BROAD
SCAN
ANALYSIS
OF
HUMAN
ADIPOSE
TISSUE:
VOLUME
111
­
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
U.
S.
Environmental
Protection
Agency
401
M
Street,
S.
W.
Washington,
DC
20460
Attn:
Ms.
Janet
Remmers
and
Mr.
Philip
Robinson,
Work
Assignment
Managers
Dr.'
Joseph
J.
Breen
and
Ms.
Cindy
Stroup,
Program
Managers
REPRODUCEDBY
U.
S.
DEPARTMENT
OF
COMMERCE
NATIC)
NALTECHNICAL
INFORMATION
SERVICE
SPRINGFIELD,
VA
22161
­.­­­­

I
1.
qE?
oaT
NO.
2.

~~
A{
56'
0/
5­
86,{
03
7
3.
TI~
LZ
.
ANO
SW~'
TI+
LE
Broad
Scan
Analysis
of
Human
Adipose
Tissue
Volume
3
­
Semivolatile
Organic
Compounds
7.
A,
L'THORIS)

John
S.
Stan'ley
3.
PERFORMjNG
ORGANIZATION
NAME
AN0
dOORESS
Midwest
Research
Institute
12.
SPONSORING
AGENCY
NAME
AND
ApoRESS
U.
S,
Environmental
Protection
AgencyOffice
of
Toxic
Substances
Branc$
(
TS­
728)
ment
ranch/
xposure
Evaluation
Division
5.
REPORT
OATB
.,

December
1986
i
6.
PERfOflMlNC
ORGANIZATION
COO 
i
Midwest
Research
Institute
]
I
8.
PERFOAMING
OACANlZATtCN
REPORT
NO.
I!

I
I
110.
PROGRAM
ELEM NT
NO.
I
i
68­
02­
4252
13.
TYPE
OF
REPORT
AND
PERIOD
COVEREO
Final
14,
SPONSORING
AGENCY
CODE
­>
The
U.
S.
EPA's
Office
of
'
Toxic,
Substances
(
OTS)
maintains
a
unique
capability
1
for
monitoring
human
exposure
to
potentially
toxic
substances
through
the
National
Human1
Adipose
Tissue
Survey
(
NHATS).­
The
primary
focus
for
NHATS
has
been
to
document
trends
in
human
exposure
to
envirp.
nrne6ta7ly.
persistent
contaminants,
specificalJy
organochlor­'
i
i
ne
pes
ticides
and@.
hi.
oad
*
z­­
Tys:
r;
­­­­.­
r:­­?
7
­­­..
L­..
biQheriyl
s
(
PCBs­)­.
x+,
*
mx­­­­
L
L
.­
2=.­­.
;"
re­­

EPA/
O$
Yhas
recognized
a
need
to
expand
the','
qse
of
the
NHATS
program
to
pro­!
vide
a
more
­,
c3%
prehensive
assessment
of
toxic
substances>.\
that
are
accumulated
in
adipose
tissue.%
This
report
deals
specifically
with
the
measwrement
of
semivolatile
or­
I
ganic
chemicals
in
cornposited
adipose
tissue
specimens
from&
he
FY82
NHATS
repository.
1
Quantitative
data
for
organochlorine
pesticides,
P'CBs,
pplynuclear
aromatic
I.
hydrocarbons,
phthalate
esters,
and­
phosphatetriesters
were
determined
for
each
composite
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
1
ing
other
halogenated
aromatic
compounds­
bcludfng
polybrominated
biphenyls,
polych?
or­
i'
inated
terphenyls,
and
polychlorinated
diphe~
e~&
he~
s+
psing
this
method
was
demonstrated
through
the
analysis
of
spiked
adipose
tissue
samples,:~......~~..~~~~..~~­!
I
:..~­..,.

7.

OESCRIPTORS
iuman
Adipose
Tissue
kmivolatile
Organic
Compounds
Irganochlorine
pesticides
'
CBs
'
hthalate
esters
'
hosp
hate
triesters
IRGC/
MS
3.
315TP13UTiGN
STdTEMENf
telease
unlimited
­­...­
I
KEY
WOROS
AN0
DOCUMEPJT
ANALYSIS
I
(~.~
DENTIPIERS/
OP NENOEO
TERMS
1..
COSA7i
FieidlCroup
:
I
I
I
I
i
119.
SECURITY
CLASS
173uReporr)
(
21.
NO..
Of
?
AGES
Unclassified
I
164
­
I
20.
SECUfilTY
CLASS
IThupgr)
Uncl
assified
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
provides
a
synopsis
of
a71
analytical
efforts
compiled
under
the
broad
scan
anal ysis
program.
Volume
I1
deals
.
ipecifica?
lywith
the
chemical
analysis
of
the
NHATS
composites.
Volume;
IV
and
V are
for
general
volatile
organics,
polychlorinated
dibenzo­
e­
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
Substances
(
OTS)
Design
and
Development
Branch
contractor,
Battelle
Columbus
Laboratories.
,
The
entire
series
of
reports
are
referenced
as
follows:
Stanley
JS.
1986.
Broad
scan
analysis
of
human
adipose
tissue:
Volume
I:
Executive
summary.
EPA
560/
5­
86­
035.
Stanley
35.
1986.
Broad
scan
analysis
of
human
adipose
tissue:
Volume
11:
Volatile
organic
compounds.
EPA
5601 
5­
86­
036,
Stanley
JS.
1986.
Broad
scan
analysis
of
human
adipose
tissue:
Volume
111:
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
Sranch
(
FSB)
broad
scan
analysis
of
human
adipose
tissue
program
(
 PA
Prime ContractNos.
68­
02­
3938and
68­
024252
Work
Assignments
8
and
21,
respectively,
Ms.
Janet
Remmers,
Work
Assignment
Manager,
and
Dr.
Joseph
Breen,
Project
Officer).

I
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
Laboratories
under
contract
to
the
EPA/
OTS
Design
and
Development
Branch
(
Mr.
Phillip
Robinson,
Task
Manager
and
Ms.
Cindy
Stroup,
Program
Manager).

Program
Manager
Director
Chemical
Sciences
Department
L
iii
TABLE
OF
CONTENTS
Page
Executive
Summary................................
xiii
r
.
Introduction
........................
1
A
.
Broad
Scan
Analysis
Strategy............
1
B.
Work
Assignme.
nt
Objectives..............
2
C
.
Organization
of
This
Report
.............
2
I1.
Recommendations.......................
2
I11
.
Experimental
........................
3
A
.
B.
C
.

C
.

D
.
Collection
and
Storage
of
NHATS
Specimens
.....
3
Sample
Compos.
iting
Activity
.............
4
Broad
Scan
HRGC/
MS
Analysis
Procedures
.......
5
1.

2
.
3
.
4
.
5
.
6
.
7.
8.
9
.
10.
11.
12.
Selection
of
Analytical
Methods/
Target
Ana
1yte
s
..................
5
Method
Summary
................
9
Reagents
and
Standards
............
10
Preparation
of
Glassware
...........
12
Extraction,
Cleanup,
and
Concentration
....
12
Lipid
Determination..............
12
Gel
Permeation
Chromatography
(
GPC)
......
12
Floris.
il
Fractionation
............
13
HRGC/
MS
Analysis
...............
13
Quality
Assurance/
Qual
ity
Control
(
QA/
QC)
...
15
Data'Interpretation..............
15
19
'
HRGC/
Selective­
Detector
Screening
.......
Toxaphene
Analysis
.................
20
1.
Carbon
Adsorbent
Chromatography
........
20
2
.
Florisil
Column
Fractionation.........
21
3
.
NRGC/
MS­
SIM
Analysis
.............
22
Method
Validation
.................
22
1.
Broad
Scan
HRGC/
MS
Analysis
..........
22
2
.
Toxaphene
Analysis
..............
26
I.
IV.
Results
...........................
26
A
.
Broad
Scan
Analysis
................
26
1.
HRGC/
MS
....................
26
2
.
HRGC/
ECD
Analysis
..................
104
B.
Toxaphene
Analysis
.................
113
..
.......

j
Preceding
page
bfank
1
{

i
'
V
L
I
TABLE
OF
CONTENTS
(
Continued)

Page
VI
e
Quality
Assurance/
Qual
ity
Control.
.
.
­.
.
.
.
.
..
.
.
.
118
A.
Spiked
Tissue
Samples
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
118
B.
Spiked
B1.
anks
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
­.
.
.
118
C.
Porcine
Fat'.
.
..
.
.
i
.
.
.
.
.
.
.
.
.
.
­.
.
.
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
,
1
2
3
4
5
6
...

LIST
OF
FIGURES
Number
Page
GPC
elution
profiles
of
selected
biogenic
compounds
and
environmental
contaminants
(
Ribick
et
al,
1982)
...
8
Ftow
scheme
for
analysis
of
semivolatile
organic
compounds
in
human
adipose
tissue.
..............
10
GPC
chromatogram
of
elution
of
(
A)
0.9g
lipid;
(
B)
0.3
g
lipid;
and
(
C)
0.1
g
lipid.
............
14
!
Separation
of
PCBs
from
toxaphene
using
Florisil
(
1.25%
deactivated)
fractionation.
...............
29
!
Separation
of
toxaphene
from
PCBs
using
Florisil
(
1.25%
deactivated)
fractionation.
................
30
Incidence
of
detection
of
semivolatile
organic
compounds
determined
in
composited
human
adipose
tissue
from
the
West
Census
Region.
...................
31
7
Incidence
of
detection
of
semivolatile
organic
compound's
determined
in
composited
human
adipose
tissue
from
the
Northeast
Census
Region
.................
32
8
Incidence
of
detection
of
semivolatile
organic
compounds
determined
in
compos
ted
human
adipose
tissue
from
the
North
Central
Census
Region
...............
33
!
9
Incidence
of
detection
of
semivolatile
organic
compolinds
determined
in
compos
ted
human
adipose
tissue
from
the
South
Census
Region
...................
'
34
I
P
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
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
'
I
composites
(
6%
diethyl
ether
F'iorisil
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
i
G
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
fcom
HRGC/
MS
(
scanning)
analysis
of
human
adipose
tissue.
............
76
17
HRGC/
MS
and
HRGC/
ECD
chromatograms
of
the
6%
diethyl
ether
Florisi'l
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
.............
111
24
HRGC/
ECD
chromatograms
of
method
blanks
from
6%
and
15/
50%
Florisil
fractionation
...............
112
I
i
viii
1
i
LIST
OF
FIGURES
(
Continued)

Number
.
Page
25
26
27
28
i
I
(
2­
min
hold)
to
34OoC
at
10
°
C/
min
.
.
.
.
.
.
.
.
.

Mass
spectrum
for
scan
no.
756
from
the
total
ion
chromatogram
from
Figure
25
(
toxaphene
standard).
.

