# SECTION 211(B) TIER 2 HIGH END EXPOSURE SCREENING STUDY OF BASELINE

AND OXYGENATED GASOLINE –2ND RENO PILOT STUDY

DRAFT REPORT

Prepared for

AMERICAN PETROLEUM INSTITUTE

1220 L Street

Washington, DC 20005-4070

Prepared by

Barbara Zielinska, John Sagebiel, David Campbe ll, Diana Ceballos, Mark McDaniel and Eric

Fujita

Desert Research Institute

2215 Raggio Parkway

Reno, NV 89512

# TABLE OF CONTENTS

1. Introduction

................................................................................................................ ........ 1-1

1

. 1 Study Overview and Technical Objectives

............................................................. 1-1

2. Experim e ntal Methods

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

2

. 1 M e a s u r e m ent Approach

........................................................................................... 2

- 1

2

. 2 Im prove m e nt in Sa m p ling Platform

........................................................................ 2-4

2

. 3 A n a l y t i c a l Methods

................................................................................................. 2

- 6

2

. 3

. 1 Breath Samples Analysis

............................................................................... 2-6

2

. 3

. 2 S P M E Methodology

...................................................................................... 2-7

2

. 4 D a t a Capture

.......................................................................................................... 2

- 1 5

3. Results

..................................................................................................................... ........... 3-1

3

. 1 Method Comparison of Redundant Data

................................................................. 3-1

3

. 1

. 1 P I D versus PID

.............................................................................................. 3-1

3

. 1

. 2 NDIR vs. Electrochem ical CO

....................................................................... 3-7

3

. 1

. 3 CO versus Canister CO

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

3

. 1

. 4 MS vs. Canister

............................................................................................ 3-12

3

. 1

. 5 SPME vs. Canisters

...................................................................................... 3-13

3

. 1

. 6 SPME vs. MS

............................................................................................... 3-17

3

. 1

. 7 DNPH vs. Form aldehyde

............................................................................. 3-21

3

. 1

. 8 Tenax vs. Canisters

...................................................................................... 3-21

3

. 2 Com p arisons of Correlated Data

........................................................................... 3-23

3

. 2

. 1 PID vs. CO

................................................................................................... 3-23

3

. 2

. 2 CO vs. Form aldehyde

.................................................................................. 3-28

3

. 2

. 3 SPME vs. PID

.............................................................................................. 3-32

3

. 3 E n v i r o n m ental Factors

........................................................................................... 3

- 3 5

3

. 4 R e c o n s t r u c t e d Data

................................................................................................ 3

- 4 0

3

. 5 B r e a t h Data

............................................................................................................ 3-46

3

. 6 Consistency of Microen v ironm ent Conditions

...................................................... 3-51

3

. 6

. 1 C O 3-51

3

. 6

. 2 P I D 3-53

4. Conclusions

................................................................................................................. ....... 4-1

5. References:

................................................................................................................. ........ 5-4

6

. A p p e n d i c i e s

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ....... 6-1

6

. 1 Appendix A: SPME

................................................................................................ 6-1

6

. 2 Appendix B: Canisters and Tenax

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

6

. 3 Appendix C: Breath Samples

................................................................................. 6-9

6

. 4 Appendix D: DNPH

............................................................................................. 6-12

ii

# LIST OF FI GURE S

Figure 2.2-1. Van inlets

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

Figure 2.2-2. Inlets m o unted on the tripod.

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

Figure 2.3-1. Set-up for tem p erature (upper pane l) and relative hum idity (lower panel)

dependence m easure m ents

.............................................................................................. 2-9

Figure 2.3-2. Tem p erature Dependence for 30, 50, and 100 ppb BTEX Concentrations.

. 2-10

Figure 2.3-2–cont’d. Tem p erature De pendence for 30, 50, and 100 ppb BTEX

Concentrations.

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

Figure 2.3-3. Concentration calibration at a given tem p erature for the BTEX

com pounds.

................................................................................................................... 2- 11

Figure 2.3-3-cont’d. Concentr ation calibration at a given tem p erature for the BTEX

com pounds.

................................................................................................................... 2- 12

Figure 2.3-4. Dyna m i c Calibration Tem p erature Dependence

............................................ 2-13

Figure 2.3-5. Static C a libration T e m p erat ure Dependence (By interpolation from

dynam i c system )

........................................................................................................... 2-13

Figure 2.3-6. Hum i dity De pendence on SPME response for a 100ppb BTEX standard

at 25C.

........................................................................................................................ ... 2-14

Figure 2.4-1. Effect of driving on continuous f o rm aldehyde analy zer, during and after

sam p ling in ME2-5.

...................................................................................................... 2-16

Figure 3.1-1a. Comparison of estim ated B TEX concentrations measured by PID

instrum e nts with inlets collocated w ithin 10 cm . Data are running 1 m i nute

averages. VR = nozzle vapor recovery.

.......................................................................... 3-2

Figure 3.1-1b – cont’d. Com p arison of estim at ed BTEX c oncentrations m easured by

PID instrum e nts with in lets collocated within 1 0 cm . Data are runn ing 1 m i nute

averages. VR = nozzle vapor recovery.

.......................................................................... 3-3

Figure 3.1-2. Com p arison of estim ated B TEX concentrations m easured by P I D

instrum e nts during freeway driving tests. Data are running 1 m i nute averages.

............ 3-5

Figure 3.1-2 –cont’d. C o m p arison of estim ated BTEX conc entrations m e asured by PID

instrum e nts during freeway driving tests. Data are running 1 m i nute averages.

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

Figure 3.1-3. Comparison of NDIR (API m odel 300) and electrochem ical (Langan

T15v) CO monitors during two freeway driving tests.

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

iii

# Figure 3.1-4. Com p arison of two gas-filter correlation NDIR CO analyzers during onroad sam p l i n g

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

Figure 3.1-6 Com p arison of canister and MS200 data for all m e asured species.

................ 3-12

Figure 3.1-7. Com p arison of MS200 a nd canister for benzene only.

.................................. 3-13

Figure 3.1-8. Scatter Plots for raw data from SPME vs canister for the Pilot Study 2003

. 3 -15

Figure 3.1 -9 . Scatter Plots for tem p eratu r e co rr e c ted SPME vs caniste r d a ta f o r the P ilot

Study 2003

.................................................................................................................... 3 -15

Figure 3.1-10. Scatter plots from SPME vs Canister for the Pilot Study 2003 with two

outliers removed.

.......................................................................................................... 3-16

Figure 3.1-11. 10 m i nutes average MS data vs SP ME benzene and toluene

concentrations: Freeway 5/02 7:35-8:15 am

................................................................. 3-18

Figure 3.1-12. 10 m i nutes average MS da ta vs SP ME benzene and toluene

concentrations: Freeway 4/30, 7:35 am

........................................................................ 3-19

Figure 3.1-13. 10 m i nutes average MS data vs SP ME benzene and toluene

concentrations: Refueling w/o VR 5/02 9:18 am

......................................................... 3-20

Figure 3.1-14 Com p arison of caniste r and Tenax data for all ME

..................................... 3-22

Figure 3.2-1. Com p arison of CO and BTEX by PID during parking garage tests.

............ 3-24

Figure 3.2-1 – cont’d. Com p arison of CO and BTEX by PID during parking garage

tests. Data are running 1 m i nute averages.

................................................................... 3-25

Figure 3.2-3. Scatter plot of CO vs BTEX by PI D during parking garage tests. Data are

running 1 minute averages.

........................................................................................... 3-26

Figure 3.2-4. Com p arison of CO and BTEX by PID during freeway driving tests.

........... 3-27

Figure 3.2-9. SPME 10 m i n total BTEX vs. PI D 10 m i n averages, Freeway, 5/02, 7:35

am

............................................................................................................................. .... 3-32

Figure 3.2-10. SPME 10 m i n total B TEX vs. PID 10 m i n averages, Refueling w/o VR

4/30 9:21am

. ................................................................................................................. 3- 32

Figure 3.2-11. SPME 10 m i n total B TEX vs. PID 10 m i n a v erages, Freeway 4/30, 7:35

am

. ............................................................................................................................ .... 3-33

Figure 3.2-12. SPME 10 m i n total B TEX vs. PID 10 m i n averages, Refueling w/o VR

5/02 9:18 am.

................................................................................................................ 3- 33

iv

# Figure 3.2-13. SPME 10 m i n total B TEX vs. PI D 10 m i n averages, Parking Garage 5/06,

16:45 pm

. ...................................................................................................................... 3-34

Figure 3.3-1. Fuel tank te m p eratures during freeway ME on 4/29/03. Ambient

tem p erature was 4.4 C during this tim e.

....................................................................... 3-37

Figure 3.5–1. CO2 values in the breath sam p le s of subjects B and J collected in all ME,

organized by the subject and by m i croenvironm ent.

.................................................... 3-47

Figure 3.6-1. Range and variability of CO con centration during tests. Statistics for each

of the five replicate tests are s hown for each m i croenvironm ent.

................................ 3-52

Figure 3.6-2. Range and variability of BT EX by PID concentration during tests.

............. 3-54

Figure 3.6-3. Range and variability of m ean CO and m ean BTEX by PID concentration

for four m i croenvironm ents.

......................................................................................... 3-55

v

# LIST OF TABLES

Table 2.1-1. Measurem ent m e thods used in the 2 nd 

# Reno Pilot Study.

................................. 2-3

Table 2.4-1. Data Capt ure Summ ary

................................................................................... 2-16

Table 3.1-1. Data com p a r ison be tween SPME and Canister

.............................................. 3-14

Table 3.1-2. Correlation of S catter Plots from SPME and Canister Com p a r i s o n

. . . . . . . . . . . . . . . 3-16

Table 3.3-1. Environm ental Conditions for Freeway Driving MEs.

................................... 3-36

Table 3.3-2. Environm ental Condi tions for Garage MEs.

................................................... 3-38

Table 3.3-3. Environm ental Conditio ns for Refue ling MEs.

............................................... 3-39

vi

# 1. INTRODUCTION

The U.S. Environm ental Protection A g ency (EPA) has recently issued req u irem ents for a test

program in accordan ce with the Alternative Tier 2 prov isio ns of the fuels and fuel additives

(F/FA) health ef f ects testing regu latio n s, whic h are required pursuant to Section 211(b) of the

Clean Air Act. In re sp onse to th es e requirem e nts, the Americ an Petro l eum Institu te (API)

contracted with a research team consisting of the Desert Research Institute (DRI), Southwest

Research I n stitu te (S wRI), Lovelace Respir atory Res e a r ch In stitute (LRRI), and TRJ

Environm ental, Inc (TRJ) to conduct a screen ing study of the high-end distribution of

inhalation exposures to evapor ative and com bus tion em issions of baseline- and oxygenated

gasoline. T h e exposure protocols and m eas urem ent methods, sampling & analytical

procedures are described in the June 13, 2002 Exposure Protocol and Study Plan. The field

m easure m ents in San Antonio, Houston

, and A tlan t a were com p leted in adheren c e to th is

written protocol during summer 2002. The work in Chicago was postponed pending further

evaluation of the m easurem ent protocol and ass e ssm ent of the data co lle c t ed to da te.

The overall approach for the e xposure study is based upon the draft S211b Tier 2 E xposure

Study Protocol that was developed in May 2001 by the API Section 211(b) Research Group

and reviewed by the EP A. DRI and LRRI cond ucted a five-day pilo t study in Reno, NV

during February 2002 to test alternative m e a s urem ent approaches in the field under

conditions that are sim ilar to those that will be encountered in the m a in study. TRJ and API

provided input in the design of the pilo t study and rev i ew ed the results and findings. The

evaluations included available m easurem ent methods for continuous and tim e-integrated

m easure m ents of carbon m onoxide (CO), to tal volatile organic com pounds (TVOC), and

designated VOC species. DRI and LRRI also evaluated th e stab ility of the designated VOC

species in breath and urine sam p les during th e pilot study. Results of the pilot study are

summarized in our pilot study report (Zielinsk a et al., 2002). The draft exposure protocols

were appropriately m odified based upon the results of the pilot study.

The work conducted last summ er was summ arized in two interim data reports, one reporting

on data collected in San Antonio, Houston a nd Atlanta, and one conducting detailed data

analys is fro m Atlanta. Based on these reports, in order to a ssess and identify th e necessity

for further refinem e nt and adjustm e nts to th e study protocol prior to the comm encem ent of

the next phase of the study EPA asked to conduct the 2 nd 

# Pilot S t udy in Reno during the

April – May 2003 tim e fram e

.

1.1 Study Overview and Technical Objectives

The m a in goal of the 2 nd 

# Reno Pilot Study was to de monstrate proper operation and

reliability of analytic al ins t rum e ntation and com p arability of tim e-in tegra t ed, sem i

continuous and continuous m e thods for com p ounds of interest. Four m i croenvironm ents

were selected for this study, as follows:

1. Morning rush hour commuter tra ffic (ME1). This test was conducted on US395.

Due to the lim ited rush hour period in Reno, a relatively small city, we sam p led for

1-1

# only 40 m i nutes. The driving route was from Parr Blvd in the north to V illanova Dr.

in the sou t h. During the test we a t te mpted to f o llow a high e m itting vehicle th at was

supplied by one of our DRI coworkers (Dat sun 280Z, 1975). W e sa m p led inside the

van under high (first 20 m i n) a nd low (second 20 m i n) ventil ation conditions . In low

ventilation condition, we used recirculated air, windows closed, fan on high and in

high ventilation conditions we ha d windows open, with fresh air, recirculated air off.

During this ME a secon d PID m onitored the air outside the van.

2. Parking garage (ME2). Due to lack of a suitable be low ground parking structure in

Reno, we used an above ground parking gara ge. W e selected the Galleria parking

garage in downtown Re no, a site that is used by county worker s in a nearby building

whose workday ends at 5:00 PM. Consequently

, this loc a tio n had a pulse of cold-sta rt

traffic em issions at 5:00 PM as workers at tem p ted to leave at the sam e tim e. Due to

our lim ited city size and m odest traffic de nsity, we anticipated th e even ing exit rus h

from the garage to be over promptly and employed one-half hour of sam p ling

(approxim a tely 1645 to 1715) from the van park ed at a location ne ar the only garage

exit. Thus, all cars had to pass our sam p li ng location as they exit the garage. T h e

sam p ling inlet was loc a ted at th e bre a th ing zone imm e diately next to the van.

3. Outdoor refueling w i th Stage 2 vapor recovery at the pump (ME3). We

conducted refueling of one vehicle (our 1996 sam p ling minivan) during a 20 m i n

period. The fuel tank of the van was m odified to enable the fuel to be drained from

the van prior to refueling. Our objective wa s to dispense approxim a tely the sam e

am ount of fuel each tim e . The vehicle was driven prior to refu eling to raise the

monitored tem p eratures on the outside surf ace of the fuel t a nk. The refueling tests

were perform e d at the service station in Reno (corner of Sun Valley Dr. and Dandini

Blv.), which has stage 2 vapor recovery nozzles. While rem o ving the nozzle from the

vehicle filler tube, we spilled a few drops of liquid gasolin e on the ground near th e

vehicle. The am ount of t h e spill was not ed. The refueling was done under calm wind

conditions (i.e., wind speed below 5 m ph). W i nd was monitored by hand-held

anem om eter. Monitoring was done at the br eathing zone of the person fueling the

van.

4. Outdoor refueling w i thout vapor recovery at the pump (ME4). This test was

conducted at a sm all gas station in Reno th at does not have stage 2 vapor recovery

nozzles. Because this s t ation sells a rela tively low volum e of fuel, it has not been

required to upgrade to the stage 2. As not ed above, we refueled one vehicle during

the 20 m i n test at the gas station. W h ile ta king the nozzle from the vehicle filler tube,

we caused a spill of a few drops of liquid ga solin e on the gro und near the vehicle. Th e

am ount of t h e spill was noted. The refueling was done under calm wind conditions

(i.e. wind speed below 5 m ph). M onitoring was done at the breathing zone of the

person fueling the van.

Figure 1-1 shows the sampling locations. The US395 driving segm ent is m a rked in blue.

1-2

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Contact the EPA Docket Center’s P ublic Reading Room to view

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# 2. EXPERIMENT AL METHODS

2.1 Measurement Approach

Our sam p ling strategy consists of a three-tiered approach sh own in Table 2.1-1, which lists

the overlapping m easurem ent m e thods used in the Section 211(B) Ti er 2 High-End Exposure

Screening Study and their intended application. T h e applications ar e classified in one of three

tie rs: ref e re nce, sur r oga te, a nd confirm a tory. The base s e t or “reference” (R) m easurem ents

consist of three well-es t ablished tim e -integ rated m easurements. Thes e include : 1 ) canis ter

sam p ling and analysis by gas chromatography w ith f l am e ion i zation de tec tion f o r m e thanize d

CO, BTEX, 1,3-butadiene, MTBE, and nonm ethane hydrocarbons (NMHC); 2) 2,4-

dinitrophenylhydrazine (DNPH) car tridge sam p ling and analysis by high perform a nce liquid

chrom a tography with UV detection for form aldehyde and acetalde hyde; and 3) solid

adsorbent sampling and analysis of ethanol by gas chrom a tography with m a ss spectrom e try

detection. T h ese three m e thods combined m eas ure all species of in terest over the entire

sam p ling period with in each m i croenvironm ent. Although these integrated m e thods do not

characterize peak exposures in m i croenvironm ents with highly varying exposure levels. They

provide a basis for validating continuous and se m i -continuous data. They also provide a basis

for deriving correlations between the integrated values and continuous “surrogates” (S ), such

as CO and photoionizable VOC (10.6 eV - photoi onization detector) PID data, in order to

reconstruct their tim e series. For ex am ple, data for BTEX, 1,3-butadiene

, and MTBE from

the canister m easure m ents can be correlated to continuous C O and PID data to reconstruct

their tim e series in exh a ust-dom inated environ m ents. The sam e m e thod is used fo r ethano l

and NMHC. In a sim ilar m a nner, the tim e series of acetald e hyde and form aldehyde can be

reconstructed from the correlation of the integr ated DNPH samples with CO or PID. Outdoor

afternoon samples should be excluded due to possible contributi on of carbonyl compounds

for m ed from atm o spheric reactions of hydrocarb ons. Table 2.1-1 shows th e other correlations

that can be used in this manner.

Three continuous m e thods were em ployed to m o n itor: 1) the arom atic hydrocarbons benzene,

toluene, ethylbenzene, and the xylenes (B TEX), 2) carbon monoxide, and 3) for m aldehyde.

These m e thods were also combined with com ponent concentration ratios fr om

contem poraneous tim e-integrated samples to rec onstruct the expected tim e series for specie s

that did not have continuous instrum e nts, e.g., 1,3-butadiene (BD), ethanol (E tOH), and

m e thyl tert-butyl ether (MTBE).

The Kore MS200 instrum e nt was used to m onitor BTE X on a one-m inute basis. This

instrum e nt uses a tim e-of-flight m a s s spectrom e ter to separate com pounds of interest. This

instrum e nt a l so uses a s o f t ware solu tion incorp o r ating the 7 0 eV electro n im pact io nization

fragm e ntatio n patterns of each com p ound to a pportion th e contribution of each com ponent o f

inte rest to th e tim e-of -f

light (TOF) m a ss spect rum seen by the instrum e nt. The software does

not distinguish between specific isom ers, thus xy lenes are reported together. The inlet uses a

polydim e thylsiloxane mem b rane preferentially to allow non-polar organic com pounds into

the ana l yze r while m a intaining the v acuum inside the analy z er cham ber. This m e m b r a ne in let

2-1

# does lim it the types of com pounds that can be analyzed, h o wever. Common air c onstitu ents

and polar organic m o lecules do not pass the m e mbrane quickly.

Carbon m o noxide was monitored by the Langan T15 CO m oni tor and the API Model 300

and ML9830 CO NDIR analyzers. T h e Langan T 15 is an electrochem i cal monitor for CO.

The response tim e of this instrum e nt is som e wha t slower than infrared-based instrum e nts.

Both the API and ML in strum e nts are specified in the EPA List of Designated Reference and

Equivalent Methods (March 24, 2000) as a federal reference m e thod operating at any

tem p erature in the range of 15 oC to 35 oC (59 oF to 95 oF).

(www.epa.gov/ttnam ti1/files/am bien t/criteria/criteria/0300co.pdf)

Continuous Form aldehyde Monitor (Alpha-Om e ga Power T e chnology, Ltd., Albuquerque,

NM) absorbs form aldehyde in acidified wate r, reacting it with 2,4-pentanedione and

ammonia to for m a cyclized produ ct, 3,5-diacet y l -1,4-dihyd ro lutid ene, wh ich is con tinuously

detected by fluorescence. The m e thod is highly specific for form aldehyde and very sensitive.

However, since this instrum e nt did not perform e d well during the summer study we

introduced several im provem e nts, as follows. The original instrument case, detector,

electronics, valves, some of th e fittings were retained. Majo r m odifications included rem oval

of the original four channel peristaltic pum p necessary for reagent delivery and fluid flows to

the detector. This pum p was found to be incapa ble of m a intaining consistent flows and was

susceptible to failure when pum p t ubing woul d rupture or pull away from the connection

fittings. In addition, flow rates h a d lim ited adjustab ility, m a king it not suitable for the

additional modifications that were perform e d on the ins t ru m e nt. The peris t altic p u m p was

replaced with four m illiGAT piston pum p s (Global FIA) with m i croprocessor-controlled

motors capable of delivering a broad range of precisely m e tered flow rates. Another m a jor

modification was replacem ent of the diffusi on scrubber assem b ly with a scrubbing coil

sim ilar to the design described in Kelly and Fortune (1994). The original diffusion scrubber

was susceptible to m a lfunction when scrubbers or driers were heavily used or contam inated

by the reagents. In contrast, the scrubbing coil is sim p le to operate and m a intain, and is

reported as being 100% efficient at rem oving gaseous form aldehyde from the air stream

being sam p led. An in-line debubbler (Global FIA) was installed betwee n the heated reaction

cell and the detector to rem ove any bubbles from the sample stream before entering the

detector. This was necessary because bubbles m a y be generated elsew h ere in the system or

when the sample m obile phase is heated in th e reaction cell. Finally

, calibration of the

instrum e nt was perform e d using a gaseous form aldehyde standard (1 ppm in N 2( g) 

# ,ApelReim er) diluted to the desired concentration (5 to 250 ppb) with UHP zero air (Airgas) and

plum bed to the sam p le inlet of the scrubbi ng coil. Calibration curves were linear (R 2 

# >0.99).

The instrument response tim e was determ ined to be 6 m i nutes from the tim e of sam p le

introduction to equilibration at the detector . Instrum e nt background was determ ined by

periodically installing a DNPH car tridge (W aters) on the inlet of scrubbing coil to rem ove

any for m aldehyde from t h e sam p le stream in order to observe the detector baseline response.

