Environmental Public Health

2 North Meridian Street, 5-E

Indianapolis, IN 46204

HOWTOSHOCKTHEPOOL
(CHLORINATETOBREAKPOINT)

Chloramines/CombinedChlorine

Ifyousmellchlorine,comingfromyourpool,whatyoureallysmellarecombinedformsofchlorine,
alsocalledchloramines.Chloraminesarechemicalcompoundsformedbychlorinecombiningwith
nitrogencontainingcontaminatesinthepoolwater.These,arestilldisinfectants,buttheyare40to60
timeslesseffectivethanfreeavailablechlorine.Contaminatescomefromswimmerwastessuchas
sweat,urine,bodyoil,etc.Thisiswhyrequiringallbatherstotakeawarm,soapywatershowerisa
goodidea.

Threetypesofchloraminescanbeformedinwatermonochloramine,dichloramine,andtrichloramine.
Monochloramineisformedfromthereactionofhypochlorousacidwithammonia.Monochloramine
maythenreactwithmorehypochlorousacidtoformadichloramine.Finally,thedichloraminemay
reactwithhypochlorousacidtoformatrichloramine.Trichloraminescausethechlorinesmelland
hangintheairdirectlyabovethepoolwaterlevel,oftencausingcompetitiveorfrequentswimmersto
haveasthmalikesymptoms.Highlevelsofchloramineswillalsocausecorrosiontosurfacesand
equipmentinthepoolarea.Thetrichloraminesareespeciallyirritatingtotheeyes,noseandlungs.

Chloraminescanusuallybeeliminatedfromthepoolwaterbyperformingbreakpointchlorinationwith
chlorineorsuperoxidationwithanonchlorineoxidizer.Ultravioletsystemsandozonesystemsare
effectiveatreducingchloraminesinpools.

Breakpointchlorination

Breakpointchlorinationisaddingenoughchlorinetoeliminateproblemsassociatedwithcombined
chlorine.Specifically,breakpointchlorinationisthepointatwhichenoughfreechlorineisaddedto
breakthemolecularbonds;specificallythecombinedchlorinemolecules,ammoniaornitrogen
compounds.Ittakesaratioofchlorinetoammoniaatomsof7.6to1toreachbreakpoint,other
contaminants(i.e.bacteria,algae)arealsopresentthatmustbeoxidized,so10timestheamountof
combinedchlorinemustbeadded.Whensufficientfreechlorine(FC)isaddedtopoolwater,the
inorganicchloraminesareconvertedtodichloramine,thentonitrogentrichloride,andthentonitrogen
gas.Anyexcesschlorineleftoverwillbecomethechlorineresidual(FC).

Thegraphbelowshowswhathappenswhenchlorine(eitherchlorinegasorahypochlorite)isaddedto
water.First(betweenpoints1and2),thewaterreactswithreducingcompoundsinthewater,suchas
hydrogensulfide.Thesecompoundsuseupthechlorine,producingnochlorineresidual.

Betweenpoints2and3,thechlorinereactswithorganicsandammonianaturallyfoundinthewater.
Somecombinedchlorineresidualisformedchloramines.

Betweenpoints3and4,thechlorinewillbreakdownmostofthechloraminesinthewater,actually
loweringthechlorineresidual.

Finally,thewaterreachesthebreakpoint,shownatpoint4.Thebreakpointisthepointatwhichthe
chlorinedemandhasbeentotallysatisfiedthechlorinehasreactedwithallreducingagents,organics,
andammoniainthewater.Whenmorechlorineisaddedpastthebreakpoint,thechlorinereactswith
waterandformshypochlorousacidindirectproportiontotheamountofchlorineadded.

Thecombinedchlorine(CC)leveliscalculatedbysubtractingthefreechlorine(FC)fromthetotal
chlorine(TC)inthepool/spawater.Rule410IAC62.130(o)2requirestestingofthepool/spawaterfor
combinedlevelsatleasttwiceaweek.

Rule410IAC62.130(e)requiresThepoolwatershallbesuperchlorinatedtobreakpointor
superoxidizedwithanonchlorineoxidizer,whenthepooltestkitrevealsacombinedchlorine
(chloramine)concentrationoffivetenths(0.5)partspermillion(ppm)orgreater.However,studies
haveshownthatswimmersfindpoolwaterthemostenjoyableifmorethan85%ofthetotalchlorineis
freechlorine.Therefore,theEnvironmentalPublicHealthStaffrecommendssuperchlorinationwhen
thecombinedchlorineconcentrationis0.2ppmorgreater(atotalchlorineof1.2ppmandafree
chlorineof1.0ppmprovides83%oftotalchlorineasfreechlorine).

