### 2215 Raggio Parkway, Reno, Ne vada 89512-1095 (775) 673-7300 

# Section 211(B) Tier 2 High End Exposure Study of Conventional and Oxygenated Gasoline

COMPILED FINAL REPORT

Prepared for

AMERICAN PETROLEUM INSTITUTE

1220 L Street Washington, DC 20005-4070

Prepared by

Barbara Zielinska, Eric M. Fujita, John C. Sagebiel, and David E. Campbell Division of Atmospheric Sciences

Desert Research Institute Nevada System of Higher Education 2215 Raggio Parkway Reno, NV 89512

March 25, 2009

### ii ACKNOWLEDGMENTS

We wish to acknowledge the financial support for this st udy by the American Petroleum

Institute and Drs . Will Ollison and Lorraine Twerdok of the API for their administrative support

and technical guidance. We also thank the API review committee and the staff of the U.S. Environmental Protection Agency for review ing the draft exposure protocols and interim project

results

. We also acknowledge the vehicle testing performed during the control experiments in

San Antonio by Lawrence Smith and Patrick Merritt at Southwest Research Institute and evaluation of potentia l biomarkers during the initial pilot study by Dr. Jacob McDonald of the Lovelace Respiratory Research Institute. We also acknowledge the assistance of Ted Johnson of TRJ Environmental, Inc . for his input on the candidate microenvironments and review of our

draft exposure protocols. We also acknowledge the following DRI personnel for their assistance: Larry Sheetz for modifications to the sampling platforms; Aaron Centric, Diana Ceballos and Mark McDaniel for field sampling ; Diana Ceballos for evaluation of the SPME method ; and

Kat a rzyna Rempala and Michael Keith for the organic speciation analysis.

### iii TABLE OF CONTENTS

Page

Acknowledgments........................................................................................................................... ii

EXECUTIVE SUMMARY .............................................................................................................1

1. Quantification of Personal Exposures to Motor Vehicle Emissions in High Exposure Microenvironments in Atlanta, Houston, and Chicago during Summer and Winter. ........... 1-1

1.1 Introduction ................................................................................................................... 1-1

1.2 Experimental .................................................................................................................. 1-2

1.2.1 Selection of Microenvironments .......................................................................... 1-2

1.2.2 Monitoring Methods ............................................................................................ 1-4

1.2.3 Exposure Biomarkers ........................................................................................... 1-5

1.3 Results and Discussion .................................................................................................. 1-6

1.3.1 Variation of day- to -day exposures by ME in each city ....................................... 1-6

1.3.2 Distribution of exposures within MEs in each city (1- minute time series) ....... 1-22

1.3.3 Oxygenated and conventional gasoline (difference between cities) .................. 1-34

1.3.4 Effect of meteorology on exposure .................................................................... 1-38

1.3.5 Comparison of summer and winter exposures ................................................... 1-40

1.3.6 Correlations to breath concentrations ................................................................ 1-44

1.4 Conclusions ................................................................................................................. 1-48

1.5 References ................................................................................................................... 1-49

2. Relative Contributions of Vehicle Evaporative and Exhaust Emission to Concentrations of Volatile Air Toxics in High Exposure Microenvironments in

Houston .................................................................................................................................. 2-1

2.1 Introduction ................................................................................................................... 2-1

2.2 Experimental Approach

................................................................................................. 2-2

2.3 Results ..................................................................................................................... 2-3

2.4 Conclusions ................................................................................................................... 2-4

2.5 References ................................................................................................................... 2-10

3. Determination of the Quantitative Relationships between Levels of Volatile Air Toxics and Carbon Monoxide Measured In High End Microenvironments and At Nearby Ai r Quality Monitoring Stations ............................................................................... 3-1

3.1 Introduction ................................................................................................................... 3-1

3.2 Experimental .................................................................................................................. 3-2

3.3 Results and Discussion .................................................................................................. 3-3

3.4 Conclusions ................................................................................................................... 3-4

3.5 Ref erences ..................................................................................................................... 3-4

4. Relationships of Attached Garage and Home Exposures to Fuel Type and Emission Levels of Garage Sources ...................................................................................................... 4-1

4.1 Introduction ................................................................................................................... 4-1

4.2 Experimental .................................................................................................................. 4-1

### iv 4.2.1 Vehicles and Vehicl e Test Methods .................................................................... 4-1 4.2.2 Fuel Testing ......................................................................................................... 4- 2

4.2.3 Test House ........................................................................................................... 4- 2

4.3 Results .................................................................................................................. ... 4-4 4.3.1 Fuel Analyses ....................................................................................................... 4-4 4.3.2 Vehicle Regulated and Hot Soak Emissions ........................................................ 4-5 4.3.3 Garage and Kitchen Exhaust/Evapora tive Fuel Component Levels .................... 4-7 4.3.3.1 Background and Overall Concentrations .............................................. 4-7 4.3.3.2 Seasonal Impacts ................................................................................... 4-8

4.3.3.3 Fuel and Vehicle Effects ....................................................................... 4-9 4.3.3.4 Comparison with Emissions Data ....................................................... 4-16 4.3.3.5 Relationships of Garage and Kitchen Concentrations ........................ 4-19

4.4 Discussion ............................................................................................................... .... 4-21

5. Effect of Ventilation, Proximity, and Em ission Levels on In-Cabin Exposures of Trailing Vehicle. ............................................................................................................. ....... 5-1

5.1 Introduction .............................................................................................................. ..... 5-1 5.2 Experimental .............................................................................................................. .... 5-1 5.2.1 Fuel Testing ......................................................................................................... 5- 2 5.2.2 Relationship between Exhaust Emi ssion Rates and In-Cabin Exposure - Trailing Vehicle Test ................................................................................... 5-2

5.2.2.1 Test Protocol ......................................................................................... 5-2

5.3 Results .................................................................................................................. ... 5-6 5.3.1 Background and Overall Concentrations ............................................................. 5-6

5.3.2 Vehicle and Fuel Effects .................................................................................... 5-12 5.3.3 Trailing Vehicle Effects ..................................................................................... 5-14 5.3.4 Comparison with FTP Data ............................................................................... 5-16

5.4 Discussion ............................................................................................................... .... 5-18

Appendix A .................................................................................................................... ............. 144*

Appendix B ..................................................................................................................................223

Appendix C ..................................................................................................................................236

Appendix D ..................................................................................................................................237

Appendix E ..................................................................................................................................300

Appendix F..................................................................................................................... ..............398

Appendix G ..................................................................................................................................450

Appendix H ..................................................................................................................................453

Appendix I ...................................................................................................................................464

* Appendix pagination corresponds to Adobe Reader page count index.

### v LIST OF FIGURES

Page

Figure E -1. Distribution of reconstructed 1-min BTEX exposures in high-end Atlanta MEs. Edges of the box = first and third quartiles; black line = median; red line = average. Minimum and maximum values (ppbv) are shown at the bottom and top of the plots. Whisker covers 99.3% of the data distribution. Filled circles > 3 times the box interval, empty circle are within that interval. The y

- axis represents the percentage of data distribution.

................................................................................ ES -9

Figure E -2A. Comparison of average concentrations of benzene, 1,3- BD, HCHO and CO

in three cities in Summer

............................................................................................. ES -10

Figu re E -2B. Comparison of average concentrations of benzene, 1,3- BD, HCHO and CO

in three cities in Winter

................................................................................................ ES -11

Figure E -3. MTBE/benzene ratio and contribution of evaporative emissions in Houston

MEs

.............................................................................................................................. ES -13

Figure E -4. Mean ratios of ME concentrations to corresponding hourly measurements at the regional air monitoring station in Houston.

........................................................... ES -14

Figure E -5. The effect of fuel and vehicle operation mode (i.e. normal or malfunction) on

observed concentrations in the kitchen

........................................................................ ES -17

Figure 1.3.1- 1. Time

- integrated ex posure levels in different MEs in Atlanta, Summer

2002 and 2003 ................................................................................................................ 1-14

Figure 1.3.1- 2. Time -integrated exposure levels in different MEs in Atlanta, Winter 2004 ..... 1-16

Figure 1.3.1- 3. Time -integrated exposure levels in different MEs in Chicago, Summer

2003

................................................................................................ ................................ 1-17

Figure 1.3.1- 4. Time -integrated exposure levels in different MEs in Chicago, Winter

2004

................................................................................................ ................................ 1-18

Figure 1.3.1- 5. Time -integrated exposure levels in different MEs in Houston, Summer

2004

................................................................................................ ................................ 1-20

Fig ure 1.3.1- 6. Time -integrated exposure levels in different MEs in Houston, Winter

2005

................................................................................................ ................................ 1-21

Figure 1.3.2-1. 1- Minute time series for in -cabin exposures: ME1 (congested freeway), ME2 (urban canyon); ME4 (underground garage) and ME5 (toll plaza) ...................... 1-30

Figure 1.3.2-2. 1- Minute time series for in -cabin exposures: ME6 (tunnel); ME13 (following high- emitting vehicle); ME3 (in

- cabin refue ling) and out- of -cabin refueling, ME7 ............................................................................................................... 1-31

Figure 1.3.2-3. 1- Minute time series for out -of cabin outdoor exposures:ME8 (sidewalk); ME10 (surface parking); ME11 (underground garage) and ME12 ( toll plaza) ............. 1-32

Figure 1.3.2-4. Correlations between 5- minute canister samples and surrogate 1

- minute values, averaged over corresponding 5 minutes. ........................................................... 1-33

### vi Figure 1.3.3-1. MTBE and EtOH concentrations in Houston and Chicago, respectively..Note different y- axis scales for Chicago Sumer and Winter .................... 1-35

Figure 1.3.3-2. Comparison of benzene, 1,3-BD, HCHO, and CO average concentrations

in three cities in Summer ............................................................................................... 1-36

Figure 1.3.3-3. Comparison of benzene, 1,3-BD, HCHO, and CO average concentrations

in three cities in Winter .................................................................................................. 1-37

Figure 1.3.5- 1. Time integrated average exposure levels in different MEs in Atlanta in

Summer and Winter season. .......................................................................................... 1-41

Figure 1.3.5-2. Time integrated average exposure levels in different MEs in Chicago in

Summer and Winter season ........................................................................................... 1-42

Figure 1.3.5- 3. Time integrated average exposure levels in differen t MEs in Houston in

Summer and Winter season ........................................................................................... 1-43

Figure 1.3.6- 1. Average breath BTEX, 1,3 -BD, MTBE, EtOH, and CO2 concentrations in

three cities in Summer ................................................................................................... 1-45

Figure 1.3.6- 2. Average breath BTEX, 1,3 -BD, MTBE, EtOH, and CO2 concentrations in

three cities in Winter ...................................................................................................... 1-46

Figure 1.3.6-3. Correlations between 1- minute su rrogate benzene and 1,3

- BD max values and post-exposure breath concentrations (upper panel) and comparison of these concentrations in different ME and cities (lower panel) ................................................ 1-47

Figure 2

- 1.Frac tional contributions of evaporative emissions to total motor vehicles emissions in Houston by ME. .......................................................................................... 2-9

Figure 3.1a. Location of ME sampling and fixed monitoring stations in Chicago Metro

Area. ................................................................................................................................. 3-9

Figure 3.1b. Location of ME sampling and fixed monitoring stations in Houston Metro

Area. ............................................................................................................................... 3-10

Figure 3 -2a. Comparison of av erage versus the maximum 1

- minute benzene levels by city, season and microenvironment. ............................................................................... 3-12

Figure 3 -2b. Comparison of average versus the maximum 1-minute 1,3- butadiene levels by city, season and microenvironment. .......................................................................... 3-13

Figure 3 -2c. Comparison of average versus the maximum 1- minute formaldehyde levels by city, season and microenvironment. .......................................................................... 3-14

Figure 4.3-1. Effect of fuel and mode on observed concentrations in the garage. The legend “N” is normal and “F” is malfunction. The 1,3-BD value for Houston- F is
suspect. ........................................................................................................................... 4-10

Figure 4.3-2. Effect of fuel and mode on observed concentrations in the kitchen. The legend “N” is normal and “F” is malfunction. The 1,3-BD value for Houston- F is
suspect. ........................................................................................................................... 4-11

### vii Figu re 4.3-3. Effect of fuel and mode on observed sedan garage levels. The legend “N” is normal and “F” is malfunction. The 1,3-BD level for Houston- F is suspect, see

text.

................................................................................................ ................................. 4-12

Figure 4.3- 4. Effe ct of fuel and mode on observed truck garage levels. The legend “N” is normal and “F” is malfunction. The 1,3-BD level for Houston- F is suspect, see

text.

................................................................................................ ................................. 4-12

Figure 4.3-5. Concentrations of 1,3-butadiene, MTBE and BTEX and CO as measured from canisters in the garage and the adjacent kitchen in Summer 2002 ........................ 4-14

Figure 4.3-6. Concentrations of 1,3- butadiene, MTBE and BTEX (A) and CO (B) as measured from canisters in the garage and the adjacent kitchen in Winter 2005. M=sample missing or invalid. ....................................................................................... 4-15

Figure 4.3-7. Comparison of SHED results with the observed canister concentration in the garage for benzene. .................................................................................................. 4-16

Figure 4.3-8. Comparison of the SHED results with the observed SPME hot soak concentration in the garage for benzene A: all data, B: two outliers removed. ............. 4-16

Figure 4.3-9. Comparison of FTP Bag 1 emissions and observed garage levels of 1,3- BD. .... 4-17

Figure 4.3-10. Comparison of FTP Bag 1 benzene emissions and observed garage levels. ..... 4-18

Figure 4.3-11. Comparison of hot soak FTP Bag 1 benzene emissions and observed SPME garage values. ..................................................................................................... 4-18

Figure 4.3-12. Comparison of garage and kitchen concentrations for 1,3- BD. A

– all data, B- with two outliers removed (see text). ........................................................................ 4-19

Figure 4.3-13. Comparison of garage and kitchen concentrations of carbon monoxide. .......... 4-20

Figure 4.3-14. Comparison of garage and kitchen concentrations of benzene. ......................... 4-20

Figure 5.2-1. Map of Driving Test Location near San Antonio. The blue markers indicate the location of the driving tests. ....................................................................................... 5-4

Figure 5.2-2. Map of Driving Test Location near Moore, TX. ................................................... 5-5

Figure 5.2-3. Elevation Profile of the Driving Route near Moore, TX. ..................................... 5-5

Figure 5.3-1. Comparison of Summer and Winter Background Concentrations with Standard Deviations. HCHO is divided by 10 for scale. ................................................. 5-7

Figure 5 .3-2. Concentrations of 1,3- BD, MTBE and BTEX (A) and CO (B) as measured in the cabin of the trailing vehicle, Summer 2002 ........................................................... 5-8

Figure 5 .3-3. Concentrations of 1,3-BD, MTBE and BTEX and CO as measured in the cabin of the trailing vehicle, Winter 2005 ....................................................................... 5-9

Figure 5.3-4. Comparison of Summer and Winter Concentrations for the Trailing tests. ......... 5-10

Figure 5.3-5. Comparison of Summer Background and Test Values. ....................................... 5-11

Figure 5.3-6. Compa rison of Winter Background and Test Values. ......................................... 5-11

### viii Figure 5.3- 7. Scatter plot of Normal Emitter and High Emitter Mean In -cabin Values for all species except HCHO and EtOH. ............................................................................. 5-13

Figure 5.3-8. Time Series of In-Cabin (PID1) and Outside (PID2) PID Values. ...................... 5-15

Figure 5.3-9. Comparison of FTP Bag 2 Benzene Emissions to In-cabin Concentration in the Trailing Vehicle. ...................................................................................................... 5-16

Figure 5.3-10. Comparison of FTP Bag 2 MTBE emissions to in-cabin concentrations in the trailing vehicle. ......................................................................................................... 5-17

Figure 5.3-11. Comparison of FTP Bag 2 1,3- BD Emissions to In -cabin Concentrations in the Trailing Vehicle. .................................................................................................. 5-17

### ix LIST OF TABLES

Page

Table E -1. Measurement methods used in the Section 211(B) Tier 2 High-End Exposure Screening Study. Data applications for specific methods are clas sified as reference, confirmatory, and surrogate. ...............................................................................3

Table E -2. The effects of changing vehicle, fuel and operational mode (i.e. normal or malfunction) on observed concentrations in the trailin g vehicle cabin. ............................17

Table 1.2.1-1. Microenvironmental Sampling. ............................................................................ 1-3

Table 1.3.1-1. Summer average, maximum, and minimum ME concentrations (ppbv) of BTEX, 1,3-BD, HCHO, CH3CHO, EtOH, MTBE, and CO (ppmv) .............................. 1-7

Table 1.3.2-1A. Correlation coefficients (R 2 

### ) and associated statistic for relationships of

time

- integrated measur ements with continuous methods (NMVOC and CO) for 3 cities, without ME3 and ME7 ........................................................................................ 1-24

Table 1.3.2- 1B. Correlation coefficients (R 2 

### ) and associated statistic for relationships of

time

- integrated measurements with continuous methods (NMVOC and CO) for

ME3 and ME7 in 3 cities ............................................................................................... 1-25

Table 1.3.2-2. Summary of the reconstructed 1-minute data (ppbv), Summer ......................... 1-26

Table 1.3.2-3. Summary of the reconstructed 1-min data (ppbv), Winter ................................. 1-27

Table 1.3.2-4. Summary of the 5-minute canister data (ppbv) .................................................. 1-28

Table 1.3.4-1. Average, minimum, and maximum ambient temperatures and RH ................... 1-38

Table 2 -1. Conventional gasoline versus reformulated gasoline RFG (from EPA OMS web page http://www.epa.gov/OMSWWW/rfgnew.htm, updated by S. Romanow, OMS).

............................................................................................................................... 2-5

Table 2 -2. Summary of sample collections in urban MEs ........................................................... 2-6

Table 2 -3. Mass ratios of MTBE to benzene in Houston by ME. ............................................... 2-7

Table 2 -4. Mass ratios of MTBE to benzene in vehicle exhaust, gasoline vapor and liquid gasoline. ........................................................................................................................... 2-8

Table 2 -5. Fractional contributions of evaporative emissions to total motor vehicles emissions in Houston by ME. .......................................................................................... 2-9

Table 3 -1. Summary of sample collections in urban microenvironments ................................... 3-5

Table 3 -2. Average and standard deviation in ratios of the time-integrated CO from canister samples to the corresponding hourly CO fr om regional ambient air monitoring sites for Houston, Atlanta and Chicago by season and

microenvironment. ........................................................................................................... 3-6

Table 3 -3. Average and standard deviations in ratios of BTEX and 1,3- BD from time

integrated canister samples to the corresponding hourly automated GC data from the ambient air monitoring sites in Houston. ................................................................... 3-7

### x Table 3 -4. Houston benzene ME/ambient ratio comparison with HAPE M benzene ME

factors ............................................................................................................................... 3-8

Table 4.2-1. Summary of vehicles used. ...................................................................................... 4-2

Table 4.2-2. Protocol for attached garage experiments. .............................................................. 4-3

Table 4.3-1. Summary of properties for the six test fuels. ........................................................... 4-5

Table 4.3-2. Regulated and Hot Soak Emissions from the Ford F-150, Summer 2002. ............. 4-6

Table 4.3-3. Regulated and Hot Soak Emissions from the Ford F-150, Winter 2005. ................ 4-6

Table 4.3-4. Regulated and Hot Soak Emissions from the Toyota Camry, Summer 2002 ......... 4-6

Table 4.3-5. Regulated and Hot Soak Emissions from the Toyota Camry, Winter 2005 ............ 4-6

Table 4.3-6. Summary of Background Concentrations in Kitchen and Garage. Units are ppbv, except as noted. ...................................................................................................... 4-7

Table 4.3-7. Summary of Test Concentration Ranges in Kitchen and G arage. Units are ppbv, except as noted. ...................................................................................................... 4-8

Table 4.3-8. Seasonal Impact on Observed Maximum Concentrations (Units are ppbv, except as noted). ............................................................................................................... 4-8

Table 4.3-9. Seasonal Impact on Observed Maximum Concentrations (Units are ppbv, except as noted), Normal Mode Vehicles Only. .............................................................. 4-8

Table 4.3-10. Seasonal Impact on Observed Average Concentrations (Units are ppbv, except as noted), Normal Mode Vehicles Only. .............................................................. 4-8

Table 4.3-11. Effect of Fuel and Operational Mode of the Sedan on Observed Levels in

the Kitchen and Gar age (Units are ppbv, except as noted). ............................................. 4-9

Table 4.3-12. Effect of Fuel and Operational Mode of the Truck on Observed Levels in the Kitchen and Garage (Units are ppbv, except as noted). ............................................. 4-9

Table 5.2-1. Protocol for Trailing Vehicle Tests ......................................................................... 5-3

Table 5.3-1. Summary of Summer and Winter Background Concentrations. ............................. 5-6

Table 5.3-2. Summary of Test Concentrations for Summer, Winter and Overall. Units are ppbv, except CO as noted. ............................................................................................... 5-7

Table 5.3-3. Summary of Concentrations Observed During Idle Tests. Units are ppbv except CO as noted. ....................................................................................................... 5-12

Table 5.3-4. Effect of Vehicle, Fuel, and Operational Mode. Units are ppbv, except CO as

noted. Numbe r of measurements = n ............................................................................. 5-13

Table 5.3- 5. Influence of high emitting vehicles and each fuel on trailing vehicle in

- cabin concentrations. Units are ppbv except CO as noted. ..................................................... 5-14

Table 5.3- 6. Summary of Seasonal Differences in the High Emitter Samples. ......................... 5- 14

Table 5.3-7. Comparison of High and Low In-cabin Ventilation Conditions, Winter 2005 only. Units are ppbv except CO as noted. ...................................................................... 5-15

### ES -1 

## EXECUTIVE SUMMARY

This study evaluated the upper -end distribution of inhalation exposures to evaporative

and combustion emissions from conventional and oxyge nated -gasoline. This final report describes the measurement methods and protocol used in the study and summarizes the validation and initial analysis of the assembled database. The main findings and conclusions are emphasized in this final report and additional details and descriptions of the data are provided in several supporting appendices.

Introduction and Background

The 211b Research Group is an unincorporated group of USA fuel and fuel additive manufacturers affiliated by contractual obligation to meet the testing requirements of Section 211(b) (2) and 211(e) of Clean Air Act. The American Petroleum Institute (API) manages the required work on behalf of the 211b Research Group.

Mobile s ource a ir t oxics (MSAT) may pose a n adverse health risk, esp ecially in microenvironments with high exposures to vehicle exhaust or evaporative emissions. Although programs such as reformulated gasoline (RFG) are inten ded to reduce the emissions of MSAT and ozone precursors , uncertainties remain regarding population exposures associated with both
oxygenate -gasoline blends and conventional gasoline. Accordingly, the EPA issued requirements for a test program in accordance with the Alternative Tier 2 provisions of the fuels and fuel additives (F/FA) regulations, which are required pursuant to Section 211 of the Clean Air Act. To satisfy those testing requirements, API contracted with a research team consisting of the Desert Research Institute (DRI), Southwest Research Institute (SwRI), Lovelace Respiratory

Research Ins titute (LRRI), and TRJ Environmental, Inc (TRJ) to conduct a study of the high-end distribution of inhalation exposures to evaporative and combustion emissions of conventional and oxygenated- gasoline (MTBE -gasoline, and ethanol-gasoline).

The results of this study provide data that will allow estimation of the upper-end of the frequency of annual average inhalation exposures to evaporative and combustion emissions of gasoline and oxygenated-gasoline. EPA may accomplish this by using the scripted exposures in high -end microenvironments with EPA regulatory exposure models, such as the Hazardous Air Pollutant Exposure Model (HAPEM). HAPEM is a screening-level exposure model for assessing average long -term inhalation exposure of the general population, or speci fic sub -populations, over spatial scales ranging from urban to national. The information from this study will permit sensitivity analyses to determine the range of these exposures, especially during heavy traffic, in residential and public parking garages and during refueling. The study also provides data for determining the relative proportion of evaporative versus combustion emissions in higher exposure microenvironments.

The specific objectives of the study are to provide information allowing EPA to:

**•** Quantify personal exposures to motor vehicle gasoline evaporative and combustion

emissions in microenvironments ( MEs ) representing the upper end of the population exposure frequency distribution (99 th 

### + percentile) of such exposures;

### ES -2 **•** Determine quantitativ e relationships between personal exposures in selected MEs and fixed site measurements in these MEs and at nearby air monitoring stations;

**•** Determine how personal exposures differ among cities and seasons in which methyl t

butyl ether ( MTBE )- and ethanol ( EtOH )- gasolines are used compared with a city where oxygenated fuels are not used.;

**•** Extrapolate study data to other cities and other oxygenated fuels;

**•** Apportion the relative contributions of vehicle fuel combustion versus evaporative emissions to personal exposures in high-end MEs;

**•** Determine the relationship between vehicle tailpipe and evaporative emissions and exposure levels in a trailing vehicle cabin and in a residence with an attached garage

.

Experimental Methods and Approach

The study was condu cted in several phases . First, DRI evaluate d the suitability of available measurement methods for meeting the technical objectives of the study. These methods included continuous and time-integrated measurements of carbon monoxide (CO), total volatile organic compounds (VOC), and the following MSAT species : benzene, toluene, ethylbenzene and xylenes (BTEX), 1,3-butadiene (1,3- BD) , methyl tertiary butyl ether (MTBE), formaldehyde and acetaldehyde

. Exposure measurements included well

- established time

- integrat ed methods for measurements of hydrocarbons and carbonyl compounds. These samples provide data of known precision and accuracy for each chemical species of interest during each exposuremeasurement, which typically covered a 20 to 40 min period. Several continuous and semicontinuous methods were used to provide time-resolved data ranging from 1 to 10 minutes. Continuous exposure measurements included benzene, toluene, ethylbenzene, and xylenes (BTEX) by a portable mass spectrometer (MS), carbon monoxide (C O) by a portable electrochemical analyzer and by a nondispersive infrared (NDIR) analyzer, and estimates of total volatile organic compounds by a portable photoionization detector (PID). Semi-continuous measurements of BTEX were also obtained from analysis of solid phase microextraction (SPME)

fibers.

Because exposure levels in most microenvironments were expected to vary with time, the measurement protocol included continuous measurements of target species wi th time resolution

of 1 minute or less. This r equirement necessitated the use of instruments such as the Kore MS200 and the Alpha Omega formaldehyde analyzer, which have not previously been proven for such application and did not perform sufficiently well in field conditions during the pilot studies. Furthermore, there are no acceptable continuous methods for 1,3-butadiene, MTBE, ethanol, acetaldehyde or nonmethane hydrocarbons (NMHC) that could be used in portable modes of operation with adequate sensitivity. Therefore, our sampling strategy consists of a

three -tier approach shown in Table E-1, which lists the overlapping measurement methods used in the Section 211(B) Tier 2 High-End Exposure Screening Study and their intended application.

### ES -3 Table E

- 1. Measurement methods used in the Section 211(B) Tier 2 High

- End Exposure Screening Study. Data applications for specific methods are classified as reference, confirmatory, and surrogate.

Continuous Semi

- Cont Integrated

Method T15 CO NDIR CO ppbRAE MS200 HCHO SPME Canister DNPH Adsorbent

Applicable Environments outdoor and

in

- cabin all outdoor and

in

- cabin higher end

MEs outdoor A ll all all all

Time Resolution 1 min seconds seconds 1 min 1 min 10 min 20

- 40&5 min 20

- 40 min 20

- 40 min

Detection Limits 0.1 ppm 0.04 ppm 1 ppb 1

- 3 ppbv 1 ppbv 0.2 ppbv 0.05 ppbC 0.1 ppbv 0.2 ppbv

Data Application S 1 S S C C C R R R

CO SC SC R

PID 2 SC

BTEX S (a) S (a) SC (c) C C R

1,3

- Butadiene S (a) S (a) S (c) R

MTBE S (a) S (a) S (c) C R
Formaldehyde S (b) S (b) S (d) C R
Acetaldehye S (b) S (b) S (d) R

Ethanol S (e) S (e) S (f) R

NMHC S (a) S (a) S (c) R

1. Category of data application include surrogate (S), confirmatory (C) reference (R), and surrogate compounds or signal (SC ) 2. Sum of molecules ionizable at 10.6 eV and detected by photoionization detector. S (a). Time series will be reconstructed from the canister/CO ratio for exhaust

- dominated samples. S (b). Time series will be reconstructed from the DNPH/CO ratio for exhaust

- dominated samples except outdoor daytime samples. S (c). Time series will be reconstructed from the canister/PID ratio for exhaust

- or evap

- dominated samples in outdoor MEs. S (d). Time series will be reconstructed from the DNPH/PID ratio fo r exhaust

- dominated samples except outdoor daytime samples. S (e). Time series will be reconstructed from the solid adsorbent/CO ratio for exhaust

- dominated samples. S (f). Time series will be reconstructed from the solid adsorbent/PID ratio for exhaus t and evap

- dominated samples.

### ES -4 The measurements are classified in one of three tiers: reference, surrogate, and confirmatory. The base set or “reference” (R) measurements consist of three well

- established

time

- integrated measurements. These include: canister sampling and analysis by gas chromatography with flame ionization detection for CO, BTEX, 1,3-butadiene, MTBE, and nonmethane hydrocarbons (NMHC); 2,4-dinitrophenylhydrazine (DNPH) cartridge sampling and analysis by high performance liquid chromatography with UV detection for formaldehyde and acetaldehyde; and solid adsorbent sampling and analysis of ethanol by gas chromatography with mass spectrometry. These three methods combined measure all species of interest over the entire sampling period within each microenvironment. Although these integrated methods do not characterize peak exposures in microenvironments with highly varying exposure levels, they serve several other purposes. They provide a basis for validating continuous and semi-continuous

dat a. They also provide a basis for deriving correlations between the time- integrated values with time averages of continuous data from the CO and PID instruments. Thus the continuous data were used as “surrogates” (S) for reconstructing the time series of specific MSAT based on these correlations. For example, data for BTEX, 1,3-butadiene

, and MTBE from the canister

measurements were correlated to continuous CO and PID data to reconstruct their time series in

exhaust -dominated environments. In a similar manne r, the time series of formaldehyde was reconstructed from the correlation of the integrated DNPH samples with CO. Outdoor afternoon samples were excluded due to potential contributions of carbonyl compounds formed from atmospheric reactions of hydrocarbons . Table E -1 shows other correlations that can be used in

this manner. Two pilot stud ies were conducted in Reno, NV to test the proposed measurement methods under field conditions and to refine the exposure protocols. T wo experimental approaches were used i n the main study.

Controlled Exposure Measurements in San Antonio

First, DRI and SwRI conducted exposure measurements in San Antonio under controlled conditions to establish quantitative relationships between vehicle tailpipe and evaporative

emissions a nd exposure levels in two specific microenvironments, a trailing vehicle cabin and in a residence with an attached garage. The two vehicles (2.2L 4 -cylinder 1993 Toyota Camry and a 5.0L V8 1995 Ford F150 Pickup truck) used in these controlled exposure expe riments were tested at the SwRI laboratory for FTP (Federal Test Procedure) exhaust and hot soak evaporative emissions (Merritt, 2005). The tests were performed with the vehicles in normal and in malfunction condition while operating on summer and winter grade fuels from Houston, Atlanta and Chicago in summer 2002 and winter 2005. Measured FTP exhaust NMHC emission rates for the sedan and truck averaged 0.21 and 0.31 g/mi, respectively, in normal mode. Both emission

rates are below the certified emission st andards. The induced malfunctions raised NMHC emission rates by a factor of 16.7 for the sedan to 3.58 g/mi and factor of 7.0 for the truck to 2.20 g/mi. Differences in NMHC emission rates among the three regional fuels were not significant. The p values of the regression between Atlanta and Houston and Atlanta and Chicago fuels were 0.07 and 0.08, respectively for normal mode and 0.01 and 0.04, respectively for malfunction mode. The percent relative standard deviations of the NMHC emission rates for the sedan and truck were 15% and 14%, respectively, in normal mode and 3% and 6%, respectively with the

induced malfunctions.

The two test vehicles in normal operation and with induced malfunction were used to determine exposure in a cabin of a third vehicle w hich trailed the test vehicle. During each test, the trailing vehicle was driven behind the test vehicle over a travel loop of several miles in a

### ES -5 rural area south of San Antonio. Measurements were made during the first 10 minutes without

the test vehicle i n order to established background exposure levels. Each trailing vehicle run

included three scenarios ( based on the proximity to the leading vehicle: far, near, and passing) for each low and high speed (30 mph and 60 mph) according to a prescribed schedule. Separate integrated samples were collected for background and separate periods corresponding to the driving and idle portions of each test for each fuel (i.e., Atlanta, Houston and Chicago) and emission condition (i.e., normal and malfunction mode). Data from the integrated reference

methods show ed observable relationships between exhaust emission rates and in-cabin exposures in a trailing vehicle.

The same two test vehicles (with and without malfunctions) were used to determine indoor exposure in a home with an attached residential garage. The vehicles were parked in a closed garage also containing a gasoline powered lawnmower and gasoline storage container filled with the test fuels, with in -garage and adjacent room monitoring conducted before, during and after the vehicle cool-down period. Time- integrated canister and cartridge samples were collected for each test (one in the garage and one in the adjacent room). A set of continuous and

semi -continuous measurements by serial 10 minute average s olid phas e micro

- extraction ( SPME ) sampling were made during test period of two hours.

Personal Exposures in Houston, Chicago and Atlanta

In the second approach, DRI measured personal exposures in selected MEs representing the upper end of the frequency distribution of potential population exposures. The study wasconducted in Houston, TX, Chicago, IL and Atlanta, GA where MTBE-gasoline, ethanolgasoline and conventional gasoline are used, respectively. These cities also satisfy additional requirements of the stu dy for ongoing ambient air monitoring programs and geographic and climatologic diversity among the three cities. Sampling was performed during winter and summer and under conditions that were conducive to higher exposures within each ME (e.g., downwind, low wind speeds, rush hour traffic). Continuous measurements included both NDIR and electrochemical CO, two PIDs and in -cabin and fuel tank skin temperature. From 3 to 5

time

- integrated canister and DNPH cartridge samples were collected for the following twe lve microenvironments;

**•** ME1 -cabin exposure in congested freeway during commute,

**•** ME2 -cabin exposure in urban canyon,

**•** ME3 -cabin exposure during refueling,

**•** ME4 -cabin exposure in underground garage,

**•** ME5 -cabin exposure at toll plaza,

**•** ME6 - cabin exposure i n on -road tunnel (Houston and Chicago only),

**•** ME7 -outside exposure during refueling,

**•** ME8 -outdoor exposure at busy street,

**•** ME9 -outdoor exposure at bus stop,

**•** ME10 -outdoor exposure at surface parking lot during and after event,

**•** ME11 -outside exposure in underground garage, 12-outdoor exposure at toll plaza,

**•** ME13 -cabin exposure following a high emitter (Atlanta only)

### ES -6 In addition, 5- minute integrated canister samples were collected for ME 6, ME7, ME10, and

ME 13 during peak exposures that corresponded to collection of breath samples.

Exposure Protocol and Study Plan, and Study Schedule

The Exposure Protocol and Study Plan was developed and refined based upon results of the pilot studies and initial field measurements during summer 2002. The following chronology describes the main stages in the study and development of the Study Plan.

**•** First Pilot Study.

**•** Prior to the main field studies, DRI and LRRI conducted a 5-day pilot study in Reno, NV, during February 2002 to test alternative measurement approaches under field conditions similar to those that were encountered in the main study (Zielinska et al., 2002c). DRI and LRRI also evaluate d the stability of the designated VOC species in breath and urine samples. Based upon the result of this pilot study, the exposure protocols and measurement methods, sampling and analytical procedures were refined and proposed in the June 13, 2002 Exposure Protocol and Study Plan (Zielinska et al., 2002a).

Summer 2002 Field Studies.

**•** The field measurements in San Antonio, Houston

, and Atlanta were completed in adherence to the June 2002 protocol during summer 2002. These data were presented in three separate reports: Interim Data Report (Zielinska et al., 2002b), Summer 2002 Atlanta Field Study Report (Zielinska et al., 2003a) and Summer 2002 San Antonio and Houston Field Study Report (Zielinska et al., 2004a). The work in Chicago in the summer of 2002 was postponed, pending further evaluation of the measurement protocol and assessment of the data collected in 2002.

Second Pilot S tudy.

**•** The final version of the protocol was applied to the summer 2003 and winter 2004/5 field study in Atlanta, Chicago and Houston and in the winter 2005 in San Antonio. A d ata report was previously prepared for the summer 2003 field study in Atlanta and Chicago (Zielinska et al. 2004b). The second pilot study in Reno was conducted to refine the exposure protocol and further evaluate the surrogate approach and SPME measurements (Zielinska et al., 2003c). Several improvements were implemented in the mobile sampling platform during this time. Additional changes were incorporated into the final version of Exposure Protocol and Study Plan (Zielinska et al., 2003d) based upon discussions between EPA and DRI on the results of these reports. The final study protocol approved by the U.S.

EPA is included in the Appendix A of this Final Report.

API Section 211(B) Tier-2 Exposure Database

The data have been organized into four data files (API Data_Continuous.xls, API Data_SPME.xls, API Data_Time -integrated.xls and API Data_Reconstructed.xls) containing the continuous, SPME, time- integrated and reconstructed exposure data. All files include data fields describing the sample collection conditions (e.g.; microenvironment, fuel type, test mode) as well as data flags ind icating problems with the analytical or sample collection methods. Tables

### ES -7 explaining the meaning of each data field are also included with each file. The files are supplied in Excel workbook format for convenience, but have been formatted to be compatible with common database software (the value -99 is used for missing data points, and time is in hhmm text format)

The time

- integrated data contains speciation results from canister, DNPH cartridge, and

TENAX adsorbe nt tubes, plus time -averaged values of pollutants and environmental parametersthat were measured continuously during the batch sample collection periods. Within the timeintegrated data file there are 4 sub

- categories that are presented separately due to the differing number of experimental variables for each type: 1) microenvironment exposure measurements from the three cities, 2) breath samples collected from subjects participating in 4 of the microenvironments, 3) residence with attached garage, and 4) trailing vehicle exposure tests.

The SPME data is assembled in essentially the same manner as the time

- integrated data, but contains only the BTEX hydrocarbon compounds and uses some different sample descriptors where necessary to identify which portion of each test the sample was collected . The same sample IDs are used to facilitate comparison of the two sampling methods.

The third data file contains 1-minute averages of the pollutants and environmental parameters that were measured continuously during the microenvironment exposure tests in the 3 cities. Data were typically logged every 10 seconds during testing, but to reduce measurement noise, make the data set more manageable, and reduce the effect of minor timing discrepancies between instruments due to imperfect clock synchronization or diff erences in sample line residence time, the data was time averaged by minute. Each data record in this file has both a time/date stamp and an identification code that relates it to the corresponding time

- integrated sample. Data flags are given to identify a ny missing or invalid data for each minute. Due to the large size of this file, the various sample descriptors have not been included but these can be derived from the identification code as described in the included key.

The fourth data file contains 1 -min reconstructed data for benzene, 1,3-butadiane and formaldehyde based on PID and NDIR CO continuous data, as described in Chapter 1 of this report. Both full time integrated canister and DNPH

- carbonyl samples and 5

- min canister samples collected over a peak exposure in selected MEs

, are included.

Study Findings

Quantification of Personal Exposures to Motor Vehicle Emissions in High Exposure Microenvironments in Atlanta, Houston and Chicago during Summer and Winter (Chapter 1)

**•** Since different fuels were used in each of the tree cities, only combined effect of city/fuel was examined in this study.

**•** Day

- to -day variations in high- end (99 th 

### + percentile) benzene, 1,3-butadiene, formaldehyde, and CO concentrations in different MEs were substantial and independent of city and season, probably related to the activity and emission rates of sources in the given MEs which differ from day to day.

### ES -8 **•** With the exception of refueling, exposure levels were generally lower in outdoor MEs and higher in enclosed MEs.

**•** The 2 0- min average exposures to benzene during refueling ranged up to few hundred ppbv and showed substantial day- to

- day variability.

**•** In -cabin exposures during on- road vehicle operation were less variable than in

- cabin exposures in garages and toll plazas.

**•** Exp osure levels of BTEX species were highest in refueling MEs, which are dominated by evaporative emissions whereas exposures to CO, formaldehyde, and 1,3- butadiene were highest in cold- start dominated MEs.

**•** BTEX and 1,3- butadiene measured by the time

- integrat ed canister method correlated well with continuous PID and CO measurements, respectively, in all MEs except refueling. Correlation of formaldehyde with continuous CO was weak, probably due to photochemical production of this compound.

**•** Continuous PID and CO (NDIR) data can be used to reconstruct 1

- minute time series for benzene and 1,3-BD, respectively, provided that the averaged continuous measurements are above the detection limits of the instruments (25 ppbv and 0.5 ppmv, respectively).

CO data can also be used to reconstruct 1 -minute formaldehyde data; however, less reliably so due to poorer correlation between these species.

**•** Reconstructed 1

- minute time

- series data for benzene and 1,3

- butadiene, averaged over five minutes, correlated well with the corresp onding 5- minute canister samples after excluding the Houston refueling ME data, which were distorted by high concentrations of

MTBE.

**•** The concentrations of benzene and 1,3-butadiene measured in post peak exposure breath samples closely tracked the correspo nding microenvironmental 1- minute maximum reconstructed surrogate values.

**•** Increases in concentrations of measured species occur in all breath samples that were collected within a minute of a peak exposure. In Atlanta and Chicago, the highest breath

concent rations of BTEX and 1,3-BD were observed in ME7 (refueling) and ME11 (underground garage), respectively. In Houston, high concentrations of MTBE were

measured in ME7.

Figure E -1 shows the distribution of reconstructed 1- min BTEX concentr ation s in high- end MEs

in Atlanta in Summer . One- min time resolution reflects the high short

- time peak concentrations necessary to characterize 99 th 

### + percentile exposure. The Atlanta winter distribution as well as Houston and Chicago MEs look very similar.

Figure E

- 2 A an d B shows the comparison of 1,3-butadiane, benzene, formaldehyde and CO averaged concentrations in three cities in Summer and Winter, respectively.

### ES -9 Figure E -1. Distribution of reconstructed 1-min BTEX exposures in high-end At lanta MEs. Edg es of the box = first and third quartiles; black line = median; red line = average. Minimum and maximum values (ppbv) are shown at the bottom and top of the plots. Whisker
covers 99.3% of the data distribution. Filled circles > 3 times the b ox interval, empty circle are within that interval. The y

- ax is r epresents the percentage of data distribution. 2.4 132

9.2 14.2

1.4 65

10.1

9.8

1.3 583

18. 0 40.0

3.1 304

17.5 25.8

0.6 25

3.7 7.3

2.2 2454

13.3 97.6

0.8 58

5.1 5.8

2.6 80

7.0 9.4

2.1 98

14.1 24.3

60.1 465

152.4 172.1

5.8 40

11.7 13. 3

2. 9 533

11.9 29.7 

### ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME8_9 ME10 ME11 ME12 ME13

0 20 40 60 80 100 120

2.4 132

9.2 14.2

1.4 65

10.1

9.8

1.3 583

18. 0 40.0

3.1 304

17.5 25.8

0.6 25

3.7 7.3

2.2 2454

13.3 97.6

0.8 58

5.1 5.8

2.6 80

7.0 9.4

2.1 98

14.1 24.3

60.1 465

152.4 172.1

5.8 40

11.7 13. 3

2. 9 533

11.9 29.7 

### ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME8_9 ME10 ME11 ME12 ME13

0 20 40 60 80 100 120

2.4 132

9.2 14.2

1.4 65

10.1

9.8

1.3 583

18. 0 40.0

3.1 304

17.5 25.8

0.6 25

3.7 7.3

2.2 2454

13.3 97.6

0.8 58

5.1 5.8

2.6 80

7.0 9.4

2.1 98

14.1 24.3

60.1 465

152.4 172.1

5.8 40

11.7 13. 3

2. 9 533

11.9 29.7 

### ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME8_9 ME10 ME11 ME12 ME13

0 20 40 60 80 100 120

1. In-Cabin Congested Freeway 5. In-Cabin Toll Plaza 10. Outdoor Surface Parking 2. In-Cabin Urban Canyon 7. Outdoor Refueling 11. Outdoor Underground Garage 3. In-Cabin Refueling 8. Sidewalk 12. Outdoor Toll Plaza 4. In-Cabin Underground Garage 9. Sidewalk/Bus Stop 13. Following High Emitters

### ES -10 Benzene

0 20 40 60 80 100 120 140

1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Houston Atlanta Chicago 1,3-Butadiene

0 2 4 6 8 10

1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Houston Atlanta Chicago

Formaldehyde

0 5 10 15 20 25 30 35

1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Houston Atlanta Chicago CO

0 2 4 6 8 10 12 14 16

1 2 3 4 5 6 7 8 9 10 11 12 13

MEppm

Houston Atlanta Chicago



### Figure E -2A. Comparison of average concentrations of benzene, 1,3-BD, HCHO and CO in three c ities in Summer

### ES -11 Benzene

0 10 20 30 40 50 60

1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Houston Atlanta Chicago 1,3-Butadiene

0 2 4 6 8 10 12

1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Houston Atlanta Chicago

Formaldehyde

0 5 10 15 20 25

1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Houston Atlanta Chicago CO

0 5 10 15 20

1 2 3 4 5 6 7 8 9 10 11 12 13

MEppm

Houston Atlanta Chicago



### Figure E

- 2B. Comparison of average concentrations of benzene, 1,3- BD, HCHO and CO in three cities in Winter

### ES -12 Relative Contributions of Vehicle Evaporative and Exhaust Emissions to Concentrations of Volatile Air Toxics in High Exposure Microenvironments (Chapter 2)

**•** MTBE/benzene ratios were used to estimate the relative contributions of evaporative and

exhaust emissions to MSAT . This basis for this approach is that the proportion of MTBE in exhaust is reduced during combustion relative to its proportion in the fuel while benzene is enriched in exhaust relative to its proportion in the fuel due to toluene and xylene dealkylation. Consequently, MTBE to benzene ratios are substantially lower in exhaust than in liquid fuel or headspace vapors. Exposures at the two refueling MEs (3 & 7) were dominated by evaporative emissions as expected, with MTBE/benzene ratios in

Houston of 20 to 30. Ratios for all other MEs were between 1 and 4.

**•** The fractional contribution of evaporative and exhaust emission were estimated fo r each ME based on exhaust MTBE/benzene ratios from several dynamometer exhaust tests and on-road tunnel measurements and evaporative MTBE/benzene ratios for the SwRI SHED tests and composition of gasoline headspace vapor. Exposures during refueling (ME3, ME7) are 100% due to evaporative emissions within the uncertainties associated with the measurements and method. All other MEs are dominated by tailpipe emissions with fractional evaporative contributions < 10%.

Figure E -3 shows the MTBE/benzene ratio and contribution of evaporative emissions in Houston

MEs

Quantitative Relationships Between Levels of Volatile Air Toxics and Carbon Monoxide Measured in High -End Exposure Microenvironments and at Nearby Air Quality Monitoring Stations (Chapter 3)

**•** MEs in c lose proximity to running vehicle engines have enhanced CO relative to ambient

levels at nearby air quality monitoring sites with enrichment ratios approaching 40 where ventilation is limited, as in underground garages. Average in- cabin CO/ambient ratios i n congested freeway traffic range from 2 -9. ME locations less proximate to operating vehicles, such as gas stations and urban sidewalks, have CO/ambient ratios of 0.5-2.

**•** The mean ratio of in -vehicle exposures on congested freeways (ME #1) to ambient leve ls at a monitoring station of 9.8 ± 3.8 ratio for Houston exceed the HAPEM5 median proximity factor of 4.9 (triangular distribution mode:range 1.9:0-14.3) and HAPEM4 proximity factor of 6.9 for this ME (Rosenbaum, 2005; Long & Johnson, 2004), although by less than expected.

Figure E -4 shows the mean ratios of ME concentrations to corresponding hourly measurements at the regional air monitoring station in Houston.

### ES -13 Figure E -3. MTBE/benzene ratio and contribution of evaporative emissions in Houston MEs Evaporative Emissions Contribution

0.0 0.2 0.4 0.6 0.8 1.0

1 2 3 4 5 6 7 8 9 10 11 12

MEFraction summer

winter MTBE/benzene

0 20 40 60 80

1 2 3 4 5 6 7 8 9 10 11 12

MERatio summer

winter

1. In-vehicle congested freeway 5. In-vehicle toll plaza 9. Outdoor bus stop
2. In-vehicle urban canyon 6. In-vehicle road tunnel 10. Outdoor surface parking
3. In-vehicle refueling 7. Outdoor refueling 11. Outdoor underground garage
4. In-vehicle underground garage 8. Outdoor sidewalk 12. Outdoor toll plaza

### ES -14 Figure E -4. Mean ratios of ME concentrations to corresponding hourly measurements at the regional air monitoring station in Houston. Houston- Summer

1 10 100 1000 10000

1 2 3 4 5 6 7 8 9 10 11 12

MicroenvironmentME/Station Ratio 

### Benzene

Toluene

m&p-Xylenes Houston - Winter

1 10 100 1000 10000

1 2 3 4 5 6 7 8 9 10 11 12

MicroenvironmentME/Station Ratio

### ES -15 Relationship of Attached Garage and Home Exposures to Fuel Type and Emission Levels of Garaged Sources (Chapter 4)

**•** Two target components, formaldehyde and ethanol, had high kitchen background values indicating indoor sources of these compounds. Average kitchen formaldehyde levels were higher in summer than winter, probably due to enhanced off -gassing of building materials and/or penetration of ambient photochemical formaldehyde.

**•** Kitchen BTEX, MTBE and CO species are higher in winter than summer. The exception

is toluene which shows a minimal difference that actually averages higher in summer for normal mode vehicles. This is consistent with indoor toluene emissions from paints, adhesives, cleaning, and personal care products.

**•** MTBE and ethanol are highest for fuels containing those species, as anticipated.

**•** FTP exhaust and SHED evaporative emissions were tested for each vehicle, fuel, and emissions mode, and compared to observed levels in the garage. Neither canister nor SPME samples show strong (r 2 

### =0.003 and 0.005, respectively ) correlations with hot soak emissions, although cold-stabilized FTP Bag 2 benzene appears reasonably correlated (r 2 

### = 0.4) to the cold- start SPME.

**•** Correlations of kitchen levels with garage concentrations were weak (r 2 

### generally bel ow 0.1) and could not be used to predict kitchen exp osures from garage levels.

Figure E

- 5 shows the effect of fuel and vehicle operational mode (i.e. normal or malfunction) on observed concentrations of 1,3-butadie ne, BTEX, MTBE, formaldehyde, ethanol , acetaldehyde,

and CO in the kitchen.

Effect of Ventil ation, Proxi mity, and Emission Levels on In -Cabin Exposures of Trailing Vehicle (Chapter 5)

**•** Summer and winter in

- cabin values were similar in magnitude with the exception of formaldehyde which was higher in the summer, possibly due to higher photochemical activity and higher temperatures that led to more off -gassing of formaldehyde in the

vehicle cabin interior.

**•** Trailing vehicle cabin values were larger than background values (as measured during the first 10 min run without the test vehicle) except for formaldehyde which was actually lower than background in winter tests.

**•** Idle test sample values were on average twice those encountered in driving tests, suggesting that proximity and proximity duration may substantially impact in

- cabin trailing vehicle conc entrations.

### ES -16 **•** Average in

- cabin levels were affected by both state of maintenance of the vehicle and fuel composition. Use of Atlanta fuel resulted in higher BTEX concentrations in the trailing vehicle cabin, which is consistent with higher aromatic contents of Atlanta fuel, especially in summer. Similarly BTEX concentrations were consistently higher during the summer, which is also in concert with higher aromatic contents of summer fuels, especially for Atlanta . Averaging over the fuels and vehicles, the hig h emitter mode resulted in 2.2 times higher in -cabin exposure levels for the trailing vehicle than the normal emitter mode except for HCHO which was relatively unchanged from background.

**•** Trailing vehicle ventilation status affected in -cabin values; the co ncentrations observed by continuous PID and CO monitors were more variable under high ventilation. This may be rationalized as the vehicle moving into and out of the exhaust plume of the leading

vehicle with in -cabin values changing rapidly under high ventilation; whereas under low ventilation, in

- cabin concentrations trapped as the vents were closed stayed relatively constant during the remainder of low ventilation conditions.

**•** Trailing vehicle tests indicated that the largest impact on in

- cabin values came from the emissions mode (normal or malfunction) of the leading vehicle.

Table E -2 shows the effects of changing vehicle, fuel and operational mode (i.e. normal or malfunction) on observed concentrations of 1,3-butadiene, BTEX, MTBE, formaldehyde, acetaldehyde, and CO in the trailing vehicle cabin.

### ES -17 0 5 10 15 20 25 30 35 40 45 50

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO,ppm Formal EtOH Acetal

compoundppbv Atlanta-N

Atlanta-F

Houston-N

Houston-F

Chicago-N

Chicago-F 339,542



### Figure E -5. The effect of fuel and vehicle operation mode (i.e. normal or malfunction) on

observed concentrations in the kitchen

Table E -2. The effects of changing vehicle, fuel and operational mode (i.e. normal or malfunction) on observed concentrations in the trailing vehicle cabin.

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO, ppm Formal Acetal Truck only (n=12) 0.64 1.40 2.32 0.45 1.46 0.61 0.87 1.56 4.55 3.67 Car only (n=12) 0.59 1.13 1.87 0.33 1.11 0.45 0.53 1.42 5.90 3.59 Atl fuel only (n=8) 0.53 1.44 2.79 0.51 1.66 0.68 0.14 1.41 5.99 3.39 Hou fuel only (n=8) 0.89 1.52 2.20 0.48 1.58 0.66 2.17 1.91 5.61 4.37 Chi fuel only (n=8) 0.48 0.87 1.32 0.20 0.66 0.28 0.03 1.22 4.20 3.19 Normal only (n=12) 0.06 0.46 1.05 0.21 0.73 0.31 0.16 0.41 5.21 3.26 High emitter only (n=12) 1.06 1.95 2.99 0.55 1.77 0.71 1.21 2.50 5.37 3.37 St Dev high emitter only 28% 36% 38% 41% 44% 44% 177% 52% 52% 64%

### ES -18 Evaluation of Measurement Method ’s Performance

The integrated canister and DNPH sampling methods produced nearly 100 percent data capture of high quality data as c onfirmed by internal consistency checks. However, some challenges were encountered in applying two continuous confirmatory measurements, the Kore MS200 and formaldehyde analyzers. In most of the MEs, the MS200 had vacuum problems, most probably due to the high humidity in Houston, Chicago and Atlanta, and did not produce useful data. The instrument performed much better during first and second Pilot Study in Reno, probably because of much lower humidity. Although the formaldehyde analyzer was upgrad ed

, it still require d extensive user intervention and did not run reliably under the conditions encountered. The sensitivity of the instrument to environmental noise associated with driving

limit ed its utility under mobile sampling . With proper operation and bet ter characterization of instrument performance, the supplemental continuous formaldehyde analyzer may prove useful

for ambient monitoring a t fixed location

. The SPME also had excellent data capture, as did the continuous instruments for CO and

PID. The tw o PIDs were compared both in controlled tests and collocated during the MEs. In both cases, they tracked each other quite well. Differences appear to be due to an offset in one unit, and a slightly different response speed between the two units. The NDIR C O and electrochemical CO (Langan T15 ) instruments compared favorably, usually within 1 ppm. The detailed description of data quality and QA/QC procedures are presented in Appendix H.

Conclusions

Exposure levels are directly related to the activity and e mission rates of sources in the microenvironment and inversely related to the distance between sources of emissions and the measurement location and extent of dilution of emissions, which are a function of meteorological conditions and the presence of physical obstruction that inhibit dispersion. All of these factors

contribute to the large temporal and spatial variations in pollutant exposures that exist within

each of the microenvironments. Testing at SwRI showed that the differences in exhaust and

evapor ative emission rates among the three regional fuels were not statistically significant except for MTBE. With the exception of MTBE, the small differences due to fuel formulation are masked by the large variations of exposure levels within each of the microenvironments.

The information from control exposure experiments in San Antonio provided useful context for interpreting the varying exposures in the high-end microenvironments in Atlanta, Houston and Chicago. We found that the results of the trailing vehi cle experiments were qualitatively consistent with our observations in the three cities . In-cabin exposure levels even in congested traffic were on the order of a factor of two higher than background. Congested stopand -go conditions result ed in some increase in exposure levels due to shorter gaps between vehicles and highest on-road exposures were measured when following high emitters. In-cabin exposures during low ventilation conditions were relatively constant and retained the levels at

the time ventilat ion wa s cut off.

Evaporative emissions were the only substantial components of high-end ME exposures during vehicle refueling operations, where they are dominant. Since refueling MEs had the highest relative levels of these components, they constituted th e peak exposures, although overall the average population time spent in these high end MEs is likely the shortest. The contributions

### ES -19 of evaporative emissions for all other MEs were typically about 5% of the total measured exposures. Results were similar fo r both seasons, although evaporative contributions during refueling were marginally less during summer, possibly due to more rapid dispersion of vapors and evaporation of fuel spilled during each refueling test at higher summer temperatures. These

results suggest that the contemporary Houston vehicle fleet contained relatively few carbureted or leaking vehicles given that evaporative emissions were not a substantial source in the nonrefueling MEs tested. Refueling emissions released from pressurized fuel systems and spilled fuels appeared to be the primary source of peak evaporative exposures. The lack of a seasonal variability in the evaporative contribution was also consistent with this supposition. Although it was not feasible to try to distinguish furth er between liquid and headspace vapor contributions by the method used, the extremely low MTBE/benzene ratios observed for the roadway, sidewalk, and parking MEs strongly suggest that the impact from leaking liquid gasoline emissions were

minor.

HAPEM5 pr oximity factors may need to be adjusted since they were based on a 1998 scoping study where measurements ‘highlighted trailing behind heavy duty diesel vehicles and diesel city buses when possible’. Houston ME/ambient ratio comparisons also generally exceed the other HAPEM factors. Refueling ratios (ME3, ME7) for benzene were higher than the corresponding HAPEM factors as expected

, given the refueling protocol provisions maximizing exposure discussed above and below. Concentrations of exhaust compounds such as CO and 1,3-

butadiene were enhanced under reduced ventilation situations.

It must be recognized that the various microenvironments were selected with a goal to capture the 99th percentile exposure levels within each type of microenvironment, as prescribed by EPA and API. We also selected specific sampling times and locations with the greatest potential for higher exposures. These selections were based on considerations of various emission surrogates such as traffic counts, diurnal variations in average highway speeds, length of queues at toll plazas, number of cars refueling or entering and exiting parking garages. Surrogates of dispersion included wind roses and diurnal variations in temperature. Measurements in microenvironments with unrestricted dispe rsion were made in the early morning or evening during calm conditions and minimal vertical mixing. In moderate wind conditions, we drove parallel to the prevailing wind to reduce the impact of cross winds. Thus, the ranges of exposures determined in this study are skewed toward the higher end of the distribution of exposures for each microenvironment.

References

Long, T. and T. Johnson (2004). Development of Penetration and Proximity Microenvironment Factor Distributions for the HAPEM5 in Support of the 1999 National- Scale Air Toxics Assessment (NATA). Memorandum prepared by TRJ Environmental, Inc. for the U.S. Environmental Protection Agency, Research Triangle Park, NC, April 5, 2004

Merritt, P. (2005). Evaporative and Tailpipe Emissions Support for S211b Tier 2 Exposure Study. Final report submitted by Southwest Research Institute to Desert Research Institute on July 29, 2005.

### ES -20 Rosenbaum, A. (2005). The HAPEM5 User’s Guide. Report prepared by ICF Consulting for the U.S. Environmental Protection Agency, Research Triangle Park, NC, March 2005.

Zielinska, B., E. M. Fujita, J.C. Sagebiel, D. E. Campbell, L.R. Smith, T. Johnson (2002a). Exposure Protocol and Study Plan for the Section 211 (B) Tier 2 High End Exposure Screening Study of Baseline and Oxygenated Gasoline. Prepared for American Petroleum Institute, 1220 L Street, Washington, DC 20005-4007. June 13, 2002

Zielinska, B., E. M. Fujita, J. C. Sagebiel, D. E. Campbell, J. McDonald (2002b). Interim Data Report for Section 211 (B) Tier 2 High-End Expos ure Screening Study of Baseline and Oxygenated Gasoline. Prepared for American Petroleum Institute, 1220 L Street, Washington, DC 20005-4007. November 15, 2002.

Zielinska, B, J. Sagebiel, E. Fujita, D. Campbell, J. McDonald, T.J. Kelly, and D. W. Joseph (2 002c). Section 211(B) Tier 2 High-End Exposure Screening Study of Baseline and Oxygenated Gasoline- Pilot Study. Prepared for American Petroleum Institute, 1220 L Street, Washington, DC 20005-4007. June 13, 2002

Zielinska, B, E.M. Fujita, and J.C. Sagebiel (2003a). Section 211 (B) Tier 2 High End Exposure Screening Study of Baseline and Oxygenated Gasoline -Summer 2002 Atlanta Field Study

on Baseline Gasoline. Prepared for American Petroleum Institute, 1220 L. Street, Washington, DC 2005-4070. March 13, 2003.

Zielinska, B., J.C. Sagebiel, D. Campbell, D. Ceballos, M. McDaniel, and E.M. Fujita (2003b). Section 211 (B) Tier 2 High End Exposure Screening Study of Baseline and Oxygenated Gasoline-2nd Reno Pilot Study. Prepared for American Petroleum Institute, 122 0 L Street, Washington, DC 20005-4007. June 13, 2003

Zielinska, B., E. M. Fujita, J.C. Sagebiel, D. E. Campbell, L.R. Smith, T. Johnson (2003d). Exposure Protocol and Study Plan for the Section 211 (B) Tier 2 High End Exposure Screening Study of Baseline a nd Oxygenated Gasoline. Prepared for American Petroleum Institute, 1220 L Street, Washington, DC 20005-4007. Final Version. October 1, 2003

Zielinska, B., J.C. Sagebiel, D. Campbell, E.M. Fujita (2004a). Section 211 (B) Tier 2 High End Exposure Screening S tudy if Baseline and Oxygenated Gasoline -Summer 2002 San Antonio and Houston Field Studies. Prepared for American Petroleum Institute, 1220 L. Street, Washington, DC 2005-4070. March 5, 2004.

Zielinska, B., J.C. Sagebiel, D. Campbell, E.M. Fujita (2004b). Section 211 (B) Tier 2 High End Exposure Screening Study if Baseline and Oxygenated Gasoline-Summer 2003 Chicago and Atlanta Field Studies. Prepared for American Petroleum Institute, 1220 L. Street, Washington, DC 2005-4070. July 5, 2004.

### 1

- 1 

## 1. Quantifica tion of Personal Exposures to Motor Vehicle Emissions in High Exposure Microenvironments in Atlanta, Houston
, and Chicago during
Summer and Winter.

1.1 Introduction

Gasoline-powered vehicles emit a portion of ozone-forming volatile organic compounds (VOC) and mobile source air toxics (MSAT) in the urban areas of the country. Elevated exposures to gasoline- related MSAT have been reported in certain microenvironments (MEs)

, such as in vehicle cabin s during commuting on congested roadways (Batterman et al., 2002; Chan et al. 1991; Rodes et al., 1998; Fedoruk and Kerger 2003; Weisel et al. , 1992; Jo and Park, 1999), refueling (Vayghani and Weisel 1999; Vainitalo et al., 1999; Lindstrom and Pliel, 1996) or in urban canyons (Rodes et al., 1998; Chan et al. 1991).

Although oxy genated fuel and reformulated gasoline (RFG) programs are intended to reduce the emissions of ozone precursors and MSAT , uncertainties remain regarding the population exposures associated with oxygenate d and conventional gasoline. According ly, in

2001 EPA issued testing requirements under Alternative Tier 2 provisions of the fuel and fuel additive (F/FA) health effects testing regulations, required pursuant to Section 211(b) of the

Clean Air Act.

The population exposure study reported her e targets conventional gasoline and two oxygenated blends containing methyl tertiary butyl ether ( MTBE ) and ethanol (EtOH) and conducts studies in prospective high-end microenvironments (MEs) likely associated with the most-exposed populations. Personal exposures are quantified in selected MEs representing the upper end of the frequency distribution of potential population exposures. The studies t ake place in cities that have ongoing ambient air monitoring programs

, located in hot and cold parts of the

coun try , using one of the three target fuels. Sampling was performed during winter and summer seasons and under conditions (e.g., downwind, low wind speeds, rush hour traffic, fuel spillage, trailing high emission vehicles ) thought to maximize exposure within each ME

. The same sampling protocols (e.g., location, duration, cabin ventilation) were used in both seasons whenever possible. A number of fuel emission and exhaust components [carbon monoxide (CO), carbon dioxide (CO 2 

### ), benzene, toluene, ethylbenzene, xylenes (BTEX), MTBE, 1,3-butadiene (1,3- BD), EtOH , formaldehyde (HCHO), and acetaldehyde (CH 3 

### CHO)] were measured with in

thirteen MEs in personal breathing zones, and in breath immediately after measured peakexposures. The results of these microenvironmental studies were intended to include the upperend (99+ th 

### percentile) of the frequency of annual average inhalation exposures to evaporative and

combustion emissions from the three targeted gasolines. The study also estimates the relative proportion of evapo rative and combustion emissions by ME in breathing zone air.

### 1

- 2 The specific objectives of the study are to provide information allowing EPA to:

**•** Quantify personal exposures to motor vehicle gasoline evaporative and combustion

emissions in MEs representing the upper end of the population exposure frequency distribution (99+ th 

### centile) of such exposures;

**•** Determine quantitative relationships between personal exposures in selected MEs and fixed site measurements in these MEs and at nearby air monitoring stati ons;

**•** Determine how personal exposures differ across seasons and cities using the three target fuels ( conventional-, MTBE -, and EtOH-gasoline);

**•** Extrapolate study data to other c it i es and other oxygenated fuels; and

**•** Apportion the relative contributions of vehicle fuel combustion vs. evaporative emissions to personal exposures in high-end MEs.

1.2 Experimental

1.2.1 Selection of Microenvironments

Houston (TX), Chicago (IL) and Atlanta (GA) were selected as the study sites. These cities have ongoing ambient monito ring programs and dispense MTBE

- RFG, EtOH

- RFG, and conventional gasoline formulations, respectively. One of the goals of the project was to sample high -end MEs , plausibly characterized in the upper 99+ th 

### percentile of exposure s to exhaust/evaporative emiss ions from gasoline- fueled vehicles. Selection of high -end MEs 1 

### was made in consultation with EPA and independent peer reviewers according to the selection criteria described in the Exposure Protocol and Study Plan (Zielinska et al, 2003a) included in Appen dix A. Table 1.2.1- 1 lists the MEs chosen along with the number of replicate

measurements taken in each ME, whether biomarker (breath ) measurements were taken for that ME, and the sampling time spent in each ME.

1 ME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin underground gar age; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

- cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop;

ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; M E13 : In

- cabin trailing high

- emitter

vehicle

### 1

- 3 Table 1.2.1-1. Microenvironmental Samplin g.

ME # ME Description Replica

tes Biomar

ker SamplingTime (min) **

1 In

- Cabin Congested Freeway 5 40 (20 H and 20 L)

2 In

- Cabin Urban Canyon 3 40 (20 H and 20 L)

3 In

- Cabin Refueling 5 20 (10 H and 10 L)

4 In

- Cabin Underground Garage 5 40 (20 H and 20 L)

5 In

- Cabin Toll Plaza 3 40 (20 H and 20 L)

6* In

- Cabin Roadway Tunnel 5 yes 40 (20 H and 20 L)

7 Out

- of

- Cabin Refueling 5 yes 20

8 Out

- of

- Cabin Sidewalk 3 40

8/9 Out

- of

- Cabin Sidewalk/Bus Stop 3 40

10 Out

- of

- Cabin Surface Parking 3 40

11 O ut

- of

- Cabin Underground Garage 5 yes 40

12 Outdoor Toll Plaza 3 40

13* In

- Cabin Trailing High

- Emitting

Vehicles 5 yes 40 (20 H and 20 L)

*ME6 was sampled in Houston & Chicago and ME13 in Atlanta ** H refers to high ventilation and L to low ventilatio n conditions (see Monitoring Methods below)

The ME number refers to the same type of ME in each city studied. Since ME6 refers to a roadway tunnel and a suitable tunnel was not found in Atlanta, ME13 (following a high emitt ing vehicle) was substituted

.

Prior to selecting specific ME locations, Desert Research Institute (DRI) personnel surveyed potential high-end MEs in each city. The objectives of the se survey s with portable gas analyzers were to determine the suitability of candidate sampling locations with respect to

access , maximal exposure levels , and the variability of these exposures. The s ampling period in

each ME was selected to coincide with maximum activity level (i.e ., emissions and exposure) as described in the Protocol (Appendix A). In the absence of data on the range of actual emission component exposures in various MEs in each city, we considered available surrogate parameters for emission and dispersion to select locations and sampling periods with the greatest potential

for maxim al exposures. These emission surrogates included diurnal traffic counts, variations in highway speeds, length of queues at toll plazas, concurrent numbers of cars refueling , and count

rate s entering and exiting parking garages. Surrogates for dispersion included diurnal wind roses and variations in temperature. Where possible we drove parallel to the prevailing wind direction to reduce the impact of cross winds and sampled downwind of the nearest emission sources. Our sampling strategy also recognized that vehicle exhaust emissions are significantly higher for identified high emitt ing vehicles and all vehicles during cold starts (e.g., at parking lots, underground garages , and service stations) and acceleration s (e.g., at toll plazas , roadway

intersections ). All of these factors are important in understanding the high -end perspective of sampling and the temporal and spatial variations that exist within these high-end MEs.

### 1

- 4 1.2.2 Monitoring Methods

Instrumented Van

. All in -cabin and out- of

- cabin exposure measurements wer e performed with the mobile sampling van, a 1996 Chrysler Minivan, DRI -modified for on-road and stationary sampling. The power system included two banks of rechargeable AGM gel batteries

with minimal H 2 

### out

- gassing during either charge or discharge. Each b ank had a 1750 watt inverter for 110v AC power and direct connections for 12v DC, giving maximum flexibility. The suspension of the vehicle was upgraded to support the additional battery and instrument weight.

Seats were removed and replaced with an adjust able equipment rack s. F or refueling experiments, a second fuel pump was installed to facilitate prompt removal of fuel. In-cabin and exterior temperature and relative humidity sensor s were installed along with an additional sensor

measur ing fuel tank tempe rature. The data acquisition system has eight analog

- to

- digital inputs to record instrument outputs, which includ e a global positioning satellite ( GPS ) sensor, and

c ompile s spatially

- located data into a single database. All in

- cabin equipment was manifold ed to sample from a point in the driver's breathing zone. This manifold inlet could also be extended outside for stationary sampling purposes (e.g., into the subject breathing zone during refueling tests) . Infiltration of outside air was adjusted by opening or closing windows in the front and rear of the cabin and switching the heating/AC system from vent to recirculate. In this manner two ventilation modes, high (all open) and low (all closed), were included in all in- cabin tests.

Equipment Cart. For sidewalk, bus stop and outdoor toll plaza tests, sampling equipment was placed on a cart that was pushed along the sidewalk of a busy street in an urban canyon (ME8), patrolled a bus stop sidewalk at a high traffic density intersection (ME9) or was stationed next to a toll booth during rush hour traffic (ME12). Sampling inlets were positioned in the subject breathing zone. Detailed protocols for sampling in each ME are described in the Exposure Protocol and Study Plan (Zielinska et al, 2003a), included in Appendix A. Measurements in each ME were repeated three to five times for each city

- season as noted in

Table 1.2.1-1.

Sampling and Analysis Methods. T hree approaches were used to measure targeted compounds in the high -end MEs : (1) reference method time -integra ted samplers to q uantify concentrations over 20-40 minute sampling periods; (2) continuous surrogate method monitors to determine short-term concentration variations over 10-60 second sampling periods; and (3) supplemental methods to provide additional sho rt

- term surrogate concentration estimates over

intermediate time frames of several minutes. Supplemental methods included newer methods that have not been fully adapted or ruggedized for field use. The supplemental methods provide independent checks and pe riodic corroboration of the surrogate approach used to estimate time

series values for species not directly measured by the surrogate methods

.

1. The reference method s include passive and pressurized whole- air canister sample rs used

to collect ambient and b reath CO, CO 2 

### , BTEX, MTBE , and 1,3- BD ; acidified 2,4-

di nitro phenylhydrazine (DNPH) cartridges to collect HCHO and CH 3 

### CHO ; and a multibed (TenaxTA

- Carbotrap -Carbosieve) solid adsorbent tube for ambient EtOH (Chicago only). After collection , these samples a re sent to the DRI Organic Analytical Laboratory for analysis. Canister CO and CO 2 

### are chromatographed and converted to methane for analysis by flame ionization detection (GC/FID) ; BTEX, MTBE, and 1,3- BD are quantified by capillary GC/FID [ GC/ mass spectro metry ( MS ) for breath samples] using a
separate system (Zielinska et al, 1998). The DNPH cartridges are eluted with acetonitrile

### 1

- 5 and aldehydes analyzed by high performance liquid chromatography (LC) with photodiode array ultraviolet ( UV ) detection of their hydrazone derivatives. The multi

- bed sorption tubes are thermally desorbed into a GC and quantified by MS . These methods are basically standard TO -15, -11A, and -17 EPA procedures with some improvements incorporated by DRI as described in Appendix B.

2. The surrogate methods include both active non-dispersive infrared (NDIR) and passive

T- 15 Langan electrochemical cell devices for CO , and an active photo-ionization detector (PID) for volatile organic compounds (VOCs) with ionization potentials below 10.6 eV (principally olefins and aromatic species). These continuous instruments respond to concentration changes within a few seconds and provide sensitive proportionate measures

of the short- term variability of exhaust and evaporative species quantified by the t ime

integrated reference methods. Surrogate methods are used to generate normalized

continuous time -series of concentrations for BTEX, MTBE, EtOH, 1,3-BD, and the aldehydes quantified by the reference methods.

3. The supplemental methods include both active continuous BTEX and HCHO instruments

with s everal minute response time s and a passive microextraction fiber sampling a flowing analyte stream for BTEX over a 10-minute period. The continuous BTEX monitor, a Kore MS200, quantifies species diffusing through its semi

- permeable

membrane inlet by 70eV electron impact ionization and time -of- flight MS

. The HCHO

instrument bubbles ambient air into a flowing aqueous 2,4-pentanedione and ammonia reagent to produce a HCHO -specific product, 3,5- diacetyl -1,4-dihydrolutidene , that is quantified by UV fluorescence. The 75 um film solid phase microextraction carboxen/polydimethylsiloxane (SPME-CAR/PDMS) fiber is passively exposed in a flowing air stream for 10 minutes, retracted into its syringe holder, and promptly inject ed into a GC with PID/FID detection optimized for BTEX quantification.

All sampling and analysis methods are described in detail in Appendix B. In addition,

the validation of the SPME method is de scribed in detail in Appendix C. Quality Assurance proced ures are described in Appendix H.

1.2.3 Exposure Biomarkers

Breath measurements were used as exposure biomarkers in four high

- end MEs: out-ofvehicle cabin refueling (ME7) ; parking in an underground garage (ME11); driving through a roadway tunnel (ME6); and trailing a high emitting vehicle (ME13). The test subject took three breath samples. One sample was taken before initiating ME sampling; the second, ten seconds immediately after completing the active refueling task or within a minute of experiencing a

mea sured peak exposure in the other three ME s , and a third

, immediately following the second.

The 3 rd 

### sample was analyzed if there was a problem with the second sample. The subject used a 1- liter evacuated canister, plac ing its inlet tube in to his mouth and b reath ing smoothly and regularly through the mouth around the tube until a resting tidal breath ing pattern was
established. At the end of a normal tidal exhalation, the subject closed his mouth around the tube, open ed the canister valve expe lling his expir atory reserve and filled the canister , c ollect ing

one liter of the expiratory reserve. When the canister was filled, the technician closed the canister valve to capture the sample (Pleil and Lindstrom, 2002; Lindstrom and Pleil, 1996). All breath samples w ere analyzed by GC/MS for BTEX, MTBE, 1,3-BD, and EtOH as described by Pleil

### 1

- 6 and Lindstrom (2002); CO 2 

### was methanized and quantified by GC/FID. Four subjects, labeled as 1, 2, 3, and 4 in the time- integrated database, were utilized for breath sample measurements.

1.3 Results and Discussion

This section summarizes the distributions of high -end exposure levels observed for each

ME by city and season. These exposure levels are examined as 20 to 4 0 min ute average s from

the integrated reference measurements , 5-10 minute averages from the surrogate data as corroborated by the supplemental measures, and as peak exposures using the one minute

reconstructed surrogate time series.

1.3.1 Variation of day- to -day exposures by ME in each city

Table 1.3.1-1 and 1.3.1- 2 summariz e the three city

, summer

- winter , 20-40 minute

average , maximum

, and minimum ME canister levels of CO, benzene, and sum of BTEX and th e HCHO and CH 3 

### CHO values from DNPH cartridges. A verage, maximum

, and minimum in /out

cabin temperature and relative humidity (T/ RH) values are also listed. In

- cabin T/RH values are in parentheses. Figures 1.3.1-1 through 1.3.1-6 show the day- to -day variations in benzene, 1,3- BD, HCHO, and CO concentrations.

In general, exposure levels should be proportionate to the number of sources and their

emission rate s in the ME and inverse to increasing distance to the emission source and t he extent

of emissions dilution. Dilution is a function of meteorology and the presence of physical

obstructions that may inhibit emissions dispersion. With the exception of refueling activities , we generally find that exposure levels are lower in outdoor environments and higher in enclosed environments. However, substantial variations exist among outdoor environments with respect to proximity to emissi on sources and the magnitude of their emissions. For example, the 40- min ute average exposures for most urban canyon sidewalk /bus stop samples are on the order of a 1-2 ppbv for benzene, whereas benzene exposures on outdoor surface parking lots or toll plaz a

aprons are usually higher. Refueling samples range up to few hundred ppbv benzene over 20

min ute sampling time s and show substantial day- to -day variability. In -cabin exposures during

vehicle roadway operation show more consistency sample to sample and mo re temporal uniformity than the other MEs

.

As it could be expected, MTBE and the BTEX species show the highest concentrations in refueling MEs dominated by evaporative emissions whereas CO, HCHO and 1,3- BD are highest

in cold- start dominated M Es (underground garage, roadway tunnel, toll plaza, surface parking).

Several Houston refueling 1,3-BD values had to be invalidated d ue to the interference s stemming

from elevated MTBE concentrations in these MEs

. MTBE decomposes slightly (on the order of

1 – 5%) at G C in jector temperature s forming isobutene (2- methylpropene) , a decomposition product that elute s just prior to 1,3-BD on the DB-1 (or equivalent) chromatographic column.

When concentration s of isobutene are much higher than 1,3- BD , they tail into the butad iene peak biasing its apparent concentration upward. This interference was confirmed by GC/MS. As noted in Tables 1.3.1-1 and 1.3.1-2, one value for ME3 and two for ME7 were invalidated in summer samples and one value for ME3 and four for ME7 in winter samples.ME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon loop ; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

- cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidew alk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza;
ME13 : In

- cabin trailing high

- emitter vehicle1-7 

### Table 1.3.1-1. Summer average, maximum, and minimum ME concentrations (ppbv) of BTEX, 1,3- BD, HCHO, CH3CHO, EtOH, MTBE, and CO (ppmv)
Atlanta (Conventional Fuel)

ME ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME9 ME10 ME11 ME12 ME13 Replicates 5 3 5 5 3 5 3 3 3 5 3 5
1,3

- butadiene Ave. 1.7 0.3 0.6 3.6 0.3 0.3 0.2 0.1 1.3 3.6 0.7 1.0

Min. 1.2 0.1 0.1 1.2 0.0 0.1 0.1 0.0 0.4 1.2 0.5 0.7

Max. 2.2 0.4 2.1 7.3 0.7 0.6 0.2 0.4 2.2 6.2 0.8 1.1

Benzene Ave. 6.8 2.0 12.3 20.4 2.4 25.9 1.0 1.6 4.6 28.1 3.6 6.0

M in. 4.2 1.4 5.8 6.0 1.7 6.2 0.9 1.4 1.6 17.7 3.0 3.7

Max. 9.3 2.4 22.9 40.3 3.7 74.2 1.1 1.8 9.0 35.3 3.9 9.3

Toluene Ave. 13.6 4.2 30.6 63.2 4.2 43.7 2.5 4.1 9.8 76.5 5.3 18.0

Min. 8.4 2.4 15.7 19.7 3.1 10.5 2.4 3.6 3.3 49.2 4.9 9.1

Max. 21.2 5.4 4 3.0 122.6 6.2 104.1 2.8 4.7 19.4 93.6 5.6 37.6 Ethylbenzene Ave. 2.2 0.7 4.1 9.9 0.7 4.6 0.4 0.7 2.0 12.8 0.8 2.6

Min. 1.5 0.4 1.8 3.4 0.5 1.1 0.4 0.6 0.6 8.2 0.8 1.6

Max. 3.5 0.9 5.1 18.7 1.0 8.7 0.5 0.9 4.0 17.2 0.9 4.8 Xylene Ave. 8.7 2.9 15.2 37. 0 2.6 17.1 1.8 3.0 8.0 48.8 3.6 10.3

Min. 5.5 1.6 6.6 12.5 1.5 4.4 1.8 2.6 2.9 30.9 3.4 6.1

Max. 13.7 3.7 18.5 69.2 3.9 29.2 1.9 3.8 15.5 63.4 3.9 19.1 Formaldehyde Ave. 6.6 6.7 9.3 25.7 5.1 10.0 10.7 11.2 12.8 33.2 7.6 8.6

Min. 3.9 5.0 5.5 15.4 4.4 7.2 9.6 10.5 8.8 22.2 7.0 7.3

Max. 8.4 8.5 11.1 32.3 6.2 11.5 11.3 12.5 19.7 50.6 8.3 11.1 Acetaldehyde Ave. 6.6 4.6 4.3 10.8 2.8 3.4 2.7 3.0 4.0 12.2 2.4 5.2

Min. 2.0 3.5 1.2 7.3 2.1 1.1 2.5 2.1 2.5 7.4 1.5 4.4

Max. 18.6 6.5 5.9 15.1 3.4 5.1 3.1 4 .0 6.8 20.9 3.5 6.7

CO canister Ave. 6.1 1.4 0.7 8.5 2.1 0.6 0.8 1.1 2.7 14.5 3.1 4.0

Min. 3.7 0.7 0.4 1.7 2.0 0.2 0.7 1.0 0.8 9.8 2.8 2.3

Max. 11.7 2.1 1.4 16.2 2.4 1.2 1.0 1.1 5.6 20.0 3.5 6.2 Temp  ̊C Ave. ( 22.3 ) ( 27.2 ) ( 31.7 ) 27.8 32.3 ( 24.6 ) (in

- cabin) Min. ( 21.2 ) ( 19.6 ) ( 30.5 ) 22.1 31.0 ( 23.6 )

Max. ( 23.9 ) ( 33.6 ) ( 33.8 ) 30.4 33.8 ( 25.6 )
RH, % Ave. ( 57.8 ) ( 60.0 ) ( 51.8 ) 65.3 47.4 ( 48.8 ) (in

- cabin) Min. ( 56.0 ) ( 43.0 ) ( 46.0 ) 56.0 41.0 ( 46.0 )

Max. ( 59.0 ) ( 73.0 ) ( 60.0 ) 86.0 51.0 ( 54.0 ) Note: Urban canyon loop for Atlanta: Peachtree Street NW, Forsyth

- Carnegie, Spring Street NW, and Harris StreetME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon loop ; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

- cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidew alk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza;
ME13 : In

- cabin trailing high

- emitter vehicle1-8 Chicago (Oxygenated Fuel

- Ethanol)

ME ME1 ME2 ME3 ME4 M E5 ME6 ME7 ME8 ME9 ME10 ME11 ME12
1,3

- butadiene Ave. 0.4 0.5 0.1 2.4 0.3 1.3 0.1 0.3 0.3 0.6 1.4 0.5

Min. 0.2 0.3 0.0 1.5 0.2 1.2 0.0 0.3 0.1 0.4 0.2 0.3

Max. 0.5 1.0 0.1 4.0 0.3 1.6 0.3 0.4 0.4 0.9 2.6 0.8

Benzene Ave. 2.7 2.9 2.1 8.9 1.5 5.8 4.9 2. 5 1.7 3.3 5.1 3.1

Min. 1.7 1.6 0.5 5.6 1.4 4.2 0.6 1.8 1.3 1.8 1.2 2.6

Max. 4.9 5.2 4.6 12.2 1.5 8.7 11.4 3.6 2.2 5.7 8.2 3.4

Toluene Ave. 4.8 4.7 6.6 23.3 2.8 15.0 11.2 3.4 2.4 7.5 11.8 3.6

Min. 2.4 2.6 1.4 13.6 2.3 6.7 0.7 2.0 1.5 3.5 3.4 2.6

Ma x. 9.3 7.5 18.6 37.8 3.3 25.5 27.3 6.1 3.5 13.6 18.4 4.3

Et hylb enzene Ave. 0.8 0.7 1.7 3.3 0.4 1.9 1.4 0.6 0.5 0.8 2.0 0.6

Min. 0.4 0.3 0.2 1.8 0.3 1.4 0.1 0.4 0.3 0.7 0.6 0.4

Max. 1.3 1.2 7.2 4.5 0.5 2.8 2.6 0.9 0.8 1.1 3.0 0.7 Xylene Ave. 3.1 2.7 7 .2 13.4 1.7 6.6 5.9 2.1 1.8 3.2 7.8 2.3

Min. 1.6 1.2 0.9 6.9 1.4 5.1 0.5 1.4 1.1 2.7 2.2 1.9

Max. 5.1 4.5 29.8 17.1 2.0 9.4 10.2 3.4 3.0 4.0 12.1 2.8

Formal dehyde Ave. 7.7 5.5 10.5 16.1 5.9 8.9 11.7 6.2 6.1 6.7 10.5 8.8

Min. 5.4 4.6 8.4 10.7 5.3 8.0 3.4 3.8 3.7 5.9 5.8 6.2

Max. 9.4 7.3 13.7 26.7 6.5 10.1 24.6 7.6 7.8 8.1 14.1 11.6

Acet aldehyde Ave. 6.3 7.7 6.3 10.9 5.1 8.4 4.5 3.8 3.7 3.4 6.5 5.4

Min. 3.6 4.1 2.8 8.1 4.5 7.4 2.5 3.7 2.2 2.5 3.4 3.8

Max. 8.6 14.7 9.4 15.0 5.8 8.8 6.1 4.0 4.5 4. 4 8.3 7.8

CO can ister Ave. 2.2 1.7 0.4 5.3 1.4 5.1 0.6 1.0 1.4 1.2 3.1 3.0

Min. 1.5 1.3 0.3 4.0 1.1 4.0 0.3 0.8 0.9 1.0 0.6 2.5

Max. 3.0 2.4 0.6 8.2 1.6 7.1 0.7 1.2 1.7 1.8 5.1 3.7

EtOH Ave. 6.7 10.5 13.0 15.4 5.7 20.6 28.3 0.0 0.8 1.3 12.2 3.1

Min

. 0.0 4.9 0.0 0.0 0.7 12.5 0.0 0.0 0.0 0.0 0.0 0.0

Max. 12.1 20.0 36.7 30.4 10.4 29.4 115.4 0.0 2.4 3.8 42.1 4.9 Temp  ̊C Ave. (23.3) (22.3) (28.3) (26.8) (21.0) ( 21.7 ) 26.7 25.0 26.0 22.6 27.3 31.5 (in

- cabin) Min. (21.2) (21.9) (25.6) (25.9) (20.3) ( 20.2 ) 23.5 23.4 24.5 20.7 22.7 30.2

Max. (25.8) (23.2) (30.2) (28.4) (21.4) ( 25.0 ) 28.8 26.5 27.8 24.6 29.7 33.5

RH , % Ave. ( 51.6 ) ( 44.7 ) ( 51.5 ) ( 60.2 ) ( 56.0 ) ( 53.0 ) 58.2 54.3 52.7 69.7 56.0 42.3 (in

- cabin) Min. ( 46.0 ) ( 41.0 ) ( 45.0 ) ( 55.0 ) ( 53.0 ) ( 50.0 ) 49.0 53.0 50.0 66.0 45.0 30.0

Max. ( 55.0 ) ( 48.0 ) ( 63.0 ) ( 65.0 ) ( 60.0 ) ( 57.0 ) 67.0 56.0 55.0 73.0 66.0 56.0

Note: Urban canyon loop for Chicago: Lake Street, Wabash Avenue, Van Buren Street, and State StreetME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon loop ; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

- cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidew alk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza;
ME13 : In

- cabin trailing high

- emitter vehicle1-9 Houston (Oxygenated Fuel

– MTBE)

ME ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12
1,3

- butadiene Ave. 0.7 0.4 0.6* 1.7 0.9 1.4 1.2* 0.3 0.1 0.4 1.6 0.9

Min. 0.3 0.3 0.3 0.2 0.6 0.8 0.5 0.2 0.1 0.3 0.5 0.4

Max. 1.0 0.5 0.7* 4.5 1.2 2.8 2.1* 0.5 0.2 0.5 2.9 1.4

Benzene Ave. 1.9 1.4 52.6 5.1 2.5 3.7 130.7 1.4 0.6 1.6 5.4 3.2

Min. 1.3 1.2 5.6 1.0 1.9 2.5 13.3 0.7 0.3 1.0 2.3 1.3

Max. 2.7 1.9 175.1 1 1.1 3.1 7.1 281.9 2.6 0.7 1.9 9.8 5.0

Toluene Ave. 3.4 2.7 80.3 11.5 4.6 6.6 183.0 3.3 1.0 2.7 12.0 5.8

Min. 2.1 2.2 15.9 2.5 3.0 4.1 27.4 1.7 0.7 1.9 5.6 1.7

Max. 4.2 3.3 277.5 22.7 5.5 13.7 425.6 4.4 1.3 3.1 19.4 12.2

Et hylb enzene Ave. 0.6 0.5 10.6 2.4 0.9 1.3 21.0 0.7 0.2 0.7 2.6 1.3

Min. 0.4 0.5 2.6 0.6 0.6 0.9 3.5 0.3 0.1 0.5 1.1 0.3

Max. 0.7 0.7 35.0 5.2 1.1 2.5 50.8 1.3 0.2 0.8 4.5 2.9 Xylene Ave. 2.6 2.3 35.7 9.3 3.8 5.4 71.5 2.7 0.9 2.6 10.1 5.6

Min. 1.7 2.0 10.2 2.5 2.6 3.8 10.2 1.1 0 .6 1.8 4.5 1.3

Max. 3.4 2.8 110.2 18.5 4.4 10.3 143.0 5.1 1.0 3.2 16.8 12.2

Formal dehyde Ave. 5.9 4.3 5.2 6.8 6.5 5.8 7.3 5.5 4.1 5.3 8.4 7.3

Min. 3.4 2.9 4.1 4.9 4.4 5.2 4.5 4.9 2.7 4.5 6.0 5.1

Max. 10.9 5.1 7.7 8.1 8.9 6.2 10.2 6.4 6.4 5.8 10.1 10 .0

Acet aldehyde Ave. 0.7 0.6 0.8 0.8 0.8 0.7 1.0 0.7 0.5 0.7 1.0 0.8

Min. 0.5 0.4 0.7 0.6 0.6 0.6 0.7 0.6 0.4 0.6 0.7 0.6

Max. 1.2 0.6 1.1 0.9 1.0 0.7 1.3 0.8 0.8 0.7 1.1 1.1

CO can ister Ave. 1.7 1.5 1.0 2.9 1.7 2.7 0.6 0.6 0.5 0.8 3.1 2.5

Min. 1.2 0.9 0.7 0.5 1.7 1.8 0.3 0.5 0.4 0.5 1.1 1.8

Max. 2.1 2.6 1.6 7.0 1.8 4.5 0.8 0.6 0.7 1.1 6.2 3.2

MTBE Ave. 2.8 1.3 1325.5 11.2 5.6 8.8 3129 2.9 1.3 2.6 12.2 8.7

Min. 2.1 0.8 79.8 4.8 3.7 5.1 414.3 1.3 1.2 2.1 6.3 1.5

Max. 3.8 1.7 4284.1 18.8 7.9 16 .5 5767 5.4 1.4 2.9 23.7 20.1 Temp  ̊C Ave. (23.7) (24.5) (28.2) (28.3) ( 22.5 ) ( 24.5 ) 33.1 31.1 31.4 31.7 28.1 30.0 (in

- cabin) Min. (22.9) (23.5) (26.0) (24.0) ( 21.3 ) ( 23.3 ) 28.4 28.5 27.9 28.5 21.8 29.5

Max. (25.2) (25.7) 30.9 (33.6) ( 24.7 ) ( 25.6 ) 35.0 33.4 33.6 36.5 37.1 30.4
RH, % Ave. ( 54.8 ) ( 47.0 ) ( 47.6 ) ( 47.0 ) ( 55.3 ) ( 50.2 ) 53.6 58.3 58.7 58.0 48.8 67.5 (in

- cabin) Min. ( 50.0 ) ( 42.0 ) ( 41.0 ) ( 36.0 ) ( 53.0 ) ( 47.0 ) 47.0 41.0 48.0 40.0 41.0 65.0

Max. ( 62.0 ) ( 51.0 ) ( 58.0 ) ( 57.0 ) ( 57.0 ) ( 57.0 ) 70.0 75. 0 77.0 69.0 58.0 70.0

Note: Urban canyon for Houston: Louisiana , Clay, Walker, and Smith Streets * For 1,3 -BD in Houston, one extreme value for ME3 and two for ME7 were invalidated

.ME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon loop ; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

- cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidew alk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza;
ME13 : In

- cabin trailing high

- emitter vehicle1-10 

### Table 1.3.1-2. Winter average, maximum, and minimum ME concentrations (ppbv) of BTEX, 1,3- BD, HCHO, CH3CHO, EtOH, MTBE, and CO (ppmv)
Atlanta (Conventional Fuel)

ME ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME9 ME10 ME11 ME12 ME13 Replicates 5 3 5 5 3 6 3 3 3 5 3 5
1,3

- BD Ave. 0.6 0.3 0.4 4.1 0.3 1.5 0.2 0.2 0.7 4.0 0.4 1.6

Min. 0.3 0.0 0.1 1.7 0.2 0.2 0.1 0.1 0.3 1.0 0.3 0.9

Max. 0.8 0.4 0.7 7.9 0.5 3.6 0.3 0.3 1.5 6.3 0.5 2.8

Benzene Ave. 2.6 1.4 8.4 26.4 1.4 38.5 0.9 1.0 3.5 21.0 2.4 6.7

Min. 1.9 0.3 1.6 6.1 1.1 10.0 0.7 0.6 1.3 3.2 1.6 3.5

Max. 3.5 2.3 17.6 49.9 1.7 99.4 1. 2 1.3 6.4 28.6 3.2 11.1

Toluene Ave. 5.3 4.0 14.5 60.5 3.5 58.8 1.5 1.8 8.7 53.0 3.7 17.7

Min. 3.7 0.8 4.0 14.5 2.2 23.3 1.0 1.2 2.8 7.1 2.2 9.1

Max. 7.3 6.5 26.4 112.7 4.5 125.1 2.5 2.7 15.4 87.4 6.0 33.5 Ethylbenzene Ave. 1.0 0.8 1.7 11.5 0.6 4.8 0 .3 0.3 1.5 9.7 0.6 2.8

Min. 0.7 0.1 0.5 2.5 0.5 2.7 0.2 0.2 0.5 1.4 0.4 1.5

Max. 1.5 1.4 2.6 22.1 0.9 7.4 0.4 0.5 2.7 15.0 1.0 5.4 Xylene Ave. 4.4 3.2 6.4 42.6 2.6 17.2 1.1 1.3 5.7 37.2 2.4 11.4

Min. 3.0 0.4 2.2 9.7 2.0 10.2 0.8 0.9 2.0 5.4 1.5 6. 0

Max. 6.2 5.7 9.3 79.7 3.7 26.4 1.6 1.8 10.5 58.5 3.8 22.1

Formal dehyde Ave. 6.2 8.6 21.9 19.6 4.6 3.4 2.6 2.0 5.0 11.4 3.4 8.4

Min. 2.6 5.1 4.1 5.6 3.3 2.3 1.4 1.1 3.4 4.0 3.0 5.7

Max. 8.0 12.4 89.1 28.1 6.0 5.0 4.1 3.1 6.2 15.7 3.7 10.4

Acet alde hyde Ave. 2.8 2.9 5.4 8.2 2.0 2.0 1.7 1.5 2.3 6.8 2.5 4.3

Min. 0.9 2.5 1.5 4.2 1.1 1.1 1.5 0.9 1.3 2.8 1.7 3.6

Max. 5.6 3.5 17.4 12.0 3.1 2.6 2.1 1.9 2.9 9.8 3.0 5.2

CO can ister Ave. 2.6 1.5 0.8 17.7 1.2 1.2 0.8 0.9 1.9 13.2 2.4 5.7

Min. 2.0 1.3 0.5 4.3 0.9 0.4 0.7 0.6 0.9 2.9 1.5 2.7

Max. 3.2 1.8 1.4 36.1 1.5 2.2 1.0 1.1 3.9 21.9 2.8 9.0 Temp  ̊C Ave. ( 21.3 ) ( 24.6 ) ( 17.9 ) ( 21.1 ) ( 22.8 ) 10.1 4.8 3.8 10.6 14.5 9.4 ( 22.2 ) (in

- cabin) Min. ( 15.2 ) ( 23.1 ) ( 15.0 ) ( 14.0 ) ( 20.6 ) 5.9 4.1 1.2 5.1 5.5 6.0 ( 17 .9 )

Max. ( 28.4 ) ( 25.8 ) ( 20.2 ) ( 24.6 ) ( 24.0 ) 16.7 5.5 5.7 14.2 19.4 15.3 ( 26.4 )
RH, % Ave. (35.0) (32.3) (40.4) (41.8) (31.0) 54.8 58.0 63.0 52.0 47.4 55.7 (37.2) (in

- cabin) Min. (21.0) (28.0) (28.0) (30.0) (27.0) 41.0 45.0 45.0 38.0 26.0 22.0 (23.0)

Max. (48.0) (36.0 ) ( 56.0 ) ( 47.0 ) ( 34.0 ) 81.0 71.0 73.0 63.0 65.0 77.0 ( 50.0 )ME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon loop ; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

- cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidew alk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza;
ME13 : In

- cabin trailing high

- emitter vehicle1-11 Chicago (Oxygenated Fuel

- Ethanol)

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12
1,3

- BD Ave. 0.6 0.4 2.8 4.4 0.2 0.5 0.7 0.3 0.3 0.5 2.4 0.3

Min. 0.2 0.2 0.0 1.6 0.1 0.4 0.2 0.2 0.2 0.1 1.3 0.2

Max. 1.2 0.6 13.2 7.7 0.2 0.9 1.2 0.5 0.3 0.8 3.2 0.4

Benzene Ave. 1.2 1.3 5.2 16.4 0.7 2.3 20.4 1.0 1.0 1.8 12.9 1.2

Min. 0.5 1.0 0.2 5.7 0.7 1.4 1.4 0.9 0.9 0.6 5.6 0.9

Max. 2.2 1.6 12.9 24.2 0.8 4.8 39.1 1.2 1.1 2 .9 20.7 1.9

Toluene Ave. 1.8 2.5 4.6 29.0 1.1 3.1 13.8 1.4 1.2 2.9 22.7 1.3

Min. 0.5 2.0 1.2 10.8 1.0 1.8 2.1 1.2 1.1 0.9 12.3 0.9

Max. 3.1 2.9 8.9 39.1 1.3 6.5 26.6 1.8 1.4 4.9 36.4 2.0

Et hylb enze ne Ave. 0.5 0.4 0.6 5.5 0.2 0.6 1.4 0.3 0.3 0.6 4.4 0 .3

Min. 0.2 0.3 0.0 1.9 0.1 0.4 0.5 0.2 0.2 0.2 2.3 0.2

Max. 0.8 0.5 1.4 7.6 0.2 1.4 3.0 0.4 0.3 1.0 7.4 0.4 Xylene Ave. 1.9 1.5 2.8 22.7 0.8 2.5 6.9 1.1 0.9 2.3 18.3 1.1

Min. 0.9 1.2 0.2 7.5 0.7 1.4 1.9 0.8 0.9 0.7 10.3 0.8

Max. 3.6 1.8 6.0 31.2 0.9 5.2 15.7 1.4 1.0 3.8 29.5 1.8

Formal dehyde Ave. 7.2 4.6 4.3 13.9 2.8 5.3 3.2 2.9 3.5 4.4 9.1 3.0

Min. 2.1 3.2 2.3 7.2 1.8 2.9 1.8 2.5 2.8 3.3 2.9 2.5

Max. 21.5 6.0 7.7 18.2 3.5 7.8 4.3 3.2 4.2 5.9 15.3 3.6

Acet aldehyde Ave. 5.0 3.1 3.6 12.7 2.3 3 .8 2.8 2.1 2.5 2.5 7.6 2.2

Min. 1.1 2.4 2.4 5.9 1.4 1.5 2.0 1.6 2.1 1.4 1.6 2.0

Max. 16.8 4.5 7.4 17.7 2.9 6.9 3.8 2.7 3.1 3.8 12.8 2.6

CO can ister Ave. 1.5 1.0 0.4 12.0 0.9 2.2 0.7 0.9 0.9 1.7 11.0 1.7

Min. 1.1 0.4 0.4 4.5 0.8 1.7 0.2 0.7 0.8 0.6 3 .8 1.3

Max. 2.1 1.4 0.5 18.4 1.0 3.4 1.8 1.1 1.0 2.7 16.8 2.0

EtOH Ave. 6.8 2.1 5.1 1.4 4.3 1.6 2.2 1.8 4.0 3.3 3.7 0.9

Min. 1.6 0.0 2.8 0.1 1.4 0.0 0.0 0.0 0.0 1.3 1.9 0.0

Max. 12.3 3.1 9.8 2.6 7.9 2.7 4.8 3.9 8.0 5.9 6.0 2.3 Temp  ̊C Ave. (21.5) (22.8) (17.3) (21.6) (22.6) (20.9) 1.6 4.9 6.5 6.4 (17.0) 1.9 (in

- cabin) Min. (18.1) (21.3) (11.2) (15.9) (21.6) (16.3)

- 3.3 1.3 2.1 4.1 (13.6) 0.0

Max. (30.6) (24.8) (19.8) (24.7) (23.5) (24.7) 6.6 9.5 12.3 8.7 (22.1) 4.6
RH, % Ave

. (19.2) (23.7) (22.0) (37.5) (17.7) (24.8) 44.7 46.3 42.7 37.0 (41.4) 53.0 (in

- cabin) Min. (9.0) (21.0) (13.0) (25.0) (13.0) (14.0) 32.0 32.0 27.0 32.0 (29.0) 25.0

Max. (25.0) (25.0) (32.0) (60.0) (21.0) (41.0) 62.0 62.0 60.0 42.0 (61.0) 77.0ME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon loop ; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

- cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidew alk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza;
ME13 : In

- cabin trailing high

- emitter vehicle1-12 Hous ton (Oxygenated Fuel

- MTBE)

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12
1,3

- BD Ave. 0.4 1.2 1.8* 3.8 0.5 1.1 1.9* 0.1 0.2 1.7 2.7 0.8

Min. 0.3 0.4 0.4 0.4 0.4 0.1 1.9* 0.1 0.1 0.2 0.4 0.5

Max. 0.6 2.7 3.6 5.7 0.6 2.3 1.9* 0.2 0.2 4.3 4.3 1 .3

Benzene Ave. 1.4 3.7 17.7 10.6 1.7 2.7 55.0 0.5 0.6 5.0 7.8 2.5

Min. 1.1 1.4 2.3 1.6 1.4 0.7 7.7 0.5 0.4 1.5 1.4 1.8

Max. 2.0 8.2 56.6 14.5 2.1 4.2 97.7 0.7 0.8 11.9 13.7 3.8

Toluene Ave. 3.0 6.5 25.6 21.8 3.6 4.6 64.3 0.8 1.1 10.5 17.3 4.2

Min. 2.3 2.9 4.2 4.2 3.2 1.6 10.9 0.7 0.8 3.5 3.1 2.7

Max. 5.2 13.4 69.7 30.9 3.8 6.7 106.0 1.0 1.4 21.7 31.4 6.3

Et hylb enzen e Ave. 0.7 1.4 2.4 4.3 0.8 0.9 4.5 0.2 0.3 1.9 3.3 0.8

Min. 0.5 0.7 0.7 1.1 0.7 0.4 1.8 0.2 0.2 0.7 0.7 0.5

Max. 1.1 2.6 4.4 5.9 0.8 1.4 8.0 0.2 0.3 4.3 5.8 1.2 Xylene Ave. 3.4 6.3 10.9 17.6 3.5 4.4 18.7 0.8 1.1 8.1 13.9 3.6

Min. 2.5 3.3 3.6 5.5 3.5 1.5 4.4 0.7 0.7 3.4 3.7 2.1

Max. 5.9 11.5 18.4 24.7 3.6 6.9 35.2 1.0 1.4 17.5 25.0 6.3

Formal dehyde Ave. 4.5 8.2 7.1 10.5 3.8 7. 6 5.7 2.1 2.5 4.0 5.7 5.0

Min. 3.0 4.7 4.6 7.9 2.7 5.4 3.5 1.9 2.0 1.2 2.9 4.0

Max. 5.1 12.6 8.4 12.1 4.5 8.8 10.6 2.3 3.1 7.6 8.6 6.1

Acet aldehyde Ave. 1.9 4.3 6.5 5.3 1.9 4.4 5.3 1.7 1.7 4.5 3.4 2.0

Min. 1.2 2.5 3.5 4.7 1.5 2.6 3.2 1.4 1.2 3.4 1.0 1.8

Max. 2.4 7.0 9.2 5.9 2.2 6.1 10.0 1.9 1.9 5.7 4.9 2.4

CO can ister Ave. 1.4 3.7 1.2 7.8 1.8 2.9 1.0 0.4 0.5 3.4 6.0 2.7

Min. 0.9 1.4 0.5 1.1 1.6 0.8 0.3 0.3 0.4 0.7 1.1 1.7

Max. 1.6 6.9 2.7 12.5 2.1 5.5 2.6 0.5 0.7 8.4 9.8 4.5

MTBE Ave. 3.9 10. 2 890.6 25.4 4.2 7.3 2568.9 0.5 0.7 15.1 26.0 6.7

Min. 1.4 2.6 23.3 1.8 3.2 3.3 347.8 0.5 0.6 6.5 2.7 2.6

Max. 8.1 25.3 3135.3 68.1 4.8 10.4 5629.9 0.6 0.8 20.9 63.6 13.2 Temp  ̊C Ave. (22.3) (22.9) (21.6) (22.6) (21.0) (22.4) 15.7 9.8 11.4 17.1 15.5 14.9 (in

- cabin) Min. (18.0) (20.4) (19.3) (19.9) (19.1) (19.9) 10.9 7.2 7.9 13.4 10.3 7.9

Max. (26.5) (24.3) (23.4) (25.2) (22.2) (24.8) 20.9 12.2 14.7 21.0 18.6 20.2
RH, % Ave. (41.2) (36.7) (52.0) (54.2) (49.3) (46.0) 67.0 61.0 55.3 63.0 69.6 77.7 (in

- cabin) Min. (29.0) (33.0) (37.0) (36.0) (43.0) (34.0) 55.0 53.0 46.0 48.0 43.0 70.0

Max. (58.0) (42.0) (61.0) (69.0) (56.0) (54.0) 77.0 71.0 67.0 76.0 87.0 83.0
*Note: For 1,3

- BD in Houston, one extreme value for ME3 and four for ME7 were invalidatedME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin ref ueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin undergroun d garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-13

Microenvironmentppbv 

### Formaldehyde

ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME9 ME10 ME11 ME12 ME13 0 5 10 15 20 25 30 35 40 45 50 55

Maximum
Minimum

75%
25%
Median
Outliers
Extremes Microenvironmentppbv 

### Atlanta, Summer 2002

- 2003

Benzene

ME1 ME2 ME3 ME

4 ME

5 ME

7 ME

8 ME9 ME10 ME11 ME12 ME13 0 8 16 24 32 40 48 56 64 72 80

Maximum
Minimum
75%
25%
Median
Outliers
Extremes

Microenvironmentsppbv 

### Atlanta, Summer 2002

- 2003

1,3

- Butadiene

ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME9 ME10 ME11 ME12 ME13 0 0.8 1.6 2.4 3.2

4 4.8 5.6 6.4 7.2

8

Maximum
Minimum

75%

25%

Median
Outliers
Extremes

Microenvironmentppm 

### CO

ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME9 ME10 ME11 ME12 ME13 0 2 4 6 8 10 12 14 16 18 20

Maximum
Minimum
75%
25%
Median Outliers

Extr emesME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin ref ueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin undergroun d garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-14 

## Atlanta Summer 2002-2003

Acetaldehyde

ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME9 ME10 ME11 ME12 ME13 0 2 4 6 8 10 12 14 16 18 20 22
Maximum
Minimum

75%
25%
Median
Outliers
Extremes



### Figure 1.3.1-1. Time -integrated exposure levels in different MEs in Atlanta, Summer 2002 and 2003

Microenvironmentppbv 

### Atlanta, Winter 2004

Benzene

ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME9 ME10 ME11 ME12 ME13 0 10 20 30 40 50 60 70 80 90 100

Maximum
Minimum

75%
25%
Median
Outliers
Extremes

Microenvironmentppbv 

### Atlanta, Winter 2004

1,3-Butadiane

ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME9 ME10 ME11 ME12 ME13 0 0.8 1.6 2.4 3.2

4 4.8 5.6 6.4 7.2

8

Maximum
Minimum

75%
25%
Median
Outliers
ExtremesME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin ref ueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin undergroun d garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-15 Microenvironmentppm 

### CO

ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME9 ME10 ME11 ME12 ME13 0 4 8 12 16 20 24 28 32 36 40

Maximum
Minimum

75%
25%
Median
Outliers
Extremes

Microenvironmentppb 

### Formaldehyde

ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME9 ME10 ME11 ME12 ME13 0 3 6 9 12 15 18 21 24 27 30

Maximum
Minimum

75%
25%
Median
Outliers
Extremes



## Atlanta Winter 2004

Acetaldehyde

ME1 ME2 ME3 ME4 ME5 ME7 ME8 ME9 ME10 ME11 ME12 ME13 0 2 4 6 8 10 12 14 16 18
Maximum
Minimum

75%
25%
Median
Outliers
ExtremesME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin ref ueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin undergroun d garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-16 

### Figure 1.3.1-2. Time -integrated exposure levels in different MEs in Atlanta , Winter 2004

Microenvironmentsppbv Formaldehyde

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 3 6 9 12 15 18 21 24 27

Maximum
Minimum

75%
25%
Median Outliers
E xtremes Microenvironmentsppbv 

### Chicago, Summer 2003

Benzene

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 1.5

3 4.5

6 7.5

9 10.5

12 13.5 Maximum
Minimum
75%

25%
Median
Outliers
Extremes

Microenvironmentsppbv 

### Chicago, Summer 2003

1, 3

-

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 0.5

1 1.5

2 2.5

3 3.5

4 4.5 Maxi mum Minimum

75%
25%
Median
Outliers
Extremes

Microenvironmentsppm CO

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 0.8 1.6 2.4 3.2

4 4.8 5.6 6.4 7.2

8 8.8
Maximum
Minimum
75% 25% Median Outliers
ExtremesME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin ref ueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin undergroun d garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-17 

### Figure 1.3.1-3. Time -integrated exposure levels in different MEs in Chicago, Summer 2003 Chicago Summer 2003

Acetaldehyde

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 2 4 6 8 10 12 14 16

Maximum
Minimum
75%
25%
Median
Outliers
Extremes

Microenvironmentppbv 

### Chicago, Winter 2004

Benzene

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 4 8 12 16 20 24 28 32 36 40

Maximum
Minimum
75%
25%
Median Outliers
Extremes

Microenvironmentsppbv 

### Chicago, Winter 2004

1,3

- Butadiene

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 0.8 1.6 2.4 3.2

4 4.8 5.6 6.4 7.2

8

Maximum
Minimum
75
% 25%
Median Outliers
ExtremesME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin ref ueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin undergroun d garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-18 Microenvironmentppbv 

### Formaldehyde

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 2 4 6 8 10 12 14 16 18 20

Maximum
Minimum

75%
25%
Median
Outliers
Extremes



### Chicago Winter 2004

Acetaldehyde

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 2 4 6 8 10 12 14 16 18

Maximum
Minimum

75%
25%
Median
Outliers
Extremes



### Figure 1.3.1-4. Time -integrated exposure levels in different MEs in Chicago, Winter 2004 Microenvironmentppm 

### CO

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 2 4 6 8 10 12 14 16 18 20

Maximum
Minimum

75%

25%
Median
Outliers

ExtremesME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin ref ueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin undergroun d garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-19 Microenvironmentsppbv 

### Houston, Summer 2004

1,3-Butadiane

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 0.5

1 1.5

2 2.5

3 3.5

4 4.5

Maximum
Minimum

75%
25%
Median
Outliers
Extremes

Microenvironmentppm 

### CO

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 1 2 3 4 5 6 7 8 9

Maximum
Minimum

75%
25%
Median
Outliers
Extremes

Microenvironmentppbv 

### Formaldehyde

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 1.5

3 4.5

6 7.5

9 10.5

12 Maximum
Minimum

75%
25%
Median
Outliers
Extremes Microenvironmentppbv 

### Houston, Summer 2004

Benzene

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 30 60 90 120 150 180 210 240 270 300

Maximum
Minimum
75%

25%
Median
Outliers

ExtremesME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin ref ueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin undergroun d garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-20 

### Houston Summer, 2004

Acetaldehyde

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 1 2 3 4 5 6 7 8 9 10
Maximum
Minimum

75%
25%
Median
Outliers
Extremes



### Figure 1.3.1-5. Time -integrated exposure levels in different MEs in Houston, Summer 2004

Microenvironmentsppbv 

### Houston, Winter 2005

1,3-Butadiane

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 0.6 1.2 1.8 2.4

3 3.6 4.2 4.8 5.4

6

Maximum
Minimum

75%
25%
Median
Outliers
Extremes

Microenvironmentppbv 

### Houston, Winter 2005

Benzene

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 10 20 30 40 50 60 70 80 90 100

Maximum

Minimum

75%

25%

Median

Outliers

ExtremesME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin ref ueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin undergroun d garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-21 Microenvironmentppm 

### CO

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 1.5

3 4.5

6 7.5

9 10.5

12 13.5

Maximum
Minimum

75%
25%
Median
Outliers
Extremes

Microenvironmentppbv 

### Formaldehyde

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 1.5

3 4.5

6 7.5

9 10.5

12 13.5

Maximum
Minimum

75%
25%
Median
Outliers
Extremes



### Houston Winter 2005

Acetaldehyde

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 1 2 3 4 5 6 7 8 9 10

Maximum
Minimum

75%
25%
Median
Outliers
Extremes



### Figure 1.3.1-6. Time -integrated exposure levels in different MEs in Houston, Winter 2005

### 1

- 22 1.3.2 Distribution of exposures within MEs in each city (1

- min ute time series)

The study protocol (Appendix A) specifies a sampling period of 20 ( ME3 /ME7) to 40

min utes beginning at the top of the hour to corre late with the local air quality monitoring

network sampling periods . Because large variations are expected within these time frames in exposures for most MEs , the protocol includes continuous measurements of target species with

time resolution s of about a minute. The supplemental Kore MS200 MS (deployed for BTEX) and Alpha Omega HCHO analyzer used to measure these species at 1 -minute resolutions directly

had not been earlier proven under such field conditions and only worked well intermittently

. Furthermore, there were no acceptable continuous methods for 1,3- BD , MTBE, EtOH

, CH 3 

### CHO, or non- methane VOCs (NMVOC ) that could be used in portable modes of operation with the necessary sensitivity . Accordingly, our sampling strategy consisted of a three- tier ed approach classified as reference, surrogate, and confirmatory measurements. The base set or reference (R) measurements consist of three well

- established time

- integrated me thods (canister s, DN PH , and solid adsorbent cartridges) as described in Section 1.2.2. These three methods together measure all species of interest over the 20-40 minute sampling periods within each ME and had excellent data capture rates. Although the integrated methods do n ot characterize shortterm peak exposures in MEs with highly varying exposure levels, they provide a basis for quantifying and deriving correlations between the integrated values and continuous surrogate (S)

measures , such as the CO and PID NMVOC monitors , in order to reconstruct short- term time series. For example, data for BTEX, and 1, 3- BD from the canister measurements can be used to

normalize continuous CO and NMVOC traces taken over the same periods to construct component time series in exhaust -domina ted environments. In a similar manner, the time series

of HCHO values can be reconstructed from the correlation of the integrated DNPH samples with

continuous CO measures

.

