AFocusonChlorineDioxide:The"Ideal"Biocide

G.D.Simpson,R.F.Miller,G.D.Laxton,andW.R.Clements
UnichemInternationalInc.
16800ImperialValleyDrive,Suite130
Houston,Texas77060

ABSTRACT
Theuseofgaseouschlorineasamicrobiocideforindustrialcoolingsystemsisdecliningbecauseofsafety,
environmentalandcommunityimpactconsiderations.Variousalternativeshavebeenexplored,including
bleach,bleachwithbromide,bromochlorodimethylhydantoin(BCDMH),nonoxidizingbiocides,ozone,
andchlorinedioxide,amongothers.Chlorinedioxideofferssomeuniqueadvantages,duetoits
selectivity,effectivenessoverawidepHrange,andspeedofkill.Safetyandcostissueshaverestrictedits
useasaviablereplacement.Thispaperreviewsthechemistryofchlorinedioxideanditsuseincooling
systems.Comparisonsaremadewithchlorine,bromineandozone.Anovelapproachtoitsuseinasafe
andeffectivewayisdescribed.

Keywords:chlorinedioxide,chlorine,ozone,bromine,oxidizer,biocide,reviewarticle

INTRODUCTION
ThediscoveryofchlorinedioxideisgenerallycreditedtoSirHumphreyDavy,whoreportedtheresultsof
thereactionofpotassiumchloratewithsulfuricacidintheearly1800's.1Chlorinedioxidetodayis
generatedforsmallerapplicationsbythereactionofsodiumchloritewithchlorine,viaeithergaseous
chlorination(Equation1)orthereactionofsodiumhypochloritewithhydrochloricacid(Equation2).

Cl2+2NaClO2>2ClO2+2NaCl(1)

HCl+NaOCl+2NaClO2>2ClO2+2NaCl+NaOH(2)

ThischemistrywasduetothepioneeringeffortsofJ.F.Synan,J.D.MacMahon,andJ.P.Vincent,2of
MathiesonChemicalCompany,nowOlinCorporation.In1944,thegenerationofchlorinedioxideto
controltasteandodorproblemsatapotablewaterfacilityatNiagaraFalls,N.Y.,wasreported.

Thisfirstsuccessfulapplicationledtoitsuseinothermunicipalpotablewatertreatmentfacilitieswhich
hadsimilarproblems.36Overthenext25yearsresearcherscomparedthedisinfectionefficiencyof
chlorinedioxidetothatoftheindustrystandard,chlorine.715

Inthemidtolate70's,researcherslinkedchlorinationofpotablewatertoincreasedcancermortality
rates.1620Thisincreaseincancermortalitywastiedtotheproductionoftrihalomethanes,THM's.21,22The
USEPAestablished0.1ppmasthemaximumTHMcontainmentlevelfordrinkingwater.Researchinthe
areaofTHMreductioninpotablewater2327ledtotheEPAin1983suggestingtheuseofchlorinedioxide
asaneffectivemeansofcontrollingTHM's.

In1986,therewereanestimated200300chlorinedioxideapplicationsforpotablewatertreatmentin
theUSA,andapplicationsinEuropenumberedinthethousands.28

Chlorinedioxideisbeingusedincreasinglytocontrolmicrobiologicalgrowthinanumberofdifferent
industries,includingthedairyindustry,2931thebeverageindustry,32thepulpandpaperindustries,3337the
fruitandvegetableprocessingindustries,3841variouscanningplants,42,43thepoultryindustry,4453thebeef
processingindustry,54andmiscellaneousfoodprocessingapplications.5559Itisseeingincreasedusein
municipalpotablewatertreatmentfacilities6165andinindustrialwastetreatmentfacilities,7580becauseof
itsselectivitytowardsspecificenvironmentallyobjectionablewastematerials,includingphenols,sulfides,

cyanides,thiosulfates,andmercaptans.81Itisbeingusedintheoilandgasindustryfordownhole
applicationsasawellstimulationenhancementadditive.82Today,domesticindustrialapplications
numberinthethousands.83

Despitethemanyadvantagesofchlorinedioxide,relativelyfewheavyindustrialplantshavemadethe
switchtothissuperiormicrobicideforcoolingsystems.6674Historically,unlesstherewassignificant
performanceorcostadvantages,therewasnoimpetustoconsiderchlorinedioxideasareplacementfor
gaseouschlorine.Inthoseinstanceswherechlorineisnoteffectiveatmicrobiologicalcontrol,suchasa
coolingtowerwithahighleveloforganics,ammonia,oramines,chlorinedioxidehasbeencalledonto
bringcontroltotheseheavilyfouledsystems.

Withtherecenttrendtowardseliminationofgaseouschlorinefromtheindustrialplantsite,thereare
increasinginterestsinexploringallthevariousalternativestogaseouschlorine.Thisreviewcomparesfour
oxidingmicrobicides:HOCl,HOBr,ClO2,andO3,inlightofthecharacteristicsofanidealmicrobicide.

