EPA-600-4-79-020-1983.pdf

United States Environmental Protection Agency OffIce of Research and Development Washmgton, DC 20460 EPAl600f4-79f020 March1983 u Manual User Date_ Last NameFIrstMIddle Imtial ZIp CodeStateCIty Address to Send Future-O;:S:“:'“tr-e-et-:- RevislOns and AdditlOns IfaddressISan employeroraffiltate (fill m) EmployerorAffiltate Name I have receIved a copyofMethods for ChemIcal AnalysIsofWater and Wastes,1979Please send me anyreVISIonsand new addItions tothISManual as theybecomeavatlable US.EnvIronmentalProtectionAgency EnvIronmental MOnItormgandSupportLaboratory 26 WSt.ClairStreet Cincmnati,OH45268 ATTN:DistributionRecordSystem Place Stamp Here EPA-600j4-79-020 METHODS FOR CHEMICAL ANALYSIS OFWATERAND WASTES March1983 SecondPnntmgJune1982 ENVIRONMENTALMONITORINGANDSUPPORT LABORATORY OFFICEOFRESEARCHANDDEVELOPMENT U SENVIRONMENTALPROTECTIONAGENCY CINCINNATI,OHIO45268 Prmted on Recycled Paper _ DISCLAIMER Thementionoftrade namesorcommercIal products m thIs manualISfor IllustratIOn purposes, and doesnotconstItute endorsementorrecommendatIon for usebytheU SEnVironmental Protection Agency 11 FOREWORD thaccomplishmentofour objective m protectmg the enVIronment reqUIres a relIable assessmentof the present condition and a determmatlonofthe effectivenessofcorrective measures DecIsions which must be made on the need for pollutIOn abatement and the most efficient meansofachlevmg environmental quahty depend upon the avatlabilltyofsound data Test procedures for measurement ofthe presence and concentrationofsubstances hazardous to human health as well as an evaluation ofthe qualItyofthe environmentare essentialto satisfactorydeclSlon-makmg This manualofchemical methods was prepared by the staffofthe Environmental Momtonng and Support Laboratoryofthe Environmental Research Laboratory, Cmcmnatl toprOVideprocedures for momtonng water supplIes, waste dIscharges, and the qualItyofambIent waters These test methods have been carefully selected to meet the needsofFederal LegIslatIOn and toprOVide gUIdance to laboratones engaged m protectmg human health and the aquatic environment The contnbuttonsandcounselofsCientists m otherEPAlaboratonesare gratefullyacknowledged Test procedures contamed herem, that are approved for water and waste momtonng under the Safe DnnkmgWater Act (SDWA) and the NatIOnal Pollutant DIscharge Eltmmatton System (NPDES), ofPL92-500are so mdicated at the bottomofeach tItle page These approved methods are also recommended for ambient momtonng needsofSection106and208ofPL92-500Methods WIthout thISstated approval are presented for mformatton only Correspondence on these methodsISmVIted RobertL Booth ActmgDIrector, EnVIronmentalMomtonngand SupportLaboratory,CmcmnatI,OhIO 45268 111 ABSTRACT This manual provides test proceduresapprovedforthemOnItonngofwater supphes, waste discharges,andambientwaters,undertheSafeDrmkmgWaterAct, the NatIOnalPollutant Discharge EhmmatlOn System,andAmbient MOnItonng ReqUIrementsofSectIOn106and208 ofPubhcLaw 92-500Thetest methods have beenselectedtomeet the needsoffederal legislatIOn andtoprovide gUidancetolaboratonesengaged m the protectIOnofhumanhealthandthe aquaticenvironment IV CONTENrs , Foreword111 , Abstract IntroductIOn SamplePreservatIon EPAQualItyAssuranceCoordmators U1rj IV , X111 xv xx 100PhysIcal Properties Color Colonmetnc,ADMI Coiorimetnc, PlatInum-Cobalt Spectrophotometnc Conductance SpecIfic Conductance Hardness, Total(mg/lasCaC03) Colonmetnc, AutomatedEDTA TItnmetnc,EDTA Odor Threshold Odor (ConSIstent Senes) pH Electrometnc Electrometnc(ContmuousMomtonng) ResIdue FIlterable Gravlmetnc,Dnedat180°C Non-FIlterable Gravimetnc,Dnedat103-105°C Total Gravimetnc,Dnedat103-105°C VolatIle Gravimetnc, IgnItIOnat550°C SettleableMatter