Table s 1.3.2-1A and 1.3.2- 1B list correlation coefficients (R 2 

### ), slopes, P- values and performance statistic for correlations of benzene, 1,3- BD

, HCHO, and CO measured from

canisters with NMVOC PID and continuous CO, measured by NDIR, for all ME with exception of ME3 and ME7, and for ME3 and ME7 only, respectively. It can be seen from Ta ble 1.3.2- 1A that 1,3- BD correlates with CO somewhat better than with NMVOC so continuous CO values were used for reconstructing 1- min ute time series for 1,3- BD for all MEs with exception of refueling experiments (ME3 and ME7). However, for refueling MEs (Table1.3.2- 1B) , the correlations are worse, although the correlations of benzene with NMVOC are still statistically significant for all three cities. The correlations of 1,3

- BD with NMVOC PID and CO_NDIR are not statistically significant, since neither 1,3 -BD, nor CO is abundant in evaporative emissions. Thus, the calculation of 1- min time series for 1,3 -BD in ME3 and ME7 is not valid for evaporative gasoline exposure. However, these species are often measured at some gas stations, since they originate from exhaust emissions of higher- emitting vehicles

. In addition, HCHO does not correlate very well with CO probably due to the photochemical production of this compound

in outdoor MEs.

The reconstructed 1- minute peak exposures were calculated based on the me thod used in the Atlanta Summer 2002 and Atlanta and Chicago Summer 2003 (Zielinska et al, 2003b, 2004b) reports. The NMVOC PID time series was used to reconstruct benzene values (the remaining TEX species follow the benzene time series) and the CO time se ries was used to reconstruct HCHO and 1,3- BD values . No CO and NMVOC data were used where the average CO or

### 1

- 23 NMVOC was below the approximate detection limit of the instruments (0.5 ppmv and 25 ppbv, respectively). In each case the approach was the same. The mean value of the compound to be reconstructed was multiplied by the ratio of the surrogate mean to the instantaneous reading. For example , to produce the 1 st 

### minute value for benzene, the mean benzene canister value was multiplied by the 1 st 

### minute NMVOC reading divided by the mean NMVOC reading. For HCHO and 1,3- BD

, the NDIR CO value was used for all cases where it was available and valid.

A summary of the reconstructed data is presented in Tables 1.3.2-2 and 1.3.2- 3 for benzene, 1,3- BD and HCHO (the c omplete data set is submitted in electronic form) for summer and winter, respectively. The average maximum and minimum values for each ME in each city and season are shown. The reconstructed time series are graphically presented in Figure 1.3.2 -1 through 1.3.2-3 for selected MEs to illustrate the variability of exposure.

For in -cabin exposures in Figure 1.3.2-1 and upper part of Figure 1.3.2-2, the first 20

min utes of measurement was carried out under high ventilation conditions (i.e. window open, air

rec irculation off), whereas for the remaining 20 min utes at low ventilation (i.e. window closed, air conditioning or heating on, air recirculation on). As can be seen , the second 20 min utes of

measurement are less variable . In addition, the concentration of b enzene is rising steadily for this latter sampling period , reflect ing the rising NMVOC signal, probably due to accumulation of outgasing emissions from vehicle cabin material and the breath of people present in the vehicle

cabin.

For refueling experiment s (in -cabin ME3 and active out-of-cabin refueling ME7) the highest exposures occurred during the active refueling performed during the second 10 min utes
of the sampling period . The highest concentrations are observed for BTEX species as expected from evapo rative and spillage emissions during active refueling. HCHO and 1,3- BD present in

exhaust emissions are lower and usually not correlated with benzene, as can be seen for ME3 in Fig. 1.3.2-2.

As shown in Figure 1.3.2-3, outdoor exposures (ME8, ME 9 and ME 12) are usually low

and less variable. HCHO seems higher than benzene and 1,3- BD as is also evident from Figures 1.3.1-1 to 1.3.1-6 and Tables 1.3.1-1 and -2. On the other hand, outdoor surface parking (ME10) and out-of-cabin underground garage (ME11) MEs show much higher variability corresponding

to vehicles exiting the parking lots after the game (ME10) or at the end of a work day (ME11).

We collected 5

- mi nute canister samples at peak of exposures for ME7, ME 11, and ME6

in Houston and Chicago and ME 13 in Atlanta. Table 1.3.2-4 shows the average concentrations of BTEX, 1,3-BD and MTBE for these selected samples (full data set provided in electronic form). Figures 1.3.2-4 show the correlations for benzene and 1,3- BD , respectively, quantified from

these 5

- min ute canisters and averaged over corresponding 5- min ute surrogate 1- minute

measurement s. ME7 values for Houston w ere removed from these correlations since high MTBE

levels distort NMVOC PID signal correlation to benzene. An obvious outlier from Atlanta (ME7, summer) was also removed. As seen from these figures, correlations are reasonable, especially for benzene (R 2 

### = 0.87).1-24 

### Table 1.3.2- 1A. Correlation coefficients (R 2 

### ) and associated statistic for relations hips of time

- integrated measurements with continuous methods ( NMVOC and CO) for 3 cities, without ME3 and ME7

PID CO_NDIR

r2 Slope Intercept df F

stat Fcrit P

- value r2 Slope Intercept df F

stat Fcrit P

- value

Atlanta

Benzene 0.88 7.36 2.38 88 675 3.9 0.0 0%
1,3

- BD 0.55 31.05 20.29 88 107 3.9 0.00% 0.68 2.43 1.25 41 88 4.1 0.00% Formaldehyde 0.39 0.35 1.79 41 27 4.1 0.00% CO_can 0.93 0.90

- 0.01 41 514 4.1 0.00% Chicago

Benzene 0.82 7.86

- 0.85 87 406 4.0 0.00%
1,3

- BD 0.61 25.55 6.33 87 136 4.0 0.00% 0.70 2.35 0.82 46 106 4.052 0.00% Formaldehyde 0.20 0.38 0.65 46 11 4.052 0. 15 % CO_can 0.94 0.95

- 0.07 46 687 4.052 0.0 0 %

Houston

Benzene 0.70 9.02 26.16 71 162 4.0 0.00%
1,3

- BD 0.70 24.86 28.75 71 169 4.0 0.00% 0.81 2.00 0.11 43 181 4.1 0.0 0 % Formaldehyde 0.29 0.70

- 1.37 43 18 4.1 0.0 1 % CO_can 0.88 1.08

- 0.38 43 309 4.1 0.0 0 %



### Notes: F- stat = performance statistic for regression slope of 2

- tailed paired data: Critical F

- value for 95% confidence is shown.

P- value = probability that correlation is not significant df = degrees of freedom (number of data pairs - 2)1-25 

### Table 1.3.2- 1B. Correlation coefficients (R 2 

### ) and associated statistic for relationships of time

- integrated measurements with continuous methods (NMVOC and CO) for ME3 and ME7 in 3 cities

PID CO_NDIR

r2 Slope Intercept df F

stat Fcrit P

- value r2 Slope Intercept df F

stat Fcrit P

- value

Atlanta

Benzene 0.57 1 2.15 1274.84 53 70 4.0 0.0 0%
1,3

- BD 0.34 159.97 729.81 47 5 4.0 2. 47 % 0.06

- 0.03 0.55 12 1 4.7 41.7 1 % Formaldehyde 0.01 0.02 1.09 2 1 18.5 38.3 1 % CO_can 0.41 0.58 0.59 2 2 18.5 28. 05 % Chicago

Benzene 0.96 15.76

- 4.47 25 590 4.2 0. 0 0%
1,3

- BD 0.04 43.11 238.60 25 1 4.2 30. 37 % insufficient data available Formaldehyde insufficient data available CO_can insufficient data available

Houston

Benzene 0.52 10.94 2896 .65 27 30 4.2 0.0 0 %
1,3

- BD 0.22 116.19 1878.18 19 5 4.4 3. 36 % 0.01 0.01 0.92 5 1 6.6 34. 28 % Formaldehyde 0.42

- 0.22 2.72 3 2 10.1 22. 15 % CO_can 0.75 0.78

- 0.08 3 11 10.1 4. 49 %



### Notes: F- stat = performance statistic for regression slope of 2

- tailed paired data: Critical F

- value for 95% confidence is shown.

P- value = probability that correlation is not significant df = degrees of freedom (number of data pairs - 2)

### 1

- 26 Table 1.3.2-2. Summary of the reconstructed 1- min ute data (ppbv), Summer

City ME Benzene 1
, 3

- B D HCHO

min max min max min max A 01 0.00 47.38 0.00 16.59 0.00 34.25

A 02

A 03 0.00 103.60 0.00 0.67 0.00 29.42

A 04 0.00 49.48 0.00 8.20 0.00 92.53

A 05

A 07 0.00 976.35

A 08

A 09

A 10 0.95 18.57 0.00 8.55 0.00 75.30

A 11 7.68 51.30 0.90 9.19 12.82 70.80

A 12 1.62 11.57 0.31 3.40 3.79 29.95

A 13 0.00 253.74 0.00 19.14 0.00 141.72

C 01 0.00 31.98 0.01 0.85 0.00 13.56

C 02 0.00 11.42 0.01 1.75 0.11 13.09

C 03 0.00 30.18

C 04 0.50 15.39 0.74 4.61 3.64 35.66

C 05 0.80 0.00 17.55

C 06 0.10 65.31 0.20 11.65 1.13 64.03

C 07 0.00 111.01

C 08 0.29 0.40 3.81 7.65

C 09 0.15 0.45 3.66 7.85

C 10 0.01 2.14 0.04 14.25

C 11 0.20 20.73 0.09 4.11 0.00 25.9 9

C 12 0.31 0.77 6.15 11.60

H 01 0.95 6.89 0.06 9.25 0.50 47.92

H 02 0.82 2.02 0.03 7.95 0.27 78.24

H 03 0.00 1346.97 0.23 3.66 1.67 26.55

H 04 2.09 13.44 0.48 6.00 1.86 23.44

H 05 1.19 4.04 0.14 2.80 0.63 26.49

H 06 1.31 16.95 0.12 6.23 0.89 25.6 1

H 07 0.00 1948.10 2.85 45.79

H 08 0.27 2.80 0.00 0.68 0.00 17.17

H 09 0.18 0.87 0.04 0.43 1.20 17.69

H 10 0.90 5.71 0.11 3.93 1.47 50.49

H 11 1.88 15.71 0.14 6.08 1.13 53.69

H 12 0.85 17.54 0.08 2.74 0.95 13.09

### 1

- 27 Table 1.3.2-3. Summary of the reconstructed 1-min data (ppbv), Winter

City ME Benzene 13

- B D Formaldehyde

min max min max min max A 01 0.02 1.28 0.25 15.70

A 02 1.60 3.87 0.07 1.34 0.82 15.71

A 03 0.59 107.31

A 04 2.71 67.30 0.07 13.32 0.22 43.93

A 05 0.02 1.98 0.24 17.4 9

A 07 0.00 1080.63 3.44 19.02

A 08 0.74 2.17 0.23 0.41 3.15 5.69

A 09 1.06 1.81 0.27 0.53 2.48 4.79

A 10 3.11 13.55 0.08 3.07 1.35 41.48

A 11 1.66 49.76 0.05 17.32 0.21 50.86

A 12 0.81 6.53 0.17 1.33 1.11 11.75

A 13 0.53 33.96 0.05 6.36 0.20 42.7 8

C 01 0.17 1.20 0.07 7.40 0.26 64.35

C 02

C 03 0.00 98.94

C 04 3.72 31.25 0.97 8.97 4.45 25.70

C 05 0.04 0.72 0.65 11.37

C 06 0.13 8.53 0.06 1.63 0.45 14.92

C 07 0.00 511.90 0.58 4.57 0.86 6.75

C 08 0.10 1.71 0.94 10.07

C 09 0.00 0.53 0.00 8.02

C 10 0.07 2.54 0.47 18.27

C 11 3.01 33.48 0.11 5.63 0.45 26.76

C 12 0.00 0.65 0.00 8.87

H 01 0.60 6.34 0.06 3.13 0.58 23.47

H 02 0.82 13.93

H 03 0.47 335.71 0.11 1.86 0.74 12.11

H 04 1.22 17.85 0.11 6.57 2.40 33.89

H 05 0.67 3.25 0.07 1.68 0.69 16.77

H 06 0.46 7.77 0.01 4.72 0.15 23.07

H 07 0.15 1203.84 0.25 20.29

H 08 0.35 0.62

H 09 0.28 1.06

H 10 1.16 32.64 0.08 12.89 0.13 22.73

H 11 3.71 18.66 1.23 12.10 2.41 16.98

H 12 1.43 3.76

### 1

- 28 Table 1.3.2-4. Summary of the 5- min ute canister data (ppbv)

City Atlanta, Summer Atlanta, Winter

ME 7 11 13 7 11 13 Replicates 5 5 4 6 5 5 1,3

- BD Ave. 1.53 5.39 1.20 6.48 7.23 1.79

Min. 0.04 3.97 0.79 0.78 0.51 0.48

Max. 4.09 7.50 1.90 15.47 10.13 2.72

B enzene Ave. 163.98 33.26 6.30 89.52 27.95 8.11

Min. 3.06 24.80 4.36 13.52 1.51 1.90

Max. 475.82 45.07 10.34 256.31 42.40 16.02

Toluene Ave. 253.17 94.52 15.30 139.88 70.84 29.44

Min. 8.90 68.88 10.97 48.39 3.94 4.62

Max. 649.81 126.79 20.41 360.24 113.45 67.34

Et hylb enzen e Ave. 23.15 16.06 2.42 8.82 11.89 3.91

Min. 1.45 11.89 1.89 3.86 0.64 0.69

Max. 57.14 22.88 2.93 20.24 19.79 8.50 Xylene Ave. 79.33 62.04 9.60 29.86 48.27 17.52

Min. 6.21 44.84 7.39 15.90 2.69 3.01

Max. 202.27 87.73 12.7 2 64.24 77.88 38.85

City Chicago, Summer Chicago, Winter

ME 6 7 11 6 7 11 Replicates 5 5 5 5 4 4 1,3

- BD Ave. 1.51 0.21 2.33 0.73 2.19 4.00

Min. 0.94 0.03 0.80 0.51 1.44 1.79

Max. 2.66 0.39 3.01 1.45 2.74 5.75

Benzene Ave. 8.87 13.56 7.75 2.22 84.25 12.00

Min. 4.11 0.56 2.50 1.59 24.98 6.15

Max. 24.00 37.23 10.00 3.94 160.53 17.32

Toluene Ave. 25.53 22.74 19.40 3.56 56.51 23.92

Min. 5.87 0.57 5.57 2.14 32.96 12.82

Max. 78.10 61.34 25.73 6.48 100.48 36.75

Et hylb enzen e Ave. 2.69 2.77 3.3 1 0.59 6.11 4.03

Min. 1.23 0.11 1.17 0.36 2.12 2.01

Max. 6.80 6.78 4.63 1.04 11.90 6.00 Xylene Ave. 9.43 11.19 12.74 2.89 25.92 18.75

Min. 4.83 0.38 4.35 1.67 9.31 9.43

Max. 23.42 26.91 18.57 5.33 51.91 27.41

### 1

- 29 City Houston, Summer Houston, Win ter

ME 6 7 11 6 7 11 Replic a tes 4 5 5 5 5 5 1,3

- BD Ave. 4.55 4.04 4.22 1.79 76.11 3.18

Min. 1.24 1.36 0.55 0.81 13.03 0.39

Max. 10.07 6.72 12.85 3.18 174.21 5.15

Benzene Ave. 12.51 918.86 11.05 4.32 379.48 9.47

Min. 4.17 181.85 1.99 2.53 49.61 1.91

Max. 27.86 2429.61 26.71 7.91 607.22 16.60

Toluene Ave. 21.28 815.73 27.31 7.30 420.64 19.84

Min. 6.59 360.54 4.79 4.98 64.85 2.98

Max. 50.32 1142.43 62.52 13.52 835.98 38.04

Et hylb enzen e Ave. 4.25 94.58 5.34 1.32 23.92 3.85

Min. 1.47 44.53 1.12 0.85 4.22 0.50

Max. 10.08 135.65 13.00 2.70 51.83 7.59 Xylene Ave. 5.31 368.47 6.40 5.78 100.90 16.07

Min. 6.74 132.36 4.38 4.13 16.87 2.14

Max. 11.78 553.69 15.03 10.98 205.55 32.78

MTBE Ave. 36.50 26977.95 30.06 15.28 9705.27 32.96

Min. 13 .65 3319.53 5.71 5.47 2019.60 14.29

Max. 67.35 61643.39 48.23 39.34 15484.50 65.53ME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin und erground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-30 ME1, Houston Summer 2004

0 2 4 6 8 10 12 14070807100712071407160718072007220724072607280730073207340736073807400742074407460748ppbv

benz_pid bud13_co form_co ME2, Atlanta Winter 2004

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.507450746074707480749075007510752075307540755075607570758075908000801080208030804080508060807080808090810081108120813081408150816081708180819082008210822082308240825Benzene, 1,3-BD, ppbv

0 2 4 6 8 10 12 14 16 18Formaldehyde, ppbv

benz_pid 13-BD_co Form_co

ME4, Atlanta Summer 2003

0 5 10 15 20 25 30

1720 1723 1726 1729 1732 1735 1738 1741 1744 1747 1750 1753 1756 1759ppbv

benz_pid 13-BD_co Form_co ME5, Houston Summer 2004

0 2 4 6 8 10070507070709071107130715071707190721072307250727072907310733073507370739074107430745ppbv

benz_pid bud13_co form_co



### Figure 1.3.2-1. 1- Min ute time series for in -cabin exposures: ME1 (congested freeway), ME2 (urban canyon); ME4 (underground garage) and ME5 (to ll plaza)ME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin und erground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-31 ME6, Houston Summer 2004

0 2 4 6 8 10 12 14 16 18074707490751075307550757075908010803080508070809081108130815081708190821082308250827ppbv

benz_pid bud13_co form_co ME13, Atlanta Winter 2004

0 5 10 15 20 25 30 35113111331135113711391141114311451147114911511153115511571159120112031205120712091211ppbv

benz_pid 13-BD_co Form_co

ME3, Chicago, Winter 2004

0 20 40 60 80 100 120

1330 1332 1334 1336 1338 1340 1342 1344 1346 1348 1350ppb

benz_pid 13BD_co Form_co



### Figure 1. 3.2-2. 1- Min ute time series for in -cabin exposures: ME6 (tunnel); ME13 (following high- emitting vehicle); ME3 (in

- cabin refueling) and out-of- cabin refueling, ME7 ME7, Houston Summer 2004

0 500 1000 1500 2000 2500124812491250125112521253125412551256125712581259130013011302130313041305130613071308ppbv

bud13_co form_co benz_pidME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin und erground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-32 ME8, Atlanta Winter 2004

0 1 2 3 4 5 611551157115912011203120512071209121112131215121712191221122312251227122912311233ppbv

benz_pid 13-BD_co Form_co ME10, Chicago, Summer 2003

0 5 10 15 20 252100210121022103210421052106210721082109211021112112211321142115211621172118211921202121212221232124212521262127212821292130213121322133213421352136213721382139214021412142214321442145214621472148214921502151215221532154215521562157215821592200Benzene, 1,3-BD,ppb

0 5 10 15 20 25 30 35 40 45Formaldehyde, ppb

benz_pid bud13_co form_co

Me11, Houston Summer 2004

0 5 10 15 20 25162016221624162616281630163216341636163816401642164416461648165016521654165616581700ppbv

benz_pid bud13_co form_co ME12, Chicago Winter 2004

0 1 2 3 4 5 6 7161616181620162216241626162816301632163416361638164016421644164616481650165216541656ppbv

benz_pid 13BD_co Form_co



### Figure 1.3.2-3. 1- Min ute time series for out

- of cab in outdoor exposures:ME8 (sidewalk); ME10 (surface parking); ME11 (underground garage) and ME12 (toll plaza)ME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin und erground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-33



### Figure 1.3.2-4. Correlations between 5- min ute canister samples and surrogate 1

- min ute values

, averaged over corresponding 5

min utes

. Benzene - No ME7 in Houston

y = 1.0955x - 2.7164

R 2 = 0.8747

0 50 100 150 200 250 300 350 400 450 500

0 50 100 150 200 250 300 350

5-Min Ave Surrogates5-Min Can 

### 1,3-Butadiane - No ME7 in Houston

y = 1.1847x + 0.5092

R 2 = 0.5695

0 2 4 6 8 10 12 14

0 2 4 6 8 10

5-min Ave Surrogates5-min Can

### 1

- 34 1.3.3 Oxygenated and conventional gasoline (difference between cities)

The MTBE and EtOH concentration variability by ME in Houston and Chicago is shown in Figure 1.3.3-1. The complete data are provided in electronic form. Although MTBE is

mea sured in all Houston MEs, the concentrations recorded during refueling are relatively high, in the range of a few ppm v. In contrast, Chicago ethanol concentrations are lower, especially during

winter time. We generally use the same gas station in each city ( absent problems with the gas

station manager) and we select a station with high traffic close to a major freeway. For example, the gas station in Houston was situated next to Tollway 8 and was always very busy.

The high concentrations of MTBE during refueling in Houston caused occasional problems with 1,3- BD quantification in canister samples as discussed at Section 1.3.1. In addition, MTBE PID response changed the slope of canister benzene and NMVOC PID regressions in Houston ME s from those observed in Chicago and Atlanta, as shown in Table 1.3.2-1. However, when ME3 and ME 7 data are removed from correlations, the slopes are more consistent among the three cities.

Figures 1.3.3- 2 and -3 show comparisons of average benzene, 1,3

- BD, HCHO, and CO

concen trations by ME in the three cities by season . Tables 1.3.1-1 and 1.3.1-2 provide the data for all species measured with the time

- integrated methods. For refueling MEs , the highest benzene concentrations are observed in Houston, in both seasons. However, fo r underground

garage MEs , Atlanta shows the highest concentrations of benzene, HCHO, and CO. It is however

not clear whether these findings result from the different fuels, choice of specific ME locations,

or the greater variability of high -end ME exposure s in general.ME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitte r vehicle1-35ppbv 

### Houston, Summer 2004

MTBE

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 600 1200 1800 2400 3000 3600 4200 4800 5400 6000

Maximum
Minimum

75%
25%
Median
Outliers
Extremesppbv 

### Houston, Winter 2005

MTBE

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 600 1200 1800 2400 3000 3600 4200 4800 5400 6000

Maximum
Minimum

75%
25%
Median
Outliers
Extremesppbv 

### Chicago, Summer 2003

Ethanol

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 15 30 45 60 75 90 105 120

Maximum
Minimum

75%
25%
Median
Outliers
Extremesppbv 

### Chicago, Winter 2004

Ethanol

ME1 ME2 ME3 ME4 ME5 ME6 ME7 ME8 ME9 ME10 ME11 ME12 0 1.5

3 4.5

6 7.5

9 10.5

12 13.5

Maximum
Minimum

75%
25%
Median
Outliers
Extremes



### Figure 1.3.3-1. MTBE and EtOH concentrations in Houston and Chicago, respectively..Note different y- axis scales for Chicago Sumer

and WinterME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitte r vehicle1-36 Benzene

0 20 40 60 80 100 120 140

1 2 3 4 5 6 7 8 9 10 11 12 13ppbv

Houston Atlanta Chicago 1,3-Butadiene

0 1 2 3 4 5 6 7 8 9

1 2 3 4 5 6 7 8 9 10 11 12 13ppbv

Houston Atlanta Chicago

Formaldehyde

0 5 10 15 20 25 30 35

1 2 3 4 5 6 7 8 9 10 11 12 13ppbv

Houston Atlanta Chicago CO

0 2 4 6 8 10 12 14 16

1 2 3 4 5 6 7 8 9 10 11 12 13ppm

Houston Atlanta Chicago



### Figure 1.3.3-2. Comparison of benzene, 1,3- BD

, HCHO, and CO average co ncentrations in three cities in SummerME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitte r vehicle1-37 Benzene

0 10 20 30 40 50 60

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Atlanta Chicago Houston 1,3-Butadiene

0 2 4 6 8 10 12

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Atlanta Chicago Houston



### Formaldehyde

0 5 10 15 20 25

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Atlanta Chicago Houston CO

0 5 10 15 20

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppm

Atlanta Chicago Houston



### Figure 1.3.3-3. Comparison of benzene, 1,3- BD

, HCHO, and CO average concentrations in three cities in Winter

### 1

- 38 1.3.4 Effect of meteorology on exposure

As shown in Figures 1.3.3-1 through 1.3.3-6 the highest day-to-day variations in in- cabin or out-of-cabin exposures occur during refueling, in ME3 and ME7. ME4 and ME11 relate to exposures in an underground garage so these MEs are not subject to different meteorological conditions. However, wind speed and direction play an important role in refueling MEs. As a general rule, we performed refueling experiments under calm conditions (wind speeds ≤ 4 mph). Also, it was usually possible to find a pump location that was relatively sheltered from the direct

influences of th e wind

. Subjects generally stood downwind during refueling tests

. As a result,

correlation s of wind speed and concentrations in the refueling ME s w ere weak

. For example,

summer ME7 BTEX levels were highest in Chicago w ith a steady wind speed of 2-3 mph and

lowest at variable wind speeds of 1-3 mph.

Table 1.3.4-1 list s average outdoor ambient temperature s and relative humidity by ME, city , and season. The detailed data recorded during each test are provided in electronic form.

Table 1.3.4-1. Average, minim um, and maximum ambient temperature s and RH City Season ME Replicate Temperature ( o C) RH (%)

ave min max ave min max A S 1 5 27.6 27 29 58.4 56 60

A S 2 3 24.3 22 27 42.6 33 63

A S 3 5 32.0 26 37 61.8 44 74

A S 4 5 32.2 31 33 52.2 46 61

A S 5 3 24.2 22 26 49.9 36 72

A S 7 5 29.5 22 34 63.0 57 86

A S 8 3 33.7 29 39 41.0 29 65

A S 9 3 33.7 29 39 41.0 29 65

A S 10 3 31.9 22 41 42.6 20 69

A S 11 5 33.2 32 35 47.8 42 51

A S 12 3 27.1 24 32 58.8 42 77

A S 13 5 41.2 37 46 49.4 47 54

C S 1 5 27.0 26 28 52.2 46 55

C S 2 3 25.0 24 26 45.7 42 49

C S 3 6 30.5 24 35 51.8 45 63

C S 4 5 26.4 23 28 60.8 56 66

C S 5 3 29.7 26 33 56.7 54 61

C S 6 5 30.0 29 31 53.4 50 57

C S 7 5 28.6 24 31 59.0 50 68

C S 8 3 25.0 23 27 55.0 54 56

C S 9 3 26.3 25 28 5 3.3 51 55

C S 10 3 21.0 20 23 70.3 67 73

C S 11 5 28.4 22 33 56.6 46 67

C S 12 3 31.7 30 34 43.0 31 57

H S 1 5 33.8 30 37 55.6 51 63

### 1

- 39 City Season ME Replicate Temperature ( o C) RH (%)

ave min max ave min max H S 3 5 36.8 30 41 48.6 42 59

H S 4 5 31.0 30 33 43.0 37 53

H S 5 3 29.3 29 30 56.0 54 58

H S 6 5 37.8 32 42 51.0 48 57

H S 7 5 36.6 29 40 54.0 48 70

H S 8 3 31.0 28 33 59.3 42 76

H S 9 3 31.7 28 34 59.3 49 78

H S 10 3 36.0 27 53 58.0 40 69

H S 11 5 31.8 27 35 49.6 41 59

H S 12 3 3 0.0 30 30 68.0 66 70

A W 1 5 12.2 4 27 35.4 21 49

A W 2 3 10.0 7 13 33.0 29 37

A W 3 5 11.8 7 18 40.8 29 56

A W 4 5 15.2 9 19 42.0 30 47

A W 5 3 13.3 7 17 31.0 27 34

A W 7 6 10.7 7 17 55.8 42 82

A W 8 3 3.7 1 6 64.3 45 76

A W 9 3 3.7 1 6 63.3 45 73

A W 10 3 10.3 7 15 52.7 38 64

A W 11 5 15.4 8 21 47.8 27 64

A W 12 3 9.3 6 15 55.7 22 77

A W 13 5 14.2 4 26 37.2 23 50

C W 1 5 7.0 0 12 19.8 10 26

C W 2 3 6.7 4 9 24.0 21 26

C W 3 5 6.3 4 11 22.0 14 32

C W 4 5 11.4 13 16 30.2 26 60

C W 5 3 7.0 3 10 18.0 13 22

C W 6 5 6.8 3 10 25.0 14 42

C W 7 5 6.9 2 9 27.0 32 63

C W 8 3 4.7 1 9 46.7 32 63

C W 9 3 6.3 2 12 43.3 28 61

C W 10 3 6.0 1 9 37.3 32 42

C W 11 5 13.6 11 15 42.0 30 62

C W 12 3 2.0 0 5 53.7 25 78

H W 1 5 14.8 9 24 41.6 30 59

H W 2 3 14.7 9 21 37.3 34 43

H W 3 5 16.2 10 23 52.8 38 62

H W 4 5 15.6 10 19 54.4 36 69

H W 5 3 15.0 8 20 49.7 44 56

H W 6 5 22.4 14 25 46.6 34 55

H W 7 5 15.8 10 22 67.6 56 77

H W 8 3 9.7 7 12 61.0 53 71

H W 9 3 11.7 8 15 56.0 47 67

H W 10 3 16.3 14 21 63.3 48 76

H W 11 5 15.4 9 19 69.8 43 87

H W 12 3 15.0 8 20 78.0 70 83

### 1

- 40 1.3.5 Comparison of summer and winter exposures

Figures 1.3.5-1 through 1.3.5- 3 shows the differences between exposures in each city during the summer and winter seasons. For Chicago, the concentrations of benzene, 1,3- BD , and CO are higher in the underground garage (ME4 and ME 11) during winter season. The same is

true for ME3 and ME 7, although CO concentrations are low and comparable for these refueling MEs, as expected. However, HCHO is clearly higher during the summer season in all MEs, perhaps a result of photochemical formation of this compound. In Houston, benzene is clearly much higher in refueling MEs in summer. However, for ME4 and ME 11, winter concentrations

are also marginally higher for benzene, 1,3- BD and CO. HCHO is less consistent, but clearly higher in summer in outdoor MEs (8, 9, 10, and 12). For Atlanta, the differences are not very large between winter and summer seasons, and not very consistent between different species a nd MEs. However, HCHO is clearly higher in summer in outdoor MEs (7, 8, 9, 10, and 12).ME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :O ut

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-41



### Figure 1.3.5-1. T ime integrated average exposure levels in different MEs in Atlanta in Summer and Winter season

. Atlanta, Benzene

0 10 20 30 40 50

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Benzene_S Benzene_W Atlanta, 1,3-Butadiane

0 1 2 3 4 5

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

1,3-BD_S 1,3-BD_W



### Atlanta, Formaldehyde

0 5 10 15 20 25 30 35

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Formal_S Formal_W 

### Atlanta, CO

0 5 10 15 20

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppmv

CO_S CO_WME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :O ut

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-42



### Figure 1.3.5-2. Time integrated average exposure levels in different MEs in Chicago in Summer and Winter season Chicago, Benzene

0 5 10 15 20 25

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Benzene_S Benzene_W Chicago, 1,3-Butadiane

0 1 2 3 4 5

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

1,3-BD_S 1,3-BD_W



### Chicago, CO

0 2 4 6 8 10 12 14

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppmv

CO_S CO_W Chicago, Formaldehyde

0 2 4 6 8 10 12 14 16 18

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Formal_S Formal_WME1 : In

- cabin congested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :O ut

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-43



### Figure 1.3.5-3. Time integrated average exposure levels in different MEs in Houston in Summer and Winter season Houston, Benzene

0 20 40 60 80 100 120 140

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Benzene_S Benzene_W 

### Houston, 1,3-Butadiane

0 1 2 3 4

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

1,3-BD_S 1,3-BD_W

Houston, Formaldehyde

0 2 4 6 8 10 12

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppbv

Formal_S Formal_W Houston, CO

0 2 4 6 8 10

0 1 2 3 4 5 6 7 8 9 10 11 12 13

MEppmv

CO_S CO_W

### 1

- 44 1.3.6 Correlations to breath concentrations

Figures 1.3.6-1 and 1.3.6-2 shows the average concentrations of BTEX, 1,3- BD , MTBE,

EtOH and CO 2



### Figure 1.3.6-3 (upper panel) shows the correlations between 1- min ute maximum surrogate values for benzene and 1,3-BD and post-exposure breath concentrations of the se species. The correlation is somewhat better for 1,3

- BD (R measured in pre - and a post-peak exposure breath for three MEs in each city and

season. D etailed data are submitted in the electronic form. As it can be seen from these figures, a considerable increase in concentrations of measured species occur s in all cases immediately after a peak exposure. In Atlanta and Chicago, the highest breath concentrations of BTEX and 1,3- BD were observed in ME7 (refueling) and ME11 (underground garage). In Houston, high concentrations of MTBE were measured in ME7 in summer and winter. Although high

concentrations of EtOH were measured in breath in all Chicago MEs, i t is not clear if this is due wholly to the presence of EtOH in Chicago fuel, since pre-exposure breath concentrations were occasionally higher than the post-exposure concentrations. Subjects were cautioned against consuming alcoholic beverages or using alcoholic personal care products prior to breath testing

but EtOH may also be a metabolic product for certain other food type s. For example, it has been reported (Turner et al., 2006) that increased ethanol levels were observed in the breath of healthy individuals if sweet drinks/food had been consumed within 2 hr prior to providing breath samples.

2 

### = 0.46) than for benzene (R 2 

### = 0.26) ; however, benzene concentrations in these MEs are much higher than breath concentrations. As shown in the lower panel of Figure 1.3.6-3, both benzene and 1,3-BD concentrations in breath

track well these compound concentrations in all MEs. Note that the logarithmic scale was used

for benzene and that no ME3 and ME7 data were included in 1,3-BD correlations for Houston. Also, some 1- min ute surrogate 1,3-BD and b enzene values are missing for certain MEs. As explained in Section 1.3.2, if the CO or NMVOC values were below the approximate detection limits of the continuous CO and PID instruments (0.5 ppmv and 25 ppbv, respectively), no 1- min surrogate data were calculated. D ata used for these plots are submitted in electronic form.ME1 : In

- cabin c ongested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME 10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-45



### Figure 1.3.6-1. Average breath BTEX, 1,3

- BD , MTBE, EtOH, and CO2 concentrations in three cities in Summer Chicago, Summer 2003

0 2 4 6 8 10 12 14

ME6pre ME6post ME7pre ME7post ME11pre ME11postBTEX, ppb

0 20 40 60 80 100 120 140EtOH, ppb

BTEX EtOHME1 : In

- cabin c ongested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME 10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-46



### Figure 1.3.6-2. Average breath BTEX, 1,3

- BD , MTBE, EtOH, and CO2 concentrations in three cities in Winte r Chicago, Winter 2004

0 5 10 15 20 25 30

ME6-pre ME6-post ME7-pre ME7-post ME11-pre ME11-
postBTEX, ppbv

0 50 100 150 200 250 300 350 400 450EtOH, ppbv

BTEX EtOHME1 : In

- cabin c ongested freeway; ME2 : In

- cabin urban canyon; ME3 : In

- cabin refueling; ME4 : In

- cabin underground garage; ME5 : In

- cabin toll plaza; ME6 : In

- cabin roadway tunnel; ME7 : Out

- of

cabin refueling; ME8 :Out

- of

- cabin sidewalk; ME9 : Out

- of

- cabin sidewalk/bus stop; ME 10 : Out

- of

- cabin surface parking; ME11 : Out

- of

- cabin underground garage; ME12 : Outside toll plaza; ME13 : In

- cabin trailing high

- emitter vehicle1-47



### Figure 1.3.6-3. Correlations between 1

- min ute surrogate benzene and 1,3

- BD max values and post-exposure breath concentrations (upper panel) and comparison of these concentrations in different ME and cities (lower panel) Benzene

y = 0.0105x + 4.7492

R 2 = 0.2314

0 5 10 15 20 25 30 35 40

0 500 1000 1500 2000 2500

1-min maxPeak Breath 1,3-Butadiane

y = 0.6102x + 0.1788

R 2 = 0.4612

0 2 4 6 8 10 12

0 2 4 6 8 10 12 14

1-min maxPeak Breath

Benzene

0 1 10 100 1000 10000AS07M_1AS07M_3AS07M_5AS11M_2AS11M_4AS13M_1AS13M_5AW07M_2AW07M_4AW07M_6AW11M_2AW11M_4AW13M_1AW13M_3AW13M_5CS06M_2CS06M_4CS07M_2CS11M_2CS11M_4CW06M_5CW07M_4CW11M_1CW11M_4HS06M_2HS06M_4HS07M_1HS07M_3HS07M_5HS11M_3HS11M_5HW06M_2HW06M_4HW07M_1HW07M_3HW07M_5HW11M_3HW11M_5

benz_1min benz_breath 1,3-Butadiane

0 2 4 6 8 10 12 14AS11B_1BAS11B_3BAS13B_1BAS13B_5BAW11B_2BAW11B_4BAW13B_1BCS06B_1BCS06B_3BCS11B_2BCS11B_4BCW06B_1BCW06B_3BCW06B_5BCW11B_1BCW11B_4BHS06B_1BHS06B_3BHS06B_5BHS11B_2BHS11B_4BHW06B_1BHW06B_3BHW06B_5BHW11B_3BHW11B_5B1-Min Max

0 2 4 6 8 10 12Breath

1,3-BD_1min 1,3-BD_breath

### 1

- 48 1.4 Conclusions

Summary findings related to the three city study are as follows:

**•** Day

- to -day variations in high

- end (99 + th



### • With the exception of refueling, exposure levels are g enerally lower in outdoor MEs and higher in enclosed MEs

. per centile) benzene, 1,3- BD, HCHO, and CO concentrations in different MEs are substantial and independent of city and

season , but related to the activity and emission rates of sources in the given MEs which differ from day to day.

**•** The 20- min average refueling benzene exposures range up to few hundred ppbv and show substantial day- to

- day variability.

**•** In -cabin exposures during on-road vehicle operation are more consisten t and un iform

than for other in

- cabin MEs

.

**•** BTEX species show the highest concentrations in refueling MEs dominated by evaporative emissions whereas CO, HCHO, and 1,3- BD are the highest in the cold

start dominated MEs

.

**•** BTEX and 1,3- BD measured by time

- integrated canister method show good

correlation s with continuous NMVOC and CO measurements, respectively. HCHO correlation with continuous CO is modest, probably due to photochemical production of this compound.

**•** Continuous NMVOC ( PID ) and CO (NDIR) data can be used to reconstruct 1- min ute time series for benzene and 1,3-BD, respectively, provided that the averaged

continuous measurements are above the detection limits of the instruments (25 ppb v and 0.5 ppmv, respectively). CO data can also be used to reconstruct 1 -m in ute HCHO

data ; however, l ess reliably so due to poorer correlation between these species.

**•** Reconstructed 1

- min ute time

- series data for benzene and 1,3- BD , averaged over the

five min ute time frame corresponding to the collection of 5- min ute canister sample s, correlate well after excludin g the Houston refueling ME with relatively high TVOC levels that distort typical correlation coefficients and elevated MTBE levels which bias 1,3- BD measurements.

**•** The concentrations of benzene and 1,3-BD measured in post peak exposure breath samples track corresponding ME 1- min ute max imum reconstructed surrogate values

well.

**•** I ncrease s in concentrations of measured species occur in all breath samples collected

within a minute of a peak exposure. In Atlanta and Chicago, the hig hest breath concentrations of BTEX and 1,3- BD w ere observed in ME7 (refueling) and ME11 (underground garage) , respectively . In Houston, high concentrations of MTBE were

measured in ME7.

**•** The largest differences in benzene, 1,3- BD , and CO concentrations between summer

and winter seasons are observed in Chicago, consistent with the largest ambient
temperature difference s for this city. The se concentrations are higher in winter. For

Atlanta and Houston such differences are less pronounced. HCHO is consistently higher in summer season in outdoor environments, probably d ue to the photochemical production of this compound.

### 1

- 49 1.5 References

Batterman, S. S, Peng C-y, Braun, J. (2002). Levels and composition of volatile organic compounds on commuting routes in Detroit, Michigan. Atmos . Environ., 36 :6013-6030.

Chan, C-C., H. Ozkaynak, J. D. Spengler and L. Sheldon (1991). Driver exposure to volatile organic compounds, CO ozone, NO2 under different driving conditions. Environ. Sci. Technol., 25 : 964-972.

Fedoruk, M.J. and Kerger, B.D. (2003). Measurements of volatile organic compounds inside

automobiles. Journal of Exposure Analysis and Environmental Epidemiology

, 13 :31-41

Lindstrom A.B. and J.D. Pleil (1996). Alveolar Breath Sampling and Analysis to Assess Exposures to Met hyl Tertiary Butyl Ether (MTBE) During Motor Vehicle Refueling. J. Air & Waste Manage. Assoc

., 46 :676-682.

Pleil, J. D.and A. Lindstrom (2002). A review of the USEPA’s single breath canister (SBC) method for exhaled volatile organic biomarkers. Biomarkers

, 7 :189-208.

Rodes, C., L. Sheldon,, D. Whitaker, et al., (1998). Measuring Concentrations of Selected Air

Pollutants Inside California Vehicles. Final report, ARB Contract # 95-339. California

Air Resources Board.

Turner, C., P. Spanel and D. Smith (2006). A longitudinal study of ethanol and acetaldehyde in the exhaled breath of healthy volunteers using selected -ion flow- tube mass spectrometry. Rapid Commun. Mass Spectrom.

, 20 :61-68.

Vayghani, S. A. and C. Weisel (1999). The MTBE air concentrations in the cabin of automobiles while fueling. Journal of Exposure Analysis and Environmental Epidemiology

, 9 :261-

267.

Weisel, C., N. J. Lawryk, P. J. Lioy (1992). Exposure to emissions from gasoline within

automobile cabins. J. Expo Anal Environ Epidem

, 2 (1):79 -96.

Zielinska, B., E. Fujita, J. Sagebiel, G. Harshfield, E. Uberna, T. Hayes, and F. Keene (1998). Arizona Hazardous Air Pollutants Monitoring Program. J. Air Waste Manage. Assoc.,
48 :1038-1050.

Zielinska, B., E. M. Fujita, J.C. Sagebiel, D. E. Campbell, L.R. Smith, T. Johnson (2003a). Exposure Protocol and Study Plan for the Section 211 (B) Tier 2 High End Exposure Screening Study of Baseline and Oxygenated Gasoline. Prepared for American Petroleum Institute, 1220 L Street, Washington, DC 20005-4007. Final Ver sion. October 1, 2003.

Zielinska, B, E.M. Fujita, and J.C. Sagebiel (2003b ). Section 211 (B) Tier 2 High End Exposure Screening Study of Baseline and Oxygenated Gasoline -Summer 2002 Atlanta Field Study

on Baseline Gasoline. Prepared for American Petroleum Institute, 1220 L. Street, Washington, DC 2005-4070. March 13, 2003.

Zielinska, B, J.C. Sagebiel, D.Campbell and E.M. Fujita, (2004a). Section 211 (B) Tier 2 High End Exposure Screening Study of Baseline and Oxygenated Gasoline-Summer 2003 Chicago and Atlanta Field Study on Baseline Gasoline. Prepared for American Petroleum Institute, 1220 L. Street, Washington, DC 2005-4070. March 13, 2003.

### 2

- 1 

## 2. Relative Contributions of Vehicle Evaporative and Exhaust Emission to Concentrations of Volatile Air Toxics in High Exposure
Microenvironments in Houston

2.1 Introduction

The Desert Research Institute (DRI) conducted measurements to quantify exposures to automotive emissions in microenvironments representing the upper- end (> 99 th 

### percentile) of the distribution of inhalation exposures to evaporative and exhaust emissions of conventional- and oxygenated -gasoline. The study was conducted as part of the Section 211(b) Tier 2 High-End Exposure Study of Conventional and Oxygenated Gasoline. DRI and SwRI conducted

measurements u nder controlled conditions to establish quantitative relationships between tailpipe and evaporative emission rates to exposure levels in a vehicle cabin and attached residential garage. Field exposures also were measured in several high -end exposure microenvironments in Atlanta, Chicago, and Houston during winter and summer. Target species (TVOC, CO, BTEX, HCHO,1,3 -BD, MTBE, EtOH) were measured within microenvironments, breathing zones, and breath. This section apportions the relative contributions of fuel combustion and evaporative emissions to exposures measured various high-end microenvironments, based on differing abundances of MTBE and benzene in exhaust and evaporative emissions. This particular analysis approach was applied to the exposure data from Houston because it is the only city included in the Section 211(b) exposure screening study to use MTBE as the oxygenated additive.

Federal reformulated gasoline (RFG) was introduced in 1995 in nine metropolitan areas

of the United States that were not in attainment of the ambient air quality standard for ozone. The RFG program is implemented year -round in these areas as an emission reduction program to

control ambient ozone and mobile source air toxics (MSAT) . Non-oxygenated conventional gasoline was used in Atlanta during the period of study. Ethanol was used to oxygenate reformulated gasoline in Chicago and MTBE in the Houston area. Table 2- 1 summarizes the major differences in fuel composition between conventional and RFG. Exhaust emissions

include a mi xture of un-combusted fuel components (e.g., BTEX, MTBE, EtOH, TVOC) and species produced during combustion (e.g., benzene, 1,3- BD, HCHO, CO). The relative abundances of combustion by-products in the exhaust profile vary with emission control technology, level of vehicle maintenance, and operating mode.

Liquid gasoline contains many target compounds (BTEX, MTBE, EtOH, TVOC) in common with gasoline- vehicle exhaust. Gasoline headspace vapor, vapor in equilibrium with liquid gasoline, also contains these combustion compounds but is enriched in the more volatile species such as benzene, MTBE, and EtOH. Composite liquid and headspace vapor profiles across different brands and grades of gasoline were developed in conjunction with the Tuscarora, Fort McHenry, and SOS on -road exhaust experiments, for the Auto-Oil program, COAST, the Paso del Norte Study, and the 1995/96 RFG Study (Zielinska et al., 1997). Gasoline compositions were also determine for western Washington (Fujita et al., 1997c), Austin (Fujita,

et al. 1999a), San Francisco Bay Area (Kirchstetter et al., 1999), Houston (Fujita et. al., 2001), and Los Angeles (Fujita et al, 1997; Fujita et al., 2003).

### 2

- 2 There are several sources of evaporative emissions including hot soak emissions driven by residual engi ne heat following cessation of vehicle operation, diurnal emissions associated with fuel tank ‘breathing’ during diurnal temperature and barometric pressure cycling, running losses resulting from fuel tank radiant heating by roadways or from injector fuel recirculation during vehicles operation, resting losses from gasoline permeation through rubber and plastic components of the fuel lines, and simple fuel system leakage. From an analysis of ambient air samples and reconciliation with VOC source profiles, Pierson et al. (1999) conclude that 71 ± 9% of motor vehicle VOC emissions are emitted from tailpipes, 17 ± 6% result from non- tailpipe liquid fuel emissions (fuel system leakage) , and 12 ± 4% are due to headspace vapor emissions.

2.2 Experimental Approach

The profiles for vehicle exhaust, liquid gasoline, and gasoline headspace vapor include many of the same species but notable differences in the ratio of species, a difference that can be used to apportion tailpipe and evaporative emission source strengths. The proportion of MTBE in exhaust is reduced during combustion relative to its proportion in the fuel. Conversely, benzene is enriched in exhaust relative to its proportion in the fuel due to toluene and xylene dealkylation. Consequently, MTBE to benzene ratios are substantially lower in exhaust than in liquid fuel or headspace vapors. MTBE and benzene were measured in all microenvironments in Houston as well as in fuel and vehicle exhaust samples. The fractional evaporative contribution, X, was estimated using following formula.

X = (R ME 

### - R EXH 

### )/ (R VAP 

### - R EXH 

### )

R ME 

### is the measured microenvironmental MTBE/benzene ratio, R EXH 

### is the exhaust

MTBE/benzene ratio, and R VAP 

### is the evaporative MTBE/benzene vapor ratio; either of whole gasoline or headspace vapor depending upon type of evaporative emissions expected in a particular ME (e.g., whole liquid gasoline for hot soak, leaks, or spills and headspace vapors if refueling). Some MEs are influenced by a combination of whole gasoline and headspace vapor

emission s.

For the present study, the Southwest Research Institute (SwRI) procured two test vehicles and determined their evaporative/tailpipe emissions in the normal/malfunction modes using the three test fuels. The test vehicles, a sedan and full -sized V8 truck, were chosen within the 1993- 1996 model years from vehicles with 90,000-110,000 odometer miles. The chosen 1993 Toyota Camry (2.2L 4 -cylinder engine) and 1995 Ford F150 Pickup truck (5.0L V8 engine) were operated in normal, as purchased, modes and in “hig h emitter” modes with the catalytic converter removed and emission levels above 2 grams per mile NMHC as measured on the FTP driving cycle. While converter removal sufficed for the F150 truck, a calibrated manifold leak

was also needed to achieve the ≥ 2g/ mile Camry emissions. SwRI determined dynamometer FTP emissions for each vehicle with all three fuels in the two emission modes (24 tests). Emission control components could be reproducibly adjusted to represent normal and reasonable high-end approximation s ( ≥ 2g/mile) of real world exhaust emissions.

The FTP exhaust emission test uses the 1372 second Urban Dynamometer Driving Schedule (UDDS) that is divided into cold/start transient 505 (Bag 1) and cold stabilized 867

### 2

- 3 (Bag 2) second segments. This portion of the FTP is followed by a 10-minute soak and a hot/start transient 505 (Bag 3) test. The FTP evaporative emission test includes one hour Diurnal Heat Build (DHB) and Hot Soak Loss (HSL) tests. THC/VOC emissions are recorded during the HSL segment of the test. Prior to the FTP cold- start exhaust test, the DHB is conducted by fueling the test vehicle to 40 percent of tank capacity with fuel < 55°F, attaching a heating blanket outside the fuel tank, placing a thermocouple in the tank fuel, hooking it up to computer control, and beginning the test as fuel reaches 60°F (increasing at 0.4°F per minute for the 60- minute test to a 84°F final temperature). In the HSL segment, conducted immediately following exhaust emission testing, the vehicle is driven into an evaporative emission enclosure and allowed to “soak” in the enclosure for one hour. THC/VOC emissions are measured at the beginning and end of the one-hour segment and hot soak evaporative emissions are calculated.

Test fuel samples were subject to standar d tests for Reid Vapor Pressure (RVP), distillation range, Specific Gravity, Sulfur, Benzene, HC Category (saturates, olefins, aromatics), Oxygenated species (MTBE/EtOH), carbon weight percent, hydrogen weight percent, oxygen weight percent, and octane number. Gasoline headspace vapor compositions were predicted from the measured composition of liquid gasoline using the Raoult’s Law method described by Kirchstetter et al. (1999). This method is based on the proportionality between the compound headspace par tial pressure and its liquid mole fraction times the vapor pressure of the pure species. The individual vapor pressures are determined using the Wagner equation (Reid et al. 1987).

DRI measured seasonal in -cabin breathing zone exposures for urban roadways and other high -end MEs in Houston (6/3-7/9/04; 2/1-2/8/05), Chicago (8/5-8/20/03; 3/3-3/17/04), and Atlanta (7/28 -8/8/02; 8/23-9/3/03; 2/10-2/29/04) using a combination of time- integrated samples and continuous instruments listed in Table 2-2. Three repli cate exposure measurements were made for low variability MEs and five for MEs with higher variability (i.e., ME13- trailing high emitting vehicles, ME11 -underground garages, and ME7-outdoor refueling). Measurements in each ME were taken over a period of 20-40 minutes beginning at the top of the hour. Shorter sampling times were used for refueling events and parking garage exits after sporting events. Sampling and analytical methods are described in Section 1 of the report and in the study plan (Zielinska et al., 2003).

2.3 Results

The measured MTBE/benzene ratios are summarized in Table 2 -3 for the Houston MEs. Exposures at the two refueling MEs (3 & 7) were dominated by evaporative emissions as expected, with MTBE/benzene ratios of 20 to 30. Ratios for all ot her MEs were between 1 and 4. The exhaust, headspace, and liquid fuel MTBE/benzene ratios measured in this and other recent

studies are shown in Table 2- 4. MTBE/benzene exhaust ratios among the dynamometer tests average slightly less than 1 with the tunnel ratios nearer 2, possibly due to the added running loss emissions in tunnels. The MTBE/benzene ratios in liquid gasoline and vapor are similar, averaging 15 -20. Ratios for the SwRI SHED tests vary somewhat with calculated headspace compositions and values from earlier listed studies.

### 2

- 4 The estimated fractional contributions of evaporative emissions to total motor vehicles emissions for the various Houston MEs, using the above method, are summarized in Table 2-5 and Figure 2-1. Uncertainties are the standard deviation of the ratios calculated from replicate

test measurements for each ME (represents the variability of ratio within observed sample set). Exposures during refueling (ME3, ME7) are 100% due to evaporative emissions within the

uncertainties associ ated with the measurements and method. All other MEs are dominated by tailpipe emissions with fractional evaporative contributions < 10%.

2.4 Conclusions

The results presented in Table 2

- 5 indicate that evaporative emissions are only substantial components of high end ME exposures during vehicle refueling operations, where they are dominant. Since refueling MEs have the highest relative levels of these components (see sections 1 and 3), they constitute the peak exposures, although overall the average population time spent in these high end MEs is likely the shortest. The contribution of evaporative emissions for all other MEs was typically about 5% of the total measured exposure. Results were similar for both seasons, although evaporative contributions during refueling were marginally less during summer, possibly due to more rapid dispersion of vapors and evaporation of fuel spilled during each refueling test at higher summer temperatures. The clear distinction in evaporative contribution between refueling and non-refueling MEs, along with the relative consistency in MTBE/benzene ratios shown in Table 2.4, gives some confidence in the approach.

These results suggest that the contemporary Houston vehicle fleet contains relatively few carbureted or leaking vehicles given that evaporative emissions are not a substantial source in the

non- refueling MEs tested. Refueling emissions released from pressurized fuel systems and spilled fuels appear to be the primary source of peak evaporative exposures. The lack of a

sea sonal variability in the evaporative contribution is also consistent with this supposition. Although it was not feasible to try to distinguish further between liquid and headspace vapor contributions by the method used, the extremely low MTBE/benzene ratios observed for the roadway, sidewalk, and parking MEs suggest that the contributions of emissions from leaking liquid gasoline is relatively small

.

The contributions of exhaust and evaporative emissions to ambient volatile air toxics were

estimated for H ouston only since it is the only city among the three in the study with oxygenated gasoline containing MTBE. While the contributions of evaporative emissions relative to exhaust

emissions may vary with differences in average prevailing meteorological condi tions, such differences are unlikely to result in significantly different conclusion s in other cities with regard

to the relative contribution s of exhaust and evaporative emissions to ambient concentrations of

volatile air toxics. It must also be noted that the vehicle used in this study for the refueling tests was a 1996 vehicle. All vehicles prior to the 1998 model year do not have onboard refueling vapor recovery (ORVR) system s, and therefore higher refueling emissions. Although refueling stations in Houston had Stage II vapor recovery systems, the ORVR system also reduces vapor losses when the fuel cap is opened by lowering the internal pressure of the fuel tank. The implementation of ORVR systems may further reduce the relative contributions of evaporat ive

emissions.

### 2

- 5 Table 2 -1. Conventional gasoline versus reformulated gasoline RFG (from EPA OTAQ web page http://www.epa.gov/OMSWWW/rfgnew.htm, updated by S. Romanow, OTAQ ).

Fuel Parameter Values (national basis)

Conventional Gasoline Gasohol Oxyfuel
(2.7% wt) "Summer"

Phase I RFG

Average a 

### Range b 

### Average Average Average e



### 8.7-S 6.9-15.1 9.7-S 8.7-S 7.0-7.9 f



### 11.5-W 11.5-W 11.5-W T50 (°F) 207 141-251 202 205 199 T90 (°F) 332 286-369 316 318 325 Aromatics (volume %) 28.6 6.1-52.2 23.9 25.8 22.3 Olefins (volume %) 10.8 0.4-29.9 8.7 8.5 12.5 Benzene (volume %) 1.60 0.1-5.18 1.60 1.60 0.64 Sulfur (ppm) 338 10-1170 305 313 269

MTBE d 

### (volume %)

-- 0.1-13.8

-- 15 11 g



### EtOH d 

### (volume %)

-- 0.1-10.4 10 7.7 10 h 

### RVP c 

### (PSI)

a As defined in the Clean Air Act.

b 1990 Motor Vehicle Manufacturer’s Associ ation (MVMA) survey. c Winter (W) Reid Vapor Pressure (RVP) higher than Summer (S) to maintain vehicle performance. d Oxygenate concentrations shown are for separate batches of fuel; combinations of both methyl tertiary butyl ether (MTBE) and ethanol (EtOH ) in the same blend can never be above 15 volume percent total. e Except as noted, values in this column are volume

- weighted average based on preliminary analysis of a portion of 1996 RFG batch reporting data submitted to EPA by refineries and importers. N umbers are subject to change. f The lower RVP number is average for RFG designated for sale in VOC Control Region 1; the higher RVP number for VOC Control Region 2. In general, Region 1 areas are to the south and/or west. g This is a “typical” value for an RFG batch containing MTBE as the sole oxygenate; this provides about 2% oxygen by weight. h This is a “typical” value for an RFG batch containing ethanol. Ethanol is not combined with other oxygenates in

VOCcontrolled RFG. There are economic incentives fo r blending ethanol at this level, which provides about 3.5% oxygen by weight i. T(50) and T(90) refers to temperatures at which 50% and 90%, respectively, of gasoline volume is distilled.

### 2

- 6 Table 2 -2. Summary of sample collections in urban MEs

ME # ME Description Replicates Biomarker 5 min

Canister Sampling Time
(min)

1 In-Cabin Congested Freeway 5 40

2 In-Cabin Urban Canyon 3 40

3 In-Cabin Refueling 5 20

4 In-Cabin Underground Garage 5 40

5 In-Cabin Toll Plaza 3 40

6* Roadway Tunnel 5 40

7 Outdoor Refueling 5 yes yes 20

8 Sidewalk 3 40

8/9 Sidewalk/Bus Stop 3 40

10 Outdoor Surface Parking 3 40

11 Outdoor Underground Garage 5 yes yes 40

12 Outdoor Toll Plaza 3 40

13* In-cabin Trailing High-Emitting Vehicles 5 yes yes 40

*ME13 was substituted for ME6 in Atlanta and Chicago.

### 2

- 7 Table 2-3. Mass ratios of MTBE to benzene in Houston by ME.

Microenvironment ME Summer Winter

Freeway 1 1.72 ± 0.49 2.88 ± 1.33

Urban Canyon 2 1.10 ± 0.41 2.56 ± 0.80

In-Cabin Refueling 3 24.91 ± 12.19 41.96 ± 21.35

In-Cabin Underground Garage 4 3.22 ± 1.49 2.35 ± 1.78

In-Cabin Toll Plaza 5 2.49 ± 0.77 2.99 ± 1.14

Tunnel 6 2.74 ± 0.42 5.33 ± 6.63

Outdoor Refueling 7 28.82 ± 12.01 55.77 ± 26.83

Sidewalk 8 2.34 ± 0.19 1.15 ± 0.06

Bus Stop 9 2.87 ± 1.13 1.31 ± 0.18

Surface Parking 10 1.94 ± 0.36 6.93 ± 6.57

Outdoor Underground Garage 11 2.60 ± 0.37 3.30 ± 1.50

Outdoor Toll Plaza 12 2.48 ± 1.81 2.78 ± 1.18

### 2

- 8 Table 2 -4. Mass ratios of MTBE to benzene in vehicle exhaust, gasoline vapor and liquid gasoline.

Test Set Fuel Year Average Stdev Reference

Ratios in LDGV Exhaust
CRPAQS/GDS dyno exhaust Los Angeles 2001 0.62 1.35 Fitz et al. 2003
CRPAQS/GDS dyno warm-starts Los Angeles 2001 0.43 1.43 Fitz et al. 2003
CRPAQS/GDS dyno hi-em Los Angeles 2001 1.11 3.17 Fitz et al. 2003

SWRI FTP - summer Houston 2004 0.44 0.24 Merritt, 2005

SWRI FTP - winter Houston 2005 1.40 0.55 Merritt, 2005

SWRI FTP- normal Houston 2004 and 2005 0.60 0.45 Merritt, 2005

SWRI FTP- malfunction Houston 2004 and 2005 1.24 0.71 Merritt, 2005
Ratios in Tunnel and Roadway Samples

WEO3 on-road Los Angeles 2000 2.96 1.03 Fujita et al.2003a; Fujita et al., 2003b
LA tunnels-corrected for running loss Los Angeles 1995 and 1996 0.32 0.99 Fujita et al., 2003b

LA tunnels, uncorrected Los Angeles 1995 and 1996 1.69 0.54 Fujita et al., 2003b
API houston tunnel (ME6) Houston 2004 and 2005 3.36 1.35 This study
Ratio in Gasoline Vapor
LA vapor Los Angeles 1995 16.63 Fujita et al., 2003b
WEO3 vapor Los Angeles 2000 44.98 Fujita et al.2003a; Fujita et al., 2003b

SWRI shed - malfunction Houston 2004 and 2005 20.52 29.20 Merritt, 2005

SWRI shed - malfunction, outlier removed Houston 2004 and 2005 5.93 1.60 Merritt, 2005

estimated from fuel content - summer Houston 2004 32.8 Merritt, 2005

estimated from fuel content - winter Houston 2005 43.9 Merritt, 2005
Ratios in Liquid Gasoline
LA gasoline - 1995 RFG Los Angeles 1995 11.79 Fujita et al., 2003b
WEO3 gasoline Los Angeles 2000 19.56 5.23 Fujita et al.2003a; Fujita et al., 2003b
gds gasoline Los Angeles 2001 17.15 5.49 Gabele, 2003
API gasoline - summer Houston 2004 13.28 Merritt, 2005
API gasoline - winter Houston 2004 17.87 Merritt, 2005

### 2

- 9 Table 2-5. Fractional contributions of evaporative emissions to total motor vehicles emissions in Houston by ME.

Microenvironment ME Summer Winter

Freeway 1 0.04 ± 0.02 0.03 ± 0.03

Urban Canyon 2 0.02 ± 0.01 0.03 ± 0.02

In-Cabin Refueling 3 0.76 ± 0.38 0.95 ± 0.50

In-Cabin Underground Garage 4 0.09 ± 0.05 0.02 ± 0.04

In-Cabin Toll Plaza 5 0.06 ± 0.02 0.04 ± 0.03

Tunnel 6 0.07 ± 0.01 0.09 ± 0.16

Outdoor Refueling 7 0.88 ± 0.37 1.28 ± 0.63

Sidewalk 8 0.06 ± 0.01 -0.01 ± 0.00

Bus Stop 9 0.08 ± 0.04 0.00 ± 0.00

Surface Parking 10 0.05 ± 0.01 0.13 ± 0.15

Outdoor Underground Garage 11 0.07 ± 0.01 0.04 ± 0.04

Outdoor Toll Plaza 12 0.06 ± 0.06 0.03 ± 0.03



## Evaporative Emissions Contribution

0.0 0.5 1.0 1.5 2.0

1 2 3 4 5 6 7 8 9 10 11 12



## MEFraction 

## summer

winter

Figure 2 -1. Fractional contributions of evaporative emissions to total motor vehicles emissions in Houston by ME.

### 2

- 10 2.5 References

Fujita, E.M., Z. Lu, L. Sheetz, G. Harshfield, T. Hayes, and B. Zielinska (1997c). Hydrocarbon

Source A pportionment in Western Washington. Report prepared for the State of Washington Department of Ecology, Lacy, WA, September, 1997.

Fujita, E.M., R.E. Keislar, J.L. Bowen, W. Goliff, F. Zhang, L.H. Sheetz, M.D. Keith, J.C. Sagebiel, and B. Zielinska (1999a). 1998 Central Texas On-Road Hydrocarbon Study. Final report prepared for the Texas Department of Transportation, Austin, TX under subcontract to PBS&J, Austin, TX, March, 1999.

Fujita E.M. (2001). Hydrocarbon Source Apportionment for the 1996 Paso del Nort e Ozone Study. Science of the Total Environment, 276 :171-184.

Fujita, E.M., D.E. Campbell, B. Zielinska, J.C. Sagebiel, J.L. Bowen, W. Goliff, W.R. Stockwell, and D.R. Lawson (2003a). Diurnal and Weekday Variations in Source

Contributions of Ozone Precursors in California’s South Coast Air Basin. J. Air & Waste Manage. Assoc. 53 :844-863.

Fujita, E.M. and D. Campbell (2003b). Validation and Application Protocol for Source Apportionment of Photochemical Assessment Monitoring Stations (PAMS) Ambient

Volatile O rganic Compound (VOC) Data. Final report prepared for the U.S. Environmental Protection Agency under EPA Star Grant #GR826237-01-0, August 31,

2003.

Gabele, P. Support of the Gasoline/Diesel Particulate Matter Split Study. Final report submitted by U.S. Environmental Protection Agency to Department of Energy through Interagency Agreement (IAG) No. DE- AI04 -2001AL67138, March 17, 2003.

Kirchstetter, T.W., B.C. Singer, R.A. Harley, G.R. Kendall, and J.M. Hesson (1999). Impact of California Reformulated Gasoline on Motor Vehicle Emissions: 2. Volatile Organic Compound Speciation and Reactivity. Environ. Sci. Technol., 33 :329-336.

Pierson, W., E. Schorran, E. Fujita, J. Sagebiel, D. Lawson, and R. Tanner (1999). Assessment of Non-Tailpipe Hydrocarbon Emissions from Motor Vehicles. J. Air Waste Manage. Assoc., 49: 498-519.

Reid, R.C., J.M. Prausnitz and B.E. Poling (1987). Composition of Vapor Emitted from a Vehicle Gasoline Tank During Refueling. SAE Technical Paper Series , paper no. 860086.

Zielinska, B. E.M. Fujita, and J.C. Sagebiel, D. Campbell, L.R. Smith and T. Johnson (2003). Exposure Protocol and Study Plan for the Section 211 (B) Tier 2 High End Exposure Screening Study of Baseline and Oxygenated Gasoline. Prepared for American Petroleum Institute, 1220 L. Street, Washington, DC 20005-4007. Final Version. October 1, 2003.

### 3

- 1 

## 3. Determination of t he Quantitative Relationships between Levels of Volatile Air Toxics and Carbon Monoxide Measured In High End Microenvironments and At Nearby Air Quality Monitoring Sta tions

3.1 Introduction

The U.S. Environmental Protection Agency conducts national- scale assessments of air toxics in order to set program priorities, characterize risks, and track progress towards achieving the goals of the national air toxics program as est ablished by the 1990 Clean Air Act Amendments (CAAA). As part of the National Air Toxics Assessment (NATA), EPA conducted a national screening -level assessment for 1996 and 1999 to characterize the potential risks associated with inhalation exposures to 33 air toxics and diesel particulates. The screening

- level

assessment estimated outdoor air toxics concentrations across the US and related these concentrations to population exposures.

The Assessment System for Population Exposure Nationwide (ASPEN) model was used by EPA to estimate outdoor air toxics concentrations across for every census tract in the continental United States, Puerto Rico and the Virgin Islands. To enable the simulation of a large number of air toxics nationwide, a number of simplified approaches are incorporated into the model. The model uses a simplified approach to simulate atmospheric chemistry such as reactive decay and secondary formation (production of an air toxics compound due to chemical reactions in the atmosphere). A uniform background concentration is added for some pollutants for which information is available to compensate because the model simulates only pollutant transport within 50 kilometers of any individual source. For those air toxics with high levels of background co ncentrations, the model’s ability to predict ambient concentrations are greatly impacted by the accuracy of background estimates. Past comparisons with limited monitoring data show that the modeled air toxics concentrations are generally within two orders of magnitude of measured concentrations.

For the exposure-modeling portion of the analysis, EPA used the Hazardous Air Pollutant Exposure Model (HAPEM). The HAPEM modeling approach simulates the movements of various population groups through zones of var ying air quality. Each zone is defined by a geographic location (typically a census tract) and a microenvironment (ME). The patterns of movements among the zones are determined by diary -derived activity data and commuting data acquired from the U.S. census. Ambient concentrations are estimated by the ASPEN dispersion model based on local emissions and meteorological data. The pollutant concentration in a specific ME is estimated as a function of the ambient concentration by a linear expression containing three terms that vary with ME: the penetration factor (the indoor/outdoor ratio in the absence of indoor sources), the additive factor (accounts for contribution of indoor sources), and the proximity factor (accounts for distance to specific outdoor sources such as roadways).

Estimates for these factors for 33 HAPS have been obtained from various field studies and from previous modeling exercises. In general, there is a high degree of uncertainty associated with HAPEM exposure estimates because of the limited data available for estimating the ME factors (Rosenbaum, 2005).

### 3

- 2 The DRI conducted measurements quantifying exposures to automotive emissions in microenvironments (MEs) representing the upper-end (> 99 th 

### percentile) of the distribution ofinhalation exposures to evaporative and exhaust emissions of conventional and oxygenatedgasoline. The study was conducted as part of the Section 211(b) Tier 2 High-End Exposure Screening Study of Baseline and Oxygenated Gasoline. DRI and SwRI conducted measurements under controlled conditions to establish quantitative relationships between tailpipe and evaporative emission rates to exposure levels in a vehicle cabin and attached residential garage. Field exposures also were measured in several high -end exposure MEs in Atlanta, Chicago, and Houston during winter and summer. Target species (TVOC, CO, BTEX, HCHO,1,3- BD, MTBE, EtOH) were measured within MEs, breathing zones, and breath. This section examines the quantitative relationships between CO exposure levels in these M Es to the corresponding fixed site measurements at nearby air monitoring stations. These comparisons are extended for Houston to volatile organic mobile source air toxics, which was the only city among the three with available data. These relationships are compared to the HAPEM proximity factors (Long and Johnson, 2004) that were used in the National Air Toxics Assessments.

3.2 Experimental

DRI measured seasonal in -cabin breathing zone exposures for urban roadways and other high -end MEs in Houston (6/3-7/9/04 ; 2/1 -2/8/05), Chicago (8/5-8/20/03; 3/3-3/17/04), and Atlanta (7/28 -8/8/02; 8/23-9/3/03; 2/10-2/29/04) using a combination of time- integrated samples

and continuous instruments for thirteen different MEs listed in Table 3- 1. Three replicate

exposure measu rements were made for low variability MEs and five for MEs with higher variability (i.e., ME13- trailing high emitting vehicles, ME11 -underground garages, and ME7- outdoor refueling). Measurements in each ME were taken over a period of 20-40 minutes beginning at the top of the hour. Shorter sampling times were used for refueling events and parking garage exits after sporting events.

The integrated samples included whole-air canister samples for CO, BTEX, MTBE, and 1,3-BD, acidified 2,4- diphenylhydrazine (DN PH) cartridges for HCHO and CH 3 

### CHO, and a

multi

- bed (TenaxTA

- Carbotrap -Carbosieve) solid adsorbent tube for EtOH. Continuous

measurements included both non- dispersive infrared (NDIR) and passive electrochemical (Langan T -15) devices for CO and an active photo-ionization detector (PID) for TVOC with an ionization potential below 10.6 eV (principally olefins and aromatic species). Sampling and analytical methods are described in Section 1 and in the study plan (Zielinska et al., 2003).

Ambient CO and VOC da ta were retrieved from EPA’s Air Quality System (AQS) for the specific periods of the field study in each city and compared to the ME measurements. The ambient monitoring and ME locations are mapped for each city in Figures 3-1a to 3- 1c although

some ME lo cations are overlapped by adjacent MEs. AQS VOC data were not available for Atlanta; incomplete data were available for a single site (Northbrook, IL) in Chicago located 20 miles N/NW of city center that is unlikely representative of urban Chicago. Speciat ed hourly

GC/FID VOC data were available from two sites in Houston for both summer and winter. All sites reporting CO and VOC data within each metropolitan area were averaged together for the purposes of comparison. The average CO and benzene concentrations did not show substantial spatial variation within each city.

### 3

- 3 3.3 Results and Discussion

Exposure levels are directly related to source emission rates in the ME and inversely related to source distance and the extent of dilution, itself a function of meteorology and any physical obstructions that inhibit dilution. Hourly values from air quality monitoring stations in urban areas typically represent neighborhood scale exposure levels while 20-40 minute measures

from MEs listed in Table 3

- 1 are intended to rep resent the high end exposures exceeding the 99th percentile. Consequently, the tabulated ME ratios reflect exposures scripted to reflect ‘worst

case’ conditions rather than population- average ME factors for these locations. Such information

should be used solely to evaluate extreme exposures and not misinterpreted as ‘typical’ ME exposures encountered by the general population.

Quantitative relationships for CO between ME measures and fixed site measurements at nearby air monitoring stations are examined first. CO is non- reactive and commonly measured

year -round as a primary mobile source emission that is generally correlated with BTEX and 1,3-

BD. Table 3 -2 shows the averages and standard deviations of the ratios of time- integrated CO from canister samples to the corresponding hourly CO from the ambient air monitoring stations in Houston, Atlanta, and Chicago by season and ME. As expected, the ratios are higher in MEs

that are nearer to operating vehicle engines, especially in underground garages where dispersion of pollutants is limited. The average ratios for in -cabin exposures in congested freeway traffic ranged from 2 to 9 with lower ratios in the winter. Ratios were highest in Atlanta and lowest in Chicago. The seasonal and city

- specific differences hold for most of the other MEs. Notable exceptions to the seasonal differences are the underground garages where the ratios are higher in the winter in all three cities, most likely due to the higher cold

- start emissions. Garage size, ventilation, and spatial- temporal vehicle activity patterns account for the variance differences between underground garages. The garage in Atlanta is smaller, less ventilated, and more used than the garages in Houston or Chicago. While CO is a good exhaust species tracer, correlation with evaporative emissions is less. ME/ambient ratios are generally lower for CO than most of the other pollutants. This is most likely due to higher urban background levels of CO.

Table 3 -3 shows average Houston BTEX and 1,3- BD ME/ambient ratios (± SD), i.e., the

time -integrated canister value to the corresponding hourly monitoring station GC/FID value. In contrast to CO, BTEX ME/ambient ratios are substantially higher for refueling (ME 3, ME 7). The BTEX ratios are closer to corresponding ratios derived for CO during winter but higher during summer. Since 1,3- BD is an exhaust species, the relative variation of ME/ambient ratios is similar to CO. 1,3 -BD measures in MEs with high MTBE were invalid due to interferences (see Section 1).

The integrated exposure measurements are 20 -40 minute averages. Continuous CO and VOC PID measurements show higher peak (1-5 minutes) exposures. Continuous instruments provide sensitive proportionate measures of short- term target species variability since continuous

tim e- averaged traces are well correlated to the corresponding time

- integrated measurements. Consequently, the normalized continuous CO or VOC PID measures were used to reconstruct 1-

minute time -series concentrations for specific components. Either CO or VOC P ID traces are suitable surrogates in exhaust

- dominated MEs; VOC PID values are suitable surrogates in evaporative emissions -dominated MEs such as refueling. Reconstructed time- series and ranges

### 3

- 4 of estimated 1 -minute values are summarized in Section 1. Figu res 3 -2a through 3-2c show 20- 40 minute average and maximal estimated 1 -minute values for benzene, 1,3- BD, and HCHO, respectively. Short-term exposures from evaporative-dominated ME3 and ME7 range more widely than those from other exhaust-dominated MEs.

3.4 Conclusions

MEs in close proximity to running vehicle engines have enhanced CO relative to ambient levels with enrichment ratios approaching 40 where ventilation is limited, as in underground garages. Average in

- cabin CO/ambient ratios in congested freeway traffic range from 2 -9 with lower winter ratios. ME locations less proximate to operating vehicles, such as gas stations and urban sidewalks, have CO/ambient ratios of 0.5-2.

The Houston benzene ME1/ambient ratio of 9.8 ± 3.8 for exceed the HAPEM5 med ian proximity factor of 4.9 (triangular distribution mode:range 1.9:0-14.3) and HAPEM4 proximity factor of 6.9 for this ME (Rosenbaum, 2005; Long and Johnson, 2004), although by less than expected. The HAPEM4 factors may be elevated compared to present con ditions since measurements occurred before 1991 when benzene fuel levels and roadway fleet emissions were higher than today. HAPEM5 proximity factors may also need to be adjusted since they were based on a 1998 scoping study where measurements ‘highlighted trailing behind heavy duty diesel vehicles and diesel city buses when possible’. Houston ME/ambient ratio comparisons also generally exceed the other HAPEM factors listed in Table 3 -4. Refueling ratios (ME3, ME7) for benzene were substantially higher than the corresponding HAPEM factors also as expected. Concentrations of exhaust compounds such as CO and 1,3-BD were enhanced under reduced

ventilation situations.

3.5 References

Rosenbaum, A. (2005). The HAPEM5 User’s Guide. Report prepared by ICF Consulting for the U.S. Environmental Protection Agency, Research Triangle Park, NC, March 2005.

Long, T. and T. Johnson (2004). Development of Penetration and Proximity Microenvironment Factor Distributions for the HAPEM5 in Support of the 1999 National- Scale Air To xics Assessment (NATA). Memorandum prepared by TRJ Environmental, Inc. for the U.S. Environmental Protection Agency, Research Triangle Park, NC, April 5, 2004.

Zielinska, B. E.M. Fujita, and J.C. Sagebiel, D. Campbell, L.R. Smith and T. Johnson (2003). Exp osure Protocol and Study Plan for the Section 211 (B) Tier 2 High End Exposure Screening Study of Baseline and Oxygenated Gasoline. Prepared for American Petroleum Institute, 1220 L. Street, Washington, DC 20005-4007. Final Version. October 1, 2003.

### 3

- 5 Table 3 -1. Summary of sample collections in urban microenvironments

ME # ME Description Replicates Biomarker 5 min

Canister Sampling Time
(min)

1 In-Cabin Congested Freeway 5 40

2 In-Cabin Urban Canyon 3 40

3 In-Cabin Refueling 5 20

4 In-Cabin Underground Garage 5 40

5 In-Cabin Toll Plaza 3 40

6* Roadway Tunnel 5 40

7 Outdoor Refueling 5 yes yes 20

8 Sidewalk 3 40

8/9 Sidewalk/Bus Stop 3 40

10 Outdoor Surface Parking 3 40

11 Outdoor Underground Garage 5 yes yes 40

12 Outdoor Toll Plaza 3 40

13* In-cabin Trailing High-Emitting Vehicles 5 yes yes 40

*ME13 was substituted for ME6 in Atlanta and Chicago.

### 3

- 6 Table 3 -2. Average and standard deviation in ratios of the time-integrated CO from canister samples to the corresponding hourly CO from regional ambient air monitoring sites for Houston, Atlanta and Chicago by season and microenvironment.

Summer Winter

Microenvironment Houston Atlanta Chicago Houston Atlanta Chicago

1 Congested Freeway, In-Cabin 4.6 ± 1.0 9.1 ± 6.5 2.6 ± 0.4 4.0 ± 1.0 5.4 ± 1.9 1.7 ± 0.4

2 Urban Canyon, In-Cabin 5.2 ± 2.5 3.9 ± 3.9 2.9 ± 1.4 12.1 ± 10.9 2.7 ± 5.6 1.0 ± 0.5

3 Refueling, In-Cabin 3.6 ± 0.9 1.4 ± 2.7 0.7 ± 0.3 4.1 ± 3.2 1.3 ± 0.6 0.5 ± 0.1

4 Underground Garage, In-Cabin 8.4 ± 8.0 16.9 ± 0.8 7.9 ± 3.4 21.4 ± 12.5 38.8 ± 0.2 12.6 ± 5.8

5 Toll Plaza, In-Cabin 4.1 ± 1.0 6.4 ± 0.0 1.6 ± 0.5 3.6 ± 0.6 2.7 ± 0.0 1.0 ± 0.1

6 Tunnel, In-Cabin 8.4 ± 1.7 6.3 ± 1.5 9.7 ± 5.2 2.5 ± 0.4

7 Refueling, Outdoor 1.9 ± 0.8 1.2 ± 1.8 0.9 ± 0.3 3.3 ± 2.5 2.1 ± 1.4 0.8 ± 0.9

8 Sidewalk 1.9 ± 0.5 1.9 ± 0.5 1.1 ± 0.2 1.3 ± 0.6 1.9 ± 0.9 0.9 ± 0.0

9 Sidewalk/BusStop 1.5 ± 0.3 2.4 ± 0.3 1.6 ± 0.6 1.8 ± 0.1 1.9 ± 0.2 1.1 ± 0.2

10 Surf Parking, Outdoor 3.3 ± 1.2 5.3 ± 0.7 2.1 ± 1.3 4.7 ± 2.9 3.3 ± 0.6 1.4 ± 0.5

11 Underground Garage, Outdoor 8.6 ± 7.4 26.8 ± 3.6 3.9 ± 2.3 17.1 ± 11.2 32.9 ± 2.0 12.4 ± 7.2

12 Toll Plaza, Outdoor 7.6 ± 2.7 6.5 ± 8.8 3.2 ± 0.2 6.2 ± 4.3 7.4 ± 16.5 1.8 ± 0.3

13 Following High Emitter, In-Cabin 8.4 ± 2.6 12.0 ± 4.2

### 3

- 7 Table 3 -3. Average and standard deviations in ratios of BTEX and 1,3- BD from time -integrated canister samples to the corresponding hourly automated GC data from the ambient air monitoring sites in Houston.

Microenvironment Benzene Toluene Etbenzene m&p-Xylene o-Xylene 1,3-Butadiene

Summer

1 Congested Freeway, In-Cabin 9.8 ± 3.8 7.8 ± 1.9 5.4 ± 1.8 5.2 ± 0.6 6.6 ± 1.5 8.1 ± 3.6

2 Urban Canyon, In-Cabin 7.4 ± 3.0 6.8 ± 1.1 5.6 ± 3.3 5.6 ± 1.4 5.8 ± 2.4 7.3 ± 1.2

3 Refueling, In-Cabin 565 ± 791 446 ± 666 140 ± 188 115 ± 136 117 ± 147

4 Underground Garage, In-Cabin 19.4 ± 13.9 17.2 ± 15.0 16.0 ± 13.7 14.2 ± 12.8 17.1 ± 17.0 50.0 ± 66.4

5 Toll Plaza, In-Cabin 9.1 ± 4.4 7.8 ± 3.6 6.8 ± 4.9 6.2 ± 3.4 7.1 ± 3.8 7.8 ± 5.2

6 Tunnel, In-Cabin 25.9 ± 14.1 12.4 ± 6.8 7.8 ± 2.9 7.5 ± 2.7 8.9 ± 2.7 37.9 ± 20.0

7 Refueling, Outdoor 1312 ± 1811 974 ± 1356 335 ± 479 219 ± 227 197 ± 198

8 Sidewalk 15.4 ± 10.6 10.6 ± 4.4 12.5 ± 15.3 11.9 ± 14.0 14.2 ± 17.1 5.8 ± 2.4

9 Sidewalk/BusStop 4.7 ± 2.0 2.9 ± 1.3 1.8 ± 0.4 1.9 ± 0.5 2.3 ± 0.6 2.0 ± 1.3

10 Surf Parking, Outdoor 11.5 ± 5.5 8.3 ± 2.8 7.4 ± 2.1 6.7 ± 3.1 7.0 ± 3.2 5.5 ± 1.9

11 Underground Garage, Outdoor 16.7 ± 5.3 15.7 ± 7.2 13.8 ± 7.2 11.1 ± 7.2 14.4 ± 9.6 39.6 ± 29.5

12 Toll Plaza, Outdoor 14.7 ± 8.5 11.3 ± 10.2 9.2 ± 8.3 8.5 ± 7.6 11.0 ± 10.6 13.4 ± 13.1

Winter

1 Congested Freeway, In-Cabin 4.6 ± 1.6 6.4 ± 3.7 6.4 ± 3.0 8.8 ± 5.2 9.7 ± 5.1 0.36 ± 0.06

2 Urban Canyon, In-Cabin 17.0 ± 21.7 22.7 ± 27.7 22.1 ± 26.4 31.1 ± 36.9 26.7 ± 28.9

3 Refueling, In-Cabin 35.0 ± 25.4 36.5 ± 27.2 22.7 ± 18.2 25.3 ± 19.2 24.2 ± 16.3

4 Underground Garage, In-Cabin 37.2 ± 15.8 32.3 ± 12.9 24.0 ± 9.4 23.2 ± 8.5 25.0 ± 9.7

5 Toll Plaza, In-Cabin 3.5 ± 1.7 3.7 ± 1.5 4.3 ± 1.7 4.6 ± 2.0 5.3 ± 2.1

6 Tunnel, In-Cabin 8.5 ± 6.7 9.0 ± 6.9 7.0 ± 4.5 8.9 ± 6.4 9.9 ± 7.2 1.91 ± 0.54

7 Refueling, Outdoor 160 ± 148 119 ± 92 49.1 ± 39.2 56.1 ± 54.3 44.6 ± 33.7

8 Sidewalk 2.8 ± 0.8 2.6 ± 1.0 2.7 ± 0.7 3.6 ± 1.7 3.7 ± 1.3 0.09 ± 0.10

9 Sidewalk/BusStop 3.3 ± 0.3 3.6 ± 0.3 3.5 ± 1.1 4.2 ± 0.7 4.3 ± 0.8

10 Surf Parking, Outdoor 4.3 ± 3.0 7.5 ± 6.4 5.7 ± 2.9 6.1 ± 2.1 6.0 ± 2.5

11 Underground Garage, Outdoor 28.3 ± 16.5 25.0 ± 13.0 20.8 ± 11.3 21.9 ± 11.1 22.9 ± 10.7 0.60 ± 0.03

12 Toll Plaza, Outdoor 4.8 ± 0.7 4.5 ± 1.4 4.5 ± 1.8 4.9 ± 1.6 5.4 ± 1.9

### 3

- 8 Table 3 -4. Houston benzene ME/ambient ratio comparison with HAPEM benzene ME factors

ME Summer Winter HAPEM4

PROX HAPEM5 PROX Distribution (mode;median) HAPEM5 PROX Range 1 Congested Freeway, In

- Cabin 9.8 4.6 5.2, 6.9* Triangular 1.9; 4 .9 0

- 14.4 2 Urban Canyon, In

- Cabin 7.4 17 4.4 Triangular 1.9; 4.9 0

- 14.4 3 Refueling, In

- Cabin 565 35 4.4 Triangular 1.6; 2.7 0

- 7.1 4 Underground Garage, In

- Cabin 19 37 1.0 Triangular 1.6; 2.7 0

- 7.1
5 Toll Plaza, In

- Cabin 9.1 3.5 4.4 Triangular 1.9; 4. 9 0

- 14.4
6 Tunnel, In

- Cabin 26 8.5 4.4 Triangular 1.9; 4.9 0

- 14.4 7 Refueling, Outdoors 1300 160 4.4 Triangular 1.6; 2.7 0

- 7.1

8 Sidewalk 15 2.8 4.4 Triangular 1.6; 2.7 0

- 7.1 9 Sidewalk, BusStop 4.7 3.3 4.4 Triangular 1.6; 2.7 0

- 7.1 10 Surface Parking , Outdoors 12 4.3 4.4 Triangular 1.6; 2.7 0

- 7.1 11 Underground Garage, Outdoors 17 28 1.0 Triangular 1.6; 2.7 0

- 7.1
12 Toll Plaza, Outdoors 15 4.8 4.4 Triangular 1.6; 2.7 0

- 7.1
* truck, car

### 3

- 9 Figure 3.1a. Location of ME sampling and fixed monitoring stations in Chicago Metro Area.

### 3

- 10 Figure 3.1b. Location of ME sampling and fixed monitoring stations in Houston Metro Area.

### 3

- 11 Figure 3.1c. Location of ME sampling and fixed mo nitoring stations in Atlanta Metro Area.

### 3-12 Benzene - Estimated Average 1-minute Concentrations

0 20 40 60 80 100 120 14001020304050708091011121301020304050708091011121301020304050607080910111213010203040506070809101112010203040506070809101112010203040506070809101112

Summer Winter Summer Winter Summer Winter

Atlanta Chicago HoustonConc (ppbv)

Benzene - Estimated Maximum 1-minute Concentrations

0 500 1000 1500 2000 250001020304050708091011121301020304050708091011121301020304050607080910111213010203040506070809101112010203040506070809101112010203040506070809101112

Summer Winter Summer Winter Summer Winter

Atlanta Chicago HoustonConc (ppbv)



### Figure 3

- 2a. Comparison of average versus the maximum 1

- minute benzene levels by city, season and microenvironment.

### 3-13 1,3-Butadiene - Estimated Average 1-minute Concentrations

0 1 2 3 4 501020304050708091011121301020304050708091011121301020304050607080910111213010203040506070809101112010203040506070809101112010203040506070809101112

Summer Winter Summer Winter Summer Winter

Atlanta Chicago HoustonConc (ppbv)

1,3-Butadiene - Estimated Maximum 1-minute Concentrations

0 5 10 15 20 2501020304050708091011121301020304050708091011121301020304050607080910111213010203040506070809101112010203040506070809101112010203040506070809101112

Summer Winter Summer Winter Summer Winter

Atlanta Chicago HoustonConc (ppbv)



### Figure 3 -2b. Comparison of average versus the maximum 1- minute 1,3-butadiene levels by city, season and microenvironment.

### 3-14 Formaldehyde - Estimated Average 1-minute Concentrations

0 10 20 30 4001020304050708091011121301020304050708091011121301020304050607080910111213010203040506070809101112010203040506070809101112010203040506070809101112

Summer Winter Summer Winter Summer Winter

Atlanta Chicago HoustonConc (ppbv)

Formaldehyde - Estimated Maximum 1-minute Concentrations

0 20 40 60 80 100 120 140 16001020304050708091011121301020304050708091011121301020304050607080910111213010203040506070809101112010203040506070809101112010203040506070809101112

Summer Winter Summer Winter Summer Winter

Atlanta Chicago HoustonConc (ppbv)



### Figure 3

- 2c. Comparison of average versus the maximum 1- minute formaldehyde levels by city, season and microenvironment.

### 4

- 1 

## 4. Relationships of Attached Garage and Home Exposures t o Fuel Type and Emission Levels of Garage So urces

4.1 Introduction

This chapter describes experiments to determine relationships between measured fuel and exhaust components in the attached garage, adjacent room (kitchen), and garaged vehicle emission levels. The same vehicles, fuels and vehicle malf unctions used here are used in Chapter 5 to explore the effects of ventilation, proximity, and leading vehicle emission levels on trailing vehicle in

- cabin exposures. These measurements are also described in the executive summary and Chapter 1.

Measureme nts were performed during June-July 2002 and February-March 2005 in San Antonio, TX on a sedan and a pickup truck using either non-oxygenated conventional gasoline, gasohol (E10), or an MTBE- oxygenated gasoline. The vehicles

were tested in both a normal em issions mode and a malfunctioning high emitter mode where emissions were adjusted to exceed 2 grams of non -methane hydrocarbons (NMHC) per mile as measured by the Federal Test Procedure (FTP).

4.2 Experimental

Methods and procedures specific to the attached garage experiments are summarized below. Sampling and analyses methods are described in Chapter 1 and Appendix B.

4.2.1 Vehicles and Vehicle Test Methods

The Southwest Research Institute (SwRI) procured two test vehicles and determined their evaporative/tail pipe emissions in the normal/malfunction modes using the three test fuels. The test vehicles, a sedan and full -sized V8 truck, were chosen within the 1993-1996 model years from vehicles with 90,000-110,000 odometer miles. The chosen 1993 Toyota Camry (2.2L 4-cylinder engine) and 1995 Ford F150 Pickup truck (5.0L V8 engine) were operated in normal, as purchased, modes and in “high emitter” modes with the catalytic converter removed and emission levels above 2 grams per mile

NMHC as measured on the FTP drivin g cycle. While converter removal sufficed for the F150 truck, a calibrated manifold leak was also needed to achieve the ≥ 2g/mile Camry emissions. SwRI determined dynamometer FTP emissions for each vehicle with all three fuels in the two emission modes (24 tests). Emission control components could be reproducibly adjusted to represent normal and reasonable high-end approximations ( ≥ 2g/mile) of real world exhaust emissions. The vehicle properties are summarized in Table 4.2-1 and included in the SwRI report (Appendix F)

.

### 4

- 2 Table 4.2-1. Summary of vehicles used.

Vehicle Make Model Year Engine Malfunction

Truck Ford F150 1995 5.0 L V8 Removed Catalyst.

Sedan Toyota Camry 1993 2.2 L 4 cylinder Removed Catalyst and added

leak to manifold.

Regulated exhaust emissions (THC, NMHC, CO, NOx), fuel economy, and specific VOCs (MTBE, EtOH, BTEX, 1,3-BD, HCHO) were determined in dynamometer FTP tests. During hot-soak SHED tests, THC and specific VOCs (minus HCHO) were also determined.

The FTP exhaust emission test uses the 1372 second Urban Dynamometer Driving Schedule (UDDS) that is divided into cold/start transient 505 (Bag 1) and cold stabilized 867 (Bag 2) second segments. This portion of the FTP is followed by a 10- minute soak and a hot/start transient 505 (Bag 3) test. The FTP evaporative emission test includes one hour Diurnal Heat Build (DHB) and Hot Soak Loss (HSL) tests. THC/VOC emissions are recorded during the HSL segment of the test. Prior to the FTP cold- start exhaust test, the DHB is conducted by fueling the test vehicle to 40 percent of tank capacity with fuel < 55°F, attaching a heating blanket outside the fuel tank, placing a thermocouple in the tank fuel, hooking it up to computer control, and beginning the test as fuel reaches 60°F (increasing at 0.4°F per minute for the 60-minute test to a 84°F final temperature). In the HSL segment, conducted immediately following exhaust emission testing, the vehicle is driven into an evaporative emission enclosure and allowed to “soak” in the

enclosure for o ne hour. THC/VOC emissions are measured at the beginning and end of the one-hour segment and hot soak evaporative emissions are calculated.

4.2.2 Fuel Testing

Test fuel samples were subject to standard tests for Reid Vapor Pressure (RVP), distillation range, S pecific Gravity, Sulfur, Benzene, HC Category (saturates, olefins, aromatics), Oxygenated species (MTBE/EtOH), carbon weight percent, hydrogen weight percent, oxygen weight percent, and octane number. These results are presented in Table

4.3-1.

4.2.3 Test House

Fuel component levels were measured in the garage and in a room (kitchen) adjacent to an attached garage using the fuels and test vehicles in normal and high emitter modes. Appendix I shows the layout of the house. The double garage contained an active ceiling fan that minimized emissions stratification and hot spots within the garage. The garage also contained a plastic gasoline container and gasoline -powered lawnmower

filled with the test fuels. The exhaust fan over the kitchen’s stove was not used dur ing the

### 4

- 3 experiments. However, the central air conditioning was active during the summer tests. Garage and kitchen monitoring was conducted according to the scenarios described in Table 4.2-2. Window and door openings, of the garage vehicle door, the kitchen door between the garage and kitchen, and kitchen window were scripted. Time- integrated canister, DNPH and solid adsorbent (for EtOH) cartridges, and SPME samples werecollected for each test. EtOH was measured for Chicago fuel only. Continuous or semicontinuous measurements were also operated during the exposure periods. Measurements were taken over scripted 30

- minute scenario intervals through collocated sampling inlets at breathing height (1.5 m) a meter distant from nearby walls in the kitchen and unventilated garage. Continuous PID TVOC and Langan CO instruments sampled from the kitchen before (background) and during 2002 tests. For the winter 2005 samples, a second PID TVOC and the NDIR CO instrument were used to monitor the garage continuously. In the summer 2002 samples, the continuous MS200 BTEX and A- Ω HCHO monitors sampled cyclically through collocated inlets in the garage and kitchen every 10 minutes.

A half

- filled two -gallon plastic gasoline storage container with vent opened was placed adj acent to a fueled lawnmower, with gas tank half filled, against the center of the rear garage wall common with the kitchen. The container and lawnmower filled with the appropriate fuel were placed in the garage one day before the series of vehicle tests fo r that fuel began and remained there over the duration of the tests. Scenario conditions were changed every 30 minutes over the 3-hour protocol as described in the Table 4.2-2. Ambient garage temperatures were recorded each 30 minutes. Tests were conducte d daily (excluding weekends) over a two week period.

Table 4.2-2. Protocol for attached garage experiments.

Condition Time (min) Garage

Door Kitchen

Door Kitchen

Window Inlet
Location Continuous

Instruments SPME Integrated
Canisters/ Cartridges Backg round No vehicle,

but lawn mower & gas 10

closed closed closed garage yes 2 2 10 kitchen yes

10 garage yes

Hot soak vehicle, lawnmower, & gas 10

closed opened 1

min

& closed closed kitchen yes 2

2 10 garage yes

10 kitchen yes
Cooling vehicle, lawnmower, & gas 10 closed closed closed garage yes 2 10 kitchen yes

10 garage yes

Cold vehicle, lawnmower, & gas 10 closed closed open kitchen yes 2 10 garage yes

10 kitchen yes

### 4

- 4 Cold start, idling, lawnmower, & gas 10 open opened 1

min

& closed closed garage yes 2 10 kitchen yes

10 garage yes

No vehicle,

but lawnmower, & gas 10 closed closed closed kitchen yes 2 10 garage yes

10 kitchen yes



### The first scena rio condition, background, assesses levels in the kitchen and garage prior to the beginning of vehicle testing. In the garage, background will include emissions from the gasoline container and lawn mower. The hot soak condition should most closely

reflect the hot soak SHED tests performed by SwRI. In this condition, the exposure scenario is that of a person coming home from shopping and conveying purchases through the kitchen-garage door into the home, allowing some enhanced air exchange between the garage and the kitchen. The next condition, cooling vehicle, reflects a period where the trapped garage air remains in the kitchen. The cold vehicle condition is performed with the kitchen window open to allow outside fresh air exchange within the kitchen (keeping the garage door closed). The cold start condition simulates a person warming up his car in an open garage prior to leaving; the kitchen door is open for one minute to account for the extra trips to and from the vehicle. The vehicle is started and then idled for the entire 30 minutes. The final condition, no vehicle, represents kitchen exposures after the vehicle has left. One integrated canister and cartridge samples were collected over background test and another one over all five phases of the garage

ex periments, as shown in Table 4.2-2.

4.3 Results

4.3.1 Fuel Analyses

The results of the fuel analyses are presented in Table 4.3

- 1. Fewer tests were run

on the Summer 2002 fuels.

The results confirm that there was no oxygenate in the Atlanta conventional fuel, that MTBE was present in the Houston fuel, and that ethanol was present in the Chicago fuel. Across seasons total aromatics were similar in the oxygenated fuels but higher in the conventional fuel. Benzene levels range from 0.5-1.2 % with the conventional s ummer fuel highest. The Reid Vapor Pressure (RVP) is higher in the winter fuels to ensure cold start reliability.

### 4

- 5 Table 4.3-1. Summary of properties for the six test fuels.

O2 Total wt% = total oxygen weight % MeOH = methanol; EtOH = ethanol

4.3.2 Vehicle R egulated and Hot Soak Emissions

The vehicle emission tests were conducted as described in Section 4.2. The details of these tests are described in the SwRI Report, attached in Appendix F. Tables 4.3-2 through 4.3-5 show the measured regulated exhaust and hot soak emissions from the test

vehicles for summer and winter test fuels. The FTP results show that all emissions increased and the high emitter target of ≥ 2 grams NMHC per mile was achieved.

### 4

- 6 Table 4.3-2. Regulated and Hot Soak Emissions from the Ford F-150, Summer 2002.

Table 4.3-3. Regulated and Hot Soak Emissions from the Ford F-150, Winter 2005.

Table 4.3-4. Regulated and Hot Soak Emissions from the Toyota Camry, Summer 2002

Table 4.3-5. Regulated and Hot Soak Emissions from the Toyota Camry, Winter 2005

### 4

- 7 4.3.3 Garage and Kitchen Exhaust/Evaporative Fuel Component Levels

This section summarize s emission component concentrations observed in the kitchen and attached garage. As discussed in Chapter 1, measured 1,3- BD levels are biased upwards in the presence of high MTBE concentrations. In addition, a single garage sample (sedan with gasohol in n ormal mode) was invalidated. The sample contained high anomalous levels of BTEX, BTEX/1,3- BD and BTEX/CO ratios were 25

- and 88-fold higher, respectively, in the normal mode than the high emitter tests, suggesting an anomalous source of BTEX such as an un recorded garage fuel spill. BTEX and 1,3-butadiane data presented in Tables 4.3-6 to 4.3-12 are from the canister samples and ethanol is from the sorbent cartridges, as described in Chapter 1 and Appendix B..

4.3.3.1 Background and Overall Concentrations

The b ackground samples, taken before the vehicle was brought into the garage, are presented in Table 4.3-6 for both the average (top section, separated for summer and winter) and ranges of the data. Note that the max -min ranges denote the single highest

values for each species individually across tests. Gaps indicate missing samples. Both HCHO and EtOH show relatively higher levels in the kitchen. HCHO off- gases from residential furnishings and construction materials. EtOH is emitted from people, foods, cleaning & personal care products, domestic garbage, and alcoholic beverages.

Table 4.3-6. Summary of Background Concentrations in Kitchen and Garage. Units are ppbv, except as noted.

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO,ppm Formal EtOH Acetal Kitchen Backgrounds

Summer 0.08 1.70 6.50 0.67 2.30 1.05 0.42 0.35 49.83 1215.58 13.57

Winter 0.21 3.93 7.47 4.82 7.47 4.32 1.31 0.87 13.51 5.47 Garage Backgrounds

Summer 0.02 2.68 8.87 0.92 3.25 1.14 0.20 0.15 20.29 6.28

Winter 0.12 2.29 5.40 0.85 3.13 1.21 1.11 0.78 7.70 2.65

Kitchen, all

Min 0.02 0.73 3.33 0.37 1.25 0.50 0.00 0.15 5.50 53.60 3.00

Max 1.33 11.76 15.49 38.21 32.27 24.64 6.16 5.29 106.63 2194.10 24.56 Garage, all

Min 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 3.85 0.90 1.20

Max 0.90 11.47 25.72 3.19 11.33 4.27 3.78 7.01 35.63 1475.60 13.89



### Budi13 = 1,3BD; Benze = benzene; Tolue = toluene, Mp_xyl = m,p-xylene; o_x yl = o -xylene, Formal = formaldehyde; EtOH = ethanol , Acetal = acetaldehyde



### The ranges of all samples taken during the vehicle

- related scenario portions are presented in Table 4.3-7. As expected, the lower concentrations stem from normal mode vehicles

and higher levels from the high emitter mode.

### 4

- 8 Table 4.3-7. Summary of Test Concentration Ranges in Kitchen and Garage. Units are ppbv, except as noted.

