EN 12393-1-2013 en Foods of plant origin - Multiresidue methods for the determination of pesticide residues by GC or LC-MS MS - Part 1 General considerations《植物食品 利用气相色谱(GC)或液相色谱-质.pdf

1、BSI Standards PublicationBS EN 12393-1:2013Foods of plant origin Multiresidue methods for thedetermination of pesticideresidues by GC or LC-MS/MSPart 1: General considerationsBS EN 12393-1:2013 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 12393-1:2013. It sup

2、ersedes BS EN 12393-1:2008 which is withdrawn.The UK participation in its preparation was entrusted to Technical Committee AW/275, Food analysis - Horizontal methods.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to

3、 include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2013. Published by BSI Standards Limited 2013ISBN 978 0 580 77445 4 ICS 67.050; 67.080.01 Compliance with a British Standard cannot confer immunity from legal obl

4、igations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 30 November 2013.Amendments issued since publicationDate T e x t a f f e c t e dBS EN 12393-1:2013EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 12393-1 November 2013 ICS 67.050 S

5、upersedes EN 12393-1:2008English 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:

6、Gnralits Pflanzliche Lebensmittel - 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

7、 for giving this European 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 t

8、hree official versions (English, 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

9、bodies of Austria, Belgium, 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

10、, Spain, Sweden, Switzerland, 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 wor

11、ldwide for CEN national Members. Ref. No. EN 12393-1:2013: EBS EN 12393-1:2013EN 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

12、 14 10 Test report . 15 Annex A (informative) Purification of solvents and reagents 16 Bibliography . 17 BS EN 12393-1:2013EN 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

13、 is held by DIN. This European Standard 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 th

14、at some of the elements of this document 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 analyte

15、s by liquid chromatography with MS/MS-detection 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 det

16、ermination of pesticide residues by GC 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-

17、up“ presents methods M, N and P for the 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 th

18、e quantitative measurements of residues 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,

19、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, Switzerland, Turkey and the United Kingdom. BS EN 1239

20、3-1:2013EN 12393-1:2013 (E) 4 Introduction 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 ha

21、ve been validated and/or are widely 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 chromatograph

22、ic conditions are appropriate to improve method performance, see 3.1. BS EN 12393-1:2013EN 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

23、for identifying and quantifying 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 ar

24、e adopted throughout Europe: 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

25、 gel permeation and silica gel 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, respe

26、ctively, is given for each method. 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 refer

27、enced document (including any 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 o

28、f pesticide residues by GC or 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 condit

29、ions. Such variations shall always 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 s

30、uitable product available commercially. This information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of this product. BS EN 12393-1:2013EN 12393-1:2013 (E) 6 Quality control procedures for pesticide residue analysis, e.g. published by

31、 the European Commission 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 se

32、paration and detection methods. 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 substanc

33、es which can give rise to 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 chromatogr

34、aphy (GC) with selective 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

35、(ECHD), atomic emission 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 q

36、uantity of observed residues 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

37、can be used for checking 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 o

38、r LC. The internal standard 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 so

39、lvents used, e.g. as described 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, adsorben

40、ts, etc. from plastics and rubber materials. BS EN 12393-1:2013EN 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 shou

41、ld not show any interfering 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 m

42、ethod and test for 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 me

43、thods. Extract the 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 m

44、ethod. The chromatogram 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

45、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 materials of at least 95 % purity and traceable quality as standards for residue anal

46、ysis. Ensure dilute solutions are prepared and checked frequently, and that standard solutions are stored in glass bottles in a refrigerator and every precaution is taken to avoid possible contamination from plastics or rubber materials. Ensure that the standard solutions are not directly exposed to

47、 sunlight or ultraviolet light for prolonged periods of time. Examine analytical standards for impurities. When stored at -20 C, standard materials are generally stable for at least a year. To allow equilibration, it is recommended to allow the standards to come up to room temperature before the con

48、tainers are opened. Stock solutions of concentration 1 mg/ml, if kept in a freezer (at about -20 C), are usually stable for 6 months, but the influence of repeated uses has to be checked. Changes in volume due to solvent evaporation, for example through the space between a glass stopper and the neck

49、 of a flask, can be a source of error. Therefore, the use of polytetrafluoroethylene (PTFE) screw-cap flasks is recommended for the storage of stock and standard solutions. Experience has shown that errors introduced in the preparation, handling and storage of standards and standard solutions are major sources of inaccuracies. Experiences obtained by other national, European and international bodies should be observed 7, 8. 4.3 Safety aspects associated with reagents 4.3.1 General The analysis of pesticide residues in a food