BROAD SCAN ANALYSIS OF HUMAN ADIPOSE TISSUE:
VOLUME II: VOLATILE ORGANIC COMPOUNDS
by
John S. Stanley
FINAL REPORT
EPA Prime Contract No. 68-02-4252
MRI Project No. 8821-A01
December 31, 1986
National Human Monitoring Program
Field Studies Branch (TS-798)
Design Development Branch
Office of Pesticide and Toxic Substances
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, DC 20460
Attn: Ms. Janet Remmers and Mr. Philip Robinson, Work Assignment Managers
Dr. Joseph Breen and Ms. Cindy Stroup, Program Managers
U.S. Environmental Protection Agency
Region V, Library
230 South Dearborn Street
Chicago, Illinois 60604
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DISCLAIMER
This document has been reviewed and approved for publication by the
Office of Toxic Substances, Office of Pesticides and Toxic Substances, U.S.
Environmental Protection Agency. The use of trade names or commercial
products does not constitute Agency endorsement or recommendation for use.
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PREFACE
This report is the second of a five-volume series that details the
broad scan chemical analysis of composite adipose tissue samples. These com-
posite samples were prepared from individual specimens obtained from the
Environmental Protection Agency's (EPA) National Human Adipose Tissue Survey
(NHATS) fiscal year 1982 (FY82) repository.
This volume summarizes data generated from the analysis of the com-
posited samples for volatile organic compounds. Volume I, the executive sum-
mary, presents a synopsis of all analysis efforts completed under the broad
scan program. Volumes III through V deal specifically with the chemical analy-
sis of the NHATS composites for general semivolatile organic compounds, poly-
chlorinated dibenzo-p_-dioxins (PCDD), and dibenzofurans (PCDF), and trace ele-
ments. The statistical analyses of the data reported in these volumes will
be reported separately by the EPA's Office of Toxic Substances (OTS) Design
and Development Branch contractor, Battelle Columbus Laboratories.
The entire series of reports are referenced as follows:
Stanley JS. 1986. Broad scan analysis of human adipose tissue:
Volume I: Executive summary. EPA 560/5-86-035.
Stanley JS. 1986. Broad scan analysis of human adipose tissue:
Volume II: Volatile organic compounds. EPA 560/5-86-036.
Stanley JS. 1986. Broad scan analysis of human adipose tissue:
Volume III: Semivolatile organic compounds. EPA 560/5-86-037.
Stanley JS. 1986. Broad scan analysis of human adipose tissue:
Volume IV: Polychlorinated dibenzo-p_-dioxins (PCDD) and poly-
chlorinated dibenzofurans (PCDF). EPA 560/5-86-038.
Stanley JS, Stockton RA. 1986. Broad scan analysis of human adi-
pose tissue: Volume V: Trace elements. EPA-560/5-86-039.
These method development, sample analyses, and reporting activities
were completed for the EPA/OTS Field Studies Branch (FSB) broad scan analysis
of human adipose tissue program (EPA Prime Contract Nos. 68-02-3938 and 68-02-
4252, Work Assignments 8 and 21, respectively, Ms. Janet Remmers, Work Assign-
ment Manager, and Dr. Joseph Breen, Project Officer).
The samples were prepared with the assistance of Ms. Leslie Moody
and Mr. Steven Turner. The HRGC/MS methods development and sample analyses
were conducted by Mr. Steven Turner, Ms. Margaret Wickham, and Mr. Gil
Radolovich. The compositing scheme used to prepare the samples from the NHATS
repository was provided by Dr. Gregory Mack, Battelle Columbus Laboratories,
under contract to the EPA/OTS Design and Development Branch (Mr. Philip
Robinson, Task Manager, and Ms. Cindy Stroup, Program Manager).
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MIDWEST RESEARCH INSTITUTE
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John E. Going Paul C. Constant
Director Program Manager
Chemical Sciences Department
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TABLE OF CONTENTS
Page
Executive Summary xi
I. Introduction 1
A. Broad Scan Analysis Strategy 1
B. Work Assignment Objectives 1
C. Background Information 2
II. Recommendations 3
III. Experimental 3
A. Collection and Storage of NHATS Specimens 4
B. Sample Compositing Activity 4
C. Sources and Preparation of Analytical Reagents . . 5
1. Internal Quantisation Standards 5
2. Reference Compounds 6
3. Spiking Solutions 7
D. Apparatus 8
1. Dynamic Headspace Purge and Trap System ... 8
2. High Resolution Gas Chromatography/Mass
Spectrometry 8
E. Analysis Procedures 10
1. Spiking Procedure 10
2. Method Blank Analysis 10
3. Calibration Curves for Reference Standards. . 10
4. Composited Sample Analysis 11
F. Quality Control Procedures 11
G. Data Interpretation 11
1. Qualitative Identification 11
2. Quantisation 14
H. Method Validation 14
IV. Results 23
V. Quality Assurance/Quality Control 75
A. Instrument Performance Checks 75
1. Internal QC 75
2. External QC 75
B. Spiked Adipose Tissue Samples 76
C. Internal Standards 76
VI. References 85
Appendix A - Analytical Method for the Determination of Volatile
Organic Compounds in Human Adipose Tissue A-l
Appendix B - Volatile Organic Compound Data from the NHATS FY82
Composite Human Adipose Tissue Samples B-l
Appendix C - Compositing Scheme for the NHATS FY82 Specimens C-l
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LIST OF FIGURES
Figure Page
1 Schematic of apparatus for volatile organic analysis ... 9
2 Analytical scheme for analysis of volatile organic
compounds from human adipose tissue 12
3 Purging efficiency of three internal standards (1 ug
each) from 20 g of human adipose tissue, over four
sequential, 40-min heating and purging cycles 19
4 Purging efficiency of eight stable isotope labeled
internal standards (1 ug each) from 20 g of human
adipose tissue over four sequential 40-min heating
and purging cycles 20
5 Purging efficiency of seven target analytes (0.20 ug
each) spiked into 20 g of human adipose tissue, over
four sequential 40-min heating and purging cycles. ... 21
6 Purging efficiency of six target analytes (0.20 ug each)
spiked into 20 g of human adipose tissue, over four
sequential 40-min heating and purging cycles 22
7 Comparison of purging efficiencies for target analyte/
deuterated analog pairs: (a) benzene/d6-benzene and
(b) toluene/d8-toluene 24
8 Comparison of purging efficiencies for target analyte/
deuterated analog pairs: (a) chlorobenzene/d5-
chlorobenzene and (b) ethylbenzene/d10-ethylbenzene. . . 25
9 Comparison of purging efficiencies for target analyte/
deuterated analog pairs for (a) 1,1,2,2-tetra-
chloroethane/d2-l,l,2,2-tetrachloroethane and
(b) l,2-dichlorobenzene/d4-l,4-dichlorobenzene 26
10 Purging efficiency of seven volatile organic analytes
endogenous to human adipose tissue over four
sequential 40-min heating and purging cycles 27
11 HRGC/MS chromatogram of purge tower standard analyzed
daily to document instrument performance 28
12 HRGC/MS chromatogram for the volatile organic analysis
of a bulk adipose (tissue standard) spiked with 1.0 pg
of each internal standard and 0.20 ug of each target
analyte 29
13 HRGC/MS chromatogram of volatile compounds from the NHATS
FY82 composite of the 0-14 yr age group from the
Middle Atlantic census division 30
vii
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LIST OF FIGURES (concluded)
Figure Page
14 Comparison of the HRGC/MS chromatograms for the volatile
organic analytes for three composite age groups from
the Middle Atlantic census division 31
15 Comparison of the HRGC/MS chromatograms for the volatile
organic analytes for three composite age groups from
the East North Central census division 32
16 Comparison of the HRGC/MS chromatograms of the volatile
organic analysis of three composite specimens repre-
senting the 15-44 age group from three census divisions. 33
17 Comparison of the HRGC/MS chromatograms of the volatile
organic analysis of three composite specimens repre-
senting the 0-14 age group from three census divisions . 34
18 Incidence of detection of volatile organic compounds in
composited human adipose tissues from the Northeast
census region 36
19 Incidence of detection of volatile organic compounds in
composited human adipose tissues from the South
census region 37
20 Incidence of detection of volatile organic compounds in
composited human adipose tissues from the North Central
census region 38
21 Incidence of detection of volatile organic compounds in
composited human adipose tissues from the West
census region 39
22 Observed HRGC/MS responses for the internal standards
d-chloroform and d6-benzene, from method blanks,
spiked tissue samples and the NHATS composite samples. . 81
23 Observed HRGC/MS responses for the internal standards
d8-toluene and d5-chlorobenzene, from method blanks,
spiked tissue samples and the NHATS composite samples. . 82
24 Observed HRGC/MS responses for the internal standards
d10-p_-xylene and d10-ethylbenzene, from method blanks,
spiked tissue samples and the NHATS composite samples. . 83
25 Observed HRGC/MS responses for the internal standards
d2-l,l,2,2-tetrachloroethane and d4-dichlorobenzene,
from method blanks, spiked tissue samples and the
NHATS composite samples 84
vm
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LIST OF TABLES
Table Page
1 Characteristic Ions, Internal Standards, and Relative
Retention Times Used to Identify and Quantitate
Target Analytes 13
2 Summary of Spiked Recovery (%) Experiments for Volatile
Analytes from 20 g of Human Adipose Tissue 16
3 Summary of Spiked Recovery (%) Experiments Based on a
Single Internal Standard Bromochloropropane versus
Multiple Deuterated Standards (Isotope Dilution) .... 17
4 Data Report - Chloroform (CAS No. 67-66-3) -
FY82 Composite Adipose Tissue Samples 40
5 Data Report - 1,1,1-Trichloroethane (CAS No. 67-66-3) -
FY82 Composite Adipose Tissue Samples 42
6 Data Report - Bromodichloromethane (CAS No. 75-27-4) -
FY82 Composite Adipose Tissue Samples 44
7 Data Report - Benzene (CAS No. 71-43-2) -
FY82 Composite Adipose Tissue Samples 46
8 Data Report - Tetrachloroethene (CAS No. 127-18-4) -
FY82 Composite Adipose Tissue Samples 48
9 Data Report - Dibromochloromethane -
FY82 Composite Adipose Tissue Samples 50
10 Data Report - 1,1,2-Trichloroethane (CAS No. 79-00-5) -
FY82 Composite Adipose Tissue Samples 52
11 Data Report - Toluene (CAS No. 188-88-3) -
FY82 Composite Adipose Tissue Samples 54
12 Data Report - Chlorobenzene (CAS No. 108-90-7) -
FY82 Composite Adipose Tissue Samples 56
13 Data Report - Ethyl benzene (CAS No. 100-41-4) -
FY82 Composite Adipose Tissue Samples 58
14 Data Report - Bromoform (CAS No. 75-25-2) -
FY82 Composite Adipose Tissue Samples 60
15 Data Report - Styrene (CAS No. 100-42-5) -
FY82 Composite Adipose Tissue Samples 62
16 Data Report - 1,1,2,2-Tetrachloroethane (CAS No. 79-34-5)
- FY82 Composite Adipose Tissue Samples 64
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LIST OF TABLES (concluded)
Table Page
17 Data Report - 1,2-Dichlorobenzene (CAS No. 95-50-1) -
FY82 Composite Adipose Tissue Samples 66
18 Data Report - 1,4-Dichlorobenzene (CAS No. 106-46-7) -
FY82 Composite Adipose Tissue Samples 68
19 Data Report - Ethyl Phenol (CAS No. 25429-37-2) -
FY82 Composite Adipose Tissue Samples 70
20 Data Report - Xylene (CAS No. 1330-20-7) -
FY82 Composite Adipose Tissue Samples 72
21 Incidence of Detection of Selected Volatile Organic
Compounds in the NHATS FY82 Composite Samples 74
22 Summary of the Internal QC Instrument Performance Checks
for Selected Volatile Organic Analytes 77
23 Average Recovery for Internal QC Instrument Performance
Checks 78
24 Summary of Results - QC Performance Audit Samples 79
25 Summary of Method Recovery (%) of Selected Volatile
Organic Analytes Spiked into 20-g Aliquots of
Human Adipose Tissue - Internal QC 80
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EXECUTIVE SUMMARY
The U.S. Environmental Protection Agency's Office of Toxic Sub-
stances (EPA/OTS) maintains a unique program for monitoring human exposure
to potentially toxic substances. The National Human Adipose Tissue Survey
(NHATS) is a statistically designed annual program to collect and analyze a
nationwide sample of adipose tissue specimens for toxic compounds. The pri-
mary focus for NHATS has been to document trends in human exposure to environ-
mentally persistent contaminants, specifically organochlorine pesticides and
polychlorinated biphenyls (PCBs).
EPA/OTS has recognized the need to provide a more comprehensive
assessment of the toxic substances that accumulate in adipose tissue. Thus,
the NHATS specimens collected during fiscal year 1982 (FY82) were designated
for "broad scan analysis" to determine volatile and semivolatile organic com-
pounds and trace elements.
This volume of the final report deals specifically with the measure-
ment of volatile organic chemicals in composited adipose tissue specimens from
the FY82 NHATS repository. The objectives of this part of the study were (1)
to develop an analytical method based on high resolution gas chromatography/
mass spectrometry (HRGC/MS) for determination of volatile organic chemicals
in human adipose tissue and (2) to complete the analysis of the FY82 NHATS
specimens as composited for volatile organic compounds.
The analytical method developed to sample volatile organic compounds
from human adipose tissue is based on a heated dynamic headspace purge and
trap technique. The volatile organic compounds were separated and detected
using HRGC/MS. HRGC was selected to achieve the best possible separation of
volatile components, and MS was selected to provide the necessary specificity
to identify positively the volatile compounds present in the tissue. Target
analytes were quantitated based on a multiple internal standard technique.
The method evaluation studies and daily quality control checks demonstrated
that method accuracy was improved for analytes which had a corresponding
deuterated analog as an internal quantisation standard.
Forty-six composite samples were prepared from the FY82 NHATS repos-
itory according to a study design prepared by the EPA/OTS Design and Develop-
ment Branch contractor, Battelle Columbus Laboratories. The composite samples
represent the nine U.S. census divisions, stratified by three age groups
(0-14, 15-44, and 45 plus).
The HRGC/MS analysis of the volatile compounds purged from the human
adipose demonstrated a complex mixture of compounds consisting primarily of
aldehydes, ketones, hydrocarbons, and carboxylic acid esters. Additional com-
pounds classified as aromatic, halogenated aliphatic, and halogenated aromatic
compounds were detected as minor constituents.
Quantitative efforts focused on target analytes classified as pri-
ority pollutants. Quantitative data are reported for 17 specific compounds.
The predominant target analytes noted included chloroform, 1,1,1-trichloro-
ethane, benzene, tetrachloroethene, toluene, chlorobenzene, ethyl benzene,
XI
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styrene, 1,1,2,2-tetrachloroethane, 1,4-dichlorobenzene, 1,2-dichlorobenzene,
xylenes, and ethyl phenol. In all composite samples several compounds were
detected including styrene, the xylene isomers, 1,4-dichlorobenzene, and
ethyl phenol. The frequencies of detection for each of the compounds by age
groups and census divisions are detailed in the report. The volatile organic
compounds were detected in the composites from all census divisions and age
group.
The quantitative data for the 17 specific compounds have been sub-
mitted along with all supporting quality control data to the OTS design and
development contractor, Battelle Columbus Laboratories, for statistical
analysis.
Characterization of additional chromatographic peaks in the HRGC/MS
data to identify other compounds of interest to the Agency has been initiated
under a separate work assignment (Contract No. 68-02-4252, Work Assignment
No. 23).
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I. INTRODUCTION
The National Human Adipose Tissue Survey (NHATS) is the main opera-
tive program of the National Human Monitoring Program. The National Human
Monitoring Program was first established by the U.S. Public Health Service in
1967 and was subsequently transferred to the U.S. Environmental Protection
Agency (EPA) in 1970. During 1979 the program was transferred within EPA to
the Exposure Evaluation Division (EED) of the Office of Toxic Substances (OTS).
NHATS is an annual program to collect a nationwide sample of adipose
tissue specimens and to chemically analyze them for the presence of toxic
compounds. The objective of the NHATS program is to detect and quantify the
prevalences of the compounds in the general population. The NHATS data are
used to address part of OTS's mandate under the Toxic Substances Control Act
(TSCA) to assess chemical risk to the U.S. population. The specimens are
collected from autopsied cadavers and surgical patients according to a statis-
tical survey design (Lucas, Pierson, Meyers, Handy 1981). The survey design
ensures that specified geographical regions and demographic categories are
appropriately represented to permit valid and precise estimates of baseline
levels, time trends, and comparisons across subpopulations.
The data for the NHATS are generated by collecting and chemically
analyzing adipose tissue specimens for selected toxic substances. Histor-
ically, organochlorines and polychlorinated biphenyls (PCBs) have been
selected for evaluation.
A. Broad Scan Analysis Strategy
EPA/OTS has recognized the need to provide a more comprehensive
assessment of the toxic substances that accumulate in adipose tissue. An
aggressive strategy to assess TSCA-related substances that persist in the
adipose tissue of the general U.S. population has been developed by EED. The
NHATS specimens collected during fiscal year 1982 (FY82) were selected for a
broad scan analysis of volatile and semivolatile organic TSCA-related chemi-
cals and trace elements (Mack, Stanley 1984).
The initiative to achieve a more comprehensive assessment necessi-
tated either the development of new methods or the modification of the exist-
ing analytical procedures, specifically high resolution gas chromatography/
mass spectrometry (HRGC/MS). Data on organochlorine pesticides and PCBs
reported for the NHATS specimens up to the FY82 collection are based on
packed column gas chromatography/electron capture detector (PGC/ECD) analysis.
B. Work Assignment Objectives
The objectives of this phase of the work assignment were (1) to
identify appropriate analytical methods for a broad scan analysis of volatile
organic compounds in human adipose tissue based on HRGC/MS detection; (2) to
conduct preliminary evaluation of the analytical procedures, and (3) to com-
plete the sample workup and HRGC/MS analysis of 46 composite samples prepared
from the NHATS specimens collected during FY82. The target detection range
for analytes by the HRGC/MS as specified in the current NHATS strategy (Mack,
Stanley 1984) was 0.05 to 0.10 pg/g.
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C. Background Information
The exposure of the general U.S. population to volatile organic
compounds has not previously been addressed through a national sampling of
biological matrices (breath, blood or tissue). Specific studies have been
conducted, however, to determine the effects of exposure to chemical solvents,
monomers such as vinyl chloride and styrene in the plastics industry, and
anesthetics (Wolff 1976; Wolff, Loumer, Selikoff, Aubrey 1977; Engstrom,
Riihimaki 1979; Engstrom 1984).
The fact that blood and breath levels of volatile organics can be
detected at declining levels from several hours to several days after a spe-
cific exposure incident indicate tissue retention (Whitcher, Cohen, Trudell
1971; Corbett 1973; Wolff 1976). Human adipose tissue has been evaluated as
a depot for storage and release of volatiles in specific exposure studies of
workers to styrene and ethyl benzene in the polymerization industry (Wolff 1976;
Wolff, Daum, Loumer, Selikoff, Aubrey 1977; Engstrom 1984).
Several analytical procedures have been developed for the measure-
ment of specific compounds from these exposure scenarios. Analytical tech-
niques have required dissolution of milligram quantities of adipose into car-
bon disulfide, or other suitable solvent, followed by direct injection onto
gas chromatographic (GC) columns with flame ionization/electron capture, mi-
crocoulometric or mass spectrometer (MS) detectors. Other analytical proce-
dures combined with these detection systems have included: (a) static head-
space analysis of heated tissue, (b) stripping volatiles from heated tissue
by flowing an inert gas directly through the rendered sample, (c) vacuum dis-
tillation and cryogenic focusing of the analytes on a high resolution gas
chromatography (HRGC) column, and (d) dynamic solution purge and trap and
headspace analysis of heated tissue water mixtures combined with cryogenic
focusing and HRGC analysis. Each of these techniques has certain advantages
and disadvantages in terms of complexity of the actual sampling procedure and
sensitivity and selectivity of the detector (Novotny, McConnell, Lee, Farlow
1974; Politzer, Githens, Dowty, Laseter 1975; Luskus, Kilian, Lackey, Biggs
1977; Snyder, Erlichman, Goldstein, Laskin 1977; Karbowski, Braun 1978;
Peoples, Pfaffenberger, Enos, Shafik 1978; Balkon, Leary 1979; Peoples,
Pfaffenberger, Shafik, Enos 1979; Pfaffenberger, Freal 1979; Michael,
Erickson, Parks, Pellizzari 1980; Pantarotto, Fanelli, Belletti, Bidoli 1980;
Reddrop, Riess, Slater 1980; Vogt, Liao, Sun 1980; Zuccato, Marcucci, Mussini
1980; Lin, Fu, Bruckner, Feldman 1982; Hiatt 1981; Reinert, Hunter, Sabatino
1983).
An analytical method for the measurement of volatile organic chem-
icals in human adipose tissue has been developed as a result of this work
assignment. This analytical method is a modification of a dynamic headspace
purge and trap procedure (Michael, Erickson, Parks, Pellizzari 1980) combined
with high resolution gas chromatography and mass spectrometry. This report
describes the method and summarizes the volatile organic data for 46 composite
specimens from the FY82 NHATS repository determined with the method.
Following this introductory section, Section II presents recommen-
dations for further activities for volatile organics. Section III is the
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experimental section and describes the collection and storage of the NHATS
specimens, the adipose tissue compositing procedures, the development of the
analytical method, and the routine analytical procedures. Section IV presents
the results of the composite tissue analyses. Section V summarizes the qual-
ity control (QC) procedures and results. Section VI contains references.
Appendices A, B, and C provide, respectively, the volatile organic analysis
method in detail, additional data tables on the results of the analyses, and
the exact compositing scheme used for the FY82 NHATS specimens.
II. RECOMMENDATIONS
Further analytical development should be pursued to improve the
determination of volatile organic compounds in human adipose tissue samples.