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO,ppm Formal EtOH Acetal
Kitchen, all

Min 0.02 0.18 2.49 0.25 0.78 0.43 0.00 0.00 0.00 158.80 0.00

Max 1.64 11.17 15.58 3.02 9.06 5.12 13.27 10.85 95.59 670.20 23.86

Garage, all

Min 0.03 1.33 2.48 0.39 1.25 0.51 0.00 0.20 0.00 5.80 0.00

Max 36.35 65.44 93.67 18.23 50.72 19.36 185.63 39.16 174.20 27.70 30.79



### Budi13 = 1,3BD; Benze = benzene; Tolue = toluene, Mp_xyl = m,p- xylene; o_xyl = o -xylene,

Forma l = formaldehyde; EtOH = ethanol , Acetal = acetaldehyde



### 4.3.3.2 Seasonal Impacts

Seasonal max trends are inconsistent. Table 4.3-8 shows that differences seen in the kitchen are smaller than in the garage. The garage has higher exhaust 1.3- BD and

HCHO in the su mmer, but lower CO values than in the winter.

Table 4.3-8. Seasonal Impact on Observed Maximum Concentrations (Units are ppbv, except as noted ).

. Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO,ppm Formal EtOH Acetal

Kitchen Max-S 1.42 7.77 14.64 1.84 6.44 2.98 10.49 1.62 95.59 670.20 23.86

Max-W 1.64 11.17 15.58 3.02 9.06 5.12 13.27 10.85 54.78 15.51 Garage Max-S 36.35 65.44 93.67 18.23 50.72 19.36 93.63 28.60 174.20 27.70 30.79

Max-W 8.47 24.68 34.61 6.05 22.78 8.04 185.63 39.16 54.78 15.51



### Budi13 = 1,3BD; Benze = benzene; Tolue = toluene, Mp_xyl = m,p- xylene; o_xyl = o -xylene,

Formal = forma ldehyde; EtOH = ethanol , Acetal = acetaldehyde



### Tables 4.3-9 and 4.3-10 provide max and average values for normal mode vehicles only. The maximum values for the normal vehicles are generally lower with winter mean values higher than summer.

Table 4.3-9. Seasonal Impact on Observed Maximum Concentrations (Units are ppbv, except as noted ), Normal Mode Vehicles Only.

Normal Only Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO,ppm Formal EtOH Acetal

Kitchen Max-S 0.29 4.87 14.35 1.80 6.44 2.48 1.59 0.81 95.59 519.70 23.86

Max-W 1.55 11.17 14.80 2.76 8.50 3.44 13.27 3.07 31.31 11.00 Garage Max-S 4.76 21.02 48.73 6.99 19.92 7.73 8.95 3.86 58.53 27.70 13.79

Max-W 8.47 24.68 34.61 6.05 22.78 8.04 185.63 39.16 54.78 15.51



### Budi13 = 1,3BD; Benze = benzene; Tolue = toluene, Mp_xyl = m,p- xylene; o_xyl = o -xylene, Formal = formaldehyde; EtOH = ethanol , Acetal = a cetaldehyde



### Table 4.3-10. Seasonal Impact on Observed Average Concentrations (Units are ppbv, except as noted ), Normal Mode Vehicles Only.

### 4

- 9 Normal Only Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO,ppm Formal EtOH Acetal

Kitchen Ave-S 0.16 3.25 11.54 1.39 4.58 1.97 0.56 0.39 53.33 339.25 13.48

Ave-W 0.43 4.38 7.24 1.31 4.12 1.72 3.76 0.92 14.54 4.99 Garage Ave-S 1.87 8.72 20.36 3.06 8.67 3.51 2.47 1.82 26.44 17.35 6.26

Ave-W 2.35 8.15 14.44 2.54 9.00 3.39 36.64 6.45 18.72 4.79



### 4.3.3.3 Fuel and Vehicle Effects

This section addresses fuel, vehicle, and operational mode separately for all

seasons . For the sedan, Table 4.3-11 indicates highest mean MTBE values for Houston fuel and EtOH for Chicago, as expected, with high- emitter/malfunction effects strongest in the garage.

Table 4.3-11. Effect of Fuel and Operational Mode of the Sedan on Observed Levels in the Kitchen and Garage (Units are ppbv, except as noted).

. Location Fuel Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO,ppm Formal EtOH Acetal Normal Garage Atlanta 0.55 2.40 6.09 0.98 3.24 1.38 0.82 0.31 7.16 1.78

Houston 0.95 3.56 9.78 1.51 5.20 2.08 10.81 0.56 22.25 5.11 Chicago 1.19 3.40 8.29 1.39 4.91 2.06 0.48 0.45 11.75 27.70 3.81

Kitchen Atlanta 0.06 2.01 8.42 1.03 3.61 1.45 0.10 0.10 63.45 16.78

Houston 0.24 2.82 7.49 1.10 3.69 1.59 3.35 0.52 24.01 6.65 Chicago 0.06 3.82 8.45 1.26 4.40 1.91 0.27 0.29 13.38 158.80 2.48

Malfunction Garage Atlanta 1.42 26.80 44.40 4.03 13.08 4.86 16.67 6.27 23.35 9.03

Houston 2.54 12.45 25.68 4.20 14.11 5.53 49.97 13.29 30.72 7.35 Chicago 1.92 9.54 11.26 1.65 5.64 2.18 1.13 12.16 13.08 19.00 7.35

Kitchen Atlanta 0.86 9.13 15.11 2.06 6.47 2.92 0.35 5.59 21.99 6.97

Houston 0.23 4.14 9.68 1.74 5.42 2.65 10.19 1.30 26.19 8.37 Chicago 0.23 2.81 6.04 1.03 3.51 1.53 0.30 0.76 25.93 670.20 9.88



### Budi13 = 1,3BD; Benze = benzene; Tolue = toluene, Mp_xyl = m,p- xylene; o_xyl = o -xylene, Formal = formaldehyde; EtOH = ethanol , Acetal = acetaldehyde



### For the truck, Table 4.3-12 indicates lesser fuel impacts on normal mode garage levels than for the sedan. For the malfunction mode, Houston fuel garage values exceed

those of the other two fuels.

Table 4.3-12. Effect of Fuel and Operational Mode of the Truck on Observed Levels in the Kitchen and Garage (Units are ppbv, except as noted).

. Location Fuel Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO,ppm Formal EtOH Acetal Normal Garage Atlanta 2.40 11.28 26.45 3.79 11.05 4.32 0.44 2.13 38.17 8.25

Houston 1.39 9.69 24.99 3.83 11.12 4.46 10.46 2.15 38.12 8.85 Chicago 2.55 9.64 15.61 2.99 8.56 3.41 1.74 2.87 0.00 7.00 0.00

Kitchen Atlanta 0.12 1.65 8.23 0.83 2.58 1.04 0.10 0.28 35.68 8.88

Houston 0.37 4.57 9.68 1.62 4.85 2.28 7.20 0.82 45.47 13.40 Chicago 0.92 8.02 14.08 2.27 6.97 2.78 1.95 1.94 21.61 519.70 7.25

Malfunction Garage Atlanta 3.74 16.19 26.42 3.87 12.22 4.58 0.38 8.03 45.11 9.79

Houston 22.41 45.06 64.14 12.14 36.75 13.70 139.63 33.88 114.49 23.15 Chicago 2.73 7.72 11.55 1.85 5.87 2.16 0.06 2.52 32.96 5.80 17.28

Kitchen Atlanta 0.24 3.25 7.65 1.99 5.67 3.15 0.13 0.68 42.56 10.91

Houston 0.80 4.23 9.05 1.42 4.25 1.89 4.57 1.33 52.72 14.55 Chicago 0.11 4.11 7.29 1.45 4.67 1.92 0.03 0.28 29.37 414.10 7.65

### 4

- 10 Figure 4.3-1 i llustrates the effect of fuel and mode (N

- normal, F -malfunction) on mean garage values averaged across vehicle and season. Figure 4.3 -2 shows the kitchen values. Both figures report relatively high 1,3-BD values for the Houston fuel high emitter mode. Since both are also associated with high MTBE values, these 1,3- BD values are suspect as discussed earlier and in Chapter 1. The same caveat applies to Figures 4.3-3 and 4.3-4.

0 10 20 30 40 50 60 70 80

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO,ppm Formal EtOH Acetal

compoundppbv Atlanta-N

Atlanta-F

Houston-N

Houston-F

Chicago-N

Chicago-F



### Figure 4.3-1. Effect of fuel and mode on observed concentrations in the garage. The legend “N” is normal and “F” is malfunction. The 1,3-BD value for Houston-F is suspect.

### 4

- 11 0 5 10 15 20 25 30 35 40 45 50

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO,ppm Formal EtOH Acetal

compoundppbv Atlanta-N

Atlanta-F

Houston-N

Houston-F

Chicago-N

Chicago-F 339,542



### Figure 4.3-2. Effect of fuel and mode on observed concentrations in the kitchen. The legend “N” is normal and “F” is malfunction. The 1,3-BD value for Houston- F is suspect.

The kitchen concentrations are dominated by HCHO and EtOH, but high background levels indicate kitchen sources rather than the garaged vehicles.

The effect in the garage is expected to be more directly correlated with the vehicle. Figure 4.3-3 shows the concentrations seen in the garage only for the sedan, looking at the effect of the fuel and operational mode. The same presentation for the truck only is in Figure 4.3-4.

### 4

- 12 0 10 20 30 40 50 60

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO,ppm Formal EtOH Acetal

compoundGarage, ppbv Atlanta-N

Atlanta-F

Houston-N

Houston-F

Chicago-N

Chicago-F



### Figure 4.3-3. Effect of fuel and mode on observed sedan garage levels. The legend “N” is normal and “F” is malfunction. The 1,3-BD level for Houston- F is suspect, see text.

0 20 40 60 80 100 120 140 160

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO,ppm Formal EtOH Acetal

compoundGarage, ppbv Atlanta-N

Atlanta-F

Houston-N

Houston-F

Chicago-N

Chicago-F



### Figure 4.3-4. Effect of fuel and mode on observed truck garage levels. The legend “N” is normal and “F” is malfunction. The 1,3-BD level for Houston- F is suspect, see text.

### 4

- 13 Comparison of 1,3- BD, BTEX and CO background concentrations with garage and kitchen concentrations for each test is shown in Figure 4.3-5 and Figure 4.3- 6 for Summer 2002 and Winter 2005, respectively. In general, these figures indicate compound range rankings of garage » kitchen ~ background, especially for vehicle in the normal mode. For vehicles in high emitting mode, the increase in kitchen levels could be seen. In Winter 2005, a few high background samples were observed, possibly due to a prolonged storage of a plastic gasoline container in the garage.

### 4

- 14 0 50 100 150 200 250 300 350 400K-BACKGG-BACKGK-TESTG-TESTK-BACKGG-BACKGK-TESTG-TESTK-BACKGG-BACKGK-TESTG-TESTK-BACKGG-BACKGK-TESTG-TESTK-BACKGG-BACKGK-TESTG-TESTK-BACKGG-BACKGK-TESTG-TESTK-BACKGG-BACKGK-TESTG-TESTK-BACKGG-BACKGK-TESTG-TESTK-BACKGG-BACKGK-TESTG-TESTK-BACKGG-BACKGK-TESTG-TESTK-BACKGG-BACKGK-TESTG-TESTK-BACKGG-BACKGK-TESTG-TESTppbv



### 0 5 10 15 20 25 30 35CO (ppm)

budi13 mtbe benze tolue etbz mp_xyl o_xyl CO Toyota,

normal Toyota,

malfunction Atlanta (Baseline) Fuel

Truck,

normal Truck,

malfunction Toyota,

normal Toyota,

normal Truck,

malfunction Toyota,

malfunction

Toyota,

malfunctio Truck,

normal Houston (MTBE) Fuel

Truck,

malfunction Truck,

normal Chicago (Ethanol) Fuel



### Figure 4.3-5. Concentrations of 1,3-butadiene, MTBE and BTEX and CO as measured from canisters in the garage and the adjacent

kitchen in Summer 2002

### 4

- 15 0 50 100 150 200 250 300G-BACKGK-BACKGG-TESTK-TESTG-BACKGK-BACKGG-TESTK-TESTG-BACKGK-BACKGG-TESTK-TESTG-BACKGK-BACKGG-TESTK-TESTG-BACKGK-BACKGG-TESTK-TESTG-BACKGK-BACKGK-TESTG-TESTG-BACKGK-BACKGG-TESTK-TESTG-BACKGK-BACKGG-TESTK-TESTG-BACKGK-BACKGG-TESTK-TESTG-BACKGK-BACKGG-TESTK-TESTG-BACKGK-BACKGG-TESTK-TESTG-BACKGK-BACKGG-TESTK-TESTppbv

0 5 10 15 20 25 30 35 40 45CO (ppm)

budi13 mtbe benze tolue etbz mp_xyl o_xyl CO_ppm Atlanta (Baseline) Fuel

Toyota,

normal Toyota,

malfunction Truck,

normal Truck,

malfunction Houston (MTBE) Fuel

Toyota,

normal Toyota,

malfunction Truck,

normal Truck,

malfunction Chicago (Ethanol) Fuel

Toyota,

normal Toyota,

malfunction Truck,

normal Truck,

malfunctio

M M 

### A



### Figure 4.3-6. Concentrations of 1,3- butadiene, MTBE and BTEX (A) and CO (B) as measured from canisters in the garage and the adjacent kitchen in Winter 2005. M=sample missing or invalid.

### 4

- 16 4.3.3.4 Comparison with Emissions Data

There are five distinct garage scenario phases after the background sample as described in Table 4.2-2. The first phase, hot soak, is best compared to the hot soak SHED test run by SwRI. Benzene canister values are comp ared in Figure 4.3-7. While there does not appear to be a strong correlation, the canister samples collected in the garage average over all five scenario s, not only hot soak. The high outlying points come from the truck in high emitter mode and are
expecte d to be high. SPME samples taken every half-hour correspond better with the phases of the experiment. Benzene winter SPME values for hot soak phase are compared with SHED values in Figure 4.3-8A (all samples) and 4.3-8B (outliers removed). Although the co rrelation is not very good for all samples (A) , it improves after removing two outliers from the truck in high emitter mode (B)

. The high emitting vehicles are generally not stable and the SHED results may be very different from the garage, due to differen t time and location.

0 10 20 30 40 50 60 70

0 20 40 60 80 100 120 140 160

SHED results, mgGarage, ppbv



### Figure 4.3-7. Comparison of SHED results with the observed canister concentration in the garage

for benzene.

0 5 10 15 20 25 30 35

0 20 40 60 80 100 120 140 160

SHED, mgGarage hot soak, ppbv (by SPME) y = 0.1317x + 4.8305

R 2 = 0.4323

0 5 10 15 20 25

0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0

SHED, MGGarage hot soak, ppbv (SPME)



### Figure 4.3-8. Comparison of the SHED results with the observed SPME hot soak concentration in the garage for benz ene A: all data, B: two outliers removed. A B

### 4

- 17 Cold start 1,3- BD and benzene canister values can be compared to the FTP Bag 1 data in Figures 4.3-9 and 4.3-10, respectively. Garage 1,3- BD values appear insensitive to FTP levels. It is possible that this may ref lect another 1,3- BD analytical challenge from NO2 scavenging in the FTP sample; the high point in Figure 4.3-7 is also suspect since 1,3-BD occurs concurrent with high MTBE levels. The Figure 4.3- 8 garage benzene scatter is similar to 1,3 -BD and also appears insensitive to FTP levels ; however, benzene is stable in canisters and these values should be accurate. Figure 4.3 -11 compares garage SPME cold start values to FTP Bag 2 values. This comparison trends upwards with garage values increasing with increasing FTP emissions, although not strongly.

0 5 10 15 20 25 30 35 40

0 10 20 30 40 50 60 70 80

FTP Bag 1, mg/miGarage, ppbv



### Figure 4.3-9. Comparison of FTP Bag 1 emissions and observed garage levels of 1,3- BD.

### 4

- 18 0 10 20 30 40 50 60 70

0 50 100 150 200 250

FTP Bag 1, mg/miGarage, ppbv



### Figure 4.3-10. Comparison of FTP Bag 1 benzene emissions and observed garage levels.

0 10 20 30 40 50 60 70 80 90

0 20 40 60 80 100 120 140

FTP Bag 1, mg/miGarage, cold start, ppbv (by SPME)



### Figure 4.3-11. Comparison of hot soak FTP Bag 1 benzene emissions and observed SPME garage values.

### 4

- 19 4.3.3.5 Relationships of Garage and Kitchen Concentrations

Kitchen values would be expected to increase with increasing garage levels from vehicle and fuel container sources. Based on their high background levels, EtOH and HCHO would not be good candidates for tests. Three other species 1,3-BD, CO, and benzene are plotted in Figures 4.3-12, 4.3-13 and 4.3-14, respectively.

Figure 4.3-12A shows a weak 1,3-BD trend which seems to be driven most ly by outliers associated with high level MTBE interference. As explained in Chapter 1 (page 1- 6) elevated MTBE concentrations biases measured 1,3 -BD levels upwards, due to the thermal decomposition of MTBE (in the order of 1 to 5 %) in a GC injector. The removal of two outliers (for the truck with MTBE fuel in malfunction mode) eliminates any correlation between garage and kitchen concentrations (Figure 4.3-12B).

Figure 4.3-13 trends toward a CO insensitivity to garage concentrations. The high value occurred for the sedan in malfunction mode; the continuous data show a 100 ppm CO spike at the beginning of the cold- start phase that may have penetrated through a briefly opened kitchen door. Figure 4.3-14 shows that there is no correlations between kitc hen and garage benzene concentrations. However, it has to be pointed out that these kitchen – benzene correlations are shown for the time-integrated canister samples that were collected over 2.5 hr duration of the experiment. During this time several 30

- mi n scenarios were executed, as shown in Table 4 -2.2. The differences in ventilation conditions between garage and kitchen are the most probably responsible for the lack of correlations between species measured from canisters

.

y = 0.0298x + 0.2539

R 2 = 0.2034

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8

0 10 20 30 40

Garage Concentration, ppbvKitchen Concentration,ppbv A

y = 0.0141x + 0.2965

R 2 = 0.002

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8

0 1 2 3 4 5 6

Garage Concentrations, ppbvKitchen Concentrations, ppbv B



### Figure 4.3-12. Comparison of garage and kitchen concentrations for 1,3- BD. A

– all data, B

with two outliers removed (see text)

.

### 4

- 20 y = 0.04x + 0.84

R 2 

### = 0.05

0 2 4 6 8 10 12

0 10 20 30 40 50

Garage Concentration, ppbvKitchen Concentration,ppbv



### Figure 4.3-13. Comparison of garage and kitchen concentrations of carbon monoxide.

y = 0.04x + 3.61

R 2 = 0.06

0 2 4 6 8 10 12

0 20 40 60 80

Garage Concentration, ppbvKitchen Concentration,ppbv



### Figure 4.3-14. Comparison of garage and kitchen concentrations of benzene.

### 4

- 21 4.4 Discussion

The objective of this section was to test the effects of attached garage on indoor home levels of fuel and exhaust components. The experiment simulates common activities such as coming home with a warm car or leaving home after starting a cold vehicle.

Various parameters are assessed in section 4.3 to determine their effects on air levels in the adjacent room (here a kitchen) connecting to the garage. Two target components, HCHO and EtOH, had high kitchen background values indicating indoor sources of these materials. Average HCHO levels were higher in summer than winter, consistent with enhanced off- gassing of building materials and/or penetration of ambient photochemical HCHO. It has been also reported (Reiss et al, 19 95; Wang and Morrison, 2006; Weschler, 2006) that a larger fraction of indoor HCHO and other oxygenated-low molecular weight hydrocarbons can result from heterogeneous processes. Ozone originating from outdoors can be deposited onto indoor surfaces

and rea ct with different materials to produce low molecular weight organic acids and aldehydes. The concentrations of these species are higher during the summer when more ozone penetrates

indoors.

Tables 4.3-8 to 4.3-10 show a seasonal impact where kitchen BTEX , MTBE and CO species are higher in winter than summer. The exception is toluene which shows a minimal difference that actually averages higher in summer for normal mode vehicles. This is consistent with indoor toluene emissions from paints, adhesives, cleaning, and personal care products. Tables 4.3-8 and 4.3-9 focus on normal mode vehicles to remove the variability of high emitter modes in assessing the seasonal effect. Since many species higher in the winter come from both evaporative and exhaust emissi ons, it is possible that winter enhanced fuel RVP contributes to the apparent seasonal effect. In addition, a large number of studies have shown that home air exchange rates are typically lower during the winter. This would result in longer residence times (thus accumulation) of pollutants generated in the garage and further infiltration to the kitchen

area.

Tables 4.3-10 and 4.3-12 show vehicle data separately for each fuel. MTBE and ethanol are highest for fuels containing those species, as anticipated. Otherwise, there is not a strong fuel

effect across vehicles.

FTP exhaust and SHED evaporative emissions were tested for each vehicle, fuel, and emissions mode, and compared to observed levels in the garage. These comparisons are challenging in that ca nisters integrate across hours covering not only hot soak, adjustments to the air exchange, and cold start. Concurrent SPME samples are collected for each condition. However, neither canister nor SPME samples show strong correlations with hot soak emission s (Figures 4.3-5 to 4.3-8), although cold- stabilized FTP Bag 2 benzene appears reasonably

correlated to the cold -start SPME (Figure 4.3-9).

Correlations of kitchen levels with garage concentrations are presented in Figures 4.3-12 to 4.3-14. These plots evidence weak correlations and could not be used to predict kitchen exposures from garage levels. 1,3-BD (Figure 4.3-12) and benzene (Figure 4.3-14) may trend weakly upwards, with kitchen levels increasing with garage levels; however CO (Figure 4.3-13)

### 4

- 22 does not. Tables 4.3-6 and 4.3-7 indicate (HCHO & EtOH excepted) compound range rankings of garage » kitchen ~ background, especially for vehicle in the normal mode. For vehicles in high emitting mode, the increase in kitchen levels is seen from Figures 4.3-5 and 4.3-6.

4.5 References:

Reiss, R., Ryan, P., Tibbetts, S. E., and Koutrakis, P., Measurement of Organic Acids, Aldehydes, and Ketones in Residential Environments and their Relationship to Ozone, Journal of the Air and Waste Management Association, 45 , 811 (1995).

Wang, H., G.C. Morrison. Ozone

- initiated secondary emission rates of aldehydes from indoor

surfaces in four homes. ES&T 40: 5262-68 (2006)

Weschler, C.J. Ozone’s impact on public health: contributions from indoor exposures to ozone and products of ozone- initiated chemistry. Environ.Health Perspective 141: 1489-96 (2006).

### 5

- 1 

## 5. Effect of Ventilation, Proximity, and Emission Levels on In

- Cabin Exposures of Trailing Vehicle.

5.1 Introduction

This chapter describes experiments designed to determ ine the relationships between ventilation, proximity, fuel, and emission levels of a leading vehicle on in- cabin exposures within a trailing vehicle. The same vehicles, fuels and induced malfunctions used for this chapter are used for Chapter 4. These meas urements are part of the program described in the executive summary and Chapter 1.

As in the preceding chapter, the vehicles used are a sedan and a pickup truck; the

fuels used are either a conventional fuel (without oxygenate), an ethanol fuel, or an

M TBE fuel. The vehicles are tested in a normal and induced -malfunction mode with nonmethane hydrocarbon (NMHC) emissions of about 2 g/mile by Federal Test Procedure (FTP).

The experiments were performed in summer (June-July 2002) and winter (February

- Mar ch 2005).

5.2 Experimental

The Southwest Research Institute (SwRI) procured two test vehicles and determined their evaporative/tailpipe emissions in the normal/malfunction modes using the three test fuels. The test vehicles, a sedan and full -sized V8 truck, were chosen within the 1993-1996 model years from vehicles with 90,000-110,000 odometer miles. The chosen 1993 Toyota Camry (2.2L 4-cylinder engine) and 1995 Ford F150 Pickup truck (5.0L V8 engine) were operated in normal, as purchased, modes and in “h igh emitter” modes with the catalytic converter removed and emission levels above 2 grams per mile NMHC as measured on the FTP driving cycle. While converter removal sufficed for the F150 truck, a calibrated manifold leak was also needed to achieve the 2g/ mile Camry emissions. SwRI determined dynamometer FTP emissions for each vehicle with all three fuels in the two emission modes (24 tests). Emission control components could be reproducibly adjusted to represent normal and reasonable high-end approximation s (2 g/mile) of real world exhaust emissions. Test vehicle evaporative emissions were also measured for test fuels in the two emission modes as reported in Chapter 4.

Regulated exhaust emissions (THC, NMHC, CO, NOx), fuel economy, and specific VOCs (MTB E, EtOH, BTEX, 1,3-BD, HCHO) were determined in the dynamometer FTP tests. During hot-soak SHED tests, THC and specific VOCs (minus HCHO) were determined.

The FTP exhaust emission test uses the 1372 second Urban Dynamometer Driving Schedule (UDDS) that is divided into cold/start transient 505 (Bag 1) and cold stabilized 867 (Bag 2) second segments. This portion of the FTP is followed by a 10- minute soak and a hot/start transient 505 (Bag 3) test. The FTP evaporative emission test

### 5

- 2 includes one hour Diurnal Heat Build (DHB) and Hot Soak Loss (HSL) tests. THC/VOC emissions are recorded during the HSL segment of the test. Prior to the FTP cold- start exhaust test, the DHB is conducted by fueling the test vehicle to 40 percent of tank capacity with fuel < 55 °F, attaching a heating blanket outside the fuel tank, placing a thermocouple in the tank fuel, hooking it up to computer control, and beginning the test as fuel reaches 60°F (increasing at 0.4°F per minute for the 60-minute test to a 84°F final temperature).

In the HSL segment, conducted immediately following exhaust emission testing, the vehicle is driven into an evaporative emission enclosure and allowed to “soak” in the enclosure for one hour. THC/VOC emissions are measured at the beginning and end of the one-hour segment and hot soak evaporative emissions are calculated.

5.2.1 Fuel Testing

Test fuel samples were subject to standard tests for Reid Vapor Pressure (RVP), distillation range, Specific Gravity, Sulfur, Benzene, HC Category (saturates, olefins, aromatics), Oxygenated species (MTBE/EtOH), carbon weight percent, hydrogen weight percent, oxygen weight percent, and octane number. These results are presented in Chapter 4, Table 4.3-1.

5.2.2 Relationship between Exhaust Emission Rates and In

- Cabin Exposure - Trailing Vehicle Test

5.2.2.1 Test Protocol

The two test vehicles were used as characterized sources of measured in -cabin exposures for an instrumented trailing vehicle. SwRI procured a 1996 Chrysler Minivan which DRI instrumented as the trailing vehicle ( described in Chapter 1) that was driven behind the test vehicles over a remote, paved, two- lane, farm

- to -market roadway loop (described below) for test periods up to 3 hours. Initial measurements made absent the test vehicles established background levels . Trailing vehicle tests then implemented far, near, and passing scenarios at low (30 mph) and high speeds (60 mph) as noted in Table

5.2- 1. During 'far' scenarios, ‘safe’ vehicle spacing (defined as one car length

- 10 feet

- for each 10 mph) was maintained. During the 'near' scenario, the trailing vehicle tailgated the lead vehicle, following at a close distance deemed 'safe' by the professional drivers under prevailing traffic and meteorological conditions. During the “passing” scenario, the trailing vehicle split its time between tailgating the lead vehicle and ‘passing,’ immediately behind the lead vehicle but in the adjacent lane. A final idling test was conducted while the trailing vehicle was parked on the road shoulder downwind and closely behind the parked idling lead vehicle. High (10 min) and low (10 min) ventilation conditions were used during all (including idling) tests.

Table 5.2- 1 details the trailing vehicle protocol. Trailing vehicle in

- cabin TVOC [ppbRAE-PID (photoionization detector)], CO (Langan T15), BTEX (Kore200MS), and HCHO (A

- Ω) were continuously monitored. Integrated VOC/NMHC (canister),

### 5

- 3 HCHO/CH 3 

### CHO (DNPH cartridge), and EtOH (sorbent tube – EtOH fuel only) samples were also collected. SPME BTEX samples were collected every 1 0 min. Appendix B describes sampling and analytical methods in detail.

The trailing vehicle tests were conducted south of San Antonio, TX on county roads 462 and 2779 off IH 35 in the vicinity of Moore, Big Foot, and Jones Mound, Texas. The position of the trailing vehicle was recorded continuously by a Garmin 12XL GPS unit recording in UTM using NAD83/WGS84. Speed and direction of the vehicle between any two points can be located on a map as illustrated in the June 19, 2002 test Figures 5.2-1, -2. The mapping software also contains a digital elevation model that creates elevation profiles as shown in Figure 5.2-3. The change in elevation over the 14.5-mile driving route is approximately 100 feet.

Table 5.2-1. Protocol for Trailing Vehicle Tests

Tim e Min. Speed Mph Ventilation Setting Distance Notes Continuous

Instruments SPME Time Integrated

10 high high background Y 1 1

10 low high far Vehicles:Toyota Camry and Ford

Pick -up truck, in

normal and

malfunction mode.

Fuels: Atlanta (conventional), Houston (MTBE), Chicago (ethanol) Y 1

One sample

in Summer

2002.

Two samples, at high/low ventilation,

for Winter

2005. 10 low high near Y 1

10 low high passing Y 1

10 high high far Y 1

10 high high near Y 1

10 high high passing Y 1

10 low low far Y 1

10 low low near Y 1

10 low low passing Y 1

10 high low far Y 1

10 high low near Y 1

10 high low passing Y 1

10 idle low adjacent Y 1 1

10 idle high adjacent Y 1

### 5

- 4 Figure 5.2-1. Map of Driving Test Location near San Antonio. The blue markers indicate the location of the driving tests.

### 5

- 5 Figure 5.2-2. Map of Driving Test Location near Moore, TX.

Figure 5.2-3. Elevation Profile of the Driving Route near Moore, TX.

### 5

- 6 5.3 Results

An initial summary of the trailing vehicle study findings, averaging across all vehicles, emission modes, and fuels, is presented below. The lead vehicles and fuels are the same as described in Chapter 4; Section 4.3.1 presents the fuel analyses and Section 4.3.2 the FTP exhaust and evapor ative vehicle emissions tests.

Note the protocol changes between Summer 2002 and Winter 2005 tests: in the Summer tests only half the sample days were begun with a background sample; in the Winter tests separate in -cabin samples were taken for the high ventilation and low

ventilation measurements as detailed in Table 5.2 -1.

5.3.1 Background and Overall Concentrations

The background sample results from the summer and winter samples are presented in Table 5.3- 1. The percent standard deviations are relatively low, suggesting that the backgrounds are relatively stable. The MTBE deviations are highest likely because this compound is principally present only in the Houston fuel. Background MTBE ranged from 0 to 0.21 ppbv. There was only one EtOH background measu rement for the Summer 2002 (261 ppb) and three valid measurements for Winter 2005. The high 2002 EtOH value could be connected with the presence of four people in the vehicle cabin and/or the presence of the continuous formaldehyde analyzer. The winter val ues range from 9 to 44 ppb and seem to be more reliable.

Table 5.3-1. Summary of Summer and Winter Background Concentrations.

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO, ppm Formal EtOH Acetal Mean Summer (n=6) 0.02 0.27 0.44 0.07 0.17 0.11 0.06 0.13 5.80 261 2.80

% std dev 54% 26% 15% 24% 46% 48% 131% 18% 84% (n=1) 90%

Mean Winter (n=12) 0.03 0.32 0.52 0.11 0.38 0.16 0.08 0.21 5.62 22.07 4.05

% std dev 46% 46% 67% 61% 63% 62% 101% 38% 63% 88% 42%

Mean all 0.03 0.31 0.49 0.10 0.31 0.14 0.07 0.19 5.68 81.81 3.64

% std dev 50% 42% 58% 59% 72% 63% 107% 41% 68% 147% 56%



### Budi13 = 1,3BD; Benze = benzene; Tolue = toluene, Mp_xyl = m,p- xylene; o_xyl = o -xylene, Formal = formaldehyde; EtOH = ethanol , Acetal = acetaldehyde



### In Figure 5.3-1 the values for formaldehyde are divided by 10 to fit on the same scale as the rest of the species and the EtOH values are not shown. Generally speaking

the in -cabin background values are < 1 ppbv, with the exception of HCHO and EtOH, and relatively consistent from summer to winter.

In -cabin HCHO measurements likely included contributions from photochemical formation from ambient VOCs and in-cabin fabric component degassing of this species. As mentioned in Chapter 1 and 4, EtOH may be emitted from people (as a metabolic product for certain food types), foods, cleaning& personal care products, etc.

### 5

- 7 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO, ppm Formal/10 Acetal/10Concentrations (ppbv or ppmv)

Mean Summer (n=6) Mean Winter (n=12)



### Figure 5.3-1. Comparison of Summer and Winter Background Concentration s with Standard Deviations. Formaldehyde and acetaldehyde divided by 10 for scale.

Mean concentrations over all tests are presented in Table 5.3 -2. Standard deviations are expressed as a percent of test value. As with the background concentrations, MTBE likely shows the greatest variability since it was prominent in only one fuel. Also, EtOH Summer 2002 measurements (3 values) are most probably artifact, whereas Winter 2005 data (6 measurements) seem to be much more reliable.

Table 5.3-2. Summary of Test Concentrations for Summer, Winter and Overall. Units are ppbv, except CO as noted.

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO, ppm Formal Acetal EtOH Mean Summer (n=12) 0.69 1.40 2.32 0.43 1.25 0.59 0.44 1.00 6.84 5.61 2308.07

% std dev 103% 69% 56% 65% 62% 63% 230% 72% 47% 71% 102%

Mean Winter (n=24) 0.59 1.20 1.99 0.37 1.30 0.50 0.83 1.72 4.82 2.54 1.70

% std dev 96% 76% 73% 77% 74% 76% 220% 91% 70% 75% 51%

Mean all 0.62 1.26 2.09 0.39 1.28 0.53 0.70 1.49 5.53 3.63 693.61

% std dev 100% 75% 67% 73% 70% 71% 233% 91% 63% 89% 250%



### Budi13 = 1,3BD; Benze = benzene; Tolue = toluene, Mp_xyl = m,p- xylene; o_xyl = o -xylene, Formal = formaldehyde; EtOH = ethanol , Acetal = acetaldehyde



### Figure 5.3-2 and 5.3-3 shows the CO, MTBE and BTEX con centrations for each

test in the Summer 2002 and Winter 2005, respectively.

### 5

- 8 0 10 20 30 40 50 60BACKG.TESTIDLETESTIDLETESTIDLEBACKG.TESTIDLEBACKG.TESTIDLETESTIDLETESTIDLETESTIDLEBACKG.TESTIDLEBACKG.TESTIDLEBACKG.TESTIDLETESTIDLEppbv

0 2 4 6 8 10 12CO (ppm)

budi13 mtbe benze tolue etbz mp_xyl o_xyl CO Truck,

malfunction

Toyota,

normal Toyta,

malfunction

Truck,

normal Toyota

malfunction Truck

malfunctio

Toyota

normal Toyota,

malfunction Track

normal Toyota,

normal

(M) Truck

malfunction

Truck,

normal Atlanta (Baseline) Fuel Houston (MTBE) Fuel Chicago (Ethanol) Fuel



### Figure 5 .3-2. Concentrations of 1,3-BD, MTBE and BTEX (A) and CO (B) as measured in the cabin of the trailing vehicle, Summer

2002

### 5

- 9 0 5 10 15 20 25 30 35 40 45BACKGTEST_HVTEST_LVIDLEBACKGTEST_HVTEST_LVIDLEBACKGTEST_HVTEST_LVIDLEBACKGTEST_HVTEST_LVIDLEBACKGTEST_HVTEST_LVIDLEBACKGTEST_HVTEST_LVIDLEBACKGTEST_HVTEST_LVIDLEBACKGTEST_HVTEST_LVIDLEBACKGTEST_HVTEST_LVIDLEBACKGTEST_HVTEST_LVIDLEBACKGTEST_HVTEST_LVIDLEBACKGTEST_HVTEST_LVIDLEppbv



### 0 2 4 6 8 10 12CO (ppm)



### budi13 mtbe benze tolue etbz mp_xyl o_xyl CO_ppm Atlanta (Baseline) Fuel

Toyota,

normal Toyota,

malfunctio Truck

normal Truck

malfunction

Toyota,

normal Toyota,

malfunctio

M Truck

normal Truck

malfunction Houston (MTBE) Fuel

Toyota,

normal Toyota,

malfunction

Truck

normal Tr

ma Chicago (Ethanol) Fu



### Figure 5. 3-3. Concentrations of 1,3-BD, MTBE and BTEX and CO as measured in the cabin of the trailing vehicle, Winter 2005

### 5

- 10 Figure 5.3-4 compares summer and winter concentrations which, like background, are similar (EtOH data not shown).

0 1 2 3 4 5 6 7 8

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO, ppm Formal AcetalConcentrations (ppbv or ppmv)

Mean Summer (n=12) Mean Winter (n=24)


### Figure 5.3-4. Comparison of Summer and Winter Con centrations for the Trailing tests.

Summer background and test values, excluding HCHO and EtOH, are compared in Figure 5.3-5. Test values show a substantial increase over background. Correlating all summer species except HCHO and EtOH against their backg round values gives a slope of 0.24 (r-square = 0.93).

Winter background and test values are presented in Figure 5.3- 6, omitting HCHO and EtOH. The observation that the winter HCHO values were, on average, lower than background values suggests that most of the HCHO observed was not coming from the lead vehicle but possibly from photochemical or off- gassing sources (e.g., fabrics) inside the trailing vehicle. EtOH background values were higher than test values, which suggest

some initial off -gassing of EtOH in the vehicle cabin (since background sample was collected at the beginning of each experiment). The correlation of all winter speciesvalues except HCHO and EtOH against their background values had a slope of 0.31 (rsquare = 0.73).

### 5

- 11 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO, ppmConcentration, ppbv or ppm

Summer Background Summer Tests


### Figure 5.3-5. Comparison of Summer Background and Test Values.

0 1 1 2 2 3 3 4

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO, ppmConcentration, ppbv or ppm

Winter Background Winter Tests


### Figure 5.3-6. Comparison of Winter Background and Test Values.

### 5

- 12 Table 5.3-3 presents the concentrations and percent standard deviations observed during the idle tests. These values showed more of a range and larger deviations than either the background or the driving tests. HCHO again appears to be an outlier with the lowest deviation of any of the species, likely indicating that this species is not coming predominantly from the upwind lead vehicle. EtOH values for Summer 2002 (3 measurements) are most probably artifact and the Winter 2005 values (4 measurements)

are more realistic. Since the main difference between the Summer 2002 and Winter 2005 experiments was the absence of the continuous formaldehyde and MS200 KORE mass spectrometer in the trailing vehicle, it is possible that one of these instruments (most probably the continuous formaldehyde analyzer, since it is based on the wet method) was

out- gassing EtOH.

Table 5.3-3. Summary of Concentrations Observed During Idle Tests. Units are ppbv except CO as noted.

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO, ppm Formal EtOH Acetal Mean Summer (n=11) 1.50 3.77 4.96 0.80 2.45 0.99 1.54 2.16 9.61 1030.68 9.04

% std dev 149% 116% 103% 110% 109% 104% 195% 160% 43% 59% 65%

Mean Winter (n=12) 0.66 2.57 3.01 0.48 1.71 0.65 0.54 3.06 6.53 3.86 3.37

% std dev 156% 137% 136% 111% 111% 96% 169% 118% 40% 61% 28%

Mean all 1.08 3.17 3.99 0.64 2.08 0.82 1.04 2.61 8.00 517.27 6.08

% std dev 163% 124% 116% 114% 110% 103% 214% 133% 46% 131% 81%



### Budi13 = 1,3BD; Benze = benzene; Tolue = toluene, Mp_xyl = m,p- xylene; o_xyl = o -xylene, Formal = formaldehyde; EtOH = ethanol , Acetal = acetaldehyde



### 5.3.2 Vehicle and Fuel Effects

The pre ceding section assessed overall mean concentrations in the trailing vehicle cabin, averaging across vehicles, emission modes and fuels; this section will separately consider these parameters.

Table 5.3- 4 details the effects of changing vehicle, fuel, an d emission mode.

The first two rows distinguish the truck and the car, averaged over all fuels and modes. These values are very similar, showing little effect of the vehicle by itself.

The next three rows distinguish the fuels, averaging over the vehicles and modes.

T he Atlanta fuel result s in higher BTEX concentrations in the trailing vehicle cabin, which is consistent with higher aromatic contents of Atlanta fuel, especially in summer (see Table 4.3 -1). The next two rows distinguish the normal and high emitter modes, averaging over the vehicles and fuels. The values clearly differ, with the high emitter mode values much higher than for the normal emitter mode.

The last line in this table presents the percent standard deviations of the high emitter values that are very similar, with the anticipated exception of MTBE which is larger due to its predominant occurrence in only one of the three fuels.

### 5

- 13 Figure 5.3- 7 presents the effect of normal versus high emitter vehicle on the trailing vehicle in -c abin concentrations in a scatter plot for all species except HCHO and

EtOH. Cabin levels of HCHO and EtOH were omitted since in-cabin upholstery and occupant sources of these compounds predominate penetration of outdoor levels. The slope indicates that in -cabin values measured during trailing the vehicle in high emitter

mode are about twice those found for the normal mode. Since lead vehicles in these tests are converted between ‘normal’ and ‘high emitter’ states by disabling control devices, not by mis -tuning the engines or opening fuel line leaks, exhaust emissions should remain roughly proportionate between both operational modes.

Table 5.3.4. Effect of Vehicle, Fuel, and Operational Mode. Units are ppbv, except CO as

noted. Number of measurements = n

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO, ppm Formal Acetal Truck only (n=12) 0.64 1.40 2.32 0.45 1.46 0.61 0.87 1.56 4.55 3.67 Car only (n=12) 0.59 1.13 1.87 0.33 1.11 0.45 0.53 1.42 5.90 3.59 Atl fuel only (n=8) 0.53 1.44 2.79 0.51 1.66 0.68 0.14 1.41 5.99 3.39 Hou fuel only (n=8) 0.89 1.52 2.20 0.48 1.58 0.66 2.17 1.91 5.61 4.37 Chi fuel only (n=8) 0.48 0.87 1.32 0.20 0.66 0.28 0.03 1.22 4.20 3.19 Normal only (n=12) 0.06 0.46 1.05 0.21 0.73 0.31 0.16 0.41 5.21 3.26 High emitter only (n=12) 1.06 1.95 2.99 0.55 1.77 0.71 1.21 2.50 5.37 3.37 St Dev high emitter only 28% 36% 38% 41% 44% 44% 177% 52% 52% 64%



### y = 2.2228x + 0.4798

R 2 

### = 0.6929

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

0.0 0.2 0.4 0.6 0.8 1.0 1.2

Normal EmitterHigh Emitter



### Figure 5.3- 7. Scatter plot of Normal Emitter and High Emitter Mean In -cabin Values for all species except HCHO and EtOH. Looking at the high emitter mode only, Table 5.3- 5 presents high emitter mean in

cabin values for each fuel separately. MTBE values present the clearest difference. This is expected based on the fuel composition. The other species show relatively little difference. EtOH values are not shown, due to the Summer 2002 artifact.

### 5

- 14 Table 5.3-5. Influence of high e mitt ing v ehicles and each fuel on trailing vehicle in

- cabin concentrations. Units are ppbv except CO as noted.

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO, ppm Formal Acetal High Emiter, Atl (n=4) 1.02 2.35 3.97 0.67 2.12 0.85 0.03 2.48 5.04 2.80 High Emiter, Hou (n=4) 1.43 2.18 3.08 0.69 2.24 0.93 3.45 2.81 6.00 5.77 High Emiter, Chi (n=4) 0.91 1.40 2.02 0.31 0.98 0.42 0.06 2.08 5.42 3.90



### The high emitter values, averaged across fuels, are presented in Table 5.3-6 separated by season. HCHO has the largest difference, summer > winter, which is likely due to more rapid photochemical reactions or in-cabin off gassing rates during the summer. In addition, BTEX concentrations are consistently higher during the summer,

which is consistent with higher aromatic content s of summer fuels, especially for Atlanta (see Table 4.3 -1).

Table 5.3- 6. Summary of Seasonal Differences in the High Emitter Samples.

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO, ppm Formal Acetal Summer High 1.23 2.15 3.33 0.61 1.79 0.82 0.76 1.52 8.02 7.66 Winter High 1.06 1.89 2.86 0.53 1.78 0.69 1.39 2.92 4.22 2.27



### 5.3.3 Trailing Vehicle Effects

In the winter 2005 tests, separate canisters were collected for the high and low cabin ventilation portions of the tests; in the summer 2002 tests, only a single canister was collected integrating these two periods. Table 5.3-7 shows the average values from the high and low ventilation winter 2005 canisters. Their values are similar across

seasons. Table 5.3-7 shows that although me an canister (integrated) in

- cabin values were similar under high and low ventilation conditions, the range of concentrations observed by continuous PID monitor was much larger under high ventilation conditions, as illustrated in Figure 5.3 -8. The high ventilation condition continues up to 60 min and is then switched to low ventilation for the remaining 60 min. The outdoor ppbRAE- PID shows generally lower values and the two indoor peaks in the first 60 min are associated with the “near” tailgating portion o f the driving sequence. The outdoor PID2 shows generally lower values that the indoor PID1, since it was mounted on the aerial on the right side of the van, thus its inlet was mostly opposite to the tr uc k’s tailpipe (that was

situated on the left side of t he truck).

### 5

- 15 ME0 - IN-CABIN TRUCK MAL BASE HV TEST 2/25 8:56

0 10 20 30 40 50 60 70 80

0 30 60 90 120

elapsed time (min)PID

PID1 PID2



### Figure 5.3-8. Time Series of In-Cabin (PID1) and Outside (PID2) PID Values. The first 60 min are under high ventilation conditions (0-60 min) and the next 60 min (60-120 min) are under low ventilation conditions.

Table 5.3-7. Comparison of High and Low In -cabin Ventilation Conditions, Winter 2005 only. Units are ppbv except CO as noted.

Budi13 Benze Tolue Etbz Mp_xyl O_xyl MTBE CO, ppm Formal Acetal High Vent only 0.52 1.15 2.07 0.40 1.35 0.54 0.74 1.54 4.38 2.13 Low Vent only 0.64 1.24 1.91 0.35 1.25 0.47 0.91 1.89 4.65 3.08

### 5

- 16 5.3.4 Comparison with FTP Data

The driving tests were all conducted while the vehicle was in a hot stabilized operating condition. The FTP test phase most comparable is phase 2 (Bag 2) and this

section will examine the correlat ion of the Bag 2 components with observed values in the driving tests.

Figure 5.3- 9 correlates Bag 2 and the trailing vehicle benzene values. There is a trend of increasing cabi n benzene concentrations with increasing benzene FTP emissions (R 2 

### =0.64). Figure 5.3- 10 presents the same correlation for MTBE although there are fewer data points since only the Houston fuel contained substantial concentrations of MTBE. Figure 5.3-11 ill ustrates the same correlation for 1,3 -BD. Unlike benzene and MTBE, 1,3-BD is primarily an exhaust component. The 1,3-BD plot shows the same correlation (R 2 

### =0.62) between the FTP emission level and the resulting trailing vehicle

cabin concentration as benzene

. The correlations are driven mostly by the vehicles in malfunction modes, since only these vehicle emissions result in significant concentrations in the trailing vehicle cabin.

y = 0.02x + 0.55

R 2 = 0.64

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

0 20 40 60 80 100 120 140

FTP Bag 2 mg/miTrailing Veh, ppbv Malfunction

Normal



### Figure 5.3-9. Comparison of FTP Bag 2 Benzene Emissions to In- cabin C oncentration in the Trailing Vehicle.

### 5

- 17 y = 0.0367x + 0.5247

R 2 = 0.5041

0 1 2 3 4 5 6 7

0 20 40 60 80 100 120 140

FTP Bag 2 mg/miTrailing Veh, ppbv Malfunction

Normal



### Figure 5.3-10. Comparison of FTP Bag 2 MTBE emissions to in-cabin concentrations in the trailing vehicle.

y = 0.02x + 0.26

R 2 = 0.62

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

0 10 20 30 40 50

FTP Bag 2 mg/miTrailing Veh, ppbv Malfunction

Normal



### Figure 5.3-11. Comparison of FTP Bag 2 1,3- BD Emissions to In -cabin Concentrations in the Trailing Vehic le.

### 5

- 18 5.4 Discussion

The overall objective of this section is to assess the various effects that might impact trailing vehicle in

- cabin levels of leading vehicle emissions. A rural test site with very little traffic was chosen to minimize non- lead vehicle i nfluences on measured incabin values. Background samples were taken prior to the driving tests to quantify other possible sources. Measured component backgrounds were low and consistent from summer to winter although HCHO backgrounds were relatively high , suggesting in -cabin

sources.

Summer and winter in

- cabin values were similar in magnitude with the exception of HCHO which was higher in the summer, possibly due to higher photochemical activity and higher temperatures that led to more HCHO off- gassing of the vehicle cabin interior. EtOH values in Summer 2002 are much higher than in Winter 2005, most probably due

to the off- gassing effect of the continuous formaldehyde analyzer that was located in the trailing vehicle cabin for Summer 2002 measurements.

Trailing vehicle cabin values were substantially larger than background values except for HCHO which was actually lower than background in winter tests. Idle test sample values were on average twice those encountered in driving tests, suggesting that

pr oximity and proximity duration may substantially impact in

- cabin trailing vehicle

concentrations.

Average in

- cabin levels were little affected by different vehicles or fuels except for an MTBE fuel effect. However, averaging over the fuels and vehicles, the high emitter mode resulted in much higher trailing vehicle in -cabin values than the normal emitter mode, on average 2.2 times higher; except for HCHO which was relatively unchanged from background. Similarly, the season had no strong effect upon the trailing

vehicle concentrations.

Trailing vehicle ventilation status also affected in -cabin values. Although mean canister (integrated) in -cabin values were similar under high and low ventilation conditions, the range of concentrations observed by continuous PID and CO monitors was much larger under high ventilation. This may be rationalized as the vehicle moving into and out of the exhaust plume of the leading vehicle with in- cabin values changing rapidly under high ventilation; whereas under low venti lation, in

- cabin concentrations trapped as the vents were closed stayed relatively constant during the remainder of low

ventilation conditions.

Trailing vehicle tests indicated that the largest impact on in

- cabin values came from the emissions mode of the leading vehicle. Emissions observed in Bag 2 of the FTP tests were compared to the observed trailing vehicle levels of benzene, MTBE and 1,3

- BD. Benzene and MTBE have both exhaust and evaporative emissions while 1,3- BD is only emitted in exhaust. In- cab in benzene and MT BE levels appear to correlate with FTP emissions, however, 1,3-BD does not but correlates with other in- cabin species.

# Appendix A

Exposure Protocol and Study Plan for th e Section 211(B) Tier 2 High End Exposure Screening Study of Baseline and Oxygenated Gasoline

## APPENDIX A

Exposure Protocol and Study Plan for th e Section 211(B) Tier 2 High End Exposu re Screening Study of Baseline and Oxygenated Gasoline

Prepared for

AMERICAN PETROLEUM INSTITUTE

1220 L Street Washington, DC 20005-4070

Prepared by

Barbara Zielinska, Eric M. Fujita, John C. Sagebiel, and David E. Campbell

Desert Research Institute

2215 Raggio Parkway Reno, NV 89512

Lawrence R. Smith

Southwest Research Institute

6220 Culebra Road San Antonio, TX 78228-0510

Ted Johnson TRJ Environmental, Inc.

713 Shadylawn Road Chapel Hill, NC 27514

Revised: October 1, 2003

### ACKNOWLEDGMENT

This work is supported by the American Petroleum Institute. We gratefully acknowledge the administrative and technical support provide by Dr. Will Ollison of API. We acknowledge Darryl Joseph and Thomas Kelly of Battelle for their assistance with the continuous formaldehyde measurements during the pilot study phase of the project.

ii

### TABLE OF CONTENTS

ACKNOWLEDGMENT ................................................................................................................. ii

LIST OF TABLES ......................................................................................................................... iv

LIST OF FIGURE S ....................................................................................................................... iv

LIST OF APPENDICES ..................................................................................................................v

1. INTRODUCTION ................................................................................................................... 1-1

2. MEASUREMENT METHODS AND PROTOCOLS ............................................................. 2-1

2.1 Biomarker Measurements 

### ..................................................................................................... 2-7

2.1.1 Breath Sample Collection 

### ........................................................................................... 2-8

2.1.2 VOC Analysis in Breath Samples 

### ................................................................................. 2-8

2.2 Instrument Measurement Protocol 

### .......................................................................................... 2-8

2.2.1 Kore MS200 

### ............................................................................................................ 2-9

2.2.2 CO Instruments 

### ........................................................................................................ 2-9

2.2.3 Continuous ppbRAE Photoionization Detector (PID) 

### ..................................................... 2-11

2.2.4 Continuous Formaldehyde Monitor 

### ............................................................................ 2-11

2.2.5 BTEX by Solid Phase Microextraction (SPME) 

### ............................................................ 2-11

2.2.6 Time-Integrated Air Sample Collection and Analysis 

### ..................................................... 2-12

3. EXPERIMENTAL Protocol .................................................................................................... 3-1

3.1 San Antonio Controlled In-Cabin and R esidential Garage Exposure Measurements 

### .............. 3-1

3.1.1 Procurement of Test Fuels from Houston, Chicago and Atlanta 

### .......................................... 3-1

3.1.2 Determination of Tailpipe and Evaporative Emissions of Test Vehicles 

### ............................... 3-5

3.1.3 Relationship Between Exhaust Emission Rates and In-Cabin Exposure 

### ............................... 3-7

3.1.4 Relationship Between Evaporative Emission Rates and Exposure in a Residence With an
Attached Garage 

### ....................................................................................................... 3-8

3.2 Microenvironmental Exposure Measurements in Atlant a, Chicago, and Houston 

### ........................... 3-10

3.2.1 Exposure Diary and Script Development 

### ..................................................................... 3-12

3.2.2 In-cabin Exposures in Urban Microenvironments 

### .......................................................... 3-12

3.2.3 Technician Biomarker Analysis 

### ................................................................................. 3-13

3.2.4 Criteria for Selecting High End Microenvironments 

### ....................................................... 3-13

3.3 Meteorology 

### .................................................................................................................... 3-17

3.4 Data Analysis 

### .................................................................................................................. 3-17

3.5 Reporting 

### ........................................................................................................................ 3-19

4. PROJECT SCHEDULE AND DELIVERABLES .................................................................. 4-1

5. REFERENCES

........................................................................................................................ 5-1

iii

### LIST OF TABLES

Table No. Page No.



### Table 3-1. Collection of Time-Integrated Sa mples for Chemical Analysis – San Antonio ....... 3-4

Table 3-2. Test Plan for Each Vehicle ........................................................................................ 3-6

Table 3-3. Summary of the FTP Driving Cycle

.......................................................................... 3-7

Table 3-4. Protocol fo r trailing vehicle tests ............................................................................... 3-8

Table 3-5.Protocol for attached garage experime nts. The sam e vehicles and fuels as for trailing vehicle experiment are used. .................................................................................... 3-9

Table 3-6. Microenv ironm ent Listing. ....................................................................................... 3-10

Table 3-7. The Number of Samples for Each Microenviron ment for Three Cities and

Two Seasons ....................................................................................................................... 3-11

LIST OF FIGURES

Figure No. Page No.



### Figure 2-1

............................................................................................................................... ...... 2-2

Figure 2-2

............................................................................................................................... ...... 2-2

Figure 2-3

............................................................................................................................... ...... 2-3

Figure 2-4

............................................................................................................................... ...... 2-3

Figure 2-5. Variability of CO Electrochem ical Cell Re sponse with Temp erature. ................... 2-10

Figure 3-1: Overall Structure of 211(b) Monitoring Requirements

............................................ 3-3

Figure 3-2. Monitoring Require ments for San Antonio Study

................................................... 3-3

Figure 3-3. FTP Driving Cycle. ................................................................................................... 3-7

iv

### LIST OF APPENDICES

APPENDIX A............................................................................................................................. A-1

APPENDIX B ..............................................................................................................................B -1

APPENDIX C ..............................................................................................................................C -1

APPENDIX D............................................................................................................................. D-1

APPENDIX E ..............................................................................................................................E -1

v

### 1. INTRODUCTION

The U.S. Environmental Protection Agency (EPA) has recently issued requirem ents for a test program in accordance with the Alternative Tier 2 provisions of the fuels and fuel additives (F/FA) health effe cts testing regulations, which are required pursuant to Section 211(b) of the Clean Air Act. In response to these requirements, the American Petroleum Institute (API) contracted with a research t eam consisting of the Desert Research Institute (DRI), Southwest Research Institute (SwRI), Lovelace Respiratory Resear ch Institute (LRRI), and TRJ Environmental, Inc (TRJ) to conduct a screening study of the high-end distribution of inhalation exposures to evaporative and combustion emissions of baseline- and oxygenated gasoline. This study plan describes the exposure protocols and specifies the measurement methods, sampling & analytical procedures, and quality assurance protocols that will be used in the study.

The goal of this research program is to screen potentia l hi g h-end inhalation exposure microenvironments dominated by evaporative and exhaust emissions of baseline- and oxyg enated-gasoline. The specifi c objectives are to provide information allowing the Agency to:

• Quantify personal exposures to motor vehicle oxygenated and non-oxygenated gasoline evaporative and

exha ust emissions in microenvironments (MEs) representing the upper end of the exposure frequency distribution of such exposures;

• Determine the quantitative relationships between personal exposures in selected MEs with fixed site

measurem ents in these MEs and at nearby air monitoring stations;

• Determine how personal exposures differ in cities and seasons in which methyl tertiary butyl ether (MTBE)-oxygenated, ethanol (EtOH)-oxygenated, and baseline gasolines are in use;

• Extrapolate to other sites and, if possible, other oxygenated fuels;

• Determine the relative contributions of vehicle fuel ex hau st and evaporative emissions to personal exposures from oxygenated and non-oxygenated gasoline.

The overall approach for the exposure study is based upon the draft June 29, 2001 S211b Tier 2 Exposure Study

Prot ocol that was developed in May 2001 by the API Section 211(b) Research Group and reviewed by the U.S. Environmental Protection Agency (EPA). The main study protocol has changed significantly from the original version based on the results from the first Reno pilot study (submitted to EPA April 25, 2002) and recommendations made by EPA during the summer Atlanta site visit in August 2002, specifically in relation to the measurement methods approach. These changes were incorporated into the second Reno pilot study in April 2003 (submitted to EPA June 13, 2003). Additional protocol adjustments incorporated into this September 4, 2003 draft have been the result of continuous dialog between EPA and DRI.

The main exposure study consists of gathering data under controlled and field conditions. First, DRI and SwRI will

condu ct ex posure measurements under controlled conditions in order to establish quantitative relationships between vehicle tailpipe and evaporative emissions to exposure leve ls in two specific microenvironments, a trailing vehicle cabin and an attached residential garage. In the field, DRI and LRRI will monitor microenvironmental and personal exposures in various potential high-end microenvironments in Houston, Chicago, and Atlanta during summer (July to September) and winter (January to March). These cities have ongoing ambient monitoring programs and have MTBE-RFG, EtOH-RFG, and baseline gasoline formulations, respectively. A number of key variables will be

measured in ambient air within microenvironments, in subjects’ personal breathing zones and in breath. Section 3 specifies the microenvironments and ex posure protocols. The results of this study will provide information to quantify the upper-end personal exposure to gasoline and oxygenated gasoline emissions and extrapolations to other cities using oxygenated fuels. The information from this st udy will permit sensitivity analyses to determine the range of these exposures, especially during heavy traffic, in residential and public parking garages and during refueling.

1-1

### 2. MEASUREMENT METHODS AND PROTOCOLS

The exposure screening study uses three approaches to measure the targeted air toxics in high-end microenvironments: (1) reference method time-integrated samplers to quantify concentrations over 5-60 minute sampling periods; (2) continuous surrogate method monitors to determine short-term concentration variations over 10-60 second sampling periods; and (3) supplementary methods to provide additional short-term surrogate

concentration estimates over intermediate time frames of one to several minutes. It should be noted that the supplemental methods are newer methods that, in many cases, utilize instrument s that have not been fully adapted for field use. These methods are independent checks on the surrogate approach, providing periodic corroboration under differing conditions and locations encountered during the tests. Th e supplementary method data are not required to conform to the CAA requir ements and therefore should not to be used in regulatory decision making.

1. The reference method s include pumped whole-air canister sample rs used for CO, CO2, benzene, toluene, ethylbenzene, xylenes (BTEX), MTBE and 1,3 butadiene (BD), acidified 2,4-diphenylhydrazine (DNPH) cartridges for formaldehyde (HCHO) & acetaldehyd e (CH3CHO) and a multi-bed (TenaxTA-CarbotrapCarbosieve) solid adsorbent tube for EtOH. Canister CO and CO2 are converted to methane for analysis by gas chromatography with flame ionization detection (GC/FID) and BTEX, MTBE, 1,3 BD are quantified by capillary GC/FID, or GC/MS for breath samples, us ing separate analysis. The aldehyde cartridges are eluted with acetonitrile and analyzed by high performance liquid chromatography with photodiode array UV detection of their hydrazone derivatives. The multi-bed tubes are thermally desorbed into a gas chromatograph and quantified by mass spectrometric detection (GC/MS). In addition, the multi-bed tubes provide the opportunity to compare the values for toluene, ethylbenzene and xylenes obtained by the canister method with those obtained by the tube method. These methods are basically standard TO-15, - 11A, and -17 EPA procedures with improvements inco rporated by the Desert Research Institute (DRI), as described in Section 2.3.5. .

2. The surrogate methods include both active non-dispersive infrared (NDIR) and passive T-15 Langan electrochemical cell devices for CO and an active p hoto-ionization detector (PID) for volatile organic compounds with an ionization potential below 10.6 eV (principally olefins and aromatic species). These continuous instruments respond to concentratio n changes of a few seconds and provide sensitive proportionate measures of the short-term variability of target exhaust and evaporative species quantified by the time-integrated reference methods. These methods are used to generate the short-term time-series of concentrations for BTEX, MTBE, EtOH, 1,3 BD, and the aldehydes quantified by the reference methods.

3. The supplemental methods include both active continuous instruments with one to several minute time responses, respectively, for BTEX and HCHO and a passive sorbent fiber sampling of a flowing analyte stream for BTEX over a 10-minute period. The continuous BTEX monitor quantifies species diffusing through a semi-permeable membrane by ionizing them at 70 eV by electron impact and pulsing them into a time-of-flight (TOF) mass spectrometer. The HCHO instrument bubbles ambient HCHO into a flowing aqueous 2,4-pentanedione reagen t to produce a formaldehyde-spe cific product, 3,5-diacetyl-1, 4- dihydrolutidene that is quantified by ultra- violet fluorescence. The 75 um solid phase (carboxen/polydimethylsiloxane) (SPME- CAR/PDMS) fiber is passively exposed for ten minutes, retracted into its syringe holder, and promptly inject ed into a GC with PID/FID detection optimized for BTEX quantification.

The surrogate approach is used to generate short-term ti me-series values for t he targ et species (MTBE, EtOH, 1,3 BD, CH3CHO) for which there are no continuous measures. In microenvironments with running engines exhaust emissions may dominate and either CO or PID surrogates sh ould provide comparable time- series measures of shortterm values, as shown in Figure 2-1. In engine-off mi croenvironments, evaporative sp ecies should dominate and the PID surrogate should provide the time- series measure since CO isn’t emitted, as shown in Figure 2-2.

2-1Continuous Measurements

0.0 5.0 10.0 15.0 20.0 25.017:0017:1017:2017:3017:4017:50CO (ppm)

0 200 400 600 800 1000PID

API CO DRI T15 CO PID (ppb) Reconstructed BTEX

0 50 100 150 200 25017:0017:1017:2017:3017:4017:50BTEX (ppbv)

BTEX (PID) BTEX (T-15 CO) BTEX (API CO)

Figure 2-1

Since collocated contemporaneous re fe re nce m easurements are paired w ith surrogate measures during each sampling period, each time-series generate d is individually calibrated to the sp ecific target compound/CO or target compound/PID relationship determined by the vehicles, fuels, and conditions measured during that period. The area under the continuous surrogate trace is nor malized to that of the integrated reference measurement which is assumed to be relatively constant over the 20-40 minute period of measurement.

Continuous Measurements

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.517:0017:1017:2017:3017:4017:50CO (ppm)

0 2000 4000 6000 8000PID

DRI T15 CO PID (ppb) Reconstructed BTEX

0 100 200 300 400 500 600 700 80017:0017:1017:2017:3017:4017:50BTEX (ppbv)

BTEX (PID) BTEX (T-15 CO)

Figure 2-2

A constant compound/surrogate ratio is required during the period of measurement to provide reliable time-series

values . Howe ver, where continuous m on itors are available (although of diff erent time resolutions), such values (e.g., BTEX, HCHO) may be compared to surrogate time series results as backup confirmatory data reducing uncertainties in the measurements, as shown in Figures 2-3 and 2-4.

2-2Figure 2-3 0 4 8 12 16 2012:0012:0312:0612:0912:1212:1512:1812:2112:2412:2712:3012:3312:3612:3912:4212:4512:4812:5112:5412:57

TimeBattelle HCHO, ppb

0 4 8 12 16 20Recon HCHO, ppb



### Measured HCHO (ppb) Reconstructed HCHO from CO and DNPH

0 100 200 300 400

7:05 7:15 7:25 7:35 7:45 7:55 TimePID Concentration (ppbv)

0 100 200 300 400SPME Concentration (ppbv)

PID (ppb) avgPID SPME

Figure 2-4

2-3Analytical method descriptions and data quality objectives are tabulated below. Note that in the Measurement Data Quality Objectives table, the Time Resolution row reflects the time resolution logged in this study rather than the higher time resolution capabilities typical of specific instruments noted in the Continuous Methods table.



### Integrated and Semi-Continuous Methods

Integrated Semi-Cont.

Method Canister DNPH Adsorbent SPME

Applicable

Environments all all all all

Time Resolution 5-60 min 20-60 min 20-60 min 10 min

Detection Limits 0.05 ppbC 0.1 ppbv 0.2 ppbv 0.2 ppbv

Data Application Reference (R) Reference (R) Reference (R) Confirmatory (C)

CO R

PID

BTEX R C

1,3-Butadiene R

MTBE R C

Formaldehyde R

Acetaldehye R

Ethanol R

NMHC R

2-4

### Continuous Methods

Continuous

Method T15 CO NDIR CO ppbRAE MS200 HCHO

Applicable Environments outdoor and incabin all all higher end stationary

Time Resolution seconds seconds seconds 1 min 1 min

Detection Limits 0.1 ppm 0.04 ppm 1 ppb 1-3 ppbv 1 ppbv

Data Application Surrogate (S) Surrogate (S) Surrogate (S) Confirmatory (C) Confirmatory (C)

CO Surrogate Surrogate

PID Surrogate

BTEX S (a) S (a) SC (c) C

1,3-Butadiene S (a) S (a) S (c)

MTBE S (a) S (a) S (c)

Formaldehyde S (b) S (b) S (d) C

Acetaldehye S (b) S (b) S (d) S (g)

Ethanol S (e) S (e) S (f)

NMHC S (a) S (a) S (c)

S (a). Time series reconstructed from canister/CO ratio for exhaust-dominated samples. S (b). Time series reconstructed from DNPH/CO ratio for exhaust-dominated samples except outdoor daytime samples. S (c). Time series reconstructed from canister/PID ratio for exhaust- or evap-dominated samples in outdoor MEs. S (d). Time series reconstructed from DNPH/PID ratio for exhaust-dominated samples except outdoor daytime samples. S (e). Time series reconstructed from solid adsorbent/CO ratio for exhaust-dominated samples. S (f). Time series reconstructed from solid adsorbent/PID ratio for exhaust and evap-dominated samples. S (g). Time series reconstructed from CH3CHO DNPH /HCHO Cont ratio for exhaust dominated samples.

2-5

### Measurement Data Quality Objectives

Instrument Canister DNPH SPME CO-T15 CO-NDIR PID HCHO (1) MS-200

Accuracy <5% <5% 3-50% +/- 1 ppm (2) <0.1 ppm or

0.5% NA <25% <8%

Precision <3% <3% 2-15% +/-0.1 ppm +/-0.1 ppm or

1% 0.1 <25% <5%

Detection

Limit 0.05 ppbC 0.1 ppbv 0.2 ppbv 0.1 ppm 0.05 ppm 1 ppb 1 ppb 1-3 ppbv

Time

Resolution (3) variable variable variable 10 sec 10 sec 10 sec 1 min 1 min

Artifacts None None None H2, very high humidity CO2>10 -4

H2O>4x10 -5 plastics,very high humidity None None

Method GC/FID HPLC/

Photodiode

array GC/FID

& PID Electrochemical

Detector NDIR 10.6 eV lamp PID Hantzch rxn

fluorescence Mass
spectrometer

Source DRI QA/QC

Ext Audits Comparisons DRI QA/QC

Ext Audits Comparisons DRI Use/intercomp

arisons Manufacturer

literature Manufacturer

literature Manufacturer

literature DRI Use/intercomp

arisons DRI Use/intercomp

arisons

(1) HCHO performance paramters based on Alpha Omega instrument's performance in the 2nd Reno pilot study. (2) Based on DRI test (3) Time resolution for continuous instruments designates data logging resolution used in the study rather than instrument time resolution

2-6The continuous Kore MS200 will be used to monitor BT EX on a one-minute basis, sampling during the initial 10 second portion of each 60 second period. This instrument uses a time-of-flight mass spectrometer to separate compounds of interest. Rather than using a gas chromatograph, this instrument uses a software solution to apportion the contribution of each component of interest to the time-of-flight (TOF) mass spectrum seen by the instrument. The software does not distinguish between specific isomers, thus xylenes and ethylbenzene are reported together. The inlet uses a polydimethylsiloxane membrane preferentially to allow non-polar organic compounds into the analyzer while maintaining the vacuum inside the analyzer chamber. This membrane inlet does limit the types of compounds that can be analyzed, however. Common air constituents and polar organic molecules do not pass the membrane quickly. The instrument performed well during th e pilot studies, comparing favorably with the canister measurements for most samples. Although we have attemp ted to secure the availability of another Kore MS200, which Horiba Instruments, Inc. in Irvine, CA, maintains, repeated shipping damage to this only other MS200 in the US has made its availability problematic. Given the periodic corroborative use proposed for this device, we do not believe the information provided by this instrument, while desirable, is necessary to fulfill the goals of the screening study. In the unlikely event this device goes out of service in the field, we will attempt to access the Horiba backup unit. Due to interferences from the vehicle’s ignition sy stem, likely the result of occasional resonances set up between engine electrical radio-frequency noise and MS200 circuits, this instrument may not provide full data capture during the mobile ME. Use of alternative instrument grounding and engine ignition filters will be investigated to remedy this occasional nuisance. Sinc e the MS200 runs directly off isolated 12V AGM battery power, it should also be isolated fr om battery inverter electrical noise

Carbon monoxide will be monitored continuously by the Langan T15 CO monitor and by the ML 9830 (Monitor Lab) N D IR instrument. Langan T15 is an electrochemical monitor for CO. The response time of this instrument is somewhat slower than the response of the infrared-based instruments.

A Continuous Formaldehyde Monitor was purchased from Alpha-Omega Power Technology, Ltd. (Albuquerque, NM). The Alpha-Omega (AO) instrum e nt utilizes the Hantzch reaction - it absorb s formaldehyde in acidified water, reacting it with 2,4-pentanedione and ammonia to form a cyclized product, 3,5-diacetyl-1, and 4-dihydrolutidene, which is continuously detected by fluorescence. The method is highly specific for formaldehyde and very sensitive. The AO device has been extensively modified by DRI to e nhance its field reliability and ruggedness to vibration and shock and is designated as the DRI-formaldehyde instrument in subsequent discussion. However, its use is limited to stationary microenvironments in the present study since sensitivity to motion remains.

2.1 Biomarker Measureme nts

Du ring the 1 st Reno pilot study both urinary and breath concentrations of MTBE and the BTEX compounds were measured in two subjects after three separate scripted e xposures. Breath measurements showed an exposure effect (post-exposure concentration in breath higher than pre-exposure concentration) when samples were collected soon after exposure (within ~2-3 minutes). Breath samples co llected after longer post-exposure durations showed no increase relative to pre-exposure breath concentrations, most likely due to the short 1-3 minute half lives of these compounds in breath (Lindstrom and Pleil, 1996). The shor t half-life of absorbed volatile vapors such as BTEX in breath will require fast, precise timing for sample collection.

Urinary measurements from the pilot st udy showe d little exposure effect from most compounds for 2 of the three exposures. In all cases the urinary concentrations of MTBE, toluene, ethyl benzene, and xylene were below detection limits. In most cases the concentrations of benzene (the only observed compound) post-exposure were similar to pre-exposure due to the fact that the exposure concentrations were low in most cases. After the highest exposure in the pilot study (refueling a vehicle - hourly canister average of about 10 ppbv benzene) there was a relatively strong exposure effect obser ved in one subject and a lesser exposure effect observed in a second subject.

There was a time course in the elimina tion of benzene that showed urinary be nzene concentrations increasing with time. This is similar to the results reported by Lee and Weis el (1998) on the behavior of MTBE in urine. Because of an inability to see the decay of urinary benzene 3 hour s post exposure, a second scri pted refueling exposure was conducted in Reno, NV, to rep eat this peak exposure and see if the urin ary VOC concentration data can be linked to an exposure effect at these levels an d to follow the full time course of elimination. The measurements of urinary MTBE/BTEX from the second refueling experiment were successful, but demonstrated no differences between preand post-exposure.

2-7Based on the pilot study results, since it was not possible to discriminate urinary benzene concentrations in postexposure as compared to pre-exposure, it was d ecided not to conduct urinary measurements.

Based on results from the 2 nd Reno pilot study, breath sampling will be conducted in three microenvironments; outdoor refueling, trailing high emitting vehicles (or roadway tunnel in Chicago and Houston), and underground

garages. Three 1 liter breath canister samples will be collected for each experiment: befo re the exposure in the isolated subject, and 10 seconds (tim ed with a stopwatch) immediately afte r active refueling or a measured peak exposure in the other MEs. In addition, a third backup br eath sample will be collected immediately after the second sample for these three microenvironments, in case there is a problem with the second sample.

2.1.1 Breath Sample Collection

Breath samples will be collected from technicians who particip ate in a scrip t ed exposure. Since this study requires the use of human subjects, the final protocol was reviewed by an Institutional Review Board certified with NIH.

Technicians will be instructed to avoid exposure t o material that may compromise the exposure assessment prior to and during the scripted exposures. This will include avoi ding alcohol ingestion (ethanol) and first-hand or secondhand cigarette smoke for at least 3 days prior to the sc ripted exposures. Breath samples collected before the exposure will be used to assess background levels in the technician.

The test subject technician will take the three breath samp le s. One sample is taken before initiating ME sampling; the second, ten seconds (timed with a stopwatch) immediately after completing ac tive refueling task or experiencing a measured peak exposure in another ME, and the third one immediately follo wing the second. The 3 rd sample will be analyzed only in case there is a problem with the second sample. The technician takes a 1-liter canister, places the tube in his mouth, and breathes smoothly and regularly through the mouth around the tube until a resting breath pattern is established. At the end of a normal exhalation, the technician closes the mouth, opens the canister valve, and continues to expel the expiratory rese rve. The canister vacuum will collect 1 L of the expiratory reserve. When the flow stops, the technician closes the canister valve to capture the sample (Pleil and Lindstrom, 1995; 2002).

2.1.2 VOC An alysis in Breath Samples

The analysis of VOC in breath samples will be conducted as described by Pleil and Lindstrom (1995, 2002) Prior to

th e com mencement of the study, the CO2 level in alveolar breath of all technicians performing breath sample collection will be measured using GC/FID. Since the FID does not respond to CO2, this species is converted to methane by a methanator, positioned after the GC column, but ahead of the FID. Three breath samples will be collected and analyzed, and the mean CO2 value will be used for further comparison. After breath sample collection, the CO2 will be measured using the same meth od. The target VOC (MTBE, 1,3-butadiene, ethanol, BTEX) will be measured using a GC/MS technique. The GC/MS system includes: Entech 7100 preconcentrator, Varian 3800 gas chromatograph with FID and column switching valve, and Varian Saturn 2000 ion trap mass spectrometer. Breath canister samples are pressurized w ith laboratory-grade zero air and a dilution factor is calculated based on initial and final pressures. An additio nal normalization factor could be determined for samples that deviate significantly from the e xpected CO2 level (subject-specific CO2 level/dilution factor). Approximately 200 to 300 ml of the breath sample is concentrated and injected at the head of a 60 m x 0.32 mm polymethylsiloxane column (CPSil-5, Varian, Inc.) held at 30 ° C. This column is connected to the switching valve leading into a 30 m x 0.53 mm GS-GasPro column (J&W Scientif ic). After approximately 7 min the valve is switched so that the effluent from the first column elute onto a second 15 m x 0.32 mm polymethylsiloxane column connected to the mass spectrometer. The column switch is timed so that the C2 and C3 compounds elute on th e FID and all C4 and higher compounds elute on the mass spectrometer.

2.2 Instrument Measurement P rotoc ol

This section describes protocols that will be applied for each method and applicable quality assurance procedures.

2-82.2.1 Kore MS200

The Kore MS200 will be used to measure BTEX in select MEs. The protocol for use includes the following

calibratio n and op erational procedures.

Calibration Procedures:

1. Start in strument and establish zero.

2. Apply span gas and allow 2 minutes to stabilize response.

3. Collect at least 5 sp ectra
4. Using calibratio n section in software, confirm calibration response or enter new calibration values as

neede d

. Daily Startup Procedures :

1. Check Battery Status (or plug in).

2. Inlet valve: Middle position (heater).

3. Inlet pump: On

4. Wait until inlet vacuum is less than 3x10 2 pa and inlet temperature LED is green

5. Sample pump On

6. TOF MS: On

7. TDC: On (unless you are on battery, then wait as this draws a lot of current.)

Once you a re ready to sample :

1. In let Valve Down position (confirm that vacuum is ok and heat is still ok)

2. Apply zero air and allow it to flow for at leas t 1 minute.

3. Collect 5 spectra of background air to assess variability.

4. Begin sampling

If p ossible, during a run perform a zero check as follows: Apply zero air for 15 to 30 seconds, allowi ng th e in strument to collect one spectrum. After a sampling run, perform a zero check as follows: Apply zero ai r and immediately collect at least 5 spectra

. Allow the zero ai r to remain on the instrument for

5 minutes and collect another 5 spectra.

During sampling runs, keep track of the main analyzer chamber vacuum. If the vacuum is regularly getting above 20

x10 -6 Pa, the instrument may need baking out. Follow the written procedures for bakeout.

2.2.2 CO I nstr ume nts

Two CO monitoring instruments will be used for the field stud y : a high sensitivity, fast response gas-correlation unit (Monitor Labs 9830) as a reference device, and a portab le, battery-powered passive electrochemical unit (Langan T15). Prior to each period of field m easurements both instruments will be ca librated using a zero-air generator and span gas (10.5 ppm) to provide two reference points encompa ssing the expected range of concentrations anticipated during actual testing. The two-point calibration procedure is as follows:

1. Collocate instruments and warm up for a minimum of 45 minutes. During the study the CO units will be powered 24/7 since the van is on AC power overnight to recharge the batteries and the passive Langan unit draws little power from its long-lasting batteries. Collocated Langans will be tested for calibration stability in high CO MEs and paired during runs if found to be unstable.

2. Record ambient concentration as determined by each instrument. 3. Connect inlet lines from both instruments to a zero-air source (for passive sampler use flooder cap

p r ov ided by manufacturer) and check for pos itive flow rate of >1 lpm with rotometer. 4. Let instruments stabilize, record current baseline, then adjust zero. 5. Connect inlet lines to a tank of span gas with ap pro p riate CO concentration for anticipated range and verify flow rate 6. Let instruments stabilize, record current re ad ing , and adjust span to correct value.

2-97. Re-connect zero-air source, let stab ilize and check baseline zero readings. 8. Repeat steps 4-7 if necessary. 9. Check third concentration level with span gas if available.

During field measurement periods the passive sampler w ill b e ch ecked against the reference unit, which has an

automatic baseline stabilization and in ternal zero-air source, at the beginning and end of each sampling day and baseline readings will be recorded. If any significant devi ations are observed a re-calibration will be performed.

The electrochemical cell in the Langan in s truments exhibits a significant response to temperature variations as shown in Figure 2.2-1. Note that these variations are due to changes in the temperature of the electrolyte in the cell, not in the ambient air temperature. Prior to field use, the temperature response will be characterized at realistic CO levels in the laboratory. If the response appears to be su fficiently reproducible, the resulting concentration data will be adjusted based on the units intern al temperature sensor, which has an accu racy of +/- 2 C. If the temperature compensation approach does not appear feasible, the instru ment will be thermally isolated and maintained as close to calibration temperature (typically 20 C) as possible during use.

Our initial evaluation indicated that the lead-acid batteries are a sou r ce of hydrogen that interferes with the Langan CO monitor. This was confirmed by observing the Langan CO monitor in the presence of the batteries when both

were removed from the vehicle. In order to eliminate this source of interference, the wet-cell lead acid batteries were replaced with AGM batteries that are sealed and hence do not outgas. We have currently installed 4 large AGM batteries and two new battery chargers in the van along with two new power inverters providing a total of approximately 3000 Watts of continuous power at 110V AC . The power system will be permanently installed so that we will not need to remove the batteries to charge them, they will simply be plugged in to charge. To handle the additional load, we have installed overload springs on the van. Furthermore, racks have been installed to secure instruments from movement and vibration; instrument & sampler inlet mounts have been installed to collocate inlets further within driver’s breathing zone (including one PID inlet with the other PID sampling outside the vehicle on the radio antenna at least six inches above the hood); a re mote switch was installed to allow cabin on/off control of the integrated samplers; and a hitch-mounted rack was insta lled to transport the instrument cart. We will continue to use the other batteries for the cart experiments since th e lack of a trapped space means we will not encounter

interferences. We will also use the NDIR-based CO instrume nt, which does not suffer from the same artifact as the Langan, inside the vehicle cabin.

Figure 2-5. Variability of CO Electrochemical Cell Response with Temperature.

2-102.2.3 C ontinuous ppbRAE Photoionization Detector (PID)

A RAE System s Mo del PGM-7240 (ppbRAE) portable PID monitor is used to continuously monitor ambient VOC

le vel s in the microenvironments. The monitor is equipped with a 10.6 eV photoionization (PID) detector and responds to organic and inorganic gases that have an ionization potential of less than 10.6 eV, which includes most compounds of interest in this study. It does not respond to light hydrocarbons such as methane, ethane, propane or to acetylene, CO, or formaldehyde. .

2.2.4 Continuo u s Formaldehyde Monitor

The continuous monitor for gaseous formaldehyde was purchased from Alpha-Omega Power Technologies. This

in st rument uses Hantzsch reaction to produce a fluorescent derivative from HCHO that is monitored with a fluorescent detector. An aqueous calibration standard in the 10 -7 to 10 -6 M range made by serial dilution of 37%

formalin solution in the 0.1 N H 2 SO 4 scrubber solution is used for the daily instrument calibration (Kelly and Fortune, 1994). This daily calibration standard is compared with the gaseous formaldehyde standard, purchased from Apel-Riemer Environmental, Inc. The monitor is zeroed by supplying high-purity air to the inlet. Span and zero samples are provided to the mon itor at regular intervals using automated valving. We’ve completed reengineering the Alpha Omega HCHO instrument to make it more field-rugged and reliable.

The modified Alpha-Omega HCHO inst rum e nt was evaluated during the 2 nd Reno Pilot study. One of the most significant limitations of the formaldehyde monitor was an apparent sensitivity to moving environments. It has been observed that when the formaldehyde instrument was warmed up and operated in a stationary environment, such as a parking garage, and then subjected to transport while still operating, response at the detector oscillated and increased overall. Another limitation of this continuous instrument was the long stabilization time required for the fluorescence detector upon instrument start-up. In some cas es, response at the detector was still stabilizing when the sampling period began. Thus, the supplemental continuous formaldehyde analyzer will be used for monitoring stationary microenvironments only.

2.2.5 BTEX by Solid Phase Microextraction (SPME)

Carboxen/(poly)dimethylsiloxane (CAR/PDMS) coated (75 μ m) q uartz fibers are used for 10 min BTEX sampling. All SPME samples are analyzed in a mobile laboratory with a Model 8610C SRI Instruments GC equipped with a heated injection port suitable for SPME desorption and a CP-Sil 5 (Varian, Inc.) capillary column (60m, 0.32mm i.d.) and a PID detector. Th e heated flash vaporization in jector is maintained at 250 ° C and PID at 150 ° C. The column temperature program was 60 ° C for 2 min, 8 ° C/min to 165 ° C and held for 1 min, and then 45 ° C/min to

240 ° C and held for 2 min. Helium carrier gas flow rate was 3 ml/min.

Blanks and calibration checks are performed daily on the SRI GC in order to determine the performance of the

instru m ent and quality of the data. Fibers are kept in the injector port throughout the sample run to guarantee that the entire sample was desorbed and to begin the conditioning of the fiber. In addition, fibers are cleaned in a fiber

conditioner at 300 ° C for at least one hour. One fiber per batch of 5 is checked for purity after conditioning. The fiber conditioner consisted of a 70 cm x 16 cm stainless steel box with 5 ports machined to fit the needle size and a Watlow heater/temperature controller capable of maintaining the temperature in the 200-300 ° C range. A helium flow of approximately 10 ml/min is maintained during fiber conditioning. Testing showed that the same fiber can be subsequently reused up to 40 times for collecting additional samples, unless breakage of the fiber or failure of the fiber mounting mechanism occurs.

The SRI GC is calibrated with 1 μ l i n jection of liquid standards prepared in pentane with BTEX at different concentrations (1, 5, 10, 20, 40, 50, and 100 ng/ μ l). Carboxen/PDMS fibers are calibrated by introducing the SPME for a defined time to a flowing standard gas containing the calibration component, which loads a known mass of standard onto the fiber. The fiber is then introduced to the analytical instrument for calibration. SPME gas calibrations are done initially and throughout the study when necessary. BTEX calibra tion is performed with certified gas standards at different concentrations (20, 80, 100 and/or 200 ppbv for each compound).

SPME is a passive method, thus the rate of the fiber uptake is controlled by the diffusion rate of the analytes to the

fiber

. In a stationary environment without any air move ment, the gradient of concentration is formed in the boundary layer between the fiber and surrounding environment. This is a situation that occurs during the fiber

2-11calibration in a static system, such as a Tedlar bag. Howe ver, in an outdoor environment there is always some air movement, so the air is passing continuously across the surface of the fiber. The sorption ra te will be higher in this situation, since the thickness of the boundary layer will be somewhat smaller.

We tested the fiber uptake in the dynamic (flow-through) conditions, in the apparatus shown in Figure 2.3-1, page 2-

9 o f the 2nd Reno Pilot Study Report (Zielinska et al., 2003) When the BTEX standard mixture was flowing through the system with the rate of 100 ml/min, the fiber uptake was approximately three times higher than in static (no flow) conditions. In addition, the dynamic calibration was more reproducible and more precise. For the summer study we will employ flow-through sampling conditions for the fiber. The calibration of the fiber will be performed in the identical flow-through conditions, using the same flow rate.

Sampling temperature is an important parameter affecting the SPME dat a . Temperature co rrections are obtained in the laboratory with an experimental set up that consists of a 1L glass bulb that has two stopcocks in each side to let the calibration gas flow through and an injection port covered with a sleeve septum to allow a SPME fiber to be introduced. The bulb is temperature controlled with a cooli ng/heating system. Temperature inside the glass bulb is measured with a thermocouple. For introducing humidity, a heated injection port is added before the glass bulb entrance in order to inject water with a syringe pump (Harvard Apparatus) to produce the desired relative humidity (Tuduri, Ludovic et al., 2001; Nelson, 1992; Martos, P. and J. Pawliszyn, 1997, and Lodge 1984).

SPME Carboxen/PDMS coated (75 μ m ) fi bers are used with portable or manual samplers. When manual samplers are used, the tip of the needle is closed with a septum or Teflon tape (Martos and Pawliszyn, 1997 and Chai and Pawliszyn, 1995). Prior to sampling, the pre-cleaned fibe rs will be kept at ambient temperature with an activated charcoal protector. This storage method has been tested in the laboratory and we have not seen any increases in the BTEX background up to 48 hours of storage following cleaning (the longest tested period). After sampling, fibers are kept in sealed Mylar bags inside a cooler with dry ice. Samples are analyzed 4-10 hours post-sampling, on average, with a minimum of 1 hour and a maximum of 20 hours between sampling and analysis.

2.2.6 Time-Integr ated Air Sample Collection and Analysis

Time-integrated monitoring methods are used primarily for quantification of the responses of continuous surrogate

in st ruments. The methods include canister sampling for VOC (BTEX, 1,3-butadiene, MTBE), solid adsorbent sampling (for ethanol) and DNPH-coated Sep Pak cartridges sampling for carbonyl compounds. The DRI Organic Analytical Laboratory (OAL) routinely uses these meth ods and DRI standard operating procedures (SOPs) for sampling and analysis are available upon request. Five to sixty minute samples will be collected depending on the ME sampled.

Sampling. The DRI custom built sampler that can sample simultaneously a canister, solid adsorbent cartridges (two in parallel) and DNPH-impregnated Sep-Pa c cartridge, is used for this study. The sampler is compact; it can be setup in a vehicle cabin and run from the battery. Prior to use the sampler is checked for cleanliness by sampling zero air through the canister inlet. If the concentration of any targeted compound exceeds 0.1 ppb, the sampler is thoroughly cleaned and re-tested. As noted earlier, a remote switch was installed to allow cabin on/off control of the sampler (no longer re quiring access through the van tailgat e) and the protocol was modifi ed to require that the van engine be off during changes of sampler media.

The canister sampler uses a differential pressure flow cont roller to su pp ly air to the sampler canister. A calibrated

mass flow controller will check the flow rate. Since the actual flow rate is less important than the fact that the flow rate remains constant, additional quality assurance checks on the flow controllers is not necessary. For the 5-min canister samples, an additional battery-operated sampler will be used, allowing up to 3 L/min flow rates to pressurize the 3 L canister.

Both the solid adsorbent and DNPH samplers use the same vacuum pump controlled by mass flow controllers.

Th ese con t rollers will be calibrated at the start of the fiel d program by using a primary flow device (e.g. Gillibrator) and then will be periodically check ed while in the field to confirm that the flow rates are accurate.

Canister samples. Prior to sampling, the canisters are cleaned by repeated evacuation and pressurization with humidified zero air, as described in the EPA document "Technical Assistance Document for Sampling and Analysis of Ozone Precursors" (October 1991, EPA/600-8-91/215). Six repeatable cycles of evacuation to ~0.5 mm Hg

2-12absolute pressure, followed by pressurization with ultra-high-purity (UHP) humid zero air to ~20 psig are used. The differences between the DRI procedure and the EPA reco mmended method are that, in the DRI method, canisters are heated to 140°C during the vacuum cycle and more cy cles of pressure and vacuum are used. According to our experience and that of others (Rasmussen, 1992), heating is essential to achieve the desired canister cleanliness. Also, the canisters are kept longer under vacuum cycles, about one hour in the DRI method, as opposed to half an hour in the EPA method. At the end of the cleaning procedure, one canister out of 12 in a lot is filled with humidified UHP zero air and analyzed by the gas chromatograph/flame ionization detection (GC/FID) method. The

canisters are considered clean if th e total non-methane organic compound (N MOC) concentration is less than 20 ppbC. The actual concentrations of blank-check canisters are typically below 10 ppbC.

Canister samples are analyzed for speciated VOC concentra ti ons promptly upon receipt of samples from the field, using gas chromatography with flam e ionization detection (G C/FID, Hewlett Packard) according to guidance provided by the EPA Method TO-15. The GC/FID response is calibrated in ppbC, using NIST Standard Reference Materials (SRM) 1805 (254 ppb of benzene in nitrogen). Based on the carbon response of the FID to hydrocarbons, the response factors determined from these calibration sta ndards are used to convert ar ea counts into concentration units (ppbC) for every peak in the chromatogram. Identification of individual compounds in an air sample is based on the comparison of linear retention indices (RI) with those RI values of authentic standard compounds. A DB-1 column (60 m long 0.32 mm i.d., 1 μm film thickness) is used for these analyses. Breath canisters will be quantified for CO2, MTBE, and BTEX by the method of Pleil & Lindstrom using GC/MS.

Blanks are performed once daily, while performance standards ar e e xecuted three times per week. Our analysis plan and data processing standards call for the replicate analysis of approximately 10% of the samples. For canisters the replicate analysis is conducted at least 24 hours after the initial analysis to allow re-equilibration of the compounds within the canister. The replicate anal yses are flagged in our database and the programs we have for data processing extract these replicates and determine a replicate precision. Replicate analysis is important because it provides us with a continuous check on all aspects of each analysis, and indicates problems with the analysis before they become significant. A portion (5%) of the canis ters will also be analyzed by a second independent laboratory (negotiations with Battelle-Columbus are currently underway).

Solid adsorbent samples. Ethanol will be quantified using solid adsorben t cartridges, in addition to canister method. Although MTBE is stable in SUMMA canisters and can be quantified with high precision and accuracy, ethanol is relatively unstable and the replicate analys es of canister samples show a high degree of scatter (Goliff and Zielinska, 2001). Thus, the solid adsorbent samples are only necessary for quantification of ethanol, although TEX data may be obtained from the solid adsorbent sample s to serve as a comparison with caniste r data for QA purposes. For sample collection we will use multibed adsorbent cartridges consisting of Tenax TA, Carbotrap (or Carboxen) and Carbosieve (Shire et al., 1996; Tsai and Weisel. 2000; Vaygha ni et al., 1999). Prior to use, the Tenax-TA solid adsorbent is cleaned by Soxhlet extraction with hexane/acetone mixture (4/1 v/v) overnight, and dried in a vacuum oven at ~80 °C. The dry Tenax is packed into Pyrex glass tubes together with Carbotrap and Carbosieve and thermally conditioned for four hours by heating in an oven at 300 ° C under nitrogen purge. Approximately 10% of the precleaned tubes are tested by GC/F ID for purity prior to sampling. Afte r cleaning, the tubes are capped tightly using clean Swagelok caps (brass) with graphite/vespel ferr ules, placed in metal containers with activated charcoal on the bottom, and kept in a clean environment at room temperature until use.

After sampling at nominal monitored flows of 200-300 ml/minute, tube samples are analyzed by the thermal desorptioncry ogen i c preconcentration method, followed by high-resolu tion gas chromatographic separation and mass spectrometric detection (MSD) of individual compounds. The Chrompack Ther mal Desorption-Cold Trap Injection (TCT) unit is used for the purpose of sample desorption and cryogenic preconcentration. The compounds are quantified by MS, using the response factors of authentic standards, prepared at five different concentrations with a static dilution bulb.

Carbonyl compounds. Formaldehyde and acetal dehyde will be collected with Se p-Pak cartridges that have been impregnated with an acidified 2,4-di nitrophenylhydrazine (DNP H) reagent (Waters, In c), according to the EPA Method TO-11A. When ambient air is drawn through the cartridge at nominal flow rates of 1 L/min, carbonyls in the air sample are captured by reacting with DNPH to fo rm hydrazones, which are separated and quantified using HPLC in the laboratory (Fung and Grosjean, 1981). Depending on the type of sorbent (C18 or silica gel) in the cartridge, the ambient measurem ent results are subject to various artifacts due to interaction with ozone, thus the ozone denuder is recommended for sample collection. We will use a honeycomb denuder coated with sodium

2-13carbonate/sodium nitrite/glycerol mixture (Koutrakis, et al ., 1993). After sampling, the cartridges will be eluted

with acetonitrile. An a liquot of the eluent will be tr ansferred into a 1-ml septum vial and injected with an autosampler into a high performance liquid chromato graph (Waters Alliance Sy stem) for separation and quantization of the hydrazones (Fung and Grosjean 1981). A portion (5%) of these aliquots will also be analyzed by a second independent laboratory (negotiations with Battelle-Columbus are currently underway). Liquid fuel samples. Liquid gasoline samples will be collected for each service station (if more than one is used per city) after ME 3/7 refueling measurements during subsequent off-loading of the van fuel tank at the mobile lab site. Composition of these fuels will be determined by GC/FID for comparison to measured species (benzene & oxygenates) reported in summer and winter gasoline surveys conducted for the three cities being sampled and for determining relative exhaust/evaporative emissions sources in measured MEs. Relative exhaust and evaporative emissions may be estimated from fuel component ratios as noted in Graboski et al., 1998.

2-143-1 

### 3. EXPERIMENTAL PROTOCOL

This section specifies the tasks require d to meet the objectives for the S211 (b ) Tier 2 Exposure Study and how each element of the proposed testing protocol will be carried out. Details of the methods and procedures and quality assurance program are described in Section 2. The exposure studies have two components. First, Desert Research Institute (DRI) and Southwest Research Institute (SwRI) will conduct exposure measurements in San Antonio under controlled conditions in order to establish quantitative relationships between vehicle tailpipe and evaporative emissions to exposure levels in a trailing vehicle cabin and in a residence with an attached garage. Second, DRI will monitor microenvironmental and personal exposures in 12 high-end exposure microenvironments in Atlanta, Chicago, and Houston during summer and winter conditions. Selection of the high-end microenvironments was made in consultation with EPA and independent peer reviewers. Figures 3-1 and 3-2 show the monitoring requirements for the overall study and for the controlled San Antonio studies, respectively.



### 3.1 San Antonio Controlled In-Cabin and Resi dential Garage Exposure Measurements

DRI and SwRI will determine the quantitative relationshi ps between evaporative and tailpipe emission from characterized test vehicles to exposure in (1) a cabin of a trailing vehicle under normal operation and with induced malfunctions and (2) a residence with an attached garage. The exposure measurements were made in San Antonio during June 2002 for summer fuels and will be made during January 2005 for winter fuels according to the following protocol. Part of the measurements made in June 2002 may be repeated in June 2004 after review of the entire San Antonio database by EPA. Table 3-1 shows the exposure matrix and the number of samples and hours of measurements for controlled in-cabin trailing vehicle and residential garage studies.

3.1.1 Procureme nt of Test Fuels from Houston, Chicago and Atlanta

With API and DRI guidance, SwRI will procure six test fuels (a su mmer regular grade and winter regular grade fuels in each of the three cities – Houston, Atlanta, an d Chicago) for the study. SwRI will procure two 55-gallon drums of each fuel from a major supplie r in each city to conduct the work in San Antonio. Three summer fuels were procured and evaluated during May 2002 and the three wi nter fuels will be procured during December 2004. SwRI will test fuels for bulk properties and DRI will speciate th e chemical composition of each of the six blended fuels.Figure 3-1: Overall Structure of 211(b) Monitoring RequirementsSegment NLeadingvehicleTrailingvehicleSegment 1CabinTestsFTPEmission TestsGarageAdjacentroomTest 1Test NGarageTestsNormalMalfunctioningSedanTruckRFG-MTBERFG-EtOHBaselineSummerWinterSan AntonioMEASUREMENTSReference integrated (20-40 min) canister-1,3 BD, MTBE, BTEX, VOC(20-40 min) DNPH cartridge - HCHO, CH3CHO(20-40 min) Multibed tube - EtOHContinuous surrogate (1 min) Langan-CO, ML-NDIR CO, ppbRAE-VOCSupplemental corroborative (1-5; 10 min): KORE-BTEX, DRI-HCHOSPME - BTEXOTHER DATADiary (ME/event)Location: GPS (lat/long, min)Meteorology: W S/W D, RH, T (min); surface roughness; stability classLocal air quality: sampling day monitoring station data (60 min)MEASUREMENTSSemi-continuous (10 min): SPME - MTBE, EtOH, BTEXOTHER DATADiary (ME/event)Location: GPS (lat/long, min)Meteorology: W S/W D, RH, T (min); surface roughness; stab. classLocal air quality: sampling day monitoring station data (60 min)Segments for Cabin Tests1 Initial background -- no test vehicles2 Idling, close spacing3 Moderate speed, moderate spacing4 High speed, greater spacing5 Final background - no test vehiclesGarage Tests1 Background, garage empty2 Car in garage, kitchen dooropen f or 1 min3 Car in garage, kitchen dooropen for entire test4 Car in garage, kitchen doorclosed -- window open5 Car in garage idling, garagedoor open, kitchen door openfor 1 min6 Back car out and close garagedoor

3-3Figure 3-2. Monitoring Requirements for San Antonio Study3-4orb.San ATable 3-1. Collection of Time-Integrated Samples for Chemical Analysis – San AntonioTestDuration(min)Sample timeSPME (min) SPME Cans DNPHSolid Adsorb.aNo. ofTests SPME Cans DNPHSolidAdsntonio- TrailingVehiclekground10 101 1 1124 24 24 24ure Measurements120 10 12 1 1124 288 24 2420 102 1 1124 48 24 2415 3 33360 72 72 12ntonio- Residential GaraInitial bac4Expos4Idle4SubtotalSan Age Exposureage (baseline)30 301 1 1124 24 24 24age (during exposure)150 305 1 1124 120 24 24ent room (baseline)(b) 301 1 1124 24 24 24ent room (during exposure)(b) 305 1 1124 120 24 2430 12 4 44288 96 72 12In-gar4In-gar4adjc4adjc4Subtotal3.1.2 Determination of T a ilpipe and Evaporat ive Emissions of Test Vehicles

SwRI will procure two test vehicles and determine evapor ativ e and tailpipe emissions for the vehicles with and without malfunctions using the six test fuels. The two test vehicles will be 1993 to 1996 model year vehicles with 90 to 110K odometer miles. One vehicle will be a sedan, and th e second a full sized pickup truck with a V-8 engine. The SWRI will measure the vehicle’s exhaust emissions on a dynamometer according to the Federal Test Procedures (FTP). SwRI will modify these vehicles so that emission control system components (e.g., ECU, O 2 sensor, catalyst) can be reversibly disconnected to represent normal and reasonable high-end approximations (e.g., ≥ 2 gm HC/mile exhaust) of real world exhaust emissions. Sw RI will determine exhaust emission rates for the two test vehicles, with and without malf unction, using three regional fuels during each of two seasons (with seasonal fuels).

This will result in 12 combinations for each season. Sw RI also will measure evaporative emissions using the same test vehicles with and without induced malfunction (e.g., di sconnecting fuel line to car bon canister). Hydrocarbon samples will be collected in canisters and analyzed by DRI for complete hydrocarbon speciation. The data will be used to apportion the relative contributions of exhaust and evaporative emissions by applying these source composition profiles to the microenvironmental measurements from the three cities using Chemical Mass Balance (CMB) receptor modeling.

The emission tests will be coordinated with the trailing vehicle tests described in Section 3.1.3 and the residential

garag e exp osure tests describes in Section 3.1.4. SwRI will install the reversible malfunction on the two test vehicles and perform all emission testing prior to start of the e xposure measurements. Two days will be required for the trailing vehicle and residential garage exposure measurements described in Tasks 2c and 2d for each of six combinations of vehicle and test fuel per season. The trailing vehicle exposure measurements will be scheduled in the morning, followed by garage exposure measurements in the afternoon. Measurements will be made on the first day with normal emissions and on the second day with induced malfunctions. During the exposure tests of one vehicle, SwRI will switch the fuel in the other vehicle a nd condition the vehicles with the new fuel prior to the
exposure measurements.

For the dynamometer FTP exhaust emissions testing, regulated exhaust emissions (total hydrocarbons, THC; nonme t hane hydrocarbons, NMHC; carbon monoxide, CO; and oxides of nitrogen, NOx, carbon dioxide, CO 2 ; and speciated VOC emissions (to include MTBE, ethanol, benz ene, toluene, ethyl benzen e, xylene, 1,3-butadiene, formaldehyde, and acetaldehyde) will be de termined for each test. During hot soak SHED tests, total hydrocarbon and VOC emissions (as above except without aldehyde/k etone measurements) will be determined. Table 3-2 presents a suggested test plan for the emissions testing at SwRI.

The exhaust emission portion of the FTP utilizes the Urban Dynamometer Driving Schedule (UDDS), which is 1372

seconds i n duration. The UDDS is divided into two segments; the first consisting of 505 seconds, and the second consisting of 867 seconds. An FTP is composed of a 505-second cold transient (bag 1) portion and an 867-second cold stabilized (bag 2) portion, followed by a ten-minute soak and then a 505-second hot transient (bag 3) portion. A summary of the cycle duration, driving distance, and average speed is given in Table 3-3. The FTP driving

schedule with the cold- and hot-transient test segments identified is given in Figure 3-1.

The evaporative emission portion of the FTP will consist of a on e-hour Diurnal Heat Build (DHB) and a one-hour Hot Soak Loss Test (HSL). Total hydrocarbons and VOC emissions will be recorded only during the HSL segment of the test. Prior to the cold-start exhaust portion of the FTP, the DHB evaporative segment of the FTP will be conducted by fueling the test vehicle to 40 percent of tank capacity with test fuel at a temperature below 55°F. A heating blanket will be attached to the outside of the fuel tank, and a thermoc ouple placed in the fuel inside the fuel tank will be connected to the computer controller. The fuel inside the tank will be raised to a nominal temperature of 60°F, at which point the DHB segment of the test will begin. The fuel temperature will be raised at a linear rate of 0.4°F per minute for the 60-minute test. The final nominal temperature will be 84°F.

The HSL segment of the evaporative emission test will be co nducted immediately following exhaust emission testing. For the HSL segment, the vehicle will be driven into the evaporative emission enclosure immediately after the exhaust emission portion of the FTP has been completed. The vehicle will be allowed to “soak” in the enclosure

3-5for one hour. Total hydrocarbon and VOC emissions will be measured at the beginning and end of the one-hour segment to permit calculation of hot soak evaporative emissions.

Table 3-2. Test Plan for Each Vehicle

STEP DESCRIPTION

1 Obtain test vehicle. Verify proper mechanical operation.
2 Determine malfunction condition to achieve 2 or more grams/mile total hydrocarbons.

3 Equip vehicle to allow switching between normal and malfunction conditions. Return vehicle to normal operating condition.

4 Remove canister from test vehicle.

5 Purge canister with 300 ° F zero nitrogen at 20L/min for five hours, reattach canister.

6 Drain fuel tank and fill to 40 percent capacity with test fuel.

7 Perform a 2-hour diurnal heat build from 70 to 120 ° F at a ramp rate of 0.4 ° F/min.

8 Operate vehicle on chassis dynamometer over one UDDS cycle.
9 Turn engine off for five minutes.
10 Start engine and idle for one minute.
11 Turn engine off for one minute.
12 Start engine and idle for one minute.
13 Remove canister from vehicle and purge canister with zero air for 60 minutes.

14 Reattach canister, drain fuel from tank, and fill to 40 percent capacity with chilled

test fuel.

15 Conduct one hour DHB (no emission measurements).

16 Operate vehicle on chassis dynamometer over one UDDS.
17 Soak vehicle overnight.
18 Next day prior to the cold-start exhaust po rtion of the FTP, conduct one-hour Diurnal Heat Build (DHB). No emission measurements.

19 Conduct 3-bag FTP exhaust emission test . Measure regulated gaseous emissions

and VOC emissions.

20 Conduct the Hot Soak segment of the SHED test immediately following the exhaust emissions testing. Measure total hydro carbons and VOC emissions (same as with exhaust except no aldehyde emissions).

21 Switch vehicle to malfunction per Step 2, and disconnect evaporative canister.

22 Repeat Steps 8 through 12 and Steps 16 through 20.
23 Repeat Steps 3 through 22 for each of the remaining five test fuels.

3-6Table 3-3. Summary of the FTP Driving Cycle



### Duration, Distance, Average Speed,

Segment Seconds Miles Miles/Hr.

Transient Phase 505 3.6 25.7

Stabilized Phase 867 3.9 16.2

UDDS 1372 7.5 19.7

F

Figure 3-3. FTP Drivi n g Cycle.

Figure 3-3. FTP Driving Cycle.

3.1.3 Relationship Between Exhaust Emission Rates and In-Cabin Exposure

DRI and SwRI will use the two test vehicles in norma l o p eration and with induced malfunction to determine exposure in a cabin of a third vehicle that is trailing the te st vehicles. In addition to the two test vehicles, SwRI will procure a third vehicle that will be used as the trailing vehicle. DRI will install the instrument and sampling systems on board the trailing vehicle. This trailing vehicle will be towed to the three cities and used to conduct the exposure measurements described in Tasks Section 3.2. The trailing vehicle tests will be conducted on a remote road upwind of San Antonio, Texas. The test matrix will mirror the dynamometer tests - two test vehicles with and without malfunction, three regional fuels, and two seasonal fuels for 12 combinations per season. Tests using summer and winter fuels will be conducted in June and January, respectively.

3-7During each test, the trailing vehicle will be driven behind th e test v e hicle over a travel loop of several miles for a period of up to 3 hours. Measurements will be made during the first 10 minutes without the test vehicles in order to establish background exposure levels. The trailing vehi cle study will implement three scenarios (far, near, and passing) for each low or high speed (30 and 60 mph) as scheduled in the table below. During each 'far' scenario, the trailing vehicle will follow continuously at the conventional 'safe' following distance for the indicated speed, defined as one car length (about 10 feet) for each 10 mph. During the 'near' scenario, the vehicle will 'tailgate' the leading vehicle continuously following at a clos er distance deemed 'safe' for professi onal drivers under low-traffic density and prevailing meteorological conditions by SwRI and DRI st aff. During the “passing” scenario, the trailing vehicle will spend 10 min at “tailgating” distance, i.e., as close as safety permits, and 10 min at “passing” distance at an adjacent lane position that maximizes potential cabin penetration (based on maximal hood TVOC).

Table 3-4 details the trailing vehicle protocol. We are continuously monitoring total VOC (with ppbRAE PID)

in si de the cabin and outside the cabin, with the inlet mounted on the radio antenna 6 inches above the hood of the vehicle. In addition, we measure TNMHC from time-integrated canister samples.