Note:Poolsusingbromineasasanitizermustalsoperformbreakpointsuperchlorinationusingchlorine.
Likechlorine,brominecombineswithorganicimpuritiestoformcombinedbromineandbromamines.

Page 2 of 9
ForamorecompletediscussionofbreakpointchlorinationseetheNorthSouthWales,Australiahealth
website:www.health.nsw.gov.au/factsheets/environmental/breakpoint_chlorinat.htmlorthe
addendumtothisdocument.

AchievingBreakpointChlorination

Toachievethebreakpoint,thefreechlorine(FC)addedtothewatermustbeabouttentimesthe
amountofcombinedchlorine(CC).Thisisanallornothingprocess.Notaddingenoughchlorineto
reachbreakpointwillmaketheproblemevenworseastheresultistheformationofmorechloramines
andredissolvingofchloraminesbackintothepoolwater.Continualshockingbutnotreaching
breakpointwillresultinthepoolreachingapointofnoreturn.Partialorcompletedrainingofthepool
waterandrefillingwithfreshwatermaybetheonlyremedyatthispoint.Ifanindoorpoolfacilityhas
inadequateairexchangewithoutdoorfreshair,itwillbenecessarytoaddaircirculationfanswithdoors
andwindowsopentokeeptheairabovethepoolwaterlevelmovingtopreventredissolvingof
nitrogen(byproductofbreakpointchlorination)leadingtomorechloramineformation.

Pleasenoteasrequiredin410IAC62.1,Sec.30(g)Thepoolshallbeclosedandremainclosedduring
breakpointchlorinationandaddingtoomuchchlorine,beyondbreakpoint,willyieldhighchlorine
residualthatmayrequirethepooltoremaincloseduntilthefreechlorineresidualdropstoan
acceptablelevelasrequiredin410IAC62.1,Sec.30(b).

CalculatingAmountofChemicaltoAchieveBreakpointChlorination

TheDPDtestdoesnotmeasurecombinedchlorine(CC)directly,itmeasuresfreechlorine(FC)inStep1
andtotalchlorine(TC)inStep2.TotalChlorineisthesumoffreechlorineandcombinedchlorine.
Thereforecombinedchlorineisthedifferencebetweentotalchlorineandfreechlorine.CC=TCFC.

Thefirststepindeterminingthenecessityofashocktreatmentistodeterminethelevelofcombined
chlorine.

UsingtheD.P.D.testingkit,testforfreechlorine(FC)andtotalchlorine(TC).Aftercompletingthewater
test,yousubtractthefreechlorinereadingfromthetotalavailablechlorinereading,theresultindicates
thecombinedchlorine(CC)orchloraminelevelinthepoolwater.
Forexample:
CombinedChlorine=TotalChlorineFreeChlorine
2.3ppm(TC)measuredfromtestkit1.5ppm(FC)measuredfromtestkit=0.8ppmCC.

Ifthewaterhasnochloramines,theanswertothesubtractionwillbezero(0)andashocktreatmentis
notneeded.Thisisadesirablelevel.Afterdeterminingthelevelofcombinedchlorineinthepoolwater,
thepooloperatormustdeterminethebreakpointchlorinationforthatvalue.

Thebreakpointchlorinationvalueis10timesthecombinedchlorine(CC)level.
Forexample:0.8ppm(CC)fromtheaboveexample10=8ppmofchlorinetoachievebreakpoint.
Takingintoaccountthefreechlorineallreadyinthepool,chlorinewillhavetobeaddedtothelevelof8
ppm.

DeterminetheAmountofchemicaltoadd*:
Page 3 of 9

Example**: Calculate the chemical change to achieve Breakpoint Chlorination in 60,000 gallon pool with FC
of 1.5 ppm and TC of 2.3 ppm. Using 67% Calcium Hypochlorite where the label states that 2 oz will
produce a chemical change of 1ppm in 10,000 gallons of water:

STEP 1: Determine the amount of Combined Chlorine (CC)
Total Chlorine (TC) Free Chlorine (FC) = Combined Chlorine (CC)
2.3 ppm 1.5 ppm = 0.8 ppm

STEP 2: Calculate the breakpoint Chlorination (BPC) amount
Breakpoint (BPC) = CC 10
0.8 10 = 8.0 ppm

STEP 3: Determine the desired change amount
Desired Change = BPC FC
8.0 ppm 1.5 ppm = 6.5 ppm

STEP 3: Determine the amount of chemical to add:

Amount of chemical
from product label
Actual Pool Volume Desired Chemical
Change
Total

60,000 6.5


10,000 from product
label
1.0 ppm from product
label

2 oz. 6 6.5 78 oz
Convert answer to pounds: 78 16 = 4.875 lbs; rounded to 5 pounds.

