# COORDINATING RESEARCH COUNCIL, INC.

3650 MANSELL ROAD·SUITE 140·ALPHARETTA, GA 30022



# CRC Report No. E

- 77

- 2c

STUDY TO DETERMINE EVAPORATIVE EMISSION BREAKDOWN, INCLUDING
PERMEATION EFFECTS AND DIURNAL EMISSIONS, USING E20 FUELS ON AGING
ENHANCED EVAPORATIVE EMISSIONS

CERTIFIED VEHICLES

December 2010Final CRC E

- 77

- 2c Report

- Dec 2010

i The Coordinating Research Council, Inc. (CRC) is a non

- profit corporation

supported by the petroleum and automotive equipment industries. CRC

operates through the committees made up of technical experts from

industry and government who voluntarily participate. The four main a reas

of research within CRC are : air pollution (atmospheric and engineering

studies); aviatio n fuels, lubricants, and equipment performance, heavy

- duty

vehicle fuels, lubricants, and equipment performance (e.g., diesel trucks);

and light

- duty vehicle fuels, lubricants, and equipment performance (e.g.,

passenger cars). CRC’s function is to provide the mechanism for joint

research conducted by the two industries that will help in determining the

optimum combination of petroleum products and automotive equipment.

CRC’s work is limited to research that is mutually beneficial to the two

industries inv olved, and all information is available to the public.

CRC makes no warranty expressed or implied on the application of

information contained in this report. In formulating and approving reports,

the appropriate committee of the Coordinating Research Cou ncil, Inc. has

not investigated or considered patents which may apply to the subject

matter. Prospective users of the report are responsible for protecting

themselves against liability for infringement of patents.Final CRC E

- 77

- 2c Report

- Dec 2010

i 

### Final Report



## STUDY TO DETERMINE EVAPORATIVE EMISSION BREAKDOWN, INCLUDING PERMEATION EFFECTS AND

DIURNAL EMISSIONS USING E20 FUELS ON AGING

ENHANCED EVAPORATIVE EMISSIONS CERTIFIED

VEHICLES

CRC E

- 77

- 2c

Submitted by

Harold M. Haskew, PE Tom Liberty

Harold Haskew & Associates, Inc. 425 W. Huron Street, Suite 230 Milford, MIFinal CRC E

- 77

- 2c Report

- Dec 2010

ii 

### Table of Contents

Page

Introduction Background

................................ ................................ ....................... 1 Contract History and Period of Performance

................................ .... 1

Program Overview

Test Fuels

................................ ................................ .......................... 3

Test Procedures

................................ ................................ ................. 5

E

- 77

- 2c Veh icle Selection

................................ ................................ 8 Composite Vehicle Fleet

................................ ................................ ... 9

Discussion of Test Results

Task 4.5

– Permeation Performance on E0, E10 and E20 Fuels

..... 12

Static Emissions Performance

................................ ................. 12 Static Permeation Relationship 86o vs. 105o F

........................ 15 Running Loss and Hot Soak Emissions Performance

............. 16

Diurnal Emissions Performance

................................ ............. 1 9 Summary of Task 4.5

................................ ................................ ....... 23

Task 4.7

– Effect of Leak Location on Permeation Emissions

........ 24

Leaks with Pre

- Enhanced and Pre

- ORVR Systems

................ 24 Leaks at Fuel Cap with ORVR Systems

................................ . 25 Alternative Implanted Leak Locations

................................ .... 27 Leak Location at Tank Top

................................ ............... 28

Leak Location at Canister Inlet

................................ ......... 29 Diurnal Leak Comparison

................................ ................. 30 Summary of Task 4.7

................................ ................................ ....... 32 Speciation of Permeation Results

................................ .................... 32 Basic Speciation File Example

................................ ............... 32 Ozone Forming Potential Methodology

................................ .. 34 Reactivity Comparison

................................ ............................ 35 Summary and Recommendations for Additional Investigations

..... 36 Acknowledgements

................................ ................................ .......... 3 7 Steering Committee

................................ ................................ ......... 3 7

Appendix I

- Task 4.5 Individual Vehicle Data and Plots

.......................... 3 8 Appendix II

- Task 4.7 Individual Vehicle Data and Plots

........................ 60 Appendix III

- E

- 77 Test Concept: Measuring Leaks,

Permeation and Diurnal Vapor Losses

................................ 69 Appendix IV

– Speciation and Rea ctivity Results

................................ ...... 80 Appendix V

– CRC E

- 77 and E

- 77

- 2 Fuel Specifications

......................... 251Final CRC E

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- 2c Report

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iii 

### List of Figures

Figure Description Page

1 Trap Canister

................................ ................................ ........................... 5

2 Static Test

– Tank Pressurization

................................ ............................ 6

3 Static Test

– Fuel Pump Energized

................................ ......................... 6

4 Test Procedure Flow Chart

................................ ................................ ..... 7

5 86o F Static Performance

................................ ................................ ........ 1 2

6 105o F Static Performance

................................ ................................ ...... 1 2

7 Temperature Effect on Static Performance

................................ ............ 1 5

8 Running Loss Performance

................................ ................................ .... 1 6

9 Hot Soak Performance

................................ ................................ ........... 16

10 Day One Diurnal Performance

................................ ............................... 19

11 Three Day Diurnal Performance

................................ ............................ 20

12 Simple Tank Venting System

................................ ................................ 2 4

13 Dodge Caravan Fuel System

................................ ................................ .. 2 6

14 Toyota Camry Fuel System

................................ ................................ ... 2 6

15 Caravan Top Tank Leak

................................ ................................ ......... 2 8

16 Camry Top Tank Leak

................................ ................................ ........... 2 8

17 Caravan Canister Inlet Leak

................................ ................................ ... 29

18 Camry Canister Inlet Leak

................................ ................................ ..... 29

19 Caravan Diurnal Leak Comparison 10psi E10 Fuel

.............................. 30

20 Caravan Diurnal Leak Comparison 7psi E10 Fuel

................................ 30

21 Camry Diurnal Leak Comparison 10psi E10 Fuel

................................ . 31

22 Camry Diurnal Leak Comparison 7psi E10 Fuel

................................ ... 31Final CRC E

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iv 

### List of Tables

Table Description Page

1 7psi E20 Fuel Properties

................................ ................................ ............ 3

2 9 psi E20 Fuel Properties

................................ ................................ ............ 4

3 E

- 77

- 2 c Vehicle Fleet

................................ ................................ ................ 8

4 E

- 77 Composite Fleet

................................ ................................ ................ 9

5 Tier 1 Vehicle Static Data

................................ ................................ ......... 13

6 Tier 2/Zero Evap Vehicle Static Data

................................ ....................... 14

7 Tier 1 Vehicle Running Loss and Hot Soak Data

................................ ..... 17

8 Tier 2/Zero Evap Vehicle Running Loss and Hot Soak Data

................... 18

9 Tier 1 Vehicle Diurnal Data

................................ ................................ ...... 21

10 Tier 2/Zero Evap Vehicle Diurnal Data

................................ .................... 22

11 Fuel Cap Leak

– Pre

- Enhanced, Pre

- ORVR

................................ ............. 25

12 Fuel Cap Leak

– Enhanced and ORVR

................................ .................... 27

13 Speciation File Example

................................ ................................ ........... 33

14 Ozone Forming Potential Methodology

................................ .................... 34

15 Reactivity Comparison

................................ ................................ .............. 36Final CRC E

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- 2c Report

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v 

### AcronymsFinal CRC E

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- 2c Report

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vi 

### Executive Summary

The National Renewable Energy Laboratories ( NREL ) , in cooperation with the US Environmental Protection Agency (US EPA , or EPA), determined the need for an evaporative emissions test program to characterize real

- world evaporative emission events for planning and inventory modeling purposes. This program (E

- 77

- 2c) adds testing on E20 (20 volume percent ethanol in gasoline) on additio nal vehicles to the E0 an d E10 fuels previously evaluated in the

CRC E

- 77 series studies, as well as additional implanted leak mechanisms.

“ Permeation ” refers to the loss of fuel vapor through the various components of a vehicle’s fuel system. Permeation occurs continuously, but the rate depends on a number of factors, including the properties of storage container (gas tank, etc.), type of fuel hoses (material, design, shape), the amount of fuel in the container, environmental factors (including temperatur e) and fuel properties (including oxygenates). Diurnal emissions are those that occur daily, or over a 24

- hour per iod of testing, and are measured while the vehicle’s propulsion system is at rest.

An addition al part of this program was to expand on the l eak study performed in E

- 77

- 2, with

additional “i mplanted leak” evaluations on vehi cles 207 and 211. Previous evaluations were made with leaks implanted at the fuel cap. For this program, leaks were implanted at the top of

the fuel tank, and separately a t the canister’s fuel vapor entry with 7 and 10 psi E10 fuel. This assignment wa s known as Task 4.7.

The fuels used to evaluate the permeation performance of the vehicles in Task 4.5 and 4.7 were 20 volume percentage ethanol mixtures, at two vapor pressures, seven (7) and nine (9) psi RVP. Task 4.5 measured the permeation performance of the two vapor pressure fuels on the selected fleet. Task 4.7 continued a previous CRC investigation into the emission effect of implanted leaks in the vapor system.

The following table summarizes the fleet as tested in the E

- 77

- 2c program. One vehicle, No. 220, a 2000 model year (MY) Chevrolet Malibu, started the test program; but was cancelled by the steering committee when it exhibited a deteriorating leak condit ion during the program.Final CRC E

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- 2c Report

- Dec 2010

vii



### This assignment (E

- 77

- 2c) only involved the performance of permeation measurements on vehicles operated on two E20 fuels. The main value of the data collected is realized when the results are viewed in the context of the prior CRC work. There are three sections in the “Discussion” portion of this report:

T he permeation performance of the “Combined E

- 77 Fleet” on the various fuels (Task

4.5 plus prior work ).