Table 3-4. Protocol for trailing vehicle tests

Time

Min. Speed Mph Ventilation Setting Distance Notes Continuous

Instruments SPME Time Integrated

10 high high background Y 1 1

10 low high far Y 1

10 low high near Y 1

10 low high passing Y 1

10 high high far Y 1

10 high high near Y 1

10 high high passing Y 1

10 low low far Y 1

10 low low near Y 1

10 low low passing Y 1

10 high low far Y 1

10 high low near Y 1

10 high low passing Y 1 1

10 idle low adjacent Y 1

10 idle high adjacent Vehicles:

To yo ta Cam ry and Pick-up truck,

in norm a l and

malfunction

mode.

Fuels: baseline,

M T B E, ethanol

Y 1 1

3.1.4 Rela ti onship Between Evaporative Emission Rates and Exposure in a Residence With an Attached Garage

The two test vehicles (with and without malfunctions) will be u sed to determine indoor exposures in homes with attached residential garages. The same test vehicles will be used to measure indoor exposures in a residence with an attached garage using the following testing matrix. The vehicles will be parked in a closed residential garage also containing a gasoline powered lawnmower and gas container with in-garage and adjacent room monitoring conducted before, during and after the vehicle cool-down period. Door openings between the garage and adjacent room and room window openings will be monitored. The vehicle will also be ‘warmed up’, idling in the garage (with the garage door open) during a period of the 3-hour monitoring process. The measurements will be made in

3-8San Antonio at the residence of a SWRI employee who has agreed to provide access to the house during the study.The test procedure will be similar to those described by Tsai and Weisel (2000). We propose to collect two timeintegrated samples of each kind per test (one in the garage and one in the ad jacent room). A set of continuous and semi-continuous methods will be operated during the vehicle exposure period of approximately two hours.

The attached garage study will implement six scenarios as described in the Table 3-5. Measurements will be taken

ov e r 30-minute periods with the collocated sampling inlets lo cated at breathing height (1 .5 m) at least three feet away from nearby walls in both the unvented garage and adjacent indoor room (kitchen). The two PID instruments will sample continuously both before (b ackground) and during the tests with one unit each having its collocated inlet in the garage and adjacent room. Langan CO and/or NDIR CO instruments will sample continuously in the garage and adjacent room. The MS200 BTEX and DRI aldehyde m onitors will sample continuously from collocated inlets in the adjacent room for corro borative purposes. A half-filled two gallon st andard plastic gasoline storage container with vent open will be placed with a lawnmower with ga s tank half filled against the center of the garage wall common to the adjacent room. The appropriate fuel (i.e. from Houston, Atlanta or Chicago) will be placed in the garage one day before the series of tests for this fuel and left there over the duration of these tests. Scenario conditions will be changed every 30 minutes over th e 3-hour protocol as described in the table.

The ambient garage temperature will be recorded ever y 30 m i n duri ng each experiment and the tests will be conducted every day (excluding weekends) over the period of two weeks.

Table 3-5.Protocol for attached garage experiments. The same vehicles and fuels as for trailing vehicle experiment

are used.

Condition Time (min) Garage

Door Kitchen

Door Kitchen

Window Inlet

Location Continuous SPME Integrated Samples

garage Langan CO

PID1Background 30 closed closed closed kitchen MS200

DRI

PID2

NDIR CO 2 2

garage Langan CO

PID1 Hot soak 30 closed open 1min

& closed closed kitchen MS200

AO

PID2

NDIR CO 2

garage Langan CO

PID1 Maximal

AER to

indoors 30 closed closed closed kitchen MS200

DRI

PID2

NDIR CO 2

garage Langan CO

PID1 Maximal

AER to

outdoors 30 closed closed open kitchen MS200

DRI

PID2

NDIR CO 2

garage Langan CO

PID1 Cold start 30 open open 1 min

& closed closed kitchen MS200

DRI

PID2

NDIR CO 2 2

3-93-10 3.2 Microenviro nmental Expos ure Measurements in Atlanta, Chicago, and Houston

One of the overall goals of the project is to sample hi gh-e nd m i croenvironments (MEs), plausibly characterized in the upper 90 th centiles of exposure that result from the impacts of exhaust/evaporative emissions from gasolinefueled vehicles. Selection of high-end microenvironments was made in consultation with EPA and independent peer

reviewers.

DRI will determine in-cabin exposure in urban roadwa y and o t her high-end exposure microenvironments in Houston, Chicago, and Atlanta over se veral weeks in each city and season duri ng July-September (summer test) and January-March (winter test). Exposure measurements will be made for thirteen different microenvironments with three replicate measurements for microenvironments with low variability and five replicate measures for highly variable MEs including trailing high emitting vehicles (ME 13), underground garages (ME 11), and outdoor refueling (ME 7). Measurements in each of the microenvironm ents will be taken over a period of 20-60 minutes and completed within the hour where possible to facilitate comparisons with local ambient monitoring values. Sampling durations will depend on the event and may range from 20 to 60 minutes in the discretion of DRI as necessary to obtain a typical sample. For example, refueling events and clearing of parking garages after sporting events usually occur over periods substantially less than an hour and do not start at the top of the hour . Continuous measurements of carbon monoxide, benzene, toluene, ethyl benzene, xylenes, photoionizable (10.6 eV) VOC, and formaldehyde will be taken during the entire sampling period. Time-integ rated canister, DNPH cartridge, and solid adsorbent (in Chicago) samples will also be collected over the full sampling period unless the next sample will be collected during a consecutive hour. In such cases, 60-minute samples will be collected during the first 50 minutes to allow time for replacement of sampling media. In addition, four SPME samples (for BTEX) will be collected during consecutive 10 -minute periods during each sampling period. Liquid fuel samples will be collected after ME3/7 measurements (during off-loading of the van fuel tank) for each service station (if more than one is used per city) sampled for this ME. Video tapes of ME sampling will be conducted as advi sable considering local privacy and security concerns; at least one videotape will be provided to EPA for each ME sampled in each city.

Table 3-6. Microenvironment Listing.

ME # ME Description Replicates Biomarker 5 min Canister Samplin g Time (min)

1 In-Cabin Congested Freeway 5 40

2 In -Cabin Urban Canyon 3 40

3 In -Cabin Refueling 5 20

4 In -Cabin Underground Garage 5 40

5 In-Cabi n Toll Plaza 3 40

6* Ro adway Tunnel 5 yes yes 40

7 Out door Refueling 5 yes yes 20

8 Si dewalk 3 40

8/9 Si dewalk/Bus Stop 3 40

10 Outdoor Surface Parking 3 40

11 Out door Underground Garage 5 yes yes 40

12 Outdoor Toll Plaza 3 40

13* In-cabin Trailing High-Emitting Vehicles 5 yes yes 40

*ME6 will be sampled in Houston & Chicago and ME13 in Atlanta..

Table 3.6 displays the planned exposure matrix with the number of replicates, and the location of biomarker and 5- minute canister peak sam pling. Table 3.7 lists the number of samples for each microenvironment.3-11Urban1. I2. I3. I4. I5. In6. Ro13SuUrbannts7. Outdoor Refueling45 20 10 10 10 5 1030 60 60 30 208. Sidewalk3 40 10 20 3 3 618 120 18 18 128/9. Sidewalkl/Bus Stop3 40 10 20 3 3 618 120 18 18 1210. Outdoor Surface Parking3 40 10 20 3 3 618 120 18 18 1211. Outdoor Underground Garage45 40 10 20 10 5 1030 120 60 30 2012. Outdoor Toll Plaza3 40 10 20 3 3 618 120 18 18 12Subtotal22110 32 22 44132 660 192 132 88Biomarker Breath Samples6. Roadway Tunnel15 401520 0 60 0 07. Outdoor Refueling5 201530 0 90 0 011. Outdoor Underground Garage5 401530 0 90 0 013. In-cabin Trailing High-Emitting Vehicles25 401510 0 30 0 0Subtotal5154590 0 270 0 0Total63220 108 48 96378 1320 648 288 1921ME6 will be done in Houston and Chicago.2ME13 will be done in Atlanta only.3Chicago only.4Includes 5 minute canister.5Only one ME counted for ME6 and ME13 for Total No. of Samples Per Site.Total No. of Samples Per SiteTotal No. of Samples for Three Cities and Two SeasonsTable 3-7. The Number of Samples for Each Microenvironment for Three Cities and Two SeasonseReplicatesTestDuration(min)Sample timeSPME (min) SPME Cans DNPHSolid Adsorb.A&B3Total No. ofTestsTotal No.SPMETotal No.CansTotal No.DNPHTotal No.SolidAdsorb.3Exposures in Vehicle Cabinn-Cabin Congested Freeway5 40 10 20 5 5 1030 120 30 30 20n-Cabin Urban Canyons3 40 10 20 3 3 618 120 18 18 12n-Cabin Refueling5 20 10 10 5 5 10 30 60 30 30 20n-Cabin Underground Garage5 40 10 20 5 5 1030 120 30 30 20-Cabin Toll plaza3 40 10 20 3 3 618 120 18 18 12adway Tunnel1,45 40 10 20 10 5 1020 80 40 20 20. In-cabin Trailing High-Emitting Vehicles2,45 40 10 20 10 5 0 10 40 20 10 0btotal526110 31 26 52156 660 186 156 104Exposures in Other Microenvironm3.2.1 Exposure Diary and Script Devel o pment

Scripted activities will be used during the exposure measur emen ts. Th is methodology, re ferred to as the indirect approach, has the advantage of providing estimates of exposure over a range of scenarios based on a limited sample size (Klepeis, 1999). This approach involves the following steps: (1) micro environmental identification, (2) quantification of time spent performing activities in a given microenvironment, and (3) measurements of pollutant concentrations during a specified activ ity. By multiplying the total time spen t during each activity by the pollutant concentrations, activity-specific exposure can be estim ated. Using EPA human activity patterns, exposure from these activities can be estimated for the total population (EPA, 1996).

One of the key aspects of the indirect approach is an accurate measure of the tim e spent perform ing a specifie d activity. In order to define exposure time in a reproducible manner, scripted activities are developed for this study by Ted Johnson of TRJ Environmental Inc. for various high-end exposure microenvironments. In this manner, different subjects can reproduce the tota l time required for a specified activity and an accurate estimate of exposure time can be determined. Scripted activity diaries are developed and completed by field personnel during the exposure measurements to document more detailed information about the sampling location and activities during each monitoring period. Examples of a diary pages are incl uded in Appendix D.

We also will compare personal exposures with ambient measur em en ts from n earby local and state monitoring sites. This can be facilitated by scheduling activities to begin on the hour and end on the hour, enabling a direct comparison with ambient network data. However, many hi gh-end microenvironmental activities take less than an hour (e.g., refueling, transiting a tunnel, leaving a parki ng garage) so scheduling of start and stop times within the same clock hour will be attempted as an alternative to increase correlation with ambient monitor sampling periods. Ambient monitor locations are provided to allow estimates of distance and directional relationships to ME

measures.

3.2.2 In-c abin E x posures in Urban Microenvironments

The trailing vehicle from the controlled exposure tests in San An tonio will be transporte d to each of the three cities and used for the in-cabin exposure meas urements in each of the three cities in both summer and winter. A driving route will be developed for each city, which includes the urban roadway microenvir onments and trailing high emitting vehicles encountered in these roadways.

ME#1 – Freeway traffic under stop-and-go conditions (40 minutes)

ME#2 – Downtown surface street loop characteri zed by an urba n canyon effect (40 minutes)

ME#3 – Refueling (20 minutes)

ME#4 – Parking garage (40 minutes)

ME#5 – Toll plaza (40 minutes)

ME#6 – Tunnel or covered roadway (40 minutes)

ME#13 – Trailing high-emitting vehicles (40 minutes)

In addition to continuous measurements, one integrated sa m p le will b e collected during each 20-40 minute exposure. Table 3-6 shows the proposed exposure matrix. We will use GPS on board the vehicle to record the location and time during the entire test. Testing over the driving route w ill be made three – five times for each city and season on rush-hour weekdays with both high ventilation (e.g., window and vent open during the summer) and lower ventilation (i.e., windows and vent closed with AC or heater on during the summer/winter).

3-12We will use scripted technicians and measure breathing zone and ME air levels in the following outdoor and indoor microenvironments: self-service refueling stations, sidewalks near high-density traffic, underground parking garage, bus stop, toll booth, and an above ground parking garage. Technicians will follow the activity scripts developed and will use diaries and/or GPS monitors to document actual exposure locations and conditions.

The exposures in each microe nvironme nt will be monitored for 20-40 minutes. We propose to repeat the

measurements in each microenvironment three to five times and collect time -integrated canister, DNPH and solid adsorbent (for Chicago only) samples during each exposure period (see Table 3-7). For all tests the inlet for portable and time-integrated instruments will be collocated at breathing zone height (i.e. 1.5 m above the ground) and in the breathing zone of th e technician as appropriate.

3.2.3 Technician Biomarker Analysis

Breath m easurement will be used as the biomarker of choi ce. Since we were not able to distinguish background

benzen e co ncentrations from low-level exposures (e.g. walking down street), we propose only to conduct biomonitoring experiments for projected “high-end” exposures such as outdoor refueling, trailing high emitters on congested roadways, and exiting an underground parking garage. Breath sampling will be conducted similar to the

2 nd pilot study, with pre- and post-exposure collections (plu s a backup sample) of the su bject’s breath. Samples will be collected and analyzed according to the protocols described in detail in Section 2.

3.2.4 Criteria for Selecting High End Micr oenvironments

General selection criteria for the 13 high-end MEs are listed belo w . These selection criteria were developed to bias selection towards sampling ME locations and conditions w ith higher levels of accum ulated emissions. Survey technicians will also use pollutant sniffers (e.g., Langan CO and ppbRAE VOC monitors) to sense relative peak pollutant levels within and among these candidate locations, choosing the ME locations with the highest levels in each category for inclusion in the city-specific sampling scri pts. Detailed descriptions of the Houston, Atlanta and Chicago microenvironments are presented in the city plans appended to the protocol.

1. Congested (stop-and-go) freeway (vehicle cabin)

• Rush hour sampling on roadway parallel to wind direction

• Locally known choke points & signaled intersections on high density routes

• Locations most shielded from air dispersion by local topography

• Lane reductions due to ongoing c o nstruction or breakdowns/accidents

• Downwind direction from traffic density centroid

• Trailing high emitting vehicles encountered

Prot oc ol : Prior to test, identify roadway segment that best satisfies above conditions and confirm high potential concentrations using sniffer. Drive back and forth on the segment continuously during the 40-minute rush-hour test period. Drive in most congested (slowest) lane. Maintain a safe following distance, about one car length (10 feet) per 10 mph speed, closing to within 3 feet during stopped conditions. Sample alternative 20-minute periods under high- and low-ventilation (vehicle window s & vents open and windows & vents closed). Trail high emitting vehicles where encountered.

2. Urban canyon (vehicle cabin)

• Rush hour sampling on roadway perpendicular to wind direction

• Greatest con t iguous length & height of high-rise buildings

• Narrowest canyon width

• Highest traffic density

• Mid-block sampling most shielded from air dispersion

Prot oc ol : Urban canyons are streets edged by tall buildings that were selected to be deep as possible generally with height/width ratios > 1. Prior to test , identify roadway segment that best satisfies above conditions and confirm high potential concentrations us ing sniffer. Drive back and forth on the segment

3-13continuously during the 40-minute rush-hour test period (an around-the-block downtown loop may be used if entire loop is associated with high canyon concentrations). Drive in most congested (slowest) lane. Maintain a safe following distance, about one car length (10 feet) per 10 mph speed, closing to within 3 feet during stopped conditions. Sample alternative 20-mi nute periods under high- and low-ventilation (vehicle windows & vents open and windows & vents closed). Trail high emitting vehicles where encountered.

Note that GPS data are often unavailable or unreliabl e in tall urban canyons as the satellite signals are

blocked.

3. Refueling (vehicle cabin)

• Peak ref u el ing period for station

• Largest number of pumps

• Downwind direction from centroid of pump locations

• Location most shielded from air dispersion by topography

• Period with the lowest achievable wind speeds

• Prot oc ol : Prior to test, identify service station that best satisfies above conditions and use sniffer to locate refueling stations associated with highest concentrations. Drive van sufficiently to elevate measured fuel tank temperature prio r to the refueling test. Park car at refueling location and sample alternative 10-minute periods under high- and low-ventilation (vehicle windows & vents open andwindows & vents closed). Refuel car over a 1 to 2-minute active refueling period at mid-point of highventilation sampling period, spilling a few drops of fuel (whose volume is estimated by spot diameter)

as the nozzle is withdrawn from the fuel tank inlet. The number of gallons dispensed will be recorded along with number and diameters of spill spots; the start and stop times of active fueling will be recorded on monitor charts. Endeavor to sample th e same service station at the same time of day on different days as is possible.

4. Parking garage (vehicle cabin) underground

• Rush hour exit sampling

• High capacity & usage

• Near internal entrance/exit lanes

• Location with smallest external openings & most shielded from air dispersion by topography

• Downwind direction from centroid on most occupied parking level

Prot oc ol : Prior to test, identify aboveground parking lot that best satisfies above conditions and use sniffer to locate parking area within lot associated with highest concentrati ons. Park car at the location and sample alternative 40- minute periods under high- and low-ventilation (vehicle windows & vents open and windows & vents closed), during most active period of vehicles exiting.

5. Toll plaza a p ron (vehicle cabin)

• Rush hour samp ling

• Gene ral location of idling traffic queue (e.g., at road toll, parking garage entrance/exit, emissions

testin g facility, controlled on-ramp, multi-road signal-controlled intersection)

• Location most shielded from air dispersion by topography

• High use location

• Downwind direction from centroid of traffic mass

Prot oc ol : Prior to test, identify toll plaza apron that best satisfies above co nditions and use sniffer to locate parking area within plaza associated with highest concentrations. Park car at the location, if feasible, and sample alternative 20-minute periods under high- and low-ventilation (vehicle windows & vents open and windows & vents closed). If not, repeatedly traverse the plaza queu e during the 40-minute te st period, sampling as above, trailing any high emitting vehicles encountered.

6. Tun nel/Covered Roadway (vehicle cabin)

• Rush hour samp ling

3-14• Stop-n-go traffic flow

• Highest traffic density

• Lack of mechanical ventilation, if available

• Smallest enclosed volume

Prot oc ol : Prior to test, identify tunnel or covered roadway that best satisfies above conditions and use sniffer to confirm high concentrations. Drive back and forth on enclosed roadway during the 40-minute test period maximizing time spent in the enclosed envi ronment. Drive in slowes t, most congested lane. Maintain a safe following distance, about one car length (10 feet) per 10 mph speed, closing to within 3 feet during stopped conditions. Note that GPS data are unavailable inside the tunnel as the satellite signals are blocked. Sample alternative 20-minute periods under high- and low-ventilation (vehicle windows & vents open and windows & vents closed). Trail high emitting vehicles where encountered. Collect 5-minute canister sample during tunnel transit of peak concentr ation. Biomarker samples (breath) will be collected from the technician, who will be isolated from further exposure before performing this task.

7. Outdoor Refueling (self-service)

• Peak refu el ing period for station

• Largest number of pumps

• Downwind direction from centroid of pump locations

• Location most shielded from air dispersion by topography

• Period with lowest achievable wind speeds

• Prot oc ol : Prior to test, identify service station that best satisfies above conditions and use sniffer to locate refueling area associated with highest concentrations. After driving car sufficiently to elevate measured temperature of fuel tank, park car at refueling location and sample alternative 10-minute background (at pump) and refueling periods. With collocated sampling inlets in the breathing zone,

refuel the vehicle over a 1 to 2-minute active refue ling period at the mid-point of the second 10 min sampling period. A 5-minute canister sample is taken to include the active refueling period. Return to the vehicle cabin for the rest of the 10-minute sampling period. During active refueling, maintain manual control of the nozzle (i.e., use an unlatched nozzle) and stand downwind of the vehicle fuel tank inlet, spilling a few drops of fuel (whose volume is estimated by spot diameter) as the nozzle is

removed from the fuel tank inlet. The number of gallons dispensed will be recorded along with number and diameters of spill spots; the start and stop times of active fueling will be recorded on monitor charts. Endeavor to sample the same service station at the same time of day on different days as is possible. Liquid fuel samples will be collected after ME7 measurements (during off-loading of the van fuel tank) for each service station (if more th an one is used per city) sampled for this ME. Biomarker samples (breath) will be collected from the tech nician, who will be isolated from further exposure before and after performing this task.

8. Sidewalk/crosswalk near high density traffic

• Rush hour sampling on roadway parallel to wind direction

• Downwind direction from traffic mass centroid

• Location most shielded from air dispersion by topography

• Highest traffic density

• In urban canyon

Prot oc ol : Prior to test, identify roadway segment with sidewalks that best satisfies above conditions and identify the highest concentration area using sniffer. With cart sampler inlet in breathing zone, walk along loop route on both sides of roadway using crosswalks to cross roadway during the 40-minute sampling period. Walk within three feet of curb.

9. Bus stop

• Ru sh hour sampling on roadway parallel to wind direction

• High traffic density route

• Located on tr affic i sland/median strip

3-15• Downwind direction near high density traffic intersection

• In urban canyon

Prot oc ol : Prior to test, identify bus stop (or cab stand) satisfies above conditions and confirm high concentrations using sniffer. With cart inlet in breathing zone, stand/sit at this location (within three feet of curb) for the entire 40-minute test.

10. Outdoor Surface Parking

• Rush hour/maximal usage sampling

• High capacity & usage location

• Near internal entrance/exit lanes

• Downwind direction from centroid of traffic mass

• Location most shielded from air dispersion by topography

Prot oc ol : Prior to test, identify stadium parking lot that best satisfies above conditions and locate parking area within lot where vehicles will queue as they a ttempt to exit. Identify approximate time that the game/event ends. Sample during 40-minute test, approximately dividing the time to see the peak number of vehicles leaving the lot. Sample with front windows down, sliding doors open and vents open, as appropriate.

11. Out door Underground Parking Garage

• Rush hour samp ling

• High capacity & usage

• Near internal entrance/exit lanes

• Lowest leve l with high capacity usage

• Lack of mechanical ventilation, or away from fans & vents if present

Prot oc ol : Prior to test, identify underground parking lot that best satisfies above conditions and use sniffer to locate parking area within garage associated with highest concentrati ons. Park car at location during 40- minute rush-hour test with front windows down and vents open. Maximize number of vehicles passing the sampling point as they exit the garage. Collect a 5-minute canister sample during a period of peak concentration. Biomarker samples (b reath) will be collected from the technician, who will be isolated from further exposure before performing this task.

12. Outdoor Toll booth

• Rush hour/maximal usage sampling

• Lack of mechanical ventilation, if available

• Enclosed queues (e.g., from parking garages, tunnels, testing facilities)

• Central booth & location most shielded from air dispersion by topography

• Downwind direction from centroid of traffic mass

Prot oc ol : Prior to test, identify tollbooth area that best satisfies above conditions and confirm highest concentrations using sniffer. With cart inlet in th e breathing zone, sample a location representative of the tollbooth operator’s exposure during the 40-minute test.

13. Trailing High Emitters

• Rush hour sampling on roadway perpendicular to wind direction

• Greatest con t iguous length & height of high-rise buildings

• Narrowest canyon widths

• Highest traffic density

Prot oc ol : Prior to test, identify roadways which have th e most high emitters using sniffers. Acquire candidate high emitters from PID/CO sensors and follow as closely as is prudent. Maintain a safe following distance, about one car length per 10 mph speed, closing to within 3 feet during stopped conditions. Sample alternative 20-minute periods under high- and low-ventilation (vehicle windows &

3-16vents open and windows & vents closed). Trail high emitting vehicles as long as possible or until a higher emitter is encountered. Collect a 5-minute canister sample during a peak concentrations period. Biomarker samples (breath) will be collected from the technician , who will be isolated from further exposure before performing this task.

Appendices A, B and C contain the specific city plans for sampling in Houston, Atlanta, and Chicago, respectively.

3.3 Mete orology

Fo r po rtions of the sampling periods involving stationary activities, local meteorological variables such as wind speed an d direction, temperature and relative humidity will be taken periodically with a handheld monitoring station. During both these and mobile sampling periods, additional information representing regional conditions will be obtained from nearby NOAA/FAA sites, or other agencies if available. Stability information requires upper air data. The closest locations to the selected cities of San Antonio, Houston, Atlanta, and Chicago, that take routine radiosonde measurements, are at Corpus Christi TX, Lake Charles LA, Peachtree City GA, and Davenport IA or

Lincoln IL. Sections of tw o of the cities, Houston and Chicago, can also be affe cted by land/ocean breezes. Although in situ surface-based observati ons are preferable, diagnostic output from operational numerical models can also be analyzed.

Field participants in the experiment will make the loca l on -site m easurements using a portable meteorological station. Dr. Kelly Redmond, Regional Climatologist, of the Western Regional Climate Center (WRCC), will undertake remaining phases. A principal role of this NOAA-funded facility, housed w ithin DRI's Division of Atmospheric Sciences, is to acquire, store, summarize, distribute, and interpret atmospheric data. The Climate Center has excellent access to past da ta nationwide through its own consid erable in-house capabilities, as well as strong programmatic ties to the other five Regional Climate Centers and to the National Climate Data Center. (The entire national program is funded thr ough DRI.) Each day WRCC processes approximately 100-200 MB of weather and climate data from the national distribution circuits, and saves indefinitely the entire feed containing observations

from all NOAA/FAA sites in North Amer ica. The Climate Center has a wide variety of software for producing climatological summaries of differing degrees of sophistication, depending on the need.

3.4 Data Analysis

Co m pile summary statistics of the data, perform consistency checks, and identify outliers.

The data validation process consists of procedures that identify deviations from measurement assumptions and

p r o cedures. We will apply the following tests to evaluate the internal, spatial, temporal, and physical consistency of each data set and identify invalid data and outliers. DRI will compile and validate the data from Tasks 2 through 4 and prepare statistical summaries of the data and perform the following validation checks.

• Compare averages derived from continuous and semi-continuous measurements with data from timein teg rated samples. Determine systematic biases.

• Derive summary statistics (mean, maximum, standard devi atio n ) for all species, sort the concentrations and note any unusually high or low concentrations.

• Determine variations in fractions of benzene, toluene, ethyl benzene, xylenes, MTBE, and ethanol,

form aldehyde, acetaldehyde to TNMHC and significant differences in the ratios among

microenvironments.

• Prepare scatter plots of mean CO and PID with BTEX f rom canister and MS200), 1,3-butadiene and MTBE from canisters, ethanol from adsorb ent cartridges, formalde hyde and acetaldehyde from DNPH cartridges, and formaldehyde from continuous measurements.

3-17• Determine ratios of the sum of formaldehyde and acetalde hyde to CO, and relate variations in the ratios with MEs and time of day with expectations in the relative contributions of direct emissions versus photochemical formation.

Evaluate the suitability of candidate measurement me thods for use in the main exposure study.

• Summarize results of laboratory evaluations of continuous and semi-continuous methods.

• Compare time-averaged continuous data from the pilot study with corresponding semi-continuous and

t i me-integrated measurements over the same time intervals. Determine significant biases among methods and determine whether continuous measurements will be suitable for determining time-integrated exposure or for documenting peak exposures only.

• For continuous and semi-continuous measurement met hods, characterize the effect of time resolution on

measurem ent of peak exposures.

Determine quantitative relationships between tailpipe emissi on rates an d variations in fuel formulations with exposures in the cabin of a trailing vehicle.

• Quantify the variations in the background values for BTEX, MTBE, 1,3-butadiene, HCHO, CH 3 CHO, EtOH, TVOC and CO during the initial and final loops without the test vehicle.

• Subtract the av era ge time-integrated background values from the corresponding time integrated exposure

levels for the default driv ing condition for each of the 24 test combin ations (i.e., two test vehicles, two emission conditions, three fuels, and two season) and four replicates.

• Quantify separately for each of the two vehicles, the s p ecific differences due to emission condition, fuel and season. Quantify absolute differences for each designated species and differences normalized to

concurrent CO data.

• Variations in MTBE/benzene and EtOH/benzene ratios (or other HC species) will be related to extent of the potential contribution of tailpipe and evaporative emissions.

• Determine the effect on cabin exposu re o f varying speed, spacing between test and trailing vehicle, and degree of ventilation.

• Determine variations of the in-cabin exposures within the test an d trailing vehicle due to variation in

normal/malfunction test vehicle emission rates under idle.

Determine quantitative relationships between evaporative emi ssion rates and variations in fuel formulations with

exposure s in a residence with an attached garage.

• Subtract the time-integrated background values of B TEX , MTBE, and TVOC from the corresponding time integrated exposure levels in the garage and in the adjacent room and determine the increased exposure due to hot-soak evaporative emissions for the vehicle and fuel combinations that were tested.

• Determine the time-evolution in the levels of the BTEX, MTBE, and TVOC above background levels and

det e rmine the penetration of evaporative emissions from the garage to the adjacent room for the vehicle and

fuel combinations that were tested.

Quantify exposures to conventional and oxygenated evap or ativ e and exhaust emission in microenvironments.

• Process GPS data and develop a log of exposure meas u r ements with respect time, location, and speed.

3-18• Compare time-integrated exposure levels measured in the microenvironments that were investigated among the three cities by season. Develop correlations of individual toxic species from time-integrated measurements with CO or PID measurements as appr opriate for microenvironmen ts dominated by vehicle exhaust or fuel evaporative emissions.

• Evaluate the consistency in time-series among con tinuo us CO , PID, MS200, and HCHO measurements in each microenvironment by city and season.

• Reconstruct the time-series of individual air toxics us i n g the surrogate CO and PID measurements and their correlations to time-integrated measurements.

• Determine the differences in mean and peak exposure s by city and season for each microenvironment and characterize the variability of replicat e tests for each microenvironment.

• Characterize th e extrem es in exposure levels for each microenvironment using the reconstructed 1-minute

data.

• Determine the effect of varying cabin ventilation conditi ons on expo sure levels using the ratios of in cabin CO concentrations to ambient CO (measured in the mobile laboratory).

• Compare CO/BTEX/HCHO/NMHC levels that were me asure d during the exposure study with nearby values from the local ambient air monitoring station.

• Estimate the relative importance of tailpipe and evaporative emissions on exposure using the ratio of

M T BE to benzene as described in the RFP.

• Determine the levels of the designated species in the urine and breath of t echnicia n s carrying out the scripted behaviors and determine significant differences due to varying fuel formulation.

3.5 Reporting

Th is task will require completion of the following:

• Rep ort after completion of the 1 st Reno Pilot Study (complete)

• Detailed p reliminary protocol (peer-reviewed by API and submitted for EPA approval prior to initiating the main exposure measurements) (complete)

• Interim Data Report after 2002 s u mmer field study (complete)

• Atlanta Summer Field Study report (complete)

• Report after completion of the 2 nd Reno Pilot Study (complete)

• Final protocol (after incorporating protocol changes) (this document)

• Comprehensive draft report (including the hypotheses, descriptions of statistical analyses, and

in terpretatio ns of the findings)Final report inco rporating reviewers’ comments (submitted to EPA for review and approval together with the reviewers’ comments and a st atement of the disposition of the reviewers’ comment)

3-19

### 4. PROJECT SCHEDULE AND DELIVERABLES

o 10/03 Final protocol submitted to EPA for formal approval

o 11/03 Send summer 2002 San Antonio & Houston data report to EPA

o 12/03 Send summer 2003 Chicago & Atlanta data report to EPA

o 1/04 EPA approves San Antonio and/or Houston re-sampling plan

o 2/04 DRI begins winter Atlanta sampling

o 3/04 DRI completes winter Chicago sampling

o 7/04 DRI begins summer re-sampling in San Antonio (if required)

o 8/04 DRI completes summer re-sampling in Houston

o 1/05 DRI begins winter San Antonio sampling

o 2/05 DRI completes winter Houston sampling

o 5/05 Send draft report to EPA & peer reviewers

o 6/05 Revise draft report incorporating peer reviewer comments

o 7/05 Send draft final report to EPA

o 9//05 Receive EPA comments

o 1/06 Address EPA comments, send final rep o rt to EPA, & archive results

4-1

### 5. REFERENCES

Cardin, D. and T. Robinson (2002). Formaldehyde and VO Cs in air-qu ality d eterminations by GC-MS. American Laboratory. 32-34

Chai, M. and J. Pawliszyn (1995) Analysis of Environm ental Air Sam ples by Solid Phase Microextraction and Gas Chromatography/Ion Trap Mass Spectrometry, Environmental Science and Technology, Vol. 29, No. 3.

Environmental Protection Agen cy (EPA) (1991). "Technical Assistance Document for Sampling and Analysis of Ozone Precursors." Document No. EPA/600-8-91/215, U.S. Environmental Protection Agency, Research Triangle Park, NC.

Environmental Protection Agency (EPA) (1996). Descript ive Statistics fro m a Detailed Analysis of the National Human Activity Pattern Survey (NHAPS) Data. Docu ment no. EPA/600/R-96/148, U.S. Environmental Protection Agency, Office of Research and Development, Washington, DC, July 1996.

Fung, K., and D. Grosjean (1981). "Determination of Nanogram Amounts of Carbonyls as 2,4-

Dini t rophenylhydrazones by High Performance Liquid Chromatography." Anal. Chem.

, 53 , 168-171.

Graboski, M.S., D.L. Mowery, J. McClelland (1998). Microenvironmental Exposure Analysis Evaluation of the Toxicity o f Conventional and Oxygenated Motor Fuels, SAE International Fall Fuels and Lubricants Meeting and Exposition, San Francisco, October 19-2 2, 1998, in Alternative Fuels 1998 (SP-1319), SAE Technical Paper 982535.

Goliff, W.S. and B. Zielinska (2001). Long-Term Stability o f Oxygenated Compounds inElectropolished Canisters, Paper #403, presented at the 94th Annual A&WMA Conference and Exhibition, June 24-28, 2001, in Orlando, Florida.

Kelly, T.J. and C.R. Fortune (1994). Continuous Monitoring of Gaseous Formaldehyde Using an Improved Fluorescence Approach. Intern. J. Environ. Anal. Chem., 54: 249-263

Klepeis, N.E. (1999). An Introduction to the Indirect Exposure Assessment Approach: Modeling Human Exposure Using Micro e nvironmental Measurements and the recent National Human Activity Pattern Survey, Environmental Health Perspectives, 107, 365-374.

Koutrakis, P., J.M. Wolfson, A. Bunyaviroch, S.E. Froehlich, K. Hirano, J.D. Mulik (1993). Measurement of

Amb i ent Ozone Using a Nitrite-Coated Filter. Anal Chem 65, 209-214.

Lee, C.W. and C.P. Weisel (2001). Toxicokinetics of Human Exposure to Methyl tertiary-butyl ether (MTBE)

Follow i ng Short-Term Controlled Exposures. JEAEE ., 11, 67-78

Lindstrom, A.B., and J.D. Pleil (1996). Alveolar Breath Sampling and Analysis to Assess Exposures to Methyl

Tertiar y Butyl Ether (MTBE) During Motor Vehicle Refueling., JAWMA . 46, p. 676-682

Martos, P. and J. Pawliszyn (1998). Sampling and Determination of Formaldehyde Using Solid-Phases

Mi croext raction with On-Fiber Derivation, Analytical Chemistry, 70, 2311-2320.

Pleil, J. and A. Lindstrom (2002). A review of the USEPA’s single breath canister (SBC) method for exhaled

vo l atile organic biomarkers. Biomarkers, 7, 189-208

Rasmussen, R.A. (1992). “The ABCs of stai nless steel canister clean-up a nd certification.” Pres ented at the 1992 U.S. EPA/A&WMA International Symposium on Measurement of Toxic and Related Air Pollutants, Durham, NC, May 1992.

5-1Shire, J.; Harshfield, G.; Zielinska, B.; Pasek, R. “A Comparison of Analytical Me thods for Oxygenated Volatile Organic Compounds in Ambient Air, ” In: Proceeding of the U.S. EP A/A&WMA International Symposium on Measurements of Toxic and Related Air Pollutants: Durham, NC May 1996.

Tsai, P. and C.P. Weisel (2000). Penetration of Evapor ative Emissio n s into a Home from an M85-Fueled Vehicle

Parked in an Attached Ga rage, JAWMA , 50:371-377.

Vayghani, S. A., C. Weisel, (1999) The MTBE air concentra tions in th e cabin of automobiles while fueling, JEAEE 9, 261-267.

5-2

## 6. APPENDICIES

A-1

### APPENDIX A

Exposure Protocol and Study Plan for th e Section 211(B) Tier 2 High End Exposure Screening Study of Baseline and Oxygenated Gasoline - Summer/Winter Sampling Plan for Houston

Prepared for

AMERICAN PETROLEUM INSTITUTE

1220 L Street Washington, DC 20005-4070

Prepared by

DESERT RESEARCH INSTITUTE 2215 Raggio Parkway Reno, NV 89512

October 1, 2003



### A-1INTRODUCTION

This sampling plan specifies the details for the field measur emen t p rogram that will be carried out in Houston, Texas during the summer of 2004 and winter of 2005 as part of a screening study of the high-end exposures to baseline and oxygenated gasoline. It specifies example dates, times and measurement locations for the twelve categories of microenvironments and explains the selections with resp ect to the objective of capt uring the upper-end of the distribution of exposures for each micr oenvironment. This document is an ad dendum to the Exposure Protocol and Study Plan, which describes the proposed measurement methods and rationale for their selection.

Exposure levels are directly related to the activity and emi ssi on rates of sources in the microenvironment and inversely related to the distances between sources of em issions and the measurement location and the extent of dilution of emissions, which is a function of meteorological conditions and the presence of physical obstruction that inhibit dispersion. The API and EPA have prescribed a goal to capture the 99 th percentile exposure levels within each type of microenvironment. Due to the scope of this study, it will not be possible to fully characterize (by measurements) the range of ex posures that include the 99 th percentile. However, we considered available surrogate parameters for emission levels and dispersion to select sampling times and locations with the greatest potential for higher exposures. These emission surrogates include traffic counts, and diurnal variations in average highway speeds, length of queues at toll plazas, number of cars refueling or entering and exiting parking garages. Surrogates for dispersion include wind roses and diurnal variations in temperature. Measurements in microenvironments with unrestricted dispersion will be made in the early morning or evening duri ng calm conditions and minimal vertical mixing. In moderate wind conditions, we will drive parallel to the prevailing wind to reduce the impact of cross winds. Our sampling strategy also recognizes that vehicle exhaust emission levels are significantly higher for high emitters and are higher for all vehicles during cold starts and accelerations. All of these factors are important in understanding the large temporal and spatial variations that are likely to exist within each of the microenvironments. We plan to examine available hourly CO data and PAMS BTEX and 1,3-butadiene data for June through September 2003 to place the field measurement data in context with seasonal variations.

Desert Research Institute personnel, accompanied by the API project officer, surveye d potential microenvironments in Houston on June 20-22, 2002 (Thursday to Saturday). The objectives of the surv ey were to ascertain the suitability of sampling locations with respect to access and potential for higher-e nd exposures, and to determine the variations in air pollutant levels in several of the microenvironments with a portable gas analyzer. We visited the following locations: I-10 during the morning commute period, urban canyons in downtown Houston, Washburn Tunnel, various toll plazas on the Sa m Houston Tollway and Hardy Toll Ro ad, toll plaza at the Ship Channel Bridge, covered terminals at the Bush International and Hobby Airports, parking garages in downtown Houston and the Texas Medical Center, underground parking garage s at the City Hall Annex and Greenway Plaza (CompaqCenter), and parking lots at Minute Maid Park after a Houston Astros baseball game. A RAE Systems Model PGM7240 (ppbRAE) portable PID monitor was used to continuously monitor ambient VOC levels in several of the microenvironments. The monitor is equipped with a 10.6 eV photoionization (PID) detector and responds to certain organic and inorganic gases that have an ionization potential of less than 10.6 eV, which includes most compounds of interest in this study. It does not respond to light hydrocarbons such as methane, ethane, and propane or to acetylene, formaldehyde or methanol. For the purposes of the survey of microenviron ments in Houston, the PID

detector was used to measure variations rather than absolute VOC levels.

SURVEY RESULTS

Figures 1 through 5 show the time-series plots of the PID response in several microenvironments. Data are plotted

for the 10-sec ond a verage and maximum PID response duri ng each 10-second interval. Because we inspected many sampling locations within a short time, many of the PID measurements do not coincide with periods of highest emissions. Coupled with expected variations in emission activity levels, these measurements may be used to assess the potential for the highest exposures. Figure 6 shows the historic mean wind speed and direction in Houston for July.

Figure 1 shows the PID response for a one-hour trip during the morning commute period on eastbound I-10 from

Bark er -Cypress Rd. to downtown Houston via southbound I-45. The trip ended south of the downtown area at the Fannin St. exit off westbound SR-59. The trip was made on Thursday, June 20, 2002 from 7:27 to 8:27 a.m. The



### A-2first 40 minutes of the trip was in congested traffic (average speed of 20-25 mph). For most of this period, the maximum PID response hovered around 100 ppb with occasional excursions to up to 200 ppb. The maximum PID response increased to between 400 and 600 ppb during a three-minute period in the first ten minutes of the trip. These high values were associated with a suspected high emitter. The vehicl e was a landscape service truck, which was towing a trailer containing lawn and garden equipment. Three spikes in the PID response coincided with slow downs in traffic followed by accelerati ons. Without concurrent CO data, we cannot rule out evaporative emissions from the lawn and garden equipment. However, we followed one other landscape service truck with no increase in the PID response. From the I-610 loop to I-45, the traffic moved near the speed limit and the PID response was consistently at or below 100 ppb. VOC concentrations were higher during the last ten minutes of the trip when we encountered congested traffic in downtown Houston and substantial backup at the junction of southbound I-45 and westbound SR-59. This trip demonstrates what we have observed with similar measurements. A great majority of the on-road vehicle fleet are relatively low emitters that have little impact on in-cabin exposure levels at highway speed. Congested stop-and-go conditions result in some increase in exposure levels due to shorter gap between vehicles and due to intermittent accelerations. Higher exposures are anticipat ed when following high emitters.

Figure 2 shows the time-series of the PID response during a 1.3-hour tour through downtown Houston. The first half

of th e t our covered the west side of downtown with potential urban canyons. The PID response varied with traffic in the area, which was relatively light during this period. We sampled in an above-ground parking garage at about 9:00

a.m. for about five minutes. The VOC levels measured in the garage were not significantly above the surrounding urban background. The second half of the tour covered the eastside of downtown near Minute Maid Park (Houston Astros baseball stadium). The large parking lot east of the stadium is a potential sampling site during ballgames (see Figure 4).



### Congested Freeway

0 100 200 300 400 500 600 700072707320737074207470752075708020807081208170822

Time, CDTPID Response (ppb) Average

Maximum

Figure 1. Eastbound I-10 from Barker-Cypress Rd. through downtown Houston via southbound I-45 and westbound

SR-59 a nd ending at Fannin exit.



### A-3Downtown Houston

0 100 200 300 400 500 60008300835084008450850085509000905091009150920092509300935094009450950

Time, CDTPID Response (ppb) Average

Maximum

Figure 2. Tour of downtown Houston.

Bush Int. Airport, Highways 8, 59, and 10, and Washburn Tunnel

0 100 200 300 400 50012401245125012551300130513101315132013251330133513401345

Time, CDTPID Response (ppb) Average

Maximum

Figure 3. George Bush International Airport and drive to Washburn Tunnel.



### A-4Minute Maid Stadium Parking Lot After Houston Astros Baseball Game

0 100 200 300 400 500 600 7002145215021552200220522102215

Time, CDTPID Response (ppb) Average

Maximum

Figure 4. Minute Maid Park at the end of a ballgame on evening of June 21, 2002.

Wahburn Tunnel and Ship Channel Bridge Toll Plaza

0 100 200 300 400 50013451350135514001405141014151420

Time, CDTPID Response (ppb) Average

Maximum

Figure 5. Tour of Washburn Tunnel and the Sh ip Chan nel Toll Plaza on the Sam Houston Tollway.



### A-5The first 20 minutes in Figure 3 show the variations in PID response at the George Bush International Airport. The

roa d through the airp ort is split into two levels at each of the four terminals with pa ssenger pick-up be ing the lower, covered level. Terminal C appeared to have the greatest length of covered roadway in front of the terminal. Traffic was light during this time and we observed about a 50 to 100 percent increase in PID response while driving past Terminal C. We expect significantly higher VOC levels du ring peak periods. We also visited the Hobby Airport (data not shown), which also has a two-level road at the terminal. The length of covered roadway is greater at Hobby and adjacent parking garage is larger. We propose to sample in-cabin exposure at the Hobby Airport terminal during peak periods.

Figure 3 also shows the variations in PID response during three trips through the Washburn Tunnel. The first three spik es i n Figure 5 correspond to trips through the tunnel on another day. Travel time through the tunnel is 52 seconds at 35 mph from portal to portal. The tunnel is book ended on each side by a rotary. Passage through the tunnel is controlled during peak periods to avoid congestion within the tunnel. A queue of vehicles develops during these controlled periods. We propose to sample during peak periods in order to measure exposure while in the queue

as well as in the tunnel.

Figure 4 shows the time-series of the PID response at Mi nute Maid Pa rk at the end of a ballgame on the evening of June 21, 2002. We were parked in the middle of Lot C and made

Figure 6. Frequencies of wind speed and direction in Houston during July.



### A-6measurements at this location for about ten minutes while vehicles began to leave the lot. The PID response was nearly constant during this period. We then walked to the parking lot exit and made measurements there. The spikes in the PID coincide with the passage of vehicles accelerating out the pa rking lot, while presumably still in cold-start mode. We then walked along the sidewa lk towards the park. These measurements were lower than at the parking lot exit but higher and more variable than at the center of the parking lot. Based upon these results, we propose to sample with a sampling cart for a one-hour peri od at the end of the game with 15-minute sampling times alternating between a fixed location at the exit of the parking lot and a walk along the sidewalk.

The second half of the time-series in Figure 5 shows the variations in the PID response at the toll plaza at the Sam

Hou s ton Tollway Ship Channel Bridge. The speed limit on the Tollway is 70 mph. As the vehicles leave the toll plaza, they accelerate rapidly leaving a puff of higher emissions at the toll booth. The emissions of vehicles are typically much higher under hard accelerations. The spikes in PID response in Figure 5 coincide with vehicles accelerating rapidly from the tollb ooth. Based on these results, we propose to sample with a sampling cart as close to a tollbooth as allowed by the Harris County Tollway Auth ority. Prior to setup, we will make one pass through the toll plaza to measure in-cabin exposure with continuous inst ruments only. We will endeavor to use the same ME locations during both the winter and summer studies.

DESCRIPTIONS OF MICROENVIRONMENTS (ME) AND SAMPLING PROTOCOL

1. In vehicle: commuter rush hour in stop-and-go traffic (ME1)

M a ke one to two 20-minute roundtrips (depending on traffic conditions) on a segment of freeway during peak weekday m orning commuter traffic (Option A or B depending upon wind speed and direction) from 7:00 to 8:00 a.m. Use high ventilation conditions (window and vent open, AC on during summer and heater on during winter) during the first half and low ventilation (windows and vent closed, AC on during summer and heater on during winter) during the second half of the ME. Maintain a safe following distance, about one car length (15 feet) per 10 mph speed, closing to within 3 feet during stopped conditions. Use the middle lane and do not follow the same vehicle for more than two minutes. Attempt to get behind at least one high-emitter.

Sample in-cabin air at driver’s breathing zone continuously with Langan T15 CO monitor, NDIR CO

in st rument, and ppbRAE, r and collect one set of canister and DNPH samples integrated over the entire sample. Collect four SPME samples, one every 10 minutes. Sample the outside air with the second portable PID monitor during the entire period without compromising the ventilation condition in the cabin. Monitor and record the van’s position (GPS), and in-cabin temperature and rela tive humidity. A forward facing camcorder will record roadway activities and locations for this and other in-cabin MEs during the sampling run. Other relevant data collected by the City of Houston include CO and meteorological data at the Lang (C408) monitoring station in west Houston at 4401 1⁄2 Lang. Check wind speed and direction at the mobile laboratory and traffic conditions (radio reports of any accidents on samp ling routes) prior to sampling run an d select the appropriate sampling route from the following options. If accidents, other h azards, or local conditions ch ange, substitute other, equivalent routes with similar distances and speeds as needed.

a. Option A (use for calm wind conditions or winds from west or east). A six-mile segment of I-10 between Dairy Ash f ord Rd. (2 mile west of the Sam Houston Tollway) and Voss Rd. (4 miles east of the SH Tollway). Start with the inbound (east) direction at Dairy Ashford Rd. Average speeds in the inbound and outbound directions are 20-25 mph and 50-60 mph, respectively.

b. Option B (use for moderate winds from south-southeast or north-northwest). An eight-mile segment of US29 0 between N. Eldridge Parkway (3 miles northwest of SH Tollway) to Bingle Rd (5 miles southeast of SH Tollway). Start with inbound (sou theast) direction from N. Eldridge Parkway. Average speeds in the inbound and outbound directions are about 30 mph and 65-70 mph, respectively.

2. In vehicle: urban street canyons (ME2)

The g reat est volume of traffic in the downtown Houston occurs during the morning and afternoon commute

pe r iods and to a lesser extent during the noon hour. We propose the weekday afternoon commute period from 4:00 to 5:00 p.m. because the vehicles exiting the park ing garages may still be in cold-start mode and because ME1 precludes ME2 during the morning commute period.



### A-7Make multiple trips during a 40-mi nute period along a four by one bloc k surface street lo op in downtown Houston. The loop consists of four one-way streets an d four left turns. Starting from the intersection of Louisiana and Clay, go northeast on Louisiana for four blocks, turn left on Walker, left on Smith, left on Clay, and left on Louisiana to complete the loop. Use high ventilation conditions (window and vent open, AC on during summer and heater on during winter) during first 20 minutes and low ventilation (windows and vent closed, AC on during summer and heater on during winter) during second 20 minutes. Drive at or near the end of a pack of vehicles as much as possible.

Sample in-cabin air at driver’s breathing zone continuously with the Langan T15 CO, NDIR CO, and ppbRAE analyzer and c o llect one set of canister and DNPH sample s integrated over the entir e period. Collect four SPME samples, one every 10 minutes Sample the outside air w ith the second portable PID monitor during the entire period without compromising the ventilation condition in the cabin. Monitor and record the van’s position (GPS), and in-cabin temperature and relative humidity. No te that GPS data is often unavailable or unreliable during this ME as the tall buildings block satellite signals. A forward-facing camcorder will record roadway activities and locations during the run. Other relevant data collected by the City of Houston include CO and meteorological data at the Houston Texas Avenue (C411) monitoring station in downtown Houston at 2311

Texas Avenue.

3. In vehicle: refueling (ME3)

Select ap propriate refu eling location(s) and sampling times b a sed on the following guidance. The fuel pump islands should be located on the lee side of the service station building or other large obstruction such as the raised section of highway. Given the prevailing southerly to southeasterly winds, the turnarounds at the north sides of I-10, South I-610 loop, or SR 59 are potential areas for the search. Conduct sampling during the peak or near-peak refueling periods for the station as indicated by service station personnel.

After driving to elevate measured fuel tank temperatur es, par k sampling van at refueling location and sample alternate 10-minute periods under background (parked at pump) and refueling conditions Park the van downwind from the centroid of the pump locations. Sample in-cabin air at driver’s breathing zone continuously with a KORE MS 200, Langan T15 CO, NDIR CO, and ppbRAE PID, and collect one set of canister and DNPH samples integrated over the sampling period. Collect two SPME samples, one 10-minute sample during the background sampling period and one 10-minute sample during the refueling period. Sample both the outside and in-cabin air with the two portable PID monitors during the entire sampling period. Monitor and record the outside wind speed, and direction, as well as th e sampling location temperature and relative humidity. A camcorder will be positioned to record the sampling scene from outside the van; a pan of the sampling site will also be provided to record details of the location. Va n windows are to be down and doors open as appropriate during this ME

4. In vehicle: parking garage (ME4)

Dri v e within a parking garage for 40 minutes. Use high ventilation conditions (window and vent open, AC on

du ring summer and heater on during winter) during first 20 minutes and low ventilation (windows and vent closed, AC on during summer and heater on during winter) during second 20 minutes. Potential garages include the Houston City Hall Annex, Greenw ay Plaza, and Hobby Airport (covered road in front of terminal and adjacent parking structure).

Sample in-cabin air at driver’s breathing zone continuously with a KORE MS 200, Langan T15 CO, NDIR CO, ppbR A E, and DRI HCHO analyzer and collect one set of canister and DNPH samples integrated over the entire hour. Collect six SPME samples, one every 10 minutes. Sample both the outside and in-cabin air with the two portable PID monitors during the entire hour without compromising the ventilation condition in the cabin. Monitor outside wind speed and direction (if any) and record the in-cabin temperature and relative humidity. A camcorder will be positioned to record the sampling scene from outside the van; a pan of the sampling site will also be provided to record details of the location.

5. In vehicle: toll plaza (ME5)



### A-8Measurements for this microenvironment are combined with the tunnel and tollbooth microenvironments. See

ME6 and ME12.

6. In vehicle: tunnel (ME6)

Make several trips though the Washburn Tunnel for one hour during peak periods when traffic through the

tunn el is co ntrolled. Use high ventilation conditions (window and vent open, AC on during summer and heater on during winter) during first 20 minutes and low ventilation (windows and vent closed, AC on during summer and heater on during winter) during second 20 minutes.

Sample in-cabin air at driver’s breathing zone continuously with a Langan T15 CO, NDIR CO, and ppbRAE,

and co llect on e set of canister and DNPH samples integr ated over the entire period. Collect a 5-minute canister sample during a peak concentration period. Collect four SPME samples, one every 10 minutes. Biomarker samples (breath) will be collected from the technician , who will be isolated from further exposure before performing this task. Sample the outside and in-cabin air with the two portable PID monitors during the entire hour without compromising the ventilation condition in the cabin. Monitor and record the van’s position (GPS), and in-cabin temperature and relative humidity. Note that the GPS data will be unavailable for the period the van is inside the tunnel as the tunnel blocks the satellite signals. A front-facing camcorder will record the roadway activities and also, when stopped, provide a pan of the sampling site location.

7. Outdoor: refueling vehicle (ME7)

Select ap propriate refu eling location(s) and sampling times b a sed on the following guidance. The fuel pump islands should be located on the lee side of the service station building or other large obstruction such as the raised section of highway. Given the prevailing southerly to southeasterly winds, the turnarounds at the north sides of I-10, South I-610 loop, or SR 59 are potential areas for the search. Conduct sampling during the peak or near-peak refueling periods for the station as indicated by service station personnel if possible and strive for as low wind speed (< 5 mph) as possible. Conduct samp ling in the morning to accommodate the collection of biomarker samples and presence of low wind speeds.

Park the van downwind from the centroid of the pump lo cation s after driving it suffici ently to elevate measured fuel tank temperatures. With sampling inlets in the breat hing zone, refuel the vehicle over a 1 to 2 minute active refueling interval within the second 10-minute sampling period. During refueling, maintain manual control of

the nozzle and stand downwind of the vehicle fuel tank inlet, spilling a few drops of fuel after removing the nozzle from the fuel tank. Sample the breathing zone continuously with a KORE MS 200, NDIR CO, and ppbRAE and collect one set of canister and DNPH sample s integrated over the entire 20-minute period. Collect a 5-minute canister sample that includes the active re fueling period. Biomarker samples (breath) will be collected from the technician, who will be isolated from further exposure before performing this task. Collect two SPME (background and refueling) samples during the initial background and final refueling periods. Record the ambient temperature and relative humidity. A camcorder will be positioned to record the sampling scene from outside the van; a pan of the sampling site will also be provided to record details of the location. Local wind speed, direction, temperature and humidity will be collected with the hand held meteorological monitor. A liquid fuel samples will be collected after ME7 measurements (during off-loading of the van fuel tank) for each service station (if more than one is used per city) sampled for this ME.

8. Outdoor: sidewalk near high-density traffic (ME8)

C o nduct sidewalk sampling by cart in downtown Houston along the city block bordered by Polk, Louisiana,

Cl ay and Smith. A portion of Polk St. is covered and se veral eating establishment are located there with outdoor seating. After the first trip around the block, remain in the covered section of Polk Street for at least 10 minutes, and then continue the walk around the block. Sampling should be conducted during the morning and afternoon commute periods and during the noon hour. A camcorder will be positioned to record the sampling scene from the cart; a pan of the sampling site will also be provided to record details of the location.

Sample the breathing zone continuously with Langan T15 CO, and ppbRAE portable PID monitor and collect

one set o f canister and DNPH samples integrated over the entire 40 minute period. Collect four SPME samples,



### A-9one every 10 minutes. Record the local wind speed, direction, ambient te mperature and relative humidity with the hand held meteorological device.

9. Outdoor: bus stop (ME9)

Sam p le the ambient air at a bus stop by cart in do wnto wn Houston during the morning and/or afternoon commute periods. Conduct as described in ME8 above.

10 Outdoor: stadium parking lot (ME10)

Sample for 40 minutes at the end of Houston Astros ba seball ga m es. Attempt to determine the end of the game time by listening to the radio to determine the progress of the game. Park the van near the exit of the parking lot where vehicles will queue up as they exit, down wind of the exhaust. Sample the breathing zone continuously with a KORE MS 200, Langan T15 CO, DRI HCHO analyzer, and portable PID monitor and collect one set of canister and DNPH samples integrated over the entir e period. Collect four SPME samples one every 10 minutes. A camcorder will be positioned to record the sampling scene outside the van; a pan of the sampling site will also be provided to r ecord details of the location.

11. Outside underground parking garage (ME11)

Sample the ambient air in an underground parking garage for one hour. Potential garages include the Houston City Hall Annex and the Gree nway Plaza. The Greenway Pl aza is preferable for several reasons. The Greenway Plaza is a business complex of ten office towers, the Re naissance Hotel and the Co mpaq center, home to the NBA Houston Rockets and the WNBA Comets. The comple x includes 13,000 parkin g spaces. A large fraction of the parking is underground. During our study period in Houston, the Comets are scheduled to play. We propose three separate 40-minute sampli ng periods. The first will start about 4:00 p.m. when the office workers leave the complex (cold start emissions). The second starts about 7:00 p.m. when the basketball fans arrive for the game (hot stabilized exhaust and hot soak emissions) and the final sampling period will be after the game (cold start emissions).

Sample the breathing zone continuously with a KORE MS 20 0, L angan T15, DRI HC HO analyzer, and portable

PID monitor and collect one set of canister and DNPH sa mples integrated over the entire period. Collect a 5- minute canister sample that includes a peak period during the crowd exit after the game. Biomarker samples (breath) will be collected from the technician, who will be isolated from further exposure before performing this task Collect four SPME samples, one every 10 minutes. Collect breath biomarker samples after a peak period encountered early during the sampli ng event. Record the local ambient wind speed, direction (if any), temperature and relative humidity with the hand held meteorological instrument. A camcorder will be positioned to record the sampling scene outside the van; a pan of the sampling site will also be provided to

record details of the location.

12, Outdoors: toll booth (ME12)

Sample the ambient air at the Ship Channel Bridge to ll plaza for 40 m i nutes. Locate the sampling cart behind the concrete barrier on the west end of the plaza as close to the tollbooth as possible. Notify Patricia Watson of the Harris County Tollway Authority (281/875-1400) of the Harris County Tollway Authority at least 24 hours prior to sampling.

Sample the breathing zone continuously with a KORE MS 200, Langan T15 CO, and portable PID monitor and

collect o n e set of canister and DNPH samples integrated over the entire hour. Collect six SPME samples with each sampling period lasting 10 minutes. Record the ambi ent wind speed, direction, temperature and relative humidity with the hand held meteorological instrument. A camcorder will be positioned to record the sampling scene from the cart; a pan of the sampling site will also be provided to record details of the location.



### A-10If time permits before or after the sampling period and suffi cient traffic exist, conduc t measurement of in-cabin exposure during one pass through the toll plaza. Collect one SPME sample during this sampling period.

DAILY SAMPLING SCHEDULE

The daily schedules for the Houston summer and wint er sam p lin g program will be finalized prior to summer 2004 and winter 2005 studies. In order to stay on project schedule as much as possible, sampling will be conducted on Saturdays in case we encounter unsuitable meteorological conditions on scheduled sampling days.



### A-11

### APPENDIX B

Exposure Protocol and Study Plan for th e Section 211(B) Tier 2 High End Exposure Screening Study of Baseline and Oxygenated Gasoline

Addendum B – Summer/Winter Sa mpling Plan for Atlanta

Prepared for

AMERICAN PETROLEUM INSTITUTE

1220 L Street Washington, DC 20005-4070

Prepared by

DESERT RESEARCH INSTITUTE 2215 Raggio Parkway Reno, NV 89512

October 1, 2003

B-1INTRODUCTION

This sampling plan specifies the details for the field meas u r em ent program that will be carried out in Atlanta, GA during the summer as part of a screening study of the high-end exposures to baseline and oxygenated gasoline. It specifies example dates, times and measurement locations for the twelve categories of microenvironments and explains the selections with respect to the objective of capturing the upper-end of the distribution of exposures for

each microenvironment. This document is an addendum to the Exposure Protocol and Study Plan, which describes the proposed measurement methods and ra tionale for their selection. We will en deavor to use the same ME locations during both the winter and summer studies.

Desert Research Institute personnel, accompanied by the API proj ect officer, surveye d potential microenvironments in Atlanta on July 24-26, 2002. The objectives of the survey were to ascertain the suitability of sampling locations with respect to access and potential for higher-end exposures, and to determine the variations in air pollutant levels in several of the microenvironments with a portable gas an alyzer. We visited the following locations: I-20 W and I75 NW during the morning commute period, urban canyons in downtown Atlanta, Justus C. Martin Jr. Tunnel, GA400 toll road plaza, parking garage s in downtown and midtown Atlanta and in Buckhead, service stations, parking garage at the Georgia Dome and parking lots at Turner Field. A RAE Systems Model PGM-7240 (ppbRAE) portable PID monitor was used to continuously monitor ambient VOC levels in several of the microenvironments. The monitor is equipped with a 10.6 eV photoionization (PID) detector and responds to certain organic and inorganic gases that have an ionization potential of less than 10.6 eV, which includes most compounds of interest in this study. It does not respond to light hydrocarbons such as methane, ethane, and propane or to acetylene, formaldehyde or methanol. For the purposes of the survey of microenvironments in Atlanta, the PID detector was

used to measure relative variations rather than absolute VOC levels.

Information for the survey were obtained from th e following Atlanta web sites:

Air Quality Agencies

http://www.dnr.state.ga.us/environ/ Georgia Environmental Protection Division http://www.air.dnr.state.ga.us/amp/index.html Current air quality http://www.cleanairforce.com/ Vehicle inspection program http://www.atlreg.com/ Atlanta Regional Commission

http://www.atlanta-airport.com/ Atlanta Airport http://www.dot.state.ga.us/ Georgia Dept. of Transportation http://www.accessatlanta.com/au tos/sp ecial/ro adwords.html Road works

http://www.georgia-navigator.com/traffic/ Real-time traffic map http://www2.georgianavigator.com/links.html Atlanta Visitor Links http://www.itsmarta.com/ Metro Atlanta Rapi d Transit Authority http://www.metrogirl.com/dna/links.htm Downtown Atlanta Links http://www.atlantadowntown.com/downtownlivedirectory.htm Downtown Events http://www.gadome.com/ Georgia Dome/World Congress Center, Falcons http://braves.mlb.com/NASApp/mlb/atl/ballpark/atl_ballpark_history.jsp Turner Field, Braves http://www.atlantaarena.co m/ st0 300/main/main.shtml Phillips Arena, Hawks http://www.aaaparking.com/property2.htm parking garages http://www.accessatlanta.com/shopping/guides/mallguide.html Mall Guide

DESCRIPTIONS OF MICROENVIRONMENTS (ME) AND SAMPLING PROTOCOL

1. In vehicle: commuter rush hour in stop-and-go traffic (ME1)

Dri v e for 40 minutes in congested freeway traffic during weekday morning rush hour from 0700 to 0800, local

ti m e or evening rush hour from 1700 to 1800. During the morning, drive southbound on I-75 beginning at S.

B-2Marietta Parkway to downtown Atlanta. Drive the oppo site direction during the evening rush hour. A forward facing camcorder will record roadway activities and lo cations for this and other in-cabin MEs during the sampling run. Use high ventilation conditions (window and vent open, AC on during summer and heater on during winter) during the first 20 minutes and low ventilation (windows and vent closed, AC on during summer and heater on during winter) during the second 20 minutes. Maintain a safe following distance, about one car length (15 feet) per 10 mph speed, closing to within 3 feet during stopped conditions. Use the middle lane and do not follow the same vehicle for more than two minutes. Attempt to get behind at least one high-emitter during each of the two ventilation conditions. If accidents, other hazards, or local conditions change, substitute other, equivalent routes with similar distances and speeds as needed.

Sample in-cabin air at driver’s breathing zone continuously with a Langan T15 CO, NDIR CO, and ppbRAE PID analyzer and collect one set of canist e r and DNPH samples integrated over the entire hour. Collect four SPME samples, one every 10 minutes. Sample the outside air with a second portable PID monitor during the entire hour without compromising the ventilation condition in the cabin. Monitor and record the van’s position (GPS), and sampling point temperature and relative humidity. Other relevant data collected by the City of Atlanta include CO and meteorological data at the Rosw ell monitoring station at 4434 Roswell Rd. and the PM Super site at 829 Jefferson St. NW.

2. In vehicle: urban street canyons (ME2)

Mak e multiple trips during a 40-minute period along a surface-street loo p in downtown Atlanta bordered by Peachtree Street NW, Forsyth/Carnegie, Spring Street NW, and Harris Street (four right turns). Make the measurements during either the morning commute period from 0700 to 0800 or evening commute period from 1700 to 1800. Use high ventilation conditions (window and vent open, AC on during summer and heater on during winter) during first half and low ventilation (windows and vent closed, AC on during summer and heater on during winter) during second half. Drive at or near the end of a pack of vehicles at stoplights as much as possible and attempt to get behind at least one high-emitter during each of the two ventilation conditions.

Sample in-cabin air at driver’s breathing zone continuously with a Langan T15 CO, NDIR CO, ppbRAE PID analyzer and c o llect one set of cani ster and DNPH samples integrated ov er the entire hour. Collect four SPME samples, one every 10 minutes. Sample the outside air with a second portable PID monitor during the entire hour without compromising the ventilation condition in the cabin. Monitor and record the van’s position (GPS), and sampling point temperature and relative humidity. Note that GPS data are often unavailable or unreliable in urban canyons as the tall buildings block satellite signals.

3. In vehicle: refueling (ME3)

Sam p le for 20 minutes at the Racetrak or Quicktrip (QT ) service station lo cated north of the Thornton Rd exit off I-20. Conduct sampling during the peak or near-peak refueling periods for the station as indicated by service station personnel.

After driving to elevate measured fuel tank temperatur es, par k sampling van at refueling location and sample alternate 10-minute periods under background (parked at pump) and refueling conditions Park the van downwind from the centroid of the pump locations. Sample in-cabin air at driver’s breathing zone continuously with a KORE MS 200, Langan T15 CO, NDIR CO, and ppbRAE PID, and collect one set of canister and DNPH samples integrated over the sampling period. Collect two SPME samples, one 10-minute sample during the background sampling period and one 10-minute sample during the refueling period. Sample both the outside and in-cabin air with the two portable PID monitors during the entire sampling period. Monitor and record the outside wind speed, and direction as well as the sampling location temperature and relative humidity. A camcorder will be positioned to record the sampling scene from outside the van; a pan of the sampling site will also be provided to record details of the location. Va n windows are to be down and doors open as appropriate during this ME.

4. In vehicle: parking garage (ME4)

B-3Drive within a parking garage for 40 minutes. Use high ventilation conditions (window and vent open, AC on during summer and heater on during winter) during the first half and low ventilation (windows and vent closed, AC on during summer and heater on during winter) during the second half. Potential garages include Colony Square parking garage at Peachtree Street and 14 th Street in Midtown Atlanta during the morning and evening commute period and prior to and after the Atlant a Falcons’ pre-season football games if possible

Sample in-cabin air at driver’s breathing zone continuously with a Langan T15 CO, NDIR CO, ppbRAE, and DRI HCHO analyzer and c ollect one set of canister and DNPH samples integrated over the entire period Collect four SPME samples, one every 10 minutes. Sample both the outside and in-cabin air with the two portable PID monitors during the entire period without compromising the ventilation condition in the cabin. Monitor outside wind speed and direction (if any) an d record the in-cabin temperature and relative humidity. A camcorder will be positioned to record the sampling scene from outside the van; a pan of the sampling site will also be provided

to record details of the location.

5. In ve hicle: toll plaza (ME5)

Sam p le during the morning commute period for 40 minutes at the toll plaza between exit 2 and 3 on the GA 400

toll ro ad

.

Sample in-cabin air at driver’s breathing zone continuously with a Langan T15 CO, NDIR CO and ppbRAE PID analyzer a nd collect one set of canister and DNPH sa mples integrated over the entire period Collect four SPME samples, one every 10 minutes. Sample the outside air with a second portable PID monitor during the entire period without compromising the ventilation condition in the cabin. Mo nitor and record the van’s position (GPS), and sampling point temperature and relative humidity.

6. In vehicle: tunnel (ME6)

The Justus C. Martin Jr. Tunnel is the only roadway tunnel in Atlan t a. It is located less than two miles south of the toll plaza on GA 400. The tunnel consists of separate bores for the northbou nd and southbound direction consisting of four lanes each. The tunnel is very short an d is unlikely to restrict dilution of emissions to any significant degree. Traffic in both directions remains uncongested during the evening commute period. No sampling is planned for this microenvironment in Atlanta.

7. Outdoor: refueling vehicle (ME7)

Sam p le at the Racetrak or Quicktrip (QT) service stat ion located north of the Thornton Rd exit off I-20.

Co n duct sampling during the peak or near-peak refueling periods for the station as indicated by service station personnel.

Park the van downwind from the centroid of the pump lo cation s after driving it suffici ently to elevate measured fuel tank temperatures. Collect biomarker samples during refueling periods with low (< 5 mph) local wind speed. Breath samples are taken before and 10 second s immediately after active refueling. A backup breath samples is taken immediately after the second breath sample. With sampling inlets in the breathing zone, refuel the vehicle over a 1 to 2 minute active refueling interval within the second 10-minute sampling period. During refueling, maintain manual control of the nozzle and stand downwind of the vehicle fuel tank inlet, spilling a few drops of fuel after removing the nozzle from the fuel tank. Sample the breathing zone continuously with a KORE MS 200, NDIR CO, and ppbRAE and collect one set of canister and DNPH samples integrated over the entire 20-minute period. Collect a 5-minute canister sample that includes the active refueling period. Collect two SPME (background and refueling) samples during the initial background and final refueling periods. Record the ambient temperature and relative humidity. A camcorder will be positioned to record the sampling scene from outside the van; a pan of the sampling site will also be provided to record details of the location. Local wind speed, direction, temperature and humidity will be collected with the hand held meteorological monitor. A liquid fuel samples will be collected after ME7 measurements (during off-loading of the van fuel tank) for each service station (if more than one is used per city) sampled for this ME.

B-48. Outdoor: sidewalk near high-density traffic (ME8)

Conduct sidewalk sampling in downt own Atlanta along the city block bordered by Peachtree Street NE,

A ndrew Young International, Spring Street NW, and Harris Street NW. Sampling should be conducted during the morning and afternoon commute periods and during the noon hour.

Sample the breathing zone continuously with a Langan T15 CO, and portable PID monitor and collect one set

of canister and DNP H samples integr ated over the entire 40 minute peri od. Collect four SPME samples, one every 10 minutes. Record the ambient temperature and relative humidity.

9. Outdoor: bus stop (ME9)

Co m bined with ME8.

10. O utdoor: stadium parking lot (ME10)

Sam p le for 40 minutes at the end of an Atlanta Braves baseball game. Because the atmosphere is more stable in the evening, night games are preferable to day games. Attempt to determine the end of the game time by listening to the radio to determine the progress of the game. Park the van near the exit of the parking lot where vehicles will queue up as they exit, down wind of the exhaust.

Sample the breathing zone continuously with a KOR E MS 200, Lang an T15 CO, DRI HCHO analyzer, and portable PID monitor and collect one set of canister and DNPH samples integrated over the entire period. Collect six SPME samples one every 10 minutes. A camcorder will be positioned to record the sampling scene outside the van; a pan of the sampling site will also be provided to record details of the location.

11. Underground parking garage (ME11)

Sam p le the ambient air in the Colony Square underground parking garage (Peachtree and 14 th Streets) for 40 minutes starting about 5:00 p.m. when office workers leave the complex (col d start emissions). Sample at exit queues and ramps.

Sample the breathing zone continuously with a KORE MS 20 0, L angan T15, DRI HC HO analyzer, and portable

PID monitor and collect one set of canister and DNPH sa mples integrated over the entire period. Collect a 5- minute canister sample after a peak exposure encountered during the sampling period. Breath biomarker samples are collected before and within 10 seconds afte r a similar peak exposure and followed immediately by backup breath canister sample. Collect four SPME samples, one every 10 minutes . Record the local ambient wind speed, direction (if any), temperature and relative humidity with the hand held meteorological instrument. A camcorder will be positioned to record the sampling scene; a pan of the sampling site will also be provided to

record details of the location.

12. Outdoors: toll booth (ME12)

Make the m eas urement on the northbound side of the to ll plaza. Access to the toll plaza is from the nort h bound direction. This is an employee pa rking lot on the eastside of the plaza. An underground tunnel accesses the southbound lanes. There is an elevator down to the tunnel. Contact the John Leonard, deputy director at the Georgia Department of Transportation, 24 hours prior to sampling (404/463-8766). On-site supervisor at the toll plaza is Robert Smith. Clarice Boone is another on-site contact (404/760-5893).

Sample the breathing zone continuously with a KORE MS 20 0, L angan T15, DRI HC HO analyzer, and portable

PID monitor and collect one set of canister and DNPH samples integrated over the entire 40 minute period. . Collect four SPME samples, one every 10 minutes. Re cord the ambient temperature and relative humidity.

If time permits before or after the sampling period and suffi cient traffic ex ist, cond uc t measurement of in-cabin exposure during one pass through the toll plaza. Collect one SPME sample during this sampling period.

B-513. Trailing high emitters (ME13)

Attempt to trail high emitters in Atlanta locations with higher fractions of high emitters. Protocol will follow ME2 except there will be no limits placed on what str eets may be driven. Collect a 5-minute canister sample after a peak exposure encountered during the sampling period. Breath biomarker samples are collected before

and within 10 seconds after a simila r peak exposure and followed immedi ately by backup breath canister sample.

DAILY SAMPLING SCHEDULE

The prospective summer 2003 schedule for the Atlanta summer sampling program is summarized in Table 1. The

samp l ing schedule is subject to change due to field conditions encountered. Actual summer and winter schedules will appear in the draft/final reports. In order to stay on project schedule as much as possible, sampling will be conducted on Saturdays in case we encounter unsuitable meteorological conditions on scheduled sampling days. However, this daily schedule doesn’t take into consideration the potential for prolonged weather delays. The winter daily sampling schedule for Atlanta will be finalized prior to the 2004 winter study.

Table 1 Prospective Summer 2003 Daily Sampling Schedule for Atlanta



## August/September 2003

Sunday Monday Tuesday Wednesday Thursday Friday Saturday

24 25 26 27 28 29 30

Arrival/ Setup 7am ME1 7am ME1 7am ME1 7am ME1 7am ME1 10am

ME3/ME7

8am ME13 8am ME13 8am ME13 8am ME13 8am ME13

5pm ME11 5pm ME11 5pm ME11 5pm ME11 5pm ME11

31 1 2 3 4 5 6

8am ME3/7 8am ME3/7 8am ME3/7 8am ME3/7

5pm ME4 5pm ME4 5pm ME4 5pm ME4 5pm ME4

7 8 9 10 11 12 13

Packing Leave

for Reno

B-6

### APPENDIX C

Exposure Protocol and Study Plan for th e Section 211(B) Tier 2 High End Exposure Screening Study of Baseline and Oxygenated Gasoline Addendum C – Summer/Winter Sampling Plan for Chicago

Prepared for

AMERICAN PETROLEUM INSTITUTE

1220 L Street Washington, DC 20005-4070

Prepared by

DESERT RESEARCH INSTITUTE 2215 Raggio Parkway Reno, NV 89512

October 1, 2003

C-1INTRODUCTION

This sampling plan specifies the details for the field measurement program that will be carried out in Chicago, IL

duri n g the summer of 2003 and winter 2004 as part of a screening study of the high-end exposures to baseline and oxygenated gasoline. It specifies the measurement locatio ns for the twelve categories of microenvironments and explains the selections with respect to the objective of capturing the upper-end of the distribution of exposures for

each microenvironment. This document is an addendum to the Exposure Protocol and Study Plan, which describes the proposed measurement methods and ra tionale for their selection. We will en deavor to use the same ME locations during both the winter and summer studies.

Desert Research Institute personnel surveyed potential mi c r o environments in Chicago on August 14-16, 2002. The objectives of the survey were to ascertain the suitability of sampling locations with respect to access and potential for higher-end exposures, and to determine the variations in air pollutant levels in several of the microenvironments with a portable gas analyzer. We visited the following locations: I-57 and I-94 during the morning commute period, urban canyons in downtown Chicago (par ticularly under the elevated trains), Tri-State Tollway ((I-294) toll plazas, parking garages in downtown Chicago (Millennium, Monroe St and Grant Park underground garages), service stations (Gas City in Tinley Park), parking lots at United Center (Chicago Bulls and Blackhawks) and ComiskeyPark (White Sox), and three centralized vehicle inspection stations (#14, 27 and 28). A RAE Systems Model PGM7240 (ppbRAE) portable PID monitor and Langan Products Inc. T15 were used to continuously monitor ambient VOC and CO levels, respectively, in several of the microenvironments. For purposes of the survey of microenvironments in Chicago, the PID was used to measure relative variations rather than absolute VOC levels.

The location of the mobile laboratory is a significant logistical consideration in the selection of some of the

microe nv ironments. Accordingly, selectin g a base of operations for the mobile laboratory was the initial task during the survey trip. A suitable RV park is located in Tinley Park (Windy City Campground at 18701 South 80 th
Avenue), which is about 20 miles southeast of Downtown Chicago. Our search for some microenvironments such as service stations, vehicle inspection stations, and c ongested freeway was focused in this general area.

DESCRIPTIONS OF MICROENVIRONMENTS (ME) AND PROPOSED SAMPLING PROTOCOL

1. In vehicle: commuter rush hour i n stop-and-go traffic (ME1)

Begin the run at 0700 in South Chicago near the I-57 and I-94 interchange and drive north on I-94 towards

Downtown C hicago. The ten miles to the I-290 (Eis enhower Expressway) and I-94 interchange will take roughly 20 minutes. Use high ventilation conditions (windo w and vent open, AC on during summer and heater on during winter) during the first half of the run. Continue north on I-94 and turn around about 5 miles north of the I-290 and I-94 interchange. Reenter the I-94 going south and exit the freeway af ter the second 20 minutes. This stretch of freeway includes a series of overpasse s, with the longest about a quarter of a mile. Use low ventilation (windows and vent closed, AC on during summer and heater on during winter) during the second half. Maintain a safe following distance, about one car length (15 feet) per 10 mph speed, closing to within 3 feet during stopped conditions. Use the middle lane and do not follow the same vehicle for more than two minutes. Attempt to get behind at least one high-em itter during each of the two ventilation conditions. If accidents, other hazards, or local cond itions change, substitute other, equiva lent routes with similar distances and speeds as needed.

Sample in-cabin air at driver’s breathing zone continuously with: Langan T15 CO monitor, NDIR CO

inst rument, and ppbRAE, and collect one set of caniste r and DNPH samples integrated over the entire sample. Collect four SPME samples, one every 10 minutes. Sample the outside air with the second portable PID during the entire period without compromising the cabin ventilation condition. Monitor and record the van’s position (GPS), and in-cabin temperature and relative humid ity. A forward facing camcorder will record roadway activities and locations for this and other in-cabin MEs during the sampling run. Relevant data collected by the Illinois EPA include CO and meteorological data at the CTA Building monitoring station at 320 S. Franklin.

C-22. In vehicle: urban street canyons (ME2)

Make multiple trips during a 40-minute period along a surface-street loop in downtown Chicago bordered by

Lake St reet , Wabash Avenue, Van Bure n Street, and State Street (four right turns). The elevated train covers three sides of this loop. Make the measurements during either the morning commute period from 0700 to 0800 or evening commute period from 1700 to 1800. Use high ventilation conditions (window and vent open, AC on during summer and heater on during winter) during first 20 minutes and low ventilation (windows and vent closed, AC on during summer and heater on during winter) during second 20 minutes. Drive at or near the end of a pack of vehicles at stoplights as much as possible and attempt to get behind at least one high-emitter during

each of the two ventilation conditions.

Sample in-cabin air at driver’s breathing zone continuously with the Langan T15 CO, NDIR CO, and ppbRAE analyzer and co llect one set of canister and DNPH sample s integrated over the entir e period. Collect four SPME samples, one every 10 minutes. Sample the outside air with the second portable PID monitor during the entire period without compromising the ventilation condition in the cabin. Monitor and record the van’s position (GPS), and in-cabin temperature and relative humidity. No te that GPS data is often unavailable or unreliable during this ME as the tall buildings block satellite signals. A forward-facing camcorder will record roadway activities and locations during the run.

3. In vehicle: refueling (ME3)

Sample at the Gas City (80 th Avenue just north of I-80) or Speedway (Harlem Avenue just north of I-80) service stations in Tinley Park. Conduct sampling during the peak or near-peak refueling periods for the station as indicated by servi ce station personnel.

After driving to elevate measured fuel tank temperatur es, par k sampling van at refueling location and sample alternate 10-minute periods under background (parked at pump) and refueling conditions Park the van downwind from the centroid of the pump locations. Sample in-cabin air at driver’s breathing zone continuously with a KORE MS 200, Langan T15 CO, NDIR CO, and ppbRAE PID, and collect one set of canister and DNPH samples integrated over the sampling period. Collect two SPME samples, one 10-minute sample during the background sampling period and one 10-minute sample during the refueling period. Sample both the outside and in-cabin air with the two portable PID monitors during the entire sampling period. Monitor and record the outside wind speed, and direction, as well as th e sampling location temperature and relative humidity. A camcorder will be positioned to record the sampling scene from outside the van; a pan of the sampling site will also be provided to record details of the location. Va n windows are to be down and doors open as appropriate during this ME. A liquid fuel sample will be collected after ME3 measurements (during off-loading of the van fuel tank) for each service station (if more than one is used per city) sampled for this ME.

In vehicle: parking garage (ME4)

Drive within a parking garage. Use high ventilation conditions (window and vent open, AC on during summer

and h eater on during winter) during the first half and low ventilation (windows and vent closed, AC on during summer and heater on during winter) during the second half. Potential garages include Millennium, Monroe Street, or Grant Park underground parking garages in Downtown Chicago. Millennium and Monroe Street garages use the same access. Millennium is to the left after entering the undergrou nd garage complex, and the Monroe Street garage is to the right. Millennium is closer to the downtown office building and has many more parked cars than the Monroe St garage, which is located closer to the Michigan La ke shoreline. Monroe St. garage was mostly empty during the weekday, but may see for use during the weekends. Grant Park garage was nearly full and appears to have high fraction of commuters. Park adjacent to the northbound pay station. We observed 150 to 500 ppbC on PID and 8 to 26 ppm CO at this location during the 1700 to 1800 period.

Sample in-cabin air at driver’s breathing zone continuously with a Langan T15 CO, NDIR CO, ppbRAE, and

DRI HCHO a n alyzer and collect one set of canister an d DNPH samples integrated over the entire 40 minute period. Collect four SPME samples, one every 10 minutes. Sample both the outside and in-cabin air with the two portable PID monitors during the entire period with out compromising the ventilation condition in the cabin. Monitor outside wind speed and direction (if any) and record the in-cabin temperature and relative humidity. A

C-3camcorder will be positioned to record the sampling scene from outside the van; a pan of the sampling site will also be provided to record details of the location.

5. In vehicle: toll plaza (ME5)

Sample during the morning commute period 0700-0800 on tollways with high traffic volume with higher fraction of time spent at toll plazas (e.g., exit on ramps in both directions within short distances before and after the toll plaza). Potential plazas include 82 nd Street (southbound)/83 rd Street (northbound) and Cermak Road (all traffic) on the Tri-State Tollway (I -294) and the York Road (all traffic) on the East-West Tollway (I-88).

Sample in-cabin air at driver’s breathing zone continuously with a Langan T15 CO, NDIR CO and ppbRAE PID analyzer and c ollect one set of canister and DNPH samples integrated over the entire 40 minute period. Collect four SPME samples, one every 10 minutes. Sample the outside air with a second portable PID monitor during the entire period without compromising the ventilation condition in the cabin. Monitor and record the van’s position (GPS), and sampling point temperature and relative humidity.

6. In vehicle: tunnel (ME6)

The tunnel in Chicago is a covered roadway with no mechanical ventilation and very limited opportunity for

na tural v entilation. The route is from West Congress Parkway (Eisenhower Freeway) eastbound, enter Lower Wacker Drive via the off ramp from Congress parkway. Begin sampling anytime after entering the underground portion of the roadway. Proceed north on Lower Wacker Drive; immediately after Lower Wacker Drive turns east, use Orleans Street to turn ar ound and proceed back south on Lowe r Wacker Drive. Just before exiting Lower Wacker Drive at the south end of the street, there is a turn-around through the center divider that allows you to return northbound again.

Make several trips though the Lower Wacker Drive route for 40 minutes during peak traffic periods. Use high

ve n tilation conditions (window and vent open, AC on duri ng summer and heater on during winter) during first 20 minutes and low ventilation (windows and vent closed , AC on during summer and heater on during winter) during second 20 minutes. Sample in-cabin air at driver’s breathing zone continuously with a Langan T15 CO, NDIR CO, and ppbRAE, and collect one set of canister and DNPH samples integrated over the entire period. Collect a 5-minute canister sample during a peak concentration period. Collect four SPME samples, one every 10 minutes. Biomarker samples (breath) will be collected from the technician, who will be isolated from further exposure before performing this task. Sample the outsid e and in-cabin air with the two portable PID monitors during the entire hour without compromising the ventilation condition in the cabin. Monitor and record the van’s position (GPS), and in-cabin temperature and relative humidity. Note that the GPS data will be unavailable for the period the van is inside the tunnel as the tunnel blocks the satellite signals. A front-facing camcorder will record the roadway activities and provid e a stopped pan of the sampling site location.

7. Outdoor: refueling vehicle (ME7)

Sample at the Gas City (80 th Avenue just north of I-80) or Speedway (Harlem Avenue just north of I-80) service stations in Tinley Park. Conduct sampling during the peak or near-peak refueling periods for the station as indicated by servi ce station personnel.

Park the van downwind from the centroid of the pump lo cation s after driving it suffici ently to elevate measured fuel tank temperatures. Refueling sampling will be co nducted during periods with local wind speed below 5 mph. With sampling inlets in the breathing zone, re fuel the vehicle over a 1 to 2 minute active refueling interval within the second 10-minute sampling period. During refueling, maintain manual control of the nozzle and stand downwind of the vehicle fuel tank inlet, spilling a few drops of fuel after removing the nozzle from the fuel tank. Sample the breathing zone continuously with a KORE MS 200, NDIR CO, and ppbRAE and collect one set of canister and DNPH samples integrated over the entire 20-minute period. Collect a 5-minute canister that includes the active refueling period. Collect breath biomarker samples, including breath prerefueling and immediately after refueling (10 second) samples and a backup breath sample immediately after the second breath sample. Collect two SPME (backgro und and refueling) samples during the initial background

C-4and final refueling periods. Record the ambient te mperature and relative humidity. A camcorder will be positioned to record the sampling scene from outside the van; a pan of the sampling site will also be provided to record details of the location. Local wind speed, direc tion, temperature and humidity will be collected with the hand held meteorological monitor. A liquid fuel samp le will be collected after ME7 measurements (during offloading of the van fuel tank) for each service station (if more than one is used per city) sampled for this ME.

8. Outdoor: sidewalk near high-density traffic (ME8)

Conduct sidewalk sampling in downtown Chicago along the city block bordered by Monroe Street, Wabash

Aven ue, Adams Street, and State Street. Sampling is conducted during the morning periods and at noon.

Sample the breathing zone continuously with Langan T15 CO, and ppbRAE portable PID monitor and collect

one set of canister and DNPH samples integrated over the entire 40 minute period. Collect four SPME samples, one every 10 minutes. Record the local wind speed, direction, ambient te mperature and relative humidity with the hand held meteorological device.

9. Outdoor: bus stop (ME9)

Combined with ME8.

10. Outdoor: stadium parking lot (ME10)

Sample at the end of a Chicago White Sox baseball game at Co m i skey Park during the summer and after a Chicago Bulls or Blackhawks game at the United Center. B ecause the atmosphere is more stable in the evening, night games are preferable to day games.

Attempt to determine the end of the game time by listening to the radio to determine the progress of the game.

Park th e v an near the exit of the parking lot where ve hicles will queue up as they exit, down wind of the exhaust. Sample the breathing zone continuously with a KORE MS 200, Langan T15 CO, DRI HCHO analyzer, and portable PID monitor and collect one set of canister and DNPH samples integrated over the entire 40 minute period. Collect four SPME samples one every 10 minutes. A camcorder will be positioned to record the sampling scene from the cart outside the van; a pan of th e sampling site will record details of the location.

11. Underground parking garage (ME11)

Sample underground parking garage starting about 5:00 p.m. when office workers leave the complex (cold start

em issio ns). Sample at exit queue and ramps. Measure temperature, humidity and ventilation velocities. Potential garages include Millennium, Monroe Street, or Grant Park underground parking garages in Downtown Chicago.

Sample the breathing zone continuously with a KORE MS 20 0, L angan T15, DRI HC HO analyzer, and portable PID monitor and collect one set of canister and DNPH samples integrated over the entire 40 minute period.

Collect a 5-minute canister that incl udes an exposure peak encountered during the sampling period. Collect biomarker samples with breath samples taken before and immediately after (10-seconds) a peak exposure; a backup breath sample will be taken immediately after this second sample. Collect four SPME samples, one every 10 minutes. Record the local am bient wind speed, direction (if a ny), temperature and relative humidity with the hand held meteorological instrument. A camcorder will be positioned to record the sampling scene; a pan of the sampling site will also be provided to record details of the location.

12. Outdoors: toll booth (ME12)

Two possible locations for this microenvironment are tollbooths on tollways or one of the centralize vehicle

i n spect ion stations. The vehicle inspection station at 3824 159 th Place is reasonably clos e to the RV Park and has good access. Sampling at the toll plaza would be conducted behind the to llbooth similar to arrangement in Atlanta. For the vehicle inspection station, we would sample near the dynamometers. We will need to obtain permission from the Illinois EPA to conduct sampling at the inspection station.

C-5Sample the breathing zone continuously with a KORE MS 200, Langan T15, and portable PID monitor and collect one set of canister and DNPH samples integrated over the entire 40 minute period. Collect four SPME samples, one every 10 minutes. Record the ambient temperature and relative humidity. If time permits before or after the sampling period and sufficient traffic exist, conduct measurement of in-cabin exposure during one pass through the toll plaza. Coll ect one SPME sample during this sampling period.

13. Trailing high emitters (ME12)

Since we’ll be sampling the Wacker Drive ‘tunnel’ (ME6), there are no plans to sample ME13 in Chicago.

DAILY SAMPLING SCHEDULE

The prospective daily schedule for the Summer 2003 Chicago sampling program is summarized in Table 1. The

sam p l ing schedule is subject to change due to field conditions encountered. Actual summer and winter schedules will appear in the draft/final reports. In order to stay on project schedule as much as possible, sampling will be conducted on Saturdays in case we encounter unsuitable meteorological conditions on scheduled sampling days. However, this daily schedule doesn’t take into consideration the potential for prolonged weather delays. The winter daily sampling schedule for Chicago will be finalized prior to the 2004 winter study.

Table 1

Prospective Summer 2003 Daily Sampling Sc hedule for Atlanta



## July/August 2003

Sunday Monday Tuesday Wednesday Thursday Friday Saturday

31

Leave Reno 1 2

3 4 5 6 7 8 9

Arrival/ Setup Setup Final preparations 7am ME1 7am ME1 7am ME1 10am ME3,

ME7

Calibrate 8am ME13 12/1pm ME3/7 8am ME13

Familiarize 5pm ME4 5pm ME4 5pm ME4 5pm ME4 10 pm ME10 10 pm ME10

10 11 12 13 14 15 16

7am ME1 7am ME1 7 am ME8/9 7 am ME5 7am ME5 10am ME3,

ME7

8am ME13 8am ME13 8am ME2 8am ME2

12pm ME8/9 12pm ME3/7

5pm ME11 5pm ME11 5pm ME 8/9 5pm ME11 5pm ME11

17 18 19 20 21 22 23

7am ME5 7am ME12 7am ME12 Leave for Arrive

8am ME2 8am ME3/7 Packing Atlanta Atlanta 5pm ME4 5pm ME11 5pm ME12 10pm ME10

24 25 26 27 28 29 30

C-6

### APPENDIX D

Example of a Diary Page

D-1

### P027 API ME Diary Page (Not for Refueling)



## Circle One: ME1 In-Cabin Freeway; ME2 In-Cabin Urban Canyon; ME4 InCabin Under-Ground Garage; ME5 In-Cabin Toll Plaza; ME6 In-Cabin Tunnel;

ME8 Outdoor Sidewalk; ME9 Outdoor Bus-Stop; ME10 Outdoor Surface

Parking; ME11 Outdoor Under-Ground Garage; ME12 Outdoor Toll Plaza; ME13

Following Hi-Emitter.

Date: Start Time: Location:

Any Possible Pre-Exposure by Breath Technician?

Weather Description:

First 10 min: SPME 1. PMI:

Time Traffic Level Windspeed

Direction Unusual Events? Vent

High

Med

Low HI

LO

Outside

Second 10 min: SPME 2. PMI:

Time Traffic Level Windspeed

Direction Unusual Events? Vent

High

Med

Low HI

LO

Outside

Third 10 min: SPME 3. PMI:

Time Traffic Level Windspeed

Direction Unusual Events? Vent

High

Med

Low HI

LO

Outside

Fourth 10 min: SPME 4. PMI:

Time Traffic Level Windspeed

Direction Unusual Events? Vent

High

Med

Low HI

LO

Outside

D-2

### Notes:

D-3

### P027 API ME Diary Page (Refueling)

Circle One: ME3 In-Cabin Refueling ME7 Outdoor Self-Serve Refueling

Date: Start Time: Location:

Any Possible Pre-Exposure by Breath Technician?

Station Description: Total # of Pumps: Van at Pump #?

Draw sketch of station with location of van (North is up).

Weather Description :



## First 10 min: SPME 1. PMI:

Time # Cars in Station Windspeed

Direction Unusual Events? Vent

HI

LO

Outside

Second: SPME 2 PMI:

Time # Cars in Station Windspeed

Direction Unusual Events? Vent

HI

LO

Outside

Refueling: Time: Start: Stop:

# Gallons: # Drops (diameters) spilled:

Notes:

D-4

### APPENDIX E

Quality Assurance

E-1APPENDIX E



### 1.0 Quality Assurance

The Desert Research Institute maintains a very complete qu ality assu rance and quality control program that is detailed in this section. This section addresses all the required components from the RFP. These include:

a. Daily calibration. All instrument s to be us ed in this st udy ha ve calibration checks run each day. These checks will confirm both response factors and retention times for both continuous and timeintegrated instruments.

b. Daily instrument blank. An ap propriate blank will be run daily for each instrume nt. Gene rally this is run after the calibration check and before any sa mples are analyzed. This confirms that there is no carryover from the calibration check as well as confirming the blank or zero level of the

instrument.

c. Duplicate analysis for every 10 samples. Our protocols ge nerally call for 10% replicate analyses. These are an important part of our QA/QC program since these are applied to determine replicate precision that allows us to calculate sample uncertainty.

d. Control samples. DRI labs analyze a variety of control samples for QA/QC purposes. These

inclu d e calibration, replicate, collocated and blind QA samples.

e. Recovery tests for selected analytes. For DNPH analyses inte rnal sta ndards are also added. Recovery for NMHC samples in internally determined by calibration standards.

f. Determine and re port minimum tra pping efficiency. For so lid adsorbent samples, the backup traps are used for approximately 5 % of samples to conf irm th at n o quantifiable levels of compounds are getting through the first trap.

Every measurement consists of four attributes: a val u e, a precision, an ac curacy, and a validity (e .g., Hidy, 1985). The measurement methods described in the previous section ar e used to obtain the value. Quality assurance is the complementary part of the measuremen t process which provides the precision , accuracy, and validity estimates and guarantees that these attributes are within acceptable limits.

Quality assurance for the project is the joint responsib ility of th e laboratory manager and the quality assurance manager. The QA manager must ensure that the program design contains adequate quality control procedures and adequate external checks to assure that the data obtained will be adequate for their intended purposes. It is the responsibility of the laboratory manager to monitor the quality assurance activities during the project and to make certain that problems are rapidly identified and solved.

The quality assurance program includes two types of activ ities: qu a lity control (QC), and quality assurance (QA). The QC activities are on-going activities of measurement an d data processing personnel. QC activities consist of written standard operating procedures to be followed during sa mple collection, sample analysis, and data processing. These procedures define schedules for periodic calibrations and performance tests (including blank and replicate analyses). They specify pre-defined tole rances that are not to be exceeded by performance tests and the actions to be taken when they are exceeded. The QC activities also include equipment maintena nce and acceptance testing, and operator training, supervision, and support.

Quality assurance is a project management responsibility that integrates quality control, quality auditing,

measurem ent m ethod validation, and samp le validation into the measurement process. Quality auditing is an external function performed by personnel who are not involved in normal operations An independent auditor will be contracted by API to conduct a quality audit during a one week period in a single city. The purpose of quality



### E-2audits is to determine whether the QC procedures are adequate and are being followed and whether the tolerances for accuracy and precision are being achieved in prac tice. The quality auditing function consists of two components: systems audits and performance audits. Systems audits include review of the operational and QC procedures to assess whether they are adequate to assure va lid data that meet the specified levels of accuracy and precision. All phases of the measurement and data processing activities are examined during the systems audit to determine whether the procedures are being followed and the operating personnel are properly trained. Performance audits establish whether the predetermined specifications for accuracy are being achieved in practice. For measurements, the performan ce audit involves challenging the measurement/analysis system with a known standard sample that is traceable to a primary standard. Perfor mance audits of data pro cessing involve independent processing of raw data and comparing the results with reports generated by routine data processing.



### 1.1 Quality Assurance Objectives

The objectives of our quality assurance measures are:

1. To maintain a continuing assessment of the quality of data generated by analysts working in the laboratory. 2. To provide a permanent record of instrument performance as a basis for validating data and projecting repairs a n d re placement needs. 3. To ensure sample integrity. 4. To improve record keeping. 5. To produce analytical results that can withstand scientific and legal scrutiny.



### 2.0 Organization and Responsibility

The general structure of the organization of the Desert Rese arch Institute, Division of Atmospheric Sciences (DAS), Organic Analytical Laboratory is indicated on the Figure 2-2. For an effective quality assurance program, all individuals must take personal responsibility for monitoring, recording, and reporting all measures that relate to the quality assurance program. Specific responsibilities include the following:

DRI DAS

Executive Director

Dr. Kent Hoekman

DRI OAL QA Manager Ms. Nancy Peneff DRI OAL

Director

Dr. Barbara Zielinska

DRI OAL Laboratory Operations Dr. Wendy Goliff and Dr. John Sagebiel DRI OAL Field Operations Mr. Larry Sheetz

DRI OAL Laboratory Technicians Ms. Anna Cunningham, Mr. Michael Keith, Mr. Mark McDaniel, Ms. Katrzyna Rempala 

### Organizational Structure of OAL

DRI DAS

Executive Director

Dr. Kent Hoekman

DRI OAL QA Manager Ms. Nancy Peneff DRI OAL

Director

Dr. Barbara Zielinska

DRI OAL Laboratory Operations Dr. Wendy Goliff and Dr. John Sagebiel DRI OAL Field Operations Mr. Larry Sheetz

DRI OAL Laboratory Technicians Ms. Anna Cunningham, Mr. Michael Keith, Mr. Mark McDaniel, Ms. Katrzyna Rempala 

### Organizational Structure of OAL

Figure 2-2. Organization of the Desert Research In stitu te

– Division of Atmospheric Sciences, Organic Analytical Laboratory.



### E-3DAS Director (Dr. S. Kent Hoekman): Overall management and supervision of the Division of Atmospheric

Sciences.

QA Manger ( M s. Nancy Peneff): Responsible for internal audits and checks of laboratory QA program, operations, and procedures. Requests performance audits, and reviews procedures and protocols. Reviews data reduction and handling procedures.

Laboratory Director (Dr. Barbara Zielinska): Responsible for direct supervision of laboratory and field operations. Super v ises QA program at the operational level. Approves analytical and sampling methods, and practices. Reviews and approves all SOPs. Reviews and approves sampling media and sampling equipment certification procedures. Reviews and approves all laboratory-generated data. Reviews and ensures continued calibration of

instruments.

Laboratory Operations (D r. Jo hn Sagebiel and Dr. Wendy Goliff): Responsible for Laboratory Information Management System (LIMS), data management software and operations. Reviews and approves data. Under general supervision from Laboratory Manager, reviews laboratory practices and corrects as needed. Performs general maintenance on analytical instruments and LIMS computers. Performs Level I validation of data and participates in general review of all laboratory-generat ed data. Performs general maintenance on laboratory analytical instruments.

Field Operations (M r . Larry Sheetz): Responsible for assembly, cleaning, maintenance, and certification of all sampling equipment. Maintains records of use of each sampler, including any modifications made. Certifies proper operation of samplers including leak checks, and calibration of flow controlling equipment. Orders certification of

flow controllers as needed. Orders ce rtification of cleanliness of sampling equipment as needed. Maintains records of sampler maintenance and cleaning. Responsible for training of field personnel in proper operation, record keeping and maintenance of sampling equipment. Performs general maintenance on laboratory analytical

instruments.

Laboratory Technicians (Mr. M i chael Keith and Mark McDaniel, Mrs. Anna Cunningham, Ms. Katarzyna Rempala). Perform calibration of analy tical instruments. Perform regular calibration checks and recalibrate if calibration does not meet specified parameters. Log in samples in project logbooks upo n receipt. Properly store samples in possession. Perform analysis of samples. Perform analysis of media, canisters, and sampling equipment to ensure cleanliness. Responsible for record keeping. Participate in internal and external audits and checks of methodology. Perform other tasks as directed by Laboratory Operations, Field Operations, Laboratory Management, Laboratory QA or Center Director. Performs general maintenance on laboratory analytical

instruments.



### 3.0 Sample Custody

For our quality assurance plan, a sample is considered in custody when it is receive d by the DRI-DAS re ceiving depa rtment from an official package courier. At this time it is logged into the general receiving department's logbook and the Organic Analytical Laboratory is notifie d of the package's arrival. A representative of the laboratory signs for the package and returns with it to th e laboratory room, where he opens it. The samples are logged into the Organic Analytical Laboratory’s LIMS system in lieu of updating the chain-of-custody form (if supplied), and the samples are stored appropriately for the sample type. At this time any unusual situations (damaged shipping container, evidence of damage and/or tampering, etc.) are brought to the attention of the laboratory manager. If necessary, a review will be initia ted to determine if the damage compromised the integrity and/or quality of the sample.

Samples are stored in the Organic Analytical Laboratory, inside the DRI Northern Nevada Science Center (2215 Raggio Parkwa y, Reno, NV). All condensed phase sample s and sample extracts are st ored in the freezers. The rooms are locked when not in use and the building has limi ted access (i.e., it is locked from 1730 to 0730 weekdays

and all weekend to ensure access only to authorized personnel).



### E-4When a sample is analyzed, its identification number (sample number) is recorded both in the written logbook for

each instrument and in the LIMS file cr eated for that analysis. The sample number serves as a tracking number, as

does the LIMS file itself. Canisters will not be cleaned until each sample has passed initial validation.

Condensed phase samples and sample extracts will be mainta ined for at least one year following the completion of the project. Samples will be stored in refrigerators or freezers.



### 4.0 Laboratory Records

Several forms of laboratory records ar e routinely m aintained. Written records include receiving l ogbooks, shipping log books, chain-of-custody forms, project log books, instrument log books, instrument service logbooks, calibration records which include a calibration standard logbook and gr aphs of response factors vs. time, a canister cleaning logbook, and sampler maintenance and cleaning logbooks. Computerized records include method files, calibration files, raw data files, processed data files, and combined data files.

Written records are maintained in the appropriate location in th e labo rat ory. Written records are always maintained in non-erasable ink so that any alteration is easily not ed. Project logbooks record sample arrival and other information about the sample. Instrument logbooks record each sample run, including all pertinent information. All

calibration runs are also recorded here. Other calibration records include the calibratio n logbook where all standard solutions made in the laboratory are logged, a graph of a ll calibration checks, and the computerized calibration files. Service logbooks show services and/or modifications done to the instruments. The canister cleaning logbook records each canister number, the project the canister was used for, date of last cleaning, and certification

information.

Computerized records are main t a i ned on a central computer (the LIMS f ile server). Our data collection system includes a history record that maintains lists of files creat ed or modified and the name of the person creating or modifying the file. Each sample has an original report printed at the time the sample run is completed and this report indicates which method and calibration file are used, including the last modification date of the file. Backups of computerized records, including but not limited to removable media (floppy disks) and tapes are stored in the LIMS manager's office as an off-site storage area.



### 5.0 Standard Operating Procedures

Standard operating procedures (SOPs) codify the actions taken to implement a measurement process over a specified

tim e period. State-of-the-art scientific information is in corporated into the SOP with each revision. SOPs include the following elements:

1. A brief summary of the measurement method, its prin ciples of operation, its expected accuracy and precision, and the assumptions which must be met for it to be valid. 2. A list of materials, equipment, reagents and supplie rs. S p ecifications are given for each expendable item and its storage location. 3. A general traceability path, the designation of primary standards or reference materials, tolerances for

transf er standards, and a schedule fo r transfer standard verification. 4. Start-up, routine, and shutdown operating procedures and an abbreviated checklist. 5. Copies of data forms with examples of filled out forms. 6. Routine maintenance schedules, maintenance procedures, and troubleshooting tips. 7. Internal calibration and performance testing procedures and schedules. 8. External performance auditing schedules. 9. References to relevant literature and related standard operating procedures.

The standard operating procedures for all analyses will b e provided upon request.



### E-5

### 5.1 Sampling Media Preparation and Certification

For commercial cartridges, e.g. Waters Si-DNPH, DRI shal l analyze 5 % of the purchase initially to ascertain the blank variability. Another 5% will be analyzed if the initial data show that the blank variability is marginally acceptable (at or slightly higher than 1/ 3 of the desired lower quantifiable limits (LQL)). This is necessary because, unless cartridges are prepared in-house, there is no other indication of th e quality of the product, such as how pure the reagent or the blank cartridges are. In carbonyl measurement, the blank variability is the single most important factor in determining the lower quantifiable limit of the measurement. The other factors, such as flow rate and analytical variability are secondary in importance.

Tenax-TA solid adsorbent is cleaned by Soxhlet extraction with hexane/acetone mixture (4/1 v/v) overnight, and

drie d i n a vacuum oven at ~80 °C. The dry Tenax is packed into Pyrex glass tubes (4 mm i.d. x 15 cm long, each tube containing 0.2 g of Tenax) and thermally conditioned for four hours by heating in an oven at 300 °C under nitrogen purge (25 ml/min nitrogen flow). Approximately 10% of the precleaned Tenax cartridges are tested by GC/FID for purity prior to sampling. If Carbotrab, Carboxen and/or Carbosieve are used, the amount of Tenax is reduced as necessary. After cleaning, the Tenax cartridge s are capped tightly using clean Swagelok caps (brass) with graphite/vespel ferrules, placed in metal containers with activated charcoal on the bottom, and kept in a clean environment at room temperature until use.



### 5.2 Analytical Systems

Prior to analysis all analytical system s (i.e., GC/ECD/FID, HPLC, GC/M S, and GC/IRD/MSD) are checked for purity and are certified clean (less than 0.1 ppbv of targeted compound). Quality control in the laboratory includes instrument calibration for each batch of samples analyzed, re plicates of standards, and reanalysis of approximately 10% of the samples for estimation of analytical precision, which historically has been less than 6%. In past programs, field blanks were at the 0.5-1 ppb levels, based on the air volume of the samples. Coefficients of variation (CV) calculated from observed differences between duplicate sample pairs were under 10%. The data quality in this program is likely to be similar.



### 5.3 Standards and Materials

Primary reference standards are traceable to an NIST Stan dard Refere nce Material (SRM). For canister hydrocarbon speciation by GC/FID, we use NIST SRM 1805, which consists of 254 ppb of benzene in nitrogen. In addition, NIST SRM 2764 (245 ppb of propane in N2), is used for calibrating the light hydrocarbon analytical system. For halogenated compound m easurements, an NIST-traceable standa rd mixture of 39 compounds is purchased from Scott Specialty Gases and diluted by DRI scientists for calibration. For VOC measurements by GC/MS system, 74 compound mixture in low ppb level (Air Environmental, Inc., Denver, CO), traceable to the NIST SRM 1805, is used for calibration. For PAH meas urements NIST SRM 1647, with the addition of other compounds not present in the mixture, is used.

Gas cylinders of helium, nitrogen, hydrogen and ultra zero air (all UHP grade) — from the best sources available —

are used for the GC/FID, GC/ M S and GC /IRD/MSD. From a single analysis, the GC/IRD/MSD system gives three dimensions of data for positive compound identification: retention times, infrared spectra, and mass spectra. Identification of individual compounds is based upon matching corresponding data for authentic samples. The current inventory of reference samples at DRI's Organic Analytical Laboratory consists of over 250 single- and multi-component reference samples, and includes most of the compounds of interest in this project.



