Of>'~e of
Tovc Substances
VV,/i>ngton DC 20461.'
EPA-560/5-86-03/
December, 1986
BROAD SCAN ANALYSIS OF THE FY82
NATIONAL HUMAN TISSUE SURVEY
SPECIMENS
VOLUME III - SEMI-VOLATILE ORGANIC
COMPOUNDS
?• East North
-^Atlantic
/East
| South*
) Central
L—,
West South Centra!
-------
BROAD SCAN ANALYSIS OF HUMAN ADIPOSE TISSUE:
VOLUME III - SEMIVOLATILE ORGANIC COMPOUNDS
By
John S. Stanley
FINAL REPORT
EPA Contract No. 68-02-4252
Work Assignment No. 21
MRI Project No. 8821-A(01)
Prepared For:
National Human Monitoring Program
Field Studies Branch (TS-798)
Design and Development Branch
Office of Toxic Substances
,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 J. Breen and Ms. Cindy Stroup, Program Managers
U.S. Environmental Protection Agency
230 South Dearborn Street
Chicago, Illinois 60504
-------
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.
-------
PREFACE
This executive summary is the third of a five-volume series that
details the broad scan chemical analysis of composite adipose tissue samples.
These composite 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 analyses of the
composite samples for general semivolatile organic compounds. Volume I pro-
vides a synopsis of all analytical efforts compiled under the broad scan
analysis program. Volume II deals specifically with the chemical analysis
of the NHATS composites. Volumes IV and V are for general volatile organics,
polychlorinated dibenzo-p_-dioxin (PCDD) and dibenzofurans (PCDF), and trace
elements, respectively. The statistical analyses of the data reported in
these volumes will be reported separately by the EPA's Office of Toxic Sub-
stances (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 (PCDDs) and
polychlorinated dibenzofurans (PCDFs). EPA 560/5-86-038.
Stanley JS, Stockton RA. 1986. Broad scan analysis of human
adipose 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. Ruth Blair, Ms. Kathy Boggess, and
Mr. Jon Onstot. The compositing scheme used to prepare the samples from the
NHATS repository was provided by Dr. Gregory Mack, Battelle Columbus Labora-
tories, under contract to the EPA/OTS Design and Development Branch (Mr. Phillip
Robinson, Task Manager and Ms. Cindy Stroup, Program Manager).
MIDWEST RESEARCH INSTITUTE
'
;s~, ! /
raV^fX^/^T"
Vaul C. Constant *
n E. Going
Director Program Manager
Chemical Sciences Department
iii
-------
TABLE OF CONTENTS
Executive Summary xiii
I. Introduction 1
A. Broad Scan Analysis Strategy 1
B. Work Assignment Objectives 2
C. Organization of This Report 2
II. Recommendations 2
III. Experimental 3
A. Collection and Storage of NHATS Specimens 3
B. Sample Compositing Activity 4
C. Broad Scan HRGC/MS Analysis Procedures 5
1. Selection of Analytical Methods/Target
Analytes 5
2. Method Summary 9
3. Reagents and Standards 10
4. Preparation of Glassware 12
5. Extraction, Cleanup, and Concentration .... 12
6. Lipid Determination 12
7. Gel Permeation Chromatography (GPC) 12
8. Florisil Fractionation 13
9. HRGC/MS Analysis 13
10. Quality Assurance/Quality Control (QA/QC). . . 15
11. Data Interpretation 15
12. HRGC/Selective Detector Screening 19
C. Toxaphene Analysis 20
1. Carbon Adsorbent Chromatography 20
2. Florisil Column Fractionation 21
3. HRGC/MS-SIM Analysis 22
D. Method Validation 22
1. Broad Scan HRGC/MS Analysis 22
2. Toxaphene Analysis 26
IV. Results 26
A. Broad Scan Analysis 26
1. HRGC/MS 26
2. HRGC/ECD Analysis 104
B. Toxaphene Analysis 113
-------
TABLE OF CONTENTS (Continued)
VI. Quality Assurance/Quality Control 118
A. Spiked Tissue Samples 118
B. Spiked Blanks 118
C. Porcine Fat 125
D. Replicate Analyses 125
E. Method Blanks 129
F. Surrogate Compound Recovery 129
G. Internal Standard Response 134
VI. References 134
Appendix A - NHATS FY82 Composite Sample Data Reported for All
Target Compounds Within a Census Division 139
VI
-------
LIST OF FIGURES
Number Page
1 GPC elution profiles of selected biogenic compounds
and environmental contaminants (Ribick et al, 1982) ... 8
2 Flow scheme for analysis of semi volatile organic com-
pounds in human adipose tissue 10
3 GPC chromatogram of elution of (A) 0.9 g lipid; (B)
0.3 g lipid; and (C) 0.1 g lipid 14
4 Separation of PCBs from toxaphene using Florisil (1.25%
deactivated) fractionation 29
5 Separation of toxaphene from PCBs using Florisil (1.25%
deactivated) fractionation 30
6 Incidence of detection of semi volatile organic compounds
determined in composited human adipose tissue from the
West Census Region 31
7 Incidence of detection of semivolatile organic compounds
determined in composited human adipose tissue from the
Northeast Census Region 32
8 Incidence of detection of semivolatile organic compounds
determined in composited human adipose tissue from the
North Central Census Region 33
9 Incidence of detection of semivolatile organic compounds
determined in composited human adipose tissue from the
South Census Region 34
10 HRGC/MS chromatograms of the 6% diethyl ether Florisil
fraction for the three age group composites (0-14,
15-44, and 45) from the Mountain (MO) census division . . 37
11 HRGC/MS chromatograms of the 15/50% diethyl ether Florisil
fraction for the three age group composites (0-14, 15-44,
and 45 plus) from the Mountain census division 38
12 Comparison of the HRGC/MS chromatograms of the 0-14 age
composites (6% diethyl ether Florisil fractions) from
three census divisions 39
13 Comparison of the HRGC/MS chromatograms of the 45 plus
age composites (6% diethyl ether Florisil fractions)
from three census divisions 40
VI 1
-------
LIST OF FIGURES (Continued)
Number Page
14 Comparison of the HRGC/MS chromatograms of the 0-14 age
composites (15/50% diethyl ether Florisil fractions)
from three census divisions 41
15 Comparison of the HRGC/MS chromatograms of the 45 plus
age composites (15/50% diethyl ether Florisil frac-
tions) from three census divisions 42
16 Selected ion plots for PCBs from HRGC/MS (scanning)
analysis of human adipose tissue 76
17 HRGC/MS and HRGC/ECD chromatograms of the 6% diethyl
ether Florisil fraction of the 45-plus age category
of the East South Central census division 105
18 HRGC/MS and HRGC/ECD chromatograms of the 15/50% diethyl
ether Florisil fraction of the 45-plus age category
of the East South Central census division 106
19 HRGC/ECD chromatogram from the analysis of the 6% diethyl
ether Florisil fraction of the three age group composites
from the East South Central (ES) census division 107
20 HRGC/ECD chromatogram from the analysis of the 15/50%
diethyl ether Florisil fraction of the three age group
composites from the East South Central census division. . 108
21 Comparison of the HRGC/ECD chromatograms of the 6%
Florisil fraction of the 45-plus age category of the
ES census division and the elution of the surrogates
and internal standards 109
22 Comparison of the HRGC/ECD chromatograms of the 6%
Florisil fraction of the 45-plus age category of the
ES census division and the elution of PCBs as a mix-
ture of Aroclors (1016, 1254, 1260) 110
23 Comparison of the HRGC/ECD chromatograms of the 6%
Florisil fraction of the 45-plus age category of the
ES census division and the elution of a commercial
mixture (Supelco) of pesticides Ill
24 HRGC/ECD chromatograms of method blanks from 6% and
15/50% Florisil fractionation 112
vm
-------
LIST OF FIGURES (Continued)
Number
25
26
27
28
Total ion chromatogram for the HRGC/MS full scan analysis
of a 0.90 ug/uL standard of toxaphene using a 30-m DB-5
fused silica column temperature programmed from 60°C
(2-min hold) to 340°C at 10°C/min
Mass spectrum for scan no. 756 from the total ion
chromatogram from Figure 25 (toxaphene standard).
ion
Mass spectrum for scan no. 825 from the total —
chromatogram from Figure 25 (toxaphene standard). .
Selected ion current plots of characteristic fragment
ions for toxaphene from an HRGC/MS-SIM analysis . .
Page
114
115
116
117
-------
LIST OF TABLES
Number Page
1 Demographic Characteristics for the FY82 NHATS Composites -
Semivolatile Organic Analysis 6
2 Characteristic Masses and Intensities for the Qualitative
Identification of the Semivolatile Target Analytes and
Chromatographic Conditions 16
3 Summary of Average Recoveries of Specific Analytes from
Triplicate Analyses of Spiked Lipid (Human Adipose)
Samples 24
4 Recoveries of Toxaphene from Carbon/Glass Fiber Adsorbent
Column 27
5 Recovery of Toxaphene from Florisil Cleanup 28
6 Incidence of Detection of Selected Semivolatile Organic
Compounds in the NHATS FY82 Composite Specimens 36
7 Data Report - Beta-BHC (CAS No. 319-85-7) - FY82 Composite
Adipose Tissue Samples 43
8 Data Report - p_,p_'-DDE (CAS No. 72-55-9) - FY82 Composite
Adipose Tissue Samples 45
9 Data Report - p_,E'-DDT (CAS No. 50-29-3) - FY82 Composite
Adipose Tissue Samples 47
10 Data Report - Mirex (CAS No. 2385-85-5) - FY82 Composite
Adipose Tissue Samples 49
11 Data Report - trans-Nonachlor (CAS No. 39765-80-5) - FY82
Composite Adipose Tissue Samples 51
12 Data Report - Heptachlor Epoxide (CAS No. 1024-57-3) - FY82
Composite Adipose Tissue Samples 53
13 Data Report - Dieldrin (CAS No. 60-57-1) - FY82 Composite
Adipose Tissue Samples 55
14 Data Report - Polychlorinated Biphenyls (CAS No. 1336-36-3) -
FY82 Composite Adipose Tissue Samples 58
15 Data Report - Trichlorobiphenyl (CAS No. 25323-68-6) - FY82
Composite Adipose Tissue Samples 60
16 Data Report - Tetrachlorobiphenyl (CAS No. 26914-33-0) -
FY82 Composite Adipose Tissue Samples 62
-------
LIST OF TABLES (Continued)
Number
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
Data Report - Pentachlorobiphenyl (CAS No. 25429-29-2) -
FY82 Composite Adipose Tissue Samples
Data Report - Hexachlorobiphenyl (CAS No. 26601-64-9) -
FY82 Composite Adipose Tissue Samples
Data Report - Heptachlorobiphenyl (CAS No. 28655-71-2) -
FY82 Composite Adipose Tissue Samples
Data Report - Octachlorobiphenyl (CAS No. 31472-83-0) -
FY82 Composite Adipose Tissue Samples
Data Report - Nonachlorobiphenyl (CAS No. 53742-07-7) -
FY82 Composite Adipose Tissue Samples
Data Report - Decachlorobiphenyl (CAS No. 2051-24-3) -
FY82 Composite Adipose Tissue Samples
Data Report - 1,2-Dichlorobenzene (CAS No. 95-50-1) -
FY82 Composite Adipose Tissue Samples . .
Data Report - 1,2,4-Trichlorobenzene (CAS No. 120-82-1) -
FY82 Composite Adipose Tissue Samples
Data Report - Hexachlorobenzene (CAS No. 118-74-1) - FY82
Composite Adipose Tissue Samples
Data Report - Triphenyl Phosphate (CAS No. 115-86-6) -
FY82 Composite Adipose Tissue Samples
Data Report - Tributyl Phosphate (CAS No. 126-73-8) -
FY82 Composite Adipose Tissue Samples
Data Report - tris(2-Chloroethyl ) Phosphate (CAS No.
115-96-8) - FY82 Composite Adipose Tissue Samples ....
Data Report - Di ethyl Phthalate (CAS No. 84-66-2) - FY82
Composite Adipose Tissue Samples
Data Report - Di-n-butyl Phthalate (CAS No. 84-74-2) -
FY82 Composite Adipose Tissue Samples
Data Report - Di-n-octyl Phthalate (CAS No. 117-84-0) -
FY82 Composite Adipose Tissue Samples
Data Report - Butyl Benzyl Phthalate (CAS No. 85-68-7) -
FY82 Composite Adipose Tissue Samples
Page
64
66
68
70
72
74
77
79
81
84
86
88
90
92
94
96
XI
-------
LIST OF TABLES (Continued)
Number Page
33 Data Report - Naphthalene (CAS No. 91-20-3) - FY82 Com-
posite Adipose Tissue Samples 98
34 Data Report - Phenanthrene (CAS No. 85-02-8) - FY82 Com-
posite Adipose Tissue Samples 100
35 Compounds Not Detected in the FY82 Composite Specimens. . . 102
36 Summary of Toxaphene Identificaton in Composited
Adipose Tissue Specimens 119
37 Recovery Efficiency of Semivolatile Organics from Spiked
Human Adipose Tissues 120
38 Method Evaluation Experiments Percent Recovery (Spiked
Solvent Blanks) 121
39 Comparison of the Average Recovery Efficiency of Semi-
volatile Organics from Spiked Lipid Samples and Spiked
Blanks 123
40 Data Summary for the HRGC/MS Analysis of an EMSL/LV
QA/QC Spiked Porcine Adipose Sample (Adipose 121) .... 126
41 Data Summary for the Broad Scan Analysis of a Homo-
genized Bulk Lipid (Human Adipose) Sample 127
42 Summary of Surrogate Compound Recoveries (%) from the
FY82 Composited Human Adipose Specimens 130
43 Summary of Surrogate Compound Recoveries (%) from the
FY82 QA/QC Samples for Human Adipose 132
XT
-------
EXECUTIVE SUMMARY
The U.S. Environmental Protection Agency's Office of Toxic Substances
(EPA/OTS) maintains a unique program for monitoring human exposure to poten-
tially 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 primary focus
for NHATS has been to document trends in human exposure to environmentally
persistent contaminants, specifically organochlorine pesticides and polychlo-
rinated biphenyls (PCBs).
EPA/OTS has recognized the need to provide a more comprehensive
assessment of the toxic substances that accumulate in adipose tissue. The
NHATS specimens collected during fiscal year 1982 (FY82) were designated for
"broad scan analysis" to determine volatile and semi volatile organic com-
pounds and trace elements.
This volume of the final report deals specifically with the measure-
ment of semivolatile 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 semivolatile organic chemicals
in human adipose tissue and (2) to complete the analysis of the FY82 NHATS
specimens as composited for semivolatile organic compounds.
An analytical method for the broad scan analysis of human adipose
tissue for semivolatile organic compounds was identified and evaluated. The
analytical method is based on gel permeation chromatography, Florisil fraction-
ation, and high resolution gas chromatgraphy/mass spectrometry (HRGC/MS).
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 contractor, Battelle Columbus Laboratories. The composite samples repre-
sented the nine U.S. census divisions and three age groups (0-14, 15-44, and
45-plus).
Quantitative data for organochlorine pesticides, polychlorinated
biphenyls (PCBs), chlorobenzenes, phthalate esters, phosphate triesters, and
polynuclear aromatic hydrocarbons were determined for each composite. This
report details the frequencies of detection for each of the compounds by age
group and census division. The feasibility of determining other halogenated
aromatic compounds, including polybrominated biphenyls, polychlorinated ter-
phenyls, and polychlorinated diphenyl ethers, using this method was demon-
strated through the analysis of spiked adipose tissue samples. The quanti-
tative data for the target analytes described in this report have been sub-
mitted along with all supporting quality control data to Battelle Columbus
Laboratories for statistical analysis.
XT 11
-------
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).
This study represents a major step in the advancement of EPA's
National Human Monitoring Program to monitor exposure to toxic organic chem-
icals. The database for the number of xenobiotic organic compounds detected
in adipose tissue has been expanded. The predominant compounds noted are
organochlorine pesticides and PCBs, which have previously been monitored
through packed column gas chromatography/electron capture detection (PGC/ECD)
techniques. The HRGC/MS method provides an additional confidence level for
determination, however, since identification is based on matches of both re-
tention time and mass spectra. The detail on PCB levels is also expanded as
a result of identifying specific degree of chlorination (homologs) and pro-
viding quantisation of individual responses. Previous NHATS analyses for
PCBs based on the PGC/ECD method have resulted in semi quantitative data
based on a single response.
xiv
-------
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 (NHMP) 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 adi-
pose 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 toxic 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 col-
lected from autopsied cadavers and surgical patients according to a statistical
survey design (Lucas, Pierson, Myers, Handy 1981). The survey design ensures
that specified geographical regions and demographic categories are appropri-
ately 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. Histori-
cally, organochlorine pesticides and polychlorinated biphenyls (PCBs) have
been the compounds of interest.
A. Broad Scan Analysis Strategy
EPA/OTS recognized the need to provide a more comprehensive assess-
ment of the toxic substances that accumulate in adipose tissue. An aggres-
sive 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 chemicals and
trace elements (Mack, Stanley 1984).
The initiative to achieve a more comprehensive assessment of toxic
substances in human adipose tissue necessitates a modification of the exist-
ing analytical procedures. Data reported on NHATS specimens up to the FY82
collection are limited to organochlorine pesticides and PCBs based on packed
column gas chromatography/electron capture detector (PGC/ECD) analysis (Yobs
1971; Kutz, Yobs, Strassman 1976; Kutz, Sovocool, Strassman, Lewis 1976; Kutz,
Yoos, Strassman, Viar 1977; Kutz, Strassman, Sperling 1979; Sherma, Beroza
1980). Limited data have been reported for mass spectrometric analysis of
pooled NHATS specimen extracts for specific compound classes such as poly-
brominated biphenyls (PBBs) (Lewis, Sovocool 1982) and polychloroterphenyls
(PCTs) (Wright, Lewis, Crist, Sovocool, Simpson 1978).
-------
B. Work Assignment Objectives
The objectives of this work assignment were to (1) identify appropri-
ate analytical methods for a broad scan analysis of human adipose tissue based
on high resolution gas chromatography/mass spectrometry (HRGC/MS) detection;
(2) conduct preliminary evaluation of the analytical procedures; and (3) com-
plete the sample workup and analysis of 46 composite samples prepared from
the NHATS specimens collected during FY82.
The broad scan analysis approach based on HRGC/MS is necessary to
identify additional compounds that may be of concern to EPA under the mandates
of TSCA. The target detection range for analytes by the HRGC/MS method, as
specified in the current NHATS strategy (Mack, Stanley 1984), was 0.05 to
0.10 ng/g.
C. Organization of This Report
This report deals specifically with the application of the broad
scan analysis concept to determine semi volatile organic compounds in human
adipose tissue. Following this introductory section, Section II presents
recommendations for additional method development and routine application of
the concept. Section III is the experimental section and describes the ex-
perimental design, analytical procedures, and results of the preliminary
method evaluation studies. Section IV reports results of the HRGC/MS and
HRGC/selective detector analyses of the composited samples. Section V pre-
sents the results of an extensive quality assurance/quality control program
conducted along with the sample analysis. Section VI provides references.
Complete data reports of the HRGC/MS analysis by specific census division
are reported in Appendix A.
II. RECOMMENDATIONS
The analytical method described in this report and modified as rec-
ommended below should be fully validated through additional intra- and inter-
laboratory analyses. This effort is necessary to define the methods limita-
tions fully (accuracy, precision, limits of detection (LOD) and limits of
quantitation (LOQ), and quality control requirements for reporting valid data.
The LODs and LOQs for individual analytes should be determined experimentally
through replicate analysis of spiked tissue samples. The HRGC/MS and the
PGC/ECD methods should be evaluated using homogenized split samples to deter-
mine the comparability of data for the organochlorine pesticides and PCBs.
This effort is necessary to determine whether it will be possible to effec-
tively extend trend lines from the PGC/ECD data from previous NHATS analysis
programs.
Before proceeding with these validation and comparability studies,
however, the analytical method described in this report should be modified
to include at least two additional internal standards for quantitation. Sur-
rogate compounds that will fractionate in the more polar Florisil fractions
are necessary to fully evaluate method performance on a per sample basis.
Deuterated phthalate esters that are commercially available should be con-
sidered as surrogates in further evaluation of the analytical method.
-------
For continued broad scan analysis projects there is a need to estab-
lish sufficient characterized reference samples for use as quality control
samples. These QC samples should be available in quantities comparable to
the 20 g composited tissue samples. This type of QC sample could be developed
from lipid materials extracted from human adipose tissue. The lipid materials
should be thoroughly homogenized and the background levels of semivolatile
organic analytes established through replicate analysis. Once this reference
material has been characterized, it could be spiked with additional analytes
for positive documentation of method performance.
Additional method development effort is needed to achieve a more
expedient of removal bulk lipid from the samples. The current analytical
methodology, although effective, requires considerable time for preparation
of the samples.
Effort is also necessary in the area of developing HRGC/selective
detector analysis methods to provide data for target analytes on a routine
basis. Specifically, HRGC/ECD analysis of adipose tissue could provide data
on chlorobenzenes, organochlorine pesticides and specific PCB isomers. This
approach would require smaller sample sizes and result in more expedient
sample preparation while maintaining the necessary sensitivity to achieve
1-10 ng/g (ppb) detection levels. HRGC/selective detector analysis could
also be applied to monitoring of phosphate triesters on a routine basis.
Some consideration should be given to evaluation of alternate HRGC/
MS techniques including selecting ion monitoring (SIM), negative chemical
ionization mass spectrometry (NCI), and mass spectrometry/mass spectrometry
(MS/MS) to lower detection limits and increase specificity for compound
classes such as organochlorine pesticide, polychlorinated biphenyls, poly-
brominated biphenyls (PBB), polychlorinated terphenyls (PCT), polychlorinated
diphenyl ethers (PCDE), and polychlorinated naphthalenes (PCN).
III. EXPERIMENTAL
This section of the report describes:
A. collection and storage of NHATS speciments;
B. sample compositing activity;
C. broad scan HRGC/MS analysis procedure;
D. the analytical procedure for toxaphene analysis; and
E. preliminary method validation experiments.
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 chemi-
cals such as solvents, paraffin, disinfectants, preservatives, or plastics.
-------
The cooperators were given no specific instructions to avoid potential con-
tamination that might arise from background contribution (airborne levels)
of solvents or metals.
The adipose tissue specimens were sealed in glass jars and frozen
(-20°C) 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 (TAC) 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 (-20°C). 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 allowed
to reach room temperature. The specimen were stored on dry ice during this
process and were returned to a freezer (-20°C) once all individual specimen
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 specimen
was handled separately and each was subsampled for the composites for both
volatile and semivolatile organic analysis. 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
± 0.1 g on a Mettler open pan balance placed in the hood.
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.
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 200°C 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
(-20°C). 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.
The composite samples ranged from 9.0 to 28.1 g total mass with an
average mass of 20.9 g for the 46 composites. The amounts of each NHATS speci-
men added to a specific composite are detailed in Volume II of this report
series (Stanley 1986b). The demographic characteristics for each composite
(Table 1) were determined by BCL from the individual specimen data.
C. Broad Scan HRGC/MS Analysis Procedures
1. Selection of Analytical Methods/Target Analytes
a. Analytical Methods
The analytical methods that have been used to achieve the
analysis of human adipose tissue samples for specific xenobiotic compounds
have been previously reviewed (Cramer, Miller, Going 1981). The biggest con-
cern in establishing any analytical method for adipose tissue is removing the
bulk matrix without losing the target analytes. This has been achieved by
various approaches including liquid-liquid partitioning (acetonitrile/hexane),
chemical degradation (alcoholic potassium hydroxide saponification or concen-
trated sulfuric acid digestion), low temperature precipitation, adsorption on
calcium or cesium silicates, and separation of the analytes based on gel per-
meation chromatography (GPC).
GPC presents the most viable option of these analytical pro-
cedures for bulk lipid cleanup for the broad scan analysis concept. The ad-
vantage of GPC is its ability to separate xenobiotic materials (polar and
nonpolar) from the lipid matrix based on size separation. The application of
GPC for the separation and cleanup of lipid materials from biological (Tessari,
Griffin, Aaronson 1980; MacLeod, Hanisch, Lewis 1982; Ribick, Dubay, Petty,
Stalling, Schmitt 1982; Norstrom, Simon, Mulvihill 1986) as well as environ-
mental samples (Lopez-Avila, Haile, Goddard et al. 1981) has been previously
documented. Figure 1 is an example of the GPC separation of various compounds
and compound classes from fish lipids using GPC. Cleanup of lipids based on
the other options may result in low recoveries or the loss of the more polar
or labile molecules.
-------
Table 1. Demographic Characteristics for the FY8<
Semivolatile Organic Analysis'
NHATS Composites -
Census,
region
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NE
NE
NE
NE
NE
NE
NE
NE
NE
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
Census
division
EN
EN
EN
EN
EN
EN
EN
EN
WN
WN
WN
WN
MA
MA
MA
MA
MA
MA
NE
NE
NE
ES
ES
ES
ES
ES
SA
SA
SA
SA
SA
SA
SA
SA
SA
SA
Age ,
group
1
1
2
2
2
3
3
3
1
2
3
3
1
1
2
2
3
3
1
2
3
1
2
2
3
3
1
1
2
2
2
2
3
3
3
3
Composite
number
1
2
1
2
3
1
2
3
1
1
1
2
1
2
1
2
1
2
1
1
1
1
1
2
1
2
1
2
1
2
3
4
1
2
3
4
No. of
specimens
18
20
20
19
19
18
18
14
13
17
15
15
11
13
24
22
20
20
16
21
19
26
16
17
17
9
20
14
25
22
19
12
25
21
9
5
Percent
white
77.8
80.0
90.0
89.5
89.5
94.4
88.9
100.0
92.3
100.0
93.3
93.3
90.9
76.9
83.3
86.4
95.0
85.0
87.5
95.2
100.0
88.5
87.5
94.1
100.0
0.0
100.0
0.0
100.0
100.0
0.0
0.0
100.0
100.0
0.0
0.0
Percent
male
100.0
0.0
50.0
42.1
52.6
55.6
55.6
50.0
53.8
64.7
60.0
53.3
81.8
61.5
50.0
54.5
50.0
40.0
56.3
57.1
47.4
53.8
100.0
0.0
52.9
55.6
45.0
64.3
100.0
0.0
100.0
0.0
100.0
0.0
100.0
0.0
-------
Table 1 (continued)
Census,
region
S
S
S
S
W
W
W
W
W
W
Census
division
WS
WS
WS
WS
MO
MO
MO
PA
PA
PA
Age d
group
1
2
2
3
1
2
3
1
2
3
Composite
number
1
1
2
1
1
1
1
1
1
1
No. of
specimens
13
19
18
23
7
12
10
7
9
15
Percent
white
69.2
78.9
83.3
87.0
85.7
100.0
100.0
85.7
88.9
80.0
Percent
male
53.8
52.6
50.0
43.5
71.4
58.3
70.0
71.4
55.6
46.7
.Data provided by Battelle Columbus Laboratories.
NC = North Central, NE = Northeastern, S = South, W = West.
CEN = East North Central, WN = West North Central, MA = Middle Atlantic,
NE = New England, ES = East South Central, SA = South Atlantic, WS = West
.South Central, MO = Mountain, PA = Pacific.
Age group 1 = 0-14 years, age group 2 = 15-44 years, age group 3 = 45+ years.
-------
O
0)
" S 2
£ £ g
t * u
19 ~ • V _ w £
lMB| i
"~Kifx5'»S
• :^|i^l
¥ u,
a, $
P Ul
O
in
•s.
O
ur>
8 S
^ a
= * I
rf£ .
E
S s!
* >• *
" i s
~ s s
" o i
.2
eft
Ui
fp
X
(/)
s
u
^^^
o
" Illll
_u ••Ills
55 l"l*
CON. 1 IS
-r (M • -
X — • • *-
Ul X
• U)
(M O
in 2
C —
(X C
cr \
0 _)
_ c
o
u> in
§
8
S
8
8
?
8
•a
c
m
in
•a
o
o
u
u
a) in
r— -P
a) c
in ro
o s
(0
in -P
-------
Fractionating of the GPC eluate is necessary to elucidate the
most data from a complex sample. The characteristics of Florisil, which has
been used extensively for the PGC/ECD method, have been studied for numerous
compounds and compound classes (Sherma, Beroza 1980). The GPC bulk lipid
cleanup and the Florisil column fraction procedures were selected for the
preparation of the NHATS FY82 specimens based on their efficiency and appli-
cability to a large number of compound classes.
b. Target Analytes
A review of the published literature on the analysis of human
adipose tissues for environmental contaminants demonstrates that the majority
of the monitoring efforts have centered on the organochlorine pesticides and
PCBs (Biros, Walker 1970; Yobs 1971; Biros, Enos 1973; Burns 1974; Sovocool,
Lewis 1975; Kutz, Yobs, Strassman 1976; Kutz, Sovocool, Strassman, Lewis 1976;
Mes, Campbell 1976; Fukano, Doguchi 1977; Kutz, Yobs, Strassman, Viar 1977;
Jensen, Clausen 1979; Kutz, Strassman, Sperling 1979; Albert, Mendez, Ipn 1980;
Dougherty, Whitaker, Smith, Stalling, Kuehl 1980; Greer, Miller, Bruscato,
Hold 1980; Sherma, Beroza 1980; Abbott, Collins, Goudling, Hoodless 1981;
Barquet, Morgade, Pfaffenberger 1981; Lopez-Avila, Haile, Goddard et al. 1981;
Mes, Davies, Turton 1982; Wolff, Anderson, Selikoff 1982; Wolff, Thornton,
Fischbein, Lilis, Selikoff 1982; Wolff, Fischbein, Thornton, Rice, Lilis,
Selikoff 1982; Mori, Kikuta, Okinaga, Okura 1983; Mes, Davies, Turton 1985).
Additional studies have addressed the presence of phthalate
esters (Mes, Coffin, Campbell 1974; Mes, Campbell 1976); phosphate triesters
(LeBel, Williams 1983); polychlorinated aromatics including chlorophenols,
specifically pentachlorophenol (Sovocool, Lewis 1975; Wolff, Thornton,
Fischbein, Lilis, Selikoff 1982); polychloroterphenyls (Fukano, Doguchi
1977; Wright, Lewis, Crist, Sovocool, Simpson 1978; Watanabe, Yakushiji,
Kunita 1980); polybrominated biphenyls (Wolff, Anderson, Camper et al. 1979;
Lewis, Sovocool 1982; Wolff, Anderson, Selikoff 1982; Eyster, Kimbrough 1983);
and polynuclear aromatic hydrocarbons.
The presence of the PCTs and PBBs has been noted both in speci-
fic exposure scenarios and through the GC/MS analysis of pooled NHATS specimen
extracts from the previous analysis years (Wright, Lewis, Crist, Sovocool,
Simpson 1978; Lewis, Sovocool 1982).
The compound classes identified in human adipose tissue samples
were selected as the target analytes for initiating the broad scan analysis
concept into the NHATS program.
2. Method Summary
Figure 2 provides a schematic of the method for the broad scan
analysis of semi volatile organic compounds. The method requires compositing
specified adipose tissue specimens from the NHATS repository. Several stable
isotope labeled compounds are added to the tissue as surrogates. The spiked
adipose tissue sample is extracted with methylene chloride using a Tekmar®
Tissumizer. The extracts are filtered through anhydrous sodium sulfate. Ex-
tractable lipid is determined using approximately 1% of the resulting extract.
-------
Composite FY82 NHATS
Specimens (BCL Protocol)
Add Stable Isotope Labeled
Surrogate Compounds
Extraction - Tissumizer
Bulk Lipid Removal
Get Permeation Chromatography
10%
90%
Florisil Fractionation
HRGC/MS (Scanning)
0.01-O.l^.g/g
(PCBs, OCI Pesticide*. Etc.)
•AMOCO PX-21/
Glass Fiber
• Florisil
HRGC/MS (SIM) For
Specific Compound Class
(Toxaphene PCDD,- PCDF)
Quantitation/Dafa Transfer
to BCL
Figure 2. Flow scheme for analysis of semi volatile organic
compounds in human adipose tissue.
10
-------
The extract is concentrated, and the lipid is separated from organic analytes
using GPC. The GPC-cleaned extracts are concentrated and then fractionated
using Florisil. The Florisil fractions are concentrated, spiked with an in-
ternal quantisation standard, and analyzed by HRGC/MS (scanning). The method
is applicable to the determination of organochlorine pesticides, PCBs, PBBs,
PCTs, polychlorinated diphenyl ethers (PCDEs), chlorobenzenes, PAHs, phthalate
esters, and phosphate esters.
3. Reagents and Standards
a. Solvents
Methylene chloride and hexane were obtained as distilled in
glass quality (B&J). Diethyl ether was analytical reagent grade, peroxide
free. Absolute ethanol was added to the diethyl ether as a preservative/
stabilizer. This solution was prepared as 2% absolute ethanol (v/v). The
diethyl ether was tested for the presence of peroxides before use. A 1-mL
aliquot of a 10% potassium iodide solution was added to 10 ml of the diethyl
ether and the mixture was shaken. The presence of peroxides was noted by the
development of a yellow color. If no color change was observed, the lot of
diethyl ether was used for preparing the Florisil eluents.
b. Chromatographic Materials
The GPC system was prepared from Biobeads SX-3 (Bio-Rad Labora-
tories). Florisil (60/100 mesh) was extracted with methylene chloride over-
night in a Soxhlet apparatus. The extracted material was air dried and then
activated at 130°C for at least 24 h prior to use. The Amoco PX-21 charcoal
used for preparation of sample extracts for toxaphene analysis was obtained
from Dr. L. Smith of the Columbia National Fisheries Research Laboratory, U.S.
Fish and Wildlife Service, Columbia, Missouri.
Anhydrous sodium sulfate was extracted 24 h in a Soxhlet appa-
ratus with methylene chloride. The material was allowed to air dry and then
was placed in a muffle oven for 2 to 6 h at 650°C. The cleaned material was
stored in an oven at 130°C.
c. Analytical Standards
The organochlorine pesticides were obtained from the EPA Ref-
erence Materials Branch, Research Triangle Park. Toxaphene was obtained from
Supelco as a stock solution. The chlorobenzenes, chlorophenol s, PCBs, PBBs,
PCTs, PAHs, and phthalate esters were obtained from Ultra Scientific, Hope,
Rhode Island. The phosphate triesters were obtained from Chem Service Chemi-
cals, West Chester, Pennsylvania, and Aldrich Chemical Company, Milwaukee,
Wisconsin.
d. Surrogate Standards
The surrogate compounds naphthalene-d8, chrysene-d12, 13C6-
1,2,4,5-tetrachlorobenzene, 13C6-hexachlorobenzene, and 13C6-pentachlorophenol
were purchased from KOR Isotopes, Cambridge, Massachusetts. The carbon-13
11
-------
labeled PCBs were prepared from stock materials synthesized under EPA Contract
68-01-5915, Task 51 (Erickson, Stanley, Radolovich 1982). The carbon-13
labeled tetra- and octachlorodibenzo-g-dioxins were obtained from Cambridge
isotope laboratories (Woburn, MA).
4. Preparation of Glassware
All glassware was washed with soap and water, and then rinsed sequen-
tially with tap water, distilled water, acetone, and hexane. Both organic
solvents were distilled in glass quality (B&J).
5. Extraction, Cleanup, and Concentration
Frozen composited adipose tissue specimens (^ 20 g) were placed in
2.2 x 15 cm culture tubes. Each composited adipose tissue specimen was spiked
with several surrogate compounds including napthalene-d8 (2 ug); chrysene-d12
(2 |jg); 13C6-l,2,4,5-tetrachlorobenzene (2 ug); 13C6-4-chlorobiphenyl, 13C12-
3,3',4,4'-tetrachlorobiphenyl (4 ug); 13C12-2,2',3,3',5,5',6,6'-octachloro-
biphenyl (8 ug); 13C12-decachlorobiphenyl (10 ug); 13C12-2,3,7,8-tetrachloro-
dibenzo-p-dioxin (1 ng); and 13C12-octachlorodibenzo-p_-dioxin (5 ng). The
spiked adipose tissues were allowed to equilibrate to room temperature and
were homogenized for approximately 1 min with a Tekmar® Tissumizer (Tekmar
18-EN probe) with at least five successive aliquots (10 ml) of methylene chlo-
ride (B&J, distilled in glass). The methylene chloride extracts were dried
by passage through anhydrous sodium sulfate. The sodium sulfate column was
rinsed with enough methylene chloride to bring the final extract volume to
100 ml.
6. Lipid Determination
The extractable lipids were determined by removing a 1.0-mL aliquot
from the final extract. This aliquot was placed in 2-dram vial preweighed to
the nearest 0.0001 g, and solvent was removed using purified nitrogen and a
heated water bath. The vial was reweighed to the nearest 0.0001 g, and the
lipid content was determined using the weight difference.
7. Gel Permeation Chromatography
The remaining extract was concentrated by Kuderna-Danish evapora-
tion. The final volume was adjusted such that the solution contained approx-
imately 0.3 g of lipid per mL. An ABC Autoprep GPC with an automated sampling
valve (23 5-mL sample loops) was used for all bulk lipid separations. GPC
columns were prepared with approximately 60 g of Biobeads SX-3 swelled in
methylene chloride and packed as a slurry. The GPC was operated using methyl-
ene chloride at 5 mL/min under a pressure of 7-15 psi. The GPC columns were
calibrated using a solution of vitamin E-acetate which was monitored by a
preparative high pressure liquid chromatograph UV detector (Chromatronix Model
230) operated at 254 nm. Collection of the GPC effluent for the semivolatile
organic compounds was initiated as the response to the vitamin E-acetate
returned to baseline. The GPC columns were also calibrated using varying
amounts of lipid material spiked with a solution of the surrogate spiking
12
-------
solution. Figure 3 is an example of the GPC elution of varying amounts of
lipid material versus the surrogate standards. Approximately 0.9-1.0 g of
lipid material was added to each sampling loop of the GPC system. The GPC
effluents for a single sample were combined and concentrated and taken through
the GPC procedure a second time (two to three sample loops as necessary) to
remove additional lipid materials. Additional detail in the GPC procedure
have been reported previously (Stanley 1985).
8. Florisil Fractionation
Florisil columns (12.5 g, 60/100 mesh, activated at 130°C) were
packed in hexane. Anhydrous sodium sulfate was added to the top of each col-
umn. The GPC extracts were concentrated and exchanged to hexane (final volume
approximately 5 mL). This extract was added to the top of the Florisil column
and eluted with 200 mL each of 6%, 15% and 50% diethyl ether in hexane. The
6% fraction was collected separately from the 15% and 50% fractions and was
concentrated and solvent exchanged to hexane using Kuderna-Danish evaporation.
The 15 and 50% eluates were combined, concentrated, and solvent exchanged to
hexane. When the eluents had concentrated to approximately 5 mL, they were
further concentrated to 1 mL under a gentle stream of dry nitrogen. The
fractions were transferred to 1-mL conical vials and concentrated again to a
final volume of 200 pL using flowing prepurified nitrogen. All extracts were
stored in a refrigerator until analyzed by HRGC/MS.
9. HRGC/MS Analysis
The semivolatile organic analyses were accomplished with a Finnigan
MAT 311A double focusing magnetic sector mass spectrometer. Separation of
the semivolatile organic analytes was achieved using a 30 m x 0.25 mm Durabond
DB-5 (J&W Scientific, Rancho Cordova, California) fused silica column. The
sample extracts were injected through a Grob-style splitless injector. The
gas chromatograph was held isothermally at 60°C for 2 min, then programmed at
10°C/min to a final temperature of 310°C. The ion source was operated at 70
eV. A mass range of 80-550 amu was repetitively scanned every 1.7 s. Mass
spectra were acquired and stored using a Finnigan-Incos 2300 data system.
As part of the daily quality assurance/quality control (QA/QC) pro-
cedures, an analytical standard solution containing compounds representative
of the PCBs, PCTs, PBBs, PCDEs, chlorobenzenes, chlorophenols, organochlorine
pesticides, phthalate esters, phosphate esters, PAHs, the surrogate compounds,
and the internal standard (anthracene-d10) was injected as a calibration stan-
dard and a check of the mass assignment. Response factors for individual com-
pounds were calculated relative to the internal standard (anthracene-d10).
The relative response factors (RRFs) were calculated as described below.
13
-------
Collection C/ci*
3 5 '0 '3 lO 25 ''O
GrC ^erann'on T*fn« ^
Figure 3. GPC chromatogram of elution of (A) 0.9 g lipid;
(B) 0.3 g lipid; and (C) 0.1 g lipid. The GPC column
contained 60 g of Biobeads SX-3 and was operated at
5 mL/min with methylene chloride with dump time of
25 min and collection of effluent from 25 to 60 min.
14
-------
Using injections of 1 to 2 pL of each calibration standard, the ob-
served peak height or area responses of the primary quantitation ion (Table 2)
for each target analyte and the internal standard were tabulated. The RRF
for each target analyte was determined from the following equation.
RRF = (ASC.S)/(A.SCS)
where A = area or peak height response for the primary quantitation ion of
s the target analyte
A. = area or peak height response for the primary quantitation ion
5 of the internal standard, anthracene-d10
C. = concentration of the internal standard (ng/(j|_)
C1S = concentration of the target analyte (ng/(jL)
o
10. Quality Assurance/Quality Control
The QA/QC procedures included analysis of method blanks, spiked re-
covery samples, replicate tissue samples, and spiked porcine fat (Adipose 121
prepared by EMSL-LV). These samples were prepared and analyzed with the ac-
tual adipose tissue samples. Additional detail on the preparation of these
samples is presented in Section V (Quality Assurance/Quality Control). In-
strumental QA/QC activities included daily instrument calibration, analysis
of at least one calibration standard to demonstrate sensitivity, consistency
of response factors, and verification of mass assignments. The area of the
internal standard d10~anthracene was recorded on a per sample basis as a means
of determining fluctuations in instrument sensitivity.
Other QA/QC procedures included daily verification of the GPC column
calibration. This was achieved using the vitamin E-acetate solution described
in the GPC procedure. The GPC collection cycle for the chlorobenzenes, PCBs
and PAH compounds was also verified by injecting an aliquot of the surrogate
spiking solution monitoring the response to the UV detector over the collec-
tion cycle (Figure 3).
11. Data Interpretation
The HRGC/MS data for each sample were interpreted with computer-
assisted quantitation routines. A mass spectral library and quantitation list
of the target analytes based on relative retention times and the primary char-
acteristic ion were used to search each data file.
a. Qualitative Identification
The automated search and quantitation routine identified posi-
tive responses based on the primary characteristic ion for each of the target
analytes. Table 2 provides a list of target analytes, surrogates, the primary
quantitation ions, and secondary ions used for compound characterization. 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.
15
-------
c
H H
•o
C
03
in
(LI
in
in
03
U
-P
in
•r-
i.
0)
-p
u
03
S-
03
.C
.
CM
Ol
03
1 —
in
C
0
•I—
-p
• 1—
-a
c
o
o
(J
f~
Q.
03
S-
0)
0
-P
(C
E
O
£-
C-5
"O
c
n3
1/5
0)
-P
>>
'm
•a:
o>
05
5-
03
1—
03
ai
E
QJ -P
c
-P 0
03 -r-
1— •p
a> c
+J
QJ
ce
^~\
N
"*\
E
in
0)
in
in
03
E
U
-P
1/5
S-
>•>
03
-o
0
(J
OJ
OO
v^
s_
03
E
•r—
J-
Q-
T3
C
^
0
a.
E
0
C_J
cnLOcnLO
LO
"*i«-^
rH
LO
co
CO
CO
^•M"'
LO
LO
oo
o
o
rH
CO
LO
CO
0)
-o
•I—
X
o
Q.
a>
i.
o
r—
f~
U
03
^_>
a.
/it
IU
rH rH
1 1
ID i — 1
<3" CM
rH rH
rH LO
LO ID
^••^ *««— S
O i — 1
r**- rH
Csl ^^
CSJ rH
00 Q}
S*M^ S"W*'/
^" Is"1*
r**- CD
CM *fr
O O
O O
rH rH
CM cn
I""*"- CD
CM <•
S-
o
p—
f~
u
c.
o
-z.
1
X in
o rr
i- 03
._. r
rH
1
cn
rH
rH
O
LO
^^
r^.
r^»
00
cn
cn
""•fc-^
LO
pN,
OO
o
0
rH
>**~S
OO
fv*.
oo
0)
c:
n3
T3
S-
o
t—
o
1
OOrHrHrHrHrHrHrHrH
I I I I I I I I I I
OOrHi—lOLOLOOOOIrH
OOOOrHrHrHrHrHrH
OOOOOCDOOOCD
OOOOOOOOOCD
cocMLOcncMiDcnooiDcn
in
GO
0
Q-
^
in
! —
]>«
r~
(U
^
a.
•i —
QQ
•a
CD
-p
03
f~
•r—
S-
0
r-~
^.
U
>1
o
a_
/~~^
in
S-
ai
E
O
in
• i —
oo
/ N
in
i-
cu
E
O
in
•r—
> — ' CM
1
O
S-
o
t-~
.c
(_)
o
c
o
s
rH
\^^/
1
O
£-
O
i—
^:
u
•'-
,^— ^
in
s-
d)
E
O
in
•i —
^«
CM
•— '
1
0
i.
o
1 —
f~
(_J
'1—
S-
^~"
in
i.
a>
E
O
in
•i—
CM
^~
•**^/
1
O
i.
o
^~
JZ
u
03
S-
+J
OJ
l~~
in
s_
QJ
E
O
in
• !—
ID
^~
>S^
1
O
S-
o
I—
^r
u
03
-P
c:
ai
°~
^
in
5-
,—
^-
CM
•***s
1
0
S-
o
1 —
.c
u
03
-P
^-^
in
s-
OJ
E
O
in
•i —
CM
i— 1
\^^
1
O
£-
O
^1
O
03
Q.-P
CD
:x:
U
°
/^^
in
S-
-------
^-^
TD
CU
3
C
'.J3
c
o
u
s~-'
CM
CU
X5
re
i—
re
CD
E
(U -P
-P 0
re •>-
r— -P
cu c
G£ CU
CU
C£
>,
re
-a
c
o
u
/-> CU
N OO
IO
ai
U)
10 >,
re i-
Ei (0
-a
u c
•i- O
•p o
10 CU
•r- CO
S-
0)
_t i
•T**
O
re
s-
re
XI
o >>
re
E
i-
Q_
•o
c
3
O
a.
E
O
O
O O CM O
ID 00 00 0
0 0 0 r-l
1 1 1 1
ID in ID rH
oo in r-- cn
O 0 0 O
CM CT) rH rH
OO ^- ID in
s^^ ^^ \^^ v^/
^J- 00 00 CM
00 rH <* 00
rH CM CM CM
S~^\ ^"N /*""•% S^\
oo r- m CM
cn r-.. v_/s_^^
0 10 0 «*•
00 rH in 00
rH CM CM CM
/*• s
10
^"^ S—
i/> a>
s- E
0) 0
E 10
0 •!-
IO
•r- oo
> — ' IO
oo i-
10 *^s i i cu
CU O O 1 +->
C 1 i- S- O 10
0) O O O S- LU
N i- r— r— O
c o x: x: r— cu
00 rH
rH CO ?H CO ^t1
'Sfc-/ ^M*^ ^^^ ^w^ SM^
"^j" r***« cj r1*^ r*^
cn r^- m ID ID
i— 1 rH rH rH rH
0 0 0 O 0
O 0 O O O
rH rH rH rH rH
^ ^^ v»-< ^ V— '
oo cn cn cn cn
ID ^" ^J" *sj" ^"
rH rH rH rH rH
O)
4^
cu re cu
•P r— -P
cu re re re
•p cu > — xi i — in
03 .p re -P re i-
i — re xi xi xi cu
re F— +j CLP -P
+J XI O.r- Q- CU
XI P >> -r-
Q.XI r— N i— S-
0. >, C >, 1—
r— -p ,i— a xi o cu
XI >,X> 0 -P
-p x: i •— i re
cu -P c| >, c| x:
E CU I 4-} 1 O.
o a o CD o o
XI
a.
CM o oo oo r--
cn o oo «3- in
O rH rH rH rH
1 1 1 1 1
«D m CM ID ID
oo cn oo oo ^t
O O rH rH rH
ID o in CM r^
rH ID *$• OO r-»
\^/ \^s >*^s '^^/ t*^^
rH rH CT1 O 00
rH in O r-- ID
CM CM CM rH OO
/^^ ^"^ ^^^ ^^ /^*^
r~- in if> cn o
CM cn (D cn oo
^M^ V*-^ ^fc-' ^**/ ^^
m cn rH m in
m "sf cn CM i-
xi a. re 73
Q. x: >,
<^N O- HC
/~> i — IO
CU i— >> 0 CU 0
-P >> Q.XI +J T-
re xi o Q. re -P
xi +J i- x: re
Q. CU a.!— O. E
m o o >, 10 o
O i- S- XI O S-
XI 0 0 -P XI , s-
r— o u x i— re
>> 1 ••- O >v CU
•P CM Q -P r— r—
3 s_/v^« 3 0 U
xi to cn _a -P 3
i. i. i. i- i. >,
1— -P -P 1— r- •—
o
a.
CMlDCnP-^CMCMLniD
Lnr-~r^coocMCM^-
OOOOrHrHrHrH
1 1 1 1 1 1 1 1
ID CD OO rH p*^ ID CD CD
<3-r».r--cocnrHCM'3-
OOOOOrHrHrH
rH ID OO "st" 00 ^i" f*^- CM
rHrH^frHrHrHrHCM
S^^/ \^_^ ^^f/ \^s v^^ \*^S ^^/ s^^
r^^* oo CM f^** * Q^ f~^ t~~\ cn
CM un in ID r***" **^ f— ^ ^\j
rHrHrHrHrHrHrHCM
^"^N S*^\ /"^ l^^N /*^N /''^N ^^ /**N
CM r**" ID OO CD OO *D CM
rHrHOOOOrHCMCMCM
v^^ S^ / ^^^ N^V S^^/ S^X S^^ N^^
CT>i— lOOincnrHrHlD
CM tn m ID r*^ co CD CM
rHrHrHrHrHrHrHCM
OOOOOOOO
OOOOOOOO
rHrHrHrHrHrHrHrH
^•^•^^^^^^
OOCM^I-IDOOCMCMOO
CM in in ID r*** CD CD CM
rHrHrHi— IrHCMCMCM
CU
C
cu cu cu cu cu
c •— c c c
CD >, OJ CU CU
re x: xi t- xi
i — 4-> -p cu x: -P cu
re xi xi c -P c c
xzQ.o.cucrecucu
•preres-res-cio
xiccocoai>,
Q. CU CU 3 CU 3 S_ fi-
re U U r— XI r— >>XI
17
-------
/"• V
T3
01
C
*,—
•p
c
o
u
CM
CU
.a
ro
(—
n
cu
.J3
fO
"cu
ry»
^>
N
E
in
0)
in
in
(0
E
U
-p
in
«^-
s_
Ol
•p
o
(0
S-
(0
c~
t 1
3
01
-P
f
o
•r-
•P
c
-p
01
s-
(0
T3
O
(J
01
to
^>^
j_
rO
-o
C
o
u
0)
to
^>.
J_
m
E
•P*"
S_
Q_
T3
3
0
Q.
E
0
O
CM ID O O O ID I--
Lf) <- OO O OO ID ID
O rH O rH rH rH rH
1 1 1 1 1 1 1
ID O IT) rH O O rH
*sj" ^^ LO O*^ O"^ **J" t*O
O rH O O O rH rH
t*~*\ /•"*> /*** S~*\ S**\ /~"^. /"""-I
rH CM en rH CD ID 00
rH CM *i- ID «tfr ID ID
ID rH «3- 00 ID <*• 00
OO -st CM CO O «*• O
rH CM CM CM OO *t" If)
*^~\ ^^\ ^"X /*"•> /*"*s ^^> /"^s
CM CM f*» CM ID r»- Is--
rH CM f^- 00 f^-- 00 00
***S ^*S *^fS '***' Vrt^ ^^ X.^
r>- oo o «3- CM o CM
oo oo CM en o ** I-H
rH CM CM CM OO <• ID
/^-\ /"** ^% /*^ /^*N ^~N ^""N
000000 0
o o o o o o o
i-l rH rH rH rH rH H
• — •» — "• — ><^'^^>^^' - — •
ID O CM CM «3- CM O
oo ^~ CM en o ^~ i — t
rH CM CM CM OO *t in
"^
c
01
01 .c
c a.
O) T-
N J3
c o
OI i- 1
.a o -
o -— m •—
I- -C - >,
o 01 u in c
r- C fC - 0)
J= (U S- - i— JZ
O N -P *t >, Ci
rO C 0) - C -r-
in i- 01 1 — *J- CD J3
T3 -P J3 1 -JC O
C OIO--Q.S- T3
3 00 1 — S--^-OO'r-O J-
O ^D 1 O *"" ** f^ r^ fO
ca i NLD i — *t cv o £: ~o
EOlrH'.^l »S-U C
O C "O *sj" U — — O fl3 *0
CJOII -tOOOCMi — U -P
•— O> CM X --.CO) to
OI03C "OIOOCMOQ
-P JC O) rH ^ 1 1 03 1 i—
CO +-> in 1 1 M CM-*-> M (T3
CT^T >> W (0 rH rH U rH C
OQ-S-OCJOOOO S-
^ (0 *"" co CO CO CO CO OI
£- "Z. O rH rH rH rH rH 4->
3 C
to i— I
o
0
rH
^— -\
ID
rH
\^^
en
CO
rH
/^^
00
rH
^^
ID
00
rH
^-•N,
0
o
rH
* — '
00
00
rH
0
rH
^2J
|
OI
c
01
u
rO
s-
.c
-p
c
,
O S-
fO fO
t- E
JC. •!-
-p i-
C Q.
rO
OI
T3 -C
S- -P
(0
T3 O
C -P
ro
•P -P
in c
OI
i— U
rO ^*
£= ai
J- a.
ai
-p c
C •!-
cu
OI (/>
JC C
-P 0
Q.
in t/)
3 0)
in £-
S-
Ol >4-
> o
•a o
0) T-
-p -P
(0 ro
•— 5-
3
O in
1— -p
(0 U
U OI
r—
10 "4-
Ol OI
E 5-
•P U)
OI
C l«
0 0)
••- .c
-p -p
r~ r~
OI Ol
-P S-
O) ro
S- Q.
Ol C
> »| —
•r—
-P 01
rO 3
f— i —
O) (0
a: >
ro .a
18
-------
b. Quant Hat ion
Data were quantitated on the internal standard method. Table 2
presents the primary quantisation ions for each of the target analytes, surro-
gates, and the internal standard.
The HRGC/MS data were quantitated using the following equation:
AS x IS
Target Analyte, |jg = ^ x RRp
_L O
where A<- = area of the primary quantitation ion of the target analyte,
AT<- = area of the primary quantitation ion (m/z 188) of the internal
standard, anthracene-d10
IS = concentration of the internal standard in micrograms (ug), and
RRF = relative response factor of the target analyte versus the
internal standard.
The concentration (CWT) of the target analyte in the original
wet tissue sample was calculated by dividing the total micrograms of target
analyte detected by the total composite weight. In this report concentration
data are expressed as micrograms per gram (ug/g). The concentration data
(C.w) on a lipid basis were calculated by dividing the wet tissue concentra-
tion (C-,-r) by the measured percent lipid value.
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). Limit of detection (LOD) and limit of quantitation (LOQ) were
estimated based on the observed instrumental response for the specific target
analyte from the low level concentration standard from preliminary calibration
procedures.
Compounds detected for which the observed response of the char-
acteristic 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 ana-
lytes detected at greater than 10 times the background signal-to-noise are
reported as greater than the limit of quantitation (LOQ).
All data were corrected for blank values observed for the sys-
tem blank run with each set of samples.
12. HRGC/Selective Detector Screening
The HRGC/MS extracts from the composited tissue samples were also
analyzed by HRGC/electron capture detector (HRGC/ECD) as a means to screen
for response to additional compounds. The sample extracts were diluted 1 to
10 (10 uL of extract to 100 uL final volume in hexane). The HRGC/ECD analy-
sis was achieved using a 30 m x 0.25 mm DB-5 fused silica column. The analy-
sis conditions (injector operation and temperature program) were identical to
the parameters specified for the HRGC/MS analysis.
19
-------
C. Toxaphene Analysis
Following the broad scan HRGC/MS analysis, selected sample extracts
from the 45+ age category were taken through additional cleanup for analysis
by HRGC/MS selected ion monitoring (SIM) techniques. The cleanup procedure
required elution through a carbon adsorbent column followed by fractionation
on a deactivated Florisil column.
1. Carbon Adsorbent Chromatography
The carbon based cleanup described below is a modification of a pro-
cedure for the isolation of polychlorinated aromatics from biological samples
(Smith, Stalling, Johnson 1984).
a. Preparation of the Carbon/Glass Fiber Adsorbent
Whatman GF/D fiber filters (600 mg) were cut into small pieces,
suspended in approximately 70 ml methylene chloride and shredded with a Tekmar®
Tissumizer. Amoco PX-21 carbon (50 mg) provided by Dr. L. Smith, U.S. Fish
and Wildlife, Columbia, Missouri, was added to this mixture, and the grinding
was continued until the carbon was uniformly distributed on the fibers. This
mixture yielded the packing required for a single adsorbent column.
b. Preparation of the Adsorbent Column
Thick-walled, 1.0 cm i.d. precision bore glass tubes (6-cm
lengths) were custom fit with TFE plugs. These plugs were bored to accommo-
date 1/16 in. o.d. stainless steel tubing. This stainless steel tubing was
used to connect the columns to the solvent reservoir. Both ends of the column
were equipped with this stainless steel tubing to allow disconnection of the
column and inversion to change the direction of the solvent flow. To pack
the column, one end was fitted with a TFE plug. Four discs of glass fiber
filters (Whatman GF/D 1.0 cm diameter) were placed flush against the TFE plug.
The carbon/glass fiber mixture consisting of 600 mg glass fibers and 50 mg
carbon was added to the column in methylene chloride. A glass rod was used
to pack the mixture. After this mixture had been added to the column, four
discs of Whatman GF/D 1.0 cm diameter glass fiber filters were gently packed
on top of the carbon/glass fiber adsorbent. The second TFE plug was pushed
into place, compressing the adsorbent. The column bed height measured 3-4
cm. It is important that the carbon adsorbent is contained between the glass
fiber discs. Once prepared, the column can be reused indefinitely when
cleaned properly between samples.
c. Column Cleanup
Prior to sample cleanup, the column was washed with 100 ml of
toluene, followed by 100 mL methanol, and then 100 mL toluene again. The re-
sidual toluene was displaced with 150 mL cyclohexane/methylene chloride (50/50).
After this solvent had eluted through the column in reverse flow, the column
was inverted for forward flow. Immediately before sample application, an ad-
ditional 50 mL of the 50/50 solvent was eluted through the column with nitro-
gen pressure to remove any air pockets. In order to maintain a flow of 3-5
mL/min, a slight nitrogen pressure was necessary.
20
-------
d. Cleanup of Composite Sample Extracts
Following the broad scan HRGC/MS analysis, the 6% and 15/50%
diethyl ether/hexane extracts for the selected composites were combined and
diluted with 5 ml of the cyclohexane/methylene chloride (50/50) solvent. This
sample was added to the column reservoir and allowed to drain onto the column.
The sample vial and column reservoir were rinsed with two 5-mL portions of
the cyclohexane/methylene chloride (50/50) solvent. The flow rate was ad-
justed to 3-5 mL/min. After the last rinse, 75 mL of the (50/50) cyclohexane/
methylene chloride solvent was added to the reservoir. This was followed by
50 ml of methylene chloride/methanol/benzene (75/20/5). The flow of the col-
umn was then reversed by inversion of the column. The reservoir was filled
with 40 ml toluene. This fraction was collected from the column at a rate no
greater than 3-4 mL/min. A positive pressure on the system with nitrogen was
necessary to achieve this flow rate.
