Title:ASimpleandAccurateMethodfortheDeterminationofCO2 LevelsinCarbonated BeveragesUsingTotalOrganicCarbon(TOC)Analysis Authors:StephenLawson,WillMcHaleandBrianWallace Introduction: Thehistoryofbeveragecarbonationislongandvaried.Chemists,suchasRobertBoyle, experimentedwithwaysofmakingcarbonatedbeveragesforthepurposeofflavor enhancementandpreservation.ThelevelofCO2 containedinmostcarbonatedbeverages todayismuchmoreofascienceinthatitisinstrumentalinachievingthedesired 1 combinationsoftaste,texture(foam/frothinbeers)andappearance. Becauseofthe diffusivepropertiesofairandCO2,levelsinplasticbottlesaresometimeshigherinitially 2 toaccountforsomeexpectedlossesovertime.

Inthecaseofbeer,itisnotonly importantduringtheproduction/fermentationprocess,butalsointhepackagingstagesin thatbottledandcannedbeersrequiremuchhigherCO2 levelsthankeggedbeers. AlthoughInfraredspectroscopyisan oftusedmeansofmonitoringCO2 levelsinsitu, ageoldandsometimescumbersomemethodsfortheofflinedeterminationofCO2 levels 3 inbeerandotherbeveragesexist(titration,CorningMethod,etc.). Theneedforfaster andmoreaccuratemeansofmeasuringCO2 inbeverageshasprecipitatedanumberof analyticaladvancementsinrecentyears,butnonemorepromisingthantheuseoftotal organiccarbon(TOC)analysis. ExperimentalDiscussion: Equipment: AsamethodofcomparisontotheTOC,aDionix ICS1000IonExchangesystemwas firstemployedwithlimitedsuccesswithanAllsep50x4.6mmcolumn4mMp Hydroxybenzoicacidmobilephase,andthebestresultswereobtainedwithaMetrosep Dual4monolithiccolumn1004.6highcapacitycolumn.Eluentswithahigherbasic ionicstrengthworkedbest(bufferedcalciumchlorideforexample),anddirect conductivitydetectionofthespecies. ATeledyneTekmarPhoenix8000whichwascalibratedforhighinorganiccarbonlevels (upto5000ppm)withbicarbonatesolutionswasusedtomeasuretheCO2 concentrations inthesamples.ThePhoenix8000employsUVPersulfateoxidationandNDIRdetection ofCO2.andwasselectedforitsfast,accurateanalysiscapabilitiesandreputationfor havingextremelylowsamplecarryover.Reagentsusedwerea10%ammonium persulfate/5%phosphoricacidoxidizingsolutionanda21%phosphoricacidsolutionfor samplepHcontrol.PurifiedwaterfortheTOCsystemandstandardpreparationwas obtainedfromaU.S.Filterion exchangepurificationsystem.Thesystemwasoperated inTICICmodeasopposedtothenonpurgeableorganiccarbonmode(TOCmode)that isusedtomonitorexclusivelyorganiccarboninsamples. Results:

TheresultsforaseriesofbeersamplesareshowninTable1andFigure1,withthesame samplespairedforTOCandIonChromatography.Althoughconditionsforthe comparisonwereimperfectinthatthehandlingofthesamplesandanalysistimeswere difficulttokeepconstant,thedataclearlyshowsagreement.Itshouldbenotedthatthese valuesarelowerthanexpectedbasedontheknowledgewehaveregardingCO2 concentrationsinbeers,whichagain,canlikelybeattributedtotheinconsistentandnon idealnatureofthesamplehandling.CO2 levelsinbeeraretypicallyaround5000ppm, 6 butvaryfrom40006000ppmingeneral. Theionchromatographyresultswere convertedfromcarbonicacidresultsintoarepresentationofCO2 inthesamples.
Sample 1 2 3 4 5 6 7 8 9 10 TOC(ppm) 4745.6 4564.8 3180.8 3384 4384 4259.2 4414.4 3203.2 3484.8 4214.4 IonChrom(ppm) 3547.2 4084.8 3430.4 2801.6 3208 3966.4 3198.4 2913.6 3661 3139.2

Table1 ComparisonofResultsforTOCandIonChromatography

Comparisonof[CO2]forIonChromatographyandTOC
[CO2]inpartspermillion 5000 4000 3000 2000 1000 0 1 2 3 4 5 6 7 8 9 10 Sample
Figure1 Comparisonof ResultsforTOCandIonChromatography

TOC(ppm) IonChrom(ppm)

Conclusion: UtilizingthefastandeasymethodofinorganiccarbonanalysisavailablewithaTeledyne TekmarPhoenix8000TOCanalyzer,itwaspossibletoobtainCO2levelsinbeer comparabletothoseobtainedbyionchromatography.With35minuteanalysistimes andnospecialsamplehandlingrequirements,themethodismuchfasterandsimplerthan traditionalmethodsforlaboratoryanalysisofCO2 inbeverages.Withananalysisrange

of010,000ppmforinorganiccarbon,thePhoenix8000isabletoaccommodateawide rangeofcarbonatedbeveragesamples.Duetotimeconstraints,thestudywaslimitedto theanalysisofbeeronly,butisbeingexpandedtoincludeothercarbonatedbeveragesat thetimeofthispublication. Acknowledgements: TeledyneTekmarwouldliketothanktheChemistryDepartmentattheUniversityof Denverforuseoftheirequipmentandfacilities.Specifically,wethankDr.Balasingam Murugaverlfortheguidanceandsupportheprovidedthroughoutthiswork.

References: 1. ManufactureandAnalysisofCarbonatedBeverages,MorrisB.Jacobs,Chemical PublishingCo.,Inc.,(NewYork,1959). 2. ChemistryandTechnologyofSoftDrinksandFruitJuices,Ed.byP.R.Ashurst, SheffieldAcademicPress(Sheffield,England,1998). 3. Stewart,GrahamD.,WortClarity:EffectsonFermentation,MBAATQ,vol41, no.1,2004,1826. 4. Fan,Hui,etal,AnalysisofCarbonicAcidinWaterSamplesbyIonExclusion ChromatographywithPureWaterasEluent,AnalyticalSciences,Vol.21(2005) ,No.2p.121. 5. Charbonneau,S.,etal,Determinationofcarbonicacidinsteamcondensatecycle samplesusingnonsuppressedionchromatography,AnalyticalChemistry, 1995,vol.67,no.7,pp.12041209. 6. http://www.brewboard.com/index.php?showtopic=56608&st=0