APPENDIX A 

Exposure Protocol and Study Plan for the Section 211(B) Tier 2 High End Exposure 

Screening Study of Baseline and Oxygenated Gasoline 

Prepared for 

AMERICAN PETROLEUM INSTITUTE 

1220 L Street 

Washington, DC 20005-4070 

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 Residential 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 Atlanta, 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 Samples 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 for trailing vehicle tests............................................................................... 3-8 

Table 3-5.Protocol for attached garage experiments. The same vehicles and fuels as for 

trailing vehicle experiment are used..................................................................................... 3-9 

Table 3-6. Microenvironment 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 Response with Temperature.................... 2-10 

Figure 3-1: Overall Structure of 211(b) Monitoring Requirements............................................ 3-3 

Figure 3-2. Monitoring Requirements 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 requirements for a test program in accordance 

with the Alternative Tier 2 provisions of the fuels and fuel additives (F/FA) health effects testing regulations, 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 team consisting of the Desert Research Institute (DRI), 

Southwest Research Institute (SwRI), Lovelace Respiratory Research 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 potential high-end inhalation exposure microenvironments dominated 

by evaporative and exhaust emissions of baseline- and oxygenated-gasoline. The specific 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 levels 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 exposure 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 study will permit sensitivity analyses to determine the range 

of these exposures, especially during heavy traffic, in residential and public parking garages and during refueling. 

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 instruments 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. The supplementary method data are not 

required to conform to the CAA requirements and therefore should not to be used in regulatory decision making. 

1. The reference methods include pumped whole-air canister samplers used for CO, CO2, benzene, toluene, 

ethylbenzene, xylenes (BTEX), MTBE and 1,3 butadiene (BD), acidified 2,4-diphenylhydrazine (DNPH) 

cartridges for formaldehyde (HCHO) & acetaldehyde (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, using 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 incorporated 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 photo-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 concentration 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 reagent to produce a formaldehyde-specific 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 injected into a GC with PID/FID detection optimized for 

BTEX quantification. 

The surrogate approach is used to generate short-term time-series values for the target 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 should provide comparable time-series measures of shortterm values, as shown in Figure 2-1. In engine-off microenvironments, evaporative species should dominate and the 

PID surrogate should provide the time-series measure since CO isn’t emitted, as shown in Figure 2-2. 

2-1
Continuous Measurements

0.0

5.0

10.0

15.0

20.0

25.0

17:0017:1017:2017:3017:4017:50

CO (ppm) 

0

200

400

600

800

1000

PID

API CO DRI T15 CO PID (ppb)

Reconstructed BTEX

0

50

100

150

200

250

17:0017:1017:2017:3017:4017:50

BTEX (ppbv)

BTEX (PID) BTEX (T-15 CO) BTEX (API CO)

Figure 2-1 

Since collocated contemporaneous reference measurements are paired with surrogate measures during each 

sampling period, each time-series generated is individually calibrated to the specific 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 normalized 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

4.5

17:0017:1017:2017:3017:4017:50

CO (ppm) 

0

2000

4000

6000

8000

PID

DRI T15 CO PID (ppb)

Reconstructed BTEX

0

100

200

300

400

500

600

700

800

17:0017:1017:2017:3017:4017:50

BTEX (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 monitors are available (although of different 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. 

2-2
Figure 2-3 

0

4

8

12

16

20

12:0012:0312:0612:0912:1212:1512:1812:2112:2412:2712:3012:3312:3612:3912:4212:4512:4812:5112:5412:57

Time

Battelle HCHO, ppb

0

4

8

12

16

20

Recon 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 Time

PID Concentration (ppbv)

0

100

200

300

400

SPME Concentration (ppbv)

PID (ppb) avgPID SPME

Figure 2-4 

2-3
Analytical 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 CH3CHODNPH/HCHOCont 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

2-6
The continuous Kore MS200 will be used to monitor BTEX 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 the pilot studies, comparing favorably with the canister 

measurements for most samples. Although we have attempted 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 system, 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. Since the MS200 runs directly off isolated 12V AGM battery 

power, it should also be isolated from 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 absorbs 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 enhance 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 1st Reno pilot study both urinary and breath concentrations of MTBE and the BTEX compounds were 

measured in two subjects after three separate scripted exposures. 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 collected 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 short half-life of absorbed volatile vapors such as BTEX in 

breath will require fast, precise timing for sample collection. 