2-2Table 2.1-1. Measurement methods used in the 2ndReno Pilot Study.Data applications for specific methods are classified as reference, confirmatory, and surrogate.A1ContinuousSemi-ContIntegratedMethodT15 CONDIRCOppbRAEMS200HCHOSPMECanisterDNPHAdsorbentpplicable EnvironmentsallallallhigherendallallallallallTimeResolutionsecondssecondsseconds1min1-2min10 min30&40min30 &40 min30 &40 minDetection Limits0.1ppm0.04 ppm1ppb1-3ppbv1ppbv0.2 ppbv0.05ppbC0.1ppbv0.2ppbvData Application1SSSC CCRRRCOSCSCRPID2SCBTEXS(a)S(a)SC(c)CCR,3-ButadieneS(a) S(a) S(c)RMTBES(a) S(a) S(c)CRFormaldehydeS (b)S(b)S(d)CRAcetaldehyeS (b)S(b)S(d)S(g)REthanolS(e)S(e)S(f)RNMHCS(a) S(a) S(c)R1.Categoryof data applicationinclude surrogate(S), confirmatory(C) reference (R), andsurrogatecompounds orsignal (SC)2.Sumofmoleculesionizable at 10.6 eVand detectedbyphotoionizationdetector.S (a). Timeseries will bereconstructedfromthe canister/CO ratioforexhaust-dominated samples.S (b).Timeseries will be reconstructed fromthe DNPH/CO ratiofor exhaust-dominatedsamples except outdoor daytime samples.S (c). Timeseries will bereconstructedfromthe canister/PIDratiofor exhaust- orevap-dominated samples inoutdoor MEs.S (d).Timeseries will be reconstructed fromthe DNPH/PID ratioforexhaust-dominatedsamples except outdoor daytime samples.S (e). Timeseries will bereconstructedfromthesolidadsorbent/CO ratio forexhaust-dominated samples.S (f). Timeseries will be reconstructedfromthe solidadsorbent/PID ratioforexhaust and evap-dominated samples.S (g).Timeseries will be reconstructed fromCH3CHODNPH/HCHOContratiofor exhaust dominated samples.2-3

# Photoionization detector (PID) m easured the total signal fr om molecules ionizable at 10.6

eV. W e used two PID monitors for the pilo t study. For the freewa y runs, one PID sam p led

outside air, and the other sam p led in-cabin air. For th e re m a ining runs, only one PID was

used, but for com p arison purposes w e ran both of them side-by-side for selected runs.

The tim e-integrated and se m i -continuous collection m e thods (canis te rs, solid ad sorbent

cartridge s, DNPH-integ r ated car tr id ges and SP ME) were d e scrib e d in d e tail bef o re ( Z ielin ska

et al, 2002, 2003). Depending on the type of sorbent (C18 or silica gel) in the DNPH

cartridge, the carbonyl com pound a m bient m eas ure m ent results are subject to various

artif acts due to in ter actio n with ozon e

. Consequently, the ozone denuder is recomm ended for

sam p le collection. For this pilot study, we used a honeycom b denuder coated with sodium

carbonate/sodium nitrite/glycerol m i xture (m ethod developed by Dr. K outrakis from the

Harvard School of Public Health). For canister sam p ling, ambient NO 2 

# is of concern, since

it m i ght react with 1,3 butadiene. Thus, we were using a honeycom b denuder coated with

triethanoloam i ne (TEA) to rem ove NO 2 

# (a m e thod developed by Dr. Koutrakis).

I n a d d i t i o n

, w e c o l l e c t e d b r e a t h s a m p les in a ll m i croenvironments. W e used 1 lite r silicostee l

canisters (Restek, Inc.) and a collection m e thod described by Pleil and Lindstrom , 1995.

Breath samples we re c o llec t ed f o r

the ref u e ling MEs imm e diately before and 10 seconds

after refueling the vehicle to provide an estim a te of the highest cum u lative exposure. For the

commuter traffic and garage MEs, breath sam p le s were collected before, and at 10 seconds

after a peak exposure indicated by the PID, an d at the end of the ME s a m p ling time. Two

breath s a m p les were co llected at refueling ME s (total of 20) and three during each co mmuter

traf f i c and garage tests. This is a total of 50 breath sam p les. The CO2 level in the breath

sam p le of pe rsons conducting the breath te st was m easured prior to the pilot study.

2.2 Improvement in Sampling Platform

The m o st significant ch ange m a de to the sa m p ling pla t f o r

m was the com b ination of all

sam p ling inlets at a single location. For the m o b ile ME (freeway driving), the inlets are all

located in the breathing zone n ear the driver’s right shoulder. Figure 2.2-1 shows the current

conf iguratio n of the inle ts. The line in th is f i gure labeled “S am ple Inle t” provides sample to

the NDIR CO, the MS200, the for m aldehyde instrum e nt, one of the two PIDs and all of the

integ r ated s a m p lers (ca n iste r, DNPH and solid adsorben t). The SPME f i ber, th e m a in inlet

and the tem p eratu r e and relative hu m i dity sensor are all within 3 cm of each other. The T-15

(ele ctro che m ical) CO instrum e nt is also very close. This configuration was designed to

m i nim i ze or elim inate p o tential va riability asso c i ated with c oncentr ation gradien t s in side the

van. In addition, we recorded the fuel tank temperature by way of a tem p erature probe

secured to the outside of the fuel tank and insulated to prev ent influence from the ground or

air heat. The video cam era reco rded the view out the front windshield during the driving ME

and was used to record other significant activ ity a t the other MEs. For exam ple, in the

garage, the cam e ra was used to record traffic driving by the sampling point.

2-4

# Figure 2.2-1. Van inlets

For the stationary MEs (refueli ng and garage), the in let was mounted on a tripod to allow for

placem ent at an appropriate lo cation outside the v a n. In th is case, the tem p eratu r e and

relative hum idity p r obe was relocated as well. T h is was acco mplished by an addition al pie ce

of Teflon tubing for the inlet and an extens ion cable for the te mp erature and relative

hum i dity probe. This allows the sampling system to be switched from one configuration to

the other relatively quickly w ithout disturbing the instrum e nt s and sam p lers. Figure 2.2-2

shows a close-up of the tripod a nd details the locations of the sam p le inlet, the T/RH probe,

and the SPME fiber. The proxim ity of all thre e ensures that no sm all-sc ale va ria tion s in

concentratio n are influen c ing the sample.

Figure 2.2-2. Inlets m o unted on the tripod.

In addition, there were several other modifications m a de to the van to im prove it for the

sam p ling program . Among these wer e the add itio n of racks to saf e ly and s ecure ly hold the

equipm ent, the upgrading of the power supply, and the addition of a pump and lines to

2-5

# withdraw the fuel from t h e fuel tank in betw een the refueling MEs. A computer-b ased data

acquisition system was a l so installed to acquire as m u ch of the data as possible in one

system . This was used to log all tem p eratur e and other environm ental param e ters, analog

outputs fro m the CO instrum e nts an d the fo rm aldehyde ins t rum e nt, and position, speed and

direction inform ation from the GPS unit.

The power system was significantly upgraded to provide power and to elim inate the

suspected artifact seen on the T-15 C O under low ventilation conditions. In these

experim e nts, no artifact was observed on the T- 15 CO m onitor, and thus we are confident

that this po tentia l conta m ination has been elim inated. However, the pow er system pr oved

incapable of providing enough power for the AP I NDIR CO monitor. Once we discovered

what was wrong (the instrum e nt did not give an error m e ssage, rather it began giving very

erratic results), we added a se t of lead -acid b a tteries outsid e the van to provide the power

necessary to supply th is one instrument.

2.3 Analytical Methods

Most of the analytical m e thods e m ployed duri ng this pilot study were described in detail

before (Zielinska et al., 2002a,b; 2003). Th e exceptions are the anal ysis of the breath

sam p les that was perform e d si m ilarly to the m e thod of Pleil and Lindstrom , 1995, by gas

chrom a tography/m a ss spectrom e try (GC/MS), a nd the determ ination of the dependence of

SPME concentrations o n tem p eratu r e and rela tive hum idity. The sections below describe

these two analytical p r ocedures.

2.3.1 Breath Samples Analysis

The GC/MS system included: Entech 7100 prec oncentrator, Varian 3800 gas chrom a tograph

with FID and colum n switching valve, and Vari an Saturn 2000 ion trap m a ss spectrom e ter.

The Entech preconcen trator consis ted of three traps: 50% glass beads/50% Tenax, held at –

100 ° C during sam p le transfer, 100% Tenax held at –40 ° C and a final focusing trap (a p i ece

of silico-s t eel capillary) held at –180 ° C. The sample is desorbed f r om the f i rst trap a t 10 ° C,

from the second trap at 200 ° C and from the third one at approxim a tely 70 ° C to a transfer

line heated to 110 ° C and connected to the h ead of the first colum n. The sam p le was injected

at the head of a 60 m x 0.32 mm polym e thylsiloxane column (C PSil-5, Varian, Inc.) held at

30 ° C. This colum n was connected to the switching valve lead ing into a 30 mx 0.53 mm GSGasPro colu mn (J&W Scientif ic). Af ter app r oxi m a tely 7 m i n the valv e was switch e d so that

the effluent from the first colum n eluted onto a second 15 m x 0.32 mm polym ethylsiloxane

colum n connected to th e m a ss spectrom e ter. The colum n switch was tim ed so tha t the C2 and

C3 com pounds eluted on the FID and all C4 and higher com pounds eluted on the m a ss

spectrom e ter. The GC program was as follows: 30 ° C held for 2 m i n, then 8 ° C/m i n up to

260 ° C.

Calibration of the system was conducted with a m i xture that contained the m o st commonly

found hydrocarbons (75 com pounds from e t hane to n-undecane, p u rchased from Air

Environm ental), MTBE, and halocarbons (23 co mpounds from F12 to the dichlorobenzenes,

purchased f r om Scott Specialty Gases). The st andards were prepared in 6 L Silco-Steel

2-6

# canis ters (R estek, Bellef onte, PA) b y m i xing three different standard s th rough a m u lti-v a lve

m a nifold us ing a Baratron absolute capacita nce m a nom e ter (MKS Instrum e nts, Andover,

MA) to determ ine the pressu re each standard added to the m i xture. Prior to m i xing,

approxim a tely 0.2 m l of ultrapure water was ad ded to the canister to hum i dify the m i xture

(for m i xture stability). T h e concentrations in the m i xture were in the range of 0.2 to 10 ppbv.

Three point external calibrations were run pr ior to analysis, and one calibration check was

run every 24 hours. If the response of individu al com pounds were m o re then 10% off, the

system was recalibrated.

Carbon dioxide (CO2) f r om breath sam p les was determ ined using GC/FID. Since the FID

does not respond to CO and CO2, these species are converted to m e thane by a m e thanator,

position e d a f ter the GC colum n, but ahead of the FID. The m e thanator com p rises a f i rebrick

powder im pregnated with nickel catalyst, th rough which a stream of hydrogen gas flows

continuously at ~550 °C. For com p ound separation, a 20-foot x 1/8-inch inner-diam eter (i.d.)

colum n, packed with a 60/80 m e sh of Carb oxen 1000 (Supelco) is used. This column

provides sufficient separation between CH4 a nd CO, without retaining CO2. Five m l

sam p les were injected using a constant vo lum e loop. The minim u m detection lim it f o r both

CO and CH4 is ~20 ppbv, whereas f o r CO2 it is ~3 ppm v. The precision of m easurem ents is

generally better than 10%.

2.3.2 SPME Methodology

During the Reno 2nd pilot project, SPME fibers were calibrated and an alyzed as described

before (Zielinska et al, 2002, 2003). However, the gas calibrat ion had to be corrected for

tem p erature, since s t atic (Tedlar b a g ) calib rati on is perform e d at room (25o C) tem p erature

and the sampling tem p eratu r e ran g ed from 4o C to 30o C (average 16o C). At lower

tem p erature the fiber uptake is higher, theref ore SPME values were expected to be higher

than canister data. The tem p erature correction factors were obtained experim e ntally in the

laboratory in a dynam i c flow-through system cons tructed for the control of te m p erature and

hum i dity of certified BTEX standards. Hum i d ity corrections are not a ddressed in this report

because the experim e ntal data obtain e d so far do esn’t show a significant change in th e SPME

response due to the change in hum idity.

2.3.2.1 Temperatu re and Humidity Calib ration Experimental Setup

Figure 2.3-1 shows the experim e ntal setup fo r tem p erature and hum i dity calibration. It

consisted of a 1L glass bulb that had two stop cocks on each side to let the calibration gas

flow through and an injection po rt covered with a sl eeve septum to allow the introduction of

a SPME fiber. The bulb was tem p erature contro lled with a cooling/ heating system. The

tem p erature inside the glass bulb was m easured with a therm o couple. For introducing the

desired humidity, a heated inject ion port was added before the gl ass bulb entrance in order to

inject water with a syringe pum p (Harvard Apparatus), Ludovic et al., 2001; Nelson, 1992;

McLaren and Zhou, 2000; Martos and Pawlis zyn, 1997). The water-dispensing rate can be

calcu lated f r o m the theor e tic al sa tura tion ratio obtained from a skew T diagram :

RH = 100 w/ws

2-7

# ws = ws(T,P)

w is set with the water-dispensing rate as g water/Kg air=RH*ws/100

The experim e ntal hum idity was m eas ured with a hum i dity se nsor (Dickson FH121).

Data from t h e static calibration was com p ared to the data obtained in the dynam i c sys t em t o

determ ine a correction factor that could be applied to the sam p ling data. Tedlar bag

calibrations are valid for the type of envir onm ents we are m easuring where wind should not

exceed 4 m iles/hou r. However, tem p eratu r e calib ration is a b e tter app r oached in a d ynam i c

system because tem p erature is the only variab le that chan ges, while in a static s y stem

pressure and volum e must be adjusted as explained by the ideal gas law and makes the

system very im precise. Som e advantages of a dynam ic syste m are greater reproducibility and

stability of the standards at lower con centration ranges (Nelson, 1992; Lodge 1984).

2-8

# Figure 2.3-1. Set-up for tem p erature (upper pane l) and relative hum i dity (lower panel)

dependence m easure m ents

2-9

# 2.3.2.2 SPME Temperature Dependence

PDMS coating has a sm all decrea se in the response of organics for sam p les with relative

hum i dity close to 100%. The prim ary experim e nt al param e ter that control the response is

tem p erature. In theory , the effect of te m p erature on the distribution constant can be

predic ted, since log(Kf g) is linea r with 1/T a nd the heat of vaporization of the pure solvent

(Kf g – partition coef f i cient). In othe r words, Kfg can be calculated f o r the given sa mpling

conditions (Pawliszyn, 2002). This theoretical a pproach is based on th e liquid properties of

the PDMS coating in th e f i ber. However, in pra c tice the theo ry doesn’t s a tisf a c t orily m a tch

the exper i mental va lues . Theref ore, we perf orm e d more experim e nts and utiliz e d the

experim e ntal approach.

Standards were m easured at different tem p eratures using the dynamic system described

above and results were com p ared to those obtained in a room tem p erature static calibration.

The experim e nts were perform e d a t different B TEX concentration levels, as shown in figure

2.3-2.

Te m p e r a t ur e de pe nd e n c e f o r

3 0 ppb B T E X

0 200 0 400 0 600 0 800 0 1000 0 1200 0 1400 0

0 1 0 2 0 3 0 4 0 5 0

Te m p e r a t ur e ( C )AreaCounts



### B enz ene T o l u ene E t hy l benz ene m

, p

- xyl e n e o

- xyl e n e



## T e m p e r a t ure D e p e nd e n c e f o r 5 0 pp b B T E X

0 4000 8000 12000 16000 20000

0 5 10 1 5 20 2 5 30 35 40 45

T e m p er a t u r e, CAreaCounts

b enz ene t o l uen e ethy l b enz en e m

, p- x y l ene o

, x y l ene



# Figure 2.3-2. Tem p erature Dependence fo r 30, 50, and 100 ppb BTEX Concentrations.

2-10

### Te m p e r at ur e D e pe nde nc e f o r

1 0 0 ppb B T E X

0 50 00 10 00 0 15 00 0 20 00 0 25 00 0 30 00 0

0 1 0 2 0 3 0 4 0 5 0

Te mp e r a t u r e

, CAreaCounts

bez ene t o l uene et hy l benz e n e m

, p- x y l ene o- x y l ene



# Figure 2.3-2–cont’d. Tem p erature De pendence for 30, 50, and 100 ppb BTEX

Concentrations.

These data can be plo tted by tem p eratu r e in order to obtain a li near relationship with

concentration as in Figure 2.3-3.

B e nz e n e Te m p e r a t u r e D e p e nde nc e

y = 188. 38x

R

2 

### = 0. 7134

y = 128.92x

R

2 

### = 0. 5 189

y = 107. 17x

R

2 

### = 0. 7398 0 5000 10000 15000 20000 25000

0 2 0 4 0 6 0 8 0 1 0 0 1 2 0

C o nc e n tr a t i o n, p p bAreaCOunts



### 10 C 25 C 40 C

Li nea r ( 10 C ) Li near ( 25 C ) Li n ear ( 40 C )

To l u e n e Te m p e r a t ur e D e pe nd e n c e

y = 178. 81 x

R

2 

### = 0. 922 7

y = 127. 49x

R

2 

### = 0. 784

y = 99. 57x

R

2 

### = 0

. 5472

0 5000 10000 15000 20000

0 2 0 4 0 6 0 8 0 100 120

C o nc e n t r a t i on, pp bAreaCOunts



### 10 C 25 C 40 C

L i near ( 10 C ) Li near ( 25 C ) Li near ( 40 C )



# Figure 2.3-3. Concentration calibration at a given tem p erature for the BTEX com pounds.

2-11

### E t hy l b e n z e ne Te m p e r a t ur e D e pe n d e n c e

y = 85

. 4 81 x

R

2 

### = 0. 77 76

y = 63.1x

R

2 

### = 0.3382

y = 46

. 488 x

R

2 

### = 0

. 6668

0 2 000 4 000 6 000 8 000 10 000

0 2 0 4 0 6 0 8 0 100 120

C o nc e n tr a t i o n

, pp bAreaCOunts



### 10 C 25 C 40 C

L i near ( 10 C ) Li ne ar ( 2 5 C ) L i near ( 40 C )



### m

, p- x y l e ne Te m p e r a t u r e D e pe nde nc e

y = 153.11x

R

2 

### = 0.7653

y = 108.77x

R

2 

### = 0.6097

y = 84

. 309 x

R

2 

### = 0

. 631 7

0 5 000 10 000 15 000 20 000 25 000 30 000 35 000

0 5 0 1 00 15 0 2 0 0 250

C onc e n t r a t i o n, pp bAreaCOunts



### 10 C 25 C 40 C

Li ne ar ( 1 0 C ) Li near ( 25 C ) L i near ( 40 C )



### o

- xy l e n e T e m p e r at u r e D e p e n d e n ce

y = 230.24x

R

2 

### = 0.8262

y = 148.82x

R

2 

### = 0.8426

y = 116.78x

R

2 

### = 0. 8 967 0 5000 10000 15000 20000 25000

0 2 0 4 0 6 0 8 0 100 120

C o n c e n tr a t i o n, pp bAreaCOunts



### 10 C 25 C 40 C

Li near ( 10 C ) Li near ( 25 C ) L i near ( 40 C )



# Figure 2.3-3-cont’d. Concentration calibrati on at a given tem p erature for the BTEX

com pounds.

2-12

# Furtherm ore, we plotted the slope s f r om this li near relationship vs. te mperature in order to

analyze the SPME response for a given temp erature. Figure 2.3-4 shows the linear

relationship between the slopes at dif f erent tem p eratures.

y = - 3

. 7813 x + 259. 81

R 2 = 0. 9405 y = - 2

. 2933x + 17 2. 73

R 2 = 0. 9731 y = - 1

. 2997x + 97. 51 5

R 2 = 0. 9928 y = -2. 6413x + 201. 32

R 2 = 0. 971 8 y = -2. 707x + 209. 17

R 2 = 0. 9329

0 50 100 150 200 250

0 5 10 15 20 25 30 35 40 45

T e mp erat u r e ( C )Slope(AC/Conc)

b e nz en e to l u e n e eh t l y b e n z e ne m, p

- x y l e n e o- py l e n e

Li ne ar ( o

- p y l en e) Li ne ar ( m

, p

- x y l en e) Li n e a r ( eht l y b e n z e ne) Li ne ar ( t o l ue ne ) Li n e a r ( b en z e ne )



# Figure 2.3-4. Dyna m i c Calibra tion Tem p erature Dependence

From this dynam i c temperature calibration we correlated the three variables analyzed (such

as area cou n ts, tem p erature, and concentratio n) and calculated the concentration of the

sam p le by t h e area cou n ts from the analysis an d the sam p ling tem p erature. Furthermore, we

com p ared the 25C dynam i c and static calibrati ons and extrapolated the other temperature

GC/PID responses in obtaining figure 2.3-5.

y = - 1

. 146 3x + 78

. 761

R 2 

### = 0. 94 05 y =

- 0

. 5 057x + 3 7

. 9 46

R 2 

### = 0.992 8

y = - 0

. 8 207 x + 61. 8 1 3

R 2 

### = 0

. 973 1 y = - 0 .7906 x + 60. 2 5 9

R 2 

### = 0

. 97 18 y = - 0 .8 3 3 6 x + 6 4 .4 1 1

R 2 

### = 0. 9 329

0 10 20 30 40 50 60 70 80

0 1 0 2 0 3 0 4 0 5 0

T e m p er a t u r e, CSlope(AC/C)

b enz e n e t o l u ene et h y l b enz ene m

, p

- xyl e n e o

- xyl e n e

Li nea r ( o

- x y l ene) Li ne ar ( e t h y l b enz e ne) Li n ear ( m

, p

- x y l en e) Li near ( t o l uene) L i near ( b enz en e)



# Figure 2.3-5. Static Calibrat ion Temperature Dependence (B y interpolation from dynam i c

system )

2-13

# The equatio ns that resu lt from these extrapo l atio ns are th e following:

S T AT I C S Y ST E M ( I N T ER P O L A T E D F R O M D Y N A M I C S Y ST E M )

Comp onent equ a tion cor r el 

## Conce n tr ation

be n z en e y = - 0 .8 336x + 6 4 .4 11 R2 = 0.9 329 AC/(

- 0 .8 336T + 6 4.4 11)

to l u ene y = - 0 .7 906x + 6 0 .2 59 R2 = 0.9 718 AC/(

- 0 .7 906T + 6 0.2 59)

EtB e n z en e y = - 0 .5 057x + 3 7 .9 46 R2 = 0.9 928 AC/(

- 0 .5 057T + 3 7.94 6)

m / p-x y len e y = - 0 .8 207x + 6 1 .8 13 R2 = 0.9 731 AC/(

- 0 .8 207T + 6 1.8 13)

o

- x y le ne y = - 1 .1 463x + 7 8 .7 61 R2 = 0.9 405 AC/(

- 1 .1 463T + 7 8.76 1)

AC/C = a T + c

C= AC /( a T + c )



# 2.3.2.3 SPME Humidity Dep e ndence

Chai and Pawliszyn, 1995, perform e d several experim e nts in orde r to determ ine the influence

of hum i dity for the 100 μ m PDMS r e sponse factor. Hum i dity usually decreases the response

factor of each individual com pound. The lower response depends on temperature. At lower

tem p eratures, the hum idity has a larger decrease in the response factor of a com pound. Som e

com pounds are not greatly affected by hum i dity. Th e highest effect of hum i dity seems to be

an approxim a tely 25% decrease when going fr om dry air at 0C-10C into 25% rela tiv e

hum i dity. Changes of the area counts at rang es of tem p erature of 0C-25C for changes in

relative hum i dity from 25%-75% are alm o st ne gligible (also discussed by Parreira et al,

2002).

