QUICK AND EASY LAB SAMPLE PREP FOR GCMSMS AND LCMSMS MULTIRESIDUE PESTICIDE ANALYSIS

Transcription

1 QUICK AND EASY LAB SAMPLE PREP FOR GCMSMS AND LCMSMS MULTIRESIDUE PESTICIDE ANALYSIS

2 is the new brand that identifies the QuEChERS Products made in Italy for the extraction and clean up of analytes from a wide variety of matrices such as fruits, vegetables, meat products, fruit juices, wine, spices, cereals, honey, dried fruit. By means of this treatment one can detect analytes as pesticides, mycotoxins, veterinary drugs, acrylamides, antibiotics, polycyclic aromatic hydrocarbons, etc. The method based on a paper published in 2003 by the US Department of Agriculture - Eastern Regional Research Center - in Wyndmoor, PA (M. Anastassiades, S.J. Lehotay, D. Stajnbaher, F.J. Schenck) admirably replaces old extraction methods drastically reducing execution and costs arising from: solvents, glassware and special laboratory equipment. Method Original of 2003 has been joined by the methods AOAC and EN approved by European and American Food Regulatory Agencies that are surely the most used and disseminated. WHAT IS? PROCEDURE INVOLVING TWO PHASES EXTRACTION (LLE) The analytes are extracted from the matrix by the use of acetonitrile and different types of salts and buffers. After the partition liquid-liquid (LLE) it follows: shaking, centrifugation and collection of acetonitrile phase. DISPERSIVE SOLID PHASE (d-spe) Deriving from the first step, the organic phase (acetonitrile extract) comes in contact with other typical clean up sorbents: primary and secondary amine (PSA), graphitized carbon black (GCB) or C18 with the purpose of removing sugars, lipids, sterols, organic acids, proteins, carotenoids, chlorophyll and other pigments in addition to the residual water by the use of magnesium sulfate. After that it follows shaking and centrifugation. The anhydrous acetonitrile phase is ready for analysis in GCMS / MS directly (LVI) or after exchange of solvent, while the injection LCMS / MS is ready after sample dilution with mobile phase. UNI EN ISO9001:2008 UNI EN ISO14001:2004 ISO/IEC 17025:2005 ISO Guide 34:2009 * ISO is a trademark of the International Standards Organization. PRODUCTS WITH LOW WATER CONTENT The extraction QuEChERS is designed primarily for food products with a high water content but it also applies to dried foods by adding during comminution step, weighted amount of water depending on the type of sample as defined in the CEN Guidelines. FRUITS AND VEGETABLES FRUITS AND VEGETABLES CEREALS (WHEAT, CORN, OATS, BARLEY, ETC.) NUTS (HAZELNUTS, ALMONDS, PISTACHIOS, ETC.)** HONEY OLIVE OIL SPICES (PEPPER, PAPRIKA, ETC.) WITH MORE THAN 80% OF WATER CONTENT WITH WATER CONTENT BETWEEN 25% AND 80% WEIGHT OF SAMPLE WATER ADDED 10 g 10 g 5 g 5 g 5 g 8 g 2 g none X* g 10 g 7,5 g 10 g 2 g 10 g * X = 10 g - water amount in 10 g of sample. ** Water may be added during shredding step of the initial sample.

3 PRODUCTS The line of products branded is the most completed line on the market. It was realized in every possible variant of packaging Ready to Use (conical tubes, self-standing tubes, packets, etc.) and in different wording so as to satisfy all the official methods (EN 15662, AOAC , etc.). The raw materials are selected and analyzed for each batch in the laboratory accredited to ISO / IEC 17025: Each batch of Falcon tubes, test tubes and caps are subjected to checks as leak and release tests. Each production lot of the is accompanied by a certificate of analysis showing the traceability of components and traceability of the analytical data as well as a safety data sheet complies with the REACH Reg. (EC) 1907/2006. SOME GOOD REASONS TO CHOOSE PRODUCTS d-spe clean up improves ms spectral library matches Higher recoveries for all classes of analytes Product code batch number color code barcode identification Better peak shape results in more accurate quantification Cleaner extracts from cleaner products Excellent lot to lot reproducibility Closely Related to CHOOSE PRODUCTS AND SAVE TILL /YEAR Estimated time and materials to process 20 samples/day Traditional Extraction Method (mini-luke-or Modified Luke Methods) QuEChERS Method Savings with QuEChERS Prod Estimated time to process 20 samples 400 min 80 min 5x faster Pure solvent used ml 200 ml 6 9x less solvent Chlorinated waste ml 0 safer, cheaper, greener Glassware and specialized laboratory equipment and disposable materials Capacity for 200 ml, quartz wool, funnel, water bath or evaporator Micropipette Centrifuge is READY TO USE *Estimate for a laboratory performing analysis multiresidual 1200 per year of pesticides in food matrices with method EN 15662