Urinary measurements from the pilot study 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 observed in one subject and a lesser exposure effect observed in a second subject. 

There was a time course in the elimination of benzene that showed urinary benzene concentrations increasing with 

time. This is similar to the results reported by Lee and Weisel (1998) on the behavior of MTBE in urine. Because of 

an inability to see the decay of urinary benzene 3 hours post exposure, a second scripted refueling exposure was 

conducted in Reno, NV, to repeat this peak exposure and see if the urinary VOC concentration data can be linked to 

an exposure effect at these levels and 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. 

2-7
Based on the pilot study results, since it was not possible to discriminate urinary benzene concentrations in postexposure as compared to pre-exposure, it was decided not to conduct urinary measurements. 

Based on results from the 2nd 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: before the exposure in the 

isolated subject, and 10 seconds (timed with a stopwatch) immediately after active refueling or a measured peak 

exposure in the other MEs. In addition, a third backup breath 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 participate 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 avoiding alcohol ingestion (ethanol) and first-hand or secondhand cigarette smoke for at least 3 days prior to the scripted 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 samples. One sample is taken before initiating ME sampling; 

the second, ten seconds (timed with a stopwatch) immediately after completing active refueling task or experiencing 

a measured peak exposure in another ME, and the third one immediately following the second. The 3rd 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 reserve. 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 method. 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 with laboratory-grade zero air and a dilution factor is 

calculated based on initial and final pressures. An additional normalization factor could be determined for samples 

that deviate significantly from the expected 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 Scientific). 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 the 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. 

2-8
2.2.1 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 3x102

 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, allowing 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 air 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 portable, battery-powered passive electrochemical unit (Langan 

T15). Prior to each period of field measurements both instruments will be calibrated using a zero-air generator and 

span gas (10.5 ppm) to provide two reference points encompassing 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 positive 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 appropriate CO concentration for anticipated range and 

verify flow rate 

6. Let instruments stabilize, record current reading, and adjust span to correct value. 

2-9
7. Re-connect zero-air source, let stabilize 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 will be checked against the reference unit, which has an 

automatic baseline stabilization and internal zero-air source, at the beginning and end of each sampling day and 

baseline readings will be recorded. If any significant deviations 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 sufficiently reproducible, the resulting concentration data will 

be adjusted based on the units internal temperature sensor, which has an accuracy of +/- 2 C. If the temperature 

compensation approach does not appear feasible, the instrument 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 remote switch was installed to allow cabin on/off control of 

the integrated samplers; and a hitch-mounted rack was installed to transport the instrument cart. We will continue to 

use the other batteries for the cart experiments since the lack of a trapped space means we will not encounter 

interferences. We will also use the NDIR-based CO instrument, 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. 

2-10
2.2.3 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 H2SO4 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 monitor 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 instrument was evaluated during the 2nd 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 cases, 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 μm) 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. The heated flash vaporization injector 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 μl injection of liquid standards prepared in pentane with BTEX at different 

concentrations (1, 5, 10, 20, 40, 50, and 100 ng/μl). 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 calibration 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 movement, 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 

2-11
calibration in a static system, such as a Tedlar bag. However, in an outdoor environment there is always some air 

movement, so the air is passing continuously across the surface of the fiber. The sorption rate 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 corrections 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 cooling/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 μm) 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 fibers 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 methods 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-Pac 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 requiring access through the van tailgate) and the protocol was modified to require that the van 

engine be off during changes of sampler media. 

 The canister sampler uses a differential pressure flow controller 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 field program by using a primary flow device (e.g. Gillibrator) 

and then will be periodically checked 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 

2-12
absolute 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 recommended method are that, in the DRI method, canisters 

are heated to 140°C during the vacuum cycle and more cycles 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 the total non-methane organic compound (NMOC) 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 concentrations promptly upon receipt of samples from the field, 

using gas chromatography with flame ionization detection (GC/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 standards are used to convert area 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 analyses 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 canisters 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 adsorbent 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 analyses 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 samples to serve as a comparison with canister 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; Vayghani 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/FID for purity prior to sampling. After cleaning, the tubes 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. 

