EN 15662:2008
(Main)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
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
This European Standard describes a method for the analysis of pesticide residues in foods of plant origin, such as fruits (including dried fruits), vegetables, cereals and processed products thereof. The method has been collaboratively studied on a large number of commodity/pesticide combinations.
Pflanzliche Lebensmittel - Bestimmung von Pestizidrückständen mit GC-MS und/oder LC-MS/MS nach Acetonitril-Extraktion/Verteilung und Reinigung mit dispersiver SPE - QuEChERS-Verfahren
Diese Europäische Norm beschreibt ein Verfahren für die Analyse von Pestizidrückständen in pflanz-lichen Lebensmitteln, wie z. B. Früchten (einschließlich Trockenfrüchten), Gemüse, Getreide und verarbei-teten Erzeugnissen davon. Das Verfahren wurde von verschiedenen Laboratorien an einer großen Anzahl an Lebensmittel/Pestizid-Kombinationen getestet.
Aliments d'origine végétale - Méthode polyvalente de détermination des résidus des pesticides par CG-SM et CL/SM/SM avec extraction/partition avec de l'acétonitrile et nettoyage par SPE dispersés - Méthode QuEchERS
La présente Norme européenne décrit une méthode d’analyse des résidus de pesticides dans les aliments
d'origine végétale, tels que les fruits (y compris les fruits secs) et légumes, les céréales, ainsi que leurs
produits dérivés. Cette méthode a fait l’objet d’une étude collaborative sur un grand nombre de combinaisons
de denrées/pesticides.
Hrana rastlinskega izvora - Določanje ostankov pesticidov z uporabo GC-MS in/ali LC-MS(/MS) po delitvi in izpiranju acenotrila z disperzivno SPE - Metoda QuEChERS
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2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.4X(&K(56Pflanzliche Lebensmittel - Bestimmung von Pestizidrückständen mit GC-MS und/oder LC-MS/MS nach Acetonitril-Extraktion/Verteilung und Reinigung mit dispersiver SPE - QuEChERS-VerfahrenAliments d'origine végétale - Méthode polyvalente de détermination des résidus des pesticides par CG-SM et CL/SM(/SM) avec extraction/partition avec de l'acétonitrile et nettoyage par SPE dispersée - Méthode QuEChERSFoods 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-method67.050Splošne preskusne in analizne metode za živilske proizvodeGeneral methods of tests and analysis for food productsICS:Ta slovenski standard je istoveten z:EN 15662:2008SIST EN 15662:2009en,fr,de01-januar-2009SIST EN 15662:2009SLOVENSKI
STANDARD
EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 15662November 2008ICS 67.050 English VersionFoods of plant origin - Determination of pesticide residues usingGC-MS and/or LC-MS/MS following acetonitrileextraction/partitioning and clean-up by dispersive SPE -QuEChERS-methodAliments d'origine végétale - Méthode polyvalente dedétermination des résidus des pesticides par CG-SM etSL/SM(SM) avec extraction/partition avec de l'acétonitrile etnettoyage par SPE dispersés - Méthode QuEchERSPflanzliche Lebensmittel - Bestimmung vonPestizidrückständen mit GC-MS und/oder LC-MS/MS nachAcetonitril-Extraktion/Verteilung und Reinigung mitdispersiver SPE - QuEChERS-VerfahrenThis European Standard was approved by CEN on 13 September 2008.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the CEN Management Centre or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same status as theofficial versions.CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2008 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15662:2008: ESIST EN 15662:2009
Examples of experimental conditions.22 Annex B (informative)
Precision data.25 Annex C (informative)
Procedure schematically (for 10 g sample).75 Annex D (informative)
Complementary information.76 Bibliography.81
1 Scope This European Standard describes a method for the analysis of pesticide residues in foods of plant origin, such as fruits (including dried fruits), vegetables, cereals and processed products thereof. The method has been collaboratively studied on a large number of commodity/pesticide combinations. 2 Principle The homogeneous sample is extracted with the help of acetonitrile. Samples with low water content (< 80 %) require the addition of water before the initial extraction to get a total of approximately 10 g of water. After addition of magnesium sulfate, sodium chloride and buffering citrate salts, the mixture is shaken intensively and centrifuged for phase separation. An aliquot of the organic phase is cleaned-up by dispersive solid phase extraction (D-SPE) employing bulk sorbents as well as magnesium sulfate for the removal of residual water. Following clean-up with amino-sorbents (e.g. primary secondary amin sorbent, PSA) extracts are acidified by adding a small amount of formic acid, to improve the storage stability of certain base-sensitive pesticides. The final extract can be directly employed for GC- and LC-based determinative analysis. Quantification is performed using an internal standard, which is added to the extract after the initial addition of acetonitrile. A brief overview of the method is shown in the flowchart in Annex C. 3 Reagents 3.1 General and safety aspects Unless otherwise specified, use reagents of recognized analytical grade. Take every precaution to avoid possible contamination of water, solvents, sorbents, inorganic salts, etc.
DISCLAIMER — This standard refers to several trade names products and instruments which are commercially available and suitable for the described procedure. This information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of the products named. Equivalent products may be used if they can be shown to lead to equivalent results. 3.2 Water, HPLC quality 3.3 Acetonitrile, HPLC quality 3.4 Methanol, HPLC quality 3.5 Ammonium formate
3.6 Magnesium sulfate, anhydrous, grit, e.g. Fluka No. 63135
Phthalates may be removed in a muffle furnace by heating to 550 °C (e.g. overnight).