### E-6

### 5.4 Calibrations

The GC/FID, HPLC, GC/MS and GC/IRD/MSD systems are ca librated in itially b y multipoint calibration (i.e., three levels plus humid zero air), and regularly checked by a one-point calibration, using appropriate NIST SRM or other standard. The day-to-day reproducibility of ±10% is acceptable for either standard. Control charts are used for assessing analytical sy stem performance.

Samples that fall outside the calibration range are diluted until bracketed by the calibration curve. Instrument

respo n ses to calibration standards for each parameter are analyzed using a least squares linear regression. The calibration must generate a correlation co-e fficient (R2) of 0.99 to be acceptable.

During the course of analysis, calibrati on standards are rout inely analyzed to en sure that the instrum ent response has not changed. The criterion of 10% of expected response is used by the anal yst to determine whether the instrument

must be recalibrated. Retention time windows for each analyt e will be established prior to analys is and re-established continuously throughout the course of the analytical period.



### 5.5 Relative Accuracy and Precision of Sampling and Analysis

Accuracy involves the closeness of a measure m ent to a reference value and reflects elements of both bias and precision. Percent relative accuracy is calculated:

% Relative Accuracy = (X - Y)/X x 100

where: Y = concentration of the targeted compound, as determined by the analytical instrument,

and

X = concentration of the targeted com p ound in the NIST standard.

If the relative accuracy does not fall within the ± 10% ra nge, the instrument is recalibrated.

Precision is a measure of the repeatability of the results. The overall precision of sampling and analysis is

d e term ined by the analysis of collocated or equivalent samples. These precision tests will depend upon available resources, and we will develop the protocol in consultation with the project officer.



### 5.6 Internal Quality Control Checks

Our entire quality assurance program is organized around prov idi n g continuing internal quality control checks. This begins with proper training of the laboratory technicians so that they can identify problems with analyses and point these out to the Laboratory Operations Manager or Laboratory Manager for resolution. Other internal quality control checks include our blank checks, certification of sa mpling media, and our data analysis system. The ability of our data analysis system to merge multiple samples in to a single database allows for rapid and accurate crosscomparisons among the samples.

Other internal quality control checks consist of those or d e red b y the QA officer and required by our standard operations. Standard operation quality control checks include the calibration procedures, the regular calibration checks, and the duplicate analyses. Dup licate analyses are essential for determ ining precision of analyses and give us information about the stability of the system over time. The QA officer may, at his discretion, order performance checks at any time. These may include verification of response factors, blank checks of sampling media, and participation in interlaboratory comparisons (see below).



### E-7

### 5.7 Preventative Maintenance

All of our equipment is on a preventative maintenance schedule. We have found that the most important

pr ev entative maintenance tool is our systematic performance checks. When an instrument is not performing up to standards, we investigate and in this way find most problems before they become significant.

All of our major equipment (the GC/MS:s and HPLC) is on a service contract with t h e original manufacturer (Hewlett-Packard and Varian). This contract calls for biannual routine service by a Hewlett-Packard or Varian service technician, and immediate response to any service ca ll. Our contract specifically states that any problem will

be corrected within 48 hours of notification of the manufacturer.

Several laboratory personnel have extensive experience wo rking with all the major laboratory equipment and DRI has extensive support facilities (electronics and machine shop s, QA lab with standard re ference materials, etc.). These personnel and facilities ensure the continued smooth operation of all analytical instruments in the Organic Analytical Laboratory.



### 5.8 Corrective Action

A need for corrective action can be triggered by a number of activities, in clu ding the assessments of precision, accuracy, and completeness listed above. The most important corrective action trigger is the response factor chart mentioned above. This is the graph of our daily response factor check and it requires a full multi-point recalibration if the response factor differs by more than ±10% from the original calibration. Other triggers can include an instrument not meeting basic performance criteria, observations by any laboratory personnel of unusual performance by an instrument, or error messages displayed by the controlling computers or the LIMS system.

Once a need for corrective action has been identified, two basic steps follow: identification of the problem, and

co rrectio n of the problem. Exactly what action is taken de pends on what is determined to be wrong. Actions can include replacement of a defective part, correction of an incorrect flow, resetting or adjusting of tuning parameters, and contacting manufacturer service personnel for corrective action through our service contract.



### 5.9 Laboratory Data Processing

The goal of our data processing is to provide accurate data com b in ed into a single database for each analysis type and to include calculations of replicate precision, mean blank values, and blank variability, and blank-corrected concentrations and standard errors for each reported va lue based on combined volume (for carbonyl and semivolatile compounds), replicate (for hydrocarbon, SVOC an d carbonyl data), and blank uncertainties (for carbonyl and SVOC data only; substitute minimum detection limits for hydrocarbon data). The uncertainty analysis allows us to present our data with absolute uncertain ties associated with each number in the report.



### 5.10 Laboratory Data Management

The primary functions of laboratory data management are to have data stored in a consistent fashion that is both

secure and ava ilable. To serve this need we have establis hed a file server system that provides a central storage area for all laboratory and field data. The databases have define d structures that are maintain ed in one area so that all field names will be consistent, which permits easy merging and comparison of the various databases. Locating all data on a central file server prevents the problems associated with having multiple copies of the same data set, and allows the individuals charged with data processing, security, validation, and QA access to the same database.



### E-8

### 5.11 External Quality Assurance

The DRI Organic Analytical Laboratory (OAL) participated in the International Hydrocarbon Intercomparison Experiment, organized by National Center for Atmospheric Research (NCAR). The results of Tasks I, II, and III ofthis intercomparison have been published (Apel et al., 1994; 1999). The first task involved the circulation of a twocomponent hydrocarbon mixture of known composition and unknown concentration, prep ared by NIST. The DRI values were within the acceptable range of 5% of the nominal values provided by NIST. In task II the participating laboratories were asked to identify and quantify 16 components present, in the ppb range, in a mixture prepared by NIST. The agreement between the DRI values and the NCAR values, as well as with no minal values provided by NIST, were within acceptable ranges (15%). Task III was more complex - it involved the analysis of 60 commonly observed hydrocarbons in low ppbv concentrations in a mixture prepared and analyzed by Scott-Marrin, Inc., NCAR and U.S. EPA laboratory. The next tasks, IV and V, which were carried out in 1996 -1997, involved the analysis of ambient air samples in the ppbv and pptv concentration ra nges, respectively. The DRI has successfully completed these tasks — the agreement between the DRI values and the NCAR values were within acceptable ranges (10%).

In the summers of 1995 and 1996 the DRI OAL pa rticipat ed in the NARS TO-Northeast hydrocarbon intercomparison study, involving the analysis of two ambient air samples by participating laboratories. Participants included Biospheric Research Corporation (BRC), State Un iversity of New York at Albany (SUNYA), EPA Region I, DRI, and 8 of the PAMS networks in the northeastern U.S. The DRI laboratory perfor med the best in comparison with all other participants (Fujita et al., 1997). In the summer of 1997, the DRI OAL participated in the SCOS97- NARSTO performance audit and laborato ry comparisons involving speciated non-methane hydrocarbons (NMHC), carbonyl compounds, halogenated compounds and biogenic hydrocarbons (Fujita et al., 2003).

During the last six years, the DRI laboratory particip ate d in non-methane hydrocarbon laboratory performance audits, organized by the Quality Assurance Section, M onitoring and Laboratory Division, CARB. The last intercomparison studies, organized in 1999-2002, involved the analysis of ambient air samples by California district laboratories and the DRI laboratory.



### 6.0 REFERENCES

Apel, E.C., J.G. Calvert, and F.C. Fehsenfeld (1994). The Nonmethane Hydrocarbon Intercomparison Experiment (NOMHICE): Tasks 1 and 2. J. Geophys. Res. 99: 16,651-16,664 Apel, E.C., J.G. Calvert, T.M. Gilpin , F. C. Fehsenfeld, D.D. Parrish, W. A. Lonneman (1999). The Nonmethane Hydrocarbon Intercomparison Experiment (NOMHICE): Task 3. Journal of Geophysical Research, 104: 20,069-26,086 Fujita, E., G. Harshfield, L. Sheetz (2003). Performance Audits and Laboratory Comparisons for SCOS97-

NARS T O Measurements of Speciated Volatile Organic Compounds. In press. Fujita, E., Z. Lu, G. Harshfield, and B. Zielinska (1997). NARSTO-Northeast: Hydrocarbon and Carbonyl

Measurement Audits for the 1995 Field Study. Final Report prepared for the Electric Power Research Institute, Palo Alto, CA, July 1997 Hidy, G.M. (1985). "NMOG in California's South Coast Air Basin." Doctoral dissertation, University of California,

Los An g eles, CA, University Microfil ms International, Ann Arbor, MI.



### E-9

# Appendix B

Sampling and Analysis Methods

# Appendix B. Sampling and Analysis Methods

Table of Contents

1.1 Time-Integrated Air Sample Collection and Analysis ................................................2

1.2 BTEX by Solid Phase Microextraction (SPME) .........................................................4

1.2.1 Sampling ............................................................................................................4

1.2.2 Analysis ..............................................................................................................5

1.3 Continuous Methods ....................................................................................................8

1.4 Breath Collection and Analysis .................................................................................10

1

### 1.1 Time-Integrated Air Sample Collection and Analysis

Time-integrated monitoring methods are used for quantification of the responses of continuous surrogate instruments. The m ethods include canister sampling for VOC (BTEX, 1,3-butadiene, MTBE), solid ad sorbent sampling (for ethanol) and DNPH-coated Sep Pak cartridges sampling for carbonyl compounds. The DRI Organic Analytical Laboratory (OAL) routinely uses these methods and DRI standa rd operating procedures (SOPs) for sampling and analysis are available upon re quest. Five to forty minute samples are collected depending on the ME sampled.

Sampling. The DRI custom built sampler used for this study can samplesimultaneously a canister, solid adsorbent cartridges (two in parallel), and a DNPHimpregnated Sep-Pac cartridge. The sampler is compact and can be set-up in a vehicle cabin and run from a battery. Prior to use, the sa mpler is checked for cleanliness by sampling zero air. If the concentration of any ta rgeted compound exceeds 0.1 ppb, the sampler is thoroughly cleaned and re-tested. As noted earlier, a remote switch is installed to allow cabin on/off control of the sampler, no longer requiring access through the van tailgate. The protocol requires that th e van engine be off during changes of sampler media.

The canister sampler uses a differential pressure flow c ontroller to suppl y air to the sampler canister and a ca librated mass flow controller to check the flow rate. Since the actual flow rate is less important than that the fl ow rate remain consta nt, additional quality

assurance checks on the flow controllers is not necessary. For the 5-minute canister samples an additional battery-operated sampler is us ed that allows flows up to 3 L/minute to pressurize the 3 L canister.

Both the solid adsorbent and DNPH sample rs use a common vacuum pump controlled by ma ss flow controllers. These controllers are ca librated at the start of the field program by using a primary flow device (e.g. Gillibrator) a nd then periodically checked in the field to

confirm that the flow rates are accurate.

Canister samples. Prior to sampling, the canisters are cleaned by repeated evacuation and pressurization with humidified zero air, as described in the EPA document "Technical Assistance Document for Sampling and An alysis of Ozone Pr ecursors" (October 1991, EPA/600-8-91/215). Six sequential cycles of ev acuation to ~ 0.5 torr absolute pressure, followed by pressurization with ul tra-high-purity (UHP) humid zero air to ~ 20 psig are used.

The differences between the DRI procedure and the EPA recommended method are that the

canisters are heated in the DRI method to 140°C during the vacuum cycle and that more cycles of pressure and vacuum are used. Acco rding to our experience and that of others (Rasmussen, 1992), heating is essential to achiev e the desired canister cleanliness. Also, the canisters are kept longer under vacuum cy cles, about one hour in the DRI method, as opposed to half an hour in the EPA method. At the end of the cleaning procedure, one

canister out of 12 in a batch is filled with hu midified UHP zero air and analyzed by the gas chromatograph/flame ionization detection (GC/ FID) method. The canisters are considered clean if the total non-methane organic co mpound (NMOC) concentration is less than 20 ppbC. The actual concentrations of blank-check canisters are typically below 10 ppbC.

2

### Canister samples are analyzed promptly upon receipt of samples from the field, using GC/FID according to guidance provided by the EPA Method TO -15. The GC/FID response is calibrated in ppbC, using NIST Standard Reference Materials (SRM) 1805 (254 ppb of benzene in nitrogen). Based on the carbon response of the FID to hydrocarbons, the response

factors determined from these calibration sta ndards are used to convert area counts into concentration units (ppbC) for every peak in the chromatogram. Iden tification of individual compounds in an air sample is based on the co mparison of linear reten tion indices (RI) with

those RI values of authentic standard com pounds. A DB-1 column (60 m long 0.32 mm i.d., 1 μm film thickness) is used for these analyses. Breath canisters are quantified for CO2, MTBE, and BTEX by the method of Pleil & Lindstrom using GC/MS.

Blank checks are performed once daily, wh ile performanc e standards are executed three times per week. Our analysis plan and da ta processing standards call for the replicate analysis of approximately 10% of the samples. For canisters the replicate analysis is

conducted at least 24 h ours after the initial analysis to allow for re-equilibration of the compounds within the canister. The replicate an alyses are flagged in our database and the programs we have for data processing extract these replicates and determine a replicate precision. Replicate analysis is important because it provides us with a continuous check on all aspects of each analysis, and indicates prob lems with the analysis before they become significant. A portion (5%) of the canisters is also anal yzed by a second independent laboratory (Battelle-Columbus).

Solid adsorbent samples. Ethanol is quantified from solid adsorbent cartridges as

well as canister methods. Alt hough MTBE is stable in SU MMA canisters and can be quantified with high precision a nd accuracy, ethanol is relativel y unstable and the replicate analyses of canister samples show a high de gree of scatter (Goliff and Zielinska, 2001). Thus, the solid adsorbent samples are necessary for quantification of ethanol. For sample collection we use multibed adsorbent cartridges consisting of Tenax-TA, Carbotrap (or Carboxen) and Carbosieve (Shire et al., 1996; Tsai and Weisel. 2000; Vayghani et al., 1999).

Prior to use the Tenax-TA solid adsorben t is cleaned by Soxh let extraction with hexane/acetone (4/1 v/v) overni ght and dried in a vacuum oven at ~ 80 °C. The dry Tenax is packed into Pyrex glass tubes together w ith Carbotrap and Carbosieve and thermally

conditioned for four hours in an oven at 300 ° C under nitrogen purge. Approximately 10% of the precleaned tubes are tested by GC/FID prior to sampling. After cleaning, the tubes are sealed with clean Swagelok caps (brass) with graphite/Vespel ferrules, placed in metal

containers with activated charcoal on the botto m, and kept in a clean environment at room temperature until use.

After sampling at monitored fl ows of 200-300 ml/ minute, tube samples are analyzed by a thermal desorption-cryogenic preconcentration method, followed by hi gh-resolution GC/MS. A Chrompack Thermal Desorption-Cold Trap Injection (TCT) unit is used for sample desorption and cryogenic preconcentration. The compounds of interest are quantified by MS, using the response factors of authentic standards, prepared at five di fferent concentrations

with a static dilution bulb.

Carbonyl compounds. Formaldehyde and acetaldehyde are collected with Sep-Pak cartridges that have been im pregnated with an acidified 2,4-dinitrophenylhydr azine (DNPH)

3

### reagent (Waters, Inc), accord ing to the EPA Method TO-11A. When ambient air is drawn through the cartridge at nominal flow rates of 1 L/min, carbonyls are captured by reaction with DNPH to form hydrazones, which are sepa rated and quantified in the laboratory using HPLC (Fung and Grosjean, 1981). The ambient measurement results ar e subject to various

artifacts due to sorbent interactions with ozone so ozone is rem oved with a honeycomb

denuder coated with sodium carbonate/sodium n itrite/glycerol mixture (Koutrakis, et al., 1993). After sampling, the cartridges are eluted w ith acetonitrile. An aliquot of the eluent is transferred into a 1-ml septum vial and in jected by autosampler in to a high performance liquid chromatograph (Waters Alliance System) for separation and quantization of the hydrazones (Fung and Grosjean 1981).

1.2 BTEX by Solid Phase Microextraction (SPME)

1.2.1 Sampling

Carboxen/(poly)dimethylsilo xane (CAR/PDMS) coated (75 μ m) quartz fibers are

used for 10-m inute BTEX sampling. SPME is a passive method, thus the rate of the fiber uptake is controlled by the diffusion rate of th e analytes to the fiber. In a stationary environment without air movement, a concentrat ion gradient is formed in the boundary layer between the fiber and the surrounding environmen t. This situation occurs during fiber calibration in a static system, such as a Tedl ar bag. However, in an outdoor environment there is always some air movement and the sorpti on rate will be higher in this situation, since the thickness of the boundary layer will be sma ller. This phenomenon explains some of the

differences observed between canister and SPM E samples collected in summer 2002. To improve the agreement between these methods the Summer 2003 SPME samples were obtained using the experimental set up in Fi gure 1. The outlet of the SPME sampling bulb was connected to the Tenax media sampling pump. Active sampling at low constant air

flows was a suitable solution of outdoor field sa mpling variability on windy days. With these modifications, wind speed influence is avoided and a common air stream is being sampled by all instruments. The SPME was exposed to the air stream at a fixed flow rate of about 300 ml/min. The sampling bulb temperature is not controlled.

4

### Figure 1. SPME Sampling System Set Up

1.2.2 Analysis

All SPME BTEX samples are analyzed in a mobile laboratory with a Model 8610C SRI Instruments GC equipped with a heated inje ction port suitable for SPME desorption, a CP-Sil 5 (Varian, Inc.) capillary column (60m, 0.32mm i .d.), and a PID detector. The heated flash vaporization injector is maintained at 250 ° C and the PID at 150 ° C. The column temperature was programmed at 60 ° C for 2 min, 8 ° C/min to 165 ° C (held for one minute), and then

45 ° C/min to 240 ° C. The helium carrier gas flow rate was 3 ml/min.

Blanks and calibration checks are performed daily on the SRI GC in or der to determine the performance of the instrument. Fibers are kept in the injector port throughout the sample run to guarantee that the entire sample was desorbed and to begin the conditioning of the fiber.

Fibers are further cleaned in a fiber conditioner at 300 ° C for at least one hour. One fiber per

batch of 5 is checked for cleanliness after c onditioning. The fiber condi tioner consisted of a

70 cm x 16 cm stainless steel container w ith 5 ports and a Watlow heater/temperature controller capable of maintaining temperatures in the 200-300 ° C range. A helium flow of approximately 10 ml/min is maintained during fiber conditioning. Testing showed that the same fiber can be reused up to 40 times absent breakage of the fiber or failure of the fiber mounting mechanism.

The SRI GC is calibrated with 1 μ l injections of liquid standards prepared in pentane with

BTEX at different concentra tions (1, 5, 10, 20, 40, 50, and 100 ng/ μ l). Carboxen/PDMS fibers are calibrated by introducing the SPME fibe r for a defined time into a flowing standard gas containing the calibration component under the same flow-through conditions used for field sampling). The fiber is then analyzed by GC/PID. SPME ga s calibrations are done throughout the study as necessary. BTEX ca libration is performed with certified gas

standards at different con centrations (20, 80, 100 and/or 200 ppbv for each compound).

5

### The dependence of the SPME uptake rate on the sa mple flow rate is shown in Figure 2. The response changes logarithmically and reaches a plateau region after approximately 0.038 cm/s when changing flow has a lesser effect on the amount of extracted mass. Optimal flow

was determined to be 0.038 cm/s. The linear velocities studied were low (0.0044-0.1126 cm/s) enough to characterize a “quasi static” en vironment. The flow profile showed two distinctive zones in Figure 2. In the first zone (0-0.0665 cm/s ) mass transfer is controlled by diffusion through the well-developed fibe r boundary layer; in the second zone (0.0665 cm/s and higher) transfer is controll ed by diffusion through the fiber pores.

Sampling was performed within the plateau re gion where the SPME response is not greatly affected by changes in the flow.

Figure 2. SPME Flow Profile

Sampling temperature and humidity are also im portant parameters affec ting the SPME data. Temperature correction factors are obtained in the laboratory. The sampling bulb is temperature controlled with a c ooling/heating system. Temperature inside the glass bulb is measured with a thermocouple. For introducing humidity, a heated injection port is added before the glass bulb entrance in order to inject water with a syringe pump to produce the desired relative humidity (Tuduri, et al., 2001; Nelson, 1992; Martos, P. and J. Pawliszyn, 1997, and Lodge 1989).

6

### Chai and Pawliszyn, 1995, performed several e xperiments to determine the influence of relative humidity (RH) on the 100 μ m PDMS partition coefficient (Boy-Boland, 1998). RH usually decreases the response factor (Kfg) of each individual compound. The decrease of the response is dependent on temper ature. At lower temperatures humidity has a larger effect on the response factor. The highest effect of humidity was observed for a 0°C-10°C temperature range for 0% to 25% RH. Change s in the area counts at 0°C-25°C for 25%-75% RH were almost negligible. It is understood that humidity affects the fiber response because water at high concentrations competitively adsorbs into the coating of the fiber. Some compounds are less affected by humidity than others.

The 75 μ m Carboxen/PDMS fiber showed no eff ect with RH at 100 ppbv of BTEX concentration. Experiments at 25°C and 12.5°C de termined that RH does not affect the fiber uptake of BTEX compounds significantly. Fi gure 3 shows toluene response at 100 ppbv for different RH. All the other BTEX species beha ved similarly. Data for BTEX showed a

standard deviation between 5 to 13% for the range of humidity analyzed, 10% to 80% RH. Sensors are accurate as long as there is no c ondensation of water, which may happen above 85% RH). These differences in the response of the fiber are within the precision of the method. Low RH effects on the fiber sensitivity may be due to the low concentration ranges

used for calibration. At low BTEX concentr ations, water is proba bly not an important competitive molecule. More research in this area is suggested.

SPME Carboxen/PDMS coated (75 μ m) fibers are used with portable or m anual samplers. When manual samplers are used, the tip of the n eedle is closed with a septum or Teflon tape(Martos and Pawliszyn, 1997 and Chai and Pawliszyn, 1995). Prior to sampling, the precleaned fibers are kept at ambient temperature within an activated charcoal protector. This storage method has been tested in the laborat ory and BTEX backgrounds are stable up to 48 hours in storage following cleaning (the longest tested period). After sampling, fibers are kept in sealed Mylar bags inside a cooler with dry ice. Samp les are analyzed 4-10 hours after sampling, on average, with a minimum of 1 hour and a maximum of 20 hours between sampling and analysis.

70 5000 10000 15000 20000 25000

0 10 20 30 40 50 60 70 80 90
Relative Humidity (%)Area Counts

Toluene 25C Toluene 12.5C Avg 25C Avg 12.5C



### Figure 3. Humidity Effect in GC/PID res ponse for a 100 ppbv BTEX standard at 25oC and 12.5oC (with a standard deviation of 5% for the 12.5 ° C and 8% for 25 ° C from the res pective mean)

1.3 Continuous Methods

The continuous Kore MS200 is used to monitor BTEX on a one-minute basis, sampling during the initial 10 second portion of each 60 sec ond period. This instrument uses a time-offlight mass spectrometer to separate compou nds of interest. Rather than using a gas chromatograph, this instrument uses a softwa re solution and a library of 70 eV electron ionization fragmentation patterns to apportion the contribution of each parent species to the time-of-flight (TOF) mass spectrum recorded by the instrument. The software program does not distinguish between specific isomers so xyl enes and ethylbenzene are reported together. The inlet uses a polydimethylsiloxane membrane preferentially to allow non-polar organic compounds into the analyzer while impeding pol ar species and air components to maintain the vacuum inside the analyzer chamber. Th e instrument performed well during the pilot studies and early field work, co mparing favorably with the canister measurements for most samples, although it became increasingly unreliabl e in subsequent field studies. Given the corroborative role proposed for this device, we do not believe the information provided by this instrument, while desirable, is necessary to fulfill the goals of the screening study.

Carbon monoxide is monitored continuously by the Langan T15 electrochemical monitor for CO and by a nondispersive infrar ed (NDIR) analyzer. The response time of Langan T15 instrument is slower than the response of the infrared-based instruments. Prior to each period of field measurement the instrument is calibrated using a zero-air generator and

8

### span gas to provide two refere nce points encompassing the exp ected range of concentrations anticipated during actual te sting. The two-point calibrati on procedure is as follows:

1. Allow instrument to stabilize for a minimum of 15 minutes.

2. Record ambient concentration as determined by the instrume nt. 3. Connect inlet lines from the instrument to a zero-air source (for a passive sampler use the flooder cap provided by manufacturer ) and check for a flow rate of >1 lpm with rotometer. 4. Let instrument stabilize, record current baseline, then adjust zero. 5. Connect inlet lines to a tank of span gas with an appropriate CO concentration for anticipated range and verify flow rate 6. Let instrument stabilize, record current r eading, and adjust span to correct value.

7. Re-connect instrument to zero-air sour ce, let stabilize and check baseline zero reading. 8. Repeat steps 4-7 if necessary.

9. Check a third concentration leve l with span gas if available.

During field measurements the passive sampler is checked against the reference unit, which

has automatic baseline stabilization and an inte rn al zero-air source. Baseline readings will be recorded at the beginning and end of each sampling day. If significant deviations are observed a re-calibration will be performed.

RAE Systems Model PGM-7240 (ppbRAE) portable PID monitors are used to continuously monitor ambient VOC levels in high end micr oenvironments. The monitor is sensitive to organic and inorganic gases that have an i onization potential of less than 10.6 eV, which includes most compounds of intere st in this study. It does no t respond to light hydrocarbons such as methane, ethane, propane, and acetyleneor to CO or formaldehyde.

A Continuous Formaldehyde Monitor was purchased from Alpha-Omega Power Technology, Ltd. (Albuquerque, NM). The Alpha-Omega (AO) a wet instrument that utilizes the Hantzch reaction, absorbing formaldehyde in acidified water, reacting it with 2,4-pentanedione and ammonia to form a cyclized product, 3,5-d iacetyl-1, and 4-dihydrolutidene, which is continuously detected by fluorescence. The me thod is sensitive and highly specific for formaldehyde.

9

### 1.4 Breath Collection and Analysis

Breath is collected from technicians who particip ate in a scripted exposure. Since this study requires the use of human subjects, the fina l protocol w as reviewed by an Institutional

Review Board that is certified with the National Institute of Health.

Technicians were instructed to avoid expos ure to materials that m ay compromise the exposure assessment prior to and during the scri pted exposures. This includes avoiding alcohol ingestion (ethanol) and cigarette smoke for at least 3 days pr ior to the scripted exposures. Breath samples collected before the exposure were used to assess background

levels in the technician.

The test subject takes the three breath samples. One sample is tak en before initiating ME sampling for background purposes; the second samp le, ten seconds (timed with a stopwatch) immediately after completing an active refuelin g task or experienci ng a measured peak exposure in another ME, and the third samp le 1 minute immediately following the second sample. The 3 rd 

### backup sample is analyzed in case there is a problem with the second sample. The technician takes a 1-liter caniste r, places the tube in his mouth, and breathes smoothly and regularly through the mouth around the tube until a resti ng breath pattern is

established. At the end of a normal exhalati on, the technician clos es the mouth, opens the canister valve, and continues to expel the expiratory reserve. The canister vacuum will collect 1 L of the expiratory reserve. When th e flow stops, the technician closes the canister valve to capture the sample (P leil and Lindstrom, 1995; 2002). Breath samples are collected

in 1 L silico-steel steel canisters (Restek, Inc). .

Gas Chromatography-Mass Spectrometry. The analysis of VOC in breath samples is conducted as described by Pleil and Lindstrom (1995, 2002). Prior to the commencement of sampling, the CO 2 

### level in alveolar breath of all t echnician subjects is measured using GC/FID. Since the FID does not respond to CO 2 

### , this species is converted to methane by a methanator, positioned after the GC column, but ahead of the FID. Three breath samples are collected and analyzed, and the mean CO 2 

### value is used for further comparison. After breath sample collection, the CO 2 

### is measured using the same method. The target VOC (MTBE, 1,3-butadiene, ethanol, BTEX) is measured using a GC/MS technique. The GC/MS system includes an Entech 7100 prec oncentrator, a Varian 3800 gas chromatograph with FID and column switching valve, and a Varian Satu rn 2000 ion trap mass spectrometer.

10

### References:

Boy-Boland, A. (1998). SPME – Solvent-free sample preparation for GC and HPLC. Chemistry in Australia , 65: 10-12

Chai, M. and J. Pawliszyn (1995) Analysis of Environmental Air Sa mples by Solid-Phase Microextraction and Gas Chromatography/Ion Trap Mass Spectrometry, Environmental Science and Technology , Vol. 29, No. 3: 693-701.

Fung, K., and D. Grosjean (1981). "Determi nation of Nanogram Amounts of Carbonyls as 2,4-Dinitrophenylhydrazones by High Perf orma nce Liquid Chromatography." Anal.

Chem. , 53: 168-171.

Goliff, W.S. and B. Zielinska (2001). L ong-Term Stability of Oxygenated Compounds in Electropolished Canisters, Pa per #403, presented at the 94 Annual A&WMA Conference and Exhibition, June 24-28, 2001, in Orlando, Florida. th



### Koutrakis, P., J.M. Wolfson, A. Bunyaviroch, S. E. Froehlich, K. Hirano, J.D. Mulik (1993).

Measurement of Ambient Ozone Us ing a Nitrite-Coated Filter. Anal Chem 65: 209-

214.

Li, K., A. Santilli, M. Goldthorp, S. Whiticar, P. Lambert, M. Fingas (200 1). Solvent vapour monitoring in work space by so lid phase micro extraction. Journal of Hazardous

Materials 83: 83-91

Lodge, J. P. (1989). Methods of Air Sampling and Analysis. Third edition, Lewis publishers. Intersociety committee, Michigan, p. 15-16

Martos, P. and J. Pawliszyn, (1997) Calibra tion of Solid Phase Microextraction for Air Analysis Based on P hysical Chemical Pr operties of the Coating. Analytical Chemistry, 69: 206-215.

Nelson, G. O. (1992). Gas Mixt ures: Preparation and Control. Lewis Publishers, CRC Press, Chelsea, MI

Pleil, J. and A. Lindstrom (1995). Measurem ent of volatile organic compounds in exhaled

breath as collected in evacuat ed electropolished canisters. J. of Chromatography B: Biomedical Applications , 665: 271-279.

Pleil, J. and A. Lindstrom (2002). A review of the US EPA’s single breath canister (SBC)

method for e xhaled volatile organic biomarkers. Biomarkers, 7: 189-208

Rasmussen, R.A. (1992). “The ABCs of stainl ess steel canister clean-u p and certification.”

Presented at the 1992 U.S. EPA/A& WMA In ternational Symposium on Measurement of Toxic and Related Air Pollutants, Durham, NC, May 1992.

11

### Shire, J.; Harshfield, G.; Zielinska, B.; Pa sek, R. (1996). “A Comparison of Analytical Methods for Oxygenated Volatile Organic Compounds in Ambient Air,” In: Proceeding of the U.S. EPA/A&WMA Intern ational Symposium on Measurements of Toxic and Related Air Pollutants: Durham, NC, May 1996. p. 740-747.

Tsai, P. and C.P. Weisel (2000). Penetration of Evaporative Emissions into a Hom e from an M85-Fueled Vehicle Parked in an Attached Garage, Journal of the Air & Waste Management Association, 50: 371-377.

Tuduri, L.; Desauziers, V.; and Fanlo, J. L. (200 1). Potential of Solid -Phase Microextraction

fi bers for the Analysis of VOC in air. Journal of Chromatographic Science , 39: 521-

529

U.S. Environmental Protection Agency (199 1). "Technical Assistance Document for

Sa mpling and Analysis of Ozone Precurs ors." Document No. EPA/600-8-91/215, U.S. Environmental Protection Agency, Research Triangle Park, NC.

US EPA Method TO-11A Determination of Fo rmaldehyde in Ambient Air Using A dsorbent Cartridge Followed by High Performan ce Liquid Chromatography (HPLC) in Compendium of Methods for the Determ ination of Toxic Organic Compounds in Ambient Air – Second Edition, EPA/625/R-96/010b, January 1999.

US EPA Method TO-15. Determination of Vo latile Organic Compounds (VOCs) In Air Collected In Specially-P repared Canisters And Analyzed By Gas Chromatography/Mass Spectrometry (GC/ MS)-Second Edition, EPA/625/R-96/010b, January 1997.

Vayghani, S. A. and Weisel, C. (1999). The MTBE air concentrations in the cabin of automobiles while fueling. Journal of Exposure Analysis and E nvironmental Epidemiology , 9, 261-267

12

# Appendix C

Characterization of Solid-Phase Microextraction and Gas Chromatography for the Analysis of Gasoline Tracers in Different Microenvironments

(Celballos, D., Zielinska, B., Fujita, E., Sagebiel, J. (2007) J. Air & Waste Manage. Assoc. 57: 355-365)

Link to JAWMA article: http://216.92.182.36/gsearch/journal/2007/3/ceballos.pdf

# APPENDIX D

Section 211(B) Tier 2 High-End Exposure Screening Study Of Baseline and Oxygenated Gasoline – 1st Reno Pilot Study

## APPENDIX D First Reno Pilot Study

Section 211(B) Tier 2 High-End Exposure Screening Study Of Baseline and Oxygenated Gasoline – Pilot Study

Final Report

Prepared for

AMERICAN PETROLEUM INSTITUTE

1220 L Street Washington, DC 20005-4070

Prepared by

Barbara Zielinska, John Sagebiel, Eric Fujita and Dave Campbell

Desert Research Institute 2215 Raggio Pkwy.

Reno, NV 89512

Jake McDonald Lovelace Respiratory Research Institute Inhalation Toxicology Laboratory

P.O. Box 5890 Albuquerque, NM 87185

Tomas J.Kelly and Darrell W. Joseph

Battelle 505 King Avenue, Columbus, Ohio 43201

June 13, 2002

### ii

### ACKNOWLEDGMENT

This work was supported by the American Pe troleum Institute (API) and was conducted

in coordination with the U.S. Environmental Pr o tection Agency. We gratefully acknowledge the technical support provided by Dr. Will Ollison of the API and Dr. Ted Johnson of TRJ Environmental during the pilot study.

iii

### TABLE OF CONTENTS

Acknowledgment ................................................................................................................. ........... ii

List of Tables .................................................................................................................

................ iii List of Figures................................................................................................................ ................ iv

1. INTRODUCTION ................................................................................................................... 1-1

1.1 Measurement Methods ......................................................................................... 1-1

1.2 Description of Microenvironm ents and Sa mp ling Procedures ............................1-2

2. RESULTS

............................................................................................................................... . 2- 1

2.1 Continuous Instruments

....................................................................................... 2-1

2.2 Integrated Samp les ............................................................................................... 2-2

2.3 Solid Phase Microextraction (SPME) .................................................................. 2-5

2.4 Biological Samp les .............................................................................................. 2-6

2.4.1 Breath VOC Concentrations .................................................................... 2-6

2.4.2 Urine VOC Concentrations ...................................................................... 2-8

2.5 Results of Additional Refueling Experim ent (June 4, 2002, Reno) ..................2-10

2.5.1 MS200 and Canister Results .................................................................. 2-11

2.5.2 Breath Sample Results ........................................................................... 2-11

2.5.3 Analysis of Urinary VOC Concentrations ............................................. 2-12

3. RECOMM ENDATIONS ......................................................................................................... 3-1

3.1 Exposure Measurements ...................................................................................... 3-1

3.2 Recommendations for M easurements of VOC in Breath ....................................3-2

3.3 Recommendations for Measurement of VOC in Urine ....................................... 3-3

4. REFERE NCES ........................................................................................................................ 4-1

iv

### LIST OF TABLES

Table 1.1 API S211 (b) Exposur e Study-Reno Pilot Study ........................................................ 1-2

Table 2.1 Canister and Te nax/Carbotrap Data............................................................................ 2-3

Table 2.2 Comparison of MS 200 with Canisters ........................................................................ 2-4

Table 2.3 Comparison of Formaldehyde Data ............................................................................ 2-4 Table 2.4 Concentrations (ppbv) of vola tile organic compounds in breath and

m icroe nvironments...................................................................................................... 2-7 Table 2.5 Urinary benzene concentrations in two subjects exposed to three

Microenvironments ................................................................................................... 2-10 Table 2.6 Breath Data (ppbC) .................................................................................................. . 2-13

Table 2.7 Concentrations of Ethanol, MTBE & BTEX in urine samples (ng/L)...................... 2-16 Table 3.1 Recommendation Summary........................................................................................ 3-1

v

### LIST OF FIGURES

Figure 2-1 Concentration Ti me Ser ies, Freeway AM ...........................................................F-1 Figure 2-2 Concentration Time Series, Surface Streets......................................................... F-2 Figure 2-3 Concentration Ti me Ser ies, Freeway PM ............................................................F-3 Figure 2-4 Concentration Time Series, Refueling In-Cabin..................................................F-4 Figure 2-5 Concentration Time Se ries, Refueling out of cabin.............................................F-5 Figure 2-6 Concentration Time Series, Walking Downtown ................................................F-6 Figure 2-7 Concentration Time Series, Underground Garage...............................................F-7 Figure 2-8 Concentration Time Series , Residential Garage Background A..........................F-8 Figure 2-9 oncentration Time Series, Residential Garage Background B.............................F-9 Figure 2-10 Concentration Tim e Series , Residential Garage Sam ple C ...............................F-10 Figure 2-11 Concentration Time Series , Residential Garage Sam ple D ...............................F-11 Figure 2-12 Concentration Time Series , Residential Garage Sam ple E................................F-12 Figure 2-13 Concentration Time Series , Residential Garage Sam ple F................................F-13 Figure 2-14 Concentration Time Series , Residential Garage Sam ple G ...............................F-14 Figure 2-15 Concentration Ti me Ser ies, Generator...............................................................F-15 Figure 2-16 MS200 Raw and Corrected Data .......................................................................F-16 Figure 2-17 MS200 Corrected Data Only .............................................................................F-17 Figure 2-18 Correlation between CO by T15 and by Innova ................................................F-18 Figure 2-19 Correlation between Innova and TEI for total hydrocarbons ............................F-19 Figure 2-20 Innova vs. TEI for total hydro carbons with three ou tliers removed..................F-20 Figure 2-21 Correlation between CO and formaldehyde ......................................................F-21 Figure 2-22 Correlation between DNP H and continuous formaldehyde...............................F-22 Figure 2-23 Pre and post exposure br eath samples during refueling.....................................F-23 Figure 2-24 Pre and post exposure breath samples during in-cabin fueling..........................F-24 Figure 2-25 Pre and post exposure breath samples during walk ........................................... F-25 Figure 2-26 Relationship between full and alveolar breath...................................................F-26 Figure 2-27 The three traces; benzene, toluene and sun of xylenes and ethylbenzene ......................................................................................................F-27 Figure 2-28 Data for BTEX and MTBE................................................................................F-28

vi

### 1. INTRODUCTION

This report summarized the results of a pilot study that was c onducted in Reno, NV, from February 25 through March 1, 2002 as part of a screening study of the high-end exposures to baseline and oxygenated gasoline. The study is being conducted for the Am erican Petroleum Institute pursuant to Sec tion 211(b) of the Clean Ai r Act. The objectives of the pilot study were to evaluate various monitoring methods under realistic field sampling conditions and to determine their suitability for use in the main exposure study to be conducted in Atlanta, Chicago, and Houston during the upcoming summer and winter seasons. We also evaluated biological sampling methods (breath and urine) for their applicability to the final study. In addition to DRI, personnel from Lovelace Re spiratory Research Institute and Battelle participated in the pilot st udy. The refueling experiment wa s repeated on June 4, 2002 to evaluate the response of the portable mass spectrometer, whic h was not available for the refueling experiment during the pilot study. Th is report includes the results of the second refueling experiment.

1.1 Measurement Methods

During the pilot ph ase of the study, we evaluated the sensitivity, precision, accuracy, selectivity, power requirements, a nd portability of sam pling and mon itoring devices to be used in the main study. The evaluations included met hods for continuous measurement of carbon monoxide (CO), methyl tertiary butyl ether (MTBE), formaldehyde (HCHO), benzene, toluene, ethylbenzene, and xylene s (BTEX), with time integration of 1-5 minutes, and time-integrated measurements of ethanol (EtOH), 1,3-butadiene, and acetaldehyde (CH 3 

### CHO). The following continuous analyzers were us ed during the pilot study:

Background CO, Monitor Labs. Research-grade non-dispersive infrared detection for carbon

monoxide. This was maintained in the m obile la b and measured CO during our runs. Property of

DRI.

T15 CO, Langan products. Electrochemical monitor for CO. Qu ite small and portab le, but it is temperature dependant. Property of DRI

Photoacoustic Gas Monitor, Innova. A photoacoustic instrument th at uses infrared light to detect CO and total hydrocarbons (calibrated as propane ). In addition, this instrume nt could provide CO 2 

### and water vapor (relative humidity). Property of Lovelace.

Continuous Formaldehyde Monitor, Battelle. This instrument mo nitors formaldehyde in a continuous mode via a reaction to a fluorescent sp ecies and detection in a fluorimeter. Property

of Battelle.

Model TVA1000 FID, Thermo Environmental Instruments. This is a flame ionization based instrument for total hydrocarbons on a continuous basis. Sold primarily for leak detection at petrochemical plants. Property of TEI, on loan to DRI for the pilot study only.

MS200, Kore Technologies. An electron impact ioni zation time-of-flight mass spectrometer was used for the detection of VOC species. Rather than using a GC to separate species, this

1-1

### 1-2 instrument uses software to quantify species by apportionment of their mass fragmentation patterns. Property of DRI.

In addition to the continuous instruments, time-integrated samples were collected in stainless steel canisters and on 2,4-dinitr ophenylhydrazine (DNPH)-imp regnated silica gel cartridges and Tenax/Carbotrap solid adsorbent tr aps. These samples were collected over a onehour exposure period. The DNPH car tridges were sampled with a potassium iodide coated

denuder to remove ozone. The canisters were analyzed by gas chromatography with flame

ionization detection for BTEX , MTBE, 1,3-butadiene, and tota l nonmethane hydrocarbons. The extracts of the DNPH cartridges were an alyzed by HPLC/UV for formaldehyde and acetaldehyde. The Tenax/Carbotrap sa mples were analyzed for EtOH.

We also tested the solid phase microextra ction (SPME) technique during the pilot study for the collection and analysis of BTEX, MT BE, ethanol, form alde hyde, and acetaldehyde. A

100 μ m (poly)dimethylsiloxane (PDMS) fibers and 75 μ m Carboxen/(poly)di methylsiloxane (CAR/PDMS) fibers were used fo r BTEX, MTBE, and ethanol and 65 μ m PDMS/divinylbenzene (DVB) fiber that was impregnated with o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride (PFBHA) was used fo r carbonyl compound collection. The fibers were exposed in parallel for 15 to 30 min and were analyzed on a gas chromatograph with both FID and photoionization detector (PID ). Some of the fibers were also analyzed by GC/MS.

1.2 Description of Microenvironments and Sampling Procedures

A summary of the samples collected is presented in Table 1-1. This table details the samples that were taken and a brief summ ary of the conditions at the time of sampling. In addition, the following notes detail the experiment s. For the three driving exposures, we also collected GPS data showing location and time. Unless noted otherwise, each run last one hour. These are presented in the appendix.

In-cabin Freeway (R02022607), Run #1

For the first 15 minutes, the sampling van drove south on US 395 from Parr Boulevard to

south Reno. This was a stretch of high rush hour traffic. The second 15 minutes, the van drove

north from south Reno to Parr Boulevard. This was a stretch of low rush hour traffic. This loop was repeated for the third and fourth 15-minute periods. Data were not collected for the Innova photoacoustic instrument due to a failure of the pump. Only limited, hand logged, data were

available for the TEI FID because of a failure of the internal memory of that instrument. A few data points are missing due to power pr oblems at the beginning of the run.

In-cabin Surface Streets (R02022612), Run #2

For the first 15 minutes, the sampling va n drove within the “urban canyon” loop, consisting of south on Sierra, east on 4th, north on Virginia, west on 5 th 

### . (This made a total of 4

left turns around the Silver Le gacy Hotel/Casino.). The sec ond 15 minutes, the van drove a surface street loop, consisting of going east on 4th to Wells, north on Wells to Oddie, south on Sutro, and west on 4th. The third 15 minutes be gan at 4th, went north on Center, stopped atTable 1-1. API S211(b) Exposure Study - Reno Pilot StudyRun#Test IDDateStartTimeEndTimeMicroenvironmentExposure LevelLocation/ActivityVentilation ConditionR0202260702/26/0207100810In-cabin - freeway395 from Parr to south RenoR02022607a02/26/0207100725higher -stop& goSB 395 from Parr to south RenoR02022607b02/26/0207250740lower - free flowSouth Reno to DRI via 395R02022607c02/26/0207400755higher -stop& goSB 395 from Parr to south Reno1R02022607d02/26/0207550810lower - free flowSouth Reno to DRI via 395D&P-side windows open halfinch, heater on and ventopen tooutside, keeptemperaturebetween 60 and 65.R0202261202/26/0212001300In-cabin -surface streetsR02022612a02/26/0212001215higher - urban canyonS onSierra, E on 4th, N on Virginia, W on5th (4 left turns around Silver Legacy)R02022612b02/26/0212151230mixed - cross I-80 w/ostopping)From urban canyon loop, go E on 4th toWells, N on Wells to Oddie, S on Sutro, Won 4thR02022612c02/26/0212301245transect across I-80 with10-min stop at bridgeFrom4th, N on Center, stop at bridge over I80 for 10 minutes, then go back to urbancanyon loop2R02022612d02/26/0212451300higher - urban canyonS on Sierra, E on 4th, N on Virginia, W on5th (4 left turns around Silver Legacy)D&P-side windows open halfinch, heater on and vent open tooutside, keeptemperaturebetween 60 and 65.R0202261602/26/0216001700In-cabin - freeway395 from Parr to south RenoR02022616a02/26/0216001615lower - free flowSB 395 from Parr to south RenoR02022616b02/26/0216151630higher -stop & goSouth Reno to DRI via 395R02022616c02/26/0216301645lower - free flowSB 395 from Parr to south Reno3R02022616d02/26/0216451700higher -stop & goSouth Reno to DRI via 395D&P-side windows open halfinch, heater on and ventopen tooutside, keeptemperaturebetween 60 and 65.R0202270802/27/0208100910Refueling/in-cabinR02022708a02/27/0208100825baselineFrontage Road just south of Gold Ranchwindow open 1 inchR02022708b02/27/0208250840refueling/in cabinGold Ranch Pump #10window open 1 inch, closedoor once at startR02022708c02/27/0208400855refueling/in cabinGoldRanch Pump#10window halfopen, opened dooronce4R02022708d02/27/0208550910refueling/in cabinGold Ranch Pump #10window half open



### 1-3Run#Test IDDateStartTimeEndTimeMicroenvironmentExposure LevelLocation/ActivityVentilation ConditionR0202271202/27/0212001300Refueling/outsideR02022712a02/27/0212001215baselineTrailer park south of Gold Ranchwindow open 1 inchR02022712b02/27/0212151230refueling/outsideVan at Gold Ranch Pump #10, filled Suburuwith midgrade gas on Pump #9sampling line to pumpR02022712c02/27/0212301245refueling/outsideVan at Gold Ranch Pump #10, filled Corollawith regular on Pump#9,collected gasolinesamplesampling line to pump5R02022712d02/27/0212451300refueling/outsideVan at Gold Ranch Pump #10, filled Volvowith premiumgas on Pump #9, collectedgasoline samplesampling line to pumpR0202281102/28/0211001200Pedestrian walk1 square block around Silver LegacyR02022811a02/28/0211001115Virginia St between 4th and 5th (southbound)R02022811b02/28/02111511304th betweenVirginia and Sierra (westbound)R02022811c02/28/0211301145Sierra between 4th and 5th(northbound)6R02022811d02/28/02114512005th betweenSierra and Virginia (eastbound)R0202281502/28/0215001600Garage undergroundR02022815a02/28/0215001515R02022815b02/28/0215151530R02022815c02/28/02153015457R02022815d02/28/0215451600Survey surrounding area, enter garage andsurveyupperlevel. Paused for 15 min toallow traffic to build up, then sampled for 1hour.D&P-side windows open 1 inchwith heater on if necessary andvent open while outside ofgaraged, window fully openinside garage, and side doorsopen when stationary.R0203010903/01/0209351340Garage residentialR02030109a03/01/0209351005Background 1R02030109b03/01/0210051035Background 2R02030109c03/01/0211101140Pull car in gar. open kitchen door 1 min andcloseR02030109d03/01/0211401210Kitchen door open.R02030109e03/01/0212101240Kitchen door closed, windows open8R02030109f03/01/0212401310Open garage door and let icar dle for 30 min.open door tokitchen for 1 minute and keepclose for remainder of period.Use house fan located in centerof room to circulate/mix air ingarage and kitchen. Measurecontinuous instruments with 10-min cycle time between garageand kitchen. Sampling linethrough deadbolt hole.



### 1-4

### 1-5R02030109g03/01/0213101340Post Exposure, back car out and close garagedoorRun#Test IDDateStartTimeEndTimeMicroenvironmentExposure LevelLocation/ActivityVentilation ConditionR0203011603/01/0216001630Generator ExhaustR02030116a03/01/0216001605Exhaust downwind (CO ~ 2-3 ppm)R02030116b03/01/0216051610Exhaust upwind (CO peak of 150 ppm)R02030116c03/01/0216101615Exhaust downwind (CO <10 ppm)R02030116d03/01/0216151620Exhaust upwind (CO 10-50 ppm)R02030116e03/01/0216201625Exhaust upwind (CO 20-150 ppm)9R02030116f03/01/0216251630Exhaust downwind (CO <5 ppm)10R0206041006/04/0210101101Refueling/outsideR02060410a10101025Parking west of Gold Ranch- backgroundSampling line outside of vehicleR02060410b10311046At Gold Ranch Pump#10, refueling Volvo (4min) with premiumgas on Pump #10Sampling line at breathing highR02060410c10471101At Gold Ranch Pump#10, refueling Corolla(2 min) with regular on Pump#9Sampling line at breathing high

### bridge over I-80 for 10 minutes, then went b ack to the urban canyon loop. The van door was open during the stop at the freeway overpass. Fo r the fourth 15 minutes, the sampling van drove the “urban canyon” loop again, completing another 4 turn s around the Silver Legacy

Hotel/Casino. Data were collected from all in struments , but the MS200 instrument shut down during the run due to vacuum becoming too low.

In-cabin Freeway (R02022616), Run #3

For the first 15 minutes, the sampling van drove south on US 395 from Parr Boulevard to

south Reno. This was a stretch of low rush hour traffic. The second 15 minutes, the van drove

north from south Reno to Parr Boulevard. This was a stretch of high rush hour traffic. This loop was repeated for the third and fourth 15-minut e periods. Data were collected from all instruments, but a few data points are missing due to power problems at the beginning of the run.

In-cabin Refueling (R02022708), Run #4

For both refueling experiments a rural but high volume service station was used. The

station is loc ated near a major interstate (I-80), bu t is otherwise in a rural area. The station has 18 fueling pumps and sells between 20,000 and 40,000 gallons of gasoline per day. The mangers indicated they are the largest gasoli ne seller in northern Nevada.

For the first 15 minutes, the sampling van pa rked on the frontage road, near the I-80 freeway, away from the filling station to coll ect a background sample. The goal was to be approximately the same distance from the freeway as we would be at the fueling station. For the next 50 minutes, samples were collected whil e the van was parked at pump number 10, the center pump of the center island. Most equipment worked well, except that the MS200 had vacuum problems and had to be shut down.

Refueling at Pump (R02022712), Run #5

Similarly as with the first experiment, during the first 15 mi nutes, the samp ling van parked on the frontage road, near the I-80 freewa y, away from the filling station to collect a background sample. For the next 45 minutes, samples were collected in the breathing zone while the van was parked at pump 10, center of th e center island. Breathing zone was at pump 9 (opposite side of a dual-side pum p), while three cars we re filled with fuel. First was a Subaru that was filled with regular. Next came a Toyota that was filled with mid-grade, and finally was a Volvo filled with super. No formaldehyde data we re collected due to power failure. In addition,

the MS200 was not run due to vacuum problems.

Refueling at Pump, Re peated (R02060410), Run #10

During the first 15 min the vehicle with sam pling equipment was park on the quiet parking area, west of Gold Ranch and away fr om the filling station to collect a background sample. Only MS and SPME samples were collect ed. For the next 30 minutes, samples were collected in the breathing zone while the vehi cle with sampling equipment was parked at pump 10, center of the center island. Brea thing zone was either at pump 10 or at pump 9 (opposite side of a dual-side pump), while two cars were filled with fuel. First was a Volvo filled with super,

1-6

### and next came a Toyota Corolla that was filled with regular grade. During 30 min one canister sample and two 15 min SPME samples were coll ected. MS200 was operat ing in a continuous

mode.

Pedestrian Walk (R02022811), Run #6

All the monitoring equipment was placed on two mobile carts with batteries and inverters. For one hour, monitoring was conducte d while the carts were slowly pushed around a large one square block area of central downtown Reno (the Silver L egacy Casino). The block was split roughly into equal time s with approximately 15 minutes spent on each leg of the block.

We started at 4 th 

### and Virginia, went south on Virginia, then west on 5 th 

### to Sierra, then north to 4 th


### and back to the starting point.

Data was collected from all instruments, except that for the first 15 minutes, no formaldehyde data was collected possibly due to a light leak in the fluorescence detector. In addition, the TEI FID did not coll ect data, although it appeared to be on the entire tim e. The

reason for this failure was never determined.

Underground Public Parking Garage (R02022815), Run#7

The van was parked in an underground parki ng garage for one and a half hours during the period of maximum car departur e. This garage has two underground levels, however the van remained on the upper of these two levels for two r easons. The first is that this level was nearly full while the lower level had only a few vehicles. The second reason is that the traffic ramps in the garage would allow travel from the first underground level down to the second, but from the second level the van could only go up to the surface, not back to the first underground level. The van’s position was relocated seve ral times to try and capture the cold start exhaust from departing vehicles. Data were collected for th e first 15 minutes, followed by a 15 minute zeroing,

and then data collection for the next hour.

Residential Kitchen and Garage without Car (R02030109a,b), Run #8

For both residential exposures a home was used that had an attached two-car garage. The home and the garage share a comm on wall and there is a door from the garage into the kitchen. For the duration of these experiments a vented 2.5 gallon gasoline storage container was also present in the garage during the sampling period, lo cated in the front center portion of the garage,

closest to the house. The can wa s approximately half-full and th e vent on the gas can was open. The sampling equipment was set up in a residentia l kitchen next to the door of the attached garage. For the first hour, the sampling was done with the garage door closed and no car. Samples were taken alternately for 10 minutes in the kitchen followed by 10 minutes in the garage for one hour.

Residential Kitchen and Garage with Car (R02030109c-g), Run #8

For these experiments the car used was a 1984 Honda Accord with a four-cylinder engine and it is carbureted. The vehicle is normally fu eled with regular gasolin e and annually passes the state smog check with no problems. Prior to pa rking the car in the garage, it was driven approximately 5 miles to warm the engine up. On ce parked in the garage, the air cleaner cover

1-7

### was removed, exposing the inlet of the carburetor and the oil filler cap on the valve cover was removed to allow additional evaporative emissions.

The sampling equipment had the same set up as the background samples. Separate integrated samples were collected in the garage and in the kitchen. The continuous instrum ents were switched between the garage and the kitchen at 10-minute intervals for 2.5 hours. The sequence of activities was as followed:

Time Activity

1110 1140 Pull car in gar. open kitchen door 1 min and close

1140 1210 Kitchen door open.

1210 1240 Kitchen door closed, windows open

1240 1310 Open garage door and let car idle for 30 min. Open door to kitchen for 1 minute and keep closed for rem ainder of period.

1310 1340 Post Exposure, back car out and close garage door

Sample probe was on the following sequence:

garage 11:10-11:20

kitchen 11:20-11:30

garage 11:30-11:40

kitchen 11:40-11:50

garage 11:50-12:00

kitchen 12:00-12:10

kitchen 12:10-12:20

garage 12:20-12:30

kitchen 12:30-12:40

garage 12:40-12:50

kitchen 12:50-13:00

garage 13:00-13:10

garage 13:10-13:20

kitchen 13:20-13:30

garage 13:30-13:40

Generator Exhaust (R02030115), Run #9

In the DRI staging lot, the exhaust hose of a gasoline powered elec trical generator was operated near th e inlet of the sampling equipment. The genera tor exhaust hose was moved to a different location every 5 minutes. Adjusting its position relative to the instrument inlets; first downwind, then upwind, downwind, upwind, upwind cl oser to exhaust, and finally downwind.

1-8

### 2. RESULTS

The results from this study are presented in four parts: 1) continuous (or semicontinuous) instruments; 2) integrated sa mples; 3) SPME samples; and 4) biological samples. Where appropriate, comparisons are made between the continuous and the integrated samples. Results from the additional refueling expe riment performed in June 2002 in Reno are

summarized in Section 2.5.

2.1 Continuous Instruments

Figures 2-1 through 2-15 present the time seri es for the continuous analyzers. For the residential garage exposures (2-8 through 2-15) the plots are only 30 minutes, not 60 m inutes as for the rest of the plots. This is because of the number of changes th at took place during these exposures. Also, during the residential garage exposures, the sample probe was moved to measure the kitchen area and the garage area as per the schedule listed a bove in the description

of the runs. This accounts for the sudden cha nges in concentration seen in the data.

The MS200 data is not presente d in these time series. Wh en we examined the raw MS data, without background correctio n, we found very high concentr ation levels being reported. The MS200 data appear high during a ll runs, especially compared to the integrated canister data, however, the structure of the data suggests that the MS200 is accurately responding to changes in

ambient concentrations. Additional work was conducte d with this instrument to help explain this

effect. As a result of this work and discussions with the manufacturer (Kore), we have been able

to better understand these data. The data that the MS200 re ports is very dependent on the blank level. In addition, the membrane-based inlet a nd the relatively slow pumping mechanism appear to have the effect of slowing the 2-3 minute reco very time of the instrument, especially when the instrument is challenged with a high concentrati on. To test this we alternatively applied a high

concentration standard and a zero air to th e inlet of the MS200. On the basis of these experiments, we applied a correction that consisted of subtracting a background value consisting of a linearly sloping zero to the data, based on our experiments with the standards. This was difficult in the case of the residential garage where the instrument was switched every 10 minutes between the relatively high concentrations in the garage w ith the much lower levels seen in the kitchen. However, once these backgrounds were subtracted, the MS200 data generally showed agreement (within a factor of 2 at pp b levels) with the canister data, which will be discussed later. We are still working with Kore to develop a pre-concentrator inlet that will allow for a much lower detection limit, however , this will sacrific e time resolution.

An example of the correction applied is in chart 2-16 which shows the original benzene concentration, the zero function applied and the resulting correct ed benzene concentration. The next figure, 2-17 shows the corrected data from this run for benzen e, toluene, and th e xylenes. In this chart, it is clear that th e corrected plots track each other in structure, as we expected. The other data sets were similarly corrected and ar e summarized in Table 2-1 with the canister data. The comparison with the canister is quite favorab le, except in the case of benzene at very low

concentrations and in some runs where limited da ta was available. This was generally due to problems with the vacuum system in the MS200.

2-1

### 2-2 To compare the responses of the various inst ruments, we produced scatter plots, Figures 2-18 through 2-21. Figure 2-18 shows the compar ison between the Innova CO and the T15 CO. There is reasonable agreement, but especially at lower concentr ations, we find that the Innova occasionally is much higher than the T15. This may be due to the method the Innova uses, which is to take a grab sample into its internal chamber, measure the components of interest and then evacuate the chamber. If this grab sample is dur ing a particularly high br ief instant, this may result in the higher response seen.

Figure 2-19 compares the two continuous hydrocarbon (HC) measuring devices, the Innova and the TEI. There are two very high values from the Innova, which Figure 2-20 removes. The Innova data are adjusted upward by 10 to account for the expected difference in response from the photoacoustic vs. the FID. Thes e two instruments use fundamentally different methods to measure hydrocarbons and may be hard to compare. In general, the two are tightly correlated, despite the different response factors.

The correlation between the Battelle continuous form aldehyde monitor and the T15 CO is presented in Figure 2-21, without the data from the generator which was significantly higher and dominated the plot. This shows a weak correlation, but includes so me very high values. At more ambient concentrations, they ar e slightly better correlated. We should expect that these two would be correlated as they both are combustion-derived.

2.2 Integrated Samples

Integrated samples consist of canister s, DNPH cartridges (for aldehydes) and Tenax/Carbotrap solid adsorbent traps. Canister data and Tenax/Carbotrap data for ethanol are presented in Table 2-1. In addition to the va lues measured, we show the sum of the BTEX compounds. Of interest was to compare these valu es to the MS200; this comparison is presented in Table 2-2. In this table, the average values (canister) from the variou s exposures are presented along with the corrected MS200 va lues for these same exposures. The corrected data are

calculated as described above (Section 2.1). Generally the av erages agree better at higher concentrations, but lower concentrations are quite reasonable, considering we are working at or

near the detection limit of the MS200. In the case of the resi dential garage e xposures this was further complicated by the 10-minute cycle time between the garage (at high concentrations) and the kitchen (at much lower concentrations). In spite of all this, the correlations between the

canister and the MS200 were on the order of r 2 

### ~ 0.87 and the slopes were ~0.75, with the MS200 reporting less th an the canisters.

The DNPH samples were compared with the av eraged data f rom the Battelle continuous formaldehyde sampler. This comparison is presented in Table 2- 3 and Figure 2-22. The agreement is excellent for the 10 samples that ar e comparable. The correlation suggests that the Battelle unit is reading about 15% less than the DNPH cartridges are reporting.Table 2-1: Canister and Tenax/Carbotrap Data (concentrations in ppbv)Test IDDateLocation1,3-butadieneEthanol(T/C)MTBEbenzenetolueneethylbenzenem/pxyleneo-xyleneSumBTEXR020226072/26/02Morning FreewayCommute1.020.790.074.3210.770.953.651.2820.98R020226122/26/02Urban canyon,surface0.550.130.041.796.080.632.350.8611.70R020226162/26/02Afternoon FreewayCommute0.68Missing0.042.245.820.531.940.7011.24R020227082/27/02In van, gas station0.16nd0.121.146.720.632.630.9912.11R020227122/27/02Gas station,refueling1.58nd2.0610.3753.382.9312.003.9682.65R020228112/28/02pedestrian walk0.160.470.010.692.290.220.850.314.35R02030109a3/1/02Res. Garage,background0.03Missing0.030.291.670.311.150.503.93R02030109b3/1/02Kitchen, background0.03Missing0.010.311.250.130.490.202.38R02030109c3/1/02Residential garage0.220.980.959.53164.4411.1848.1717.39250.71R02030109d3/1/02Kitchen0.10nd0.363.6655.343.6015.545.6883.82R0203010163/1/02Mobile gasgenerator17.38nd0.5841.03123.239.9534.2112.16220.57



### 2-3Nd = not detectedMissing – missing sampleaa



### 2-4Table 2-DateTable 2-3. Comparison of Formaldehyde DataDate Time Test ID DNPH-HCHO Battelle-HCHO2/26/02 0710R020226076.667.92/26/02 1200R020226129.667.92/26/02 1600R020226166.846.22/27/02 0810R020227084.135.52/27/02 1200R020227124.622/28/02 1100R020228112.301.12/28/02 1503R02028154.963.53/1/02 0935R02030109a3.564.63/1/02 0935R02030109b2.393/1/02 1110R02030109c6.275.43/1/02 1110R02030109d4.155.23/1/02 1600R02030101623.2920.72. Comparison of MS200 with CanistersMS200CanistersSummary Corrected Values, ppbvLocationbenzene toluene ethyl benzem/p-xylene o-xylene Sum Xylenes Benzene Toluene XylenesMorning Freeway Commute 4.32 10.77 0.95 3.65 1.28 4.93 4.38 10.69 5.15Urban canyon, surface 1.79 6.08 0.63 2.35 0.86 3.20 9.20 8.66 4.33 Limite2/26/022/26/02d Dat2/26/022/27/02dDatAfternoon Freeway Commute 2.245.82 0.53 1.940.70 2.65 12.53 5.89 4.90In van, gas station1.14 6.72 0.63 2.63 0.99 3.62 9.17 4.71 4.82 Limite2/27/02Data2/28/023/1/023/1/023/1/023/1/023/1/02Gas station, refueling 10.37 53.38 2.93 12.00 3.96 15.96Nopedestrian walk0.69 2.29 0.22 0.85 0.31 1.16 3.11 2.37 2.60Res. Garage, background 0.29 1.67 0.31 1.15 0.50 1.65 2.57 5.21 11.76Kitchen, background0.31 1.25 0.13 0.49 0.20 0.69 8.69 5.84 10.40Residential garage9.53 164.44 11.18 48.17 17.39 65.56 9.30 91.20 46.59Kitchen3.66 55.34 3.60 15.54 5.68 21.22 13.95 66.25 32.15Mobile gas generator 41.03 123.23 9.95 34.21 12.16 46.37 38.33 115.25 51.79

### 2.3 Solid Phase Microextraction (SPME)

We tested the SPME technique during the pilo t study for the collection and analysis of BTEX, MTBE, ethanol, formal dehyde, and acetaldehyde. A 100 μ m (poly)dimethylsiloxane (PDMS) fibers and 75 μ m Carboxen/(poly)dimethylsiloxane (C AR/PDMS) fibers were used for BTEX, MTBE, and ethanol and 65 μ m PDMS/divinylbenzene (DVB) fiber that was impregnated with o-(2,3,4,5,6-pentafluorobenz yl)hydroxylamine hydrochloride (PFBHA) was used for carbonyl compound collection. The fibers were exposed in parallel for 15 min, with exception of the residential garage microenvironment where the fi bers were exposed for 30 min. The fibers were analyzed by inje ction into a GC housed in the m obile laboratory. Some of the fibers were also analyzed by GC/MS. The anal ysis was performed immediately after collection, when possible. However, some of the fibers had to be stored on dry ice in the cooler for a period

of several hours.

The initial SPME results from the pilot study are more qualitative than quantitative. The techniqu e is new method for us and requires additional calibration work in the laboratory. Our major findings from the pilot study include:

• 75 μ m CAR/ PDMS fibers are more sensitive than 100 μ m PDMS fibers and are thus more suitable for ambient measurements. We will be using 75 μ m PDMS fibers in the main study for the measurements of MTBE and BTEX.

• Although ethanol peak was observed in all ch romatograms , the etha nol concentrations were clearly too high. This is most probably due to the adso rption of ethanol from breath into the fibers. We measured up to 200 ppbv of ethanol concentr ation in the breath samples collected during this pi lot study. The fibers were situ ated in the br eathing zone during each experiment.

• Formaldehyde and acetaldehyde concentrations are too high as well when compared with

continuous form aldehyde analyzer data and integrated DNPH cartridge data. This may also be due to the presence of acetaldehyde in breath (we measured up to 25 ppbv of acetaldehyde in the breath samples). In addition, formaldehyde may be present in the mobile lab where the PFBHA impregnation of the PDMS/DVB fibers took place. We are getting the continuous formalde hyde analyzed from Battelle, thus we do not see any need to monitor formaldehyde with SPME technique and we propose to drop this analysis. Acetaldehyde data are less important for this study and we will obtain this data from integrated DNPH cartridge method.

In summary we are still working on the develo pment of the standard p rocedures for the SPME technique. The calibration, storage, and op timal sampling time are being addressed. We will be ready for the main study starting in Ju ne and we propose to use the SPME method for

measurements of BTEX and MTBE.

2-5

### 2-6 2.4 Biological Samples

2.4.1 Breath VOC Concentrations

Breath concentrations are portrayed in Tabl e 2-4 and Figures 2-23 through 2-25 for two separate subjects during three sep arate scripted ex posures. For the pilot pr oject the subjects were two of the technicians collecting samples for micro-environmental concentrations. The objectives of this pilot program for the breath monitoring were to 1) evaluate the ability to analyze breath concentrations of VOC’s accordin g to methods developed by Pleil and Lindstrom (1995), 2) to see differences betw een full and alveolar breath co llections, 3) to assess breath concentrations between two subject s prior to and after scripted e nvironmental exposures, and 4) to develop a recommendation for the final sampling protocol and bi ological monitoring technique of choice. All of the samples shown and discusse d are “alveolar” samples unless designated as “full-breath” samples. Alveolar samples were collected to represent material that has undergone gas exchange in the lung. These sa mples were collected by breathing the end part of a breath directly into an evacu lated cylinder (1 or 3L). The re sults of the breath measurements

are described below.

Refueling

Subject 7: The out of cabin re-fueling experiment showed the highest average exposure

concentratio ns for all of the samples where biolog ical samples were collected, by at least a factor of 5 for most analytes. As expected from results published by Philips and Greenberg (1992), all of the analytes (except MTBE) show a negative al veolar gradient (concen tration in breath lower than ambient air) relative to the average exposure concentrations of 60 minutes. Unfortunately there is no real time data for these compounds, and the elimination rate via breath is rapid enough that real-time levels towards the end of exposure would be most important for these compounds. For subject 7 there is an observed exposure effect, with pos t exposure alveolar concentrations higher than pre-exposure concentr ations by at least a fa ctor of 2. With the exclusion of MTBE and ethyl benzene, this exposure effect was not observed for most compounds in subject 3. Exposure for the outsid e refueling was terminated at 1300 hours. The mobile lab was located approxi mately 1-2 minutes walking di stance away from the exposure area and the exposure subjects were also responsibl e for much of the sampling responsibilities. Expired breath was not collected from subj ect 7 until 1302, and not from subject 3 until 1304. These short differences in times between sample s may explain the lack of an exposure effect observed in subject 3. This can be confirmed by the breath elimin ation half-lives published to be between 1 and 3 minutes for MTBE, benzene, an d toluene (Lindstrom and Pleil, 1996).

In-Cabin Refueling

Subject 7 was the only subject sampled for bo th pre and post sam ples of the in-cabin refueling exposure. With the exception of MTBE , there is no exposure e ffect. This is most likely due to the fact that the post-exposur e breath sample was no t collected until 0919, 9 minutes after exposure. This may be enough time to eliminate back down to background levels.

### 2-7Table 2-microFuAlvmicroenmicroFuAlv4. Concentrations (ppbv) of volatile organic compounds in breath and micro-environments.Sample Collection Time LocationSubject MTBE benzene toluene ethylbenzene m/p xylene o-xyleneBreath800In Cabin fueling PRE70.32 0.92 2.05 0.330.84 0.23Breath919 In Cabin fueling POST70.79 0.82 1.92 0.330.89 0.23environmentvan, Verdi gas station microenviront conc. 0.12 1.14 6.72 0.632.63 0.99Breath1149Refueling PRE70.35 0.75 1.74 0.330.85 0.27Breath1302Refueling POST73.99 1.83 5.73 1.063.70 1.58Breath1415Midday Background70.08 0.58 1.41 0.001.01 0.32Breath1150Refueling PRE30.22 1.34 2.62 0.001.86 0.41ll Breath1304Refueling POST31.54 1.52 3.16 0.671.76 0.44eolar Breath1305Refueling POST31.84 1.24 2.53 0.481.29 0.31vironmentVerdi gas station, refuel microenviront conc. 2.06 10.37 53.38 2.93 12.00 3.96Breath1415Midday Background30.47 1.10 2.26 0.551.44 0.33Breath1422Midday Background70.80 0.76 1.83 0.000.86 0.25environmentpedestrian walk microenviront conc. 0.01 0.69 2.29 0.220.85 0.31Breath924Morning Background30.28 1.18 2.42 0.631.63 0.00Breath1043Walk PRE30.69 1.56 0.00 0.651.70 0.43Breath1201Walk POST30.31 1.44 3.00 0.731.87 0.45Breath1047Walk PRE70.79 0.99 2.34 0.411.30 0.42Breath1200Walk POST70.32 0.84 2.18 1.165.25 2.18ll Breath1623 Direct Exhaust Exposure30.12 1.36 2.73 0.411.20 0.33eolar Breath1623 Direct Exhaust Exposure30.09 1.38 3.79 0.591.56 0.42

### Pedestrian Walk

Again for the pedestrian walk there is very little exposure effect observed from subject 3 while subject 7 shows at least a factor of 2 increa se in alveolar concentr ations after exposure for ethyl benzene, m /p xylene, and o-xylene. Similar to the refueling samples, subject 3 was did not give their sample at the same time as subjec t 7. There was a one-minute difference between subject 3 (1201) and subject 7 (1200). There wa s a negative exposure effect for MTBE in both subjects, suggesting that pre-exposure background or residual subject concentrations are higher than the exposure. The un-observable exposur e effect for benzene and toluene are not explainable, as the exposure to these compounds was actually higher than the compounds where an exposure effect was observed.

Full versus Alveolar Breath

Figure 2-26 shows the relationship between fu ll and alveolar breath. Full and alveolar breath are defined here by how the sample was colle cted. Full is th e entire breath blown into the canister sample, while the “alveolar” breath consists of partially reserved tidal volume and some expiratory reserve. The alveolar sample is collected at the end of a regular breath. As observed the agreement between the two br eath collection methods are reas onable, but vary slightly by analyte. Agreement is between 15-25% for MTBE, benzene and toluene; and about 40% for ethyl benzene and the xylenes. In general, th e difference is higher for compounds where the concentrations are less, indicating some contri bution from measurement uncertainty may affect

observed differences. Since the observed concentr ations are higher in the full breath samples (with the exception of MT BE), it is obvious that there are levels of these compounds in the “dead-space” region of the subject that has not undergone any gas exchange. CO 2 

### measurement between the two samples shows a difference of 10%, which is 5% less than the difference observed by Pleil and Lindstrom (1995). 15% is the expected am ount, based on a 15% dilution

of a 1 liter tidal volume. The full and alveolar br eath sample in this pilot study was taken from a 3 liter evacuated canister, which is different than the 1 L canister used by the second subject and in the Pleil and Lindstrom paper. Additiona l experiments should be completed comparing

full/alveolar breath CO2 dilution between the 1 and 3 liter canisters.

2.4.2 Urine VOC Concentrations

Urinary concentrations of MT BE, benzene, toluene, ethylbenzene, and the xylenes were measured for backgrounds and pre/post exposure le vels in two subjects from three scripted exposures. Shown in Table 2-5 are the urinary concentrations of benzene, which was the only urinary constituent consistently above the anal ytical limit of quantitation of 100 ng/L. The objectives of this pilot study was to apply the technique of 1) Fusti noni (1999) to measure urinary volatile organic compoun ds, 2) to measure concentra tions (and variability) in two separate subjects, and 3) to evaluate results in terms of their ability to relate to exposure concentrations. In the original proposal one objective was also to measure urinary creatinine levels. This was not conducted for this report because this is not conduc ted in the contemporary literature to report urinary conc entrations of VOC’s. “Older” literature used to measure

creatinine in order to normalize urinary components for dilution. The current be lief is that this is not necessary. The benzene results are di scussed below for each scripted exposure.

2-8

### In-cabin Refueling

Subject 3 had a high pre-exposure background (208 ng/L) prior to the in-cabin refuel. There was a negative exposure effect after the in-cabin exposure (<100 ng/ L), and a higher concentration one hour after exposure (138 ng/L) th an immediately after exposure. This sample was similar to the next pre-exposure concentration taken one hour later (120 ng/L). Subject 7 had both pre and post exposure levels for the in-cab in re-fuel that were below the detection limit of 100 ng/L (3 x baseline).

Table 2-5. Urinary benzene concen trations in two subjects exposed

to three micro-environents

Benzene Time Date subject activity ng/L 520 227 3 background 118.3 520 227 3 background 141.8 755 227 3 preexpos in cabin refuel 208.1

920 227 3 postexpos in cabin refuel 90.4 a


### 1010 227 3 mid background 139.8 1148 227 3 preexpos refuel 118.6

1308 227 3 post expos refuel 3.1 a


### 1417 227 3 post expos refuel 166.3 1524 227 3 post expos refuel 465.8 1645 227 3 post expos refuel 1100.6

950 228 3 pre walk 276.7 1225 228 3 post walk 335.5

445 227 7 background 163.9

752 227 7 preexposin cabin refuel 26.4 a



### 924 227 7 postexpos in cabin refuel 0.0 a



### 1150 227 7 preexpos refuel 15.4 a



### 1312 227 7 post expos refuel 11.4 a



### 1424 227 7 post expos refuel 18.1 a


### 1620 227 7 post expos refuel 101.8

545 228 7 background 0 a


### 1229 228 7 prewalk 106.5 1415 228 7 post walk 131.0 a: below the limit of quantitation of 100ng/L



### 2-9

### Refueling

Subject 3 showed a negative exposure effect immediately after exposure, but saw a steady increase in urinary be nzene excretion thr oughout the day. Measurements were ma de approximately every hour until 1645, and the hourly concentrations were 166, 465, and 1100 ng/L at 1417, 1524, and 1645, respectively. This indicates that for these samples the time course for urinary excretion is much slower than it is fo r breath, and there is a lag in the excretion. The exposure concentrations observed for subject 7 were all below 100 ng/L, with the exception of the post exposure sample collected at 1620, where the concentration was about 100 ng/L. These results are comparable to MTBE data repor ted by Lee and Weisel (1998) who showed an increase in urinary MTBE after exposure (1 pp m for 10 min) at about 1 hour, remaining about the same at 3.5 hours and dropping several-fold by 6 hours.

Pedestrian Walk

There was a slight positive e xposure effect for benzene in both subjects from the in-town walk. Subject 3 had a pre-exposure urinary benzene concentrations of 276 ng/L and postexposure concentrations of 335 ng/L, while subj ect 7 had levels of 106 and 135 ng/L. For both subjects the starting background wa s different, and their increase wa s approxim ately the same for this exposure.

2.5 Results of Additional Refuelin g Experiment (June 4, 2002, Reno)

This experiment was conducted in order to test the respon se of MS200 (since we were not able to operate the instrum ent during the refueling experiment in February) in this microenvironment and to repeat breath and urine testing to confirm the conclusions drawn from the pilot study. There were important differences between this refueling and the one conducted for the pilot study. Most importantly:

• We only filled the canister during the actu al exposure period of 30 min. During the pilot study, we filled the canister over 1 hour, which consisted of 15 min of background plus 45 min of exposure.

• Used one exposure subject rather than two.

• Refueled two vehicles instead of three.

• The MS200 data output was adjusted to sum the xylenes and ethyl benzene using a single library spe ctra. The reason for this is that there is very little difference between the spectra of these four compounds and we found th at the software did not do well trying to separate them.

In addition to the MS200 and the canister, we also collected 5 breat h samples and 8 urine samples that were analyzed by LRRI. The five breath samples were: Pre test; 15 min into test; approximatelly 2 min post test; 5 min later; a nd 10 min later. The urin e samples included: pretest; approximately15 min post exposure (no urin ary output between these two); approximately

2-10

### every hour thereafter for 6 more hours. All the vo ids from the test subj ect between the hours of

0730 and 1800 were collected.

2.5.1 MS200 and Canister Results

Figure 2-27 shows the time series of the concen trations of benzene, tolu ene and the sum of xylenes and ethylbenzene in parts per million by volume, ppmv. The data are one-minute averages recorded by the MS200. To convert this unit to canister data units (which are parts per billion of carbon or ppbC), multiply by the number of carbons and by 1000 to adjust ppm to ppb. For example, the highest spike seen (at a ppx 21 min) is 0.173 ppmv for toluene, which is equivalent to 1211 ppbC. Benzene in the same sp ike is 0.104 ppmv or 624 ppbC. Sum of xylenes highest reading at about 22 min is 0.135 ppmv or1080 ppbC.

The averages of the MS200 data are in good agreement with the can ister measureme nts. The data are as follows (units are ppbC):

Compound MS200 (ppbC) Canister (ppbC) % error
(difference/can value)


### Benzene 128.2 142.1 9.7

Toluene 413.8 438.4 5.6 Sum Xyl+EBz 336.6 368.2 8.6

2.5.2 Breath Sample Results

As explained above, the breath samp les were co llected in 1-liter stai nless steel canisters from one subject. Table 2-6 below lists the resu lts obtained from these samples (the units are ppbC):

Table 2-6 Breath Data in ppbC

Site/Compound Pre refueling
breath Middle of run
breath Post exposure
breath # 1 (2 min) Post exposure breath #2 (5 min) Post exposure breath #3 (1 0 min) sample_time (hr) 0945 1046 1103 1107 1111 sample_date 6/4/02 6/4/ 02 6/4/02 6/4/02 6/4/02
1,3-butadiene 0.21 0.83 7.46 0.44 0.41

MTBE 0.00 3.03 1.34 1.91 1.14

benzene 2.65 14.76 7.82 10.76 9.78

toluene 5.98 47.32 123.54 27.59 25.17 ethyl benzene 0.83 1.01 2.77 8.46 7.75 m/p-xylene 2.61 14.12 18.77 28.75 46.36 o-xylene 1.66 5.59 3.82 7.03 16.88



### 2-11

### These data are consistent with the data obtained during the pilot study, confirming very

short breath elimination half-liv es of the compounds measured. In addition, this elimination time is different for every compound. Whereas benzene concentration is the highest in the middle point of the exposure, and declines signif icantly two minutes after exposure, toluene concentrations are the highest 2 min after expo sure, declining sharply five minutes after the exposure. Thus, breath data obtained after an in tegrated exposure period of an hour will not accurately measure the biological uptake that occurs under variable condition during the exposure period.

2.5.3 Analysis of Urinary VOC Concentrations

Urinary concentrations of MTBE , benzene, toluene, ethyl B e nzene, and the xylenes were analyzed utilizing the same methods described fo r the Reno pilot study protocol. In addition, for these data we analyzed urinary creatinine values and urinary ethanol. Creatinine values were obtained using a standard creatinine analysis kit on a Monarch 2000 clinical chemistry

instrument. Ethanol data were obt ained utilizing the same solid pha se extraction fibers that were used for the other chemical species.

Table 2-7 lists the concentrations of measur ed species, including creatinin e, and Figure 2- 28 shows the data for BTEX and MTBE. Urinary concentrations of all of the measured VOC’s except ethanol were present in detectable limits in most of the samples. The absence of ethanol may be due to the high detection limits of (0.5 ng/L) relative to the other analytes, which are

detectable in much lower concentrations. If urinary ethanol is to be monitored in follow on studies additional method development will be c onducted to decrease the limits of detection on this assay.

Concentrations of the other volatile organi cs reported here are co mplicated by the relatively high concentration observed in the pre-exposure samples. Concentrations postexposure increased throughout the day for benzene and toluene, which is similar to what was observed in the pilot study. Howe ver, at their peak, the concentr ations of these compounds were only slightly larger than the pr e-exposure backgrounds. The concen trations observed in the urine for benzene were consistent with what was observed during the pilot study and in the literature, with values in the range of 100-200 ng/L. Th e concentrations post-ex posure did not increase much beyond 200 ng/L for benzene. These low post- exposure concentrations are consistent with the results from subject 7. While the highest urinary concentrations for subject 7 in this study do not reach levels reported for subject 3 in the p ilot study, subject 7 does show an increase in urinary benzene and toluene through out the day, which is consistent with subject 3 in the pilot study. The currently reported results do show concentr ations of toluene that are increased relative to benzene, which is consistent with the higher concentrations of toluene that the subject was exposed to. The toluene concentrations do not , however, increase well above the pre-exposure background concentrations.

Creatinine was measured during this follow-on study in response to some criticism from

an external reviewer that crea tinine values would help determine concentration effects resulting from dilution. As reported in th e pilot study report, th e concentrations of urinary VOC’s in the contemporary literature are typica lly not normalized to creatinine concentrati on. One example of the rationale for not using creatinine correction is given in Albertin e et al. (2001), where

2-12

### 2-13 statistical relationships between exposure and urinary concentra tions of butadiene biomarkers

were m ore significant when not normalized.Table 2-7Concentrations of Ethanol, MTBE and BTEX in urine samples (ng/L)



### 2-14Re-do of Refueling ExperimentConcentrations in ng/LSample#SubjectTimeDateDescriptionEthanolMTBEBenzeneTolueneEthBenzenep/mxyleneo-xyleneCreatininegm/dL178206/4/02pre exposure-morningnd0.0240.1650.2650.0620.0570.08072711156/4/02post exposurend0.0520.1030.1120.0390.0390.066333712156/4/02post exposurend0.0300.1350.1490.0570.0570.098564713276/4/02post exposurend0.0330.0890.1350.0470.0460.066235714306/4/02post exposurend0.0210.1430.2020.0510.0350.066266715226/4/02post exposurend0.0170.2030.2830.0420.0420.066137716246/4/02post exposurend0.0090.2380.2790.0510.0440.071138717186/4/02post exposurend0.0130.1060.1140.0460.0400.07022

### 3. RECOMMENDATIONS

This section describes the equipment and protocols we recomme nd for this program. We first summarize the equipment in Table 3- 1 and then discuss each individually.

Table 3-1 Recommendation Summary

Instrument Recommendation Notes

Battelle HCHO Yes We have requested Battelle build one for DRI.

Kore MS-200 Yes Needs protocol development and possibly
preconcentrator.
TEI TVA1000 No Not sensitive enough.

Innova

Photoacoustic No Grab sampling method; overlap with other

instruments. Langan T15 CO Yes Need to develop temperature dependence. Integrated Samples Yes

SPME Yes Would be used only for MTBE and BTEX

3.1 Exposure Measurements

Formaldehyde Monitor . The Battelle instrument appears to have performed quite well. We

evaluated a similar commercial instrument made by Alpha Omega during a three-day evaluation period at the end of May 2002. The evaluation consisted of collocated measurements with our CO analyzer, Kore MS200 analyzer and integrated DNPH measurements using microenvironmental exposures similar to those used during the pilot study. Base upon the results of this evaluation, we conclude d that the Alpha Omega HCHO monitor would be suitable for the main study.

Kore MS200 . The MS200 appears to have performed rather well in the pilot study. We are currently refining the protocol fo r using this instrume nt, based on the results from the field study as well as the results of many e xperiments we have conducted since that time. We hope to install an automated system for zeroing the instrument dur ing the run times to confirm the zero point of the instrument as it changes during the day. In addition, we will be standardizing the zeroing procedure and are working on methods to auto mate the background subtraction process. We recommend the use of the instrument in the main study.

TEI TVA1000 . The TVA1000 is a FID based detector for total hydrocarbons. As such it responds approximately equally to the concentra tion of oxidizable carbon in the air. In the present experiment that means it has the ch allenge of measuring small amounts of the hydrocarbons of interest in the presence of a relatively high concentration of methane. In

3-1

### addition since there is no specia tion, we are not obtaining any information about the relative contribution of any of the components. Also, the ba seline is not very stab le and we do not think it

adds a lot of useful information. Our recomm endation is to not use this instrument.

Innova Photoacoustic . This instrument can measure CO, CO 2 

### , total hydrocarbons and water vapor (dew point). However, the instrument is no t a true “continuous” monito r, but rather it takes grab samples, measures that sample and then takes another grab sample. This means that the value determined may not accurately represent the average over the time period it is applied to. We feel that a better way to obtain total hydrocarbons is to compar e CO and BTEX from continuous instruments to the same compounds in the canisters. Our reco mmendation is to not

use this instrument.

Langan T15 CO monitor. This instrument appear s accurate and easy to use in addition to being portable with very low power consumption. It is , however, temperature dependant and we will

need to dev elop a temperature based calibration to maintain accuracy. In addition, it appears to have a slower response time, es pecially post-exposure to a high concentrati on, but this was only noticeable in the extreme case of the generator at DRI where concentration changes were over 100 ppm in less than 1 minute. We do recommend using this instrument.

Integrated Samples . We recommend collecting integrated samples as a check on the continuous samples and to get more detailed speciation of VOCs. The association between the continuous

CO and BTEX data with the data from time-inte grated measurements can provide estimates of the time series for species wi thout feasible methods for con tinuous measurement such as 1,3 butadiene, acetaldehyde, et hanol, MTBE, and total nonmethane hydrocarbons..

SPME . Based on our pilot study, we consider this technique as very promising. We propose to use SPME for MTBE and BTEX, but not for etha nol, formaldehyde and acetaldehyde. We are currently working on perfecting ou r calibration procedure. We ar e also performing the series of experiments to determine th e optimal exposure time and the dependence of measured concentrations on storage conditions.

3.2 Recommendations for Measurements of VOC in Breath

During the pilot study breath concentrations of MT BE, benzene, toluene, ethylbenzene, and the xylenes was successfully conducted. Analysis of alveolar and full breath showed that the sampling technique to target alveolar breath excluded contributions of VOC’s present in th e “dead-space” air present in a full breath becaus e their concentrations were lower. Breath concentrations between the two separate subjects differed in many cases most likely because of slight differences in the time of sample collecti on. This is because the breath elimination halflives of the compounds measured are between 1 and 3 minutes (Lindstrom and Pleil, 1996), so slight differences in the time of collection can make large differences in observed breath concentrations. This can also explain why for many of the samples there was little or no exposure effect observed. These samples were generally collected minutes af ter the end of the exposures, after which much of the target compounds would have been eliminated. This effect was observed by Lioy et al. (1991), who saw little co rrelation with breath benzene concentrations and microenvironmental exposure concentrations, a nd attributed their lack of agreement to the

short time course of benzene elimination via breath.

3-2

### When collected in exposure environmen ts where the concentrations are above background (e.g. refueling) there is an observable exposure effect when the sample is collected very close to the end of exposure. However, these breath concentrations will only reflect what the subject is exposed to in the last portion of the exposure, as the ma jority of the one-hour exposure will have been eliminated by the time the samples are collect ed. Therefore single

breath measurements at the termination of e xposures are not a good in dex of cumulative onehour exposures. Therefore, we do not recomm end breath measurements for urban exposure experiments during the main study.

3.3 Recommendations for Measurement of VOC in Urine

The m ethod of Fustinoni (1999) based on a se nsitive SPME technique was developed for application to this study. Work at LRRI was conducted with the same i nstrument as used in that study, but the published quantitation limits of 12-34 ng/L were not attainable. We were able to observe good signal/noise for all of the analytes in what would likely be the sensitivity range published by Fustinoni (1999). However, the de uterated internal st andards utilized for quantitation had small amounts of the parent (u n-deuterated) compound pr esent that limited the limit of detection. The area counts of the parent compound in blanks showed integrated area counts from the mass spectrometer of approximately 600 for benzene, when the 100 ng/L

standard had area counts of about 2500. The use of the internal standards is necessary to reduce sample to sample variability in the uptake of the VOC’s by the SPME fiber.

Because of the low exposure concentrations observed in this study, the amount of urinary

benzene an d other VOC’s were extremely low. Although published excretion rates vary, a typical amount of un-metabolized benzene rela tive to exposure is on the order of 0.1% (Waidyanatha et al. (2001)). Fu stinoni (1999) showed urinary concentrations of benzene to be around 114 ng/L after an approximate 3.5 ppb exposur e, and Waidyanatha et al. (2001) have shown 145 ng/L concentrations in “non-exposed” subjects from an occupational exposure study. Similarly, Ghittori et al (1995) showed back ground levels of benzene in non-smokers of approximately 131 ng/L (geometric mean). Most of the urinary benzene concentrations observed in the currently reported pilot st udy are in the range of the low level exposures from previous

studies described above. Since the scripted exposures were low there was no strong correlation between exposure and urinary benzene in the pilot study. This is slightly in contrast to published results of Waidyanatha et al. ( 2001), who saw an exposure effect with benzene, but the exposure concentrations were in the ppm range.

After the highest exposure ther e was a relatively strong exposure effect observed in one subject and a lesser exposure effect observed in a second subject. There was a time course in the elimination of benzene that showed urinary benz ene concentrations increasing with time. These results are comparable to MTBE data repor ted by Lee and Weisel (1998) who showed an increase in urinary MTBE after exposure (1 pp m for 10 min) at about 1 hour, remaining about the same at 3.5 hours and dropping several-fold by 6 hours. Here urinary concentrations were only measured 3 hours post exposure, so we were not able to observe the start of elimination from the body. Because of an inab ility to see the decay of urinar y benzene after exposures, and the slight inconsistency in the two subjects ( one showed much higher urinary benzene), we repeated this highest end exposur e on June 4, 2002, to see if the urinary VOC concentration data

3-3

### can be linked strongly to an expos ure effect at these levels and to see the full time course of

elimination.

Because the additional measurements of ur inary MTBE/BTEX from the second refueling experim ent were promising, we recommend this measurement as the biomonitoring technique of choice. We will pay special attention to the pre-exposure background urine sample collection, making sure that the subject is not exposed to gasoline exhaust at least 10 hours pr ior to sample

collection. Since we were not able to discrimina te urinary benzene concen trations in low-level exposures (e.g. walking down street), we pr opose to only conduct biomonitoring experiments from projected “high-end” exposures such as re fueling. Monitoring will be conducted similar to the pilot study, with pre and post exposure collections of the s ubject’s urine.

3-4

### 4. REFERENCES

Albertini et al. (2001). Chem. Boil ineract. Vol 135-137, pg 429-453

Fustinoni, S., R. Giampiccolo, S. Pulvirenti, M. Buratti, and A. Colombi (1999). Headspace solid-phase mi croextraction for the determina tion of benzene, toluene, ethylbenzene and xylenes in urine. J. Chromatogr. B 723 : 105-115.

Ghittori, S., Maestri, L., Fiorentino, M.L. and Imbriani, M. (1 995). Evaluation of occupational exposure to benzene by urin alysis. Int. Arch. Occup. Environ. Health, 67, 195-200

Lee, C.W. and C.P. Weisel (2001). Toxic okinetics of Human Exposure to Methyl tertiary-butyl ether (MT BE) Following S hort-Term Controlled Exposures. J. Exposure Anal. And Environ. Epi., 11, 67-78

Lindstrom, A.B., and J.D. Pleil (1996). Alveol ar Breath Sampling and Analysis to Assess Exposures to Methyl Tertiary Butyl Ether (MTB E) During Motor Vehicle Refueling., J. Air and Waste Management, V. 46, p. 676-682

Lioy, P.J., Wallace, L., and E. Pelizzari ( 1991). Indoor/Outdoor, and Personal Monitor and Breath Analysis Relationships for Se lected Volatile Organic Com pounds Measured at Three Homes During New Jersey T eam, J. Exposure Anal. And Envir. Epi., Vol. 1, No. 1, pp 45-61

Philips, M. and J. Greenberg (1992). Ion-Trap Detection of Volatile Organic Com pounds in Alveolar Breath, Clin. Chem. 38/1, 60-65

Pleil, J.D., and A.B. Lindstrom (1995). Collec tion of a Single Alveolar Exhaled Breath for Volatile Organic Compound Analysis., Amer ican J. Industrial Medicine, 28; 109-121

Waidyanatha, S., N. Rothman, S. Fustinoni, M. T. Smith, R. B. Hayes, W. Bechtold, M. Dosemeci, L. Guilan, S. Yin, and S. M. Rappaport (2001). Urinary benzene as a biomarker of exposure among occupationally exposed and unexposed subjects. Carcinogenesis 22 : 279-286.

4-1

### FIGURE FOR SECTION 2Figure 2-1 ConcentrationTime Series, Freeway AMFreeway AM (R02022607)0.05.010.015.020.025.0 7:10 7:15 7:20 7:25 7:30 7:35 7:40 7:45 7:50 7:55 8:00 8:05CO0.02.04.06.08.010.012.0HC & HCHObkgdCO(ppm)T15 CO(ppm)THC byFID(ppm)HCHO(ppb)F-1Figure 2-2 Concentration Time Series, Surface StreetsSurface Streets (R02022607)0.02.04.06.08.010.012.014.016.018.020.0 12:00 12:05 12:10 12:15 12:20 12:25 12:30 12:35 12:40 12:45 12:50 12:55CO0.02.04.06.08.010.012.0HC & HCHObkgdCO(ppm)T15 CO(ppm)InnovaCO(ppm)THC byFID(ppm)THC asPropane(ppm*10)HCHO(ppb)F-2Figure 2-3 Concentration Time Series, Freeway PMFreeway PM (R02022616)0.05.010.015.020.025.0 16:00 16:05 16:10 16:15 16:20 16:25 16:30 16:35 16:40 16:45 16:50 16:55CO0.02.04.06.08.010.012.0HC & HCHObkgdCO(ppm)T15 CO(ppm)InnovaCO(ppm)THC byFID(ppm)THC asPropane(ppm*10)HCHO(ppb)F-3Figure 2-4 Concentration Time Series, Refueling In-CabinRefueling In-Cabin (R02022708)0.01.02.03.04.05.06.07.08.09.010.0 8:10 8:15 8:20 8:25 8:30 8:35 8:40 8:45 8:50 8:55 9:00 9:05CO0.01.02.03.04.05.06.07.0HC & HCHObkgdCO(ppm)T15 CO(ppm)THC byFID(ppm)HCHO(ppb)F-4Figure 2-5 Concentration TimeSeries, Refueling out of cabinRefueling Out of Cabin (R02022712)0.01.02.03.04.05.06.07.0 12:00 12:05 12:10 12:15 12:20 12:25 12:30 12:35 12:40 12:45 12:50 12:55CO0.05.010.015.020.025.030.035.040.0HC & HCHObkgdCO(ppm)T15 CO(ppm)InnovaCO(ppm)THC byFID(ppm)THC asPropane(ppm*10)F-5Figure 2-6 Concentration TimeSeries, Walking DowntownWalking Downtown (R02022811)0.01.02.03.04.05.06.07.0 11:00 11:05 11:10 11:15 11:20 11:25 11:30 11:35 11:40 11:45 11:50 11:55CO0.01.02.03.04.05.06.07.0HC & HCHObkgdCO(ppm)T15 CO(ppm)InnovaCO(ppm)THC asPropane(ppm*10)HCHO(ppb)F-6Figure 2-7 Concentration TimeSeries, Underground GarageUnderground Garage (R02022815)0.02.04.06.08.010.012.0 15:00 15:05 15:10 15:15 15:20 15:25 15:30 15:35 15:40 15:45 15:50 15:55CO0.01.02.03.04.05.06.07.08.09.0HC & HCHObkgdCO(ppm)T15 CO(ppm)InnovaCO(ppm)THC byFID(ppm)THC asPropane(ppm*10)HCHO(ppb)F-7Figure 2-8 Concentration Time Series, Residential Garage Background AResidential Garage Background A (R02030109a)0.00.10.20.30.40.50.6 9:35 9:40 9:45 9:50 9:55 10:00 10:05CO0.01.02.03.04.05.06.07.0HC & HCHObkgdCO(ppm)T15 CO(ppm)InnovaCO(ppm)THC byFID(ppm)THC asPropane(ppm*10)HCHO(ppb)F-8Figure 2-9Concentration Time Series, Residential Garage Background BResidential Garage Background B (R02030109b)0.00.10.10.20.20.30.30.40.40.50.5 10:05 10:10 10:15 10:20 10:25 10:30 10:35CO0.01.02.03.04.05.06.07.0HC & HCHObkgdCO(ppm)T15 CO(ppm)InnovaCO(ppm)THC byFID(ppm)THC asPropane(ppm*10)HCHO(ppb)F-9Figure 2-10 Concentration Time Series, Residential Garage Sample CResidential Garage Sample (R02030109c)0.00.10.20.30.40.50.60.70.8 11:10 11:15 11:20 11:25 11:30 11:35 11:40CO0.02.04.06.08.010.012.014.016.018.0HC &HCHObkgdCO(ppm)T15 CO(ppm)InnovaCO(ppm)THC byFID(ppm)THC asPropane(ppm*10)HCHO(ppb)F-10Figure 2-11 Concentration Time Series, Residential Garage Sample DResidential Garage Sample (R02030109d)0.00.10.20.30.40.50.60.70.80.91.0 11:40 11:45 11:50 11:55 12:00 12:05 12:10CO0.02.04.06.08.010.012.014.016.018.0HC & HCHObkgdCO(ppm)T15 CO(ppm)InnovaCO(ppm)THC byFID(ppm)THC asPropane(ppm*10)HCHO(ppb)F-11Figure 2-12 Concentration Time Series, Residential Garage Sample EResidential Garage Sample (R02030109e)0.00.10.20.30.40.50.6 12:10 12:15 12:20 12:25 12:30 12:35 12:40CO0.02.04.06.08.010.012.014.016.0HC & HCHObkgdCO(ppm)T15 CO(ppm)InnovaCO(ppm)THC byFID(ppm)THC asPropane(ppm*10)HCHO(ppb)F-12Figure 2-13 Concentration Time Series, Residential Garage Sample FResidential Garage Sample (R02030109f)0.00.20.40.60.81.01.21.41.61.82.0 12:40 12:45 12:50 12:55 13:00 13:05 13:10CO0.02.04.06.08.010.012.014.0HC & HCHObkgdCO(ppm)T15 CO(ppm)InnovaCO(ppm)THC byFID(ppm)THC asPropane(ppm*10)HCHO(ppb)F-13Figure 2-14 Concentration Time Series, Residential Garage SampleGResidential Garage Sample (R02030109g)0.00.10.20.30.40.50.60.70.80.9 13:10 13:15 13:20 13:25 13:30 13:35 13:40CO0.01.02.03.04.05.06.07.0HC & HCHObkgdCO(ppm)T15 CO(ppm)InnovaCO(ppm)THC byFID(ppm)THC asPropane(ppm*10)HCHO(ppb)F-14Figure 2-15 Concentration Time Series, GeneratorResidential Garage Sample (R02030116)0.0100.0200.0300.0400.0500.0600.0700.0800.0900.0 16:00 16:05 16:10 16:15 16:20 16:25 16:30CO0.020.040.060.080.0100.0120.0HC & HCHObkgdCO(ppm)T15 CO(ppm)InnovaCO(ppm)THC byFID(ppm)THC asPropane(ppm*10)HCHO(ppb)Generator Sample(R02030116)F-15Figure 2-16 MS200 Raw and Corrected DataFreeway AMMS200 Raw Benzene, Zero, and Corrected-0.0100.010.020.030.040.050.060.070.080.090.10.11

ppmv0:00:00 0:07:12 0:14:24 0:21:36 0:28:48 0:36:00 0:43:12 0:50:24 0:57:36 1:04:48Elapsed timebenzenebz zerobz corrF-16Figure 2-17 MS200 Corrected Data OnlyFreeway AMMS200 Corrected Data Only-0.0100.010.020.03

ppmv0:00:00 0:07:12 0:14:24 0:21:36 0:28:48 0:36:00 0:43:12 0:50:24 0:57:36 1:04:48Elapsed timebz corrtol corrxyl corrF-17Figure 2-18. Correlation between CO by T15 and by Innova.y = 0.8754x + 0.4195R2= 0.7709024681012141618

Innova CO (ppm)024681012141618T15 CO (ppm)F-18Figure 2-19 Correlation between Innovaand TEI for total hydrocarbons.Chart Titley = 0.0703x + 3.0835R2= 0.287802468101214020406080100120140Innova HC as propane (ppm*10)

TEI HC as methane (ppm)F-19Figure 2-20 Innova vs.TEI for total hydrocarbons with three outliers removed.Chart Titley = 0.209x + 2.4854R2= 0.68190.002.004.006.008.0010.0012.0014.0016.0018.00

TEI HC as methane (ppm)0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00Innova HC as propane (ppm*10)F-20F-21Figure 2-21 Correlation betweenCO and formaldehyde.y = 0.5062x + 4.5338R2= 0.262102468101214160510152025T15 CO (ppm)

Battelle HCHO (ppb)

### Figure 2-22 Correlation between DNPH and continuous formaldehyde.

F-22 

### HCHO

y = 0.8543x + 0.6638

R 2

= 0.9532

15 20 25

25le-HCHO

0

5 10

0 5 10 15 20

DNPH-HCHOBattelFigure 2-23. Pre and post exposure breath samples during refueling.Refueling01234567mtbebenzetolueetbzmp_xylo_xyl

ppbv7 Refueling PRE7 Refueling POST3 Refueling PRE3f Refueling POSTF-23Figure 2-24 Pre and post exposure breathsamples during in-cabin fueling.In-cabin Fueling00.511.522.533.544.55mtbebenzetolueetbzmp_xylo_xyl

ppbvIn Cabin fueling PREIn Cabin fueling POSTF-24Figure 2-25 Pre and post exposure breath samples during walk.Walk012345678910

ppbvmtbebenzetolueetbzmp_xylo_xylWalk PREWalk POSTWalk PREWalk POSTF-25Figure 2-26 Relationship betweenfull and alveolar breath.Realationship Between Full and Alveolar Breath0.000.501.001.502.002.503.003.50MTBEbenzenetoluene ethylbenzene m/p xylene o-xylene

ppbvFull BreathAlveolar BreathF-26Figure 2-27The three traces; benzene, toluene and sun of xylenes andethylbenzeneRefuel00.020.040.060.080.10.120.140.160.180.20:00:000:07:120:14:240:21:360:28:480:36:00Elapsed time

ppmvBenzeneTolueneSum xylenes+ethylbenzeneF-27Figure 2-28 Data for BTEX and MTBE0.0000.0500.1000.1500.2000.2500.3000 2 4 6 810Sample Number

ng/LMTBEBenzeneTolueneEth Benzenep/m xyleneo-xylenePre-exposure Post exposureF-28

# Appendix E

Section 211(B) Tier 2 High-End Exposure S creening Study of Baseline and Oxygenated Gasoline – 2nd Reno Pilot Study

### SECTION 211(B) TIER 2 HIGH END EXPOSURE SCREENING STUDY OF BASELINE

AND OXYGENATED GASOLINE –2ND RE NO PILOT STUDY

DRAFT REPORT

Prepared for

AMERICAN PETROLEUM INSTITUTE

1220 L Street Washington, DC 20005-4070

Prepared by

Barbara Zielinska, John Sagebiel, David Campbe ll, Diana Ceballos, Mark McDaniel and Eric Fujita
Desert Research Institute

2215 Raggio Parkway Reno, NV 89512

### TABLE OF CONTENTS

1. Introduction

................................................................................................................ ........ 1-1

1.1 Study Overview and Technical Objectives ............................................................. 1-1

2. Experimental Methods

....................................................................................................... 2 -1

2.1 Measurement Approach

........................................................................................... 2-1

2.2 Improvement in Sa mpling Platform

........................................................................ 2-4

2.3 Analytical Methods

................................................................................................. 2-6

2.3.1 Breath Samples Analysis

............................................................................... 2-6

2.3.2 SPME Methodology

...................................................................................... 2-7

2.4 Data Capture

.......................................................................................................... 2-15

3. Results

..................................................................................................................... ........... 3-1

3.1 Method Comparison of Redundant Data

................................................................. 3-1

3.1.1 PID versus PID

.............................................................................................. 3-1

3.1.2 NDIR vs. Electrochemical CO

....................................................................... 3-7

3.1.3 CO versus Canister CO

................................................................................ 3-10

3.1.4 MS vs. Canister

............................................................................................ 3-12

3.1.5 SPME vs. Canisters

...................................................................................... 3-13

3.1.6 SPME vs. MS

............................................................................................... 3-17

3.1.7 DNPH vs. Formaldehyde

............................................................................. 3-21

3.1.8 Tenax vs. Canisters

...................................................................................... 3-21

3.2 Comparisons of Correlated Data

........................................................................... 3-23

3.2.1 PID vs. CO

................................................................................................... 3-23

3.2.2 CO vs. Formaldehyde

.................................................................................. 3-28

3.2.3 SPME vs. PID

.............................................................................................. 3-32

3.3 Environmental Factors

........................................................................................... 3-35

3.4 Reconstructed Data

................................................................................................ 3-40

3.5 Breath Data

............................................................................................................ 3-46

3.6 Consistency of Microenvironment Conditions ...................................................... 3-51

3.6.1 CO 3-51

3.6.2 PID 3-53

4. Conclusions

................................................................................................................. ....... 4-1

5. References:

................................................................................................................. ........ 5-4

6. Appendicies

................................................................................................................. ....... 6-1

6.1 Appendix A: SPME

................................................................................................ 6-1

6.2 Appendix B: Canisters and Tenax

.......................................................................... 6-3

6.3 Appendix C: Breath Samples

................................................................................. 6-9

6.4 Appendix D: DNPH

............................................................................................. 6-12

ii

### LIST OF FIGURES

Figure 2.2-1. Van inlets

....................................................................................................... .. 2-5

Figure 2.2-2. Inlets mounted on the tripod.

........................................................................... 2-5

Figure 2.3-1. Set-up for tem perature (upper pane l) and relative hum idity (lower panel) dependence measurements

.............................................................................................. 2-9

Figure 2.3-2. Temperature Dependence for 30, 50, and 100 ppb BTEX Concentrations. . 2-10

Figure 2.3-2–cont’d. Tem perature De pendence for 30, 50, and 100 ppb BTEX
Concentrations.

............................................................................................................. 2-11

Figure 2.3-3. Concentration calibration at a given tem perature for the BTEX compounds.

................................................................................................................... 2-11

Figure 2.3-3-cont’d. Concentr ation calibration at a given tem perature for the BTEX compounds.

................................................................................................................... 2-12

Figure 2.3-4. Dynamic Calibration Temperature Dependence ............................................ 2-13

Figure 2.3-5. Static C alibration T emperat ure Dependence (By interpolation from dynamic system)

........................................................................................................... 2-13

Figure 2.3-6. Hum idity De pendence on SPME response for a 100ppb BTEX standard

at 25C.

........................................................................................................................ ... 2-14

Figure 2.4-1. Effect of driving on continuous formaldehyde analy zer, during and after sampling in ME2-5.

...................................................................................................... 2-16

Figure 3.1-1a. Comparison of estim ated B TEX concentrations measured by PID
instruments with inlets collocated w ithin 10 cm . Data are running 1 m inute averages. VR = nozzle vapor recovery.

.......................................................................... 3-2

Figure 3.1-1b – cont’d. Com parison of estim ated BTEX c oncentrations m easured by PID instrum ents with in lets collocated within 1 0 cm . Data are runn ing 1 m inute averages. VR = nozzle vapor recovery.

