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Atomicabsorptionspectroscopy
FromWikipedia,thefreeencyclopedia

Atomicabsorptionspectroscopy(AAS)isa
spectroanalyticalprocedureforthequantitative
determinationofchemicalelementsusingthe
absorptionofopticalradiation(light)byfreeatomsin
thegaseousstate.
Inanalyticalchemistrythetechniqueisusedfor
determiningtheconcentrationofaparticularelement
(theanalyte)inasampletobeanalyzed.AAScanbe
usedtodetermineover70differentelementsinsolution
ordirectlyinsolidsamplesusedinpharmacology,
biophysicsandtoxicologyresearch.
Atomicabsorptionspectroscopywasfirstusedasan
Flameatomicabsorptionspectroscopyinstrument
analyticaltechnique,andtheunderlyingprincipleswere
establishedinthesecondhalfofthe19thcenturyby
RobertWilhelmBunsenandGustavRobertKirchhoff,bothprofessorsattheUniversityofHeidelberg,
Germany.[1]
ThemodernformofAASwaslargelydevelopedduringthe1950sbyateamofAustralianchemists.They
wereledbySirAlanWalshattheCommonwealthScientificandIndustrialResearchOrganisation
(CSIRO),DivisionofChemicalPhysics,inMelbourne,Australia.[2][3]
Atomicabsorptionspectrometryhasmanyusesindifferentareasofchemistrysuchas:
Clinicalanalysis:Analyzingmetalsinbiologicalfluidsandtissuessuchaswholeblood,plasma,
urine,saliva,braintissue,liver,muscletissue,semen
Pharmaceuticals:Insomepharmaceuticalmanufacturingprocesses,minutequantitiesofacatalyst
thatremaininthefinaldrugproduct
Wateranalysis:Analyzingwaterforitsmetalcontent.

Contents
1 Principles
2 Instrumentation
2.1 Atomizers
2.1.1 Flameatomizers
2.1.2 Electrothermalatomizers
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2.1.3 Specializedatomizationtechniques
2.1.3.1 Glowdischargeatomization
2.1.3.2 Hydrideatomization
2.1.3.3 Coldvaporatomization
2.2 Radiationsources
2.2.1 Hollowcathodelamps
2.2.2 Electrodelessdischargelamps
2.2.3 Deuteriumlamps
2.2.4 Continuumsources
2.3 Spectrometer
2.3.1 SpectrometersforLSAAS
2.3.2 SpectrometersforCSAAS
3 Backgroundabsorptionandbackgroundcorrection
3.1 BackgroundcorrectiontechniquesinLSAAS
3.1.1 Deuteriumbackgroundcorrection
3.1.2 SmithHieftjebackgroundcorrection
3.1.3 Zeemaneffectbackgroundcorrection
3.2 BackgroundcorrectiontechniquesinHRCSAAS
3.2.1 Backgroundcorrectionusingcorrectionpixels
3.2.2 Backgroundcorrectionusingaleastsquaresalgorithm
4 Seealso
5 References
6 Furtherreading

Principles
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Thetechniquemakesuseofabsorptionspectrometrytoassesstheconcentrationofananalyteinasample.
Itrequiresstandardswithknownanalytecontenttoestablishtherelationbetweenthemeasuredabsorbance
andtheanalyteconcentrationandreliesthereforeontheBeerLambertLaw.
Inshort,theelectronsoftheatomsintheatomizercanbepromotedtohigherorbitals(excitedstate)fora
shortperiodoftime(nanoseconds)byabsorbingadefinedquantityofenergy(radiationofagiven
wavelength).Thisamountofenergy,i.e.,wavelength,isspecifictoaparticularelectrontransitionina
particularelement.Ingeneral,eachwavelengthcorrespondstoonlyoneelement,andthewidthofan
absorptionlineisonlyoftheorderofafewpicometers(pm),whichgivesthetechniqueitselemental
selectivity.Theradiationfluxwithoutasampleandwithasampleintheatomizerismeasuredusinga
detector,andtheratiobetweenthetwovalues(theabsorbance)isconvertedtoanalyteconcentrationor
massusingtheBeerLambertLaw.

Instrumentation
Inordertoanalyzeasampleforitsatomicconstituents,ithasto
beatomized.Theatomizersmostcommonlyusednowadaysare
flamesandelectrothermal(graphitetube)atomizers.Theatoms
shouldthenbeirradiatedbyopticalradiation,andtheradiation
sourcecouldbeanelementspecificlineradiationsourceora
continuumradiationsource.Theradiationthenpassesthrougha
monochromatorinordertoseparatetheelementspecific
radiationfromanyotherradiationemittedbytheradiation
source,whichisfinallymeasuredbyadetector.