Each solvent that eluted through the carbon/glass fiber adsor-
bent was collected separately. The method evaluation studies described later
in this section demonstrated that toxaphene was eluted with the cyclohexane/
methylene chloride (50/50). The toluene fraction collected in the reverse
elution sequence was reserved for analysis of polychlorinated dibenzo-p_-
dioxins (PCDDs) and dibenzofurans (PCDFs). The methylene chloride/methanol/
benzene fraction was collected but was not targeted for specified compound
analysis.
2. Florisil Column Fractionation
Additional fractionation of the sample extract was necessary to
avoid interference problems that might arise from the presence of PCBs co-
eluted in the methylene chloride/cyclohexane fraction (50/50) from the carbon
adsorbent column. The Florisil fractionation procedure described below has
been previously reported for the separation of toxaphene from PCBs in biolog-
ical samples (Zell, Ballschmiter 1980).
a. Florisil Preparation
The Florisil was precleaned by methylene chloride extraction
for 13 h followed by oven activation at 130°C. For optimum separation the
Florisil was deactivated with 1.25% water. A portion of the Florisil was re-
moved from the oven and cooled to room temperature. The Florisil was weighed,
and the required amount of doubly distilled water was added. The Florisil/
water mixture was then tumbled on a mechanical roller allowing at least 3 h
for equilibration.
b. Preparation of the Chromatography Column
The column (260 mm x 17 mm) equipped with a TFE stopcock and a
250-mL solvent reservoir was packed with a small plug of glass wool and 13.0
g (± 0.1 g) Florisil (deactivated with 1.25% water) as a slurry in hexane.
Additional hexane was added to the reservoir and allowed to drain through the
Florisil. Slight tapping of the column helped to settle the Florisil and
eliminate air channels. When the hexane was within 1/4 in. of the Florisil,
the stopcock was closed.
21
-------
c. Elution Procedure
Ten milliliters of the methylene chloride/cyclohexane fraction
from the charcoal adsorbent column was exchanged to 1-mL hexane for applica-
tion to the Florisil column. The sample extract was transferred to the top
of the column directly onto the hexane. The extract was allowed to drain onto
the column. The sample vial was rinsed with two 2.5-mL portions hexane which
were each applied to the column separately and allowed to drain within 1/4
in. of the Florisil. The column was eluted with 55 mL of hexane followed by
50 ml of 10% diethyl ether in hexane. The 10% diethyl ether fraction was con-
centrated to less than 0.5 ml under a gentle stream of flowing prepurified
nitrogen and transferred. The final volume was transferred to 1.0 mL conical
vials. The extract was reduced just to dryness and reconstituted to 20 pL of
isooctane prior to HRGC/MS analysis.
3. HRGC/MS-SIM Analysis
Analysis of the sample extract was achieved using a Kratos MS50TC
double focusing magnetic sector mass spectrometer operated in the SIM mode.
The characteristic ions for toxaphene were determined from the full scan
analysis of a 90 ng/pL toxaphene standard. The results section of this report
demonstrates that the electron impact ionization of toxaphene results in com-
plex fragmentation pattern with no major ion of significant intensity. As a
result of the full scan analysis, nine ions (m/z 231, 233, 235, 269, 271, 273,
305, 307, 309) characteristic of toxaphene were used to monitor the response
from the extracts of 14 selected samples. A second HRGC/MS-SIM analysis of
three of the extracts using ions at m/z 305, 307, 309, 327, 329, 331, 341,
343 and 345 provided additional information on the presence of toxaphene.
Although higher masses were noted in the mass spectra from full scan analyses
of toxaphene, the response intensity was minimal. Hence, ions at masses
higher than m/z 345 were not included in the analysis scheme.
D. Method Validation
1. Broad Scan HRGC/MS Analysis
Two analytical procedures were initially evaluated for the analysis
of a wide range of organic compounds including organochlorine pesticides,
chlorobenzenes, PCBs, PBBs, PCTs, PCDEs, PAHs, PCDDs, PCDFs, phthalates, and
organophosphorous esters. Analytes representing the nine compound classes
were spiked at concentrations equivalent to 0.10 pg/g into six replicate lipid
samples of approximately 15 g each. The lipid used for the spiking procedures
was obtained from approximately 120 g of human adipose tissue. This adipose
tissue was extracted using methylene chloride and a Tekmar® Tissumizer. The
resulting extract was chromatographed with an ABC gel permeation chromatog-
raphy system using Biobeads SX-3 and methylene chloride following the condi-
tions previously identified. The lipid material eluting from the column was
collected separately from the specific xenobiotic analytes collected from this
material.
22
-------
One procedure required the use of approximately 200 g of Micro Cell
E (Johns Manville Corporation), a commercial calcium silicate adsorbent, to
remove bulk lipid material (Rogers 1972). The spiked lipid material was ad-
sorbed on the Micro Cell E (MCE), and the adsorbent was then extracted with
5% acetone/acetonitrile. The resulting extract contained 2 to 3 g of lipid
material, which required at most three passes through the GPC system. This
provided a distinct saving in the total time required for bulk lipid removal
for large samples.
The other procedure relied on elution of the entire lipid extract
through the GPC system as previously described. A minimum of 15 injections
were required for each of the spiked 15 g of lipid material. Fractionation
of the extracts from both bulk lipid removal procedures required Florisil
activated at 130°C and eluted with solvents of 6%, 15%, and 50% diethyl ether/
hexane.
The extracts were analyzed using either a 15-m or 30-m J&W DB-5 HRGC
column and the Finnigan MAT 311A double focusing mass spectrometer. A mass
range of 90-600 atomic mass units (amu) was scanned for the analysis of the
extracts. Both direct on-column and Grob type split/splitless injection sys-
tems were investigated for extract analysis.
The results of the method evaluation experiments are presented in
Table 3. The data represent the average recovery of the range of analytes
for triplicate analyses of spiked lipid using each procedure. Although the
method using Micro Cell E provided a distinct advantage in sample turnaround
time, the recoveries of the analytes were considerably less (approximately
50%) than recoveries achieved using only GPC for removal of bulk lipid.
Most of the analytes were eluted from the Florisil column in the 6%
diethyl ether/hexane fraction. The results of the method evaluation studies
indicated that the organochlorine pesticides (with the exception of dieldrin),
chlorobenzenes, PCBs, PBBs, PCTs, lower molecular weight PAHs and tetra- and
pentachloro-dioxins were eluted in the 6% diethyl ether hexane fraction from
the Florisil. Phthalates, phosphate esters, dieldrin, chlorophenols, higher
molecular weight PAHs, and hexa- and heptachlorodibenzo-p-dioxins were iden-
tified in the 15 and 50% diethyl ether hexane Florisil fractions. Some com-
pounds, including octa-dioxins and furans and some phosphate esters, were not
effectively recovered from Florisil.
An important aspect for the analysis of the sample extracts was
determined to be the selection of the injection technique for HRGC/MS. The
on-column injection technique required that the extract contain little or no
lipid material. On column injection of an extract containing lipid material
led to considerable broadening of peaks and poor chromatography. This in turn
affected the detection limit for the various compounds. The Grob style injec-
tor, however, provided much better chromatography and was determined to be
the technique of choice for the analysis of the composite samples.
23
-------
Table 3. Summary of Average Recoveries of Specific Analytes from
Triplicate Analyses of Spiked Lipid (Human Adipose) Samples
Analyte
GPC/Florisil
average
recovery (%)
MCE/GPC/Florisil
average
recovery (%)
Chlorobenzene
1,2-Di chlorobenzene
2,4-Dichlorophenol
1, 2, 4-Tri chlorobenzene
Naphthalene
2,4,6-Trichlorophenol
Acenaphthylene
Dimethyl phthalate
Acenaphthene
Pentachl orobenzene
13C-Monochlorobiphenyl
Fluorene
Di ethyl phthalate
4-Chlorodiphenyl ether
4-Bromobiphenyl
a-BHC
Hexachl orobenzene
tri s(2-Chl oroethyl )phosphate
p-BHC
Phenanthrene
A-BHC
Heptachlor
Di-n-butyl phthalate
Pentachl orophenol
Aldrin
4,4' -Dibromobiphenyl
2,4,6-Tribromobiphenyl
Heptachlor epoxide
Fluoranthene
o,p_'-DDE
Pyrene
Chrysene
trans-Nonachlor
p,p'-DDE
23
42
52a
62
65
63a
56
61a
74
66
73
72
140
77
81
97
80
ND
101°
91
108C
87
120
106C
102
86
126
92
99
102
87
98
98
120
5
24,
NDb
30
35
ND
26
4
40
36
42
45
150
40
56
74
36
ND
82
60
44
45a
125a
44
54
44a
56
52
58
64
55
65
57
69
24
-------
Table 3 (continued)
GPC/Florisil
average
Analyte recovery (%)
Dieldrin
13C12-Tetrachlorobiphenyl
o,p_'-DDD
£,E'-DDD
2,2' ,4,4' ,5-Pentachlorodiphenyl ether
tris(Dichloropropyl)phosphate
2,3,7,8-Tetrachlorodibenzofuran
Butyl benzyl phthalate
2,2' ,4' ,5-Tetrabromobiphenyl
p_,p_'-DDT
1,2,3, 4-Tetrachl orodi benzo-p_-di oxi n
Tributoxyethyl phosphate
4-Chl oro-£~terphenyl
2,5-Dichloroterphenyl
1 , 2-Benzanthracene
13C12~Octachlorobiphenyl
2,5-Dichloro-m-terphenyl
2,2' ,4,5' ,6-Pentabromobiphenyl
1,2,3, 7 ,8-Pentachl oro-£-di oxi n
Mi rex
2,2' ,4,4' ,6,6'-Hexabromobiphenyl
2,4' ,5-Trichloro-o-terphenyl
l,2,3,4,7,8-Hexachlorodibenzo-£-dioxin
Benzo-k-f 1 uoranthene
2,4,4' ,6-Tetrachl oro-o-terphenyl
13C-Decachlorobiphenyl
1,2,3,4,6,7, 8-Heptachl orodi benzo-p_-di oxi n
Decachlorodiphenyl ether
Octachl orodi benzo-p_-di oxi n
Octachlorodibenzofuran
1,2,5,6-Dibenzanthracene
Benzo-g,h,i-perylene
98C
77
84
110
96
48
81
130
100
84
80a
160a
110a
100
140a
80a
110a
85a
79a
110a
63a
120
78a
85
140
noa
62
120
ND
ND,
91a
51a
MCE/GPC/Florisil
average
recovery (%)
64a
43a
52
61
54
13
32
78a
50
55a
39a
113
53
61
46
38
58
53a
37a
49
ND
51a
29a
56a
56
26
11
37r
57C
114C
37
32
Two determinations.
ND = not detected.
One determination.
25
-------
2. Toxaphene Analysis
Method evaluation of the toxaphene separation schemes was limited
to the analysis of spiked blanks for both the carbon and Florisil column
cleanup. As described earlier, the sample extracts were chromatographed
first on the Amoco PX-21 charcoal glass fiber column and then the Florisil
column. The charcoal column was included in the cleanup primarily as a
means of isolating PCDDs and PCDFs as part of a separate task under the
broad scan analysis work assignment. The inclusion of the carbon based
cleanup system did provide the opportunity to isolate the toxaphene from
other potentially interfering analytes.
Recovery of toxaphene from the carbon based column was first inves-
tigated to determine which eluate should be taken through further fractiona-
tion on the Florisil column. Approximately 5 ug of toxaphene was spiked onto
a carbon column, and the column was eluted as described earlier. The three
fractions of cyclohexane/methylene chloride (50/50); methylene chloride/meth-
anol/benzene (75/20/5); and toluene were collected separately and screened
for toxaphene recovery by HRGC/ECD. Recovery calculations were based on sum-
mation of areas for the toxaphene respone in a retention time window estab-
lished from the analysis of the toxaphene standard. Recoveries were calcu-
lated by direct comparison to a toxaphene standard and two internal standards
(1,2-dichloronaphthalene and octachloronaphthalene). The results of these
recovery calculations are summarized in Table 4.
As noted in Table 4, the recoveries from the three different quan-
titation procedures indicate that toxaphene was recovered at approximately
80% in the first eluate from the carbon column. Based on these results, the
methylene chloride/cyclohexane fraction of the carbon column cleanups for the
composite extracts from the 45+ age category were reserved for further cleanup
on Florisil.
The recovery of toxaphene from the Florisil column procedure was
also investigated. Table 5 summarizes the recovery of toxaphene from this
cleanup procedure using 1.0 and 0.1 ug spike levels. These results demon-
strate that the toxaphene is recovered from 80 to 100% in the 10% acetone in
the hexane fraction. The data presented in Table 5 also demonstrates that
the Florisil column fractionation does provide separation of equal spike
levels of toxaphene and Aroclor 1260. Figures 4 and 5 are examples of the
separation of the mixture of PCBs and toxaphene achieved using packed column
(1.5% SP-2250, 1.95% SP-2240 on 100/120 Supelcoport) GC/ECD.
IV. RESULTS
A. Broad Scan Analysis
1. HRGC/MS
The HRGC/MS analyses for the 46 composite samples and the associ-
ated QC samples (blanks, replicates, and spikes) were completed following
the method evaluation studies. Figures 6 to 9 illustrate the incidence of
detection of specific target analytes or compound classes that were deter-
mined using the automated HRGC/MS search and quantisation routines based
on the mass spectral library established in the method evaluation studies.
26
-------
Table 4. Recoveries of Toxaphene from Carbon/Glass Fiber
Adsorbent Column
Fraction
Direct
comparison to
toxaphene standard
Relative to
1,2-dichloro-
naphthalene (IS)1
Relative to
octachloro-
naphthalene (IS)
Methyl ene chloride/
cyclohexane (50/50)
Methylene chloride/
79.6
1.4
79.9
1.4
87.5
1.4
cyclohexane/benzene
(75/20/5)
Toluene
1.8
2.1
NCL
.IS = internal standard.
DNC = not calculated.
27
-------
Table 5. Recovery of Toxaphene from Florisil Cleanup
Amount of spike
1 (jg toxaphene
100 ng toxaphene
1 pg toxaphene +
1 ug Aroclor 1260
Fraction
50 mL hexane
50 mL 90/103
50 mL hexane
50 mL 90/10
50 mL hexane
50 mL 90/10
Recovery
0.13 ug
0.81 ug
23 ng
90 ng
1-2 ug (A)b
i.o Mg (T)
% Recovery
of spike
13
81
23
90
120 (A)
100 (T)
*90% hexane, 10% acetone.
(A) = Aroclor standard recovery; (T) = toxaphene standard recovery.
28
-------
asuodsay
asuodsay
o
•g
T3 C
CD O
•P •.-
ro -P
> U
•i- n3
-(-> S-
U *+-
n3
QJ OJ
T3 C
TO
&§ X
LT> O)
CM x:
••- T3
in s-
•i- m
s- -a
o c
r— O)
U_ +J
in
O)
C T3
0)
c:
OJ
cu
Q.-C "O
(0 Q. S-
x 03 ro
o x -o
-p o c
•p ro
E \ +>
O o in
S-
in CM
CD S- rH
O O
Q- .— S-
U O
4- O r-
O S- (J
U E
S- rd O
3 S- £-
O54-
-------
2 c
§ 2
asuodsay
J-i
« s
a u_
asuodsay
-o
5
1
^
-2-g.
t-
s~^ ID
-a j=
cu -P
U +J
ns cu
O) •!-
•a -o
LD O
CSJ rH
V—<• QQ
•i- T) .
en 1- T3
•i- ro S-
S- TD ro
O C TD
(0
I/)
U- -P
O)
d ~u
•i- CU CU
in X C
3 -i- CU
E -C
in Q.
QQ CU ro
Q- CU O
-C -P
E Q.
o fd /-^
S- X O
•4— O
at \ r—
c o ••-
cu ^D in
J= CM -r-
Q.I—I S-
(XJ O
X S- i—
O O Ll_
-P 1—
U E
M- O O
O S- 5-
< 4-
U
(0
•i- <: o
(0 ""
ro
Q. O S-
cu -i- t-
CO -P
rO CU
C. C
• O ro
LD •!- X
•P CU
cu u £:
S- ro
3 S- C
O54- -i-
ssuodsay
30
-------
Census region
Census division
Compound
West
Mountain
Pacific
0-14
15-44
45+
0-14
45+
1,2-Dichlorobenzene
1,2,4-Trichlorobenzene
Naphthalene
Pentachlorobenzene
Diethyl phthalate
Tributyl phosphate
Hexachlorobenzene
p-BHC
Phenanthrene
Di-rrbutyl phthalate
Heptachlor epoxide
Pyrene
trans-Nonachlor
jJTpT^DDE
Dieldrin
p_,E'-DDT
Butyl benzyl phthalate
Triphenyl phosphate
Di-n-octyl phthalate
Mi rex
tris(2-Ch1oroethyl) phosphate
Total PCBs
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Nonachlorobiphenyl
Decachlorobiphenyl
Figure 6. Incidence of detection of semivolatile organic compounds de-
termined in composited human adipose tissue from the West Census Region.
A positive (+) value indicates the compound was detected at a trace or
positive quantifiable level. A negative (-) value indicates the compound
was not detected. The number of symbols for each age group indicates the
number of composites analyzed.
31
-------
Census region Northeast
Census division New England Middle Atlantic
0-14 15-44 45+ 0-14 15-44 45+
Compound
1,2-Dichlorobenzene - + — -+
1,2,4-Trichlorobenzene - -
Naphthalene - +----+-+
Pentachlorobenzene - - - — --
Diethyl phthalate + ++-++---
Tributyl phosphate - -
Hexachlorobenzene - +++++++-
p-BHC - ++++++++
Phenanthrene - -__-+___
Di-n-butyl phthalate - - + +- ++ ++
Heptachlor epoxide - +-+++++-
Pyrene - ________
trans-Nonachlor - + ++ ++ +-
Dieldrin - - — — -+
p_,p_'-DDT - +++++--+
Butyl benzyl phthalate - ---+++-+
Triphenyl phosphate - ---+-+-+
Di-rroctyl phthalate + +---+--+
Mi rex - + + --
tris(2-Chloroethy1) phosphate - ________
Total PCBs - ++++++++
Trichlorobiphenyl - -
Tetrachlorobiphenyl - + + ++ ++ +-
Pentachlorobiphenyl - + + ++ ++ ++
Hexachlorobiphenyl - +-++++++
Heptachlorobiphenyl - - — +- -
Octachlorobiphenyl - _+______
Nonachlorobiphenyl - -
Decachlorobiphenyl - __-_--__
Figure 7. Incidence of detection of semivolatile organic compounds deter-
mined in composited human adipose tissue from the Northeast Census Region.
A positive (+) value indicates the compound was detected at a trace or
positive quantifiable level. A negative (-) value indicates the compound
was not detected. The number of symbols for each age group indicates the
number of composites analyzed.
32
-------
Census region North Central
Census division East North Central West North Central
0-14 15-44 45+ 0-14 15-44 45+
Compound
1,2-Dichlorobenzene -- --+ — - -
1,2,4-Trichlorobenzene -- — --+ - _ __
Naphthalene — +— ++- + - +-
Pentachlorobenzene -- — — - -
Diethyl phthalate -+ -+- -+- - + ++
Tributyl phosphate -+ — — - -
Hexachlorobenzene -- ++- +++ + + +-
p-BHC -+ +++ +++ + + ++
Phenanthrene -+ — —
Di-n-butyl phthalate -+ -+- -++ + -+
Heptachlor epoxide -+ -++ +++ + + ++
Pyrene -- — — - _ __
trans-Nonachlor -- —+ -++ - + ++
p_,p_' -DDE ++ +++ +++ + + ++
Dieldrin — -+- -++ + + +-
p_,p_'-DDT -+ ++- — - +-
Butyl benzyl phthalate ++ -+- +++ + + ++
Triphenyl phosphate -+ -+- -+- - - -+
Di-n-octyl phthalate -- -+- --+ - - +-
Mirex -- — —
tris(2-Ch1oroethyl) phosphate -- — — - -
Total PCBs -- +++ +++ + + ++
Trichlorobiphenyl -- — +++ - - +-
Tetrachlorobiphenyl -- -+- -++ - + ++
Pentachlorobiphenyl -- -++ -++ + + ++
Hexachlorobiphenyl -- -++ -++ + + ++
Heptachlorobiphenyl -- +-- -++ - + ++
Octachlorobiphenyl -- +-- -++ - + ++
Nonachlorobiphenyl -- — — - +-
Decachlorobiphenyl -- — -+- - -
Figure 8. Incidence of detection of semivolatile organic compounds deter-
mined in composited human adipose tissue from the North Central Census
Region. A positive (+) value indicates the compound was detected at a
trace or positive quantifiable level. A negative (-) value indicates the
compound was not detected. The number of symbols for each age group indi-
cates the number of composites analyzed.
33
-------
Census region South
Census division South Atlantic East South Central West South Central
0-14 15-44 45+ 0-14 15-44 45+ 0-14 15-44 45+
Compound
1,2-Dichlorobenzene -- - - +
1,2,4-Trichlorobenzene — —+ - - --
Naphthalene ++ --+- +-+- - + -+ + +-
Pentachl orobenzene — - _ __ _ __
Diethyl phthalate — -++- -+— + + -- + +-
Tributyl phosphate ~ - - — - --
Hexachlorobenzene +-
p-BHC ++
Phenanthrene
Di-n-butyl phthalate -+
Heptachlor epoxide +-
Pyrene
trans-Nonachlor +-
Dieldrin
p_,p_'-DDT
Butyl benzyl phthalate
Triphenyl phosphate
Di-n-octyl phthalate
Mi rex
tris(2-Ch1oroethy1)
phosphate
Total PCBs
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Nonachlorobiphenyl
Decachlorobiphenyl
Figure 9. Incidence of detection of semivolatile organic compounds determined
in composited human adipose tissue from the South Census Region. A positive
(+) value indicates the compound was detected at a trace or positive quanti-
fiable level. A negative (-) value indicates the compound was not detected.
The number of symbols for each age group indicates the number of composites
analyzed.
34
-------
The analyses for the PCBs was accomplished through manual identification and
quantisation within designated retention windows established for each of the
homologs. These figures summarize the incidence of detection of each of the
target analytes based on the specific census regions and divisions. A posi-
tive (+) value indicates that the compound was detected at a trace or posi-
tive quantifiable level. A negative (-) value indicates that the compound
was not detected. These figures also indicate the number of composite sample
analyses completed for each age group within a specific census division. The
number of composite samples analyzed for a specific age group is noted by the
number of positive and negative symbols. Table 6 presents the frequency of
observation of these target analytes from the 46 composite samples.
Figures 10 and 11 present examples of the HRGC/MS chromatograms of
the 6% and 15/50% diethyl ether Florisil fractions for the three age group
composites within a specific census division. The HRGC/MS chromatograms for
a specific age group composite across three different census divisions is pre-
sented in Figures 12 to 15.
The most notable differences between the HRGC/MS analyses for the
three age groups within a specific census division is the chromatogram char-
acteristic in the time frame of 13 to 30 min (6% diethyl ether Florisil frac-
tion). This difference, noted as a significant response to a complex matrix,
is attributed to the efficiency of the GPC cleanup with respect to differences
in the composition of adipose tissue with age (Spearman 1982). Some differ-
ences were noted for the three age groups in the response of the UV-detector
used to monitor the GPC effluent during bulk lipid cleanup. The lipid profile
(noted as the UV response from GPC cleanup) for the 15-44 and particularly
the 45+ age groups were typically noted to tail significantly in comparison
with the 0-14 age groups.
An automated search of the major chromatographic peaks versus the
National Bureau of Standards (NBS) mass spectral reference library indicates
that the major peaks in these chromatograms are due to biogenic materials
(e.g., fatty acids and cholesterol related components) which are not removed
by GPC. A review of the elution profiles presented in Figure 1 demonstrates
that these materials elute within the same retention window as the phthalate
esters.
a. Organochlorine Pesticides
As noted in Table 6, organochlorine pesticides and related
metabolites were determined in a majority of the composite samples analyzed.
Trace or positive quantifiable levels of beta-BHC, p_,p_'-DDE, p_,p_'-DDT, mirex,
trans nonachlor, heptachlor epoxide, and dieldrin are reported for the compos-
ite samples in Tables 7 to 13. These compounds have been routinely detected
with the packed GC/electron capture detector (PGC/ECD) method in past NHATS
analysis programs. However, the PGC/ECD data from previous NHATS analysis
programs have indicated a higher incidence of detection for many of these
compounds. The difference in the incidence of detection between the methods
can be attributed to the relative sensitivities of the two instrumental
techniques.
35
-------
Table 6. Incidence of Detection of Selected Semi volatile
Organic Compounds in the NHATS FY82 Composite Specimens
Compound Frequency of observation (%)
a
1,2-Dichlorobenzene 9
1,2,4-Trichlorobenzene 4
Naphthalene 40
Diethyl phthalate 42
Tributyl phosphate 2
Hexachlorobenzene 76
p-BHC 87
Phenanthrene 13
Di-n-butyl phthalate 44
Heptachlor epoxide 67
trans-Nonachlor 53
E,P_'-DDE 93
Dieldrin 31
p_,P_'-DDT 55
Butyl benzyl phthalate 69
Triphenyl phosphate 36
Di-n-octyl phthalate 31
Mi rex 13
tris(2-Chloroethyl)phosphate 2
Total PCBs 83
Trichlorobiphenyl 22
Tetrachlorobiphenyl 53
Pentachlorobiphenyl 73
Hexachlorobiphenyl 73
Heptachlorobiphenyl 53
Octachlorobiphenyl 40
Nonachlorobiphenyl 13
Decachlorobiphenyl 7
aSample size = 46 composites.
36
-------
l-MO-SVO-0-14
I
4i2» 1141 IIiM
Ml IM>
I7t2> 2114*
lUi
3414»
SCON
TIIC
(1C .
1-MO-SVO-15-44
1-MO-SVO-45+
4,2* tut HIM in:
im I«H icn sow
2bM Mill MUt TIW
Figure 10. HRGC/MS chromatograms of the 6% diethyl ether Florisil
fraction for the three age group composites (0-14, 15-44, and 45)
from the Mountain (MO) census division.
37
-------
(1C
bjp J»
iJL A>
.i. T «
1-MO-SVO-0-14
Ml !Wt 12M
ma 2114* %IM
1SW SCUM
n.«a TIIC
1M.I-I
III
i alii... ...TI...II
1XMII.
l-MO-SVO-15-44
2N
4< 3t
Il4* UlW
IN*
UI4*
UN
XiM
I4H
Ml 3*
ICW
Ml 41
SOW
TIIC
uata.
££.
» I 8P V
I. ^Lt «!V L en T.
1-MO-SVO-45+
12M I4M ICW SCAN
Figure 11. HRGC/MS chromatogram of the 15/50% diethyl ether Florisil
fraction for the three age groups (0-14, 15-44, and 45 plus) from
the Mountain census division.
38
-------
l-SA-SVO-0-14
SCAN
TIIC
l-WN-SVO-0-14
R1C.
SCHN
TUE
1-MO-SVO-0-14
I —
„ ijj
CM
lllW
M» IMt
12M MM 1
-------
M.*1
we.
1.1
i an
" p<<• SON
2H4I aiM Ilia Ml-44 TIK
Figure 13. Comparison of the HRGC/MS chromatograms of the 45 plus age
composites (6% diethyl ether Florisil fractions) from three census
divisions.
40
-------
nc.
l-SA-SVO-0-14
l-WN-SVO-0-14
T«
1-MO-SVO-O-H
Mix.
CM
UtW
!}• !«• 1CM SOW
2ClM 3»i2J Mi4« TIIC
Figure 14. Comparison of the HRGC/MS chromatograms of the 0-14 age
composites (15/50% diethyl ether Florisil fractions) from three
census divisions.
41
-------
1-SA-SVO-45+
1-WN-SVO-45+
J J _ Ml
unto.
1-MO-SVO-45+
2" 4«
IN* 1ZM 14M t(M SUM
2iiw 3t>m *ti* un* TIIC
Figure 15. Comparison of the HRGC/MS chromatograms of the 45 plus age
composites (15/50% diethyl ether Florisil fractions) from three
census divisions.
42
-------
C
U)
o>
1
PO
QJ
t/)
in
o
CL
i
01
o
C.
o
CM
CO
u_
(
,— V
^
in
co
en
rH
ro
O
Z
ii
£
CO
m
4-*
Or-
CO
4->
S-
O
0.
QJ
ex.
ro
(0
O
^
r^
.0
ro
r-
in
in 01
r— <0
ro T3
C
D)
Ol
1 3-
C
o T:
4-> a.
ro —
£; "~
C 01
Ol •—
u .D
C ro
O J->
c_> o
ro
s-
4_>
X
01
t;
I Ol
c a>
o n.
ro 01
t. 3
4-> in
C in
OJ •>-
U *>
C
0
o
.a
^^
l/i 3.
I/) S^>
ro
E "O
01
(0 U
4-> (U
0 4J
r- 01
•o
l~
% r
ro
4-> 4->
u .C
S- -i-
X S
UJ
0) Oi
D
in i
in
4-> .iz
Ol
4-* -i-
3 3
01
'o. s-
ro JD
t/) £
— I C
cc
z
01
.,_
in
o
£ 01
o ja
u E
01 C
t
ro
«• * *
CO CO CO
en en o
rH rH rH
/~*.
ro rH LO
O rH CM
O O O
s^ '
O
Z
CM en
CM r>- CM
O O CM
o o o
o
•z.
^
O ro
CM LO 1C
O rH <3-
O
z
ro rH ro
CM -9- «•
LD r«fc CO
cover-
tn ro r^
o m o
Ol CO r-H
i— ( CSJ
Ji^ f«^ r-4
ro PO *tf-
o o o
1 1 1
CSJ CSJ CSJ
CO CO CO
•CJ-
i in in
O iH *i-
t 1 I
o o o
CO l/> tA
1 1 1
t 1 I
«3- <*•<*•
CO CO CO
V£> U"> U3
/^s
cri in
t-f r-^ cri
o in o
000
^v
O
Z
o in
rH O r-~
O in o
000
0
z
^^
o o
csj o
O rH CM
O
Z
rH 1C CM
LO r^ en
LO CO r~
in CM rH
o en rH
I-H en r»-
Cn rH LO
i— 1 CM CM
CM CO «3-
«i- *d- *f
o o o
1 1 1
CM CM CM
CO CO CO
•a-
t-t 1 +
i in in
O rH O-
1 1 1
CO CO CO
1 1 1
LU LU LU
z z z
1 1 1
* «3-
co co
en en
rH rH
co
ro
o
o u
L.
**
CM
0
o u
t-
co
0 0
i-
4J
en I-H
CM f—
LD CO
f CM
CM en
P~- O
en CM
rH CM
LD CO
o o
1 [
CM CSJ
co co
i-H +
i in
o «•
1 1
0 O
CO CO
1 1
O. Q-
1 t
*J- *f *3"
S«9- ^- CO CO CO
co co \\--v
^^•^.\ CM CM CM
1C LO rH rH rH rH
^ ttf" VC 1C LO LO
o r* r-~
en in in co vc CM
O «S" rH O O CM
O O O O O O
O TJ- ro
r^ LO CM r^ in en
O ro i-H O O rH
0 0 O 0 0 O
O
LD I-H o m «a- •»
i-H CD CM rH rH ro
in r^ LO r^ CM cn
r^ o CM ^t co ro
CO CO *}• i-H «3- rH
r-- o ro r^ o in
O CM CM CM i-H O
ro in LD o ic co
CM CSJ rH CM CSJ rH
en o rn CM ro «a-
**• LO in in LO in
o o o o o o
1 1 1 1 1 1
CSJ CM CM CM CM CM
co co co co co co
*r ^~
rH I + i-H 1 +
i in LO i in in
O rH TJ- O rH *J-
1 1 1 1 1 1
0 0 O O O O
CO CO CO CO CO LO
1 1 1 1 1 1
1 > 1 1 1 t
"^ ~^ **^ CO CO CO CO CO
r*i en CO r^ en r^
OOCMOOOOrH
oooooooo
s-^
O £- &-
Z 4J 4J
rH en en T-H CM rH
rHineniHCOCOrOLO
OOrHOOOOrH
oooooooo
a i- s-
^_,
O CM ro
CMrocotr^csiLD*}-
OrHroOrHCMOro
0 i- i-
Z 4-> 4->
LDLOLOrOCslCMCMro
§rC§SSSSc2
oo*'oors««cocococo
cOsD^^rr^i^vDcn
r-Hl£)COCSJ^j-CSJCSJCsJ
C0>— IO^»-Hi-H(JDOro
rHCsli— ICsJCSlCSJCsJCSj
miDr-«-cocriOr-icsj
oooooooo
1 1 1 1 1 1 1 1
cocococococococo
^1- «d- ^
r- 1 1 4. i— 1 | 4- | 4-
i un m i in in in in
1 1 1 1 1 1 1 1
llllliil
1 1 1 t 1 1 1 1
1 1 1 1 1 1 1 1
CO CO CO CO
h*- ^ f^. in
in in in vo
CSJ
in csj o i— t
O rH PO »H
o o o o
&_
"*"*
ro O <£>
n crt r^. ro
0 O Csj 0
o o o o
i-
r- c^ o co
O iH VO rH
i-
4->
r-H CM 00 ^3-
ro un o> o
1£> h< CO CO
CO N* CSJ CSJ
«3- in o r-
^- i£> in ^~
ro O CS1 rH
CSJ CSJ CSJ CSJ
ro «*• in vO
VD ID <£> ^O
0000
1 1 1 1
csr csj csj csj
CO CO CO CO
^
«a- ^~
rH 1 + 4.
i m m m
O rH **• *fr
1111
oo o o
(/> t/) t/J t/5
1 1 1 1
1 1 1 1
rH r- 1 r- 1 CSJ
43
-------
•o
Ol
3
C
C
0
u
f^
Ol
JD
re
in
(/) Ol
•— re
ro TJ
c
^^
en
CD
c
O TJ
•P o.
re ••-
4J
C O!
O) r—
u -a
c re
O 4->
o u
ro
s-
X
ai
.p
oi
i "5
C D>
o a.
re a>
S- 3
4-> in
c in
ai -i-
O 4J
c
o
o
.Q
OJ
W 3.
I/} ^^
ro
E TJ
Ol
I— 4J
ro u
4-> 01
O 4->
1— 01
•o
TJ
D.'--
Gl CO
X) 1
4-> 4->
u .c
ro CT>
UJ
01 CD
3
in
4-> .C
*>•?
01 Ol
3 2
ai
E 01
1-4 I
as
z
o>
r—
o
Q. S-
E 01
O XI
(J E
a> c
i
ro
CO
,g. „ ,3. «r «r ,3-
-N^ -s^ "NS^ QO """•••• CO "V. CO "^v.
rHCSICSJunr-tLnrHVOrH
in ^ ^ ^O y? ID fcO (^ tD
^D «tf- r- t LH
CXJOCSJOOOCsli— trH
OOOOOOOOO
S_
fO ^H *!(" fO rHCSJ
^
cn^-mtHfo^-r^oin
M^CMcncnoiDCMO
oooooocooOf^oor^r^
OOOOinCMTl-lDUOrH^J-
CDCMlDCOI~-CMinoOCM
r~«3-or-iinenocMco
ocoocncnr^oocot~.
§§§S555o5
1 1 1 1 1 1 1 1 t
cooococococococooo
^t" ^f ^ t^
iH 1 H- iH 1 1 + 1 +
i in in i m m in in in
t i i i i i i i i
Illllllli
i i i i i i * * i
cococococococococo
1 1 1 1 1 1 1 t 1
«r •*
fl- CO CO "3-
l— 1 rH rH CO
uo in in co
en rH ro oo
ro «tf- in CM
o o o o
o ^- r^ CM
ro ro ^- CM
o o o o
in co co ID
oo co en ^*
CM CM ^- CM
r^- ro oo 00
i^ oo co r^
r^ co ro in
rH ID 00 ID
?"H Cn p^ rH
oo en o r-i
i^ co en ^H
o oo o
i i i i
CM CM CM CM
00 00 00 00
^>
1-1 1 + +
i in in in
O iH «3- »)-
1 1 1 1
O 0 O O
CO CO 4y} CO
i i l i
CO CO CO CO
UJ LU LU CU
1 1 1 1
rH rH rH CM
q.
*j- -a- «s- oo
CO CO CO^.
^.^.^co
CO ^ t^" rH
in in en co
P"» r*^
in ^ ID en
o ro en o
o o o o
i-
oo «•
ro en ro co
o CM in o
0 0 O 0
i.
4J
ro
«S- ID 00
O CO CM rH
rH
^
CO p^ CO ro
r^« ID ^~ co
co co en co
in r^ CM en
r-. en rH oo
rH p- «*• en
rH CM CM rH
rH CM CM CM
CM ro ^4- in
§00 00 CO
0 O O
4 1 I 1
CM CM CM CM
00 CO CO 00
*f *^
rH t -4- 1
i in en in
O rH ^- rH
4141
CO CO CO CO
1411
CO CO CO CO
1141
rH 1-4 rH CM
i-
O
It- r—
O)
O- 0)
O i—
•^ ro
C 4->
o re
ro c
4J OI
4-) 0)
C i-
3
CT l/l
t4»
O T3
C
•r- O
E O.
"- E
r— 0
U
TJ
Ol 01
re r—
E
4->
in o>
01 U
re
01 i-
-C 4->
II
s-
•z.
CO
/•-^
X O
0
in — i
CM
o
01 •!-
1— 4->
E Ol
re 4->
l/) O)
'*v, ^O
CD
a. <4-
o
o
CM 4->
0 E
U) l —
TJ
TJ 0)
3 re
0 B
E 43
O in
01
•i- -C
-C 4->
• to
t- ^^'r-
O 31
"4-*^ V*
CO O)
/~s in
f-\ ^ QJ
So5
C i.
o 01 ro
•.- r— Q.
4J Q.
U E C
Ol TO -r-
4-> in
Ol \ O)
T3 D) 3
«- ro
o o >
oo • •
4-> • O"tJ
•r- O • O Ol
E -a -> n
•r- in O) ••-
— ••- 4J TJ i.
u c ro
TJ "o o) re E
01 C *J E
4-> 3 01 O 3
re o TJ o w>
E a. —i
•r- E 4J 4J
4-> O O C O
in o c ai c
ai ai
in || » re
0)-r- 4J 4J
j= f o 01 re
« .a u
44
-------
D
V)
01
Q.
E
IB
CO
01
v>
in
r—
CD
O
Q.
ITI
*
4J
• !b
in
O
0
CM
00
t
s—^
Ol
in
i
CM
o
CO
^
o
o
"cy
QJ
1
o
Q.
OJ
a:
4J
to
o
00
01
^
ro
r-
[2
ul O>
m XJ
c
<
01
en
1 2-
c
O "O
4-> a.
10 •r-
£ "~
C OJ
0 S
c ni
O J->
CJ) U
re
i-
X
O)
Ol
2
i en
c o>
o n.
m ai
t- 3
4^ in
c u>
O) •.-
U 4->
c
o
ja
Ol
m n
Ul *-^
m
E TI
0)
ro o
•>-> ai
O -4->
r- ai
TJ
TS
£«
r_
ja i
U JT
S- •!-
x 5
LJJ
OJ Ol
(/) 1
I/)
•M -C
O)
01 OJ
f S
Ol
'o. s-
ro JD
in E
3
r- 1 C
ce
£
o>
ti
o
0. S-
E OJ
Si
7
Q) C
Q.
E
TO
t/)
*i- «d- ^J-
00 00 00
Cft
CO CO CO
ggg
1 1 1
rH rH rH
OO CO CO
co in co
*^
•a- m
0 CM O
^.
O rH P^
O CM O
•a-
rH r^ O
•a- CM
rH CD CM
m P-- 01
m oo r^
in CM *H
0 01 rH
rH rH CM
rH Ol r-
Ol rH CO
rH CM CM
CM ro ^j-
•a- •«- i i
CM CM CM
CO CO CO
q.
rH 1 +
i in in
O -H q-
1 1 1
CO CO CO
1 1 1
LU LJJ CU
Z Z Z
1 1 1
rH rH rH
f <»•
CO CO
Ol Ol
rH rH
— ^
o
CO rH
CM O
0 0
O
Z
Ol
CO O
rH 0
0 0
Z
o
CM CM
ro o
O
Z
Ol rH
CM r»
co 00
«>• CM
CM Ol
r-. o
Ol CM
rH CM
ID CO
«*• *r
o o
i i
CM CM
CO CO
rH -t-
i in
0 *±
1 1
UO m f-H rH rH rH
«3- «T <£> "X> ID UD
m
in in ^ r*«« 10
oo csj r^. m ro o
O CNI 0 0 0 0
CNJ
ID CNJ CD CH LT)
tO CO V£> ^- CNJ O
O T-H O O O O
PO LO cn
in in o en r^ o
rH ^- f— 1
in f^ tn P** CNJ en
r>. o CM «3- oo ro
r^ oo oo oo r*. co
CO ro *J- T-H ^- rH
o. O ro r^- o m
O CNI CNJ CNI rH O
ro in VD o ID co
CNI CM rH CNJ CNJ rH
Ol O rH CNJ CO «3-
^ in m m m tn
o o o o o o
1 1 1 1 1 1
CNJ CNJ CNJ CNJ CNI CNI
"3- «*•
rH r + rH I +
i un m i m m
O rH «*• O r-l ^d-
r i i I i t
o o o o o o
V> V) t/> LO V) CO
1 1 1 1 1 1
ggg g gg
1 1 1 1 1 1
r-t rH r-t CNJ CNJ CNI
^- «3- <•
\ ® 5 S CO 00 00 00
rHCNjCNILnm^UOiD
^^^^^il5^
in
CM rH in CM O ^J- rH
rHinOrHOrHroOl
OOrHOOrHOO
i.
O rH
cooiroocMCMCjir^
OrOCOrHOOlCMf^
OOOOOOOO
L.
4J
w
rH ro CM "3- CO
rHOOCOCMO-a-inOO
rH CM rH
S-
4^
coincorocMCMCMro
ooinooirororoin
*j-r^cocoooooooco
coroor^oooooooo
OOCOlD«a-r»rHCOOl
rHCDCOCM^a-CMCJCM
COrHOlrHrHCOOro
rHCMi-HCMCMCMCMCM
mcor*.COO)OrHCM
mininininiDcoco
OOOOOOOO
i i i i i i i i
CMCMCMCMCMCMCMCNJ
cococococooococo
•a- o- q-
«s- «*• «• * ^»-
rH I -*• rH 1 H- 1 4-
i in in i in in in in
i i t i i i i i
CO l/l CO l/l l/> l/> (/I I/}
t 1 1 1 1 1 1 1
zzzzzzzz
1 1 1 1 1 1 1 1
co co co co
r^ ^ r*» in
in in in co
O CM CSJ
0 0 rH 0
SS^-S
0 0 iH 0
^>
^- ^j- rH rH
rH CO t-f
rH CNI 00 O-
ro i^ cr* o
VD r^ oo oo
co r-»- CNJ CNJ
*f ir> o r*.
<- ya m -a-
ro C3 CNI rH
CNJ CNJ CNI CNI
ro ^- un ID
ID VD ID *^> l/> V/)
1 1 1 1
1 1 1 1
fH rH r-l CM
45
-------
y**.
*O
S
c
c
o
u
oo
0)
XI
ro
in ru
i — ro
ro TJ
c
^^
O)
O)
1 ^
c
o -a
*j a.
ro •!-
^ '
C O)
u !o
c ro
0 4->
<-> u
ro
•u
X
o
-p
ai
s ^
i 'S
C CD
O 3.
ro aj
U 3
4-> in
c in
0) t-
U 4->
c
o
u
.0
CO
U> 3.
in ^-*
ro
E -0
O>
ro u
*> 01
O *J
r— OJ
•o
•o
£»«
r- ^
,_
.a 1
ro
U -C
i- "-
LLJ
0) O>
3
in i
in
+J f
a>
at a)
2 S
01
'a. s-
ro .a
>-4 C
or
s:
oj
^
in
o
a. s.
E . CO CO \ CO "X.
rHCMCMinrH^-inrHlOrH
in ^~ "& to to ^o '•O ^o to yD
ro ^~
CM CM co m rH r-- ro
*3-inoiPoinoinrocMO
OOOOOOr-trHrHO
t-
rH ^"
rO^-COCM«d-OOrHCOO
OOOOOOrHrHOO
i.
+J
ro
PO tD CTi tD *(f
r^CMVD^cdrHCOOUDd
rH rH rH CNJ rH
t.
a>^-LnrHrocn^-r^oin
rotDCSjCncnrootDCMO
cococotDcooor^oor^r*.
CO CO in CM ^ 01 1C 10 rH ^
^DCMvoror^rHCMinrocM
l^^OrHinrSCnOCMtD
oiDCDcna>tDr»-o6o6r^
CMCMCMrHrHCMrHr-lr-lrH
^COCnOrHCMfO^'invD
oooooooooo
1 1 1 1 1 1 1 1 1 1
CMCMCMCMCMCMCMCSJCMCM
^" *^ ^ ^
r-( , + r-f , + | + , +
i mm i in tn m in m m
O rH *^~ CD rH ^ rH ^" rH ^
t 1 1 1 f 1 1 1 1 1
lllllllill
i i i i i i i i i i
t/) LO OO OO OO OO OO OO OO OO
1 1 1 1 1 1 1 1 1 1
*r S S «• «s-
oo \\ oo oo
rH rH rH ID UD
!£ LO LO 1^ 'C*
/-«^
cn
o
r^« oo ^ o ^f
rH CM CM O CM
^^
O
z
00
o
ro ro rH o en
rH CM CM O rH
,^
O
CM
oo ^0 r*^ o en
a
CM CM «S- ID CM
r^. ro oo f^* 00
r^ oo oo 00 r^.
r-^coLOif.
rH ID 00 CM ID
rHOir-r^rH
00 OH O LO rH
CM rH CM CM CM
r*^ oo en o rH
r^i r^ f^ oo oo
0 0 O 0 0
1 1 1 I 1
CM CM CM CM CM
CO CO CO CO 00
*^ ^
rH I 4- | +
i in m in in
0 t-l *fr r-t T3-
1 I 1 1 1
O O O O O
to m to to to
1 1 1 1 1
to to to t/) to
UJ LLJ UJ ' ' ' UJ
1 I 1 1 C
rH rH rH CM CM
^t" ^ ^t" CO
CO CO CO \
00 ^t r- rH
m m in to
CM rH
co CM co r^
O rH UD O
in rH
m o ^- to
O rH l& O
rH
ro o ro
CM ^- rH
rH
to r-N. to ro
r^. to ^ to
tD CO Cfi 00
m p-- CM co
r- en rH co
rH CM CM rH
rH CM CM CNJ
CM ro ^- in
CO CO 00 CO
o o o o
1 1 1 1
CM CM CM CM
CO CO CO 00
^ ^
rH 1 + 1
1 IT) LO in
O rH «J- rH
1 1 1 1
O O O O
OO OO OO OO
1 1 1 1
OO OO OO OO
^K ^C jg ^f
rH rH rH CM
j_
O
t*— i —
ai
O" ai
o •—
**^ ro
c -u
O ro
4-> 4-J
ro c
•i— in
4_> ai
C i-
ro a.
O- tn
t*-
O ID
c
•<-> 3
•r- 0
•I? t
i— O
U
•D
ro i—
•r-
in ai
ai u
ro
O) i-
II
^^ 4^
J2
LO
/-^y
X O
o
un —i
CM
**^ c
o
at *r-
"o- u
ro 4->
tn at
~v. -a
O!
3.
d 'i
in i —
^j
T3 OJ
3 ro
0 E
o m
U 0)
in ai
• in
o z
i*- ""^ in
oo o>
/-N tn
C3 X OJ
O f
—1 0 4J
^_-rH c
***s OJ
C S-
o oj ro
.r- 1— 0.
4^ a.
DEC
OJ 10 -r-
4J in
TJ O) 3
3.r—
t*- ro
o o >
oo
*j . cy
— o • o
E TJ _l
•r- in OJ
r- -r- *J T3
U C
T5 T3 OJ ro
OJ C *->
4-> 3 ai a
ro o "D o
ED. —1
•r- E •(->
+J O O C
m u c OJ
0) OJ
in u 5
.c ^c o at
ro -O
46
-------
0
in
CU
CL
E
ro
i/)
OJ
3
tn
1 —
CU
in
O
Q.
s
01
+J
in
O
i-
o
CM
CO
LU
1
^s
1
CM
O
o
<
si
r—
O
1
OJ
OJ
1
+J
o
Q.
O>
ro
a
cn
at
.a
ID
'"
in
in LD
i— O>
ro 4->
C CO
O>
cn
1 a.
c
o T:
•P Q.
(O *r-
4-}
C CU
CU r—
U -Q
C ro
o *J
o u
CO
i.
•u
X
a>
CU
3
i O
c cn
0 3.
+J ^
4-> in
c in
a> —
0 •>->
c.
o
o
.0
m a.
CO
r- 4J
•p a>
O +->
-o
^•^
cu cn
(0
+j -J
ra o>
!_ •!-
4_> CU
UJ
01 D>
3
"— 1 *
cn
cu a>
S 3.
CO rH
rH CM
UD f^. rH
O O O
1 1 1
CM CM CM
CO CO 00
rH t -f
i tr> m
O rH ^f
1 1 1
000
on t/i co
i i i
iii
i i i
CO 00 CO
»**
Sin^-
o ro ro
o o o
o
o
rH rH r^
O ro CM
O O O
o
o
CM CO rH
O ID P~
**^
o
T— 1 ID CM
in co r—
in CM I-H
o cn rH
rH rH CM
rH cn r-
Cn rH ID
rH CM CM
CM ro "Cp
O O O
1 1 1
CM CM CM
CO CO CO
rH 1 +
i in in
O rH <3-
1 1 1
§§§
LU LU LU
1 1 1
CO CO
cn en
i?^
CM O
CM rH
O O
O O
S- O
4-> Z
*3-
S- O
«-> z
en rH
CM r^
ID CO
*3- CM
CM cn
i-H rH
r^ O
Cn CM
rH CM
l£> 00
O O
1 1
CSJ CM
CO CO
rH +
i in
o *»•
i i
1/1 1/1
i i
CL. 0-
1 1
SI- «3-
CO CO
^^ "^^ ^ CM CM CM
^^ID ID ID ID
^j- in r-^ o
in «^- rH ro rH in
O CM O O O rH
O O O O O O
a i- o
Z *J Z
CM CM rH CO
«3- cn rH ro O ro
O rH O O O rH
O O O O O O
0 !- 0
Z •!-> Z
o ro o
O CO CM ID CM ro
rH «»• O O O CM
O S- Q
Z •<-> Z
in p^ in r^ CM cn
P- O CM tj- CO ro
P^ co co co P^ co
CO ro *t rH ^- rH
p»- o ro p— o in
rH CM rH rH CM rH
O CM CM CM rH O
ro in ID O v£> oo
CM CM rH CM CM rH
Cn O rH CM CO «!•
O O O O O O
1 1 1 1 1 1
CM CM CM CM CM CM
CO CO CO CO CO CO
rH 1 + rH 1 +
i in in i in in
O rH «* O rH «t
1 1 1 1 1 1
000000
1 1 1 t 1 1
1 1 1 1 1 1
co co cog cSS go g
SSSi^Ln^into
*»»«»^»
CM cn ro cn cn cn o
CM Cn rH rH CM O rH
O O O O O O O
000000 0
o o u !_ a o
Z Z J-> +-> Z O Z
rH in o ro ^- co cn
rH p» rH rH CM O O
O O O O O O O
O O O O O O O
o o s- s- o a
Z Z +•> *J Z U Z
O O CO CM O O
CM ID CM CM in CSJ CM
O rH O O O O O
O O S- S- O O
z z •!-> ••-> z u z
UDiniDrOCMCMCMrO
comocnrororoin
ooroop^cocococo
COlDUO^-P^rHsDCn
rH rH rH rH CM rH rH
rHlDOOCMTj-CMCMCM
COrHcnrHrHlDOrO
rHCMrHCMCMCMCMCM
invDp^cocnOrHCM
1 1 1 1 1 1 1 1
CMCMCMCMCMCMCMCM
cooocococooococo
rH 1 + rH 1 + 1 +
i in in i in in in in
i i i i i i i i
oooooooo
1 1 t 1 1 1 1 1
LLJ Lil III III III 111 III III
1 t 1 1 1 1 1 1
CO CO CO CO
i^ ^ r>^ ir>
in in in LD
rH CM
0 rH
0 0
0
U Z U
2"
rH rH
0 rH
O 0
Q
U Z U
0
CM «3"
O CSJ
^^
u z u
rH CSJ CO •*
ro ID cn O
CO P~ CM CM
«»• in o P»
rH rH CM rH
* 10 in ti-
ro o CM -H
CM CM CM CM
m *t in ID
o o o o
i i i i
CM CM CM CM
CO 00 CO CO
rH 1 -r -r
O rH *J- <9-
1 1 1 1
0 O O O
V> V) IO V^
1 1 1 1
1 1 1 1
rH rH rH CSJ
47
-------
^^
TJ
Oi
3
C
C
O
u
en
Ol
XI
ro
r-
in
in tx>
>,
— Ol
ro 4->
c ro
CO
CO
I 3.
c
O T3
*» O.
ro *<"-
i- •—
c o>
Ol •—
U JO
c ro
O 4J
o u
ro
X
o>
4J
OJ
, — ,
1 CO
C CO
0 3.
4->
ro o>
S- 3
4-> in
c in
Ol •«—
U 4->
c
o
o
, — ,
CO
in 3.
in *— '
ro
S T:
01
ro u
4-> O>
0 ->
r- Ol
"O
•0
D.^^
1^^
Ol CO
ro
u -C
ro co
4-> OJ
01 CO
3
in i
•r— 4J
4-> f~
CO
4-> T-
Ol OJ
3: 3
o>
Q. S-
E 01
in E
HH C
ce
^
-2
10
o
C. S-
E Ol
O XI
U E
Ol C
Q.
E
ro
00
»oooogoo§»§SO
rHCMCMLnrHLDrHlOrH
in«f«-U3lClDlDlClC
^^
O O in ro
O O rH O rH ID O CM
OOOOOOO 0
i- 0
*-> z. o
rH rH OO rH
OOrHOrHrOO rH
OOOOOOO O
Nuf
;- a
4-> Z (J
CM O
rHlC"3-P^CMCOCM CO
rHrHCMOCMlX>O CM
1- 0
•W 'Z. U
cn«3-inrHro«s-r--oin
S 00 00 £ S ° TO £ r?
OOOOinCM«-lClC?HTj-
ixiCMioror^cMinrocM
r-^^OrnincnocMic
oicocncnh~cooor^
CMCMCMrHrHrHrHrHrH
000000000
1 1 1 1 1 1 1 1 1
oocoaococooocoooco
,3.5 si-5? ?
rH 1 + rH 1 1 -1- 1 +
i in in i in in in in in
i i i i i i i i i
ooooooooo
l/> I/} I/") OO 1^0 I/) OO OO OO
1 1 1 I 1 1 1 1 1
I/) I/) l/> LO to t/1 OO OO OO
1 1 1 1 1 1 1 1 1
*}• 00 1- CO
i—t rH VD rH
vo in 03 ic
^
en
CM O P--
«d~ o co
o o o
o
•z. u
oo
CM o en
no O CM
00 0
0
z u
O 1C
O CM rH
en o 10
o
•z. u
CM «d- en CM
r^» oo !**• co
p^. oo co r*-
i — ro in in
rH 00 CM 1C
CO O in rH
CM CM CM CM
r~ cn o rH
r^ f^ co co
o o o o
1 1 1 1
CM CM CM CSJ
co GO co co
«*•
«• «•
rH + 1 +
i in in in
O ^J" rH «•
1 1 1 1
O O O O
00 OO OO OO
1 1 1 1
oo oo oo oo
LLJ LLJ LU LU
1 1 1 1
rH rH CM CM
•3- «3" O -Z.
rH 00
ro in o
O CM O
0 00
S- 0
4-> U Z
•«• o
ro i — CM
o in o
!- 0
4-1 U Z
ic r^ ic no
r^ UD *j- ic
03 oo en oo
in r^ CM en
r^ cri I-H oo
rH CM CM rH
rH CM CM CM
CM CO *f in
00 00 0000
O O O O
1 1 1 1
CM CM CM CM
0000 COCO
•a-? ?
rH 1 4. 1
i in m in
O rH Tf rH
1 1 1 1
O O O O
oo oo oo oo
1 1 1 1
OO OO 00 OO
till
rH rH rH CM
Z 01
•^ 01
00 S
X 01
XI
0
^"0)
01 01
tro
ro
in 4-1
\ ro
CO
c
0 01
oo in
d i-
o.
in
•r- W
S--D
_l 3
"*~s O
ct
o o
•r- U
ro oi
•r- x:
c
cr oi
u
4- ro
o s-
••- II
E
— S.
•a
Ol •
re o
E 0
in
01 c
Q
J= 4->
t— u
01
4->
. Ol
z.
00 O
X 4->
m E
CM ^~
^^-o
f^ +1
Q. (0
ro •!-
"^. in
01 0)
(U
O jC
CxJ 4-J
O tn
•r-
t/)
QJ
r-N (/)
a QJ
O -C
*— ' C
OJ
c u
O (O
"- CL
u c
O> -r-
QJ QJ
n- ro
0 >
4J -a
•r- . 0)
E T3 N
.,— oi -i-
u ro
•0 CD E
0) 4-> . E
4J 0) C3- 3
ro ^3 ^^ in
E -J
4-> o -n o
in C £ C
oi ro
II ro
Ol O 4->
j= o o ro
1— Z — 1 £3
ro xi u
48
-------
in OJ
to T:
•P O.
ro •<-
OJ
i£> in ro en r-* en
ro f—t r-l rH CO CM
ooo ooo
ID O
1-4 f—I
O O
oooooo
CSJr-HrMr-4rHOr-lrH
OOOOOOOO
OOO OOO
D o o a t- s-
o o
oo
QOOOOOQO
Ol
in
o
Q.
o
a.
a>
C in
0) -.-
O *->
O 4-*
h- Ol
•o
D)
S i
(D O)
3
in i
O
o> OJ
CNJr-HO O CM CO O O"> Cn CO CM O CO i—I r-iO^OCT^CTtCOOCT} CT» O CT> O"i
esj,_)rH rH CO CM rH O O O rH rH O r-H rHOi-+OOOrHO Or-( O O
ooo ooo oo oooooo oooooooo oooo
ooo ooo oo oooooo oooooooo oooo
OOO O t- I- OO O O O O O O OOQOOOQO OOOO
Z.-Z.-Z z: *•> +-> Z.ZL -z.-z.-z.-z.-z.-z •z.z.'Z.'z.z.z.-z.z. •z.-z.z.'z.
CM CM CM CM r- l£> CM CM CM CM CM CM CM CM CMCMCMCMCMCMCMCM CM CM CM CM
OOO O J- S- OO OOOOOO OOOOOOOO OQOO
Z.Z.-Z. z •*->+J z.z. -Z.Z.Z.VZ.Z.-Z. •z.-z.'z.-z.-z-z-z.'z. -Z.-Z.Z.Z.
roi-Hro i—t us CM en i—i in r»- LO f^- CM en voLO^rocMCMCMro i—tcjoo^
CM ^ «3- in r^ en CM r^ r- o CM ^- 06 rr> 06 m o 01 ro no ro LO ro ^ cri o
uar^oo mooj^ ix>co r-oocooor-oo «3-r^cotr>oooooooo r^ooco
Lf) C\J rH ^J- CM 00 ro «*• i—I «=T rH OO CO O r*- CO CO QO CO CO r^ CNJ CSI
ocnr-t csicn f^-oror^ou^
oroo i-HCir-- r-o CDCMc\jCMr-tcD I
OtrHtri CT^CO rnmt^JOlDCO COt—)CT)rH)-Hir>o'm nOOC\Jr—1
tCNJ rHCNJCXj iMCN) CsJCSJrHCMCSJT-H rHCNJi—IC\JCNICsJC\JC\J CNJCSJCSJCSJ
O. s-
E 01
re JD
ooo ooo
III III
CM C\J CM CM CSJ CM
CO CO CO CO CO CO
CM CM
CO CO
i I I I I I
CM CM CM CM CM CM
CO CO CO CO CO CO
oooo
i i i i i i i i i i i i
CSJCNJCNJCSJCMCSJCXJCM CMCNJCSJCSf
CO OD OD CO CO CO OD CO 00 CO CO 00
O
O. S-
£ HI
49
-------
i— re
re T3
c
01
Ol
o T;
a.
re -r-
s_ i—
+J
C 01
i oo «a- oo -a- oo «t oo
•" • . oo "N.
