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

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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

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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

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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

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Automated sample clean-up

The search for simplifications in the manual sample processing

1. prototype

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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

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Automated sample clean-up

pilot series:

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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

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Recovery Feed fat: n = 9 ; sample weight 1 to 5 g

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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

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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

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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

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GC-HRMS vs. GC-MS/MS Results

(upperbound dl-PCB-TEQ)

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GC-HRMS vs. GC-MS/MS Results

(sum of 6 indicator PCB)

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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

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Recovery of the last twenty sample preparation

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Feed fat: n = 9 last twenty sample preparation n = 20

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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

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24

and

you for

your attention!

Many thanks to the people

„behind the work“