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APPENDIX B
This section contains the results of the Quality Assurance
Program. Data for all compounds are reported in this appendix.
-------
LIST OF TABLES AND FIGURES
I. INTERNALLY SPIKED LIPID SAMPLES
Table B-l. Percent Recovery of Measurements for Compounds from
the Twenty Internal Spiked Lipid Samples.
Table B-2. Average Percent Recovery of Measurements of PCDDs and
PCDFs From the Spiked Lipid Samples.
Figures B-l to B-5. Percent Recovery of Spiked Internal QC
Samples.
II. SPLIT SAMPLES
Tables B-3 to.B-9. Results of Split Sample Analyses.
III. UNSPIKED CONTROL LIPID SAMPLES
Figures B-6 to B-21. Concentration in Unspiked Control Lipid
Samples.
Table B-10. Mean Measurements in the Unspiked Control Lipid
Samples.
IV. CALIBRATION DATA
Figures B-22 to B-47. RRF Control Charts.
V. INTERNAL QUANTITATION STANDARDS
Figures B-48 to B-56. Internal Quantitation Standards Recovery
Plots.
B-2
-------
I. INTERNAL SPIKED LIPID SAMPLES
Table B-l and Figures B-l through B-5 present the accuracy
and precision data for all compounds from the internal spiked
lipid samples. Table B-2 shows the % recovery for each
measurement broken down by spike level. The recovery data in
Figures B-l through B-5 are plotted in the order of analysis.
Three hundred seven of the 320 measurements were within the data
quality objectives of 50 - 130% accuracy. The 13 data points
that were outside the data quality objectives occurred in five
compounds:
Compound Number of data Number of data
points below points above
50% recovery 130% recovery
2,3,7,8-TCDD 0 1
2,3,4,7,8-PeCDF 1 2
1,2,3,4,7,8-7
1,2,3,6,7,8-HxCDD 0 6
1,2,3,4,6,7,8-HpCDD 0 1
OCDD 2 0
Eleven of the 13 points outside of the data quality
objectives occurred in samples which were spiked at the low spike
level. A high background level in the lipid matrix relative to
the low spike level resulted in, percentage-wise, more
variability in the results. In 10 of these 11 cases the amount
of the spike added was less than 14% of the background level.
The amount of the low level spike for OCDD was 6% of the
background level.
The two data points that were not low-level-spiked samples
were for 2,3,7,8-TCDD, which was spiked at the high level and had
a recovery of 135%, and for 1,2,3,4,7,8-HxCDD which was spiked at
the medium spike level and had a recovery of 143%.
The 1,2,3,4,7,8-HxCDD and 1,2,3,6,7,8-HxCDD isomer
concentration levels were reported throughout this study as a
combined response. This was necessary because these isomer pairs
were not completely resolved on the 60-meter DB5 column. The
1,2,3,4,7,8-HxCDD is typically less than 20% of the 1,2,3,6,7,8-
HxCDD concentration.
B-4
-------
II. SPLIT SAMPLES
Tables B-3 through B-9 present the data on the split
samples. The precision of the measurements are generally very
good, with the relative percent differences (RPD) usually less
than 20%. Fifty-eight of the 81 RPD values were less than 10%.
Seventeen RPD values were between 10 and 20%. Only 6 values were
greater than 20% RPD. These measurements are discussed below.
The four highest RPD values (90.8% for OCDF; 80.1% for OCDF;
36.6% for OCDF; 23.6% for 2,3,4,6,7,8-HxCDF) were from samples
in which the measurements were close to the detection limits. In
each of these four occurrences one of the measurements was a
trace value and the other was a positive quantifiable value. The
comparison of a trace value to a positive quantifiable value
resulted in a high RPD. The remaining two occurrences above 20%
RPD were only slightly above (20.2% 1,2,3,6,7,8-HxCDF; 23.6%
2,3,4,6,7,8-HxCDF). In both of these cases, both pairs of
measurements were positive quantifiable values.
There were 21 data pairs in which both measurements were
"not detected" (ND). Data on the level of detection on these
measurements can provide some information on the variability of
the detection limit from analysis to analysis.
There were 5 data pairs in which one measurement was a trace
value and the other was not detected (ND). In two of those cases
the level of detection (LOD) for the ND value was higher than the
trace value. In two other cases the LOD for the ND value was
lower than the trace value. And in the fifth case the LOD in the
ND sample was the same as the trace value.
There were 5 data pairs in which one measurement was a
positive quantifiable (PQ) value and the other was a ND value.
In 4 of the cases the LOD for the ND value was greater than the
PQ value. In one case the LOD was lower.
B-5
-------
III. UNSPIKED CONTROL LIPID SAMPLES
Plots of the measurements of the compounds in the unspiked
control lipid samples are given in Figures B-6 through B-21. The
mean and 95% confidence interval established in the Method
Evaluation Study25 are indicated on each plot.
Three hundred of the 320 data points were within the 95%
confidence intervals (CI). The following compounds had data
values that were outside the 95% CI:
2,3,4,7,8-PeCDF 1 point higher than 95% CI
1,2,3,4,7,8-HxCDF 5 points lower than 95% CI
1,2,3,4,7,8-/
1,2,3,6,7,8-HxCDD 8 points lower than 95% CI
1,2,3,4,6,7,8-HpCDD 5 points higher than 95% CI
OCDD 1 point higher than 95% CI
The mean values from the 20 samples run during the study
from January 1987 through November 1987, were compared to the
mean estimated from the Method Evaluation Study25 which was run
about a year earlier in April 1986. The summary data are
presented in Table B-10. The same source of homogenized lipid
material was used in both studies.
B-6
-------
IV. CALIBRATION DATA
The daily analyses of calibration standards bracketing the
sample analysis were conducted. The relative response factors
(RRF) for the native compounds and the internal quantitation
standards were calculated according to the protocol25 and are
plotted in Figures B-22 through B-47. The data quality
objectives for the RRF values stated that the variability for
TCDD and TCDF should be within + 20%, and the variability for the
remaining compounds should be within ± 30%. The calibration
standard analysis was repeated if any of the 26 measured events
were outside the limits.
In some instances data points were noted outside the RRF
control limits. When this occurred the analysis for the
calibration standard was repeated. Since a small percentage of
the data points in any one calibration were expectedly outside
the control criteria, the analyst proceeded with the analysis of
samples. Typically the compounds for which data points were
outside the control limits were the carbon-13 labeled compounds.
A comparison of the native PCDD and PCDF RRF values versus the
corresponding carbon-13 labeled internal standards demonstrated
greater consistency for the native compounds. No exceptions were
made for TCDD. If the RRF data for TCDD were outside the control
limits, no sample analyses were run until calibration criteria
were achieved.
