**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

Jacob D. McDonald

Lovelace Respiratory Research Laboratory

P.O. Box 5890

Albuquerque, NM 87185

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: September 30, 2002

**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.

**TABLE OF CONTENTS**

######### Acknowledgment ii {#acknowledgment-ii .unnumbered}

######### Table of Contents iii {#table-of-contents-iii .unnumbered}

######### List of Tables iv {#list-of-tables-iv .unnumbered}

List of Figures iv

[1. INTRODUCTION 1-1](#introduction)

[2. PROPOSED MEASUREMENT METHODS AND PROTOCOLS
2-1](#proposed-measurement-methods-and-protocols)

[2.1 Proposed Exposure Measurement Methods
2-1](#proposed-exposure-measurement-methods)

[2.2 Proposed Biomarker Measurements
2-3](#proposed-biomarker-measurements)

[2.2.1 Urine and Breath Sample Collection
2-4](#urine-and-breath-sample-collection)

[2.2.2 VOC Analysis in Breath and Urine Samples
2-4](#voc-analysis-in-breath-and-urine-samples)

[2.3 Proposed Measurement Protocol 2-5](#proposed-measurement-protocol)

[2.3.1 Kore MS200 2-5](#kore-ms200)

[2.3.2 CO Instruments 2-6](#co-instruments)

[2.3.3 Continuous Formaldehyde Monitor
2-8](#continuous-formaldehyde-monitor)

[2.3.4 BTEX and MTBE by Solid Phase Microextraction (SPME)
2-8](#btex-and-mtbe-by-solid-phase-microextraction-spme)

[2.3.5 Time-Integrated Air Sample Collection and Analysis
2-9](#time-integrated-air-sample-collection-and-analysis)

[3. EXPERIMENTAL PLAN 3-1](#experimental-plan)

[3.1 Controlled In-Cabin and Residential Garage Exposure Measurements
(Task 2)
3-1](#controlled-in-cabin-and-residential-garage-exposure-measurements-task-2)

[3.1.1 Procurement of Test Fuels from Houston, Chicago and Atlanta (Task
2a)
3-1](#procurement-of-test-fuels-from-houston-chicago-and-atlanta-task-2a)

[3.1.2 Determination of Tailpipe and Evaporative Emissions of Test
Vehicles (Task 2b)
3-7](#determination-of-tailpipe-and-evaporative-emissions-of-test-vehicles-task-2b)

[3.1.3 Relationship Between Exhaust Emission Rates and In-Cabin Exposure
(Task 2c)
3-11](#relationship-between-exhaust-emission-rates-and-in-cabin-exposure-task-2c)

[3.1.4 Relationship Between Evaporative Emission Rates and Exposure in a
Residence With an Attached Garage (Task 2d)
3-12](#relationship-between-evaporative-emission-rates-and-exposure-in-a-residence-with-an-attached-garage-task-2d)

[3.2 Microenvironmental Exposure Measurements in Atlanta, Chicago, and
Houston (Task 3)
3-13](#microenvironmental-exposure-measurements-in-atlanta-chicago-and-houston-task-3)

[3.2.1 Exposure Diary and Script Development (Task 3a)
3-14](#exposure-diary-and-script-development-task-3a)

[3.2.2 In-cabin Exposures in Urban Microenvironments (Task 3b)
3-14](#in-cabin-exposures-in-urban-microenvironments-task-3b)

[3.2.3 Outdoor and Indoor Exposure in Urban Microenvironments (Task 3c)
3-15](#outdoor-and-indoor-exposure-in-urban-microenvironments-task-3c)

[3.2.4 Technician Biomarker Analysis (Task 4)
3-15](#technician-biomarker-analysis-task-4)

[3.2.5 Approach for Selecting High End Microenvironments
3-15](#approach-for-selecting-high-end-microenvironments)

[3.3 Meteorology (Task 5) 3-20](#meteorology-task-5)

[3.4 Data Analysis (Task 6) 3-20](#data-analysis-task-6)

[3.5 Reporting 3-23](#reporting)

[4. PROJECT SCHEDULE AND DELIVERABLES
4-1](#project-schedule-and-deliverables)

[5. REFERENCES 5-1](#references)

**LIST OF TABLES**

[Table No.]{.underline} [Page No.]{.underline}

Table 2-1. Proposed Measurement Method 2-2

Table 3-1. Collection of Time-Integrated Samples for Chemical Analysis
3-4

Table 3-2. Suggested Test Plan for Each Vehicle 3-9

Table 3-3. Summary of FTP Driving Cycle 3-10

Table 3-4 API Trailing Vehicle Protocol
........................................................3-11

Table 3-5 API Garage Study Protocol
.........................................................\...3-13

**LIST OF FIGURES**

[Figure No.]{.underline} [Page No.]{.underline}

Figure 2-1. Variability of CO Electrochemical Cell Response with
Temperature. 2-7

Figure 3-1. Overall Structure of 211 (b) Monitoring Requirements 3-2

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

Figure 3-3. FTP Driving Cycle 3-10

**LIST OF APPENDICES**

Appendix A Summer 2002 Sampling Plan for
Houston...........................A1

Appendix B Sampling Plan for Atlanta
..............................................B1

Appendix C Sampling Plan for Chicago
.............................................C1

Appendix D Example of a Diary
...................................................................D1

#  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 MTBE-oxygenated , 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
> 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). DRI and LRRI conducted a
> five-day pilot study (Task 1) in Reno, NV during February 2002 to test
> alternative measurement approaches in the field under conditions that
> are similar to those that will be encountered in the main study. TRJ
> and API provided input in the design of the pilot study and reviewed
> the results and findings. The evaluations included available
> measurement methods for continuous and time-integrated measurements of
> carbon monoxide (CO), total volatile organic compounds (TVOC), and
> designated VOC species. DRI and LRRI also evaluated the stability of
> the designated VOC species in breath and urine samples during the
> pilot study. Results of the pilot study are summarized in Appendix A.
> The draft exposure protocols were appropriately modified based upon
> the results of the pilot study. Section 2 describes the proposed
> exposure measurement approaches and calibration and other quality
> control procedures.

Two approaches are proposed for the main exposure study. 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 second approach, 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 2002) and winter (January to March 2003). 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 urine. Section 3 specifies the
microenvironments and exposure protocols. The results of this study will
provide information that would permit quantification of 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.

#  PROPOSED MEASUREMENT METHODS AND PROTOCOLS

This section describes the measurement methods that are proposed for the
exposure study and provides the rationale for their selection. Results
of the evaluation of the methods during the pilot study are summarized
in the Pilot Study Report, which is attached to this study plan.

## Proposed Exposure Measurement Methods

The methods we propose to use to measure the exposures in the various
microenvironments (MEs) are summarized in Table 2-1 and will be
discussed below.

Three continuous methods will be employed to monitor 1) the aromatic
hydrocarbons benzene, toluene, ethylbenzene and the xylenes (BTEX), 2)
carbon monoxide, and 3) formaldehyde. These methods will be also
combined with component concentration ratios from contemporaneous
time-integrated samples to reconstruct the expected time series for
species, e.g., 1,3 butadiene (BD), ethanol (EtOH), and methyl tert-butyl
ether (MTBE), for which we do not have continuous instruments.

The Kore MS200 will be used to monitor BTEX on a one-minute basis. 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 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
orgainic molecules do not pass the membrane quickly. The instrument
performed well during the pilot study, comparing favorably with the
canister measurements for most samples. Part of the challenge during the
pilot study was that the instrument had not fully recovered from the
long delay it was held in customs prior to the study. Once the vacuum
system had fully recovered, we had no problems with the instrument.
Since the pilot study we have been further researching this instrument
and are confident that this instrument will perform well. In addition,
we have secured the availability of another Kore MS200, which is
maintained by Horiba Instruments, Inc. in Irvine, CA. In the event there
are further difficulties with our MS200, we can get this one on loan
very quickly.

Carbon monoxide will be monitored by the Langan T15 CO monitor and by
the API 300 CO NDIR instrument (courtesy of the US EPA). Langan T15 is
an electrochemical monitor for CO. The response time of this instrument
is somewhat slower than infrared-based instruments.

Since Battelle was unable to construct a Continuous Formaldehyde Monitor
for DRI, we purchased this instrument from Alpha-Omega Power Technology,
Ltd. (Albaquerque, NM). The Alpha-Omega instrument utilizes the same
reaction as the Battelle monitor - it absorbs formaldehyde in acidified
water, reacting it with 2,4-pentanedione and ammonia to form a cyclized
product, 3,5-diacetyl-1,4-dihydrolutidene, which is continuously
detected by fluorescence. The method is highly specific for formaldehyde
and very sensitive.

####### Table 2-1 Proposed Measurement Methods {#table-2-1-proposed-measurement-methods .unnumbered}

<table>
<colgroup>
<col style="width: 13%" />
<col style="width: 8%" />
<col style="width: 9%" />
<col style="width: 8%" />
<col style="width: 7%" />
<col style="width: 8%" />
<col style="width: 15%" />
<col style="width: 9%" />
<col style="width: 6%" />
<col style="width: 11%" />
</colgroup>
<tbody>
<tr class="odd">
<td><strong>Method</strong></td>
<td colspan="9"><p id="species"
class="heading unnumbered">Species</p></td>
</tr>
<tr class="even">
<td><strong>Continuous</strong></td>
<td>BTEX</td>
<td>1,3-BD</td>
<td>MTBE</td>
<td>EtOH</td>
<td>HCHO</td>
<td>Acetaldehyde</td>
<td>NMHC</td>
<td>CO</td>
<td>Time</td>
</tr>
<tr class="odd">
<td>MS200</td>
<td>X</td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td>1 min</td>
</tr>
<tr class="even">
<td>T15 CO</td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td>X</td>
<td>1 min</td>
</tr>
<tr class="odd">
<td>API 300 CO</td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td>X</td>
<td>Seconds</td>
</tr>
<tr class="even">
<td>HCHO</td>
<td></td>
<td></td>
<td></td>
<td></td>
<td>X</td>
<td></td>
<td></td>
<td></td>
<td>1 min</td>
</tr>
<tr class="odd">
<td>ppbRAE</td>
<td>X</td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td>Seconds</td>
</tr>
<tr class="even">
<td><strong>Surrogate</strong></td>
<td></td>
<td>A</td>
<td>B</td>
<td>C</td>
<td></td>
<td>D</td>
<td>E,F</td>
<td></td>
<td></td>
</tr>
<tr class="odd">
<td><strong>Semi-Cont.</strong></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
</tr>
<tr class="even">
<td>SPME</td>
<td>X</td>
<td></td>
<td>X</td>
<td>X(?)</td>
<td></td>
<td></td>
<td></td>
<td></td>
<td>15 min</td>
</tr>
<tr class="odd">
<td><strong>Integrated</strong></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
<td></td>
</tr>
<tr class="even">
<td>Can</td>
<td>X</td>
<td>X</td>
<td>X</td>
<td>X(?)</td>
<td></td>
<td></td>
<td>X</td>
<td>X</td>
<td>60 min</td>
</tr>
<tr class="odd">
<td>DNPH</td>
<td></td>
<td></td>
<td></td>
<td></td>
<td>X</td>
<td>X</td>
<td></td>
<td></td>
<td>60 min</td>
</tr>
<tr class="even">
<td>Solid Adsob.</td>
<td>X</td>
<td></td>
<td>X</td>
<td>X</td>
<td></td>
<td></td>
<td></td>
<td></td>
<td>60 min</td>
</tr>
</tbody>
</table>

