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 ii 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. iii TABLE OF CONTENTS Acknowledgment ........................................................................................................................ ii Table of Contents....................................................................................................................... iii List of Tables............................................................................................................................. iv List of Figures............................................................................................................................ iv 1. INTRODUCTION ............................................................................................................... 1 1 2. PROPOSED MEASUREMENT METHODS AND PROTOCOLS ...................................... 2 1 2.1 Proposed Exposure Measurement Methods ................................................................ 2 1 2.2 Proposed Biomarker Measurements ........................................................................... 2 3 2.2.1 Urine and Breath Sample Collection ................................................................. 2 4 2.2.2 VOC Analysis in Breath and Urine Samples ..................................................... 2 4 2.3 Proposed Measurement Protocol ................................................................................ 2 5 2.3.1 Kore MS200 ..................................................................................................... 2 5 2.3.2 CO Instruments................................................................................................. 2 6 2.3.3 Continuous Formaldehyde Monitor.................................................................. 2 8 2.3.4 BTEX and MTBE by Solid Phase Microextraction ( SPME).............................. 2 8 2.3.5 Time Integrated Air Sample Collection and Analysis........................................ 2 9 3. EXPERIMENTAL PLAN.................................................................................................... 3 1 3.1 Controlled In Cabin and Residential Garage Exposure Measurements ( Task 2).......... 3 1 3.1.1 Procurement of Test Fuels from Houston, Chicago and Atlanta ( Task 2a)......... 3 1 3.1.2 Determination of Tailpipe and Evaporative Emissions of Test Vehicles ( Task 2b) .......................................................................................................... 3 7 3.1.3 Relationship Between Exhaust Emission Rates and In Cabin Exposure ( Task 2c)......................................................................................................... 3 11 3.1.4 Relationship Between Evaporative Emission Rates and Exposure in a Residence With an Attached Garage ( Task 2d) ............................................... 3 12 3.2 Microenvironmental Exposure Measurements in Atlanta, Chicago, and Houston ( Task 3)............................................................................................................. 3 13 3.2.1 Exposure Diary and Script Development ( Task 3a) ......................................... 3 14 3.2.2 In cabin Exposures in Urban Microenvironments ( Task 3b)............................ 3 14 3.2.3 Outdoor and Indoor Exposure in Urban Microenvironments ( Task 3c)............ 3 15 3.2.4 Technician Biomarker Analysis ( Task 4) ........................................................ 3 15 3.2.5 Approach for Selecting High End Microenvironments .................................... 3 15 3.3 Meteorology ( Task 5)............................................................................................... 3 20 3.4 Data Analysis ( Task 6)............................................................................................. 3 20 3.5 Reporting ................................................................................................................. 3 23 4. PROJECT SCHEDULE AND DELIVERABLES ................................................................ 4 1 5. REFERENCES .................................................................................................................... 5 1 iv LIST OF TABLES Table No. Page No.

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. Page No.

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 1 1 1. INTRODUCTION The U. S. Environmental Protection Agency ( EPA) has recently issued requirements for a test program in accordance with the Alternative Tier 2 provisions of the fuels and fuel additives ( F/ FA) health effects testing regulations, which are required pursuant to Section 211( b) of the Clean Air Act. In response to these requirements, the American Petroleum Institute ( API) contracted with a research team consisting of the Desert Research Institute ( DRI), Southwest Research Institute ( SwRI), Lovelace Respiratory Research Institute ( LRRI), and TRJ Environmental, Inc ( TRJ) to conduct a screening study of the high end distribution of inhalation exposures to evaporative and combustion emissions of baseline and oxygenated gasoline. This study plan describes the exposure protocols and specifies the measurement methods, sampling & analytical procedures, and quality assurance protocols that will be used in the study.

The goal of this research program is to screen potential high end inhalation exposure microenvironments dominated by evaporative and exhaust emissions of baseline and oxygenated gasoline. The specific objectives are to provide information allowing the Agency to:

  Quantify personal exposures to motor vehicle oxygenated and non oxygenated gasoline evaporative and exhaust emissions in microenvironments ( MEs) representing the upper end of the exposure frequency distribution of such exposures;

  Determine the quantitative relationships between personal exposures in selected MEs with fixed site measurements in these MEs and at nearby air monitoring stations;

  Determine how personal exposures differ in cities and seasons in which MTBEoxygenated , 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 1 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. 2 1 2. 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.