These improvements should specifically include smaller sample sizes (1.0 to
5.0 g), more efficient transfer of volatile organics onto the HRGC column,
and further development of the isotope dilution quantitation technique, these
modifications can possible be achieved by using widebore HRGC columns and/or
cryofocusing techniques.
The analytical method should be modified to provide quantitative
information on compounds of greater volatility than chloroform (such as
methylene chloride, vinyl chloride, etc.). This possibly could be accom-
plished by conducting two analyses on each tissue sample. The first analysis
should be conducted for the more volatile compounds with the sample heated in
the range of 50-80ฐC and the headspace sampled for 15 min or less. The second
sample analysis should be conducted with the procedures specified in this re-
port to provide quantitative data for compounds ranging in volatility from
chloroform through the dichlorobenzene isomers.
Stability studies should be conducted to determine the effects of
long-term storage at subzero temperature, and repeated thawing and freezing
on the integrity of the volatile organic content in the sample. The results
of the sample analysis conducted for the FY82 composites indicate considerable
differences in the absolute quantities of the major volatile constituents
(hydrocarbons, aldehydes, ketones, etc.) for samples analyzed within 6 mo of
collection and the NHATS specimens that have been archived prior to analysis
for up to 2 yr.
III. EXPERIMENTAL
This section of the report describes:
A. collection and storage of NHATS specimens;
B. sample compositing activity;
C. sources and preparation of analytical standards;
D. apparatus;
E. analysis procedures;
F. quality control procedures;
G. data interpretation; and
H. method validation.
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A. Collection and Storage of NHATS Specimens
The adipose specimens were originally collected during FY82
(October 1, 1981, through September 30, 1982) for determination of organic
chlorine pesticide and PCB residues. The specimens were collected during
surgical procedures or as part of postmortem examinations. The cooperating
physicians and pathologists were requested to acquire at least 5 g of high
lipid adipose (subcutaneous, perirenal, or mesenteric), taking precautions to
avoid contamination that might result in direct contamination from chemicals
such as solvents, paraffin, disinfectants, preservatives, or plastics. The
cooperators were given no specific instructions to avoid potential contamina-
tion that might arise from background contribution of solvents or metals.
The adipose tissue specimens were sealed in glass jars and frozen
(-20ฐC) following collection. The specimens were shipped in insulated coolers
packed on dry ice. The FY82 specimens were originally received and stored at
EPA's Toxicant Analysis Center (TAG) at Bay St. Louis, MS. The NHATS reposi-
tory was transferred to Midwest Research Institute (MRI) during September
1982. The specimens were shipped in insulated coolers and packed on dry ice.
The specimens were inventoried at MRI upon receipt and were then stored in
freezers (-20ฐC). Precautions were taken to ensure that the specimens re-
mained frozen during all inventory and sample handling procedures.
B. Sample Compositing Activity
The NHATS FY82 adipose tissue specimens were subsampled and compos-
ited as specified by EPA's Design and Development Branch contractor, Battelle
Columbus Laboratories (BCL). Prior to preparation of the composites, all of
the FY82 specimens were retrieved from the NHATS repository and the individual
specimens bottles were grouped according to the designated compositing scheme
provided by BCL. Care was taken to ensure that the specimens were not al-
lowed to reach room temperature. The specimen were stored on dry ice during
this process and were returned to a freezer (-20ฐ) once all individual speci-
men for a specific composite had been located.
All specimens for a specific composite were removed from the freezer
at the same time for the compositing effort. The specimens were placed on
dry ice so they would remain frozen during the compositing effort. Each spe-
cimen was handled separately and each was subsampled for the composites for
both volatile and semivolatile organic anlaysis. This resulted in minimum
handling of each specimen. Once the speciment had been subsampled for each
composite it was placed on dry ice. After all specimen had been added to the
composites, the batch was returned to the freezer.
All samples were handled in a positive pressure Plexiglas hood of
approximately 94.5 L volume to prevent contamination from laboratory air.
Compressed air was filtered through a charcoal trap to remove potential vola-
tile contaminants from air supply before it entered the hood. The subsamples
were manipulated with the rounded end of a lab spoon-type stainless steel
spatulas and placed in 40-mL vials with TFE septa caps. Each specimen was
manipulated with a separate clean spatula. All weighings were performed to
ฑ 0.1 g on a Mettler open pan balance placed in the hood.
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The nominal mass of each individual specimen necessary to achieve a
final composite mass of 20 g was determined before proceeding with the phys-
ical compositing. For example, if a composite consisted of 20 specimens,
1.0 g of each specimen was necessary to achieve a final composite mass of
20 g. Separate composite samples were prepared for both semivolatile (Stanley
1986c) and volatile organic analysis. The individual specimens were added
first to the composites for the semivolatile organic analysis. This resulted
in the addition of a total available specimen, in some cases, to the semivola-
tile organic composite only. As a result, several of the volatile organic
composites contain somewhat less than the target 20 g of tissue mass. The
samples resulting from the 46 volatile organic composites ranged from 5.1 to
25.6 g total mass with an average mass of 19 g. Appendix C provides a summary
of the exact compositing scheme for both the volatile and semivolatile organic
analyses.
Prior to the compositing effort, the vials were washed in soap and
water, rinsed thoroughly with tap water, deionized water, bulk acetone,
Burdick and Jackson (B&J) acetone, and B&J hexane, and then placed in an oven
at 200ฐC for 48 h before use. The spatulas were washed and rinsed as above
and were dried for at least 5 min in the oven.
All composites were stored on dry ice until transfered to a freezer
(-20ฐC). Before being placed in the freezer in the 40-ml vials, the compos-
ited samples were grouped by census division and placed in 1.0-qt jars
(cleaned as above) containing a layer of activated charcoal and closed with a
TFE-lined cap. The samples were stored in the freezer until analysis.
As a QA/QC check, six of the empty vials used for compositing were
placed in the hood on the weighing balance for approximately 15 min (approxi-
mating the time needed for compositing), and then were capped, sealed, and
stored with the samples. These blank vials were included with the analysis
of the composited specimen as method blanks.
The samples resulting for the 46 composites ranged from 5.1 to
25.6 g total mass with an average mass of 19 g. Appendix C provides a sum-
mary of the exact compositing scheme.
C. Sources and Preparation of Analytical Reagents
The sources of the internal standards and reference compounds and
the procedures for preparing spiking and calibration standards are described
below.
1. Internal Quantitation Standards
A three-component internal quantisation standard mixture was ob-
tained from Supelco, Inc. (Catalog No. 4-8823, Lot No. LA 11802). This mix-
ture contained bromochloromethane, 1,4-dichlorobutane, and l-chloro-2-bromo-
propane at 20 mg/mL each in 1.0 mL of methanol. This mixture was used as re-
ceived and was stored in the freezer in its original resealable ampule.
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A second stock solution of deuterated internal quantisation stan-
dards was prepared from the compounds listed below by aliquoting each with a
100-uL syringe into a 10-mL volumetric flask and diluting to the mark with
methanol (B&J high purity, Lot No. AJ029). The volume of each compound neces-
sary to achieve the desired concentration was determined by the density of
the specific compound. The final concentration was approximately 10 mg/mL
for each deuterated internal standard. Because the l,4-d4-dichlorobenzene is
a solid, a separate stock was prepared in methanol before addition to the so-
lution containing the other deuterated analogs. The final mixture was sealed
in two 5-mL vials and stored in the freezer until just prior to use.
Compound
d6-benzene
d-chloroform
I,l,2,2-d2-tetrachloroethane
d2-methylene chloride
ds-chlorobenzene
l,4-d4-dichlorobenzene
dxo-ethylbenzene
d8-toluene
d10-p_-xylene
2. Reference Compounds
Supplier
Aldrich Gold Label (99.5% D) No.
Aldrich Gold Label (99.8% D) No.
M and D Isotopes No. MD-1416
M and D Isotopes No. MD-53
KOR Isotopes (99% D5) No. 521510
KOR Isotopes (98% D4) No. 521530
Isotopes (98% D10) No. 521443
Isotopes (99.9% D8) No. 510041
Isotopes (98% D10) No. 521133
15,
15,
181-5
182-3
KOR
KOR
KOR
Several compounds characteristic of aromatic compounds, chlorinated
and brominated aliphatic compounds, and chlorinated aromatic compounds were
selected for preparation of analytical standards. These reference compounds
were also selected as a preliminary list of target analytes as a result of
their presence in tissue from the preliminary method development and their
classification as priority pollutants.
The compounds listed below were aliquotted with a 100-fjL syringe
into a 10-mL volumetric flask that was partially filled (approximately 5 mL)
with methanol. The volume of each compound necessary to achieve the desired
concentration was determined from the density of each specific compound. The
solution was diluted to the mark and stored in the same manner as the internal
quantisation standard solutions. The compounds were aliquotted to obtain a
final stock concentration of approximately 10 mg/mL for each compound.
Compound
bromoform
di bromochloromethane
toluene
1,1,2-trichloroethane
styrene
tetrachloroethylene
bromodi chloromethane
chlorobenzene
1,2-dichlorobenzene
ethylbenzene
Supplier
Aldrich Gold Label (99%/l% EtOH)
Columbia No. D1843
B&J H.P. No. Al-857
Aldrich No. JB-070177 (95%)
Eastman No. 1465
Aldrich Gold Label No. 120457
Aldrich No. 7628AH (98%)
Aldrich No. 120277 (99%)
Aldrich No. D5-680-2 (98%)
Aldrich No. El-250-8 (99%)
-------
Compound
1,1,2,2-tetrachloroethane
1,1,1-trichloroethane
chloroform
benzene
carbon disulfide
3. Spiking Solutions
Supplier
Baker No. 017386
Fisher No. 775974
B&J H.P. (1% EtOH preservative)
No. AG594
MCB Pest. Grade No. U2738
Mallinckrodt No. KMEE
The reference stock solution and the two internal quantitation stan-
dard stock solutions (Supelco mixture and the deuterated analog mixture) were
used to make up the spiking solutions necessary for HRGC/MS analysis. The
three separate stock solutions allowed manipulation of the concentrations of
the spiking levels to verify method calibration and accuracy of the analyses
from spiked tissue and blank samples.
Spiking solutions were prepared fresh weekly from the three stock
solutions. The spiking solutions were prepared in 1.0-mL microreaction vials
(Supelco No. 3-3292) with Mim'nert Valves (Supelco No. 3-301). Tetraglyme
was used as the solvent for the spiking solutions to enhance their stability.
All spiking solutions were stored in the refrigerator and transported between
the GC/MS facility and the laboratory on ice in a cooler. Following sample
spiking, the solutions were immediately returned to the cooler.
The spiking solutions were prepared by aliquoting tetraglyme into
the 1.0-mL reaction vials and then spiking the tetraglyme with the stock solu-
tions. For example, a 500-ng/uL internal standard spiking solution was made
by injecting 975 uL of tetraglyme with a 1.0-mL syringe (available from
Supelco, Inc.) into the reaction vial and then injecting 25.0 uL of the three-
component (20 mg/mL) Supelco internal quantitation standard stock solution
into the tetraglyme. A 500-ng/uL spiking solution of the deuterated internal
standards was similarly prepared by spiking 950 uL of tetraglyme with 50.0 uL
of the 10-mg/mL deuterated internal standard stock solution.
The target analyte spiking solution was prepared in the same manner
but at 100 ng/uL. This was accomplished by spiking 990 uL of tetraglyme with
10.0 uL of the target analyte stock solution.
When the actual sample analyses were initiated, only two spiking
solutions were necessary. A 500-ng/uL solution of the three internal stan-
dards from the Supelco mixture and the nine deuterated internal standards were
combined. This mixed internal quantitation standard solution was prepared
with 925 |jL of tetraglyme, 25.0 uL of the three-component Supelco standard,
and 50.0 pL of the deuterated internal standard stock solution. The target
analyte spiking solution was prepared at the 100-ng/uL level as described
above.
-------
D. Apparatus
The design of the dynamic headspace purge and trap system used to
collect the volatile organics and the HRGC/MS system used for separating and
identifying these compounds are described below.
1. Dynamic Headspace Purge and Trap System
Method development for volatile organic analytes in human adipose
tissue led to the system shown in Figure 1. Several Wheaton purge and trap
vessels (No. 991765) were modified for the analyses. The thermometer and
funnel arms were cut near the vessel and replaced by 1/4-in. Kovarฎ to PX seal
tubes (Ace Glass, Inc., No. PT.976). This allowed the inlet and outlet lines
to be connected with standard 1/4-in. Swagelockง fittings and provided leak-
tight connections.
The Wheaton vessel was connected to a hot water circulating bath
(Haake, No. F4391) maintained at 95ฐC. Approximately 5 min was required for
the solution within the vessel to reach the maximum purge temperature. The
vessel was placed on a magnetic stirrer (Ace Glass, Inc., No. 12064-08), and
a 1.0-in. TFE stirring bar agitated the solution. Helium was directed into
the vessel to displace the headspace at 40 mL/min. All metal gas carrier
lines beyond the vessel outlet were wrapped with heat tape maintained at 150ฐC
to prevent condensation of the target analytes and internal standards. The
effluent from the vessel line flowed into a column equipped with a stopcock
and frit that contained 1.0 ml of volatile-free water. This column was used
as a condenser to remove excess moisture from the purge gas. The outlet line
from this purge tower was attached to a six-way Carle valve. A GC carrier
gas line of helium was attached to the Carle valve. The Carle valve was at-
tached to a glass-lined U-tube (1/8 i.d.) packed with a 1.0-in. plug of Tenax.
Glass wool was used to maintain the position of the Tenax in the center of
the U-tube. The U-tube was rapidly heated (within 5 to 8 s) to 250ฐC. A
resistance circuit with a thermocouple was used to heat and regulate the U-
tube's temperature. In the purge mode the Carle valve directed the purge gas
and analytes into the U-tube, which was at ambient temperature. The analytes
were trapped and the purge gas vented. The helium carrier gas was directed
onto the HRGC column during the purge mode. After the purge time had elapsed,
the Carle valve was switched to the desorb mode and the U-tube was heated to
flash volatilize the analytes. The helium carrier gas was then routed through
the U-tube in the opposite direction of the purge mode and directed onto the
HRGC column.
2. High Resolution Gas Chromatography/Mass Spectrometry
The volatile organic compounds were analyzed using a Finnigan 9610
GC and a Finnigan 4000 quadrupole MS equipped with an INCOS data system.
Separation of the volatile organic compounds was achieved with a Durabond DB-5
fused silica capillary column, 30 m x 0.25 mm, 0.25-|jm film thickness (J&W
Scientific, Rancho Cordova, CA). The capillary column was routed directly
into the ion source. The helium carrier gas was adjusted at 12 psi head pres-
sure. The GC was equipped with a Grob type split/splitless injector. The
effluent from the adsorbent trap was adjusted to 5 to 10 mL/min and directed
-------
High Amoerage
Low Volfage /
Transformer
Flow Controller
for He
Temperature
Controller
Purge Tower
with Glass Frit
Water
Heated line
H2O In
Figure 1. Schematic of apparatus for volatile organic analysis.
-------
into the Grob injector with a syringe needle attached to the stainless steel
tubing from the adsorbent trap. The injector was operated in the split mode
with a 10:1 split ratio.
The GC was held isothermally at 30ฐC for 5 min and then programmed
at 6ฐC/min up to 125ฐC where it was held for 10 min. Mass spectral data were
acquired across the mass range of 35-275 amu for 20 min from initiation of
the program. The HRGC column was programmed to 200ฐC between sample analyses
as a precaution to ensure that all materials desorbed from the Tenax adsorbent
had been eluted from the column prior to the next analysis.
E. Analysis Procedures
The procedures for spiking internal quantitation standards, the
method blank analysis, generation of calibration curves, and composited sample
analysis are described below.
1. Spiking Procedure
Internal quantitation standards and target analytes were added to
the purge tower, method blanks, spiked adipose tissue matrix and composite
samples using the following procedure. A 35-mm length of TFE tubing was in-
serted over the needle port on the Leur lock assembly of a 10.0-mL syringe.
The syringe was filled with 3.0 mL of volatile organic-free water and the TFE
tubing removed. The water in the syringe was spiked with the working stan-
dards (using a 5.0-pL syringe and needle) through the needle port, and the
TFE tubing was replaced. An additional 2 ml of water and 1.0 ml of air was
then drawn into the 10-mL syringe, and the syringe was inverted several times
to ensure mixing of the tetraglyme and water solution. The contents of the
syringe were quantitatively transferred to the sample vessel. The sample
vessel was tightly capped and the sample was allowed to sit at room tempera-
ture for 30 min prior to initiating the analysis.
2. Method Blank Analysis
The Wheaton vessel was filled with 80 mL of the volatile organic-
free water and spiked with 1.0 pg of each of the internal quantitation stan-
dards. The vessel was quickly capped and the gas flow turned on. The purge
tower valve was kept in the off position, and the vessel and lines were leak
checked with volatile organic-free water. Following the leak check, the purge
tower valve was opened, the hot water bath valves opened, and the stirring
bar turned on. The headspace above the stirred mixture was purged for 40 min
and collected on the Tenax trap.
3. Calibration Curves for Reference Standards
Calibration curves for the compounds selected as reference standards
were developed using a spiked human adipose tissue matrix. The spiked adipose
tissue matrix is referred to as the tissue standard. A separate 20-g aliquot
of a bulk adipose matrix was used to prepare each tissue standard. These
tissue standards were prepared immediately prior to analysis. Preparation of
the spiked tissue samples as homogenized matrices for repeated analysis was
not evaluated in this study.
10
-------
The analysis of the tissue standard was performed in the same way
as the analysis of the blank but with 20 g of human adipose tissue added to
the Wheaton vessel. A spatula was used to remove the frozen tissue from the
sample vials. The tissue samples were spiked with 1.0 ug of each of the in-
ternal standards and 0.2 to 1.4 ug of each of the target analytes. Purge time
was 40 min.
4. Composited Sample Analysis
The composited samples were analyzed in exactly the same manner as
the tissue standard except that only the internal standard spiking solution
was added to the aqueous mixture.
F. Quality Control Procedures
Figure 2 shows the general volatile organic analysis scheme and the
related quality control (QC) procedures. Daily QC procedures included the
analysis of reference standards and internal standards spiked in the purge
tower (instrument performance check); a system blank with internal standards;
a reference adipose tissue spiked with standards; and a QC sample. The QC
sample consisted of either an additional instrument performance check to
verify calibration or an adipose tissue spiked at a known level by the MS
analyst. These QC samples were included for several days at the initiation
of the analysis of the composites. Also, the MRI quality control coordinator
(QCC) periodically submitted blind spikes to the MS analyst to assess instru-
ment performance. These blind spikes were added to the purge tower before
proceeding with the anlaysis.
The results of these analyses are provided in Section V. Before
proceeding with the FY82 composite specimens, the MS analyst was required to
complete successfully the analyses of check samples submitted by the QCC.
G. Data Interpretation
The HRGC/MS data for each sample were interpreted with computer-
assisted quantisation routines. A mass spectral library and quantisation
list of the target analytes, based on relative retention times and the pri-
mary characteristic ion, were used to search each data file.
1. Qualitative Identification
The automated search quantisation routine identified positive re-
sponses based on the primary characteristic ion for each of the target ana-
lytes. Table 1 provides a list of the target analytes, primary characteristic
quantisation ions, internal standards, and the relative retention times. In
addition to the automated search, the MS analyst identified compounds by re-
viewing the total mass spectra at the specified HRGC/MS scan number. This
effort was required to avoid the inclusion of false positives in the sample
set. The HRGC/MS data were also reviewed at ฑ 30 s of the retention time of
each of the compounds to avoid reporting of false negatives.
11
-------
Purge Tower Standard
Purge Tower QC
Internal QC Spike - Daily
Blind QC Spike - Weekly
I
Instrument
Performance
Evaluation
System Blank
I
Spiked Adipose Tissue
Standard (20 g)
(0.2
Analytical Method
)>- Calibration and
Evaluation
Spiked Adipose Tissue
Sample (20 g)
Internal - QC
I
Composite FY82
Adipose Tissue Samples
(5 - 20 g)
2-5 Samples/Day
Figure 2. Analytical scheme for analysis of volatile organic
compounds from human adipose tissue.
12
-------
Table 1. Characteristic Ions, Internal Standards, and Relative Retention Times
Used to Identify and Quantitate Target Analytes
Target analyte
Primary
characteristic
quantisation
ion (m/z)
Internal .
quantisation standard
RRTa
Bromochloropropane
Chloroform
d-Chloroform
1,1,1-Trichloroehtane
Bromodichloromethane
Benzene
d6-Benzene
Tetrachloroethene
Dibromochloromethane
1,1,2-Trichloroethane
Toluene
d8-Toluene
Chlorobenzene
ds-Chlorobenzene
Ethyl benzene
d10-Ethylbenzene
Bromoform
Styrene
1,1,2,2-Tetrachloroethane
d2-l,1,2,2-Tetrachloro-
ethane
1,2-DiChlorobenzene
d4-l,4-Dichlorobenzene
1,4-Dichlorobenzene
Xylene
d10-p_-Xylene
Ethylphenol
77
79
82
97
129
78
84
166
129
97
91
100
112
117
106
116
173
104
83
84
146
150
146
106
116
122
Bromochloropropane
d-Chloroform
Bromochloropropane
Bromochloropropane
d6-Benzene
Bromochloropropane
Bromochloropropane
Bromochloropropane
d8-Toluene
ds-Chlorobenzene
d10-Ethylbenzene
Bromochloropropane
Bromochloropropane
d2-l,1,2,2-Tetrachloroethane
d4-l,4-Dichlorobenzene
d4-l,4-Dichlorobenzene
d10-p_- Xylene
d10-Ethyl benzene
1.00
0.20-0.43
0.20-0.43
0.35-0.58
0.53-0.76
0.39-0.62
0.39-0.62
1.16-1.39
1.05-1.28
0.88-1.11
0.83-1.07
0.83-1.07
1.48-1.72
1.48-1.72
1.62-1.85
1.62-1.85
1.79-1.96
1.85-2.08
2.05-2.28
2.05-2.28
2.88-3.11
2.73-2.96
2.73-2.96
1.65-1.88
1.65-1.88
2.19-2.43
Relative retention times calculated versus the internal quantisation standard,
.bromochloropropane.
