CHLORINATION,CHLORAMINATION

ANDCHLORINEMEASUREMENT

ByTerryL.Engelhardt,ApplicationDevelopmentManager,DrinkingWater
VadimB.Malkov,PhD,ProductApplicationsManager,ProcessInstrumentation

The purpose of this document is to summarize basic information about use of chlorine as a
disinfectant and to convey information about the chlorination and chloramination processes.
This document will also explore measurement of chlorine and chloramine residuals. There is
noattempttoprovideanexhaustivedescriptionofchemicalreactions,variouschlorinationor
chloraminationschemes,oracomparisonofrelativemeritsofthevariousapproaches.

Consultcitationsinthelistofreferencesifinformationthatismoredetailedisdesired.

2
TableofContents
TableofFigures.............................................................................................................................................................................4
HistoricalPerspective....................................................................................................................................................................6
OverviewofChlorineChemistryinWaterTreatment..................................................................................................................7
FreeResidualChlorination............................................................................................................................................................9
Chloramination.............................................................................................................................................................................9
NaturalOrganicMatter.......................................................................................................................................................12
Nitrification.........................................................................................................................................................................13
EffectofTemperatureonNitrification................................................................................................................................13
EffectofpHonNitrification................................................................................................................................................14
AnalyticalToolsforMonitoringforNitrification.................................................................................................................17
AnalyticalLaboratoryMethodsforMeasurementofChlorineResiduals...................................................................................18
DPDColorimetricandTitrimetricMethods................................................................................................................................18
Liquidvs.PowderedReagents.............................................................................................................................................18
DPDColorimetricMethod...................................................................................................................................................20
DPDTitrationMethod.........................................................................................................................................................20
DPDUltraLowRangeColorimetricMethod.......................................................................................................................21
IndophenolMethodforMonochloramineinWaterandWastewater.......................................................................................23
ChemicalReactions.............................................................................................................................................................24
IndophenolFreeChlorineMethod..............................................................................................................................................24
MethodDescription............................................................................................................................................................26
IodometricTitration....................................................................................................................................................................26
AmperometricTitrationMethods...............................................................................................................................................27
AmperometricTitrationforFreeResidualChlorine............................................................................................................28
AmperometricTitrationforCombinedandTotalResidualChlorine..................................................................................28
BacktitrationforTotalChlorine..........................................................................................................................................29
UseofStandardsandDevicesforMethodAccuracyandPerformanceVerification..................................................................30
LowLevelChlorineStandardsforMethodVerification......................................................................................................31
PrecautionsUsingPermanganateasanEquivalentStandard.............................................................................................33
UseofSpecColorStandards.........................................................................................................................................34
MethodInterferencesandSourcesof Errors..........................................................................................................................35
SamplingConsiderations.....................................................................................................................................................35
InterferencesCommontoAllChlorineMethods................................................................................................................36
OtherDisinfectants.............................................................................................................................................................36
ManganeseCompounds......................................................................................................................................................36
OrganicChloramines...........................................................................................................................................................37
BromideinChlorinatedWaters...........................................................................................................................................38
ErrorsCommontoTotalChlorineDeterminations.............................................................................................................38
InterferencesintheDPDMethods.............................................................................................................................................39
CalibrationNonLinearity....................................................................................................................................................39
MonochloramineInterferenceintheFreeChlorineTest....................................................................................................40
CompensationforSampleColorandTurbidity...................................................................................................................40
InterferencesintheAmperometricTitrationMethods..............................................................................................................41
ChoiceofReductant............................................................................................................................................................43
EffectofIodineDemandonEndPointDeterminations......................................................................................................44
OrderofReagentAdditionforSalineWaterorSeawater...................................................................................................44
ComparingPortableandLaboratoryMeasurements.................................................................................................................45
ContinuousOnlineMeasurementofChlorineResidual............................................................................................................46
3
ColorimetricDPDProcessChlorineAnalyzer......................................................................................................................46
CL17WasteDischargeAnalysis...........................................................................................................................................48
AmperometricSensors........................................................................................................................................................49
Internal/ExternalpHCompensationforAmperometricProbes.........................................................................................53
TemperatureEffect/CalibrationRequirementsforAmperometricProbes.........................................................................54
CLF10andCLT10AmperometricProbeChlorineResidualAnalyzers.................................................................................55
OpenCellChlorineAmperometricTechnologies................................................................................................................56
Limitationsofonlinemeasurementinstruments...............................................................................................................57
StepstoSelectinganOnlineMeasurementTechnology.....................................................................................................58
ContinuousOnlineMeasurementofChloramination...............................................................................................................62
ComparisonofOnlinetoGrabSampleMeasurements.............................................................................................................63
Acknowledgements.....................................................................................................................................................................64
AppendixA:Otheranalyticalmethods.......................................................................................................................................65
OrthotolidineMethod.........................................................................................................................................................65
Syringaldazine(FACTS)Method..........................................................................................................................................65
PotentiometricElectrodeMethod......................................................................................................................................65
AppendixB:CalculationofCTValues.........................................................................................................................................66
DefinitionofCT....................................................................................................................................................................66
DisinfectionStrategies.........................................................................................................................................................67
KindandConcentrationofOrganismsAddressed...............................................................................................................67
RequirementsforGiardiaandViruses................................................................................................................................68
RequirementsforCryptosporidiumunderLT2ESWTR........................................................................................................68
SummaryofMicrobialToolboxOptions..............................................................................................................................69
DeterminingCTRequirements............................................................................................................................................71
TheEntireTreatmentSystemisImportant.........................................................................................................................72
UnderstandingLogRemoval...............................................................................................................................................73
CalculatingDetentionTime.................................................................................................................................................74
BafflingFactor.....................................................................................................................................................................74
UseHachWIMStoCalculateCT..........................................................................................................................................75
EPAAutomatedCTCalculationToolsAvailable..................................................................................................................75
AppendixC:PlumbingSampletoaProcessAnalyzer................................................................................................................76
Ifthesampleisnotright,theanalysisiswrong!.................................................................................................................76
Keepitshort,keepitsimple,anddontdelay.....................................................................................................................76
Donotmixandmatchplumbingfittings!............................................................................................................................77
Provideproperflowcontrol................................................................................................................................................77
Makethecorrectsampletap..............................................................................................................................................78
SamplePumping..................................................................................................................................................................78
AppendixD:FeedingAmmoniaforChloramination...................................................................................................................79
ExampleCalculation:UsingLiquidAmmoniumSulfate(LAS).............................................................................................79
SimpleStepstocontrollingchlorineandammoniaforchloramination.............................................................................80
StabilityofAmmoniaandBleachSolutions.........................................................................................................................80
References..................................................................................................................................................................................81

4
TableofFigures
Figure1:Typhoiddeathsvs.treatmenttechniquesforDenver,Colorado...................................................................................6
Figure2:pHvs.chlorinespecies...................................................................................................................................................7
Figure3:Typicalstylizedbreakpointcurve...................................................................................................................................8
Figure4:CTValuesforchlorinevs.chloramines........................................................................................................................10
Figure5:Breakpointcurvewithammonia..................................................................................................................................10
Figure6:BreakpointcurveduetoasignificantamountofNOM...............................................................................................12
Figure7:Freeammoniavs.chlorineadded................................................................................................................................12
Figure9:Effectoftemperatureonnitrification..........................................................................................................................13
Figure8:Nitrification,acircularproblem...................................................................................................................................13
Figure10:EffectofpHonnitrification........................................................................................................................................14
Figure11:Parametersassociatedwithpossibleonsetofnitrification.......................................................................................15
Figure12:Possiblecorrectiveactionsfornitrification................................................................................................................16
Figure13:Analyticaltoolsformonitoringnitrification...............................................................................................................17
Figure14:ComparisonofDPDandAmperometricLaboratoryMethodsforFreeandTotalChlorine.......................................18
Figure15:FoilpackagedDPDFreeChlorineReagent...............................................................................................................19
Figure16:ChlorineResidualAccuVacAmpules..........................................................................................................................19
Figure17:DPDchlorinereactionproducts.................................................................................................................................20
Figure18:AbsorptionspectraforDPD.......................................................................................................................................20
Figure19:DPDFASorDPDFEASTitration.................................................................................................................................21
Figure20:AmpuledReagentsfortheHach................................................................................................................................21
Figure21:ComparisonofHachsULRTotalChlorineResidualmethodwithamperometrictitration.......................................23
Figure22:Indophenolformationfordeterminationofmonochloramine.................................................................................24
Figure23:ComparisonofDPDvs.Indophenolforfreeresidualchlorineat3.1mg/linthepresenceofmanganese...............24
Figure24:ComparisonofDPDvsIndophenolforfreeresidualchlorineat1.0mg/linthepresenceofmanganese................25
Figure25:ComparisonofDPDvs.Indophenolforfreeresidualchlorineat0.12mg/linthepresenceofmanganese.............25
Figure26:ChloramineinterferenceintheDPDfreechlorinetest.............................................................................................25
Figure27:Thiosulfatevs.PAOTitrantforAmperometricTitration............................................................................................27
Figure28:Forwardtitration(left),Backtitration(right)............................................................................................................27
Figure29:AmperometricForwardTitrationforFreeResidualChlorine....................................................................................28
Figure30:AutoCAT9000AmperometricTitrator.......................................................................................................................30
Figure31:TypicalForwardTitrationforfreeresidualchlorinewhenusing...............................................................................30
Figure32:PourRite(left)andVoluetteAmpuleChlorineStandardSolutions...........................................................................32
Figure33:OrderofSampletoReagentAdditionUsingPermanganateEquivalentStandards..................................................33
Figure35:SpecColorStandards..............................................................................................................................................34
Figure34:SpecColorStandardsforDPDChlorine.................................................................................................................34
Figure36:FillinganAccuVacAmpule.........................................................................................................................................35
Figure37:Typicalprocedureforcompensatingformanganeseorchromiuminterferenceinchlorineresidualtesting..........37
Figure38:StandardMethodCalibrationDBDColorimetricMethod.......................................................................................39
Figure39:OrifloFilterApparatusandglassfiberfilters..........................................................................................................41
Figure40:Nitriteinterferenceinamperometricchlorinemethods...........................................................................................43
Figure41:ComparisonofthiosulfateandPAOastitrants..........................................................................................................44
Figure42:ColorComparatortestkitforchlorineresidual.........................................................................................................45
Figure43:HachDR6000UVVisSpectrophotometer.................................................................................................................46
Figure44:HachPocketColorimeterII........................................................................................................................................46
Figure45:Cl17ChlorineAnalyzer...............................................................................................................................................47
Figure46:Cl17FlowPathDiagram.............................................................................................................................................47
Figure47:SummaryofCL17DischargeAnalysis........................................................................................................................48
Figure48:DiagramofHachCompanys3ElectrodeAmperometricChlorineProbe.................................................................50
Figure49:Effectofflowrateonanampermetricsensor...........................................................................................................51
Figure50:Amperometricprobemembranesdemonstratingironfoulinganddelamination....................................................52
Figure51:HypochlorousAcidDissociationCurvevs.pH............................................................................................................52
Figure52:DPDvs.AmperometricprobeaspHisvaried............................................................................................................53
5
Figure53:TemperatureEffectonanAmperometricSensor......................................................................................................54
Figure54:HachCLF10AmperometricChlorineAnalyzer...........................................................................................................55
Figure55:Opencellamperometricsensorillustration..............................................................................................................56
Figure56:ProsandConsofCLF10orCLT10andtheCL17Analyzers.........................................................................................58
Figure57:SelectionGuideofCLF10orCLT10andtheCL17Analyzer........................................................................................60
Figure58:Graphicalexpressionofcalculatedresponses...........................................................................................................61
Figure59:APA6000Ammonia/MonochloramineAnalyzer.......................................................................................................62
Figure60:Reactionofsyringaldazinewithfreechlorine............................................................................................................65
Figure61:Variablesaffectingeffectivenessofdisinfection.......................................................................................................67
Figure62:SWTRAllowedremovalcreditfortreatmentanddisinfectionincombination.........................................................68
Figure63:Binclassificationandadditionaltreatmentrequirementsforfilteredsystems........................................................68
Figure64:LT2ESWTRTreatmentrequirementsforunfilteredsystems.....................................................................................69
Figure65:Microbialtoolboxoptions.........................................................................................................................................70
Figure66:RequiredCTValues(mgmin/L)for3logInactivationofGiardiaCystsbyFreeChlorine,pH6.09.0.......................71
Figure67:UnitProcessInventoryforLogCredit........................................................................................................................72
Figure68:Percentvs.LogRemoval............................................................................................................................................73
Figure69:TableofBafflingfactors.............................................................................................................................................75
Figure70:HachWIMS.................................................................................................................................................................75
Figure71:SampleQuill...............................................................................................................................................................78
Figure72:Ammoniacompoundsusedforchloramination........................................................................................................79

6
HistoricalPerspective

KarlScheele,aSwedishchemist,identifiedChlorineasachemicalelementin1774.Chlorinehasanatomic
numberof17andatomicmassof35.45.ItisamemberofthehalogenfamilyonthePeriodicChart.Other
membersofthefamilyincludeFluorine,BromineandIodine.Eachofthesecompoundsplaysanimportantrole
inwatertreatment.

OneofthefirstusesofchlorineinwaterandwastewatertreatmentwasadditiontosewersinLondon,Englandin
the1830s,notasadisinfectantbutratherasadeodorantfollowingcholeraoutbreaks.Itwasbelieved
controllingtheodorfromthesewersmighthelpcontrolthespreadofthedisease.Thegermtheoryofdisease
andthusthepracticeofpurposelyaddingchlorinefordisinfectingwaterdidnotoccuruntilnearly70yearslater.

Disinfectionofwaterisnotthesoledomainofachemicalsuchaschlorine.Whetherfortreatingmunicipal
drinkingwater,wastewater,oruseinmanufactureofanotherbeverage,disinfectionistheresultoftheproper
applicationandoperationofphysical,biologicalandchemicaltreatmentprocesses.Thisprincipleisillustratedby
thechartbelowdemonstratingimplementationofvarioustreatmenttechniquesvs.theincidenceoftyphoidin
Denver,Coloradofromapproximately1887to1940.

Figure1:Typhoiddeathsvs.treatmenttechniquesforDenver,Colorado.
UsedwithpermissionofDenverWater.

Inthepracticeofwatertreatmentoneshouldkeepinmindproperoperationandcontrolofallthestepswithin
thetreatmentprocessareimportanttoachievingaproperlydisinfectedeffluent.Thebalanceofthisdocument
willfocussolelyontheuseofchlorinefordisinfection.


7
OverviewofChlorineChemistryinWaterTreatment

WhenchlorineisaddedtowateratapHgreaterthan4,hypochlorousacid(HOCl)isformedasillustratedbythe
empiricalequationbelow
1
:

Cl
2
+ H
2
O HOCl + H
+
+ Cl

AsthepHincreasesabove4,thehypochlorousacidwilldissociatetoformthehypochloriteion(OCl

):
HOCl H
+
+ OCl

Theprocessesofchlorinationandchloraminationaremorecomplexthantheyappeartobefromtheempirical
reactions.Thereactionsdepictedcontainadoubleheadedarrowtodenotereversiblereactions.Inthefirst
equation,ifthepHisgreaterthan4,thereactionistotheright,favoringformationofhypochlorousacid.Ifthe
pHshoulddropbelow4,chlorinegascancomeoutofsolution.

Undertheproperconditions,mostifnotallthereactionsoneencountersinchlorinationandchloraminationare
reversible.Atagivensetofconditions,manydifferentchlorinespeciesmaybepresentinwatersimultaneously.
Forexample,seeWhite,5
th
ed.,page95,figure2.4.

Chlorineexistinginwaterashypochlorousacidorasthehypochloriteionistermedfreeavailablechlorine.The
followingfigureillustratestherelationshipofthesetwospeciestopHandtemperature.

1
Onemayseethemolecularformulaforhypochlorousacid,HOCl,alsowrittenasHClO.Similarly,onemayseetheformula
forthehypochloriteion,OCl

,writtenasClO

.However,mostrecentreferencesusetheformsHOClandOCl

becausethey
mostaccuratelydescribethestructureofthesespecies;butHClOandClO

arealsoacceptable.
Figure2:pHvs.chlorinespecies
8
Hypochlorousacidandhypochloriteionspeciesaredisinfectants.Hypochlorousacid(1.4eV)isabetter
disinfectantthanthehypochloriteion(0.9eV).
Reactionsofchlorinewithnitrogencontainingcompounds(ammonia,nitritesandorganicamines)areof
particularinterestwhendisinfectingwater.Thereactionsnormallyofgreatestinterestarethosewithchlorine
andammoniatypicallyrepresentedbythesimplifiedempiricalreactionsthatfollow.Notethatasabove,the
reactionsarereversible:

1. Chlorinereactswithammoniatoformmonochloramine
2
,NH
2
Cl.
2. Withcontinuedadditionofchlorine,chlorinereactswithmonochloraminetoformdichloramine,NHCl
2
.
3. Continuedadditionofchlorineresultsinformationofnitrogentrichloride(NCl
3
),alsocalled
trichloramine,whichisveryunstable.
4. Ifchlorineadditioniscontinued,thenitrogentrichlorideisdestroyedleavingprimarilyhypochlorousacid
andotherproducts(*=N
2
,Cl

,H
2
O,H
+
,NO
3

andotherspecies).

Thebreakpointcurveisusedtorepresentthereactionsrepresentedabove.Thebreakpointreaction(and
resultingbreakpointcurve)typicallyiscreditedtotheworkoftwoindividuals,A.E.GriffinandC.K.Calvertinthe
late1930s,althoughmanyindividualshadbeenstudyingthereactions.Aswiththereactionsabove,oneshould
notinterpretthebreakpointcurveasabsolute.ThecurvedepictedassumesthemolarratiosoftheCl
2
andNH
3
N
fromtheempiricalequationsshownabove.Inactualpractice,theshapeofthebreakpointcurvevariesbasedon
pH,temperature,theformofnitrogenpresentandtime.

Oneshouldtakecareininterpretingthese
simplifiedreactions.Theydonottellthewhole
story.

Thegoalofdisinfectionwithchlorineinwater
treatmentistomaintainpredominatelyeitherfree
residualchlorineortomaintainpredominately
monochloramine.Ifonepurposelycontrolsthe
ratioofchlorinetoammonia(nitrogen)tomaintain
monochloramine,thepracticeisreferredtoas
chloramination.Iftheonlynitrogencompound

2
Reaction1illustratesonemole(mol)ofhypochlorousacidcombineswithonemoleofammoniaandsinceeachmoleof
ammoniacontainsonenitrogenatom.Correspondingly,eachmoleofhypochlorousacidrepresentsonemoleculeofCl
2
that
combineswithonemoleofnitrogen.Thus,onecanrepresentthemolarratioofhypochlorousacidtoammoniaas1:1Cl
2
:N.
Thisshouldnotbeconfusedwithweightratioasitisnormallyusedintheindustryandwhichbecomes71.5:14or5:1.
1. HOCl + NH
3
NH
2
Cl + H
2
O
2. HOCl + NH
2
Cl NHCl
2
+ H
2
O
3. HOCl + NHCl
2
NCl
3
+ H
2
O
4. HOCl + NCl
3
HOCl + *
Figure3:Typicalstylizedbreakpointcurve
9
presentisammonia,monochloraminewillpredominateifaCl
2
:Nmolecularweight(mass)ratiooflessthan5:1is
maintained.Freeresidualchlorination(orbreakpointchlorination)resultsbymaintainingaCl
2
:Nweightratioof
greaterthan9:1.Thelinelabeledbreakpointinfigure3correspondstoapointwheretotalammoniashould
reachzero.Inactualpracticetheremaybemeasureabletotalammoniabeyondthebreakpointbutitshouldbea
verylittle.
FreeResidualChlorination

Ifoneconsidersonlytheempiricalchemicalequations,onlyfreeresidualchlorine(thesumofhypochlorousacid,
HOCl,andthehypochloriteion,OCl

)existsbeyondthebreakpoint.Duetothecomplexityofthechemical
reactions,thismaynotbetrue.Somereferenceswillprovidearuleofthumbstatingwhenfreeresidualchlorine
isacertainpercentageoftotalresidualchlorine(typicallystatedasatleast9395%)thenoneisbeyondthe
breakpoint.Oneshouldnotrelyonsuchrulesofthumborguidelines.Theycanbeverymisleading.Toassure
theprocessisbeyondbreakpointoneneedstomeasure!Totalammoniamustbezeroorverynearzero.Hach
CompanysuggestsmeasurementoftotalammoniawiththeSalicylateMethod.

Atthebreakpoint,therearecompetingreactionsproducingfreechlorine,monochloramine,dichloramine,
trichloramine,andorganicchloramines.Identificationofthesespeciesindividuallyinthemixtureisdifficult,
especiallyinasolutionthatisnotparticularlystable.Itisreasonabletoassumethatnuisanceresidualsformed
justbeyondthebreakpoint,andintheabsenceoforganicnitrogen,consistprimarilyoftrichloramineand
monochloramine.Whenorganicnitrogenispresent,thenuisanceresidualtitratesasifitwerecomposedof
dichloramine,butitisprobablymadeupmostly(about90%)oforganicchloramines,withmuchlesseramounts
ofmonochloramineandtrichloramine(Whites5
th
ed.,pg121).

Theonlywaytobecertainoneisbeyondthebreakpointistomeasure!

Measurethefreeandtotalresidualchlorine.Freeresidualchlorineshouldapproachthesamevalueas
totalresidual,FreeResidualChlorineTotalResidualChlorine
Measurethetotalammonia.Totalammoniashouldbezeroorveryneartozero.

Chloramination

Chloraminationreferstothepurposefulmixingofchlorineandammoniatocontrolthechlorinetonitrogenratio.
Chloraminationindrinkingwaterhasbeenpracticedsinceabout1917.

ChloraminationincreasedinuseuntilthebeginningofWorldWarII.DuringWorldWarII,ammoniawasneeded
forthewareffortandthusitsuseinwatertreatmentwasdiscouraged.Chloraminationhasreemergedsincethe
mid1970sandtheusecontinuestospread.AccordingtoLi(WaterConditioningandPurification,2011),from
2007to2010thenumberofwaterutilitiesintheUnitedStatespracticingchloraminationincreased37%from944
to1,298;andthetotalpopulationservedbychloraminatedwaterincreasedfromapproximately54millionto
over68million.By2010,oneormorewatersystemsin43Statespracticedchloramination.

10
Concernaboutformationofundesirabledisinfectionbyproducts(DBPs)fromchlorinationgeneratedrenewed
interestinchloraminationinthe1970s.DBPsareproducedbythereactionofchlorinewithorganicmatterinthe
water.Usingmonochloramineformedbyprereactionofthechlorinewithammonialowerstheformation
potentialforDBPs.However,chloraminationisnotthepanaceaforDBPsitwasoncebelievedtobe.Research
indicatesotherDBPs(e.g.,Nitrosodimethylamine,NDMA)aregeneratedbythechloraminationprocess.The
DBPsresultingfromchloraminationarebeingstudiedtodeterminethenegativehealthimpact,ifany.

Duetotheloweroxidationpotential(~0.60.8eV)chloraminesarenotaseffectivedisinfectantsaseither
hypochlorousacid(~1.4eV)orthehypochloriteion(0.9eV).

Log
Removal
Giardia Viruses
<1C 10C 20C <1C 10C 20C
Cl
2
NH
2
Cl

Cl
2
NH
2
Cl

Cl
2
NH
2
Cl

Cl
2
NH
2
Cl

Cl
2
NH
2
Cl

Cl
2
NH
2
Cl

0.5 40 635 21 310 10 185

1 79 1270 42 615 21 370
2 158 2535 83 1230 41 735 6 1243 3 643 1 321
3 237 3800 125 1850 62 1100 9 2063 4 1067 2 534
Figure4:CTValuesforchlorinevs.chloramines.
Source:USEPALT2ESWTRT&CDocument,Exhibit2.1,Dec.2005Exhibit2.1demonstratesthatchloramineisrelativelyineffective
comparedtofreechlorineforGiardiaandvirusinactivation.Inaddition,chloramineisineffectiveforinactivationofCryptosporidium
(Peetersetal.1989,Korichetal.1990).USEPALT2ESWTRandT&CDocument

Monochloramineisconsideredagooddisinfectant.Itdoesnotcontributesignificanttasteorodorandismore
stableinsolutionthanfreeresidualchlorine.Chloraminationoftenisusefulinsystemswithlongdistribution
linesorwithlargeamountsofstoragewherethewateragemightbetoolongtomaintainfreechlorineresidual.

Dichloramineisabetterdisinfectantthanmonochloramine,butitcontributesundesirabletasteandodor.
Nitrogentrichlorideortrichloramineisundesirablebecauseithasadisagreeabletasteandodorandisvery
unstableinsolution.
Thekeytochloraminationiscontrollingtheratio
ofchlorinetonitrogentofavorformationof
monochloramineandpreventformationof
dichloramineandtrichloramine.Thebreakpoint
curvebestillustratesthispoint.Additionofa
secondaryverticalaxistorepresentammonia
helpstoillustratetheimportantconsiderations.

Aschlorineisadded,itreactswithammoniato
formmonochloramine.Noticetotalammonia
remainsunchangedaschlorineisaddedaslong
Figure5:Breakpointcurvewithammonia
11
astheratioofchlorinetonitrogen(Cl
2
:N)islessthan5:1.Totalammoniaistheammonianaturallyoccurringin
thewaterplusammoniaaddedpurposely,includingtheformedchloramines.
3
Monochloramineisanammonia
compound.Usingaportionoftheammoniatoformmonochloraminedoesnotchangethetotalammonia!
Monochloramineisincludedinthetotalammoniameasurement.

