determination of pcdd/f and pcb with a new automated ...prague 2013; rafa cvua-mel t. bernsmann...
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Thorsten Bernsmann; Ursula Möhlenkamp; Peter Fürst
Chemical and Veterinary Analytical Institute
Münsterland-Emscher-Lippe
Joseph-König-Str. 40, 48147 Münster/Germany
(thorsten.bernsmann@cvua-mel.de)
Aulwurm U2, Baumann M2
LCTech GmbH, Bahnweg 41, Dorfen, Germany
Determination of PCDD/F and PCB
with a new automated approach
for fast sample preparation and
measurement with GC-HRMS and
GC-MS/MS
Prague; 07.11.2013
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
26.08.2013 / 2
Outline
Manual sample clean-up; history in our
laboratory
Manual sample clean-up today
Development of a new automated
approach for fast sample preparation
First results
Effect on GC-HRMS versus GC-MS/MS
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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Manual sample clean-up Sulphuric acid
column GPC Florisil
column
Active carbon
column (2x)
Every time the solvents
were removed by rotary
evaporation
• time consuming
• possible losses
6 x
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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Manual sample clean-up: today
Sulphuric
acid
column
Florisil
column
Active
carbon
column
PCB Nono und
diortho PCB
n-h
exane
n-h
exane/D
CM
tolu
ene
Non
ortho
PCB
PC
B a
ctive c
arb
on c
olu
mn
Flo
risil
colu
mn
PC
DD
/F-a
ctive c
arb
on c
olu
mn
tolu
ene
tolu
ene
PCDD/F
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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Automated sample clean-up
The search for simplifications in the manual sample processing
1. prototype
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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Automated sample clean-up
2. prototype
pump
High-quality
switching valves
low dead
volume
4.colum: active carbon
for PCDD/F
3/4 column can
be used with
back flush
Electric pressure
closure
Columns are purged
with nitrogen after
the clean up
Equal
sample loading
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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Automated sample clean-up
pilot series:
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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sulphuric acid
column
Florisil
column
active
carbon
column
PCB
active
carbon
column
PCDD/F
sample
• toluene
Fr. 1: ndl-PCB
Fr. 2: mono ortho PCB
Fr. 3 non ortho PCB
Fr. 4: PCDD/F
• n-hexane
• n-hexane/DCM
• toluene
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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Recovery Feed fat: n = 9 ; sample weight 1 to 5 g
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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EURL assigned
value (Huber
robust mean)
ng/kg produkt
(12 % moisture
content)
EURL robust
standard
diviatio; ng/kg
produkt (12 %
moisture
content)
Mean
[ng/kg
produkt (12
% moisture
content)]
standard
diviation
[ng/kg
produkt (12
% moisture
content)]
Variation
koeffizient
mean of
calculated z-
Score of
each
analysed
sample
(n=9)
2,3,7,8-TeCDD
1,2,3,7,8-PeCDD
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-HpCDD 0,255 0,0434 0,286 0,024 8,4 0,72
OCDD Octachlordibenzodioxin 2,42 0,318 2,573 0,200 7,8 0,48
2,3,7,8-TeCDF 0,306 0,0381 0,298 0,021 7,0 -0,21
1,2,3,7,8-PeCDF 0,132 0,0284 0,133 0,019 14,3 0,04
2,3,4,7,8-PeCDF 0,139 0,032 0,171 0,018 10,6 0,98
1,2,3,4,7,8-HxCDF 0,142 0,0253 0,185 0,023 12,4 1,70
1,2,3,6,7,8-HxCDF 0,0869 0,0254 0,081 0,015 18,1 -0,23
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF 0,197 0,0385 0,211 0,020 9,4 0,37
1,2,3,4,7,8,9-HpCDF
OCDF Octachlordibenzofuran
WHO-PCDD/F-TEQ (WHO-TEF
2005) upper bound 0,206 0,0444 0,248 0,028 11,3 0,95
WHO-PCDD/F-PCB-TEQ (WHO-
TEF 2005) upper bound 2,17 0,254 2,109 0,048 2,29 -0,24
Feed fat: n = 9 ; sample weight 1 to 5 g
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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GC-HRMS vs. GC-MS/MS Results (upperbound TEQ)
LOD animal feed: GC-HRMS: 0.01 - 0.06 pg/g;
GC-MS/MS: wide/wide: 0.02 - 0.08 pg/g; unit/wide: 0.03 - 0.1 pg/g
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
26.08.2013 / 15
Feed fat: n = 9 ; sample weight 1 to 5 g EURL assigned value
(Huber robust mean)
ng/kg produkt (12 %
moisture content)
EURL robust
standard diviatio;
ng/kg produkt (12 %
moisture content)
Mean [ng/kg
produkt (12 %
moisture
content)]
standard diviation
[ng/kg produkt (12 %
moisture content)]
Variation
koeffizient
mean of calculated
z-Score of each
analysed sample
(n=9)
PCB 77 85,2 8,34 74,7 4,6 6,1 -1,26
PCB 81 2,63 0,47 3,09 0,33 10,7 0,97
PCB 126 18 2,1 17,9 0,5 3,1 -0,07
PCB 169
PCB 105 546 53,4 503 47 9,3 -0,81
PCB 114 30,1 6,09 21,7 4,1 19,0 -1,38
PCB 118 990 96,8 1003 74 7,4 0,13
PCB 123 22,1 3,68 17,9 3,3 18,4 -1,14
PCB 156 136 11,9 135 14 10,2 -0,07
PCB 157 34,5 5,15 35,5 3,9 10,9 0,19
PCB 167 53,3 7,02 53,6 7,7 14,3 0,04
PCB 189
WHO-PCB-TEQ
(WHO-TEF 2005)
upper bound 1,89 0,213 1,861 0,055 3,0 -0,10
PCB 28
PCB 52 0,251 0,0348 0,288 0,041 14,2 1,07
PCB 101 0,629 0,0778 0,627 0,085 13,6 -0,02
PCB 138 0,966 0,146 0,823 0,077 9,3 -0,98
PCB 153 0,749 0,0855 0,691 0,096 13,9 -0,68
PCB 180 0,245 0,0361 0,250 0,040 16,2 0,13
Sum ndl PCB 3,16 0,46 2,755 0,311 11,3 -0,88
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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GC-HRMS vs. GC-MS/MS Results
(upperbound dl-PCB-TEQ)
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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GC-HRMS vs. GC-MS/MS Results
(sum of 6 indicator PCB)
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
26.08.2013 / 19
sulphuric acid
column
Flroisil
column
active
carbon
column
PCB
active
carbon
column
PCDD/F
sample
• toluene
Fr. 1: ndl-PCB
Fr. 2: mono ortho PCB
Fr. 3 non ortho PCB
Fr. 4: PCDD/F
• n-hexane
• n-hexane/DCM
• toluene
• n-hexane/DCM
waste
back flush
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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Recovery of the last twenty sample preparation
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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Feed fat: n = 9 last twenty sample preparation n = 20
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
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sulphuric acid column filling: Silica gel impregnated with sulfuric acid,
silica gel, basic silica gel
Drying agents: sodium sulphate
Layers are separated by glass fiber filter.
Capacity: matrix dependent
Possible: 5 grams of fat 1 g
2 g
3 g
4 g
5 g
tested with feed fat;
Proficiency Test of the EURL
for Dioxin and PCB, Freiburg
2013
CVUA-MEL Prague 2013; RAFA
T. Bernsmann
26.08.2013 / 24
24
and
you for
your attention!
Many thanks to the people
„behind the work“
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