T he additional leak testing that was done in this project, combin e d with the prior work to

overview the effect of leak location. It also points out that the later vehicles with ORVR systems had different leak effects. (Task 4.7 plus prior work)

Description and details of the evaporative emission speciation measurements, and the methodology of the “Average Reactivity” calculations that were made.

Task 4.5 demonstrated that while the sample sizes are still too small to make comparisons with statistical significance, sever al trends are suggested. Referring to the data presented, and comparing the average permeation performance for various groups, the following trends and

observations are offered:

The newer Tier 2 vehicles have lower permeation than Tier 1 on all fuels.

P ermeation is higher with E10 or E20 compared to an ethanol

- free (E0) fuel.

The tests performed for Task 4.7 demonstrated two findings that may have significance for air quality modelers:

Vehicles fitted with ORVR systems may have changed the emission imp act of a small leak at the fuel cap. Leaks added at the fuel cap for the two ORVR vehicles tested produced one day diurnal emissions almost an order of magnitude lower than was seen with a previously tested non

- ORVR Cavalier

. This change in the emissions measured is thought to be due to the addition of “check valves,” or “anti

- spitback valves” added to the systems to improve the fuel fill control.

Diurnal emissions measured with leaks implanted at the top of the fuel tank, o r at the entry to the carbon canister, were significantly higher than the emissions with a leak implanted at the fuel cap on the two ORVR

- equipped vehicles tested. I t was expected that the permeation emissions from a leak at the top of the tank might be higher than those from a leak at the fuel cap

.

The E

- 77

- 2c scope of work request included gas chromatographic speciation of all the vehicle tests, including the static tests, the dynamic, and the diurnals on both fuel vapor pressures. This generated a sizable file of test results. Analysis, or commen t on the content on the speciation other than the calculation of reactivity was not attempted, and is beyond the scope of this investigation. The detailed speciation summaries are presented at the end of this report in Appendix IV.Final CRC E

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- 2c Report

- Dec 2010

1



### ST UDY TO DETE RINE EVAPORATIVE EMISSION BREAKDOWN, INCLUDING

PERMEATION EFFECTS AND DIURNAL EMISSIONS USING E20 FUELS ON AGING

ENHANCED EVAPORATIVE EMISSIONS CERTIFIED VEHICLES

CRC E

- 77

- 2c

Introduction

Background

- The National Renewable Energy Laboratories ( NREL ) , in cooperation with the US Environmental Protection Agency (US EPA , or EPA), determined the need for an evaporative emissions test program to characterize real

- world evaporative emission events for plannin g and inventory modeling purposes. Coordinating Research Council’s (CRC) “ E

- 77 Pilot Study 1 

### ” demonstrated that segregation of evaporative emis sion components was possible, where f uel system permeation emissions were measured separately from fuel tank and c arbon canister venting emissions. Later CRC studies, E

- 77

- 2 2 

### , and E

- 77

- 2b 3 

### , continued these measurement techniques, and added to a data base that was created to support new concepts in air inventory modeling. This program (E

- 77

- 2c) adds testing on E20 (20 volume percent ethanol in gasoline)

on additional vehicles to the E0 an d E10 fuels previously evaluated in the CRC E

- 77 series

studies.

“ Permeation ” refers to the loss of fuel vapor through the various components of a vehicle’s fuel system. Permeation oc curs continuously, but the rate depends on a number of factors, including the properties of storage container (gas tank, etc.), type of fuel hoses (material, design, shape), the amount of fuel in the container, environmental factors (including temperature) and fuel properties (including oxygenates). Diurnal emissions are those that occur daily, or over a 24

- hour per iod of testing, and are measured while the vehicle’s propulsion system is at rest.

An addition al part of this program was to expand on the lea k study performed in E

- 77

- 2, with

additional “implanted leak” evaluations on vehi cles 207 and 211. Previous evaluations were made with leaks implanted at the fuel cap. For this program, leaks were implanted at the top of

the fuel tank, and separately at the canister’s fuel vapor entry with 7 and 10 psi E10 fuel. This assignment wa s known as “Task 4.7.”

Contract History and Period of Performance

- Harold Haskew & Associates, Inc. (HH&A) 4


### was awarded the contract for this program, and shared the testing responsibility with Automotive Testing Laboratories, Inc. (ATL) 5 

### in Mesa AZ. The contract was dated June 1, 2009, and the first test was conducted on August 12, 2009 (Task 4.7 leak test on Vehicle 211c with the E10 fuel). Weekly progress reports were made each Sunday, with Number 1 dated August 9, 2009, and the final, number 31, dated March 4, 2010.

1 Available for download at CRC’s web site, www.crcao.org , in the Emissions Publications section.

2 Ibid. CRC E

- 77

- 2, “ Enhanced Evaporative Emission V ehicles ,” March 2010

3 Ibid, CRC E

- 77

- 2b, “ Evaporative Emissions from In

- Use Vehicles: Test Fleet Expansion,” SwRI ® Project No.

03.14936.05 , June 2010

4 Harold Haskew & Associates, Inc., 425 W Huron, Su ite 230, Milford, MI, (248) 684

- 3410

5 Automotive Testing Laboratories, Inc., 263 S Mulberry Street, Mesa, AZ (480) 649

- 7906, Greg Barton, PresidentFinal CRC E

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- 2c Report

- Dec 2010

2



### This report is the fourth in a series of CRC E

- 77 reports, but is organized to be a stand

- alone report, without excessive reference to the previous publications. Much of the documentation concerning the theory and practice of the test procedure has been placed in A ppendix III , but captured within this publication.Final CRC E

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- 2c Report

- Dec 2010

3 

### Program Overview

Test Fuels

The fuels used to evaluate the permeation performance of the vehicles in the permeation performance task, and the implanted leak investigation were 20 volume percentage ethanol mixtures, a t two vapor pressures, seven (7) and nine (9) psi RVP. The properties of the t wo test
fuels are listed in T ables 1 and 2. Fuel properties from previous CRC E

- 77 studies are contained in Appendix V.

Table 1. 7 RVP E20 Fuel PropertiesFinal CRC E

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4 

### Table 2. 9 RVP E20 Fuel PropertiesFinal CRC E

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- 2c Report

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5



### Test Procedures

A Test Method for Separating Permeation from Tank Venting and Leaks

– In a previous CRC Project (E

- 65), the laboratory separated the canister loss from the permeation measurement by venting the losses from the carbon canister outside the SHED. For Project E

- 77, the canister

vent losses were collected and measured in a separate “trap canister” on a scale outside the
SHED, as shown in Figure 1 . This vent line was capped off, i.e., sealed during the Static Test, but connected as shown in the figure for the Dynamic and the Diurnal Test. The ambient temperature in the SHED was constant during the static test, and

there was no vapor created at constant temperature. This vent was closed to pressurize the system for the leak evaluations. The resulting SHED increase in HC mass was permeation 6 

### . The last mechanism that needed to be evaluated was leaks. Leaks can be both vapor and liquid. A liquid leak can have significant mass, currently undetected by the vehicle’s on

- board diagnostic system. Considerable thought and effort have gone into the creation of a simple and effective liquid leak detection methodology, without success. The techniques used in this project required the use of a SHED for measurements. The techniques were not simple, but they proved

effective.

Based on experience, a vehicle’s permeation rate is expected to lie between 4 and 90 mg/hour. The presence of a static liquid leak is expected to overwhelm this value; such a leak would (or could) be apparent by inspection. Leaks from the vehicles were quantified in a three

- step test process. The first step was to measure the static permeation rate of the vehicle at 86oF. The vehicle was allowed to stabilize at 86oF in the SHED and the permeation rate was calculated from the mass increase in the SHED. The second part of the test, looking for pressure driven leaks in the vapor system , was performed by pressurizing the vehicle’s tank to 5” H 2 

### O through a special fuel cap and tubing from outside the SHED (Figure 2 ). The special fuel cap, the hose and the pressurization apparatus was installed before the start of the sequence. The HC co ncentration in the SHED was monitored, and the increase in the mass of HC in the SHED was compared to the static permeation rate. If there was no (or insignificant) rate of increase, it was deduced that no vapor leak is present.

6 This is a simplification. There are other HC sources present that are not fuel permeation. These include tire, paint, adhesives and vinyl emissions, and the possibility of fuel leaks from the fu el injectors. The investigators believe these to be a minor component of the emissions measured in this study. Figure 1 Trap CanisterFinal CRC E

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6



### The third and final part of the test was to energize the vehicle’s fuel pump and pressurize the system up to and including the injectors (Figure 3 ). If there were a pressure leak in the liquid system, an increase in the SHED mass over time would be seen, i.e., the leak would be additive to the permeat ion rate.

Figure 3 Static Test

– Fuel Pump Energized

Other Tests (Dynamic, Hot Soak, and Diurnal)

- A similar configuration is used to isolate the tank venting losses from the permeation measurements determined by other test procedures. The vehicle’s canister vent is connected with a low permeation hose (TeflonTM) to a bulk

- head fitting in the SHED wall and then to a separate “trap canister” on a top

- loading scale. Any HC

emis sions that escape from the vehicle’s canister are captured in the trap canister, and measured at a 0.01 g (10 milligram) precision. The trap canister (a 1 Liter Ford model) is purged before

each test and maintained at a “dry” condition so that it captures all of the vehicle’s escaping emissions. This assumption is probably violated during high v apor pressure tests where there are

30 or more grams of daily emissions

. Figure 2

- Static Test

– Tank PressurizationFinal CRC E

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- 2c Report

- Dec 2010

7 

### Figure 4

– Test Procedure Flow ChartFinal CRC E

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- 2c Report

- Dec 2010

8



### E

- 77

- 2c Vehicle Selection

The vehicle mix was specified in the CRC Request for Proposal as eight vehicles for Task 4.5, and a repeat of two vehicles previously tested in CRC programs with implanted leaks for Task 4.7. Task 4.5 vehicles included five Tier 1 vehicles, two Tier 2 vehi cles, and one “Zero Evap”

vehicle.