Designation indicates the pairing of the target analytes with the respective
internal standards.
13
-------
2. Quantitation
Data were quantitated based on either the internal standard or the
isotope dilution principle. The isotope dilution principle applies to the
quantisation of target analytes for which a deuterated analog was available
as an internal standard. Where possible, the deuterated analog of a target
analyte was used for quantitation. Other compounds' concentrations were cal
culated versus the internal standard, bromochloropropane (l-chloro-2-bromo-
propane).
The HRGC/MS data were quantitated using the following equation:
AS x IS
Target analyte, ug =
J. O
where A,- = area of the characteristic quantitation ion of the target analyte,
AT<- = area of the characteristic quantitation ion of the internal
standard,
IS = amount of the internal standard in micrograms (ug),
RRF = relative response factor of the target analyte versus the re-
spective internal standard
The concentration (|jg/g) of the target analyte in the original sam-
ple was calculated by dividing the total micrograms of target analyte detected
by the composite weight. In this report concentration data are expressed in
either micrograms per gram (ug/g) or nanograms per gram (ng/g).
The quantitative data were qualified based on the observed response
for each target analyte and the corresponding internal standard. Compounds
for which no positive response was observed are reported as not detected (ND).
An estimated limit of detection (LOD) was calculated based on the observed
instrumental response for the specific target analyte and corresponding in-
ternal standard in each sample. The LOD was estimated as the amount of a
specific analyte that must be present to give rise to a signal at least 2.5
times the background signal-to-noise.
Compounds detected for which the observed response of the character-
istic quantitation ion was greater than 2.5 times but less than 10 times the
background signal-to-noise are reported as trace (tr) values. Target analytes
detected at greater than 10 times the background signal-to-noise, limit of
quantitation (LOQ), are reported as positive quantifiable values.
All data were corrected for blank values observed for the system
blank run daily with each set of samples.
H. Method Validation
The analytical method was evaluated by analyzing adipose tissue
specimens fortified with known levels of specific volatile organic compounds.
14
-------
These experiments were designed to evaluate the use of the internal standards
recommended for EPA Method 624 (USEPA 1984) for determination of volatile or-
ganics in water and wastewater (bromochloromethane, bromochloropropane, and
1,4-dichlorobutane), as well as multiple deuterated analogs of specific target
analytes (isotope dilution). Preliminary studies demonstrated that the inter-
nal standards, bromochloromethane and 1,4-dichlorobutane, were not adequately
recovered from the adipose tissue/water mixtures. Bromochloropropane provided
reasonable response from the spiked adipose matrix and was further evaluated
as a quantisation standard.
The results of the analysis of adipose tissue spiked with nine vola-
tile compounds at four concentration levels ranging from 5 to 75 ng/g (ppb)
are presented in Table 2. In general, the average recovery of the analyses
for these compounds was good, except for chloroform, which demonstrated an
average recovery of 264%. Although the average recovery for the other com-
pounds was quite good (62 to 116%), wide variability was noted for the indi-
vidual analyses at each spike level.
The high recovery of chloroform from this study may be a result of
a difference in the background chloroform concentration in the adipose tissue
used for this spiking experiment as compared to the tissue used for calibration.
An absolute value for the background contribution of each target analyte was
not determined from unspiked tissued used in these experiments. Another factor
that may have resulted in the high recovery of chloroform is the possible con-
version of trichloroacetic acid (present as a metabolite of tetrachlroethylene,
trichloroethane, etc.). to chloroform at the elevated temperatures required to
complete the analyses (Peoples, Pfaffenberger, Shafik, Enos 1979).
The impact of the use of multiple internal standards versus a single
internal standard was evaluated as a separate experiment. Deuterated analogs
of several target analytes were added to fortified tissue samples in addition
to bromochloropropane. Table 3 presents the comparison of the single versus
multiple internal standard quantisation techniques. As noted in Table 3, a
deuterated analog was not available for tetrachloroethene. The data generated
for the target analytes demonstrate average recoveries ranging from 82 to 136%
for the multiple internal standard quantisation as compared to average recover-
ies of 74 to 143% for the same compounds quantitated versus bromochloropropane.
The somewhat tighter range of recoveries or accuracies of quantisation with
incorporation of the multiple internal standards results from the fact that
the deuterated analogs behave similarly to the target analytes.
The purging efficiencies of the target analytes and the internal
standards were evaluated from replicate analyses of a single fortified adipose
tissue. This experiment was necessary to (1) demonstrate the difference in
partitioning of the various target analytes from the water/tissue mixture to
the headspace and (2) compare the partitioning characteristics of the avail-
able internal standards versus the target analytes. A 20-g aliquot of tissue
was spiked with 1.0 pg each of the internal standards and 0.20 (jg of the tar-
get analytes. The sample was heated to approximately 80ฐC, and the headspace
above the stirred mixture was sampled for 40 min. The volatile compounds were
desorbed from the Tenax adsorbent and analyzed by HRGC/MS. The heating, purg-
ing, sampling, and analysis procedures were repeated an additional three times.
15
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The absolute area counts for the characteristic quantisation ion for each com-
pound were recorded. The data for each compound monitored are provided in
Figures 3 to 6 and are plotted as absolute area counts versus the sample run
number.
Figure 3 is a plot of the three internal standards used in EPA
Method 624 for volatiles in water and wastewater. Three distinctive plots
for the three internal standards are presented. These data demonstrate that
bromochloromethane is not an acceptable internal standard due to low response.
The breakthrough volume for the volatile components is based on the total
sample volume mass of adsorbent and sampling temperature. Based on sampling
volumes extrapolated by Brown and Purnell (1977), it is expected that the op-
timum sampling volume for the more volatile components, such as bromochloro-
methane, are approximately 9 to 10 L per gram of Tenax adsorbed. The total
sample volume used in these experiments was 1.6 L (40 mL/min for 40 min) and
the total mass of Tenax was approximately 0.2 g. Hence, the low response
observed for bromochloromethane is probably due to the low capacity of the
Tenax adsorbent system for the more volatile compounds rather than to the
purging efficiency from the matrix.
The plot of bromochloropropane indicates that this internal standard
is effectively partitioned from the adipose/water mixture to air for all four
analyses. The plot for 1,4-dichlorobutane, on the other hand, indicates that
this compound is fairly soluble in the adipose/water matrix. The adipose/air
partitioning constant is obviously low. Hence, this compound was not consid-
ered as a quantitative internal standard for further sample analyses.
Figure 4 presents additional plots of the observed purging efficien-
cies for eight deuterated internal standards spiked initially at 1.0 pg in
the 20-g adipose tissue sample. Again it is noted that the deuterated analog
of chloroform was detected only in the first sample analysis. This observa-
tion is possibly due to the fact that chloroform has the lowest boiling point
(b.p. 60.5-61.5ฐC), hence greatest volatility, of the compounds analyzed.
Deuterated methylene chloride (d2-CH2Cl2) was also added to these samples but
was not detected even in the first analyses. The plots of the other internal
standards appear to reflect the effect of boiling point on purging efficiency
from the heated mixture. The d6-benzene and d8-toluene demonstrate the most
significant differences in absolute response for the sequential analysis of
the spiked adipose sample. The boiling points for these compounds range from
approximately 80 to 111ฐC as compared to 135 to 173ฐC for d10-p_-xylene and
d4-l,4-dichlorobenzene.
The absolute responses of several target analytes spiked (0.20 ug
each) into the same 20-g aliquot of human adipose are plotted for the four
sequential analyses (Figures 5 and 6). The plots for these target analytes
also appear to correspond with the boiling points of the specific compound.
The more volatile compounds such as chloroform (b.p. 60.5-61.5ฐC), 1,1,1-tri-
chloroethane (b.p. 74-76ฐC), and dibromochloromethane (b.p. 119-120ฐC) were
detected in only the first and second analyses, indicating better purging ef-
ficiency, although less retention on the Tenax adsorbent, than demonstrated
for the other compounds. The response profiles noted for compounds such as
benzene, toluene, chlorobenzene, tetrachloroethene, ethylbenzene, and dichlo-
robenzene are very similar to the plots of the deuterated analogs presented
in Figure 4.
18
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The similarity in the response profiles for several target analytes
and the corresponding deuterated analogs are presented in Figures 7 to 9.
These plots reflect that the purging efficiencies of each pair of compounds
are equivalent from the spiked adipose tissue. These plots demonstrate the
advantages of the isotope dilution (target analyte/deuterated internal stan-
dard pair) technique versus a single internal standard for quantitation of
volatile organics in human adipose tissue. With the exception of toluene,
the differences of responses noted for these pairs are roughly a factor of 5
for each analysis, which corresponds to the spike ratio of 0.20 |jg of target
analyte versus 1.0 |jg for the deuterated internal standard. The difference
noted for the toluene/d8-toluene plot is the result of the endogenous toluene
concentration in the tissue sample used for these analyses.
Figure 10 provides a plot of the observed responses for several com-
pounds not spiked into the tissue sample. These compounds include 1,4-dichlo-
robenzene, two xylene isomers, and three C3-alkyl benzenes (trimethyl, methyl-
ethyl, or propyl isomers). These results indicate that the method might be
capable of detecting and quantitating compounds with boiling points ranging
up to approximately 175ฐC.
IV. RESULTS
The analyses for the NHATS FY82 composite samples were completed
following the method evaluation studies. Figures 11 to 17 provide examples
of the HRGC/MS chromatograms for the analysis of instrument performance
checks, spiked tissue samples, and actual composite samples.
Figures 12 and 13 compare the HRGC/MS chromatogram of the bulk adi-
pose tissue used to establish method performance and one of the composite
samples. The HRGC/MS chromatogram of the composite sample appears to have
considerably more volatile material than the bulk adipose used to prepare the
tissue standard. Tentative identifications for some of the major peaks in
Figure 13 were assigned based on the comparison of the mass spectra to library
spectra.
Figures 14 and 15 provide comparisons of the composite specimens
for three age groups within the same census division. All of the samples from
each census division were analyzed on the same day. The results demonstrate
that the elution profiles of all samples are comparable although the absolute
responses of the peaks vary.
Figures 16 and 17 provide comparisons of three composite samples
representing the 15-44 and 0-14 age groups from three census divisions. Again
the general HRGC/MS profiles appear to be consistent although the absolute
response of each peak varies from sample to sample.
23
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1. Benzene/d^-benzene
2. Bromodichloromethane
3. Toluene/d8-toluene
4. Bromochloropropane/
1,1,2-trichloroethane
5. Dibromochloromerhane
6. Tetrachloroethene
7. Chlorobenzene/
d~ch I orobe nze ne
8. d]0~ethylbenzene
9. Ethylbenzene
10. djQ-p-xylene
11. Bromoform
12. Styrene
13. Dichlorobutane
14. 1,1,2,2-telrachloroethane
15. d4~1,4-dichlorobenzene
16. 1,2-dichlorobenzene
Purge Tower Standard
10
3:20
6:40
10:00
13:20
16:40
20:1* TIHF
Figure 11. HRGC/MS chromatoqram of purge tower standard analyzed
daily to document instrument performance.
28
-------
1. Chloroform/d-chloroform 11.
2. Bromochloromethane 12.
3. 1, 1, 1-trichioroethane 13.
4. Benzene/d^-benzene 14.
5. Bromodichloromel-hane 15.
6. Toluene/dg-toluene 16.
7. 1,1, 2-irichloroel'hane
8. Dibromochloromethane 17.
9. Tetrachloroethene 18.
10. Chlorobenzene/
d5-ch lorobenzene
d]Q-ethylbenzene
Ethylbenzene
dlQ-p-xylene
Bromoform
Styrene
1,1,2,2-tetrachloroethcme/
d2~l, 1,2,2-tetrachloroethane
d4~l ,4-dichlorobenzene
1,2-dichlorobenzene
tee. 9-1
RIC
J4
Tissue Standard
\
11 12
16
3:29
6:40
19-.M
13:29
16:40
TIHF
Figure 12. HRGC/MS chromatogram for the volatile organic analysis of a bulk
adipose (tissue standard) spiked with 1.0 ng of each internal standard
and 0.20 |jg of each target analyte.
29
-------
Tentative Identification
of Major Peaks
1. Acetic acid ethyl ester/
Propanoic acid propyl ester
2. Heptanal
3. Decane
4. Dimethyloctane
5. Trimethylcyclohexane
6. Nonanal
7. Undecene
8. Ethyl ester, carboxylic acid
9. Nonadienal
Middle Atlantic, 0-14 years
3:20
6:40
Figure 13. HRGC/MS chromatogram of volatile compounds from the
NHATS FY82 composite of the 0-14 year age group from
the Middle Atlantic census division.
30
-------
vj\
J
Middle Atlantic
45 plus years
Middle Atlantic
15-44 years
Middle Atlantic
0-14 years
Figure 14. Comparison of the HRGC/MS chromatograms for the volatile
organic analytes for three composite age groups from the
Middle Atlantic census division.
31
-------
East North Central
45 plus years
East North Central
15-44 years
East North Central
0-14 years
Figure 15. Comparison of the HRGC/MS chromatograms for the volatile
organic analytes for three composite age groups from the
East North Central census division.
32
-------
Middle Atlantic
15-44 years
East North Central
15-44 years
West North Central
15-44 years
Figure 16. Comparison of the HRGC/MS chromatograms of the volatile
organic analysis of three composite specimens representing
the 15-44 age group from three census divisions.
33
-------
Middle Atlantic
0-14 years
East North Central
0-14 years
West North Central
0-14 years
Figure 17. Comparison of the HRGC/MS chromatograms of the volatile
organic analysis of three composite specimens representing
the 0-14 age group from three census divisions.
34
-------
Seventeen target analytes were determined using the automated
HRGC/MS search routines and the mass spectral library established in the
method evaluation studies. Figures 18 to 21 summarize the incidence of de-
tection of each of these analytes by age and by census division within the
four regions. A plus indicates that the compound was detected in the analysis
of a particular composite. A minus indicates the compound was not detected
above the estimated limit of detection. The number of symbols shown under
each age category for a specific compound indicates the total number of com-
posites analyzed.
The quantitative data for the 17 target analytes are shown in Tables
4 through 20 by census division and age group. The tables provide the total
wet tissue weight composited, the total mass of the specific analyte detected,
the concentration based on the original wet tissue weight, and the analysis
date. The tables provide estimated limits of detection for composites for
which a compound was not detected (ND) and for composites for which the com-
pound is reported as a trace (tr) value. Trace values are reported for re-
sponses observed at greater than 2.5 times the signal-to-noise but less than
10 times signal-to-noise. Data reported with no qualifier indicate a posi-
tive response detected above the limit of quantisation (LOQ) or greater than
10 times the background signal-to-noise.
Upon reviewing the data in Tables 4 through 20 reported as not de-
tected (ND), it is noted that the level of detection (total micrograms) varies
from one sample to another. This results from a combination of the observed
background in a sample at the characteristic ion for a specific analyte and
the intensity of the response of the characteristic ion for the corresponding
internal standards. Hence, the calculated limits of detection were higher in
some instances due to high background at the charasteric ions for the target
analytes and/or low recovery (observed as intensity of repsonse) of the asso-
ciated internal standards.
Table 21 presents the frequency of observation of the target ana-
lytes from the 46 composite samples. Styrene, 1,4-dichlorobenzene, xylene
isomers, and ethyl phenol were detected in all 46 composites. Two responses
were observed that corresponded to xylene isomers. However, the isomers are
not specified since the order of elution of the three possible compounds was
not determined. Benzene, chlorobenzene, ethylbenzene, and toluene were de-
tected in nearly all composites. Tetrachloroethane, 1,2-dichlorobenzene, and
1,1,1-trichloroethane were detected in approximately 50 to 60% of all compos-
ite specimens. 1,1,2,2-Tetrachloroethane was detected in less than 10% of
all composite samples (4 of the 46). The three brominated target analytes
and 1,1,2-trichloroethane were not detected in any of the composite specimens.
The quantitative data for all compounds detected in a specific com-
posite are reported in Tables B-l to B-18 in Appendix B.
35
-------
Census Region Northeast
Census division: New England Middle Atlantic
Age group: 0-14 15-44 45+ 0-14 15-44 45+
Compound
Chloroform
1,1,1-Trichloroethane
Bromodi chloromethane
Benzene
Tetrachloroethene
Di bromochloromethane
1,1,2-Tri chloroethane
Toluene
Chlorobenzene
Ethylbenzene
Bromoform
Styrene
1,1,2,2-Tetrachloroethane
1,2-Dichlorobenzene
1,4-Dichlorobenzene
Xylenea
Ethylphenol
aThe exact isomers were not determined.
Figure 18. Incidence of detection of volatile organic compounds in
composited human adipose tissues from the Northeast census region.
The total number of + and - symbols for a specific compound indicates
the number of composites analyzed for each age group.
36
-------
Census Region
Census division:
Age group:
Compound
South Atlantic
South
East South Central
West South Central
0-14 15-44 45+ 0-14 15-44 45+ 0-14 15-44 45+
Chloroform
1,1,1-Trichloroethane
Bromodi chloromethane
Benzene
Tetrachloroethene
Di bromochloromethane
1,1,2-Trichloroethane
Toluene
Chlorobenzene
Ethylbenzene
Bromoform
Styrene
1,1,2,2-Tetrachloroethane
1,2-DiChlorobenzene
++
-+
++
+++-
+++-
++++
++++
+++-
+++-
++++
-++-
+-
++
++
++
-+
++++
++++
++++
++++
-+--
+++-
-++-
++++
++++
+
1, 4- Di Chlorobenzene
Xylene3
Ethylphenol
++
++
++
++++
++++
++++
++++
++++
++++
+ ++ ++ + ++ +
+ ++ ++ + ++ +
+ ++ ++ + ++ +
The exact isomers were not determined.
Figure 19. Incidence of detection of volatile organic compounds in
composited human adipose tissues from the South census region. The
total number of + and - symbols for a specific compound indicates
the number of composites analyzed for each age group.
37
-------
Census Region Northcentral
Census division: East North Central West North Central
Age group: 0-14 15-44 45+ 0-14 15-44 45+
Compound
Chloroform ++
1,1,1-Trichloroethane
Bromodichloromethane
Benzene ++
Tetrachloroethene +-
Dibromochloromethane
1,1,2-Trichloroethane
Toluene ++
Chlorobenzene ++
Ethyl benzene ++
Bromoform
Styrene ++
1,1,2,2-Tetrachloroethane
1,2-Dichlorobenzene ++
1,4-Dichlorobenzene ++
Xylene3 ++
Ethylphenol ++
aThe exact isomers were not determined.
Figure 20. Incidence of detection of volatile organic compounds in
composited human adipose tissues from the North Central census region.
The total number of + and - symbols for a specific compound indicates
the number of composites analyzed for each age group.
38
-------
Census Region
Census division:
Age group:
Compound
West
Mountain
Pacific
0-14 15-44 45+ 0-14 15-44 45+
Chloroform
1,1,1-Trichloroethane
Bromodi chloromethane
Benzene
Tetrachloroethene
Dibromochloromethane
1,1,2-Trichloroethane
Toluene
Chlorobenzene
Ethyl benzene
Bromoform
Styrene
1,1,2,2-Tetrachloroethane
1,2-Dichlorobenzene
1,4-Dichlorobenzene
Xylene3
Ethylphenol
The exact isomers were not determined.
Figure 21. Incidence of detection of volatile organic compounds in
composited human adipose tissues from the West census region. The
total number of + and - symbols for a specific compound indicates
the number of composites analyzed for each age group.
39
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Table 21. Incidence of Detection of Selected Volatile Organic
Compounds in the NHATS FY82 Composite Samples
Compound Frequency of observation (%)
Chloroform 76
1,1,1-Trichloroethane 48
Bromodichloromethane 0
Benzene 96
Tetrachloroethene 61
Dibromochloromethane 0
1,1,2-Trichloroethane 0
Toluene 91
Chlorobenzene 96
Ethyl benzene 96
Bromoform 0
Styrene 100
1,1,2,2-Tetrachloroethane 9
1,2-Dichlorobenzene 63
1,4-Dichlorobenzene 100
Xylene 100
Ethylphenol 100
74
-------
V. QUALITY ASSURANCE/QUALITY CONTROL
As mentioned in Section IV, several procedures were included with
the analysis of the composite specimens to document the quality of the data
reported. These procedures included instrument performance checks using re-
agent spikes at the purge tower. These were performed daily following initial
instrument calibration by the HRGC/MS analyst. The quality control procedures
also required that the analyst demonstrate background contribution of the
headspace analysis system through the analysis of system blanks. Adipose tis-
sue samples were spiked with known amounts of the target analytes and internal
standards to verify consistency of response factors before proceeding with
the sample analyses. When necessary, the analyst completed the analysis of a
three-point calibration curve before proceeding with sample analysis. Typical
spike levels of the target analyte ranged from 0.2 to 1.4 ug per 20-g aliquot
of tissue. These spike levels were equivalent to concentrations from 0.010
to 0.070 ng/g.
A. Instrument Performance Checks
Instrument performance checks were completed using quality control
samples prepared by the MS analyst (internal QC) or by the project quality
control coordinator (external QC). These instrument performance checks were
completed to demonstrate that the HRGC/MS system was properly calibrated and
to document method performance (precision) over time. The instrument perfor-
mance checks were achieved by spiking a solution of the reference compounds
into the purge tower and then proceeding with the sampling and analyses events
as described earlier in the experimental section.
1. Internal QC
Table 22 presents a summary of the internal QC instrumental perfor-
mance check completed for 10 different analysis days. Spike levels for these
instrument performance checks were from 0.20 to 0.40 ug for each of the spe-
cified target analytes. Table 23 provides the average recovery and range of
measured recoveries for each compound. As noted, the method recoveries for
all compounds were typically within the range of 80 to 120% with the exception
of bromochloromethane. The method precision for the internal QC measurements
was generally within ฑ 15%. These accuracy and precision estimates reflect
day-to-day performance of the analytical method.
