RTI7140/03 February 26, 1990
BREATH MEASUREMENTS OF INDIVIDUALS
EXPOSED TO CHEMICALS DURING PERSONAL ACTIVITIES
FINAL REPORT
'by
E. D. Pellizzari, K. W. Thomas, J. H. Raymer,
D. J. Smith and S. D. Cooper
RTI Work Assignment Leader: E. D. Pellizzari
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, NC 27709-2194
Contract Number: 68-02-4544
Work Assignment Number: 11-40
Project Officer: David 0. Hinton
Atmospheric Research and Exposure Assessment Laboratory
Exposure Assessment Division
Environmental Monitoring Branch
Task Manager: W. C. Nelson
Atmospheric Research and Exposure Assessment Laboratory
Exposure Assessment Division
Environmental Monitoring Branch
PREPARED FOR
United States Environmental Protection Agency
Research Triangle Park, NC 27711
INTERNATIONAL
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RTI/140/03
February 26, 1990
BREATH MEASUREMENTS OF INDIVIDUALS
EXPOSED TO CHEMICALS DURING PERSONAL ACTIVITIES
FINAL REPORT
by
E. D. Pellizzari, K. W. Thomas, J. H. Raymer,
D. J. Smith and S. D. Cooper
RTI Work Assignment Leader: E. D. Pellizzari
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, NC 27709-2194
Contract Number: 68-02-4544
Work Assignment Number: 11-40
Project Officer: David 0. Hinton
Task Manager: W. C. Nelson
Submitted by:
K. W. Thomas
Task Leader
Approved by:
ASN^JWL.
E. D. PeTnVzari
Project Director
PREPARED FOR
United States Environmental Protection Agency
Research Triangle Park, NC 27711
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NOTICE
This document is a preliminary draft. It has not been formally
released by the U.S. Environmental Protection Agency and should not at this
stage be construed to represent Agency policy. It is being circulated for
comments on its technical merit and policy implications.
ii
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ABSTRACT
Breath measurements offer the potential for a direct and noninvasive
evaluation of human exposure to volatile organic compounds (VOCs) in the
environments in which people live and work. This research study was
conducted to further develop the potential of this exposure assessment
methodology. A new alveolar breath measurement technique was developed and
tested. Air samples were collected in 32 microenvironments and above 6
consumer products to determine a few potential sources of human exposures
to selected VOCs. Several people were exposed to the atmosphere in six
microenvironments for several hours. Air concentrations of VOCs were
measured during these exposures and breath samples were collected and
analyzed at multiple time points after the exposure to evaluate elimination
kinetics for 21 VOCs. Elimination half-lives were estimated using a mono-
and biexponential model. Several other mathematical functions were tested
for their ability to accurately describe the breath decay curves for VOCs.
The alveolar breath collection and analysis methodology proved to be very
useful for collecting many samples in short time intervals and this
capability was very important for accurately describing the initial phase
of the decay curves. Analysis of microenvironment air samples from homes,
businesses, workplaces, vehicles, etc., revealed a wide range of potential
sources of human exposures to VOCs at concentrations from 1 to 16,000
/*g/m3. Breath decay curves were developed over a four hour period after
exposure for 21 of 24 target VOCs. A biexponential function provided a
better fit for the decay data than did the monoexponential function,
suggesting a multi-compartment uptake and elimination model for the human
body.
iii
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CONTENTS
Page
Abstract i ii
Figures vi
Tab! es xi
1 Introduction 1
2 Conclusions 4
Microenvironment and Consumer Product Screening 4
Breath Analysis as a Measure of Exposure 5
3 Recommendations '.... .8
Sample Collection and Analysis 8
Microenvironment Screening 8
Further Data Analysis 9
Future Experiments 9
4 Sample Collection and Analysis 11
Introducti on 11
Collection of Screening Samples 11
Collection of Exposure Experiment Samples 19
Sample Analysis 36
5 Quality Assurance 47
Analytical Protocols 47
Field Operations/Sample Collection 47
Sample Analysis 49
QC Sample Analysis (Field Blanks and Controls) 59
Duplicate Sample Analysis 66
Performance Evaluation Sample Analysis 72
6 Results and Data Analysis 76
Introduction 76
Screening Results 76
Exposure Experiment Results 94
Mathematical Treatment of the Data 109
IV
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CONTENTS (CONT'D.)
Page
References 138
Appendices
A Initial Feasibility Study for an Alveolar Spirometer
B Refinement, Testing, and Construction of a Portable Alveolar
Spirometer
C Breath Exposure Study Establishment Consent Form
D Breath and Air Concentration Tables for Exposure Experiments
E Decay Data in Graphical Form
F Calculated Half-Life Data for Alveolar and Whole Breath Decay
Curves
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FIGURES
Number Page
4-1 Dynamic headspace purge apparatus for measuring consumer
product emi ss i ons 15
4-2 Canister cleaning system diagram 30
4-3 Schematic diagram of the alveolar spirometer system 31
4-4 Exhale valve and sample port 33
4-5 Schematic diagram of the whole breath spirometer system 34
4-6 Schematic diagram of the canister analysis system 38
6-1A Breath levels of toluene post exposure to furniture stripping
operati ons 101
6-1B Breath levels of p_-xylene post exposure to furniture stripping
operati ons 101
6-2 Decay of 1,1,1-trichloroethane in alveolar breath after
exposure to an active wood working shop 103
6-3 Schematic of a physiologically based model for metabolism of
inhaled gases and vapors Ill
6-4 Ln-linear display of decay data measured for dichloromethane
in alveolar and whole breath 119
6-5 Ln-linear display of decay data measured for dichloromethane
in alveolar and whole breath 120
6-6 Concentration of n-pentane in alveolar breath as a function
of time post exposure 125
6-7 Concentration of n-pentane in alveolar breath as a function
of time post exposure 126
6-8 Concentration of n-pentane in alveolar breath as a function
of time post exposure 127
6-9 Concentration of n-pentane in alveolar breath as a function
of time post exposure 128
6-10 Concentration of n-pentane in alveolar breath as a function
of time post exposure 129
VI
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FIGURES (cont'd.)
Number Page
6-11 Concentration of n-pentane in alveolar breath as a function
of time post exposure 130
6-12 Concentration of n-pentane in alveolar breath as a function
of time post exposure 131
A-l Schematic diagram of the device used to study effects of
tube diameter and sampling flow rate A-15
A-2 C02 profile with continuous sampling A-18
A-3 Device used to test precision based on syringe samples A-20
A-4 Device as configured for precision study based on canister
sampl es A-22
A-5 Exhale valve and sample port A-24
A-6 Device used to generate synthetic breath for recovery studies.A-25
A-7 Forward profile of m/z 44 (C02) with time and repetitive
breathi ng A-6
B-l Schematic diagram of the analytical system sued for the
analysis of canister air or breath samples B-15
B-2 Synthetic breath generator including verification canister
and switcshing valves prior to spirometer B-24
B-3 Portable spirometer for the collecting VOCs in alveolar
breath B-44
B-4 Exhale valve and sample port B-50
breathi ng A-29
E-l Breath level of dichloromethane post exposure to furniture
stripping operations E-2
E-2 Breath level of 1,1,1-trichloroethane post exposure to
furniture stripping operations E-2
E-3 Breath level of toluene post exposure to furniture stripping
operati ons E-3
E-4 Breath level of ฃ-xylene post exposure to furniture stripping
operati ons E-3
E-5 Breath level of dichloromethane post exposure to hardware
store environment E-4
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FIGURES (cont'd.)
Number Page
E-6 Breath level of 1,1,1-trichloroethane post exposure to
hardware store envi ronment E-4
E-7 Breath level of toluene post exposure to hardware store
envi ronment E-5
E-8 Breath level of tetrachloroethylene post expousre to hardware
store envi ronment E-5
E-9 Breath level of ethyl benzene post exposure to hardware store
envi ronment E-6
E-10 Breath level of ฃ-xylene post exposure to hardware store
envi ronment E-6
E-ll Breath level of n-nonane post exposure to hardware store
envi ronment E-7
E-12 Breath level of o-xylene post exposure to hardware store
envi ronment E-7
E-13 Decay is isopentane and chloroform in alveolar breath after
exposure to an indoor swimming pool E-8
E-14 Decay of pentane and vinylidene chloride in alveolar breath
after exposure to an active wood working shop and metal
shop E-9
E-15 Decay of 1,1,1-trichloroethane in alveolar breath after
exposure to an active wood working shop and metal shop E-9
E-16 Decay of toluene in alveolar breath after exposure to an
active wood working and metal shop E-10
E-17 Decay of limonene and a-pinene in whole breath after exposure
to consumer products as determined by Tenax-based
sampling and anlaysis E-ll
E-18 Decay of ฃ-dichlorobenzene in whole breath after exposure to
consumer products as determined by Tenax-based sampling
and analysis E-ll
E-19 Breath level of isopentane post exposure to staining in
home garage E-12
E-20 Breath level of pentane post exposure to staining in home
garage E-12
viii
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FIGURES (cont'd.)
Number Page
E-21 Breath level of 2-methylpentane post exposure to staining
in home garage E-13
E-22 Breath level of 2-methylhexane post exposure to staining
in home garage E-13
E-23 Breath level of 3-methylhexane post exposure to staining
in home garage E-14
E-24 Breath level of benzene post exposure to staining in home
garage E-14
E-25 Breath level of toluene post exposure to staining in home
garage E-15
E-26 Breath level of n-octane post exposure to staining in home
garage E-15
E-27 Breath level of ethylcyclohexane post exposure to staining
in home garage E-16
E-28 Breath level of 3-methyloctane post exposure to staining
in home garage E-16
E-29 Breath level of ethyl benzene post exposure to staining in
home garage E-17
E-30 Breath level of ฃ-xylene post exposure to staining in home
garage E-17
E-31 Breath level of n-nonane post exposure to staining in home
garage E-18
E-32 Breath level of o-xylene post exposure to staining in home
garage E-18
E-33 Breath level of n-decane post exposure to staining in home
garage E-19
E-34 Breath level of n-undecane post-exosure to staining in home
garage E-19
E-35 Decay of dichloromethane in alveolar breath for two partici-
pants exposed at the same time in a hardware store
env i ronment E-20
IX
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FIGURES (cont'd.)
Number Page
E-36 Decay of 1,1,1-trichloroethane in alveolar breath for two
participants exposed at the same time in a hardware
store environment E-20
E-37 Decay of toluene in alveolar breath for two participants
exposed at the same time in a hardware store environment.E-21
E-38 Decay of ethylbenzene in alveolar breath for two participants
exposed at the same time in a hardware store environment.E-21
E-39 Decay of p_-xylene in alveolar breath for two participants
exposed at the same time in a hardware store environment.E-22
E-40 Decay of n-nonane in alveolar breath for two participants
exposed at the same time in a hardware store environment.E-22
E-41 Decay of o-xylene in alveolar breath for two participants
exposed at the same time in a hardware store environ-
ment E-23
E-42 Decay of n-decane in alveolar breath for two participants
exposed at the same time in a hardware store environment.E-23
E-43 Decay of dichloromethane in alveolar breath for two partici-
pants exposed at the same time in a hardware store
envi ronment E-24
E-44 Decay of 1,1,1-trichloroethane in alveolar breath for two
participants exposed at the same time in a hardware
store envi ronment E-24
E-45 Decay of toluene in alveolar breath for two participants
exposed at the same time in a hardware store environ-
ment E-25
E-46 Decay of tetrachloroethylene in alveolar breath for two
participants exposed at the same time in a hardware
store envi ronment E-25
E-47 Decay of p_-xylene in alveolar breath for two participants
exposed at the same time in a hardware store environ-
ment E-26
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FIGURES (cont'd.)
Number Page
E-48 Decay of n-nonane in alveolar breath for two participants
exposed at the same time in a hardware store environ-
ment E-26
E-49 Decay of n-decane in alveolar breath for two participants
exposed at the same time in a hardware store environ-
ment E-27
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TABLES
Number Page
4-1 Target Chemicals for Screening and Breath Exposure Study
Samples 12
4-2 Microenvironment Screening Sample Locations for Canister
Air Sampling 16
4-3 Microenvironment Screening Sample Locations for Tenax Air
Sampl ing 18
4-4 Consumer Product Emission Samples Collected on Tenax Using
A Dynamic Headspace Purge 18
4-5 Microenvironments and Chemicals Selected for Breath Exposure
Experiments 20
4-6 Exposure Experiment Sample Collection Outline 22
4-7 Consumer Product Exposure Experiment Sample Collection
Outl ine 24
4-8 Experimental Conditions and Samples Collected During Exposure
Experiments 25
4-9 Participant Characteristics and Approximate Alveolar
Spirometer Breathing Rates 28
4-10 Analytical Conditions for Canister Sample Analysis 39
4-11 Additional Compounds and Their Quantitation Basis 42
4-12 Limits of Detection and Quantifiable Limits for Canister and
Tenax Analysis 43
4-13 GC/MS Tenax Analysis Parameters 45
5-1 Analytical Protocols Prepared for Exposure Assessment Study 48
5-2 Completeness of Sample Collection and Analysis 50
5-3 Sample Receipt Report 51
5-4 Levels of Target Analytes Loaded onto Tenax Cartridges for
Calibration 53
5-5 Relative Response Factors Used for Quantitation of Volatile
Organics in Tenax Samples 54
5-6 Results of Analyses of Daily Response Factor Tenax Cartridges...55
xii
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TABLES (cont'd.)
Number Page
5-7 PFT Tune Data, Daily Check - Finnigan 4021 56
5-8 Levels of Standards Used to Prepare Canister Sample Calibra-
tions 58
5-9 Daily Calibration Checks - Canister Whole Breath Calibration 60
5-10 Daily Calibration Checks - Canister Alveolar Breath 61
5-11 Daily Calibration Checks - Canister Air 62
5-12 Summary of External Standard Peak Height Measurements -
LKB 2091 System 63
5-13 Results of Analysis of Tenax Control Samples 64
5-14 Results of Analysis of Tenax Blank Samples 65
5-15 Results of Analysis of Canister Whole Breath Control Samples 67
5-16 Results of Analysis of Canister Alveolar Breath Control
Sampl es 68
5-17 Results of Analysis of Canister Whole Breath Blank Samples 69
5-18 Results of Analysis of Canister Alveolar Breath Blank Samples...70
5-19 Percent Relative Standard Deviation (%RSD) for Duplicate
Tenax Samples (Interlaboratory) 71
5-20 Results of Analysis of Tenax Quality Control Samples by the
Independent Laboratory 71
5-21 Percent Relative Standard Deviation (%RSD) for Duplicate
Tenax Samples (Intralaboratory) 73
5-22 Percent Relative Standard Deviation (%RSD) for Duplicate
Canister Samples (Intralaboratory) 74
5-23 Results of Analysis of Performance Evaluation Canisters 75
6-1 Air Concentrations (/
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TABLES (cont'd.)
Number Page
6-4 Qualitative Results of the GC/MS Analysis of Product Head-
space Samples for a-Pinene and Limonene 93
6-5 Percent Difference Between Alveolar and Whole Breath Organic
Compound Concentrations at 12, 60, and 185 Minutes
Post exposure 107
6-6 Calculated Half-Lives for Halogenated Hydrocarbons in
Al veol ar Breath 113
6-7 Calculated Half-Lives for Aromatic and Halogenated Hydrocar-
bons in Whole Breath 116
6-8 Comparison of Calculated Half-Lives for Whole Breath Data
With and Without First Time Point (Garage Experiment) 121
6-9 Mathematical Functions Used in the Bivariate Curve Fit
Analyses 124
6-10 Results of STATPLAN Bivarate Curve-Fitting Survey for
Alveolar Breath Samples 132
6-11 Comparison of Predictive Abilities of Two Functions for
The Decay of 1,1,1-Trichloroethane in Alveolar Breath
(Experiment WS1) 134
6-12 Results of STATPLAN Bivarate Curve-Fitting Survey for
Whole Breath Samples 136
6-13 Effect of Data Set Completeness on Predictive Abilities of
Fitted Bivarate Curves for Benzene (Experiment GS1) 137
A-l Concentrations of Target Compounds in the Primary Standard....A-26
A-2 Effect of Tube Diameter and Sampling Rate on Alveolar Air
Plug A-30
A-3 Fraction of Alveolar Air Sampled as a Function of Type of
Breathing, Breathing Rate and Continuous Sampling A-33
A-4 Determination of Alveolar C02 Concentration and Dilution of
Alveolar Air in Whole Breath A-35
A-5 Results of Syringe Sampling A-36
A-6 Canister Precision Study Results A-37
A-7 GC/MS Peak Heights from Analyses of Zero (Z) Level
Cani sters A-39
xiv
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TABLES (cont'd.)
Number Page
A-8 Recoveries of Target Compounds at Low (4.4 ng/L) Level A-41
A-9 Recoveries of Target Compounds at High (36 ng/L Level) A-42
B-l Analytical Conditions for Canister Sample Analysis B-16
B-2 List of Target Compounds for Evaluating the Effectiveness
of Respirator Cartridges B-19
B-3 Target Compounds for Adsorptive Loss and Carryover
Experiments B-25
B-4 Sample Collection Regimen for the Adsorptive Loss
Experiments B-27
B-5 Sample Collection Regimen for the Carryover Experiments B-29
B-6 Estimated Quantifiable Limits for Target Compounds for
Canister Air Analyses Using MID B-33
B-7 Concentrations (/tg/m3) of Target Compounds Found in Centered
Laboratory Air B-34
B-8 Concentrations of Target Compounds in Air with Continuous
Filtering at Low Concentrations B-35
B-9 Concentrations of Target Compounds in Air with Approximately
Continuous Filtering at Higher Concentrations B-37
B-10 Concentrations of Target Compounds in Air Collected Over
5 Filtering Cycles (Days) B-38
B-ll Results of Multiple Analysis Capacity of 1-Liter Canisters....B-39
B-12 Percent Recovery from Adsorptive Loss Experiments for the
First and Second Spirometer USe for Each Sampling Pair...B-41
B-13 Percent Recovery Relative to Verification Sample for Each
High Level/Low Level Pair to Test Carryover B-42
B-14 Portable Spirometer Parts List B-45
F-l Calculated Half-Lives for Halogenated Hydrocarbons in
Al veol ar Breath F-2
F-2 Calculated Half-Lives for Aromatic Hydrocarbons in
Alveolar Breath F-3
F-3 Calculated Half-Lives for Aliphatic Hydrocarbons in
Al veol ar Breath F-4
xv
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TABLES (cont'd.)
Number Page
F-4 Calculated Half-Lives for Aromatic and Halogenated Hydro-
carbons in Whole Breath F-5
F-5 Calculated Half-Lives for Aliphatic and Cyclic Hydrocarbons
in Whole Breath F-6
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SECTION 1
INTRODUCTION
For nearly a decade, the U.S. EPA has been conducting studies of perso-
nal exposure to volatile organic compounds (VOCs) [1-5]. Participants in
these studies have also provided breath samples and measured VOC concen-
trations in breath have demonstrated strong correlations with actual
exposure levels. For a few chemicals, e.g. 1,1,1-tn'chloroethane, tri-
chloroethylene, tetrachloroethylene, ฃ-dichlorobenzene, m,ฃ-xylenes and
ethylbenzene, the correlations have been extended further to suggest a link
between exposure levels, breath concentrations, and a person's activity or
microenvironment [1]. Consequently, two general questions have arisen:
(a) what are the common personal activities and microenvironments that may
lead to elevated human exposure to VOCs and (b) can breath measurements
provide a quantitative measurement of VOC exposure?
The ability to use breath measurements HI lieu of personal monitoring
would circumvent the participant burden experienced with personal moni-
toring. It would also provide a noninvasive alternative to blood collec-
tion and analysis methods for determining body burden. Currently employed
models, however, that relate breath to the immediate periods of exposure
are imprecise. The VOC residence time in the body is a parameter that is
important in perfecting prediction models but is not well described in the
literature for nonoccupational situations. Although the breath excretion
rates of a few VOCs have been measured in a few subjects [6,7], further
information is needed for more compounds, subjects, and exposure levels for
the development of accurately predictive models.
A study to further examine the parameters governing breath VOC levels
after exposure was sponsored by the U.S. Environmental Protection Agency
and is the subject of this report. This research was conducted in three
separate phases. First, the feasibility of a device capable of the rapid
collection of alveolar breath was studied. The results of these initial
investigations are presented in Appendix A. A prototype version of this
device was used for breath measurements of individuals exposed to various
1
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microenvironments as described in the body of this report. After
completion of these microenvironmental exposure studies, the third phase of
the research culminated in the design, testing, and construction of a
portable alveolar spirometer. This work is described in Appendix B.
The principal objectives of this microenvironmental exposure study were
to
a. test the prototype canister based sampling system for measuring
VOC concentrations in alveolar breath over short (2 to 5 min) time
intervals,
b. examine personal activities and microenvironments commonly encoun-
tered by the general population that might lead to elevated VOC
exposures,
c. determine the breath VOC concentrations that result from exposure
to a variety of different chemicals, and
d. calculate residence times for VOCs in the body, including half-
lives and best-fit curve functions, that can be used for
developing exposure-prediction models.
In order to achieve these objectives a list of 24 target VOCs was
selected covering a wide range of volatilities and chemical functional
groups that included halogenated, aliphatic, and aromatic compounds.
Approximately 40 microenvironments, consumer products, and human activities
were evaluated to determine if they would result in elevated human expo-
sures to the selected VOCs. Specific microenvironments, consumer products,
and activities were chosen to represent common sources of exposure in the
general population and included stores, businesses, homes, workplaces,
swimming pools, automobiles, and solvent containing consumer products.
Screening samples were collected and analyzed to determine the identity and
levels of the target VOCs associated with these sources.
Based upon the screening analysis results, six microenvironments were
chosen for conducting the exposure and breath residence time experiments.
The choices were made to include as many target compounds within each
microenvironment as possible and to study as many of the 24 target
compounds as possible using the six microenvironments. In order to be
included in the exposure experiments, the target compound concentrations
had to be sufficiently high to provide elevated breath concentrations for
decay curve experiments.
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Human exposure experiments were conducted in each of the six micro-
environments to determine the VOC breath concentration resulting from
exposure and subsequent decay in breath levels over a period of several
hours. Participants provided a breath sample immediately prior to exposure
in the selected microenvironment to determine baseline levels for breath
VOCs. They were then exposed to the microenvironment for two to four
hours. Eight to eleven breath samples were collected over the four hours
after exposure to measure residence times for each elevated compound. Air
samples were collected within the subject's microenvironment before,
during, and after the exposure to determine intended and unintended expo-
sure concentrations. Experiments within one microenvironment were
conducted for four different people to provide some data on the interper-
sonal variability in breath residence time and decay curve characteristics.
A modified spirometer system capable of collecting alveolar breath
canister samples over short time intervals was employed for five of the six
microenvironments. This device had been developed and tested during an
earlier phase of this research (Appendix A). One advantage of the alveolar
spirometer system was the ability to rapidly collect multiple samples after
the exposure was completed which allowed for a precise definiton of the
early portion of the breath decay curve. Concurrent sample collection
using a whole breath spirometer that has been used extensively in previous
work [1-8] was conducted during three exposure experiments to allow a side-
by-side comparison with the new alveolar system. This whole breath
spirometer system was also used for the sixth microenvironment where Tenax
cartridges were used to collect those compounds for which canister sample
collection and analysis has not been validated.
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SECTION 2
CONCLUSIONS
MICROENVIRONMENT AND CONSUMER PRODUCT SCREENING
Air samples were collected in 32 microenvironments and from the head-
space above 6 consumer products to identify potential human exposure sour-
ces for selected VOCs. Microenvironments were defined as discrete loca-
tions where people live, work, or visit with distinct sets of activities or
characteristics that affect VOC emissions and airborne concentrations.
Examples of the microenvironments sampled in this study included homes,
offices, hardware stores, garages, vehicles, and indoor swimming pools.
The microenvironmental screening in this research study was directed to
find specific target chemicals at sufficiently high concentrations so that
human breath concentrations and elimination kinetics after exposure could
be examined. The screening also served a broader purpose of increasing our
knowledge about VOC pollutant sources and the myriad routes to human expo-
sure.
The concentrations for target VOCs measured in the 32 microenvironments
ranged from not detected to 16,000 /*g/m3. Several locations were found in
which several compounds were present at concentrations ranging from 10 to
2000 /*g/m3. One of the hardware stores was a good example of this type of
microenvironment. Other locations had only one or two target compounds
present at elevated concentrations. For example, a chloroform level of 600
/jg/m3 was measured at an indoor swimming pool while the dichloromethane and
toluene concentrations at a furniture stripping shop were 5000 and 5700
/ig/m3 respectively. In some places, for example, a home with moth
crystals, ฃ-dichlorobenzene levels remained elevated over long time
periods. In other locations, such as in a home garage, short term
activities like wood staining and fuel handling increased aliphatic and
aromatic hydrocarbon concentrations over a short time period.
Six microenvironments were found that satisfied the exposure study
requirement for 21 of the 24 targeted compounds. Microenvironments with
sufficiently elevated concentrations of vinyl chloride, carbon
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tetrachloride, or styrene were not found. Exposure experiments were
conducted in a hardware store, furniture stripping shop, indoor swimming
facility, wood/metal shop, garage with wood staining and fuel handling, and
in a home with moth crystals and wood polish. Each experiment represents a
location or activity to which many members of the general population might
be exposed. The general results of the screening provide an interesting
snapshot of potential VOC exposure possibilities, but one which should not
be inferred to all similar microenvironments or activities.
BREATH ANALYSIS AS A MEASURE OF EXPOSURE
The various exposure situations resulted in measureable levels of a
wide range of VOCs in the breath. Among the compounds measured in breath
were straight-chain aliphatic hydrocarbons, branched-chain aliphatic hydro-
carbons, cyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydro-
carbons.
The experiments indicated that alveolar breath samples could preserve
the time resolution lost in whole breath collection and thus define the
very early phases of VOC elimination. Alveolar samples collected with the
new device could be obtained within one minute vs. the several minutes
required for a whole breath sample using the old spirometer system. This
short collection and turn-around time facilitated characterizing the
initial portion of elimination decay curves for 18 VOCs in alveolar breath.
Analogous data for whole breath provided curves for the same compounds as
in alveolar breath with the addition of alpha-pinene, limonene, and 2-
dichlorobenzene, compounds for which Tenax-based sampling was needed. The
alveolar samples often indicated a "second wave" in the decay curves that
might be a decay from a second body compartment; such information was not
immediately evident from data on whole breath samples. The increased VOC
concentrations expected in alveolar samples relative to whole breath
samples were not observed. This phenomenon might be related to the slight
exertion needed to exhale into a spirometer.
The decay data were mathematically analyzed assuming both a one- and a
two-compartment pharmacokinetic model in order to estimate elimination
half-lives. In general, the two compartment model provided a better fit to
the data as indicated by the F test. One compartment half-lives ranged
from 0.08 h for n-nonane to 4.3 h for 1,1,1-tetrachloroethylene. Two
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compartment half-lives ranged from 0.03 for m,j)-xylene to 0.78 h for one
dichloromethane measurement for the first half-life and from 0.61 (n-
octane) to 11.6 h (vinylidene chloride) for the second half-life. Although
the second half-lives were generally less than 8 h, the longest half-life
was noted for ฃ-dichlorobenzene, a compound of relatively low volatility
known to have a long residence time in the body. The application of
generic curve fitting routines to the decay data indicted some promise for
modeling the decays for eventual predictive purposes.
The calculated half-lives for a given chemical were examined for trends
that might be related to exposure level or study participant. Unfortuna-
tely, the data were too limited to make any definitive conclusions to this
effect. There appeared to be no dependence of the half-life on exposure
level, a conclusion that would make predictive breath studies less com-
plicated in that the exposure level would not need to be considered in the
predictive process. The limited data also suggest that the variability of
half-life for a particular compound within a single individual is rela-
tively small; the variability among different individuals appeared to be
small but more study is needed to verify this conclusion.
QUALITY ASSURANCE
Screening Analysis
No quality control or quality assurance samples were scheduled or
collected for this portion of the study. The results were used to select
microenvironments for exposure experiments.
Exposure Experiment Samples
Tenax Samples--
The quality control data for analysis of Tenax samples show that the
analytical sustem was in control during the entire analysis period. The
parameters measured were
daily RRF value for each target analyte,
instrument tune as measured by PFT fragment ions,
system performance characteristics.
The results of the analysis of control samples show consistently high
recovery; the data quality objectives were met for all target compounds.
-------
The results of analysis of blanks show that the Tenax used for sampling was
uniform and has very low background of target compounds. No spirometer
blanks were collected.
The results of the analysis of QA samples was inconclusive. The
agreement with the independent laboratory was not good, but the amount of
data was very small. Intralaboratory precision, measured as average %RSD
between duplicate sample pairs, was very good.
Canister Samples
The performance of the analytical sustem used to analyze all canister
samples was not monitored adequately. Data showing that the system was in
control are not available for all analysis days.
Blank and control samples were prepared and anayzed for whole breath
and alveolar breath, but not for air samples. No spirometer blanks were
collected. For whole breath, recovery was greater than 80% for all
compounds except vinyl chloride, n-pentane, 2-methylpentane, n-nonane, and
p-xylene. For alveolar breath, recovery was greater than 80% for all
compounds except 2-methylpentane and benzene. The results of analysis of
blanks show low background of all target compounds, except for the alveolar
breath blank, experiment FS1.
No duplicate samples were analyzed by an independent laboratory.
Intralaboratory precision was very good for most analytes. The results of
the analysis of performance evaluation samples (2 canisters) show a high
negative bias.
-------
SECTION 3
RECOMMENDATIONS
SAMPLE COLLECTION AND ANALYSIS
During this research study, further experience was gained in using
canisters for collection and direct GC/MS analysis for exhaled human
breath. A modified spirometer designed for sampling alveolar breath was
used for the first time. The following recommendations are suggested to
further improve this methodology:
1. Miniaturize the alveolar spirometer system so that it can be
carried by hand and simplify the design so that it can be widely
employed for environmental and industrial hygiene exposure
measurements.
2. Field test a miniaturized version of the alveolar spirometer and
correct any problems before its use in larger studies.
3. Prepare all breath calibration and control standards with humidity
and carbon dioxide levels that are comparable to those in human
breath. Instrumental responses may be significantly affected by
the presence of these breath constituents.
4. Examine the feasibility of expanding the analyte list for very
volatile compounds such as ethane and acetylene that may be found
in breath. The chromatographic separation and mass spectral
analysis methodology may need modification for these compounds.
5. Examine the feasibility of expanding the analyte list for polar
organic compounds in breath. The method of sample drying and
introduction will need modification for effective analysis of
polar analytes.
MICROENVIRONMENT SCREENING
We recommend that screening of the wide variety of microenvironments
and consumer product emissions for VOCs be continued in future studies.
Further examination of the microenvironments in which people spend much of
their time can fill in gaps in our knowledge about the magnitude and
sources of human exposure to VOCs.
8
-------
FURTHER DATA ANALYSIS
Data collected during this study should be analyzed further to maximize
the information gained from this work. Recommendations are listed below.
1. Additional mathematical modeling should be performed. The use of
a three compartment pharmacokinetic model could be applied to see
if there is practical importance for these volatile compounds.
Additional information might be obtained from this sort of analy-
sis for the less volatile p_-dichlorobenzene and limonene. More
complex functions, such as polynomials and other equations of
higher order should be applied to the data to further define the
shape of the curve. Careful attention should be paid to trends
among compound class.
2. The half-lives calculated in this project should be compared to
those available from previous work. The method by which breath
was collected should be an important consideration in making com-
parisons.
FUTURE EXPERIMENTS
Several experiments can be envisioned that would advance the predictive
ability of breath measurements. Such work should include:
1. Decay curves and half-lives should be measured using multiple
exposures to a variety of exposure concentrations. The
experiments should help define intraindividual variability and any
dependence of the half-life on the exposure level. Experiments
should be performed on individuals chosen to reflect different,
types of people e.g., body builds, weight, etc. in the general
population. Such a study would also define interindividual
variability. The number of compounds targeted should be increased
so that additional decay information is obtained.
2. The importance of various physiological parameters on the measured
decays and half-lives should be determined. Such factors include
body build, physical activity during exposure, and the effect of
breathing technique during sample collection. The effect of such
parameters on the measured half-life and blood:breath partition
ratio will have profound effects on the utility of breath measure-
ments as predictors of exposure. The effect of the time at which
-------
the breath is sampled after the end of the exposure should be
studied because the apparent blood/breath ratio might be expected
to change as different body compartments clear. Again, this is
extremely important for predicting exposure based on breath
measurements.
3. The effect of the exposure time on the half-life and partition
ratio should be determined under constant exposure levels. Changes
in the values as the exposure time changes will reflect the
equilibration of different body compartments to differing extents.
These experiments will help define the optimal time after the
exposure to make the breath measurement. That is, the post
exposure sampling time will define which compartment decay is
being measured.
4. Studies testing the predictive abilities of the developed models
should be performed using participants not involved in the above
experiments. Based on breath measurements for a range of
compounds, the exposure level should be predicted and compared to
the measured air level.
QUALITY ASSURANCE
1. The canister loading/instrument calibration procedures need to be
reviewed and revised.
2. The usefulness of QC checks for the canister analytical system
should be reviewed. Priority should be given to development of QC
checks and control limits.
3. Insufficient quality control and quality assurance samples were
scheduled for the exposure study (canisters). Blanks and controls
should be scheduled for each matrix/sampling devise combination.
Results of analysis of duplicate samples by an independent
laboratory provides important precision estimates than cannot be
obtained by intralaboratory analysis of duplicates. Analysis of
canister samples should be included in the interlaboratory
program.
4. Two ions, at least, should be utilized for the identification of
target analytes by 6C/MS. This is an essential QC check for all
Tenax data, and similar procedures should be developed for
analysis of canister samples.
10
-------
SECTION 4
SAMPLE COLLECTION AND ANALYSIS
INTRODUCTION
Sample collection activities were divided into two phases during this
research project. First, screening samples were collected to evaluate VOC
concentrations and emissions from a large number of microenvironments and
consumer products. Results of the screening sample analyses were used to
select exposure environments for the breath decay experiments. Screening
samples were collected with both canisters and Tenax cartridges, followed
by GC/MS analysis. In the second phase, exposure experiments were
conducted in which both breath and air samples were collected to determine
the exposure level, the breath concentration after exposure, and the decay
in breath concentration over time. Alveolar canister breath samples were
collected in nine of the ten exposure experiments while whole breath
canister samples were collected concurrently in three of those experiments.
Canister air samples were collected before, during, and after participant
exposure in each experiment to determine the exposure concentration and any
possible confounding exposure to the selected compounds outside of the
chosen microenvironment. Tenax cartridges were used to collect whole
breath and air samples during the tenth exposure experiment in which the
target compounds had low volatility or had not been previously validated
for canister collection and analysis. All exposure experiment samples were
analyzed by GC/MS.
COLLECTION OF SCREENING SAMPLES
Screening Sample Collection Procedures
Both canisters and Tenax cartridges were used to monitor target VOC
concentrations (Table 4-1) in numerous microenvironments. These
microenvironments were selected as areas or activities that might provide
VOC exposures to portions of the general population. They included homes,
offices, vehicles, light industry, and commercial establishments. Several
microenvironments were located on the RTI campus or at the homes, vehicles,
and garages to which RTI employees had access. Many other
11
-------
TABLE 4-1. TARGET CHEMICALS FOR SCREENING AND
BREATH EXPOSURE STUDY SAMPLES
Compound Canister Tenax
Vinyl chloride 4
Isopentane 4
Vinylidene chloride 4
n-Pentane 4
Dichloromethane 4
2-Methylpentane 4
Chloroform 4
1,1,1-Trichloroethane 4
Carbon tetrachloride 4
Benzene 4
Trichloroethylene 4
n-Octane 4 4
Toluene 4
n-Nonane 4
Tetrachloroethylene \
Ethyl benzene 4
E-Xylene (or m-) 4 4
Styrene ' 4
o-Xylene 4 4
o-Pinene 4
n-Decane 4 4
Limonene 4
2-Dichlorobenzene 4
n-Dodecane 4
12
-------
microenvironments were commercial or municipal establishments, and special
permission was secured for collecting screening samples in these areas. A
copy of the consent form used to gain entry to these establishments is
presented in Appendix C. Establishment confidentiality was assured in all
cases.
In most microenvironments, an evacuated canister was simply opened and
allowed to fill to ambient pressure in under one minute. A data sheet was
used to record activities, apparent ventilation, establishment volume,
characteristics, and other information that might be useful for evaluating
analytical results. Some activities required sample collection over time
intervals ranging from several minutes to several hours. For long exposure
times, a fixed needle orifice of a selected diameter was attached to the
canister inlet to regulate the flow rate. These samples were slightly
time-weighted since the sampling flow rate decreased after the canister
reached 50% of ambient pressure. All canister samples were stored sealed
at room temperature until analysis.
Fixed-site air samples were also collected at three locations by
pulling air through a 6.0 x 1.4 cm i.d. bed of Tenax GC contained in a
glass tube using a constant flow pump (DuPont Model P125A). Preparation of
these cartridges followed an extremely rigorous procedure, described in
detail in a standard operating procedure [8] to ensure minimal organic
contamination of the sorbent cartridge. Glass fiber filters (Gelman,
25 mm) were attached to the inlet end of the Tenax cartridge to remove
particulates from the sampled air. For fixed-site air sampling, the pump
and cartridge were placed inside a metal box for protection, with only the
inlet end of the sample cartridge protruding. Tenax cartridges were stored
in sealed cans in a solvent-free environment at all times, except during
actual sample collection. Tenax cartridges were used to collect less
volatile compounds such as ฃ-dichlorobenzene and n-dodecane and compounds
that have not been previously validated for canister collection and
analysis, including a-pinene and limonene.
Two target compounds, limonene and a-pinene, were not found in any
microenvironment at concentrations sufficiently elevated for conducting
exposure experiments. These compounds were believed to be common
ingredients of a number of deoderizers and home cleaning products. Several
such products were selected based on their listed ingredients or claims of
13
-------
pine or lemon scent. They were tested for emissions of both o-pinene and
limonene. Emission samples were collected using a dynamic headspace purge
apparatus described in Figure 4-1. The headspace samples were collected
for qualitative analysis only. Sample collection conditions were not
tightly controlled but in general the product temperature ranged from 30*
to 40ฐC and headspace was purged with helium at a flow rate ranging from 20
to 50 mL/min for 10 to 15 minutes. The headspace was swept through a Tenax
cartridge which was analyzed by GC/MS to determine the approximate amount
of a-pinene and limonene.
Screening Sample Collection
Canister screening samples were collected in the 32 different micro-
environmental locations listed in Table 4-2. The microenvironments
included homes, businesses, garages, repair shops, vehicles, etc. These
particular microenvironments were chosen for two reasons. First, most
locations were chosen because it was hypothesized that a particular
compound or group of compounds might be present. For example, chloroform
should be present at high concentrations at the swimming pool while the
refueling experiment was chosen for the.aliphatic and aromatic compounds
that should be present in gasoline. Each microenvironment and the
rationale for its inclusion will be described in Section 6 of this report
along with a discussion of the screening results. Second, a large part of
the general population has potential exposure to these or similar
microenvironments. A few were opportunistic sample collections, for
example a laboratory that had recently been re-roofed in which a strong
asphalt odor was noticed.
Three of the microenvironments sampled using canisters were also
sampled using Tenax cartridges. Tenax was used to collect samples in the
furniture stripping shop, a hardware store, and in a woodworking shop
(Table 4-3) to determine if elevated levels of a-pinene and/or limonene
were present. These three areas were thought to be excellent candidates
for emissions of these compounds since all three dealt in wood products and
wood finishes. Samples of air at these three locations were collected over
a four hour period and analyzed to determine the approximate concentrations
of Tenax target compounds. Six consumer products (Table 4-4) were obtained
at a local grocery store and tested for emissions of o-pinene and limonene
14
-------
Vent
f\\ Tenax cartridge
Teflon head
Glass chamber
Figure 4-1.
Dynamic headspace purge apparatus for measuring consumer
product emissions.
15
-------
TABLE 4-2. MICROENVIRONMENT SCREENING SAMPLE LOCATIONS FOR
CANISTER AIR SAMPLING
Microenvironment
Photocopier room
High volume photocopy/print center
Room painting (oil based paints)
Metal shop
Woodshop
Wood staining area
Home No. 1 with moth crystals
Home No. 2 with moth crystals
Office with one heavy smoker
Indoor swimming pool
Furniture stripping shop
Hardware store No. 1
Hardware store No. 2
Interior decorating store No. 1
Interior decorating store No. 2
Beauty school No. 1
Beauty school No. 2
Laundromat
Bar/nightclub with smoking
Driving and smoking during rush hour
Outdoors at a truckstop
Auto and mower refueling
Inside a new pickup truck cab
Home garage, morning
Home garage, evening after driving in car
Commercial repair garage
Body and repair shop
Paint and body shop
Home with diapers soaking in bleach
Sample Collection
Duration
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
1 h
<1 min
20 min
<1 min
<1 min
<1 min
<1 min
<1 min
<1 min
12 h
Full Scan or MID*
GC/MS Analysis
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
FS
MID
MID
MID
MID
MID
MID
MID
MID
MID
MID
MID
(continued)
16
-------
TABLE 4-2 (cont'd.)
Mlcroenvironnent Sa^Conectlon
Mass spectrometer laboratory facility <1 min MID
Laboratory recently re-roofed <1 min MID
Packaging facility with much styrofoam <1 min MID
= full scan, MID = multiple ion detection.
17
-------
TABLE 4-3. MICROENVIRONMENT SCREENING SAMPLE LOCATIONS
FOR TENAX AIR SAMPLING
Microenvironment Sample Collection Duration
Furniture stripping shop 4 h
Hardware store No. 1 4 h
Wood shop 4 h
TABLE 4-4. CONSUMER PRODUCT EMISSION SAMPLES COLLECTED ON
TENAX USING A DYNAMIC HEADSPACE PURGE
Test Headspace Volume
Product Name Temperature Analyzed
Pine-Solฎ (19% pine oil) 40'C 0.23 L
Airwickฎ Solid Room Deoderizer 30ฐC 0.45 L
(lemon scent)
Wood Plusฎ Polish (lemon scent) 30'C 0.48 L
Johnny Freshฎ Bathroom Bowl 26'C 0.30 L
Cleaner (pine scent)
Old Englishฎ Furniture Polish 26'C 0.23 L
Renuzit Roomateฎ Liquid Air 26'C 0.22 L
Freshner
18
-------
after elevated concentrations of these two compounds were not found in any
microenvironment. Headspace samples collected on Tenax were analyzed to
determine if the compounds were present and, if so, the amount relative to
the other products. Potential interfering compounds were also examined in
the headspace samples.
Quality control samples, including blanks, controls, and duplicate
samples were not employed during screening sample collection and analysis
activities. Analytical instruments were calibrated using single
concentration calibrations for both canister and Tenax screening analyses.
The sample concentrations reported in Section 6 for screening samples
should be used as close approximations. The screening sample data were
used only to select microenvironments and were not used to evaluate actual
exposure concentrations.
COLLECTION OF EXPOSURE EXPERIMENT SAMPLES
Selection of Exposure Microenvironments
Exposure experiments were conducted to measure participant breath
levels of VOCs after spending time in selected microenvironments. A second
goal was the measurement of breath clearance rates of different VOCs from
the body after the participant left the exposure microenvironment. Several
microenvironments were chosen for conducting the exposure experiments based
on the identities, number, and concentrations of target VOCs detected
during screening experiments. Each chemical had to have sufficiently high
exposure levels so that the participant's breath concentration was still
measureable several hours after leaving the exposure site.
Six microenvironments were selected as sites for exposure experiments
to measure breath concentrations and clearance rates. These sites were the
furniture stripping shop, hardware store no. 1, wood and metal shop,
swimming pool, garage with fuel handling and wood staining, and a home with
moth crystals and furniture polish. The chemicals targeted for each
microenvironment are listed in Table 4-5. The targeted chemicals were
found at each microenvironment, except for the less volatile aliphatic
hydrocarbons in the wood and metal shop. An absence of freshly stained
wood was the most likely reason the concentrations of aliphatic compounds
in the wood and metal shop air were lower than those measured during
screening. All of the microenvironments except the swimming pool had
19
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TABLE 4-5. MICROENVIRONMENTS AND CHEMICALS SELECTED FOR
BREATH EXPOSURE EXPERIMENTS
Microenvironment
Intended Target Chemicals
Furniture stripping
shop
Hardware store no. 1
Indoor swimming pool
Wood and metal shop
Home garage with fuel
handling and wood
staining
Home with consumer
products (moth crystals
and wood polish)
Dichloromethane, toluene, 1,1,1-
trichloroethane, other aromatic
and aliphatic hydrocarbons
Dichloromethane, 1,1,1-trichloro-
ethane, tetrachloroethylene,
aliphatic and aromatic
hydrocarbons
Chloroform
Less volatile aliphatic hydrocarbons,
1,1,1-trichloroethane, vinylidene
chloride
Very volatile and less volatile
aliphatic hydrocarbons, aromatic
hydrocarbons including benzene
Limonene, a-pinene, p_-dichlorobenzene
20
-------
multiple target compounds at elevated concentrations. Decay curves were
obtained for all target compounds except vinyl chloride, carbon tetra-
chloride, and styrene. Sufficient resources remained after the first six
microenvironment experiments to perform repeat experiments at one location.
The hardware store was chosen as the location for repeat experiments. A
total of four different participants were exposed in the hardware store at
three different times. On two of those occasions, two participants were
exposed at the same time and breath samples were collected simultaneously.
These repeat experiments were conducted to examine interpersonal variations
in breath decay curves. Examination of intrapersonal variability was made
possible because a participant may have been exposed to the same chemical
in more than one exposure experiment.
Description of Exposure Experiments
Each breath exposure experiment was conducted to determine a partici-
pant's breath concentration of one or more target chemicals after spending
time in an area with a measured air concentration of the same chemical(s).
An air sample was collected in each microenvironment so that the exposure
concentration was known. The participant spent several hours in the
microenvironment while the air sample was collected. Then the participant
left the exposure area and immediately began providing breath samples.
Breath samples were collected at multiple time points after the termination
of exposure to develop a decay curve of breath VOC concentrations with
enough time resolution to calculate a best fit linear function and
clearance half-lives. Samples of air that the participant breathed during
the 12 hours prior to entering the exposure environment and while providing
breath samples after exposure were collected and analyzed to evaluate any
confounding exposure to target VOCs outside of the selected microenviron-
ment.
Most of the experiments were conducted using the same sample collection
conditions, but there were some differences. An outline of the intended
exposure and sample collection pattern is presented in Table 4-6 for five
of the six exposure environments. Alveolar breath samples were collected
in these five experiments. The fast collection rate using the alveolar
method allowed more samples to be collected shortly after exposure ended.
This allowed more accurate decay curves to be developed, particularly
21
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TABLE 4-6. EXPOSURE EXPERIMENT SAMPLE COLLECTION OUTLINES
Activity
Collection Time
Collect air sample prior to
entering exposure environment
Provide breath sample prior to
entering exposure environment
Enter exposure environment,
collect air sample
Leave exposure environment,
provide breath samples:
Alveolar breath
Whole breathb
Collect air sample at breath
collection site
12 h, prior to exposure
15 min prior to exposure
2-4 h, during exposure
3, 8, 18, 28, 38, 53, 68,
98, 128, 173, 218 min
after exposure
10, 30, 48, 70, 104, 134,
178, 223 min after
exposure
0 to 240 min after exposure
concurrent with breath
collection
aFor all exposure experiments except consumer product experiment.
bwhole breath collected during three experiments; furniture stripping
shop, hardware store No. 1, home garage.
22
-------
during the initial phase of clearance from the body. Whole breath samples
were collected along with alveolar breath samples during three experiments
(furniture stripping, hardware store No. 1, home garage) to allow
comparisons using this previously employed method [1-7,9]. The consumer
product exposure experiment was conducted somewhat differently than the
other experiments. Tenax cartridges were used to collect both breath and
air samples to measure limonene, a-pinene, and j>-dichlorobenzene concentra-
tions. Since it was thought that the ฃ-dichlorobenzene decay rate was much
slower than those of the more volatile target chemicals breath, samples
were collected over a much longer time period. An outline for the consumer
product sample collection scheme is presented in Table 4-7. For all
exposure experiments, one breath sample was collected immediately before
the participant entered the exposure environment. This sample was intended
to measure baseline breath concentrations for comparison to the measured
concentrations after exposure.
Specific sample collection conditions for each of the 10 participant
exposure experiments are described in Table 4-8. Two people alternated as
the exposure participants for the first six exposures. These two
participants were exposed to the hardware store atmosphere on the same day
at the same time during another experiment (HS2, HS3). Two different
people served as the participants in another experiment in which they were
exposed to hardware store atmosphere at the same time (HS4, HS5). A
description of the participants and their approximate breathing rates using
the alveolar spirometer is presented in Table 4-9. A small meal was eaten
by each of the participants approximately 30 to 50 minutes before the end
of the exposure period. One exception to eating during the exposure phase
was the swimming pool study in which the exposure period was cut short
because the pool managers were going to open the pool area to the outside
air. This action would have drastically altered the exposure concentration
so the exposure was terminated after 2.3 h instead of 4 h. The exposure
time in the garage experiment was limited to 2.2 h because this time was
considered realistic for the acti- vity and the temperature was very high
(37ฐC) in the garage. Conditions and activities at each exposure
experiment microenvironment will be described in more detail in Section 6.
23
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TABLE 4-7. CONSUMER PRODUCT EXPOSURE EXPERIMENT SAMPLE
COLLECTION OUTLINE
Activity
Collection Time
Collect air sample prior to
entering exposure enviroment
Provide breath sample prior to
entering exposure environment
Enter exposure environment,
collect air sample
Leave exposure experiment,
provide whole breath samples
Collect air samples during
breath collection time period.
Samples collected at:
12 h, prior to exposure
15 rain prior to exposure
4 h, during exposure
3, 21, 38, 57, 75, 100,
130, 175, 219, 433 min
after exposure and 18,
31, 50, 68 h after
exposure
0 to 6 h after exposure
6 to 25 h after exposure
25 to 50 h after exposure
50 to 68 h after exposure
24
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TABLE 4-8. EXPERIMENTAL CONDITIONS AND SAMPLES COLLLECTED
DURING EXPOSURE EXPERIMENTS
Experiment:
Experiment Code:
Participant:
Hours exposed:
Experiment date:
Furniture
Stripper Shop
FS1
1
3.4 h
3/29/89
Hardware
Store
HS1
2
3.7 h
4/7/89
Swimming
Pool
SP1
2
2.3 h
4/21/89
Sample Collection
Alveolar Breath
Sample Type
Number collected
Number duplicates
Number blanks
Number controls
Whole Breath
Sample type
Number collected
Number duplicates
Number blanks
Number controls
Air
Sample type
Number collected
Number duplicates
Number blanks
Number controls
2-L Canister
12
0
1
1
6-L Canister
9
1
1
1
6-L Canister
3
0
0
0
2-L Canister
12
1
1
1
6-L Canister
9
1
1
1
6-L Canister
3
0
0
0
2-L Canister
12
1
1
1
Not
Collected
6-L Canister
3
0
0
0
(continued)
25
-------
TABLE 4-8 (cont'd.)
Experiment:
Experiment Code:
Participant:
Hours exposed:
Experiment date:
Wood and Metal
Shop
WS1
1
4.0 h
5/9/89
Consumer
Products
CP1
2
5.2 h
5/12/89
Garage, Fuel
Wood Stain
GS1
1
2.2 h
5/25/89
Sample Collection
Alveolar Breath
Sample type 6-L Canister Not 6-L Canister
Number collected 12 Collected 12
Number duplicates 0 0
Number blanks 1 1
Number controls 1 1
Whole Breath
Sample type
Number collected
Number duplicates
Number blanks
Number controls
Air
Sample type
Number collected
Number duplicates
Number blanks
Number controls
Not
Analyzed
6-L Canister
3
1
0
0
Tenax
15
14
4
4
Tenax
6
3
3
3
6-L Canister
8
1
1
1
6-L Canister
3
0
0
0
(continued)
26
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TABLE 4-8 (cont'd.)
Experiment:
Experiment code:
Participant:
Hours exposed:
Experiment date:
Hardware
Store
HS2
2
3.7 h
6/7/89
Hardware
Store
HS3
1
3.7 h
6/7/89
Hardware
Store
HS4
3
3.9 h
6/21/89
Hardware
Store
HS5
4
3.9 h
6/21/89
Sample Collection
Alveolar Breath
Sample Type
Number collected
Number duplicates
Number blanks
Number controls
Whole Breath
Sample type
Number collected
Number duplicates
Number blanks
Number controls
Air
Sample type
Number collected
Number duplicates
Number blanks
Number controls
6-L Canister
12
2
1
1
Not
Collected
6-L Canister
12
2
1
1
Not
Collected
6-L Canister
12
2
1
1
Not
Collected
6-L Canister
12
2
1
1
Not
Collected
6-L Canister
1
0
0
0
6-L Canister
3
1
0
0
6-L Canister
3
0
0
0
6-L Canister
2
0
0
0
27
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TABLE 4-9. PARTICIPANT CHARACTERISTICS AND APPROXIMATE
ALVEOLAR SPIROMETER BREATHING RATES
Participant
Number Sex
1 Male
2 Male
3 Male
4 Female
Age
35
31
32
25
Height
178 cm
168 cm
185 cm
180 cm
Alveolar Spire-meter
Breathing Rate
Weight (breaths/min)
82 kg
57 kg
79 kg
61 kg
4.8
5.2
5.6
8.0
28
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Exposure Experiment Sample Collection
Several sample types were collected during the exposure experiments
including canister alveolar breath, canister whole breath, Tenax whole
breath, canister air, and Tenax air samples. The Summaฎ polished stainless
steel canisters were cleaned prior to sample collection by evacuation to 50
mtorr while being heated to 140*C for at least four hours in an oven
(Figure 4-2). Canisters were stored under vacuum and the pressure dif-
ferential was used to pull air and breath samples into the canister. Tenax
GC was purified by extensive Soxhlet extraction in methanol and pentane
followed by thermal desorption at 255*C under a purge of cryogenically
cleaned helium. Tenax cartridges were stored in glass culture tubes inside
a can in a solvent-free room before sample collection and in the tubes and
can inside a freezer at -20*C after sample collection.
Two spirometer systems were used to collect breath samples during this
study. The older spirometer, which has been used in many previous studies,
collects the entire portion of exhaled breath expired over a period of 3 to
6 minutes, until a 40 L Tedlar bag is filled. Then the whole mixed breath
contained in the bag is pulled into canisters or across a Tenax sorbent bed
to trap the analytes. In contrast, the modified spirometer is designed to
collect primarily alveolar breath into canisters while the participant is
breathing into the device. Collection of whole breath samples requires 15
to 20 minutes while the new device allows sample collection times as short
as two minutes.
Alveolar breath samples were collected using a modified spirometer
system developed during the initial stages of this research project (Figure
4-3). Descriptions of the work performed to develop the alveolar
spirometers are presented in Appendices A and B. Appendix A describes the
initial feasibility study and Appendix B describes how, based on the
results of the current work, the alveolar spirometer was made portable and
characterized further. Briefly, the Tedlar bag used to store clean inhale
air was rinsed with helium several times before each exposure experiment
and was stored full of helium until collection of the first breath sample.
The Teflon and stainless steel mouthpieces were steam sterilized prior to
use. Immediately prior to collection of the first breath sample, the
helium was expelled from the bag and the mouthpiece was installed on the
van-mounted spirometer. The participant inhaled humidified ultrapure air
29
-------
Caniiter Cleaning Oven
Butterfly Valve
Thermocouple Gauge
LO
O
Figure 4-2. Canister cleaning system diagram.
-------
Air Lint from Tank
Plug Valve
Mouthpiece Union and One-Way Valves
Flew
Controlling
OrMitt
Swnplt
Collection Curator
Figure 4-3. Schematic diagram of the prototype alveolar
spirometer system.
31
-------
from the bag through one unidirectional valve and exhaled through a second
specially designed unidirectional Teflon ball valve (Figure 4-4). The
breath flowed past a port connecting a canister to the exhale valve exhaust
and into a 1.27 cm i.d. x 7.6 m long Teflon FEP tube. At the end of the
fourth exhale the canister valve was opened and exhaled breath flowed
through a fixed needle orifice at a controlled flow rate into the canister.
After the canister was approximately 80% filled (610 torr) the valve was
closed and the subject ceased breathing into the spirometer. A fresh
canister was then placed on the exhale valve port before collection the
next sample.
Previous work (Appendix A) has demonstrated that, based on carbon
dioxide concentrations, samples collected using the modified spirometer
consist of over 97% alveolar breath. As the participant exhales,
nonalveolar breath from his airways pass by the sampling port very quickly.
Only a small portion of this nonalveolar breath is sampled. As the
participant continues to exhale, breath from his alveoli pass the sampling
port. The exhaled breath is contained in the long Teflon tube, with the
nonalveolar breath farthest from the sampling port and end-expired
(alveolar) breath closest to the sampling port. As the participant inhales
the breath is pulled back down the tube towards the sampling port and into
the canister. Sample collection flow rates and tube dimensions have been
selected so that only alveolar breath is pulled into the canister from the
tube during the inhale portion of the breath cycle.
The procedure for collection of VOCs in whole exhaled breath is
described in the analytical protocol [9] and will be briefly summarized
here. A Teflon and polyethylene mouthpiece with Tedlar flap valves and
stainless steel ball valves was used (Figure 4-5). A gas impimger filled
with distilled deionized water was placed in-line with the air tank to
humidify the air for subject comfort. Each Tenax cartridge was connected
to a separate Nutech 221 gas sampling pump so that the amount of air drawn
through each cartridge could be accurately measured with the dry gas meter
in the Model 221 pump. The inlet to the Tenax cartridge was connected to
the Tedlar exhale bag using a 6 mm o.d. Teflon tube. Canister samplers
were connected to flow controlling orifices placed in the Teflon tube
between the exhale bag and Tenax cartridges. Breath samples were collected
in evacuated canisters by opening the canister valves for a specified time
32
-------
Breath
Flow
u>
Side view; sample port coming 1n
from opposite side.
Breath"
-^ 4" l.d. Teflon Tube
Flow
i" o.d. Stainless Steel Sampling Port
Top View
Figure 4-4. Exhale valve and sample port.
-------
Ultrapure Air
(u)
-B-
Tenax
Cartridges
Flow-
Control
Orifices
Tedlar
Exhale
Bag
Stainless
Steel
Canisters
Stand
Charcoal
Filter
Humidifier
One-Way Valves
Mouthbit
Tedlar
Inhale
Bag
1
Figure 4-5. Schematic diagram of the whole breath spirometer system.
-------
period; the volume of exhaled breath collected in the canisters did not
have to be accurately determined.
Immediately prior to the subject being seated at the spirometer, the
inhale bag was installed and filled with approximately 40 L of purified,
humidified air. A new piece of cleaned polyethylene tubing was used to
connect the mouthpiece union to the elbow unions. The subject was seated
on a stool and the mouthpiece height adjusted to a comfortable level. The
subject was asked to wear nose clips and to inhale/exhale through the
mouthpiece only. The Teflon plug was replaced with a sterilized Teflon
mouthbit, the ball valves were opened and the participant began to breathe
into the apparatus. When the sample bag was full, the subject was asked to
stop breathing and the ball valves were closed. The Tenax cartridges were
placed in line with the pumps and one or two canisters were connected to
flow controlling orifices. The plug valve to the pump was opened and the
sample is withdrawn from the bag through the cartridges. Approximately two
minutes after beginning the sample flow through the Tenax cartridges the
canister valves were opened. Exhaled whole breath was collected passively
in the evacuated canisters due to the differential in pressure. The
canisters were closed after 4.5 L of exhaled breath was collected in each;
the amount of time open depended upon the size of the flow controlling
orifice. Collection on the Tenax cartridges continued until the exhale bag
was empty; approximately 15 to 16 L of exhaled breath was sampled on each
of two Tenax cartridges.
After Tenax samples were collected, the cartridges were placed in
culture tubes containing ca. 5 g of CaS04 and stored in sealed paint cans
for 24 hours to dry the samples. The CaS04 was removed after 24 hours and
the Tenax cartridges were placed in a freezer as soon as possible. The
mouthbit was removed and replaced with the solid Teflon plug. The used
collection bag (exhale bag) and polyethylene tubing were removed from the
spirometer and replaced with clean materials before collection of the next
sample.
Air samples were collected in canisters over 4-h periods in the
exposure environment and in the van while breath samples were collected.
Samples were collected over 12-h periods from the participant's air space
during the period immediately prior to entering the exposure environment.
Sample collection was initiated by attaching a flow controlling orifice to
35
-------
the canister and then opening the canister valve. A 4-h orifice was
constructed for 6-L canisters by inserting three pieces of fused silica
capillary tubing, each 60 /ปm i.d. x 25 mm long, through septum material in
stainless steel tubing. The 12-h orifice used one piece of the fused
silica capillary tubing. Each orifice was tested to ensure that a 4.5 L
sample would be collected in each canister over the desired time period.
Air samples collected in canisters using fixed orifices were slightly time
weighted. The flow rate remained nearly constant until the canister was
half-full (3 L) and then declined 15% to 20% as it approached three-
quarters full (4.5 L). The air sampling canisters could not be worn due to
their large size. The participant carried the canisters by hand whenever
he/she moved.
The procedure for collecting VOCs in air using Tenax cartridges was
described previously in this section for screening samples; this method was
also applicable to collection of air samples during the exposure experi-
ments. Personal air samples were collected by attaching the pump to the
belt and the head of the cartridge to the collar in the breathing zone.
Blood samples were not collected and analyzed during these exposure
experiments. The methodology developed for measuring low concentrations of
VOCs in blood [10] was not suitable for conducting accurate decay
measurements without modifications [7]. In an earlier phase of this
research, attempts were made to improve the sensitivity of the blood method
using alternative mass spectrometry procedures [11]. The goal of that
research was to decrease the blood sample volume needed to measure
exposures. A smaller sample size was mandatory because many samples needed
to be collected over a short time period to accurately describe the
elimination kinetics. The desired improvement in sensitivity was not
achieved so blood samples were not collected.
SAMPLE ANALYSIS
Canister Analysis
The canister samples from air and breath were analyzed similarly.
Because of differences in the mass spectrometer response due to different
carbon dioxide and/or humidity levels, there were 3 separate calibrations
for quantitative analysis. Alveolar breath calibration standards were
prepared at 100% relative humidity and 4.8% C02. whole breath standards
36
-------
were prepared at 100% relative humidity and 3.8% C02, while air standards
were prepared at about 25% relative humidity with no C02. In addition, the
nominal sample volumes were 60, 80 and 200 ml for alveolar breath, whole
breath and air samples, respectively, due to cryogenic trap freezing
considerations. Each calibration consisted of a zero concentration level
and 3 nonzero levels (ranging from 1.5 to 140 /tg/m3 for air and from 11 to
400 /ig/m3 for breath) appropriate for the concentrations expected. A
point-to-point calibration was used in each case.
All samples and standards were analyzed by drying the air or breath
through a Perma-Pureฎ dryer, then trapping a known volume in a cryo-cooled
(-150*0) trap (Figure 4-6). An additional volume of d6-benzene, perfluoro-
toluene and perfluorobenzene was also trapped separately to act as external
standards. The trap was ballistically heated to transfer the trapped vapor
onto a DB-624 fused silica capillary column which was temperature
programmed. The analytical parameters are contained in Table 4-10.