It is understood that hum i dity a ffects the fiber response because water at high concentrations

is com p letely adsorbed into the co ating of the fiber.

Initial d a ta f r om the experim e ntal se t up described earlier is shown below:

0 50 00 100 00 150 00 200 00 250 00

0 1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0

Re l a t i ve Hu m i d i t y ( % )AreaCounts



### Be n z e n e To l u e n e eh t y l b en z e n e m

, p- x y l e ne o- x y l e ne



# Figure 2.3-6. Hum i dity Dependence on SPME response for a 100ppb BTEX standard at

25C.

2-14

# Current experim e nts at 25C determined that hum i dity in the BTEX compounds does not

af

f ect the GC/PID respo n se signif i c a ntly, a lthou gh is lowers the respon s e sligh tly a t RH >

75% .

2.4 Data Capture

The overall data capture rate for all the 2 nd 

# Reno Pilot Study m easure m ents is provided in

Table 2.4 -1, with the co mplete details for each ME presen ted in Appen d ix A. Overall the

data capture for the in tegrated m e thods was nearly com p lete . Only one solid adorbent tube

was lost to breakage. The “Refuel Can” in Table 2.4-1 refers to the 5-m i nute integrated

canis ter co llected durin g the actu a l refueling event. One canis ter cou l d not be s a m p led

because it was at atm o spheric p r essu re when opened in the field, and the data obtaine d from

the other one were invalidated, thus leading to a 80% capture rate for this category. The

“Breath Can ” refers to the breath canisters (2 o r 3 per ME) which were all co lle cted . For the

continuous and sem i -continuous m e thods, we had very good data captur e with only one run

m i ssing for the Outside PID (the one m easuring outsid e th e vehicle cab in during the freeway

ME). This was due to a software difference between this and our older instrum e nt that

resulted in the data logg ing function being accid e ntally turned off. The NDIR instrument lost

som e data due to insuf f i cient power in a f e w early runs; f o rtunately the T-15 CO functioned

perfectly for these runs. For the few runs wher e the T-15 CO data loggi ng had problem s , we

have the NDIR data thus at l east one instrum e nt was functioni ng for CO during all MEs. The

MS200 worked very w e ll du ring most of the early runs, but som e detector sen s itiv ity

problem s and other undiagnosed problem s resulted in com p lete loss of data for the last four

runs. One freeway run had m o stly good data with 5 m i nutes out of the 40 m i nute total being

lost due to electrical noise of undeterm ined origin. This is a sim ilar problem we had during

the San Antonio study and m a y be related to the van’s electrical system since proxim ity to

the other instrum e nts in the refueling MEs did not cause sim i lar noise.

The form aldehyde instrum e nt showe d som e good da ta but overall data capture rate was low

, mostly due to an electrical shortage in the ther m o couple that controls th e heated reaction cell.

This problem was not identified and fixe d until th e afternoon of May 2, 2003. W ithout

adequate co ntrol of the tem p erature of the heated reaction cell, th ere is little ce rtainty that th e

for m aldehyde collected was actua lly derivatized in a consistent m a nner. This m a lfunction

was diagnosed and fixed prior to the parking garage sample ME2-4, and did not reoccur.

Another m a j o r source of m a lfunction was the pres ence of air in the sample stream r eaching

the detector. Although an in-line debubbler wo rked well for rem oving air bubbles from the

sam p le strea m , air m a y still have r e ached the detector if pump flow rates were not properly

balanced among the 4 pum ps and air was accide ntally pum p ed into the detector. This

occurred during the freeway (ME1-5) and refuel ing without vapor recovery (ME4-4) tests on

May 5, 03. Another limitation of this continuou s instrum e nt was the long stabilization time

required for the fluorescence dete ctor upon instrum e nt start-up. In some cases, response at

the dete ctor was still stabiliz ing when the sam p ling period began. One of the m o st

significan t lim itations o f the for m aldehyde m o nitor was an apparen t sensitiv ity to moving

environm ents. It has been observed that when the form aldehyde instrum e nt was warm ed up

and operated in a stationary e nviro nm ent, such as a parkin g garage, and then subjected to

transport w h ile still operating, re sponse at the detector oscillat ed and increased in overall.

2-15

# Figure 2.4-1 shows the response of the contin uous for m aldehyde analyzer, stabilized and

“zeroed ” with a DNPH cartridge at the inlet, when statio nary and following startup and

driving of the sam p ling van where the response of the detector incr eases and oscillates.(V)ponCHOH

-0

. 2 -0

. 1

0 0. 1 0. 2 0. 3 0. 4 0. 5 0. 616:40:4816:48:0016:55:1217:02:2417:09:3617:16:4817:24:0017:31:1217:38:2417:45:3617:52:48

Ti m eResse i n s t a l l ed D N P H o n inle t

a t 17 : 2 2 an d c o n t in u e d

s a m p l i n g i n ga ra g e St a r t e d va n an d d r o v e b a c k to

DRI, DN PH s t il l o n in l e t a n d

s t il l a c q u i r i n g



# Figure 2.4-1. Effect of driving on continuou s for m aldehyde analyzer, during and after

sam p ling in ME2-5.

The environm ental conditions (temperature, relative hum idity, position, speed and other

param e ters) had one run where the logging system apparently locked up about 6 m i n into the

run and gave no further data. This was a 20 min refueling run and does not represent a

significan t loss in data since th e tem p eratur es and hum i d ity probably did not change

appreciably.

Table 2.4-1. Data Capture Summ ary

Par a m e te r Data Captur e

Am bient Can 100%

Ref uel Can 80%

Br eath Can 100%

DNPH 100%

Solid Ads

. 95%

SPME 100%

PID In ( 1 ) 100%

PID O u t ( 2 ) 80%

NDIR CO 85%

T

- 15 CO 85%

MS200 70%

F o r m aldehy de 10%

Env. Cond. 95%



# 2-16

# 3. RES U L T S

The m a in goal of the 2 nd 

# Reno Pilot Study was to demonstrate proper operation and

reliability of analytic al ins t rum e ntation and com p arability of tim e-in tegra t ed, sem i

continuous and continuous m e thods for com pounds of interest. The results section exam ines

the consistency between redundant m easure m ents and co-pollutants, evaluates tem poral and

spatial variations, and correlations among the vari ous data sets for m easured param e ters that

we expect will be correlated. One key aspect of the study des i gn was the built-in redu ndancy

between the continuous m e thods and the tim e -integrated m e thods. For exam ple, CO was

m easured from the tim e -integrated canis ter sam p les and from the T-15 and NDIR

instrum e nts. W e m easured BTEX fr om canis ters, continuous MS-200 and sem i - continuous

SPME as well as a surrogate m easure in the PID signal. F o rm aldehyde was m easured by the

continuous HCHO instrum e nt and by the DNPH car tridges

. In additio n, we m easured PID

signal from two independent ppbRAE units p o s ition e d in -cabin and outside the cabin, o r

collocated in outdoor microenvironm e nts.

3.1 Method Comparison of Redundant Data

3.1.1 PID versus PID

Two identical ppbRAE continuous PID mon itors were used to estim ate total VOC

concentrations, ionizable at 10.6 eV, inside and outside the ve hicle cabin. Prio r to and after

the pilot study, both units were ca librated using an activated car bon inlet filter for the zero

point and a certified BTEX m i xture (tot al concentration 3700 ppb) for span.

During several tests, the second unit was collocated with its inlet within 10 cm of the inlet of

the prim ary unit for quality assu ran ce purpos es. The resu lting data is s hown in Fig u re 3.1-

1a,b. W h ile the two units track each other accurate ly, after adjusting for differences in in let

trans it tim e, the abso lu te concen tr ations r ecorded differ significantly. The prim ary unit

(PID1) dem onstrated a positiv e offset of 40-50 ppb, which was expected since it w ould not

read below ~40 ppb eve n when the carbon inlet filter was in place. This behavior is eviden t

in the tests shown in Figure 3.1-1b. No consis tent bias was observed at the high peak

concentrations shown in Figure 3.1-1a, with bot h units reading higher at tim es. Since this

tim e a dif f e rence in sof t ware was identif ied, and they h a v e been h a rmonized for future

studies.

3-1

### M E 4 - R e f u el i n g w / o V R : t e st 4

0 100 0 200 0 300 0 400 0 500 0 600 0 700 0 800 0 900 0

0 5 1 0 1 5

e l a p s e d t i m e ( m in )BTEXestimatedbyPID(ppb)

P I D 1 PI D2

2 0



### M E 4 - R e f u el i n g w / o V R : t e s t 5

0 50 00 10 0 0 0 15 0 0 0 20 0 0 0 25 0 0 0 30 0 0 0

0 5 1 0 15 20

el a p se d t i m e ( m i n )BTEXestimatedbyPID (ppb)

PI D 1 PI D 2



# Figure 3.1-1a. Com p arison of estim a t ed BTEX c oncentrations m easured by PID instrum e nts

with in lets c o lloca ted within 10 cm . Data ar e running 1 m i nute averages. VR = nozzle vapor

recovery.

3-2

### M E 3 - R e f u e l i n g w / V R : t est 5

0 5 0 10 0 15 0 20 0 25 0

0 5 1 0 1 5

e l a p s e d t i m e ( m i n )BTEXestimatedbyPID(ppb)

PI D1 PI D2

2 0



### M E 2 - P a r k i n g G a r a g e : t est 5

0 10 20 30 40 50 60 70 80 90 1 0 0

0 5 1 0 1 5

e l a p s e d t i m e ( m i n )BTEXestimatedbyPID(ppb)

PI D1 PI D 2

2 0



# Figure 3.1-1b – cont’d. Com p arison of estim at ed BTEX c oncentrations m easured by PID

instrum e nts with inle ts c o lloca ted within 10 cm . Data are run n ing 1 m i nute averages. VR =

nozzle vapor recovery.

3-3

# Figure 3.1-2 shows the corresponding total VOC conce n trations, ionizable at 10.6 eV,

record ed by the two p pbRAE m o nitors during four freeway driving tes t s (d ata f o r the

am bient unit during test 2 was lost due to a da ta logger configuration error) where the second

unit m easured am bient VOC conce n trations outs ide the vehicle. As in the collocated unit

tests, the tw o m onitors track e ach o t her well during the high ventilati on segm ent of the test

(first 20 m i nutes). The less dynam i c variations in concentration recorded by the in-cabin unit

are consistent with expectations.

After the switch to low ventilat ion conditions at 20 m i nutes el apsed tim e , the in-cabin unit

shows very little correl ation to the am bient unit and, while not always stable, shows no

accum u latin g drift evid ence of interi or sources o r interferences.

3-4

### M E 1 - Free w a y: tes t 3

0 10 0 20 0 30 0 40 0 50 0 60 0 70 0 80 0 90 0

0 5 1 0 1 5 20 2 5 30 35 4 0

e l a p s e d t i m e ( m i n )BTEXestimatedbyPID(ppb) 

### in

- c a b in P I D am bi e n t PI D 

### M E 1 - F r ee w a y: te s t 1

0 20 0 40 0 60 0 80 0 10 00 12 00

0 5 10 1 5 2 0 25 30 3 5 40

e l a p s e d ti m e (m i n )BTEXestimatedbyPID(ppb) 

### in

- c a b in P I D am bi en t PI D



# Figure 3.1-2. Com p arison of estim ated BTEX concentration s m easured by PID instrum e nts

during freeway driving tests. Da ta are running 1 m i nute averages.

3-5

### M E 1 - F r ee w a y: tes t 4

0 10 0 20 0 30 0 40 0 50 0 60 0 70 0

0 5 10 1 5 20 2 5 30 35 4 0

el ap se d t i m e ( m i n )BTEXestimatedbyPID(ppb) 

### in

- c a b in P I D am bi e n t P I D



### M E 1 - Free w a y: tes t 5

0 100 200 300 400 500 600

0 5 10 15 20 25 30 3 5 40

el ap s e d t i m e ( m i n )BTEXestimatedbyPID(ppb) 

### i n

- c abi n PI D am bi en t PI D



# Figure 3.1-2 –cont’d. Com p arison of estim a t ed BTEX concentrations m easured by PID

instrum e nts during freeway driving test s. Data are running 1 m i nute averages.

3-6

# 3.1.2 NDIR vs. Electrochemical CO

Both an EP A-certified gas-filt er correlation N D IR optical CO analyzer (API m odel 300) and

a portable battery-operated pass ive electrochem i cal cell instrum e nt (Langan T-15) were

operated during all tests to m easure CO. Although data recovery was less than 100% f o r each

m e thod, and the electrochem i cal instrum e nt was not equipped to sam p le outside the in-cabin

breathing zone during the refueling and garage te sts, collocated m easurem ents were collected

during the two tests shown in Figure 3.1-3.

Although the NDIR instrum e nt recorded higher p eak values, due to its faster reponse tim e

, the m easurem ents are generally consistent to within about 1 ppm

. During the low-ventilation,

half of the tests shown the CO concentrations rem a in at or d ecrease tow a rds th e low e st level

m easured during the high-vent phase. This beha vior suggests that no in-c abin so urces o r

interferences are presen t.

There was good agreem ent betwe e n the two types of CO analyzers, due to the NDIR

instrum e nt’s intern al adaptive filterin g. This f ilter, which is required for EPA certification, is

intended to adjust the response ra te of the instrum e nt with respect to the stability of the raw

detector sig n al during a precedi ng tim e period, to reduce no ise. The len g th of the ‘filtering ’

period can range from 10 seconds up to 2 m i nutes , accord in g to the m a nufacturer. In practice,

the adap tive filter effectively averag es the out pu t data over a variable tim e period, resulting

in concen tra tion f l uctu ations tha t are broader and have a peak th at o ccur s later in tim e and a

lower m a ximum height. This effect can be s een in Figure 3.1-4, whic h shows the measured

CO concentrations from two si m ilar instrum e nt s drawing air f

r om the sam e inlet ins i de the

cabin of the test van while driving o n freew ay and surface streets with windows open (this

test was pe rf orm e d later in the d a y than the ME1 tests, concentr ations are low e r). The

API300 was the sam e instrum e nt used in the pilot study, while the ML9830 (Monitor Labs)

was an equivalent EPA-certif i ed gas

- f ilte r co rr elation NDIR instrum e nt that was operated

with the ad aptive filter turned off (a fixe d 10 second filtering period was selected). Both

instrum e nts have the sa m e perf ormance specif i cation s and were calib ra ted just pr io r to the

test using zero air and a 10.0 ppm CO standa rd, yet the ML9830 tim e series is m u ch m o r e

dynam i c and shows higher peak concentrations. Figure 3.1-4 also shows a tim e series of the

ML9830 data in which the four m i nutes preceding each data point were averaged. T h is series

m a tches the API300 data alm o st exactly, except for the first large peak w h ich was apparently

steep enough to trigger the API300’s adap tive filter into fast response m o de.

Despite the differences in response rate, the ov erall average concentrat ions recorded for the

test period shown were very com p arable: 1.26 ppm from the ML9830 versus 1.31 ppm from

the API300. Fast respon s e is des i red in order to b e tter characterize the v a riability of p o llutant

concentrations in a m i croenvironm ent, so the ML9830 is preferable for the field study. In

addition to the convenience of front panel conf iguration of t h e data filter, the ML9830 also

uses about 50% less pow er and has an internal ze ro air gene ra tor to allow autom a tic b a seline

checks.

3-7

### M E 1 - Fr e e w a y : t e st 3

0 5 10 15 20 25 30 35 40 45 50

0 5 1 0 15 2 0 25 3 0 35 4 0

el ap se d t i m e ( m i n )CO(ppm) ND I R

_ C O La nga n

_ C O



### M E 1

- Fr e e w ay: t est 4

0 2 4 6 8 10 12 14

0 5 1 0 15 20 25 3 0 35 40

el ap se d t i m e ( m i n )CO(ppm) ND I R

_ C O L a n g an _C O



# Figure 3.1-3. Com p arison of NDIR (API m odel 300) and electrochem i cal (Langan T15v)

CO m onitors during two freeway driving tests.

The NDIR CO data are running 1 m i nute averag es, while the electrochem ical instrum e nt

record ed data is in d i screte 1 m i nute averages. In test 3, the N D IR inst rument’s analog output

range (0 -20 ppm ) was exceeded during the firs t 4 m i nutes.

3-8024681012 15: 40 15: 45 15: 50 15: 55 16: 00 16: 05 16: 10 16: 15 16: 20

C O ( ppm )ML9830API300ML9830_4min.AvgFigure 3.1-4. Comparison of two gas-filter correlation NDIR CO analyzers during on-road sampling.Data fromthe ML9830 instrument are shown as recorded(10 second averages) and as4 minute running averages.3-9

# 3.1.3 CO versus Canister CO

Average CO concentrations were also m easured by GC analysis of the integ r a t e d canis te r

sam p les that were collected for the d u ration of each test. Fig u re 3.1-5 sh ows a scatter plot of

the average continuous data from t h e NDIR or electrochem ical CO i n strum e nts versus the

CO from the corresponding canister. The canister CO is generally about 8% higher, but there

is no consistent bias. The com p arison is also m a de on a test-by-test basis in the second chart

of this figure, showing that discrepanc ies between the two methods occur in all

m i croenvironm ents and at both high and low co ncentrations. The underestim ation of CO by

the NDIR instrum e nt in the two tests with the hig h est average concentration (ME1- test 3 and

ME2 – test 2) is due, at least in part, to exceed ences of the instrum e nts output rang e which

resulted in truncation of peak concentrations abov e about 23 ppm

. This over-ranging problem

was identified and corrected befo re the end of the pilot study.

3-10

## y = 1

. 0 8 x

R 2 

## = 0

. 8 5

0 2 4 6 8 10 12

0 246 8 1 0 1 2

a v e r a g e o f c o nt i n uous C OCanisterCO



## 0 2 4 6 8 10 12

ME 1 M E 2 M E 3 M E 4CO (ppm) 

## a v e r ag e of c o nt i n u o us C O

Ca n i s t e r C O



# Figure 3.1-5

. Average CO concentration for each test m easured by continuous m o nitor and

GC analysis of integrated canister sam p le. ME1= morning rush hour commute;

ME2=parking garage; ME3= refueling with va por recovery; ME4= refueling without vapo r

recovery.

3-11

# 3.1.4 MS vs. Canister

The MS200 perform e d well in 16 of the 20 ME test s. For all of those runs we can com p are

the integrated MS200 response to the caniste r data. Figure 3.1-6 shows the correlation for

benzene, to luene and th e sum of the C8 benzenes (ethylb e nzene, o, m

, & p-xylene). The C8

benzenes are presented together because we cannot separate them us ing the MS 200. The

correlations are all very good, with > 0.9 R-square . The correlation for toluene is the best

with a 0.99 R-square. B o th toluene and the C8 benzenes show a clos e 1:1 correlation, but

benzene seem s to be overpredicted by the MS200.

Bz = 1.1 5 37 x + 1. 0 948

R 2 

### = 0

. 9 0 16

T o l = 0.97 0 3 x + 1

. 8 0 68

R 2 

### = 0. 9 914

C8 = 1.0 6 38 x + 0. 6 664

R 2 

### = 0. 9 529

0 10 20 30 40 50 60 70 80

0 2 0 4 0 6 0 8 0

Ca ni s t er, pp b vMS200,ppbv 

### B enz e n e

To l u e n e

C 8 Be nz en e s

Li ne a r ( B e n z e ne )

L i ne a r ( T o l u ene )

L i n e ar ( C 8 B e n z e n e s )



# Figure 3.1-6 Com p arison of canister and MS 200 data for all m e asured species.

To further investigate the com p arison for benzen e, we plotted the benzene concentrations in

Figure 3.1-7. This figure shows random sca tter around the trend line over the range of 25

ppbv down to less than 2 ppbv. Overall the MS200 performed very well for runs with valid

data. W e are still inves t igating the causes of th e f a ilures of this instru m e nt and f e el that it

provides excellent supplem ental data but s hould not be relied upon as a prim ary m e thod.