2.1 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. 2 2 Table 2 1 Proposed Measurement Methods Method Species Continuous BTEX 1,3 BD MTBE EtOH HCHO Acetaldehyde NMHC CO Time MS200 X 1 min T15 CO X 1 min API 300 CO X Seconds HCHO X 1 min ppbRAE X Seconds Surrogate A B C D E, F Semi Cont. SPME X X X(?) 15 min Integrated Can X X X X(?) X X 60 min DNPH X X 60 min Solid Adsob. X X X 60 min 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 CH3CHODNPH/ HCHOContinuous ratio for exhaustdominated 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 evaporativedominated 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 2 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.

2.2 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 preexposure 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 preexposure 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. 2 4 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.

2.2.1 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).

2.2.2 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 2 5 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. 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 1 µ g/ ul of benzene d6, toluene d8, xylened10 and ethyl alcohol d6 that will serve as internal standards for the analysis.

Head Space Solid Phase Microextraction. The sample will be heated to approximately 40 º 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. 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 200 º C 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/ µ l 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. The analysis of VOC in breath samples will be conducted as described below in Section 2.3.5 for canister VOC analysis.

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

2.3.1 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:

1. Start instrument and establish zero. 2. Apply span gas and allow 2 minutes to stabilize response. 3. Collect at least 5 spectra 2 6 4. Using calibration section in software, confirm calibration response or enter new calibration values as needed.

Daily Startup Procedures:

1. Check Battery Status ( or plug in). 2. Inlet valve: Middle position ( heater). 3. Inlet pump: On 4. Wait until inlet vacuum is less than 3x102 pa and inlet temperature led is green 5. Sample pump On 6. TOF MS: On 7. TDC: On ( unless you are on battery, then wait as this draws a lot of current.)

Once you are ready to sample:

1. Inlet Valve Down position ( confirm that vacuum is ok and heat is still ok) 2. Apply zero air and allow it to flow for at least 1 minute. 3. Collect 5 spectra of background air to assess variability. 4. Begin sampling If possible, during a run perform a zero check as follows: Apply zero air for 15 to 30 seconds, allowing the instrument to collect 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.

2.3.2 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. 2 7 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. 2 8 Figure 2 1. Variability of CO Electrochemical Cell Response with Temperature.

2.3.3 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 H2SO4 scrubber solution is used for the daily instrument calibration ( Kelly and Fortune, 1994). This daily calibration standard is compared with the gaseous formaldehyde standard, purchased from Apel Riemer Environmental, Inc. The monitor is zeroed by supplying high purity air to the inlet. Span and zero samples are provided to the monitor at regular intervals using automated valving. We are presently working on re engineering the Alpha Omega HCHO instrument to make it more field rugged and reliable.

2.3.4 BTEX and MTBE by Solid Phase Microextraction ( SPME)

Based on the results of our pilot study, we propose to use 75 µ m 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, 2 9 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 µ m film thickness, Varian, Inc.) optimized for quantification of BTEX and MTBE.

Calibration. 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 µ l 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. 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.

2.3.5 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. 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. 2 10 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. 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 µ m 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. Ethanol and MTBE will be quantified using solid adsorbent cartridges, in addition to canister method. Although MTBE is stable in SUMMA canisters and 2 11 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. 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). 3 1 3. 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.

3.1 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.

3.1.1 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. 3 2 Figure 3 1: Overall Structure of 211( b) Monitoring Requirements Scenario 1 Scenario 2 ... Scenario N Summer Winter Houston RFG MTBE Atlanta Baseline Chicago RFG EtOH San Antonio ( Chart B)

Section 211( b)

Exposure Study Scenarios In vehicle: commuter rush hour ( stop and go)

In vehicle: urban street canyons In vehicle: refueling*

In vehicle: parking garage In vehicle: toll plaza In vehicle: tunnel Outdoors: refueling vehicle*