After sampling at nominal monitored flows of 200-300 ml/minute, tube samples are analyzed by the thermal desorptioncryogenic preconcentration method, followed by high-resolution gas chromatographic separation and mass spectrometric 

detection (MSD) of individual compounds. The Chrompack Thermal 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 acetaldehyde will be collected with Sep-Pak cartridges that have been 

impregnated with an acidified 2,4-dinitrophenylhydrazine (DNPH) reagent (Waters, Inc), 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 form 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 measurement 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 

2-13
carbonate/sodium nitrite/glycerol mixture (Koutrakis, et al., 1993). After sampling, the cartridges will be eluted 

with acetonitrile. An aliquot of the eluent will be transferred into a 1-ml septum vial and injected with an 

autosampler into a high performance liquid chromatograph (Waters Alliance System) 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.

2-14
3-1

3. EXPERIMENTAL PROTOCOL 

This section specifies the tasks required 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 Residential Garage Exposure Measurements 

DRI and SwRI will determine the quantitative relationships 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, and Chicago) for the study. SwRI will procure two 55-gallon 

drums of each fuel from a major supplier in each city to conduct the work in San Antonio. Three summer fuels were 

procured and evaluated during May 2002 and the three winter fuels will be procured during December 2004. SwRI 

will test fuels for bulk properties and DRI will speciate the chemical composition of each of the six blended fuels. 
Figure 3-1: Overall Structure of 211(b) Monitoring Requirements 

Segment N

Leading

vehicle

Trailing

vehicle

Segment 1

Cabin

Tests

FTP

Emission Tests

Garage Adjacent

room

Test 1 Test N

Garage

Tests

Normal Malfunctioning

Sedan Truck

RFG-MTBE RFG-EtOH Baseline

Summer Winter

San Antonio

MEASUREMENTSReference integrated (20-40 min) canister-1,3 BD, MTBE, BTEX, VOC

(20-40 min) DNPH cartridge - HCHO, CH3CHO(20-40 min) Multibed tube - EtOH

Continuous surrogate (1 min) Langan-CO, ML-NDIR CO, ppbRAE-VOCSupplemental corroborative (1-5; 10 min): KORE-BTEX, DRI-HCHO

SPME - BTEX

OTHER DATA

Diary (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)

MEASUREMENTS

Semi-continuous (10 min): SPME - MTBE, EtOH, BTEX

OTHER DATA

Diary (ME/event)Location: GPS (lat/long, min)Meteorology: W S/W D, RH, T (min); surface roughness; stab. class Local air quality: sampling day monitoring station data (60 min)

Segments for Cabin Tests

1 Initial background -- no test vehicles2 Idling, close spacing3 Moderate speed, moderate spacing4 High speed, greater spacing5 Final background - no test vehicles

Garage Tests

1 Background, garage empty2 Car in garage, kitchen door

open f or 1 min

3 Car in garage, kitchen door 

open for entire test

4 Car in garage, kitchen door

closed -- window open

5 Car in garage idling, garage

door open, kitchen door openfor 1 min

6 Back car out and close garage

door

3-3

Figure 3-2. Monitoring Requirements for San Antonio Study 
3-4

San A

Table 3-1. Collection of Time-Integrated Samples for Chemical Analysis – San Antonio 

Test 

Duration 

(min)

Sample time 

SPME (min) SPME Cans DNPH

Solid Adsorb. 

a

No. of 

Tests SPME 

ntonio - Trailing Vehicle

kground 10 10 1 1 1 1 24 24 

ure Measurements 120 10 12 1 1 1 24 288 

20 10 2 1 1 1 24 48 

15 3 3 3 360 

ntonio - Residential Gara

 Initial bac  Expos  Idle  SubtotalSan A ge Exposure

age (baseline) 30 30 1 1 1 1 24 24 

age (during exposure) 150 30 5 1 1 1 24 120 

ent room (baseline) (b) 30 1 1 1 1 24 24 

ent room (during exposure) (b) 30 5 1 1 1 24 120 

30 12 4 4 4 288 

 In-gar  In-gar  adjc  adjc  Subtotal
3.1.2 Determination of Tailpipe and Evaporative Emissions of Test Vehicles 

SwRI will procure two test vehicles and determine evaporative 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 the 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, O2

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. SwRI will determine exhaust emission rates for the two test 

vehicles, with and without malfunction, using three regional fuels during each of two seasons (with seasonal fuels). 

