1、PUBLISHED DOCUMENT PD CEN/TR 14823:2003 Durability of wood and wood-based products Quantitative determination of pentachlorophenol in wood Gas chromatographic method ICS 71.100.50; 79.040 PD CEN/TR 14823:2003 This Published Document was published under the authority of the Standards Policy and Strat
2、egy Committee on 6 November 2003 BSI 6 November 2003 ISBN 0 580 42885 0 National foreword This Published Document is the official English language version of CEN/TR 14823:2003. The UK participation in its preparation was entrusted by Technical Committee B/515, Wood preservation, to Subcommittee B/51
3、5/2, Specifications and chemical testing of wood preservatives, which has the responsibility to: A list of organizations represented on this subcommittee can be obtained on request to its secretary. Cross-references The British Standards which implement international or European publications referre
4、d 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. aid enquirers to understand the text; present to the responsible Europe
5、an 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 inside front cover, the CEN/TR title page,
6、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 CommentsTECHNICALREPORT RAPPORTTECHNIQUE TECHNISCHERBERICHT CEN/TR14823 September2003 ICS71.100.50;79.040 Englishversion
7、DurabilityofwoodandwoodbasedproductsQuantitative determinationofpentachlorophenolinwoodGas chromatographicmethod Durabilitduboisetdesmatriauxdrivsdubois Analysequantitativedupentachlorophnoldanslebois Mthodeparchromatographieenphasegazeuse DauerhaftigkeitvonHolzundHolzproduktenQuantitative Bestimmun
8、gvonPentachlorphenolinHolz GaschromatographischeVerfahren ThisTechnicalReportwasapprovedbyCENon27July2003.IthasbeendrawnupbytheTechnicalCommitteeCEN/TC38. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Hungary,Iceland,Ireland,Italy,Luxem
9、bourg,Malta,Netherlands,Norway,Portugal,Slovakia,Spain,Sweden,SwitzerlandandUn ited Kingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2003CEN Allrightsofexploitationinanyformandbyanymeansreserved worldw
10、ideforCENnationalMembers. Ref.No.CEN/TR14823:2003ECEN/TR14823:2003(E) 2 Contents Page Foreword3 Introduction .4 1 Scope 5 2 References5 3 Safetyprecautions .5 4 Principle5 5 Reagents.5 6 Apparatus .6 7 Preparationofthetestsample .7 8 Procedure .7 8.1General .7 8.2Standardsolutions . 7 8.3Preparation
11、ofthecalibrationsolutions. 8 8.4Determination 8 9 Calculationandexpressionofresults. 10 10 Qualityassurance 11 11 Precision.11 12 Testreport 11 AnnexARingtestresults 12 Bibliography 13CEN/TR14823:2003(E) 3 Foreword Thisdocument(CEN/TR14823:2003)hasbeenpreparedbyTechnicalCommitteeCEN/TC38“Durabilityo
12、fwood andwoodbasedproducts”,thesecretariatofwhichisheldbyAFNOR. ThisstatusofthisdocumentasTechnicalReporthasbeenchosenbecausethismethoddescribedisanexample ofalaboratorymethodvalidatedbyaringtest.Itisrecognizedthat,forexample,differenttechniquesofextraction mightbeemployedbytheanalystwithoutlossofan