B-7
-------
V. INTERNAL QUANTITATION STANDARDS
Figures B-48 through B-56 present the data on the % recovery
of the internal quantitation standards from each sample. The
data are plotted in the order of analysis. The data quality
objective was that the recovery of the internal quantitation
standards should be 50 - 115%.
Some of the recoveries were outside the data quality
objectives. Even so, the sample analyses were not repeated since
the recoveries of the other internal quantitation standards were
within the data quality objectives and the observed signal-to-
noise ratio was greater than 10.
B-8
-------
TABLE B-l
Percent Recovery of Measurements for Compounds from
the Twenty Internal Spiked Lipid Samples (%)
Spike Level % Recovery
2.3.7.8-TCDF
Low (10 pg/g): 94.4, 98.0, 91.8, Mean=93.1 CV=4.0%
90.1, 86.1, 91.9,
97.1, 92.3, 96.2
Medium (25 pg/g): 105, 103, 106, 121, Mean=107 CV=7.7%
99.8
High (50 pg/g): 99.2, 92.6, 102, 104, Mean=100 CV=6.0%
109, 94.8
2.3.7.8-TCDD
Low (10 pg/g): 102, 112, 93.1, 106, Mean=110 CV=8.6%
111, 127, 109, 117,
113
Medium (25 pg/g): 110, 117, 122, 125, Mean=119 CV=4.8%
120
High (50 pg/g): 104, 107, 111, 123, Mean=ll4 CV=ll%
135, 102
B-9
-------
TABLE B-l (continued)
Spike Level
% Recovery
1.2.3.7.8-PeCDF
Low (10 pg/g):
Medium (25 pg/g):
High (50 pg/g):
106, 104, 105, 104,
117, 104, 108, 101,
115
104, 112, 112, 99.6,
109
99.6, 102, 108, 97.8,
103, 101
Mean=107 CV=5.0%
Mean=107 CV=5.0%
Mean=102 CV=3.4%
2.3.4.7.8-PeCDF
Low (10 pg/g):
Medium (25 pg/g):
High (50 pg/g):
145, 52, 34.6, 180,
129, 102, 98.3, 95.3,
127
99.6, 113, 125, 95.2,
109
109, 106, 112, 112,
66.7, 107
Mean=107 CV=42%
Mean=108 CV=11%
Mean=102 CV=17%
1.2.3.7.8-PeCDD
Low (10 pg/g):
Medium (25 pg/g)
High (50 pg/g):
95.0, 101, 86.1, 88.3,
96.7, 103, 112, 105,
101
86.9, 108, 102, 94.0,
114
98.2, 102, 90.6, 98.8,
100, 100
Mean=98.7 CV=8.3%
Mean=101 CV=11%
Mean=98.3 CV=4.0%
B-10
-------
TABLE B-l (continued)
Spike Level
% Recovery
1.2.3.4.7.8-HXCDF
Low (25 pg/g):
Medium (62.5 pg/g)
High (125 pg/g):
76.1, 106, 97.2, 80.3,
85.9, 93.6, 107, 110,
124
104, 97.1, 84.6, 106,
110
106, 105, 98.7, 99.4,
102, 104
Mean=97.8 CV=16%
Mean=100 CV=9.9%
Mean=103 CV=2.9%
1.2.3.6.7.8-HXCDF
Low (25 pg/g):
Medium (62.5 pg/g)
High (125 pg/g):
118, 109, 96.0, 88.8,
89.9, 95.2, 103, 107,
118
100, 97.0, 88.7, 100,
107
108, 110, 97.4, 103,
101, 104
Mean=103 CV=11%
Mean=98.5 CV=6.7%
Mean=104 CV=4.4%
2.3.4.6.7.8-HXCDF
Low (25 pg/g):
Medium (62.5 pg/g)
High (125 pg/g):
77.9, 95.2, 86.7, 102,
98.5, 95.2, 97.4, 100,
106
101, 102, 103, 96.2,
97.4
96.7, 93.2, 91.7, 98.3,
96.9, 96.2
Mean=95.4 CV=8.9%
Mean=99.9 CV=3.0%
Mean=95.5 CV=2.6%
B-ll
-------
TABLE B-l (continued)
Spike Level
% Recovery
1.2.3.7.8.9-HXCDF
Low (25 pg/g):
Medium (62.5 pg/g)
High (125 pg/g):
82.9, 92.0, 79.0, 89.6,
98.0, 91.6, 98.0, 90.8,
102
89.5, 89.3, 88.5, 98.2,
92.7
95.2, 92.1, 89.5, 96.8,
100, 89.5
Mean=91.5 CV=8.0%
Mean=91.6 CV=4.4%
Mean=93.9 CV=4.5%
1.2.3.4.7.8-/1.2.3.6.7.8-HxCDD
Low (50 pg/g):
79.7, 150, 159, 148,
107, 86.3, 102, 171,
161
Medium (125 pg/g): 103, 109, 143, 95.2,
113
High (250 pg/g):
91.9, 110, 101, 111,
102, 98.0
Mean=129 CV=27%
Mean=113 CV=16%
Mean=102 CV=7.1%
1.2.3.7.8.9-HXCDD
Low (25 pg/g):
Medium (62.5 pg/g)
High (125 pg/g):
99.2, 93.2, 93.2, 83.1,
105, 84.7, 98.0, 85.1,
94.4
87.6, 98.1, 104, 95.2,
93.3
86.0, 91.7, 89.6, 93.4,
91.1, 90.2
Mean=92.9 CV=8.0%
Mean=95.6 CV=6.3%
Mean=90.3 CV=2.8%
B-12
-------
TABLE B-l (continued)
Spike Level
% Recovery
1.2.3.4.6.7.8-HPCDF
Low (25 pg/g):
Medium (62.5 pg/g):
High (125 pg/g):
97.6, 94.2, 98.4, 90.8,
98.0, 75.1, 95.6, 98.8,
97.2
90.1, 95.7, 99.2, 101,
102
92.2, 90.6, 92.5, 99.8,
92.4, 93.0
Mean=94.0 CV=8.0%
Mean=97.6 CV=4.9%
Mean=93.4 CV=3.5%
1.2.3.4.7.8.9-HPCDF
Low (25 pg/g):
62.2, 97.2, 77.5, 87.6,
119, 97.2, 98.8, 98.4,
109
Mean=94.1 CV=18%
Medium (62.5 pg/g): 82.0, 85.3, 100, 105,
107
Mean=95.9 CV=12%
High (125 pg/g):
90.3, 92.1, 95.0, 106, Mean=99.2 CV=8.0?