Outdoors: sidewalk near high density traffic Outdoors: bus stop Indoors: underground parking garage Indoors: toll booth Indoors: auditorium with auto show or similar event MEASUREMENTS Continuous ( 1 5 min) Langan  CO, MS200  BTEX, Battelle  HCHO Semi continuous ( 15 20 min): SPME  MTBE, EtOH, BTEX Integrated ( 60 min): canister  1,3 BD, MTBE, EtOH, BTEX, TVOC DNPH cartridge  HCHO, CH3CHO Tenax tube  MTBE, EtOH, BTEX OTHER DATA Diary ( ME/ event)

Location: GPS ( lat/ long, min)

Biomarkers*: urine ( MTBE, BTEX)

Meteorology: WS/ WD, RH, T ( min); surface roughness; stability class Local air quality: sampling day monitoring station data ( 60 min) 3 3 Figure 3 2. Monitoring Requirements for San Antonio Study Segment N Leading vehicle Trailing vehicle Segment 1 Cabin Tests FTP Emission Tests Garage Adjacent room Test 1 Test N Garage Tests Normal Malfunctioning Sedan Truck RFG MTBE RFG EtOH Baseline Summer Winter San Antonio MEASUREMENTS Continuous ( 1 5 min) Langan  CO, KORE  BTEX, Battelle  HCHO Semi continuous ( 15 20 m in): SPME  MTBE, EtOH, BTEX Integrated ( 60 m in): canister  1,3 BD, M TBE, E tOH, BTEX, TVOC DNPH cartridge  HCHO, CH3CHO Tenax tube  MTBE, E tOH, BTEX OTHER DATA Diary ( ME/ event)

Location: GPS ( lat/ long, m in)

Meteorology: W S/ WD, RH, T ( min); surface roughness; stability c lass Local air quality: sampling day m onitoring station data ( 60 m in)

MEASUREMENTS Semi continuous ( 15 20 m in): SPME  MTBE, EtOH, BTEX OTHER DATA Diary ( ME/ event)

Location: GPS ( lat/ long, m in)

Meteorology: W S/ WD, RH, T ( min); surface roughness; stab. c lass Local air quality: sampling day m onitoring station data ( 60 m in)

Segm ents for Cabin Tests 1 Initial background  no test vehicles 2 Idling, c lose spacing 3 Moderate speed, m oderate spacing 4 High speed, greater spacing 5 F inal background  no test vehicles Garage Tests 1 Background, garage em pty 2 Car in garage, kitchen door open f or 1 m in 3 Car in garage, kitchen door open for entire test 4 Car in garage, kitchen door closed  window open 5 Car in garage idling, garage door open, kitchen door open for 1 min 6 Back car out and close ga rage door 3 4 Table 3 1 Collection of Time Integrated Samples for Chemical Analysis Number of Samples Per Exposure Period Total Durat ion of Measurement and Samples Test Duration ( min) Sample t ime SPME ( min) SPME1 SPME2 Cans DNPH Solid Adsorb. a No. of Tests Test Durat ion ( hrs) SPME1 SPME2 Cans DNPH Solid Adsorb.

Task 1 Lab evaluation and Pilot Study Pilot  In cabin, Freeway am & pm 60 30 2 2 1 1 1 2 2.0 4 4 2 2 2 Pilot  In cabin, surface street 60 30 2 2 1 1 1 2 2.0 2 2 1 1 1 Pilot  In cabin, refueling 60 30 2 1 1 1 1 2 2.0 2 2 1 1 1 Pilot  Refueling at pump 60 30 2 1 1 1 1 2 0.5 2 2 1 1 1 Pilot  Parking Garage 60 30 2 2 1 1 1 2 0.5 2 2 1 1 1 Pilot Residential Garage 180 30 6 6 4 4 4 1 180.0 6 6 4 4 4 Pilot  Pedestrian Walk 360 30 12 12 1 1 1 2 12.0 2 2 1 1 1 Subtotal 840 28 26 10 10 10 199 20 20 11 11 11 Task 2b: FTP Dynamometer Tests ( Optional Measurements by DRI)

FTP composite exhaust emissions 22.86 NA NA 1 1 1 NA NA 24 24 4 Diurnal Evap Test NA NA 1 0 1 NA NA 24 0 4 Subtotal 0 0 2 1 2 0 0 48 24 8 Task 2c: Controlled Exposures  Trailing medium/ high emitters ( Table 3 4)

