EN ISO 15913-2003 en Water quality - Determination of selected phenoxyalkanoic herbicides including bentazones and hydroxybenzonitriles by gas chromatography and mass spectrometry .pdf

1、BRITISH STANDARD BS EN ISO 15913:2003 Incorporating Amendment No. 1 to BS 6068-2.70:2000 (renumbers the BS as BS EN ISO 15913:2003) Water quality Determination of selected phenoxyalkanoic herbicides, including bentazones and hydroxybenzonitriles by gas chromatography and mass spectrometry after soli

2、d phase extraction and derivatization The European Standard EN ISO 15913:2003 has the status of a British Standard ICS 13.060.50 BS EN ISO 15913:2003 This British Standard, having been prepared under the direction of the Health and Environment Sector Committee, was published under the authority of t

3、he Standards Committee and comes into effect on 15 June 2000 BSI 18 June 2003 ISBN 0 580 34801 6 National foreword This British Standard is the official English language version of EN ISO 15913:2003. It is identical with ISO 15913:2000. The UK participation in its preparation was entrusted by Techni

4、cal Committee EH/3, Water quality, to subcommittee EH/3/2, Physical, chemical and biochemical methods, which has the responsibility to: A list of organizations represented on this subcommittee can be obtained on request to its secretary. This is one of a series of standards on water quality that hav

5、e been published as sections of BS 6068. The various sections of BS 6068 are comprised within Parts 1 to 7,which, together with Part 0, are listed below: Part 0 Introduction; Part 1 Glossary; Part 2 Physical, chemical and biochemical methods; Part 3 Radiological methods; Part 4 Microbiological metho

6、ds; Part 5 Biological methods; Part 6 Sampling; Part 7 Precision and accuracy. As and when the different sections of BS 6068 are amended or revised, they will be renumbered with the identifier of the corresponding international standard. For example, this standard has been renumbered from BS 6068-2.

7、70 to BS EN ISO 15913:2003. NOTE The test described in this British Standard should only be carried out by suitable qualified persons with the appropriate level of chemical expertise. Standard chemical procedures should be followed throughout. Cross-references The British Standards which implement i

8、nternational or European publications referred to in this document may be found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. This publication does not

9、purport to include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible international/European comm

10、ittee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments and promulgate them in the UK. Summary of pages This document comprises a front cover, an inside front cover, the EN ISO title page, the EN

11、ISO foreword page, the ISO title page, pages ii to iv, pages 1 to 22, the Annex ZA page and a back cover. The BSI copyright date displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. Date Comments 14422 18 June 2003 Renumbers BS 6068-2.7

12、0:2000 as BS EN ISO 15913:2003EUROPEANSTANDARD NORMEEUROPENNE EUROPISCHENORM ENISO15913 March2003 ICS13.060.50 Englishversion WaterqualityDeterminationofselectedphenoxyalkanoic herbicides,includingbentazonesandhydroxybenzonitrilesby gaschromatographyandmassspectrometryaftersolidphase extractionandde

13、rivatization(ISO15913:2000) QualitdeleauDosagedecertainsherbicides phnoxyalcanoques,ycomprisbentazoneset hydroxybenzonitriles,parchromatographieenphase gazeuseetspectromtriedemasseaprsextractionen phasesolideetdrivatisation(ISO15913:2000) WasserbeschaffenheitBestimmungausgewhlten Phenoxyalkancarbons

14、ureHerbiziden,einschlielich BentazonundHydroxybenzonitrilenmittels Gaschromatographieundmassenspektrometrischer DetektionnachFestFlssigExtraktionundDerivatisierung (ISO15913:2000) ThisEuropeanStandardwasapprovedbyCENon9January2003. CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhich

15、stipulatetheconditionsforgivingthisEurope an Standardthestatusofanationalstandardwithoutanyalteration.Uptodatelistsandbibliographicalreferencesconcernings uchnational standardsmaybeobtainedonapplicationtotheManagementCentreortoanyCENmember. ThisEuropeanStandardexistsinthreeofficialversions(English,F

16、rench,German).Aversioninanyotherlanguagemadebytra nslation undertheresponsibilityofaCENmemberintoitsownlanguageandnotifiedtotheManagementCentrehasthesamestatusasthe official versions. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Hungar

17、y,Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,SlovakRepublic,Spain,Sweden,Switzerland and UnitedKingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2003CEN Allrightsofexploitationin

