1、BRITISH STANDARD BS EN 12260:2003 BS 6068-2.83:2003 Water quality Determination of nitrogen Determination of bound nitrogen (TN b ), following oxidation to nitrogen oxides The European Standard EN 12260:2003 has the status of a British Standard ICS 13.060.50 BS EN 12260:2003 This British Standard, w
2、as published under the authority of the Standards Policy and Strategy Committee on 25 September 2003 BSI 25 September 2003 ISBN 0 580 42692 0 National foreword This British Standard is the official English language version of EN 12260:2003. It supersedes DD ENV 12260:1996 which is withdrawn. The UK
3、participation in its preparation was entrusted by Technical 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. Cross-
4、references The British Standards which implement international 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 Br
5、itish Standards Online. 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 does not of itself confer immunity from legal obligations. aid enquirers to understand the text; pres
6、ent to the responsible international/European committee 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
7、inside front cover, the EN title page, pages 2 to 13 and a back cover. The BSI copyright notice displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. Date CommentsEUROPEANSTANDARD NORMEEUROPENNE EUROPISCHENORM EN12260 September2003 ICS13
8、060.50 SupersedesENV12260:1996 Englishversion WaterqualityDeterminationofnitrogenDeterminationof boundnitrogen(TN b ),followingoxidationtonitrogenoxides QualitdeleauDosagedelazoteDosagedelazoteli (TN b)aprsoxydationenoxydesdazote WasserbeschaffenheitBestimmungvonStickstoff BestimmungvongebundenemSt
9、i ckstoff(TN b)nach OxidationzuStickstoffoxiden ThisEuropeanStandardwasapprovedbyCENon1August2003. CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhichstipulatetheconditionsforgivingthisEurope an Standardthestatusofanationalstandardwithoutanyalteration.Uptodatelistsandbibliographical
10、referencesconcernings uchnational standardsmaybeobtainedonapplicationtotheManagementCentreortoanyCENmember. ThisEuropeanStandardexistsinthreeofficialversions(English,French,German).Aversioninanyotherlanguagemadebytra nslation undertheresponsibilityofaCENmemberintoitsownlanguageandnotifiedtotheManage
11、mentCentrehasthesamestatusasthe official versions. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Hungary,Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Slovakia,Spain,Sweden,SwitzerlandandUn ited Kingdom. EUROPEANCOM
12、MITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2003CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.EN12260:2003EEN12260:2003(E) 2 Contents page Foreword. 3 Introduction 4
13、 1 Scope . 5 2 Normativereferences . 5 3 Principle. 5 4 Interferences 5 5 Reagents 6 6 Apparatus 6 7 Samplingandsamplepreparation . . 7 8 Procedure 7 9 Establishmentofthecalibrationcurve . 7 10 Systemcheck . . 8 11 Calculation. 8 12 Expressionofresults . 8 13 Testreport . 9 14 Precisiondata. . 9 Ann
14、exA (informative) Determinationofboundnitrogenusingothertechniques 10 AnnexB (informative) Recoveryratesofsinglecompoundsusingoxidationand chemiluminescencedetection(seetableB.1) . 11 AnnexC (informative) Precisiondata. 12 Bibliography . 13EN12260:2003(E) 3 Foreword Thisdocument(EN12260:2003)hasbeen
15、preparedbyTechnicalCommitteeCEN/TC230“Wateranalysis”, thesecretariatofwhichisheldbyDIN. ThisEuropeanStandardshallbegiventhestatusofanationalstandard,eitherbypublicationofanidentical textorbyendorsement,atthelatestbyMarch2004,andconflictingnationalstandardsshallbewithdrawnat thelatestbyMarch2004. Thi
16、sdocumentsupersedesENV12260:1996 AnnexesAB,andCareinformativeannexes. AccordingtotheCEN/CENELECInternalRegulations,thenationalstandardsorganizationsofthefollowing countriesareboundtoimplementthisEuropeanStandard:Austria,Belgium,CzechRepublic,Denmark, Finland,France,Germany,Greece,Hungary,Iceland,Ire
17、land,Italy,Luxembourg,Malta,Netherlands, Norway,Portugal,Slovakia,Spain,Sweden,SwitzerlandandtheUnitedKingdom.EN12260:2003(E) 4 Introduction WARNINGPersonsusingthisstandardshouldbefamiliarwithnormallaboratorypractice.This standarddoesnotpurporttoaddressallofthesafetyproblems,ifany,associatedwithitsu