CriteriaforIdealBiocide
Whatcriteriawouldbeexpectedforan'IdealBiocide'?Meitz84discussedseveralcriteriaofanideal
biocide;thesecriteriaaresummarizedintofourbasiccategories:

Performance Itmustexhibitrapidkilloftargetorganisms,withahighLC50 towardnontarget

organisms.Itmustbeabletokeepsystemscleanofbiofilm;ideallyitshouldbeableto
cleanupalreadyfouledsystems.Itshouldnotbeconsumedbymaterialscommonly
encounteredincoolingsystems,e.g.,hydrocarbons,wood,plastic,orothertreatment
chemicals.Finally,itmustbeeffectiveoverawiderangeofoperatingconditions.
Environment Sideorbyproductreactionsshouldbeminimizedandreactionproductsshouldbe
environmentallyfriendly;neitherit,itsbyproducts,noritsreactionproductsshould
persistintheenvironment.
Safety

Itmustbesafeandeasytohandle.

Economics

Itmustbeaffordable.

Thesecharacteristicsarediscussedinthefollowingpages.Acomparisonbetweenchlorinedioxideand
chlorineismade;hypobromousacidandozoneareincluded.

DisinfectionEfficiencyandpH
Manystudieshavebeenmadecomparingthedisinfectionefficiencyofchlorinedioxidetochlorine.Inone
suchstudy,varyingdosagesofchlorinedioxideorchlorinewereaddedtosolutionscontaining15,000
viablecells/mlofE.coliatpH'sof6.5and8.5.Theabscissaisthetimeinsecondsrequiredtokill99%of
theviablebacterialcells.Theordinateistheinitialdosageofoxidant.TheresultsareshowninFigure1.8


Fig.1.ComparisonoftheDisinfectionEfficienciesofClO2withCl2atpHsof6.5and8.5

TheseresultsclearlyshowsthedecreasingeffectivenessofchlorineasthepHincreases.Thisistobe
expectedbecausechlorineresetswithwaterrapidlytoformhypochlorousandhydrochloricacids.
Hypochlorousacid,theprimarybiocide,dissociatesasafunctionofpH,formingthehypochloriteion.
Hypochloriteisreportedtobefrom1/20to1/300aseffectiveatmicrobiologicalcontrolashypochlorous
acid.85,86

Unlikechlorine,chlorinedioxideremainsatruegasdissolvedinsolution.Thelackofanysignificant
reactionofchlorinedioxidewithwaterispartlyresponsibleforitsretainingitsbiocidaleffectivenessover
awidepHrange.ThispropertymakesitalogicalchoiceforcoolingsystemsoperatedinthealkalinepH
range,orcoolingsystemswithpoorpHcontrol.

HypobromousacidalsodissociateswithpH.Thedissociationcurveisessentiallyequivalenttothatof
chlorine;itscurveisoffsetbyabout1pHunittowardthealkalinerangefromthatofhypochlorousacid.
Forexample,thepHof50%dissociationofthehypohalousacidtothehypohaliteanionisabout7.5and
8.7forchlorineandbromine,respectively.

Thedisinfectionefficiencyofozone,likethatofchlorinedioxide,isrelativelypHindependent.87However,
asthepHincreasesaboveabout8.5,thehalflifedecreasesduetotherapidformationofsignificant
amountsofhydroxylradicals.Thesehydroxylradicalsaremuchmorereactivethanozoneandhaveahalf
lifeofmicroseconds.TheneteffectisthatathighpH'sneitherdisinfectionnoroxidationwilloccur.105

KineticsofDisinfection
Figure2showsacomparisonofdosagesofseveralcommonlyusedbiocidesusedashardsurface
sanitizers,i.e.,forhospitals,foodapplications,dentaloffices,etc.Comparisonsaremadefordosages
requiredtoachieveafivelogreductioninbacterialpopulationsforseveralstrainsofbacteriawitha60
secondcontacttime.88Itisclearfromthisfigurethatchlorinedioxidereactsveryrapidly,achievinga
99.999%reductioninviablebacterialcellsinoneminute.


Fig.2.ComparisonoftheDosageRequiredtoAchievea5LogReductioninViableBacteriaat60Second
ContactTime.

TheseresultsconfirmthoseshowninFigure1alongwiththoseofearlierworkers,whodemonstratedthe
veryrapidkillofbacterialpopulationsbychlorinedioxideattimesmuchlessthanthe30minuteperiod
normallyusedindisinfectionstudies.7,9,89,98

Thespeedofdisinfectionofbromineissubjecttosomecontroversy.Manyearlyresearchersindicated
thatHOBrkillsbacteriasignificantlyfasterthanchlorinealone,86,91whileothersindicateitisslowerat
disinfectionthanchlorine.92Mostprobably,thisdiscrepancyisduetoworkdoneondifferentstrainsof
bacteria,asotherresearchershavenotedthedifficultyofestablishingaclearcriteriaofwhichdisinfectant
ismosteffectiveforthesamereason.94Moreworkisneededheretoestablishclearlytherelativebiocidal
efficiencyofbromineascomparedtothatofchlorine.

Itisgenerallyagreedthatozoneisthemostrapiddisinfectant.93,94Thisrapidreactionin'dirty'systems
resultsinashorthalflifeofozoneindisinfectionapplications,e.g.,from1020minutes,atapH<8.5.