18、anyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.ENISO15913:2003EForeword ThetextofISO15913:2000hasbeenpreparedbyTechnicalCommitteeISO/ TC147, Water quality,oftheInternationalOrganizationforStandardization(ISO)andhasbeentakenoveras ENISO15913:2003byTechnicalCommitteeCEN/TC230,Wate

19、ranalysis,theSecretariatof whichisheldbyDIN. ThisEuropeanStandardshallbegiventhestatusofanationalstandard,eitherbypublicationof anidenticaltextorbyendorsement,atthelatestbySeptember2003,andconflictingnational standardsshallbewithdrawnatthelatestbySeptember2003. AccordingtotheCEN/CENELECInternalRegul

20、ations,thenationalstandardsorganizationsof thefollowingcountriesareboundtoimplementthisEuropeanStandard:Austria,Belgium,Czech Republic,Denmark,Finland,France,Germany,Greece,Hungary,Iceland,Ireland,Italy, Luxembourg,Malta,Netherlands,Norway,Portugal,SlovakRepublic,Spain,Sweden, SwitzerlandandtheUnite

21、dKingdom. Endorsementnotice ThetextofISO15913:2000hasbeenapprovedbyCENasENISO15913:2003withoutany modifications. NOTENormativereferencestoInternationalStandardsarelistedinAnnexZA(normative). ENISO15913:2003Reference number ISO 15913:2000(E) INTERNATIONAL STANDARD ISO 15913 First edition 2000-04-01 W

22、ater quality Determination of selected phenoxyalkanoic herbicides, including bentazones and hydroxybenzonitriles by gas chromatography and mass spectrometry after solid phase extraction and derivatization Qualit de leau Dosage de certains herbicides phnoxyalcanoques, y compris bentazones et hydroxyb

23、enzonitriles, par chromatographie en phase gazeuse et spectromtrie de masse aprs extraction en phase solide et drivatisation ENISO15913:2003ii ENISO15913:2003iii Contents Page Foreword.iv 1 Scope 1 2 Normative references 2 3 Term, definition, abbreviations and subscripts2 4 Principle3 5 Interference

24、s 3 6 Reagents.3 7 Apparatus .6 8 Sampling.7 9 Procedure .7 10 Calculation14 11 Precision.15 12 Test report 15 Annex A (informative) Results of an interlaboratory trial .16 Annex B (informative) Further substances which may be analysed by this procedure17 Annex C (informative) Example of hydrolysis

25、of phenoxyalkanoic carbonic esters .18 Annex D (informative) Mass spectra for some phenoxyalkanoic herbicides.19 ENISO15913:2003iv Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing Inter

26、national Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison wit

27、h ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 3. Draft International Stand

28、ards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. Attention is drawn to the possibility that some of the elements of this International Standard may

29、 be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. International Standard ISO 15913 was prepared by Technical Committee ISO/TC 147, Water quality, Subcommittee SC 2, Physical, chemical and biochemical methods. Annexes A, B, C and D of t

30、his International Standard are for information only. ENISO15913:20031 Water quality Determination of selected phenoxyalkanoic herbicides, including bentazones and hydroxybenzonitriles by gas chromatography and mass spectrometry after solid phase extraction and derivatization WARNING Diazomethane is

31、explosive, extremely toxic and severely irritating, causing pulmonary oedema when inhaled in high concentrations. Long-term, low-level exposure may lead to sensibilization, resulting in asthma-like symptoms. Also, diazomethane and several of its chemical precursors have been cited as carcinogens. 1

32、Scope This International Standard specifies a method for the determination of phenoxyalkanoic acids in ground and drinking water in mass concentrationsW 50 ng/l (detailed information is given in Table A.1 of annex A). Examples of phenoxyalkanoic acids which can be determined by this method are given

33、 in Table 1. This method may be applicable to compounds not mentioned in Table 1 or to other types of water. However, it is necessary to verify the applicability of this method for these special cases (see annex B). Table 1 Plant treatment agents determined by this method Name Molecular formula Rela

34、tive molecular mass CAS registry No. (2,4-Dichlorophenoxy) acetic acid C 8 H 6 Cl 2 O 3 221,0 94-75-7 Mecoprop C 10 H 11 ClO 3 214,65 93-65-2 Dichlorprop C 9 H 8 Cl 2 O 3 235,06 120-36-5 MCPA C 9 H 9 ClO 3 200,6 94-74-6 MCPB C 11 H 13 ClO 3 228,67 94-81-5 (2,4,5-Trichlorophenoxy)acetic acid C 8 H 5