Steps 1 must be done using a DPD test, using the test kit instructions.
*Foranalternateandsomewhatsimplermethodforcalculatingchemicalamountsfor
breakpointchlorinationseetheaddendumtothisdocument.
**Foradditionalinformationoncalculatingchemicalamountstoaddtopoolssee:
www.in.gov/isdh/files/Chemical_adjustment_pool.pdf

Stabilizedchlorinecompounds,suchasDICHLORorTRICHLORmaynotbeusedforshockingbecause
thepermittedlevelofcyanuricacidwouldbeexceededovertheseason.Italsowouldcausethe
watertohaveelevatedchlorinelevelsfordays.

NONCHLORINEOXIDIZERS

Nonchlorineoxidizersmaybeusedinsteadofchlorinebreakpointchlorination,butthepoolwillstill
havetobesuperchlorinatedperiodicallywithachlorinecompoundtokilloffthebacteriathatbecome
resistanttoconstantexposuretolowlevelsofdisinfectant(chlorineorbromine).Nonchlorineoxidizer
productswilloxidizeordestroyammonia,nitrogenandsomeswimmerwaste,butwillnotkillbacteria
oralgae.

Althoughanadvertisedadvantagetousinganonchlorineoxidizeristheshutdowntimemaybeaslittle
asonehalfhour;410IAC62.130(s)requiresthatThepoolshallbeclosedforaperiodequaltoatleast
one(1)hourfollowingthemanualadditionofchemicals.

Page 4 of 9
Ifthemanufacturerslabelrequiresclosureformorethanonehour,then410IAC62.130(h)statesthat
thepoolshallbeclosedandshallremainclosedinaccordancewiththespecificationsontheproduct
label.

Potassiummonopersulfateistheingredientusedinmostnonchlorineoxidizers.Asanoxidizer,itreacts
withcontaminantsandpreventscombinedchlorinefromforming(shortterm).Theuseofpotassium
monopersulfatewillresultinfalsereadingsofchlorineforupto6hoursasitoxidizestheiodideinthe
reagentasifitwerecombinedchlorine.Thereisareagentavailabletocorrectthis.

Theuseofnonchlorineshockchemicalswillalsointerferewithoxidationreductionpotential(ORP)
readingsbecauseitmeasurestheoxidizingpotentialofthewater.Theseproductsareanoxidizer
causinghighORPreadings,butagainitisnotadisinfectant.Intheend,therequiredfreechlorine
residuallevelfordisinfectioninthepoolwatermaybebelowtherequiredlevelasstatedin410IAC6
2.1.

Otheroptions:
1. AddingamediumpressureUV(ultraviolet)lightorozonesystemtoeliminatechloraminesinthe
poolwater.Manylargeindoorpoolsusedforcompetition(i.e.collegesandhighschools)have
hadsuccesswithusingUV.Pleasenote,intheStateofIndiana,eithersystemcanonlybe
permittedassupplementaldisinfectiontochlorinedisinfection.

2. Inadditiontothedisinfectionofbacteriaandviruses,UVCwilloxidizechloramines.UVCthat
isusedforchloraminedestructioninindoorpoolsandspasmustbepolychromaticthat
produceswavelengthsof200350nanometerswithaminimumdosage(fluence)of600J/m2
(60mJ/cm2).Multiplewavelengthsarenecessarytodestroychloraminesaslistedbelow:

Monchloramine 245nanometers
Dichloramine 297nanometers
Trichloramine 260and340nanometers

3. Somemunicipalwatercompaniesareusingchloraminesforadditionaldisinfectioninthe
distributionsystem,sotheremaybesignificantbackgroundlevelsinthepoolsupplywater.In
thiscase,carbonfiltersmaybeanoptiontoreducethechloraminesinthesourcewater.
4. Increasingtheamountoffreshwateraddeddailytothepool.
5. Forspas,itmaybebesttodrainandrefillwithfreshwatermoreoften.Recommendeddrain
andrefillcalculationis:Spagallons3usersperday=replacementinterval(days).

Thesciencebehindthechloramineproductionisevolvingandasscienceaddstotheknowledge,this
documentwillbechanged,asappropriate,toreflectthoseimprovements.Forthemostuptodate
informationonchloraminesinindoorswimmingpoolsseetheEnvironmentalPublicHealthDivisions
swimmingpoolwebpageatwww.pools.isdh.in.gov.