Mass
spectrum
for
scan
no.
825
from
the
total
ion
chromatogram
from
Figure
25
(
toxaphene
standard).
.

Selected
ion
current
plots
of
characteristic
fragment
ions
for
toxaphene
from
an
HRGC/
MS­
SIM
analysis
Total
ion
chromatogram
for
the
HRGC/
MS
full
scan
analysis
of
a
0.90
pg/
pL
standard
of
toxaphene
using
a
30­
m
DB­
5
fused
si1ica
column
temperature
programmed
from
6OoC
.
.
.
114
.
.
.
115
,
.
.
116
.
.
.
.
.
117
ix
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
Targ­
et
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/
Gl
ass
Fiber
Adsorbent
Column..
.........................
27
5
Recovery
of
Toxaphene
from
Florisil
Cleanup.
........
28
6
Inti­
dence
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,
p'­
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
fl
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.
Ti
sue
­
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
X
LIST.
OF
TABLES
(
Contiwed)

Number
&

17
Data
Report
­'
Pentachlorobiphenyl
(
CAS
No.
25429­
29­
2)

.
FY82
Composite
Adipose
Tissue
Samples
..
:
.......
64
18
Data
Report
­
Hexachlorobiphenyl
(
CAS
No.
26601­
64­
9)
­
FY82
Composite
Adipose
Tissue
Samples
..........
66
19
Data
Report
­
Heptachlorobiphenyl
'(
CAS
No.
28655­
71­
2)
­
FY82
Composite
Adipose
Tissue
Samples
..........
68
20
Data
Report
­
Octachlorobiphenyl
(
CAS
No.
31472­
83­
0)
­
FY82
Composite
Adipose
Tissue
Samples
..........
70
21
Data
Report
­
Nonachlorobiphenyl
(
CAS
No.
53742­
07­
7)
­
FY82
Composite
Adipose
Tissue
Samples
...........
72
22
Data
Report
­
Oecachlorobiphenyl
(
CAS
No.
2051­
24­
3)
­
FY82
Composite
Adipose
Tissue
Samples
..........
74
23
Data
Report
­
1,
Z­
Dichlorobenzene
(
CAS
No.
95­
50­
1)­
FY82
Composite
Adipose
Tissue
Samples
..........
77
24
Data
Report
­
1,2,4­
Trichlorobenzene
(
CAS
No.
120­
82­
1)
­
FY82
Composite
Adipose
Tissue
Samples
..........
79
25
Data
Report
­
Hexachlorobenzene
(
CAS
No.
118­
74­
1)­
FY82
Composite
Adipose.
TissueSamples.
............
81
26
Data
Report
­
Triphenyl
Phosphate
(
CAS
No.
115­
86­
6)
­
FY82
Composite
Adipose
Tissue
Samples
..........
84
27
Data
Report
­
Tributyl
Phosphate
(
CAS
No.
126­
73­
8)­
FY82
Composite
Adipose
Tissue
Samples
...........
86
I
28
Data
Report
­_
c
tris(
2­
Chloroethyl)
Phosphate
(
CAS
No.
115­
96­
8)
­
FY8E
Composite
Adipose
Tissue
Samples
.
.
­.
88
29
Data
Report
­
Diethyl
Phthalate
(
CAS
No.
84­
66­
2)
­
FY82
Composite
Adipose
Tissue
Samples.
............
90
30
'
DataReport
­
Di­
n­
butyl
Phthalate
(
CAS
No.
84­
74­
2)
­
FY82
Composite
Edipose
Tissue
Samples
..........
92
31
Data
Report
­
Di­
n­
octyl
Phthalate
(
CAS
No.
117­
84­
0)
­
FY82
Composite
Adipose
Tissue
Samples
..........
94
32
Data
Report
­
Butyl
Benzyl
Phthalate
(
CAS
No.
85­
68­
7)
­
FY82
Composi,
teAdipose
Tissue
Samples
..........
96
'
xi
I
LIST
OF
TABLES
(
Continued)

Number
Page
33
34
35
36
37
38
39
40
41
42
43
Data
Report
­
Naphthalene
(
CAS
No.
91­
20­
3)
­
FY82
Corn­.
posite
Adipose
Tissue
Samples
................
98
Data
Report
­
Phenanthrene
(
CAS
No.
85­
02­
8)
­
FY82
Com
posite
Adipose
Tissue
Samples
..............
100
Compounds
Not
Detected
in
the
FY82
Composite
Specimens.
..
102
Summary
of
Toxaphene
Identificaton
in
Composited
Adipose
Tissue
Specimens­................
119
Recovery
Efficiency
of
Semivolatile
Organics
from
Spiked
Human
Adipose
Tissues
..................
120
Method
Evaluation
Experiments
Percent
Recovery
(
Spiked
Solvent
Blanks)
.....................
121
Comparison
of
the
Average
Recovery
Efficiency
of
Semi­
volatile
Organics
from
Spiked
Lipid
Samples
and
Spiked
Blanks..
........................
123
Data
Summary
for
the
HRGC/
MS
Analysis
of
an
EMSL/
LV
QA/
QC
Spiked
Porcine
Adipose
Sample
(
Adipose
121)
....
126
i
Data
Summary
for
the
Broad
Scan
Analysis
of
a
Homogenized
Bulk
Lipid
(
Human
Adipose)
Sample
........
127
I
Summary
of
Surrogate
Compound
Recoveries
(%)
from
the
FY82
Composited
Human
Adipose
Specimens
.........
130
Summary
of
Surrogate
Compound
Recoveries
(%)
from
the
.

FY82
QA/
QC
Samples
for
Human
Adipose.
..........
132
xi
i
EXECUTIVE
SUMMARY
'

The
U.
S.
Environmental
Protection
Agency's
Office
of
Toxic
Substances
(
EPA/
OTS)
maintains
a
unique
program
for
monitoring
human
exposure
to
potential'lytoxic
substances.
The
National
Human
Adfpose
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
polychlorinated
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
semivolatile
organic
compounds
and
trace
elements.

This
volume
of
the
final
report
deals
specifically
with
the
measurement
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
fractionation
and
high
resolution
gas
chromatgraphy/
mass
spectrometry
(
HRGC/
MS).

Forty­
six
composite
samples
were
prepared
from
the
FY82
NHATS
repository
according
to
a
study
design.
prepared
by
the
EPA/
OTS
design
and
development
contractor,
Battelle
Columbus
Laboratories,
The
composite
samples
represented
thenine
U.
S.
census
divisions
and
three
age
.
groups(
0­
14,15­
44,
and
45­
pius).

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
terphenyls
and
polychlorinated
diphenyl
ethers,
using
this
method
was
demonstrated
through
the
analysis
of
spiked
adipose
tissue
samples.
The
quantitative
data
for
the
target
analytes
described
in
this
report
have
been
submitted
along
with
all
supporting
quality
control
data
to
Battelle
Columbus
Laboratories
for
statistical
analysis.

xiii
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
chemicals
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
retention
time
and
mass
spectra.
The
detail
on
PCB
levels
is
also
expanded
as
a
result
of
identifying
specific
degree
of
chlorination
(
homologs)
and
providing
quantitation
of
individual
responses.
Previous
NHATS
analyses
for
PCBs
based
on
the
PGC/
ECD
method
have
resulted
in
semiquantitative
data
based
on
a
single
response.

I
I
xi
v
I3
I
t
I.
INTRODUCTION
I
The
National
Human
Adipose
Tissue
Survey
(
NHATS)
is
the
main
operative
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).
t
I
NHATS
is
an
annual
program
to
collect
a
nationwide
sample
of
adipose
tissue
specimens
and
to
chemically
analyze
them
for
the
presence
of
toxic
compounds.
The
objective
of
the
NHATS
program
is
to
detect
and
quantify
the
prevalences
of
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
collected
from
autopsied
cadavers
and
surgical
patients
according
to
a
statistical
survey
design
(
Lucas,
Pierson,
Myers,
Handy
1981).
The
survey
design
ensures
t
I
 

E
that
specified
geographical
regions
and
demographic
categories
are
appropriately
represented
to
permit
valid
and
precise
estimates
of
baseline
levels,
 
.
time
trends,
and
comparisons
across
subpopulations.

t
The
data
for
the
NHATS
are
generated
by
collecting
and
chemically
analyzing
adipose
tissue
specimens
for
selected
toxic
substances.
Historically
organochlorine
pesticides
and
polychlorinated
biphenyls
(
PCBs)
have
been
the
compounds
of
interest.

i
*
A.
Broad
Scan
Analysis
Strategy
t
EPA/
OTS
recognized
the
need
to
provide
a
more
comprehensive
assess­
ment
of
the
toxic
substances
that
accumulate
in
adipose
tissue.
An
aggressive
strategy
to
assess
TSCA­
related
substances
that
persist
in
the
adipose
tissue
of
the
general
U.
S.
population
has
been
developed
by
EED.
The
NHATS
specimens
collected
during
fiscal
year
1982
(
FY82)
were
selected
for
a
broad
scan
analysis
of
volatile
and
semivolatile
organic
TSCA­
related
chemicals
and
trace
elements
(
Mack,
Stanley
1984).
c.
1
The
initiative
to
achieve
a
 
more
comprehensive
assessment
of
toxic
substances
in
human
adipose
tissue
necessitates
a
modification
of
the
existing
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/
efectron
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
polybrominated
biphenyls
(
PBBs)
(
Lewis,
Sovocool
1982)
and
polychloroterphenyls
(
PCTs)
(
Wright,
Lewis,
Crist,
Sovocool,
Simpson
1978).
I
I
F
I
1
L
B.
Work
Assignment
Objectives
The
objectives
of
this
work
assignment
were
to
(
1)
identify
appropriate
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)
complete
the
sample
workup
and
analysis
of
46
composite
samples
prepared
from
the
NHATS
specimens
collected
during
FY82.

The
broad
scan
analysis
approach
based
on
HRWMS
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
pg/
g.

C.
Organization
of
This
Report
This
report
deals
specifically
with
the
application
of
the
broad
scan
analysis
concept
to
determine
semivolatile
organic
compounds
in
human
adipose
tissue,
Following
this
introductory
section,
Section
I1
presents
recommendations
for
additional
method
development
and
routine
application
of
the
concept.
Section
111
is
the
experimental
section
and
describes
the
experimental
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
presents
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.

I
I.
RECOMMENDATIONS
The
analytical
method
described
in
this
report
and
modified
as
recommended
below
should
be
fully
validated
through
additional
intra­
and
inter­
laboratory
analyses.
This
effort
is
necessary
to
define
the
methods
limitations
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
experimentalty
through
replicate
analysis
of
spiked
tissue
samples.
The
HRGC/
MS
and
the
PGC/
ECD
methods
should
be
evaluated
using
homogenized
split
samples
to
determine
the
comparability
of
data
for
the
organochlorine
pesticides
and
PCBs.
This
effort
is
necessary
to
determine
whether
it
will
be
possible
to
effectively
extend
trend
lines
from
the
PGC/
ECD
data
from
preyious
NHATS
analysis
programs.
r
* 

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.
Surrogate
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
considered
as
surrogates
in
further
evaluation
of
the
analytical
method.