Table 3 summarizes the fleet as tested in the E

- 77

- 2c program. One vehicle, No. 220, a 2000 model year (MY) Chevrolet Malibu, (not shown in Table 3) started the test program; after exhibiting a deteriorating leak cond ition during the program, it was cancelled by the steering

committee.

A “Tier 1” vehicle is one that certified to the EPA’s “Enhanced Evaporative Emission”

standards 7 

### . These evaporative standards were phased in starting in Model Year 1996 (see also 40

CFR 86.096

- 8 (b)), with all light dut y vehicles compliant by MY 1998. Vehicles certified to the evaporative emissions standards prior to the enhanced standards are referred to as “Tier 0.” The enhanced standards required control of diurnal emissions for up to three days (previously a one

da y tank temperature rise, compressed into a one hour time requirement), as well as control the evaporative (i.e., non

- tailpipe) emissions during vehicle operation (known as running losses) at high (95°F) ambient conditions, and a one

- hour “high

- temperature hot soak” period immediately following the drive. Tier 2 standards 8 

### used similar test procedures and conditions, but lowered the allowable limits to less than half the previous standards. California required that a fraction of the vehicles produced for C alifornia meet new “Zero Evaporative Emission” standards. 9 

### A vehicle certified to the zero evap standards had diurnal plus hot soak fuel emissions at levels less

7 http://www.epa.gov/otaq/standards/light

- duty/tier1evap.htm

. See this EPA web page for a comprehensive chart showing the various standards and the implementation schedules.

8 Tier 2 Evaporative Emission Standards; http://www.epa.gov/otaq/standar ds/light

- duty/tier2evap.htm

, ; and 40 CFR 86 Subpart S

. 9 Note: several other states have adopted vehicle emissions standards identical to those of California. 

### Table 3

.

Veh Evap Standards

No. Year Make Model (all are ORVR)

221 2000 Mitsubishi Galant Tier 1

206 2002 Nissan Altima Tier 1

208 2002 Chevrolet Trailblazer Tier 1

209 2004 Chrysler Stratus Tier 1

210 2004 Chevrolet Impala Tier 2

213 2004 Dodge Ram 1500 Tier 2

222 2004 Ford Focus ZX3 Zero Evap

207 2001 Dodge Caravan Tier 1

211 2004 Toyota Camry XLE Tier 2 E

- 77

- 2c Vehicle Test Fleet Summary

Task 4.5

- E20 Fuel Effect on Emissions

Task 4.7

- Implanted Leak Effect with E20 FuelFinal CRC E

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- 2c Report

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9



### than 0.0 grams per test 10 

### . The 0.0 gram requirement was later defined and accepted to be 0.054 grams, or 54 milligrams, to include round off of the measurement. A whole vehicle performance limit of 350 mg/test was included to allow for non

- fuel test contributors (e.g., tires, adhesives, etc.) on a whole vehicle test.

Composite Vehicle Fleet

As stated previously , the Task 4.5 of the E

- 77

- 2c program added seven vehicles tested on E20

fuel to the E

- 77 program database. Table 4 below lists the “composite E

- 77 vehicle fleet,” sorted by evap standard, with the 2c vehicles indicated by the “/c” notati on in the vehicle number

column of the light blue rows . Not all data from the composite fleet are usable for later analysis, as the use of the INNOVA analyzer for identification of methanol (probably from windshield washer fluid) and refrigerant (R

- 134a) l eaks did not become available until the latter part of the Pilot Program. Pre INNOVA data tests that were not used in the analysis are indicated with the yellow shading.

Table 4.

10 “ CALIFORNIA EVAPORATIVE EMISSION STANDARDS AND TEST PROCEDURES FOR 2001 AND
SUBSEQUENT MOD EL MOTOR VEHICLES ,” California Air Resources Board, 1999, ... Vehicles demonstrating compliance with these evaporative emission standards shall also have zero (0.0) grams of fuel evaporative emissions per test for the three

- day and two

- day diurnal

- plus

- hot

- soak tests

...Final CRC E

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- 2c Report

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10



### It seemed desirable to combine as much as possible of the previous E

- 77 data (E

- 77 Pilot Study,

E

- 77

- 2, and E

- 77

- 2b) with the newly gathered data into the discussion of results. Not all of the

data were comparable

. The following summary is offered to explain the various choices.

While not part of the contracted E

- 77 Pilot Study, the laboratory found that the vehicle tests needed to be corrected for the presence of the methanol and the refrigerant R134a. The INNOVA analyzer that the laboratory purchased and used to make these corrections was not available for testing until vehicle 006. Of the remaining vehicles tested, only 006 and 008 were Tier 1 models. (Vehicle 007 was an implanted leak test, and vehicles 009

an d 010 were pre

- enhanced Tier 0 models.) The Pilot Study only ran a one

- day diurnal,

rather than the three

- day test that became the norm.

The 105oF static tests were first introduced in the E

- 77

- 2b test sequence to enhance the evidence that permeation is directly affected by temperature. The earlier test programs

did not have that information.

Emission results are presented in later sections of the report for each of the four evaporative emission elements (static, running loss, hot soak and diurnal), with data averaged for selected and representative vehicles tested in the E

- 77, E

- 77

- 2 and E

- 77

- 2b programs that were opera ted on the four fuels used in this (2 c ) study.Final CRC E

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- 2c Report

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11 

### Discussion of Test Results

While this assignment (E

- 77

- 2c) involved only permeation performance on two E20 fuels,

additional value of this E

- 77

- 2c data is realized when the results are viewed in the context of the prior CRC work. T here may be misleading conclusions when comparing d ata across fuels where a different number of vehicles contribute to the bars within a technology group. D rawing inferences in fuel effects based on these averages is inappropriate because individual vehicle effects come into play.

There are three sectio ns in the “Discussion” portion of this report:

T he permeation performance of the “Combined E

- 77 Fleet” on the various fuels (Task

4.5 plus prior work ).

T he additional leak testing that was done in this project, combine d with the prior work to

overvie w the effect of leak location. It also points out that the later vehicles with ORVR systems had different leak effects. (Task 4.7 plus prior work)

Description and details of the evaporative emission speciation measurements, and the methodology of the “Av erage Reactivity” calculations that were made.

The actual test summaries and the plots of the results of each of the test vehicles on the two volatilities of the E20 fuel are contained in the Appendices, starting at page 3 8

.Final CRC E

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- 2c Report

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12



### Task 4.5

- Permeation Performance on the E0, E10 and E20 F uels

Static Emissions Performance

– Figures 5 and 6 below present the static permeation results for the composite fleet and include the E20 results on the right side of each figure. The static performance averages gave similar fuel rankings to that which was seen with the more significant d iurnal test result averages

.

Figure 5 86o F Static Performance

Figure 6 105o F Static PerformanceFinal CRC E

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- 2c Report

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13



### Tables 5 and 6 contain the data used in Figures 7 and 8, respectively

, as well as data from the pressurizing of the tank and activating the fuel pump ; these features of the test were to check for leaks, and are discussed in detail in Appendix III

.

Table 5. Tier 1 Vehicle Static DataFinal CRC E

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- 2c Report

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14 

### Table 6. Tier 2 Vehicle Static Data

Zero Evap Vehicle Static DataFinal CRC E

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- 2c Report

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15



### Permeation Rate Relationships at 86o and 105oF

- The relationship between the static permeation rates measured at 86oF and 105oF have been previously shown to generally follow a relationship of 105oF = 2 x 86oF 11 

### . This is usually stated as the relationship that follows a doubling of t he permeation rate for each 10oC (18oF) temperature increase. The data measured during this program is plotted in Figure 7 below, with a 2:1 reference line added.

Figure 7

– Temperature Effect on Static Permeation

The measurements made in this E

- 77

- 2 c program appear to be consistent with previous trends.

11 See SAE 2001

- 01

- 0730 , “Estimating Real Time Diurnal Permeation from Constant Temperature Measurements” by Marek Lockhart, et al. , March 2001, and CRC “E

- 65 Final Report

- Fuel Permeation from Automo tive Systems”, Harold Haskew, et al., September 2004, Figures 19 & 20

.Final CRC E

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- 2c Report

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16



### Running Loss and Hot Soak Performance

- Permeation rate comparisons are shown below in Figures 8 and 9 for the running loss and hot soak measurements for the composite fleet, with permeation trends similar to the diurnal and static results. The units for the running loss measurements are expressed in time units, mg/hour, which the authors feel are more appropriate than the regulatory units of grams per mile. The conversion back to grams per mile co uld be made by multiplying by 48/60 to get the mass per test, and dividing by 20 to get the miles traveled (2 x 10 miles per LA92).

Figure 8

– Running Loss Performance

Figure 9

– Hot Soak Permeation

Tables 7 and 8 contain the data used in Figures 8 and 9, respectively.Final CRC E

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- 2c Report

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17 

### Table 7
Tier 1 Vehicle Running Loss and Hot Soak DataFinal CRC E

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- 2c Report

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18 

### Table 8

Tier 2 Vehicle Running Loss and Hot Soak Data

Zero Evap Vehicle Running Loss and Hot Soak DataFinal CRC E

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- 2c Report

- Dec 2010

19



### Diurnal Emissions Performance

- Figure 10 shows the Day One diurnal emission results for

the E

- 77 composite fleet, segregated by ethanol level, fuel vapor pressure, and vehicle technology group. The “Day One” performance is presented here because it includes the

maximum number of tes ts to include in the averages

– t he earlier Pilot Study program did not

include three

- day diurnal evaluations. The cumulative diurnal performance for the three

- day diurnal test is presented in Figure 11 with slightly fewer tests, but a similar permeation performance pattern.