2. External QC
A mixed volatile stock standard was prepared containing chloroform,
benzene, bromodichloromethane, toluene, chlorobenzene, ethylbenzene, 1,2-di-
chlorobenzene, 1,1,2,2-tetrachloroethane, and tetrachloroethene at a concen-
tration of 10 mg/mL for each compound. One portion of the stock solution was
diluted and used for internal QC, and another was diluted and used for per-
formance audit samples.
Five dilutions of the stock solution were prepared in tetraglyme,
sealed in microreaction vials sealed with Mininert valves, and stored in a
freezer until needed. The concentration of each compound per dilution was:
75
-------
Audit sample no. Concentration
VOA 1 0.41 |jg/|jL
VGA 2 0.80 ug/pL
VOA 3 0.80 ug/nL
VOA 4 0.68 ug/ML
VOA 5 0.81 ug/|jL
The results of the QC performance audit samples are found in Table 24.
B. Spiked Adipose Tissue Samples
An additional QC control check included the analysis of spiked adi-
pose tissue samples. Table 25 summarizes the results for five spiked adipose
tissue specimens analyzed with the first sample batches. The mean accuracy
of these measurements ranged from 94% for 1,1,2-trichloroethane to 141% for
1,1,2,2-tetrachloroethane. The range of recoveries for each compound is some-
what broader than noted for the instrument performance checks due to the in-
fluence of the matrix on recovery efficiency and background contribution.
C. Internal Standards
The absolute responses of the internal standards were noted for each
QC check sample and composite adipose tissue sample to document instrument
operating parameters. The absolute responses of the internal standards in
the first composite sample analyzed were observed to decrease markedly in com-
parison to the responses observed for the instrument performance check and
system blank. A reduction in the response can be attributed to the adipose
tissue matrix. Obviously, the presence of oily lipid materials affects the
aqueous to air partitioning of the volatile internal standards.
Differences in the recovery of the internal standard from the FY82
composite specimens and the bulk adipose tissues used for method calibration
were also observed. The absolute responses of the internal standards from the
bulk adipose tissue samples were nearly always greater than the responses for
the NHATS composites. This indicates that the recoveries or observed parti-
tioning of the internal standards from the spiked samples to the headspace was
greater for the QC samples than the FY82 composites. This observed recovery
might indicate some difference in the two sources of adipose tissues. This
bulk adipose tissue had been collected within 6 mo of the volatile organic
analysis as compared with the FY82 specimens, which had been stored for up to
2 yr.
After observing the reduction in response with the first composite
sample, the instrument performance was verified through reanalysis of a vessel
blank (water plus internal standards). This analysis demonstrated that the
instrument was properly calibrated and that the matrix was responsible for
the reduction in response of the internal standards.
Figures 22 to 25 are plots of several of the internal standard re-
sponses from the system blanks, spiked reference tissue samples, and NHATS
composite samples. These plots demonstrate that the differences in the ob-
served internal standards responses for the method blanks, spiked reference
tissues, and the NHATS composites were noted for each day that the composites
were analyzed.
76
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Table 23. Average Recovery for Internal QC
Instrument Performance Checks
Average
Compound recovery (%) Range (%)
1,1,1-Trichloroethane
Bromochl oromethane
Benzene
Tetrachl oroethene
Di bromochl oromethane
1,1,2-Trichloroethane
Toluene
Chlorobenzene
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Bromoform
Styrene
1,1,2, 2-Tetrachl oroethane
1,2-Di chlorobenzene
105 ฑ 11.8
121 ฑ 71
98.3 ฑ4.9
99.3 ฑ 8.9
98.8 ฑ 6.1
101 ฑ5.7
103 ฑ 12.1
103 ฑ6.7
100 ฑ5.3
99.5 + 12.3
103 ฑ 14.6
101 ฑ9.4
102 ฑ7.9
90-125
50-280
90-105
88-115
90-110
90-110
88-120
95-120
90-110
80-115
90-140
80-110
90-115
aThese data were summarized to include accuracy for
isotope dilution measurements where possible.
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A NHATS FY 82 Composite Specimens
ง
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S
1
d-chloroform
I
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Analysis Date (1984)
II
12
13
16
17
18
20
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A NHATS FY 82 Composite Specimens
do-benzene
8.
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6/19 21 22 26
27 28 29 7/2 3 9 10
Analysis Date (1984)
12
13
16
17
18
20
Figure 22. Observed HRGC/MS responses for the internal standards
d-chloroform and d6-benzene, from method blanks, spiked
tissue samples and the NHATS composite samples.
81
-------
Method Blonk
o Spiked Reference Tisiue
O Spiked Reference Tisiue - Internal QC
A NHATS FY 82 Composite Specimens
dg-toluene
J
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8 '
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6/19 21 22 26 27 28 29 7/2 3 9
Analysis Date (1984)
10
12
13
17
18
20
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A NHATS FY 82 Composite Specimens
4r-
1 3
> 2
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S
I
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6/19 21 22 26 27 28 29 7/2 3 9
Analysis Date (1984)
10
II
12
13 16
17
18
20
Figure 23. Observed HRGC/MS responses for the internal standards
ds-toluene and d5-ch1orobenzene, from method blanks, spiked
tissue samples and the NHATS composite samples.
82
-------
4i
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>:
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O Spiked Reference Tissue - Internal QC
A NHATS FY 82 Composite Specimens
dig-p-xylene
1
1
1
1
1
1
6/19 21 22 26
27 28 29 7/2 3 9
Analysis Dote (1984)
10
12
13
16
17
18 20
Method Blank
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A NHATS FY 82 Composite Specimens
4
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6/19 21 22 26 27 28 29 7/2 3 9 10 11 12
Analysis Date (1984)
__-ป *
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A A A
A A A
A A A
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1 1 1 1 1
13 16 17 18 20
Figure 24. Observed HRGC/MS responses for the internal standards
d10~P-xylene and d^-ethyl benzene, from method blanks, spiked
tissue samples and the NHATS composite samples.
83
-------
Method Blank
O Spiked Reference Tisiue
O Spiked Reference Tissue - Internal QC
A NHATS FY 82 Composite Specimens
7 3
2~ 1,1,2,2-tetrach I ore-ethane
J1 ol
_L
6/19 21 22 26 27 28 29 7/2 3 9
Anal/lit Date (1984)
10
12
13
16
17
18
20
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O Spiked Reference Tissue - Internal QC
A NHATS FY 82 Composite Specimens
Hi
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v
I H
I I I I
6/19 21 22 26 27 28 29 7/2 3 9
Analysis Date (1984)
10
12
13
16
17
18
20
Figure 25. Observed HRGC/MS responses for the internal standards
d2-"l J ,2,2-tetrachloroethane and d4-dichlorobenzene, from
method blanks, spiked tissue samples
and the NHATS composite samples.
84
-------
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J Chromatog Sci 13:378-379.
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Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans
(PCDFs). EPA-560/5-86-038.
Snyder CA, Erlichman MN, Goldstein BD, Laskin S. 1977. An extraction method
for determination of benzene in tissue by gas chromatography. Am Ind Hyg
Assoc J 38:272-276.
USEPA. 1984. U.S. Environmental Protection Agency. Method 624purgeables.
(49 FR 141-152).
Vogt CR, Liao JC, Sun AY. 1980. Extraction and determination of chloroform
in rat blood and tissues by gas chromatography-electron-capture detection:
distribution of chloroform in the animal body. Clin Chem 26(l):66-68.
86
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Whitcher CE, Cohen EN, Trudell JR. 1971. Chronic exposure to anesthetic
gases in the operating room. Anesth 35:349.
Wolff MS. 1976. Evidence of existence in human tissues of monomers for
plastic and rubber manufacture. Environ Health Perspect 17:183-187.
Wolff MS, Daum SM, Loumer WV, Selikoff IJ, Aubrey BB. 1977. Styrene and re-
lated hydrocarbons in subcutaneous fat from polymerization workers. Toxicol
Environ Health 2:997-1005.
Zuccato E, Marcucci F, Mussini E. 1980. GLC determination of ethylene di-
chloride (EDC) in biological samples. Anal Ltr 13(B5):363-370.
87
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APPENDIX A
ANALYTICAL METHOD FOR THE DETERMINATION OF VOLATILE
ORGANIC COMPOUNDS IN HUMAN ADIPOSE TISSUE
A-l
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ANALYTICAL METHOD FOR THE DETERMINATION OF VOLATILE
ORGANIC COMPOUNDS IN HUMAN ADIPOSE TISSUE
1.0 SCOPE AND APPLICATION
1.1 This method covers the determination of volatile organic compounds
in human adipose tissue. The following compounds have been eval-
uated and determined by this method.
Compound CAS no.
Chloroform 67-66-3
1,1,1-Trichloroethane 71-55-6
Bromodichloromethane 75-27-4
Benzene 71-43-2
Tetrachloroethene 127-18-4
Dibromochloromethane 124-48-1
1,1,2-Trichloroethane 79-00-5
Toluene 108-88-3
Chlorobenzene 108-90-7
Ethyl benzene 100-41-4
Bromoform 75-25-2
Styrene 100-42-5
1,1,2,2-Tetrachloroethane 79-34-5
1,2-Dichlorobenzene 95-50-1
1,4-Dichlorobenzene 106-46-7
Ethyl phenol 25429-37-2
Xylene 1330-20-7
1.2 This is a dynamic headspace high resolution gas chromatography/
mass spectrometry (HRGC/MS) method applicable to the determina-
tion of volatile organic compounds in human adipose tissue.
1.3 The method detection limit (MDL) for each parameter is estimated
to range from 0.001-0.10 pg/g for a 20-g sample. The MDL for a
specific sample of human adipose tissue may differ depending upon
the nature of interferences in the sample matrix and the specific
analyte determined.
2.0 METHOD SUMMARY
Helium gas is swept through the head space of a specially designed
purging chamber containing water and the adipose tissue sample. The
water and sample are heated and stirred to aid in the efficient trans-
fer of the analytes from the adipose tissue and water mixture to the
gaseous phase. The vapor is swept through a cooling tower at ambient
temperature to remove excess water vapor and onto a Tenax sorbent trap
where the volatile analytes are captured. After the sampling is com-
plete, the sorbent trap is heated and backflushed with helium to desorb
A-2
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the analytes onto a HRGC column. The gas chromatograph is temperature
programmed to separate the compounds which are then detected by the
mass spectrometer. Figure A-l provides a schematic of the dynamic head-
space purge and trap HRGC/MS analysis system.
3.0 CONTAMINATION AND INTERFERENCES
3.1 Impurities in the purge gas, organic compounds out-gassing from
the plumbing upstream of the trap, and solvent vapors in the
laboratory account for the majority of contamination problems.
The analytical system is demonstrated to be free from interfer-
ences under conditions of the analysis by analyzing blanks ini-
tially and with each sample set analyzed daily.
3.2 Samples can be contaminated by diffusion of volatile organic com-
pounds through the bottle seal during preparation, handling, or
storage. A sample container blank carried through the sampling
and handling protocol serves as a check on such contamination.
3.3 Contamination by carry-over can occur when high level and low
level samples are analyzed sequentially. To reduce carry-over,
a clean headspace chamber is used for each sample analysis and
sample syringes are rinsed between samples with reagent water.
Instrument performance checks and QC samples are followed by
analysis of a reagent water blank to check for carry-over. The
headspace device is washed with soap solution, rinsed with tap
and distilled water, and dried in an oven at 100-125ฐC overnight.
The Tenax adsorbent trap and other parts of the system are also
subject to contamination; therefore, frequent bakeout and purging
of the entire system may be required.
3.4 Interferences resulting from samples may vary considerably, de-
pending on the length of sample storage.
4.0 SAFETY
4.1 The toxicity or carcinogenicity of each compound used in this
method has not been precisely defined; however, each compound
should be treated as a potential health hazard. Exposure to
these chemicals should be maintained at the lowest possible level.
4.2 The glass purging apparatus used in this method is of fairly re-
cent design and has apparent limitations which must be observed.
The pressure in the system should not exceed 10 psi. Excessive
pressure above this limit may result in the possible explosion of
the purging vessel or purge tower. Monitoring the gas pressure
is easily accomplished by placing a pressure gauge between the
helium source and the gas inlet at the vessel. At no time should
any glassware be pressurized without the analyst wearing approved
safety goggles.
A-3
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5.0 APPARATUS AND MATERIALS
5.1 Gas pressure gauge - Supelco No. 2-0392 or equivalent.
5.2 Spatulas, stainless steel - Fisher No. 14-375-10.
5.3 Volumetric flask - 10.0 mL - Ace No. 7100-02.
5.4 Syringes
5.4.1 Syringe - 10.0 mL - Hamilton No. 1010.
5.4.2 Syringe - 1.0 mL - Hamilton No. 1001.
5.4.3 Syringe - 100.0 uL - Hamilton No. 710N.
5.4.4 Syringe - 25.0 uL - Hamilton No. 702N.
5.4.5 Syringe - 2 x 5.0 uL - Hamilton No. 75N.
5.5 Vials - 2 x 5.0 mL microreaction vessels - Supelco No. 3-3298.
5.6 Vials - 2 x 1.0 mL microreaction vessels - Supelco No. 3-3292.
5.7 Mininert valves - (x2) - Supelco No. 3-3301.
5.8 Teflonฎ tubing (1/8-in. ID) - Ace No. 12687-08.
5.9 Funnel (1.0 L) - Ace No. 7249-40.
5.10 Three-way stopcock - Ace No. 8143-05.
5.11 Vinyl tubing - Ace No. 12679-24.
5.12 Hot water bath/circulator - HAAKE No. F-4391.
5.13 Teflonฎ stir bars - Ace No. 13654-10.
5.14 Stirrer - Ace No. 13635.
5.15 Heat tape - Ace No. 12064-08.
5.16 Powerstat - Ace No. 12077.
5.17 Headspace vessel - Wheaton No. 991765.
5.18 Kovar to PX seal tubes - Ace No. Pt.976.
5.19 Stainless steel tubing - Supelco No. 2-0526.
5.20 Six-way Carle valve.
A-5
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5.21 Stainless steel glass lined U-tube (1/8 in. ID).
5.22 Chromatography gravity flow column - Howe Scient. Inc., No.
3060-13 "purge tower".
5.23 Heat controller and thermocouple.
5.24 Glass wool "silanized".
5.25 HRGC column (30 m x 0.25 mm ID) Durabond DB-5, 0.25 pm film
thickness (J&W Scientific, Rancho Cordova, CA) or equivalent.
5.26 Gas chromatograph - Finnigan 9610 or equivalent capable of main-
taining 30ฐC isothermal and programmable to 200ฐC. The gas chro-
matograph must be equipped with a Grob split/splitless type
injector.
5.27 Mass spectrometer - Finnigan 4000 quadrupole or equivalent, 70
eV electron impact ionization; capable of repetitive scan from
35-275 amu every 2-3 s, and produce a unit resolution (valleys
between m/z 174-176 less than 10 percent of the height of the
m/z 175 peak), background corrected mass spectrum from 50 ng
4-bromo-fluorobenzene (BFB) injected into the GC. The BFB spec-
trum must meet the mass intensity criteria in Table A-l. All
portions of the HRGC column, transfer lines, and the HRGC column
routed directly to the ion source shall remain at or above the
column temperature during analysis to preclude condensation of
less volatile compounds.
Table A-l. BFB Mass Intensity Specifications
Mass Intensity required
50 15 to 40 percent of mass 95.
75 30 to 60 percent of mass 95.
95 base peak, 100 percent.
96 5 to 9 percent of mass 95.
173 < 2 percent of mass 174.
174 > 50 percent of mass 95.
176 95 to 100 percent of mass 174.
177 5 to 9 percent of mass 176.
5.28 Data system - Capable of collecting and recording MS data, stor-
ing mass intensity data in spectral libraries, processing HRGC/MS
data and generating quantitation reports, and calculating and
recording response factors.
A-6
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5.28.1 Data acquisition - Mass spectra shall be collected con-
tinuously throughout the analysis and stored on a mass
storage device.
5.28.2 Mass spectral libraries - User created libraries contain-
ing mass spectra obtained from analysis of authentic stan-
dards must be used to reverse search GC/MS runs for the
compounds of interest.
5.28.3 Data processing - The data system shall be used to search,
locate, identify, and quantitate the compounds of inter-
est in each HRGC/MS analysis. Software routines shall be
employed to compute retention times and extracted ion
current plot (EICP) areas. Displays of spectra, mass
chromatograms, and library comparisons are required to
verify results.
5.28.4 Response factors and multi-point calibrations - The data
system shall be used to record and maintain lists of re-
sponse factors (response ratios for isotope dilution)
and generate multi-point calibration curves. Computa-
tions of relative standard deviation (coefficient of
variation) are useful for testing calibration linearity.
5.29 Balance - Analytical, capable of weighing 0.1 mg.
6.0 REAGENTS
6.1 Volatile organic-free water - prepare as described in Section 8.1.
6.2 Prepurified nitrogen.
6.3 Prepurified helium.
6.4 Tenax absorbent.
6.5 Internal standard compounds
6.5.1 Bromochloromethane, 1,4-dichlorobutane, and l-chloro-2-
bromopropane (a 20-mg/mL mixture, Supelco, Inc. , No.
4-8823).
6.5.2 d6-Benzene - Aldrich gold label (99.5% D) No. 15, 181-5.
6.5.3 d-Chloroform - Aldrich gold label (99.8% D) No. 15, 182-3.
6.5.4 d2-l,l,2,2-Tetrachloroethane - M and D Isotopes No. MD-1416.
6.5.5 d2-Methylene chloride - M and D Isotopes No. MD-53.
A-7
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6.5.6 d5-Chlorobenzene - KOR Isotopes (99% Ds) No. 521510.
6.5.7 l,4-d4-Dichlorobenzene - KOR Isotopes (98% D4) No. 521530.
6.5.8 d10-Ethylbenzene - KOR Isotopes (98% D10) No. 521443.
6.5.9 d8-Toluene - KOR Isotopes (99.9% D8) No. 510041.
6.5.10 d10-p-Xylene - KOR Isotopes (98% D10) No. 521133.
6.6 Target analytes
6.6.1 Bromoform - Aldrich gold label (99%/lX EtOH) (d 2.894 g/mL).
6.6.2 Dibromochloromethane - Columbia No. D1843 (d 2.45 g/mL).
6.6.3 Toluene - Burdick and Jackson H.P. No. Al-857 (d 0.867 g/mL).
6.6.4 1,1,2-Trichloroethane - Aldrich No. JB-070177 (95%)
(d 1.435 g/mL).
6.6.5 Styrene - Eastman No. 1465 (d 1.34 g/mL).
6.6.6 Tetrachloroethene - Aldrich gold label No. 120457 (d 1.54
g/mL).
6.6.7 Bromodichloromethane - Aldrich No. 7628AH (98%) (d 1.49
g/mL).
6.6.8 Chlorobenzene - Aldrich No. 120277 (99%) (d 1.107 g/mL).
6.6.9 1,2-Dichlorobenzene - Aldrich No. D5-680-2 (98%) (d 1.306
g/mL).
6.6.10 Ethylbenzene - Aldrich No. El-250-8 (99%) (d 0.867 g/mL).
6.6.11 1,1,2,2-Tetrachloroethane - Baker No. 017386 (d 1.586 g/mL).
6.6.12 1,1,1-Trichloroethane - Fisher No. 775974 (d 1.338 g/mL).
6.6.13 Chloroform - Burdick and Jackson H.P. No. AG594 (d 1.492
g/mL).
6.6.14 Benzene - MCB pest, grade No. U2738 (d 0.874 g/mL).
6.7 Methanol - Burdick and Jackson, high purity distilled in glass.
6.8 Tetraglyme - Aldrich 17-240-5.
6.9 Acetone - Burdick and Jackson, high purity distilled in glass.
6.10 Hexane - Burdick and Jackson, high purity distilled in glass.
A-8
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7.0 HEADSPACE APPARATUS PREPARATION
7.1 Glassware preparation - All glassware is washed with a laboratory
grade soap (i.e., Sparkleen or equivalent) and rinsed with de-
ionized water, bulk grade acetone, B&J acetone, and finally B&J
hexane. The glassware is air dried to remove traces of hexane
and then dried in an oven at 200ฐC for 48 h before use.
7.2 Wheaton purge vessel - The Wheaton purge vessel thermometer and
funnel arms were modified as follows. The threaded arms were cut
near the vessel and replaced by 1/4-in. Kovarฎ to PX seal tubes
(Ace Glass, Inc., No. PT.976). The Kovarฎ length was 1.0 in.
The arms were made as short as possible to minimize dead volume.
The vessel is integrated in the system as in Figure A-l.
7.3 Chromatographic gravity flow column (purge tower) - The column is
connected to the system as displayed in Figure A-l. Two milli-
liters of volatile organic-free water is placed in the tower to
trap excess water vapor.
7.4 Glass-lined U-tube sorbent trap - A 1.0-in. plug of Tenax is
placed in the tube, and a plug of silanized glass wool placed at
both ends. Do not overpack the Tenax. Pack only tight enough to
avoid any dead volume in the Tenax. Overpacking will make it
difficult to maintain a 40.0-mL/min helium flow under the 10.0 psi
safety pressure.
Refer to Figure A-l for a detailed orientation of all system com-
ponents.
8.0 REAGENT PREPARATION
8.1 Volatile-free water - Volatile organic compounds are purged from
water, taken from the Mi Hi pore system, by bubbling the prepuri-
fied nitrogen through the water for 24 h prior to use.
8.2 Internal standard preparation
8.2.1 Internal standard stock solution - The internal standard
stock solution is prepared from compounds 6.5.2 through
6.5.10 by aliquotting each compound with a 100.0-ul_
syringe into a 10.0-mL volumetric containing 5.0 mL of
methanol. The exact volume of each target analyte neces-
sary to achieve a final concentration of 10 mg/mL for
each compound can be determined from the density of the
compound. After aliquotting all compounds, dilute to the
mark with the methanol. Transfer the 10.0-mL solution to
two 5.0-mL vials and seal tightly with the TFE-lined caps.
Store in the freezer until needed.