.......................................................................... 3-3

Figure 3.1-2. Com parison of estim ated B TEX concentrations m easured by P ID instruments during freeway driving tests. Data are running 1 minute averages. ............ 3-5

Figure 3.1-2 –cont’d. C omparison of estimated BTEX concentrations measured by PID instruments during freeway driving tests. Data are running 1 minute averages. ............ 3-6

Figure 3.1-3. Comparison of NDIR (API m odel 300) and electrochem ical (Langan T15v) CO monitors during two freeway driving tests. ................................................... 3-8

iii

### Figure 3.1-4. Com parison of two gas-filter correlation NDIR CO analyzers during onroad sampling.

................................................................................................................. 3-9

Figure 3.1-6 Comparison of canister and MS200 data for all measured species. ................ 3-12

Figure 3.1-7. Comparison of MS200 a nd canister for benzene only. .................................. 3-13

Figure 3.1-8. Scatter Plots for raw data from SPME vs canister for the Pilot Study 2003 . 3-15

Figure 3.1-9. Scatter Plots for temperature co rrected SPME vs canister data for the Pilot Study 2003

.................................................................................................................... 3 -15

Figure 3.1-10. Scatter plots from SPME vs Canister for the Pilot Study 2003 with two
outliers removed.

.......................................................................................................... 3-16

Figure 3.1-11. 10 m inutes average MS data vs SP ME benzene and toluene concentrations: Freeway 5/02 7:35-8:15 am

................................................................. 3-18

Figure 3.1-12. 10 m inutes average MS da ta vs SP ME benzene and toluene concentrations: Freeway 4/30, 7:35 am

........................................................................ 3-19

Figure 3.1-13. 10 m inutes average MS data vs SP ME benzene and toluene concentrations: Refueling w/o VR 5/02 9:18 am ......................................................... 3-20

Figure 3.1-14 Comparison of caniste r and Tenax data for all ME ..................................... 3-22

Figure 3.2-1. Comparison of CO and BTEX by PID during parking garage tests. ............ 3-24

Figure 3.2-1 – cont’d. Com p arison of CO and BTEX by PID during parking garage tests. Data are running 1 minute averages.

................................................................... 3-25

Figure 3.2-3. Scatter plot of CO vs BTEX by PID during parking garage tests. Data are running 1 minute averages.

........................................................................................... 3-26

Figure 3.2-4. Comparison of CO and BTEX by PID during freeway driving tests. ........... 3-27

Figure 3.2-9. SPME 10 m in total BTEX vs. PID 10 m in averages, Freeway, 5/02, 7:35

am

............................................................................................................................. .... 3-32

Figure 3.2-10. SPME 10 m in total B TEX vs. PID 10 m in averages, Refueling w/o VR
4/30 9:21am.

................................................................................................................. 3-32

Figure 3.2-11. SPME 10 m in total BTEX vs. PID 10 min averages, Freeway 4/30, 7:35

am.

............................................................................................................................ .... 3-33

Figure 3.2-12. SPME 10 m in total B TEX vs. PID 10 m in averages, Refueling w/o VR
5/02 9:18 am.

................................................................................................................ 3-33

iv

### Figure 3.2-13. SPME 10 min total BTEX vs. PI D 10 min averages, Parking Garage 5/06, 16:45 pm.

...................................................................................................................... 3-34

Figure 3.3-1. Fuel tank te mperatures during freeway ME on 4/29/03. Ambient temperature was 4.4 C during this time.

....................................................................... 3-37

Figure 3.5–1. CO2 values in the breath sam ple s of subjects B and J collected in all ME, organized by the subject and by microenvironment. .................................................... 3-47

Figure 3.6-1. Range and variability of CO con centration during tests. Statistics for each of the five replicate tests are s hown for each microenvironment. ................................ 3-52

Figure 3.6-2. Range and variability of BT EX by PID concentration during tests. ............. 3-54

Figure 3.6-3. Range and variability of m ean CO and mean BTEX by PID concentration
for four microenvironments.

......................................................................................... 3-55

v

### LIST OF TABLES

Table 2.1-1. Measurement methods used in the 2 nd 

### Reno Pilot Study. ................................. 2-3

Table 2.4-1. Data Capt ure Summary

................................................................................... 2-16

Table 3.1-1. Data comparison be tween SPME and Canister .............................................. 3-14

Table 3.1-2. Correlation of S catter Plots from SPME and Canister Comparison ............... 3-16

Table 3.3-1. Environmental Conditions for Freeway Driving MEs. ................................... 3-36

Table 3.3-2. Environmental Condi tions for Garage MEs. ................................................... 3-38

Table 3.3-3. Environmental Conditio ns for Refueling MEs. ............................................... 3-39

vi

## 1. INTRODUCTION

The U.S. Environmental Protection Agency (EPA) has recently issued requirements for a test program in accordance with the Alternative Tier 2 provisions of the fuels and fuel additives (F/FA) health effects testing regulations, whic h are required pursuant to Section 211(b) of the Clean Air Act. In re sponse to th ese requirem e nts, the Americ an Petro leum Institu te (API) contracted with a research team consisting of the Desert Research Institute (DRI), Southwest Research I nstitute (S wRI), Lovelace Respir atory Res earch In stitute (LRRI), and TRJ Environmental, Inc (TRJ) to conduct a screen ing study of the high-end distribution of inhalation exposures to evapor ative and com bustion emissions of baseline- and oxygenated gasoline. T he exposure protocols and m eas urement methods, sampling & analytical procedures are described in the June 13, 2002 Exposure Protocol and Study Plan. The field measurements in San Antonio, Houston

, and A tlanta were com pleted in adheren ce to th is written protocol during summer 2002. The work in Chicago was postponed pending further evaluation of the measurement protocol and assessment of the data collected to date.

The overall approach for the e xposure study is based upon the draft S211b Tier 2 E xposure Study Protocol that was developed in May 2001 by the API Section 211(b) Research Group and reviewed by the EP A. DRI and LRRI cond ucted a five-day pilo t study in Reno, NV during February 2002 to test alternative m e asurement approaches in the field under
conditions that are sim ilar to those that will be encountered in the m ain study. TRJ and API provided input in the design of the pilo t study and rev iewed the results and findings. The
evaluations included available m easurement methods for continuous and tim e-integrated measurements of carbon m onoxide (CO), to tal volatile organic com pounds (TVOC), and designated VOC species. DRI and LRRI also evaluated th e stab ility of the designated VOC species in breath and urine sam ples during th e pilot study. Results of the pilot study are summarized in our pilot study report (Zielinsk a et al., 2002). The draft exposure protocols were appropriately modified based upon the results of the pilot study.

The work conducted last summ er was summarized in two interim data reports, one reporting on data collected in San Antonio, Houston a nd Atlanta, and one conducting detailed data analysis from Atlanta. Based on these reports, in order to a ssess and identify th e necessity for further refinem ent and adjustm ents to th e study protocol prior to the comm encement of the next phase of the study EPA asked to conduct the 2 nd 

### Pilot S tudy in Reno during the April – May 2003 time frame.

1.1 Study Overview and Technical Objectives

The m ain goal of the 2 nd 

### Reno Pilot Study was to de monstrate proper operation and reliability of analytic al ins trumentation and com parability of tim e-integrated, sem icontinuous and continuous m ethods for com pounds of interest. Four m icroenvironments were selected for this study, as follows:

1. Morning rush hour commuter traffic (ME1). This test was conducted on US395. Due to the lim ited rush hour period in Reno, a relatively small city, we sam pled for

1-1

### only 40 minutes. The driving route was from Parr Blvd in the north to V illanova Dr. in the south. During the test we a ttempted to follow a high e mitting vehicle that was supplied by one of our DRI coworkers (Dat sun 280Z, 1975). W e sampled inside the van under high (first 20 min) a nd low (second 20 min) ventil ation conditions . In low ventilation condition, we used recirculated air, windows closed, fan on high and in high ventilation conditions we ha d windows open, with fresh air, recirculated air off. During this ME a second PID m onitored the air outside the van.

2. Parking garage (ME2). Due to lack of a suitable be low ground parking structure in Reno, we used an above ground parking gara ge. W e selected the Galleria parking garage in downtown Re no, a site that is used by county worker s in a nearby building whose workday ends at 5:00 PM. Consequently , this location had a pulse of cold-start
traffic emissions at 5:00 PM as workers at tempted to leave at the sam e time. Due to our limited city size and m odest traffic de nsity, we anticipated th e evening exit rus h from the garage to be over promptly and employed one-half hour of sam pling (approximately 1645 to 1715) from the van park ed at a location ne ar the only garage exit. Thus, all cars had to pass our sam pli ng location as they exit the garage. T he sampling inlet was located at the breath ing zone immediately next to the van.

3. Outdoor refueling with Stage 2 vapor recovery at the pump (ME3). We conducted refueling of one vehicle (our 1996 sam pling minivan) during a 20 m in period. The fuel tank of the van was m odified to enable the fuel to be drained from the van prior to refueling. Our objective wa s to dispense approxim ately the sam e
amount of fuel each tim e. The vehicle was driven prior to refu eling to raise the monitored temperatures on the outside surf ace of the fuel t ank. The refueling tests were performed at the service station in Reno (corner of Sun Valley Dr. and Dandini Blv.), which has stage 2 vapor recovery nozzles. While rem oving the nozzle from the vehicle filler tube, we spilled a few drops of liquid gasolin e on the ground near th e vehicle. The amount of the spill was not ed. The refueling was done under calm wind conditions (i.e., wind speed below 5 m ph). W ind was monitored by hand-held anemometer. Monitoring was done at the br eathing zone of the person fueling the

van.

4. Outdoor refueling without vapor recovery at the pump (ME4). This test was conducted at a sm all gas station in Reno th at does not have stage 2 vapor recovery
nozzles. Because this s tation sells a rela tively low volum e of fuel, it has not been required to upgrade to the stage 2. As not ed above, we refueled one vehicle during the 20 min test at the gas station. While ta king the nozzle from the vehicle filler tube, we caused a spill of a few drops of liquid ga soline on the ground near the vehicle. The amount of t he spill was noted. The refueling was done under calm wind conditions (i.e. wind speed below 5 m ph). M onitoring was done at the breathing zone of the person fueling the van.

Figure 1-1 shows the sampling locations. The US395 driving segment is marked in blue.

1-2

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## 2. EXPERIMENTAL METHODS

2.1 Measurement Approach

Our sampling strategy consists of a three-tiered approach sh own in Table 2.1-1, which lists the overlapping measurement methods used in the Section 211(B) Ti er 2 High-End Exposure Screening Study and their intended application. The applications ar e classified in one of three tiers: reference, surrogate, a nd confirmatory. The base s et or “reference” (R) m easurements consist of three well-es tablished tim e-integ rated m easurements. Thes e include : 1 ) canis ter sampling and analysis by gas chromatography w ith flame ionization detection for methanized CO, BTEX, 1,3-butadiene, MTBE, and nonm ethane hydrocarbons (NMHC); 2) 2,4- dinitrophenylhydrazine (DNPH) car tridge sampling and analysis by high perform ance liquid chromatography with UV detection for form aldehyde and acetalde hyde; and 3) solid adsorbent sampling and analysis of ethanol by gas chrom atography with m ass spectrometry
detection. T hese three m ethods combined m eas ure all species of in terest over the entire sampling period with in each m icroenvironment. Although these integrated m ethods do not characterize peak exposures in microenvironments with highly varying exposure levels. They provide a basis for validating continuous and se mi-continuous data. They also provide a basis for deriving correlations between the integrated values and continuous “surrogates” (S), such as CO and photoionizable VOC (10.6 eV - photoi onization detector) PID data, in order to
reconstruct their tim e series. For ex ample, data for BTEX, 1,3-butadiene

, and MTBE from
the canister m easurements can be correlated to continuous C O and PID data to reconstruct
their time series in exh aust-dominated environments. The sam e method is used fo r ethanol and NMHC. In a sim ilar manner, the tim e series of acetald ehyde and form aldehyde can be reconstructed from the correlation of the integr ated DNPH samples with CO or PID. Outdoor afternoon samples should be excluded due to possible contributi on of carbonyl compounds formed from atmospheric reactions of hydrocarb ons. Table 2.1-1 shows th e other correlations
that can be used in this manner.

Three continuous methods were employed to mon itor: 1) the aromatic hydrocarbons benzene, toluene, ethylbenzene, and the xylenes (B TEX), 2) carbon monoxide, and 3) for maldehyde.
These m ethods were also combined with com ponent concentration ratios fr om contemporaneous time-integrated samples to rec onstruct the expected tim e series for specie s
that did not have continuous instrum ents, e.g., 1,3-butadiene (BD), ethanol (E tOH), and methyl tert-butyl ether (MTBE).

The Kore MS200 instrum ent was used to m onitor BTE X on a one-m inute basis. This instrument uses a tim e-of-flight mass spectrometer to separate com pounds of interest. This instrument also uses a s oftware solution incorp orating the 7 0 eV electro n impact ionization fragmentation patterns of each compound to a pportion the contribution of each component of interest to the time-of-flight (TOF) mass spect rum seen by the instrument. The software does not distinguish between specific isomers, thus xy lenes are reported together. The inlet uses a polydimethylsiloxane mem brane preferentially to allow non-polar organic com pounds into the analyzer while maintaining the vacuum inside the analyzer chamber. This membrane inlet

2-1

### does limit the types of com pounds that can be analyzed, however. Common air c onstituents and polar organic molecules do not pass the membrane quickly.

Carbon monoxide was monitored by the Langan T15 CO monitor and the API Model 300 and ML9830 CO NDIR analyzers. The Langan T 15 is an electrochemical monitor for CO. The response time of this instrument is somewhat slower than infrared-based instruments. Both the API and ML instruments are specified in the EPA List of Designated Reference and Equivalent Methods (March 24, 2000) as a federal reference method operating at any temperature in the range of 15 oC to 35 oC (59 oF to 95 oF). (www.epa.gov/ttnamti1/files/ambien t/criteria/criteria/0300co.pdf)

Continuous Form aldehyde Monitor (Alpha-Om ega Power T e chnology, Ltd., Albuquerque, NM) absorbs form aldehyde in acidified wate r, reacting it with 2,4-pentanedione and ammonia to form a cyclized product, 3,5-diacet yl-1,4-dihydrolutidene, which is continuously detected by fluorescence. The method is highly specific for formaldehyde and very sensitive. However, since this instrum ent did not perform ed well during the summer study we introduced several im provements, as follows. The original instrument case, detector, electronics, valves, some of th e fittings were retained. Majo r modifications included removal of the original four channel peristaltic pump necessary for reagent delivery and fluid flows to the detector. This pum p was found to be incapa ble of maintaining consistent flows and was susceptible to failure when pum p t ubing woul d rupture or pull away from the connection fittings. In addition, flow rates h ad lim ited adjustability, m aking it not suitable for the additional modifications that were perform ed on the ins trument. The peris taltic pump was replaced with four m illiGAT piston pum ps (Global FIA) with m icroprocessor-controlled motors capable of delivering a broad range of precisely metered flow rates. Another m ajor modification was replacem ent of the diffusi on scrubber assem bly with a scrubbing coil similar to the design described in Kelly and Fortune (1994). The original diffusion scrubber was susceptible to m alfunction when scrubbers or driers were heavily used or contam inated by the reagents. In contrast, the scrubbing coil is sim ple to operate and m aintain, and is reported as being 100% efficient at rem oving gaseous form aldehyde from the air stream being sampled. An in-line debubbler (Global FIA) was installed betwee n the heated reaction cell and the detector to rem ove any bubbles from the sample stream before entering the detector. This was necessary because bubbles m ay be generated elsew here in the system or when the sample m obile phase is heated in th e reaction cell. Finally , calibration of the instrument was perform ed using a gaseous form aldehyde standard (1 ppm in N 2(g) 

### ,ApelReimer) diluted to the desired concentration (5 to 250 ppb) with UHP zero air (Airgas) and plumbed to the sample inlet of the scrubbi ng coil. Calibration curves were linear (R 2 

### >0.99). The instrument response tim e was determ ined to be 6 m inutes from the tim e of sam ple introduction to equilibration at the detector . Instrum ent background was determ ined by periodically installing a DNPH car tridge (Waters) on the inlet of scrubbing coil to rem ove any formaldehyde from the sample stream in order to observe the detector baseline response.

2-2Table 2.1-1. Measurement methods used in the 2ndReno Pilot Study.Data applications for specific methods are classified as reference, confirmatory, and surrogate.A1ContinuousSemi-ContIntegratedMethodT15 CO NDIR CO ppbRAE MS200 HCHO SPME Canister DNPH Adsorbentpplicable Environments all all all higher end all all all all allTime Resolutionseconds seconds seconds 1 min 1-2 min 10 min 30 & 40 min 30 & 40 min 30 & 40 minDetection Limits0.1 ppm 0.04 ppm 1 ppb 1-3 ppbv 1 ppbv 0.2 ppbv 0.05 ppbC 0.1 ppbv 0.2 ppbvData Application1SSSCCCRRRCOSC SCRPID2SCBTEXS (a) S (a) SC (c) CCR,3-ButadieneS (a) S (a) S (c)RMTBES (a) S (a) S (c)C RFormaldehydeS (b) S (b) S (d)CRAcetaldehyeS (b) S (b) S (d)S (g)REthanolS (e) S (e) S (f)RNMHCS (a) S (a) S (c)R1. Category of data application include surrogate (S), confirmatory (C) reference (R), and surrogate compounds or signal (SC)2. Sum of molecules ionizable at 10.6 eVand detected by photoionization detector.S (a). Time series will be reconstructed from the canister/CO ratio for exhaust-dominated samples.S (b). Time series will be reconstructed from the DNPH/CO ratio for exhaust-dominated samples except outdoor daytime samples.S (c). Time series will be reconstructed from the canister/PIDratio for exhaust- or evap-dominated samples in outdoor MEs.S (d). Time series will be reconstructed from the DNPH/PID ratiofor exhaust-dominated samples except outdoor daytime samples.S (e). Time series will be reconstructed from the solid adsorbent/CO ratio forexhaust-dominated samples.S (f). Time series will be reconstructed from the solid adsorbent/PID ratio for exhaust and evap-dominated samples.S (g). Time series will be reconstructed from CH3CHODNPH/HCHOContratio for exhaust dominated samples.2-3

### Photoionization detector (PID) m easured the total signal fr om molecules ionizable at 10.6 eV. We used two PID monitors for the pilo t study. For the freewa y runs, one PID sampled outside air, and the other sam p led in-cabin air. For th e re maining runs, only one PID was used, but for comparison purposes we ran both of them side-by-side for selected runs.

The tim e-integrated and se mi-continuous collection m ethods (canis ters, solid ad sorbent cartridges, DNPH-integrated cartridges and SPME) were described in detail before (Zielinska et al, 2002, 2003). Depending on the type of sorbent (C18 or silica gel) in the DNPH cartridge, the carbonyl com pound a mbient m eas urement results are subject to various
artifacts due to interaction with ozone

. Consequently, the ozone denuder is recommended for sample collection. For this pilot study, we used a honeycom b denuder coated with sodium carbonate/sodium nitrite/glycerol m ixture (m ethod developed by Dr. K outrakis from the Harvard School of Public Health). For canister sam pling, ambient NO 2 

### is of concern, since it might react with 1,3 butadiene. Thus, we were using a honeycom b denuder coated with triethanoloamine (TEA) to remove NO 2 

### (a method developed by Dr. Koutrakis).

In addition, we collected breath samples in all microenvironments. We used 1 liter silicosteel canisters (Restek, Inc.) and a collection m ethod described by Pleil and Lindstrom , 1995. Breath samples we re c ollected f or the ref ue ling MEs imm ediately before and 10 seconds after refueling the vehicle to provide an estim a te of the highest cum ulative exposure. For the commuter traffic and garage MEs, breath sam ple s were collected before, and at 10 seconds after a peak exposure indicated by the PID, an d at the end of the ME s ampling time. Two breath samples were collected at refueling ME s (total of 20) and three during each co mmuter traffic and garage tests. This is a total of 50 breath sam ples. The CO2 level in the breath sample of persons conducting the breath te st was measured prior to the pilot study.

2.2 Improvement in Sampling Platform

The m ost significant ch ange m ade to the sa mpling pla tform was the com bination of all sampling inlets at a single location. For the m ob ile ME (freeway driving), the inlets are all located in the breathing zone n ear the driver’s right shoulder. Figure 2.2-1 shows the current configuration of the inlets. The line in this fi gure labeled “Sample Inle t” provides sample to the NDIR CO, the MS200, the for maldehyde instrume nt, one of the two PIDs and all of the integrated samplers (canister, DNPH and solid adsorbent). The SPME f iber, the main inlet and the temperature and relative humidity sensor are all within 3 cm of each other. The T-15 (electrochemical) CO instrum ent is also very close. This configuration was designed to minimize or eliminate potential variability associ ated with concentration gradients inside the van. In addition, we recorded the fuel tank temperature by way of a tem perature probe
secured to the outside of the fuel tank and insulated to prev ent influence from the ground or
air heat. The video camera recorded the view out the front windshield during the driving ME and was used to record other significant activ ity a t the other MEs. For exam ple, in the garage, the camera was used to record traffic driving by the sampling point.

2-4

### Figure 2.2-1. Van inlets

For the stationary MEs (refueli ng and garage), the in let was mounted on a tripod to allow for placement at an appropriate location outside the van. In this case, the temperature and relative humidity probe was relocated as well. This was accomplished by an additional piece of Teflon tubing for the inlet and an extension cable for the temp erature and relative humidity probe. This allows the sampling system to be switched from one configuration to the other relatively quickly w ithout disturbing the instrument s and samplers. Figure 2.2-2 shows a close-up of the tripod a nd details the locations of the sample inlet, the T/RH probe, and the SPME fiber. The proximity of all thre e ensures that no small-scale variations in concentration are influencing the sample.

Figure 2.2-2. Inlets mounted on the tripod.

In addition, there were several other modifications made to the van to improve it for the sampling program. Among these were the addition of racks to safely and securely hold the equipment, the upgrading of the power supply, and the addition of a pump and lines to

2-5

### withdraw the fuel from the fuel tank in betw een the refueling MEs. A computer-based data acquisition system was also installed to acquire as much of the data as possible in one system. This was used to log all temperatur e and other environmental parameters, analog outputs from the CO instruments and the fo rmaldehyde instrument, and position, speed and
direction information from the GPS unit.

The power system was significantly upgraded to provide power and to eliminate the suspected artifact seen on the T-15 CO under low ventilation conditions. In these experiments, no artifact was observed on the T- 15 CO monitor, and thus we are confident that this potential contamination has been eliminated. However, the power system proved incapable of providing enough power for the AP I NDIR CO monitor. Once we discovered what was wrong (the instrument did not give an error message, rather it began giving very erratic results), we added a se t of lead-acid batteries outside the van to provide the power necessary to supply th is one instrument.

2.3 Analytical Methods

Most of the analytical m ethods e mployed duri ng this pilot study were described in detail before (Zielinska et al., 2002a,b; 2003). Th e exceptions are the anal ysis of the breath samples that was perform ed si milarly to the m ethod of Pleil and Lindstrom , 1995, by gas chromatography/mass spectrom etry (GC/MS), a nd the determ ination of the dependence of SPME concentrations o n tem perature and rela tive hum idity. The sections below describe these two analytical procedures.

2.3.1 Breath Samples Analysis

The GC/MS system included: Entech 7100 prec oncentrator, Varian 3800 gas chrom atograph with FID and colum n switching valve, and Vari an Saturn 2000 ion trap m ass spectrometer. The Entech preconcen trator consisted of three traps: 50% glass beads/50% Tenax, held at –

100 ° C during sample transfer, 100% Tenax held at –40 ° C and a final focusing trap (a piece of silico-steel capillary) held at –180 ° C. The sample is desorbed from the first trap at 10 ° C, from the second trap at 200 ° C and from the third one at approxim ately 70 ° C to a transfer

line heated to 110 ° C and connected to the h ead of the first column. The sample was injected
at the head of a 60 m x 0.32 mm polymethylsiloxane column (C PSil-5, Varian, Inc.) held at

30 ° C. This column was connected to the switching valve lead ing into a 30 m x 0.53 mm GSGasPro column (J&W Scientific). After approxi mately 7 min the valve was switched so that
the effluent from the first colum n eluted onto a second 15 m x 0.32 mm polymethylsiloxane column connected to the mass spectrometer. The column switch was timed so that the C2 and C3 com pounds eluted on the FID and all C4 and higher com pounds eluted on the m ass spectrometer. The GC program was as follows: 30 ° C held for 2 m in, then 8 ° C/min up to

260 ° C.

Calibration of the system was conducted with a mixture that contained the m ost commonly found hydrocarbons (75 com pounds from e t hane to n-undecane, p urchased from Air Environmental), MTBE, and halocarbons (23 co mpounds from F12 to the dichlorobenzenes, purchased f rom Scott Specialty Gases). The st andards were prepared in 6 L Silco-Steel

2-6

### canisters (Restek, Bellefonte, PA) by mixing three different standard s through a multi-valve manifold us ing a Baratron absolute capacita nce m anometer (MKS Instrum ents, Andover, MA) to determ ine the pressu re each standard added to the m ixture. Prior to m ixing, approximately 0.2 m l of ultrapure water was ad ded to the canister to hum idify the m ixture (for mixture stability). The concentrations in the mixture were in the range of 0.2 to 10 ppbv. Three point external calibrations were run pr ior to analysis, and one calibration check was run every 24 hours. If the response of individu al compounds were m ore then 10% off, the system was recalibrated.

Carbon dioxide (CO2) f rom breath sam ples was determined using GC/FID. Since the FID does not respond to CO and CO2, these species are converted to m ethane by a m ethanator, positioned after the GC column, but ahead of the FID. The methanator comprises a firebrick powder im pregnated with nickel catalyst, th rough which a stream of hydrogen gas flows continuously at ~550 °C. For compound separation, a 20-foot x 1/8-inch inner-diameter (i.d.) column, packed with a 60/80 m esh of Carb oxen 1000 (Supelco) is used. This column provides sufficient separation between CH4 a nd CO, without retaining CO2. Five m l samples were injected using a constant vo lume loop. The minim um detection lim it for both CO and CH4 is ~20 ppbv, whereas for CO2 it is ~3 ppmv. The precision of measurements is generally better than 10%.

2.3.2 SPME Methodology

During the Reno 2nd pilot project, SPME fibers were calibrated and an alyzed as described before (Zielinska et al, 2002, 2003). However, the gas calibrat ion had to be corrected for temperature, since s tatic (Tedlar b ag) calibrati on is perform ed at room (25o C) tem perature and the sampling tem perature ran ged from 4o C to 30o C (average 16o C). At lower temperature the fiber uptake is higher, theref ore SPME values were expected to be higher than canister data. The tem perature correction factors were obtained experim entally in the laboratory in a dynam ic flow-through system cons tructed for the control of te mperature and humidity of certified BTEX standards. Hum id ity corrections are not a ddressed in this report because the experimental data obtained so far do esn’t show a significant change in the SPME response due to the change in humidity.

2.3.2.1 Temperature and Humidity Calib ration Experimental Setup

Figure 2.3-1 shows the experim ental setup fo r tem perature and hum idity calibration. It consisted of a 1L glass bulb that had two stop cocks on each side to let the calibration gas flow through and an injection po rt covered with a sl eeve septum to allow the introduction of a SPME fiber. The bulb was tem perature contro lled with a cooling/ heating system. The temperature inside the glass bulb was m easured with a therm ocouple. For introducing the desired humidity, a heated inject ion port was added before the gl ass bulb entrance in order to inject water with a syringe pum p (Harvard Apparatus), Ludovic et al., 2001; Nelson, 1992; McLaren and Zhou, 2000; Martos and Pawlis zyn, 1997). The water-dispensing rate can be
calculated from the theoretical saturation ratio obtained from a skew T diagram:

RH = 100 w/ws

2-7

### ws = ws(T,P) w is set with the water-dispensing rate as g water/Kg air=RH*ws/100

The experimental humidity was measured with a humidity se nsor (Dickson FH121).

Data from the static calibration was com pared to the data obtained in the dynam ic system to
determine a correction factor that could be applied to the sam pling data. Tedlar bag calibrations are valid for the type of envir onments we are m easuring where wind should not exceed 4 m iles/hour. However, tem perature calibration is a b etter approached in a d ynamic system because tem perature is the only variab le that chan ges, while in a static s ystem pressure and volum e must be adjusted as explained by the ideal gas law and makes the system very imprecise. Some advantages of a dynamic system are greater reproducibility and stability of the standards at lower con centration ranges (Nelson, 1992; Lodge 1984).

2-8

### Figure 2.3-1. Set-up for tem perature (upper pane l) and relative hum idity (lower panel) dependence measurements

2-9

### 2.3.2.2 SPME Temperature Dependence

PDMS coating has a sm all decrea se in the response of organics for sam ples with relative humidity close to 100%. The prim ary experim ent al param eter that control the response is temperature. In theory , the effect of te mperature on the distribution constant can be predicted, since log(Kf g) is linea r with 1/T a nd the heat of vaporization of the pure solvent (Kfg – partition coef ficient). In othe r words, Kfg can be calculated f or the given sa mpling conditions (Pawliszyn, 2002). This theoretical a pproach is based on th e liquid properties of the PDMS coating in th e fiber. However, in practice the theory doesn’t satisfactorily match the exper imental va lues. Theref ore, we perf ormed more experim ents and utiliz ed the experimental approach.

Standards were m easured at different tem p eratures using the dynamic system described above and results were com pared to those obtained in a room temperature static calibration. The experiments were performed at different B TEX concentration levels, as shown in figure

2.3-2. Temperature dependence for 30 ppb BTEX

0 2000 4000 6000 8000 10000 12000 14000

0 1 0 2 0 3 0 4 0 5 0 Temperature (C)Area Counts

Benzene Toluene Ethylbenzene m,p-xylene o-xylene

Temperature Dependence for 50 ppb BTEX

0 4000 8000 12000 16000 20000

0 5 10 15 20 25 30 35 40 45 Temperature, CArea Counts

benzene toluene ethylbenzene m,p-xylene o,xylene



### Figure 2.3-2. Temperature Dependence fo r 30, 50, and 100 ppb BTEX Concentrations.

2-10Temperature Dependence for 100 ppb BTEX

0 5000 10000 15000 20000 25000 30000

0 10 2 0 3 0 40 5 0 Temperature, CArea Counts

bezene toluene ethylbenzene m,p-xylene o-xylene 

### Figure 2.3-2–cont’d. Tem perature De pendence for 30, 50, and 100 ppb BTEX
Concentrations.

These data can be plo tted by tem perature in order to obtain a li near relationship with concentration as in Figure 2.3-3.

Benzene Temperature Dependence

y = 188.38x

R

2 = 0.7134

y = 128.92x

R

2 = 0.5189

y = 107.17x

R

2 = 0.7398 0 5000 10000 15000 20000 25000

0 20 40 60 80 100 120 Concentration, ppbArea COunts

10 C 25 C 40 C Linear (10 C) Linear (25 C) Linear (40 C)

Toluene Temperature Dependence

y = 178.81x

R

2 = 0.9227

y = 127.49x

R

2 = 0.784

y = 99.57x

R

2 = 0.5472
0 5000 10000 15000 20000

0 20 40 60 80 100 120 Concentration, ppbArea COunts

10 C 25 C 40 C Linear (10 C) Linear (25 C) Linear (40 C)



### Figure 2.3-3. Concentration calibration at a given temperature for the BTEX compounds.

2-11Ethylbenzene Temperature Dependence

y = 85.481x

R

2 = 0.7776

y = 63.1x

R

2 = 0.3382

y = 46.488x

R

2 = 0.6668

0 2000 4000 6000 8000 10000

0 20 40 60 80 100 120 Concentration, ppbArea COunts

10 C 25 C 40 C Linear (10 C) Linear (25 C) Linear (40 C)

m,p-xylene Temperature Dependence

y = 153.11x

R

2 = 0.7653

y = 108.77x

R

2 = 0.6097

y = 84.309x

R

2 = 0.6317

0 5000 10000 15000 20000 25000 30000 35000

0 50 100 150 200 250 Concentration, ppbArea COunts

10 C 25 C 40 C Linear (10 C) Linear (25 C) Linear (40 C)

o-xylene Temperature Dependence

y = 230.24x

R

2 = 0.8262

y = 148.82x

R

2 = 0.8426

y = 116.78x

R

2 = 0.8967 0 5000 10000 15000 20000 25000

0 20 40 60 80 100 120 Concentration, ppbArea COunts

10 C 25 C 40 C Linear (10 C) Linear (25 C) Linear (40 C)



### Figure 2.3-3-cont’d. Concentration calibrati on at a given tem perature for the BTEX compounds.

2-12

### Furthermore, we plotted the slope s from this li near relationship vs. te mperature in order to analyze the SPME response for a given temp erature. Figure 2.3-4 shows the linear relationship between the slopes at different temperatures.

y = -3.7813x + 259.81

R 2 = 0.9405 y = -2.2933x + 172.73

R 2 = 0.9731 y = -1.2997x + 97.515

R 2 = 0.9928 y = -2.6413x + 201.32

R 2 = 0.9718 y = -2.707x + 209.17

R 2 = 0.9329

0 50 100 150 200 250

0 5 10 15 20 25 30 35 40 45 Temperature (C)Slope (AC/Conc)

benzene toluene ehtlybenzene m,p-xylene o-pylene

Linear (o-pylene) Linear (m,p-xylene) Linear (ehtlybenzene) Linear (toluene) Linear (benzene) 

### Figure 2.3-4. Dynamic Calibra tion Temperature Dependence

From this dynam ic temperature calibration we correlated the three variables analyzed (such as area cou nts, tem perature, and concentratio n) and calculated the concentration of the sample by the area counts from the analysis an d the sampling temperature. Furthermore, we compared the 25C dynam ic and static calibrati ons and extrapolated the other temperature GC/PID responses in obtaining figure 2.3-5.

y = -1.1463x + 78.761

R 2 = 0.9405 y = -0.5057x + 37.946

R 2 = 0.9928

y = -0.8207x + 61.813

R 2 = 0.9731 y = -0.7906x + 60.259

R 2 = 0.9718 y = -0.8336x + 64.411

R 2 = 0.9329

0 10 20 30 40 50 60 70 80

0 1 0 2 0 3 0 4 0 5 0 Temperature, CSlope (AC/C)

benzene toluene ethylbenzene m,p-xylene o-xylene

Linear (o-xylene) Linear (ethylbenzene) Linear (m,p-xylene) Linear (toluene) Linear (benzene)



### Figure 2.3-5. Static Calibrat ion Temperature Dependence (B y interpolation from dynam ic system)

2-13

### The equations that result from these extrapolations are the following:

STATIC SYSTEM (INTERPOLATED FROM DYNAMIC SYSTEM)

Component equation correl 

### Concentration
benzene y = -0.8336x + 64.411R2 = 0.9329AC/( -0.8336T+64.411) toluene y = -0.7906x + 60.259R2 = 0.9718AC/( -0.7906T+60.259) EtBenzene y = -0.5057x + 37.946R2 = 0.9928AC/(-0.5057T+37.946) m/p-xylene y = -0.8207x + 61.813R2 = 0.9731AC/( -0.8207T+61.813) o-xylene y = -1.1463x + 78.761R2 = 0.9405AC/(-1.1463T+78.761)

AC/C=aT+c C=AC/(aT+c)



### 2.3.2.3 SPME Humidity Dependence

Chai and Pawliszyn, 1995, performe d several experiments in order to determine the influence of humidity for the 100 μ m PDMS response factor. Humidity usually decreases the response factor of each individual com pound. The lower response depends on temperature. At lower temperatures, the humidity has a larger decrease in the response factor of a compound. Some compounds are not greatly affected by hum idity. The highest effect of humidity seems to be an approxim ately 25% decrease when going fr om dry air at 0C-10C into 25% rela tive humidity. Changes of the area counts at rang es of tem perature of 0C-25C for changes in relative hum idity from 25%-75% are alm ost ne gligible (also discussed by Parreira et al, 2002).

It is understood that hum idity a ffects the fiber response because water at high concentrations is completely adsorbed into the coating of the fiber.

Initial data from the experimental se t up described earlier is shown below:

0 5000 10000 15000 20000 25000

0 10 20 30 40 50 60 70 80

Relative Humidity (%)Area Counts

Benzene Toluene ehtylbenzene m,p-xylene o-xylene



### Figure 2.3-6. Hum idity Dependence on SPME response for a 100ppb BTEX standard at

25C.

2-14

### Current experim ents at 25C determined that hum idity in the BTEX compounds does not affect the GC/PID respo nse significantly, although is lowers the respon se slightly at RH >

75% .

2.4 Data Capture

The overall data capture rate for all the 2 nd 

### Reno Pilot Study m easurements is provided in Table 2.4-1, with the co mplete details for each ME presen ted in Appen dix A. Overall the data capture for the in tegrated methods was nearly com plete . Only one solid adorbent tube was lost to breakage. The “Refuel Can” in Table 2.4-1 refers to the 5-minute integrated canister co llected durin g the actu al refueling event. One canis ter cou ld not be s ampled because it was at atm ospheric pressure when opened in the field, and the data obtaine d from the other one were invalidated, thus leading to a 80% capture rate for this category. The “Breath Can” refers to the breath canisters (2 or 3 per ME) which were all co llected. For the continuous and semi-continuous methods, we had very good data captur e with only one run missing for the Outside PID (the one m easuring outside the vehicle cab in during the freeway ME). This was due to a software difference between this and our older instrum ent that resulted in the data logging function being accide ntally turned off. The NDIR instrument lost some data due to insuf ficient power in a f ew early runs; fortunately the T-15 CO functioned perfectly for these runs. For the few runs wher e the T-15 CO data loggi ng had problems, we
have the NDIR data thus at l east one instrument was functioni ng for CO during all MEs. The MS200 worked very w ell du ring most of the early runs, but som e detector sen sitivity problems and other undiagnosed problem s resulted in complete loss of data for the last four runs. One freeway run had m ostly good data with 5 m inutes out of the 40 m inute total being
lost due to electrical noise of undetermined origin. This is a similar problem we had during the San Antonio study and m ay be related to the van’s electrical system since proxim ity to the other instruments in the refueling MEs did not cause similar noise.

The formaldehyde instrument showed some good da ta but overall data capture rate was low , mostly due to an electrical shortage in the thermocouple that controls th e heated reaction cell. This problem was not identified and fixe d until th e afternoon of May 2, 2003. W ithout adequate control of the temperature of the heated reaction cell, there is little certainty that the formaldehyde collected was actua lly derivatized in a consistent m anner. This m alfunction was diagnosed and fixed prior to the parking garage sample ME2-4, and did not reoccur. Another major source of m alfunction was the pres ence of air in the sample stream reaching the detector. Although an in-line debubbler wo rked well for rem oving air bubbles from the sample stream, air m ay still have r eached the detector if pump flow rates were not properly balanced among the 4 pum ps and air was accidentally pum ped into the detector. This occurred during the freeway (ME1-5) and refuel ing without vapor recovery (ME4-4) tests on May 5, 03. Another limitation of this continuou s instrument was the long stabilization time required for the fluorescence dete ctor upon instrum ent start-up. In some cases, response at the dete ctor was still stabiliz ing when the sampling period began. One of the m ost significant lim itations o f the for maldehyde m o nitor was an apparen t sensitiv ity to moving
environments. It has been observed that when the formaldehyde instrument was warmed up and operated in a stationary e nvironment, such as a parkin g garage, and then subjected to transport w hile still operating, re sponse at the detector oscillat ed and increased in overall.

2-15

### Figure 2.4-1 shows the response of the contin uous for maldehyde analyzer, stabilized and “zeroed” with a DNPH cartridge at the inlet, when statio nary and following startup and driving of the sampling van where the response of the detector incr eases and oscillates.(V)ponCHOH

-0.2 -0.1

0 0.1 0.2 0.3 0.4 0.5 0.616:40:4816:48:0016:55:1217:02:2417:09:3617:16:4817:24:0017:31:1217:38:2417:45:3617:52:48

TimeRes se installed DNPH on inlet

at 17:22 and continued sampling in garage Started van and drove back to
DRI, DNPH still on inlet and still acquiring



### Figure 2.4-1. Effect of driving on continuou s for maldehyde analyzer, during and after sampling in ME2-5.

The environm ental conditions (temperature, relative hum idity, position, speed and other parameters) had one run where the logging system apparently locked up about 6 m in into the run and gave no further data. This was a 20 min refueling run and does not represent a significant loss in data since th e tem peratur es and hum idity probably did not change appreciably.

Table 2.4-1. Data Capture Summary

Paramete r Data Capture

Ambient Can 100%

Refuel Can 80%

Breath Can 100%

DNPH 100%
Solid Ads. 95%
SPME 100% PID In (1) 100% PID Out (2) 80%

NDIR CO 85%
T-15 CO 85%
MS200 70% Formaldehyde 10%

Env. Cond. 95%



### 2-16

## 3. RESULTS

The m ain goal of the 2 nd 

### Reno Pilot Study was to demonstrate proper operation and reliability of analytic al ins trumentation and com parability of tim e-integrated, sem icontinuous and continuous methods for compounds of interest. The results section examines the consistency between redundant m easurements and co-pollutants, evaluates tem poral and spatial variations, and correlations among the vari ous data sets for measured parameters that we expect will be correlated. One key aspect of the study des ign was the built-in redundancy
between the continuous m ethods and the tim e -integrated m ethods. For exam ple, CO was measured from the tim e-integrated canis ter sam ples and from the T-15 and NDIR
instruments. We measured BTEX fr om canis ters, continuous MS-200 and semi- continuous SPME as well as a surrogate m easure in the PID signal. F o rmaldehyde was measured by the continuous HCHO instrum ent and by the DNPH car tridges. In additio n, we m easured PID signal from two independent ppbRAE units p os itioned in -cabin and outside the cabin, o r
collocated in outdoor microenvironments.

3.1 Method Comparison of Redundant Data

3.1.1 PID versus PID

Two identical ppbRAE continuous PID mon itors were used to estim ate total VOC concentrations, ionizable at 10.6 eV, inside and outside the ve hicle cabin. Prio r to and after the pilot study, both units were ca librated using an activated car bon inlet filter for the zero point and a certified BTEX mixture (tot al concentration 3700 ppb) for span.

During several tests, the second unit was collocated with its inlet within 10 cm of the inlet of the primary unit for quality assurance purposes. The resulting data is s hown in Fig ure 3.1- 1a,b. While the two units track each other accurate ly, after adjusting for differences in in let transit tim e, the abso lute concen trations r ecorded differ significantly. The prim ary unit (PID1) demonstrated a positiv e offset of 40-50 ppb, which was expected since it w ould not read below ~40 ppb eve n when the carbon inlet filter was in place. This behavior is eviden t in the tests shown in Figure 3.1-1b. No consis tent bias was observed at the high peak concentrations shown in Figure 3.1-1a, with bot h units reading higher at tim es. Since this time a dif ference in sof tware was identif ied, and they h ave been h armonized for future
studies.

3-1M E4 - Refueling w/o VR: test4

0 1000 2000 3000 4000 5000 6000 7000 8000 9000

0 51 0 1 5

elaps ed tim e (m in)BTEX estimated by PID (ppb)

P ID1 PID2

2 0

M E4 - Refueling w/o VR: test5

0 5000 10000 15000 20000 25000 30000

0 5 10 15 20

ela pse d tim e (m in)BTEX estimated by PID (ppb)

PID 1 PID2



### Figure 3.1-1a. Comparison of estimated BTEX concentrations measured by PID instruments
with inlets collocated within 10 cm. Data ar e running 1 minute averages. VR = nozzle vapor

recovery.

3-2ME3 - Refueling w/ VR: test5

0 5 0 100 150 200 250

0 51 0 1 5

e la pse d tim e (m in)BTEX estimated by PID (ppb)

PID1 PID2

2 0

ME2 - Parking Garage: test5

0 10 20 30 40 50 60 70 80 90 100

0 51 0 1 5

e la pse d tim e (m in)BTEX estimated by PID (ppb)

PID1 PID 2

2 0



### Figure 3.1-1b – cont’d. Com parison of estim at ed BTEX c oncentrations measured by PID
instruments with inle ts collocated within 10 cm . Data are run ning 1 m inute averages. VR = nozzle vapor recovery.

3-3

### Figure 3.1-2 shows the corresponding total VOC conce ntrations, ionizable at 10.6 eV, recorded by the two p pbRAE monitors during four freeway driving tes ts (d ata f or the ambient unit during test 2 was lost due to a da ta logger configuration error) where the second
unit m easured am bient VOC conce ntrations outs ide the vehicle. As in the collocated unit tests, the two monitors track e ach other well during the high ventilati on segment of the test (first 20 minutes). The less dynamic variations in concentration recorded by the in-cabin unit are consistent with expectations.

After the switch to low ventilat ion conditions at 20 m inutes el apsed time, the in-cabin unit shows very little correl ation to the am bient unit and, while not always stable, shows no accumulating drift evidence of interi or sources or interferences.

3-4ME1 - Freeway: test3

0 100 200 300 400 500 600 700 800 900

0 5 10 1 5 20 2 5 30 35 40

e la psed tim e (m in)BTE X estim ated by P ID (ppb) in-cabin PID ambient PID ME1 - Freeway: test1

0 200 400 600 800 1000 1200

0 5 10 15 2 0 25 30 35 40

elaps ed tim e (m in)BTEX estim ated by P ID (ppb) in-cabin PID ambient PID



### Figure 3.1-2. Com parison of estimated BTEX concentrations measured by PID instrum ents during freeway driving tests. Da ta are running 1 minute averages.

3-5ME1 - Freeway: test4

0 100 200 300 400 500 600 700

0 5 10 1 5 20 25 30 35 40

elapse d tim e (m in)BTEX estim ated by PID (ppb) in-cabin PID ambient PID

ME1 - Freeway: test5

0 100 200 300 400 500 600

0 5 10 15 20 25 30 35 40

elaps ed tim e (m in)BTEX estimated by PID (ppb) in-cabin PID ambient PID



### Figure 3.1-2 –cont’d. Com parison of estim ated BTEX concentrations m easured by PID instruments during freeway driving test s. Data are running 1 minute averages.

3-6

### 3.1.2 NDIR vs. Electrochemical CO

Both an EPA-certified gas-filt er correlation NDIR optical CO analyzer (API model 300) and a portable battery-operated pass ive electrochem ical cell instrum ent (Langan T-15) were operated during all tests to measure CO. Although data recovery was less than 100% for each method, and the electrochemical instrument was not equipped to sample outside the in-cabin breathing zone during the refueling and garage te sts, collocated measurements were collected during the two tests shown in Figure 3.1-3.

Although the NDIR instrum ent recorded higher p eak values, due to its faster reponse tim e, the measurements are generally consistent to within about 1 ppm. During the low-ventilation,
half of the tests shown the CO concentrations remain at or d ecrease towards the lowest level measured during the high-vent phase. This beha vior suggests that no in-c abin so urces o r interferences are present.

There was good agreem ent betwe en the two types of CO analyzers, due to the NDIR instrument’s internal adaptive filtering. This f ilter, which is required for EPA certification, is intended to adjust the response ra te of the instrum ent with respect to the stability of the raw detector signal during a precedi ng time period, to reduce no ise. The len gth of the ‘filtering ’ period can range from 10 seconds up to 2 minutes , according to the manufacturer. In practice, the adaptive filter effectively averag es the out put data over a variable tim e period, resulting
in concentration fluctuations that are broader and have a peak th at occurs later in tim e and a lower maximum height. This effect can be s een in Figure 3.1-4, whic h shows the measured
CO concentrations from two si milar instrument s drawing air from the sam e inlet ins ide the cabin of the test van while driving o n freew ay and surface streets with windows open (this test was pe rformed later in the d ay than the ME1 tests, concentr ations are low er). The API300 was the same instrument used in the pilot study, while the ML9830 (Monitor Labs) was an equivalent EPA-certif ied gas -filter co rrelation NDIR instrum ent that was operated with the ad aptive filter turned off (a fixe d 10 second filtering period was selected). Both instruments have the sa me performance specifications and were calib rated just pr ior to the test using zero air and a 10.0 ppm CO standa rd, yet the ML9830 tim e series is m uch more dynamic and shows higher peak concentrations. Figure 3.1-4 also shows a tim e series of the ML9830 data in which the four minutes preceding each data point were averaged. This series matches the API300 data almost exactly, except for the first large peak which was apparently steep enough to trigger the API300’s adap tive filter into fast response mode.

Despite the differences in response rate, the ov erall average concentrat ions recorded for the test period shown were very com parable: 1.26 ppm from the ML9830 versus 1.31 ppm from the API300. Fast response is desired in order to better characterize the variability of pollutant concentrations in a m icroenvironment, so the ML9830 is preferable for the field study. In addition to the convenience of front panel conf iguration of t he data filter, the ML9830 also uses about 50% less power and has an internal ze ro air generator to allow automatic baseline
checks.

3-7ME1 - Freeway: test3

0 5 10 15 20 25 30 35 40 45 50

0 5 10 15 20 25 30 35 40

elapsed tim e (m in)CO (ppm) ND IR_CO Langan_CO

ME1 - Freeway: test4

0 2 4 6 8 10 12 14

0 5 10 15 20 25 30 35 40

elapsed tim e (m in)CO (ppm) NDIR_CO Langan_CO



### Figure 3.1-3. Com parison of NDIR (API m odel 300) and electrochem ical (Langan T15v) CO monitors during two freeway driving tests.

The NDIR CO data are running 1 m inute averag es, while the electrochem ical instrum ent recorded data is in discrete 1 minute averages. In test 3, the NDIR inst rument’s analog output range (0-20 ppm) was exceeded during the first 4 minutes.

3-8024681012 15:40 15:45 15:50 15:55 16:00 16:05 16:10 16:15 16:20

CO (ppm )ML9830API300ML9830_4min.AvgFigure 3.1-4. Comparison of two gas-filter correlation NDIR CO analyzers during on-road sampling.Data from the ML9830 instrument are shown as recorded(10 second averages) and as4 minute running averages.3-9

### 3.1.3 CO versus Canister CO

Average CO concentrations were also m easured by GC analysis of the integ rated canis ter samples that were collected for the d uration of each test. Figure 3.1-5 shows a scatter plot of the average continuous data from t he NDIR or electrochemical CO i nstruments versus the CO from the corresponding canister. The canister CO is generally about 8% higher, but there is no consistent bias. The com parison is also ma de on a test-by-test basis in the second chart of this figure, showing that discrepanc ies between the two methods occur in all microenvironments and at both high and low co ncentrations. The underestimation of CO by
the NDIR instrument in the two tests with the highest average concentration (ME1- test 3 and ME2 – test 2) is due, at least in part, to exceed ences of the instrum ents output rang e which resulted in truncation of peak concentrations abov e about 23 ppm. This over-ranging problem
was identified and corrected befo re the end of the pilot study.

3-10y = 1.08x

R 2 = 0.85

0 2 4 6 8 10 12

0 2 4 6 8 10 12

average of continuous COCa nister CO



### 0 2 4 6 8 10 12

ME1 ME2 ME3 ME4CO (ppm) 

### average of continuous CO

Canister CO



### Figure 3.1-5. Average CO concentration for each test measured by continuous m onitor and GC analysis of integrated canister sample. ME1= morning rush hour commute; ME2=parking garage; ME3= refueling with va por recovery; ME4= refueling without vapo r

recovery.

3-11

### 3.1.4 MS vs. Canister

The MS200 performed well in 16 of the 20 ME test s. For all of those runs we can com pare the integrated MS200 response to the caniste r data. Figure 3.1-6 shows the correlation for benzene, toluene and the sum of the C8 benzenes (ethylb enzene, o, m, & p-xylene). The C8 benzenes are presented together because we cannot separate them us ing the MS 200. The correlations are all very good, with > 0.9 R-square . The correlation for toluene is the best with a 0.99 R-square. B oth toluene and the C8 benzenes show a clos e 1:1 correlation, but benzene seems to be overpredicted by the MS200.

Bz = 1.1537x + 1.0948

R 2 = 0.9016

Tol = 0.9703x + 1.8068

R 2 = 0.9914

C8 = 1.0638x + 0.6664

R 2 = 0.9529

0 10 20 30 40 50 60 70 80

0 2 0 4 0 6 0 8 0

Canister, ppbvMS200, ppbv Benzene

Toluene

C8 Benzenes
Linear (Benzene)
Linear (Toluene)
Linear (C8 Benzenes)



### Figure 3.1-6 Comparison of canister and MS 200 data for all measured species.

To further investigate the com parison for benzen e, we plotted the benzene concentrations in Figure 3.1-7. This figure shows random sca tter around the trend line over the range of 25 ppbv down to less than 2 ppbv. Overall the MS200 performed very well for runs with valid data. We are still inves tigating the causes of th e failures of this instru ment and f eel that it provides excellent supplemental data but s hould not be relied upon as a primary method.

3-12Bz = 1.1537x + 1.0948

R 2 = 0.9016

0 5 10 15 20 25 30

0 5 10 15 20 25 30

Canister, ppbvMS200, ppbv

Benzene
Linear (Benzene)



### Figure 3.1-7. Comparison of MS200 and canister for benzene only.

3.1.5 SPME vs. Canisters

Table 3.1-1 shows the com parison of canister B TEX data with averaged and temperature corrected S PME data. In general, SPME BT EX concentrations are higher than canis ter concentrations. This is most probably due to the temperature differences between the sta tic calibration and sampling conditions and inadequate correction for temper ature. However, the passive SPME sampling rate coul d also be affected by the local wind speed, especially if the local gusts are close to 5 mph threshold. We observed higher SPME uptake of analytes in the dynamic system, if the flow rate of a standa rd gas mixture was higher than 100 ml/min.

After clean ing and con ditioning, th e SPME fibers were sto red in the freezer and taken to sampling sites in a cooler with dr y ice. Although the fibers were taken out of th e cooler prior to sam pling, we are no t ce rtain if suf ficient tim e was allowed f or f iber equ ilibrations to ambient temperature. In retrospect, it was an e rror, since we dete rmined later that the f iber uptake is highly dependent on temperature (see Section 2.3.2). For the primary study we will change the SPME f iber storage con ditions and w ill store them in m etal cans with activa ted charcoal at the bottom (similar to Te nax tubes) at ambient temperature.

3-13Table 3.1-1. Data comparison between SPME and Canistercan spme can spme can spme can spme can spmesite datestrthhmm benze benze toluetolue etbz etbz mp_xyl mp_xyl o_xyl o_xylFreeway4/29/03742-822 9.10 15.03 45.35 87.42 7.48 18.37 24.92 50.53 9.94 15.96Refueling W/Vapor Recovery 4/29/031200-1220 3.38 11.94 9.91 52.85 1.43 10.70 4.82 27.04 1.85 10.03Garage4/29/031642-1712 5.65 19.00 14.67 56.49 3.10 16.11 10.52 43.12 4.20 14.04Freeway4/30/03739-819 10.01 24.01 53.75 127.78 8.69 25.11 29.48 72.93 11.74 23.15Refueling W/O Vapor Recovery 4/30/03921-941 9.46 29.04 34.27 112.88 5.50 18.02 19.02 66.76 7.31 19.75Refueling W/Vapor Recovery 4/30/031045-1105 1.30 4.66 4.53 20.46 0.97 6.93 3.50 19.48 1.47 5.00Refueling W/O Vapor Recovery 4/30/031205-1245 2.13 11.02 7.85 51.68 1.15 14.11 3.96 31.28 1.52 7.29Garage4/30/031645-1715 9.94 37.25 31.92 110.84 6.98 26.43 24.06 87.42 9.75 31.54Freeway5/1/03720-800 18.13 32.60 75.57 146.83 12.28 26.77 40.13 84.28 15.46 28.29Refueling W/O Vapor Recovery 5/1/031106-1126 2.34 6.80 10.10 49.24 1.83 14.57 6.48 39.62 2.51 10.41Refueling W/Vapor Recovery 5/1/031225-1245 1.61 5.61 6.28 17.02 1.20 4.60 4.21 13.58 1.68 3.23Garage5/1/031642-1717 10.63 20.33 34.25 71.17 7.23 13.91 25.35 45.99 9.81 15.34Freeway5/2/03735-815 7.27 22.62 30.81 114.78 4.77 24.76 15.66 67.07 6.09 21.03Refueling W/O Vapor Recovery 5/2/03918-938 20.49 44.77 59.93 154.25 8.13 31.25 28.70 92.90 10.71 29.19Refueling W/Vapor Recovery 5/2/031036-1056 2.30 20.44 9.28 67.20 2.10 12.17 7.83 42.82 3.06 12.74Garage5/2/031645-1715 5.29 6.07 17.10 22.80 3.79 5.55 13.53 15.84 5.36 4.58Freeway5/5/03750-830 9.60 19.25 44.69 108.01 8.31 18.21 28.76 63.52 11.35 20.17Refueling W/O Vapor Recovery 5/5/03923-943 66.93 52.76 142.14 198.26 11.17 18.30 36.03 63.81 11.75 16.26Refueling W/Vapor Recovery 5/5/031045-1105 1.55 5.75 7.23 18.13 1.39 2.49 4.96 9.74 1.91 2.09Garage5/6/031645-1715 4.86 6.29 14.16 22.39 3.25 5.82 11.75 20.92 4.55 6.853-14

### Figure 3.1-8 shows the scatter plots for canis ter and S PME data before temperature
corrections.

0 50 100 150 200 250

0 50 100 150 200 250 Canister Concentration (ppb)SPME Concentration (ppb)

benzene toluene ethylbenzene m,p-xylene o-xylene


### Figure 3.1-8. Scatter Plots for raw data fr om SPME vs canister for the Pilot Study 2003

Scatter plots after temperature correction.

0 50 100 150 200

0 50 100 150 200 Canister Con centratio n (p pb)SPME Con centration (pp b)

benzene toluene ethylbenzene m,p-xylene o-x ylene



### Figure 3.1-9. Scatter Plots for temperature corrected SPME vs canister data for the Pilot Study 2003

Figure 3.1-10 and Table 3.1-2 show s the correla tions after removing th e two visible outliers (benzene and toluene from refueling w/ o vapor recovery May 5th at 923-943):

3-150 40 80 120 160

0 40 80 120 160 Canister Con centratio n (p pb)SPME Con centration (pp b)

benzene toluene ethylbenzene m,p-xylene o-x ylene



### Figure 3.1-10. Scatter plots from SPME vs Canister for the Pilot S tudy 2003 with two
outliers removed.

Table 3.1-2. Correlation of Scatter Plot s from SPME and Canister Comparison

Compound Equation Correlation Benzene y = 1.8365x + 4.9732 R 2 = 0.7291 Toluene y = 1.9202x + 22.617 R 2 = 0.7936 Ethylbenzene y = 1.6894x + 7.1997 R 2 = 0.5255 m,p-xylene y = 1.7814x + 17.323 R 2 = 0.6452 o-xylene y = 1.6367x + 4.0433 R 2 = 0.6526



### The scatter plots show linearity of the SPME data compared to canister data but the relatively
low correlation values and the slope in the range of 1.6 – 1.9 can be associated with the differences in storage of the c onditioned fibers before sampli ng. As noted above, m ost fibers were not probably stabilized to am bient temper ature before sam pling. Since the fibers were colder than the environ ment, so me variability of the data is expected. This proble m will be corrected in the primary study.

Sampled fibers were s tored an average of 5 hours and all s amples were analyzed the same sampling day.

3-16

### 3.1.6 SPME vs. MS

Data from SPME se mi-continuous sam ples compar ed satisfactorily with continuous data obtained from the MS 200. In general concentra tions are within the same ranges and changes
in concentration levels track each other most of the time. However, the SPME concentrations are higher in m ost cases. As explained before, this may be due to the inadequate c orrection for temperature and hu midity differences as co mp ared with static calibration conditions and cold fiber storage conditions prior to sampling.

3-17Ethylbenzene and xylenes

0 40 80 120 160

7:30:43 7:37:55 7:45:07 7:52:19 7:59:31 8:06:43 8:13:55 8:21:07

TimeConcentration, ppb

MS SPME

Benzene

0 10 20 30

7:30:43 7:37:55 7:45:07 7:52:19 7:59:31 8:06:43 8:13:55 8:21:07

TimeConcentration, ppb

MS SPME

Toluene

0 40 80 120 160

7:30:43 7:37:55 7:45:07 7:52:19 7:59:31 8:06:43 8:13:55 8:21:07

TimeConcentration, ppb

MS SPME



### Figure 3.1-11. 10 m inutes average MS data vs SPME benzene and toluene concentrations: Freeway 5/02 7:35-8:15 am

3-18Benzene

0 10 20 30 40

7:33:36 7:40:48 7:48:00 7:55:12 8:02:24 8:09:36 8:16:48 8:24:00

TimeConcentration, ppb

MS SPME

Toluene

40 80 120 160

7:33:36 7:40:48 7:48:00 7:55:12 8:02:24 8:09:36 8:16:48 8:24:00
TimeConcentration, ppb

MS SPME

Ethylbenzene and xylenes

0 40 80 120 160

7:33:36 7:40:48 7:48:00 7:55:12 8:02:24 8:09:36 8:16:48 8:24:00
TimeConcentration, ppb

MS SPME



### Figure 3.1-12. 10 m inutes average MS data vs SPME benzene and tolu ene concentrations: Freeway 4/30, 7:35 am

3-19benzene

0 30 60 90

9:15:50 9:18:43 9:21:36 9:24:29 9:27:22 9:30:14 9:33:07 9:36:00 9:38:53

TimeConcentration, ppb

MS SPME

Toluene

0 50 100 150 200 250 300

9:15:50 9:18:43 9:21:36 9:24:29 9:27:22 9:30:14 9:33:07 9:36:00 9:38:53

TimeConcentration, ppb

MS SPME

Ethylbenzene and xylenes

0 50 100 150 200 250 300

9:15:50 9:18:43 9:21:36 9:24:29 9:27 :22 9:30:14 9:33:07 9:36:00 9:38:53

TimeConcentration, ppb

MS SPME



### Figure 3.1-13. 10 m inutes average MS data vs SPME benzene and toluene concentrations: Refueling w/o VR 5/02 9:18 am

3-20

### 3.1.7 DNPH vs. Formaldehyde

Comparisons of for maldehyde data are few si nce the supplem ental continuous analyzer provided little reliable data due to flow fluxuation and unstability during movem ent Comparison of formaldehyde data from DNPH w ith the final garage sampling event (ME2-5) shows that average concentrati on of formaldehyde detected by the continuous instrument was 11.5 ppb, and the tim e integrated D NPH sample for the sam e event was only 5.41 ppb. I f
data from the continuous CO m onitor from th e sam e experim ent is used to reconstruct concentrations of formaldehyde for the earlier portions of the run, the average form aldehyde concentration may be estim ated and compared to the DNPH tim e-integrated formaldehyde data (described in 3.2.2.).

The continuous for maldehyde detector is desi gned for stationary laboratory use, which accounts for its poor perfor mance on a m obile pl atform. Based on these pilot study results, continuous formaldehyde measurements will only be made for stationary m easurements in the 3 city field studies.

3.1.8 Tenax vs. Canisters

Appendix B list the full data sets for canister and Tenax samples. Si nce Tenax and canister samples overlap at C8-C12 carbon num bers, it is possible to com pare concentrations for toluene, ethylbenzene, m/p-xylene and o-xylen e obtained from both me thods. Figure 3.1-14
shows that the correlations between both m et hods are good. The scatte rplots exclude the 5/5/03 refueling without vapor r ecovery (ME4) sam ples. For th is one ME4 replicate, the canister value was m uch higher than the Te nax sam ple, suggestive of a Tenax tube breakthrough. for this ME. This c ould be due to the extremely high gasoline concentrations encountered in this ME. It is possible that the breakthrough occurred for Tenax sample. One issue with the Tenax samples is the accurate determination of the volume sampled. Since the flow rate is measured at the beginning and at the end of all sampling periods, and the average
flow is used for volum e calculati on, it is poss ible that the volume is not very pr ecise, if the flow drop over the sampling peri od is substantial and non-linear . We are currently improving on the standard m ethod by adding the data logger to the canis ter-Tenax-DNPH cartr idge sampling system that will a llow us to continu ously m onitor f low rate s, thus allo wing f or
accurate volume determination.

3-21Toluene

y = 0.8853x + 8.4119

R 2 = 0.8595

0 50 100 150 200 250 300 350 400 450

0 50 100 150 200 250 300 350 400 450

Cans, ppbCTenax, ppbC Ethylbenzene

y = 0.9935x - 3.7545

R 2 = 0.9089

0 10 20 30 40 50 60 70 80 90

0 10 20 30 40 50 60 70 80

Cans, ppbCTenax, ppbC

m/p-Xylene

y = 1.1225x - 11.694

R 2 = 0.9236

0 50 100 150 200 250 300 350

0 50 100 150 200 250

Cans, ppbCTenax, ppbC o-Xylene

y = 1.0321x - 6.038

R 2 = 0.9258

0 20 40 60 80 100 120

0 2 0 4 0 6 0 8 0 1

Cans, ppbCTenax, ppbC

0 0



### Figure 3.1-14 Comparison of canis ter and Tenax data for all ME

3-22

### 3.2 Comparisons of Correlated Data

3.2.1 PID vs. CO

Since both carbon m onoxide a nd BTEX are produced by gasoline com bustion, they are expected to track each other in an automobile exhaust domin ated environments. Figure 3.2-1 shows the two m easurements track well during th e parking garage tests that are focused on cold-start emissions, although the ratio is variable as indicate d by the scatter in Figure 3.2-3. The apparent time lag for the smaller peaks is an artifact of the API NDIR CO instrum ent’s adaptive filtering, described in the previous section, and subsequent averaging of the data.

During the freeway driving tests, shown in Figure 3.2-4, the correlation between CO and VOC is good, but not as high as the parking garage data.

3-23ME2 - Parking Garage: test1

0 2 4 6 8 10 12 14 16 18

0 5 10 15 2 0 25 30

elapse d tim e (m in)CO (ppm)

0 5 0 100 150 200 250 300 350 400BTEX estimated by PID (ppb) ND IR_C O PID1

ME2 - Parking Garage: test2

0 5 10 15 20 25 30

0 5 10 15 20 25 30

elapsed tim e (m in)CO (ppm)

0 100 200 300 400 500 600BTEX estimated by PID (ppb) NDIR_CO PID1



### Figure 3.2-1. Comparison of CO and BTEX by PID during parking garage tests.

Data are running 1 m inute averages. The CO instrument’s analog out put range (0-20 ppm ) was exceeded briefly during the two la rge peaks near the end of test 2.

3-24ME2 - Parking G arage: test3

0 5 10 15 20 25

0 5 10 15 20 2 5 30

elapse d tim e (m in)CO (ppm)

0 100 200 300 400 500 600BTEX estimated by PID (ppb) ND IR_C O P ID 1

ME2 - Parking G arage: test4

0 2 4 6 8 10 12 14 16

0 5 10 15 20 2 5 30

e lapse d tim e (m in)CO (ppm)

0 5 0 100 150 200 250 300 350BTEX estimated by PID (ppb) N D IR_C O P ID 1

ME2 - Parking G arage: test5

0 5 1 0 1 5 2 0 2 5

0 5 10 1 5 2 0 25 30

e laps e d tim e (m in)CO (ppm)

0 100 200 300 400 500 600BTEX estimated by PID (ppb) ND IR_CO PID 1



### Figure 3.2-1 – cont’d. Com par ison of CO and BTEX by PID dur ing parking garage tests. Data are running 1 minute averages.

3-25p arking garage tes ts

y = 17.48x + 13.46

R 2 = 0.76

0 100 200 300 400 500 600

0 5 10 15 20 25 30

CO (ppm)BTEX by PID (ppb)



### Figure 3.2-3. Scatter plot of CO vs BTEX by PID during parking gara ge tests. Data are running 1 minute averages.

3-26ME1 - Freeway: test3

0 5 10 15 20 25 30

0 5 10 1 5 20 2 5 30 35 40

e lap s e d tim e (m in)CO (ppm)

0 100 200 300 400 500 600 700 800 900BTEX estimated by PID (ppb) ND IR_CO PID 1

ME1 - Freeway: test4

0 2 4 6 8 10 12 14

0 5 10 1 5 20 2 5 30 35 40

e lap s e d tim e (m in)CO (ppm)

0 100 200 300 400 500 600 700BTEX estimated by PID (ppb) ND IR_C O P ID 1

ME1 - Freeway: test5

0 1 2 3 4 5 6 7 8 9 10

0 5 10 1 5 20 2 5 30 35 40

e lap s e d tim e (m in)CO (ppm)

0 100 200 300 400 500 600BTEX estimated by PID (ppb) ND IR_CO PID 1



### Figure 3.2-4. Comparison of CO and BTEX by PID during freeway driving tests.

Data are running 1 minute averages. In test 3, the CO instrument’s an alog output range (0-20 ppm) was exceeded during the first 4 minutes.

3-27

### 3.2.2 CO vs. Formaldehyde

For the last two garage sam pling e vents (M E2-4 and ME2-5), tim e series for continuous formaldehyde and CO show inconclusive results. Figure 3.2-5 shows tim e series data for CO and for maldehyde for ME2-4. During the ME2- 4 period in which form aldehyde data was above the detection limit, both the CO and formaldehyde appear to respond to the same event, but the peaks are not in phase with each other.

0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.0016:40:4816:48:0016:55:1217:02:2417:09:3617:16:48

TimeHCHO (ppb)

0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00NDIR CO (ppm) HCHO (ppb)
NDIRCO (ppm)



### Figure 3.2-5 ME2-4 continuous HCHO and CO tim e series with unexpla ined difference in lag between the two instruments.

Approximately 2.5 minutes separate the instrum ent responses. This indicates that either the time lag correction of 6 m inutes is not accura te for this test, or the adaptive s moothing feature of the CO instrum ent is caus ing a dela yed peak rise in CO. Figure 3.2-6 shows the same ti me series data following adjustm ent of the for maldehyde data by 2.5 minutes t o compensate for the undetermined source of erro r. The data track each other very well.

3-280.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.0016:40:4816:48:0016:55:1217:02:2417:09:3617:16:48

TimeHCHO (ppb)

0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00NDIR CO (ppm) HCHO (ppb)
NDIRCO (ppm)



### Figure 3.2-6. ME2-4 continuous H CHO ti me s eri es shifted back 2.5 minutes to match CO
time series.

Once this tim e adjustment was m ade, CO an d HCHO concentration s were com pared by regression, and the res ulting eq uation ([HCHO] = [CO]*1.2996-1.14587, R 2 

### = 0.91) was
used to estimate HCHO concentrat ions for the period prior to su ccessful data capture for this experiment. The resulting average concentr ation for the estim ated for maldehyde data combined with the actual form aldehyde data was 5.414 ppb. The tim e integrated formaldehyde data from the DNPH for the ME 2-4 experiment was 7.348 ppb. The estimated value is 74 % of the o bserved tim e integra ted sam ple. Despite the discrepancy in phase between the continuous CO and for maldehyde an alyzers, this experi ment is the best indication that the continuous for maldehyde an alyzer may work well if properly tuned and operated in a suitable environment. It also indi cates that CO may serve as a useful surrogate for formaldehyde. To explore this relationshi p further, formaldehyde results from the DNPH cartridges were plotted in a scatter plot agains t CO from time integrated canister samples for each m icroenvironment. Figure 3.2-7 shows the plot with different m icroenvironments having unique symbols on the plot. Formalde hyde from the Freeway microenvironment does not correlate with CO sam ples from the sam e environment. The garage and refueling microenvironments app ear to have a positive corr elation with CO but clu ster f or each microenvironment. Fitting a linear regre ssion through data points for the Garage and Refueling m icroenvironments, neglecting th e Freeway m icroenvironment, gives a good correlation ([HCHO] = 0.594*[CO] + 0.397, R 2 

### = 0.793).

3-290 5 10 15 20 25

0 2 4 6 8 10 12 14

Can CO (ppm)DNPH HCHO (ppb)

Garage
Freeway

Refuel w/o V.R.

Refuel w/ V.R.



### Figure 3.2-7. Scatter plot of formaldehyde (fro m DNPH) and CO for all microenvironments.

3-30

### Finally, comparison of continuous for maldehyde and CO m easurements for the last garage sampling event (ME2-5) shows poor correlation in phase and tim ing (Figure 3.2-8). The unexplained 2.5 m inute lag that resolved peak s in the ME2-4, did little to help this comparison.

0.00 5.00 10.00 15.00 20.00 25.0016:4016:4816:5517:0217:0917:16

TimeHCHO (ppb)

0.00 5.00 10.00 15.00 20.00 25.00NDIR CO (ppm) HCHO (ppb)
NDIR CO (ppm)



### Figure 3.2-8. Formaldehyde and CO time series for ME2-5.

3-31

### 3.2.3 SPME vs. PID

SPME total BTEX se mi-continuous data com par es reasonably with the continuous signal obtained from the interior PID situated righ t next to the fiber while sampling. The SPME concentrations are with in the rang e of the PID signal and follow the changes in PI D
concentrations.

100 200 300 400

7:35 7:41 7:48 7:55 8:01 8:08 8:15

TimePID Concentration (ppbv)

100 200 300 400SPME Concentration(ppbv)

PID1 SPME tot BTEX



### Figure 3.2-9. SPME 10 min total BTEX vs. PI D 10 min averages, Freeway, 5/02, 7:35 am

0 100 200 300 400 500 600 700

9:21 9:27 9:34 9:41

TimePID Concentration (ppbv)

0 100 200 300 400 500 600 700SPME Concentration (ppbv)

PID1 SPME tot BTE X



### Figure 3.2-10. SPME 10 m in total BTEX vs. PI D 10 m in averages, Refueling w/o VR 4/30

9:21am.

3-320 100 200 300 400 500 600 700

7:39 7:45 7:52 7:59 8:05

TimePID Concentration (ppbv)

0 100 200 300 400 500 600 700SPME Concentration(ppbv)

PID1 SPME tot BTE X



### Figure 3.2-11. SPME 10 min total BTEX vs. PI D 10 min averages, Freeway 4/30, 7:35 am.

0 200 400 600 800 1000 1200 1400 1600 1800

9:18 9:24 9:31 9:38

Tim ePID Concentration (ppbv)

0 200 400 600 800 1000 1200 1400 1600 1800SPME Concentration (ppbv)

P ID 1 S P M E tot B TE X



### Figure 3.2-12. SPME 10 m in total BTEX vs. PI D 10 m in averages, Refueling w/o VR 5/02

9:18 am.

3-330 50 100 150 200

16:45 16:51 16:58 17:05 17:11

TimePID Concentration (ppbv)

0 50 100 150 200SPME Concentration (ppbv)

PID1 SPME tot BTE X



### Figure 3.2-13. SPME 10 m in total BTEX vs. PI D 10 m in averages, Pa rking Garage 5/06, 16:45 pm.

Continuous estimates of total VOC by a PID pp bRAE monitor compared reasonably to the semi-continuous measurements of BTEX obtained from analysis of SPME fibers.

3-34

### 3.3 Environmental Factors

The various environm ental conditions m onito red during this study are presented in this section by microenvironment. These data were collected once every 10 seconds, to sim plify the presentation, we present the average for each 10 m in se gment (to correspond w ith the SPME time interval) and the overall average va lue In addition, we present tem perature and wind data collected at a weather station on top of DRI’s building. These data are useful as a general reference for local c onditions, however, it is im portan t to point out that DRI’s building is on top of a hill with nothing to block winds for approximately 270 degrees around and is noted as being one of the windiest sp ots in th e a rea. Th is is im portant since we selected the refueling stations in a location at the bottom of a nearby valley approxim ately 250 feet lower in elevation with a large ridge bl ocking the prevailing winds. For all stationary
MEs we monitored wind with a hand-held anemomet er that had a lower-li mit of detection of approximately 1 mph.

For the freeway microenvironment (ME1), we meas ured temperature and relative humidity at the driver’s breathing zone which was also the sample inlet location for all equipment except the second PID which was m onitoring the air outside the van. The outside PID inlet was located on the radio antenna on the right front co rner of the van. Since the sampling location was inside the van, the tem perature is typicall y higher than the am bient. We also m onitored the temperature on the outside surface of the fuel tank. These data are presented in Table 3.3- 1 along with the average conditi ons for the DRI weather stati on. The average temperature in the van climbed during the runs partially due to the f act tha t we started low ventilation conditions h alfway thro ugh the run. Relativ e hu midities were relativ ely constan t. The fuel tank tem perature clim bed steadily during the run, which was interesting considering the ambient temperatures did not. This was due to the recirculation of fuel af ter is passes the fuel injectors and picks up heat from the engine. Th e 10 second data of fuel tank tem peratures for an example run are presented in Figure 3.3-1.

3-35

### Table 3.3-1. Environmental Conditio ns for Freeway Driving MEs.

Fuel Tank

ME Date Start End Data Set Temp, C Humidity, % Temp, C Wind, mph Temp, C ME1 - Freeway 4/2 9 04/29/03 7:42 8:22 avg. of 1st 10 minutes: 12 37 5 avg. of 2nd10 minutes: 12 32 7 avg. of 3rd 10 minutes: 16 32 11 avg. of 4th 10 minutes: 21 32 13 Average of all 15 33 9 1.8 4.4

ME1 - Freeway 4/3 0 04/30/03 7:39 8:19 avg. of 1st 10 minutes: 10 42 4 avg. of 2nd10 minutes: 13 34 7 avg. of 3rd 10 minutes: 21 28 11 avg. of 4th 10 minutes: 25 26 14 Average of all 17 33 9 3.0 1.5

ME1 - Freeway 5/0105/01/03 7:20 8:00 avg. of 1st 10 minutes: 11 44 7 avg. of 2nd10 minutes: 16 31 8 avg. of 3rd 10 minutes: 20 30 10 avg. of 4th 10 minutes: 21 34 12 Average of all 17 35 9 1.2 4.4

ME1 - Freeway 5/0 2 05/02/03 7:35 8:15 avg. of 1st 10 minutes: 16 36 11 avg. of 2nd10 minutes: 20 30 12 avg. of 3rd 10 minutes: 23 30 15 avg. of 4th 10 minutes: 23 33 16 Average of all 20 32 14 4.5 7.8

ME1 - Freeway 5/0 5 05/05/03 7:50 8:30 avg. of 1st 10 minutes: 15 39 7 avg. of 2nd10 minutes: 17 33 9 avg. of 3rd 10 minutes: 20 36 12 avg. of 4th 10 minutes: 22 39 16 Average of all 18 37 11 1.8 5.4 Sampling Point Measures Ambient Conditions (DRI Weather Station)



### 3-360 2 4 6 8 10 12 14 16 18

7:33 7:40 7:48 7:55 8:02 8:09 8:16 8:24 8:31 8:38

TimeFuel Tank Temp, C

Start Motor

Start Sampling End Sampling



### Figure 3.3-1. Fuel tank tem peratures during freeway ME on 4/29/03. Ambient temperature was 4.4 C during this time.

For the garage m icroenvironment (ME2) we meas ured temperature and relative humidity at the sampling point, which was also the sam ple inlet location for all equipment located on the tripod near the van. These da ta are presented in Table 3.3-2 along with the average
conditions for the DRI weather station. The average temperature and relative humidities were relatively constant, as was the fuel tank tem perat ure as might be expected for this stationary and mostly indoor ME. While the average winds at DRI were quite high (twice in excess of 10 m ph) inside the garage the w inds were calm and undetectab le by the hand-held anemometer. The above-ground garage is also approximately 3.5 m iles south and slightly west of the DRI building (measured in a straight line).

3-37

### Table 3.3-2. Environmental Conditions for Garage MEs.

Fuel Tank Local

ME Date Start End Data Set Temp, C Humidity, % Temp, C Wind, mph Temp, C Winds ME2 - Parking Garage 4/29 04/29/03 16:42 17:12 avg. of 1st 10 minutes: 11 35 15 avg. of 2nd10 minutes: 10 35 15 avg. of 3rd 10 minutes: 10 36 15 Average of all 10 35 15 8.3 9 Calm, not measureab l

ME2 - Parking Garage 4/30 04/30/03 16:45 17:15 avg. of 1st 10 minutes: 12 33 14 avg. of 2nd10 minutes: 11 33 14 avg. of 3rd 10 minutes: 11 33 14 Average of all 11 33 14 10.4 10 Calm, not measureab l

ME2 - Parking Garage 5/01 05/01/03 16:42 17:17 avg. of 1st 10 minutes: 16 24 16 avg. of 2nd10 minutes: 14 25 16 avg. of 3rd 10 minutes: 14 26 16 Average of all 15 26 16 4.9 14 Calm, not measureab l

ME2 - Parking Garage 5/02 05/02/03 16:45 17:15 avg. of 1st 10 minutes: 14 46 15 avg. of 2nd10 minutes: 14 48 15 avg. of 3rd 10 minutes: 14 47 15 Average of all 14 47 15 4.5 12 Calm, not measureab l

ME2 - Parking Garage 5/06 05/06/03 16:45 17:15 avg. of 1st 10 minutes: 14 34 16 avg. of 2nd10 minutes: 13 34 16 avg. of 3rd 10 minutes: 14 35 15 Average of all 14 34 16 11.7 11 Calm, not measureab l Sampling Point Measures Ambient Conditions (DRI Weather Station)



### For the ref ueling m icroenvironments (ME3 was with vapor recovery, ME4 w as without vapor recovery), we measured temperature and relative humidity at the sampling point which was also the sample inlet location for all equipm ent. This was located on the tripod between the van and the fuel pump to allow us to asse ss the conditions at the breathing zone of the person refueling the van. These data are presented in Table 3.3-3 along with the average
conditions for the DRI weather station. The average temperature and relative humidities were relatively constant, as was the fuel tank tem perat ure as might be expected for this 20 m inute stationary ME. While the averag e winds at DRI did go above the 5 mph threshold for three of the MEs, the winds at the refueling stations we re much lower as monitored by the hand-held
anemometer. The stations are 1.3 and 1.9 miles fr om the DRI building (meas ured in a straight line). Also presented in Table 3.3-3 are the maxi mum numbers of cars seen in the station, the amount of fuel dispensed and the amount dropped on the ground following refueling. The station with the vapor recovery was a m uch busier station with more than twice the num ber
of cars as the other station. Th e station used for refueling without vapor recovery (ME4)
could refuel a m aximum of four vehicles at one time, as it had two p umps and each pum p
could be used from either side. The station used for refueling with vapor recovery (ME3) could refuel a maximum of 8 vehicles at once, as it had two islands with two pumps each and each pum p could be approached from either side. For all MEs we managed a relatively consistent number of gallons dispensed which was possible since we could unload fuel from the van to a nearly cons tant level. For each refueling ME, we filled up until th e automatic shutoff stopped the filling process. The num b er of drops spilled was not as co nsistent partially due to the difficulty in precisely dropping a fixed amount of fuel out of the nozzle.
The number in Table 3.3-3 is th e number of drops spilled whic h was an approximate count of the number of wet spots noted on the pavem ent. The exception is the fi rst ME where a large amount of fuel unexpectedly cam e out of the nozzle and left a single spot approxim ately 5
cm in diameter.

3-38

### Table 3.3-3. Environmental Conditions for Refueling MEs.

Fuel Tank Max. Cars Gallons Drops of Local
ME Date Star t End Data Set Temp, C Humidity, % Temp, C In Station Dispensed Fuel Spilled Wind, mph Temp, C Winds ME3 - Refueling w/ VR 4/29 04/29/03 12:00 12:20 avg. of 1st 10 minutes: 11 28 12 avg. of 2nd10 minutes: 11 28 13 Average of all 11 28 13 6 16.50 5 cm pool 5.9 7.4 1 - 2 mph

ME3 - Refueling w/ VR 4/30 04/30/03 10:45 11:05 avg. of 1st 10 minutes: 9 37 14 avg. of 2nd10 minutes: 9 36 15 Average of all 9 36 15 4 16.25 25 3.8 6.5 2 mph from SE

ME3 - Refueling w/ VR 5/01 05/01/03 12:25 12:45 avg. of 1st 10 minutes: 14 24 16 avg. of 2nd10 minutes: 14 24 16 Average of all 14 24 16 3 16.42 5 7.6 11.9 2 - 4 mph from SE va r

ME3 - Refueling w/ VR 5/02 05/02/03 10:36 10:56 avg. of 1st 10 minutes: 11 53 15 avg. of 2nd10 minutes: 10 54 14 Average of all 11 53 15 5 15.40 10 2.5 8.5 < 1 mph, some drizzl e

ME3 - Refueling w/ VR 5/05 05/05/03 10:45 11:05 avg. of 1st 10 minutes: 12 35 17 avg. of 2nd10 minutes: 12 35 16 Average of all 12 35 17 6 17.50 12 3.9 9.0 <1 mph from SSE

ME4 - Refueling w/o VR 4/3 0 04/30/03 9:21 9:41 avg. of 1st 10 minutes: 14 28 14 avg. of 2nd10 minutes: 14 28 14 Average of all 14 28 14 3 15.80 6 2.9 3.6 1 - 2 mph from NNW

ME4 - Refueling w/o VR 4/3 0 04/30/03 12:01 12:21 avg. of 1st 10 minutes: 12 30 16 avg. of 2nd10 minutes: 13 28 16 Average of all 13 29 16 1 15.40 12 3.2 7.9 2 - 4 mph variable dir.

ME4 - Refueling w/o VR 5/0 05/01/03 11:06 11:26 avg. of 1st 10 minutes: 15 22 14 avg. of 2nd10 minutes: 14 22 14 Average of all 14 22 14 1 14.18 3 6.6 9.8 2 - 3 mph from SSE

ME4 - Refueling w/o VR 5/0 2 05/02/03 9:18 9:38 avg. of 1st 10 minutes: 11 42 18 avg. of 2nd10 minutes: 10 44 17 Average of all 11 43 18 2 17.31 12 3.5 8.7 1 - 2 mph, overcast

ME4 - Refueling w/o VR 5/0 5 05/05/03 9:23 9:43 avg. of 1st 10 minutes: 17 28 18 avg. of 2nd10 minutes: 17 30 18 Average of all 17 29 18 1 14.50 20 3.9 8.3 < 1 mph from W Sampling Point Measures Ambient Conditions (DRI Weather Station)



### 3-39

### 3.4 Reconstructed Data

One of the objectives of this study was to de termine if the original objective of using surrogate measures to determ ine the tim e seri es of com pounds of interest was valid. To answer this question, this section details the reconstruction of the time series for benzene and
BTEX from the PID data and th e comparison of this to the be nzene and BTEX determined by the MS200 portable mass spectrometer.

The procedure is first to average the 10 second data that is recorded by the PID instrument up to 1 minute data for com p arison with the MS200 data set (1 m inute increments). This tim e series is then used along with the integrat ed canister value to
reconstruct a tim e series of the canister concen trations. To accom plish this, a ratio is taken between th e PID value at each point and the average P ID value for th e tim e series. This number is multiplied b y the integr ated canister value to g ive a reconstructed value for that data point and is compared to the time- corresponding data point from the MS200.

The first example presented is for the fr eeway driving (ME1) on 4/29/03. Figure 3.4-1
shows the tim e series f or benzene in this ME. A few data points are m issing from the MS
data where some electrical noise ren dered thos e data points invalid. Th e general trend of the peaks is reproduced by both the MS200 and the PID reconstructed data, however, the peak values are much higher in the MS200. This is confirmed by the comparison of the integrated values, where the MS200 showed 14.7 ppb and th e canister 9.1. ppb. This ratio (1.6) nearly accounts for the differences and may be due to offs et (zero point) or cal ibration differences in the MS200. Comparing the time series for the su m of the BTEX species, we obtain the plot in Figure 3.4-2. In this figure, the structure of the time series and the magnitude of the peaks are both much more precisely reproduced than is the case with just ben zene. Due to both the higher concentrations of toluene and the C8 benzenes, and the better perform ance of the MS200 with these species. S ection 3.1.9 details the performance of th e MS200 versus the canisters an d shows that benzene is consis tently the m ost difficult s pecies to measure, especially at the lower levels. The integra ted canister measurement for this sam ple was 97 ppb for the sum of the BTEX species while the MS200 reported 123 ppb . Looking at the two highest peaks in this tim e series (8:01 and 8:03 am ) it appears that the tim ing is slightly off with the MS200 lagging the PID reconstructed data.

To further investigate the tim ing between these two instrum e nts, we looked at a higher concentration sam ple with a si gnificant spike in the concentration (ME4 refueling w ithout vapor recovery from 5/2/03). Figure 3.4-3 shows the reconstructed tim e series for benzene along with the MS200 values for benzene. Figure 3.4-4 presents the same data for B TEX. In both figures, the series is well reproduced how ever the peak values reco rded by th e MS200
are much lower than the reconstructed. Duri ng the “non-peak” part of the ME, the MS200 appears to be reading consisten tly higher than the r econstructed values. Ov erall, however, the values match quite well with the ratio of MS200/canister of 1.05 for the BTEX species and 1.18 for benzene. As with the previous exampl e, it appears that th e tim ing of the peak concentration is out of phase by one m inute. To look more closely at the peak concentration, we used the original 10 second data from the PID to reconstruct a 10 second tim e series for the BTEX species and plotted th at along with the 1 m inute data in Figure 3.4-5. This figure

3-40

### does not show the entire time series; rather it fo cuses on the period of the peak exposure from 9:27 to 9:33 a m. In this figure, the 10-second reconstructed data shows two peaks where the
1-minute reconstructed and the MS200 data show one peak. The 1-minute time averaged data may better represent what the MS200 is m easuring, since the MS200 does not integrate samples over the 1-m inute period. Rather, the natu re of the flow-through system smears the peaks out over a longer tim e due to the tim e it takes analytes to di ffuse through the inlet system and into the mass analyzer. The flow-through system also means that some very short duration high peaks may not be seen at all.

Overall the com parison of the reconstructed BTEX and MS200 BTEX values substantially agree and this provides added confidence that we can represen t the peak exposures well by using the PID values to reconstr uct time series for the BTEX species. While we do not have a direct m easure for 1,3-butadie ne, we would suggest that it could also be adequately represented by the PID values, especi ally for exhaust-dominated MEs.



### 0 5 10 15 20 25 30 35

7:26 7:40 7:55 8:09 8:24

Timeppbv 

### MS200 Benzene

Reonstructed Bz

Figure 3.4-1. ME1 (freeway driving) on 4/29/03: Time series of benzene from the MS200
and reconstructed benzene concentrations from the PID and canister measurements.

3-41

### 0 50 100 150 200 250

7:26 7:40 7:55 8:09 8:24

Timeppbv 

### MS200 BTEX

Reonstructed BTEX



### Figure 3.4-2. ME1 (freeway driving) on 4/29/03 : Time series of BTEX from the MS200 and
reconstructed BTEX concentrations fr om the PID and canister measurements.

3-42

### 0 50 100 150 200 250

9:14 9:21 9:28 9:36 9:43

Timeppbv 

### MS200 Benzene

Reonstructed Bz

Figure 3.4-3. ME4 (refueling without vapor rec overy) on 5/2/03: Tim e series of benzene
from the MS200 and reconstructed benzene c oncentrations from t he PID and canister

measurements.

3-43

### 0 200 400 600 800 1000 1200 1400

9:14 9:21 9:28 9:36 9:43

Timeppbv 

### MS200 BTEX

Reonstructed BTEX

Figure 3.4-4. ME4 (refueling without vapor recove ry) on 5/2/03: Tim e series of BTEX from
the MS200 and reconstructed BTEX concentratio ns from the PID and canister measurements.

3-44

## 0 1000 2000 3000 4000 5000 6000 7000

9:27 9:30 9:33

Timeppbv 

## MS200 BTEX

Reonstructed BTEX

10 Sec BTEX

Figure 3.4-5. ME4 (refueling without vapor recove ry) on 5/2/03: Tim e series of BTEX from
the MS200 and reconstructed BTEX concentra tions at both 1 m inute and 10 second time
resolution.

3-45

### 3.5 Breath Data

Two subjects, labeled “B” and “J”, perform ed breath sample collections . The CO2 level in their breath sam ples was m easured prior to the comm encement of the pilot study, and averaged 5.4% for B and 6% for J. As de scribed in Section 2.1, tw o breath sam ples were collected at refueling ME (prior to refueling and 10 sec after refueling), and three during each commuter traffic and garage test (before, after a peak exposu re, and at the end of the ME sampling time). All breath sam ples were an alyzed for CO2, BTEX, 1,3-butadiene, ethanol
and MTBE as described in Section 2.3. The whole data set is presented in Appendix C.

Figure 3.5–1 shows the CO2 values in the breath samples of subjec ts B and J collected in all ME, organized by the subject and by the m icroenvironment. It is clear that one pre- test freeway sample collected by J is in valid, sin ce CO2 value is below 1%. Excluding this one sample, the m ean CO2 value for subject B averages at 5.4%, and for subject J at 6.07% for
all ME.

Figure 3.5-2A shows the concentrations of 1,3-but adiene, benzene, ethylbenzene, m/p- and oxylenes in the breath samples for all freeway tests (organized in th e chronological order) and Figure 3.5-2B shows the c oncentrations of toluene and etha nol for the sam e ME. Figures 3.5-3 A and B and Figure 3.5-4 A and B shows the same compound concentrations for the garage and refueling ME, respectively. The range of concentrations for 1,3-butadiene, benzene, ethylbenzene, m/p- and o-xylenes agre e reasonably well for bo th subjects, there is clearly a large difference in the toluene conc entrations. Subject B contains m uch higher
toluene concentrations in the breath – it looks lik e the toluene is present in the b reath of this subject, regardless of the exposure. The reason of this phenom enon is unknown to us.
Ethanol concentrations are rath er high and variable, not dependa nt on the exposure. MTBE concentrations are very low and are not shown on these figures. Neither MTBE nor ethanol are present in the Reno fuel at this time of the year.

3-46Carbon Dioxide0123456789

%----------------------------------------------------------- B ------------------------------------------------------------------------------------------------------------------------------------ J -------------------------------------------------Figure 3.5–1. CO2 values in the breath sam ples of subjects B and J collected in all ME, organized by the subject and bymicroenvironment.3-47Freeway

0 2 4 6 8 10 12Freeway, PreFreeway, PeakFreeway, PostFreeway, PreFreeway, PeakFreeway, PostFreeway, Pre,JFreeway, Peak,JFreeway, Post,JFreeway, PreFreeway, PeakFreeway, PostFreeway, Pre,JFreeway, Peak,JFreeway, Post,Jppb bud13

benze

etbz
mp_xyl
o_xyl A

Freeway

0 20 40 60 80 100 120 140 160Freeway, PreFreeway, PeakFreeway, PostFreeway, PreFreeway, PeakFreeway, PostFreeway, Pre,JFreeway, Peak,JFreeway, Post,JFreeway, PreFreeway, PeakFreeway, PostFreeway, Pre,JFreeway, Peak,JFreeway, Post,Jppb tolue

ethoh B



### Figure 3.5-2. The concentrations of 1,3-butadie ne, benzene, ethylbenzene, m /p- and oxylenes (A) and toluene and ethanol (B) in the breath samples of subjec t B (not labeled) and J in the freeway driving ME. The r uns are shown in chronological order

3-48

### Garage

0 1 2 3 4 5 6 7 8Garage, PreGarage, PeakGarage, PostGarage, PreGarage, PeakGarage, PostGarage, Pre,JGarage, Peak,JGarage, Post,JGarage, PreGarage, PeakGarage, PostGarage, Pre,JGarage, Peak,JGarage, Post,Jppb bud13

benze

etbz
mp_xyl
o_xyl A



### Garage

0 20 40 60 80 100 120 140 160 180Garage, PreGarage, PeakGarage, PostGarage, PreGarage, PeakGarage, PostGarage, Pre,JGarage, Peak,JGarage, Post,JGarage, PreGarage, PeakGarage, PostGarage, Pre,JGarage, Peak,JGarage, Post,Jppb tolue

ethoh B



### Figure 3.5-3. The concentrations of 1,3-butadie ne, benzene, ethylbenzene, m /p- and oxylenes (A) and toluene and ethanol (B) in the breath samples of subjec t B (not labeled) and J in the garage ME. The runs are shown in chronological order

3-49Refueling

0 5 10 15 20Ref. W/O V, PreRef. W/O V, PostRef. W/O V, PreRef. W/O V, PostRef. W/O V, Pre,JRef. W/O V, Post,JRef. W/O V, PreRef. W/O V, PostRef. W/O V, Pre,JRef. W/O V, Post,JRef. W/V, PreRef. W/V, PostRef. W/V, PreRef. W/V, PostRef. W/V, Pre,JRef. W/V, Post,JRef. W/V, PreRef. W/V, PostRef. W/V, Pre,JRef. W/V, Post,Jppb bud13

benze

etbz

mp_xyl

o_xyl 80 ppb A



### Refueling

0 50 100 150 200 250Ref. W/O V, PreRef. W/O V, PostRef. W/O V, PreRef. W/O V, PostRef. W/O V, Pre,JRef. W/O V, Post,JRef. W/O V, PreRef. W/O V, PostRef. W/O V, Pre,JRef. W/O V, Post,JRef. W/V, PreRef. W/V, PostRef. W/V, PreRef. W/V, PostRef. W/V, Pre,JRef. W/V, Post,JRef. W/V, PreRef. W/V, PostRef. W/V, Pre,JRef. W/V, Post,Jppb tolue

ethoh B



### Figure 3.5-4. The concentrations of 1,3-butadie ne, benzene, ethylbenzene, m /p- and oxylenes (A) and toluene and ethanol (B) in the breath samples of subjec t B (not labeled) and J during refueling. The runs ar e shown in chronological order

3-50

### 3.6 Consistency of Microe nvironment Conditions

Each of the four m icroenvironments included in this pilot study was repeated 5 tim es to assess the v ariability of the environ mental c onditions and precision of the characterization methods. During the testing periods there were no significant variatio ns in m eteorological conditions and the sam e protocols were obser ved, so it is reasonable to attribute any variations in the range or m a gnitude of m easurements to di fferences in activity in the microenvironment, daily variations in background concentrations, or m easurement uncertainty. Statistical summaries of the conti nuous CO and BTEX by PI D data are presented in this section to exam ine this var iability. The statistics represented are the m aximum and mean of the running 1 m inute averages of th e continuous concentration m easurements recorded every 10 seconds during each test. The 10t h and 90th percentile values for each test are also represented to g ive a better repres en tation of the range of conc entrations observed. Charts of the average for each m icroenvironm ent and standard dev iation of the average among the 5 replicates are al so included in Figure 3.6-3.

3.6.1 CO

Figure 3.6-1 shows the API NDIR CO data except for the first two repetitions of ME1 and
the first ME3 for which the NDIR d ata was inva lid because of insuffici ent battery. For those three tests discrete 1 m inute av erages from the electrochem ical CO instru ment are
summarized in the chart.

The range of concentrations is large for all tests, with the exceptio n of several of the refueling tests (ME3 and ME4) where CO c oncentrations were ne ar background throughout the tes ts. Despite the large rang e, the differen ces between m icroenvironments are clearly evident. The parking garage tests, ME 2, had higher m aximum and 90th percentile
concentrations than all but one of the freeway tests even th ough the average concentrations are similar. The two refueling MEs are cons isten tly lower than the freeway or garage in both the mean and maximum values. The third freeway (ME1) test appears to be an outlier due to a high initial level of CO (see Figure 3.2-4), po ssibly a result of capturing exhaust from the van in the cabin prior to the start of the driving cycle.

3-510 5 10 15 20 25

M E 1 M E 2 M E 3 M E 41 m inute running avg CO (ppm ) 10th to

90th %

MAX

MEAN



### Figure 3.6-1. Range and variability of CO con centration during tests. S tatistics for each of the five replicate tests are shown for each microenvironment.

Data summarized are running 1-minute averages (at 10 second interval s) of NDIR CO data, except for the first two ME1s and fi rst ME3 which are dis crete 1 m inute averages from the
electrochemical CO instrum ent. The shaded ba rs indicate the range from the 10th to 90th percentile. Microenvironments are: freeway driv ing (ME1), parking garage (ME2), refueling with vapor recovery (ME3), and refu eling without vapor recovery (ME4).

3-52

### 3.6.2 PID

The range and variability of BTEX concentrations estim a ted by the prim ary ppbRAE VOC monitor (PID1) are summarized in Figure 3.6-2. As with CO, the range of the m ean and maximum values is larg e for all tests, but s till smaller than the overa ll difference between microenvironments. The largest range occurred for refueling w ithout vapor recovery (ME4), which is to be expected since very high VOC levels occurred dur ing the refueling process. In all cases, the 10th percentile values were near th e lower limit of detection (they appear to be zero in the chart due to scale) suggesting that background levels of BTEX were very low.

3-530 2000 4000 6000 8000 10000 12000 14000 16000 18000

ME1 ME2 ME3 ME41 m inute running avg BTE X by PID (ppb) 10th to

90th %

MAX

MEAN

0 100 200 300 400 500 600 700 800 900 1000

ME1 M E2 ME3 ME41 m inute running avg BTE X by PID (ppb) 10th to

90th %

MAX

MEAN



### Figure 3.6-2. Range and variability of BT EX by PID concentration during tests.

Statistics for each of th e five rep licate te sts are shown for each m icroenvironment. Data summarized are running 1-minute av erages (at 10 second intervals) The shaded bars indicate the range from the 10th to 90th percentile. The lower chart shows the sam e dat a on an expanded s cale. M icroenvironments are: free way driving (ME1), parking garage (ME2), refueling with vapor recovery (ME3), and refueling without vapor recovery (ME4).

3-54A verage of replicate test mean c onc entrations

0 1 2 3 4 5 6 7 8 9

ME1 ME2 ME3 ME4CO (ppm)

0 200 400 600 800 1000 1200 1400

ME1 ME2 ME3 ME4BT EX by PID (p pb)



### Figure 3.6-3. Range a nd variability of mean CO and m ean BTEX by PID concen tration for
four microenvironments.

Data summarized are running 1-minute averages (at 10 second interval s) The error bars
indicate the standard de viation of the average of five repl icate tests. Microenvironments are: freeway driving (ME1), parking garage (ME2), refueling with vapo r rec overy (ME3 ), and refueling without vapo r recovery (ME4).

3-55

## 4. CONCLUSIONS

Overall, the 2nd Reno Pilot study was a success. Specifically, we completed the stated goal of the study: to dem onstrate the proper operation and reliability of analytical instrumentation and com parability of tim e-integrated, se mi-continuous and continuous m ethods for compounds of interest. In addition, we dem onstrated the validity of the method of reconstructing time series for compounds of intere st by using surrogate m easurements. In this case, we specifically demonstr ated the validity of using the PID signal and the canister data
to reconstruct the time series for BTEX.

The following conclusions are drawn from the 2nd Reno Pilot Study results:

Modifications to the sampling van and addition of the data acquisition system were significant improvem ents that allow ed for more com plete d ata collectio n. The new power system does not produce artifacts; howev er, it is insufficient to power the API
CO instrument. Possible alternatives include use of a different brand of NDIR CO or the addition of m ore battery banks to sup port the A PI NDIR CO. Severa l improvements ar e still planned to the sa mpling van inc luding the ad dition of a continuously logged barom etric pressure se nsor, direct logging of flow to the integrated samplers, and loggi ng of canister pressure.

Data capture was generally quite good with near 100% data capture for the reference samples, canisters, DNPH and solid adsorbent. The SPME also had excellent data capture, as did the continuous instrum ent s for CO and PI D. The MS200 performed well in the beginning of the study however at the end it was not working. The supplemental continuous for maldehyde instru ment is not reliable during m obile measurements, and should only be used for statio nary m easurements. Our environmental m onitoring equipm ent for te mperatures, hum idity, etc., lost only 14
minutes of data over the entire study.

The MS200 generally perform ed well agai nst the canister when comparing the average value from the MS to the integrat ed canister measurement for the same ME. However, there are still concerns with th is supplemental measurement system. There appears to be a concentration bias, especially for benzene. The instrum ent appears to miss very rapid changes in concentration su ch as those that occur du ring refueling
events. There are still so me electrical nois es that appear in the van when in m otion. We did not detect these in the stationary ME s, and they did not invalidate more than a few spectra in a run. The MS200 did not run during the last day of the study due to several f actors re lating to th e sens itivity of th e dete ctor a nd the f ilament voltage control. Some of this appears to be electr onic related and may be fixed when we send the electron ics box back to be upgraded to the new interface. The MS200 is a developing instrument that s hould provide interesting supple mental data to the study.

The continuous for maldehyde analyzer wo rked well for two of the five garage sampling microenvironm ents (ME2-4 and ME 2-5) but did not work well for the freeway (ME1) or ref ueling (ME3 a nd ME 4) microenvironments. The se nsitivity of
the instrument to environmental noise asso ciated with d riving while co llecting data may limit its utility under any so rt of mobile environment. With proper operation and

4-1

### better characterization of instrument perform ance, the supplem ental continuous formaldehyde analyzer may prove useful fo r monitoring a stationary environment.

Both an EPA-certified gas- filter correlation NDIR CO an alyzer (API model 300) and a portable battery-operated pa ssive electrochem ical cell instrum ent (Langan T15v) agree rea sonably well to within ab out 1 ppm . During low-ventil ation (half of the freeway tests) the CO concentration s remain at or decrease toward the lowest level measured during the high-vent phase. This be havior suggests that no in-cabin sources or interferences are present.

In general the continuous PID and CO in struments perform ed very well. The two PIDs were compared both in controlled te sts and collocated during the MEs. In both cases, they tracked each other qu ite well. Diffe rences appear to be due to an offset in one unit, and a slightly different respons e speed between the two units. The NDIR CO and electrochemical CO instruments compar ed favorably, usually within 1 ppm . This was partially attributed to the adaptive filtering of the API NDIR CO as demonstrated when comparing it to another NDIR instru ment made by Monitor Labs, Inc. For the purposes of this study, we strongly reco mmend using an instrum ent without the adaptive f ilter sin ce th e f ilter caus es change s in concentration to app ear le ss sha rp than actua l and causes peaks to shif t to later tim es which interf eres with intercomparisons among methods and instruments.

Comparison of CO from the continuous inst ruments to that measured by GC from the
canisters sh owed that the canister CO wa s generally 8% higher with no consistent bias correlated to any particular ME nor with concentration. The correlation between the CO and PID data was strongest for the garage ME.

SPME sa mples show overall higher concen trations than MS200 (10-min averaged) concentrations. Also, S PME data averaged o ver th e entire sam pling period s are generally higher than canister data, due possibly to inadequate tem perature
corrections of the SPME data. SPME fibers ar e very sensitive to temperature changes (they absorb m ore analytes under cold condi tions, as in this pilot study) and they might not be fully equilibrated to am bien t temperatures prior to sampling. In the future study , the clean f ibers will be stored a t am bient tem perature in a closed
container with activated charcoal.

The proced ure f or collecting and a nalyzing b reath samples worked well; ther e was only one invalid sam ple (based on CO 2 

### concentration) during this study. The data shows consistently higher BTEX c oncentr ations after the peak exposure and are comparable between the two subjects collecti ng the samples. One exception is toluene where it ap pears that o ne of the su bjects ha s toluene p resent in the b reath samples, regardless of the exposure.

The 5-m inute canister sam ples had lower da ta recov ery (80%). Th is was partia lly because the sampler that was used to fill this canister wa s not optimal for the task. A relatively high flow rate was needed to pressurize a canister in only 5 m in and the sampler used was not designed for this m u ch flow. For the final study, we have designed and built a new sampler specifically for this task.

4-2

### The reconstruction of the be nzene and BTEX tim e series from the PID data showed overall good com parison with the MS200 data . However, som e concentration peaks were not reproduced in m agnitude and appear ed to be tim e shifted, a consequence of the averagin g of the PID data from 10 seconds down to 1 m inute. In addition, the MS200 does not integrate sam ples over the 1- minute period; rather the nature of the flow-through system smears the peaks over a longer period due to the tim e it takes to diffuse through the inlet system and into the m ass analyzer. Because of the flowthrough system , very short duration high p eaks m ay not be see n. In summ ary, for
most of the MEs the reconstructed data and the MS200 data agr eed reasonably well, suggesting that the reconstruction m ethod works and should provide a m ethod to calculate the peak exposures during sampling at the MEs.

4-3

## 5. REFERENCES:

Chai, M. and J. Pawliszyn, 1995. Analysis of Environm ental Air Sam ples by Solid-Phase Microextraction and Gas Chrom atogr aphy/Ion T rap Mass Spectrom etry, Environmental Science and Technology, Vol. 29, No. 3. Pag 693-701.

Grote C.and J.Pawlinszyn, 1997. Solid Phase Mi croextraction for the analysis of Hum an Breath. Anal Chem.. Volume 69, 587-596

Kelly, T.J. and C.R. Fortune (1994). C ontinuous Monitoring of Gaseous Formaldehyde Using an Improved Fluorescence Approach. Intern. J. E nviron. Anal. Che m., 54:

249-263

Koziel, Jaceb, et al., 1999 Field air analysis with SPME device. Analytical Chimica Acta 400

153-162

Koziel, Jacek A. and Novak, I. 2002. Sa mpling and Sample-preparation Strategies Based on Solid-phase Microextraction for Analysis of Indoor Air. Trends in Analytical Chemistry, Vol 21, No.12.

Lodge, James P. Methods of air sam pling an d analysis. Third edition. Lewis publishers. Intersociety committee. Michigan, 1989. pp15-16.

Martos, P. and J. Pawliszyn, 1997. Calibratio n of Solid Phase Microextraction for Air Analysis B ased on Physical Chem ical Pr operties of the Coating. . Analytical Chemistry. 69: 206-215. 1997

Martos, P. and J. Pawliszyn, 1999. Ti me-Weighted Average Sa mpling with Solid-Phase Microextraction Device: Implications for Enhanced Personal Exposure Monitoring to Airborne Pollutants, Analytical Chemistry, Vol. 71, No. 8, April 15.

McLaren and Zhou, 2000. Measurem ent of Oxyge nated Hydrocarbons in Outdoor Air using
Sold-Phase Microextraction Gas Ch romatography. AAA Conference 2000.

Namiesnik, Jacek. Generation of standard gaseous m ixtures. Journal of Chrom atography. 300. 1984. pp. 79-108.

Nelson, Gary O. Gas Mixtures: P reparation and Control. Lewis Pl ublishers. 1992. CRC

Press.

Parreira, F et al. Evaluation of Indoor Exposit ion to BTEX and Styren by passive sampling
with SPME. Journal of Chroma tography, Vol. 40, March 2002. 122-126.

