1、BRITISH STANDARD BS EN ISO 16588:2003 BS6068-2.82:2003 Water quality Determination of six complexing agents Gas-chromatographic method ICS 13.060.50 +A1:2005National foreword This British Standard is the UK implementation of EN ISO 16588:2003+A1:2005. It is identical with ISO 16588:2002, incorporati
2、ng amendment 1:2004. It supersedes BS EN ISO 16588:2003, which is withdrawn. The UK participation in its preparation was entrusted by Technical Committee EH/3, Water quality, to Subcommittee EH/3/2, Physical, chemical and biochemical methods. A list of organizations represented on this subcommittee
3、can be obtained on request to its secretary. This is one of a series of standards on water quality, others of which have been, or will be, 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 Introd
4、uction Part 1 Glossary Part 2 Physical, chemical and biochemical methods Part 3 Radiological methods Part 4 Microbiological methods Part 5 Biological methods Part 6 Sampling Part 7 Precision and accuracy NOTE The tests described in this British Standard should only be carried out by suitably qualifi
5、ed persons with an appropriate level of chemical expertise. Standard chemical procedures should be followed throughout. This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance with a British Standard canno
6、t confer immunity from legal obligations. BS EN ISO 16588:2003+A1:2005 This British Standard was published under the authority of the Standards Policy and Strategy Committee on 23 January 2003 BSI 2009 Amendments/corrigenda issued since publication Amd. No. Date Comments 14910 23 January 2004 Implem
7、entation of the European Standard 31 October 2009 Implementation of ISO amendment 1:2004 with CEN endorsement A1:2005. Addition of Clause 10 and Annex B. ISBN 978 0 580 69331 1EUROPEANSTANDARD NORMEEUROPENNE EUROPISCHENORM ENISO16588: 2003+A1 June 2005 ICS13.060.50 Englishversion WaterqualityDetermi
8、nationofsixcomplexingagentsGas chromatographicmethod(ISO16588:2002) QualitdeleauDosagedesagentscomplexants Mthodeparchromatographieenphasegazeuse(ISO 16588:2002) WasserbeschaffenheitBestimmungvonsechs KomplexbildnernGaschromatographischesVerfahren (ISO16588:2002) ThisEuropeanStandardwasapprovedbyCEN
9、on3November2003. CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhichstipulatetheconditionsforgivingthisEuropean Standardthestatusofanationalstandardwithoutanyalteration.Uptodatelistsandbibliographicalreferencesconcerningsuchnational standardsmaybeobtainedonapplicationtotheManagement
10、CentreortoanyCENmember. ThisEuropeanStandardexistsinthreeofficialversions(English,French,German).Aversioninanyotherlanguagemadebytranslation undertheresponsibilityofaCENmemberintoitsownlanguageandnotifiedtotheManagementCentrehasthesamestatusastheofficial versions. CENmembersarethenationalstandardsbo
11、diesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Hungary,Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Slovakia,Spain,Sweden,SwitzerlandandUnited Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMU
12、NG ManagementCentre:ruedeStassart,36B1050Brussels 2003CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.ENISO16588:2003E2 Foreword ThetextofISO16588:2002hasbeenpreparedbyTechnicalCommitteeISO/TC147“Water quality”oftheInternationalOrganizationforStandard
13、ization(ISO)andhasbeentakenoveras ENISO16588:2003byTechnicalCommitteeCEN/TC230“Wateranalysis“,thesecretariatof whichisheldbyDIN. ThisEuropeanStandardshallbegiventhestatusofanationalstandard,eitherbypublicationof anidenticaltextorbyendorsement,atthelatestbyMay2004,andconflictingnationalstandards shal
14、lbewithdrawnatthelatestbyMay2004. AccordingtotheCEN/CENELECInternalRegulations,thenationalstandardsorganizationsof thefollowingcountriesareboundtoimplementthisEuropeanStandard:Austria,Belgium,Czech Republic,Denmark,Finland,France,Germany,Greece,Hungary,Iceland,Ireland,Italy, Luxembourg,Malta,Netherl
15、ands,Norway,Portugal,Slovakia,Spain,Sweden,Switzerlandand theUnitedKingdom. Endorsementnotice ThetextofISO16588:2002hasbeenapprovedbyCENasENISO16588:2003withoutany modifications. NOTENormativereferencestoInternationalStandardsarelistedinAnnexZA(normative). ENISO16588:2003+A1:2005 Foreword toamendmen
16、tA1 The text of this Amendment ISO 16588:2002/Amd1:2004 to the EN ISO 16588:2003/A1:2005 from Technical Committee ISO/TC 147 “Water quality“ of the International Organization for Standardization (ISO) has been taken over as a European Standard by Technical Committee CEN/TC 230 “Water analysis“, the
17、secretariat of which is held by DIN. This Amendment to the European Standard EN ISO 16588:2003/A1:2005 shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by December 2005, and conflicting national standards shall be withdrawn
18、 at the latest by December 2005. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Ic
19、eland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. BS EN ISO 16588:2003+A1:2005Contents Page 1 Scope . 1 2 Normativereferences . 1 3 Principle 2 4 Interferences. 2 5 Reagents 2 6 Appar
20、atus . 4 7 Samplingandsamplestabilization . 4 8 Procedure. 5 9 7 9 12 9 Annex A 10 13 EN ISO 16588:2003+A1:2005 BS EN ISO 16588:2003+A1:2005 ii Resultsofaninterlaboratorytrial 12 B 11 9 10Precision Calibration . Expressionofresults Te s t r e p o r t . . . . . . . . . . . . . . . . . . . . . . . . .