This will result in 12 combinations for each season. SwRI also will measure evaporative emissions using the same 

test vehicles with and without induced malfunction (e.g., disconnecting fuel line to carbon 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 exposure 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 and 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, CO2; and 

speciated VOC emissions (to include MTBE, ethanol, benzene, toluene, ethyl benzene, xylene, 1,3-butadiene, 

formaldehyde, and acetaldehyde) will be determined for each test. During hot soak SHED tests, total hydrocarbon 

and VOC emissions (as above except without aldehyde/ketone 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 thermocouple 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 

3-5 
for 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 portion 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 hydrocarbons 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. 

3-6 
Table 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 normal operation and with induced malfunction to determine 

exposure in a cabin of a third vehicle that is trailing the test 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. 

3-7 
During each test, the trailing vehicle will be driven behind the 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 vehicle 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 closer distance deemed 'safe' for professional drivers under low-traffic density 

and prevailing meteorological conditions by SwRI and DRI staff. 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 

3-8 
San 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 adjacent 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 located 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 (background) 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 monitors will sample continuously from collocated inlets 

in the adjacent room for corroborative purposes. A half-filled two gallon standard plastic gasoline storage container 

with vent open will be placed with a lawnmower with gas 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 the 3-hour protocol as described in the table. 

The ambient garage temperature will be recorded every 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 

PID1 

Background 

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 

Maximal PID1 

AER to 

indoors 

30 closed closed closed kitchen MS200 

DRI 

PID2 

NDIR CO 

2 

garage Langan CO 

Maximal PID1 

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 

3-9 
3-10

3.2 Microenvironmental Exposure Measurements in Atlanta, Chicago, and Houston 

One of the overall goals of the project is to sample high-end microenvironments (MEs), plausibly characterized in 

the upper 90th 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 roadway and other high-end exposure microenvironments in 

Houston, Chicago, and Atlanta over several weeks in each city and season during 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 microenvironments 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-integrated 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 advisable 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 Sampling Time 

(min) 

1 In-Cabin Congested Freeway 5 40 

2 In-Cabin Urban Canyon 3 40 

3 In-Cabin Refueling 5 20 

4 In-Cabin Underground Garage 5 40 

5 In-Cabin Toll Plaza 3 40 

6* Roadway Tunnel 5 yes yes 40 

7 Outdoor Refueling 5 yes yes 20 

8 Sidewalk 3 40 

8/9 Sidewalk/Bus Stop 3 40 

10 Outdoor Surface Parking 3 40 

11 Outdoor Underground Garage 5 yes yes 40 

12 Outdoor Toll Plaza 3 40 

13* In-cabin Trailing High-Emitting Vehicles 5 yes yes 40 

*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. 
3-11 

Urban 

 1. I 2. I 3. I 4. I 5. In 6. Ro 13 Su

Urban nts

 7. Outdoor Refueling4 5 20 10 10 10 5 10 30 60 

 8. Sidewalk 3 40 10 20 3 3 6 18 120  8/9. Sidewalkl/Bus Stop 3 40 10 20 3 3 6 18 120  10. Outdoor Surface Parking 3 40 10 20 3 3 6 18 120 

 11. Outdoor Underground Garage4 5 40 10 20 10 5 10 30 120 

 12. Outdoor Toll Plaza 3 40 10 20 3 3 6 18 120  Subtotal 22 110 32 22 44 132 660 

Biomarker Breath Samples

 6. Roadway Tunnel 1 5 40 15 20 0 

 7. Outdoor Refueling 5 20 15 30 0  11. Outdoor Underground Garage 5 40 15 30 0 

 13. In-cabin Trailing High-Emitting Vehicles2 5 40 15 10 0 

 Subtotal5 15 45 90 0 

 Total 63 220 108 48 96 378 1320 

1ME6 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 Site Total No. of Samples f

Table 3-7. The Number of Samples for Each Microenvironment for Three Cities and Two Seasons 

e

Replicates

Test 

Duration 

(min)

Sample time 

SPME (min) SPME Cans DNPH

Solid Adsorb. 