18、se.Itis theresponsibilityoftheusertoestablishappropriatesafetyandhealthpracticesandtoensure compliancewithanynationalregulatoryconditions. ItisabsolutelyessentialthattestscarriedoutaccordingtothisEuropeanStandardarecarriedoutbysuitably qualifiedstaff. ThisEuropeanStandardspecifiesamethodforthedeterm
19、inationoftotalboundnitrogenafteroxidationof inorganicandorganicnitrogencompoundsbycombustiontonitrogenoxides.Quantificationiscarriedoutby chemiluminescence. Theprocedurereferredtointhenormativepartisthereferencemethod.Whilststayingwithinthescopeofthis standard,itispermissibletousesuchalternativesasg
20、iveninannexAonly,providedthattheirperformanceis equaltoorbetterthanthatgiveninclause13andtablesinannexBandC,whencalculatedusingprocedures giveninISO57252,andwhenthecomparisonofperformancedatabetweenthisEuropeanStandardandany alternativetechniqueiscarriedoutusingtheproceduresdescribedinISO2854. Allre
21、ferencestonitrogenconcentrationsareexpressedinunitsofmg/lN,i.e.milligramsofnitrogenperlitre solution.EN12260:2003(E) 5 1Scope ThisEuropeanStandardspecifiesamethodforthedeterminationofnitrogeninwaterintheformoffree ammonia,ammonium,nitrite,nitrateandorganiccompoundscapableofconversiontonitrogenoxides
22、under theoxidativeconditionsdescribed.Determinationiscarriedoutinstrumentally.Dissolvednitrogengasisnot determinedbythismethod. Thismethodisapplicabletotheanalysisofsurfacewater,wastewaterandtreatedsewageeffluent. Theconcentrationrangeofthemethodwilldependontheinjectionvolumeusedwhichisinstrumentspe
23、cific. Totalnitrogencanbedeterminedintherangefrom1mg/lupto200mg/l.Higherconcentrationscan,if necessary,bedeterminedbydilutionofthesample.Thelimitofdetectionwilldependontheinstrumentin use.Usingasuitableinjectionvolume,thelimitofdetectionistypicallyroundabout0,5mg/l. 2 Normativereferences ThisEuropea
24、nStandardincorporatesbydatedorundatedreference,provisionsfromotherpublications. Thesenormativereferencesarecitedattheappropriateplacesinthetext,andthepublicationsarelisted hereafter.Fordatedreferences,subsequentamendmentstoorrevisionsofanyofthesepublicationsapplyto thisEuropeanStandardonlywhenincorp
25、oratedinitbyamendmentorrevision.Forundatedreferencesthe latesteditionofthepublicationreferredtoapplies(includingamendments). ENISO3696, WaterforanalyticallaboratoryuseSpecificationandtestmethods(ISO3696:1987) . ENISO56673, WaterqualitySamplingPart3:Guidanceonthepreservationandhandlingofsamples (ISO5
26、6673:1994) . ISO57252,Accuracy(truenessandprecision)ofmeasurementmethodsandresults Part 2:Basic methodsforthedeterminationofrepeatabilityandreproducibilityofastandardmeasurementmethod. ISO84661, WaterqualityCalibrationandevaluationofanalyticalmethodsandestimationofperformance characteristicsPart1:St
27、atisticalevaluationofthelinearcalibrationfunction . ISO84662,WaterqualityCalibrationandevaluationofanalyticalmethodsandestimationofperformance characteristicsPart2:Calibrationstrategyfornonlinearsecondordercalibrationfunction. 3Principle Oxidationofthesamplecontainingnitrogenbycatalyticcombustionina
28、noxygenatmosphereat700C,to nitrogenoxides.Quantificationofnitrogenconcentrationiscarriedoutbychemiluminescencedetection(after reactionwithozone). 4Interferences Dependingontheinstrumentinuse,interferencesmayarisefrommemoryeffects.Thesemayoccureither fromsamplesorstandardsolutionswithhighamountsofbou
29、ndnitrogen. NOTE Potentialproblemscanarisewithsamplescontainingsignificanttotalorganiccarbon(TOC)concentrations. TheanalysisofsamplescontaininglargeamountsofTOCwillleadtothereportingoflowerresultsfornitrogen.Suspected problemscanbeidentifiedbydeterminingnitrogenbeforeandaftersuitabledilution,orbyusi
30、ngstandardaddition techniques. Notallorganicnitrogencompoundsarequantitativelyconvertedtonitrogenoxidesbytheoxidationprocedure used(seerecoveryratesintableB.1).EN12260:2003(E) 6 Ifahomogenizedsamplecontainingsuspendedmaterialproducesresults(obtainedfromreplicate measurements)whichdeviatebymorethan10