Selectivity
Inpotableandwastetreatmentapplications,anumberofresearchershavecommentedonthe
significantlylowerdemandofthewaterforchlorinedioxidethanforchlorine.11,13,98Anexampleisshown
inFigure3.11

Fig.3.ComparisonoftheMeasuredResidualvs.DosageofClO2withCl2foraHeavilyContaminated
Water.

Equivalentamountsofchlorinedioxideandchlorinewereaddedtowaterstreamswithvariouslevelsof
contamination.Thisfigureshowstheresultsforahighlypollutedwaterstream.Residualsweremeasured
after30minutesofcontact,andtheresultswereplottedagainsttheinitialdosage.Thechlorinewas
largelyconsumed,regardlessofhowmuchwasadded.Chlorinedioxide,aftersomeinitialconsumption,
remainedmostlyunreacted.Thischaracteristicisindicativeofthemuchgreaterselectivityofchlorine
dioxidethanchlorine.

Chlorineisknowntoreactwithawidevarietyofcompounds.9597Itreactsprimarilythroughoxidation,
althoughitcanreactbybothsubstitutionandadditionreactions.

Therearemanyreportsofthelimitedreactionofchlorinedioxidewithorganics.11,67,77,81,98100This
indicatesthatmuchmoreofthechlorinedioxideaddedtoasystemisavailableasabiocidalagent,andis
notconsumedtothedegreethatchlorinewouldbeunderthesamecircumstances.

Inaddition,chlorinewillreactwithammoniaoranyamine,whilechlorinedioxidereactsveryslowlywith
secondaryamines,andnotatallwithprimaryaminesorammonia.

Brominehasaloweroxidationpotentialthanchlorine,andthuswouldbeexpectedtoreact
predominantlybysubstitution,andnotoxidationreactions.Thereissomecontroversyastowhether
bromineactsmoreasanoxidizerorhalogenator.Bromineisthoughttooxidizefasterthanchlorineby
some,producingfewerhalogenatedhydrocarbonsthanchlorine.101Otherresearchershavedemonstrated
inthelaboratorythatbrominetendstohalogenateorganics,whilechlorinepredominantlyoxidizes,when
chlorineandbrominereactincombination.155Thebrominatedorganicswhichareformedaresuspected
tobemoreharmfulthantheirchlorinatedcounterparts.85

Brominealsoreactswithaminesandammonia.Unlikechlorine,bromamineslargelyretaintheirbiocidal
effectiveness,beingalmostaseffectiveashypobromousacid.102Inaddition,thebromaminesformed
haverelativelyshorthalflives,thuseliminatingtheneedfordechlorinationinsomeplants.103

Ozoneisthestrongestoxidantwhichisusedindisinfection.Theproductsformedduringreactionswith
organicsaresmallerorganicswhicharemoreeasilymetabolizedbybacteriathanthoseformedfrom
otheroxidants.104,105Thismaycreateaprobleminpotablewatersystemswhereozoneisusedasthesole
disinfectant,astherapidlossofaresidualmayresultinaresurgenceofmicrobiologicalgrowth
downstreaminthedistributionsystem.104Itmayalsobeaproblemincoolingwaterapplicationswhere
thetimetoturnoverthesystemisgreaterthanthehalflifeofozone,becausetheresidualdoesnot
persist.106

Comparedtootheroxidizers,ozoneisrelativelynonselective,asitwillreactwithmanysubstances.107It
reactswithammoniaatmostcoolingtowerpH's,i.e.,<8.0.105

BacterialRecoveryafterDisinfection
Thephenomenonofrapidregrowthofbacteriainahighlyorganicallyloadedsystemafterhigh
chlorinationiswellestablished.l08110,112Howrapidlyabacterialpopulationreestablishesitselfafter
sterilizationisaninterestingphenomenonandiscalledbacterialrecovery.Thisphenomenonhasbeenthe
subjectofsomeresearch.TheresultsofoneinvestigationisdemonstratedinFigure4.Thisfigure,after
Roberts,et.al.,showsthataftersterilizationofawastewaterstreamwithchlorine,thebacterial
populationreestablishesitselfrelativelyrapidly.111Forthesamestreamsterilizedwithchlorinedioxide
bacterialrecoveryissomewhatslower.


Fig.4.RecoveryofBacterialActivityAfterShockDosagewithClO2andCl2.

AsimilarphenomenonwasobservedbyMcGuireandDishinger.70Inacoolingtowerusedforphenol
destruction,onecriticalexchangerexperiencedfoulingproblems.Chlorinedioxidewasfedjustpriorto
thisexchanger,keepingtheexchangerclean.Evenoneweekafterthechlorinedioxidefeedwasstopped,
theprocessoutlettemperaturehadnotreachedthelevelitwaspriortotheintroductionofthechlorine
dioxide.