Screening samples were analyzed by electron impact ionization MS in
full scan or multiple ion detection (MID) mode. In some cases, a lower
sample volume was trapped when VOC levels were expected to be elevated
beyond the linear range of the instrument.
The amounts of target VOCs were calculated using the response ratio of
ds-benzene to each of the analytes. The calculations for all compounds
except dichloromethane were carried out using a multi-level point-to-point
calibration. Each level of concentration was based on a single analysis of
a standard. Each standard injection consisted of the target compounds at
one of the three concentration levels plus the external standards. The
analytes were introduced at low levels (0.4 - 2 ng), medium levels (2 -
11 ng) or high levels (12 - 44 ng) into the instrument while the level of
de-benzene was held constant (1.86 ng). The relative response factor (RRF)
was calculated for each calibration level from
RRF
where AT = the integrated peak area of the target analyte,
Astd = the integrated peak area of the external standard,
d6-benzene,
= the micrograms of a target analyte analyzed from a
standard mixture of known composition
37
-------
Pressure/Vacuum
Gauge
Drying Tube
o
Vent
Glass
Injection Port
Flow
Controller
Vacuum
Pump
Ballast
Tank
Pressure/Vacuum
Gauge
Ha
Data System
G/C
MIS
Figure 4-6. Schematic diagram of the canister analysis system,
-------
TABLE 4-10. ANALYTICAL CONDITIONS FOR CANISTER SAMPLE ANALYSIS
Instrument
Component
Parameter
Setpoint or Condition
Canister interface
Gas Chromatograph
Mass Spectrometer
Temperature:
valve, 6-port
transfer lines
trap
Sample Flow
Trapping Time:
alveolar breath
whole breath
air
external standard
Dryer
drying flow
Model
Temperature:
injector
column
transfer line
Column:
dimensions
phase
Carrier gas:
flow
head pressure
Model
Type
Operation modes
lonization
lonization potential
Trap current
Multiplier:
preamplifier
setpoint
Temperature:
inlet
source
Full scan mode:
accelerating voltage
magnetic sweep range
scan speed
200'C
200*C
-150ฐC + 200*C
20 seem, nominal
3.0 min, nominal
4.0 min, nominal
10.0 min, nominal
2.5 min
Perma Pure, 1.1 m x 1/8" o.d.
80 mL/min nitrogen
Varian 3700
200* C
-20*C (0 min) @ 5'C/min +
200ฐC
200'C
30 m x 0.32 mm i.d.
DB-624
Helium
~2.7 mL/min
10 psig (70 KPa)
1KB 2091
magnetic sector, single
focusing low resolution
multiple ion detection (MID),
full scan
electron ionization
70 eV
50 /(A
1
500
160'C
180ฐ C
3.5 kV
1 + 256 m/z
1.5 sec/scan cycle
(continued)
39
-------
TABLE 4-10 (cont'd.)
Instrument
Component
Parameter
Setpoint or Condition
Mass spectrometer
(continued)
Data Acquisition
MID mode:
magnetic setpoint
ions: min. and max.
scan speed, cycle
Reference standard
Vacuum
Computer
MS interface and software
Sampling rate
MID mode:
sweep across ion
sample time
samples averaged per ion
A/D resolution
57 m/z @ 3.5 kV
57, 104 m/z
1 scan/sec
tri s-(heptaf1uoropropyl)-s-
triazine
2 x 10-5 torr
Tandy 3000 microcomputer
Teknivent Vector/1 system
10000 samples/sec
+0.2 m/z by 0.033 m/z
1 mS " "
4 summed x 2 averagings
16 bit
40
-------
/*9std = the micrograms of the external standard added to the
analyzed standard aliquot.
By calculating the RRF for each calibration level, a point-to-point
calibration could be constructed (RRF v^. the area ratio of the analyte to
d6-benzene). When a target compound was analyzed the area ratio
(areaUnk/areaES) was used to determine the RRF from the curve. For levels
below the low concentration level, the RRF of the low concentration
standard is used. Once the RRF is determined, the amount (fig) can be
calculated from
AT x
~ Astd x RRFj/std
For dichloromethane, there often was splitting of the peak into two so
the calculation was manually carried out on the sum of the areas using only
a single RRF. This RRF was the average RRF of the three standards
analyzed. The amount was calculated from the above equation.
Concentrations of several compounds that were not on the target list
were estimated by using the response of similar target compounds. The
compounds used are shown in Table 4-11. An average relative response
factor (RRF) of the target compound across all concentrations was assumed
to estimate the RRF of the nontarget compounds.
The garage experiment exposure air sample had analyte concentrations
that resulted in signals that were far above the data system's range. This
sample and one high level calibration standard were analyzed by full scan
mass spectrometry at a reduced multiplier voltage. Analyte concentrations
were estimated using a RRF based on the single calibration standard
analysis.
A limit of detection (LOD) was determined for canister breath samples
(Table 4-12). The LOD was calculated after the analysis of seven canisters
fortified at very low concentrations of VOCs using 100% relative humidity
and 4.8% C02- The LOD values were calculated using the equation:
LOD = Sr (to. 99)
where:
Sr = standard deviation of the response for replicate
samples, in ng,
to. 99 = Student's t value appropriate for a one-tailed test
at the 99% confidence level and a standard deviation
estimate with n-1 degrees of freedom
41
-------
TABLE 4-11. ADDITIONAL COMPOUNDS AND THEIR QUANTITATION BASIS
Nontarget Compound Target Compound with RRF Used
2-Methylhexane n-Octane
3-Methylhexane n-Octane
3-Methyloctane n-Octane
n-Undecane n-Decane
n-Dodecane n-Decane
Ethylcyclohexane 2-Methylpentane
1,2,4-Trimethyl benzene ฃ-Xylene
Trimethyl benzene isomer ฃ-Xylene
n-Butyl acetate 1.2 x n-Octanea
2-Methylpropyl acetate 1.2 x n-0ctanea
^Previous work on this instrument indicated a relative response factor
1.2 times that of octane for n-butyl acetate.
42
-------
TABLE 4-12. LIMITS OF DETECTION AND QUANTIFIABLE LIMITS FOR
CANISTER AND TENAX SAMPLE ANALYSIS
Canister
Target Compound
Vinyl chloride
Isopentane
Vinyl idene chloride
n-Pentane
Dichloromethane
2-Methylpentane
Chloroform
1,1,1-Trichloroethane
Carbon tetrachloride
Benzene
Tr i ch 1 oroethy 1 ene
n-Octane
Toluene
n-Nonane
Tetrachl oroethy 1 ene
Ethyl benzene
m,j)-Xylene
Styrene
o-Xylene
o-Pinene
n-Decane
Limonene
2-Dichlorobenzene
n-Dodecane
LOO*
0.07
0.06
0.03
0.07
0.09
0.08
0.03
0.17
0.02
0.06
0.04
0.02
0.02
0.02
0.09
0.01
0.01
0.01
0.02
NT
0.02
NT
NT
NT
QLb
All values
0.27
0.25
0.13
0.30
0.34
0.32
0.10
0.66
0.10
0.24
0.17
0.07
0.08
0.07
0.36
0.05
0.04
0.05
0.09
NT
0.10
NT
NT
NT
Tenax
LOD
in ng
NTC
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
6
NT
6
NT
NT
7
7
7
6
9
7
18
9
QL
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
NT
24
NT
24
NT
NT
28
28
28
24
36
29
72
36
aLOD = limit of detection.
bQL = quantifiable limit.
CNot a target compound.
43
-------
A quantifiable limit (QL) was calculated as four times the LOD. The QL was
used as the conservative cut-off point for concentration data to be
included in curve fitting and half-life analyses of breath decay curves.
Canister Data Processing
The data from the GC/MS was put into an ASCII file format on a computer
diskette. This included the compounds found and the amount detected.
Irregularities in the data (e.g. incorrect peak assignment, etc.) were
corrected by hand using a text editor. All corrected values were entered
by hand into the ASCII report file.
Once the ASCII report file was corrected, the data was then imported
into a Lotus Symphony spreadsheet. The spreadsheet was designed to
automatically import data from each ASCII report file with minimal operator
effort. Once all files for an experiment are imported, calculations are
performed to verify that the measured VOC amount was equal or greater than
the quantifiable limit. All concentration data were reported in concentra-
tion units of /
-------
TABLE 4-13. GC/MS TENAX ANALYSIS PARAMETERS
Parameter
Setting
Inlet-manifold
Desorption chamber and valve
Capillary trap - minimum
- maximum
Thermal desorption time
He purge flow
GC
MS
Column
Temperature
Carrier (He) flow
Separator Oven
Scan range
Scan cycle, automatic
Emission current
Electron multiplier
Hold time
270ฐC
-195'C
240'C
8 min
15 mL/min
60 m DB1 wide bore fused silica
40' (hold 5 min) - 240ฐC, 4'C/min
1.0 mL/min
240*C
Finnigan 4000
m/z 35 -ป 350
0.95 sec/cycle
0.5 mA
1000 voltsa
0.05 sec
^Typical value.
45
-------
Astd x RRFj/std
where: AT = integrated peak area of a target analyte
Astd = integrated peak area of a quantitation standard
/tgstd = micrograms of quantitation standard added to the
Tenax cartridge
RRFT/std = relative response factor of target analyte response
to quantitation standard response
Since the volume of air collected for a sample was accurately known and
the quantity of analyte per cartridge was determined, the breath
concentration was calculated from:
x 1000 L/m3
Volume sampled (L)
Calibration and daily response factor cartridges were prepared using flash
evaporation techniques for all target compounds. The LODs and QLs for the
target analytes were calculated as described above and are displayed in
Table 4-12. Concentration values were not corrected for background amounts
of the analytes or recovery of analytes from the Tenax cartridges.
Background and recovery values are reported in Section 5.
46
-------
SECTION 5
QUALITY ASSURANCE
ANALYTICAL PROTOCOLS
A Work Plan [12] and four Analytical Protocols [9] were prepared for
this study. These protocols covered all study activities except alveolar
breath sampling and analysis and are listed in Table 5-1. In addition, a
Quality Assurance Project Plan (QAPP) [13] was prepared for this study to
outline quality assurance (QA) and quality control (QC) objectives and
procedures. Adherence to analytical protocols
was not monitored during this study.
FIELD OPERATIONS/SAMPLE COLLECTION
Collection of screening samples was performed between January and June,
1989. Exposure experiment samples were collected between March and June,
1989.
Air and breath samples for screening and exposure experiments were
collected in the Research Triangle Park area by two RTI chemists, each
having over 10 years of Total Exposure Assessment Methodology (TEAM) field
sampling experience. In addition, the Task Leader was present in the field
during all exposure experiment sampling.
Samples were identified by sample codes generated for this study in the
form:
140-EEE-MSTx
where the first three numbers identify the study. The next 3 letters (EEE)
identify the experiment. The codes are:
SCR Screening
FS1 Furniture stripping experiment
HS1
HS2 Hardware Store
HS3 Experiments 1-5
HS4
HS5
WS1 Wood/Metal Shop Experiment
SP1 Swimming Pool Experiment
GS1 Garage/Stain Experiment
CP1 Consumer Product Experiment
47
-------
TABLE 5-1. ANALYTICAL PROTOCOLS PREPARED FOR EXPOSURE ASSESSMENT STUDY
RTI/ACS - Protocol No. Analytical Protocol Title
AP-202-004 Fixed-Site and Personal Monitoring of Vapor-
Phase Organic Compounds in Ambient Air -
Tenax
AP-203-008 Determination of Volatile Organic Compounds
in Whole Blood
AP-203-007 Sampling and Analysis Procedure for Organics
in Human Breath Samples
AP-203-003 Indoor and Outdoor Monitoring of Vapor-Phase
Organics in Ambient Air - Canisters
48
-------
The next three letters (MST) identify the sample type. Matrix type (M)
codes are:
A Alveolar Breath
W Whole Breath
E Air-Exposure Experiment
0 Overnight Air (before Exposure Experiment)
B Air collected during breath collection
Sampling Device (S) codes are:
C Canister
T Tenax
Sample Type (T) codes are
F Field Sample
D Duplicate Sample
Q Duplicate sample collected for analysis by the
independent laboratory
FB Field Blank
FC Field Control
The last identifier is the sample sequence (x) number, usually 0-11.
A sample collection schedule was prepared at the start of the exposure
experiment study. The schedule identified the times at which duplicate
samples were to be collected and when field blanks and controls were to be
utilized.
The study participants were RTI chemists. The exposure experiments
were selected from potential activities and chemicals based on the results
of the analysis of screening samples.
Projections for this study included collection of screening samples,
and collection of air and breath samples immediately prior to, during, and
after exposure to selected microenvironments. The exposure study sample
projections were based on results of screening experiments and differ
slightly from the numbers projected in the Work Plan (12). The completion
rates for sample collection and analysis are shown in Table 5-2. A sample
receipt report showing losses is shown in Table 5-3.
SAMPLE ANALYSIS
Screening Analysis
Screening samples collected on Tenax and in canisters were analyzed by
capillary column gas chromatography/mass spectrometry/computer (GC/MS/-
COMP) techniques. Full scan (FS) and multiple ion detection (MID) modes
49
-------
TABLE 5-2. COMPLETENESS OF SAMPLE COLLECTION AND ANALYSIS
Scheduled/Collected/Analyzed
Screening
Samples
Sample Type
Field Samples
Duplicate Samples
QA Samplesc
Field Blanks
Field Controls
Totals
Air
Canister
32/32/32
0/0/0
0/0/0
0/0/0
0/0/0
32/32/32
Exposure Experiment
Samples3
Breath
Tenax
9/9/9
0/0/0
0/0/0
0/0/0
0/0/0
9/9/9
Canister
144/144/134&
14/14/13&
0/0/0
12/12/12
12/12/12
182/182/171
Tenax
15/15/15
10/10/10
4/4/4
4/4/4d
7/7/4d
37/37/37
Air
Canister
24/24/22b
3/3/3
7/7/0
2/0/0
2/0/0
37/34/25
Tenax
6/6/6
1/1/1
3/3/2
3/2/2
3/2/2
16/16/14
^Numbers scheduled were based on results of analysis of screening samples.
^Explanation of sample losses given in Table 5-3.
CQA samples include performance evaluation samples and samples analyzed by an
independent laboratory.
done blank and one control analyzed by independent laboratory.
50
-------
TABLE 5-3. SAMPLE RECEIPT REPORT
Sample Losses
1. Experiment SP1
Sample 140-SP1-ACF11 had a leaky value, sample collected but not
analyzed.
2. Experiments HS2 and HS3
Sample 140-HS2-BCF1; canister was not opened; - not collected
3. Experiment WS1
Whole breath samples not analyzed because only a few of the target
compounds were found at levels sufficient for decay curves.
Only alveolar samples analyzed for this experiment. Whole
breath samples shifted to GS1 experiment.
4. Canister air sample blanks and controls
There were not enough canisters to allow sample collection, breath
blanks and controls and air blanks and controls.
5. Canister QA analysis
- No independent laboratory was found for analysis of breath samples.
- No independent laboratory was found that could analyze all target
compounds at a reasonable price.
- EPA supplied 3 canister air performance evaluation samples - these
are the only canister QA samples.
51
-------
were used to determine, in a semi quantitative manner, the target compounds
present. The results were used to select microenvironments for exposure
experiments.
Exposure Experiment Samples
Tenax Samples--
Air and breath samples collected on Tenax were analyzed on a Finnigan
4021 quadrupole mass spectrometer on 8 analysis days between June 2 and
June 14, 1989.
Prior to sample analysis, relative response factors (RRF) for each
target compound were established by analyzing calibration cartridges
prepared at 4 levels. Each cartridge also contained the quantitation
standards perfluorobenzene (PFB) and perfluorotoluene (PFT). The levels of
target compounds loaded onto Tenax cartridges for calibration are shown in
Table 5-4. Based on the data from these analyses, average RRF values were
calculated and used to quantitate the volatile organic levels in the
samples.
A response factor cartridge was run at the beginning of each analysis
day and agreement with the previously determined RRF values recorded. Each
compound was considered in-control when the daily RRF was within +30 of the
mean calibration RRF.
The RRF values used for quantitation of volatile organic levels and the
variability associated with the analyses are shown in Table 5-5. A summary
of data from the daily response factor cartridges is shown in Table 5-6.
Included for each analyte are the mean response factor (RRF) and the
variability (%RSD) for the analysis period and the dates when the
calculated daily RRF did not fall within the control limits. These results
show that there were no instances when the daily response factors were
outside the control limits.
In addition, the instrument tune was checked by measuring the intensity
of PFT fragment ions relative to the base peak in the daily response factor
cartridge. Control limits were based on +20% of the mean values
established during calibration (15 values). The PFT tune data acquired
during sample analysis are shown in Table 5-7. The tune as measured by PFT
relative ion abundances was within the acceptable range during the analysis
period.
52
-------
TABLE 5-4. LEVELS OF TARGET ANALYTES LOADED ONTO TENAX CARTRIDGES
FOR CALIBRATION
Amount Loaded, ng/cartridge
Compound
n-Octane
ฃ-Xylene
Styrene
o-Xylene
n-Nonane
a-Pinene
ฃ-Dichlorobenzene
n-Decane
Limonene
n-Dodecane
IX
211
260
272
260
216
256
284
219
252
224
2X
422
520
544
520
432
512
568
438
504
448
4X
844
1040
1088
1040
846
1024
1136
876
1008
896
10X
2110
2600
2720
2600
2160
2560
2840
2190
2520
2240
53
-------
TABLE 5-5. RELATIVE RESPONSE FACTORS USED FOR QUANTITATION OF
VOLATILE ORGANICS IN TENAX SAMPLES
Compound
n-Octane
ฃ-Xylene
Styrene
o-Xylene
n-Nonane
a-Pinene
ฃ-Dichlorobenzene
n-Decane
Limonene
n-Dodecane
Ion
71
114
103
106
78
104
91
103
106
99
128
93
121
113
146
148
150
99
142
68
121
136
85
170
RRF
.47
.12
.10
.86
.63
1.3
1.6
.10
.76
.11
.10
1.1
.11
.18
.92
.62
.11
.10
.11
1.0
.13
.17
.50
.09
%RSD
7.7
5.3
4.7
5.3
4.7
3.9
4.8
6.8
6.1
5.7
6.3
6.2
5.8
6.4
6.5
7.0
11
11
11
8.5
7.1
6.7
7.0
8.1
Na
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
^Duplicate analyses of calibration cartridges at IX, 2X, 4X, and 8X
levels.
54
-------
TABLE 5-6. RESULTS OF ANALYSES OF DAILY RESPONSE FACTOR
TENAX CARTRIDGES
RRFa
Compound
n-Decane
ฃ-Xylene
Styrene
o-Xylene
n-Nonane
o-Pinene
2-Dichlorobenzene
n-Decane
Limonene
n-Dodecane
m/z
71
114
103
106
78
104
91
103
106
99
128
93
121
136
113
146
148
150
99
142
68
121
136
85
170
Mean
0.42
0.12
0.10
0.80
0.60
1.2
1.6
0.11
0.71
0.10
0.10
1.0
0.10
0.10
0.16
0.84
0.57
0.09
0.09
0.10
0.09
0.12
0.15
0.45
0.08
%RSD Out-of-Control Situations*)
3.0
7.6
6.4
2.6
3.2
2.8
2.6
4.7
4.2
3.4
3.4
4.4
4.3
5.3
4.2
2.2
3.2
4.6
3.5
4.0
5.6
5.2
5.5
2.8
4.0
aEight analysis days; mean of six values. No daily values for 6/2,
6/6/89.
bDaily value did not fall within control limits - +30% of calibration
RRF.
55
-------
TABLE 5-7. PFT TUNE DATA, DAILY CHECK - FINNIGAN 4021
Date:
6/2/89
6/5/89
6/6/89
6/7/89
6/8/89
6/9/89
6/12/89
6/13/89
6/14/89
MEAN
SD
CV
Target Value^
Acceptable Range
69
43
44
41
43
42
42
43
1
2
43
35
52
.1
.5
.2
.9
.8
.3
.0
.1
.5
.7
.0-
.4
79
10
11
10
12
11
10
11
0
4
11
8
14
.9
.8
.6
.0
.1
.8
.2
.5
.6
.4
.0-
.8
PFT %
93
18.8
19.0
17.9
19.6
18.7
18.1
18.7
0.6
3.0
19.0
13.3-
24.7
Relative Abundance, m/z:
117
42.1
42.8
41.7
45.1
42.6
41.4
42.6
1.2
2.8
42.3
29.6-
55.0
167
14.1
14.4
13.9
14.5
13.8
14.4
14.2
0.3
1.9
14.2
9.9-
18.5
186
59.4
59
58
60
59
59
59
0
0
59
41
76
.5
.8
.3
.1
.1
.4
.5
.8
.1
.4-
.8
217
100
100
100
100
100
100
100
0.0
0.0
100
236
71.9
71.2
70.1
64.9
69.0
72.9
70.0
2.6
3.7
70.9
49.6-
92.2
aEstablished 6-2/ - 6/5/89.
56
-------
The performance of the sample inlet/chromatography system was checked
before analysis of samples was begun and again near the end of sample
analysis. Peak resolution (o-xylene and n-nonane) and separation number
(n-octane and n-decane) were monitored. These values were acceptable for
both determinations.
Canister Samples--
Three matrix types (whole breath, alveolar breath and air) collected in
canisters were analyzed on an 1KB 2091 GC/MS/COMP system on 43 analysis
days between April 6 and July 5, 1989.
Prior to sample analysis, calibration was established for each target
compound for each matrix type by analyzing calibration canisters. A
minimum of three concentrations and a blank were analyzed to prepare each
calibration. The calibration canisters were prepared using a canister
loading system [9]; the blank was a canister filled with clean ("zero")
air. Quantisation standards (ds-benzene, perfluorobenzene, perfluoro-
toluene) were added to each analytical aliquot (standards and samples)
during the cryofocussing step, prior to injection into the GC/MS/COMP
system. The target compound levels used for calibration are shown in
Table 5-8. A separate calibration series was prepared for each matrix
type - whole breath, alveolar breath and air. Relative response factors
(RRF) at each of the 4 points (zero air and 3 concentrations) were
calculated using the de-benzene quantisation standard. The Teknivent
software system utilized single RRFs at each level and interpolated on a
point-to-point basis. This point-to-point calibration was then used to
calculate the ng of each target compound in the samples analyzed. A new
calibration was prepared when more than 3 analytes were out-of-control on
an analysis day. The calibrations prepared were:
Matrix Calibration Prepared Analysis Days
Whole Breath 4/4 - 4/6/89 4/6 - 4/20/89
6/2 6/2 - 6/5/89
Alveolar Breath 4/11/89 4/12 - 4/25/89
4/26/89 4/26 - 6/1/89
6/7 - 6/8/89 6/8 - 7/4/89
Air 4/14/89 4/14 - 4/17/89
5/2/89 5/2 - 6/6/89
6/16 - 6/18/89 6/16 - 7/5/89
57
-------
TABLE 5-8. LEVELS OF STANDARDS USED TO PREPARE CANISTER SAMPLE CALIBRATIONS
Alveolar Breath Levels
ng/Aliquot Analyzed
Compound
Isopentane
Pentane
It-Octane
C-Nonane
A-Decane
Tetrachloroethylene
Trichloroethylene
Vinyl idene chloride
1.1.1-Trlchloroethane
Vinyl chloride
Toluene
2-Methylpentane
Benzene
Carbon tetrachlorlde
Chloroform
Olchloromethane
Ethylbenzene
p-Xylene
ฃ-Xylene
Styrene
Low
0.67
0.67
0.74
0.74
0.78
0.67
0.94
0.78
0.86
1.52
0.74
0.70
0.74
0.67
0.94
0.82
0.74
0.74
0.74
0.78
Medium
2
2
2
2
2
2
3
2
2
4
2
2
2
2
3
2
2
2
2
2
.16
.16
.41
.41
.53
.16
.05
.53
.80
.94
.41
.27
.41
.16 .
.05
.66
.41
.41
.41
.53
High
10.7
10.7
11.9
11.9
12.5
10.7
15.1
12.5
13.9
24.5
11.9
11.3
11.9
10.7
15.1
13.2
11.9
11.9
11.9
12.5
Whole Breath Levels
ng/Aliquot Analyzed
Low
2.
2.
2.
2.
2.
2.
3.
2.
2.
4.
2.
2.
2.
2.
3.
2.
2.
2.
2.
2.
16
16
41
41
53
16
05
53
80
94
41
27
41
16
05
66
41
41
41
53
Medium
4.70
4.75
5.33
5.45
5.54
4.93
6.66
5.52
6.09
11.00
5.26
4.95
5.30
4.84
6.79
6.03
5.26
5.26
5.27
5.52
High
18.8
19.0
21.3
21.8
22.2
19.7
26.7
22.1
24.4
44.1
21.0
19.8
21.2
19.3
27.2
24.1
21.0
21.0
21.1
22.1
Air Levels
ng/Aliquot Analyzed
Low
0.36
0.36
0.41
0.42
0.42
0.38
0.51
0.42
0.46
0.84
0.40
0.38
0.40
0.37
0.52
0.46
0.40
0.40
0.40
0.42
Medium
2.36
2.38
2.67
2.73
2.78
2.47
3.34
2.77
3.08
5.52
2.64
2.48
2.66
2.42
3.40
3.02
2.64
2.63
2.64
2.76
High
11.8
11.9
13.3
13.6
13.8
12.3
16.7
13.8
15.2
27.5
13.2
12.4
13.3
12.1
17.0
15.1
13.2
13.1
13.2
13.8
Levels for first calibration. Anounts varied slightly, depending on volume analyzed.
Quantltation standards approximately the
dg-Benzene ซ 1.87 ng.
for all matrix types; PFB 0.29 ng. PFT 0.54 ng.
58
-------
A calibration standard (high level) was run once during each analysis
day and the agreement with previously determined control limits recorded.
The ng of each target compound calculated for this daily standard must be
within +30% of the known amount. Values more than +30% from this known
value were considered out-of-control. Corrective action was taken when
more than 3 analytes were out-of-control on a given day. A summary of the
daily checks for whole breath calibration is shown in Table 5-9, alveolar
breath calibration in Table 5-10, and air calibration in Table 5-11.
In addition, the peak heights of the quantitation standards for each
analysis were tabulated. This was to monitor the consistency of the
GC/MS/COMP system. A summary of this QC check is shown in Table 5-12.
The performance of the sample inlet/chromatography system was checked
June 2, 1989. Peak resolution (ethylbenzene and ฃ-xylene) and separation
number (n-octane and n-decane) were calculated. Both values were
acceptable (resolution >1.0, separation number >40).
QC SAMPLE ANALYSIS (FIELD BLANKS AND CONTROLS)
Tenax Samples
The results of the analysis of Tenax field control samples are shown in
Table 5-13. Three breath and two air controls were utilized. The results
show consistently high recovery (87-98%) of all analytes. The data quality
objectives [13] for recovery were met for all target compounds.
The results for the analyses of Tenax field blank samples are shown in
Table 5-14. Four breath and two air blanks were utilized; no spirometer
blanks were collected. The results show that the Tenax used for sampling
was uniform and had very low background of target compounds.
Canister Samples
Blanks and controls were prepared for 2 of the 3 canister sample
matrices - whole breath and alveolar breath. There were no blanks or
controls for canister air samples. A QC set of one blank and one control
canister was utilized for each breath matrix sampled during each exposure
experiment. One alveolar breath blank and control were utilized for each
exposure experiment; one whole breath blank and control were utilized
during each of the three experiments where whole breath samples were
collected. No spirometer blanks were collected during this study.
59
-------
TABLE 5-9. DAILY CALIBRATION CHECKS - CANISTER WHOLE BREATH CALIBRATION
APRIL 6 - APRIL 20, 1989, JUNE 2 - JUNE 5, 1989
Compound
Isopentane
Pentane
n-OctaneC
n-NonaneC
n-DecaneC
Tetrachloroethylene
Trichloroethylene
Vinylidene chloride
1,1,1-Trichloroethane
Vinyl chloride
Toluene^
2-Methylpentane
Benzene
Carbon tetrachloride
Chloroform
Methyl ene chloride
n-Octane
n-Nonane
n-Decane
Toluene
Ethyl benzene
ฃ-Xylene
o-Xylene
Styrene
m/z
57
57
57
57
57
59
60
61
61
62
62
71
78
82
83
84
84
84
84
91
91
91
91
104
Target
Amount
ng
4.70
4.75
5.33
5.45
5.54
4.93
6.66
5.52
6.09
11.00
5.26
4.95
5.30
4.84
6.79
6.03
5.33
5.45
5.54
5.26
5.26
5.26
5.27
5.52
Daily
Checks
Mean
ng
4.64
4.82
4.91
4.76
4.66
5.00
6.24
5.29
5.63
10.42
4.91
4.47
5.00
4.55
6.48
5.42
5.09
4.85
5.96
4.84
4.98
4.64
5.05
5.07
%RSD Out-of -Control Situations!*
18 6/5
16
18
15
53d 4/11
11
10
10
10
13
10
15
11
7
12
7
12
9
7
9
8
12
6
10
analysis days; mean of 5 values - no data for 4/7, 4/10, 4/20, 6/2/89.
^Results of daily check greater than +30% of target amount. Corrective
action not required if fewer than 3 target compounds are out-of-control on
a given day.
CTwo ions monitored for these compounds.
dLarge %RSD due to a single value which may be an outlier.
60
-------
TABLE 5-10. DAILY CALIBRATION CHECKS - CANISTER ALVEOLAR BREATH
APRIL 12 - 25, 1989; APRIL 26 - JUNE 1, 1989; JUNE 8 - JULY 4, 1989
Compound
Isopentane
Pentane
n-OctaneC
n-NonaneC
n-Decanec
Tetrachloroethylene
Trichloroethylene
Vinylidene chloride
1 , 1 , 1-Trichloroethane
Vinyl chloride
Toluenec
2-Methylpentane
Benzene
Carbon tetrachloride
Chloroform
Methyl ene chloride
n-Octane
n-Nonane
n-Decane
Toluene
Ethyl benzene
2-Xylene
o-Xylene
Styrene
m/z
57
57
57
57
57
59
60
61
61
62
62
71
78
82
83
84
84
84
84
91
91
91
91
104
Target
Amount
ng
2
2
2
2
2
2
3
2
2
4
2
2
2
2
3
2
2
2
2
2
2
2
2
2
.16
.16
.41
.41
.53
.16
.05
.53
.80
.94
.41
.27
.41
.16
.05
.66
.41
.41
.53
.41
.41
.41
.41
.53
Daily
Check*
Mean
ng
1.85
1
2
2
2
2
2
2
2
4
2
1
2
2
2
2
2
2
2
2
2
2
2
2
.85
.12
.15
.47
.10
.98
.29
.66
.49
.32
.92
.09
.19
.87
.54d
.26
.29
.35
.30
.33
.34
.33
.44
%RSD
16
17
17
14
8
13
10
9
9
12
11
18
16
8
9
14
25
20
14
12
12
11
10
9
Out-of-Control Situations^1
5/31
4/21, 5/12, 5/15, 5/31
6/22
6/22
6/22
6/9, 6/12, 6/30
5/31
6/26
6/22, 6/26
6/22
6/30
6/22
6/22
6/22
6/22
^Twenty-nine analysis days; mean of twenty-three values. No data 4/12, 4/19,
4/25, 4/26, 5/9, 6/28/89.
^Results of daily check greater than +30% of target amount. Corrective
action not required if fewer than 3 target compounds are out-of-control on
a given day.
CTWO ions monitored for these compounds.
= 20.
61
-------
TABLE 5-11. DAILY CALIBRATION CHECKS - CANISTER AIR
APRIL 14-17, 1989; MAY 2 - JUNE 6, 1989; JUNE 16 - JULY 5, 1989
Compound
Isopentane
Pentane
n-0ctanec
n-Nonanec
n-DecaneC
Tetrachloroethylene
Trichloroethylene
Vinyl idene chloride
1,1,1-Trichloroethane
Vinyl chloride
Toluenec
2-Methylpentane
Benzene
Carbon tetrachloride
Chloroform
Methyl ene chloride
n-Octane
n-Nonane
n-Decane
Toluene
Ethyl benzene
E-Xylene
o-Xylene
Styrene
m/z
57
57
57
57
57
59
60
61
61
62
62
71
78
82
83
84
84
84
84
91
91
91
91
.104
Target
Amount
ng
11.8
11.9
13.3
13.6
13.8
12.3
16.7
13.8
15.2
27.5
13.2
12.4
13.3
12.1
17.0
15.1
13.3
13.8
13.8
13.2
13.2
13.1
13.2
13.8
Daily
Checka
Mean
ng
11.5
11.3
13.1
12.9
13.5
12.0
16.1
13.4
15.7
26.2
12.4
11.9
11.8
11.8
16.0
14.0
12.2
12.2
12.4
12.0
11.9
12.1
12.0
12.3
%RSD Out-of-Control Situations^
17
15
17
15
16
7
7
12
6
14
11
16
13
4
7
6
11
16 7/5
15 7/5
10
10
13
9
9
aNine analysis days; mean of 5 values - no data for 4/14, 5/5, 5/10, 6/16/89.
^Results of daily check greater than +30% of target amount. Corrective
action not required if fewer than 3 target compounds are out-of-control on
a given day.
CTWO ions monitored for these compounds.
62
-------
TABLE 5-12. SUMMARY OF EXTERNAL STANDARD PEAK HEIGHT MEASUREMENTS - 1KB 2091 SYSTEM
PFB
Matrix
Whole Breath
Experiment 1
Alveolar Breath
Experiment 1
Air. Experiment 1
Air. Experiment 2
Whole Breath
Experiment 2
Alveolar Breath
Experiment 2
Alveolar Breath
Experiment 3
LOO Determinations
Air. Experiment 3
Whole Breath Standards
A1r. Experiment 4
Alveolar Breath
Experiment 4
Alveolar Breath
Experiment 5
Whole Breath
Experiment 5
Air. Experiment 5
Alveolar Breath
Experiments HS2. HS3
Air. Experiments
HS2, HS3
Alveolar Breath
HS4. NS5
Dates
4/4-4/10/89
4/11-4/12/89
4/13-4/17/89
4/17/89
4/18-4/20/89
4/20-4/25/89
4/25-4/27/89
5/1-5/2/89
5/2-5/3/89
5/4/89
4/9-5/10/89
5/10-5/15/89
5/26-5/31/89
6/2-6/6/89
6/6/89
6/6-6/14/89
6/16-6/18/89
6/22-7/5/89
N
20C
5"
19ซ
4
18
19
27
9
7
4
if
169
26
19"
3
42
9
49<
Ave.
Height*
591
580
648
740
577
596
728
676
908
743
858
661
685
575
836
512
1002
555
USD
14
11
15
5.0
6.5
11
5.6
3.6
6.1
2.2
16
7.4
11
28
12
16
10
22
PFT
Ave.
Height*
1220
1170
1260
1490
1240
1210
1560
1460
1700
1520
1630
1490
1510
1360
1600
1160
1820
1190
USD
12
2.8
12
11
6.9
4.1
5.5
2.7
10
6.9
12
6.7
12
23
12
16
16
16
tig-Benzene
Ave.
Height0
3970
4070
4390
5050
3980
4200
5220
4620
6290
5450
6040
4550
4590
3590
5650
3010
6940
2980
*RSD
18
12
18
5.8
7.9
8.1
9.9
7.6
7.0
1.6
17
10
12
22
16
10
10
32
Average peak height meausred for m/z 69.
ฐAverage peak height measured for m/j 84.
C23 Analyses, data available for 20.
ซ13 Analyses, data available for 5.
21 Analyses, data available for 19.
*9 Analysis, data available for 7; Includes 2 alveolar breath samples.
018 Analyses, data available for 16.
"20 Analyses, data avaiable for 19.
*50 Analyses, data available for 49.
63
-------
TABLE 5-13. RESULTS OF ANALYSIS OF TENAX CONTROL SAMPLES
Breath Controls
Amount
Loaded
ng
n-Octane
2-Xylene
Styrene
o-Xylene
n-Nonane
a-Pinene
E-Dichlorobenzene
n-Decane
Limonene
n-Dodecane
211
260
272
260
216
256
284
219
252
224
Amount Found,
a^ncra
WTFC2
195
245
277
248
198
230
274
198
231
205
WTFC3
179
251
270
253
205
242
278
200
229
200
WTFC4
184
242
255
243
194
236
251
191
231
196
-or\i_u
Mean
88
95
98
95
92
92
94
90
91
89
Air Controls
Amount Found,
ng
ETFC1
194
258
276
259
210
251
269
204
241
202
ETFC6
173
233
252
238
193
227
251
193
220
186
%REC
Mean
87
94
97
96
93
93
92
91
91
87
a%REC = % Recovery.
-------
TABLE 5-14. RESULTS OF ANALYSIS OF TENAX BLANK SAMPLES
Breath Blanks8
Aoount Found, ng
Compound
fl-Octane
fi-Xylene
Styrene
ฃ-Xy1ene
g-Nonane
o-Plnene
fi-Dich lorobenzene
fl-Oecane
Linonene
jj-Oodecane
WTFB2
NDซ
NO
7
NO
NO
NO
6
NO
NO
NO
WTFB3
ND
NO
ND
NO
ND
NO
6
ND
ND
ND
HTFB4
2
ND
4
ND
ND
2
8
ND
2
2
MTFBB
2
ND
2
ND
ND
ND
ND
ND
ND
ND
Mean
ND
ND
4
ND
ND
NO
6
ND
ND
^2
Air Blanks'
Amount Found, ng
ETFB1
ND
ND
3
NO
ND
2
5
3
3
ND
ETFB6
2
ND
2
ND
ND
ND
ND
ND
NO
ND
Mean
2
ND
3
ND
ND
<1
ND
<*
13
ND
All reported values were at or beloH the quantifiable Unrlt but above the LOD.
DND = not detected.
65
-------
Results of the analysis of control canisters are shown in Tables 5-15
(whole breath) and 5-16 (alveolar breath). The results for whole breath
show good recovery for most compounds, between 80 and 98%. The data
quality objectives for recovery [13], >80%, were met for all compounds
except vinyl chloride, n-pentane, 2-methylpentane, n-nonane, and ฃ-xylene.
The variability (%RSD) was acceptable for most compounds. Higher
variability for vinyl chloride, 2-methylpentane and tetrachloroethylene was
due to one value being very different from the other two.
Results for alveolar breath controls show good recovery for most
compounds, between 80 and 95%. The data quality objectives for recovery
[13], >80%, were met for all compounds except 2-methylpentane and benzene.
The results for n-pentane and dichloromethane are quite variable; all
alveolar breath results for these compounds must be used with caution.
Results of the analysis of field blank canisters are shown in Tables
5-17 (whole breath) and 5-18 (alveolar breath). The results show very low
background for all target compounds with one exception. Sample FS1-ACFB1
(alveolar breath blank, experiment FS1) showed measurable amounts of six
target compounds.
DUPLICATE SAMPLE ANALYSIS
Tenax Samples
Seven duplicate pairs of samples were analyzed, one of the pair at RTI
(F-type sample) and the other at the independent reference laboratory (D or
Q-type sample). In addition, one control and one blank sample were
analyzed by the independent laboratory. Only 3 target compounds were
quantitated - a-pinene, limonene, and g-dichlorobenzene. The average
percent relative standard deviation (%RSD) between sample pairs is shown in
Table 5-19, and results of analysis of QC samples by the independent
laboratory are shown in Table 5-20.
The amount of data is not sufficient to draw conclusions. A minimum of
2 blanks and 2 controls is recommended for each batch of samples analyzed
by an independent laboratory and only one of each were analyzed for this
study. Two pairs of air sample duplicates did not result in enough data to
determine if data quality objectives were met [13] - <30% RSD. The results
for analysis of breath samples all show %RSD values greater than the
objective and greater than other recent data [5]. All of the values
66
-------
TABLE 5-15. RESULTS OF ANALYSIS OF CANISTER WHOLE BREATH
CONTROL SAMPLES
Whole Breath
Controls
Compound
, Vinyl chloride
Isopentane
Vinylidene chloride
n-Pentane
Dichloromethane
2-Methylpentane
Chloroform
1,1,1-Trichloroethane
Carbon tetrachloride
Benzene
Trichloroethylene
n-Octane
Toluene
n-Nonane
Tetrachl oroethyl ene
Ethyl benzene
E-Xylene
Styrene
o-Xylene
n-Decane
ng/L
Loaded
82.3
36.0
42.1
36.0
44.4
37.9
50.9
46.7
36.0
40.2
50.9
40.2
40.2
40.2
36.0
40.2
40.2
42.1
40.2
42.1
% Recovery
FS1
46
80
81
77
83
88
89
88
94
85
86
83
82
79
84
84
73
85
91
91
HS1
71
74
83
79
104
82
89
87
102
77
84
73
87
71
84
84
69
83
93
103
GS1
84
80
83
62
99
59
90
86
98
84
86
84
87
77
113
83
81
82
82
77
Mean
67
78
82
73
95
76
89
87
98
82
85
80
85
76
94
84
74
83
89
90
%RSDa
29
4
1
13
12
20
<1
1
4
5
1
8
3
6
18
<1
8
2
7
14
a%RSD = % Relative Standard Deviation.
67
-------
TABLE 5-16. RESULTS OF ANALYSIS OF CANISTER ALVEOLAR BREATH CONTROL SAMPLES
Alveolar Breath Controls
Compound
Vinyl chloride
Isopentane
Vinyl idene chloride
n-Pentane
Olchlorone thane
2-Methylpentane
Chloroform
1.1.1-Trlchloroethane
Carbon tetrachloride
Benzene
THchloroethylene
fl-Octane
Toluene
jj-Nonane
Tetrachloroethylene
Ethylbenzene
fi-Xylene
Styrene
fi-Xylene
ji-Oecane
ng/L
Loaded
82.3
36.0
42.1
36.0
44.4
37.9
50.9
46.7
36.0
40.2
50.9
40.2
40.2
40.2
36.0
40.2
40.2
42.1
40.2
42.1
* Recovery
FS1
70
67
80
744
331
62
75
58
56
61
58
49
62
58
70
66
72
67
66
84
HS1
96
83
92
121
86
91
94
87
94
88
91
83
95
87
92
98
98
101
98
102
SP1
85
82
82
85
99
87
92
87
94
87
89
80
88
82
94
89
89
90
89
86
MSI
90
78
81
73
101
64
92
94
106
79
90
85
86
81
97
91
95
94
93
85
6S1
75
64
76
68
106
58
83
79
97
59
87
66
75
72
90
81
85
87
85
89
NS2
99
93
98
93
90
75
99
105
106
96
108
100
97
103
95
98
99
105
98
101
HS3
79
78
85
76
89
78
89
SO
96
80
90
84
85
91
90
90
92
95
93
94
HS4
86
89
88
88
111
72
90
101
92
84
99
96
89
95
95
90
92
100
94
113
HS5
82
83
85
79
114
71
88
91
93
80
94
90
83
94
91
88
90
95
90
111
Mean
85
80
85
159t>
125C
73
89
88
93
79
90
91
84
85
90
88
90
93
90
96
kRSD9
11
11
7
131
59
14
7
15
15
14
14
18
12
15
8
10
8
11
10
11
kRSD ซ * Relative standard deviation.
>>Mean * Recovery (*RSD) without FS1 85(19).
CMean * Recovery (KRSD) without FS1 ซ 100(10).
68
-------
TABLE 5-17. RESULTS OF ANALYSIS OF CANISTER WHOLE BREATH
BLANK SAMPLES
Whole Breath Blanks
Amount Found ng/L
FS1 HS1 GS1
Compound WCFB1 WCFB1 WCFB1
Vinyl chloride NDa ND ND
Isopentane ND ND ND
Vinylidene chloride ND ND ND
n-Pentane ND ND ND
Dichloromethane ND ND ND
2-Methyl pentane ND ND ND
Chloroform ND ND ND
1,1,1-Trichloroethane ND ND ND
Carbon tetrachloride ND ND ND
Benzene 0.8 1.0 0.7
Trichloroethylene ND ND ND
n-Octane ND ND ND
Toluene ND ND ND
n-Nonane ND 0.3 0.4
Tetrachloroethylene ND ND ND
Ethyl benzene ND ND ND
2-Xylene ND ND ND
Styrene ND ND ND
o-Xylene ND ND ND
n-Decane ND 0.1 0.3
=>ND = not detected.
69
-------
TABLE 5-lfi. RESULTS OF ANALYSIS OF CANISTER ALVEOLAR BREATH BLANK SAMPLES
Alveolar Breath Blanks
Conpound _
Vinyl chloride
Isopentane
Vlnylldene chloride
B-Pentane
Dichloroaethane
2-Methylpentane
Chloroforn
l.I.l-Trlchloroethane
Carbon tetrachlorlde
Benzene
THchloroethylene
ji-Octane
Toluene
jj-Nonane
Tetrachloroethylene
Ethylbenzene
fi-Xylene
Styrene
ฃ-Xy1ene
j)-0ecane
FS1
ACFB1
NDป
NO
NO
NO
NO
NO
NO
NO
NO
5.4
NO
NO
0.5
NO
15.6
1.5
5.9
NO
2.9
0.2
HS1
ACFB1
NO
NO
NO
NO
NO
NO
NO
NO
NO
3.1
NO
NO
NO
0.2
3.4
0.3
0.7
NO
0.5
0.2
SP1
ACFB1
NO
ND
NO
NO
ND
ND
ND
ND
ND
1.2
ND
ND
0.3
ND
ND
ND
ND
ND
ND
0.3
WS1
ACFB1
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.8
ND
ND
ND
0.2
ND
ND
ND
ND
ND
0.3
Awxmt
GS1
ACFB1
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.7
ND
0.5
ND
0.5
ND
ND
ND
ND
ND
0.5
found, ng/L
HS2
ACFB1
ND
ND
NO
NO
NO
ND
ND
NO
NO
0.3
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
HS3
ACFB1
ND
ND
ND
ND
ND
NO
ND
1.0
NO
0.7
ND
ND
ND
NO
ND
ND
ND
ND
ND
NO
NS4
ACFB1
ND
ND
ND
ND
ND
ND
ND
ND
NO
NO
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
NFS
ACFB1
ND
ND
ND
ND
ND
ND
ND
ND
NO
0.7
ND
ND
1.2
1.7
ND
ND
ND
ND
ND
ND
NO not detected.
70
-------
TABLE 5-19. PERCENT RELATIVE STANDARD DEVIATION (%RSD) FOR
DUPLICATE TENAX SAMPLES (INTERLABORATORY)a
Analyte
a-Pinene
ฃ-Dichlorobenzene
Limonene
Pairs Analyzed
NC
2
3
4
4
Breath Samples^
Average %RSD
43
75
60
Air
N
1
1
1
2
Samples
%RSD
33
122
60
aDuplicate samples, one of the pair analyzed by the independent
laboratory, the other by RTI.
bwhole breath samples.
CNumber of pairs where both samples have measurable data.
TABLE 5-20. RESULTS OF ANALYSIS OF TENAX QUALITY CONTROL SAMPLES
BY THE INDEPENDENT LABORATORY
Analyte
a-Pinene
E-Dichlorobenzene
Limonene
Blank
ng Found
_a
18
-
Control
ng Loaded %
256
284
254
Recovery
57
57
35
found.
71
-------
reported by the independent laboratory (including the control) are
approximately half of the RTI values. Apparently there is a systematic
error in the procedures used at one of the laboratories. It will be
difficult to find the source of such an error since no standard reference
materials are available and no performance evaluation samples were
analyzed.
Additional duplicate sample pairs were collected and analyzed at RTI to
obtain a measure of the variability of the sampling and sample handling
procedures. The average %RSD between sample pairs is shown in Table 5-21.
These data, though limited, show excellent intralaboratory precision.
Canister Samples
No canister samples were analyzed by an independent laboratory; no
interlaboratory precision data are available. Intralaboratory precision
was estimated by calculating the %RSD between duplicate pairs of samples
analyzed at RTI. The average %RSD for duplicate canister samples is shown
in Table 5-22. All of the values show good agreement, <30% RSD, except for
several analyte/matrix combinations where there are only a single pair - n-
octane in alveolar breath and chloroform in whole breath.
PERFORMANCE EVALUATION SAMPLE ANALYSIS
Three canisters, supplied by RTI, were fortified by AREAL/EPA-RTP.
Each canister was given a legitimate study number and chain-of-custody form
before being introduced into the sample analysis chain. The results were
reported to EPA as ppb at reference conditions and without correcting for
background and recovery. The results are shown in Table 5-23. The results
show a high negative bias. No canister air matrix control samples were
analyzed, so no % recovery results are available for comparison. All of
the performance evaluation samples were run on a single analysis day
(7/5/89). It appears likely that poor instrument performance, not detected
by analysis of the daily calibration standard check, is the cause.
72
-------
TABLE 5-21. PERCENT RELATIVE STANDARD DEVIATION (%RSD) FOR
DUPLICATE TENAX SAMPLES (INTRALABORATORY)
Breath Samples^ Air
Analyte
n-Octane
E-Xylene
Styrene
o-Xylene
n-Nonane
a-Pinene
2-Dichlorobenzene
n-Decane
Limonene
n-Dodecane
Pairs Analyzed
Nb Average %RSD
0
1 3.8
0
0
0
7 5.0
10 2.6
0
10 4.8
0
10
Range N
0
0
0
0
0
0.0 - 12 1
0.4 - 6.9 1
0
0.0 - 9.1 1
0
1
Samples
%RSD
_
-
-
-
-
3.5
9.1
-
3.6
-
awhole breath.
^Number of pairs where both samples have measurable data.
73
-------
TABLE 5-22. PERCENT RELATIVE STANDARD DEVIATION (%RSD) FOR
DUPLICATE CANISTER SAMPLES (INTRALABORATORY)
Alveolar Breath
Samples
Analyte
Vinyl chloride
Isopentane
Pentane
Vinylidene chloride
2-Methylpentane
Methyl ene chloride
Chloroform
1,1,1-Trichloroethane
Carbon tetrachloride
Benzene
Trichloroethylene
Toluene
n-Octane
Tetrachloroethylene
Ethyl benzene
2-Xylene
n-Nonane
Styrene
o-Xylene
n-Decane
Number analyzed
Whole Breath
Samples
Air
Samples
Na Average %RSD N Average %RSD N Average %RSD
0
6
3
0
1
9
5
9
0
0
0
10
1
5
6
9
8
0
3
7
10
-
6.2
12.9
-
7.1
3.4
10.7
3.6
-
-
-
5.2
31.8
1.9
10.9
4.0
6.5
-
7.1
12.8
0
2
1
1
1
2
1
1
0
1
0
3
1
1
2
3
2
0
2
1
3
-
7.1
6.1
6.7
1.9
2.8
44.8
4.2
-
0.0
-
2.5
18.9
9.6
3.4
4.0
4.3
-
2.9
1.5
0
2
2
2
2
2
1
2
0
1
1
2
2
2
2
2
2
2
2
2
2
_
5.2
4.1
2.2
2.7
5.1
3.8
2.4
-
0.0
3.1
3.6
1.2
1.5
1.0
1.2
4.6
5.3
1.7
11.9
aNumber of pairs where both samples have measurable data.
74
-------
TABLE 5-23. RESULTS OF ANALYSIS OF PERFORMANCE EVALUATION CANISTERS
Compound
Vinyl chloride
Dichloromethane
Chloroform
1,1, 1-Trichloroethane
Carbon tetrachloride
Benzene
Trichloroethylene
Toluene
Tetrachloroethylene
Ethyl benzene
o-Xyl ene
Sample No. 205 - zero
aReported at reference
Spiked,
No. 204 No
4.1
3.3
3.9
8.1
3.8
4.2
4.4
8.2
4.3
7.5
7.2
air.
conditions.
ppb
. 206
2.0
1.7
1.9
4.1
1.9
2.1
2.2
4.1
2.2
3.7
3.6
Reported
No. 204
2.7
3.0
2.9
6.0
4.0
2.4
3.4
5.6
3.2
4.9
5.1
, ppba
No. 206
0.9
0.9
1.1
2.8
1.8
0.6
1.3
1.6
1.3
1.5
1.5
%
No. 204
-34
-9.1
-26
-26
5.3
-43
-23
-32
-26
-35
-29
Biasb
No. 206
-55
-47
-42
-32
-5.3
-71
-41
-61
-41
-59
-58
bg1as = reported-spiked x ^
75
-------
SECTION 6
RESULTS AND DATA ANALYSIS
INTRODUCTION
The primary goal of this research study was to increase our knowledge
of the factors that affect the use of breath measurements as a tool for
evaluating human exposure to VOCs. There were four principal objectives in
this study, as described in Section 1. The first objective was to develop
and test a canister based system for measuring VOC concentrations in
alveolar breath. A system was developed and is described in Appendices A
and B. This alveolar breath technique was employed to investigate
elimination kinetics and was compared to a previously employed whole breath
method. The second objective was to examine activities and
microenvironments commonly encountered by the general population to deter-
mine the potential for exposure to VOCs. In this study the concentrations
of 24 target compounds were measured in 32 microenvironments and in the
headspace above six consumer products. A third objective was to determine
breath VOC concentrations' that resulted from exposure to a variety of
chemicals in several microenvironments. Results are presented here for the
breath concentrations before and at multiple time points after exposures in
six micro-environments. The final objective was to calculate VOC residence
times in the body, including half-life and best-fit curve functions.
Breath decay half-lives were calculated using both a mono- and biexponen-
tial model. Several other mathematical curve-fit functions were evaluated
for their fit against the experimental data.
SCREENING RESULTS
Introduction
Screening samples were collected in the air of 32 microenvironments and
in the headspace above six consumer products. Target chemical concentra-
tions were measured in each microenvironment screening sample. Results of
the screening sample analyses were used to select several microenvironments
for conducting exposure and breath elimination kinetics experiments. A
primary goal of the microenvironmental screening was to find exposure
76
-------
scenarios for all target compounds that had concentrations high enough
(typically >100 ;ปg/m3) for breath concentrations to be measurable for at
least four hours after exiting the exposure location. A secondary goal of
the screening was to provide a survey of microenvironments where a large
portion of the population might be exposed to VOCs through short visits or
under working conditions.
Three types of air samples were collected for screening purposes.
Canisters were used to collect air samples in all 32 microenvironments and
were analyzed for all target compounds except a-pinene and limonene. Air
samples were collected on Tenax cartridges at 3 of the 32 locations in an
effort to locate elevated concentrations of o-pinene and limonene.
Headspace samples were collected over six consumer products using Tenax,
also in an effort to locate a source of a-pinene and limonene that could
be used in an exposure experiment.
Microenvironment Canister Screening Results
Air samples were collected using evacuated stainless steel canisters in
32 microenvironments that included homes, businesses, vehicles, and a
swimming pool. All canisters were analyzed by GC/MS to determine the
concentration of 22 target compounds including halogenated organics,
aliphatic hydrocarbons and aromatic hydrocarbons. Most screening samples
were collected as grab samples while several were collected over times
ranging from 20 min to 12 h depending upon the exposure activity being
characterized. Analytical results for the 32 microenvironment screening
samples are presented in Table 6-1. Short descriptions of the conditions
and results at each location are provided below.
Photocopier Room
The copier room, located in a laboratory building, was a relatively
small room with a Kodak copier. A small exhaust fan was in the room and
the copier was in use for a short period just prior to air collection. The
copier room was on the floor below organic and analytical chemistry labs.
Low concentrations of several chlorinated compounds were observed as were
very low levels of benzene and toluene.
77
-------
TABLE 6-1. AIR CONCENTRATIONS (UQ/R3) IN H1CROENV1RONMENT SCREENING CANISTER SAMPLES
Conpound
Vinyl chloride
Isopentane
jj-Pentane
Vinyl idene chloride
2-Methylpentane
Dichloronethane
Chloroforo
1.1.1-Trlchloroethane
Carbon tetrachloride
Benzene
Trichloroethylene
Toluene
g-Octane
Tetrachloroethylene
Ethylbenzene
l,fi-Xylene
fl-Nonane
fi-Xylene
Styrene
H-Oecane
ฃ-Dichlorobenzene
U-Oodecane
Compound
Vinyl chloride
Isopentane
fl-Pentane
Vinylidene chloride
2-Methylpentane
Dichloromethane
Chloroform
1.1.1-Trichloroethane
Carbon tetrachloride
Benzene
Trichloroethylene
Toluene
fl-Octane
Tetrachloroethylene
Ethylbenzene
fl.fi-Xylene
j)-Nonane
fi-Xylerte
Styrene
fl-Decane
ฃ-D1chlorobenzene
fl-Oodecane
Photocopier
Room
NDซ
NO
ND
NO
2
20
7
2
ND
3
35
8
ND
ND
ND
ND
ND
ND
ND
NO
ND
NO
Hone No. 2
With Moth
Crystals
ND
3
3
ND
3
77
ND
34
ND
2
ND
61
1
ND
47
180
5
11
ND
9
>540
3
Photocopy ft Oil-Based Metal Wood Wood
Hone No. 1
Mlth Moth
Print Center Painting Shop Shop Staining Crystals
ND
ND
180
ND
2
10
50
5
ND
6
ND
9
ND
ND
1
5
2
4
ND
ND
ND
ND
Office
With One
Smoker
ND
ND
66
ND
ND
39
36
7
ND
9
ND
21
ND
ND
1
7
ND
ND
ND
ND
ND
NC
ND
ND
150
. ND
ND
25
77
3
ND
ND
5
20
16
ND
24
88
230
39
ND
1200
NO
46
Indoor
Swimming
Pool
ND
24
15
NO
7
ND
240
2
ND
6
ND
7
1
ND
3
10
2
4
ND
4
18
ND
ND
ND
62
4
12
23
36
21000
NO
ND
8
130
27
1200
4
11
26
4
ND
63
ND
NCb
ND ND
ND ND
ND 1100
ND ND
ND 58
5 2
ND ND
140 18
ND ND
ND 10
15 5
120 2700
53 350
100 2
90 11
200 30
8200 340
75 11
ND 2
1500 810
ND ND
NC NC
Furniture Hardware
Stripping
Shop
ND
10
6
3
26
7100
2
280
ND
4
120
2500
29
23
120
430
61
160
68
180
ND
35
Store
No. 1
ND
29
16
2
41
900
ND
210
ND
9
ND
650
80
27
590
1700
290
110
38
570
39
57
ND
56
28
ND
1
3
14
ND
ND
8
ND
26
ND
ND
7
13
ND
9
ND
ND
22
NC
Hardware
Store
No. 2
ND
630
180
NO
120
100
1
46
ND
34
6
250
50
6
17
64
200
23
7
390
ND
25
(continued)
78
-------
TABLE 6-1 (cont'd.)
Compound
Vinyl chloride
Isopentane
H-Pentane
Vinyl Idene chloride
2-Methylpentane
Olchloroaethane
Chloroform
I.l.l-Trlchloroethane
Carbon tetrachloHde
Benzene
Trlchloroethylene
Toluene
jv-Octane
Tetrachloroethylene
Ethylbenzene
j.B-Xylene
jl-Nonane
fi-Xylene
Styrene
H-Decane
p.-D1chlorobenzene
,Q-Oodecane
Compound
Vinyl chloride
Isopentane
fl-Pentane
Vlnylldene chloride
2-Methylpentane
Dlchloronethane
Chloroforo
I.l.l-Trlchloroethane
Carbon tetrachlorlde
Benzene
Trlchloroethylene
Toluene
fl-Octane
Tetrachloroethylene
Ethylbenzene
fj. fi-Xylene
fl-Nonane
fi-Xylene
Styrene
jt-Decane
e-01chlorobenzene
jl-Dodecane
Interior
Decorating
Store No. 1
NO
35
19
NO
12
240
ND
22
ND
9
ND
310
21
9
28
93
380
22
6
700
ND
NC
Truckstop
Outdoors
NC
80
32
ND
18
ND
ND
1
ND
B
NO
21
2
ND
5
16
2
6
NO
2
NC
NC
Interior
Beauty Beauty
Decorating School School
Store No.
ND
9
5
ND
5
74
ND
12
ND
3
ND
37
53
ND
7
26
190
11
ND
590
90
NO
Auto A
Mower
Refueling
1
>1500
>3600
1
>1900
NC
NC
2
NC
>380
ND
920
22
ND
110
340
20
120
13
10
NC
NC
2 No. 1
ND
21
10
ND
3
17
20
72
ND
15
12
240
2
ND
5
16
6
5
7
14
3
6
Inside
Net* Truck
Cab
ND
11
8
1
15
7
2
160
3
3
1
240
3
2
27
140
8
68
33
45
NC
NC
No. 2 Laundrout
ND
43
11
NO
3
. ND
6
8
ND
8
7
320
ND
4
2
8
3
2
ND
2
3
2
Nome
Garage
A.M.
NO
250
120
ND
62
2
1
3
ND
30
ND
120
4
ND
26
93
4
32
6
5
NC
NC
ND
11
11
NO
3
6
36
2
ND
4
ND
6
ND
17
1
3
ND
1
ND
ND
2
ND
Hone
Garage
P.M.
ND
>370
222
ND
110
1
1
2
3
53
ND
160
7
ND
32
110
7
40
10
8
NC
NC
Bar/Club Rush Hour
with Driving With
Smokers
ND
74
27
NO
22
6
6
3
ND
20
ND
54
2
1
10
31
6
13
6
7
NC
NC
Commercial
Repair
Garage
ND
79
28
ND
19
4
NO
1
ND
10
ND
36
2
ND
7
22
3
10
ND
8
NC
NC
Sacking
ND
61
30
ND
24
5
2
5
NC
52
ND
120
3
6
23
72
3
23
17
3
NC
NC
Body ft
Repair
Shop
ND
88
28
1
23
4
ND
68
1
10
ND
520
7
16
56
>210
56
71
46
56
NC
NC
(continued)
79
-------
TABLE 6-1 (cont'd.)
Compound
Vinyl chloride
Isopentane
ji-Pentane
Vlnylldene chloride
2-tfethylpentane
Diehloromethane
Chloroform
1,1, 1-Tr ichloroethane
Carbon tetrachloride
Benzene
Trichloroethylene
Toluene
n-Octane
Tetrach loroethy lene
Ethylbenzene
l.fi-Xylene
jj-Nonane
$-Xylene
Styrene
U-Oecane
p.-Dichlorobenzene
ji-Dodecane
Paint ซ
Body
Shop
NO
260
110
ND
61
7
1
3
ND
68
ND
2100
35
ND
67
220
36
80
19
5
NC
NC
Hone
Diapers
In Bleach
ND
20
16
ND
ND
41
94
ND
ND
4
ND
11
ND
ND
1
7
2
2
2
3
NC
NC
Mass Spec.
Laboratory
Facility
NC
4
56
NO
9
450
49
13
1
3
5
180
5
NC
NC
Laboratory
with New
Roof
ND
4
4
2
2
>1400
3
53
ND
2
1
3
ND
ND
1
2
2
1
ND
37
NC
NC
Packaging
Facility With
Styrofoam
ND
ND
ND
ND
ND
97
100
ND
ND
ND
ND
14
ND
ND
ND
14
ND
ND
1
ND
NC
NC
ND - not detected.
ฐNC = not calculated.