Starting at the left edge of F igure 10 , there are two bars representing the average permeation

measured for the 24

- hour (or the first 24 hours of a longer test) diurnal test (1

- day) with the 7 psi E0 fuel. The left blue bar represents the average for the nine Tier 1 vehicles that have been

tested in the E

- 7 7 programs. The six newer Tier 2 vehicles’ permeation average is shown with the green bar. While the number of observations is small, it indicates that, on average, the newer vehicles have lower permeation on the 7 psi E0 fuel.

A similar trend is indica ted in the second pair of bars, showing the permeation performance of

the E

- 77 vehicles tested with the higher vapor pressure (9 psi) E0 fuel. The nine Tier 1 vehicles’ average indicated an increase in permeation with the higher vapor pressure fuel. The third and fourth pairs of bars in the figure show the results when the vehicles were tested with an E10 fuel. The permeation of the Tier 1 vehicles increased on average with the E10 fuels compared to the ethanol free (E0) test fuels. For the newer Tier 2 vehicles, the average permeation was not markedly different when comparing the E10 to the E0 results.

The performance of the vehicles with the E20 fuels is represented by the right two pairs of bars. Addressing first the Tier 1 vehicles, it appears that the permeation is higher with the E20 fuel than the E0, but lower with E20 compared to E10. The Tier 2 vehicles do not indicate a marked increase or difference with the E10 or E20 fuels, although the numeric values are higher.

Figure 10

– Day One Diu rnal PerformanceFinal CRC E

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### Similar observations are made when the data for the cumulative three

- day diurnal permeation emissions are charted in a similar fashion, as shown in Figure 11, below

. In Figure 11, it should be noted that the 10 psi E10 averages for the Tier 1 vehicles are highly driven by the results for 206(b), and the results for the Tier 2 vehicles are highly driven by the results for vehicle 214.

Figure 11

– Three Day Diurnal Performance

Tables 9 and 10 contain the data used in Figures 10 and 11, respectively.Final CRC E

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### Table 9

Tier 1 Vehicle Diurnal DataFinal CRC E

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### Table 10

Tier 2 Vehicle Diurnal Data

Zero Evap Vehicle Diurnal DataFinal CRC E

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### Summary of Task 4.5

While the sample sizes are still too small to make comparison with statistical significance, several trends are suggested. Referring to the figures shown above, comparing the average permeation performance for various groups, the following trends and observations are offered:

1. The newer Tier 2 vehicles have lower permeation than Tier 1 on all fuels.

2. Permeation is higher with E10 or E20 compared to an ethanol

- free (E0) fuel.

3. Permeation is lower with E20 compared to E10 on the Tier 1 vehicles, but the presence of

a reduction is less clear for the newer Tier 2 vehicles based on the few tests available for analysis. Further research may be needed to determine the sensitivity of newer vehicle technologies to fuel effects.

4. Higher average permeation emissions may be associated with increased fuel vapor pressure for the Tier 1 vehicles tested in this program, but the average permeation

emissions for the newer Tier 2 test vehicles show no clear trend with vapor pressure.Final CRC E

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### Task 4.7

- Effect of Leak L ocation on Permeation Emissions

For the last four decades 12 

### , vehicles sold in the United States have been equipped with evaporative emission control (evap) systems that are remarkably effective in r educing fuel evaporative emissions from automotive fuel systems. Light Duty Vehicles (LDV) starting in model year 1998 e ven control refueling emission to a very high degree. The performance of these evap systems are, however, affected by leaks that may exist in the fuel system of a vehicle. These leaks can be the result of, among other things, poor connections, scratched or misaligned seals, loose fuel caps, and improper maintenance , such as improper repairs done to other fuel

system component s that could result in leaks. Undetected (and un

- repaired) leaks in automotive fuel systems can be a potentially significant source of vehicle emissions.

This source of emissions (leaks) was addressed by regulation starting in MY 1998 with the implemen tation of onboard detection of fuel system leaks (OBD and a later OBDII). Current OBDII systems are capable of detecting vapor leaks of 0.020” diameter

- equivalent or larger equivalent d iameter, and alerting the operator to bring the vehicle in for service . As a result,

leaks of this scale (if corrected) can become a much smaller contributor to vehicle fuel

emissions.

Leaks with Pre

- Enhanced, Pre

- ORVR Systems

- There is a need to understand the frequency and nature of leaks that may still exist in the inv entory. The Coordinating Research Council (CRC) sponsored test programs (E

- 77, E

- 77

- 2) in recent periods that were designed to measure emissions from implanted 0.020 ” diameter leaks located in the gas cap in several test vehicles.

The test vehicles were s ubjected to a series of emission tests, including a summertime (65 ° to
105 ° F) diurnal event.

In the initial test program (CRC E

- 77), a 1996 Cavalier with Enhanced Evap control hardware was selected as the test vehicle. The Cavalier was equipped with a simple tank venting system ( Figure 12 ) with an inline 0.055” orifice in the vent line from the tank and leading forward to the canister. Because of the flow restrictions caused by the 0.055” orifice, the length of the vent

12 The first federal requirement for fuel evaporative emission control was model year 1971. California required systems a year earlier (1970) 

### Figure 1 2

– Simple Tank Venting SystemFinal CRC E

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### line, the multiple bends, and the carbon bed in the canister, the 0.020” leak implanted in th e cap provided a convenient, parallel path to the atmosphere. With a n implanted leak in the fuel cap, about 21 grams of HC wer e emitted into the SHED (Table 11 ) during the diurnal test with E0 fuel, while the baseline test with no leak resulted in only 0. 4 grams of diurnal emissions. It was

estimated , using contemporary vapor generation models, that the uncontrolled vapor emissions

from this test 13 

### would have been 23.2 grams if the cap had been left off completely. The 20.7 gram emissions level corresponds to a 89% loss to the environment.

Table 11

Impact of 0.020” Leak on Diurnal Emissions

65°

– 105° F Diurnal

1996 Cavalier

Test fuel Baseline

emissions (gms/day) Emissions with

0.020” leak (gms/day) Increase in

emissions (gms/day)

1996 Chevrolet Cavalier E0 0.38 20.70 20.32

Discussions about this test result created the realization that the location of the leak, and the configuration of the vehicle’s fuel system, would probably have a significant effect on the resulting emissions. Even though the leak in the fuel cap was smaller than the 0.055” orifice in the tank vapor line, most of the HC vapors passed through the leak to the atmosphere because it was a path of relatively low resistance.

Leaks at the Fuel Cap with ORVR Systems

- In a subsequent test program (E

- 77

- 2), a similar

diur nal test was conducted on a 2001 Dodge Caravan (Fig

. 13 ) and a 2004 Toyota Camry (Fig

. 14 ) using E10 fuel. Both vehicles were equipped with Onboard Refueling Vapor Recovery (ORVR) systems as well as OBDII and Tier 1 Evap. A 0.020” leak was implanted in the fuel cap of each vehicle and the resulting SHED emissions are shown in Table 6 . The resulting net increases in emissions were 1 gram for the Caravan and 0.4 grams for the Camry, much lower

than the results measured during the evaluation of the Cavalier.

The following discussion attempts to explain the hardware and component differences that

contributed to the different results.

13 7.0 psi RVP fuel, 15.3 gallon tank 40% full, 17.6 gallons total tank volume with a 67° to 103°F temperature

increase.Final CRC E

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### Figure 1 3 Dodge Caravan Fuel System with Enhanced Evap and ORVR

Figure 1 4 Toyota Camry Fuel System with Enhanced Evap and ORVRFinal CRC E

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### Table 12

Impact of 0.020” Leak on Diurnal Emissions

65°

– 105° F Diurnal 2002 Caravan and 2004 Camry

Test fuel Baseline

emissions (gms/day) Emissions with

0.020” leak (gms/day) Increase in

emissions (gms/day) 2001 Dodge Caravan E10 1.09 2.13 1.04 2004 Toyota Camry E10 0.24 0.68 0.44 (The use of E10 test fuel should not have a significant e ffect on diurnal emissions)

There is an important difference in the configurations of these two vehicles compared to the

Cavalier that contributed to the low effect of leak implantation on diurnal permeation emissions

. An Inlet Check Valve (ICV) is located in the fill pipe of the Dod ge Caravan (i tem 11 on Figure

13 ) at the entrance to the tank. The ICV is a common component in ORVR systems and is designed to prevent spitback from the fuel tank during a refueling event. During the diurnal tests

on the Caravan

, the ICV seal prevented HC vapors from taking a direct communication path up the fill pipe and thus into the SHED. There is a path from the top of the tank’s vapor space that communicates with the area near the fuel cap, (shown as i tem 2, a “recirculation tube.” in Figure

13 ) bu t this appears to be a less attractive path compared to the refueling vapor path to the

canister.

The Camry system shown in Figure 14 is more complex than the Caravan , as the Toyota system

uses a “vent switching” configuration during refueling events.

I n each of the test vehicles, the only flow path from the tank vapor space to the cap is through the vapor recirculation line shown in Figures 13 and 14 . This line contains an orifice ; the accompanying restrictions offered by the tubes and turns in the flo w path to the cap significantly reduced the emissions from the implanted leak. The more open path for vapors is through the large refueling vent to the low restriction carbon canister. This effect could also be a result of the cap ”seeing” an effective v apor space volume equivalent to the volume of t he filler neck. Assuming a 2ft, 2” diameter filler neck, this could amount to 1⁄2 gallon of vapor space. S c aling

the uncontrolled result of 23.2 grams by the Cavalier vapor space vs. 1⁄2 gallon results in a diurnal emission rate of about 1 gram.

Alternative Implanted L eak Locations

- In order to evaluate the effect of other leak locations and system configurations on the emissions fr om small leaks, a test plan was included in E

- 77

- 2c that expanded on the data already observed from the tests with leaks implanted in the cap. In this test series, a 0.020 leak was implanted separately in two new locations, in or near the top of the tank, and at the vent line hose connecting to the canister. The test vehicles were the same 2002 Dodge Caravan and 2004 Toyota Camry used in the previous testing. The previous data from

these vehicles w ere then compared to the data for the two new leak locati ons to add to the understanding of the impact of small leaks on emissions.