Relativelylittleinformationonbacterialrecoveryafterdisinfectionwithbrominewasfound.However,it
islikelythatrecoveryafterdisinfectionwithbrominewouldbecomparabletothatwithchlorine.
Forozone,duetotherapidoxidationoforganicsintosmaller,moreeasilymetabolizedfragments,rapid
regrowthofbacteriaisexpectediftheozoneresidualislost.105

EffectivenessonBiofilmControl/Removal
Thedisinfectionrequirementsofanopenrecirculatingindustrialcoolingsystemaremarkedlydifferent
fromthoseofapotablewatertreatmentfacility.Thedisinfectiongoalofpotablewaterfacilitiesisthe
sterilizationofwaterasmeasuredbyspecificwaterbornepathogens.Thegoalofdisinfectionfor
industrialcoolingsystemsistheremovalorminimizationofanybiofilm,whichretardsheattransfer,
causesbiofouling,providesaplaceofagglomerationformarginallysolubleorinsolublesalts,andprovides
aplacewhichnurturesandpromotesthegrowthofhighlycorrosiveanaerobicbacteria.112

Onepossiblereasonfortherelativelyslowregrowthofbacteriaaftersterilizationbychlorinedioxide
(Figure4)liesinitssuperiorabilitytopenetrateanddisperseabiomass.Byeffectivelykillingandstripping
offanybiofilm,bacteriaaremuchslowertoreestablishthanwhenthebiofilmisleftintact.112

Manyresearchershavecitedtheexcellentbiofilmremovingpropertiesofchlorinedioxide.3437,41,43,66,67,69
74,113
Inatleastonepreviouslyreportedcasehistory,69theintroductionofchlorinedioxideintoaheavily
fouledcoolingsystemresultedinanincreaseinbothturbidityandcalcium.Thesewereexplainedbya
dispersingofthebiofilmwhichbothincreasedturbidityandreleasedsmallcalciumcarbonateparticulates
whichhadbeentrappedinthebiofilm.

Otherindustrieshavemadeuseoftheexcellentbiofilmremovalpropertiesofchlorinedioxide,
particularlythefoodindustry.41,43Smallcoolingtowers,frequentlycontaminatedbyfoodproductsorby
products,havetremendousslimeformingpotential.Chlorinedioxidehasachievedwidespreadusagein
suchsystems,duetoitsexcellentbiofilmdispersing/bacterialdisinfectingproperties.

Brominehasbeenshowntobesignificantlybetterthanchlorinewithregardtobiofilmcontrolbysome
researchers,114whileothershavefoundtheretobelittledifferencebetweenchlorineandbromine.86,115

Thereissomecontroversysurroundingtheeffectivenessofozoneonbiofilms.Somehavereportedthat
ozonecaneffectivelycontrolorremovebiofilms116,117,whileotherreportsindicatethatozoneisrelatively
ineffectiveonbiofilms.118,121

EffectsofSystemContamination
Chlorinedioxidehasahistoryofworkingexceptionallywellinsystemswhicharecontaminatedwith
ammonia.69,122Ithasalsobeenveryeffectiveincoolingsystemswithahighleveloforganic
contamination.67,69,72,74

Anumberofcasehistorieswereanalyzed.67,69,123125Figure5showsaroughrelationshipbetweenoxidant
demandandincreasingsystemcontamination.Itisclearfromthisfigurethatassystemcontamination
increasesHOCl/NaBrbecomesmoreeconomicalthanchlorine.Ascontaminationcontinuestoincrease,
chlorinedioxidebecomeseconomicallyfavored.

Fig.5.GeneralOverviewofRelationEconomicsofSeveralOxidantswithIncreasingSystem
Contamination.

Theproblemswithuseofbromine,particularlythehydantoinbasedmaterial,becomesapparentin
'stressed'systems,suchasinoneGulfCoastrefinery,whererainwaterandotherrunoffwateriscollected
inponds,andusedassupplementalcoolingmakeupwater.128Inthisrefinery,one40,000gpm
recirculatingcoolingtowerhasachlorinedemandof2000lbs/day.Inanattempttomoveawayfrom
gaseouschlorine,bleachwasused.Adeliverywasrequiredeveryfewdays,creatingunacceptablerisks
andinconvenience.Frombleach,theplantmovedtoahydantointypebrominematerial.Inthishigh
demandsystem,costswentupbyafactorofeight,andthiswaslimitedonlybytheinabilitytodissolve
morehydantoin.Thesecostsdidnotincludingthetremendousincreaseinthefeedrateofnonoxidizing
biocides.Despitetheseefforts,theplantdidnotachieveormaintainadequatemicrobiologicalcontrol.
Theplanthassincemovedbacktogaseouschlorineonthiscoolingsystem.

Inadditiontothisexample,othershaveagreedthatbromineisnotrecommendedforuseinhydrocarbon
contaminatedsystems.129

Ozoneworkswellinsystemsthatareclean.Asthedemandforoxidantincreases,requiredfeedratesfor
ozonedramaticallyincrease.Forexample,studiesontheeffectivenessofozoneforvirusdestructionhas
shownozonetobeveryeffective,incleansystems.93Otherwork,oncontaminatedsystemswithvirus
incorporatedintobacterialcells,haveindicatedthatozone,probablybecauseofitslackofselectivity,is
relativelyineffective,evenathighfeedrates.86,94

Insummary,for'stressed'systems,e.g.,systemswhicharecontaminatedwithhydrocarbonsorother
contaminants,thereisgenerallymuchlessofademandincreaseforchlorinedioxidethanforother
oxidizingbiocideswhichmaybeusedformicrobiologicalcontrol.