110, 102
1.2.3.4.6.7.8-HPCDD
Low (25 pg/g):
Medium (62.5 pg/g):
High (125 pg/g):
112, 104, 59.5, 52.2,
68.5, 60.2, 104, 72.3,
137
85.8, 93.9, 88.1, 90.6,
95.4
104, 88.1, 96.0, 104,
96.8, 91.9
Mean=85.5 CV=34%
Mean=90.8 CV=4.4%
Mean=96.8 CV=6.6%
B-13
-------
TABLE B-l (continued)
Spike Level
% Recovery
OCDF
Low (50 pg/g):
Medium (125 pg/g)
High (250 pg/g):
90.4, 83.4, 74.9, 92.9,
107, 80.3, 86.7, 83.2,
89.9
77.7, 105, 94.6, 101,
86.4
86.7, 90.2, 81.6, 108,
95.5, 85.1
Mean=87.6 CV=10%
Mean=92.9 CV=12%
Mean=91.2 CV=10%
OCDD
Low (50 pg/g):
Medium (125 pg/g)
High (250 pg/g):
67.7, 130, 27.8, 82.3,
80.6, 112, 70.3, 104,
26.1
107, 103, 92.0, 88.1,
105
80.6, 100, 88.0, 108,
94.8, 81.1
Mean=77.9 CV=45%
Mean=99.0 CV=8.5%
Mean=92.1 CV=12%
Data quality objectives for the % recovery for the internal
spiked lipid samples was 50% - 130%.
% Recovery = 100% x cone, spiked sample - cone, control sample
spike level
B-14
-------
FIGURE B-l
Percent Recovery of Spiked Internal QC Samples
Tetrachlorlnated Congeners
Batches 1 to 20
%
Recovery
140 •
120 •
100 j
80 •
60 •
40 •
20 •
r .. . .?.
! * • 8 9 ? ° \ * * . * • . • 8 •
• 2.3.7.8-TCOF
O 2.3.7.8-TCDD
— control
•" limits
123456789 10 11 12 13 14 15 1 S 17 18 19 20
Batch Number
FIGURE B-2
Percent Recovery of Spiked Internal QC Samples
Pentachlorlnated Congeners
Batches 1 to 20
180 •
160 '
140 •
120 '
M
% 1°°;
Recovery 80 -
60 •
40 •
20 •
n -
0
•
5
f
'~°"° A' £
A A A A
0
O"
i i 1 1 1 i 1 i 1 1 i i i i i i i i i
• 1.2,3.7.8-PeCDF
O 2.3.4.7.8-PeCDF
A 1,2.3.7.B-PeCDD
••• control
1 2 3 4 5 6 7 8 91011121314151617181920
Batch Number
B-15
-------
Recovery
FIGURE B-3
Percent Recovery of Spiked Internal QC Samples
Hexachlorlnated Congeners
Batches 1 to20
180 '
160 '
140 •
120 i
'
80 !
60 '
40 •
20 •
n •
A
A A
. A * A
' 00 « A A. ,SA ?
J^Ag^wSA Z
— 1 — 1 — 1 — 1 — 1 — 1 1 1 — 1 — 1— I — 1 — 1 — t— 1 — t— l — i — i
• 1.2,3.4.7,8-HxCDF
O 1,2,3.6.7.8-HxCDF
• 2.3.4.6.7.8-HxCDF
C3 1. 2.3.7 ,8,9-HxCDF
A 1.2.3,4.7.8-/1.2.3,6.7.8-HxCDD
A 1,2.3.7.8,9-HxCDD
"•control
— limit*
1 2345678 91011121314151617181920
Batch Number
FIGURE B-4
Percent Recovery of Spiked Internal QC Samples
Heptachlorinated Congeners
Batches 1 to20
Recovery
140 I
120 '
[
100 (
80 '
60 C
40 •
20 •
[ 5
'• o
3 O o O
|8"6 38? a- n - ' °D
' w ° n •
> o n
1 1 1 1 1 1 k— 1 1 1 1 1 1 1— < 1 1 K— 1
• 1 ,2,3.4.6.7 ,8-HpCDF
O 1,2,3.4.7,8.9-HpCDF
D 1,2.3,4.6.7,8-HpCDD
•• control
•• limits
1234567
8 91011121314151617181920
Batch Number
B-16
-------
FIGURE B-5
Percent Recovery of Spiked Internal QC Samples
Octachlorinated Congeners
Batches 1 to 20
140'
120 '
100 •
<
80-
j
60 '
40 •
20 •
0 ~ • ° 0 « n
oO • OO
1 • •* So o°« •«•
. 0 • o o o •• • 8
\ o
0 0
• OCOF
o ocoo
••• control
— limits
123456
7 8 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
B-17
-------
TABLE B-2
Average Percent Recovery of Measurements of
PCDDs and PCDFs From the Spiked Lipid Samples
Compound
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,7,8/
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7, 8-HpCDF
1,2,3,4,7,8, 9-HpCDF
1,2,3,4,6,7,8-HpCDD
OCDF
OCDD
Low
93.1
110
107
107
98.7
97.8
103
95.4
91.5
129
92.9
94.0
94.1
85.5
87.6
77.9
Spike Level*
Medium
107
119
107
108
101
100
98.5
99.9
91.6
113
95.6
97.6
95.9
90.8
92.9
99.0
High
100
114
102
102
98.3
103
104
95.5
93.9
102
90.3
93.4
99.2
96.8
91.2
92.1
Spike levels based on a 10-gram lipid sample.
Tetra and penta compounds: Low, Medium, High =10, 25, 50 pg/g.
Hexa and Kepta compounds: Low, Medium, High = 25, 62.5, 125 pg/g.
Octa compounds: Low, Medium, High = 50, 125, 250 pg/g.