For the Task 4.7 assignment, the laboratory staff placed (implanted) a 0.020 inch internal diameter hole at various places in the vehicle’s fuel system. Carburetor jets of the 0.0 20 inchFinal CRC E

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### internal diameter size were purchased from a local source, fixed into a small disc, clamped into a stainless compression fitting and screwed into the desired position.

Previous tests had been performed with a similar size “leak” in the vehicle’s fuel cap. The 0.020
inch diameter hole was placed in two different locations on each vehicle:

1. at the top of the fuel tank in the tank sending unit cover, and

2. at the connection to the canister inlet from the fuel tank.

Leak Location at the Top o f the Tank

- Figure 15 shows the fitting in the Caravan (207) cover

with a red arrow pointing to the position of the

“leak”. This was sealed when the leak was

moved to the canister inlet.

Similarly, Figure 16 shows the fitting in position on the Toyota Camry tank. Figure 15 Caravan Top Tank Leak

Figure xx. Camry Top Tank Leak



### Figure 16 Ca mry Top Tank LeakFinal CRC E

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### Leak Location at the Canister Inlet

- Again, Figures 1 7 and 1 8 show the implanted leak location
on the Caravan and Camry respectively.

Fig ure 18 Canister Inlet Leak Location for Camry Fig ure 17 Canister Vent Leak Location for CaravanFinal CRC E

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### Comparison of the Diurnal Permeation Results with Leaks in Various Locations

– Vehicle 207 Figures 19 and 20 are summary plots of the day one diurnal results for Vehicle 207 using the 10 psi E10 and the 7 psi E10 fuel, with the leaks in various locations. The “no leak” and the “fuel cap” leak are from the previous test programs. The green and blue traces show a small effect of the leak, while the leak implanted in the top of the tank (red trace), and at the canister inlet (gold trace) show a much larger effect (compared to the “no

- leak” condition).

Figure 19

– Caravan Diurnal Leak Comparison

– 10psi E10 Fuel

Figure 20

– Caravan Diurnal Leak Comparison

– 7psi E10 FuelFinal CRC E

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### Figures 21 and 22 show the diurnal performance of Vehicle 211 with leaks in various positions

. The results were similar to those seen in Figures 19 and 20.

Figure 21

– Camry Diurnal Leak Comparison

– 10psi E10 Fuel

Figure 22

– Camry Diurnal Leak Comparison

– 7psi E10 FuelFinal CRC E

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### Summary of Task 4.7

The tests performed for Task 4.7 demonstrated two findings that may have significance for air quality modelers:

Vehicles fi tted with ORVR systems may have changed the emission impact of a small leak at the fuel cap. Leaks added at the fuel cap for the two ORVR vehicles tested produced one day diurnal emissions almost an order of magnitude lower than was seen with a previously tested non

- ORVR Cavalier. This change in the emissions measured is thought to be due to the addition of “check valves,” or “anti

- spitback valves” added to the systems to improve the fuel fill control.

Diurnal emissions measured with leaks implanted at t he top of the fuel tank, or at the entry to the carbon canister, were significantly higher than the emissions with a leak implanted at the fuel cap on the two ORVR

- equipped vehicles tested. While it was expected that the permeation emissions from a leak at the top of the tank might be higher than those from a leak at the fuel cap, a similar difference in emissions between an implanted leak at the canister inlet versus one at the fuel cap was not.

Speciation of the Permeation Results

The E

- 77

- 2c scope of work request included gas chromatographic speciation of all the vehicle tests, including the static tests, the dynamic, and the diurnals on both fuel volatilities. This generated a sizable file of test results. The detailed speciatio n summaries are presented at the end of this report in Appendix II. The implanted leak tests on Vehicles 207 and 211 (Task 4.7) were also speciated, but must be analyzed separately from the Task 4.5 results, as the analysis contains not only the vehicle’s permeation, but the vapor from the induced leak. The next few pages will be used to explain the project’s file structure, and the calculations used to speciate and calculate the reactivity of the various tests.

Basic Speciation File Example

- Table 13 is a truncated example of the basic speciation file that is generated by the laboratory (ATL). While it has been cut off after elution number 26, there are 172 species in the total report, plus methanol, ethanol and R

- 134a (refrigerant) 14 

### . This selected

fi le exists as one of the tabs in the project data file set identified as “206cgc.xls.” This example

summarizes the results for the 72

- hour diurnal results on vehicle 206c

– Test number 7703. For

the 72

- hour test, sample bags of the VT

- SHED are collected a t the start of the diurnal (T 0 

### ), at 24 hours (T 24 

### ), at 48 hours (T 48 

### ), and finally at 72 hours (T 72 

### ). In this example, the results are summarized for the composite 72

- hour test.

14 Stating again, the permeation performance values used in this report have corrected the FID’s misidentification

of the ethanol mole cule, and the identified non

- fuel components, methanol and refrigerant (R

- 134a), have been

subtracted from the totals.Final CRC E

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### Table 13

Speciation File Example

The file is org anized in the following fashion: Column 1 is the elution number, Column 2 is the species name and Column 3 is the CAS Number (with leading zeros as necessary to maintain a 10 digit format). The CAS number is a unique number created and maintained by the CAS Registry ® 

### (http://w ww.cas.org) that provides a name and property resource for recognized substances.

The right hand four columns in the figure are the test results. The EXCELTM file contains six or more digits of precision, but the precision in the figure has been reduced for clarity. The net concentration in ppmC is calculated by subtracting (for each species) the start of test concentrations (T 0 

### ) from the 72

- hour results, yielding the net increase in concentration for the

three

- day period. One could obtain the speciatio n results for the third day, for example, by subtracting the concentrations at T 48 

### from the T 72 

### measurement. The net mass for each of the species is calculated by using appropriate volume, concentration and density values. The last two columns are the relative contribution (% of total present) of the species to the total of all the

concentrations measured.Final CRC E

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### Ozone Forming Potential (Reactivity) Methodology

- The speciation information is further analyzed by calculating the composite ozone forming potential of the speciate. Table 14 below illustrates the concept. The order of presenting the individu al species has been changed by

Table 14 Ozone Forming Potential Methodology

Species CAS No. MIR Composite

VOC

mg Ozone

mg
Ethanol 00064

- 17

- 5 1.45 1017.48 1474.297

2

- Methylbutane (Isopentane) 00078

- 78

- 4 1.35 379.67 514.406

n

- Pentane 00109

- 66

- 0 1.21 335.10 407.124

n

- Butane 00106

- 97

- 8 1.08 320.07 344.688

Toluene 00108

- 88

- 3 3.93 279.47 1096.913

2

- Methyl

- 1

- pentene & 1

- Hexene 00592

- 41

- 6+00763

- 29

- 1 5.30 272.63 1444.528

Benzene 00071

- 43

- 2 0.69 205.86 142.938

n

- Hexane 00110

- 54

- 3 1.13 183.93 208.697

n

- Heptane 00142

- 82

- 5 0.97 172.84 166.926

t

- 2

- Pentene 00646

- 04

- 8 10.47 162.60 1702.998

2

- Methyl

- 2

- butene 00513

- 35

- 9 14.20 152.72 2167.853

2

- MePentane & 4

- Me

- c

- 2

- Pentene 00691

- 38

- 3+00107

- 83

- 5 1.40 146.70 205.061

3

- Me

- 1

- Hexene 03404

- 61

- 3 4.27 103.91 444.084

2

- Methylpropane 00075

- 28

- 5 1.18 101.16 119.030 Methylcyclopentane 00096

- 37

- 7 2.05 88.84 182.111
2,2

- DiMeHexane 00590

- 73

- 8 0.94 82.00 77.181

meta

- & para

- Xylenes 00108

- 38

- 3+00106

- 42

- 3 7.76 78.81 611.209

c

- 2

- Pentene 00627

- 20

- 3 10.28 76.70 788.622

3

- Methylpentane 00096

- 14

- 0 1.69 76.68 129.648

2

- Methyl

- 1

- butene 00563

- 46

- 2 6.38 62.75 400.280

1

- Pentene & 2

- Butyne 00109

- 67

- 1+00503

- 17

- 3 11.70 52.23 611.345

t

- 2

- Hexene 04050

- 45

- 7 8.55 41.65 356.031

2

- Methylhexane 00591

- 76

- 4 1.09 36.43 39.538

1

- Methyl

- 3

- Ethylbenzene 00620

- 14

- 4 7.39 35.13 259.471

1,2,4

- TriMeBenz & t

- Butylbenzene 00095

- 63

- 6+00098

- 06

- 6 5.37 32.93 176.785 Cyclohexene & 3

- Methylhexane 00110

- 83

- 8+00589

- 34

- 4 3.19 32.63 104.117

n

- Octane 00111

- 65

- 9 0.80 32.49 25.870
2,2,4

- TriMePentane (IsoOctane) 00540

- 84

- 1 1.20 32.46 38.925

c

- 2

- Butene 00590

- 18

- 1 14.26 30.92 440.893

1

- Methylcyclopentene 00693

- 89

- 0 12.45 30.43 379.046 Vehicle 206c

- Fuel 9 psi E20

- 3 Day Diurnal

- Test 7703

Non Zero Mass Species Sorted By VOCFinal CRC E

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### listing the species by decreasing mass in the sample. The blue arrow in the middle of the figure indicates where lines of data were eliminated from the table, to keep the figure to a convenient height. In the figure above, and typical for the E20 test res ults, the ethanol species has the highest mass in the sample, and thus appears as the first data line. The next largest mass is the isopentane, and so on. The next column lists the MIR value for that species. The Maximum Incremental Reactivity scale ( MI R ) scale 15 

### created by William Carter, and adopted by CARB, has been used to estimate the equivalent ozone that would be produced by the various species found in this measurement. The report listed in the footnote contains the following quote:

The methods and procedure used to derive the MIR scale presented in this report are comprehensively documented by Carter (2009a) and references therein, and those reports

should be consulted for details. Briefly, the reactivity scale is based on calculations of relati ve ozone impacts, expressed as mass of additional ozone formed per mass VOC added to the emissions, for various compounds under various atmospheric conditions, given a chemical mechanism for the compounds and other relevant atmospheric species, models for various atmospheric conditions, and a modeling and reactivity assessment procedure. The methods, atmospheric scenarios, and modeling and reactivity assessment procedures were the same as employed in previous calculations of the MIR scale (Carter, 1994a, 2 000, 2003), and are based on those first developed by Carter (1994a,b), with a few modifications as described by Carter (2000). The only difference between this updated scale and the previous MIR scales of Carter (2000, 2003) concern the chemical mechanism used and the number and types of

VOCs whose ozone impacts are calculated.