13、alyticalperformanceandquality.However,whenusingdifferent techniquesthecomparabilitytothemethoddescribedinthisTechnicalReportshouldbedemonstrated,e.g.by usingacertifiedreferencematerial(CRM).CEN/TR14823:2003(E) 4 Introduction Atpresent,nostandardisedmethodfortheanalysisofpentachlorophenol(PCP)inwoodi
14、srecognizedinEurope. Onlyafewnationalstandardsareavailableworldwide,egBS5666,Part6andAWPAStandardA5andthese methodsaredesignedfortheanalysisoftimbertreatedwithlevelsofPCPthatarenecessarytoprevent degradationofthetreatedtimberbyfungi. ThisTechnicalReporthasbeenissuedinordertofacilitatetheanalysisofPC
15、Ptreatedwoodandpanelsandin particularlowlevelsofPCPthatcanbepresentinpackagingtimbersandpallets.LowlevelsofPCPandother chlorophenols,andtheanisolesderivedfromthem,cancausetaintsinfoodstuffs.PCPcanbepresentasresidues fromoldantisapstaintreatmentorsometimbertreatedagainstdecaycouldinadvertentlyhavebee
16、nincorporated intothepanelproduct.CEN/TR14823:2003(E) 5 1Scope ThisTechnicalReportspecifiesalaboratorymethodofdeterminingthepentachlorophenolcontentofwood.The methodisapplicabletoalltypesofPCPtreatedwoodandwoodbasedmaterialsaswellasfortheanalysisof wastetimberwithrespecttoitsPCPcontent. Themethodhas
17、aquantificationlimitcorrespondingto100gPCPperkilogramofwoodmaterialexpressedasdry matter.ThemethoddescribedhasameasurementrangeuptoPCPcontentsof25mg/kgofdrymatter.These figuresrefertothegivenexample(whereanaliquotof1mloftheextractisusedforacetylation,see8.4). NOTE1 Iflowerquantificationlimitsarerequ
18、ired,ahighervolumeofextractaliquotcanbeusedforderivatisation. NOTE2 Thismethodcouldhavesomemodificationswithsomewoodspeciesashardwoods. 2References EN212, WoodpreservativesGeneralguidanceonsamplingandpreparationforanalysisofwoodpreservatives andtreatedtimber. EN322, WoodbasedpanelsDeterminationofmoi
19、sturecontent. ENISO3696, WaterforanalyticallaboratoryuseSpecificationandtestmethods(ISO3696:1987). ISO57252, Accuracy(truenessandprecision)ofmeasurementmethodsandresultsPart2:Basicmethodforthe determinationofrepeatabilityandreproducibilityofastandardmeasurementmethod . ISO11465, SoilqualityDetermina
20、tionofdrymatterandwatercontentonamassbasisGravimetricmethod . 3Safety precautions Personsusingthismethodshouldbefamiliarwithnormalanalyticallaboratoryproceduresandpractice. Thismethoddoesnotpurporttoaddressallthesafetyproblems,ifany,associatedwithitsuse. Itistheresponsibilityoftheusertoestablishsafe
21、tyandhealthpracticesandtoensurecompliancewithany Europeanornationalregulatoryconditions. 4Principle Pentachlorophenolisextractedfromthewoodmaterialusingmethanol.Theextractedpentachlorophenolis transformedtopentachlorophenolacetatebyderivatisationofanaliquotoftheextractinaqueouspotassium carbonatesol
22、utionwithaceticanhydride.Theacetatederivativeformedisextractedfromthisaqueoussolutionwith nhexaneandanalysedbygaschromatographywithelectroncapturedetection. 5Reagents Duringtheanalysis,unlessotherwisespecified,useonlyreagentsofrecognizedanalyticalgradewhichhavebeen checkedinadvanceastonotinterferewi
