Resonance ionization spectroscopy for the ultratrace detection of mercury

158 Pages·1997·1.8 MB·English

by  Clevenger, Wendy Leigh, 1970-

RESONANCEIONIZADTEITOENCSTPIEOCNTORFOSMCEORPCYUFROYRTHEULTRATRACE
By
WENDYLEIGHCLEVENGER
OAFDTIHSESOEUFRNTITAVHTEEIRROSENIDQTPOUYRCIOETRSFOEEFRMNLEOTONFERTDIPSDTHAFIOOLITRONHSTPEOHAPGREHRTYDIAEADGLURFAEUTELEFOSIFCLHLMOEONLT
UNIVERSITYOFFLORIDA
1997
ClevengeTrh,isadnidssmerytagtriaonndimsodtehdeirc.atAegdnteostChreemaesmmoarnyWoofotmeyngGraanmdefra.ther.CharlesAnderson
ACKNOWLEDGMENTS
Ihaveoftenthoughtaboutallofthethings1couldhavedonewiththepastfour
syfmuelaelrlysliroenafglimtzhyeearlnoisdfee:sa.pptrNreaocviwealtitenhgat,thesIpseexenpedetirhineegnltcigeihsmteIathwaitvtheheehfnaaddmioalsfytaahgenrdgardfaurdaiuteaentdsset,usdtceahnkotio.nlgtuitnneeals,yIacnadn
ThemainthanksforgettingmethroughanyofthisgotoDr.JamesWinefordner.
Hisawe-inspiringenthusiasm,knowledge,andlaughterhavesetanexamplethatIhope
tocarrywithmealways.Hisunderstandingandrespectforhisstudentsaresomethingto
becherishedandhasmademerealizehowluckyIamtohavebeeninhisgroup.
EqualthanksgotoDr.BenjaminSmithforhisfriendshipandconstantsupport.
Hwaissnv'itssiuonreoIfcwohualdt.goodscienceishasalwaysinspiredmetoexcelandshineinwaysI
whomIFhuratvheerbegernatfiotrutduenaisteexetneonudgehdttoobDersa.ssOolcieagteMdawtivtehevforantdheNpiacsotlotwOomcyemaerts.to.Olweigt'hs
emMnoetrhdwuohsahitaRsicmtheaarrn,adcStucersreaiansttaiivcCisatyb1raewndodouNliadcnodl’iQskielnogtvoeSohuafnvhfeiosrawtsoheraikrsacasinesdnitstitshaton.sceesIinhmaturhisinstgwaoilnrskio.thtahvaenkshLoewahn
andforIgniavdidnigtimoen.aInwoeuxladmplliekeotfothhoawnkhaDrr.dKwaotrhkryfnorWisltludieanmtssfcoarnheprasyuopfpfo.rtIamnudsatdvailcseo
thankDr,RobertKennedy.Dr.JosephDclfino.Dr.JimDeyrupandDr.RickYostfor
theirhelpandsupport,aswellastheUSNationalInstitutesofHealth,theUSDepartment
ofEnergy,andespeciallytheUSEnvironmentalProtectionAgencyfortheirhelpin
fundingthiswork.
Mostimportantly,Imustthankmyparents,JerryandLindaClevenger,forthe
love,support,andencouragementIhavebeenluckyenoughtoreceivemywholelife.
today-IamalsogratefultomybrotherChuckandsisterChristyaswellastherestofmy
family.Ifeelmostblessedtohaveallofthemandtheknowledgethattheyarealways
thereforme.
supportIovmeurstthaelpsaostthfaonukrtyheaersf.rieTnhdesstehaitncIlhudaeveJDmaWdeg,rofurpommewmhbeormsIRhoabveGugeanianredd,mDuacvhe
Rusak,ArthurBestcman,ScottBaker,AndreaCroslyn,BryanCastle,andBeckyLitteral.
EquallyimportantareTradeWilliams.EveHunovice,SundayBrooks.BrendanBoyd,