A-9
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8.2.2 Internal standard spiking solution - A SOO-ng/pL internal
standard spiking solution is prepared in tetraglyme by
injecting 925.0 |jL of tetraglyme into a 1.0-mL reaction
vial with mininert cap. This is then spiked with 25.0-uL
of the 3-component (20 mg/mL) Supelco standard and 50.0-uL
of the 10.0-mg/mL internal standard stock of 8.2.1. Store
in the freezer until needed.
8.3 Target analyte preparation
8.3.1 Target analyte stock solution - A 10.0-mg/mL each solution
of the analytes from 6.6.1 through 6.6.14 is prepared as
described for the internal standard stock solution in
8.2.1. Store in the freezer.
8.3.2 Target analyte spiking solution - A 100.0-ng/uL solution
of each of the target analytes is prepared by injecting
990.0 uL of tetraglyme into a 1.0-mL reaction vial with
mininert cap and spiking the tetraglyme with 10.0 uL of
the stock solution of 8.3.1. Store in the refrigerator.
9.0 ANALYSIS ROUTINE
This routine must be followed after any system shutdown or at least
once every 8 h prior to any sample analysis.
9.1 Perform an instrument mass calibration using bromofluorobenzene
(BFB) to achieve the mass intensity specifications in Table A-l.
9.2 Conduct a purge tower instrument evaluation with the system set
up as in Figure A-l.
9.2.1 Conduct a leak test by squirting VOA-free water around
all connections, vessel cap, etc. Correct as needed.
Check the bubble meter for the correct 40.0-mL/min flow.
The Carle valve must be in the purge position.
9.2.2 Turn off the purge tower stopcock and immediately turn
the helium supply off. Check the pressure gauge for a
slow pressure falloff. If the gauge reading drops, check
again for leaks.
9.2.3 Remove the purge tower cap.
9.2.4 Connect a 30-cm length of Teflonฎ tubing to the 10.0-mL
syringe. Draw 3.0 mL of VOA-free water into the syringe.
Remove the Teflonฎ tubing and draw 1.0 mL of air into the
syringe. Using two separate 5.0-|jL syringes, withdraw
2.0 uL of each working solution of 8.2.2 and 8.3.2. Spike
the 10.0 mL syringe with each of the standard spiking
A-10
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solutions. Be sure to inject directly into the water.
Reseal the mininert valves and return the standards to a
refrigerator. Replace the Teflonฎ tubing on the 10.0-mL
syringe. Invert the syringe several times to ensure
adequate mixing of the tetraglyme and water.
9.2.5 Inject the contents of the 10.0-mL syringe directly into
the water at the bottom of the purge tower. The air in
the syringe should push the water solution completely out,
but should not be allowed to bubble out the end of the
Teflonฎ tube. Immediately withdraw the Teflonฎ tube and
recap the purge tower.
9.2.6 With the Carle valve in the purge mode, the Tenax trap
at ambient temperature, and all heat tape lines at 150ฐC,
turn on the helium supply valve and then the stopcock at
the purge tower.
NOTE: If the stopcock on the purge tower is left closed,
the helium gas may rupture the purge vessel.
Check the system for leaks. If a leak is detected, the
system must be shut down and the purge tower cleaned as
outlined below.
9.2.7 Purge the purge tower for 12 min at 40 mL/min.
9.2.8 After the purge is complete, turn the Carle valve to the
desorb mode, heat the Tenax trap to approximately 250ฐC
and initiate the HRGC/MS data acquisition. These three
procedures are done as quickly as possible to maintain
the absolute retention times between analysis. The gas
chromatograph should be held isothermal at 30ฐC for 5 min
then programmed to 125ฐC at 6ฐC/min. Hold at 125ฐC for
10 min and then program to 200ฐC before returning to 30ฐC.
9.2.9 During the HRGC/MS data acquisition, remove the purge
tower cap and rinse the tower. Using the 10.0-mL syringe
and Teflonฎ tube, alternately add and withdraw 10.0-mL
portions of VOA-free water. Repeat this procedure a
minimum of six times and discard each rinse. Reassemble
the tower with 2.0 mL of VOA-free water.
9.2.10 After data acquisition is complete, check the HRGC/MS re-
sponse to the internal standards. Note that often the
initial analysis of the system following instrument shut-
down will give variable responses. If this is observed
and the responses are not equivalent to that previously
regarded as optimum performance, the purge tower instru-
ment evaluation must be repeated. Refer to Calculations
(Section 11.0) for response factor calculations. Figure
A-2 is an example of an HRGC/MS chromatogram obtained
for an instrument performance check.
A-11
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1. Benzene/d^-benzene
2. Bromodichloromethane
3. Toluene/ds-toluene
4. Bromochloropropane/
1,1,2-trichloroethane
5. Dibromochloromethane
6. Tetrachloroethene
7. Chlorobenzene/
d5-chlorobenzene
8. diO~ethylbenzene
9. Ethyl benzene
10. d]Q-p-xylene
11. Bromoform
12. Styrene
13. Dichloroburane
14. 1,1 , 2,2-telrachloroef'hane
15. d4~l ,4-dichlorobenzene
16. 1,2-dichlorobenzene
tee.t
B1C.
Purge Tower Standard
10 ]5
8
13
i
12
16
3:29
13:2ซ
:*J TIHF
Figure A-2. HRGC/MS chromatogram of purge tower standard analyzed
daily to document instrument performance.
A-12
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9.3 External quality control check - External quality control checks
(blind samples) should be conducted by the project Quality Control
Coordinator (QCC) to demonstrate proper instrument calibration.
These QC checks are performed periodically (typically on the first
analysis day of each week).
9.3.1 Allow the Tenax trap to return to room temperature.
9.3.2 The QC check is conducted in the same manner as the purge
tower instrument check, but the target analyte spiking
solution is provided by the project Quality Control Coor-
dinator (QCC).
9.3.3 The recoveries of the target analytes are calculated and
provided to the QCC for evaluation. If the evaluation is
adequate, the analyst proceeds with the system blank after
completing the system rinse as in 9.2.9. If the QC check
does not demonstrate acceptable performance, the analyst
must recalibrate the system and repeat the QC check.
9.4 System blank
9.4.1 With the system set up as in Figure A-l, with the Carle
valve in purge mode, add 80.0 ml_ of VOA-free water in the
Wheaton vessel and check for leaks.
9.4.2 Turn the purge tower valve off and helium supply off.
9.4.3 Remove the Wheaton vessel cap and inject 2.0 uL of the
internal standard solution. Follow 9.2.4, but substitute
the vessel for the purge tower and omit the analyte solu-
tion.
9.4.4 Reseal the vessel, turn on the helium at the helium sup-
ply valve. When a pressure reading is observed in the
system, open the stopcock at the purge tower; this will
prevent water from seeping into the lines at the bottom
of the purge tower. Check for leaks.
9.4.5 Turn on the stirrer and the valve at the three-way hot
water junction, so that the heated (95ฐC) water will flow
through the vessel jacket. Purge the system for 40.0 min.
9.4.6 After the 40.0-min purge, desorb as in 9.2.8.
9.4.7 Remove the modified Wheaton vessel and replace with a
clean headspace apparatus containing 80.0 ml VOA-free
water and clean stirring bar.
A-13
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9.4.8 Determine the level of contaminants and record. If ex-
cessive background is observed, clean the purge tower,
the transfer lines and repeat the system blank using a
clean headspace apparatus.
9.5 Tissue standard - A tissue sample (20 g) spiked with known levels
of the series of target analytes and internal standards should be
analyzed daily to document relative response factors from the
tissue matrix. Prior to initiating actual sample analysis, the
analyst should analyze a series of adipose tissue samples spiked
with 0.20 to 1.4 pg of each of the target analytes and 1.0 ng of
each internal standard. The analyst should require a relative
response factor consistency of ฑ 40% variability for the cali-
bration curve and for day to day verification of the calibration.
If the measured response factors are determined to vary by more
than 40% of the average, the calibration curve must be re-estab-
lished. The analyst must be aware that the background contribu-
tion of the tissue selected for spiked samples will effect the
measured response factors. If the background contribution is
significant, the analyst must analyze an unspiked sample to de-
termine the level of background. Figure A-3 is an example of a
spiked tissue standard.
9.5.1 With the system as in Figure A-l, turn off the purge tower
stopcock and helium supply valve. Remove the Wheaton ves-
sel cap and place 20.0 g of frozen adipose tissue in the
80.0 mL of water. Use the Fisher spatula to manipulate
the frozen tissue. The adipose tissue used for the tis-
sue standard analysis should be from a bulk supply so
that each tissue standard will be subjected to the same
matrix effects. Recap the vessel.
9.5.2 Spike this solution with 2.0 |j|_ of each spike solution
as in 9.2.4. Quickly recap the vessel.
9.5.3 Turn on the helium supply valve and open the purge tower
stopcock. Be sure the Carle valve is in the purge posi-
tion and the Tenax trap is at ambient temperature. Check
for leaks.
9.5.4 Purge the vessel for 40 min. After the 40 min, desorb as
in 9.2.8.
9.5.5 During data acquisition, clean and replace the Wheaton
vessel.
9.5.6 Check the instrument response to the internal standard
compounds. Calculate the response factor for each tar-
get analyte versus the respective internal standard and
record.
A-14
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1. Chloroform/d-chloroform 11.
2. BromochIoromethane 12.
3. 1,1,1-trichloroethane 13.
4. Benzene/d^-benzene 14.
5. Bromodichloromethane 15.
6. Toluene/dg-toluene 16.
7. 1,1,2-trichloroethane
8. Dibromochloromethane 17.
9. Tetrachloroethene 18.
10. Chlorobenzene/
d5~ch lorobenzene
d]0~ethylbenzene
Ethyl benzene
dlQ-p-xylene
Bromoform
Styrene
1,1,2,2-tetrachloroethane/
d2~lป1,2,2-tetrachloroethane
d4~l ,4-dichlorobenzene
1,2-dichlorobenzene
Tissue Standard
199.9-1
BIC.
3:20
6:46
13:29
16:48
2ซi m
Figure A-3. HR6C/MS chromatogram for the volatile organic analysis of a
bulk adipose tissue spiked with 1.0 yg of each internal
standard and 0.20 yg of each target analyte.
A-15
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9.6 Sample analysis
9.6.1 Sample analysis is achieved exactly the same manner as
the tissue standard with the exception that the target
analyte spiking solution is omitted. Figure A-4 is an
example of the volatile organic analysis of a composite
adipose tissue sample analyzed with the National Human
Adipose Tissue Survey Fiscal Year 1982 samples.
9.6.2 Checking the instrument response after each acquisition
and before proceeding to the next analysis will help pre-
vent the loss of valuable samples.
10.0 QUALITATIVE IDENTIFICATION
Obtain EICPs for the primary quantitation ion and at least one secondary
masses for each parameter of interest. The following criteria must be
met to make a qualitative identification. Table A-2 provides a summary
of the primary quantitation ions and the HRGC characteristics for each
of the target analytes and internal standards.
10.1 The characteristic masses of each parameter of interest must maxi-
mize in the same or within one scan of each other.
10.2 The retention time must fall within ฑ 30 s of the retention time
of the authentic compound.
10.3 The relative peak heights of the characteristic masses in the
EICPs must fall within ฑ 20% of the relative intensities of these
masses in a reference mass spectrum. The reference mass spectrum
can be obtained from a standard analyzed in the HRGC/MS system or
from a reference library.
11.0 CALCULATION
11.1 Relative response factors - Analyze each instrument performance
check standard and spiked adipose tissue sample. Tabulate the
area response of the characteristic quantitation ion against the
concentration for each target analyte and its corresponding inter-
nal standard (Table A-2) and calculate relative response factors
(RRF) using Equation 1:
A-16
-------
Tentative Identification
of Major Peaks
1. Acetic acid ethyl ester/
Propanoic acid propyl ester
2. Heptanal
3. Decane
4. Dimethyl octane
5. Trimethylcyclohexane
6. Nonanal
7. Undecene
8. Ethyl ester, carboxylic acid
9. Nonadienal
BIC_
Middle Atlantic, 0-14 years
3:29
6:40
ID: (Hi
13:2ft
16:40
2U-.M TINS
Figure A-4. HRGC/MS chromatogram of volatile compounds from the
NHATS FY82 composite of the 0-14 yr age group from
the Middle Atlantic Census Division.
A-17
-------
Table A-2. Characteristic Ions, Relative Retention Times (RRT),
and Internal Standards Used to Quantitate
Target Volatile Organic Analytes
Compound
Characteristic
quantitation
ion (m/z)
RRTC
Internal standard
Bromochl oropropane
Chloroform
d-Chloroform
1,1,1-Trichloroehtane
Bromodi chl oromethane
Benzene
d6-Benzene
Tetrachloroethene
Dibromochl oromethane
1,1,2-Trichloroethane
Toluene
dg-Toluene
Chlorobenzene
ds-Chlorobenzene
Ethyl benzene
d10~Ethylbenzene
Bromoform
Styrene
1,1,2, 2-Tetrachl oroethane
d2-l, 1,2, 2-Tetrachl oro-
ethane
1,2-Di chlorobenzene
d4-l,4-Di chlorobenzene
1,4-Di chlorobenzene
Xylene
d10-p_-Xylene
Ethylphenol
77
79
82
97
129
78
84
166
129
97
91
100
112
117
106
116
173
104
83
84
146
150
146
106
116
122
1.00
0.20-0.43
0.20-0.43
0.35-0.58
0.53-0.76
0.39-0.62
0.39-0.62
1.16-1.39
1.05-1.28
0.88-1.11
0.83-1.07
0.83-1.07
1.48-1.72
1.48-1.72
1.62-1.85
1.62-1.85
1.79-1.96
1.85-2.08
2.05-2.28
2.05-2.28
2.88-3.11
2.73-2.96
2.73-2.96
1.65-1.88
1.65-1.88
2.19-2.43
Bromochl oropropane
d-Chloroform
-
Bromochl ororopane
Bromochl oropropane
d6-Benzene
Bromochl oropropane
Bromochl oropropane
Bromochl oropropane
d8-Toluene
ds-Chlorobenzene
diQ-Ethylbenzene
Bromochl oropropane
Bromochl oropropane
d2-l, 1,2, 2-Tetrachl oroethane
d4-l,4-Di chlorobenzene
d4-l,4-Di chlorobenzene
d10-p_- Xylene
d10-p- Xylene
d10-Ethylbenzene
Relative retention times calculated versus the internal standard, bromochloropropane.
A-18
-------
Equation 1.
(A )(C. )
RRF - s TS
RRF ~ (A1s)(Cs)
, . = area of the characteristic quantitation ion for
wnere: As the target ana1yte.
A. = area of the characteristic quantitation ion for
15 the internal standard.
C. = Concentration of the internal standard (pg).
C = Concentration of the compound to be measured.
If the RRF value over the working range is a constant (< 40% RSD),
the RRF can be assumed to be invariant and the average RRF can be
used for calculations. Alternatively, the results can be used to
plot a calibration curve of response ratios, A /A. vs. RRF.
11.2 When a target analyte has been identified, the quantitation of
that compound should be based on the integrated abundance from
the EICP of the primary quantitation ion given in Table A-2.
Calculate the concentration in the sample using the relative re-
sponse factor (RRF) determined in Section 11.1 and Equation 2.
Equation 2.
(As)(Cis)
Concentration (Mg/g) = (A.s)(RRF)(wt)
where: A = area of the characteristic quantitation ion for
the target analyte.
A. = area of the characteristic quantitation ion for
the internal standard.
C. = concentration of the corresponding internal stan-
dard (|jg).
Wt = wet tissue weight (g).
12.0 REPORTING
12.1 Report target analyte results are demonstrated in Figures A-5 and
A-6.
12.2 Quantitative data must be qualified to provide an indication of
the intensity of response. Quantitative data for target analytes
A-19
-------
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Report Date:
Prepared By:
Reviewed By:
HUMAN ADIPOSE TISSUE DATA REPORTING FORM - VOLATILE ORGANICS
Total pg/Composite Specimen
Census Division ES - East South Central
Composite No. (1) (1) (2) (1) (2)
Age Group 0-14 15-44 15-44 45+ 45+
Sample Weight 25.6 g 19.0 g 24.3 g 20.6 g 19.3 g
Compound
Chloroform
1,1,1-Tri chloroethane
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Benzene
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Toluene
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Styrene
1,1,2,2-Tetrach1oroethane
1,2-DiChlorobenzene
1,4-Di chlorobenzene
Xylene
Ethylphenol
Figure A-6. Example data report format for volatile organic analytes
detected in composite samples from a specific census division.
A-21
-------
responses of less than 2.5 times background signal-to-noise (limit
of detection, LOD) are labeled as not detected (ND). Target ana-
lyte responses ranging from 2.5 to 10 times the background signal-
to-noise are reported as trace (tr) values. Target analytes with
response greater than 10 times the background signal-to-noise
(limit of quantitation, LOQ) are considered positive quantifiable
(PO) values.
13.0 METHOD PERFORMANCE
The method performance as determined by a single laboratory for instru-
ment performance checks and spiked adipose tissue specimens are pre-
sented in Tables A-3 and A-4. These data were generated using a Finnigan
4000 quadrupole mass spectrometer for the analysis of 46 composite speci-
mens from the National Human Adipose Tissue Survey (NHATS) Fiscal Year
1982 collection. The method detection limits are estimated to range
from 0.001 to 0.10 pg/g from 20-g tissue samples depending on the spe-
cific analyte and the observed interferences.
A-22
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A-24
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APPENDIX B
VOLATILE ORGANIC COMPOUND DATA FROM THE NHATS FY82 COMPOSITE
HUMAN ADIPOSE TISSUE SAMPLES
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Table B-2. Summary of the Total Mass (ng) of Selected Volatile Organic
Compounds Determined in the Composited Human Adipose
Tissues Representing the Mountain (MO)
Census Division
Total ug/composite specimen'
Census division
Composite no.
Age group
Sample weight
(1)
0-14
5.1 g
MO - Mountain
(1)
15-44
18.8 g
(1)
45+
22.4 g
Compound
Chloroform
1,1,1-Trichloroethane
Bromodi chl oromethane
Benzene
Tetrachloroethene
Di bromochl oromethane
1,1,2-Trichloroethane
Toluene
Chlorobenzene
Ethyl benzene
Bromoform
Styrene
1,1,2,2-Tetrachloroethane
1,2-Di chlorobenzene
1, 4- Di chlorobenzene
Xylene
Ethylphenol
0.21.
ND (1.2)
ND (2.3)
0.49
ND (0.12)
ND (0.12)
ND (0.23)
0.18
Tr, 0.011
0.12
ND (0.23)
1.8
ND (0.007)
ND (0.001)
0.091
0.62
1.4
1.54
0.33
ND (1.0)
0.38
ND (0.07)
ND (0.1)
ND (0.07)
0.28
0.12
0.40
ND (0.10)
1.8
ND (0.005)
Tr, 0.015
1.1
2.0
1.2
2.78
1.1
ND (1.2)
0.26
Tr, 0.10
ND (0.12)
ND (0.08)
0.55
0.090
0.66
ND (0.12)
1.7
ND (0.009)
Tr, 0.016
0.80
3.4
2.3
Data for chloroform, benzene, toluene, chlorobenzene, ethylbenzene, xylene,
ethylphenol, 1,1,2,2-tetrachloroethane and dichlorobenzene calculated by iso-
tope dilution. Deuterated analogs of all compounds, with the exception of
ethylphenol where deuterated ethylbenzene was used, were available as in-
ternal standards. All other compounds were quantitated versus the internal
.standard bromochloropropane (BCP).
ND = Not determined. Value in parenthesis represents the estimated
detection limit. Tr signifies trace level between limit of detection (LOD)
and limit of quantitation (LOQ).
Two responses were quantitated, howver, the specific isomers were not deter-
mined.
B-3
-------
Table B-3. Summary of the Total Mass of Selected Volatile Organic
Compounds Determined in the Composited Human Adipose
Tissues Representing the West South Central (WS)
Census Division
Census division
Composite no.
Age group
Sample weight
(1)
0-14
6.0 g
Total ug/composite specimen3
WS - West South Central
(1) (2)
15-44 15-44
22.4 g 21.9 g
(1)
45+
22.0 g
Compound
Chloroform
1,1,1-Trichloroethane
Bromodichloromethane
Benzene
Tetrachloroethene
Di bromochloromethane
1,1,2-Trichloroethane
Toluene
Chlorobenzene
Ethyl benzene
Bromoform
Styrene
1,1,2,2-Tetrachloroethane
1,2-DiChlorobenzene
1,4-Di chlorobenzene
Xylenec
Ethyl phenol
ND
(0.60)"
5.0
(3.0)
(0.08)
(0.20)
(0.20)
(0.30)
0.22
0.015
1.7
(0.30)
1.5
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ND (0.004)
2.1
8.6
2.4
ND
ND
ND
ND
ND
ND
0.29
ND (1.6)
ND (3.2)
0.31
(0.16)
(0.16)
(0.32)
(0.004)
0.063
5.6
(0.32)
1.4
ND (0.03)
0.037
2.6
25
3.0
ND
ND
ND
ND
ND
Tr
0.12
1.6
(1.8)
0.067
0.35
(0.08)
(0.06)
0.18
0.031
1.4
(0.08)
0.90
ND (0.008)
ND (0.004)
11
7.8
0.28
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(0.74)
(1.9)
(3.7)
0.51
(0.19)
(0.19)
(0.37)
0.76
0.19
3.7
ND (0.37)
3.0
ND (0.03)
Tr,
0.022
4.3
18
0.96
Data for chloroform, benzene, toluene, Chlorobenzene, ethyl benzene, xylene,
ethylphenol, 1,1,2,2-tetrachloroethane and dichlorobenzene calculated by iso-
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ND = Not determined. Value in parenthesis represents the estimated
detection limit. Tr signifies trace level between limit of detection (LOD)
and limit of quantisation (LOQ).
Two responses were quantitated, however, the specific isomers were not deter-
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B-6
-------
Table B-6. Summary of the Total Mass of Selected Volatile Organic Compounds
Deterined in the Composited Human Adipose Tissues Representing
the West North Central (WN) Census Division
Census division
Composite no.