«t •» •* oo
co oo oo ^-
ooooooooo
en CM CM CM r^-Oi-^tH
Or-It—t i—* csjt-H^J-r-1
oooo oooo
ooooooooo oooo oooo
os-ooot-s-oo oooo oo a
01
ocoooor^CMr-ir-i r^. o T—I en oocncn<
CO! T—t O i—t*Hi—t r-i fO T—I i—I Or—t t—I O rHOrOO C
03. ooooooooo oooo oooo re
ooooooooo o'o'o'o oooo ~ _
_^ s_/ s_/^ s_/x_- >_.x_/s_/^^ v^v^ *_/ ^ U
os-oaai-uoo aooo oa o a t-
c — • • - -
z •*, .g „
o ••- t-
•o
V
JQ
/—, re o
3. OOJOOOrHOOOO OOOO OOO3O
c in s—' csicsjcxicvjCNjromcNjcxj CSJCSJCNJCM CMCSI -csj
re .... . . o •
ETJ OOOOOOOOO OOOO OO O 0)
O r— 4J
O h- OJ *J
•O . JIJ
ai
JD l/l O
re ~
X •
\fl
CS( CM *i- CM
oooocoiDcor^oor^r- r^cooor^ U3 cb mr^cNjcn o.re
ro 01 ID CM CD ro ^ CM u"i ro CM I~H ID oo 10 r^ Cfi f~( oo ro •*••
!-••- rHCMfHi-Hf-Hr-irHt—*r-4 CMrHiHT-H r-*CSJT-f in*-*
OJ "v> (/)
3 O) 01
UJ
O J=
CM 4->
_ Ol O Ul
< en r^ T—t I-H r^ «a- en
Ol CMCMCSIt—(^HrHrHi—It—) CMfHCSJCM r-HCMCMCSJ OO1
••- O J=
01 Ol —I 4->
~ s
a>
c i-
o re
•i- a.
u c
a. i-
~ 01
re jo
ooooooooo
CxJOvJCSJCMCNJCsJCSJCsJCsJ
COCOCDCOODOOOOOOCO
r*~ 00 Ol rH
r^ f*-* r*. oo
oooo
iiii
CM CM CM CM
00 00 00 OO
o
CL i.
E 01
O -Q
i-H I + +
I If) U"! LD
O iH «- »)•
IIII
OOOO
CO CO l/l OO
LU UJ UJ LU
CM PO *}• to
oo oo co oo
oooo
i i i i
CM CSJ CM CM
00 OO 00 00
i in in in
O r-l «S- 1-1
IIII
LO I/) CO I/)
IIII
CO OO CO CO
X 4-1
ai
o J2
D.—
E
re re
o c
oo 01
o a>
in D.
•—' 3
O
C Q.
O E
•r- O
4J O
re
E T3
•r- 0)
U
"O O)
ai 4-> •
*j 01 o-
re TJ o
Z> o T>
ui c c
o re
II
01 o
f 13
ro .a
50
-------
ro
cn
O 4J
T5
73
D.'—
OJ Ol
re
-P 4J
re oi
"x 3
UJ
V O)
(A 1
(A
4J ^
Di
1$
Ol
O. i-
£
o
a s-
E D
0 .0
U E
3
(U C
D.
£
re
CO
4/19/84
4/19/84
5/10/84
rH cn CD
r^ CM in
O O rH
o o o
•N^— -
z z
•9- rH
«3- CM ro
0 0 rH
O O O
0 0
Z Z
0 0
*r * oo
O O CM
o o
z z
ro rH ro
CM «3- «3-
co r- oo
ID co r^.
in ro p*-
CD ro o
cn oo rH
rH CM
CD P~ rH
ro ro **•
o o o
1 1 1
CM CM CM
CO CO CO
rH l +
i in in
O rH TT
1 1 1
1 1 1
iii
rH rH rH
* * «t
00 00 CO
10 in co
oo en
CO CM rH
o m o
o o o
§ §
rH in
CM in rH
o n- o
o o o
o a
z z
o o
1- cn fl-
o cn o
a o
z z
rH CD CM
in p^ cn
in oo P*.
in CM rH
o cn rH
rH Cn r-.
Cn rH CO
rH CM CM
CM ro it-
O 0 O
CM CM CM
00 CO 00
«*•
«»• t
rH 1 +
i in in
O rH •*•
1 1 1
o o o
CO CO CO
1 1 1
LU LU LU
Z Z Z
1 1 1
•3- *J"
oo co
cn cn
rH rH
CM rH
ro CM
O O
o o
Z Z
O 00
CM rH
O O
O O
a o
z z
o o
o o
0 0
z z
Cn rH
CM r^
CD 00
•a- CM
CM cn
cn CM
rH CM
ID 00
o o
t 1
CM CM
00 00
•a-
rH -r
i in
o «3-
i i
O O
1 1
f. CO 0 ft
O CT> O O r-H O
i_ t_ s- i. o
LO r*"« LT> r^* c\i o~i
r- o CM ^r oo ro
r-» 00 OO 00 h^ CO
00 rO «Cf rH «S" r— 1
r-« o ro r>*> o to
CD csj eg cxj i— i o
ro ID O tjD 00
CSJ CM T— 1 Csj CSI rH
Oi O rH CM rO id-
*d" to m to m ID
o o o o o o
i i i i i i
CM C\J CM CM CM CM
00 CO 00 GO CO OO
tH | + rH l +
i in LO i LT> ub
i i i i i i
o o o o o o
I/) IO -P
cMcnocncn^J-rHco
CMrHCMiHlHr-CMin
OOOOOOOO
oooooooo
O O O O O i- i-
Z Z Z Z Z +•> 4->
O O O O O CM
OOOOOrHOrH
00000 f- t-
CQincDroCMCMCsirO
ooinocncororoin
coroop**cocococo
COCDlO«3-P~rHCDCn
rHCOCOCM«3-CMCMCM
OOrHCnrHiHCDOrO
rHCMrHCMCMCMCMCM
OOOOOOOO
1 1 1 1 1 1 1 1
CMCMCMCMCMCSICMCM
oocooooooooococo
*S- Tt «3- *J- «•
<-l 1 + r-4 1 + 1 +
i in in i in in in in
i t i i i i i i
oooooooo
COCOCOCOCOCOCOCO
i i i i i i i i
zzzzzzzz
LJJ LJJ LJJ LU LU LU LU LU
1 1 1 1 t 1 1 1
00 CO CO CO
p- TJ- p~ in
in in in CD
p-~ *f- ID rH
CM ro p** in
0000
o o o o
Z +J -P -P
P~ U3 CO r-4
rH CM CO *)•
o o o o
0000
O t- i- (-
Z -r-> 4-> -P
o «• f-
^ LTJ in oo
0 0 rH 0
O i- i. i.
rH CM 00 >3-
co co cn O
co r~ oo oo
oo r*- CM CM
«*• in o P~
**• CD in *j-
ro o CM rH
CM CM CM CM
ro ^ in CD
CD CO ID ID
0000
(III
CM CM CM CM
oo oo oo oo
rH 1 + +
i in in in
O i— 4 "31 ^
CO CO CO CO
1 1 1 1
1 1 1 1
rH rH iH CM
51
-------
T3
Ol
3
C
Xa
C
O
o
rH
rH
01
^
re
r-
in 01
r- CO
re -0
c
Ol
01
1 3.
C
O T3
•P D.
1- i —
C OJ
u !Z
c ro
O -P
o u
(0
^_,
X
01
Ol
1 Ol
C Ol
O 3.
4J
re 01
i. 3
•p in
c in
oi —
u -t->
c
o
o
"^^
Ol
in n.
Ul • — <
E "o
Ol
re u
*J 0)
o -p
r- Ol
-O
•o
'o.~
£?5
Ol Ol
re
•P -P
O *"•
ro Ol
"X I
UJ
Ol Ol
3
in t
in
•p j=
•P •?
01 Ol
3 5
,_
Q. i-
re .Q
in £
r- 1 C
CC
r
Ol
•-
o
ts-
01
o .0
u E
3
01 c:
¥
re
oSoS^oW" *
•s^ v^ *»s, 00 \. 00 *"*•••. CO "^
rHCMCMmrHLOrHt£)rH
m<-*3-irJt£)LDl£>V£>iD
rH co *3" C3 in r** o^ ro
oooo oooo
OOOO 0000'
UOOO E-S-S-O
/*^> /"^> ^^ S~*
rOrHCSJOJ *X)OJl£>OJ
OOOO OOOO
oooo oooo
S-OOO i- I- J- O
4->zzz u -rJ +•> +J z:
OOOO r-f O
OOOO rHOrHO
S-OOO f. &. (. O
-PZZZ u 4-J 4-> w z;
cn^-inrHfo-^r^om
fOiDC\icr»cr»oiDcsio
ooooco^cor^cor^-r^
COCOinCSJ^-kDVjOrH^-
vDcousPor^ojinmoj
r^^-OrHinCTtOCNJlD
o^ooicnrvcocor^
OJOJOJ rHrHrHrHrH
fx. 00 CT\ C3 rH CO ^ Ltt *£
ooooooooo
1 1 1 1 f 1 1 1 1
CNJCSJOJOJOJOJOJOJOJ
*s~ ^i" ^" ^~
rH I 4- rH 1 I + I +
i in m i in m in in in
i i i i i i i i i
ooooooooo
*^> to t/) t/> t/> t/> LO t/i
1 1 1 1 1 1 1 1 1
1 1 1 1 1 1 1 1 1
«a- co co **-
rH rH rH l£>
CD in in yD
VD
O CSI CM rH
OOOO
in ro o *3-
O CM OJ rH
OOOO
m l£> rH ffi
rH «0- ^]- OJ
CM OJ ^- OJ
§00
P-*
r»- ID n in
rH UD 00 IX)
rH CT> t^« rH
CO CT» O rH
OJ rH OJ OJ
r»- 00 Cn rH
OOOO
1 1 1 1
CM CM CM CM
CO CO COCO
*3"
rH i -f 4-
i in m in
O rH ^- ^~
i i i i
i/> ty> (/^ to
i i i i
(/) ^ (/> LO
LU LU LU UJ
1 1 1 1
rH rH rH OJ
^ ^ TJ- CO
CO CO CO\
\ \ ^s. CO
CO •«• r^ rH
LO LD LT> (£>
ro LT> OJ rH
in Ln cn in
oooo
oooo
01- S-
^>
oooo
oooo
o t- t.
Z t-> -U
o r**
«a- rH O Ctt
O rH CM O
r*t ^ ^
cor^iom
r^ CD ^* CD
CD CO O> 00
in r^ CM cn
r^* 01 rH co
rH r»- ^- en
rH CM CM rH
rH CM CM CM
CM ro «• m
§§§§
i i i i
CM CM CM CM
oo oo oo co
^~ ^~
rH 1 + t
i in m in
O rH *f rH
1 1 1 1
l/> CO CO CO
lilt
CO CO CO CO
1 1 1 1
rH rH rH CM
•— ^ C
Z 01
\ 01
X Ol
0 ^
*^ Ol
Ol 01
o.
E re
CO
in 4^
\ CO
Ol
3.-1-'
CD Ol
• in
rH Ol
i.
in Q.
in
o-""
_! C
O
C Q.
0 £
•r- O
*J O
CO
•P 01
•P t—
C
re
rr oi
U
t- re
o <-
+J
••- 1!
E
I — 4J
•a
01 •
re o
E O
•r- _J
a> c
o
Ol T-
r- O
01
• ai
z
CO O
X
E E
t± C
O) OJ
H.
OJ
O JZ
o in
in
•r- (/) *O
^> in r\i
O Cf T—
O -C U
— J ••-> (t)
s^x C E
Oi E
C i- 3
o re 1/1
£ °- *J
u c o
01— C
ai ai re
•D 3 .p
»— re
*4- re "o
0 >
*> 3
'i-o "°
r- *J C
u ai
*O Oi in
01 4J • Ol
•p 01 o- i-
re T3 o a.
E —I
•r- *J -O
•p o -a c
in c C 3
ai re o
II a.
01 0 E
•c. o o o
I — Z to
re ^a u
52
-------
0
in
Ol
O-
£
TO
00
01
in
in
JZ
Cv
(/I
0
0.
•o
t/i
o
Q.
E
O
CM
co
1
ro
l
in
i
o
rH
O
•z.
l/l
o
Ol
TJ
X
O
o.
LLJ
O
r~
U
4J
o.
Ol
X
1
4-J
S-
o
D.
ce
TO
TO
O
CSJ
^
^
_Q
fO
r-
(ft
in 01
>,4->
i — TO
TO -0
C
«
Ol
Dl
I H.
C
O T3
4-1 O.
TO *r~
S- . —
C CJ
0) r-
U .O
C TO
O 4-1
C-> U
TO
4-1
X
01
jj
CJ
i ^
1 Ol
C Dl
O 2.
4J
TO Ol
L, 3
4-1 in
C U!
OJ -r-
U 4-1
c
o
o
.0
Ol
I/) ~1
If) *~S
£ -0
OI
10 U
4-1 0)
O 4-1
h- O)
•o
^3
"o.^-
r^?S
Cl Ol
TO
U ^
TO Ol
•3 O>
X S
LU
HJ Ol
3
i/l 1
in
4-1 .C
o>
4-1 -r-
QJ CU
01
0. S-
TO £1
HH C
ce
s:
O)
o
Q. !-
E 01
0 .0
00 i-H
rH CM
ID r- r-l
O O O
CM CM CM
CO 00 CO
rH 1 4-
i in in
O rH «3-
1 1 1
O O O
OO CO LO
1 1 1
iii
i i t
rH rH rH
CO CO CO
U3 tn *£>
***
en en
rH ro O
O CM O
000
O 0
z z
o r^
rH rH O
O CM O
O O O
O O
z z
/•^ /"^
O O
CM in CM
O «3- O
S— ' *—^
Q O
Z Z
rH ID CM
in i — en
in oo r-.
LO CM rH
O Cn rH
rH en r-~
CTl rH ID
r-l CM CM
CM ro ^
o o o
1 1 1
CM CM CM
CO 00 CO
rH 1 4-
i «n in
O rH «O-
1 1 1
000
OO CO CO
1 1 1
LU LLJ LU
z z z
1 1 1
rH rH rH
^ *!}•
co co
en en
rH rH
**
LD O
rH rH
O O
O O
li
o en
rH O
0 0
0 0
0 0
z z
f**~\
o o
CM CM
O O
^^ ****
0 0
2Z Z
CD rH
csJ r^
ID CO
«a- CM
CM en
r--. o
en CM
rH CM
ID OO
O O
1 1
CM CM
oo oo
rH 4^
i in
o «s-
i i
CO CO
O- 0.
rH rH
•a- «- ^i- oo oo oo
00 00 00 \\\
— \ ' — . CM CM CM
ID LO rH rH r-l rH
^ISioD-^
CO U3 ro CO OO
rO rH ^t- CsJ CSJ r-t
O ro O O O O
O O O O O O
i- E» L. £- Q
^ 4J +J 4_> -Z
in CO O CSJ rH
cst in oo csj csj rH
O CSI O O O O
o o o o o o
i_ L. S. &- O
*•> 4J 4-> -f-* 2
r— *\
co CM o r^ o
in ro tjo ^" tn csj
O *JO O O O O
Sw/
u j- s- ;- o
4J H-> -P *J 2
m r^- tn r-^ csj en
r^. o csj *a- co ro
r- co co co r»- co
CO CO ^a- r-H "9- rH
r*. o ro r- o in
O CSJ CSJ CSJ rH O
ro m o o *J3 co
CSJ CSJ rH CSJ CSJ rH
cn o rH csj ro «3-
O O O O O O
< 1 1 1 1 1
CSJ C-J CSJ CSJ CSJ CSJ
5T + ST +
i m in i in in
0 rH «T 0 rH <3-
1 1 1 1 1 1
0 0 O 0 0 O
CO CO t/> LO CO CO
1111(1
g ggg g g
1 1 1 1 I 1
rH rH rH CSJ CSJ CSJ
sss^SI.?:!
•a- * «r VD LO ID ID ID
csjrHrorHcsjmcsjin
oooooooo
OOOOOOOO
O Q S- t- I- I-
2 2: -U -P 4J -M
rHOCSJrHrH^-CSJ^J-
OOOOOOOO
OOOOOOOO
Q O S- t- S- S-
2 2 -P -(-> -U -4-1
/•S/"^
o o m tjo VD m
csjcsjmcsjrorH«a-o
OOOOOrHOrH
•*~*>*>~r
O Q 1- t- L. t.
tjOtnuDrocsjcsjcsiro
ODinoo^rororoin
«a-h-COt£tCOCOCOCO
coroor*.cocococo
CO^»X>*J-r^rHlXJCn
T-HV£>COCNJ^CSJCSJCS)
COrHCnrHrHlDOro
f— ICSJi— ICSJCSJCSJCSJCSJ
in^r-COOOrHCSJ
OOOOOOOO
1 1 1 1 1 1 1 1
csjesjesjcMcsjCsjcsjcsj
cocococococococo
T-H \ + rH 1 4- 1 +
i in m i m in m m
1 1 1 1 1 1 1 1
OOOOOOOO
tfOcOCOcOCOCOCOcO
1 1 1 1 1 1 1 1
LU LLJ LLJ LU QJ LL1 (A1 LJ i
1 1 1 f 1 1 1 1
1-HrHrHCSJCSJCSjrOrO
CO CO CO CO
m LT) tn t£
co *JD r^. o
csj «3- m ro
o o o o
o o o o
i. i. s-
r*- in rH
4J 4-1 4J
rH ro rH
fl- 1^ CM LO
O O rH O
i- 1_ i-
rH CM 00 "9-
ro ID en o
VD P-. 00 00
oo r-- csj csi
«3- LO o r-~
^j- ID in ^r
ro O CM rH
CM CSI CM CM
ro ^r in CD
CO ID ID ID
0000
1 1 1 1
CM csj csj esj
CO CO CO CO
rH I + +
i in m tn
O rH ^J- ^~
0 0 0 O
CO CO CO CO
1(11
2222
3* ^ ,5 3:
III!
rH rH rH CSJ
53
-------
f~*.
•o
Ol
3
C
Jj
c
o
u
CM
fH
Ol
XI
re
t—
in
in OJ
— re
re -o
c
Ol
Ol
1 —
c
o -o
W 0.
J_ ^
C CD
O •—
U X)
c re
O 4->
o u
re
4-J
X
OJ
4-1
Ol
1 O)
C 01
0 3.
4J
re 01
S- 3
4-> in
c in
Ol •!-
U 4->
c
o
o
X)
^**
Ol
in 3.
m — '
E -0
01
re o
4J OJ
o »J
h- OJ
•o
•o
a.*-^
£?S
Ol Ol
1 —
re
4-> 4-1
U *""
re 01
s- •»-
4J Ol
x s
LU
Oi Ol
3
in
£ x:
Ol
01 CD
3 3
01
CX t-
E 01
re xi
in £
i—i C
a:
^_>
—
in
O
O- t-
£ 01
O S2
u E
o> c
Q.
S
re
OO
SSSgSgSgoo
rH C\) CM LO rH LO fH LD fH
LO^^ISLDLD^DUDUD
^~^^^-^v
rH Cn CM LO fO LD ""fl" CO rH
OOOOOOOOO
OOOOOOOOO
t- o o o t- i- i- t.
VD 00 O O O 00 LO ^" LD
CSJ O rH rH CO rH LO CM PO
ooooooooo
OOOOOOOOO
1- O O Q S- t- J- i-
lO C3 O C3 CO ro ro "sf1
LOc\icsic\jLOroo*3-LO
OOOOOOrHOO
1- Q Q O i- S- t-t.
^->ZZ24J*J *J+J
cn^LOrHro^-r^OLO
rOLDCNJCnCTtOLDCXJO
OOOOCOLDCOP^COr^r^
COCOLOC^^LDLDiHTj-
LDCSILDfOrv-CMLOC^iCXJ
r^<3-OrHLOCnOCsJLD
OLDOCncr>r>-oocor^
C\lC\jesirHrHrHr-*i— trH
r*1* CO en o pH ro ^ to ^
OOOOOOOOO
1 1 1 1 1 1 1 1 1
c\je\jc\jc\jcsjcsjcjc\jc\j
00 CO CO 00 CO CO 00 CO 00
^ ^" ^ ^t"
pH i + r- 1 1 14-1 +
1 LO LO t LO LO LO LO LO
1 1 1 1 1 1 1 1 1
ooooooooo
LO (y) LO •+->
rH CM Cn
rH ^- CO CM
0 rH 0 O
O O O O
U t-
rH CM
ro 00 P*» LD
O CM rH O
L. L.
CM CM *• CM
f**. ro co oo
r*« oo co f-*
r^« LD ro LO
rH LD CO LD
CM rH rH rH
rH Cn f^s rH
CO Cn O rH
CM rH CM CM
f — CO en rH
oooo
i t i i
eg CM c\j CM.
OO 00 CO 00
«3-
LO LO
O i— 1 «3~ rH
1 1 1 1
LO OO OO OO
1 1 1 1
00 LO 00 OO
S 3: 3 S
itil
^
z c
\ 01
00 Ol
X 4->
Ol
O XI
01
Ol >
i— OJ
re re
01 ro
••^^
o c.
co a>
• in
o 01
L.
ift D.
in
o- ""
O T3
—1 c
n^^ , ^
O
•— O
4-> (J
re
4-> Ol
•r- x:
4-> r—
c:
re
o~ oi
u
x- re
0 S-
•i- II
E
Ol •
re o
E O
•S ±i
O) C
o
Ol •<-
x: 4^
t— u
Ol
• Ol
•z
oo o
X 4->
LO E
^^ *"
•o
^ 4^
a. re
re -i-
in 4-1
Ol 01
3-
o x:
CM 4->
o in
•t- in
s-^ in
O O>
o x:
— 1 4-J
•~^ C
0)
C (-
o re
•c- Q.
U C
01 1-
Ol Ol
p^
•4- re
o >
E -d
.r- Ol
u
•a 0)
01 4-> .
4-> Ol O-
re -o o
E —1
4J O "O
in c c
oi re
II
ai a
x: o o
I- Z -J
re xi
54
-------
D
tn
o
o.
•5
4-J
'tfi
O
O.
E
O
CSI
co
U-
l
p
r-.
in
o
o
z
OO
o
c
•o
CO
'
i.
o
CL
01
c^
ro
ro
o
ro
i-H
O)
^
TO
1 —
in
O U
TO
S_
X
CO
^
CO
s
1 C7]
C CJ1
0 3.
IJ
TO QJ
I_ o
.*-> in
C tn
OJ -r-
0 +•>
C
o
XI
D>
in NV'
TO
E "O
ai
TO U
O 4J
r- CO
•D
•o
£•»
CO Oi
4-> *J
TO "§>
L. •!-
X 3
o> en
tn i
in
4-> X
CJ)
-U -i-
01 CO
31 *
01
'D. j_
TO XI
tn E
rH C
CC
s:
O)
-u
••-
o
a. s-
E CO
O Xv
U E
a> c
|-
TJ
00 CO CO
*3- ^- *3-
CSJ CVJ rH
^ \ ***.
oo rt In
rH O O
O O O
000
ZZZ
/*~«in oo
rH in *}•
rH O O
000
O O O
zzz
o o o
a o o
zzz
ro rH ro
csj *s- ^~
UD r*- co
to iD r*~
in ro r^
o ro o
en co rH
rH CSJ
iD r^- rH
ro ro ^l"
o o o
1 1 1
CSI CSJ CSJ
CO CO CO
•3"
rH 1 +
i in in
O rH «3-
1 1 1
o o o
00 00 OO
1 1 1
ggg
1 1 1
CO CO CO
ro o ro
CSJ rH CSI
\ ' \
in csi r-~
en m «3-
000
o o o
o o o
zzz
csj UD r^
in «3- ro
o o o
o o o
o o a
zzz
o o o
000
zzz
rH ID CSJ
in i — en
in oo r-
LO CSJ rH
o en T-H
T-H en r~
Cn rH UD
rH CSI CSI
csj ro ^3-
•=f W ^f
o o o
1 1 1
CSI CSI CSJ
CO 00 00
^
rH 1 +
i un in
O rH O-
1 1 1
O O O
oo oo oo
1 1 1
LJJ LU LJJ
ZZZ
1 1 1
CO CO CO
«3- r^ m
CSJ CSJ CSI
^ ^ ^-
rH CO CSI
co UD in
o o o
o o o
o o o
zzz
rH iD in
tn «g- *3-
o o o
o o o
a o o
zzz
°.°.°.
o a o
zzz
en o rH
csj CO r-
ID UD CO
TJ- r^ csi
csi *3- en
r^. ID o
en rH csj
1 — 1 CSJ CSJ
UD r^ CO
0 0 O
t i i
CSI CSI CSI
co co co
**•
rH 1 H-
i in in
0 rH «-
1 1 1
000
oo oo oo
1 1 1
Q_ Q_ CX
1 1 1
co co co co co co
ro csi **- ro ro ro
CSJ rH CSJ rH rH rH
«j- ^TT ^r To To ?o
m en tn co o^
in «3- P-* in ^3- in
o o o o o ro
000000
a o o oo
z z z z z
ro o csi o co
«a~ «g- tD u~> ro en
o o o o o csj
o o o o o o
a o o o o
z z z z z
O O O O o ro
00000
z z z zz
in r^ in r^. csj en
r- o csj «3- co ro
CO rO »»• rH «t rH
i — o ro r^ o in
O CSI CSI CSJ rH O
ro in UD O UD co
CSI CSJ 1 — 1 CSJ CSI rH
en o rH csi ro *j-
«d- in in in tn un
i i i i i i
CSJ CSJ CSJ CM CSJ CSJ
CO CO CO CO CO CO
*3- *J-
*3" ^^ ^r *^"
rH 1 + rH 1 +
i in in i in in
O rH «1- O rH «3"
1 1 1 1 1 1
O O O O 0 0
oo oo oo oo oo oo
1 1 1 1 1 1
i i T i i i
CO CO CO CO CO CO CO
Lf> ^D ID ^- ^- ^j- iC
CSJ CSJ CSJ t-H rH i— t rH
*^ ^J1 «^ ^O VO l& ^D
?~>.i—* ro co
•—* i^ ixi UD en un o
rH O O O rH CSJ CSJ
0000000
Q O O O S- S-
z: z z z -i-> 4->
LT> UD rH r-..
LO ^J- in ^~ UD rH r**.
O O O O rH Csi rH
O O O O O O O
O O O O I- 5-
Z Z Z Z 4-> -P
O O O O CO UD CTl
O O O O 1- S-
•z.-z.-z.-z.+i 4->
UD in UD ro csi csi ro
co m o en ro ro m
^- r^. co UD co co co
00 ro o r^. co co co
CO UD UD *f r-. rH O*
rH CSJrH
rH UD CO CSJ ^- CSJ Csi
OO rH Ch rH rH UD ro
rH CSI rH CSJ CSI CSJ CSI
tn UD r^ co cn o csi
>n in m m m UD UD
i i i i i i i
CSI CSI CSJ CSI CSJ CSI CSI
CO CO CO CO CO CO CO
*3- ^t-
^" ^f ^ ^"
rH | + rH 1 + +
i in in i in m in
O rH ^- O rH ^- ^*
t t 1 J 1 1 1
O O O O O O O
<*n co to co LO to
i i i i i i i
z zz z z z z
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
1 1 1 1 1 1 1
co oo oo co
O rH O LTJ
rH fH rH rH
in tn tn ID
CO
ro *3" CO in
T-H rH ro o
0000
i. i- 0
•!-> 4-> Z
O r--
OOrH *3- «3-
O rH ro O
O O O O
t- t- 0
en csj r^ o
rH CSJ p*- rH
f- i- 0
•!-> 4-> Z
rH CSJ CO «*
^o UD en o
iO r^ CO CO
00 I — CSJ CSJ
«3- in o r-.
rHrH CSJrH
<3- UD tn «3-
ro O CSI rH
CSI CSJ CSJ CSJ
ro ^j- in UD
O O O O
i i i i
CSJ CSJ CSJ Cst
OO CO CO CO
•d"
rH 1 -f- +
i in in in
CD rH «3- «3-
1 1 1 1
O O O O
OO UO 00 OO
1 1 1 1
§z z z
^^^
1 1 1 1
55
-------
•o
Ol
3
C
4-1
C
O
u
Ol
-D
t—
in
l/l Ol
i— 10
C
^
Ol
01
1 2.
C
O TJ
4-1 O.
S- i —
4-1
C 01
01 —
O X!
c ro
O 4-1
CJ U
ro
4-1
X
01
4J
Ol
5
I Ol
C Ol
O 2-
4-1
re 01
S- 3
4-1 in
C l/l
Ol —
O 4-1
c
o
XI
Ol
I/I 2,
re
E "0
01
r— 4-1
re u
4-1 O)
O 4-1
1— 01
^3
•o
Q-'TX
<- ^
Ol Ol
XI 1
4J 4-1
u x:
S- •*-
4-1 01
x i
UJ
01 Ol
in
•p x:
Ol
4-1 -r-
01 Ol
3 S
Ol
"ci. t-
E 01
re X!
»— i C
CC
z:
01
4-1
in
o
O. l-
E oi
O XI
u E
01 C
1
co
cocooScScocococooSco
ic^^in^roiovDOOOO
^•^J-^-cotgQcDcOcococO
r~*s~* >~\ s-*s~* *~*
in ^" co PX f) t**- r— co co
OOOOrHCMOO O
oooooooo o
*y z 4-1 Z 4-* Z Z Z
.*x^-x ^x /-x^-x *~*
OOOO>-ICMOO O
oooooooo o
o Q s- a i- oo a
ZZ4JZ4J ZZ Z
oo^omaioo o
o a (- Q t- oo o
ZZ4->Z4-l ZZ Z
CT>«-ir)rHiri
oooooooooo
i i i i i i i i i i
OJCSIOviCMCNICMCSJCMCNJCSJ
rH 1 + rH 1 4. 1 + 1 +
O rH ^" O rH *^ rH *S^ rH ^T
1 1 1 1 1 1 1 1 1 1
1 1 1 t 1 1 t 1 1 1
1 1 1 1 1 1 1 1 1 1
00 00 00 00
i^lnuD
m m ID ixi
r^s~*
^- o> ^" 1C
rH IO O O
O O O O
i- a o
4-1 Z Z
^-s^v
01 r»-
rH rx, m «±
rH ITI O O
o o o o
^ C3 O
4-1 Z Z
rH rH O O
f^l i— t rH
i- O O
4-1 Z Z
<\j csj in e\j
^^ ro r^» co
r*- co CO f^
i — LD LD in
rH l£J CM l£>
C\J rH CM rH
CO Ol in rH
CSJ rH C\J CM
^™§oo
o o o o
1 t 1 1
CM CM CNI CSJ
co oo co co
rH 1 1 +
i in in in
O rH rH ^>
1 1 1 1
O O O O
LO l/l CO to
1 t t 1
CO CO I/I CO
UJ LU UJ LU
1 t 1 1
rH rH CM CM
CO «=T CO 00
*? "o^ri
* *^ ^ v^
in in in co
^^
^~v ro
ro in in
rH rH rH O
O O t O
OS- O
Z 4-1 Z
^•N . .
o uo
en ro «3- ^j-
0 rH CO 0
O O ro O
os- a
Z 4-1 Z
o o us o
rH ro CO rH
OS- O
Z 4-1 Z
co r^ CD ro
r^» co ^" UD
ID co en co
CO fx. CM CT>
fx. CTl rH CO
rH CM rH
rH CM CM rH
rH CM CM CM
CM ro ^- in
CO CO 00 CO
o o o o
1 1 1 1
CXI CM CM CM
co co co co
rH 1 4- 1
i in in in
O rH «3- rH
1 1 1 1
0000
> > > >
CO CO CO l/>
t 1 1 1
l/l CO CO CO
lilt
rH rH rH CM
•r- *oi
x: >
4J 01
o re
•+-
c re
o
4J C
4-1 in
•r- 01
C CL
re
3 in
cr •r-
•*- "O
o c
4-> 0
'i ^"
r- O
•o 01
01 JT
4J I—
re
E
4-> Ol
l/l U
ai re
i-
01 4-1
r- II
i.
4-1
Z
CO /-^,
O
X 0
in ^-s
CM C
01 4-1
r- O
Q. 01
E 4-1
re at
01 14-
3. 0
O 4-1
rH 'i
in r—
"O
"O 01
C 4-1
3 ro
o E
S £
O l/l
Ol
in 01
•r- x:
4-1
O "~
•*- in
01
^x in
O ^xjz
— 1 Z 4J
-— '"x, C
CO Ol
C !-
o x re
••- o.
4J O
U rH C
Qj SM^'F—
•*J
CD QJ CD
•0 r- 3
"slS
in
4-1 \ Q.
— Ol . O
E 3. ID — 1
•r- 01
r- O 4-1 -O
• U C
"o ^- 01 re
01 4-1
4-1 w 01 o
m — -o o
•r- T3 4->
4-1 C O C
in 3 c oi
01 O Ol
D. II 5
Ol E 4->
J^ 0 0
-------
b. Polychlorinated Biphenyls
Tables 14 to 22 summarize the data on PCBs. Table 14 presents
total PCB data while Tables 15 to 22 detail the analytical results obtained
for the trichloro- through decachloro-biphenyl homologs on a composite basis.
The total PCB value includes the sum of all homolog data reported as trace
values as well as the positive quantifiable data. The level of detail on the
presence of PCBs in human adipose tissue determined by HRGC/MS presents a
definite advantage over the PGC/ECD approach. The detection and quantisation
of PCBs by the existing PGC/ECD method relies on the measurement of a single
response peak at a specified retention time. The concentration of PCBs in
human adipose tissue up to this point has been reported on a semi quantitative
method via the PGC/ECD method. Data have been reported as not detected, or
detected above or below a certain concentration value.
The determination of the PCBs by the HRGC/MS method described
in this report provides (1) a quantitative measure of PCBs, (2) the distribu-
tion of PCBs by homolog, and (3) the potential to identify specific PCB homo-
log peaks that persist in the human adipose tissue. This distribution of PCB
homologs or specific congeners provides the potential for identifying the
source of exposure (e.g., specific Aroclor) and determining whether this
source varies with geographical location. Figure 16 is an example of the
HRGC/MS PCB data for the analysis of human adipose tissue. Figure 16 illus-
trates the responses for the predominant molecular ions for trichloro through
octachlorobiphenyls. The peaks with the shaded area represent the responses
that were noted as positive identifications within the specific PCB homolog.
c. Chlorinated Benzenes
Tables 23 to 25 present the analytical results for chloroben-
zenes by the HRGC/MS method. Only hexachlorobenzene (HCB) had been included
as a target analyte in previous NHATS analyses programs based on the PGC/ECD
method.
Table 23 indicates that 1,2-dichlorobenzene was detected in
only four of the composites analyzed (frequency of < 10%). A heated dynamic
headspace analysis of adipose tissue for volatile organic compounds indicated
that this compound was present at concentrations of approximately 0.001 ng/g
in nearly 63% of the samples analyzed. As noted in Table 23, the estimated
limit of detection for 1,2-dichlorobenzene by this analysis method is 0.010
ug/g for a 20-g sample. Trichlorobenzene (1,2,4-isomer) was also detected in
a minimum number of samples, but the tetrachlorobenzene isomers and pentachlo-
robenzene were not detected in any of the composited tissue samples. The pres-
ence of pentachlorobenzene in adipose tissues has been reported (Mes, Davies,
Turton 1985) at 0.001 ug/g, which is below the detection level of the HRGC/MS
method described in this report.
Hexachlorobenzene (HCB) has been routinely included as one of
the target pesticides in the analysis of the NHATS composite specimens by the
PGC/ECD method. HCB was detected in 76% of the composite samples analyzed by
the HRGC/MS method. As noted for the organochlorine pesticide, HCB has been
detected at a higher frequency by the PGC/ECD method. Differences in the in-
cidence of detection may be attributed to the respective method sensitivities.
57
-------
o>
1
uo
0)
in
in
h-
OJ
in
O
o.
•o
OJ
4->
•r-
in
O
CL
E
O
CM
CO
u_
1
,^-n,
ro
i
t^j
ro
i
ro
ro
rH
O
Z
tn
o
f^
^.
c:
OJ
CL
•a
oj
ru
£
o
u
o
Q_
1
S-
o
CL
QJ
ce
ro
ro
O
rH
O)
fi
ro
r-
cn
\
2.
c -o
O •<-
••- o.
ro • —
s.
C i—
OJ -C
U 03
C +J
o u
£
X
o>
OJ
^^
1 D>
""*••*
C D>
O "Z-
ro QJ
•p in
c in
QJ »r—
U 4->
C
o
0
01
in ~
in «*^
ro
e -o
, ^j
ro o
O •*•>
h- OJ
•a
3 C
z n- ro
o u
cr
in
in OJ
ro -0
c
*
TJ
•i-
•r- S
t
JO 1
ro
S- ••-
•*-> OJ
X S
LLJ
o> cn
u
cn t
in
O)
0) 01
3 *
0)
D. !-
E 01
cn E
U
Ol
"u>
o
Q. t-
E 01
0 -0.
U E
3
OJ C
t
ro
CD CO
ro CO CM
O O ID
O O O
0
CM ID
CM ID CM
o o m
000
o
z
o
CM CM
O rH rH
^s rH
O
•z.
O CM CO
CO CO CO
cn cn o
rH rH rH
^* ^x. \,
<»•«• in
ro rH ro
CM ^- ^
UD P~ CO
in ro r-v
O ro CD
Cn CO rH
r-H CM
ID r»- rH
ro ro «*•
000
> 1 J
CM CM CM
CO CO CO
•w?
rH 1 +
i in in
O rH *}•
O O O
in in co
O O O
i i i
rH rH rH
cn
rH O ID
0 rH rH
O O O
0
O rH
I-H cn ro
0 0 rH
0 0 O
Q
z
o
CM o -a-
O CM ro
^•^
o
z
Q r— m
«j- *r co
oo co \
ID LT) rH
v^_ ^»^ "^
^••a- «r
i—t ID CM
in f^- cn
in co r~
O Cn rH
rH Cn P*-
CT) rH ID
rH CM CM
CM ro ^r
•a- -a- >s-
000
t i i
CM CM CM
00 CO CO
* 5
I-H 1 +
i LD in
O r-l f
O O O
in LO tn
LLJ LLJ UJ
Z Z Z
i-H rH i-H
ID
rH in
O ro
0 0
So
O ro
0 0
o
CM r**-
o to
^•^
>
Z
CO CO
CTi O^
rH rH
**"•» ^^v.
•3- 0 IA
1 1
Q. 0-
t 1
—4 rH
O^ CM CM in VD rH
rH CM CM rH CM rH
O O O O O O
m co cn CM o tn rH rH rH rH
""*•» """x **•«•. ^x. ^x. *x.
*!- *3- U) i£) ^0 <£>
in rx m r**. CM cri
r^. o CM «* co ro
r*- co co co r*"- oo
COrO^rH^-rH
r*- o ro rx o m
O CM CM CM rH O
ro in UD o ui CO
CM CM rH CM CM rH
cn o rH CM ro «a-
^- in in m m in
o o o o o o
i i i i i i
CM CM CM CM CM CM
CO CO CO CO 00 CO
«=j- 5 Lf) i in in
O rH ^- O 1 — I *S~
f 1 I 1 1 1
O O O O O O
to t/ii to to to
1 1 1 1 1 1
1 1 1 1 1 t
rH rH rH CM CM CM
ro fx CTt ^f" rH rx
OOOOrHlDOrO
OOOOOOOO
**** s-^
O 0
z z
rH i-H in Cn ^- LO
ooooomom
oooooooo
^^ v^
0 O
z z
o o o
CM rH ro CM CO ro in
OrHOOrHinrHlx,
x^ XiX rH
jT^l Q
Z Z
oinrHouscomro
Z Z rH rH
cococo^^^^^-
x^ x^ x^ oo CO CO CO CO
rH CM CM in *^ i i i
zzzzzzzz
1 1 1 1 1 1 1 1
T-HrHrHCMCMCMroro
rH ro CO I-H
O O O O
CO
ID OO U5 «J-
O CM r~ rH
O 0 O 0
VD CO O
rH in r^. ro
rH
VD CM i-H Cn
i-H CM
^- ^. ^j. ^.
CO CO CO CO
r*^ ^" r^ ^1
X^ X^ x^ x».
in m m u?
rH CM CO •«•
ro ti> cr> o
VD rx oo oo
oo r-- CM CM
«3- in o rx
rH rH CM rH
^- UD in ^t
ro O CM rH
CM CM CM CM
ro *f tn VD
(£> t£> l£> \D
O O O O
1 1 1 1
CM CM CM CM
CO CO CO CO
«f •*
«-H I + -r-
i m m m
01-*^-^-
iiii
0 O 0 O
<-O l/l CO I/)
g g g §
rH rH tH CM
58
-------
Ol
Ol
Sir3
"- D.
C i—
U -Q
in oo
rr> 1-1 rH in
CO CM CM CO
rH CM ro O
OOOOOOOrHOrH OrHOrH
O O O O
C Ol
O 3.
Or- (r- tOrOlDOOCOCMCSJ
f^ O CO 00 Cn O CM
CM Cn rH CM OrHfOCO
OOOOOOOOOrH OOOrH OOOO
C
o
o
01
i/> n.
in x-*
re
E -a
01
o
CM rH
•o
OJ
01
3
C
13
c
o
u
cu ro <->
E Q.-I-!
3 C
z f — rH
CSJCNJC\Jr-(«— ICMr— tr-l»H
CO Cn O rH
CM TH CM CM
oooooooooo
r~. co cn rH
OOOO
CM CM CM CM
00 00 00 CO
CM ro «± in
00 00 00 00
OOOO
till
CM CM CM CM
00 00 CO CO
o
O. i-
S 01
U E
3
OJ C
Q.
E
re
§§
§§§§
t 1 1 I 1
co co co co
i i i i
CO CO CO CO
LU LJJ LU LU
I I I I
CO CO CO CO
59
-------
tl
l/l
Ol
o.
E
re
00
01
in
in
*~
Ol
in
o
0.
•5
01
£
o
o.
E
o
0
CM
co
u_
CO
ro
CM
in
CM
O
Z
00
5
p~
c
O)
0.
J3
o
i-
o
u
r-
'
i-
o
c.
01
ex.
re
in
i— i
01
&
ra
\
3.
I * —
C ^S
O *r~
•r- Q.
i.
«*-> Ol
C r—
Ol JD
O TO
C 4->
O U
c_3 to
*J
X
01
4->
Ol
S
i '5
C CT
O 2.
TO 01
S— 2
4-> in
c in
Ol '^
o *•>
c
0
o
J3
'o>
I/) ••— '
re
E "O
01
<0 U
•P Ol
0 J->
Ol
in •*->
i. ^ fO
f> Q] tr—
£ 0. *J
3 C
Z •+- re
O 3
o-
in
in 01
re "D
c
•o
O--~>
s r
O -C
U -r-
X S
UJ
01 Ol
rj
in i
in
•4-> .C
Ol
01 Ol
2 2
Ol
CL s-
E 01
re J3
Z
01
in
O
O. S-
E 01
O °
U £
01 C
g-
oo
^£1 in rH
CO rH rH
O O O
O O O
§O O
Z Z.
CM rH O
CM rH rH
O O O
000
000
Z.Z.Z.
000
CM CM CM
O O O
o o o
Z.Z.Z.
000
sss
CT> cr> o
rH rH i— 1
^- fl- to
ro -H ro
C\J **• ^"
voior-
in ro r^
o ro o
cn oo i— i
T-H C\l
VD f^*- r~<
ro ro ^~
000
1 1 1
C\J CSJ C\J
OO CO 00
«s- 5
I— 4 1 +
i LO m
1 1 1
o o o
(-O V> tO
o o o
1— 1 T— t t— 1
c^ o cn
tH rH O
o o o
o o o
O Q O
z z z
o cri r^.
rH CD O
000
o o o
o a o
Z.-Z.Z.
000
CM CM CM
000
o a o
o o o
Z.Z.Z.
CO CO CO
ID ID in
^" *?" "sf
rH ID CM
in r^ cn
tn co r^-
in CM rH
O Cn rH
rH cn r-.
Cn rH l£J
rH CM CM
CM ro «st
•a- «3- "3-
o o o
1 1 1
CM CM CM
CO CO CO
•a- ?
i m in
i i i
> > >
oo oo oo
1 1 1
UJ UJ UJ
1 1 1
rH rH rH
ID O
rH rH
O O
0 0
0 0
O cn
T~l O
O O
0 0
00
z. z.
o o
CM CM
O O
0 0
z. z.
0 0
z z
*r *f
coco
cn cn
rH rH
•C" ^
Cn rH
CM r-
ID CO
«3- CM
CM cn
r~ o
cn CM
rH CM
ID CO
0 0
1 1
CM CM
CO CO
,j.
rH +
i in
i i
oo oo
1 1
U> in rH rH rH rH
^f ^ VD 1C tr* (£
in r^ in r^ CM cn
r^ o CM ^j- co ro
CO ro «3" rH ^- rH
r^ o ro r^- ^3 in
O CM CM CM rH O
ro in to o ID co
CM CM rH CM CM rH
Cn O rH CM ro «}•
<*• in in in in in
000000
i i i i i i
CM CM CM CM CM CM
co co co co co co
q. 5 «* 5
rH 1 + rH 1 +
i in in i in in
i i i i i i
iioliil
i i i i i >
gggggg
i i i i i i
rH rH rH CM CM CM
rocMcn^rcMCOCM^-
CM rH rH rH rH rH rH rH
OOOOOOOO
OOOOOOOO
OOt-OOi-Oi-
rHCnincnomocM
oooooooo
oooooooo
oo s- o a s- o i.
Z. Z 4-) 2C Z 4*^ Z 4^
oooooooco
CMCMCOCMCM«J-CMCM
oooooooo
oos-aos-a •-
22"zz"z"
OOrHOOrHOrH
z z z z z.
SSSggggg
rHCMCNJin^^J-intD.
rocMCMCMco
COinocnrororoin
coroor^cocococo
coioiD»»-r— rHu>cn
rHVDCOCM^rCMCMCM
COrHCnrHrHt^Oro
rHCMrHCMCMCMCsJCM
iniDr^cocnorHCM
oooooooo
1 1 1 1 1 1 1 1
CMCMCMCMCMCMCMCM
cocococococococo
.^ 5 «a- 5 S
rH 1 + i-H 1 + 1 +
i in in i in in in in
i i i i i i i i
oooooooooooooooo
i i i i i i i i
zzzzzzzz
1 1 1 1 1 1 1 1
rHrHrHCMCMCMrorO
i— 1 ro ^- CM
CM rH CM rH
O O O 0
O O O O
0 0 i- O
Z Z 4-> Z
w o CM en
o o o o
o o o o
O O i- O
Z Z 4-> Z
o o cn o
CM CM * CM
0000
0 0 S. 0
Z Z 4-> Z
§0 rH 0
Z Z
co co co co
r^
-------
Table 15 (continued)
'S
3.
O T-
- wet Concent
g) extractablf
C CT
ro oj
C ifi
QJ -r-
u +•>
c
o
.0
en
15
OJ
ro u
o •*-»
"•S
•O
111
tfi 4-1
s- .* ro
01 10 4J
XI 01 •-
E Q.4^
3 C
Z >4- ro
o 3
CT
in 01
c
x:
0)
flJ QJ
2 ?
0)
a. i-
ro x:
s:
01
o
a. i-
Sf
01 C
D.
£
ro
CO
CMCn'ro^rHcnooro'Lo'ro
OOOOOOOOOO
OOOOOOOOOO
OO S- O 1- £-OOO S-
OCOCnOOCOrHrHrHm
OOOOOOOOOO
OOOOOOOOOO
aos-ai-i-ooos-
OOOOOOOOOOrH
oooooooooo
OO S-O S- S-OOO S-
OOrHOrHrHOOOrH
Z Z Z Z Z Z
•9- -a- «t t o- f
oocooo*j-co«i-»3-cO'O-co
cn^-tr>rHroen*^OLO
SSSSooSSS^0.
co co LO CM * en ID co rH «•
IX>CMlDror-.rHCMtnrOCM
CMCMCMrHrHCMrHrHrHrH
OOOOOOOOOO
1 1 1 1 1 1 1 1 t 1
CMCMCMCMCMCMCMCMCMCM
cooooocococococococo
i-H 1 + rH 1 + 1 + 1 H-
II 1
OOOOOOOOOO
1 1 1 1 1 1 1 1 1 1
1 1 1 1 1 1 1 1 1 1
en CM rH CM
O O O O
o o o o
s- a o o
4-> Z Z Z
r~- o o en
o o o o
o o o o
S-OOO
4-> Z Z Z
o o o o
CM CM CM CM
o o o o
s- a o o
4-> Z Z Z
rH O O O
z z z
•s- oo oo «*
\ o o \
I-H rH rH 1X>
co tn in LD
CM CM q- CM
r^ PO oo co
f^ t^ ro m
rH ID CO VD
oo en o rH
CM rH CM CM
r- oo en rH
o o o o
CM CM OJ CM
00 00 00 CO
r-H 1 + +
1 if) ID LD
till
o o o o
L/l CO CO CO
1 1 t 1
CO CO CO CO
UJ LU UJ UU
lilt
rH i-( T-H CNJ
r^- o o --I
o o o o
O O 0 O
o o s- o
•Z.-Z -^ -z.
00 O"t CTl O^
o o o o
o o o o
Q O t- O
z: z .M z:
O O CM O
c\j csj ^- CM
o o o o
a a s- o
z z -P z:
O a rH O
z: z z
«d-
*r Lf> LT> CD
CD ^-- CD ro
r^ CD tj- co
en r*-v csi en
r-» CTI ^H oo
i— t r*-* <3- en
rH CSJ CSJ rH
rH CM CNJ CM
CM en «3- LO
o o o o
1 1 1 1
CM CM CM CM
CO 00 00 00
rH I + l
1 LD LO LO
CO CO CO CO
1 1 1 1
CO CO CO CO
1 1 1 1
rH rH rH CM
TD
c
3
0
E
u c
4->
OJ
S- XI
o
4- 1 —
01
O* 01
0 —
_J
^^ (0
C 4->
o ro
•P 4->
ro c
•r- l/l
c s-
3
"4-
O "O
c
4-> 3
— o
E a.
r^ O
u
Ol Ol
ro H-
E
4->
a> u
to
01 t-
x: 4->
r-
II
S-
/-s 4J
z
^
00
X 0
o
LO —1
^>
CM
•*^ c
o
r- £
a. u
E 01
ro 4J
tn ai
•v, -0
01
a "S
o
CM 4->
o 'i
tn < —
•O 0)
3 ro
0 E
E 4->
o in
•r- .C
x: 4-1
4^
tn
S- •!-
0
1- in
ai
^~> in
0 x:
—1 4->
•*-* c.
Ol
c t-
o ro
•r- Q.
4J •
u ***• c
01 Z •«-
4J ^>«
•a 3
X i—
**- ro
o o >
rH
4-> >^>
E 01 tJ
•r- r- Ol
T3 rtJ Ol
4-> ^-» oi o-
ro cn"o o
4-> O O T3
U) CD C C
Ol • (0
0 II
01 O
.c in 0 O
r- •<- Z —I
ro X3
61
-------
0
IA
0)
!
GO
01
3
(A
(A
K
0>
(A
O
Composite Adi
CM
oo
>-
^N
o
ro
ro
«t
fH
Ol
ID
CM
6
Z
I/I
«r
o
>.^
£
.e
0.
.5
o
i.
0
jC
lt>
S-
OJ
h-
1
4->
i-
o
CL
Ol
C£
re
4->
o
id
rH
01
.O
10
t-
^-•v
D)
\
O)
a.
i ^^
C -D
O i-
•i- o.
.p -i-
S-
+-> 01
C i—
,ion - wet Conce
(MQ/9) extractab
Q 01
i- 3
4-> IA
C 1A
Ol -f-
U 4->
C
O
cj
J3
/— s
01
in a.
tfl ^>
(0
01
ro u
4-} +J
U -C
t- -r-
X S
LJJ
at oj
D
in i
V)
4-> x:
D)
4J -r-
3§!
01
¥fe
(0 .Q
(A E
3
en
s.
^*.
(A LD in
ro r-l csi
o o o
000
^-s *»*
Z Z *>
x^s /->
CsJ rH rH
CM rH CM
0 O 0
000
VvS ^w'
O O S-
Z Z 4->
o o <•
CSI CM *}•
o o o
<**f *^
O O S-
Z Z J->
O D rH
Z Z
1- «*• fl-
oo oo co
U> (Tl O
rH rH fH
ro rH m
CM «t 0-
i£> r~ oo
(£> U3 f^
in PO r^
o ro o
CT> 00 rH
rH CM
1£> r*- rH
rfi m t
000
CM CM CM
00 00 00
*
rH 1 4-
i in in
i i i
°°§
oo (/) eo
i i i
O O O
i r l
rH fH rH
s-^
Ol 00 rH
rH rH rH
O O O
o o o
^
Z HJ J->
O U) Ol
rH rH O
O O O
O O O
**^
O S- S-
Z H-> 4->
/-**
O i£) ro
CM ro CM
000
>M>
O t i-
Z •!-> •(->
Q tH rH
Z
«•
«• * oo
oo oo v.
^^ in
to in rH
rH IO CM
in r«v eft
in oo r~
tn CM rH
O CT> rH
rH Ol p^
Ol rH U3
rH CM CM
CM CO "9-
«• «3- > >
to i/> to
1 1 1
UJ UJ UJ
z z z
1 1 1
rH rH rH
/~\ r~*
ID CM
rH in
O O
0 0
•^^^^
z z
o m
rH V
O O
O O
o o
z z
^ s~*
0 0
CM CM
0 0
tv* ^*
o a
z z
a a
z z
«t •»
oo co
Ol Ol
rH rH
Ol rH
CM r^
to oo
CM
rH CM
ID 00
«3- -3-
O O
1 1
CM CM
co oo
-H +
i in
i i
o o
> >
LO l/>
1 1
< >>>>>
i/> to i/) ty> oo oo
i i i i i i
i t i i i i
rH rH rH CM CM CM
COCMrO^fCMrHCMr*.
CMrHrHrHrH^-rHfO
oooooooo
oooooooo
'**' *~* **s°*s ^~s
Z Z Z Z •!-> Z *>
tHOlOOiOfOCM
THOrHOrHrOrHrO
OOOOOOOO
OOOOOOOO
N*** >**'*^**S ^^
a a o o t- o s-
z z z z *> z <->
0 0 00 CM O 0 «f
CNJCMCMCMCMOlCMr^
OOOOOOOO
S^/ v_x Sws<^' <^
o a o o i- o s-
Z Z Z Z *J Z 4->
QOOOrHiHOrH
Z Z Z Z Z
1- ^f «J-
oooooo«-'S-«-^j-«i-
rHCMCMinrJ-Tj-lDlO
iDiniorocMCMCMro
comooirororoin
4-f->ooiDoooocooo
ooroop~oooooooo
OOlOlOfr-rHlDO!
rHlDOOCMfl-CMCMCM
OOrHOlrHrHUSOro
rHCMrHCMCSJCMCMCM
iniDt^OOOlOrHCM
inmminintDiDvD
oooooooo
t t i i i i i i
CMCMCMCMCMCMCMCM
«s- «*• >>>>>>>
OOOOLOOOOOtOLOOO
1 1 1 1 1 1 1 1
zzzzzzzz
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 i 1 1 1 1 1 1 1 1
1 1 t 1 1 1 1 1
rHrHrHCNJCMCMrOrO
/-^
^- rH in in
rH ro in rH
O O O O
O O O O
**s
Z 4-> 4->
/— \
en ro 01 CM
O CM *t rH
o o o o
o o o o
****
OS- t-
Z .P *>
(^S
o oo m
CM *t rH CM
O O rH O
^r
O S- (•
Z 4-> J->
O rH rH rH
Z
oo oo oo oo
r-- «a- t»- m
rH CM 00 f
ro ID 01 o
ID r~ CO 00
OO P*- CM CM
«t in o r~-
t ID in «•
rO O CM rH
CM CM CM CM
ro «*• in ID
ID ID ID ID
O O O O
1 t 1 1
CM CM CM CM
OO 00 00 OO
^f
I"! 1 + +
i in m in
§§§§
IS) l/> (/I CO
i i i i
i i i i
•-H rH r-t C\J
62
-------
•o
o>
3
C
C
O
u
<£>
rH
01
XI
re
r-
Cn
CD
3.
1 s^
C "O
O •!-
• r- Q.
TO r—
s-
+J 01
c: i —
O) XI
(J TO
C 4->
O 0
O TO
t-
^j
x
01
^J
o>
J
i en
c en
O 3.
ID OJ
S- 3
4^ in
c i/j
O) -r-
O 4-^
C
o
^^
Cn
»/) 3.
in ^/
TO
0)
« — 4J
TO (J
O 4-»
r- CO
•o
01
i- J2 TO
Ol TO 4->
£ p is
3 C
Z it- TO
0 3
cr
1/1
V) 0)
>,*>
•— TO
10 -D
c
•o
'•?£
XJ <
U -C
t- -r-
X S
UJ
01 en
3
U) 1
I/)
£ x:
tu'cf
01
TO Xl
l-i C
ce
z
o>
•—
o
0, i-
E 0>
0 -Q
u E
3
O) C
¥
TO
oo
c7£"cv7£^ in cniDr-.no
oooooooooo
oooooooooo
^*s *^s ^— • s^
OQOOi- !_£-[-
OCOOOCnCOroOOvD
rHOrHrHrorOrH^"CMt£>
OOOOOOOOOO
OOOOOOOOOO
S*. J •*^f *^ "^rf
oocaos- s-i-s-
O O O O VD 00 ^" CSI VD
ojojcsicsjr^cncMr-oocs)
OOOOOOOOOrH
s»^\_ /SM / X*>
OOOOI- t-t-t-
y ^^ ^ 2;
00 CO CO ^" CO ^" ^f 00 ^" CO
•Ni^ V^ ^^ iflQ -^^ QQ QQ *x^ QQ ^^
rH C\J C\J LO r~t ^" L/> rH tD rH
cn^-inrHPom^r^Oin
ScocoSSSSSKg
CO CO « CSJ * ^> U) rH ^
«X)CMi£)ror^rHcga-)roeM
rH CS| rH OO rH
f^*-OrHtnrHcnOC\J
ovDOcncn^r^cdcd^
oooooooooo
11(1111111
CMCMCMCSJCMCMCSJCSJCNJCNJ
^" <3" ^" ^"
rH I + rH I -f 1 + 1 +
i in in > ID LO LD m tn tn
t 1 1 1 t 1 1 t 1 (
oooooooooo
OO t/7 tO OO d/1 OO l/> 4/1 V7 4/1
1 I 1 1 1 1 1 1 I 1
1 1 1 1 1 1 1 1 1 1
STrHrnV
O O 0 0
0 O O O
v«^ **~s
o s- o i.