23、ththeanalyticalresults,andwatercomplyingwithgrade3asdefinedin ENISO3696. 5.1 Aceticanhydride (C 4 H 6 O 3 ).CEN/TR14823:2003(E) 6 5.2 Methanol (CH 3 OH). NOTE Othersolventscanbeusedinsteadofmethanol,someextractiondifficultiescanoccurwithsomewoodspecies (e.g.hardwoods).Itisrecommendedtocrosscheckthee
24、xtractionefficiencyofanyothersolventorsolventmixturewiththat of methanol. 5.3 nHexane (C 6 H 14 ). 5.4 Potassiumcarbonate ,solution, c(KCO 3 )=0,1mol/l. 5.5 Sodiumsulfate ,anhydrous(Na 2 SO 4 ). 5.6 Pentachlorophenol (PCP,(C 6 Cl 5 OH)ofcertifiedpurity(99%),e.g.IPO560 1) . 5.7 2,4,6tribromophenol (T
25、BP,(C 6 H 2 Br 3 OH)ofcertifiedpurity(98%)asaninternalstandard. 5.8 Purifiedsand ,(ignitedat900Cafteracidtreatment) NOTE Anuntreatedwoodsample(ofthesamewoodspeciesasthesampleforanalysis)knowntobefreeof pentachlorophenolcanalsobeusedinsteadofpurifiedsandbutbeforeuseitshouldbecheckedforinterferencewit
26、hthe analyticalmethod. 6Apparatus Ordinarylaboratoryapparatusandthefollowing. NOTE Glasswareshouldbethoroughlycleanedpriortouse. 6.1 Analyticalbalance ,accurateto0,01mg. 6.2 Ultrasonicbath equippedwithathermostatcapableofcontrollingandmaintainingatemperatureof40C. 6.3 DisposablePasteurpipettes madeo
27、fglass,2,0mlcapacity. 6.4 Separatingfunnel ,150mlcapacity. 6.5 Volumetricpipettes ,1,0mland10mlor20mlcapacity. 6.6 Microlitresyringes ,25l,100land500lcapacity. 6.7 Volumetricflasks ,10ml,25mland50mlcapacity. 6.8 Conicalflasks 100mlcapacity,withscrewcapsprovidedwithaninsertofpolytetrafluoroethylene(P
28、TFE)or alternativelywithstandardgroundstoppersprovidedwithPTFEstandardgroundsocketsandconicaljointclips. 6.9 Gaschromatograph equippedwithasplitless/splitoranondiscriminatinginjectionsystemandanelectron capturedetector(ECD) 6.10 Separationcolumn .Onecapillarycolumn,orpreferablytwo,withstationaryphas
29、eofdifferentpolaritye.g. DB1,DB5,DB17 2) ;length:25mto30m;internaldiameter:0,2mmto0,32mm;filmthickness:0,25mto0,33 m. 1) IPO560isanexampleofasuitableproductavailablecommercially,suppliedbyPromochem.Thisinformationisgivenfor theconvenienceofusersofthisCENTechnicalReportanddoesnotconstituteandendorsem
30、entbyCENofthisproduct.CEN/TR14823:2003(E) 7 6.11 Precolumn coatedwithdeactivatedsilica. 7 Preparationofthetestsample Collectatleast10gofthesamplematerialtakenaccordingtoe.g.EN212.Thissamplematerialispreferably groundundermildconditions(e.g.cryogenicgrinding)tochipswithanapproximateparticlesizeof0,5m
31、mto1,0 mmdiameter. NOTE 1 Woodshavingscanalsobemadeforanalysis(especiallyifothercompoundse.g.trichlorophenolsor trichloroanisolshavetobeanalysedatthesametime). Homogenisethegroundsamplematerialtoobtainarepresentativesample,andstoreitinabrownglassvessel withscrewcapswithaPTFEinsert.Thisisthetestsampl
32、e. NOTE2 Ifpossible,thesampleforanalysisshouldbepreparedfromaminimumoffiveindependentpiecesorsections representativelytakenfromthequantityofwoodmaterialtobeanalysed. 8Procedure 8.1General Itisrecommendedtocarryoutatleasttwoparallelanalyses.Ifresultsdifferbymorethan10%anadditional analysisshallbecarr