Additionofchlorinecorrespondstoadecreaseinunreactedammoniafreeammonia.Thecloserfreeammonia
istozero,thebetterthechloraminationsystemwilloperate.Freeammonialeftinthewaterisanutrientfor
microorganisms.Underfavorableconditionsoftemperature,pH,andtime,organismscanflourishcausing
significantoperationalandaestheticproblemsinthewaterdistributionsystem.Excessammoniacanlead
negativehealtheffectduetonitrificationandformationofnitritesandnitratesinwater.

Theproblemmostcommonlyassociatedwithchloraminationisnitrification.Aspreviouslycited,thereaction
formingmonochloramineisreversible.Withtimeandunderfavorableconditions,aseriesofreactionscancause
monochloraminetodeteriorateandresultinreleaseoffreeammoniaaddingevenmorenutrienttothesystem.

Thestartofundesirableformationofdichloraminecorrespondstothepointwherethefreeammonia(unreacted
ammonia)reacheszero.Lookingatthesimplifiedempiricalequations,itappearsonlymonochloraminecanexist
aslongasCl
2
:Nislessthan5:1.Hence,onemightexpectfreechlorineresidualtobezeroandmonochloramine
residualtoequaltotalchlorineresidual.Alternately,onemightexpect,ifatleastsomeamountoffreechlorineis
present,themonochloramineshouldequaltotalresidualchlorineminusfreeresidualchlorine.Inreality,this
chemistryismorecomplex.Totalresidualchlorineminusfreeresidualchlorinedoesnotnecessarilyequal
monochloramine!Theonlywaytoknowmonochloramineconcentrationistomeasuremonochloramine!

AmethoddevelopedbyHachCompanymeasuresmonochloraminespecificallywithoutinterferencefromorganic
amines,dichloramines,freechlorine,organicchloramines,nitritesormanganese.SeeIndophenolMethodfor
Monochloramine,below.

Duetothecomplexnatureofthereactions,onecannotrelyonrulesofthumb.Measure!

Measuretotalresidualchlorine(TRC),monochloramine(Mono)andfreeresidualchlorine(FRC)TRC
Mono>FRC
Measuretotalammoniathroughouttheprocess,totalammoniashouldnotchangeifaratioofCl
2:
N
remainslessthan5:1
Measurefree(unreacted)ammonia(FA).FA>0duringmonochloramineformation

Itiscommontooperateandachievelessthan0.1mg/lfreeammonia.Manywatersystemswillattemptto
operateat0.05mg/lorless.Attemptingtooperateatverylowconcentrationsoffreeammoniamakesattention
todetailintheindophenolmethodcritical.

3
Anhydrousammonia,granularammoniumsulfate((NH
4
)
2
SO
4
)liquidammoniumsulfate(LAS,3840%)andaquaammonia
(ammoniumhydroxide,19%),arecommonlyusedforadditionofammonia.SeeAppendixD.
12
1. Thereactionrateofthefreeammoniatestistemperaturesensitive.Thereactiontimeat25C(77F)is2
minutes.Thereactiontimeatabout16C(61F)is6minutes.Thefreeammoniaanalyticalprocedures
forHachspectrophotometersandcolorimeterscontainachartofreactiontimesvs.sampletemperature.
Itisimportanttofollowthechartfortheproperreactiontime.
2. Atlowfreeammoniaconcentrations,thecolorcontributedbythereagentscanbesignificant.Determine
reagentblankbyusingchlorineandammoniafreeDIwater.Subtractthereagentblankfromthefree
ammoniaresultforthesample.Hachsanalyticalproceduresforfreeammoniacontaininstructionsthat
aremoredetailed.
NaturalOrganicMatter

Naturalorganicmatter,NOMandothernitrogencompoundspresentinwaterotherthanammoniacanhavea
significantimpactonchlorination,chloraminationandthustheshapeofthebreakpointcurve.
ThecurvesrepresentedinFigures3and5donotnecessarilyrepresentwhatonemayencounterataspecific
watersource.TheGoldenStateWater
Companywasattemptingtosolvea
problemwithformationofTHMsintheir
distributionsystemduetohighamountsof
NOMinawellsource.Noticetheeffectof
theNOMontheshapeofthecurveaswell
astheimpactoftime.PointlabeledA
typicallycorrespondstoaCl
2
:Nratioof5:1.
Inthisinstance,thepointisgreaterthan
6:1!Wherethebreakpointnormallyoccurs
ataratioofabout9:1,thesedataindicate
thebreakpointoccurredatgreaterthan
14:1,pointB.

Thewatercompanydecidedthebestsolution
wastodestroyallnitrogencompoundsby
passingthebreakpoint;thatis,driving
ammoniatozero.Asonecanseefromthe
chartatright,itwasdeterminedtheywould
havetoestablishaCl
2
:Nratioof
approximately16.4:1,pointC,wellin
excessofwhattheoreticaldatawould
suggest.
Processcontrol,especiallyinchlorinationand
chloramination,requiresmeasurementof
multipleanalytes!
Figure6:BreakpointcurveduetoasignificantamountofNOM.
UsedwithpermissionoftheGoldenStateWaterCompany.
A B
C
Figure7:Freeammoniavs.chlorineadded.
UsedwithpermissionoftheGoldenStateWaterCompany.
13
Nitrification

Nitrificationoccursinawatersystemusingchloraminationwhenfavorableconditionsoftime,temperature,pH
andavailabilityofammoniacombinetopermitcertainorganismstoflourish.OrganismsincludingNitrosomonas,
NitrosococcusandNitrosospiraassistthefollowingreactionwhereammoniaisoxidizedtoformnitrite:

NH
3
+ O
2
NO
2

+ 3H
+
+ 2e

OrganismssuchasNitrobacter,Nitrospina,NitrococcusandNitrospiracontinuethereactionconvertingnitriteto
nitrate:
NO
2

+ H
2
O NO
3

+ 2H
+
+ 2e

EffectofTemperatureonNitrification

Variousreferencesprovideslightlydifferentguidanceonthetemperaturerangesthatarefavorableor
unfavorableforoccurrenceofnitrification.Thefigurebelowoffersageneralguideline.

32F 50F 77F 80100F 104F 122F

Nitrification
ceases
Nitrificationslows

Favorablefor
nitrification
Mostfavorablefor
nitrification
Nitrificationslows
andceases
0C 10C 25C 2639C 40C 50C
Figure9:Effectoftemperatureonnitrification
Figure8:Nitrification,a circular problem.

14
EffectofpHonNitrification

ResearchershaveobservedvaryingeffectsofpHonnitrification.SomehaveobservednitrificationatpHashigh
as9.7.OthershaveobservedpHgreaterthan9inhibitsnitrification.Thereislittlevariation,however,in
observingthatnitrificationispossibleoveraverywidepHrange.ItencompassesthepHrangeinmostpotable
watersystems.Thefigurebelowprovidesageneralguide.

Nitrosomonas
ActivitypHrange 6.59
OptimalpHrange 7.08.0
Nitrobacter
ActivitypHrange 6.59
OptimalpHrange 7.58.0
Source:Nitrification,OfficeofWater,OfficeofGroundWaterandDrinking
Water,DistributionSystemissuepaper,U.S.EPA,August15,2002
Figure10:EffectofpHonnitrification
Oxidationofammoniatonitriteduringnitrificationrequires(consumes)7.2mg/lasCaCO
3
ofalkalinityforeach1
mg/lofammonia.Additionalalkalinityisconsumedinconversionofnitritetonitrate.Inlowalkalinitywater
(lessthan30mg/lasCaCO
3
)thismayleadtoadecreaseinpH.ThedecreaseinpHthenmayhaveother
consequencesincluding:

Increasingtherateofnitrification
Contributingtoincreasedcorrosioninthedistributionsystem
Possiblyincreasetheleachingofleadand/orcopperthushavinganegativeimpactontheutilitys
compliancewiththeLeadandCopperRule(intheUnitedStates)

Evenwhenthealkalinity(buffercapacityofthewater)issufficientlyhighsothatpHisnotsignificantlyaffectedby
onsetofnitrification,itisstillimportanttomeasureandmonitorpHinthedistributionsystem.Measurementof
pHisimportantforcorrosioncontrolandforcalculationofCTvalues.ChangeinpHmaysignalotherproblemsin
awatersystemsuchasanintroductionofforeignmaterialintothewaterduetoasystemmalfunction,amain
break,backflow,ordeliberatecontamination.

15
Observedparameter
Possiblesignalsofonsetof
nitrification
pH

DissolvedOxygen(DO)
Approximately4.6mg/lofoxygenarerequiredtooxidize1mg/lofNH
3
N
toNO
3

AlkalinityApproximately7.2mgofalkalinityasCaCO
3
isrequiredto
oxidize1mg/lofNH
3
NtoNO
2

MonochloramineResidual

FreeAmmonia
Asmonochloraminerevertstofreeammonia
andchlorine,freeammoniawillinitiallyincrease
thentobeconsumedasitisconvertedtonitrite.

WaterAge

WaterTemperature

Nitrite

Nitrate

HeterotrophicPlateCounts(HPC)and/orATP

Sloughingofbiofilmincreasescustomerturbiditycomplaints

Increaseofbiofilmreducespipeflow(increasesfriction).Thiscanbe
detectedbyHPCorATPanalysis.

DecreaseIncrease

Figure11:Parametersassociatedwithpossibleonsetofnitrification

Respondingtoonsetofnitrificationcanbedifficult.Thereisnosinglecorrectresponse.Thecorrectresponse
variesbasedonwaterqualityandtheresourcesathand.Thefollowingfigurecontainssomepossiblecorrective
measures.

16
CommonPossible
CorrectiveActions
Possiblestepsto
consider
Discussion
pH

Ifthealkalinityofthewaterisrelativelyhigh,this
maynotbepractical
DissolvedOxygen(DO)

Aeratebyuseofanaeratororimprovedcirculation
inastoragetank
Monochloramine
Residual

Increaseresidualandoperatechloraminationcloser
to5:1Cl
2
:Nratioifpractical
FreeAmmonia
Operatechloraminationcloserto5:1Cl
2
:Nratio
whenpractical
WaterAge

Improvecirculationinstoragetanks,increase
flushing,decreasestoragecapacity
DecreaseIncrease

Figure12:Possiblecorrectiveactionsfornitrification

Acombinationoftacticstypicallyisnecessarytocontrolnitrification.Certainly,thebestpracticeistowork
diligentlytominimizetheopportunityfornitrificationtooccur,including:

Maintainverylowfreeammoniaresidual.
Attempttolimitwaterage.
Ensurewaterstoragetanksandreservoirsproperlycirculate.

17
AnalyticalToolsforMonitoringforNitrification

Analyte Laboratorytoolsavailable Onlinetoolsavailable

Chlorineresidual
Laboratoryandportablecolorimetersand
spectrophotometersandreagentsforfreeand
totalresidualchlorine
ColorimetricAnalyzeror
amperometricprobesforfreeor
totalresidualchlorine.
Monochloramine
residual
Laboratoryandportablecolorimetersand
spectrophotometersandreagentsfor
monochloramineresidual
Ammonia/Monochloramine
Analyzerformonochloramine,free
andtotalAmmonia
Freeandtotal
ammonia*
Laboratoryandportablecolorimetersand
spectrophotometersandreagentsforfreeand
totalammonia
Ammonia/Monochloramine
Analyzerformonochloramine,free
andtotalAmmonia
pH
LaboratoryandportablepHmeters**and
electrodes
pHprobesandcontrollers***
DissolvedOxygen
Laboratoryandportablemeters*and
electrodes
DOprobesandcontrollers***
Temperature IncludedaspartofallpHandDOprobesforlaboratory,portableoronlineuse
Alkalinity
Laboratoryandportabletitrationwiththe
DigitalTitrator
AlkalinityAnalyzer
Nitrite
Laboratoryandportablecolorimetersand
spectrophotometerswiththeDiazotization
method
N/A
Nitrate
Laboratoryandportablecolorimetersand
spectrophotometerswiththecadmium
reductionorDimethylphenolmethods,or
NitrateISE*
Nitrateprobe
AdenosineTriphosphate
(ATP)
Apparatus,reagentsandluminometer N/A
Heterotrophicplate
counts(HPC)
Media,platesandapparatus N/A
Nitrifyingbacteria NBBART
#
fornitrifyingbacteria N/A
*NesslerandSalicylatemethodsareavailablefortotalammonia.HachCompanyrecommendstheSalicylate
method.
**TheHQdfamilyofmeterspermituseofanumberofHachssmartsensorsincludingprobesforpH,
conductivity,DOandmanyionselectiveelectrodesincludingnitrate.
***SelectfromtheHachfamilyofsccontrollersincludingthesingleordualsensorinputsc200orupto8sensor
inputsc1000
#
BARTisatrademarkandpatentedproductofDroyconBioconcepts,
Figure13:Analyticaltoolsformonitoringnitrification
18
AnalyticalLaboratoryMethodsforMeasurementofChlorineResiduals

Therearemanypossiblemethodsfordeterminationofchlorineresidual.Onlytwoanalyticallaboratorymethods
arewidelyusedfordaytodayoperationaluse,theDPDmethodandamperometrictitration.Thetablebelow
summarizesbasicinformationaboutthesemethods.

Method*
AnalysisRange,
mg/l
Estimated
Precision**
Application
TechnicianSkill
Level***
DPD
Colorimetric
05 12% FreeandTotal 1
UltralowRange
Colorimetric
00.500 56% Total 2
FEASTitration
03 27% FreeandTotal 2
AmperometricTitration

ForwardTitration
Upto10 12% FreeandTotal 3
BackTitration
0.0061.00 15% Total 3
*SeeAppendixAfordetailsaboutorthotolidineandsyringaldazine(FACTS)methods.Thesemethods
areinfrequentlyused
**%RelativeStandardDeviation
***Technicianskilllevel:1Minimaltraining2Moderatelyskilledwiththemethod
3Experiencedwiththemethod
Figure14:ComparisonofDPDandAmperometricLaboratoryMethodsforFreeandTotalChlorine
DPDColorimetricandTitrimetricMethods

Dr.ThomasPalinintroducedtheDPD(N,Ndiethylpphenylenediamine)methodforresidualchlorinein1957.
Overtheyearsithasbecomethemostwidelyusedmethodfordeterminingfreeandtotalchlorineinwaterand
wastewater.HachCompanyintroduceditsfirstchlorinetestkitbasedontheDPDchemistryin1973.
Liquidvs.PowderedReagents

Procedurespublishedinwidelyusedmethodmanuals(i.e.StandardMethods)callforliquidDPDreagents
preparedfromDPDsulfateorDPDoxalatesalts.

LiquidDPDreagentsaresubjecttooxidationfromeitheratmosphericoxygenordissolvedoxygenpresent
inthepreparationwater.OxidationofDPDbyoxygenispHdependent(StandardMethods,20
th
ed.).The
liquidDPDformulationsattempttoretardoxidationbyloweringthepHoftheindicatorreagent.
Theliquidformulationsincorporatedisodiumethylenediaminetetraacetate(Na
2
EDTA)inordertoretard
deteriorationduetooxidationand,inthetestitself,providesuppressionofdissolvedoxygenerrorsby
preventingtracemetalcatalysis(StandardMethods,20
th
ed.).
19
PhosphatebuffersusedinStandardMethodsadjustthesamplepHtobetween6.26.5.Theslightly
acidicpHispreferredtoresolvethechloraminespeciesquantitativelyandtominimizeinterferences.
Phosphatebuffers,however,donotperformwellinhardorbrackishwaters.Calciumandmagnesium
ionsinthesamplewillprecipitatethephosphateanddestroythebufferingcapacity(Sengupta).Because
aqueousphosphatesolutionsareexcellentgrowthmediaformicroorganisms,highlytoxicmercuric
chlorideisaddedtopreservethereagent.

HachCompanyDPDpowderformulationsovercomethedisadvantagesofusingliquidreagents.HachsDPD
indicatorandbuffer,combinedinpowderform,minimizedegradationbyoxidationandmicrobialaction.Hachs
DPDpowderindicatordoesnotexistinanionizedstatethusisnotsubjecttoairoxidationasisliquidDPD
reagent.Thecombinedreagentsareformulatedtopreventmetalcatalyzedoxidation.

Hachsbuffermakesuseofacarboxylatephosphatesystemthatworksextremelywellinhighhardnessand
brackishwatersamples.Thereagentscantolerateupto1000mg/lasCaCO
3
hardnesswitheitherthefreeor
totalchlorinepowderformulations.HachCompanyDPDformulationsdonotcontainmercuricsalts.

Figure15:FoilpackagedDPDFreeChlorineReagent
HachCompanysDPDpowderPermaChem

Reagentsarequitestablewhenprotectedfromtemperature
extremes.Excellentreagentstabilityisachievedbysealingthereagentinunitdosefoilpouchesthatprotect
themfromexposuretoair,moistureandlight.TheDPDpowderedreagentsarealsoavailableinAccuVac

DPD
reagentampules.

Figure16:ChlorineResidualAccuVacAmpules
Theampulesareairevacuatedtoprotect
reagentsfromoxidationandmoisture.Storage
containersprotectthereagentsfromexposureto
sunlight.Storagecontainersshouldbekept
closedbetweenusestoprotecttheampulesfrom
light.AllofHachsDPDreagents,bothliquidsand
powders,shouldbestoredbetween10to25C
(5077F)forgreateststability.

20
HachCompanyusesliquidformulationsfortheCL17onlinechlorineanalyzer
4
andforHachsUltralowRange
DPDmethod,describedbelow.OnecanusetheCL17liquidreagentsinthelaboratory.
DPDColorimetricMethod

ThefollowingfiguredepictsreactionofchlorinewithDPD.ChlorineoxidizestheDPDaminetotwooxidation
products.

AtanearneutralpH,theprimaryoxidationproductis
asemiquinoidcationiccompoundknownasa
Wrsterdye.Thisrelativelystablefreeradicalspecies
accountsforthemagentacolorintheDPD
colorimetrictest.Continuedoxidizationformsa
relativelyunstable,colorlessiminecompound.When
DPDreactswithsmallamountsofchlorineatanear
neutralpH,theWrsterdyeistheprincipaloxidation
product.Athigheroxidantlevels,theformationofthe
unstablecolorlessimineisfavoredresultingin
apparentfadingofthecoloredsolution.

TheabsorptionspectrumoftheDPD
Wrsterdyeindicatesadoublet
peakwithmaximaat512and553
nm.
HachCompanyuses530nmasthe
measuringwavelengthformostof
itslaboratoryDPDsystems.This
relativelybroadsaddlebetween
thepeaksminimizesanyvariationin
wavelengthaccuracyamong
differentinstrumentsandextends
theworkingrangeoftheteston
someinstruments.Italsopermitsaccuratemeasurementswithaninexpensivecolorimeter.TheUltralowRange
methodusesawavelengthof515nm.Therelativelysteepslopeat515nmmakesitnecessarytousea
spectrophotometerfortheUltralowRangemethod.TheCL17Analyzeroperatesatawavelengthof510nm.
DPDTitrationMethod

TheDPDtitrationmethodusesaferrousreducingagentasthetitrantsolution.DPDisoxidizedbychlorine(or
iodineinthecaseofchloramines)tothemagentacolorspecies.Thesolutionthenistitratedtoacolorlessend

4
TheDPDpowderedindicatorandtheliquidsolventfortheindicatorarekeptseparateandmixedimmediatelypriortouse.
Therefore,thereagentstabilityisnotaffected.
Figure17:DPDchlorinereactionproducts
Figure18:AbsorptionspectraforDPD
21
point.Thetitranttypicallyusedisasolutionofferrousammoniumsulfate(FAS),(NH4)
2
Fe(SO
4
)
2
6H
2
O.FAS
titrantsolutionisunstable(typicallyonemonthshelflife).FASissubjecttooxidationandrequiresfrequent
standardizationagainstapotassiumdichromatesolution.

HachCompanysuggeststheuseofferrous
ethylenediammoniumsulfate,FEAS,FeC
2
H
4
(NH
3
)
2
(SO
4
)
2
4H
2
O
(Oespersreagent)forthetitrant.HachCompanypreparesthe
FEAStitrantandpackagesitinasealedDigitalTitratorCartridge
thuspreventingitsexposuretoair.Hachspreparationand
packagingofthereagentprovidesashelflifeofuptosix
months.

DPDUltraLowRangeColorimetricMethod

HachCompanyhasdevelopedastableliquidDPDreagentsystem(U.S.PatentNo.5,362,650)forusein
determinationofultralowrange(ULR)levelsoftotalresidualchlorine.Thisreagentisforuseintrace
determinationsoftotalchlorineinwaterandwastewater.Liquidreagentsarepreferredfortracelevelsof
chlorinelessthan20g/l(ppb).

Tracedeterminationofchlorinerequireshighpuritybufferandindicatorcomponents.PowderedDPDreagents
typicallyleaveaverysmallamountofundissolvedresiduewhenaddedtothewatersample.Althoughthe
resultingturbidityisinsignificantinnormalmeasurements,itmaybesufficienttointerfereintracecolorimetric
measurements.

Organicbufferimpuritiescanexhibitachlorinedemandwhenaddedtoasamplecontainingtraceamountsof
chlorine.Asstatedpreviously,phosphatebuffersgenerallyareproblematicinsamplescontaininghardness.
Liquidphosphatebufferscancontaininsolubleimpuritiesormicrobiologicalgrowthsthatmaycauseturbidity
whenaddedtothesample.IodideoftencontainsiodineoriodateimpuritiesthatreactdirectlywiththeDPD
indicator.Exposuretooxygenandlightwillgraduallyconvertiodidetotriiodideioneveninthesolidstate.

HachsULRreagentsaddresstheseproblems.Thespecially
compoundedULRChlorineBufferisfreefromanychlorinedemand.
CarefulpreparationofIodidecontainingreagentminimizesoxidation
impurities.TheULRChlorineBufferandULRDPDIndicatorsolutions
aresealedinunitdoseampulesunderargongas.Anamberglass
ampuleisusedforthebuffersolution.Bothsolutionsshouldbe
protectedfromambientlightduringstorage.

Figure19:DPDFASorDPDFEASTitration
Figure20:AmpuledReagentsfortheHach
UltralowRangechlorineresidualtest
22
ShelflifestudiesindicatetheULRDPDreagentsexhibitnolossinsensitivitytochlorineoveraoneyearperiod
whenproperlystored.

Anotherimportantconsiderationfortraceanalyticalmeasurementsisthereagentblank.Reagentblankisthe
amountofinterferencecontributedonlybytheadditionofthereagents.IntheDPDcolorimetrictestforchlorine,
oxidationoftheDPDindicatorgivesthesamecoloredWrsterdyeproductasthereactionoftheDPDindicator
withchlorine.

WhenDPDreagentisaddedtoasamplecontainingchlorine,theabsorbancemeasuredwillbethesumofthe
DPDchlorinereactionproductandtheoxidizedDPD(reagentblankvalue).Contributionofthereagentblankis
insignificantforhigherrange(mg/l)measurements.However,onemustaccuratelycompensateforreagentblank
whenmakingtrace(g/l)measurements.

Ideally,theamountofcolorduetothereagentadditioncanbedeterminedbyusingasampleknowntocontain
nooxidant.Unfortunately,atrulyoxidantfreesampledoesnotexist.

HachCompanysproceduretodeterminethereagentblankvaluefortheULRDPDmethodusesdechlorinated
samplewithoutaffectingthecolorcontributedbytheindicatorreagent.

Inthereagentblankcompensationprocedure

Anagentisaddedtothesampletoremovefreeandcombinedchlorine.
Next,indicatorandbufferreagentsareaddedtothedechlorinatedsample,followingthenormaltest
procedure.
Measuretheresultingabsorbanceandthenuseittocorrecttheactualsampleanalysisresults.

Consistentreagentblankvalues,equivalenttolessthan3g/lchlorine,areobtainedwhenusingtheULRDPD
reagents.UsingHachCompanysmethodforULRtotalchlorinetesting,chlorineresidualsaslowas2g/lcanbe
determined.ThislevelofdetectionwasdeterminedusingtheU.S.EnvironmentalProtectionAgency(USEPA)
procedureforestimatingthemethoddetectionlimit(MDL,Title40,andCongressionalFederalRegister;
AppendixB,Section136,7194.).

Theupperrangeforthetestis500g/l(0.5mg/l)asCl
2
.Monitoringapplicationsforthetotalresidualchlorine
ULRDPDmethodincludedechlorinationoffeedwatertoreverseosmosismembranesorionexchangeresins,
makeupwaterforthepharmaceuticalandbeverageindustries,andwastewaterdischargetomeetNPDES
requirements.

In1993,anumberoftestswerecompletedcomparingHachCompany'sultralowrangechlorineDPD(ULRDPD)
methodtotheStandardMethodsbackamperometrictitrationmethod(4500ClC.)usingiodinetitrant.Treated
wastewatersamples(seeCompensationforSampleColorandTurbidity,below)wereobtainedfromlargeand
smallpubliclyownedtreatmentworks,anelectricutility,anationalsecurityinstallation,aninorganicchemical
manufacturerandanorganicchemicalmanufacturer.Thesamplesrepresenteddiversematricesofdomestic
sewageeffluents,coolingwater,boilerblowdownandmanufacturingwastes.
23
Chlorinedemandofthesampleswassatisfiedwithasuitableamountofhypochlorite.Whileaginginthedark
undernitrogengas,thesampleswerechlorinatedtoobtaintotalchlorineresidualbetween5400g/l.Aliquots
weretestedbyboththeULRDPDandamperometricbacktitrationmethods.Atleasteightdatapairs(ULRDPD
vs.amperometric)werecollectedforeachsamplewithinthe5400g/lchlorinerange.Inaddition,asecond
aliquotofeachsamplewastestedbythetwoanalysismethodsafterbeingtreatedwithsmallamountofknown
hypochloriteaddition(aspike).Thisprovidedanestimateoftheaccuracyofthemethods,aspercentrecovery
ofthespike.