A&B3

Total No. of 

Tests

Total No. 

SPME

Exposures in Vehicle Cabin 

n-Cabin Congested Freeway 5 40 10 20 5 5 10 30 120 

n-Cabin Urban Canyons 3 40 10 20 3 3 6 18 120 

n-Cabin Refueling 5 20 10 10 5 5 10 30 60 

n-Cabin Underground Garage 5 40 10 20 5 5 10 30 120 

-Cabin Toll plaza 3 40 10 20 3 3 6 18 120 

adway Tunnel1,4 5 40 10 20 10 5 10 20 80 

. In-cabin Trailing High-Emitting Vehicles2,4 5 40 10 20 10 5 0 10 40 

btotal5 26 110 31 26 52 156 660 

Exposures in Other Microenvironm
3.2.1 Exposure Diary and Script Development 

Scripted activities will be used during the exposure measurements. This methodology, referred 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 activity. By multiplying the total time spent during each activity by the pollutant 

concentrations, activity-specific exposure can be estimated. 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 total 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 included in Appendix D. 

We also will compare personal exposures with ambient measurements 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 high-end microenvironmental activities take less than an 

hour (e.g., refueling, transiting a tunnel, leaving a parking 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 transported to each of the three cities 

and used for the in-cabin exposure measurements 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 microenvironments 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 characterized 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 sample 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 will 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). 

3-12
We 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 microenvironment 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 the technician as appropriate. 

3.2.3 Technician Biomarker Analysis 

Breath measurement will be used as the biomarker of choice. Since we were not able to distinguish background 

benzene 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 

2nd pilot study, with pre- and post-exposure collections (plus a backup sample) of the subject’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 with higher levels of accumulated 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 scripts. 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 windows & 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 using sniffer. Drive back and forth on the segment 

3-13
continuously 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-minute 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 unreliable 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 prior to the refueling test. Park car at refueling location and sample 

alternative 10-minute periods under high- and low-ventilation (vehicle windows & vents open and 

windows & 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 the 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 concentrations. 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 conditions 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 queue during the 40-minute test 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 environment. Drive in slowest, 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 concentration. 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 refueling 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 than 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 attempt 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 concentrations. 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 (breath) 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 the 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 the 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 & 

3-16
vents 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 two of the cities, Houston and Chicago, can also be affected by land/ocean breezes. 

Although in situ surface-based observations are preferable, diagnostic output from operational numerical models can 

also be analyzed. 

Field participants in the experiment will make the local 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 within DRI's Division of 

Atmospheric Sciences, is to acquire, store, summarize, distribute, and interpret atmospheric data. The Climate 

Center has excellent access to past data nationwide through its own considerable 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 through 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 America. 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 deviation) 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 adsorbent cartridges, formaldehyde and acetaldehyde from DNPH cartridges, 

and formaldehyde from continuous measurements. 

3-17
• Determine ratios of the sum of formaldehyde and acetaldehyde 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 methods, characterize the effect of time resolution on 

measurement of peak exposures. 

Determine quantitative relationships between tailpipe emission 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, CH3CHO, 

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 driving condition for each of the 24 test combinations (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 exposure 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 emission 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 evaporative and exhaust emission in microenvironments. 

• Process GPS data and develop a log of exposure measurements 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 appropriate for microenvironments dominated by vehicle 

exhaust or fuel evaporative emissions. 

• Evaluate the consistency in time-series among continuous CO, PID, MS200, and HCHO measurements in 

each microenvironment by city and season. 

• Reconstruct the time-series of individual air toxics using the surrogate CO and PID measurements and their 

correlations to time-integrated measurements. 