Notes:

A.  Time series will be reconstructed from the canister/CO ratio for
    exhaust-dominated samples.

B.  Time series will be reconstructed from the canister/CO ratio for
    exhaust-dominated samples.

C.  Time series will be reconstructed from the solid adsorbent/CO ratio
    for exhaust-dominated samples.

D.  Time series will be reconstructed from
    CH~3~CHO~DNPH~/HCHO~Continuous~ ratio for exhaust-dominated samples.

E.  Time series will be reconstructed from the canister/CO ratio for
    exhaust-dominated samples.

F.  Time series will be reconstructed from the canister/MS200 ratio of
    BTEX for evaporative-dominated samples.

It would be preferable to have continuous measurement methods for
several other compounds; however, there are no acceptable methods for
1,3-butadiene, MTBE, ethanol, acetaldehyde or NMHC, which could be used
in portable modes of operation with the necessary sensitivity. There are
methods that will allow us to correlate the integrated values with a
continuous method in order to reconstruct a time series. For example,
both 1,3-butadiene and MTBE can be determined from the canister. We will
also determine the integrated CO value from the canister. We will start
from the assumption that the MTBE/CO and 1,3-butadiene/CO ratios will be
constant in MEs that are exhaust dominated over the hour integrated by
the canister measurement. Thus, by ratioing to the continuous trace of
CO, we can reconstruct the time series of MTBE and 1,3-butadiene. The
same method will be used for ethanol and NMHC. In the case of
microenvironments that are dominated by evaporative emissions (for
example, refueling) we would not expect the ratio of hydrocarbons/CO to
be consistent. In these ME's we will use the MS200 time series values
and correlate these with the BTEX concentrations from the integrated
samples. The assumption is that the MTBE/BTEX ratio will be constant and
we can thus reconstruct the time series for MTBE, ethanol and NMHC in
this manner. Neither should 1,3-butadiene be present in evaporative
emissions. In addition, we will collect SPME samples over a shorter time
period (10-20 min) to measure the concentrations of MTBE and BTEX. These
data can also be used to derive the time series for various pollutants.

In a similar manner, acetaldehyde and formaldehyde should be correlated
in exhaust dominated samples and we will reconstruct the time series for
acetaldehyde from the continuous formaldehyde data and the ratio of
acetaldehyde to formaldehyde from the contemporaneous hourly integrated
DNPH samples.

In addition we will be monitoring total BTEX using hand-held portable
PID monitor. A new instrument, ppbRAE from Pine Environmental Services,
is highly sensitive with ppb detection level. The ppbRAE measures
continuously total volatile compounds excluding methane and C2 -- C4
saturated hydrocarbons. We will use this device also as a "pollutant
sniffer" to help us selecting the microenvironments with the highest
pollutant levels.

## Proposed Biomarker Measurements

During the 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 is a
limitation in terms of its use as a biomarker of exposure. Unless breath
samples are collected throughout the scripted exposure, a breath sample
at the end of the exposure will only measure what the subject is exposed
to during the last few minutes before sampling.

Urinary measurements from the pilot study also 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. During the pilot study
urinary concentrations were only measured 3 hours post exposure, so we
were not able to observe what may have been a peak concentration of the
compound or the start of elimination from the body. Because of an
inability to see the decay of urinary benzene after exposures, and the
slight inconsistency in the two subjects (one showed much higher urinary
benzene), we conducted another scripted refueling exposure in Reno, NV,
to repeat this peak exposure and see if the urinary VOC concentration
data can be linked strongly to an exposure effect at these levels and to
follow the full time course of elimination. This experiment was
conducted on June 4, 2002, in Reno and the results are described in the
Pilot Study Report.

Since the additional measurements of urinary MTBE/BTEX from the second
refueling experiment were promising, we propose to use this measurement
as the biomonitoring technique of choice. Since we were not able to
discriminate urinary benzene concentrations in low level exposures (e.g.
walking down street), we propose to only conduct biomonitoring
experiments from projected "high-end" exposures such as refueling.
Monitoring will be conducted similar to the pilot study, with pre and
post exposure collections of the subject's urine. The complete time
course of collection will be lengthened based on the results of the
additional experiments that will be conducted. Collection and analysis
will be conducted as described below.

In addition, we will include breath measurements for the two
microenvironments judged to be the highest: refueling and underground
garage. We propose to collect three 1 liter canister samples for each
experiment: before the exposure, immediately after the peak of the
exposure, and after the 1-hr exposure scenario measurement period.

### Urine and Breath Sample Collection

Urine 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 that is certified
with the National Institute of Health.

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 second-hand cigarette smoke for at least 3 days prior to
the scripted exposures. Urine samples (voids) collected before the
exposure will be used to assess background levels in the technician.
Urine biomarker samples are taken immediately before and after
completion of the exposure scenario and at hourly intervals thereafter
until substantial declines in oxygenate and BTEX species were noticed
(about 6-8 hours) in pilot studies.

All voids will be encoded for confidentiality. During and after
exposures, voids will be collected every hour for a time course based on
additional measurements described above.

Urine samples will be collected in 100 ml polyethylene collection
containers. Immediately after collection, a 50 ml portion of the sample
will be transferred via disposable pipette to a glass storage vial with
an airtight Teflon seal. Samples will then be immediately placed on dry
ice or in a freezer prior to shipment to LRRI. Samples will be shipped
priority overnight to LRRI on dry ice, where they will be immediately
placed in a freezer at --80°C prior to analysis.

The breath measurements will be accomplished by having the technician,
immediately after completing the exposure, take a 1-liter canister,
place the tube in his mouth, waste the first half of a breath, turn the
valve to allow the evacuated cylinder to suck the second half into the
canister, and close the valve (Pleil and Lindstrom 2002).

### VOC Analysis in Breath and Urine Samples

The analysis of VOCs in urine will be conducted according to the methods
derived from Fustinoni et al. (1999). This technique will meet the
analytical detection limits required to measure the target analytes at
concentrations that would be present after environmental exposure. The
analysis of VOC in breath samples will be conducted as described by
Pleil and Lindstrom (2002). The approach for these analyses is described
below.

[Sample Preparation.]{.underline} The VOCs of interest here are stable
in urine for up to 2 months (Fustinoni et al., 1999). All extractions
and analyses will be conducted within 1 month after receipt at LRRI.
Frozen urine samples will be left at room temperature until completely
thawed. After mixing, an aliquot of the urine will be transferred to an
analysis vial containing 1 g of NaCl. The vial will then be sealed after
addition of approximately 1μg/ul of benzene-d6, toluene-d8, xylene-d10,
and ethyl alcohol-d6 that will serve as internal standards for the
analysis.

[Head Space-Solid Phase Microextraction.]{.underline} The sample will be
heated to approximately 40º C and held at this temperature to allow
analytes to reach equilibrium between the headspace (HS) gas and aqueous
solution. Analytes will then be sampled from the HS by use of a
polydimethylsiloxane SPME fiber. During sampling, the fiber will be
exposed directly to the HS for about 15 minutes. At the end of this
period, the sample will be directly injected into the gas chromatograph
(GC).

[Gas Chromatography-Mass Spectrometry.]{.underline} HS fiber extracts
will be thermally desorbed onto a GC (Hewlett Packard, 5890) coupled to
a Hewlett Packard 5972 mass selective detector (GCMS). Desorption will
occur at approximately 200ºC for 3 minutes. An Agilent DB-624 column (30
m x 0.25 mm) will be applied to attain the necessary chromatography in
order to selectively analyze MTBE, ethanol, and the BTEX compounds in
the scan mode. The compounds will be quantified by comparing the
response of the analytes and spiked internal standards to those of
calibration curves created from authentic analytical standards. The
limit of detection for this analysis is approximately 15 ng/μl for BTEX
(Fustinoni et al., 1999). The specific limits of detection for MTBE and
ethanol are expected to be in the same range and will be evaluated
during method development.

[Breath Samples Analysis.]{.underline} The analysis of VOC in breath
samples will be conducted as described below in Section 2.3.5 for
canister VOC analysis.

## Proposed Measurement Protocol

This section describes the protocols that will be applied for each
method and applicable quality assurance procedures.

### Kore MS200

The Kore MS200 will be used to measure BTEX in the MEs. The protocol for
use includes the following calibration and operational procedures.

[Calibration Procedures:]{.underline}

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]{.underline}:

1.  Check Battery Status (or plug in).

2.  Inlet valve: Middle position (heater).

3.  Inlet pump: On

4.  Wait until inlet vacuum is less than 3x10^2^ pa and inlet
    temperature led is green

5.  Sample pump On

6.  TOF MS: On

7.  TDC: On (unless you are on battery, then wait as this draws a lot of
    current.)

[Once you are ready to sample]{.underline}:

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 1 spectra.
>
> 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.

### CO Instruments

Two CO monitoring instruments will be used for the field study: a high
sensitivity, fast response gas-correlation unit (API 300 and Monitor
Labs 9830) as a reference device, and a portable, battery-powered
passive electrochemical unit (Langan T15) for exposure measurements.

Prior to each period of field measurements both instruments will be
calibrated using a zero-air generator and span gas 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 both instruments and allow to stabilize for a minimum of
> 15 minutes.
>
> 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.
>
> 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, we will attempt to characterize this temperature response 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 been
observed to be sufficiently accurate (+/- 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. The
reference unit will be kept in a climate-controlled environment (mobile
laboratory) so temperature response is not a concern in that case.

In addition, the Langan T15 monitor encounters an artifact under low
vent conditions inside the vehicle cabin. We suspect that there is an
interference that is vented out under the high ventilation conditions.
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 help
eliminate possible sources of interference, we have eliminated the
wet-cell lead acid batteries and replaced them 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. 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 only the NDIR-based CO instrument inside the vehicle cabin which
does not suffer from the same artifact as the Langan.

![](media/image1.png){width="6.498611111111111in"
height="4.325694444444444in"}

Figure 2-1. Variability of CO Electrochemical Cell Response with
Temperature.

