A Brief 25-year History and Recent Developments in Automated High- Throughput Sample Preparation of Human Specimens for the Measurement of PCDDs, PCDFs, cPCBs, PCNs, PBDDs, PBDFs, PCBs, PBDEs and OC Pesticides by GC/ID-HRMS. A Brief 25-year History and Recent Developments in Automated High- Throughput Sample Preparation of Human Specimens for the Measurement of PCDDs, PCDFs, cPCBs, PCNs, PBDDs, PBDFs, PCBs, PBDEs and OC Pesticides by GC/ID-HRMS. Wayman Turner - Senior Laboratory Scientist – Centers for Disease Control and Prevention Foundation 4th International Seminar on Total Solutions for POPs Analysis Workshop at Dioxin 2011, Brussels, Belgium
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• Akins J.R., Waldrep K., and Bernert J.T. Jr. The Estimation of Total Serum Lipids by a Completely Enzymatic 'Summation' Method. Clin. Chim. Acta. 184: 219-226 (1989).
• Phillips D.D., Pirkle J.L., Burse V.W., Bernert J.T., Henderson L.O. and Needham L.L. Chlorinated Hydrocarbon Levels in Human Serum: Effects of Fasting and Feeding. Arch. Environ. Contam. Toxicol. 18: 495-500 (1989).
• Bernert J.T., Turner W.E., Patterson D.G. Jr. and Needham L.L. Calculation of Serum “Total Lipid” Concentrations for the Adjustment of Persistent OrganohalogenToxicant Measurements in Human Samples. Chemosphere 68: 824-831 (2007)
Short Formula = (2.27*TCHOL + TRIG + 62.3Long Formula = 1.667*((TCHOL-FCHOL) + FCHOL +TRIG + PLIPID
• Akins J.R., Waldrep K., and Bernert J.T. Jr. The Estimation of Total Serum Lipids by a Completely Enzymatic 'Summation' Method. Clin. Chim. Acta. 184: 219-226 (1989).
• Phillips D.D., Pirkle J.L., Burse V.W., Bernert J.T., Henderson L.O. and Needham L.L. Chlorinated Hydrocarbon Levels in Human Serum: Effects of Fasting and Feeding. Arch. Environ. Contam. Toxicol. 18: 495-500 (1989).
• Bernert J.T., Turner W.E., Patterson D.G. Jr. and Needham L.L. Calculation of Serum “Total Lipid” Concentrations for the Adjustment of Persistent OrganohalogenToxicant Measurements in Human Samples. Chemosphere 68: 824-831 (2007)
Short Formula = (2.27*TCHOL + TRIG + 62.3Long Formula = 1.667*((TCHOL-FCHOL) + FCHOL +TRIG + PLIPID
NOTHING IS IMPOSSIBLEFor those who don’t have to do the work!
NOTHING IS IMPOSSIBLEFor those who don’t have to do the work!
Analyte List
Polychlorinated Dibenzo-p-dioxins and Dibenzofurans Polybrominated Dibenzo-p-dioxins and Dibenzofurans1,2,3,4,6,7,8,9-Octachlorodibenzo-p-dioxin (OCDD) 2,3,7,8-Tetrabromorodienzo-p-dioxin (TBDD)
We Have Come a Long WayAutomation has significantly changed our throughput
• In 1987 one person (original LLE & semi-automated cleanup method) could process 10 samples for TCDD only in 5 days.
• Today one person (using SPE & PowerPrep) can process 60 samples in 5 days for PCDDs/PCDFs/cPCBs + PCNs and PBDDs/PBDFs.
• In addition today one person (using SPE & Rapid Trace) can process 150 samples in 5 days for PCBs (including mPCBs for TEQ), OC pesticides and PBDEs.
Polychlorinated Dibenzo Dioxins and Furans
Figure 3
Native Dioxins
13C Labeled Dioxins3355P
3445P3344P
3344P
3445P
2378F
2378F
2378D
2378D
33445P
33445P
1234D
12378F
23478F
12378D334455P
12378F
23478F
334455P12378D
123478F
123678F234678F
123478D123678D
123789D
123789F
123478F
123678F
234678F
123478D
123678D
123789D
123789F
OCDF
OCDD
OCDD
OCDF
1234678F
1234679D
1234678D
1234789F
1234678F1234789F
1234679D
1234678D
Polychlorinated Naphthalens
Figure 4
Native PCNs
13C Labeled PCNs
N42
N42
N28
N27
N27
N48
N52/60
N50N54
N53
N52/60
N66/67
N71/72N64/68
N69
N73
N66/67 N64/68
N73
1234D
Native Pesticides
13C Labeled Pesticides
Pesticides 2010
Figure 2
a-HCCHHCB
PCAnisol
b-HCCH
g-HCCH
HCB PCAnisol
a-HCCH
b-HCCH
g-HCCH
Aldrin
Aldrin
OCS
OCS
Isodrin
Isodrin
Oxychlor
Oxychlor
H.Epox
H.Epox
g-Chlrdn
g-Chlrdn
a-Chlrdn
a-Chlrdn
t-Nona
t-Nona
op-DDE
op-DDE
pp-DDE
pp-DDE
Dieldrin
Dieldrin
Endrin
Endrin
op-DDT
op-DDT
pp-DDT
pp-DDT
Par50
Par50
Par62
Par62
Par2
6P
ar2
6
Mirex
Mirex
c-N
ona
c-N
ona
pp-Moxyc
pp-Moxyc
1234D
Observation from the ‘real world’ by an analytical
chemist who retired after 57 years from NIST ...
It has been estimated that concentrations of 1 in 1018 of almost any
substance can be expected to be present in almost any sample. This
translates to approximately a thousand molecules. In: Quality Assurance of
Chemical Measurements by John K. Taylor (1987, p48).
Top : Native PCBs
Bottom: 13C-labeled PCBs
Figure 118
28
52
49
4474
66
101
15
199
87
110
14
9
11
8
32
28
52
37
70
101111
118
153
105
138178
128
167
15
6
15
7
18
0
17
0
18
9
19
4
209
20
6
209206
10
5
14
61
53
19
6-2
03
13
8-1
58
17
8
18
7 18
31
28
16
7
17
71
56 15
71
72
18
0
17
02
01
19
51
89
19
4
Figure 2
Top : Native Pesticides
Bottom: 13C-labeled Pesticides
HCB
HCCHOXYCHLOR
H. EPOX
T-NONA
ppDDE
DIELDRIN
opDDTppDDT
MIREX
HCB
OXYCHLOR
H. EPOX
T-NONA
ppDDE
DIELDRIN
opDDT
ppDDT
MIREX
HCCH
HCCH
HCCH
LOD (pg/g Lipid) for TCDD MAT95 vs. DFSAssumptions: 70% Recovery & Total Lipid 0.6 %
LOD (pg/g Lipid) for TCDD MAT95 vs. DFSAssumptions: 70% Recovery & Total Lipid 0.6 %
SWEIGHT MAT95 DFS
5 1.786 0.595
10 0.893 0.298
15 0.595 0.198
20 0.446 0.149
25 0.357 0.119
30 0.298 0.990
35 0.255 0.085
40 0.223 0.074
45 0.198 0.066
50 0.179 0.060
High Resolution Mass SpectrometersHigh Resolution Mass Spectrometers