Age group
Sample weight
(1)
0-14
18.9 g
Total pg/composite specimen
WN - West North Central
(1) (1)
15-44 45+
21.6 g 21.6 g
(2)
45+
18.3 g
Compound
Chloroform
1,1,1-Trichloroethane
Bromodi chl oromethane
Benzene
Tetrachl oroethene
Di bromochl oromethane
1,1,2-Trichloroethane
Toluene
Chlorobenzene
Ethyl benzene
Bromoform
Styrene
1,1,2, 2-Tetrachl oroethane
1,2-Di chlorobenzene
1,4-Di Chlorobenzene
Xylene
Ethylphenol
NO (0.032.)
ND (0.47)D
ND (0.94)
0.090
0.51
ND (0.14)
ND (0.094)
0.15
0.020
0.32
ND (0.094)
0.30
ND (0.001)
Tr, 0.007
1.1
1.5
1.4
0.31
ND (0.47)
ND (0.94)
0.34
0.39
ND (0.14)
ND (0.094)
0.40
0.020
0.99
ND (0.094)
0.61
ND (0.001)
ND (0.010)
0.48
1.7
0.10
0.15
0.58
ND (1.0)
0.10
0.79
ND (0.21)
ND (0.021)
0.13
0.020
0.16
ND (0.052)
0.18
ND (0.003)
0.040
1.1
0.59
Tr, 0.01
0.23
ND (0.40)
ND (1.6)
0.12
0.58
ND (0.16)
ND (0.08)
0.055
0.032
0.53
ND (0.080)
0.55
ND (0.09)
ND (0.017)
0.301
1.5
0.12
Data for chloroform, benzene, toluene, chlorobenzene, ethylbenzene, xylene,
ethylphenol, 1,1,2,2-tetrachloroethane and dichlorobenzene calculated by iso-
tope dilution. Deuterated analogs of all compounds, with the exception of
ethylphenol where deuterated ethylbenzene was used, were available as in-
ternal standards. All other compounds were quantitated versus the internal
.standard bromochloropropane (BCP).
ND = Not determined. Value in parenthesis represents the estimated detection
limit. Tr signifies trace level between limit of detection (LOD) and limit
of quantitation (LOQ).
Two responses were quantitated, however, the specific isomers were not deter-
mined.
B-7
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B-8
-------
Table B-8. Summary of the Total Mass of Selected Volatile Organic Compounds
Determined in the Composited Human Adipose Tissues
Representing the New England (NE)
Census Division
Census division
Composite no.
Age group
Sample weight
(1)
0-14
20.0 g
Total ug/composite specimen
NE - New England
(1) (1) "repeat"
15-44 15-44
23.6 g 23.6 g
(1)
45+
25.5 g
Compound
Chloroform Tr, 0.
1,1,1-Trichloroethane ND (0.
Bromodichloromethane ND (2.
Benzene 0.
Tetrachloroethene ND (0.
Dibromochloromethane ND (0.
1,1,2-Trichloroethane ND (0.
Toluene 0.
Chlorobenzene 0.
Ethylbenzene 2.
Bromoform ND (0.
Styrene 2.
1,1,2,2-Tetrachloroethane ND (0.
1,2-Dichlorobenzene Tr, 0,
1,4-Dichlorobenzene 0.
Xylene 3,
Ethylphenol 2,
070,
44)b
2)
69
08)
22)
22)
44
040
9
22)
2
020)
019
45
8
3
Tr
ND
ND
ND
ND
ND
ND
, 0.070
(0.44)
(2.2)
0.58
(0.08)
(0.22)
(0.22)
1.0
0.10
1.7
(0.22)
4.1
c
c
c
8.2
0.91
Tr
0.060
0.39
(4.2)
0.63
(0.15)
(0.42)
(0.42)
1.2
0.10
2.1
(0.42)
3.7
ND (0.030)
0.020
2.6
11
4.2
ND
ND
ND
ND
ND
Tr
0.16
ND (2.7)
ND (5.4)
0.50
ND (0.80)
ND (0.50)
ND (0.50)
0.38
0.060
1.7
ND (0.30)
3.2
(0.020)
(0.010)
0.30
9.7
3.9
ND
ND
Data for chloroform, benzene, toluene, chlorobenzene, ethylbenzene, xylene,
ethylphenol, 1,1,2,2-tetrachloroethane and dichlorobenzene calculated by iso-
tope dilution. Deuterated analogs of all compounds, with the exception of
ethylphenol where deuterated ethylbenzene was used, were available as in-
ternal standards. All other compounds were quantitated versus the internal
.standard bromochloropropane (BCP).
ND = Not determined. Value in parenthesis represents the estimated
detection limit. Tr signifies trace level between limit of detection (LOD)
and limit of quantisation (LOQ).
The HRGC/MS program was interrupted before the analysis was completed.
Two responses were quantitated, however, the specific isomers were not
determined.
B-9
-------
Table B-9. Summary of the Total Mass of Selected Volatile Organic Compounds
Determined in the Composited Human Adipose Tissues
Representing the Pacific (PA) Census Division
Total ug/composite specimen'
Census division
Composite no.
Age group
Sample weight
(1)
0-14
15.0 g
PA - Pacific
(1)
15-44
17.4 g
(1)
45+
20.7 g
Compound
Chloroform
1,1,1-Trichloroethane
Bromodichloromethane
Benzene
Tetrachloroethene
Dibromochloromethane
1,1,2-Trichloroethane
Toluene
Chlorobenzene
Ethyl benzene
Bromoform
Styrene
1,1,2,2-Tetrachloroethane
1,2-Di chlorobenzene
1,4-Dichlorobenzene
XyleneC
Ethylphenol
1.1
4.2
ND (0.80)
0.14
ND (0.060)
ND (0.050)
ND (0.30)
0.17
0.030
ND (0.040)
ND (0.30)
0.75
ND (0.010)
0.009
1.7
0.35
0.72
Tr
Tr,
ND
ND
ND
ND
0.10
1.8
(2.3)
0.22
0.19
(0.23)
ND (0.23)
0.34
0.040
0.68
(0.23)
2.5
(0.020)
0.073
0.29
0.81
0.55
Tr, 0.050
ND (0.30)
ND (1.1)
0.17
Tr, 0.11
ND (0.11)
ND (0.11)
0.26
0.020
0.58
ND (0.11)
1.0
ND (0.010)
Tr, 0.011
0.30
0.62
0.35
Data for chloroform, benzene, toluene, chlorobenzene, ethylbenzene, xylene,
ethylphenol, 1,1,2,2-tetrachloroethane and dichlorobenzene calculated by
isotope dilution. Deuterated analogs of all compounds, with the exception
of ethylphenol where deuterated ethylbenzene was used, were available as
internal standards. All other compounds were quantitated versus the in-
. ternal standard bromochloropropane (BCP).
ND = Not determined. Value in parenthesis represents the estimated
detection limit. Tr signifies trace level between limit of detection (LOD)
and limit of quantisation (LOQ).
cTwo responses were quantitated, however, the specific isomers were not deter-
mined.
B-10
-------
Table B-10. Summary of the Concentration (ng/g) of Target Volatile Organic
Compounds in Composite Human Adipose Tissue Specimens
Representing the East South Central (ES)
Census Division
Census division
Composite no.
Age group
(1)
0-14
ES - East South Central
(1) (2) (1)
15-44 15-44 45+
(2)
45+
Compoundc
Chloroform
1,1,1-Trichloroethane
Bromodi chl oromethane
Benzene
Tetrachl oroethene
Di bromochl oromethane
1,1,2-Trichloroethane
Toluene
Chlorobenzene
Ethyl benzene
Bromoform
Styrene
1,1,2, 2-Tetrachl oroethane
1, 2- Di chlorobenzene
1, 4- Di chlorobenzene
Xylenec
Ethylphenol
ND (8)u
18
ND (21)
11
ND (2)
ND (2)
ND (4)
13
3.8
ND (2)
ND (6)
38
ND (0.2)
1.8
180
49
50
ND (11)
ND (28)
ND (28)
7.9
29
ND (3)
ND (6)
18
1.7
9.0
ND (8)
79
ND (0.2)
ND (0.1)
40
56
17
Tr, 3.6
66
ND (74)
4.0
Tr, 4.6
ND (3)
ND (2)
7.6
3.9
12.1
ND (3)
28.4
2.1
Tr, 0.7
49
55
8
ND (10)
ND (21)
ND (21)
8.3
ND (3)
ND (2)
ND (5)
16
2.6
13
ND (8)
46
ND (0.3)
Tr, 0.2
300
57
40
ND (10)
100
ND (73)
2.6
12
ND (6)
ND (4)
2.5
1.6
16
ND (6)
46
8.0
Tr, 0.3
320
60
29
Data for chloroform, benzene, toluene, chlorobenzene, ethylbenzene, xylene,
ethylphenol, 1,1,2,2-tetrachloroethane and dichlorobenzene calculated by iso-
tope dilution. Deuterated analogs of all compounds, with the exception of
ethylphenol where deuterated ethylbenzene was used, were available as in-
ternal standards. All other compounds were quantitated versus the internal
.standard bromochloropropane (BCP).
ND = not detected. Value in parenthesis signifies an estimated detection
limit. Tr signifies trace level between limit of detection (LOD) and limit
of quantitation (LOQ).
Two responses were quantitated, however, the specific isomers were not deter-
mined.
B-ll
-------
Table B-ll. Summary of the Concentration (ng/g) of Target Volatile Organic
Compounds in Composite Human Adipose Tissue Specimens
Representing the Mountain (MO) Census Division
Census division
Composite no.
Age group
(1)
0-14
MO - Mountain
(1)
15-44
(1)
45+
Compound
Chloroform
1,1,1-Trichloroethane
Bromodichloromethane
Benzene
Tetrachloroethene
Dibromochloromethane
1,1,2-Trichloroethane
Toluene
Chlorobenzene
Ethyl benzene
Bromoform
Styrene
1,1,2,2-Tetrachloroethane
1,2-Di chlorobenzene
1,4-Dichlorobenzene
Xylene
Ethylphenol
41
NO (240)D
ND (450)
97
ND (24)
ND (24)
ND (45)
35
Tr, 2.2
24
ND (45)
353
ND (2)
ND (0.2)
18
120
270
ND
82
18
(53)
20
ND (4)
ND (5)
ND (4)
15
6.4
21
ND (5)
96
ND (0.3)
Tr
0.8
59
110
64
120
49
ND (50)
12
Tr, 5
ND (4)
ND (4)
25
4.0
30
ND (5)
76
ND (0.4)
Tr, 0.7
36
150
100
Data for chloroform, benzene, toluene, chlorobenzene, ethylbenzene, xylene,
ethylphenol, 1,1,2,2-tetrachloroethane and dichlorobenzene calculated by iso-
tope dilution. Deuterated analogs of all compounds, with the exception of
ethylphenol where deuterated ethylbenzene was used, were available as in-
ternal standards. All other compounds were quantitated versus the internal
.standard bromochloropropane (BCP).
ND = not detected. Value in parenthesis signifies an estimated detection
limit. Tr signifies trace level between limit of detection (LOD) and limit
of quantitation (LOQ).
GTwo responses were quantitated, however, the specific isomers were not deter-
mined.
B-12
-------
Table B-12. Summary of the Concentration (ng/g) of Target Volatile Organic
Compounds in Composite Human Adipose Tissue Specimens
Representing the West South Center (WS)
Census Division * *ง
Census division
Composite no.
Age group
(1)
0-14
WS - West South Central
(1) (2)
15-44 15-44
(1)
45+
Compound
Chloroform
1,1,1-Trichloroethane
Bromodi chl oromethane
Benzene
Di bromochl oromethane
1,1,2-Trichloroethane
Toluene
Chlorobenzene
Ethylbenzene
Bromoform
Styrene
1,1,2, 2-Tetrachl oroethane
1, 2- Di chlorobenzene
1,4-Di chlorobenzene
Xylenec
Ethylphenol
ND
ND
ND
ND
ND
ND
ND
ND
1
door
830
(500)
(13)
(33)
(50)
37
2.5
280
(50)
250
(2)
(0.7)
350
,400
400
ND
13
(71)
ND (140)
ND
ND
ND
ND
ND
Tr
1,
14
(7)
(14)
(0.2)
3.0
250
(14)
63
(1)
, 1.7
120
100
140
ND
ND
ND
ND
ND
ND
5.
75
(82)
3.
(4)
(3)
8.
1.
64
(4)
41
(0.
(0.
500
360
13
3
1
4
4
4)
2)
ND
ND
ND
ND
ND
ND
ND
Tr
(34)
(84)
(170)
23
(9)
(17)
35
8.
168
(17)
136
6
(1-4)
, 1.0
200
810
44
Data for chloroform, benzene, toluene, chlorobenzene, ethylbenzene, xylene,
ethylphenol, 1,1,2,2-tetrachloroethane and dichlorobenzene calculated by iso-
tope dilution. Deuterated analogs of all compounds, with the exception of
ethylphenol where deuterated ethylbenzene was used, were available as in-
ternal standards. All other compounds were quantitated versus the internal
.standard bromochloropropane (BCP).
ND = not detected. Value signifies an estimated detection limit. Tr
signifies trace level between limit of detection (LOD) and limit of quanti-
ctation (LOQ).
Two responses were quantitated, however, the specific isomers were not deter-
mi ned.
B-13
-------
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B-14
-------
Table B-14. Summary of the Concentration (ng/g) of Target Volatile Organic Compounds in
Composite Human Adipose Tissue Specimens Representing
the Middle Atlantic (MA) Census Division
Census division
Composite no.
Age group
MA - Middle Atlantic
(1)
0-14
(2)
0-14
(1)
15-44
(2)
15-44
(1)
45+
(1)
45+
Compound6
Chloroform
1,1,1-Trichloroethane
Bromodichloromethane
Benzene
Tetrachloroethene
Di bromochl oromethane
1,1,2-Trichloroethane
Tol uene
Chlorobenzene
Ethyl benzene
Bromoform
Styrene
1,1,2,2-Tetrachloroethane
1,2-Di chlorobenzene
1, 4- Di chlorobenzene
Xylenec
Ethylphenol
6.4
ND (17)D
ND (37)
6.4
49
ND (10)
ND (5)
4.4
2.0
8.4
ND (5)
41
ND (0.3)
Tr, 1.4
30
19
21
7.7
ND (19)
ND (39)
11
16
ND (4)
ND (3)
Tr, 0.7
0.6
6.6
ND (4)
44
ND (0.4)
Tr, 0.3,
24
28
47
6.4
97
ND (40)
8
75
ND (10)
ND (6)
6.8
2.4
14
ND (6)
39
ND (0.4)
Tr, 1.1
18
57
66
79
30
ND (91)
25
30
ND (9)
ND (5)
9.1
6.7
12
ND (8)
39
ND (0.4)
Tr, 1.4
320
52
68
14
ND (28)
ND (61)
13
94
ND (15)
ND (9)
14
3
14
ND (9)
45
ND (1)
Tr, 1.4
59
54
120
Tr, 5.6
ND (30)
ND (100)
15
46
ND (10)
ND (5)
ND (0.2)
2.5
0.1
ND (8)
42
ND (0.6)
Tr, 0.8
220
41
31
Data for chloroform, benzene, toluene, chlorobenzene, ethylbenzene, xylene, ethylphenol,
1,1,2,2-tetrachloroethane, and dichlorobenzene calculated by isotope dilution. Deuterated
analogs of all compounds, with the exception of ethylphenol where deuterated ethylbenzene
was used, were available as internal standards. All other compounds were quantitated
.versus the internal standard bromochloropropane (BCP).
ND = not detected. Value in parenthesis signifies an estimated detection limit. Tr
signifies trace level between limit of detection (LOD) and limit of quantitation (LOQ).
Two responses were quantitated, however, the specific isomers were not determined.
B-15
-------
Table B-15. Summary of the Concentration (ng/g) of Target Volatile
Organic Compounds in Composite Human Adipose Tissue Specimens
Representing the West North Central (WN) Census Division
Census division
Composite no.
Age group
(1)
0-14
WN - West
(1)
15-44
North Central
(2)
45+
(2)
45+
Compound
Chloroform
1,1,1-Tri chloroethane
Bromodichloromethane
Benzene
Tetrachloroethene
Di bromochloromethane
1,1,2-Trichloroethane
Toluene
Chlorobenzene
Ethyl benzene
Bromoform
Styrene
1,1,2,2-Tetrachloroethane
1,2-Dichlorobenzene
1,4-DiChlorobenzene
Xylene
Ethyl phenol
ND (2)
ND (24)ฐ
ND (50)
4.8
27
ND (7)
ND (5)
8.0
1.1
17
ND (5)
16
ND (0.1)
Tr, 0.4
58
79
72
14
ND (22)
ND (43)
16
18
ND (7)
ND (4)
19
0.9
46
ND (4)
28
ND (0.1)
ND (0.5)
22
81
5
7.0
27
ND (48)
4.6
37
ND (0.9)
ND (1)
6
0.9
7.4
ND (2)
8
ND (0.1)
1.9
51
27
Tr, 0.4
13
ND (22)
ND (87)
6.5
32
ND (9)
ND (4)
3
1.7
29
ND (4)
30
ND (5)
ND (0.4)
16
81
7
Data for chloroform, benzene, toluene, chlorobenzene, ethylbenzene, xylene,
ethylphenol, 1,1,2,2-tetrachloroethane and dichlorobenzene calculated by iso-
tope dilution. Deuterated analogs of all compounds, with the exception of
ethylphenol where deuterated ethylbenzene was used, were available as in-
ternal standards. All other compounds were quantitated versus the internal
.standard bromochloropropane (BCP).
ND = not detected. Value in parenthesis signifies an estimated detection
limit. Tr signifies trace level between limit of detection (LOD) and limit
of quantitation (LOQ).
Two responses were quantitated, however, the specific isomers were not de-
termined.
B-16
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B-17
-------
Table B-17. Summary of the Concentration (ng/g) of Target Volatile Organic
Compounds in Composite Human Adipose Tissue Specimens
Representing the Pacific (PA) Census Division
Census division
Composite no.
Age group
(1)
0-14
PA - Pacific
(1)
15-44
(1)
45+
Compound
Chloroform
1,1,1-Trichloroethane
Bromodi chloromethane
Benzene
Tetrachloroethene
Di bromochloromethane
1,1,2-Trichloroethane
Toluene
Chlorobenzene
Ethyl benzene
Bromoform
Styrene
1,1,2,2-Tetrachloroethane
1,2-Di chlorobenzene
1,4-Dichlorobenzene
Xylene
Ethylphenol
75
280
ND (53)
9.0
ND (4)
ND (3)
ND (20)
11
2
ND (3)
ND (20)
50
ND (0.7)
Tr, 0.6
110
24
48
Tr, 5.7
100
ND (130)
13
11
ND (13)
ND (13)
20
2.3
39
ND (13)
140
ND (1)
4.2
17
46
32
Tr, 2.4.
ND (14r
ND (53)
8.2
5.5
Tr
ND
ND
(5)
(5)
13
1.0
28
ND (5)
50
ND (0.5)
Tr, 0.5
15
30
17
Data for chloroform, benzene, toluene, chlorobenzene, ethylbenzene, xylene,
ethylphenol, 1,1,2,2-tetrachloroethane and dichlorobenzene calculated by iso-
tope dilution. Deuterated analogs of all compounds, with the exception of
ethylphenol where deuterated ethylbenzene was used, were available as in-
ternal standards. All other compounds were quantitated versus the internal
.standard bromochloropropane (BCP).
ND = not detected. Value in parenthesis signifies an estimated detection
limit. Tr signifies trace level between limit of detection (LOD) and limit
of quantitation (LOQ).
cTwo responses were quantitated, however, the specific isomers were not de-
termined.
B-18
-------
Table B-18. Summary of the Concentration (ng/g) of Target Volatile Organic
Compounds in Composite Human Adipose Tissue Specimens
Representing the New England (NE) Census Division
Census division
Composite no.
Age group
NE - New England
(1)
0-14
(1) (1)
15-44 15-44
(repeat)
(1)
45+
Compound*1
Chloroform
1,1, 1-Tri chl oroethane
Bromodichloromethane
Benzene
Tetrachl oroethane
Di bromochl oromethane
1,1,2-Tri chl oroethane
Tol uene
Chlorobenzene
Ethyl benzene
Bromoform
Styrene
1,1,2, 2-Tetrachl oroethane
1, 2- Di chlorobenzene
1, 4- Di chlorobenzene
MyTphenol
Tr, 3.5
ND (22)c
ND (110)
59
ND (4)
ND (14)
ND (11)
22
2
145
ND (11)
110
ND (1)
Tr, 1.0
i?3
120
Tr, 3
ND (19)
ND (93)
25
ND (3)
ND (9)
ND (9)
42
4.2
72
ND (9)
170
b
b
35&
38
Tr, 2.5
17
ND (180)
27
ND (6)
ND (18)
ND (18)
51
40
89
ND (18)
160
ND (1)
Tr, 1
488
180
6.3
ND (110)
ND (310)
20
ND (31)
ND (20)
ND (20)
15
2.4
67
ND (12)
124
ND (0.8)
ND (0.4)
38ง
150
Data for chloroform, benzene, toluene, chlorobenzene, ethylbenzene, xylene,
ethylphenol, 1,1,2,2-tetrachloroethane and dichlorobenzene calculated by iso-
tope dilution. Deuterated analogs of all compounds, with the exception of
ethylphenol where deuterated ethylbenzene was used, were available as in-
ternal standards. All other compounds were quantitated versus the internal
.standard bromochloropropane (BCP).
The HRGC/MS analysis was interrupted before the sample analysis was
completed.
ND = not detected. Value in parenthesis signifies an estimated detection
limit. Tr signifies trace level between limit of detection (LOD) and limit
.of quantitation (LOQ).
Two responses were quantitated, however, the specific isomers were not de-
termined.
B-19
-------
APPENDIX C
COMPOSITING SCHEME FOR THE NHATS FY82 SPECIMENS
C-l
-------
COMPOSITING SCHEME
The NHATS FY82 specimens were composited according to a scheme pro-
vided by the OTS Design and Development Branch (DDB) prime contractor, Battelle
Columbus Laboratories (BCL). The following tables provide the details of the
actual compositing effort. Composites for semivolatile organic analysis were
completed first. Thus, many of the specimens identified by BCL were depleted
before the volatile composite was prepared.