3-12

### Bz = 1

. 1 5 37 x + 1. 094 8

R 2 

### = 0

. 9 0 16

0 5 10 15 20 25 30

0 5 1 0 15 20 25 30

C a nist e r

, ppb vMS200,ppbv



### B e n z ene

Li ne a r ( B e n z ene )



# Figure 3.1-7. Com p arison of MS200 and canister for benzene only.

3.1.5 SPME vs. Canisters

Table 3.1-1 shows the com p arison of canister B TEX data with averaged and temperature

corrected S P ME data. In general, SPME BT EX concentrations are higher than canis ter

concentrations. This is most probably due to th e tem p erature differences between the sta tic

calibration and sam p ling conditions and inadequate correction for tem p er ature. However, the

passive SP ME sam p ling rate coul d also be affected by the local wind speed, especially if the

local gusts are close to 5 mph threshold. W e observed higher SPME uptake of analytes in the

dynam i c system , if the fl ow rate of a standa rd gas m i xture was higher than 100 m l/m i n.

After clean ing and con d ition i ng, th e SPME fibers were sto r ed in the freezer and taken to

sam p ling sites in a cooler with dr y ice. Although the fibers w e re taken out of th e cooler prior

to sam p ling

, we are no t ce rta i n if suf f i cient tim e was allowed f o r f i ber equ i libr ations to

am bient temperatu r e. In retro s pec t , it was an e r ror, sin ce we dete rm ined late r tha t the f i ber

uptake is h i ghly depend ent on tem p eratu r e (see Section 2.3. 2). For the prim ary stud y we will

change the SPME f i ber storage con d itions and w ill sto r e th em in m e tal cans with activa t ed

charcoal at the bottom (sim ilar to Te nax tubes) at am bient temperature.

3-13Table 3.1-1. Data comparison between SPME and Canistercanspmecanspmecanspmecanspmecanspmesitedatestrthhmmbenzebenzetoluetolueetbzetbzmp_xylmp_xylo_xylo_xylFreeway4/29/03742-8229.1015.0345.35 87.427.4818.3724.9250.539.9415.96RefuelingW/VaporRecovery4/29/031200-12203.3811.949.9152.851.4310.704.8227.041.8510.03Garage4/29/031642-17125.6519.0014.67 56.493.1016.1110.5243.124.2014.04Freeway4/30/03739-81910.01 24.0153.75127.788.6925.1129.4872.9311.7423.15RefuelingW/OVaporRecovery4/30/03921-9419.4629.0434.27112.885.5018.0219.0266.767.3119.75RefuelingW/VaporRecovery4/30/031045-11051.304.664.5320.460.976.933.5019.481.475.00RefuelingW/OVaporRecovery4/30/031205-12452.1311.027.8551.681.1514.113.9631.281.527.29Garage4/30/031645-17159.9437.2531.92110.846.9826.4324.0687.429.7531.54Freeway5/1/03720-80018.13 32.6075.57146.8312.28 26.7740.1384.2815.4628.29RefuelingW/OVaporRecovery5/1/031106-11262.346.80 10.1049.241.8314.576.4839.622.5110.41RefuelingW/VaporRecovery5/1/031225-12451.615.616.2817.021.204.604.2113.581.683.23Garage5/1/031642-171710.63 20.3334.25 71.177.2313.9125.3545.999.8115.34Freeway5/2/03735-8157.2722.6230.81114.784.7724.7615.6667.076.0921.03RefuelingW/OVaporRecovery5/2/03918-93820.49 44.7759.93154.258.1331.2528.7092.9010.7129.19RefuelingW/VaporRecovery5/2/031036-10562.3020.449.2867.202.1012.177.8342.823.0612.74Garage5/2/031645-17155.296.0717.1022.803.795.5513.5315.845.364.58Freeway5/5/03750-8309.6019.2544.69108.018.3118.2128.7663.5211.3520.17RefuelingW/OVaporRecovery5/5/03923-94366.93 52.76142.14198.2611.17 18.3036.0363.8111.7516.26RefuelingW/VaporRecovery5/5/031045-11051.555.757.2318.131.392.494.969.741.912.09Garage5/6/031645-17154.866.2914.1622.393.255.8211.7520.924.556.853-14

# Figure 3.1-8 shows the scatter plots for canis ter and S P ME data before temperature

c o r r e c t i o ns

.

0 50 100 150 200 250

0 5 0 100 150 200 250

Ca n i s t e r Co n c e n t r a t i o n ( p p b )SPMEConcentration(ppb)



### benz ene tol uene ethy l benz ene m

, p- x y l ene o- x y l ene



# Figure 3.1-8. Scatter Plots for raw data fr om SPME vs canister for the Pilot Study 2003

Scatter plots after tem p erature correction.

0 50 100 150 200

0 5 0 100 1 5 0 200

C a ni s t e r C o n c e n t r a t i o n ( p pb)SPMECon centration(pp b)

benz ene to l u e n e et hy l b e n z ene m

, p- x y l ene o- x y l ene



# Figure 3.1-9. Scatter Plots for temperature corrected SPME vs canister data for the Pilot

Study 2003

Figure 3.1-10 and Table 3.1-2 show s the correla tions after rem oving th e two visible outliers

(benzene an d toluene fro m refueling w/ o vapor recovery May 5th at 923-943):

3-150 40 80 120 160

0 4 0 8 0 1 2 0 160

C a n i st er C o n c en t r a t i o n ( p p b )SPMECon centration(pp b)

benz ene t o l uen e et hy l b e n z ene m

, p

- xyl e n e o- x y l ene



# Figure 3.1-10. Scatter plots from SPME vs Canister for the Pilot S t udy 2003 with two

outliers removed.

Table 3.1-2. Correlation of Scatter Plot s from SPME and Canister Com p a r ison

Compo und E q u a t i o n Corr elation

Be n z e n e y = 1. 83 6 5 x + 4. 97 32 R 2 

### = 0

. 72 91

T o lue n e y = 1. 92 0 2 x + 22 .6 17 R 2 

### = 0

. 79 36

Et h y l b en z e ne y = 1. 68 9 4 x + 7. 19 97 R 2 

### = 0

. 52 55

m

, p-x y len e y = 1. 78 1 4 x + 17 .3 23 R 2 

### = 0

. 64 52

o

- x y le n e y = 1. 63 6 7 x + 4. 04 33 R 2 

### = 0

. 65 26



# The scatter plots show linearity of the SPME data com p ared to canister data but th e rela tive l y

low correlation values and the slope in the range of 1.6 – 1.9 can be associated with the

differences in storage of the c onditioned fibers before sam p li ng. As noted above, m o st fibers

were not probably stabilized to am bient tem p er ature before sam p ling. Since the fibers were

colder than the environ m ent, so m e variab ility o f the data is expected. This proble m will be

corrected in the prim ary study.

Sam p led fibers were s t o r ed an average of 5 hou rs and all s a mples were analyzed th e sam e

sam p ling day.

3-16

# 3.1.6 SPME vs. MS

Data from SPME se m i -continuous sam p les compar ed satisfactorily with continuous data

obtained from the MS 200. In general concentra tions are within the sam e ranges and changes

in concentration lev e ls track each oth e r m o st of t h e tim e. However, the S P ME concentrations

are higher in m o st cases. As explained before, this m a y be due to the inadequate c o rrec tio n

for tem p erature and hu m i dity differences as co mp ared with static calibration conditions and

cold fiber storage condit ions prior to sam p ling.

3-17

### E t hy l b e n z e ne a n d x y l e ne s

0 40 80 120 160

7:30:43 7:37: 5 5 7 : 45 : 0 7 7 :52:19 7 : 59 : 3 1 8 :06:43 8:13:55 8: 2 1 : 0 7

Ti m eConcentration,ppb



### MS SP M E



### Be n z e n e

0 10 20 30

7:30:43 7 : 37:55 7: 45 : 0 7 7 : 5 2: 19 7: 5 9 : 3 1 8 :06: 4 3 8:13:55 8:21:07

Ti m eConcentration,ppb



### MS SP M E



### Tol ue n e

0 40 80 12 0 16 0

7 : 30:43 7:37:55 7:45: 0 7 7 : 52:19 7: 5 9 : 3 1 8 :06:43 8:13:55 8: 2 1 : 0 7

Ti m eConcentration,ppb



### MS SP M E



# Figure 3.1-11. 10 m i nutes average MS data vs SPME benzene and toluene concentrations:

Freeway 5/02 7:35-8:15 am

3-18

### Be n z e n e

0 10 20 30 40

7 : 3 3 : 3 6 7 : 4 0: 4 8 7: 48 : 0 0 7 : 5 5 : 1 2 8: 02 : 2 4 8 : 0 9 : 36 8: 1 6 : 4 8 8 : 24: 00

Ti m eConcentration,ppb



### MS SP M E

Tol ue ne

40 80 12 0 16 0

7: 33 : 3 6 7 : 4 0 : 48 7: 48 : 0 0 7 : 5 5 : 12 8: 0 2 : 2 4 8 : 0 9: 36 8: 1 6 : 4 8 8 : 2 4: 00

Ti m eConcentration,ppb

MS SP M E

E t hy l b e n z e ne a nd x y l e n e s

0 40 80 12 0 16 0

7: 33 : 3 6 7 : 4 0: 48 7 : 48: 0 0 7: 55 : 1 2 8 : 0 2: 24 8 : 09: 3 6 8: 16 : 4 8 8 : 2 4: 00

Ti m eConcentration,ppb

MS SP M E



# Figure 3.1-12. 10 m i nutes average MS data vs SPME benzene and tolu ene concentrations :

Freeway 4/30, 7:35 am

3-19be nz e n e

0 30 60 90

9:15: 50 9:1 8 :43 9 : 21:3 6 9 : 24: 29 9:27: 22 9: 30:1 4 9:33: 07 9:36: 00 9: 38:53

Ti m eConcentration,ppb

MS SP M E



### Tolue ne

0 50 10 0 15 0 20 0 25 0 30 0

9:15:50 9:18 : 4 3 9 :21 : 3 6 9 : 2 4 :29 9 :27 : 2 2 9 : 3 0 :14 9 : 3 3:07 9:36 : 0 0 9 : 3 8:53

Ti m eConcentration,ppb

MS SP M E



### E

t hy l b e n z e ne a n d x y le n e s

0 50 10 0 15 0 20 0 25 0 30 0

9:1 5 :5 0 9 :18:43 9:2 1 :3 6 9 :24:29 9 : 27 :22 9 :3 0:1 4 9 : 33 :07 9 :3 6:0 0 9:3 8 :5 3

Ti m eConcentration,ppb

MS SP M E



# Figure 3.1-13. 10 m i nutes average MS data vs SPME benzene and toluene concentrations:

Refueling w/o VR 5/02 9:18 am

3-20

# 3.1.7 DNPH vs. Formaldehyde

Com p arisons of for m aldehyde data are few si nce the supplem e ntal continuous analyzer

provided little reliable data due to flow fluxuation and unstability during movem e nt

Com p arison of for m alde hyde data from DNPH w ith the final garage sampling event (ME2-5)

shows that average concentrati on of for m aldehyde detected by the continuous instrum e nt was

11.5 ppb, and the tim e integrated D N PH sa mple for the sam e event was only 5.41 ppb. I f

data from the continuous CO m o nitor from th e sam e experim e nt is used to reconstruct

concentrations of for m al dehyde for the earlier portions of the run, the average form aldehyde

concentratio n m a y be estim ated an d com p ared to the DNPH tim e-integrated form aldehyde

data (described in 3.2.2.).

The continuous for m aldehyde detector is desi gned for stationary laboratory use, which

accounts for its poor perfor m ance on a m obile pl atform . Bas e d on these pilot study results,

continuous form aldehyde m easurements will only be m a de for stationary m e asure m ents in

the 3 city field studies.

3.1.8 Tenax vs. Canisters

Appendix B lis t the f u ll data s e ts f o r

canis te r and Tenax samples. Si n c e Tenax and canis ter

sam p les overlap at C8-C12 carbon num bers, it is possible to com p are concentrations for

toluene, ethylbenzene, m / p-xylene and o-xylen e obtained from both me thods. F i gure 3.1-14

shows that the correlations between both m e t hods are good. The scatte rplots exclude the

5/5/03 refueling without vapor r ecovery (ME4) sam p les. For th is one ME4 replicate, the

canister value was m u ch higher than the Te nax sam p le, suggestive of a Tenax tube

breakthrough. for this ME. This c ould be due to the extrem ely high gasoline concentrations

encountered in this ME. It is possible that the breakthrough occurred for Tenax sam p le. One

issue with th e Tenax samples is the a ccura te dete rm ination of the volum e sam p led. Since the

flow rate is m easured at the beginning and at the end of all sampling periods, and the average

flow is used for volum e calculati on, it is poss i ble tha t the v o lum e is not very pr ecis e, if the

flow drop over the sampling peri od is substantial and non-linear . W e are currently improving

on the standard m e thod by adding the data lo gger to the canis ter

- Ten a x-DNPH cartr i dge

sam p ling system that will a llow us to continu ously m onitor f l ow rate s, thus allo wing f o r

accurate volum e determ ination.

3-21Tol u e ne

y = 0

. 88 53 x + 8. 4 1 1 9

R 2 = 0. 85 9 5

0 50 100 150 200 250 300 350 400 450

0 5 0 100 15 0 2 00 2 5 0 300 350 40 0 4 50

C a n s

, pp bCTenax,ppbC Et h y l b e n z e n e

y = 0. 993 5x

- 3

. 75 45

R 2 = 0

. 90 89

0 10 20 30 40 50 60 70 80 90

0 1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0

C a n s

, pp bCTenax,ppbC

m / p- X y l e ne

y = 1

. 12 25 x - 11

. 6 9 4

R 2 = 0

. 92 36

0 50 10 0 15 0 20 0 25 0 30 0 35 0

0 5 0 100 150 2 0 0 2 50

C a n s

, pp bCTenax,ppbC o- X y l e n e

y = 1

. 03 21 x - 6. 0 3 8

R 2 = 0. 925 8

0 20 40 60 80 10 0 12 0

0 2 0 4 0 6 0 8 0 1

C a n s

, pp bCTenax,ppbC

0 0



# Figure 3.1-14 Com p arison of canis ter and Tenax data for all ME

3-22

# 3.2 Compariso n s of Correlated Data

3.2.1 PID vs. CO

Since both carbon m o noxide a nd BTEX are produced by gasoline com bustion, they are

expected to track each other in an autom obile exhaust dom in ated environm ents. Figure 3.2-1

shows the two m easurem ents track well during th e parking garage tests that are focused on

cold-start em issions, although the ratio is variable as indicate d by the scatter in Figure 3.2-3.

The apparen t tim e lag f o r the sm alle r peaks is an artifact of the API NDIR CO instrum e nt’s

adaptive filtering, described in the previous sect ion, and subsequent averaging of the data.

During the freeway driving tests, shown in Figure 3.2-4, the correlation between CO and

VOC is good, but not as high as the parking garage data.

3-23M E 2

- P a r k i n g G a r a ge: t e s t 1

0 2 4 6 8 10 12 14 16 18

0 5 10 1 5 2 0 25 30

e l a p s e d t i m e ( m i n )CO(ppm)

0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 3 5 0 4 0 0BTEXestimatedbyPID(ppb) ND I R

_ C O PI D1

M E 2 - Pa r k i n g G a r a g e : te s t 2

0 5 10 15 20 25 30

0 5 10 15 20 25 30

e l a p sed t i m e ( m i n )CO(ppm)

0 100 200 300 400 500 600BTEXestimated byPID(ppb) ND I R

_ C O PI D 1



# Figure 3.2-1. Com p arison of CO and BTEX by PID during parking garage tests.

Data are running 1 m i nute averages. The CO instrum e nt’s analog out put range (0-20 ppm )

was exceeded briefly during the two la rge peak s n ear th e end of test 2.

3-24M E 2

- P a r k i n g G a r a g e : te s t 3

0 5 10 15 20 25

0 5 10 15 20 2 5 30

e l a p s e d t i m e ( m i n )CO(ppm)

0 1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0BTEXestimatedbyPID(ppb) ND I R

_ C O P I D 1

M E 2 - P a r k i n g G a r a g e : te s t 4

0 2 4 6 8 10 12 14 16

0 5 1 0 15 20 2 5 30

e l a p s e d t i m e ( m in )CO(ppm)

0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 3 5 0BTEX estimatedbyPID(ppb) NDI R

_ C O P I D 1

ME2

- Pa r k i n g G a r a ge : t e s t 5

0 5 1 0 1 5 2 0 2 5

0 5 10 1 5 2 0 25 30

e l a p s e d t i m e ( m i n )CO(ppm)

0 10 0 20 0 30 0 40 0 50 0 60 0BTEXestimatedbyPID(ppb) ND I R

_ C O PI D 1



# Figure 3.2-1 – cont’d. Com p ar ison of CO and BTEX by PID dur i n g pa r k i n g ga r a ge t e s t s

. Data are run n ing 1 m i nute averag es.

3-25p a r k i n g ga r a ge t e s t s

y = 1 7

. 48x + 13. 4 6

R 2 = 0. 76

0 100 200 300 400 500 600

0 5 10 15 20 2 5 30

C O ( ppm )BTEXbyPID(ppb)



# Figure 3.2-3. Scatter plot of CO vs BTEX by PID during parking gara ge tests. Data are

running 1 minute averages.

3-26M E 1

- F r eew ay: te st3

0 5 10 15 20 25 30

0 5 10 1 5 20 2 5 30 35 40

e l a p sed t i m e ( m i n )CO(ppm)

0 1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 8 0 0 9 0 0BTEX estimatedbyPID(ppb) ND I R

_ C O PI D 1

M E 1

- Fr eew ay: t e st 4

0 2 4 6 8 10 12 14

0 5 10 1 5 20 2 5 30 35 40

e l a p sed t i m e ( m i n )CO(ppm)

0 1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0 7 0 0BTEXestimatedbyPID(ppb) ND I R

_ C O P I D 1

M E 1

- F r eew ay: te st5

0 1 2 3 4 5 6 7 8 9 10

0 5 10 1 5 20 2 5 30 35 40

e l a p sed t i m e ( m i n )CO(ppm)

0 1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0BTEXestimatedbyPID(ppb) ND I R

_ C O PI D 1



# Figure 3.2-4. Com p arison of CO and BTEX by PID during freeway driving tests.

Data are run n ing 1 m i nute averages. In test 3, th e CO instrument’s an alog output range (0-20

ppm ) was exceeded during the firs t 4 m i nutes.

3-27

# 3.2.2 CO vs. Formaldehyde

For the last two garage sam p ling e v ents (M E2-4 and ME2-5), tim e series for continuous

for m aldehyde and CO show inconclusive results. Figure 3.2-5 shows tim e series data for CO

and for m aldehyde for ME2-4. During the ME2- 4 period in which form aldehyde data was

above the detection limit, both the CO and form aldehyde appear to respond to the same

event, but th e peaks are not in phas e with each o t her.

0. 0 0 2. 0 0 4. 0 0 6. 0 0 8. 0 0 10

. 0 0 12

. 0 0 14

. 0 0 16

. 0 0 18

. 0 0 20

. 0 016:40:4816:48:0016:55:1217:02:2417:09:3617:16:48

Ti m eHCHO (ppb)

0. 0 0 2. 0 0 4. 0 0 6. 0 0 8. 0 0 10

. 0 0 12

. 0 0 14

. 0 0 16

. 0 0 18

. 0 0 20

. 0 0NDIRCO(ppm) HC H O ( p pb )

ND IRC O ( p pm )



# Figure 3.2-5 ME2-4 continuous HCHO and CO tim e series with unexpla ined difference in

lag between the two ins t r u m e nts.

Approxim a tely 2.5 m i nutes separate the instrum e nt responses. This indicates that either the

tim e lag correction of 6 m i nutes is not accura te for this test, or the adaptive s m oothing

feature of the CO instrum e nt is caus i ng a dela yed peak rise in CO. Figure 3.2-6 shows the

sam e ti m e series data following adjustm e nt of the for m aldehyde data by 2.5 minutes t o

com p ensate for the undeterm ined source of erro r. The data track each other very well.

3-280. 00 2. 00 4. 00 6. 00 8. 00 10

. 0 0 12

. 0 0 14

. 0 0 16

. 0 0 18

. 0 0 20

. 0 016:40:4816:48:0016:55:1217:02:2417:09:3617:16:48

Ti m eHCHO(ppb)

0. 00 2. 00 4. 00 6. 00 8. 00 10

. 0 0 12

. 0 0 14

. 0 0 16

. 0 0 18

. 0 0 20

. 0 0NDIRCO(ppm) HC HO (p pb )

ND IR C O ( p pm )



# Figure 3.2-6. ME2-4 continuous H C HO ti m e s e ri es shifted back 2.5 minutes to match CO

tim e series.

Once this tim e adjustment was m a de, CO an d HCHO concentration s were com p ared by

regres sion, and the res u lting eq u a tion ([HCHO] = [CO]*1.2996-1.14587, R 2 

# = 0.91) was

used to estim ate HCHO concentrat ions for the period prior to su cces s ful data captu r e for this

experim e nt. The resulting average concentr ation for the estim ated for m aldehyde data

com b ined with the actual form a l dehyde data was 5.414 ppb. The tim e integrated

for m aldehyde data from the DNPH for the ME 2-4 experim e nt was 7.348 ppb. The estim ated

value is 74 % of the o b served tim e integra t ed sam p le. Despite the discrepancy in phase

between the continuous CO and for m aldehyde an alyzers, this experi m e nt is the best

indication that the continuous for m aldehyde an alyzer m a y work well if properly tuned and

operated in a suitable environm ent. It also indi cates that CO m a y serve as a useful surrogate

for for m aldehyde. To explore this relationshi p further, form aldehyde results from the DNPH

cartridges were plotted in a scatter plot agains t CO f r om tim e integra t e d caniste r sa mples f o r

each m i croenvironm ent. Figure 3.2-7 shows the plot with different m i croenviro nm ents

having unique sym bols on the plot. Form alde hyde from the Freeway m i croenvironment does

not correlate with CO sam p les from the sam e environment. The garage and refueling

m i croenviro nm ents app ear to have a positive corr ela tion with CO but clu s te r f o r each

m i croenvironm ent. Fitting a linear regre ssion through data points for the Garage and

Refueling m i croenvironm ents, neglecting th e Freeway m i croenvironm ent, gives a good

correlation ([HCHO] = 0.594*[CO] + 0.397, R 2 

# = 0.793).

3-290 5 10 15 20 25

0 2 4 6 8 10 12 14

Ca n CO ( p p m )DNPHHCHO(ppb)

Ga r a ge

Fre e w a y

R e fu e l w / o V

. R.