2
15
j
For
continued
broad
scan
analysis
projects
there
is
a
need
to
establish
sufficient
characterized
reference
samp?
es
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.
L.

Effort
is
also
necessary
in
the
area
of
developing
HRWselective
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
(
MUMS)
to
lower
detection
limits
and
increase
specificity
for
compound
classes
such
as
organochlorine
pesticide,
polychlorinated
biphenyls,
polybrominated
biphenyls
(
PBB),
polychlorinated
terphenyls
(
PCT),
polychlorinated
diphenyl
ethers
(
PCDE),
and
polychlorinated
naphthalenes
(
PCN).

111.
EXPERIMENTAL
This
section
of
the
report
describes:

A.
collection
and
storage
of
NHATS
speciments;
B.
sample
compositing
activity;
C.
broad
.
scanHRGC/
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
chemicals
such
as
solvents,
paraffin,
disinfectants,
preservatives,
or
plastics3
16
The
cooperators
were
given
no
specific
instructions
to
avoid
potential
contamination
that
might
arise
from
background
contribution
(
airborne
levels)

 
.
of
solvents
or
metals.

The
adipose
tissue
specimens
were
sealed
in
glass
jars
and
frozen
(­
20OC)
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
repository
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
(­
20OC).
Precautions
were
taken
to
ensure
that
the
specimens
remained
frozen
during
all
inventory
and
sample
handling
procedures.

B.
 
Sample
Cornpositing
Activity
The
NHATS
FY82
adipose
tissue
specimens
were
subsampled
and
composited
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
cornpositing
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
cornpositing
effort.
The
specimens
were
placed
on
dry
ice
so
they
would
remain
frozen
during
the
cornpositing
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
?
aboratory
air.
Compressed
air
was
filtered
through
a
charcoal
trap
to
remove
potential
volatile
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
IFE
septa
caps.
Each
specimen
was
manipulated
with
a
separate
clean
spatula.
All
weighings
were
performed
to
f
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
physical
compositing.
For
example,
ifa
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
semivolatile
organic
composite
only.
As
a
result,
several
of
the
volatile
organic
4
composites
contain
somewha$.
less
than.
thetarget
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
9..

Prior
to
the
compqsiting
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
@
laced
in
an
oven
at
200OC
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
(­
20OC).
Before
being
placed
in
the
freezer
in
the
40­
mL
vials,
the
composited
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
free­
zeruntil
analysis.

The
compo'site
samples
ranged
from
9.0to
28.1
g
total
mass
with
an
average
mass
of
20.9
g
for
the
46
composites.
The
amounts
of
each
NHATS
specimen
added
to
a
specific
composite
are
detailed
in
Volume
I1
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
f.
Selection
of
Analytical
MethoddTarget
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
concern
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
concentrated
sulfuric
acid
digestion),
low
temperature
precipitation,
adsorption
on
calcium
or
cesium
silicates,
and
separation
of
the
analytes
based
on
gel
permeation
chromatography
(
GPC).

GPC
presents
the
most
viable
option
of
these
analytical
procedures
for
bulk
lipid
cleanup
for
the
broad
scan
analysis
concept.
The
advantage
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,
Aarorkon
1980;
MacLeod,
Hanisch,
Lewis
1982;
Ribick,
Dubay,
Petty,
Stalling,
Schmitt
1982;
Norstrom,
Simon.,
Mulvihill
1986)
as
well
as
environmental
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.

5
Table
1.
Demographic
Characteristics
for
the
FY8$
NHATS
Composites
­
Semivolatile
Organic
Analysis
Census,.,
Census
Age
d
Composite
No.
of
Percent
Percent
region
division
group
number
specimens
white
mal
e
6
1
s
Table
1
(
continued)
­~

1
Censusb
region
Census
division
Age
d
group
Cornposite
number
No.
of
specimens
Percent
white
Percent
mal
e
S
WS
1
1
13
69.2
53.8
s
S
ws
ws
2
2
1
2
19ia
78.9
83.3
52.6
50.0
S
ws
3
1
23
87.0
43.5
­

aData
provi
ded
by
Battell
e
Col
umbus
Laboratories.
bNC
=
North
Central,
NE
=
Northeastern,
S
=
South,
W
2
West.
 
EN
=
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.
dAge
group
1
=
0­
14
years,
age
group
2
=
15­
44
years,
age
group
3
=
45+
years.

!
Y
E
K
U
­.
..

8
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
applicability
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,
Strassrnan,
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
specific
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
semivolatile
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
Tekmam
Tissumizer.
The
extracts
are
filtered
through
anhydrous
sodium
sulfate.
Extractable
lipid
is
determined
using
approximately
I%
of
the
resulting
extract.

9
21
Composite
FY82
NHATS
~­

Add
Stable
Isotope
LobeledI
Surrogate
Compounds
Extraction­
Tissumircr
I

.! 

HRGC/
MS
(
SIM)
for
Specific
Compound
CIoss
(
Toxophene
PCDDi
KDF
1
I
Quonti
tootion/
Dato
Tmnsfer
to
BCL
Figure
2.
Flow
scheme
for
analysis
of
compounds
in
human
adipose
tissue.
1
AMOCO
PX
­
21/

Florki
I
I
semivolatile
organic
10
23
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
internal
quantitation
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
I­
mt
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
Laboratories
Florisil
(
60/
100
mesh)
was
extracted
with
methylene
chloride
overnight
in
a
Soxhlet
apparatus.
The
extracted
material
was
air
dried
and
then
activated
at
13OoC
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
Or.
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
Spxhlet
apparatus
with
methylene
chloride.
The
material
was
allowed
to
air
dry
and
then
was
placed
in
a
muffle
oven
for
2
to
6
h
at
65OoC.
The
cleaned
material
was
stored
in
an
oven
at
13OOC.

C.
Analytical
Standards,

The
organochlorine
pesticides
were
obtained
from
the
EPA
Reference
Materials
Branch,
Research
Triangle
Park.
Toxaphene
was
obtained
from
Supelco
as
a
stock
solution.
The
chlorobenzenes,
chlorophenols,
PCBs,
PBBs,
PCTs,
PAHs,
and
phthalate
esters
were
obtained
from
Ultra
Scientific,
Hope,
Rhode
Island.
The
phosphate
triesters
were
obtained
from
Chem
Service
Chemicals
West
Chester,
Pennsylvania,
and
Aldrich
Chemical
Company,
Milwaukee,
Wi
sconsi
n.

d.
­
Surrogate
Standards
The
surrogate
compounds
naphthalene­
d8,
chrysene­
d,,
,
13C6­
I,
2,4,5­
tetrachlorobenzene,
13C6­
hexachl
orobenzene,
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
p­
dioxins
were
obtained
from
Cambridge
i
isotope
laboratories
(
Woburn,
MA).
.

4.
Preparation
of
Glassware
All
glassware
was
washed
with
soap
and
water,
and
then
rinsed
sequentially
with
tap
water,
distilled
water,
acetone,
and
hexane.
80th
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
pg);
chrysene­
d12
(
2
pg);
13C6­
l,
2
,4,5­
tetrachlorobenzene
(
2
pg);
13C6­
4­
chlorobiphenyl,
13C123,3
,4,4'­
tetrachlorobiphenyl
(
4
pg);
13C12­
Z,
2',
3,3'
,5,5',
6,6'­
octachlorobiphenyl
(
8
pg);
13C12­
decachlorobiphenyl
(
10
pg);
f3Cl~­
2,3,7,8­
tetrachlorodibenzo
p­
dioxin
(
1ng);
and
13C12­
octachlorodibenzo­~­
dioxin(
5
ng).
The
spiked
adipose
tissues
were
allowed
to
equilibrate
to
room
temperature
and
were
homogenized
for
approximately
1min
with
a
Tekma­
Tissumizer
(
Tekmar
18­
EN
probe)
with
at
least
five
successive
aliquots
(
10
mL)
of
methylene
chloride
(
B&
J,
distilled
in
glass).
The
methylene
chloride
extracts
were
dried
by
passage
through
anhydrous
sodium
sulfate.
The
sodilim
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
evaporation
The
final
volume
was
adjusted
such
that
the
solution
contained
approximately
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
methylene
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
 ­
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
i.

t
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
13OoC)
were
packed
in
hexane.
Anhydrous
sodium
sulfate
was
added
to
the
top
of
each
column
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
OB­
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
6OoC
for
2
min,
then
programmed
at
10
°
C/
min
to
a
final
temperature
of
31OoC.
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)
procedures
an
analytical
standard
so'lution
containing
compounds
representative
of
the
PCBs,
PCTs,
PBBs,
PCDEs,
chlorobenzenes,
chlorophenols,
organochlorine
pesticides,
phthalate
esters,
phosphate
esters,
PAHs,
the
surrogate
compounds,
and
the
internal
standa.
rd
(
anthracene­
dlo)
was
injected
as
a
calibration
standard
and
a
check
of
the
mass
assignment.
Response
factors
for
individual
compounds
were
calculated
relative
to
the'internal
standard
(
anthracene­
dlo).
The
relative
response
factors
(
RRFs)
were
calculated
as
described
below.

13
A.)
3.93
Lipid
t
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
E
I
I
I
I
I
1
1
t
I
c
I
I
I
b
I
1
I
i
Using
injections
of
1
to
2
pL
of
each
calibration standard,
the
observed
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
=
(
ASCis)/(
AisCs)

where
AS
=
area
or
peak
height
response
for
the
primary
quantitation
ion
of
the
target
analyte
Ais
=
area
or
peak
height
response
for
the
primary
quantitation
ion
of
the
internal
standard,
anthracene­
dIo
Cis
=
concentration
of
the
internal
standard
(
ng/
pt)

Cs
=
concentration
of
the
target
analyte
(
ng/
pL)

10.
Quality
Assurance/
Qual
ity
Control
The
QA/
QC
procedures
included
analysis
of
method
blanks,
spiked
recovery
samples,
replicate
tissue
samples,
and
spiked
porcine
fat
(
Adipose
121
prepared
by
EMSL­
LV).
These
samples
were
prepared
and
analyzed
with
the
actual
adipose
tissue
samples.
Additional
detail
on
the
preparation
of
these
samples
is
presented
in
Section
V
(
Quality
Assurance/
Quality
Control).
Instrumen
al
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
dlo­
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
collettion
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
characteristic
ion
were
used
to
search
each
data
file.

a.
Qualitative
Identification
 ,

The
automated
search
and
quantitation
routine
identified
positive
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
reviewing
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.