31、thesampleneedstobefilteredthrougha0,45mfilter, freeofnitrogencontainingcompounds.Inthiscase,onlythedissolvedportionoftheboundnitrogenwillbe determinedandreported. 5Reagents 5.1General Usereagentsofrecognizedanalyticalgrade. 5.2Water DuringanalysisuseGrade3puritywaterasspecifiedinENISO3696.Theconte
32、ntsofbo undnitrogenin waterbeingusedforthepreparationofcalibrationsolutionsshallbenegligiblylowcomparedwiththelowest concentrationtobedetermined. 5.3Hydrochloricacid, (HCl)=1,12g/ml. 5.4Nitrogenstocksolutionforcalibration, (N)=1,000g/l. 5.4.1 Dissolve(4,717 0,001)gofammoniumsulfate,(NH 4 ) 2 SO 4 ,
33、previously dried at (1052)C to constantweight,ina1000mlvolumetricflask,andmakeuptovolumewithwater. 5.4.2 Dissolve(7,2190,001)gofpotassiumnitrate,KNO 3 ,previouslydriedat(1052)Ctoconstant weight,ina1000mlvolumetricflask,andmakeuptovolumewithwater. 5.4.3 Mixequalvolumesoftheabovesolutions(see5.4.1and5
34、4.2)toproduceamixedstandardsolution. Storedinarefrigeratorat(42)C,thestandardsolutioncanbeusedforaboutonemonth. 5.5Nicotinicacid, C 6 H 5 NO 2 ,99,5%. 5.6Nitrogenstocksolutionsforsystemcheck, (N)=1,000g/l. 5.6.1 Prepareseparatelystocksolutionscorrespondingto5.4.1and5.4.2. 5.6.2 Dissolve(8,7930,001)
35、gofnicotinicacid(5.5),previouslydriedat(1052)Ctoconstantmass, transfertoa1000mlvolumetricflaskandmakeuptovolumewithwater(5.2). Storeinarefrigeratorat(42)C,thestandardsolutioncanbeusedforaboutonemonth. 5.7Oxygen, O 2 ,withavolumefractionof99,7%. 6Apparatus 6.1Apparatussuitableforthedeterminationoftot
36、alboundnitrogenbyoxidation Thisapparatuswillbeinstrumentdependantandcomprisesforexamplereactionvessel,automaticsample injectiondevice,samplehomogenizingequipment,suitabledetectorsorsensorsandcomputingsystem.A manualinjectionsystemmayalsobeused.Forrequirementsforasuitablesystemseeclause10.EN12260:200
37、3(E) 7 6.2Homogenizer 6.3Filtrationapparatus, withmembranefilters(porewidth0,45m). 6.4Syringes 7 Samplingandsamplepreparation Whensampling,ensurethatarepresentativesampleisobtained(thisisparticularlyimportantforsamples containinganyundissolvedmatter),andthatthesampleisnotcontaminated.Inaddition,seeE
38、NISO56673. Withdrawsamplesinsuitablecontainersconsistingofglassorsuitableplastics,appropriatelysealed. Analyzesamplesassoonaspossible. NOTE Delaymayresultinthereportingoflowvalues(especiallyinthecaseofbiologicallyactivesamples). Samplesmaybestabilizedbytheadditionofhydrochloricacid(5.3)toachieveapHv
39、alueoflessthan2,and storedinarefrigeratorat(4 2) C.Stabilisedsamplesmaybestoredforaperiodofupto8 days. Alternativelystoresmallersamplevolumes(e.g.50mlto100ml)at15Cto20Cupto14days. Ifnecessary,homogenizethesampleinordertoobtainarepresentativealiquotforthedetermination(see clause4).Ifthisisimpracticab
40、le,filterthrougha0,45mfilter(6.3). 8Procedure Followtheinstrumentmanufacturersinstructions. Priortothedeterminationofboundnitrogen,ensurethatinstrumentoperationaltestsandtheverificationof theresponsestoblankandstandardsolutionsarecarriedoutwithintheintervalsspecifiedbythe manufacturer. Adjusttheinst
41、rumentaccordingtothemanufacturersinstructionsforeachseriesofmeasurements. Ifaninstrumentisfittedwithanautomatedinjectionsystem,ensurethatthesampleisunlikelytocauseany interferencewiththeinjectionprocedureby,forexample,homogenizingthesample(seealsoclause4). Injectidenticalvolumesofblanksolutionsandsa
42、mplesintotheinstrumentaccordingtothemanufacturers instructionsandmeasuretheresponsesobtainedforaliquotsofeachsolutionatleastthreetimes. Rejectthefirstandusethemeanresponsefromatleasttwoinjectionstakingintoaccountanymemoryeffects likelytooccur(seeclause4).Usethecalibrationgraph(seeclause9)todetermine
43、theconcentrationoftotal boundnitrogeninthesample. 9 Establishmentofthecalibrationcurve Usethemixedstandardsolution(5.4.3)topreparecalibrationsolutionsinaccordancewiththerangeof concentrationsoftotalboundnitrogenexpectedinthesamplestobedetermined. Usethecalibrationsolutionsonthedayofpreparationonly.Calibratewithinonedecadeofconcentration.For theconcentrationrangeof10mg/lto100mg/l,proceed,forexample,asfollows: Into7separatevolumetric100mlflasks,pipette0,(blank)1,0ml;2,0ml;3,0ml;6,0ml;8,0m