Re fu e l w / V

. R.



# Figure 3.2-7. Scatter plot of for m aldehyde (fro m DNPH) and CO for all microenvironm e nts.

3-30

# Finally, comparison of continuous for m aldehyde and CO m easure m ents for the last garage

sam p ling event (ME2-5) shows poor correlation in phase and tim ing (Figure 3.2-8). The

unexplained 2.5 m i nute lag that resolved peak s in the ME2-4, did little to help this

com p arison.

0. 0 0 5. 0 0 10

. 0 0 15

. 0 0 20

. 0 0 25

. 0 016:4016:4816:5517:0217:0917:16

Ti meHCHO (ppb)

0. 0 0 5. 0 0 10. 0 0 15. 0 0 20. 0 0 25. 0 0NDIRCO (ppm) HC H O ( ppb )

N D IR C O ( p p m )



# Figure 3.2-8. Form aldehyde and CO tim e series f o r ME2-5.

3-31

# 3.2.3 SPME vs. PID

SPME total BTEX se mi-continuous data com p ar es reasonably with the continuous signal

obtained from the interior PID situated righ t next to the fiber while sampling. The SPME

concentratio ns are with in the rang e of the PID signal and follow the changes in PI D

concentratio ns.

10 0 20 0 30 0 40 0

7: 3 5 7: 4 1 7 : 48 7 : 55 8 : 01 8: 0 8 8: 1 5

Ti m ePID Concentration (ppbv)



### 10 0 20 0 30 0 40 0SPME Concentration(ppbv)



### PI D 1 SP M E to t B T E X



# Figure 3.2-9. SPME 10 m i n total BTEX vs. PI D 10 m i n averages, Freew ay, 5/02, 7:35 am

0 10 0 20 0 30 0 40 0 50 0 60 0 70 0

9 : 21 9: 27 9 : 34 9 : 41

Ti m ePIDConcentration (ppbv)



### 0 10 0 20 0 30 0 40 0 50 0 60 0 70 0SPMEConcentration (ppbv)



### PI D 1 S P M E to t BT E X



# Figure 3.2-10. SPME 10 m i n total BTEX vs. PI D 10 m i n a v erages, Refueling w/o VR 4/30

9:21am

.

3-32

### 0 10 0 20 0 30 0 40 0 50 0 60 0 70 0

7 : 39 7 : 45 7: 5 2 7: 5 9 8: 05

Ti m ePIDConcentration(ppbv)



### 0 10 0 20 0 30 0 40 0 50 0 60 0 70 0SPMEConcentration(ppbv)



### PI D 1 SPM E to t BT E X



# Figure 3.2-11. SPME 10 m i n total BTEX vs. PI D 10 m i n averages, Freew ay 4/30, 7:35 am

.

0 2 0 0 4 0 0 6 0 0 8 0 0 100 0 120 0 140 0 160 0 180 0

9 : 1 8 9 : 2 4 9 : 3 1 9 : 3 8

T i m ePID Concentration(ppbv)

0 2 0 0 4 0 0 6 0 0 8 0 0 1 000 1 200 1 400 1 600 1 800SPMEConcentration(ppbv)

P I D 1 S P M E to t B T E X



# Figure 3.2-12. SPME 10 m i n total BTEX vs. PI D 10 m i n a v erages, Refueling w/o VR 5/02

9:18 am

.

3-33

### 0 50 10 0 15 0 20 0

16 : 4 5 1 6: 5 1 16 : 5 8 1 7: 0 5 17 : 1 1

Ti m ePIDConcentration(ppbv)



### 0 50 10 0 15 0 20 0SPMEConcentration(ppbv)



### PI D 1 S P M E to t BT E X



# Figure 3.2-13. SPME 10 m i n total BTEX vs. PI D 10 m i n averages, Pa rking Garage 5/06,

16:45 pm

.

Continuous estim ates of total VOC by a PID pp bRAE moni tor com p ared reasonably to the

sem i -continuous m easurem ents of BTEX obtained from analysis of SPME fibers.

3-34

# 3.3 Environmental Factors

The various environm ental conditions m onito red during this study are presented in this

section by m i croenvironm ent. These data were collected once every 10 seconds, to sim p lify

the presentation, we present the average for each 10 m i n se gm ent (to correspond w ith th e

SPME tim e interval) and the overall average va lue In addition, we present tem p erature and

wind data collected at a weather station on top of DRI’s building. These data are useful as a

general reference for local c onditions, however, it is im portan t to point out that DRI’s

building is o n top of a hill with nothing to block winds for approxim a tely 270 degrees around

and is noted as being one of the windiest sp ots in th e a r ea. Th is is im portant since we

selec t ed the ref u eling stations in a location at the bottom of a nearby valley approxim ately

250 feet lower in elevation with a large ridge bl ocking the prevailing winds. For all stationary

MEs we m o nitored wind with a hand -held anem om et er that h a d a lower-li m it of detection of

approxim a tely 1 m ph.

For the freeway m i croenvironm ent (ME1), we m eas ured temperature and relative hum i dity at

the driver’s breath i ng zo ne which was also the sa mple inle t lo cation f o r all equipm ent excep t

the second PID which was m onitoring the air outside the van. The outside PID inlet was

located on the radio antenna on the right front co rner of the van. Since the sam p ling location

was inside the van, the tem p erature is typicall y h i gher than the am bient. We also m o nitored

the tem p erature on the outside su rface of the fu el tank. These data are p r esented in Tab l e 3.3-

1 along with the average conditi ons for the DRI weather stati on. The average tem p erature in

the van climbed during the runs partially due to the f a c t tha t we started low ventilation

conditions h a lfway thro ugh the run. Relativ e hu m i dities were relativ ely constan t . The fuel

tank tem p erature clim bed steadily during the run, which was interesting considering the

am bient temperatures did not. This was due to the recirculation of fuel a f ter is passe s the f u el

injectors and picks up heat from the engine. Th e 10 second data of fuel tank tem p eratures for

an exam ple run are presented in F i gure 3.3-1.

3-35

# Table 3.3-1. Environm ental Conditio ns for Freeway Driving MEs.

Fue l T a nk

M E D a t e S t a r t E n d Da ta Set T em p, C H u m i d ity

, % T e m p, C W i n d, m p h T e m p, C

M E 1 - F r ee wa y 4 / 2 9 04 / 2 9/ 03 7: 42 8: 22 a v g. o f 1 s t 1 0 m i n u t es: 1 2 3 7 5

a v g. o f 2nd 10 m i n u t e s : 1 2 3 2 7

a v g. o f 3 r d 10 m i nu t e s : 1 6 3 2 1 1

a v g. o f 4t h 10 m i n u t e s : 2 1 3 2 1 3

A v e r a g e of a l l 1 5 3 3 9 1

. 8 4

. 4

M E 1 - F r ee wa y 4 / 3 0 04 / 3 0/ 03 7: 39 8: 19 a v g. o f 1 s t 1 0 m i n u t es: 1 0 4 2 4

a v g. o f 2nd 10 m i n u t e s : 1 3 3 4 7

a v g. o f 3 r d 10 m i nu t e s : 2 1 2 8 1 1

a v g. o f 4t h 10 m i n u t e s : 2 5 2 6 1 4

A v e r a g e of a l l 1 7 3 3 9 3

. 0 1

. 5

M E 1 - Fre e w a y 5/ 01 05 / 0 1/ 03 7: 20 8: 00 a v g. o f 1 s t 1 0 m i n u t es: 1 1 4 4 7

a v g. o f 2nd 10 m i n u t e s : 1 6 3 1 8

a v g. o f 3 r d 10 m i nu t e s : 2 0 3 0 1 0

a v g. o f 4t h 10 m i n u t e s : 2 1 3 4 1 2

A v e r a g e of a l l 1 7 3 5 9 1

. 2 4

. 4

M E 1 - F r ee wa y 5 / 0 2 05 / 0 2/ 03 7: 35 8: 15 a v g. o f 1 s t 1 0 m i n u t es: 1 6 3 6 1 1

a v g. o f 2nd 10 m i n u t e s : 2 0 3 0 1 2

a v g. o f 3 r d 10 m i nu t e s : 2 3 3 0 1 5

a v g. o f 4t h 10 m i n u t e s : 2 3 3 3 1 6

A v e r a g e of a l l 2 0 3 2 1 4 4

. 5 7

. 8

M E 1 - F r ee wa y 5 / 0 5 05 / 0 5/ 03 7: 50 8: 30 a v g. o f 1 s t 1 0 m i n u t es: 1 5 3 9 7

a v g. o f 2nd 10 m i n u t e s : 1 7 3 3 9

a v g. o f 3 r d 10 m i nu t e s : 2 0 3 6 1 2

a v g. o f 4t h 10 m i n u t e s : 2 2 3 9 1 6

A v e r a g e of a l l 1 8 3 7 1 1 1

. 8 5

. 4 Sam p lin g Po in t Me a s u r e s Am b i e n t C o n d itio n s

( D R I W e a t her S t a t i o n)



# 3-36

### 0 2 4 6 8 10 12 14 16 18

7: 33 7:40 7: 48 7: 55 8: 02 8: 09 8: 16 8: 24 8:31 8: 38



## Ti m eFuel TankTemp,C

St a r t M o t o r

St a r t S a mpli n g En d Sa m p l i n g



# Figure 3.3-1. Fuel tank tem p eratures during freeway ME on 4/29/03. Ambient temperature

was 4.4 C during this tim e.

For the garage m i croenvironm ent (ME2) we meas ured temperatu r e and rela tiv e hu m i dity at

the sam p ling point, which was also the sam p le inlet loc a tion f

o r all equipm ent located on the

tripod near the van. These da ta are presented in Table 3.3-2 along with the average

conditions f o r the DRI weather station. The average tem p erature and relative hum idities were

relatively co nstant, as was the fuel tank tem p erat ure as m i ght be expected for this stationary

and m o stly indoor ME. While the average winds at DRI were quite high (twice in excess of

10 m ph) inside the garage the w i nds were calm and undetectab le by the hand-held

anem om eter. The above-ground garage is also approxim a tely 3.5 m iles south and slightly

west of the DRI building (m easured in a straight line).

3-37

# Table 3.3-2. Environm ental Conditions for Garage MEs.

F uel T a n k Lo c a l

ME D a te S t ar t E n d D a t a Se t T em p

, C H um i d i t y

, % T em p

, C W i n d

, m p h T em p

, C W in ds

M E 2

- P a r k i n g G a r a g e 4 / 29 0 4 / 29 / 0 3 1 6 : 42 17 : 1 2 a v g . o f 1s t 1 0 m i n u te s : 1 1 35 15

a v g. o f 2 n d 10 m i n u t e s : 10 3 5 1 5

a v g. o f 3 r d 10 m i n u t e s : 10 3 6 1 5

Av e r a g e of all 1 0 3 5 1 5 8

. 3 9 C al m

, no t m e a s u r ea b l

M E 2

- P a r k i n g G a r a g e 4 / 30 0 4 / 30 / 0 3 1 6 : 45 17 : 1 5 a v g . o f 1s t 1 0 m i n u te s : 1 2 33 14

a v g. o f 2 n d 10 m i n u t e s : 11 3 3 1 4

a v g. o f 3 r d 10 m i n u t e s : 11 3 3 1 4

Av e r a g e of all 1 1 3 3 1 4 1 0

. 4 1 0 C al m

, no t m e a s u r ea b l

M E 2

- P a r k i n g G a r a g e 5 / 01 0 5 / 01 / 0 3 1 6 : 42 17 : 1 7 a v g . o f 1s t 1 0 m i n u te s : 1 6 24 16

a v g. o f 2 n d 10 m i n u t e s : 14 2 5 1 6

a v g. o f 3 r d 10 m i n u t e s : 14 2 6 1 6

Av e r a g e of all 1 5 2 6 1 6 4

. 9 14 C a l m

, no t m e a s u r ea b l

M E 2

- P a r k i n g G a r a g e 5 / 02 0 5 / 02 / 0 3 1 6 : 45 17 : 1 5 a v g . o f 1s t 1 0 m i n u te s : 1 4 46 15

a v g. o f 2 n d 10 m i n u t e s : 14 4 8 1 5

a v g. o f 3 r d 10 m i n u t e s : 14 4 7 1 5

Av e r a g e of all 1 4 4 7 1 5 4

. 5 12 C a l m

, no t m e a s u r ea b l

M E 2

- P a r k i n g G a r a g e 5 / 06 0 5 / 06 / 0 3 1 6 : 45 17 : 1 5 a v g . o f 1s t 1 0 m i n u te s : 1 4 34 16

a v g. o f 2 n d 10 m i n u t e s : 13 3 4 1 6

a v g. o f 3 r d 10 m i n u t e s : 14 3 5 1 5

Av e r a g e of all 1 4 3 4 1 6 1 1

. 7 1 1 C al m

, no t m e a s u r ea b l S a m p l i ng Po i n t M e as ur e s A m bie n t C o nd i t i o n s

(D RI W e a t h e r S t a t io n )



# For the ref u eling m i croenvironm ents (ME3 was with vapor recovery, ME4 w a s without

vapor recov e ry), we m easured tem p eratu r e and relative hum i d ity at the sam p ling point which

was also the sam p le inle t loc a tion f

o r all equ i pm ent. This was loca ted on the tripod b e tween

the van and the fuel pump to allow us to asse ss the conditions at the breathing zone of the

person refueling the van. These data are presented in Table 3.3-3 along with the average

conditions f o r the DRI weather station. The average tem p erature and relative hum idities were

relatively constant, as was the fuel tank tem p erat ure as m i ght be expected for this 20 m i nute

stationary ME. W h ile the averag e winds at DRI did go above the 5 m ph threshold for three of

the MEs, th e winds at the refueling stations we re m u ch lower as m onitored by the hand-held

anem om eter. The stations are 1.3 and 1.9 m iles fr om the DRI building (meas ured in a straight

line). Also presented in Table 3.3-3 are the m a xi mum numbe r s of cars seen in the station, the

am ount of fuel dispensed and the amount dropped on the ground following refueling. The

station with the vapor recovery was a m u ch busi e r station with m o re than twice the num b er

of cars as the other station. Th e station used for refueling without vapor recovery (ME4)

could refuel a m a xi m u m of four vehicles at o n e tim e, as it had two p u m p s and each pum p

could be used from either side. The station used for refueling with vapor recovery (ME3)

could refuel a m a xi m u m of 8 vehicles at once, as it had two is lands with two pum p s each and

each pum p could be approached from either side. For all MEs we managed a relatively

consistent num b er of gallons dispensed which was possible since we could unload fuel from

the van to a nearly cons tant leve l. F o r each refu eling ME, we filled up until th e au tom a tic

shutoff stopped the filling process. The num b er of drops spilled was not as co nsisten t

partially due to the difficulty in precisely dropping a fixed amount of fuel out of the nozzle.

The num b er in Table 3.3-3 is th e number of drops spilled whic h was an approxim a te count of

the num ber of wet spots noted on the pavem e nt. The exception is the fi rs t ME where a large

am ount of fuel unexpectedly cam e out of the nozzle and left a single spot approxim a tely 5

cm in dia m e t er.

3-38

# Table 3.3-3. Environm ental Conditions for Refue ling MEs.

F u e l T ank M a x

. C a rs G a l l on s D ro p s of Loc al

ME D a t e S t ar t E n d D at a Set T e m p, C H umid i t y

, % T em p, C I n St a t io n D is p e ns e d F u el S p i l le d W i n d, m p h T em p

, C W i n d s

M E 3

- R e f u el i n g w / V R 4/ 29 0 4 / 2 9 / 0 3 1 2: 00 1 2 : 2 0 a v g

. o f 1 s t 1 0 m i nu t e s : 1 1 2 8 12

av g

. o f 2n d10 m i n u t e s : 1 1 2 8 1 3

A v er age o f a l l 1 1 2 8 1 3 6 16

. 5 0 5 c m p o ol 5. 9 7

. 4 1

- 2 m p h

M E 3

- R e f u el i n g w / V R 4/ 30 0 4 / 3 0 / 0 3 1 0: 45 1 1 : 0 5 a v g

. o f 1 s t 1 0 m i nu t e s : 9 3 7 1 4

av g

. o f 2n d10 m i n u t e s : 9 3 6 1 5

A v e r a g e o f al l 9 3 6 15 4 1 6. 25 25 3

. 8 6

. 5 2 m p h f r o m S E

M E 3

- R e f u el i n g w / V R 5/ 01 0 5 / 0 1 / 0 3 1 2: 25 1 2 : 4 5 a v g

. o f 1 s t 1 0 m i nu t e s : 1 4 2 4 16

av g

. o f 2n d10 m i n u t e s : 1 4 2 4 1 6

A v er age o f a l l 1 4 2 4 1 6 3 16

. 4 2 5 7. 6 1 1. 9 2

- 4 m p h f r om S E v a r

M E 3

- R e f u el i n g w / V R 5/ 02 0 5 / 0 2 / 0 3 1 0: 36 1 0 : 5 6 a v g

. o f 1 s t 1 0 m i nu t e s : 1 1 5 3 15

av g

. o f 2n d10 m i n u t e s : 1 0 5 4 1 4

A v er age o f a l l 1 1 5 3 1 5 5 15

. 4 0 1 0 2

. 5 8

. 5 < 1 m p h

, s o m e d r i z z l e

M E 3

- R e f u el i n g w / V R 5/ 05 0 5 / 0 5 / 0 3 1 0: 45 1 1 : 0 5 a v g

. o f 1 s t 1 0 m i nu t e s : 1 2 3 5 17

av g

. o f 2n d10 m i n u t e s : 1 2 3 5 1 6

A v er age o f a l l 1 2 3 5 1 7 6 17

. 5 0 1 2 3

. 9 9

. 0 < 1 mp h fr o m S S E

ME4 - R e fu e l i n g w / o VR 4 / 3 0 04/ 30 / 0 3 9 : 2 1 9 : 4 1 a v g

. o f 1s t 10 m i n u t e s : 1 4 2 8 1 4

av g

. o f 2n d10 m i n u t e s : 1 4 2 8 1 4

A v er age o f a l l 1 4 2 8 1 4 3 15

. 8 0 6 2. 9 3

. 6 1

- 2 m p h f r om N N W

ME4 - R e fu e l i n g w / o VR 4 / 3 0 04/ 30 / 0 3 1 2 : 0 1 1 2 : 2 1 a v g

. o f 1s t 10 m i n u t e s : 1 2 3 0 1 6

av g

. o f 2n d10 m i n u t e s : 1 3 2 8 1 6

A v er age o f a l l 1 3 2 9 1 6 1 15

. 4 0 1 2 3

. 2 7

. 9 2

- 4 m p h v a r i a b l e d i r

.

M E 4

- R e f uel i n g w / o V R 5 / 0 05/ 01 / 0 3 1 1 : 0 6 1 1 : 2 6 a v g

. o f 1s t 10 m i n u t e s : 1 5 2 2 1 4

av g

. o f 2n d10 m i n u t e s : 1 4 2 2 1 4

A v er age o f a l l 1 4 2 2 1 4 1 14

. 1 8 3 6. 6 9

. 8 2

- 3 m p h f r o m S S E

ME4 - R e fu e l i n g w / o VR 5 / 0 2 05/ 02 / 0 3 9 : 1 8 9 : 3 8 a v g

. o f 1s t 10 m i n u t e s : 1 1 4 2 1 8

av g

. o f 2n d10 m i n u t e s : 1 0 4 4 1 7

A v er age o f a l l 1 1 4 3 1 8 2 17

. 3 1 1 2 3

. 5 8

. 7 1

- 2 m ph, o v e r c a s t

ME4 - R e fu e l i n g w / o VR 5 / 0 5 05/ 05 / 0 3 9 : 2 3 9 : 4 3 a v g

. o f 1s t 10 m i n u t e s : 1 7 2 8 1 8

av g

. o f 2n d10 m i n u t e s : 1 7 3 0 1 8

A v er age o f a l l 1 7 2 9 1 8 1 14

. 5 0 2 0 3

. 9 8

. 3 < 1 m p h f r o m W Sa m p l i n g Po in t M e a s ur e s A m bi e n t C o n d i t i o ns

( D R I W e at he r St a t i o n )



# 3-39

# 3.4 Reconstructed Data

One of the objectives of this study was to de term ine if the original objective of using

surrogate measures to determ ine the tim e seri es of com p ounds of interest was valid. To

answer th is question, this sec tion de tails the reco nstruc tion of the tim e ser i es f o r ben z ene and

BTEX from the PID data and th e co mparison of this to the b e nzene and BTEX determ ined by

the MS200 portable m a ss spectrometer.

The procedure is first to average the 10 second data that is recorded by the PID

instrum e nt up to 1 minute data for com p arison with the MS200 data set (1 m i nute

increm ents). This tim e series is then used along with the integrat ed canister value to

reconstruct a tim e series of the canister concen trations. To accom p lish this, a ratio is taken

between th e PID value at each point and the average P I D value for th e tim e series. This

num b er is multiplied b y the integr ated canis te r valu e to g i ve a re cons truc ted va lu e f o r th at

data point and is com p ared to the tim e- corresponding data point from the MS200.

The first example pres en ted is for the fr eeway driving (ME1) on 4/29/03. Figure 3.4-1

shows the tim e series f o r benzene in this ME. A few data points are m i ssing from t h e MS

data where s o m e electrical noise ren d ered thos e data points invalid. Th e general trend of the

peaks is reproduced by both the MS200 and the PID reconstructed data, however, the peak

values are much higher in the MS200. This is confirm e d by th e com p arison of the integrated

values, where the MS200 showed 14.7 ppb and th e canister 9.1. ppb. This ratio (1.6) nearly

accounts for the differences and m a y be due to offs et (zero point) or cal ibration differences in

the MS200. Com p aring the tim e series for the su m

of the BTEX species, we obtain the plot

in Figure 3.4-2. In this figure, the structure of th e tim e series and th e m a gnitude of the peaks

are both m u ch m o re precisely repro duced than is the case with just ben z ene. Due to both the

higher concentrations of toluene and the C8 benzenes, and the better perform a nce of the

MS200 with these species. S ection 3.1.9 details the perform a nce of th e MS200 versus the

canis ters an d shows that benzene is consis ten tly the m o st difficult s p ecies to measure,

especially a t the lower levels. The integra t ed canister m easurem ent for this sam p le was 97

ppb for the sum of the BTEX species while the MS200 reported 123 ppb . Looking at the two

highest peak s in this tim e series (8 :0 1 and 8:03 am ) it appear s that the tim i ng is slig htly off

with the MS 200 lagging the PID reconstructed data.