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18
b.
Quantitation
Data
were
quantitated
on
the
internal
standard
method.
Table
2
presents
the
primary
quantitation
ions
for
each
of
the
target
analytes,
surrogates
and
the
internal
standard.

The
HRGC/
MS
data
were
quantitated
using
the
following
equation:

where
AS
=
area
of
the
primary
quantitation
ion
of
the
target
analyte,
AIS
=
area
of
the
primary
quantitation
ion
(
m/
z
188)
of
the
internal
standard,
anthracene­
dlo
IS
=
concentration
of
the
internal
standard
in
micrograms
(
pg),
and
RRF
=
relative
response
factor
of
the
target
ana'lyte
versus
the
internal
standard.

The
concentration
(
C
)
of
the
target
analyte
in
the
original
wet
tissue
sample
was
calculated
byqividing
the
total
micrograms
of
target
analyte
detected
by
the
total
composite
weight.
In
this
report
concentration
data
are
expressed
as
micrograms
per
gram
(
pg/
g).
The
concentration
data
(
C
1
on
a
lipid
basis
were
calculated
by
dividing
the
wet
tissue
concentratibb
(
CwT)
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
characteristic
quantitation
ion
was
greater
than
2.5
times
but
less
than
10
times
the
background
signa?­
to­
noise
are
reported
as
trace
(
tr)
values.
Target
analytes
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
system
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
HRGWelectron
capture
detector
(
HRGC/
ECD)
as
a
means
to
screen
for
response
to
additional
compounds.
:
The
sample
extracts
were
diluted
1
to
10
(
10
pL
of
extract
to
100
pL
final
volume
in
hexane).
The
HRGC/
ECD
analysis
was
achieved
using
a
30
m
x
0.25
mm
OB­
5
fused
silica
column.
The
analysis
conditions
(
injector
operation
and
temperature
program)
were
identikal
to
the
parameters
specified
for
the
HRGC/
MS
analysis,

19
32
C.
Toxaphene
Analysis
Fol
lowing
the
broad
scan
HRGC/
MS
analysi
s,
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
procedure
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
Tekmam
Tissumizer.
Amoco
PX­
21
carbon
(
50
mg)
provided
by
Or.
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
accommodate
1/
16
in.
0.
d.
stainless
steel
tubing.
This
stainless
steel
tubing
was
used
tp
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
cotumn,
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
carbodglass
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
mt
methanol,
and
then
100
ml
toluene
again.
The
residual
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
additional
50
mC
of
the
501 
50
solvent
was
eluted
through
the
column
with
nitrogen
pressure
to
remove
any
air
pockets.
In
order
to
maintain
a
flow
of
3­
5
ml/
rnin,
a.
slight
nitrogen
pressure
was
necessary.

20
33
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
adjusted
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
column
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
adsorbent
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
pdioxins
(
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
coeluted
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
biological
samples
(
Zell,
Ballschmiter
1980).

a.
Florisil
Preparation
The
Florisil
was
precleaned
by
methylene
chloride
extraction
for
13
h
followed
by
oven
activation
at
13OOC.
For
optimum
separation
the
Florisil
was
deactivated
with
1.25%
water.
A
portion
of
the
Florisil
was
removed
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
equi
1ibration.
­

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
woo1
and
13.0
g
(
5
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
application
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
cancentrated
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
MSSOTC
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
cornplex
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
rn/
z
345
were
not
included
in
the
analysis
scheme.

0.
Method
Val
idati
on
1.
Broad
Scan
HRGC/
MS
Analysis
e
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
Tekmam
Tissumizer.
The
resulting
extract
was
chromatographed
with
an
ABC
gel
permeation
chromatography
system
using
Biobeads
SX­
3
and
methylene
chloride
following
the
conditions
previously
identified.
The
lipid
material
eluting
from
the
column
was
collected
separately
from
the
specific
xenobiotic
analytes
collected
from
this
materia1.

22
35
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
adsorbed
on
the
Micro
Cell
E
.(
MCE),
and
the
adsorbent
was
then
extracted.
with
5%
acetone/
acetonitrile.
T.
he.
resu1ting
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
requizred
Florisil
activated
at
13OoC
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/
splitl.
ess
inj.
ection
systems
were
investigated
for
extract
analysis.

The
results
of
the
method
evaluation
experiments
are
presented
fn
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.
PhthaTates,
pho,
sphate
esters,
dieldrin,
chlorophenols,
higher.
molecular
weight
PAHs,
and
hexa­
and
heptachlorodibenzo­
p­
dioxins
were
identified
in
the
15
and
50%
diethyl
ether
hexane
Florisil
fractions.
Some
compounds
including
octa­
dioxins
and
furans
and
some
phosphate
esters,
were
not
effectively
recovered
from
Florisil.

An
impor'tant
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
injector
however,
provided
much
better
chromatography
and
was
determined
to
be
the
technique
of
choice
for
the
analysis
of
the
composite
samples.

23
36
i
Table
3.
Summary
of
"
gerage
Recoveries
of
Specific
Analytes
from
Triplicate
Analyses
of
Spiked
Lipid
(
Human
Adipose)
Samples
Analyte
Chlorobenzene
1,2­
Dichlorobenzene
2,4­
Dichlorophenol
1,2,4­
Trichlorobenzene
Naphthalene
GPC/
F
1oris
i
1
MCE/
GPC/
Florisil
average
average
recovery
(%)
recovery
(%)

23
5
3
i3
­
.,
62
30
65
35
.
Acenaphthylene
Dimethyl
phthalate
Acenaphthene
Pentachlorobenzene
3
74
66
26
4
40
.
36
13C­
Monochlorobiphenyl
Fluorene
73
72
42
45
Diethyl
phthalate
4­
Chlorodipheiyl
ether
140
77
150
40.

4­
Bromobiphenyl
a­
BHC
81
97
56
74
Hexachlorobenzene
80
36
­
tris(
2­
Ch1oroethyl)
phosphate
P­
BHC
'

NDc101
ND
'

82
Phenanthrene
91
60
A­
BHC
.
~

108'
44
2,4,6­
Trichlorophenol
63a
ND
..
Heptachlor
.._.
c
i
­.
87
45a
Di­
c­
butyl
phthalate
120,
125
Pentachlorophenol
A1
drin
.
4,4'­
Dibromobiphenyl
2,4,6­
Tribromobiphenyl
Heptachlor
epoxide
F1uoranthene
­
o
,
E'
­
DD 
Pyrene
Chrysene
trans­
Nonachlor
p,
p'­
DDE
106
44
102
54,.
86
44
126
56
92
52
99
58
102
.64
87
55
.

98
65
98
57
120
69
24
37
..
..
160,
43
'
Table
3
(
continued)

GPC/
Flori
si4
average
recovery
(%)

98'
77
84
110
96
48
81
130
100
04
8oa
110
1
100,
140.
8oa
110
85a
7ga
110
63a
120,
MCE/
GPC/
Fl
orisi1
average
recovery
(%)

64a
52
61
54
13
32a
78
50
39
113
53
61
46
38
58
53a
37
49
ND
56
26
11
114'
37
32
Analyte
Dieldrin
3C
­
Tetrachlorob
ipheny1
__
gyp:
­
DDD
p,
p
­
DDD
2,2',
4,4',
5­
Pentachlorodiphenyl
­
tri
s(
Di
ch7
oropropyl)
phosphate
2,3,7,8­
Tetrachlorodibenzofuran
ether
I'

Butyl
benzyl
phthalate
2,2',
4',
5­
Tetrabromobiphenyl
2,
e'­
DDT
1,2,3,4­
Tetrachlorodibenzo­~­
dioxin
Tributoxyethyl
phosphate
4­
Chloro­
e­
terphenyl
2,5­
Dichloroterphenyl.
1,2­
Benzanthracene
3C
2­
Oc
tactilor0b
ipheny1
2,5­
Dichloro­
m­
terphenyl
2,2',
4,5',
6­
Pentabromobiphenyl
1,2.,
3,7,8­
Pentachloro­
p­
dioxin
Mirex
2,2',
4,4',
6,6'­
Hexabromobipheny?
.

2,4',
5­
Trichloro­
o­
terphenyl
.

1,2,3,4,7,8­
Hexac6lorodibenzo­
p­
dioxin
.
78
Benzo­
k­
fluoranthene
85
­

2,4,4',
6­
Tetrachloro­
o­
terphenyl
140,
13C­
Decachlorobiphenyi
110
1,2,3,4,6,7,8­
Heptachlorodi~
benzo­
p­
dioxin
62
Decachlorodiphenyl
ether
120
Octachlorodibenzo­
p­
dioxin
Octachlorodibenzofuran
1,2,5,6­
Dibenzanthracene
Benzo­
g,
h,
i­
perylene
aTwo
determinations.
bND
=
not
detected.
'
One
determination.
ND
25
38
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
investigated
to
determine
which
eluate
should
be
taken
through
further­
fractionation
on
the
Florisil
column.
Approximately
5
pg
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/
methanol
benzene
(
75/
20/
5);
and
toluene
were
collected
separately
and
screened
for
toxaphene
recovery
by
HRGC/
ECD.
Recovery
calculations
were
based
on
summation
of
areas
for
the
toxaphene
respone
in
a
retention
time
window
established
from
the
analysis
of
the
toxaphene
standard.
Recoveries
were
calculated
by
direct
comparison
to
a
toxaphene
standard
and
two
internal
standards
(
1,
Z­
dichloronaphthalene
and
octachloronaphthalene).
The
results
of
these
recovery
calculations
are
summarized
in
TabSe
4.

As
noted
in
Table
4,
the
recoveries
from
the
three
different
quantitation
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
pg
spike
levels.
These
results
demonstrate
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
(
I.
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
associated
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
determined
using
the
automated
HRGC/
MS
search
and
quantitation
routines
based
on
the
mass
spectral
library
established
in
the
method
evaluation
studies.

26
3q
Table
4.

Fraction
Methylene
chloride/
cyclohexane
(
50/
50)

Methylene
chloride/
cycl
ohexane/
benzene
(
75/
2O/
5)

To1uene
Recoveries
of
Toxaphene'
from
&
arbon/
Glass
Adsorbent
Column
Fiber
Relative
to
octachloro­.
naphthalene
('
IS)

87.5
1.4
RCb
40
Direct
comparison
to
toxaphene
standard
79.6
1.4
1.8
Relative
to
1,
Z­
di
chl
oronaphthalene
(
IS)
a
79.9
1.4
2.1
aIS
=
internal
standard.
bNC
=
not
calculated.

27
Table.
5.
Recovery
of
Toxaphene
from
Florisil
Cleanup
Amqunt
of
spike
Fraction
Recov
ery
%
Recovery
of
spike
11­
14
toxaphene
50
mL
hexang
50
mL
90/
10
0.13
pg
0.81
pg
13
81
100
ng
toxaphene
50
mL
hexane
50
mL
90/
10
23
ng
90
ng
.23
90
11­
14toxaphene
+
50
mL
hexane
1.2
IJg
(
AIb
120
(
A)
1
pg
Aroclor
1260
50
m~
go/
ia
1.0
f­
Jg
(
TI
100
(
T)

hexane,
10%
acetone.
b(
A)
=
Aroclor
standard
recovery;
(
T)
=
toxaphene
standard
reco.
very.