3.7 Magnesium sulfate, anhydrous, fine powder
Phthalates may be removed in a muffle furnace by heating to 550 °C (e.g. overnight). 3.8 Sodium chloride 3.9 Disodium hydrogencitrate sesquihydrate SIST EN 15662:2009
3.11 Sodium hydroxide solution, substance concentration c = 5 mol/l Dissolve 2 g of sodium hydroxide in approximately 5 ml of water and dilute to 10 ml. 3.12 Buffer-salt-mixture for second extraction and partitioning:
Weigh 4 g ± 0,2 g of magnesium sulfate anhydrous (3.6), 1 g ± 0,05 g of sodium chloride, 1 g ± 0,05 g of trisodium citrate dihydrate and 0,5 g ± 0,03 g of disodium hydrogencitrate sesquihydrate into a cup (4.11). These amounts refer to approximately 10 ml water in the sample. For highly acidic samples (with pH < 3) the pH-value achieved after the addition of buffering salts is usually below 5. To better protect acid labile compounds the pH-value can be elevated by adding 5 mol/l sodium hydroxide solution (3.11): For lemons, limes and currants add 600 µl and for raspberry 200 µl of sodium hydroxide solution directly to the salt mixture.
NOTE It is advisable to prepare a sufficient number of buffer-salt-mixtures in advance so that extraction series can be performed quickly without interruption. The preparation of the salt mixtures can be enormously facilitated using a sample divider (4.12). The amounts of salts given above are to be used for sample portions containing approximately 10 g water. 3.13 Formic acid solution in acetonitrile, volume fraction 3 = 5 ml formic acid/100 ml
Dilute 0,5 ml of formic acid (mass fraction w = > 95 %) to 10 ml with acetonitrile (3.3).
3.14 Primary secondary amin sorbent For example, Bondesil-PSA® 40 µm Varian No. 122130231). Other amino sorbents may be used, but investigations may be necessary to prove equivalency especially regarding analyte losses and pH value of the end extracts.
3.15 Graphitised Carbon Black sorbent (GCB), e.g. Supelco Supelclean Envi-Carb® 1) SPE Bulk Packing, No. 57210U Other graphitised carbon sorbents may be used, but investigations will be necessary to prove equivalency especially regarding analyte losses.
3.16 Sorption mixture 1: GCB (3.15)/ magnesium sulfate anhydrous fine powder (3.7)-mixture, 1 + 59 mass portions
Mix the two components intensively to form a visually homogeneous mixture.
3.17 Sorption mixture 2: GCB (3.15)/ magnesium sulfate anhydrous fine powder (3.7)-mixture, 1 + 19 mass portions
Mix the two components intensively to form a visually homogeneous mixture. NOTE It is highly advisable to prepare the sorption mixtures 1 (3.16) and 2 (3.17) in advance and store them in sealable vessels. For the extract clean-up according to 5.4.3 the pre-mixed sorption mixtures 1 or 2 are weighed into the centrifuge tubes (4.4).
1) Bondesil-PSA® is a product supplied by Varian, Inc. (Palo Alto, CA, USA). Envi-Carb is a product supplied by Supelco. This information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of the products named. Equivalent products may be used if they can be shown to lead to the same results. SIST EN 15662:2009
= 10 µg/ml to 50 µg/ml Table 1 shows a list of potential internal standards (ISTDs) and quality control (QC) standards that may be used in this method. The suggested concentration values (CISTD) listed refers to the ISTD solutions that should be added at the first extraction step (5.2). An appropriate dilution of this solution (mixcalISTDC) should be prepared to be used for the preparation of the standard solutions. For more details see 3.22. Table 1 — Potential internal standards (ISTDs) or quality control (QC) standards GC LC Name of the compound Log P (octanol-water partition coefficient) Chlorine atoms Sugges-ted concen-trationCISTD [µg/ml]a ECDNPDMSD EI (+) MSD
CI (-) MS/MS
ESI (+) MS/MS ESI (-) Potential Internal Standards PCB 18
5,55 3 50 +++ - ++ +++ - - PCB 28
5,62 3 50 +++ - ++ +++ - - PCB 52 6,09 4 50 +++ - ++ +++ - - Triphenyl phosphate 4,59 - 20 - +++ +++ - +++ - Tris-(1,3-dichlorisopropyl)-phosphate
3,65 6 50 +++ +++ +++ +++ +++ + Triphenylmethane 5,37 - 10 - - +++ - - - Bis-nitrophenyl urea (nicarbazin) 3,76 - 10 - - - - - +++ Potential Quality Control Standards (may be contained in the same mixture as the other ISTDs used or added at a different stage of analysis to detect and localize sources of error) PCB 138b 6,83 6 50 +++ - ++ +++ - - PCB 153b 7,75 6 50 +++ - ++ +++ - - Anthracene (or its d10 analogue)c 4,45 - 100 - - ++ - - - a
Exemplary concentrations of the ISTD solutions to be added to the test samples in 5.2, use acetonitrile as solvent. b
Recoveries of PCB 138 and 153 drop as lipid amount in the sample increases, recoveries of those two compounds exceeding 70 % indicate that no unacceptable partitioning losses have occurred even for the most lipophilic pesticides. c
Recoveries of anthracene exceeding 70 % will indicate that no unacceptable losses of pesticides with high carbon affinity have occurred during dispersive SPE with GCB.
3.20 Pesticide stock solutions Prepare individual stock solutions of analytical standards at concentrations that are sufficient to allow the preparation of complex pesticide working solutions (3.21) that are used for the preparation of standard solutions.
Usually, store stock solutions at ≤ -18 °C. Check the stability of stock solutions during storage regularly [2]. In some cases the addition of acids or bases can be helpful to enhance stability and extend the acceptable SIST EN 15662:2009
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