80
-------
Photocopy and Print Center
A high volume reproduction room was equipped with 3 Xerox copiers (in
operation), an offset printer (off), and 4 binding machines. Chemicals in
storage in this area were isopropyl alcohol, 1,1,1-trichloroethane,
kerosene, 1,4-dioxane, butylene oxide, nitromethane, and styrene/ aery late
polymer ink black. An outside door was open to the room and several
exhaust fans were on. A photo processing lab was located in an adjacent
room. Pentane and chloroform were found at moderately high concentrations
at this location (180 and 50 /ปg/m3) with all other target compounds present
at <10 /*g/m3.
Oil -Based Painting
A screening sample was collected from the air in an analytical
laboratory in which the cabinets, doors, and trim were being painted with
Glidden Wood Undercoater Oil Primer 310. Paint application began 1 h
before the sample was collected. The normal building ventilation system
was functioning and two doors leading to the hallway were open. Relatively
high concentrations of some of the aliphatic hydrocarbons were measured as
were somewhat lower levels of the aromatic hydrocarbons.
Metal Shop
A metal shop, which was also adjacent to a woodworking shop, was
sampled. The chemical products in use were a cutting fluid (1,1,1-
trichloroethane), a degreasing solvent and, a safety coolant concentrate
(including diethanolamine and monoethanolamine) . The primary ventilation
was from an open door and an open ceiling (in a larger building). Some
machinery work had taken place prior to sampling. Very high 1,1,1-
trichloroethane (21,000 /*g/m3) and tetrachloroethylene (1200 /*g/m3)
concentrations were observed. These probably resulted from the cutting
fluid in which the tetrachloroethylene may have been a minor component.
Vinyl idene chloride was found to be present as a trace component in the
cutting fluid and was measured in the metal shop air at a concentration of
4
Woodworking Shop
A woodworking shop, adjacent to the metal -working shop, had a light
wood cutting schedule. Exhaust and recirculating (filtered) fans were on
during cutting. Some wood glue was present but not in use. The main door
81
-------
to the shop was open to the rest of the building. Several target compounds
were observed at concentrations above 50 pg/m$ with n-nonane (8200 /*g/m3)
and n-decane (1500 /*g/m3) the most prominant.
Wood Staining--
The wood staining air sample was collected in an area near the metal
shop and the wood shop in the same building. The staining of recently
constructed bookshelves had been completed just prior to the time of air
sampling. The ventilation in this part of the building was relatively
poor. High concentrations (>350 /*g/ni3) of n-pentane, n-octane, n-decane,
toluene were observed.
Moth Crystals; Home No. 1
A bedroom, with mothballs in a closet, was sampled. The mothballs were
p-dichlorobenzene and were in an open chest inside of a closet with the
door kept closed. The bedroom was 10' x 12' and an interior room fan was
on prior to air sampling. The ฃ-dichlorobenzene concentration was
relatively low at 22 /tg/m3 compared to concentrations measured in many
homes during previous TEAM studies (1-5).
Moth Crystals; Home No. 2
Two 4-oz moth crystals were located in a small closet in a den. The
closet door was open while the den door was closed and there was no active
ventilation. Results of the analysis of a screening sample collected in
the den showed that ฃ-dichlorobenzene was present at >540 /*g/m3 (the GC/MS
signal was saturated during this analysis). It should be noted that the
manufacturer recommended using four 4-oz moth crystals in a closet the size
of the one in this house. Dichloromethane, toluene, and m,p_-xylene were
also present in this room and the source of these compounds was probably a
sealed bottle of furniture refinishing solution stored in the closet.
Office with One Smoker--
A small office had one smoker who had smoked a cigarette prior to
sampling. Several other cigarettes had been smoked earlier that same
morning. The hallway door was open as well as a small exterior window.
The office was located in a laboratory building, but was not directly
connected to a laboratory. Only low concentrations (<10 /ig/m3) were
82
-------
observed for the tobacco combustion products benzene, ethylbenzene, m,ฃ-
xylene, and styrene.
Indoor Swimming Pool
A screening sample was collected several feet above and away from the
edge of an indoor swimming pool. The pool building's main ventilation
system was not in operation and only one exhaust fan was blowing into an
attached utility room. Chloroform was the target of this screening and was
measured at a concentration of 240 /*g/m3. A block of deoderizer was found
in an attached bathroom. It had the odor of ฃ-dichlorobenzene which was
present in the pool building air at a concentration of 18 /ig/m3.
Furniture Stripping Shop
A furniture stripping/refinishing shop had furniture stripping
operations underway prior to collection of the screening sample.
Additionally, some carpentry was done and touch-up spray finish was used
before or during air sampling. A number of pieces of furniture were
sitting in the main area, presumably in the final stages of drying. The
exterior doors were closed though there were exhaust fans on at the rear of
the building. The furniture stripping solvent was primarily toluene and
dichloromethane. Moderate to high air concentrations of many target
compounds were observed.
Hardware Store No. 1
A screening sample of air was collected in the center of the hardware
store during business hours. The store stocked a wide variety of products
including paints, paint removers, thinners, pesticides, home cleaning
products, degreasing products, and bulk solvents as well as standard
hardware and wood products. Most wood cutting and storage operations were
performed in a separate building. A wide range of halogenated, aromatic,
and aliphatic hydrocarbon target compounds was observed at concentrations
ranging from 100 to 1700 /
-------
at this store while aliphatic hydrocarbons were at similar or higher
levels.
Interior Decorating Store No. 1
The interior redecorating store No. 1 contained primarily samples of
vinyl flooring and rugs as well as various solvents and paints. A larger
quantity of paints was stored in the rear of the building. Paint was mixed
shortly before an air sample was collected. The solvents present included
xylenes, toluene, paint stripper (dichloromethane), paint thinner, stains
and oils. No obvious ventilation was noticed in the sales area. Many
target compounds were observed in the screening sample, with levels above
200 /tg/m3 found for dichloromethane, toluene, n-nonane, and n-decane.
Interior Decorating Store No. 2
The interior redecorating store No. 2 was similar to the previous one,
though slightly smaller. Most of the target compounds measured in this
screening location were at concentrations lower than the first store.
Moderately high levels of n-nonane (190 /tg/m3) and n-decane (590 /jg/m3)
were observed. The ฃ-dichlorobenzene level (90 /tg/m3) was greater in this
microenvironment than in any other except home No. 2 with moth crystals.
Beauty School No. 1
The beauty school No. 1 had a low level of activity in a large room. A
few permanents were being given at the time of sampling. Only a few hair
products were visible, though more were probably stored in the cabinets.
Ventilation, similar to that provided in most office buildings, was
present. Many target compounds were observed at low levels while toluene
was present at 240 ^g/m3.
Beauty School No. 2--
The beauty school No. 2 was similar to the first, though the activity
for the size of the room was slightly greater. More hair products were on
the shelf than at the first school. Once again, toluene was the only
target compounds measured at an elevated concentration (320 /tg/m3).
Laundromat--
A screening sample was collected at a large, new, coin operated
laundromat facility. Water used at this laundromat was supplied by a
municipal water authority. Samples of this water supply have been analyzed
84
-------
in previous years and have contained chloroform levels ranging from
approximately 50 ppb to above 100 ppb. During collection of the screening
sample there were five washers and seven dryers in operation. Ceiling
exhaust vents were in operation. A dry-cleaning operation was located
within the same building next door to the laundramat. A door between the
two was closed. The screening sample chloroform concentration was
36 /*g/m3.
Bar/Club with Smokers
A small bar and nightclub facility was located in a basement area. The
club was divided into two sections. The front section contained a bar,
seating, and small stage. Several pool tables were located in the rear
section. A short narrow hallway connected the two sections. The front
section was nearly filled with approximately 45 patrons and the rear
section contained approximately 15 patrons during sampling. Approximately
18-20 patrons were smoking cigarettes at the time of sample collection.
One exhaust fan was operating in each section and a rear outside door was
open. Benzene, toluene, xylenes, and styrene were observed at concentra-
tions ranging from 6 to 54 /*g/m3.
Rush Hour Driving with Smoking
An air sample was collected over a 75 minute period while the driver
smoked 7 cigarettes and drove a crowded interstate and downtown loop route
during morning rush hour traffic in Raleigh, NC. The car windows were
closed and the ventilation system was set to the fresh air setting with a
medium fan speed 30% of the time. The lighter aliphatic hydrocarbons and
aromatic compounds were measured at concentrations ranging from 23 to 120
/ig/m3.
Truckstop, Outdoors--
A screening sample was collected outdoors at a large truckstop located
at an interstate highway exit. The sample was collected about 20 m
downwind from a row of 14 diesel and 2 gasoline pumps. Four diesel trucks,
one small truck, and two cars were refueling during sample collection. The
temperature was above 30'C at the time of sampling. Aliphatic and aromatic
hydrocarbons were observed, with only isopentane (80 /*g/m3) and n-pentane
(32 ^g/m3) at concentrations greater than 30 /
-------
Auto and Mower Refueling--
A screening sample was collected over a 25 minute period during which
time a car was driven to a gas station, the car fuel tank was filled, a
10 L fuel can was filled, the car was driven home, and fuel was added to a
lawn mower. The fuel can was sealed and transported in the passenger
compartment of the car in both directions. The air temperature was 25ฐC.
The sample was collected near the breathing zone of the driver, who also
did all fuel handling operations. Very high concentrations of the light
aliphatic hydrocarbon (>1500 /380
/*g/m3) were measured. Other target aromatic hydrocarbons were present at
110 to 340 /jg/m3.
Inside New Truck Cab~
An air sample was collected inside the cab of a new (<300 odometer
miles) Chevy S-10 pickup truck to determine if a source of vinyl chloride
could be found. The truck's dashboard, seats, and floor coverings were
constructed from a plastic believed to be vinyl. The interior temperature
was 42*C at the time of sampling. Vinyl chloride was not detected but
moderately high levels of 1,1,1-trichloroethane, toluene, and m,ฃ-xylene
(140 to 240 /ig/m3) were observed.
Home Garage A.M. and P.M.--
The home garage was a 2-car detached garage that had some paint, paint
thinner, gasoline, oil and kerosene stored in it. No appreciable
ventilation was present. The P.M. sample was collected after a fully
warmed up car was driven into it, the door was closed, and the engine
turned off -15 sec later. The air sample was collected 30 min later. The
A.M. sample was collected before any activity occurred in the garage for
the day, after the car had been parked overnight. Light aliphatic and
aromatic hydrocarbons, consistent with fuel constituents, were observed in
both samples. The concentrations were higher in the afternoon sample after
the car was driven into the garage.
Commercial Repair Garage
The repair garage was a bay-type repair garage with bays on each side
of the building. Most bay doors were open. No other ventilation was
present. Cars were inside all bays and active repair work was underway at
the time of sample collection. All hydrocarbon concentrations were less
86
-------
than 100 /;g/m3. The concentrations measured under these highly ventilated
conditions may be different in cooler weather when the bay doors are
closed.
Body and Repair Shop
The body and repair shop was a large building with approximately 10-12
cars inside. The building had its bay doors open and the building had some
forced ventilation present. No automobiles were being painted and repair
work in progress was relatively light. Toluene (520 /jg/m3) and m,ฃ-xylene
(>210 /jg/m3) were the most significant target compound concentrations
measured at this microenvironment. Low levels of the aliphatic hydrocar-
bons (7 to 88 ^g/m3) were present. The highest microenvironmental styrene
concentration (46 /*g/m3) was recorded at this location.
Paint and Body Shop
The paint and body shop was a moderately sized shop with approximately
5 cars inside. No painting was going on at the time of collection. Two
bay doors were open though no forced ventilation was present except for
fans. A high toluene concentration was measured (2100 /tg/m3). Isopentane
(260 ^g/m3) and m,ฃ-xylene (220 pg/m3) levels were observed as were lower
concentrations of other aliphatic and aromatic hydrocarbons.
Home; Diapers in Bleach
This sample was actually collected as one of the overnight 12-h samples
prior to an exposure experiment. An unusually high chloroform concentra-
tion (94 /*g/m3) was observed in this sample. The home water supply came
from a well and was not chlorinated, so it was unlikely that water was a
source. No chloroform was observed in a similar sample from an earlier
experiment. The only difference was the presence of soiled diapers soaking
in a bleach solution in a closed pail in the bathroom. It was surmised,
but not verified, that the soaking diapers was the source of the
chloroform.
Mass Spectrometry Laboratory Facility
A screening sample was collected in a laboratory facility containing
five operating mass spectrometers in an effort to locate a source of the
heavier aliphatic hydrocarbons for an exposure experiment. It was thought
that the large number of vacuum pumps using oil might be an emission
87
-------
source. Only very low concentrations of these compounds were observed.
Two common laboratory solvents, dichloromethane (450 /*g/m3) and toluene
(180 /1400 /*g/m3)
resulted from extractions underway in the laboratory at the time of sample
collection.
Packaging Facility with Styrofoam--
A screening sample was collected in a small room used for packaging
materials for shipping. A large volume of styrofoam beads and shipping
containers was stored in this room. This sample was collected in an
attempt to find a source of styrene at levels high enough to conduct an
exposure experiment. The measured styrene concentration was only 1 pg/m3.
The source of chloroform in this sample (100 0g/m3) was not determined.
Nontarget Chemical Identifications
Nine of the screening samples were further examined to identify non-
target compounds present in significant amounts. Because this was a time
consuming process, only nine samples were selected for qualitative
analysis. Samples were selected based upon peaks observed in the original
chromatographic traces. Results of this secondary data analysis are
reported in Table 6-2. In most cases, aliphatic and aromatic hydrocarbons
were identified along with an occasional fluorochlorocarbon or oxygenated
compound. Dimethyl disulfide was tentatively identified in the swimming
pool air. These identifications were not used for selecting exposure
locations and were intended to provide general information on chemicals
present in some microenvironments.
Compound identifications were made using a mass spectra library
database. The spectrum of each unknown compound was compared to similar
spectra in the library using a computer matching routine. A mathematical
calculation was used to describe the degree of fit between the unknown
compound spectra and the library spectra. The fit, measured as an R2
-------
TABLE 6-2. LIST OF NONTARGET COMPOUNDS PRESENT IN SELECTED SCREENING CANISTER SAMPLES
Furniture Stripper
Interior Decorating
Store ซ1
Interior Decorating
Store *2
trichlorofluoroBethane
trlnethylsllanol
2-Mthyhexane
3-aethylhexane
acetic add, 2-ซethylpropyl
ester (tent.)a
ethylcyclohexane (tent.)
tMaethylcyclohexane 1so.b
3-Mthyloctane
butanoic add. 2-ซ*thylpropyl
ester (tent.)
decane. branched chain (tent.)
4-Mthylnonane
l.2.4-tr1nethylbenzene (tent.)
l-ethyl-2-ซethylbenzene (tent.)
tHaethylbenzene 1so.
2-aethyl-l,3-butadlene
(tent.)
3-Kthylhexane (tent.)
trlMthylcyclohexane Iso.
ethylcyclohexane
triMthylcyclohexane
2-rcthyloctane
3-ซethy1octane
ethylethylcyclohexane
propylcyclohexane
4-cyclohexadecane (tent.)
2-aethylheptane
3-*ethylheptane
dlwthylcyclohexane 1so.
dlnethylcyclohexane
ethylcyclohexane (tent.)
trInethyIcyclohexane Iso.
2-aethyloctane
3-nethyloctane
ethyInethy1eye1ohexane
alkylcyclohexane (tent.)
alkane. branched
ji-undecane
alkylcyclohexane
HardMare Store *1
HardNare Store 12
Beauty School *1
1.2-pentadlene (tent.)
ethylcyclopentane
2-nethylhexane
3-nethylhexane
ethylethylhexane (tent.)
ketone (tent.)
2-aethylheptane
3-ซethylheptane (tent.)
acetic add. 2-ซethylpropyl ester
aldehyde or ketone (tent.)
1,3.5-trlaethylcyclohexane
2-nethyloctane (tent.)
3-cethyloctane
trans-l-ethyl-4-nethylcyclohexane
(tent.)
ethylnonane Iso. (tent.)
(J-oethylethyl)-benzene
ethylnonane Iso. (tent.)
trInethyIbenzene Iso. (tent.)
1,3-eyclopentadiene.5-(1-methyl-
propylldene) (tent.)
ketone (tent.)
trIchlorofluoromethane
pentene 1so.
alkane (tent.)
alkane (tent.)
hexane
ethylcyclohexane (tent.)
dlaethylpentane (tent.)
ethylhexane
branched alkane
branched alkane
alkyl cyclopentane (tent.)
branched alkane
alkyl cyclohexane
trlnethyIcyclonexane
ethyloctane Iso.
ethyloctane 1so.
branched alkene iso.
alkyl cyclohexane
alkane, branched
alkane, branched
alkane. branched
tr1chlorof1uoronethane
pentadiene
2-ethylcyclobutanol (tent.)
cyclic alkene or diene (tent.)
ฃ-undecane
Beauty School 92
SMlnlng Pool
Laundromat
With Peroa Pure Dryer:
trIchlorofluoronethane
pentadlene (tent.)
decane. branched (tent.)
decane. branched (tent.)
undecane, branched (tent.)
alkane. branched
alkane, branched
Hlthout Peru-Pure Dryer:
acetic add. anhydride (tent.)
acetic acid, butyl ester
dlnethyl dlsulflde (tent.)
ester (tent.)
tent. Tentative GC/NS Identification.
b1so. Isomer.
89
-------
value, generally had to be above 0.8 (on a scale from 0.0 to 1.0) for the
tentative identification to be acceptable. One sample, from Beauty School
No. 2, was analyzed both with and without the Perma-Pure dryer installed
in the analytical system. The dryer was removed to determine if polar
compounds were present in the sample. The drying tube prevents polar
compounds from reaching the GC/MS system.
Microenvironment Tenax Screening Results
Air samples were collected on Tenax cartridges in three microenviron-
ments in an attempt to locate a source of elevated a-pinene and limonene
concentrations for an exposure experiment with those chemicals. The
furniture stripping shop, hardware store, and woodshop were selected for
screening since a-pinene was believed to be a natural wood emission product
and because limonene was believed to be in wood finishing and care products
used or sold at these locations. Each Tenax sample was collected over a
4 h period and was analyzed by GC/MS for 10 target compounds. The
analytical results are reported in Table 6-3.
Most of the target compounds were found at measurable levels in each
sample. Aliphatic and aromatic hydrocarbon concentrations were often above
100 /jg/m3 at all three locations with n-nonane and n-decane above 700 pg/m$
in the wood shop and m,ฃ-xylene above 600 /jg/m3 in the hardware store.
Both a-pinene and limonene were found in all three locations but at
relatively low concentrations. The highest a-pinene (34 /ig/m3) and
limonene (12 /ig/m3) concentrations were measured at the woodshop. These
concentrations were not believed to be sufficiently elevated to provide a
measurable breath concentration several hours after an exposure. Since a
suitable microenvironment for exposures to these compounds could not be
identified, several consumer products were evaluated for a-pinene and
limonene emissions.
Consumer Product Emissions Results
Six consumer products were tested including a pine oil, two furniture
polishes, two room deoderizers, and one bathroom bowl cleaner. Samples
were collected by a dynamic headspace purge onto Tenax cartridges followed
by GC/MS analysis. Mass spectral data were examined for the presence of a-
pinene and limonene plus any interfering components that could create
problems during a later exposure experiment. There are many compounds
90
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TABLE 6-3. AIR CONCENTRATIONS (/ig/m3) IN MICROENVIRONMENTAL
SCREENING TENAX SAMPLES
Furniture Stripping Hardware Store
Compound Shop No. 1 Wood Shop
n-Octane
m,ฃ-Xylene
Styrene
o-Xylene
n-Nonane
o-Pinene
p_-Dichlorobenzene
n-Decane
Limonene
n-Dodecane
26
280
35
110
71
11
2
120
2
25
29
620
15
230
110
24
3
100
5
1
110
180
3
80
730
34
NDa
770
12
68
= not detected.
91
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that are structurally similar to o-pinene and limonene that could have
created data interpretation problems if present at significant quantities
relative to the target compounds. Results of the qualitative analyses are
presented in Table 6-4.
Both target compounds were observed in the Pine-Solฎ samples, but there
were also many other compounds present that had mass spectra similar enough
to the targets to create interferences. The same result was also obtained
for the Airwickฎ and Renuzitฎ room deoderizers. The Johnny Freshฎ bathroom
bowl cleaner emitted ฃ-dichlorobenzene almost exclusively, with a small
amount of a compound tentatively identified as o-fenchene that may have
been responsible for the pine scent. Neither a-pinene or limonene were
observed in the Old Englishฎ furniture polish. Both compounds were
observed in the Wood Plusฎ furniture polish, and there were fewer potential
interferents in this product than in the other products that were tested.
Based on these results, Wood Plusฎ polish was chosen for use during an
exposure experiment so that the breath levels of a-pinene and limonene
could be examined.
Screening Results Discussion
The microenvironmental screening conducted during this research study
was not intended as an exhaustive evaluation of all possible locations.
Nor was it intended to define the range of concentrations that might be
found across the country at all locations and under all conditions. At
most, only one or two examples of each category were sampled at only one
time point. Different results would undoubtedly be obtained for locations
with different operating procedures, product lines, or ventilation
conditions. For example, the auto repair garages were sampled in warm
weather with the garage bays open. Higher concentrations of VOCs may have
been measured in the winter with all bay doors closed. The screening
results obtained during this study should not be extrapolated to represent
all similar microenvironments. The results should instead be considered a
snapshot at one time and place that might be an indicator of potential
human exposure to volatile organic compounds.
The intent of screening microenvironments during this study was
specifically to locate as many target compounds at the highest concentra-
tions as possible. The screening results were evaluated and several
92
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TABLE 6-4. QUALITATIVE RESULTS OF THE GC/MS ANALYSIS OF
PRODUCT HEADSPACE SAMPLES FOR o-PINENE AND LIMONENE
Product Name
Pine-Solฎ
(19% pine oil)
Airwickฎ Solid Room
Deoderizer (lemon scent)
Wood Plusฎ Polish
(lemon scent)
Johnny Freshฎ Bathroom
Bowl Cleaner (pine scent)
Old Englishฎ Furniture
Polish
Renuzit Roomateฎ Liquid
Air Freshner
a-Pinene
Present
Present
Present
Absent
Absent
Present
Limonene
Present
Present
Present
Absent
Absent
Present
Potential
Interfering
Compounds
Many
Many
Few
-a
-
Many
aNot applicable since target compounds were absent.
93
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microenvironments were selected as locations for conducting exposure
experiments. Measurements of exhaled breath VOC levels were made after
exposure to the microenvironment to evaluate whether such measurements
can be a quantitative indicator of the original exposure.
EXPOSURE EXPERIMENT RESULTS
Introduction
Six microenvironments were selected for exposure experiments based upon
the identities and amounts of VOCs in the screening samples. These
locations included the furniture stripping shop, hardware store No. 1, the
wood/metal shop, the indoor swimming pool, a home garage with wood staining
and fuel handling, and a home with moth crystals and furniture polish. For
each experiment, one participant was exposed to VOCs in the microenviron-
mental air for several hours. This participant provided one breath sample
before, and multiple breath samples after the exposure. The goal was to
determine the degree to which breath concentrations of each chemical were
elevated by the exposure and the kinetics of elimination after the
exposure. Air samples were collected within the microenvironment during
each experiment to determine the VOC exposure levels. Air samples were
also collected from the participant's airspace before and after each
experiment to determine if they had unintended exposures to the target
compounds.
The measured concentrations of organic compounds in each breath sample
were studied in a number of ways. First, if the overnight air sample
showed an insignificant exposure level when compared to the experimental
exposure, and the pre-exposure breath concentration was low, then the
measured breath levels were plotted as a function of post-exposure time.
In this manner, qualitative information regarding the observed decays was
acquired. Of special concern were the differences observed between decay
curves for the same compound derived from whole breath and alveolar breath
collections. Second, concentration/time data for each compound were
subjected to a bivariate curve-fitting analysis to screen and study the
ability of seven different mathematical functions to define the observed
decay. Of particular interest was the ability of each equation to
accurately predict a breath concentration for times throughout the entire
range of collection times. Third, the data were fit to mono- and
94
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biexpontial (e-kt and e-kjt + e-^t) curves, corresponding to one and two
physiological compartments, respectively, in an attempt to estimate the
elimination half-life of each compound from the body and to study the
effects of multiple compartment assumptions. Finally, these half-lives
were examined for evidence of dependence on exposure level or the
individual exposed.
Selection of Exposure Microenvironments
Six microenvironments were chosen for exposure experiments based on
screening results. The screening samples were collected in two phases.
The first phase included samples from the furniture stripping shop and
hardware store No. 1. These two locations contained many of the target
compounds at concentrations believed to be high enough for measuring breath
decays over 4 h time period after exposure. Target compounds present at
these two locations included halogenated organics, aromatics, and the less
volatile aliphatic hydrocarbons. Breath decay data were collected
successfully for many of the target compounds in these two microenviron-
ments.
Chloroform was found at an indoor swimming pool at a concentration
sufficiently high to allow breath decay measurements and an exposure
experiment was successfully completed there. Screening samples from the
wood/metal shop indicated large amounts of the less volatile aliphatic
compounds might be found. However, the high concentrations were not
observed during the exposure experiments. One surprising compound,
vinylidene chloride, provided measurable breath concentrations after
exposure in the wood/metal shop. This compound was found to be a trace
component of the metal cutting fluid for which 1,1,1-trichloroethane was
the primary constituent.
The second phase of the screening sample collection was used to try to
locate sources of compounds not found in the first four experiments. These
included benzene, styrene, vinyl chloride, carbon tetrachloride, the
aliphatic hydrocarbons, a-pinene and limonene. Sources tested included
smoking areas and vehicle related activities. One exposure experiment was
conducted in a home garage which included fuel handling and wood staining.
This experiment resulted in successful breath decay measurements for
virtually every aromatic and aliphatic hydrocarbon except styrene. The
95
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last exposure experiment was conducted in a home with two consumer
products, wood polish and moth crystals. Breath decay measurements were
made for p_-dichlorobenzene, limonene, and a-pinene in this microenviron-
ment.
No sources suitable for decay studies were found for vinyl chloride,
carbon tetrachloride, and styrene. Styrene was observed in several
microenvironments, but always at concentrations lower than 45 /ig/m3, which
was too low for breath decay measurements. No measurable concentrations of
vinyl chloride were found in any microenvironment, including a new truck
cab with copious amounts of vinyl maintained at a high temperature. No
carbon tetrachloride levels above 3 /jg/m3 were measured in any screening
samples.
Since exposure locations for three compounds (vinyl chloride, carbon
tetrachloride, and styrene) could not be readily found, a decision was made
to eliminate breath decay studies for these compounds. Repeat exposure
experiments were performed at one location for several other compounds to
provide some data for inter- and intraperson variability in breath levels
and elimination kinetics. The hardware store was chosen for these repeat
experiments because of the wide range of compounds measured successfully in
the first experiment. In a second experiment, the two participants who had
alternated exposures in the earlier experiments were both exposed to
hardware store air at the same time. Both participants provided breath
samples at the same time points after exposure using two separate alveolar
spirometers. A final experiment was conducted in which two new
participants were exposed to hardware store air and then provided
breath samples during the same time period.
Description of Exposure Experiments
Furniture Stripper Shop-
Participant No. 1 was exposed to the air in a furniture stripping and
refinishing shop for 3.5 h. Shop operations during the exposure period
included dipping furniture into stripping vats, gluing, and a small amount
of finishing. Chemicals known to be in use included toluene and dichloro-
methane in the stripping vats. Large exhaust fans were on at one end of
the building while a small door was open at the other end. The participant
provided both alveolar and whole breath samples over a 4 h period after
exposure.
96
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Hardware Store, First Exposure-
Participant No. 2 was exposed to the air inside a hardware store for
3.7 h. Several shelves were stocked with paints, thinners, degreasers,
stripping agents, and bulk solvents. Pesticides and home cleaning products
were also on sale at this store. No solvent handling or paint mixing was
observed in the store during the exposure period. A ceiling mounted heater
was blowing warm air down the aisle with paints and solvents toward the
participant. The participant provided alveolar and whole breath samples
over a 4 h period after exposure.
Indoor Swimming Pool
Participant No. 2 was exposed to the air in an indoor swimming pool for
2.3 h. The exposure was scheduled for 4 h but was cut short when the
manager decided to open a wall of exterior doors to increase the ventila-
tion. This likely would have decreased the indoor chloroform concentration
making data analysis more difficult. Very little ventilation occurred in
the building during the exposure period. The participant sat approxima-
tely 3 m from the side of the pool and 1.5 m above the pool surface. A
group of approximately 15 children were completing a swimming lesson as the
exposure period started. A free swim period attended by 10 persons was the
only activity during the exposure. The participant provided alveolar
breath samples over a 4 h period after exposure. It should be noted that
this participant was exposed to a relatively high time weighted average
concentration of chloroform (94 /ig/m3) during the 12 h prior to the
exposure experiment. It was surmised that diapers soaking in bleach in his
home were the source of this exposure. The swimming pool air concentration
was 600 /ig/n)3, which was over five times higher than the overnight
exposure. The first breath concentration after exposure was 81 /jg/m3,
compared to 9 pg/m$ before exposure.
Wood/Metal Shop--
Participant No. 1 was exposed to the air in a wood and metal shop for
4.0 h. Wood shop operations included sawing, sanding, and gluing. Metal
shop operations were performed during the last hour of the exposure period
and included metal cutting using a cutting fluid. The participant divided
his time equally between the two adjacent shops during the last hour of
exposure. Both alveolar and whole breath samples were collected over a 4 h
97
-------
period after exposure. Only the alveolar samples were analyzed since the
less volatile aliphatic hydrocarbons were not found as expected.
Consumer Products--
Participant No. 2 was exposed to the air in one room of a house with
moth crystals and furniture polish in use. Two four ounce p_-dichloro-
benzene moth crystals had been placed in the room two days prior to the
experiment. An open container of Wood Plusฎ furniture polish was placed in
the room. Every 40 minutes the polish was applied to both sides of a 0.2 x
0.9 m board with a rag. The participant wore gloves during each
application to avoid dermal exposure. To avoid re-exposure, the partici-
pant changed clothes immediately before beginning the post-exposure breath
sample collection. Breath samples were collected over a 68 h period after
exposure since the half-life of p_-dichlorobenzene elimination was expected
to be much longer than that of most other target compounds [7]. Multiple
air samples were collected in the participant's breathing zone over time
after the exposure to determine if he was exposed to other sources of ฃ-
dichlorobenzene. The p_-dichlorobenzene levels in these air samples
decreased over time but were measurable even when the participant was at
home, where the air sample prior to exposure showed very little ฃ-dichloro-
benzene. It was believed that the Tenax cartridge in the participant's
breathing zone was adsorbing p_-dichlorobenzene being exhaled by the
participant.
Garage with Staining and Fuel Handling-
Participant No. 1 was exposed to emissions from automobiles, fuel
handling, and wood staining operations during a 2.2 h period in a garage.
The 2 car detached garage had very little ventilation and the temperature
reached 37ฐC so the exposure period was reduced from 4 h. Several
activities occurred during this exposure experiment. Two warm cars were
driven into the garage and run 1 min. Stain was applied to 0.8 m2 of
plywood by someone other than the participant twice during the exposure
period. Gasoline was transferred between a can and lawnmower four times
and kerosene was also transferred between a nonfunctioning heater and can
E
four times. All fuel was handled by someone other than the participant.
The participant sat approximately 3 m from the staining and fuel handling
operations. The participant changed clothes immediately before providing
98
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breath samples. Alveolar and whole breath samples were collected over a
4 h period after exposure.
Hardware Store, Second Exposure-
Participant Nos. 1 and 2 were exposed to air in the same hardware store
at the same time for 3.7 h. The participants were seated approximately 2 m
apart in the crowded store. The heating system was off and the air
conditioning system was on; otherwise conditions were identical to those in
the first hardware store exposure. The participants changed clothes
immediately prior to collection of breath samples. Alveolar breath samples
were collected at the same time from each participant using two spirometer
systems over a 4 h period after exposure.
Hardware Store, Third Exposure-
Participants No. 3 and 4 were exposed to air in the same hardware store
at the same time for 3.9 h. All conditions were the same as the second
exposure in the hardware store. The participants changed clothes
immediately prior to collection of breath samples. Alveolar breath samples
were collected at the same time from each participant using two spirometer
systems over a 4 h period after exposure.
Decay Data from the Exposure Experiments
In this section, the main observations regarding the types of compounds
measured in the breath will be summarized for each exposure experiment.
Complete information regarding the measured concentrations of organic
compounds in breath for each experiment can be found in Appendix D. All of
the air data for each experiment are included in Appendix D before the
corresponding breath data. In addition, for those compounds that provided
measurable concentrations in breath for seven or more collection periods,
breath VOC data were plotted as a function of time after exposure ended.
These plots are presented in Appendix E. The QL for the compound is given
with each graph. Because the QL was dependent upon the volume of sample
analyzed, it was not the same for every experiment or breath type. Any
point that appears on a graph was above the QL for that particular
analysis. Selected examples will be presented in the text along with
appropriate comments.
99
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Furniture Stripper Shop (Figures E-l through E-4)--
The measurement of the organic compounds in the breath after exposure
in the furniture stripper shop showed that four compounds were present in a
sufficient number of samples to provide decay information. These compounds
were dichloromethane, 1,1,1-trichloroethane, toluene, and m,ฃ-xylene.
Meta- and para-xylene are reported as one compound because they were not
chromatographically resolved. Breath concentrations ranged from a high of
460 /*g/m3 for toluene to 15 ^g/m3 for m,ฃ-xylene. Even at the relatively
low levels measured for rn,ฃ-xylene, a decay was observed. For illustra-
tion, these decays are shown in Figure 6-1. The decay for toluene (Fig. 6-
1A) is clearly defined. The short sampling times and higher collection
frequency for the alveolar samples helped to define the very early phase of
the decay curve. Although the measurements of the compound in whole breath
provided a very good decay curve, rapid changes and possible subtle
features in the curve were missed because of these samples. The longer
time required to collect whole breath samples also restricted the number of
data points that could be generated during the first few minutes after
exposure ended. A more detailed discussion of the comparison of alveolar
breath with whole breath appears later.
Figure 6-1B shows a clearly defined decay for m,j>-xylene, even at
levels near the QL. The alveolar values at 17 and 102 minutes are
presumably the result of contamination of the 2 L canisters used here
because this phenomenon was observed in another experiment that used the
same canisters. In addition, these canisters had been used previously to
collect samples with high levels of aromatic compounds. No such concen-
tration deviations were observed in the whole breath samples. This
potential contamination illustrates the importance of using clean
canisters. The fact that we were measuring a series of concentrations
and studying the kinetics made this contamination more evident.
Hardware Store, First Exposure (HS1, Figures E-5 through E-12)--
This experiment provided data for the elimination decays of
dichloromethane, 1,1,1-trichloroethane, toluene, tetrachloroethylene,
ethylbenzene, m.fi-xylene, n-nonane, and o-xylene. This exposure situation
resulted in moderate levels of at least two classes (chlorinated hydro-
carbons and aromatic compounds) of chemicals. Deviations from the curves
100
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IO
o
ฃ
m
440-
400-
MO-
S20-
280'
240-
200
160
120
60
40
0
A Alveolor Breoth
Whole Breoth
Figure 6-1A.
Time (Min.)
Breath levels of toluene post-exposure to furniture
stripping operations. Exposure: 5700 vg/m';.QL !
6 ug/m3.
12-
4)
*->
D
i_
OD
A Alveolar Breoth
Whole Breoth
A
Time (Min.)
Figure 6-1B. Breath levels of m,ฃ-xylene post exposure tOgfurniture
strippina operatations. Exposure: 240 ug/m ; QL
0.7
101
-------
in the alveolar breath samples were observed for ethylbenzene, o-xylene,
m.g-xylene and possibly toluene. Although smaller than those observed for
m.E-xylene in FS1 above, these deviations might be due to contaminated
canisters. We did not use the 2 I canisters in subsequent experiments
where the collection of aromatic hydrocarbons was likely. The unusual
curve for tetrachloroethylene (Figure E-8) might be the result of the
compound elimination from multiple body compartments (see later section).
Indoor Swimming Pool (Figure E-13)--
Data from the alveolar samples provided by participant No. 2 showed
decays for both chloroform and isopentane. The chloroform decay was
consistent with decays measured for other organic compounds in other
experiments. The isopentane decay should be interpreted with great caution
because uncontrolled exposure to this compound was very likely, especially
at low levels. Such levels were easily encountered while driving to the
exposure site and reexposure could have occurred if there was any heavy
traffic near the sample collection area.
Wood/Metal Shop (E-14 through E-16)
This exposure experiment resulted in a very high exposure to 1,1,1-
trichloroethane and the resulting decay is shown in Figure 6-2. This
compound was the major component of the cutting fluid used during the last
hour of the exposure. This decay also showed what might be a second
elimination from another body compartment at 35-40 minutes. Such subtle
elevations were also observed in a number of samples from this and other
exposure situations. The individual canister samples were analyzed in the
order of last collected to first collected; the last seven canisters were
analyzed on the day immediately preceeding the analysis of the first three
canisters. This increase was determined from measurements made during one
day. If the maximum of the elevation (a break in the curve) was from the
first measurement from a new day, the value would be more suspect than one
in a series from the same day. The observation that similar concentration
elevations were measured at similar times from a number of experiments
suggests that this phenomenon is real rather than the result of random
variability in the measurement technique. If random variability were the
cause, the variations would also be expected to appear at random times.
102
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o
E
O^
3
QJ
0
I
MM
ฃ
"5
^
CD
6400 -i
6000
5600 -i
5200 -i
4*00 -
4400 -
4000 -
3ซ00 -
3200-
2800
2400
2000
1600
1200
BOO
400 -
A
A 1,1.1-Trichloroethone
A
A
A
A
A
A
A
A
0 J5 50 75 100 125 150 175 2C
Time (Min.)
Figure 6-2. Decay of 1,1,1-trichloroethane in alveolar breath after
exposure to an active wood working shop. Exposure:
16000 yg/m3; QL = 12 yg/md.
103
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This experiment also measured a decay for vinylidene chloride, that was
found to be a trace component of the cutting fluid. Decays for n-pentane
and toluene were also observed.
Consumer Products (Figures E-17,18)
In this experiment, decays for limonene, a-pinene, and ฃ-dichloro-
benzene were observed. The decays'for alpha-pinene and 2-dichlorobenzene
were quite smooth. The results for limonene were quite erratic; the reason
for this is unclear, although shortterm reexposures that might not be
obvious in the integrated air samples, could cause this effect. Data were
not plotted beyond 17.8 hours because there was evidence of a reexposure
in the air samples. (See Tables D-12, D-13)
Garage with Staining and Fuel Handling (Figures E-19 through E-32)
This experiment resulted in the best exposure to aliphatic hydrocarbons
of any of the situations studied. Moderate to high levels of isopentane,
n-pentane, 2-methylpentane, 2-methylhexane, 3-methylhexane, n-octane,
ethylcyclohexane, 3-methyloctane, n-nonane, n-decane, and n-undecane were
measured in both whole and alveolar breath. The aromatic compounds
benzene, toluene, ethylbenzene, m,ฃ-xylene, and o-xylene were also detected
at moderate levels. Most of the curves generated from the data of this
experiment showed distinct secondary decay features and some even had
features which might suggest a third decay. The very high exposure levels
for some of these compounds could have resulted in better equilibration
with deep compartments in the body, as discussed further in the section
where the half life data are presented. In addition, because this was the
only experiment where both the alveolar and whole breath samples were
collected in 6 L canisters, thus minimizing canister volume variabilities,
this data will also be the focus of the section comparing whole and
alveolar breath.
Hardware Store, Second Exposure (Figures E-35 through E-42)
Because of the variety of compounds detected in the breath after the
first hardware store experiment, we chose this environment to study the
effect of replicate exposure (one person two separate times) and interindi-
vidual variability (different people, same environment) on measured decays
and half lives. These two topics will be discussed in a later section.
The compounds detected in breath after this exposure were very similar to
104
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those found after HS1. This experiment (HS2.3) provided decay data for
dichloromethane, 1,1,1-trichloroethane, toluene, ethylbenzene, m.^-xylene,
n-nonane, o-xylene, and n-decane. The decay data for dichloromethane and
toluene (Figures E-35 and E-36, respectively) show that participant No. 2
was emitting substantially higher levels of these two compounds even though
the exposure of both participants was the same. Analytical results of the
overnight air samples (Table D-17, 140HS20CF1) indicated that participant
No. 2 was exposed to these two compounds at levels comparable to those
measured in the hardware store during the night before the experiment.
This difference in breath levels between the two participants shows that a
longer exposure would result in a more complete equilibration of the body
with the compounds in the exposure environments and a measurable,
cumulative effect of exposure to VOCs. This has relevance for estimating
different body burdens after acute vs. chronic exposure, even to low air
concentrations of VOCs.
Hardware Store, Third Exposure (Figures E-43 through E-49)--
The experiment was repeated a third time with two participants diffe-
rent from those exposed earlier in an attempt to collect more information
of interindividual variability. In this situation, dichloromethane, 1,1,1-
trichloroethane, toluene, tetrachloroethylene, m,ฃ-xylene, n-nonane, and n-
decane were present in the breath at levels sufficient to provide decay
information. Participant No. 3 generally had higher levels of VOCs in his
breath than did participant No. 4. This might be a result of sex or body
build differences between the participants as well as somewhat different
exposure air concentrations for each participant (Table D-21). The data
are too limited to be certain.
An interesting observation was found in the duplicate samples for
participant No. 4 where the measured concentrations were often below the
levels expected based on the shape of the decay curve. This was true for
time points 3 and 10 minutes for dichloromethane, 1,1,1-trichloroethane,
toluene, tetrachloroethylene, and n-nonane. No such trend was observed for
participant No. 4. Such a situation could happen if oversampling of the
exhaled breath from the spirometer were occuring. Since the total
volumetric flow of 3.2 L/min (1.6 L/min into each of two 6 L canisters) was
collected from the spirometer and given that this participant breathed at a
105
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faster rate (Table 4-9), which suggests a smaller alveolar volume, an
oversampling situation might have occurred here. The further delopment
work on this spirometer system (work assignment 50 of this contract) has
indicated that a sampling flow of 1 L/min. into a 1.8 L canister should
work well. Even duplicate sampling, with a total sampling flow of 2 L/min
should not result in oversampling.
Comparison of Alveolar and Whole Breath
At the onset of this work, two main advantages of sampling alveolar
breath with the new device over sampling whole breath with the old device
were seen. First, the new spirometer design would allow for the rapid
collection of samples and thus allow the elucidation of the early phase of
the elimination kinetics. Second, alveolar air normally accounts for two-
thirds of the tidal volume, so the concentration of VOCs in whole breath
would be expected to be approximately two-thirds of the concentration in
alveolar breath. All else being equal, the collection of alveolar air
would be the method of choice for maximum analytical sensitivity. Although
several of the exposure experiments (FS1, HS1, GS1) utilized both alveolar
and whole breath collection, only GS1 collected both types of breath into
canisters of the same size. Because sampling and analysis parameters were
identical for both alveolar and whole breath in this experiment, data from
this experiment were used for comparative purposes.
A visual comparison, with the aid of the decay plots of Figures E-19
through E-34, indicates that the consistently higher organic concentrations
expected in alveolar breath were not measured. To quantify some of these
differences, the concentrations in the two types of samples were directly
compared at three different time points. Because the samples physically
could not be collected at the same time, the concentrations for whole
breath, at 12 and 185 minutes, and alveolar breath at 60 minutes were used
as measured values. The corresponding concentrations in alveolar breath at
12 and 185 minutes and whole breath at 60 minutes were estimated using the
equation of best fit from the bivarate curve fit analysis, discussed in the
next section. For our purposes here, the estimations provided by the curve
fitting routines were adequate, a conclusion supported by comparing the
concentrations in Table 6-5 with the curves in Appendix E cited above.
Table 6-5 presents the concentrations of each measurable compound from GS1
106
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TABLE 6-5. PERCENT DIFFERENCE BETWEEN ALVEOLAR AND WHOLE BREATH ORGANIC COMPOUND CONCENTRATIONS
AT 12, 60. AND 185 MINUTES POST-EXPOSURE9
12
Min
Concentrations
Compound
Isopentane
jj-Pentane
2-Methylpentane
2-Methylhexane
3-Methylhexane
Benzene
Toluene
fl-Octane
Ethylcyclohexane
3-Hethyloctane
Ethylbenzene
fi-Xylene
jj-Nonane
o-Xylene
jt-Oecane
C-Undecane
Whole
180
99
50
44
27
24
40
8.6
20
120
36
23
230
8.5
160
36
Alveolar
140
67
66
36
25
17
35
5.4
24
131
36
27
154
8.6
143
61
60 Min
Concentrations
Whole
71
42
25
11
11
13
22
4.3
9
62
21
11
90
4.6
71
15
Alveolar
64
43
29
13
9.2
10
23
2.4
11
52
26
18
90
4.1
83
23
185 Min
Concentrations
Whole
38
19
12
8.8
6.3
6.2
8.8
1.5
4.9
25
8.5
4.7
37
1.9
28
6
Alveolar
42
26
15
7.5
5.7
6.5
15
1.5
5.5
16
17
7.3
50
2.6
55
11
(Alveolar-Whole)/
Alveolar
Tซ12
-28.6
-13.8
24.2
-15.8
-8.0
-41.2
-14.3
-59.3
16.7
8.4
-5.6
14.8
-49.4
1.2
-11.9
41.0
Tป60
-10.9
2.3
13.8
15.4
-19.6
-30.0
4.3
-79.2
18.2
-19.2
19.2
36.9
0.0
-12.2
14.5
34.8
T-185
9.5
26.9
20.0
-17.3
-10.5
4.6
41.3
0.0
10.9
-56.3
50.0
35.6
26.0
26.9
49.1
45.5
Concentration (tg/m3) for whole breath at 12 and 185 nlnutes and alveolar breath at 60 minutes
Mere as measured. The corresponding data point in whole or alveolar breath was calculated using
the equation of best fit from StatPlan as In Table 6-10 or 6-12.
Both alveolar and whole breath samples mere collected into 6 L canisters and analyzed 1n the
sane manner.
107
-------
for both whole and alveolar breath at times 12, 60, and 185 minutes post-
exposure. For clarity, the percent difference of the alveolar concentra-
tions from the whole breath concentrations were calculated. A negative
value corresponds to a situation where the alveolar breath concentration
was less than the whole breath concentration.
Table 6-5 shows that only for 2-methypentane, ethylcyclohexane, m,ฃ-
xylene, and n-undecane were the alveolar concentrations consistently
higher. In no case were the alveolar concentrations consistently lower
than the whole breath concentrations. In examining the differences as
function of time, it can be seen that isopentane, n-pentane, benzene,
toluene, ethyl benzene, n-nonane, o-xylene, and n-decane apparently become
more concentrated in the alveolar breath sample relative to the whole
breath sample. The reason for this is unclear. The expected trend would
be for the alveolar to be much larger than the whole breath concentrations
early in the decay and assume a more constant difference later in the
elimination. The reasoning behind this is that early in the elimination
process the concentration is changing rapidly and the whole breath sample
is integrated over several minutes thus possibly underrepresenting the
concentration at the time corresponding to the start of the collection. As
the changes become less rapid, the integrated values would become more
accurate with regard to the actual concentration at any time during the
collection of that sample and the differences between alveolar and whole
breath concentrations would become constant.
Oversampling of the alveolar air could result in alveolar levels lower
than the corresponding whole breath levels but this should be consistent
throughout the collection of samples from a given individual. This is not
the case. In addition, earlier work (task #1 of this work assignment)
indicated that a sampling flow or 1.7 liters/minute should not lead to
oversampling. Adsorption of the analytes to the alveolar spirometer,
especially the tube, would cause the lower relative alveolar concentra-
tions. This, too, should be consistent, especially over the small range of
concentration changes measured for any given analyte in this experiment.
Finally, forced exhalation, such as would occur if some resistance in the
spirometer was encountered, could lead to an enrichment of the whole breath
with alveolar air. That is, the percentage of deadspace air in the whole
108
-------
breath would decrease under these circumstances and the apparent concentra-
tion of the organic compounds would increase. Such a situation would be
expected to cause the whole breath concentrations to become more similar to
the alveolar concentrations. This effect would be constant over the course
of the experiment.
Despite an incomplete understanding of the significance of the above
phenomena noted in a single experiment, the importance of collecting breath
samples in rapid succession cannot be disputed. This work has shown that
the higher number of data points can more accurately describe the decay
kinetics compared to collection of sequential whole breath samples. The
data of Appendix C clearly indicate subtle concentration changes in the
decay that are ambiguous if only whole breath data is examined. As
mentioned above, these subtle changes are not likely to be artifacts.
In addition, the alveolar spirometer has the potential for being truly
portable, unlike the current, whole breath spirometer, and could make the
collection and analysis of breath samples very near the exposure site more
feasible. The ease of use would facilitate the application of this non-
invasive exposure assessment method to a much broader application than has
been the case to date.
MATHEMATICAL TREATMENT OF THE DATA
This section describes the manner in which the data collected during
this task was treated in order to gain information on the elimination half
lives of the different organic compounds and the potential for mathematical
curve fitting routines to define an equation to describe the elimination
decays. The understanding of the nature of the decay for a given chemical,
as measured in the breath, is a first step in the evaluation of the
potential of breath analysis to predict actual exposure. What follows is a
brief description of the view of the body as a multicompartment system,
into which the organic compounds in air can be partitioned and eliminated
at differing rates, followed by estimates of the elimination half lives of
the measured compounds, assuming both a one compartment and a two compart-
ment model, and an application of several bivan ate mathematical functions
to the decay data.
109
-------
Compartmentalization
When a volatile organic compound is inhaled, it partitions into the
blood via diffusion through the alveolar membrane. Each compound would be
expected to have a distinct partition factor depending upon its volatility
and solubility in the bood. Once dissolved in the blood, the compound
circulates throughout the body where it can partition into other tissues,
such as fat, each with a differing partition factor. The rate at which a
compound can enter or exit a particular tissue depends not only on its
partition factor, but also to the extent that blood flows through that
tissue, i.e., the extent of perfusion. These tissues have been grouped
according to the extent of perfusion and termed "compartments." Such a
compartmentalized view of the body has been described by Anderson [14] and
is depicted in Figure 6-3. The elimination of organic compounds from these
compartments can occur at different rates. For example, a lipophilic
compound such as ฃ-dichlorobenzene, would be expected to be stored and
released from fat tissue at a rate different from that of blood. Once the
compound reenters the blood, it can partition, if it is sufficiently
volatile, into the alveolar air space and be exhaled. What results during
elimination is the composite clearance from these different compartments
with a resulting array of elimination half-lives. Thus, the determination
of the elimination kinetics and the corresponding elimination half-lives
can be greatly affected by the number of compartments assumed. In this
work, we considered both a one compartment and a two compartment
pharmacokinetic model. The half-lives were determined using both models
and the bivarate curve fitting analysis used a one compartment model.
Half-Life Estimations
In keeping with the Compartmentalization models described above, the
data were studied in terms of both one compartment and two compartment
models consistent with the pharmacokinetic elimination of substances from
the body. The measured breath concentrations and their corresponding times
(post exposure) were fit to equations of the form B = C~Et and B = Ci-Eit +
C2-E2* corresponding to a one compartment and two compartment decay,
respectively, where B is the concentration in the breath at any time t, Ci
and C2 are constants, and E is the exponential constant that determines the
rate of the exponential decay. This curve fitting was accomplished using
110
-------
CINHALE
CARTERIAL
DEAD SPACE
ALVEOLAR
SPACE
BLOOD
CEXHALE
CVENOUS
LUNG
t
LIVER
METABOLISM
COUT
t
KIDNEY
RENAL EXCRETION
OTHER WELL-PERFUSED
A ORGANS |
A MODERATELY WELL-
T PERFUSED ORGANS I
t
POORLY PERFUSED
TISSUES
Figure 6-3. Schematic of a physiologically based model for metabolism
of inhaled gases and vapors. This scheme assumes metabolism
to occur only in the liver and excretion of the parent
chemical to occur via the breath and to a lesser extent the
kidney. Remaining tissues are grouped together on the
basis of their perfusion characteristics. In a complete
model each organ or set of organs has a designated volume,
blood flow, and tissue:blood partition coefficient [14].
ill
-------
NLIN, a nonlinear curve fitting routine incorporated into SAS software (SAS
Institute, Gary, NC). Initial estimates of the coefficients and exponents
were obtained via visual inspection of the data. These values were then
used in a iterative process to minimize the sum of squares in the model
being used at the time, i.e., one or two compartment. If no minimum was
found after 50 iterations, the model failed to converge and the values of
the exponents could not be estimated. Such a failure has little to do with
the initial estimates, but rather, reflects the poor fit of the data to the
model in question.
Mathematically, the time needed for the concentration to decrease by
one half is determined by the exponential term. The elimination half-life
is obtained by dividing this term (E) into the natural log of 2. The half-
lives for the two compartment model are found in the same manner using EI
and E2 independently. Both the alveolar and whole breath data were treated
in this manner. In addition, the first time point was eliminated from the
whole breath data and the decays resubjected to the NLIN curve fitting. If
substantially better fits were found with the first time point removed,
this would suggest that the lack of time resolution in the early phase
simply reduces the reliability of the predicted half-lives, especially if a
one compartment model is assumed. The nature of the decay associated with
a second compartment, and reflective of a second, longer elimination half-
life, might be adequately followed through the collection and analysis of
whole breath samples.
Tables 6-6 and 6-7 show the half-lives calculated for both alveolar and
whole breath, respectively. All of the compounds for which we could
measure decays are presented along with the experiment, measured exposure
air concentration, and study participant. Compound decays measured in more
than one experiment are presented together in decreasing order of exposure
concentration. They are also grouped according to compound class so that
the decay behavior associated with particular chemical features, if any,
could be more easily seen. Tables containing more complete information are
found in Appendix F. These tables include values of R2, which are
indicative of the goodness of fit for a particular model with a value of 1
representing a perfect fit, the 95% confidence interval for the half life
calculated from the confidence interval of the exponent, and an F test
comparison of the one and two compartment models.
112
-------
TABLE 6-6. DECAY PARAMETERS CALCULATED FROM ALVEOLAR BREATH DATA
One Compartment Model
Compound
Exposure
Cone.
ug/m3
Expt.
Code Participant Cj
One
Compart .
EI ti/z (h) Ci
Aliphatic Hydrocarbons:
n-Pentane
fl-Pentane
fl-Octane
fl-Octane
fl-Nonane
fl-Nonane
fl-Nonane
fl-Nonane
fl-Nonane
fl-Nonane
n-Oecane
fl-Decane
n-Oecane
fl-Decane
fl-Oecane
fl-Decane
jป-Undecane
3400
340
320
39
12000
210
210
180
130
110
14000
360
360
260
210
170
5600
GS1
WS1
GS1
HS2
GS1
HS2
HS3
HS1
HS4
HS5
GS1
HS2
HS3
HS1
HS4
HS5
GS1
1
1
1
2
1
2
1
2
3
4
1
2
1
2
3
4
1
126.0
14.04
7.91
2.40
175.5
8.25
7.09
14.46
19.28
3.87
165.2
22.49
16.50
30.64
31.96
18.39
127.0
0.0166
0.0100
0.0172
0.0132
0.00842
0.0102
0.0170
0.132
0.0552
0.0188
0.0086
0.0524
0.0691
0.129
0.0421
0.105
0.0412
0.70
1.15
0.67
0.87
1.37
1.13
0.68
0.08
0.21
0.61
1.35
0.22
0.17
0.08
0.27
0.11
0.28
Aliphatic Hydrocarbons:
Isopentane
2-Hethylpentane
2-Methylhexane
3-Methylhexane
3-Hethylhexane
2-Methyloctane
Ethylcyclohexane
10000
2000
340
410
39
5400
900
GS1
GS1
GS1
GS1
FS1
GS1
GS1
1
213.3
83.4
84.8
45.38
5.67
182.2
30.38
0.0177
0.0136
0.0450
0.0299
0.0276
0.0193
0.0129
0.65
0.86
0.26
0.39
0.42
0.60
0.89
Two Compartment Model
First
El t1/2 (h)
C2
Second Better
E2 ti/2 (h) Fit
Straight-Chain
146.7
8.81
6.87
1.65
250.1
8.48
5.77
17.05
32.68
CF<ซ
85.1
23.55
25.96
29.87
30.54
22.46
139.1
Branched
252.7
68.56
83.3
44.88
CF
149.5
23.26
0.137
0.175
0.0612
0.0678
0.477
0.189
0.0749
0.626
0.299
CF
0.0644
0.144
0.311
0.161
0.0605
0.221
0.155
Chain
0.142
0.0556
0.0891
0.0899
CF
0.0408
0.0621
0.08
0.07
0.19
0.17
0.02
0.06
0.15
0.02
0.04
CF
0.18
0.08
0.04
0.07
0.19
0.05
0.07
0.08
0.21
0.13
0.13
CF
0.28
0.19
61.2
10.96
3.00
1.22
153.2
5.98
3.39
4.79
5.79
CF
115.8
6.16
4.97
1.91
3.83
2.41
43.04
100.9
35.78
16.1
13.25
CF
53.00
15.09
0.00494
0.00557
0.00407
0
0.00688
0.00576
0.00561
0.0236
0.00756
CF
0.00495
0.00834
0.0110
0
0.00409
0
0.00849
0.00496
0.00363
0.00366
0.00455
CF
0.00466
0.00456
2.34 2
2.07 1
2.84 2
id3 NCC
1.73 2
2.01 2
2.06 2
0.48 2
1.53 2
CF NC
2.33 2
1.39 2
1.06 2
1C NC
2.82 1
1C NC
1.36 2
2.33 2
3.18 2
3.16 2
2.54 2
CF NC
2.48 2
2.53 2
-------
TABLE 6-6 (CONT'D.)
One Compartment Model
Compound
Exposure
Cone. Expt.
ug/m3 Code Participant Cj
One
Compart.
EI tj/2 (h) Cj
Two Compartment Model
First
EI tj/2 (h) C2
E2 t
Second
1/2
Better
Fit
Aromatic Hydrocarbons
Benzene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Ethylbenzene
Ethylbenzene
Ethylbenzene
Ethylbenzene
m.jj-Xylene
n.C-Xylene
m.fi-Xylene
B.fi-Xylene
n.Q-Xylene
ffl.fi-Xylene
o-Xylene
o-Xylene
fi-Xylene
430
5700
1200
640
640
510
460
320
280
2600
360
150
150
1600
1700
560
560
230
160
440
700
190
GS1
FS1
GS1
HS2
HS3
WS1
HS4
HS1
HS5
GS1
HS1
HS2
HS3
HS1
GS1
HS2
HS3
HS4
HS5
HS1
GS1
HS2
1
1
1
2
1
1
3
2
4
1
2
2
1
2
1
2
1
3
4
2
1
2
18.22
384.7
37.71
33.39
27.77
21.45
36.77
25.14
21.26
37.67
19.04
2.83
2.47
41.58
29.23
16.42
13.90
26.14
4.50
15.19
12.67
2.90
0.00688
0.0142
0.00627
0.00756
0.0109
0.00999
0.0103
0.0220
0.00705
0.00469
0.0550
0.00679
0.0113
0.0127
0.00721
0.0181
0.0255
0.135
0.0199
0.0465
0.0172
0.00717
1.68
0.82
1.84
1.53
1.06
1.15
1.13
0.52
1.64
2.46
0.22
1.70
1.02
0.92
1.60
0.64
0.45
0.08
0.58
0.25
0.67
1.61
12.10
295.7
30.81
15.04
19.19
CF
67.67
20.99
CF
23.2
17.36
3.08
1.14
18.81
CF
15.46
13.88
41.76
5.07
12.92
13.66
2.89
0.0855
0.116
0.223
0.172
0.138
CF
0.221
0.0441
CF
0.338
0.130
0.263
0.150
0.410
CF
0.0870
0.102
0.350
0.137
0.134
0.103
0.272
0.14
0.10
0.05
0.07
0.08
CF
0.05
0.27
CF
0.03
0.08
0.04
0.08
0.03
CF
0.13
0.11
0.03
0.08
0.08
0.11
0.04
12.69
231.3
31.35
29.54
20.80
CF
21.22
6.31
CF
34.92
4.34
2.34
2.04
36.09
CF
7.24
5.25
3.43
2.12
4.75
5.32
2.23
0.00342
0.00637
0.00438
0.00613
0.00687
CF
0.00285
0.00357
CF
0.00398
0.00545
0.00464
0.00806
0.0104
CF
0.00478
0.00537
0.00533
0.00546
0.00985
0.00393
0.00116
3.38
1.82
2.64
1.88
1.68
CF
4.05
3.23
CF
2.90
2.12
2.49
1.43
1.10
CF
2.42
2.15
2.16
2.12
1.17
2.94
9.95
2
2
2
1
2
NC
2
2
NC
2
2
2
1
2
NC
2
2
2
2
1
2
2
-------
TABLE 6-6 (CONT'D.)
One Compartment Model
Compound
Exposure
Cone.
ug/m3
Expt.
Code Participant C\
One
Compart.
EI tj/2 (h) Ct
Two Compartment Model
First
EI ti/2 (h)
C2
Second
E2 t1/2 (h)
Better
Fit
Haloaenated Hydrocarbons
Vinyl idene chloride
Dichloromethane
Dlchloromethane
Dlchloromethane
Oichloromethane
Dlchloromethane
Chloroform
1. . -Tr i chl or oe thane
1. . -Trlchloroethane
1. . -Trichloroethane
1. . -Trlchloroethane
1. . -Trichloroethane
1. , -Trlchloroethane
Tr ich loroethy lene
Tetrachloroethylene
Tetrachloroethylene
Tetrach loroethy 1 ene
56
5000
470
460
320
220
600
16000
340
200
200
200
140
77
280
190
150
WS1
FS1
HS1
HS3
HS4
HS5
SP1
WS1
HS1
HS2
HS3
HS5
FS1
FS1
HS1
HS4
HS5
1
1
2
1
3
4
2
1
2
2
1
4
1
1
2
3
4
12.27
299.7
64.62
26.17
45.20
23.11
69.44
5150.1
73.15
107.7
42.93
26.52
46.94
6.41
45.81
57.33
22.47
0.00388
0.0192
0.0283
0.0108
0.0177
0.006
0.0161
0.0131
0.00940
0.00269
0.0117
0.0034
0.0115
0.0176
0.00477
0.0137
0.00559
2.97
0.60
0.40
1.07
0.65
1.86
0.72
0.88
1.22
4.33
0.99
3.39
1.00
0.65
2.42
0.85
2.06
9.80
227.7
45.02
23.45
27.41
3.03
49.82
4316.7
46.76
12.33
36.14
10.82
30.56
4.70
14.64
40.79
CF
0.0937
0.0859
0.121
0.0147
0.142
0.0695
0.125
0.123
0.0903
0
0.0697
0.0697
0.145
0.058
0.0601
0.105
CF
0.12
0.13
0.10
0.78
0.08
0.17
0.08
0.10
0.13
0.00
0.17
0.17
0.08
0.20
0.18
0.11
CF
8.72
144.3
31.16
3.50
31.94
21.64
42.70
3223.4
47.09
95.43
22.18
22.01
33.65
2.53
37.54
37.08
CF
0.000996
0.00640
0.0108
0
0.0101
0.00559
0.00731
0.00608
0.00445
0.00303
0.00363
0.00190
0.00644
0
0.00311
0.00693
CF
11.60
1.80
1.07
1C
1.14
2.07
1.58
1.90
2 60
3.81
3.18
6.08
1.80
1C
3.70
1.67
CF
2
2
2
NC
2
1
2
2
2
1
2
1
2
NC
2
2
NC
aModel showing better fit based on the F-test at the 95* confidence interval. 1 = one compartment. 2 = two compartment.
bIC o data reflected insufficient change in concentration to calculate a second half-life over this time interval.