DisinfectionEffectivenessComparison:
Thequestionhasarisenastohowchlorinedioxidecanbesoeffectiveatsuchlowdosages.Figure6shows
anoverviewofoxidizingbiocidesusedasdisinfectantsincoolingsystems.Theleftmostcolumn,labeled
OxidizingStrength,istheoxidationpotentialinvolts.Thisparameterdescribeshowstronglytheoxidant
reactswithanoxidizablesubstance.Thusozone,whichisthestrongestagentlisted,hasahigher
oxidationpotentialandwillreactstronglywitheverythingthatisoxidizable.105,106Hypochlorousacid,the
activebiocidalagentwhichisformedfromthereactionofwaterandchlorinegas,isweakerthanozone,
butstrongerthanhypobromousacidandchlorinedioxide.Finally,chlorinedioxideistheweakestagent
shown.Hypochloriteandhypobromiteareshownforcomparison,butsincetheseareinequilibriumwith
theircounterparts,theseshouldnotbeconsideredasseparateentities.

Fig.6.ComparisonofOxidationPotentialandOxidationCapacityofSeveralOxidantsAlongwithRelative
OxidationofMaterialsCommonlyFoundinCoolingWater.

Column2showstheOxidationCapacityofthevariousoxidizingbiocides.Thatis,howmanyelectronsare
transferredduringanoxidationreductionreaction.Becausethechlorineatominchlorinedioxidehasan
oxidationnumberof+4,chlorinedioxidecanaccept5electronsinanoxidationreductionreaction,ifitis
reducedtochloride.Accountingformolecularweights,chlorinedioxidehas263%'availablechlorine',or
slightlymorethan2.5timestheoxidizingcapacityofchlorine.

Finally,column3showsasubjectiveoverviewofthe"oxidizability"ofcertainmaterialscommonly
encounteredincoolingsystems,orinotherwords,howeasilythesematerialsareoxidized.Asonegoes
downthistable,thematerialsshownarelesseasilyoxidized.Forexample,ammonia,knowntobe
oxidizedbyozoneandhypochlorousacid,reactsreversibility,withbromineanddoesnotreactwith
chlorinedioxideatall.

Woodisanothermaterialcommonlyfoundincoolingsystemswhichisattackedbyozoneandchlorine.
DelignificationisawellknownphenomenonwhichoccursbychlorineattackatrelativelyhighpH's.
Chlorinedioxidewillreactwithonlythephenolictypecompoundsinwood.Inotherwords,chlorineand
ozonereactwithfarmoreofthecompoundsinwoodthandoeschlorinedioxide.

Insummary,Figure6showsthatofthematerialscommonlyfoundinopenrecirculatingcoolingsystems,
chlorinedioxidereactswithmuchfewerthanchlorineorozone,i.e.,itisamuchmore'selective'oxidant
thaneitherchlorineorozone.Thuswhenaddedtoacoolingsystem,farmoreofthechlorinedioxideis
availabletoreactwiththeintendedtarget,e.g.,bacteriaandbacterialslimesthaneitherchlorineor
ozone.

Figure6showsoxidationreactionsonly.Forchlorineandbromine,bothadditionandsubstitution
reactionscanalsooccur,producingorganichalides.Inaddition,thisfigureisbasedonthermodynamic
considerations.Butkineticsalsoplaysaveryimportantpart.Forexample,althoughozonehasthe
potentialtoreactwithmanyorganics,someofthesereactionsarenotablyveryslow.

ENVIRONMENTAL
FormationofTrihalomethanes
Inthemidtolate70'sresearcherslinkedthechlorinationofpotablewatertoincreasedcancermortality
rates.1620Thisincreaseincancermortalitywasrelatedtoincreasedlevelsoftrihalomethanes,THM's,
primarilychloroform.21,22Researchersfoundthatchlorinereactedwithcertainnaturallyoccurring
organicstoproducechloroform.Asaresultofthiswork,theUSEPAset0.1ppmasthemaximumTHM
containmentlevelfordrinkingwater.Subsequently,researchintheareaofTHMreductioninpotable
water2327ledtotheEPAin1983citingchlorinedioxideasaneffectivemeansofcontrollingTHM's.
PracticalapplicationhasshownasignificantreductionorabsenceofTHM'sinsystemstreatedwith
chlorinedioxide.28,61,64,89,98AndalthoughTHMproductionhasbeenconsideredpredominantlyinthe
drinkingwaterindustry,theproductionofchloroformisseeingincreasedpressurefromenvironmental
regulatorsinindustrialplants.InColoradorecently,oneindustrialplantwhichusedgaseouschlorine
madetheswitchtochlorinedioxidebecausetheeffluentlimitforchloroformwasreducedto6ppb,and
theplantcouldnotmeeteffluentguidelineswhileutilizingchlorineastheprimarycoolingtower
microbicide.130

Brominereactswithnaturallyoccurringorganicsmuchlikechlorine,producingTHM's.Asmentioned
earlier,themutagenicityofbrominatedorganicsisthoughttobeworsethanitschlorinatedcounterparts.