Z -P Z -P
O CO r- 1 CO
O O O O
O O O O
^«rf* s— «•
o s- o s-
Z -*J Z 4-5
O CO O CO
CM oo csj r--
0000
v> •*->
o t- o s-
Z -M Z -M
O rH O rH
Z Z
^ CO 00 ^~
I— 1 r-* rH \£>
ID Lf) ifl UD
CM CM ^- CM
h1* CO CO 00
r- co co r-
r^* vD PO to
rH i£) CO U3
CM
CO Cn O rH
r^ co en i-t
r— . i — r*- co
O 0 0 0
ttti
CSJ CM CM CM
CO CO CO CO
^~
rH i + -f
i ur> in LO
O rH «3- ^3-
) I I I
OO OO OO *S)
1 1 1 1
OO OO OO 00
LU LU LU LU
1111
rH rH rH CM
("••» CO ro i~H
CSJ rH CSI <~~t
0000
o o o o
**** *^^
O S- I- O
Z +> +> Z
oo in rH en
rH rH CSI O
O O O O
O O O O
^•- ^rf'
a s- i- a
Z -U *J Z
o m oo o
CSI CO rj- CSI
o o o o
^^ ^-x
o i- i- a
Z 4-> 4-> Z
0 rH i-H Q
Z Z
^ ^J- ^f CO
QD 00 OO-v.
oo «• r-. I-H
in in in ID
VD r^- ID ro
r^ UD •cj- ID
ID oo en oo
in r^ csj en
r— en rH oo
rH CSJ CSJ rH
csi ro «t in
00 00 00 00
o o o o
1 1 1 1
CSI CSI CSJ CSJ
oo oo oo oo
^" ^~
rH 1 + 1
i in in in
O rH «J- i-H
1 t 1 1
l/> OO l/> (JO
1 1 1 1
LO c/i t/)
1 1 1 1
rH rH rH CSJ
TJ
^
O
CL
E
Q
U
£
i/) a>
•f- Q)
-c 5
4J *J
a>
S- J3
o
OJ
•*""*• >
cr a>
O r-
^> TO
C *J
o to
>r~-
4-J -P
(C C
4J 0)
•r- CA
•P 0)
c s_
(TJ Q_
3
cr w>
M-
O -D
c
•U 3
•r- O
- t
r- 0
u
T3
a a>
-»-> j:
TO r-
E
4->
V) O>
O) U
TO
a> '-
-C 4->
h-
II
s.
/-^ 4J
Z
•*^
l/>
^•^
x o
0
in —i
w
CSJ
^ c
o
01 -r-
CJ. U
D a>
TO 4J
t/> a)
•V T3
CD
3- 1-
O
0
CSJ 4->
o i
U) r—
u
•D 01
CZ | '
3 TO
° J
E 4->
O m
OJ
— j;
.C 4-1
(/)
f~ >p-
o
**- in
aj
' — • W>
a ai
o x:
01
c s-
O TO
£ . D'
U *"* C
Ol Z -r-
Ol Ifl «)
•a 3
X i—
4- TO
0 O >
rH
4-> --^
E 0) T3
•P* r— Qf
•— Q.4J
S U
•O TO 0)
QJ I/I 4^ •
4J \ OJ O*
10 CDTJ O
E 3. 1
.1- 4_>
4-> O O "O
VI 00 C C
ai . ra
O II
d) " 0.
-C ifl Q O
r- *r- Z 1
re xi
63
-------
tl
in
OJ
I
ro
to
01
in
1
OI
in
o
0.
^
01
in
O
O
CM
CO
u_
1
CM
1
cn
CM
i
en
CM
in
CM
o
z
CO
CJ
,—
C
JL
Q.
O
O
f-
u
(0
0)
0.
1
+J
i.
o
Q.
Ol
01
c •—
at .0
u in
c m
0) -r-
0 -P
o
CJ
•°^
D)
in n
in • — '
ro
a>
10 U
4^ ai
O *J
r- 01
T3
TJ
0>
in 4->
i. jx m
ai ro •*•>
jQ at 'r-
3 C
Z M- (0
O =
CT
in
in a>
•— IO
10 "U
C
73
"£•*
-H C
CC
E:
ai
>p.
in
O
Q. S.
E Ol
O ^3
<-> E
ai c
CL
E
(O
^~
rH en
r^ CM ro
O O rH
O O O
Z Z
*»• CM
O- CM rH
O O rH
000
O O
Z Z
00
«i- *r CM
o o CM
o o
z z
O O rH
Z Z
CO 00 OO
en en o
rH rH rH
*J- «!}• in
ro rH ro
CM *t ^f
in ro p-
rH rH
O ro O
en co I-H
rH CM
VD P-- rH
O O O
1 1 1
CM CM CM
oo oo oo
^_
f—t 1 +
i in in
0 rH *t
1 1 1
l/> VO LO
< 1 1
o o o
rH rH rH
^
00 «•
ro CM ro
O O rH
O O O
CD $—
Z 4->
rH rH
CM CM O
O O rH
O O O
Vw*
o •—
z ••->
o vc
•s- «d- r-
o o CM
O i-
o CM ro
z
*c «- oo
ID m rH
•s- «• *
rH VD CM
in r-- en
in co r~.
o a> rH
rH rH CM
rH cn r^
Cn rH VD
rH CM CM
CM ro «f
S«- "9-
o o
1 1 1
CM CNJ CM
00 00 OO
•3-
rH 1 +
i in in
i i <
vn to vo
LU LU LU
Z Z Z
rH rH rH
-*
CM P~
ro ro
O O
0 0
CD >>
z -u
O CM
CM ro
0 0
o o
^^
o (-
Z •*->
0 rH
0 0
O S-
z *•>
O CM
Z
oo co
en en
rH rH
^ «3"
Cn rH
CM P^
VD 00
CM en
r~ o
en CM
rH CM
VD CO
0 0
1 1
CM CM
00 00
rH +
i in
o «»•
i t
CO 1-0
1 1
«£ <:
0.0-
i i
rH rH
CM 00 CM rH rH
P*- VD OO *}• O CO
O O O O rH O
O O O O O O
4-> +J *J *J 4J
VD in oo tn o oo
LO in vo ro CO VD
o o o o o o
000000
i. S- i- !~ i.
*J*J 4J *J -r>
o
rO ^J- rH p*. rH CM
rH rH rH O CM rH
S- i- i. i- i-
*J *J *J *J +J
in in ro CM •«*• rH
«3- rr «a- oo oo oo
oo co oo \ *^^ ^^
VD LO rH rH rH rH
*r «J- vo VD VD VD
in r^ in p^ csj en
r~ o CM *3- co ro
p^ CD ro P*^ o in
O CM CM CM rH O
ro in VD o VD CO
CM CM rH CM CM rH
cn o rH CM ro «t
4~ LO in LO in in
o o o o o o
i i i i t i
CM CM CM CM CM CM
^ <•
rH 1 + rH 1 +
1 LO LO 1 LO LO
O rH fl- O rH «S-
1 1 1 1 1 1
OO 0 O O O
>>>>>>
CO CO VO VO l/> VO
1 1 1 1 1 1
S S «E S Z Z
1 1 1 1 1 I
rH rH rH CM CM CM
^-^^-S/-N^-X
LO LO LO p^ rH CTi CM
*rCMCMCMrOrHOJI —
OOOOOiHOO
OOOOOOOO
^M'^O'^M' ^v*1
Z Z Z Z *J •!-> *J
CMCnCMrHCMCnCMVD
OrHOOOOOO
OOOOOOOO
^^•^^Sv^^^
O O O O VD CO
OOOOOCMOrH
OOOOrororoCM
Z Z Z Z
^^^SoSSoSoo
rH CSj C\J in ^J" ^" lO CD
^•^^•CDVDCDCOCD
cDLncDrocMCsjcsico
oomocftrororom
coroc^r^cocococo
odcDco'^r^r-icD'c^
CM
rHCDOOCSJ-cfCSJCsJCsj
COrHCnrHrHCDOro
rHCsJrHCSJCSJCNJCSJCSI
mcDr^-cocnorHcsi
gggggggg
1 1 1 1 1 1 1 1
C\ICSJCSJCSJC\JC\IO\1C\1
^J- ^- ^_
rH I -r- rH l -r- 1 +
i in in t m in in tn
i < i i i i i t
OOOOOOOO
VO V/> VO CO CO CO CO CO
1 1 1 1 1 1 1 1
zzzzzzzz
1 1 1 1 1 1 1 1
rHrHrHCMCMCMroro
CM CM OO
SVD VD ^~
O 1-H O
O O O O
*-> +J *J
VD 00 cn
CM «3- «»• ro
0 0 rH 0
O O 0 0
CM 00 ro
VD cn CM oo
o o ro o
ro CM ro ro
aooo oS oo
p*« ^" p^ in
in in in VD
rH CM 00 «S-
ro VD en o
VD p~ 00 OO
OO P^ CM CM
«• LO o r~
rH rH CM rH
^^ VD tn ^
ro o CM I-H
CM CM CM CM
ro ^}- LO VD
VD VD VD VD
O 00 0
CM CSJ CM CM
oo oo oo oo
^>
rH 1 + +
1 LO LO LO
O rH «• «t
1 1 1 1
O O O O
CO CO CO CO
1 t 1 1
§z z z
S3 »
1 1 1 1
rH rH rH CM
64
-------
•o
3
C
C
O
0 0
o ro
X
at
^
at
S
I 01
c en
O ~*
ro ai
i- 3
4-> in
C in
at .r-
U 4J
c
o
.0
Ol
in 3.
ro
a>
ro u
4-> at
O 4->
r— ai
•o
•a
01
in 4J
s_ -* ro
at ro 4^
f~> ai •*—
E 0.4-1
3 C
z >»- ro
0 3
cr
in at
2"S
ro TJ
c
•0
Q.-^N
~5S
»— -
JD i
4-9 4J
U -C
s- •<-
4-> (11
X 5
UJ
QJ O>
tn i
i/>
•r- -P
O>
CD a>
0)
"a. s-
UJ .Q
(/) £
i— t C
CC
OJ
•P
w
o
a. s-
E QJ
Si
c
CL
E
(TD
l-O
X-N
*j- r^- o o **• r^
OOOOOi— tOCMtCrH
oooooooooo
S.*'
s- s- o s- s-
CTtO^O'-H^'OOrH P11^
OOOOOOOCSJOt-^
oooooooooo
\^f
t_ t- o s- s-
+) +J Z 4J 4->
O"» O O *£>
OrHOOrHCsJr-l^-OCM
I- ^ O iL. i-
*^ CO CNJ O *"O C\J LO ^f" ^H C^
•zr
|||s|ss|s|
tHC\JC\jLnrH^'U^rH^r-H
LO ^" tf t£ t^ i»D y? U3 *^ US
av^-Lnr-iroOTa-r-oin
roCOCMCTiCnrOOCDCMO
oocoooiDODoor^oor^r^
OOOOCOCM»3-CniDlDrH«t
VDCMlDror^r-ltSlinroCM
r-«-OrHLnrHClOCS|lD
oiDOcncncor^cooor^
CMCMCMrHrHCMt— IrHrHrH
r-coa^o.-HeMro^Ln^
oooooooooo
I I 1 1 1 1 1 1 1 1
CsJCMCMOJCNJCSICMCSICSICXJ
rH t + rH t + 1 + 1 +
1 1 1 1 1 1 1 1 1 1
oooooogooo
t/)C-*>tOt/lt/>(/)t/)t-O(/i(^<^>t/)
1 1 1 1 1 1 I 1 1 1
T— tt— 4t-Hcsjc\ie\jrin(vi^j'^'
^^
CM r*-. 10 r»»
O CM O i-l
o o o o
^M*1
0 t-
Z 4J
oo ko
rH CM If) CO
O CM O rH
O O O O
•^^
0 S-
Z -P
o
*j- ^J- Csj 00
O ^j- rH CM
0 I-
o in csj ro
z
^- oo oo «*•
"^v O O \
i-l rH •-, U3
ID LO m iD
CM CSJ *f CM
r*» fo oo co
i*- co co r-.
r^- M> PO i/^
rH ID CO VD
i— t Cft P-. rH
00 CT> O rH
CM rH CM CM
r^ co cn •-«
o o o o
1)11
CM CM CM CM
CO CO 00 CO
rH 1 + +
1 IT) LO Ift
1 1 1 1
0 0 0 O
IrO <^> t/1 <^
till
vi t/i
UU UU UJ LU
I 1 1 1
rH iH rH CM
^"^ x-s
n LO O rH
LO ^- ^J- CM
O O O O
o o o o
N^X ^^^
0 i- U 0
Z 4J 4J Z
ID ai oo ^
ro co ro CO
0 0 0 rH
O O O O
S,,^, s.^*
o u *- o
Z *J *J Z
O CO V£) O
^- oo oo ^~
0000
Q S- S- 0
Z *J J-* Z
o m CM o
z z
S^- ^- oo
CO CO^x
CO ^" f""- rH
UD LO LO ^
vo r^ i£> co
r»- 1^0 ^- to
^o CO en oo
LO r*- CM en
N- CT» rH CO
rH r-* *fr CA
rH CM CM rH
rH CM CM CM
CM ro ^- in
CO 00 CO CO
1 1 1 1
CM CM CM CM
CO CO 00 00
rH i + I
i tn LO LO
1111
o o o o
to to c/i t-o
1 1 1 1
<»O (/> CO t/i
i 3C S 3:
1 1 1 1
rH rH rH CN)
X)
D.
U
in a
•r- 0)
-C 2
a>
i- ^
o
*+— ^~
a>
O r—
__l
**ta^ ro
C -P
O ft3
.) i +j
ro c
•»~ in
4-> at
C l-
(0 Q.
3
CT in
14-
0 -a
c
•i- o
E CL
•— O
U
T3
at at
•p J=
ro r-
4^
10 at
at u
ro
at s-
r—
II
*—* 4-1
Z
CO
X 0
o
en —i
CM
•*-> C
O
at ••-
a. u
E at
ro 4J
in at
01
3. «-
o
o
0 E
in . —
u
T3 0)
3 ro
0 E
E -P
O in
•j= 5
4-t
in
o "
«*- in
OJ
^^ (f)
O .c
±J 4J
-— < C
OJ
C i-
o ro
4-*
U • C
at -~.-r-
•P Z
•O CO 3
>»- x ro
0 >
o
4-> rH
'i ^"'•a
•p- at ai
r- ,— 4J
o. u
•o E at
at ro 4-> .
4J in at O*
4J "^ 0 -O
in CO C C
a> - ro
rH ||
at o
.c in o o
f— -r- Z — J
re -O
65
-------
ro
W
1
HJ
CO
cu
w
in
h—
O
in
o
CL
•c
«q:
cu
4J
•r—
in
0
t
o
CM
CO
u.
1
en
^f
ID
1
rH
O
ID
ID
CM
O
z
IS)
o
r-
C
< — to
ro -53
C
•o
•r- &•?
— ^
r—
JO 1
•P 4->
U JC
S- -i-
X 5
LU
Ol Ol
in i
-p .c
0)
3.1
01
"a. i-
fO jO
01 E
3
i— i c
ce
01
.P
in
CL S-
e 01
O JO
u e
3
OJ C
CL
E
ro
^^
rH O
r*-v en i^«
O O CM
O O O
o s-
^r^
«3- ID ro
O O CM
O O O
x>
O S-
Z. -P
o
*r CM co
O rH "3"
O i-
Z. -P
o CM ro
z
CO CO CO
en en o
rH rH rH
«!• «• in
nr-in
CM «t ^*
ID P^ CO
ID ID r^
in ro r^
i— t rH
O CO O
Cn CO rH
rH CM
ID r-~ rH
ro ro *f
O O O
1 1 1
CM CM CM
oo oo oo
«r?
i in in
O rH «fr
1 1 1
o o o
» >
I/) I-O l/l
i i i
iii
^-^ /*N
co «- en
CO ID rH
0 O O
000
O S- O
Z 4-> Z
rH ID LT)
CM in rH
0 0 O
O O O
"•^ x*'
o s- o
Z 4J Z
0 0
•3- CM TJ-
0 rH O
O S- O
o o- o
z z
*j- «*• S
co co\
UO in rH
^ ^- ^3-
rH 1C CM
in r*»- en
in co P*.
un CM rH
o en rH
CM
rH Cn t~-
Cn rH ID
rH CM CSI
CM ro ^J-
000
t 1 1
CM CM CM
00 CO 00
•=r 5
i in in
O rH *}"
O O O
LO I-O 1^1
( 1 1
UJ UJ UJ
Z Z Z
1 1 1
^^
CM ro
ro CM
O 0
o o
*— '
O i-
Z -P
O O
CM CM
O 0
O O
x«*
o s-
Z. 4J
i?
0 0
O !-
Z -P
O rH
Z
CO CO
on en
^- ^f
en rH
CM r~
ID CO
* CM
CM cn
r~- o
en CM
rH CM
ID CO
0 O
1 1
CM CM
CO CO
4-
i in
0 •*
i i
i/> 1/1
i i
4J
rH CO U3 Cn r~
r** r^ oo ID rH CM
O O O O rH O
O O O O O O
us- s-
•P 4-> 4->
ID o «j- «a- co ««•
rH CM rH rH CM O
S- S- (-
•p 4-> 4->
rH ro ro ro ro CM
gggSSS
•\**x.*\ PO CM CM
CD in rH rH rH rH
<-f ^f- t|ft y3 ^£ ^Q
in r*^ in f*»- CM cr>
r*v o CM ^" co PO
r** co oo oo f^« co
CO PO tf rH tj" rH
r-. o PO f^-. o tn
O CM CM CM rH O
ro tO ID O VD CO
CM CM rH CM CM rH
CT> O rH CM CO ^>
§m in in m in
0 O 0 0 0
i i i i i i
CM CM CM CM CM CM
00 00 CO CO CO 00
i m in i in in
CD rH ^ O rH ^1
1 1 1 1 1 1
000000
>>>>>>
CO CO CO CO CO CO
1 1 1 1 1 1
ffffff
/— %/— v *-"\/~S
in in in i — r^. co
OOOOOCMOi-t
oooooooo
o o o o t. t-
z z z z +•> -P
CM cn o cn oo o
OOOOOCMOrH
OOOOOOOO
X^ *M* ^^'Xtf'
o o o a i- s-
Z Z Z Z -P -P
o o o o o
OOOOrHLOOCM
s^^^ v^x**
a o o o t- u
z z z z -P -P
OOOOCMrOCMCM
z z z z
SSSggggg
rHCMCMin^'^'LnCD
^"^"^•iOVD*fi^DlD
iDiniDPOCMCMCMPO
comocTtrocorom
•ej-PvCO^DCOCOCOCO
copoorN.cooococo
COVD^D-O-r^rHvOCTJ
CM rH
rHlTiOOCM^-CMCMCM
COrHCnrHrHCDOPO
rHCMrHCMCMCMCMCM
LniX)r*-.COCftOrHCM
OOOOOOOO
l 1 1 1 1 1 t 1
CMCMCMCMCMCMCMCM
cocococococococo
^? ^5 5
i m m i in m in in
O rH *^ O^ rH ^^ rH ^f
I i i I i i I i
COCOCOCOCOCOCOCO
1 1 1 1 1 1 1 1
UJ LU LU LU UJ UJ LJJ LU
1 1 1 1 1 1 1 1
rHfHrHCMCMCMPOPO
CO PO
tD P^* CM r*^
O rH ro 0
O O O O
I- S_
PO CTt
^3- PO CTi in
O rH CM O
0000
i. i.
O Is- «fr PO
rH CM <£> rH
S- I-
CO CM ^3- CM
CO CO CO CO
p*- *s- P*- in
IT) LO ID kO
rH CM CO «!fr
PO tD CT> O
co r^. CM CM
*tf* in/ o P^»
«3- vo tn ^t
PO O CM rH
CM CM CM CM
ro ^3- in ID
0 O 0 0
1 1 1 1
S CM CM CM
CO CO CO
^r?
i in ID m
Oi-H ^ <-
till
O O O O
CO CO CO CO
1 1 1 1
I 1 1 1
rH rH rH CM
66
-------
O)
3.
C T3
O •*-
•r- O.
c —
at .a
u ro
C 4->
o u
cj ro
•o
ai
3
C
C
O
u
at
.o
c 01
O 3.
4-1 in
C in
at -i-
U +J
c
o
a>
re u
4j a>
O 4J
t— o
T3
•o
at
in 4->
s- ^ ro
a> re 4->
<~> QJ «^
!«•£
z x- ro
o 3
cr
r— ro
ro "o
c
rH «3- CM CM VD rH CO CO
CM ^- CM LT) OrHrHO
tOOOOOO OOOO OOOO
O !- !-
r- vo o »-H
^rrHCMC\Jl£>r^tr)
OOOOfHr-fi— f
(CM
en <-H co CM
ID ID rH rH ^J" Cn C\J Co
rH CO O «*• OOrHO
OOOOOOOOOO OOOO OOOO
S- i- O O O S- i-
00 CM O O
O
LO CM nj- VD
I- !- O O
•M 4-> Z Z
O CM CM O
S- i.
CM CM *J- CM ID f
at Di ........._. ....
^- CO CO 00 P^ VD ^" ID
r-cocor-- iDCoenco
4J 4->
u J^ co oo m CM ^ en tj3 ID rH *f r^*- tD co to to r*~ CM CTI
ro en
- - ~~~.rHCMincOCM rHlX>OO^D r^-CnrHCO
ICMrHrHrHrH CMrHrHrH rHCMrH
X 3
LLJ
0) O)
I/) I _ _
rH Cn f^* rH rH r*~ ^J" Cn
.. _ . .. ._ .. cdcno'r-! rHCMCMrH
D) CMCMCMrHrHCMrHrHrHrH CMrHCMCM rHCMCMCM
Ol
roxi oooooooooo oooo oooo
E I i i i i i i i i i
3 CMCMCMCSJCMCMCMCMCMCM CMCMCMCM CMCMCMCM
i-HC COCOOOCOCOCOCOCOOOCO COCOCOOO COOOCOOO
at
f «3- O- «3" "3- "3- . .
O rHl+rHl + 14.14. rH i 4> + ...
iLomiLOLnLDLOLOun JLDLDUD ILOLDLD
_ OrH^-OrH>a-rH«fr-H»)- OrH^TO" OrH^J-rH
OX) I I I I I I I I I I
UE OOOOOOOOOO OOOO OOOO
Q)C UOOOOOOOoOOOOOOOOOOO OOOOOOOO OOOOVOOO
. . I I I I I
Q. ^T«a;«=c^
u
10
4J
ro
4->
c
in
at
u
a.
I
O
a>
u
ro
o
o
c
o
•D
u_
o
T3
a>
4-»
re
c
0)
£-
IB
Q.
QJ ->^ O
T3 00 3
M- x re
o =>
o
E ^3
•r- at at
r- r- 4->
Q. U
•a E at
at re 4J •
4-s in at o*
ro — ID o
E O) —t
•P o T!
in ID c: c
at a
XZ in o. O
I— -i- Z —I
67
-------
0
in
OJ
Q.
E
re
to
OJ
tn
H-
tn
o
CL
«t
OJ
.^f
in
O
O.
O
CM
CO
U_
1
CM
1
rH
1
LD
LC
CO
CM
c!
z
to
C
01
a.
.0
o
S-
o
u
re
o.
OJ
X
i
s-
o
Q.
OJ
re
ro
o
en
rH
OJ
JD
ro
r-
Ol
o>
t *w*
o ••-
-i- Q.
re —
C r-
01 XI
u ro
C. 4->
o u
u re
S-
X
OJ
OJ
3
1 O>
C Ol
O ~L
ro QJ
4-> in
c in
OJ •—
o 4J
c
o
J3
01
in 2-
in *^s
ro
£ "O
OJ
ro u
O 4->
1 — OJ
T3
•0
OJ
in 4->
s- .* ro
oj re 4J
XI OJ -r-
3 C
z t- ro
O 3
rj-
in
in OJ
r- re
re -o
c
•s
•O
•r-
•|~ &•?
r- x^
S 1
re
u .c
ro O)
!- -f—
4-1 Ol
X 3
QJ Ol
3
in i
in
4-> .C
o>
OJ OJ
IX 3
OJ
f" V
n
in E
r-i C
s:
O
Q. S-
£ 01
O .O
u e
0) C
Q.
e
ro
rH O
f"** ro en
O O rH
ooo
o a
z z
«3- CM
«- CM 1C
O O rH
OOO
§i~\
Z
o o
O O ro
a o
z z
O O ro
Z Z
CO CO CO
en en o
rH rH rH
^ ^" LD
ro rH ro
CM «3- «•
LC f"» OO
ID to r-
O ro o
en oo rn
rH CM
ro co ^
ooo
i i i
CM CM CM
00 00 OO
1 LD ID
O rH *3-
1 1 1
OOO
t/> to to
1 1 1
1 1 1
rH rH rH
CO rH Cn
CO CM rH
OOO
OOO
OOO
z z z
rH CO ID
CM rH rH
000
ooo
000
z z z
o o o
ooo
ooo
z z z
ooo
z z z
w
f ^" 00
oo oo \
\^ LO
1C ID i-H
^" ^f *3"
rH ID CM
LD f^» en
LD co r*-
LD CM rH
O O> rH
rH en r-.
Cn rH LC
rH CM CM
CM ro «S-
ooo
1 1 1
CM CM CM
oo oo oo
1 LD LD
O rH «*•
1 1 1
§§§
to to to
1 1 1
UJ LU LLJ
Z Z Z
1 1 1
rH rH rH
CM
CO «•
O rH
O O
a
z
o
CM ro
0 rH
O O
0
Z
O
*r co
O CM
o
z
O CM
z
oo oo
en en
rH rH
^- ^~
Cn rH
CM r^
LC 00
«J- CM
rH-H
r>» o
en CM
rH CM
LC 00
O O
1 1
CM CM
CO CO
1 LO
o *r
i i
o o
to to
i i
Cj- O-
1 1
rH rH
CM ro o ro o ic
CM CM CO CM CM CM
o o o o o o
o o o o o o
o i- oo o a
Z 4-> Z Z Z Z
p~ co r~ o tn CM
rH rH CM CM rH CM
O O O O O O
0 O O 0 O O
a s- o o o a
Z 4-> Z Z Z Z
O 1C O O O O
0 0 O 0 0 O
a i- o o o o
z <-> z z z z
0 ro 0 0 0 0
z z z z z
* «• • *r *r GO
\ \ \ ro CM CM
tD LD rH rH -H rH
^^ ^ tD tD ID tD
LD !-- to r-. CM en
r*- o CM ^~ oo ro
00 ro ^- rH «t rH
O CM CM CM rH O
CO LD ID O 1C 00
CM CM rH CM CM i—*
en o rH CM ro «3-
^- LD ID LD LD LD
O O O O O O
1 1 1 1 1 1
CM CM CM CM CM CM
CO CO CO CO 00 00
1 tO LD 1 LD LD
O rH *J- O rH ^T
O O O O O O
t/) LO tO to t/) I/I
1 1 1 1 1 1
z^MSSs
1 1 1 1 1 1
rH rH rH CM CM CM
?~^ O r*- r^ CM *tf~ CM
rHOOOOrHOO
OOOOOOOO
o ooo a
z z z z z
tc CM en en en o co
LDPOCMrHrHCnCMr^
oooooooo
oooooooo
*""' " ' ^"^
0 000 0
z z z z z
O LD O O O O
OOOOOCMOrH
o ooo o
z z z z z
§CM O O O *»• O ro
z z z z
^^^SoSoSoSoS
Ol tiDkD
uDLT)i£)rocstesic\)ro
«3-r^OOU50000COOO
ooroor^cocooooo
r- 1 (— t I—t rH CM rH rH
rH(i>COeNJ«3-eNJLD
CS ^5 C3 ^3 <^ ^3 ^5 Q
1 f 1 1 1 1 1 1
CSJCMCvJCMCMCSJCSJOxJ
cocococococococo
i in in i m m tn m
i i t i i i t i
§§!§§§§§
i i i i i i i i
i i t i i i i t
T-HrHrHCMCSIOjrOro
r*- to ^f
c\i rv oo ro
O O rH O
O O O 0
ii i
r-. r-. o
rH ID LC ro
0 0 rH O
0 O 0 0
"""^
OS- t-
z -*-> +->
O IT)
«^- esj m i£>
O rH ro O
OS- L.
Z -P ^->
O O- i£) ro
Z
00 00 CO 00
i*- «* r-. in
in LO tn ^o
rH CM CO «*
ro VD Ci o
^ r*^ co co
CO r^ CM CM
i—t rH CM rH
^5- CD tn ^~
CO O CM rH
CM CM CM CM
ro *}• in o
<£> l£> l£> 4£>
O 0 0 0
1 i 1 i
CM CM CM CM
CO 00 CO OO
i in m m
O rH *3- *fr
t t 1 i
§§§§
to oo to oo
1 1 1 1
1 1 1 I
rH rH rH CM
68
-------
-TJ
Ol
D
C
C
O
u
CT1
r- 1
Ol
XI
re
Ol
^»
O)
! '•^
c -o
O T-
«p- a.
rer-
C p—
ai xi
u ro
C 4J
o u
o re
S-
x
01
^J
ai
i o>
C O3
O 3.
re ai
i. 3
4-1 I/)
c to
01 -P-
U 4J
c
o
o
XI
D5
t/i 3.
re
ai
I — 4->
re u
O 4J
h— Ol
•D
o>
L. -^ re
01 re 4->
X! O) -P-
3 C
2 <4- re
0 3
cr
Ul
u) 0>
p— re
re -D
T3
£*
s r
u x:
S- -P-
X 5
LU
Ol D)
3
(/I 1
in
+J x;
01
ai aJ
^ j
ai
Q. S-
re x)
ai E
3
C£
£
O
O. S-
E 0)
S|
QJ C
a.
E
re
CO
m o o o CK o
OOOOOrHrHrHOrH
OOOOOOOOOO
0 1. 0 I- (- (- S-
Z 4-> Z 4J 4J 4J 4J
CTl I— t rH rH LD O CM ro
OOOOOOOrHOrH
OOOOOOOOOO
O S- O !- t !- U
O ro O O 00
OrHOOOOOr-HesiOp-l
O !- O <~ S- S- S-
OfO^'Or-*<}'Vj'COrO^
z z
™"\oS"rooS\oo\
p-HCNJCSJinrH^-LOrH^Oi-H
cn^inrHnai-srr-oin
S co S S S S ° g £ S
co co LT, CM » a. vo vc r-, »
tOMtDnr^p-HCMinrocsi
i-.^-OrHinrtcnocsiu=
SSSSSS^SSS
r^cocnorHCMro«^-LnLD
OOOOOOOOOO
1 1 1 1 1 1 1 1 1 1
CMCMCMCMCMCMCsJCMCSJCM
cocococooocococococo
^ * «• ^
rH t + rH I + i + i +
lltliillll
OOOOOOOOOO
LO LO LO LO LO L/l t/1 LO LO LO
1 1 1 > 1 1 1 1 1 1
^C ^C ^C ^ ^C LO L.O (^
1 1 1 1 1 1 1 1 1 1
rHr-lr— ICMCMCxirOfO^^J-
CO Cn CM CT*
O rH O ro
O O O O
£
in o
LD LD CM O
0 rH 0 ro
O O O O
t,
4J
CM
CO CM ^- •!}•
rH rO O V£>
L.
+J
ff *f rH ^I
** CO CO ^
rH rH rH LD
uD in m LO
CM CM ^J- CM
r^ ro co CO
r** CO CO f^*
r-vcmen
1-H 1£1 00 UO
oo cn o P-H
C\J r— t CSJ CsJ
f^- 00 OT rH
o o o o
1 1 1 1
CM Psl PJ CM
CO OD CO 00
*.
rH r + +
1 If) IT) LO
O r-l ^T 'J'
1 1 I 1
O O O O
LO LO LO tO
1 1 1 I
L/> LO LO LO
LU LU LU LU
1 1 1 1
I— 1 r-H i— 1 CM
CO On O iH
Lf) <3- r^-. csi
o o o o
o o o o
a i- s- a
Z 4J 4-1 Z
LO CSJ LD CO
CO ^" LD r-t
0000
O O O O
v^ •— '
§!- S- O
4-> 4-> Z
O LD O
«t O) LT> *3-
O O i-l O
t*** ^— '
O i- i- O
Z 4-> 4-> Z
O «3- •*• O
Z Z
<*• ^- ^3- CO
CO 00 00 -v.
CO "3" l>- rH
LD LD LO LD
LD r^. LO ro
h~ LO *}• v LD
o o o o
1 1 1 1
CM CSI CM CM
CO CO CO CO
•s- *
rH 1 + T
1 LO LO LO
O rH rj- i— 1
O O O O
CO LO V> LO
1 1 1 1
LO CO CO CO
^ ^ "* ^
1 1 1 1
rH rH TH CM
•o
C
3
O
&
O
u
c
t/i ai
• r- Ol
x: a
4-1 4-1
Ol
i- XI
o
*fc- p—
Ol
l~> >
o- 01
o p—
i
^-* re
C 4J
o ro
4-J 4^
re c
4J Ol
+J 01
c t.
ro Q.
3
CT u>
t+^
o -o
C
4-> 3
•P- O
E CL
•r— £
*~ o
u
•D
O> CO
+-> ^r
TO t—
M
4->
in O)
QJ u
ID
O) i-
XI 4_>
r-
II
fc.
*— s -*J
Z
•"s^
LO
*r^V
X
o i
Ul I —
TJ Ql
3 re
0 E
E 4J
O (/)
•p- x:
x: 4-1
in
t- -p-
o
**- V)
01
<--> w
O Ol
o x:
— 1 4-1
01
C i.
o ro
•p- D.
u • c
Ol /^-r-
4-J Z
Ol *^. Ol
•D LO 3
«*- x re
0 >
o
4-> rH
•p- Ol Ol
Q. U
•D E 01
o) re 4-9 •
4-> Wl Ol O*
ED) —I
4J "^ o -a
U) LD C C
ai • re
rH ||
01 O
x: u> o o
(— -r- Z — 1
re xi
69
-------
TO
l/l
01
Q.
E
TO
O>
13
in
OJ
to
o
CL
"O
§
,_
C
01
CL
.5
O
s-
o
u
TO
4-*
U
O
1
Jj
S-
o
CL
Ol
ce
TO
4->
TO
o
O
CM
O>
XI
TO
1
-v.
Ol
3.
C "O
o ••-
•r- O-
TO T~
OJ XI
U TO
C *->
O U
(_} ro
s_
+J
X
Ol
Ol
1 Ol
C Ol
O 3.
TO Ol
4J jfl
c in
Ol •!-
u +•>
c
o
o
XI
O)
t/1 12.
in *— '
TO
E *O
TO U
*-> Ol
O *->
t— 0)
•D
T3
Ol
i- .* ro
Ol TO 4->
XI 0) •—
3 C
Z t- (0
0 3
O-
in
l/l Ol
i — TO
TO "O
C
•o
•1—
•r- £
•^ x:
CO
•+-> •>-
_o> i
01
1" oi
TO XI
I/I E
3
s:
o
Q. !-
E 01
O XI
U E
01 C.
i
TO
l/l
rH cn ro
r^ CM CM
O O O
O O O
000
Z Z Z
•3- CM cn
W CM rH
O O O
O O O
O O O
Z Z Z
o o o
o o o
o o o
zz z
000
z z z
CO CO CO
cn cn o
rH rH rH
*s~ «3" in
CO rH CO
CM ^- *fr
ID f«- CO
ID ID p-
in ro f^
rH rH
O CO O
Cn CO rH
rH CM
ID r^- rH
O O O
1 1 1
CM CM CM
CO 00 00
rH I +
i m m
O t-H "3-
1 1 1
o o o
to to uo
1 1 1
1 1 1
00 rH 0
ro CM CM
o o o
o o o
O O t-
Z Z •(->
rH CO ID
CM rH rH
000
000
001-
z z -u
o O ro
T «3- *r
o o o
o o (-
Z Z *>
O O rH
Z Z
**• *}• co
co co "^
U3 in rH
*3" ^" ^"
rH tD CM
in co r-*
LO CM r-H
O Cn rH
rH rH CM
rH Cn r--
Cn rH ID
rH CM CM
CM ro *T
O O O
1 1 1
CM CM CM
CO OO 00
rH 1 +
i to in
O rH «•
1 1 1
o o o
to to to
1 1 1
LJJ LU L1J
Z Z Z
1 1 1
CM
ro CM
0 rH
0 0
O
Z
0
CM O
O rH
O O
O
Z
o
*J- CM
O CM
O
Z
O ro
Z
oo oo
cn cn
rH rH
^" •*}•
cn rH
CM I-.
10 CO
•9- CM
CM cn
T-H rH
r- o
cn CM
rH CM
ID CO
0 0
1 1
CM CM
00 CO
rH -f-
i in
O -3-
1 1
0 0
tO LO
1 1
1 1 1 1 1 1
1 1 1 1 1 1
OOOOOOOO
OOOOOOOO
§000 o s-
Z Z Z Z 4->
CMroincncnrHOCM
CMCMCMrHrHtDCMLD
OOOOOOOO
OOOOOOOO
o o a o o i-
Z Z Z Z Z 4->
o cn o o o o
OOOOOrHOrH
^-"*^
O O O O O S-
Z Z Z Z Z *J
oroaooino«3-
z z z z z
|||sssss
f— *C\JC\jLf>^*J'LOy3
Lr3t£>rocsjc\jCMm
ooLDOo^rororom
oomor^cococooo
eouDi£>^j-f^'-Hii3cr>
iH r- 1 rH r- 1 CSJ rH rH
i— i«^ooesi«3-csicsjcxj
COr-*Cni-*f- 1 1 1 1 1 <
OOOOOOOO
>>>>>>>>
1 1 1 1 1 t i 1
ZZZZZZZ2Z
1 I 1 LU ii 1 LLl LXJ UJ LJJ ' ' '
1 1 1 1 1 1 1 1
rHr-HrHe\JC\JCSimn
p*« 01 ^~ ro
CM CNJ r*. csj
o o o o
o o o o
a i- s- o
2 *J 4JZ
r^ csj 10 o
rH CXI VD rH
o o o o
0000
0 s- i- o
Z -P -M 2
O V£> O
^ ^" if) •«*•
O O rH O
^^ S**'
O t- t. Q
2 4J 4-> Z
0 ro ««• Q
CO OO CO 00
PN» ^- P>* LO
LD Lf> LT) tX)
rH CM 00 *J-
ro VD CTv O
o r^ oo oo
00 f- CM ^J-
ro O csj rH
CSI CSJ CSJ CSJ
ro «*• m vo
VD VO |*D iC
0 O 0 0
1 1 1 1
CM CSI CSJ CSI
00 00 CO OO
rH 1 H- +
i m m LO
O rH ^J- q-
1 1 1 1
0 0 O 0
I/) tO U") tO
1 1 1 1
1 1 t 1
rH rH rH CSJ
70
-------
-rj
D
C
C
o
u
o
CM
CU
.Q
re
r—
cn
a.
i •--'
Q *r-
— D-
ro r—
4.
4J qj
C. t—
OJ X)
u ro
C -p
o u
o ro
X
01
^
OJ
1 CTI
C Ol
O 1
ro 01
i- 3
c in
0) •!-
o <->
c
o
o
.a
/— v
01
in ^^
ro
E ~O
OJ
TO U
•P 01
O 4->
1 — OJ
ai
in -P
£- ^^ re
01 re -p
fpl _4J
C
z: 14- re
O 3
CT
.2
in a>
>,-P
i — ro
ro t3
c
•o
O.-*^
,_
Xi I
•P -P
U JC
i- -r-
X S
UJ
OJ CD
in i
in
•P f
O)
01 01
01
a. s-
ro xi
m E
1-4 C
or
Ol
4_>
•r-
o
a. s-
O XI
u e
01 C
Q.
E
re
t/i
Jo'cocno'roiorounrH'
oooooooooro
oooooooooo
aos-oos-(-s_o
CTt IT} 4" t— 4. r~ ( CTi rH 91 CM
OOOOOOOOOCM
OOOOOOOOOO
S^^S.^ \^^ v^/ N.^
oos-oos-s-s-Q
^ *y +3 21 Z *^ +^ +•* 21^
oor^oo e\joo
OOOOOi-IOOO-S-
Q O ^ (O CD t- ^ I- f"s
2ZZ*J-2Z4-i4-J-*-)Z
o ^^ ro o o c\j ^}~ c\j <"** ro
*y 2» ~y ~^ "^
^^^ ^ ^
^\\S\3S\S\
rHCMCMmrH^-Lf>rH»»C>rH
m^-mrHrocji^-r^ou-)
fOiDCMcncnmotocMo
OOCOOOtDOOCOr^-CDr^P^
cocoLncM^tenixt^DrH^-
l£>CMlDror-rHCMinrOCM
rHCMtHrHrHCMrHr-trHrH
r- «• o rn tn ^ cn o CM ic
O"X)OcncritDr^o6c6r^
CMCMCMtHfHCMrHrHrHrH
r*.OOCnOrHCMPO^-LntD
OOOOOOOOOO
1 1 1 1 1 1 1 1 i 1
CMCMCMCMCMCMCMCMCMCM
aooococococooococooo
^- ^- ^- ^f-
rH 1 + rH 1 + 1 -t- 1 +
1 1 1 1 1 1 1 1 1 1
OOOOOOOOOO
tntotncot/}(X>coi/)LOto
i i i i i i i i i i
tO<-OtO(^LOCOtOU*)LOCn
1 1 1 1 1 1 1 t 1 1
rHrHrHCMCXjCsJfOPO^d-*^
cn CTi
<• O V£> CM
O rH O rO
OOOO
i- S-
00 ^f rH
ro OO *£> m
O 0 0 CM
OOOO
t- i.
4^ 4-5
rH t^. CO CM
rH rH rH in
i— S—
4j 4j
oo ro ro in
- UD ro in
i-H ID 00 <£>
OO CH O rH
CM T-H CM CM
r^ co r-t
OOOO
1114
CM CM CM CM
00 CO 00 00
*J"
i vn in to
i i i i
OOOO
i/> ^/) i/i i/>
i i i i
co t/) i/)
UJ LU UJ LU
1 t < 1
T— 1 rH rH CM
CT1 S^J- rn"
ID CM CO CM
OOOO
OOOO
!- O i- O
4-> Z -4-> Z
r^ oo CM oo
^- rH rO rH
OOOO
OOOO
'*•" s— '
I- O t- O
+^ z ^ z
CM O rH O
tn «^- r- ^~
OOOO
S. 0 i- 0
•4-> Z +J Z
rH 0 •* Q
Z Z
<3_
SoS S\
00 ^- P** T-H
tn m LT> uo
101^ i£> ro
f^ ^O ^" UD
o oo cn oo
in P^ c\) rj*
r~ a> rH CD
rH CM rH
rH CM CM rH
rH CM CM CM
CM ro *t in
oo oo oo oo
OOOO
1 4 t 1
CM CM CM CM
00 OO 00 00
^" *5"
rH 1 + t
4 ID IT) LT)
1 1 1 1
OOOO
tn oo i/)
i i i i
S ^ S 3E
I I 1 I
rH rH rH eg
•0
C
O
g-
u
in 01
5 3
01
o
O)
O1 O)
1
"•^ ro
C ' 4->
o ro
•£ £
*j ai
jj Ol
c s-
re Q.
Cr in
14-
O T3
c
•i- o
e a.
i— O
u
•a
ai ai
re i —
.E
4_>
in 0)
O) u
re
QJ S-
J= ^
l —
II
z
l/>
X 0
o
m _j
CM
^-/ c
o
"a u
E 01
re 4*>
Ul 01
•^x TD
D>
3. "r-
o
0
o 'i
in i —
"O 01
= ro
0 E
I" 'Z
O in
•^ ji
^ •*->
in
S- •!-
0
ai
'"^ in
a ai
O f
— i -P
a>
c t-
o re
•- a.
u . c
0) /-^»r-
+J Z
01 \ 0)
•D CO 3
*4- x ro
0 >
o
•4-i rH
i '~'-a
•r- Ol 01
Q. U
•a E 01
01 re *J
•P ift 0> O*
•^- 5-p —
•P O 13
in u> c c
ai • ro
rH )|
01 0
-C l/l O O
1 r- Z — 1
re js
71
-------
D
in
QJ
Q-
e
ro
to
O>
D
(/)
in
^~
OJ
t/)
O
Q.
•5
<
QJ
."Jj
l/)
O
(_}
CM
00
U_
1
p-.
1
r-*
o
1
CSJ
^>
<>-
ro
in
o
z
to
^
o
"^ar1
1—
c?
O)
.C
Q.
X2
O
i-
o
^
o
TO
C
O
z
1
4J
o
Q.
01
CC
re
•4->
re
Q
CM
O)
C P—
(U _Q
u re
C 4J
o u
c_? re
S-
4J
X
OJ
J->
OJ
S
1 O)
C O)
o n.
re 01
t— 3
+J in
C in
o; •--
U -t->
c
o
o
.Q
^•~*
D)
in 2.
U) W
re
£ "U
01
^~ •*"*
re u
•!-> OP
0 •!->
r- O
TJ
•c
O>
in -u
s- ^ re
o» re -*J
JD Q) -P-
E Q.4->
D C
z t- re
O 3
cr
t/>
(/) OI
>>•*->
p— re
re -D
c
«
•D
D-^~s
••-«
QJ O)
-C i
fC
*-» *J
U XT
fO D)
i- "-
*-> QJ
X 5
QJ O)
in i
to
+•> x:
01
+J *r~
Of OJ
^ 2
QJ
Q. t-
E OJ
TO XI
IS) E
•—) C
ce
s
QJ
4->
(A
o
Q. U
E 0)
O XI
U E
3
OJ C
I
(C
to
O O> ro
r* c\j CM
o o o
o o o
§§§
^J- CSJ O1
•9- CM rH
000
o o o
o o o
zzz
o o o
«3- *!- «S-
000
o o o
zzz
o o o
zzz
«3- *J- ^>
oo oo oo
en en o
rH rH rH
^r ^- in
OO rH CO
CM ^- *3-
ir> r^ oo
ID ID r^
in ro r^
o ro o
<7i OO i-H
rH CM
ID f^ t-H
ro ro ^~
000
i i t
CM CM CM
oo oo oo
•SI-
'S- 1-
rH l +
i in in
O rH -3-
1 1 1
O O O
> > >
to to p-o
1 1 1
1 t 1
rH rH rH
00 rH O1
ro CM rH
O O O
000
§ii
rH CO in
CM rH rH
000
O O O
000
o o o
«r *r «3-
000
0 O 0
zzz
o o o
zzz
«3-
«}• -a- oo
00 CO -x
ID UO rH
*f «3- fl-
rH VD CM
in r* o%
in co r*^
in CM rH
O CT1 rH
rH en r^
en rH PJD
rH CM CM
CM ro «T
*1- *t ^~
000
1 1 1
CSJ CM CM
00 CO 00
«3-
*J- ^J*
rH 1 +
i m in
O rH > >
t/) tn to
i t i
LU LU UU
ZZZ
1 1 1
rH rH rH
CM cn
ro CM
0 0
0 0
0 (-
Z 4->
o in
CM CM
o o
0 0
o s-
z *>
O U3
«s- in
0 0
0 i-
z +•>
O rH
z
^}- "3-
oo»
cn cn
rH rH
<3- «»•
Cn rH
CM r~
ID OO
*3- CM
csj en
t»- o
cn CM
rH CM
ID 00
«3- ^J-
O O
1 1
CM CM
00 00
•3-
rH +
i in
o >a-
i i
0 O
:> >
to to
i i
x, ro CM CM
ID in rH rH rH rH
^- «3- tD ID ID tD
in r^ in r^- CM cn
r^ o CM <3- oo cn
r^ OO OO OO r^v 00
ozn^^^r*
r-. o ro r»- o un
O CM CM CM r- 1 O
ro in VD o to co
CM CM »— 1 CM CM rH
CF> O rH CM CO *3-
^)- un LO tn tf) to
i t i i i i
CM CM CM CM CM CM
«3- ^3-
*r ^r <-r **•
rH 1 4- rH I +
1 LO Lf) 1 ID LD
O rH ^- O i-H ^~
1 1 1 1 1 1
O O 0 0 O O
>>>>>>
t/> to to to to tn
1 1 1 1 1 1
iiiiii
i i i i i »
i— 1 rH rH CM CM CM
Lnininr~CMOO*i-o
«3-CMCMCSJCMrHCSJCM
OOOOOOOO
OOQOOOOO
zzzzzzzz
cMcnocncninor~
CMrHCSIrHrHrHCMrH
OOOOOOOO
ZZZZZZZZ
o'o'o'o'o'o'o'o^
^•*3-«4-^"^'^S-«3-«3-
OOOOOOOO
§§§§§§§§
OOOOOOOO
zzzzzzzz
GOCOCO^J'^"^*^'^
\ "*x. \ CO CO CO CO CO
f-HCMCMir>*fr*3-LfttD
^"^•^•tDtDtDVOtD
tDLniX>fOCMCMCN(rO
COinocr>fOrorotf)
*3-r^covr>cocooooo
ooroor-^cocococo
COtDt£)«3-.Kxi-HtDC.n
rHtOOOCM^CMCMCM
COfHOi— trHtOOPO
rHCMrHCMCMCMCNJCM
Lntor-»cocr>OrHCM
mmmmintX)tDtx>
OOOOOOOO
t i i i i i i i
CMCMCMCMCMCMCMCM
*? *f *f
^3- «5J- ^J- "*• ^S"
rH i + r-t t + t +
1 ID LO 1 ID tO tn LO
OrH«3-O'-H«c!-i-H*J-
1 1 I 1 1 1 1 t
OOOOOOOO
tototototoi/it/>to
1 1 1 1 1 1 1 1
zzzzzzzz
1 1 i LU LU i ' ' LU ' ' ' ' i ' UJ
1 t 1 1 1 1 1 1
rHrHrHCMCMCMrOro
n* in ix> ro
CM CSJ CM CSJ
O O O O
o o o o
O 0 i- 0
z z •>-> z
P^ O"> ro CTi
rH rH CM rH
O O O O
o o o o
O O (. O
Z Z -4-> Z
O O CM O
«t *• in «-
0000
§O S- O
Z *J Z
O O CM O
z z z
ss; s; s
00 00 CO CO
r>» fl- r^ in
in in in PX>
rH CM 00 «-
ro us cn o
ID r~ 00 00
eo r- csi CM
^- in o r-^
•s- to in «3-
ro O CM rH
CM CSJ CM CM
ro «3- in «
ID ID tD ID
o o o o
1 1 1 1
CM CM CM CM
00 00 00 00
•o-
«3- <*•
rH 1 + +
i in in in
O rH «• «S-
1 1 t 1
O O 0 O
l/> P-0 OO t/^
i i i i
ilii
i i i i
rH rH rH CM
72
-------
>le 21 (continued)
ro
r-
O)
01
O-r-
•t- a.
ror-
- wet Concent
g) extractable
C 01
o a.
ro Ol
4-1 in
C in
O) -r-
O 4->
O
O
01
(/) ^^
ro
01
Number
llysis of peaks Tota
late quantltated detec
C
O)
in i
in
4-> -C
O)
Ol Ol
0)
'o. s-
ro -O
in e
3
ce
z
01
in
O
Q. '-
0 .0
U E
3
O) C
m
oo
OOOOOOOOOPO
oooooooooo
OOOOOOOOO
CnmOrHrHLnCSICMCM
OOOOOOOOOCM
OOOOOOOOOO
ooaoo.oo.oo
ooooooooo
oooooooooro
aoooooooo
zzzzzzzzz
OOOOOOOOOCM
zzzzzzzzz
..........
a^^runi-iPOcn^r^OLn
roiDCMCTiCTiroOiDCMO
oo co en CM «• en ID to r-. *
IDCMlDCOr^rHCMinrOCM
CMCMCMrHrHCMrHrHrHrH
OOOOOOOOOO
1 1 1 1 1 1 1 1 1 1
CMCMCMCMCMCMCMCMCMCM
rH 1 + i-H F + 1 + 1 4.
1 1 1 1 1 t 1 1 1 1
OOOOOOOOOO
1 1 1 1 1 1 1 1 1 1
1 1 1 1 1 1 1 1 1 1
00 rH CM in
rH -3- CM ID
O O O O
O O O O
Z 4J 4-J 4J
«3- «- CTV i-H
rH +J
o oo o
O O O rH
O !- S- t-
Z 4-> 4J 4J
O CM rH rH
Z
TJ- co co «»•
CNJ CM ^- CM
r~- co co co
r^ co co f^-
r- ID ro in
rH ID 00 ID
rH Cn !^ rH
00 Ol O rH
CM rH CM CM
r^ co cn rH
O O O O
1 1 1 1
CM CM CM CM
00 CO CO CO
•3-
rH I -f H-
i in in in
i i i i
0000
wo to uo to
1 1 1 1
i/> to t/> to
LU LU LU LU
1 1 1 1
rH rH rH CM
CO O CJl rH
in CM rH CM
O O O O
o o o o
a o o o
z z z z
ID CO CO 00
CO rH rH rH
O O O O
O O O O
O O Q O
Z ZZZ
o o o o
o o o o
ii-ii
0000
z z z z
CO 00 CO\
LD LT> ID t£)
O r- i£> ro
f**- <^ «J- ID
tx> oo 01 oo
in r*- c\j o^
f-- CT1 rH CO
r"t P** *}• CTl
i— 1 CM CM rH
rH CNJ CM CM
CM m «j- in
0000
1 1 t 1
CM CM CM CM
00 OO 00 00
rH 1 H- 1
i in m in
i i i i
o o o o
i i i i
co to co to
1 1 1 1
rH rH r-H CM
C
O
i
0
o
4-> 4->
01
o
ai
•^^ >
C^ O)
o •—
^
^.^ ro
C 4-J
O ro
4J 4->
ro C
•r- in
4-> 01
C !-
3
14—
O "O
C
•r- O
•— O
U
01 a>
m (—
E
4J
01 U
ro
01 '-
t—
II
z
X O
0
CO —1
CM
•— • C
o
a. u
E Ol
ro 4->
vi 01
a 'o
o
o 'i
t/i i —
3 ro
0 E
E £
O in
•i- -C
4->
in
i- 't~
O
01
, — ' in
0 .C
V C
C S-
O ro
"- O.
U • C
Ol /~s't-
4-> Z
•O CO 3
»- X ro
o >
o
4J rH
O. U
•0 E 0)
Ol ro 4-^
+J O T3
in 1C C C
ai • ro
rH ||
ttl O
x: in o O
I— -t- Z _1
73
-------
0
l/l
OJ
1
l/l
1>
w
r-
S!
o
a.
T3
o u
O TO
i.
X
01
OJ
S
1 Ol
C Ol
O ~*
TO OJ
4-1 in
C (/I
Ol •!-
U 4->
o
u
XI
Ol
(n 3-
Ul ^^
ro
E T3
OJ
r- 4->
TO U
4-> OJ
0 4-1
t— 01
•o
•a
ai
in 4-1
s- -* ro
OJ TO 4^
XI Ol •*-
E a.4-1
3 C
z M- ro
O 3
cr
in
In OJ
TO T3
C
•a
•£•»«
r-^
f— -
XI 1
TO
4J 4J
u x:
TO Ol
S- ••-
4J OJ
X 5
ai 01
ui i
*> x:
01
OJ O)
01
Q. i-
B OJ
TO XI
i-H C
cz
S
HI
m
O
Q. S-
§0)
XI
U E
3
OJ C
a.
E
TO
OO
00 rt LO
rH O O
o o o
O 0 0
z z z
.— ,in OD
rH in *3-
i-H 0 0
o o o
o o o
z z z
o o o
o o a
z z z
o o o
z z z
CO CO OO
en en o
rH rH rH
f -3- LTJ
CO rH rO
CM "9- «•
ID r- CO
ID ID r~
in ro r-
rH rH
o ro o
Cn 00 rH
rH CM
ID F^ rH
CO rO Tl-
000
1 1 (
CM CM CM
00 CO CO
«3- ?
i-H 1 +
i in in
O i-H -S-
i i i
O 0 O
» >
co to to
1 1 1
iii
rH rH i-H
in CM r--
O LO W
o o o
o o o
o o a
z z z
CM ID r^
in *3~ co
o o o
o o o
a o o
z z z
o o o
a a o
z z z
o o o
z z z
•a- «s- co
oo co\
\ \ LO
ID in I-H
^^ ^f ^
rH ID CM
in r*- en
in eo f~
in c\j rH
o en rH
rH rH CM
rH en r~.
en rH ID
rH CM CM
CM ro «4-
•a- ^- 1-
o o o
1 1 1
CM CM CM
CO CO CO
•*• «*
i-H 1 +
1 LO LO
O i-H «3-
i I I
OO LO CO
1 1 1
LU LU LU
Z Z Z
1 1 1
rH rH rH
rH O
00 ID
00
0 0
0 O
Z Z
O CM
LO LO
0 0
0 0
a a
z z
o o
1-H rH
a o
z z
00
z z
co oo
en en
rH rH
^^ *^
en rH
CM r-
1X1 CO
«• CM
CM en
rH rH
F^ O
en CM
rH CM
ID CO
O O
t J
CM CM
00 00
^.
rH +
1 LO
O tf
1 1
O O
l/l OO
CL. a.
rH rH
in en in co en f~-
LO ^f P^ LO ^T CM
oooooo
oooooo
oooooo
z z z z z z
ro o CM o eo ro
«*- *4- ID LO ro CM
oooooo
oooooo
oooooo
z z z z z z
oooooo
000000
z z z z z z
O. O. ^3 **** ' *"** C3
-z.-z.-z.-z.-z.-z.
«± ^- «3- CO 00 CO
CO 00 CO *"•««. ^^ "s*x.
VD Lf) rH r-t r-t rH
*^ *- o m
rH OJ rH t-t CM rH
O CM OJ OO rH O
ro m CD o CD co
OJ OJ rH OO OO rH
CT% O 'H OO fO ^~
^- in in m in in
oooooo
i i i i i i
oo oj oo oj oo oj
^.5 ^-5
rH 1 + rH 1 +
1 U~) U") ! U~> LT)
O rH ^3- O rH -cr
1 I 1 1 1 1
OOOOOO
CO CO CO CO CO t/)
1 1 1 i 1 1
1 1 1 1 1 1
rH T— 1 rH OO OJ OJ
i*~ N rH ro CO CD CD O rH
rHOOOOOOO
OOOOOOOO
§0000 s- o o
Z Z Z Z -4-> Z Z
in CD rH r*- 1^ in o^f*^
oooooooo
oooooooo
OOOOO S- O O
ZZZZZ-MZZ
oooooooo
OOOOO £-00
ZZZZZ-PZZ
OOQQOrHOO
-z.-z.-z.-z.-z. z z
SSoS^-^r^^^-
^x "*•** **x. CO 00 00 00 00
r- tojojcn^-^f-LDCD
^f ^f ^" CD CD CD CD CD
COLOCDrOOJOJOJPO
ooinocnrororoun
^•r*-cocDcocococo
coroor»-ooooooco
cocDco^r-rHcocn
rH t-t r-t rH OJ rH rH
rHCDCOCM^-OjOJOJ
COi— HCr>i— (i— ICDOro
rHOJrHOJOJOJOOOJ
LncDr*.COCT»OrHOj
gggggggg
1 1 1 l 1 1 > 1
OJOJOJOJOJOJOJOJ
oocooocooooococo
^.5 ^-5 5
rH 1 + rH 1 -t- 1 +
i LO m i m m ID m
C> rH ^}- C^ rH ^ rH ^~
1 1 1 1 1 1 1 1
OOOOOOOO
CO CO CO CO CO CO CO CO
> 1 t 1 I I i 1
ZZZZZ2TZZ
LU LU LU LU LU LU LL1 LU
1 1 t 1 1 1 1 1
rHrHiHCMCMCMrOro
oo ^~ en oo
VD ID «3- LO
o o o o
o o o o
O 0 0 O
z z z z
co en *^ p^
o o o o
o o o o
a o o o
z z z z
o o o o
o o a o
z z z z
o o o o
z z z z
^.,3. ^.,4.
co oo co co
r^ ^- f^ LO
in in in ID
rH CM CO <*•
ro ID en o
ID f-~ 00 CO
CO f^ CM CM
«f LO o r-.
rH rH CM rH
«d- ID in *+•
ro o CM i-H
CM CM CM CM
ro «3- in ID
ID ID ID ID
O O O O
1 1 1 1
CM CM CM CM
CO CO CO CO
«• S
rH 1 + +
i in in in
O rH «»• «-
1 1 1 1
0 O O O
oo oo oo oo
1 1 t 1
z z z z
1 1 1 1
rH i-H rH CM
74
-------
O>
3
C
4J
C
0
u
CM
CM
c
o
o
.a
/-",
Ol
in 3.