28
a
c­

E
2
31
23
0
A
u
­
0
2
h
m
i
0
mrca
no
L
o)
­

tv
om
Ln
*(
C
x
1
'
t
LL
30
..
.
I
L13
4
Census
region
West
Census
division
Mountain
Pacific
0­
14
15­
44
45+
0­
14
45+
Compound
1,2­
Dichlorobenzene
1,2,4­
Trichlorobenzene
Naphtha1ene
Pentachlorobenzene
Diethyl
phthalate
Tributyl
phosphate
Hexachlorobenzene
8­
BHC
Phenanthrene
Di­
n­
butyl
phthalate
Hepzachlor
epoxide
Pyrene
trans­
Nonachlor
p,
p'­
DDT
Butylbenzyl
phthalate
Tripheny1
phosphate
Di­
n­
octyl
phthalate
.

Mi
rFx
­
tris(
2­
Chloroethyl)
phosphate
Total
PCBs
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptach1orobiphe.
ny1
Octachlorobiphenyl
Nonachlorobiphenyl
Decachlorobiphenyl
Figure
6.
Incidence
of
detection
of
semivolatile
organic
compounds
determined
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
(­
1
value
indicates
the
compound
was
not
detected.
The
number
of
symbols
for
each
age
group
indicates
the
.
number
of
composites
analyzed.

31
YY
­­
­­

­­

­­
­­

­­
­­

­­
­­
­­
­­
­­
­­
­­

­­
­­
­­
Census
region
Census
division
0­
14
Compound
1,2­
Dichlorobenzene
1,2,4­
Trichlorobenzene
Naphthalene
Pentachlorobenzene
Diethyl
phthalate
Tributyl
phosphate
Hexachlorobenzene
8­
BHC
Phenanthrene
Di­
n­
butyl
phthalate
Hephchlor
epoxide
Pvrene
tians­
Nonachlor
p,
p'
­
DOE
Dieldrin
p,
p'­
DDT
Butylbenzyl
phthalate
Tri
phe
ny
1
phosph
ate
Di­
n­
octyl
phthalate
Mi
rex
­
tris(
2­
Chloroethyl)
phosphate
Total
PCBs
Tri
ch
1or0b
ipheny1
Tetrachl
orobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachl
orobiphenyl
Nonach'
1
orob
i
pheny
1
Decachlorobiphenyl
­~
Northeast
New
England
Middle
Atlantic
15­
44
45+
0­
14
15­
44
45+

­+
+


++
++
++
+

++
U
++
++
++
++

++
+

++'
­+
­+
+


++

++
++
++
++
++
++

'
+­

,
F
gure
7.
Incidence
of
detection
of
semivolatile
organic
compounds
determined
in
cornposited
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
114
­­­
­­­
­­­

­­­

­­

­­­
­­­

­­
­
­­­

­­­
­­­

­­­

­­­

­­­
­­­

­­­
­­
­­

­­

­­

­­
­­

­­
Census
region
North
Central
Census
division
East
North
Central
West
North
Central
0­
14
15­
44
'
45+
0­
14
15­
44
45+
8
Compound
I
1,2­
Dichlorobenzene
1,2,4­
Trichlorobenzene
Naphthalene
Pentachlorobenzene
Diethyl
phthalate
Tributyl
phosphate
Hexachlorobenzene
$­
BHC
Phenanthrene
Di­
n­
buty7
phthalate
HepTachlor
epoxide
Pyrene
trans­
Nonachlor
p,
e'­
DDE
Dieldrin
p,
p'
­
DDT
Butvlbenzyl
Dhthalate
Tripheny1­
phosphate
Di­
n­
octyl
phthalate
Mirex
­
tris(
2­
Chloroethyl)
.
phosphate
Total
PCBs
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octach1orobipheny1
Nonachiorobipheny1
Decach1orobipheny1
­­+
­­+
+­­++­+

++

++­+++
+

+++
++

­+­­++
­+
­++
+++
++

­

4
­++
++
+++
+++
++
­+­
­++
+


++
­+­
­+­­+
­+­­­+
+


+++
++
­­..
+++
+

­++
++
­++
­++
++
­++
­++
++
+­­
­++
++
+­­­++
++
+


Figure
8.
Incidence
of
detection
of
semivolatile
organic
compounds
determined
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
indicates
the
number
of
composites
analyzed.

33
­­

­­

­­
­­
­­
­­
1.2.4­
Trichlorobenzene
­­
Naphthalene
Pentachlorobenzene
Diethyl
phthalate
Tributyl
phosphate
Hexachlo
robenzene
$­
BHC
Phenanthrene
Di­
n­
butyl
phthalate
HepEachlor
epoxide
Pyrene
trans­
Nonachlor
p,
E'
­
DDT
Butylbenzyl
phthalate
Triphenyl
phosphate
Di­
2­
octyl
phthalate
Mirex
.
­
tris(
2­
Chl
oroethyl)
phosphate
Total
PCBs
~
..

15­
44
45+
0­
14
15­
44
45+
&
ompound
­
1,2
Dichlorobenzene
­


­

+
+
­

+
+
+
+

+
+
+
­

i
+
+
+
+
+

+
+
+
­
+

..
Trichlorobiphenvl
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
quantifiab'le
level.
A
negative
(­)
value
indicates
the
compoun'd
was
not
detected,
The
number
of
symbols
for
each
age
g.
roup
indicates
the
number
of
composites
analyzed.

34
47
The
analyses
for
the
PCBs
was
accomplished
through
manual
identification
and
­
quantitation
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
positive
(+)
value
indicates
that
the
compound
was
detected
at
a
trace
or
positive
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
11present
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
presented
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
characteristic
in
the
time
frame
of
13
to
30
min
(
6%
diethyl
ether
Florisil
fraction
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
differences
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
li'brary
indicates
that
the
major
peaks
in
these
chromatograms
are
due
to
biogenic
materials
(
e.
g.,
fatty
acids
and
cholesterol
re'lated
components)
which
are
not
removed
by
GPC.
A
review
of
the
elution
profiles
presented
in
Figure
1demonstrates
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,
e'­
DDT,
mirex,
trans
­
nonachlor,
heptachlor
epoxide,
and
dieldrin
are
reported
for
the
composite
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
Semivolatile
Organic
Compounds
.
in
the
NHATS
FY82
Composite
Specimens
Compound
Frequency
of
observation
(%)
a
Iy2­
Dichlorobenzene
1,2,4­
Trichlorobenzene
Naphtha1ene
Diethyl
phthalate
Tri
butyl
phosphate
Hexachlorobenzene
p­
BHC
Phenanthrene
Di­
n­
buty1
phtha1ate
HepTachlor
epoxide
trans­
Nonachl
or
&
E'
­
DDE
Dieldrin
p,
p'­
DDT
'

Butvlbenzvl
phthalate
Tribhenyl­
phosphate
Di­
n­
octyl
phthalate
Mi
rex
­
tris(
2­
Ch1oroethyl)
phosphate
Total
PCBs
Trichl
orobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Nonachlorobiphenyl
­.
Decachl
orobiphenyl
aSample
size
=
46
composites.
9
4
40
42
2
76
87
13
44
67
53
93
31
55
69
36
31
13
2
83
22
53
73
73
53
40
13
?

36
YY
­­
..___­­______
­
­.
I
!
Reproduced
fromi
best
available
copy..
.
I
I
1­
MO­
SVO­
O­
l4
RlC
i'
T
I
I
1­
MO­
SVO­
I
5­
44
1.
L
1­
MO­
SV0­
45+
me
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
50
.
..
...
..

1­
MO­
SVO­
O­
II
Itt
I
lJFPU.

tu
_
I
ita
It
ll
Figure
71.
HRGC/
MS
chromatogram
of
the
15/
50%
diethy
,
ether
Florisil
fraction
for
the
three
age
groups
(
0­
14,
15­
44,
and
45
plus)
from
the
Mountain
census
division.

38
r
..
I
_
yLlil_­
Ly­­
IIIII­­­


­
1
Reproduced
from
best'
available
copy.

1­
SA­
SVO­
O­
14
T
1­
MD­
SVO­
O­
I
4
Figure
12.
Comparison
of
the
HRGC/
MS
chromatograms
of
the
0­
14
age
composites
(
6%.
diethyl
ether
Florisil
fractions)
from­
three
census
divisions.

39
52
T
1­
SA­
SVO­
45+

1­
WN­
SVO­
45+

1­
MO­
SVO­
45+

Figure
13.
Comparison
of
the
HRGC/
MS
chromatograms
of
the
45
plus
age
composites
(
6%
diethyl
ether
Florisil
fractions)
from
three
census
divisions.
i
40
53
I
1­
SA­
SVO­
0­
14
'
F
1­
WN­
SVO­
0­
14
ECW
ruc
Ilc
Figure
14.
Comparison
of
the
HRGC/
MS
chromatograms
of
the.
0­
l4.
age
composites
(
15/
50%
diethyl
ether
Florisil
fractions)
from
three
census
divisions.

41
54
,
.
..

'.
.
I
1­
SA­
SVO­
45+

9
I
F
1­
WN­
SVO­
45+

pu
nm
ZIM
1­
MO­
SVO­
45+

F
gure
15.
Comparison
of
the
HRGC/
MS
chromatograms
of
the
45
plus
age.
composites
(
15/
50%
diethyl,
ether
Florisi.
1
fractions)
from
three
census
divisions.

42
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56
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
quantitation
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
semiquantitative
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
distribution
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
illustrates
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
chlorobenzenes
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
pg/
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
pg/
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
pentachlorobenzene
were
not
detected
in
any
of
the
composited
tissue
samples.
The
presence
of
pentachlorobenzene
in
adipose
tissues
has
been
reported
(
Mes,
Davies,
Turton
1985)
at
0.001
pg/
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
incidence
of
detection
may
be
attributed
to
the
respective
method
sensitivities.

57
70
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16.
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MS
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d.
Phosphate
Triesters
Tables
26
to
28
summarize
data
for
triphenyl­,
tributyl­
and
tris(
2­
ch1oroethyl)
phosphate.
Triphenylphosphate
was
detected
in
the
associated
method
blanks
as
well
as
in
the
samples.
The
data
in
Table
26
were
corrected
for
this
background
contribution.
The
data
for
tributyl­
and
tris(
2ch7oroethyl
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
(
teBelL,
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
cornposited
FY82
NHATS
specimens,
including
the
diethyl,
di­
n­
butyl­,
di­
n­
octyl­,
and
the
butyl­
benzyl
analogs,
It
should
be
noted
that
these
phtEalate
esters
were
also
detected
in
method
blanks
prepared
and
analyzed
with
the
composite
samples
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
1­
19
for
diethyl
phthlate,
1.2
to
12
pg
for
di­
n­
butyl
phthalate,
and
2.9
to
20
pg
for
di­
n­
octyl
phthalate.
Blank
values
for­
butylbenzyl
phthalate
ranged
from
not
detected
at
0.20
pg
to
0.78
pg.