OzonedoesnotdirectlyproduceTHM's.However,inwaterswithsignificantbromidelevels,theformation
ofbromoformhasbeenobserved.126,127

FormationofHaloorganics
Itisacommonlyheldbeliefthatforeveryorganicmoleculewhichexiststhereareoneormorebacteria
whichcanmetabolizepartorallofit.131However,researchhasshownthatsomemolecules,particularly
halogenatedhydrocarbons,areatbestveryslowlymetabolizedifatallbybacteria.132,133Thiscanresultin
abuildupofthesechlorinatedhydrocarbonsintheenvironment.Currentlyheldtheoriesofbacterial
evolutionsuggestthatsynthetichalogenatedmoleculeswillbedegradedonlyiftheybearastructural
resemblancetothosewhichoccurinnature.Besidesbeingquiteresistanttobiodegradation,manyof
thesechlorinatedhydrocarbonshavebeenshowntobetoxicforvariouslifeforms.59,134Thesefactors
haveresultedinmorethanoneenvironmentalgroupbecomingalarmedbecauseoftheuseof
halocarbons,e.g.,chlorinatedsolvents.

Asignificantamountofhalogenatedhydrocarbonsresultsfromthereactionofchlorineorbrominebased
microbicides,includinggaseouschlorine,withorganicsincoolingtowers.131,135Theseorganicsarepresent
becauseofprocessleaksfrompetroleumrefineriesorpetrochemicalplants,airbornecontamination,or
asnaturallyoccurringorganicspresentinthemakeupwater.

InadditiontothelackofTHMs,theamountoftotalorganichalides,TOX,foundinsystemstreatedwith
chlorinedioxideisextremelylowornonexistent.136138

Asmentionedearlier,brominecanreactbysubstitutionandadditionreactionsaswellasbyoxidation.
Thebrominatedhydrocarbonsformedaremoretoxicthanthoseproducedbychlorine.

Ozonedoesnotproducehalogenatedorganics,exceptinwaterswhereasignificantbromidelevelis
found.Insuchcasesseveralbrominatedorganicspecieshavebeenfound.126,127

ToxicitytoAquaticOrganisms
Indiscussingrelativetoxicities,fouraspectsmustbeconsidered:therelativetoxicityofthedisinfecting
agent,thehalflifeofthedisinfectingagent,therelativetoxicityofitsbyproducts,andtherelative
toxicityofthereactionproducts.Freeresidualchlorine,alongwithitsbyproductsaretoxictoaquatic
organisms.139142Chloraminesarealsoverytoxictoaquaticorganisms.Inaddition,thechlorinated
organicsareknowntobetoxic.

Thereissomecontroversysurroundingthetoxicityofchlorinedioxidetoaquaticorganisms.Some
researchersreportthatchlorinedioxideistwotothreetimesmoretoxicthanchlorine.142Anumberof
othershavereportedthatchlorinedioxideisseveralordersofmagnitudelesstoxicthanchlorineorits
residualbyproducts.86,113,143,144Itislikelythatsomeofthesestudieshavenotseparatedthetoxicitiesof
thechlorinedioxidefromthatofthechloriteformedinthegenerationofchlorinedioxide.

Chlorite,thepredominantoxidationbyproductofchlorinedioxide,hasbeenshowntoproducesignsof
hemolyticstresswhenfedtoanimals,atlevelsaslowas50ppm.Theconcernoverindividualssusceptible
tooxidativestresshasledtothelimitfortotalchlorinedioxide,chlorite,andchlorateindrinkingwater
beingsetat1.0ppm.However,inseveralstudiesperformedonhumansubjects,noeffectwas
observed.145148

Thetoxicityofbromineresidualissimilarandinsomecasesnotassevereasthatofchlorine.144
Bromaminesdonotappeartobeastoxicaschloramines,primarilyduetotherelativelyshorthalflife.
Brominatedhydrocarbonsarethoughttobesignificantlymoretoxicthanchlorinatedhydrocarbons.

Ozoneisverytoxictoaquaticlife.150Itsshorthalflifeinmostcasesresultsinthedissipationoftheozone
wellbeforedischargetoeffluent.Insystemswithrelativelyshortresidencetimes,thetoxicityofozone
willbeasignificantconsideration.Ozonereactswithnaturallyoccurringorganicswhicharepresentin
surfacewatertoproduceperoxidesandepoxideswhichareknowntobecarcinogenic.151154

SAFETY
Thesafetysurroundingtheuse,storage,andhandlingofgaseouschlorineisanincreasingconcern.The
safetyaspectsofchlorinearewellestablishedandhavebeenreviewedelsewhere.86Thesafety
considerationsinvolvedwiththeuseofchlorinedioxidearethreefold.

First,thereistheconsiderationofchlorinedioxideasagas.Duetoitsinstability,itmustbegeneratedon
site.Thegeneratorchosenmustbedesignedinsuchawaythatgaseouschlorinedioxidecannot
accumulate.Mostgenerationsystemsaredesignedwithsafetyfeatureswhichwillautomaticallyshutthe
systemdownifcatastrophicfailuresoccur,suchasthelossofdilutionwater.

Theconstructionofachlorinedioxidegeneratorisnotdifficult.Commerciallyavailableonesarerelatively
simple,withpumpstomovetheprecursors.Forthesetypesofsystems,thesafetyaspectsofthedesign
havetobebuiltin.Thatis,variouscontrolsareinstalledwhicharedesignedtoworkincaseofaproblem.