To further investigate the tim ing between these two instrum e nts, we looked at a higher

concentration sam p le with a si gnificant spike in the concentration (ME4 refueling w ithout

vapor recovery from 5/ 2/03). Figure 3.4-3 shows the reconstructed tim e series for benzene

along with the MS200 values for benzene. Figure 3.4-4 presents the same data for B TEX. In

both figures, the series is well reproduced how ever the peak values reco rded by th e MS200

are m u ch lower than the reconstructed. Duri ng the “non-peak” part of the ME, the MS200

appears to b e read ing co nsisten tly higher th an th e r econstructed values. Ov erall, ho wever, the

values m a tch quite well with the ratio of MS200/canister of 1.05 for the BTEX species and

1.18 for benzene. As with the previous exampl e, it appears that th e tim ing of the peak

concentration is out of phase by one m i nute. To l ook m o re closely at the peak concentration,

we used the original 10 second data from the PID to reconstruct a 10 second tim e series for

the BTEX species and plotted th at along with the 1 m i nute data in Figure 3.4-5. This figure

3-40

# does not show the entire tim e series; rather it fo cuses on the period of the peak exposure from

9:27 to 9:33 a m . In this figure, the 10-second reconstructed data shows two peaks where the

1-m i nute reconstructed and the MS200 data show one peak. The 1-m i nute tim e averaged data

m a y better represent what the MS200 is m easuring, since the MS200 does not integrate

sam p les over the 1-m i nute period. R a ther, the natu re of the flow-through system s m e a rs the

peaks out over a longer tim e due to the tim e it takes analytes to di ffuse through the inlet

system and into the m a ss analyzer. T h e flow-through system also m eans that som e very short

duration high peaks m a y not be seen at all.

Overall the com p arison of the reconstructed BTEX and MS200 BTEX values substantially

agree and this provides added confidence that we can represen t the peak exposures well by

using the PID values to reconstr uct tim e series for the BTEX species. W h i l e we do not have a

direct m easure for 1,3-butadie ne, we would suggest that it could also be adequately

repres ented by the PID values, esp eci ally for exhaust-dom inated MEs.



# 0 5 10 15 20 25 30 35

7: 26 7: 40 7: 55 8: 09 8: 24

Ti m eppbv 

# M S 200 Benz ene

R

eonst r u c t ed Bz

Figure 3.4-1. ME1 (freeway driving) on 4/29/03: Tim e series of benzene from the MS200

and reconstructed benzene concentrations from the PID and canister m easurem ents.

3-41

# 0 50 100 150 200 250

7: 26 7: 40 7: 55 8: 09 8: 24

Ti m eppbv 

# M S 2 0 0 BT EX

R

eonst r uc t ed B T E X



# Figure 3.4-2. ME1 (freeway driving) on 4/29/03 : Tim e series of BTEX from the MS200 and

reconstructed BTEX concentrations fr om the PID and canis ter m easurem ents.

3-42

# 0 50 100 150 200 250

9: 14 9: 21 9: 28 9: 36 9: 43

Ti m eppbv 

# M S 200 Benz ene

R

eonst r u c t ed Bz

Figure 3.4-3. ME4 (refueling without vapor rec overy) on 5/2/03: Tim e series of benzene

from the MS200 and reconstructed benzene c oncentrations from t h e PID and canister

m easurem ents.

3-43

# 0 200 400 600 800 1000 1200 1400

9: 14 9: 21 9: 28 9: 36 9: 43

Ti m eppbv 

# M S 200 B T E X

R

eonst r uc t ed B T E X

Figure 3.4-4. ME4 (refueling without vapor recove ry) on 5/2/03: Tim e series of BTEX from

the MS200 and reconstructed BTEX concentratio ns from the PID and canister m easurem ents.

3-44

# 0 1000 2000 3000 4000 5000 6000 7000

9: 27 9: 30 9: 33

Ti m eppbv 

# M S 200 BT E X

R

eonst r uc t ed BT EX

1 0 Se c BT EX

Figure 3.4-5. ME4 (refueling without vapor recove ry) on 5/2/03: Tim e series of BTEX from

the MS200 and reconstructed BTEX concentra tions at both 1 m i nute and 10 second time

resolution.

3-45

# 3.5 Breath Data

Two subjects, labeled “B” and “J”, perform e d breath sam p le collections . The CO2 level in

their breath sam p les was m easured prior to the comm encem ent of the pilot study, and

averaged 5.4% for B and 6% for J. As de scribed in Section 2.1, tw o breath sam p les were

collected at refueling ME (prior to refueling and 10 sec after refueling), and three during each

commuter traffic and garage test (b efore, after a peak expo su re, and at the end of the ME

sam p ling tim e). All breath sam p les were an alyzed for CO2, BTEX, 1,3-butadiene, ethanol

and MTBE as described in Section 2.3. The whole data set is presented in Appendix C.

Figure 3.5–1 shows the CO2 values in the breath sam p les of subjec ts B and J collected in all

ME, organized by the subject and by the m i croenvironm ent. It is clear that one pre- test

freeway sample collected by J is in valid, s i n ce CO2 value is below 1%. Excluding this one

sam p le, the m ean CO2 value for subject B averages at 5.4%, and for subject J at 6.07% for

all ME.

Figure 3.5-2A shows the concentrations of 1,3-but adiene, benzene, ethylbenzene, m /p- and oxylenes in the breath samples for all freeway tes t s (o rganize d in th e chronological order) and

Figure 3.5-2B shows the c oncentrations of toluene and etha nol for the sam e ME. Figures

3.5-3 A and B and Figure 3.5-4 A and B shows the sam e com pound concentrations for the

garage and refueling ME, respectively. The range of concentrations for 1,3-butadiene,

benzene, eth y lbenzene, m / p- and o-xylenes agre e reasonably well for bo th sub j ects, there is

clearly a large difference in the toluene conc entrations. Subject B contains m u ch higher

toluene con centr ation s in the bre a th – it look s lik e the to lue n e is pr esent in the b r ea th of this

subject, regardless of the exposure. The reason of this phenom enon is unknown to us.

Ethanol concentrations are rath er high and variable, not dependa nt on the exposure. MTBE

concentratio ns are very low and are not shown on these figures. Neither MTBE nor ethanol

are present in the Reno fuel at th is tim e of the year.

3-46CarbonDioxide0123456789

%----------------------------------------------------------- B------------------------------------------------------------------------------------------------------------------------------------ J-------------------------------------------------Figure 3.5–1. CO2 values in the breath samples of subjects B and J collected in all ME, organized by the subject and bymicroenvironment.3-47

### Fre e w a y

0 2 4 6 8 10 12Freeway,PreFreeway,PeakFreeway,PostFreeway,PreFreeway,PeakFreeway,PostFreeway,Pre,JFreeway,Peak,JFreeway, Post,JFreeway,PreFreeway,PeakFreeway,PostFreeway,Pre,JFreeway,Peak,JFreeway, Post,Jppb 

### bu d 1 3

ben z e

et bz

m p

_ xyl

o_x y l A



### Fre e w a y

0 20 40 60 80 100 120 140 160Freeway,PreFreeway,PeakFreeway,PostFreeway,PreFreeway,PeakFreeway,PostFreeway,Pre,JFreeway,Peak,JFreeway,Post,JFreeway,PreFreeway,PeakFreeway,PostFreeway,Pre,JFreeway,Peak,JFreeway,Post,Jppb 

### to l u e

et h o h B



# Figure 3.5-2. The concentrations of 1,3-butadie ne, benzene, ethylbenzene, m /p- and oxylenes (A) and tolu ene and ethano l (B) in the breath sam p les of subjec t B (not labeled) and

J in the freeway driving ME. The r uns are show n in chronological order

3-48

## Ga rage

0 1 2 3 4 5 6 7 8Garage, PreGarage,PeakGarage, PostGarage, PreGarage,PeakGarage, PostGarage,Pre,JGarage, Peak,JGarage,Post,JGarage, PreGarage,PeakGarage, PostGarage,Pre,JGarage, Peak,JGarage,Post,Jppb 

### bu d 1 3

be n z e

et bz

m p

_ xyl

o_ x y l A



## Garage

0 20 40 60 80 100 120 140 160 180Garage,PreGarage,PeakGarage,PostGarage,PreGarage,PeakGarage,PostGarage,Pre,JGarage,Peak,JGarage,Post,JGarage,PreGarage,PeakGarage,PostGarage,Pre,JGarage,Peak,JGarage,Post,Jppb 

### to l u e

et hoh B



# Figure 3.5-3. The concentrations of 1,3-butadie ne, benzene, ethylbenzene, m /p- and oxylenes (A) and tolu ene and ethano l (B) in the breath sam p les of subjec t B (not labeled) and

J in the garage ME. The runs are shown in chronological order

3-49

## Re fue ling

0 5 10 15 20Ref.W/OV,PreRef.W/OV,PostRef.W/OV,PreRef.W/OV,PostRef.W/OV,Pre,JRef.W/OV,Post,JRef.W/OV,PreRef.W/OV,PostRef.W/OV,Pre,JRef.W/OV,Post,JRef.W/V,PreRef.W/V,PostRef.W/V,PreRef.W/V,PostRef.W/V,Pre,JRef.W/V,Post,JRef.W/V,PreRef.W/V,PostRef.W/V,Pre,JRef.W/V,Post,Jppb 

### b ud13

b enz e

etb z

mp

_ x y l

o

_

xyl 80 ppb 

### A



## Re f u e l i n g

0 50 10 0 15 0 20 0 25 0Ref.W/OV,PreRef.W/OV,PostRef.W/OV,PreRef.W/OV,PostRef.W/OV, Pre,JRef.W/OV, Post,JRef.W/OV,PreRef.W/OV,PostRef.W/OV, Pre,JRef.W/OV, Post,JRef.W/V,PreRef.W/V,PostRef.W/V,PreRef.W/V,PostRef.W/V,Pre,JRef.W/V,Post,JRef.W/V,PreRef.W/V,PostRef.W/V,Pre,JRef.W/V,Post,Jppb 

### to lu e

et h o h B



# Figure 3.5-4. The concentrations of 1,3-butadie ne, benzene, ethylbenzene, m /p- and oxylenes (A) and tolu ene and ethano l (B) in the breath sam p les of subjec t B (not labeled) and

J during refueling. The runs ar e shown in chronological order

3-50

# 3.6 Consistency of Microe n v ironment Conditions

Each of the four m i croenvironm ents included in this pilot study was repeated 5 tim e s to

assess the v a riab ility of the environ m ental c onditions and precision of the characterization

m e thods. During the testing periods there were no significant variatio ns in m e teorological

conditions and the sam e protocols were obser ved, so it is reasonable to attribute any

variations in the range or m a gnitude of m e a s urem ents to di f f e rence s in activity in the

m i croenvironm ent, daily variations in background concentrations, or m e asurem ent

uncertainty. Statis tical su mmaries of the conti nuous CO and BTEX by PI D data are p r esented

in th is se ction to exam ine this var i ability. The statis tics re presented a r e the m a ximum and

m ean of the running 1 m i nute averages of th e continuous concentration m easurem ents

record ed ev ery 10 secon d s during each tes t . The 10t h and 90th percentile values for each test

are also represented to g i ve a better repres en tation of the range of conc entrations observed.

Charts of the average for each m i croenvironm ent and standard dev i ation of the average

am ong the 5 replicates are al so included in Figure 3.6-3.

3.6.1 CO

Figure 3.6-1 shows the API NDIR CO data except for the first two repetitions of ME1 and

the first ME3 for which the NDIR d a ta was inva lid b ecause of insuffici ent battery. F o r thos e

three tests discrete 1 m i nute av erages from the electrochem i cal CO instru m e nt are

summarized in the ch art.

The range of concentrations is large for all tests, with the exceptio n of several of the

refueling tests (ME3 and ME4) where CO c oncentrations were ne ar background throughout

the tes t s. Despite the large rang e, the differen ces between m i croenvironm ents are clearly

evident. The parking garage tests, ME 2, had higher m a xi m u m and 90th percentile

concentrations than all but one of the freeway tests even th ough the average concentrations

are sim ilar. The two refueling MEs are cons isten tly lower than the freeway or garage in both

the m ean and m a xi m u m values. The third freew ay (ME1) test appears to be an outlier due to

a high initial level of CO (see Figure 3.2-4), po ssibly a result of capturing exhaust from the

van in the cabin prior to the start of th e driv ing cy cle.

3-51

### 0 5 10 15 20 25

M E 1 M E 2 M E 3 M E 41minuterunning avgCO(ppm) 

### 1 0 th t o

9 0 th %

MA X

ME A N



# Figure 3.6-1. Range and variability of CO con centration during tests. S t atistics for each of

the five rep l icate tests are shown for each m i croenvironm ent.

Data summ arized are ru nning 1-m i nute averages (at 10 second interval s) of NDIR CO data,

except for the first two ME1s and fi rst ME3 which are dis c rete 1 m i nute averages from the

electrochem i cal CO instrum e nt. The shaded ba rs indicate the range from the 10th to 90th

percen tile. Microenv iro n m e nts are: freeway driv ing (ME1), parking garage (ME2), refueling

with vapor recovery (ME3), and refu eling without vapor recovery (ME4).

3-52

# 3.6.2 PID

The range and variability of BTEX concentrations estim a ted by the prim ary ppbRAE VOC

monitor (PID1) are summarized in Figure 3.6-2. As with CO, the range of the m e an and

m a xim u m values is larg e f o r all tests, but s till s m aller than the overa ll dif f e rence between

m i croenvironm ents. The largest range occurred f o r refueling w ithout vapor recovery (ME4),

which is to be expected since very high VOC levels occurred dur ing the refueling process. In

all ca ses, th e 10th perce n tile values were near th e lower lim it of detectio n (they appe ar to b e

zero in the chart due to scale) suggesting that background levels of BTEX were very low.

3-53

### 0 20 0 0 40 0 0 60 0 0 80 0 0 10 0 0 0 12 0 0 0 14 0 0 0 16 0 0 0 18 0 0 0

M E 1 M E 2 M E 3 M E 41minuterunning avgBTEXbyPID(ppb) 

### 10 t h t o

90 t h %

M A X

M E A N

0 10 0 20 0 30 0 40 0 50 0 60 0 70 0 80 0 90 0 10 0 0

ME1 M E 2 M E 3 M E 41minuterunning avg BTEXbyPID(ppb) 

### 10 t h t o

90 t h %



### MAX



### MEA N



# Figure 3.6-2. Range and variability of BT EX by PID concentration during tests.

Statis tics for each of th e five rep l icate te s t s are shown for each m i cro e nvironm ent. Data

summarized are running 1-m i nute av erages (at 10 second intervals) The shaded bars indicate

the range from the 10th to 90th percentile. The lower chart shows the sam e dat a on an

expanded s cale. M i cro e nvironm ents are: free way driving (ME1), parking garage (ME2),

refueling with vapor recovery (ME3), and refueling without vapor recovery (ME4).

3-54

### A v e r ag e of rep l i c at e t e s t m ean c o n c en t r at i o n s

0 1 2 3 4 5 6 7 8 9

ME 1 M E 2 ME 3 M E 4CO(ppm)

0 20 0 40 0 60 0 80 0 10 0 0 12 0 0 14 0 0



### ME 1 M E 2 ME 3 M E 4BTEX byPID(ppb)



# Figure 3.6 -3 . Range a n d variability of m ean CO and m ean BTEX by PID concen tr ation f

o r

four m i croenvironm ents.

Data summarized are running 1-minute averages (at 10 second interval s) The error bars

indicate the standard de viation of the average of five repl icate tests. Microenvironm ents are:

freeway driving (ME1), parking garage (ME2), refueling with vapo r rec overy (ME3 ), and

refueling without vapo r recovery (ME4).

3-55

# 4. CONCLUSIONS

Overall, the 2nd Reno Pilot study was a success. Specifically, we com p leted the stated goal

of the study: to dem onstrate the proper operation and reliability of analytical ins t rum e ntation

and com p a r ability of tim e-integ r ated, se m i -continuous and continuous m e t hods for

com pounds of interest. In addition, we dem onstrated the validity of the method of

reconstructing tim e series for com pounds of intere st by using surrogate m easure m ents. In this

case, we specifically demonstr ated the validity of using the PID signal and the canister data

to recons tru c t the tim e series f o r BT EX.

The following conclusions are drawn from the 2nd Reno Pilot Study results:

Modif i catio ns to the sampling van and addition of the data acquisition system were

significant improvem e nt s that allow e d for m o re com p lete d a ta collectio n. The new

power system does not produce artifacts; howev er, it is ins u f f i cient to power the API

CO instrum e nt. Poss ible alterna tiv es inc l ude use of a different brand of NDIR CO or

the addition of m o re battery banks to sup port the A P I NDIR CO. Severa l

im provem e nts ar e still planned to the sa m p lin g van inc l u d ing the ad dition of a

continuously logged barom e tric pressure se nsor, direct logging of flow to the

integrated samplers, and loggi ng of canister pressure.

Data capture was generally quite good with near 100% data capture for the reference

sam p les, canisters, DNPH and solid adsorbent. The SPME also had excellent data

capture, as did the continuous instrum e nt s for CO and PI D. The MS200 performed

well in the beginning of the study however at the end it was not working. The

supplem ental continuous for m aldehyde instru m e nt is not reliable during m obile

m easure m ents, and should only be used for statio nary m e asurem ents. Our

environm ental m onitoring equipm ent for te m p eratures, hum idity, etc., lost only 14

m i nutes of data over the entire study.

The MS200 generally perform e d well agai nst the canister when comparing the

average value from the MS to the integrat ed canister m e asurem ent for t h e sam e ME.

However, there are still concerns with th is supplem ental m e asurem ent system . Ther e

appears to b e a concentration bias, especially for benzene. The instrum e nt appears to

m i ss very rapid changes in concentration su ch as those that occur du ring refueling

events. Th ere are still so m e electrical nois e s that appear in the van when in m o tion.

W e did not detec t the s e in the sta tio nary ME s, and they did not invalidate m o re than a

few spectra in a run. The MS200 did not run during the last day of the study due to

severa l f actors re la ting to th e sens itiv ity of th e dete ctor a nd the f i la m e nt voltage

contro l. So m e of this a ppears to b e ele c tr onic related and m a y be fixed when we send

the electron ics box back to be upgraded to the new interface. The MS200 is a

developing instrum e nt that s hould provide interesting supple m e ntal data to the study.

The continuous for m aldehyde analyzer wo rked well for two of the five garage

sam p ling microenvironm e nts (ME2-4 and ME 2-5) but did not work well for the

f r eeway (M E1) or ref u eling (ME3 a nd ME 4) m i croenvironments. The se nsitiv ity of

the instrum e nt to enviro nm ental no ise asso cia t e d with d r iv ing while co llec ting data

m a y lim it its utility under any so rt of m obile environm ent. W i th proper operation and

4-1

# better characterization of instrum e nt perform a nce, the supplem ental continuous

for m aldehyde analyzer may prove useful fo r m onitoring a stationary environm ent.

Both an EPA-certified gas- filter correlation NDIR CO an alyzer (API model 300) and

a portable battery-operated pa ssive electrochem i cal cell instrum e nt (Langan T15v)

agree rea s o n ably well to within ab out 1 ppm . During low-ventil ation (half of the

freeway tests) the CO concentration s rem a in at or decrease toward the lowest level

m easured during the high-vent phase. This be havior suggests that no in-cabin sources

or interferen ces are pres ent.

In general the continuous PID and CO in strum e nts perform e d very well. The two

PIDs were com p ared both in controlled te sts and collocated during the MEs. In both

cases, they tracked each other qu ite well. Diffe rences appear to be due to an offset in

one unit, and a slightly different respons e speed between the two units. T h e NDIR CO

and electro c hem i cal CO instrum e nts com p ar ed favorably, usually within 1 ppm . This

was partially attr ibuted to the adap tive f ilter i ng of the API NDIR CO as dem onstrate d

when com p aring it to another NDIR instru m e nt m a de by Monitor Labs, Inc. For the

purposes of this study, we strongly reco mm e nd using an instrum e nt without the

adaptiv e f ilter sin ce th e f ilter caus e s change s in concentration to app e ar le ss sha r p

than actua l and causes peaks to shif t to later tim e s which interf ere s with

intercom parisons am ong m e thods and instrum e nts.

Com p arison of CO f r om the con tinu ous inst ruments to that m easured by GC from the

canis ters sh owed that the canister CO wa s generally 8% higher with no consistent

bias correlated to any particular ME nor with concentration. The correlation between

the CO and PID data was strongest for the garage ME.

SPME sa mples show overall higher concen trations than MS200 (10-min averaged)

concentratio ns. Also, S P ME data averaged o v er th e entire sam p ling period s are

generally higher than canister data, due possibly to inadequate tem p erature

corrections of the SPM E data. SPME fibers ar e very sensitiv e to tem p erature chang e s

(they absorb m o re analytes under cold condi tions, as in this pilot study) and they

m i ght not be fully equilibrated to am bien t temperatures prior to sampling. In the

f u ture study , the clean f i bers will be stored a t am bient tem p erature in a closed

contain e r with activated charcoal.

The proced ure f o r collecting and a n alyzing b r e a th sam p les worked well; ther e was

only one invalid sam p le (based on CO 2 

# concentration) during this study. The data

shows consistently higher BTEX c oncentr ations after the peak exposure and are

com p arable between the two subjects collecti ng the sam p les. One exception is toluene

where it ap pears that o n e of the su bjects ha s toluene p r es ent in the b r eath sam p les,

regardless of the exposure.

The 5-m i nute canister sam p les had lower da ta recov e ry (80%). Th is was partia lly

because the sam p ler that was used to fill this can iste r wa s no t optim al for the task. A

relatively high flow rate was needed to pressurize a canister in only 5 m i n and the

sam p ler used was not designed for this m u ch flow. For the final study, we have

designed an d built a ne w sam p ler s p ecif i ca lly f o r this task.