Volumetnc, Imhoff Cone v Method1101 Method1102 Method 110 3 Method 1201 Method 1301 Method1302 Method 1401 Method 1501 Method1502 Method 1601 Method1602 Method 1603 Method1604 Method 1605 Temperature Thermometnc TurbIdIty Nephelometnc 200Metals AtomIC AbsorptIon Methods InductIvelyCoupledPlasma Aluminum AA, DIrect AspIratIon AA, Furnace Antimony AA, DIrect AspiratIOn AA, Furnace. Arsemc AA, Furnace AA, Hydnde Spectrophotometnc. SDDC DIgestion Method for Hydnde and SDDC Banum AA, DIrect AspiratIOn AA, Furnace Berylhum AA, Direct AspIratIOn AA, Furnace Boron Colonmetnc, Curcumm CadmIUm AA, DIrect AspIration AA, Furnace. CalcIUm AA, DIrect AspIratIOn TItnmetnc, EDTA VI Method 1701 Method 1801 SectIon 200 0 Method2007 Method 2021 Method2022 Method 2041 Method2042 Method2062 Method 2063 Method2064 Method 2065 Method 2081 Method 2082 Method2101 Method 210 2 Method 2123 Method2131 Method 2132 Method2151 Method 2152 Chromium AA, Direct AspiratIOn AA, Furnace ChelatlOn-Extraction Hexavalent, Chelation-Extraction Hexavalent, DIssolved Cobalt AA, Direct AspiratIOn AA, Furnace Copper AA, Direct Aspiration AA, Furnace Gold AA, Direct AspIratIOn AA, Furnace IndIUm AA, Direct AspIratIOn AA, Furnace Iron AA, Direct AspIration AA, Furnace Lead AA, Direct AspiratIOn AA, Furnace MagnesIUm AA, Direct Aspiration Manganese AA, Direct Aspiration AA, Furnace Mercury Cold Vapor, Manual Cold Vapor, Automated Cold Vapor, Sediments Vll Method2181 Method2182 Method2183 Method2184 Method2185 Method 2191 Method2192 Method 2201 Method2202 Method 2311 Method2312 Method 2351 Method2352 Method 2361 Method2362 Method 2391 Method2392 Method 2421 Method 2431 Method2432 Method 2451 Method2452 Method2455 Molybdenum AA, DIrectASpIratIOnMethod 2461 AA, FurnaceMethod2462 NIckel AA, DIrectASpIratIOnMethod 2491 AA, FurnaceMethod2492 OsmIUm AA, DIrect AspiratIOnMethod 2521 AA, FurnaceMethod2522 Palladium AA, DIrect AspIrationMethod2531 AA, FurnaceMethod2532 Platmum AA, DIrect AspirationMethod2551 AA, FurnaceMethod2552 PotassIUm AA, Direct AsprrationMethod2581 RhenIUm AA, DIrect AspIratIonMethod 2641 AA, FurnaceMethod2642 RhodIum AA, DIrect AsprratlonMethod 2651 AA, FurnaceMethod2652 Ruthemum AA, DIrect AspIratIon. Method2671 AA, FurnaceMethod2672 Selemum AA, FurnaceMethod2702 AA, HydndeMethod 2703 StIver AA, DIrect AspirationMethod 272 1 AA, FurnaceMethod2722 Vl1l Sodmm AA, DIrect ASpIratIOn AA,Furnace Thalhum AA,DIrectASpIratIOn AA, Furnace Tm AA, DIrect AspIration AA, Furnace Titamum AA, DIrect AspIratIOn AA, Furnace Vanadmm AA, DIrect AspIratIOn AA, Furnace Zmc AA,DIrect AspIratIon AA, Furnace 300Inorgamc, Non-metalllcs ACIdIty TItnmetnc Tltnmetnc(aCIdram) Alkallmty TItnmetnc (pH 45) Colonmetnc, Automated Methyl Orange BromIde TItnmetnc Chlonde Colonmetnc, Automated Ferncyamde,AAI Colonmetnc, Automated Ferncyamde,AII TItnmetnc, Mercunc NItrate Chlonne, Total ResIdual TItnmetnc, Amperometnc TItnmetnc, Back-Iodometnc IX Method 2731 Method2732 Method 2791 Method2792 Method 2821 Method2822 Method 2831 Method2832 Method 2861 Method2862 Method 2891 Method2892 Method 3051 Method 305I Method 310 1 Method 310 2 Method 320 I Method325I Method3252 Method3253 Method 330 I Method3302 '“ , '. Method350.2 Method350.3 Method350.1 Nitrogen Ammonia ,Colorimetric, Automated Phenate. Colorimetric;Titrimtric;Potentiometric - Distillation Procedure. Potentiometric, Ion Selective Electrode. Kjeldahl, Total Colorimetric, Automated Phenate;'Method351.1 Colorimetric, Selpi-Automated Block DigesterAAII.Method351.2 . Colorimetric; Titrimetric; PotentiometricMethod351.3 Potentiometric, Ion Selective ElectrodeMethod351.4 Nitrate-Nitrite Colorimetric, Automated Hydrazine Reduction.Method-353.1 Colorimetric, Automated Cadmium ReductionMethod353.2 