### Continuous Formaldehyde Monitor

The continuous monitor for gaseous formaldehyde analyzer was purchase
from Alpha-Omega Power Technologies. This instrument uses Hantzsch
reaction to produce a fluorescent derivative from HCHO that is monitored
with a fluorescent detector. An aqueous calibration standard in the
10^-7^ to 10^-6^ M range made by serial dilution of 37% formalin
solution in the 0.1 N H~2~SO~4~ scrubber solution is used for the daily
instrument calibration (Kelly and Fortune, 1994). This daily calibration
standard is compared with the gaseous formaldehyde standard, purchased
from Apel-Riemer Environmental, Inc. The monitor is zeroed by supplying
high-purity air to the inlet. Span and zero samples are provided to the
monitor at regular intervals using automated valving. We are presently
working on re-engineering the Alpha Omega HCHO instrument to make it
more field-rugged and reliable.

### BTEX and MTBE by Solid Phase Microextraction (SPME)

Based on the results of our pilot study, we propose to use 75 μm
Carboxen/(poly)dimethylsiloxane (CAR/PDMS) fibers for BTEX, MTBE, and
possibly ethanol. The fibers are exposed for 15 to 30 min, depending on
the specific microenvironment, and are analyzed by injection into a
model 8610C gas chromatograph (SRI), which will be housed in the mobile
laboratory. The analysis is performed immediately after collection in
most cases, but the fibers can be stored on dry ice in a cooler for a
period of several hours (Chai and Pawliszyn, 1995), if necessary. The
gas chromatograph is configured with FID and PID detectors and a 60 m
capillary column (CPSil 5, 0.32 mm i.d., 1 µm film thickness, Varian,
Inc.) optimized for quantification of BTEX and MTBE.

[Calibration.]{.underline} The GC is calibrated in the laboratory prior
to deployment in the field, using a method described by Martos and
Pawliszyn (1997). Briefly, we constructed a standard gas mixture
generating device that consisted of a 20 L stainless steel chamber,
Hamilton syringe pump, and an air dilution system. The outside of the
chamber is covered with a heating blanket, allowing for controlling and
maintaining constant temperature in the chamber. A 20 μl gas-tight
Hamilton syringe is used to deliver the analyte mixture with a
controlled speed. An ultra-high purity air is mixed with the upcoming
liquid in a mixing tee and delivered to the chamber. By controlling the
air and liquid mixture delivery speed, the desired concentration of the
analytes can be achieved in the chamber (ranged from low ppb to ppm
levels). The chamber is allowed to reach a steady state after a minimum
of 10 volume exchanges after each alteration of gas concentration. The
concentrations of standard compounds in the calibration mixture is
verified by collecting a canister sample and analyzing it by our
standard GC/FID method.

The SPME fibers are exposed to the mixture in the chamber for an
appropriate time and then thermally desorbed in the injector of the
GC/PID/FID unit for 2 minutes at 200 C. Each fiber is exposed to the
same mixture at least three times to ensure the desired repeatability of
measurements and three different calibration mixture concentrations are
used for the GC/PID/FID system calibration. Using the SRI software
system, the calibration curve is constructed for each analyte.

[Daily calibration check.]{.underline} For the daily calibration check,
the SPME fiber will be exposed to one concentration of the calibration
mixture. We will collect several canister samples from the dilution
chamber to take these mixtures on the road in the mobile laboratory. A
small aliquot of the mixture will be placed in a 1 L Tedlar bag to allow
for the fiber exposure. The canisters could be shipped back to the DRI
laboratory for refilling them with a new calibration mixture, when the
pressure in the canister becomes too low.

### Time-Integrated Air Sample Collection and Analysis 

Time-integrated monitoring methods are used primarily for verification
of the responses of continuous instruments. The methods include canister
sampling for VOC (BTEX, 1,3-butadiene, MTBE), solid adsorbent sampling
(for ethanol and MTBE) and DNPH-coated Sep Pak cartridges sampling for
carbonyl compounds. These methods are routinely used by the DRI Organic
Analytical Laboratory (OAL) and DRI standard operating procedures (SOPs)
for sampling and analysis are available upon request**.** One-hour
samples will be collected.

[Sampling.]{.underline} 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 set-up 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.

The canister sampler uses a differential pressure flow controller to
supply air to the sampler canister. The flow rate will be checked by a
calibrated mass flow controller. 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.

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.]{.underline} 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
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 uniform 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.

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 20% 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.

[Solid adsorbent samples.]{.underline} Ethanol and MTBE 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 rather unstable and the
replicate analysis of canister samples show high degree of scatter
(Goliff and Zielinska, 2001). Thus, the solid adsorbent samples are only
necessary for quantification of ethanol. MTBE and BTEX data will be
obtained from the solid adsorbent samples to serve as a comparison with
canister data for QA purpose. 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 cartridges are tested by GC/FID for
purity prior to sampling. After cleaning, the 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.

After sampling, cartridge samples are analyzed by the thermal
desorption-cryogenic preconcentration method, followed by high
resolution gas chromatographic separation and Fourier transform
infrared/mass spectrometric detection (IRD/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.]{.underline} 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, 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 carbonate/sodium nitrite/glycerol
mixture (method developed by Dr. Koutrakis from Harvard School of Public
Health). 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
quantitation of the hydrazones (Fung and Grosjean 1981).

#  EXPERIMENTAL PLAN

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
proposed exposure study consists of two parts. 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. In the second approach, DRI
and LRRI will monitor microenvironmental and personal exposures in
various potential high-end exposure microenvironments in Atlanta,
Chicago, and Houston during summer and winter conditions. Figures 3-1
and 3-2 show the monitoring requirements for the overall study and for
Task 2, respectively. Table 3-1 shows the planned exposure matrix and
the number of samples and hours of measurements for each
microenvironment.

## Controlled In-Cabin and Residential Garage Exposure Measurements (Task 2)

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 will be made in San Antonio during June 2002
for summer fuels and during January 2003 for winter fuels according to
the following protocol.

### Procurement of Test Fuels from Houston, Chicago and Atlanta (Task 2a)

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 will be procured and
evaluated during May/June of 2002 and the three winter fuels during
December 2002. SwRI will test fuels for bulk properties and DRI will
speciate the chemical composition of each of the six blended fuels.

![](media/image2.wmf)

![](media/image2.wmf)

> **Table 3-1**

**Collection of Time-Integrated Samples for Chemical Analysis**

![](media/image3.wmf){width="9.125in" height="5.022222222222222in"}

**Table 3-1 (Continued)**

####### Collection of Time-Integrated Samples for Chemical Analysis {#collection-of-time-integrated-samples-for-chemical-analysis .unnumbered}

![](media/image4.wmf){width="8.93125in" height="3.5347222222222223in"}

**Table 3-1 (Continued)**

**Collection of Time-Integrated Samples for Chemical Analysis**

![](media/image5.wmf){width="5.829861111111111in"
height="6.822222222222222in"}

### Determination of Tailpipe and Evaporative Emissions of Test Vehicles (Task 2b)

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, O~2~
sensor, catalyst) can be reversibly disconnected to represent normal and
reasonable high-end approximations (e.g., ≥ 2 gm HC/mile exhaust) of
real world exhaust emissions. 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 would 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; non-methane hydrocarbons, NMHC;
carbon monoxide, CO; and oxides of nitrogen, NOx), carbon dioxide,
CO~2~; and speciated VOC emissions (to include MTBE, ethanol, benzene,
toluene, ethylbenzene, 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 a 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 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**

**Suggested Test Plan for Each Vehicle**

![](media/image6.wmf){width="6.346527777777778in"
height="7.116666666666666in"}

![](media/image7.wmf){width="4.646527777777778in"
height="2.183333333333333in"}**Table 3-3**

**Summary of the FTP Driving Cycle**

![](media/image8.wmf){width="6.875in" height="3.7493055555555554in"}

**F**

**Figure 3-3.** FTP Driving Cycle.

### Relationship Between Exhaust Emission Rates and In-Cabin Exposure (Task 2c) 

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 which 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
2002 and January 2003, respectively.

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 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 5 min at
"tailgating" distance, i.e., as close as safety permits, and 5 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 during the
entire test. In the future experiments we will also monitor TVOC on the
hood of the vehicle. In addition, we measure TNMHC from time-integrated
canister samples.

Table 3-4. Protocol for trailing vehicle tests

+----+-----+---------+-------+----------+----------+-----+--------+
| Ti | Sp  | Vent    | Dis   | Notes    | Co       | S   | Time   |
| me | eed | ilation | tance |          | ntinuous | PME |        |
|    |     |         |       |          |          |     | Inte   |
| mi | mph | Setting |       |          | Ins      |     | grated |
| n. |     |         |       |          | truments |     |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | h   | high    |       | ba       | Y        | 1   | 1      |
|    | igh |         |       | ckground |          |     |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | low | high    | far   | V        | Y        | 1   | 1      |
|    |     |         |       | ehicles: |          |     |        |
|    |     |         |       | Toyota   |          |     |        |
|    |     |         |       | Camry    |          |     |        |
|    |     |         |       | and      |          |     |        |
|    |     |         |       |          |          |     |        |
|    |     |         |       | Pick-up  |          |     |        |
|    |     |         |       | truck,   |          |     |        |
|    |     |         |       | in       |          |     |        |
|    |     |         |       | normal   |          |     |        |
|    |     |         |       | and      |          |     |        |
|    |     |         |       | mal      |          |     |        |
|    |     |         |       | function |          |     |        |
|    |     |         |       | mode.    |          |     |        |
|    |     |         |       |          |          |     |        |
|    |     |         |       | Fuels:   |          |     |        |
|    |     |         |       | b        |          |     |        |
|    |     |         |       | aseline, |          |     |        |
|    |     |         |       | MTBE,    |          |     |        |
|    |     |         |       | ethanol  |          |     |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | low | high    | near  |          | Y        | 1   |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | low | high    | pa    |          | Y        | 1   |        |
|    |     |         | ssing |          |          |     |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | h   | high    | far   |          | Y        | 1   |        |
|    | igh |         |       |          |          |     |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | h   | high    | near  |          | Y        | 1   |        |
|    | igh |         |       |          |          |     |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | h   | high    | pa    |          | Y        | 1   |        |
|    | igh |         | ssing |          |          |     |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | low | low     | far   |          | Y        | 1   |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | low | low     | near  |          | Y        | 1   |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | low | low     | pa    |          | Y        | 1   |        |
|    |     |         | ssing |          |          |     |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | h   | low     | far   |          | Y        | 1   |        |
|    | igh |         |       |          |          |     |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | h   | low     | near  |          | Y        | 1   |        |
|    | igh |         |       |          |          |     |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | h   | low     | pa    |          | Y        | 1   |        |
|    | igh |         | ssing |          |          |     |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | i   | low     | adj   |          | Y        | 1   | 1      |
|    | dle |         | acent |          |          |     |        |
+----+-----+---------+-------+----------+----------+-----+--------+
| 10 | i   | high    | adj   |          | Y        | 1   |        |
|    | dle |         | acent |          |          |     |        |
+----+-----+---------+-------+----------+----------+-----+--------+

### Relationship Between Evaporative Emission Rates and Exposure in a Residence With an Attached Garage (Task 2d)

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 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 time-integrated 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 alternatively over 10-minute
periods with the sampling inlet located at breathing height at least
three feet away from nearby walls in both the unvented garage and
adjacent indoor room. 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. We will measure total VOC in the garage \[with ppbRAE
photoionization (PID) detector\] before the test and the tests will be
conducted every day (excluding weekends) over the period of two weeks.