The aliquot for each individual specimen added to the composites is
specified and the approximate mass of each individual specimen remaining after
compositing is listed. Most samples contain up to 20 g total adipose tissue.
However, two samples (WS - Composite 1, 0-14 yr and MO - Composite 1, 0-14 yr)
consist of only 5-10 g total. This is a result of the very small sample sizes
that were available. Many of the samples for the MO census division could
not be located in the repository. The notation, NS, indicates no sample was
found.
One error in the actual compositing should be noted. Sample 8202780
was included in the WS Composite 1, 45 plus sample instead of the 15-44 com-
posite as specified in the BCL plan.
C-2
-------
Census Division = PA, Age Group = 0-14 Years, Composite 1
Semi volatile Volatile Approximate
FY 82 organic composite organic composite mass
specimen no. amount added (g) amount added (g) remaining (g)
8206310
8206336
8206344
8206351
8206294
8206328
8206369
3.1
2.9
2.4
2.8
2.7
2.9
2.9
0.8
3.2
0
3.2
2.9
2.3
2.6
0
3
0
1.0
1.5
0
0
Total composite (g) 19.7 15.0
Date composited: 2/27/84
C-3
-------
Census Division = PA, Age Group = 15-44 Years, Composite 1
Semi volatile Volatile Approximate
FY 82 organic composite organic composite mass
specimen no. amount added (g) amount added (g) remaining (g)
8206153
8206195
8206229
8206419
8206211
8206237
8206245
8206260
8206203
2.2
2.6
2.8
2.4
2.2
2.3
2.3
2.6
2.2
2.2
2.2
2.2
2.6
1.1
2.3
2.2
2.6
0
4
4
4
3
2
4
3
4
0
Total composite (g) 21.6 17.4
Date composited: 2/27/84
C-4
-------
Census Division = PA, Age Group = 45 + Years, Composite 1
FY 82
specimen no.
8206278
8206286
8206302
8206435
8205346
8205353
8205361
8206252
8206377
8206385
8206393
8205387
8206401
8206427
8206443
Semi volatile
organic composite
amount added (g)
1.3
1.3
1.1
1.8
1.9
1.6
1.7
1.5
1.2
1.2
1.4
1.2
1.8
1.4
1.6
Volatile
organic composite
amount added (g)
1.3
1.5
1.7
1.3
1.3
1.1
1.5
1.4
1.4
1.2
1.8
1.6
1.3
0.9
1.4
Approximate
mass
remaining (g)
25
10
15
20
10
5
.5
20
15
10
15
15
10
25
10
Total composite (g) 22.0 20.7
Date composited: 2/27/84
C-5
-------
Census Division = NE, Age Group = 0-14 Years, Composite I
Semivolatile Volatile Approximate
FY 82 organic composite organic composite mass
specimen no. amount added (g) amount added (g) remaining (g)
8110678
8110686
8110710
8110736
8110744
8110751
8111072
8303737
8303794
8110975
8111007
8111015
8111049
8111098
8303778
8303711
8303919
Total composite
Date composited:
0.8
0.9
0.9
1.5
1.3
1.4
1.1
NS
0.9
1.4
1.2
1.2
1.2
1.4
1.2
1.5
1.2
(g) 19.1
2/27/84
1.5
1.1
1.6
1.4
1.2
0.5
1.2
NS
1.2
0.9
1.4
1.4
1.0
1.1
1.3
1.9
1.3
20.0
3
1
3
3
0
0
1
NS
0.5
3
5
7
4
1
4
3
7
C-6
-------
Census Division = NE, Age Group = 15-44 Years, Composite 1
FY 82
specimen no.
8110660
8110728
8110769
8110777
8110785
8110793
8110801
8303661
8303679
8303687
8303729
8303810
8303927
8110827
8110983
8110991
8111031
8111056
8111064
8111080
8303802
8303851
8110702
8303893
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
1.0
1.0
1.0
1.1
1.0
1.1
1.1
1.0
1.1
1.1
NS
1.0
1.0
1.1
1.0
1.2
1.1
1.2
0.8
1.0
1.0
NS
1.0
NS
(g) 21.9
2/27/84
Volatile
organic composite
amount added (g)
1.0
1.2
1.0
1.0
1.0
1.3
1.1
1.0
1.1
1.1
NS
1.0
1.1
1.7
1.0
1.0
1.1
1.1
1.3
1.1
1.2
NS
1.2
NS
23.6
Approximate
mass
remaining (g)
5
3
4
4
4
5
2
2
3
3
NS
2
5
1
2
2
2
2
2
2
3
NS
2
NS
C-7
-------
Census Division = NE, Age Group = 45 + Years, Composite 1
FY 82
specimen no.
Semi volatile
organic composite
amount added (g)
Volatile
organic composite
amount added (g)
Approximate
mass
remaining (g)
8110819
8110835
8110843
8110876
8110884 '
8110934
8110959
8111023
8303752
8303828
8303877
8110694
8110850
8110868
8110892
8110900
8110918
8110926
8110942
8110967
8303836
Total composite
Date composited:
1.2
1.3
1.2
1.3
1.3
1.8
2.0
1.1
NS
1.2
NS
1.2
1.0
1.2
2.2
1.5
1.6
2.2
1.1
1.3
1.0
(9) 26.7
2/27/84
1.0
1.5
1.3
1.3
1.5
1.4
1.6
1.0
NS
1.0
NS
1.6
1.3
1.8
1.0
1.2
1.6
1.9
1.4
1.3
0.8
25.5
3
5
3
5
4
5
3
7
NS
6
NS
7
1
3
6
3
2.5
2
6
8
2
C-8
-------
Census Division = MA, Age Group = 0-14 Years, Composite 1
FY 82
specimen no.
8205023
8205031
8205049
8201790
8201808
8206062
8206088
8206187
8201485
8206021
8110595
8110652
8205007
8300006
Semi volatile
organic composite
amount added (g)
0.7
0.9
0.5
2.5
2.7
2.8
3.0
3.0
2.8
3.1
NS
NS
1.0
NS
Volatile
organic composite
amount added (g)
0
0
0
3.0
3.0
2.6
3.1
3.0
2.6
3.0
NS
NS
0
NS
Approximate
mass
remaining (g)
0
0
0
25
20
20
20
25
20
20
NS
NS
0
NS
Total composite (g) 23.0
Date composited: 2/28/84
20.3
C-9
-------
Census Division = MA, Age Group = 15-44 Years, Composite 1
FY 82
specimen no.
8201584
8201659
8205965
8205999
8206013
8203143
8203176
8203358
8203366
8203374
8201642
8201832
8205817
8205833
8205841
8205882
8206161
8203168
8203226
8203325
8205973
8203408
8201543
8205858
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
1.0
1.1
1.1
1.1
1.0
1.0
1.0
1.1
1.0
1.0
1.0
0.9
1.0
1.2
0.9
1.1
1.0
1.1
1.2
1.0
1.1
1.0
1.1
1.2
(g) 25.2
2/28/84
Volatile
organic composite
amount added (g)
1.1
1.2
1.0
1.2
1.1
0.7
1.0
1.2
1.4
1.1
1.1
1.0
1.1
1.2
0.9
1.1
0.9
1.0
1.0
1.0
1.1
0.4
1.2
1.0
25.0
Approximate
mass
remaining (g)
10
10
5
5
10
3
5
10
5
10
10
10
10
10
5
10
10
10
5
10
10
2
2
5
C-10
-------
Census Division = MA, Age Group = 45 + Years, Composite 1
FY 82
specimen no.
8201469
8201501
8201576
8201675
8201717
8201782
8203135
8203184
8203291
8203341
8300584
8201451
8201519
8201535
8201600
801667
8203192
8203317
8300600
8300618
8300642
8207185
8201816
8300444
8201447
Total composite
Date composited:
Semivolatile
organic composite
amount added (g)
0.7
0.9
0.9
0.6
0.9
1.0
0.9
0.7
0.9
0.8
NS
0.8
0.8
0.9
0.7
0.7
0.7
0.7
NS
NS
NS
1.0
0.8
NS
0.8
(g) 16.2
2/28/84
Volatile
organic composite
amount added (g)
0.7
1.0
0.9
1.0
0.7
0.9
0.8
0.7
0.8
0.9
NS
0.7
1.0
0.9
0.7
0.8
0.8
0.8
NS
NS
NS
0.8
0.6
NS
0.8
16.3
Approximate
mass
remaining (g)
20
25
15
25
25
20
20
15
20
25
NS
25
25
20
25
25
20
25
NS
NS
NS
15
25
NS
-
C-ll
-------
Census Division = MA, Age Group = 0-14 Years, Composite 2
FY 82
specimen no.
8300030
8201550
8201691
8206104
8206112
8206120
8206179
8206005
8206039
8206047
8206054
8205056
8206070
8201626
Semi volatile
organic composite
amount added (g)
NS
1.6
1.4
1.3
1.5
1.4
1.2
1.2
2.4
1.5
1.7
1.1
2.5
1.4
Volatile
organic composite
amount added (g)
NS
1.6
1.5
1.5
1.3
1.5
1.2
1.2
1.7
1.4
2.3
0
1.4
1.5
Approximate
mass
remaining (g)
NS
15
25
20
20
20
10
20
20
25
15
0
20
25
Total composite (g) 20.2
Date composited: 2/29/84
18.1
C-12
-------
Census Division = MA, Age Group = 15-44 Years, Composite 2
FY 82
specimen no.
8201634
8201824
8205890
8205916
8205924
8205932
8205940
8205957
8205981
8203267
8205791
8205825
8205866
8205874
8206146
8203127
8203218
8203234
8203333
8201840
8203283
8206138
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
1.3
1.1
1.6
1.3
1.1
1.4
1.1
1.2
1.3
0.6
1.2
1.1
1.5
1.2
1.2
1.1
1.0
1.0
1.6
1.1
1.0
1.1
(g) 26.1
2/29/84
Volatile
organic composite
amount added (g)
1.2
1.1
1.2
1.6
1.2
1.1
1.3
1.0
1.4
0.6
1.0
1.3
1.2
1.3
1.0
0.9
1.0
1.0
' 1.2
1.2
1.0
1.5
25.3
Approximate
mass
remaining (g)
10
10
10
10
10
10
10
10
10
5
10
10
10
10
10
5
10
10
8
10
5
10
C-13
-------
Census Division = MA, Age Group = 45 + Years, Composite 2
FY 82
specimen no.
8201493
8201568
8201592
8201709
8201725
8201774
8203150
8203259
8300451
8300485
8201618
8201733
8201758
8201766
8201857
8203200
8203275
8203382
8203424
8300568
8300634
8300659
8201527
8201683
8203309
Semi volatile
organic composite
amount added (g)
0.8
0.8
0.7
0.8
0.7
0.8
0.8
0.8
NS
NS
1.2
0.7
1.2
1.3
1.4
0.9
0.8
0.9
0.8
NS
NS
NS
0.9
1.0
0.7
Volatile
organic composite
amount added (g)
0.8
0.8
0.8
0.9
1.0
1.0
0.7
0.7
NS
NS
0.8
0.7
1.1
1.0
0.6
1.0
0.7
1.2
0.9
NS
NS
NS
0.9
1.4
0.8
Approximate
mass
remaining (g)
20
25
25
25
25
20
25
15
NS
NS
20
25
25
25
20
20
20
20
20
NS
NS
NS
20
25
25
Total composite (g) 18.0
Date composited: 3/1/84
17.8
C-14
-------
Census Division = EN, Age Group = 0-14 Years, Composite 1
FY 82
specimen no.
8201246
8203101
8207979
8206864
8206930
8200065
8200230
8200354
8201360
8203077
8203119
8200214
8203416
8210189
8210247
8203010
8203465
8210205
8210403
8210379
Semi volatile
organic composite
amount added (g)
1.3
1.0
1.5
1.0
1.2
0.8
0.6
0.5
1.1
1.4
1.0
1.0
1.0
1.0
NS
1.2
0.8
NS
0.9
0.8
Volatile
organic composite
amount added (g)
1.4
0
1.1
1.2
1.2
0
0
0
1.1
0.8
1.0
1.2
0.5
1.5
NS
0.9
0
NS
0.8
0
Approximate
mass
remaining (g)
5
0
1
5
5
0
0
0
2
0
1
0
0
0.5
NS
2
0
NS
1
0
Total composite (g) 18.1
Date composited: 2/28/84
12.7
C-15
-------
Census Division = EN, Age Group = 15-44 Years, Composite 1
FY 82
specimen no.
Semi volatile
organic composite
amount added (g)
Volatile
organic composite
amount added (g)
Approximate
mass
remaining (g)
8201162
8201170
8201188
8201238
8201345
8203630
8205288
8200297
8210171
8201352
8201386
8201436
8203028
8205163
8200370
8200388
8203432
8203499
8210346
8200081
8210270
Total composite
Date composited:
0.8
1.2
1.0
0.9
0.9
0.9
1.3
1.1
0.9
1.2
1.1
0.8
2.2
0.8
1.0
0.8
0.9
1.3
NS
1.2
1.3
(g) 21.6
2/28/84
0.9
1.1
0.9
0.9
1.1
1.1
0.9
1.4
1.1
0.9
1.4
1.1
3.3
0.7
0.8
1.0
0.8
0.5
NS
0
0.9
20.8
5
10
5
10
15
5
2
2
5
10
10
15
2
10
0
3
10
0
NS
0
4
C-16
-------
Census Division = EN, Age Group = 45 + Years, Composite 1
FY 82
specimen no.
8201287
8201378
8201410
8203051
8205148
8200313
8200487
8200503
8207201
8201212
8205171
8205320
8200438
8200453
8200461
8210148
8210353
8207243
8210320
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
1.2
1.1
1.4
1.1
1.0
1.1
1.0
1.3
1.0
1.1
1.1
1.0
1.0
1.3
1.0
NS
1.0
1.0
1.1
(g) 19.8
2/28/84
Volatile
organic composite
amount added (g)
1.1
1.1
1.2
1.2
1.0
1.1
1.4
1.0
1.0
1.0
1.1
1.1
1.0
1.0
1.0
NS
0.1
1.1
1.1
18.6
Approximate
mass
remaining (g)
10
5
5
5
2
10
. 2
2
5
5
5
5
1
2
2
NS
0
10
2
C-17
-------
Census Division = EN, Age Group = 0-14 Years, Composite 2
FY 82
specimen no.
8207961
8206922
8205304
8203085
8207953
8206880
8206856
8206872
8200396
8203440
8210221
8206914
8200040
8200404
8210254
8210288
8210411
8203036
8203069
8200412
8203457
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
1.5
1.0
0.9
1.8
1.1
1.2
1.1
1.2
1.1
1.1
0.2
1.0
1.1
0.9
0.9
NS
1.1
1.1
0.6
1.3
1.0
(g) 21.2
3/1/84
Volatile
organic composite
amount added (g)
1.4
1.1
0
2.0
1.0
1.2
1.6
0.6
0.3
1.1
0
0.9
0
1
0
NS
1.2
1.2
0.8
1.0
0.9
17.3
Approximate
mass
remaining (g)
2
4
0
0
5
1
2
1
0
1
0
4
0
1
0
NS
1
1
1
5
1
C-18
-------
Census Division = EN, Age Group = 15-44 Years, Composite 2
FY 82
specimen no.
8201204
8201311
8201428
8200255
8200271
8203507
8210262
8210296
8207169
8201337
8201394
8203002
8205254
8205270
8200339
8203481
8210387
8207177
8207235
3200511
8205155
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
1.1
1.1
1.2
1.4
1.5
NS
1.4
NS
1.0
1.1
1.0
1.0
1.0
0.9
1.0
1.0
1.2
0.7
1.1
1.6
1.1
(g) 21.4
3/1/84
Volatile
organic composite
amount added (g)
1.1
1.1
1.0
0.8
1.1
NS
1.4
NS
0.9
0.9
1.0
1.5
1.0
1.2
0.9
1.0
1.0
1.2
1.4
1.2
1.4
21.1
Approximate
mass
remaining (g)
10
10
20
2
8-
NS
4
NS
7
20
20
20
4
3
10
10
20
20
15
0
10
C-19
-------
Census Division = EN, Age Group = 45 + Years, Composite 2
FY 82
specimen no.
Semi volatile
organic composite
amount added (g)
Volatile
organic composite
amount added (g)
Approximate
mass
remaining (g)
8201220
8201261
8201279
8201444
8205106
8205239
8302853
8200115
8200156
8207946
8205189
8205205
8200420
8200446
8210163
8210213
8210395
8205130
8203507
1.7
1.7
1.8
1.5
1.3
1.0
1.7
1.4
1.6
1.1
1.2
1.6
1.0
1.6
NS
1.6
1.7
1.4
1.3
1.8
1.6
1.5
1.7
1.3
1.5
1.4
1.2
1.5
0.5
1.6
1.3
0
1.4
NS
1.6
1.6
1.1
0
5
5
10
5
4
1
5
4
2
5
2
2
0
3
NS
2
2
2
0
Total composite (g) 26.2
Date composited: 3/1/84
22.6
C-20
-------
Census Division = EN, Age Group = 15-44 Years, Composite 3
FY 82
specimen no.
Semivolatile
organic composite
amount added (g)
Volatile
organic composite
amount added (g)
Approximate
mass
remaining (g)
8201295
8206898
8205114
8205197
8205262
8302838
8200131
8200172
8210155
8210239
8201196
8203044
8206831
8205296
8200198
8203473
8210130
8210361
8207193
8207268
8210338
8207136
Total composite
Date composited:
1.2
1.0
1.1
1.7
1.0
1.2
0.4
1.0
1.1
NS
0.9
1.2
1.3
0.9
1.2
1.0
NS
NS
1.3
1.0
0.9
0.8
(g) 20.2
3/1/84
1.5
1.6
0.9
1.1
0.8
1.1
0
0.8
1.1
NS
0.8
1.0
1.5
1.0
0.8
1.1
NS
NS
1.4
1.1
1.2
0.8
19.6
10
15
10
6
6
6
0
0
10
NS
6
4
10
6
1
4
NS
NS
10
20
15
20
C-21
-------
Census Division = EN, Age Group = 45 + Years, Composite 3
FY 82
specimen no.
8201329
8205213
8205221
8200495
8210197
8210304
8210312
8207151
8207227
8201253
8201303
8201402
8205122
8205247
8302820
8200479
8207219
Semi volatile
organic composite
amount added (g)
1.9
1.6
1.8
0.8
NS
NS
1.9
2.3
1.7
1.6
1.6
1.4
1.4
1.6
NS
1.6
2.0
Volatile
organic composite
amount added (g)
1.5
1.3
1.5
0
NS
NS
1.7
2.0
1.9
1.6
1.6
1.8
1.5
2.2
NS
1.3
1.5
Approximate
mass
remaining (g)
8
2
8
0
NS
NS
2
5
5
5
5
2
0
0.5
NS
2
8
Total composite (g) 23.2
Date composited: 3/1/84
21.4
C-22
-------
Census Division = WN, Age Group = 0-14 Years, Composite 1
FY 82
specimen no.
8201980
8205478
8205551
8205577
8205619
8205635
8205668
8205569
8205684
8205692
8205734
8205783
8201949
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
1.0
2.0
1.4
1.1
2.0
2.0
2.5
2.5
1.3
1.5
2.0
2.3
1.8
(g) 23.4
2/28/84
Volatile
organic composite
amount added (g)
1.5
2.4
1.1
0
0
2.4
1.8
3.5
2.7
0
1.5
1.1
0.9
18.9
Approximate
mass
remaining (g)
1
2.5
0
0
0
5
5
3
1.0
0
1
0
0
C-23
-------
Census Division = WN, Age Group = 15-44 Years, Composite 1
FY 82
specimen no.
8202012
8210833
8205486
8205536
8205544
8205585
8205601
8205643
8205676
8205718
8205742
8210759
8205593
8205627
8205700
8205759
8205767
Semi volatile
organic composite
amount added (g)
1.2
0.9
0.9
1.4
1.1
1.1
1.1
1.1
1.2
1.2
1.7
1.2
1.2
1.6
1.3
1.2
1.2
Volatile
organic composite
amount added (g)
1.6
1.0
1.2
1.9
1.3
1.0
0.9
1.2
1.5
1.5
1.7
1.1
1.0
1.2
1.0
1.1
1.4
Approximate
mass
remaining (g)
10
20
10
7
7
10
8
6
1
4
2
10
5
20
10
10
5
Total composite (g) 20.6 21.6
Date composited: 2/29/84
C-24
-------
Census Division = WN, Age Group = 45 + Years, Composite 1
Semi volatile Volatile Approximate
FY 82 organic composite organic composite mass
specimen no. amount added (g) amount added (g) remaining (g)
8201964
8202004
8210783
8210841
8205429
8205452
8205502
8205510
8201998
8210791
8205395
8205403
8205437
8205445
8205650
Total composite
Date composited:
1.7
1.6
1.5
1.5
1.7
1.7
1.1
1.5
1.2
1.4
1.8
1.6
1.5
1.7
1.0
(g) 22.5
2/28/84
1.5
1.7
1.5
1.6
1.4
1.6
1.3
1.5
1.1
1.1
1.8
1.9
1.6
1.0
1.0
21.6
10
5
5
10
5
5
5
5
5
5
1
5
2
2
2
C-25
-------
Census Division = WN, Age Group = 45 + Years, Composite 2
FY 82
specimen no.
8201956
8202038
8202053
8210817
8205411
8205494
8205809
8201972
8202020
8202046
8210767
8205460
8205528
8205775
8205726
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
1.4
1.4
1.6
1.3
1.3
1.2
1.3
1.4
1.4
1.5
1.3
1.6
1.4
1.3
2.0
(9) 21.4
2/28/84
Volatile
organic composite
amount added (g)
1.2
1.3
1.5
1.3
1.1
1.2
1.1
1.4
1.1
1.2
1.3
1.1
1.2
1.3
1.0
18.3
Approximate
mass
remaining (g)
5
15
15
5
5
9
0
8
6
10
5
8
10
15
2
C-26
-------
Census Division = SA, Age Group = 0-14 Years, Composite 1
FY 82
specimen no.