B-18
-------
TABLE B-3
Results of Split Sample Analysis for #00609
Compound
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,3,7,8-PeCDF
2,3,4,7, 8-PeCDF
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,7,8/
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8-HpCDD
OCDF
OCDD
First Second
Analysis Analysis
(pg/g) (pg/g)
2.93
8.93
ND1 (0
11.0
17.5
9.76
5.30
1.94
ND1 (0
107
14.5
10.4
ND1 (0
164
TR2 (1
491
1 Not detected above Limit of
2 Trace
Relative Percent Difference (%)
2.83
9.09
. 7 ) ND1 ( 0 . 8 )
13.3
20.6
9.09
5.73
2.46
.6) ND1 (0.2)
117
16.2
10.6
.7) 0.69
177
.34) 3.57
594
Detection (LOD)
= hicrh value
Relative Percent
Difference (%)
3.47
1.78
18.9
16.3
7.11
7.80
23.6
8.93
11.1
1.90
7.62
90.8
19.0
low value x 100
average value
B-19
-------
TABLE B-4
Results of Split Sample Analysis for #29810
Compound
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,7,87
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8-HpCDD
OCDF
OCDD
1 Not detected above
2 Trace
First Second
Analysis Analysis
(pg/g) (pg/g)
2.20
11.3
ND1 (0
25.3
14.8
21.3
11.1
2.52
ND1 (0
109
15.9
33.5
TR2 (1
201
ND1 (0
936
Limit of
Relative Percent Difference (%)
2.29
11.8
.3) ND1 (0.5)
24.7
15.0
25.7
13.6
2.85
.3) ND1 (0.2)
127
15.7
34.1
.56) ND1 (1.9)
210
.8) TR2 (1.6)
868
Detection (LOD)
= hiah value -
Relative Percent
Difference (%)
4.0
4.3
1.6
1.3
18.7
20.2
12.3
15.2
1.3
1.8
4.4
7.5
low value x 100
average value
B-20
-------
TABLE B-5
Results of Split Sample Analysis for #12823
Compound
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,7,87
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8-HpCDD
OCDF
OCDD
Not detected above
First Second Relative Percent
Analysis Analysis Difference (%)
(pg/g) (pg/g)
TR2 (0
10.9
ND1 (0
25.4
18.1
16.9
6.90
2.45
ND1 (0
176
17.8
22.0
ND1 (0
138
2.52
843
Limit of
.72) ND1 (0.6)
11.2
.2) ND1 (0.2)
24.2
17.0
16.5
6.16
2.24
.9) ND1 (0.3)
156
ND1 (18.3)
22.4
.5) ND1 (0.6)
134
TR2 (1.74)
822
Detection (LOD)
2.71
4.84
6.27
2.40
11.3
8.96
12.0
1.80
2.94
36.6
2.52
Relative Percent Difference (%) = high value - low value x 100
average value
A response was noted in the second analysis for 1,2,3,7,8,9-
HxCDD but the ratio of the characteristic ions was outside the
qualitative criteria.
B-21
-------
TABLE B-6
Results of Split Sample Analysis for #29805
Compound
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,7,8/
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8-HpCDD
OCDF
OCDD
1 Not detected above
2 Trace
First Second Relative Percent
Analysis Analysis Difference (%)
(pg/g) (pg/g)
ND1 (0
6.99
ND1 (0
15.5
10.7
12.5
6.91
2.95
ND1 (0
129
10.5
25.6
ND1 (2
145
2.13
986
Limit of
Relative Percent Difference (%)
.9) ND1 (0.5)
7.73 10.0
.5) ND1 (0.5)
14.6 6.0
9.33 13.7
12.8 2.40
7.67 10.4
ND1 (2.6)
.6) ND1 (0.9)
116 10.6
9.47 10.3
26.7 4.2
.0) ND1 (1.9)
132 9.4
ND1 (2.3)
997 1.1
Detection (LOD)
= hicfh value - low value x 100
average value
A response was noted in the second analysis for 2,3,4,7,8,9-
HxCDF but the ratio of the characteristic ions was outside the
qualitative criteria.
B-22
-------
TABLE B-7
Results of Split Sample Analysis for #29806
Compound
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,7,87
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8-HpCDD
OCDF
OCDD
First
Analysis
(pg/g)
ND1 (0.7)
6.48
ND1 (0.2)
9.06
7.53
8.55
4.43
1.26
ND1 (0.4)
81.6
7.84
15.0
ND1 (0.6)
101
ND1 (0.8)
507
Second Relative Percent
Analysis Difference (%)
(pg/g)
ND1 (1.0)
6.41 1.1
ND1 (0.3)
9.75 7.3
7.02 7.0
8.40 1.8
4.81 8.3
TR2 (1.47) 15.4
ND1 (0.4)
86.8 0.3
7.17 8.9
15.7 4.6
ND1 (1.3)
98.9 2.1
ND1 (1.0)
562 10.3
1 Not detected above Limit of Detection (LOD)
2 Trace
Relative Percent Difference (%) = high value - low value x 100
average value
A response was noted in the second analysis for 2,3,7,8-TCDF but
the ratio of the characteristic ions was outside the qualitative
criteria.
B-23
-------
TABLE B-8
Results of Split Sample Analysis for #18801
Compound
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,7,8/
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8-HpCDD
OCDF
OCDD
First Second Relative Percent
Analysis Analysis Difference (%)
(pg/g) (pg/g)
2.80
7.32
ND1 (0
21.0
12.8
21.0
9.14
1.53
ND1 (0
120
10.3
23.6
ND1 (1
184
TR2 (2
1340
1 Not detected above Limit of
2 Trace
Relative Percent Difference (%)
2.77 1.1
6.74 8.3
.3) ND1 (0.4)
20.3 3.4
13.0 1.6
22.2 5.6
9.83 7.3
TR2 (1.94) 23.6
.4) ND1 (0.3)
113 6.0
9.93 3.7
25.1 6.2
.4) TR2 (1.4)
177 3.9
.73) 6.38 80.1
1400 4.4
Detection (LOD)
= hicrh value - low value x 100
average value
B-24
-------
TABLE B-9
Results of Split Sample Analysis for #06509
Compound
2,3,7 , 8-TCDF
2,3,7, 8-TCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,7,8/
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8-HpCDD
OCDF
OCDD
First
Analysis
(pg/g)
ND1 (0.6)
106
ND1 (0.7)
25.3
19.8
28.8
11.7
TR2 (2.6)
ND1 (0.7)
151
20.6
42.8
TR2 (1.8)
235
3.1
2500
Second Relative Percent
Analysis Difference (%)
(pg/g)
ND1 (0.7)
113 6.3
ND1 (0.7)
24.7 2.4
19.6 1.0
26.6 7.9
11.0 6.2
TR2 (2.39) 8.4
ND1 (0.5)
164 8.3
19.9 3.5
47.6 10.6
ND1 (2.5)
223 5.2
ND1 (3.2)
2530 1.2
1 Not detected above Limit of Detection (LOD)
Trace
Relative Percent Difference (%) = high value - low value x 100
average value
The first analysis was in batch 3, the second analysis was in
batch 6.
B-25
-------
FIGURE B-6
2,3,7,8-TCDD
Concentration In Unsplked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval (or Individual Analyses from Method
Evaluation Data
16 I
15 •
14 •
13 •
12
pg/g 1t .
2,3,7,8-TCDD ,
10 •
9-
7-
6.