For all tests the inlet for portable and time-integrated instruments
will be placed at breathing zone height (i.e. 1.5 m above the floor).

Table 3-5. Protocol for attached garage experiments. The same vehicles
and fuels as for trailing vehicle experiment are used.

+-------+-----+-----+------+--------+------+---------+-----+-------+
| Cond  | T   | Gar | Kit  | K      | I    | Con     | S   | Integ |
| ition | ime | age | chen | itchen | nlet | tinuous | PME | rated |
|       | (m  | D   | Door | Window | Loca |         |     | Sa    |
|       | in) | oor |      |        | tion |         |     | mples |
+-------+-----+-----+------+--------+------+---------+-----+-------+
| B     | 10  | clo | cl   | closed | ga   | y       | 2   | 2     |
| ack-g |     | sed | osed |        | rage |         |     |       |
| round |     |     |      |        |      |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
|       | 10  |     |      |        | kit  | y       |     |       |
|       |     |     |      |        | chen |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
|       | 10  |     |      |        | ga   | y       |     |       |
|       |     |     |      |        | rage |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
| Hot   | 10  | clo | open | closed | kit  | y       | 2   | 2     |
| soak  |     | sed | 1min |        | chen |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
|       | 10  |     | &    |        | ga   | y       |     |       |
|       |     |     | cl   |        | rage |         |     |       |
|       |     |     | osed |        |      |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
|       | 10  |     |      |        | kit  | y       |     |       |
|       |     |     |      |        | chen |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
| Ma    | 10  | clo | cl   | closed | ga   | y       | 2   |       |
| ximal |     | sed | osed |        | rage |         |     |       |
|       |     |     |      |        |      |         |     |       |
| AER   |     |     |      |        |      |         |     |       |
| to    |     |     |      |        |      |         |     |       |
|       |     |     |      |        |      |         |     |       |
| in    |     |     |      |        |      |         |     |       |
| doors |     |     |      |        |      |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
|       | 10  |     |      |        | kit  | y       |     |       |
|       |     |     |      |        | chen |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
|       | 10  |     |      |        | ga   | y       |     |       |
|       |     |     |      |        | rage |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
| Ma    | 10  | clo | cl   | open   | kit  | y       | 2   |       |
| ximal |     | sed | osed |        | chen |         |     |       |
|       |     |     |      |        |      |         |     |       |
| AER   |     |     |      |        |      |         |     |       |
| to    |     |     |      |        |      |         |     |       |
|       |     |     |      |        |      |         |     |       |
| out   |     |     |      |        |      |         |     |       |
| doors |     |     |      |        |      |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
|       | 10  |     |      |        | ga   | y       |     |       |
|       |     |     |      |        | rage |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
|       | 10  |     |      |        | kit  | y       |     |       |
|       |     |     |      |        | chen |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
| Cold  | 10  | o   | open | closed | ga   | y       | 2   |       |
| start |     | pen | 1    |        | rage |         |     |       |
|       |     |     | min  |        |      |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
|       | 10  |     | &    |        | kit  | y       |     |       |
|       |     |     | cl   |        | chen |         |     |       |
|       |     |     | osed |        |      |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+
|       | 10  |     |      |        | ga   | y       |     |       |
|       |     |     |      |        | rage |         |     |       |
+-------+-----+-----+------+--------+------+---------+-----+-------+

##  Microenvironmental Exposure Measurements in Atlanta, Chicago, and Houston (Task 3)

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 2002 (summer test)
and January-March 2003 (winter test). Exposure measurements will be made
for up to twelve different microenvironments with three replicate
measurements for each microenvironment. Measurements in each of the
microenvironments will be taken over a period of one hour beginning at
the top of the hour. Continuous measurements of carbon monoxide,
benzene, toluene, ethylbenzene, xylenes and formaldehyde will be taken
during the entire hour. Time-integrated canister, DNPH cartridge, and
solid adsorbent (in city with ethanol-containing fuel) samples will also
be collected over the full hour unless the next sample will be collected
during a consecutive hour. In such cases, the sample will be collected
during the first 50 minutes to allow time for replacement of sampling
media. In addition, four SPME samples (for MTBE and BTEX) will be
collected during four consecutive 15-minute periods during each one-hour
exposure period. Table 3-1 shows the planned exposure matrix and the
number of samples and hours for each microenvironment.

### Exposure Diary and Script Development (Task 3a)

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 (Kleipas, 1999). This approach involves the
following steps: (1) microclimate identification, (2) quantification of
time spent performing activities in a given microclimate, 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 (EPA, 1996), exposure from these activities can
be estimated for the total population.

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. The
example of a diary is included in Appendix D.

We also will compare personal exposures with ambient measurements from
nearby local and state monitoring sites. This can be accomplished by
scheduling activities to begin on the hour and end on the hour, enabling
a direct comparison with ambient network data.

### In-cabin Exposures in Urban Microenvironments (Task 3b)

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.

1.  Parking garage (60 minutes).

2.  Downtown surface street loop characterized by an urban canyon effect
    (60 minutes).

3.  Toll plaza or crowded inspection station (60 minutes).

4.  Freeway traffic under stop-and-go conditions (60 minutes)

5.  Tunnel or covered roadway (60 min)

6.  Refueling (60 min)

In addition to continuous measurements, one integrated sample will be
collected during each one-hour exposure. Table 2-1 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 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). Carbon monoxide will be measured in
the mobile laboratory, which will trail the test vehicle in order to
compare the outdoor (roadway) ambient CO mixing ratios to in-cabin CO
for each of the three runs. The effect of varying ventilation will be
normalized to this ratio.

### Outdoor and Indoor Exposure in Urban Microenvironments (Task 3c) 

We will use scripted technicians with "luggage cart" sampling stations
to 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 by Ted Johnson and will use diaries and/or
GPS monitors to document actual exposure locations and conditions.

The exposures in each microenvironment will be monitored for
approximately one hour. We propose to repeat the measurements in each
microenvironment three times and collect time-integrated canister, DNPH
and solid adsorbent (for ethanol only) samples during each exposure
period (see Table 3-1). For all tests the inlet for portable and
time-integrated instruments will be placed at breathing zone height
(i.e. 1.5 m above the ground) and in the breathing zone of the
technician as appropriate.

### Technician Biomarker Analysis (Task 4)

Urinary MTBE/BTEX as well as breath measurements will be used as the
biomarkers 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 bio-monitoring experiments for
projected "high-end" exposures such as refueling or underground parking
garage. Urine sampling will be conducted similar to the pilot study,
with pre- and post-exposure collections of the subject's urine. The
complete time course of collection will be lengthened based on the
results of additional experiments that was conducted on June 4. Samples
will be collected and analyzed according to the protocol described in
Section 2.

### Approach for Selecting High End Microenvironments

One of the overall goals of the project is to sample high-end
microenvironments (MEs), plausibly characterized in the upper 90^th^
centiles of exposure, that result from the impacts of
exhaust/evaporative emissions from gasoline-fueled vehicles. Two
approaches to selecting high-end MEs would include urban rush-hour
sampling of high-density traffic patterns (e.g., congested roadways) and
concentrations of vehicles in enclosed spaces (e.g., underground parking
garages). Twelve categories of high-end MEs listed below (and in Tasks
3a & b of the protocol) include bulleted selection criteria that should
lead to sampling ME locations with higher levels of accumulated
emissions. Survey technicians will also use pollutant sniffers (e.g.,
hand-held CO/BTEX monitors) to sense relative peak pollutant levels
within and among these candidate locations, choosing the MEs with the
highest levels in each category for inclusion in the city-specific
sampling scripts.

1.  Congested (stop-n-go) commuter roadway (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

[Protocol]{.underline}: Prior to test, identify roadway segment that
satisfies above conditions and confirm high potential concentrations
using sniffer. Drive back and forth on the segment continuously during
the 60-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 30-minute periods under high- and low-ventilation
(vehicle windows & vents open and windows & vents closed).

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]{.underline}: Prior to test, identify roadway segment that
satisfies above conditions and confirm high potential concentrations
using sniffer. Drive back and forth on the segment continuously during
the 60-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
30-minute periods under high- and low-ventilation (vehicle windows &
vents open and windows & vents closed).

3.  Refueling (vehicle cabin)

    -   Lack of pump nozzle vapor controls, if available

    -   Peak refueling period for station

    -   Largest number of pumps

    -   Downwind direction from centroid of pump locations

    -   Location most shielded from air dispersion by topography

[Protocol]{.underline}: Prior to test, identify service station that
satisfies above conditions and use sniffer to locate refueling area
associated with highest concentrations. Park car at refueling location
and sample alternative 30-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
high-ventilation sampling period.

4.  Parking garage (vehicle cabin) above ground

    -   Rush hour 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]{.underline}: Prior to test, identify aboveground parking lot
that satisfies above conditions and use sniffer to locate parking area
within lot associated with highest concentrations. Park car at the
location and sample alternative 30-minute periods under high- and
low-ventilation (vehicle windows & vents open and windows & vents
closed).

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]{.underline}: Prior to test, identify toll plaza apron that
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 30-minute periods under high- and
low-ventilation (vehicle windows & vents open and windows & vents
closed). If not, repeatedly traverse the plaza queue during the
60-minute test period, sampling as above.

6.  Tunnel/Covered Roadway (vehicle cabin)

    -   Rush hour sampling

    -   Stop-n-go traffic flow

    -   Highest traffic density

    -   Lack of mechanical ventilation, if available

    -   Smallest enclosed volume

[Protocol]{.underline}: Prior to test, identify tunnel or covered
roadway that satisfies above conditions and use sniffer to confirm high
concentrations. Drive back and forth on enclosed roadway during the
60-minute test period maximizing minimizing 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. Sample alternative
30-minute periods under high- and low-ventilation (vehicle windows &
vents open and windows & vents closed).

7.  Refueling (self-service)

    -   Lack of pump nozzle vapor controls, if available

    -   Peak refueling period for station

    -   Largest number of pumps

    -   Downwind direction from centroid of pump locations

    -   Location most shielded from air dispersion by topography

> [Protocol]{.underline}: Prior to test, identify service station that
> satisfies above conditions and use sniffer to locate refueling area
> associated with highest concentrations. Park car at refueling location
> and sample alternative 30-minute periods under high- and
> low-ventilation (vehicle windows & vents open and windows & vents
> closed). With sampling inlet in the breathing zone, refuel the vehicle
> over a 1 to 2-minute active refueling period at the mid-point of the
> high-ventilation sampling period. Return to the vehicle cabin for the
> rest of the 60-minute sampling period. During refueling, maintain
> manual control of the nozzle (i.e., use an unlatched nozzle) and stand
> downwind of the vehicle fuel tank inlet. Once per week, biomarker
> samples will be collected from the technician performing this
> self-service refueling 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]{.underline}: Prior to test, identify roadway segment with
> sidewalks that satisfies above conditions and identify high
> 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 60-minute sampling period. Walk within
> three feet of curb.