8201113
8303042
8202145
8204059
8202277
8203572
8203978
8202327
8202343
8202426
8200149
8200222
8203986
8202350
8201089
8202129
8202160
8202194
8203952
8202244
Semi volatile
organic composite
amount added (g)
1.0
1.4
1.2
1.3
0.9
1.2
0.9
1.4
1.1
0.9
1.1
0.6
1.3
0.8
1.3
0.8
0.9
0.8
0.8
1.0
Volatile
organic composite
amount added (g)
1.0
1.6
0
0
0.9
1.4
0
0.8
1.5
1.7
0.7
0
0.3
0.8
1.0
0
0
0
0
0.9
Approximate
mass
remaining (g)
10
0.5
0
0
4
0.5
0
10
1
4
0
0
0
15
2.5
0
0
0
0
15
Total composite (g) 20.7
Date composited: 2/29/84
12.6
C-27
-------
Census Division = SA, Age Group = 15-44 Years, Composite 1
FY 82
specimen no.
8203515
8203671
8203762
8203796
8203853
8202269
8202509
8207003
8201105
8203895
8203929
8204000
8202251
8202616
8207086
8203606
8201139
8201147
8203788
8203820
8208316
8110041
8200206
8200248
8204042
8202434
8202525
Semi volatile
organic composite
amount added (g)
1.0
1.3
1.1
1.1
1.0
1.1
0.9
0.8
0.9
1.1
1.5
0.9
1.0
0.8
0.9
0.8
1.0
0.8
1.0
0.9
0.9
NS
1.3
0.8
1.0
1.1
1.4
Volatile
organic composite
amount added (g)
1.0
0
0
0.9
0.9
1.1
1.0
0.9
0.8
1.0
1.1
0.7
0.7
0.8
1.5
0.8
0.8
1.3
0.9
0.9
0.8
NS
0.6
0.7
1.4
1.2
1.0
Approximate
mass
remaining (g)
10
0
0
2
1
10
2
1
10
5
0
0.5
2
5
0
3
4
2
2
1
1
NS
0
0
0
10
4
Total composite (g) 26.4
Date composited: 2/29/84
22.8
C-28
-------
Census Division = SA, Age Group = 45 + Years, Composite 1
FY 82
specimen no.
8206963
8203556
8203580
8201014
8200073
8202186 '
8203747
8203879
8204034
8202384
8206989
8207037
3203598
8201055
8303083
8203705
8203713
8208332
8202301
8207011
8110058
8200164
8203655
8203721
8202210
8202392
8202558
8202632
Total composite (
Date composited:
Semi volatile
organic composite
amount added (g)
0.8
0.8
0.7
0.7
0.6
0.5
0.6
0.5
0.6
0.7
0.9
0.6
1.4
0.9
NS
0.7
0.6
0.7
0.9
0.8
NS
1.2
1.0
0.8
1.0
1.0
1.0
NS
g) 20.0
2/29/84
Volatile
organic composite
amount added (g)
0.7
0.7
0.6
0.6
0.6
0
0.8
0.6
0.7
0.7
1.2
0.7
0.9
0.8
NS
0.8
0.9
0.7
0.7
0.7
NS
0
0
0
0.6
0.6
0.8
NS
15.4
Approximate
mass
remaining (g)
4
10
6
6
0
0
. 0
0
7
20
10
6
15
6
NS
7
3
8
8
5
NS
0
0
0
15
20
10
NS
C-29
-------
Census Division = SA, Age Group = 0-14 Years, Composite 2
FY 82
specimen no.
8303257
8208506
8202368
8202533
8303273
8200305
8202079
8201121
8303232
8204018
8202285
8202376
8303067
8303091
Semi volatile
organic composite
amount added (g)
1.8
0.3
1.6
1.2
1.2
1.0
1.2
2.3
1.8
0.6
1.7
1.6
1.1
1.7
Volatile
organic composite
amount added (g)
1.6
0
2.1
2.3
1.2
0
0.6
1.9
1.5
0
1.7
1.5
0.8
1.5
Approximate
mass
remaining (g)
2
0
5
1
1
0
0
1
0
0
5
8
0
0
Total composite (g) 19.1 16.7
Date composited: 3/1/84
C-30
-------
Census Division = SA, Age Group = 15-44 Years, Composite 2
FY 82
specimen no.
8207078
8302986
8203887
8208472
8110025
8201154
8202111
8203770
8207060
8207144
8203622
8200321
8203754
8202103
8203739
8202236
8202608
8202335
8202442
8208522
8202459
8203994
8202400
8203804
8203911
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
0.7
NS
0.8
1.0
NS
0.7
0.9
0.6
0.9
0.7
1.3
0.7
1.1
0.9
0.9
1.0
1.0
0.7
0.8
NS
1.0
1.0
1.1
1.0
0.7
(g) 19.5
3/1/84
Volatile
organic composite
amount added (g)
0.8
NS
0.9
0.7
NS
0.8
0.7
0.7
0.7
0.8
0.8
0.6
1.2
1.1
1.4
1.1
1.2
0.8
0.6
NS
0.6
0.6
0.8
0.9
0.9
18.7
Approximate
mass
remaining (g)
1
NS
0.5
0.5
NS
10
10
2
1
6
10
2
5
1
0
20
10
15
5
NS
20
0
15
1
4
C-31
-------
Census Division = SA, Age Group = 45 + Years, Composite 2
FY 82
specimen no.
Semi volatile
organic composite
amount added (g)
Volatile
organic composite
amount added (g)
Approximate
mass
remaining (g)
8206971
8110033
8202061
8207052
8203531
8201006
8203812
8203861
8208514
8202483
8202574
8202178
8204026
8208480
8202202
8202467
8202590
8201022
8202137
8202152
8208399
8202418
8202624
1.2
NS
0.8
1.6
1.1
1.3
1.0
1.1
NS
1.6
1.4
1.1
1.1
1.2
1.3
1.1
1.2
1.6
1.1
1.3
1.3
1.3
1.4
1.1
NS
0.7
1.2
1.3
1.3
0.9
1.1
NS
1.4
1.1
1.4
0.9
1.2
1.0
0.9
1.3
1.3
0.4
1.0
1.2
1.3
1.2
2
NS
0
2
5
5
0
2
NS
5
10
1
1
5
8
8
5
10
0
1
2
10
5
Total composite (g) 26.1
Date composited: 3/1/84
23.2
C-32
-------
Census Division = SA, Age Group = 15-44 Years, Composite 3
FY 82
specimen no.
8203523
8203546
8201071
8202087
8203697
8208407
8109993
8302937
8303240
8200362
8203937
8208365
8207110
8110066
8303117
8202293
8202582
8303109
8200347
8203960
8202491
8202517
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
0.8
0.7
0.9
1.1
0.4
1.5
NS
0.9
1.3
1.1
1.2
0.6
0.7
NS
0.7
0.8
0.6
1.5
0.7
1.0
NS
1.4
(g) 17.9
3/1/84
Volatile
organic composite
amount added (g)
0.6
1.2
0.7
0.7
0
0
NS
0.8
0.6
0
0
0.7
0.9
NS
0.7
0.9
0.6
0.9
0
0
NS
0.8
10.1
Approximate
mass
remaining (g)
8
3
4
1
0
0
NS
8
5
0
0
0
6
NS
5
6
10
5
0
0
NS
10
C-33
-------
Census Division = SA, Age Group = 45 + Years, Composite 3
FY 82
specimen no.
Semivolatile
organic composite
amount added (g)
Volatile
organic composite
amount added (g)
Approximate
mass
remaining (g)
8207029
8302960
8201048
8201063
8110009
8200123
8202566
8201030
8303125
8203846
Total composite (g'
1.7
2.7
2.0
2.0
NS
1.8
2.4
2.2
2.0
1.2
) 18.0
0
2.2
2.3
2.5
NS
0.6
2.5
1.9
1.8
0
13.8
0
2
0
2
NS
0
5"
6
2
0
Date composited: 3/1/84
C-34
-------
Census Division = SA, Age Group = 15-44 Years, Composite 4
FY 82
specimen no.
Semi volatile
organic composite
amount added (g)
Volatile
organic composite
amount added (g)
Approximate
mass
remaining (g)
8203838
8208415
8202228
8207128
8203663
8202541
8207102
8302978
8203689
8202319
8303059
8208530
8202475
8202491
Total composite
Date composited:
1.3
NS
1.4
1.4
1.4
1.6
1.4
1.7
1.4
1.5
1.3
NS
2.0
1.8
(g) 18.2
3/1/84
0.6
NS
1.4
1.3
1.4
1.5
1.2
1.7
1.6
1.9
1.8
NS
1.9
1.5
17.8
0
NS
10
1
2
20
0
25
0.5
20
4
NS
15
20
C-35
-------
Census Division = SA, Age Group = 45 + Years, Composite 4
Semivolatile Volatile Approximate
FY 82 organic composite organic composite mass
specimen no. amount added (g) amount added (g) remaining (g)
8206955
8206948
8207045
8206997
8203945
5.3
3.3
3.0
4.9
1.1
4.5
0
2.6
4.5
0
0
0
0
0
0
Total composite (g) 17.6 11.6
Date composited: 3/1/84
C-36
-------
Census Division = ES, Age Group = 0-14 Years, Composite 1
FY 82
specimen no.
Semi volatile
organic composite
amount added (g)
Volatile
organic composite
amount added (g)
Approximate
mass
remaining (g)
8200628
8200636
8200685
8200792
8200800
8200867
8201881
8201915
8204190
8204208
8204216
8204273
8204497
8200677
8200768
8200883
8201923
8201931
8204174
8204182
8204224
8204240
8204257
8204406
8200560
8204299
0.8
0.6
2.2
0.8
1.0
0.8
0.8
0.6
0.7
1.0
1.4
0.9
1.1
0.5
0.8
1.2
1.0
1.6
1.5
1.5
1.1
1.0
1.3
1.2
1.1
1.6
0
0.8
0.6
0.6
0.9
0.8
1.9
0.6
1.0
1.2
1.0
1.0
1.0
0.6
1.8
1.1
1.2
1.2
1.1
1.4
1.1
0.8
1.3
0.7
0.8
1.1
0
2
2
1
5
2
2
2
2
1
1
1
2
2
2
2
3
0
2
1
2
2
2
2
2
2
Total composite (g) 28.1
Date composited: 2/29/84
25.6
C-37
-------
Census Division = ES, Age Group = 15-44 Years, Composite 1
FY 82
specimen no.
Semi volatile
organic composite
amount added (g)
Volatile
organic composite
amount added (g)
Approximate
mass
remaining (g)
8200586
8200727
8201865
8204232
8204281
8204430
8204554
8200610
8200719
8200818
8201873
8204265
8204307
8204323
8200750
8204489
Total composite (g)
1.2
1.3
1.3
1.0
1.3
1.0
1.3
1.1
1.7
1.1
1.3
1.0
1.3
1.4
1.5
1.1
19.9
1.1
1.2
1.3
1.4
1.1
1.1
1.5
1.0
0.3
1.2
1.2
1.1
1.2
1.4
1.4
1.5
19.0
20
6
6
2
4
3
3
4
4
10
10
3
2
4
5
5
Date composited: 2/29/84
C-38
-------
Census Division = ES, Age Group = 45 + Years, Composite 1
FY 82
specimen no.
8200644
8200669
8200735
8204398
8204414
8204448
8204455
8204463
8204513
8200552
8200776
8200784
8200834
8200875
8204422
8204521
8204547
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
1.1
1.2
1.1
1.2
1.4
1.3
1.4
1.2
1.2
1.2
1.1
1.4
1.4
1.0
1.2
1.2
1.1
(9) 20.7
2/29/84
Volatile
organic composite
amount added (g)
1.3
1.2
1.0
1.4
1.4
1.3
1.0
1.2
1.2
1.1
1.0
1.6
1.2
1.0
1.2
1.2
1.3
20.6
Approximate
mass
remaining (g)
5
4
2
2
2
2
2
2
2
2
3
4
5
2
2
2
3
C-39
-------
Census Division = ES, Age Group = 15-44 Years, Composite 2
FY 82
specimen no.
8200578
8200594
8200529
8200693
8200826
8204315
8204331
8204356
8204539
8204372
8200743
8200859
8200891
8201899
8204349
8204364
8204380
Total composite
Semi volatile
organic composite
amount added (g)
1.5
1.2
1.9
0.9
1.7
1.7
1.7
1.5
2.2
1.9
1.8
1.4
0.5
1.5
1.5
1.2
1.6
(g) 25.7
Volatile
organic composite
amount added (g)
1.5
0.7
2.0
2.0
1.6
1.6
1.6
1.3
1.6
2.0
1.1
1.4
0.1
1.4
1.7
1.2
1.5
24.3
Approximate
mass
remaining (g)
5
0
10
0
4
2
2
2
1
2
5
5
5
5
2
2
2
Date composited: 3/1/84
C-40
-------
Census Division = ES, Age Group = 45 + Years, Composite 2
Semi volatile Volatile Approximate
FY 82 organic composite organic composite mass
specimen no. amount added (g) amount added (g) remaining (g)
8200537
8200602
8200651
8200701
8200842
8200545 '
8204471
8204505
8204562
2.2
1.9
2.1
2.6
2.4
2.1
2.5
2.9
2.4
2.3
1.8
1.9
2.4
3.4
2.0
1.8
1.6
2.1
4
1
4
5
6
4
2
1
2
Total composite (g) 21.1 19.3
Date composited: 3/1/84
C-41
-------
Census Division = WS, Age Group = 0-14 Years, Composite 1
FY 82
specimen no.
8202848
8206773
8206781
8206799
8202798
8202897
8286757
8206807
8206849
8202889
8206732
8206755
8206823
8206815
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
1.2
1.1
0.3
0.6
1.8
1.2
1.2
0.3
0.5
NS
0.4
0.7
1.3
0.5
(g) n.i
2/29/84
Volatile Approximate
organic composite mass
amount added (g) remaining (g)
1.2
1.1
0
0
1.6
1.4
0.7
0
0
NS
0
0
0
Q
6.0
2
0
0
0
3
3
0
0
0
NS
0
0
0
0
C-42
-------
Census Division = WS, Age Group = 15-44 Years, Composite 2
FY 82
specimen no.
Semi volatile
organic composite
amount added (g)
Volatile
organic composite
amount added (g)
Approximate
mass
remaining (g)
8202640
8202723
8202772
8202988
8206625
8206690
8206708
8202665
8202756
8202780a
8202806
8202939
8206583
8206617
8206633
8206658
8202863
8202970
8202921
8202889
1.7
0.9
1.0
1.5
0.9
0.8
1.8
1.2
1.7
a
1.3
1.1
1.5
1.0
1.2
1.1
0.9
1.0
1.1
1.0
1.3
0.8
0.8
1.1
1.4
1.7
1.2
0.9
1.0
a
1.2
1.7
1.4
1.6
1.0
1.0
1.1
1.0
1.3
0.9
25
3
1
8
25
8
15
25
0
a
1
4
25
20
15
15
15
5
5
20
Total composite (g) 22.7
Date composited: 2/29/84
22.4
Sample included in the 45 + composite.
C-43
-------
Census Division = WS, Age Group = 45 + Years, Composite 1
FY 82
specimen no.
8202681
8202699
8202749
8202814
8202830
8206450
8206500
8206526
8206724
8202657
8202673
8202707
8202715
8202731
8202855
8206484
8206534
8206542
8206567
8206716
8206641
8206609
8202780
Total composite
Date composited:
Semivolatile Volatile
organic composite organic composite
amount added (g) amount added (g)
0.8
0.9
1.1
0.8
0.9
0.9
0.9
1.0
1.1
1.2
0.9
0.9
0.9
1.1
0.9
1.3
1.0
1.1
0.9
0.9
0.9
1.0
1.0
(g) 22.4
2/29/84
0.8
0.9
1.0
0.8
1.0
1.1
1.0
0.8
0.9
1.0
1.0
1.0
0.8
0.9
0.9
1.4
0.9
1.0
0.8
1.0
1.0
1.0
1.0
22.0
Approximate
mass
remaining (g)
4
9
8
3
5
5
5
5
10
8
8
5
8
5
4
8
9
10
10
8
9
8
8
C-44
-------
Census Division = WS, Age Group = 15-44 Years, Composite 2
FY 82
specimen no.
8202764
8202962
8206476
8206492
8206575
8206666
8206740
8202822
8202871
8202913
8202947
8206559
8206591
8206674
8206682
8202954
8202996
8206518
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
1.2
1.0
1.2
0.7
1.1
1.2
1.1
1.3
1.1
1.4
1.6
0.9
1.3
1.1
1.5
1.9
0.9
1.4
(9) 21.9
3/1/84
Volatile
organic composite
amount added (g)
1.8
1.3
0.9
1.0
1.1
1.0
0.8
1.7
1.6
1.5
1.3
0.9
1.1
1.2
1.4
1.3
1.0
1.0
21.9
Approximate
mass
remaining (g)
5
10
10
10
10
10
10
1
5
5
10
10
5
10
10
5
10
5
C-45
-------
Census Division = MO, Age Group = 0-14 Years, Composite 1
Semivolatile Volatile Approximate
FY 82 organic composite organic composite mass
specimen no. amount added (g) amount added (g) remaining (g)
8110199
8110207
8110256
8110272
8110116
8206468
8110157
0.8
2.6
1.0
0.2
2.4
1.3
0.7
0
2.4
0
0
2.7
0
0
0
1
0
0
8
0
0
Total composite (g) 9.0 5.1
Date composited: 2/29/84
C-46
-------
Census Division = MO, Age Group = 15-44 Years, Composite 1
FY 82
specimen no.
8110090
8110124
8110215
8110231
8110306
8110397
8204067
8204083
8204158
8110108
8110132
8110165
8110249
8110348
8110363
8110371
8110488
8204075
Semi volatile
organic composite
amount added (g)
1.4
1.3
1.3
1.4
NS
NS
1.5
1.7
1.8
1.3
2.0
1.4
1.8
NS
NS
NS
NS
1.4
Volatile
organic composite
amount added (g)
1.4
1.2
2.1
1.4
NS
NS
1.5
1.2
1.5
1.3
1.5
1.4
2.8
NS
NS
NS
NS
1.5
Approximate
mass
remaining (g)
6
1
15
10
NS
NS
7
10
15
10
2.0
5
0
NS
NS
NS
NS
10
Total composite (g) 18.3
Date composited: 2/29/84
18.8
C-47
-------
Census Division = MO, Age Group = 45 + Years, Composite 1
FY 82
specimen no.
8110140
8110173
8110181
8110330
8110421
8110439
8110454
8110462
8204117
8204133
8204141
8204166
8110264
8110280
8110298
8110322
8110389
8110447
8110470
8204109
8204125
Total composite
Date composited:
Semi volatile
organic composite
amount added (g)
2.0
2.0
2.2
NS
NS
NS
NS
NS
2.0
2.1
2.1
2.2
2.1
NS
NS
NS
NS
NS
NS
2.2
2.1
(g) 21.0
2/29/84
Volatile
organic composite
amount added (g)
2.2
2.7
2.0
NS
NS
NS
NS
NS
2.1
2.0
2.1
2.0
2.6
NS
NS
NS
NS
NS
NS
2.2
2.5
22.4
Approximate
mass
remaining (g)
5
0.5
4
NS
NS
NS
NS
NS
5
5
5
4
5
NS
NS
NS
NS
NS
NS
5
5
C-48
-------
TECHNICAL REPORT DATA
(Pfcese read tusoiicaons on the reverse before completing)
aSPORT iNO.
EPA-560/5-86-036
I 2-
3. RECIPIENT'S ACCSSSlONปNO.
4. riTU= ANQ SU8T1TUS
Broad Scan Analysis of Human Adipose Tissue
Volume II - Volatile Organic Compounds
S. PERFORMING ORGANIZATION COOS
Midwest Research Institute
5. REPORT OATS
December 1986
7. AUTHQR(S)
John S. Stanley
3. PERFORMING ORGANIZATION REPORT NO.
8821-A(01)
9. PERFORMING ORGANIZATION NAME ANO AOORSSS
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
10. PROGRAM ELEMENT NO.
11. CONTRAC7/GRANTNO.
68-02-3938
68-02-4252
12. SPONSORING AGENCY NAME ANO AOOB6SS
U.S. Environmental Protection Agency
Office of Toxic Substances
Field Studies Branch (TS-798)
Desiqn Development Branch/Exoosure Evaluation Division
401 M Street. SW
Ulaeh-i nn+nn nC. 7n/lฃn
18. SUPPUEMENf AR Y NOTES
J. Remmers and P. Robinson, Work Assignment Managers
J. Breen and C. Stroup, Program Managers
13. TYPS OP REPORT ANO PERIOD COVER6O
Final
1*. SPONSORING AGENCY coos
16. ABSTRACT
The U.S. EPA's Office of Toxic Substances (OTS) maintains a unique capability
for monitoring human exposure to potentially toxic substances through the National Human
Adipose Tissue Survey (NHATS). The primary focus for NHATS has been to document trends
in human exposure to environmentally persistent contaminants, specifically organochlor-
ine pesticides and polychlorinated biphenyls (PCBs).
EPA/OTS has recognized a need to expand the use of the NHATS program to pro-
vide a more comprehensive assessment of toxic substances that are accumulated in adipose
tissue. This report deals specifically with the measurement of volatile organic chemi-
cals in composited adipose tissue specimens from the FY82 NHATS repository.
Quantitative data are reported for 17 specific volatile compounds that are
classified as aromatic, chlorinated aromatic, or halogenated aliphatic. The frequency
of detection of each compound based on age group (0-14, 15-44, and 45 plus years) are
detailed in the report. The analytical procedures and QA/QC efforts are also described.
17.
GN 3TA7SMSNT
Release unlimited
SPA rorm 222Q.I (9-73)
19. SECURITY CLASS . T'nu degorti
Unclassified
21.
188
1 20. SECURITY C'-ASS i f?iu ou%ei
Unclassified
------- |