Pawliszyn, J., 1997. Solid Phase Microextract ion: Theory and Practice, Wiley-VCH.

Pawliszyn, J., 1999. Applications of Solid phase Microextra ction. Royal Society of Chemistry.

Pawliszyn, 2002. Sam pling and Sa mple Pr eparation for Field and Laboratory. Comprehensive Analytical Chemistry, Vol 37. Elsevier.

5-4

### Pleil J.D. and A. B. Li ndstrom. (1995). Me asurement of volatile organic com pounds in
exhaled breath as collected in evacuated el ectropolished canisters. J. Chromatogr. B,

665: 271-279

Tuduri, Ludovic et al. Potential of Sollid-Ph ase Microextraction fibers for the Analysis of VOC in air. Journal of Chrom atographic Science, Vol. 39, Decem ber 2001. pp 521-

529.

Zielinska, B., E. M. Fujita and J. C. Sage biel (2003). Section 211(B) Tier 2 High End Exposure Screening Study of Bas eline a nd O xygenated Gasolin e - Summ er 2002 Atlanta Field Study on Baseline Gasoline. Feb. 2003

Zielinska, B., E. M. Fujita, J. C. Sagebiel, D. E. Campbell, J. D. McD onald, L. R. Smith, T. Johnson (2002). Exposure Protocol and St udy Plan for the Section 211(B) Tier 2 High End Exposure Screening Study of Base line and Oxygenated Gasoline. Revisied edition,Sept.30,2002

5-5

## 6.APPENDICIES

6.1 Appendix A: SPME

ppb

me date strthhmm stophhmm an_date Storage T avg RHavg benze tolue etbz mp_xyl o_xyl

ME3 4/29/03 1210 1220 4/29/03 2:40 10.69 28.03 6.66 47.13 10.18 29.32 7.99

ME3 4/29/03 1200 1210 4/29/03 3:15 10.69 28.03 17.21 58.56 11.22 24.76 12.06

ME1 4/29/03 812 822 4/29/03 7:33 20.78 31.90 18.80 114.09 19.42 51.10 15.56

ME1 4/29/03 802 812 4/29/03 8:18 15.80 31.81 12.50 98.24 18.51 51.17 16.44

ME1 4/29/03 752 802 4/29/03 9:08 12.32 31.89 15.69 70.86 15.95 45.05 14.50

ME1 4/29/03 742 751 4/29/03 9:38 11.71 37.73 13.12 66.47 19.61 54.81 17.34

ME2 4/29/03 1652 1702 4/29/03 1:08 10.28 34.59 24.70 66.85 19.49 49.33 14.83

ME2 4/29/03 1702 1712 4/29/03 1:28 10.08 35.88 28.21 90.12 26.36 73.08 25.69

ME2 4/29/03 1642 1652 4/29/03 2:18 10.56 34.60 4.08 12.49 2.48 6.95 1.59

ME4 4/30/03 1211 1221 4/30/03 1:04 27.68 12.82 11.74 65.18 15.12 34.53 7.41

ME4 4/30/03 1201 1211 4/30/03 1:34 29.14 12.21 10.29 38.17 13.10 28.02 7.16

ME3 4/30/03 1045 1055 4/30/03 3:15 8.93 36.59 6.61 24.51 6.31 20.73 5.50

ME3 4/30/03 1055 1105 4/30/03 3:35 8.99 36.32 2.71 16.40 7.55 18.23 4.50

ME1 4/30/03 809 819 4/30/03 6:36 25.54 25.88 20.41 155.78 22.19 66.59 19.90

ME1 4/30/03 759 809 4/30/03 7:11 20.69 28.02 21.92 139.74 30.27 80.99 27.37

ME1 4/30/03 739 749 4/30/03 7:56 9.72 42.59 27.17 113.76 33.86 84.96 27.28

ME1 4/30/03 749 759 4/30/03 8:26 12.98 34.35 26.52 101.84 14.13 59.19 18.05

ME4 4/30/03 921 931 4/30/03 7:39 14.10 27.98 17.04 85.61 15.34 57.68 17.01

ME4 4/30/03 931 941 4/30/03 7:49 14.03 28.33 41.04 140.14 20.70 75.84 22.48

ME2 4/30/03 1645 1655 4/30/03 3:35 32.77 11.59 28.60 89.19 13.52 49.40 16.85

ME2 4/30/03 1655 1705 4/30/03 3:45 32.71 10.84 19.14 69.59 16.89 58.29 19.66

ME2 4/30/03 1705 1715 4/30/03 3:55 33.04 11.07 64.00 173.74 48.88 154.57 58.11

ME1 5/1/03 720 730 5/1/03 2:30 11.32 43.40 49.70 152.00 36.87 104.52 34.61

ME1 5/1/03 750 800 5/1/03 2:30 21.41 33.72 29.58 195.04 24.92 81.88 26.47

ME1 5/1/03 730 740 5/1/03 3:10 15.96 30.60 29.78 130.20 26.21 87.38 28.80

ME1 5/1/03 740 750 5/1/03 3:30 19.82 30.06 21.32 110.07 19.09 63.33 23.26

ME4 5/1/03 1116 1126 5/1/03 2:44 13.72 21.79 8.05 54.91 14.50 44.03 12.10

ME4 5/1/03 1106 1116 5/1/03 3:24 14.50 22.27 5.55 43.57 14.64 35.20 8.71

ME3 5/1/03 1225 1235 5/1/03 2:20 13.54 24.52 5.61 17.02 4.60 13.58 3.23

ME2 5/1/03 1647 1656 5/1/03 1:13 14.92 24.64 6.53 38.15 8.80 23.63 6.48

ME2 5/1/03 1707 1717 5/1/03 1:13 16.18 35.42 24.17 83.75 16.99 56.15 20.52

ME2 5/1/03 1657 1707 5/1/03 2:03 14.31 25.74 30.28 91.61 15.95 58.19 19.01

ME3 5/2/03 1036 1046 5/2/03 2:39 10.76 52.57 33.56 94.44 16.85 61.89 19.50

ME3 5/2/03 1046 1056 5/2/03 2:59 10.34 53.49 7.32 39.96 7.48 23.74 5.97

ME3 5/2/03 918 928 5/2/03 4:52 10.77 42.35 4.85 27.41 6.35 18.09 4.01

ME3 5/2/03 928 938 5/2/03 5:12 10.48 43.85 84.69 281.09 56.15 167.71 54.37

ME1 5/2/03 735 745 5/2/03 7:40 16.18 35.42 16.85 83.28 20.74 56.96 17.37

ME1 5/2/03 745 755 5/2/03 8:15 19.57 29.39 22.92 121.35 30.46 86.71 27.35

ME1 5/2/03 745 805 5/2/03 8:20 22.74 29.85 28.56 104.73 18.11 55.28 16.95

ME1 5/2/03 805 815 5/2/03 8:35 22.95 33.30 22.15 149.75 29.73 69.31 22.45



### 6-1ME2 5/2/03 1645 1655 5/2/03 1:30 14.18 47.03 4.21 19.10 5.85 18.00 5.11

ME2 5/2/03 1655 1705 5/2/03 1:40 13.67 47.85 7.92 26.49 5.24 13.67 4.05

ME1 5/5/03 750 800 5/5/03 5:00 14.99 39.76 15.94 75.70 17.13 53.58 16.78

ME1 5/5/03 800 810 5/5/03 5:10 17.22 33.13 15.05 66.46 0.00 0.00 0.00

ME1 5/5/03 820 830 5/5/03 6:20 21.77 38.99 21.32 151.16 12.04 46.64 13.37

ME1 5/5/03 810 820 5/5/03 6:50 19.78 35.90 24.70 138.72 25.47 90.35 30.36

ME4 5/5/03 923 933 5/5/03 5:57 17.46 28.63 1.76 10.36 1.61 5.98 1.23

ME4 5/5/03 933 943 5/5/03 6:07 16.70 29.65 103.75 386.16 34.98 121.64 31.29

ME 3 5/5/03 1045 1055 5/5/03 5:15 12.42 35.10 4.94 14.62 2.06 8.31 1.89

ME 3 5/5/03 1055 1105 5/5/03 5:25 12.31 35.33 6.55 21.64 2.92 11.16 2.29

ME2 5/6/03 1645 1655 5/6/03 1:10 13.70 33.79 4.95 17.18 2.82 9.78 2.06

ME2 5/6/03 1655 1705 5/6/03 1:20 13.49 34.22 1.39 1.26 0.32 1.07 0.23

ME2 5/6/03 1705 1715 5/6/03 1:30 13.59 34.62 12.52 48.73 14.31 51.91 18.25

avg 4:29 16.54 32.25

max 9:38 33.04 53.49

min 1:04 8.93 10.84



### 6-2

### C2-C12 Hydrocarbons Target List

Mnemonics Names Formula MW Group

1 ETHENE ethene C2H4 28.05 O

2 ACETYL acetylene C2H2 26.04

3 ETHANE ethane C2H6 30.07 P

4 PROPE Propene C3H6 O

5 N_PROP n-propane C3H8 44.10 P

6 I_BUTA isobutane 58.12 P

7 LIBUTE isobutene C4H8 56.11 O

8 LBUT1E C4H8 56.11 O

9 BUDI1,3 1,3-butadiene C4H6 54.1 O

10 n-butane C4H10 58.12 P

11 T2BUTE t-2-Butene C4H8 56.11 O

C2BUTE c-2-butene C4H8 56.11 O

13 IPENTA isopentane C5H12 72.15 P

14 PENTE1 1-pentene C5H10 70.13 O

15 N_PENT n-pentane C5H12 72.15

16 I_PREN isoprene C5H8 68.11 O

17 T2PENE t-2-Pentene C5H10 O

18 C2PENE c-2-pentene C5H10 70.13 O

19 BU22DM 2,2-dimethylbutane 86.17 P

20 CPENTA cyclopentane C5H10 70.13 P

21 BU23DM C6H14 86.17 P

22 PENA2M 2-methylpentane C6H14 86.17 P

23 

### 6.2 Appendix B: Canisters and Tenax

Y

42.08

C4H10

1-butene

N_BUTA

12

P

70.13

C6H14

2,3-dimethylbutane

PENA3M 3-methylpentane C6H14 86.17 P

24 P1E2ME 2-methyl-1-pentene C6H12 84.16 O

25 N_HEX n-hexane C6H14 86.17

26 MCYPNA Methylcyclopentane C6H12 84.16 P

27 PEN24M 2,4-dimethylpentane C7H16 100.20

28 BENZE benzene C6H6 78.11 A

29 CYHEXA cyclohexane C6H12 84.16

30 HEXA2M 2-methylhexane C7H16 98.19 P

31 PEN23M P

P

P

2,3-dimethylpentane C7H16 100.20 P

32 HEXA3M 3-methylhexane C7H16 100.20 P

33 PA224M 2,2,4-trimethylpentane C8H18 114.23 P

34 N_HEPT n-heptane C7H16 100.20 P

35 MECYHX methylcyclohexane C7H14 98.19 P

36 PA234M 2,3,4-trimethylpentane C8H18 114.23 P

37 TOLUE toluene C7H8 92.14 A

38 HEP2ME 2-methylheptane C8H18 114.23 P

39 HEP3ME 3-methylheptane C8H18 114.23 P

40 N_OCT n-octane C8H18 114.22 P

41 ETBZ ethylbenzene C8H10 106.16 A

42 MP_XYL mp-xylene C8H10 106.16 A

43 STYR styrene C8H8 104.14 A

44 O_XYL o-xylene C8H10 106.17 A

45 N_NON n-nonane C9H20 128.26 P



### 6-346 IPRBZ isopropylbenzene C9H12 120.20 A

47 N_PRBZ n-propylbenzene C9H12 120.20 A

48 M_ETOL m-ethyltoluene C9H12 120.20 A

49 P_ETOL p-ethyltoluene C9H12 120.20 A

50 BZ135M 1,3,5-trimethylbenzene C9H12 120.20 A

51 O_ETOL o-ethyltoluene C9H12 120.20 A

52 BZ124M 1,2,4-trimethylbenzene C9H12 120.20 A

53 N_DEC n-decane C10H22 142.29 P

54 BZ123M 1,2,3-trimethylbenzene C9H12 120.20 A

55 DETBZ1 m-diethylbenzene C10H14 134.22 A

56 DETBZ2 p-diethylbenzene C10H14 134.22 A

57 N_UNDE n-undecane C11H24 156.30 P

58 MTBE methyl t-butyl ether C5H12O 88.14 E

TNMHC

A = aromatic, AL = Aldehyde, O = alkene (olefin), P = parafin, Y = alkyne, K = ketone, E = ether, X = haogenated, OH = alcohol



### 6-4Concentrations in ppbC, Tenaxsitedatestarthhmmstophhmmduration(min)ethohmtbetolueetbzmp_xylo_xylFreeway4/29/0307420822400.000.00215.2243.24166.0861.29Freeway4/29/0307420822400.000.00229.5444.83170.3962.76Refueling W/Vapor Re4/29/0312001220200.000.0082.0611.6548.3914.41Garage4/29/0316421712304.240.00105.0223.0895.9732.16Freeway4/30/030739081941.10.000.00342.3864.43247.2689.48Refueling W/O Vapor4/30/030921094119.920.000.00240.6838.40165.0251.89Refueling W/Vapor Re4/30/0310451105200.000.0019.614.2017.135.91Refueling W/O Vapor4/30/0312051225200.000.0049.125.2020.246.35Garage4/30/0316451715300.000.00187.1947.86200.4772.90Refueling W/O Vapor5/1/031106112620.430.000.00146.4810.8945.2211.69Refueling W/Vapor Re5/1/031225124521.30.000.0035.576.6731.1210.55Garage5/1/0316471717300.000.00222.6154.49208.2974.62Freeway5/2/0307350815400.000.00238.4739.24152.5657.05Refueling W/O Vapor5/2/0309180938200.000.00330.8453.26223.4571.59Refueling W/Vapor Re5/2/0310361056200.000.0051.2011.9358.0417.54Garage5/2/0316451715300.000.00137.4336.88145.8649.65Garage5/2/0316451715300.000.00159.0040.65161.5256.03Garage-Blank5/2/031710171000.000.000.190.000.000.00Freeway5/5/0307500830400.000.00396.2781.14304.94108.37Refueling W/O Vapor5/5/0309230943200.000.00270.8124.4794.6825.35Refueling W/Vapor Re5/5/0310451105200.000.0010.472.379.103.62Garage5/6/0316451715300.000.0043.2011.7752.2917.476-5Canister BTEX, ppbCsitedatetimeTime (min)an_typebudi13benzetolueetbzmp_xylo_xyltnmhcFreeway4/29/03742-82220p10.7854.57317.4359.84199.3479.522999.48Refueling W/Vapor Recovery4/29/031200-12055p8.8615.3588.9714.9647.7417.41894.91Refueling W/Vapor Recovery4/29/031200-12055r8.7915.5291.1815.3350.5718.452020.37Refueling W/Vapor Recovery4/29/031200-122020p1.1520.2769.3611.4638.5414.82685.11Garage4/29/031642-171220p6.7833.88102.6724.8184.1933.61234Refueling W/Vapor Recovery4/30/031045-110520p0.997.7431.647.7927.9711.75649.59Refueling W/Vapor Recovery4/30/031045-110520r0.997.8431.817.828.0711.73631.17Refueling W/Vapor Recovery4/30/031055-11005p0.8316.788.0917.559.1222.261718.23Refueling W/O Vapor Recovery4/30/031205-124520p0.5312.854.959.1731.6812.131694.75Refueling W/O Vapor Recovery4/30/031212-12175p0.146.9723.53.019.833.651171.77Garage4/30/031645-171520p11.5259.62223.4555.82192.4677.972081.38Freeway4/30/03739-81920p12.6760.04376.2769.5235.8393.923423.75Refueling W/O Vapor Recovery4/30/03921-92720p1.41247.58708.871.8223.8877.1646526.7Refueling W/O Vapor Recovery4/30/03921-94120p1.0856.75239.8644.01152.1658.448873.4Refueling W/O Vapor Recovery5/1/031106-112620p0.6614.0270.6814.651.820.041967.44Refueling W/O Vapor Recovery5/1/031117-11235p0.89132.77385.7137.26123.0941.8425852.97Refueling W/Vapor Recovery5/1/031225-124520p1.069.6643.999.6233.6713.441061.07Garage5/1/031642-171720p13.1863.78239.7857.81202.7878.492437.45Freeway5/1/03720-80020p21.38109.66534.7599323.27124.464797.09Freeway5/1/03720-80020r20.43107.86523.1797.41318.88122.914718.69Refueling W/Vapor Recovery5/2/031036-105620p0.613.7864.9916.7662.624.44991.98Refueling W/Vapor Recovery5/2/031046-10515p0.194.9735.091661.0325.1673.83Garage5/2/031645-171520p6.9331.72119.6730.29108.2542.871269.07Freeway5/2/03735-81520p10.2243.61215.6538.17125.2748.753511.63Refueling W/O Vapor Recovery5/2/03918-93820p49.8122.93419.5465.06229.5785.6621721.07Refueling W/O Vapor Recovery5/2/03929-9345p2.94458.681320.65199.46674.97254.191380.02Refueling W/Vapor Recovery5/5/031045-110520p0.549.350.5911.1139.6415.3699.04Refueling W/Vapor Recovery5/5/031055-11005p1.3314.6582.7916.551.2321.15980.43Freeway5/5/03750-83020p10.6657.6312.8566.46230.0690.793246.66Refueling W/O Vapor Recovery5/5/03923-94320p1.38419.621093.91101.8328.81109.5373618.24Garage5/6/031645-171520p6.3529.1899.132693.9736.3710456-6Canisters - Full C2-C12 Speciation (ppbC)siteRefuelingW/VaporRecoveryRefuelingW/VaporRecoveryRefuelingW/O VaporRecoveryRefuelingW/VaporRecoveryRefuelingW/O VaporRecoveryRefuelingW/O VaporRecoveryRefuelingW/VaporRecoveryRefuelingW/O VaporRecoveryRefuelingW/O VaporRecoveryRefuelingW/VaporRecoveryRefuelingW/VaporRecoverydate4/30/034/30/034/30/035/5/035/5/034/30/034/29/035/2/035/1/035/1/035/2/03time1045-11051045-1105921-9411045-1105923-9431205-12451200-1220918-9381106-11261225-12451036-1056an_typeprpppppppppcanisterC073C073C095C136C186C085C046C153C227C076C010ethane5.205.268.834.5834.045.385.9114.874.604.805.00ethene10.8210.936.985.705.325.4810.9611.464.098.257.79acetyl35.9037.3013.6012.674.1014.6928.9020.415.2222.1613.31prope4.424.4120.393.04555.076.259.4384.863.664.74.69n_prop3.033.0444.313.37654.8822.0711.72138.739.065.84.97i_buta8.398.37292.118.363119.1149.7976.51781.185.7935.3614.52lbut1e1.021.0214.770.6468.502.324.0425.0610.583.810.86libute1.691.6753.120.60335.617.860.00127.695.553.742.21budi130.990.991.080.541.380.531.1549.80.661.060.6n_buta42.9742.251350.1352.0815644.09217.4398.793806.37354.28158.677.7t2bute1.441.549.991.13404.029.1612.28114.9617.446.292.11c2bute0.790.8331.441.58179.854.117.2353.9811.384.072.81ipenta99.6699.213079.399.9625116.14557.31812.578387.13474.96233.46176.62pente11.311.4177.44.41428.67.3314.96150.0610.495.036.71n_pent16.716.89496.4717.434118.1983.55137.591229.9383.2941.9227.72i_pren0.470.471.430.413.580.8511.350.690.560.45t2pene8.538.59253.289.081998.1642.7172.47596.8345.3924.8513.25c2pene3.424.02100.553.73795.7716.8729.41235.5718.8110.715.35bu22dm2.041.9941.612.523708.7211.7116.556.163.423.66cpenta1.911.8542.072.44386.018.4511.17112.468.764.183.03bu23dm3.123.1673.754.58623.6512.0123.03170.6514.379.996.11pena2m12.5712.62265.5119.012433.148.1681.18653.2550.3525.2522.83pena3m7.568.25149.7711.811379.4227.4946.61366.9228.714.2413.94p1e2me0.90.912.441.52156.272.43.828.523.371.551.72n_hex5.325.3789.448.95840.1217.8428.87219.9616.878.729.71mcypna8.738.85142.415.071332.1227.1945.25352.7328.5914.2716.54pen24m0.97114.41.79112.792.894.5232.784.33.782.13benze7.777.79579.26419.6212.820.36123.0514.039.6713.826-7cyhexa2.382.4235.484.22291.397.9810.3190.557.390.325.59hexa2m5.575.486210.02467.7314.1819.39145.5414.937.8811.42pen23m2.031.9925.293.57171.675.377.4654.367.465.334.25hexa3m0.30.283.320.4321.310.560.846.210.740.380.44pa224m2.192.123.453.75173.55.217.1355.494.763.054.2n_hept4.254.4945.478.45278.3910.6613.79103.5111.516.4110.54mecyhx4.674.7247.998.5308.1410.5614.49105.312.116.4510.63pa234m0.640.675.230.920.081.011.96.692.652.331.28tolue31.6431.81239.9750.591093.9154.9569.39419.5470.6843.9864.99hep2me2.292.3417.193.6467.263.624.9129.514.613.024.88hep3me2.62.5817.283.8665.213.85.5129.535.033.215.26n_oct1.961.9611.362.5733.322.523.7717.782.522.233.75etbz7.917.8645.2411.05101.89.2211.566.1414.889.6216.9mp_xyl28.3928.07152.2639.78328.8131.7238.56229.8452.4333.6862.6styr1.411.274.371.374.230.91.433.811.041.361.49o_xyl11.7211.7558.8315.37109.5312.1115.6585.9120.2313.3824.36n_non1.091.035.511.447.091.111.657.480.721.192.08iprbz0.690.663.480.814.190.760.824.341.090.81.29n_prbz2.72.6211.773.0612.852.383.0514.764.032.774.62m_etol9.178.7634.1410.4136.043.624.4542.7613.279.5416.57p_etol4.384.1216.914.6815.857.539.4120.546.114.527.53bz135m4.32414.924.6113.893.534.418.185.984.157.81o_etol4.113.9512.94.514.293.515.0916.695.574.026.6bz124m13.9512.8947.2415.4340.5411.1414.3852.4920.0814.6325.18n_dec1.972.271.720.391.731.181.363.260.461.010.73bz123m3.483.391.090.387.522.553.430.980.653.235.13detbz10.991.042.250.781.920.741.542.981.090.81.22detbz23.243.146.542.785.082.012.937.313.282.474.01n_unde1.471.513.531.42.11.051.833.31.111.141.84tnmhc656.76646.788908.0670272023.31690.042706.5721748.671976.271062.58996.546-86.3 Appendix C: Breath SamplesSiteDateTimebud13CO2,%ethohmtbebenzetolueetbzmp_xylo_xylRefueling W/Vapor Recovery , PreFuel4/2912005.090.27133.860.740.8799.310.531.360.33Refueling W/Vapor Reco very, PostFuel4/2912154.380.1087.750.460.8978.420.491.200.29Garage, Pre4/2916425.910.2178.100.460.8172.490.461.090.27Garage, Peak4/2916546.060.0412.110.180.232.120.160.610.16Garage, Post4/2917156.160.043.260.070.060.450.040.130.03Freeway, Pre4/297315.350.2051.260.270.70137.390.721.800.43Freeway, Peak4/298005.002.7726.901.134.73150.462.839.213.06Freeway, Post4/298265.440.8526.600.361.88125.080.992.720.76Refueling W/Vapor Recovery , PreFuel4/3010476.240.12138.930.691.1668.790.441.130.27Refueling W/Vapor Reco very, PostFuel4/3010595.790.65153.240.642.2877.750.782.250.62Refueling W/O Vapor Recover y, PreFuel4/3012034.930.1854.350.401.0150.460.441.180.31Refueling W/O Vapor Recovery, PostFuel4/3012165.800.00201.011.805.4775.040.651.660.41Garage, Pre4/3016436.111.35137.300.321.8760.470.621.610.43Garage, Peak4/3017076.013.65107.430.335.3561.731.735.531.80Garage, Post4/3017215.835.24123.880.577.1763.391.685.291.72Freeway, Pre4/307275.640.1586.910.480.6487.070.571.340.31Freeway, Peak4/307574.714.4851.230.757.92102.673.4911.353.69Freeway, Post4/308224.500.6954.620.361.8182.250.862.320.60Refueling W/O Vapor Recover y, PreFuel4/309234.920.1865.020.461.2275.460.691.790.50Refueling W/O Vapor Recovery, PostFuel4/309354.740.0064.675.0416.8099.082.146.551.94Refueling W/O Vapor Recover y, PreFuel5/111076.710.05103.180.350.972.720.150.430.126-9Refueling W/O Vapor Recovery, PostFuel5/111197.740.15176.981.222.764.980.270.860.28Refueling W/Vapor Recovery , PreFuel5/112276.020.11118.300.691.272.630.150.460.13Refueling W/Vapor Reco very, PostFuel5/112385.210.2181.070.551.142.610.180.590.18Garage, Pre5/116487.240.6545.680.341.412.900.290.820.26Garage, Peak5/117035.823.3699.740.373.975.920.641.900.61Garage, Post5/117196.300.7560.610.331.793.430.280.960.27Freeway, Pre5/17126.330.0736.680.240.290.640.040.150.04Freeway, Peak5/17355.053.7936.450.677.0319.531.935.912.03Freeway, Post5/18025.353.5823.500.466.1423.471.574.801.55Refueling W/Vapor Recovery , PreFuel5/210374.820.1242.470.450.9930.160.250.710.19Refueling W/Vapor Reco very, PostFuel5/210505.700.1328.590.471.2535.160.521.600.49Garage, Pre5/216455.250.9372.420.001.3229.850.341.000.29Garage, Peak5/217065.250.5669.430.181.0127.710.260.760.21Garage, Post5/217166.001.4563.470.182.7231.490.601.810.54Freeway, Pre5/27295.310.19113.500.200.4941.320.260.720.19Freeway, Peak5/27494.931.9666.010.353.6546.591.143.471.16Freeway, Post5/28164.572.1436.270.333.3650.420.912.530.75Refueling W/O Vapor Recover y, PreFuel5/29205.520.4270.740.200.7232.430.290.740.18Refueling W/O Vapor Recovery, PostFuel5/29326.090.0064.885.1516.0762.341.303.801.02Refueling W/Vapor Recovery , PreFuel5/510455.990.1092.421.092.855.580.290.850.24Refueling W/Vapor Reco very, PostFuel5/510585.590.0533.130.863.527.340.361.190.32Freeway, Pre5/57440.980.0617.620.270.310.530.050.140.04Freeway, Peak5/57555.892.0317.710.482.934.800.501.610.49Freeway, Post5/58325.252.1710.050.354.2915.671.223.791.29Refueling W/O Vapor Recover y, PreFuel5/59236.300.1888.500.230.671.770.130.460.13Refueling W/O Vapor Recovery, Post-5/59366.420.0084.8716.3680.6879.302.737.742.116-10FuelGarage, Pre5/616446.160.49175.180.301.422.650.321.000.34Garage, Peak5/617065.591.37102.340.221.973.930.552.000.67Garage, Post5/617186.480.6558.690.271.573.050.340.980.276-11

### 6.4 Appendix D: DNPH

Site Date Start

time Stop

time Duration V (L) Vu (L) formal formalu acetal acetalu aceto acetou

Freeway 4/29/03 0742 0822 40 47.1 2.36 17.38 0.95 5.27 0.80 32.18 1.85 Freeway 4/30/03 0739 0819 41 45.2 2.26 19.02 1.04 4.67 0.80 28.35 1.64 Freeway 5/1/03 0720 0800 41.1 45.3 2.27 19.80 1.07 8.22 0.95 57.34 3.24 Freeway 5/2/03 0735 0815 40 44.1 2.21 19.13 1.05 4.84 0.82 20.67 1.23 Freeway 5/5/03 0750 0830 40 44.1 2.21 17.56 0.97 5.24 0.83 61.17 3.45 Garage 4/29/03 1642 1712 30 33.0 1.65 5.59 0.43 2.83 0.99 34.36 2.01 Garage 4/30/03 1645 1715 30 33.0 1.65 7.58 0.52 3.50 1.01 27.38 1.63 Garage 5/1/03 1642 1717 30 33.0 1.65 9.12 0.58 3.76 1.01 20.23 1.27 Garage 5/2/03 1645 1715 30 33.1 1.66 7.35 0.49 2.76 0.99 21.77 1.35 Garage 5/6/03 1645 1715 30 33.1 1.66 5.44 0.42 2.50 0.98 44.91 2.58 Garage-Blank 5/2/03 1706 1706 0 30.6 1.53 0.00 0.23 1.85 0.27 1.68 0.19 Garage-Blank 5/6/03 1612 1612 0 30.6 1.53 0.00 0.23 0.43 0.21 0.87 0.17 Refueling W/O Vapor 4/30/03 0921 0941 19.9 21.9 1.10 3.62 0.52 3.37 1.47 13.31 1.12 Refueling W/O Vapor 4/30/03 1205 1225 20 22.0 1.10 2.12 0.46 2.57 1.46 10.66 1.03 Refueling W/O Vapor 5/5/03 1106 1126 20.4 22.4 1.12 5.52 0.55 2.72 1.43 31.06 1.92 Refueling W/O Vapor 5/2/03 0918 0938 20 22.0 1.10 4.03 0.53 3.26 1.46 5.98 0.89 Refueling W/O Vapor 5/5/03 0923 0943 20 22.0 1.10 5.52 0.56 3.17 1.46 20.10 1.40 Refueling W /Vapor

Re 4/29/03 1200 1220 20 22.0 1.10 4.35 0.54 2.97 1.46 20.00 1.39

Refueling W /Vapor

Re 5/1/03 1225 1245 21.3 23.4 1.17 3.29 0.49 1.77 1.36 10.01 0.96

Refueling W /Va p or Re 4/30/03 1045 1105 20 22.0 1.10 2.87 0.47 1.38 1.44 12.90 1.11

Refueling W /Vapor

Re 5/2/03 1036 1056 20 22.0 1.10 4.67 0.54 2.47 1.46 9.07 0.97

Refueling W /Vapor

Re 5/5/03 1045 1105 20 22.0 1.10 3.29 0.52 1.78 1.44 7.94 0.95

formal =Formaldehyde acetal = Acetaldehyde formalu =Formaldehyde uncertainty acetalu =Acetaldehyde uncertainty

aceto=Acetone acetou=Acetone uncertainty



### 6-12

# Appendix F

Evaporative and Tailpipe Emissions Support for S211b Tier 2 Exposure Study SwRI® Project 03.05383 – Final Report

# SOUTHWEST RESEARCH INSTITUTE ®

6220 CULEBRA ROAD i POST OFFICE DRAWER 28510 i SAN ANTONIO, TEXAS, USA 78228-0510 i (210) 684-5111 i WWW.SWRI.ORG
HTTP://ENGINEANDVEHICLE .SWRI.ORG

ENGINE, EMISSIONS, AND VEHICLE RESEARCH DIVISION ISO 9001 CERTIFIED FAX: (210) 522-3950 ISO 14001 Certified

SAN ANTONIO, TEXAS

HOUSTON, TEXAS i WASHINGTON, DC i ANN ARBOR, MI 

### July 29, 2005

TO: Desert Research Institute

2215 Raggio Parkway Reno, NV 89512-1095

ATTN: Dr. Barbara Zielinska

SUBJECT: Final repo rt for SwRI ® 

### Project 03.05383, “Evaporativ e and Tailpipe Em issions Support for S211b Tier 2 Exposure Study”

1.0 INTRODUCTION

This report describes the work performed during the summe r of 2002 and the winter of 2004/2005 by the Department of Engine and Emissi ons Research (DEER) at Southwest Research
Institute ® 

### (SwRI) in support of Desert Research Inst itute’s (DRI) project entitled “S 211b Tier 2 Exposure Study.”

2.0 STATEMENT OF WORK

The objective of this project was to provide DR I with a variety of s upport activities, test vehicles, a support vehicle, and to perform laborat ory testing, all in suppo rt of DRI’s S211b Tier 2 Exposure Study perform ed for the Am erican Petr oleum Institute. The portion of DRI’s study performed in the San Antonio, Texas area consis ted of on-road em issions measurements using a trailing vehicle, garage testing of exhaust and evaporative emissions, and laboratory exhaust and evaporative emissions measuremen ts. SwRI provided logistics support to DRI personnel for the on-road and garage testing, but perform ed no emissi ons measurements for these tasks. Two test vehicles were procured f or the program (a 1993 Toyota Camry V6 and a 1995 Ford F-150 V8), as well as a Dodge Caravan as a trailing vehicle for the on-road work in San Antonio. These
vehicles were used for the on-road testing and garage te sting, and then were utilized for hot soak evaporative and FTP exhaust emissi ons testing in the SwRI laborat ory. All tests were performed
with the vehicles in norm al and in a m alf unction condition. Tests were perform ed while operating on summ er and winder grade fuels, fr om Houston, Atlanta, and Chicago. Summ er grade fuels were used in 2002 and winter grade fuels were used in 2005. Selected properties of these fuels are presented in Table 1.Dr. Barbara Zielinska
Desert Research Institute July 29, 2005 Page 2 of 9

Report 03-05383 

### TABLE 1. TEST FUEL PROPERTIES

Summer 2002 Winter 2005

Houston Atlanta Chicago Houston Atlanta Chicago Parameter, method

GA-4614 GA-4637 GA-4640 GA-5427 GA-5437 GA-5440

ASTM D5845 Petrospec ®

MeOH, wt% N/A N/A N/A 0 0 0

EtOH, wt% (D5599) N/A (0) (10.75) 0 0 10

MTBE, wt% (D5599) (9.86) N/A N/A 10.7 0.4 0.6

ETBE, wt% N/A N/A N/A 0 0 0

TAME, wt% N/A N/A N/A 1.4 0 0

DIPE, wt% N/A N/A N/A 0 0.2 0.5

TBA, wt% N/A N/A N/A 0.3 0 0

O 2 Total wt% (D5599) (1.81) (0.01) (3.73) 2.23 0.1 3.66

Benzene, vol% (D5580) (0.62) (1.24) (0.84) 0.5 1.06 1.03

Aromatic, vol% (D1319) (19.9) (38.4) (17.1) 17.5 21.4 16.3

Olefins, vol% (17.3) (10.5) (9.1) 9.4 6.0 15.2

Saturate, vol% (52.8) (51.1) (70.9) 60.8 72.0 58.0

RON N/A N/A N/A 92.2 90.5 92.3

MON (D2700) N/A (81.9) (83.0) 83.5 82.9 82.8

R+M/2 N/A N/A N/A 87.8 86.7 87.5

T50, degF (D86) (190) N/A N/A 184 208 164

T90, deg F (D86) (327) N/A N/A 330 336 319

E200, % N/A N/A N/A 52 40 59

E300, % N/A N/A N/A 82 83 83

RVP, ASTM D5191 7.01 6.29 6.93 10.20 10.87 14.16

API Gravity, ASTM D4052 61.1 55.5 63.7 62.1 60.3 62.8

Specific Gravity,
ASTM D4052 0.7347 0.7568 0.7390 0.7308 0.7379 0.7282

Carbon content, wt%,
ASTM D5291 84.77 86.76 82.30 83.99 86.28 80.85

Hydrogen content, wt%,
ASTM D5291 14.04 13.14 13.71 13.95 13.25 13.64

In some instances, two different methods were utilized to determine fuel properties. In these instances, the second method and corresponding re sults are presented in parentheses.



### SwRI utilized malfunction conditions determin ed in the 2002 portion of the study to give exhaust hydrocarbon emissions on th e order of two grams per mile . These induce d malfunctions included re moval of th e ca talyst s on both vehicles plus a calibra ted m anifold air leak on th e Toyota Camry. The m alfunction for the hot soak por tion of the SHED test consisted sim ply of disconnecting the evaporative can isters from the vehicles.Dr. Barbara Zielinska
Desert Research Institute July 29, 2005 Page 3 of 9

Report 03-05383 

### For the dynam ometer FTP exhaust em issions te sting, regulated exhaust em issions (total hydrocarbons, THC; non-m ethane hydrocarbons , NMHC; carbon m onoxide, CO; and oxides of nitrogen, NO

x 

### ), carbon dioxide, CO 2 

### ; and speciated volatile orga nic compound (VOC) emissions (to include MTBE, ethanol, benzene, toluen e, ethy lbenzene, xylene, 1, 3-butadiene, formaldehyde, and acetaldehyde) were determ ined for each test. During hot soak tests, tota l hydrocarbon and VOC emissions (a s above except without aldehyde /ketone measurements) were determined. A sealed housing for evaporative determinations (SHED) was utilized f or the hot soak tests. The test plan followed for th e laboratory testing is presented in Table 2.

TABLE 2. TEST PLAN

STEP DESCRIPTION

1 Verify proper mechanical ope ration of the test vehicle.

2 Remove canister from test vehicle.

3 Purge canister with 300°F “zero” nitrogen at 20L/min for five hours, reattach canister.

4 Drain fuel tank and fill to 40 percent capacity with test fuel.

5 Perform a 2-hour diurnal heat build from 70 to 120°F at a ramp rate of 0.4°F/min.

6 Operate vehicle on chassis dynamometer over one UDDS cycle.

7 Turn engine off for five minutes.

8 Start engine and idle for one minute.

9 Turn engine off for one minute.

10 Start engine and idle for one minute.

11 Remove canister from vehicle and purge ca nister with “zero” air for 60 minutes.

12 Reattach canister, drain fuel from tank, and fill to 40 percent capacity with chilled test fuel.

13 Conduct one hour DHB (no emission measurements).

14 Operate vehicle on chassis dynamometer over one UDDS.

15 Soak vehicle overnight.

16 Next day prior to the cold-start exhaust portion of the FTP, conduct one-hour Diurnal Heat Build. (DHB).

17 Conduct 3-bag FTP exhaust emission test. Measure regulated gaseous emissions and VOC. emissions.

18 Conduct th e Hot Soak segmen t o f th e SHED test imme diately fo llowing t he ex haust em issions testing.

19 Switch vehicle to malfunction condition, and disconnect evaporative canister.

20 Repeat Steps 6 through 10 and Steps 14 through 18.

21 Repeat Steps 1 through 20 for each of the remaining two test fuels.

22 Switch to next test vehicle, and repeat Steps 1 through 21.Dr. Barbara Zielinska
Desert Research Institute July 29, 2005 Page 4 of 9

Report 03-05383 

### 3.0 TEST PROCEDURES

The exhaust em ission portion of the FTP utilizes the Urban Dyna mometer Driving Schedule (UDDS), which is 1372 seconds in durati on. The UDDS is divided into two segm ents; the first consisting of 505 seconds, and the second consisting of 867 seconds. A FTP i s composed of a 505-second cold-transient (bag 1) portion and an 867-second cold stabilized (bag 2) portion, followed by a ten-mi nute soak and then a 505-second hot-transient (bag 3) portion. A summary of the cycle duration, driv ing distance, and average speed is given in Table 3. The FTP driving schedule with the cold- a nd hot-transient test segments identified is given in Figure 1.

The evaporative em ission portion of the FTP as conducted in this study consisted of a one-hour Diurnal Heat Build (DHB) (40 CFR 86.133-90) and a one-hour Hot Soak Loss Test (HSL) (40 CFR 86.138-90). Total hydrocarbons and VOC em issi ons were record ed only during the HSL se gment of th e te st. Prior to the c old-start ex haust po rtion of the FT P, the DHB evaporative segment of the FTP was conducted by fu eling the test vehicle to 40 percent of tank capacity with test fuel at a te mperature below 55°F. A heating blan ket was a ttached to th e outside of the fuel tank, and a thermocouple placed in the fuel inside the fuel tank was connected to the computer controller. The fuel inside the tank was raised to a nominal temperature of 60°F, at which point the DHB segm ent of t he test began. The fuel tem perature was raised at a linea r rate of 0.4°F per minute for the 60 minute test . The final nominal temperature was 84°F.

The HSL segment of the evaporative emissi on test was conducted immediately following FTP exhaust emission testing. The vehicle was allo wed to “soak” in the enclosure for one hour. Total hydrocarbon and VOC e missions were measured at the beginning a nd end of the one hour segment to perm it calculation of hot soak evapo rative emissions. Alcoh ol measurements were included only for the Chicago fuel.

FIGURE 1. FTP DRIVING SCHEDULEDr. Barbara Zielinska
Desert Research Institute July 29, 2005 Page 5 of 9

Report 03-05383 

### TABLE 3. SUMMARY OF FTP DRIVING SCHEDULE

Segment Duration,

Seconds Distance,

Miles Average Speed,

Miles/Hr.

Transient Phase 505 3.60 25.7

Stabilized Phase 867 3.90 16.2

UDDS 1372 7.50 19.7

The following sections describe the sampling a nd analytical procedures that were utilized for this study.

3.1 Exhaust Emissions

Emissions of THC, NMHC, CO, NO

x 

### , and CO 2 

### were quantif ied in a m anner consistent with EPA protocols for light-duty em issions testing as given in the Code of Federal Regulations, Title 40, Part 86, Subpart B. Em issions of THC, CO, NO

x 

### , and CO 2 

### were s ampled using proportional exhaust gas sam ples collected in Te dlar bags. Total hydrocarbon em issions were measured using a flame ionization detector, while CO and CO 2 

### were determ ined using nondispersive infra-red instru ments. Em issions of NO

x 

### were m easured using a chem iluminescent instrument. W et absorption techniques were employed to collect alco hol and aldehyde VOC. Alcohol analysis was perform ed with gas chro matography – fla me ionization detection and aldehydes were m easured by high performance liquid chrom atography with ultra-violet
absorbance detection. Values for NMHC were de termined by subtracting methane (co rrected for FID response factor) from THC.

3.2 Evaporative Emissions

At the beginning and end of each Hot So ak Loss (HSL) segm ent, total hydrocarbon evaporative emissions were measured according to methods described in 40 CFR 86.138-90. In addition to total hydrocarbon em issions, bag samp les were taken at the beginning and end of each of the evaporative em ission test segm ents to permit hydrocarbon speciation an alyses to b e performed, and to collect sufficient sample for al cohol analyses (when an alcohol fuel blend was used during testing). Because approximately two minutes were required to adequately fill a bag for analys is, sam pling was initia ted one m inute before the start poin t and continu ed until one minute after the stop point.

3.3 Hydrocarbon Speciation Procedures for VOC Determinations

The analytical procedures used for conducting hydroc arbon speciation (C 2 

### to C 12 

### hydrocarbons, aldehydes and ketones, and alcohols ) are similar to the CRC Auto/Oil Phase II methods. W ith these m ethods, exhaust and evapor ative emissions samples are analyzed for the presence of m ore than 200 different exhaust species. Four GC pro cedures and one HPCL procedure are used to identify and quantify compounds. In general, all emission “sample” bagsDr. Barbara Zielinska
Desert Research Institute July 29, 2005 Page 6 of 9

Report 03-05383 

### were analyzed before the “background” bags so that reactive exha ust com pounds can be analyzed as quickly as possible. A brief desc ription of these procedures is given below.

3.3.1 C 2 

### -C 4 

### Species

The first GC procedure uses a 15 m x 0.53 mm I.D. DB-WAX (1Fm film ) pre-column and a 50 m x 0.53 mm I.D. (10 Fm film) Alumina PLOT/KCI (Carbopack ® 

### ) column to pe rmit the separation and determ ination of exhaust concentrations of C 1 

### -C 4 

### individual hydrocarbon species, including ethan e; ethylene; acetylene; pr opane; propylene; propadiene; butane; trans-2 - butene; 1-butyne; and cis-2-buten e. Bag sam ples were analyzed using a gas chrom atograph equipped with a F ID. The gas chrom atograph sy stem utilizes two an alytical colu mns. The carrier gas is helium. An external multiple compone nt standard in zero air is used to quantify the
results. Detection lim its for th e procedure are on the order of 5 ppbC in d ilute exhaust for all compounds.

3.3.2. C 5 

### -C 12 

### Species

The second GC procedure uses a 60 m x 0.32 mm I.D. (10 Fm fil m) DB-1 column to provide separation and exhaust concentrations for m ore than 100 C 5 

### -C 12 

### individual HC compounds. Bag sam ples are analyzed using a ga s chromatograph equipped with a FID. The GC system utilizes a FI D, a pneumatic ally ope ra ted and electrically co ntrolled valve, and an analytical column. The carrier gas is helium . An external multiple co m ponent standard in zero air is used to quantify the results. Detection limits for the procedure are on the order of 10 ppbC in dilute exhaust for all compounds.

3.3.3 Benzene and Toluene

The third GC procedure uses a separate syst em configured sim ilarly to the second GC
method to determ ine individual concentration s of benzene and tolu ene accord ing to CRC
Auto/Oil Phase II Protocols. The third GC utili zes a 30 m x 0.25 mm I.D. (0.25 Fm film) DB-5
column instead of a DB-1 column.

3.3.4 Aldehydes and Ketones

A HPL C wi th a Zorbax ® 

### ODS column was utilized for the analysis of aldehydes and ketones. Samples are collected by bubbling dilute exhaust at a nom inal flow rate of 4 L/ min through chilled glass im pingers containing an ac etonitrile solution of 2,4-DNPH and perchloric acid. For analysis, a p ortion of the acetonitrile so lution is injected in to a liquid chrom atograph equipped with a UV detector. External standard s of the aldehyde and ketone DNPH derivatives are used to quantify the resu lts. The aldeh ydes and ketones that were m easured include: formaldehyde, acetaldehyde, ac rolein, acetone, propionaldehyde, crotonaldehyde, nbutyraldehyde, benzaldehyde, is ovaleraldehyde, valeraldehyde, o -tolualdehyde, m+ptolualdehyde (not resolved from each other dur ing normal operating conditions, and so reported together), dimethylbenzaldehyde, and hexanaldehyde . Detection limits for this procedure are on the order of 0.005 ppm aldehyde or ketone in dilute exhaust.Dr. Barbara Zielinska
Desert Research Institute July 29, 2005 Page 7 of 9

Report 03-05383 

### 3.3.5 Alcohols

The fourth GC is utilized to analyze alcohol s. The collection of ethanol in exhaus t and from the SHED was a ccomplished by bubbling the sam ple through glass im pingers. Each impinger contains 25 mL of dei onized wa ter m aintained at ice -bath tem perature. Exhaus t samples were collected continuously during test cycles at a nomina l flow rate of 4 L/min through a Teflon sample line held at 102°C (215°F). Ev aporative emissions were sampled from Tedlar bags using a system configured similarly to that used for exha ust emissions (except an unheated sample line is used to transfer the sample to impingers).

For analysis, a portion of the liquid sample is injected into a GC equipped with a FID and an analytical column. The anal ytical column is a 3 m x 0.53 mm I.D. capillary column with a 1- μm film of DB-WAX as the statio nary phase. The GC carrier gas is helium with a column head pressure of approxim ately 4 psi. External stan dards prepared in deion ized water are used to quantify the results. Detection lim its for this procedure are on the order of 0.06 ppm in dilute
exhaust.

4.0 RESULTS

Regulated emissions results for the Ford F-150 and the Toyota Cam ry are presented in Tables 4 through 7. Results are presented for the normal and m alfunction modes by fuel type. During the W inter 2005 season, fo r the Ford operating in norm a l mode on the Chicago fuel, a second exhaust emissions test was performed because the CO result appeared unexpectedly high. The CO result remained relatively high, however.

TABLE 4. REGULATED AND HOT SOAK EMISSIONS FOR FORD F-150, SUMMER 2002

Houston Fuel Atlanta Fuel Chicago Fuel
Parameter Units

Normal Malfunction Normal Malfunction Normal Malfunction HC g/mi 0.397 2.19 0.469 2.45 0.430 2.27 NMHC g/mi 0.296 2.09 0.366 2.35 0.281 2.17 CO g/mi 2.19 15.6 1.88 16.89 1.66 15.2 NOx g/mi 0.989 2.11 1.05 2.13 1.40 2.07 Fuel Economy mi/gal 14.9 15.0 15.3 15.1 14.5 14.8 Hot Soak HC g 0.00 2.60 0.07 2.18 0.00 1.95Dr. Barbara Zielinska
Desert Research Institute July 29, 2005 Page 8 of 9

Report 03-05383 

### TABLE 5. REGULATED AND HOT SOAK EMISSIONS FOR FORD F-150, WINTER 2005

Houston Fuel Atlanta Fuel Chicago Fuel
Parameter Units

Normal Malfunction Normal Malfunction Normal Normal Malfunction HC g/mi 0.570 2.39 0.588 2.63 0.795 0.794 2.41 NMHC g/mi 0.464 2.23 0.487 2.54 0.637 0.637 2.31 CO g/mi 2.95 16.3 2.90 17.2 9.32 8.19 16.4 NOx g/mi 1.04 2.02 1.08 2.20 1.12 1.26 2.27 Fuel Economy mi/gal 13.6 14.1 14.2 14.0 13.4 13.5 13.8 Hot Soak HC g 0.21 6.83 0.28 13.9 0.42 N/C* 21.0

*N/C = not conducted



### TABLE 6. REGULATED AND HOT SOAK EMISSIONS FOR TOYOTA CAMRY, SUMMER 2002

Houston Fuel Atlanta Fuel Chicago Fuel
Parameter Units

Normal Malfunction Normal Malfunction Normal Malfunction HC g/mi 0.227 4.05 0.288 3.89 0.244 4.21 NMHC g/mi 0.186 3.55 0.249 3.49 0.208 3.71 CO g/mi 3.18 64.4 2.64 59.5 2.61 60.4 NOx g/mi 0.525 2.56 0.581 2.64 0.516 2.44 Fuel Economy mi/gal 26.8 19.5 22.2 19.9 22.8 19.7 Hot Soak HC g 0.09 0.77 0.01 0.62 0.05 2.16



### TABLE 7. REGULATED AND HOT SOAK EMISSIONS FOR TOYOTA CAMRY FOR TOYOTA CAMRY, WINTER 2005

Houston Fuel Atlanta Fuel Chicago Fuel
Parameter Units

Normal Malfunction Normal Malfunction Normal Malfunction HC g/mi 0.268 3.99 0.384 4.03 0.388 3.75 NMHC g/mi 0.199 3.47 0.346 3.58 0.276 3.29 CO g/mi 2.72 64.5 3.78 63.0 3.89 55.0 NOx g/mi 1.15 1.98 0.877 2.46 0.873 2.76 Fuel Economy mi/gal 24.3 19.8 23.2 20.1 21.9 19.3 Hot Soak HC g 0.02 8.02 0.00 4.84 0.11 8.66Dr. Barbara Zielinska
Desert Research Institute July 29, 2005 Page 9 of 9

Report 03-05383 

### The speciated hydrocarbon resu lts are presented in Appendix A for the Ford F-150 and in Appendix B for the Toyota Camry.

5.0 SUMMARY

This report describes a project in w hich SwRI provided logistic support to DRI for onroad and garage exposure studies, and for laborator y exhaust and evaporative em issions testing. Hot Soak evaporative and FTP tailpip e vehicle emissions were m easured for two vehicles operating on six fuels, to include operati on in normal and in malfunction conditions.

6.0 CLOSURE

It has been a pleasure to perform this proj ect for DRI. If you have any questions of a technical nature, please contact Patrick Merr itt by telephone at (210) 522 -5422, by fax at (210) 522-3950, or by e-mail at pmerritt@swri.org

.

Prepared by: Reviewed by:

Patrick M. Merritt Lawrence R. Smith Senior Research Scientist Manage r, Light-Duty and Unregulated Emissions Department of Engine and Emissions Research Department of Engine and Emissions Research

Approved by:

Jeff J. White Director of Development Department of Engine and Emissions Research

c: Sherry Twilligear, SwRI Contracts

### APPENDIX A

HYDROCARBON SPECIATION DATA

FOR FORD F-150

TABLE OF CONTENTS FOR APPENDIX A

FTP Composite Results, Winter 2005, pp. A1-A5

SHED Test Results, Winter 2005, pp. A6-A10 FTP Composite Results, Summer 2002, pp. A11-A15 SHED Test Results, Summer 2002, pp. A16-A20

A blank space in the tables indicates that the compound was not detected during analysis. A “Trace” value indicates that th e compound was dete cted, but computations of mass or mass rate
resulted in a value of less than 0.05. An “*” in the table indicates a malfunction of the analytical equipment during sample analysis and that no data are available.HYDROCARBON SPECIATION DATA:

FTP COMPOSITE

FORD F-150

FTP Composite, mg/mi

F-HOU-N F-HOU-MF F-ATL-N F-ATL-MF F-CHI-N F-CHI-MF

COMPOUND 3/16/2005 3/17/2005 3/23/2005 3/24/2005 3/28/2005 3/29/2005

METHANE 101.9 91.2 100.3 95.3 147.5 92.8

ETHANE 29.9 31.9 29.8 34.2 34.8 34.4

ETHYLENE 40.9 261.7 37.4 269.6 78.7 276.7

PROPANE 3.3 2.5 2.5 2.5 3.1 3.3

PROPYLENE 9.3 143.2 11.2 158.2 13.6 145.0

ACETYLENE 6.9 139.3 3.7 147.6 8.0 139.5

PROPADIENE 0.2 9.6 0.3 8.6 0.2 7.7

BUTANE 35.6 39.9 61.0 61.7 96.9 81.1

TRANS-2-BUTENE 1.4 10.9 1.6 11.7 3.6 11.7

1-BUTENE 2.0 25.5 2.0 25.6 3.9 24.7

2-METHYLPROPENE (ISOBUTYLENE) 11.6 104.1 3.8 57.4 5.3 44.6

2,2-DIMETHYLPROPANE (NEOPENTANE) 57.6 87.0 60.6 88.6 78.2 104.7

PROPYNE 0.3 11.6 0.3 10.6 0.2 1.1

1,3-BUTADIENE 0.7 32.9 1.0 33.7 1.1 39.1

2-METHYLPROPANE (ISOBUTANE) 5.0 5.8 5.4 5.5 6.1 5.4

1-BUTYNE

METHANOL

CIS-2-BUTENE 0.3 8.3 0.6 8.8 3.3 8.6

3-METHYL-1-BUTENE

ETHANOL 21.1 120.3

2-METHYLBUTANE (ISOPENTANE) 1.0 10.8

2-BUTYNE

1-PENTENE 0.9 8.9 0.5 3.2 1.3 2.0

2-METHYL-1-BUTENE 1.0 18.5 1.2 12.2 2.2 16.2

PENTANE 24.4 43.5 32.5 54.8 32.2 47.0

UNIDENTIFIED C5 OLEFINS Trace 1.7 Trace 0.5 0.3

2-METHYL-1,3-BUTADIENE 0.1 10.8 0.3 10.0 0.3 12.3

TRANS-2-PENTENE 1.4 11.5 1.3 8.1 3.2 14.4

3,3-DIMETHYL-1-BUTENE 0.4 0.1 0.5 Trace 0.5

CIS-2-PENTENE 0.7 6.4 0.6 4.7 1.8 8.5

2-METHYL-2-BUTENE 0.7 13.5 1.2 11.1 3.1 21.7

TERT-BUTANOL

CYCLOPENTADIENE 2.4 2.4 2.2

2,2-DIMETHYLBUTANE 6.3 10.6 4.9 8.0 2.8 5.4

CYCLOPENTENE 0.4 4.3 0.4 3.2 1.6 6.0

4-METHYL-1-PENTENE 0.3 3.5 1.0 2.3 0.5 3.7

3-METHYL-1-PENTENE

CYCLOPENTANE 1.4 5.8 1.3 4.4 2.1 4.5

2,3-DIMETHYLBUTANE 4.8 13.3 6.2 12.7 6.0 11.5

MTBE 7.5 83.7 0.1 1.7 0.2 2.4

4-METHYL-CIS-2-PENTENE

2-METHYLPENTANE 30.0 64.8 18.5 41.6 19.8 40.8

4-METHYL-TRANS-2-PENTENE 3.4 0.2 1.7 0.5 3.4

3-METHYLPENTANE 20.6 44.2 12.5 27.0 12.8 26.6

2-METHYL-1-PENTENE 0.3 3.4 0.4 2.8 0.5 4.0

1-HEXENE 0.3 3.4 0.4 2.8 0.5 4.0

HEXANE 18.3 43.6 11.5 26.4 9.6 21.9

UNIDENTIFIED C6 0.2 12.0 0.7 7.1 0.2 10.7

TRANS-3-HEXENE

CIS-3-HEXENE 0.4 2.6 0.3 1.4 0.6 3.3

DI-ISOPROPYL ETHER

TRANS-2-HEXENE 0.5 3.7 0.4 2.7 0.8 5.1 Houston Fuel Atlanta Fuel Chicago Fuel

PAGE A-1HYDROCARBON SPECIATION DATA:

FTP COMPOSITE

FORD F-150

FTP Composite, mg/mi

F-HOU-N F-HOU-MF F-ATL-N F-ATL-MF F-CHI-N F-CHI-MF

COMPOUND 3/16/2005 3/17/2005 3/23/2005 3/24/2005 3/28/2005 3/29/2005 Houston Fuel Atlanta Fuel Chicago Fuel

3-METHYL-TRANS-2-PENTENE 0.7 5.7 0.6 3.8 1.6 9.1

2-METHYL-2-PENTENE 0.4 3.4 0.4 2.7 0.9 5.5

3-METHYLCYCLOPENTENE Trace

CIS-2-HEXENE 0.2 2.0 0.2 1.0 0.5 2.7

ETBE

3-METHYL-CIS-2-PENTENE 0.4 3.2 0.4 2.1 1.1 5.8

2,2-DIMETHYLPENTANE, NOTE A 4.6 13.1 3.2 8.9 4.4 12.0

METHYLCYCLOPENTANE, NOTE A 4.5 12.8 3.1 8.7 4.3 11.8

2,4-DIMETHYLPENTANE 2.5 7.4 3.5 9.4 1.9 6.2

2,2,3-TRIMETHYLBUTANE 0.3 1.3 0.4 0.9 0.1 0.8

3,4-DIMETHYL-1-PENTENE 0.4 0.3 0.7

1-METHYLCYCLOPENTENE 1.0 5.6 1.0 4.7 1.2 7.6

BENZENE 6.5 46.5 10.6 81.3 14.8 80.5

3-METHYL-1-HEXENE 1.4 0.3 1.2

3,3-DIMETHYLPENTANE 2.1 3.9 1.4 2.3 0.9 0.5

CYCLOHEXANE 0.4 2.0 1.0 2.7 1.1 5.5

2-METHYLHEXANE

2,3-DIMETHYLPENTANE 14.4 43.5 12.4 38.7 7.8 23.4

1,1-DIMETHYLCYCLOPENTANE 0.1 Trace 0.5 0.3 1.2

TERT-AMYL METHYL ETHER

CYCLOHEXENE 0.8 11.1 0.1 1.3 0.2 2.7

3-METHYLHEXANE 12.1 35.6 8.4 26.5 4.9 14.3

CIS-1,3-DIMETHYLCYCLOPENTANE 0.3 4.0 1.0 2.7 2.3 6.4

3-ETHYLPENTANE 1.2 3.3 1.4 5.6 1.5 7.9

TRANS-1,2-DIMETHYLCYCLOPENTANE

TRANS-1,3-DIMETHYLCYCLOPENTANE 0.9 1.7 1.1 3.4 0.6 5.7

1-HEPTENE

2,2,4-TRIMETHYLPENTANE 3.8 15.4 21.7 57.4 6.7 17.9

2-METHYL-1-HEXENE

TRANS-3-HEPTENE 1.0 0.2 1.6 0.5 3.9

HEPTANE 7.5 27.0 6.8 23.1 4.3 14.0

CIS-3-HEPTENE

UNIDENTIFIED C7 1.0 6.5 0.3 2.9 1.3 6.7

2-METHYL-2-HEXENE 0.5 1.3 0.5 2.9

3-METHYL-TRANS-3-HEXENE

TRANS-2-HEPTENE 0.2 1.4 0.1 1.2 0.3 2.1

3-ETHYL-CIS-2-PENTENE Trace

2,4,4-TRIMETHYL-1-PENTENE 0.2 1.7 0.3 1.5 0.4 2.5

2,3-DIMETHYL-2-PENTENE

CIS-2-HEPTENE 0.1 1.1 1.0 0.2 1.5

METHYLCYCLOHEXANE 1.8 8.0 2.4 9.4 4.5 16.8

CIS-1,2-DIMETHYLCYCLOPENTANE

2,2-DIMETHYLHEXANE

1,1,3-TRIMETHYLCYCLOPENTANE 0.5 2.4 0.5 2.0 0.4 2.1

2,4,4-TRIMETHYL-2-PENTENE 0.1 Trace 0.2 0.1 Trace 0.3

2,2,3-TRIMETHYLPENTANE 0.5 2.6 2.2 9.4 1.1 6.8

2,5-DIMETHYLHEXANE

ETHYLCYCLOPENTANE

2,4-DIMETHYLHEXANE 1.4 9.1 2.8 11.9 1.0 6.2

1-TRANS-2-CIS-4-TRIMETHYLCYCLOPENTANE 0.5 2.3 0.3 2.3 0.5 2.1

3,3-DIMETHYLHEXANE

1-TRANS-2-CIS-3-TRIMETHYLCYCLOPENTANE 0.1 0.8 0.2 0.7 0.3 2.0

PAGE A-2HYDROCARBON SPECIATION DATA:

FTP COMPOSITE

FORD F-150

FTP Composite, mg/mi

F-HOU-N F-HOU-MF F-ATL-N F-ATL-MF F-CHI-N F-CHI-MF

COMPOUND 3/16/2005 3/17/2005 3/23/2005 3/24/2005 3/28/2005 3/29/2005 Houston Fuel Atlanta Fuel Chicago Fuel

2,3,4-TRIMETHYLPENTANE 1.0 4.1 4.8 16.9 2.5 10.0

2,3,3-TRIMETHYLPENTANE 0.9 2.0 2.6 11.4 2.9 9.0

TOLUENE 8.4 85.5 20.7 189.2 14.7 114.8

2,3-DIMETHYLHEXANE 1.2 3.6 1.7 11.9 1.1 7.9

1,1,2-TRIMETHYLCYCLOPENTANE

2-METHYLHEPTANE 0.2 0.1 1.7

3,4-DIMETHYLHEXANE, NOTE B 1.9 1.6 0.8

4-METHYLHEPTANE 3.2 13.2 3.1 9.9 1.8 7.6

3-METHYLHEPTANE 3.3 12.9 3.1 11.3 1.8 6.6

1-CIS,2-TRANS,3-TRIMETHYLCYCLOPENTANE

CIS-1,3-DIMETHYLCYCLOHEXANE

TRANS-1,4-DIMETHYLCYCLOHEXANE

3-ETHYLHEXANE 0.4 2.7 0.2 2.6 0.7 3.6

2,2,5-TRIMETHYLHEXANE 0.3 1.4 0.8 3.6 1.5 5.6

TRANS-1-METHYL-3-ETHYLCYCLOPENTANE

CIS-1-METHYL-3-ETHYLCYCLOPENTANE 0.3 2.2 0.2 2.0 0.5 2.1

1,1-DIMETHYLCYCLOHEXANE

TRANS-1-METHYL-2-ETHYLCYCLOPENTANE

1-METHYL-1-ETHYL-CYCLOPENTANE

2,4,4-TRIMETHYLHEXANE 0.1 1.0 0.1 0.7 0.1 1.3

2,2,4-TRIMETHYLHEXANE

TRANS-1,2-DIMETHYLCYCLOHEXANE 0.1 1.6 0.2 1.0 0.2 2.0

1-OCTENE

TRANS-4-OCTENE 0.3 0.1 1.9 0.9

OCTANE 1.6 7.7 1.7 7.9 1.2 4.5

UNIDENTIFIED C8 1.2 3.4 0.3 4.2 0.9 4.4

TRANS-2-OCTENE

TRANS-1,3-DIMETHYLCYCLOHEXANE, NOTE C

CIS-2-OCTENE Trace 0.7 0.1 0.5 0.1 0.6

ISOPROPYLCYCLOPENTANE

2,2-DIMETHYLHEPTANE Trace

2,3,5-TRIMETHYLHEXANE Trace 0.4 0.1 0.8 0.3 1.0

CIS-1-METHYL-2-ETHYLCYCLOPENTANE 0.1 1.0 0.1 0.9 0.1 1.0

2,4-DIMETHYLHEPTANE 0.2 1.0 0.1 1.0 0.2 0.7

4,4-DIMETHYLHEPTANE 0.1 0.5 0.1 0.3 0.1 0.5

CIS-1,2-DIMETHYLCYCLOHEXANE

ETHYLCYCLOHEXANE

2,6-DIMETHYLHEPTANE, NOTE D 0.3 1.7 0.3 2.1 0.7 1.7

1,1,3-TRIMETHYLCYCLOHEXANE

2,5-DIMETHYLHEPTANE, NOTE E 0.2 1.2 0.2 1.2 0.2 1.0

3,3-DIMETHYLHEPTANE

3,5-DIMETHYLHEPTANE, NOTE E 0.2 1.2 0.2 1.2 0.2 1.0

ETHYLBENZENE 3.1 33.3 4.4 43.7 3.3 22.1

2,3,4-TRIMETHYLHEXANE

2,3-DIMETHYLHEPTANE

m-& p-XYLENE 9.6 110.1 12.8 122.9 9.6 65.2

4-METHYLOCTANE

3,4-DIMETHYLHEPTANE

4-ETHYLHEPTANE

2-METHYLOCTANE 1.0 6.5 0.8 5.0 0.6 3.8

3-METHYLOCTANE 0.7 4.2 0.6 3.4 0.4 2.3

STYRENE 0.3 15.5 0.8 19.4 0.3 11.2

PAGE A-3HYDROCARBON SPECIATION DATA:

FTP COMPOSITE

FORD F-150

FTP Composite, mg/mi

F-HOU-N F-HOU-MF F-ATL-N F-ATL-MF F-CHI-N F-CHI-MF

COMPOUND 3/16/2005 3/17/2005 3/23/2005 3/24/2005 3/28/2005 3/29/2005 Houston Fuel Atlanta Fuel Chicago Fuel

o-XYLENE 3.5 42.6 5.0 48.1 3.3 23.5

1-NONENE 0.1 1.1 0.2 1.4 0.1 1.9

TRANS-3-NONENE

CIS-3-NONENE

NONANE 0.3 3.0 0.4 2.9 0.4 2.6

TRANS-2-NONENE

ISOPROPYLBENZENE (CUMENE) 0.5 0.1 0.6 Trace 0.5

2,2-DIMETHYLOCTANE Trace 0.6 0.1 0.5 0.1 0.9

2,4-DIMETHYLOCTANE 0.1 0.7 0.1 0.3 0.1 1.0

n-PROPYLBENZENE 0.5 9.8 0.8 12.0 0.6 6.7

1-METHYL-3-ETHYLBENZENE 2.3 52.6 3.3 47.0 2.6 31.8

1-METHYL-4-ETHYLBENZENE 0.9 7.9 1.5 21.5 0.8 10.6

1,3,5-TRIMETHYLBENZENE 1.1 19.4 1.7 19.6 0.8 13.2

1-METHYL-2-ETHYLBENZENE 0.8 15.7 1.5 19.8 0.7 10.4

1,2,4-TRIMETHYLBENZENE 1.6 70.5 5.4 77.5 2.5 47.8

TERT-BUTYLBENZENE

1-DECENE

DECANE, NOTE F 0.1 1.3 0.3 1.4 Trace 2.4

ISOBUTYLBENZENE, NOTE F 0.1 1.2 0.3 1.3 Trace 2.3

1,3,-DIMETHYL-5-ETHYLBENZENE
METHYLPROPYLBENZENE (sec butylbenzene) 0.8 0.1 1.4 0.2 0.9

1-METHYL-3-ISOPROPYLBENZENE Trace

1,2,3-TRIMETHYLBENZENE 0.4 14.2 1.2 18.4 0.4 11.3

1-METHYL-4-ISOPROPYLBENZENE 0.9 0.1 1.0 0.2 0.9

INDAN

1-METHYL-2-ISOPROPYLBENZENE 6.6 0.4 5.4 0.1 7.6

1,3-DIETHYLBENZENE

1,4-DIETHYLBENZENE 0.1 0.5 Trace 0.7

1-METHYL-3-N-PROPYLBENZENE 0.1 5.7 0.2 10.3 0.2 6.8

1-METHYL-4-N-PROPYLBENZENE, NOTE G 0.4 14.4 0.8 16.8 0.5 13.4

1,2 DIETHYLBENZENE 0.2 1.0 1.0

1-METHYL-2-N-PROPYLBENZENE 2.3 0.1 4.0 2.4

1,4-DIMETHYL-2-ETHYLBENZENE 5.8 0.7 8.5 6.5

1,3-DIMETHYL-4-ETHYLBENZENE 4.4 0.7 8.8 0.4 5.6

1,2-DIMETHYL-4-ETHYLBENZENE 0.8 1.9 1.7 0.9 1.8

1,3-DIMETHYL-2-ETHYLBENZENE 1.9 1.4 0.9

UNDECANE Trace 3.7 0.2 4.5 0.1 2.8

1,2-DIMETHYL-3-ETHYLBENZENE

1,2,4,5-TETRAMETHYLBENZENE 2.7 4.5 5.6

2-METHYLBUTYLBENZENE (sec AMYLBENZENE)

3,4 DIMETHYLCUMENE

1,2,3,5-TETRAMETHYLBENZENE 0.3 7.6 0.7 10.4 0.5 2.2

TERT-1-BUT-2-METHYLBENZENE 2.4 Trace 3.6 Trace 4.9

1,2,3,4-TETRAMETHYLBENZENE 4.3 4.8 Trace 4.1

N-PENT-BENZENE 2.0 2.2 2.0

TERT-1-BUT-3,5-DIMETHYLBENZENE

TERT-1-BUTYL-4-ETHYLBENZENE 5.0 3.3 6.2

NAPHTHALENE

DODECANE Trace 2.4 Trace 4.1 0.1 1.0

1,3,5-TRIETHYLBENZENE

1,2,4-TRIETHYLBENZENE

HEXYLBENZENE

PAGE A-4HYDROCARBON SPECIATION DATA:

FTP COMPOSITE

FORD F-150

FTP Composite, mg/mi

F-HOU-N F-HOU-MF F-ATL-N F-ATL-MF F-CHI-N F-CHI-MF

COMPOUND 3/16/2005 3/17/2005 3/23/2005 3/24/2005 3/28/2005 3/29/2005 Houston Fuel Atlanta Fuel Chicago Fuel

UNIDENTIFIED C9-C12+ 3.7 76.1 3.6 92.4 5.2 94.8

FORMALDEHYDE 9.3 56.5 5.4 38.7 6.6 34.1

ACETALDEHYDE 2.2 17.3 2.1 16.9 4.9 32.0

ACROLEIN 0.1 4.6 0.2 6.6 0.2 8.2

ACETONE 0.8 7.5 0.3 5.9 0.8 4.4

PROPIONALDEHYDE Trace 8.2 0.3 5.1 0.3 4.3

CROTONALDEHYDE 0.3 5.4 0.2 4.9 0.2 5.3

ISOBUTYRALDEHYDE, NOTE H 0.1 1.2 Trace 1.0 0.2 1.2

METHYL ETHYL KETONE, NOTE H 0.1 1.2 Trace 1.0 0.2 1.2

BENZALDEHYDE 0.5 10.2 0.6 13.8 0.1 7.8

ISOVALERALDEHYDE 0.2 1.2 0.9 Trace 1.5

VALERALDEHYDE 1.1 0.8 0.8

O-TOLUALDEHYDE 4.0 0.1 4.0 Trace 2.3

M/P-TOLUALDEHYDE 0.2 13.0 0.4 13.6 0.1 8.2

HEXANALDEHYDE 0.2 Trace 0.5 Trace 1.3

DIMETHYLBENZALDEHYDE 0.1 4.1 Trace 5.2 0.1 3.7

A - 2,2-Dimethylpentane and methylcyclopentane co-elute. GC peak area split equally between the two compounds.
B - 3-Methyl-3-ethyl-pentane co-elutes with reported compound. Not reported separately. C - Cis-1,4-Dimethylcyclohexane co-elutes with reported compound. Not reported separately.
D - Propylcyclopentane co-elutes with reported compound. Not reported separately. E - 2,5-Dimethylheptane and 3,5-dimethylheptane co-elute. GC peak area split equally between the two compounds. F - Decane and isobutylbenzene co-elute. GC peak area split equally between the two compounds. G - n-Butylbenzene co-elutes with reported compound. Not reported separately. H - Isobutyraldehyde and methyl ethyl ketone co-elute. LC peak area split equally between the two compounds.

PAGE A-5HYDROCARBON SPECIATION DATA

SHED TEST

FORD F-150

SHED results, mg

F-HOU-N F-HOU-MF F-ATL-N F-ATL-MF F-CHI-N F-CHI-MF

COMPOUND 3/16/2005 3/17/2005 3/23/2005 3/24/2005 3/28/2005 3/29/2005

METHANE

-- -- -- -- -- --

ETHANE 1.5 3.3 0.9 4.6 5.6 6.7

ETHYLENE 0.3 0.4 0.3 0.6 0.2

PROPANE 1.1 40.5 1.5 82.6 57.1 145.8

PROPYLENE 0.2 5.7 0.6 15.6 7.4 22.5

ACETYLENE

PROPADIENE

BUTANE 53.8 2311.0 106.2 3837.5 494.4 4161.4

TRANS-2-BUTENE 2.1 50.2 2.8 117.8 7.7 211.3

1-BUTENE 0.7 27.8 0.9 61.2 6.1 115.1

2-METHYLPROPENE (ISOBUTYLENE) 1.2 33.2 1.3 70.8 7.3 134.3

2,2-DIMETHYLPROPANE (NEOPENTANE) 43.9 1183.5 61.9 2925.1 151.9 4437.8

PROPYNE

1,3-BUTADIENE 1.2 2.4 7.9

2-METHYLPROPANE (ISOBUTANE) 5.7 199.7 10.4 481.5 68.0 792.8

1-BUTYNE

METHANOL

CIS-2-BUTENE 38.9 96.4 5.7 162.6

3-METHYL-1-BUTENE

ETHANOL 227.0 3370.0

2-METHYLBUTANE (ISOPENTANE)

2-BUTYNE

1-PENTENE 56.0 1.0 104.5 6.4 234.0

2-METHYL-1-BUTENE 125.1 2.7 238.4 14.1 500.5

PENTANE 21.0 506.3 25.7 1109.7 65.4 1711.8

UNIDENTIFIED C5 OLEFINS

2-METHYL-1,3-BUTADIENE 1.6 4.9 7.9 35.9

TRANS-2-PENTENE 5.2 129.2 2.4 245.5 5.4 530.8

3,3-DIMETHYL-1-BUTENE 2.6 14.2

CIS-2-PENTENE 2.9 73.9 1.1 134.6 2.1 291.7

2-METHYL-2-BUTENE 9.8 220.7 6.4 414.3 30.7 883.9

TERT-BUTANOL

CYCLOPENTADIENE 1.5 4.3 4.7 15.3

2,2-DIMETHYLBUTANE 2.6 27.8 1.8 59.8 2.8 96.4

CYCLOPENTENE 24.6 44.7 4.0 96.2

4-METHYL-1-PENTENE 0.4 12.6 2.4 23.4 1.2 49.6

3-METHYL-1-PENTENE

CYCLOPENTANE 28.1 55.3 4.2 96.2

2,3-DIMETHYLBUTANE 5.5 58.6 3.3 118.7 6.9 200.6

MTBE 170.1 46.9 1.1 78.2

4-METHYL-CIS-2-PENTENE

2-METHYLPENTANE 30.1 219.1 15.5 389.8 25.9 673.2

4-METHYL-TRANS-2-PENTENE 20.0 2.0 44.3

3-METHYLPENTANE 9.1 118.0 7.2 222.2 15.1 384.3

2-METHYL-1-PENTENE 1.1 12.1 0.6 22.7 2.0 50.0

1-HEXENE 1.1 12.1 0.6 22.7 2.0 50.0

HEXANE 8.7 90.4 7.5 167.0 13.6 279.1

UNIDENTIFIED C6 0.7 6.7 1.0 5.8 13.7 28.3

TRANS-3-HEXENE

CIS-3-HEXENE 1.7 10.7 0.8 20.9 46.9

DI-ISOPROPYL ETHER

TRANS-2-HEXENE 14.3 1.4 30.0 3.5 66.6 Houston Fuel Atlanta Fuel Chicago Fuel

PAGE A-6HYDROCARBON SPECIATION DATA

SHED TEST

FORD F-150

SHED results, mg

F-HOU-N F-HOU-MF F-ATL-N F-ATL-MF F-CHI-N F-CHI-MF

COMPOUND 3/16/2005 3/17/2005 3/23/2005 3/24/2005 3/28/2005 3/29/2005 Houston Fuel Atlanta Fuel Chicago Fuel

3-METHYL-TRANS-2-PENTENE 4.2 29.1 1.7 51.9 4.8 116.1

2-METHYL-2-PENTENE 1.5 17.8 1.8 30.7 3.6 66.8

3-METHYLCYCLOPENTENE

CIS-2-HEXENE 1.0 9.1 16.0 1.7 36.3

ETBE

3-METHYL-CIS-2-PENTENE 2.0 18.7 1.0 34.2 2.1 77.1

2,2-DIMETHYLPENTANE, NOTE A 3.5 38.5 2.5 68.2 6.7 132.1

METHYLCYCLOPENTANE, NOTE A 3.4 37.6 2.5 66.8 6.5 129.4

2,4-DIMETHYLPENTANE 1.9 17.3 1.6 35.5 2.7 59.2

2,2,3-TRIMETHYLBUTANE 2.4 1.7 7.0

3,4-DIMETHYL-1-PENTENE 0.8 1.4 3.7

1-METHYLCYCLOPENTENE 1.8 17.5 1.9 34.0 83.1

BENZENE 6.7 27.2 7.3 65.6 0.2 133.8

3-METHYL-1-HEXENE 2.1 5.0

3,3-DIMETHYLPENTANE 4.0 1.6 3.8 5.2 3.0

CYCLOHEXANE 1.3 11.6 20.0 44.8

2-METHYLHEXANE

2,3-DIMETHYLPENTANE 7.0 44.4 5.3 84.0 8.4 120.0

1,1-DIMETHYLCYCLOPENTANE 1.6 2.8 6.3

TERT-AMYL METHYL ETHER

CYCLOHEXENE 2.2 3.3 0.5 7.7

3-METHYLHEXANE 5.8 33.1 3.9 52.8 5.1 73.2

CIS-1,3-DIMETHYLCYCLOPENTANE 1.3 9.5 0.8 17.3 2.1 35.0

3-ETHYLPENTANE 1.2 10.4 0.9 24.4 2.0 43.4

TRANS-1,2-DIMETHYLCYCLOPENTANE

TRANS-1,3-DIMETHYLCYCLOPENTANE 1.3 7.8 0.6 15.0 1.6 28.8

1-HEPTENE

2,2,4-TRIMETHYLPENTANE 2.7 21.4 4.0 59.6 4.0 65.7

2-METHYL-1-HEXENE

TRANS-3-HEPTENE 0.5 4.0 0.4 7.3 0.9 15.8

HEPTANE 5.5 21.4 4.1 39.7 5.0 60.2

CIS-3-HEPTENE

UNIDENTIFIED C7 0.4 3.4 17.1 0.5 42.4

2-METHYL-2-HEXENE 18.4

3-METHYL-TRANS-3-HEXENE 1.6

TRANS-2-HEPTENE 0.2 2.3 0.2 3.0 0.5 5.5

3-ETHYL-CIS-2-PENTENE 3.1

2,4,4-TRIMETHYL-1-PENTENE 0.6 3.6 0.4 6.3 1.0 14.1

2,3-DIMETHYL-2-PENTENE

CIS-2-HEPTENE 1.5 0.2 2.8 0.4 6.0

METHYLCYCLOHEXANE 2.7 18.1 2.2 32.8 4.8 66.4

CIS-1,2-DIMETHYLCYCLOPENTANE

2,2-DIMETHYLHEXANE

1,1,3-TRIMETHYLCYCLOPENTANE 1.3 0.2 2.5 0.3 5.1

2,4,4-TRIMETHYL-2-PENTENE 0.9 0.2

2,2,3-TRIMETHYLPENTANE 1.6 3.7 0.9 8.1 1.7 23.6

2,5-DIMETHYLHEXANE

ETHYLCYCLOPENTANE

2,4-DIMETHYLHEXANE 1.8 11.0 0.5 8.9 2.0 13.5

1-TRANS-2-CIS-4-TRIMETHYLCYCLOPENTANE 0.2 3.4 0.4 6.3

3,3-DIMETHYLHEXANE

1-TRANS-2-CIS-3-TRIMETHYLCYCLOPENTANE 1.7 0.2 5.2

PAGE A-7HYDROCARBON SPECIATION DATA

SHED TEST

FORD F-150

SHED results, mg

F-HOU-N F-HOU-MF F-ATL-N F-ATL-MF F-CHI-N F-CHI-MF

COMPOUND 3/16/2005 3/17/2005 3/23/2005 3/24/2005 3/28/2005 3/29/2005 Houston Fuel Atlanta Fuel Chicago Fuel

2,3,4-TRIMETHYLPENTANE 2.4 11.2 1.6 17.7 2.4 29.2

2,3,3-TRIMETHYLPENTANE 1.0 7.8 1.3 12.9 22.4

TOLUENE 12.8 37.6 15.1 82.5 125.9

2,3-DIMETHYLHEXANE 4.1 7.8 15.9

1,1,2-TRIMETHYLCYCLOPENTANE

2-METHYLHEPTANE 1.1 0.2 3.8

3,4-DIMETHYLHEXANE, NOTE B

4-METHYLHEPTANE 1.6 6.9 1.3 10.2 1.6 15.8

3-METHYLHEPTANE 1.7 7.0 1.3 11.4 1.9 11.6

1-CIS,2-TRANS,3-TRIMETHYLCYCLOPENTANE

CIS-1,3-DIMETHYLCYCLOHEXANE

TRANS-1,4-DIMETHYLCYCLOHEXANE

3-ETHYLHEXANE 0.3 0.8 7.1

2,2,5-TRIMETHYLHEXANE 0.6 3.3 0.5 4.2 0.8 7.8

TRANS-1-METHYL-3-ETHYLCYCLOPENTANE

CIS-1-METHYL-3-ETHYLCYCLOPENTANE 0.6 1.5 0.1 1.2 0.2 1.8

1,1-DIMETHYLCYCLOHEXANE

TRANS-1-METHYL-2-ETHYLCYCLOPENTANE

1-METHYL-1-ETHYL-CYCLOPENTANE

2,4,4-TRIMETHYLHEXANE 0.2

2,2,4-TRIMETHYLHEXANE

TRANS-1,2-DIMETHYLCYCLOHEXANE 0.4 0.6 0.2 0.1 3.0

1-OCTENE

TRANS-4-OCTENE 0.6 1.7

OCTANE 1.2 2.8 0.9 3.4 1.2 7.0

UNIDENTIFIED C8 6.0 18.1 0.3 9.8

TRANS-2-OCTENE 0.4 0.7 0.8 2.6

TRANS-1,3-DIMETHYLCYCLOHEXANE, NOTE C

CIS-2-OCTENE 0.9

ISOPROPYLCYCLOPENTANE

2,2-DIMETHYLHEPTANE

2,3,5-TRIMETHYLHEXANE 0.3 0.3 0.9

CIS-1-METHYL-2-ETHYLCYCLOPENTANE 0.3 0.3 0.9

2,4-DIMETHYLHEPTANE 0.2 0.5 0.1 0.1 0.3

4,4-DIMETHYLHEPTANE 0.1 0.6

CIS-1,2-DIMETHYLCYCLOHEXANE

ETHYLCYCLOHEXANE

2,6-DIMETHYLHEPTANE, NOTE D 0.4 1.0 0.2 1.5 0.3 3.3

1,1,3-TRIMETHYLCYCLOHEXANE

2,5-DIMETHYLHEPTANE, NOTE E 0.1 0.3 0.4 0.1 0.9

3,3-DIMETHYLHEPTANE

3,5-DIMETHYLHEPTANE, NOTE E 0.1 0.3 0.4 0.1 0.9

ETHYLBENZENE 3.0 5.2 2.8 9.4 3.3 10.8

2,3,4-TRIMETHYLHEXANE

2,3-DIMETHYLHEPTANE

m-& p-XYLENE 7.4 12.6 6.0 25.7 7.6 31.8

4-METHYLOCTANE

3,4-DIMETHYLHEPTANE

4-ETHYLHEPTANE

2-METHYLOCTANE 1.4 0.1 2.5

3-METHYLOCTANE 1.1 1.6

STYRENE

PAGE A-8HYDROCARBON SPECIATION DATA

SHED TEST

FORD F-150

SHED results, mg

F-HOU-N F-HOU-MF F-ATL-N F-ATL-MF F-CHI-N F-CHI-MF

COMPOUND 3/16/2005 3/17/2005 3/23/2005 3/24/2005 3/28/2005 3/29/2005 Houston Fuel Atlanta Fuel Chicago Fuel

o-XYLENE 1.5 2.6 0.9 8.6 1.3 10.0

1-NONENE 0.3 0.4 0.1 0.4

TRANS-3-NONENE

CIS-3-NONENE

NONANE 0.1 0.5

TRANS-2-NONENE

ISOPROPYLBENZENE (CUMENE) 0.1 0.2

2,2-DIMETHYLOCTANE 0.2

2,4-DIMETHYLOCTANE 0.1

n-PROPYLBENZENE 0.1 0.2

1-METHYL-3-ETHYLBENZENE

1-METHYL-4-ETHYLBENZENE

1,3,5-TRIMETHYLBENZENE

1-METHYL-2-ETHYLBENZENE 0.3

1,2,4-TRIMETHYLBENZENE 2.0

TERT-BUTYLBENZENE

1-DECENE

DECANE, NOTE F

ISOBUTYLBENZENE, NOTE F

1,3,-DIMETHYL-5-ETHYLBENZENE
METHYLPROPYLBENZENE (sec butylbenzene)

1-METHYL-3-ISOPROPYLBENZENE 0.5

1,2,3-TRIMETHYLBENZENE 0.3 0.3

1-METHYL-4-ISOPROPYLBENZENE

INDAN

1-METHYL-2-ISOPROPYLBENZENE

1,3-DIETHYLBENZENE

1,4-DIETHYLBENZENE

1-METHYL-3-N-PROPYLBENZENE

1-METHYL-4-N-PROPYLBENZENE, NOTE G

1,2 DIETHYLBENZENE

1-METHYL-2-N-PROPYLBENZENE

1,4-DIMETHYL-2-ETHYLBENZENE

1,3-DIMETHYL-4-ETHYLBENZENE

1,2-DIMETHYL-4-ETHYLBENZENE

1,3-DIMETHYL-2-ETHYLBENZENE

UNDECANE

1,2-DIMETHYL-3-ETHYLBENZENE

1,2,4,5-TETRAMETHYLBENZENE
2-METHYLBUTYLBENZENE (sec AMYLBENZENE)

3,4 DIMETHYLCUMENE

1,2,3,5-TETRAMETHYLBENZENE

TERT-1-BUT-2-METHYLBENZENE

1,2,3,4-TETRAMETHYLBENZENE

N-PENT-BENZENE

TERT-1-BUT-3,5-DIMETHYLBENZENE

TERT-1-BUTYL-4-ETHYLBENZENE

NAPHTHALENE

DODECANE 0.1

1,3,5-TRIETHYLBENZENE

1,2,4-TRIETHYLBENZENE

HEXYLBENZENE

PAGE A-9HYDROCARBON SPECIATION DATA

SHED TEST

FORD F-150

SHED results, mg

F-HOU-N F-HOU-MF F-ATL-N F-ATL-MF F-CHI-N F-CHI-MF

COMPOUND 3/16/2005 3/17/2005 3/23/2005 3/24/2005 3/28/2005 3/29/2005 Houston Fuel Atlanta Fuel Chicago Fuel

UNIDENTIFIED C9-C12+ 0.2 1.6 2.2 1.1 8.4

A - 2,2-Dimethylpentane and methylcyclopentane co-elute. GC peak area split equally between the two compounds.
B - 3-Methyl-3-ethyl-pentane co-elutes with reported compound. Not reported separately. C - Cis-1,4-Dimethylcyclohexane co-elutes with reported compound. Not reported separately.
D - Propylcyclopentane co-elutes with reported compound. Not reported separately. E - 2,5-Dimethylheptane and 3,5-dimethylheptane co-elute. GC peak area split equally between the two compounds. F - Decane and isobutylbenzene co-elute. GC peak area split equally between the two compounds. G - n-Butylbenzene co-elutes with reported compound. Not reported separately.

PAGE A-10HYDROCARBON SPECIATION DATA

FTP COMPOSITE

FORD F-150

FTP Composite, mg/mi

FT-4614-S FT-4614-M FT-4637-S FT-4637-M FT-4640-S FT-4640-M

COMPOUND 7/17/2002 7/19/2002 7/24/2002 7/23/2002 7/26/2002 7/29/2002

METHANE 97.4 100.8 101.5 104.5 94.3 95.0

ETHANE 32.7 37.0 27.0 35.9 35.3 34.9

ETHYLENE 27.7 245.4 30.1 255.5 25.0 232.7

PROPANE 3.8 3.6 4.1 3.8 2.9 6.4

PROPYLENE 7.2 108.8 12.2 132.7 7.4 124.7

ACETYLENE 3.4 121.1 5.3 102.1 1.9 70.1

PROPADIENE

BUTANE 3.8 9.1 7.5 12.6 3.2 4.3

TRANS-2-BUTENE 1.0 7.3 2.0 6.6 5.2 17.6

1-BUTENE 2.3 19.2 1.6 18.6 1.2

2-METHYLPROPENE (ISOBUTYLENE) 8.8 100.9 4.2 60.4 3.4 64.4

2,2-DIMETHYLPROPANE (NEOPENTANE) 0.4 2.0 0.6 2.0 0.2 1.0

PROPYNE

1,3-BUTADIENE 1.5 37.6 1.2 48.9 0.3 32.9

2-METHYLPROPANE (ISOBUTANE) 0.2 8.6 3.8 9.3 0.2 6.9

1-BUTYNE

METHANOL

CIS-2-BUTENE 1.3 6.0 9.1 0.4 6.3

3-METHYL-1-BUTENE

ETHANOL 12.1 182.6

2-METHYLBUTANE (ISOPENTANE) 23.1 49.3 13.7 59.4 29.6 46.9

2-BUTYNE

1-PENTENE 0.4 7.8 0.8 1.2 0.4 6.8

2-METHYL-1-BUTENE 0.7 13.6 0.6 11.2 0.5 12.5

PENTANE 10.9 27.6 12.6 33.5 4.3 10.9

UNIDENTIFIED C5 OLEFINS 0.1 0.5 2.0 0.7 12.3

2-METHYL-1,3-BUTADIENE 0.2 6.6 10.3 0.2 11.9

TRANS-2-PENTENE 0.8 10.9 0.4 8.2 0.7 7.6

3,3-DIMETHYL-1-BUTENE 0.4 0.7 0.4 Trace 1.0

CIS-2-PENTENE 0.4 6.2 Trace 4.6 2.4 4.5

2-METHYL-2-BUTENE 1.1 14.9 1.1 12.1 1.3 16.8

TERT-BUTANOL

CYCLOPENTADIENE 0.1 2.8 8.4 0.1 7.4

2,2-DIMETHYLBUTANE 1.8 4.6 2.1 6.2 2.6 7.0

CYCLOPENTENE 0.3 4.0 0.3 2.9 0.2 3.4

4-METHYL-1-PENTENE 0.1 2.0 0.2 2.0 0.1 2.8

3-METHYL-1-PENTENE

CYCLOPENTANE 0.9 3.2 0.6 3.4 0.7 2.7

2,3-DIMETHYLBUTANE 3.6 11.1 2.3 9.2 5.6 17.0

MTBE 0.9 41.9

4-METHYL-CIS-2-PENTENE

2-METHYLPENTANE 11.7 39.4 7.9 31.2 7.8 26.5

4-METHYL-TRANS-2-PENTENE

3-METHYLPENTANE 8.9 32.2 5.3 20.9 5.7 20.6

2-METHYL-1-PENTENE 0.1 2.5 0.1 2.5 0.1 2.0

1-HEXENE 0.2 2.8 0.1 2.5 0.1 2.0

HEXANE 8.7 31.2 5.2 19.3 4.6 14.4

UNIDENTIFIED C6 0.1 6.2 2.0 7.3 0.5 9.5

TRANS-3-HEXENE

CIS-3-HEXENE 0.1 1.6 0.1 1.0 0.1 0.9

DI-ISOPROPYL ETHER

TRANS-2-HEXENE 0.2 2.4 0.1 1.9 0.1 1.8 Houston Fuel Atlanta Fuel Chicago Fuel

PAGE A-11HYDROCARBON SPECIATION DATA

FTP COMPOSITE

FORD F-150

FTP Composite, mg/mi

FT-4614-S FT-4614-M FT-4637-S FT-4637-M FT-4640-S FT-4640-M

COMPOUND 7/17/2002 7/19/2002 7/24/2002 7/23/2002 7/26/2002 7/29/2002 Houston Fuel Atlanta Fuel Chicago Fuel

3-METHYL-TRANS-2-PENTENE 0.3 4.1 0.3 3.2 0.2 3.5

2-METHYL-2-PENTENE 0.2 2.9 0.1 2.1 0.1 2.5

3-METHYLCYCLOPENTENE

CIS-2-HEXENE 0.1 1.5 0.1 0.9 0.1 0.8

ETBE

3-METHYL-CIS-2-PENTENE 0.3 2.7 0.2 1.9 0.5 1.7

2,2-DIMETHYLPENTANE, NOTE A 1.6 7.3 1.4 7.2 2.1 9.5

METHYLCYCLOPENTANE, NOTE A 1.6 7.1 1.4 7.0 2.0 9.3

2,4-DIMETHYLPENTANE 1.7 5.5 1.6 5.6 3.5 11.7

2,2,3-TRIMETHYLBUTANE 0.3 3.0 Trace 0.4 0.2 0.4

3,4-DIMETHYL-1-PENTENE 0.3

1-METHYLCYCLOPENTENE 0.7 2.9 2.6 3.1

BENZENE 6.1 60.5 14.2 103.6 6.0 62.0

3-METHYL-1-HEXENE

3,3-DIMETHYLPENTANE 0.6 1.4 0.5 1.2 0.2 0.8

CYCLOHEXANE 0.4 2.8 0.8 5.3 1.9 10.7

2-METHYLHEXANE

2,3-DIMETHYLPENTANE 6.4 20.9 6.0 22.9 10.2 32.8

1,1-DIMETHYLCYCLOPENTANE 1.3

TERT-AMYL METHYL ETHER

CYCLOHEXENE Trace 1.0 1.2 Trace 1.8

3-METHYLHEXANE 4.6 15.4 4.4 15.8 5.0 16.7

CIS-1,3-DIMETHYLCYCLOPENTANE 0.3 2.1 0.3 2.0 0.6 3.3

3-ETHYLPENTANE 0.3 2.6 0.4 1.2

TRANS-1,2-DIMETHYLCYCLOPENTANE

TRANS-1,3-DIMETHYLCYCLOPENTANE 0.4 2.1 0.4 2.0 0.8 3.2

1-HEPTENE

2,2,4-TRIMETHYLPENTANE 10.4 26.2 13.9 41.0 15.5 43.2

2-METHYL-1-HEXENE

TRANS-3-HEPTENE 0.1 1.7 1.1 0.2

HEPTANE 2.9 10.1 4.6 16.2 5.3 14.9

CIS-3-HEPTENE

UNIDENTIFIED C7 0.2 1.3 0.2 2.9 0.1 1.9

2-METHYL-2-HEXENE 1.3

3-METHYL-TRANS-3-HEXENE

TRANS-2-HEPTENE 0.1 1.1 Trace 0.7 Trace 0.7

3-ETHYL-CIS-2-PENTENE

2,4,4-TRIMETHYL-1-PENTENE 0.2 1.4 0.1 0.6 0.1 0.8

2,3-DIMETHYL-2-PENTENE

CIS-2-HEPTENE 0.1 1.1 0.1 0.8 0.1 1.0

METHYLCYCLOHEXANE 0.9 4.5 1.4 7.6 2.1 11.1

CIS-1,2-DIMETHYLCYCLOPENTANE

2,2-DIMETHYLHEXANE

1,1,3-TRIMETHYLCYCLOPENTANE 0.2 0.8 0.3 1.1 0.4 1.4

2,4,4-TRIMETHYL-2-PENTENE

2,2,3-TRIMETHYLPENTANE 2.0 6.0 1.3 6.1 2.6 9.9

2,5-DIMETHYLHEXANE

ETHYLCYCLOPENTANE

2,4-DIMETHYLHEXANE 1.2 6.4 1.5 8.3 1.7 8.3

1-TRANS-2-CIS-4-TRIMETHYLCYCLOPENTANE 0.2 1.4 0.5 1.1 0.3 1.9

3,3-DIMETHYLHEXANE

1-TRANS-2-CIS-3-TRIMETHYLCYCLOPENTANE 0.1 0.3 0.1 0.4 0.1 0.7

PAGE A-12HYDROCARBON SPECIATION DATA

FTP COMPOSITE

FORD F-150

FTP Composite, mg/mi

FT-4614-S FT-4614-M FT-4637-S FT-4637-M FT-4640-S FT-4640-M

COMPOUND 7/17/2002 7/19/2002 7/24/2002 7/23/2002 7/26/2002 7/29/2002 Houston Fuel Atlanta Fuel Chicago Fuel

2,3,4-TRIMETHYLPENTANE 3.8 12.2 3.8 11.3 5.7 18.5

2,3,3-TRIMETHYLPENTANE 3.6 21.6 3.0 13.4 6.6 31.8

TOLUENE 6.5 87.5 27.1 232.4 8.0 102.1

2,3-DIMETHYLHEXANE 1.8 16.0 3.2 20.1 3.0 20.0

1,1,2-TRIMETHYLCYCLOPENTANE

2-METHYLHEPTANE 6.7 1.8 7.3

3,4-DIMETHYLHEXANE, NOTE B 0.1 0.1 1.6 1.1

4-METHYLHEPTANE 2.2 1.1 0.2 1.5 2.8 9.8

3-METHYLHEPTANE 2.2 7.7 1.8 7.8 2.3 8.8

1-CIS,2-TRANS,3-TRIMETHYLCYCLOPENTANE 0.1

CIS-1,3-DIMETHYLCYCLOHEXANE

TRANS-1,4-DIMETHYLCYCLOHEXANE

3-ETHYLHEXANE Trace 1.8 0.2 1.7 0.4 2.0

2,2,5-TRIMETHYLHEXANE 1.0 3.8 1.2 5.4 2.7 10.6

TRANS-1-METHYL-3-ETHYLCYCLOPENTANE

CIS-1-METHYL-3-ETHYLCYCLOPENTANE 0.2 1.9 0.1 2.5 0.2 2.0

1,1-DIMETHYLCYCLOHEXANE

TRANS-1-METHYL-2-ETHYLCYCLOPENTANE

1-METHYL-1-ETHYL-CYCLOPENTANE

2,4,4-TRIMETHYLHEXANE 0.1 0.8 Trace 0.8 Trace 0.6

2,2,4-TRIMETHYLHEXANE

TRANS-1,2-DIMETHYLCYCLOHEXANE Trace 1.0 0.1 0.8 0.1 0.7

1-OCTENE

TRANS-4-OCTENE

OCTANE 1.1 4.4 1.6 6.5 1.7 6.7

UNIDENTIFIED C8 0.2 3.6 0.3 1.2 4.9 1.1

TRANS-2-OCTENE 0.1 1.2 0.1 0.7 Trace 0.5

TRANS-1,3-DIMETHYLCYCLOHEXANE, NOTE C

CIS-2-OCTENE 0.1 0.7 Trace 0.3 0.3

ISOPROPYLCYCLOPENTANE

2,2-DIMETHYLHEPTANE

2,3,5-TRIMETHYLHEXANE 0.1 0.7 0.1 1.0 0.3 1.9

CIS-1-METHYL-2-ETHYLCYCLOPENTANE 0.1 0.7 0.1 0.6 Trace 0.7

2,4-DIMETHYLHEPTANE 0.1 0.3 0.2 0.9 2.6 1.0

4,4-DIMETHYLHEPTANE Trace 1.2 0.2 0.1 0.2

CIS-1,2-DIMETHYLCYCLOHEXANE

ETHYLCYCLOHEXANE

2,6-DIMETHYLHEPTANE, NOTE D 0.4 0.6 0.2 1.6 0.5 2.2

1,1,3-TRIMETHYLCYCLOHEXANE

2,5-DIMETHYLHEPTANE, NOTE E 0.4 1.6 0.6 2.1 0.6 2.7

3,3-DIMETHYLHEPTANE

3,5-DIMETHYLHEPTANE, NOTE E

ETHYLBENZENE 2.6 22.1 5.2 37.8 1.9 17.8

2,3,4-TRIMETHYLHEXANE

2,3-DIMETHYLHEPTANE

m-& p-XYLENE 6.9 61.5 18.0 120.0 5.7 57.6

4-METHYLOCTANE

3,4-DIMETHYLHEPTANE

4-ETHYLHEPTANE

2-METHYLOCTANE 0.8 5.4 1.2 6.8 0.8 6.4

3-METHYLOCTANE 0.6 3.0 0.7 3.3 0.6 4.9

STYRENE 0.4 11.8 1.4 20.6 0.3 12.6

PAGE A-13HYDROCARBON SPECIATION DATA

FTP COMPOSITE

FORD F-150

FTP Composite, mg/mi

FT-4614-S FT-4614-M FT-4637-S FT-4637-M FT-4640-S FT-4640-M

COMPOUND 7/17/2002 7/19/2002 7/24/2002 7/23/2002 7/26/2002 7/29/2002 Houston Fuel Atlanta Fuel Chicago Fuel

o-XYLENE 2.9 27.8 7.6 48.6 2.4 27.1

1-NONENE 0.1 2.3 0.2 3.1 0.3 3.8

TRANS-3-NONENE

CIS-3-NONENE

NONANE 0.5 3.1 1.2 3.6 0.8 4.7

TRANS-2-NONENE

ISOPROPYLBENZENE (CUMENE) 0.9 1.4 0.2 3.4 0.1 1.8

2,2-DIMETHYLOCTANE 0.1 0.4 0.1 Trace 0.2

2,4-DIMETHYLOCTANE Trace 0.3 0.1 0.3 Trace 0.3

n-PROPYLBENZENE 0.5 6.4 1.5 13.4 0.4 6.1

1-METHYL-3-ETHYLBENZENE 2.7 32.2 6.8 12.6 1.9 26.0

1-METHYL-4-ETHYLBENZENE 1.0 13.6 3.1 50.5 0.6 10.3

1,3,5-TRIMETHYLBENZENE 1.0 11.3 3.1 24.6 0.7 10.9

1-METHYL-2-ETHYLBENZENE 1.0 12.2 2.9 22.0 0.7 7.4

1,2,4-TRIMETHYLBENZENE 3.0 46.6 11.2 96.2 2.4 44.3

TERT-BUTYLBENZENE

1-DECENE

DECANE, NOTE F 0.1 1.1 0.3 2.3 0.1 1.1

ISOBUTYLBENZENE, NOTE F 0.1 1.0 0.3 2.1 0.1 1.0

1,3,-DIMETHYL-5-ETHYLBENZENE
METHYLPROPYLBENZENE (sec butylbenzene)

1-METHYL-3-ISOPROPYLBENZENE 1.9

1,2,3-TRIMETHYLBENZENE 0.6 10.8 2.7 23.2 0.5 9.1

1-METHYL-4-ISOPROPYLBENZENE 0.4

INDAN

1-METHYL-2-ISOPROPYLBENZENE 1.8

1,3-DIETHYLBENZENE

1,4-DIETHYLBENZENE Trace

1-METHYL-3-N-PROPYLBENZENE 0.1 5.5 1.0 7.7 0.3 7.4

1-METHYL-4-N-PROPYLBENZENE, NOTE G 0.5 13.0 1.9 21.8 0.3 11.7

1,2 DIETHYLBENZENE 0.1 0.2

1-METHYL-2-N-PROPYLBENZENE 0.2 2.0 0.1 2.9 0.2 2.1

1,4-DIMETHYL-2-ETHYLBENZENE 6.1

1,3-DIMETHYL-4-ETHYLBENZENE 0.4 16.3 1.1 18.9 0.3 5.3

1,2-DIMETHYL-4-ETHYLBENZENE 0.1 10.9 1.4 9.5 0.4 1.8

1,3-DIMETHYL-2-ETHYLBENZENE 3.9

UNDECANE Trace 2.3 0.5 6.3 0.1 2.3

1,2-DIMETHYL-3-ETHYLBENZENE 0.7

1,2,4,5-TETRAMETHYLBENZENE Trace 3.7 0.6 9.9 0.1 4.0

2-METHYLBUTYLBENZENE (sec AMYLBENZENE)

3,4 DIMETHYLCUMENE

1,2,3,5-TETRAMETHYLBENZENE

TERT-1-BUT-2-METHYLBENZENE 5.7

1,2,3,4-TETRAMETHYLBENZENE

N-PENT-BENZENE 1.9

TERT-1-BUT-3,5-DIMETHYLBENZENE 0.1 0.8 0.2 2.6 17.1

TERT-1-BUTYL-4-ETHYLBENZENE

NAPHTHALENE 0.3

DODECANE 0.1 0.3 0.8 5.8 1.6

1,3,5-TRIETHYLBENZENE

1,2,4-TRIETHYLBENZENE

HEXYLBENZENE

PAGE A-14HYDROCARBON SPECIATION DATA

FTP COMPOSITE

FORD F-150

FTP Composite, mg/mi

FT-4614-S FT-4614-M FT-4637-S FT-4637-M FT-4640-S FT-4640-M

COMPOUND 7/17/2002 7/19/2002 7/24/2002 7/23/2002 7/26/2002 7/29/2002 Houston Fuel Atlanta Fuel Chicago Fuel

UNIDENTIFIED C9-C12+ 3.0 81.0 18.8 238.9 4.6 105.3

FORMALDEHYDE 9.4 94.0 14.6 75.5 12.7 85.2

ACETALDEHYDE 4.6 22.6 4.3 21.1 5.7 36.2

ACROLEIN 1.2 11.0 0.9 13.4 0.3 11.6

ACETONE 5.6 12.5 4.3 7.4 4.1 7.3

PROPIONALDEHYDE 0.5 8.9 0.5 4.7 0.5 6.5

CROTONALDEHYDE 2.0 9.9 0.8 6.4 1.1 7.6

ISOBUTYRALDEHYDE, NOTE H 0.8 3.0 0.6 2.2 0.4 2.1

METHYL ETHYL KETONE, NOTE H 0.8 3.0 0.6 2.2 0.4 2.1

BENZALDEHYDE 0.1 10.5 0.7 19.5 0.3 10.9

ISOVALERALDEHYDE 0.3 2.1 0.1 1.7 0.1 1.4

VALERALDEHYDE 0.2 1.1 0.3 1.6 0.2 0.3

O-TOLUALDEHYDE 0.3 4.0 5.6 3.2

M/P-TOLUALDEHYDE 0.3 11.8 0.8 18.9 0.3 11.0

HEXANALDEHYDE 0.3

DIMETHYLBENZALDEHYDE 0.4 4.0 0.2 6.9 0.4 3.9

A - 2,2-Dimethylpentane and methylcyclopentane co-elute. GC peak area split equally between the two compounds.
B - 3-Methyl-3-ethyl-pentane co-elutes with reported compound. Not reported separately. C - Cis-1,4-Dimethylcyclohexane co-elutes with reported compound. Not reported separately.
D - Propylcyclopentane co-elutes with reported compound. Not reported separately. E - 2,5-Dimethylheptane and 3,5-dimethylheptane co-elute. GC peak area split equally between the two compounds. F - Decane and isobutylbenzene co-elute. GC peak area split equally between the two compounds. G - n-Butylbenzene co-elutes with reported compound. Not reported separately. H - Isobutyraldehyde and methyl ethyl ketone co-elute. LC peak area split equally between the two compounds.