Dimethyl
phthalate
was
also
included
in
the
analytical
standard
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
quantitation
routine
for
the
composite
sample
extracts.
Naphthalene
and
phenanthrene
were
determined
.
at
trace
lev.
els
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
comp'osite
specimens.
Estimated
detection
limits
for
these
analytes
are.
provided
based'on
the.
observed
instrumental
sensitivity
from
the
calibration
standards.
It
should
be
noted
that
the
estimated
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.

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Table
35.
Compounds
Not
Detected
in
the
FYSZ
Composite
Specimens
Estimated
detection
level
(
dg)
a
Analytes
for
20­
9
sample
6­
BHC
Aldrin
Heptachlor
Endrin
y­
Chl
ordane
Polychlorinated
biphenyls,
PCBs
Monochlorobiphenyl
Dich7orobiphenyl
Chlorobenzenes
Trichlorobenzene
(
1,2,3­;
1,3.5­)
Tetrachlorobenzene
(
l,
2,3,4L
;­
l,
Z,
3,5­;
1,2,4,5­)
Pentachlorobenzene
Phthalate
esters
Dimethyl
phthalate
Phosphate
triesters
tris­(
Dich1oropropyl)
phosphate
ester
._
Tributoxyethyl
phosphate
ester
Polynuclear
aromatic
hydrocarbons,
PAH
Acenaphthylene
Acenaphthene
F1uorene
F1uoranthene
Chrysene
I
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.050
0.010
0.01 
0
0.010
0.010
0,010
0.010
0.010
0.,
050
0.050
0.010
0.010
0.010
0.010
0.010
r
.


.
10.2
_­>
­
Analytes
Polybrominated
biphenyls,
PBBs
Bromobiphenyl
Dibromobiphenyl
Tribromobiphenyl
Tetrabromobiphenyl
Pentabromobiphenyl
Hexabromobiphenyl
Polychlorinated
diphenyl
ethers,
PCDEs
Ch?
orodiphenyl
ether
Pentachlorodiphenyl
ether
;
Decachlorodiphenyl
ether
Polychlorinated
terphenyls,
PCTs
Chloroterphenyl
Dichloroterphenyl
Trichf
oroterpheny1
Chlorophenols
OichloroDhenol
Trichlorbphenol
Pentachlorophenol
Estimated
detection
level
oJ9/!
2)
a
for
20­
9
sample
0.010
0.010
0.025
Ot.
050
0.050
0.100
0.010
0.050
0.100
0.010
0.010
0.025
0.010
0.025
0.050
.

aThe
estimated
detection
1imits
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
components
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
remain
unidentified.
The
importance
of
characterizing
these
unidentified
peaks
is
recognized
to
be
necessary
in
achieving
the
goals
of
the
broad
scan
analysis
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
Assi
gnment
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
responses
of
the
6%
and
15/
50%
Florisil
fraction
extracts
of
a
specific
composite
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
completed
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
demonstrate
response
corresponding
to
the
internal
standards
(
dichloro­
and
octachloronaphthalene
the
surrogate
compounds,
organochlorine
pesticides,
and
PCBs.
Figures
21
to
23
are
provided
as
a
matter
of
reference
to
determine
the
el'ution
characteristics
of
specific
compounds
and
compound
classes
with
respect
to
the
response
noted
for
the
6%
Fl.
orisi1
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
background
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
additional
compounds
of
interest
may
have
been
overlooked
in
the
HRGC/
MS
interpretation
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
responses
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
spectrome'try
techniques
such
as
negative
chemical
ionization
(
NCI)
or
mass
spectrometry/
mass
spectrometry
(
MS/
MS).
The
selection
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
quantitation
of
specific
organochlorine
pesticides,
chlorobenzenes,
and
PCB
isomers
and
HRGC/
MS­
SIM
or
to
generate
data
on
specific
target
analytes
or
compound
classes.

104
IC
1­
ES­
SWO­
45+
HRGC/
MS'.

too1
I­
ES­
SVO­
45+
HRGC/
ECD
B
a
5
15
2%
25
35
Figure
17.
HRGC/
MS
and
HRGC/
ECD
chromatograms
of
the
6%
dieth.
y.
1
ether
Tlorisil
fraction
of
the
45­
plus
age
category
of
the
East
Sooth
Central
census
division.

105
1­
ES­
SVO­
45+
HRGC/
MS
I008
­

I
I
I
1­
ES­
SVO­
45+
HPGC/
ECD
i
5
IB
Figure
18.
HRGC/
MS
and
HRGC/
 CD
chromatograms
of
the
15/
50%
'
diethyl
ether
Fforisil
fraction
of
the
45­
plus
age
category
of
the
East
South
Central
census
division.

106
0
I
­
ES­
SVO­
O­
i
4
1aoo
1
I
I
\

..

­
ES­
SVO­
15­
44
I
00
0
5
le
1s
20
25
3e
35
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.

TO7
t
08
j+

e
5
ita
IS
El
30
35
Figure
20.
HRGC/
ECD
chromatogram
from
the
analysis
of
the
15/
50%
diethyl
ether
Flgrisif
fraction
of
the
three
age
group
composites
from
the
East
South
Central
(
ES)
census
division.

7
08
0
I
1
aim
i
I
II'
i
0
J
"
­
L­
LL_
l.._
I
30
35
5
tff
15
20
25
L1s
Wl.
1
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
I
OD1
0
­
ES­
SVO­
45+

5
10
15
20
25
I
I
30
35
IWI
Figure
22.
Comparison
of
the
HRGC/
ECD
chromatograms
of
the
6%
klorisil
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).

110
1
8
I
I
I
I
I
D
I
I
I
I
I
I
I
I
I
I
I­
ES­
SVO­
4S­
t
I
I
17
I­
L
10
15
20
25
38
35
IO
Supclco
St&
d
Peitlcld.
MU(

I.
Dlchleramph+
holem,
K(
1)
2.
0­&
IC
3.
P­
MC
4.
8HC
5.
&
IBHC
6.
Hcptechia
7.
Aldrin
8.
Heplochlw
epoxide
9.
Endautfon
I
I
ID.
Dicldrln
'
IS
I)
It.
pap'­
ODE
12.
Endrin
13.
p.
p'­
DDD
14­
Endrin
oldehydc
15.
fndnwllon
wlMc
16.
p.
p'­
DOT
17.
Octnchlawaphtholcrr,
tsjz)

J
Retcntlon
llm.
Mmh,

Figure
23:
Comparison
of
the
HRGC/
ECD
chromatograms
of
the
6%
Florist1
fraction
of
the
45­
plus
age
category
of
the
ES
census
division
and
the
elution
of
a
commercial
mixture
(
Supel­
co)
of
pesticides.

717
7
I
I
Figure
24,
HRGC/
ECD
chromatograms
of
method
blanks
from
6%
and
3.5/
150%
Florisi
1
fractionation.

112
4­
B.
Toxaphene
Analysis
The
sample
extracts
from
the
45+
age
category
that
were
taken
through
additional
cleanup
and
fractionation
procedures
for
toxaphene
determination
were
analyzed
by
both
HRGC/
ECD
and
HRGC/
MS
in
the
SIM
mode.
The
methylene
chloridelcyclohexane
fraction
from
the
carbodglass
fiber
column
contained
the
organochlorine
pesticides,
PCBs,
and
the
toxaphene
components.
This
required
further
fractionation
on
Florisil
as
described
in
the
experimental
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
toxaphene
mixture.

Since
toxaphene
is
a
multicomponent
mixture
of
polychlorinated
compounds
it
was
determined
that
HRGC/
MS­
SIM
techniques
were
necessary
to
determine
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
components
within
technical
toxaphene
range
from
177
to
670
compounds
resulting
frotp
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
polychlorinated
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
same
interferences
still
persisted
even
after
the
extensive
cleanup
procedures.
Ineparticular,
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
sqmple
analysis
has
been
noted
in
other
studies
(
Ribick,
Dubay,
Petty,
Stalling,
Schmitt
1982;
Jansson,
Wideqvist
1983).
Quantitation
of
the
data
is
not
possible
due
to
these
drastic
differences
in
the
sample
extracts
and
the
standard.
However,
the
low
level
toxaphene
standard
that
was
analyzed
was
equivalent
to
approximately
0.10
Vg/
g
in
the
tissue
extracts.
Based
on
the
responses
observed
in
the
selected
composite
specimens
the
residue
levels
of
toxaphenes
in
the
composite
tissues
were
less
than
the
0.10
pg/
g
level.

113
I
1­
6
114
0;
i
m
1
e:
C..
P..
..

116
12­
9
=
1
u
m
u­
LW
rn+

U
.
I­

C,
v)

.
C
L
s
U
..
m
z
a
ua
23
8 
0
al
­#
alC
me
t
Q
.
­
m
ax
 
3
d,

i
tL
30
mv117
VI
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
characteristic
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
QWQC
program
included
analysis
of
spiked
lipid
samples,
spiked
blanks,
replicate
analysis
of
homogenized
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
response
of
the
internal
standard
(
anthracene­
dlo)
for
each
sample
analyzed.
Also,
the
identification
of
a
compound
via
the
automated
quantitation
routine
wa5
verified
by
retrieving
and
verifying
the
full
scan
mass
spectra
for
each
identification
versus
the
NBS
mass
spectra?
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
yelatively
free
of
contamination
from
the
target
analytes:
The
homogenized
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
ZZ%.(
tris(
l,
3
dichloropropyl)
phosphate/
tri­
m­
tolylphosphate)
to
204%
for
p,
p­
DDE.
.
The
high
recovery
of
e,
p­
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
1%
for
the
p,
g­
DDE
to
74%
for
the
2,4,5­
trichIoro­
g­
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
procedures
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
131
Table
36.
Qualitative
Summary
of
Toxaphene
Identification
in
45+
Age
Category
Sample
no.