Moreelegantdesignsarethosesystemswhichareeductordriven.Suchsystemsareinherentlysafe.Loss
ofdilutionwaterleadstolossofvacuumandthegenerationofClO2isinterrupted.Thesesystemsrelyon
simplecheckvalvestopreventthebackflowofprecursors.Thesystemshouldbedesignedsothat
nowhereinthesystemdoestheconcentrationofchlorinedioxideexceeditssolubilitylimit.

Thesecondaspectisthestorageoftheprecursorsonsite.Forthoseplantsdesiringtoeliminategaseous
chlorinestorage,athreechemicalfeedapproachwouldbeappropriate(equation2).Storageof
precursorscanbedonesafely.However,ofalltheincidentswhichhavearisenoutoftheuseofchlorine
dioxide,byfarthelargestnumberhavebeenbecauseofimproperstorageorhandlingofthesodium
chloritesolution.Attentiontoproperequipmentselectionandinstallationwillsolvetheseproblems.

Thethirdsafetyaspectistheoperationofequipmentbyplantoperators.Althoughmoderngenerators
canbemadewithpropersafeguards,someknowledgeofthegenerationprocessisrequired.Anoperator
whooperatesthegeneratorparttime,andthenonlyintermittentlywithshiftwork,willnotbeasalertto
problemsasonewhooperatestheunitashisprimaryresponsibility.

BCDMHinsmallquantities,requiresattentionandfrequentrefillingofbrominators.Problemswith
controlofsuchafeedsystemarenotable.ThegenerationofdustbytheBCDMHisonesignificant
disadvantagetousingsmallquantitiesofthematerial.

Theuseofchlorineandsodiumbromideaddsanotherdegreeofcomplexitytotheuseofgaseous
chlorine.Theuseofbleachandsodiumbromideisperhapsthesafestofallthealternativesdiscussed
here.

Ozoneequipmentisreportedtobemaintenanceintensiveandexpensive.Destructionoftheexcess
ozonewhichisproduced(andventsthesystemtoatmosphere)isarequirementforsystemsusedtotreat
potablewater,swimmingpools,andotherapplications.

Inaddition,thereareconcernsabouthumancontactwithwatertreatedwithozone,asbothozoneand
thehydroxylfreeradicalwhichareformedareverystrongoxidizingfreeradicals;somemedicalresearch
hassuggestedafreeradicalmechanismfortheinitiationofcancer.

ECONOMICS
Althoughthepropertiesdiscussedpreviouslymakechlorinedioxideanidealchoiceasamicrobicidefor
industrialcoolingtowers,itsuseasachlorinereplacementhasbeenlimited.Onereasonistheissueof
costs.Theusecostofchlorinedioxidecanbeseveraltimesthatofgaseouschlorine.Withthepressureto
eliminategaseouschlorine,chlorinedioxidecostsbecomefavorabletomanyoftheconventionalchlorine
replacements.Infact,forheavilycontaminatedsystems,theusecostofchlorinedioxidecanrivalthatof
chlorine.66Therelativecostsforcommonchlorinealternativesissimilartothatreportedpreviously,with
somenotableexceptions.

Forcleansystems:

pH6.88.0

Cl2<NaOCl<HOCl+NaBr<ClO2<BCDMH<ozone

pH8.09.3

HOCl+NaBr<ClO2<BCDMH<Cl2<NaOCl<ozone

Forsystemswithhighorganicloading:

pH6.89.3

ClO2<HOCl+NaBr<BCDMH<Cl2<NaOCl<ozone

Forsystemswithammoniacontamination

pH6.89.3
ClO2<HOCl+NaBr<BCDMH<Cl2<NaOCl<ozone

ANOVELAPPROACH
UnichemInternationalhasadoptedanapproachwhichminimizestheimpactofthethreeconsiderations
describedabove.Aneductordrivengeneratorandthethreeprecursorsrequiredformostefficient
generationhavebeenmountedonatruck.Theprecursorsareinindividualdoublecontainment
compartments,eachprecursorhavingitsowncatchbasinincaseofaleak.DOTapprovedcontainers
allowtransportonpublichighways,andtherollprotectionandcompartmentalizationinsuresafe
transportation,evenincaseofanaccident.Minimalquantitiesoftheprecursorsarecarriedoneach
truck,i.e.,justenoughprecursoriscarriedforthatday'sgeneration.Trucksareequippedwith
appropriatesafetyequipment.Deactivatingsolutionsfortheprecursorsandthechlorinedioxidesolution
arecarriedonthevehicle.

UnichemGenerationEngineersarededicatedtothevehicle.Theirjobistogeneratechlorinedioxide
safelyandefficiently.Theylocatethevehiclenearthecoolingtowerofinterestandthenattachshort,
chemicallyresistantflexiblehosesfromtheinletandoutletofthegeneratortoaspeciallydesignedpiping
arrangement.Thepipewhichprovidesmotivewatercomesfromthedischargeofthecoolingtower
recirculationpumps.Thiswaterispipedtothesiteofthegeneratorhookup.Generateddiluteaqueous
chlorinedioxideisreturnednormallytothepumpsumpthroughpipestoaheader.Diluteaqueous
chlorinedioxideisgeneratedandintroducedintothepumpsump.Thequantity,frequency,andduration
havebeenpreviouslydeterminedduringaninitialtwophasetrialperiodwhichincludedsystemcleaning
followedbyfeedrateoptimization.Whileattendingthegeneratorduringthegenerationprocess,the
generationengineerperformssomeroutinetests.