CNC ซ not calculated.
dCF " convergence failure; residuals failed to converge in 50 steps during iterative computation and reflects the poor fit of the data to the
model in question.
-------
TABLE 6-7. DECAY PARAMETERS CALCULATED FORM WHOLE BREATH DATA
One Compartment Model
Compound
Exposure
Cone . Expt .
ug/m3 Code Participant Cj
One
Compart .
EI ti/2 (h) Ci
Aliphatic Hydrocarbons;
n-Pentane
n-Octane
fl-Nonane
ri-Decane
ij-Undecane
3400
320
12000
14000
5600
GSI
GSI
GSI
GSI
GSI
104.7
9.25
264.4
175.58
38.24
0.0132
0.0122
0.0157
0.0131
0.0135
0.88
0.95
0.74
0.88
0.86
Aliphatic Hydrocarbons;
isopentane
2-Methylpentane
2-Methylhexane
3-Methylhexane
2-Methyloctane
Ethylcyclohexane
a-Pinene
Limonene
10000
2000
340
400
5400
900
97
160
GSI
GSI
GSI
GSI
GSI
GSI
CP1
CP1
185.5
51.3
28.4
28.53
134.4
1 21.17
2 26.26
2 5.35
0.0130
0.0113
0.0133
0.0131
0.0121
Cyclic
0.0116
0.877
0.2857
0.89
1.02
0.87
0.88
0.96
Two Compartment Model
First
El t1/2 (h)
C2
Second
E2 t1/2 (h)
Better
Fit
Straight-Chain
95.77
1.23
257.1
110.9
32.41
0.0443
0
0.0278
27.2
0.0594
0.26
0.00
0.42
0.00
0.19
46.13
9.03
49.8
175.6
21.88
0.00499
0.0190
0.00208
0.0131
0.00718
2.32
0.61
5.55
0.88
1.61
2
1
2
1
2
Branched-Cha i n
190.3
43.01
28.51
27.81
121.2
0.0472
0.0448
0.0398
0.0370
0.0204
0.24
0.26
0.29
0.31
0.57
76.7
26.82
9.996
9.77
28.40
0.00406
0.00514
0.00333
0.00324
0.00222
2.85
2.25
3.47
3.57
5.20
2
2
2
2
1
Hydrocarbons
0.99
0.79
2.43
19.51
4.10
3.19
0.0292
5.33
2.87
0.40
0.13
0.24
6.55
3.74
3.63
0.00174
0.433
0.1007
6.64
1.60
6.88
2
2
1
(continued)
-------
TABLE 6-7 (CONT'O.)
One Compartment Model
Compound
Exposure
Cone . Expt .
ug/m3 Code Participant Cj
One
Compart.
El *l/2 '") cl
Two Compartment Model
First
EI tj/2 (h)
C2
Second
E2 t1/2 (h)
Better
Fit
Aromatic Hydrocarbons
Benzene
Toluene
Toluene
Toluene
Ethylbenzene
Ethylbenzene
m.fi-Xylenc
Jfi'fi-Xylene
m.Q-Xylene
o-Xylene
o-Xylene
430
5700
1200
320
2600
360
1600
1700
240
440
700
GS1
FS1
GS1
HS1
GS1
HS1
HS1
GS1
FS1
HS1
GS1
1
1
1
2
1
2
2
1
1
2
1
24.44
293.5
41.90
13.70
40.10
6.24
21.21
24.56
7.28
4.91
8.83
0.00887
0.0112
0.00935
0.0113
0.00922
0.0121
0.0110
0.0109
0.0211
0.0124
0.00958
.30
.03
.24
.03
.25
0.95
1.05
1.06
0.55
0.93
1.21
19.16
216.8
20.81
CF<ซ
24.64
4.72
12.09
21.47
7.41
4.63
7.59
0.0250
0.0369
0.0370
CF
0.024
0.0470
0.0640
0.0223
0.0446
0.1322
0.0216
0.46
0.32
0.31
CF
0.48
0.25
0.18
0.52
0.25
0.08
0.53
10.26
145.1
28.93
CF
20.84
3.20
14.87
6.90
1.65
3.50
2.74
0.00280
0.00507
0.00620
CF
0.00471
0.00532
0.00719
0.00233
0.00460
0.00780
0.00192
4.12
2.28
1.86
CF
2.45
2.17
1.60
4.98
2.52
1.48
6.02
2
2
2
2
2
2
2
2
2
2
Haloaenated Hydrocarbons
Dichloromethane
Dichloromethane
1.1. 1-Tr Ichloroethane
1 . 1 . 1-Tr Ichloroethane
Tetrachloroethylene
ฃ-01 ch lorobenzene
5000
470
340
140
280
9400
FS1
HS1
HSi
FSI
HSI
CP1
1
2
2
1
2
2
212.6
48.95
49.55
31.34
35.96
309.9
0.0121
0.0207
0.00861
0.0105
0.00541
0.442
0.95
0.55
1.33
1.10
2.13
1.57
203.8
47.73
39.71
28.60
27.77
260.2
0.0284
0.0337
0.0137
0.0222
0.00685
1.30
0.40
0.33
1.38
0.52
1.68
0.53
54.66
7.11
10.58
7.38
6.93
103.3
0.00145
0.00213
0
0
0
0.0326
7.98
5.40
ICb
1C
1C
21.00
2
2
NC
NC
NC
2
'Model showing better fit based on the F-test at the 95* confidence Interval. 1 = one compartment. 2 = two compartment.
ฐIC = data reflected Insufficient change in concentration to calculate a second half-life over this time interval.
CNC " not calculated.
dCF = convergence failure; residuals failed to converge 1n 50 steps during iterative computation and reflects the poor fit of the data to the
model In question.
-------
Almost without fail, the two compartment model was better able to
accurately describe the measured decays. This is illustrated for the decay
of dichloromethane (experiment FS1) in alveolar breath and whole breath for
both the one compartment model, Figure 6-4, and the two compartment model,
Figure 6-5. In both cases, the actual data are shown as points on a In-
linear scale along with the similarly transformed theoretical equation that
appears as a solid curve. If the data were a perfect match to the
theoretical in a one compartment model (Fig. 6-4), all of the points would
fall on a straight line. This is clearly not the case for the dichloro-
methane data in either alveolar or whole breath. A perfect fit in the two
compartment case would result in the data falling exactly onto an
exponential curve. Figure 6-5 shows that the two compartment description
of the decay is a far better fit than was the one compartment case. The
differing curve shapes in the two compartment case for alveolar and whole
breath suggest that an inadequate definition of the first phase decay i.e.,
whole breath, alters the predicted half life.
The half-lives calculated for whole breath when the first data point
was removed from the set are shown in Table 6-8 for data from the garage
experiment. For the one compartment model, the removal of the first time
point resulted in the estimated half-lives becoming longer suggesting that
a failure to measure data from the early phase of the elimination can skew
the results. With the two compartment model, the reduction of the data set
size caused a significant number of convergence failures. As described
above, this implies that the data no longer fit a two compartment model
very well. Because the F test results with full data sets (Appendix F)
show that the two compartment model is generally superior to the one
compartment model, we can conclude that data points collected early in the
elimination decay are crucial to the accurate representation of the decay.
Observations Regarding the Dependence of Half Life on Exposure Level and
Study Participant--
One question we asked at the beginning of this study was whether or not
the measured half-life was dependent upon the level of exposure. This
question is particularly relevent if elimination half-lives are to be used
in a model to predict exposure based on post exposure breath measurements.
To answer this question, refer to the measured half-lives for toluene and
118
-------
One Compartment Fit
CHEMICAL-DCM METHOD-Alveolปr
1000
100
10
100 ฃ00
Minutes
soo
One Compartment Fit
CHEMICAL-DCM METHOD-Whole Breปth
1000
I
a
_0
5 100
10-
I
100
I
ฃ00
SOO
Minutes
Figure 6-4. Ln-linear display of decay data measured for dichloromethane
in alveolar (A) and whole (B) breath. The solid line indicates
a curve defined by data showing an ideal fit to a one compartment
model.
119
-------
Two Compartment Fit
OEMICAL4CM tCTMOOAlvvolcr
1000
100
10
0
100
coo
800
Minutes
Two Compartment Fit
CHEMICAL-DCM METHOD-Wholป Brปปth
1000
1
ฃ 100
10
100
too
800
Minutes
Figure 6-5.
In-linear display of decay data measured for dichloromethane
in alveolar (A) and whole (B) breath. The solid curve indi-
cates a curve defined by data showing an ideal fit to a two
compartment model.
120
-------
TABLE 6-8. COMPARISON OF CALCULATED HALF-LIVES FOR WHOLE BREATH DATA WITH AND WITHOUT
FIRST TINE POINT (GARAGE EXPERIMENT)
One
Coepartaent
Exposure Cone
Coapound ug/nr
Isopentane
Pentane
2-Methylpentane
2-Methylhexane
3-Methylhexane
Benzene
Toluene
Ethylcyclohexane
2-Methyloctane
Ethylbenzene
fi-Xylene
p.-Xylene
D-Octane
H-Nonane
jj-Oecane
jj-Undecane
10.000
' 2.000
1.200
550
340
250
740
590
3.800
1.500
1.000
420
320
7.100
8,200
3.200
* *l/2 tl/2
With Without
0.89
0.88
1.02
0.87
0.88
1.30
1.24
0.99
0.96
1.25
1.06
1.21
0.95
0.74
0.88
0.86
1.47
1.29
1.44
1.37
1.36
1.60
1.43
1.32
1.05
1.42
1.27
1.45
1.18
0.94
1.11
1.23
First ti/2
With
0.24
0.26
0.26
0.29
0.31
0.46
0.31
0.40
0.57
0.48
0.52
0.53
0.61
0.42
4 x 10~4
0.19
Two Conpartwnt
Second \\n First *\n Second tj/2
With Without Without
CF*
CF
CF
0.01
0.13
0.29
CF
0.12
0.12
CF
0.34
CF
2.9 x 10~4
6.7 x ID'5
0.17
0.67
2.85
2.32
2.25
3.47
3.57
4.12
1.86
6.64
5.20
2.45
4.98
6.02
CF
5.55
0.88
1.61
CF
CF
CF
1.37
2.31
2.79
CF
2.17
1.53
CF
2.64
NC
1.18
0.94
1.81
10.4
Exposure concentrations are approximate.
bCF ป convegence; residuals failed to converge 1n 50 steps during Interactive computation.
121
-------
dichloromethane of Table 6-6. No consistent correlation of half-life with
exposure level is observed. The data, however, are quite limited which
makes a definitive statement impossible. A lack of dependence on the level
of exposure would support the use of half-life in a predictive process.
Two other important questions are (1) what is the observed variability
in the measured half lives for a particular compound within one individual?
and (2) what is the observed variability between individuals for exposure
to the same compound? For those compounds which were measured in several
experiments, the results in Table 6-6 suggest that in some cases the intra-
and interindividual variability is small and in other cases the variability
is larger. Because of the limited number of observations, no firm
conclusions can be drawn. The fact that in many cases intra- and
interindividual variabilities were small suggests that further evaluations
are required. Experiments where several people are exposed several times
at several different levels could be designed to address this question.
Practical Results of This Work
Without question, one of the main results of this work is that
significant exposure to a variety of volatile organic compounds can occur
in a variety of everyday situations. Beyond this, we have demonstrated
that exposures are, in many cases, high enough to characterize elimination
decays of VOCs in breath. This is significant in that elimination half-
lives can be mesured without using exposure chambers which should allow
more widespread study of elimination kinetics.
The alveolar breath sampling device developed and used during this work
has also proven to be very useful. The ability to collect many samples in
rapid succession beginning just after exposure cessation greatly improves
the quality of the data needed to accurately represent the decay profile.
In addition, this device could be further developed so that it is rendered
more portable and even simpler to use than was the case in this work. Such
development has the capability of expanding the application of breath
measurements and its potential use as a noninvasive exposure assessment
tool.
Bivariate Curve Fitting Results
A knowledge of the kinetics of the elimination of a VOC from the body
through the breath can provide a foundation for the mathematical
122
-------
description of this process and its eventual use in predicting recent
exposure. Towards that end, we studied how well each data set fit each of
six bivariate equations encorporated into the software package "StatPlan
III" published by The Futures Group of Glastonbury, CT. In each case, the
time post-exposure at which the sample was collected was the independent
variable and the measured breath concentration of the particular VOC was
the dependent variable. The equations used are shown in Table 6-9. For
illustrative purposes, the fit of the alveolar n-pentane decay data from
the GS1 experiment is shown for each equation type in Figures 6-6 through
6-12. In each case the experimental data are represented as distinct
points along with the best possible curve permitted by an equation of that
type as a solid line. The value of R2, a measure of the goodness of fit,
is included for reference. For the case of this pentane decay, the power
function best described the observed curve.
The treatment of the decay data in this manner was done solely to study
how other mathematical descriptions might apply. Unlike the exponential
equations described above, these mathematical functions, to the best of our
knowledge, do not have a physical basis. This fact would not diminish the
ability of the function to describe the decay but would alter the manner in
which it was interpreted with regard to the physiological process.
The curves of best fit for the decays measured in alveolar air are
listed in Table 6-10. It should be stressed here that these equations all
assume a one compartment scenario. In all cases, the two compartment,
exponential equations discussed above provided a higher R2 value and,
hence, a better fit than these one compartment description. Each target
compound is listed along with the experiment in which it was measured and
the participant providing the data. The experiments are listed in
decresing order of exposure level to make any trends related to exposure
level more evident. The power, inverse concentration, and natural log
functions appeared most frequently as the best fit. The equation that
provides the best fit as measured by the R2 value can be deceptive insofar
as the predictive value of the curve is concerned. For example, Table 6-11
shows the residual (actual value - predicted value) as a percentage
difference from the actual value for 1,1,1-trichloroethane from experiment
WS1 (alveolar breath) for two curves. The inverse concentration function
indicated an R2 of 0.974 and the Ln function indicated an R2 of 0.973; each
123
-------
TABLE 6-9. MATHEMATICAL FUNCTIONS USED IN THE
BIVARIATE CURVE FIT ANALYSES
Curve Type Mathematical Description
Linear C = mt + b
Exponential InC = mt + b
Power InC = mint + b
Logarithmic C = mint + b
Inverse C 1/C = mt + b
Inverse t and C 1/C = m/t + b
Inverse t C = m/t + b
Where:
C = value of dependent variable (concentration)
t = value of independent variable (time)
m = slope
b = intercept
124
-------
:12C
QJ
0
ง 4C
I
100 200
Time (minutes)
300
Figure 6-6. Concentration of n-pentane in alveolar breath as a function
of time post exposure. Decay data fit to the linear func-
tion. R2 = 0.538.
125
-------
200
IK
5 120
en
3-
c
O)
c
O
i
-^i
40-
100 200
Time (minutes)
300
Figure 6-7. Concentration of ji-pentane in alveolar breath as a function
of time post?exposure. Decay data fit to the exponential
function. R = 0.803.
126
-------
Time (minutes)
Figure 6-8. Concentration of n-pentane in alveolar breath as a function
of time post exposure. Decay data fit for the power function,
R = 0.977.
127
-------
20Q
CT)
3.
160
1120
c
O)
u
c
o
o
40
U-T
100 200
Time (minutes)
300
Figure 6-9. Concentration of n-pentane in alveolar breath as a function
of time post?exposure. Decay data fit to the natural log
function. R = 0.919.
128
-------
"eiH
en
12C
o
4C
100 200
Time (minutes)
300
Figure 6-10.
Concentration of ฃ-pentane in alveolar breath as a function
of time post exposure. ^Decay data fit to the inverse con-
centration function. R = 0.959.
129
-------
200
-I
ro
E
^
en
120-
c
o
c
-------
200r
cn
-120
c
o
<0 I
-!->
OJ
U *fi
ง 4ฐ
(_)
I
100
200
300
Time (minutes)
Figure 6-12.
Concentration of n-pentane in alveolar breath as a function
of time post?exposure. Decay data fit to the inverse time
function. R = 0.920.
131
-------
TABLE 6-10. RESULTS OF STATPLAN BIVARIATE CURVE-FITTING SURVEY FOR ALVEOLAR BREATH SANPLES
Coapound
Isopentane
Pentane
Vinyl idene Chloride
2-Methylpentane
Dichloronethane
Chloroforn
1.1.1-Trtchloroethane
2-Nethylhexane
3-Hethylyhexane
Benzene
Trichloroethylene
Toluene
jt-Octane
Tetrachloroethylene
Ethylcyclohexane
3-Methyloctane
Ethylbenzene
g.fi-Xylene
Experinent
GS1
GS1
WS1
HS1
GS1
FS1
HS1
HS2>>
HS3
NS4
HSS
SP1
MSI
HS1
HS4&
HSS
HS2
HS3
FS1
6S1
GS1
GS1
FS1
FS1
GS1
HS2
HS3
MSI
HS4
HSS
HS1
6S1
HS1
HS4
HSS
GS1
GS1
GS1
HS1
HS2
HSS
GS1
HS1
HS2
HSS
HS4
HSS
Participant
1
I
1
1
1
1
2
2
1
3
4
2
1
2
3
4
2
1
1
1
1
1
1
1
1
2
1
1
3
4
2
1
2
3
4
1
1
1
2
2
1
2
1
2
1
3
4
Exposure Level8
(ug/m3)
10.000
3.400
440
56
2.000
>5.000
480
450
450
270
270
600
16.000
330
210
210
200
200
120
340
406
427
13
5.700
1.200
640
640
510
370
370
320
320
260
170
170
900
5.400
2,610
470
150
150
1.600
1.700
570
570
190
190
Best Fit
Power
Power
Inv. cone.
Ln
Ln
Ln
Inv. cone.
Ln
Inv. cone.
Ln
Exponential
Ln
Inv. cone. (In)
Ln
Inv. tine
Power
Ln
Power
Ln
Power
Power
Ln
Ln
Ln
Ln
Inv. cone.
Inv. cone.
Inv. cone.
Inv. tine
Ln
Inv. cone.
Power
Inv. cone.
Ln
Inv. time
Ln
Ln
Inv. cone.
Power
Inv. cone.
Inv. cone.
Exponential
Exponential
Inv. cone.
Inv. cone.
Inv. tine
Ln
R?
0.971
0.977
0.718
0.863
0.964
0.983
0.995
0.956
0.977
0.995
0.939
0.987
0.974 (0.973)
0.996
0.955
0.817
0.916
0.987
0.993
0.926
0.982
0.949
0.966
0.982
0.969
0.965
0.990
0.954
0.979
0.880
0.967
0.965
0.952
0.983
0.840
0.981
0.971
0.961
0.934
0.923
0.963
0.961
0.944
0.933
0.967
0.985
0.875
(continued)
132
-------
TABLE 6-10 (cont'd.)
Compound
ฃ-Nomne
ฃ-Xylene
ji-Decane
ji-Undecane
Experiment
GS1
HS2
H53
HS1
H54
HS5
G51
HS1
HS2
GS1
HS2
HS3
HS1
H54
HS5
GS1
Participant
1
2
1
2
3
4
2
1
2
1
2
J
2
3
4
1
Exposure Level
(ug/ซ3)
12.020
200
200
160
120
120
440
701
200
13.800
330
330
280
190
190
5.600
Best Fit
Inv. cone.
Power
PoNer
Power
Inv. tine
Ln
Ln
Power
Inv. tine
Ln
Inv. cone.
Inv. tine
Inv. cone.
Power
Inv. tine
Power
R2
0.983
0.960
0.956
0.989
0.983
0.900
0.911
0.973
0.974
0.955
0.929
0.989
0.980
0.921
0.989
0.991
'Exposure levels for garage expeMoent (GS1) as approximate.
bSignifleant exposure occurred during the night before the exposure experiment.
133
-------
TABLE 6-11. COMPARISON OF PREDICTIVE ABILITIES OF TWO FUNCTIONS FOR
THE DECAY OF 1,1,1-TRICHLOROETHANE IN ALVEOLAR BREATH
(EXPERIMENT WS1)
% Difference from Measured
Time Post-Exposure Inverse Concentration Ln
(min) (R2 = 0.974) (R2 = 0.973)
3 30 6
8 13 -0.6
18 2 -5
28 -20 -23
38 6 5
54 -1 -1
69 -8 -8
98 -2 0.3
134 -6 -0.008
176 -2 11
218 6 28
134
-------
provides more accurate predictions in different portions of the curve. The
inverse concentration function clearly performs better at longer times
while the Ln function handles the early time points better. Some of the
time points are very accurately predicted. The elevation in breath
concentration measured at 28 minutes, presumably related to a second
physiological compartment, is not effectively predicted by either function.
From this we can conclude that the predictive power of each function cannot
be gleaned from R2 alone and that more complex mathematical functions will
be required to very accurately predict multicompartment systems.
The analogous results for the whole breath data are shown in Table
6-12. As for the half-life determinations, the whole breath data were
first subjected to the curve fitting analysis with all of the data points
included and then with the first time point eliminated from the data set.
When all of the data points were included in the analyses, the most
frequently selected curves were power, Ln, and inverse concentration. When
the first point was eliminated, inverse concentration and inverse time
became the dominant functions. This supports the idea that the early time
points are very important in accurately defining the elimination of an
organic compound from the body. Table 6-13 presents the % difference of
the predicted value from the actual value for the benzene decay of
experiment GS1 for whole breath (all data points and without the first
point) and alveolar breath. The comparison of actual vs. predicted
concentration values for whole breath indicated that the best-fit equation
could predict the actual values quite well. Through the elimination of the
first data point, the values were predicted with only a 4% deviation
compared to the 8% for the case when all points were included but such an
analysis clearly fails to provide information on the early-phase
elimination. The alveolar data indicate that as the number of data points
increases and the resulting curve contains more subtleties, the
mathematical functions required to accurately define the curve become more
complex.
135
-------
TABLE 6-12. RESULTS OF STATPLAN BIVARIATE CURVE-FITTING SURVEY FOR WHOLE BREATH SAMPLES
Compound
Isopentane
D-Pentane
2-Hethylpentane
OlchloroMthane
l.l.I-Trlchloroethane
2-Methylhexane
3-Hethylhexane
Benzene
Toluene
fl -Octane
Tetrachloroethylene
Ethyleyelehexane
3-flethyloctane
Ethylbenzene
f.B-Xylene
ji-Nonane
ฃ-Xylene
jj-Decane
ji-Undecane
o-Pinene
D.-01eh]orobenzene
LlMnene
Experiment
651
6S1
GS1
FS1
HS1
HS1
FS1
6S1
GS1
GS1
FS1
GS1
HS1
GSI
HS1
GSI
GSI
GSI
HS1
HS1
GSI
HS1
GSI
GSI
CP1
CP1
CP1
Participant
1
1
1
1
2
2
1
1
1
1
1
1
2
1
2
1
1
1
2
2
1
2
1
1
2
2
2
Exposure Level*
5000
480
330
120
342
406
427
5700
1,240
320
319
260
590
3,800
2.610
470
1.600
12.800
440
13.800
5.600
95
10.000
160
Best Fit
(All)
Power
Inv. cone
Ln
Ln
Power
Ln
Ln
n
rower
Power
Inv. cone.
Inv. cone.
Ln
Ln
Ln
Ln
Ln
Ln
Ln
Ln
Ln
Inv cone.
Ln
Inv. cone.
Inv. cone.
Ln
Power
Power
R'
0.983
0.985
0.966
0.957
0.963
0.972
0.982
0.965
0.970
0.991
0.997
0.988
0.967
0.966
0.965
0.981
0.973
0.990
0.981
0.988
0.987
0.989
0.998
0.996
0.997
0.967
0.881
Best Fit
(Less 1st pt.)
Power
Inv. cone.
Inv. tine
Inv. tine
Inv. tine
Inv. tine
Power
Inv. time
Inv. t1ซe
ป-. i
rower
Inv. cone.
Inv. cone.
Inv. cone.
Inv. cone.
Inv. flaw
Inv. tine
Inv. tine
Inv. cone.
Power
Ln
Inv. tine
Exponential
Inv. cone.
Inv. cone.
Ln
Power
Inv. tine
R2
0 972
0 981
0.952
0.967
0 987
0 947
0.967
0.965
0.982
0.995
0.996
0.985
0.932
0.950
0.915
0.989
0.985
0.989
0.966
0 969
0 992
0.993
0 998
0.994
0.998
0 988
0.837
Exposure levels for garage experiment (GSI) are approximate.
136
-------
TABLE 6-13. EFFECT OF DATA SET COMPLETENESS ON PREDICTIVE ABILITIES OF
FITTED BIVARIATE CURVES FOR BENZENE
(EXPERIMENT GS1)
Time Post-Exposure
(min)
3
8
12
16
25
30
42
48
60
69
76
107
111
136
140
181
185
227
232
% Difference from
Whole
(All Points)a (Less
_d
-
8
-
-
8
-
-4
-
-0.9
-
-
-0.9
-
-0.6
-
-2
-
+4
Measured
Whole
First
-
-
_e
-
-
-2
-
-3
-
3
-
-
4
-
-3
-
-2
-
-0.2
Alveolar
Point)b (All Points)c
6
-12
-
3
8
-
-22
-
6
-
2
9
-
2
-
3
-
3
-
ainv. cone.; R2 = 0.991.
bpower; R2 = 0.967.
CLn; R2 = 0.947.
dNot collected.
ฃData point not used in this analysis.
137
-------
REFERENCES
Wallace, L. A., "Total Exposure Assessment Methodology (TEAM) Study:
Summary and Analysis," Volume I, EPA Final Report Contract No. 68-02-
3679, August, 1986.
Pellizzari, E. D., K. Perritt, T. D. Hartwell, L. C. Michael, C. M.
Sparacino, L. S. Sheldon, R. Whitmore, C. Leninger, H. Zelon, R. W.
Handy, and D. Smith, "Total Exposure Assessment Methodology (TEAM)
Study: Elizabeth and Bayonne, New Jersey, Devils Lake, North Dakota
and Greensboro, North Carolina," Volume II, EPA Final Report Contract
No. 68-02-3679, 1986.
Pellizzari, E. D., K. Perritt, T. D. Hartwell, L. C. Michael, C. M.
Sparacino, L. S. Sheldon, R. Whitmore, H. Zelon, R. W. Handy and D. J.
Smith, "TEAM Final - Volume III: Total Exposure Assessment
Methodology (TEAM) Study: Elizabeth and Bayonne, New Jersey, Devils
Lake, North Dakota, and Greensboro, North Carolina," prepared for U.S.
Environmental Protection Agency, Contract No. 68-02-3679, Office of
Research and Development, Washington, DC, 1986.
Pellizzari, E. D., L. C. Michael, K. Perritt, D. J. Smith, T. D.
Hartwell, and J. Sebestik, "Comparison of Indoor and Outdoor Toxic Air
Pollutant Levels in Several Southern California Communities," Final
Report for EPA Contract No. 68-02-4544, August 12, 1988.
Pellizzari, E. D., K. W. Thomas, D. J. Smith, R. L. Perritt, and M. A.
Morgan, "Total Exposure Assessment Methodology (TEAM): 1987 Study in
New Jersey," Final Report for EPA Contract No. 68-02-4544, March 15,
1989.
Gordon, S. M., L. A. Wallace, E. D. Pellizzari, and H. J. O'Neill,
"Human Breath Measurements in a Clean-Air Environment to Determine
Half-Lives for Volatile Organic Compounds," Atmos. Environ., 22, 2165-
70, 1988.
Pellizzari, E. D., K. W. Thomas, S. D. Cooper, and C. S. Smith, "Pilot
Study for Volatile Organics in Blood and Breath," Draft Final Report
for EPA Contract No. 68-01-7350, June 30, 1989.
138
-------
8. Handy, R. W., D. J. Smith, N. P. Castillo, C. M. Sparacino, K. Thomas,
D. Whitaker, J. Keever, P. A. Blau, L. S. Sheldon, K. A. Brady, R. L.
Porch, J. T. Bursey, and E. D. Pellizzari, "Standard Operating
Procedures Employed in Support of an Exposure Assessment Study,"
Volume IV, RTI Final Report, 2392/00-12F for U.S. EPA Contract No. 68-
02-3679, 1985.
9. Thomas, K., S. Cooper, R. Dishakjian, and E. Pellizzari, "Breath
Measurements of Individuals Exposed to Chemicals During Personal
Activities," Part II: Analytical Protocols for U.S. EPA Contract No.
68-02-4544.
10. Cramer, P. H., K. E. Boggess, and J. M. Hosenfeld, "Volatile Organic
Compounds in Whole Blood - Determination by Heated Headspace Purge and
Trap Isotope Dilution GC/MS," EPA Report EPA-650/5-87-008, July, 1987.
11. Smith, C. and E. Pellizzari, "VOC Breath Measurement Study:
Optimization and Validation of Blood Analysis Protocol," Final Report
for EPA Contract No. 68-02-4544, May, 1989.
12. Pellizzari, E. D., J. Raymer, K. Thomas and S. Cooper, "Breath
Measurements of Individuals Exposed to Chemicals During Personal
Activities," Part I: Study Design, Draft Work Plan, for U.S. EPA
Contract No. 68-02-4544.
13. Smith, D. J. "Breath Measurements of Individuals Exposed to Chemicals
During Personal Activities," Part III: Quality Assurance Project
Plan, prepared for U.S. EPA Contract No. 68-02-4544, July 25, 1989.
14. Anderson, M. E. "A Physiologically Based Toxicokinetic Description of
the Metabolism of Inhaled Gases and Vapors: Analysis at Steady
State", Toxicol. Appl. Pharmacol, 60, 509-26, 1981.
139
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APPENDIX A
INITIAL FEASIBILITY STUDY FOR AN ALVEOLAR SPIROMETER
A-l
-------
RTI/140/01 April, 1989
VOC BREATH MEASUREMENT STUDY: ALVEOLAR BREATH METHOD
FINAL REPORT
by
J. Raymer, K. Thomas, S. Cooper, and E. Pellizzari
RTI Work Assignment Leader: E. D. Pellizzari
Task 1 Leader: J. Raymer
Research Triangle Institute
Research Triangle Park, NC 27709
Contract Number: 68-02-4544
Work Assignment No. 11-40, Task 1
Project Officer: David 0. Hinton
Atmospheric Research and Exposure Assessment Laboratory
Exposure Assessment Research Division
Environmental Monitoring Branch
Task Manager: W. C. Nelson
Atmospheric Research and Exposure Assessment Laboratory
Exposure Assessment Research Division
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NC 27711
A-2
-------
RTI/140/01
April, 1989
VOC BREATH MEASUREMENT STUDY: ALVEOLAR BREATH METHOD
FINAL REPORT
by
J. Raymer, K. Thomas, S. Cooper, and E. Pellizzari
RTI Work Assignment Leader: E. D. Pellizzari
Research Triangle Institute
Research Triangle Park, NC 27709
Contract Number: 68-02-4544
Work Assignment No. 11-40, Task 1
Project Officer: David 0. Hinton
Task Manager: W. C. Nelson
Author:
J.y Raymer
Task Leader
Approved by:
E. D. PellizzarT
Project Director
PREPARED FOR
United States Environmental Protection Agency
Research Triangle Park, NC 27711
A-3
-------
DISCLAIMER
This document is a preliminary draft. It has not been formally
released by the U.S. Environmental Protection Agency and should not at this
stage be construed to represent Agency policy. It is being circulated for
comments on its technical merit and policy implications.
Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
A-4
-------
CONTENTS
Page
Disclaimer A-4
Fi gures A-6
Tables A-7
1. Introduction and Background A-8
2. Conclusions A-12
3. Recommendations A-13
4. Experimental A-14
Effect of Tube Dimension and Sampling Flow Rate on
Preservation of Alveolar Air Plug A-14
Mode of Sampling A-17
Determination of Alveolar C02 Concentration and Its
Dilution in Whole Breath A-17
Precision Studies A-19
Recoveries of Organic Test Compounds Through Newly-Designed
Exhale Valve A-23
5. Results and Discussion A-28
Effect of Tube Diameter and Sampling Flow Rate on
Preservation of Alveolar Air Plug A-28
Mode of Sampl ing A-31
Determination of Alveolar C02 Concentration A-34
Precision Studies A-34
Recoveries of Organic Test Compounds Through Newly-Designed
Exhale Valve A-38
References A-43
A-5
-------
FIGURES
Number Page
A-l Schematic diagram of the device used to study effects of
tube diameter and sampling flow rate A-15
A-2 C02 profile with continuous sampling A-18
A-3 Device used to test precision based on syringe samples A-20
A-4 Device as configured for precision study based on
canister sample A-22
A-5 Exhale valve and sample port A-24
A-6 Device used to generate synthetic breath for recovery
studi es A-25
A-7 Forward profile of m/z 44 (C02) with time and repetitive
breathing A-29
A-6
-------
TABLES
Number Page
A-l Concentrations of Target Compounds in the Primary Standard...A-26
A-2 Effect of Tube Diameter and Sampling Rate on Alveolar Air
PI ug A-30
A-3 Fraction of Alveolar Air Sampled As A Function of Type of
Breathing, Breathing Rate and Continuous Sampling A-33
A-4 Determination of Alveolar C02 Concentration and Dilution of
Alveolar Air in Whole Breath A-35
A-5 Results of Syringe Sampling A-36
A-6 Canister Precision Study Results A-37
A-7 GC/MS Peak Heights from Analyses of Zero (Z) Level Canisters.A-39
A-8 Recoveries of Target Compounds at Low (4.4 ng/L) Level A-41
A-9 Recoveries of Target Compounds at High (36 ng/L Level) A-42
A-7
-------
SECTION 1
INTRODUCTION AND BACKGROUND
For nearly a decade, the U.S. EPA has been conducting studies of per-
sonal exposure to volatile organic compounds (VOCs) [1-3]. Participants in
these studies have also provided breath samples which have confirmed actual
exposure. For a few chemicals, e.g., 1,1,1-trichloroethane, trichloro-
ethylene, tetrachloroethylene, p_-dichlorobenzene, m.p-xylenes and
ethyl benzene, correlations have been demonstrated between a person's
activity, his/her personal exposure and breath levels [1]. Consequently,
two general questions have arisen: (a) what are the common personal
activities which may lead to elevated VOC exposure, and (b) can breath
measurements provide a quantitative measurement of VOC exposure?
The collections of exhaled air for the determination of levels of
organics in the studies mentioned above were made using a dual Tedlar bag
spirometer. This device consists of a 40 L Tedlar bag, which holds clean,
humidified, inhale air, connected through a mouthpiece assembly containing
unidirectional flow valves, to a 40 L Tedlar bag which collects the whole
breath provided by the subject. During sample collection, the subject
draws air through the inhale bag and exhales into the Tedlar exhale bag
through the one-way, Tedlar flap valve. Whole breath from this bag is then
pumped out through a Tenax cartridge, which adsorbs the organic compounds
present in the sample, for later analysis.
Except for demonstrating actual exposure through breath monitoring,
little is known concerning personal activities and sources of VOCs which
are responsible for exposure. Recently, a study was conducted in Northern
New Jersey to examine the impact of activities such as dry cleaning
clothes, smoking, home renovations, driving a car into an attached garage
and use of room deodorizers on VOC levels in personal and indoor air [4].
Results from this study indicate that some VOC levels become elevated in
some cases during these activities. In many cases, however, elevated
levels of VOCs were observed which could not be explained entirely by the
A-8
-------
activities described above. Further research is needed to establish
plausible links between sources and elevation of VOCs.'
An interesting corollary question is - can breath measurements predict
the VOC exposure level? The ability to use breath measurement data jm lieu
of personal monitoring would circumvent the participant burden experienced
with personal monitoring and provide an alternative to blood collection and
analysis, an invasive technique, for determining body burden. Currently
employed models, however, which relate breath to the immediate periods of
exposure are imprecise or need to be validated. The VOC residence time in
the body is not well described in the literature for non-occupational
situations, a parameter which is important in perfecting prediction models.
To address the above issues, research on breath monitoring techniques
and breath monitoring during selected exposure situations was undertaken.
The first two phases of this effort have been recently completed. First, a
VOC canister based breath sampling method was validated. The addition of a
canister technique to the spirometer method for breath sampling has expan-
ded the spectrum of VOCs which may be collected and anlayzed from breath,
specifically for VOCs with high vapor pressures and low breakthrough
volumes on Tenax GC.
Secondly, a VOC exposure-breath montioring study in a clean-air chamber
was conducted to produce high exposure to VOCs during usage of selected
consumer products. This study provided an opportunity to (a) evaluate the
canister based sampling method for breath, (b) compare blood-breath
measurements, (c) calculate residence times for VOCs, and (d) demonstrate
that some personal activities may lead to elevated VOCs in breath. Parti-
cipants underwent presumed exposure, followed by post-exposure breath
sampling over an extended period of time (greater than 8 hours). Results
of this study indicate a successful accomplishment of the objectives [5]
for some of the chemicals.
The chamber study, however, was only a first step in achieving these
objectives, since several chemicals (e.g. dichloromethane, chloroform,
vinylidene chloride, n-octane, n-decane, n-dodecane, etc.) were not suffi-
ciently elevated to allow either a comparison of blood-breath levels, or a
demonstration of the canister's ability to collect and preserve these
chemicals from breath.
A-9
-------
In addition, the desire to collect breath samples more rapidly and to
use these to define early phase decay, requires the development of
methodology for collection of alveolar air. The development of such a
methodology is the subject of this report.
The device developed during the project is based on a simple open tube.
Breath exhaled from the study participant is allowed to enter a Teflon open
tube, rather than a Tedlar bag through a one-way valve where it is stored
until the next exhalation. The breath is sampled into a canister through a
sampling port just downstream of the exhale valve, i.e., breath is drawn
from the tube into the canister. Because the last portion of breath to be
exhaled is alveolar air, all of the breath collected after the initial
passage of the deadspace air until the next exhalation is alveolar air. It
is this alveolar air which has the highest levels of any compound which
partitions from the blood into the alveolar sac and, hence, would be
reflective of environmental exposure. A device of this sort will allow the
rapid collection (in approximately one minute) of the breath so that
detailed kinetic information regarding the elimination of the compound from
the body can be obtained. This collection time compares favorably to the
spirometer system, currently in use, where sample collection can take
upwards of 15 minutes and limit the number of data point for a given study.
The ability to collect breath samples quickly is only one of the goals
of this development effort. Another goal is that the device be miniatur-
ized so that field transport is not a problem. The ability to bring the
sampling device to the subject with a minimal effort will allow the
acquisition of samples representing the earliest eliminations and provide
the best resolution for characterization of the decay process. The other
goal, which is consistent with the miniaturization, is that of simplicity.
Although simplicity is not a prerequisite for usefulness, a device which is
difficult to use and requires a fair degree of knowledge and skill will not
be widely utilized and this will limit its impact. Throughout the
development of this device, ease of use was always a main consideration.
Several experiments or groups of experiments were designed to answer
questions critical to the optimal performance of the device. Starting from
the concept of a breath collection system based on an open tube, the
dimensions of this tube were studied with regard to the preservation of a
high level C02 "plug" as determined by monitoring the COz level with a mass
A-10
-------
spectrometer (MS). The effect of sample collection flow rate into a
canister was also studied here. Second, having decided upon the optimal
dimensions of the tubing, the fraction alveolar air collected using
continuous sampling into a canister was studied. Several breathing rates
and breath volumes were studied. Third, the precision of replicate breath
samples was studied as a function of sample collection time. Finally, the
recoveries of organic compounds through the newly-designed exhale valve
were determined. Each of these considerations is presented, in turn, in
the following sections.
A-ll
-------
SECTION 2
CONCLUSIONS
Work performed under this task has shown that a miniaturized breath
sampling device is feasible and quite simple to operate. The device col-
lects a portion of exhaled breath from a 0.5 inch internal diameter open
tube through a sampling port, located very near the place where the breath
enters the tube, into a 2 L canister. Unidirectional flow valves control
air flow as in the current spirometer. Carbon dioxide measurements showed
that greater than 95% of the breath sampled continuously into a canister at
3 L/minute is alveolar in origin. When breath was sampled continuously
into a canister at a flow of 1.5 L/minute, this value increased to 97+%.
The ability to sample and collect such high fractions of alveolar air
without the need to open and close a valve to the canister greatly
simplified the method. Using the described device and 2 L canisters with
inlet flow rates of 1.5 L/minute, it was shown that sufficient sample for
analysis could be collected in one minute. The collection of breath volumes
larger than the anticipated alveolar volumes is unlikely under these
conditions. In addition, when sampling sequential breaths from a single
subject, the device can be ready to collect the next sample in only a
minute or two. Such a short sampling time when combined with a rapid
exchange of the sampling canister will allow for detailed descriptions of
decay kinetics. The concentrations of organic compounds in the breath
collected with the new device were higher than are those in whole breath,
as in the currently used spirometer. Recoveries of a variety of organic
compounds at both 4.4 and 36 /ig/m3 were found to average 101% and 96%,
respectively, with no indications of cross-contamination between streams
with the different concentrations of organic compounds.
A-12
-------
SECTION 3
RECOMMENDATIONS
Given the success of phase one of this work (proof of concept and pre-
liminary validation), field comparisons to the current spirometer and
further validation studies are recommended. The validation studies should
include an expansion of the target chemical list to include other compounds
of interest and the utilization of 1 L canisters for sample collection.
The smaller canister volume will contribute to the compact nature of the
device as well as reduce the bulk of the canister samples to be shipped to
the laboratory for analysis. Furthermore, the device should be refined to
optimize the compact nature and resultant packaging to maximize portability
while at all times keeping simplicity as a prime concern. Finally, the
device as used here required a source of clean air for inhalation;
alternatives should be investigated. For example, a small filter and
battery powered pump might allow the use of ambient air rather than having
to depend on an inhale bag filled at a location other than the exposure
site. Such alternatives will optimize the portability and utility of the
device.
A-13
-------
SECTION 4
EXPERIMENTAL
EFFECT OF TUBE DIMENSION AND SAMPLING FLOW RATE ON PRESERVATION OF ALVEOLAR
AIR PLUG
The first step in the development of the alveolar air sampling device
based on sampling from an open tube is to consider the effects of gaseous
diffusion and sampling rate on the preservation of the "plug" of exhaled,
alveolar air. Once the tube is filled with exhaled breath, diffusion of
both the alveolar air (high carbon dioxide level) and deadspace air (low
carbon dioxide level) begins with the result that the C02 concentration
gradient between the two regions becomes more shallow with time. The opti-
mal geometric configuration will minimize the diffusion and maintain a
distinct C02 concentration "step change." In this regard, a small diameter
tube should better maintain the alveolar air plug than a larger diameter
tube which allows for more diffusion because of its larger cross sectional
area.
The rate at which the exhaled, alveolar air is sampled is also impor-
tant; the optimal sampling rate is expected to be dependent on the internal
diameter of the tube. In this case, laminar flow is an issue and should
cause more profile distortion in narrow tubes than in wide tubes and at
fast flow rates compared to slow flow rates. For the experiments described
here, we used both 0.5 and 1.0 inch i.d. Teflon tubing to hold the exhaled
breath, and sampling flow rates of 1.2, 2.3, and 3.3 L/minute. A
laboratory worker served as the source of the exhaled breath. Carbon
dioxide levels were monitored with a mass spectrometer.
The device used in these experiments is shown, in a general sense, in
Figure A-l and consisted of a custom Teflon mouthpiece connected through a
1 inch ball valve to the custom Teflon sampling port/tubing adapter, the
Teflon tubing to contain the exhaled air, a Precision Dynamics three-way
solenoid valve, a Tylan flow meter, and a Thomas double diaphram pump
connected through a 2 L ballast and a needle valve to provide the desired
flow rate. Two tubing adapters were used, one for 0.5 inch tubing and one
A-14
-------
Mouth-
piece
Ball
Valve
Tubing adapter and
sampling port
Teflon Tube, 0.5 or 1" i.d.
Sampling
Port
To MS
"forward"
\
1 1
r n r n n
f 3 way S' ' "I!
Solenoid ( Flow Needle
t Meter Valve
To MS
"reverse"
' rUIUp
21
Ballast
Figure A-l- Schematic diagram of the device used to study effects of tube
diameter and sampling flow rate.
A-15
-------
for 1 inch tubing. They were identical up to the point of decreasing
diameter for connection to the Teflon tubing. A small fraction of air was
sampled continuously for C02 using an 1KB mass specrometer connected,
through the direct probe inlet, to the device via a 170 cm section of 50 /im
i.d. fused silica tubing (dimensions of which were chosen to maintain a
vacuum of 3 x 10-5 torr in the mass spectrometer). The sweep time of the
fused silica tube transfer line was 6 seconds. That is, there was a delay
of six seconds after C02 passed the end of the tube before an increased
level of C02 was measured in the mass spectrometer. The actual
configuration was dependent on the experiment in progress and will be
described at the appropriate time.
In order to describe the degree to which the alveolar profile is
preserved, the alveolar air profile into the device must first be
characterized. In this case, the silica transfer line was inserted into
the sampling port until it was flush with the interior flow path of the
adapter fitting. The three way solenoid was used to isolate the pumping
system from the collection system, i.e., essentially a no sampling
situation. The breath donor breathed repeatedly (inhalation through nose,
exhalation through mouth) into the device without removing his mouth from
the mouthpiece while the mass spectrometer was set to continuously monitor
m/z 44, the parent ion for CO?. Each breath profile was studied closely
and the slope (intensity change per scan) of the linear portion of the C02
increase was determined. The value obtained for each tube diameter was
termed "Input (forward) slope."
The next experiment studied how well the input profile was preserved by
the device as a function of both sampling flow rate and tube diameter. For
this experiment, the fused silica line was moved to the port downstream of
the three way solenoid valve, as shown in Figure 4-1, and the flow rate was
set using the needle valve as the pump drew in air through the unconnected
leg of the solenoid. The "forward" port was closed. After the subject
exhaled, he simultaneously closed the ball valve and activated the solenoid
so that air was now pumped from the 0.5 or 1.0 inch Teflon tube. In this
case, a rapid increase in the C02 level was observed as the last portion of
the alveolar air exhaled was drawn past the silica MS inlet tube. This
elevated C02 level was observed until the first portion exhaled was drawn
A-16
-------
past the inlet to the MS whereupon the C02 level returned to baseline.
Four breaths were studied in each case.
MODE OF SAMPLING
The determination of the fraction of alveolar air collected was accom-
plished in the following manner. The participant was asked to breathe
repeatedly into the device (Figure 4-1), by inhaling through the nose and
exhaling through the mouth into the mouthpiece. Breathing rate was consci-
ously controlled by the subject with the aid of audible timers. In
addition, the participant was asked to control breath volume to the best of
her ability. The C02 levels were monitored with the mass spectrometer with
the fused silica MS inlet connected to the port labeled "Reverse" while the
pump drew air from the device at two flow rates. Before each experiment,
i.e., each breathing rate, volume, and sampling flow, several single
breaths were given and sampling was started after the exhalation. The
sampling was continued until the C02 level returned to baseline. Through a
knowledge of the sampling flow rate, the apparent alveolar volumes were
calculated.
After it was clear that the participant was breathing appropriately for
a given experiment, repeated breaths were given and sampling was started
after the first breath and continued for 1.5-2 minutes. The type of
information obtained from the mass spectrometer is shown in Figure 4-2
which shows the result of slow and shallow breathing with continuous (3 L/-
minute sampling. The total area (positive) under the curve between the
user-defined points (indicated by arrows in Figure A-2) was determined
using the MS data system software as were the areas of the "dips" corres-
ponding to the passage of deadspace air (negative areas). The absolute
value of the sum of all of the dips was added to the total area and divided
into the absolute area sum of the dips. This value is the fraction of the
area corresponding to the contribution of deadspace air. This value was
then subtracted from 1 to obtain the fraction of alveolar air sampled.
DETERMINATION OF ALVEOLAR C02 CONCENTRATION AND ITS DILUTION IN WHOLE
BREATH
The purpose of this study was two-fold. First, the concentration of
C02 in alveolar air was needed to allow the preparation of standards for
task 3 of this project as well as for the later validation experiments in
A-17
-------
23
50 75
Scan Number
let*
L25
Figure A-2. CO- profile with continuous sampling.
A-18
-------
the current task. Second, the C02 concentration in whole breath needed to
be determined so that claims to the superiority of the open tube sampling
device could be justified.
For this experiment, five different people provided at least three
breaths into the open tube device, with the fused silica inlet to the mass
spectrometer in the same position as for the characterization of the
forward profile. The plateau ion current intensity of m/z 44 for each
breath was determined, i.e., the ion current given by room air was
subtracted, and the values were averaged. Breaths from two of the
participants were also collected in a Tedlar bag; the silica transfer line
was placed into the bag and a small amount of whole breath was drawn into
the mass spectrometer to determine the response of the diluted alveolar
air. It was assumed that the breath in the Tedlar bag was uniformly mixed.
For the estimation of the C02 concentration, the average ion intensities
for each subject were compared to the ion intensities observed, using the
same measurement system, of 6% C02 in air.
PRECISION STUDIES
Syringe Sampling
One of the intended uses of the miniaturized breath collection device
is for kinetic studies to determine the elimination half lives of organic
compounds from the body. Because the early phase of elimination can be
very rapid, the ability to collect and analyze single breaths would be an
advantage. Towards this end, we investigated the constancy of the levels
of both C02 and an organic (toluene) in breath using 100 ml gas syringes
(Precision Sampling Corp.) for sample collection from the new device. In
addition, a Tedlar bag was filled with breath and air was withdrawn into a
canister which was analyzed to determine the dilution of the organic in
whole breath.
The device used for this experiment is shown in Figure A-3 and is basi-
cally one-half of the spirometer currently in use. The exhalation part of
the spirometer was modified by attaching the newly designed collection
system to the outlet of the mouthpiece union through a 1 inch ball valve
which was used to isolate the Teflon tube/sampling part from the mouthpiece
for the single breath experiments. During the experiment, study
participant, who had been working with toluene, breathed normally from the
A-19
-------
Air Line from Tank
Mouthpiece Union and One-Way Valves
Mouth Bit
Figure A-'3. Device used to test precision based on syringe
samples.
A-20
-------
inhale bag and, after an exhalation, closed the ball valve and a 100 ml
sample was withdrawn through the sampling port while the subject continued
to exhale through his nose. Each sample was derived from one breath.
After the sample was collected, the valve was reopened and the process was
repeated until a total of six samples was collected. All six samples were
collected within a few minutes during which time the subject exhaled 37
breaths. Immediately following the syringe sampling, a Tedlar bag was also
filled and a 6 L sample transferred to a canister to allow a comparison of
alveolar and whole breath levels.
The collected samples were analyzed the same day by slowly expelling
the contents of the syringe through a length of Nafion tubing to remove
water, and into a cryotrap held at -150*C to focus the contents for gas
chromatographic/mass spectrometric (GC/MS) analysis. This was a
modification of the method developed for the analysis of breath samples
from canisters [5]. The canister was analyzed as described in reference
5. Both carbon dioxide and toluene were quantified.
Canister-Based Sampling
We also chose to test the precision of the system configured in a
manner similar to the way in which it would be used in the field, i.e.,
continuous breathing and continuous sampling into a 2 L canister. In order
to test the reliability of the sample if the number of breaths integrated
during collection was not constant, we collected triplicate canisters at
three different flow rates using the device shown in Figure A-4. Using
three different flow controlling orifice giving flow rates of 2.31, 1.63,
and 0.99 L/minute, and sampling times of 39 s, 55 s, and 91 s, respecti-
vely, a 1.5 L volume was delivered into all of the 2 L canisters. This
volume was chosen to allow replicate GC/MS analyses of the same sample; the
method requires that the canister be approximately 75% full for reliable
replicate analyses. The use of 2 L canisters makes this situaiton possible
in a minimal time and will allow for kinetic studies of organics in breath.
The experiment was performed as follows. First, the volunteer
participant worked with toluene and dichloromethane for 30 minutes and then
waited for 45 minutes to allow the initial decay to occur. At the sampling
device, the participant took five breaths from the clean air inhale bag
before beginning the three collections at the highest flow rate. Each
A-21
-------
Air Line from Tank
Plug Valve
Mouthpiece Union and One-Way Valves
Flow
Controlling
Orifice
Sample
Collection CanisteT
Figure A-4. Device as configured for precision study based on
canister sample.
A-22
-------
collection was begun at the end of an exhalation for greatest reproduci-
bility. The three collections at each of the other two flow rates were
then made as above while the subject continued to inhale clean air.
following the triplicate collections, one breath sample was collected into
a canister at each flow rate in sequence, starting with the slowest flow to
be opposite to the order above. Finally, a Tedlar bag was filled and 1.5 L
of this whole breath was transferred to a 2 L canister at the intermediate
flow rate. Aliquots of the contents of each canister were then analyzed
via GC/MS as before.
RECOVERIES OF ORGANIC TEST COMPOUNDS THROUGH NEWLY-DESIGNED EXHALE VALVE
In the conventional, dual Tedlar bag spirometer, the Tedlar flap valves
(one way valves) can often fail to seal or fail to open resulting in an
inoperable device. These valves cannot be easily checked before starting
sample collection and, once found to be the problem, correction requires
partial dissassembly of the spirometer mouthpiece and a delay in sample
acquisition. This can be very inconvenient if rapid sample collection for
kinetic studies is an issue. As a result, we have investigated an
alternate design as shown in Figure A-5. It is constructed entirely of
Teflon and operates by a Teflon ball which seats in a conical opening and
permits flow in only one direction. Stainless steel screws, isolated from
the flow path, are used to hold the top plate in place and allow for easy
disassembly. The valve has been heated to over 100'C with no adverse
effect on its operation. This last aspect is of importance because of the
need to have a design which permits sterilization of the valve between
different participants.
The recovery experiment was carried out using the device shown in
Figure A-6. For several hours prior to the start of the experiment, the
standard containing 4.8% C02 in air was allowed to bubble through the
controlled temperature impingers to humidify the stream and to bring the
C02 concentration in the water to equilibrium. After humidification, the
gas stream passed by the outlet of a pressurized fortification canister,
the flow from which was controlled by a Tylan flow controller, to receive
known amounts of the target compounds (Table A-l) into the stream. After
the gas stream was thoroughly mixed, part of it was sampled into a
verification canister, to provide a reference for recovery calculations,
A-23
-------
Breath
Flow
___ _____
Side View
>
ro
(S)
(D
Top View
Side view, sample port coming in
from opposite side.
Breath
*
Flow
i" i.d. Teflon Tube
o.d. Stainless Steel Sampling Port
0
Figure A-5. Exhale valve and sample port.
-------
I
no
en
4.8% CO,
In Air'
Gas Mixing
Bulb
Flow
Controlling
Controller Orifice
Constant Temperature
Bath 37 C
Verification
Canister
Flow
Controlling
Orifice
Sample
Collection Canister
.Exhale valve
.Teflon tube
Figure
A- & Device used to generate synthetic breath for recovery studies,
-------
TABLE A-l. CONCENTRATIONS OF TARGET COMPOUNDS IN THE PRIMARY STANDARD
Compound Prim. Std. Cone. (ng/mL @ STP)
Vinyl chloride 39
Isopentane (2-methylbutane) 17
Vinylidene chloride 20
n-Pentane 17
Dichloromethane 21
2-Methylpentane 18
Chlorofonn 24
1,1,1-Trichloroethane 22
Carbon tetrachloride 17
Benzene 19
Trichloroethylene 24
n-Octane 19
Toluene 19
n-Nonane 19
Tetrachloroethylene 17
Ethyl benzene 19
2-Xylene 19
Styrene 20
o-Xylene 19
n-Decane 20
A-26
-------
before passing through a 1 inch i.d. Teflon elbow which held the new exhale
valve. The gas stream exiting the valve was collected in the sample
canister. The sample canister was connected directly to the sampling port
of the valve. The 2 L canisters were each filled for 60 seconds using the
21 ga. orifice which permitted a flow of 1.5 L/minute. All of the tubing
and the mixing chamber up to the Teflon elbow were heated to 37*F. The gas
flow into the new exhale valve was 5.45 L/minute as determined by the flow
meter and verified downstream through periodic checks with a bubble flow
meter during the course of the experiment.
The approximate concentration of each target compound in the primary
standard was 20 ng/mL and was bled into the gas stream at a flow rate of 0,
1.15, or 9.45 mL/minute to yield final concentrations for each compound of
approximately 0, 4,4, or 36.3 ng/L (/jg/m3). For convenience, these levels
were termed zero, low, and high. These levels were introduced into the
stream in the order zero, low, high, low, zero, high, and low to elucidate
any potential problems with sample carry-over. The system was swept only
briefly after changing the level before beginning the sampling. In a field
application, this would be equivalent to having the participant provide a
few breaths into the device prior to the collection of the sample. The
canisters were analyzed as described in reference 5.
A-27
-------
SECTION 5
RESULTS AND DISCUSSION
EFFECT OF TUBE DIAMETER AND SAMPLING FLOW RATE ON PRESERVATION OF ALVEOLAR
AIR PLUG
Output from the mass spectrometer (MS) for the determination of the
forward COz profile in the 0.5 inch i.d. tube is shown in Figure A-7. The
rapid increase in C02 level associated with the beginning of the alveolar
air is clearly visible for each breath as are the "dips" which are
associated with the passage of deadspace air over the silica tube with each
new exhalation. The forward slope for both tube diameters are listed in
Table A-2.
The rate at which the profile returned to baseline (Reverse C02 Slope)
was indicative of the diffusion and mixing within the Teflon tube and the
connecting tubing up to the point of the MS inlet. Because only the Teflon
tube was changed at any given flow, changes in the slope observed upon
changing tube diameters were caused by the Teflon tubing itself. An
ideally preserved profile would have a slope equal to and opposite in sign
from the input slope. The slopes compiled in Table A-2 clearly show that
the profiles are better preserved using the smaller tube and fast sampling
flow rates. As a result, it was decided that the 0.5 inch i.d. tube would
be used to contain the exhaled breath. The data also show that a sampling
flow as fast as possible should be used to preserve the profile. There are
several considerations other than the profile preservation which needed to
be considered before deciding on the "best" sampling flow; these are the
subject of this section.
A-28
-------
File UNI FomrJ C02 Profile, Snail Bore Me
R/Ztt
J1CJ
a
T
1/1
01
O)
O-
^J^ ...I,,. ...I I I I I I I...
Scan Number
Figure A-7. Forward profile of m/z^ 44 (CCL) with time and repetitive
breathing.
A-29
-------
TABLE A-2. EFFECT OF TUBE DIAMETER AND SAMPLING RATE
ON ALVEOLAR AIR PLUG
Input (Forward) Slope = 132 (17% RSD)
Large (1 inch) Tube n = 10
Sampling Rate (L/Min)
1.2
2.3
3.2
Slope (% RSD) n
-2.5 (23)
-4.4 (13)
-6.1 (22)
= 4
Input (Forward) Slope = 111.7 (19% RSD)
Small (0.5 inch) Tube n = 10
Sampling Rate (L/Min) Slope (% RSD) n = 4
1.2 -13.6 (10)
2.3 -22.7 (5)
3.2 -31.3 (9)
A-30
-------
MODE OF SAMPLING
Introduction
One of the goals of this project was to develop a device which samples
exhaled breath and collects predominately alveolar air. Two modes of
breath collection are possible with the device described in Section 4. The
first is continuous sampling where breath is continuously drawn into the
canister as the participant repeatedly exhales. This mode would be expec-
ted to collect some of the deadspace air in addition to the alveolar air.
The second mode is the pulsed mode of sampling in which sampling is inter-
mittent and is timed such that collection is allowed to occur only after
the passage of the deadspace air for each breath. This mode would be
expected to provide the highest fraction of alveolar air in the collected
breath. The work described in this section deals with the determination of
the fraction of alveolar air collected under a variety of breathing and
sampling conditions using constant sampling.
At this point, the recall of some terms relevant to the physiology of
respiration are needed. The "tidal volume" is the volume of air inspired
and exspired with each normal breath and is equal to approximately 500 ml
in the normal young adult male. Of this 500 ml, approximately 150 ml is
termed "deadspace air" and is air which filled the nasal passages, the
pharynx, the trachea, and the bronchi, and never entered the alveoli. The
"inspiratory reserve volume" is the extra volume and is usually equal to
approximately 3000 ml in the young adult male. The "expiratory reserve
volume" is the amount of air that can be exhaled by forceful expiration
after the end of the normal tidal expiration. This value is typically
1100 ml in the young adult male. The "residual volume" is the volume of
air still remaining in the lungs after the most forceful expiration and
this volume averages 1200 ml in the young adult male (6). All of these
volumes are 20 - 25% lower in the female. With a "normal" breath, the
fraction alveolar air in whole breath is expected to be 1 - (150/500) or
0.7. Although the deadspace volume remains constant, it is clear that if
the participant draws on the reserve volumes, the resulting fraction of
alveolar air would increase. This possibility was considered during the
course of these experiments.
A-31
-------
Results
Different types of breathing were investigated because of the variety
of types found in actual sampling situations. A normal breathing rate is
considered to be 12 breaths/minute yet there are extremes which could be
encountered and, as a result, information on the fraction of alveolar air
collected is required so that potential problem situations can be identi-
fied. The results of this series of experiments are summarized in Table A-
3 from which several conclusions can be drawn. First, greater than 95%
alveolar air was sampled in each situation and that at a flow rate of 1.5
L/minute, the fraction of alveolar air was 97+%. Thus, if the device was
used to sample a person breathing at a rate of 15 breaths/minute and using
a sampling flow of 1.5 L/minute, the alveolar volume would have to be below
100 ml for oversampling to occur. Such a small alveolar volume is unlikely
in a healthy person and, even if such a small volume were encountered, the
subject's rate naturally would be much faster to compensate for the small
volume. Therefore, pulsed sampling would provide no real improvement and,
given the goal of simplicity of the device design and operation, would
actually be a hindrance because of the extra mechanical devices required.
The information about the apparent alveolar volumes indicates that when
a person breathes into a device which does require some exertion, be it
from this device or the currently used spirometer, some of the lung's
reserve volume capacity is drawn upon. This is actually a benefit with
either device as it makes more alveolar air available for collection with
the open tube design and dilutes the deadspace air when sampling into a
Tedlar bag with the current spirometer system.
The measured fraction was much higher than would be expected using the
assumptions of an average volume for a young adult male of 500 mL/breath
with 150 ml of that from deadspace air. In addition to the reserve
volumes, as discussed above, we feel that discrimination against sampling
the deadspace air arises from the air velocity during exhalation. The open
tube device under study here samples at a constant rate and, if the breath
is exhaled at a constant velocity, the fraction of alveolar air to be
expected is approximately 85%, assuming 150 ml deadspace and 770 ml alveo-
lar volume. From this, it is apparent that the exhalation velocity is not
constant but rther the initial portion of the exhalation, which includes
the deadspace air, passes over the sampling port much more quickly than the
A-32
-------
TABLE A-3. FRACTION OF ALVEOLAR AIR SAMPLED AS A FUNCTION OF
TYPE OF BREATHING, BREATHING RATE AND CONTINUOUS SAMPLING
Measured Fraction of Alveolar Air
Breathing Type
Breathing
Rate
Avg.