21、 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Examplesofcolumns,chromatogramsandmassspectra
22、. Bibliography This page deliberately left blankISO85612002:8)E( v Introduction ItisessentialthatthetestdescribedinthisInternationalStandardbecarriedoutbysuitablyqualifiedstaff. Itshouldbeinvestigatedwhetherandtowhatextentparticularproblemswillrequirethespecificationofadditional conditions. EN ISO 1
23、6588:2003+A1:2005 i BS EN ISO 16588:2003+A1:2005ANRETNIITOTSLANDNADRA ISO85612002:8)E( ISO2002rllAithgsreservde 1 WaterqualityDeterminationofsixcomplexingagents Gaschromatographicmethod WARNINGPersonsusingthisInternationalStandardshouldbefamiliarwithnormallaboratorypractice. Thisstandarddoesnotpurpo
24、rttoaddressallofthesafetyproblems,ifany,associatedwithitsuse.Itisthe responsibilityoftheusertoestablishappropriatesafetyandhealthpracticesandtoensurecompliancewith anynationalregulatoryconditions. 1 Scope ThisInternationalStandardspecifiesamethodforthedeterminationofthewatersolubleorganiccomplexinga
25、gents listedinTable1intheconcentrationrangefrom to ,ifasamplevolumebetween and is used.Theconcentrationrangemaychangeifdilutedsolutionsareanalysed.Themethodisapplicabletodrinking, ground,surfaceandwastewater. Inwastewateranalysis,itisrecommendedthatasmallersamplevolume,e.g. or ,beusedinorderto reduc
26、ematrixeffects. Theadsorptionofthesixcomplexingagentsonsolidmaterialsisnegligiblylow. Othercomplexingagentsofsimilarcompositionmayalsobedeterminedusingthismethod,providedtheybehave similarly during sample pretreatment, derivatization and gas chromatography. This shall be checked in each individualca
27、se. 2 Normativereferences Thefollowingnormativedocumentscontainprovisionswhich,throughreferenceinthistext,constituteprovisionsof this International Standard. For dated references, subsequent amendments to, or revisions of, any of these publicationsdonotapply.However,partiestoagreementsbasedonthisInt
28、ernationalStandardareencouragedto investigate the possibility ofapplyingthe most recent editions of the normative documentsindicated below. For undated references, the latest edition of the normative document referred to applies. Members of ISO and IEC maintainregistersofcurrentlyvalidInternationalS
29、tandards. ISO3696:1987,WaterforanalyticallaboratoryuseSpecificationandtestmethods ISO56671:1980,WaterqualitySamplingPart1:Guidanceonthedesignofsamplingprogrammes ISO56672:1991,WaterqualitySamplingPart2:Guidanceonsamplingtechniques Table1Complexingagentsdeterminablebythismethod No. Name Composition M
30、olecularmass CASnumber a 1 EDTAethylenedinitrilotetraaceticacid C 10 H 16 O 8 N 2 292,25 60004 2 NTAnitrilotriaceticacid C 6 H 9 O 6 N 191,14 139139 3 DTPAdiethylenetrinitrilopentaaceticacid C 14 H 23 O 10 N 3 393,35 67436 4 MGDAmethylglycinediaceticacid C 7 H 11 O 6 N 205,17 29578050 5 ADA alanined
31、iaceticacid C 7 H 11 O 6 N 205,17 6245756 6 1,3PDTA1,3propylenedinitrilotetraaceticacid C 11 H 18 O 8 N 2 306,27 1939362 a CAS:ChemicalAbstractsSystem 0,5 g/l 200 g/l 50ml 100ml 5ml 10ml ENISO16588:2003+A1:2005 BS EN ISO 16588:2003+A1:2005ISO:88561(2002)E 2 ISO2002Arllithgrseresvde 3 Principle Atest
32、sampleisstabilizedwithformaldehydeandevaporatedtodryness.Hydrochloricorformicacidisaddedand thesampleagainevaporatedtodryness.Thecomplexingagentsarethenesterifiedtothenpropyl,isopropylor nbutyl esters. Water is added and the esters are extracted with nhexane, separated and identified by gas chromato
33、graphy,anddeterminedquantitativelywithanitrogensensitivedetectororbymassspectrometry. ForthedeterminationofEDTA,DTPA,and1,3PDTA,1,2propylenedinitrotetraaceticacid(1,2PDTA)isusedasan internalstandardthroughthewholeprocedure.Whenanitrogensensitivedetectorisused,heptadecaneand/or octadecanenitrileisuse