Figure21:ComparisonofHachsULRTotalChlorineResidual
methodwithamperometrictitration
Thefigureillustratestheresultsofthemethod
comparisonstudyofallpaireddata.The45line
representsidealcorrelationbetweenthetwo
analyticalmethods.Statisticalevaluationofthe
data,usinganalysisofvarianceandapairedttest
ata95%confidencelevel,indicatedmeasurements
madewiththeULRDPDmethoddidnotdiffer
significantlyfrommeasurementsmadewiththe
amperometricmethodwithinthisconcentration
range.

TheULRDPDmethodisUSEPAacceptedfortotalchlorinedeterminationsindrinkingwaterandwastewaters.
IndophenolMethodforMonochloramineinWaterandWastewater

Watersystemspracticingchloraminationandwastewaterfacilitiesneedtomeasuremonochloramine.Ithas
beencommonpracticetoattempttoestimatemonochloraminebysimplymeasuringfreeandtotalresidual
chlorineandthenassumingthedifferenceismonochloramine.Thatapproachisaveryinaccurate.Numerous
referencetextsincludingStandardMethods,20
th
ed.,5
th
ed.ofWhitesbookandtheHachWAHcontain
instructionsformeasuringandspeciationoffree,totalresidualchlorine,andmono,di,trichloramines.
However,theseproceduresareverytechniquedependentandtimeconsuming.Forchloramination,theprimary
specieofinterestismonochloramine;therefore,Hachchemistsdevelopedasimplemethodfordetermining
monochloramine.

Hachmethodsformonochloramineincludemethods10200forWaterand10172forwastewater(U.S.Patent
6,315,950).Themethodisbasedontheindophenolchemistryfordeterminingammonia.Thetestisspecificfor
monochloramine,withoutinterferencefromorganicorinorganicamines,dichloramine,freechlorine,organic
chloramines,nitritesormanganese.

24
ChemicalReactions

Figure22:Indophenolformationfordeterminationofmonochloramine

Monochloraminereactswithasubstitutedphenatetoformaquinoneimineintermediate.Inthepresenceofa
cyanoferrate,theintermediatecoupleswithexcessphenatetoformagreencoloredindophenolcompound.The
amountofindophenolformedisproportionaltoconcentrationofmonochloramineinthesample.

Controllingthechloraminationprocesstoproducepredominatelymonochloraminenecessitatescontrolof
ammoniatoassuretheratioCl
2
:Nislessthan5:1.Designoftheindophenoltestpermitsdeterminationoffree
ammoniaaswellsotheanalystcanassurefreeammoniaisgreaterthanzero.
IndophenolFreeChlorineMethod

Chloramine,manganeseandchromiumarepositiveinterferencesintheDPDmethod.Theprocedurefor
addressingtheseinterferencesintheDPDmethodistimeconsumingandsometimesimpossible.

HachCompanydevelopedtheIndophenolmethod10241fordeterminingfreechlorineresidual(U.S.PatentNo.
2009/0320570).Themethoddeterminesfreechlorineconcentrationswithoutinterferencefrommanganese,
chromiumorchloramines.Onlytworeagentsarerequired.

TheIndophenolfreechlorinemethodeliminatesthestandardpracticeofaddingsodiumarsenite(andthe
resultingwaste)tocorrectformanganeseorchromiuminterferenceintheDPDfreechlorinemethod.This
greenalternativemethodrequiresnopretreatmentsteps.

Figure23:ComparisonofDPDvs.Indophenolforfree
residualchlorineat3.1mg/linthepresenceof
manganese.
25

ChloraminesbreakthroughandcausehighresultsinaDPDfreechlorinedetermination.Thelevelof
breakthroughisdependenton
chloraminetype,concentrationaswellas
samplepHandtemperature.Oneoften
observesthepresenceofchloraminesas
aslowsteadilyincreasingfreechlorine
value.Thecurrentguidanceforanalysts
usingDPDistoreadthechlorineassoon
aspossible(withinoneminute)to
minimizetheinterference.Indophenol
method10241forfreechlorine
eliminateschloramineinterference.

Figure26:ChloramineinterferenceintheDPDfreechlorinetest
vs.Indophenolfreechlorinetest
Figure25:ComparisonofDPDvs.Indophenolfor
freeresidualchlorineat0.12mg/linthepresence
ofmanganese.
Figure24:ComparisonofDPDvsIndophenol
forfreeresidualchlorineat1.0mg/linthe
presenceofmanganese.
26
MethodDescription

Collectasampleandsplitintotwoportions,asampleandablank.
Treatoneportion,theblank,withadditionofMonochlorFReagent.
Tothesecondportion,addFreechlorFReagentSolution,Thefreechlorineinthisportionisconverted
immediatelytomonochloramine.
Thedevelopedcolorinbothportionsismeasuredwithacolorimeterorspectrophotometer.
Subtractingtheblankvaluefromthesamplevalueprovidestheconcentrationoffreeresidualchlorine.
mg/lsampleportionmg/lblankportion=mg/lfreeresidualchlorine

Colordevelopmenttimeoffiveminutesorlongerisnecessarydependinguponsampletemperature.Thistime
maybeofconcernbutitrequireslesstimethanthedechlorinationprocedureusingsodiumarseniteandtheDPD
method.Therangeofthemethodis0.044.50mg/lasCl
2
.
IodometricTitration

Thestarchiodidetitrationmethod,oneoftheoldestmethodsfordeterminingchlorine,isverynonspecificfor
oxidantsandgenerallyusedfortotalresidualchlorinetestingatlevelsabove1mg/lCl
2
.HachCompanyuses
iodometricprocedurestodeterminechlorineincommercialbleachsolutionsandinchlorinatedwastewaters.
Severaltotalchlorinetestsystemsusingtheiodometrictitrationmethodareavailablewithrangesashighasa
15%chlorinesolution.

Intheiodometrictitrationmethod,afteradditionofpotassiumiodide(KI)tothesample,chlorinereactswiththe
KItoproduceIodine
5
.Theiodinethenreactswithsodiumthiosulfate(Na
2
S
2
O
3
)titrantsolution.Starchisusedas
anindicator:
Cl
2
+ 3KI I
3

+ 3K
+
+ 2Cl

I
3

+ 2Na
2
S
2
O
3
3I

+ 4Na
+
+ S
4
O
6
2

Theendpointofthetitrationcorrespondstothedisappearanceofthebluecolored,starchiodidecomplex.The
pHrangeforthetitrationisusually34.ResearchbyHatchandYangdeterminedthatsampletemperaturesabove
20Ccouldintroducesignificanterrorsintheiodometrictitration.Thus,itisadvisabletoconductiodometric
titrationsatasampletemperaturelessthan20C(68F).

Backtitrationforsamplescontainingpotentialchemicalinterferencesisrecommended.Inthiscase,adda
knownamountofthiosulfateinexcesstothechlorineinthesample.Theamountofunreactedthiosulfateis
titratedwithastandardiodinesolution.Thetotalchlorine,basedonthethiosulfateequivalencyinthesample,is
thencalculated.Thechemicalreactionsare:
Cl
2
+ 2S
2
O
3
2
2Cl

+ S
4
O
6
2
I
3

+ 2S
2
O
3
2
(excess)
3I

+ S
4
O
6
2

5
Moleculariodine(I
2
)inaqueoussolutionistypicallypresentasatriiodideionI
3

.
27
AmperometricTitrationMethods

Amperometryisanelectrochemicaltechniquethatappliesasmallelectricalvoltageacrosstwoelectrodesand
measuresthechangeincurrentresultingfromthechemicalreactionstakingplace.Amperometrictitration
measuresthecurrentchangeasafunctionoftitrantadded.Typicalamperometrictitrationinstrumentation
includesaprobeorcellcontainingdualplatinumelectrodes(biamperometric)ortwodissimilarelectrodes(for
example,silver/platinum),amicroamperemeterandatitrantdispensationdevice.Sodiumthiosulfateor
phenylarsineoxide(PAO)titrantsmaybeused.ThefigurebelowillustratesPAO(b)istypicallypreferredasit
providesasharperendpointthanthiosulfate(a).

Figure27:Thiosulfatevs.PAOTitrantforAmperometricTitration.
Thereareapplicationsforbothforwardandbacktitrations.Forwardtitrationdescribesaprocessofaddinga
standardreducingtitrantsolutiontothesampleuntiladefinedendpointisreached.Backtitrationdescribesa
processwhereasampleisfixedbyaddingexcessreducingagentandthentheexcessistitratedtoanendpoint.

Figure28:Forwardtitration(left),Backtitration(right)
28
AmperometricTitrationforFreeResidualChlorine

Freeresidualchlorinedeterminationusingforwardamperometrictitrationinvolvestitrationwithastandard
reducingagentsuchasphenylarsineoxide(PAO)atpH7.Asmallpotentialisappliedacrosstheelectrodesbefore
thetitrationbegins.Anelectricalcurrentcannotflowbetweentheelectrodesunlesstwosubstancesarepresent
oneisoxidizedattheanodeandanotherreducedatthecathode.Duringthecourseofthetitration,free
chlorineisreducedatthecathodetochloride(Cl

)fromthereactionwithPAOtitrant.Arsenic(As)inthePAOis
oxidizedfromthe+3tothe+5attheanode:

Figure29:AmperometricForwardTitrationforFreeResidualChlorine
PhAsO + HOCl

+ H
2
O PhAsO(OH)
2
+ H
+

+ Cl

PhAsO + OCl

+ 2H
2
O PhAsO(OH)
2
+ H
2
O + Cl

Or
PhAsO + Cl
2
+ 2H
2
O PhAsO(OH)
2
+ 2H
+
+ 2Cl

(Ph=C
6
H
5

,phenyl)
Aslongastheoxidant(freechlorine)ispresentinthetitratedsample,currentflowsthroughthecell.Whenallof
theoxidantisreacted,therateofcurrentchangeiszero,signalingtheendpointofthetitration.Afterreaching
theendpoint,thesolutioncannotconductelectricalcurrenteventhoughadditionofPAOcontinues.Theamount
ofPAOusedatthetitrationendpointisproportionaltothechlorineconcentrationinthesample.Thekeyis
accuratelydeterminingwhentheelectricalcurrentiszero.
AmperometricTitrationforCombinedandTotalResidualChlorine

Inthecaseofchloramine(monochloramineanddichloramine)determination,thepHisloweredto4and
potassiumiodideisaddedtoconvertthechloraminespeciestoanequivalentamountoftriiodideion(I
3

):

NH
2
Cl + 3I

+ H
2
O + H
+
NH
4
OH + I
3

+ Cl

NHCl
2
+ 3I

+ 2H
+
+ H
2
O NH
4
OH + I
3

+ 2Cl

29
ThetriiodideistitratedwithPAOwiththecurrentchangemeasuredamperometrically:

PhAsO + I
3

+ 2H
2
O PhAsO(OH)
2
+ 2H
+
+ 3I

Onecandeterminemonochloramineanddichloramineseparatelybyperformingasequentialtitration:

First,inthepresenceofpotassiumiodideatpH7,titratetodeterminemonochloramine.Theamountof
titrantrequiredisrecorded.
DeterminedichloraminebyloweringthepHto4andmoreaddiodide.Continuetitrationtoresolvethe
dichloraminefraction.

Titrantmustbeaddedinslightexcess(overshot)toassuretheendpointhasbeenreached.Onemustaccount
forexcessvolumeoftitrant.Thispracticeleadstosomeambiguityinthedeterminationofmonochloramineand
dichloraminefractions,especiallywhendetermininglowconcentrations.

Totalresidualchlorineconcentrationcanbemeasuredbysequentialtitration:

First,thefreechlorineresidualisdeterminedasabove.
Thenpotassiumiodide,KIisaddedandthepHadjustedto4.Thetitrationisresumed.Totalresidual
chlorinethenisthetotalamountofPAOtitrantusedinbothsteps.
Iftotalresidualchlorineistheonlyinterest,treatthesampleimmediatelywithKI,adjustthepHtoabout
pH4andthentitratewithPAOuntilthereiszerochangeinthecurrentflow.

Someusersattempttodeterminetheendpointbysimplevisualobservationofthecurrentflowtodeterminethe
zeroendpoint.Determiningtheendpointgraphicallyismoreaccurateandprecise.
BacktitrationforTotalChlorine

Backtitrationiswidelyusedforthedeterminationoftotalchlorineinwater.Theamperometricbacktitration
methodhasbeenpopularinwastewaterlaboratoriesfortworeasons:

1.Thesamplechlorinecanbefixedatthesamplingsitewiththeadditionofexcessreducingagent
(reductant).
2.Thereislessinterferencefromiodinedemandsubstancesinthesample.Beginningofcurrentflow
betweentheelectrodescorrespondstothepresenceoffreeiodine(triiodideion,I
3

)andsignalsthe
endpointoftheamperometricbacktitrationprocedure.

Amperometrictitrationsrequireahigherlevelofskillsandcarethanthecolorimetricmethodsforchlorine
analysis.Somereferencesconsidertheamperometricmethodtobethestandardofcomparisonfordetermining
freeortotalchlorine.Thereisconsiderableconflictinginformationaboutinterferencesintreatedwastewater
andeffluents(seeInterferencesintheAmperometricMethods,below).

30
Mostconventionalamperometrictitrationsystemsrelyonthetechniciantodeterminevisuallythetitration
endpointbyobservingchangesinadigitaloranalogmeter.Ineithercasetheoperator,throughobservationof
themetersdisplayissupposetojudgewhenthecurrentflowexactlyreacheszeroinforwardtitrationsor
becomespositiveinbacktitrations.

HachCompanyofferstheAutoCAT9000AmperometricTitrator.
Theinstrumentsmicroprocessorcontinuouslymonitorsthe
titration.Theunitcollectsandplotsmultiplepointsbeforeand
aftertheendpointisreached.Themicroprocessorcalculatesthe
exactendpoint.

UseofStandardsandDevicesforMethodAccuracyandPerformanceVerification

Standardsarerequiredtoestablishaccuracyofanyanalyticalmethod.

Ifstandardsarenotused,inconsistentresultscanleavetheanalystwonderingabouttheaccuracyofthe
instrument,reagent,andtechnique.Knowingthatstandardresultsarecorrectcanhelpinmanyways:

Usestandardstoestablishtheentiretestsystemisfunctioningcorrectlybeforespendingtimeand
reagentstestingactualsamples.
Usestandardstohelpevaluateandimprovetheskillsandtechniquesoftheanalyst.
Usestandardstoprovideproofofaccuracyforregulatorycomplianceorcustomers.
Usestandardstocompareperformancebetweentwoinstruments,forexample,alaboratory
spectrophotometerwithanonlinechlorineanalyzer.Ifreadingsfromanonlinechlorineanalyzerand
laboratoryinstrumentdonotmatch,theanalystshouldrunastandardtotroubleshootanddetermine
whethertheerrorisinthelaboratoryorwiththeonlineinstrument.However,thefirststepshouldbeto
ensurethelaboratoryandonlineanalyzersareusingexactlythesamesample!

Figure31:TypicalForwardTitrationforfreeresidualchlorinewhenusing
theHachAutoCAT9000AmperometricTitrator.
Figure30:AutoCAT9000Amperometric
Titrator
31
Runningastandardsolutionmaynotprovideananswertoameasurementproblem,butitnarrowsdownthe
troubleshootingoptionsinanotherwisecomplicatedsituation.Formoreinformationaboutuseofstandardsand
qualitycontrol,thebooklet,AnIntroductiontoStandardsandQualityControlfortheLaboratory,isavailablefor
downloadatwww.Hach.com.
LowLevelChlorineStandardsforMethodVerification

Whenusingstandardsformethodverification,oneperformsananalysisofastandardatasimilarconcentration
tothatofatypicalsample.However,suchaprocedureisnotalwaysfeasible.Suchisthecasewithlowrange
chlorineanalysis.

Forverificationoflowrangechlorineanalysis,Hachrecommendsthepreparationofchlorinestandardsolutions
atconcentrationsnolowerthan0.10mg/l.

Itisimportanttounderstandthepracticallimitationsofpreparingalowlevelchlorinestandard.Someofthe
potentialerrorsourcesinthepreparationofalowconcentrationchlorinestandardsolutioninclude:

1.DilutionWaterThedilutionwaterusedtoprepareachlorinestandardmustbechlorinedemandfree.For
accurateresults,thewaterusedtoprepareachlorinedilutionshouldbe18megaohm,organicfree(<20g/l
oftotalorganiccarbon),amineandaldehydefree,andsterile(thiscanbeachievedbyfiltrationthrougha0.2
mfilter).OnemayfollowtheprocedureinStandardMethods,20
th
ed.,method2350Btodeterminechlorine
demandofthedilutionwater.
2.AtmosphericExposureToavoidoxidationandlossofchlorine,lowlevelchlorinestandardsmustbe
preparedunderahighpurityinertgasheadspace.Nitrogenandargonareacceptablegasestouseinthis
application.Avoidcontactwithatmosphericgases,ammoniavaporsandexposuretoambientlight.
3.ContainersThecontainersinwhichchlorinestandardsarepreparedandhandledwillaffectaccuracy.Itis
importantthatallcontainersbechlorinedemandfree.Avoidplasticcontainersastheycanleachorganicsinto
waterandbeasourceofchlorinedemand.Glass,Teflon,andPETarepreferredmaterialsforwettedpartsof
thesystem.Pretreatallpartsforchlorinedemandbysoakinginadilutebleachsolution(5dropsof
commercialbleachperliterofwater)followedbyrinsingwithcopiousamountsofchlorinedemandfree
deionizedwater.Avoidamberglasscontainers.
4.pHThesolutionpHalsoaffectsthestabilityofapreparedchlorinestandardsolution.Chlorineismorestable
ashypochloriteion(pHgreaterthan9)thanashypochlorousacid.Chlorinestandardsolutionspreparedin
deionizedwateraretypicallylessthanpH9.Thus,thepreparedstandardsolutionisunstableandmustbe
preparedimmediatelypriortoanalysis.
5.EquivalentStandardsWiththemanypotentialsourcesoferrorinthepreparationofchlorinestandard
solutions,itmaybetemptingtoprepareachlorineequivalentstandardfrompotassiumpermanganate.Hach
Companydoesnotrecommendtheuseofpermanganatestandardsforchlorineverification.Precautions
UsingPermanganateasanEquivalentStandard,below,containsmoredetailedinformation.

Themanysourcesofpotentialerrormeanthattheactualconcentrationofthestandardsolutionmaynotmatch
itstheoreticalcalculatedconcentration.Theactualconcentrationofthepreparedchlorinestandardusedfor
verificationshouldbedeterminedthroughaseparatereferencemethod,suchasamperometrictitration.
32
Amperometrictitrationistraceabletoaprimarystandard.ThePAOtitrantistraceabletoarsenictrioxide,a
primarystandard.UseaninstrumentsuchastheAutoCAT9000AmperometricTitratortostandardizePAOversus
arsenictrioxide.AcertificateofanalysisforthePAOtitrantisalsoavailablefordownloadfromwww.hach.com.

Additionally,thecalibrationcurvesforcolorimetricchlorineanalysesprogrammedintoHachcolorimetersand
spectrophotometersaretheresultofmultiplestandards(referencedtoamperometrictitration)analyzedwith
multiplelotsofreagent.Verificationofthemethodwithchlorinestandardsisrecommendedadjustmentofthe
existingcalibrationcurveorrecalibrationoftheinstrumentsisnotrecommended.

Standardadditions(samplespike)isanothermethodforverification.Proceduresforstandardadditionsare
publishedintheAccuracyCheck,StandardAdditionsMethodsectionofmanyHachproceduresorintheHach
WaterAnalysisHandbook.Chlorinatedwastewaterortapwatershouldbedechlorinatedbyexposureto
ultravioletlightUV,priortotheadditionofachlorinespike.Chemicalmethodsofdechlorinatingcannotbe
used,asanyresidualofthedechlorinatingagentwouldinterferewiththespike.

HachCompanyrecommendsthestandardadditionstechniqueusingChlorinePourRite

AmpuleStandardsor
Voluette

AmpuledStandards
6
forroutineverificationofpreprogrammedcalibrations.

Figure32:PourRite(left)andVoluetteAmpuleChlorineStandardSolutions
TheChlorineampuledstandardsarepureaqueousfreechlorinesolutionspreparedintworanges,2530mg/l
(PourRiteampules)or,5075mg/lchlorine(PourRiteorVoluetteampules).Theactualvalueisprovidedforeach
lotofstandards.HachCompanyresearchhasshownthattheampuledchlorinestandardsexhibitexcellent
stability,whenstoredattemperaturesbetween2to8C(33to47F.).Useasimpleproceduretoverifythe
accuracyofthechlorinecalibration.Forexample:

a) SnapthetopoffaChlorinePourRiteorVoluetteAmpuleStandardSolution.
b) UsetheTenSette

Pipettoadd0.1,0.2and0.3mlofstandardtothree25mlsamples.Swirlgentlytomix.
c) AnalyzeeachsampleimmediatelypertheHachDPDcolorimetricprocedures.
d) Each0.1mlofstandardwillcauseanincrementalincreaseinchlorinecontent.Theexactvaluedependson
theactualconcentration.

6
PourRiteAmpuledStandard,2mleach,20/pkg;VoluetteAmpuledStandard,10mleach,16/pkg
33
Checkthecertificateenclosedwiththeampulesforthisvalue.RefertoHachCompanysWaterAnalysis
Handbook,formoreinformationonthestandardadditionstechniqueforverificationofaccuracy.

Ifyouhaveanyquestionsorconcernsregardingthepreparationofchlorinestandardsolutionsformethod
verification,contactHachTechnicalSupportat18002274224oremailtechhelp@hach.com.
PrecautionsUsingPermanganateasanEquivalentStandard

StandardMethods,20
th
ed.,containsinstructionsforusingdilutesolutionsofpotassiumpermanganateas
equivalentstandardsforestablishingachlorinecalibration.AsnotedbyGordon,etal.permanganateoxidizes
DPDtoboththecoloredandcolorlessoxidationproduct.

HachCompanyresearchershavenotedtheorderofaddingreagenttosamplewillaffecttheratioofoxidizedDPD
products.Forexample,ifthepermanganateequivalentstandard
isplacedinacontainer(suchasaDRsamplecell)andthefreechlorinereagentisaddedtoit,theoxidantisin
excessduringtheadditionprocess.Therefore,moreofthecolorlessimineproductcanform,resultinginless
colorinthetest.

Conversely,addingfreechlorineDPDindicator/bufferreagentinthesamplecellandthenthepermanganate
solution,theDPDindicatorremainsinexcess,withproperformationofthecoloredproduct.Inpracticalterms,
thedifferencesbetweenreagenttosampleandsampletoreagentadditionsusingpermanganatestandardsand
HachsDPDreagentarerelativelysmall.

Equivalent
mg/lCl
2
Reagentaddedtosample Sampleaddedtoreagent Difference
Abs Conc.mg/l Abs Conc.mg/l Abs Conc.mg/l
0.20 0.108 0.20 0.109 0.21 0.001 0.01
0.50 0.271 0.51 0.271 0.51 0.000 0.00
0.80 0.427 0.80 0.432 0.81 0.005 0.01
1.00 0.530 0.99 0.543 1.02 0.013 0.03
1.20 0.613 1.15 0.632 1.19 0.019 0.04
1.40 0.727 1.36 0.743 1.39 0.016 0.03
1.50 0.764 1.43 0.791 1.49 0.027 0.06
1.60 0.815 1.53 0.834 1.57 0.019 0.04
1.80 0.920 1.73 0.928 1.74 0.008 0.01
MeanDifference 0.012 0.03
StandardDeviation 0.009 0.02
Range 0.027 0.06
UsingHachCompanysDPDFreeChlorinePowderPillows,Cat.No.14070,andusingaHachDR3000
Spectrophotometerwithpreprogrammedcalibrations.1995
Figure33:OrderofSampletoReagentAdditionUsingPermanganateEquivalentStandards
Thefigureaboveillustratesthedifferencesobtainedoveraseriesofpermanganatestandardsintherangeof0.2
1.8mg/laschlorine.Theaveragedifferencebetweenthetwoadditiontechniqueswas0.03mg/laschlorine.The
34
greatestdiscrepancieswerenotedatconcentrationsgreaterthan1.0mg/l.Theorderofadditioneffecthas
beennotedonlywhenusingpermanganate.

Afewprecautionsinthepreparationanduseofpermanganatestandards:

Glasswareusedinthepreparationanddilutionofpermanganatesolutionsshouldbetreatedwith
chromicacidcleaningsolutiontoremoveanyorganiccontamination.Thenrinsetheglasswarecopiously
withloworganicswater.
Waterusedfordilutionofstockpermanganatesolutionshouldbelowinorganicsandshouldexceed
AmericanSocietyforTestingandStandards(ASTM)TypeIqualityspecifications.Dilutionwaterfor
permanganateshouldneverbestoredinplasticcontainersorexposedtoairbornecontamination.
Standardizethestocksolutionroutinelywithdriedsodiumoxalate(Vogel).
Diluteequivalentstandardsarenotstableandshouldbepreparedasneeded.Neverstoredilute
permanganateinplasticcontainers.