1­
WN­
45+
2­
WN­
45+
I­
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+
Presence
of
toxaphenea
+
+
++
b
++
b
+
++
b
aIons
monitored
for
HRGC/
MS
analysis
included
m/
z
231,
233,
235,
269,
271,
273,
305,
307,
and
309.
bAdditional
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
SemivolatJle
Organics
from
Spiked
Human
Adipose
Tissues
MRI
sample
number
Average
'
Standard
Compound
QC
223
QC
229
QC
234
QC
239
QC
240
Recovery
Deviation
1.2­
Dichlorobenzene
51
54
39
ND~
ND
48
8
2.4­
Di
chlorophenol
48
ND
82
63
103
74
24
1.2,4­
Trichlorobenzene
56
40
57
ND
ND
51
10
Naphthalene
127
140
97
ND
ND
120
22
2.4,6­
Tri
chlorophenol
30
ND
41
30
45
37
8
Acenaphthylene
62
55
40
32
33
44
13
Dimethyl
phthalate
39
88
53
48
54
56
19
Acenaphthene
67
53
40
34
32
46
16
Pentachlorobenzene
54
42
30
25
21
34
14
F1uorene
71
54
44
41
35
50
15
Diethyl
phthalate
55
87
59
58
59
65
13
4­
Chlorodiphenyl
ether
61
50
38
31
26
41
14
4­
Bromobiphenyl
68
61
47
45
37
52
13
0­
BHC
103
100
83
66
62
83
19
Hexachlorobenzene
67
45
47
44
39
49
12
p­
BHC
97
ND
62
56
50
66
21
Phenanthrene
83
75
65
61
60
70
11
A­
BHC
58
53
74
61
66
62
8
Heptachlor
71
77
93
58
66
73
13
Di­
n­
butyl
phthalate
110
126
55
46
86
85
34
Aldyin
80
87
71
67
66
*
74
9
4,4'­
Dibromobiphenyl
96
115
98
76
89
95
14
2,4,6­
Tribromobiphenyl
70
79
70
55
58
66
10
Heptachlor
epoxide
67
111
106
79
91
91
18
Fluoranthene
81
97
93
64
73
79
14
.­
e.'
­
ODE
65
63
61
42
50
56
10
Pyrene
68
96
94
58
69
78
16
Chrysene
66
70
67
45
55
61
10
y­
Chlordane
65
83
78
59
67
71
10
trans­
Nonachlor
78d
6:
90
6od
77
76d
l2
214
220
217d
165
203d
204
23
136
75
41
42
ND
74
45
0­
p'
­
DDD
63
77
69
42
56
61
13e­
e'
­
DDD
69
136
116
66
79
93
31
2,2',
4,4',
5­
Pentachlorodiphenyl
ether
58
102
85
51
69
73
21
'­
DDT
54
136
116
66
79
90
35
­
tris(
1­
dichloropropyl)
phosphate
37
31
15
17
12
22
11
Butyl
benzyl
phthalate
74
55
27
26
22
41
23
2,2'.
4'
,5­
Tetrabromobipheny1
64
128
116
58
68
87
33
E­
e
'­
DDT
63
126
126
43
62
84
39
Triphenyl
phosphate
51
40
21
17
17
29
15
4­
Chloro­
e­
terphenyl
33
70
57
27
38
49
25
2.5­
Dichloro­
g­
terphenyl
45
91
77
32
45
58
25
Di­_
n­
octy1
phthalate
143
55
46
29
43
63
46
Mirex
48
102
68
31
42
58
28
Tri­
nrto1y1
phosphate
ND
32
23
15
18
22
7
2,4",
5­
Tr
ichloro­
g­
terphenyl
35
143
115
26
43
72
53
2.4.4"
,6­
Tetrachloro­~­
terphenyl
48
160
114
32
39
80
57
d
Naphthalene
59
54
38
18
26
39
17
4­&~­
1,2,4,5­
Tetrachlorobenzene
57
52
40
21
24
39
16
13C6­
Hexachlombenzene
65
47
46
43
39
48
9
d,*­
Chrysene
40
51
47
21
24
37
11
aA
bulk
lipid
sample
was
spiked
with
the
following
compounds
at
concentrations
equivalent
to
0.1
pg/
g.
The
,,
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.

120
133
>

­­
m
w
e
m
.
c
­
0
VI
k
L
W
rl
>
N
0
cu
V
W
p:

U
W
4
U
N
L
W
0
L
0)
V)
n
cr
EW
c
arlE"
CN
.
i
­
0,

W
n
n
SW
W
WO
N
c
"
0
.
r
B
U
23
rn
0
N
ai
m
I
­
w
n
cr
m
I
I­
r
n
LV)
wo
cr
en
121
01
r;
0,
>
0
V
L
W
En
m
L
v
>
m
al
5
e
0
c
E2
0
122
(
n
=
5)
(
n
=
6)
Averaae
..
Compound
recovery
RSD
(%)
recovery
RSD
(%)

1,2­
Dichlbrobenzene
48
17
60
33
2,4­
Dichlorophenol
74
32
62
20
1,2,4­
Trichlorobenzene
51
20
61
14
Naphthalene
120
18
74
46
2,4,6­
Trichlorophenol
37
22
65
23
Acenaphthylene
44
30
65
17
Dimethyl
phthalate
56
34
55
22
.
Acenaphthene
46
34
65
12
Pentachlorobenzene
34
30
61
18
F1uorene
50
20
65
15
Diethyl
phthalate
65
34
49
13
4­
Chlorodiphenyl
ether
41
25
66
14
4­
Bromobi
phenyl
wBHC
Hexachlorobenzene
f3­
BHC
Phenanthrene
A­
BHC
Heptachlor
Di­
n­
butyl
phthalate
A1dFi
n
4,4'­
Dibromobiphenyl
2,4,6­
Tribromobiphenyl
Heptachlor
epoxide
F1uoranthene
­
o,
p'­
DDE
Pyrene
Chrysene
w­
Chl
ordane
trans­
Nonachl
or
~,
p'
­
DDE
Dieldrin
o.
D'­
DDD
­,
J­­~


p,
p'
­
DDD
2,2',
4,4'.
5­
Pentachlorodi~
henvI
52
23
79
19
83
25
78
16
49
24
73
35
66
32
104
20
70
16
82
8
62
13
86
19
73
18
98
30
85
40
57
52
74
12
78
15
95
15
96
16
'

66
15
100
17
91
20
89
25
79
18
104
24
56
18
94
20
78
21
100
26
61
16
97
21
71
14
94
22
76
16
86
34
204
11
104
29
74
61
90
28
61
21
109
21
93
33
117
30
.­"
ether
73
29
108
28
.
~,~
DDT
90
39
102
22
­
tris(
l,
3­
Dichloropropyl)
phosphate
22
50
29
21
Butvl
benzvl
Dhthalate
41
56
52
21
2,2i
,4'
,5­?
etrabromobiphenyl
87
38
120
18
g,
p'­
DDT
84
41
110
17
Triphenyl
phosphate
29
52
78
17
123
I3b
Table
39
(
continued)

Compound
4­
Chloro­
yterphenyl
2,5­
Dichloro­
o­
terphenyl
Di­
n­
octyl
phxhalate
Mi
rex
Tri­
m­
tolyl
phosphate
2,4,'
5­
Trichloro­
o­
terphenyl
'
,6­
Tetrac
hl­
dro­
o­
terpheny
1
­
Lipid
samples
Blanks
.

(
n
=
5)
(
n
=
6)
Average
recovery
RSD
(%)
recovery
RSD
(%)

49
51
113
22
58
43
113
21
63
73
41
39
58
48
116
21
22
32
42
24
72
74
131
32
2,4,4
80
71
133
33
d
­
Naphthalene
39
44
69
30
*
C6­
1,2,4,5­
Tetrachlorobenzene
39
41
63
22
f3C6­
Hexachlorobenzene
48
19
74
36
d12­
Chrysene
37
30
127
21
\

124
I37
C.
Porcine
Fat
A
porcine
fat
sample
(
Adipose
121)
provided
by
EPA­
EMSL/
LV
was
analyzed
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.
tai1
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
tissue
samples.
Table
40
also
reports
the
actual
concentrations
of
porcine
fat
as
reported
by
 PA­
EMSL/
LV
and
the
accuracy
of
each
of
$
he
measurements.
Positive
identification
and
quantitation
of
each
of
the
spiked
analytes
was
not
possible
due
to
the
limitation
encountered
for
the
analysis
of
1.13
g
sample
aliquots.
Trace
levels
of
trans­
nonachlor
and
p,
p'­
DDT
were
detected
in
the
sample
extracts.
The
p,
e'­
DDE
residue
was
detected
in
all
five
of
the
analyses
with
an
accuracy
ranging
from
76
to
210%.
The
levels
of
2,
p­
DDE
were
detected
as
positive
quantifiable
values.
Responses
to
characteristic
ions
from
the
molecular
clusters
for
hexachlorobenzene,
fi­
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
1­
or
4­
9
aliquots
of
the
homogenized
lipid.
The
HRGC/
MS
analysis
resulted
in
the
detection
of
several.
'
organochlorine
pesticides,
PCBs,
phthalate
esters,
and
PAHs.
The
results
of
the
replicate
analysis
­&
re
presented
in
Table
41.
The
compounds
that
were
detected
.
consistently
in
the
4­
g
samples
included
hexachlorobenzene,
f3­
BHC,
heptachlor
epoxide,
trans­
nonachlor,
p,
p'­
DDE,
p,
e'­
DDT,
diethyl
phthalate,
and
di­
n
octyl
phthalate,

The
results
for
e,
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
e,
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
9
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
13%
r
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U
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128
IUI
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
chloride
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
typically
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
pg
for
diethyl
phthalate,
1.2
to
12
pg
for
di­
n­
butyl
phthalate,
and
2.9
to
20
pg
for
di­
n­
octyl
phthalate
Butyl
benzyl
phhalate
ranged
from
not
detected
at
0.2
pg­
to
0.78.
pg.
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
bJank
values.
Ifthe
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
pg,
and
the
level
of
tributyl
phosphate
esters
was'detected
as
7
pg
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
detection
level
of
the
phosphate
triesters
was
handled
as
described
for
the
phthalate
esters.

F.
Surrogate
Compound
Recovery
'

The
stable
isotope
labeled
surrogate
compounds
representative
of
chlorobenzenes,
PCBs,
and
PAHs
were
spiked
into
all
composite
samples,
QC
samples
and
method
blanks
prior
to
sample
preparation
to
assess
method
performance
on
a
per
sample
basis.
The
absolute
recovery
of
each
of
the
surrogates
was
measured
versus
the
internal
standard,
anthracene­
d,,,
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
1,2,4,5­
tetrachlorobenzene
and
13C12­
decachl
orobiphenyl
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
(
Figure
21).
The
results
from
the
HRGC/
ECD
determination
generally
demonstrate
higher
recoveries
than
by
the
HRGC/
HS
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
standard
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.

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ew
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c
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0,

4
c,
3
t
J
,
Cn
n
Un
U
in
i
Q
7
00
U
X
.
r
L
cl
i2
As
noted
in
Figure
21,
the
13Cl~­
decachlorobiphenyland
the
octachloronaphthalene
elute
within
a
narrow
retention
window
as
compared
to
the
retention
window
for
anthracene­
dlo
and
the
surrogate.
These
results
suggest
that
additional
internal
standards
are
necessary
to
provide
better
quantitation
in
the
broad
scan
analysis
scheme.
Estimates
of
the
recoveries
of
the
13C,­
monochloroand
13C,
2­
octachlorobipheny~
surrogates
by
HRGC/
ECD
are
difficult
because
of
coelution
of
other
compounds.