TO
E -0
TO U
4J Q)
O +->
(— 01
T3
•a
ai
in 4^
i- Ji TO
a) ro 4->
XI 0) •!-
EC. £
z <»- ro
O 3
cr
l/>
l/l OJ
i— TO
TO T3
C
T3
-D 1
4-1 4->
U -C
t. -r-
uj S
CD D)
in i
•u .c
4-1 •(-
ai a>
QJ
CO .O
w E
i-« C
CC
QJ
4->
in
o
a. i-
O J3
ZZZ4->
OOOOOrHOOOrH
zzzzz zzz
cnsrLnrHrocn^i-r^Oin
3 o? S S S S S oo S S
00 CO in CM * f^ rH
00 Ol O rH
N. oo en rH
1 1 1 1
CM CM CM CM
CO 00 CO CO
rH 1 + +
i in in co
III)
CO CO CO CO
1 1 1 1
CO CO CO CO
LU LU LJJ LU
1 1 1 1
m m *r in
rH O O O
o o o o
a o o o
z z z z
O «3- in co
en ^" *3° ^*
o o o o
o o o o
o o o a
z z z z
o o o o
o o o a
z z z z
§§§§
f -3- «• OO
oo oo oo **>*
co ^- r^ rH
en en in co
CD f^ CD n
f^ co «• co
CD oo en oo
co r-* csi o
r^^ en rH GO
rH CM CM rH
csj ro ^- in
O O O O
1 1 1 1
CM CM CM CM
CO CO CO 00
•3- «3-
rH 1 4- 1
i in en in
i i i i
OO O O
CO CO CO CO
1 1 1 1
CO CO CO CO
1 1 1 1
•o
c
3
a.
o
01
•- S
JZ 4->
4-> Ol
i.
o •—
, — * 01
cr i—
0
— 1 TO
4->
C TO
o
•1- 4J
4-> C
4-> in
• i- Ol
4-1 i-
TO
CT •!-
>*- TJ
o c
3
4-> 0
•i %
•i- O
i — U
TD 01
01 f
TO
E
4-> ai
in u
aj TO
i.
01 4->
JZ
r- II
S-
4-J
z
•v.
CO ^^
0
X O
_l
in >~^
CM C
^> o
01 4->
r— O
a. QJ
E 4->
TO ai
in -D
*-^
CJ) *+-
n o
O 4J
rH E
in i —
•D 0)
3 re
0 E
E 4J
O in
U 01
.C 4J
4->
in
t- •!-
o
n- in
ai
, — ^ in
O JC
^^ c
Ol
C i-
O TO
•p- Q.
U . C
Q) - — .-i-
4-> Z
T3 CO 3
<*- x re
o >
o
4-> l-H
E -0
•^ QJ Q)
i— »— *J
o. u
•0 E QJ
QJ (O 4-> .
+J in QJ O'
fO \ "D O
•M O "D
w o c c
(U ' (C
Q) O
.C tn Q O
(— ••- 2 -J
75
-------
255 .
232 .
N 32S
c
o
-------
in
E
fl3
in
O
Q.
•5
VJ
i-
o
eg
00
i
Lf)
1
O1
O
OJ
c
O)
N
0)
o
s_
0
1
CSJ
rH
1
O
Q.
o:
m
TO
o
ro
CM
(TJ
r—
-ig
TO 4->
c TO
1 3.
O ~D
•p a.
S- f-^
wet Concent
) extractable
C O)
o a.
*J "^
. Concentre
) tissue
*n 3-
V) ^ —
E -0
l— *->
re o
4-> 0)
o 4->
r- CU
•a
a> cn
ro
TO O)
t- •,-
4-> 0)
X 5
LU
cu Cn
I/) 1
in
D>
CU
ts-
TO .a
I-H C
oc
o
in
o
a. s-
E QJ
O .O
U E
01 C
CL
E
TO
CO CO 00
cn cn o
rH rH rH
in in rH
o o o
o o o
o o o
CM rH O
CM rH rH
O O O
000
O O O
o o o
CM CM CM
000
O O O
Z Z Z
ro rH ro
CM <* f
CD ID r-
in ro r*-
rH rH
Cn CO rH
rH CM
O O O
CM CM CM
CO CO 00
•ea-
rn i •*-
i in in
O rH «3-
1 1 1
O O O
OO CO CO
1 1 1
1 1 1
rH rH rH
CO 00 CO
CD in CD
cn o CD
o o o
o o o
o o s-
z z ••->
o cn cn
rH O CM
O O O
O O O
O O i.
Z Z +J
o o r^
CM CM !•••.
o o o
001-
Z Z 4J
rH CD CM
in r^ cn
in co f^-
in CM rH
O Cn rH
r-H rH CSJ
rH Cn N.
CD rH CD
rH CM CSJ
CM ro W
000
1 1 1
CSJ CS) CM
CO 00 CO
•a- w
rH 1 -f
i in in
O r-t *t
1 1 1
§§§
t/) LO t/1
1 1 1
UJ LU UJ
1 1 1
rH rM r-H
00 00
O^ CTl
rH tH
ID O
0 0
O O
ii
o cn
rH 0
O O
0 0
a o
z z
0 0
CM CM
0 0
o o
z z
Cy> rH
CM r^.
CD CO
«3- CSJ
CM cn
rH rH
r^« o
cn CM
rH CSJ
CD CO
o o
CM CM
co oo
<*•
rH +
i m
o ^i-
i t
CO 00
t 1
<£ •
rH 1 -t- rH ( •*•
i in in i in un
O rH tj- O rH ri-
UO CO CO OO CO CO
1 1 1 1 1 1
t 1 1 1 1 1
rH rH rH CM CM CM
77
OOOOOOOO
OOOOOOOO
oooooo s-o
rHOrHOOOCSJO
OOOOOOOO
OOOOOOOO
OOOOOO L.O
ZZZZZZ4JZ
oooooocno
CMCMCSICMCMCM^rCM
OOOOOOOO
OOOOOO i-O
ZZZZZZ4->Z
cDincDrocsiCMCsiro
ooinocnmroroin
•a-i~-cocDcoooooeo
coroor^cocococo
rH rH rH rH CM I-H rH
rHlDOOCSI^-CMCSJCM
OOrHCnrHrHCDOrO
rHCMrHCMCSJCMCMCsl
cocor^oocnorHcsj
Ill
CSICMCMCMCMCMCMCM
•a- tt «*
rH 1 + rH 1 + | +
i in in i LO in un Lfi
OrH^J-Oi — ("ej-i — 1^-
1 1 1 1 1 1 1 1
=>>>>>>>>
COCOCOCOCOCOOOCO
1 1 1 1 1 1 1 1
zzzzzzzz
1 I 1 U 1 1 I 1 1 I 1 1 1 1 1 1 1 1 I 1 1 l 1
1 1 1 1 1 1 1 1
T-HrHrHCMCMCMroro
00 co co co
r-» «a- r** m
•o- ro o csj
oooo
oooo
oooo
cn o ?> cn
O rH O O
OOOO
OOOO
oooo
z z z z
oooo
CSJ CM CM CM
OOOO
oooo
z z z z
r-H CSI CD -3-
ro CD cn o
co r~. oo co
CO r-. CM CM
>a- in o r-
rH rH CM rH
^}- CD ID ^>
ro O CM rH
CM CSJ CM CM
ro *j- in CD
oooo
fill
CM CSJ CM CM
CO 00 CO 00
•a-
I-H 1 + +
i in in in
0 rH «J- <*•
I 1 1 1
OOOO
OO CO CO CO
1 1 1 1
z z z z
1 1 1 1
rH rH rH CM
-------
s**,
•o
3
C
4->
O
U
ro
CM
C ro
r-
•4-> Ol
X S
LU
0) Ol
3
in i
in
+•> -d
Ol
Ol 01
OJ
D- !-
in £
H-< C
Ol
Ul
O
0 -Q
U E
D.
ro
rHCMCMinrHinrHlDrH
CMCnCMr-*rHlX>rOLniX>
OOOOOOOOO
OOOOOOOOO
O Q O S- O Q O Q O
ZZZ4->ZZZZZ
OCOOCMOrHrHrHrH
OOOOOOOOO
OOOOOOOOO
OOO S- O O O O O
ZZZ-I->ZZZZZ
OOOCMOOOOO
CSICVJCMCMCSICMCMCMCNJ
OOOOOOOOO
000 S- 0 0 0 0 0
ZZZ-PZZZZZ
OT3-LOrHro*l-r^Oin
S3 S co S S °. co R S
CO CO UO CM * ID *, rH *
CMCMCMrHrHi— trHf-HrH
OOOOOOOOO
1 1 1 1 1 1 1 1 1
CMCMCMCMCMCMCMCMCM
cococococococococo
rH 1 + rH 1 1 + 1 +
i in in i in ui in un LO
i i i i i i i i i
OOOOOOOOO
i i i i > i i i i
i t i i i i i i i
V CO CO *J-
rH rH r-t LD
10 in in VD
Cn CM rH CM
O O O O
0 0 O 0
o a o o
z z z z
r^ o o en
0 0 O 0
0000
ooao
z z z z
0000
CM CM OJ CM
0000
o o o a
z z z z
CM OJ «• CM
r- ro CO CO
t^ co co r^-
^^crom
rH IO 00 VO
CM t— 1 i— 1 i— 1
r- 1 OT r*-. r-H
CO O^ O rH
Csj rH CM Csl
^- CO CH rH
O O O O
1 1 1 1
CM c\j csj csj
CO CO CO CO
rH 1 + +
i tn m m
O rH *J- «3-
1 1 1 1
O O O O
to co on LO
iiii
UJ UJ UJ LLJ
iiil
t— 1 r-l rH CM
«3-
^- «3- ^- 00
00 CO 00\
oo^r^S
Lf) Lf> ID VD
r^ o r^- o
0 0 O O
0 O 0 0
O O Q
z z -z.
co en «s- ai
0000
o o o o
§§ i
00 0
CM CM CM CM
0 0 rH 0
a Q o
Z Z Z
dO r** ^D ro
r*- **• ID
rH CO
rH CM rH
rH CSI CM rH
rH CM CM CM
CM ro ^d- in
o o o o
i i i i
CM CM CM CM
CO CO 00 CO
*f **•
<$• ^ «d-
rH \ + 1
i LO un uo
O rH «d~ rH
IIII
O O O O
U> t/> t/) LO
t t 1 1
t/> LO CO CO
< > 1 1
rH rH rH CM
C
tn 4->
a'
t- J2
o
a>
0 OJ
O r-
_J
^ m
o n?
*J 4->
4J 0
•r- V)
•P 0)
C t-
re CL
O" V)
H—
O "O
c
-*-> 3
i 1
r- O
•o °
01 ai
1o i^
Ul OJ
1C
ai s.
f -u
r-
II
S.
*^S 4->
Z
^^
to
X O
in 3
. •*>
>— ' C
1.20 pg/sample
lit of detectit
"* -o
C J->
3 ro
a. ••-
s •+>
o in
U Ol
in QJ
•f- .C
jC +J
4^
ul
S_ -r-
o
H- Ul
*-^ . Ul
Q <-^ O)
O Z .C
— 1 \ 4->
•^— ' l/) CZ
01
C X S-
o
-------
l/l
E
CO
01
3
in
if)
r-
O.
U r-
wet Concent
l) extractable
C D)
o a.
•u
. Concentre
) tissue
E TJ
to u
+-> QJ
0 4J
h- OJ
•o
TD
r^JS
OJ CT
TO
TO CJJ
i- -•—
-P O)
X ?
UJ
0) O)
V)
+-> JZ
en
(U
Q. t.
Sample composite MRI san
number numbf
CO CO 00
01 en o
*H -^ rH
LO ID rH
000
o o o
000
z z z
CM rH O
CM rH rH
O O O
O O O
O O O
Z Z Z
000
CM CM CM
o o o
Hi
ro rH ro
CM O- •el-
CD r- CO
co cor-
in ro r—
rH rH
O ro O
en co rH
rH CM
O O O
CM CM CM
co co co
rH 1 H-
O rH *
1 1 1
O O O
CO CO CO
1 1 1
1 1 1
•3- «• «3"
co co co
en o en
o o o
o o o
000
z z z
o en r—
rH O O
000
O O O
O O O
Z Z Z
000
CM CM CM
O O O
000
z z z
rH CD CM
in co r~
LO CM rH
o en t-H
rH rH CM
rH en r~
en rH CD
rH CM CM
CM ro «3-
000
1 1 1
CM CM CM
00 CO CO
r-l i +
O rH *
1 1 t
§§§
CO CO CO
1 1 1
LLJ LU LU
Z Z Z
1 1 1
4/19/84
4/19/84
CO O
o o
0 0
o o
z z
o en
rH 0
o o
o o
o a
z z
0 0
CM CM
O O
ii
en rH
CM r»
CO CO
* CM
CM en
i— 1 rH
r~ o
en CM
rH CM
0 0
p 1
CM CM
CO CO
rH H-
1 LO
O *
> >
CO CO
CL. CL.
I p
rH rH
•a- «3- *
* *• * OO OO CO
CD in i-H rH rH rH
* «- CO CO CD CO
rH O LO CM O CO
0 0 0 O 0 O
O O O O O O
000000
Z Z Z Z Z Z
en co CM o co rH
O O rH rH O rH
O O O O O O
O O O O O O
a o a a o o
z z z z z z
o o o o o o
CM CM CM CM CM CM
0 0 0 O 0 O
o o a o o o
z z z z z z
LO r*. LO r— CM en
r— o CM * co ro
r- co co co r- co
CO ro * rH * rH
r— o ro f— o in
rH CM rH rH CM rH
O CM CM CM r-l O
ro LO co O co CO
CM CM rH CM CM rH
Cn O rH CM ro «3-
O O O O O O
> 1 1 1 1 1
CM CM CM CM CM CM
CO CO CO CO CO CO
rH 1 + rH 1 +
i LO LO i in in
O rH *3- o rH CO CO LO LO CO
1 1 1 1 1 1
11(111
tH rH rH CSJ CM CM
slisisS
roCMm«a-rHcncMr-
00000000
OOOOOOOO
OOOOOOO i-
ZZZZZZZ+J
rHcnocncncooco
rHOrHOOOrHrH
OOOOOOOO
OOOOOOOO
ooooooo s-
ZZZZZZZ4->
OOOOOOO*
CMCMCMCMCMCMCMrO
OOOOOOOO
OOOOOOO L.
ZZZZZZZ*->
coincDrocMCMCMro
cotnocnrororoin
•o-r^cocococococo
coroor~-cocococo
COCOCO*r—rHCQCn
rH rH rH rH CM rH rH
rHCDCOCM*CMCMCM
COrHCnrHrHCDOfO
rHCMrHCMCMCMCMCM
uncDr^COCnOrHCM
OOOOOOOO
1 1 1 1 1 1 1 1
CMCMCMCMCMCMCMCM
COCOOOCOCOQOCOCO
rH 1 + rH 1 + p +
i LO in i in in in in
i i i i i i i i
OOOOOOOO
cocococococococo
1 1 1 1 1 1 1 1
zzzzzzzz
H 1 1 M 1 1 1 1 ] 1 1 1 1 1 1 1 i 1 1 i 1 1
1 1 1 1 I 1 1 1
co co co co
r~ •!)• F-- in
LO in in co
* CM o CM
o o o o
o o o o
a o o a
z z z z
en o en en
O rH O O
o o o o
o o o o
o a o a
z z z z
o o o o
CM CM CM CM
O O O O
liii
rH CM CO V
ro co en o
co f*^ co co
CO P-. CM CM
«3- LO O 1^
rH rH CM rH
•9- CO LO «3-
ro O CM rH
CM CM CM CM
ro ^3- in CD
O O O O
CM CM CM CM
00 CO CO CO
•a- *
rH 1 + +
1 I/) LD Lf)
O i— t ^- ^J-
1 1 t l
0 O O O
LO
-------
^•^
"O
3
C
*J
O
u
CM
Ol
^
ro
r-
ui 1C
i — Ol
(0 4-J
£•§
Ol
O)
' <3
0 TJ
4J D.
!- i—
C QJ
01 i —
U .Q
C ro
O 4J
U U
m
s-
4J
X
Ol
Ol
S
I .01
o n
4J
S_ =3
4-> in
C m
oi -r-
0 4J
o
c_>
.O
' — >
in n
in < —
E-D
ro u
4J Ol
0 4->
h- O>
•o
•o
'o.^
£>_/
01 Ol
•—
ro
R3 Ol
*J OJ
x S
LU
Ol Ol
3
in
4J i:
Ol
o< oi
01
e~\ £»
10 *"*
in E
ci c
ce
o>
r—
in
S.I-
E 01
o .a
U E
3
01 C
a.
E
LO
sss»s**s»s
***«, *^v **^ CO ""*••» 00 00 *"*Vi CO s*-v
Ln^^lDlDtDlDtDlDtO
r- ( O i— 1 rH rH O i-H r- 1 CM rH
OOOOOOOOOO
OOOOOOOOOO
0000,0000 s- a
ZZZZZZZZ4-IZ
OOOOOOOOi-lrHini-l
oooooooooo
OOOOOOOOOO
aoaaaooo s- a
ZZZZZZZZ4JZ
OOOOOOOOtOO
CMCMCMCMCMCMCMCMCMCM
OOOOOOOOOO
aooooooo (.a
ZZZZZZZZ-PZ
ai«-ir>rHrocn«-rvOLn
rOVDCMCflCrtrOOtOCMO
flOOOODlDOOOOr-COr^r--
CDCOmCMTj-cnioiDrH*)-
IDCMlDrOr^rHCMLOroCM
rH CM rH CM r-i rH rH
r^^-OrHLOrHCHOCMlD
ocMOericrivor-icdodr^
CMlDCMi— (rHCMfHr— IrHrH
r^- oo en o rH CM PO ^^ LO UD
OOOOOOOOOO
1 1 1 1 1 1 t 1 1 1
CMCMCMCMCMCMCMCMCMCM
oooooooooocooooocooo
^ ^j- ^- ^j-
T-t 1 + l-t 1 + 1 + 1 +
1 LDLD 1 LnLDLDLflLnLn
O rH ^ O rH ^ i"H ^^ rH ^
iiiiiiiiii
I/} to tO LO to to to tO t/) to
1 1 1 1 1 t 1 t 1 1
t/)toi/>tototototot*oto
1 1 1 1 1 1 1 1 1 1
rHrHrHCMCMCMrOrO^-^-
»t 00 00 T «•
rH rH rH tD tD
tD LO tO tD tD
Ol CM rH CTl CM
O rH rH O rH
O O O O O
O O O O O
o a o o o
z z z z z
r^ o o oo en
o o o o o
o o o o o
a a o o o
z z z z z
0 0 0 O 0
CM CM CM CM CM
O O O O O
o o o a a
z zzz z
CM CM ^J- ID CM
P^ ro CO r*. CO
r*- CO 00 CO P^
i — to ro in in
rH VO CO CM tD
CO en o in rH
CM r-t CM CM CM
r«- co en o rH
o o o o o
1 1 1 1 1
CM CM CM CM CM
^ "SJ"
rH 1 -f- 1 +
i LO m tn ir>
O r- 1 ^- r-t ^-
ooiii
LO t/) to to to
1 1 1 1 1
to oo i/> to to
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
1 1 1 1 1
r-4 i-H r-l CM CM
«r «• "3- eo
oo co oo \
m in tn tD
1^. O Cn rH
CM i-H O i-H
O O O O
O O O O
§OOO
ZZZ
oo en en en
0000
o o o o
o o o o
z z z z
o o o o
CM CM CM CM
O O O O
§000
zzz
ID n^ VD ro
r- VD «J- ID
to oo en oo
LO r^- CM en
r-. en I-H oo
rH CM CM r-i
rH CM CM CM
CM CO ^3- LO
§00 CO CO
000
1 1 1 1
CM CM CM CM
GO 00 00 00
^* ^"
r-l I + I
1 LO LT> LO
O rH «3- rH
1 1 1 1
O O O O
to to to oo
1 1 1 1
to oo oo to
S3: 3: 2
i i i i
rH rH rH CM
s~^
Z C
^ Ol
00 Ol
X 4J
o>
O -O
rH
Ol
01 >
i— a>
e^
••£+>
Oi *
"'"jj
o c
CO 01
'4J £
re
cr oi
H- (0
o t-
•i- II
•r- i.
I — 4->
•D
Ol .
ro o
E O
•r- — 1
4J ^
01 C
o
JZ 4J
r- U
ai
• Ol
z""0
00 O
X 4-1
in E
^^ *"
T5
I— 4->
o. m
E E
*-C in
Ol Ol
n.
01
0 -C
CM 4-1
O in
in
•i- t/i
^— > in
O QJ
O -C
_J 4->
*^ C
ai
c u
•r- O.
u c
Ol Ol
"O 3
U- nj
o >
'i-d
•r- OJ
I — 4-1
u
•o 01
Ol 4-1 •
4j oi o-
ro "O O
E — 1
4J 0 -0
in c c
0) ro
II
01 O
-COO
h— Z — 1
ro -Q
80
-------
TJ
in
Q)
CL
1
to
0>
=
in
1 —
01
o
o.
•O
4J
in
O
O.
o
o
oo
U-
,
rH
1
1
CO
r-t
O
•a
0
*»*
c
O)
c
J2
0
o
f
u
X
Ol
I
1
£_
o
O)
a:
TO
4->
ro
o
LTJ
CM
Ol
S
TO
r-
in
in OJ
>,*•>
r— TO
ro "o
c
Ol
O)
c
o ~o
4-> Q.
ro 'f-
^ f~
c o>
0) I—
U °
c nj
O +J
o u
ro
4-»
X
Ol
^
O)
1 01
C Ol
O 3.
TO in
OJ -r-
O -P
C
o
u
J2
O)
in U.
IS) •*—•
ro
01
TO U
4-> OJ
O 4->
r- OJ
•o
'o.-^
•r- ^
*~ ^
r—
JD 1
•2 *-*
u JT
t- T-
X 5
LU
OJ OJ
in i
tn
•r— -i>J
+•> JZ
cn
4_> «f—
S 3
01
"o. t.
ro ja
in E
3
I-H C
£
0)
in
o
o -o
u E
D
01 C
a.
e
m
uo
00 OO 00
O"> ff^ ^5
---
i?m ro
ro CM ro
O O O
o o o
O !- «-
Z *J 4J
CM r**« GO
CM rH CM
O O O -
o o o
O t- S—
Z 4J +^
O rH Cn
CM CO ID
O O O
Q t- S-
Z 4^ 4->
rO rH CO •
CSJ «3" ^t"
to r- oo
CD to r^-
in ro r--
O ro o
cn co rH
ro ro
^5?
O rH
c^) CT1
O O
O O
*"
cn cn
rH r^
0 0
O O
•*
ro r^
O rH
j_
Cri rH
CSJ r»
l£> 00
«3- CM
CM O
r- o
cn CM
i— 1 CM
IO CO
0 0
1 1
CSI CM
CO OO
«c
rH +
1 LO
1 1
O O
to to
1 1
CL. CL.
' '
^- ^- *f oo oo oo
oo oo oo "^. *^^ \
\. ^x.' — CM CM CM
**»*«»
LO o LO cn ro
CM *J- CO rH rH rH
O LO O O O O
O O O O O O
^w'
cn m ro LO i—t
r-t ^- CM rH T— t rH
o «*• o o o o
o o o o o o
^ o LO cn o
^- ^- CM ro CM
O rH O O O O
rH ^-^
S- S- t- S- O
4J 4J 4J +J Z
LO T*** LO r-« CM Cn
P^ o CM «3- CO ro
r^. co co co r^- co
CO CO ^- rH "fl- rH
p1^ o ro r*^ o in
O CM CSJ CM rH O
CO LO tD O tD CO
CSJ CM rH CM CM rH
Cn O rH CM rO ^*
^ m in m LO m
o o o o o o
1 1 1 1 1 1
CM CM CM CM CM CM
00 CO CO 00 CO 00
^.5 ^- S
rH 1 + rH 1 •+•
i in LO i m in
O rH ^- O rH ^f
1 1 1 1 1 1
O O O O O O
to to to to to t/)
1 1 1 1 1 1
y jg^ Z y ^" 5^
rH rH rH CM CM CM
c?;o-o-"""^
^ ^ ^ tD IJD 10 « tD
PTcMro^-'cncMCM'S-
CMrO^J-rHCMCMrHCM
OOOOOOOO
OOOOOOOO
^^ ^— • •>*>
Ot-S-OkUOt-
rH^LOC7><-OOOO
1-HCMroOCMrHrHCM
OOOOOOOO
OOOOOOOO
CMLntDCMLO'S-CMtl-
OOOOOOOO
^> *•_ -* s^
Z4->*JZJJ-PZ4->
tDLT>tOCOCMCMCMrO
cOLnocnroromin
«a-t^ootooooDoooo
coroor-.oooooooo
co to dD *^ r*1* rH to cn
rHLDCOCM^-CSJCSjCSJ
COrHCnr-trHtOOCO
i-HCMrHCMCMCSJCMCM
LntDP^COCnOrHCM
OOOOOOOO
1 1 1 1 1 1 1 1
esjCMCMCMCMCMCMCM
OOCOOOOOOOCOCOCO
^. 5 ^j- 5 5
rH 1 + rH 1 + | 4-
\ in in i in LO LO in
1 1 1 1 t i 1 I
OOOOOOOO
>>>>>>>>
1 1 1 1 1 1 1 1
UJ LU LU LU LU LU LU LU
1 1 1 1 1 1 1 1
r-trHrHCMCSJCMPOrO
CO CO CO CO
in m m to
o ^r LO CM
> > >
to to to to
1 t t 1
^t 3J j£ ^f.
1 1 1 1
<— i f^l __J pvl
81
-------
T5
Ol
3
C
in
CM
Ol
Ol
c
°J°
4J Q.
TO -i-
C Ol
01 •—
U XI
C TO
O *->
LJ O
TO
C Ol
O 2.
C in
01 -1-
u -u
c
o
Ol
m a.
in ^*
ID
E -O
Ol
r— *)
TO U
4-3 Ol
O *->
I— 0)
•o
Q. i-
E 01
TO X)
ro f*1 ^- iH r~4 f"t (M rH CO
ooooooooo
f*^ in UD to r^* in no
CM CM CM CM CM CO rH CM
OOOO OOt-HO
ooooooooo oooo oooo
Z -U 4-> 4J 4-> 4J
r-4 r-l ro O 00 O O
_ CM CM CM CM t-4 no o c\j
OOOOOOOOO OOOO O O rH O
OOOOOOOOO OOOO OOOO
i- S~ O i- i- i- i- i- S- t- S- S- Q t- S-
4-14J 2E 4J 4-> 4-» 4J 4J 4-> +J 4-> 4J Z 4-> -4-1
C^t CM P"- CM O OT HO
d d i-i d d d d d d dddd d d c\i d
S-I- O t- i- S- 1- S_ i- i. i- i- O t. S-
r^-oooOf^ IDOO^OD
)CSJtHr-(i—)t-lr-*rHt—I CMr-trHiM iHCMt-H
___-_-. OOOldi-i r4csjc\ji-l
CSJCMCNJr-t^HrHrHrHr-t CSJr—ICMCSJ ^HCMCSJCSJ
r*^ co CTI I~H cvj fi ^^ in
ooooooooo oooo oooo
i i i i
i i
i
i
CM CM CM CM
CO CO CO 00
1 1
1
CM CM CM CM
GO CO CO CO
O* 01
O —
c
ro
•o
Ol
Ol
Ol
X
m
c
O Ul
U Ol
Ul 01
l/l Ol
/^^- Ul
O X O)
q -c
_j o *->
^^-'rH C
v> Ol
C i-
O Ol TO
•^- — Q.
*-> Q.
O E C
Ol TO -r-
4-) in
*- TO
o o :»
CO
•u • o-
••- o • o
E -D -J
•r- l/l Ol
f— -i- 4J T3
U C
T3 "O Ol TO
O) C 4J
4-> 3 Ol O
TO O "D O
E Q. -1
h- 4J .
TO XI
82
-------
d. Phosphate Triesters
Tables 26 to 28 summarize data for triphenyl-, tributyl- and
tris(2-chloroethyl)phosphate. Triphenylphosphate was detected in the associ-
ated method blanks as well as in the samples. The data in Table 26 were cor-
rected for this background contribution. The data for tributyl- and tris(2-
chloroethyl)phosphate indicate that these compounds were detected at trace
levels in only one sample each. Prior to this study, the only information on
the presence of phosphate triesters in human adipose tissues was reported by
Health and Welfare Canada (LeBel, Williams 1983). In that study, 16 adipose
tissue samples were analyzed as part of a method development program. The
sample analysis was based on GPC separation of the lipid, fractionation of
the extract on a microflorisil column and analysis by either HRGC/MS or HRGC/
SIM. The data from the 16 samples indicated the presence of n-butyl, butoxy
ethyl, and 1,3-dichloropropyl phosphate triesters.
e. Phthalate Esters
Four phthalate esters were determined in the composited FY82
NHATS specimens, including the diethyl, di-n-butyl-, di-n-octyl-, and the
butyl-benzyl analogs. It should be noted that these phthalate esters were
also detected in method blanks prepared and analyzed with the composite sam-
ples. All phthalate data reported in Tables 29 to 32 were corrected for a
specific blank taken through the Florisil column with a designated set of
samples. Blank values ranged from 0.079 to 1.5 [jg for diethyl phthlate, 1.2
to 12 ug for di-nrbutyl phthalate, and 2.9 to 20 ug for di-rroctyl phthalate.
Blank values for butylbenzyl phthalate ranged from not detected at 0.20 ug to
0.78 ug.
Dimethyl phthalate was also included in the analytical stan-
dard and automated search and quantitation routines. This phthalate ester
was not detected in any of the samples.
f. Polynuclear Aromatic hydrocarbons (PAH)
The method evaluation studies indicated that PAH compounds are
recovered in both the 6% and 15/50% diethyl ether in hexane Florisil fraction
via the HRGC/MS analysis procedure. Tables 33 and 34 summarize the data for
naphthalene and phenanthrene that were included in the automated HRGC/MS quan-
titation routine for the composite sample extracts. Naphthalene and phenan-
threne were determined at trace levels in a few of the sample extracts.
g. Additional Compounds
In addition to the data reported in Tables 7 to 34, the HRGC/
MS data were also searched for additional compound classes including PBBs,
PCDEs, PCTs, and chlorophenol. Table 35 includes compounds or compound
classes that were included in the method evaluation studies and spiked QC
samples but were not detected in the composite specimens. Estimated detection
limits for these analytes are provided based on the observed instrumental sen-
sitivity from the calibration standards. It should be noted that the esti-
mated detection limits for the compound classes such as the chlorobenzenes,
chlorophenols, PCBs, PBBs, PCTs, etc., represent the method sensitivity for a
single isomer rather than the entire homolog.
83
-------
in
Q.
E
CO
ite Adipose Tissue
o
o.
£
O
CM
00
>-
LJ_
1
s~^
ID
1
ID
oo
in
rH
1-1
o
z
oo
re
.c
in
.c
o.
^
01
C-
s_
1 —
4J
i.
Q.
CD
ac.
re
.»-»
ro
o
CM
O.
i- 1 —
wet Concent
]) extractable
-V
C D)
o n
j->
Concentre
g) tissue
in ^— '
ro
01
ro u
*J O>
0 4J
t— 01
T3
T3
£«
S i
*J 4->
u x:
!- -r-
"x S
UJ
OJ D>
3
in i
in
-T> ^=
D)
*J -r-
£S
O)
'a. s-
Sample composite MRI san
number numbe
00
•a- f
CM rH
«*• If)
O "9-
rH in
O O
J_
4->
•a-
r*- ID
o >a-
0 0
i.
.!_>
01
03 ID
o en
S_
.(->
rH ro
* -a-
r^- oo
to r*~
ro i^
ro o
00 T-H
rH CM
r~~ I-H
o o
> t
CM CM
00 00
«3-
*
I +
in in
rH *
1 1
O O
> >
OO OO
1 1
S£
1 1
rH r-t
00 00 00
ro O CO
CM r-l CM
•a- «a- «•
00 r-4 Ol
CO CM r-l
O O O
O O O
0 0 O
z z z
rH 00 in
CM rH rH
000
000
000
Z Z Z
000
•3- -a- -a-
000
a o a
z z z
rH ID CM
in r*~ cn
in oo r~
in CM rH
O O> rH
rH > >
oo oo oo
1 1 1
QJ LU UJ
z z z
1 1 1
rH rH rH
00 00 00
*j- r^- in
CM CM CM
* «• "3-
CM f» rH
CO CM CM
O O O
O O O
O O O
Z Z Z
o en oo
CM rH rH
000
O O O
000
z z z
o o o
«S- «3- %3-
000
o o o
z z z
Cn 0 rH
CM 00 r~-
l£> LO CO
«}• r^ CM
csi <• en
r^ ixi o
Cn rH CM
rH CM CM
10 r^ oo
o o o
i t i
CM CM CM
oo oo oo
«•
* *
rH 1 +
i in in
0 rH *C
1 1 1
o o o
> > >
OO OO 00
> 1 1
us
CM O O
CM CM CO CM CM ro
O O O CM «3- i-H
000000
a o o
z z z
i~- ID in
rH rH CM Cn ro rH
O O O r-H ro rH
O O O O O O
O O O
Z Z Z
o o o
*r «d- «*- oo r^ en
O O O CO 00 rH
000
z z z
in f^* in r^ CM en
r-~ o CM «• oo ro
r^* oo oo oo r^ oo
00 ro *fr rH <3- rH
r^ o ro r^ o in
O CM CM CM rH O
CO in l£> O ID CO
CM CM rH CM CM rH
CO O rH CM CO ^T
O O O O O O
1 1 1 1 1 1
CM CXJ CM CM CM CVJ
*!• «•
*t -a- «• «•
rH 1 -f- rH 1 H-
i in in i in m
O rH «J- O i-H «S-
iiiiii
OO OO 00 OO OO OO
1 1 1 1 1 1
z
CM en o oo r-~
CM rH CM CM CO rH
O O O f O O
o o o in o o o
o a o s. o
Z Z Z J-> Z
o o o r~ en o
O O O rH CO O O
0 O 0 (-0
Z Z Z J-> Z
ir> in m ro CM CM ro
oo in o en ro ro in
•3- r^ oo ID oo oo oo
00 ro o r** oo oo oo
oo us vc «s- r~ rH en
rH V£> CO CM «• CM CM
00 rH Cn rH rH l£> ro
rH CM rH CM CM CM CM
in ID I — oo cn O CM
1 1 1 1 1 1 1
CM CM CM CM CM CM CM
«»• «*•
«* •* «*• «3-
rH F H- rH 1 + +
i in in i in in in
O rH «• O rH * •»•
1 t 1 1 1 1 1
O O O O O O O
»»>»
OO OO 00 OO OO 00 OO
1 1 1 1 1 1 1
z z z z z z z
111 yj u 1 ti I t i I f i 1 1 \ I
1 1 1 1 1 1 1
rH r-4 i— 1 CSJ C\J CO m
00 00 CD GO
O rH O IT*
rH rH rH rH
U"> Lf> If) t£>
rH rH '-N
m UD rH CM
O O CM CS|
o o o o
iii
CM r^ ^-N
ro •»• en oo
0 0 rH rH
O O O O
000
Z Z Z
u u
in i£> -*^
r^ Co co oo
o o *]• ro
a o o
z z z
rH CM OS «"
ro ic cn o
u> r^ oo 00
oo r-- CM CM
> »
oo oo oo oo
1 1 1 1
1 1 1 1
rH rH rH CM
84
-------
/->
01
3
,f—
4J
C
o
u
CO
CM
01
.G
t—
in
in 01
ro "o
c
^^
o>
ro
c
O "C
4-> O.
I- i —
4->
C 01
01 < —
U -C
c ro
O 4-J
o u
re
1 1
X
01
4J
Ol
s
1 CD
c ro
o a.
4J ^"^
ro 01
!_ 3
c in
Ol 'r-
U *•>
c
o
o
ro
in n
in s-'
ro
01
re u
4-> 01
O 4->
1 — Ol
•O
•o
C^1*^
ir~ &^
,_
JD 1
4J 4-*
u -c
re 01
t. -r-
4-> 01
X *
LU
01 ro
3
in i
•" 4->
4-> -C
CT
4-> *r-
01 Ol
3 ?
01
o. s-
E 01
ro J2
m E
3
t— i C
g
£
01
r—
in
O
til
U E
3
01 C
i-
0
-o
cocooococococococo
CMCMCMrHrHrHrHrHr-t
/~^^-\»— \ /-N*— v^-.
ro CO ^ O ^" CM csj VD CM
OOOOOOOOO
OOOOOOOOO
Sfcrf" ^S *M* S^"^S S_^
O O O S- O O O
Z Z Z 4-> Z Z Z
rH rH CM ID CO ID CM CM CM
OOOOOOOOO
OOOOOOOOO
O O O t- O O O
Z Z Z 4J Z Z Z
o o o o o o
OOOrHrHrHOOO
0 0 0 S- 000
Z Z Z 4-> Z Z Z
cn»j-inrHcocn*i-r~.u->
roiDCMencnrooiDO
coooooiDCOCO^cor~.
COOOLOCM«a-CniDV£>*l-
LOCNllDror^rHCMinCM
i — ICMrHrHrHCMrHrHrH
r--a-Orttr>rHcnoii>
oiDOcncnuDf^cor^
CNJCSJCMrHrHCMrHrHrH
r^- QQ en O rH CM CO ^ liD
OOOOOOOOO
t 1 1 1 1 1 1 1 1
ScocococococoSoo
^J" ^f ^
rH 1 + rH 1 -r 1 + -f
i LO Ln i in in LO LO in
i i i t i i i i i
ooooooooo
t/> l/l t/) ly) LO LO I/} L/l t/>
1 1 1 1 > 1 1 1 1
^^^^LOLOLOLOLn
1 1 1 1 1 1 1 1 1
rHrHrHCMCMCMCOOO^
OO CO CO CO
rH rH rH rH
in tn ID LD
r-N^~>
«*• oo «a-
CM O rH CM
rH CM O O
O O O O
*•-"«-•'
0 0
Z Z
Cn ID rH rH
O rH O O
O O O O
O O
Z Z
0 0
CM ro O O
0 0
Z Z
CM CM LD CM
r^ ro i^» co
r** oo co r^»
p*- ID in in
rH VD CNJ ID
CM rH CM rH
rH en f*^ rH
CO Cn LO rH
CM rH CM CM
P*. CO 0 iH
O O O O
1 1 t 1
CM CM CM CM
co co co co
•a- «•
rH 1 i +
i in in in
O rH rH -a-
1 I 1 1
L/) LO I/} I/)
1 1 1 1
LO LO CO CD
LLJ LLJ LU UJ
1 1 1 1
rH rH CM CM
CO «3" CO CO
3 cnS rH
in in in LD
^^
r~~, f^. CJ1
in o co o
o o o o
s-^s«^
O O i-
Z Z 4->
O CO O ID
•a- o co o
o o o o
o a s-
z z •>->
/TS ^*\
•a- en in
• co
^- rH rH rH
00 t.
IDI^lDro
r^ ID ^* LO
LD oo en co
in p^ CM en
t-^ en rH co
rH CM rH
rH r~ «- CT>
rH CM CM rH
rH CM CM CM
CM ro «* in
co co co co
o o o o
i i j i
CM CM CM CSJ
oo co oo oo
^- ^~
rH 1 4- 1
i in in in
O rH *a- rH
1 1 1 1
O O O O
LO CO LO CO
1 1 1 1
^ COCO CO
1 1 1 1
rH rH rH CM
01
D.
E
ro
in
\
ro
ID
rH
in
«r-
/-^
Cr
O
_l
\^^
c
0
re
4->
4->
C
ro
3
cr
n-
o
4J
E
r—
•o
01
4->
ro
E
4J
U)
01
01
-C
[
/•^
z
•^
en
X
in
CM
s^/
01
Q_
E
in
\
Cn
o
d
in
• r—
Q
o
— 1
c
o
4-J
u
01
4->
01
•o
K-
o
.t?
E
r"
TJ
Ol
4-> .
re '-v
•»-> CO
Ol X
OJ 0
.C rH
r- s_.
ro .£
, —
01
> 01
01 3
re
ro >
4-> 01
ro ^
r-
C
01
in -*:
01 C
^ ro
o. »—
^3
in
•r- TJ
o
T3 ^
C 4J
3 01
0 E
Q.
E 01
O >
O •!-
4^
41 U
^ Ol
r- CL
in
01
c.
01
U 01
ro .e
t. 4->
c
II "-
S. C
4-» O
4_J
ro
/-s t
O 4->
o c
—1 01
^s O
c o
o u
4-> T3
01 >
4J C_
01 a1
T3 in
>*- O
0
ai
4-> .C
•r- 4-> Ol
E 3
•i- C r—
r- re re
JC. >
T3 4J
01 -*
re in re
_E ^01-
4J
in in 01
2 4J
ai
f 01 O
4-> r— 4J
in E in
•i- re "o
in c
in o
01 01 CX
in .c tn
.C !~
4-> C t.
C -r- O
01 U
i- 01
ro 4-> 4-1
c "re -^
•r- C i —
ro
fll C
3 Ol O
• ^C. •!-
re 4-> w
^* u
. I*- 01
O- 0 4->
• o ai
T3 — 1 C T3
01 o
•*•> "D ••- 01
U C 4-> f
ai re ro 4J
4-> i-
01 O 4-^ in
•a o c: re
1 01
4J U "O
o c c 01
C 01 O *J
ai o s-
II i o
4J 01 a.
O 01 -C 01
2 U
85
-------
3
HI
D.
e
ro
Ol
3
IA
.£
O>
(/)
0
o.
'^
^
.3
*IA
o
Q.
E
O
o
CM
00
1
co
i
ro
i
VD
CM
rH
O
z
§
w
ro
Q.
o
ex
J->
XI
t—
^
O
Q.
QJ
(D
4->
ro
o
CM
O)
ro
r-
tA
>,-2
ro ~o
c
•a
I?
o>
i a
c
O "O
ro ••-
C 0)
0) r-
U XI
c ro
O 4J
vo u
ro
S-
4^
X
a>
ct
2
1 O)
C 01
•S v3
ro a>
i- 3
c: to
0> -r-
U 4->
c
o
o
XI
i/) n
£ -0
0)
I 4->
ro o
0 4->
r- 0)
"°
•D
•£-
•r- X
XI 1
(0
U -C
ro 01
**
O) Ol
in i
i/i
4J .C
Ol
Q) QJ
3: *
01
Ife
S|
r-l C
ce
OJ
l(_
V)
o
Q, i-
0 XI
u s
a> c
i
(U
•a- f
00 00
»^
CM rH
Q" ID
*f VD
0 0
O O
O O
Z Z
ID 00
ID -a-
o o
o o
o o
z z
0 O
o o
z z
rH ro
r^ oo
vDr-
ro (-.
ro O
00 rH
rH CM
O O
1 1
CM CM
CO CO
^.
•a-
i +
vn urt
•-H «a-
i i
CO CO
1 1
1 1
rH rH
00 CO 00
ro o ro
CM rH CM
^^ ^ ^
ID CM f^
O O O
O O O
O O O
Z Z Z
CM VD r~—
vn Q- ro
o o o
o o o
a o o
z z z
o o o
000
z z z
rH ID CM
ID r^. cn
ID oo r~.
VO CM rH
O Cn rH
rH cn r~-
Cn rH VD
rH CM CM
CM ro «a-
O O O
1 1 1
CM CM CM
00 CO 00
<*•
rH 1 +
1 ID ID
O rH *)•
1 1 1
000
CO CO CO
1 1 1
LU LLJ UU
z z z
1 1 1
rH rH rH
GO CO OO
*)- r^ in
\ ^1 ^
^* ^ ^
i—t CO CM
000
000
o o o
z z z
rH VD ID
ID «a- ^~
o o o
000
000
z z z
o o o
o o o
z z z
Cn O rH
CM oo r*.
VD ID OO
*r i^ CM
CM «*• cn
r^ VD o
Cn rH CM
rH CM CM
vc r» oo
000
1 1 1
CM CM CM
oo co co
^.
•a- *
rH 1 4-
i in ID
O rH -a-
1 1 1
0 0 O
> > >
CO CO CO
1 1 1
*z
Tj- in in in in cn
0 o O o 0 o
i i t i i i
CM CM CM CM CM CM
CO CO 00 00 CO 00
^* 4"
*^ ^ ^ *^
rH 1 + rH 1 +
i in in i ID ID
O rH «3- O rH ^>
1 1 1 1 1 1
O O O O O O
CO CO CO CO CO CO
1 1 1 1 1 1
gggggg
1 1 1 1 1 1
rH i-H rH CSJ CS) CSJ
CO CO 00 CO CO CO CO
in tO iJD •«• ^- «d- *£>
^^^^^•^^
^^ "Ct" *^ VO VD *X> >*&
*~^r-\ CO tO VD UD
rH VD VD CSJ if) tf «CT
rH O O rH O O O
O O O O O O O
0 O 0 £-000
Z Z Z -P Z Z Z
IT) VJO rH lT> ^ CO fO
iT) *d- tn co **• ro ^~
o o o o o o o
0000000
000 £-000
Z Z Z 4J Z Z Z
O O O CO O O O
o o o s- o o o
Z Z Z •!-» Z Z Z
V£> in VD CO CNJ CSJ CO
co to o cri ro co in
•Cf r^ CO VO CO QD CO
CO ro O P*- CO CO CO
CO VO V£> *J- r-^ rH CD
rH VO CO Cst *S- CSJ CSJ
CO rH CT> r-l rH VO ro
i—l CSJ rH CSJ CSJ CSJ CSJ
in v£> r^- co cn o CM
in tn in LD in vo vo
0000000
1 1 1 1 1 1 1
CSJ CSJ CSJ CSJ CSJ CSJ CSJ
CO CO CO 00 00 00 CO
*J- ^J-
^J" ^" ^f" ^
rH 1 -r rH 1 -f -f
i tn LO i tn tn in
O rH ^- O rH -CJ- "tf
1 1 1 1 1 1 1
CO LO tO t/> V/> V/> C/>
1 1 1 1 1 1 1
z z z z z z z
1 1 i 1 1 i LI i 1 1 1 ijj LU LlJ
1 1 1 t 1 1 1
rH rH rH CSJ CSJ CSJ CO
«*• T * ^>
CO CO CO CO
O rH O tn
\ \ \ \
in in in vo
co *r tn co
vo VD ^- tn
o o o o
o o o o
0000
z z z z
ro cn ^a* ^
*- «a- «s- -a-
o o o o
o o o o
o a o o
z z z z
0000
o a o o
z z z z
rH CM OO «•
ro VD cn o
vo p^ co oo
CO r^ CM CM
•a- in o r~
«)• VC ID «t
ro O CM rH
CM CM CM CM
ro «a- ID VD
VD VD VD VD
o o o o
1 1 1 1
CM CM CM CM
CO CO 00 00
^.
«* -a-
rH 1 + +
1 ID ID ID
O T-H ^- «J-
1 1 1 1
o o o o
CO CO CO CO
1 1 1 1
liii
1 1 1 1
rH rH rH CSJ
86
-------
/-**
Ol
3
4-»
C
O
u
r**
CM
0>
.O
(B
r-
V}
in 01
£3
re x>
c
<
,-^
O)
\
01
i 3.
c
O TJ
« -i-
wet Concentr
extractable
I 01
•>.
C Ol
•r— -*^
. Concentrat
)) tissue
m a.
in *~s
E T3
O)
1— <->
ro u
4-> 01
O 4J
h— 0)
•o
•o
o.^^
••-»«
S i
*J 4->
o .c
i. •<-
4J 01
x y
LU
0) O)
3
V) 1
I/)
*J .C
O)
11
O>
O. I-
ro £1
in E
3
az
01
+j
in
o
D. S-
O &
U E
01 C
I
TO
UO
«--3-«l-«3-^-«3-«3-«r«-
aocDcocoaooacooooo
VD^-^)-iri^-roiI3iX)00
OJC\JOJf-li-liHrHr-lr-l
<-^-*3-lDlDlCI£>lDVD
oo«»-r-iiiir^iDai^-i-i
iD«s-ii3r^in*1-r^iDco
ooooooooo
ooooooooo
ooaooaooo
zzzzzzzzz
OOGOOCSJrHCOlOlDr^
•a-roinminmminin
ooooooooo
ooooooooo
ooocioaooo
zzzzzzzzz
ooooooooo
C2OOOOOOOO
zzzzzzzzz
o>^-ir>i-HPOcr>^-r^ir)
ni£>cvjc^CT^noix>o
oacooo^ococof^oor^
oooomMfl-cniDiii^}-
IDCSIlDfnr^-rHCSIknCM
F-ICSlr-frHi-HCsJrHrHr-4
r^^j-oi— tiDf— iff^oin
OlOOCTlOllDI^-OON-
CNjCMCSJf-HrHCMt— lr-H»— 1
1 — COOOr- )esjf^)*3-^o
OOOOOOOOO
1 I 1 t i I I I i
CSjCsJCSJCsJCMCvJCVJCMCsJ
OOCOCOCOO3COCOCOCO
«*• I" f
«3- <9- ^5- »t «t
rH 1 + i-t 1 + 1 + +
i tn tn i m in in Lf> in
1 1 1 1 1 1 1 1 1
ooooooooo
>>=>>>>>>>
ooi/>i/)t/imi/)i/iv)to
i i i i i i i t i
OOLOO^COl/>C/}l/>l/)
1 1 1 1 1 1 1 1 1
rHrHr— tCSJCSJCSjmro^J-
«r «s- 1>- «>• -SI-
GO co oo oo co
*r ^- ^- ij) ID
t-H f— t i— ) r-t f-H
m ID in «> <£>
V£> O Lf> *y- r-t
*r VD in «r ^D
O 0 0 O 0
0 0 0 O 0
a o o a o
z z z z z
i£> o oo 01 r^
ro in T>- m -a-
o o o o o
00000
o o o o. o
z z z z z
o o o o o
0 0 0 0 Q
z z z z z
CM cvj ^- in eg
r*. ro oo P^ oo
t^ oo oo co r^
r- us « in in
rH ID OO ^ 1C
CM rH 1-4 CsJ T— t
CO O> O in r- 1
CM f-H CM CM CM
f^ 00 O^ O rH
O O O O O
I 1 I I 1
CM CM CM CM CM
t o-
•o- «s- *r
rH 1 + 1 +
i tn in m tr>
00000
l/> I/) I/) V) I/)
1 1 1 I 1
t/> to co i/i uo
1 1 1 1 1 1 1 1 1 1 l_l L 1 1
1 1 1 1 1
rH rH r-t CNJ CM
^f "3- *f
CO f 00 00
r-t CT> rH rH
in in tn VD
- — »rH r^ ro
m in ^t- in
rH 0 O 0
o o o o
o o o o
z z z z
o ««• in i£>
0000
o o o o
§000
z z z
o o o o
o o o o
z z z z
ID r-~ tx> ro
r^ U3 «f ID
ID 00 Ol 00
in r-*. CM c^
N- O1 rH OO
rH CM rH
rH CM CM rH
rH CM CM CM
CM PO «}• IT)
o o o o
iiit
CM CM CM CM
00 00 00 00
«• Tf
V •>
OO to VI I/)
IIII
C0g£g
1 t 1 t
i-H rH f-1 Cg
. c.
/—s
QJ
to *->
(/> TO
>s.
D)*J
O. C
0,
VD (A
• QJ
i— t i-
Q.
w
•»- in
•r-
i?
—I 3
'—' O
§1
"- (J
rrj 01
•r- 1—
4->
C
(0 .
3 01
O" U
to
H- i.
O j->
•M II
'i t.
•r- 4^
T3 .
0> ^^
S/N). The estimal
. of detection (LOI
X •>-
Lf) *r-
•^^ -rj
(U
r— ftJ
i^
03 4^
U) (/>
"S,0'
a. 01
.c
O *J
r-i in
ction (LOD) is
n parentheses
4-3
Ol 0)
•0 3
i- "re
0 >
4->
i -o
•r- Ol
r— 4J
U
T3 0)
Ol 4J
4-> Ol O1
m-oo
•r- +J
4J O TJ
in c c
01 tu
II
Ol O
J= o o
1— Z — 1
1C A
87
-------
re
U)
o>
D-
E
re
to
01
3
Ul
U)
r-
Ol
Ul
0
D.
•5
Ol
O
SJ
CM
co
U-
1
r~\
00
ID
en
in
rH
rH
O
Z
to
E 1
01
re
o.
Ul
o
Q.
^
rr
C.
Ol
O
o
<_J
1
CM
Ul
"r"
J->
I
&.
O
cc
4->
re
0
CO
CM
r-
0
O
X)
CT
u> a.
U) s— '
(0
E -0
Ol
i— *>
re u
H-> 01
0 .U
t— 0)
•o
•D
Q./-^
CJ Ol
£1 1
re
*> -4->
U -C
re 01
i- —
LU
O) Ol
1/1 1
Ul
Ol
OJ (V
3: S
o>
fri
re xi
VI E
3
i— I C
ce
^
01
o
E O)
U E
3
Ol C
o.
E
re
to
T)- 1- «!•
CO CO CO
Tj- «S- «•
sss
f^O ID
in *D ^~
rH O O
000
o o o
z z z
o «• en
en ^- ro
o o o
0 O 0
z z z
o o o
co oo co
o o o
z z z
ro rH ro
CM «a- «a-
ID to r^
in ro r~
r-l rH
o ro o
en co IH
rH CM
ID r- rH
ro ro *^
0 O 0
1 1 1
CM CM CM
00 CO 00
I-H 1 +
i in in
i i i
o o o
to to to
i i i
iii
i i i
«*•«»••>*•
co co co
ro o ro
^i?^?
rv CM 00
r-» ^~ CO
O O O
0 0 O
O O O
CM r-. o
Sro ro
0 O
0 0 O
o o o
z z z
o o o
co co co
o o o
ggz
rH ID CM
in r- en
m co r-
in CM I-H
O O1 rH
rH rH CM
rH cn r~
en I-H to
rH CM CM
CM ro -sj-
^" ^" ^
O O O
1 1 1
CM CM CM
00 00 00
•* •*
rH 1 +
i in in
0 rH «S-
1 1 1
O O O
to to to
i i i
UJ UJ LU
Z Z Z
1 1 1
rH rH rH
S* f
co co
w r-. in
«r CM re
in in CM
ID in «a-
000
o o o
o o a
z z z
rHoo r-
«- ro ro
000
O O O
000
z z z
000
00 00 00
o o o
§o a
z z
Cn O rH
CM oo r-
tO ID CO
«• r» CM
CM «• cn
rH rH rH
r- us o
Cn rH CM
rH CM CM
ID r- CO
sss
1 1 1
CM CM CsJ
CO 00 CO
rH I +
i in ID
O rH ^*
1 1 1
000
10 to to
1 1 1
a. a. a.
i i i
rH rH rH
SSScooSS
ro CM «*• ro ro ro
^^^ tO VD a- «»• ID «• TJ- m
o o o o o o
o o o o o o
a o o o a o
z z z z z z
in CM cn o rH m
ro ro ^- ^- ro ^*
o o o o o o
0 0 O 0 0 O
zizizi
0 00 0 O O
o o o o o o
o a o o o o
zz z z z z
in r^- in r*> CM cn
r~ O CM ^- CO ro
r— 00 00 00 r*. 00
r» o ro r- o in
rH CM rH rH CM rH
O CM CM CM rH O
ro in ID o ID co
CM CM f-H CM CM rH
Cn O rH CM ro ^T
<• in in in in in
0 00 O 0 O
i i i i i i
CM CM CM CM CM CM
rH 1 + rH I +
i in in i in in
0 rH<3- 0 rH «*•
1 1 1 1 1 1
000000
tO tO tO IO tO t/5
1 1 1 1 1 1
1 1 1 1 I 1
rH rH rH CM CSJ Csl
coScocococococo
Lntoto-^^^aouD
^^^ii
CMOrHintDr^COrH
OOOOOOOO
oooooooo
zzzzzzzz
incOrHCOOOrHOin
oooooooo
oooooooa
zzzzzzzz
oooooooo
cooocococoooaoco
oooooooo
00000000
toingDcocsjcsjcsiro
COinocnoororom
CO rr, o f-. 00 co co CO
cdtoirj^r^rHtoai
rH rH i-H rH CM «-H rH
rH(X>COCM^J-CMCMCM
COrHCnrHr-HVDOfO
rHCMrHCMCMCMCMCM
LOLnLnLnmiDiotD
oooooooo
i i i t i i i i
CNJCMCSJCMCMCMCMCM
rH i + rH 1 + t H-
i in m i m LCI m LD
i i i i i i i i
V) IS) tO tO V) tO (/} tO
1 1 1 1 1 1 1 1
zzzzzzzz
1 1 1 QJ 1 t 1 i 1 1 1 1 1 |JJ 1 1 t 1 1 1
1 1 1 1 1 1 1 1
rHi—irHCMCMCMrOrO
00 CO CO 00
o r-i o m
in in in ID
in CM o r^
in in ^- «*•
0 0 0 O
0 0 0 O
o a o o
z z z z
in cn us co
ro ro ro ro
O O O O
d d o d
o a a o
z z z z
o o o o
00 00 CO 00
o o o o
§i§i
rH CM 00 «3-
ro to cri o
u> r*. co oo
co r*. CM CM
^- m o rs.
rH rH CM rH
•fl- 10 uo «a-
ro o CM rH
CM CM CM CM
oo •«• in ID
tO ID tO ID
o o o o
III!
CM CM CM CM
CO GO CO CO
rH t + H-
i in m in
i i i i
to 10 to
i i i i
iill
i i i i
rH rH rH CM
88
-------
Ol
•1-
c.
o
u
CO
r\l
01
re
r-
in 01
re T>
c.
Ol
Ol
1 3.
•P O.
2 P^
wet Concent
) extractable
C 01
0 3-
*J
. Concentr<
)D tissue
m a.
in -^
E -a
m o
4-> Ol
o *->
P— Ol
•o
•o
s P
U .C
4-> OJ
X 3
LU
OJ
¥fc
ro ^
in E
rH C
OC
Ol
O
QL S-
E 01
O -D
U E
01 C
it
cooococococococoooco
oooooooooo
oooooooooo
OOOOOOOO.OO
zzzzzzzzzz
oooooooooo
oooooooooo
OOOOOOOOOQ
zzzzzzzzzz
oooooooooo
'oooooooooo
aooaoooooo
zzzzzzzzzz
er,«j-inrHrocn.«-r^Oin
cococooococor^cor^r—
00 00 in CM «t 0> 1C U3 rH «•
oooooooooo
1 1 1 1 1 1 1 1 1 1
CMCMCMCMCMCMCMCMCMCM
cocococococococococo
rH 1 + iH 1 + 1 + 1 +
1 1 1 1 1 1 1 1 1 1
oooooooooo
1 1 1 1 1 1 1 1 1 1
1 1 1 1 1 1 1 1 1 1
«• «s- «• in co
in in in co CD
o o o o o
o o o o o
00000
z z z z z
Ch rH CTI r-i r—
CM *r ro ro •»•
00000
o o o o o
o o a a o
z z z z z
O 0 0 0 0
o o o o o
a o a o a
z z z z z
CM CM «t in CM
P-* co oo co r**
f^ ID ro in in
r-l ID CO CM CD
CM r-l rH CM rH
CO Cn O m l— 1
CM rH CM CM CM
r^ co en o rH
o o o o o
11)11
CM CM C\J CM CM
r-l 1 + 1 +
i in in m m
O rH -3- rH -3-
» » >
CO CO 00 CO CO
1 1 1 1 1
CO CO CO CO CO
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
1 1 1 1 1
r-l r-* r-l CM CM
CO ^ CO CO
-v. 00 >»»•»
^ ^^ o m
in in m CD
rH CO ro
rH ^t" ft ^
CM O O O
O 0 0 0
i- a o o
•P Z Z Z
^ ro ro ro
r-l O O O
0000
1-000
•P Z Z Z
o o o
co oo oo oo
i-l O O O
s- a a o
4-> Z Z Z
ID r^ CD ro
!»* ID »}• CO
co co en co
in r-- CM en
r^ en i— i oo
r-l CM iH
l— 1 CM CM rH
rH CM CM CM
CM ro *j- in
o o o o
1 1 1 1
CM CM CM CM
CO CO CO CO
rH 1 + 1
i in in in
0 rH .3- rH
1 1 I 1
O O O O
CO CO CO CO
1 1 1 1
CO CO CO OO
1 1 1 1
rH rH rH CM
•o
C
3
O
U
c
in at
£ 1
01
o
II- f—
i 1
•*~s to
mit of quantitation
ipound is present at
i— O
u
•o
•P -C
in 01
Ol U
re
Ol i.
r-
II
S-
Z
CO
o
!0 pg/sample (?..'