### Multiplying the mass of the individual species by the MIR factor yields the last column, the mass of ozone that might be produced by that mass of speciate. The “average reactivity” of the sample is calculated (and shown at the bottom of each file) by summing up the speciated mass, and the estimated ozone mass, and dividing the total ozone value by the total VOC (fuel) mass. In this example, the average reactivity is 3.362 (in grams of ozone per gram of volatile organic compound).

Reactivity Comparison for Various Fuels and Test Sequences Table 15 offers a summary of

the Vehicle 206c data measured and calculated using the E20 fuel. Similar summaries for the other vehicles appear with the data listings in the Appendix. Columns 4 and 6 compare the mass estimates by two different techniques. Column 4 is the mass estimate one would obtain using the SHED technique. Column 6 lists the gas chromatograph mass estimate. This technique

a ccumulates the total mass in the sample from the sum of the individually identified molecules. The first line of data in the figure indicates good correlation, 168 mg versus 162. The second line indicates that the GC measured 17% more in the sample (colum n 5, GC as % of THC = 116.9%), which is less than one would hope to see. Plus or minus 10% in readings is a goal the author would hope to achieve.

15 UPDATED MAXIMUM INCREMENTAL REACTIVITY SCALE FOR REGULATORY

APPLICATIONS

, William P. L. Carter, College of Engineering Center for E nvironmental Research and Technology, University of California, Riverside, CA 92521, March 23, 2009, available at http://citeseerx.ist.psu.eduFinal CRC E

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### The last column (Species Present) indicates the number of species identified using the GC. Thirty (30) or more is an indication that there was a high enough level of permeation that the chromatograph identified. Other projects, where the permeation level is low (

~ 30 mg) can give a much lower number of species identified.

Table 15 Reactivity Comparison

S ummary and Recommendations for Additional Investigations

There are several subjects that are recommended for additional investigation.

1. The Tier 2 (Near Zero) vehicles suggest that the effect of ethanol on permeation may be reduced (or zero?) based on th e limited number of tests available to date. The indication may change if the Tier 2 vehicles are tested after they are five or more years old.

2. The Tier 2 vehicles also show a mixed effect of fuel v apor pressure on permeation. Permeation was higher in many cases with the lower v apor pressure (7 psi E20) fuel. The order of testing was always first on the 9 psi fuel, and then a week later on the 7 psi fuel.

Should the order have been mixed?

3. Is it possible that the newer adv anced materials (tanks, hoses, seals) used in the Tier 2 vehicles are more resistant to changes in permeation, and take longer to stabilize than previously thought?Final CRC E

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### Acknowledgements

The authors gratefully acknowledge the contributions and support offered by the management and staff of the Automotive Test Laboratories, Inc. at Mesa, Arizona. The E

- 77 test series was a significant undertaking of a unique testing regimen, and would not have succeeded without their

efforts and dedication.

Our sincere thank s are offered to:

Greg Barton

- President

Kevin Brown

- Technician

Brian Hall

- Engineer

Stuart Seale

- Data and Quality Manager

Kevin Winkler

- Engineer



### Steering Committee

David Brzezinski

................. US Environmental Protection Agency
Wendy Clark

..................... National Renewable Energy Laboratory

Dominic DiCicco

................................ .......... Ford Motor Company
King Eng

................................ .............. Shell Global Solutions (US)

Jim Frusti

................................ ................................ ... Chrysler LLC

Pam Graham

................................ ...................... Inergy Automotive
Benjamin Hancock

........................ California Air Resources Board

Constance Hart

.................... US Environmental Protection Agency

Phil Heiri gs

................................ ....... Chevron Global Downstream

Jeff Jetter

................................ .............. Honda R&D Americas Inc.

Keith Knoll

....................... National Renewable Energy Laboratory

John Koupal

......................... US Environmental Protection Agency

David Lax

................................ ................................ .................. API
Jeffrey E Long

. .............................. California Air Resources Board

Hector Maldonado

......................... California Air Resources Board

Mani Natarajan

................................ .......... Marathon Oil Company

David Patterson

..................... Mitsubishi Motors R&D of America

Charles H

. Schleyer

. ............ ExxonMobil Research & Engineering
Jenny Sigelko

................................ ............................. Chrysler LLC

Nakia L. Simon

................................ ............... Chrysler Group LLC

James P. Uihlein

............................... Chevron Global Dow nstream

Michael B. Viola

............................... General Motors R&D Center

Ken Wright

................................ .............................. ConocoPhillipsFinal CRC E

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## Appendix I

– Task 4.5

Appendix I contains the individual vehicle data and plots that display the fuel vapor pressure effect on evaporative emission tests run for Task 4.5 of this program.

For each vehicle there are tables of the evaporative test results, reactivity results and plots of the 86o and 105o F static tests, the running loss and hot soak test and the cumulative three day diurnal

test.Final CRC E

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### Evaporative Test Results

Vehic le 206c

Reactivity ResultsFinal CRC E

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40Final CRC E

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41Final CRC E

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### Evaporative Test Results

Vehicle 208c

Reactivity ResultsFinal CRC E

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43Final CRC E

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44Final CRC E

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### Evaporative Test Results

Vehicle 209c

Reactivity ResultsFinal CRC E

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46Final CRC E

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47Final CRC E

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### Evaporative Test Results

Vehicles 210c

Reactivity ResultsFinal CRC E

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49Final CRC E

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50Final CRC E

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### Evaporative Test Results

Vehicle 2 13c

Reactivity ResultsFinal CRC E

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52Final CRC E

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53Final CRC E

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### Evaporative Test Results

Vehicle 221 c

Reactivity ResultsFinal CRC E

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55Final CRC E

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### Evaporative Test Results

Vehicle 222 c

Reactivity Results

This is the “Zero Evap” model tested in this program, and has very low emission levels . On many of the speciated tests in the table above, the individual species were below the GC detection limit. As such, the results appear as 0.Final CRC E

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## Appendix II

– Tas k 4.7

Appendix I I contains the individual vehicle data and plots that display the effect of leak location on permeation emissions as run for Task 4.7 of this program.

For each vehicle there are tables of the evaporative test results, reactivity results and plots of the 86o F static tests, the running loss and hot soak test and the cumulative three day diurnal test with the implanted leak in the tank top and the canister inlet.Final CRC E

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### Evaporative Test Results

Vehicle 207c

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### Evaporative Test Results

Vehicle 2 11 c

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## Appendix III

– Test Concept

The testing concept and procedures used in this program have evolved throughout the CRC E

- 77 program series, and are included here for reference.

The E

- 77 Test Concept: Measuring Leaks, Permeation and Diurnal Vapor Losses

CRC’s E

- 77 emission test programs have developed (and strive to continually improve) new methodologies for understanding and quantifying vehicle evaporative emission rates. The concept partitions and assigns the vehicle’s contribution to the evaporative emission inventory

into three mechanisms:

1. Permeation

2. Tank vapor venting

3. Leaks (with two subsets

- Liquid and Vapor)

Permeation is the migration of HC through the various elastomers in a vehicle fuel system 16



### . Previous testing has shown that permeation rate is strongly affected by the material’s temperature, doubling for each 10oC (18oF) increase in the range of normal summer temp eratures (See, among others, CRC E

- 65.3 report) It is also strongly affected by gasoline composition, especially with ethanol

- containing fuels.

Tank vapor venting emissions are controlled by fitting a carbon canister to the atmospheric tank vent. Figure A1 is a schematic of a typical early control system. During a daily heating period, the temperature of the vehicle’s fuel tank increases, forcing HC vapors from the tank. Excess emissions, exceeding the carbon canister’s capacity, are vented to the atmos phere.

Figure A

- 1. Control System Schematic

16 “Fuel Permeation from Automotive Systems: Final Report CRC Project E

- 65,” Haskew, Liberty and McClement, Sept ember 2004, available on the CRC and California Air Resources Board websites.Final CRC E

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### Leaks can be liquid or vapor. Mass emissions are measured in a VT SHED or Variable Temperature Sealed Housing for Evaporative

Determination. The SHED test method combines all

three emission mechanisms (leaks, diurnal venting, and permeation) into a single test result.

The SHED technique involves placing the vehicle in a sealed enclosure (Figure A2), and calculating the mass in the enclosure from the volume, density and

concentration in the enclosure at the start and end of a time period. The difference between the mass at the start and end of test is the emission rate, e.g., grams per

unit time.

Permeation and tank venting losses are stron gly driven by fuel composition, ambient temperature, and ambient temperature change. Liquid leaks are not strongly affected by normal summer temperatures, and are thought to have two components:

1. Static leaks occurring while the engine is turned off and the vehicle is stationary

2. Increase in leak rate caused by the system pressure increase during engine operation.

Each is described in detail below.

1. Static Permeation Testing

The constant tem perature (static) permeation rate is measured in a traditional SHED (Constant temperature) in the following manner.