9.  Parking garage (underground)

    -   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]{.underline}: Prior to test, identify underground parking
> lot that satisfies above conditions and use sniffer to locate parking
> area within garage associated with highest concentrations. Park car at
> location during 60-minute rush-hour test with front windows down and
> vents open. Sample 10 minutes in cabin during entry and parking of
> vehicle. Close vehicle windows. With cart inlet in breathing zone,
> sample next 10-minute period exiting vehicle and making way to street
> level exit; repeating sampling in the reverse direction for the next
> 10-minute period. Return to closed vehicle cabin for next 10-minute
> period. Open vehicle windows and sample during final 10-minute period
> exiting the garage and paying toll.

10. Bus stop

    -   Rush hour sampling on roadway parallel to wind direction

    -   High traffic density route

    -   Located on traffic island/median strip

    -   Downwind direction near high density traffic intersection

    -   In urban canyon

> [Protocol]{.underline}: 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 60-minute test.

11. 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]{.underline}: Prior to test, identify tollbooth that
> satisfies above conditions and confirm high concentrations using
> sniffer. With cart inlet in the breathing zone, sample in the booth
> and externally within three feet of booth door or window (conditions
> permitting) alternatively for 30-minute intervals during the 60-minute
> test.

12. Auditorium/stadium external parking lots

    -   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]{.underline}: Prior to test, identify stadium parking lot
> that satisfies above conditions and use sniffer to locate parking area
> within lot associated with highest concentrations. Sample during
> 60-minute test with front windows down and vents open. Sample 20
> minutes in cabin during entry and parking of vehicle beginning at the
> time that the parking lot is approximately half-filled to capacity
> (usually about one hour before the start of the sports/exhibition
> event - e.g., professional baseball, football, basketball home game,
> ice-skating event). With cart inlet in breathing zone, sample next
> 20-minute period outside near rear of parked vehicle with open
> hatch/trunk to simulate 'tailgate' picnic. Close vehicle
> windows/doors. With cart inlet in breathing zone, sample next
> 20-minute period making way through parking lot to stadium entrance.
> Reverse this process in a second ME test to sample exposures during
> exiting of the parking lot beginning near the end of the sports event.
> With cart inlet in breathing zone, sample during initial 20-minute
> sampling period making way through parking lot to parking location.
> Stand near the rear of the parked vehicle during the next 20-minute
> period to simulate packing up the vehicle after the game. Open vehicle
> windows & vents. Sample during the final 20-minute period in the
> vehicle cabin making way from the parking location to the parking lot
> exit.
>
> Appendices A, B and C contain the draft protocols for sampling in
> Houston, Atlanta, and Chicago, respectively.

## Meteorology (Task 5)

For portions of the sampling periods involving stationary activities, a
portable weather station will be set up at an adjacent location. 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.

The local on-site measurements using a portable meteorological station
will be made by field participants in the experiment. Remaining phases
will be undertaken by Dr. Kelly Redmond, Regional Climatologist, of the
Western Regional Climate Center (WRCC). 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.

## Data Analysis (Task 6)

Task 6a: 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 time-integrated 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.

-   Compare sum of designated species to TVOC.

-   Determine variations in fractions of benzene, toluene, ethylbenzene,
    xylenes, MTBE, and ethanol, formaldehyde, acetaldehyde to TVOC and
    significant differences in the ratios among microenvironments.

-   Prepare scatterplots of CO with TVOC, BTEX, 1,3-butadiene, MTBE,
    ethanol, formaldehyde and acetaldehyde.

-   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.