Initial background 10 10 1 1 1 1 24 4.0 24 0 24 24 4 Exposure Measurements ( Table 3 4) 140 10 15 2 2 2 24 56.0 360 0 48 48 8 In cabin exposure in lead car ( b) 3 0 0 0 24 72 0 0 0 0 Subtotal 150 19 0 3 3 3 60.0 456 0 72 72 12 Task 2d: Controlled Exposure  Residential Garage Exposure ( Table 3 5)

In garage ( background) 30 30 1 1 1 1 24 12.0 24 0 24 24 4 In garage ( during exposure) 150 30 5 1 1 1 24 60.0 120 0 24 0 adjcent room ( background) ( b) 30 1 1 1 1 24 ( b) 24 0 24 24 4 adjcent room ( during exposure) ( b) 5 1 1 1 24 ( b) 120 0 24 0 Subtotal 180 30 12 4 4 4 72.0 288 0 96 48 8 3 5 Table 3 1 ( Continued)

Collection of Time Integrated Samples for Chemical Analysis Number of Samples Per Exposure Period Total Duration of Measurement and Samples Test Duration ( min) Sample time SPME ( min) SPME1 SPME2 Cans DNPH Solid Adsorb. a No. of Tests Test Duration ( hrs) SPME1 SPME2 Cans DNPH Solid Adsorb.

Task 3a: Urban Exposures in Vehicle Cabin Commuter Rush Hour ( stop n go) 60 15 3 1 1 1 18 18.0 54 18 18 3 Urban canyons 60 15 3 1 1 1 18 18.0 54 18 18 3 Refueling  in cabin 60 15 3 1 1 1 18 18.0 54 18 18 3 Parking garage 60 15 3 1 1 1 18 18.0 54 18 18 3 Toll Plaza 60 15 3 1 1 1 18 18.0 54 18 18 3 Tunnel 60 15 3 1 1 1 18 18.0 54 18 18 3 Subtotal 360 18 0 6 6 6 108 324 0 108 108 18 Task 3b: Urban Exposures in Outdoor and Indoor Microenvironments Refueling at pump 60 15 3 1 1 1 18 18.0 54 18 18 3 Sidewalk near high density traffic 60 15 3 1 1 1 18 18.0 54 18 18 3 Underground parking garage 60 15 3 1 1 1 18 18.0 54 18 18 3 Bus Stop 60 15 3 1 1 1 18 18.0 54 18 18 3 Toll Booth 60 15 3 1 1 1 18 18.0 54 18 18 3 Auditorium with Auto Show 60 15 3 1 1 1 18 18.0 54 18 18 3 Subtotal 360 18 0 6 6 6 108 324 0 108 108 18 3 6 Table 3 1 ( Continued) Collection of Time Integrated Samples for Chemical Analysis Test Duration ( hrs) SPME1 SPME2 Cans DNPH Solid Adsorb. Totals Task 1 199.0 20 20 11 11 11 Task 2b 0.0 0 0 48 24 8 Task 2c 60.0 456 0 72 72 12 Task 2d 72.0 288 0 96 48 8 132.0 744 0 216 144 28 Task 3a 108.0 324 0 108 108 18 Task 3b 108.0 324 0 108 108 18 216.0 648 0 216 216 36 All Tasks 547 1412 20 443 371 75 a. Collected for ethanol containing fuels only. b. Combined with initial background. c. Two out of three runs.