. of detection (
in i—
•o
•O Ol
3 re
o E
Q. ••-
E <->
o in
u 01
in 01
in
i- •!-
ction (LOD) fo
.
n parentheses
•P Z
01 \ Ol
-O CO 3
•t- X ro
O >
O
*-> rH
E "^-d
•r- Ol Ol
>— r— 4->
a. u
•0 E Ol
+•* W 01 O*
It >v T3 O
E Ol —1
•P O T3
U) CM C C
oi . re
ro II
01 o
.c in o o
P— T- Z — 1
1C JS
89
-------
in
OJ
I
re
oo
01
i/i
in
r-
01
in
O
Q.
T3
OJ
,,_
in
O
Q.
E
O
CM
co
i
*~*
CM
1
1
CO
O
Z
OO
•t^
01
4->
re
ro
4-}
jz
^
-C
-t->
o
1
s_
o
Q.
01
o:
re
re
Q
en
CM
ai
re
h~-
in
Ul
r^ .S
re re
c o
ai
Ol
i a
c
O XI
4J O.
S- r—
4J
c ai
cu • —
O JD
c re
O -r>
O (J
re
.4_>
X
a>
0)
?
1 O)
C Dl
o a
+3 ^~*
re 01
i- D
-r> in
c in
01 *r-
U H->
C
O
^r\
Dl
in a
in -^
re
E -O
, ^J
re u
4-> a;
o -u
r-
U J=
i. -r-
X X
UJ
cu cn
3
in i
in
•r— | '
•P J=
Ol
•*-» *r-
CU CU
!S 3
a>
'a. s-
E cu
re JD.
VI E
3
1-H C
DC
OJ
o
a. i-
E cu
u E
ai c
§-
ro
oo
CO CO
«3- **•
CSJ rH
«S- in
^^
r~- cn
ro «r
0 0
o o
*^s
0
z
,-^
r^ csj
CM •»
0 0
o o
o
z
u
o r-
in co
o o
o
z
rH ro
r-~ co
in r-
ro r~
ro o
CO rH
rH CM
r~ rH
0 0
1 t
CM CM
CO 00
1 +
in in
j i
O O
oo oo
1 1
ii
1 1
rH rH
CO CO CO
ro O ro
CM rH CM
ff ^- ^
CSJ p^ CO
rO rH rH
O O O
O O O
t- S- fc.
co in ^i-
rH rH rH
O O O
O O O
i~ t- S.
+J +J .4-)
•53- CM 00
PO ro ro
O O O
S_ £_ S_
4_] +J 4J
i-t UD CM
in co r^
tn CM rH
0 0> rH
rH cn r^
Cn rH UD
rH CM CM
CM ro ^~
O O O
1 1 1
CM Csj CM
CO CO CO
rH | +
i in in
O rH «3-
1 1 1
O O O
t/> to t/>
1 1 1
UJ LU UJ
Z Z Z
1 1 i
rH rH rH
CO CO CO
*3- r^ in
CM CM CM
«• w «»•
^**s-*, *-%
1C ^f 1C
ro ro CM
o o o
o o o
a o a
z z z
^-S^N^->
ro ro csj
CM CM CSJ
o o o
o o o
o a a
z z z
u u u
in O en
«3- in *}•
o o o
a o a
z z z
Ol O rH
csi oo r—
ic Z Z Z
S-* s~^ s~*s~>
en ic CM in CO rH
O >H rH CO O rH
O O O O O O
o o o o o o
0 rH 0 O O
CM <3" CM r^* C-J CM
O O O rH O O
o t- Q o a
Z -M Z Z -Z.
m r-. m r**. CM cri
p*- o CM «tf co ro
CO ro **• rH ^- rH
r** o ro r**» o in
O CM CM CSJ rH O
ro in UD O UD CO
CM CM rH CM CM rH
cn o rH CM ro <&•
*$• in m m m u^
o o o o o o
i i i i i i
CM CM CM CM CM csj
rH i + rH 1 +
i in in i m m
O rH ^- O rH "sf
1 1 1 t 1 1
oooooo
to co to to oo <-o
1 1 1 1 1 1
gggggg
1 1 1 1 1 1
rH rH rH CM CM CSJ
CO CO CO CO CO CO 00
in UD UD^^^ UD
^ ^f ^ ic yo ic ic
>-N^— . /-^ /-^
cn o r^ in rH o
«• CM ro Ol 1C CSJ rH
o o o in o o o
o o o o o o o
aoo i- a
Z Z Z *J Z
, — ts^r~* *-<*
CM rH ro rH in rH O
O O O «3- O O O
O O O O O O O
O O O i- C3
Z Z Z *-> Z
u u u
PO ro O 1C ^3
«• ro 1C ic CM ^J- csj
O O O CO i-H O O
o o o t- a
zzz *> z
oo in ic ro CM CM ro
oo in o cn ro ro m
«!• r-. eo oo CO co co
CO ro o r^ CO co co
CO ID ID fl- 1^- rH 01
i— 1 1C OO CM «9- CM CM
CO rH Cn rH rH 1C C*O
rH CM rH CM CM CM CM
in ic r^. oo cn o CM
o o o o o o o
1 1 1 1 t t t
CM CM CM CM Csl CM CM
CO CO 00 CO CO CO CO
ST + ST + +
i in in i m in in
O rH 1
ooooooo
OO l/> ^ OO CO OO
1 1 1 1 1 1 1
Z ZZZZ Z Z
1 1 1 t 1 1 1
rH rH rH CM CM CM ro
CO 00 CO CO
o I-H o in
m in in UD
^^
^j- tjj p\j
rH i*^. CO CT)
0 0 0 rH
O O O O
s»x
0 i-
Z 4J
^^^
c>n co cn
o in CM m
0 0 0 rH
0000
O t-
z •>->
O «i-
CM csj ic ro
O rH O ro
Z 4->
rH CM 00 ^J-
ro ic cn o
10 r^ co co
CO f» CM CSJ
«- in o r--
•3- ID in «^-
ro o CM rH
CM CM CM CSJ
ro «3- in ID
1C 1C 1C OO
o o o o
1 1 1 1
CM CM CM CM
CO CO CO CO
rH 1 + -f
i in in in
O rH <3- «3-
1 1 t 1
§§§§
OO CO OO OO
lilt
1 1 1 I
rH rH rH CM
90
-------
^•x.
OJ
u
•r-
+j
c
0
u
Ol
CM
01
^~
JS
K
in
>, Ol
• — 4->
re re
c o
^Ht,
Ol
Ol
1 ^
c
o "a
•P a.
re ^
.p
c 01
Ol i—
0 JD
c re
O -P
o o
re
i-
4->
X
a>
4j
f
r~^
( Ol
c o>
>r- *3
4->
re ai
S- 3
.P in
C l/>
Ol 'r-
O -P
c
o
C)
.O
*— \
01
in a.
in •<~'
re
E 73
p— -p
re o
.p 01
o 4->
1— 01
73
•o
•^>
Cv^«
lr~ ^
"~^
,_
.Q 1
u -c
i- •>—
x 3
LLJ
Ol Ol
3
in i
in
•r- -P
-P XI
Ol
•P -i-
01 01
S 3
01
fl i-
re J3
3
l-H C
cc.
S
01
r-
in
O
a. t-
5 01
O JD
U E
3
01 C
§- •
6
S)
COCQCQCOCOCQCOCOCO
cD^'tf'in^J'rocOCDOO
^- ^- ^- 1,0 VD t& CD CD UD
CD Cn CM LT) P1* CD Cn ro CD
OOOOOOOOO
ooooooooo
N,^/ V^ S^X X_ / '«»^\^'
a o o o s- i- a o
/^>> /**s /-^, ^»s /^^/^^
CO f^ fH rH CM CO CM rH rH
OOOOOOOOO
ooooooooo
QOOQI- t-OO
u
i*^s o o o r** cn c^ o
rocncMCM^-O^fCMCM
rHOOOOrHOOO
OOOOI- S-QQ
cn«frcnrHeocn*rr^cn
fOcDCMCncnroocDO
oooooocDoooor-«*oop^
00 00 *> CV, » 0. 10 1C «J-
cDCMcDf^r^fHCMmCM
rHCMrHrHrHCMi—trHrH
ocDocncncor^odr«.'
CMCMCMrHrHCMrHrHrH
f*** co cn, o rH CM ro ^ VD
ooooooooo
1 1 1 1 1 1 1 1 1
ooooooooScooococo
^ ^" ^1
rH I -f rH i + i -f- 4-
i in m i m m m tn m
t i i i i i i i i
OOOOOOOOO
cococolocococococo
1 1 1 1 1 1 1 1 1
1 1 1 1 1 f 1 1 t
00 CO 00 GO
*j- ^ m CD
in in CD CD
rH CO CM
00 CM CM rH
O rH O O
0000
'^f
!- 0
•4-* Z
CD o CM o
O rH O O
o o o o
i- O
•+-> z
r^ o
00 rH LT> CM
rH CM O O
S_rf
t- o
CM CM m CM
r*. PO P-*. oo
r*. co oo f^-
h^ CD m in
rH CD CM CD
CM rH CM rH
oo cn LO r-t
CM rH CM CM
r-. oo o r-i
r^- r*«- oo oo
o o o o
till
CM CM CM CM
00 CO 00 00
^' ^f
rH 1 1 +
i in m tn
O rH rH ^>
1 1 1 1
O 0 0 O
CO CO CO CO
1111
CO CO CO CO
LU UJ LU LU
I 1 1 1
r-t rH CM CM
GO «*• 00 00
^" m ^ *"
in in m CD
Cn rH
r^. ro o rH
cn *& o o
o o o o
*W1»~ /
0 0
z z:
^^v/—N
cn cn
in r^. o o
CD CO O O
O O O O
a a
z z
0 0
CM in CM CM
r^ co o o
S_ ^ s^s
Q a
z z
cor^ com
r*-. CD ^- CD
CD oo cn oo
in r«* CM cn
P^ Cn rH CO
rH CM rH
rH r- *3- cn
r-i CM CM rH
rH CM CM CM
CM ro ^- in
CO 00 00 CO
0000
1 1 > 1
CM CM CM CM
00 CO CO CO
^J- <^-
rH | + i
i m m m
O rH *$• rH
1 1 1 1
o o o o
CO CO CO CO
1 1 1 1
1 1 1 1
rH rH r-t CM
S-
o
M- f—
a'
^ > cu
cy cu 3
0 i— —
_J rO
v^ ID >
c ^ a>
O TO JZ
•r- r-
*J 4->
TO C
-^ a*
•r- W) ^
4-i O) C
C t- TO
TO CL r-
2 JD
cr in
4- O
O *O JT
+-> 3 Q)
•r- O E
•E I" 01
•— o >
U •!-
•D 4J
01 O) l_)
+J -C 0)
re (— a.
E m
.,- 01
4-> • i.
in ai
Ol U Ol
re .c
J= 4-1
>— c
II •!-
i- C
/-» -P 0
z —
\ 4J
ui . re
-^ S-
X O -P
o c
in — i o)
. *— ' u
CsJ C
v_- C 0
o u
Ol ••-
i S 1
re 5 *
l/> Ol 01
01 JD
a. K- o
o
O 01
esj +J .c .
•i- *J 01
0 E 3
•r- C I—
in t— re re
•»- ^1 >
^ 4-1
•a 01 ji
3 re in re
O E Ol i—
O Ul in 01
5 -p
l/l 01
•r- .C 01 O
4T 4J r— +J
•p a.
.in Em
s- r-\ .1- re T:
O Z in c
«*- \ l/l O
(/> Ol 01 Cu
' — ' in jr in
O X 01 -p Ol
O J= 1-
— 1 O •U C i-
^—'f— 1 C •!- O
^-^ 01 U
C S- 01
o a> re 4-> 4J
•^ f>— Cu ^s'^
*-> a. i— E
o E c re -i-
01 re •<- c •—
4J i/) re
01 ^N. Ol C
^3 Ol 3 01 O
a.-— .c -p-
*^- re 4^ 4-1
o o > u
OO .14-01
4-> • O1 O 4->
•i- O . O 01
E TJ -J C 73
•i- Ul 01 O
1— •!- *J T3 T- 01
U C 4-> J=
73 ^3 01 re re 4-^
Ol C 4^ U
4-> 3 01 O 4J I/I
re o 73 o c re
SO. —1 01
•r- E 4-> U 73
4-> O O C C O)
W U C 01 O 4J
01 01 O 1-
m tl 3 O
01 -r- 4j oi a.
•c jc o ai x: ai
K- 4^ Z jO h— t-
re .0 u
91
-------
3
in
^
Q.
E
ro
oo
o>
in
m
JZ
0)
in
O
Q.
•5
**•
OJ
in
o
Q.
E
O
u
CM
00
I
CM
1
00
d
•z.
00
o
ro
JZ
a.
^
4J
=1
.Q
C|
O
1
^
i.
O
O.
ai
ce
ID
ID
O
O
ro
01
J2
ID
1 —
in
£0,
U) IB
C O
Ol
01
i 3.
C
o -o
•w a.
2 r^-
c: a>
u u
ro
t-
X
ai
0)
1 Ol
O """
ro a»
S- 3
4-> in
C
Ol -r-
u 4->
c
o
JD
O)
in rt
l/> s— '
ID
E-0
r— -»J
ro (J
4J OJ
O 4->
r- 01
T3
T3
-Q 1
ID
U J=
!_ ••-
4J O)
X 3
UJ
3
in
4J ^
CD
aj ai
s s
HI
Q. !-
E O)
ID JD
in E
rn C
CC
Z
a>
lf_
in
o
ex t-
e a;
O JD
U E
u
(U C
a.
E
ID
00
CO CO
CM rH
>3- in
s~^
^~M-H
rH 0
0 0
o o
•z. -z.
^— .0
ro rH
rH O
0 0
O O
•z. z
o ^
«• CM
CM O
0 0
Z. 'Z.
rH ro
r- oo
UD r-
ro r-
rH rH
ro O
O3 rH
T—t CM
ro -a-
o o
i i
CM CM
CO 00
•a-
1 4-
in in
i i
oo oo
ii
i i
oo oo co
CM rH CM
«•«•«•
/*»*/—>
en o ro
o o o
o o o
o o s~
'Z.'Z. +1
o en rH
rH O rH
O O O
O O O
§o s~
Z. 4J
o o co
CM CM CM
0 0 O
O O S-
Z. Z. 4->
rH ID CM
in r*. en
m co r^
in CM rH
o en rH
rH rH CM
rH cn r^
en rH ijo
rH CM CM
CM ro «a-
o o o
1 1 1
CM CM CM
CO CO 00
«j-
«»• «fr
rH 1 +
i in in
O rH «*•
1 1 1
o o o
> »
oo oo oo
1 1 1
UJ UJ UJ
z z z
1 1 1
CO CO CO
CM CM CM
^- «J- ^"
^^
rH *-^r~.
O rH rH
O O O
000
•ZZ.TC.
en CM — -
ro CO CM
0 0 rH
O O O
O O O
Z.-Z.-Z.
u
^~*J U
r~ co ID
O rH CM
V^ >*V'*M'
O O O
•Z.Z.-Z
en o rH
CM co r~
ID ID CO
•a- r~ CM
CM «- en
rH rH rH
r— uo o
Cn rH CM
rH CM CM
U3 r^ oo
o o o
t 1 1
CM CM CM
CO CO 00
<4-
rH 1 +
i in in
O rH «•
1 1 1
O O O
oo oo oo
1 1 1
<£ <. *r
•^^ ^o
&-£-£- O
*J 4-1 -4-> 2
m r^ in Is*- CM o^
r^- o CM *3- oo ro
OOrO*rH«-rH
r^* o ro f^ c^ ix^
rH CM rH »H CM rH
O CM CM CM rH O
ro m o o co
CM CM rH CM CM rH
01 o rH CM ro «3-
^- in to to m m
o o o o o o
i i i i i i
CM CM CM CM CM CM
00 CO 00 00 CO CO
*}• «*•
rH 1 + rH | +
i LO in i m tn
O rH <• O rH «a-
1 1 1 1 I I
O O O O O O
LO tO l/l tn tO tO
1 1 I 1 1 1
1 t 1 1 1 1
oocoooooooSS
CM CM CM rH rH rH i— 1
^- ^- ^- UD *O \£> iD
/^-s^-^,"^,
^ *"* ^" rs
o o o r^ » CM
O O O CM CO rH tD
O O O rH O O O
Q O Cl
Z Z Z
u
ro CM Lft en UD
rH r-t o UD r»- *a- *?•
s— •"•••'"•— ^ CM rH
O O O
z z z
ix> m ^ ro CM CM ro
oo LCI co 0*1 ro co u">
oo ro o r*» oo oo co
00 l£> ^D ^h r*. rH Crt
rH rH rH rH CM rH
rH i£) CO CM ^- CM CM
00 rH C7i r-H rH VD PO
rH CM rH CM CM CM CM
LD ir> r^ oo cn o CM
tn LD in tn m co «js
i i i i i i i
CM CM CM CM CM CM CM
00 00 00 CO 00 CO 00
«*• LO tn i/)
i i i i i i i
Z 3= Z Z Z Z Z
LU UJ UJ UJ UJ UU UU
1 1 1 t 1 1 1
S^f ^ *S"
CO CO 00
rH rH rH rH
in m in LD
,~^
ro i£>
1-H O rH O
O O O O
0
z
rH O O
CH rH rH |--
O O rH O
0 0 O 0
Q
Z
O
rH CM *3- 1C
CM O CM rH
0
Z
rH CM CO ^~
ro ir> CTJ o
co r^. CM CM
^- in o r»-
rH rH CM rH
*r & m ^t
rO O CM rH
CM CM CM CM
ro ^- m tx>
^ ^£> ^O IX)
o o o o
I I I 1
CM CM CM CM
CO CO 00 CO
cj.
rH 1 + +
i tn m m
0 rH ^- *}•
i i i i
t-o eo i/) i/>
i i i i
i i i i
rH rH rH CM
92
-------
T>
Ol
3
•r-
C
O
U
o
ro
01
.0
ro
r-
in
in
~%
c o
^•^
D!
\
O)
I 3.
C
O -D
4-> CX
S- i—
C O)
01 r~
U -G
C Q
0 -l->
(-> U
ro
1 1
X
01
4->
Ol
3
1 Ol
C O)
•r— v^
4J
ro 01
S- 3
*-> in
c in
Ol —
u 4->
c
o
ej
JD
O)
i/> 3.
in s^ •
ro
E T>
01
4_> O)
O *->
r— Ol
T3
•D
•r- &3
1 "
U -C
ro O)
4J O>
x 3
LU
Ol O>
in i
•£ +>
cn
4-> •»-
01 01
01
ew
ro JD
3
t— t C
cr
s:
01
r—
O
§- |j
O J3
U S
Ol C
t"~
ro
uo
Q.^.^.^.^.^^.q.^.
oocooocoaooocooooo
to^^kn^rotDiDCO
^ ^^ ^ tO ID VO Id 'O tD
^^ ^v
y*"N^-^/*"», CO ^^ O"^
l-HrHi-HrHOinOOO
OOOOOOrHOO
o a a o o
t**. /—N ^••s ^^
OO /~>O 03 «S- O
OrHOrHO^-f^OO
OOOOOOOOO
o o a a a
z z z z z
u
U O U U '—
O3 CO CO O f*^ CM <"O
rHrOrHCMrHrHrOrHO
o o o a a
z z z z z
crvTj-inrHcoo-n»-f~.in
SSSSSSSSS
CO CO in CM «• C« 10 ID «-
VDCNJlDfOr-'rHCVJlTiCS)
rHCMi— trHrHCslr-lt— t?-H
r-^-Or^mrHO>0«X>
CSIcgc\Jf-trHCMrHrHrH
r^COCT>Of-ICNjrO^J-(£i
OOOOOOOOO
i l l i l l l l l
^ ^" 'Sj"
«-H 1 -f i-H | -f l -f +
1 ITJ LD 1 LO LO LO LO LO
t 1 1 1 f 1 1 1 1
OOOOOOOOO
1 1 1 t 1 1 1 1 1
^C ^Z ^C
11(111111
i— Ir-trHCNJCNjOjrOfO^-
^j. ^. ^. ^
00 00 00 CO
^f- ^- tn ^D
in tn us IP
^*s /"X
un co
r-< r-* O 0
0000
0 0
/— \*— V
OJ CTl
CM ^*- eg o
i-H rH O O
O O O O
^~r*S^>^
Q Q
Z Z
U
t^ O
<*• CO iD CSJ
CO CM O O
^-'Sw/
O O
•z. z
csj CM m csj
p*- ro r*^ GO
r^ oo oo?^.
t"* i^ LO ID
rH O CM l£)
CM i-H CM r-i
r-(CT>r^ rH
CSJ rH CM CM
P-* CO O rH
O 0 O 0
1 1 l 1
csj CM CM CM
00 00 00 CO
^ ^J~
l-H 1 1 +
i ui LO in
0 rH rH «3-
1 1 1 1
O 0 O O
LO eo to
iiit
(-O <^) LO tO
UJ LU UJ UJ
1 1 1 1
i— 1 r-H CM CM
•a- ^t- -«d-
co <• co co
^\o in
\ \ "^^ *N*.
m in m id
/^^,
r**">> rH
CM rH
CM rH ^- O
CM O CsJ O
0 Q
Z Z
s~~\
/-^ en
rH O
tn rH ro o
i-H O CM O
'•M' N»_i'
0 0
z z
U '— •>
^**, cs
m CM
r*. CSJ rH O
s-r-Ln v—
o o
z z
uo r^ to ro
r*»« *}• ^
ID CO Cn CO
m r^. CM en
r^- en rH co
rH CM t-H
rH r^- «tf- cn
rH CM CSJ CM
CM CO
1 1 1 1
to co t-o to
j£ ^ 3 2C
1 1 1 1
rH rH rH CM
i.
4- r-
QJ
r^. > QJ
8" r? =
—i ro
^ ro >
c: •*-> 01
o ro ^
••- h-
4-J •!->
ro c
•4-> 01
4-> 01 C
ro D. r-
3 .n
CT t/)
•r- T3
!•- O
O T3 JZ
C 4^
*-> 3 Ol
•r- 0 E
E Q.
E 01
i— O >
U *>~
•D 4J
Ol O) U
*J J= Ol
« r— D.
E m
•r- 01
JJ . i.
in 01
O) U 01
TO -C
Ol i- i *
f *->
t— c
II "-
S- C
y^ -«-> o
Z -r-
\ *->
oo . ro
^ S.
x a 4->
o c
in — i oi
^** u
CM C
-^ C 0
o o
Ol •!-
i— *J IS
Q. U Ol
E Ol >
ro *-> s.
— *D S
ra .a
3. Ol
0 E 3
tn p — ro ro
•r- .C >
^ *J
T3 01 -^
3 ro t/i ro
O E fll i—
o i/i w ai
3 4J
in 01
•.- j: oi o
4-> D.
• i/i Em
i- <~ST- ro T3
o z in c
u- -v. in o
OO Ol 01 Q.
O X 01 4-1 01
0 -c S-
— ) O 4J c i-
v^rH C -.-0
**^ 01 (J
C S- 01
o oi re 4-* 4->
•r- ^ Q. >,•!-
4-> Q. 1— E
u E c ro ••-
O) ro *r— C r-
4-* in ro
Ol ^s Ol C
•a O) 3 oi o
i*- ro *j 4J
o o > u
oo . *- 01
4-> . O- O 4->
•i- O • O 01
E -a —) c -a
•r- 1/1 01 O
r- M- 4-> T> T- Ol
u c 4-> j:
•o "o oi ro ro *J
0) C 4J !-
*J 3 01 O 4-> in
ro o -D o c ro
E Q. — 1 01
•r- E 4J U "D
-t-> O O C C U
in u c oi o 4->
01 01 O i-
in II 3 o
Ol •>- 4-> 01 Q.
f f a oi x: ai
r- *-> Z a3 r- (.
ro ^ u
93
-------
TO
CO
.—
CX
E
rc
CO
as
3
I/I
CO
£
t/)
O
CX
E
o
CJ
CM
CO
U.
1
o
1
«!}-
00
1
rH
O
Z
CO
o
•^ff
O)
TO
TO
JZ
f:
Q.
r~
£
U
o
C|
o
4->
s_
o
Q.
01
ce
TO
+J
re
a
rH
ro
01
JO
TO
r—
in
in
^*J
TO TO
C O
'3
Ol
I 3.
O T3
•"-> Q.
t- r—
C O)
OJ •—
U XI
C TO
O 4J
U U
TO
S-
X
OJ
a>
I 01
•v.
C 01
•r- .3
TO 0>
i. 3
c in
O> -r-
u •<->
c
o
CJ
.0
"3
in n.
in « — '
TO
E -0
— 4->
4J QJ
O -U
1— 01
•o
."2
•-«
r-s^
.Q 1
TO
o .c:
TO OJ
x 3
UJ
QJ Ol
3
cn i
cn
+J -C
01
OJ ai
3 3
a>
'o. i-
e m
re .a
cn E
3
i— 1 C
cc
s:
at
>p_
in
o
ex s-
E 01
U E
0) C
Q.
E
ro
CO
00 CO
^^
CM r-4
«j" in
in *•""*
rH cn
O CD
o o
• " -
0 0
z z
rH 00
O in
0 0
a o
z z
u
O CM
CM .
• CM
O rH
O O
z z
rH ro
r-- co
VD r*"»
ro f*^
ro o
00 rH
r — rH
O O
I |
PsJ C\)
00 CO
^.
«*
I -f
LT) IT)
r-t ^~
1 t
LO LO
1 I
ii
i-H r-l
CO CO CO
ro 0 ro
CM rH CM
T *f «•
CD ro cn
CD rH O
O O O
O O O
* '
i~ i. O
4-> *J Z
CO rH O
O O O
o o o
S~ i- O
4-> 4J Z
cn ^r o
CD CM CM
O O O
i- i. O
*-> *J Z
rH VD CM
in oo r-
cn CM rH
O Cn rH
rH Cn f^
Cn rH CD
rH CM CM
CM CO «3~
O O O
1 1 1
CM CM CM
oo co co
^.
^ 4~
rH 1 +
i in in
O rH •«•
1 1 1
CO CO CO
1 1 1
CU LU LU
Z Z Z
1 1 1
CO CO CO
^p^in
\ \ ^1
^ ^- ^
<-^CM
ro cn tn
rH O CO
O O O
0 0
z z
^~% CO
CM VD «t
I-H o r~
o o o
o o
z z
u u
CO «•
CM r-l VD
o o
z z
cn o rH
CM co r~
VD VD CO
«3- r» CM
CM «»• cn
r^ CD o
cn i-H CM
rH CM CM
CO r- CO
«3- ^- *}•
o o o
1 1 1
CM CM CM
CO CO CO
^.
^ ^
i-H 1 +
i in in
O rH •*
O O O
> > >
CO CO CO
1 1 1
Z Z Z
in r^ tn r^ CM cn
r-. o CM «»• oo co.
co co *f I-H *r I-H
r>^ o co r^ o tn
O CM CM CM rH O
CO in VD O CD CO
CM CM rH CM CM rH
Cn O rH CM rO *3-
<*• in in in in tn
o o o o o o
t 1 1 1 1 4
CM CM CM CM CM CM
co co co oo oo co
^. ^.
*a" *^ *^ ^^
rH 1 4- i-H i H-
i in in i in in
C5 rH *5J" O rH ^~
1 1 1 1 1 1
0 O O O O O
CO CO CO CO CO CO
1 t 1 1 1 1
rH rH rH CM CM CM
CO CO CO 00 CO CO CO
in CD CD «s- ^r ^- vo
*^ ^ *^ VD VD VD VD
^*, o 1™H ^** CTl VD
co in VD CM *j- o cn
CM O O CM CO O O
o o o o o o o
o o a o o
z z z z z
^^ co cn *—s r^ CM
rH CO *• CD CO O CO
rH O O rH CM O O
0 0 0 0 O 0 0
0000 0
Z Z Z Z Z
u u
*"^ CM 00 ^^ O
O 00 cn co i— i CM cn
CM O O no VD O rH
O O O O O
z z z z z
VD in VD co CM CM co
co in o cn co co in
•3- r^ co CD co co oo
co co o r^- co co co
CO VD vD «1- r- rH cn
rH CD CO CM «J- CM CM
CO rH cn rH rH VD CO
rH CM rH CM CM CM CM
in VD r~ CO cn o CM
in in in in in VD VD
o o o o o o o
i i i i i i i
CM CM CM CM CM CM CM
I- "3-
«J- «*• *)• «}•
rH 1 + rH 1 + +
i in m > in in in
O rH «J" O rH
-------
CO
•S
c
o
u
rH
CO
0>
JD
r-
in
V)
^.s
fO ro
C O
^-N
^
en
i n
c
o -o
*J Q.
(C "r-
S- r—
C QJ
O> r-
U JD
C (D
O +J
O U
(0
S_
+J
X
QJ
CO
1 O)
C Dl
•t- si;
re o>
S- D
4-^ in
0) -r-
O +•>
C
o
CT
in n.
in ^-^
ro
S 13
— 4->
(0 (J
4-» QJ
O 4-=
r- 0)
•o
•o
•r- &•?
,_
JD 1
+J -M
U JT.
S- •!-
4-> 01
x 5
LU
CO D!
3
in i
in
•r- 4->
+-> J=
O)
^ 5
(U
Q. !-
E Q>
fU ^3
in E
r- 1 c
"Xi
z
CO
o
g- S-
5.0
U 6
3
0) C
~*
J
rc
10
^.^.^^.q.^.^.^.^.
cooooooocooocooooo
to^^in^roiDcoco
^-^•^•l0UD»4DtJ3^DVD
»— 1 O rH O rH fO lO i~H C\J
ooooooooo
O O Q O O O S- O
O '•"'* O O CO /"^ ifl tO
OCMO^OOrHOO
OOOOOOOOO
s^/s^ys^ \»^\^. f^^ ^*>
OQQ OOQt-O
U U
o i*^* o o ^ i***» r-1- r^*
csjcOfMcncsjr-N.a>c\jcsi
0«X>Or^OOrHOO
Q Q O O Q O I- Q
cn«-ini-Hrocn«-r-~in
coiDCMcncnrooiDO
cooocotocooor^oor^
oocoincM-a-cniDvo^t-
IDCMWDCOr^rHCMinCM
rHCMi— lT-HrHCMrHrHi— 4
r^^J-OrHinrHCnOtO
oiDOCncniDr^oor^
CMCMCMrHrHCMrHr— IrM
r^- co en o rH c\j ro ^° ID
ooooooooo
i i i i i i i i i
CMCMCMCSJCMCMCMCMCM
CO CO 00 OO CO CO CO 00 00
rH 1 +• rH 1 + 1 + -f
i m in i m in tn in in
ii ii
ooooooooo
i i i i i i i i i
^ ^ *I ^C ^C • in to
in m ID ID
"9- CM CM
cn ro rH T-H
O 1-H O O
O 0 0 0
O O O
Z Z Z
ro rH cn
O rH O O
O O O O
S""' ^^' '
o a o
z z z
-—- 00
O rH CM CM
CM CM O O
0 0 O
Z Z Z
CM CM UO CM
r^. ro r~ 00
r^ oo co r^
r^ to in in
rH tD CM tD
CM rH CM rH
rH Cn r^ rH
co cn m I-H
CM rH CM CM
1^ 00 0 rH
r-^ r*^ oo oo
0000
i i i i
CM CM CM CM
00 CO 00 00
•3- "3-
rH 1 1 +
i in in in
O rH rH «•
1 1 1 1
O O O O
t/> to to to
1 1 1 1
oo to to <^>
UJ LU UJ LU
1 1 1 1
rH i— 1 CM CM
» «• «r
eo «t co co
^l-\0 IT)
to in in to
in •-»
Cn rH CO
in CM o CM
CM O O O
S- 0
*-> z
in /->
VD rH CO
r~ CM O CM
rH O O O
(- 0
*-> Z
U
CO • — v
CO CO <3-
cn in o Q-
^>
i- 0
4-> 'Z.
ID t^ to ro
r~ to -9- ID
ID oo cn oo
tn r^ CM cn
r^ cn rH 00
rH CM rH
i— i r^ «i- cn
rH CM CM 1-H
rH CM CM CM
CM ro «• in
CO 00 CO CO
o o o o
i i i i
CM CM CM CM
CO CO CO CO
"9- «•
rH I 4- i
i in in in
O rH q- rH
§i§§
00 LO CO IO
1 1 1 1
to co to t/>
3333:
i i i i
1-H rH rH CM
i-
i2 ,
QJ
O Q) 3
O r— r-
— J 10
— ' (0 >
C -M CO
O TO JT.
•r- r—
*-> Q>
*-> Q) C
C t- IB
3 JD
CT in
•i- T3
t- 0
o -a j=
C *J
4-> 3 Q)
— 0 E
JS t a,
r- 0 >
U •!-
•o *->
co a> u
*> jr Q)
nj i— o.
E m
— Q)
in a>
ro j:
CO 1— 4-*
II 1-
!- C
/—. 4-> O
Z ••-
to . m
X O *J
o c
m — i o>
• *~- ' U
c-j c
^^ C 0
o o
r— 4-> ^J
Q. U CO
ID *J £
\ *O in
D) JD
a. t- o
o
o o>
CM +-> JT .
•1- -4-J Q)
O E 3
in r— ro ro
•— jz >
•D co .*
3 to in (0
0 E Q) —
Q, *^ »— ^3
E -P
o in cn QJ
S -P
tf) QJ
•i~ JZ QJ O
JC 4-> r— 4->
•P Q.
• (/> E in
t- y^ST- TO TJ
O Z in c
H- \ tfl O
CO QJ QJ O.
•— *. in jz in
O -C i-
— J o -P c i.
s-rH C -r- O
^^ QJ O
C S- QJ
O QJ TO -P 4J
"^3 'a. ^ r^'i
U E C TO •!-
QJ TO •»- C r-
-P in TO
QJ X^ Q) C
TO cn 3 QJ o
o o > u
CO . <*- QJ
•P . O" O -P
•r- O • O QJ
E -D -f C -0
•r- in QJ O
•— •»- -P "D "- QJ
U C -P JZ
"D T3 QJ TO TO -P
QJ C -P t-
•P D QJ O -P VI
TO O "U O C TO
E O. —1 QJ
•»- E -P U -D
•P O O C C QJ
in u c QJ o v
w) || jfc o
QJ *r- 4J Qj Q
JZ JZ O QJ JZ OJ
TO JQ U
95
-------
in
01
E
re
oo
01
in
ui
h-
O)
in
0
o.
T3
in
Q.
0
CO
>-
LL.
1
s-^
r*
i
oo
CO
1
00
O
oo
<
u
•^
Co
+J
re
re
jr.
jz
,_
Nl
C
CO
5-
3
m
i
4-»
O
O.
Ol
a:
re
4->
re
0
CM
co
a>
JD
re
h—
in
in CO
£>£
re -o
c
/•*•.
Ol
\
Ol
1 2.
C
*•> Q.
TO 'r-
4-J
wet Concer
) extractabU
\
O 3.
•M
Concentr;
g)a tissiK
1/1 **•••
re
OJ
re o
•P CO
O 4J
1— Ol
•o
T3
5ff
JD t
-4J *->
U -C
(- -r-
x 1
LJJ
01 Ol
3
in i
Ul
4-> .C
Ol
4-> -1-
22
CO
i-Jr.
Sample composite MR I san
number numb«
co co
-v'-v
•a- «r
CM rH
r~ >a-
CM «•
O O
CM ro
O O
in co
ro r^
rH CO
r^ co
U3 f^
ro r^
CO O
00 r-l
i-H CM
r^ i-H
o o
CM CM
00 CD
«t
*f
1 +
in in
r-l «•
1 1
O O
> >
CO 00
1 1
1 1
r-H rH
CO CO CO
ro o cr>
CM r-l CM
Ol O cn
i— 1 i— 1 O
O O O
O O O
Odd
z z z
O Ol !•»
o o o
o o o
000
z z z
000
CM CM CM
O O O
o o o
z z z
rH ID CM
m r~ cn
in co r*-
IT) CM rH
O CTl rH
rH CJ! T1^
C71 rH ID
rH CM CM
CM ro >s-
O O O
1 t 1
CM CM CM
CO CO 00
*
* *
rH 1 4-
i in in
O rH «!}-
1 1 1
o o o
> > >
l/l OO OO
1 1 1
tu uj uj
z z z
1 1 1
rH rH rH
CO CO CO
«3- r^ in
CM CM CM
ID -a- cn
rH rH CO
O O O
O O O
a o
z z
o CTI r»
o o o
o o o
0 0
z z
0 0
CM CM r~
0 0 rH
o a
z z
CTl 0 rH
CM CO r^
ID ID CO
<»• r~ CM
CM «J- cn
r~- ID o
Cn rH CM
rH CM CM
ID r~ co
o o o
1 1 1
CM CM CM
00 00 00
•*
* > >
00 OO OO
1 1 1
O rH CM rO T}-
O O O O O O
1 1 1 1 1 1
CM CM CM CM CM >>>>>
CO OO OO OO OO OO
1 1 1 1 1 1
< < +J
o cn CM in CM
o o o o r- CM o
o o o o o o o
0 i- i.
Z 4-> 4J
O fl" CM
rH CM CM ro O h*
rH O O O rH r^ rH
O S- S-
Z *> -P
CD in ID ro CM CM ro
co in o cr> ro ro in
q- r~ oo CD oo oo co
00 ro O t-- 00 00 00
00 02 03 «- p- rH O>
rH ID CO CM >3- CM CM
00 rH cn rH rH CO rO
rH CM i-H CM CM CM CM
in CD r~ oo cn o CM
O O O 0 O O O
1 1 1 1 1 1 1
CM CM CM CM CM CM CM
co co co co oo oo oo
>>>>>>
CO OO OO OO CO OO OO
1 1 1 1 1 1 1
z z z z z z z
LLJ UJ LLJ LLI LLJ ' ' ' ' ' '
1 1 1 1 1 1 1
rH rH rH CM CM CM ro
co co oo co
O rH O in
i-H rH rH rH
O CM ro LO
CM rH ro CM
O O O O
CM
rH O CM CM
O O O O
O cn ID ro
ro rH ID ^~
rH CM 00 "*•
ro co cn o
CO r~ CO CO
CO r-v CM CM
«!- in O r^
•3- ID in **•
ro O CM rH
CM CM CM CM
ro «j- in co
O O O O
i i i i
CM CM CM CM
oo oo GO oo
«J-
1 1-
rH 1 -r -r
i in in in
O rH «3- «•
lilt
0 O O O
> > > >
OO OO 00 OO
1 1 1 1
1 1 1 1
rH rH rH CM
96
-------
/— -V
^2
O)
3
C
4->
C
o
u
CM
ro
o>
J3
t—
in
tn OJ
f^lo
n TJ
D.
re ••-
4_> '
C O)
O» i—
U JO
c re
0 -P
o o
re
E.
X
01
4J
0)
3
I Ol
C Ol
0 3.
'•£ ^^
re o>
j-> in
C in
U *>
C
o
^•^
O)
W 3-
1/1 ^— •
re
o>
re u
0 ->->
h- 0)
•o
-t-,
o.^^
• •— ^5
,__
JD I
^j 4J
U JC
i- "-
4-= 0
X 3
UJ
0) 01
D
in i
in
*J .c
Ol
*J •--
O> 01
3 a
01
D. !-
re jo
en E
3
i— c C
O£
s:
Ol
^
o
O. 1-
E o>
O JO
u E
3
0) C
'o.
E
v/i
cooococooococococo
vo^^in^c^vD^OO
CMCMCMrHi— 4 i— Hi— IrHi— H
^* ^" ^* ID ID ' ri VD VD ID
^^^
ooorocsjoooo
ooooooooo
i- S- 5- O
J-> <-> -U Z
^^
oo VD o en m I-H I-H
OOOCMrHOOOO
ooooooooo
^"^
S- !- S- 0
oo oo o o
in O VD C\J ID CvJ CM CM
C3 Cvl i—4 ^^ ro i-H O O O
s^
S- i. t. O
•U *J *> Z
CTH3-in^HrOO-l«T^in
rotDCMCncnroovDO
COCOCOtDCOOOf^-COP^
OOOOincM«3-cnuDiD«S-
IDCMlDCOr^r-fCSJinCSl
r~-»rOrHini-HcnovD
oiDocndiDr^cor^
CM CM CM rH T— 4 CM rH r~4 i~4
r^OOOlO^HCMfO«3-lD
OOOOOOOOO
1 1 1 1 1 1 1 1 1
CMCMCMCMCMCMCMCMCM
COODCOCOOOCOCOODCO
«t «3- «»•
^f- ^- ^J- 1^ ^f
1-H 1 + 1-H 1 + 1 + +
i m in i in in in in in
OrH^-Oi—i^'t-H^'^-
1 1 1 1 1 1 1 1 1
1 1 1 1 1 1 1 1 1
t/1 t/1 I/} l/l IS) I/) l/l VI (^1
1 1 1 1 1 1 1 1 1
** ^- *3" ^3"
oo co co co
«j- "a- m VD
1-4 rH iH i-H
in in VD VD
/•^.."N
cn CM
in f-^ o I-H
ro in o o
O o o o
0 0
z z
I"— \.*^
oo on
r^ r~ o o
CM «• o o
o o o o
**-"•—'
a o
z z
o o
VD ^- CM CM
r> en o O
*- -•*_ -
0 0
z z
CM esj tn CM
r*^ *^ i^^ oo
r-. co oo r*-
r*- VD in LT>
rH i»D CM 1C
CM rH CM rH
rH Cn r- rH
co cn in rH
CM rH CM CM
r-. CO O rH
0000
till
CM CM CM CM
COCO CO CO
^" ^f
T-H 1 I 4-
i in m in
O rH rH ^J-
o o o o
lilt
UJ LU UJ UJ
till
rH rH CM CM
«fr «S- ^J-
CO ^ 00 00
^- ^v. o m
rH Cn rH rH
in in in
rH
rH CO
f^ O r*. rH
rH O rH O
CM
Cn rH
CM O UD rH
rH O rH O
rH «sj-
PO • in •
VD P*- VD CO
i***- ID ^* *&
to oo cn oo
in r-- CM cn
r^ cn rH co
rH CM rH
rH r^- <<}• cn
rH CM CM rH
rH CM CM CM
CM ro ^ in
CO 00 00 00
o o o o
1 1 1 1
CM CM CM CM
00 00 CO 00
^" ^f
rH 1 + i
i in in in
0 rH ^J- rH
1 1 I I
O 0 0 O
> > > >
l/> LO L/) t/1
3^ 3^ 3 jS
1 1 1 1
rH rH rH CM
0)
CL
E
n
in
\
D)
3.
O
CO
0
t/J
o-
o
t
o
4->
re
4->
4->
c
re
cr
iw
o
^
e
1 —
•o
ai
re
E
4J"
in
a>
Ol
jz.
^
^^
z
~>«
v/1
X
in
CM
^*-^
Ol
CL
Ul
~s>
3.
O
CM
0
l/l
>^>
r~\
O
^-^
c
o
u
ai
+j
QJ
ID
M—
O
.^f
.E
r^
•o
01
4-> .
re <->
E Z
"-V.
vn
0) X
ai o
J= i-H
re J,
p—
Ol
>
Ol
TO
4-J
re
c
a>
in
Ol
s.
r*i
•o
C
3
O
t
O
u
Ol
JZ
1—
cj
u
re
s_
4_>
II
1-
+J
O
0
>*^
c
o
(J
Ol
jp
o>
TD
vt-
o
*J
E
r—
"^5
Of
ft!
E
-13
V)
3
UJ
>
O
OJ
^_j T-,
U C
a> m
OJ Q
^ o
w rj
•+->
o c
C O)
II 1
4->
a ai
97
-------
0
CD
r>
E
10
OO
o
ex
01
4J
m
o
ro
ro
Ol
ns
h-
1/1
in o>
r- (0
(0 TD
C
•s
"5
01
1 3.
C
O "D
•<-> Q.
re *^~
•p
C CD
4) r—
U -0
c nj
O 4->
o u
<0
^_)
X
01
CD
a^
1 Ol
c o>
O Z2.
IO QJ
L. 3
4-> I/)
C 1/1
a; •!-
o *>
c
0
.0
Ol
1/1 a.
in v—'
E -0
O)
(O O
•4-1 a>
o •<->
r- Ol
•O
•o
Q./—.
^aj 01
J2 1
U -C
S_ T-
X S
UJ
ai 01
in i
in
•P JZ
Cn
ai
a. s-
E QJ
re -Q
in E
H- 1 C
cc
s
01
£
o
a. s-
E ai
O JD
U E
3
01 C
CL
E
re
oo
«»• * *r
00 00 CO
en en o
rH rH rH
«3- Tl- m
f^Xf-r^/-1^
1C in rH
0 0 O
O O O
^^^^S»>'
000
z z z
CM rH O
CNJ rH rH
O O O
O O O
O O O
Z Z Z
/-~\^"> <•->
O O 0
CNJ CM CM
O O O
S*x^*-'S1r/
000
ro rH ro
CM «• -a-
ID t^ O3
1C 1C P^
in ro f^
O ro o
Cyi 00 rH
rH CM
1C I-- rH
ro ro ^J~
O O O
i i i
CM CM CM
CO 00 CO
«•
rH I +
r in in
O rH Tt
i i i
oo oo oo
i i i
iii
i i i
*f «3- *•
00 CO 00
ID in UD
*^^
.**. ^*\
en rH 1C
rH rO rH
O O O
O O O
*~s ^^
O i- O
Z *J Z
o r~ o
rH CM rH
000
O O O
0 W 0
Z -U Z
r~* s~*
000
CNJ ID CM
O O O
N-^ V-'
0 i- 0
Z 4-> Z
rH 1C CM
in r»- en
in oo r~
in CM rH
O Cn rH
rH en r^.
en rH tx>
rH CM CM
CM ro «S-
w «• <»•
o o o
1 1 1
CM CM CM
oo co oo
*
rH { +
i in in
i i i
°°§
t/) l/> (/>
t 1 1
UJ UJ UJ
z z z
1 1 1
00 00
01 en
r-H rH
»*
^^
LD O
O O
00
SM/
O t-
z •>->
r~ o
O rH
O O
o o
0 i-
Z 4->
^^,
o
CM O
• CM
O •
N-^ O
o s-
z •<->
en rH
CM f^.
CD CO
"»• CM
CM en
r^ o
en CM
rH CM
vO CO
0 0
I 1
CM CM
CO CO
rH +
i in
i i
o o
OO OO
i i
0. Q-
I t
rH rH
to oo «s- oo oo co
tc m \ CM CM CNJ
rH rH rH rH rH rH
•a- fl- ic ic vc ic
ff^ ^-^ ff^ ^^
rH O in CM rH Cn
0 O 0 0 0 0
O 00 0 0 0
*M* **^^~* *^S
o o o o s- t-
Z Z Z Z 4J *J
en oo CNJ o co vo
0 O 0 0 0 0
0 0 0 0 0 O
0000 i- S-
Z Z Z Z i-> *J
^^/^^/^N/^N
o o o o CM en
CM CM CM CM CM CSJ
0 0 0 O O 0
^-/ V*-/ N»X Vrf*
O O O O i- t-
Z Z Z Z 4-> •!->
in r*»- in r*»- CM en
r- o CM ^- oo ro
r*- CO oo co f^^ co
CO ro «}• rH Tj- rH
r** o ro r*^ CD in
O CM CM CM rH O
ro in ID o ID CO
CM CM rH CM CM rH
-
en o rH CNJ ro ^j-
Sin in in in m
o o o o o
t i i t i i
CM CM CNJ CM CM CM
oo co oo oo oo oo
*i- -a-
rH 1 + rH 1 +
i LO in p in LO
»»»
i i i i i i
rH rH rH CM CM CM
S S S «j- * «• * ^
CT> O O "X. \ \ ^v "V.
T-HCSJCMLOLn^J-U^iO
^^^^volo^^
,—, /— M^-N S~\ S~+,
roro<*D«d-?HLnojo
oooooooo
oooooooo
\^t ^^ \^s \^ \^
OS-(-OOS-OCl
Z +J 4-* iZl Z *J Z Z
r-HOrOO^O'iCMOO^
rHrHrHOOrHi-HO
oooooooo
oooooooo
O S- i- Q O S- O Q
Z -M •*-* ^E Z *^ Z Z
S"*> ^-X/^S r^N/— S
OrHtnOOCMOO
csjcsjesjcsJCsirocMCM
oooooooo
^.^ '**''**' ^-^^^
o i- t- o o s-oo
Z 4-1 +^ Z Z 4*^ "Z> Z
IDLDUOroCMCsJCSJfO
oomocnmromm
ooroor-coooooco
cotx>v£»^r^THi£>ai
f— IVDOOCM^S-CSJCMCM
OOr-HCDrHrHVDOn
f-HCSJr-HCMCMCNJCMCsJ
invDrvCOC^iOrHCSt
oooooooo
1 1 1 1 1 t I 1
CMCMCSICMCMOsjesJCM
cocooooocooooooo
^- ^ <•
rH t + TH 1 4- I +
i in un i in m m ID
i t i t i i i i
t/)C/)l/>l/)V7l/)t^>ttO
1 1 t 1 t 1 1 |
zzzzzzzz
^j,i u i 1 1 1 yj uj u i uj m
1 f I f I 1 I 1
i-ir-irHeMcvjcsjnorn
^.^.^.^
\ ^ 'V, "\
h*> -^ r** in
tn if) tn VD
/™N /*^>
^3- CO Lft CSJ
0000
0000
^^ ^^
i- O i- O
-P Z J-> Z
co o ro en
O rH rH O
O O O O
o o o o
i- O S- O
*J Z *> Z
^*t /~s
o o o o
CM CNI CO CM
0 0 O O
*~r **-*
s- o u a
•P Z -P Z
rH CM 00 T
ro 10 en o
vo r» co co
CO f^ CM CM
«t in o r-
^- vo in «*•
ro O CM rH
CM CM CM CM
ro w in ID
1C UD 1C 1C
0000
1 1 t I
CNJ CM CM CM
oo oo oo oo
•ej-
rH 1 + +
i in in tn
0 r-l«3- t
1 1 1 1
§§§§
LO t/) CO LO
1 1 1 1
ilii
i i i i
—4 ,—1 —| CSI
98
-------
•o
01
3
C
4J
C
o
u
ro
co
Ol
XI
h-
in
i/> 01
r— ro
ro TJ
^
Ol
CTl
i 3.
_ ^" '
O "CT
•p'a
i. r^
40
a> i2
U XI
c ro
o *->
u u
ro
S-
4->
X
•s
f "S
C CTl
O 2.
ro 01
S- 3
•p in
5 •!-
U
U JC
i. •!-
X S
UJ
01 CTl
3
in i
in
•r- 4-J
•P J=
CTl
fl) Q)
3 S
01
CL S-
ro S
in E
3
>-i C.
CL
Z:
01
^
in
O
a. (-
E ai
O XI
U E
3
01 C
i.
TO
./)
SSrrgSg cog&
rHCMininrHLnrHlJDrH
tf> ^ ^D IQ ^D dD dD ^& ^C
/^i /--^ ,«**s .-^
ro O"* cr> ^H HH ro vc to y3
yD ^3 Z40*JZZ
OOOrHO^-t-HOO
i— IOOOOOOOO
Z 4-* *J Z *J «P Z ^
oi«s-ir>r-(rOTj-r^oin
roixicMCncnoixiCMO
oococoiocof^coi^r-
COCOinCM
ooooooooo
1 1 1 1 1 1 1 1 1
CMCMCMCMCMCMCMCMCSJ
oooooocooocooooooo
^j- ^^ ^ ^
iH 1 + rH 1 1 4. 1 +
i m in i in tn in in in
i i i i i i i i i
CO C? O O O C2 C3 C^ O
OO oo OO to OO (/> OO OO OO
1 1 1 1 1 1 1 1 1
1 1 1 1 1 1 1 1 1
rHrHfHCMCMrOrO^-^-
W CO CO «J"
-^ O O \
rH rH rH ID
iX" in in in
/^-s /*^
en in *-t CM
O r-t rH CM
O O O O
O O O O
o t- o s-
Z 4-> Z 4J
P«a- o
O rH rH 1^
O O O rH
O 0 0 O
01-01-
Z *J Z -P
o r~. o ID
CM CM CM CO
O O O O
O i. O S-
Z 4-> Z *J
CM CM * CM
r~ ro CO CO
r~ co oo r^
r- 10 ro in
rH l^ 00 l£l
CM rH rH rH
(^ cn r^* 7*4
00 en O i-H
CM rH CM CM
^» CO en rH
o o o o
1 1 1 1
CM CM CM CM
00 00 03 CO
«(J-
•3- *-> Z Z
r- CM o o
CM in CM CM
o o o o
<- S- O Cl
•P *-> Z Z
vn PV m co
r- 10 «t 10
in co cn co
in r^ CM cn
p~. cn ^H co
rH CM rH
rH r^ ^S- Cn
rH CM CM rH
rH CM CM CM
CM ro ^r in
co co co oo
o o o o
i i i i
CM CM CM CM
00 CO CO CO
^ *3t*
rH 1 + 1
i in in in
0 '-If r-t
I I I I
0 O O O
> i- > >
OO OO 00 OO
1 1 1 1
1 1 1 1
rH rH rH CM
i.
O
OJ
O* 01
O i—
i
C 4->
o ro
lp 4-1
ro c
•P 01
•r- in
4-> 01
c t_
ro a.
3
CT in
u—
c
4-> 3
•r— O
E CL
••- E
r— O
U
•o
01 01
+j x:
in ai
01 U
ro
O) ^
-C 4->
II
!-
Z
00
x o
o
m —i
• s^
CM
O
01 •!-
r^~ 1 '
O. U
E ai
ro 4->
in ai
~^ T3
CT)
3. «-
0
O
CM 4-1
0 E
in i —
•i-
TJ Ol
3 ro
0 E
e -p
o in
•2 X-
5 **
S- J^>»f-
o ^
s- -~v in
00 Ol
o x:
-J 0 -P
^^ 01
c s-
o 01 ro
•r— r— O
•P CL
u e c
01 ro T-
4J in
01 "*•*. OJ
T3 CTl 3
M- ro
O O >
00
•P • 0-
•i-O -0
e -u _i
•r- in Ol
*~ O C
•a TJ 01 ro
Ol C 4->
4J 3 OJ O
ro o -o o
ED. —1
•i- E -P
-P O O C
in u C OJ
ai o>
m M 3
r— *-> Z XI
ro xi
99
-------
10
01
i
(O
o>
in
in
r-
Ol
in
o
Q.
01
'v>
o
0
CM
CO
1
So
1
rH
o
i
in
oo
o
z
OO
>*>
i— TO
IO T5
C
O!
cn
0 T3
•P D.
m -r-
C Ol
U J2
C (0
O -4-1
u u
(0
s-
X
Ol
4_>
Ol
C D!
o a.
*J *~^
i_ 3
•*-> in
c: in
OJ ••-
u -4->
c
o
.a
in n
in *-*
£ -0
OJ
1 — •*->
ro u
•<-> OJ
O 4J
r- OJ
•o
•o
•£•£«
s •
TO
-*-> -(J
U -C
t. *»-
X ?
UJ
C) Ol
in i
in
•^ -C
D>
ai ai
oj
'o. s-
E CU
TO XI
m £
r-H C
a:
2:
a>
*t^
in
o
CL S-
O -Q
U E
QJ C
1
10
00 00 OO
cn en o
rH rH rH
*J- *>• LO
in in rH
ooo
000
000
CM rH 0
CM rH rH
000
OOO
o a o
z z z
ooo
CM CM CM
000
ooo
ro rH ro
CM -a- rf
to r— oo
ID CD r^
LO ro r~-
rH I
O ro o
en oo rH
r-t CM
LD r^ rH
ro PO ^
000
t 1 1
CNJ CSJ CM
CO 00 CO
^
rH I 4-
1 LD tO
O rH ^~
1 1 1
00 00 00
1 1 1
iii
rH rH rH
S<3-
00
\ LO ID
ID rH rH
n- «»• *•
cn o cn
ooo
ooo
o o a
o cn r^
rH O O
ooo
ooo
ooo
z z z
ooo
CM CM CM
OOO
000
z z z
rH VD CM
LO ^ cn
in oo r-~
in CM rH
0 Cn rH
rH rH CM
rH Cn r~
Cn rH ID
rH CM CM
CM ro ^3-
OOO
1 1 1
CM CM CM
00 CO 00
•3-
rH 1 +
< in in
O rH «J-
1 t 1
OOO
OO OO 00
1 1 1
LU LU LU
Z Z Z
1 1 1
i-H rH rH
oo oo
rH rH
«•<•
LO O
O O
o o
o a
z z
o en
rH O
o o
o o
o o
z z
o o
CM CM
O O
0 0
Z Z
Cn rH
CM r-
ID OO
«r CM
CM cn
rH rH
r-. o
cn CM
rH CM
ID 00
O O
1 1
CM CM
00 CO
rH +
i in
o «*•
> i
o o
00 00
i i
Q_ Q-
1 1
rH rH
ZZZZ
OOO«3-OOOO
CMCMCMrOCMCMCMCM
OOOOOOOO
ooo t-aooo
ZZZ-PZZZZ
COLOCOroCMCMCMrO
COinocnrororoin
•3-f^cocooocoooflo
ooroor-oooooooo
OOCDCOfr^rHCOCn
rH rH i—t rH CM rH rH
rHCOOOCM«3-CMCMCM
OOrHCnrHrHCOOrO
rHCMrHCMCMCMCMCM
LOCOr^COCnOrHCM
OOOOOOOO
1 1 1 1 1 1 1 1
CMCMCMCMCMCMCMCM
oococooocooooooo
•3- -3- «S-
rH 1 -f rH 1 -r 1 -f
< in in i in LO in in
O rH ^ O rH ^~ rH ^
1 1 1 1 1 1 1 1
cooooooocooooooo
1 1 1 1 1 1 1 (
LU LU LU LU LU LU LU LU
1 1 1 1 I 1 1 1
rHrHrHCMCMCMrOro
oo oo oo oo
r^* «d~ rv in
LO LO LO CO
»»• ro o CM
O O O O
O 0 0 0
§o a o
z z z
cn o cn cn
O rH O O
0 0 O 0
0 0 0 O
a o a o
z z z z
OO 0 O
CM CM CM CM
0000
o o o o
z z z z
rH CM OO *f
ro CD cn o
CD r- 00 00
00 r^ CM CM
•3- to o rv
rH rH CSJ rH
^l- CO LO "fl-
CO O CM rH
CM CM CM CM
ro ^- LO ID
CD CD CO CD
o o o o
CM CM CM CM
CO CO CO CO
q.
•a- ^
rH 1 -r H-
i in in LO
O rH *}• ^~
1 I 1 I
O O O O
OO OO CO OO
1 1 1 1
ilii
1 1 t 1
rH i— 1 r-t CM
100
-------
-Q
GJ
c
c
o
(J
^— '
^-
m
QJ
.Q
t—
in
i/j cjj
fO T3
C
<:
,-_N
en
CT
l 3.