Becauseoftheseconstraints,HachCompanydoesnotrecommendtheuseofpermanganateequivalent
standardswithHachDPDreagents.
UseofSpecColorStandards

HachCompanymanufacturesSpecColorStandardsforusein
rapidmethodperformancechecks.Thestandardsareagel
coloredtosimulatespecificconcentrations.Threesetsare
availablefortheDPDchlorinemeasurement.

Method Concentration
DPDChlorine
Lowrange
02mg/lCl
2

Midrange
04mg/lCl
2

Highrange
06.5mg/lCl
2

Indophenolmethodfor
ammonia/monochloramine
Freeammonia(00.50mg/lNH
3
N),
Monochloramine(04.5mg/lCl
2
)
Ozone 00.75mg/lO
3

Fluoride 02.00mg/lF

Figure35:SpecColorStandards
Eachsetincludesthreedifferentcolorstandardsandablank.SpecColorStandardscanbeusedwithallHach
Companycolorimetersandspectrophotometers.

Figure34: SpecColorStandardsforDPDChlorine
35
MethodInterferencesandSourcesof Errors
SamplingConsiderations

Perhapsthemostcommonsourceoferrorintestingforchlorineinwateristhefailuretoobtainarepresentative
sample.Becausefreechlorineisastrongoxidizingagent,itsstabilityinnaturalwatersisrelativelylow.Chlorine
readilyreactswithvariousinorganiccompounds.Itwillslowlyoxidizeorganiccompounds.

Variousfactors,includingreactantconcentrations,pH,temperature,salinityandsunlight,influencethe
decompositionoffreechlorineinwater.Monochloramine,ontheotherhand,ismuchmorepersistentinthe
environment.Typically,thedecayrateofmonochloramineistenfoldslowerthanthedecayoffreechlorinein
naturalwaters(Jolly,et.al.).

Ideally,analyzesamplesforchlorineonsite.Ifsamplingfromatap,allowwatertoflowatleastfiveminutes
beforesamplingtoensurearepresentativesample.

Samplecontainersshouldbepretreatedtoremoveanychlorinedemand.ApretreatedglassBODbottle,
withgroundglassstopper,makesanidealsamplecontainerforchlorineanalysis.Avoidplasticsample
containersbecausetheymightexertanappreciablechlorinedemand.
Pretreatcleanglasssamplecontainersbysoakinginadilutebleachsolution(1mlcommercialbleach
solutionto1literofwater)foratleastonehour.Aftersoaking,rinsethemthoroughlywithdeionizedor
distilledwaterorthesample.Anothersuchtreatmentisrequiredonlyoccasionallyifsamplecontainers
arealwaysrinsedwithdeionizedordistilledwateraftereachuse.
Ideally,separateanddedicatedsamplecontainersshouldbeusedforfreeandtotalchlorine
determinations.Traceiodide(fromthetotalchlorinereagent)maybecarriedoverintothefreechlorine
determination.Monochloraminewillinterfereinthefreechlorinetest.
Avoidexcessagitationandexposuretosunlightandhightemperatureswhensampling.Allowseveral
volumesofthecontainertooverflowandcapthesamplecontainertoeliminateheadspaceabovethe
sample.
ForonsitedeterminationsusingHachDPDcolorimetricprocedures,theoneinchsquareorcylindricalDR
cellservesasanexcellentsampler.
IfsamplingwiththeDRcell,rinsethecellwithseveralvolumesofsample;thencarefullyfilltothe25mL
(or10mL)mark.
ForAccuVacampules,collectsampleinawidemouthcontainer,suchasabeaker,rinsingseveraltimes
withsample.Immersetheampuleasillustratedatrightandsnapoffthe
neckallowingittofill.Proceedwiththeanalysisimmediately.
Iftheiodometricbacktitrationmethodsareusedfortotalchlorine
analyses,thesamplecanbefixedonsite.Thisinvolvestheadditionofa
preciseamountofstandardreducingagenttothesampleatthecollection
site.Thefixingprocedurecallsfortheadditionof1.00ml0.00564NPAOor
standardthiosulfate,potassiumiodide,and1.0mlpH4AcetateBufferinto
aclean,dryglasscontainerwithacapacityofatleast250ml(suchasaBOD
bottle).
Figure36:FillinganAccuVac
Ampule
36

o Atthesamplingsite,collect200mlofsamplewiththesamplecontainerandswirltomix.
o Minimizethedelaybetweensamplefixingandanalysis(usuallylessthanonehour)toprevent
bacterialdecompositionofPAO(orthiosulfate)excessinthesample.
o Itisimportanttotransfertheentirecontentsofthesamplecontainertotheanalysisglasswareusedin
thetitration.
InterferencesCommontoAllChlorineMethods

Allofthecommonanalyticalmethodsforchlorineorchloraminesinwaterarebasedonchemicaloxidation
reductionreactions.Eachofthechlorinemethodsdependsonthetotaloxidizingcapacityofthesamplebeing
analyzedandisreadilysubjecttointerferencesfromoxidizingagentsotherthanchlorine.Generally,allofthe
acceptedmethodsforchlorinearesubjecttopotentialinterferencesfromparticles(turbidity),color,inorganic
andorganiccompounds,andbufferingcapacity(acidityoralkalinity)ofthesample.Thereisnoidealmethod
forchlorineanalysis,whichisspecificandselectiveforthefreechlorineand/orchloraminespecies.
OtherDisinfectants

Ingeneral,allofthecommonchlorinemethodswilldetectotheroxidantsusedasdisinfectantssuchas
chlorinedioxide(ClO
2
),ozone(O
3
),bromine(Br
2
),hydrogenperoxide(H
2
O
2
),permanganateanddisinfectant
byproductssuchaschloriteandchlorateifpresentinsufficientamounts.Inthefreechlorinedeterminations,
theseoxidantscanreactdirectlywiththecolorimetricindicatorortheywillbereducedwiththiosulfateorPAOin
thetitrationmethod.Eachoftheseoxidantswilloxidizeiodidetoiodinetoacertaindegree,therebyinterfering
inthetotalchlorinedetermination.Ontheotherhand,thisinterferencemakesitpossibletousetotalchlorine
methodsfordeterminationofTRO(totalresidualoxidant)concentration,asitisrequiredinsomeapplications
(e.g.seawaterbasedtreatments).

HachCompanyhasdevelopedmethodsbasedonstandardchlorinechemistriesforBr
2
,I
2
andH
2
O
2
.Analytical
methodsthatattempttodistinguishbetweencombinationsofoxidantstrytoconvertalloxidants,exceptthe
analyte,toanonreactiveform.Inreality,therequiredadditionalmanipulationsmaymeansomelossofthe
analyte,duetotheextratimeinvolvedorchangesofreactionconditionsforthetest.
ManganeseCompounds

Manganeseisthe2
nd
mostabundantmetal(12
th
mostabundantelement)onearthandestimatedtobepresent
atnuisancelevelsinnearly70%ofwatersupplies.Manganesecanexistinoxidationstatesof+2through+7.The
higheroxidationstates,typically+3to+7,willinterferewithallthecommonchlorinemethods.Freechlorine
reactstooxidizesolublemanganesecompounds.Forexample:

Mn
2+
+ HOCl + 3OH

MnO
2
+ Cl

+ 2H
2
O

Apparently,chloramineswillnotoxidizemanganouscompounds.Oxidizedmanganesewillreactdirectlywiththe
DPDindicator.ItisclaimedthatMn
4+
doesnotinterfereintheFACTSmethodata1.0mg/llevel(Cooper,et.al.).
37
At2.6mg/lMn
4+
,interferencehasbeenobservedafterfiveminuteswiththeFACTStest.Oxidizedmanganese(+4
to+7)willalsointerfereintheamperometrictitrationmethodforfreechlorine.Iodidecanbeoxidizedby
manganese(+4to+7)toI
2
,whichwillinterfereinboththecolorimetricandtitrimetricmethodsfortotalchlorine.
Theinterferenceofoxidizedmanganeseinbacktitrationmethodsappearstobeafunctionofiodide
concentrationandthetestpH(Bongers,et.al.).

ManganeseinterferenceissocommonthattestinstructionsforHachCompanyslaboratoryandportableDPD
testprocedurescontaininstructionsforcompensatingformanganeseinterference.Thecustomaryprocedureto
compensateformanganeseinterferenceintheDPDmethodsistofirstdechlorinatethesamplewithsodium
arsenite,whichdoesnotaffectthemanganese,andthenproceedwiththetest.Theresultobtainedwiththe
dechlorinatedsampleissubtractedfromthenormaltestresulttoobtainthecorrectchlorineconcentration.

CompensatingforManganese,Oxidized(Mn
4+,
Mn
7+
)orChromium,Oxidized(Cr
6+)

1.Collectaportionofsampleandsplititintotwo10mlsamples,testportion1forchlorinefollowingthe
normaltestprocedure.Treatportion2asfollows:
2.AdjustsamplepHto67.
3.Add3dropsPotassiumIodide(30g/l)toa10mLsample.
4.Mixandwaitoneminute
5.Add3dropsSodiumArsenite1(5g/l)andmix.
6.Analyze10mlofthetreatedsampleasdescribedintheprocedure.
7.Subtracttheresultfromthistestportionfromtheresultobtainedfromtheuntreatedportion(1)to
obtainthecorrectchlorineconcentration:
mg/l(portion1)mg/l(portion2)=Correctmg/lchlorineconcentration
Figure37:Typicalprocedureforcompensatingformanganeseorchromiuminterferenceinchlorineresidualtesting.
HachCompanysuggestsuseoftheIndophenolFreeChlorineMethod(Method10241)forUseinWaters
ContainingManganeseorChloramines(seeabove)asasimpleralternativetomeasurementoffreeresidual
chlorinewithoutinterferenceduetomanganese.
OrganicChloramines

Thereisconsiderabledebateovertheinterferenceoforganicchloraminecompoundswiththecitedfreechlorine
tests.Organicnitrogencompoundscancombinewithchlorineanalogoustothereactionwithammonia:

RNH
2
+ HOCl RNHCl + H
2
O
whereR=theorganicmoiety.

Typicalorganicnitrogencompoundswouldincludecommonamines,aminoacidsandheterocyclicbases.Free
chlorinereactsquicklywiththesetypesofcompoundstoformnongermicidalorganicchloramines.While
formationoforganicchloraminesmaybemorecommoninwastewatereffluent,organicnitrogenistypically
38
absentorinverylowlevelsindrinkingwatersupplies.Still,studieshaveindicatedpossibleinterferencefrom
organicchloramineswithanalyticalmethodsforfreeandtotalchlorine.

Ingeneral,methodsthatdeterminefreechlorineandmonochloramineatneutralpHvalues(67),includingthe
amperometricmethod(forwardtitration),theDPDmethods,andtheFACTSmethod,arenotverysusceptibleto
interferencefromorganicnitrogen.Methodsthatincludedichloramineandthosethatuseacidicconditions(pH
4orlower)todeterminefreeorcombinedchlorine,suchasthestandardbacktitrationmethod,theorthotolidine
method,theLCVmethodandtheMOmethodarevulnerabletointerferencebyorganicchloramines.(White,5
th

ed.,p184.)
BromideinChlorinatedWaters

Seawaterandestuarywatermaycontainnaturallevelsofbromideionsupto65mg/l.Theadditionofchlorineto
waterscontainingbromidewillproducehypobromousacidandhypobromiteion:

Br

+ HOCl HOBr + Cl

Thisreactionisirreversibleandtheproductwillinterferewithallcommonfreeresidualchlorineanalytical
procedures.Ifammoniaispresentinthesample,HOBrwillreactwithammoniaformingbromamines.
Bromamineswillreactwithiodidereagentanalogouslytothechloraminereaction,indicatingapositive
interferenceinthetotalchlorinetest.Bromide,whenpresentinachlorinatedsample,formsadisinfectant
(hypobromiteand/orbromoamines)and,technically,theanalyticalresultswouldindicatethetotaloxidizing
capacityofthesample.Inthiscase,theanalytetermedTotalResidualOxidant(TRO)anditsconcentrationis
reportedasppmormg/lofchlorineorbromine.
ErrorsCommontoTotalChlorineDeterminations

Allofthecommontotalchlorinemethodsarebasedontheoxidationofiodidetoiodine(triiodideion)followed
bydeterminationofitsconcentration.Thereareseveralpotentialsourcesoferrorsrelatedtotheiodide/iodine
reaction,including:

Airoxidationoftheiodidereagent
Volatilizationofproducediodine
Iodineoriodatecontaminationintheiodidereagent
Consumptionoftriiodidebysamplecomponents

Potassiumiodide(KI)reagentissubjecttoairoxidationbythereaction:
4I

+ O
2
+ 4H
+
2I
2
+ H
2
O
DecreasingthepHandtracesofmetalionswillacceleratethereaction.Iodidereagentsolutionsarequite
susceptibletooxidationfromexposuretolightandoxygen.ResearchsponsoredbytheElectricPowerResearch
Institute(EPRI)hasshownanamountofoxidantequivalentto1mg/lchlorinecanbegeneratedinonedayina
0.1M(molar)KIstocksolution(Sengupta).ProvidingalkalineconditionsimprovesstabilityofKIsolutions.Itis
39
prudenttoprepareorpurchasethesolutionsinsmallquantities,storethesolutionsinambercontainers,and
protectthemfromdirectsunlightandtemperatureextremes.Italsoisimportanttocompletetheanalysis
quicklytominimizeiodinelossbyvolatilization.

Thepurityofpotassiumiodideiscriticalwhenmeasuringtotalchlorineattracelevels.Theiodideshouldbefree
ofiodineoriodate,whichcanreactdirectlywithchlorine,chloraminesortheindicatorreagentitself.Evensolid
potassiumiodidecanbeoxidizedprovidedsufficientexposuretooxygenandultravioletlightoccurs.

Adsorptionoftheproducediodineonsuspendedparticlescanbeaseriousprobleminmuddyorhighlyorganic
richwaters.AperfectexampleofthistypeofadsorptionisthebluecomplexformedbetweenI
2
andstarch,the
visualindicatorfortheiodometrictitrationmethod.Inadditiontoadsorption,iodinecanreactwithorganic
mattertoformcarboniodinebonds(Sengupta).Thisisonereasonforthetraditionalpreferenceoftheback
titrationmethodfortotalchlorineinwastewater.

InterferencesintheDPDMethods

CalibrationNonLinearity

ThereactionofchlorinewithDPDresultsintwooxidationproducts:thecoloredWrsterdyeandthecolorless
imine.TheproportionofcoloredtocolorlessproductisrelatedtotheratioofDPDindicatortooxidant.When
DPDreactswithsmallamountsofchlorine,theWrsterdyeproductisfavored.Athigheroxidantlevels,the
formationoftheunstable,colorlessimineisfavoredresultinginapparentfadingofthecoloredsolution.Itis
necessarythattheratioDPDtooxidantremainhightominimizefadingoftheresultingcolor.

Gordon,et.al.(Talanta)reportedthenonlinearityoftheDPDcolorimetricmethodcalibrationusingtheStandard
Methodsprocedure.

Theconcentrationrangeisstatedtobe04.0
mg/lCl2,usingeitherchlorinestandardsor
secondarystandardsmadefrompotassium
permanganate.GordonreportedtheStandard
Methodsprocedureusingpermanganate
exhibitedanonlinearresponseabove1.0mg/l
equivalentchlorine.HachCompanyalsohas
confirmedthenonlinearityoftheStandard
Methodsprocedureusingfreechlorine
standards.

ThenonlinearityoftheStandardMethods
calibrationisattributedtotheincreased
formationofthecolorlessimineproductat
higheroxidantconcentration.

Figure38:StandardMethodCalibrationDBDColorimetricMethod
40
IntheStandardMethodsformulation,theamountofDPDaddedtothesampleisinsufficienttooptimizethe
oxidationtotheWrsterproductstage.TheinstabilityoftheliquidDPDreagentisalsoacontributingfactorto
thenonlinearchlorinecalibration.AstheDPDindicatorsolutionages,thereislessoftheactiveDPDamineform
availabletoreactwithsamplechlorine,therebyshiftingtheratioofDPDtooxidant.ChangingtheratioofDPDto
oxidantleadstoincreasingnonlinearityatthehigherchlorinelevelsastheDPDreagentsolutionagesand
becomesoxidized.HachDPDreagentsmaintainahigherratioofindicatortooxidantandthereforedonotsuffer
thesamenonlinearityastheStandardMethodsformulations.

HachDPDpowderedformulationsoffersuperiorstabilityovertheliquidreagentformulations;therefore,a
reproducibleandlinearresponsetochlorinewillbeobtainedforalongerperiodoftime.IntheDPDtitration
methodbothDPDoxidationproductsaretitratedbytheferroustitrant.Asaresult,thetitrationmethoddoesnot
sufferfromthecolorfadingphenomenon.
MonochloramineInterferenceintheFreeChlorineTest

ThereisconsiderablecontroversyaboutmonochloramineinterferenceinthefreechlorineDPDtest.
MonochloraminebreakthroughismoreofaproblemintheDPDtitrimetricmethodforfreechlorinebecauseof
theadditionaltimenecessarytoperformthetest.StandardMethodsrecommendstheuseofthioacetamideto,
completelystopfurtherreactionwithcombinedchlorineinthefreechlorinetest.Thethioacetamide
modificationisrecommendedfortheDPDtitrationmethodforfreechlorine,ifchloraminesare0.5mg/lor
greater.

HachCompanydoesnotrecommendtheuseofthioacetamideinthefreechlorineDPDmeasurementsfortwo
reasons:

1.Thioacetamideisatoxinandconfirmedcarcinogen.
2.ThereactionofthioacetamidetopreventoxidationofDPDbymonochloramineisnotthoroughlyunderstood.
ItisnotclearifthioacetamidereducesDPDoxidizedbymonochloramineorjustreducesthecombinedchlorine.
IfitdoesreducetheoxidizedDPD,whydoesitnotreduceDPDoxidizedbyfreechlorine?

Otherreferencesciteuseofmercuricsalttoaidininhibitingmonochloramineinterference.HachCompanydoes
notuseorrecommenduseofmercuricsalts.

HachCompanysuggestsuseoftheIndophenolFreeChlorineMethod(Method10241)topreventinterference
frommanganese,chromiumorchloraminesasasimplerandsaferalternativeuseofthioacetamideormercuric
salts.(SeeIndophenolFreeChlorineMethodforUseinWatersContainingManganese,Chromiumor
Chloramines,above.)
CompensationforSampleColorandTurbidity

Onecriticalproblem,especiallywhenapplyingcolorimetricprocedurestotreatedwastewaters,isinterference
fromturbidityandcolorinthewater.Preliminaryfiltrationcanbeperformedtoremoveparticulatematterfrom
thesampleforcertainparameters.Theresidualsamplecoloriszeroedatthemeasurementwavelengthwith
41
thecolorimeter.Inmanyinstances,samplecolorandturbiditycanbecompensatedforbysimplyzeroingthe
photometerwiththesampleblankpriortoreagentaddition.Thisisappropriateformostcolorimetrictesting.

WhentestingfortracelevelsoftotalchlorineintreatedwastewaterusingHachCompanysULRDPDprocedure,
fineparticulatemattermaycauseanoiselevelofupto0.010absorbance(usinga1"pathlengthcell).This
levelofvariationisunacceptablewhenmeasuringtracecolordevelopedfromthereactionofDPDwithlow
concentrationsoftotalchlorine.Preliminaryfiltrationofthewatersampleisnotappropriatewhentestingfor
chlorine.Whetherornotchlorinelossoccursduringthesamplefiltrationdependsonthepredominantchlorine
speciespresentinthesampleandthenatureofthefiltermedia.Somelosscanbeattributedtotherelative
volatilityandinstabilityofchlorinecompoundsinnaturalwaters.Certainfiltermaterialsalsocanleadtochlorine
lossduringthefilteringprocessduetoadsorptionofthehypochloriteionsorexistingchlorinedemand.

HachCompanystudiesindicateiffiltrationisperformedafterthedevelopmentofthecoloredproduct(apost
filtration),removalofinterferingsampleturbiditycanbeaccomplishedwithoutconcernforchlorineloss.The
selectionofthefiltermediaisimportantbecausetheWrsterdyeproductisapositivelychargedion.Membrane
filtercompositionshavingasurfacechargecannotbeused.Theselectionoffilterporosityalsoiscriticalinterms
ofadequateremovaloftheparticlesizesthatcouldinterfereattheabsorptionwavelength.

IntheULRDPDTotalChlorineprocedurefortreated
wastewater,sampleturbidityisremoved,usinga
syringefilterapparatus(OrifloFilterApparatus,U.S.
Patent#5549816)withaspecialinert3micronfilter.
Apreliminaryfiltrationisperformedonthesampleto
zerothephotometer.Asecondportionofsampleis
reactedwiththereagentsandafiltrationis
performedonthereactedsample.Whenthepostfiltrationprocedureisused,thenetabsorbanceisadequately
correctedforsamplecolorandturbidity.
InterferencesintheAmperometricTitrationMethods

StandardMethodsstatestheamperometrictitrationmethodisthemethodofchoicebecauseitisnotsubjectto
interferencefromcolor,turbidity,iron,andmanganeseornitritenitrogen(Ref.3.21).Inreality,severalofthese
factorsdoaffectthedeterminationofchlorinespecieswhenusingamperometricmethods.Abriefreviewof
someofthecommonsourcesoferrorsencounteredwithrealworldsamplesfollows.

DepositiononElectrodeSurfaces:Cleanandregularlyconditionedelectrodesarenecessaryforsharp
amperometrictitrationendpoints.Becausetheelectrodescontactthesample,certainspeciesinthesample
mayplateoutorcoattheelectrodesmetallicsurface.Metallicionssuchascopper(+2),silver(+1)andiron(+3)
havebeenreportedaseitherinterferencesintheforwardamperometricmethodormaydiminishtheelectrode
Figure39:OrifloFilterApparatusand
glassfiberfilters
42
response.Insomewaters,foamingoroilysurfaceactiveagentswillcoatthemetallicelectrodes,resultingin
decreasedsensitivity.Followinstructionsfromthemanufacturerformaintainingtheelectrodesurfaces.

ManganeseInterference:Thereisacertainambiguityintheliteratureconcerningmanganeseinterferenceinthe
amperometricforwardandbacktitrationforchlorine.Asdiscussedabove,ifthesamplecontainsfreechlorine,
anysolublemanganesewillbeoxidized:
Mn
2+
+ HOCl + 3OH

MnO
2
+ Cl

+ 2H
2
O
Theoxidizedformsofmanganese(+4to+7)willtitratewithphenylarsineoxide(PAO)intheforwardtitration
procedureforfreechlorine.OxidizedformsofmanganesewillreactwithiodideatpH4,producingiodine,which
titrateswithPAO,causinganinterference.

NitriteInterference:Nitritecanexistasatransitorycompoundincertainwaters,duetothebiologicaloxidation
ofammonia:
2NH
4
+
+ 3O
2
2NO
2

+ 4H
+
+ 2H
2
O
Thereisconflictinginformationabouttheinterferenceofnitritesineithertheforwardorbackward
amperometrictitrationmethodsfortotalchlorine.Nitritesareseldomsignificantindrinkingwaterapplications.
Nitriteinterferencemaygounnoticedinwastewatermeasurements.

AccordingtoStandardMethods,20
th
ed.,nitritesdonotinterfereintheforwardtitrationmethods(4500ClD,pg
459).Insection4500ClC.1b,statesthatnitriteinterferencecanbeminimizedbybufferingtopH4.0before
additionofiodide.Itindicatesinterferencefrommorethan0.2mg/lofnitritescanbecontrolledbytheuseofa
phosphoricacidsulfamicacidreagent.

HachCompanyresearchershaveinvestigatedtheeffectofnitritesinthedeterminationofmonochloramineusing
theforwardandbacktitrationprocedures.Monochloraminewasselectedsinceitisslowtoreactwithnitrites
(Margerum,D,et.al.)andrepresentstheprimarydisinfectantformintreatedwastewater.Freechlorinehas
beenshowntoreactdirectlywithnitrites(White,3
rd
,ed.,pg226):
HOCl + NO
2

NO
3

+ HCl
Toinvestigatetheeffectofnitritesonthedeterminationoflowconcentrationsofmonochloramine,sixvariations
intheamperometricprocedureswerestudied:

1. ForwardtitrationwithKIaddedfirst,thenpH4buffer(PAOastitrant)
2. Forwardtitrationwithbufferaddedfirst,thenKI(PAOastitrant)
3. Backtitration,excessPAO,KI,andthenpH4buffer(iodineastitrant)
4. Backtitration,excessPAO,buffer,andthenKI(iodineastitrant)
5. Backtitration,excessPAO,KI,thenH
3
PO
4
/sulfamicacid(iodateastitrant)
6. Backtitration,excessPAO,H
3
PO
4
/sulfamicacid,thenKI(iodateastitrant).

No.1,No.3andNo.5followtheStandardMethodsproceduresforforwardtitration,backtitrationwithiodine,
andbacktitrationwithiodate,respectively.ThetestingforNo.1throughNo.4wasperformedatpH4,because
thisisthepHusedtospeciatetotalchlorine.Allofthetitrationendpointsweredeterminedamperometrically.
43

Amonochloraminestandardwaspreparedintherangeof70to80g/l(Cl
2
).Smallportionsofastocknitrite
standard,equivalenttotheadditionof0to50mg/lnitrites,wereaddedto200mlofthemonochloramine
standard.Analyseswereperformedintriplicateaccordingtothesequenceslistedabove.Meanpercentage
recoveriesasafunctionofnitriteconcentrationareshowngraphicallyinthefollowingfigure:

Figure40:Nitriteinterferenceinamperometricchlorinemethods
InvariationsNo.5andNo.6,withtheadditionofnitritetothechlorinestandard,alargeamountofiodinewas
generatedalmostinstantaneouslyaftertheadditionofthereagents.Thissuggestedthatnitrites,at
concentrationsbetween550mg/l,wouldreactreadilywithiodideatthelowerpH,eveninthepresenceof
excessreductantandsulfamicacid.StandardMethodsdirectstheanalysttotitrateimmediatelywithiodate.
HachCompanystudies,however,indicatenitriteaslowas5mg/lwillbreakthrough(interfere)within30
secondsafteradditionoftheKIandacidmixture.