Task 6b: 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.

```{=html}
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-   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.

Task 6c: 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, CH~3~CHO, EtOH, TVOC and CO during the initial
    and final loops without the test vehicle.

-   Subtract the average time-integrated background values from the
    corresponding time integrated exposure levels for the default
    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.

Task 6d: 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.

Task 6e: Quantify personal 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.

-   Compare time-integrated exposure levels measured in the
    microenvironments that were investigated in Task 3 among the three
    cities and season. Quantify absolute differences for each designated
    species and differences normalized to concurrent CO data.

-   Characterize the extremes in exposure levels during the test
    periods.

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-   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).

Task 6f: Quantify personal exposures scripted activity.

-   Process GPS data and develop a log of the measurements of scripted
    worker exposures with respect time and location.

-   Compare time-integrated exposure levels measured in the
    microenvironments that were investigated in Task 4 among the three
    cities and season. Quantify absolute differences for each designated
    species.

-   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. Relative contributions will be determined by
    the Chemical Mass Balance (CMB) receptor modeling if the optional
    speciation profiles for exhaust and evaporative are obtained. The
    default approach is only applicable to cities with oxygenated fuels,
    while the CMB approach can also be applied to the city with
    conventional gasoline.

-   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.

## Reporting

This task will require completion of the following:

-   Interim report after completion of the pilot study

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

-   Final protocol (after incorporating protocol changes)

-   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' comments)

###  {#section .unnumbered}

#  PROJECT SCHEDULE AND DELIVERABLES

The following is list of major milestones and deliverables.

1.  Pilot Study 2/25/02 to 3/1/02

2.  Pilot study report 4/12/02

3.  Draft Exposure Protocol and Study Plan 4/19/02

4.  Final Exposure Protocol and Study Plan 5/30/02

5.  Controlled Exposure Tests in San Antonio (summer fuels) 6/17/02 to
    7/03/02

6.  Urban Exposure Measurements in three cities (summer) 7/08/02 to
    8/30/02

7.  Controlled Exposure Tests in San Antonio (winter fuels) 1/06/03 to
    1/24/02

8.  Urban Exposure Measurements in three cities (winter) 1/27/03 to
    3/21/03

9.  Draft Final Report 6/30/03

10. Final Report ten days after receipt of comments

#  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.

Fustinoni, S., R. Giampiccolo, S. Pulvirenti, M. Buratti, and A. Colombi
(1999). Headspace solid-phase microextraction for the determination of
benzene, toluene, ethylbenzene and xylenes in urine. *J. Chromatogr.*
**B 723**: 105-115.

Goliff, W.S. and B. Zielinska (2001). Long-Term Stability of Oxygenated
Compounds in

Electropolished Canisters, Paper #403, presented at the 94^th^ N+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

Kleipas, 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.

Lee, C.W. and C.P. Weisel (2001). Toxicokinetics of Human Exposure to
Methyl

tertiary-butyl ether (MTBE) Following Short-Term Controlled Exposures.
J.

Exposure Anal. And Environ. Epi., 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., *J. Air and Waste Management*, V. 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.

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, *Journal of the Air
&*

*Waste Management Association,* **50:**371-377.

Vayghani, S. A., C. Weisel, (1999) The MTBE air concentrations in the
cabin of

automobiles while fueling, *Journal of Exposure Analysis and
Environmental*

*Epidemiology,* **9**, 261-267.

####### APPENDIX A {#appendix-a .unnumbered}

**Exposure Protocol and Study Plan for the Section 211(B) Tier 2 High
End Exposure Screening Study of Baseline and Oxygenated Gasoline**

**- Summer 2002 Sampling Plan for Houston**

DRAFT

Prepared for

AMERICAN PETROLEUM INSTITUTE

1220 L Street

Washington, DC 20005-4070

Prepared by

DESERT RESEARCH INSTITUTE

2215 Raggio Parkway

Reno, NV 89512

July 1, 2002

**INTRODUCTION**

This sampling plan specifies the details for the field measurement
program that will be carried out in Houston, Texas during the summer of
2002 as part of a screening study of the high-end exposures to baseline
and oxygenated gasoline. It specifies the 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 June 13, 2002 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 99^th^ percentile exposure levels within each type of
microenvironment. Due to the scope of this study, it will not be
possible to fully characterize (by measurements) the range of exposures
that include the 99^th^ percentile. However, we considered available
surrogate parameters for emission levels and dispersion to select
sampling times and locations with the greatest potential for higher
exposures. These emission surrogates include traffic counts, and diurnal
variations in average highway speeds, length of queues at toll plazas,
number of cars refueling or entering and exiting parking garages.
Surrogates for dispersion include wind roses and diurnal variations in
temperature. Measurements in microenvironments with unrestricted
dispersion will be made in the early morning or evening 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 2002 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 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. Comparisons of the ppbRAE data with integrated canister and
DNPH samples are currently underway. 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, much 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 high 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 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
westside 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 aboveground 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).

![](media/image9.wmf){width="6.375694444444444in"
height="3.904166666666667in"}

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.

![](media/image10.wmf){width="6.308333333333334in"
height="3.8722222222222222in"}

Figure 2. Tour of downtown Houston.

![](media/image11.wmf){width="6.308333333333334in"
height="3.8722222222222222in"}

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

![](media/image12.wmf){width="6.180555555555555in" height="3.78125in"}

Figure 4. Minute Maid Park at the end of a ballgame on evening of June
21, 2002.

![](media/image13.wmf){width="6.315277777777778in"
height="3.863888888888889in"}

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

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

![](media/image14.png){width="6.5in" height="4.875in"}

Figure 6. Frequencies of wind speed and direction in Houston during
July.

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.

**DESCRIPTIONS OF MICROENVIRONMENTS (ME) AND SAMPLING PROTOCOL**

1.  In vehicle: commuter rush hour in stop-and-go traffic (ME1)

Make two roundtrips 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. Each roundtrip will take 25 to 30 minutes with
the inbound and outbound directions of the freeway segment taking 16 to
20 minutes and 8 to 10 minutes, respectively. Use high ventilation
conditions (window and vent open, AC on during summer and heater on
during winter) during the first roundtrip and low ventilation (windows
and vent closed, AC on during summer and heater on during winter) during
the second roundtrip. 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 inbound trips.

Sample in-cabin air at driver's breathing zone continuously with a KORE
MS 200, Langan T15, and Alpha Omega HCHO analyzer and collect one set of
canister and DNPH samples integrated over the entire hour. Collect three
SPME samples, one for each of the two inbound trips (approximately 15
minutes) and one during the first outbound trip (approximately 8
minutes). Begin each SPME sample when the sampling van has entered the
freeway and is in the middle lane and stop the sample just before
exiting the freeway at the end of the trip. Sample the outside air with
a portable PID monitor during the entire hour without compromising the
ventilation condition in the cabin. The effect of high and low
ventilation conditions will be normalized to the PID data. The portable
PID monitor replaces the second CO analyzer (in the trailing mobile
laboratory) that is specified in the Exposure Protocol and Study Plan of
June 13, 2002. Monitor and record the van's position (GPS), and in-cabin
temperature and relative humidity. Ancillary data from the mobile
laboratory include ambient CO, wind speed and direction, temperature and
relative humidity. The mobile laboratory will remain at the RV Park
during these measurements. 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 ½ Lang. Check wind data 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.

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 US-290 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.

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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.

Make multiple trips during a one-hour 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 30
minutes and low ventilation (windows and vent closed, AC on during
summer and heater on during winter) during second 30 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 a KORE
MS 200, Langan T15, and Alpha Omega HCHO analyzer and collect one set of
canister and DNPH samples integrated over the entire hour. Collect three
SPME samples, two 15-minute samples during the high ventilation
condition and one sample during the first 15 minutes of the low
ventilation condition. Sample the outside air with a portable PID
monitor 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. Ancillary data from the
mobile laboratory include ambient CO, wind speed and direction,
temperature and relative humidity. The mobile laboratory will remain at
the RV Park during these measurements. 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.

Park sampling van at refueling location and sample alternate 30-minute
periods under high and low ventilation. 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, and Alpha
Omega HCHO analyzer and collect one set of canister and DNPH samples
integrated over the entire hour. Collect three SPME samples, two
15-minute samples during the high ventilation sampling period and one
15-minute sample at the midpoint of the low ventilation sampling period.
Sample the outside air with a portable PID monitor during the entire
hour without compromising the ventilation condition in the cabin.
Monitor and record the in-cabin temperature and relative humidity.
Ancillary data from the mobile laboratory include ambient CO, wind speed
and direction, temperature and relative humidity. The mobile laboratory
will remain at the RV Park during these measurements.

4.  In vehicle: parking garage (ME4)

Drive within a parking garage for one hour. Use high ventilation
conditions (window and vent open, AC on during summer and heater on
during winter) during first 30 minutes and low ventilation (windows and
vent closed, AC on during summer and heater on during winter) during
second 30 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, and Alpha Omega HCHO analyzer and collect one set of
canister and DNPH samples integrated over the entire hour. Collect three
SPME samples, two 15-minute samples during the high ventilation
condition and one sample during the first 15 minutes of the low
ventilation condition. Sample the outside air with a portable PID
monitor during the entire hour without compromising the ventilation
condition in the cabin. Monitor and record the in-cabin temperature and
relative humidity. Ancillary data from the mobile laboratory include
ambient CO, wind speed and direction, temperature and relative humidity.
The mobile laboratory will remain at the RV Park during these
measurements.

5.  In vehicle: toll plaza (ME5)

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. Obtain
information regarding peak traffic periods and average queue times from
the gate operator. Use high ventilation conditions (window and vent
open, AC on during summer and heater on during winter) during first 30
minutes and low ventilation (windows and vent closed, AC on during
summer and heater on during winter) during second 30 minutes.

Sample in-cabin air at driver's breathing zone continuously with a KORE
MS 200, Langan T15, and Alpha Omega HCHO analyzer and collect one set of
canister and DNPH samples integrated over the entire hour. Collect three
SPME samples, one 15-minute samples each during midpoint of the high
ventilation and the midpoint of the low ventilation sampling period, and
one sample during time spent in the queue. Sample the outside air with a
portable PID monitor 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.
Ancillary data from the mobile laboratory include ambient CO, wind speed
and direction, temperature and relative humidity. The mobile laboratory
will be located on-site just south of the south entrance to the Tunnel.
There should be space just south of the rotary. Park the RV with the
generator exhaust downwind relative to the inlet for the CO monitor.

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. Conduct samplng in the
morning to accommodate the collection of biomarker samples.

Park the van downwind from the centroid of the pump locations. With
sampling inlet in the breathing zone, refuel the vehicle over a 1 to 2
minute active refueling period. During refueling, maintain manual
control of the nozzle and stand downwind of the vehicle fuel tank inlet.
Ask to refuel other vehicles on the other side of the pump island as the
opportunity arises or stand as close as possible to the person refueling
the vehicle. Sample the breathing zone continuously with a KORE MS 200,
Langan T15, Alpha Omega HCHO analyzer, and portable PID monitor and
collect one set of canister and DNPH samples integrated over the entire
hour. Collect three SPME samples during three separate active refueling
periods. Record the ambient temperature and relative humidity. Ancillary
data from the mobile laboratory include ambient CO, wind speed and
direction, temperature and relative humidity. The mobile laboratory will
remain at the RV Park during these measurements.

8.  Outdoor: sidewalk near high-density traffic (ME8)

Conduct sidewalk sampling 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. Start at this location and walk around the block. After the
first trip around the block, remain in the covered section of Polk
Street for at least 15 minutes, then continue the walk around the block.
Sampling should be conducted during the morning and afternoon commute
periods and during the noon hour.

Sample the breathing zone continuously with a KORE MS 200, Langan T15,
Alpha Omega HCHO analyzer, and portable PID monitor and collect one set
of canister and DNPH samples integrated over the entire hour. Collect
three SPME samples, two samples during the walk around the block and one
sample at the covered section of Polk Street. Record the ambient
temperature and relative humidity. Ancillary data from the mobile
laboratory include ambient CO, wind speed and direction, temperature and
relative humidity. The mobile laboratory will remain at the RV Park
during these measurements.

9.  Outdoor: bus stop (ME9)

Sample the ambient air at a bus stop in downtown Houston during the
morning and afternoon commute periods.

10. Outdoor: stadium parking lot (ME10)

Sample for 1 hour at the end of Houston Astros baseball game Games are
scheduled on July 11 (Thu) at 7:05 PM, July 12 (Fri) at 7:05 PM, July 13
(Sat) at 12:15 PM, July 14 (Sun) at 1:35 PM, July 15 (Mon) at 7:05 PM,
and July 16 (Tue) at 3:05 PM. Because the atmosphere is more stable in
the evening, night games are preferable to day games. Sample ambient air
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
south exit of parking lot C and a walk along the sidewalk toward the
Park and back

Sample the breathing zone continuously with a KORE MS 200, Langan T15,
Alpha Omega HCHO analyzer, and portable PID monitor and collect one set
of canister and DNPH samples integrated over the entire hour. Collect
three SPME samples, two samples at the exit of Lot C and one sample
during the walk. Record the ambient temperature and relative humidity.
Ancillary data from the mobile laboratory include ambient CO, wind speed