Otherresourcesaboutindoorairirritantsandbreakpointchlorination:

www.cdc.gov/healthywater/swimming/pools/irritants-indoor-pool-air-quality.html
www.health.nsw.gov.au/factsheets/environmental/breakpoint_chlorinat.html
www.in.gov/isdh/files/Chemical_adjustment_pool.pdf
www.pested.msu.edu/Resources/bulletins/pdf/2621/E2621chap7.pdf
Page 5 of 9

Addendum



Breakpoint Chlorination*

GraphicalRepresentationofBreakpointChlorination


Theabovegraphdemonstratesthetheoryofcontinuousbreakpointchlorination.Ontheleftverticalaxisisthe
chlorineconcentrationinmg/Lwhichiszeroatthebottomoftheaxisandincreaseswithheight.Ontheright
verticalaxisistheammonianitrogen(i.e.ammoniameasuredasnitrogen)concentrationalsoinmg/Lwhichiszero
atthebottomoftheaxisandincreaseswithheight.Thebottomhorizontalaxisrepresentstheratioofchlorine
(Cl
2
)toammonia(NH
3
)byweightwhichiszeroontheleftandincreasestotheright.Thebottomhorizontalaxis
alsorepresentstimeandincreasesfromlefttoright.Therearethreeinterrelatedlinesonthegraph:

NCONC.:(sigmaammonianitrogenconcentration)representstheconcentrationofthesumofallforms
ofammonianitrogeninthepool.
TotalChlorineApplied:theconstantdoseofchlorinebeingintroducedintothepool.
MeasuredChlorineResidual:themeasuredtotalchlorineresidualinthepool.

Thebreakpointcurveisagraphicalrepresentationofchemicalrelationshipthatexistswithconstantadditionof
chlorinetoswimmingpoolwatercontainingasmallamountofammonianitrogen.Thisgraphrepresentsa
swimmingpoolwherebathinghasceasedandnofurtherammonianitrogenisintroducedintothepool.Duringan
overnightperiodsodiumhypochloriteisaddedataconstantrate.Thiscurvehasthreezones.

Page 6 of 9
Zone1
Staringfromtheleftsideofthegraph;thereisalreadyaconcentrationofammonianitrogen(NCONC)inthepool
frombathers.ChlorinehasbeenallowedtofalltozeroandTotalAppliedChlorineandMeasuredChlorineResidual
arebothzero.Chlorineisthenaddedataconstantrate.TheprincipalreactioninZone1isthereactionbetween
chlorineandtheammoniumion.ThisreactionresultsinaMeasuredTotalChlorineofonlymonochloraminetothe
humpinthecurve.Thehumpoccurs,theoretically,atchlorinetoammonianitrogenweightratioof5:1.Thisratio
indicatesthepointwherethereactingchlorineandammonianitrogenmoleculesarepresentinsolutioninequal
numbers.Monochloraminedoesnotreadilydegrade.
Zone2
Thebreakpointphenomenonoccursinthiszonewhichisalsoknownasthechloraminedestructionzone.Asthe
weightratioexceeds5:1,someofthemonochloraminestartsreactingwithfurtheradditionofchlorinetoform
dichloramine,whichisabouttwiceasgermicidalasmonochloramine.Apuredichloramineresidualhasa
noticeabledisagreeabletasteandodour,whilemonochloraminedoesnot.TotalChlorineAppliedisstillincreasing
andboththeConcentrationofammonianitrogenandMeasuredChlorineResidualdecreaserapidly.Thisrapid
decreaseoccursbecausethedichloramineisreactingimmediatelywithadditionalhypochlorousacidinaseriesof
destructionreactionstoformvolatilecompoundsandotherbyproductssuchasnitrogengas,nitrateandchloride.
Therefore,ammoniaandchlorineareconsumedinthereactionsandlostfromthepool.Thus,additionalchlorine
isrequiredtodestroyammoniaandchloramines.
Thebreakpoint(PointA)isthepointofthelowestconcentrationofMeasuredChlorineResidualwherenuisance
chlorineresidualsremainandwhereammonianitrogenisnotdetected.Thenuisancechlorineresidualsaremainly
organicchloramineswhichcannotbeoxidisedanyfurtherbyreactingwithhypochlorousacid.
Zone3
Zone3istotherightofthebreakpoint(PointA)andiswhereafreechlorineresidualwillappear.Thetotalresidual
consistsofthenuisanceresidualsplusfreechlorine.Iftrichloramineisformed,itwillappearinthiszone.In
practiceithasbeenfoundthemostpleasantwaterforbathingwilloccurifmorethan85%ofthetotalchlorineis
freechlorine.
Inreality,ammonianitrogendoesnotstaystaticbutiscontinuallyaddedwhilethepoolisopentothepublic.To
achievebreakpointchlorination,chlorinationmustcontinueafterthepoolhasbeenclosedtothepublicto
ensureoxidationoftheadditionalchloramines.
Theshapeofthebreakpointcurveisaffectedbycontacttime,temperature,concentrationofchlorineand
ammonia,andpH.Higherconcentrationsofthechemicalsincreasethespeedofthereactions.
*From www.health.nsw.gov.au/factsheets/environmental/breakpoint_chlorinat.html
Page 7 of 9
AlternateMethodforCalculatingChemicalAdditionstoAchieve
Breakpoint*