4 ORIGINAL (1) AOAC (2) EN (3) EXTRACTION (LLE) Depending on the nature of the commodity, cut and/or grind until the homogenization is reached Depending on the nature of the commodity, cut and/or grind until the homogenization is reached Depending on the nature of the commodity, cut and/or grind until the homogenization is reached Weigh 10 g of homogenized/hydrated(*) sample in a 50 ml centrifuge tube Weigh 15 g of homogenized/hydrated(*) sample in a 50 ml centrifuge tube Weigh 10 g of homogenized/hydrated(*) sample in a 50 ml centrifuge tube 10 ml of ACN 15 ml of 1 % HOAc in ACN 10 ml of ACN ISTD ISTD ISTD Cod. Q17B14H093 (4 g MgSO g NaCl) vigorously for 1 min. Cod. Q17B15E092 (6 g MgSO 4 + 1,5 g NaOAc) vigorously for 1 min. Cod. Q17B14F091 (4 g MgSO g NaCl + 1 g Na 3 Citrate 2H 2 O + 0,5 g Na 2 HCitrate 1.5H 2 O) vigorously for 1 min. Centrifuge for 5 minutes at 5000 rpm Centrifuge for 1 minute at >1500 rcf Centrifuge for 5 minutes at >3000 g Transfer 1 ml aliquot of supernatant to a dispersive tube (2 ml), d-spe, containing MgSO 4 + PSA (plus GCB to remove pigments and C18 to remove fatty compounds and n-polar interferences). Choice the right d-spe Tube. (See next page) for 1 min. DISPERSIVE SPE CLEAN-UP Transfer 8 ml aliquot of supernatant to a dispersive tube (15 ml), d-spe AOAC, containing MgSO 4 + PSA (plus GCB to remove pigments and C18 to remove fatty compounds and non-polar interferences). Choice the right d-spe Tube. (See next page) 30 seconds Transfer 6 ml aliquot of supernatant to a dispersive tube (15 ml), d-spe EN 15662, containing MgSO 4 + PSA (plus GCB to remove pigments and C18 to remove fatty compounds and non-polar interferences). Choice the right d-spe Tube. (See next page) for 30 seconds (when using GCB 2 minutes) Centrifuge for 1 minute at 6000 rpm Centrifuge for 1 minute at >1500 rcf Centrifuge for 5 minutes at >3000 g Transfer into vial. Analyze directly or acidify if necessary (LC-MS/ MS) or protect with sorbitol and preserve with toluene (GC-MS/MS). Depending on the nature of the commodity and pesticides see detailed procedure. Transfer into vial. Analyze directly or acidify if necessary (LC-MS/ MS) or protect with sorbitol and preserve with toluene (GC-MS/MS). Depending on the nature of the commodity and pesticides see detailed procedure. Transfer into vial. Analyze directly or acidify if necessary (LC-MS/ MS) or protect with sorbitol and preserve with toluene (GC-MS/MS). Depending on the nature of the commodity and pesticides see detailed procedure. Bibliography: (1) Fast and easy multiresidue method employing acetonitrile extraction/partitioning and dispersive solid-phase extraction for the determination of pesticide residues in produce. J. AOAC International 86 (2003) 412. M. Anastassiades, S.J. Lehotay, D. Stajnbaher, F.J. Schenck. (2) AOAC Official Method Pesticide Residues in Foods by Acetonitrile Extraction and Partitioning with Magnesium Sulfate. (3) EN November Foods of plant origin - Determination of pesticide residues using GC-MS and/or LC-MS/MS following acetonitrile extraction/partitioning and clean-up by dispersive SPE - QuEChERS-method. (*) Dry commodities must be hydrated in order to improve the extraction. CHOOSING A dspe SORBENT For each type of matrix you can choose the most appropriate d-spe. Tubes d-spe with MgSO 4 and PSA effectively remove polar organic acids, sugars, anthocyanine, lipids and sterols. Some fruits and vegetables (spinach, red peppers, carrots, etc.) with a high content of non-polar pigments such as carotenoids, chlorophyll, etc. require d-spe with graphitized carbon black (GCB) for the discoloration. The elimination of pigments is necessary to avoid accumulations in the liners of GC s injector. PSA Primary and secondary amine REMOVE sugar, fatty acids, organic acids, anthocyanine pigments PSA is the base sorbent used for QuEChERS clean-up (dspe tube) because removes substances that might act as instrumental interferences. C18 Octadecyl REMOVE lipids, non polar interferences In addition to PSA, C18 removes lipids and non polar interferences. GCB Graphitized carbon black REMOVE pigments, sterols, non polar interferences GCB removes pigments that can degrade GCMS performance but EN15662 recommends less GCB because can have a negative effect on the recoveries of certain pesticides like : Chlorothalonil, Permethrin, Deltamethrin, Coumaphos,Thiabendazole, Quintozene, etc. Further Information: itional information useful to the analyst planning QuEChERS analysis may be found to the following website:

5 GENERAL Fats and waxes Pigment High Pigment EN Pigments and Fats AOAC GENERAL Fats and waxes Pigment High Pigment EN Pigments and Fats AOAC FRUITS Citrus Juices Grapefruit Lemon / Lime Orange Orange Peel Nectarines Tangerine Apple Apple, Dried Apple Sauce Apple Juice Pear Quince Blackberry Blueberry Currant Elder Gooseberries, Red Red Grapes Green Grapes Raspberry Raisins Cranberry Strawberry Apricot Apricots, Dried Apricot Nectar Cherry Mirabelle Nectarines Peach Fishing, Dried Plum Dried Plum Pineapple Banana Avocado Olives Fig, Dried Melon Kiwi Mango Papaya OTHER FOODS Fish, Honey, Oil, Eggs Spices (Pepper, Paprika, etc.) Meat, etc. *Other Method * VEGETABLES Beet Carrot Celeriac Horseradish Parsley Root Radish Salsify Potato Garlic Onion Shallot Leek Chive Eggplant Cucumber Green Pepper Red Bell Pepper Pumpkin Tomato Zucchini Broccoli Brussels Sprouts Cauliflower Chinese Cabbage Kale Kohlrabi Red Cabbage Savoy Cabbage White Cabbage Varieties of lettuce Endive Watercress Valerianella Cilantro Basil Parsley Arugula Spinach Asparagus Celery Leek Rhubarb Artichoke Beans, Peas (Fresh) Lentils, Beans (Dry) Wheat, Corn, Rice Flour, Etc. Coffee Beans Tea Leaves HIGH RECOVERIES FOR ALL CLASSES OF ANALYTES PESTICIDES Thiophanate-methyl Thiabendazole Propoxur Penconazole Metalaxyl Kresoxym-methyl Imidacloprid Ethoprophos Dichlorvos Cyprodinil Azinphos-ethyl Acephate RECOVERY % PESTICIDES Acephate Azinphos-ethyl Cyprodinil Dichlorvos Ethoprophos Imidacloprid Kresoxym-methyl Metalaxyl Penconazole Propoxur Thiabendazole Thiophanate-methyl RECOVERY % RSD (n=6) 0,32 1,22 4,98 4,26 4,93 2,40 4,67 3,86 4,85 4,74 4,78 4,96 Pesticide Recoveries and RSDs obtained by d-spe Cleanup of apple sample fortified at 100 ng/g using EN PSA.