and direction, temperature and relative humidity. The mobile laboratory
will remain at the RV Park during these measurements.

11. In-doors: underground parking garage (ME11)

Sample the ambient air in an underground parking garage with a sampling
cart for a 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 only once on Tuesday
July 9 at 7:30 p.m. We propose three separate one-hour sampling periods
on that day. The first will be from 4:00 to 5:00 p.m. when the office
workers leave the complex (cold start emissions). The second is from
7:00 to 8:00 p.m. when the basketball fans arrive for the game (hot
stabilized exhaust and hot soak emissions) and the final sampling period
will be from after the game (cold start emissions).

Sample the breathing zone continuously with a KORE MS 200, Langan T15,
Alpha Omega HCHO analyzer, and portable PID monitor and collect one set
of canister and DNPH samples integrated over the entire hour. Collect
four SPME samples with each sampling period lasting 15 minutes. Record
the ambient temperature and relative humidity. Ancillary data from the
mobile laboratory include ambient CO, wind speed and direction,
temperature and relative humidity. The mobile laboratory will remain at
the RV Park during these measurements.

12. Outdoors: toll booth (ME12)

Sample the ambient air at the Ship Channel Bridge toll plaza for one
hour from 7:00 to 8:00 a.m. 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,
Alpha Omega HCHO analyzer, and portable PID monitor and collect one set
of canister and DNPH samples integrated over the entire hour. Collect
four SPME samples with each sampling period lasting 15 minutes. Record
the ambient temperature and relative humidity. Ancillary data from the
mobile laboratory include ambient CO, wind speed and direction,
temperature and relative humidity. The mobile laboratory will be located
on-site near the toll plaza office building. Park the RV with the
generator exhaust downwind relative to the inlet for the CO monitor. .

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 schedule for the Houston summer sampling program is summarized
in Table 1. In order to stay on project schedule as much as possible,
sampling will be conducted on weekends in case we encounter unsuitable
meteorological conditions on scheduled sampling days. Possible
alternative microenvironments on weekends include outdoor cafes in the
theater district in downtown Houston, parking garages at malls, sporting
events or other special event.

**Table 1**

**Daily Sampling Schedule for Houston**

![](media/image15.wmf){width="6.55625in" height="6.35in"}

**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 2002 Sampling Plan for Atlanta**

DRAFT

Prepared for

AMERICAN PETROLEUM INSTITUTE

1220 L Street

Washington, DC 20005-4070

Prepared by

DESERT RESEARCH INSTITUTE

2215 Raggio Parkway

Reno, NV 89512

July 26, 2002

**INTRODUCTION**

This sampling plan specifies the details for the field measurement
program that will be carried out in Atlanta, GA during the summer of
2002 as part of a screening study of the high-end exposures to baseline
and oxygenated gasoline. It specifies the 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 June 13, 2002 Exposure Protocol and Study
Plan, which describes the proposed measurement methods and rationale for
their selection.

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 I-75 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. Comparisons of the
ppbRAE data with integrated canister and DNPH samples are currently
underway. For the purposes of the survey of microenvironments in
Houston, 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]{.underline}

<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**

13. In vehicle: commuter rush hour in stop-and-go traffic (ME1)

Drive 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. Marietta Parkway
to downtown Atlanta. Drive the opposite direction during the evening
rush hour. Use high ventilation conditions (window and vent open, AC on
during summer and heater on during winter) during the first 30 minutes
and low ventilation (windows and vent closed, AC on during summer and
heater on during winter) during the second 30 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.

Sample in-cabin air at driver's breathing zone continuously with a KORE
MS 200, Langan T15, and Alpha Omega HCHO analyzer and collect one set of
canister and DNPH samples integrated over the entire hour. Collect three
SPME samples, two 15-minute period during the high ventilation condition
and one 15-minute period during the midpoint of the low ventilation
condition. Sample the outside air with a portable PID monitor during the
entire hour without compromising the ventilation condition in the cabin.
The effect of high and low ventilation conditions will be normalized to
the PID data. Monitor and record the van's position (GPS), and in-cabin
temperature and relative humidity. Ancillary data from the mobile
laboratory include ambient CO, wind speed and direction, temperature and
relative humidity. The mobile laboratory will remain at the RV Park
during these measurements. 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 Supersite at 829 Jefferson St.
NW.

14. In vehicle: urban street canyons (ME2)

Make multiple trips during a one-hour period along a surface-street loop
in downtown Atlanta bordered by Peachtree Street NW, Forsyth/Carnegie,
Spring Steet 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 30 minutes and low ventilation (windows and
vent closed, AC on during summer and heater on during winter) during
second 30 minutes. Drive at or near the end of a pack of vehicles at
stop lights 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 KORE
MS 200, Langan T15, and Alpha Omega HCHO analyzer and collect one set of
canister and DNPH samples integrated over the entire hour. Collect three
SPME samples, two 15-minute samples during the high ventilation
condition and one 15-minute sample during the midpoint of the low
ventilation condition. Sample the outside air with a portable PID
monitor 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.

15. In vehicle: refueling (ME3)

Sample for one hour 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 sampling van at the center downwind pump of the center pump
station island and sample alternate 30-minute periods under high and low
ventilation. Sample in-cabin air at driver's breathing zone continuously
with a KORE MS 200, Langan T15, and Alpha Omega HCHO analyzer and
collect one set of canister and DNPH samples integrated over the entire
hour. Collect three SPME samples, two 15-minute samples during the high
ventilation sampling period and one 15-minute sample at the midpoint of
the low ventilation sampling period. Sample the outside air with a
portable PID monitor during the entire hour without compromising the
ventilation condition in the cabin. Monitor and record the in-cabin
temperature, relative humidity, and wind speed. Note the number of
gallons dispensed.

16. In vehicle: parking garage (ME4)

Drive within a parking garage for one hour. Use high ventilation
conditions (window and vent open, AC on during summer and heater on
during winter) during first 30 minutes and low ventilation (windows and
vent closed, AC on during summer and heater on during winter) during
second 30 minutes. Potential garages include Colony Square parking
garage at Peachtree Street and 14^th^ Street in Midtown Atlanta during
the morning and evening commute period and prior to and after the
Atlanta Falcons' pre-season football game at the Georgia Dome parking
garage on the evening of August 9.

Sample in-cabin air at driver's breathing zone continuously with a KORE
MS 200, Langan T15, and Alpha Omega HCHO analyzer and collect one set of
canister and DNPH samples integrated over the entire hour. Collect three
SPME samples, two 15-minute samples during the high ventilation
condition and one sample during the first 15 minutes of the low
ventilation condition. Sample the outside air with a portable PID
monitor during the entire hour without compromising the ventilation
condition in the cabin. Monitor and record the in-cabin temperature and
relative humidity. Ancillary data from the mobile laboratory include
ambient CO, wind speed and direction, temperature and relative humidity.

17. In vehicle: toll plaza (ME5)

Sample during the morning commute period between 0700 and 0800 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 KORE MS 200, Langan
T15, and Alpha Omega HCHO analyzer and collect one set of canister and
DNPH samples integrated over the entire hour. Collect three SPME
samples, one 15-minute samples each during midpoint of the high
ventilation and the midpoint of the low ventilation sampling period, and
one sample during time spent in the queue. Sample the outside air with a
portable PID monitor 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.

18. 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.

19. Outdoor: refueling vehicle (ME7)

Sample for one hour 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. With
sampling inlet in the breathing zone, refuel the vehicle over a 1 to 2
minute active refueling period. During refueling, maintain manual
control of the nozzle and stand downwind of the vehicle fuel tank inlet.
Ask to refuel other vehicles on the other side of the pump island as the
opportunity arises or stand as close as possible to the person refueling
the vehicle. Sample the breathing zone continuously with a KORE MS 200,
Langan T15, Alpha Omega HCHO analyzer, and portable PID monitor and
collect one set of canister and DNPH samples integrated over the entire
hour. Collect three SPME samples during three separate active refueling
periods. Record the ambient temperature and relative humidity. Ancillary
data from the mobile laboratory include ambient CO, wind speed and
direction, temperature, relative humidity, and wind speed. The mobile
laboratory will remain at the RV Park during these measurements. Note
the number of gallons of fuel dispensed. Urine samples are also
collected for this microenvironment in accordance with the study
protocol.

20. 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 KORE MS 200, Langan T15,
Alpha Omega HCHO analyzer, and portable PID monitor and collect one set
of canister and DNPH samples integrated over the entire hour. Collect
three SPME samples, two samples during the walk around the block and one
sample at the covered section of Polk Street. Record the ambient
temperature and relative humidity. Ancillary data from the mobile
laboratory include ambient CO, wind speed and direction, temperature,
relative humidity, wind speed and direction. .

21. Outdoor: bus stop (ME9)

Combined with ME8.

22. Outdoor: stadium parking lot (ME10)

Sample for 1 hour at the end of Atlanta Braves baseball game Games are
scheduled on July 27 (Sat) at 1:15 PM, July 28 (Sun) at 1:05 PM, July 30
(Tue) at 7:35 PM, July 31 (Wed) at 7:05 PM, Aug 1 (Thu) at 7305 PM, Aug
2 (Fri) at 7:35 PM, Aug 3 (Sat) at 1:15 PM, Aug 4 and (Sun) at 8:05 PM.
Because the atmosphere is more stable in the evening, night games are
preferable to day games. Sample ambient air with a sampling cart for a
one-hour period at the end of the game with 15-minute sampling times
alternating between a downwind fixed location at the south exit of the
green parking and a walk along the sidewalk toward the Park and back

Sample the breathing zone continuously with a KORE MS 200, Langan T15,
Alpha Omega HCHO analyzer, and portable PID monitor and collect one set
of canister and DNPH samples integrated over the entire hour. Collect
three SPME samples, two samples at the exit of Lot C and one sample
during the walk. Record the ambient temperature and relative humidity.
Ancillary data from the mobile laboratory include ambient CO, wind speed
and direction, temperature, relative humidity, wind speed and direction
at the site.

23. Underground parking garage (ME11)

Sample the ambient air in the Colony Square underground parking garage
(Peachtree and 14^th^ Streets) for a one hour from 5:00 to 6:00 p.m.
when office workers leave the complex (cold start emissions). Sample at
exit queue and ramps. Measure temperature, humidity and ventilation
velocities.

Sample the breathing zone continuously with a KORE MS 200, Langan T15,
Alpha Omega HCHO analyzer, and portable PID monitor and collect one set
of canister and DNPH samples integrated over the entire hour. Collect
four SPME samples with each sampling period lasting 15 minutes. Record
the ambient temperature and relative humidity. Ancillary data from the
mobile laboratory include ambient CO, wind speed and direction,
temperature and relative humidity. The mobile laboratory will remain at
the RV Park during these measurements.

24. 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. The southbound lanes are
accessed by an underground tunnel. 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,
Alpha Omega HCHO analyzer, and portable PID monitor and collect one set
of canister and DNPH samples integrated over the entire hour. Collect
four SPME samples with each sampling period lasting 15 minutes. Record
the ambient temperature and relative humidity. Ancillary data from the
mobile laboratory include ambient CO, wind speed and direction,
temperature and relative humidity. The mobile laboratory will be located
on-site near the toll plaza office building. Park the RV with the
generator exhaust downwind relative to the inlet for the CO monitor. .

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.

25. Trailing high emitters (ME12)

Attempt to trail high emitters in Atlanta locations with higher
fractions of high emitters.

**DAILY SAMPLING SCHEDULE**

The daily schedule for the Atlanta summer sampling program is summarized
in Table 1. In order to stay on project schedule as much as possible,
sampling will be conducted on weekends in case we encounter unsuitable
meteorological conditions on scheduled sampling days.

**Table 1**

**Daily Sampling Schedule for Atlanta**

![](media/image16.wmf){width="6.465972222222222in"
height="7.677777777777778in"}

**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 - Sampling Plan for Chicago**

DRAFT

Prepared for

AMERICAN PETROLEUM INSTITUTE

1220 L Street

Washington, DC 20005-4070

Prepared by

DESERT RESEARCH INSTITUTE

2215 Raggio Parkway

Reno, NV 89512

August 21, 2002

**INTRODUCTION**

This sampling plan specifies the details for the field measurement
program that will be carried out in Chicago, Il during the summer of
2002 or 2003 and winter 2002/3 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 June 13, 2002 Exposure Protocol and
Study Plan, which describes the proposed measurement methods and
rationale for their selection.

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 PGM-7240
(ppbRAE) portable PID monitor and Langan Products Inc. T15d were used to
continuously monitor ambient VOC and CO levels, respectively, in several
of the microenvironments. For the purposes of the survey of
microenvironments in Chicago, the PID detector 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 80^th^
Avenue), which is about 20 miles southeast of Downtown Chicago. Our
search for some microenvironments such as service stations, vehicle
inspection stations, and congested freeway was focused in this general
area.

**DESCRIPTIONS OF MICROENVIRONMENTS (ME) AND PROPOSED SAMPLING
PROTOCOL**

26. 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 30 minutes. Use high ventilation conditions (window and
vent open, AC on during summer and heater on during winter) during the
first 30 minutes 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 30 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 30
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

Sample in-cabin air at driver's breathing zone continuously with a KORE
MS 200, Langan T15, API CO analyzer, and Alpha Omega HCHO analyzer and
collect one set of canister and DNPH samples integrated over the entire
hour. Collect three SPME samples, two 15-minute period during the high
ventilation condition and one 15-minute period during the midpoint of
the low ventilation condition. Sample the outside air with a portable
PID monitor during the entire hour without compromising the ventilation
condition in the cabin. The effect of high and low ventilation
conditions will be normalized to the PID data. Monitor and record the
van's position (GPS), and in-cabin temperature and relative humidity.
Relevant data collected by the Illinois EPA include CO and
meteorological data at the CTA Building monitoring station at 320 S.
Franklin.

27. In vehicle: urban street canyons (ME2)

Make multiple trips during a one-hour 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 30 minutes
and low ventilation (windows and vent closed, AC on during summer and
heater on during winter) during second 30 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 a KORE
