pesticides and pcb in food and feed according to method l ... s19.pdf · visit us at ! pesticides...
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Visit us at www.Lctech.de!
Pesticides and PCB in Food and Feed According to Method L 00.00-34
(§ 64 LFGB)
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What LCTech does
supplies innovative products and methods for the preparation and analysis of food, feed and environmental samples.
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The Extended and Revised DFG S19 Method L 00.00-34 § 64 LFGB (former § 35 LMBG)
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Official Manual of Test Methods According to § 64 LMBG
Modular Multiple Analytical Method for the Determination of Pesticide Residues in
Foodstuffs(Modified Version of the DFG Method S 19)
Analysis of FoodstuffsL 00.00
34
"Beuth" publishing house www.beuth.de
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Content
General Questions
The Fields of Application
The Method in Detail
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General Questions
Why to analyse e.g. pesticides?
Why to use a MMM (Modular Multi-Residue Method)?
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Why to analyse e.g. pesticides?
165149
124121105100
6884
Vegetable
Fruit
Number of different pesticides found
736949
158144
121100
8368
4046444037
1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005
?
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Why to analyse e.g. pesticides?
• Improved detection technologies
• Resistant pests on crops (e.g. grape 10 20 pesticdes)
• Old or forbidden pesticides
?
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Occurrence of pesticides (40.000 samples)
Pesticide Occurrence in samples
Carbendazim 1931Chlorpyrifos 1735Iprodion 1447Bromide (inorg.) 1383Azoxystrobin 1245Imazalil 921Cyprodinil 889Thiabendazol 748Cypermethrin 703Captan 673Metalaxyl/Metalaxyl M 670Fludioxonil 623Pyrimethanil 609Bromopropylat 603Malathion 582
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Example Turkish Grapes
Compound Application Conc. mg/kg
MRL mg/kg % MRL
Quinalphos Insectizide 0,22 0,05 440,00Imazalil Fungicide 0,14 0,02 700,00
Unfortunately very often 10 to 15 different pesticides can be found on grapes!
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Why to use a MMM (Modular Multi-Residue Method)?
Sample Reception
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Why to use a MMM (Modular Multi-Residue Method)?
• Pesticides can be found in nearly any food or feed
• Matrices differ strongly in their composition (e.g. fat, water, acid, carbohydrate, …)
• In general the analytes are not known
• Single or group methods are not practical in routine labs for a general use
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• > 1000 pesticides are sold world-wide• In Germany, residues of approx. 550 pesticides in > 25
crop types and 5 animal materials are regulated• Each year 10 new pesticides are registered in Germany• Additionally, residue chemists have to determine
forbidden pesticides and contaminants (e.g. DDT, PCB, Nitro musk, TBT)
Conclusion: Multi-residue methods are needed!
Why to use a MMM (Modular Multi-Residue Method)?
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• DFG S19
• Pesticides (X-, P-, N-containing) Pyrethroids
• Polyhalogenated Biphenyls
• Non-polar to semi-polar
The Fields of Application
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Gel Permeation Chromatography GPC
Eluate 1 65% Hexane 35% Toluene
Mini Silica Column Chromatography MSC
Eluate 2
100% Toluene
Eluate 3 5% Acetone 95% Toluene
Eluate 4 20% Acetone 80% Toluene
Eluate 5 100% Acetone
Extraction modules
E1 E2 E3 E4 E5 E6 E7 E8 E9
The Method in Detail
MSDPNDFPD
ECD ECD ECD FPD PND
LC-MS
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Extraction Modules
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Since 1995 ‚NEW‘
Till 1995 ‚OLD‘
Ethyl acetate Cyclohexane
Dichloro methane
Extraction Modules
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• Extraction modules are choosen according to matrix composition
• E1/E4: water > 70 %, fat < 2,5 %
• E2/E5: water < 70 %, fat < 2,5 %
• E3: see E1, but high acid content (buffered to pH 7)
•Type: Extraction with liquid/liquid partitioning
• Typically for vegetables, fruit, juice
Extraction Modules
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• Why is the water content so important?
• Adjusting to 100 mL total water content (E1 – E5)
• Soaking time (30 min) is essential, if water < 70 %!