Alveolar
Volume
XRSD 1.5 L/mln
Number of Breaths
Integrated
3.0 L/mln
Number of Breaths
Integrated
Fast and shallow 30/mln 9 359 mL 28X 98.6%
Normal 12/min 6 776 mL 29! 97.8%
Slow and shallow 15/mln 4 454 mL 6X 97.1%
Long 6/mln 5 770 mL 1% 97.9X
17
21
15
95.8%
97. OX
97.4%
97.7X
6
18
20
24
A-33
-------
alveolar air, with the result that it is under-sampled in proportion to its
volume contribution. This is a major benefit to the open tube device
because such velocity differences make no difference when whole breath is
collected into a Tedlar bag.
DETERMINATION OF ALVEOLAR C02 CONCENTRATION
The results of this experiment are shown in Table A-4. From the data
it can be seen that the average C02 concentration in alveolar air was 4.8%.
The fraction of alveolar air in whole breath was determined to be 0.75 for
one donor (female) and 0.88 for donor #2 (male). These values are greater
than the literature fraction (350/500) of 0.7 and, again, is suggestive of
some use of the reserve capacity [6].
PRECISION STUDIES
Syringe Sampling
The results of this experiment are shown in Table A-5. The variability
of the toluene peak is quite large, particularly in view of the time dura-
tion of the experiment. Thirty seven breaths seems little enough time to
result in a 30% decrease in the measured toluene level, especially since 40
minutes were allowed to elapse after exposure before starting the breath
collections. That is, the initial, rapid decrease in the breath levels
should have passed and the decay over the time of this experiment would
have been expected to be much slower. In addition, the results of the
analysis of the air captured in the canister from the Tedlar bag indicate
that toluene was present at a level of 0.92 the alveolar value, which is
greater than expected, and that the apparent level of C02 increased in
whole breath. These inconsistencies suggested problems with the analytical
method and our comparisons between the syringe samples and the canister
sample. Because the syringe collection method had not been validated, its
performance was questioned as was the dissimilar manner in which the
syringe and canister samples were treated. As a result, we chose to repeat
the experiment using canisters for the collections of all samples. Each
was filled to the same extent so that analysis variations would be
minimized. This work is described in the next section.
Canister-Based Sampling
The results of this experiment are presented in Table A-6. It is ap-
parent that the levels of both dichloromethane and toluene decreased
throughout the course of the experiment with the triplicate samplings.
A-34
-------
TABLE A-4. DETERMINATION OF ALVEOLAR CO? CONCENTRATION AND DILUTION OF ALVEOLAR AIR
IN WHOLE BREATH
Donor
1
2
3
4
5
6X C02
Number of
Breaths (n)
3
3
7
3
3
-
Average Intensity at Plateau of
E/z 44 In Alveolar Air C02 Cone. In
(XRSD) Alveolar Air
27,128 (2X)
32,200 (0.5%)
29,200 (8%)
24,551 (435)
29,341 (4X)
35,180 (n=1)
4.6X
5.4%
4.9X
4. IX
4.9X
_a
Intensity of C02
In Whole Breath Fraction Alveolar Air
(Tedlar) In Whole Breath
20,380
27,720
_a
_a
_a
_a
0.75
0.88
_a
_a
_a
_a
Average Alveolar C02 Concentration = 4.8X (10% RSD)
aNot applicable.
A-35
-------
TABLE A-5. RESULTS OF SYRINGE SAMPLING
Breath Number
6
12
17
22
27
37
Tedlar Bag Sample
(100 ml)
C02 Area (m/z 44)
3.4 x 105
3.4 x 105
3.7 x 105
3.6 x 105
3.6 x 105
3.7 x 105
x = 3.6 x 105
%RSD =3.5
3.7 x 105
Toluene Peak Height (m/z 62)a.b
15,494
12,819
13,647
15,427
11,699
10,907
x = 13,332
%RSD = 13
12,265
am/z 62 was used because of saturation of m/z 91, a more intense ion.
bpeak height in arbitrary units.
A-36
-------
TABLE A-6. CANISTER PRECISION STUDY RESULTS
Sampling Time
Triplicates
39s
55s
91s
Sequential
91s
55sฐ
55s
(second analysis)
39s
Whole Breath (55s)
Time of
Sample Collection
After Start of Exp.
0-4:26
6:32-10:35
13:18-18:24
21:43
24:42
26:52
30:50-33:14
Average Peak Intensitya (%RSD)
Dichloromethane
10953 (6.8)
8764 (1.8)
7694 (12)
6759
6003
6100
6333
5525
Toluene
21734 (10.1)
17885 (3.7)
14926 (4.4)
14794
19125
19341
13434
10841
^Arbitrary units, n = 3.
^Canister suspected to be contaminated, values were excluded.
A-37
-------
This continued decrease was seen in the sequentially collected canisters as
well. The fact that this trend continued, despite a reversal in the
sequence of flow rates, suggests that the measured concentration decreases
were real and not dependent on sampling flow rate. If the average of the
39 s and 91 s sequential canister values from Table A-6 are taken for each
compound, the relative standard error estimates (n=2) are 4.6% for
dichloromethane and 6.8% for toluene. These lie well within the
variabilities observed for the triplicate canisters (shown in Table A-6)
and support our conclusions regarding the independence of measured
concentration on the sampling flow rate. The sequential canister sample
for 55 s was suspected to be contaminated as there were a great many
chromatographic peaks containing m/z = 57 (alkane). Canister samples
collected at 91 s and 39 s showed no such contamination. The contents of
this canister were also analyzed a second time and the same extraneous
peaks were observed. Consequently, the values were not included in the
calculations.
Upon comparison of the whole breath peak heights to those obtained by
averaging the sequential alveolar samples at 39 and 91 seconds, the
dilution observed in whole breath relative to alveolar air (fraction of
alveolar air) was 0.84 for methylene chloride and 0.77 for toluene. These
values compare well to those determined for C02 above. Although the C02
values were acquired from two donors, the organic dilutions were obtained
from one person and the resulting different dilutions may be the result of
differing solubilities of the organic compounds in the moist, mucous
membranes of the airways. An increased solubility and later release ("off-
gassing") could result in apparent lower dilution factors for more soluble
compounds. These dilutions are also higher than the theoretical 0.7,
supporting the hypothesis that some of the reserve capacity is used during
sample donation.
RECOVERIES OF ORGANIC TEST COMPOUNDS THROUGH NEWLY-DESIGNED EXHALE VALVE
The results of the zero level canister analyses are shown in Table A-7,
and indicate there was a problem with contamination of some of the canis-
ters, especially the verification canister collected at 35:08 past time
zero (to). The values shown represent raw peak height of the mass chroma-
tograms. Low levels of benzene and dichloromethane are often seen as low
A-38
-------
TABLE A-7. GC/MS PEAK HEIGHTS FROM ANALYSES OF ZERO (Z) LEVEL CANISTERS
Compound
Isopentane
D-Pentane
D-Octane
H-Nonane
D-Decane
Tetrachloroethylene
Trlchloroethylene
Vinyl Idene chloride
1,1,1-Trlchloroethane
Vinyl chloride
2-Methylpentane
Benzene
Carbon tetrachlorlde
Chloroform
Dlchloromethane
Toluene
Ethyl benzene
a-Xyiene
fl-Xylene
Styrene
Ion d/z]
57
57
57
57
57
59
60
61
61
62
71
78
82
83
84
91
91
91
91
104
I tg Zero Sample
0
0
0
0
55
0
0
0
0
0
0
416
0
0
241
0
0
0
0
0
t0 Zero Verlf .
462
5104
0
0
0
0
0
0
0
0
0
179
0
49
125
0
0
0
0
0
35:08 Z Sample
0
47
0
0
44
0
0
0
0
0
0
339
0
0
0
0
0
0
0
0
35:08 Z Verif.
185
999
0
44
88
0
51
0
135
0
0
541
0
2054
537
210
0
76
0
0
A-39
-------
level contaminants in the analytical system when sampling from a clean
canister filled with alveolar air. This contamination reemphasizes the
importance of knowing the history of the canisters to be used in a sampling
effort and the importance of extensive background checks. These canisters
had been used to sample stack gases.
The calculated recoveries ("sample" peak height/"verification" peak
height) are summarized in Tables A-8 and A-9 for the low level and high
level tests, respectively. For the low level recoveries, one of the three
sample canisters was quite contaminated containing high levels of vinyl
chloride, benzene, ethylbenzene, xylenes, and styrene. As a result, this
collection was excluded from the summary table. Carbon tetrachloride was
not found in one of the samples because of the low MS response typical for
this compound, so the indicated recovery is derived from one analysis. The
xylenes and styrene were excluded from the average recovery value because
of the large variabilities which are consistent with low-level contamina-
tion, already known to be a problem. Overall, the recoveries are quite
good and there was no evidence of sample carry-over. The high level
recoveries showed much better overall precision, as would be expected. It
is interesting to note that vinylidene chloride, 1,1,1-trichloroethane,
vinyl chloride, benzene, carbon tetrachloride, chloroform, and dichloro-
methane all showed recoveries in the 79-88% range. The reason for this is
not clear.
A-40
-------
TABLE A-8. RECOVERIES OF TARGET COMPOUNDS AT
LOW (4.4 NG/L) LEVEL
Compound Average % Recovery
Isopentane
n-Pentane
n-Octane
n-Nonane
n-Decane
Tetrachloroethylene
Trichloroethylene
Vinyl idene chloride
1,1, 1-Tri chl oroethane
Vinyl chloride
2-Methylpentane
Benzene
Carbon tetrachloride
Chloroform
Dichloromethane
Toluene
Ethyl benzene
p_-Xylene
o-Xylene
Styrene
Average Recovery
% RSD of Avg.
95.9
99.1
93.9
82.6
97.0
102.7
107.1
103.6
96.6
97.6
98.5
107.6
97.6*
99.7
89.8
112.2
133.5
136.0*
111.9*
244.0*
101.1% (Excluding "*")
11%
% RSD
7
25
2
20
28
2
2
5
3
4
10
5
_a
8
6
7
2
8
35
46
*This recovery determined from one value only.
A-41
-------
TABLE A-9. RECOVERIES OF TARGET COMPOUNDS AT
HIGH (36 NG/L) LEVEL
Compound
Isopentane
n-Pentane
n-Octane
n-Nonane
n-Decane
Tetrachloroethylene
Trichloroethylene
Vinylidene chloride
1,1, 1-Trichloroethane
Vinyl chloride
2-Methylpentane
Benzene
Carbon tetrachloride
Chloroform
Dichloromethane
Toluene
Ethyl benzene
2-Xylene
o-Xylene
Styrene
Average
% RSD of
Average % Recovery
97.2
98.5
103.6
102.1
104.0
101.9
104.5
88.8
92.7
90.9
92.2
89.6
88.3
88.5
87.1
96.2
99.3
102.3
103.4
92.8
Recovery 96.2%
Avg. 6.4%
% RSD
1.3
2.7
7.4
3.0
4.7
3.0
4.5
15.0
11.0
4.4
1.0
14.5
9.3
15.5
11.0
2.9
1.0
5.5
4.3
13.6
A-42
-------
REFERENCES
1. "Total Exposure Assessment Methodology (TEAM) Study: Summary and
Analysis," Volume I, Lance A. Wallace, EPA Final Report, August, 1986.
2. "Total Exposure Assessment Methodology (TEAM) Study: Elizabeth and
Bayonne, New Jersey, Devils Lake, North Dakota and Greensboro, North
Carolina," Volume II, E. D. Pellizzari, K. Perritt, T. D. Hartwell, L.
C. Michael, C. M. Sparacino, L. S. Sheldon, R. Whitmore, C. Lininger,
H. Zelon, R. W. Handy and D. Smith, EPA Final Report, 1986.
3. "Total Exposure Assessment Methodology (TEAM) Study: Selected
Communities in Northern and Southern California," Volume III, E. D.
Pellizzari, K. Perritt, T. D. Hartwell, L. C. Michael, R. Whitmore, R.
W. Handy, D. Smith and H. Zelon, EPA Final Report, prepared for U.S.
Environmental Protection Agency, Office of Research and Development,
Washington, DC, 1986.
4. "Total Exposure Assessment Methodology (TEAM) Study: 1987 Study in
New Jersey," E. D. Pellizzari, K. W. Thomas, D. J. Smith, K. Perritt,
and M. A. Morgan, EPA Final Report on Contract No. 68-02-4544, in
preparation.
5. "Methods for Volatile Organics in Blood and Breath: Chamber Study,"
Final Report on EPA Contract No. 68-01-7350, in preparation.
6. Basic Human Physiology; Normal Function and Mechanisms of Disease.
2nd Edition, A. C. Guyton, pp. 393-438. Copyright 1977 by W. B.
Saunders Co., Philadelphia, PA.
A-43
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APPENDIX B
REFINEMENT, TESTING, AND CONSTRUCTION OF A
A PORTABLE ALVEOLAR SPIROMETER
B-l
-------
RTI/150/01/01F September 30, 1989
DEVELOPMENT OF AN ALVEOLAR SAMPLING DEVICE
DRAFT FINAL REPORT
by
J. H. Raymer, K. W. Thomas, S. D. Cooper,
D. A. Whitaker, and E. D. Pellizzari
RTI Work Assignment Leader: J. H. Raymer
Research Triangle Institute
Research Triangle Park, NC 27709
Contract Number: 68-02-4544
Work Assignment Number 11-50
Project Officer: David 0. Hinton
Atmospheric Research and Exposure Assessment Laboratory
Exposure Assessment Research Division
Environmental Monitoring Branch
Task Manager: W. C. Nelson
Atmospheric Research and Exposure Assessment Laboratory
Exposure Assessment Research Division
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
B-2
-------
RTI/150/01
September 30, 1989
Submitted by:
DEVELOPMENT OF AN ALVEOLAR SAMPLING DEVICE
DRAFT FINAL REPORT
by
J. H. Raymer, K. W. Thomas, S. D. Cooper,
D. A. Whi taker and E. D. Pellizzari
RTI Work Assignment Leader: 0. H. Raymer
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, NC 27709-2194
Contract Number: 68-02-4544
Work Assignment Number: 11-50
Project Officer: David 0. Hinton
Task Manager: W. C. Nelson
Approved by:
J.H. Raymer '
Work Assignment Leader
E. D. Pellizz^Vi
Project Director
PREPARED FOR
United States Environmental Protection Agency
Research Triangle Park, NC 27711
B-3
-------
DISCLAIMER
This document is a preliminary draft. It has not been formally
released by the U.S. Environmental Protection Agency and should not at this
stage be construed to represent Agency policy. It is being circulated for
comments on its technical merit and policy implications.
Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
B-4
-------
ABSTRACT
A portable spirometer, suitable for field use, and designed to sample
primarily alveolar breath in under two minutes resulted from this research.
Six devices were manufactured for use in breath sampling studies. Collec-
tion of breath samples into 1.8 L Sumrna polished canisters will allow for
at least four or five replicate GC/MS analyses from each canister. Trial
use of a prototype device demonstrated its applicability to the collection
of organic compounds present in breath at concentrations ranging from low
ppb to ppm levels. This suggests great potential for application to breath
analysis in both ambient and occupational environments. The use of organic
vapor respirator cartridges to filter inhalation air used for removed all
of the test compounds except dichloromethane to levels below the quantita-
tion limit (QL) of the analytical method. Detected dichloromethane levels
were generally not much greater than the QL. It is not known if the detec-
tion of this compound represents emission from the filter or if it was
background from the laboratory environment in which the analyses were
performed. Dichloromethane was retained by the filter up to a volume of
320 L after which breakthrough was detected. Thus, for the compounds tes-
ted, each filter can be used to provide up to 320 L of clean air before
replacement is required, two filters are used in each spiro- meter.
Recoveries of test organic compounds from the device at the 5 ppb level
ranged from 89 to 112% with the exceptions of n-dodecane and 4-phenylcyclo-
hexene. At the 50 ppb level, recoveries ranged from 91 to 109% with the
exceptions of n-dodecane and 4-phenylcyclohexene. The results indicated no
significant problem from either adsorption or carryover at these levels.
B-5
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CONTENTS
Page
Abstract B-5
Figures B-7
Tables B-8
1 Introduction and Background B-9
2 Conclusions B-ll
3 Recommendations B-12
4 Experimental B-13
Sources of Air for Inhalation B-13
Choice of Optimal Canister Size B-21
Additional Recovery Studies B-23
Portable Spirometer Design B-28
5 Results and Discussion B-32
Sources of Air for Inhalation B-32
Choice of Optimal Canister Size B-36
Additional Recovery Studies B-40
Portable Spirometer Construction B-43
References B-53
B-6
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FIGURES
Number Page
B-l Schematic diagram of the analytical system used for the
analysis of canister air or breath samples B-15
B-2 Synthetic breath generator including verification canister
and switching valves prior to spirometer B-24
B-3 Portable spirometer for the collecting of VOCs in alveolar
breath B-44
B-4 Exhale valve and sample port B-50
B-7
-------
TABLES
Number Page
B-l Analytical Conditions for Canister Sample Analysis B-16
B-2 List of Target Compounds for Evaluating the Effectiveness
of Respirator Cartridges B-19
B-3 Target Compounds for Adsorptive Loss and Carryover
Experiments B-25
B-4 Sample Collection Regimen for the Adsorptive Loss
Experiments B-27
B-5 Sample Collection Regimen for the Carryover Experiments B-29
B-6 Estimated Quantifiable Limits for Target Compounds for
Canister Air Analyses Using MID B-33
B-7 Concentrations (/
-------
SECTION 1
INTRODUCTION AND BACKGROUND
Methods that determine the concentrations of volatile organic compounds
(VOCs) in human breath as indicators of environmental exposure are attrac-
tive both because the sample collection procedure is noninvasive and
because those compounds that can be measured in breath are indicative of
actual exposure. Such measurements should better reflect body burden than
the presumed exposure information derived from air measurements. Despite
the potential of breath analysis for exposure evaluation, it is not rou-
tinely used for exposure monitoring. Two main factors have been identified
as contributing to the limited use of breath sampling and analysis (1).
First, data interpretation is difficult. The relationships between breath
concentrations and exposure levels are not clear, especially for environ-
ments with fluctuating VOC concentrations. In addition, there is limited
information on the magnitude, origin, and significance of individual varia-
tions in VOC concentrations. Second, reliable and simple field methods are
rare. Without a simple method for routine application, the studies needed
to address the exposure level/breath level correlations and other issues
will not be forthcoming. How we have addressed the methodological aspects
of breath collection to build a portable spirometer system is the subject
of this report.
Work performed under EPA Contract 68-02-4544, WA 40, Tasks 1 and 3,
demonstrated that the alveolar breath sampling device, partially developed
during Task 1, is capable of collecting principally alveolar air into an
evacuated canister in a short time, approximately one minute. This device
was subsequently used in Task 3 to help define the elimination of VOCs from
the body after exposure to microenvironments. Although the device
developed and applied in Tasks 1 and 3 showed a great deal of promise, it
still utilized aspects of the whole breath collection system. For example,
both methods required the production and storage of clean, humidified air
for inhalation. Zero grade compressed air was filtered through a charcoal
bed and then humidified before storage in a 40 L Tedlar bag. Air was drawn
B-9
-------
from the bag as needed through the spirometer inhale valve (Tedlar flap
valve). This approach provided clean air for inhalation but severely limi-
ted the portability of the device; all samples were collected in a van
driven to the site.
This report documents modifications made to the alveolar sampling
device and collection procedures used in Task 3 (microenvironmental
exposure study). Primary consideration was given to portability and ease
of use. Aspects of the device studied and described in this report are (1)
the source of clean air for inhalation, (2) the choice of the smallest
possible canister for the collection of breath samples, and (3)
characterization of the recovery and carryover behavior of the complete
device, less the inhale portion. The results of these experiments were
used to design and build six portable, field sampling devices.
B-10
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SECTION 2
CONCLUSIONS
This work resulted in a field portable, useable spirometer, that was
designed to sample primarily alveolar breath in under two minutes. Six
devices were manufactured for use in breath sampling studies. Collection
of breath samples into 1.8 L Summary polished canisters will allow for at
least four or five replicate GC/MS analyses from each canister. Trial use
of a prototype device in Task 11-40 of this contract demonstrated its
applicability to the collection of organic compounds present in breath at
concentrations ranging from low ppb to ppm levels. This suggests great
potential for application to breath analysis in both ambient and occupa-
tional environments. The use of organic vapor respirator cartridges to
filter the air used for inhalation provided removal of all of the test
compounds except dichloromethane to levels below the QL of the analytical
method. Detected dichloromethane levels were generally not much larger
than the QL. It is not known if the detection of this compound represents
emission from the filter or if it was background from the laboratory
environment in which the analyses were performed. Dichloromethane was
retained by the filter up to a volume of 320 L after which breakthrough was
detected. Thus, for the compounds tested, each filter can be used to
provide up to 320 L of clean air before replacement is required; two
filters are used in each spirometer. Recoveries of test organic compounds
from the device at the 5 ppb level ranged from 89 to 112% with the
exceptions of n-dodecane and 4-phenylcyclohexene. At the 50 ppb level,
recoveries ranged from 92 to 109% with the exceptions of n-dodecane and 4-
phenylcyclohexene. The results indicated no significant problem from
either adsorption or carryover at these levels.
B-ll
-------
SECTION 3
RECOMMENDATIONS
Based on the results of this research, the following recommendations
can be made. First, a field trial of the complete portable spirometer is
recommended. This trial should be designed to evaluate the ruggedness of
the device, its ease of use, the sampling procedures employed, and the
background obtained from the device in a variety of sampling situations.
Second, a protocol for field use of the system should be written. Finally,
it is recommended that an alternate collection method e.g., the use of
Tenax sampling cartridges, be validated for compounds less volatile than p_-
dichlorobenzene.
B-12
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SECTION 4
EXPERIMENTAL
SOURCES OF AIR FOR INHALATION
For maximum flexibility in a breath collection method, it is desirable
that the collection of sample be possible at any location and not limited
to any fixed site far removed from the exposure area. The source of clean
air for inhalation was, therefore, one of the most important aspects of
this effort. At the start of this work, several options were considered
for a clean air source. They were:
1. Ambient air to be inhaled through carbon respirator cartridges,
2. Air to be inhaled from a stream of filtered (cleaned) air provided
by a high volume pump,
3. Filtered air to be inhaled from a small reservoir that is conti-
nuously filled by a low flow rate pump,
4. Clean, compressed air to be inhaled through an on-demand valve,
5. Air to be inhaled from a reservoir continuously filled by a small
tank of clean, compressed air, and,
6. Clean air to be inhaled from a large Tedlar bag filled at a remote
location and brought to the sampling system as needed.
Although all of these options could supply clean air for inhalation,
not all of the choices met the overall goals of miniaturization,
portability, and simplicity. For example, any source that requires the use
of a pump, reservoir, or tank of compressed air severely compromises the
portable nature of the device. In addition, a high volume pump would
either require electricity or a very large portable power supply that
would, again, compromise the portability feature. Therefore, we chose
first, to investigate the potential of carbon (charcoal) VOC respirator
cartridges to provide the clean air for inhalation. These devices do not
need an external power supply or other bulky accessories, and therefore
have the advantages of portability, simplicity, relatively low cost, and
small size. The experiments designed to test the suitability of these
B-13
-------
cartridges are described below. As will be seen, the results indicated
that no other option needed to be examined.
The respiratory cartridge filter was tested to evaluate the following:
(1) the VOC background of the respirator cartridge, (2) the effectiveness
and duration of VOC removal during continuous filtration of air spiked at
~1 ppm and -10 ppm, and (3) the effectiveness of trapping organics on the
same cartridge when intermittent sampling at ~10 ppm was conducted over
several days. This last experiment was designed to ascertain if potential
migration of VOCs within the adsorbent bed during storage between sample
collections could cause alterations in the volume of air that could be
filtered effectively. Along with these considerations were the cost of
replacing respirator cartridges and the number of samples that could be
collected using a single respirator cartridge without compromising the
quality of the results.
Filter Background
The VOC background of the potential inhalation system was addressed in
a relatively simple experiment. A respirator cartridge (Survivair Chemical
Cartridge for organic vapors, P/N 1001-00) was attached to a machined
teflon pipe that also had two other parts: one for drawing air through the
respirator cartridge and one to sample the filtered air. Each respirator
cartridge was used to filter laboratory air at 2 L/min for 37 minutes. Air
samples were collected into an evacuated, 2 L canisters starting at 0, 15
and 35 min after filtration began. An orifice rated at 1.6 L/min at full
vacuum was used to sample the filtered air for 75 sec so the canister would
be filled to a pressure close to atmospheric. Laboratory air and labora-
tory air collected in the teflon pipe without the respirator cartridge were
also collected. This experiment was repeated three times.
The analyses of the canister samples were carried out using a gas chro-
matograph/mass spectrometer system (GC/MS) with a canister air sampling
interface. The canister air sampling interface is essentially a cryofocus-
sing device that traps organic vapors from an air sample as the air is
pumped from the canister. A Nafion drying tube was used to dry the air
sample before cryotrapping. A schematic of the entire analytical system is
shown in Figure B-l. A more complete description of the system can be
found elsewhere (2). GC/MS analysis parameters are shown in Table B-l.
B-14
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Priiiure/Vacuum
Gauge
Drying Tub* Clan
Injection Port
ro
i
01
o
Vent
Flow
Controller
Vacuum
Pump
Ballast
Tank
Presjure/Vacuum
Gauge
Data System
G/C
M/S
Figure B-l,
Schematic diagram of the analytical system used for the analysis of canister air or
breath samples.
-------
TABLE B-l. ANALYTICAL CONDITIONS FOR CANISTER SAMPLE ANALYSIS
Instrument
Component
Parameter
Setpoint or Condition
Canister interface
Gas Chromatograph
Mass Spectrometer
Temperature:
valve, 6-port
transfer lines
trap
Sample Flow:
Trapping Time:
alveolar breath
air
external standard
Dryer:
drying flow
Model:
Temperature:
injector
column
transfer line
Column:
dimensions
phase
Carrier Gas:
flow
head pressure
Model:
Type:
Operation Modes:
lonization:
lonization Potential:
Trap Current:
Multiplier:
preamplifier
setpoint
Temperature:
inlet
source
Full Scan Mode:
accelerating voltage
magnetic sweep range
scan speed
200ฐC
200'C
-150*C ป 200'C
20 seem, nominal
3.0 min, nominal
10.0 min, nominal
2.5 min
Perma Pure, 1.1 m x 1/8" o.d.
80 mL/min nitrogen
Varian 3700
200ฐ C
-20*C (0 min)
200ฐ C
200* C
5*C/nrin
30 m x 0.32 mm i.d.
DB-624
Helium
-2.7 mL/min
10 psig (70 KPa)
LKB 2091
magnetic sector, single
focusing low resolution
multiple ion detection (MID),
full scan
electron impact
70 eV
50 pK
1
500
160ฐC
180'C
3.5 kV
1 ป 256 m/z
#2 (1.5 sec/scan cycle)
(continued)
B-16
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TABLE B-l (cont'd.)
Instrument
Component
Parameter
Setpoint or Condition
Mass Spectrometer
(continued)
Data Acquisition
MID Mode:
magnetic setpoint
ions: min. and max.
scan speed, cycle
Reference Standard:
Vacuum:
Computer:
MS Interface and Software:
Sampling Rate:
MID Mode:
sweep across ion
sample time
samples averaged per ion
A/D resolution
57 m/z @ 3.5 kV
57, 104 m/z
1 scan/sec
tri s-(heptaf1uoropropyl)-s-
triazine
~2 E-5 torr
Tandy 3000 microcomputer
Teknivent Vector/1 system
10000 samples/sec
+0.2 m/z by 0.033 m/z
T mS
4 summed x 2
16 bit
averagings
B-17
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For the analysis, the full scan mode of the GC/MS was used initially to
verify the identity of any major constituents. Some samples were analyzed
a second time without a drying tube in line to avoid losses of polar com-
pounds of potential interest. Later experiments utilized the multiple ion
detection mode (MID) for a selected list of hydrocarbons, aromatics and
halogenated alkyl compounds. In this manner, maximum sensitivity would be
available for target compounds.
Breakthrough Volumes of Target Compounds
Another test conducted on the respirator cartridge was designed to
determine the breakthrough volume of a set of target compounds shown in
Table B-2. Breatkthrough volume is defined as the filtration volume beyond
which a VOC is no longer effectively removed from the gas stream. A
knowledge of the breakthrough volumes is essential to determine how long a
cartridge could be used in the spirometer before the cleanliness of the air
for inhalation was compromised. The experiment provided levels of the
compounds to the filter ranging from 550 /*g/m3 to 2800 /*g/m3 in ambient
air. A liquid mixture of the analytes was prepared and placed into a
reservoir through which nitrogen was bubbled. The effluent was then added
to a stream of ambient air to provide the general levels of the compounds
desired. This air mixture was delivered to a chamber constructed from a
12 L Pyrex bell jar on a polystyrene base covered with aluminum foil. A
respirator cartridge was placed inside the chamber and connected to an
external pump and to a sampling canister that collected the cleaned air.
Another sampling canister collected chamber air that had not passed through
the cartridge so that the levels of the compounds could be determined.
Also, an additional port was used to vent excess spiked air from the
chamber and prevent any pressure increase. These experiments were
conducted at ambient temperature (~25*C).
The respirator cartridge filtered -16 L/min of the spiked polluted air
from the chamber. Samples of the filtered air were collected by 6 L canis-
ters using art orifice rated at 2.3 L/min at full vacuum. Each sample was
collected over 2 min. There were two levels of organics in air that were
used to challenge the respirator cartridge, both of which were well above
the levels generally encountered in environmental samples. This was
carried out to probe the limits of the respirator cartridge applicablity.
B-18
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TABLE B-2. LIST OF TARGET COMPOUNDS FOR EVALUATING
THE EFFECTIVENESS OF RESPIRATOR CARTRIDGES
Isopentane
n-Pentane
2-Methylpentane
Benzene
Dichloromethane
Chloroform
Carbon tetrachloride
n-Butanol
n-Butyl acetate
Vinylidene chloride
1,1,1-Trichloroethane
B-19
-------
For the lower level, filtered samples were collected beginning at 0, 82,
490, 980 and 2020 liters of total volume filtered. Unfiltered samples were
collected beginning at 0 and 2020 liters of total volume. For the higher
level, filtered samples were collected beginning at 0, 320, 650, 960 and
1290 liters of total volume filtered. Because of rapid depletion of the
volatile analytes were rapidly depleted from the liquid mixture used in the
bubbler, the solution was changed five times over the course of the experi-
ment. Since some depletion occurs even with the solution change, the
unfiltered samples were collected at the beginning and end of the third
segment of the respirator cartridge loading to verify the levels used. For
each level, the entire experiment required approximately 2 hours of
essentially continuous filtering with intermittent sampling.
The analyses were carried out as for the previous experiment to deter-
mine the VOC background of the respirator. The analyses were accomplished
using the MID mode of the GC/MS and the canister air samples were all dried
through the tube drier prior to introduction into the instrument. In addi-
tion, the filtered and unfiltered air samples collected at 2020 L were
analyzed without the tube drier to allow detection of n-butanol and n-butyl
acetate. To expedite results for these two compounds, only the areas were
reported as no previous standard was available. All other compounds were
quantitated to provide concentrations.
Effect of Filter Storage and Reuse
Questions remained concerning the possibility of the reusing of the
respirator filters and if storage in a relatively clean environment with
intermittent use was possible. This would allow maximal use of the filters
and result in cost reductions in materials required for breath sampling.
Additionally, the higher levels of the organics would be of interest in
case a breath sample from an individual in an occupational setting was
desired. These data would help provide critical information regarding the
range of applicablity with the respirator cartridges.
Essentially the same experiment as for breakthrough was performed
except that the compound levels ranged from 0.5 to 23 mg/m3 in air and
samples were collected intermittently over a five day period. Approxi-
mately 320 liters of air were filtered each day over five days. Between
days, the outlet of the respirator cartridge was capped and the cartridge
B-20
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was left in the chamber after the chamber was flushed out with ambient air.
A slow nitrogen purge was provided overnight in the chamber to prevent
possible contamination by laboratory air.
Each day before the start of the experiment, the solution of organic
compounds used to introduce the test components into the chamber was
replaced with fresh solution so that the level of each compound in the air
stream would be essentially the same from day to day. Sample collection
began at the start of each filtering cycle, 5 sec after filtering started.
As before, the air flow was -16 L/min and canister samples were collected
at 2.3 L/min. Unfiltered samples were collected on the third day at the
beginning and end of the filtering period to measure the concentration of
organics delivered to the chamber. Due to the organic mixture in the
bubbler, some more volatile compounds were depleted significantly during
each day of the sample collection period.
The GC/MS analyses were carried out in the same manner as for the
continuous filtering experiment.
CHOICE OF OPTIMAL CANISTER SIZE
Another parameter studied was the size of the canister used to collect
the breath sample. The optimal canister should have a small volume so that
it will fit easily into a portable sampling system yet should have a
volume large enough to permit replication of the analysis. The volume
should also be such that an adequate breath sample can be collected in 1-2
minutes so that kinetic studies for VOC elimination are possible. There
are essentially two elements that define the limits of analyses from
canisters: (1) trapping flow to the GC/MS cannot be quantitatively
monitored when the vacuum in a canister exceeds 15" Hg, and (2) the trapped
volume cannot exceed 60 mL for alveolar breath samples due to cryotrap
freezing problems associated with high concentration of water and C0ฃ in
breath samples. Both of these elements interact to define a minimum
canister volume. With regard to sample collection, the flow rate into a
canister through a critical orifice employing a tube section drops once the
canister vacuum is less than ~7.5" Hg. This element serves to under-
represent VOC concentration for samples collected at later times and can be
neglected here since a constant flow rate for a breath sample is not
critical when the sample is collected over approximately 2 minutes. This
B-21
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would allow a canister to be filled close to ambient pressures, thus
increasing the volume that can be analyzed from a given canister.
As mentioned before, another consideration of canister size is the
ability of a given canister to permit replicate analyses of the same sample
given the above constraints. In general, two analyses are the minimum
needed, though three is a safer number to allow for instrumental failure or
a slightly less than desired sample volume. Of course, greater numbers of
analyses could be desired, but the physical size of the canister then
becomes a problem for a portable spirometer system. Additionally, a large
canister volume requires sampling flow rates too large for a slow breathing
human subject, thus sampling ambient air along with the breath through the
exhaust tube of the portable spirometer. Slower sample collection could be
utilized but this would be at the expense of the time resolution desired.
To provide a reasonable compromise, a minimum of three sample analyses from
the same canister should be possible. Therefore the canisters must contain
enough volume for: (1) residual nonanalyzable volume, or 1/2 of the
canister volume, (2) the actual volume required per analysis step multi-
plied by three, and (3) the volumes consumed during an analysis which are
not actually trapped multiplied by three.
As a first step, a simple experiment was devised to test the analytical
capacity of 1 L air sampling canisters for breath samples. A spirometer
was set up to provide the alveolar breath for the canister. Using a
0.99 L/min orifice (rated at full vacuum) over 1.0 min and an evacuated 1 L
canister, the exhaled breath was collected leaving a vacuum in the canister
of 3.8" Hg.
The canister was put through three analytical cycles of cryo-trapping.
Each cycle included: (1) the initial flow surge from the canister as the
valve is opened, but before the flow is regulated by the Tylan flow
controller, (2) a 2.0 min x 20 standard cubic centimeters per minute (seem)
flush out period, (3) a 3.0 min x 20 seem loading period, and (4) .a 0.5 min
x 20 seem post-loading period. The measured volumes total 110 seem, though
somewhat more will have been expended per analysis cycle due to the initial
surge. At each sample withdrawal, the remaining pressure in the canister
was noted as was the ability of the system to maintain a flow of 20 seem.
As more sample is withdrawn from the canister, the vacuum increases which
B-22
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at some point will result in a drop in flow below 20 seem. When the flow
is not constant, quantification becomes difficult and unreliable.
ADDITIONAL RECOVERY STUDIES
The recoveries of several aliphatic, aromatic, and chlorinated hydro-
carbons through the Teflon exhale valve were studied during VIA 40, Task 1
of this contract and were found to average 101% and 96% for the test
compounds at levels of 4.4 and 36 /*g/m3, respectively. This study tested
the exhale valve only and was performed with a continuous flow of contami-
nated air through the system. What remained to be determined were the
recoveries of a range of compounds from the system as it will be used in
the field. That is, an investigation of the compound recoveries from air
that has occupied the 0.5" Teflon sample collection tube was needed. This
was accomplished by introducing a synthetic breath stream into the device
in a manner that mimicked the inhale and exhale breath cycles. Adsorptive
losses of compounds at low levels and carryover of compounds at higher
levels were studied during this phase of the work and are described below.
The adsorptive loss and carryover experiments were quite similar so the
same appratus was used for each. The system was essentially a synthetic
breath generator with a (verification) canister to collect its effluent and
two valves that were switched simultaneously so flow was directed either to
the spirometer (exhalation) or out the side tube (inhalation). The
apparatus is shown in Figure B-2. In addition, the spirometer had its own
canister for sampling purposes.
Synthetic breath was generated by delivering air with 4.8% carbon
dioxide to a flow control valve then to a humidifier. This humidified air
was then mixed with a high concentration organic mixture (Table B-3) from
the fortification canister at a known rate. Once the gas leaves the gas
mixing bulb it is the final synthetic breath mixture spiked with known
levels of organics.
Adsorption Studies
One of the major areas of interest was to characterize the adsorptive
behavior of the spirometer system when used to collect a breath sample
containing low levels of organics. Unsuspected losses would severely
affect the accuracy of the analytical results. The approach taken here was
to start with a clean and dry spirometer and to collect two sequential
B-23
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Gat Mixing
Bulb
CD
ro
Tylan
Flow
Controller
Flow
Controlling
Orifice
Valve
Spiromater
Verification
Canister
Zero
Grade Air
Figure B-2.
Constant Temperature
Bath 37 C
Synthetic breath generator including verification canister and switching valves prior to
spirometer. The air contains 4.8% C02-
-------
TABLE B-3. TARGET COMPOUNDS FOR ADSORPTIVE LOSS AND
CARRYOVER EXPERIMENTS
Compound
Vinyl idene chloride
Methyl ene chloride
trans-l,2-Dichloroethy1ene
1,1-Dichloroethane
cis-Dichloroethylene
Chloroform
1,1,1-Trichloroethane
Carbon tetrachloride
Benzene
Trichloroethylene
Toluene
n-Octane
Tetrachloroethylene
1,2-Dibromoethane
Chlorobenzene
Ethyl benzene
2-Xylene
o-Xylene
Styrene
1,1,2, 2-Tetrachl oroethane
n-Decane
m-Di chlorobenzene
2-Di chlorobenzene
o-Di chlorobenzene
n-Dodecane
4-Phenylcyclohexene
Cone - Low Level ,
^g/m3
5.0
5.4
5.2
5.6
5.3
5.1
5.5
5.5
5.4
5.0
5.3
4.8
5.6
6.0
5.3
5.3
5.3
5.4
5.6
5.4
5.0
5.3
5.4
5.4
5.1
5.4
Cone - High Level, a
pg/m3
49
54
51
56
52
51
55
54
54
50
50
48
55
59
53
53
53
53
56
54
50
52
53
53
51
54
only in carryover experiments.
B-25
-------
breath samples each with low levels of organics (5 /*g/m3). if, upon
analysis, the first breath sample was found to have lower levels than the
second, then the losses were probably due to adsorption. To assure that
variations in the synthetic breath generator did not provide erroneous
results, a verification canister was used to simultaneously collect an
upstream sample simultaneously for comparison to the sampling canister that
is part of the spirometer. In this manner, a % recovery for the first and
second breath samples was calculated.
A flow rate of 6.2 standard L per minute (Slpm) of air with C02 and
humidity was mixed with the analytes to provide the low concentration
levels shown in Table 4-3. The mixture was passed through the valve
shunting it away from the spirometer prior to beginning the experiment. In
this manner, the synthetic stream could be established without "condi-
tioning" the surfaces of the spirometer. After equilibration of the
stream, a clock was started and the two valves, immediately before the
spirometer in Figure 4-2, were reversed so that the mixture flowed into the
spirometer. Four seconds later the valves were reversed to shunt (vent)
the flow, then four seconds later flow was switched back to the spirometer.
This switching was designed to simulate an actual breathing pattern
(approximately eight breaths per minute) in order to properly fill the
exhaust tube of the spirometer. This breathing cycle was carried out four
times then on the fifth "exhale" the sampling with the verification and
sampling canisters was started simultaneously. Each canister had a 2.3
L/min orifice (rated at full vacuum) so that sampling for 2.0 min would
collect approximately 4.6 L in a 6 L canister. When sampling by the
canisters was complete, the flow was left shunted away from the spirometer.
The experiments were carried out as indicated in Table B-4, where each
replicate collection was started with a cleaned and dried spirometer.
Within each replicate set, the spirometer was reused approximately 5 min
later for the second sample collection. During this time, the canisters
were replaced and the air stream was vented before the spirometer. The
zero concentration air was used to check for organic background contami-
nation in the synthetic breath generator when the fortification canister
was detached.
The spirometer was recycled (cleaned and dried) by rinsing the mouthbit
and valves with Milli-Q treated water then baking the parts in a vacuum
B-26
-------
TABLE B-4. SAMPLE COLLECTION REGIMEN FOR THE
ADSORPTIVE LOSS EXPERIMENTS
Replicate Experimental
No. Description
1 Zero cone, level3
Low cone, level
Low cone, level
2 Low cone, level
Low cone, level
3 Low cone, level
Low cone, level
determine VOC background in the synthetic breath generator and
spirometer.
B-27
-------
oven at 105'C for at least 30 min. The exhaust tube was simply backflushed
with helium until condensation on the walls was removed. Once the appara-
tus was cooled and reassembled, it was ready to be reused.
The analysis of the collected air samples were carried out using the
same procedure as for the filtering experiments, except that a somewhat
different set of ions were monitored during GC/MS analysis.
Carryover Studies
Another area of interest was how well the spirometer would perform for
the collection breath sample with a high concentration of organics
immediately followed by a breath sample with a low VOC concentration. Any
carryover would make the characterization of rapidly-changing breath levels
difficult. This experiment was carried out by generating and collecting a
high concentration (50 0g/m3) breath sample through the spirometer followed
by shunting the flow away while the level was adjusted to a low concentra-
tion (5 /tg/m3). After equilibration (10 min), the low concentration sample
was collected in the same manner as for the high concentration sample. The
"breathing" cycle was held constant at 8 sec as before and the other
parameters were unchanged. The spirometer was cleaned, as described above,
between each replicate sample collection. The sample collection regimen
used is shown in Table B-5.
The analyses were carried out using the GC/MS system and the same
method as for the adsorptive loss experiments.
PORTABLE SPIROMETER DESIGN
A design for a portable spirometer for collecting VOCs in alveolar
breath over a concentration range from low ppb to ppm was formulated based
on the results of previously described experiments. The primary design
goals were portability and ease of use for both the operator and
participant. The design was driven by the desire to collect a representa-
tive sample of alveolar breath in stainless steel canisters in under two
minutes. Breath samples could then be stored for later analysis by GC/MS.
Based on design goals, a number of desirable features were incorporated
into the final design and are briefly described here.
Portability
The need for a portable device drove the entire design process. Our
previous spirometer design required a large van for transport and required
B-28
-------
TABLE B-5. SAMPLE COLLECTION REGIMEN FOR THE
CARRYOVER EXPERIMENTS
Replicate Experimental
No. Description
1 High cone, level
Low cone, level
2 High cone, level
Low cone, level
3 High cone, level
Low cone, level
Zero cone, level a
determine background levels from carryover.
B-29
-------
the participant going to the van to supply the breath sample. The goal for
this alveolar spirometer was to produce a device that could be easily
carried by one person. Such a portable device could be carried to the
participant in their home or workplace, and could be easily transported to
the sampling site.
Speed of Sample Collection
The whole breath spirometer used in previous studies required approxi-
mately 10 minutes for set-up and another 15 to 20 minutes for sample
collection. This length of time was inconvenient during field studies of
human exposures and created difficulties in time resolution during kinetic
studies on chemical elimination from the body. The design goal for the
alveolar spirometer was a device that could be set-up in under 5 minutes
and could collect breath samples in 2 minutes or less. Such a device
should ease the time burden during field studies and improve the accuracy
of measuring the initial decay rate during elimination kinetics studies.
Ease of Use
Part of the improvement in sample collection times will result from
making the alveolar device simple for the operator and participant to use.
For ease of use and portability reasons, no pumps, bags, gas cylinders, or
electronic components were incorporated into the spirometer design. The
operator is required only to connect tubing and canisters in the system and
then open and close the canister valves at specified times. Sample collec-
tion is driven by the pressure difference between the evacuated canister
and the breath collection tube. The sampling rate is governed by a simple
fixed needle orifice. Breath samples are contained in a simple long open
Teflon tube. Clean inhale air, requiring no humidification, is provided
when the participant inhales through respirator cartridges charcoal filled.
The flow of breath is directed using custom designed unidirectional Teflon
float ball valves.
Participant convenience is improved since the breath sample is provided
in under 2 minutes instead of the 4 to 6 minutes required using the
previously designed, whole breath spirometer. A new Teflon mouthbit was
designed to increase participant comfort and new, foam padded noseclips
have been obtained to ease the discomfort encountered when the participant
seals his nasal airway.
B-30
-------
The spirometer was also designed so that it could be used easily by
people of all ages. A mounting plate was designed to pivot up on hinges
and then slide partially out of the case. This design will allow placement
of the device on a table with a height adjustment so people of different
sizes can comfortably reach the mouthbit.
Duplicate Sample Collection
In order to measure precision of the sampling and analysis procedure,
the spirometer must be capable of duplicate sample collection. This
feature was incorporated into the spirometer design so that simultaneous
sampling of a breath sample into two canisters can be performed.
Prevention of Pathogen Transfer
Any spirometer system used for multiple participants must prevent the
potential spread of pathogens from one participant to the next. The spiro-
meter must also be designed for disinfection under field use where elabo-
rate equipment is not available. With this in mind, all spirometer parts
were selected so that the materials could be autoclaved or disposed of and
that the parts could be easily disassembled for cleaning.
Tenax Sampling Option
The alveolar spirometer was designed with the idea that it may be
desirable in the future to collect breath samples on Tenax cartridges
instead of canisters. This capability would expand the range of target
compounds available to this method. The design incorporated a removable
mounting plate so that a new plate can be installed that will hold a pump
and Tenax cartridges should this be required in future work.
B-31
-------
SECTION 5
RESULTS AND DISCUSSION
SOURCES OF AIR FOR INHALATION
Background from Filter
The quantifiable limits (QLs) for the compounds studied in these
experiments are listed in Table B-6 for various breath volumes analyzed.
In the following tables, the QLs are shown for the analytical volumes used
in that experiment. The analytical results for the air samples collected
to determine the background from the VOC are shown in Table B-7. In
general, the background was quite low. Only dichloromethane and tetra-
chloroethylene were measured at levels above the QL. Concurrent measure-
ments of the laboratory air indicated relatively high levels of the
chlorinated compounds. It is possible that chlorinated compounds detected
in the samples might well be derived from residual lab air in the system
after filter or cannister installation. Consequently, the true source of
these compounds is unclear. The presence of organic compounds, even at
these levels, could present a problem for the analysis of compounds in
breath if the exposure level was very low. It should be noted that the
filtration flow rate used here was 2 L/min. In an application where air is
inhaled through the filters, the flow rate will be much faster, approxi-
mately 20 L/min. Thus, the low flow rate used for this background check
maximizes the likelyhood of detecting compounds released from the filter
cartridge and represents a worst case situation. The final spirometer
design will allow for the collection of spirometer blanks for evaluating
contamination during field studies.
Breakthrough Volumes of Target Compounds
The results of the experiments designed to challenge the cartridge
with low levels of organic compounds using a continuous air flow are shown
in Table B-8. Overall, the data indicate that the charcoal filters perform
very well. Dichloromethane was the only compound consistently detected and
it was measured at levels near the QL of the method and less than 0.4% of
the inlet concentration.
B-32
-------
TABLE B-6. ESTIMATED QUANTIFIABLE LIMITS FOR TARGET COMPOUNDS
FOR CANISTER AIR ANALYSES USING MID
Compound
Isopentane
n-Pentane
2-Methylhexanea
3-Methylhexanea
Vinylidene chloride
1,1,1-Trichloroethane
Tetrachloroethylene
2-Methylpentane
Benzene
Carbon tetrachloride
Chloroform
Dichloromethane
Toluene
2-Xylene
n-Nonane
n-Decane
n-Undecanea
n-Butanolb
n-Butyl acetate
Cone.
20 ml
12
15
3.5
3.5
6.5
33
18
16
12
5.0
5.0
17
4.0
2.0
3.5
5.0
5.0
40
40
(/jg/m3) for Volume
150 ml
1.7
2.0
0.5
0.5
0.9
4.4
2.4
2.1
1.6
0.7
0.7
2.3
0.5
0.3
0.5
0.7
0.7
40
40
Analyzed
200 mL
1.2
1.5
0.35
0.35
0.65
3.3
1.8
1.6
1.2
0.5
0.5
1.7
0.4
0.2
0.35
0.5
0.5
40
40
^Concentrations are estimates based on similar compounds.
^Minimum ion intensity detectable.
B-33
-------
TABLE B-7. CONCENTRATIONS (ug/m3) OF TARGET COMPOUNDS FOUND IN FILTERED LABORATORY AIRa
Compound
Vol. Analyzed:
Dichloromethane
Chloroform
1.1. 1-Trichloroethane
Benzene
Toluene
Tetrachloroethylene
n-Nonane
n-Decane
First
35 min
150 ml
4.2
NDC
NO
T
ND
ND
ND
ND
Cartridge0
unfiltered
150 mL
35
67
513
3.9
10.5
12.7
0.5
0.83
Second Cartridge
0 min
200 ml
2.9
ND
ND
T
ND
ND
ND
ND
35 min
200 ml
3.2
ND
ND
T
ND
ND
ND
ND
unfiltered
150 ml
DC
0
D
D
D
ND
ND
ND
0 min
200 mL
T<ป
T
T
T
T
8.6
T
T
Third Cartridge
35 min
200 iM.
T
ND
T
T
ND
5.2
ND
ND
unfiltered
200 mL
13.4
33
16.6
2.3
10.1
7.7
ND
T
'Samples of filtered air were collected starting at 0 or 35 min. Unfiltered air samples mere
collected immediately before or after the corresponding set of filtered air samples were
collected.
DThe 0 min sample was not analyzed by MID.
CD = Detected by full scan but not quantitated; ND = not detected.
*T = Trace level detected, below QL.
B-34
-------
TABLE B-8. CONCENTRATIONS OF TARGET COMPOUNDS IN AIR WITH CONTINUOUS FILTERING
AT LOW CONCENTRATIONS
Cone, in
Unfiltered air
(ug/ra3)
Compound
OL (ug/m3)
Volume Analyzed:
Isopentane
1-Pentane
2-Methylhexaneb
3-Methylhexaneb
Vinylidene chloride
1.1. 1-Trichloroethane
2-Methylpcntane
Benzene
Carbon tetrachlonde
Chloroform
Dichloromethane
Toluene0
B-Xylene"
n-Butanol
n-Butyl acetate
1.25
1.5
0.35
0.35
0.65
3.3
1.6
1.2
0.5
0.5
1.7
0.4
0.2
NAd
0.4
0 L
20 ml
>1720
1860
1.8
4.2
>1090
2140
900
780
3310
710
710
2.8
1.3
NTซ
NT
2022 L
10 ml
795
990
NO
4.7
855
1860
1290
773
2620
6190
552
2.2
NO
35300f
14200f
0 L
200 ml
NO*
NO
NO
TC
NO
T
NO
T
NO
T
2.5
NO
NO
NT
NT
Cone, in Filtered Air
-------
Analogous results for the experiment using higher level of organics are
shown in Table B-9. In this case, the dichloromethane levels found in the
samples collected at 0 and 320 L represent less than 0.2% of the inlet
levels. That such levels were not measured in the blanks and were measured
in the filtered air samples suggests that the flow rate might be too rapid
for complete removal of the dichloromethane. To overcome this, we have
designed the spirometer system to operate with two cartridges in parallel
such that the flow rate through each cartridge is reduced by 50%. As noted
in the background experiments, the presence of this compound could be an
artifact of the laboratory environment where dichloromethane is commonly
used. This aspect does indicate caution when planning and interpreting
measurements of dichloromethane at low levels. The data also show that at
646 L, dichloromethane has begun to break through the sorbent bed. There-
fore, a volume up to 320 L per cartridge would provide clean air for
inhalation for conditions similar to these experiments.
Effect of Filter Storage and Reuse
The results of the experiment where the cartridge was -used intermit-
tently over 5 days and stored between uses are shown in Table B-10. These
data are consistent with those of Table B-9 in that increased levels of
dichloromethane were measured in the sample collection begun at 643 L (day
2) suggesting a safe volume of 320 L. Thus, under these conditions, the
effect of storage and multiple use of the filter is minimal.
CHOICE OF OPTIMAL CANISTER SIZE
As indicated in the experimental section, we wished to choose a canis-
ter as small as possible for use in the portable spirometer system. AIL
Summa polished canister was evaluated according to the criteria outlined
above. The results of these repeated analyses are shown in Table B-ll.
The data show that the vacuum and flow rate were acceptable for the first
two analyses. With the third analysis, the flow rate dropped below 20 seem
and the canister vacuum increased to 16"Hg which would result in difficu-
ties with quantisation. Consequently, we decided that a larger canister
was needed. According to Scientific Instrumentation Specialists, the
supplier of the canisters, the next larger canister that could be
manufactured from readily available materials would result in a volume of
1.8 L. Given that two good samples could be withdrawn from the 1 L
B-36
-------
TABLE B-9. CONCENTRATIONS OF TARGET COMPOUNDS IN AIR WITH APPROXIMATELY CONTINUOUS FILTERING AT
HIGHER CONCENTRATIONS
Cone, in air
(rag/m3)
Compound
Volume Analyzed:
Isopentane
n-Pentane
Vinylidene chloride
1,1.1-Trichloroethane
2-Methylpentane
Benzene
Carbon tetrachloride
Chloroform
Oichloromethane
n-Decanec
n-Butanol
n-Butyl acetate
OL
1
1
0
3
1
1
0
0
1
0
N
0
(ug/m3)
.2
.5
.65
.3
.6
.2
.5
.5
.7
.50
Ad
.4
650 L
20
5
7
6
16
13
>6
26
6
5
mL
.4
.0
.0
.8
.7
.3
ND
NT6
NT
940 L
20 mL
0
1
2
13
6
>7
23
6
3
.49
.50
.4
.4
.0
.1
.6
ND
33265 f
178930f
0 L
200 mL
NDa
Tฐ
ND
ND
ND
T
ND
T
7.2
ND
NT
NT
Cone, in Air
(ug/m3)
320 L
200 mL
ND
T
ND
ND
ND
T
ND
0.66
9.0
ND
NT
NT
650 L
200 mL
ND
T
ND
ND
ND
T
ND
T
24
ND
NT
NT
960 L
200 mL
ND
T
ND
ND
ND
T
ND
T
96.
T
NT
NT
1290 L
200 mL
ND
T
ND
ND
ND
T
ND
T
330.
ND
128d
147d
aND means not detected.
bT = trace; detectecd but below QL.
cNot added to mixture.
dNA = not determined.
eNT = not tested.
flon intensity normalized to 100 mL; 55.6 mL analyzed.
B-37
-------
TABLE B-10 CONCENTRATIONS OF TARGET COMPOUNDS IN AIR COLLECTED OVER 5 CYCLES (DAYS)
Cone, in air (mg/m^)
Compound
Volume Analyzed:
Isopentane
n-Pentane
2-MethylhexaneC
3-Methylhexanec
Vinylidene chloride
1.1. 1-TMchloroethane
2-Hethylpentane
Benzene
Carbon tetrachloride
Chloroform
Methylene chloride
n-Undecanec
n-Butanol
n-Butyl acetate
Cumulative Volume
at start of sample
collection
Day 4: Start
20 mL
7.1
8.2
ND
ND
7.5
18
12
7.8
28
6.1
5.1
ND
NT"
NT
Day 4: End
20 mL
1.3
2.3
ND
ND
4.1
18
7.8
8.0
30
E.6
4.1
ND
20.200ฎ
107,400*
Day 0
200 mL
ND*
ND
ND
ND
ND
ND
ND
T
NO
ND
2.8
ND
NT
NT
0
Cone.
Day 1
200 mL
ND
ND
ND
ND
ND
ND
ND
T
ND
ND
4.2
ND
NT
NT
323
in air (ug/m3)
Day 2
200 mL
ND
Tฐ
ND
ND
ND
ND
ND
T
ND
ND
61
ND
NT
NT
643
Day 3
200 mL
ND
ND
ND
ND
ND
T
ND
T
ND
ND
190
T
NT
NT
966
Day 4
200 mL
ND
ND
ND
ND
T
T
T
T
ND
ND
370
ND
ND
140e-f
1287
*ND = ion not detected.
bT = trace detected (below quantifiable limit).
cNot added to mixture.
dNT = not tested.
elon intensity for 100 mL.
f!47.7 mL analyzed.
B-38
-------
TABLE B-ll. RESULTS OF MULTIPLE ANALYSIS CAPACITY
OF 1-LITER CANISTERS
Analysis
Number
Canister Vacuum
("Hg)
Trapping Flowa
(seem)
1
3.8 (initial)
7.3 (final)
11.8 (final)
16 (final)
20 throughout
20 initial and until
2 minutes
19.8 final
20 initial
18.6 after 2 minutes
16.5 after 3 minutes
(final)
aTotal trapping time is 10 minutes.
B-39
-------
samples, and probably four or five, could be withdrawn from a 1.8 L canis-
ter. This larger canister is approximately 5 inches in diameter and 10
inches tall compared to 4" by 9" for the 1 L canister. This small increase
in size was not anticipated to cause any major problem with portability so
the 1.8 L canister was chosen for use in the final system.
ADDITIONAL RECOVERY STUDIES
Adsorption Studies
The results of the experiment to study the adsorptive behavior of the
spirometer to the test compounds are shown in Table B-12 . The first and
second uses of the spirometer are grouped together and the replicate number
is indicated. The mean recovery, relative to the verification canister, of
the first use was 94% and was 100% for the second use. This shows that
there are no major losses associated with adsorption. At the low levels
used in this experiment, the lesser volatile compounds n-dodecane and 4-
phenylcyclohexene were poorly recovered. Thus, compounds more volatile
than these two compounds can most likely be collected successfully with the
new spirometer. Where the most accurate measurements possible are
required, a small amount of conditioning of the spirometer might be neces-
sary to maximize the recoveries of the organic compounds. This could be
accomplished by requiring the study participant to breath through the
device for two minutes prior to the collection of the sample. When the
spirometer is to be used multiple times by the same person, as for kinetic
studies, this conditioning would only be needed for the first sample.
Carryover Studies
The results of the carryover experiments are shown in Table B-13. The
high level and the low level results for each high level/low level pair are
grouped together. If carryover were a problem, recoveries greatly in
excess of 100% would be expected for the low level samples. This clearly
was not the case indicating that, in general, there are no problems asso-
ciated with the carryover of the test compounds. Note however, that the
percent recoveries for n-dodecane and 4-phenylcyclohexene in the low level
cases in this experiment are higher than those in the adsorptive loss
experiment. This suggests that as analytes become less volatile, they are
B-40
-------
TABLE B-12 PERCENT RECOVERY* FROM ADSORPTIVE LOSS EXPERIMENTS
FOR THE FIRST AND SECOND SPIROMETER USE FOR EACH SAMPLING PAIR
First
Use
Second Use
ft Recovery
Compound
Vinyl idene chloride
Dich lor one thane
trans-Dichloroethylene
1.1-Dichloroethane
cis-Dichloroethylene
Chloroform
1.1.1-Trichloroethane
Carbon tetrachloride
Benzene
Tnchloroethylene
Toluene
n-Octane
Tetrachloroethylene
1,2-Dibromoethane
Chlorobenzene
Ethylbenzene
fi-Xylene
o-Xylene
Styrene
1,1.2. 2-Tetrachloroethane
n-Decane
m-Dichlorobenzene
e-Dichlorobenzene
o-Dichlorobenzene
n-Dodecane
4-Phenylcyhclohexene
AVERAGE
JD/zb
61
84
61
63
61
83
61
82
78
60
91
57
59
107
77
91
91
91
104
83
57
75
75
75
57
104
1
93
99
95
94
92
102
99
128
102
92
90
91
84
100
101
97
96
94
92
100
93
85
102
110
62
NDC
96
2
98
90
103
98
91
125
96
72
94
97
96
90
98
94
89
97
96
98
96
92
93
95
92
94
61
ND
94
3
97
100
98
92
87
110
86
117
90
95
95
93
80
96
93
94
89
90
79
92
98
89
97
97
70
54
91
Mean
96
96
99
95
90
112
94
106
96
95
94
91
87
97
94
96
94
94
89
95
95
90
97
100
64
54
94
SO
2
4
3
3
2
10
5
24
5
2
3
1
8
2
5
2
3
3
7
4
2
4
4
7
4
2
ftRSD
2
5
3
3
2
8
6
23
5
2
3
1
9
2
5
2
4
4
8
4
3
5
4
7
4
2
ft Recovery
1
97
78
99
91
92
86
92
120
105
104
99
104
95
104
97
102
99
100
110
105
107
91
105
102
106
ND
100
2
95
93
97
103
105
106
103
114
90
95
100
95
87
100
93
100
102
99
108
100
106
100
106
95
129
114
101
3
92
87
104
99
96
119
100
107
96
100
100
96
71
94
94
102
99
97
105
92
102
96
107
108
130
92
99
Mean
95
86
100
98
98
104
98
114
97
100
100
98
84
99
95
101
100
99
108
99
105
96
106
102
121
103
100
SO
2
6
3
5
5
13
5
5
6
4
0
4
10
4
2
1
1
1
2
5
2
4
1
5
11
11
1
ftRSD
2
7
3
5
6
13
5
5
6
4
0
4
12
4
2
1
1
1
2
5
2
4
1
5
9
10
1
aPercent recovery relative to the verification canister before the spirometer.
blon monitored during sample analysis.
CND = not detected.