MS 200, Langan T15, API CO analyzer, and Alpha Omega HCHO analyzer and
collect one set of canister and DNPH samples integrated over the entire
hour. Collect three SPME samples, two 15-minute samples during the high
ventilation condition and one 15-minute sample during the midpoint of
the low ventilation condition. Sample the outside air with a portable
PID monitor 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.

28. In vehicle: refueling (ME3)

Sample for one hour at the Gas City (80^th^ Avenue just north of I-80)
or Speedway (Harlem Avenue just north of I-80) service stations in
Tinley Park. Conduct sampling during the peak or near-peak refueling
periods for the station as indicated by service station personnel.

Park the sampling van at the center downwind pump of the center pump
station island and sample alternate 30-minute periods under high and low
ventilation. Sample in-cabin air at driver's breathing zone continuously
with a KORE MS 200, Langan T15, API CO analyzer and Alpha Omega HCHO
analyzer and collect one set of canister and DNPH samples integrated
over the entire hour. Collect three SPME samples, two 15-minute samples
during the high ventilation sampling period and one 15-minute sample at
the midpoint of the low ventilation sampling period. Sample the outside
air with a portable PID monitor during the entire hour without
compromising the ventilation condition in the cabin. Monitor and record
the in-cabin temperature, relative humidity, and wind speed. Note the
number of gallons dispensed.

29. In vehicle: parking garage (ME4)

Drive within a parking garage for one hour. Use high ventilation
conditions (window and vent open, AC on during summer and heater on
during winter) during first 30 minutes and low ventilation (windows and
vent closed, AC on during summer and heater on during winter) during
second 30 minutes. 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 KORE
MS 200, Langan T15, and Alpha Omega HCHO analyzer and collect one set of
canister and DNPH samples integrated over the entire hour. Collect three
SPME samples, two 15-minute samples during the high ventilation
condition and one sample during the first 15 minutes of the low
ventilation condition. Sample the outside air with a portable PID
monitor during the entire hour without compromising the ventilation
condition in the cabin. Monitor and record the in-cabin temperature and
relative humidity. Ancillary data from the mobile laboratory include
ambient CO, wind speed and direction, temperature and relative humidity.

30. In vehicle: toll plaza (ME5)

Sample during the morning commute period between 0700 and 0800 on
tollways with high traffic volume and higher fraction of time spent at
toll plazas (e.g., exit with ramps in both directions within short
distances before and after the toll plaza). Potential plazas include
82^nd^ Street (southbound)/83^rd^ Street (northbound) and Cermak Road
(all traffic) on the Tri-State Tollway (I-294) and the York Road (all
traffic) on the East-West Tollway (I-88). Sample in-cabin air at
driver's breathing zone continuously with a KORE MS 200, Langan T15, API
CO analyzer, and Alpha Omega HCHO analyzer and collect one set of
canister and DNPH samples integrated over the entire hour. Collect three
SPME samples, one 15-minute samples each during midpoint of the high
ventilation and the midpoint of the low ventilation sampling period, and
one sample during time spent in the queue. Sample the outside air with a
portable PID monitor 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.

31. In vehicle: tunnel (ME6)

There are no tunnels in Chicago. There are freeway overpasses (see #1).

32. Outdoor: refueling vehicle (ME7)

Sample for one hour at the Gas City (80^th^ Avenue just north of I-80)
or Speedway (Harlem Avenue just north of I-80) service stations in
Tinley Park. Conduct sampling during the peak or near-peak refueling
periods for the station as indicated by service station personnel.

Park the van downwind from the centroid of the pump locations. With
sampling inlet in the breathing zone, refuel the vehicle over a 1 to 2
minute active refueling period. During refueling, maintain manual
control of the nozzle and stand downwind of the vehicle fuel tank inlet.
Ask to refuel other vehicles on the other side of the pump island as the
opportunity arises or stand as close as possible to the person refueling
the vehicle. Sample the breathing zone continuously with a KORE MS 200,
Langan T15, Alpha Omega HCHO analyzer, and portable PID monitor and
collect one set of canister and DNPH samples integrated over the entire
hour. Collect three SPME samples during three separate active refueling
periods. Record the ambient temperature and relative humidity. Ancillary
data from the mobile laboratory include ambient CO, wind speed and
direction, temperature, relative humidity, and wind speed. The mobile
laboratory will remain at the RV Park during these measurements. Note
the number of gallons of fuel dispensed. Urine samples are also
collected for this microenvironment in accordance with the study
protocol.

33. 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 should be conducted during the morning periods and
during the noon hour.

Sample the breathing zone continuously with a KORE MS 200, Langan T15,
Alpha Omega HCHO analyzer, and portable PID monitor and collect one set
of canister and DNPH samples integrated over the entire hour. Collect
three SPME samples, two samples during the walk around the block and one
sample at the covered section of Polk Street. Record the ambient
temperature and relative humidity. Ancillary data from the mobile
laboratory include ambient CO, wind speed and direction, temperature,
relative humidity, wind speed and direction. .

34. Outdoor: bus stop (ME9)

Combined with ME8.

35. Outdoor: stadium parking lot (ME10)

Sample for 1 hour 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. Sample ambient air
with a sampling cart for a one-hour period at the end of the game with
15-minute sampling times alternating between a downwind fixed location
at the south exit of the green parking and a walk along the sidewalk
toward the Park and back

Sample the breathing zone continuously with a KORE MS 200, Langan T15,
Alpha Omega HCHO analyzer, and portable PID monitor and collect one set
of canister and DNPH samples integrated over the entire hour. Collect
three SPME samples, two samples at the exit of Lot C and one sample
during the walk. Record the ambient temperature and relative humidity.
Ancillary data from the mobile laboratory include ambient CO, wind speed
and direction, temperature, relative humidity, wind speed and direction
at the site.

36. Underground parking garage (ME11)

Sample in an underground parking garage for a one hour from 5:00 to 6:00
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,
Alpha Omega HCHO analyzer, and portable PID monitor and collect one set
of canister and DNPH samples integrated over the entire hour. Collect
four SPME samples with each sampling period lasting 15 minutes. Record
the ambient temperature and relative humidity. Ancillary data from the
mobile laboratory include ambient CO, wind speed and direction,
temperature and relative humidity. The mobile laboratory will remain at
the RV Park during these measurements.

37. Outdoors: toll booth (ME12)

Two possible locations for this microenvironment are toll booths on
tollways or one of the centralize vehicle inspection stations. The
vehicle inspection station at 3824 159^th^ Place is reasonably close to
the RV Park and has good access. Sampling at the toll plaza would be
conducted behind the toll booth 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.

Sample the breathing zone continuously with a KORE MS 200, Langan T15,
Alpha Omega HCHO analyzer, and portable PID monitor and collect one set
of canister and DNPH samples integrated over the entire hour. Collect
four SPME samples with each sampling period lasting 15 minutes. Record
the ambient temperature and relative humidity. Ancillary data from the
mobile laboratory include ambient CO, wind speed and direction,
temperature and relative humidity. The mobile laboratory will be located
on-site near the toll plaza office building. Park the RV with the
generator exhaust downwind relative to the inlet for the CO monitor. .

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.

38. Trailing high emitters (ME12)

Attempt to trail high emitters in Chicago locations with higher
fractions of high emitters.

**DAILY SAMPLING SCHEDULE**

The daily schedule for the Chicago sampling program will be determined
after a decision has been made to proceed with sampling in Chicago. In
order to stay on project schedule as much as possible, sampling will be
conducted on weekends in case we encounter unsuitable meteorological
conditions on scheduled sampling days.

**APPENDIX D**

**Example of a Diary Page**

+-----------------------------------+-----------------------------------+
| START TIME\*                      | STOP TIME\*                       |
|                                   |                                   |
| AM PM                             | AM PM                             |
+-----------------------------------+-----------------------------------+
| A. [ACTIVITY]{.underline} (please | D. [SMOKING]{.underline}          |
| specify)                          |                                   |
|                                   | > I am smoking 33                 |
| \_\_\_\_                          | >                                 |
| \_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\ | > Others are smoking 34           |
| _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ | >                                 |
|                                   | > No one is smoking 35            |
| \_\_\_\_                          |                                   |
| \_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\ | E. [ONLY IF INDOORS OR IN         |
| _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ | VEHICLE]{.underline}              |
|                                   |                                   |
| \_\_\_\_                          | > \(1\) Windows open?             |
| \_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\ | >                                 |
| _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ | > Yes 36                          |
|                                   | >                                 |
| B. [SPECIAL                       | > No 37                           |
| CONDITIONS]{.underline}           | >                                 |
| [Me]{.underline}                  | > Uncertain 38                    |
| [Others]{.underline}              | >                                 |
|                                   | > \(2\) Air conditioning on?      |
| Cooking with gas 01 02            | >                                 |
|                                   | > Yes 39                          |
| Cooking with other fuel 03 04     | >                                 |
|                                   | > No 40                           |
| Eating hot food 05 06             | >                                 |
|                                   | > Uncertain 41                    |
| Drinking alcoholic beverage 07 08 |                                   |
|                                   | F.  [ONLY IF INDOORS OR           |
| Cleaning with detergents 09 10    |     OUTDOORS]{.underline}         |
|                                   |                                   |
| Using personal care products 11   | Give address or nearest           |
| 12                                | intersection:                     |
|                                   | \_\_\_\_                          |
| Newly-cut vegetation/wood 13 14   | \_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\ |
|                                   | _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ |
| Solvent use 15 16                 |                                   |
|                                   | > \_\_\_\_                        |
| Gasoline handling 17 18           | \_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\ |
|                                   | _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ |
| Gasoline-powered tool 19 20       | >                                 |
|                                   | > G. [NEAREST ROAD (ALL           |
| Clothes recently dry-cleaned 21   | > LOCATIONS)]{.underline}         |
| 22                                |                                   |
|                                   | Give route number or street name  |
| [Other]{.underline} (open flame,  | of                                |
| smoke, odor, etc.) 23             |                                   |
|                                   | nearest road and [circle          |
| Specify condition, potential      | type]{.underline}:                |
| emission source,                  | \_\_\_\_                          |
|                                   | \_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\ |
| and proximity                     | _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ |
| \_\_\_\_\_\_\_\_\                 |                                   |
| _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ | > \_\_\_\_                        |
|                                   | \_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\ |
| \_\_\_\_                          | _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ |
| \_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\ |                                   |
| _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ | Highway 42                        |
|                                   |                                   |
| C. [LOCATION]{.underline}         | Arterial road 43                  |
|                                   |                                   |
| > In transit, car 24              | Residential area 44               |
| >                                 |                                   |
| > In transit, other vehicle 25    | Downtown street 45                |
| >                                 |                                   |
| > Specify                         | Urban street canyon 46            |
| > \_\_\_\_\_\_\_\_\_\_\           |                                   |
| _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ | Other 47                          |
| >                                 |                                   |
| > Indoors, residence 26           | Specify                           |
| >                                 | \_\_\_\_\_\_\_\_\_\_\             |
| > Indoors, garage 27              | _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ |
| >                                 |                                   |
| > Indoors, service station 28     | H. [TOWN]{.underline}             |
| >                                 |                                   |
| > Indoors, other 29               | > Reno 48                         |
| >                                 |                                   |
| > Specify                         | Other 49                          |
| > \_\_\_\_\_\_\_\_\_\_\           |                                   |
| _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ | Specify                           |
| >                                 | \_\_\_\_\_\_\_\_\_\               |
| > Outdoors, within 10 yards of    | _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ |
| >                                 |                                   |
| > road or street 30               |                                   |
| >                                 |                                   |
| > Traffic count: \_\_\_\_\_\_\_\_ |                                   |
| > vehicles/minute                 |                                   |
| >                                 |                                   |
| > I am \_\_ upwind \_\_ downwind  |                                   |
| > of road.                        |                                   |
| >                                 |                                   |
| > Outdoors, other 31              |                                   |
| >                                 |                                   |
| > Specify                         |                                   |
| > \_\_\_\_\_\_\_\_\_\_\           |                                   |
| _\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ |                                   |
| >                                 |                                   |
| > Uncertain 32                    |                                   |
+-----------------------------------+-----------------------------------+