Intheforwardtitrations(No.1andNo.2),nitritesseemtoindicateeitherapositiveornegativeinterference
dependingontheorderofreagentaddition.IfiodideisaddedtothesamplepriortopH4buffer,theerror
increasesasafunctionofnitriteconcentration.Ifbufferisaddedpriortotheiodide,alargenegativeerror,
independentofthenitritelevel,occurs.

Thepreferredprocedure,withtheleastinterferencefromnitrites,isthebacktitrationatpH4,usingstandard
iodinetitrant,(No.3andNo.4).TheiodometricprocedureinwhichKIisaddedfirst,thenbuffer,seemsto
providetheleastamountofvariationwithincreasingamountsofnitrites.Thisprocedureisrecommendedfor
theamperometrictitrationoftotalchlorineintreatedwastewaters,agriculturalwatersandindustrialdischarges.
ChoiceofReductant

Intheforwardamperometrictitrationmethod,itisimportantthatonlyphenylarsineoxide(PAO)beusedasthe
titrantwhenmeasuringtotalchlorine.PAOwillgivesharperendpointsthanstandardthiosulfateatpH4.0.
44

Thetitrationplotsshowthetitrationofan82g/l
monochloraminestandard,usingacontinuoustitrant
feedof:a)standardthiosulfateandb)standardPAO.
Therateofreactionofgeneratedtriiodidewith
thiosulfateevidentlychangesastheendpointis
approached.Thiscanleadtouncertaintywhen
determiningtheendpointgraphically.PAOgivesa
relativesharperendpointdetermination.Inthe
caseoftheamperometricbacktitrationmethod,the
additionofeitherexcessPAOorthiosulfateis
acceptable.Thetitrationendpointsforbothreductantsareequivalentwhenstandardiodineisthetitrant.

EffectofIodineDemandonEndPointDeterminations

Certainsamplescontainingorganiccompoundsmayexhibitaniodinedemandthatcanshiftthetitrationend
point,evenwhenabacktitrationprocedureisused.

Ifthesamplecontainssuspendedparticles,iodinewilladsorbreadilyontotheparticles,resultinginashiftofthe
currentreadings.Inadditiontoadsorption,iodinecanreactwithdissolvedorganicmatterinthesampleforming
carboniodinebonds.Forsamplescontainingappreciableiodinedemand,itmaybedifficulttoachievean
accurateestimationoftheendpoint.Continuingthetitrationtoobtainseveralreadingsaftertheendpointwill
helpdeterminetheintersectionofthetwolines.Inaddition,thespeedatwhichthetitrationisperformedwillbe
afactorinminimizingiodinedemandandidentifyingtheactualendpoint.Dilutionofthesamplewithchlorine
demandfreewateralsowillminimizeiodinedemand,althoughwithacertainsacrificeinsensitivity.
OrderofReagentAdditionforSalineWaterorSeawater

Thechemistryofchlorineinseawateriscomplex.Measurementofchlorineinsalineandestuarywateror
seawaterisexceedinglydifficultwithanyoftheavailableanalyticalmethods.Thereisconflictinginformationin
theliteraturepertainingtotheamperometricdeterminationoftotalchlorineinsaltwater.Severalstudieshave
indicatedtheorderofKIandbufferreagentadditionmaycauseunderestimationofthetotalchlorine
concentrationwhendeterminedamperometrically.Salinewatersusuallycontainanappreciablechlorine
demand,dueinparttooxidationofcarbonandnitrogencontainingcompounds.Bromide,usuallypresentin
seawater,willoxidizetohypobromousacidandhypobromitewhenchlorineisadded.

Furthermore,theconcentrationofchlorinecontainingandsecondaryoxidantsproducedbychlorinationare
dependentonthecharacteristicsofthewaterbeingchlorinated,suchasbromideconcentration,salinity,organic
load,watertemperatureandincidentsunlight.Thereisgeneralconsensusthatiodidereagentshouldbeadded
beforeorsimultaneouslywiththepH4bufferintheamperometricdeterminationfortotalchlorineinsaline
Figure41:ComparisonofthiosulfateandPAOastitrants
45
waters.Ifthesalinesampleisbufferedpriortoadditionoftheiodide,thetotalresidualoxidant(TRO)
concentrationmaybeunderestimated.
ComparingPortableandLaboratoryMeasurements

Avarietyofchlorinetestplatformsisavailableforthelaboratoryandforportableuseinthefield.Themost
practicalfieldmethodforchlorineresidualistheDPDcolorimetricmethod.Whetherusedinthelaboratoryorin
afieldenvironment,thereagentsarethesame.Thevariablesdeterminingaccuracyoffield/portable
measurementcomparedtoalaboratoryresultare:

Whencomparingalaboratoryresulttoaportableresultthesamplemustbeascloseaspracticaltobe
thesamesample.Withananalyteasreactiveandvolatileaschlorine,itisunlikelyonecanobtainagrab
sampleonsitethentransportaportiontothelaboratoryandexpecttheresultstobecomparableto
measurementsmadeonsite.Evenwhenasampleisfixedasdescribedaboveforamperometricback
titration,someuncertaintywillresultfromthetransportanddelayinmeasurement.
Thesamplingpointmustbecleanandfreefromcontamination.
Removeaeratorsandscreenspriortosampling.
Allowthesamplelinetorunforatleast5minutestoensurethesampleisrepresentativeoftheprocess.
Choiceofmeasurementplatform
o TeststripsandVisualcolorcomparisonTeststripsandvisualcolorcomparatorsshouldbeavoided
whenmakingmeasurementforregulatoryreportingorotherinstanceswhenagooddegreeof
accuracyisdesiredforthefollowingreasons:
o Judgmentofthecolorthatdevelopsisdependentontheindividualanalystsabilitytojudgesubtle
differencesincolor.
o Theapparentcolororintensityofcolorcanvarywith
lightsource.Whetherateststriporcolorcomparator
isviewedinbrightsunlight,heavyovercast,fluorescent
lamps,mercuryvaporlamps,etc.willchangetheresult
ofthevisualcolorjudgment.
o Visualcomparatorkitsandteststripsmaybe
appropriatefornonregulatoryreportingsuchaspools
andspasorotherchlorineconcentrationmeasurement
whereahighlevelofaccuracyisnotrequired.
Aphotometer(colorimeterorspectrophotometer)should
beusedwhenabetterdegreeofaccuracyandprecisionisneededthancanbeachievedwithvisual
methods.Photometerscanrangeinpricefromafewhundreddollarstoseveralthousanddollars.For
purposesofmeasurementofchlorineresidualgreaterthanapproximately0.05mg/ltoseconddecimal
placeaccuracy,aninexpensivehandheld,portablecolorimeterisjustasreliableasamuchmore
expensivelaboratoryspectrophotometerprovidedtheinstrumentismaintainedingoodcondition.Itis
prudenttocheckperiodicallythehandheldportableinstrumentwithstandardstoverifyperformance.It
isgoodpracticetodothesamewithexpensivelaboratoryspectrophotometers.

Figure42:ColorComparatortestkitforchlorine
residual
46

Formeasurementofverylowresiduals(i.e.useoftheULRDPDmethod)oneshouldusealaboratory
spectrophotometerandworkinthelaboratoryenvironment.WhileHachCompanymanufactures
portableinstrumentationsuitablefortheULRDPDmethod,itisverydifficultinthefieldtocontrol
variableswhenoneistryingtomeasureconcentrationsof20g/lorless.Workinginthelaboratory
providestheabilityto:

o Controlinterferencesandperformotherqualitycontrolmeasures.
o Protectreagentsfromtemperatureextremesanddirectsunlight.
o Maintaincleanlinessofapparatusandinstruments.
o Usestandardsandstandardadditionstoverifyperformance.

ContinuousOnlineMeasurementofChlorineResidual

Thetwomostcommonmethodsforonline(process)chlorineanalysisarecolorimetricandamperometric
detection.DPDcolorimetricanalysisisamethodbasedonN,NDiethylpPhenylenediamine(DPD)reactionwith
activehalogensandamperometricprobesuseelectrochemicaldeterminationofchlorinebasedonredox
processesoccurringattheelectrodes.SeeAppendixAfordiscussionofpotentiometricinstruments.

AnothermethodcurrentlyusedforchlorinemonitoringisORPoxidationreductionpotential.Thisisnota
primarymethodformeasuringconcentrationofchlorine,becauseitisneitherselectivenorspecifictothe
analyte.Sincethereareprimarymethodsavailableformeasuringchlorine,itisusuallynotjustifiedtosubstitute
theanalysiswithasecondarytrendingtechnique.Insomecases,theORPmayprovideanadditionalvalueand
thereismoreinformationavailableinthereferencesattheendofthisdocument.

ColorimetricDPDProcessChlorineAnalyzer

AnonlinechlorineresidualanalyzerbasedonDPDcolorimetricmeasurementisappealingbecausethemajority
ofwaterandwastewaterutilitiesandmanyindustrialsitesusethelaboratoryDPDcolorimetricmethod.Having
thesamebasicmeasurementtechnologyinthelaboratory,portableandonlineconfigurationspermitsgood
comparisonbetweenthelaboratoryandprocessmeasurements.Thisisespeciallytruewhenitbecomes
Figure44:HachPocket
ColorimeterII
Figure43:HachDR6000UVVisSpectrophotometer
47
necessarytocheckorvalidateperformanceoftheonlineinstrument.Itisalwaysprudenttocheckthe
performanceofanyonlineinstrumentperiodicallyagainstalaboratorymethod.

ThesamecharacteristicsoftheDPDmethodthatmakeiteasyandreliableforlaboratoryandportabletesting
applyalsotoonlinemeasurement.UseofabuffertocontrolpHduringsamplemeasurementmakesthe
methodlargelyindependentoffluctuationsinsamplepH.Inaddition,DPDindicatorandbufferreagents
preparedwithstringentqualitycontrolsprovidestabilityforlongtermuseinanonlineanalyzer.

TheHachCL17ChlorineAnalyzerutilizestheDPDcolorimetricmethod.Theanalyzercanbeconfiguredforeither
freeresidualchlorineortotalresidualchlorineanalysisbysimplyinstallingtheproperreagents.Nootherchange
totheinstrumentisnecessary.

Theanalyzercompletesasampleanalysisevery2.5minutes.Thesampleisfed
intothecolorimetersmeasuringcell.Thesampleblankabsorbanceis
measuredfirst.

Measurementofsampleblankabsorbanceallowscompensationforturbidity
ornaturalcolorinthesample,andprovidesanautomaticzeroreference
point.Reagentadditionfollowsafterzeroisset.
Alinearperistalticpump/valvemodulecontrolstheflowofincomingsample
andinjectsmeteredvolumesofthebufferandindicatorreagentsduringthe
2.5minutemeasurementcycle.

Thepump/valvemoduleusesamotordrivencam
tooperatepinchblocksthatsqueezespecialthick
walledtubingagainstafixedplate.Thecycle
operatesasfollows:

Thesampleinletlineopensallowingsample
underpressuretoflushsampletubingand
thecolorimetersamplecell.Thesample
inletlineisclosed,leavingfreshsamplein
thecell.
Ameasurementofuntreatedsamplemakesanaveragereferencemeasurementpriortoreagent
addition,i.e.,thezerovalueisdetermined,thuscompensatingforbackgroundcolorand/orturbidity.
Reagentlinesopen,allowingbufferandindicatorsolutionstoenterthecolorimetercelltomixwiththe
sample.
Aftermixingthesolutionwithastirbarandanadditionaldelaytoensurefullcolordevelopment,a
measurementismadetodeterminethechlorineconcentration.
Figure45:Cl17ChlorineAnalyzer
Figure46:Cl17FlowPathDiagram
48
Thesequencerepeatsevery2.5minutes.ThechemistryusedisbasedontheEPAspecifiedlaboratorymethod
withadjustmentsmadetothebufferstopermiteitherfreeresidualchlorineortotalresidualchlorineanalysis
withinthe2.5minutecycletime.

CL17WasteDischargeAnalysis

ThewastestreamgeneratedbytheDPDbasedanalyzersmightbeofconcern,asdischargefromallanalyzers
shouldbe.HachCompanyconductedacomprehensiveanalysisofthedischargegeneratedbytheHachCL17
analyzerbyfarthemostpopularonlinechlorineanalyticalsystem.Hachcollectedthesamplesformultiple
analyses.Twoindependentconsultinglaboratorieswereemployedtocompletetheanalyses.Duetothe
absenceoffederalregulations(RCRA)forthiskindofdischarge,theconsultinglaboratoriesperformedthe
analysesinaccordancewiththeEPAmethods
7
toidentifycompoundsregulatedforDrinkingWater.Theresults
werecomparedwithMaximumContaminationLevels(MCL)listedforthosechemicals.Inordertoidentify
chemicalsproducedbythereagentsandanalyzer,additionalanalysesofthesamplematrixandpurereagents
alsowereconducted.Obviously,comparisontodrinkingwaterstandardsisaverystringenttesttoapplytoa
dischargesamplethatiswastewater.
a
MethodDetectionLimit;
b
SecondaryDWRegulations;
c
Lifetimelevel(HealthAdvisory)
d
DWadvisory,healthbasedvalue
Figure47:SummaryofCL17DischargeAnalysis

7
CleanWaterActMethodsofInterestApprovedforuseat40CFR136
http://www.epa.gov/waterscience/methods/method/)andDrinkingWaterStandardsandHealthAdvisories(2006Ed.)
UnitedStatesEnvironmentalProtectionAgencyhttp://www.epa.gov/waterscience/criteria/drinking/dwstandards.pdf)
SAMPLE
ID
ANALYTE METHOD RESULT UNITS MDL
a
MCL
(DW)
6
CAS
TC
Bis(2ethylhexyl)
phthalate[DEHP]
M8270CGC/MS 12 g/l 4

6 117817
TC Chloroform M8260BGC/MS 15.7 g/l 0.5

80 67663
TC Aluminum,total M200.8ICPMS 5 g/l 1

50200
b
7429905
TC Boron(dissolved) EPA6010B 0.043 mg/l 0.006 1
c
7439921
TC Potassium,total M200.7ICP 3.2 mg/l 0.3 NA 7440097
TC Sodium,total M200.7ICP 13.1 mg/l 0.3 20
d
7440235
TC Zinc,total M200.8ICPMS 3 g/l 2 5000
b
7440666
FC Chloroform EPA8260BGC/MS 5.1 g/l 0.5 80 67663
FC Al(dissolved) EPA6010BICP 20 g/l 10 50200
b
7429905
FC Zn(dissolved) EPA6010BICP 5 g/l 2 5000
b
7440666
DIW Chloroform EPA8260BGC/MS 13.9 g/l 0.5 80 67663
DIW Zn(dissolved) EPA6010BICP 4 g/l 2 5000
b
7440666
49
TheexperimentwasconductedonthemostcommonconfigurationoftheCL17analyzerinvolvingastandpipe
providingsteadysampleflow/pressuretotheanalyzer.Thetestwasconductedwithtwoanalyzersonewith
FreeResidualChlorinereagentsandanotherwithTotalResidualChlorinereagents.Twodifferentlaboratories
conductedtheanalysesonthedischargesamples.Asseeninthedata,theanalysesidentifiedonlyoneregulated
compoundthatexceededthelimitsforDWsamplesDEHP,whichisacommonplasticizerleachingoutofvarious
polymericmaterials(pipes,tubing,etc.).Thecompound,identifiedonlyinthedischargeoftheCL17equipped
withTotalChlorinereagents,butnotwiththeFreeChlorinereagents,wasofconcern.Afteradditionaltesting,
thesourceofDEHPwasfoundtobeaplasticdraintube,whichisnotasuppliedanalyzeraccessory.

DPDreagent,alsofoundinthedischarge,isnotreportableaccordingtothecurrentEPAmethodsand
regulations,therefore,itdidnotappearontheofficiallaboratoryreports.ThestudiesconfirmHachCompanys
CL17ChlorineAnalyzerproducesnoregulatedcompoundatconcentrationsexceedingthefederaldrinkingwater
regulationswhenusedwithHachCompanysmanufacturedreagents.

AmperometricSensors

Amperometryisanelectrochemicaltechniquethatmeasuresthechangeinelectricalcurrentresultingfrom
chemicalreactionstakingplaceattheelectrodesasafunctionoftheanalyteconcentration.Atypical
amperometricsensorconsistsoftwodissimilarelectrodesananodeandacathode(i.e.silver/platinumor
copper/gold).Somedesignscovertheelectrodewithamembrane;othersdonothaveamembrane.

Sensorswithamembraneprovidebetterselectivityduringtheanalysis.Additionally,asmallelectricalvoltage
appliedacrosstheelectrodeprovidesgreatersensorstabilityandminimizesinterferences.Theappliedvoltage
alsopermitsuseofasmallerelectrodearea,thusasmallersensor.

Whennomembraneisused,thesystemistermedbareelectrodeamperometricandinthecaseofnoapplied
voltage,thesystemistermedgalvanic.

Fromatechnicalstandpoint,manyelectrochemicalmethodsfallundertheamperometricmeasurement
category,includingbareelectrode(opencell)andgalvanicsystems.Thesearesometimesareincorrectlyreferred
toaspolarographic.Thepolarographicmethodinvolvesadrippingmercuryelectrodeandthereforethisnameis
notapplicabletothesensorsasdescribedabove.

Belowisageneralrepresentationoftheoxidationreductionreactiontakingplaceintheamperometricsystem:

Cathode(workingelectrode):

HOCl+H
+
+2Cl

+H
2
O(reductionofhypochlorousacid)

Anode(referenceelectrode):

Cl

+MeMeCl+(oxidationofanodicmaterial,whereMe=metal)

50
Theanodemaybecomposedoftwoparts:areferenceandanauxiliary(orcounter)electrodemakingthe
measurementmorestable.Suchsystemsaretermedthreeelectrodesensors.Thefollowingdiagramillustrates
thegeneralconstructionofthethreeelectrodeamperometricsensor(probe)usedbyHachCompany.

Figure48:DiagramofHachCompanys3ElectrodeAmperometricChlorineProbe

Onlineamperometricsensorsandlaboratoryamperometrictitrationaredifferentmeasurementtechnologies
andshouldnotbeconfusedasbeingthesame.Additionally,theDPDmethodologyandamperometrictitration
arestandardmeasurementmethodsthatprovideadequateaccuracythroughouttheentiremeasurementrange.
Incontrast,onlineamperometricsensorsaredesignedmainlyforprocesscontrol,andthereforeprovide
adequateaccuracyonlyaroundthecalibratedsetpoint(normally,within12mg/lor~20%ofthesetpoint).

Thiscalibrationdependencyoftheonlineamperometricsensorsisafundamentaldifferencebetweenonline
amperometricandcolorimetrictechnology.Theamperometricmethodconsumestheanodicmaterialand
electrolyte.Thecolorimetricmethodconsumesonlyreagents.Thisdifferenceprovidesfullunderstandingofthe
calibrationdependencyoftheamperometricsensors.Amperometricsensorperformanceisdependentupon
shapeandmassoftheelectrodes,whichchange(theyarebeingconsumed)whileinoperation.Inorderto
compensateforthechanges,onemustconductcalibrationandrecalibrationonaregularbasis.

Otherfactorsinfluencingamperometricsensorsincludefluctuationinsampleflowandpressure,presenceofair
bubbles,foulingofthemembranebysolids,ironormanganese,membranedelamination,andperhapsthemost
important,samplepH.

FlowandPressureUsually,membranecoveredsensorsrequireaflowthroughcell.Theredox(oxidation/
reduction)reactionreliesonstableequilibrium(masstransferprocess)acrossthemembrane.Thesampleflow
51
Amperometric Sensor Flow Dependency
1.5
1.7
1.9
2.1
2.3
2.5
2.7
2.9
3.1
3.3
0.5 0.7 0.9 1.1 1.3 1.5 1.7
Flow, L/min
C
h
l
o
r
i
n
e
,

p
p
m
rateandpressuremustbeconsistentasthesamplepassesthemembrane.Fluctuationsinfloworpressuremay
easilycontributeinvariationsofthereadingsandthereforepooraccuracy.Onecanseethesefactorsplaya
crucialroleinattemptingdirectsensorinsertioninapressurizedsampleflow(inpipemounting).

Thefollowingfiguredemonstratestheeffectofflowchangesonanamperometricprobewithaconstantchlorine
concentrationofapproximately2mg/l.

Insomecases,amperometricsensorshavebeen
mountedinpipe
8
withnoflowcelltoconditionthe
sampleandithasbeenreportedthatthesensors
accuracyiscompletelylostifthesamplepressure
changesmorethan5psi.Inanymembrane
basedmeasurementsystem,varyingsample
pressurewillchangethethicknessofthemicron
sizedelectrolytelayerbetweenthemembraneand
electrodesurfaceleadingtoerraticresponses.

LossofFlowAproperlydesignedflowcellshouldpreventthemembranesurfacefromdryingoutincaseofloss
ofthesampleflow.Iftheonlinesensorlosessampleandthemembranedriesoutoriftheminimumflow
requirementisnotmaintained,calibrationwillbelostandthensensorreconditioninginthesamplestream
followedbyrecalibrationisrequired.

AirbubblesAmperometricchlorinesensorsar'erelativelyintolerantofairbubblesontheprobemembrane.Air
bubblesthatcollectonmembraneinhibitchlorinefromeasilypassingthroughthemembraneintothe
electrolyte.Therefore,theflowcelldesignforprobesshoulddiscourageaccumulationofairbubbles.

MembranefoulingThepresenceofhighsolids,andironormanganeseorothersubstancescanfoulmembranes
reducingoreliminatingthepassageofchlorinespeciesthroughthemembraneintotheelectrolyteinsidethe
probe.

Themembranesoutercoatingcanalsodelaminateunderinfluenceofharshwaterconditions,whichwill
diminishperformance.Examplesofeffectsofhighironcontentinthewateranddelaminatedmembranescanbe
seeninthefollowingphotoarray.

8
Severalconsiderationsshouldbestudiedbeforeattemptingtoinstallachlorineorothersensordirectlyintoapipeforpotable
watermonitoring,including,butnotlimitedtoNSFInternationalapprovalforthedevice,safetyandeaseofinserting/
withdrawingthesensorformaintenance,dynamicandstaticpressureandvelocityextremesthatmaybeencountered.
Figure49:Effectofflowrateonan
ampermetricsensor
52

Figure50:Amperometricprobemembranesdemonstratingiron
foulinganddelamination

Photo1,ontheleft,isanewmembrane;ontherightisamembraneremovedfromserviceafterjust30daysinwater
containinghighironcontent.Photo2showsagoodmembrane.Photos3areexamplesofpartial(top)andcomplete
(bottomright)delaminationofthemembranecoating.

EffectofpHonAmperometricMeasurementsForfreeresidualchlorineapplications,apHof5.0to7.0isthe
idealoperationrangeforanamperometricsensorbecauseofthehighpercentageofhypochlorousacid(HOCl)
(>80%)inthesampleandthesteepnessofthefreechlorinedissociationcurve(below)inthisrange.ThepHcan
movewithinthisrangeandthechlorineconcentrationcandriftwithoutsignificantlydiminishingtheaccuracyof
theinstrument.ThispHrange,however,isnottypicallypresentindrinkingwaterapplications.

ApHof7.0to8.0istypicallythenormaloperatingrangeformostdrinkingwaterfacilities.

TheHOClconcentrationismuchlowerversustheOCl

(hypochloriteion)inthisrange.Amperometricfree
chlorinesensorsdirectlymeasureonlyHOCl,notOCl

orCl
2
,soanychangeinpHwithinthisrangewill
substantiallyaffecttheaccuracyoftheonlineunit.

1 2
3
Figure51:HypochlorousAcidDissociationCurvevs.pH
53
pH
CL17,
mg/l
Avg.Amperometric,
Chlorine,mg/l
Difference
8.44 0.99 1.00 1.1%
7.85 0.99 1.06 6.5%
7.21 0.99 1.12 13%
6.80 0.99 1.24 25%
6.48 1.00 1.38 39%
6.01 1.01 1.55 54%
8.42 1.00 1.01 0.36%
Figure52:DPDvs.AmperometricprobeaspHisvaried.
(Averagefor5amperometricprobes(calibratedin1mg/lchlorinesampleatpH=8.4)

Incontrast,theDPDmethodisequallysensitivetoallspeciespresent.Moreover,thepHofthereactionis
controlledintheDPDmethodbecausethesampleisbufferedduringonlinemeasurement.

AtapH8.0orgreater(oftentheoperatingrangeforfacilitiesexperiencingproblemswithDBPs),theHOClpartof
freechlorineconcentrationisverylow(<20%),thereforeaccuracyoftheamperometricprobemaysuffer
significantlywithevenslightchangesinpH.

Internal/ExternalpHCompensationforAmperometricProbes

ChangeinpHaffectsalltypesofamperometricchlorineanalyzers.Manymanufacturesclaimthattheprobescan
accuratelymeasurechlorineinthepresenceofminorpHfluctuations.Inreality,theprobesalwaysexperience
somesignallossduetovariationsinthesamplepH.Onemanufacturerclaimsthatthesignallossis5%perevery
unitofpHchangeover7.0,however,amorecommon10%changeshouldbeexpected.