6 EXTRACTION LLE EN APPLICATIONS SCREENING 135 PESTICIDES IN FAST GC-MSMS CLEAN-UP/dSPE GC CONDITION : Q1B14F mg MgSO₄, 150 mg PSA : Q2A22Z391 Carrier Gas : Injector : PTV Temp. Program : ChromLab Column : Split : Transer line Temp : GC Oven program : He, constant flow 1 ml/min PTV Splitless Mode with Siltek baffled liner 2 mm ID 70 C for 0,02 min; 12 C/s to 280 C, 1,2 min; 14,5 C/s to 320 C 6 min, clean flow 80 ml/min 5 MS, L: 20 mt - ID: 0,18 mm - F.T.: 0,18µm Cod. CHL-5MS20HS1818 Splitless injection, splitflow 50 ml/min at C 80 C for C/min to 210 C 20 C/min to 320 C C for 120 MS CONDITION Sorce Temp. : 260 C Emission Current : 25 µa Ionization Mode : EI at 70 ev Mass Resolution : Q1 and Q3 at 0,7 Da (FWHM) Collision Gas : Ar at 1,5 mtorr Cycle Time : 0,30 s Acquisition Mode : Timed-SRM Mass table : 276 Timed-SRM transition/fas GC run MATERIALS: Pesticide Stock Solution : Multicomponents Kit 135 Pesticides Cod. KIT4T3L135 Internal Standard : Malathion d6 Cod. CRM2A2L1285 Surrogate : TPP 100 mg/l Cod. CRM2B3L760 EXTRACTION LLE EN SCREENING 510 PESTICIDES IN LC-HRMS CLEAN-UP/dSPE HPLC CONDITION : Q1B14F mg MgSO₄, 150 mg PSA : Q2A22Z391 Column : 100 x 2,1-1.9µm p.z. Chrom-Lab C18 : Cod. CH Flow Rate : 0,5 ml/min H₂0 with 0,1% formic acid A Mobile Phase : + 4mM ammonium formate CH₃OH with 0,1% formic acid B + 4mM ammonium formate Time: ,5 14 Gradient A%: B%: MS CONDITION Mass Range : Resolution : Automatic Gain Control : 10 e 6 HEATED ELETTROSPRY IONIZATION SORCE CONDITIONS: Spray Voltage : 2200 V Capillary Temperature : 280 C Sheat gas : 32au Auxiliary gas : 7au Vaporizer Temp. MATERIALS: : 200 C Pesticide Stock Solution : Multicomponents Kit 510 Pesticides Cod. KIT4V3L510 Internal Standard : Parathion-ethyl d10 Cod. CRM2A2L1409 Surrogate : TPP 100 mg/l Cod. CRM2B3L760 CONTINUITY AND COMPLEMENTARITY WITH THE CRM BRANDED is closely related to the certified reference materials. There are a variety of standards available: QC Standard, internal standards, Standard deuterated surrogates ready to use for the extraction and some kits Multi Components mixtures of pesticides. Consult the catalog containing over 2000 products on Parathion-Ethyl d mg/l Malathion-d6 100 mg/l Surrogate TPP 100 mg/l Mix A26 EN QuEChERS QC Spike Multi Components Kit 510 Pesticides Multi Components Kit 218 Pesticides Multi Components Kit 135 Pesticides CODE CRM2A2L1409 CRM2A2L1285 CRM2B3L760 CRM3B3L115 KIT4V3L510 KIT4B3L218 KIT4T3L135 Moreover, in our catalog, all accessories are available for the execution of the method QuEChERS: bottle top dispenser solvent, tube racks, micropipettes, GC and HPLC columns, inlet liners, vials, etc. which can be purchased on e-commerce: REGISTER ON OUR SITE AND YOU WILL GET AN IMMEDIATE DISCOUNT OF UP TO 40% ON MORE THAN ITEM CATALOG