Notes Controlled Exposure All Fuels EtOH only Fuels ( Houston, Chicago, Atlanta) 3 1 Seasons ( summer, winter) 2 1 Vehicle Condition ( normal, malfunction) 2 2 Vehicles ( car, truck) 2 2 Total Combinations 24 4 Grand Total 24 4 Urban Exposure in Vehicle Cabin Fuels ( Houston, Chicago, Atlanta) 3 1 Seasons ( summer, winter) 2 1 Number of runs 3 3 Default condition on weekday Low ventilation on weekday Total Combinations 18 3 Other Microenvironments and Scripts Fuels ( Houston, Chicago, Atlanta) 3 1 Seasons ( summer, winter) 2 1 Replicates for each ME 3 2 Total Combinations 18 2 Pilot Test Number of replicates 2 3 7 3.1.2 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, O2 sensor, catalyst) can be reversibly disconnected to represent normal and reasonable high end approximations ( e. g.,   2 gm HC/ mile exhaust) of real world exhaust emissions. SwRI will determine exhaust emission rates for the two test vehicles, with and without malfunction, using three regional fuels during each of two seasons ( with seasonal fuels). This will result in 12 combinations for each season. SwRI also will measure evaporative emissions using the same test vehicles with and without induced malfunction ( e. g., disconnecting fuel line to carbon canister). Hydrocarbon samples will be collected in canisters and analyzed by DRI for complete hydrocarbon speciation. The data will be used to apportion the relative contributions of exhaust and evaporative emissions by applying these source composition profiles to the microenvironmental measurements from the three cities using Chemical Mass Balance ( CMB) receptor modeling.

The emission tests will be coordinated with the trailing vehicle tests described in Section 3.1.3 and the residential garage exposure tests describes in Section 3.1.4. SwRI will install the reversible malfunction on the two test vehicles and perform all emission testing prior to start of the exposure measurements. Two days will be required for the trailing vehicle and residential garage exposure measurements described in Tasks 2c and 2d for each of six combinations of vehicle and test fuel per season. The trailing vehicle exposure measurements 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, CO2; 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 3 8 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. 3 9 Table 3 2 Suggested Test Plan for Each Vehicle STEP DESCRIPTION 1 Obtain test vehicle. Verify proper mechanical operation.

2 Determine malfunction condition to achieve 2 or more grams/ mile total hydrocarbons.

3 Equip vehicle to allow switching between normal and malfunction conditions. Return vehicle to normal operating condition.

4 Remove canister from test vehicle.

5 Purge canister with 300 ° F zero nitrogen at 20L/ min for five hours, reattach canister.

6 Drain fuel tank and fill to 40 percent capacity with test fuel.

7 Perform a 2 hour diurnal heat build from 70 to 120 ° F at a ramp rate of 0.4 ° F/ min.

8 Operate vehicle on chassis dynamometer over one UDDS cycle.

9 Turn engine off for five minutes.

10 Start engine and idle for one minute.

11 Turn engine off for one minute.

12 Start engine and idle for one minute.

13 Remove canister from vehicle and purge canister with zero air for 60 minutes.

14 Reattach canister, drain fuel from tank, and fill to 40 percent capacity with chilled test fuel.

15 Conduct one hour DHB ( no emission measurements).

16 Operate vehicle on chassis dynamometer over one UDDS.

17 Soak vehicle overnight.

18 Next day prior to the cold start exhaust portion of the FTP, conduct one hour Diurnal Heat Build ( DHB). No emission measurements.

19 Conduct 3 bag FTP exhaust emission test. Measure regulated gaseous emissions and VOC emissions.

20 Conduct the Hot Soak segment of the SHED test immediately following the exhaust emissions testing. Measure total hydrocarbons and VOC emissions ( same as with exhaust except no aldehyde emissions).

21 Switch vehicle to malfunction per Step 2, and disconnect evaporative canister.

22 Repeat Steps 8 through 12 and Steps 16 through 20.

23 Repeat Steps 3 through 22 for each of the remaining five test fuels. 3 10 Table 3 3 Summary of the FTP Driving Cycle F Figure 3 3. FTP Driving Cycle. Duration, Distance, Average Speed,

Segment Seconds Miles Miles/ Hr.

Transient Phase 505 3.6 25.7 Stabilized Phase 867 3.9 16.2 UDDS 1372 7.5 19.7 3 11 3.1.3 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 timeintegrated canister samples.

Table 3 4. Protocol for trailing vehicle tests Time min. Speed mph Ventilation Setting Distance Notes Continuous Instruments SPME Time Integrated 10 high high background Y 1 1 10 low high far Y 1 10 low high near Y 1 10 low high passing Y 1 10 high high far Y 1 10 high high near Y 1 10 high high passing Y 1 10 low low far Y 1 10 low low near Y 1 10 low low passing Vehicles: Toyota Camry and Pick up truck, in normal and malfunction mode.