Thismobileapproachallowsthecostofsuchaprocesstobespreadoverseveralcoolingsystems.The
intermittenttreatmentapproachandtheperformancecharacteristicsofchlorinedioxidemakesucha
systemidealformostcoolingsystems.Ofcoursetherewillbethosesystemswhichrequireatreatment
morethanonceevery1to3days.Forsuchsystems,orforthosesystemswhichexperiencesevere
hydrocarbonleakswhichcreatesubstantialincreasesindemand,andforperiodswherethetruckis
undergoingmaintenance,atrailermountedunitisused.Forisolatedsystems,anonsitefixedgeneration
systemcanbeemployed.Theonsitefixedsystemdoesnotansweralloftheitemslistedabove,however,
theperformancecharacteristicsmayoutweighotherconsiderationsinchoosingachlorinereplacement.

TheareaswhichhavelimitedtheuseofchlorinedioxideinmanyindustrialplantsaretheSafetoUse/Easy
toHandleareas.Theseareasareaddressedbytheintroductionofthemobileconcept.Mobilegeneration
systemshavebeenusedsuccessfullyintheoilfieldforseveralyears.Themobilesystembringsthe
followingbenefits:
Nostorageofhazardouschemicalsonsite.
Minimalchemicalsbroughtonsite.
Noplanthandlingofhazardouschemicals.
EconomicswhicharecomparabletoBCDMH.
Nocapitalinvestment.
Safety.

SUMMARY
Thepropertiesofanidealmicrobicidehavebeendescribed.Thecommonlyusedoxidizingbiocides,
chlorine,bromine,chlorinedioxideandozonehavebeenreviewedinthelightoftheseproperties.The
resultsaresummarizedinFigure7.


COMPARISONOFOXIDIZINGBIOCIDESINLIGHT
OFTHECRITERIAOFAN'IDEAL'BIOCIDE
ReportCard

HOCl HOBr ClO2 O3

PERFORMANCE
HighpH

Kinetics

Selectivity

Biofilm

SystemContamination

BacterialRecovery

THM

TOX

ofprimaryoxidant

ofoxidationbyproducts

ofoxidationreactionproducts B

residuallife(shortlifebest)

EasytoUse

SafetoHandle

CleanSystem

ContaminatedSystem

2.6

2.8

3.3 2.7

ENVIRONMENTAL

Toxicity

SAFETY

ECONOMICS

CumulativeGPA

Fig.7.RelativeRankingsforChlorineBromine,ChlorineDioxideinViewofCharacteristicsofanIdeal
Biocide.

Althoughtheserelativerankingsaresomewhatsubjective,therankingsarebasedondatafromthe
literature.Gradeshavebeenassignedtoeachcategory,andacumulativegradepointaveragehasbeen
computed.

Itshouldbeclearfromthisthatalthougheachoftheoxidizerslistedexcelinoneormoreareas,when
reviewedasawhole,chlorinedioxidecomesclosertoachievingthestatusof'Ideal'biocidethananyof
theothers.

CONCLUSIONS
Theshorttermdrivingforceforthemoveawayfromgaseouschlorinetothevariousalternativesis
predominantlythehealthandsafetyissuesrelatingtothehandling,storageandintegrityofoneton
cylinders.Iftherecenttrendcontinues,thelongtermforcedrivingthemoveawayfromgaseouschlorine

willbethereactionproductsbetweenchlorineandorganics,andtheimpactthatthesechemicalshaveon
theenvironment.

Wehaveseenamoveintobrominechemistry,althoughthiswillbeundoubtedlyarelativelyshortterm
measureforthesamereasonifthetrendcontinues.Notmuchworkenvironmentallyhasbeendonewith
brominatedorganics,althoughtheyareexpectedtobemoreharmfulthanstructurallysimilarchlorinated
organics.

Ozoneasaviablelongtermreplacementforchlorineisbeingexplored,duetoitsexcellentbiocidal
activity.However,ozonedoessufferfromseveralseriousdrawbacks.Becauseofitsstrongoxidizing
ability,itwillnotdifferentiatebetweenthetargetorganismsandthecorrosioninhibitorpackagesused
withittocontrolscaleandcorrosion.107Itseffectivenessonbiofilmcontrolisquestionable.

Iftheindustrytrendcontinues,theusefullifeofhypohalousacidbasedoxidizingbiocideswillbelimited.
Withtheadditionalfactorsofincreasingwaterreuse,i.e.,increasingsystemcontamination,and
regulatoryrequirementsofnonoxidizingbiocidereregistrations,i.e.,decreasingavailabilityofnon
oxidizingbiocides,theneedforahighperformancechlorinereplacementisbecomingincreasingly
apparent.Thesuperiorperformancecharacteristicsofchlorinedioxidecoupledwiththemobilefeed
systemmakeschlorinedioxidethe'Ideal'biocide.

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