34、dasacontrolstandardinthegaschromatographicstep.1Chorotetradecanemaybeused asthecontrolstandardifdetectionbymassspectrometryischosen. Alternatively, 13 Clabelledstandardsmaybeused. 4 Interferences Inspiteoftheir stability,complexesofthesecomplexingagentswithheavymetalsarebrokenupandthecomplexing agen
35、tsdetermined,exceptinthecaseofbismuth.Withsamplescontainingbismuthinconcentrations , lossescanbeexpected. In the case of high salt concentrations ( of NaCl, corresponding to an electrical conductivity of about ),completeevaporationtodrynessmaybedifficult.Thecompleteremovalofwaterisnecessary,however,
36、 forthesubsequentesterification.Therefore,sampleshavetobedilutedorsmallersamplevolumeshavetobetaken. Inthepresenceofcalciumionsinconcentrationsexceeding ofCa 2+ ,lossesofEDTAwilloccur. 5 Reagents Allreagentsshallbefreefromimpuritieswhichcouldinterferewiththereactions.Throughouttheprocedure,useonly d
37、eionizedwater(5.1). 5.1 Deionizedwater ,grade1asspecifiedinISO3696. 5.2 Gasesforgaschromatographyandmassspectrometry ,asspecifiedbytheinstrumentmanufacturers. 5.3 Nitrogen,ofpurity . 5.4 nPropanol orisopropanol ornbutanol forthepreparationofesterificationreagent(5.6). 5.5 Acetylchloride . 5.6 Esteri
38、ficationreagent . Cautiouslymixbyswirlingina beaker ofnpropanolorisopropanolor nbutanol(5.4)with of acetylchloride(5.5). CAUTIONConsiderableheatisevolved. Themixtureisstableforatleast1monthifstoredatroomtemperature. 5.7 Referencecompounds . 5.7.1 Nitrilotriaceticacid(NTA) ,C 6 H 9 O 6 N,ofpurity . 5
39、.7.2 Ethylenedinitrilotetraaceticacid(EDTA) ,C 10 H 16 O 8 N 2 ,ofpurity . 5.7.3 Diethylenetrinitrilopentaaceticacid(DTPA) ,C 14 H 23 O 10 N 3 ,ofpurity . 100 g/l 2g/l 400mS/m 200mg/l 99,996% 400ml 90ml 10ml 99% 99% 99% EN ISO 16588:2003+A1:2005 BS EN ISO 16588:2003+A1:2005ISO85612002:8)E( ISO2002rl
40、lAithgsreservde 3 5.7.4 Methylglycinediaceticacid(MGDA) ,C 7 H 11 O 6 N. 5.7.5 Alaninediaceticacid( ADA) ,C 7 H 11 O 6 N. 5.7.6 1,3Propylenedinitrilotetraaceticacid(1,3PDTA) ,C 11 H 18 O 8 N 2 ,ofpurity . 5.7.7 13 Clabelledreferencecompounds aslistedin5.7.1to5.7.6(optional). 5.8 Controlstandardsandi
41、nternalstandard . 5.8.1 Octadecanenitrile ,C 18 H 35 N,ofpurity . 5.8.2 Heptadecanenitrile ,C 17 H 33 N,ofpurity . 5.8.3 1Chlorotetradecane ,C 14 H 29 Cl,ofpurity . 5.8.4 1,2Propylenedinitrilotetraaceticacid(1,2PDTA) ,C 11 H 18 O 8 N 2 ,ofpurity . 5.9 Formaldehyde, byvolumeaqueoussolution. 5.10 nHex
42、ane . 5.11 Sodiumsulfate ,anhydrous. 5.12 Sodiumhydroxidesolution , . 5.13 Hydrochloricacid , . 5.14 Hydrochloricacid , . 5.15 Formicacid , byvolumeaqueoussolution. 5.16 Stocksolutionsforcalibrationpurposes , . Prepare stocksolutionsasfollows.Weigh ofeachofthecomplexingagents5.7.1to5.7.6and 5.8.4int
43、o volumetricflasks,dissolvein ofsodiumhydroxidesolution(5.12)andmakeuptothemarkwithwater (5.1). Storedinarefrigeratorinbrownglassbottles,thestocksolutionsarestableforatleast3months. 5.17 Intermediatestocksolutions , and . Priortoeachseriesofanalyses,prepareintermediatestocksolutionsof and bydiluting
44、the stock solutions(5.16)withwater(5.1). 5.18 Nitrilecontrolstandard , solutioninhexane. Dissolve ofoctadecanenitrile(5.8.1)and/orheptadecanenitrile( 5.8.2)in ofnhexane(5.10). Storethesolutioninarefrigeratorat . Thesolutionisstableforatleast3months. Beforeuse,dilutethissolutionto . 5.19 1Chlorotetradecanecontrolstandard , solutioninhexane. Dissolve of1chlorotetradecane(5.8.3)in ofnhexane(5.10). 99% 98% 98%