B-41
-------
TABLE B-13. PERCENT RECOVERY* RELATIVE TO VERIFICATION SAMPLE FOR EACH
HIGH LEVEL/LOW LEVEL PAIR TO TEST CARRYOVER
High Level
* Recovery
Compound
Vinyl idene chloride
Dichloromethane
trans-Dichloroethylene
1,1-Dichloroethane
cis-Oichloroethylene
Chloroform
1.1.1-Trichloroethane
Carbon tetrachloride
Benzene
Trichloroethylene
Toluene
n-Octane
Tetrachloroethylene
1.2-Dibromoethane
Chlorobenzene
Ethylbenzene
p.-Xylene
o-Xylene
Styrene
1.1.2. 2-Tetrach loroethane
n-Decane
m-Dichlorobenzene
p.-Dichlorobenzene
o-O i Chlorobenzene
n-Oodecane
4-Pheny 1 cyhc lohexene
AVERAGE
Jป/lb
61
84
61
63
61
83
61
82
78
60
91
57
59
107
77
91
91
91
104
83
57
75
75
75
57
104
1
79
93
81
80
104
119
103
111
116
100
124
69
94
122
106
114
119
110
126
113
98
107
109
105
64
NOC
103
2
102
104
95
99
105
97
102
98
98
101
100
97
102
100
101
103
99
104
103
106
100
98
104
98
92
92
100
3
101
103
107
98
103
100
101
101
102
100
59
91
106
101
99
99
97
104
98
105
94
107
104
97
98
90
99
Mean
94
100
95
92
104
105
102
103
105
100
94
92
101
107
102
105
105
106
109
108
97
104
105
100
85
91
101
SO
11
5
10
9
1
9
I
6
8
1
27
3
5
10
3
6
10
3
12
3
2
4
3
4
15
43
2
ซRSD
11
5
11
10
1
9
1
6
7
1
28
4
5
10
3
6
10
4
11
3
2
4
3
4
17
47
2
Low
Level
% Recovery
1
95
100
98
99
104
101
105
107
98
107
99
92
101
88
98
95
99
94
105
100
100
94
109
111
76
151
99
2
97
93
94
89
92
104
89
84
103
103
87
90
84
86
83
82
81
86
75
101
81
88
92
79
60
46
86
3
90
105
87
88
92
102
93
95
94
85
93
87
106
105
91
94
90
90
87
90
97
99
96
99
110
93
94
Mean
94
99
93
92
96
102
96
95
99
99
93
90
97
93
91
91
90
90
89
97
92
93
99
96
82
97
93
SD
3
5
5
5
5
1
7
10
4
9
5
2
10
8
6
6
7
3
12
5
8
5
7
13
21
43
5
*RSD
3
5
5
6
6
1
7
10
4
10
6
2
10
9
7
7
8
4
14
5
9
5
7
14
26
44
6
aPercent recovery relative to the verification canister before the spirometer.
blon monitored during sample analysis.
CND ซ not detected.
B-42
-------
not released easily from the spirometer. The results for these two com-
pounds in both experiments are consistent and suggest a volatility limit
for compounds to be sampled with this device.
PORTABLE SPIROMETER CONSTRUCTION
Six portable spirometers were constructed for the collection of VOCs in
alveolar breath. The spirometers were designed to collect breath VOCs at
concentrations ranging from low /Kj/m3 (ppb) levels, that might result from
environmental exposures, up to mg/m3 (ppm) levels that might result from
occupational exposures. The spirometers were designed and constructed with
portability, ease of use, and effective analyte collection as primary
goals. Each device can be carried by one person, set-up in the field in
less than five minutes, collect alveolar breath samples in less than two
minutes. All spirometer materials were chosen to be light weight, to lack
analyte adsorption or emission properties, and to allow sterilization or
disposal to prevent pathogen transmission between subjects.
A diagram of the portable spirometer is presented in Figure B-3.
Detailed part descriptions, corresponding to the numbers on the figure, are
presented in Table B-14. The spirometer is housed in an aluminum case to
protect the device during shipment and to provide a rugged support frame
for the interior components. All components are attached to an aluminum
plate that in turn is mounted on pivoting slides. These slides allow the
entire mounting plate to slide out horizontally and elevate vertically from
pivot points at the rear of the case. This feature is incorporated so that
the spirometer mouthbit can be easily reached by children and adults when
the spirometer is placed on a table. A simple lever is used to adjust the
mounting plate to six different heights to accommodate a wide range of
participant heights. The overall device size is 61.5 x 48 x 22.5 cm when
the case is closed. The device weighs 10.5 kg with two 1.8 L canisters
enclosed. Spare parts can be carried in the space beneath the mounting
plate.
Spirometer functions were designed to be as simple as possible, with no
electricity, air cylinders, humidifiers, or collection bags required for
operation. A brief description will be provided here on the intended
B-43
-------
Figure B-a Portable spirometer for the collection of VOCs in alveolar breath.
-------
TABLE B-14. PORTABLE SPIROMETER PARTS LIST*
1. Carrying case
Source: Jensen Tools Inc., Phoenix, AZ
Dimensions: Interior dimensions 60 x 44 x 22 cm
Material: Aluminum with rubber gasket
2. Mounting plate slide
Source: Local hardware store, custom construction at RTI
Dimensions: 40 cm long, 1.3 cm wide
Material: Aluminum channel
3. Mounting plate
Source: Comfort Engineers, Durham, NC
Dimensions: Overall 58 x 43 x 0.32 cm
Material: Aluminum
4. Handle
Source:
Dimensions:
Local hardware store
11 x 3.2 cm
Material: Aluminum
5. Vertical elevation lever
Source: Edgecomb Steel, Charlotte, NC
Dimensions: 24 cm long, 1.2 cm diameter rod
Material: Aluminum
6. Canister well plate
Source: Comfort Engineers, Durham, NC
Dimensions: 30.6 x 19.5 x 0.32 cm
Material: Aluminum
7. Inhale respirator cartridge
Source: Survivairฎ, Santa Ana, CA
Dimensions: 8.8 cm diameter, 3.5 cm deep
Materials: Activated charcoal encased in plastic with gauze
supports
8. Respirator cartridge adapter
Source: Custom construction at RTI, 0-ring from Dixie
Bearings, Durham, NC
Dimensions: One end threaded to mate cartridge, other end
2.54 cm o.d., 1.3 cm i.d.
Materials: Adapter is Teflonฎ TFE, 0-ring is Vitonฎ
9. Union-T
Source:
Dimensions:
Material:
Filtration Technology, Inc., Greensboro, NC
2.54 cm i.d.
Teflonฎ TFE
(continued)
B-45
-------
TABLE B-14 (cont'd.)
10.
Union clamp
Source: Local hardware store, custom constructed
Dimensions: 6.0 x 4.4 x 4.2 cm
Materials: Aluminum angle, aluminum channel, steel thumbscrew,
steel spring
11.
Tubing adapter
Source:
Dimensions:
Material:
Custom construction at RTI
2.54 cm o.d. on union-T end, tapers 2.1 to 1.9 cm
o.d. on tubing end, 1.2 cm i.d.
Teflonฎ TFE
12. Flexible polyethylene tubing
Source: Dayco Corp., Dayton, OH
Dimensions: 1.9 cm i.d., 2.5 cm o.d., 18 cm long
Material: Polyethylene, flexible
13. Unidirectional inhale valve
14.
Source:
Dimensions:
Materials:
Mouthbit
Source:
Dimensions:
Material:
Custom constructed at RTI
(a
8
(d
Inlet end tapers 2.1 to 1.9 cm o.d., 12 cm i.d.
Union-t end 2.54 cm o.d., 12 cm i.d.
Float ball 1.0 cm diameter
Valve interior orifices 0.6 cm i.d.
Body and ball are Teflonฎ TFE, screws are stainless
steel
Custom constructed at RTI
Overall length 7.5 cm, Union end 2.54 cm o.d. and
1.2 cm i.d., mouth end 2.8 cm wide x 1.4 cm deep
Teflonฎ TFE
15. Unidirectional exhale valve
16.
Source:
Dimensions:
Materials:
Sampling port
Source:
Dimensions:
Material:
Custom constructed at RTI
(a) Union-t end 2.54 cm o.d., 12 cm i.d.
(b) Outlet end 1.27 cm o.d., 1.2 cm i.d.
(c) Float ball 1.0 cm diameter
(d) Valve interior orifices 0.6 cm i.d.
Body and ball are Teflonฎ TFE, screws are stainless
steel
Custom constructed at RTI
5.1 cm long, 0.6 cm o.d., 0.4 cm i.d.
Stainless steel
(continued)
B-46
-------
TABLE B-14 (cont'd.)
17. Union-T
Source:
Dimension:
Material:
18. Connector tubing
Sources:
Dimensions:
Materials:
19. Elbow union
Source:
Dimensions:
Materials:
21.
Swagelokฎ, Raleigh Valve and Fitting, Raleigh, NC
0.6 cm tube o.d. fitting
Stainless steel except Teflonฎ TFE ferrules at
sampling port connection
(a) Swagelokฎ fittings, Raleigh Valve and Fitting,
Raleigh, NC
(b) Tubing, Atlantic Plastics, Raleigh, NC
4.4 cm long, 0.6 cm o.d., 0.4 cm i.d.
a) Fittings are stainless steel
b) Tubing is Teflonฎ TFE
Swagelokฎ, Raleigh Valve and Fitting, Raleigh, NC
0.6 cm tube o.d. fitting
Stainless steel
20. Flow control orifice
Source:
Dimensions:
Materials:
(a) Orifice needle Becton Dickinson, Rutherford, NJ
(b) Fittings, Swagelokฎ, Raleigh Valve and Fitting,
Raleigh, NC
ffl
Septum, Supleco, Bellefonte, PA
Needle, 22 gauge, 2.2 cm long
Tube, 2.4 cm long, 0.6 cm o.d., 0.4 cm i
Septum, 0.75 cm long, 0.6 cm diameter
Needle and fittings are stainless steel
Septum is Thermogreenฎ rubber
d.
Canister valve
Source: Nupro Co., Willoughby, OH
Dimensions: 0.6 mm tube fittings on bellows valve
Materials: Stainless steel
22. Canister
Source:
Dimensions:
Materials:
23. Canister straps
Source:
Dimensions:
Material:
Scientific Instrumentation Specialist, Moscow, ID
Nominal 1.8 L cylindrical, 25 cm long, 12.7 cm
diameter
Summaฎ polished stainless steel
Locally purchased
50 cm long, 2 cm wide
Nylon straps with Velcroฎ closure
(continued;
B-47
-------
TABLE B-14 (cont'd.)
24. Breath containment tube
Source: Atlantic Plastics, Raleigh, NC
Dimensions: 1.27 cm i.d., 0.076 cm wall thickness, 762 cm long
Material: Teflonฎ FEP
apart number corresponds to numbers in Figure B-3.
B-48
-------
sample collection procedure with a discussion of the function of each com-
ponent. Initial set-up is accomplished by placing the spirometer compo-
nents in their proper places. A 1.8 L stainless steel canister is placed
into the holding well and strapped into place (two canisters are used if
duplicate samples are to be collected). A previously sterilized mouthpiece
unit, consisting of an inhale valve, exhale valve, mouthbit, and sampling
orifice, are clamped into place. The Teflon and stainless steel valves are
custom built with a Teflon float ball to provide uni-directional flow
(Figure B-4). These valves will operate over the angles created by pivot-
ing the mounting plate and can be autoclaved for sterilization. The
orifice union is connected to the canister valve. A precleaned poly-
ethylene tube is connected, using a friction fit, from the respirator out-
let to the inhale valve inlet. The Teflon breath containment tube is
connected, using a friction fit, to the exhale valve outlet. The partici-
pant is seated in front of the spirometer and the mounting plate is raised
to a height which will be comfortable to the participant. The participant
dons pinch-type nose clamps to prevent breathing through the nostrils.
The participant is instructed to place his mouth tightly over the
mouthbit and to begin breathing as normally as possible. Some resistance
to normal breathing is encountered due to the constrictions of the valves
and long breath containment tube. People generally breathe through this
device at a slower and deeper rate than is normal which should enhance the
portion of alveolar breath being sampled. As the participant inhales, air
is pulled through the two charcoal filled respirator cartridges to remove
VOCs in the inhale air. The subject is asked to provide four full breaths
before sample collection is initiated. This ensures that the spirometer
and participant airways are cleared of analytes found in the ambient air at
the sampling location. As the participant breathes, clean inhale air
passes through the unidirectional inhale valve and into the lungs. As the
participant exhales the breath passes out through the unidirectional exhale
valve and into the breath containment tube.
Sample collection is initiated at the end of the fourth exhalation by
opening the canister valve. The canister is at an initial pressure of 5 x
10-2 torr, so the pressure differential drives the sample collection. Flow
control is achieved using a simple fixed needle orifice. The orifice is
designed to collect 1.4 L of breath in canisters with a nominal volume of
B-49
-------
Breath
Flow
L
Side View
TO
I
c_n
O
5>
0)
Top View
E
Side view; sample port coming in
from opposite side.
_^^_^^_^^^^^^^^^^^^^^^^*m
^ 4" i.d. Teflon Tube
Flow
J" o.d. Stainless Steel Sampling Port
0
Figure B-4. Exhale valve and sample port.
-------
1.8 L over a 1.5 min time period. Breath samples in the canisters are
maintained at sub-ambient pressures in order to reduce water condensation
inside the canisters. Collection of the breath sample is slightly time
weighted since the fixed needle is not a critical orifice. The collection
rate remains nearly constant from the beginning of the sample collection
until the canister reaches approximately 50% of ambient pressure (0.9 L in
a 1.8 L canister). From that point, the flow rate decreases approximately
30% until 1.4 L of sample has been collected and the canister valve is
closed.
The breath containment tube was designed to allow the collection of
breath that is over 95% alveolar by composition. As the participant
exhales, the deadspace air from his breathing airways passes rapidly by the
sampling part in the exhale valve. The deadspace air is briefly sampled as
it passes, but passage time is fast because there is little restriction to
its exhalation in the body. The remaining portion of the exhaled breath
comes from the alveoli in the lungs, and it is also sampled as it passes by
the collection port during exhalation. The volume of alveolar to deadspace
air is typically 2:1 to 3:1 and it takes longer to exhale since there is
more resistance in the lungs. Therefore, a much larger volume of alveolar
air is sampled as compared to deadspace air during each exhalation.
As inhalation begins, a plug of exhaled breath remains in the breath
collection tube. The portion of the plug nearest the sampling port repre-
sents the last portion of exhaled breath. This last portion is composed
entirely of alveolar breath. The breath containment tube dimensions and
sample collection rates have been selected so that only alveolar breath is
collected from the containment tube while the participant inhales, even if
duplicate samples are collected. The participant keeps breathing into the
spirometer until sample collection has been completed, then the canister
valve is closed and the participant can release his mouth from the mouth-
bit.
In order to prevent pathogen transmission between participants the
entire mouthpiece unit is washed with organic free water and autoclaved
between uses. The flexible polyethylene tubing is disposed of after each
participant has provided a sample. Breath containment tubes are purged
with clean air between uses to remove residual water condensate. As pre-
viously described each respirator cartridge is effective in removing
B-51
-------
ambient air VOCs from air volumes less than or equal to 320 L over several
days. We recommend that the cartridges be replaced after the collection of
10 samples or in three days, whichever comes first, to ensure that break-
through volumes are not exceeded. This decision was made from the estimate
that the maximum amount of air inhaled by a participant in two minutes
would be 40 L. Thus, 400 L for ten participants would be safely below the
combined 640 L breakthrough volume established for two charcoal cartridges.
B-52
-------
APPENDIX C
BREATH EXPOSURE STUDY ESTABLISHMENT CONSENT FORM
C-l
-------
BREATH EXPOSURE STUDY
ESTABLISHMENT CONSENT FORM
The Research Triangle Institute (RTI) is under contract with the
U.S. Environmental Protection Agency to develop and test a device which
can be used to measure the amounts of volatile organic chemicals inhaled
and exhaled by humans. As part of this research contract we would like
to evaluate the Inhalation of airborne chemicals by people in common
environments like homes, stores, vehicles, recreational areas, and the
workplace. The data we collect will help us determine if people are
exposed to pollutants In these everyday situations and whether breath
easurements can be used to estimate these exposures.
We would like to ask you to participate in this research by
allowing us to sample the air at your establishment. We wish to
emphasize that this is strictly a research project and that RTI will not
disclose the Identities of participants to anyone, including the
contract sponsor, within RTI knowledge of establishment identities will
be strictly limited to the one or two chemists who visit your
establishment. The test data which is reported to the EPA and other RTI
personnel will be coded to eliminate all participant Identities and
protect your privacy. Our report to the EPA will include only generic
descriptions of establishment types (i.e. hardware store, laundramat,
etc.) and not the name or location of specific establishments. Your
participation would be strictly voluntary and would not result in
disruption of your business operations.
If you agree to participate, a chemist from RTI will collect an
Initial sample of the air at your establishment for evaluation purposes.
This would take approximately 10 to 30 minutes. If specific chemicals
are found in this sample then we may ask our chemist to make a return
visit and spend up to four hours in your establishment during normal
buislness hours. The chemist would collect an additional air sample
during this visit. Several different establishments will be chosen to
participate in this final visit. These visits would be carried out
between now and Nay 1989. Results of the analysis at your establishment
can be obtained by written request to RTI at the completion of the
project in June, 1989.
Your participation In this scientific study is very important in
answering questions about human exposure and would be greatly
appreciated. If you have any further questions about this research
study please call RTI chemist Mr. Kent Thomas at 541-6610 (toll-free
from Raleigh. Durham, and Chapel Hill) from 8:30 a.m. to 5:00 p.m.
Thank you for your time.
I have read and understand the above statements and do hereby
willingly allow RTI to collect air samples at this establishment.
ESTABLISHMENT NAME:
MANAGER SIGNATURE: DATE:
RTI CHEMIST SIGNATURE: DATE:
C-2
-------
APPENDIX D
BREATH AND AIR CONCENTRATION TABLES FOR
EXPOSURE EXPERIMENTS
D-l
-------
DEFINTIONS OF TERMS
Experiment Title: Describes whether samples are air, alveolar or
whole breath in addition to exposure situation.
Spreadsheet File Name: Name of Symphony spreadsheet work file where data
is stored.
Exposure End Time: Time at which exposure ended (24 hour clocks,
HH;MM).
Chemical name of compound measured.
EPA identification number for the chemical
compound.
Mass in blank to be subtracted from measured mass
to correct for background. This was not used for
this work.
Fractional recovery (1=100%) to correct for
incomplete recovery from canister and analysis
step. For this work 100% recovery was assumed.
Method LOD as described in Section 4.
Generally, four times the LOD. Measured
concentration less than the QL divided by the
volume analyzed (in L) are reported as *ND*.
Sample code as defined in QA section.
Volume of sample in liters drawn from the canister
and analyzed by GC/MS. For Tenax-based
collections, this volume represents the volume of
whole breath pulled through the Tenax cartridge.
Time (24 hr clock) at which breath collection was
started. The Real Time indicated in the air
samples corresponds to the time at which collection
terminated.
Time in minutes at which the collection of breath
was begun minus the time at which the exposure
ended.
Compound:
CMPD ID:
Mean Blank:
Mean Recov.:
LOD (ng):
QL (ng):
SAMP. ID:
Volume Analyzed (L):
Real Time (HH:MM):
Elasped Time (Min):
D-2
-------
Expenient Mle ) MR SAIPLES; FURNITURE STR!PฐER ซ1
SprsadsHeet File HIM---> MRFS1.
Exposure End Tine ' 13:48
TABLE D-l
CONCENTRATIONS (HICROGRAMS/CUBIC DETER 3 K dej. C. 1 ato.)a
CWPQ
cofpouw :o
Vinyl Chloride 42
Isopentane 57
Pentane 57
Vinyl idene Chloride 41
2-Hethylpentane 71
Dichlorcnethane 84
Chlorofore 83
lilil-Trichloroettiane 41
2-Methylhexane 57 t
Carbon Tetrachloride 62
3-flethylhexane 57 ซ
Benzene 76
Tnchloroethylene 40
Toluene 91
n-Octane 57
2-Hethylpropyl acetatel
Tetrachloroethylene 59
Ethyl cyclohexane (lent.W
Butyl acetate 41 H
3-Hethyloctane 57 0
Ethylbenzene 91
p-Xylene 91 c
n-Nonane 57
Styrene 104
0-Xylene 91
Ii2i4-Tniethylben!ene#
n-Oecane 57
Truethylbeniene isn.J
n-Und?csre 57 (?
n-Oodecane 57 8
1
34
45
44
1
47
34
2
4
56
4
59
5
7
ID
28
40
It
41
42
43
19
22
33
15
21
57
23
44
29
24
Slant
Hear
Recov
LOO
(NG)
, ,._
im iitir AtiAi vTrn ti \
0.00
0.00
000
0 00
000
D 00
000
0.00
0 00
000
0.00
0.00
ODD
0.00
000
0.00
oco
0.00
000
000
0.00
0.00
0 00
000
C 00
0 00
0.00
000
0 00
0 00
vvi.mil. nnr
REAL TIPE
ELAPSED i
1 00
1 00
1 00
1 00
1.00
1 00
1 00
1 00
1. 00
l.OD
1 00
1 00
1 00
1 00
1.00
1.00
1 00
l.OD
1.00
1 00
1.00
1 00
1 00
1 00
1 00
! 00
1 00
1 00
1 00
1 00
UlltlS \L/
f UU MM 1
HE (MINI -
0 07
0 04
0 07
0 03
0.06
0.09
0.03
0.17
0.02
0.02
0.02
0 04
0.04
0.02
0.02
0.02
0.09
D.OB
0.02
0.02
0.01
0.01
0.02
0.01
0 02
D.01
0 02
0.01
0.02
0.02
OL SAW 10
(NG) UDF510CF1
0.27
0.25
0 3D
0 13
032
034
0 10
0 44
0.07
0 ID
007
024
0 17
O.OB
0.07
C CB
034
032
006
007
005
004
007
005
009
0.04
0 1C
004
0 10
0 I?
'
ซ NO >
54
5.1
ND
ป NO *
24
3 5
32
05
ซ ND i
0 7
1 2
I NO i
9.2
NO i
ND ซ
ND I
NO I
ND ป
0.4
0.4
2.3
0 4
20
08
i ND I
1 4
ซ ND ซ
1 7
ND ซ
SAHP ID SAHP ID
140FS1ECF1 140F51ECF1
D7nn
ฃUU
13'48 13
b i ND i
22.9
87
1 0
5.5
NC
09
141.1
359
* ND ป
36.6
2.5
77.4
NCd
25.5
8.4
129
24 D
1 5
728
792
240 0
44.4
31 9
92.1
2 D
1045
3.2
91 2
153
46
ป ND i
21 0
ND ป
i ND i
> ND i
5038.4
NO
120 9
35 B
i ND *
41.4
> ND i
80.4
54799
IB 9
ป ND >
i ND >
23.4
ND >
59 1
4Z.B
2382
554
227
71 5
i ND ป
965
30
74 7
* ND *
SAHP ID SAHP 10 SAHP [1 SปHP. 10 SAHP ID SซHP ID SAHP ID SAHP ID SAHP 10 SAHP ID
140FS1BCF1
Djnn
tuu
1725
> ND i
5 9
2 4
ND <
NO i
ND ซ
ND i
ND i
1 0
* ND ซ
0 4
1 4
ป NO i
2.6
> ND i
I ND
> ND *
i ND i
ซ ND I
i MO i
0.4
1 7
ป NO ป
31.9
0 5
* NO I
I ND *
> NO *
ND I
i ND ซ
8A11 concencracions are to be interpreted only to two significant figures.
Not detected or below QL.
clncludes both meta- and para-isoraers.
Not calculated because of Instrument saturation.
Indicates a non-target compound.
-------
Experiment Title > ALVEOLAR BREATH CANISTER; FURNITURE STRIPPER II
Spreadsheet Fi le Naie> ABCFS1
Exposure End Tin > 13:48
TABLE D-2
CONCENTRATIONS (MICROGRANS/CUBIC METER 3 25 des. Ci 1 atป.)ฃ
CHPO.
COMPOUND 10
(lean Mean
Blank Recov.
LOD
(ME)
OL SANP. ID SAW. ID SAW. [0 SANP. 10 SAMP. ID SAMP. ID SAMP. 10 SAW. ID SANP. ID SANP. ID SAW. ID SAMP 10 SAW
(NG) 140FS1ACFO 140F51ACF1 140F51ACF2 140FS1ACF3 140FS1ACF4 14DFS1ACF5 140F51ACF4 140FS1ACF7 UOFS1ACFB 140F51ACF9 140FS1ACF1D140F51ACF11
VOLUME ANALYZED (L) ) D.05B D.057 D.D59 0.040 0.040 0.040 0.040 0.059 0.040 0.059 0 059 0 040
REAL TIME (rtwm) ) 9:57 13=50 13^55 14:05 14:15 14:25 U'ปl 11=55 15 '30 14:00 14:45 17-29
ELAPSED TIME (HIM) )
Vinyl Chloride 42
Iiopentane 57
Pentani 57
Vinyl idene Chloride 41
2-flethylpentane 71
Dichloroiethane 84
Chloroform 83
lilil-Trlchloroethine 41
2-Mtthylhexane 57 t
Carbon TetracMoride 62
3-flethylhexane 57 9
Benzene 7B
Trichloroethylene 40
Toluene 91
n-Octane 57
2-Methylpropyl acetate*
Tetrachloroethylene 59
Ethyleyclohexane (tent.) 9
Butyl acetate 61 #
3-Hethyl octane 57 t
Ethylbeniene 91
p-Xylene 91
n-Nonane 57
Styrene 10*
o-Xylene 91
I>2f4-Triiethylbemeneff
n-Oecane 57
Triiethyl benzene no. I?
n-Undecane 57 9
n-Dodecane 57 9
34
45
44
1
47
3i
2
4
5B
A
59
5
7
10
28
40
11
41
42
43
19
ZZ
33
15
21
57
23
44
29
24
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
ODD
0 00
0.00
0.00
0.00
00
.00
.00
00
.00
.00
.00
.00
.00
.00
.00
00
.00
.00
.00
.00
.00
.00
.00
.00
00
.00
.00
.00
.00
.00
.00
.00
.00
.00
0.07
0.04
0.07
0.03
o.oa
0.09
0.03
0.17
0.02
0.02
0.02
0.04
0.04
0.02
0.02
0.02
0.09
0 OB
0.02
0.02
0.01
0.01
0.02
001
0.02
0.01
0.02
0.01
0.02
0.02
027
0.25
0.30
0 13
0.32
0 34
0 10
0.44
0 07
0.10
0.07
0.24
0 17
O.OB
007
O.OB
0.34
0.32
o.oa
0.07
0.05
0.04
0 07
0.05
0.09
0.04
0.10
0.04
0.10
0.10
t NO ib
> ND
25.
IND
I NO
I ND
3.
NO
NO
* ND *
i NO i
ปND t
i ND I
1.5
NO*
ซ ND i
i ND i
ซ ND 1
i NO ซ
> ND l
I ND *
IND i
i NO I
IND *
> ND I
i NO *
ND i
i ND i
1 ND 1
I ND l
2
IND i
IND i
IND*
I ND ซ
i ND I
339.1
1 ND 1
54.3
4.9
> ND
5.B
i ND i
48
442.9
2.3
> ND i
I NO i
l ND I
I NO i
3.2
2.2
15. 2
2.2
ND i
1.9
i ND I
l.B
* ND *
1.7
i ND i
7
NO i
l ND ป
ปNOป
l NO ป
l ND *
251.5
1 ND *
42.5
3.4
l ND
4.Z
1 ND l
5.4
350.9
l ND ป
i ND i
i ND ป
* ND *
i NO *
2.4
1.4
5.5
1 4
l ND *
1 NO I
1 ND l
l ND l
l NO i
IND l
l ND i
17
IND ซ
l ND *
l ND
l NO *
i ND *
193.3
1 ND 1
34.4
2.5
* ND ป
3.3
tND
4 7
240.9
ป ND ป
i ND i
i ND *
ป ND 1
l NO
l.B
1.4
12.2
1.2
ND l
3.1
l ND i
i ND i
l ND l
IND 1
l NO l
27
l ND
IND *
IND ป
i ND *
IND*
134.4
5.7
27.0
1.5
NO*
2.B
IND *
3.2
1B4.3
NO*
IND *
IND*
l ND *
* NO *
1.2
1.0
3.0
i ND *
IND*
IND *
0.9
1.7
l ND *
1 ND ป
12.B
37
IND *
i ND *
NO ซ
* ND *
i NO
134.7
1 NO 1
27.B
1.7
l NO *
2.3
l ND *
3.1
190.3
IND *
i ND *
IND *
* ND *
t NO *
1.5
O.B
2.7
l ND *
l ND *
l NO *
1 ND ป
i NO *
l ND l
1 ND l
l ND ซ
53
IND *
* ND *
* ND *
* ND *
* ND ป
105.9
1 ND *
24.2
ND *
IND *
1.3
l ND *
2.7
148.8
ป ND *
* ND ซ
* NO ซ
i ND *
* ND *
*ND ป
ป ND *
1.9
ซ ND *
* ND *
IND *
ป ND *
ซ ND *
* ND ป
* NO *
l ND *
47
* ND *
ND *
NO l
* ND *
l NO *
B9.1
1 ND >
21.1
* ND *
ND ป
* ND *
ป ND *
2.7
149.7
* NO *
* ND ป
ซ ND ป
* ND *
l ND *
* ND ป
* ND l
l.B
* ND *
1 ND *
ซ ND *
ND *
* ND ซ
ป ND
NO *
i ND ป
102
> ND i
* ND i
ป ND i
< ND i
* ND l
71.3
1 ND I
17.4
* ND ซ
* ND *
* NO i
ซ ND ซ
* ND l
133.2
* ND *
ซ ND *
t m *
* ND *
* ND l
ป ND *
1.5
4.9
ซ NO ป
1.9
22
* ND *
* ND ป
> ND *
* ND ป
15.4
132
i ND l
1 ND 1
i ND i
l ND l
i ND i
55.0
2 5
14.0
* ND i
NO l
* ND i
* ND *
IND i
100 5
ND i
* NO l
* ND 1
i ND l
1 ND i
IND i
ป ND *
1.1
NO i
1 ND 1
* ND 1
l ND i
i NO l
i ND i
ซ ND l
* ND *
177
i ND
i ND i
i NO
l ND i
i ND >
55.0
ป ND l
11.4
I NO i
1 ND 1
I ND i
* ND l
l ND l
81.7
* NO ป
l ND l
1 ND l
ซ ND i
* ND *
ND l
i NO l
0.9
NO l
1 NO l
l NO i
l ND l
l NO ซ
ป ND i
ND >
i ND i
221
l ND i
i ND i
134
1 NO *
I ND
37 3
IB 5
l ND
> NO >
i ND *
i ND i
ป NO i
l ND *
39.1
> ND *
i ND i
1 ND >
i ND *
l ND i
i ND i
i ND *
1 1
l NO i
l ND 1
l ND *
l ND i
l ND l
> ND ซ
i ND ป
ป ND i
BA11 concentrations are to be interpreted only to two significant figures.
Not detected or below QL.
clncludes both meta- and para-isomers.
Indicates a non-target compound.
-------
on
Eipernent Title > WHOLE BREATH CANISTER! FURNITURE STRIPPER II
Spreadsheet File Na.e> UBCFS1
Exposure End TIM ) 13'4B
TABLE 0-3
CONCENTRATIONS (MICROGRAMS/CUBIC METER 3 25 deg. Ci 1 ati.P
CMPD.
COMPOUND 10
1 1 1
Mean Mean
Blank Recov.
LOO
(NG)
1
OL SAMP. ID SAMP. 10 SAMP. ID SAMP. ID SAMP. ID SAMP. 10 SAMP. ID SAMP. ID SAMP. 10 SAMP. ID SAMP. ID SAMP. ID SAMP. ID
(NG) 140FS1UCFO 140FS1UCF1 140FS1UCF7 140FS1UCF3 140FS1UCF4 140FS1UCF5 I40FS1UCD5 140FS1UCF4 140FS1UCF7 140FS1UCFB
VOLUME ANALYZED (L) > 0.077 0.079 0.074 0.077 0.080 D.DBO D.DBO 0.060 0.076 0.073
REAL TIME (HH=m) > 10=04 13:58 I4M7 14:34 14=58 15-34 15=34 14=02 14=47 17=31
ELAPSED TIME (M1N) >
Vinyl Chloride 42
Isopintane 57
Pentane 57
Vinyl idene Chloride 41
2-Nethylpentane 71
Dichloroiethane 64
Chlorofon 83
lilil-TricSlaroethane 41
2-Hethylhexane 57*
Carbon Tetrachloride 62
3-flelhylhexane 57*
Bemene 76
Trichloroethylene 40
Toluine 91
n-Octane 57
2-Methylpropyl acetate *
Tetrachloroethylene 59
Ethylcyclohexane (tent.)*
Butyl acetate 41*
3-Methyloctane 57*
Ethylbenzenec9l
p-Xylene 91
n-Nonane 57
Styrene 104
o-Xylene 91
Ii2i4-Triiethylbenzene *
n-Oecane 57
Triiethylbenzene iso. *
n-Undecane 57*
n-Oodecane 57*
34
45
44
1
47
34
2
4
58
4
59
5
7
10
26
40
11
41
42
43
19
22
33
15
21
57
23
44
29
24
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
O.OD
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0 00
000
0.00
0.00
0.00
O.OD
0.00
0.00
0.00
1.00
1.00
1.00
l.OD
1.00
1.00
1.00
1.00
1 00
1.00
1.00
l.OD
l.OD
1.00
l.OD
1.00
l.OD
1.00
l.OD
l.OD
1.00
1.00
1.00
1.00
1 00
1.00
1.00
l.OD
l.OD
1.00
0.07
0.04
0.07
0.03
0.08
0.09
0.03
0.17
0.02
0.02
0.02
0.04
004
0.02
0.02
0.02
0.09
0.08
0.02
0.02
001
0.01
0.02
0.01
0.02
0.01
0.02
0.01
002
0.02
0.27
0.25
0.30
0.13
0.32
0.34
0.10
0.44
0 07
0.10
0.07
0.24
0.17
0.06
0.07
0.08
0 34
0.32
0.08
0.07
0.05
D.D4
0.07
0.05
0.09
0.04
0.10
0.04
0 10
0.10
,NO.b
INDI
i ND i
NDi
ND i
ND l
2.2
ND l
ND 1
INDI
1 NDI
l ND i
IND l
1 7
l ND i
l MO l
l ND l
1 ND 1
l ND i
ND
NO
ND
ND
ND
ND
l ND l
INDI
INOI
i ND l
l ND i
10
i NO i
INDI
INDI
*ND*
i ND i
205.9
l ND l
30.3
1 9
i ND i
2.4
1 ND l
4.4
268.0
INDI
INDI
5.4
IND I
i ND i
1.3
1.2
4.3
1.4
IND i
1.1
* ND *
l NO l
IND i
l ND i
1 ND l
29
iND i
INDซ
IND l
*ND*
i ND i
144.3
1 ND l
21.9
1 4
i ND 1
1.9
i ND i
3.0
198.4
1 ND l
1 ND 1
INDซ
INDI
i NO i
1.0
1.3
3.4
2.8
1.5
1.4
i ND i
1.9
i ND l
IND l
INOI
44
i NO i
IND 1
l ND i
*ND*
l ND i
109.4
l NO l
18.4
1.1
l ND l
1.7
i ND i
2.5
157.0
i ND i
l ND l
i ND i
1 ND I
INDI
l ND i
04
2.1
l ND i
i ND i
i ND i
INDI
i ND i
i ND i
i ND i
1 ND 1
70
i NO i
INDI
i ND i
*ND*
i ND l
70.2
l ND l
1Z.9
IND l
INDI
i ND l
i ND i
INDI
114.9
NO l
INDI
IND i
l ND I
INDI
i ND l
INDI
1.4
INDI
Hffl i
l ND I
i ND i
INDI
i ND i
INDI
l ND l
104
i NDi
i NDi
i ND i
l ND l
i ND i
54.1
INDI
10.1
1 ND l
l ND l
l ND l
l NO l
l ND 1
933
i ND i
INDI
i NO i
1 NO l
i ND i
i ND i
INOI
1.1
INDI
l ND l
INDI
l ND l
l ND l
INDI
i ND 1
l ND 1
104
i NO i
1 ND l
i ND i
l ND l
i ND l
59.2
i ND l
10.2
IND I
l ND l
1 ND l
l ND l
1 ND 1
69.3
l ND l
INDI
i ND i
IND l
i ND i
i ND i
i ND l
1.1
INDI
i ND l
l ND l
l ND l
1 ND l
1 ND 1
i ND i
l ND l
134
i ND l
l ND i
l ND i
l ND l
l ND i
45.7
2.1
6.2
l ND 1
i ND i
i ND l
l ND l
1 ND l
72.7
1 ND l
IND I
i ND i
i ND i
i ND i
i ND i
l ND l
D.9
l ND l
INO i
i ND i
i ND l
i ND i
1 ND 1
i ND i
1 ND 1
179
i ND l
l NO 1
i ND i
l ND l
i ND
55.7
1.5
6.4
1 ND 1
i ND i
l ND i
l ND l
l ND l
54.5
l ND l
1 ND 1
l ND l
i ND l
l ND l
l ND l
1 ND 1
0 7
l ND l
i ND i
i ND i
1 ND 1
l ND 1
1 ND i
i ND i
1 ND l
223
i ND i
l ND l
l ND l
l ND l
IND i
32.9
l ND i
i ND i
i ND I
l ND l
1 7
IND l
i ND i
48.8
1 ND l
1 ND i
i ND i
l ND l
l NO i
i ND i
i ND i
0.4
i ND i
i ND i
i ND i
l ND l
l ND i
1 ND 1
l ND l
l ND l
3All concentrations are to be interpreted only to two significant figures.
bNot detected or below QL.
Includes both meta- and para-isomers.
Indicates a non-target compound.
-------
CTป
Experiment Title > AIR SAMPLES; HARDWARE STORE U
Spreadsheet File Naie> AIRHS1
Exposure End Tue > 13!34
TABLE D-4
CONCENTRATIONS (MICROGRAHS/CUB1C METER 3 25 de9. Ci 1 at..)
COMPOUND
CHPD.
10
Mean Mean
Blank Recov.
LOO
(NG)
OL
(NG)
SAMP. ID SNIP. 10 SNIP. ID SAMP. 10 SANP. ID SAMP. ID SANP. 10
140HS10CF1 liOHSIECFl I4DHS1ECF1 140HS1BCF1
SANP. 10
1 I
SAMP. ID
1
SANP. ID
.1
SAMP
.1
10
SAMP. ID SAI
-1- 1
VOLUME ANALYZED (L) ) O.ZOD
REAL TINE
D.1DO D OZD D.ZDD
5 13=35 17-14
Vinyl Chloride 42
Isopentane 57
Pentane 57
Vinylidene Chloride 41
2-Hethylpentane 71
DicMoroiethane 84
Chloroforo 63
1,1,1-Trichlornelhane 41
2-nethylhexane 579
Carbnn Tetrachlaride 62
3-flethylhexane57tf
Benzene 76
Trichloroethylene 40
Toluene 91
n-Octane 57
2-HethylprDpyl acetate 8
Tetrachloroethylene 59
Ethylcyclohexane (tent.) I
Butyl acetate 410
3-Methyloctane 57 9
Cthylben:ene 91
p-Xylene 91C
n-Nonane 57
Styrene 104
o-Xylene 91
1121 i-Tr i ซthy I benieneff
n-Oecane 57
Triiethylbeniene iso. 6
n-Undecane 57tf
n-Dodecane 570
ฐA11 concentrations are to be interpreted only to two significant figures.
Not detected or below QL.
^Includes both meta- and para-isoners.
flat calculated because of instrument saturation.
Indicates a non-target compound.
34
45
44
I
47
34
2
4
58
t
59
5
7
ID
28
60
11
41
42
43
19
22
33
15
21
57
23
44
29
24
D.OO
D.OD
0.00
D.OO
0.00
D.OD
0.00
a. oo
D.OO
0.00
D.OO
0.00
0.00
D.OD
0.00
D.OD
0.00
D.OD
000
D.OD
O.OD
D.OD
D.OO
O.OD
O.OD
D.OD
0.00
D.OD
0.00
D.OD
.00
.00
.00
.00
.00
.00
00
.00
.00
.00
.00
.00
.00
,OD
.00
.00
.00
.OD
.00
.DD
.00
.OD
.00
.OD
.00
.OD
.00
.OD
.00
.DD
0.07
0.04
0.07
0.03
0.08
0.09
003
0.17
0.02
0.02
0.02
0.04
0.04
0.02
0.02
0.02
0.09
0.08
0.02
0 02
0 111
0.01
0.02
0.01
0.02
0.01
0.02
D.01
002
002
027
0.25
0.30
0.13
0.32
0.34
0.10
0.44
0.07
0.10
0.07
0.24
0.17
0.08
0.07
DOB
0.34
0.32
0.08
0.07
0.05
0.04
0.07
0.05
009
O.D4
0.10
0.04
0 10
0.10
NDซD
41.8
24.9
IND>
94
17.5
24
1 NO 1
1.4
> NO >
2.1
2.5
IND>
13.4
> ID i
ป NO ป
INO>
I NO I
* NO ซ
05
0.8
3.1
NO
NDI
0.8
ND *
ปNOป
0.2
0.7
t ND f
NO i
24.0
142
5.5
24.1
447.2
i NO ป
341.7
1.0
INDป
14.3
4.4
I NO l
339.9
39.8
i ND ป
2747
259
ซND *
95.3
359.1
NCd
1832
33.5
433.3
8.3
288.4
19.7
154.7
24.4
l ND l
21.5
ปND i
7.5
22.3
481.0
i ND i
324.4
13.2
ND >
12.7
ซ ND ซ
1 NO l
314.1
34.7
* ND l
240.4
21.4
ป ND *
74.2
447.2
1412.3
141.7
32.1
435.2
4.5
245.2
15.0
126.0
11.2
i ND i
3D.3
11.7
ซNDi
5.8
l ND ป
NO
< ND *
3.8
ND ป
2.3
3.3
1 ND l
9.4
-------
Experiment Title > ALVEOLAR BREATH CANISTER: HARDUARE STORE ป1
Spreadsheet File Naie---> ABCH51
Exposure End TIK > 13=34
TABLE D-5
CONCENTRATIONS (MICROGRAH5/CUB1C HETER 9 25 deg. Ci 1 att.)a
CHPO.
COMPOUND 10
Ii 1
Mean Mean
Blank Recov.
1 i
LOO
(NE)
1
QL SAMP. 10 SAMP. ID SAMP. ID SAMP. ID SAMP. 10 SAMP. 10 SAMP. 10 SAMP. ID SAMP 10 SAMP. ID SAMP. ID SAMP. 10 SAMP ID
(NG) 140H51ACFO 14DH51ACF1 140H5IACF2 140H51ACF3 140HS1ACF4 140HS1ACF5 140H51ACF6 14DHS1ACF7 I40HS1ACFB 140HS1ACF9 140HS1ACF1D14DH51ACD10140HS1ACF11
lllll|ia|||||l
VOLUME ANALYZED
REAL TIHE 9
0.055
39 13
ELAPSED TIKE (MINI >
Vinyl Chloride 62
lupentane 57
Pentane 57
Vinyl idene Chloride 61
2-Nethylpentane 7r
Dichlnrnethine B4
CMorolori 83
Iilil-Trichloroethane61
2-Hethylhexane 57
Carbon Tetrachloride 82
3-Hethylhexane 570
Benzene 78
Trichloroethylene 60
Toluene 91
n-Octane 57
2-Hethylpropyl acetate t
Tetrachloroethylene 59
Ethylcyclohexane (tent.)#
Butyl acetate US
3-Hethyl octane 57 8
Ethylbeniene 91
p-Xylene 9r
n-Nonane 57
Styrene 104
o-Xylene 91
li2i4-TriNthylbemene
n-Oecane 57
Truethylbeniene iso. f
n-Undfcant 57 8
n-Dodecane 571?
36
45
46
1
47
34
2
4
SB
6
59
5
7
10
28
60
11
61
62
63
19
22
33
IS
21
57
23
64
29
24
0.00
0.00
0.00
0.00
0.00
D.OD
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
ODD
0.00
0.00
0.00
0.00
0.00
0.00
0 DO
0.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
00
.00
0.07
0.06
0.07
0.03
O.OB
0.09
0.03
0.17
0.02
0.02
0.02
0.06
0.04
0.02
0.02
0.02
0.09
O.OB
0.02
0.02
0.01
0.01
0.02
0.01
0.02
0.01
0.02
0.01
0.02
0.02
027
0.25
0.30
0.13
0 32
0 34
0.10
0.66
0.07
0.10
0.07
0.24
0.17
0.08
0.07
D.OB
0.36
0.32
O.OB
0.07
0.05
0 04
0.07
0.05
0.09
0.04
0.10
0.04
0.10
0 ID
IND ib
411.1
150.3
i ND l
68.5
B.3
2.3
NO l
22.1
i ND l
108
13.5
i ND i
14.7
(NO l
1 ND I
17.3
i ND i
ป NO i
1 ND 1
1 ND l
2.1
l ND i
INDi
ซND i
INDI
INDi
1 ND I
INO l
INDi
0.057 0 060 0.060 0.052 0.053 0.057 0.056 0.056 0.055 O.D55 D.D53 D 056
37 13:41 13:51 14:02 14M3 14:29 14:42 15=10 15:40 16=29 16=29 17:11
1
INO i
13.6
7.5
i NO i
IND i
71.7
l ND l
92.3
27
INO i
2.B
4.3
i ND i
27.8
2 1
IND 1
69.5
i ND i
l NO i
4.4
19 1
48.2
13.8
INO l
155
INO I
27.2
i ND i
9.4
i ND i
5
l ND i
10.8
7.2
l ND i
INDI
52.0
INDi
707
2.1
l ND l
2.2
5.4
INO l
20.4
1 3
i ND i
51.7
i ND i
1 ND I
3.6
14.4
36.7
5.0
i NO l
12.4
l ND I
15.7
i ND l
3.8
l ND >
15
INDi
16.1
47.D
l ND i
l ND l
35.7
38
58.5
2.6
l HO i
2.5
iMDi
IND i
17.9
1.2
INDi
383
iHDi
ป ND i
2.3
5.4
30.5
3.6
INDi
4.2
\ NDI
3.9
i ND i
2.0
i ND l
26
i ND i
10.2
6.3
i NO i
i ND l
259
NO i
68.2
1.5
i NO l
IND l
l NO i
i ND l
14.4
ND *
l NO i
36.3
IND i
i NO i
1.5
4.1
25.5
2.3
l ND i
4.6
IND I
2.7
ND i
l ND 1
i NO l
37
1 NO i
7.5
60.4
INDi
IND l
21.9
l ND i
41.7
l NO l
1 ND l
1 ND 1
4.7
1 ND l
7.5
l NO i
INDI
38.1
INDi
INDi
1.2
4.0
25.0
l.B
INDi
3.2
1 ND l
2.1
i ND i
l NO l
INDI
53
1 ND l
5.3
l NO i
i ND l
l ND 1
16.7
l ND l
37.7
i ND i
INDi
IND 1
l ND *
NO i
6.4
i ND i
i ND i
35.0
i NO *
i ND i
l ND i
3.1
21.2
1.4
IND l
2.5
i ND i
i ND *
i ND i
i NO i
i ND l
66
i ND i
5.9
5.0
i ND i
i ND i
16.4
i ND l
35.0
i ND i
a ND i
ซ ND i
* ND i
l ND i
7.3
INDi
i ND i
29.6
l ND i
i ND l
1.3
4 4
21.7
1.3
IND l
4 D
IND i
1.8
NO i
a ND i
i ND l
94
l ND l
1 ND l
l ND i
l NO i
l ND l
10.0
l ND i
28.0
iNOi
i ND i
1 ND l
1 ND l
l NO l
6.9
l ND l
i ND *
266
l ND l
i ND i
l ND l
2.1
15.3
i NO l
l NO l
1.7
l ND l
i ND l
i NO l
ND i
i ND l
126
i NO l
l ND l
i NO l
I ND 1
I ND 1
7.9
l ND i
25.2
l ND l
l ND i
1 ND 1
INO 1
l ND l
4.0
1 ND 1
i ND i
23.5
l ND l
i NO i
l ND 1
1.9
6.0
i ND i
l ND l
i ND i
i ND i
IND l
i ND i
i ND i
l ND i
173
i ND *
i ND i
9.8
i ND
l ND i
6 1
l ND i
23.6
l ND i
l NO i
1 NO 1
1 ND 1
l ND 1
3.6
l NO l
i ND i
22.5
l ND i
i ND
l ND i
1.6
5 2
1.4
l ND l
l NO i
l ND *
1 ND i
l ND i
l NO i
l ND i
173
i NO i
l ND t
i ND i
i ND *
l ND i
6.5
i ND i
23. D
1 ND 1
i ND i
l ND l
1 ND l
i ND i
3.5
1 ND l
i NO i
22.3
l ND i
i ND
l ND i
2.0
5.6
i ND >
l ND l
1 6
l ND i
1 NO l
i ND l
i ND l
* ND
215
ป ND ป
l ND i
ND <
NO
l ND
i ND ป
i ND >
18.6
I ND >
I ND >
1 ND I
1 ND ป
i ND >
2.7
l ND >
i ND *
20 0
i ND ป
i ND *
i ND i
1.1
3 6
ป NO ป
I NO l
i ND >
ซ ND ป
l NO
l ND ซ
> ND >
ป ND ป
BA11 concentrations are to be interpreted only to two significant figures.
Not detected or below QL.
CIncludes both meta- and para-lsomers.
Not calculated because of instrument saturation.
Indicates a non-target compound.
-------
TABLE D-6
CO
Experiment Title ) WHOLE BREATH CANISTER! HARDUARE STORE II
Spreadfheel File Ns.e> UBCHS1
Enposure End Tiie > 13=34
CONCENTRATIONS (MICROGRAMS/CUBIC METER 3 25 deg. Ci 1 at..)8
CHPD.
COMPOUND ID
....-,-
Mean Hean
Blank Recov.
VOLUME ANAl
REAL TIME
ELAPSEOTI
LOO
(NG)
.YZED ID-
HH'HM)--
1E (WIN)
OL SAMP. ID SAMP. ID SAMP. ID SAHP. 10 SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAW ID SAMP. ID SAMP. 1
(NG) UOHS1UCFO UOHS1UCF1 140HS1VCF2 UDHS1UCF3 UOHSlUCFi 140HS1UCF5 UOHS1UCD5 140H51UCF6 140HS1UCF7 140HS1UCFB
i i i i i i i _ i i i i 1 1
)
) 9
V
0.079 0.069 0.071 0.072 0.076 0.077 0.077 D.OBD 0.079 0 078
43 13.44 14:05 14:23 14:45 15=12 15=12 15=42 16=33 17-14
8 29 47 49 96 96 126 177 218
h
Vinyl CKIoride 62
Isopentane 57
Pentane 57
Vinyl idene CKIoride U
2-HetMpenUne 71
Oichlornethane 84
Oilorofori 83
l.lil-Trichlnroethane 41
2-netMซeปane 57*
Carbon TetracMoride 82
3-MetHylheซaปe 57*
Benzine 7B
TrieMoroBlMene 40
Toluene 91
n-Octane 57
2-flethylpropyl acetate *
Tetrachloroethylcne 59
Ethyl eye loKexane (tent.)'
Butyl acetate 41*
3-iletnyloctane 57*
Ethylbenzene^l
p-Xylene 91
n-Nonane 57
Styrene lOi
a-Xylene 91
Ii2i4-Triiettiylbeniene '
n-Oecane 57
Triiethylbeniene iso.0
n-Undecane 57*
n-Dodecane 57*
34
45
44
1
47
31
2
4
SB
4
59
5
7
ID
26
40
11
41
42
43
19
22
33
IS
21
57
23
64
Z9
24
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
O.OD
00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
00
.00
.00
.00
.00
.00
.00
.00
00
.00
.00
.00
.00
.00
.00
.00
.00
.00
0.07
0.06
0.07
0.03
0.08
0.09
0.03
0.17
0.02
.02
.02
.04
.04
.02
.02
0.02
0.09
0.08
0.02
0.02
0.01
0.01
0.02
0.01
0.02
0.01
0.02
0.01
0.02
0.02
0 27
025
0.30
0.13
0.32
0.34
0 10
O.A4
0.07
0.10
0.07
0.24
0.17
D.08
0.07
o.oa
034
0.32
0.08
0.07
O.DS
0.04
0.07
0.05
0.09
0.04
0.10
0.04
0.10
0.10
i NO *
240.4
89.6
IND ซ
29.3
7.2
2.0
9.7
140
IND i
6.6
7.3
IND i
8.0
l NO I
NO i
7.6
1 NO 1
I NO I
i NO i
1 NO 1
1.4
i NO i
1 ND l
IND i
l ND l
i ND i
l ND l
l ND l
l ND *
INOl
108
6.9
i ND >
l ND i
43.6
i NO l
51 4
IND l
*ND*
1.7
ND '
IND 1
14.1
1.0
l ND i
36.4
1 ND 1
NO t
1.9
6.3
21.3
4 0
1 ND >
4 9
l ND 1
3.7
\ ND i
l ND ป
ซ ND >
l ND i
6.7
52
IND i
ND
23.9
NO i
36.9
1.2
*ND*
i ND i
i ND i
IND l
8.D
IND i
i ND l
35.0
IND l
l NO l
2.2
4.0
13.9
2.2
INDI
2.9
1 ND 1
2.0
INOl
l NO ซ
l ND l
* ND i
5.2
4.3
i ND i
i ND i
16.9
i ND l
3D.7
l ND l
l ND l
l ND l
l ND i
1 ND 1
8.1
INOl
l ND l
24.1
IND l
i ND i
1.4
2.9
11.3
1.6
INOl
2.4
1 ND 1
1 5
i ND i
i ND i
i ND i
i ND i
4.7
5.1
i ND l
i NO l
10.7
i ND l
23.0
1.0
l NO 1
i ND 1
NO l
1 ND 1
5.3
IND l
i ND l
21.6
NO 1
IND l
2.0
2.4
9.
1.
IND
2.
l ND
IND
IND l
NO i
iNDi
i ND i
3.2
6.3
i ND l
ND i
8.1
i NO i
21.4
i ND i
i ND l
IND l
i ND i
l ND l
5.0
i ND i
INDI
19.1
1 ND 1
NO i
i NO i
2.0
7.3
1.0
NO i
1.6
i ND i
i NO i
l ND l
i ND i
i ND i
i ND i
3.8
5.8
i ND i
IND i
7.9
i ND i
20.2
l ND ป
i ND i
i ND i
l ND l
l ND 1
4.6
IND i
i ND l
22.1
1 ND *
IND l
l ND l
2.2
8.5
0.9
i ND l
1.7
i ND i
l ND i
1 ND 1
i ND i
i ND i
i NO l
3.7
4 2
l ND l
i ND l
5.2
i ND i
14.3
l ND 1
l ND l
l ND l
l ND i
l ND l
3.2
i ND l
i ND l
14 0
l ND l
l ND i
i ND l
1.4
4.8
l ND l
1 ND >
1.3
i ND i
i ND >
l ND i
i ND >
i ND i
> ND l
i ND >
4.0
l ND l
l NO l
4.9
i ND i
15.8
i NO i
l ND 1
l ND l
l ND i
l ND i
28
l ND l
i ND i
16.8
i ND i
i ND i
l ND l
1.2
4.2
i ND i
i ND i
l ND i
l ND *
l ND i
l ND l
l ND l
l ND l
l ND l
3.0
4 4
1 ND l
1 ND 1
4.8
i ND i
14.4
l NO l
l ND l
IND l
i ND i
i ND i
2.7
1 NO 1
ป ND i
15.8
i ND ป
ND i
l ND l
1.1
36
i ND i
i ND i
l ND l
i ND ซ
i ND i
l ND i
i NO l
1 ND l
aAll concentrations are to be interpreted only to two significant figures.
u '
Not detected or below QL.
clncludes both meta- and para-lsomers.
Indicates a non-target compound.
-------
TABLE 0-7
Eiperiient Title > AIR SAMPLESi SUimtNG POOL t\
Spreadsheet File Haie) AIRSPl
Enpoture End Tiw > 11-34
CONCENTRATIONS (MICROGRAMS/CUBIC METER 9 25 in- C; 1 at..P
O
I
vo
COMPOUND
ChPO
ID
Mean Mean
Bland Recav
LOO
(KG)
01
(NG)
.1..
SAMP. ID SAMP. ID SAMP 10 SAMP 10 SAMP. 10 SAHP. ID SAMP. 10
UOSPIOCF1 140SP1ECF1 J40SP1BCF1
SAHP. 10
SAHP. ID
1
SAHP. 10
SAMP. ID
.1
SAMP. ID
SAMP. 1
VOLUME ANALYZED (L) >
REAL TIME (HH'NN) >
ELAPSED TINE (HIM) >
0.060 O.OS7 0 2DO
9:15 11'34 15'U
Vinyl Chloride 42
Isopentane 57
Pentane 57
Vinylidene Chloride 41
2-Hethylpentane 71
Dichloroiethane Bi
Chlorolon 83
l>lil-Trichloroethane 41
2-flethylhexane 57*
Carbon Tetrachloride 82
3-flethylhesane 57*
Beniene 78
Tnchloroethylene 10
Toluene Tl
n-Octane 57
2-Methylpropyl acetate 9
TetracMoroethylene 59
Ethylcycloheiane (tent.)?
Butyl acetate 41*
3-MethyI octane 57*
Ethylbeniene 91
p-Xyline 91
n-Nonane 57
Styrene 104
o-Xylene 91
liZit-Triiethylbeniene t
n-Oecane 57
Triiethylbeniene iso.0
n-Undecane 570
n-Oodecane 570
aAll concentrations are to be interpreted only to two significant figures.
Not detected or below QL.
clncludes both meta- and para-isomers.
Indicates a non-target compound.
34
45
44
1
47
34
2
4
58
4
59
5
7
10
28
40
11
41
42
43
19
22
33
IS
21
57
23
44
29
24
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
000
0.00
0.00
0.00
0.00
0 00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
00
00
00
.00
00
.00
.00
.00
.00
00
.00
.00
00
.00
.00
.00
00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
00
.00
0.07
0.04
0.07
0.03
0 OB
0 07
0.03
0.17
0.02
0.02
0.02
0.04
0.04
0.02
0.02
0.02
009
D.08
0.02
0.02
0.01
0.01
0.02
0.01
0.02
0.01
0.02
0.01
0.02
0.02
0.27
025
0.30
0.13
0.32
0 34
0 10
0.44
0.07
0.10
0.07
024
0 17
0.08
007
0.08
0.34
0.32
0.08
0.07
0.05
004
0.07
0.05
0.09
0.04
0.10
0.04
0.10
0.10
IND i
20.3
159
IND *
i NO l
41.1
94.4
IND I
22
I NO i
1.1
3.7
I NO i
10.7
I NO >
1 NO ซ
l NO I
1 NO ซ
i NO i
1.2
1.4
7.1
1.5
1.7
20
NO*
25
IND l
1 NO *
i NO ซ
* NO i
54.4
29.7
1 NO l
21.7
l NO i
403.2
l NO l
i NO i
l NDl
14.7
7.8
i NO *
11.0
3.8
1 NO l
IND l
IND l
iNDi
5.7
1.5
4.7
2.5
28
2.0
i KD i
9.9
1 NO l
1D.1
l NO
HOI
40.4
124
i NDl
4.5
ป NO i
1 1
l NDl
1.3
l NDl
1.7
2.8
l NO l
7.0
0.3
1 NO I
2.2
1 NDl
i NO i
1.3
1.2
4.5
1.2
20
1.9
i NO i
2.0
0.2
0.9
3.5
-------
TABLE D-8
o
i-"
o
Experiment Title ) ALVEOLAR BREATH CANISTER; SHIMMING POOL II
Spreadsheet File Naie> ABCSPI
Exposure End Tue ) 11:34
CONCENTRATIONS (HICROGRAHS/CUB1C METER a 25 dej. Ci 1 ati.)
CMPD.
COMPOUND ID
Mean Mean
Blank Recov.
i i
LOO
(NG)
OL SAMP. 10 SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP ID
(NG) 140SP1ACFO 1405P1ACF1 140SP1ACF2 140SP1ACF3 140SP1ACF4 140SP1ACF5 14D5P1ACF6 140SP1AC06 1405P1ACF7 14D5P1ACF6 1405P1ACF9 1405PIACF10
VOLUME ANALYZED (L) > 0.058 0.059 0.060 O.D60 0.060 0.060 0.060 0.060 0.060 O.D5B 0 056 0.059
REAL TIKE (HH'NII) > 9=06 11=36 11'42 11 '52 12-02 12-12 12>27 12=27 12:44 13:12 13-42 14 '27
ELAPSED TIME (HIM) >
Vinyl Chloride 62
Isopentane 57
Pentane 57
Vinyl idem CMoride 61
2-Nethylpentane 71
Dichloroietkane 64
CHorofon 83
lilil-TricMoroethane 61
Z-Hethylhexane 57'
Carbon Tetrachloride BZ
3-rlelMhexane 57 '
Benzene 76
Trichloroethylene 60
Toluene 91
n-Octane 57
Z-Metnylprnpyl acetate'
Tetrachloroethylene 59
Ethylcyclohexane (tent.)'
Butyl acetate 61 '
3-Hethyloctane 57 '
Ethylbenieqg 91
p-Xylene 91
n-Ngnane 57
Styrene 104
o-Xylene 91
liZi4-Triiethylbeniene'
n-Oecane 57
Truethylbeniene iso/
n-Undecane 57 '
n-Oodecane 57'
36
45
46
1
47
34
2
4
56
6
59
5
7
10
28
60
11
61
62
63
19
22
33
IS
21
57
23
64
29
24
0.00
0.00
000
000
0.00
0.00
0.00
0.00
0.00
0 00
0 00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
D.OO
.00
.00
.00
.00
00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
0.07
0.06
0.07
0.03
0 06
0.09
0.03
0.17
0.02
0.02
o.oz
D.06
004
0.02
O.DZ
O.OZ
0.09
o.oa
0.02
0.02
0.01
0.01
0.02
0.01
0.02
0.01
0.02
0.01
0.02
0.02
027
0.25
0.30
0.13
0 32
0.34
0.1D
0.66
0.07
0.10
0.07
0 24
0.17
0.08
0.07
0.08
0.36
032
008
0.07
005
004
0.07
0.05
0.09
0.04
0.10
0.04
0.10
0.10
i ND i
64.3
26.6
i NO l
8.5
6.4
9.Z
l ND 1
3.5
l NO l
Z 0
4.B
l ND l
3.Z
i ND
ป ND ป
l ND l
* ND l
l NO l
IND l
1 ND l
1.0
NO
i ND i
i ND *
i ND >
NO i
ND i
NO ป
> ND i
2
iND
22.7
9.3
i ND i
l ND i
i ND i
61.4
1 ND 1
6.0
1 ND l
3.1
INDI
l ND l
2.0
i ND
ND i
IND l
i ND l
l NO l
l ND ป
l ND l
l ND >
IND l
1 ND l
ป ND
ND
i ND I
NO
ND l
l ND *
6
i ND i
19.2
9.1
i ND
i ND ป
l ND l
57.1
1 ND 1
4 1
1 ND 1
l.S
I ND
1 ND l
3.2
i ND *
* ND i
i NO i
i ND <
IND *
i ND i
l ND i
i ND i
i ND >
i ND *
i ND i
i ND
i ND i
IND
l NO l
IND l
IB
l ND i
14.4
7.7
ปNDซ
i ND
l ND l
43.0
1 ND ซ
2.4
< ND 1
I ND
l ND
IND i
1.6
i NO i
IND l
l ND *
i ND l
i ND >
i ND i
ป ND *
i ND i
IND i
INDI
IND i
i ND i
i ND ป
i ND l
l NO *
> ND
2B
i ND l
7.B
5.2
IND i
i ND l
l ND I
39.9
1 ND *
2.3
I ND 1
I ND 1
1 ND 1
INDI
1.9
i ND l
* ND l
i ND l
i ND l
INDI
INDI
i ND l
INDI
l NO 1
INDI
INDI
INDI
ป NO 1
l ND *
i ND 1
l ND l
36
IND l
5.7
IND
l ND l
l NO ซ
ป ND l
32.8
1 NO I
1 2
i ND l
i ND >
l ND l
l ND l
1.6
l ND I
l ND i
IND I
INDI
l ND l
ซNDป
i ND l
i ND i
INDI
IND*
IND l
iNOi
iND i
i ND
ND l
1 ND 1
53
ป ND l
4.D
ND
NO
NO
NO l
29.6
l ND 1
l ND
l ND 1
i ND i
l ND l
l ND 1
1.3
IND i
*ND i
i ND i
IND i
ND i
i ND i
NO
i ND i
NO
ND i
ND i
ND l
1 ND l
1 ND 1
1 NO 1
i NO l
53
l ND
3.9
i ND *
i ND *
I ND I
1 ND
27.6
l ND
1.5
i ND
ND
l ND l
l ND i
1.6
i ND i
i ND
NO
l ND
l ND
ซ ND
ND
0.9
i ND
i ND i
i ND i
ND 1
1 ND l
i ND ป
l ND *
ป NO *
70
NO l
69
ND l
ND i
l ND l
ป ND
232
* ND l
1.1
1 ND 1
ND l
ND l
NO
1 NDI
l ND ซ
ND
ซ ND i
* NO l
i ND i
* ND i
l ND
NOi
l ND l
* ND l
ป ND l
l ND
ND i
ND l
ND i
ND l
98
1 ND i
6.D
l ND l
l ND ซ
l ND >
l ND
17.9
1 ND 1
1.4
1 ND 1
1 ND
l ND l
l ND
IND 1
l ND l
l ND l
* ND l
l ND l
l ND i
l ND i
1 ND i
l ND l
i ND i
l ND 1
l ND 1
l ND i
ND l
l ND *
1 ND l
ป ND ป
128
ND
7.3
6.2
ND ป
i ND
1 ND
16.7
I ND l
1.2
i ND l
l NO l
ND
l ND l
1.3
IND
i ND l
i ND i
i ND i
NO
ND
NO i
ND
ND
NO l
l ND >
l ND l
ND
ND
ND
ซ ND
173
l ND
4 4
1 NO
i ND
i ND
i ND
16 1
* ND
* ND
1 ND
1 ND
ND
ND
ND
l ND
ND
l ND l
* ND
ND
* ND
ซ ND
i NO
ND
l ND
1 ND
l ND
l NO
i ND
< ND >
ND *
aAll concentrations are to be interpreted only to two significant figures.