7 ORDERING INFORMATION Method : EN Citrate LLE 4,8 g MgSO₄, 1,2 g NaCl, 1,2 g SCTD, 0,6 g SCTS Method : Original LLE Unbuffered 4 g MgSO₄, 1 g NaCl (sample=10g) 6 g MgSO₄, 1,5 g NaCl (sample=15g) Method : A.O.A.C Acetate LLE 6 g MgSO₄, 1,5 g NaAcetate 6 g MgSO₄, 1,5 g NaAcetate Method : Acrylamides LLE 4 g MgSO₄, 0,5 g NaCl Method : Mycotoxins LLE 4 g MgSO₄, 1 g NaCl EXTRACTION LLE 50 Tubes (50ml) Ready to Use 50 Packets + 50 empty Tubes (50ml) 250 Transfer Tubes w/o Tubes (50 ml) 300 Packets w/o Tubes (50 ml) 300 Packets empty Tubes (50ml) 50 Transfer Tubes + 50 Self Standing Tubes (50ml) 50 Packets + 50 Self Standing Tubes (50ml) 50 Packets + 50 empty Tubes (50ml) Q17B14F091 Q1B14F091 Q5B14F091 Q15D14F091 Q16E14F091 Q18B14F091 Q20B14F091 Q19B14F091 Q17B16N091 Q17B14H093 Q17B15I093 Q17B15E092 Q5B15E092 Q17B14L095 Q17B14H096 KIT CLEAN-UP Method : EN d-spe 900 mg MgSO₄, 150 mg PSA 900 mg MgSO₄, 150 mg PSA Varian* 900 mg MgSO₄, 150 mg PSA, 150 mg C18EC 900 mg MgSO₄, 150 mg PSA Varian*, 150 mg C18EC 900 mg MgSO₄, 150 mg PSA, 15 mg GCB 900 mg MgSO₄, 150 mg PSA Varian*, 15 mg GCB 900 mg MgSO₄, 150 mg PSA, 45 mg GCBmide LLE 900 mg MgSO₄, 150 mg PSA Varian*, 45 mg GCB Method : A.O.A.C d-spe 1200 mg MgSO₄, 400 mg PSA 1200 mg MgSO₄, 400 mg PSA Varian* 1200 mg MgSO₄, 400 mg PSA, 400 mg C18EC 1200 mg MgSO₄, 400 mg PSA Varian*, 400 mg C18EC 1200 mg MgSO₄, 400 mg PSA, 400 mg GCB 1200 mg MgSO₄, 400 mg PSA Varian*, 400 mg GCB 1200 mg MgSO₄, 400 mg PSA, 400 mg C18EC, 400 mg GCB 1200 mg MgSO₄, 400 mg PSA Varian*, 400 mg C18EC, 400 mg GCB Method : C18 d-spe Tube 900 mg MgSO₄, 150 mg C18 Method : Mycotoxins d-spe Tube 900 mg MgSO₄, 300 mg PSA Method : PSA/C18/GCB dspe Tube 900 mg MgSO₄, 300 mg PSA, 300 mg C18EC, 45 mg GCB KIT CLEAN-UP Method : EN d-spe 150 mg MgSO₄, 25 mg PSA 150 mg MgSO₄, 25 mg PSA Varian* 150 mg MgSO₄, 25 mg PSA, 25 mg C18EC 150 mg MgSO₄, 25 mg PSA Varian*, 25 mg C18EC 150 mg MgSO₄, 25 mg PSA, 2.5 mg GCB 150 mg MgSO₄, 25 mg PSA Varian*, 2.5 mg GCB 150 mg MgSO₄, 25 mg PSA, 7.5 mg GCB 150 mg MgSO₄, 25 mg PSA Varian*, 7.5 mg GCB Method : A.O.A.C d-spe 150 mg MgSO₄, 50 mg PSA 150 mg MgSO₄, 50 mg PSA Varian* 150 mg MgSO₄, 50 mg PSA, 50 mg C18EC 150 mg MgSO₄, 50 mg PSA Varian*, 50 mg C18EC 150 mg MgSO₄, 50 mg PSA, 50 mg GCB 150 mg MgSO₄, 50 mg PSA Varian*, 50 mg GCB 150 mg MgSO₄, 50 mg PSA, 50 mg C18EC, 50 mg GCB 150 mg MgSO₄, 50 mg PSA Varian*, 50 mg C18EC, 50 mg GCB Method : C18 d-spe Tube 150 mg MgSO₄, 25 mg C18 Method : Mycotoxins d-spe Tube 150 mg MgSO₄, 50 mg PSA Method : PSA/C18/GCB dspe Tube 150 mg MgSO₄, 50 mg PSA, 50 mg C18EC, 7.5 mg GCB * Varian is a trademark of Varian inc. Palo Alto, CA USA. d-spe TUBES (15 ml) mg MgSO4, 400 mg PSA d-spe TUBES (2 ml) mg MgSO4, 400 mg PSA Q2A22Z391 Q2A22Z891 Q2A22C391 Q2A22C891 Q2A22Z331 Q2A22Z831 Q2A22Z341 Q2A22Z841 Q2A23Z592 Q2A23Z1092 Q2A23D592 Q2A23D1092 Q2A23Z582 Q2A23Z1082 Q2A23D582 Q2A23D1082 Q2A22G094 Q2A22Z496 Q2A22O447 Q1C21Z191 Q1C21Z691 Q1C21A191 Q1C21A691 Q1C21Z111 Q1C21Z611 Q1C21Z121 Q1C21Z621 Q1C21Z292 Q1C21Z792 Q1C21B292 Q1C21B792 Q1C21Z252 Q1C21Z752 Q1C21B252 Q1C21B752 Q1C21M094 Q1C21Z296 Q1C21B227

8 Accreditations and Certifications ISO Guide 34:2009 ISO/IEC 17025:2005 UNI EN ISO 14001:2004 UNI EN ISO 9001:2008 Download certificates alessandronitti graphicdesigner Produced by: LAB. INSTRUMENTS S.r.l. - High Pure Standard & Chemicals Division Tel Fax: SS 172 (Putignano-Alberobello) km Castellana Grotte (BA) Site: quelab@labinstruments.it and are a trademark of Lab.Instruments srl (Italy). All rights reserved. Specifications, term and pricing are subject to change. Not all products is available in all countries. Please consult your local rapresentative to details. QL 01 E 02/15