A. The fuel tank is drained and filled to 40% tank capacity with the test fuel.

B. The day before testing, the vehicle is driven over four road t rips of 7.5 miles each to precondition the canister. 17 

### (These drives are similar to the LA

- 4)

C. Upon return from the road pre

- conditioning, the fuel tank is drained and filled to 40% tank capacity with the test fuel. 18



### D. Vehicle is parked for 18

- 22 hours in a controlled temperature environment at test temperature (86oF)

E. The vehicle is then moved (without starting) into the test (86oF) SHED

F. The canister vent is connected to the SHED bulkhead fitting which routes the vapor to the trap canister outside the SHED

G. T he tank system pressurization hose is connected

H. The fuel pump electrical connection is connected

17 This conditioning can be done in the laboratory on a chassis dynamometer if proper attention is paid to underbody cooling and unrepresentative fuel tank temperatures are avoid ed.

18 Vehicles with ORVR systems will add the refueling vapors to the canister. This is OK. Figure A

- 2. S ealed H ousing for E vaporative

D eterminationFinal CRC E

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### I. The SHED is sealed, the inside temperature is allowed to stabilize and the test is started. Continuous total hydrocarbon (THC) measurements are made using a FI D. Ethanol, methanol and R134a concentrations are measured using an INNOVA analyzer. All measurements are made at least every minute for one hour to determine the stabilized permeation rate.

J. At the end of the static test (60 minutes), the vehicle’s vapo r system is pressurized to 5 inches of water for thirty minutes. Measurements are made to quantify vapor leaks as determined by a change in the SHED uncorrected mass.

K. The fuel pump is then energized for 30 minutes while maintaining the 5 inches of water on the vapor system. Liquid leaks are quantified as determined by a change in the SHED

concentrations.

The purpose of steps J and K above is to validate that the permeation rate measurement was made without the presence of any leak

– either liquid o r vap or.

2. Running Loss Test (Dynamic Test)

A. The vehicle is placed in the RL

- SHED and prepared for test. (The fuel level and condition for the dynamic test is the fuel remaining after completion of the static test

– 40% fresh fill of the appropriate test fuel)

B. Outside air source for the engine is connected

C. Vehicle exhaust is connected

D. Fuel tank thermocouple is connected

E. Canister vent is connected to the SHED bulkhead fitting which routes the vapor to the

trap canister outside the SHED

F. Vehicle is allowed to stabilize in the RL

- SHED at test temperature (86°F) for a minimum

of 12 hours

– preferably overnight.

G. Two cycles of the Unified Cycle (LA

- 92) driving schedule (48 min utes .) are driven while measuring the mass emissions in the SHED. Vehicle is allowed to idle (in drive) for 30 seconds between the two cycles. Ambient air temperature is maintained (to the extent possible) at 86°F. Fuel tank surface temperature is monitored during vehicle operation. It

should inc rease during the drive from 10 to 18°F to simulate expected on

- road temperature increase. Measured mass emissions are corrected using the INNOVA data for the ethanol, methanol and refrigerant emissions.

3. Hot Soak 19


### This procedure is executed immediatel y following the Running Loss Test procedure

described above.

A. Engine is turned off, transmission selector is placed in park, and driver exits the enclosure, using the double door air lock, taking care to minimize any air exchange between the laboratory and the SHED. This starts the one hour “hot soak” period.

19 Our definition is that the “hot soak” is the temporary increase in emission rate caused by the vehicle’s immediately preceding operation. It is the increase in the SHED mass (corrected for EtOH, MeOH and R

- 134a) over the one hour period minus the previously established “static” permeation rate.Final CRC E

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### B. Measurement of mass emissions in the SHED are continued for another 60 minutes (until time = 108 minutes), correcting for the ethanol, methanol and refrigerant mass using the

INNOVA instrument data. T his ends the hot soak. Hot soak emissions are calculated as the net difference for the one hour hot soak (CorrMass 108


### – CorrMass 48 

### minus the 86°F static hourly rate, all mass rates in mg/hour).

4. Diurnal Test

A. The fuel tank is drained and filled to 40% tank capacity with the test fuel.

B. The day before testing, the vehicle is to be driven over four road trips of 7.5 miles each to precondition the vehicle and the canister.

C. Upon return from the road pre

- conditioning, the fuel tank is drained and filled t o 40% tank capacity with the test fuel.

D. The vehicle is parked for 18

- 22 hours in a controlled temperature environment at the initial diurnal test temperature (65oF).

E. The SHED is sealed, allowed to stabilize at the 65°F temperature and the 3

- day

California Diurnal Test is started.

F. “Continuous” (every 30 seconds) total hydrocarbon (THC) measurements are made using a FID. Ethanol, methanol and R134a (refrigerant) concentrations are measured using an INNOVA analyzer, at least every 10 minutes for the duration of the test (72 hours).

Static Permeation Test

– Leak Validation

If a leak is detected during either the vapor system pressure portion (Step J) or the pump energized portion (Step K) of the Static Permeation Test procedure, it calls into question wheth er the permeation rate measurement accurately reflects fuel system permeation or if instead a combination of permeation and the implied leak was measured. If a leak is confirmed, the permeation rate measurement is called into question, and an investigatio n, possible remedy, and

retest is indicated.

The permeation rate measurement must be corrected for the FID’s ethanol misrepresentation, and the presence of non

- fuel hydrocarbons (methanol and refrigerant). The leak check however, is made using the change in mass increase in the SHED using the uncorrected FID mass calculation as the determinate. We found that the corrections for ethanol, methanol and refrigerant were introducing “noise” into the trace that we were misinterpreting as leak(s).Final CRC E

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### Figure A

- 3 represents the calculations made during the inspection of data from a successful test.

EXCEL’s © 

### “SLOPE” function is used to calculate the linear regression values based on the FID

calculation for mass for: Time 0 to 60 min utes, Time 64 to 90 minutes, and Time 94 to 120 minutes. A 4 minute gap was included between each sequence to establish the new mass emission rate during the “pressure on,” (T 60 

### to T 90 

### ), and the “pump energized” periods.

The slope of 70.6 mg/hr for the “Tank Pressurized” period in the example above i s compared to the slope of 70.5 mg/hr calculated for the permeation rate (or hot soak) peri od. If the “Tank Pressurized” slope is not more t han 10% higher than the 0 to 60 minute permeation rate, we

assume t hat there is no leak present. A similar comparison is made for the slope determined during the “pump on” period. The choice of a 10% allowance is arbitrary and is used here to

allow for normal and unavoidable test variation.

For tests in which the above procedure determines that no leak is present, a value of zero is reported in the test summary for the leak results. If a positive value is reported, it calls that test into question, and an investigation, possible repair, and retest is indicated. Figure A

- 3. Leak TestFinal CRC E

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### Stati c Permeation Rate Determination

The static permeation rate is determined based on a linear regression through the individual

corrected f

uel data points (30 second data) for the first 60 minutes of testing as illustrated by the

corrected FID data shown in the red trace in Figure A

- 3 above; in this case 72.1 mg/hour

.

Dynamic (Running Loss) and Hot Soak Test

The preceding section addressed the concepts of separating the permeation emissions from the tank venting emissions, and establishing the presence or a bsence of leaks. The second part of this study includes a dynamic test to measure the permeation and tank venting emissions during vehicle operation (“running losses”) and the temporary condition following vehicle operation

known as the “hot soak.”

This is considered a “dynamic” test because the vehicle is driven and the fuel and vapor system temperatures rise during the test. The ambient temperature in the Running Loss SHED during test was held constant at 86°F, while the vehicle’s fuel system temperatu re rose during the test. Two 1435 second (23.9

- minute) LA

- 92 driving cycles were performed consecutively during the running loss measurements with a 30 second idle in

- between. During this test, tank fuel temperature was expected to rise by an average appr oximately 18°F above the initial ambient temperature. The running loss air handling system included a proportional speed under

- car blower operated as a slave to dynamometer speed. This apparatus was used during running loss testing with minor tuning for specific vehicles. It is, without additional input, capable of reasonable fuel tank temperature control. Each vehicle was fitted with a surface

- mount thermocouple at the front of the fuel tank, located at approximately the 1/8 th 

### fill level to measure

the fuel liquid temperature. No attempt was made to follow a predefined fuel tank temperature profile (FTTP) in this program. Fuel temperatures were recorded, and results are available in the

real

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### Vehicle running loss emissions are measured in a special version of a SHED known as a Running Loss SH ED (RL

- SHED) 20 

### , shown in Figure A

- 4 . Special features of the RL

- SHED include a sealed chassis dynamometer for simulating vehic le driving loads, a sealed outside air supply for engine intake, a sealed exhaust conduit for engine exhaust, and an under

- chassis fan for simulating underbody air flow as described above. A vehicle is operated inside the RL

- SHED over a chosen driving cycl e. The increase in HC emissions inside the enclosure are measured and calculated as mass emissions per 40 CFR §86.163

- 96. Vehicle testing in an RL

- SHED is complicated by several factors, including:

1. The engine must be supplied with external induction air. 2. The exhaust must be conducted externally without any leaks. 3. The load supplied to the vehicle through the chassis dynamometer must not create or

allow external leaks. 4. The internal SHED temperature must be maintained while sizable heat is r ejected to the ambient by the running engine and exhaust. 5. The cooling air supplied to the radiator must be modulated to represent the vehicle’s road speed. 6. The underbody (and especially the fuel system) temperature should represent the rate

of rise experienced by a real road

- drive.