Not detected or below QL.
'includes both meta- and para-isomers.
Indicates a non-target compound.
-------
Experiment Title ) UOOO SHOP ซti CANISTER AIR SAMPLES
Spreadsheet File Naie> AIRUS1
Exposure End TUB > 14:02
TABLE 0-9
CONCENTRATIONS (MICROGRAMS/CUBIC HETER 3 25 deg. Ci 1 atป.)a
COMPOUND
CHPO
ID
(lean Mean
Blank Recov.
LOO
ING)
I 1.
OL
(NG)
SAMP ID SAMP. ID SAW1. ID SAMP ID SAMP ID SAMP ID SAMP. ID
liOUSlOCFl UOUS1ECF1 140US1ECD1 UOUS1BCF1
.1 i 1 1 1 1 1
SAMP. 10
1 i
SAMP ID
| 1
SAMP. ID
1
SAMP. 10
1
SAMP. ID
1
SAMP ID
1
VOLUME ANALYZED (L) >
REAL TIME (HH:MM) >
ELAPSED TIME (MINI >
0.200 0 05D 0.050 0 20D
9 i? 14:02 14.02 17.46
34
15
46
1
17
34
2
*
SB
&
59
5
7
10
28
ID
11
61
42
43
19
22
33
15
21
57
23
44
29
24
0.00
D.OO
D.OO
0.00
DOD
D.OO
0.00
D.OO
0.00
0.00
0.00
D.DD
0.00
D.OO
0.00
D.DD
0.00
D.OO
D.OO
0.00
ODD
ODD
D DO
O.OD
ODD
DOD
0.00
ODD
ODD
0.00
.00
00
.00
.DO
.00
.00
.00
DO
.00
.00
.00
.00
00
.00
.00
.00
00
.00
DO
.00
.00
.00
.00
.00
.00
.00
.DO
.00
.00
,DD
D.D7
004
007
D.03
DOB
0.09
0.03
D 17
0 02
0.02
002
0.04
0.04
0.02
0.02
0.02
009
o.oa
OD2
0.02
D.Ol
0.01
0.02
0.01
0.02
0.01
002
001
002
0.02
0.27
025
0.30
0.13
0 32
0.34
0.10
0.44
0 07
0.10
007
024
0.17
0.08
0.07
O.OB
0.34
0.32
DOB
0.07
0.05
D.04
0.07
0.05
0.0?
OOi
0 10
0.04
0 10
0.10
ป ND ปb
12.1
10.4
l ND I
30
1 8
21
l ND 1
0 4
D9
04
24
i ND l
173
1.0
l NDI
i ND l
i ND ป
l ND I
0.5
1.2
59
DB
7.4
24
i ND>
2.0
i ND ซ
1 D
l ND <
ป ND *
28.4
333.5
56.1
293
30 B
35
144B4.5
&i
NC3
6.7
6.7
14.1
534 8
104.3
1 ND
37.9
ND ป
1 ND 1
37.D
5 1
17.2
50 4
4.0
4 4
INTJI
91 4
i ND >
8.9
1 9
i NO l
30 2
342 4
55.7
29 3
27.1
3 7
15514.6
S-'H
NCd
6 6
6.7
135
487.4
106.1
l ND l
39.9
l ND i
ซ ND 1
33.2
S.O
16.6
530
3.6
ป 3
IND 1
BOB
> ND <
88
ซ ND
I ND 1
11.8
S.B
0 7
l ND i
56
1.7
599
l ND 1
ND l
ป ND i
1.6
l ND l
8.8
0.8
i ND i
l ND ซ
i ND ป
IND i
INO l
0.7
3.4
1.4
09
0.9
l ND l
2.5
ซ ND >
0 6
1 NO l
Vinyl Chloride 62
Uopentane 57
Pentane 57
Vinylidene Chloride 61
2-Nethylpentane 71
OicMoroiethane 64
Chlorofon 83
lilil-Trichloroethane 82
2-Methylheiane 57 0
Carbon Tetrachloride 82
3-Nethplhexane 57 f
Benzene 78
TncKloroethylene 60
Toluene 91
n-Octane 57
2-MetMpropyl acetate*
Tetrackloroethylene 59
Ethylcyclohexane (tent Iff
Butyl acetate 61 t
3-MelhyI octane 57 9
Ethylbenieng 91
p-Xylene 91
n-Nonane 57
Styrene 104
o-Xylene 91
1i2i4-Triiethylbeniene^
n-Oecane 57
Tmethylbenzene isal
n-Undecane 57f
n-Dodecane 57*
aAll concentrations are to be interpreted only to two significant figures.
Not detected or below QL.
CIncludes both meta- and para-isomers.
Not calculated; large mass of 1,1,1-trichloroethane might have observed this ion for carbon tetrachlorlde.
Indicates a non-target compound'
-------
TABLE D-10
o
i>
ro
Expernent Title > ALVEOLAR BREATH CANISTER; 1)000 SHOP II
Spreadsheet File Nan> ABCUSt
Exposure End Tme > U-Q2
CONCENTRATIONS (HICROGRANS/CUBIC METER 3 25 deg. Ci 1 atii.f
CMPO
COnPOUNO ID
i . . __ _!. 1
Vinyl Chloride 62
Isopentane 57
Pentane 57
Vinyl idene Chloride 61
Z-Methylpentane 71
Dichlornethane 84
Chloroton 83
1.1.1-Trichloroethane 61
Z-Nethylhexane 57 t
Carbon TetracMoride 82
3-rIethylr.exane 57 9
Benzene 78
TricMoroethylene 60
Toluene 91
n-Octane 57
Z-Hethylprapyl acetate*
TetracMoroethylene 59 .
Ethy 1 eye lohexaneJ tent.)
Butyl acetate 61 .
3-Hethyloctane 57
Ethyl benzene 91
p-Xylene 71C
n-Nonane 57
Styrene 104
o-Xylene 91 .
hZii-Trimthylbenzene
n-Oecane 57
Troethylbenzene iso. 0
n-Undecane 57 9
n-Dodecane 570
36
45
46
1
47
34
2
4
58
6
59
5
7
10
28
60
11
61
62
63
19
22
33
15
21
57
23
64
29
24
dean Mean
Blank Recov
i i
VOLUME ANA!
REAL TINE
ELAPSED TIP
0.00
0 00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
D.DO
000
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
000
0.00
0.00
0.00
000
000
0.00
00
.00
00
.00
00
.00
.00
.00
.00
00
.00
.00
.00
DO
00
00
.00
.00
00
00
.00
00
.00
DO
.00
.00
00
.00
.00
00
LOO
ING)
.YZEO (L)
HH:m|-
C (DIN)
O.D7
0.06
0.07
0.03
0.08
0.09
0.03
0.17
O.OZ
0.02
O.OZ
0.06
0.04
O.OZ
0 02
0.02
0.09
0 08
0.02
0.02
001
0.01
0.02
0.01
002
0.01
0 OZ
O.DI
O.OZ
O.DZ
01 SAMP ID SANP ID SAMP 10 SAMP ID SAMP. ID SAMP. 10 SAMP. 10 SAMP. ID SAMP. ID SAMP. ID SAMP ID SAMP. 10 SAMP 10
(NG) UDUS1ACFO UHUSIACFI 140W51ACFZ 140US1ACF3 140U51ACF4 KOUS1ACF5 UOU5IACF6 140US1ACF7 UOU51ACF8 UOU51ACF9 140U51ACF10140U51ACF11
i i _i i i i i_ _ i_ i_ i i _i _i
>
> 9
0.27
0 25
0 3D
0.13
0.3Z
034
0 10
0.66
0.07
0.10
0.07
0.24
0.17
008
0.07
0.08
036
0 32
0.08
0.07
0.05
0.04
0.07
0.05
0.09
0.04
0 10
004
0 10
0.10
0.059 0 058 0 060 0.060 0.060 0 060 0.060 0 060 0 060 0.060 0 060 0 060
16 14=05 14-10 14:20 14:30 14:40 14:56 15'U 15:40 16-16 11:58 1740
3 8 18 28 38 54 69 98 134 176 218
NO ปb
NO ซ
l NO >
i NO ป
NO l
l NO l
22
i HO i
i NO *
i NO i
ซ NO i
l NO
l NO ป
1 3
t NO >
l NO ซ
1 NO 1
l NO >
> NO ป
i NO i
> NO >
i NO >
i NO l
i NO <
l NO i
1 NO l
l NO >
l NO ซ
l NO >
ซ NO i
i NO i
NO ซ
15.8
16.0
NO i
l NO 1
NO i
6169*
l NO l
ซ NO l
i NO i
ซ NO *
ปND >
ZZ 8
2.2
i NO
13.8
(NO l
i NO ป
IND ซ
NO >
> NO
IND l
i NO l
NO i
ซ NO 1
ซ NO *
l NO 1
1 NO 1
l NO >
l NO ป
i NO t
13.3
13.7
* NO i
ป NO 1
i NO *
4605.7
> NO <
* NO >
i NO >
* NO *
i NO *
18 6
1 8
i NO i
11.5
NO ป
> NO ซ
1 ND l
NO l
i NO l
l NO 1
i NO *
l ND i
1 ND 1
NO l
l ND l
l NO 1
l ND l
i ND l
l NO l
9 5
9.4
i ND i
l ND 1
l ND i
35054
l ND l
ซ ND l
l ND l
l ND i
i NO l
16 1
1.5
l NO i
10.2
ND i
ป ND *
l ND l
> ND l
* ND i
l ND l
> ND ซ
i ND *
1 ND 1
1 ND l
l ND 1
ป ND ป
1 ND l
l NO 1
i NO l
7.9
9.6
i ND i
5 4
i ND l
2573.5
IND i
ND i
l ND l
i ND l
l NO l
18.2
1.5
l NDซ
7.6
IND i
> NO i
l ND l
l ND l
i ND l
IND l
IND l
l ND l
1 ND 1
1 NO 1
l ND ซ
IND l
IND l
i ND i
i ND ซ
8.5
95
1 ND I
* ND l
i ND i
2955.3
NO i
i ND i
ปND i
* ND ป
i ND i
14.2
1.6
iNDi
10.4
i ND l
i ND i
* ND l
l ND l
l ND
i NO i
i ND i
* ND i
l ND 1
IND 1
l ND ซ
1 NO *
1 ND l
iNO ป
i ND i
12.8
8.9
iNO i
l ND I
> NO *
2355.8
1 NO i
i ND *
l NO
NO l
l NO i
11.9
1 3
i ND l
6.1
i ND i
ป ND l
1 ND l
ป NO ป
i ND i
l ND i
i ND i
l ND l
l NO i
IND i
i ND i
l ND l
l ND l
l ND i
ND l
6.3
a z
I ND i
1 ND l
l NO i
194Z.6
l ND l
l ND i
l ND l
l ND i
i ND i
11 3
1.1
1 ND 1
176
l ND l
ป NO ป
* ND i
i ND i
l ND l
ND i
i ND
l ND 1
l ND l
l ND 1
l ND l
l ND l
IND l
i ND ป
l ND ซ
5.0
7.3
i ND i
1 ND l
l ND i
1689.7
l ND l
l ND l
l ND l
l ND l
i NO t
59
i ND >
l ND i
59
i ND
i NO i
i ND *
i NO i
l ND l
i ND i
i ND i
1 ND l
1 ND l
I ND l
1 ND l
> ND l
1 ND l
IND i
i ND i
l ND l
6.1
l NO ป
ซ ND 1
i ND i
1316. Z
l ND l
ป ND l
i ND i
i ND l
ป ND l
5 5
ป ND i
ป NO >
58
* ND ป
i ND i
ND l
l NO *
l ND l
> ND >
> ND *
* ND ซ
l ND ป
ND *
1 ND ซ
* ND *
l ND ป
> NO i
i ND i
l ND l
7.1
ป ND
1 ND 1
l ND ป
1125 7
I ND l
l ND ซ
l ND l
l ND *
> ND i
5 Z
i ND >
ND i
6.1
l ND l
i ND >
* ND >
l NO ป
l ND l
i ND >
i ND *
l NO ป
i ND ป
l NO *
1 ND I
* ND ป
l ND i
ซ ND ป
ND ซ
ป ND l
8 Z
ป ND ป
I ND ซ
ซ ND >
1040 3
l NO i
i ND ซ
l NO i
l NO *
ป ND ป
4.0
i NO i
i NO i
l ND >
i ND l
> ND >
> ND *
> NO ซ
ซ NO ป
ป ND >
ND
> NO l
ซ NO '
ป ND >
ซ ND <
ป NO ป
ป ND l
All concentrations are to be Interpreted only to two significant figures.
Not detected or below QL.
Includes both meta- and para-lsoners.
Indicates a non-target compound.
-------
Eปptrnent Title > AIR DATA. CONSUMER PRODUCTS U> TENAX SAMPLES
Spreadsheet File Na.e~> AIRCP1
Exposure End Ti.e > 13 57 5/12/89
TABLE D-ll
CONCENTRATIONS (M1CROGRANS/CUBIC METER)3
CHPO
COMPOUND ID
1 1
lean Mean
Blank Ricov.
LOO OL SAW. 10 5AHP. ID SAMP. 10 SAMP. ID SAMP. ID SAMP. ID SAW. 10 SAMP. ID SAMP. ID SAMP ID SAMP. ID SANP. ID SAKP 10
ING) ING) 140CPIOTF1 140CP1ETF1 UOCP1ETD1 140CP1BTF1 UOCP1BTF2 HOCP1BTF3 140CP18TF4
VOLUME ANAUZED (L) > It. 4 3.1 2.8 11.0 24.2 33.D 25.9
START TINE/OATE > 20-44 5/11 BUI 5/12 8:41 5/12 14=03 5/12 20:05 5/12 15:26 5/13 15:52 5/14
STOP TIME/DATE
ii-Octane 71
ip-Xylene 104
Styrene 10(
o-Xylene 104
n-Nonane 128
alpha-Pinene 93
p-DicMorobeniene 17
n-Oecane liZ
Liionene 46
n-Oodecane 17D
All concentrations are
Not detected or below
O
i
26
22
15
21
33
31
17
23
32
24
to
QL.
O.OD 00
O.OD .00
O.OD .00
O.OD 00
O.OD .00
O.OD .00
0.00 .00
O.OD .00
O.OD .00
O.OD 1.00
570
7.00
7. DO
450
430
5.70
16.00
9. DO
7.30
9.30
be Interpreted only
7-50 5/12 13-
23.00
28.00
28.00
24.00
2500
23.00
7200
34.DD
29. OD
37.0D
to two
NO ป b
34
INOI
ป NO l
NO 1
4.2
> NO >
1 ND I
10 1
l ND i
58 5/12 13:58 5/12 20:15 5/12 15-25 5/13 15 ND <
I NO I
ป NO ป
i ND ป
946
9354 6
l ND 1
142.4
< ND <
i ND >
ND i
NO ป
l ND ซ
> ND ซ
92.1
10442.9
ND 1
154.6
1 ND 1
l NO i
3.2
i ND l
IND i
i ND i
i ND <
2176
l ND i
l ND l
l ND >
1.2
3.4
l ND 1
1.1
1.2
4.0
27.1
l ND l
4.3
ซ ND i
2.1
3.6
1 NO l
1.2
l.S
4.0
10.2
1.9
4.2
* ND i
2.0
5.4
IND 1
1.9
1.3
6.9
5.5
IND 1
7.6
IND l
significant figures.
CO
-------
Expernenl Title > UffiLE BREATH. CONSUMER PRODUCTS II. TENAX SAMPLES
Spreadsheet File Mane) UBTCP1A
Eปposure End Tin > 13:57 5/1Z/8?
TABLE D-12
CONCENTRATIONS (IHCROGRAMS/CUBIC HETER)a
COMPOUND
n-Octane 71
np-Xylene 106
Styrene 104
o-Xylene IDA
n-Nonane 1ZB
alpha-Pinene 73
p-OicMorobeniene 17
n-Oecane 142
Lnonene 68
n-Oodecane 170
CMPD
ID
i
(lean Mean
Blank Recov
LOO
(NG)
01 SAMP. ID SAMP ID SAMP ID SAMP 10 SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP. 10 SAMP. 10 SAMP ID SAMP ID
(NG) 140CP1UTFO UOCP1UTF1 140CP1UTF2 140CP1UTF3 140CP1UTF4 UOCP1UTF5 140CP1UTF6 140CP1UTF7 14DCPIWTFB I4DCP1UTF7 140CP1UTF10140CP1UTF11I40CP1UTF12
VOLUME ANALYZED (L) >
ELAPSED TIME (MRS) >
ZB
22
IS
21
33
31
17
23
32
24
0.00
0 OD
D.DD
0.00
0.00
000
0.00
000
0.00
0 00
.00
.00
.00
00
00
.00
.00
.00
.00
.00
570
7.00
700
6.50
6.30
5.70
18.00
9.00
7.30
9.30
23.00
26 00
2B.OO
26.00
25.00
2300
72.00
36.00
2700
3700
18.4
b
l NO i
i NO *
ND ป
l ND >
NO*
l ND >
ป ND ป
l ND l
7.4
ND >
11. B
005
i ND l
l ND ป
NO *
l NO ป
ปNDป
6.7
349.4
IND >
6.4
IND ซ
11.9
0.35
l ND I
ND
l NO ซ
1 ND 1
l ND
38
245.0
ป ND i
45
ป NO ซ
11 9
0.63
l ND l
l ND i
l ND *
l ND ป
l ND ป
3.1
209.5
* ND i
4.2
ป ND *
11.9
0.75
* ND l
ซ ND >
ป ND i
* ND
* ND *
2.4
177.4
ป ND l
3.4
ป ND i
15.3
1.25
*ND l
l NO i
ป ND >
l ND i
ซ ND *
2.2
1575
ซ ND i
3.3
i NO >
16.B
1.47
l ND *
> NO >
ND
> NO >
ซ ND l
1.7
137 7
i ND
2.7
i ND >
IB 3
2.17
i NO I
i NO
> NO i
t NO ป
> ND ป
1 5
130.2
l ND ซ
33
l ND ซ
2D.9
2.92
* ND >
ND ซ
* ND
l ND l
l ND
1.1
81. t
ซ ND l
2.2
ป ND ป
17.5
365
l ND <
i ND l
ป NO ซ
t ND ป
l ND ป
l ND ซ
102.0
l NO 1
2.7
i ND *
16. D
7.22
ป ND
ป ND >
< ND
l ND i
ป ND
l NO ซ
70 2
I ND
2.8
ป ND
1-
17.3
1780
* ND >
> ND i
> NO *
i NO i
ND ซ
ซ ND l
435
l NO
2 3
ND ป
1
16 6
30 70
ND 1
ND i
ป ND i
ND i
* ND i
1 8
34 2
ND i
6 2
> ND *
All concentrations are to be Interpreted only to two significant figures.
Not detected or below QL.
-------
Etpement Title > UHOLE BREATH, CONSIDER PRODUCTS H. TENAX SAHPLESi CONTINUED
Spreadsheet File Hue> UBTCPIB
Exposure End Ti.e > 13:57 5/12/89
TABLE D-13
CONCENTRATIONS (NICROGRAI1S/CUBIC METER)8
COMPOUND
n-Octane 71
np-Xylene 104
Strrene 104
o-Xylene 104
n-Nonane 128
alpha-Pinene 93
p-DicMorobentene 17
n-Oecane U2
Lnonene 48
n-Oodecane 170
CMPO
ID
28
22
15
21
33
31
17
23
32
24
Nun Nun LOO
Blank Recov. (KG)
VOLUME ANALYZED (L)
ELAPSED TIME (MRS)
0.00 1.00 5.70
0.00 1 00 7 00
0.00 1.00. 7.00
0.00 .00 4.50
0.00 .00 4.30
0 00 .00 5.70
0.00 .00 18.00
0 00 .00 9.00
0.00 1.00 7.30
0 00 1.00 9.30
QL SAMP. 10 SAMP. ID SAKP
(NG) 140CP1UTF13140CP1UTF14
>
23.00
28.00
28.00
24.00
25.00
23.00
72.00
34.00
29.00
37.00
19.t
50.00
ND b
NO
NO
ND
ND
1.3
30.4
l ND l
5.7
l ND i
15.7
48.40
l ND t
1.8
l ND l
l NO i
ND ป
l NO i
224
IND ป
34.1
i ND l
ID SAKP ID SAMP. ID SAMP. 10 SAKP. 10 SAKP. ID SAMP. 10 SAKP. ID SAMP. ID SAKP ID SAKP ID
140CP1UTD1 140CP1UTD3 140CP1UTD4 I40CP1UTD5 HOCP1UTD6 14DCP1UT08 140CP1UT09 140CP1UTD11140CP1UT012140CP1UTD14
12.2
0.05
l ND l
i ND i
i ND l
l ND l
ND i
7.0
349.1
l NO l
7.0
1 ND 1
12.5
0.43
i ND i
i ND i
ซ ND i
i ND i
i ND i
3 1
202.2
> ND l
4 3
1 NO l
12.4
0.95
l ND l
i NO l
l ND l
i ND >
i ND i
2.4
175.7
ND l
34
ซ ND i
14.3
1.25
INDI
ND i
l ND i
INDI
i ND i
2.0
154.7
IND l
3.4
IND l
17.7
1.47
INDI
l ND l
l ND l
l ND i
l ND i
1.6
143.8
i ND l
3.3
l ND 1
220
2.92
IND l
i ND i
NO i
i ND i
i ND l
1.3
83.7
l ND l
25
l ND i
18.7
3.45
l ND i
i ND i
l ND i
i ND l
INDI
i ND i
101.2
1 NO l
2.7
1 ND i
17.2
17.80
i ND l
i ND >
l NO l
l ND i
ซ ND i
i ND l
45.8
i ND i
25
ซ ND ซ
17.3
30.70
IND i
i ND i
i ND i
l ND i
i ND
1 7
35.5
l NO l
5.8
l ND l
14.3
48.40
l ND 1
1 9
i ND >
ซ ND *
i ND ซ
ป ND >
24 7
I ND ป
34.9
ซ ND i
All concentrations are to be Interpreted only to two significant figures.
Not detected or below QL.
t
en
-------
I
!
CTป
TABLE D-14
E>periซnt Title > AIR MONITORING RESULTS FOR GS1 EXPOSURE EXPERIMENT; CANISTER COLLECTION
Spreadsheet File Hare> AIRGS1
Exposure End Tup > 13 47 CONCENTRATIONS (MICROGRAH5/CUBIC METER 3 25 des. Ci 1 ati )
CMPO.
COMPOUND ID
Mean lean
Blank Recov.
LOO
(ME)
01 SAMP. 10 SAW. ID SAMP. 10 SAMP. ID SAW. 10 SAW. ID SAW. ID SAW ID SAW. ID SAW. ID SAMP ID SAMP. 10 SAMP. 1
(NG) 140SS10CF1 14DES1ECF1 I40GS1BCF1
VOLUME ANALY2ED (L) > 0.20D 1.000 0200
REAL TINE (HH'HM) > 11-30 13'47 17:38
ELAPSED TINE (HIM) >
Vinyl Chloride 62
Isopentane 57
Pentane 57
Vinyl idene Chloride 41
2-Hethylpentane 71
Dichloroiethane 84
CMorotori 83
1.1,1-TrichloroBthanc 61
2-Helhylheปane 57 1
Carbon Tetrachlonde 82
3-ซethylhexane57tf
Benzene 7B
Trichloroethylene 40
Toluine 91
n-Octane 57
2-Nethylpropyl acetate?
Tetrachloroethylene 59
Ethylcyclotaiane (tent.) 9
Butyl acetate ฃ10
3-flethyloetane 57 9
Ethylbeniene 91
p-Xylene 91C
n-Nonane 57
Styrene 104
o-Xylene 91
Ii2r4-Truethylbenzene 9
n-Oecane 57
Truethyl benzene iso. 9
n-Undecane 570
n-Dodecane 57*
36
45
44
1
17
34
2
4
SB
6
59
5
7
10
28
60
11
61
62
63
19
22
33
15
21
57
23
64
29
24
0.00
0.00
0.00
0.00
0 00
000
000
0.00
0.00
O.OD
0.00
0.00
0.00
0.00
0.00
O.OD
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
O.OD
0.00
O.OD
0 00
0.00
.00
00
00
.00
00
.00
DO
.00
.00
00
.00
.00
.00
00
.DO
.00
00
.00
.00
.00
.00
.00
00
.00
.00
.00
.00
.00
.00
.00
0.07
0.06
0.07
0.03
D.OB
0.09
0.03
D.17
0 02
D.02
0.02
D.06
0.04
0.02
0.02
0.02
0.09
0.08
D.02
0.02
0.01
0.01
D.02
0.01
D.02
0.01
0.02
0.01
002
D.02
0.27
0 25
0.30
0.13
032
0.34
0.10
066
D 07
0 ID
0.07
0.24
0 17
D.08
0.07
0.08
0.36
0.32
0.08
0.07
0.05
0.0*
0.07
0.05
0.09
0.04
0.1D
0.04
0.10
D ID
iNOib
32.6
35.3
ป ND ป
7.9
8.6
11.5
6.7
1.6
1 ND 1
2.4
2.7
ND
IB. 4
0.6
NO l
l NO I
I ND I
I ND 1
1.2
1.4
5.9
0.8
6.8
2.5
0.2
15.0
0.6
54. 5
0.8
l ND <
10100.0
3440.0
ND ป
1990.0
1 NO ซ
ป ND l
ND i
342.0
1 ND i
406.0
427.0
i ND >
1240.0
319.0
l ND ป
ND l
904.0
f ND l
2610.0
1680.0
12020.0
NDi
701.0
113.0
13800.0
300.0
5590.0
446.0
l NO 1
15. i
5 6
i NO i
2.8
l ND l
ป ND ซ
1 NO
0.6
< ND
0.5
1.2
ป ND i
3.1
IND >
ป ND
NO*
i ND ซ
l ND 1
0.8
0.6
1 9
1.4
2.4
D.6
i ND ป
3.3
i ND ซ
3.4
0.6
All concentrations are to be interpreted only to two significant figures.
Not detected or below QL.
'includes both meta- and para-isomers.
Indicates a non-target compound.
MOTE: Concentrations for the garage exposure sample (ECF1) were calculated from full scan MS data and relative response factors using a one-point
calibration.
-------
TABLE D-15
Expedient Title > ALVEOLAR BREATH EXPOSURE EXPERIMENT; GS1 (GARAGE/SOLVENT); CANISTER COLLECTION
Spreadsheet Pile Nase> ABCGS1
xpD5uret.no me -i u=ปr
CMPO.
COMPOUND ID
Mean Mean
Blank Recov.
LOO
(NG)
Lunutninrtiiura iniiKUBRnrariuoii ncicn o a oeg. LI j oiw.i
OL SAMP. 10 SAMP. 10 SAMP. 10 SAMP. 10 SAMP. 10 SAMP. 10 SAMP. 10 SAMP. [0 SAMP 10 SAMP. 10 SAMP. ID SAMP ID SAMP 10
(NG) 14DGS1ACFD 14DGS1ACF1 UQGS1ACF2 140GS1ACF3 140GS1ACF4 140GS1ACFS HOGS1ACF4 16DGS1ACF7 140GS1ACFB UOGSIACF7 140G51ACF10140G51ACF11
VOLUME ANALYZED (L) ) 0 060 0.058 0.060 0 060 0.060 0.060 0.060 0.060 0.057 0.060 0 060 0.060
REAL TIME (HH=MM) > 11:00 13:50 13:55 14:03 14:12 14:2? 14:47 15:03 15:34 16:03 16:68 17 34
ELAPSED TIME (NIN) >
Vinyl Chloride 62
Isopentane 57
Pentane 57
Vinyl idene Chloride 61
Z-Ht thy 1 pent ant 71
Oichlornethane 66
Chlorofori 83
lilil-Trichloroethane 61
2-Hetnylhexane 57 *
Carbon Tetraehlonde 82
3H1ethylhe>ane 57 1?
Bemene 78
Trichloroethylene 60
Toluene 91
n-Octane 57
2-Methylpropyl acetate ป
Tetrachloroethylene 57
Ethylcyclohexane (tent.)'
Butyl acetate 41*
3-Hethyl octane 57*
Ethylbenienec71
p-Xylene 71
n-Nonane 57
Styrene 104
o-Xylene 71
liZi4-Triiethylbeniene t
n-Qecane 57
Triiethylbeniene iso. t
n-Undecane 570
n-Oodecane 570
36
45
46
1
47
34
2
4
58
6
57
5
7
ID
28
60
11
61
62
63
19
22
33
15
21
57
23
64
29
24
O.OD
0.00
0.00
O.OD
D.OO
0.00
0.00
0.00
O.OD
0.00
0.00
0.00
0.00
D.OO
0.00
fl.Dfl
0.00
O.OD
0.00
0.00
0.00
0.00
0.00
000
0 00
0.00
0.00
0.00
0 00
0.00
.00
.00
.00
.00
00
.00
.00
.00
.00
.00
.00
.00
.00
OD
.00
00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
007
0.06
0.07
0.03
0.08
0.07
0.03
0.17
0.02
O.OZ
0 OZ
0.06
0 04
O.OZ
O.OZ
0.02
0.07
O.OB
002
D.OZ
0.01
0.01
O.OZ
0.01
O.OZ
0.01
O.OZ
0.01
O.OZ
D.OZ
0.27
0.25
0.30
0 13
0.32
0.34
0.10
0.66
0.07
0.10
0.07
D.Z4
0 17
0.08
0.07
0.08
0.36
0 32
0.08
007
0.05
0.04
0.07
0.05
0.07
004
0 10
0.04
0.10
0 10
NO i
5.4
7.8
i ND l
1 ND l
i ND i
3.4
i ND i
l ND i
l ND i
ND l
l ND l
i ND i
Z.6
l ND >
IND l
IND ป
l ND i
iND i
3.8
1 3
1.2
6.7
i ND i
ND
ND
3.
ND
ND
ND
3
l NO l
267.1
160.3
i ND i
72.2
l ND i
2.8
i ND i
81.4
iND i
48.1
23.3
i ND i
46.7
8.5
IND l
INK ซ
34.6
l ND i
171.7
43.4
32.4
213 7
i NO l
It. 7
1.7
173.3
2.6
127.3
7.7
8
INO 1
160.7
97.4
i ND ซ
80.4
IND l
1 7
i ND i
53.3
l ND i
33.2
16.2
l ND i
34.5
7.4
1 NDI
l ND l
27.0
NO t
146.8
35.2
26.5
153 0
i NO
11.7
1.7
147.2
2.5
77 8
4.3
16
l ND l
135.0
84.0
i ND l
64.2
l ND l
1.7
i ND ซ
37.5
i ND i
24.2
15.8
l ND i
33.2
5.4
l ND l
i ND i
23.4
IND i
125. 8
34 8
25.6
153.0
i ND i
6.6
1.4
136.5
2 1
SO 6
1.7
25
i ND l
102.5
57.2
IND i
48.8
i ND i
l ND *
l ND l
27.2
l ND l
17.2
15.0
IND l
30.4
4.1
1 ND 1
ND l
17.5
i ND i
101.4
33.0
23.8
136.4
IND l
6.3
1.6
128.6
1.8
41.1
l ND l
62
1 ND 1
74 3
47 Z
i ND l
33.7
i ND l
l ND 1
i ND l
7.8
i ND i
12.3
7.8
i ND i
23.3
2.7
IND l
IND l
13.1
l ND l
71.4
265
18.4
97.3
i ND l
4.6
1.0
92.5
1 0
288
i ND i
60
IND l
64.0
4Z.6
IND l
Z9.3
l ND l
l ND 1
l ND i
13.2
l ND i
7.2
10.0
INO l
22.5
2 4
l ND l
l NO l
11.1
l ND i
51.6
26.3
17.6
87.8
i ND i
4.1
0.6
83.2
0.7
22.8
i ND i
76
l NO l
70.7
62.6
I ND l
34 0
i ND i
l NO 1
i ND l
14.1
i ND l
9 7
10.0
i ND l
22.7
2.4
1 ND 1
l ND l
11.7
l ND i
56.3
26 4
18.0
71.0
l ND i
4.1
0.9
84.8
1.2
21.1
l ND l
107
l ND i
64.5
37.7
i ND
22.1
i ND i
l ND l
l ND l
13.6
l ND l
7.1
7.3
i ND i
17.9
2.3
l ND l
i ND i
7.6
i ND i
18.5
24.0
155
77.9
i ND i
3.9
D.B
70 7
0.8
17.8
ND i
136
l ND l
50.0
298
l ND i
24 7
i ND i
l ND l
l ND i
9.0
l ND l
6.5
7.B
i ND i
17.3
1.6
l ND i
i ND *
8.0
i NO l
31.9
20.6
13.7
60.2
i ND l
3.0
0.7
58.3
i ND l
13.5
l NO l
181
I ND 1
43.0
25 6
i ND i
15 8
l ND i
l ND i
l ND i
7 7
i ND i
58
6.B
l ND l
14 9
1.3
l ND l
i ND i
6.5
i ND i
26.4
17.2
6.2
50.0
> NO
2.4
0.7
46.0
0.6
10.1
i ND l
227
i ND i
326
17 6
ป ND
14.0
ซ ND >
1 8
ซ ND >
6.5
i ND i
5 0
5.7
i ND >
12.4
1 2
i ND <
i ND l
5.3
1 NO 1
20.3
14 0
5.0
42 6
* ND ซ
2 2
i ND ซ
38 0
ป ND
7 1
l ND i
aAll concentrations are to be interpreted only to two significant figures.
Not detected or belou QL.
'includes both meta- and para-isomers.
Indicates a non-target compound.
-------
Eปperiaent Title > UHOLE BREATH EXPOSURE EXPERIMENT
Spreadsheet Fi le Naie> UBCGS1
Exposure End Tiie ) 13=47
TABLE D-16
G51 (GARAGE/Fua/SOLVENT)i CANISTER COLLECTION
CONCENTRATIONS (NICROGRANS/CUBIC HETER a 25 deg. Ci 1 at..)8
CHPO
COMPOUND ID
Mean Mean
Blank Recov.
1 1
LOO
(NG)
VOLUME ANALYZED (L)
REAL TINE IHH m)ซ
OL SAW. ID SAMP. 10 SAW. ID SAW. ID SAW. ID SAW. ID SAW. ID SAW. ID SAW. ID SAW. ID SAW ID SAW ID SAMP. 10
(NG) 140GSIUCFD 140G51UCF1 140GS1UCF2 140GS1UCF3 14DGS1UCF4 140G51UCD4 140GS1UCF5 140GS1UCF4 140GS1UCF7 140GS1UCFB
i | | I | | 1 _ 1 _ 1 1 1 1
> 1
0.075 0.077 0.074 0.078 0.077 0.074 O.D78 0.079 0.07B 0 078
04 13:59 14-17 14:35 14:54 14:54 15:38 14:07 14=52 17-39
ELAPSED TIHE WIN) >
o
1
CO
Vinyl Chloride 42
Isopentane 57
Pentane 57
Vinylidene Chloride 41
2-flethylpentane 71
Dichloroiethane 84
Chlorofori 83
lilil-Trichloroethant 41
2-Methylheปane 57 9
Carbon Tetrachlonde 82
3-flethylhexane 57 #
Beniene 76
Trichloroethylene 40
Toluene 91
n-Octane 57
2-flethylpropyl acetate?
Tetrachloroethylene 59
Ethy 1 eye 1 ohexane ( tent . ) f
Butyl acetate 41 f
3-rlethyloctane 57 If
Ethyl bentene 91
P-Xylene 91C
n-Nonane 57
Styrene 104
o-Xylene 91
Ii2i4-Trimhylbenitnrf
n-Oecane 57
Triiethyl beniene iso. S
n-Undecane 57 #
n-Oodecane 57 t
34
45
44
1
47
34
2
4
SB
4
59
5
7
10
28
40
11
41
42
43
19
22
33
15
21
57
23
44
29
24
0.00
0.00
0 00
0.00
0.00
0.00
0.00
0.00
0.00
O.OD
0.00
0.00
000
D.OD
0.00
O.OD
0.00
0.00
0.00
D.OD
0.00
O.OD
0.00
0.00
O.OD
0.00
0.00
0.00
0.00
0.00
.00
.00
.00
.00
.00
.00
.00
.00
00
.00
.00
00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
00
.00
.00
.00
.00
0.07
0.04
0.07
0.03
0.08
0.09
D.D3
0.17
0.02
0.02
0.02
0.04
0.04
0.02
0.02
0.02
0.09
0.08
0.02
0.02
0.01
0.01
0.02
0.01
0.02
0.01
0.02
0.01
0.02
0.02
0.27
0.25
0 30
0.13
0.32
0.34
0.10
0.44
0 07
0.10
007
0.24
0.17
0.08
O.D7
0.08
0.34
0.32
008
0.07
005
0.04
0.07
0.05
0.09
004
0.10
0.04
0.10
0.10
,NO,b
22.0
13.1
* ND *
IND 1
1 ND 1
3.0
l ND l
IND l
i ND l
0.9
l NO l
IND i
2.3
l ND l
l ND l
i ND i
i NO
IND l
1.8
0.6
0.6
3.2
IND i
NO
ND
2.
NO
ND
NO
12
INOI
182.5
989
i ND l
49.7
l ND l
2.0
l ND l
43.6
i ND i
27.3
23.9
iNOi
39.8
8.4
l ND l
l ND l
19.4
i ND l
1229
37.7
22.9
231.4
i ND i
8.5
1.2
1584
1.3
35.8
1.8
30
NO i
123.7
49.4
*ND*
34.0
ND l
1.9
l ND l
29.5
l ND l
19.0
190
i NO i
32.3
5.9
i ND l
l ND l
15.3
NO 1
101.3
31.1
17.9
149.1
IND i
48
1.2
120.1
1.3
23. 0
NO i
48
i NO i
72.2
41 0
*ND*
23.2
l ND l
1.5
l ND l
17.7
i ND l
11.5
13.7
.NO!
23.5
4.9
l ND i
l ND l
10.3
NO l
45.0
23.5
13.1
103.4
i ND i
4.7
l ND 1
79.4
D.7
17.3
1 NO *
49
l ND l
49.4
41.2
*ND*
21.3
4.5
1.4
l ND l
14.5
l ND l
10.1
12.2
IND l
20.4
3.3
i ND l
INDI
8.4
INOi
54.1
20.2
10.4
62.9
INDI
4.2
0.4
43.9
0.7
143
l ND l
49
1 NO i
44.6
37.1
*ND*
21.9
1 ND l
2.7
1 ND i
14 1
l ND i
10.1
12.2
IND l
20.8
4.5
l ND i
1 ND l
8.4
IND 1
54.0
20.3
10.7
82. 1
1.4
4 3
0.4
42.4
0.5
14.9
5.5
111
i ND i
5D.4
28.3
*ND*
14.2
l ND l
1.3
l ND l
10.9
l ND l
7.7
9.0
INDI
15.4
2.1
l ND l
IND i
4.4
l NO l
35.1
14.9
7.4
54.5
i ND i
3.0
l ND l
454
l ND i
9.1
l ND l
140
l ND l
40.5
22.0
*ND*
12.5
l ND i
1 ND
l ND i
8.4
l NO i
5.9
7.3
IND i
10.7
1.8
i ND i
l ND l
5.1
IND l
24.7
11.2
5.9
41.2
l ND 1
2.4
l ND l
35.3
i ND
7.2
i ND i
165
i ND i
38.0
19 1
*ND*
11.8
i ND i
1 5
IND i
8.8
i ND i
4 3
4.2
i NO i
8.8
1 5
i ND i
l ND i
49
i NO i
24.7
8.5
4.7
37.4
1 ND 1
1.9
i ND I
26.1
i ND i
4.0
i ND i
232
l ND l
29.3
13.7
i ND i
7.1
I ND I
1.5
l ND i
5.2
i ND i
40
5.5
l NO l
7.5
1.4
i ND i
l ND ป
1 ND 1
l ND l
15.9
7.5
4.2
30.1
1 ND 1
1.9
IND i
23.1
i ND i
4.9
I ND *
All concentrations are to be interpreted only to two significant figures.
Not detected or below QL.
CIncludes both raeta- and para-isomers.
Indicates a non-target compound.
-------
O
H-ซ
10
TABLE 0-17
Etptriient Title > AIR DATA FOR HAROUARE STORE Z.3i TUO PEOPLE EXPOSED SIMULTANEOUSLY! CANISTER ALVEOLAR BREATH COLLECTIONS*
Spreadsheet File Naป> AIRHS-23
Exposure End Tiie > 11=50 CONCENTRATIONS (M1CROGRAHS/CUBIC METER 3 25 deg. Ci 1 at..)
CMPD.
COMPOUND ID
1 1 '
Mean Mean
Blank Recov.
1 1
LOO 01 SAHP ID SAMP. ID
(NG) ING) 140HS20CF1 140H53ECD1
II 1
VOLUME ANALYZED (L) >
REAL TIME
(HH:MH)
> 1
0.200
8:02 11
0.030
50
SAMP. ID
140HS3ECF1
0.030
11-50
SAHP. ID
140HS30CF1
_ 1
0.200
08-02
aAPSED TIME (HIM) >
Vinyl Chloride 42
Isopentane 57
Pentane 57
Vinyl idene Chloride ฃ1
2-Hethylpentane 71
Oichloroiethine 84
Chlorotori 63
liIil-TrichlaratthimM
2-Hethylhexane 57*
Carbon Tetrachloride 82
3-flethylheปane 57 &
Beniene 78
Trichloroethylene 40
Toluene 71
n-Octane 57
2-flethylpropyl acetate *
Tetrachloroethylene 59
Ethylcyclohenane (tent.)'
Butyl acetate 41*
3-ftethyl octane 57 9
Ethylbenieig 71
p-Xylene 91
n-Nonane 57
Styrene 104
o-Xylene 91
Ii2i4-Triiethylbenienrf
n-Oecane 57
Truethylbenzene isoJ?
n-UndecaneS7*
n-Oodecane 57 9
*
34
45
14
1
47
34
2
4
58
6
59
5
7
10
28
40
11
61
42
43
19
22
33
15
21
57
23
44
29
24
i *
0.00
0.00
0.00
0.00
0.00
0.00
000
D.DO
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
O.DD
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0 00
0.00
0.00
0.00
.00
.00
00
.00
.00
.DO
00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
00
.00
.00
.00
00
00
.00
DO
.00
00
/\U4* 9BS*W\ 1 ___
0.07
0.06
0.07
0.03
0.00
0.09
0.03
0.17
0.02
0.02
0.02
0.06
0.04
0.02
0.02
0.02
0.09
0.06
0.02
0.02
0.01
0.01
0.02
0.01
0.02
0.01
0.02
0.01
0.02
0.02
027
025
0.30
0.13
0.32
0.34
o to
0.64
0.07
0.10
0 07
0.24
0.17
0.06
0.07
0.06
0.34
0.32
0.06
0.07
0.05
0 04
0.07
0.05
0.09
0.04
0 10
0 04
0 10
0 10
,ND,b
25.5
15.3
2.2
5.4
452.1
4.3
102.6
l ND l
l ND i
NO i
1.7
l ND i
6.3
i NO
i ND i
4 3
NO l
l ND i
l ND
1.4
4.7
0.8
8.9
1.2
i ND *
1.8
i ND *
INDI
l ND i
i ND i
106
37.6
5.6
24.7
451.9
l ND l
197.9
i ND i
l ND *
i ND i
1 ND 1
i ND l
635.2
38.2
i ND
16.1
i ND i
i ND i
l NO
147.5
568.0
1936
39 1
199.1
l ND *
301.7
INDI
l ND I
i ND *
aa /rtl
i NO I
9.4
342
5.3
22.8
455.0
t NO I
199.1
i NO
1 NDI
I NO 1
IND 1
I NO <
635.2
38.8
I NO i
16.8
f ND*
i ND
i ND ป
146.6
561.9
210 4
37.6
193.6
i ND ป
360.3
ซ ND ซ
(NO >
ซNO ซ
1f>f*tปA A
i ND ป
21.7
12.6
( ND i
8.6
1.6
12.6
7.0
ND i
l ND ซ
i ND i
2.1
1 0
18.5
0.4
l ND
* ND ป
IND ป
IND i
l ND *
1 3
38
0 7
28.4
1.5
l ND ป
3.3
i ND ป
l ND *
ND
urine ev
SAMP. 10 SAHP. 10 SNIP. ID SAMP. ID SAMP. ID SAMP. ID SAHP. ID SAMP. 10 SAMP ID
Samples 140HS3ECF1 and 14UH53ECD1 represent duplicate samples conceit UUL*..B =^^o-. = . Samples 140HS20CF1 an i.,!^"*^"
overnight, pre-exposure air samples collected by each of the two participants. No sample was collected during breath collection for
this experiment because of a sample collection failure.
aAll concentrations are to be interpreted only to two significant figures.
Not detected or below QL.
CIncludes both meta- and para-isomers.
Indicates a non-target compound not quantitated in this experiment.
-------
TABLE D-18
Expernent Title > HARDUARE STORE I2i ALVEOLAR BREATH COLLECTION
Spreadsheet File Haw> ABCHS2
Exposure End Tiie > II SO
CANISTER; TUO PEOPLE EXPOSED SIMULTANEOUSLY
CONCENTRATIONS (HICROGRAHS/CUB1C HETER 9 25 de9. Ci 1 at..)
COT).
COMPOUND 10
Mean (lean
Blank Recov
LOO
(KG)
OL SAMP ID SAMP. 10 SAHP. ID SAMP. 10 SAMP. ID SAMP. ID SAHP. ID SAHP. 10 SAHP. 10 SAMP. ID SAMP. ID SAMP. ID SAHP. ID
(KG) 140H52ACFO I40HS2ACF1 140HS2ACF2 140H52ACF3 140H52ACF4 140HS2ACF5 14DHS2ACF4 140HS2ACF7 I40HS2ACFB 140HS2ACF9 140HS2ACF10140HS2ACF11
VOLUME ANAtrTED (L) > O.D40 0 038 0.059 0.059 0 059 0.057 0.059 0.057 0.059 0.060 0.059 0.040
REAL TIME (HH=rJ1) > 07:52 11:53 12-00 12 '04 12:14 12:24 12=41 12=54 13=24 13=57 14-40 15:28
ELAPSED TIME (MINI >
Vinyl Chloride 42
Isopentane 57
Pentane 57
Vinyl idene Chloride 41
2-Hethylpentane 71
OicMoroiethane 64
Chlorotori 83
I.lil-Trichloroethane 41
2-Nethylhe>ane 57 *
Carbon TetracMoride 82
3-Hethylheปanป 570
Beniene 76
Triehloroethylene 40
Toluene 11
n-Octane 57
2-Hethylpropyl acetate 0
^ TetracMoroethylene 5?
no Ethylcyclohe>ane (tent.)ff
0 Butyl acetate 410
3-Methyloctane 57 It
Ethylbenzene 91
p-Xylene 91ฐ
n-Nonane 57
Styrene 104
o-Xylene 91
l>2.4-TriietMbeniene 0
n-Decane 57
Triiethylbentene iso. f
n-Undecane 57 f
n-Oodecane 57 9
34
45
14
1
47
34
2
4
56
4
59
5
7
10
26
4D
11
61
42
43
19
22
33
15
21
57
23
U
29
24
0.00
0.00
0 00
0.00
0 00
0.00
0.00
0.00
0.00
0.00
0.00
.00
.00
.00
.00
.00
.00
.00
00
00
00
0.00
0.00
O.DD
0.00
O.DD
0.00
O.DD
0 00
0.00
.00
.00
.00
.OD
.00
.00
.OD
.OD
.00
.00
.00
.00
.DO
.00
.00
.00
.00
.OD
.00
.00
00
.00
.00
.00
.00
.00
.00
.00
.00
.00
0.07
004
0.07
0.03
0.08
0 09
003
0.17
0 02
0.02
0.02
0.04
0.04
0.02
O.D2
0.02
0.09
0.08
0.02
0.02
0.01
001
002
0.01
0.02
0.01
0 02
0.01
0.02
0.02
027
0.25
0.30
0.13
032
0.34
0.10
0.44
O.D7
0.10
0.07
0.24
0.17
0.08
0.07
0.08
0.34
0.32
0.08
0.07
0.05
0.04
0.07
D.05
0.09
0.04
O.lfl
0.04
0.10
0.10
i ND i
150.9
78 4
1 ND ซ
34.4
41.5
3.1
84.2
i ND I
ซ ND <
IND I
4.4
1 ND I
53
ปND
l ND *
i ND >
iND ซ
i ND i
INDI
l ND l
1.1
1 5
l ND l
1 ND *
IND*
l ND i
l ND ซ
i ND l
i ND *
3
i ND
17.0
13 3
1 ND l
> ND i
592
> ND
124.2
i NO i
l ND ป
i ND
l ND l
l NO l
38.2
2.4
l ND *
l ND *
i ND *
l NO *
l NO l
3.7
19.D
10.7
1 ND 1
3.5
l ND l
20.8
l ND i
IND l
l ND i
10
i ND i
4.7
4 4
l ND l
l NO I
52.7
l ND i
101.5
i ND ป
IND l
ป ND i
l ND 1
l ND l
29.4
1.9
1 NO i
6.2
i ND l
i ND l
l ND l
2.5
133
4.9
* ND i
2.4
IND i
12.4
i ND l
l ND 1
l ND i
14
l NO l
4.3
8.5
l ND 1
l ND i
47.0
i NO 1
101.1
l ND i
1 ND i
i ND i
IND i
l ND l
29.1
2.0
i ND i
NO i
IND l
IND l
i ND l
2.1
11.7
5.9
l ND l
2.2
i ND ซ
5.4
IND l
IND i
i ND ซ
24
NDi
8.2
B.5
1 ND 1
l ND l
42.7
ป ND l
95.2
i ND l
1 ND ป
l ND l
l ND l
l NO l
24.5
1 4
l ND l
4.1
* NO *
l ND l
INO *
2.0
4.6
5.Z
i ND
2.3
l NDi
5 1
i ND i
IND i
INOป
36
NO i
12.8
9.5
1 ND 1
l NO l
34.4
IND *
95.3
l ND l
l ND ป
IND*
1 ND *
1 ND 1
22.1
1.4
i NO ป
l ND *
ซ ND ซ
IND *
i ND ซ
2.0
6.4
5.3
1 ND ซ
2.0
l ND *
S.I
t NDป
l ND l
i ND
51
i ND *
6.7
7.6
l NO 1
1 NO l
29.9
i ND i
83.9
i ND i
IND l
1 ND i
IND l
l NO l
20.7
1.2
i ND i
*NO l
* ND i
IND i
ซ ND l
1.9
6.1
4.1
1.0
2.1
ND i
5 1
IND *
ปND i
i ND ซ
66
l ND
14.2
12.4
1 ND 1
l ND l
29.9
1.8
94.0
NO l
l ND 1
1 ND l
1 ND 1
l ND i
24.6
1.3
IND i
INO l
*NO ซ
l ND 1
*ND i
2.1
6.7
4.4
* ND i
2.1
I ND i
4.1
ป ND l
l NO ซ
i ND l
94
l ND l
4 5
5 5
1 ND 1
IND l
26.8
i NO i
74.5
i ND i
l ND l
l ND 1
t ND l
IND l
14.6
IND t
1 ND l
l ND i
i ND *
l ND l
IND l
1.2
3.9
2.9
1 ND I
INO l
l ND 1
2.1
* ND i
i ND l
i ND i
127
i ND i
ซ ND i
5 3
1 ND l
* ND l
28.0
3 7
74.7
i NO l
ป ND i
1 ND 1
l ND l
l ND i
13.1
ซ NO l
l ND l
IND i
l ND i
ซ NO l
l ND i
1 2
3.7
2 6
0.8
l ND i
l ND i
1.8
i ND i
i ND *
i ND i
170
IND i
i ND i
i ND i
l ND l
IND l
22 1
1.6
68.8
* ND l
i ND i
ป ND 1
l ND l
ND l
9.3
1 NO >
l ND l
I ND i
l ND l
l ND i
i ND l
1.1
3.1
2.3
l ND i
i ND *
l ND l
l ND l
l ND ซ
l NO i
i ND i
218
i ND i
* ND ป
i NO i
* ND i
i ND i
23.8
1.4
69.8
ซ NO *
ซ ND i
ซ NO 1
l ND l
l ND l
8.3
ป ND l
i ND i
* ND 1
i ND l
l ND l
i ND l
0.9
2.8
2.2
ND i
i ND i
ND ป
> ND ป
i ND i
i ND >
l ND i
aAll concentrations are to be Interpreted only to two significant figures.
Not detected or below QL.
CIncludes both meta- and para-isomers.
Indicates a non-target compound not quantitlfed in this experiment.
-------
TABLE D-19
Eปperiient Title > HARDWARE STORE 13; ALVEOLAR BREATH COLLECTION, CANISTER; TUO PEOPLE EXPOSED SIMULTANEOUSLY
*(> cauancc * lie IIBHC r nuhiMW
Exposure End Tue > 11*50
CMPO
COMPOUND ID
1 1 '
(lean Heen
Blank Recov.
i i
LOD
(HE)
1
CONCENTRATIONS (HICROGRAM5/CUB1C KETER 3 25 des. Ci 1 ata.)a
OL SAW ID SAW. ID SAMP ID SAW. ID SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAH>. ID SAMP. ID SAMP. ID SAMP. 10 SAMP ID
(ME) 140HS3ACFD 140HS3ACF1 140H53ACF2 UDHS3ACF3 140HS3ACF4 140H53ACF5 140HS3ACF6 140HS3ACF7 140H53ACFB 140H53ACF9 140HS3ACF10140HS3ACF1 1
VOLUME ANALYZED (L) > 0.060
REAL TIME (HH-MH) > 07:52 11
ELAPSED TIME (M!N) )
Vinyl Chloride 62
Isopentane 57
Pentane 57
Vinyl idene Chloride 61
2-Methylpentane 71
DicMoroiethane B4
Chlorolori 83
lilil-Trichloroethane 61
2-Methylhexane 57 9
Carbon Tetrachloride 82
3-Methylnexane 57 t
Beniene 78
Trichloroethylene 60
Toluene 91
n-Octane 57
2-flethylpropyl acetate 9
Tetrachloroethylene 59
Ethylcyclohexane (tent.)*
Butyl acetate 41*
3-Hethyloctane 57 *
Ethylbenieng 91
p-Xylene 91
n-Nonane 57
Styrene 104
o-Xylene 91
Ii2.4-Triiethylbeniene 0
n-Oecane 57
Triiethylbeniene iso. t
n-Undecane 57 f
n-Oodecane 57 1
34
45
46
1
47
34
2
4
58
6
59
5
7
10
28
60
11
61
62
63
19
22
33
15
21
57
23
64
29
24
0.00
O.DD
O.DO
O.OD
D.OO
0.00
0.00
O.DO
O.DO
D.DD
0.00
0.00
0.00
O.OD
DOO
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0 00
O.OD
0.00
0.00
0.00
0.00
0.00
O.OD
.DO
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.DO
.00
.00
.00
.00
.00
.00
0.07
0.06
0.07
003
0.08
0.09
0.03
0.17
0.02
D.02
0.02
0.06
004
0.02
0.02
0.02
0.09
0.08
0.02
D 02
0 01
O.D1
002
0.01
0 02
0.01
0.02
0.01
0.02
D.02
027
0.25
0.30
0.13
0.32
0.34
0.10
0.66
O.D7
D.10
0.07
0.24
0 17
D OB
0.07
0.08
0.36
0.32
0.08
0.07
0 05
0.04
0.07
0.05
0.09
0.04
0.10
O.D4
0.10
0.10
INDlb
65.1
348
iNDl
19.2
ND i
2.5
ND l
I NO i
i ND l
1 ND 1
l ND l
IND l
4 3
l ND i
l ND 1
INO l
l ND l
ND
ND
ND
ND
NO
ND
l NO i
l ND i
IND
l ND l
NO
0.059 0.059 0 058 G.059 0.059 0.059 D.06D 0 040 0.060 D.04D 0.040
:53 12:00 12-04 12:16 12-26 12:41 12:56 13-26 13:57 14-40 15:28
3
NO l
17.5
11.4
*HD*
l NO l
24 9
1.8
51. B
i ND l
l NO l
i NO i
l ND 1
IND
33.2
2 6
ND l
58
1 ND ซ
i NO
l ND
2.7
14.8
7.9
l ND ป
2.9
i ND i
14 9
IND <
NO l
i ND
10
NO >
59
50
i ND
l ND
24 D
i ND
38.5
l ND
l ND l
i NO
IND l
i ND
24.6
1.9
1 ND 1
i NO
i ND
t ND
ND
23
12.1
6.4
l ND l
2.3
IND l
57
NO
1 ND 1
ND
14
ND i
4.4
I ND l
IND 1
l ND 1
23.1
NO l
32.0
NO i
3.2
INO i
IND 1
1 ND i
IB. 8
i ND i
IND 1
i ND ป
l ND l
IND l
NO
1 4
5.2
4.0
i ND
1.4
i ND l
4 0
IND
IND l
NO
24
l ND l
4.3
55
IND i
i ND l
20.0
1.6
27.B
l ND'i
i ND i
i ND i
1 ND 1
l ND l
20.4
i NO
t ND 1
IND l
l ND l
i ND l
l ND l
1.9
6.0
4.1
INO
1.9
NO
4.1
l ND l
IND l
ND >
36
IND i
5.4
INDl
l ND l
1 NO 1
17.9
1.7
23.2
INO i
l NO 1
INO l
1 ND l
NO l
16.4
l ND i
l ND l
7 2
INO l
i NO l
l ND l
1.5
4.9
34
IND i
1.5
NO l
3.1
INDl
IND I
NDi
51
l ND l
6.2
INO 1
ND l
l ND l
12.4
l NO l
19.5
l NO
l ND l
l ND l
1 ND l
l ND
14.5
i ND i
l ND 1
IND l
l ND l
INO i
ND l
1.4
4.2
2.9
t ND l
1 ND 1
ND l
34
ND i
l ND I
ND ซ
66
l ND l
5.7
5.5
l ND l
i ND i
129
1 7
17.7
l ND l
1 ND l
l NO
l ND
1 ND l
13.7
i ND t
l ND l
INO l
l ND l
l ND l
i ND l
1.1
3.9
2.1
l ND i
1.4
l ND >
2.0
ND i
i ND i
ND i
96
IND >
i NO i
l ND i
l ND l
1 NO l
9.5
i ND
15.5
i ND
i ND i
i ND
l ND 1
l ND l
9.7
l ND
i ND
i ND
l ND
l ND
l ND
09
3.0
1.9
l ND
l ND l
IND
l NO ป
l ND l
l NO
i ND >
127
INO l
i ND
l ND l
i ND
l ND l
7.3
i ND l
13.4
l ND i
i ND l
i ND 1
l ND 1
l ND l
B.D
NO i
i ND i
i ND i
IND
l ND l
l ND
0.8
2.5
1.4
l ND ซ
INO i
i ND l
l ND
i ND
i ND
l ND *
170
1 ND l
l ND i
l ND 1
i ND i
l NO l
5.3
NO i
11.7
l ND i
i ND l
1 ND i
l ND l
i ND i
6.9
l ND i
i ND i
i ND i
l ND l
l ND l
i ND i
1 ND 1
2.2
1.3
ND i
l ND 1
i ND i
l ND i
1 ND l
i ND i
1 ND l
21B
l ND i
i ND i
1 ND l
ND i
1 NO l
i ND
i ND i
11.5
l NO
NO i
l ND i
i ND i
1 ND I
5.5
ND
i ND i
i ND >
i ND i
IND 1
l ND *
l ND l
1 6
1.3
ND i
l ND i
i ND i
l NO
l ND l
i ND ป
1 ND l
aAll concentrations are to be interpreted only to two significant figures.
bNot detected or below QL.
clncludes both meta- and para-isomers.
Indicates a non-target compound not quantltifed in this experiment.
-------
TABLE D-20
Experiment Title > HARDWARE STORE 2 AND 3i DUPLICATE ALVEOLAR CANISTER COLLECTIONS
Spreadsheet File Naie> ABCHS23D
Exposure End Tiปe > 1P50
CONCENTRATIONS (M1CROGRAMS/CUBIC METER 3 25 deg. C; 1 ati.f
COMPOUND
CHPO.