Fuels: Y 1 1 3 12 10 high low far Y 1 10 high low near Y 1 10 high low passing Y 1 10 idle low adjacent Y 1 10 idle high adjacent baseline, MTBE, ethanol Y 1 1 3.1.4 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). 3 13 Table 3 5. Protocol for attached garage experiments. The same vehicles and fuels as for trailing vehicle experiment are used.

Condition Time ( min) Garage Door Kitchen Door Kitchen Window Inlet Location Continuous SPME Integrated Samples 10 closed closed closed garage y 10 kitchen y Background 10 garage y 2 2 10 closed open 1min closed kitchen y 10 & closed garage y Hot soak 10 kitchen y 2 10 closed closed closed garage y 10 kitchen y Maximal AER to indoors 10 garage y 2 10 closed closed open kitchen y 10 garage y Maximal AER to outdoors 10 kitchen y 2 10 open open 1 min closed garage y 10 & closed kitchen y Cold start 10 garage y 2 2 3.2 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. 3 14 3.2.1 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.

3.2.2 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 3 15 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.

3.2.3 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: selfservice 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 timeintegrated 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.

3.2.4 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.

3.2.5 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 90th centiles of exposure, that result from the impacts of exhaust/ evaporative emissions from gasoline fueled vehicles. Two approaches to selecting highend 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 3 16   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: 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 lowventilation ( 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: 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: 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 3 17   Location with smallest external openings & most shielded from air dispersion by topography   Downwind direction from centroid on most occupied parking level Protocol: Prior to test, identify aboveground parking lot that 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 signalcontrolled intersection)   Location most shielded from air dispersion by topography   High use location   Downwind direction from centroid of traffic mass Protocol: Prior to test, identify toll plaza apron that 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: 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 3 18 Protocol: 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 lowventilation ( 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: 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: 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 3 19   In urban canyon Protocol: Prior to test, identify bus stop ( or cab stand) satisfies above conditions and confirm high concentrations using sniffer. With cart inlet in breathing zone, stand/ sit at this location ( within three feet of curb) for the entire 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: 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: 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. 3 20 3.3 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.

3.4 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. 3 21   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.

  Compare time averaged continuous data from the pilot study with corresponding semicontinuous 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, CH3CHO, EtOH, TVOC and CO during the initial and final loops without the test vehicle.

  Subtract the average time integrated background values from the corresponding time integrated exposure levels for the default driving condition for each of the 24 test combinations ( i. e., two test vehicles, two emission conditions, three fuels, and two season) and four replicates.

  Quantify separately for each of the two vehicles, the specific differences due to emission condition, fuel and season. Quantify absolute differences for each designated species and differences normalized to concurrent CO data.

  Variations in MTBE/ benzene and EtOH/ benzene ratios ( or other HC species) will be related to extent of the potential contribution of tailpipe and evaporative emissions.

  Determine the effect on cabin exposure of varying speed, spacing between test and trailing vehicle, and degree of ventilation.

  Determine variations of the in cabin exposures within the test and trailing vehicle due to variation in normal/ malfunction test vehicle emission rates under idle. 3 22 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.

  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. 3 23   Determine the levels of the designated species in the urine and breath of technicians carrying out the scripted behaviors and determine significant differences due to varying fuel formulation.

3.5 Reporting This task will require completion of the following:

  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) 4 1 4. 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 5 1 5. REFERENCES Cardin, D. and T. Robinson ( 2002). Formaldehyde and VOCs in air quality determinations by GC MS. American Laboratory. 32 34 Chai, M. and J. Pawliszyn ( 1995) Analysis of Environmental Air Samples by Solid Phase Microextraction and Gas Chromatography/ Ion Trap Mass Spectrometry, Environmental Science and Technology, Vol. 29, No. 3.

Environmental Protection Agency ( EPA) ( 1991). " Technical Assistance Document for Sampling and Analysis of Ozone Precursors." Document No. EPA/ 600 8 91/ 215, U. S. Environmental Protection Agency, Research Triangle Park, NC.

Environmental Protection Agency ( EPA) ( 1996). Descriptive Statistics from a Detailed Analysis of the National Human Activity Pattern Survey ( NHAPS) Data. Document no. EPA/ 600/ R 96/ 148, U. S. Environmental Protection Agency, Office of Research and Development, Washington, DC, July 1996.