4-2

# The reconstruction of the be nzene and BTEX tim e series from the PID data showed

overall good com p arison with the MS200 data . However, som e concentration peaks

were not reproduced in m a gnitude and appear ed to be tim e shifted, a consequence of

the averagin g of the PID data from 10 seconds down to 1 m i nute. In addition, the

MS200 does not integrate sam p les over the 1- m i nute period; rather the nature of the

flow-through system s m ears the peaks over a longer period due to the tim e it takes to

diffuse through the inlet system and into the m a ss analyzer. Because of the flowthrough system , very short duration high p eaks m a y not be see n. In summ ary, for

most of the MEs the reconstructed data and the MS200 data agr eed reasonably well,

suggesting that the reconstruction m e thod wor k s and should provide a m e thod to

calculate the peak exposures during sam p ling at the MEs.

4-3

# 5. REFERENCES:

Chai, M. and J. Pawliszyn, 1995. Analysis of Environm ental Air Sam p l e s by Solid-Phase

Microextraction and Gas Chrom a togr aphy/Ion T r ap Mass Spectrom e try,

Environm ental Science and Technology, Vol. 29, No. 3. Pag 693-701.

Grote C.and J.Pawlinszyn, 1997. Solid Phase Mi croextraction for the analysis of Hum a n

Breath. Anal Che m .. Vol u m e 69, 587-596

Kelly, T.J. and C.R. Fortune (1994). C ontinuous Monitoring of Gaseous Formaldehyde

Using an Improved Fluorescence Approach. Intern. J. E nviron. Anal. Che m ., 54:

249-263

Koziel, Jaceb, et al., 1999 Field air analysis with SPME device. Analytical Chim ica Acta 400

153-162

Koziel, Jacek A. and Novak, I. 2002. Sa m p ling and Sam p le-preparation Strategies B a sed on

Solid-phase Microextraction for Analysis of Indoor Air. Trends in Analytical

Che m istry, Vol 21, No.12.

Lodge, James P. Methods of air sam p ling an d analysis. Third edition. Lewis publishers.

Intersociety comm ittee. Michigan, 1989. pp15-16.

Martos, P. and J. Pawliszyn, 1997. Calibratio n of Solid Phase Microextraction for Air

Analysis B a sed on Physical Chem ical Pr operties of the Coating. . Analytical

Che m istry. 69: 206-215. 1997

Martos, P. and J. Pawliszyn, 1999. Ti m e

- W ei ghted Average Sa m p ling with Solid-Phase

Microextraction Device: Im plications for Enhanced Personal Exposure Monitoring to

Airborne Pollutants, Analytical Chem istry, Vol. 71, No. 8, April 15.

McLaren and Zhou, 2000. Measurem ent of Oxyge nated Hydrocarbons in Outdoor Air using

Sold-Phase Microextraction Gas Ch ro m a tography. AAA Co nference 2000.

Na m i esnik, Jacek. Generation of standard gaseous m i xtures. Journal of Chrom a tography.

300. 1984. pp. 79-108.

Nelson, Gary O. Gas Mixtures: P r eparation and Control. Lewis Pl ublishers. 1992. CRC

Press.

Parreira, F et al. Evaluation of Indoor Exposit ion to BTEX and Styren by passive sampling

with SPME. Journal of Chrom a tography, Vol. 40, March 2002. 122-126.

Pawliszyn, J., 1997. Solid Phase Microextract ion: Theory and Practice, W iley-VCH.

Pawliszyn, J., 1999. Applications of Solid phase Microextra ction. Royal Society of

Chem istry.

Pawliszyn, 2002. Sam p ling and Sa m p le Pr eparation for Field and Laboratory.

Com p rehensive Analytical Chem istry, Vol 37. Elsevier.

5-4

# Pleil J.D. and A. B. Li ndstrom . (1995). Me asurem ent of volatile organic com p ounds in

exhaled b r eath as collected in evacu ated el ec tro polished can iste rs. J. Chrom a togr. B,

665: 271-279

Tuduri, Ludovic et al. Potential of Sollid-Ph a se Microex t raction fibers for the Analysis of

VOC in air. Journal of Chrom a tographic Scien ce, Vol. 39, Decem ber 2001. pp 521-

529.

Zielinska, B., E. M. Fujita and J. C. Sage biel (2003). Section 211(B) Tier 2 High End

Exposure Screening Study of Bas e line a nd O xygenated Gasolin e - Summ er 2002

Atlanta F i eld Study on Baseline Gasoline. Feb. 2003

Zielin ska, B., E. M. Fujita, J. C. Sagebiel, D. E. Cam pbell, J. D. McD onald, L. R. Smith, T.

Johnson (2002). Exposure Protocol and St udy Plan for the Section 211(B) Tier 2

High End Exposure Screening Study of Base line and Oxygenated Gasoline. Revisied

edition,Sept.30,2002

5-5

# 6.APPENDICIES

6.1 Appendix A: SPME

p p b

m e d a t e strth h m m stophhm m an _d a t e Storage T avg R H a vg benz e t o l u e etbz mp_xyl o_xyl

M E 3 4 / 2 9 / 0 3 12 1 0 12 2 0 4/ 2 9 / 0 3 2: 4 0 10 .6 9 2 8

. 0 3 6. 6 6 47 .1 3 10 .1 8 29 .3 2 7. 9 9

M E 3 4 / 2 9 / 0 3 12 0 0 12 1 0 4/ 2 9 / 0 3 3: 1 5 10 .6 9 2 8

. 0 3 17 .2 1 58 .5 6 11 .2 2 24 .7 6 12 .0 6

M E 1 4 / 2 9 / 0 3 81 2 82 2 4/ 2 9 / 0 3 7: 3 3 20 .7 8 3 1

. 9 0 18 .8 0 11 4. 0 9 19 .4 2 51 .1 0 15 .5 6

M E 1 4 / 2 9 / 0 3 80 2 81 2 4/ 2 9 / 0 3 8: 1 8 15 .8 0 3 1

. 8 1 12 .5 0 98 .2 4 18 .5 1 51 .1 7 16 .4 4

M E 1 4 / 2 9 / 0 3 75 2 80 2 4/ 2 9 / 0 3 9: 0 8 12 .3 2 3 1

. 8 9 15 .6 9 70 .8 6 15 .9 5 45 .0 5 14 .5 0

M E 1 4 / 2 9 / 0 3 74 2 75 1 4/ 2 9 / 0 3 9: 3 8 11 .7 1 3 7

. 7 3 13 .1 2 66 .4 7 19 .6 1 54 .8 1 17 .3 4

M E 2 4 / 2 9 / 0 3 16 5 2 17 0 2 4/ 2 9 / 0 3 1: 0 8 10 .2 8 3 4

. 5 9 24 .7 0 66 .8 5 19 .4 9 49 .3 3 14 .8 3

M E 2 4 / 2 9 / 0 3 17 0 2 17 1 2 4/ 2 9 / 0 3 1: 2 8 10 .0 8 3 5

. 8 8 28 .2 1 90 .1 2 26 .3 6 73 .0 8 25 .6 9

M E 2 4 / 2 9 / 0 3 16 4 2 16 5 2 4/ 2 9 / 0 3 2: 1 8 10 .5 6 3 4

. 6 0 4. 0 8 12 .4 9 2

. 4 8 6. 9 5 1. 5 9

M E 4 4 / 3 0 / 0 3 12 1 1 12 2 1 4/ 3 0 / 0 3 1: 0 4 27 .6 8 1 2

. 8 2 11 .7 4 65 .1 8 15 .1 2 34 .5 3 7. 4 1

M E 4 4 / 3 0 / 0 3 12 0 1 12 1 1 4/ 3 0 / 0 3 1: 3 4 29 .1 4 1 2

. 2 1 10 .2 9 38 .1 7 13 .1 0 28 .0 2 7. 1 6

M E 3 4 / 3 0 / 0 3 10 4 5 10 5 5 4/ 3 0 / 0 3 3: 1 5 8. 9 3 36 .5 9 6

. 6 1 24 .5 1 6

. 3 1 20 .7 3 5. 5 0

M E 3 4 / 3 0 / 0 3 10 5 5 11 0 5 4/ 3 0 / 0 3 3: 3 5 8. 9 9 36 .3 2 2

. 7 1 16 .4 0 7

. 5 5 18 .2 3 4. 5 0

M E 1 4 / 3 0 / 0 3 80 9 81 9 4/ 3 0 / 0 3 6: 3 6 25 .5 4 2 5

. 8 8 20 .4 1 15 5. 7 8 22 .1 9 66 .5 9 19 .9 0

M E 1 4 / 3 0 / 0 3 75 9 80 9 4/ 3 0 / 0 3 7: 1 1 20 .6 9 2 8

. 0 2 21 .9 2 13 9. 7 4 30 .2 7 80 .9 9 27 .3 7

M E 1 4 / 3 0 / 0 3 73 9 74 9 4/ 3 0 / 0 3 7: 5 6 9. 7 2 42 .5 9 2 7

. 1 7 11 3. 7 6 33 .8 6 84 .9 6 27 .2 8

M E 1 4 / 3 0 / 0 3 74 9 75 9 4/ 3 0 / 0 3 8: 2 6 12 .9 8 3 4

. 3 5 26 .5 2 10 1. 8 4 14 .1 3 59 .1 9 18 .0 5

M E 4 4 / 3 0 / 0 3 92 1 93 1 4/ 3 0 / 0 3 7: 3 9 14 .1 0 2 7

. 9 8 17 .0 4 85 .6 1 15 .3 4 57 .6 8 17 .0 1

M E 4 4 / 3 0 / 0 3 93 1 94 1 4/ 3 0 / 0 3 7: 4 9 14 .0 3 2 8

. 3 3 41 .0 4 14 0. 1 4 20 .7 0 75 .8 4 22 .4 8

M E 2 4 / 3 0 / 0 3 16 4 5 16 5 5 4/ 3 0 / 0 3 3: 3 5 32 .7 7 1 1

. 5 9 28 .6 0 89 .1 9 13 .5 2 49 .4 0 16 .8 5

M E 2 4 / 3 0 / 0 3 16 5 5 17 0 5 4/ 3 0 / 0 3 3: 4 5 32 .7 1 1 0

. 8 4 19 .1 4 69 .5 9 16 .8 9 58 .2 9 19 .6 6

M E 2 4 / 3 0 / 0 3 17 0 5 17 1 5 4/ 3 0 / 0 3 3: 5 5 33 .0 4 1 1

. 0 7 64 .0 0 17 3. 7 4 48 .8 8 15 4. 5 7 58 .1 1

M E 1 5 / 1/ 0 3 72 0 73 0 5/ 1/ 0 3 2: 3 0 11 .3 2 4 3

. 4 0 49 .7 0 15 2. 0 0 36 .8 7 10 4. 5 2 34 .6 1

M E 1 5 / 1/ 0 3 75 0 80 0 5/ 1/ 0 3 2: 3 0 21 .4 1 3 3

. 7 2 29 .5 8 19 5. 0 4 24 .9 2 81 .8 8 26 .4 7

M E 1 5 / 1/ 0 3 73 0 74 0 5/ 1/ 0 3 3: 1 0 15 .9 6 3 0

. 6 0 29 .7 8 13 0. 2 0 26 .2 1 87 .3 8 28 .8 0

M E 1 5 / 1/ 0 3 74 0 75 0 5/ 1/ 0 3 3: 3 0 19 .8 2 3 0

. 0 6 21 .3 2 11 0. 0 7 19 .0 9 63 .3 3 23 .2 6

M E 4 5 / 1/ 0 3 11 1 6 11 2 6 5/ 1/ 0 3 2: 4 4 13 .7 2 2 1

. 7 9 8. 0 5 54 .9 1 14 .5 0 44 .0 3 12 .1 0

M E 4 5 / 1/ 0 3 11 0 6 11 1 6 5/ 1/ 0 3 3: 2 4 14 .5 0 2 2

. 2 7 5. 5 5 43 .5 7 14 .6 4 35 .2 0 8. 7 1

M E 3 5 / 1/ 0 3 12 2 5 12 3 5 5/ 1/ 0 3 2: 2 0 13 .5 4 2 4

. 5 2 5. 6 1 17 .0 2 4. 6 0 13 .5 8 3. 2 3

M E 2 5 / 1/ 0 3 16 4 7 16 5 6 5/ 1/ 0 3 1: 1 3 14 .9 2 2 4

. 6 4 6. 5 3 38 .1 5 8. 8 0 23 .6 3 6. 4 8

M E 2 5 / 1/ 0 3 17 0 7 17 1 7 5/ 1/ 0 3 1: 1 3 16 .1 8 3 5

. 4 2 24 .1 7 83 .7 5 16 .9 9 56 .1 5 20 .5 2

M E 2 5 / 1/ 0 3 16 5 7 17 0 7 5/ 1/ 0 3 2: 0 3 14 .3 1 2 5

. 7 4 30 .2 8 91 .6 1 15 .9 5 58 .1 9 19 .0 1

M E 3 5 / 2/ 0 3 10 3 6 10 4 6 5/ 2/ 0 3 2: 3 9 10 .7 6 5 2

. 5 7 33 .5 6 94 .4 4 16 .8 5 61 .8 9 19 .5 0

M E 3 5 / 2/ 0 3 10 4 6 10 5 6 5/ 2/ 0 3 2: 5 9 10 .3 4 5 3

. 4 9 7. 3 2 39 .9 6 7. 4 8 23 .7 4 5. 9 7

M E 3 5 / 2/ 0 3 91 8 92 8 5/ 2/ 0 3 4: 5 2 10 .7 7 4 2

. 3 5 4. 8 5 27 .4 1 6. 3 5 18 .0 9 4. 0 1

M E 3 5 / 2/ 0 3 92 8 93 8 5/ 2/ 0 3 5: 1 2 10 .4 8 4 3

. 8 5 84 .6 9 28 1. 0 9 56 .1 5 16 7. 7 1 54 .3 7

M E 1 5 / 2/ 0 3 73 5 74 5 5/ 2/ 0 3 7: 4 0 16 .1 8 3 5

. 4 2 16 .8 5 83 .2 8 20 .7 4 56 .9 6 17 .3 7

M E 1 5 / 2/ 0 3 74 5 75 5 5/ 2/ 0 3 8: 1 5 19 .5 7 2 9

. 3 9 22 .9 2 12 1. 3 5 30 .4 6 86 .7 1 27 .3 5

M E 1 5 / 2/ 0 3 74 5 80 5 5/ 2/ 0 3 8: 2 0 22 .7 4 2 9

. 8 5 28 .5 6 10 4. 7 3 18 .1 1 55 .2 8 16 .9 5

M E 1 5 / 2/ 0 3 80 5 81 5 5/ 2/ 0 3 8: 3 5 22 .9 5 3 3

. 3 0 22 .1 5 14 9. 7 5 29 .7 3 69 .3 1 22 .4 5



# 6-1

## M E 2 5 / 2/ 0 3 16 4 5 16 5 5 5/ 2/ 0 3 1: 3 0 14 .1 8 4 7

. 0 3 4. 2 1 19 .1 0 5. 8 5 18 .0 0 5. 1 1

M E 2 5 / 2/ 0 3 16 5 5 17 0 5 5/ 2/ 0 3 1: 4 0 13 .6 7 4 7

. 8 5 7. 9 2 26 .4 9 5. 2 4 13 .6 7 4. 0 5

M E 1 5 / 5/ 0 3 75 0 80 0 5/ 5/ 0 3 5: 0 0 14 .9 9 3 9

. 7 6 15 .9 4 75 .7 0 17 .1 3 53 .5 8 16 .7 8

M E 1 5 / 5/ 0 3 80 0 81 0 5/ 5/ 0 3 5: 1 0 17 .2 2 3 3

. 1 3 15 .0 5 66 .4 6 0. 0 0 0. 0 0 0. 0 0

M E 1 5 / 5/ 0 3 82 0 83 0 5/ 5/ 0 3 6: 2 0 21 .7 7 3 8

. 9 9 21 .3 2 15 1. 1 6 12 .0 4 46 .6 4 13 .3 7

M E 1 5 / 5/ 0 3 81 0 82 0 5/ 5/ 0 3 6: 5 0 19 .7 8 3 5

. 9 0 24 .7 0 13 8. 7 2 25 .4 7 90 .3 5 30 .3 6

M E 4 5 / 5/ 0 3 92 3 93 3 5/ 5/ 0 3 5: 5 7 17 .4 6 2 8

. 6 3 1. 7 6 10 .3 6 1. 6 1 5. 9 8 1. 2 3

M E 4 5 / 5/ 0 3 93 3 94 3 5/ 5/ 0 3 6: 0 7 16 .7 0 2 9

. 6 5 10 3. 7 5 38 6. 1 6 34 .9 8 12 1. 6 4 31 .2 9

M E 3 5/ 5/ 0 3 10 4 5 10 5 5 5/ 5/ 0 3 5: 1 5 12 .4 2 3 5

. 1 0 4. 94 14 .6 2 2. 06 8. 31 1. 89

M E 3 5/ 5/ 0 3 10 5 5 11 0 5 5/ 5/ 0 3 5: 2 5 12 .3 1 3 5

. 3 3 6. 55 21 .6 4 2. 92 11 .1 6 2. 29

M E 2 5 / 6/ 0 3 16 4 5 16 5 5 5/ 6/ 0 3 1: 1 0 13 .7 0 3 3

. 7 9 4. 9 5 17 .1 8 2. 8 2 9. 7 8 2. 0 6

M E 2 5 / 6/ 0 3 16 5 5 17 0 5 5/ 6/ 0 3 1: 2 0 13 .4 9 3 4

. 2 2 1. 3 9 1. 2 6 0

. 3 2 1. 0 7 0. 2 3

M E 2 5 / 6/ 0 3 17 0 5 17 1 5 5/ 6/ 0 3 1: 3 0 13 .5 9 3 4

. 6 2 12 .5 2 48 .7 3 14 .3 1 51 .9 1 18 .2 5

a v g 4 : 2 9 16 .5 4 3 2

. 2 5

m a x 9 : 3 8 33 .0 4 5 3

. 4 9

m i n 1 : 0 4 8. 9 3 10 .8 4



# 6-2

# C2-C12 Hydrocarbons Target List

Mnem o n i c s N a m e s Form u l a MW G r o u p

1 E T H E N E et h e n e C 2 H 4 28 .0 5 O

2 A C E T Y L a c e t y l e n e C 2 H 2 26.04

3 E T H AN E et h a n e C 2 H 6 30 .0 7 P

4 P R O P E Prope n e C 3 H 6 O

5 N

_ PR O P n- pr o p a n e C 3 H 8 44 .1 0 P

6 I

_ B U T A i s ob ut a n e 58 .1 2 P

7 L I B U T E i s ob ut e n e C 4 H 8 56 .1 1 O

8 L B UT 1 E C 4 H 8 56 .1 1 O

9 B U D I 1

, 3 1, 3- b u t a di e n e C 4 H 6 54 .1 O

1 0 n- b u t a n e C 4 H 1 0 58 .1 2 P

1 1 T 2 B U T E t

- 2-B u t e n e C 4 H 8 56 .1 1 O

C 2 B U T E c-2

- b u t e n e C 4 H 8 56 .1 1 O

1 3 I P E N T A i s ope nt a n e C 5 H 1 2 72 .1 5 P

1 4 P E N T E 1 1- pe nt e n e C 5 H 1 0 70 .1 3 O

1 5 N

_ PEN T n- pe nt a n e C 5 H 1 2 72 .1 5

1 6 I

_ P R E N i s op r e n e C 5 H 8 68 .1 1 O

1 7 T 2 P E N E t

- 2- Pent e n e C 5 H 1 0 O

1 8 C 2 PE N E c-2

- pe nt e n e C 5 H 1 0 70 .1 3 O

1 9 B U 2 2 DM 2, 2- di m e t h y l but a n e 86 .1 7 P

2 0 C P ENT A cy cl opent a n e C 5 H 1 0 70 .1 3 P

2 1 B U 2 3 DM C 6 H 1 4 86 .1 7 P

2 2 P E N A 2M 2-m e t h y l pent a n e C 6 H 1 4 86 .1 7 P

2 3 

# 6.2 Appendix B: Canisters and Tenax

Y

42.08

C 4 H 1 0

1- b u t e n e

N

_ B U T A

1 2

P

70 .1 3

C 6 H 1 4

2, 3- di m e t h y l but a n e

P E N A 3M 3-m e t h y l pent a n e C 6 H 1 4 86 .1 7 P

2 4 P 1 E 2 M E 2-m e t h y l -1- p e n t e n e C 6 H 1 2 84 .1 6 O

2 5 N

_ HE X n- he x a n e C 6 H 1 4 86 .1 7

2 6 M C YPN A M e t h y l cy cl opent a n e C 6 H 1 2 84 .1 6 P

2 7 P E N 24M 2, 4- di m e t h y l pent a n e C 7 H 1 6 10 0. 2 0

2 8 B E N Z E benze n e C 6 H 6 78 .1 1 A

2 9 C YHE X A cy cl ohexa n e C 6 H 1 2 84 .1 6

3 0 H E X A 2 M 2-m e t h y l hexan e C 7 H 1 6 98 .1 9 P

3 1 P E N 23M P

P

P

2, 3- di m e t h y l pent a n e C 7 H 1 6 10 0. 2 0 P

3 2 H E X A 3 M 3-m e t h y l hexan e C 7 H 1 6 10 0. 2 0 P

3 3 P A 22 4M 2, 2, 4-t r i m et hy lpent a n e C 8 H 1 8 11 4. 2 3 P

3 4 N

_ HEP T n- he pt a n e C 7 H 1 6 10 0. 2 0 P

3 5 M E C Y H X m e t h y l cy cl o h e x a n e C 7 H 1 4 98 .1 9 P

3 6 P A 23 4M 2, 3, 4-t r i m et hy lpent a n e C 8 H 1 8 11 4. 2 3 P

3 7 T O L U E t o l u e n e C 7 H 8 92 .1 4 A

3 8 H E P 2 M E 2-m e t h y l hept a n e C 8 H 1 8 11 4. 2 3 P

3 9 H E P 3 M E 3-m e t h y l hept a n e C 8 H 1 8 11 4. 2 3 P

4 0 N

_ OC T n- oct a n e C 8 H 1 8 11 4. 2 2 P

4 1 E T B Z et hy l b enze n e C 8 H 1 0 10 6. 1 6 A

4 2 M P _X Y L m p -xy l e n e C 8 H 1 0 10 6. 1 6 A

4 3 S T Y R st y r e n e C 8 H 8 10 4. 1 4 A

4 4 O

_ X Y L o- xy l e n e C 8 H 1 0 10 6. 1 7 A

4 5 N

_ N O N n- n ona n e C 9 H 2 0 12 8. 2 6 P



# 6-3

## 4 6 I P R B Z i s op ro py l b e n ze n e C 9 H 1 2 12 0. 2 0 A

4 7 N

_ PR B Z n- pr o p y l benze n e C 9 H 1 2 12 0. 2 0 A

4 8 M

_ ET O L m

- et hy lt ol uene C 9 H 1 2 12 0. 2 0 A

4 9 P

_ E T O L p-et hy l t o l u ene C 9 H 1 2 12 0. 2 0 A

5 0 B Z 13 5M 1, 3, 5-t r i m et hy lbenze ne C 9 H 1 2 12 0. 2 0 A

5 1 O

_ ETO L o-et hy l t o l u ene C 9 H 1 2 12 0. 2 0 A

5 2 B Z 12 4M 1, 2, 4-t r i m et hy lbenze ne C 9 H 1 2 12 0. 2 0 A

5 3 N

_ DEC n- deca n e C 1 0 H 2 2 14 2. 2 9 P

5 4 B Z 12 3M 1, 2, 3-t r i m et hy lbenze ne C 9 H 1 2 12 0. 2 0 A

5 5 D E T B Z 1 m

- di et hy l b e n z e n e C 1 0 H 1 4 13 4. 2 2 A

5 6 D E T B Z 2 p- di et hy l b e n ze n e C 1 0 H 1 4 13 4. 2 2 A

5 7 N

_ U

N D E n- u ndeca n e C 1 1 H 2 4 15 6. 3 0 P

58 M T B E m e t h y l t

- but y l et her C 5 H 1 2 O 88 .1 4 E

T N M H C

A = a r om ati c , AL = Al dehy d e , O = al ke ne ( o l e fi n )

