Pesticides and PCB in Food and Feed According to Method L ( 64 LFGB) Visit us at

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1 Pesticides and PCB in Food and Feed According to Method L ( 64 LFGB) Visit us at

2 What LCTech does supplies innovative products and methods for the preparation and analysis of food, feed and environmental samples.

3 The Extended and Revised DFG S19 Method L LFGB (former 35 LMBG)

4 Official Manual of Test Methods According to 64 LMBG L Analysis of Foodstuffs Modular Multiple Analytical Method for the Determination of Pesticide Residues in Foodstuffs (Modified Version of the DFG Method S 19) "Beuth" publishing house

5 Content General Questions The Fields of Application The Method in Detail

6 General Questions Why to analyse e.g. pesticides? Why to use a MMM (Modular Multi-Residue Method)?

7 Why to analyse e.g. pesticides? Number of different pesticides found Fruit Vegetable ?

8 Why to analyse e.g. pesticides?? Improved detection technologies Resistant pests on crops (e.g. grape pesticdes) Old or forbidden pesticides

9 Occurrence of pesticides ( samples) Pesticide Occurrence in samples Carbendazim 1931 Chlorpyrifos 1735 Iprodion 1447 Bromide (inorg.) 1383 Azoxystrobin 1245 Imazalil 921 Cyprodinil 889 Thiabendazol 748 Cypermethrin 703 Captan 673 Metalaxyl/Metalaxyl M 670 Fludioxonil 623 Pyrimethanil 609 Bromopropylat 603 Malathion 582

10 Example Turkish Grapes Compound Application Conc. mg/kg MRL mg/kg % MRL Quinalphos Insectizide 0,22 0,05 440,00 Imazalil Fungicide 0,14 0,02 700,00 Unfortunately very often 10 to 15 different pesticides can be found on grapes!

11 Why to use a MMM (Modular Multi-Residue Method)? Sample Reception

12 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

13 Why to use a MMM (Modular Multi-Residue Method)? > 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!

14 The Fields of Application DFG S19 Pesticides (X-, P-, N-containing) Pyrethroids Polyhalogenated Biphenyls Non-polar to semi-polar

15 The Method in Detail Extraction modules E1 E2 E3 E4 E5 E6 E7 E8 E9 Gel Permeation Chromatography GPC LC-MS FPD PND MSD Mini Silica Column Chromatography MSC 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 ECD ECD ECD FPD PND

16 Extraction Modules

17 Extraction Modules Since 1995 NEW Ethyl acetate Cyclohexane Till 1995 OLD Dichloro methane

18 Extraction Modules 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

19 Extraction Modules 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 Extraction modules are choosen according to matrix composition E6: E7: E8: Water 0 %, fat 100 % Oil, Tallow Water low, fat > 2,5 % Nuts, Oil Seeds

20 Extraction Modules Extraction modules are choosen according to matrix composition E6: E7: E8: Water 0 %, fat 100 % Oil, Tallow Water low, fat > 2,5 % Nuts, Oil Seeds Water high, fat > 2,5 % Meat, Fish, Cheese E6: E7: E8: Dissolving fat in GPC eluent Extraction in the presence of large amounts of fat Cold extraction with hexane / acetone

21 Extraction Modules 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

22 Gel Permeation Chromatography Module (GPC) See previous presentation: Introduction into Gel Permeation Chromatography

23 Module C1 C2 Mini Silica Column Cleanup Extraction modules E1 E2 E3 E4 E5 E6 E7 E8 E9 Gel Permeation Chromatography GPC LC-MS FPD PND MSD OPP Pesticides < 3 ppb Mini Silica Column Chromatography MSC 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 ECD ECD ECD MS-NCI FPD PND OCP Pesticides < 3 ppb

24 Module C1 C2 Mini Silica Column Cleanup PCB expected Eluate 0 100% Hexane GPC Concentrate 5,0 ml Isooctane Concentrate Mini Silica Column Solvent Exchange 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

25 GPC and Mini-Silica Testmix Pesticide GPC E 1 E 2 E 3 E 4 E 5 ng / µl notes Aldrine ,9 Eluate 1 (ECD) + Rt check HCB ,5 "evaporate"- check Trifluraline ,9 Eluate 1 (ECD) Bromophos ,8 Eluate 1 (NPD + FPD) Bifenthrine ,5 GPC cut - large molecules Endosulfansulfate ,5 Eluate 2 (ECD) Parathion ,7 Eluate 2 (NPD + FPD) Chinomethionate ,0 GPC cut end Bromopropylate ,7 Eluate (ECD) Captane ,0 Eluate 3 (NPD)// + Insert check Metalaxyl ,0 Eluate 4 (NPD) Triamiphos ,0 Eluate 5 (NPD + FPD)

26 Official Manual of Test Methods According to 64 LFGB Analysis of Foodstuffs L Analysis of Foodstuffs Residue analysis of plant protective substances in Food (Table of relative retention time of plant protective substances with gas chromatography

27 696 peaks with Rt times 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, ,47 0, xxx xx x Acephate ,47 0, xx x xx Aclonifen ,40 1, xxx x x Acrinathrin, ,57 1, xx xxx xx Acrinathrin, ,58 1, xxx xxx xx Alachlor ,89 0, xxx xxx x Aldrin ,97 0, xxx xxx Allidochlor ,40 0, xxx xx xx Alodan ,09 1, xx xxx Ametryn ,89 0, xxx xx Amidithion ,96 1, x x x Aminocarb ,73 0, xx xx Amitraz ,56 1, xx x

28 Thanks for your attention! Bahnweg Dorfen Germany

GPC Gel Permeation Chromatography

GPC Gel Permeation Chromatography The proved clean-up method for food, feed, and environmental laboratories Preparative Gel Permeation Chromatography GPC = Gel Permeation Chromatography - Separation of