ID
1
Dean Hean
Blank Recov.
i i
LOO
(NG)
1
VOLUME ANALYZED (L)-
REAL TIME
(HH'HM)
aAPSEO TIME (KIN) -
Vinyl Chloride 42
liopentane 57
Pentane 57
Vinylidene Chloride 41
2-Hetnylpentane 71
Dichloroiethane B4
Chloroton 83
Mil-Trichloroethane 41
2-flethylhexane 57(7
Carbon TetracMonde 82
3-Metnylhexane 570
Beniene 78
Tnehloroethylene 40
Toluene 91
n-OcUne 57
2-Hethylpropyl acetate t
*p Tetrachloroethylene 59
ro Ethylcyclohexane (tent.)*
^ Butyl acetate 41*
3-Methyloctane 57 9
Ethylbenzene 91
p-Xylene 91 C
n-Nonane 57
Styrene 104
o-Xylene 91
I>2i4-Triiethylbenzene 9
n-Oecane 57
Trmethy (benzene iso. f
n-Undecane 57 t
n-Oodecane 57 t
34
45
44
1
47
34
2
4
58
4
59
5
7
ID
28
40
11
41
42
43
19
22
33
15
21
57
23
44
29
24
0.00
D.DO
D.OO
0.00
0.00
D.DO
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
O.OD
0.00
O.OD
0.00
O.OD
0.00
O.OD
0.00
D.OD
0.00
O.OD
0.00
O.OD
0 00
0.00
00
.00
.00
.00
.00
.00
.00
.00
.00
.00
00
.00
.00
00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
0 07
0 04
0 07
0.03
0.08
009
003
0.17
0.02
0.02
0.02
0.04
004
0.02
0.02
0.02
0.09
0.08
0.02
0.02
0.01
0.01
0.02
0.01
0.02
001
0.02
0.01
0.02
0.02
OL
(NG)
->
>
>
0.27
0.25
0.30
0.13
0.32
0.34
0 10
0.44
0.07
D.10
0.07
0.24
0.17
O.OB
0.07
O.DB
0.34
0.32
0.08
0.07
0.05
0.04
0.07
0.05
0.09
0.04
0.10
0.04
0.10
0.10
SAHP. 10 SAMP. ID SAHP. 10 SAMP. 10 SAMP. ID SAHP. ID SAHP. ID SAHP. 10 SAMP. ID SAMP. ID SAHP. ID SAHP ID SAHP. ID
140HS2ACD4 140HS2AC09 140HS3AC07 140H53ACD10
0.058
0.04D 0 059 0.05B
12-41 13'57 12=54 14:40
l ND 1 b
7.1
127 44 170
l ND i 1 ND 1 ND
5.7 4.9 ND
42 *ND
1 ND l
2
(NO i >ND
30.0
i ND i
78.7
* NO >
* ND i
>ND ป
i ND ป
i ND >
IB. 2
IND l
l NO *
IND i
* ND *
* NO *
* ND *
1.4
5.3
3.7
*ND *
1.7
INDป
3.4
ป ND l
ND i
l ND l
24.
i ND
73.
ND
ND
ND
ND
ND
12.
ND
ND
ND
ND
ND
ND
1
3.
2.
ND
ND
ND
1.
ND
ND
ND
* ND l ND
l ND ND
4.7 ND
12.8 4 3
14 IB
17.7 15.0
NO ซ
ND*
ND *
ND ป
ND *
14.5
ND l
ND *
ND *
ND*
NO*
ND*
1 2
39
3 2
* ND ป
l.S
l ND *
2.1
ND >
1 ND *
l NO ป
ND *
ND *
ND *
ND l
ND *
4.3
NO l
ND l
ND l
ND i
NO l
NO *
ND *
2.1
1.3
ND ป
ND i
ND ซ
ND ซ
ND >
ND l
ND l
aAll concentrations are to be Interpreted only to two significant figures.
Not detected or below QL.
'includes both meta- and para-lsomers.
Indicates a non-target compound not quantltlfed In this experiment.
-------
Experiment Tltlf > HARDWARE STORE 1.5; CANISTER AIR DATA
Spreadsheet File Mate) AIRH545
Eปpnure End Tiป ) 12.13
TABLE D-21
CONCENTRATIONS (HIHOGRAHS/CIBIC ffiTER 3 25 dag. Ci 1 ati.)
CWD.
COMPOUND ID
' '
Dean Mean LOO OL SAW. ID SAW. ID SAW
Bland Recov. (NG) (NG) 140HS40CF1 140H550CF1
VOLUME ANALYZED -
REAL TIME IHH-m)
Vinyl Chloride 42
liopentane 57
Pentane 57
VinylidM* CMoridt 41
2-fletkylpentine 71
Oichloroiethane 84
CMorolon 83
l.l.l-Trickloroetkane 41
Z-Methylkซanป 57 i
Carbon Tetraeklonde 82
3-nethylhe>ane 57 *
Beniene 78
Trickloroethylene 40
Toluine 91
n-Octane 57
2-ncthylpropyl acetate*
TetracMoroetkylene 59
*p Ethylcyclokeiane (tcnt.)f
ro Butyl acetate 411
00 3-Hetkyl octant 57*
Ethylbenient 91
p-Xylene 9r
n-Nonane 57
Stynne 104
0-Xylene 91
Ii2i4-Trmtkylbenient 1
n-Oecane 57
Triietkylbeniene IID. i
n-Undecane 57 f
n-Oodecane 57 f
34
45
44
1
47
34
2
4
58
&
59
5
7
10
28
40
11
41
42
43
19
22
33
15
21
57
23
44
29
24
ELAPSED TIME
0.00
000
0 00
000
0.00
000
0.00
000
0.00
000
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
O.DO
000
OD
DO
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.OD
.00
.00
.00
.00
.00
.00
.00
.00
00
.00
.00
.00
.00
.00
.OD
(HINI -
0.07
0.04
0.07
0.03
0.08
0.09
0.03
0.17
0.02
0.02
0.02
0.04
0.04
0.02
0.02
0.0?
0.09
0.08
0.02
0.02
0.01
0.01
002
0.01
0.02
0.01
0.02
001
0.02
0.02
)
> B
>
0 27
0 25
030
0.13
0.32
0 34
0.10
D44
0.07
010
0.07
0.24
0.17
O.OB
007
D.OB
0.34
0.32
o.oa
0.07
0.05
0.04
007
DOS
0.09
0.04
0.10
O.D4
0.10
0.10
D.20D
IB 8
1 ND lb
13.0
4.9
1.7
2.7
28.5
54
135.1
IND i
i ND i
I ND I
1.7
I ND i
41 5
10.3
INO i
4.2
INO*
IND l
l ND i
1.4
5.5
3.2
4.4
1.4
IND*
5.5
IND*
INDi
i ND l
0.200
IB
INO i
21 3
103
i ND i
39
17.1
5.3
i ND i
i ND i
1 ND I
i NO i
1.8
1.3
54.3
0.5
NDi
NDป
NO*
ND l
NOi
.3
.7
.0
1
.7
l ND l
1.1
l ND l
INO i
IND i
. ID SAW. ID
140HS4ECF1
005D
12-13
i ND i
7.0
13.4
5.0
14.2
320.4
4 4
225.4
l ND i
l ND *
i ND i
44
INDi
454.2
33.0
i ND *
185.1
NO i
l NO l
i ND i
57.2
234.5
1250
18.7
101.
NO
212.
ND
i NO
i ND
SAW. ID SAW
140H5SECF1
0.050
12:13
IND*
4.3
124
3.1
104
218.0
38
201.5
l NDi
i ND *
i NO i
l NO*
l NO *
282. 2
23.1
l NO *
154.5
l ND *
1 NO*
l ND ซ
37.7
155.0
107.2
13.8
44.1
1 NO *
149.5
l NO *
l NO l
i ND *
. 10 SAW. 10
140H54BCF1
1 !
0.200
15:54
INO l
8.5
2.9
1 NO l
2.0
NO i
1 ND 1
l NO *
IND *
IND i
INO i
1.4
INDi
7.3
0.5
IND i
3.0
IND i
IND ป
i ND i
1.3
5.8
2.5
1.2
24
IND *
9.9
IND i
IND I
IND i
SAW. ID SAW. ID SAW. ID SAW. ID SAW. ID SAW. 10
aAll concentrations are to be Interpreted only to two significant figures.
bNot detected or below QL.
Includes both meta- and para-lsomers.
Indicates a non-target compound not quantltlfed In this experiment.
-------
o
no
Expenient Title > Hardware Store 14; canister collection o< Alveolar Breath
Spreadsheet File Na.e> ABCHS4
Eiposure End Tiซe > 12-13
TABLE 0-22
CONCENTRATIONS (MICROGRAMS/CUBIC METER 3 25 dej. Ci 1 at>.)
CHPD.
CONFOUND ID
Mean Mean
Blank Recou.
1 t
LOO
(NG)
QL SAMP. ID SAMP. ID SAMP. ID SAMP. 10 SAMP. 10 SAMP. ID SAHP. ID SAHP. ID SAMP. ID SAMP. ID SAMP. ID SAMP 10 SAMP ID
(NG) 140H54ACFD 140HSWCF1 14DH54ACF2 140HS4ACF3 140H54ACF4 140HS4ACF5 140HS4ACF4 140HS4ACF7 140HS4ACF8 140HS4ACF9 140HS4ACF10140HS4ACF11
VOLUME ANALrZED (L) >
REAL TIME (HHiMH) > 6
005B
04 12
ELAPSED TIME (MIN) >
Vinyl Chloride 42
Isopentane 57
Pentane 57
Vinylidene Chloride 41
2-Hethylpentane 71
Dichloroiethane 84
Chlorotori 83
lilil-TricMoroethane 41
2-Hethylheซane 57 9
Carbon TetracMonde 82
3-Methylhexane 57 9
Benune 78
Triehloroethylene 40
Toluene 91
n-Octane 57
2-Hethylpropyl iceititt
Tetrachloroethylene 59
Ethyl eye loheปane (lent.)*
Butyl acetate 41 9
3-Methyl octane 57 9
Ethyl beniene 91
p-Xylene 91C
n-Nonane 57
Styrene 104
o-Xylene 91
Ii2i4-Triiethylben>ene0
n-Oecane 57
Truethylbenzene iso. t
n-Undecane 57 t
n-Dodecane 57 f
34
45
44
1
47
34
2
4
58
6
59
5
7
10
28
40
11
41
42
43
19
22
33
15
21
57
23
44
29
24
0 00 1.00
0 DO 1.00
0.00
0.00
0.00
ODD
0 00
0.00
0.00
0.00
0.00
0.00
0 00
0.00
0.00
D.OD
0 00
0.00
0.00
D.OD
0.00
0.00
0.00
0.00
0 00
0.00
000
0.00
0.00
0.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
0.07
0.04
0.07
O.D3
O.OB
0.09
0.03
0.17
0.02
O.D2
O.D2
0.04
0.04
0.02
0.02
0.02
0.09
0.08
0.02
0.02
0.01
0.01
0.02
O.DI
0.02
0.01
0.02
001
002
0.02
0.27
025
0 30
0.13
032
0.34
0 10
0.44
0.07
0.10
0 07
0 24
0.17
O.OB
0.07
0.08
0.34
032
O.OB
007
0.05
0.04
0.07
0.05
0.09
0.04
0 10
004
0 10
0 10
l ND ib
42.9
27.8
ซ ND i
12.1
1 ND l
5 5
455
l ND *
l ND l
l NO i
i ND >
ป ND l
3.7
NO i
l ND ป
> ND >
l NO l
1 ND l
NO
NO
ND
ND
NO
ND
ND
ND
ND
NO
ND l
0.059 0 040 0 040 0 040 0.040 0 040 0.040 0.040 0.040 0 059 0 058
14 12:23 12:31 12:41 12-51 13=04 13:22 13=51 14 23 15-04 IS 52
3
INO i
i ND l
9.0
38
INO l
<8.5
4 5
905
IND i
i ND i
i NO i
3 9
i NO i
55 7
5.0
i ND i
44.9
l ND i
i ND i
IND *
3.2
1B.4
18.9
i ND i
3.9
IND i
31.4
IND l
IND i
i ND i
10
i ND l
4 0
l ND i
i ND >
i ND l
34.5
2.2
58.5
i ND i
IND l
i ND i
l ND i
i ND i
24.8
2.2
l ND l
44.1
INDI
i ND l
l ND l
1 3
4.4
4.8
INDI
1.4
l ND i
14.2
1 ND l
INO i
I ND 1
IB
l ND l
4.0
l ND i
l ND i
i ND i
2B4
3.1
54.2
IND i
IND l
l ND i
i ND i
i ND i
24.4
1.9
l ND 1
39.7
IND l
IND i
l ND l
1.2
4 1
43
l ND l
1 4
l ND l
14.7
l ND l
l ND l
l ND l
28
i ND i
l ND l
9.7
l ND >
1 ND l
24.0
2.4
50.2
i ND i
i ND 1
l ND l
i ND l
l ND t
21.1
1.4
l ND i
34.8
l ND
t ND l
1 ND *
0.8
2.9
4.4
l ND l
l ND l
1 ND *
12.4
INDI
l ND l
ND l
38
l ND l
ซ ND 1
i ND i
1 ND *
* ND l
21.4
2.3
47.2
l ND i
l ND i
l ND l
l ND i
1 ND l
19.3
1.3
1 ND *
31.9
l ND i
1 ND
l ND l
IND i
2.5
4.1
1 ND 1
l ND l
l ND l
4.4
l ND l
l ND l
l ND l
53
l ND 1
39
l ND l
l ND l
l ND l
17.7
3 1
43.1
l ND l
IND l
i ND 1
i ND 1
1 ND *
18.5
1.5
IND l
25.1
l ND l
l ND i
IND l
1 ND l
2.5
3.8
ND l
i ND i
i ND i
4.2
1 ND l
IND i
l ND l
49
i ND i
65
44
i ND i
IND l
14.7
20
420
l ND i
l ND l
l ND l
l ND l
i ND i
15.4
1 3
IND i
20 4
1 ND t
I NO ป
1 ND l
l ND l
20
2 7
l ND i
l ND l
i ND i
3 0
1 NO l
1 NO l
I ND i
98
l ND ป
1 ND I
i ND >
i ND i
i ND i
13.0
2.7
38.8
i ND i
IND i
i ND l
l NO i
l ND i
14.3
2.8
NO i
15 4
i ND i
i ND >
l NO l
l ND l
1.7
2.3
l ND i
IND i
l ND l
23
I NO l
1 ND 1
I ND l
130
ป ND l
l ND 1
ป ND 1
ป ND *
1 ND I
l ND i
1.8
37 7
i NO
l ND *
i NO l
* ND *
i ND l
13.2
NO i
i ND i
14.2
i ND ป
> ND ป
l ND *
NO ป
1.4
1.9
i NO
i NO i
i ND ป
2.2
1 ND 1
i ND i
l ND i
173
ป NO i
l ND l
l NO i
ND
i ND i
9.2
2 1
387
> ND ซ
* ND *
ป NO i
ND ป
ป NO
12 4
* NO i
ป ND ป
12.4
l ND l
ป ND i
ปND ป
ป ND ซ
1 4
1 9
ND i
ป NO
i ND ป
1 4
i ND ป
l ND i
* ND i
219
I ND l
l ND 1
i ND i
I ND I
1 NO 1
4 2
30
44 3
i NO i
i ND i
* ND i
l ND l
I NO ซ
150
1 3
i ND i
12.3
* ND l
i ND i
i ND l
i NO *
1.9
2.2
ป ND i
ซ NO >
ป ND i
2.2
l ND >
i ND i
i ND ซ
All concentrations are to be interpreted only to two significant figures.
Not detected or below QL.
CIncludes both meta- and para-isomers.
Indicates a non-target compound not quantitifed in this experiment.
-------
o
I
ro
en
Expedient Title > HARDWARE STORE ซ5i CANISTER COLLECTION OF ALVEOLAR BREATH
Spreadsheet File Naie> ABCHS5
Exposure End Ti.e > 12-13
TABLE D-23
CONCENTRATIONS (MICROGRANS/CUBIC METER 3 25 de9. Ci 1 at. )
CNPD.
COMPOUND ID
Mean Mean
Blank Recov.
LOO
(ME)
OL SAMP ID SAMP. ID SAMP. ID SAKP. 10 SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP ID SAMP ID SAMP. ID SAMP. ID SAMP 10
(NG) 140H55ACFO 140H55ACF1 140H55ACF2 140H55ACF3 140H55ACF4 140H55ACF5 140HS5ACF6 140H55ACF7 140H55ACF6 140H55ACF9 140H55ACF1014DHS5ACFI1
VOLUME ANALrZEO (L) >
REAL TINE (HH-MN) > 8
0 060 0.040 0.060 0.060 0.060 0.060 0.060 0.060 0 060 0 060 0.060 0.060
06 12 16 12-23 12:31 12-41 12:51 13-04 13:22 13:51 14:23 15:06 15-52
ELAPSED TIME (MINI >
Vinyl Chloride 62
Isopentane 57
Pentane 57
Vinyl idene Chloride 61
2-Hethylpentane 71
Dichloronthane B4
Chlnrotori 83
lilil-Trichloroethane 61
Z-Methylhexane 57 t
Carbon TetracMoride 82
3-MethylhMane 570
Benzene 78
Trichloroethylene 60
Toluene 91
n-Octane 57
2-Hethylpropyl acetate 8
Tetrachloroethylene 59
Ethyl eye lohexane (tent.))?
Butyl acetate 61 0
3-Hethyl octane 570
Ethyl benzene, 91
p-Xytene 91
n-Nonane 57
Styrene 104
o-Xylene 91
Ii2i4-Triiethylfaenzene#
n-Oecane 57
Triiethylbentene ISO,'1
n-Undecane 57 t
n-Oodecane 57 t
36
45
46
1
47
34
2
4
56
6
59
5
7
10
28
60
11
61
62
63
19
22
33
15
21
57
23
64
29
24
0.00
0.00
0.00
0.00
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
000
0.00
0.00
0.00
0.00
0.00
0.00
0.00
000
0.00
ODD
0.00
0.00
0.00
000
0.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
00
.00
.00
00
.00
.00
.00
.00
00
.00
00
0.07
0 D6
0.07
003
0.08
0 09
0.03
0.17
0.02
0.02
002
0.04
0 04
0.02
0 02
0.02
0.09
O.OB
0.02
0.02
0 01
0.01
0.02
0.01
002
0.01
0.02
0.01
002
0.02
0 27
025
0 30
0.13
0 32
0.34
0.10
0.64
0 07
0.10
0 07
0.24
0 17
0 08
0 07
0.08
0 36
0.32
0.08
007
005
0.04
0.07
005
0.09
0.04
0.10
0.04
0.10
0 10
NDi
2172
81.2
NO
U B
ND
1.9
i ND
ซ NO *
i ND
ซ ND
ND ซ
i ND
6.7
i ND
ซ ND 1
l ND
< ND 1
i ND
ซ ND
i ND
1.2
> ND
l ND
l ND
l ND
ND
ND
l ND
l ND
3
ND
165
7 9
*ND*
l ND ป
23 5
2.2
32.4
ND
ND
ND
ND
ND
269
1 1
ND >
325
ND
ND
ND
1 5
5.4
4.1
ND
1.6
ND
14.0
1 ND I
NO
* ND
ID
ND
27.2
153
ซ ND
55
20.2
1.6
22.0
ND
NO
l ND
ND *
ND
16.6
ND
1 ND
16.8
ND
ND
l ND
1 1
3.5
27
ND
ND
ND *
48
ND
ND l
l ND *
18
ND
102
5.8
ND
l ND
24 3
2.3
29.4
ND 1
NO
ND >
ND
ND >
17.4
t 3
NO
23.1
ND l
ND
ND
ND
2.1
3 0
NO
ND
l ND
3 1
ND
ND >
ND *
28
ND >
15.6
90
ND
ND ป
19.2
2.2
21 7
l ND
ND
ND
NO ซ
ND
13 7
ND
1 ND 1
15.7
NO 1
ND >
l ND
NO
1.7
1.9
ND
NO
ND
2.3
ND l
ND l
ND
36
NO ป
13.9
6 2
ND
l ND
14.4
2.0
18.5
1 ND
1 ND
ND
ND
* ND
13.6
ND
1 ND *
11.8
t ND ซ
NO
(NO I
* NO >
2.0
1 6
ND
i ND
* ND
1.9
ND
NO
ND ซ
53
i NO ซ
14 3
6 4
> ND
l NO >
16 3
2.2
20.2
ND
NO i
ND
l ND
ND
15.3
ND
NO ซ
15.2
ND
ND
ND
l ND
2.2
1.9
ND
1 ND
ND
2.9
ND
ND
ND
69
ND >
9.0
4.7
l ND
1 NO >
16.0
24
20 3
l ND
ND
ND
ND
NO i
15.4
ND >
l ND ซ
13.4
ป ND ซ
ND
ND >
l ND
1.1
1.2
l ND
1 ND 1
ซ ND >
1.6
l NO ซ
ND *
ND ซ
98
NO
ND
ND
ND
ND l
13.5
2.1
18.8
ND
ND >
NO
ND
ND
11 5
ND
ND
10.5
ND ซ
ND
ND
ND
1 0
l ND i
l ND >
IND
ND
NO
l ND
ND i
ND ซ
130
ND
4 6
l ND ซ
ซ ND I
NO
10.5
1.9
16. B
ND
ND
l ND
ND
ND
6.8
ND
ND ซ
11.0
NO ป
NO
ND
ND
0.9
NO
ND >
1 ND
1 ND
ป ND ป
ND
NO
ND
173
ND ป
7.3
ND
ND
ND
7.4
NO
14 5
ND
l ND
ND
ND
* ND
5 5
ND
ND
11.3
1 ND
ND
ND
ND
0.7
ND
ND
ND
NO ซ
ND
ND ซ
l ND >
ND >
219
ป NO ป
9 0
4 B
ND
ซ ND
5.7
I 7
15 1
NO
ND
ND
NO
NO
7.4
ND
ND ซ
12 1
ND
ND
ND
ND
l.D
ND
ซ NO
ซ ND
* ND
ND
ND
ป NO ป
ND
All concentrations are to be interpreted only to two significant figures.
Not detected or below QL.
Includes both meta- and para-isomers.
Indicates a non-target compound not quantitifed in this experiment.
-------
TABLE D-24
Enpernent Title > HARDWIRE STORE 4i5i ALVEOLAR BREATH, CANISTER COLLECTION DUPLICATES
Spreadsheet File Naซe---> ABCHS4SO
End Tiซe > 12=13
CONCENTRATIONS (M1CROGRANS/CUBIC METER 3 25 deg. Ci 1 etป.)ฃ
COMPOUND
i
ro
Vinyl Chloride 62
Isapentane 57
Pentane 57
Vinylidene Chloride
2-Methylpentane 71
Oichloroiethane 64
Chlorafon 83
lilil-Trichloroethane 61
2-Methylheปane 57 S
Carbon Tetrachlonde 82
3-Methylhexane 57 8
Benzene 78
Triehloroethylene 60
Toluene 91
n-Octane 57
2-Hethylpropyl acetatrf
Tetrachloroethylene 57
Ethylcyclohexane (
Butyl acetate 610
3-Methylor.tane 57 9
Ethylbeniene 71
p-Xylene 91C
n-Nonane 57
Styrene 104
o-Xylent 91
I>2i4-Triiethylbeniene
n-Oecane 57
Triiethylbeniene iso. $
n-Undecane 570
n-Oodecane 57f
CHPD
ID
Mean Mean
Blank Recou.
l a
LOO
(ME)
OL SAMP
(NG)
VOLUME ANALYZED
REAL TIME (HH'HM) >
ELAPSED TIME (KIN) >
Je61
I
i
iane 61
9
de 82
8
60
tatetf
ie59
tent.)?
9
nene 9
so. f
36
45
46
1
47
34
2
(
SB
6
59
5
7
10
28
60
11
61
62
63
19
22
33
15
21
57
23
64
29
24
0.00 1.00
0.00
0.00
0.00
0.00
0.00
0 00
0.00
0.00
0.00
0.00
0 00
0.00
0.00
0.00
0.00
000
0.00
0 00
000
000
000
000
000
0.00
0.00
0.00
0.00
0.00
0 00
.00
.00
.00
.00
00
00
DO
.00
.00
.00
.00
00
.00
.00
.00
00
.00
00
.00
.00
.00
00
.00
00
.00
00
.00
00
00
0 07
0.06
0.07
0 03
0 08
0.09
0.03
0.17
0.02
0.02
0.02
0.06
0 04
0.02
0.02
0.02
0.09
0 06
0 02
0.02
0 01
0 01
0.02
0.01
0.02
0.01
0.02
0 01
0.02
0 02
0.27
0.25
0.30
0.13
0.32
0.34
0.10
0 66
0.07
0 10
0.07
0.24
0 17
O.OB
0.07
O.OB
0.36
0.32
O.OB
0.07
005
O.D4
0.07
0.05
0 09
0.04
0.10
004
0 10
0.10
10 SAMP. 10 SAMP. 10 SAMP.
140HS5AC01 14DHSSACD2
0.060
12:16 12
3
1 NO ซb
16.5
7.7
i ND
ป NO
27.5
1.8
362
i NO i
i ND
l NO i
ซ ND
1 NO I
23.5
2.0
i ND
31 8
INDI
1 ND 1
1 ND *
1.3
5.8
4 7
l ND *
1 8
i ND i
145
l ND i
INDI
* ND >
0 060
23
10
* ND
25.
11
ND
5
20
l ND
22
i ND
NO
NO
NO
1 ND
15.
NO
IND
17
i ND
l ND
IND
0.
3
1
ND
ND
NO
3.
ND
ND
ND
1
3
8
ซ
0
5
i
6
i
t
l
i
i
7
l
7
i
l
l
9
1
5
l
1
ป
1
l
1
ID SANP 10 SAMP. ID SAMP. 10 SAMP ID SAMP. ID SAMP. ID SAMP. ID SAMP. ID SAMP ID
14DHS4AC07 140HS4ACOB
D 060 0.060
13:22 13'51
69
l ND l
5.4
l ND
i ND l
i ND l
14.0
2.1
41.9
i ND l
i ND l
l ND ซ
l ND l
1 ND 1
14.7
l NO *
NO l
20.4
IND i
l ND *
l ND l
IND
2.0
2.8
l ND i
i NO l
l ND i
2.9
i NO <
NO
ND l
i
t
i
ซ
l
ซ
i
i
i
l
i
ซ
i
l
i
l
>
98
ND >
ND*
ND i
ND ป
NO l
12.4
2.0
38.1
ND >
NDi
ND i
ND*
ND >
14.1
ND *
ND*
16.4
ND i
ND *
ND*
ND*
1.9
2.2
ND ซ
NO *
NDi
2.2
ND *
ND i
ND*
All concentrations are to be interpreted only to two significant figures.
Not detected or below QL.
Includes both meta- and para-lsomers.
Indicates a non-target compound not quantitifed in this experlmenC.
-------
APPENDIX E
DECAY DATA IN GRAPHICAL FORM
E-l
-------
f -.
~)
E
X
cr>
' -
>
_j
s:
~o
i
-ฃ-
D
^
QD
55 -
50 -
45 -
40 -
35 -
30 -
25 -
20 -
15 -
10 -
5-
ri -
A
A Alveolar Breath
Whole Breath
A
A
A A
A
A
A
A
*
50
100
150
200
250
Time (Min.)
Figure E-2. Breath level of 1,1,1-trichloroethane post exposure to
furniture stripping operations. Exposure: 120 //g/m3;
QL = 8 /jg/m3.
E-2
-------
0^
E
ST
v3
1 1 1 r 1 , 1 r-
50
100 150
Time (Min.)
200
250
Figure E-3. Breath level of toluene post exposure to furniture
stripping operations. Exposure: 5700 /*g/m3; QL =
1.4
1 D -
o
^ "-
^v
en
13 B-
_)
-C
o ซ-
m
n -
A
A Alveolar Breath
A Whole Breath
A
A
A A
* * A.
^ 4,
50
100 150
Time (Min.)
200
250
Figure E-4. Breath level of p_-xylene post exposure to furniture
stripping operations. Exposure: 240 /Kj/m3; QL =
0.7
E-3
-------
D
0)
L.
m
80
72 -k
64 -
56 -
48 -
40 -
32 :
24 -
16 -
8 -
0
A Alveolar Breath
Whole Breath
A
50
100 150
Time (Min.)
200
250
Figure E-5. Breath level of dichloromethane post exposure to
hardware store environment. Exposure: 480 /jg/m3;
QL = 0.4 jtg/m3.
100
E
O1
QJ
0)
_J
_c
-^
o
\_
m
90 -
80 -
70 -
60 -
50 -
40 -
30
20 -
10 -
A Alveolar Breath
Whole Breath
50
100 150
Time (Min.)
200
250
Figure E-6. Breath level of 1,1,1-trichloroethane post exposure
to hardware store environment. Exposure: 330 /
-------
30
25 -
E
\
en 20 -
D
CD
m
15 -
10 -
5 -
A Alveolar Breath
Whole Breath
50
i
100
i
150
200
Time (Min.)
Figure E-7
Breath level of toluene post exposure to hardware
store environment. Exposure: 320 /jg/m3; Q|_ =
1.4 / > 1 ,..,,,..,.
0 50 100 150 200 2J
Time (Min.)
Figure E-8. Breath level of tetrachloroethylene post exposure
to hardware store environment. Exposure: 260 /jg/m3;
QL = 6.3 /ig/u)3.
E-5
-------
,3
n>
0)
o
0)
ffi
10 -
5 -
A Alveolar Breath
Whole Breath
A* A
50
100
150
200
250
Time (Min.)
Figure E-9. Breath level of ethylbenzene post exposure to
hardware store environment. Exposure: 470
QL = 0.9 /*g/m3.
rj
E
cr>
3
~a>
CD
_J
_c
"o
0)
CD
aw -;
45 ^
40 -
35 -
30 -
25 -
20 -
15 -
10 -
5 -
n -
i
A Alveolar Breath
Whole Breath
A
A
A A
A A
A
ป
* *
50
100 150
Time (Min.)
200
250
Figure E-10. Breath level of ฃ-xylene post exposure to hardware
store environment. Exposure: 1600 /*g/m3; QL =
0.7
E-6
-------
15
ro
v
-C
D
i_
CD
9-
6 -
3 -
1
50
A Alveolar Breath
Whole Breath
i
100
150
200
250
Time (Mln.)
Figure E-ll. Breath level of n-nonane post exposure to hardware
store environment. Exposure: 160 /*g/m3; Q|_ =
0.9
18
T 15 -
E
O"> 12 -
QJ
6
_J
_c
"o
CD
9 -
6 -
3-
I
50
A Alveolar Breath
Whole Breath
100
150
200
Time (Min.)
250
Figure E-12. Breath level of o-xylene post exposure to hardware
store environment. Exposure: 440 /jg/m3; Q|_ =
1.1
E-7
-------
n* X
")
J
E
ซv
\
CT>
Sw"'
0)
>
_c
O
0
m
90 -
80 -
70 -
60 -
50 -
40 -
30 -
20 -
10 -
0 -
A Isopentane
Chloroform
,
*
I
A *
*
A
* *
, , , , 1 , 1 , . 1 1 1 . . 1 1 ' i ' 1 ' ' ' 1 ' ' ' '
3 25 50 75 100 125 15
Time (Min.)
Figure E-13. Decay of isopentane and chloroform in alveolar breath
after exposure to an indoor swimming pool. Isopentane
exposure: 55 /
-------
en
0>
D
CD
j
-C
-* ป
D
0>
m
6400 -
6000 -
5600 -
5200 -
4800 -
4400 -
40OO -
3600 '-
3200 -
2800 -
2400 -
2000 -
1600 -
1200 -
800 -
400 -
n _
A
A 1 ,1.,1-Trichloroethone
A
A
A
A
A
A
25
50
75
100
125
150
175
200
Time (Min.)
Figure E-15. Decay of 1,1,1-trichloroethane in alveolar breath after
exposure to an active wood working and metal shop.
Exposure: 16000 /
-------
25 -
E20 ~
.
en
^ 15 -
"a;
I J
-+
0
0) 5-
m
0 -
A Toluene
* A
A
A
A
*
. 1 1 1 1 1 1 1 1 1 1 . 1 1 1 1 I 1 I | r 1 1 r | 1 1 1 1 | 11 11 | ' i i i
) 25 50 75 100 125 150 175 2C
Time (Min.)
Figure E-16. Decay of toluene in alveolar breath after exposure
to an active wood working and metal shop. Exposure:
510 /ig/m3; QL = 1.4 jnP.
E-10
-------
CD
D
a)
^
CD
6 -
2 -
A Limonene
aPinene
10
15
20
Time (Mrs.)
Figure E-17. Decay of limonene and a-pinene in whole breath after
exposure to consumer products as determined by Tenax-
based sampling and analysis. Limonene exposure:
160 pg/m3, QL = 1.4 fig/ml; a-pinene exposure:
95 fig/ml; 1.1 pg/m3.
<")
_E
CJ1
3
cp
CD
i
c~
O
0)
m
j/j -
350 -
325 -
300 -
275 -
250 -
225 -
200 -
175 -
150 -
125 -
100 -
75 -
50 -
25 -
o
c
A p-Dichlorobenzene
A
A
A
A
A
A
A
A
* A
1 10 20 30 40 50 60 7
Time (Mrs.)
Figure E-18. Decay of ฃ-dichlorobenzene in whole breath after
exposure to consumer products as determined by Tenax-
based sampling and analysis. Exposure: 10000 /
-------
_^
ro
E
\
^s,
3
ID
0)
i
~
D
-------
i
E
^\
CJ>
"-'
T>
(U
_j
-C
o
0)
CD
90 -
so :
70 -
.
60 -
50 -
40 -
30 -
;
20 -;
10 -
0 -
A
A Alveolar Breath
ซ Whole Breath
A
A
A A
A
A
A
*
1 1 ' 1 1 1 1 1 1
0 50 100 150 200 2J
Time (Min.)
Figure E-21. Breath level of 2-methylpentane post exposure to
staining in home garage. Exposure: 2000 /*g/m3;
QL = 4.2 /ig/m3.
*)
E
^
3
QJ
1
_c
-t-'
D
(U
^_
CD
90 -
80 -
70 -
60 -
50 -
40 -
30 -
20 :
10 -
0 -
A Alveolar Breath
Whole Breath
A
*
A
A
A A
A*
50
100
150
200
250
Time (Min.)
Figure E-22. Breath level of 2-methylhexane post exposure to
staining in home garage. Exposure: 340 ug/m3;
QL = 0.9 /ig/m3.
E-13
-------
c* X
N
)
E
>v\
en
3
0)
CD
_J
-C
t -J
0
CD
i^
DO
50 :
45 -
40 -_
35 -
30 -,
25 :
20 -
15 -
10 -
5 -
n -
A
A Alveolar Breath
Whole Breath
A
A
A
A
A ป * A
* A
50
100
ISO
200
Time (Min.)
Figure E-23. Breath level of 3-methylhexane post exposure to
staining in home garage. Exposure: 410 /
-------
50
45-
40 -
30
25
20
15
D
-------
D
OJ
m
30 -
25 -
20 -
15 -
10 -
5 -
A Alveolar Breath
Whole Breath
A
A
50
100 150
Time (Min.)
200
Figure 1-27. Breath level of ethylcyclohexane post exposure to
staining in home garage. Exposure: 900 uq/m3;
Ql = 4.2 /ig/m3.
200
180 -
C '60 -
\ 140 -
3? '20 -
-------
o~^
E
\
-.
^.
v> x
QJ
5.)
_j
JC
0
a>
m
0^
E
en
^^
^ '
"QJ
OJ
'
JT
4-*
0
2.
m
40 -
35 -
30 -
25 -
20 -
15-
10 -
5-
0 -
A
^ A Alveolor Breoth
A A Whole Breath
A
A A A
A
A
A
A
.
1 1 . 1 1 1 1 1 1 1 1 . 1 1 , 1
0 50 100 150 200 25
Time (Min.)
Figure ฃ-29. Breath level of ethylbenzene post exposure to
staining in home garage. Exposure: 2600 ug/m3;
QL = 0.7 /ig/m3.
35 -
30 -
25 -
20 -
15 -
10 -
5 -
n -
A Alveolar Breath
* Whole Breath
A
0 A
A A A
A
t
A
*
50
100 150
Time (Min.)
200
250
Figure E-30. Breath level of ฃ-xylene post exposure to staining
in home garage. Exposure: 1700 /*g/m3; QL = 0.5 /ig/m3.
E-17
-------
J~)
E
"er>
3
0)
0)
1
-C
D
(U
-------
^
}
CP
2
-3
"oJ
]>
0)
1
_c
o
Q)
\^
m
. v.
T
ฃ
en
3=
(D
>
CD
JC
"o
ฃ_
m
200 n
180 :
160 -i
140 -
:
120 -
100 -
80 -
60 -
40 -
20 -
A
A Alveolor Breath
Whole Breath
A
A
A
*
A
ซ * *
A
A
^
ฐ 0 50 100 150 200 250
Time (Min.)
Figure E-33. Breath level of n-decane post exposure to staining
in home garage. Exposure: 14,000 fig/m*; QL =
1.3 /*g/nH .
130 -
120 -
110 -
100 -
90 -
80 -i
70 -.
60 -
50 -
40 -
30 -
20 -
10-
X
A Alveolar Breath
Whole Breath
A
A
A
A
9 A A
A
ซ 0 0
50 100 150 200 250
Time (Min.)
Figure E-34. Breath level of n-undecane post exposure to staining
in home garage. Exposure: 5600 /ig/m3; QL = 1.3
E-19
-------
^^
i-O
E
en
^2>
1
0)
_c
4 '
D
ฃ_
CD
60 -T
55 -i
50 -.
45 -
40 -
35 -
30 -
25 -
20 -
15 -
10
5
w
A Participant
Participant
*
* * . t
* A
A
A
A A
A
A
0 -| 1 ' ' 1 ' ' ' ' 1 ' ' i
0 50 100 150
Time (Min.)
1 (expt. HSZ)
2 (expt. HS2)
200 250
Figure E-35. Decay of dichloromethane in alveolar breath for two
participants exposed at the same time in a hardware
store environment. Exposure: 450 /*g/m3; QL = 6 /*g/m3.
^-^
^E
"cri
^_
y '
-------
.,
~)
E
i
~
CD
40 -
35 -
30 -
25 -
20 -
15 -
10 -
5 -
n -
#
A Porticipont 1 (expt. HS3)
A
Participant 2 (expt. HS2)
A
A
*
A
* i ซ
A ซ
* A
A
50
100
150
200
250
Time (Min.)
Figure E-37. Decay of toluene in alveolar breath for two partici-
pants exposed at the same time in a hardware store
environment. Exposure: 640 fig/m^; QL = 1.4
rO
Ql
Brea
3-
A Participant 1 (expt. HS3)
Participant 2 (expt. HS2)
ซ
A
i
50
I
100
I
150
I
200
Time (Min.)
250
Figure E-38. Decay of ethyl benzene in alveolar breath for two
participants exposed at the same time in a hardware
store environment. Exposure: 150 /*g/m3; QL = 0.9 /*g/m3.
E-21
-------
20 -r
KP
\ 15 -
cn '
~oJ 10 -
_i
ji
.*->
0
CO
0
A Participant 1 (expt. HS3)
Participant 2 (expt. HS2)
A
* * *
A A ป
* A ซ
' ' '
, , 1 , 1 , . 1 1 1 i i i i | ' ' ' ' 1 ' ' ' '
3 50 100 150 200 2!
Time (Min.)
Figure E-39. Decay of ฃ-xylene in alveolar breath for two partici
pants exposed at the same time in a hardware store
environment. Exposure: 570 /*g/m3; Ql_ = 0.7 /jg/m^.
cr>
-------
-3 1
03
-C
-t->
D
^
CD
I -
A Porticipont 1 (expt. HS3)
Porticipant 2 (expt. HS2)
50
100
150
200
Time (Min.)
Figure E-41. Decay of o-xylene in alveolar breath for two partici
pants exposed at the same time in a hardware store
environment. Exposure: 200 ^g/m3; QL = 1.6 /jg/m3.
25
E
CP
-------
50
CP
D
QJ
1_
m
. A
40
30-
20-
10 -
A Porticipont 3 (expt. HS4)
Participant 4 (expt. HS5)
50
100 150
Time (Min.)
200
250
Figure E-43. Decay of dichloromethane in alveolar breath for two
participants exposed at the same time in a hardware
store environment. Mean exposure: 270 //g/m3; Q|_ =
6
E
5
100
90
60
0) 50
_J 40
-C 30
4~l
o
-------
60
T 50 -
E
O"> 40 -
(U 30 -
0,1
20 -
_C
D
m
10 -
A Participant 3 (expt. HS4)
Participant 4 (expt. HS5)
A
I *
A
I
50
l
100
I
150
200
250
Time (Min.)
Figure E-45. Decay of toluene in alveolar breath for two partici-
pants exposed at the same time in a hardware store
environment. Mean exposure: 370 /ig/m3; QL = 1.4 /jg/m3.
70
rO
CP
0
-------
r-O
CD
>
0)
D
0)
CD
20
15 -
10 -
5 -
A Participant 3 (expt. HS4)
Participant 4 (expt. HS5)
.
A
I
50
100
150
200
250
Time (Min.)
Figure E-47. Decay of p_-xylene in alveolar breath for two partici-
pants exposed at the same time in a hardware store
environment. Mean exposure: 190 ^g/m3; QL = 0.7 fig/ml.
20
Cf>
CD
_l
JC
t-j
O
L.
CD
15 -
10 -
5 -
A Porticipont 3 (expt. HS4)
Participant 4 (expt. HS5)
A
A
I
50
I
100
150
200
250
Time (Min.)
Figure E-48. Decay of n-nonane in alveolar breath for two partici-
pants exposed at the same time in a hardware store
environment. Mean exposure: 120 /*g/m3; QL = 1.2 /jg/m3.
E-26
-------
en
D
0)
m
35
JO -
25 -
20 -
-------
APPENDIX F
CALCULATED HALF-LIFE DATA FOR ALVEOLAR AND WHOLE BREATH DECAY CURVES
F-l
-------
TABLE F-l. CALCULATED HALF-LIVES FOR HALOGENATED HYDROCARBONS IN ALVEOLAR BREATH
rss
One Coipanenl Node)
Exposure
Cone.
Coipound uj/i3
Halogenated Hydrocarbons
Vinyl idem chloride Si
OicMoroiehtane 5000
Dichloronthane 470
Dichloroiethane 440
OlchloroietKane 320
Dichloroiethine 220
CKIorolon MO
1 -Triehloroethane 14000
1 -Trlchloroethane 340
1 -Trichloroethane 200
1 -Trichloroethane 200
1 -Trichloroethane 200
1 -TricMorocthane UO
TrlcMoroethylene 77
Tet rich loroethy lent 280
Tetrachloroethylene 190
Tetrachlororthylene 150
Eซpt. Parlic-
Code ipant
US1 1
FS1 1
H51 2
HS3 1
HS4 3
HS5 4
SP1 2
US1 1
H51 2
HS2 2
HS3 1
HSS 4
FS1 1
FS1 1
HS1 2
H54 3
HSS 4
One
Coipart.
tl/2 (h)
2.97
0.40
0.40
1.07
0.45
1.8*
0.72
0.68
1.22
4.30
0.99
3.39
1.00
0.45
2.42
0.85
2.01
95X
Cont. Int.
Ranje (h)
1.70-11.6
0.43-1.02
0.30-0.42
0. 91-1.31
0.47-1.07
1.40-2.7&
D.52-1.17
0.40-1.43
0.87-2.05
2.84-8.47
0.47-l.BB
2.11-8.40
0.70-1.77
0.4S-1.19
1.87-3.43
0.41-1.40
1.11-15.4
Tvo Caipartient Node)
First
tl/2 (h)
0.12
0.13
0.10
0.78
0.08
0.17
0.08
0.10
0.13
0.00
0.17
0.17
D.OB
0.20
0.18
0.11
95X
Conf. Int.
Ran9e (h)
0.07-3.25
0.10-0.25
0.07-0.15
0.23-NE
0.04-0.43
0.02-NE
0.05-0.22
0.07-0.23
0.08-0.27
0.01-NE
0.13-0.24
0. OS-HE
0.05-0.15
O.Oi-0.20
0.07-NE
0.04-0.53
Second
tl/2 (h)
11.40
1.80
1.07
If
1.14
2.07
1.58
1.90
Z.40
3.81
3.1B
6.08
1.60
1C
3.70
1.47
95X
Conf. Int.
Ranje (h)
S.BS-NE*
1.25-3.22
0.82-1.53
HC*
0.79-2.03
1.15-10.0
1.10-2.43
1.38-3.05
1.92-4.03
0.03-NE
2.18-5.95
2.20-NE
1.45-2.35
NC
2.23-10.8
1.13-3.13
Residual Conversance Failure
r2
One
Coipart.
0.942
0.944
0.971
0.994
0.985
0.987
0.948
0.941
0.945
0.990
0.942
0.979
0.974
0.987
0.989
0.970
0.925
r2
Tvo
Coipart.
0.994
0.998
0.998
0.997
0.999
0.988
0.997
0.997
0.998
0.990
0.999
0.987
0.999
0.998
0.994
0.995
NC
Calculated
F2,d.f
18.2
S0.8
61. 9
NC
31.5
0.3
34.4
40.7
57.3
0.1
103.4
2.2
74.4
NC
4.5
1B.4
NC
Beit
Coipart.
Fit (9511 C.I.)
2
2
2
NC
2
1
2
2
2
1
2
1
2
NC
2
2
NC
aExposure concentrations for the garage experiment (GS1) are approximate.
bNE " Confidence interval included negative exponents which can't be transformed into half-life values using this method.
CIC Model reflects insufficient change in concentration to calculate a second half-life over this time interval.
dNC - Not calculated.
-------
TABLE F-2. CALCULATED HALF-LIVES FOR AROMATIC HYDROCARBONS IN ALVEOLAR BREATH
Coipound
One Coiparnnt Model
Exposure3 One 95X
Cone. Eipt. Par tic- CflipJrt. Conl. Int.
119/iS Code ipant tl/2 (k) Range (K)
Tun Cmpartient Model
951 "Si""
First Cont. Int. Second Cont. Int.
tl/2 (M Ranse (h) tl/2 (h) Ran,e (k)
tZ r2 Best
One Tuo Calculated Coipart.
Coipart. Coipart. F, , , Fit (951 C.I.)
Z.d.r.
Aroiitic Hydrocarbons
Beniene
Toluene
Tolutne
Tolwnt
Toluene
Toluene
Toluene
Toluene
Toluene
EtMbentene
Ethylbentene
Ethyl benzene
Ethylbeniene
ip-Xylene
np-Xylene
ip-Xylene
np-Xylene
np-Xylene
up-Xylene
o-Xylene
o-Xylene
o-Xylene
Exposure
430
5700
1ZOD
MO
UO
510
440
3ZO
260
2600
340
150
ISO
1600
1700
540
540
230
140
440
700
190
G51
FSI
GSI
H52
HS3
US1
H54
HS1
N55
651
HS1
HS2
H53
HS1
GSI
HS2
HS3
HS4
HS5
HS1
GSI
HS2
concentrations
HE - Confidence interval
CNC - Hot
calculated.
1
1
1
2
1
1
3
2
4
1
2
2
1
2
1
2
1
3
4
2
1
2
for the
1.4B
0.82
1.64
1.53
1.04
1.15
1.13
0.52
1.4*
2.44
0.22
1.70
1.02
0.72
1.40
0.4*
0.45
0.08
0.56
0.25
0.47
1.41
1.14-3.16
0.55-1 .52
1.30-3.14
1.15-2.27
0.74-1.73
0.92-1. ss
0.40-6.63
0.36-0.82
1.09-4.79
1.91-3.45
0.13-0.42
1.11-3.41
0.72-1.72
0.72-1.23
1.27-2.17
0.41-1.36
0.28-1.13
0.05-0.23
0.35-1.42
0.15-0.58
0.42-1.49
0.73-7.84
garage experiment
Included negative
0.1*
0.10
0.05
0.07
0.08
0.05
0.27
0.03
o.oa
0.0*
0.08
0.03
0.13
0.11
0.03
0.06
0.08
0.11
0.0*
0.04-NEb 3.38 1.80-29.1
0.07-0.18 1.82 1.36-2.43
0.03-IC 2.44 1.94-4.04
0.02-fC 1.88 1.33-3.24
0.05-0.41 1.48 1,25-2.54
Residual Convergence Failure
0.03-0.11 4.05 2.41-12.6
0.15-1.23 3.23 0.83-NE
REdldual Convergence Failure
0.01-NE 2.90 2.28-4.00
0.07-0.15 2.12 1.10-29.3
0.02-flE 2.49 1.73-4.48
0.02-NE 1.43 0.80-7.13
0.01-NE 1.10 0.86-1.45
Residual Convergence Failure
0.08-0.37 2.42 1.23-40.5
0.04-1.05 2.15 0.88-NE
0.02-0.04 2.16 1 24-8.75
0.05-0.54 2.12 1.07-64.2
0.04-NE 1.17 0.35-fE
0.08-0.20 2.94 1.49-11.2
0.02-NE 9.95 1.83-NE
0.949
0.958
0.977
0.984
0.975
0.989
0.995
0.947
0.947
0.992
0.931
0.944
0.964
0.983
0.990
0.943
0.922
0.695
0.91S
0.941
0.927
0.979
0.992
0.998
0.994
0.993
0.997
NCC
0.995
0.989
NC
0.997
0.992
0.994
0.993
0.995
NC
0.992
0.960
0.995
0.785
0.983
0.994
0.999
99
46.9
16
4.1
22
K
4.7
6.4
NC
7.1
32.4
16.4
2.9
9.4
NC
22.2
10.3
66.9
16.3
4
56.1
30.8
2
2
2
1
2
NC
2
2
NC
2
2
2
1
2
NC
2
2
2
2
1
2
2
(GSI) are approximate.
exponents which
can't be transformed Into half-life
values
using this
method.
-------
TABLE T-3. CALCULATED HALF-LIVES FOR ALIPHATIC HYDROCARBONS IN ALVEOLAR BREATH
Cnpound
Exposure8
Cone. Expt.
ug/aS Code
One Cnparnnt Model
Partic-
ipant
On*
Coipart.
tl/2 (h)
951
Cant. Int.
Range (h)
Tn Coapartaent Model
951
First Coni. Int. Second
tl/2 (h) Rang* (h) il/2 (h)
951
Cant. Int.
Rang* (h)
r2
On*
Coipart.
r2
Tra
Coipart
Calculated
F2,d.f
Best
Coipart.
.Fit (95XC.I.)
Aliphatic Hydrocirbom, Straight-Chain
n-Pmtana
n-Ptntint
n-Octani
n-Octam
n-Nonani
n-Honant
iHbnanf
n-Honani
n-tbnana
n-Manani
n-Oecant
n-Onani
n-Oecane
n-Otcane
n-Otcane
n-Onani
n-Undnanc
Aliphatic HydrocarboiMi
liopintant
2-Htthylpintant
2-flethylhaxani
3-fltthylhnam
3-fttthylhixint
2-HtthylDctam
Ethylcyclohnani
3400 GS1
340 USl
320 GS1
39 HS2
12000 GS1
210 H52
210 H53
180 H51
130 HS4
110 HSS
14000 GS1
360 HS2
360 HS3
260 HS1
210 HS4
170 HSS
5400 ESI
Branchtd-Chain
10000 GS1
2000 651
340 ESI
410 GS1
39 FS1
5400 651
900 GS1
1
1
2
1
2
1
2
3
4
1
2
1
2
3
4
1
0.7D
1.15
0.67
0.87
1.37
1.13
0.68
0.08
0.21
0.61
1.35
0.22
0.17
0.08
0.27
0.11
0.28
0.65
0.86
0.26
0.39
0.42
0.60
0.89
0.43-1.81
0.60-17.2
0.47-1.14
0.54-2.30
1.01-2.15
0.74-2.34
0.47-1.23
0.05-6.33
0.13-0.58
0.39-1.46
1.03-1.96
0.14-0.57
0.09-1.10
0.07-0.17
0.20-0.44
0.06-0.74
0.18-0.58
0.40-1.77
0.60-1.48
0.17-0.49
0.26-0.77
0.30-0.65
0.46-0.85
0.64-1.48
0.08
0.07
0.19
0.17
0.02
0.06
0.15
0.02
0.04
0.18
0.08
0.04
0.07
0.19
0.05
0.07
0.08
0.21
0.13
0.13
0.28
0.19
0.04-0.16 2.34
0.01-NEb 2.07
0.14-0.28 2.84
0.04-NE ICC
0.01-NE 1.73
0.04-0.18 2.01
0.08-0.82 2.06
0.01-0.17 0.48
D.02-D.1D 1.53
Residual Convergence
0.092-3.89 2.33
0.04-0.81 1.39
D.02-NE 1.06
0.02-KE 1C
0.10-1.24 2.82
0.03-NE 1C
0.06-0. ID 1.36
0.05-0.19 2.33
0.14-0.42 3.18
0.09-0.21 3.16
0.10-0.17 2.54
Residual Convergence
0.16-1.07 2.48
0.12-0.40 2.53
1.51-5.13
0.48-0.90
1.74-7.70
NC<1
1.31-2.55
1.50-3.02
1.05-6.12
0.30-1.17
0.97-3.53
Failure
1.55-4.95
0.47-NE
0.43-NE
NC
0.41-0.58
NC
1.04-1.95
1.38-7.45
1.67-35.2
1.25-NE
1.62-5.88
Failure
0.85-NE
1.53-7.36
0.925
0.954
0.962
0.985
0.978
0.958
0.961
0.918
0.886
0.978
0.984
0.927
0.911
0.990
0.962
0.938
0.941
0.920
0.965
0.948
0.946
0.993
0.981
0.969
D.966
0.967
0.999
D.995
0.994
0.997
0.992
0.999
0.993
NC
0. 997
0.987
0.997
0.999
0.974
0.997
0.999
0.993
0.997
0.994
0.998
NC
0.995
0.997
58.5
0.8
75.3
NC
8.9
42.4
13.1
109.0
56.5
NC
13.8
11.1
51.0
NC
1.6
NC
142.0
37.5
35.9
26.2
101.0
NC
8.7
34.3
2
1
2
NC
2
2
2
2
2
NC
2
2
2
NC
1
NC
2
2
2
2
2
NC
2
2
"Exposure concentrations for the garage experiment (GS1) are approximate.
NE Confidence interval included negative exponents which can't be transformed into half-life values using this method.
ฐIC - Model reflects insufficient change in concentration to calculate a second half-life over this time interval.
dNC ซ Not calculated.
-------
TABLE F-4. CALCULATED HALF-LIVES FOR AROMATIC AND HALOGENATED HYDROCARBONS IN WHOLE BREATH
U1
One Coipanent Node)
Exposure8
Cone.
Covound ug/i
Armatlc Hydrocarbons
Benitne 430
Toluene 5700
Toluene 1200
Toluene 320
Ethylbemene 2400
Ethylbeniine 340
np-Xylene 1400
np-Xylena 1700
np-Xylene 240
o-Xylene 440
o-Xyleai TOO
Halogenated Hydrocarbons
DlcKlorosetkane 5000
OichloroiethlM 470
liM-Trichloroethane 340
lilil-Trlchloroethane 140
Tetrachloroethylene 280
p-Olchlorobenione 9400
EซPt.
Code
GS1
FS1
G51
HSI
GS1
HSI
HSI
GS1
FS1
HSI
GS1
FS1
HSI
161
FS1
HSI
CPl
Partic-
ipant
1
1
1
2
1
2
2
1
1
2
1
1
2
2
I
2
2
One
Coipart.
tl/2 (h)
.30
.03
.24
.03
.25
.95
.05
.04
0.55
0.93
1.21
0.95
0.55
1.33
1.10
2.13
1.57
951
Conf. Int.
Range (h)
1.01-1.82
0.82-1.38
1.01-1.58
0.75-1.57
1.05-1.56
0.13-0.72
0.83-1.42
0.85-1.42
0.42-0.82
0.46-1.47
0.94-1.48
.72-1.45
.45-0.75
.00-2.07
.87-1.52
.45-4.02
.11-2.42
Tun Coipartient
951
First Conf. Int.
tl/2
0.44
0.32
0.31
(h) Range (h)
0.29-1.06
0.23-0.45
0.12-fE
Model
Second
tl/2 (h)
4.12
2.26
1.84
Residual Convergence
0.46
0.25
0.18
0.52
0.25
0.06
0.53
0.40
0.33
1.36
0.52
1.48
O.S3
0.22-NE
0.15-0.73
0.07-NE
0.33-1.28
0.20-0.37
0.03-NE
0.26-NE
0.25-1.25
0.28-0.45
0.30-2.47
0.30-1.85
0.07-0.07
0.40-0.81
2.45
2.17
1.40
4.98
2.52
1.46
4.02
7.98
5.40
if
1C
1C
21.00
951
Conf. Int.
Range (h)
.75-NEb
.48-3.48
.04-7.75
Failure
.02-NE
.32-4.20
.05-3.32
.28-2.42
.33-20.9
.18-1.97
.28-9.47
1.28-NE
1.67-4.35
NC
NC
NC
13.0-58.2
r2
One
Coipart.
0.988
0.987
0.977
0.974
0.994
0.979
0.986
0.989
0.973
0.965
0.987
0.975
0.982
0.981
0.989
0.980
0.957
r2
Tm
Coipart.
0.999
0.999
0.996
NCd
0.999
0.996
0.997
0.999
0.999
0.999
0.998
0.997
0.999
0.998
0.999
0.982
0.994
Calculated
F2,d.f
44.9
123
6.5
NC
10.9
28.7
10
27.9
70.8
112
13.1
17.1
58.4
NC
K
NC
29.6
Best
Coipart.
Fit (951 C.I.)
2
2
2
NC
2
2
2
2
2
2
2
2
2
NC
NC
NC
2
aExposure concentrations for the garage experiment (GS1) are approximate.
bNE - Confidence Interval Included negative exponents which can't be transformed into half-life values using this method.
CIC Model reflects insufficient change in concentration to calculate a second half-life over this time Interval.
dNC - Not calculated.
-------
TABLE F-S. CALCULATED HALF-LIVES FOR ALIPHATIC AND CYCLIC HYDROCARBONS IN WHOLE BREATH
(hit Cnpawnt IMtl
Cnpound
Aliphatic Mrourteni
n-ffntai*
n-Octint
_ Jhna-a
II IWIMIIOJ
n-Otcint
HMKIM
Aliphatic HrdracartaMi
IfBPfntaM
ZHhtliylptnUM
Z-tbthrlhnana
3HkthythniM
Z-fkthyloctant
Cirellc HytYocarblM
EtMcytlalitซiiw
a-Plmnt
Llventnt
Eipnarta
Core. Eipt.
ui/i3 Cede
Straight-Chain
3100 SI
320 GSI
tzoiro GSI
14000 GSI
5600 GSI
BrafKhfd-Chaln
tonon GSI
zooo GSI
340 GSI
400 ESI
5*00 651
910 GSI
77 CM
ItO (71
Om
Partlc- Cotwrt.
Ipanl 11/2 (h)
0.88
o.ซ
0.74
0.88
0.66
O.B9
1.02
O.B7
0.88
D.%
1 0.19
2 0.7?
2 2.63
951
CoM. Int.
Raw (M
O.M-l.tl
0.74-1.32
0.57-1.05
0.49-1.72
0.65-1.24
0.42-1 .58
0.75-1.60
0.60-1.52
0.63-1.46
0.77-1.26
0.73-1.56
0.56-1.35
1.56-5.49
Tuo Crapartiei
Pint
tl/2 (M
0.26
0.00
0.42
0.00
0.19
0.24
0.26
0.29
0.31
0.57
0.40
0.13
0.24
951
Conl. Int.
Raw (h)
0.13-4.13
0.42-*b
0.25-1.23
0.00-0.00
0.12-0.60
0.14-0.81
0.13-NE
0.16-1.64
0.19-O.B7
0.27-tE
0.21-3.96
0.04-0.22
0.11-NE
tlWel
Cm .J
avcuno
tl/2 (h)
2.32
0.61
5.55
0.68
1.61
2.85
2.25
3.47
3.57
5.20
6.64
1.60
6.88
951
COM. Int.
Rinfe (h)
1.10-K
0.27-NE
0.9Z-NE
0.66-1.22
1.17-2.60
1.40-NE
1.17-fC
1.2Z-K
1.39-HE
0.57-tC
1.00-NE
I.Z9-6.98
2.54-NE
2
r
Out
Ceipart.
0.973
0.985
0.982
0.986
0.982
0.965
0.978
0.966
0.971
0.990
0.983
0.972
0.976
2
r
Tra
Coipart.
0.976
0.991
0.997
0.986
0.999
0.997
0.997
0.996
0.998
0.997
0.998
0.999
0.996
Cileulatid
h.&.i.
15.3
3.2
13.6
0
34.1
28.2
14.6
17.9
28.4
5.5
19.8
163.6
2.01
Beit
Coipart.
Fit (951 C.I.)
2
1
2
I
2
2
2
2
2
1
2
2
il
"Exposure concentrations for the garage experiment (GSI) are approximate.
bHE - Confidence interval Included negative exponents which can't be transformed Into half-life values using this method.
-------
TABLE F-S. CALCULATED HALF-LIVES FOR ALIPHATIC AND CYCLIC HYDROCARBONS IN WHOLE BREATH
Onซ CoiMWnt Nodfl
Exposure a
Cone. Expt.
Compound us/i3 Code
Aliphatic Hydrocarbons Straljht-Gilin
n-Pntlnt 34CD G51
n-Octani 329 GS1
n-Nonant 1ZOOD GS1
n-Oecane 14000 GS1
iHJndecane 5400 GS1
Aliphatic Hydrocarbons Bfanct.fd-O.aln
lioptntane 10000 GS1
2-nfthylptntlit 2000 GS1
2-Hitr,ylKซxini 340 G51
3-nethylhexine 400 GS1
2-HitMoctant 5400 GS1
Cyclic Hydrocarbon!
Ethylcycloliexant 900 GS1
a-Pineni 97 CPI
LiiflMM 140 CPI
One
Partle- Coipart.
ipant tl/2 (h)
1
1
1
1
1
2
2
D.B8
o,1s
H.74
0.88
0.86
.69
.02
.87
.88
.94
0.99
0.79
2.43
951
CoM. Int.
Raw (h)
0.64-1.41
0.74-1.32
0.57-1.05
0.49-1.22
0.45-1.24
0.62-1.58
0.75-1.40
0.40-1.52
0.43-1.44
0.77-1.24
0.73-1.54
0.54-1.35
1.56-5.49
Tra Coipartient
951
Pint Conf. Int.
tl/2 (h) Range M
0.24
0.00
0.42
0.00
0.19
0.24
0.24
0.29
0.31
0.57
0.40
0.13
0.24
0.13-4.13
0.ป2-ซEb
0.25-1.23
0.00-0.00
0. 12-0.40
0. 14-0.81
0.13-NE
0.14-1.44
0.19-0.87
0.274C
0.21-3.94
0.04-0.22
O.ll-NE
Indel
Sicond
tl/2 (M
2.32
0.41
5.55
0.88
1.41
2.85
2.25
3.47
3.S7
5.20
4.44
1.40
6.88
951
Conf. Int.
Ranje (h)
1.10-NE
0.27-NE
0.92-NE
0.48-1.22
1.17-2.40
1.40-NE
1.17-NE
1.22-NE
1.39-NE
0.57-NE
1.00-NE
1 29-6.98
2.54-NE
2
On*
Cotpart
0.973
0.985
0.9B2
0.984
0.982
0.945
0.978
0.964
0.971
0.990
0.983
0.972
0.976
2
Tun
Coipart.
0.996
0 994
0.997
0.986
0.999
0.997
0.997
0.996
0.998
0.997
0.996
0.999
0.996
Calculated
%.d.f
15.3
3.-2
13.6
0
34.1
28.2
14.4
17.9
28.4
5.5
19.6
163.8
2.01
Bnt
Coipart.
Fit (951 C.I.)
2
1
2
1
2
2
2
2
2
1
2
2
11
aฃxposure concentrations for the garage experiment (GS1) are approximate.
bNE - Confidence Interval included negative exponents which can't be transformed into half-life values using this method.
------- |