Addingathirdelectrode(3electrodedesign)canincreasestabilityandpHvariationscanbetolerateduptopH8
oreven9withsomeadditionalefforts,suchasinternalpHcompensationasemployedinHachCLF10andCLT10
analyzers.Inthiscase,abufferedfillingsolution(electrolyte)helpstoconvertfreechlorinespeciesinto
hypochlorousacid,whichbecomestheonlysubstancereactingwithelectrodes.However,toensurethebest
accuracy,atsamplepHgreaterthan8.5(certainlyatpH>9.0)oneshouldconsiderexternalpHadjustmentwith
eitheranacid(e.g.aceticacid)orCO
2
gas.

InexternalpHcompensationapplications,abufferfromanexternalreservoirisaddedtothesampletoadjust
andcontrolsamplepH.Thebuffermaybeassimpleasvinegarorcomplexasnecessarytoprovideadditional
benefits.Althoughthisapproachprovidesimprovedaccuracy,theonlineinstrumentationoftenlosesits
reagentlessappealduetoadditionalongoingbuffer(reagent)expensesandwastestreamcontaining
chemicals.

SomemanufacturersaddpHprobestotheamperometricchlorineanalyzertoprovidefeedbacktotheunit.The
pHmeasurementisusedtocompensatefortheratioofhypochlorousacidandhypochloriteion.Bymeasuring
thepHofthewater,thesoftwareintheanalyzerattemptstocorrectforfluctuationsinthepHandmaintainan
54
Response of Amperometric Sensor to Uncompensated
Temperature Change
0
0.5
1
1.5
2
2.5
3
3.5
4
12:28:48 12:57:36 13:26:24 13:55:12 14:24:00 14:52:48 15:21:36 15:50:24 16:19:12
C
h
l
o
r
i
n
e
,

p
p
m
0
5
10
15
20
25
30
35
40
45
50
T
e
m
p
e
r
a
t
u
r
e
,

C
11 Meas
DPD Cl2
11 Temp
accuratechlorinereading.ThedegreetowhichthisschemecansuccessfullycorrectforpHchangesdependson
themanufacturer,onthemembranematerialandtheimplementedalgorithm.Somemanufacturersclaimthat
withsuchcompensationthechlorinemeasurementcanbeconducteduptopH7.5,whileothersclaimtheycan
makethecorrectionupto8.0orevenhigher.ItisimportanttonotethatjustbecauseananalyzerhasapHinput,
itdoesnotalwaysmeanthatthepHprobeisprovidingfeedbacktocorrectthechlorinemeasurement.

HachCompanyisnotconvincedthisapproachworksverywellandhencehaselectednottoemploysuchpH
compensation.Asexplainedabove,HachhaschosenfortheCLF10andCLT10analyzerstoprovideaninputfor
pH,butdonotattemptanymathematicalcompensationforvariationsinpH.

Whetherusingopencellorprobestyleamperometricanalyzerstomeasurefreeortotalresidualchlorine,pHisa
majorvariable.WhenthepHofthesamplecanbemaintainedatastablevalueandwithoutfluctuation,itmay
notbenecessarytoaddacidorcarbondioxidetothesample.However,ifachangeinpHweretooccur,the
signalgeneratedbythesensorwouldbereducedandanerrorwouldbeintroducedintothemeasurement.Itis
alwaysadvisabletomonitorpHofthesamplealongsidethechlorineprobe.WhenpHishighlyvariableor
exceedspH9,itisadvisabletoacidifythesampleexternally(usinganacidorCO
2
gas)tomaintainastablepHin
therangeofpH4.56,eveninthecaseofinternalpHcompensation.

TemperatureEffect/CalibrationRequirementsforAmperometricProbes

Amperometricsensorsarealwayssensitivetotemperaturechanges.Twoareasaffectedbytemperaturearethe
membranepermeabilityrateandthepHcompensation,whichisalwaysdonebycalculation.Nomathematical
algorithmcanaccuratelyreflectallchangesinthewatermatrixandtheresponseofchlorinetothosechanges.

Responseofanamperometricchlorine
sensortotemperaturechangevs.DPD
readingsisdemonstratedinthisfigure.
ThedownwardtrendoftheDPD
measurementsreflectslossofchlorine
fromthesolutionattheelevated
temperature.

Inaddition,anyessentialchangesto
thewatersamplematrixmayrequire
recalibrationoftheamperometric
sensor.Whenthewater
characteristicsareconstantlychanging,thiswilloftenrequireweeklyandsometimesdailycalibrationofthe
amperometricinstrumenttoretainoverallaccuracy.Incontrast,DPDtechnologydoesnotrequirecalibrationdue
totheestablishedproportionalitybetweenchlorineconcentrationandlightabsorbance.

Figure53:TemperatureEffectonan
AmperometricSensor
55
CLF10andCLT10AmperometricProbeChlorineResidualAnalyzers

Themembranetypeamperometricprobescontainingelectrolytesolutionandtheelectrodes,separatedfromthe
processbyahydrophobicmembrane,areusuallyselectiveforchlorinespeciesanddonotrequireadditionof
externalacidsorpotassiumiodide(KI,fortotalchlorineresidual).Theseparationoftheanalyticalsystemwitha
membrane,especiallyalongwitha3electrodedesign,helpstoensurebetterstabilityofthereadingsand
provideslesssusceptibilitytocontaminationandinterference.Theelectrolytecanprovideadditionalcapabilities,
especiallyfortotalchlorineanalysis.

Availableforeitherfree,CLF10,ortotalresidualchlorine,
CLT10,theHachamperometricchlorineanalyzersusea3
electrodesensorandaproprietaryfillingsolution
(electrolyte)tocompensateforpHfluctuationsfrom4to9.

AnoptionalpHelectrode(showntotherightofchlorine
sensor,above,canbeusedtoindependentlymonitor
samplepHandprovidesadditionalmeansof
troubleshooting.Forexample,thepHmeasurementsare
usedbytheinstrumentscontrollertodeterminewhether
theelectrolytehaslostitsstrengthandthentoalertthe
operatoroftheneedtoreplacetheelectrolyte.This
featureiscalledCALWATCH.

CALWATCHmonitorsthedeviationsofchorineconcentrationand/orpHreadingsfromthepreviouslycalibrated
level.Ifthedeviationsexceedthepresetlevel,awarningoralarmisdisplayed.Ifchlorineconcentrationchanges
aspHswings(especiallydecreasesaspHincreases),itisnormallyanindicationofwornoutelectrolyteand
thereforetheusercanbewarnedtoreplaceit.TheCALWATCHfeatureiscompletelyuserconfigurableandcan
besettoactivateanddeactivateanalarmautomaticallybasedontheprocessrealitiesandtheuserpreferences.

TheCLF10scandCLT10scareidenticalinstrumentsexceptforthesensors(probes),whichareinterchangeable
andelectrolytethatisspecifictothesensortype.Thus,theinstrumentcanbeeasilyreconfiguredinthefield
fromfreetototalchlorineorviceversaifneeded.Thetotalchlorinesensorisdesignedtomeasurealltypesof
chlorinespecies.However,thefreechlorinesensormayexperienceinterferencefromthecombinedchlorine
species,primarilymonochloramine.ThefreechlorinesensorswillbetterwithstandpHfluctuationsthatare
morecommoninsuchapplications.

Modernamperometricanalyzersautomaticallycompensatechlorinemeasurementsforsampletemperature
fluctuations.However,thechlorinesensorsmaynotdisplaythesampletemperature.Aseparatetemperature
sensororanoptionalpHprobeequippedwithtemperaturesensorisneededtodisplaysampletemperatureon
thecontroller.InthecaseofCLF10andCLT10analyzers,allthreemeasurements(chlorineconcentration,pH,
andtemperature)willbedisplayedonthecontrollerwhentheoptionalpHprobeisadded.Thecommon
Figure54:HachCLF10AmperometricChlorineAnalyzer
56
controller(sc200orsc1000)provideseasymanagementoftheinstrumentinallconfigurations(calibration,data
logging,etc.)andvariousexternalcommunicationoptions(e.g.,withSCADA,PLCs,etc.)

Aswasmentionedabove,unlikecolorimetricanalyzers,theamperometricinstrumentsdorequirecalibration,
simplybecausetheirperformanceisbasedonconsumptionofelectrodesandelectrolyteinadditiontoallthe
otherfactors.Usually,thecalibrationconsistsoftwopointszeroandprocess.

Thezerocalibrationmaypresentthebiggestchallenge,especiallywitholder2electrodesystems.Thebestand
mostaccuratezerocalibrationrequirestheoperatortointroduceadechlorinatedsampleintothemeasuringcell
orprobeflowthroughcell.Becausebackgroundmatricesneedtobeaccountedforinthecalibration,DIor
distilledwatershouldnotbeusedtoperformthezero,oranyothercalibration.

Dechlorinationofsampleisthefirststepintheprocess.Thesecondstepistointroducethezerowaterintothe
analyzeratthesameratethatthesamplenormallyflowsthroughthecell.

Providingzerochlorinesamplewatertothesamplelineisnotalwayseasyandcanrequireanexternalpumpor
largequantitiesinagravityfeedconfiguration.Someinstallationsactuallyrunaparallelsamplethrougha
dechlorinatingfilterandthenintotheanalyzertoproducezerowater.Avalveisolatesthesamplefromflowing
directlyintotheanalyzer,androutesthesamplethroughthefilterbeforeenteringthemeasuringcellwhena
zerocalibrationisneeded.Afterthezerocalibrationiscompleted,thetechnicianscollectamanualgrabsample
andtestitwithacolorimeterorspectrophotometertodeterminethechlorineresidual.Thevalueobtainedwith
thegrabsampleisenteredintotheonlineanalyzertocompletethecalibrationprocedure.

Anothermethodofzeroinganamperometricanalyzeristoperformanelectronicorelectricalzero.Essentially,
theanalyzersimulatesazerocurrentthroughtheelectrodesandstoresthereadinginthesoftware.An
electroniczeroisconvenientandcompensatesforelectricalnoiseinthehardware,howeveritdoesnot
compensateforbackgroundinterferencesinthewater.

Sincethe3electrodesensorsareconsiderablymorestableagainsttheinterferences,theelectricalzero
calibrationispreferablefortheinstrumentsemployingsuchsensors,includingtheHachCLF10andCLT10
analyzers.
OpenCellChlorineAmperometricTechnologies

Amperometrictechnologydoesnotrelyontheuseofreagentstoconditionthesampleorcreateareaction,but
mayrequiretheuseofacidsorcarbondioxidegastoestablishandcontrolthepHofthesample.Whentotal
chlorineisbeingmeasuredpotassiumiodideandacidorCO
2
gasmaybeaddedtothesamplestream.

Typically,twoelectrodes,agoldcathodeandcopper
anode,areusedtogenerateasmallelectricalcurrent
proportionaltothechlorineresidualinthesample.As
chlorinepassestheelectrodes,thesacrificialcopper
electrodegivesoffelectronscreatinganelectrical
currentflowinthemeasuringcell.
Figure55:Opencellamperometricsensorillustration
57
Theamperometriccellcanbeanopendesignwherethegoldandcopperelectrodesaresituatedinanon
pressurizedsamplingchamber.Ifnoexternalvoltageisappliedacrossthetwoelectrodessuchasensorisusually
referredtoasgalvanic.

ThesamplepHmustbeintherangeofpH4.56.0forsuchsystemstooperateproperly.Acidadditionistypically
themethodusedtoadjustandcontrolthesamplepH;however,CO
2
gascanalsobeused.Whenacidisused,
somemanufacturersrecommendabufferofglacialaceticacidandsodiumacetate,andothersrecommend
vinegar.Itisimportanttofollowmanufacturersinstructions.Whenconfiguredtomeasuretotalresidual
chlorine,potassiumiodide(KI)mustalsobeaddedtothesample.WhenacidsareusedforpHadjustment,theKI
maybeaddedtothebufferorvinegar.OnceKIisaddedtothebufferorvinegaritisnotstableforlongperiods.
Whenvinegarisused,thestabilitymaybeonlyaweek.Whentheglacialaceticacid/sodiumacetatebufferis
used,thesolutionwithKImaybestableforupto2weeks.Consultthemanufactureraboutstabilityofthe
solutionscontainingKI.

InadditiontomaintainingastablepH,therateofflowthroughthecellmustbemaintainedataconstantlevelto
ensuremeasurementaccuracy.Thecellmustalsobekeptcleantomaintainastablesignalproportionaltothe
chlorinecontentinthewater.

Tokeepthecellandelectrodesclean,somemeansistypicallyprovidedtoremovecorrosionproductsandother
deposits.Somestylesofopencellamperometricchlorineanalyzersemployasystemofupto200rotating
spheres,thatrotatearoundthetwoelectrodes.Thespheresscourtheelectrodesandremovebiofoulingor
oxidesthatcanaccumulateontheelectrodes.Otherdesignsmayemployuseofawiperorsandtokeepthe
electrodesclean.

HachCompanyofferedanopencellonlineinstrumentformanyyears,butnolongeroffersthisconfigurationas
webelievetheDPDcolorimetricorprobestyleamperometricsensorsaresuperiortechnologies.

Limitationsofonlinemeasurementinstruments

Currently,noidealmethodexistsforquantifyingchlorineandchloraminesinwater.Allcommonmethodsof
chlorineanalysisdisplaysomelackofspecificityandarenotadequatelyselectivetobecompletelyfreeof
interferences.However,mostofthelimitationsassociatedwiththetraditionalDPDchemistry(e.g.,calibration
linearity,reagentstability,reactionproductstability,etc.)havebeenaddressedsufficientlythroughprocedures
andreagentformulationsincethefirstHachCompanychlorinetestkitbasedontheDPDchemistrywas
introducedin1973.Ontheotherhand,newmethodsincludingtheonlineamperometricchlorinedetermination
shouldbecharacterizedverythoroughlyfromtheinterferencestandpoint.Oncethereisacomplete
understandingofthosemethods,especiallyintermsoftheapplicationspecifics,theycanbesuccessfullyusedfor
onlinechlorinemonitoringandmayprovideadditionalbenefitstousers.

Severalinterferenceshavebeenidentifiedthatcanpresentlimitationswhenamperometricsensorsareusedfor
continuousonlineprocessmeasurements.Someofthemorenotedvariablesprovidinginterferencearebased
onsampleandsamplingenvironmentswithchangingchlorineconcentration,pH,temperature,sampleflow,and
pressure.Othervariablesareapplicationbasedinvolvingeaseofuse,sensorfouling,interferencesand
58
calibration.Incontrast,theEPAapprovedDPDcolorimetricmethod(SM4500G)isindependentoftemperature,
pH,andsampleflow/pressurefluctuations.

Bothcolorimetricandamperometricmethodssufferfrominterferencesduetopresenceofsomespecific
compounds.Forexample,thereiswellknownpositiveinterferenceofDPDanalysistothepresenceofchromium
andmanganesespeciesinwater.Chemically,theamperometricmethodismoretolerantofthisinterference,
howeveramperometricsensorsaremorepronetofoulingwiththepresenceofironormanganeseinthesample
(aswellasinthepresenceofhighturbidity),andthiswillresultinincreasedcleaningandcalibrationfrequency.

StepstoSelectinganOnlineMeasurementTechnology

Priortochoosinganonlinechlorineanalyzer,theapplicationshouldbeevaluatedtodefinewhattechnologywill
bemostsuitableDPDoramperometric.Utilizationofamperometrictechnologyrequiresmuchbetter
understandingofthenatureofthesampletobetestedandtheapplicationrealities,makingitdifficulttoperform
consistentlywell.Itisperceivedthatamperometricsensorsdesignedforprocesscontrolmayworkwellin
applicationswherechlorineconcentration,sampleflow,pressure,temperatureandpHarestable,i.e.ground
watermonitoring,orincertaindistributionsystems.Nevertheless,thisisaperceptiononly,because,evenin
suchapplicationschlorineconcentrationmaychangeovertime,lengthofdistributionsystem,andnatureofthe
samplematrix;thereforetradeoffsinprecisionandaccuracycanbeexpected.

Amperometric
(e.g.HachCLF10scorCLT10sc)
Colorimetric
(e.g.HachCL17)

Pros
FastresponsetochangesinCl2concentration
Reagentless
Noreagentsinthewastestream
Rangefrom0to10mg/l

Pros
Accuracy(nocalibrationneeded)
Unattendedoperationforupto30days
ResultsindependentofchangesinsamplepH,
temperature,Cl2concentration,etc
Canbeusedfordechlorinationapplications
approachingzerochlorine

Cons
GreaterinterferencefromsamplepH,
temperature,pressure,Cl2concentration
Cannotbeusedtomonitorzerochlorine.Some
measurablechlorinemustbepresentto
maintainpropersensorfunctionality

Cons
Reagentsandwastestreammanagement
Rangeof05mg/l
Mustmaintainconstantflowtotheinstrument
Figure56:ProsandConsofCLF10orCLT10andtheCL17Analyzers

Inviewoftherelativeinstabilityofchlorineandchloraminesinaqueoussolutions,especiallyinmanyprocess
applications,aswellastheassociateddynamicwaterconditionsoftheseprocesses,onlinechlorine
measurementusingtheDPDisusuallysuitableformostapplications.
59

Theprocessofmakingtherightchoicestartswithmovingthroughthefollowingsimplesteps,eachofthoseis
referredtointheguide(Fig.58)below.

Step1.Lookattheinstrument'sspecifiedchlorinemeasurementrangeandsamplepHrangetomakeyourinitial
decision.Ifthesimplecomparisonofmainspecificationssuchasmeasurementrangeisnotenoughto
chooseproceedtothenextstep.

Step2.Considereachtechnology'skeydifferentiatorstodeterminewhichtechnologyispreferredforyour
application.
Step3.Considertheadditionaldetailedspecificationstounderstandnuancesimportanttodeterminethe
suitability.
Step4.Finally,considerthekeystoapplicationsuccesstomakesurethatyourpreferredinstrumentisrightfor
yourapplication.

WhenyouhaveansweredallquestionspresentedintheStep4,thepictureshouldbecomecleareronwhich
technologyisbetterforyourapplication.

60
CL17FreeorTotalChlorine CLF10scFree,CLT10scTotal
TheOnlineChlorine
MonitoringInstrumentation
SelectionGuide

1.BasicSpecifications
ChlorineConcentration
Range
05mg/l 010mg/l
SamplepHrange(w/o
buffering)
NA pH49
2.KeyDifferentiators
SamplepH,chlorine
concentration,temp,flow
and/orpressurechanges
Noimpactonreadings
Readingsmaybeimpacted.Adjustmentto
calibrationmaybeneeded.
Calibration Calibrationnotneeded.
Yes.Frequencybaseduponthe
application.
RoutineMaintenance
Tubingreplacementevery6
months
Membraneandelectrolytereplacement
every36months
Reagents
Reagentreplacementevery
30days
NA
ReagentWasteStream Yes No
RegulatoryMethod
SM4500CLG,40CFR141.74
orEPAMethod334.0
OnlyEPAMethod334.0
Multiparameter Singleparameter OptionalpHandTemperature
3.InstrumentSpecifications
Accuracy
5%or0.03mg/l
whicheverisgreater
CLF10sc:3%atpH<7.2(0.2pHunit),
10%atapH<8.5(0.5pHunit)
CLT10sc:10%atapH<8.5(0.5pHunit)
LimitofDetection(LOD) 30ppb 30ppb(orless)
ResponseTime Batchanalysis,150seconds
Continuous,CLF10scT
90
=140s,
CLT10scT
90
=100s
Technology DPDColorimetricMethod AmperometricMethod
AutomatedCleaning No Yes
4.KeystoApplicationSuccess
AppropriateApplications
(Requirements)
Mustbeabletoreplace
reagentsmonthly
Musthaveasystemto
managethewastestream
(ifrequired)
Musthaveuninterruptedsampleflow
Musthaveuninterruptedpower
SamplepHshouldbestablewithin+/
0.5pHunitfromtheaveragevalue
Chlorineconcentrationshouldbestable
within+/20%fromtheaveragevalue
Figure57:SelectionGuideofCLF10orCLT10andtheCL17Analyzer
61
Severalmajorconclusionsleadingtodefiningthepreferredmethodforonlinechlorinemonitoringmaybemade
basedontheguideabovebyanalyzingthedifferencesinspecificationforthesetwomethods.Forexample,
complexaccuracyspecificationsestablishedfortheamperometricinstrumentsclearlyindicatedependencyofthe
readingsonpHofthesample,eveninthecaseofavailablepHcompensation.

LimitofDetection(LODorMDLminimumdetectionlimit)isaqualitativeparametershowingaborderline
betweendetectableandundetectableconcentrationoftheanalyte.Theinterpretationofthisparameteris
simpleanalyteispresentinthesampleonlyatthereadingabovetheLOD.Whiletheamperometricand
colorimetricanalyzersappeartohaveasimilarLOD,theymaynotbeequallysuitedtomeasuringverylowlevels
ofchlorineresidual.

Ifnopositiveinterferencesarepresent,andthechlorineisinfactzero,thecolorimetricanalyzermaydisplaya
zerovalueandthusitmaybeusedindechlorinationapplications.However,anamperometricsensormust
continuouslyseetheanalyte(chlorine)oritwilllosecalibration.Hence,ifchlorineresidualwillapproachlevels
aslowastheLDOorlessandeffectivelyreachzerochlorine,anamperometricsensormaynotbeagoodchoice.
Ifthesensorseesnochlorineforanextendedperiod,itwilllosesensitivitytochlorine.Thisphenomenonis
sometimescalledsleepingsensorandtheamperometricprobemustberecalibratedtorestoreaccuracyafter
chlorinefeedisrestored.

However,themostdifficultspecificationtounderstandmaybetheresponsetimeexpressedinnumberof
secondstodetectacertainlevelofthechlorineconcentrationwhenithaschangedinthesample.

InHachinstrumentationitiseither100%forabatchmethodor90%(T
90
)forcontinuousanalysis,assumingthe
chlorineconcentrationhasreacheditsfinallevelandisnotchanginganymoreatthetimethereadingis
recorded.Inordertoexplainthisdifference,resultsofcalculationsconductedforthetwotypesofanalyzers
wereplottedagainsteachotherandtheresultinggraphsarepresentedinthefollowingfigure:

Datapresentedinthisfigureillustratethat
absoluteaccuracyoftheresponsetoa
changeinchlorineconcentrationisreached
atapproximatelythesametimebyeither
instrument(CLF10scandCL17).However,
theamperometricinstrumentstarts
providingtheresponsenearly
instantaneouslyandthereforeitcanbe
configuredformuchtightercontrolofthe
chemicalpumps.

Moreover,ifthesamplewastakenbythe
CL17alittleearlierthanthedosagechange
happened,theaccurateconcentrationreadingbecomesavailableonlyaftertwocyclesofmeasurement.This
situationdisplaysoneadvantageofthecontinuousamperometrictechnologyoverDPDbasedbatchanalysis.
Figure58:Graphicalexpressionofcalculatedresponses
oftheCl17vs.amperometricprobe
62
Figure59:APA6000Ammonia/MonochloramineAnalyzer

TheCLT10sc/CLF10scandtheCL17havethecapabilityforsignalaveragingwhichisveryusefulforstable
chlorineconcentrationconditionsandhelpstoavoidfalsepositiveresponsescausedbysomeunexpectedevents,
mostlyairbubblesinthesample.However,whenactivated,thisfeaturewillextendthetimeforreactingto
changesinthechlorineconcentrationshouldtheyhappenfastandthechangeissignificant.Withanequal
amountofsignalaveragingprogrammedintothetwostylesofinstrumentation,theamperometricprobewillstill
providefasterresponse.

Oneshouldresistthetemptationtoreacttooquicklytoapparentchangesinconcentration.Chemicalfeed
systems,includingchlorination,willperformbestwhencontrolledatnearlyconstantfeedratespacedtothe
flow.Reactingtooquicklytomeasuredchangesinconcentrationcanleadtoundesirablecyclicoperationofa
chemicalfeedsystem.Takeninthislight,whileitiscertainlytruetheamperometricplatformcanprovidemore
rapidupdatesofmeasuredchlorineresidual,itisnotnecessarilyagoodideatoactonsuchrapidchanges.Inthis
regard,thesignalaveragingfunctionplaysanimportantroleinminimizingthepotentialforchangesthataretoo
rapidandtoofrequent.Whenonecarefullyconsidersalltheprocesscontrolvariables,theapparentadvantagein
responsetimebetweentheamperometricplatformandtheCL17analyzermaybecomemuchlessimportant.

ContinuousOnlineMeasurementofChloramination

TheAPA6000analyzerusesthemodifiedPhenateapproach
optimizedforstability,dynamicrange,andfastreactiontime.The
chemistryisverysimilartothatusedforthelaboratoryindophenol
methodformonochloramineandfreeammonia.

Thesamechemicalmethodisusedtomonitorbothtotalammonia
andmonochloramine.ThemethodusedintheAPA6000isapatented
(U.S.PatentNo.5849592)techniquecalledCarrierlessSequential
InjectionAnalysis(CSIA).Thistechniquemixessampleandreagentsin
smallvolumesinaveryreproduciblewayforfasteranalysis.
MeasurementsarecompletedinasinglewavelengthLEDbased
colorimeteroperatingat650nm.

Tomeasuremonochloramine,abufferandindicatorareaddedstepwisetothesample.Thebufferandindicator
formagreencolorwhenmonochloramineispresent.Thecolorincreasesinintensitywithincreasing
monochloramine.Ashortreactiontimeisallowedandthemixtureofsampleandreagentsflowthroughthe
colorimeter.Theconcentrationisdeterminedbasedonthelightabsorbanceat650nm.

