclohexane a 1158.21 0.019 0.03

t

- 1

- But

- 3,5

- DiMeBenzene a 1174.77 0.010 0.01

Unknown u 1175.94 0.009 0.00

t

- 1

- But

- 4

- Ethylbenzene a 1183.89 0.000 0.01

Naphthalene n 1189.56 0.004 0.00

n

- Dodecane p 1200.00 0.000 0.00

% Listed Peaks are of TotalVOC 97.56 92.90

## 24 Table 11. Summary statistics for the hydrocarbon composition of Fuel 27.



# Summary Statistics for Fuel# 27

HS Whole



# % Ethanol 26.52 12.35

%Paraffins 44.27 44.76

%Olefins 13.33 8.87

%Aromatics 12.17 24.02

%Unknowns 1.22 2.79

%Fused Rings 0.05 0.10

## 25 Table 12. Headspace and whole fuel composition of Fuel 28.

Fuel # 28 Headspace@25C and Whole Fuel Composition

Compound Type RTINDEX HS Whole

Propane p 300.00 0.009 0.02

Isobutane p 361.88 0.099 0.04

Butene

- 1 o 389.97 0.065 0.00

Isobutylene o 390.92 0.092 0.03

n

- Butane p 400.00 6.827 1.98

t

- Butene

- 2 o 411.64 0.319 0.11

2,2

- Dimethylpropane* p 413.35 0.024 0.04

c

- Butene

- 2 o 425.94 0.340 0.11

3

- Methyl

- 1

- Butene o 457.43 0.202 0.07

Ethanol ox 461.50 27.854 11.10

Isopentane p 474.54 8.310 3.58

Pentene

- 1 o 489.36 0.868 0.38

2

- Methyl

- 1

- Butene o 496.17 1.305 0.61

n

- Pentane p 500.00 1.951 0.95

Isoprene o 504.19 0.029 0.01

trans

- 2

- Pentene o 508.72 2.025 1.00

Unknown u 513.67 0.015 0.01

cis

- 2

- Pentene o 516.35 1.107 0.55

2

- Methyl

- 2

- Butene o 521.04 2.425 1.24

2,2

- Dimethylbutane p 535.47 0.060 0.03

Cyclopentene o 551.84 0.439 0.24

3

- Methyl

- 1

- pentene o 557.98 0.247 0.14

Cyclopentane p 562.82 0.198 0.12

2,3

- Dimethylbutane p 565.46 1.336 0.83

2

- Methylpentane p 570.09 3.393 2.20

3

- Methylpentane p 583.52 2.261 1.54

2

- Methyl

- 1

- Pentene o 588.52 0.401 0.27

Hexene

- 1 o 589.36 0.248 0.18

n

- Hexane p 600.00 2.724 2.03

trans

- 3

- Hexene o 602.80 0.416 0.31

trans

- 2

- Hexene o 604.98 0.607 0.45

2

- Methyl

- 2

- Pentene o 607.37 0.551 0.41

Unknown u 608.87 0.179 0.12

cis

- 3

- Hexene o 610.49 0.334 0.25

4

- Methylcyclopentene* o 612.17 0.090 0.06

cis

- 2

- Hexene o 614.50 0.331 0.25

cis

- 3

- Methyl

- 2

- pentene* o 620.74 0.472 0.38

2,2

- DiMethylpentane p 625.13 0.082 0.07

Methylcyclopentane p 627.20 1.480 1.18

2,4

- Dimethylpentane p 631.38 0.706 0.62

2,2,3

- TriMethylbutane p 637.00 0.057 0.05

2,4

- DiMethyl

- 1

- Pentene o 647.79 0.017 0.02

1

- Methylcyclopentene o 651.00 0.433 0.37

Benzene a 651.21 1.021 0.95

3,3

- DiMethylpentane p 657.00 0.061 0.05

Cyclohexane p 660.96 0.595 0.55

4

- Me

- 1

- Hexene o 665.23 0.031 0.03

2

- Methylhexane p 668.68 0.541 0.60

2,3

- Dimethylpentane p 670.80 0.367 0.38

1,1

- DiMeCyclopentane p 674.11 0.012 0.01

3

- Methylhexane p 677.22 0.412 0.47

5

- Methyl

- 2

- hexene* o 680.55 0.014 0.02

c

- 1,3

- DiMeCyclopentane p 684.41 0.090 0.10

t

- 1,3,

- DiMeCyclopentane p 687.12 0.112 0.14

2,2,4

- TriMethylpentane p 690.72 2.981 3.53

3

- Methyl

- 3

- hexene o 695.08 0.012 0.02

## 26 trans

- 3

- Heptene o 697.82 0.023 0.03

n

- Heptane p 700.00 0.133 0.18

3

- Me

- cis

- 3

- Hexene o 701.44 0.080 0.11

2,4,4

- TriMethyl

- 1

- Pentene o 712.30 0.019 0.02

MethylCyclohexane p 724.30 0.056 0.07

2,5

- DiMethylhexane p 733.56 0.562 0.96

2,4

- DiMethylhexane + EthylCyclopentane p 735.91 0.806 1.38

3,3

- DiMethylhexane + 1,2,4

- TriMeCyclopentane p 743.87 0.004 0.01

ctc

- 1,2,3

- TriMeCyclopentane p 751.44 0.000 0.00

2,3,4