TheformulaforbreakpointchlorinationusingLIQUIDchlorine(sodiumhypochlorite):
Volumeofthepoolingallons,times8.3(weightofonecubicft.water),timesthecombinedchlorinelevel(total
chlorineminusthefreeavailablechlorine)times1.0(lbs.ofchlorineinonegallonofliquidchlorine)times10(ten
timescombinedchlorinelevel)dividedbyonemilliontocalculatetheamountofgallonsofchlorineneededto
reachbreakpointchlorination.

(POOLVOLUME(ingallons)8.3CombinedChlorine1.010)1,000,000=Gallonsofsodiumhypochlorite
(12%)neededtoreachbreakpointchlorination

Example: Calculate the chemical change to achieve Breakpoint Chlorination in 60,000 gallon pool with FC of
1.5 ppm and TC of 2.3 ppm. Using 12% Sodium Hypochlorite

STEP 1: Determine the amount of Combined Chlorine (CC)
Total Chlorine (TC) Free Chlorine (FC) = Combined Chlorine (CC)
2.3 ppm 1.5 ppm = 0.8 ppm

STEP 2: Determine the amount of chemical to add:

Actual
Pool
Volume
Weight of
Cubic Foot
of Water
Combined
Chlorine
Lbs. of
chlorine in
1 gallon
10 Times
CC Level
Divide by one million Total
60,000 8.3 .8 1 10 1,000,000
4 gallons

Step 1 must be done using a DPD test, using the test kit instructions.

Inthisexample,4gallonsofsodiumhypochloriteisneededtoproperlyreachbreakpointchlorination.

NOTE:Whenshockingapool,thechlorinebasedchemicalusedforshockingthewatermustbeaddedallatonce
sothattheconcentrationthroughoutthepoolreachesbreakpointchlorination.




Theformulaforbreakpointchlorinationusinggranularchlorine(calciumhypochlorite)is:
Volumeofpoolwateringallonstimes8.3(weightofonecu.ft.ofwater)timescombinedchlorine(CC)level(total
chlorineminusthefreeavailablechlorine,determinedfromtheD.P.D.testkit)times1.5lb.(weightofonepound
ofcalciumhypochlorite)times10ppmrepresenting10new,freeavailablechlorinepartspermillion.Divideallthe
aboveby1,000,000todeterminebreakpointinpoundsofgranularchlorine(calciumhypochlorite67%)needed.
POOLVOLUME(ingallons)8.3COMBINEDCHLORINEx1.5101,000,000=Freechlorineresidualneededto
reachbreakpointchlorinationinpoundsofgranularchlorine
Page 8 of 9
Page 9 of 9
Example: Calculate the chemical change to achieve Breakpoint Chlorination in 60,000 gallon pool with FC of
1.5 ppm and TC of 2.3 ppm. Using 67% Calcium Hypochlorite

STEP 1: Determine the amount of Combined Chlorine (CC)
Total Chlorine (TC) Free Chlorine (FC) = Combined Chlorine (CC)
2.3 ppm 1.5 ppm = 0.8 ppm

STEP 2: Determine the amount of chemical to add:

Actual
Pool
Volume
Weight of
Cubic Foot
of Water
Combined
Chlorine
Weight of
Calcium
Hypochlorite
10
Times
CC
Level
Divide by one
million
Total
60,000 8.3 .8 1.5 10 1,000,000
6 Lbs.

Step 1 must be done using a DPD test, using the test kit instructions.

Inthisexample,6poundsofcalciumhypochloriteisneededtoproperlyreachbreakpointchlorination.
*Thesecalculationsassumeafreechlorinelevelof0.0ppm.Theymayleaveahigherconcentrationoffreechlorine
afterreachingbreakpoint,butwillensurethatbreakpointisreached.
Foradditionalinformationoncalculatingchemicalamountstoaddtopoolssee:
www.in.gov/isdh/files/Chemical_adjustment_pool.pdf