1、January 2014 Translation by DIN-Sprachendienst.English price group 11No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).IC
2、S 67.050!%+KD“2084033www.din.deDDIN EN 12393-1Foods of plant origin Multiresidue methods for the determination of pesticide residues by GCor LC-MS/MS Part 1: General considerations;English version EN 12393-1:2013,English translation of DIN EN 12393-1:2014-01Pflanzliche Lebensmittel Multiverfahren zu
3、r Bestimmung von Pestizidrckstnden mit GC oder LC-MS/MS Teil 1: Allgemeines;Englische Fassung EN 12393-1:2013,Englische bersetzung von DIN EN 12393-1:2014-01Aliments dorigine vgtale Mthodes multirsidus de dtermination de rsidus de pesticides par CPG ouCL-SM/SM Partie 1: Gnralits;Version anglaise EN
4、12393-1:2013,Traduction anglaise de DIN EN 12393-1:2014-01SupersedesDIN EN 12393-1:2009-02www.beuth.deDocument comprises 19 pagesIn case of doubt, the German-language original shall be considered authoritative.01.14 DIN EN 12393-1:2014-01 2 A comma is used as the decimal marker. National foreword Th
5、is document (EN 12393-1:2013) has been prepared by Technical Committee CEN/TC 275 “Food analysis Horizontal methods” (Secretariat: DIN, Germany), Working Group WG 4 “Pesticides in foods of plant origin” (Secretariat: DIN, Germany). The responsible German body involved in its preparation was the Norm
6、enausschuss Lebensmittel und landwirtschaftliche Produkte (Food and Agricultural Products Standards Committee), Working Committee NA 057-01-08 AA Pestizide. Amendments This standard differs from DIN EN 12393-1:2009-02 as follows: a) method L: “Extraction with acetone, liquid-liquid partition with di
7、chloromethane and clean-up on a silica gel/charcoal column” has been deleted; b) methods N and P now also allow the separation of analytes by liquid chromatography with MS/MS-detection; c) the scope of method N has been extended to include a definite range of pesticides and their validation data; d)
8、 information on GC-MS/MS detection has been incorporated; e) the standard has been editorially revised and references have been updated. Previous editions DIN EN 12393-1: 1998-12, 2009-02 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 12393-1 November 2013 ICS 67.050 Supersedes EN 12393-1:2008
9、English Version Foods of plant origin - Multiresidue methods for the determination of pesticide residues by GC or LC-MS/MS -Part 1: General considerations Aliments dorigine vgtale - Mthodes multirsidus de dtermination de rsidus de pesticides par CPG ou CL-SM/SM - Partie 1: Gnralits Pflanzliche Leben
10、smittel - Multiverfahren zur Bestimmung von Pestizidrckstnden mit GC oder LC-MS/MS - Teil 1: Allgemeines This European Standard was approved by CEN on 21 September 2013. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European
11、Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (En
12、glish, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium
13、, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerla
14、nd, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Me
15、mbers. Ref. No. EN 12393-1:2013: EEN 12393-1:2013 (E) 2 Contents Page Foreword 3 Introduction .4 1 Scope 5 2 Normative references 5 3 Principle 5 4 Reagents .6 5 Apparatus .9 6 Procedure 11 7 Determination 13 8 Confirmatory tests 14 9 Evaluation of results 14 10 Test report . 15 Annex A (informative
16、) Purification of solvents and reagents 16 Bibliography . 17 DIN EN 12393-1:2014-01 EN 12393-1:2013 (E) 3 Foreword This document (EN 12393-1:2013) has been prepared by Technical Committee CEN/TC 275 “Food analysis - Horizontal methods”, the secretariat of which is held by DIN. This European Standard
17、 shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by May 2014, and conflicting national standards shall be withdrawn at the latest by May 2014. Attention is drawn to the possibility that some of the elements of this documen
18、t may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. This document supersedes EN 12393-1:2008. The following significant technical changes have been made: a) separation of analytes by liquid chromatography with MS/MS-d
19、etection in methods N and P; b) incorporation of information on GC-MS/MS detection; c) deletion of method L as no longer in use; d) editorial updating of the document according to references, etc. EN 12393, Foods of plant origin Multiresidue methods for the determination of pesticide residues by GC
20、or LC-MS/MS is divided into three parts: Part 1 “General considerations“ provides general considerations with regard to reagents, apparatus, gas chromatography, etc., applying to each of the selected analytical methods; Part 2 “Methods for extraction and clean-up“ presents methods M, N and P for the
21、 extraction and clean-up using techniques such as liquid-liquid partition, adsorption column chromatography or gel permeation column chromatography, etc.; Part 3 “Determination and confirmatory tests“ gives some recommended techniques for the qualitative and the quantitative measurements of residues
22、 and the confirmation of the results. According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugos
23、lav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. DIN EN 12393-1:2014-01 EN 12393-1:2013 (E) 4 Intr
24、oduction This European Standard comprises a range of multi-residue methods of equal status: no single method can be identified as the prime method because, in this field, methods are continuously developing. The selected methods included in this European Standard have been validated and/or are widel
25、y used throughout Europe. Because these methods can be applied to the very wide range of food commodities/pesticide combinations, using different systems for determination, there are occasions when variations in equipment used, extraction, clean-up and chromatographic conditions are appropriate to i
26、mprove method performance, see 3.1. DIN EN 12393-1:2014-01 EN 12393-1:2013 (E) 5 1 Scope This European Standard gives general considerations for the determination of pesticide residues in foods of plant origin. Each method specified in this European Standard is suitable for identifying and quantifyi
27、ng a definite range of those organohalogen, and/or organophosphorus and/or organonitrogen pesticides which occur as residues in foodstuffs of plant origin. This European Standard contains the following methods that have been subjected to interlaboratory studies and/or are adopted throughout Europe:
28、method M: Extraction with acetone and liquid-liquid partition with dichloromethane/light petroleum, if necessary clean-up on Florisil 1)1, 2, 3; method N: Extraction with acetone, liquid-liquid partition with dichloromethane or cyclohexane/ethyl acetate and clean-up with gel permeation and silica ge
29、l chromatography 4, 5; method P: Extraction with ethyl acetate and, if necessary, clean-up with gel permeation chromatography 6. The applicability of the three methods M, N and P for residue analysis of organohalogen, organophosphorus and organonitrogen pesticides, respectively, is given for each me
30、thod. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any
31、 amendments) applies. EN 12393-2:2013, Foods of plant origin Multiresidue methods for the determination of pesticide residues by GC or LC-MS/MS Part 2: Methods for extraction and clean-up EN 12393-3:2013, Foods of plant origin Multiresidue methods for the determination of pesticide residues by GC or
32、 LC-MS/MS Part 3: Determination and confirmatory tests 3 Principle 3.1 General As already described in the introduction, in certain occasions it is possible to improve the method performance by variations in equipment used, extraction, clean-up and chromatographic conditions. Such variations shall a
33、lways be clearly documented and demonstrated to give valid results. The methods described in this European Standard are based on a four-stage process (in some cases two stages may be combined, in whole or in part), as given in 3.2 to 3.5. 1) Florisil is an example of a suitable product available com
34、mercially. This information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of this product. DIN EN 12393-1:2014-01 EN 12393-1:2013 (E) 6 Quality control procedures for pesticide residue analysis, e.g. published by the European Commission
35、 7, should be followed in its updated versions. The principles laid down in this guidance document such as initial method validation, on-going performance verification and calibration should be followed carefully in order to ensure a proper use of different combinations of separation and detection m
36、ethods. Also, further information such as in 8 might be helpful. 3.2 Extraction Extraction of the residues from the sample matrix by the use of appropriate solvents, so as to obtain the maximum efficiency of extraction of the residues and minimum co-extraction of any substances which can give rise t
37、o interferences in the determination. 3.3 Clean-up Removal of interfering materials from the sample extract to obtain a solution of the extracted residue in a solvent which is suitable for determination by the selected method of determination. 3.4 Determination Gas chromatography (GC) with selective
38、 detectors may be used: electron-capture detection (ECD) for organohalogen, thermionic detector (NPD, P-mode or N/P mode) for organophosphorus and organonitrogen compounds and flame-photometric detector (FPD) for organophosphorus and organosulfurous pesticides. Hall detector (ECHD), atomic emission
39、detector (AED) and mass spectrometry (MS) and tandem mass spectrometry may also be used for a large class of pesticides. As alternative, liquid chromatography (LC) with MS-MS-detection has been proven to be successful. 3.5 Confirmation Procedures to confirm the identity and quantity of observed resi
40、dues should be used, particularly in those cases where it would appear that the maximum residue limit (MRL) has been exceeded. 3.6 Use of internal standards An internal standard may be added in a constant amount to samples, the blank and calibration standards. This substance can be used for checking
41、 critical points of methods (e.g. volatile or unstable compounds) and/or for quantification purposes, if appropriate. This is done to correct for the loss of analyte during sample preparation and sample clean-up or to check reproducibility of final determination steps by GC or LC. The internal stand
42、ard should be preferably a compound that has very similar physico-chemical and chemical properties compared to the analyte. 4 Reagents 4.1 General Use reagents of purity suitable for pesticide residue analysis and check their purity (see 4.2). If required, purify water and solvents used, e.g. as des
43、cribed in Annex A, and check their purity (see 4.2). Purify and periodically activate adsorbents according to the requirements of the different analytical methods; check their purity (see 4.2). Take every precaution to avoid possible contamination of water, solvents, adsorbents, etc. from plastics a
44、nd rubber materials. DIN EN 12393-1:2014-01 EN 12393-1:2013 (E) 7 4.2 Check for purity of reagents 4.2.1 Solvents Concentrate solvents by the factor involved in the respective method to be used. Test for purity under the same conditions as used in the method. The chromatogram should not show any int
45、erfering impurity. 4.2.2 Water Extract 10 parts by volume of water with one part by volume of n-hexane or light petroleum, dichloromethane or any other non-water miscible solvent used in the method. Separate the organic phase, concentrate by the factor involved in the respective method and test for
46、purity under the same conditions as used in the method. The chromatogram should not show any interfering impurity. 4.2.3 Inorganic salts Extract inorganic salts, for example sodium chloride, after purification according to Annex A or the requirements of the different analytical methods. Extract the
47、salts and any aqueous solution used, with n-hexane or light petroleum, dichloromethane or any other non-water miscible solvent used in the method. Concentrate the extract by the factor involved in the respective method and test the purity under the same conditions as used in the method. The chromato
48、gram should not show any interfering impurity. 4.2.4 Adsorbents Elute an amount of adsorbent equal to that used in the analytical method with the corresponding type and volume of solvent or solvent mixture. Concentrate the eluate as indicated in the analytical method and test for purity. The chromatogram should not show any interfering impurity. Check the activity of adsorbents regularly as described in the methods M to P (see EN 12393-2). 4.2.5 Standard materials and solutions Use standard