MikeBruner,AaronWilliams,ScottGordon,andYannisKarayannis.Ialsogivemany
ThankyouGodforallofthewonderfulopportunitiesandexperiencesyouhave
TABLEOFCONTENTS
lIF-nuadrsunccartciIevnedAlutycoeCmdoiucBprlNeneandk-dPTlhoaewisnrmSospaeMlcaEtaxrscoimStepatetrciyotnroSmpeetcrtyrom
SpecianuuCoupledwithlnd;
CHASSRPeuPsTmEoPRmErCneaiRasTnrnocRyc3niOepaolnSfleAcosCTNeo-Oe—iAlczPLoahYimnYiziToaqniIuieSCopsnAecLStpreTocLstcMrooEpsyRcoEpSyOolf.MVerEcDurRyE.SONANCEIONIZATION....33335696
CHARPYTDEBRE4RGRSETSAOTNEASNCEIONIZATIONSPECTROSCOPYOfMERCURY 69
SBAtusafsrfikegrnEifGnfaegscStPpsreecstsrualrelaShniefstsandBroaden ,...7777266*
CHASIPINTGERENTARLA5:TMROESSPOHNEARNECEWIITOHNIAZVATAILOANNOCFHMEEARMCPUURFYIACTAOHMOSNIONFADNIE $1
ResultsandDiscussion
CHACPOTNESRID6:ERMAETTIHONOSDOPTIMIZATIONANDANALYTICAL
ERexspueAPPlrneetairr!lmffyeaootnnrritdmmcaaaaDllnniccsCeecuuoorsffvte-EEtlxoeoccntartotnonC-oSucnIhtee”rme’
CHAPTER7FUTUREWORK
USTOFREFERENCES
BIOGRAPHICALSKETCH
3- LISTOFTABLES
4-
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10-48 73-5
1.lEexvceilt),ataisontatbrualnastietdiobnysfMooroHrgeffoorrlnas=er6,-c7o,n9n-ec1t3e.dlevels1,2,3and4(Rydberg 95
AbosRfletrqhaueciiUrnoeifmveeDnritsssisetfryotroatftihFoelnoDPrerigedrsaeeienntoPefadrDttoioactlthoFeurlGofrfialdPluhmaietlneotsSoocfphhtoyhoel
RESONANCEIONIZADTEITOENCSTPIEOCNTORFOSMCEORPCYUFROYRTHEULTRATRACE
By
August1997
MajorDepartment:Chemistry
Resonanceionizationspectroscopy(RIS)hasbeenproventobeoneofthemost
method(i.e„astreamofineitgas)insteadofaflameorfiimace.Forthesereasons,itis
thewell-establishedmetl
RISinvolvesthe
s.The
0
novelelectroncounterintowhichthemercuryatomsweresweptbyastreamofbuffer
gas.Ahighvoltage(0-3.5kV)wasappliedbetweentwoelectrodestoallowcollection
oftheelectrons.Thesignalwasamplifiedandrecordedonadigitizingoscilloscopeand
laptopcomputer.
FundamentalstudiesofmercuryRydbergstateswerecarriedoutinordertofind
theoptimalconditionsforultratracedetection.Thesestudiesincludedtheeffectofthe
choiceofgaspressureandappliedhighvoltageonthespectrallines.Inaddition,theuse
ogifvaevaalsaingcnahle6a.m6plxif1icsattiiomnesofhitghheereltehcatnrictahlessiiggnnaallowbasserivnevdeswtiitghattehdeannodtmdaelteRr1mSinseedtupt.o
detectionexperimentallydeterminedis1.9X10satomsinthemeasurementvolume.
whichwaslimitedbypoorionizationefficiency.Apreliminarystudyinvolvingthe
generationofmercurybythecoldvapormethodhornaqueousstandards,usingan
unoptimizedRISdetectionschemeandsampleintroductionapparatus,showedlinearity