C
o -o
•P D.
i_ r—
-P
C QJ
0) i—
U J2
c re
0 -P
o u
CD
S-
X
a-1
a>
* ^->,
\
O ZL
-P
TO QJ
5- U
J— > in
C VI
QJ *r-
(J -P
C
o
_o
/—**
CT
in s^
E "D
OJ
re u
0 -P
•0
•o
•r- ^?
QJ CT
.O i
•P -P
u JT
s- •--
x 5
UJ
QJ CT
i/i t
'.P jc
CT
a> a;
3 S
QJ
Q- S-
TO ^
in E
*— ' C
OJ
o
CL S.
E OJ
0 .Q
U E
a> c
O.
E
rD
t-O
ooobcS^-co^-ao^co
^-K V^V^-S^-S ^-^^-,,-^S
csjuncsiLnr-HicmLn^D
ooooooooo
ooooooooo
O S-QOO I-OOO
OCMOOOi— It— li— lf-4
ooooooooo
ooooooooo
Q S-OQQ t-QOO
OCMOOOOOOO
ooooooooo
O £-OOO S-OOO
aitnLnrHm^-r-.OLn
f^CSJCNJO^O^OUDCMO
cococo^cor-oor*.r-
cooomcsj-o-^^r-*^-
^tMi£>O^f**-OOCOr*-
CSJ C\l CsJ r— t rH rH r*H rH rH
r^-COCnOrHm^-LDtD
ooooooooo
1 1 1 1 1 t 1 1 1
CNJCNJCMCSICSJCNJCSJOOCSJ
CO CO CO CO CO CO CO CO CO
rH 1 + r-t 1 1 + t +
1 LO LD 1 LD LO Lfl LTJ LO
1 t 1 1 t 1 t I 1
ooooooooo
t/> tX> (^ t/> LO t/) CO CO CO
:> i i i i i i I
I/) tO i/> ^/) t-O ^/l t/) V) l/l
1 1 1 1 1 1 1 1 1
rHrHr-tCNJCSjrOrO^^"
^J- CO CO •»•
CO \\ CO
-^ o o \
rH rH rH lp
^^ ^^
cr> csj r-v c\i
o o o o
o o o o
S- Q S- O
4-> Z 4J Z
r^- o LO en
o o o o
o o o o
s- a i- o
•*-> Z *J Z
O O rH O
csj CM ro csj
O O O O
L- O C- O
-M Z -P Z
CSJ C\J ^- CSJ
[*•* m CO CO
r*^ co co r**-
r^. to ro LO
rH tD CO tD
rH CTi r- rH
CO cn O -H
CSJ rH CSJ CSt
r*- co cn rH
o o o o
1 1 1 1
csi esj csj csj
CO CO CO CO
rH I + +
1 tTJ ID LD
O rH «3- Q-
1 1 1 1
o o o o
to to to <-o
1 1 1 1
to co to co
UJ UJ UJ LU
! 1 1 1
rH rH rH CSJ
SCO ^3- CO
-v. CO >v
CO rH P*- rH
LO IT) LO tD
-— >/— >^-s-— s
tO O O"l rH
O O O O
O O O O
§0. o o
Z Z Z
CO CTt Cn CT)
o o o o
o o o o
r~*i Q r~i Q
Z Z Z Z
o o o o
CSJ CSJ CSJ CSJ
o o o o
O O O Q
Z Z Z Z
to f*«. to ro
r*« to ^ to
to co cn co
in r-- csj cn
r*-. cn I-H co
rH f"^. «^- CTi
rH CSJ CSJ rH
rH CSJ CSJ CSJ
CSJ <*O ^" Lf"J
CO CO CO CO
o o o o
1 1 1 1
CSJ CSJ CSJ xc
ro t—
E
•p
l/l Ol
Ol U
0) 1-
1 —
II
, t_
Z
CO
x a
0
in — i
N*-'
CM
* — • C
O
OJ —
D. O
E 01
ro -P
l/> Ol
\ TD
cn
3. ro
0 E
E -P
O Wl
u
I ^
O Z
CO Ol
^ t/1
Q _£-
_JO 4J
^-- rH C
^- OJ
C S-
O 01 ro
— r— O.
P O.
0 E C
flj ro -p-
T3 Ol 3
*^ ro
O O >
CO
•P • O-
•r- O • O
E -0 _J
•r- Ul 01
I r- .p "D
0 C
T3 T3 Ol ro
01 c -p
-p 3 01 O
ro o T3 O
so. —i
"- S 4J
-P O O C
in u c 01
OJ Ol
l^ II *
(U -r- *J
-c jz Q ai
t— V Z J2
ro x:
101
-------
Table 35. Compounds Not Detected in the FY82 Composite Specimens
Estimated detection
level (|jg/g)
Analytes for 20-g sample
Organochlorine pesticides
o,p_'-DDT 0.010
o,p_'-DDE 0.010
£,p_'-DDD 0.010
o,p_'-DDD 0.010
a-BHC 0.010
6-BHC 0.010
Aldrin 0.010
Heptachlor 0.010
Endrin 0.050
y-Chlordane 0.010
Polychlorinated biphenyls, PCBs
Monochlorobiphenyl 0.010
Dichlorobiphenyl 0.010
Chlorobenzenes
Trichlorobenzene (1,2,3-; 1,3,5-) 0.010
Tetrachlorobenzene (1,2,3,4-; 1,2,3,5-; 1,2,4,5-) 0.010
Pentachlorobenzene 0.010
Phthalate esters
Dimethyl phthalate 0.010
Phosphate triesters
tris-(Dich1oropropy1)phosphate ester 0.050
Tributoxyethyl phosphate ester 0.050
Polynuclear aromatic hydrocarbons, PAH
Acenaphthylene 0.010
Acenaphthene 0.010
Fluorene 0.010
Fluoranthene 0.010
Chrysene 0.010
102
-------
Table 35 (continued)
Estimated detection
level (|jg/g)
Analytes for 20-g sample
Polybrominated biphenyls, PBBs
Bromobiphenyl 0.010
Dibromobiphenyl 0.010
Tribromobiphenyl 0.025
Tetrabromobiphenyl 0.050
Pentabromobiphenyl 0.050
Hexabromobiphenyl 0.100
Polychlorinated diphenyl ethers, PCDEs
Chlorodiphenyl ether 0.010
Pentachlorodiphenyl ether 0.050
Decachlorodiphenyl ether 0.100
Polychlorinated terphenyls, PCTs
Chloroterphenyl 0.010
Dichloroterphenyl 0.010
Trichloroterphenyl 0.025
Chlorophenols
Dichlorophenol 0.010
Trichlorophenol 0.025
Pentachlorophenol 0.050
The estimated detection limits for polychlorinated compounds represent
response from a single isomer rather than the entire homolog.
103
-------
As indicated earlier in this section, mass spectra of the com-
ponents in the sample extracts were compared to the NBS mass spectral library.
This approach yielded the identification of biogenic materials, particularly
fatty acids and cholesterol related compounds, although many of the peaks re-
main unidentified. The importance of characterizing these unidentified peaks
is recognized to be necessary in achieving the goals of the broad scan analy-
sis program. The effort to assign identifications to these data points is
currently being addressed under a separate work assignment for OTS (Contract
68-02-4252, Work Assignment 23).
2. HRGC/ECD Analysis
The sample extracts analyzed by HRGC/MS were also screened by HRGC/
ECD. Figures 17 and 18 provide comparison of the HRGC/ECD and HRGC/MS re-
sponses of the 6% and 15/50% Florisil fraction extracts of a specific compos-
ite. It should be noted that the HRGC/ECD analysis required that the extracts
be diluted by a factor of 10 before analysis. The HRGC/ECD screen was com-
pleted using the same HRGC separation parameters (column dimension, tempera-
ture program, etc.) as were used to achieve the HRGC/MS analysis'.
Figures 19 and 20 provide examples of the HRGC/ECD analysis of the
6% and 15/50% Florisil column extracts from three age groups within a specific
census division. The chromatograms for the 6% fraction Florisil fraction dem-
onstrate response corresponding to the internal standards (dichloro- and octa-
chloronaphthalene) the surrogate compounds, organochlorine pesticides, and PCBs.
Figures 21 to 23 are provided as a matter of reference to determine the elu-
tion characteristics of specific compounds and compound classes with respect
to the response noted for the 6% Florisil fraction.
Much of the response noted for the HRGC/ECD chromatogram in the
range of 0 to 15 min for the 15/50% Florisil fraction is attributed to back-
ground from solvents. Figure 24 is an example of the HRGC/ECD response noted
for the 6% and 15/50% Florisil fractions of a method blank. It should be
noted that the response from the 6% Florisil fraction corresponds with the
elution of the surrogates and internal standards.
The HRGC/ECD chromatograms are useful for determining whether addi-
tional compounds of interest may have been overlooked in the HRGC/MS inter-
pretation. As an example, a review of the 15/50% Florisil fractions analyzed
by HRGC/ECD indicated that dieldrin is present in practically all of the FY82
NHATS composites based on the response at a specific retention time relative
to the two internal standards. The increased number of positives detected by
HRGC/ECD as compared to the HRGC/MS analysis of the same extracts is due to
the differences in method sensitivity. An increased number of positive re-
sponses by HRGC/MS for dieldrin and the other chlorinated pesticides would be
expected if the data acquisition parameters were changed from full scan to a
SIM technique or other mass spectrometry techniques such as negative chemical
ionization (NCI) or mass spectrometry/mass spectrometry (MS/MS). The selec-
tion of HRGC/MS-SIM, however, would restrict the broad scan analysis approach.
A possible approach for future NHATS monitoring programs might combine the
HRGC/ECD analysis to provide identification and quantisation of specific or-
ganochlorine pesticides, chlorobenzenes, and PCB isomers and HRGC/MS-SIM or
to generate data on specific target analytes or compound classes.
104
-------
IM.t-1
T
U3C
479
1-ES-SVO-45+
HRGC/MS
2M
41 2i
9i4»
CM
111 It
8M 1M 12M t4M
17i2t
1SN
341 <•
SOW
nre
1000
J \.
uy
1-ES-SVO-45+
HRGC/ECD
15
25
35
Figure 17. HRGC/MS and HRGC/ECD chromatograms of the 6% diethyl ether
Florisil fraction of the 45-plus age category of the East South Central
census division.
105
-------
IM.*-,
RIC.
129
24MB8.
1498
1295
173
1-ES-SVO-45+
HRGC/MS
2*8
4i M
12M
2(iM
14M
38l28
SC«H
Tilt
{000
JWJUuuJLi
1-ES-SVO-45+
HRGC/ECD
15
20
25
35
Figure 18. HRGC/MS and HRGC/ECD chromatograms of the 15/50% diethyl
ether Florisil fraction of the 45-plus age category of the East
South Central census division.
106
-------
-ES-SVO-0-1
-ES-SVO-15-44
_JviA-U
1-ES-SVO-45+
LJJ
Figure 19. HRGC/ECD chromatogram from the analysis of the 6% diethyl
ether Florisil fraction of the three age group composites from the
East South Central (ES) census division.
107
-------
l-ES-SVO-0-14
l-ES-SVO-15-44
1-ES-SVQ-45+
Figure 20. HRGC/ECD chromatogram from the analysis of the 15/50% diethyl
ether Florisil fraction of the three age group composites from the
East South Central (ES) census division.
108
-------
innn ,
15 20 25 30
1000,
1. l3C6-l,2.O-l.rrochlorab«ni.n.
2. DIchloronaphlhol.n. . 15(1)
3. l3C6-h.Mochlorob.n2.n«
/
4. I3ci2-l.trachloroblph.nxl
5. l3C|2-octachloroblph«nyl ,
6. OclachloronaphlhaUn., IS(2)
7. l3C|2-d.cochlo(oblph.nxl
2
IS(
i
\l i L. 1 .1.1- iX .*- 1
0 5 10 IS
1)
4
..u
^
i
IS(2)
_
20 2) 30 35
R.l.nlfon Tlma, MJnut.i
Figure 21. Comparison of the HRGC/ECD chromatograms of the 6% Florisil
fraction of the 45-plus age category of the ES census division and
the elution of the surrogates and internal standards.
109
-------
1000
IS(2)
10 15
Aroclo. Mixture (1016, 1254, 1260) IS(1)
20
25
30
35
15(2)
L
20
Tlnw, MlnutM
25
35
Figure 22. Comparison of the HRGC/ECD chromatograms of the 6% Florisil
fraction of the 45-plus age category of the ES census division and
the elution of PCBs as a mixture of Aroclors (1016, 1254, 1260).
no
-------
1000
-ES-SVO-45+
U!
J
.-17
10
15
20
25
1 15
30
35
-
Supelco Standard Pettlelde MIX
1. Dicriloronaphlhalene, IS(1)
2. a- BHC
3. /3-BHC
4. y-BHC
5. 8 -BHC
6. Heptachlor
7. Aldrin
8. Heplachlor epoxide
9. Endosulfan 1 |
10. Dieldrin |S ,)
11. p.p'-DDE
12. Endrin
13. p,p'-DDD
14. Endrin aldehyde
15. Endoiullnn lulFate
16. p.p'-DDT
17. Oclachloronaprithalene, IS(2)
J^^^-JL-^JL-^
2
U
4 5
I
.1
0 5 10 15 20
Retention Tlm«, Mlnutel
7
1
-/
10
.
16
4
17
IS (2)
"f : ; r 1 •-
1 I__J 1 1 1 1 1 1 1 1 1 1 1
25 30 35
Figure 23. Comparison of the HRGC/ECD chromatograms of the 6% Florisil
fraction of the 45-plus age category of the ES census division and
the elution of a commercial mixture (Supelco) of pesticides.
Ill
-------
Method llonlc - o% Florllll Fraction
I. '3C6-l,2,4,5-tetracrilorobenzene
2. Dlchloronaphthalene, IS( I)
4. l3C|2-telrochlorobiphenyl
6. Octachloronophlholene, IS(2)
7. '3C|2-decochloroblphenyl
I
-.V' . ' . - 1- . M $ . -V—r^
IS{2)
15 20
Retention Time, MInutel
Method Blank - 15/50% Florllll Froctlo
15 20
Retention Time, MInutel
Figure 24. HRGC/ECD chromatograms of method blanks from 6% and
15/50% Florisil fractionation.
112
-------
B. Toxaphene Analysis
The sample extracts from the 45+ age category that were taken
through additional cleanup and fractionation procedures for toxaphene deter-
mination were analyzed by both HRGC/ECD and HRGC/MS in the SIM mode. The
methylene chloride/cyclohexane fraction from the carbon/glass fiber column
contained the organochlorine pesticides, PCBs, and the toxaphene components.
This required further fractionation on Florisil as described in the experi-
mental section. Although this procedure was demonstrated to be effective for
the separation of PCBs from toxaphene, the HRGC/ECD analysis of the sample
extract demonstrated considerable response to compounds other than the toxa-
phene mixture.
Since toxaphene is a multicomponent mixture of polychlorinated com-
pounds, it was determined that HRGC/MS-SIM techniques were necessary to deter-
mine the presence of this pesticide in the composited adipose tissue extracts.
The HRGC/MS chromatogram in Figure 25 is presented as an example of
the complexity of the toxaphene mixture. Estimates of the number of compo-
nents within technical toxaphene range from 177 to 670 compounds resulting
from hexachloro- through nonachloroboranes and borenes. Figures 26 and 27
are examples of the mass spectra of two chromatographic peaks achieved by
electron impact ionization. Due to the extensive fragmentation of these poly-
chlorinated compounds, the HRGC/MS-SIM technique was necessary to determine
if toxaphene was present in the sample extract.
Figure 28 presents plots of some of the characteristic ions from
the toxaphene mixture. Although significant response is noted for ions at
masses as high as 377 amu, the literature indicates that these components are
degraded extensively in environmental samples (Ribick, Dubay, Petty, Stalling,
Schmitt 1982; Jansson, Wideqvist 1983). Therefore, ions selected for HRGC/MS
analysis were selected in the range of 231 to 345 amu. The extracts were first
analyzed using ions at 231, 233, 235, 269, 271, 273, 305, 307, and 309 amu.
Several of the extracts were selected for additional analyses using ions at
305, 307, 309, 327, 329, 331, 341, 343, and 345 (amu).
The results of these analyses indicated that some interferences
still persisted even after the extensive cleanup procedures. In- particular,
significant responses were noted at the lower mass ranges possibly resulting
from the presence of chlordane related components. These interferences were
also noted in the HRGC/ECD screening of these sample extracts.
The ion profile responses for the sample extracts indicated that
the toxaphene pattern is significantly degraded from the toxaphene standard
used to establish the HRGC/MS-SIM monitoring parameters. Degradation of the
toxaphene pattern in environmental sample analysis has been noted in other
studies (Ribick, Dubay, Petty, Stalling, Schmitt 1982; Jansson, Wideqvist
1983). Quantisation of the data is not possible due to these drastic differ-
ences in the sample extracts and the standard. However, the low level toxa-
phene standard that was analyzed was equivalent to approximately 0.10 ug/g in
the tissue extracts. Based on the responses observed in the selected compos-
ite specimens the residue levels of toxaphenes in the composite tissues were
less than the 0.10 ug/g level.
113
-------
\ 01
CD E
ZL E
(0
O 1.
CTi CO
• O
O S-
Q.
(0
0)
<+-• i.
O 3
-(->
in , Q-
CO OJ
ro ^
u i—
in o
u
i— 03
^ u
O t3
C3 O) .
a: in c
I 3 •!-
«t- E
0) \
JC LT> C_3
-P I O
03 O
S- a rH
O
t- E 4->
I (0
E O
ro oo o
S- O
CO (0 O
o 53-
_ in ••
(JLf O'J
ro C
E T- O
O in -P
S- 3
.C s-~*
U Ol T3
C i—
C -P I
O C\J
rr\
CO
=.8
• -a o
in s- o
C\J (0 UD
-a
CU C E
S- (0 O
3 -P 5-
CO in M—
114
-------
fO
S-
O)
o
+->
fO
E
O
S-
_c
u
(0
-p
o
-p
Ol
o
S-
UD
o ^-s
c -a
s-
c to
(0 T3
U C
in to
-p
S- U)
o
1- Q.
•P 10
U X
QJ O
0.-P
(/) * — '
in LT>
in c\j
tO
s: cu
3
• D>
UD -r-
CM LJ_
O) E
S- O
3 S-
D5M-
115
-------
(0
5-
CD
00-
m
E
O
c:
o
(0
+-)
o
0)
.c
o
i.
U1
00
00
O ^~N
c -a
s-
C (TJ
(0 T3
O C
S-
o
CU
C
s- a.
U X
a> o
-d"
s: a)
^
• en
r^ -r-
c\j u_
OJ E
i- o
3 S-
am-
116
-------
8!
ffi
e
CT)
ro
u
•i —
-p
1/1
s-
Ol
-P
L)
rtJ
S-
ro .
^ LO
u -i-
(0
in c:
-P (0
o
i— s:
Q.I— I
(-O
-P I
C CO
s- o
u o;
or
o c
•r- ro
(U O
-P S-
U <4-
01
r— (1)
0) C
t/5 OJ
£
o.
• to
00 X
-------
Table 36 presents a qualitative summary of the identification of
toxaphene in the composite adipose tissues representing the 45+ age category.
As noted in the table, 12 of the 14 sample extracts exhibited responses char-
acteristic to the toxaphene standard. Although these results suggest the
presence of toxaphene, it is recommended that further analysis be conducted
using an alternate MS technique, such as negative chemical ionization mass
spectrometry (NCI-MS) to provide additional confirmation. The advantage of
NCI-MS is the generation of less complex mass spectra which contain prominent,
characteristic ions that can be used to establish confirmation and can be used
for quantitative efforts.
V. QUALITY ASSURANCE/QUALITY CONTROL
As discussed in the experimental section, the QA/QC program included
analysis of spiked lipid samples, spiked blanks, replicate analysis of homog-
enized lipid samples, analysis of a reference material prepared by EPA/EMSL-LV
(porcine fat), and analysis of method blanks. Other QA/QC facets included
documentation of the absolute recovery of the surrogate compounds and the re-
sponse of the internal standard (anthracene-d10) for each sample analyzed.
Also, the identification of a compound via the automated quantitation routine
was verified by retrieving and verifying the full scan mass spectra for each
identification versus the NBS mass spectral reference library.
A. Spiked Tissue Samples
A bulk lipid sample was prepared by homogenizing and extracting
human adipose tissue. The homogenized sample was filtered through anhydrous
sodium sulfate to remove water and particulate matter. The resulting extract
was taken through the GPC cleanup procedure, and the lipid was recovered from
the discard fraction of the procedure. This process provided a homogeneous
matrix relatively free of contamination from the target analytes. The homog-
enized lipid matrix was spiked with known levels of the target analytes and
taken through the entire cleanup procedures (GPC/Florisil) along with actual
samples. Table 37 provides a summary of the analysis of five spiked matrix
samples (10% of all composite samples analyzed). As noted from the table,
recoveries of the various compounds ranged from an average of 22% (tris(l,3-
dichloropropyl)phosphate/tri-m-tolylphosphate) to 204% for £,p_-DDE. The high
recovery of p_,]3-DDE may be a result of incomplete separation from the original
lipid matrix. An unspiked sample of this material was not analyzed to confirm
the background contribution. Precision of the five replicate analyses ranged
from 11% for the p_,g-DDE to 74% for the 2,4,5-trichloro-o-terphenyl.
B. Spiked Blanks
Table 38 summarizes the recovery data for target analytes spiked
into aliquots of solvent that were taken through the GPC/Florisil cleanup pro-
cedures and analyzed under the same HRGC/MS conditions as required for the
composite sample analysis. A comparison of the recoveries of the analytes
from the spiked lipid samples and the spiked blanks is provided in Table 39.
The method recoveries from the spiked blanks are greater than determined from
the spiked lipid samples. As expected, these differences may be attributed
to the effect of the sample matrix on method recovery.
118
-------
Table 36. Qualitative Summary of Toxaphene Identification
in 45+ Age Category
Sample no. Presence of toxaphene
1-WN-45+
2-WN-45+
1-SA-45+
3-SA-45+
4-SA-45+
1-ES-45+
2-ES-45+
1-WS-45+
1-MO-45+
1-MA-45+
2-MA-45+
1-PA-45+
2-EN-45+
3-EN-45+
Ions monitored for HRGC/MS analysis included m/z 231,
,233, 235, 269, 271, 273, 305, 307, and 309.
Additional ions monitored for HRGC/MS characterization
included m/z 305, 307, 309, 327, 329, 331, 341, 343,
and 345.
119
-------
Table 37. Recovery Efficiency of Semivolatile Organics from
Spiked Human Adipose Tissues
Compound
1,2-Dichlorobenzene
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
2,4,6-Trichlorophenol
Acenaphthylene
Dimethyl phthalate
Acenaphthene
Pentachlorobenzene
Fluorene
Diethyl phthalate
4-Chlorodiphenyl ether
4-Bromobiphenyl
a-BHC
Hexachlorobenzene
p-BHC
Phenanthrene
A-BHC
Heptachlor
Di-n-butyl phthalate
Aldrin
4,4'-Dibromobiphenyl
2,4,6-Tribromobiphenyl
Heptachlor epoxide
Fluoranthene
c-£'-DDE
Pyrene
Chrysene
y-Chlordane
trans-Nonachlor
£-£'-DDE
Dieldrin
o-g'-DDD
£-£'-DDD
2,2' ,4,4' ,5-Pentachlorodiphenyl ether
o-£'-DDT
tris(l-dichloropropyl } phosphate
Butyl benzyl phthalate
2,2' ,4' ,5-Tetrabromobiphenyl
£-£'-DDT
Triphenyl phosphate
4-Chloro-£-terphenyl
2,5-Dichloro-o-terphenyl
Di-n-octyl phthalate
Mi rex
Tri-m-tolyl phosphate
2,4" ,5-Trichloro-o-terphenyl
2,4,4" ,6-Tetrachloro-o-terphenyl
do-Naphthalene
lSC6-l,2,4,5-Tetrachlorobenzene
13C6-Hexachl orobenzene
d12-Chrysene
QC 223
51
48
56
127
30
62
39
67
54
71
55
61
68
103
67
97
83
58
71
110
80
96
70
67
81
65
68
66
65
78^
214d
136
63
69
58
54
37
74
64
63
51
33
45
143
48
NO
35
48
59
57
65
40
MR I
QC 229
54
ND
40
140
ND
55
88
53
42
54
87
50
61
100
45
ND
75
53
77
126
87
115
79
111
97
63
96
70
83
6H
220d
75
77
136
102
136
31
55
128
126
40
70
91
55
102
32
143
160
54
52
47
51
sample number
QC 234
39
82
57
97
41
40
53
40
30
44
59
38
47
83
47
62
65
74
93
55
71
98
70
106
93
61
94
67
78
9°*
217d
41
69
116
85
116
15
27
116
126
21
57
77
46
68
23
115
119
38
40
46
47
QC 239
NDb
63
ND
ND
30
32
48
34
25
41
58
31
45
66
44
56
61
61
58
46
67
76
55
79
64
42
58
45
59
60.
165d
42
42
66
51
66
17
26
58
43
17
27
32
29
31
15
26
32
18
21
43
21
QC 240
ND
103
ND
ND
45
33
54
32
21
35
59
26
37
62
39
50
60
66
66
86
66 •
89
58
91
73
50
69
55
67
11 A
203d
ND
56
79
69
79
12
22
68
62
17
38
45
43
42
18
43
39
26
24
39
24
Average
Recovery
48
74
51
120
37
44
56
46
34
50
65
41
52
83
49
66
70
62
73
85
74
95
66
91
79
56
78
61
71
76ri
204d
74
61
93
73
90
22
41
87
84
29
49
58
63
58
22
72
80
39
39
48
37
Standard
Deviation
8
24
10
22
8
13
19
16
14
15
13
14
13
19
12
21
11
8
13
34
9
14
10
18
14
10
16
10
10
12
23
45
13
31
21
35
11
23
33
39
15
25
25
46
28
7
53
57
17
16
9
11
aA bulk lipid sample was spiked with the following compounds at concentrations equivalent to 0.1 ug/g.
.samples were taken through GPC and Florisil fractionation prior to HRGC/MS analysis.
Not determined. Not included in the average recovery calculation.
^Not included in average.
High recovery due to contribution from the adipose tissue matrix.
The
120
-------
U1
c
03
C
0>
' —
o
•o
0
u
0)
Qi
01
U
I-
0)
0.
in
-P
c
O1
E
s.
OJ
a
X
c
o
ro
3
«
UJ
13
o
.c
4-*
Ol
oo
ro
01
.a
(T3
^—
CO
ID
00
00
S
'_£
nj
01
ce
d^
s.
-a
c
ro
t/>
**
m
Ol
ro
OJ
C
O
«
>
01
•o
^
S-
01
>
o
u
ai
S-
rH
CM
CM
CM
CO
i-H
CM
ID
CM
•3-
O
CM
m
o
C\l
•0
C
3
O
a.
E
O
CO
cnroorn^ror~CMCMOOrHinm<3-cnu3inr--oaia>OCMC>ir)irir~in«j-ou3rH«!)-
«J-rOCMCM«-CslrHCSlrHrHrOrHrHr-4rHrHrO«3- CMCM
i-HCMrHrHrOrHrHrH rHCMrH rH rH CM CM CM rHCMCOrHrHrHrHCMCNJi-HCMCMCSJ
lDOCMrH^inir>lTlinrHOlf)CTilr>CriCO<'0<3'^'CMlDCOf^'OCOl£lOCJl«J-«3-Cir*vir,
c\j(i3vouDS-uciu3LnuDU5FN^v£)^j'i£)p^f^r^LnococochLnoor^c^oooocTiocftco
rH rH
.0 .0 J2
csj in <^ LO Lfi t^ to ij"> *£> VD vo ".o tf) to r^ r**« r^ rH oo co fo ^~ r^ co CT> cr^ r*^ o^ oo 01 oo
rH
r-4 rH
O CSJ CO O m *f l£ 00 ^" f** 00 CO CO 00 U^ CT1 LD f~l rO O tf) rH 00 CO O CSJ O^ CSJ LO VD CO *^" Csj
^co^^oo^^^^r^lC^^f^cJ^^^u^^^ocTlO^cslc^^r^^o^o^v.o^csJcsJOOr^O'HLf)
OrOr^r^Lni^inrO^rHtnrHCOCNJrHmO^gU^gC^rH^CO^^QCOgiH^CNI
rH
m
rH i— 1 iH rH
O^ t£ o p^ en iH oo ro LO ^D r**. oo o ^D o rH oo ro ro o tD f*^ cr> o r** o o csj CO f*^ *o ^ f^o
Csj^rOfO^^rOLnintTJLn^Lfll^lD^f^COO^f^COr^iHOOrHrHrHrOrH'Q'CSJO
0
J_>
^
o.
o
OJ F— S- ^ r-
C — >> OJ O. >>
OJ O C -C 0) r- C
tt)NC OJ-P '^ -P >, 01
C i— C Qj QJ GJ -f ^ r— fO C j~ Qj
OJO0X:4->CO.CU O>>» r- r- 01 D. TJ
fsicjD Q. ro O»T- 4->r— c^: mo -c *r- •*-
ccuo Of— N^3 m >>r— OJ-P x:c o.^2X i-
a* — t- j-oifo co ' — c>) NOI -Pd) •'"Go o
OI.QQ.O OC^ 0)t- (DQJC CO -C ,C ^OEQ. (^
COO «~~ *••• Ol +J 0 -G O -C -C QJ OJ t- O) O. O. O O QJ Ol -C
oit-t.^a>^r- ^cor- +-> o-£ jaoc oEt-c u
NOOUCU>)Q.O>l-.C ^-i-Q. O<— QJ t-r—S- O^i-O) fO
C t— i— T- 0) -r- ^1 .COU tt "O «r- i-^ i- O>iO t-'r-O-C C
Ol^^^r-i_4Jr— jJr-OOt O^ OU .C r— 4Jr— jDfc-r-^JUJ CDO
^iuur-mr-i:>,^r:ccf-t.o r-i 4J ^IDJ: -i-r-x:cQ cz
o-r-.r-t^:iD--CQ.uoo)>>OE ^rcsj c uj3ucQiurooo)OJi
Oil *• *" * C O> C 4^ I O +^ i^* S- T" (0 i/> "f" c Z +•* C |-*J t- — *• +J O — 0) >> C
i — CslsfCSJ Q. ^ O> E O* CO 3 QJ O CD 03 XT- CD O"CQ D.I C"O^-
CTiOOCOrHOOOCMfHrHCOr^.
CSJ CSJ
rOCSJCSlCSJfOrOCSJ rHCSJrH
*j'Ocsjcr>r--cocsjO"!Csjoo
OCTiOOiHOOCslLDCSJiH
rH rH
^
CnO^CTir-lrHCTlCnrOLnrHO
rH rH rH
S S co K ° rt § 1 5 S; co
^ rH L/1 CO ^ OT rH CO O ID rH
CMrH^rOfSJCMCMCMlOLnfO
girirOgCMrHCOUDCOI-~lO
rH rH rH rH r-l rH
CO CM f** rH r^ CSJ U1 If) ^ ^ CT>
rH rH
CM tD rH lrt LD f^* ID O CT1 ro rH
incMCMCMr^lDroCMf^fOro
O)
ro
a.
i. 01
ai o
J-> Q.
01
c o.
01 O i—
a. o. c
•— -i- O Ol
> -o i. jz
c o o a.
s: o !c +» 5
Q. -— u ro o
"- £ •!- r— £
^a u *D ro o
o ro i JL i-
o c - j: ro
•— Ol CM D. !-
x: a. 4J
U 1 i- i— 01
re LTJ o >, (—
1- - N I
*•> - i c in
O'i-r-OQ «O "J3- O
OS-IOQ^-OrH B-o
— r— **— — — — in >, — —
OJ 01 O QJ OJCM QJ"- +J CM OJ
OJO- OIOJCM Oil— CO CM OJ
121
-------
4J
oi ro
CNJCsJOOlOLfl
01
.0
00
ro
01
r^oro»HO*3-ooair>inf-H*f
LnoocnooooiDZZzoocnr^-oo
2
>>
c
01
a.
i
f— C
I— C .C .
O
o
. a. i o
s- oi ro
a> i t-
oj o c o i— -
r— p i— ro i— >>-
>, o -c N .c +J ui
c s- u c u u -
.e r— Q ca o i - )
i-
ai o>
a. i c
s- o|a.
i s- s- c
O|C -C O)
. i ^- *> i—
o-— s- c a.
!'•-(—-'- -CTO^-TOOOI*'-
01 Q.JD
JZ — O
i— O.J3 S-
>,— o o
O 1-
r— O
>>-n s- • — u o.4-> -
3 .
U 01
10 -p-
u o.
OH- o s-
c i i— o
: z o
I I
-•£•
o u
,c s-
-OIOIS-'!-S-UI—
UT1 IT) *t » " O
- » • ^- - (.
<-- en o
*J-CMfHOOOC>J
• F- S- - - - Ol
Si— CM Co t—t DO
0) -O
4-> 01 T!
01 4-> 01
•o ro T>
U 3
*-> 4->
Q O O
z z z
ro aO LI
122
-------
Table 39. Comparison of the Average Recovery Efficiency of Semivolatile
Organics from Spiked Lipid Samples and Spiked Blanks
Lipid samples
(n = 5)
Compound
1,2-Dichlorobenzene
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
2,4,6-Trichlorophenol
Acenaphthylene
Dimethyl phthalate
Acenaphthene
Pentachlorobenzene
Fl uorene
Diethyl phthalate
4-Chlorodiphenyl ether
4-Bromobiphenyl
o-BHC
Hexachlorobenzene
p-BHC
Phenanthrene
A-BHC
Heptachlor
Di-n-butyl phthalate
Aldrin
4,4'-Dibromobiphenyl
2,4,6-Tribromobiphenyl
Heptachlor epoxide
Fl uoranthene
o,p_'-DDE
Pyrene
Chrysene
y-Chlordane
trans-Nonachlor
p_,p_'-DDE
Dieldrin
o,p_'-DDD
p_,p_'-DDD
2,2' ,4,4' ,5-Pentachlorodiphenyl ether
o,p_'-DDT
tris(l,3-Dichloropropyl ) phosphate
Butyl benzyl phthalate
2,2' ,4' ,5-Tetrabromobiphenyl
p_,£'-DDT
Triphenyl phosphate
Average
recovery
48
74
51
120
37
44
56
46
34
50
65
41
52
83
49
66
70
62
73
85
74
95
66
91
79
56
78
61
71
76
204
74
61
93
73
90
22
41
87
84
29
RSD (%)
17
32
20
18
22
30
34
34
30
20
34
25
23
25
24
32
16
13
18
40
12
15
15
20
18
18
21
16
14
16
11
61
21
33
29
39
50
56
38
41
52
Blanks
(n = 6)
recovery
60
62
61
74
65
65
55
65
61
65
49
66
79
78
73
104
82
86
98
57
78
96
100
89
104
94
100
97
94
86
104
90
109
117
108
102
29
52
120
110
78
RSD (%)
33
20
14
46
23
17
22
12
18
15
13
14
19
16
35
20
8
19
30
52
15
16
17
25
24
20
26
21
22
34
29
28
21
30
28
22
21
21
18
17
17
123
-------
Table 39 (continued)
Compound
Lipid samples
(n = 5)
Average
recovery
Blanks
(n = 6)
RSD (%) recovery RSD (%)
4-Chloro-p_-terphenyl
2,5-Dichloro-o-terphenyl
Di-rroctyl phthalate
Mi rex
Tri-m-tolyl phosphate
2,4,'5-Trichloro-o-terphenyl
2,4,4',6~Tetrachloro-£-terphenyl
d8-Naphthalene
13C6-l,2,4,5-Tetrachlorobenzene
13C6-Hexachlorobenzene
d12-Chrysene
49
58
63
58
22
72
80
39
39
48
37
51
43
73
48
32
74
71
44
41
19
30
113
113
41
116
42
131
133
69
63
74
127
22
21
39
21
24
32
33
30
22
36
21
124
-------
C. Porcine Fat
A porcine fat sample (Adipose 121) provided by EPA-EMSL/LV was ana-
lyzed periodically as another means of determining the accuracy of the method
for selected organochlorine pesticides. A primary difference in the porcine
fat sample and the human adipose tissue samples was noted in the difference
of the GPC profiles. The lipid peak from the porcine fat eluted from the GPC
column at an earlier retention time and as a well defined Gaussian peak shape
as compared to human adipose tissues. Typically, the lipid peak from the
human adipose tissue was noted to tail into the collection cycle of the GPC
cleanup.
Table 40 summarizes the results from the analysis of five aliquots
of the reference material over the course of the analysis of the adipose tis-
sue samples. Table 40 also reports the actual concentrations of porcine fat
as reported by EPA-EMSL/LV and the accuracy of each of the measurements. Pos-
itive identification and quantisation of each of the spiked analytes was not
possible due to the limitation encountered for the analysis of 1.0 g sample
aliquots. Trace levels of trans-nonachlor and p_,p_'-DDT were detected in the
sample extracts. The £,p'-DDE residue was detected in all five of the analy-
ses with an accuracy ranging from 76 to 210%. The levels of £,p-DDE were de-
tected as positive quantifiable values. Responses to characteristic ions from
the molecular clusters for hexachlorobenzene, p-BHC, heptachlor epoxide, mirex,
and oxychlordane were observed. However, the intensities of the responses
were less than the 2.5 times signal-to-noise as required for establishing the
detection limit.
D. Replicate Analyses
Replicate sample analyses were completed using a bulk homogenized
lipid sample extracted from composited adipose tissue samples. The replicate
analyses were achieved using either I- or 4-g aliquots of the homogenized
lipid. The HRGC/MS analysis resulted in the detection of several organochlo-
rine pesticides, PCBs, phthalate esters, and PAHs. The results of the repli-
cate analysis are presented in Table 41. The compounds that were detected
consistently in the 4-g samples included hexachlorobenzene, (3-BHC, heptachlor
epoxide, trans-nonachlor, p_,g'-DDE, j},jD'-DDT, diethyl phthalate, and di-n-
octyl phthalate.
The results for p_,p_'-DDE provide the most consistent data. The data
point for sample QC-235 is considered an outlier by using a simple Q-test.
The reported concentration for the remaining 15 samples range from 1,600 to
3,000 ng/g with an average of 2,260 ng/g and precision of 20%. Since p,p_'-DDE
is the analyte present at the highest concentration, it is expected that it
would provide the best measure of method precision. The variability in the
concentration of other analytes is in part due to the small sample sizes (1
to 4 g) in comparison to the 20-g composite adipose samples. Responses for
the characteristic ions for hexachlorobenzene, naphthalene, phenanthrene, and
penta- through heptachloro-PCBs were observed in each of the replicate tissue
samples. However, the responses for these components were below the estimated
limit of detection and thus were considered as not detected in these analyses.
Further studies based on this broad scan analysis approach should require the
use of replicate samples of equivalent size to the composite samples.
125
-------
^
CM
rH
QJ
tn
CL
•a
s^/
OI
CL
E
ro
u/)
OJ
in
O
CL
•D
CJ
C
o
i-
O
Cu
•o
OJ
•*
'5.
cr
^
rC
C
l/>
5-
CJ
X
o>
J-
o
«*-
s-
rC
3
t/)
fO
o
CD
^~
.Q
m
r—
oo «r
CXJ CO
CM OJ""N.
CJ r-^ "^
r- m
CNJ <7>
1 i— 1 r~H
CJ --v
Cr «r
^s
en
CT
c
^^
C ID ^
O rH CO
•r- CSI C7>^.
fl (J rH v
S- O- IT!
C
0!
U
C
o
CJ
CM CO
CM «*
O ^,
O" «f
CM ro
c_) >^
o- *r
ro
en
ra
c
c
o
ro
C
Ol
u
c
o
u
•o
OJ
o.
CO
• -t-> rjj
O JZ 4->
c en ro
oj rjj
r— S Ul -O
CL -i- C
E OJ Ul 3
ro • — >, o
W .fro I"
CJ ro C O
O'co ^ O
»— 4
ce
s:
^-v ^^ ^^ ^->
o o o o
o o o o
CM CM CM CM
O Q O O
Z Z Z Z
0000
O «)• O CM
CM CM CM rH
O O O O
Z *f Z CM
CM CM
O O O O
o o o o
CM CM CSJ CM
o o a o
z z z z
o o o o
o o o o
CSI CM CM CSJ
O O O O
z z z z
n
O O O O
O O O rH
CM CM CM rH
0 0 0 0
Z Z Z 0
CM
O 01 O O
LO Ol CO CC
rH
OJ
oj -a
OJ X t-
N O O
C O. r—
OJ OJ JZ
o L)
o t. m
i. O C
0 i— 0
•— •=. z
J= U 1
LJ c_> ro in
ro 1. *J C
X CD a. ro
OJ 1 flj S-
3Z CO. ^ +>
^_^ ^-s ^^
r-^ / — . O O O
LO CO O O O
^ CO CM CM CM
o o Q a o
O CO Z Z Z
LD CM
rt
O O O 0 O
rH CSI TJ- O O
CM CM CM CM CM
o ro o o Q
O rH «3- Z Z
ro r^ CM
^
^ o o o o
rH rH O O O
CO rH CM CM CM
O 0 0 Q D
O LO Z Z Z
r-. ro
rH
/*•* O O O O
o o o o o
CTi CM CM CM CM
o a a o a
o z z z z
rH
U
/«s ro O O O
cn o o o o
r~ rH CSJ CM CM
o o a o o
LO ro z Z Z
to ro
rH
O 0 O O O
O CSJ O *}" O
rH ro rH rH CM
CSI
OJ
C
ro
•o
LU r- t- c
Q O O v-
Q O •— t-
i i x J= -a
- OJ U >—
CU CX| !- >> OJ
. .r- X —
QJ cu z o a
OJ
>J
u
OJ
-*->
OJ
Ul
re
*
ro
3 -0
+J C
o
C CL
O E
V) O
•r- O
i.
D.
O O
U «*-
(U tn
c w
•r-
CU
cnx:
C r~
ro -
•r— O
L) i-
•1- 4J
4J O
ro -n
CL OJ
•D
in
OJ t-
•r- O
O -U
ro 'i
i- •!- .
J3 "~ O
ro TJ -t-
i— OJ +J
4J (0
O ro S-
4-> E +J
C *J OJ
O V> U
••- OJ C
4J O
ro oj u
U J=
c ro
3 in 3
E "~ O
o - — - ro
u Q
Z OJ
1- +->
cn a» o
rH j-> +J
U
- OJ 4->
cn *J o
OJ OJ
>>T3 CL
t- in
ro *J OJ
3 O (-
u c
OJ £ *J •
LL. JJ -r- O)
C X D)
*" XI U
> ai ro C
—1 +J i- -r-
•v. t. 3
— 1 O U +J
co a, u -i-
Z OJ (0 E
UJ L. -r-
< in c
a. T- oj c
UJ I/I U O
QJ L- *r~
>,J= OJ *J
J2 +J O. CJ
C CD
•O oj a) •*->
OJ J- -C CU
TJ ro *J TJ
•r- CL
O C OJ OJ
CL ro ro
OJ U E
ro 3 •!-•!-
<4J r~ TJ 4-*
ro ro c in
a > -r- LU
ro J3 U
126
-------
^
r—
C
C
ro
>
ro
E
E
13
CO
ro
+j
rO
f~i
r-i
^~
dJ
r—
O
ro
I—
CT
\^
a>
t~
^^y
c
o
rO
£-
+J
C
O)
(J
f~
o
C_3
rH
OO
CNJ D1
1
f 1 ^-
cy
o
OO
CNJ Ol
i
C_3 rH
o-
LD
CNJ
CNJ CJ>
C_5 rH
cy
rH
rH
CNJ O>
1
C_J *3~
cy
o
rH
CNJ O)
1
O •*
cy
cn
o
CNJ O5
i
O it
cy
00
o
CNJ 0)
1
O "3-
cy
r^
o
CNJ O)
1
C_3 •=)-
cy
• • • •
* *
O +J
Z 3: -0
c
a> cu ^
C_J r— • r— O
ex a. Q. a.
E E E
i— i ro rO O
ce. co co o
2:
O Q O
00 Z ID
\^f
S~*i ^— ^
Q O Q O
Z O Z O
CNJ CNJ
'*•«••'' S»M*'
,— V ^-N
f~^ f~l f*^ f~!i
Z 0 Z 0
CNJ CNJ
^
o a o
00 Z LD
rH ^
^^
00 Q O
CD Z LD
O O
i cn
rH LD
0 -3-
cn ^
rH
o cn
oo uo
t-H
at
-a
•i —
X
o
Q.
a>
j_
0
i —
f™
u
O ro
QQ Q.
1 O)
CO. 1C
o o oo
cn o cn
rH CO
rH
^^N /^^
Q O O O CD
Z O O Z O
CNJ «t CNJ
N— ' CNJ ^— '
/^^N ^"^
Q 0 0 Q 0
Z O O Z O
CNJ O CNJ
\^> (V) • t
O O -3"
cn o r~~
oo cn
CNJ
o o o
00 O rH
CNJ CNI CNJ
CNJ
O O «3-
r — o cn
cn oo
rH
O O OO
0 0 CTI
00 rH
CNJ
O O O
LD O O
OO CO rH
CNJ
S-
o
r— •
f
U
ro
C
O LU I—
Z Q Q
i Q a
in i i
c - -
ro o [ o i
£_ r> f.
•4-> aj Q4
CD O LD
z LD cn
\^s
^*^
a o CD
z o cn
CNJ rt
^^
o O
Q O O
Z O OO
CNJ CNJ
\^ /
t N
Q 0 0
Z LD 00
-^s CNJ
CNJ CD
LD *t
rH
^^
Q O CD
z LD r^
00 O
oo cn
rH
CNJ O
CD OO
rH
CD
ro
O> i—
+-> ro
ro -C
rO c^
-c a_
^j
_g~- 1—
Q- >>
-(->
^>> <^
-C 1
ai i
a a
t ^ CD
Z O
CNJ
<*^s
s~ ~\
Q O
Z O
CNI
Sw>
/-^
Q O
Z 0
CNJ
\^^
O
CD
t—t
O
^~
oo
^
Q O
Z LD
/— ^
a o
Z LD
^^
o
ID
*^-
a>
4^
rO
'ro
1 ^
( —
a.
r—
^^
N
C
CD
JO
^^
I %
^
03
Q O
Z O
CNJ
^^
/^*,
Q O
Z O
CNJ
*-»^
O
00
LD
O
O
^t
O
o
cn
rH
LD
cn
CD
CNJ
rH
O
O
CNJ
a>
ro
ro
i *
t —
a.
, —
^~
+j
u
o
r^ i
1
•i —
127
-------
/•""•N
"O
QJ
ZJ
tz
-p
o
(J
S^y-
T-H
^-
QJ
-O
re
h—
^— \
en
\^
co
c
s^^
c
o
•1 —
-p
re
i-
-P
c
QJ
(J
O
O
en
«^-
CM CO
1
O 3-
Cf
ro
^J-
CM CO
1
C_3 rH
O'
rH
^-
CM cn
i
O rH
cy
LO
cn
CM CO
i
C_5 rH
o-
CM
ro
CM CO
i
C_3 i — 1
cy
. • . .
O -P
•z.~3. ~a
c:
QJ QJ 3
C_3 r— r- 0
O' Q. O. Q.
E E E
i — i re re o
O£ CO CO C_5
^.
/•"""x ^"">
Q O Q O O
z. LO z LO cn
s_^ ^ rH
/ — s
cn a o o
CO Z LO O
> — ' CM
rH Q O O
^-^ CM
,^-s
r-- Q o o
i^O ~f£"_ LO LQ
<-^ CM
/""""% (**""%
Q O Q O Q
Z 0 Z 0 Z
CM CM
^w1 S^
^ ^-N
Q O Q O Q
Z 0 Z 0 Z
CM CM
^~s v«/
^^
O Q O O
CM Z O «tf-
CM CM CD
v^^
^— ^
O Q O Q
*t Z O Z
CM CM
^-^
0)
TJ
X S-
0 0
O. r—
cu ^
u
s- re
o c
i— O
.c z
U 1
O rO CO
IE -P C
QQ ex. re
1 QJ £_
CO. IT -P
O QO QO QO QO QO
CO ZLO ZLO ZLO ZLO ZLO
CO *••— ^ ^—S SB^ ''XJ^ V^
CM
0 QO QO O QO 0
O ZLO ZLO CM ZLO CM
CT> v— ' \~s r— 1 ^— s CO
t— t
OQOQOCD CO CM
CTl -^^ v_^ rH
rH
/*~N /^*N /^^ /""^
O QOCJOQOQO
O ^3 ZLO ZLO ZLO ZLO
C\J ^•M*' S*— ^" 'N^rf' S»— n^
CM
/"^ /*^ /^*N *^*S
O CD QO QO O QO O
0 0 ZO ZO *t ZO 0
CM CD CM CM CM CM CO
s^^ f-H \^s ^^ ^^
^-> /— S S~^ /-> /— S
O O QO O QO QO QO
0 0 ZO -3- ZO ZO ZO
CM •=*• CM rH CM CM CM
^^ CM "s— ^ i — 1 '***s "^^ ^^
, s / S /— S
O O QO QO QO O
0 LO ZO ZO ZO CM
ro «d- CM CM CM oo
CD ^— ^ ^--^ ^— '
/^•^ /^^. /— ~> ^~^
O O QO O QO QO O
O O ZO O ZO ZO O
CM CT> CM CO CM CM LO
•*-s CM ^^ ^— ' s_^ rH
QJ
Ol -P QJ
-p re -P
re i— re
ro ^: Q. ^
jc a. a.
-p t—
^ r- >, r-
CL >, N >,
LU t— -P C -P
Q a i— zs cu u
Q a >, & ^2 o
II -C 1 r— |
- -P E| >, C|
oj aj QJ i -P i
*• " •! •! 3 •!—
CM CXI Q C3 CO Q
t
.^
E
•r—
i—
C
o
•i —
-P
u
QJ
4^>
QJ
T3
•a
QJ
-P
re
E
•1 —
•P
CO
QJ
-P
IO
-P
C
QJ
LO
QJ
i-
Q.
QJ
S- .
T3
co a>
OJ N
LO •!-
O) S-
^: re
c E
ai 3
I- CO
re
Q.-P
o
c c
"~ re
QJ +J
zs re
re
> -P
3
_a
.
"O TJ
QJ QJ
•P -P
U U
QJ QJ
•P -P
QJ QJ
•a -a
•p -a
o c
Z 3
O
i ex
E
Q O
Z O
re .a
128
-------
E. Method Blanks
Method blanks were generated as composites during the GPC cleanup
of the composited adipose tissue samples. At least one loop of the automated
GPC unit was run as a blank for each day's operation. Enough methylene chlo-
ride was added to each composite blank to bring the total volume up to the
equivalent of a GPC cleanup of a 20-g sample. These composite blanks were
taken through Florisil fractionation with the actual samples and analyzed by
HRGC/HRMS.
As discussed in the results section of this report, the blanks typ-
ically demonstrated background levels of phthalates and phosphate triesters.
Blank values for these compounds were noted to fluctuate over a wide range.
For example, blank values range from 0.079 to 1.5 ug for diethyl phthalate,
1.2 to 12 ug for di-rrbutyl phthalate, and 2.9 to 20 |jg for di-n-octyl phthal-
ate. Butyl benzyl phthalate ranged from not detected at 0.2 ng to 0.78 ug.
The phthalate data were corrected for a specific blank taken through Florisil
with a set of samples. Hence, trends that may occur in these data might be
associated with the blank values. If the detection level in a sample was less
than the associated blank value, the blank value was reported as the estimated
detection limit for that sample.
The phosphate triesters were detected in the method blanks less
frequently than phthalate esters. The blank levels for triphenyl phosphate
ranged from 2.4 to 26 ug, and the level of tributyl phosphate esters was de-
tected as 7 ug for a single method blank. The values for the phosphate tri-
esters reported are corrected for the observed background concentrations noted
in the associated blanks. The criterion for the determination of the detec-
tion level of the phosphate triesters was handled as described for the phthal-
ate esters.
F. Surrogate Compound Recovery
The stable isotope labeled surrogate compounds representative of
chlorobenzenes, PCBs, and PAHs were spiked into all composite samples, QC sam-
ples, and method blanks prior to sample preparation to assess method perfor-
mance on a per sample basis. The absolute recovery of each of the surrogates
was measured versus the internal standard, anthracene-d10, which was added
immediately prior to extract analysis by HRGC/MS. The absolute recoveries of
the surrogates from the composited samples and the associated QC samples are
tabulated in Tables 42 and 43.
As noted in Table 42, the recoveries of 13C6-l,2,4,5-tetrachloro-
benzene and 13C12-decachlorobiphenyl were determined by both HRGC/MS and
HRGC/ECD. The recoveries for the HRGC/ECD analyses were determined from the
internal standards, dichloronaphthalene and octachloronaphthalene, which
elute within the same retention windows as the two surrogate compounds (Fig-
ure 21). The results from the HRGC/ECD determination generally demonstrate
higher recoveries than by the HRGC/MS methods, especially the recovery of
the 13C12"decachlorobiphenyl. The differences in the recoveries from the
two methods may be attributed to selection of the internal quantitation stan-
dard, matrix effects, or both. The sample extracts analyzed by HRGC/ECD were
diluted by a factor of 10 as compared to the extracts analyzed by HRGC/MS.
129
-------
en
c
OJ
E
o
OJ
Q.
OJ
in
O
a.
•a
^
c
(U
E
X
TJ
4-=
O
Q.
O
co -o
>- C
U- 3
O
OJ Q.
4-> O
U
E
O OJ
i~ 4->
it- CO
01
^ o
3
in cyi
0<
'H
OJ
o
U
o>
a:
•O
3
0
£-
o
aj
t!
Cn
0
s-
3
to
14-
o
;>j
t-
(U
E
e
3
i/l
CNJ
OJ
.O
10
t—
1 C
a> "5.
a —
i ^
CM O
- S-
0 0
fo *—
U
1 C
ro OJ
+J .C
U D.
O —
1 -D
CM 0
« S-
O O
U
'T
c
1 OJ
- JC
•3- Q.
• O
t-
-r-
1 U
CM 10
rt t-
~ OJ
o
i. ,—
o >>
1— C
-C CD
i a.
1C
_
c
1 OJ
X C
CO 0)
1 O
0 0
o
ai
c.
QJ
1 N
in c
•3- -D
- O
- O
CD U
c-> ro
n I-
01
a>
c
01
in
jr
0
i
CM
•a
OJ
c
OJ
r—
ro
^
^
Q.
go
•o
O
c
O) QJ
E in
(0 O
on a.
E
O
U
o o
t— » i-H
LO "H
(\J
r— t r--
ro LP
T O
ID ID
i— 1 f-H
in LTJ
VD fH
ro ro
in I-H
ro r-v
r^ CTl
Q" CNJ
rH +
t LO
o «•
1 |
O 0
CO tO
«c
rH CO PO
ro O rH
rH O ro
CM
CM CM
to ro O
rH CM Tj-
-H
to m r^
in rH
rH | -f
i m m
O rH td-
i i i
CO LO LO
1 1 1
UJ UJ LLJ
1 1 1
rH rH rH
CM CD
r-. co
O CM CO
i — |
CM
r-. ro to
ro CM
|J3 ro r~->
m ^~
r-- r— to
r- CM en
TO
en ro
m r*.
CM en *±
LT) CM CM
CO ro r-.
*$• ro CM
PO ro CO
PO CM rH
rH 1 +
i in in
O rH <^-
1 1 1
O O O
to ^/) to
1 1 1
ggf
rH rH rH
en r-- CM
r-. r^- to
in CM jo
rH «^-
O Q J3
rH
O Q- JO
co r- to
^r co oo
O- rH rH
*fr CO tD
m co en
^j- tO CO
O «3- J2
PO ^J-
^- ro
co cn I-H
CM PO to
rH 1 +
i in in
O rH **•
1 1 1
§§§
CO LO LO
1 1 1
•z. z z
UJ UJ UJ
1 1 1
rH rH rH
rO rH CO
cy> co r*^
ro CM CM
ro ro in
CM to CM
in in r*.
rH o en
r- en co
rH rH P*
r-^- co co
ro CM ^*
r^* co P^-
PO r^ m
en r^ co
O CO
to to
CO CM O
CD ro o
rH
CM CM
m m
rH 1 +
i m in
0 rH <-
i i i
o o o
tO CO CO
1 1 1
1 1 1
rH rH rH
en ao o
r*-- to co
ro O Cn
CM UO rH
P*- rH CM
p*- to CM
CD co en
ro P*- ^f-
r*«- en 0*1
rH PO in
P-» P-- CO
CT^ CM O
r*- r^. oo
CM ^s- en
in *f *n
*f CD tD
in en CD
p- en o
in in co
rH 1 +
i m un
O rH «3-
g 00
to co to
1 1 1
Cn p««
ro cr> ^~
^- in ro
to o ^J-
rH P*.
rH
O O O
O CM rH
rH rH rH
in p*-. ro
CD CO CO
CO P*. rH
CO O <7>
O 00 CD
m CD in
CD CO P*-
m to in
PO rH rH
«3~ to m
rH 1 +
i in m
O rH *J-
1 t I
§§§
LO tO CO
1 1 1
CO CO CO
UJ UJ UJ
1 1 1
rH rH rH
^- ro to
CT OO CO
O CT. rH
CM CO ro
rH
§rH CM
m to
O ro p^-
CM en en
rH
CM ^ rH
CD en en
CO PO CO
in en p^
r-?*?p*-
CD ro P*-
"3- CO CO
in co co
CM in o
CO CO CD
ro 00 *t
*t to PO
rH 1 4-
i in in
O rH *J-
) 1 1
to to to
1 1 1
1 1 1
rH rH rH
CM to LO
CM ro rH
in to en
o m o
PO CM ^~
rH rH
O O O
rH rH
CT> CD O
m CD o
rH
o o *s-
CD "O" 00
O m «f
r-^ PO ro
ro o m
in ^r P^
Sen p^«
CD 00
rH
CO 00 rH
rH i +
i m in
O i— t *f
i i i
O 0 O
LO CO tO
1 1 1
iii
i i \
rH rH rH
O PO rH
rH
r- O rH
CM CM CD
rH
rH rH CO
CD px en
CH rH CO
PO in in
o PN» CD
«tf- ^- CM
^p in ro
PO ro «tf-
So ? S
PO en in
csj CM ro
rH 1 +
i in m
O rH «t
1 1 1
§§§
CO LO LO
< 1 1
CM CM CM
130
-------
I C
(TJ QJ
cj* O
O
cn
CM O
-H C.
CJ O
GO cn cn
«3- r-t CO
O >,
i— C
x: cj
m xi
131
-------
§
CU
o
D.
C
(tj
E
3
S-
O
>*-
in
OJ
O.
E
00
o-
-
Ll-
CU
.C
4J
E
O
£-
U"
in
01
a1
o
u
OJ
•o
c
3
O
o.
E
O
CJ
CU
.*->
re
en
o
s-
S-
3
U-
O
^
ro
fi
•a-
r^
JD
1C
in
c
3
O
gj
O
u
a>
TO
CT
O
I_
D
t/>
t C
TO Of
U -C
Qj CL
Q —
I -D
CM O
•H S-
o o
CO r-
U
I C
TO O)
-P .c
U D.
O "-
r .Q
N O
O O
CO r—
LJ
1 C
- a>
* a.
- o
ro t.
* O
ro i—
CO U
C_J S-
ci -P
-H 0>
o
o •—
!c c1
LJ flJ
I -C
LJ
en
a>
c
1 OJ
X C
X il
1 O
so i-
LJ O
C*5 r—
u
OJ
c
1 Nl
IT) C
- at
- o
CM {.
- o
rH r-
1 JT
to u
LJ TO
m s-
0)
c
tu
Ul
^
^
Is
OJ
c
QJ
-P
a.