1
o
0
o ° ° o o
° 0
2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
FIGURE B-7
2,3,7,8-TCDF
Concentration In Unsplked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval for Individual Analyses from Method
Evaluation Data
6 •
5
4 •
pg/g 3
2,3,7,8-TCDF
2 ,
1 -
0 •
o
'o00° 00°o0o oo°0o0
7 8 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
B-26
-------
FIGURE B-8
1,2,3,7,8-PeCDF
Concentration In Unsplked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval tor Individual Analyses from Method
Evaluation Data
5 -I
4
3 •
2 •
PS'g ,
1,2.3,7,8-PeCDF
0 •
-1 •
-2 •
-3 .
o
'"ooooOo0 oo°ooooooo
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 I 1 1
9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
FIGURE B-9
2,3.4,7,8-PeCDF
Concentration In Unsplked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval for Individual Analyses from Method
Evaluation Data
35
30
25
pg/g
2,3.4.7,8-PeCDF
20
15
10
0 ° o " ° o 0 °
o o
1 2 3 4 5 6 78 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
B-27
-------
FIGURE B-10
1,2,3.7.8-PeCDD
Concentration In Unspiked Control OC Sample (Pfl/fl)
Control Limits: 95% Confidence Interval lor Individual Analyses from Method
Evaluation Data
25-
24 •
23 •
22 •
21 •
PO'B 20
1, 2.3,7, 8-PeCDO
19'
18'
17 •
16 J
15 •
0 ° L ° o o o
° 0 ° °
o o o «
o
I
1 1 1 1 1 1 f I 1 1 1 1 1 1 1 1 1 I 1
1 23 4 56 78 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
B-28
-------
FIGURE B-ll
1.2.3,6,7.8-HxCDF
Concentration In Unsplked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval lor Individual Analyses from Method
Evaluation Data
IO •
16
14
12 •
pg/g 10 c
1,2,3, 6,7, B-HxCDF 6.
6 •
4 •
2 •
n .
° Oo0o0°c0°
> ° ° o °
0 0
o
1 1 1 1 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1
pg/g
1,2.3.4,7,8-HxCDF
1 2 3 4 5 6 7 6 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
FIGURE B-12
1,2,3,4,7,8-HxCDF
Concentration In Unsplked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval for Individual Analyses from Method
Evaluation Data
25 •
23
21 •
19 !
17 •
11 •
o
0
° ° o
£
o o '° <=
o
1 2 3 4 S 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
B-29
-------
FIGURE B-13
2,3,4,6,7,8-HxCDF
Concentration In Unsplked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval for Individual Analysea from Method
Evaluation Data
pg/g
2.3,4.8,7,8-HKCDF
12 T
10
8
6
4
2
0
•2
-4
« c 0 o
O O
I I I 1 I I 1 1 *——I 1 1 1 1 1 I I 1 I
1 2 3 4 5 6 7 B 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
FIGURE B-14
1.2.3.7,8,9-HxCDF
Concentration In Unsplked Control QC Sample (pg/g)
Control Limit*: 95% Confidence Interval for Individual Analyses from Method
Evaluation Data
pg/g
1.2.3.7.8.9-HxCDF
15 T
10
Sf
0
-5
•10
•15
1
7 8 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
B-30
-------
pg/g
1,2,3,7,8,9-HxCDD
FIGURE B-15
1,2.3,7.8.9-HxCDD
Concentration In Unsplked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval for Individual Analyses from Method
Evaluation Data
fin I
50
40
30
20
i
10
0
-m
) 0 o0
1 1 1 1 1 1 1 1 1 1 1 I I I I I I I I
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
FIGURE B-16
1,2,3,4,7,8/1,2,3,6,7,8-HxCDD
Concentration In Unsplked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval for Individual Analyses from Method
Evaluation Data
220
200
180
pg/g
1.2,3,4,7,8- & 160 •
1,2,3,6,7,8-HxCDD
140
120
100
1
-I-
-t-
-*-
8 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
B-31
-------
FIGURE B-17
1,2/3.4,7,8,9-HpCDF
Concentration In Unspiked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval for Individual Analyses from Method
Evaluation Data
5
4
2
1
pg/g °
1.2,3,4,7,8,9-HpCDF -1 -
-2
-3
-4
-5
-6
> o o
o o o
o o
o „ o °
o
0«"o"00o°0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
FIGURE B-18
1.2,3,4,6.7.8-HpCDF
Concentration In Unspiked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval for Individual Analyses from Method
Evaluation Data
pg/g
1,2,3,4,6,7,8-HpCDF
40
35
30 •
25
20 •
15 •
10
-4
1 - 1-
I I
1
1
\-
-4
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
B-32
-------
FIGURE B-19
1,2.3,4,6,7,8-HpCDD
Concentration In Unsplked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval for Individual Analyses from Method
Evaluation Data
PS/0
1,2,3.4,6.7,8-HpCDD
250
240
230
220
210 •>
200
190
o o
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
B-33
-------
FIGURE B-20
OCDD
Concentration In Unsplked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval lor Individual Analyses from Method
Evaluation Data
pg/g
OCDD
880 I
860
840
820
800 •
780 •
760 •
740 •
720 •
700 •
o
0 0
o
0 0 ° 0 ° 0 0 00
o o
o
1 2 3 4 5 6 76 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
FIGURE B-21
OCDF
Concentration In Unsplked Control QC Sample (pg/g)
Control Limits: 95% Confidence Interval for Individual Analyses from Method
Evaluation Data
pg/g
OCDF
10 •
8 •
6 •
4 •
2<
0
-2
-4 •
-fi •
-fl •
o0oo00o°00o°oooo 00°
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Batch Number
B-34
-------
TABLE B-10
Mean Measurements in the Unspiked Control Lipid Samples
Congener
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,7,87
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8-HpCDD
OCDF
OCDD
Mean measured
in this study
(pg/g)
1.94
10.06
0.81
27.65
18.46
20.24
11.11
3.76
0.39
155.20
15.70
27.69
1.25
223.70
2.11
813.85
Mean estimated from the
Method Evaluation Study
(pg/g)
ND1 (3
11.8
ND1 (1
22.2
19.8
22.4
11.2
4.3
ND1 (2
184.3
26.5
25.7
ND1 (0
214
ND1 (1
800
.6)
•1)
.3)
.3)
.0)
Not Detected. The number in parenthesis is the estimated
level of detection.
Calculations included all values. Not detected values were set
equal to the level of detection and trace values were used as the
level reported.
B-35
-------
FIGURE B-22
CONTROL CHART 2,3,7,8-TCDD
1.2
1.1 •
1
RRF 0.9 •
0.8 •
0.7
n R •
•
; f ;
?.*•
• *•••• ,! * „*••
* - A * * '%*«"• *«*- 'i"'l MEAN
«*. * »'. 5? *• ••*•• .»a «-.- v*« Mt/xr<|
?; «?*•* • *; fttf
« ; 8 •
•
-20%
10/27/86 12/16/06 2/4/87 3/26/87 5/15/87 7/4/87 8/23/87 10/12/07 12/1/87
DATE
FIGURE B-23
CONTROL CHART 2,3,7,0-TCDF
1.1 •
1.3
1.2
RRF 1.1
1
0.9 •
n n •
;* ™
':*
•£• «
s*j !t* *'!