, P = pa r a fi n, Y = al ky n e , K = ket o ne,

E = ethe r, X = haoge n ated, OH = alc o hol



# 6-4Concentrations in ppbC, Tenaxsitedatestarthhmmstophhmmduration(min)ethohmtbetolueetbzmp_xylo_xylFreeway4/29/0307420822400.000.00215.2243.24166.0861.29Freeway4/29/0307420822400.000.00229.5444.83170.3962.76Refueling W/Vapor Re4/29/0312001220200.000.0082.0611.6548.3914.41Garage4/29/0316421712304.240.00105.0223.0895.9732.16Freeway4/30/030739081941.10.000.00342.3864.43247.2689.48Refueling W/O Vapor4/30/030921094119.920.000.00240.6838.40165.0251.89Refueling W/Vapor Re4/30/0310451105200.000.0019.614.2017.135.91Refueling W/O Vapor4/30/0312051225200.000.0049.125.2020.246.35Garage4/30/0316451715300.000.00187.1947.86200.4772.90Refueling W/O Vapor5/1/031106112620.430.000.00146.4810.8945.2211.69Refueling W/Vapor Re5/1/031225124521.30.000.0035.576.6731.1210.55Garage5/1/0316471717300.000.00222.6154.49208.2974.62Freeway5/2/0307350815400.000.00238.4739.24152.5657.05Refueling W/O Vapor5/2/0309180938200.000.00330.8453.26223.4571.59Refueling W/Vapor Re5/2/0310361056200.000.0051.2011.9358.0417.54Garage5/2/0316451715300.000.00137.4336.88145.8649.65Garage5/2/0316451715300.000.00159.0040.65161.5256.03Garage-Blank5/2/031710171000.000.000.190.000.000.00Freeway5/5/0307500830400.000.00396.2781.14304.94108.37Refueling W/O Vapor5/5/0309230943200.000.00270.8124.4794.6825.35Refueling W/Vapor Re5/5/0310451105200.000.0010.472.379.103.62Garage5/6/0316451715300.000.0043.2011.7752.2917.476-5Canister BTEX,ppbCsitedatetimeTime(min)an_typebudi13benzetolueetbzmp_xylo_xyltnmhcFreeway4/29/03742-82220p10.7854.57317.4359.84199.3479.522999.48Refueling W/VaporRecovery4/29/031200-12055p8.8615.3588.9714.9647.7417.41894.91Refueling W/VaporRecovery4/29/031200-12055r8.7915.5291.1815.3350.5718.452020.37Refueling W/VaporRecovery4/29/031200-122020p1.1520.2769.3611.4638.5414.82685.11Garage4/29/031642-171220p6.7833.88102.6724.8184.1933.61234Refueling W/VaporRecovery4/30/031045-110520p0.997.7431.647.7927.9711.75649.59Refueling W/VaporRecovery4/30/031045-110520r0.997.8431.817.828.0711.73631.17Refueling W/VaporRecovery4/30/031055-11005p0.8316.788.0917.559.1222.261718.23RefuelingW/OVapor Recovery4/30/031205-124520p0.5312.854.959.1731.6812.131694.75RefuelingW/OVapor Recovery4/30/031212-12175p0.146.9723.53.019.833.651171.77Garage4/30/031645-171520p11.5259.62223.4555.82192.4677.972081.38Freeway4/30/03739-81920p12.6760.04376.2769.5235.8393.923423.75RefuelingW/OVapor Recovery4/30/03921-92720p1.41247.58708.871.8223.8877.1646526.7RefuelingW/OVapor Recovery4/30/03921-94120p1.0856.75239.8644.01152.1658.448873.4RefuelingW/OVapor Recovery5/1/031106-112620p0.6614.0270.6814.651.820.041967.44RefuelingW/OVapor Recovery5/1/031117-11235p0.89132.77385.7137.26123.0941.8425852.97Refueling W/VaporRecovery5/1/031225-124520p1.069.6643.999.6233.6713.441061.07Garage5/1/031642-171720p13.1863.78239.7857.81202.7878.492437.45Freeway5/1/03720-80020p21.38109.66534.7599323.27124.464797.09Freeway5/1/03720-80020r20.43107.86523.1797.41318.88122.914718.69Refueling W/VaporRecovery5/2/031036-105620p0.613.7864.9916.7662.624.44991.98Refueling W/VaporRecovery5/2/031046-10515p0.194.9735.091661.0325.1673.83Garage5/2/031645-171520p6.9331.72119.6730.29108.2542.871269.07Freeway5/2/03735-81520p10.2243.61215.6538.17125.2748.753511.63RefuelingW/OVapor Recovery5/2/03918-93820p49.8122.93419.5465.06229.5785.6621721.07RefuelingW/OVapor Recovery5/2/03929-9345p2.94458.681320.65199.46674.97254.191380.02Refueling W/VaporRecovery5/5/031045-110520p0.549.350.5911.1139.6415.3699.04Refueling W/VaporRecovery5/5/031055-11005p1.3314.6582.7916.551.2321.15980.43Freeway5/5/03750-83020p10.6657.6312.8566.46230.0690.793246.66RefuelingW/OVapor Recovery5/5/03923-94320p1.38419.621093.91101.8328.81109.5373618.24Garage5/6/031645-171520p6.3529.1899.132693.9736.3710456-6Canisters-Full C2-C12 Speciation (ppbC)siteRefuelingW/VaporRecoveryRefuelingW/VaporRecoveryRefuelingW/OVaporRecoveryRefuelingW/VaporRecoveryRefuelingW/OVaporRecoveryRefuelingW/OVaporRecoveryRefuelingW/VaporRecoveryRefuelingW/OVaporRecoveryRefuelingW/OVaporRecoveryRefuelingW/VaporRecoveryRefuelingW/VaporRecoverydate4/30/034/30/034/30/035/5/035/5/034/30/034/29/035/2/035/1/035/1/035/2/03time1045-11051045-1105921-9411045-1105923-9431205-12451200-1220918-9381106-11261225-12451036-1056an_typeprpppppppppcanisterC073C073C095C136C186C085C046C153C227C076C010ethane5.205.268.834.5834.045.385.9114.874.604.805.00ethene10.8210.936.985.705.325.4810.9611.464.098.257.79acetyl35.9037.3013.6012.674.1014.6928.9020.415.2222.1613.31prope4.424.4120.393.04555.076.259.4384.863.664.74.69n_prop3.033.0444.313.37654.8822.0711.72138.739.065.84.97i_buta8.398.37292.118.363119.1149.7976.51781.185.7935.3614.52lbut1e1.021.0214.770.6468.502.324.0425.0610.583.810.86libute1.691.6753.120.60335.617.860.00127.695.553.742.21budi130.990.991.080.541.380.531.1549.80.661.060.6n_buta42.9742.251350.1352.0815644.09217.4398.793806.37354.28158.677.7t2bute1.441.549.991.13404.029.1612.28114.9617.446.292.11c2bute0.790.8331.441.58179.854.117.2353.9811.384.072.81ipenta99.6699.213079.399.9625116.14557.31812.578387.13474.96233.46176.62pente11.311.4177.44.41428.67.3314.96150.0610.495.036.71n_pent16.716.89496.4717.434118.1983.55137.591229.9383.2941.9227.72i_pren0.470.471.430.413.580.8511.350.690.560.45t2pene8.538.59253.289.081998.1642.7172.47596.8345.3924.8513.25c2pene3.424.02100.553.73795.7716.8729.41235.5718.8110.715.35bu22dm2.041.9941.612.523708.7211.7116.556.163.423.66cpenta1.911.8542.072.44386.018.4511.17112.468.764.183.03bu23dm3.123.1673.754.58623.6512.0123.03170.6514.379.996.11pena2m12.5712.62265.5119.012433.148.1681.18653.2550.3525.2522.83pena3m7.568.25149.7711.811379.4227.4946.61366.9228.714.2413.94p1e2me0.90.912.441.52156.272.43.828.523.371.551.72n_hex5.325.3789.448.95840.1217.8428.87219.9616.878.729.71mcypna8.738.85142.415.071332.1227.1945.25352.7328.5914.2716.54pen24m0.97114.41.79112.792.894.5232.784.33.782.13benze7.777.79579.26419.6212.820.36123.0514.039.6713.826-7cyhexa2.382.4235.484.22291.397.9810.3190.557.390.325.59hexa2m5.575.486210.02467.7314.1819.39145.5414.937.8811.42pen23m2.031.9925.293.57171.675.377.4654.367.465.334.25hexa3m0.30.283.320.4321.310.560.846.210.740.380.44pa224m2.192.123.453.75173.55.217.1355.494.763.054.2n_hept4.254.4945.478.45278.3910.6613.79103.5111.516.4110.54mecyhx4.674.7247.998.5308.1410.5614.49105.312.116.4510.63pa234m0.640.675.230.920.081.011.96.692.652.331.28tolue31.6431.81239.9750.591093.9154.9569.39419.5470.6843.9864.99hep2me2.292.3417.193.6467.263.624.9129.514.613.024.88hep3me2.62.5817.283.8665.213.85.5129.535.033.215.26n_oct1.961.9611.362.5733.322.523.7717.782.522.233.75etbz7.917.8645.2411.05101.89.2211.566.1414.889.6216.9mp_xyl28.3928.07152.2639.78328.8131.7238.56229.8452.4333.6862.6styr1.411.274.371.374.230.91.433.811.041.361.49o_xyl11.7211.7558.8315.37109.5312.1115.6585.9120.2313.3824.36n_non1.091.035.511.447.091.111.657.480.721.192.08iprbz0.690.663.480.814.190.760.824.341.090.81.29n_prbz2.72.6211.773.0612.852.383.0514.764.032.774.62m_etol9.178.7634.1410.4136.043.624.4542.7613.279.5416.57p_etol4.384.1216.914.6815.857.539.4120.546.114.527.53bz135m4.32414.924.6113.893.534.418.185.984.157.81o_etol4.113.9512.94.514.293.515.0916.695.574.026.6bz124m13.9512.8947.2415.4340.5411.1414.3852.4920.0814.6325.18n_dec1.972.271.720.391.731.181.363.260.461.010.73bz123m3.483.391.090.387.522.553.430.980.653.235.13detbz10.991.042.250.781.920.741.542.981.090.81.22detbz23.243.146.542.785.082.012.937.313.282.474.01n_unde1.471.513.531.42.11.051.833.31.111.141.84tnmhc656.76646.788908.0670272023.31690.042706.5721748.671976.271062.58996.546-86.3Appendix C: Breath SamplesSiteDateTimebud13CO2,%ethohmtbebenzetolueetbzmp_xylo_xylRefueling W/Vapor Recovery, PreFuel4/2912005.090.27133.860.740.8799.310.531.360.33Refueling W/Vapor Recovery, PostFuel4/2912154.380.1087.750.460.8978.420.491.200.29Garage,Pre4/2916425.910.2178.100.460.8172.490.461.090.27Garage,Peak4/2916546.060.0412.110.180.232.120.160.610.16Garage,Post4/2917156.160.043.260.070.060.450.040.130.03Freeway,Pre4/297315.350.2051.260.270.70137.390.721.800.43Freeway,Peak4/298005.002.7726.901.134.73150.462.839.213.06Freeway,Post4/298265.440.8526.600.361.88125.080.992.720.76Refueling W/Vapor Recovery, PreFuel4/3010476.240.12138.930.691.1668.790.441.130.27Refueling W/Vapor Recovery, PostFuel4/3010595.790.65153.240.642.2877.750.782.250.62Refueling W/O Vapor Recovery, PreFuel4/3012034.930.1854.350.401.0150.460.441.180.31Refueling W/O Vapor Recovery, PostFuel4/3012165.800.00201.011.805.4775.040.651.660.41Garage,Pre4/3016436.111.35137.300.321.8760.470.621.610.43Garage,Peak4/3017076.013.65107.430.335.3561.731.735.531.80Garage,Post4/3017215.835.24123.880.577.1763.391.685.291.72Freeway,Pre4/307275.640.1586.910.480.6487.070.571.340.31Freeway,Peak4/307574.714.4851.230.757.92102.673.4911.353.69Freeway,Post4/308224.500.6954.620.361.8182.250.862.320.60Refueling W/O Vapor Recovery, PreFuel4/309234.920.1865.020.461.2275.460.691.790.50Refueling W/O Vapor Recovery, PostFuel4/309354.740.0064.675.0416.8099.082.146.551.94Refueling W/O Vapor Recovery, PreFuel5/111076.710.05103.180.350.972.720.150.430.126-9Refueling W/O Vapor Recovery, PostFuel5/111197.740.15176.981.222.764.980.270.860.28Refueling W/Vapor Recovery, PreFuel5/112276.020.11118.300.691.272.630.150.460.13Refueling W/Vapor Recovery, PostFuel5/112385.210.2181.070.551.142.610.180.590.18Garage,Pre5/116487.240.6545.680.341.412.900.290.820.26Garage,Peak5/117035.823.3699.740.373.975.920.641.900.61Garage,Post5/117196.300.7560.610.331.793.430.280.960.27Freeway,Pre5/17126.330.0736.680.240.290.640.040.150.04Freeway,Peak5/17355.053.7936.450.677.0319.531.935.912.03Freeway,Post5/18025.353.5823.500.466.1423.471.574.801.55Refueling W/Vapor Recovery, PreFuel5/210374.820.1242.470.450.9930.160.250.710.19Refueling W/Vapor Recovery, PostFuel5/210505.700.1328.590.471.2535.160.521.600.49Garage,Pre5/216455.250.9372.420.001.3229.850.341.000.29Garage,Peak5/217065.250.5669.430.181.0127.710.260.760.21Garage,Post5/217166.001.4563.470.182.7231.490.601.810.54Freeway,Pre5/27295.310.19113.500.200.4941.320.260.720.19Freeway,Peak5/27494.931.9666.010.353.6546.591.143.471.16Freeway,Post5/28164.572.1436.270.333.3650.420.912.530.75Refueling W/O Vapor Recovery, PreFuel5/29205.520.4270.740.200.7232.430.290.740.18Refueling W/O Vapor Recovery, PostFuel5/29326.090.0064.885.1516.0762.341.303.801.02Refueling W/Vapor Recovery, PreFuel5/510455.990.1092.421.092.855.580.290.850.24Refueling W/Vapor Recovery, PostFuel5/510585.590.0533.130.863.527.340.361.190.32Freeway,Pre5/57440.980.0617.620.270.310.530.050.140.04Freeway,Peak5/57555.892.0317.710.482.934.800.501.610.49Freeway,Post5/58325.252.1710.050.354.2915.671.223.791.29Refueling W/O Vapor Recovery, PreFuel5/59236.300.1888.500.230.671.770.130.460.13Refueling W/O Vapor Recovery, Post-5/59366.420.0084.8716.3680.6879.302.737.742.116-10FuelGarage,Pre5/616446.160.49175.180.301.422.650.321.000.34Garage,Peak5/617065.591.37102.340.221.973.930.552.000.67Garage,Post5/617186.480.6558.690.271.573.050.340.980.276-11

# 6.4 Appendix D: DNPH

S i t e D a t e Sta r t

time Stop

time Dur a ti on V (L ) V u

(L) form al form alu a cetal a c e t a l u a c e t o a cetou

Free way 4 / 2 9 / 0 3 07 4 2 08 2 2 40 47 .1 2. 36 17 .3 8 0

. 9 5 5

. 2 7 0. 8 0 32 .1 8 1

. 8 5

Free way 4 / 3 0 / 0 3 07 3 9 08 1 9 41 45 .2 2. 26 19 .0 2 1

. 0 4 4

. 6 7 0. 8 0 28 .3 5 1

. 6 4

Free way 5 / 1/ 0 3 07 2 0 08 0 0 41 .1 45 .3 2. 27 19 .8 0 1

. 0 7 8

. 2 2 0. 9 5 57 .3 4 3

. 2 4

Free way 5 / 2/ 0 3 07 3 5 08 1 5 40 44 .1 2. 21 19 .1 3 1

. 0 5 4

. 8 4 0. 8 2 20 .6 7 1

. 2 3

Free way 5 / 5/ 0 3 07 5 0 08 3 0 40 44 .1 2. 21 17 .5 6 0

. 9 7 5

. 2 4 0. 8 3 61 .1 7 3

. 4 5

Gara g e 4 / 2 9 / 0 3 16 4 2 17 1 2 30 33 .0 1. 65 5. 59 0. 43 2. 8 3 0. 9 9 34 .3 6 2

. 0 1

Gara g e 4 / 3 0 / 0 3 16 4 5 17 1 5 30 33 .0 1. 65 7. 58 0. 52 3. 5 0 1. 0 1 27 .3 8 1

. 6 3

Gara g e 5 / 1/ 0 3 16 4 2 17 1 7 30 33 .0 1. 65 9. 12 0. 58 3. 7 6 1. 0 1 20 .2 3 1

. 2 7

Gara g e 5 / 2/ 0 3 16 4 5 17 1 5 30 33 .1 1. 66 7. 35 0. 49 2. 7 6 0. 9 9 21 .7 7 1

. 3 5

Gara g e 5 / 6/ 0 3 16 4 5 17 1 5 30 33 .1 1. 66 5. 44 0. 42 2. 5 0 0. 9 8 44 .9 1 2

. 5 8

Gara ge-B l a n k 5 / 2/ 0 3 17 0 6 17 0 6 0 3 0

. 6 1

. 5 3 0

. 0 0 0

. 2 3 1

. 8 5 0. 2 7 1. 68 0. 19

Gara ge-B l a n k 5 / 6/ 0 3 16 1 2 16 1 2 0 3 0

. 6 1

. 5 3 0

. 0 0 0

. 2 3 0

. 4 3 0. 2 1 0. 87 0. 17

R e fuel i n g W/ O Va po r 4/ 3 0 / 0 3 09 2 1 09 4 1 19 .9 21 .9 1. 10 3. 62 0. 52 3. 37 1. 47 13 .3 1 1

. 1 2

R e fuel i n g W/ O Va po r 4/ 3 0 / 0 3 12 0 5 12 2 5 20 22 .0 1. 10 2. 12 0. 46 2. 57 1. 46 10 .6 6 1

. 0 3

R e fuel i n g W/ O Va po r 5/ 5/ 0 3 11 0 6 11 2 6 20 .4 22 .4 1. 12 5. 52 0. 55 2. 72 1. 43 31 .0 6 1

. 9 2

R e fuel i n g W/ O Va po r 5/ 2/ 0 3 09 1 8 09 3 8 20 22 .0 1. 10 4. 03 0. 53 3. 26 1. 46 5. 98 0. 89

R e fuel i n g W/ O Va po r 5/ 5/ 0 3 09 2 3 09 4 3 20 22 .0 1. 10 5. 52 0. 56 3. 17 1. 46 20 .1 0 1

. 4 0

R e fuel i n g W / Va po r

Re 4/ 2 9 / 0 3 1 2 0 0 12 2 0 20 22 .0 1. 10 4. 35 0. 54 2. 9 7 1. 4 6 20 .0 0 1

. 3 9

R e fuel i n g W / Va po r

Re 5/ 1/ 0 3 1 2 2 5 12 4 5 21 .3 23 .4 1. 17 3. 29 0. 49 1. 7 7 1. 3 6 10 .0 1 0

. 9 6

Refu eling W / Va p or

Re 4/ 3 0 / 0 3 1 0 4 5 11 0 5 20 22 .0 1. 10 2. 87 0. 47 1. 3 8 1. 4 4 12 .9 0 1

. 1 1

R e fuel i n g W / Va po r

Re 5/ 2/ 0 3 1 0 3 6 10 5 6 20 22 .0 1. 10 4. 67 0. 54 2. 4 7 1. 4 6 9. 07 0. 97

R e fuel i n g W / Va po r

Re 5/ 5/ 0 3 1 0 4 5 11 0 5 20 22 .0 1. 10 3. 29 0. 52 1. 7 8 1. 4 4 7. 94 0. 95

form al =Form a ldehyde acetal = Acetaldehy de

form alu =Formaldehyde unc e rtainty acetalu =Aceta l dehyde unce rtainty

aceto=Acet one

acetou= Acetone uncertainty



# 6-12