TO
i
00
X
TO
s:
o
S §" d
S nJ z
CO
O O CM O O ^~
O O O O O CO
IT) CM CM CM rH CTi
rH CM rH rH rH
O O O O O O
(D rH CM O O rH
rH CM rH rH rH rH
^D to P^» ro u") CD
ID P*» LT> CO P~» CT^
rH PN> CT) P*» CM O">
vD P^ ID p*« ro r^»
rH CO *f CM O P*-
O O O O 0 O
CM r- o r*~ ro *-H
O ro en P-. CM i^
c c c c c
'o "o 'S 0 >*- 'o 3
in t/J t/> Q. t/> f
rH CM ro LT) ID P*-
O O O O O O
CM CM CM CM CM CM
O CO ro P- O U3r--O
^" CD CO ^" LO LDCOCM
CM rH rH
rO UD CM 00 O COCMO
CO ^ O"» un p»~ tniDro
rH rH
CM ID O CM O COrOO
O"i ID rH p~- ro LO P*» O
rH rH i-H
p»- ro *r P*- ui ooro
CTi ID rH CM CM P--OU")
oo to in lA+^-POJ
O O O O 0 OCCC
CuC Q.C CXC O.C Q. C CXOJ OJ-i—
"O E"D E"O E"D E"O E "O »— •— t. TO
TO3f03TO3TO=JTO3(COOOS-
^c .c ^: ^: ^ W(/>Q.
co en o I-H CM ro^-co
CM CM CM CM CM CMCSJCM
132
O
(J3
O
rH
«(S-
O
CM
fs^,
CTi
If)
00
o
rH
rH
O
O
O
rH
0)
c
•r-
-- TO
O M~
CL
r^
CM
oo-cj-inroo o o
rH rH rH rH
OOOlDrOCM CTi CM
rH rH rH
OrHororom co ro
rH rH
P*- CO *D P^ CO ^ LO CO
o uo co co CTI cn en o
O r— i in r»* ro CM P^- ID
i — i
OlDCTilDCMrH O CO
corHr*-un*a-ro o ^~
rH
OOOOOtD O P-*
CPiUDCOlDrOro CTi ^~
a>
(U tn
-p 4-> .P .P -P m oa>
CCCCE O Q.C
at aja)-
^r_^_r_r_ gT;, E m s_ ^
OOOOO3TOD OM-
winiflwtnjr .c CL
00 CTi O f— ' CM LD P^. CO
CMCVJCMCSJCMCM CM CM
CTl ^" rH C?
Ln ^- CM co
rH
p- cr> co csj
ro CM in
CM O CM CO
LO ^- "Q" LO
r— ( ^- CM "«f
Q~ CM ro u*)
r-- ^- en in
^- ro ro *d"
CM «*" CSJ LT>
uo ro ro <^
rH CO ro ro
LO o
in ro CM ps.
QJ QJ OJ QJ
ui in ui t/i
o o o o
CCXCO.CQ.CO.
E-Dg-OE'DE'D
-c JT £ x:
CD O rH CM
CM co ro fO
CM CM CM CSJ
-------
TO at
U £
a> a.
M O
O O
O ID rH r^
rH CO CO rH
I C
ro QJ
H-> x:
u o.
CM o
o o
Ln rH 00 rO
cn 01 r*-
CM
«5"
I C
- OJ
"3- x:
- O-
o oo m o
Cn ID ID ro
CO
ID
O f—
!c c
O OJ
i x:
•s- o.
0X1
TJ
OJ
=>
O)
c
I 01
ro NI
X C
O) O)
ac xi
i o
10 !-
CJ O
CO r-
- o
CM t-
* O
x:
Q-
OJ
in
O!
in
OJ
in .
OJ
t/j
OJ
in
OJ
in
v
in
OJ
in
O O OCCC O O O O O O O O
CQ.CQ.CQ.O) > > ro 'i— ro *r" ro *^ ro *r- ro '^" re 'r- ro *^ ro *r-
ET3 ETJ E "O r- r-t— ET3 E-D 6TJ ETJ ET3 ET3 ETT E"O
•jresrerjroooorjrorjrenrouroDrerirezirerjre
x: x: x: inminx: x: x: x: x: xi x: x:
a. •
E o
ID r- oo cn
CM CM CM CM
o
•J-
CM
133
-------
As noted in Figure 21, the 13C12-decachlorobiphenyl and the octachloronaphtha-
lene elute within a narrow retention window as compared to the retention window
for anthracene-d10 and the surrogate. These results suggest that additional
internal standards are necessary to provide better quantisation in the broad
scan analysis scheme. Estimates of the recoveries of the 13C6-monochloro-
and 13C12-octachlorobiphenyl surrogates by HRGC/ECD are difficult because of
coelution of other compounds.
G. Internal Standard Response
The response of the internal quantisation standard anthracene-d10
was routinely monitored and recorded to determine if there were apparent prob-
lems resulting from instrument stability. If drastic changes (greater than
50% of standard) in the anthracene-d10 response were noted, the HRGC/MS ana-
lyst was required to reanalyze a calibration standard to determine if the
response difference was due to instrument operation or sample extract matrix
interferences.
A difference in the internal standard response was noted for the 6%
and 15/50% Florisil fraction extracts. The differences were noted as signif-
icant changes in response when both the 6% and 15/50% extracts of a composite
sample were analyzed within the same day. The internal standard response for
the 15/50% was noted to range from 50 to 90% less than that observed for the
calibration standards and 6% Florisil fractions. The difference in response
is attributed to a sample matrix effect. Calibration standards and 6% Florisil
extracts analyzed before and after the 15/50% Florisil extracts clearly demon-
strated that the instrument stability was not responsible for the observed
internal standard fluctuations.
VI. REFERENCES
Abbott PC, Collins GB, Goudling R, Hoodless RA. 1981. Organochlorine pesti-
cide residues in human fat in the United Kingdom 1976-7. British Medical
Journal 283:1425-1428.
Albert L, Mendez F, Ipn C. 1980. Organochlorine pesticide residues in human
adipose tissue in Mexico: results of a preliminary study in three Mexican
cities. Archives of Environmental Health 35:262-269.
Barquet A, Morgade C, Pfaffenberger CD. 1981. Determination of organochlo-
rine pesticides and metabolites in drinking water, human blood serum, and
adipose tissue. Journal of Toxicology and Environmental Health 7:469-479.
Biros FJ, Enos HF. 1973. Oxychlordane residues in human adipose tissue.
Bulletin of Environmental Contamination and Toxicology 10(5):257-260.
Biros FJ, Walker FJ. 1970. Pesticide residue analysis in human tissue by
combined gas chromatography-mass spectrometry. J Agr Food Chem 18(3):
425-429.
134
-------
Burns JE. 1974. Organochlorine pesticide and polychlorinated biphenyl resi-
dues in biopsied human adipose tissue - Texas 1969-72. Pesticides Monitoring
Journal 7:122-125.
Cramer PH, Miller HH, Going JE. 1981. Literature review summary of analyt-
ical methods for adipose tissue and blood. Interim Report. EPA Contract
68-01-5915, Task 24.
Dougherty RC, Whitaker MJ, Smith LM, Stalling DL, Kuehl DW. 1980. Negative
chemical ionization studies of human and food chain contamination with xeno-
biotic chemicals. Environmental Health Perspectives 36:103-118.
Erickson MD, Stanley JS, Radolovich G, Turman K, Bauer K, Onstot J, Rose D,
Wickham M. 1982. Analytical methods for by-product PCBs--preliminary vali-
dation and interim methods. Washington, DC: Office of Toxic Substances,
U.S. Environmental Protection Agency. EPA-500/5-82-006; NTIS No'. PB83 127
696.
Eyster JT, Kimbrough RD. 1983. Partitioning of polybrominated biphenyls
(PBBs) in serum, adipose tissue, breast milk, placenta, cord blood, biliary
fluid, and feces. Archives of Environmental Health 38(1):47-53.
Fukano S, Doguchi M. 1977. PCT, PCB, and pesticide residues in human fat
and blood. Bulletin of Environmental Contamination and Toxicology 17(5):613.
Greer ES, Miller DJ, Bruscato FN, Hold RL. 1980. Investigation of pesticide
residues in human adipose tissue in the northeast Louisiana area. J Agric
Food Chem 28:76-78.
Jansson B, Wideqvist U. 1983. Analysis of toxaphene (PCC) and chlordane in
biological samples by NCI mass spectrometry. Intern J Environ Anal Chem 13:
309-321.
Jensen GE, Clausen J. 1979. Organochlorine compounds in adipose tissue of
Greenlanders and Southern Danes. Journal of Toxicology and Environmental
Health 5:617-629.
Kuehl DW, Dougherty RC. 1980. Pentachlorophenol in the environment; evidence
for its origin from commercial pentachlorophenol by negative chemical ioniza-
tion mass spectrometry. Anal Chem 14:447-449.
Kutz FW, Sovocool GW, Strassman S, Lewis RG. 1976. trans-Nonachlor residues
in human adipose tissue. Bull Environ Cont Toxicol 16:9-14.
Kutz FW, Strassman SC, Sperling JF. 1979. Survey of selected Organochlorine
pesticides in the general population of the United States: fiscal years 1970-
1975. Annals N Y Acad Sci 31:60-68.
Kutz FW, Yobs AR, Strassman SC. 1976. Organochlorine pesticide residues in
human adipose tissue. Bull Soc Pharmacol Environ Pathol 4:17-19.
135
-------
Kutz FW, Yobs AR, Strassman SC, Viar JR Jr. 1977. Pesticides in people,
effects of reducing DDT usage on total DDT storage in humans. Pest Mon J
LeBel GL, Williams DT. 1983. Determination of organic phosphate triesters
in human adipose tissue. J Assoc Off Anal Chem 66(3):691-698.
Lewis RG, Sovocool WG. 1982. Identification of polybrominated biphenyls in
the adipose tissues of the general population of the United States. Journal
of Analytical Toxicology 6:196-198.
Lopez-Avila V, Haile CL, Goddard PR, Malone LS, Northcutt RV, Rose DR, Robson
RL. 1981. Development of methods for the analysis of extractable organic
priority pollutants in municipal and industrial wastewater treatment sludges.
In: Advances in the identification and analysis of organic pollutants in
water. Keith LH, ed. Ann Arbor Sci.
Lucas RM, Pierson SA, Myers DL, Handy RW. 1981. National Human Adipose
Tissue Survey Quality Assurance Program Plan. Preliminary draft. RTI/
1864/21-11.
Mack GA, Stanley J. 1984. Preliminary strategy on the national human adipose
tissue survey. Washington, DC: Office of Toxic Substances, Contracts 68-01-
6721 (Task 21) and 68-02-3938 (Work Assignment 8).
MacLeod KE, Hanisch RC, Lewis RG. 1982. Evaluation of gel permeation chro-
matography for cleanup of human adipose tissue samples for GC/MS analysis of
pesticides and other chemicals. Journal of Analytical Toxicology 6:38-40.
Mes J, Campbell DS. 1976. Extraction efficiency of polychlorinated biphenyl,
organochlorine pesticides and phthalate esters from human adipose tissue.
Bulletin of Environmental Contamination and Toxicology 16(1):53-60.
Mes J, Coffin DE, Campbell DS. 1974. Di-n-butyl- and Di-2-ethylhexyl phthal-
ate in human adipose tissue. Bull Environ Contam Toxicol 12(6): 721-725.
Mes J, Davies DJ, Turton D. 1982. Polychlorinated biphenyl and other chlo-
rinated hydrocarbon residues in adipose tissue of Canadians. Bull Environm
Contam Toxicol 28:97-104.
Mes J, Davies DJ, Turton D. 1985. Environmental contaminants in human fat:
a comparison between accidental and nonaccidental causes of death. Ecotoxi-
cology and Environmental Safety 10:70-74.
Mori Y, Kikuta M, Okinaga E, Okura T. 1983. Levels of PCBs and organochlo-
rine pesticides in human adipose tissue collected in ehime prefecture. Bull
Environm Contam Toxicol 30:74-79.
Norstrom RJ, Simon M, Mulvihill MJ. 1986. A gel permeation/column chromatog-
raphy cleanup method for determination of CDDs in animal tissue. Intern J
Environ Anal Chem 23:267-287.
136
-------
Ribick MA, Dubay GR, Petty JD, Stalling DL, Schmitt CJ. 1982. Toxaphene
residues in fish: identification, quantification, and confirmation at part
per billion levels. Environ Sci Tech 16:310-318.
Rogers WM. 1972. JAOAC 55:22-38.
Sherma J, Beroza M. 1980. Analysis of Pesticide Residues in Human and Envi-
ronmental Samples: A Compilation of Methods Sected for Use in Pesticide Mon-
itoring Programs. EPA-600/8-80-038, Section 5,A,(l),(a) pp. 1-19.
Smith LM, Stalling DL, Johnson JL. 1984. Determination of part-per-trillion
levels of polychlorinated dibenzofurans and dioxins in environmental samples.
Anal Chem 56:1830-1842.
Sovocool GW, Lewis RG. 1975. The identification of trace levels of organic
pollutants in human tissues: compounds related to chlordate heptachlor expo-
sure. In: Trace substances in environmental health. Hemphill DD, ed. pp.
265-286.
Spearman R. 1982. Biochemistry of adipose tissue and its regulation.
Physiology and Pathophysiology of the Skin 7:2283-2325.
Stanley JS. 1985. MRI analytical method for the determination of semivolatile
organic compounds in human adipose tissue. Interim Report, Revision No. 2 to
Washington, DC: Office of Toxic Substances, U.S. Environmental Protection
Agency. Contract 68-02-3938, Work Assignment No. 8.
Stanley JS. 1986a. Broad scan analysis of human adipose tissue: Volume I:
Executive summary. EPA 560/5-86-035.
Stanley JS. 1986b. Broad scan analysis of human adipose tissue: Volume II:
Volatile organic compounds. EPA 560/5-86-036.
Stanley JS. 1986c. Broad scan analysis of human adipose tissue: Volume III:
Semivolatile organic compounds. EPA 560/5-86-037.
Stanley JS. 1986d. Broad scan analysis of human adipose tissue: Volume IV:
Polychlorinated dibenzo-g-dioxins (PCDDs) and polychlorinated dibenzofurans
(PCDFs). EPA 560/5-86-038.
Stanley JS, Stockton RA. 1986. Broad scan analysis of human adipose tissue:
Volume V: Trace elements. EPA 560/5-86-039.
Tessari JD, Griffin L, Aaronson MJ. 1980. Comparison of two cleanup proce-
dures (Mills, Onley, Gaither versus automated gel permeation) for residues of
organochlorine pesticides and polychlorinated biphenyls in human adipose tis-
sue. Bull Environ Contain Toxicol 25:59-64.
Watanabe I, Yakushiji T, Kunita N. 1980. Distribution differences between
polychlorinated terphenyls and polychlorinated biphenyls in human tissues.
Bull Environm Contain Toxicol 25:810-815.
137
-------
Wolff MS, Anderson HA, Camper F, Nikaido MN, Daum SM, Haymes N, Selikoff IJ.
1979. Analysis of adipose tissue and serum from PBB (polybrominated biphenyl)-
exposed workers. Journal of Environmental Pathology and Toxicology 2:1397-1411.
Wolff MS, Anderson HA, Rosenman KD, Selikoff IJ. 1979. Equilibrium of poly-
brominated biphenyl (PBB) residues in serum and fat of Michigan residents.
Bull Environm Contam Toxicol 21:775-781.
Wolff MS, Anderson HA, Selikoff IJ. 1982. Human tissue burdens of halogen-
ated aromatic chemicals in Michigan. JAMA 247(15):2112.
Wolff MS, Fischbein A, Thonton J, Rice C, Lilis R, Selikoff IJ. 1982. Body
burden of polychlorinated biphenyls among persons employed in capacitor manu-
facturing. Int Arch Occup Environ Health 49:199-208.
Wolff MS, Thornton J, Fischbein A, Lilis R, Selikoff IJ. 1982. Disposition
of polychlorinated biphenyl congeners in occupationally exposed persons.
Toxicology and Applied Pharmacology 62:294-306.
Wright LH, Lewis RG, Crist HL, Sovocool GW, Simpson JM. 1978. The identifi-
cation of polychlorinated terphenyls at trace levels in human adipose tissue
by gas chromatography/mass spectrometry. Journal of Analytical Toxicology
2:76-79.
Yobs AR. 1971. The national human monitoring program for pesticides. Pestic
Monitor J 5:46.
Zell M, Ballschmiter K. 1980. Baseline studies of the global pollution II.
Global occurrence of hexachlorobenzene (HCB) and polychlorocamphenes (toxa~
phene) (PCC) in biological samples. Fresenius Z Anal Chem 300:387-402.
138
-------
APPENDIX A
NHATS FY82 COMPOSITE SAMPLE DATA REPORTED FOR ALL
TARGET COMPOUNDS WITHIN A CENSUS DIVISION
139
-------
Table A-l. Summary of the Total Mass of Selected Semivolatile Organic
Compounds Determined in the Composited Human Adipose Tissues
Representing the Mountain (MO) Census Division
Census division
Composite no.
Age group
Wet tissue weight
% lipid
Compound
Dichlorobenezene
Trichlorobenzene
Naphthalene
Pentachlorobenzene
Diethyl phthalate
Tri butyl phosphate
Hexachlorobenzene
p-BHC
Phenenthrene
Di-n-butyl phthalate
Heptachlor epoxide
Pyrene
trans-Nonachlor
p,p' -DDE
Dieldrin
£,p_'-DDT
Butyl benzyl phthalate
Triphenyl phosphate
Di-n-octyl phthalate
Mi rex
Tris (2-chloroethyl) phosphate
Total PCB's
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Nonachlorobiphenyl
Decachlorobiphenyl
Total
(1)
0-14
9.0 g
62.3
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.20)
b
b
ND (0.20)
ND (0.20)
ND (0.20)
b
ND (0.20)
ND (0.20)
ND (0.40)
5.1
ND (1.0)
tr 0.21
b
b
b
ND (0.20)
b
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.40)
ND (0.40)
ND (0.40)
ND (0.40)
ND (0.40)
ND (1.0)
jjg/composite
MO - Mountain
(1)
15-44
18.3 g
74.1
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.50)
ND (1.0)
0.31
1.5
ND (0.20)
ND (2.4)
ND (0.20)
ND (0.20)
ND (0.40)
8.1
ND (1.0)
0.90
3.6
tr 0.89
ND (0.20)
ND (0.20)
ND (0.80)
1.2
ND (0.20)
ND (0.20)
ND (0.40)
tr 1.2
ND (0.40)
ND (0.40)
ND (0.40)
ND (1.0)
specimen3
(1)
45+
21.0 g
84.3
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.20)
0.87
ND (1.0)
0.59
4.6
ND (0.20)
ND (0.20)
1.0
ND (0.20)
2.8
24
ND (1.0)
2.4
7.8
9.6
ND (12.2)
ND (0.20)
ND (0.80)
11
ND (0.20)
tr 0.44
tr 2.2
4.8
3.3
ND (0.40)
ND (0.40)
ND (1.0)
ND = not detected. Value in parentheses is the estimated limit of detection (LOD).
,tr = trace. The compound is present at a level between LOD and LOQ.
Data not summarized.
140
-------
Table A-2. Summary of the Total Mass of Selected Semivolatile Organic
Compounds Determined in the Composited Human Adipose Tissues
Representing the New England (NE) Census Division
Census division
Composite no.
Age group
Wet tissue weight
% lipid
Compound
Dichlorobenezene
Trichlorobenzene
Naphthalene
Pentachlorobenzene
Diethyl phthalate
Tributyl phosphate
Hexachlorobenzene
p-BHC
Phenenthrene
Di-n-butyl phthalate
Heptachlor epoxide
Pyrene
trans-Nonachlor
p,p' -DDE
Dieldrin
E,2'-DDT
Butylbenzyl phthalate
Triphenyl phosphate
Di-jr-octyl phthalate
Mi rex
Tris (2-chloroethyl) phosphate
Total PCB's
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Nonachlorobiphenyl
Decachlorobiphenyl
Total
(1)
0-14
19.1 g
55.1
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.20)
tr 0.34
ND (1.0)
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.40)
1.4
ND (1.0)
ND (0.20)
ND (0.20)
ND (0.40)
tr 0.69
ND (0.20)
ND (0.80)
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.40)
ND (0.40)
ND (0.40)
ND (0.40)
ND (0.40)
ND (1.0)
ug/composite specimen
NE - New England
(1)
15-44
21.9 g
87.6
ND (0.20)
ND (0.20)
tr 0.60
ND (0.20)
tr 0.32
ND (1.0)
24
11
ND (0.20)
ND (0.20)
4.48
ND (0.20)
9.9
47
ND (1.0)
6.8
ND (0.20)
ND (0.40)
tr 0.24
tr 0.70
ND (0.80)
2.0
ND (0.20)
tr 0.36
tr 0.46
tr 1.2
ND (0.40)
ND (0.40)
ND (0.40)
ND (1.0)
(1)
45+
26.7 g
79.2
tr 0.77
ND (0.20)
ND (0.20)
ND (0.20)
tr 0.38
ND (1.0)
tr 0.31
2.0
ND (0.20)
tr 0.28
ND (0.20)
ND (0.20)
ND (0.40)
20
ND (1.0)
7.1
ND (0.20)
ND (0.40)
ND (0.20)
tr 0.60
ND (0.80)
3.4
ND (0.20)
tr 0.23
tr 2.72
ND (0.40)
ND (0.40)
tr 0.43
ND (0.40)
ND (1.0)
ND = not detected. Value in parentheses is the estimated limit of detection (LOD).
tr = trace. The compound is present at a level between LOD and LOQ.
141
-------
Table A-3. Summary of the Total Mass of Selected Semivolatile Organic
Compounds Determined in the Composited Human Adipose Tissues
Representing the Pacific (PA) Census Division
Total ng/composite specimen
Census division
Composite no.
Age group
Wet tissue weight
% lipid
Compound
Dichlorobenezene
Trichlorobenzene
Naphthalene
Pentachlorobenzene
Diethyl phthalate
Tributyl phosphate
Hexachlorobenzene
p-BHC
Phenenthrene
Di-n-butyl phthalate
Heptachlor epoxide
Pyrene
trans-Nonachlor
£,p_'-DDE
Dieldrin
p_,2'-DDT
Butyl benzyl phthalate
Triphenyl phosphate
Di-n-octyl phthalate
Mi rex
Tris (2-chloroethyl ) phosphate
Total PCB's
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Nonachlorobiphenyl
Decachlorobiphenyl
PA -
(1)
0-14
19.7 g
62.9
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.45)
ND (1.0)
tr 0.37
tr 0.48
ND (0.20)
ND (0.76)
ND (0.20)
ND (0.20)
ND (0.40)
3.2
ND (1.0)
tr 0.27
ND (0.20)
ND (0.40)
ND (2.3)
ND (0.20)
ND (0.80)
ND (0.20)
ND (0.20)
ND (0.20)
ND (0.40)
ND (0.40)
ND (0.40)
ND (0.40)
ND (0.40)
ND (1.0)
Pacific
(1)
45+
22.0 g
19.2
ND (0.20)
ND (0.20)
tr 0.20
ND (0.20)
ND (0.49)
ND (1.0)
1.7
b
ND (0.20)
ND (2.6)
ND (0.20)
ND (0.20)
ND (0.40)
ND (0.20)
ND (1.0)
ND (0.20)
1.7
ND (0.40)
16
ND (0.20)
ND (0.80)
6.7
ND (0.20)
ND (0.20)
tr 0.71
tr 0.44
2.8
2.2
tr 0.56
ND (1.0)
a
ND = not detected. Value in parentheses is the estimated limit of detection (LOD;
. tr = trace. The compound is present at a level between LOD and LOQ.
Data not summarized.
142
-------
T3 C
O) O
C •!-
•r- O>
C OJ
3 O
O
U U
E 4J
ro C
Ol TO
S- t—
O 4->
s£
01 4J
Ol
"D C
OJ • ,-
u c
Ol OJ
I— t/>
QJ 0>
I/) S-
•3-
*-» in CM h~-
/^«t . .
: rH i m o
: s^in CM co
«Sr c\] r—
> t-H
'O CM CO
«• O IT)
f-~* rH .
[ f-H i C"o r*v
: ^o CM r-
w o
o>
• r- O) Q- 3
"O 4-* 3 Ifl
•r- O OJ TJ
3 O Ol+J O-
l/> CL •>—
e E 01 4J _i
QJ O CD Ol
O c_> - -
O
D.
E
O
O O O O *3" OOrH OO COOOO *^^
OOOOOrHOrOO*3-OOOOinCMl£JrHOOO rHOOi-HOOOOrH
S-Ot-OOOO O OOO OOO OQS-S-OOOO
OOOOO'-^O O^£)C\JOCM *^sOOOrHOrH OO OOO-—-
O
QOOOOrHOCMOOOOOrHrHOOOOOO rOOOrHr-tOOOrH
OOOOOOS- OS-S-OS- OOOOS-OO Ot-S-S-OOOO
OOCMOO'—>Z4^ ZZ ZZZ Z4-> ZZZZ
OOOOrH^ COCM O r-~ CMO OrH Oro lOOO^-
C\J CM C\J CM "et" O rH ^ f^ ro C\J CD O CD CO ^ t~* CM CO LT1 CM to ^f1 O ^ ^ ^" O
rH in
OOOOOrHrHCnOOU3OCTl«d-rH*}-OOrHOO *3-OOrHCMOOOrH
OOOOS-O S-S- O O O OO OI-S- S-OOO
ZZZZ4->Z 4->4J Z Z Z ZZ Z4J4J 4JZZZ
O O C3 O ^N m O O O C3 O '*"^ rO O O *^ O O"> O O O O ^**
OOOOrHr-iorHOOOOOCnrHOCOrOOOO CMOC3C5rHOOOrH
oooo as- oas-at- a aoa os-s-s-oooo
ZZZZ Z4-> ZZ4->Z-r' Z ZZZ Z4->4->4->ZZZZ
O O O O O '"•N ^* O rH CO O l£> ''^ OOOOrH OrH OOO '"*
U1
OOOOOrHOrHOOOOOrHrHrHOOOOO COOOrHrHOOOrH
D O Q
O S- S- O S-
Z 1J 4-> Z 4J
a o o o a
z z z z z
O S- !-
Z 4J 4->
O 1
z :
!§§
OJ
c:
OJ
C OJ •
Ol 4J
N TO .
C r-
Ol TO
o a> o a.
o "TO jE •— ":
— .c u >,4
o.caj'
ina)"-
ZQ-Or
ro 01
•— T3
TO •(-
4-> O
jz a.
OJ CL O>
Ol — t-
s- >> o
u
TO
C
O LJJ C r-
Oj
4J Ol
TO 0) 4J
4-J O.JC
J= t/J 4->
a. o £
f CL
r- CL
CL
O
a.
^
>> >)!— >1F- r— r—
c"*"
OJ O
OJ CL
Q.-D
•r- O
J3 t-
O O
i. i—
O .C
r- U
~ TO
CLJ1
•r- CL
o !£
s- o
o s-
•— o
T- Q. CL Q.
o o
S. i.
o o
s- o
O i.
r- O
ro u ro u u u
JOTOl TOCUlll'Oli— .
: CD Ol I CL S- TO ICU OJ CU-r^ T- 1 S- -r-
j i f -i- ai >t s- -"- - 3 s- T- -f- i.
: cao- o x ex 4J1040 cgco 1—02:1-
O-XZOZO
0>
a.
o
a.
E
01
01
CL
c
O Ol
~O —I rg
01 -r-
4J T3 S-
O C TO
ai ro E
OJ O 3
"D O w>
H S re
143
-------
•o
QJ
'«
CL
e
Q
CJ
-c
c
c
•O O
QJ .—
c m
E >
0) O
Q 3
in
in C
T3 O>
C C_J
3
O >— *
CL-Z.
E LU
o *— •"
o
U TO
c: 4-J
en TO
E
OJ OJ
^J
QJ CJ)
•M C
U -r-
cu v
QJ OJ
*4— U
OJ
in Cd
E: QJ
=3
TO l/>
4-> .,-
O r—
I —
CD
-C 0
4-J O.
!4— "D
o «o:.
>> c
t- TO
i ^
LO
LT>
1
0)
.Q
TO
**~
TO
C
QJ
E
OJ
Q
in
QJ
4-9
I/)
O
E
0
u
CT
H
TO
O
r-
^ cxj no
Z ro in ro LD
LU • — - ^- CM CO
CM CM
z CM m tn ro
LU v- - ^r- CM co
CO i£>
Z rH LD Cn O
^— ' ^" CO
^3- CM CM
Z ro i o ro
LU *— ' Lf) C\J CO
i-H
^^^ *3- CM
Z CM 1 rH CO
LU s— ' Lf) CM CO
rH
«=r «x> LTJ
Z rH ( rH UO
rH
^" CM ro
Z CM^T1 rH Cn
^ rH i£>
Z rH t CO 00
UJ >«' O rH ^~
CT
XI
C O^
o •*—
•r— . QJ
(/) O ?
•r- C
> CD
•r- OJ CL 3
•r- O in -C C
in in t. •»- *r- u
3 O CT-P Q. O
i/) >Q. *r- Q.
C E QJ +J —1 E
QJ O CT QJ O
OTfOOO'-^r- O 0 O O OrH
OOOOOrHOroCSr-lrHOrH rO O rH O •— 1 O O
^^ s^/^,, ^x^, s^ s^, s_^ S«/ S«^ S^
OI-QOOOt- O S-Qw t-O Q OQ
Z-*->ZZZZ-*-> Z ^Z^-J *->Z Z ZZ
O O CM O tD - — > U3O O OCTiOOrH
, (Sg , , ,
X^V-' S_^ S^- S_> S_^ S_^ S^"^XV^
oos-os-oi- o s-o o s-ooo
ZZ-*-)Z*JZ-»-> Z -*->Z Z -4-^ZZZ
is s s § o s oo s s s i~§s sis §s?s s
OOOOOrHOrOOOOOO rHOOOOOO
O O S- O O O i~ O Q t- O C? CD O t- C^ Q Q C^
Z Z +^ Z Z Z 4-1 Z Z •*-* Z Z Z Z 4^ T?" Z Z Z
^*S ^^« ^V /**\ ^~N /"> /""N
O «S-CM«3-CO CMCO
OOOO^JDOO r>r->(~^r^Lnjj-Q_f).p_Qgnf7i
«*^ ' *v* •**** ^-^ CD ^^ s^^ s^^-
S-QOQ OS- t-Ot.. QO
4JZZZ 2-*JO *->Z*J ZZ
O O O O ^^» rH O LD O O *^ CM O rH
esjcMCMCMCMOLnr^cMcnrocM^-^-roLn OIHCMCO
OOOOr- IrHOrHOr-OOOOrOOrHCTiiXJOO
OOOO OS- O S-QC2S- S- QQ
ZZZZ Z*J Z 4-JZZ-4J 4-J ZZ
O O rH O rO '""•> i-H O /™^ O O O *•""*« O CD CM O rH
CMCMCMCMrOOLOmCMCMCMCM^-roO^CM^-COCMCO
OOOOOrHOrHOrHOOOcdrHrHOOOOO
QOt-OOOS- QOOOO Q DOOOO
ZZ-MZZZ*-) ZZZZZ Z ZZZZZ
O O O O O CsJ *^~ t^ O O ""^ CO CM O1 -^^ O rH
C\JCMCMCMl£>COCM«3-CO CMCM^CMOCMrOgroCNJCO
OOOOOOrHOOOCMOOOCMrHOOrHrOOO
OOOQ &. O L. &. t-QO OS-I- OOO
^ Q Q Q prj ^^^ Q Q Q ^.^ O O O •-•*• O O ' • O rH
CMCMCNjCM*a-OCMCMCMrOCMCM1Cj-rHOC\JrH ^N
QJ QJ -^J TO C TO *r- _r* ^7 oj _g~
CQJ C r— CL N -*->O O jCin-*-J Q>
islC -G -C O QJ QJCLQJ XI J^CL S-
OI^SCi-^CLO O)r-S- TO >) •— —
^JOCUOCL i- S->iO C Mf— >, -C
OS--—P- r-o z:-pr— OLUCI— c >,-P a
i_ o TO .c i— >^r— 4-^rj^ zo-i-oojcu i
O-'-CLCOJ-'-XCDOJl CLS-TOQ4CU OJ-*-> T- ( i- ••-
•f- i- TO OJ *r- S- QJ t JZ -r- QJ >> I_ - *r- -3 U -r- 'i- t.
Or-zn-ot—z cacL.oxci-4-)| ojo taico t— Q s; f—
CO «3- O *-*
LncMr-*^"COCO^-|'!t'O
r-.OOrHCMjrHi— IOrH
' -^-^
t- i- I- t. Q O
•4-> -t-> 4-> *J Z Z
O O O
rHOOCMLOCMrHOr-H
*~*
S- Q J_
*J Z 4^
OOOOOOOO-— v
ro ro c\| ^ ^- ^" ^f- <}• O
OOOOOOOOr- 1
I-QOQOQOO
^MZZZZZZZ
^"N f~*. ^™N f~*, /**>.
OQCOOOOQ^-
fOCMCM«3'CO'^-«3-^'O
rHOOOOOOOrH
QO t- £~OOOO
ZZ-P-PZZZZ
O CM LD O O O *-*•
cocMCMLno^i-^-«d-o
iHOOOrHOOOrH
O t- S- S-OQQO
24->4-)+^ZZZZ
O O O O Lf) Cn O '•"I
rHCMCM«eJ-^-l£l^-^J-O
rHOOOOOOOrH
OOOO S- I-OQ
ZZZZ-«->4->ZZ
OOOOOOOO'^
C\jCMCM*c}-^-^,f^-^3-O
OOOOOOOOrH
ooooooooo
ZZZZZ2IZZZ
oooooooo-*-^
CMCMCMrf-^-«^«^^-O
OOOOOOOOrH
oooaoaoao
zzzzzzzzz
^1 >>l~~ 5*1 <~~ r— 1—
•— ccxc^^^
^QJQJCCUCCC:
O CL Q. ^ d.^ f*- _c-
-C -r- -r- O..F- Q. Q, Q.
a. JQ .a ••- .a -i- -r- -r-
*r— O O -O O JD ^ ^
^3S-1-OS-OOO
OOOS-OS-t-S-
in--r-r— Or- OOO
CO O-C^ — ^Ir— -— r-
Or— u u-c UJ^^:^
£i-.CTOTO
^
r—
QJ
OJ
TO
TO
,p
C
a>
tn
OJ
S-
CL
I/)
•o
3
O
i-
o
u
01
.c
I—
a>
(j
ro
I
O
3
c
o
4->
o
OJ
(1J
^_
0
+•>
E
r-
•Q
OJ
ro
B
'_C>
ul
x:
in
•r-
in
01
jr.
4-'
c
£.
r:.
c.
c
a
^
ro
•D
. QJ
•a M
OJ -r-
u ro
OJ E
4_> t=
QJ 2
"D in
O O
C C
II ro
4->
O ro
•z. o
(O J3
144
-------
Ol
.C
C
•r- C
o
•O •!-
c •'-
E"~ lr_
Q
OJ
4-1 in
01 3
Q in
C
i/) 01
•o o
C
3 X-N
0 2
O-S
O ^^
LJ l—
0 S-
C C
(D OJ
i-
O -C
4->
OJ i-
•— O
~4J
ftJ 4->
0 01
> u
E 01
iX 4->
TJ D;
Ol C
U 4->
01 C
i— OJ
O> in
t-
i*- O-
O OJ
l/>
JO OJ
l/l
F— 1/1
(0 .r-
o
r— OJ
in
Ol O
.C D.
4-J -f-
•o
"- «
o
C
>, ra
i- £
re 3
l/> Ol
.,_
- If)
l£> O
it
o
01 O
.0
re
1 —
C
01
•1?
O)
D.
in
OJ
in
0
a
E
o
U
CT
ro
o
x-, *•*•
§ Si if? CM S
in ao
H >*-^ <3- CM 00
^- l^ C\)
x-^«3- . .
3 ^-^ LTJ c\j r~~
.—.r-H . .
^ ^— ' O C\J l£)
Ol
C O)
O T-
i/JO 3
r- C
> OJ
i- aj a. 3
•i- O in T3 C
in in s_ "- -r- a
3 O Ol+J Q. O
W Q. -r- Q.
C E Oi J-> -J E
Ol O O 01 O
OOOO x-s
0 0 0 0 rr> rH
O Q Q O Q
_^ ^
C\J C\J ro OJ VD O
O CD O O O i— t
o o s- a s- o
OOOO /— ^
O O O O r-l rH
OOOO O
O O O O O .-—s
0 0 0 0 0 rH
^~S^~' S^-'S^/S^-
Q O I- O O 0
Z "Z. •*-> Z Z 2
a> QJ
QJ QJ -M re
QJ C M TO -C
CO) C f— Q.
QJ N QJ (0 CO
N C o XI O
C QJ QJ O +•* f"
O S- r— f— f—
o •— x: u >>4J
-.- s_ re a> ••— s-
O J— Z G_ O t—
o o
0 rH 0 rH
o o
_
o o c\j *r
^H tX> OCNJ
s- o o
C\J O O
10 CT) CM C\J
O rH O O
s- o o
en r^ o
o o o esj
'^^
s- o
4-> Z
QJ
4->
TO
c re
Q) J*"
Nt -l->
QJ QJ O
J2 C
O OJ i—
O x: 4->
QJ r x: •—
Z CC.Q- O
rH O P^-
°s°
t- o s-
^
rH CSJ in
i-l 0 rH
t. O 1-
ro O «*•
000
i~ O !-
i-l O O
000
^ ••**'
i- a o
4J 2 2
OJ
X 1-
o o
D. •—
(J
!- to
i— O
£" >> 2|
z£V
O ^^ O rH
rH rH ^3 «• "^,0,°,
o a o o
x^x^
»3- x~. O rH
pr, 1^ cvj IC^CSl 0_0
a o o
rH O kD O O rH
ro CM 01 01 c\j <\j co
i— ICMOrHOOOO
1- O Q O O O
ID O O rH
^"
1— 4-) 10 r—
TO ro i— >,
4-> D.^ *J
j: in 4J 01
-CO. S-
— O- O
>>"—•—
UJ C 1 — C >)4-> U
-a/aT^I'l-f^!'
CUO CUCO r- D Z r-
o m
f> O O
O fc.
"• rH
rH O rH
k. S-
O 00
CO , OJ
ai a.
•r- O
JD !-
o o
l« !- r-
CO O .C
O — (J
ro s- 01
o
r-
S3«
O rH
<- *-
CM «3-
rr> ID
CO
O CM
CM O
O rH
S- £-
*>, p—
01 C
o.^
•i- a.
o 5
i- O
O I-
j: i —
U -C
C X
01 Ol
siio
O 0 O rH
^ Q O O
m tn LO o
OO r_( o rH
i- i~ O
l£> O^^-^
CsJ O- ^f O
rH O O rH
o o o /- N
O O O rH
^"^ ^^ s"-1 ' s""'
OOOO
.z z 2:
>1 r— r>— r—
QJ C C C
Q.X: x: x:
"~ o. a. a.
.O -^ -1- T-
i- O O O
O t- S- S-
i — O O O
O XI XT -.C
CL-*J C U
QJ {J O QJ
TO
re
c
QJ
U)
QJ
S-
D.
-o
c
3
o
Q_
o
u
OJ
r-
a^
u
re
i_
II
s-
^
o
o
_J
's-^
c
o
'•£
u
QJ
-D
^_
o
4->
E
l~~
•o
a>
re
E
in
Jl
^_)
•r—
in
QJ
QJ
x:
•*->
c
QJ
S-
re
CL
c
QJ O1
3 O
1 — — J
ro
> T3
re ~o
a>
•CON
QJ O •'-
4.J — 1 1-
U TO
Q) C E
•f-9 QJ E
QJ OJ 13
*-> QJ -t-J
O JD O
c c
li 'a! re
Z i — O
re £3
145
-------
:>mposited
CJ>
tu
.c
+>
•o
cu c
c o
t- •!-
cu >
4-> ••-
OJ O
o
in
i/l 13
•D ui
C C
13 OJ
O O
CL
E "->
LJ UO
(J
•r- U
C •<-
fO -P
O) C
S- ft!
o •—
-P
o>
-,- o>
15
oo
Ol
•o c
Q) ««-
-P +J
u c
1 — I/)
O) QJ
00 S-
CL
*t- 0!
0 CC
in U)
in OJ
(D 13
(/I
•P
h- in
O
QJ D.
_C -r-
•P -O
> E
S- 3
E "~
3
oo
r-
t
^~
OO ^^-'LTi T— ( rH
i-H
•^ •• 4- o r*-
tn i— i co
rH
«3- C- <3-
/-^. «y . .
00 '*- ' ID CSJ CO
«3- rH t-H
00 '^-'O rH \£>
^r rv. en
CO **^ O C\J CO
D)
s« '
4->
J=.
C O)
o •*-
•r- . OJ
WO S
• f- C
> 0)
•r- at ex 3
"D 4-> 3 i/> "O
•r- O in ~O C
Ul I/) S- •)—•(— ^
13 o Cn-P CL O
i/) CL T- CL
c E a* -P _ J E
'^ OOr--GO
CsJCsOCsJC\JCsOO«a-CSJCsjrOVr)C\J^-^-OCOCNJ^-C\JC\jCO
OOOOO<— IOCNJOOOOOO-— ICXJOOOOO
QOOOOOI- OOS-QOt-O OOOOO
2i2:zz2:z4-> ZZ-^ZZ-MZ: zzzzz
OCOOO'^>roo O O
C\(CJC\|C\J OCMLDCM OOOCNJ C\)
OOOO^lrHO'-IO rH O .— 1 rH O
Ol-OOQS-O QS- Q
2=4->ZZZ-«->Z Z-P Z
oorHoo-^^r^- o-^sroot-n '~-vOOor*.coo
C\JC\J^-C\JCsJOC\JCVCSJC\J*3-CSJ^I- C^C\jCSJQ-CS)LncO
OOOOOrHOrOCDrHOOOfO"— tOOOOOO
QOt-OOOS- OQt-OS- QQS-QUS-Q
zz-^zizz^ zz4Jz:+j zz*J24J*J2:
^-- ^^
^-s m ^- o
O O ID CT> U5 r^ CO
rHrH rH rHLOrHrHOO
•*— ' %^ ^w'
a o o
z: z 2
oocooo^-- o^-^ooo oooo
C\JC\J^-C\JC\JOf\jr^CvJCOCSJ(\J^- 'H^J-ID'^-CSJCSJCO
OOOOOf— trH^-OrHOOOrHrHC\Ji-HOOOO
QOI-OOQ OOOC3O i- OQOO
zz:-^z2:z ziz^izz -^ zzzz:
oor-ocr>'->^rLno rooo ^^> coo^^-rHo
C\IC\|(-DCM«3-OCsjCrtC\l fOCSJCSJ OOOC^^CTiroCO
CDOOOOrHOOOi— tOOrHrHrHl£tOOrHOO
OQt-OI-Qi- I- (-OS- O S-QOI-Q
zz*->2*JZ-*-> -u *J2*J z *JZZ4->z:
OOOOOl^sO O COO r-l OOO
cxjcsjCMexj^ocMrHcx/r^Lncsj (nroesjcDU><\jc\jco
OOOOOrHOf-HOrHOO^lCO«\|C\irOrHOOO
OQQOi-O£- O S-O i- OOQ
zzzz^z^ z: 4^z 4-; zzz
OOvcoO'^^ro OO/^NOOO ^N o-^-esJO
CMCNJrHCSJO^CSr^CSjrOrOCNJCM^J- O<^O^J-OC)C\JCO
OOCZ)OOrHOC\)OrOOOOrHrHrH£SJOtDCDO
OOQOOQS- s-aoao a oot-o
ZZZZZZ-t-> ^ZZZZ Z =Z4->Z
oorHoO'-^ocno ooo /— >csj oo
c\jcsj^rcMCNjoc>oLncx(OCMr\j^-(jDor^cMC\icriC\ico
OOOOOrHOOOrvJOCDO^fi— lO^rHr^OO
QQS-OQQOS-Q OOQ OS- t- OO
SZ-MZZZ-E-MZ ZZ3E Z-*J ^-> ZZ
oo O'-NOvn O'-s<3-oo '-s ^oooo
^JC\JrHC\jrOrHl^LnCNIOOLnC\JP*«-f1OOrHLn^'CSjrsJCO
OOrHOt— tOOrOOrHOOOr--i— trHOOOOO
QO OQOt- OOi-OS- O i-OOOQ
ZZ ZZZ*J ZZ-*JZ-M Z -»->ZZZZ
O)
CD 4J QJ i
-p 03 QJ 4-> •— s
atai roa) *— 4-> TO ! —
COJ4-JQJ i — "D fOfD' — >^
a> ai+Jfoc: w-r- ^^TTOX:
OiC rxirC-CCU ^IX t- -P CL^r •*->
CO) C f— CL N +^O O .Cin+J tti
OIM airomc .CCL-— CLOX: o
NJC: ^^roo) OJCLOJ .c -CCL t-
ccuajo*J-c^: c (j •— c- OQJ
ai^cs-^rcLO cu — t. TO >^ r— i— *j
.OOCUOCL s- s->,o c H-— >^ x:ro
os-i— •— r- o -C4J-— oujCh-c^-*-) ux:
s- o TO j=. *— >,•— *JZ3jr zo"-oa>cu i CL
O *— XT U X-i-» ^ CJ3UO)lOS-OJ2QJO CSiW
r— ^l4->fDX:3UOTOl TO C ifl 1 I "D 1 ^- .C 1 X ^~* O
.cu^-t->-*->^TOzcc|-*-iatch f— - >}CLCia)vi-c
UT-o.caiT-XQDa»i CLS-TOOJOJ aj-t-1 •>- i s- ••- CL
••- (_ in a *r- i- a> i -c •*- oj >> i- -••- * 3 s- •-- -r- i-
o)~ ZQ.QI— _rca.a.a:ra--p| ajo ajca h- o 2: h-
i — i
«j-c\jro«3-cncr>cocn
C^OrHCXJ^-1— («3-POrH
t- i-
4-J ^J
O
Oc\jrocoor-'Q-^o
^•OOOCMOOOrH
OS- fc. O O O
Z 4J +J Z Z Z
O C\J O O '— •
csjr**-ix>OLor--^-o
rHOO^-r-vCSJOOrH
01- S- 0 Q
2 •»-> -P Z Z
^-s
O CO O
csjcnroLOroo^rH
rHOOCMC-CNJrHOfO
t- i- O t-
+J -P Z -*->
cooooror^o^^
N-rOCM^«3-COCO^"O
CsioOOOOOOrH
s-o t-a t- s-oo
•PZ-MZ-P+JZZ
r- ^- CNJ o '-^
Q-r-IC\JrHi£>Lncn^-^3-o
roOOrHOr-HOO'-H
O O i- O O O
Z Z -P Z Z Z
oooooooo-—>.
fSJCNJCNj«3-^-«g-^^j-o
OOOOOOOOrH
ooooaaooo
zzzzzzzzz
O O CTi CO O O O '•"v
LDcsje\imcn^-«3-^to
rHOOOOOOOrH
Total PCBs
Trichlorobiphenyl ND
Tetrachlorobiphenyl ND
Pentachlorobiphenyl tr
Hexachlorobiphenyl tr
Heptachlorobiphenyl ND
Octachlorobiphenyl ND >
Nonachlorobiphenyl ND
Decachlorobiphenyl ND >
CX
O
_j
•D
C
TO
O
0
evel between
TO
4-J
TO
4->
C
CD
VI
OJ
s_
CL
ie compound is
H-
O>
U
TO
s_
4->
II
i.
O
o
-J
c
0
4->
OJ
•p
o>
•D
<4-
o
*->
-o
estimate
.c
4->
in
)arentheses
,ND ~ not detected. Value ir
Data not summarized.
146
-------
QJ
4->
C
""" o
OJ in
C T-
E —
QJ
4-J tn
QJ 3
O tn
c
u> at
"O O
c
O
c c
ro QJ
CT5C-J
O JZ
QJ D
r— O
"- I/)
TO 4->
• — in
0 to
> LU
E O>
QJ JZ
tn 4->
"D D)
at c
u Zi
QJ C
•— QJ
QJ in
LO QJ
I-
M- Q.
O OJ
C£.
if)
TO QJ
s: D
in
i— in
ro -r-
o
f— ai
QJ O
x: a.
4-> ••—
0
c
>> ro
s- e
TO 3
E 31
E
uO QJ
• r—
• in
CO O
i CL
Cn ro
rH i— 1 CO
<*n i— t i co r*-
UJ s— •* O C\| p^
D)
4_3
C Ol
o —
•I- • QJ
wo 2
> at
••— QJ O. 2
T5 4-1 3 W ^
-(— o m "D c
1/1 in i- -i— -i— 3
3 o 0^4-* a. o
tn CL -r- CL
c E OJ 4-> _j E
o 0 Z24JZ 2 ZZZZZ
OOOO r^. f— 1 O O Or-4
CMCsjcsiCM ^rcoro r--CMT-< CM CMCO
OOOOJ2JSOCT»OXlr-tO^-^- OJ2X1JOOO
OOQO S-I- O O OO
O O f-». O *^*N CM O O ^" O rH
CMCMCSjCMi-HO^rCOCMOOCOCSJ^D • ^J-fOr-ICMCO
OOOOCMrHOtX>OCMCMO^-^rHJDCT>rOCMOO
QOi-OOt-O O OQ
Z24-)2:2:4->Z 2: 2Z
CNlCMCsjCMOOOLnLOCM^rrOCMlT)t-HO«X>r^OCMOO
O O CD O i~H tH O CO O ro O O ^^ ro ro 0"* Is*". CM C\l O O
•s^ ' S.^ Sfc^ \^S ^^ '**S S_^ S^ S_^
O2OQ OS- i- S-QI- S- OOO
OJ
TO
Q.
in
O
OJ CL
QJ 4-> at
QJOJ TOO* f^4_>TO'—
COJ4JQJ -— TD TOTOr— X
QJ QJ4JTOC TO--- -C-CTO-C
OJC tsiTOJTOJ JZX E- 4-> Q.J^ 4J
CQJ C r— a. NJ 4JO O xrin4-> QJ
QJ Nl QJ TO in C -f~ f*> ^— Q_ o .C O
NC J3JZOOJ OJCLQJ JZ JZQ. S-
OS-i — i— -— O JZ4-ii— OUJCI— C X-r-J U
!- o re JT: •— X-— 4J3jr ZO-I-OQJCU i
i— jr-*-»fOx:3| OJQ OJCQ f— O 21 r—
o o ^->
CMCMCOV£>«3-CMrHO
j_O
CMOOCSJCO\DLOi-*rH
O O S- Q
z z: 4-j 2:
O O O CM O <-^
roc\iCMCM^'^d-ro^-o
rOOOrHOOrHOrH
oot-os-s-s-o
zz:4-'z:4J4J4Jz:
O CO CO '-N
CMl£t^J-CMCMf^-U2O
r— tOO*3-r-.rO-— IOrH
o s- t. s- o
2 4-> 4-» 4-> Z
OOO O ^-s
*X>CMCMn-LOCOi— t^"O
r^OOO^-i-Hr- IOr— 1
•s— ' V S^-'v^'
i- O Q O Q
4-> Z 21 2: 2:
X >>»— X— — <—
^CCXCXX>,
XQJQJCQJCCC
c ^r jz QJ j~ QJ at at
OJ CL Q.JT CLX: x: x:
-C ••- -r- Q..P- CL CL Q.
CL XI XI •— J3 T- -r- •»-
•t— o OJ3 OXSX1X1
X)!-l-Oi-OOO
OOOi-OL-S-S-
ini-r— r— Or— OOO
CO O-CJZr— JT«— •— »—
o— u DJ= UJT.CJS
CL.JCTOTOC(J
rot-atajQja'UOQj
4Jr— r- C_3ZZCO2:Q
O
t—
QJ
TO
4->
^
C
QJ
t.
D.
W
C
o
CL
0
U
at
x:
r—
at
u
TO
&_
II
i.
+3
o
-J
c
0
4->
U
at
at
^3
O
«r—
e
-a
QJ
TO
E
•*J
m
QJ
QJ
^5
in
in
QJ
in
QJ
.C
C
at
TO
Q.
C
OJ
ro
. o ai
at T-
4J T3 S-
u c ro
at TO E
at o 13
"O O m
I
O C O
C QJ C
QJ
M 2 TO
Q QJ TO
21 XI O
TO XI
147
-------
OJ
5
c
o
•Q -P-
C 'r-
E •'-
QJ
QJ 3
O in
c
in QJ
T) 0
c
3 -—^
O on
0.3:
E *— '
0
O i—
u t-
c c
ro QJ
OJC-J
O -C
-p
OJ 3
i— o
•r- 00
TO -P
r— in
O OJ
> 3:
E OJ
00 -P
Q) C
U -P
QJ C
QJ in
on QJ
«*- Q-
O Q)
cc
m
in in
fO Q»
Zl 3
in
r— in
fO -i-
4-> I—
O
in
OJ O
.c CL
•5
O
c
>^ ro
C E
ro 3
E in
3 "O
on QJ
•t-*
. in
1 CL
in
O
Q
E
O
U
a
3.
'fU
O
^—
TJ- ro
oo £H L?) csj ix>
3: "— ' -3- csj oo
^
on CN?**" m ^
3: ^^ m r-H ID
00
^
^s *3" r*- f^«.
on ^n i • •
3: s^ in csj VD
**•> i-H
3: ^-^ O T— i IJD
OJ
C OJ
O •r-
.i- . QJ
WO 5
> QJ
•»- QJ CL 3
"D -P 3 10 "O
•r- O in ID C
V) ui (- *i— •<— 3
3 o en -P a. o
I/) Q. *r" Q»
OJ O Dl OJ O
^s^^,
CSJ CSJ CSJ CM
rH 0 0 0
Q O 0
"Z. Z
o cTo o"
CSJ CSJ CSJ CSJ
o o o o
o o o o
z z z z
0 O csj O
o o o o
O O S- Q
Z Z -P Z
o o r*- o
csj csj csj esj
0000
O O 6- O
QJ
c
CJ C N
C QJ C
QJ M QJ
N c .a
r-> O
CSJ O Csj
r*. rH 0
0 O
a>
aj -P a>
i— O. N
x: o QJ
.c a. o
o. s-
•— Sir-
5 5 TO
OJ — X
-i- J- QJ
o
CSJ
o
o
rH O
o
o
i^D CSJ
ID O
o
z
ro o
^- csj
0 0
t- o.
QJ
c
QJ
i_
^_>
I C
CO OJ
1 ^
CQ.Q-
Ci
o
o" m <^ r^ ^->
o !- o i- a
^^ o
Lf> O CSJ I— 1 O
CM ?-* O rH CM ro
O O i-
Z Z 4J
o o o ^
CSJ CSJ <3- r- 1 O
rH 0 0 0 ID r-l
o o o o
z z z z
a>
*-J
re
i— "O
-C X i-
-t-> O O
j: a. r—
CL QJ -C
u
r- i- ro
>, 0 C
3 £: Z O -r-
i re c ml i "D
•r- OJ >> i- -•!-
o z a- J-MOJO
n oo o
r^ ro oo oo
i. O
*J Z
o" ^> 0*0^
CM «3- ID fl- (SI 00
O CM r-< *t O O
o o o o
z z z z
-> o o
rH O> CO CM 00
.O CM rH Lf) O O
O O 0
z z z
^- ^—v O
m *?• c\j i£>
fO . en • -
0 O !-
•Z. Z 4->
OJ
ro
a.
in
o
OJ p
*J OJ
re oj +J '•>
r— 4>J fl3 r—
.c in -u OJ
D. 0 .C 0
j: Q. s-
i-O. 0
N •— ">, !c
)— C >>4J U
o a» c u t
1 J— .C 1 X --^
- >, CL E|OJ in
QJ+J -r- 1 i. .f
ajco I— o s I—
CM CO U3
«x> o o o
S- t. !-
o o o o
o o o o
0 i. i.
o LD co
•9- (M ro 00
•3-000
O i- i-
Z *J 4-1
en (M CM «a-
o o o o
o o o
>> >,
>j QJ OJ
OJ CX CL
a. .a £>
f O C
.a i- i-
o o o
in i- *— i—
CO O .C j=
CL. .£! to re
'm T "a! £
+->t—l — a_
o
1 —
r~- ur>
CM r-l
i-
^J.
in in
1-H O
i- i.
4_> ^_;
(^
CM en
CM 0
i-
4->
^- fl-
o o
i- O
1- >!
C QJ
-C CL
— 5
XI 0
0 I-
s- o
O i—
r— JI
LJ re
ou S"
f— 1 O '•^
O O r-l
t- 0 0
^2* ' .
«r «• o
O O ^H
^— '^-^s.^
o o o
o o ^~-
0 0 rH
000
z z z
LO "3- O
O O i-H
i- O O
f^ r— r~
c c c
^ £ J=
CL O. Q.
^ £ £
o o o
i- i- S-
o o o
u u o
"u o oi
re
c
OJ
OJ
i-
a.
in
c
3
Q
o.
o
u
OJ
r"
r-
ai
re
i-
II
i.
o
o
c
0
u
OJ
•f>
-a
o
+J
S
r-
•o
OJ
ro
•'-
in
OJ
OJ
•^
in
"~
in
OJ
in
OJ
j:
c
OJ
ro
0.
c
flj o-
3 O
a
> -a
re TD
OJ
T3ON
O> O "-
+-> — 1 i-
u re
OJ C E
*J OJ E
0) OJ 3
"D » in
] 1 QJ ^J
O J3 O
c c
M oj re
> 4->
o ai (o
Z i— O
re X)
148
-------
TECHNICAL REPORT DATA
(Please read [nuntcnons on the reverse before completing/
• =I£,JORT NO. 2.
EPA-560/5-86-037
4 7ITL3 AND SUBTITLE
Broad Scan Analysis of Human Adipose Tissue
Volume 3 - Semi volatile Organic Compounds
7 AUTHOR(S)
John S. Stanley
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Midwest Research Institute
425 Vol ker Boulevard
Kansas City, Missouri 64110
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Office of Toxic Substances
Field Studies Branch (TS-798)
Design Development Branch/Exposure Evaluation Division
4m M Stppt sw
^Ih^f.n^'nr ?n4fin
3. RECIPIENT'S ACC£SSIOf*NO
5. REPORT DATE
December 1986
6. PERFORMING ORGANIZATION CODE
Midwest Research Institute
8. PERFORMING ORGANIZATION REPORT NO.
8821-A(01)
10. PROGRAM ELEMENT NO.
1 1. CONTRACT/GRANT NO.
68-02-3938
68-02-4252
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
J. Remmers and P. Robinson, Work Assignment Managers
J. Breen and C. Stroup, Program Managers
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). . j
EPA/OTS has recognized a need to expand the use of the NHATS program to pro- i
vide a more comprehensive assessment of toxic substances that are accumulated in adi- i
pose tissue. This report deals specifically with the measurement of semivolatile or- j
ganic chemicals in composited adipose tissue specimens from the FY82 NHATS repository. J
Quantitative data for organochlorine pesticides, PCBs, polynuclear aromatic J
hydrocarbons, phthalate esters, and phosphate triesters were determined for each com- |
posite. The frequencies of detection for each of the compounds based on the specific !
age group and census division are detailed in the report. The feasibility of determin- !
ing other halogenated aromatic compounds, including polybrominated biphenyls, polychlor-j
inated terphenyls, and polychlorinated diphenyl ethers, using this method was demon- {
strated through the analysis of spiked adipose tissue samples. !
17 KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
Human Adipose Tissue
Semivolatile Organic Compounds
Orqanochlorine pesticides
PCBs
Phthalate esters
Phosphate triesters
HRGC/MS
13. 3I3TPI3UTION STATEMENT
Release unlimited
b. IDENTIFIERS/OPEN ENDED TERMS
Analysis
Determination
19 SECURITY CLASS fT'fiis Report!
Unclassified
20 SECURITY CLASS /This payei
Unclassified
c. COSATi Field/Group
21. NO. OF PAGES
162
22. PRICE
SPA Form 2220-1 (R»». 4_77) previous eoi TION i s o BSOLETE
------- |