* s • 1 •: t;t &- /•;;
l .;r rr ^:'
^ •
^
•
1 1 1 1 1 1 1 1
10/27/86 12/16/86 2/4/87 3/26/87 5/15/87 7/4/07 8/23/87 10/12/07 12/1/87
DATE
B-36
-------
RRF
FIGURE B-24
CONTROL CHART 1,2,3,7,8-PeCDD
2
1.8 +
1.6
1.2
1 -
0.8
.
I
-»l»—*-
V*
f
+30%
MEAN
-30%
H
10/27/86 12/16/86 2/4/87 3/26/87 5/15/87 7/4/87 8/23/87 10/12/87 12/1/87
DATE
FIGURE B-25
CONTROL CHART 1,2,3,7,8-PeCDF
1.4 -r
1.3
1.2 •
1.1 •
1 •
0.9 •
0.8
430%
?.;
MEAN
0.7
10/27/86 12/16/86 2/4/87 3/26/07 5/15/87 7/4/87 8/23/87 10/12/87 12/1/87
DATE
-30%
B-37
-------
RRF
RRF
FIGURE B-26
CONTROL CHART 2,3,4,7,8-PeCDF
1.5
1.4
1.3 •
1.2 -
1.1 •
1 •
0.9 -
0.0 •
•
.•
•* • »*•* M*
• £ • • • i*
:s v i.t >>
• •" "• 5?;! •"
.**»
• •
+30%
MEAN
0.7-
Ofi -
1 1 1 1 1 1 1 1
-30%
10/27/86 12/16/06 2/4/87 3/26/07 5/15/87 7/4/07 8/23/87 10/12/87 12/1/87
DATE
FIGURE B-27
CONTROL CHART 1,2,3,4,7,0-HxCDD
2
1.9
1.8
1.7
1.6
1.5
1.4 H
1.3
1-2 i
1.1
1
- +30%
••• •
'?. •
ts
MEAN
-f-
-f-
H
-30%
10/27/86 12/16/06 2/4/87 3/26/87 5/15/07 7/4/07 0/23/07 10/12/07 12/1/07
DATE
B-38
-------
FIGURE B-28
CONTROL CHART 1,2,3,7,8,9-HxCDD
2.4-
2.2-
2
RRF 1 fl
1.6 -
1.4
* $• •
. * :<• * A
\ '•*" 1 • v** *•
• •* «• § ft Ji
* • *
I 1 1 1 1 II 1 1
• +30%
MEAN
-30%
10/27/86 12/16/06 2/4/87 3/26/67 5/15/87 7/4/87 8/23/87 10/12/87 12/1/87
DATE
FIGURE B-29
CONTROL CHART 1,2,3,6,7,8-HxCDD
2 T
1.8
1.6
RRF 1.4
1.2
1
• «*
. •
+30%
MEAN
-30%
0.8
10/27/06 12/16/86 2/4/07 3/26/87 5/15/87 7/4/87 8/23/87 10/12/07 12/1/87
DATE
B-39
-------
FIGURE B-30
CONTROL CHART 1,2,3,4,7,8-HxCDF
RRF
1.3 ••
1.2-
1.1
1
o.g
0.8 i
0.7
.
r.
**:
•&
+30%
MEAN
-30%
0.6 -J 1 1 1 1 1 H
10/27/86 12/16/86 2/4/87 3/26/87 5/15/87 7/4/87 8/23/87 10/12/87 12/1/87
DATE
FIGURE B-31
CONTROL CHART 1,2,3,6,7,8-HxCDF
RRF
1.3
1.2
1.1
1 •
+30%
*i
*
if
s
*
t
MEAN
o.g
0.8
0.7
0.6
10/27/86 12/16/86 2/4/07 3/26/07 5/15/07 7/4/07 8/23/07 10/12/07 12/1/07
DATE
-30%
-+•
B-40
-------
RRF
RRF
FIGURE B-32
CONTROL CHART 2,3,4,6,7,8-HxCDF
1.3 •
1.2--
1.1
1
0.9
0.8
0.7
0.6
+30%
•
*.»
••
•
r»:
•flt
MEAN
-30%
•4-
•4-
•4-
-4-
H
10/27/8612/16/86 2/4/87 3/26/87 5/15/87 7/4/87 8/23/87 10/12/87 12/1/87
DATE
FIGURE B-33
CONTROL CHART 1,2,3,7,8,9-HxCDF
1.2 j
1.1 •'
1
0.9
0.8
0.7
0.6
0.5
4-30%
r
MEAN
-30%
-4-
•4-
-t-
10/27/86 12/16/86 2/4/87 3/26/07 5/15/07 7/4/87 0/23/87 10/12/87 12/1/87
DATE
B-41
-------
FIGURE B-34
CONTROL CHART 1,2,3,4,6,7,0-HpCDD
1.6
1.5
1.4 •
1.3
RRF 1.2
1.1 -
1 •
0.9 •
0.8 -
\
* •
0» •
5 • 4 j».
• &•'* '*>£ .*** Jrf
• "
•
a
i— — 1 1 1 1 1 1 1
+30%
MEAN
-30%
10/27/86 12/16/86 2/4/87 3/26/87 5/15/87 7/4/87 8/23/87 10/12/87 12/1/87
DATE
FIGURE B-35
CONTROL CHART 1,2,3,4,6,7,0-HpCDF
RRF
1.6 j
1.5 ••
1.4 •
1.3
1.1
1
0.9 |
+30%
MEAN
-30%
-+-
0.8
10/27/86 12/16/86 2/4/87 3/26/87 5/15/87 7/4/87 0/23/87 10/12/87 12/1/87
DATE
B-42
-------
FIGURE B-36
CONTROL CHART 1,2,3,4,7,0,9-HpCDF
1.8
1.6
1.4
RRF
1.2 •
1
0.0 •
0 fi -
•
•
• •
V
•
S
i 1
•
%
•• •*
• *s* 0 • •
'• • t?«
#
1 1 1
•
t£
p'&'& «'•
/• <«» fe40-fe
?*
'• •
•
1 1 1
+30%
MEAN
-30%
10/27/06 12/16/06 2/4/87 3/26/07 5/15/87 7/4/07 0/23/87 10/12/87 12/1/87
DATE
FIGURE B-37
CONTROL CHART OCDF
1.0 i
1.7
1.6 •
1.5 •
1.4 -
RRF 1.3 -
1.2 •
1.1 •
1 •
0.9 -
n R .
