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Determination of Chloroparaffins in Foodstuffs by GC MS-MS
Determination of Chloroparaffins in Foodstuffs by GC MS-MS
Determination of Chloroparaffins in Foodstuffs by GC MS-MS
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Determination of Chloroparaffins
in Foodstuffs by GC-MS/MS
Content
Chloroparaffins:
1. Applications, regulations, levels in the food chain
2. Analytical methods for food and human milk
Extraction and clean up
GC-MS/MS
3. Results for CPs in samples of this study
Molecular Structure
Use
textile industry as flame retardants, for repelling water and as anti-fouling agent
Toxicology
SCCP
classified as persistent
high potential for bioaccumulation
classified as toxic to aquatic organisms
carcinogenic to rats and mice
EU Regulations
Directive 2002/45/EC
SCCP were banned for certain applications
- in metal and leather industry
Stockholm Convention
on Persistent Organic Pollutants (POPs)
Aim:
Stockholm Convention
on Persistent Organic Pollutants (POPs)
http://chm.pops.int
State Institute for Chemical and Veterinary Analysis of Food
Freiburg (Germany)
CP levels
in human milk from UK
Content
Chloroparaffins:
1. Applications, regulations, levels in the food chain
2. Analytical methods for food and human milk
Extraction and clean up
GC-MS/MS
3. Results for CPs in samples of this study
Literature
Literature
Reth M. and Oehme M. Limitations of low resolution mass spectrometry in the electron capture
negative ionization mode for the analysis of short and medium chain chlorinated paraffins Anal.
Bioanal. Chem. 2004, 378, 1741-1747
Reth M., Zencak Z. and Oehme M. First study of congener group patterns and concentrations of
short- and medium-chain chlorinated paraffins in fish from the North and Baltic Sea
Chemosphere 2005, 58, 847-854
Z. Zencak, A. Borgen, M. Reth and M. Oehme Evaluation of four Mass Spectrometric Methods
for the Analysis of Polychlorinated n-Alkanes J. Chromatogr. A 2005, 1067, 295-301
Analytical procedure
1. fat extraction
different procedures depending on matrix and fat content
2.
removal of fat
column chromatography with silica gel impregnated with sulphuric acid
3.
clean up
adsorption chromatography on Florisil
4. Determination by GC/MS
Analytical procedure
Internal standards:
1.[13C10]-trans-Chlordane
2. -Hexachlorocyclo-hexane
Fat Extraction
2 5 g sample
melted fat
Fat Extraction
Fat Extraction
Na2SO4
conditioning:
silica gel/
sulfuric acid (44 %)
elution:
n-hexane / dichloromethane (1:1)
Na2SO4
glas wool
plant oil
conditioning:
n-hexane / dichloromethane (1:1)
elution:
silica gel/
sulfuric acid (44 %)
plant oil
silica gel/
sodium hydroxide
conditioning:
n-hexane / dichloromethane (1:1)
silica gel/
sulfuric acid (44 %)
Na2SO4
glass wool
elution:
n-hexane / dichloromethane (1:1)
C
conditioning:
n-hexane
Na2SO4
florisil
deactiviated with
1.5 % water
Na2SO4
glass wool
Florisil column
pre-wash:
n-hexane
dichloromethane
elution:
dichloromethane
evaporate with turbo vap
dissolve residue in
cyclohexane
Florisil column
Content
Chloroparaffins:
1. Applications, regulations, levels in the food chain
2. Analytical methods for food and human milk
Extraction and clean up
GC-MS/MS
3. Results for CPs in samples of this study
GC/HRMS
Analysis of CP
Analysis of CP
CPs are complex technical mixtures with thousands of isomers
Chromatograms with broad humps instead of single peaks
Determination of all homologue groups very time-consuming
Quantification of CP extremely difficult
response factor depends on the chlorine content
m/z 110
EI Scan; MCCP 42 % Cl
m/z 110
Precursor Ion
(m/z)
Product Ion
(m/z)
Collision Energy
(V)
CPs
91 [C7H7]+
53 [C4H5]+
-16
CPs
102 [C5H7Cl]+
65 [C5H5]+
-10
CPs
102 [C5H7Cl]+
67 [C5H7]+
-18
[13C10]-transChlordane
383 [M-Cl]+
276 [M-4Cl]+
-20
-Hexachlorocyclohexane
181 [M-3Cl]+
145 [M-4Cl]+
-15
-Hexachlorocyclohexane
181 [M-3Cl]+
109 [M-5Cl]+
-31
Analyte
Parameters of GC-EI-MS/MS
instrument:
column:
HP-5MS
fused silica capillary column (15 m length x 0.25 mm i.d.),
