## 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

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 FIGURES ....................................................................................................................... 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 same vehicles and fuels as for trailing vehicle experiment are used. .................................................................................... 3-9

Table 3-6. Microenv ironment Listing. ....................................................................................... 3-10

Table 3-7. The Number of Samples for Each Microenvironment 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 Electrochemical Cell Re sponse with Temperature. ................... 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 high-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 exhaust 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

measurements 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 exhaust 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 Protocol 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 conduct exposure 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 the 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 ference measurements 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. However, where continuous mon 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) NDIR 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) instrument 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 Measurements

During 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 showed 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 scripted 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 to 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 les. 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 Analysis in Breath Samples

The analysis of VOC in breath samples will be conducted as described by Pleil and Lindstrom (1995, 2002) Prior to the commencement 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 Protocol

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 calibration and operational procedures.

Calibration Procedures:

1. Start instrument and establish zero.

2. Apply span gas and allow 2 minutes to stabilize response.

3. Collect at least 5 spectra

4. Using calibration section in software, confirm calibration response or enter new calibration values as
needed.

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 are ready to sample :

1. Inlet Valve Down position (confirm that vacuum is ok and heat is still ok)

2. Apply zero air and allow it to flow for at least 1 minute.

3. Collect 5 spectra of background air to assess variability.

4. Begin sampling

If possible, during a run perform a zero check as follows: Apply zero air for 15 to 30 seconds, allowi ng the instrument to collect one spectrum. After a sampling run, perform a zero check as follows: Apply zero air 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 Instruments

Two CO monitoring instruments will be used for the field study: 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 provided 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 propriate CO concentration for anticipated range and verify flow rate 6. Let instruments stabilize, record current re ading, 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 be checked 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 instruments 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 source 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 Continuous ppbRAE Photoionization Detector (PID)

A RAE Systems Model PGM-7240 (ppbRAE) portable PID monitor is used to continuously monitor ambient VOC levels 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 Continuous Formaldehyde Monitor

The continuous monitor for gaseous formaldehyde was purchased from Alpha-Omega Power Technologies. This instrument 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 rument 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) quartz 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 instrument 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 injection 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 of 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 data. 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) fibers 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-Integrated Air Sample Collection and Analysis

Time-integrated monitoring methods are used primarily for quantification of the responses of continuous surrogate instruments. 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 supply 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.
These controllers 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 tions 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 are executed 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 desorptioncryogenic 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 Procurement of Test Fuels from Houston, Chicago and Atlanta

With API and DRI guidance, SwRI will procure six test fuels (a summer 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 Tailpipe and Evaporat ive Emissions of Test Vehicles

SwRI will procure two test vehicles and determine evapor ative 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 garage exposure 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; nonmethane 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 in 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 one-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 conducted 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 Driving 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 operation 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 vehicle 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) inside 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: Toyota Camry

and Pick-up truck,

in normal and

malfunction

mode.

Fuels: baseline, MTBE, ethanol

Y 1 1

3.1.4 Relationship Between Evaporative Emission Rates and Exposure in a Residence With an Attached Garage

The two test vehicles (with and without malfunctions) will be used 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 over 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 min during 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 Microenvironmental Exposure Measurements in Atlanta, Chicago, and Houston

One of the overall goals of the project is to sample hi gh-end microenvironments (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 other 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 sampling. 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 Development

Scripted activities will be used during the exposure measur ements. This 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 time spent performing a specified 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 ements from nearby 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-cabin Exposures in Urban Microenvironments

The trailing vehicle from the controlled exposure tests in San Antonio 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 urban 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 mple will be 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 nvironment 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 measurement will be used as the biomarker of choi ce. Since we were not able to distinguish backgroundbenzene concentrations 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 Microenvironments

General selection criteria for the 13 high-end MEs are listed below. 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 construction or breakdowns/accidents

• Downwind direction from traffic density centroid

• Trailing high emitting vehicles encountered

Protocol : 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 contiguous length & height of high-rise buildings

• Narrowest canyon width

• Highest traffic density

• Mid-block sampling most shielded from air dispersion

Protocol : 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 refueling 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

• Protocol : 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

Protocol : 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 apron (vehicle cabin)

• Rush hour sampling

• General location of idling traffic queue (e.g., at road toll, parking garage entrance/exit, emissions testing 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

Protocol : 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. Tunnel/Covered Roadway (vehicle cabin)

• Rush hour sampling

3-14• Stop-n-go traffic flow

• Highest traffic density

• Lack of mechanical ventilation, if available

• Smallest enclosed volume

Protocol : 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 refueling 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

• Protocol : 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 technician, 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

Protocol : 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

• Rush hour sampling on roadway parallel to wind direction

• High traffic density route

• Located on traffic island/median strip

3-15• Downwind direction near high density traffic intersection

• In urban canyon

Protocol : 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

Protocol : 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. Outdoor Underground Parking Garage

• Rush hour sampling

• High capacity & usage

• Near internal entrance/exit lanes

• Lowest level with high capacity usage

• Lack of mechanical ventilation, or away from fans & vents if present

Protocol : 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

Protocol : 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 contiguous length & height of high-rise buildings

• Narrowest canyon widths

• Highest traffic density

Protocol : 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 Meteorology

For portions of the sampling periods involving stationary activities, local meteorological variables such as wind speed and 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 measurements 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

Compile 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 procedures. 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 timeintegrated samples. Determine systematic biases.

• Derive summary statistics (mean, maximum, standard devi ation) 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, formaldehyde, acetaldehyde to TNMHC and significant differences in the ratios among
microenvironments.