•
*
. .*
• ! !l
• * r
-------
FIGURE B-38
CONTROL CHART OCDD
RRF
1.5--
1.3
1.2
1.1
1 ••
0.9 -
0.0 •
0.7
•S
.*«-
MEAN
MtAN
-30%
o.e ^ 1 1 1 1 1 1 h-
10/27/86 12/16/06 2/4/07 3/26/07 5/15/07 7/4/07 0/23/07 10/12/07 12/1/07
DATE
B-44
-------
FIGURE B-39
CONTROL CHART 13C12-2,3,7,8-TCDD
2.2
1.0 •
RRF
1.6
1.4
-4-
fr
' '
a
v
•<;•?•
**•
•
+20%
MEAN
.... _20o/o
1.2
10/27/06 12/16/06 2/4/07 3/26/07 5/15/07 7/4/07 0/23/87 10/12/87 12/1/87
DATE
RRF
2.5 T
2.4
2.3
2.2
2.1
2 •
1.9
1.8
1.7
1.6
1.5
FIGURE B-40
CONTROL CHART 13C12-2,3,7,8-TCDF
l !
«5.
-TT-H-
-f-
-4-
-I-
4-20%
MEAN
• '• /r*^ w m
.••%»•« v
..§.».
-20%
10/27/06 12/16/06 2/4/07 3/26/07 5/15/07 7/4/07 0/23/07 10/12/07 12/1/87
DATE
B-45
-------
FIGURE B-41
CONTROL CHART 13C12-1,2,3,7,8-PeCDD
RRF
0.75
0.7 -
0.65 •
0.6 -
0.55 -
0.5 -
0.45 -
0.4 •
0.35 -
:
*..
2*8
+30%
MEAN
-30%
0.3 -\ 1 1 1 1 1 H
10/27/86 12/16/86 2/4/07 3/26/87 5/15/87 7/4/87 8/23/87 10/12/87 12/1/87
DATE
RRF
FIGURE B-42
CONTROL CHART 13C12-1,2,3,7,8-PeCDF
1.4 •
1.3
1.2
1.1 -
1
0.9 •
0.8 •
0.7
n R .
4-30%
• • A*
• * • «• *
*• * ** «*'? *A*
. • • ££. »?••• a% MEAT-
1* A •
". *. - •
-oUVo
1 1 1 1 1 1 1 1
10/27/86 12/16/86 2/4/87 3/26/87 5/15/87 7/4/87 8/23/87 10/12/87 12/1/87
DATE
B-46
-------
FIGURE B-63
CONTROL CHART 13C12-1,2,3,6,7,8-HxCDD
0.75 -r
0.7
0.65
0.6
RRF
0.55
0.5
0.45
0.4 -
0.35 -
0.3
«*—•-
*'9
i
+30%
MEAN
»'.
«
-30%
-f-
•+•
-f-
-+-
10/27/86 12/16/86 2/4/87 3/26/87 5/15/87 7/4/87 0/23/87 10/12/87 12/1/87
DATE
FIGURE B-44
CONTROL CHART 13012-1,2,3,4,7,8-HxCDF
2
1.8
RRF 1.6
1.4 •
1.2
1 -
+00%
•
*
' I * • * 8 *
t • * • m ... - IJICAM
» «? «r« • '»• ••• • ^ MtAN
• **
-JU To
1 1 1 1 1 1 1 1
10/27/06 12/16/86 2/4/87 3/26/87 5/15/87 7/4/87 8/23/87 10/12/87 12/1/87
DATE
B-47
-------
FIGURE B-45
CONTROL CHART 13C12-1,2,3,4,6,7,8-HpCDD
RRF
1.1
1 •
0.9 •
0.8 •
0.7
0.6
0.5
0.4
0.3
.....jj.
'
+30%
0.2 -\ 1 1 1 1 1 1 1 1
10/27/86 12/16/86 2/4/87 3/26/87 5/15/87 7/4/87 8/23/87 10/12/87 12/1/87
DATE
FIGURE B-46
CONTROL CHART 13C12-1,2,3,4,6,7,8-HpCDF
1.4 -
1.3 •
1.2 •
1.1 -
RRF 1 •
0.9 •
0.0 •
0 7 •
n fi .
' • •" *f
«• .•. «s
* i* «•'• . 3 * Vp
•
* J
"""£
1 1 1 1 1 1 1 — 1
+30%
MEAN
10/27/86 12/16/86 2/4/87 3/26/87 5/15/07 7/4/07 8/23/87 10/12/87 12/1/07
DATE
B-48
-------
FIGURE B-47
CONTROL CHART 13C12-OCDD
RRF
0.9
0.0
0.7
0.6
0.5
0.4
0.3
0.2
0.1
*
* *
""£•"
MEAN
•
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10/27/86 12/16/06 2/4/07 3/26/07 5/15/87 7/4/07 0/23/07 10/12/87 12/1/07
DATE
B-49
-------
FIGURE B-48
13C12-TCDF Recoveries for Batches 1-20
50
100
150 200
Samples
250
300
120
FIGURE B-49
13C12-TCDD Recoveries for Batches 1-20
100
80
o
I 60
40
20
0
50
100
150
Samples
200
250
300
B-50
-------
FIGURE B-50
13C12-PeCDF Recoveries for Batches 1-20
140
300
FIGURE B-51
13C12-PeCDD Recoveries for Batches 1-20
140 i
120 •
100 •
1" 80 •
§ ,
cc 60 •
<£
40 •
20 •
C
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) 50 100 150 200 250 300
Samples
B-51
-------
120
100
e-80
$
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-------
FIGURE B-54
13C12-HpCDF Recoveries for Batches 1-20
300
140
120
100
a)
> 80
o
0}
60
40
20
0
FIGURE B-55
13C12-HpCDD Recoveries for Batches 1-20
bo
50
100
150
Samples
200
250
300
B-53
-------
180
160
140
fc* 120
1
8 100
cc
S* 80
60
40
20
0
FIGURE B-56
13C12-OCDD Recoveries for Batches 1-20
<%
50
100 150 200
Samples
250
300
B-54
-------
APPENDIX C
This section contains the results of the externally spiked
lipid samples. The measurements were precise to three
significant digits. This work was conducted under the
direction of Jay Glatz, OTS QA Officer. This section
was prepared by Jay Glatz.
-------
I. EXTERNAL QUALITY CONTROL AUDIT SAMPLES
The external QC laboratory, Battelle Columbus Division,
prepared 3 identical 7-sample sets. Triplicate aliquots were
spiked with various PCDD/PCDF congeners at seven concentrations.