Totalammoniaisdeterminedinmuchthesameway.However,priortoaddingthebufferandindicator,anexcess
ofhypochloriteatahighpHisaddedtoconvertanyfreeammoniapresentinthesampletomonochloramine.
Theremainderoftheanalysisisidenticaltothemonochloraminemethod.Thetotalammoniaresultindicatesthe
combinationofanymonochloramineinitiallypresentinthesampleandanymonochloramineformedfromfree
ammonia.MaintainingtheproperpHpreventsformationofdichloramineevenwhenexcesschlorineispresent.

63
Themonochloramineanalysisandthetotalammoniaanalysiscyclealternately.Followingeachcycle,thefree
ammoniaandthechlorinetonitrogenratioiscalculatedandtheresultisdisplayed.

Ifthetotalammoniaandmonochloraminevaluesareequal(indicatingnofreeammoniaispresent)theanalyzer
defaultstodashedlinesforboththetotalammoniaandfreeammoniavalues,indicatingapotentialoverfeedof
chlorine.

Theanalyzerautocalibratesusingtwopreparedammoniastandards.Ittreatstheseknownconcentration
standardsthesameasasample.Toassurethereagentshavenotdegraded,athirdstandardismadebythe
analyzer.Thisthirdstandardisanequalmixtureofthetwoprovidedstandards.Theanalyzerdeterminesifthe
absorbanceofthethirdstandardiswithintheproperrange.Ifnot,itwarnsofthepotentialdegradationofa
reagent.ThereagentmostsusceptibletodegradationisReagent3(thehypochloritesolution)becauseitishighly
reactiveandlightsensitive.TypicalshelflifeforReagent3issixmonths.Failuretoprotectitfromlightmaylead
tofasterdegradation.
ComparisonofOnlinetoGrabSampleMeasurements

Itisalwaysprudenttocomparetheresultsofanalysisfromanonlineinstrumenttoalaboratorymeasurement.
Forchlorinemeasurementitisnecessarytoperformthegrabsampleanalysisonsitewithportable
instrumentation,mostfrequentlywiththeDPDmethod.

Whenconductingcomparisonofgrabsamplestotheonlineinstrumentonemust:

1.Ensuretheexactsamesampleisbeingmeasured.Thebestlocationtodrawagrabsamplefromistheeffluent
oftheonlineinstrument(separatefromonecontainingreagentdischarge,ifapplicable)orassecondbest,a
threewayvalveonthesamplelineimmediatelybeforethesampleenterstheprocessanalyzer.
2.Ensureallpossiblesourcesofinterferenceareknownandcompensatedforinthegrabsampleanalysis.

USEPAMethod334indicatesthatmeasurementsfromanonlinechlorineanalyzermustbewithin15%ofthe
grabsamplemeasurement.Ifthevarianceexceeds15%,Method334saystheonlineinstrumentmustbe
recalibrated.However,beforerecalibration,oneshouldcheckagaintobecertaintheportableinstrumentis
accurate,samplesbeingcomparedareexactlythesameandthatallinterferencesareaccountedfor.
Interferencesmayincludemanganese,chromiumandnaturallyoccurringammoniaororganiccompoundsfrom
NOM(naturallyoccurringorganicmatter).Thesampleflow,conditionoftheonlineinstrumentforreagents,
cleanlinessofthesamplecelloramperometricprobe,etc.shouldalsobecheckandcorrectedasneeded.

Sometimes,well(ground)waterischlorinatedandthendischargedintothedistributionsystemwithnoother
treatmentormeasurement.Whilethisapproachislegitimate,itmaypresentsomeunforeseensituationsifthe
groundwatercontainselevatedamountsofnaturallyoccurringammonia,NOM(naturalorganicmatter)oriron
andmanganese.Theproblemmayoccurwhenanamperometricchlorineanalyzerisusedformonitoringofthe
sample.Unaccountedforinterferencesmaycausecalibrationfailureinanamperometricprobe.

64
Inwastewaterdechlorinationapplications,similarsituationsmayoccurduetothepresenceoforganic
chloraminesinthewaterthatwouldcausepositiveinterferencetoDPDanalysisandnottotheamperometric
method.Inbothsituations,theoperationshappeninlowchlorineconditionsandthiswouldcausecalibration
failure,becausethecorrectionfactoratlowconcentrationishigherthancanbeacceptedbytheanalyzer.An
attempttointroducetoohighacalibrationfactorwillleadtorejectionofthecalibrationvaluebytheanalytical
system,andanerrormessage.Amperometricsensorsarenotagoodchoicefordechlorinationsystemsbecause,
asnotedabove,theymustcontinuallyseesomelevelofchlorinetomaintainsensitivitytotheanalyte.

Theruleofthumbinsuchsituationsistoevaluateallpossiblecomponentsofthecalibration/verification
processthereferencemethodandinstrument,thesamplematrixinfluence(potentialinterference),andtheon
lineanalyzer,priortomakinganyconclusion.

Acknowledgements

SignificantportionsofthisdocumentarebasedontheworkandpublicationsofDanialHarpandPatrickWiese,
retiredHachCompanyresearchchemists.Otherpersonscontributingcontentandeditorialassistanceinclude
ChadBertramandRebeccahEngelhardt.Theauthorsthanktheseindividualsfortheircontributionstothis
publication.
65
AppendixA:Otheranalyticalmethods
OrthotolidineMethod

Theorthotolidine(OT)methodforchlorinewasfirstreportedbyEllmsandHauser.Theorthotolidinemethod
wasdroppedfromthe14theditionofStandardMethodsaftertheresultsoftworoundrobinstudieswere
released(WaterChlorine(Residual)No.1;AnalyticalReferenceServiceReportNo.35,UnitedStates
EnvironmentalProtectionAgency,Cincinnati,Ohio,1969.And,WaterChlorine(Residual)No.2;Analytical
ReferenceServiceReportNo.40,UnitedStatesEnvironmentalProtectionAgency,Cincinnati,Ohio,1971.).

BothstudiesindicatedtheOTmethodgavepooraccuracyandprecisionandahighoverallerrorincomparison
withtheotherchlorinemethods.Twoaquatictoxicitystudies(Tompkins,J.;et.al.).AndFava,J,et.al.),compared
theDPDcolorimetric,amperometrictitrationandorthotolidinemethodsfordeterminingchlorineresiduals.In
bothstudies,theOTmethodgavelowervaluesatallconcentrationsoftotalchlorinerelativetotheothertwo
methods.Becauseofrelativelypooraccuracyandprecisionandalackofspecificity,theorthotolidinemethod
generallyisnotacceptedintheUnitedStatesandmostdevelopedcountries.Usageofthismethodismainly
confinedtolowcostpooltestingapplications.HachCompanydoesnotprovideatestingplatformforuseofOT.
HachCompanyalsodoesnotrecommenditsuseevenforpooltestingapplications.
Syringaldazine(FACTS)Method

Thismethodisbasedonthereactionof3,5
dimethyl4hydroxybenzaldazine(syringaldazine)
withfreechlorineona1:1basis:

Theproductisaredpurplecompoundwitha
absorptionmaximumat530nm.Thepublished
methodgenerallyisknownastheFACTSmethod
(freeavailablechlorinetestingwithsyringaldazine).
Theapplicationrangeisreportedas0.110mg/lCl
2
.
Thetesthasbeenadaptedtothedeterminationof
totalchlorineaswellasotheroxidants(Leiberman).
TheFACTSmethodhasbeenreportedtobespecific
forfreechlorine,withlittleinterferencefrom
manganese(+4)andmonochloramine.(Standard
Methods,20
th
ed.)

Duetothedifficultiesofnonreproducibleindicatorsolutions,inadequatebuffercapacitywithcertainsamples,
andcolorfading,HachCompanydoesnotofferafreechlorinetestbasedontheFACTSmethod.
PotentiometricElectrodeMethod

Theelectrodemethodisbasedonthepotentiometricmeasurementoffreeiodineproducedwheniodideis
addedtoanacidicsamplecontaininganoxidant.Themethodisanalogoustotheiodometrictitrationmethodin
thattotaloxidantismeasuredandspeciationofdisinfectantsresidualsisnotpossible.

Figure60: Reactionofsyringaldazinewithfreechlorine
66
ThemethodisbasedontheNernstequation:

E=E
o
+[2.303RT/2F]log[I
2
]/[I

Where:
E=measuredpotential
E
o
=standardpotential
2.3RT/2F=Nernstconstant
[I
2
]=iodineconcentration
[I

]=iodideconcentration

Inpractice,aplatinum/iodideelectrodepairisusedincombinationwithamillivolt(pH)meter.Theiodideion
specificelectrode(ISE)servesasthereferenceelectrode.Aconstantexcessofiodide(I

)isrequiredinthe
measuredsample.Thisisnecessarytofixtheconcentrationoftriiodide(I
3

)formed,sofreeiodine(I
2
)canbe
measured.Itisimportantthatthesameamountofiodideisaddedtobothcalibrationstandardsandthesample.

Theelectrodemethodsuffersfromseveralinterferences.Chlorideioncanformtheiodinechloridecomplex(I
2
Cl

)whichisnotsensedbytheelectrode.Organicsinthewatersamplecanreactwiththefreeiodinereleased
duringtheprocedure,yieldinglowreadings.Theelectrodewillsenseanyoxidantcapableofoxidizingiodide.
Hence,speciessuchasmanganese,iodate,bromineandcupricwillinterfere.AswithallISEprocedures,accurate
compensationforsampletemperatureisnecessary.

AlthoughitisclaimedthataMDLof5g/l(asCl
2
)totaloxidantcanbeachieved(Dimmock),thisinvolvestightly
controlledconditionsinthenonlinearareaoftheelectroderesponse.Theprocedurerequiresatleasttwo
minutesunderconstantstirringforacompleteresponse.Consideringthevolatilityofchlorineandiodinein
naturalwaters,apracticallevelofdetectionusingtheelectrodemethodiscloserto50g/l.

Wilde(Wat.Resources,25,1303)comparedtheelectrodemethodtotheforwardamperometricmethodandthe
DPDcolorimetricmethodonstandardsandcoolingwatersamplesfortotalresidualchlorineattheSavannah
RiverSite(SRS).Standardtestingwithhighpuritywaterdosedwithchlorineshowednostatisticaldifference
amongthethreemethods.However,measurementsmadewiththeelectrodeoncoolingwatersampleswere
significantlylowerthanthoseobtainedwiththeothertwomethodswere.WildeconcludedtheDPDmethod
(usingaHachColorimeterKit
9
)istherecommendedmethodforfuturemonitoringatSRSduetoitssimplicityand
suitabilityforbothfieldandlaboratorymeasurements.

AppendixB:CalculationofCTValues

TheintentofthisdiscussionistoprovidecursoryinformationaboutcalculationofCT.Enforcementofdisinfection
rulesandestablishmentofmeasurementcriteriamayvaryfromstatetostate.Thereadershouldalwaysconsult
withlocalregulatoryofficialsregardingmonitoringrequirementsandinterpretationofregulations.
DefinitionofCT

CTisanexpressionoftheconcentrationofachemicaldisinfectant,Cinmg/l,multipliedbythecontacttime,Tin
minutes.TheunitofmeasureforCTthenis(mgmin)/l.Mostprimacyagenciesenforcedisinfectionrulesbased
oncalculationofCT.

9
WildespecificallyreferencedtheHachDR100Colorimeterthatisnolongeravailable.TheHachPocketColorimeterIIisthe
directreplacement.
67
EmphasisonexpressionanduseofCTbecamecommoninthedrinkingwaterfieldduringthelate1970stomid
1980s.However,itwasfirstsuggestedasapublichealthtoolintheearly1900s.IncreaseduseofCTinthe
drinkingwaterfieldwaslargelypromptedbywaterbornediseaseoutbreakscausedbytwotroublesome
protozoa,Giardialamblia(causesGiardiasis)andCryptosporidiumparvum(causesCryptosporidiosis).Bothof
theseorganismsandtheircysts(oocysts)cancauseseverediarrhealeadingtodehydration.Personswith
weakenedimmunesystemsorthosewhoareotherwisesusceptiblecanexperiencemoreserioushealth
problemsincludingdeath.SeveraloutbreaksofGiardiasisinthemidtolate1970sspurredmoreemphasisonthe
useofCTtomeasureandmonitordisinfection.

OveronehundredpeoplediedastheresultofaCryptosporidiosisoutbreakinMilwaukee,Wisconsinin1993.
Thousandsofpeoplebecameill.TheoutbreakisthelargestwaterbornediseaseoutbreakrecordedintheUnited
Statestodate.

Notethathandtomouthtransferofcystsduetocontactwithfecalmatterfromwildordomesticanimals(or
otherinfectedhumans)notdrinkingwateristhemostcommonmodeoftransmissionofthesediseases.
DisinfectionStrategies

Drinkingwaterdisinfectionanddisinfectionstrategiesdependonrecognitionand,wherepossible,controlofa
numberofvariables.First,recallthatoneshouldnotconsiderdisinfectionasresultingonlyfromapplicationofa
singlechemical(chlorine,ozone)orphysical(highheat)stepintheprocess.Theentirewatertreatmentprocess
contributestodisinfection(themultiplebarrierapproach),andthus,mustbeconsidered.Physicalbarrierssuch
asinfiltrationschemes(riverbankfiltration),coagulation,flocculation,sedimentationandfiltration,and
membranesallcontributetoremovalofpathogenicorganismsandarepartofthedisinfectionprocess.Clear
wells,storagereservoirsandtransmissionpipespriortothefirstcustomerprovidecontacttimeforthe
disinfectantandthusarepartofthedisinfectionprocess.

Whetherdisinfectioniseffectivedependson:

Kindandconcentrationoforganismtoberemoved,inactivatedordestroyed
Kindandconcentrationofchemicaldisinfectant
Kindandeffectivenessofothertreatmenttechniques/processes
Watertemperature
pH
Timecontacttime.Howlongthechemicaldisinfectantwillbeincontactwiththewater
priortothefirstuseofthewaterbyaconsumer.
Figure61:Variablesaffectingeffectivenessofdisinfection
USEPArulesestablishedundertheSafeDrinkingWaterAct(SDWA);LongTerm1EnhancedSurfaceWater
TreatmentRule,LT1ESWTR;LongTerm2EnhancedSurfaceWaterTreatmentRule,LT2ESWTR;andtheGround
WaterRulealladdresstheimportanceofconsideringthesixvariableslistedabovetosomeextent.
KindandConcentrationofOrganismsAddressed

U.S.EPArulesandregulationsspecificallyaddressthecoliformgroup(TotalColiformRule),Giardialamblia,
Cryptosporidiaandviruses.Notethatonlythespecies,lambliaisaddressedforthegenusGiardia.Whileall
membersofthegenusCryptosporidiaareaddressed,notjustthespeciesparvum.
Treatmentrequirementsfortheseorganismsareexpressedintermsoflogremoval(seeUnderstandingLog
Removal,below).
68
RequirementsforGiardiaandViruses

RequirementsforremovalofGiardiaandvirusesaresetoutintheSurfaceWaterTreatmentRuleassummarized
inthetablebelow.Therulerequiresaminimum3log(99.9%)removal/inactivationofGiardiaand4log(99.99%)
removal/inactivationofviruses.Notethecaveatthatthestatedexpectedremovalsareinawelloperated
plant.Differentprimacyagenciesmayadoptdifferentcriteriaforwelloperated.

ExceptedLogRemovalsinWellOperated
Plant
RecommendedDisinfection(Log
Reduction)
Filtrationtype Giardia Viruses Giardia Viruses
Conventional 2.5 2.0 0.5 2.0
Direct 2.0 1.0 1.0 3.0
SlowSand 2.0 2.0 1.0 2.0
DiatomaceousEarth 2.0 1.0 1.0 3.0
Figure62:SWTRAllowedremovalcreditfortreatmentanddisinfectionincombination
RequirementsforCryptosporidiumunderLT2ESWTR

LT2ESWTR(FederalRegister/Vol.71,No.3/Thursday,January5,2006/RulesandRegulations)requirescertain
treatmentandCTvaluesbasedonwhetherornotthesystemisfilteredandontheconcentrationofcysts
(oocysts).TherequirementsforfilteredsystemsaresummarizedinthetablesbelowfromtheFederalRegister:

IfyourCryptosporidium
concentration(oocysts/l)
is
1
Yourbin
classification
is
Andifyouusethefollowingfiltrationtreatmentinfullcompliance
withexistingregulations,thenyouradditionaltreatment
requirementsare
Conventional
filtration
Direct
filtration
Slowsandor
diatomaceous
earthfiltration
Alternative
filtration
technologies
<0.075 1
Noadditional
treatment
No
additional
treatment
Noadditional
treatment
Noadditional
treatment
>0.075<1.0 2
1log
treatment
2

1.5log
treatment
2

1logtreatment
2

Asdetermined
bytheState
2,4

>1.0and<3.0 3
2log
treatment
3

2.5log
treatment
3

2logtreatment
3

Asdetermined
bytheState
3,6

>3.0 4
2.5log
treatment
3

3log
treatment
3

2.5log
treatment
3

2.5log
treatment
3,6

1.
40CFR141.710and40CFR141.711
2.
Systemsmayuseanytechnologyorcombinationoftechnologiesfromthemicrobialtoolbox.
3
Systemsmustachieveatleast1logoftherequiredtreatmentusingozone,chlorinedioxide,UV,membranes,
bagfiltration,cartridgefiltrationorbandfiltration.
4
TotalCryptosporidiumremovalandinactivationmustbeatleast4.0logs.
5
TotalCryptosporidiumremovalandinactivationmustbeatleast5.0logs.
6
TotalCryptosporidiumremovalandinactivationmustbeatleast5.5logs.
Source:LongTerm2EnhancedSurfaceWaterTreatmentRuleToolboxGuidanceManual,UnitedStatesOfficeof
WaterEnvironmental,USEPA,April2010.
Figure63:Binclassificationandadditionaltreatmentrequirementsforfilteredsystems

69
Unfilteredsystemsmustmeetavarietyofcriteria.Asummaryofsomeoftheimportantinformationfollows:

AverageCryptosporidiumconcentration(oocysts/l) AdditionalCryptosporidiuminactivation
requirements
0.01 2log
1
>0.01 3log
1

1
Overalldisinfectionrequirementsmustbemetwithaminimumoftwodisinfectants
Unfilteredsystemsmustusechlorinedioxide,ozone,orUVtomeettheCryptosporidiuminactivation
requirementsandmustmeetoveralldisinfectionrequirements(i.e.,Cryptosporidium,Giardia,andvirus
inactivation)withaminimumoftwodisinfectants[40CFR141.712(d)].Eachofthetwodisinfectants
mustachievebyitselfthetotalinactivationrequiredforoneofthethreepathogentypes.
Figure64:LT2ESWTRTreatmentrequirementsforunfilteredsystems
SummaryofMicrobialToolboxOptions

TheLT2ESWTRrequiressystemstouseoneormoreofthemicrobialtoolboxoptionsdescribedinTable1.3(40
CFR141.722).Componentsofthetoolboxincludewatershedcontrolprograms,alternativesources,pretreatment
process,additionalfiltrationbarriers,inactivationtechnologies,andenhancedplantperformance.Theintentof
thetoolboxistoprovidesystemswithflexibilityinselectingcosteffectiveLT2ESWTRcompliancestrategies.

Inmostcases,systemswillreceivepresumptivelogcreditforatoolboxoptionbydemonstratingcompliance
withrequireddesignandimplementationcriteria.ThedemonstrationofperformanceoptionallowsStatesto
approveatreatmentcreditgreaterthanthepresumptivelogcreditbasedonasitespecificortechnologyspecific
demonstrationofperformance(40CFR141.727(c)).

Systemsmayuseacombinationoftoolboxoptionstoachievetherequiredlogtreatment.Forexample,a
conventionalfiltrationsystemassignedtoBin3,requiringanadditional2logtreatment,canimplementozone
withacontacttimeandconcentrationyielding1.5logcreditsandachievetherequirementsforcombinedfilter
performance,thusreceivinganadditional0.5logcreditforatotalof2logcredit.

70

ToolboxOption CryptosporidiumTreatmentCreditwithDesignandImplementationCriteria
SourceToolboxComponents
Watershedcontrol
program
0.5logcreditforStateapprovedprogramcomprisedofEPAspecifiedelements.Specific
criteriaarein40CFR141.725(a)..
Alternativesource/
intakemanagement
Nopresumptivecredit. SystemsmayconductsimultaneousmonitoringforLT2ESWTRbin
classificationatalternativeintakelocationsorunderalternativeintakemanagement
strategies.
PreFiltrationToolboxComponents
Bankfiltration
0.5logcreditfor25foot setback;1.0logcreditfor50footsetback.Aquifermustbe
unconsolidatedsandcontainingatleast10%fines.Averageturbidityinwellsmustbe<1NTU.
Systemswithexistingwellsmustmonitorwelleffluenttodeterminebinclassificationandare
noteligibleforpresumptivecredit.See40CFR141.726(c).
Presedimentation
basinwith
coagulation
0.5logcreditfornewbasinswithcontinuousoperationandcoagulantaddition.Basinsmust
achieve0.5logturbidityreductionbasedonthemonthlymeanofdailymeasurementsin11of
the12previousmonths.Allflowmustpassthroughbasins.Systemswithexistingpre
sedimentationbasinsmustmonitorafterbasinstodeterminebinclassificationandarenot
eligibleforpresumptivecredit.
Twostagelime
softening
0.5logcreditfortwostagesofteningwithcoagulantaddition.Coagulantmustbepresentin
bothclarifiersandincludesmetalsalts,polymers,lime,ormagnesiumprecipitation.Both
clarifiersmusttreat100%offlow.
TreatmentPerformanceToolboxComponents
Combinedfilter
performance
0.5logcreditforcombinedfiltereffluentturbidity0.15NTUin95%ofsampleseachmonth.
Individualfilter
performance
1.0logcreditforindividualfiltereffluentturbidity#0.1NTUin95%ofdailymaximumsamples
eachmonth(excluding15minutesfollowingbackwash)andnofilter>0.3NTUintwo
consecutivemeasurementstaken15minutesapart.See40CFR141.727(b).SeeChapter7.
Demonstrationof
performance
CreditbasedonademonstrationtotheStatethroughStateapprovedprotocol.See40CFR
141.727(c).
AdditionalFiltrationToolboxComponents
Bagfilters
1logcreditwithdemonstrationofatleast2logremovalefficiencyinchallengetest;Specific
criteriaarein40CFR141.728(a).
Cartridgefilters
2logcreditwithdemonstrationofatleast3logremovalefficiencyinchallengetest;Specific
criteriaarein40CFR141.728(a).
Membranefiltration
Logremovalcredituptothelowervalueoftheremovalefficiencydemonstratedduringthe
challengetestifverifiedbydirectintegritytesting.See40CFR141.728(b).SeetheGuidance
ManualforMembraneFiltration.
Secondstage
filtration
0.5logcreditforasecondseparatefiltrationstage;treatmenttrainmustincludecoagulation
priortofirstfilter.Nopresumptivecreditforroughingfilters.See40CFR141.728(c).
Slowsandfilters
2.5logcreditforsecondseparatefiltrationprocess.Nodisinfectantresidualpresentin
influent.See40CFR141.728(d).
InactivationToolboxComponents
Chlorinedioxide LogcreditbasedondemonstrationofcompliancewithCTtables.See40CFR141.729(b
Ozone LogcreditbasedondemonstrationofcompliancewithCTtables.See40CFR141.729(c).
UV
LogcreditbasedondemonstrationofcompliancewithUVdosetable;reactortestingrequired
toestablishvalidatedoperatingconditions.See40CFR
Figure65:Microbialtoolboxoptions
71
DeterminingCTRequirements

Fromthepreviousdiscussiononecanseehowwatersources,kindandconcentrationoforganisms,and
treatmenttechniquesallfactorintothedisinfectionprocessandwhatsortofcreditisapplicabletoaparticular
factor.Thefinalquestionis,justhowdoescalculationofCTplayintoallofthis?TodetermineCTrequirements
onemustfirstmeasuretodeterminethechlorineresidual,sampletemperatureandsamplepH.Onecanthen
refertotablestodeterminewhatcontacttime,T,isneeded.TherequirementforGiardiaandCryptosporidium
mustbedeterminedseparately.

DeterminationoftherequiredCTrequirescertaininformationtobeknownpriortobeginningcalculation
includingthedisinfectantbeingused,disinfectantresidualandtemperature.Thenonereferstoatableofvalues
(seebelow).

Forexample,ifthetemperatureis5C,thepHis7.5,andthefreechlorineresidualis1.6mg/l,thenaCTof192
mgmin/lisrequiredtoachieve3loginactivation(CT
3
log)ofGiardia.Thetreatmentsystemincludesgranular
mediafiltrationmeetingturbidityof<0.1NTUoncombinedfiltereffluent95%ofthetime.

Figure66:RequiredCTValues(mgmin/L)for3logInactivationofGiardiaCystsbyFreeChlorine,pH6.09.0
Then,comparethattotheactualCTifonehascalculatedthedetentiontimetobe100minutes(seeCalculating
DetentionTime,below).ThecalculatedCTwouldbe:CT
calc
=1.6mg/lX100min.or160mgmin./l.Thus,the
currentsystemisnotenoughtomeettherequiredCT.