• Determine the differences in mean and peak exposures by city and season for each microenvironment and 

characterize the variability of replicate 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 conditions 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 measured 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 technicians 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 1st 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 2nd 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 incorporating reviewers’ comments (submitted to EPA for 

review and approval together with the reviewers’ comments and a statement 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 VOCs in air-quality determinations by GC-MS. American 

Laboratory. 32-34 

Chai, M. and J. Pawliszyn (1995) Analysis of Environmental Air Samples by Solid Phase Microextraction and Gas 

Chromatography/Ion Trap Mass Spectrometry, Environmental Science and Technology, Vol. 29, No. 3. 

Environmental Protection Agency (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). Descriptive Statistics from a Detailed Analysis of the National 

Human Activity Pattern Survey (NHAPS) Data. Document 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 19-22, 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.” Presented at the 1992 

U.S. EPA/A&WMA International Symposium on Measurement of Toxic and Related Air Pollutants, 

Durham, NC, May 1992. 

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Shire, J.; Harshfield, G.; Zielinska, B.; Pasek, R. “A Comparison of Analytical Methods for Oxygenated Volatile 

Organic Compounds in Ambient Air,” In: Proceeding of the U.S. EPA/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 Evaporative Emissions into a Home from an M85-Fueled Vehicle 

Parked in an Attached Garage, JAWMA , 50:371-377. 

Vayghani, S. A., C. Weisel, (1999) The MTBE air concentrations 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 the 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-1
INTRODUCTION 

This sampling plan specifies the details for the field measurement 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 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 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 emissions 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 99th 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 exposures that include the 99th 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 during 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 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-10 during the morning commute period, urban canyons in downtown Houston, Washburn 

Tunnel, various toll plazas on the Sam Houston Tollway and Hardy Toll Road, 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 garages at the City Hall Annex and Greenway Plaza (Compaq 

Center), 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 microenvironments 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 during 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-2
first 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 vehicle 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 accelerations. 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 anticipated 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

700

072707320737074207470752075708020807081208170822

Time, CDT

PID 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-3
Downtown Houston

0

100

200

300

400

500

600

08300835084008450850085509000905091009150920092509300935094009450950

Time, CDT

PID 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

500

12401245125012551300130513101315132013251330133513401345

Time, CDT

PID Response (ppb)

Average

Maximum

Figure 3. George Bush International Airport and drive to Washburn Tunnel. 

 A-4
Minute Maid Stadium Parking Lot After Houston Astros Baseball Game

0

100

200

300

400

500

600

700

2145215021552200220522102215

Time, CDT

PID 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

500

13451350135514001405141014151420

Time, CDT

PID Response (ppb)

Average

Maximum

Figure 5. Tour of Washburn Tunnel and the Ship Channel Toll Plaza on the Sam Houston Tollway. 

 A-5
The 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 passenger pick-up being 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 during 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 Minute 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-6
measurements 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 parking lot, while presumably 

still in cold-start mode. We then walked along the sidewalk 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 period 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 tollbooth. 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 tollbooth. Based on these results, we propose to sample with a sampling cart as close 

to a tollbooth as allowed by the Harris County Tollway Authority. Prior to setup, we will make one pass through the 

toll plaza to measure in-cabin exposure with continuous instruments 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 relative 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 sampling routes) prior to sampling run and select the appropriate sampling 

route from the following options. If accidents, other hazards, or local conditions change, 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 (southeast) 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 parking garages may still be in cold-start mode and because 

ME1 precludes ME2 during the morning commute period. 

 A-7
Make multiple trips during a 40-minute period along a four by one block surface street loop in downtown 

Houston. The loop consists of four one-way streets and 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 samples integrated over the entire 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. Note 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 temperatures, 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. Van 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, Greenway 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-8
Measurements 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 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 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 sampling 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 locations after driving it sufficiently to elevate measured 

fuel tank temperatures. 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. 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 several 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-9
one every 10 minutes. Record the local wind speed, direction, ambient temperature 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 downtown 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 baseball 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 entire 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 record 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 Plaza is preferable for several reasons. The Greenway 

Plaza is a business complex of ten office towers, the Renaissance Hotel and the Compaq center, home to the 

NBA Houston Rockets and the WNBA Comets. The complex includes 13,000 parking 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 sampling 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 HCHO analyzer, and portable 

PID monitor and collect one set of canister and DNPH samples 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 sampling 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 toll 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 ambient 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-10
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. Collect one SPME sample during this sampling period. 