Canister vent losses were isolated from permeation emissions using the technique described previously. The vehicle’s carbon canister fresh air vent was connected to the outside of the RL

SHED using a leak

- tight Teflon ® 

### hose connected to a small carbon “trap” canister located on a

20 See SAE 1999

- 01

- 1464, “Running Loss Emissions from In

- Use Vehicles, Harold Haskew, et al., May 1999, for

a more c omprehensive discussion of running loss measurement detail. Also available as CRC Report 612, Project E35

- 2, “Running Loss Emissions from In

- Use Vehicles”, available in the engineering report section of

the CRC web

- site www. crcao .org



### Figure A

- 4

- Vehicle Installed in Running

Loss SHED SHEDSHEDFinal CRC E

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### top

- loading precision scale outside the SHED . The scale precision was 0.01 grams (10 milligrams). There were no tank venting emissions measured on any of the running loss test

measurements. A ll of the vehicles appeared to be actively “purging” the vehicle’s control canister and drawing fresh air during the test. If there were any emissions from the vehicle’s canister, as might have occurred if there were no vehicle purge or if very high volat ility fuels with excessive vapor generation were used, it would have been measured.

The Running Loss Driving Cycle consisted of two cycles of the “Unified Driving Cycle,” otherwise

known as the LA

- 92. A velocity versus time plot for one cycle is shown in Figure A

- 5

.

The LA

- 92 cycle takes 24 minutes to complete, and covers 9.8 miles, with many speed changes.

Two back

- to

- back cycles were driven, the first as a “cold start,” and the second following a 30

sec ond vehicle idle. The “cold start” condition was created by soaking the vehicle for a minimum of 18 hours at 86°F, moving it to the stabilized 86°F RL

- SHED, making the test connections, and then waiting a minimum of one hour before the initial start and r un.

The SHED emissions were measured during the 48 minutes of engine operation, and then continuously for one hour after the engine was turned off. This one hour, engine

- off duration was the “hot soak” period. The total test time is 1 hour and 48 minutes.

Figure A

- 6 shows results from the 9 psi E20 fuel test on Vehicle 209c . The horizontal axis is test time in minutes, and the vertical axis is the HC mass measured in the RL

- SHED during the test period.

The engine was shut off at the end of the second LA92 drive cycle (~48 minutes), and the analysis system continued to measure the HC emissions in the SHED for the next 60 minutes. This represented the “hot soak” portion of the test. Figure A

- 5

- Running Loss Driving CycleFinal CRC E

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### The “True” Hot Soak

The traditional hot soak is determined from the increase in SHED emissions as measured for one hour following a prescribed drive to heat up the vehicle (2 LA

- 92 cycles during the Running Loss Test). Hot soak emissions, however, have two c omponents; one that is caused by the elevated temperature resulting from the drive, and another that results from one hour of static permeation.

To separate these two components and determine the “true” hot soak emissions, the following procedure was used . “Traditional” hot soak emissions were first calculated by subtracting the “start of hot soak” cumulative SHED hydrocarbon value (i.e., 293.6 mg @ t = 48 minutes) from the final cumulative SHED hydrocarbon value (i.e., 379.3 mg @ t = 108 min.). This res ulted in a cumulative SHED hydrocarbon value of 85.7 mg for the one hour hot soak. The previously

determined 86oF static permeation value (i.e., 42.0 mg /hr ) was then subtracted to arrive at the

“true” hot soak value of 43.7 mg.

In Figure A

- 6 , the stati c permeation rate is superimposed as a solid blue line on the plot from the starting point of the hot soak until its end (one hour). While the “traditional” hot soak would be

calculated as 85.7 mg, the “true” hot soak is determined as 4 3.7 mg . True hot s oak values reported here were determined in this manner. Figure A

- 6

- Running Loss and Hot Soak

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### Diurnal Test

Diurnal permeation was determined by su bjecting the vehicle to a three

- day period in a

temperature con trolled SHED while recording the total hydrocarbon every 30 seconds. The

SHED env ironmental temperature was varied from 65°F to 105°F per the California Diurnal Test protocol. Canister vent losses were isolated from permeation emissions using the technique described previously. The vehicle’s carbon canister fresh air vent was connecte d to the outside

of the RL

- SHED using a leak

- tight Teflon ® 

### hose connected to a small (1 L) carbon “trap” canister located on a top

- loading precision scale. The scale precision was 0.01 grams (10 milligrams).

ATL’s Speciation Method

ATL has developed a hydrocarbon speciation method that is functionally equivalent to the dual

GC AQIRP method. The AQIRP, or “Auto/Oil Program,” test method was fir st documented in two SAE papers :

1. SAE 920320, Advanced Emission Speciation Methodologies for the Auto/Oil Air Quality Improvement Research Program

- I. Hydrocarbons and Ethers; and

2. SAE 920321, Advanced Emissions Speciation Methodologies for the Auto/Oil Air Quality Improvement Research Program

– II. Aldehydes, Ketones, and Alcohols

A later update to the HC and Oxygenates procedures was published as:

SAE 930142, Improved Emissions Speciations Methodology for Phase II of the Auto/Oil Air Quality Improvement Program Hydrocarbons and Oxygenates

(See also, for reference, ARB’s SOP NO. MLD 115, “Procedure for the De termination of Ethers and Alcohols in Gasoline by Gas Chromatography ” , January 2003, and SOP NO. MLD 118, “Procedures for the Detailed Hydrocarbon Analysis of Gasolines by Single Column High Efficiency (Capillary) Column Gas Chromatography ” , August 1997)

Instrumentation demands are simplified, and overall analysis time is shortened; yet high resolution and sensitivity are still achieved. In this single

- GC/dual column method, all components are separated using on column type and temperature program. Ana lysis time for a cycle is 65 minutes. Each exhaust or evaporative gas sample is simultaneously injected (using a single sampling from the bag) into two identical columns present in the GC. A Varian Model

3400 GC is used for hydrocarbon (HC) analy sis. Th e GC is equipped with a dual temperature

controlled Valco 6

- port valve injector; dual flame ionization detectors (FID), and dual 60 meter x

0.32

- mm ID fused silica capillary columns with 1.0μ polydimethylsiloxane stationary phase (J&W DB

- 1). One of the in jectors uses an 85 μL sampling loop for low sensitivity analysis of

C 1 

### - C 12 

### while the other injector either uses a 1000 μL loop for high sensitivity analysis of C 4 

### - C 12 

### (for simultaneous low/high sensitivity analysis of a single bag sample). Column A contai ns a 85μl sample loop (splitless injection) that provides an injection volume that is small enough to

allow resolution of the C 1 

### through C 4 

### hydrocarbons while large enough to retain the highest sensitivity possible. Column B receives a 1000μl splitless in jection, providing higher sensitivity for components eluting after isobutane. Quantitative comparison of two overlap componentsFinal CRC E

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### (butane and isopentane) provides a quality control measure. Data from Column A is used to detect and quantitate the 12 earlies t eluting hydrocarbons with detection limits of 15

- 25 ppb

v 

### C corresponding to 0.2

- 0.3 mg/mi hydrocarbon for FTP stages 1 and 3, and 0.3

- 0.5 mg/mi for FTP stage 2. Data from Column B gives detection limits 0.017

- 0.04 mg/mi HC for components eluting after isopentane (18 th 

### in elution order). The components eluting between the 9 th 

### and 18 th


### in elution order have detection limits ranging between the levels listed above for each column.

The advantage of this approach is that, even for relatively clean vehicles , essentially all of the first 12 species are typically present at levels exceeding the Column A detection limit. Those speciated components that are below the first column detection limit tend to be in the molecular weight range best suited for the 1000μ l injection analysis, which provides the limits 0.017

- 0.04 mg/mi HC for components eluting after isopentane (18 th 

### in elution order), where additional sensitivity is needed. In previous work that applied this analysis approach, detection limits were

determ ined to be between 0.02

- 0.06 mg/mi for the toxics 1,3

- butadiene and benzene. ATL’s hydrocarbon method uses Varian 3600 GCs with dual injectors, columns, and flame ionization detectors, allowing two similar analyses to be run simultaneously, as mentioned

ab ove. A Varian Star PC

- based (using Microsoft Windows TM ) data system is used for data acquisition. Custom

- made software is used for peak identification and converting data into a

Microsoft Excel TM spreadsheet format. A comparison of the total hydrocarbon d etermined using the GC versus the CVS (“speciation recovery”) is used as a quality control measure, and ATL routinely achieves hydrocarbon speciation recoveries ranging from 93% to 105% for lower emitting vehicles. A 23 hydrocarbon component standard mixt ure is analyzed at the start of each day on each GC to provide quantifying coefficients and a quality control check on daily reproducibility of instrument performance.Final CRC E

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## Appendix IV

– Speciation and Reactivity Results

Appendix I contains the individual vehicle data generated from the speciation tests performed on all the evaporative tests run for this program.

For each vehicle there is a summary table reactivity results followed by the speciation results for

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195Final CRC E

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196Final CRC E

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197Final CRC E

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207Final CRC E

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209Final CRC E

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213 continuedFinal CRC E

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218 continuedFinal CRC E

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219Final CRC E

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220Final CRC E

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221 continuedFinal CRC E

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222 continuedFinal CRC E

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223Final CRC E

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224 continuedFinal CRC E

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225 continuedFinal CRC E

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226Final CRC E

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227Final CRC E

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228 continuedFinal CRC E

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229Final CRC E

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230 continuedFinal CRC E

- 77

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231Final CRC E

- 77

- 2c Report

- Dec 2010

232 continuedFinal CRC E

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233Final CRC E

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- Dec 2010

234 continuedFinal CRC E

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235Final CRC E

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236 continuedFinal CRC E

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237Final CRC E

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238 continuedFinal CRC E

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239Final CRC E

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240 continuedFinal CRC E

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241Final CRC E

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- Dec 2010

242 continuedFinal CRC E

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- Dec 2010

243 continuedFinal CRC E

- 77

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- Dec 2010

244Final CRC E

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- Dec 2010

245Final CRC E

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- 2c Report

- Dec 2010

246 continuedFinal CRC E

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- Dec 2010

247Final CRC E

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- Dec 2010

248 continuedFinal CRC E

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249Final CRC E

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250 continuedFinal CRC E

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251 

## Appendix V

– Fuel Inspections

– Previous ProgramsFinal CRC E

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