• Ratio of water / extraction solvent is the same
Extraction Modules
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• Extraction modules are choosen according to matrix composition
• E6: Water 0 %, fat 100 % Oil, Tallow
• E7: Water low, fat > 2,5 % Nuts, Oil Seeds
• E8: Water high, fat > 2,5 % Meat, Fish, Cheese
• E6: Dissolving fat in GPC eluent
• E7: Extraction in the presence of large amounts of fat
• E8: Cold extraction with hexane / acetone
Extraction Modules
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• Automated extraction with the ASE system from Dionex
• Typically used for dry matrices (Tea, Cereals, Spices)
• Extraction is performed with elevated temperature (120 °C) and pressure (100 bar)
• ‚Pressure Cooking Pot‘-Principle
Extraction Modules
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Gel Permeation Chromatography Module (GPC)
• See previous presentation:
• ‘Introduction into Gel Permeation Chromatography’
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Gel Permeation Chromatography GPC
Eluate 1 65% Hexane 35% Toluene
Mini Silica Column Chromatography MSC
Eluate 2
100% Toluene
Eluate 3 5% Acetone 95% Toluene
Eluate 4 20% Acetone 80% Toluene
Eluate 5 100% Acetone
Extraction modules
E1 E2 E3 E4 E5 E6 E7 E8 E9
MSDPNDFPD
ECD ECD ECD FPD PND
LC-MS
OCP Pesticides < 3 ppb
OPP Pesticides < 3 ppb
MS-NCI
Module C1 – C2 Mini Silica Column Cleanup
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GPC Concentrate 5,0 mL
Isooctane Concentrate
Solvent Exchange
Mini Silica Column
Ethyl acetate musn‘t be present!
Eluate 1 65% Hexane 35% Toluene
Eluate 2
100% Toluene
Eluate 3 5% Acetone 95% Toluene
Eluate 4 20% Acetone 80% Toluene
Eluate 5 100% Acetone
Combined Combined
Eluate 0
100% Hexane
PCB expected
Module C1 – C2 Mini Silica Column Cleanup
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Pesticide GPC E 1 E 2 E 3 E 4 E 5 ng / µl notes
Aldrine 120-150 5 0 0 0 0 0,9 Eluate 1 (ECD) + Rt check
HCB 140-165 5 0 0 0 0 0,5 "evaporate" - check
Trifluraline 100-130 5 0 0 0 0 0,9 Eluate 1 (ECD)
Bromophos 120-150 4 2 0 0 0 1,8 Eluate 1 (NPD + FPD)
Bifenthrine 60-120 2 3 0 0 0 4,5 GPC cut - large molecules
Endosulfansulfate 100-140 0 5 0 0 0 0,5 Eluate 2 (ECD)
Parathion 110-140 0 4 1 0 0 2,7 Eluate 2 (NPD + FPD)
Chinomethionate 170-200 0 1 4 0 0 27,0 GPC cut end
Bromopropylate 95-135 0 0 4 2 1 2,7 Eluate 3 + 4 (ECD)
Captane 120-150 0 0 5 0 0 45,0 Eluate 3 (NPD) // + Insert check
Metalaxyl 115-150 0 0 0 5 1 45,0 Eluate 4 (NPD)
Triamiphos 125-160 0 0 0 0 4 90,0 Eluate 5 (NPD + FPD)
GPC and Mini-Silica Testmix
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Official Manual of Test Methods According to § 64 LFGB
L Analysis of FoodstuffsResidue analysis of plant protective substances
in Food (Table of relative retention time of plant
protective substances with gas chromatography
00.00
38
Analysis of Foodstuffs
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Pesticide CAS-Nr.RRT
HP5MS
(Parathion)
RRT DB35MS
(Parathion)
Ion 1 Ion 2 Ion 3 Ion 4 MS
D
EC
D
NP
D
Dichloranilin, 3,5- 626-43-7 0,47 0,54 161 163 90 99 xxx xx x
Acephate 30560-19-1 0,47 0,58 136 94 95 96 xx x xx
Aclonifen 74070-46-5 1,40 1,34 264 266 212 77 xxx x x
Acrinathrin, 1 101007-06-1 1,57 1,41 207 181 281 208 xx xxx xx
Acrinathrin, 2 101007-06-1 1,58 1,46 181 208 207 93 xxx xxx xx
Alachlor 15972-60-8 0,89 0,88 160 188 146 237 xxx xxx x
Aldrin 309-00-2 0,97 0,93 263 66 265 261 xxx xxx
Allidochlor 93-71-0 0,40 0,47 56 138 132 70 xxx xx xx
Alodan 2550-75-6 1,09 1,04 229 272 237 273 xx xxx
Ametryn 834-12-8 0,89 0,93 227 212 170 185 xxx xx
Amidithion 919-76-6 0,96 1,03 125 131 93 143 x x x
Aminocarb 2032-59-9 0,73 0,79 151 150 136 208 xx xx
Amitraz 33089-61-1 1,56 1,46 121 162 132 293 xx x
696 peaks with Rt times
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