Spiking was conducted by adding known volumes of 4 stock
solutions containing known concentrations of the isomers of
interest. The stock solutions were prepared from crystalline
material obtained from several suppliers, see Table C-l.
One set of samples was analyzed by Battelle, (reference:
Determination of Polychlorinated Dibenzo-p-dioxins and
Dibenzofurans in Adipose Tissue; D.G. Aichele, et al.; Battelle
Columbus Division, January 8, 1987). The second set was archived
at Battelle and the third was sent to the MRI QA manager for
incorporation as blind samples into the various batches which
were to be analyzed. A solution prepared from the stock spiking
solutions was sent to MRI so that comparability of the results
would be known. This solution contained the isomers of interest
at a nominal concentration of 250 pg/ul. The results of MRI's
analysis of this solution are shown in Table C-2. The correction
factors obtained from this table were used to adjust the spiking
levels reported by Battelle into MRI "measured" spiking levels
for recovery calculations.
The results of the external audit samples are listed in
Table C-3 through C-10, and summarized in Table C-ll. The
percent recovery was calculated using the following formula:
% Recovery = [ ] Found - f ] Background X 100%.
[ ]Spiked level X Conversion factor
Except for sample no. 29, the resolution between 123478-
HxCDD and 123678-HxCDD was not sufficient to allow individual
quantitation. Therefore, recovery was calculated for the summed
isomers. The results are shown graphically in Figure C-l. All
data points fell between the stated objectives of 50-130%
recovery. The vast majority of data points fell between 80 and
110% recovery indicating highly acceptable performance.
C-2
-------
TABLE C-l
Spiking Standards for External Audit Samples
Compound
Commercial Source
Lot Number
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8-HpCDD
OCDD
OCDF
KOR Isotope
EPA Repository
Wellington Science
Wellington Science
KOR Isotope
Wellington Science
Wellington Science
Wellington Science
Cambridge Isotope
Cambridge Isotope
EPA Repository
EPA Repository
Cambridge Isotope
Cambridge Isotope
Cambridge Isotope
Cambridge Isotope
Cambridge Isotope
55y-7-22
CR82-2-2
N/A
N/A
AA-VIII-185
N/A
N/A
N/A
MB-13106-47
830-244
C25042
C14829-7
AWN-729-22
13106-7
MLB-706-21
F-2831
F-2832
C-3
-------
TABLE C-2
MRI Analysis of External Audit Sample Spiking Solution
PCDD/PDCF BCL Reported
Values (pg/ul)
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PCDD
1,2,3,7,8-PCDF
2,3,4,7, 8-PCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
250
250
250
250
250
250
250
250
250
250
250
250
250
250
250
250
250
MRI Analysis
Mean (pg/ul)
379
169
163
320
323
266
283
263
281
113
215
232
233
216
223
239
215
Conversion
Factor
1.52
0.68
0.65
1.28
1.29
1.06
1.13
1.05
1.12
0.45
0.86
0.93
0.93
0.86
0.89
0.96
1.26
C-4
-------
TABLE C-3
Background Concentrations
PCDD/PCDF
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PCDD
1,2,3,7,8-PCDF
2,3,4,7,8-PCDF
1,2,3,4,7,8-HxCDD/
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
Concentration
Mean (ppt)
10.064
1.943
18.455
0.845
27.650
155.200
15.695
20.240
11.147
0.880
3.788
223.700
27.690
1.380
813.850
2.110
Standard
Deviation
1.062
0.209
0.908
0.049
2.790
15.105
0.974
1.137
1.182
0.328
7.981
1.177
0.181
23.725
0.328
Standard
Error
0.23739
0.04801
0.20294
0.03500
0.62380
3.37764
0.21770
0.25417
0.27849
0.07517
1.78458
0.26317
0.09065
5.30505
0.08778
N1
20
19
20
2
20
20
20
20
18
1
19
20
20
4
20
14
Number of positive quantifiable results
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50272-101
REPORT DOCUMENTATION
PAGE
1. REPORT NO.
EPA 560/5-89-002
Recipient* > Accession No.
4. TKlt and Subtitle
Dioxins and Dibenzofurans in Adipose Tissue of U.S. Vietnam
Veterans and Controls.
S. Report Date
7. Autno<<<> Han K. Kang, and Kevin Watanabe, Dept. of Veterans Affairs
Joseph Breen, Janet Remmers, and Margaret Conomos. EPA
«. Performing Organization Ret*. No.
9. Performing Organization Name and Addre**
U.S. Environmental Protection Agency
Office of Toxic Substances
401 M Street, S.W.
Washington, B.C.' 20460
10. Pro|«ct/Ta«k/Work Unit No.
II. ContracKC) or Grant(G) No.
12. Spoatorlnc Omanlzatfon Name and Addms
U.S. Department of Veterans Affairs
810 Vermont Ave., N.W.
Washington, D.C. 20420
13. Type of Report & Period Covered
IS- Supplementary Note*
14. Abxtract (UmK: 200 worth)
Concern about the adverse effects of exposure to Agent Orange is for
the most part attributable to its toxic contaminant, 2,3,7,8-
tetrachlorodibenzo-p-dioxin (TCDD). TCDD accumulates preferentially in bods
fat and has a long half life in humans. Therefore, TCDD levels in adipose
tissue can serve as a biological marker of exposure to Agent Orange. The
adipose tissue collected for the EPA's National Human Adipose Tissue Survey
(NHATS) was made available to the study as a source of tissue specimens. A
total of 40 Vietnam veterans, 80 non-Vietnam veterans and 80 civilian men
were selected from males born between 1936 and 1954 and their adipose
tissues were analyzed for 17 2,3,7,8-substituted dioxins and dibenzofurans.
TCDD levels were log normally distributed and the mean level of 2,3,7,8-TCDE
in adipose tissue of the Vietnam veterans (13.4 ppt) was not significantly
different from that of the non-Vietnam veterans (12.5 ppt) or civilian men
(15.8 ppt). Adjusting for demographic variables did not change the
conclusions. The study results suggest that heavy exposure to Agent Orange
for most Vietnam veterans was very 'unlikely "and 'that there is no readily
available and reliable indirect 'method of assessing exposure to Agent Orange
for Vietnam veterans.
17. Document Analyst a. O«*crfp«r«/Op«n-C/y4»d
COSATI Ffeld/Group
IS. Availability Statement
19. S*curtty Clau CThtt R«portJ
2a Security Ct*»« (Thl« P»l«>
21. No. 0<
22. Price
(S*e ANSW39.18)
S«« fnctrvctfone on
(Formerly NTIS-35)
Department o< Commerce
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