- TriMethylpentane p 753.56 2.393 4.73

Toluene a 758.58 10.859 23.35

2,3

- DiMethylhexane p 762.98 0.581 1.26

2

- Methyl

- 3

- Ethylpentane p 765.00 0.024 0.05

2

- Methylheptane p 767.55 0.038 0.08

4

- Methylheptane p 769.28 0.016 0.03

3,4

- DiMethylhexane p 772.50 0.116 0.25

3

- Methylheptane p 775.34 0.041 0.07

ctc

- 1,2,4

- TriMeCyclopentane p 781.70 0.006 0.01

t

- 1,4

- DiMeCyclohexane p 783.92 0.002 0.00

2,2,5

- Trimethylhexane p 785.98 0.963 2.59

1,1

- DiMethylCyclohexane p 790.50 0.000 0.00

2,2,4

- TriMethylhexane p 794.85 0.012 0.03

n

- Octane p 800.00 0.018 0.03

cis

- 2

- Octene o 812.37 0.024 0.08

2,3,5

- TriMethylhexane p 819.44 0.127 0.42

2,4

- DiMethylheptane p 825.88 0.017 0.06

2,6

- DiMethylheptane p 831.77 0.024 0.07

1c2

- DiMethylcyclohexane n

- Propylcyclopentane p 834.70 0.000 0.00

2,5

- DiMeHeptane p 838.60 0.047 0.18

Ethylbenzene a 855.40 0.750 2.88

ctt

- 1,2,4

- TriMeCyclohexane p 860.26 0.028 0.11

m

- & p

- Xylene a 863.65 2.515 10.26

3

- Methyloctane p 873.73 0.005 0.01

ctc

- 1,2,4

- TriMeCyclohexane p 881.42 0.088 0.43

o

- Xylene a 887.56 0.401 1.69

Nonene

- 1 o 889.31 0.061 0.27

Nonane p 900.00 0.008 0.01

trans

- 2

- Nonene o 902.49 0.031 0.15

cis

- 2

- Nonene o 912.37 0.001 0.01

Isopropylbenzene a 920.34 0.019 0.08

3,5

- DiMethyloctane p 927.97 0.005 0.01

2,6

- DiMethyloctane p 937.70 0.016 0.02

n

- Propylbenzene a 950.95 0.047 0.19

m

- Ethyltoluene a 957.45 0.168 0.76

p

- Ethyltoluene a 960.02 0.093 0.46

1,3,5

- TriMethylbenzene a 964.32 0.090 0.43

3

- Methylnonane p 973.55 0.002 0.01

o

- Ethyltoluene a 976.97 0.064 0.28

Unknown u 986.65 0.011 0.05

Unknown u 988.06 0.000 0.00

1,2,4

- TriMethylbenzene a 991.48 0.235 1.23

n

- Decane p 1000.00 0.022 0.00

Isobutylbenzene + 1

- Me

- 2

- Propylcyclohexane a 1008.16 0.007 0.02

sec

- Butylbenzene a 1010.39 0.007 0.02

m

- Cymene a 1018.22 0.008 0.03

1,2,3

- TriMethylbenzene a 1022.13 0.000 0.37

Unknown u 1031.59 0.048 0.12

Indane n 1036.98 0.012 0.07

Unknown u 1040.81 0.019 0.05

Unknown u 1048.17 0.074 0.26

n

- Butylbenzene + p

- Diethylbenzene a 1054.69 0.000 0.13

## 27 1

- Me

- 4

- isoPropylbenzene a 1059.44 0.018 0.04

Unknown u 1062.68 0.006 0.04

1

- Me

- 2

- n

- Propylbenzene a 1067.27 0.010 0.14

1,4

- DiMe

- 2

- Ethylbenzene a 1075.98 0.038 0.06

Unknown u 1078.46 0.007 0.08

1,2

- DiMe

- 4

- Ethylbenzene a 1084.27 0.008 0.29

Unknown u 1086.66 0.011 0.08

1,3

- DiMe

- 2

- Ethylbenzene a 1092.85 0.020 0.00

Unknown u 1094.62 0.003 0.01

n

- Undecane p 1100.00 0.002 0.03

1,2

- DiMe

- 3

- Ethylbenzene a 1107.49 0.004 0.04

1,2,4,5

- Tetra

- Me

- Benzene a 1119.01 0.006 0.09

Unknown u 1123.00 0.006 0.14

t

- 1

- But

- 2

- MeBenzene a 1139.52 0.019 0.01

Unknown u 1144.96 0.000 0.05

Methylindane n 1156.53 0.004 0.05

n

- Pentylbenzene + t

- 1

- Me

- 2

- (4MP)cyclohexane a 1158.21 0.005 0.04

t

- 1

- But

- 3,5

- DiMeBenzene a 1174.77 0.000 0.00

Unknown u 1175.94 0.000 0.00

t

- 1

- But

- 4

- Ethylbenzene a 1183.89 0.010 0.00

Naphthalene n 1189.56 0.000 0.00

n

- Dodecane p 1200.00 0.000 0.00

% Listed Peaks are of TotalVOC 99.18 98.46

## 28 Table 13. Summary statistics for the hydrocarbon composition of Fuel 28.



# Summary Statistics for Fuel# 28

HS Whole



# %Ethanol 27.85 11.10

%Paraffins 40.85 34.20

%Olefins 13.66 8.18

%Aromatics 16.42 43.86

%Unknowns 0.38 1.01

%Fused Rings 0.02 0.12