Colorimetric, Manual Cadmium ReductionMethod353.3 x Titrimetric, IodometricMethod3g0.3 Titrimetric, DPD-FAS;'Method330.4 Spectrophotometric,DPDMethod330.5 Iodide Titrimetric. Method345.1 Nitrate Colorimetric, Brucine. Method352.1' Fluoride Colorimetric, SPADNS with Bellack Distillation;. Method340.1 Potentiometric, Ion Selective ElectrodeMethod340.2 Colorimetric, Automated Complexone. Method340.3 Cyanide Amenable to Chlorination Titrimetric, SpectrophotometricMethod335.1 Total Titrimetric, SpectrophotometricMethod335.2 Colorimetric, Automated UV .;,;.Method335.3 Nttrtte Spectrophotometnc Oxygen, Dtssolved Membrane Electrode Modified Wmkler (Full Bottle Techmque) Phosphorus All Forms Colonmetnc, Automated, AscorbicACid Colonmetnc, Ascorbtc Actd, Smgle Reagent Colonmetnc, AscorbtcACid, Two Reagent Total Colonmetnc, Automated, Block Dtgestor,AAII Stltca, Dtssolved Colonmetnc Sulfate Colonmetnc, Automated Chloramlate Colonmetnc, Automated Methyl Thymol Blue,AAII Gravlmetnc Turbldlmetnc Sulfide Tltnmetnc, Iodme Colonmetnc, Methylene Blue Sulfite Tttnmetnc 400Orgamcs Btochemtcal Oxygen Demand BOD(5day, 20 DC) Chemtcal Oxygen Demand Tttnmetnc, Mtd-Level Tttnmetnc, Low Level Tttnmetnc, Htgh Level for Saltne Waters Colonmetnc, Automated, Manual Xl . Method 354 1 Method 3601 Method3602 Method 3651 Method3652 Method3653 Method3654 Method 370 1 Method 3751 Method3752 Method3753 Method 375.4 Method 3761 Method3762 Method3771 Method 405I Method 410.1 Method 410 2 Method 410 3 Method4104 011and Grease, TotalRecoverable Gravimetnc, Separatory Funnel ExtractIon Spectrophotometnc, Infrared OrganIc Carbon, Total CombustionorOXidatIOn UV Promoted, PersulfateOXidation. Petroleum Hydrocarbons, Total, Recoverable Spectrophotometnc, Infrared PhenolIcs, Total Recoverable Spectrophotometnc, Manual 4-AAP wIth DIstIllatIOn Colonmetnc, Automated 4-AAP wIth DIstIllatIOn Spectrophotometnc,MBTHwIth DIstIllatIOn Methylene Blue Active Substances (MBAS) Colonmetnc. NTA Colonmetnc, Manual, Zmc-Zmcon Colonmetnc, Automated, Zmc-Zmcon, XlI Method 413 1 Method 413 2 Method 415 1 Method4152 Method 418 1 Method4201 Method4202 Method4203 Method4251 Method4301 Method4302 INTRODUCTION NOT£SmcethefzrstprzntmgofthzsedztwnmMarch1979,varzousedztorzal errorshavebeen broughttoourattentwnwhzchhavebeen corrected m thzssecondprmtmgIn addztwn,zthas beenfoundnecessary toaddto thzsprzntmganupdatedpreservatzon andholdmgtzmes table(Table1),aswellas szxnewmethodsTheyareunder-pH, £leetrometrzcs(contmuousmonztormg),Method1502,underMetals,Inductzvely CoupledPlasma,2007,underMetalslChromzumHexavalent,Dzssolved,Method 2185,underMetalslSodzumAA,Furnace,Method2732,underInorganzc,non- metallzcslAczdzty Tztrzmetrzc(aczd ram),Method3051,andunderOrganzcs, Organzc Carbon,TotalUVPromoted,Persulfate, Oxzdatzon,Method415 2 Theseaddztwnshavebeenmadeso as to keep usersofthemanualcurrentwzththe procedurestheAgencyuses mdetermmmgcomplzancewzthapplzcable waterand effluentstandardszthas establzshed Personswhoalready possess acopyofthe1979edztwnofthemanualandwhowzsh to updateztbymcludmgthecztedaddztwnsneednotrequestanothercopyThenew materzalzsavazlable as a separatevolume,entztled,“TechnzcalAddzt'wnstoMethods forChemzcalAnalyszsofWaterandWastes, £PA-60014-79-020,“ £PA-60014-82-055, fromORDPublzcatwns,C£RI,us£nvzronmentalProtectwnAgency,Cmcmnatz, OH45268 Th1Sth1rded1tlOnof“Methods for Chem1cal Analys1sofWater and Wastes“ contams the chem1cal analytlCal procedures used mUS Env1ronmental ProtectlOn Agency (EPA) laboratones for the exammatlOnofground and surface waters, domest1c and mdustnal waste eftluents, and treatment process samples Except where noted under “Scope and ApphcatlOn“, the methods are-appllcable to both water and wastewaters, and both fresh and sahne