DAILY SAMPLING SCHEDULE 

The daily schedules for the Houston summer and winter 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 the Section 211(B) Tier 2 High End Exposure 

Screening Study of Baseline and Oxygenated Gasoline 

Addendum B – Summer/Winter Sampling 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-1 
INTRODUCTION 

This sampling plan specifies the details for the field measurement 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 rationale for their selection. We will endeavor 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 analyzer. 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 garages 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/autos/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 Rapid 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.com/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-2 
Marietta Parkway to downtown Atlanta. Drive the opposite direction during the evening rush hour. A forward 

facing camcorder will record roadway activities and locations 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 Roswell 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 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. 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 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. 

After driving to elevate measured fuel tank temperatures, 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. Van windows are to be down and doors open as appropriate 

during this ME. 

4. In vehicle: parking garage (ME4) 

 B-3 
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 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 14th Street in Midtown Atlanta during the morning and evening 

commute period and prior to and after the Atlanta 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) 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) 

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 samples 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. Monitor 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 northbound and southbound direction 

consisting of four lanes each. The tunnel is very short and 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 station 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 locations after driving it sufficiently 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 seconds 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-4 
8. Outdoor: sidewalk near high-density traffic (ME8) 

Conduct sidewalk sampling in downtown 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 integrated over the entire 40 minute period. 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 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 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 14th Streets) for 40 

minutes starting about 5:00 p.m. when office workers leave the complex (cold start emissions). Sample at exit 

queues and ramps. 

Sample the breathing zone continuously with a KORE MS 200, Langan T15, DRI HCHO analyzer, and portable 

PID monitor and collect one set of canister and DNPH samples 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 after 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 toll plaza. Access to the toll plaza is from the northbound 

direction. This is an employee parking 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 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. 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. Collect one SPME sample during this sampling period. 

 B-5 
13. 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 streets 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 similar peak exposure and followed immediately 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 the 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-1 
INTRODUCTION 

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 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 rationale for their selection. We will endeavor to use the same ME locations 

during both the winter and summer studies. 

Desert Research Institute personnel surveyed potential microenvironments 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 (particularly 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 Comiskey 

Park (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, selecting 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 80th

Avenue), which is about 20 miles southeast of Downtown Chicago. Our search for some microenvironments such as 

service stations, vehicle inspection stations, and congested 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 (Eisenhower Expressway) and I-94 interchange will take 

roughly 20 minutes. Use high ventilation conditions (window 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 after the second 20 minutes. 

This stretch of freeway includes a series of overpasses, 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-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: Langan T15 CO monitor, NDIR CO 

instrument, and ppbRAE, 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 during 

the entire period without compromising the cabin ventilation condition. Monitor and record the van’s position 

(GPS), and in-cabin temperature and relative humidity. 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-2 
2. 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 Buren 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 samples integrated over the entire 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. Note 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 (80th 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 service station personnel. 

After driving to elevate measured fuel tank temperatures, 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. Van 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 underground 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 Lake 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 and 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 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 

 C-3 
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 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 82nd Street (southbound)/83rd 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 around and proceed back south on Lower 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 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 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 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 provide a stopped pan of the sampling site location. 

7. Outdoor: refueling vehicle (ME7) 

Sample at the Gas City (80th 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 service station personnel. 

Park the van downwind from the centroid of the pump locations after driving it sufficiently to elevate measured 

fuel tank temperatures. Refueling sampling will be conducted during periods with local wind speed below 5 

mph. 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 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 (background and refueling) samples during the initial background 

 C-4 
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 sample 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 temperature 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. 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 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 the 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 HCHO 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 includes 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 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) 

Two possible locations for this microenvironment are tollbooths on tollways or one of the centralize vehicle 

inspection stations. The vehicle inspection station at 3824 159th Place is reasonably close to the RV Park and 

has good access. Sampling at the toll plaza would be conducted behind the tollbooth 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-5 
Sample 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. Collect 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 ME8/9 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 

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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-1
APPENDIX 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 instruments to be used in this study have 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 appropriate blank will be run daily for each instrument. Generally this 

is run after the calibration check and before any samples 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 internal standards are also added. 