Fung, K., and D. Grosjean ( 1981). " Determination of Nanogram Amounts of Carbonyls as 2,4 Dinitrophenylhydrazones by High Performance Liquid Chromatography." Anal. Chem., 53, 168 171.

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 94th 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 5 2 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. A 1 APPENDIX A Exposure Protocol and Study Plan for the Section 211( B) Tier 2 High End Exposure Screening Study of Baseline and Oxygenated Gasoline  Summer 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 A 2 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 99th percentile exposure levels within each type of microenvironment. Due to the scope of this study, it will not be possible to fully characterize ( by measurements) the range of exposures that include the 99th percentile. However, we considered available surrogate parameters for emission levels and dispersion to select sampling times and locations with the greatest potential for higher exposures. These emission surrogates include traffic counts, and diurnal variations in average highway speeds, length of queues at toll plazas, number of cars refueling or entering and exiting parking garages. Surrogates for dispersion include wind roses and diurnal variations in temperature. Measurements in microenvironments with unrestricted dispersion will be made in the early morning or evening during calm conditions and minimal vertical mixing. In moderate wind conditions, we will drive parallel to the prevailing wind to reduce the impact of cross winds. Our sampling strategy also recognizes that vehicle exhaust emission levels are significantly higher for high emitters and are higher for all vehicles during cold starts and accelerations. All of these factors are important in understanding the large temporal and spatial variations that are likely to exist within each of the microenvironments. We plan to examine available hourly CO data and PAMS BTEX and 1,3 butadiene data for June through September 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 A 3 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 A 4 near Minute Maid Park ( Houston Astros baseball stadium). The large parking lot east of the stadium is a potential sampling site during ballgames ( see Figure 4).

Congested Freeway 0 100 200 300 400 500 600 700 0727 0732 0737 0742 0747 0752 0757 0802 0807 0812 0817 0822 Time, CDT PID Response ( ppb) Average Maximum Figure 1. Eastbound I 10 from Barker Cypress Rd. through downtown Houston via southbound I 45 and westbound SR 59 and ending at Fannin exit.

Downtown Houston 0 100 200 300 400 500 600 0830 0835 0840 0845 0850 0855 0900 0905 0910 0915 0920 0925 0930 0935 0940 0945 0950 Time, CDT PID Response ( ppb) Average Maximum A 5 Figure 2. Tour of downtown Houston.

Bush Int. Airport, Highways 8, 59, and 10, and Washburn Tunnel 0 100 200 300 400 500 1240 1245 1250 1255 1300 1305 1310 1315 1320 1325 1330 1335 1340 1345 Time, CDT PID Response ( ppb) Average Maximum Figure 3. George Bush International Airport and drive to Washburn Tunnel.

Minute Maid Stadium Parking Lot After Houston Astros Baseball Game 0 100 200 300 400 500 600 700 2145 2150 2155 2200 2205 2210 2215 Time, CDT PID Response ( ppb) Average Maximum Figure 4. Minute Maid Park at the end of a ballgame on evening of June 21, 2002. A 6 Wahburn Tunnel and Ship Channel Bridge Toll Plaza 0 100 200 300 400 500 1345 1350 1355 1400 1405 1410 1415 1420 Time, CDT PID Response ( ppb) Average Maximum 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 incabin 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 A 7 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 8 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 eightmile segment of US 290 between N. Eldridge Parkway ( 3 miles northwest of SH A 9 Tollway) to Bingle Rd ( 5 miles southeast of SH Tollway). Start with inbound ( southeast) direction from N. Eldridge Parkway. Average speeds in the inbound and outbound directions are about 30 mph and 65 70 mph, respectively.

2. In vehicle: urban street canyons ( ME2)

The greatest volume of traffic in the downtown Houston occurs during the morning and afternoon commute periods and to a lesser extent during the noon hour. We propose the weekday afternoon commute period from 4: 00 to 5: 00 p. m. because the vehicles exiting the parking garages may still be in cold start mode and because ME1 precludes ME2 during the morning commute period.

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 A 10 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 incabin 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 A 11 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) A 12 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 A 13 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.