35、Cl 3 O 3 255,5 93-76-5 Bentazone C 10 H 12 N 2 O 3 S 240,3 25057-89-0 Bromoxynil C 7 H 3 Br 2 NO 276,9 1689-84-5 4-(2,4-Dichlorophenoxy)-butanoic acid C 10 H 10 Cl 2 O 3 249,1 94-82-6 Fenoprop C 9 H 7 Cl 3 O 3 269,51 93-72-1 ENISO15913:20032 2 Normative references The following normative documents c

36、ontain provisions which, through reference in this text, constitute provisions of this International Standard. For dated references, subsequent amendments to, or revisions of, any of these publications do not apply. However, parties to agreements based on this International Standard are encouraged t

37、o investigate the possibility of applying the most recent editions of the normative documents indicated below. For undated references, the latest edition of the normative document referred to applies. Members of ISO and IEC maintain registers of currently valid International Standards. ISO 5667-1:19

38、80, Water quality Sampling Part 1: Guidance on the design of sampling programmes. ISO 5667-2:1991, Water quality Sampling Part 2: Guidance on sampling techniques. ISO 5667-3:1994, Water quality Sampling Part 3: Guidance on the preservation and handling of samples. 3 Term, definition, abbreviations a

39、nd subscripts 3.1 Term and definition For the purposes of this International Standard, the following term and definition applies. 3.1.1 phenoxyalkanoic herbicides herbicides which undergo derivatization with diazomethane and which may subsequently be determined by gas chromatography EXAMPLE Typical

40、phenoxyalkanoic herbicides include alkylhalogenated phenoxy acids, hydroxybenzonitriles and bentazone. 3.2 Abbreviations 2,4-D (2,4-dichlorophenoxy) acetic acid 2,4-DB 4-(2,4-dichlorophenoxy) butanoic acid 2,4-DP dichlorprop MCPP mecoprop 2,4,5-T (2,4,5-trichlorophenoxy) acetic acid 2,4-TP fenoprop

41、3.3 Subscripts c calibration step using an external standard g overall procedure i identity of the substance i is internal standard j consecutive figure j for pairs of values sam sample sol solvent ENISO15913:20033 4P r i n c i p l e After acidification, substances are enriched on solid phase adsorb

42、ent material for example RP 1) -C18 material, eluted with solvent, methylated with diazomethane and then determined by gas chromatography using a mass spectrometric detector. In some cases, the substances may be present as their esters, for example octanoic esters. Hydrolysis of the water sample (se

43、e annex C) may lead to higher concentrations of the free acids. 5 Interferences 5.1 Occurrence Interferences may occur especially when examining other types of water, for example surface water. 5.2 Sampling To avoid interferences collect the sample as described in clause 8. 5.3 Enrichment The commer

44、cially available adsorbent materials are often of varying quality. Considerable batch-to-batch differences in quality and selectivity of this material are possible. The recovery may vary with the concentration. Therefore, check recovery regularly at different concentrations. Perform calibration and

45、analysis with material taken only from the same batch. Suspended matter in the water sample (such as iron hydroxide, calcium carbonate) occurring during sampling, storage and sample preparation, or an increase in the concentration of microorganisms may clog the packing. In this case, filter the wate

46、r sample through a glass fibre filter prior to enrichment. 5.4 Gas chromatography and mass spectrometry Use the operational conditions set in accordance with manufacturers instructions. Check these settings at regular intervals. General interferences, caused by the injection system or insufficient s

47、eparation can be eliminated with the help of special laboratory experience and the instruments manuals. 6 Reagents 6.1 General Use, as far as available, “for residual analysis“ reagents. Use only reagents and water with negligibly low impurities, i.e. resulting in clean blanks. 6.2 Operating gases f

48、or the gas chromatography/mass spectrometry, of high purity and in accordance with manufacturers specifications. 6.3 Nitrogen, of high purity, i.e. minimum 99,996 % by volume, for drying and eventually for concentration by evaporation. 6.4 Hydrochloric acid, c(HCl) = 2 mol/l. 6.5 Diethyl ether,C 4 H 10 O, stabilized. 1) RP = reversed phase ENISO15