coated with 0.25 m of 5%-phenyl-methylpolysiloxane
injector temperature:
injection:
injection volume:
280 C
splitless
2.5 l
transferline:
ion source temperature:
electron energy:
carriergas:
280 C
200 C
70 eV
helium, constant flow of 2 ml/ min
temperature programme:
GC-EI-MS/MS
GC-MS/MS (EI-mode)
GC-MS/MS (EI-mode):
Allows determination of total CP concentration
Advantage
Disadvantage:
Advantage
no strong fragmentation of CPs under ECNI conditions
leads to formation of [M-Cl]- as major fragment
allows the evaluation of all congener and homologue groups
of SCCP and MCCP
allows a differentation between SCCP and MCCP
Disadvantage
GC-ECNI-MS does not detect lower chlorinated CPs
high number of runs per sample is necessary
the quantification depends on the degree of chlorination
of the used standard
GC-ECNI-MS is time consuming
Chemisches und Veterinruntersuchungsamt
Freiburg
Method Blanks
glassware
CP bind to active surface
chemicals
Method Blanks
measures to reduce the risk of contamination during clean up
Method Blanks
no plastic materials
Level 1
[2 ng/g]
Recovery
[%]
Level 2
[10 ng/g]
Recovery
[%]
Sample 1
1.82
91
9.50
95
Sample 2
1.66
83
10.0
100
Sample 3
1.46
73
9.30
93
Sample 4
2.42
121
9.74
97
Sample 5
2.06
103
11.7
117
number of samples
mean [ng/ l]
1.88
94
10.1
0.19
0.49
20
10
101
Content
Chloroparaffins:
1. Applications, regulations, levels in the food chain
2. Analytical methods for food and human milk
Extraction and clean up
GC-MS/MS
3. Results for CPs in samples of this study
Samples
Samples analysed:
10 samples of cheese
6 samples of meat
mirco1 / pixelio.de
Raw Milk
pooled samples of
severals farms
CP
CP
[ng / g fat]
raw milk 1
Tour I
< LOD
< LOD
raw milk 2
Tour 13
< LOD
< LOD
raw milk 3
Tour 7
< LOD
< LOD
raw milk 4
Tour 6
< LOD
< LOD
raw milk 5
Tour 8
< LOD
< LOD
raw milk 6
Tour 1
< LOD
< LOD
raw milk 7
Tour 12
< LOD
< LOD
raw milk 8
Tour Ellrich
< LOD
< LOD
raw milk 9
Tour Frankenhardt
< LOD
< LOD
raw milk 10
Tour Eckartshausen
Raw Milk
Cheese
Brie
lipid
content
[%]
CP
CP
[ng / g fat]
[ng / g wet
weight]
24,1
41
5.0
country of
origin
The Netherland
animal
organic
goat
Feta cheese
24,4
122
24
Greece
organic
sheep and
goat
Feta cheese
26,2
94
19
Germany
organic
sheep
Feta cheese
28,4
38
7.5
Germany
organic
sheep
Cheese
26,5
France
conventional
cow
Mozzarella
21,0
55
11
Italy
conventional
buffalo
Cheese
32,0
Italy
organic
sheep
Feta cheese
22,7
47
9.3
Greece
organic
sheep
Goat cheese
27,1
42
8.4
Germany
organic
goat
10
Goat cheese
27,8
< LOQ[3.6]
Germany
organic
goat
Cheese
Brie
lipid
content
[%]
CP
CP
[ng / g fat]
[ng / g wet
weight]
24,1
41
5.0
country of
origin
The Netherland
animal
organic
goat
Feta cheese
24,4
122
24
Greece
organic
sheep and
goat
Feta cheese
26,2
94
19
Germany
organic
sheep
Feta cheese
28,4
38
7.5
Germany
organic
sheep
Cheese
26,5
France
conventional
cow
Mozzarella
21,0
55
11
Italy
conventional
buffalo
Cheese
32,0
Italy
organic
sheep
Feta cheese
22,7
47
9.3
Greece
organic
sheep
Goat cheese
27,1
42
8.4
Germany
organic
goat
10
Goat cheese
27,8
< LOQ[3.6]
Germany
organic
goat
Cheese
Feta cheese, greece
122 ng/ g CP
Human Milk
Human Milk
Human Milk
Human Milk
Human Milk
Asia
Pacific Island
Europe
Human Milk
Asia
Pacific Island
Europe
Human Milk
Human Milk
Wild Boar
Sample
age
[month]
CP
[ng/ g fat]
HCB
[ng/ g
fat]
12
951
< LOD
< LOD
< LOD
12
8.4
2.9
23.0
< LOD
14.2
78.1
54.1
< LOD
12
12.9
12.4
5.9
< LOD
200
200
100
20
alpha-HCH
[ng/ g fat]
beta-HCH
[ng/ g fat]
lindane [ng/
g fat]
Chloroparaffins
LOD: 13 ng/ g fat
LOQ: 30 ng/ g fat
Meat
CP
[ng/ g fat]
chicken
country of origin
Germany
turkey
< LOD
Germany
goose
34
Germany
beef
Germany
beef
60
Germany
beef
Germany
Chloroparaffins
LOD: 13 ng/ g fat
LOQ: 30 ng/ g fat
Meat
beef
60 ng/ g fat CP
goose
34 ng/ g fat CP
Olive Oil
CP
[ng/ g fat]
olive oil
< LOD
olive oil
75
olive oil
olive oil
98
olive oil
38
olive oil
37
Outlook
Actual activity:
Determination of CPs with GC-ECNI-MS as second type of
detection
Final
Patricia Fischer,
Sebastian Schelb,
Katrin Thoma,
Nadine Singler