• Prepare scatter plots of mean CO and PID with BTEX from 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 methods 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 time-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 measurement of peak exposures.

Determine quantitative relationships between tailpipe emissi on rates and 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 average 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 specific 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 of varying speed, spacing between test and trailing vehicle, and degree of ventilation.

• Determine variations of the in-cabin exposures within the test and 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 exposures in a residence with an attached garage.

• Subtract the time-integrated background values of BTEX, 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 determine 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 orative and exhaust emission in microenvironments.

• Process GPS data and develop a log of exposure meas urements 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 tinuous CO, PID, MS200, and HCHO measurements in each microenvironment by city and season.

• Reconstruct the time-series of individual air toxics us ing 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 the extremes in exposure levels for each microenvironment using the reconstructed 1-minute

data.

• Determine the effect of varying cabin ventilation conditi ons on exposure 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 asured 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

MTBE to benzene as described in the RFP.

• Determine the levels of the designated species in the urine and breath of t echnicians carrying out the scripted behaviors and determine significant differences due to varying fuel formulation.

3.5 Reporting

This task will require completion of the following:

• Report after completion of the 1 st Reno Pilot Study (complete)

• Detailed preliminary protocol (peer-reviewed by API and submitted for EPA approval prior to initiating the main exposure measurements) (complete)

• Interim Data Report after 2002 summer 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 interpretations 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 report to EPA, & archive results

4-1

### 5. REFERENCES

Cardin, D. and T. Robinson (2002). Formaldehyde and VO Cs in air-quality determinations by GC-MS. American Laboratory. 32-34

Chai, M. and J. Pawliszyn (1995) Analysis of Environm ental Air Samples 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 from 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- Dinitrophenylhydrazones 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 of 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 of 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 Microenvironmental 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 Ambient 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) Following 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 Tertiary 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 Microextraction 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 volatile organic biomarkers. Biomarkers, 7, 189-208

Rasmussen, R.A. (1992). “The ABCs of stainless steel canister clean-up and 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 Emissions 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 the 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 ement program 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 emission 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, surveyed 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-second average 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 Barker-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 the tour 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 and 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 Channel 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 road through the airport 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 spikes in 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 Park 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 Houston 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)

Make one to two 20-minute roundtrips (depending on traffic conditions) on a segment of freeway during peak weekday morning 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 instrument, 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 Ashford 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 US290 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 greatest volume of traffic in the downtown Houston occurs during the morning and afternoon commute periods 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 collect 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 appropriate refueling location(s) and sampling times based 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, park 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)

Drive 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 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, ppbRAE, 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 tunnel is controlled. 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 collect one 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 appropriate refueling location(s) and sampling times based 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 cations 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)

Conduct sidewalk sampling by cart in downtown Houston along the city block bordered by Polk, Louisiana, Clay 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 of 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)

Sample the ambient air at a bus stop by cart in do wntown 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 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 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 Greenway 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 200, Langan 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 minutes. 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 one 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 sampling 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 urement 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 project officer, surveyed 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 the 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/special/roadwords.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/st0300/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)

Drive for 40 minutes in congested freeway traffic during weekday morning rush hour from 0700 to 0800, local time 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 canister 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)

Make multiple trips during a 40-minute period along a surface-street loop 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 collect 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)

Sample 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, park 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 collect 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 vehicle: toll plaza (ME5)

Sample during the morning commute period for 40 minutes at the toll plaza between exit 2 and 3 on the GA 400

toll road.

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 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 Atlanta. 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)

Sample at the Racetrak or Quicktrip (QT) service stat ion located 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.

Park the van downwind from the centroid of the pump lo cations 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, Andrew 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 DNPH 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)

Combined with ME8.

10. Outdoor: stadium parking lot (ME10)

Sample 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, Langan 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)

Sample 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 200, Langan 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 measurement on the northbound side of the to ll plaza. Access to the toll plaza is from the northbound 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 200, Langan 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 exist, conduc 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 sampling 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 during 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 croenvironments 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 microenvironments. 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 in 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 Chicago. 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 instrument, 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 Street, 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 collect 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, park 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 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 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 analyzer 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 collect 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 natural ventilation. 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 ventilation 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 cations 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 Avenue, 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 Comiskey 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 the van 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 emissions). 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 200, Langan 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 inspection 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 sampling 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 Schedule 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 quality assurance 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 used in this study 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 instrument. Generally 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 generally 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 include calibration, replicate, collocated and blind QA samples.

e. Recovery tests for selected analytes. For DNPH analyses inte rnal standards are also added. Recovery for NMHC samples in internally determined by calibration standards.

f. Determine and report minimum tra pping efficiency. For so lid adsorbent samples, the backup traps are used for approximately 5 % of samples to conf irm that no quantifiable levels of compounds are getting through the first trap.

Every measurement consists of four attributes: a value, 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 the 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: quality 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, measurement method 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 and replacement 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 stitute – 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 (Ms. 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. Supervises 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 (Dr. John 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 (Mr. 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. Michael 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 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 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 Parkway, 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 maintained. 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 the laboratory. 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 tained 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 time 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 principles 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. Specifications 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 transfer 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 be 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 dried in 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 systems (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 Standard Reference 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/MS 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 initially by 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 responses 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 routinely analyzed to en sure that the instrument 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 measurement 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 compound in the NIST standard.

If the relative accuracy does not fall within the ± 10% range, the instrument 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 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 iding 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 dered by 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 preventative 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 the 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, including 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 correction 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 combin 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 available. 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 rticipated 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 ated 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- NARSTO 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 Angeles, CA, University Microfil ms International, Ann Arbor, MI.



### E-9