Recovery for NMHC samples in internally determined by calibration standards. 

f. Determine and report minimum trapping efficiency. For solid adsorbent samples, the backup traps 

are used for approximately 5 % of samples to confirm that no quantifiable levels of compounds are 

getting through the first trap. 

Every measurement consists of four attributes: a value, a precision, an accuracy, and a validity (e.g., Hidy, 1985). 

The measurement methods described in the previous section are used to obtain the value. Quality assurance is the 

complementary part of the measurement 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 responsibility 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 activities: quality control (QC), and quality assurance (QA). 

The QC activities are on-going activities of measurement and data processing personnel. QC activities consist of 

written standard operating procedures to be followed during sample 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 tolerances 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 maintenance 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 sample 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-2
audits 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 practice. 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 valid 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 performance audit involves challenging the measurement/analysis system with a known standard 

sample that is traceable to a primary standard. Performance audits of data processing 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 Research 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 Institute – Division of Atmospheric Sciences, Organic 

Analytical Laboratory. 

 E-3
DAS 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-generated 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 certification 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 analytical instruments. Perform regular calibration checks and recalibrate if 

calibration does not meet specified parameters. Log in samples in project logbooks upon 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 received 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 notified of the package's arrival. A representative of the 

laboratory signs for the package and returns with it to the 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 initiated 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 samples and sample extracts are stored in the freezers. The 

rooms are locked when not in use and the building has limited access (i.e., it is locked from 1730 to 0730 weekdays 

and all weekend to ensure access only to authorized personnel). 

 E-4
When a sample is analyzed, its identification number (sample number) is recorded both in the written logbook for 

each instrument and in the LIMS file created 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 maintained 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 are routinely maintained. Written records include receiving logbooks, 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 graphs 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 noted. 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 calibration logbook where all standard 

solutions made in the laboratory are logged, a graph of all 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 maintained on a central computer (the LIMS file server). Our data collection system 

includes a history record that maintains lists of files created 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 incorporated 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 suppliers. 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 for 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 shall 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 the 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 cartridges 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/MS, 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, replicates 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 measurements, an NIST-traceable standard 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 measurements 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 calibrated 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 system 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-efficient (R2) of 0.99 to be acceptable. 

During the course of analysis, calibration standards are routinely analyzed to ensure that the instrument response has 

not changed. The criterion of 10% of expected response is used by the analyst to determine whether the instrument 

must be recalibrated. 

Retention time windows for each analyte will be established prior to analysis 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 providing 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 sampling media, and our data analysis system. The ability 

of our data analysis system to merge multiple samples into a single database allows for rapid and accurate crosscomparisons among the samples. 

Other internal quality control checks consist of those ordered 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. Duplicate analyses are essential for determining 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 call. Our contract specifically states that any problem will 

be corrected within 48 hours of notification of the manufacturer. 

Several laboratory personnel have extensive experience working with all the major laboratory equipment and DRI 

has extensive support facilities (electronics and machine shops, QA lab with standard reference 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 depends 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 combined 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 value based on combined volume (for carbonyl and semivolatile compounds), replicate (for hydrocarbon, SVOC and 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 uncertainties 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 established a file server system that provides a central storage area 

for all laboratory and field data. The databases have defined structures that are maintained 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 of 

this 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, prepared 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 nominal 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 ranges, 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 participated in the NARSTO-Northeast hydrocarbon 

intercomparison study, involving the analysis of two ambient air samples by participating laboratories. Participants 

included Biospheric Research Corporation (BRC), State University of New York at Albany (SUNYA), EPA Region 

I, DRI, and 8 of the PAMS networks in the northeastern U.S. The DRI laboratory performed 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 laboratory 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 participated in non-methane hydrocarbon laboratory performance 

audits, organized by the Quality Assurance Section, Monitoring 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 Microfilms International, Ann Arbor, MI. 

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