33、iedout. 8.2Standardsolutions 8.2.1Preparationofstocksolutions(calibrantandinternalstandard) Preparethestocksolutionsbyweighingabout12,5mgofPCP(5.6)andTBP(5.7)separatelytothenearestof 0,01mganddissolveeachin25mlmethanol(5.2). NOTE Thesestocksolutionswithnominalconcentrationsof0,5mg/mlcanbestoredinthe
34、darkat18Cforthree months. 8.2.2Preparationofworkingsolutions Transferbypipette(6.5)1,00mlofstockPCPsolution(8.2.1)toa10mlonemarkvolumetricflaskandmakeupto themarkwithmethanol(5.2)togiveasolutionhavinganominalconcentrationof50g/mlPCP.Repeatwiththe TBPstocksolutiontogiveasolutionhavinganominalconcentr
35、ationof50g/mlTBP. 8.2.3Preparationofcalibrationstandards Toaseriesoffiveconicalflasks(6.8)containing(5,00,1)gofpurifiedsand(5.8),transfer25l,50l,100l, 250land500lofPCPworkingsolution(8.2.2).Toeachofthefiveflasksandanotherflaskcontainingsandbut noaddedPCP,add250lofTBPworkingsolution(8.2.2)togiveaseri
36、esofstandardscontaining0,0g,1,25g, 2,5g,5g,12,5gand25gofPCPwith12,5gTBPasinternalstandardineach. NOTE Thisprocedureassumesthat1mlofthemethanolextractwillbetakenforpreparationofthecalibrationsolutions.If a greatervolumeofextractistobetaken,forexample5ml,theabovestandardsshouldbepreparedfromworkingsol
37、utionseach withanominalconcentrationof10g/ml. 2) DB1,DB5,DB17areexamplesofasuitableproductavailablecommercially,suppliedbyJ&W.Thisinformationisgivenfor theconvenienceofusersofthisCENTechnicalReportanddoesnotconstituteanendorsementbyCENoftheseproducts.CEN/TR14823:2003(E) 8 8.3Preparationofthecalibrat
38、ionsolutions 8.3.1Extraction Toeachflaskadd50mlofmethanolandswirltoensurethatallthewoodiswetted.Toquantifypossible evaporationlossesofthesolventduringtheextractionproceduredeterminethegrossmassesofallflasks(dryand cleanoutside)atambienttemperaturebeforeandaftersonication.Placetheflasksinanultrasonic
39、bathfor1hat 40C.Performallthefollowingstepsundergravimetriccontrolusingananalyticalbalance.Afterweighing,allow thewoodtosettleand,bymeansofaseries(oneperflask)of10mlor20mlvolumetricpipettes(6.5)and/or Pasteurpipettes(6.3),transferasmuchaspossibleoftheclearsupernatantsolutiontoaseriesof50mlonemark vo
40、lumetricflasks(6.7).Makethecontentsofeachflaskuptothemarkwithmethanol. Table1Exampleofcalibrationsolutions Calibrationsolution PCPconcentration(ng/ml) TBPconcentration(ng/ml) 1 1,0 10,0 2 2,0 10,0 3 4,0 10,0 4 10,0 10,0 5 20,0 10,0 Themaximumstoragetimeofthesesolutionsisonemonthatapproximately5C,e.g
41、.inarefrigerator. NOTE Theconcentrationofthecalibrationsolutionsaswellasthevolumeofthealiquotofthemethanolicextracttaken foracetylationcanbevariedtocovertheexpectedlevelofPCPcontaminationofthewoodsampleuptoatleast100mg/kg. 8.3.2Acetylation Add301mlofthepotassiumcarbonatesolution(5.4)toaseriesofsixse
42、paratingfunnels(6.4).Usingapipette (6.5),transfer1mloftheextractsolution(8.3.1)toitsallottedseparatingfunnel,shaketomixthecontentsofthe separatingfunnelthoroughly.Toeachseparatingfunnel,add(2 0,2)mloftheaceticanhydride(5.1)andshake themixturefor2min.Extracttheacetylatedpentachlorophenolandtribromophenolwith10mlofthenhexane (5.3)byshakingthemixturefor10min.BymeansofacleanPasteurpipette,transfertheupper(organic)layerinto a25mlonemarkvolumetricflask(6.7)viafilter