G.
Internal
Standard
Response
The
response
of
the
internal
quantitation
standard
anthracene­
dIo
was
routinely
monitored
and
recorded
to
determine
if
there
were
apparent
problems
resulting
from
instrument
stability.
Ifdrastic
changes
(
greater
than
50%
of
standard)
in
the
anthracene­
dlo
response
were
noted,
the
HRGC/
MS
analyst
was
required
to
reanalyze
a
calibration
standard
to
determine
ifthe
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
significant
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
demonstrated
that
the
instrument
stability
was
not
responsible
for
the
observed
internal
standard
fluctuations.

VI.
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016721
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polychlorinated
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EPA
560/
5­
86­
038,

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Broad
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Volume
V:
Trace
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EPA
560/
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86­
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MJ.
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Comparison
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(
Mills,
Onley,,
Gaither
versus
automated
gel
permeation)
for
residues
of
organochlorine
pesticides
and
polychlorinated
biphenyls
in
human
adipose
tissue
Bull
Environ
Contam
Toxicol
25:
59­
64.

Watanabe
I,
Yakushiji
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Kunita
N.
1980.
Distribution
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and
polychlorinated
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in
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Bull
Environm
Contam
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25:
810­
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137
Wolff
MS,
Anderson
HA,
Camper
F,
Nikaido
MN,
Daum
SM,
Haymes
N,
Selikoff
13.
1979.
Analysis
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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
polybrominated
biphenyl
CPBB)
residues
in
serum
and
fat
of
Michigan
residents.
Bull
Envirdnm
Contam
Toxicol
21:
775­
781.

Wolff
MS,
Anderson
HA,
Selikoff
IJ.
1982.
Human
tissue
burdens
of
halogenated
aromatic
chemicals
in
Michigan.
JAMA
247(
15):
2112.

Wolff
MS,
Fischbein
A,
Thonton
J,
Rice
C,
Lilis
R,
Sefikoff
IJ.
1982.
Body
burden
of
polychlorinated
biphenyls
among
persons
employed
in
capacitor
manufacturing
Int
Arch
Occup
Environ
Health
49:
199­
208.

Wolff
MS,
Thornton
3,
Fischbein
A,
Lilis
R,
Selikoff
13.
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
identification
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
11.
Global
occurrence
of
hexachlorobenzene
(
HCB)
and
polychlorocamphenes
(
toxaphene
(
PCC)
in
biological
samples.
Fresenius
Z
Anal
Chem
300:
387­
402.

,
138
I51
I
I
I
8
8
1
I
I
I
I
APPENDIX
A
NHATS
FY82
COMPOSITE
SAMPLE
DATA
REPORTED
FOR
ALL
TARGET
COMPOUNDS
WITHIN
A
CENSUS
DIVISION
139
Table
A­
1.
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
Compos
ite
no.
Age
group
Wet
tissue
weight
%
lipid
Compound
Dichlorobenezene
Trich!
orobenzene
Naphtha1ene
Pentachlorobenzene
Diethyl
phthalate
Tributyl
phosphate
Hexac
h
1o
robenzene
f3­
BHC
Phenenthrene
Di­
n­
butyl
phthalate
Hepzachlor
epoxide
Pyrene
trans­
Nonachfor
p,
p'­
DDE
Dieldrin
p,~'
­
DDT
Butylbenzyl
phthalate
Triphenyl
phosphate
Di
­
n­
octy1
phtha1ate
Mi
rex
Tris
(
2­
chloroethyl)
phosphate
Total
PCB'S
Tr
ich1orobipheny1
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobipheny?
Octachlorobiphenyl
Nonachlorobiphenyl
Decachlor0b
ipheny1'
Total
pg/
composi
te
specimena
MO
­
Mountain
(
1)
(
1)
(
1)
0­
14
15­
44
45+
9.0
g
18.3
g
21.0
g
62.3
74.1
84.3
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
NO
(
0.20)
ND
(
0.20)
ND'(
0.20)
ND
(
0.20)
ND
(
0:­
20)
ND
(
0.20)
NO
(
0.20)
ND
(
0.20)
ND
(
0.20)
b
ND
(
0.50)
0.
a7
b
ND
(
1.0)
ND
(
1.0)
ND
(
0.20)
0.31
I
0.59
ND
(
0.20)
1.5
4.6
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
b
ND
(
2.4)
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
.
1.0
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
ND
(
0.40)
ND
(
0.40)
2.8
5.
I
8.1
24
ND
(
1.0)
ND
(
1.0)
NO
(
1.0)
tr
'
o.
2i
0.90
2.4
b
3.6
7.8
b
tr
0.89
9.6
b
ND
(
0.20)
ND
(
12.2)
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
b
ND
(
0.80)
ND
(
0.80)
NO
(
0.20)
1.2
11
NO
(
0.20)
NO
(
0.20)
ND
(
0.20)
NO
(
0.20)
ND
(
0.20)
tr
0.44
ND
(
0.40)
ND
(
0.40)
tr
2.2
ND
(
0.40)
tr
1.2
4.8
ND
(
0.40)
ND
(
0.40)
3.3
NO
(
0.40)
ND
(
0.40)
ND
(
0.40)
ND
(
0.40)
ND
(
0.40)
ND
(
0.40)
ND
(
1.0)
ND
(
1.0)
ND
(
1.0)

aND
=
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.
%
ata
n,
ot
summarized.

140
I
I
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
DivisionI
I
Census
division
Composite
no.
Age
group
Wet
tissue
weight
%
lipid
I
1
Compound
I
Dichlorobenezene
Trichlorobenzene
Naphthalene
Pentachlorobenzene
Diethyl
phthalate
Tributyl
phosphate
Hexachlorobenzene
8­
BHC
Phenenthrene
D
i­
n­
bu
ty1
phthalate
Hephch7
or
epoxide
Pyrene
trans­
Nonachlor
I
I
I
D
p,
p
­
DDE
Dieldrin
p,
E'
­
DDT
Butylbenzyl
phthalate
Triphenyl
phosphate
Di
­
n­
octy1
phthalate
Mirex
I
I
,.
Total
pg/
composi
te
specimena
NE
­
New
England
(
1)
(
1)
(
1)
0­
14
15­
44
45+
19.1
g
21.9
g
26.7
g
55.1
87.6
79.2
ND
(
0.20)
ND
(
0.20)
tr
0.77
ND
(
0.20)
N5
(
0.20)
ND
(
0.20)
ND
(
0.20)
tr
0.60
ND
(
0.20)
ND
(
0.20)
ND
(
a.
20)
ND
(
0.20)
tr
0.34
tr
0.32
tr
0.38
ND
(
1.0)
NO
(
1.0)
ND
(
1.0)
ND
(
0.20)
24
\
tr
0.31
ND
(
0.20)
11
2.0
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
tr
0.28
ND
(
0.20)
4.48
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
ND
(
0.40)
9.9
ND
(
0.40)
1.4
47
20
ND
(
1.0)
ND
(
1.0)
ND
(
1.0)
ND
(
0.20)
6.8
7.1
ND
(
0­
20)
ND
(
0.20)
ND
(
0.20)
ND
(
0.40)
ND
(
0.40)
ND
(
0.40)
tr
0.69
tr
0.24
ND
(
0.20)
ND
(
0.20)
tr
0.70
tr
0.60
Tris
(
2­
chloroethyl)
phosphate
ND
(
0.80)
ND
(
0.80)
NO
(
0.80)
Total
PCB's
ND
(
0.20)
2.0
3.4
Trichlorobiphenyl
ND
(
0.20)
ND
(
0­
20)
ND
(
0.20)

I
Tetrachlorobiphenyl
ND
(
0.20)
tr
0.36
tr
0.23
Pentachlorobiphenyl
ND
(
0.40)
tr
0.46
tr
2.72
I
Hexachlorobiphenyl
ND
(
0.40)
tr
1.2
ND
(
0.40)
Heptachlorobiphenyl
ND
(
0.40)
ND
(
0.40)
h#
(
0.40)
Octach1
orobipheny7
ND
(
0.40)
ND
(
0.40)
tr
0.43
Nonachlorobiphenyl
ND­(
0.40)
ND
.
(
0.40)
ND
(
0.40)
Decachlorobiphenyl
ND
(
1.0)
ND
(
1.0)
ND
(
1.0)

D
D
aND
=
not
detected.
Value
in
parentheses
is
the
estimated
limit
of
detection
(
LOD).
tr
=
trace.
The
compound
is
present
at
a
level
between
LOD
and
1OQ.

I
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
Census
division
Composite
no.
Age
group
Wet
tissue
weight
%
lipid
Compound
Dichlorobenezene
Trichlorobenzene
Naphtha1ene
Pentachlorobenzene
Diethyl
phthalate
Tributyl
phosphate
Hexachlorobenzene
p­
BHC
Phenenthrene
Oi­
n­
butyl
phthalate
HepEach?
or
epoxide
Pyrene.
trans­
Nonachlor
p,
e ­
ODE
Dieldrin
p,
p ­
DDT
Butylbenzyl
phthalate
Triphenyl
phosphate
0i­
n­
octy1
p
htha1ate
Mi
rex
Tris
(
2­
chloroethyl)
phosphate
Total
PCB s
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyt
Octachlorobiphenyl
Nonachlorobiphenyl
Decachlorobiphenyl
Total
pg/
composi
te
specimena
PA
­
Pacific
(
1)
(
1)
0­
14
45+
19.7
g
22.0
g
62.9
19.2
ND
(
0.20)
1
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
tr
0.20
ND
(
0.20)
ND
(
0.20)
ND
(
0.45)
ND
(
0.49)
ND
(
1.0)
ND
(
1.0)
tr
0.37
1.7
tr
0.48
b
ND
(
0.20)
ND
(
0.20)
ND
(
0.76)
ND
(
2.6)
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
ND
(
0.40)
ND
(
0.40)
3.2
ND
(
0.20)
ND
(
1.0)
ND
(
1.0)
tr
0.27
ND
(
0.20)
ND
(
0.20)
1.7
ND
(
0.40)
ND
(
0.40)
ND
(
2.3)
16
ND
(
0.20)
ND
(
0.20)
ND
(
0.80)
NO
(
0.80)
ND
(
0.20)
6.7
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
ND
(
0.20)
NO
(
0.40)
tr
0.71
NO
(
0.40)
tr
0.44
ND
(
0.40)
2.
a
NO
(
0.40)
2.2
ND
(
0.40)
tr
0.56
ND
(
1.0)
ND
(
1.0)

aND
=
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,
bData
not
summarized.

142
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