Giardiainactivationwiththecurrentschemeisshortoftherequirement.Calculatehowmuchadditionalcredit
isneededbythefollowingcalculation:

ForGiardiainactivation:=3X(CT
calc
/CT
3log
)=3X(160/192)=2.5logremoval.
72
So,inthisexample,eitherthroughadditionaldetentiontime,additionalchlorineoranadditionaltreatment
technique,thesystemneedstoprovideanadditional0.5logofcredit.Butnoticethetreatmentplantincludes
filtrationandaccordingtothetableinfigure2,filtrationprovidesacreditof2.5logs.Therefore,thisentire
treatmentsystemisproviding5logremovalofGiardia:2.5logfromfreechlorineandthedetentiontimeplus
2.5logfromfiltration.Ifoneweredeterminingvirusinactivationtheequationwouldbe:

4logvirusinactivation=4X((CT
calc
/CT
4log
)

AsimilarcalculationisusedforcalculationofCryptosporidiuminactivation.
TheEntireTreatmentSystemisImportant

Asthisexampleillustrates,calculationofCTisrelativelystraightforward.Determininghowthetreatmentsystem
complieswithlogremovalrequirementsrequiresdocumentingthecontributionofeachportionofthetreatment
system.Inmostcases,theworstcasescenariosareassumed:

Peakhourlyflow,Q,ingallonsperminute.
Temperatureatthesamplingpoint
pHatthesamplingpoint
Typeofdisinfectantused
Residualdisinfectantconcentration(C)atthesamplepoint
Detentiontimecreatedbybasins/piping/unitprocess(T).Notethevolumeusedforcalculationmustbe
theminimumworkingvolumenotthedesigncapacity.(seeCalculatingDetentionTime,below)
Bafflefactor(seeBafflingFactor,below)

Documenteachpart(unitprocess)ofthetreatmentandtheamountoflogcredittheprocessprovides.
Constructingatablelikethefollowingmaybeuseful.

CityofAnywhereProcessInventory
UnitProcess LogCreditfor
Giardia
LogCreditfor
Crypto
LogCreditforViruses
Approvedwatershedcontrol
program
0.5
Riverbankinfiltrationgallery
50ftsetback
1.0
Ozonation 0.5
Conventionalfiltration 2.5 0.5 2.0
DetentionTimeInventory
Device Capacity DTatmax
flowtotal
BafflingFactor DT(min)atMaxflow
(13,888gal./min)w
bafflingfactor
36transmission
mainfromCWto8
MGtank,3mileslong
837,083
gallons
60.3 1.0 60.3min
0.2MGCW 200,000 14.4min. 0.1 1.4
8MGtank 8,000,000 576min 0.1 57.6
Figure67:UnitProcessInventoryforLogCredit
73
UnderstandingLogRemoval

Thetermslogremovalandlogcreditsarewidelyusedtoexpressperformanceofvarioustreatmentprocesses.
Thetermscanbesomewhatconfusing.Alogarithmistheexponenttowhichanumberisraisedforaparticular
numberbase,inthe10basecountingsystem(log
10
)itistheexponenttowhich10israised.Thelogremoval
calculationisstraightforward:log
10
(Influent/effluent)whichcanalsobecalculatedaslog
10
(influent)log
10

(effluent).(Recallfromalgebra,log(a/b)=logalogb.)

Figure68:Percentvs.LogRemoval
Forexample,ifarawwaterhas16,000particles/ml>2m:

16,000=1.6X10
4
,orlog
10
16,000=4.204,or16,000=10
4.204

Ifafterfiltrationthewaterhas16particles/ml>2m,therewasa3logremoval(10
3
)thedecimalmovedtothe
left3places.

Or99.9%oftheparticles(16,00016/16,000=0.999or99.9%)

Iftheeffluentcountswere123,thelogremovalwouldbelog
10
(16,000/123)orlog
10
(16,000)log
10
(123)=
2.114.

%=10010(2logvalue)so,percent=10010(22.114)=100.769
Or99.23%

Forsometreatmentprocesses,itisproblematictoexpressresultsintermsoflogremoval.Whenmonitoring
membraneswithaparticlecounter,permeate(effluent)mayapproachzeroparticlecounts.Asthepermeate
approacheszeroparticlecounts,log(influent/effluent)becomesundefineddivisionbyzero.Rearrangingthe
expressiontolog(influent)log(effluent)doesnotsolvetheproblem.Thereisnoexponenttowhichany
numbercanberaisedwhichwillyieldzero.Log(0)isundefined.Hence,iftheeffluentapproacheszero,itisbest
toexpresstheremovalasapercentremoval.

Likewise,forsomeapplicationsexpressionasapercentisproblematic.Fordrinkingwaterapplicationsavariety
ofrulesapplywhichstipulateacertainminimumremovalofproblemorganisms,i.e.,4logremovalofviruses.
Whycouldnttherulejustsay99.99%?Well,itcouldexceptitwouldactuallymakecalculationmoredifficult.

PercentRemoval Decimalequivalent LogRemoval

68.4 0.684 0.5
90 0.90 1
99 0.99 2
99.684 0.99684 2.5
99.9 0.999 3
99.968 0.99968 3.5
99.99 0.9999 4
99.9968 0.999968 4.5
99.9990 0.99999 5
99.99968 0.999997 5.5
99.99990 0.999999 6
74
Thesamerulesthatstipulateremovalalsostipulateblanketcreditsforcertaintreatmenttechniques.A
particularutilitymayreceiveafiltrationcreditof2.5logremoval(99.68%);riverbankfiltrationmayprovide
another0.5log(68.4%)ofcredit.So,howcloseisthistotherequired4logremoval?Well,addingthetwolog
removalvaluestogether,onegets3.0logremoval(99.9%).Butonecannotaddthepercentagevaluesinthe
sameway(tryingtoaddtheequivalentpercentages,theresultis1.681or168.1percent!).Itismuchmore
convenienttoexpressthesesortsofrequirementsasalogremoval.

CalculatingDetentionTime

Peakhourlyflow,temperature,pHandresidualconcentrationshouldallbeknownfrompreviousmeasurements.
Thebafflingfactorwillbeobtainedfromareferencetable(seebelow).Onlythedetentiontimerequires
calculationpriortodeterminingCT.Thesimplestwaytothinkofdetentiontimeistorephraseitashowlong
willittaketofill?

Forapipe:

Forarectangularbasin: Foracirculartank:

Note:Forastoragetank/reservoir/basin,theheightordepthMUSTbetheminimumactivelevel.Thatis,whatis
theoperationalminimumlevelthetankispermittedtodroptoduringnormaloperationsonthepeakhourofthe
day?So,ifthemaximumwaterdepth(height)is20ft,buttheminimumlevelis12feet,then12feetmustbe
usedincalculationofdetentiontime,TforCT

DetentionTime=Volume(gallons)/flow(gallons/min)orgallonsxmin./gallons=minutes.
BafflingFactor

Finally,onemustconsiderhowwellbaffledthepipe/basin/reservoiris.Thatis,doesacertainvolumeofwater
travelthroughthedeviceasaplugflow(firstin,firstout)orcantheflowshortcircuit?Thefollowingtable
shouldbeusedtoaccountforbaffling.

Volume (gallons) = L x W x H ft
3
X 7.48
gal/ft
3
(l, w, h in feet)
Volume (gallons) = r
2
l ft
3
X 7.48 gal/ft
3
(r and l in feet)
Volume (gallons) = r
2
h ft
3
X 7.48
gal/ft
3
( r and h in feet)
75
BafflingConditions BafflingFactor BafflingDescription
Unbaffled(mixed
flow)
0.1 None,agitatebasin,verylowlengthtowidthratio,high
inletandoutletflowvelocities.Canbeapproximately
achievedinflashmixtank.
Poor .0.3 Singleormultipleunbaffledinletsandoutlets,nointra
basinbaffles
Average 0.5 Baffledinletoroutletwithsomeintrabasinbaffles
Superior 0.7 Perforatedinletbaffle,serpentineorperforatedintra
basinbaffles,outletweirorperforatedlaunders
Perfect(plugflow) 1.0 Veryhighlengthtowidthration(pipelineflow),
perforatedinlet,outletandintrabasinbaffles
Figure69:TableofBafflingfactors
ActualDetentionTime=CalculatedDetentionTimeXBafflingFactor

Forexample,ifacircularbasinis20feethigh,60feetindiameterwithaminimumworkinglevelof12feet,the
detentiontimeataflowof5000gallons/min.is50.7minutes(Vol.ingal.=r
2
hX7.48=253,661gallons.
Detentiontime=volume/flow=50.7minutes.)

But,ifthebasinisunbaffled,then,

ActualDetentionTime=50.7minutesX0.1or5.1minutes!
UseHachWIMStoCalculateCT

ForusersofHachWaterInformationManagementSolutions(HachWIMS)
calculationofCTisveryeasy.DataneededareextractedfromHACHWIMSand
allcalculationsperformed!Thatsit!CTtablesforGiardia,Cryptosporidiumand
virusesarebuiltin.Tablesofotherinformationneededsuchasinfigure9are
createdinHACHWIMSbytheuser.ThenwhenitstimefortheCTcalculations,a
fewclicksinHACHWIMSanditsdone.Adrinkingwatercustomerpurchasing
HACHWIMSforthefirsttimeorperforminganupgradecansimplytelltheHach
WIMScontacttheywanttodoCTandtheHACHWIMSpersonwillassistthemis
seeingthesystemisproperlysetup.Thefollowinglinkprovidesadetailed
descriptionofCTcalculationswithinHACHWIMS(holdCtrlandclickonthelink).
http://www.opssys.com/instantkb/article.aspx?id=10095&query=CT+Calculations.
EPAAutomatedCTCalculationToolsAvailable

TwotoolsareavailablefromUSEPAforcalculatingCT.TwoExcelworkbooks,ashortformandalongform,are
availabletospeedcalculationandtokeeptrackofCTrequirements.Bothcanbedownloadedfromthewebsites
indicated.Theworkbooksalsocontaindetailedinstructionsfortheiruse.

TheShortFormisintendedforsimplesystemswithasingledisinfectionstage;basically,chemicaldisinfection
only:chloramines,chlorine,andozoneorchlorinedioxide.Oncethestartingdatebafflingfactor,disinfectant
typeisselectedandtheresidual,pH,temperature,flowandvolumeareentered,thebalanceofthesheetself
calculates.http://www.epa.gov/safewater/mdbp/lt1/xls/profile_benchmark_calculator_short.xls.

Thelongformissimilarexceptacomplexchainoftreatmentprocessescanbe
accommodated:http://www.epa.gov/safewater/mdbp/lt1/xls/profile_benchmark_calculator_long.xls.
Figure70:HachWIMS
76
AppendixC:PlumbingSampletoaProcessAnalyzer

Ifthesampleisnotright,theanalysisiswrong!

1.Isthesamplewellmixedandrepresentative?

a.Anychemicaladditionwhichcanaffectthemeasurementshouldbeaddedfarenoughaheadofthesample
pointthatitiswellmixedandinsolution.Forexample,ifpHistobemeasuredafterlimeisaddedforpH
adjustment,themeasurementneedstobemadedownstreamthatallthelimeisinsolution.

b.Ifachemicaladditionwillinterferewithmeasurementoftheparameterofinterestthesampleshouldbe
drawnbeforethepointofchemicaladdition.Forexample,suspendedlimeparticlescancausepositive
errorinparticlecountmeasurementsfollowingfiltration.Measureparticlecountsinfiltereffluentpriorto
limeaddition.

2.Wherepossible,avoidturbulentflowconditionse.g.,samplelocationsnearvalves,ells,tees,flanges.
Turbulentflowconditionsmaydislodgescale,introducesevereentrainedairandcauseothersample
anomaliesthatwillleadtoinaccuratemeasurement.
Keepitshort,keepitsimple,anddontdelay

Theinstrumentshouldbelocatedascloseasispracticaltothesamplelocation.Ifthesampletobemeasuredis
inthepipegallery,thentheinstrumentshouldbetheretoo!Avoidpipingthesamplelongdistances.Exceptions
tothekeepitshortruleinclude:

Donotmountinstrumentsinlocationswheretheenvironmentwillbehostiletothefunctionandlifeof
theinstrument,e.g.,areaswithcorrosivegasesorstrongelectromagneticfields.
Donotmountinstrumentsinlocationsthatarehazardousordifficultforoperationsandmaintenance
personneltoaccess.Allinstrumentsrequireperiodicmaintenance.Ifinstrumentsaredifficultor
hazardoustoaccessforrequiredmaintenance,theywontbemaintainedandtheywontwork!
Usesamplelinesthatarecorrosionresistant,smalldiameterandmaintainhighsamplevelocity.

Wherepossible,useopaque,blackplasticormetallicpipesandtubingcompatiblewiththesampletobe
measured.Thesamplelinemustbeopaquetoblockalllightthusdiscouraginggrowthofbiofilm.Avoiduseof
copperpipeorcoppertubing.

Usethesmallestdiametertubingthatwilldeliveradequatevolumeandmaintainhighvelocity.

Selectsmalldiametersamplelinetominimizethevolumecontainedinthesamplelineandtomaintainahigh
velocity.Maintaininghighvelocityinthetubingwilldiscourageaccumulationofbiofilmandsolids,whichwill
affectaccuracy.

DontdelayKeepitshort,keepitsimple,maintainhighvelocity.

77
SampleDelayinMinutesPerFootofSampleLine
(neglectingfrictionlosswhichwillfurtherincreasethedelay)

Sample
FlowRate,
ml/min
Sample
FlowRate,
gal/min
CopperTubing(Nominalsize,ID) Sch40PVC(Nominalsize,ID)

1/4" 0.315 3/8" 0.43 1/2" 0.545 1/4" 0.364 3/8" 0.493 1/2" 0.602
300 0.08 0.051 0.095 0.153 0.068 0.125 0.186
500 0.13 0.031 0.057 0.092 0.041 0.075 0.112
750 0.20 0.020 0.038 0.061 0.027 0.050 0.075
1000 0.26 0.015 0.029 0.048 0.020 0.038 0.058
1500 0.40 0.010 0.019 0.031 0.014 0.025 0.037
2000 0.53 0.008 0.014 0.023 0.010 0.019 0.028
3785 1.00 0.004 0.008 0.012 0.005 0.010 0.015

Sch80PVC(Nominalsize,ID) TygonTubing(Nominalsize,ID)

1/4" 3/8" 1/2" 0.562 1/4" 0.125 3/8" 0.25 1/2" 0.375
300 0.08 N/A N/A 0.162 0.008 0.032 0.072
500 0.13 N/A N/A 0.097 0.005 0.019 0.043
750 0.20 N/A N/A 0.065 0.003 0.013 0.029
1000 0.26 N/A N/A 0.049 0.002 0.01 0.022
1500 0.40 N/A N/A 0.032 0.002 0.006 0.014
2000 0.53 N/A N/A 0.024 0.001 0.005 0.011
3785 1.00 N/A N/A 0.013 0.001 0.003 0.006

Donotmixandmatchplumbingfittings!

Donotconnecttoasteelpipewithagalvanizednipple,connectedtoabrassvalvethatwillthenconnecttoa
coppersamplelinebeforegettingtotheanalyzer.Thisscenarioisalltoocommonandcreatesagalvanic
corrosioncellateverypointofcontactbetweendissimilarmetals.Itcanresultinsamplelinefailureand
corrosionproductsthatinterferewithsamplemeasurement.

Useresistantmaterialswhereverpracticalwithminimalchangesinthecompositionoftheplumbingfittings
materials.Preferably,installcorrosionresistantmetalorplasticmaterials.
Provideproperflowcontrol

Controllingflowandpressureisimportantforallmeasurements,criticalforothers.Instrumentssuchas
amperometricchlorineanalyzers,particlecountersandturbidimetersareverysensitivetochangesinflowand
pressure.Valvessomanychoices.Ballvalves,needlevalves,gatevalves,globevalves.

Needlevalvesavoid.Needlevalvesoftencausesamplingdifficulty.
o Easilybecomecloggedwithsampledebrisand/orcorrosionproductsfromsampleplumbing.
o Rapidvelocitychangesaroundaneedlevalvecancauseentrainedairbubblesinthesample.

Optionally,usearotametertomeasureflow.Theyaresimple,easytoinstallandprovidesufficient
accuracy.
o Donotuserotameterswithintegralneedlevalvesforflowcontrol.
o Installaglobevalvewitharotametertosettheproperflow.

Useballandgatevalvesforon/offcontrol.Ballandgatevalvesarecommonlyusedtothrottle(control)
flow.Ballvalvesareconvenientinthattheyarenormallyturnfromclosedtoopenmakingoperation
fastandeasy.
Globevalvesaredesignedtocontrolflow.
78
Figure71:SampleQuill
Makethecorrectsampletap

Makethecorrectsampletaptoavoiderrorsinmeasurement.Donotuseanexistingsampletapsimplybecause
italreadyexists.Ifanexistingsampletapdoesnotsatisfythefollowingcriteria,makeanewtap.

If,aswithchlorine,thepurposeofthemeasurementisto
monitorchemicaldoseorresidual,sampleatapointwherethe
sampletobemonitorediswellmixed.Ideally,provideaninpipe
staticmixerbetweenthepointofchemicalinjectionand
sampling.
Avoidsamplingfromthetoporbottomofapipe.
o Samplingfromthetopwilloftenresultinproblemswithair
inthesample.
o Samplingfromthebottomwillbenonrepresentativedueto
solidsthatwillinevitablyaccumulateatthebottomofthe
pipe.
Itistypicallybesttosamplefromthesideofapipe45.
Itisdesirabletosamplefromthemiddleofthepiperatherthan
fromtheedge,especiallyonlargerdiameterpipe(say,6
diameterorlarger).Samplesdrawnfromtheedgeofapipecan
benonrepresentativeduetofoulingfromsedimentorbiofilm
accumulatedonthewallofthepipe.
Sampleprobesorsamplequillsareavailablefromanumberofmanufacturers.Someofthesearefixedin
place,othersareretractable.Theprobes/quillsareavailableinavarietyofmaterials.Somequillshave
multipleportssothesampleisacrosssectionofthepiperatherthanonepointafeaturewhichmaybe
desirableinsomeinstances,especiallyinlargerdiameterpipes.
SamplePumping

Avoidpumpingsamplewherepossible.Pumpingcanchangethesamplebyentrainingair,changingsample
temperature(thuschangingsolubilityofsomesubstances),contributingcorrosionproductsand/orchangingthe
nature(i.e.,sizeorshape)ofsuspendedmaterial.

Whenpumpingisunavoidable:

Avoidpumpsthatcausepulsation(diaphragm,piston,andperistalticpumps).Pulsationscancause
measurementirregularity.Ifunavoidable,useapulsedampenerafterthepump.
Centrifugalpumpsaretypicallypreferredtopositivedisplacementpumpsforprovidingsamplesto
analyzersduetolowercost,andcentrifugalpumpsareeasiertothrottle(controlflowandpressure).
Selectapumpwithcomponentscompatiblewiththesample.Apumpwithallcomposite(nonmetallic)
wettedpartsisdesirable.Pumpswithmetallicwettedpartscancreatemeasurementerrorsby
introducingcorrosionproducts.
Avoidexcessivesuctionlift.Atsealevel,anidealpumphasamaximumliftofabout34feet.Considering
pumpefficienciesandotherfactors,evenatsealevelthepracticalsuctionliftisonlyabout25feet.Ata
mileabovesealevel(Denver,CO)thepracticalliftisonlyabout21feet.Pumpmanufacturerswill
typicallyspecifythemaximumliftfortheirpump.Operatingapumpnearsuctionliftdesignlimitswill
causecavitationandotherproblems.Thesuctionsideofacentrifugalpumpshouldnotberestricted
thevalveonthesuctionsideshouldalwaysbefullyopen.Wheresuctionliftistoogreat,oneshould
considerasubmersiblepump.

79
Whengoodsamplingpracticesarenotfollowed,donotblameinaccuratemeasurementontheinstrument!If
thesampleisnotright,theanalysisisnotright!

AppendixD:FeedingAmmoniaforChloramination

Severaldifferentcompoundsarecommonlyusedtoaddammoniatowaterforthepurposeofchloramination

Compound
Chemical
formula
Form
PercentPurity/
Solution
Strength
Molecular
Weight
(mass)
Percent
Composition
asNitrogen
PoundsNitrogen
perPoundorgallon
ofcompound
Anhydrous
Ammonia
NH
3

Compressed
liquefiedgas
100% 17 82.35%asN 0.82#/poundofNH
3

Ammonium
Sulfate
(NH
4
)
2
SO
4

Granularor
powder
99% 132 21.21%asN
27#/poundof
AmmoniumSulfate
Liquid
Ammonium
Sulfate(LAS)
(NH
4
)
2
SO
4
Liquid
40%(specific
gravity1.216
1.228)
132 21.21%asN 0.84#/gallonofLAS
AquaAmmonia NH
4
OH Liquid
19%(typical,
specificgravity
0.897)
111 12.61%asN
0.94#/gallonifAqua
Ammonia
Figure72:Ammoniacompoundsusedforchloramination

ExampleCalculation:UsingLiquidAmmoniumSulfate(LAS)

MostsuppliersofLASprovidea3840%aqueoussolutionofammoniumsulfate,(NH
4
)
2
SO
4
.EachgallonofLAS
hasaspecificgravityfrom1.216to1.228or10.15to10.25,soitistypically10%asammonia(NH
3
).Forcoarse
control,seesteponeabove.WecansimplifythisusingtheapproximationthatLASis10lbs./gallon.SinceLASis
10%asammonia,eachgallon(10lbs.)containsapproximately1lb.ofammoniaor0.84lb.asN:

PercentCompositionofAmmoniumSulfate(NH
4
)
2
SO
4

Element AtomicWeight X NumberofAtoms = Weight(Mass)

Nitrogen 14 2 28
Hydrogen 1 8 8
Sulfur 32 1 32
Oxygen 16 4 64
Total 132
Portionthatisammonium(2N+8H) 36
%ammoniumNH
4
27%
Portionthatisnitrogen(2N) 28
%N 21%
TypicalLASSolution Density10#/gal.
40%(NH
4
)
2
SO
4
by
weight
10%NH
3
#N

=
10#
solution
X
0.4#(NH
4
)
2
SO
4

X
0.21#N

GalLAS40%solution
of(NH
4
)
2
SO
4

GalLAS 1#solution 1#(NH

4
)
2
SO
4

#N

=
0.84#N
GalLAS(40%solution) GalofLAS
Or,a40%solutionofLAShasaweightof10lbs./gallonandcontains0.84#asN.
80
Example:Iftheexpectedchlorinefeedrateis4lbs./hour,howmuchLASshouldbefedperhourtoachievean
approximateratioof4.5:1(chlorine:nitrogen)

Gal.ofLASassumesa40%solutionof(NH
4
)
2
SO
4

=
4#Cl
2

X
1#N
X
1Gal.LAS
hr hr 4.5#Cl
2
0.84#N

Gal.ofLAS
=
1.1Gal.LAS
hr hr
Ifaquaammonia(ammoniumhydroxide),granularammoniumsulfateoranhydrousammoniaisbeingused,usea
similarprocedureasabovetocalculatethecorrectdosagerate.

SimpleStepstocontrollingchlorineandammoniaforchloramination

1. MeasuretotalammoniawithaHachtestkit(#5870040PocketColorimeterII)orlabmethods,for
examplethesalicylatemethod,todetect/controltheammoniafeedrate.Thismightbeconsideredasa
coarsecontroltomonitortheammoniafeedrate.

2. MeasuremonochloramineandfreeammoniawithHachsmonochloramine/freeammoniakit(#5870026
PocketColorimeterII)orlabmethods.Thiswecanrefertoasafinecontrol.Finecontrolisusedto
adjustthechlorinetoammoniaratiotoachievechloraminationwithmonochloraminekeepfree
ammoniagreaterthanbutclosetozero.
a. Ifonehastoomuchfreeammonia,eitherslightlyincreasethechlorinefeedordecreasetheammonia
feed.
b. Ifonehastoolittlefreeammonia,eitherincreaseammoniafeedordecreasechlorinefeed.
c. Typicallyoneshouldchangeonlyonevariable.Thatis,oneshouldseteitherammoniaorchlorine
feedrateandvarytheotherone.Differentutilitieswillhavetheirownpreferenceastowhichoneto
fixandwhichonetovary.Thispreferencewillbebasedonconsultingadvice,chemicalfeedschemes
andotheroperationalconsiderations.

3. ForfinecontrolmeasuremonochloramineandfreeammoniausingHachstestkitorlabmethods.Isthe
freeammoniaclosetobutgreaterthanzero(manyoperatorsfindoperatinginarangeof0.05to0.1mg/l
NH3Nisagoodrange)?Ifyes,great!Iffreeammoniaiszero,decreasechlorinefeed(orincrease
ammoniafeed)untilaslightlypositivefreeammoniaisobtained.Remember,itisbesttofixonevariable
andmakechangeswithonlyone.

StabilityofAmmoniaandBleachSolutions

Solutionsofaquaammoniaarerelativelyunstableandmaydeteriorateovertime.Itisprudenttochecksolution
concentrationafterpreparationorwhenacommerciallypreparedsolutionisdelivered.Checkthesolution
weeklyandadjustthechemicaldoseaccordingly.Hachoffersanacidbasetitrationprocedurefordetermining
thestrengthofaquaammoniasolutions.Hachrecommendssettingtheaquaammoniafeedratebasedonthis
titrationprocedureandnotonthecertificateofanalysisthatistypicallybasedonthespecificgravityofthe
solution.
Similarly,commercialbleach,solutionsofsodiumhypochlorite,istypicallyavailableasa12%solution.
Hypochloritesolutions,asaquaammonia,arenotstable.Shipmentsshouldbetestedupondeliveryandagain
aboutonceperweek.

Chlorinebleachandaquaammoniasolutionsshouldbestoredinawellventilated,temperaturecontrolled
environmentwithnodirectsunlight.
81
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