PAGE A-15HYDROCARBON SPECIATION DATA

SHED TEST

FORD F-150
SHED results, mg

FT-4614-S FT-4614-M FT-4637-S FT-4637-M FT-4640-S FT-4640-M

COMPOUND 7/17/2002 7/19/2002 7/24/2002 7/23/2002 7/26/2002 7/29/2002

METHANE

ETHANE 7.2 Trace 0.6

ETHYLENE 7.3 2.8

PROPANE 0.4 6.0 4.3

PROPYLENE 1.2 0.6

ACETYLENE

PROPADIENE

BUTANE 2.0 123.7 3.1 94.8 2.3 70.5

TRANS-2-BUTENE 3.8

1-BUTENE 2.8

2-METHYLPROPENE (ISOBUTYLENE) 3.4 2.1 6.0

2,2-DIMETHYLPROPANE (NEOPENTANE) 2.8 3.0 0.7

PROPYNE

1,3-BUTADIENE

2-METHYLPROPANE (ISOBUTANE) 0.6 22.7 25.6 1.1 16.2

1-BUTYNE

METHANOL

CIS-2-BUTENE

3-METHYL-1-BUTENE

ETHANOL 10.6 193.4

2-METHYLBUTANE (ISOPENTANE) 647.3 687.0 5.7 532.7

2-BUTYNE

1-PENTENE 1.8 27.2 25.3 23.4

2-METHYL-1-BUTENE 1.0 38.4 8.6 38.4 36.9

PENTANE 3.2 105.9 0.7 118.6 0.8 87.0

UNIDENTIFIED C5 OLEFINS

2-METHYL-1,3-BUTADIENE 1.4 2.7 1.1 2.5 1.1

TRANS-2-PENTENE 1.2 43.6 0.9 39.5 37.6

3,3-DIMETHYL-1-BUTENE 0.4 0.3 1.1 0.4

CIS-2-PENTENE 0.5 24.0 0.5 21.9 0.5 21.1

2-METHYL-2-BUTENE 2.4 59.0 2.4 56.4 2.2 54.2

TERT-BUTANOL

CYCLOPENTADIENE 0.8 0.5 0.5

2,2-DIMETHYLBUTANE 0.5 21.3 0.4 23.3 0.5 23.1

CYCLOPENTENE 7.6 0.3 7.5 0.4 6.7

4-METHYL-1-PENTENE 3.5 2.6 3.1

3-METHYL-1-PENTENE

CYCLOPENTANE 0.6 12.2 0.6 13.7 0.5 12.1

2,3-DIMETHYLBUTANE 1.7 47.4 1.3 48.3 1.6 51.3

MTBE 97.0

4-METHYL-CIS-2-PENTENE

2-METHYLPENTANE 6.7 77.1 6.6 86.6 6.9 81.1

4-METHYL-TRANS-2-PENTENE

3-METHYLPENTANE 3.4 57.7 2.8 52.5 2.9 50.4

2-METHYL-1-PENTENE 0.2 2.9 0.3 2.8 0.4 2.5

1-HEXENE 0.2 2.9 0.3 2.8 0.4 2.5

HEXANE 3.6 40.1 2.9 35.7 3.4 33.1

UNIDENTIFIED C6 1.9 4.6 12.4 11.3

TRANS-3-HEXENE Houston Fuel Atlanta Fuel Chicago Fuel

PAGE A-16HYDROCARBON SPECIATION DATA

SHED TEST

FORD F-150
SHED results, mg

FT-4614-S FT-4614-M FT-4637-S FT-4637-M FT-4640-S FT-4640-M

COMPOUND 7/17/2002 7/19/2002 7/24/2002 7/23/2002 7/26/2002 7/29/2002 Houston Fuel Atlanta Fuel Chicago Fuel

CIS-3-HEXENE 2.5 2.1 2.1

DI-ISOPROPYL ETHER

TRANS-2-HEXENE 0.4 4.0 3.2 3.3

3-METHYL-TRANS-2-PENTENE 5.9 0.3 6.1 5.5

2-METHYL-2-PENTENE 0.3 3.7 0.4 3.4 0.4 3.1

3-METHYLCYCLOPENTENE

CIS-2-HEXENE 2.5 0.3 5.6 0.3 2.5

ETBE

3-METHYL-CIS-2-PENTENE 4.6 0.6 4.2 0.5 4.0

2,2-DIMETHYLPENTANE, NOTE A 1.9 16.8 1.1 17.5 1.3 18.7

METHYLCYCLOPENTANE, NOTE A 1.9 16.4 1.1 17.1 1.2 18.4

2,4-DIMETHYLPENTANE 1.5 13.5 1.2 15.2 1.5 17.1

2,2,3-TRIMETHYLBUTANE 1.1 0.9 1.0

3,4-DIMETHYL-1-PENTENE

1-METHYLCYCLOPENTENE 0.9 13.9 2.1 9.1 0.9 8.5

BENZENE 3.8 23.1 5.6 25.2 5.6 21.4

3-METHYL-1-HEXENE

3,3-DIMETHYLPENTANE 0.4 0.8 1.9 1.1

CYCLOHEXANE 16.9 16.3 21.3

2-METHYLHEXANE

2,3-DIMETHYLPENTANE 5.1 32.2 4.1 34.7 4.5 38.0

1,1-DIMETHYLCYCLOPENTANE

TERT-AMYL METHYL ETHER

CYCLOHEXENE 0.4 0.5 0.3

3-METHYLHEXANE 3.0 17.3 2.7 18.5 3.0 18.1

CIS-1,3-DIMETHYLCYCLOPENTANE 0.6 3.0 0.5 3.3 0.5 4.1

3-ETHYLPENTANE 0.6 0.5 0.6 6.6

TRANS-1,2-DIMETHYLCYCLOPENTANE

TRANS-1,3-DIMETHYLCYCLOPENTANE 0.4 2.4 0.3 3.1 0.4 3.2

1-HEPTENE

2,2,4-TRIMETHYLPENTANE 4.2 34.8 3.6 38.2 4.2 31.8

2-METHYL-1-HEXENE

TRANS-3-HEPTENE 1.2 1.1

HEPTANE 4.2 15.5 4.0 17.8 4.6 17.2

CIS-3-HEPTENE

UNIDENTIFIED C7 1.4 3.3 0.5

2-METHYL-2-HEXENE

3-METHYL-TRANS-3-HEXENE

TRANS-2-HEPTENE 1.4 0.7 0.7

3-ETHYL-CIS-2-PENTENE

2,4,4-TRIMETHYL-1-PENTENE 0.3 1.9 0.3 1.0 1.2

2,3-DIMETHYL-2-PENTENE

CIS-2-HEPTENE 1.1 0.5 0.6

METHYLCYCLOHEXANE 1.7 6.0 1.5 7.4 1.7 9.5

CIS-1,2-DIMETHYLCYCLOPENTANE

2,2-DIMETHYLHEXANE

1,1,3-TRIMETHYLCYCLOPENTANE 1.0 1.0 1.2

2,4,4-TRIMETHYL-2-PENTENE 0.3

2,2,3-TRIMETHYLPENTANE 1.3 6.9 0.4 6.3 9.0

PAGE A-17HYDROCARBON SPECIATION DATA

SHED TEST

FORD F-150
SHED results, mg

FT-4614-S FT-4614-M FT-4637-S FT-4637-M FT-4640-S FT-4640-M

COMPOUND 7/17/2002 7/19/2002 7/24/2002 7/23/2002 7/26/2002 7/29/2002 Houston Fuel Atlanta Fuel Chicago Fuel

2,5-DIMETHYLHEXANE

ETHYLCYCLOPENTANE

2,4-DIMETHYLHEXANE 0.8 5.9 0.3 1.4 0.6 3.5

1-TRANS-2-CIS-4-TRIMETHYLCYCLOPENTANE 0.3 1.5 0.3 1.3 1.6

3,3-DIMETHYLHEXANE

1-TRANS-2-CIS-3-TRIMETHYLCYCLOPENTANE 0.6 0.5 0.6

2,3,4-TRIMETHYLPENTANE 2.7 13.8 2.6 10.8 2.9 13.9

2,3,3-TRIMETHYLPENTANE 2.1 17.5 1.9 10.6 2.4 19.3

TOLUENE 10.2 31.4 14.8 44.4 15.7 32.3

2,3-DIMETHYLHEXANE 10.2 8.3 9.5

1,1,2-TRIMETHYLCYCLOPENTANE

2-METHYLHEPTANE 1.7

3,4-DIMETHYLHEXANE, NOTE B

4-METHYLHEPTANE 1.5 7.9 6.6 1.9 8.0

3-METHYLHEPTANE 1.7 8.4 1.4 4.7 1.9 8.0

1-CIS,2-TRANS,3-TRIMETHYLCYCLOPENTANE

CIS-1,3-DIMETHYLCYCLOHEXANE

TRANS-1,4-DIMETHYLCYCLOHEXANE

3-ETHYLHEXANE

2,2,5-TRIMETHYLHEXANE 0.8 3.7 0.6 3.8 1.1 5.3

TRANS-1-METHYL-3-ETHYLCYCLOPENTANE

CIS-1-METHYL-3-ETHYLCYCLOPENTANE 0.7 0.5 0.6

1,1-DIMETHYLCYCLOHEXANE

TRANS-1-METHYL-2-ETHYLCYCLOPENTANE

1-METHYL-1-ETHYL-CYCLOPENTANE

2,4,4-TRIMETHYLHEXANE 0.4

2,2,4-TRIMETHYLHEXANE

TRANS-1,2-DIMETHYLCYCLOHEXANE 0.3 0.4

1-OCTENE

TRANS-4-OCTENE

OCTANE 1.3 4.1 1.5 4.0 1.5 4.8

UNIDENTIFIED C8 0.3 1.1 1.7

TRANS-2-OCTENE 0.4

TRANS-1,3-DIMETHYLCYCLOHEXANE, NOTE C

CIS-2-OCTENE

ISOPROPYLCYCLOPENTANE

2,2-DIMETHYLHEPTANE

2,3,5-TRIMETHYLHEXANE 0.3 0.3 0.3 0.7

CIS-1-METHYL-2-ETHYLCYCLOPENTANE 0.3

2,4-DIMETHYLHEPTANE 0.6 0.7

4,4-DIMETHYLHEPTANE

CIS-1,2-DIMETHYLCYCLOHEXANE

ETHYLCYCLOHEXANE

2,6-DIMETHYLHEPTANE, NOTE D 0.3 1.1 0.5 1.0 0.5 1.5

1,1,3-TRIMETHYLCYCLOHEXANE

2,5-DIMETHYLHEPTANE, NOTE E 0.3 0.9 0.4 1.0 0.5 1.5

3,3-DIMETHYLHEPTANE

3,5-DIMETHYLHEPTANE, NOTE E

ETHYLBENZENE 2.9 6.0 4.4 7.3 3.8 6.4

PAGE A-18HYDROCARBON SPECIATION DATA

SHED TEST

FORD F-150
SHED results, mg

FT-4614-S FT-4614-M FT-4637-S FT-4637-M FT-4640-S FT-4640-M

COMPOUND 7/17/2002 7/19/2002 7/24/2002 7/23/2002 7/26/2002 7/29/2002 Houston Fuel Atlanta Fuel Chicago Fuel

2,3,4-TRIMETHYLHEXANE

2,3-DIMETHYLHEPTANE

m-& p-XYLENE 7.7 14.3 13.8 23.1 10.9 18.4

4-METHYLOCTANE

3,4-DIMETHYLHEPTANE

4-ETHYLHEPTANE

2-METHYLOCTANE 0.4 1.4 0.7 2.3 0.6 1.6

3-METHYLOCTANE 0.3 1.0 1.1 1.3

STYRENE

o-XYLENE 0.5 5.1 1.6 8.0 10.2 8.7

1-NONENE 7.0 1.3

TRANS-3-NONENE

CIS-3-NONENE

NONANE 2.5 0.6 0.9 0.6 1.1

TRANS-2-NONENE

ISOPROPYLBENZENE (CUMENE) 0.5 1.8 0.5

2,2-DIMETHYLOCTANE 0.9

2,4-DIMETHYLOCTANE

n-PROPYLBENZENE 1.3 1.3 0.5 0.4

1-METHYL-3-ETHYLBENZENE 3.5 3.4 0.9

1-METHYL-4-ETHYLBENZENE 0.5 0.9 0.3

1,3,5-TRIMETHYLBENZENE 2.5 1.8 0.3

1-METHYL-2-ETHYLBENZENE 1.8 0.4 0.6

1,2,4-TRIMETHYLBENZENE

TERT-BUTYLBENZENE

1-DECENE

DECANE, NOTE F 1.4 2.3

ISOBUTYLBENZENE, NOTE F 1.3 2.1

1,3,-DIMETHYL-5-ETHYLBENZENE

METHYLPROPYLBENZENE (sec butylbenzene)

1-METHYL-3-ISOPROPYLBENZENE

1,2,3-TRIMETHYLBENZENE 2.2 0.7

1-METHYL-4-ISOPROPYLBENZENE 1.0 1.1

INDAN

1-METHYL-2-ISOPROPYLBENZENE 0.3

1,3-DIETHYLBENZENE

1,4-DIETHYLBENZENE

1-METHYL-3-N-PROPYLBENZENE 0.3 0.3

1-METHYL-4-N-PROPYLBENZENE, NOTE G 1.8

1,2 DIETHYLBENZENE 1.8

1-METHYL-2-N-PROPYLBENZENE 0.5

1,4-DIMETHYL-2-ETHYLBENZENE 0.7

1,3-DIMETHYL-4-ETHYLBENZENE 0.4 1.1 1.5 0.6

1,2-DIMETHYL-4-ETHYLBENZENE

1,3-DIMETHYL-2-ETHYLBENZENE

UNDECANE 0.4

1,2-DIMETHYL-3-ETHYLBENZENE

1,2,4,5-TETRAMETHYLBENZENE

2-METHYLBUTYLBENZENE (sec AMYLBENZENE)

PAGE A-19HYDROCARBON SPECIATION DATA

SHED TEST

FORD F-150
SHED results, mg

FT-4614-S FT-4614-M FT-4637-S FT-4637-M FT-4640-S FT-4640-M

COMPOUND 7/17/2002 7/19/2002 7/24/2002 7/23/2002 7/26/2002 7/29/2002 Houston Fuel Atlanta Fuel Chicago Fuel

3,4 DIMETHYLCUMENE

1,2,3,5-TETRAMETHYLBENZENE

TERT-1-BUT-2-METHYLBENZENE

1,2,3,4-TETRAMETHYLBENZENE

N-PENT-BENZENE 0.3

TERT-1-BUT-3,5-DIMETHYLBENZENE 0.1

TERT-1-BUTYL-4-ETHYLBENZENE 1.3

NAPHTHALENE

DODECANE 0.8

1,3,5-TRIETHYLBENZENE

1,2,4-TRIETHYLBENZENE

HEXYLBENZENE

UNIDENTIFIED C9-C12+ 7.5 3.3 15.8 16.7 4.5 8.6

A - 2,2-Dimethylpentane and methylcyclopentane co-elute. GC peak area split equally between the two compounds.
B - 3-Methyl-3-ethyl-pentane co-elutes with reported compound. Not reported separately. C - Cis-1,4-Dimethylcyclohexane co-elutes with reported compound. Not reported separately.
D - Propylcyclopentane co-elutes with reported compound. Not reported separately. E - 2,5-Dimethylheptane and 3,5-dimethylheptane co-elute. GC peak area split equally between the two compounds. F - Decane and isobutylbenzene co-elute. GC peak area split equally between the two compounds. G - n-Butylbenzene co-elutes with reported compound. Not reported separately.

PAGE A-20

### APPENDIX B

HYDROCARBON SPECIATION DATA

FOR TOYOTA CAMRY

TABLE OF CONTENTS FOR APPENDIX B

FTP Composite Results, Winter 2005, pp. B1-B5

SHED Test Results, Winter 2005, pp. B6-B10 FTP Composite Results, Summer 2002, pp. B11-B15 SHED Test Results, Summer 2002, pp. B16-20

A blank space in the tables indicates that the compound was not detected during analysis. A “Trace” value indicates that th e compound was dete cted, but computations of mass or mass rate
resulted in a value of less than 0.05. An “*” in the table indicates a malfunction of the analytical equipment during sample analysis and that no data are available.HYDROCARBON SPECIATION DATA

FTP COMPOSITE

TOYOTA CAMRY

FTP Composite, mg/mi

C-HOU-N C-HOU-MF C-ATL-N C-ATL-MF C-CHI-N C-CHI-MF

COMPOUND 3/31/2005 4/1/2005 4/5/2005 4/6/2005 4/12/2005 4/13/2005

METHANE 67.0 497.2 37.8 441.0 104.6 422.3

ETHANE 6.0 29.1 7.6 31.1 8.5 29.8

ETHYLENE 19.7 317.6 27.6 323.9 29.0 309.1

PROPANE 0.4 2.4 1.0 2.6 1.2 2.6

PROPYLENE 11.0 127.8 16.5 148.6 15.8 123.1

ACETYLENE 8.5 772.5 10.7 736.3 9.9 621.4

PROPADIENE 0.6 11.5 0.8 10.7 8.8

BUTANE 5.5 58.8 10.3 82.0 16.5 95.5

TRANS-2-BUTENE 0.9 9.2 1.3 10.3 1.4 9.2

1-BUTENE 2.2 21.7 2.9 22.6 3.1 20.8

2-METHYLPROPENE (ISOBUTYLENE) 8.7 80.1 6.1 49.9 5.1 38.2

2,2-DIMETHYLPROPANE (NEOPENTANE) 9.4 131.9 11.6 115.4 17.9 128.1

PROPYNE 0.1 1.0 0.1 1.1

1,3-BUTADIENE 2.7 32.0 3.7 34.3 4.3 36.7

2-METHYLPROPANE (ISOBUTANE) 0.8 9.4 1.0 7.0 1.1 7.1

1-BUTYNE

METHANOL

CIS-2-BUTENE 0.7 7.4 0.9 8.1 1.0 6.9

3-METHYL-1-BUTENE

ETHANOL 15.0 165.2

2-METHYLBUTANE (ISOPENTANE) 0.6 14.5 0.7 1.2 0.9 11.9

2-BUTYNE

1-PENTENE 0.7 10.7 0.7 6.3 1.4 8.0

2-METHYL-1-BUTENE 1.3 18.5 0.8 11.3 1.6 15.6

PENTANE 4.0 65.4 6.6 70.1 7.4 51.7

UNIDENTIFIED C5 OLEFINS 0.8 2.5 Trace 0.7 0.6

2-METHYL-1,3-BUTADIENE 0.5 9.5 0.8 8.6 1.3 9.0

TRANS-2-PENTENE 0.8 14.7 0.7 8.7 1.7 14.8

3,3-DIMETHYL-1-BUTENE 0.1 0.5 Trace 0.4 Trace 0.4

CIS-2-PENTENE 0.4 7.9 0.4 5.0 0.9 6.9

2-METHYL-2-BUTENE 0.5 21.2 0.8 11.6 2.5 22.9

TERT-BUTANOL

CYCLOPENTADIENE 3.4 0.1 1.9 0.1 1.6

2,2-DIMETHYLBUTANE 1.0 13.8 1.0 9.5 0.8 5.1

CYCLOPENTENE 0.3 4.5 0.3 3.1 0.6 5.3

4-METHYL-1-PENTENE 0.3 3.2 0.3 2.0 0.5 3.0

3-METHYL-1-PENTENE

CYCLOPENTANE 0.4 8.1 0.4 5.4 0.6 4.5

2,3-DIMETHYLBUTANE 1.5 19.4 1.6 15.9 1.8 12.1

MTBE 3.8 149.5 1.9 0.2 2.5

4-METHYL-CIS-2-PENTENE

2-METHYLPENTANE 7.2 98.2 5.5 53.7 6.5 44.5

4-METHYL-TRANS-2-PENTENE 1.4 1.7 0.1 1.6 0.2 3.1

3-METHYLPENTANE 4.8 66.8 3.7 34.7 4.4 28.8

2-METHYL-1-PENTENE 0.3 4.5 0.3 3.1 0.6 4.0

1-HEXENE 0.3 4.5 0.3 3.1 0.6 4.0

HEXANE 4.7 68.9 3.5 35.6 3.6 24.7

UNIDENTIFIED C6 0.9 9.5 0.6 5.5 0.7 5.4

TRANS-3-HEXENE

CIS-3-HEXENE 0.2 3.7 0.1 1.8 0.4 3.8

DI-ISOPROPYL ETHER 0.1

TRANS-2-HEXENE 0.3 5.9 0.2 3.0 0.7 5.7 Houston Fuel Atlanta Fuel Chicago Fuel

PAGE B-1HYDROCARBON SPECIATION DATA

FTP COMPOSITE

TOYOTA CAMRY

FTP Composite, mg/mi

C-HOU-N C-HOU-MF C-ATL-N C-ATL-MF C-CHI-N C-CHI-MF

COMPOUND 3/31/2005 4/1/2005 4/5/2005 4/6/2005 4/12/2005 4/13/2005 Houston Fuel Atlanta Fuel Chicago Fuel

3-METHYL-TRANS-2-PENTENE 0.3 7.1 0.3 4.4 1.0 9.3

2-METHYL-2-PENTENE 0.2 5.8 0.2 2.7 0.6 5.8

3-METHYLCYCLOPENTENE 0.1 Trace

CIS-2-HEXENE 0.1 1.7 Trace 1.6 0.3 3.1

ETBE

3-METHYL-CIS-2-PENTENE 0.6 5.0 0.7 2.9 0.7 6.7

2,2-DIMETHYLPENTANE, NOTE A 1.2 20.6 0.9 11.9 1.9 13.6

METHYLCYCLOPENTANE, NOTE A 1.2 20.2 0.9 11.7 1.9 13.4

2,4-DIMETHYLPENTANE 0.8 10.8 1.3 11.9 1.0 6.3

2,2,3-TRIMETHYLBUTANE 0.1 1.5 0.1 0.9 Trace 0.4

3,4-DIMETHYL-1-PENTENE Trace 0.4 Trace 0.4 0.1 0.5

1-METHYLCYCLOPENTENE 0.3 6.4 0.5 4.5 0.6 4.8

BENZENE 5.0 78.4 9.9 116.0 8.3 84.6

3-METHYL-1-HEXENE 0.1 0.6 1.3 1.2

3,3-DIMETHYLPENTANE 0.6 5.9 0.4 3.3 0.4 0.4

CYCLOHEXANE 0.2 2.8 0.3 3.7 0.6 6.3

2-METHYLHEXANE

2,3-DIMETHYLPENTANE 5.0 69.0 5.5 51.6 3.8 26.2

1,1-DIMETHYLCYCLOPENTANE 0.1 0.1 0.8 0.1 1.1

TERT-AMYL METHYL ETHER

CYCLOHEXENE 0.6 20.4 0.1 1.2 0.3 2.2

3-METHYLHEXANE 4.4 57.2 3.8 36.1 2.4 16.2

CIS-1,3-DIMETHYLCYCLOPENTANE 0.5 7.0 0.5 4.9 1.0 7.7

3-ETHYLPENTANE 0.8 11.5 0.8 7.8 1.2 8.8

TRANS-1,2-DIMETHYLCYCLOPENTANE

TRANS-1,3-DIMETHYLCYCLOPENTANE 0.4 6.1 0.5 4.7 0.9 7.1

1-HEPTENE

2,2,4-TRIMETHYLPENTANE 1.2 14.3 8.2 72.9 2.9 19.9

2-METHYL-1-HEXENE

TRANS-3-HEPTENE 0.2 2.1 0.1 1.8 0.4 4.1

HEPTANE 3.1 41.0 3.5 34.0 2.6 17.4

CIS-3-HEPTENE

UNIDENTIFIED C7 0.3 6.6 0.1 2.3 0.6 5.0

2-METHYL-2-HEXENE 1.9 0.6 3.8

3-METHYL-TRANS-3-HEXENE

TRANS-2-HEPTENE 0.1 2.6 0.1 1.7 0.2 2.5

3-ETHYL-CIS-2-PENTENE

2,4,4-TRIMETHYL-1-PENTENE 0.1 3.0 0.1 1.6 0.3 3.2

2,3-DIMETHYL-2-PENTENE

CIS-2-HEPTENE 0.1 1.6 0.1 1.2 0.2 1.7

METHYLCYCLOHEXANE 1.0 13.4 1.5 14.1 2.9 20.7

CIS-1,2-DIMETHYLCYCLOPENTANE

2,2-DIMETHYLHEXANE

1,1,3-TRIMETHYLCYCLOPENTANE 0.1 2.4 0.3 2.6 0.3 1.9

2,4,4-TRIMETHYL-2-PENTENE 0.1 0.1 0.1 0.1 0.1

2,2,3-TRIMETHYLPENTANE 0.6 7.5 1.2 13.5 0.9 7.2

2,5-DIMETHYLHEXANE

ETHYLCYCLOPENTANE

2,4-DIMETHYLHEXANE 0.7 9.0 1.4 15.6 1.0 5.9

1-TRANS-2-CIS-4-TRIMETHYLCYCLOPENTANE 0.2 4.2 0.2 3.2 0.4 2.7

3,3-DIMETHYLHEXANE

1-TRANS-2-CIS-3-TRIMETHYLCYCLOPENTANE 0.1 1.6 0.1 1.3 0.2 2.4

PAGE B-2HYDROCARBON SPECIATION DATA

FTP COMPOSITE

TOYOTA CAMRY

FTP Composite, mg/mi

C-HOU-N C-HOU-MF C-ATL-N C-ATL-MF C-CHI-N C-CHI-MF

COMPOUND 3/31/2005 4/1/2005 4/5/2005 4/6/2005 4/12/2005 4/13/2005 Houston Fuel Atlanta Fuel Chicago Fuel

2,3,4-TRIMETHYLPENTANE 0.5 7.0 1.9 24.0 1.8 12.1

2,3,3-TRIMETHYLPENTANE 0.2 3.1 2.1 19.8 0.8 9.8

TOLUENE 8.4 121.2 21.8 242.4 9.9 107.2

2,3-DIMETHYLHEXANE 1.0 10.9 1.4 20.4 0.5 9.4

1,1,2-TRIMETHYLCYCLOPENTANE

2-METHYLHEPTANE 1.0 0.2 1.6

3,4-DIMETHYLHEXANE, NOTE B 0.4 4.7 0.7 3.0 0.1 0.3

4-METHYLHEPTANE 1.5 18.6 1.0 16.4 1.4 10.1

3-METHYLHEPTANE 1.8 22.5 0.1 18.6 1.2 8.1

1-CIS,2-TRANS,3-TRIMETHYLCYCLOPENTANE 0.3 0.4

CIS-1,3-DIMETHYLCYCLOHEXANE

TRANS-1,4-DIMETHYLCYCLOHEXANE

3-ETHYLHEXANE 4.9 1.6 3.6 0.7 6.0

2,2,5-TRIMETHYLHEXANE 0.2 2.3 0.6 5.2 1.0 6.8

TRANS-1-METHYL-3-ETHYLCYCLOPENTANE Trace

CIS-1-METHYL-3-ETHYLCYCLOPENTANE 0.2 3.2 0.2 2.1 0.6 3.6

1,1-DIMETHYLCYCLOHEXANE

TRANS-1-METHYL-2-ETHYLCYCLOPENTANE

1-METHYL-1-ETHYL-CYCLOPENTANE

2,4,4-TRIMETHYLHEXANE 0.1 2.0 0.1 1.1 0.1

2,2,4-TRIMETHYLHEXANE

TRANS-1,2-DIMETHYLCYCLOHEXANE 0.1 2.5 0.1 1.6 0.2 2.6

1-OCTENE

TRANS-4-OCTENE 0.1 2.3 Trace 1.0 1.0

OCTANE 1.1 14.3 1.4 12.4 0.9 6.1

UNIDENTIFIED C8 0.9 10.9 0.3 3.7 0.4 4.2

TRANS-2-OCTENE 2.0 1.6

TRANS-1,3-DIMETHYLCYCLOHEXANE, NOTE C

CIS-2-OCTENE 0.1 1.1 0.1 0.7 0.1 0.8

ISOPROPYLCYCLOPENTANE

2,2-DIMETHYLHEPTANE

2,3,5-TRIMETHYLHEXANE 0.1 0.6 0.1 1.0 0.1 1.3

CIS-1-METHYL-2-ETHYLCYCLOPENTANE 1.7 0.1 1.2 0.1 1.2

2,4-DIMETHYLHEPTANE 0.2 1.6 0.1 1.4 0.1 0.9

4,4-DIMETHYLHEPTANE 0.1 1.0 0.1 0.6 0.1 0.7

CIS-1,2-DIMETHYLCYCLOHEXANE

ETHYLCYCLOHEXANE 0.2

2,6-DIMETHYLHEPTANE, NOTE D 0.3 3.2 0.3 2.7 0.4 2.8

1,1,3-TRIMETHYLCYCLOHEXANE

2,5-DIMETHYLHEPTANE, NOTE E 0.2 2.4 0.2 2.0 0.2 1.2

3,3-DIMETHYLHEPTANE

3,5-DIMETHYLHEPTANE, NOTE E 0.2 2.4 0.2 2.0 0.2 1.2

ETHYLBENZENE 3.7 45.8 6.2 54.5 3.5 23.3

2,3,4-TRIMETHYLHEXANE

2,3-DIMETHYLHEPTANE

m-& p-XYLENE 13.2 165.9 19.2 170.4 10.9 75.3

4-METHYLOCTANE

3,4-DIMETHYLHEPTANE

4-ETHYLHEPTANE

2-METHYLOCTANE 0.9 12.2 0.9 8.6 0.6 5.0

3-METHYLOCTANE 0.6 8.1 0.7 5.7 0.4 3.2

STYRENE 1.1 16.1 1.8 19.7 9.2

PAGE B-3HYDROCARBON SPECIATION DATA

FTP COMPOSITE

TOYOTA CAMRY

FTP Composite, mg/mi

C-HOU-N C-HOU-MF C-ATL-N C-ATL-MF C-CHI-N C-CHI-MF

COMPOUND 3/31/2005 4/1/2005 4/5/2005 4/6/2005 4/12/2005 4/13/2005 Houston Fuel Atlanta Fuel Chicago Fuel

o-XYLENE 5.3 64.1 7.7 66.7 3.9 27.3

1-NONENE 0.2 2.0 0.2 2.4 0.3 2.6

TRANS-3-NONENE

CIS-3-NONENE

NONANE 0.4 5.9 0.5 4.9 0.4 3.6

TRANS-2-NONENE

ISOPROPYLBENZENE (CUMENE) Trace 0.8 Trace 0.6 Trace 0.4

2,2-DIMETHYLOCTANE 0.1 1.4 0.1 0.9 0.1 1.3

2,4-DIMETHYLOCTANE 0.1 1.4 0.1 0.7 0.2 1.6

n-PROPYLBENZENE 1.0 16.1 1.6 17.5 0.9 8.3

1-METHYL-3-ETHYLBENZENE 4.5 66.5 7.1 69.6 3.7 34.2

1-METHYL-4-ETHYLBENZENE 1.9 27.3 2.7 27.7 1.5 12.5

1,3,5-TRIMETHYLBENZENE 2.3 32.6 2.8 30.4 2.3 17.9

1-METHYL-2-ETHYLBENZENE 1.9 23.6 2.6 26.9 1.8 12.2

1,2,4-TRIMETHYLBENZENE 7.2 105.3 10.8 114.8 6.6 58.7

TERT-BUTYLBENZENE

1-DECENE

DECANE, NOTE F 0.2 2.5 Trace 1.8 0.8 3.3

ISOBUTYLBENZENE, NOTE F 0.2 2.4 Trace 1.7 0.7 3.1

1,3,-DIMETHYL-5-ETHYLBENZENE
METHYLPROPYLBENZENE (sec butylbenzene) 0.1 1.3 0.3 2.0 0.1 1.2

1-METHYL-3-ISOPROPYLBENZENE

1,2,3-TRIMETHYLBENZENE 1.6 23.9 2.5 28.0 1.9 14.4

1-METHYL-4-ISOPROPYLBENZENE 0.1 1.3 0.1 1.4 0.1 1.2

INDAN

1-METHYL-2-ISOPROPYLBENZENE 0.8 11.3 1.3 9.0 1.1 10.0

1,3-DIETHYLBENZENE

1,4-DIETHYLBENZENE Trace 0.3

1-METHYL-3-N-PROPYLBENZENE 0.5 11.0 2.4 19.4 0.9 9.0

1-METHYL-4-N-PROPYLBENZENE, NOTE G 1.2 17.7 1.9 24.7 1.8 15.5

1,2 DIETHYLBENZENE 1.8 0.1 1.4 0.2

1-METHYL-2-N-PROPYLBENZENE 0.2 2.3 0.5 6.9 0.3 1.3

1,4-DIMETHYL-2-ETHYLBENZENE 1.3 11.1 1.1 7.9

1,3-DIMETHYL-4-ETHYLBENZENE 1.3 13.3 1.3 7.4 1.9 9.5

1,2-DIMETHYL-4-ETHYLBENZENE 2.1

1,3-DIMETHYL-2-ETHYLBENZENE 1.6 0.1 2.9 0.2 1.3

UNDECANE 0.2 4.9 0.7 7.3 0.7 3.7

1,2-DIMETHYL-3-ETHYLBENZENE 0.4 5.3

1,2,4,5-TETRAMETHYLBENZENE 0.1 7.2 0.7 9.3 1.0 9.7

2-METHYLBUTYLBENZENE (sec AMYLBENZENE)

3,4 DIMETHYLCUMENE 0.1

1,2,3,5-TETRAMETHYLBENZENE 1.0 11.8 1.4 17.4 0.9

TERT-1-BUT-2-METHYLBENZENE 0.2 7.1 0.6 8.0 1.2 7.1

1,2,3,4-TETRAMETHYLBENZENE 0.1 10.7 0.8 8.6

N-PENT-BENZENE 0.3 7.0 0.5 7.8 0.1 3.0

TERT-1-BUT-3,5-DIMETHYLBENZENE

TERT-1-BUTYL-4-ETHYLBENZENE Trace 8.0 0.3 5.8 0.2 2.6

NAPHTHALENE 2.5 1.3

DODECANE 0.2 5.1 0.2 4.3 0.1 1.5

1,3,5-TRIETHYLBENZENE

1,2,4-TRIETHYLBENZENE

HEXYLBENZENE

PAGE B-4HYDROCARBON SPECIATION DATA

FTP COMPOSITE

TOYOTA CAMRY

FTP Composite, mg/mi

C-HOU-N C-HOU-MF C-ATL-N C-ATL-MF C-CHI-N C-CHI-MF

COMPOUND 3/31/2005 4/1/2005 4/5/2005 4/6/2005 4/12/2005 4/13/2005 Houston Fuel Atlanta Fuel Chicago Fuel

UNIDENTIFIED C9-C12+ 6.3 136.7 9.4 120.6 13.9 144.1

FORMALDEHYDE 4.8 36.2 4.0 48.7 3.6 49.6

ACETALDEHYDE 1.1 9.3 1.3 9.1 3.0 18.7

ACROLEIN 0.4 3.8 0.3 4.4 0.1 2.5

ACETONE 0.8 5.5 0.4 2.1 0.4 1.7

PROPIONALDEHYDE 0.2 4.2 0.2 2.9 0.5 4.7

CROTONALDEHYDE 0.3 4.0 0.3 2.8 0.5 2.9

ISOBUTYRALDEHYDE, NOTE H Trace 0.8 0.2 0.8 0.2 0.7

METHYL ETHYL KETONE, NOTE H Trace 0.8 0.2 0.8 0.2 0.7

BENZALDEHYDE 0.4 5.4 0.9 8.1 0.6 4.6

ISOVALERALDEHYDE Trace 0.6 0.1 0.7 0.1 0.8

VALERALDEHYDE 0.5 0.1 0.6 0.1 0.6

O-TOLUALDEHYDE 0.1 1.7 0.2 0.9 0.1 1.5

M/P-TOLUALDEHYDE 0.9 7.4 1.2 7.7 0.7 4.3

HEXANALDEHYDE 0.1 0.1 0.1 0.1 0.1 0.1

DIMETHYLBENZALDEHYDE 0.2 3.5 0.5 3.3 0.4 2.1

A - 2,2-Dimethylpentane and methylcyclopentane co-elute. GC peak area split equally between the two compounds.
B - 3-Methyl-3-ethyl-pentane co-elutes with reported compound. Not reported separately. C - Cis-1,4-Dimethylcyclohexane co-elutes with reported compound. Not reported separately.
D - Propylcyclopentane co-elutes with reported compound. Not reported separately. E - 2,5-Dimethylheptane and 3,5-dimethylheptane co-elute. GC peak area split equally between the two compounds. F - Decane and isobutylbenzene co-elute. GC peak area split equally between the two compounds. G - n-Butylbenzene co-elutes with reported compound. Not reported separately. H - Isobutyraldehyde and methyl ethyl ketone co-elute. LC peak area split equally between the two compounds.

PAGE B-5HYDROCARBON SPECIATION DATA

SHED TEST

TOYOTA CAMRY

SHED results, mg

C-HOU-N C-HOU-MF C-ATL-N C-ATL-MF C-CHI-N C-CHI-MF

COMPOUND 3/31/2005 4/1/2005 4/5/2005 4/6/2005 4/12/2005 4/13/2005

METHANE

-- -- -- -- -- --

ETHANE 0.2 6.8 1.6 0.1 3.3

ETHYLENE 1.0 0.4 0.4

PROPANE 34.4 22.8 0.1 55.6

PROPYLENE 0.2 9.3 11.2 0.2 7.7

ACETYLENE

PROPADIENE

BUTANE 4.9 2046.6 8.8 1982.4 22.2 2917.3

TRANS-2-BUTENE 0.6 80.8 0.5 43.9 0.9 69.3

1-BUTENE 49.3 19.3 0.2 38.3

2-METHYLPROPENE (ISOBUTYLENE) 0.4 39.5 0.2 18.5 0.4 45.2

2,2-DIMETHYLPROPANE (NEOPENTANE) 7.5 1790.2 6.9 1065.8 14.3 1695.8

PROPYNE

1,3-BUTADIENE 3.7 0.5 1.6

2-METHYLPROPANE (ISOBUTANE) 356.6 0.4 225.1 1.0 266.1

1-BUTYNE

METHANOL

CIS-2-BUTENE 0.4 74.1 0.2 42.7 0.6 53.2

3-METHYL-1-BUTENE

ETHANOL 44.7 1301.8

2-METHYLBUTANE (ISOPENTANE)

2-BUTYNE

1-PENTENE 0.4 73.7 3.3 20.6 0.7 67.6

2-METHYL-1-BUTENE 0.9 95.6 1.1 42.6 1.6 163.0

PENTANE 2.8 675.1 5.8 480.1 8.9 611.6

UNIDENTIFIED C5 OLEFINS

2-METHYL-1,3-BUTADIENE 9.6 0.7 7.0

TRANS-2-PENTENE 1.2 128.2 0.9 41.9 2.9 169.2

3,3-DIMETHYL-1-BUTENE 4.0 2.6

CIS-2-PENTENE 0.7 67.2 0.4 21.5 1.3 93.2

2-METHYL-2-BUTENE 2.8 140.4 1.8 63.6 4.6 292.2

TERT-BUTANOL

CYCLOPENTADIENE 3.6 3.3

2,2-DIMETHYLBUTANE 0.3 76.3 0.3 33.7 0.4 27.9

CYCLOPENTENE 22.1 6.8 0.7 32.2

4-METHYL-1-PENTENE 0.8 12.8 0.5 3.7 16.0

3-METHYL-1-PENTENE

CYCLOPENTANE 48.4 20.7 0.9 32.2

2,3-DIMETHYLBUTANE 0.6 96.9 0.8 48.9 1.1 65.5

MTBE 1529.3 6.3 25.2

4-METHYL-CIS-2-PENTENE

2-METHYLPENTANE 3.2 414.3 8.6 152.5 4.6 218.8

4-METHYL-TRANS-2-PENTENE 2.1 25.5 7.6 1.9 15.0

3-METHYLPENTANE 2.0 252.0 2.3 85.2 2.8 124.8

2-METHYL-1-PENTENE 0.4 0.2 3.5 0.4 16.0

1-HEXENE 0.4 0.2 3.5 0.4 16.0

HEXANE 3.4 208.1 3.3 67.5 3.5 90.1

UNIDENTIFIED C6 0.4 39.2 0.3 4.2

TRANS-3-HEXENE

CIS-3-HEXENE 12.2 4.0 0.6 14.6

DI-ISOPROPYL ETHER 21.4

TRANS-2-HEXENE 0.4 15.8 0.4 5.3 0.8 37.2 Houston Fuel Atlanta Fuel Chicago Fuel

PAGE B-6HYDROCARBON SPECIATION DATA

SHED TEST

TOYOTA CAMRY

SHED results, mg

C-HOU-N C-HOU-MF C-ATL-N C-ATL-MF C-CHI-N C-CHI-MF

COMPOUND 3/31/2005 4/1/2005 4/5/2005 4/6/2005 4/12/2005 4/13/2005 Houston Fuel Atlanta Fuel Chicago Fuel

3-METHYL-TRANS-2-PENTENE 1.3 25.8 0.6 8.8 1.3 21.7

2-METHYL-2-PENTENE 0.5 16.8 0.3 5.4 0.5

3-METHYLCYCLOPENTENE 0.2

CIS-2-HEXENE 0.3 10.4 3.3 0.4 11.2

ETBE

3-METHYL-CIS-2-PENTENE 0.4 15.5 0.4 5.3 0.5 23.4

2,2-DIMETHYLPENTANE, NOTE A 1.2 54.8 0.9 19.9 1.4 42.8

METHYLCYCLOPENTANE, NOTE A 1.2 53.6 0.9 19.5 1.4 41.9

2,4-DIMETHYLPENTANE 24.1 0.3 15.8 0.1 18.1

2,2,3-TRIMETHYLBUTANE 0.2 3.5 1.2 0.5 2.2

3,4-DIMETHYL-1-PENTENE 1.2 1.0

1-METHYLCYCLOPENTENE 0.9 11.5 1.0 6.2 1.1 24.2

BENZENE 3.1 23.8 2.6 28.2 5.4 41.4

3-METHYL-1-HEXENE

3,3-DIMETHYLPENTANE 10.0 0.6 3.9 1.0 2.1

CYCLOHEXANE 6.9 14.3

2-METHYLHEXANE

2,3-DIMETHYLPENTANE 1.8 91.1 2.0 42.5 2.7 40.9

1,1-DIMETHYLCYCLOPENTANE 1.6

TERT-AMYL METHYL ETHER 2.6

CYCLOHEXENE 21.9 0.5

3-METHYLHEXANE 1.3 79.2 1.8 27.2 1.8 23.1

CIS-1,3-DIMETHYLCYCLOPENTANE 0.4 11.5 0.2 4.4 0.4 11.1

3-ETHYLPENTANE 0.4 13.4 0.3 6.0 0.5 12.1

TRANS-1,2-DIMETHYLCYCLOPENTANE

TRANS-1,3-DIMETHYLCYCLOPENTANE 0.3 7.7 0.2 3.7 0.3 9.6

1-HEPTENE

2,2,4-TRIMETHYLPENTANE 0.6 13.6 0.5 39.7 1.4 20.7

2-METHYL-1-HEXENE

TRANS-3-HEPTENE 0.2 1.4 0.4 5.0

HEPTANE 1.6 36.4 1.9 20.2 2.4 19.8

CIS-3-HEPTENE

UNIDENTIFIED C7 0.8 6.6 0.6 0.3 6.0

2-METHYL-2-HEXENE 3.9 5.4

3-METHYL-TRANS-3-HEXENE

TRANS-2-HEPTENE 2.7 0.8 2.4

3-ETHYL-CIS-2-PENTENE

2,4,4-TRIMETHYL-1-PENTENE 0.2 3.4 1.2 0.2 4.2

2,3-DIMETHYL-2-PENTENE

CIS-2-HEPTENE 1.7 0.6 1.8

METHYLCYCLOHEXANE 1.1 12.2 0.7 7.7 1.3 21.7

CIS-1,2-DIMETHYLCYCLOPENTANE

2,2-DIMETHYLHEXANE

1,1,3-TRIMETHYLCYCLOPENTANE 0.7 1.9 1.0 1.3

2,4,4-TRIMETHYL-2-PENTENE 3.3 0.5 1.7 0.3

2,2,3-TRIMETHYLPENTANE 3.3 4.3 0.4 3.7

2,5-DIMETHYLHEXANE

ETHYLCYCLOPENTANE

2,4-DIMETHYLHEXANE 0.3 4.3 0.3 4.3 0.3 7.0

1-TRANS-2-CIS-4-TRIMETHYLCYCLOPENTANE 1.5 0.8 1.8

3,3-DIMETHYLHEXANE

1-TRANS-2-CIS-3-TRIMETHYLCYCLOPENTANE 0.5 1.4

PAGE B-7HYDROCARBON SPECIATION DATA

SHED TEST

TOYOTA CAMRY

SHED results, mg

C-HOU-N C-HOU-MF C-ATL-N C-ATL-MF C-CHI-N C-CHI-MF

COMPOUND 3/31/2005 4/1/2005 4/5/2005 4/6/2005 4/12/2005 4/13/2005 Houston Fuel Atlanta Fuel Chicago Fuel

2,3,4-TRIMETHYLPENTANE 0.5 5.9 0.4 8.4 1.0 9.5

2,3,3-TRIMETHYLPENTANE 0.3 1.4 0.4 4.7 0.4 5.7

TOLUENE 4.8 31.3 8.2 48.9 11.8 43.5

2,3-DIMETHYLHEXANE 4.1 1.7 2.4

1,1,2-TRIMETHYLCYCLOPENTANE

2-METHYLHEPTANE 1.2

3,4-DIMETHYLHEXANE, NOTE B 0.6 0.4

4-METHYLHEPTANE 8.8 0.5 5.1 0.9 5.1

3-METHYLHEPTANE 0.6 9.2 0.5 4.8 0.9 5.9

1-CIS,2-TRANS,3-TRIMETHYLCYCLOPENTANE

CIS-1,3-DIMETHYLCYCLOHEXANE

TRANS-1,4-DIMETHYLCYCLOHEXANE

3-ETHYLHEXANE

2,2,5-TRIMETHYLHEXANE 1.6 0.1 1.3 0.3 3.1

TRANS-1-METHYL-3-ETHYLCYCLOPENTANE

CIS-1-METHYL-3-ETHYLCYCLOPENTANE 1.2 0.4 0.2 1.1

1,1-DIMETHYLCYCLOHEXANE

TRANS-1-METHYL-2-ETHYLCYCLOPENTANE

1-METHYL-1-ETHYL-CYCLOPENTANE

2,4,4-TRIMETHYLHEXANE 0.2

2,2,4-TRIMETHYLHEXANE

TRANS-1,2-DIMETHYLCYCLOHEXANE 1.1

1-OCTENE

TRANS-4-OCTENE 0.2 0.6

OCTANE 0.4 4.2 0.5 2.2 0.5 2.8

UNIDENTIFIED C8 0.8 2.3 0.3 0.2

TRANS-2-OCTENE 0.8 0.2 0.5

TRANS-1,3-DIMETHYLCYCLOHEXANE, NOTE C

CIS-2-OCTENE 0.2

ISOPROPYLCYCLOPENTANE

2,2-DIMETHYLHEPTANE

2,3,5-TRIMETHYLHEXANE 0.5

CIS-1-METHYL-2-ETHYLCYCLOPENTANE 0.3 0.2

2,4-DIMETHYLHEPTANE 0.1 0.2 0.4

4,4-DIMETHYLHEPTANE 0.4

CIS-1,2-DIMETHYLCYCLOHEXANE

ETHYLCYCLOHEXANE

2,6-DIMETHYLHEPTANE, NOTE D 0.7 0.4 0.9

1,1,3-TRIMETHYLCYCLOHEXANE

2,5-DIMETHYLHEPTANE, NOTE E 0.3 0.1 0.2

3,3-DIMETHYLHEPTANE

3,5-DIMETHYLHEPTANE, NOTE E 0.3 0.1 0.2

ETHYLBENZENE 1.6 5.2 2.0 4.4 2.2 5.2

2,3,4-TRIMETHYLHEXANE

2,3-DIMETHYLHEPTANE

m-& p-XYLENE 3.3 11.4 4.3 10.0 3.0 11.9

4-METHYLOCTANE

3,4-DIMETHYLHEPTANE

4-ETHYLHEPTANE

2-METHYLOCTANE 0.6

3-METHYLOCTANE

STYRENE

PAGE B-8HYDROCARBON SPECIATION DATA

SHED TEST

TOYOTA CAMRY

SHED results, mg

C-HOU-N C-HOU-MF C-ATL-N C-ATL-MF C-CHI-N C-CHI-MF

COMPOUND 3/31/2005 4/1/2005 4/5/2005 4/6/2005 4/12/2005 4/13/2005 Houston Fuel Atlanta Fuel Chicago Fuel

o-XYLENE 1.8 0.7 2.2 0.2 2.2

1-NONENE 0.2

TRANS-3-NONENE

CIS-3-NONENE

NONANE 0.3

TRANS-2-NONENE

ISOPROPYLBENZENE (CUMENE)

2,2-DIMETHYLOCTANE

2,4-DIMETHYLOCTANE

n-PROPYLBENZENE

1-METHYL-3-ETHYLBENZENE

1-METHYL-4-ETHYLBENZENE

1,3,5-TRIMETHYLBENZENE

1-METHYL-2-ETHYLBENZENE

1,2,4-TRIMETHYLBENZENE 0.2 0.3

TERT-BUTYLBENZENE

1-DECENE

DECANE, NOTE F

ISOBUTYLBENZENE, NOTE F

1,3,-DIMETHYL-5-ETHYLBENZENE
METHYLPROPYLBENZENE (sec butylbenzene)

1-METHYL-3-ISOPROPYLBENZENE

1,2,3-TRIMETHYLBENZENE

1-METHYL-4-ISOPROPYLBENZENE

INDAN

1-METHYL-2-ISOPROPYLBENZENE

1,3-DIETHYLBENZENE

1,4-DIETHYLBENZENE

1-METHYL-3-N-PROPYLBENZENE

1-METHYL-4-N-PROPYLBENZENE, NOTE G

1,2 DIETHYLBENZENE

1-METHYL-2-N-PROPYLBENZENE

1,4-DIMETHYL-2-ETHYLBENZENE

1,3-DIMETHYL-4-ETHYLBENZENE

1,2-DIMETHYL-4-ETHYLBENZENE

1,3-DIMETHYL-2-ETHYLBENZENE

UNDECANE

1,2-DIMETHYL-3-ETHYLBENZENE

1,2,4,5-TETRAMETHYLBENZENE
2-METHYLBUTYLBENZENE (sec AMYLBENZENE)

3,4 DIMETHYLCUMENE

1,2,3,5-TETRAMETHYLBENZENE

TERT-1-BUT-2-METHYLBENZENE

1,2,3,4-TETRAMETHYLBENZENE

N-PENT-BENZENE 0.2

TERT-1-BUT-3,5-DIMETHYLBENZENE

TERT-1-BUTYL-4-ETHYLBENZENE

NAPHTHALENE

DODECANE

1,3,5-TRIETHYLBENZENE

1,2,4-TRIETHYLBENZENE

HEXYLBENZENE

PAGE B-9HYDROCARBON SPECIATION DATA

SHED TEST

TOYOTA CAMRY

SHED results, mg

C-HOU-N C-HOU-MF C-ATL-N C-ATL-MF C-CHI-N C-CHI-MF

COMPOUND 3/31/2005 4/1/2005 4/5/2005 4/6/2005 4/12/2005 4/13/2005 Houston Fuel Atlanta Fuel Chicago Fuel

UNIDENTIFIED C9-C12+ 1.3 0.4 0.3

A - 2,2-Dimethylpentane and methylcyclopentane co-elute. GC peak area split equally between the two compounds.
B - 3-Methyl-3-ethyl-pentane co-elutes with reported compound. Not reported separately. C - Cis-1,4-Dimethylcyclohexane co-elutes with reported compound. Not reported separately.
D - Propylcyclopentane co-elutes with reported compound. Not reported separately. E - 2,5-Dimethylheptane and 3,5-dimethylheptane co-elute. GC peak area split equally between the two compounds. F - Decane and isobutylbenzene co-elute. GC peak area split equally between the two compounds. G - n-Butylbenzene co-elutes with reported compound. Not reported separately.

PAGE B-10HYDROCARBON SPECIATION DATA

FTP COMPOSITE

TOYOTA CAMRY

FTP Composite, mg/mi

TC-4614-S TC-4614-M TC-4637-S TC-4637-M TC-4640-S TC-4640-M

COMPOUND 7/18/2002 8/20/2002 8/2/2002 8/9/2002 8/14/2002 8/15/2002

METHANE 39.8 482.9 39.0 395.1 34.7 480.9

ETHANE 5.2 * 8.2 27.6 * 38.8

ETHYLENE 11.4 * 19.9 344.8 * 337.8

PROPANE * 0.3 3.0 * 6.4

PROPYLENE 0.2 * *

ACETYLENE 3.9 * 4.9 528.6 * 530.1

PROPADIENE * *

BUTANE 1.3 * 1.2 14.4 * 8.8

TRANS-2-BUTENE * 0.6 6.9 * 1.9

1-BUTENE 1.0 * 2.0 22.4 * 2.4

2-METHYLPROPENE (ISOBUTYLENE) 6.0 * 4.2 56.5 * 6.1

2,2-DIMETHYLPROPANE (NEOPENTANE) 0.3 * 0.7 *

PROPYNE * *

1,3-BUTADIENE * 0.3 7.7 *

2-METHYLPROPANE (ISOBUTANE) * 166.5 *

1-BUTYNE * *

METHANOL * *

CIS-2-BUTENE * 0.1 16.0 *

3-METHYL-1-BUTENE * *

ETHANOL * 7.2 256.2

2-METHYLBUTANE (ISOPENTANE) 3.5 * 0.6 11.0 * 71.7

2-BUTYNE

1-PENTENE 0.4 9.0 6.2 0.4 2.1

2-METHYL-1-BUTENE 0.6 14.5 0.4 10.7 0.5 13.5

PENTANE 2.4 40.6 1.1 42.8 1.0 17.5

UNIDENTIFIED C5 OLEFINS 0.2 6.3 0.3 2.9 9.0

2-METHYL-1,3-BUTADIENE 0.5 9.1 2.4 8.3 0.6 11.2

TRANS-2-PENTENE 0.7 14.2 0.7 9.1 0.6 11.4

3,3-DIMETHYL-1-BUTENE 0.3 0.4 0.3 4.8

CIS-2-PENTENE 0.4 8.3 0.3 5.0 0.3 6.0

2-METHYL-2-BUTENE 1.1 20.4 0.9 13.5 1.2 19.9

TERT-BUTANOL

CYCLOPENTADIENE 0.2 7.3 5.3 0.3 6.3

2,2-DIMETHYLBUTANE 0.5 6.4 0.5 7.2 0.6 9.7

CYCLOPENTENE 1.2 4.8 0.2 3.2 0.2 4.1

4-METHYL-1-PENTENE 0.2 2.8 0.2 2.6 0.1 1.8

3-METHYL-1-PENTENE 1.7

CYCLOPENTANE 0.3 4.9 0.2 4.4 0.3 2.4

2,3-DIMETHYLBUTANE 0.9 16.8 0.8 11.8 1.5 24.7

MTBE 1.3 54.8

4-METHYL-CIS-2-PENTENE

2-METHYLPENTANE 2.6 62.7 2.5 40.0 2.6 44.5

4-METHYL-TRANS-2-PENTENE 0.2 2.2 Trace 0.9

3-METHYLPENTANE 2.5 47.5 1.8 26.9 1.6 32.1

2-METHYL-1-PENTENE 0.2 4.1 0.2 2.5 0.1 2.4

1-HEXENE 0.2 3.5 0.2 2.5 0.1 2.5

HEXANE 2.8 50.8 1.8 26.8 1.3 27.4

UNIDENTIFIED C6 0.4 61.2 0.5 7.9 0.3 6.6

TRANS-3-HEXENE

CIS-3-HEXENE 2.8 0.1 1.3 1.6

DI-ISOPROPYL ETHER

TRANS-2-HEXENE 0.1 4.5 0.1 2.1 0.1 2.5 Houston Fuel Atlanta Fuel Chicago Fuel

PAGE B-11HYDROCARBON SPECIATION DATA

FTP COMPOSITE

TOYOTA CAMRY

FTP Composite, mg/mi

TC-4614-S TC-4614-M TC-4637-S TC-4637-M TC-4640-S TC-4640-M

COMPOUND 7/18/2002 8/20/2002 8/2/2002 8/9/2002 8/14/2002 8/15/2002 Houston Fuel Atlanta Fuel Chicago Fuel

3-METHYL-TRANS-2-PENTENE 0.2 6.6 0.2 16.6 0.2 4.4

2-METHYL-2-PENTENE 0.3 4.3 0.1 2.4 0.1 3.1

3-METHYLCYCLOPENTENE 0.2

CIS-2-HEXENE 0.2 2.5 0.1 1.2 1.4

ETBE

3-METHYL-CIS-2-PENTENE 0.4 5.2 0.3 2.6 0.2 3.5

2,2-DIMETHYLPENTANE, NOTE A 0.6 11.5 0.5 9.6 0.8 16.5

METHYLCYCLOPENTANE, NOTE A 0.6 11.3 0.5 9.4 0.8 16.2

2,4-DIMETHYLPENTANE 0.7 9.2 0.7 8.0 1.3 20.3

2,2,3-TRIMETHYLBUTANE 0.9 0.5 1.1

3,4-DIMETHYL-1-PENTENE 0.1

1-METHYLCYCLOPENTENE 0.4 8.2 0.2 6.5 0.3 6.2

BENZENE 3.8 95.9 9.0 138.3 42.9 99.3

3-METHYL-1-HEXENE Trace

3,3-DIMETHYLPENTANE 0.3 2.1 0.1 1.4 1.6

CYCLOHEXANE 0.2 3.4 0.4 5.6 0.9 11.9

2-METHYLHEXANE

2,3-DIMETHYLPENTANE 2.7 33.0 2.8 30.5 4.3 56.6

1,1-DIMETHYLCYCLOPENTANE 0.6 1.3

TERT-AMYL METHYL ETHER

CYCLOHEXENE 0.1 1.2 0.1 1.0 1.3

3-METHYLHEXANE 2.4 23.2 2.0 21.7 2.3 28.8

CIS-1,3-DIMETHYLCYCLOPENTANE 0.2 3.6 0.2 2.9 0.3 6.3

3-ETHYLPENTANE 0.1 3.9 3.3

TRANS-1,2-DIMETHYLCYCLOPENTANE

TRANS-1,3-DIMETHYLCYCLOPENTANE 0.1 3.4 0.2 2.6 0.4 6.3

1-HEPTENE

2,2,4-TRIMETHYLPENTANE 3.4 38.1 5.4 51.8 5.9 66.5

2-METHYL-1-HEXENE

TRANS-3-HEPTENE 0.1 2.6 0.1 1.0 0.6

HEPTANE 0.8 15.7 0.5 21.9 2.8 32.7

CIS-3-HEPTENE

UNIDENTIFIED C7 0.2 2.4 1.1 1.7

2-METHYL-2-HEXENE 2.6

3-METHYL-TRANS-3-HEXENE

TRANS-2-HEPTENE 0.1 1.9 Trace 0.8 0.8

3-ETHYL-CIS-2-PENTENE

2,4,4-TRIMETHYL-1-PENTENE 0.1 2.3 0.1 1.2 1.4

2,3-DIMETHYL-2-PENTENE

CIS-2-HEPTENE 0.1 1.6 0.1 0.9 0.1 1.1

METHYLCYCLOHEXANE 0.6 7.6 0.8 11.2 1.4 20.6

CIS-1,2-DIMETHYLCYCLOPENTANE

2,2-DIMETHYLHEXANE

1,1,3-TRIMETHYLCYCLOPENTANE 0.1 1.2 0.1 1.5 0.1 2.3

2,4,4-TRIMETHYL-2-PENTENE

2,2,3-TRIMETHYLPENTANE 0.5 9.3 0.9 6.6 16.6

2,5-DIMETHYLHEXANE

ETHYLCYCLOPENTANE

2,4-DIMETHYLHEXANE 0.3 9.2 0.8 8.5 2.3 12.2

1-TRANS-2-CIS-4-TRIMETHYLCYCLOPENTANE 0.2 2.2 0.2 2.0 0.2 3.3

3,3-DIMETHYLHEXANE

1-TRANS-2-CIS-3-TRIMETHYLCYCLOPENTANE 0.0 0.9 Trace 0.5 1.4

PAGE B-12HYDROCARBON SPECIATION DATA

FTP COMPOSITE

TOYOTA CAMRY

FTP Composite, mg/mi

TC-4614-S TC-4614-M TC-4637-S TC-4637-M TC-4640-S TC-4640-M

COMPOUND 7/18/2002 8/20/2002 8/2/2002 8/9/2002 8/14/2002 8/15/2002 Houston Fuel Atlanta Fuel Chicago Fuel

2,3,4-TRIMETHYLPENTANE 1.8 19.3 1.6 15.0 2.8 30.7

2,3,3-TRIMETHYLPENTANE 2.3 34.8 1.5 18.2 2.9 52.4

TOLUENE 7.9 142.2 24.6 309.2 9.2 154.3

2,3-DIMETHYLHEXANE 1.3 18.0 1.7 2.5 29.1

1,1,2-TRIMETHYLCYCLOPENTANE

2-METHYLHEPTANE 0.9

3,4-DIMETHYLHEXANE, NOTE B 1.1 0.1 0.8 0.1 1.7

4-METHYLHEPTANE 0.3 12.2 1.4 12.1 1.5 17.1

3-METHYLHEPTANE 1.0 12.4 0.9 10.3 1.3 14.1

1-CIS,2-TRANS,3-TRIMETHYLCYCLOPENTANE 0.7

CIS-1,3-DIMETHYLCYCLOHEXANE

TRANS-1,4-DIMETHYLCYCLOHEXANE

3-ETHYLHEXANE 0.1 3.0 0.3 2.0 0.4 4.3

2,2,5-TRIMETHYLHEXANE 0.4 5.8 0.6 7.0 1.7 17.3

TRANS-1-METHYL-3-ETHYLCYCLOPENTANE

CIS-1-METHYL-3-ETHYLCYCLOPENTANE 1.0 3.1 0.3 2.0 0.3 3.3

1,1-DIMETHYLCYCLOHEXANE

TRANS-1-METHYL-2-ETHYLCYCLOPENTANE

1-METHYL-1-ETHYL-CYCLOPENTANE

2,4,4-TRIMETHYLHEXANE 0.1 1.5 0.1 0.9 0.9

2,2,4-TRIMETHYLHEXANE

TRANS-1,2-DIMETHYLCYCLOHEXANE 0.1 2.0 0.1 1.0 0.1 1.2

1-OCTENE

TRANS-4-OCTENE

OCTANE 0.7 8.4 1.0 9.6 1.0 11.8

UNIDENTIFIED C8 0.2 3.8 0.7 0.1 1.7

TRANS-2-OCTENE 0.1 2.4 0.9 0.3

TRANS-1,3-DIMETHYLCYCLOHEXANE, NOTE C

CIS-2-OCTENE 0.1 1.1 Trace 0.4 0.2 0.3

ISOPROPYLCYCLOPENTANE

2,2-DIMETHYLHEPTANE

2,3,5-TRIMETHYLHEXANE 0.1 1.1 0.1 1.3 0.3 3.0

CIS-1-METHYL-2-ETHYLCYCLOPENTANE 0.1 1.1 0.1 0.9 1.0

2,4-DIMETHYLHEPTANE 0.1 1.0 0.1 1.3 0.2 1.5

4,4-DIMETHYLHEPTANE Trace 0.5 Trace 0.3 0.5

CIS-1,2-DIMETHYLCYCLOHEXANE

ETHYLCYCLOHEXANE 0.3 0.1

2,6-DIMETHYLHEPTANE, NOTE D 0.1 1.8 0.2 1.7 0.5 3.7

1,1,3-TRIMETHYLCYCLOHEXANE

2,5-DIMETHYLHEPTANE, NOTE E 0.2 2.4 0.4 3.4 0.5 4.9

3,3-DIMETHYLHEPTANE

3,5-DIMETHYLHEPTANE, NOTE E

ETHYLBENZENE 2.4 28.5 4.3 42.5 2.3 23.4

2,3,4-TRIMETHYLHEXANE

2,3-DIMETHYLHEPTANE

m-& p-XYLENE 7.7 82.8 15.1 147.7 8.3 78.8

4-METHYLOCTANE

3,4-DIMETHYLHEPTANE

4-ETHYLHEPTANE

2-METHYLOCTANE 0.7 8.1 1.1 7.1 0.9 9.0

3-METHYLOCTANE 0.5 4.6 0.5 4.6 0.6 6.1

STYRENE 0.7 12.0 1.2 16.1 0.7 9.7

PAGE B-13HYDROCARBON SPECIATION DATA

FTP COMPOSITE

TOYOTA CAMRY

FTP Composite, mg/mi

TC-4614-S TC-4614-M TC-4637-S TC-4637-M TC-4640-S TC-4640-M

COMPOUND 7/18/2002 8/20/2002 8/2/2002 8/9/2002 8/14/2002 8/15/2002 Houston Fuel Atlanta Fuel Chicago Fuel

o-XYLENE 3.6 35.3 6.1 57.3 3.7 33.0

1-NONENE 0.2 2.7 0.2 2.0 0.4 4.3

TRANS-3-NONENE

CIS-3-NONENE

NONANE 0.4 3.1 0.7 5.3 0.9 8.0

TRANS-2-NONENE

ISOPROPYLBENZENE (CUMENE) 0.1 0.2 0.3 0.3 0.8

2,2-DIMETHYLOCTANE 0.1 0.4 0.1 0.8

2,4-DIMETHYLOCTANE 0.3 0.7 0.1 0.5 0.7

n-PROPYLBENZENE 0.8 8.6 1.7 15.6 0.7 8.5

1-METHYL-3-ETHYLBENZENE 2.9 42.6 7.1 53.4 4.6 39.3

1-METHYL-4-ETHYLBENZENE 0.8 19.5 3.4 19.4 12.2

1,3,5-TRIMETHYLBENZENE 1.5 19.5 3.8 29.7 1.5 14.4

1-METHYL-2-ETHYLBENZENE 1.3 16.2 3.1 24.4 0.9 12.5

1,2,4-TRIMETHYLBENZENE 7.0 76.8 14.8 79.5 6.1 70.2

TERT-BUTYLBENZENE

1-DECENE

DECANE, NOTE F 0.3 0.5 1.0 3.6 0.3 2.0

ISOBUTYLBENZENE, NOTE F 0.3 0.4 0.9 3.4 0.2 1.9

1,3,-DIMETHYL-5-ETHYLBENZENE
METHYLPROPYLBENZENE (sec butylbenzene) 0.3 2.2 0.7

1-METHYL-3-ISOPROPYLBENZENE 19.2

1,2,3-TRIMETHYLBENZENE 1.3 0.5 3.5 30.6 1.2 15.6

1-METHYL-4-ISOPROPYLBENZENE 0.2 1.7

INDAN

1-METHYL-2-ISOPROPYLBENZENE 14.7 0.2 1.6 0.2 3.9

1,3-DIETHYLBENZENE

1,4-DIETHYLBENZENE 6.3 1.0 0.5 1.2

1-METHYL-3-N-PROPYLBENZENE 0.6 1.9 21.1 0.9 14.7

1-METHYL-4-N-PROPYLBENZENE, NOTE G 1.6 0.6 0.1 39.2 1.4 0.2

1,2 DIETHYLBENZENE 0.1 1.2

1-METHYL-2-N-PROPYLBENZENE 0.2 1.2 0.2 1.5 0.2 4.5

1,4-DIMETHYL-2-ETHYLBENZENE 29.2 2.0 13.8 1.8 12.3

1,3-DIMETHYL-4-ETHYLBENZENE 2.1 3.2 13.0 3.3

1,2-DIMETHYL-4-ETHYLBENZENE 1.1 20.9 3.2 28.6 17.6

1,3-DIMETHYL-2-ETHYLBENZENE 2.6 0.3 0.3

UNDECANE 0.3 2.5 0.3 2.6 0.3 1.6

1,2-DIMETHYL-3-ETHYLBENZENE

1,2,4,5-TETRAMETHYLBENZENE 0.1 9.0 2.0 17.9 0.4 11.7

2-METHYLBUTYLBENZENE (sec AMYLBENZENE)

3,4 DIMETHYLCUMENE

1,2,3,5-TETRAMETHYLBENZENE 2.0 0.2 0.1 0.8 0.4

TERT-1-BUT-2-METHYLBENZENE 10.8 Trace 0.7

1,2,3,4-TETRAMETHYLBENZENE 6.5 0.2 5.7 0.3 4.0

N-PENT-BENZENE 0.3

TERT-1-BUT-3,5-DIMETHYLBENZENE 0.1 11.2 1.1 23.2 29.0

TERT-1-BUTYL-4-ETHYLBENZENE

NAPHTHALENE 0.4 0.2 3.4 0.5 0.6

DODECANE 0.3 3.2 0.4 1.1 0.1 3.0

1,3,5-TRIETHYLBENZENE

1,2,4-TRIETHYLBENZENE

HEXYLBENZENE

PAGE B-14HYDROCARBON SPECIATION DATA

FTP COMPOSITE

TOYOTA CAMRY

FTP Composite, mg/mi

TC-4614-S TC-4614-M TC-4637-S TC-4637-M TC-4640-S TC-4640-M

COMPOUND 7/18/2002 8/20/2002 8/2/2002 8/9/2002 8/14/2002 8/15/2002 Houston Fuel Atlanta Fuel Chicago Fuel

UNIDENTIFIED C9-C12+ 8.4 152.9 22.0 175.3 9.9 184.7

FORMALDEHYDE 2.2 59.2 2.6 53.0 2.3 63.6

ACETALDEHYDE 5.0 13.9 1.7 13.5 2.6 34.5

ACROLEIN 1.2 8.2 0.4 6.3 0.4 8.6

ACETONE 6.4 6.1 0.8 4.0 0.6 5.7

PROPIONALDEHYDE 0.8 2.7 0.4 6.4 0.2 3.0

CROTONALDEHYDE 2.9 4.0 0.8 4.8 0.3 3.9

ISOBUTYRALDEHYDE, NOTE H 1.1 2.1 0.2 1.4 0.2 1.5

METHYL ETHYL KETONE, NOTE H 1.1 2.1 0.2 1.4 0.2 1.5

BENZALDEHYDE 0.3 6.6 0.7 11.6 0.2 5.3

ISOVALERALDEHYDE 0.4 1.2 0.1 0.2 1.2

VALERALDEHYDE 0.6 0.8 0.1 1.0 0.1 1.1

O-TOLUALDEHYDE 0.4 2.1 0.3 3.3 0.1 2.1

M/P-TOLUALDEHYDE 0.4 7.0 0.6 11.2 0.2 6.6

HEXANALDEHYDE Trace Trace 0.1 Trace

DIMETHYLBENZALDEHYDE 0.2 4.0 Trace 2.4

*C1 - C4 DATA NOT AVAILABLE DUE TO INSTRUMENT MALFUNCTION A - 2,2-Dimethylpentane and methylcyclopentane co-elute. GC peak area split equally between the two compounds.
B - 3-Methyl-3-ethyl-pentane co-elutes with reported compound. Not reported separately. C - Cis-1,4-Dimethylcyclohexane co-elutes with reported compound. Not reported separately.
D - Propylcyclopentane co-elutes with reported compound. Not reported separately. E - 2,5-Dimethylheptane and 3,5-dimethylheptane co-elute. GC peak area split equally between the two compounds. F - Decane and isobutylbenzene co-elute. GC peak area split equally between the two compounds. G - n-Butylbenzene co-elutes with reported compound. Not reported separately. H - Isobutyraldehyde and methyl ethyl ketone co-elute. LC peak area split equally between the two compounds.

PAGE B-15HYDROCARBON SPECIATION DATA

SHED TEST

TOYOTA CAMRY

SHED results, mg

TC-4614-S TC-4614-M TC-4637-S TC-4637-M TC-4640-S TC-4640-M

COMPOUND 8/19/2002 8/20/2002 8/2/2002 8/9/2002 8/14/2002 8/15/2002

METHANE

ETHANE * * *

ETHYLENE * * *

PROPANE * * 6.0 * 9.2

PROPYLENE * * *

ACETYLENE * * *

PROPADIENE * * *

BUTANE * * 2.0 81.0 * 76.7

TRANS-2-BUTENE * * *

1-BUTENE * * 1.6 *

2-METHYLPROPENE (ISOBUTYLENE) * * 7.7 13.5 *

2,2-DIMETHYLPROPANE (NEOPENTANE) * * *

PROPYNE * * *

1,3-BUTADIENE * * * *

2-METHYLPROPANE (ISOBUTANE) * * 0.6 29.9 * 34.0

1-BUTYNE * * *

METHANOL * * *

CIS-2-BUTENE * * 3.5 *

3-METHYL-1-BUTENE * * *

ETHANOL * * 21.0 301.1

2-METHYLBUTANE (ISOPENTANE) * * * 495.8

2-BUTYNE

1-PENTENE 7.1 3.5

2-METHYL-1-BUTENE 1.3 10.6 6.9 18.7

PENTANE 4.1 48.4 0.5 46.1 1.1 38.2

UNIDENTIFIED C5 OLEFINS 11.1 2.2

2-METHYL-1,3-BUTADIENE 1.7 0.6 2.6 0.3 2.9 76.2

TRANS-2-PENTENE 13.0 7.2 0.6 0.7

3,3-DIMETHYL-1-BUTENE 0.9 1.0 35.5

CIS-2-PENTENE 3.2 7.5 0.4 3.7 0.6 19.2

2-METHYL-2-BUTENE 0.5 18.3 1.2 11.4 1.5 54.7

TERT-BUTANOL

CYCLOPENTADIENE 0.3

2,2-DIMETHYLBUTANE 3.0 4.1 1.7 23.4

CYCLOPENTENE 0.7 2.9 0.3 1.6 0.6 6.6

4-METHYL-1-PENTENE 0.7 1.3 0.8 2.7

3-METHYL-1-PENTENE

CYCLOPENTANE 4.2 0.4 3.4 0.9 11.9

2,3-DIMETHYLBUTANE 1.9 7.5 0.8 6.0 1.4 49.3

MTBE 59.8

4-METHYL-CIS-2-PENTENE

2-METHYLPENTANE 10.6 20.2 7.8 20.6 7.6 71.6

4-METHYL-TRANS-2-PENTENE 0.5 0.4

3-METHYLPENTANE 4.1 18.9 2.4 12.5 2.7 46.8

2-METHYL-1-PENTENE 1.7 0.2 0.7 2.6

1-HEXENE 1.7 0.2 0.7 2.6

HEXANE 4.8 19.4 3.4 10.2 3.5 31.9

UNIDENTIFIED C6 0.3 1.0

TRANS-3-HEXENE

CIS-3-HEXENE 1.0 0.4 1.8

DI-ISOPROPYL ETHER

TRANS-2-HEXENE 1.0 0.3 2.2 Houston Fuel Atlanta Fuel Chicago Fuel

PAGE B-16HYDROCARBON SPECIATION DATA

SHED TEST

TOYOTA CAMRY

SHED results, mg

TC-4614-S TC-4614-M TC-4637-S TC-4637-M TC-4640-S TC-4640-M

COMPOUND 8/19/2002 8/20/2002 8/2/2002 8/9/2002 8/14/2002 8/15/2002 Houston Fuel Atlanta Fuel Chicago Fuel

3-METHYL-TRANS-2-PENTENE 0.7 2.3 0.7 1.1 4.6

2-METHYL-2-PENTENE 0.5 1.8 0.9 0.6 3.1

3-METHYLCYCLOPENTENE

CIS-2-HEXENE 0.5 1.4 0.6 1.9

ETBE

3-METHYL-CIS-2-PENTENE 0.8 2.4 0.4 0.9 0.5 3.2

2,2-DIMETHYLPENTANE, NOTE A 1.9 4.0 0.7 3.3 1.3 18.2

METHYLCYCLOPENTANE, NOTE A 1.8 3.9 0.7 3.3 1.3 17.8

2,4-DIMETHYLPENTANE 1.8 3.5 0.7 3.0 1.6 17.3

2,2,3-TRIMETHYLBUTANE 0.4 0.9

3,4-DIMETHYL-1-PENTENE 0.5

1-METHYLCYCLOPENTENE 2.5 0.8 2.4 1.1 9.7

BENZENE 7.0 8.2 4.2 12.7 6.6 29.8

3-METHYL-1-HEXENE

3,3-DIMETHYLPENTANE 0.5 0.3 0.3 1.0 0.7

CYCLOHEXANE 1.6 2.0 0.6 2.6 3.5 16.7

2-METHYLHEXANE

2,3-DIMETHYLPENTANE 6.8 10.8 2.8 8.8 5.1 34.6

1,1-DIMETHYLCYCLOPENTANE

TERT-AMYL METHYL ETHER

CYCLOHEXENE

3-METHYLHEXANE 3.9 7.2 1.9 5.8 3.4 18.3

CIS-1,3-DIMETHYLCYCLOPENTANE 0.7 1.1 0.7 4.0

3-ETHYLPENTANE 0.8 0.7 0.6 5.9

TRANS-1,2-DIMETHYLCYCLOPENTANE

TRANS-1,3-DIMETHYLCYCLOPENTANE 0.5 0.7 0.5 0.7 3.4

1-HEPTENE

2,2,4-TRIMETHYLPENTANE 4.4 8.5 2.2 8.9 3.7 28.2

2-METHYL-1-HEXENE 0.8

TRANS-3-HEPTENE

HEPTANE 4.3 5.4 2.7 6.7 4.2 16.6

CIS-3-HEPTENE

UNIDENTIFIED C7 1.5 0.9

2-METHYL-2-HEXENE

3-METHYL-TRANS-3-HEXENE

TRANS-2-HEPTENE 0.3 0.6 0.7

3-ETHYL-CIS-2-PENTENE

2,4,4-TRIMETHYL-1-PENTENE 0.5 0.8 0.4 0.7 1.2

2,3-DIMETHYL-2-PENTENE

CIS-2-HEPTENE 0.4 0.4

METHYLCYCLOHEXANE 2.3 2.2 0.9 2.5 1.9 9.6

CIS-1,2-DIMETHYLCYCLOPENTANE

2,2-DIMETHYLHEXANE

1,1,3-TRIMETHYLCYCLOPENTANE 0.3 0.3 1.4 0.8

2,4,4-TRIMETHYL-2-PENTENE

2,2,3-TRIMETHYLPENTANE 0.7 1.0 0.3 0.6 7.1

2,5-DIMETHYLHEXANE

ETHYLCYCLOPENTANE

2,4-DIMETHYLHEXANE 0.3 0.6 3.9

1-TRANS-2-CIS-4-TRIMETHYLCYCLOPENTANE 0.5 0.4 0.5

3,3-DIMETHYLHEXANE

1-TRANS-2-CIS-3-TRIMETHYLCYCLOPENTANE

PAGE B-17HYDROCARBON SPECIATION DATA

SHED TEST

TOYOTA CAMRY

SHED results, mg

TC-4614-S TC-4614-M TC-4637-S TC-4637-M TC-4640-S TC-4640-M

COMPOUND 8/19/2002 8/20/2002 8/2/2002 8/9/2002 8/14/2002 8/15/2002 Houston Fuel Atlanta Fuel Chicago Fuel

2,3,4-TRIMETHYLPENTANE 3.9 4.9 1.4 3.3 2.2 10.8

2,3,3-TRIMETHYLPENTANE 1.7 0.7 2.4 12.4

TOLUENE 28.7 18.2 17.2 38.9 29.7 51.7

2,3-DIMETHYLHEXANE 5.4 6.3

1,1,2-TRIMETHYLCYCLOPENTANE

2-METHYLHEPTANE

3,4-DIMETHYLHEXANE, NOTE B

4-METHYLHEPTANE 2.1 2.7 1.0 2.5 1.0 6.7

3-METHYLHEPTANE 2.5 2.8 1.1 2.0 1.7 6.7

1-CIS,2-TRANS,3-TRIMETHYLCYCLOPENTANE

CIS-1,3-DIMETHYLCYCLOHEXANE

TRANS-1,4-DIMETHYLCYCLOHEXANE

3-ETHYLHEXANE

2,2,5-TRIMETHYLHEXANE 1.3 1.3 0.4 0.9 1.0 4.2

TRANS-1-METHYL-3-ETHYLCYCLOPENTANE

CIS-1-METHYL-3-ETHYLCYCLOPENTANE 0.3 0.3 0.4

1,1-DIMETHYLCYCLOHEXANE

TRANS-1-METHYL-2-ETHYLCYCLOPENTANE

1-METHYL-1-ETHYL-CYCLOPENTANE

2,4,4-TRIMETHYLHEXANE

2,2,4-TRIMETHYLHEXANE

TRANS-1,2-DIMETHYLCYCLOHEXANE

1-OCTENE

TRANS-4-OCTENE

OCTANE 1.8 1.7 0.8 1.9 2.1 4.2

UNIDENTIFIED C8 0.4 0.3 1.6

TRANS-2-OCTENE

TRANS-1,3-DIMETHYLCYCLOHEXANE, NOTE C

CIS-2-OCTENE 0.9

ISOPROPYLCYCLOPENTANE

2,2-DIMETHYLHEPTANE

2,3,5-TRIMETHYLHEXANE 0.4

CIS-1-METHYL-2-ETHYLCYCLOPENTANE

2,4-DIMETHYLHEPTANE 1.7 0.4

4,4-DIMETHYLHEPTANE

CIS-1,2-DIMETHYLCYCLOHEXANE

ETHYLCYCLOHEXANE

2,6-DIMETHYLHEPTANE, NOTE D 0.6 0.7 0.3 1.1 1.0

1,1,3-TRIMETHYLCYCLOHEXANE

2,5-DIMETHYLHEPTANE, NOTE E 0.4 0.4 0.6 0.9

3,3-DIMETHYLHEPTANE

3,5-DIMETHYLHEPTANE, NOTE E

ETHYLBENZENE 6.0 5.7 3.6 6.7 6.3 8.0

2,3,4-TRIMETHYLHEXANE

2,3-DIMETHYLHEPTANE

m-& p-XYLENE 17.4 14.6 9.6 21.4 18.1 23.7

4-METHYLOCTANE

3,4-DIMETHYLHEPTANE

4-ETHYLHEPTANE

2-METHYLOCTANE 0.7 0.6 0.8

3-METHYLOCTANE 0.7 0.6 0.7

STYRENE

PAGE B-18HYDROCARBON SPECIATION DATA

SHED TEST

TOYOTA CAMRY

SHED results, mg

TC-4614-S TC-4614-M TC-4637-S TC-4637-M TC-4640-S TC-4640-M

COMPOUND 8/19/2002 8/20/2002 8/2/2002 8/9/2002 8/14/2002 8/15/2002 Houston Fuel Atlanta Fuel Chicago Fuel

o-XYLENE 7.0 5.7 3.1 8.3 6.2 8.5

1-NONENE

TRANS-3-NONENE 0.7

CIS-3-NONENE

NONANE 0.3 0.4

TRANS-2-NONENE

ISOPROPYLBENZENE (CUMENE) 0.4

2,2-DIMETHYLOCTANE

2,4-DIMETHYLOCTANE 0.5

n-PROPYLBENZENE 0.7 0.3

1-METHYL-3-ETHYLBENZENE 2.6

1-METHYL-4-ETHYLBENZENE

1,3,5-TRIMETHYLBENZENE 0.8

1-METHYL-2-ETHYLBENZENE 0.3 0.3 1.1 0.9

1,2,4-TRIMETHYLBENZENE

TERT-BUTYLBENZENE

1-DECENE

DECANE, NOTE F 0.3 1.6 1.0 0.8

ISOBUTYLBENZENE, NOTE F 0.3 1.5 0.9 0.7

1,3,-DIMETHYL-5-ETHYLBENZENE
METHYLPROPYLBENZENE (sec butylbenzene)

1-METHYL-3-ISOPROPYLBENZENE 2.6

1,2,3-TRIMETHYLBENZENE

1-METHYL-4-ISOPROPYLBENZENE

INDAN

1-METHYL-2-ISOPROPYLBENZENE 1.5

1,3-DIETHYLBENZENE

1,4-DIETHYLBENZENE

1-METHYL-3-N-PROPYLBENZENE

1-METHYL-4-N-PROPYLBENZENE, NOTE G

1,2 DIETHYLBENZENE

1-METHYL-2-N-PROPYLBENZENE 2.4 0.6

1,4-DIMETHYL-2-ETHYLBENZENE 0.3

1,3-DIMETHYL-4-ETHYLBENZENE

1,2-DIMETHYL-4-ETHYLBENZENE 0.6

1,3-DIMETHYL-2-ETHYLBENZENE

UNDECANE

1,2-DIMETHYL-3-ETHYLBENZENE

1,2,4,5-TETRAMETHYLBENZENE
2-METHYLBUTYLBENZENE (sec AMYLBENZENE)

3,4 DIMETHYLCUMENE

1,2,3,5-TETRAMETHYLBENZENE

TERT-1-BUT-2-METHYLBENZENE

1,2,3,4-TETRAMETHYLBENZENE

N-PENT-BENZENE 0.5

TERT-1-BUT-3,5-DIMETHYLBENZENE

TERT-1-BUTYL-4-ETHYLBENZENE 0.6

NAPHTHALENE

DODECANE

1,3,5-TRIETHYLBENZENE

1,2,4-TRIETHYLBENZENE

HEXYLBENZENE

PAGE B-19HYDROCARBON SPECIATION DATA

SHED TEST

TOYOTA CAMRY

SHED results, mg

TC-4614-S TC-4614-M TC-4637-S TC-4637-M TC-4640-S TC-4640-M

COMPOUND 8/19/2002 8/20/2002 8/2/2002 8/9/2002 8/14/2002 8/15/2002 Houston Fuel Atlanta Fuel Chicago Fuel

UNIDENTIFIED C9-C12+ 0.4 4.7 4.8 0.5

*C1 - C4 DATA NOT AVAILABLE DUE TO INSTRUMENT MALFUNCTION A - 2,2-Dimethylpentane and methylcyclopentane co-elute. GC peak area split equally between the two compounds.
B - 3-Methyl-3-ethyl-pentane co-elutes with reported compound. Not reported separately. C - Cis-1,4-Dimethylcyclohexane co-elutes with reported compound. Not reported separately.
D - Propylcyclopentane co-elutes with reported compound. Not reported separately. E - 2,5-Dimethylheptane and 3,5-dimethylheptane co-elute. GC peak area split equally between the two compounds. F - Decane and isobutylbenzene co-elute. GC peak area split equally between the two compounds. G - n-Butylbenzene co-elutes with reported compound. Not reported separately. H - Isobutyraldehyde and methyl ethyl ketone co-elute. LC peak area split equally between the two compounds.

PAGE B-20

# Appendix G

API Section 211(B) Tier-2 Exposure Database – Naming Convention

## API Section 211(B) Tier-2 Exposure Database

The data have been organized into four data files (API Da ta_Continuous.xls, API Data_SPME.xls, API Data_Time-integrat ed.xls and API Data_Reconstructed.xls) containing the continuous, SPM E, time-integrated and reco nstructed exposure data. All files include data fields describing the sample collection conditions (e.g.; microenvironment, fuel type, test mode) as well as data flags i ndicating problems with the analytical or sample coll ection methods. Tables explaini ng the meaning of each data

field are also included with each file. The fi les are supplied in Excel workbook format for convenience, but have been formatted to be compatible with common database software (the value -99 is used for missing data poi nts, and time is in hhmm text format)

The time-integrated data contains speciation results from canister, DNPH cartridge, and TENAX adsorbent tubes, plus time-averaged values o f pollutants and environmental parameters that were meas ured continuously during the batch sample collection periods. Within the time-integrated data file there are 4 sub-categories that are presented separately due to the differing numbe r of experimental variables for each type: 1) microenvironment exposure measurements from the three cities, 2) breath samples collected from subjects participating in 4 of the microenvironments, 3) residence with attached garage, and 4) trai ling vehicle exposure tests.

The SPME data set is assembled in essentially the same manner as the timeintegrated data, but contai ns only the BTEX hydrocarbon compounds and uses some different sample descriptors where necessary to identify which portion of each test the sample was collected. The same sample IDs are used to facilitate comparison of the two sampling methods.

The third data file contains 1-minute averages of the pollutants and environm ental parameters that were measured continuously during the microenvironment exposure tests in the 3 cities. Data were typically logged every 10 seconds during testing, but to reduce measurement noise, make the data set more manageable, and reduce the effect of minor timing discrepancies between instruments due to imperfect clock synchronization or differences in sample line residence time, the data was time averaged by minute. Each

data record in this file has both a time/date stamp and an identification code that relates it to the corresponding time-integrated sample. Data flags are given to identify any missing or invalid data for each minute. Due to the large size of this file, the various sample descriptors have not been incl uded but these can be derived from the identification code as described in the included key.

The fourth file contains 1-min reconstr ucted data for benzene, 1,3-butadiane and formaldehyde based on PID and NDIR CO continuous data, as described in Chapter 1 of this report. Both full tim e canister a nd DNPH-carbonyl samples and 5-min canister samples collected over a peak expos ure in selected MEs are included.

Table G-1 contains the key to the name of the samples collected during this study.Table G-1. Naming convention for the API dataExperimentPositionType1stLocation2ndSeason3rd+ 4th5thMode6th7th8thMEAtlantaAS-SummerW-winterME number(01, etc)M-mainP- 5 minB-breathUnderscoreReplicatenumberBreath: A-pre;B-peak, C-postMEChicagoCS-SummerW-winterME numberM-mainP- 5 minB-breathUnderscoreReplicatenumberBreath: A-pre;B-peak, C-postMEHoustonHS-SummerW-winterME numberM-mainP- 5 minB-breathUnderscoreReplicatenumberBreath: A-pre;B-peak, Cpost; NOxdenuder: DtrailingVehicleVS-SummerW-winterFuel (a,c,h) +vehicle (ttruck, s-sedan)MalFunction(F)Normal (N)UnderscoreHigh (H), Low(L) vent, orcoMbined (m)Background –A; Main-B;Idle-CResidencew/attachedgarageRS-SummerW-winterFuel (a,c,h) +vehicle (ttruck, s-sedan)MalFunction(F)Normal (N)UnderscoreKichen (K) orGarage(G)locationBackground:A; Main - BFor example: AS02M_1 means Atlanta, summer, ME#2, first replicate. HW11B_3B means Houston, winter, ME#11, breath sample,peakVWasN_HC means trailing vehicle,winter, Atlanta fuel, sedan, normal mode, high vent, idle. RSctF_KA means garage, summer,Chicago fuel, truck, malfunction, kitchen, background

# Appendix H

Measurement Data Quality Objectives

# Appendix H. Data Quality

Table of Contents

1.1 Measurement Data Quality Objectiv es ..................................................................... 2

1.2 Quality Control and Assurance

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

1.2.1 External Performance Audit for the API Section 211(b) Study

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

1.2.2 Laboratory Comparison and Ex ternal Performance Audits

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

1.2.3 Time-Integrated Methods

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

1.2.4 Semi -Continuous Methods ................................................................................ 7

1.2.5 Continuous Methods ......................................................................................... 8

1

### 2 1.1 Measurement Data Quality Objectives

Data quality objectives, including m easures of accuracy, precision, detection limit, time resolution, and known interferences, are su mmarized in Table H-1. For the two CO

instruments and the P ID, we use manufacturer ’s specifications for most data quality
parameters.

There are also some limitations that are not covered by the tabular summary. For the T-15 CO (electrochem ical detector), we find that although the data system can collect data every 10 sec, the response of this in strument responds to rapid cha nges in concentration on a longer time frame. This may occur since CO must di ffuse across a membrane to be measured. The finite diffusion time means that rapid spikes in concentration may not achieve steady-state

values across the membrane and are thus not fully measured. Comparisons among CO methods are good over integration times greater than one minute. There were interferences from batteries (H 2 

### emissions) that were used to power in struments inside the van that showed up as a rising signal from the T-15 CO unit wh en the vehicle windows were closed. Under high-ventilation conditions in the vehicle or outdoors, no su ch interferences were observed. At high humidity near saturatio n we did observe high T-15 CO re adings that we suspect are due to the humidity.

The PID does not have an accuracy measure since this instrum ent reports the total ion signal,

which will differ with the dist ribution of compounds ionizable at 10.6 eV. However, since we find a good correlation of PID signal with BTEX as measured in the canisters, we feel this measurement provides a reasonable surrogate time series signal for these compounds. This instrument does respond to very high humid ity where there is condensation of water on the lamp and other areas of the electrometer that are exposed to air. In addition, we observed

some summer instances where th e PID readings increased inside the vehicle cabin under low ventilation conditions with no change in any ot her measurement. This may be a response to off-gassing of plasticizers in cabin materials that are mostly phthalate esters.InstrumentAccuracyPrecisionDet LimTime Res.ArtifactsSpecificationsSourceCO-T15+/- 1 ppm+/-0.05 ppm0.1 ppm10 secH2, very high humidityElectrochemical DetectorManufacturer literatureCO-NDIR0.50%+/-0.02 ppm0.04 ppm1 secNoneNDIRManufacturer literaturePIDNA10%1 ppb1 secPlasticizers, very highhumidity10.6 eV lamp PIDManufacturer literatureHCHO (a)<15%<5%1 ppb1 minNoneHantzch rxn/fluorescenceDRI Use/intercomparisonsMS-200<8%<5%1-3 ppbv1 minNoneMass spectrometerDRI Use/intercomparisonsSPME3-50%2-15%0.2 ppbvvariableNoneGC/FID & PIDDRI Use/intercomparisonsCanister<5%<3%0.05 ppbCvariableNoneGC/FIDDRI Use/intercomparisonsDNPH<5%<3%0.1 ppbvvariableNoneHPLC/Photodiode arrayDRI Use/intercomparisons(a) HCHO performance parameters based on Battelle instrument performance in the Reno pilot study.3Table H-1. Measurement data quality

### 1.2 Quality Control and Assurance

1.2.1 External Performance Audit for the API Section 211(b) Study

A site vis it to the mobile laboratory and all twelve mi croenvironment (ME ) sampling sites in Atlanta, GA was conducted duri ng February 23-27, 2004, by the independent auditor, Christine Sexsmith, Sexsmith Consu lting Services, LLC. The auditor was on site at the mobile lab or in the sampling van and witnessed measurement in at least one of each of the 12 microenvironments sampled. A technical procedure inspection was conducted to verify that DRI personnel were following the approved exposure protocol and that no special circumstances occurred th at could affect the out come of the study. This audit was followed up by the DRI Organi c Analytical Laboratory audit in April 2005. The reports from these two audits are available from the API upon request.

1.2.2 Laboratory Comparison and External Performance Audits

The DRI Organic Analytical L aboratory ( OAL) participated in the Internat ional Hydrocarbon Intercomparison Experime nt, organized by National Center for Atmospheric Research (NCAR). The results of Tasks I, II, and III of this laboratory intercomparison have been published (Apel et al., 1994; 1999). Task I involved analysis of a two-component hydrocarbon mixture of known composition and unknown concentration prepared by NIST. The DRI results were within the acceptable range of ± 5% of the nominal values provided by NIST. In Task II the participating laboratories were asked to identify and quantify 16 component s present, in the ppb range, in a mixture prepared by NIST. The agreement between the DRI values and the NCAR values, as well as with nominal values provided by NIST, were within acceptable ranges ( ± 15%). Task III was more complex, involving th e analysis of 60 commonly observed hydrocarbons at low ppbv concentrations in a mixture prepared and analyzed by ScottMarrin, Inc., NCAR and U.S. EPA laboratory. The next tasks, IV and V, which were carried out in 1996 -1997, involved the analys is of ambient air samples in the ppbv and pptv concentration ranges, respectively. Th e DRI has successfully completed these tasks with agreement between the DRI values and the NCAR values for Tasks III – V within the acceptable range ( ± 10%).

In the summers of 1995 and 1996 the DRI OA L participated in the NARSTO-Northeast hydrocarbon intercomparison study, involving the analysis of two ambient air sam ples by participating laboratories. Participants incl uded Biospheric Research Corporation (BRC), State University of New York at Albany (S UNYA), EPA Region I, DRI, and eight of the

PAMS network labs in the northeastern U. S. The DRI laboratory performed best in comparison with all other participants (Fujit a et al., 1997). In the summer of 1997, the DRI OAL participated in the SCOS97-NARSTO performance audit and laboratory comparisons involving speciated non- methane hydrocarbons (NMHC), carbonyl compounds, halogenated compounds and biogen ic hydrocarbons (Fujita et al., 2003). Again, the agreement between DRI values and nominal values were within the acceptable range ( ± 10%).

4

### During the last six years, the DRI laboratory participated in non-methane hydrocarbon laboratory performance audits, organized by the Quality Assurance Section, Monitoring and Laboratory Division, CARB. The last intercompariso n studies, organized in 1999- 2002, involved the analysis of ambient air samp les by California district laboratories and the DRI OAL laboratory. The results of these intercomparison studies were always very

favorable for OAL.

1.2.3 Time-Integrated Methods

Sa mple Custody. For our quality assurance plan, a sample is considered in custody when it is received by the DRI Division of Atmosphe ric Sciences (DAS) receiving department from an official package courier. At this time it is logged into the general receiving department's logbook and the Organic Analytical Laboratory is notified of the package's arrival. A representative of the laboratory si gns for the package and returns with it to the laboratory where he opens it. The sample s are logged into the Organic Analytical Laboratory’s receiving logbook, th e chain-of-custody form is updated, and the samples are stored appropriately for the sample t ype. At this time any unusual situations (damaged shipping container, evidence of damage and/or tampering, etc.) are brought to the attention of the laboratory manager. If necessary, a re view will be initiated to determine if the damage compromised the integrity and/or quality of the sample.

Samples are stored in the Organic Analyt ical Laboratory, inside the DRI Northern Nevada Science Center (2215 Raggio Parkwa y, Reno, NV). The room is locked when not in use and the building has limited access (i.e., it is locked from 1730 to 0730 weekdays and all weekends to ensure access only to authorized personnel).

When a sample is analyzed, its identificati on number (sample number) is recorded both in the written log book for each inst rume nt and in the Laboratory Information Management System (LIMS) file created for that analys is. The sample number serves as a tracking number, as does the LIMS file its elf. Canisters will not be cleaned until each sample has passed initial validation.

Sampling Systems. The sampling equipment is leak-t ested and the electronic flow controllers are calibrated prior to the delivery to the field. The flow controllers are recalibrated after the program to determine if any significant change in the calibration has occurred. In addition, the flow controllers are checked at least weekly in the field with a Galibrator (an instrumented soap bubble flow meter). The average of the pre- and postsampling flow rates is used to determine the sample volume.

Sampling systems that have internal surfaces upstream of the collection m edia (e.g., canister sampler), must be cleaned and certi fied for cleanliness prior to sampling.

Sampling Media Prepara tion and Certific ation. Multibed adsorbent cartridges consisting of Tenax TA, Carbotrap (or Carboxen) and Carbosieve are used for ethanol sample collection. Prior to use, the Tenax-TA so lid adsorbent is cleaned by Soxhlet extraction with hexane/acetone mixture (4/1 v/v) overni ght, and dried in a vacuum oven at ~ 80 °C. The dry Tenax is packed into Pyrex glass t ubes together with Car botrap and Carbosieve and thermally conditioned for f our hours in an oven at 300 ° C under nitrogen purge. Approximately 10% of the precleaned cartridges are tested by GC/FID prior to sampling.

5

### After cleaning, the cartridges are sealed using clean Swagelok caps (brass) with graphite/Vespel ferrules, placed in metal contai ners with activated charcoal, and kept in a clean environment at room temperature until use.

The DNPH impregnated SiO2 cartridges are purch ased from Waters, Inc., in batches of 25. One cartridge from each batch is te sted for background contamination by the High Performance Liquid Chromatography (HPLC) method prior to sampling.

The canisters are cleaned by repeated evacuatio n and pressurization w ith humidified zero air, as described in th e EPA document "Technical Assistance Document for Sampling and Analysis of Ozone Precursors" (Oct ober 1991, EPA/600-8-91/215 ). Six sequential cycles of evacuation to ~ 0.5 torr absolute pressure and pr essurization with ultra-highpurity (UHP) humid zero air to ~ 20 psig are used. The DRI procedure differs from the

EPA method in that canisters are heated to 140 °C during the vacuum cycle in the DRI procedure and more vacuum-pressure cycles ar e used. According to our experience and that of others (Rasmussen, 1992), heating is essential to achieve the desired canister cleanliness. Also, the canisters are maintained longer under vacuum, about one hour in the DRI method, as opposed to half of an hour in the EPA method.

At the end of the cleaning procedure, one canister out of twelve in a lot is filled with

humidified UHP zero air and an alyzed by the gas chro matograph/flame ionization detection (GC/FID) method. The canisters are considered clean if the total non-methane organic compound (NMOC) concentration is le ss than 10 ppbC, and the concentration of any individual targeted compound is less than 0.2 ppbv. Canister cleaning and

certification are describe d in the DRI SOP1-701.4 .

Analytical Systems. Prior to analysis, all analytical systems (i.e., GC/ECD/FID, HPLC, GC/MS, and GC/IRD/MSD) are checked for clea nliness and are certified clean (less than 0.1 ppbv of targeted compound). Quality contro l in the laboratory includes instrument calibration for each batch of samples analyzed, re plicates of standards, and reanalysis of approximately 10% of the samples for es timation of analytic al precision, which historically has been be tter than 6%. In past programs, field blanks have come in at 0.5-1 ppb levels, based on the air volume of the sa mples. Coefficients of variation (CV)

calculated from observed differences be tween duplicate samples were less than 10%. The data quality in this program was within DRI’s historical range.

Standards and Materials. Each primary reference standard is traceable to an NIST Standard Reference Material (SRM). For canister hydrocarbon speci ation, we use NIST SRM 1805, which consists of 254 ppb of benzene in nitrogen.

Gas cylinders of helium, nitrogen, hydrogen, an d ultra zero air (all UHP grade) — from

the best so urces available — are used fo r the GC/FID and GC/MSD. The current inventory of reference samples at DRI's Organic Analytical Laborat ory consists of over 250 single- and multi-component reference samples, and includes compounds of interest in this project.

Calibrations. The GC/FID, HPLC, and GC/MS sy stems are calibrated initially by multipoint calibration (i.e., three levels plus humid zero air), and regularly checked by a one-point calibration, using the appropriate NIST SRM or other standard. A day-to-day

6

### reproducibility of ±10% is acceptable for either standard. Control charts are used for assessing analytical system performance.

Samples that fall outside the calibration range are diluted until bracketed by the

calibration curve. Instrum ent responses to calibration standards for each parameter are analyzed using a least squares linear re gression. The calibrati on must generate a correlation co-efficient (R 2 

### ) of 0.99 to be acceptable.

During the course of analysis, calibration standa rds are routinely analyzed to ensu re that the instrument response has not changed. The criterion of an instrument response within 10% of the expected response is used by the analyst to determine whether the instrument

must be recalibrated.

Relative Accuracy and Precisi on of Sampling and Analysis. Accuracy involves the

closeness of a measurement to a reference va lue and reflects elemen ts of both bias and precision. Percent relative accuracy is calculated:

% Relative Accuracy = X - Y x 100

X

where:

Y = concentration of the targeted compound, as determined by the analytical instrument,

and

X = concentration of the targeted com pound in the NIST (or traceable) standard.

If the percent relative accuracy does n ot fa ll below 20%, the instru me nt is recalibrated.

Precision is a measure of the repeatability of the results. The overall precision of sampling and analysis is determined by the analysis of collocated samples. These precision tests depend upon availa ble resources. Historically, we have performed collocated sampling of all samplers, of each t ype, that were deployed in the measurement program to establish equivalency and overall measurement precision prior to actual field sampling. Overall precision was within 20%.

Removal of Ozone and NOx Interferences. Since the carbonyl compound ambient measurement results are subject to various artif acts due to interaction with ozone, we use either a honeycomb O 3 

### denuder coated with sodium car bonate/sodium nitrite/glycerol mixture (method developed by Dr. Koutrakis from the Harvard School of Public Health), or a copper tube O 3 

### denuder coated with KI, as r ecommended by EPA Method TO-11a.

Since ambient NO 2 

### might react with 1,3 butadiene, we use a honeycomb NO 2 

### denuder coated with triethanolamine (a met hod also developed by Dr. Koutrakis).

1.2.4 Semi-Continuous Methods

For SPME fibers, blanks and calibration ch ecks were performed daily in order to

determ ine the performance of the instrument and quality of the data. Fibers were kept in the injector port throughout the sample run in order to guarantee that the entire sample had been desorbed and to aid in conditioning of the fiber. In addition, fibers were

cleaned in a fiber conditioner at 300 ° C for at least one hour. The fiber conditioner

7

### consisted of a 304 SS container with 5 ports and a Watlow heater/tem perature controller capable of maintaining te mperatures in the 200-300 ° C range. A helium flow was maintained during fiber conditioning. One fiber per batch of 5 was checked for

cleanliness afte r conditioning.

Multi-level calibrations were done initially and throughoutthe summer field study. Liquid calibration was done by injecting 1 μ l of a liquid standard prepared in pentane with benzene, toluene, ethylbenzene, and xyl enes (BETX) at different concentrations (1, 5, 10, 20, 40, 50, and 100 ng/ μ l). Gas calibration was perf ormed with certificated

standards at different concentrations (20, 80, 100, 200, a nd 500 ppbv for each compound). Gas standards were stored in caniste rs and transferred to 1L Tedlar bags for static exposures of SPME fibers. Gas calib rations were performe d for different fiber exposure times.

SPME 75 μ m Carboxen-PDMS fibers were used w ith portable or manual samp lers. When manual samplers were used, the tip of the ne edle was closed with a septum or Teflon tape. Fibers were kept after samp ling in sealed Mylar bags inside a cooler with dry ice. Storage stability tests showed that samples were preserved without any loss of analyte up to 5 hours (and reasonably preserved without subs tantial losses for as long as three days) when stored at dry ice temperature. In Atlanta, SPME samples were analyzed, on average, 10 hours after sampling, with a mi nimum of 1 hour and a maximum of 26 hours between sampling and analysis; 54% of the sa mples were analyzed before 10 hours of storage at dry ice temperature).

Detection limits for the BTEX com pounds were benzene 0.2 ppbv, toluene 0.3 ppbv, ethylbenzene 0.2 ppbv, m- p-xylene 0.2 ppbv, and o-xylene 0.2 ppbv. Precision was

evaluated in the laboratory by comparing repli cates and standards reproducibility. Two sets of replicates were placed side by side for 10 minutes inside solvent cabinets. Also, three replicates of 4 different standard c oncentrations were incl uded in the analysis. Replicates ranged from 2 to 15% error for a ll species. Accuracy was determined by daily calibration checks that varied within a rang e of 3-30% for benzene. When the relative accuracy did not fall within the 0-30% range for benzene, the GC was recalibrated.

The agreement between canis ter and SPME methods during the Atlanta field study wa s within 3-50%. For comparison, Li et al ., 2001, shows an agreement between SPME and a charcoal sampling method within a factor of two (100%), with a fiber repeatability of
20-30%, for 75 μ m Carboxen/PDMS.

1.2.5 Continuous Methods

The CO instruments were calibrated by standards purch ased from Scott Specialty and zero points were established by zero air purchas ed from Air Gas. Since both the T-15 and NDIR instruments have only zero and span controls, we used a span gas close to our expected concentrations, in this case 10 ppmv. For the T-15 CO instru ment, a cap is used

to flood the sensor with either zero or span gas. The cap is kept in place until a stable reading is obtained. For the NDIR, the gas was introduced through th e sample inlet line.

8

### Instruments were checked weekly and reca librated as needed. In general the CO instruments were very stable. The PID was calibrated with isobutene as a span gas as recommended by the manufacturer.

The MS-200 is calibrated by a standard containing pe ntane, isopentane, benzene, toluene, and o-xylene. This standard is mixed at DRI and tested against NIST traceable standards before being used in the field. Although the MS-200 is very stable once calibrated and essentially needs only zero checks before each run with the zero air cylinder carried with the instrument, calibration checks are made every few days to confirm instrument calibration. DRI purchased an Alpha Omega continuous HCHO instrument, the only commercially available instrument of its t ype, for use in the Atlanta field study. The instrument is, in theory, identical to the Battelle instrument that performed well in our Reno pilot study in February 2002. It uses the same reagents, the same reaction, and the same fluorescence basis for detection. However, there are engineering differences in the air/fluid interface, the pumping system, the mi xing of the reagents, the flow through the reactor, and the detectors. Although we have made a number changes to the instrument, it did not performed well in this study.

Precision evaluation of porta ble PID instrum ents. A series of tests were performed to evaluate the precision of the estimated VOC concentrations measured by the ppbRAE portable PID instruments. Although it is known that the concentrations recorded by these instruments vary with changes in the co mposition of the ambient VOC, making the accuracy of the instruments hard to quantif y, the precision can be evaluated by comparing the concentrations measured by two identical instruments sampling from the same source. This measure of precision is important if simultaneous measurements of VOC

concentration in two locati ons are to be compared.

In each test, both instruments were connected to the same in let using a stainless steel ‘T’ and tubing. After synchronizing th e internal clocks, data lo gging was started and a VOC source was introduced at varyi ng concentrations up to 10 ppm for a period of 20 to 45 minutes. The resulting 1-minute average co ncentrations from the two units were compared by linear regression to determine the level of correlation a nd bias. The test was repeated on 4 separate days over a 10-day pe riod. Zero checks and calibrations with 10 ppm isobutylene were made prior to the fi rst test and between the second and third.

In all tests, the correlation was high (R 2 

### = 0.97 or better) with a ze ro intercept. Slopes ranged from 0.79 to 1.45, indicating no consiste nt comparative bias. Since the average

concentration in most microenvironments is typically less than 100 ppb, we also evaluated the precision in this range. In two tests following the calibrations, the correlation was good (R 2 

### = 0.98)with the slope varying from 0.75 to 1.36. For two other tests, correlations were less (R 2 

### = 0.45 and 0.66) with slopes of 0.73 and 0.55. As earlier, the intercepts were zero. Overall, the test results suggest that instrument sensitivity varies, even with frequent calibration. Averag ed ambient data may have a precision of

about ± 35% or higher when comparing small numb ers of measurements or when at nearbackground concentrations.

9

### References:

Apel, E.C., J.G. Calvert and F.C. Fehsenfe ld (1994). “The Nonmethane Hydrocarbon Intercomparison Experim ent ( NOMHICE): Tasks 1 and 2.” J. Geophys. Res ., 99: 16,651-16,664.

Apel, E.C., J.G. Calvert, T.M. Gilpin, F.C. Fehsenfeld, D.D. Parrish, W. A. Lonneman (1999). The Nonmethane Hydrocar bon Intercomparison Experiment (NOMHICE): Task 3. Journal of Geophysical Research , 104: 20,069-26,086

Fujita, E., Z. Lu, G. Harshfield, and B. Zielinska (1997). NARSTO-Northeast: Hydrocarbon and Carbonyl Measurement Audits for the 1995 Field Study. Final Report prepared f or the Electric Power Research Institute, Palo Alto, CA, July

1997

Fujita, E., G. Harshfield, L. Sheetz (2003 ). Performance Audits and Laboratory Comparisons for SCOS97-NARSTO Measur ements of Speciated Volatile Organic Compounds. Atmos. Environ. 37, Supplement No. 2, S135-S147.

Li, K.; A. Santilli, M.; Goldthorp, S.; Whiticar , P.; and Lambert, M. F.; Solvent vapour monitoring in work space by solid phase mi croextraction. J. Hazard. Mater. 2001, 83, 83-91.

10

# Appendix I

Houston Test House Floor Plan Schematic

### Two-Car Garage Pantry Kitchen Breakfast Room

Family Room Dining

Room Living

Room

Stairs

Foyer

Study Powder Master
Suite