water samples The manual prov1des test procedures for the measurementofphyslCal, morgamc, and selected orgamc const1tuents and parameters Methodsfor pestic1des, mdustnal orgamc waste matenals, and sludges are givenmother publlcatlOnsofthe Agency The methods were chosen through the combmed effortsoftheEPA Regional Quahty Assurance Coordmators, the staffofthe PhyslCal and Chem1cal Methods Branch, Env1ronmental Momtonng and Support Laboratory, and other semor chem1sts m both federal and statelaboratones Methodselectionwas basedonthefoUowmgcntena (1)The method should measure the des1red propertyorconst1tuentw1thpreclSlon, accuracy, andspec1fic1tysuffic1ent to meet the data needsofEPA, m the presenceofthe mterfenng matenals encounteredm waterand wastesamples (2)The procedure should utihze the eqUlpment and slalls aval1able m modem water pollutlOncontrollaboratones (3)The selected method1Smusem many laboratonesorhas been suffic1ently tested to estabhsh1tSvahd1ty (4)The method should be rap1d enough to perm1t routme use for the exammationofa large numberofsamples Xlll Instrumental methods have been selected m preference to manual procedures becauseofthe Improved speed, accuracy,andpreCISIOnInkeepmg wIththISpolIcy, procedures for the Techmcon AutoAnalyzer have been mcluded for laboratones havmgthISeqUIpment avaIlableOther contmuousflow automatedsystems usmgthese IdentICal proceduresare acceptable IntralaboratoryandInterlaboratorypreCISIonandaccuracy statements areprOVIdedwhere such data areavaIlable These Interlaboratory statements are denved from Interlaboratory studIes conducted by the QUalIty Assurance Branch, EnVIronmental MomtonngandSupport Laboratory, the AmericanSOCIetyfor TestIng Matenals,ortheAnalytIcal ReferenceSerVIceofthe US PublIc Health ServIce,DHEWThese methods may be used for measurIng both totalanddIssolved constItuentsof thesampleWhenthe dIssolved concentratIOnISto be determmed, the sampleISfiltered through a o45-mIcronmembranefilterandthefiltrate analyzed bytheprocedurespeCIfiedThesample should be filtered as soon aspOSSIbleafter ItIScollected, preferably m the field Where field filtratIOnISnot practIcal,thesampleshouldbefiltered as soon as ItISreceIved Inthelaboratory Many waterandwaste samples are unstableInSItuatIons where the Interval between sample collectIOnandanalySISISlong enough to produce changes m eIther the concentratIonorthe phySIcal stateoftheconstItuent to bemeasured, the preservatIOn practIces m Table I are recommended ThIS manualISabaSICreference formomtonngwaterandwastes m complIanceWIththe reqUIrementsoftheFederal Water PollutIOn ControlActAmendmentsof1972 Although other test procedures maybe used, asprOVIdedmtheFederal RegIster IssueofOctober16,1973 (38FR 28758) andIn subsequent amendments, the methods descnbed InthISmanual wIll be used by the EnVIronmental ProtectIOn Agency m determmIng complIanceWIthapplIcable waterandeffluent standards establIshedby theAgency Although a SIncere effort has been made to select methodsthatare applIcable to theWIdestrangeof sample types, sIgmficant mterferences may be encountered m certam Isolated samplesInthese SItuatIons,theanalystWIllbe provIdmg a valuable servIcetoEPAby defimng the natureofthe mterferenceWIththe methodandbnngIngthISInfOrmatIon to the attentIOnofthe DIrector, EnVIronmentalMomtonngandSupport Laboratory, through the appropnate QualIty Assurance CoordInator xu' SAMPLE PRESERVATION Complete and uneqUIvocal preservatIOnofsamples, eIther domestic sewage, mdustnal wastes,or natural waters,ISa practlcallmposslblhty Regardlessofthe natureofthe sample, complete stablhty for every constItuent can never be achIevedAtbest, preservatIOn techmques can only retard the chemIcal andbIOlogiCalchangesthatmevltably co