Atomicabsorptionspectrometerblock
diagram

Atomizers
Theatomizersmostcommonlyusednowadaysare(spectroscopic)flamesandelectrothermal(graphite
tube)atomizers.Otheratomizers,suchasglowdischargeatomization,hydrideatomization,orcoldvapor
atomizationmightbeusedforspecialpurposes.
Flameatomizers
TheoldestandmostcommonlyusedatomizersinAASareflames,principallytheairacetyleneflamewith
atemperatureofabout2300Candthenitrousoxidesystem(N2O)acetyleneflamewithatemperatureof
about2700C.Thelatterflame,inaddition,offersamorereducingenvironment,beingideallysuitedfor
analyteswithhighaffinitytooxygen.
Liquidordissolvedsamplesaretypicallyusedwithflameatomizers.Thesamplesolutionisaspiratedbya
pneumaticanalyticalnebulizer,transformedintoanaerosol,whichisintroducedintoaspraychamber,
whereitismixedwiththeflamegasesandconditionedinawaythatonlythefinestaerosoldroplets(<
10m)entertheflame.Thisconditioningprocessisresponsiblethatonlyabout5%oftheaspiratedsample
solutionreachestheflame,butitalsoguaranteesarelativelyhighfreedomfrominterference.
Ontopofthespraychamberisaburnerheadthatproducesaflamethatislaterallylong(usually510cm)
andonlyafewmmdeep.Theradiationbeampassesthroughthisflameatitslongestaxis,andtheflamegas
flowratesmaybeadjustedtoproducethehighestconcentrationoffreeatoms.Theburnerheightmayalso
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beadjusted,sothattheradiationbeampassesthroughthezoneof
highestatomclouddensityintheflame,resultinginthehighest
sensitivity.
Theprocessesinaflameincludethefollowingstages:
Desolvation(drying)thesolventisevaporatedandthedry
samplenanoparticlesremain
Vaporization(transfertothegaseousphase)thesolid
particlesareconvertedintogaseousmolecules
Atomizationthemoleculesaredissociatedintofreeatoms
Ionizationdependingontheionizationpotentialofthe
analyteatomsandtheenergyavailableinaparticularflame,
atomsmightbeinpartconvertedtogaseousions.

Alaboratoryflamephotometerthat
usesapropaneoperatedflame
atomizer

Eachofthesestagesincludestheriskofinterferenceincasethedegreeofphasetransferisdifferentforthe
analyteinthecalibrationstandardandinthesample.Ionizationisgenerallyundesirable,asitreducesthe
numberofatomsthatareavailableformeasurement,i.e.,thesensitivity.
InflameAASasteadystatesignalisgeneratedduringthetimeperiodwhenthesampleisaspirated.This
techniqueistypicallyusedfordeterminationsinthemgL1range,andmaybeextendeddowntoafewg
L1forsomeelements.
Electrothermalatomizers
ElectrothermalAAS(ETAAS)using
graphitetubeatomizerswaspioneered
byBorisV.LvovattheSaint
PetersburgPolytechnicalInstitute,
Russia,[4]sincethelate1950s,and
investigatedinparallelbyHans
MassmannattheInstituteof
SpectrochemistryandApplied
Spectroscopy(ISAS)inDortmund,
Germany.[5]
Althoughawidevarietyofgraphitetube
designshavebeenusedovertheyears,
thedimensionsnowadaysaretypically
2025mminlengthand56mminner
diameter.Withthistechnique
liquid/dissolved,solidandgaseous
GFAAmethoddevelopment
samplesmaybeanalyzeddirectly.A
measuredvolume(typically1050L)
oraweighedmass(typicallyaround1mg)ofasolidsampleareintroducedintothegraphitetubeand
subjecttoatemperatureprogram.Thistypicallyconsistsofstages,suchas:
Dryingthesolventisevaporated
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Pyrolysisthemajorityofthematrixconstituentsare
removed
Atomizationtheanalyteelementisreleasedtothegaseous
phase
Cleaningeventualresiduesinthegraphitetubeareremoved
athightemperature.
Thegraphitetubesareheatedviatheirohmicresistanceusingalow
voltagehighcurrentpowersupplythetemperatureintheindividual
stagescanbecontrolledveryclosely,andtemperatureramps
betweentheindividualstagesfacilitateseparationofsample
Graphitetube
components.Tubesmaybeheatedtransverselyorlongitudinally,
wheretheformeroneshavetheadvantageofamorehomogeneous
temperaturedistributionovertheirlength.Thesocalledstabilizedtemperatureplatformfurnace(STPF)
concept,proposedbyWalterSlavin,basedonresearchofBorisLvov,makesETAASessentiallyfree
frominterference.Themajorcomponentsofthisconceptare:
Atomizationofthesamplefromagraphiteplatforminsertedintothegraphitetube(Lvovplatform)
insteadoffromthetubewallinordertodelayatomizationuntilthegasphaseintheatomizerhas
reachedastabletemperature
Useofachemicalmodifierinordertostabilizetheanalytetoapyrolysistemperaturethatis
sufficienttoremovethemajorityofthematrixcomponents
Integrationoftheabsorbanceoverthetimeofthetransientabsorptionsignalinsteadofusingpeak
heightabsorbanceforquantification.
InETAASatransientsignalisgenerated,theareaofwhichisdirectlyproportionaltothemassofanalyte
(notitsconcentration)introducedintothegraphitetube.Thistechniquehastheadvantagethatanykindof
sample,solid,liquidorgaseous,canbeanalyzeddirectly.Itssensitivityis23ordersofmagnitudehigher
thanthatofflameAAS,sothatdeterminationsinthelowgL1range(foratypicalsamplevolumeof
20L)andngg1range(foratypicalsamplemassof1mg)canbecarriedout.Itshowsaveryhighdegree
offreedomfrominterferences,sothatETAASmightbeconsideredthemostrobusttechniqueavailable
nowadaysforthedeterminationoftraceelementsincomplexmatrices.
Specializedatomizationtechniques
Whileflameandelectrothermalvaporizersarethemostcommonatomizationtechniques,severalother
atomizationmethodsareutilizedforspecializeduse.
Glowdischargeatomization

Aglowdischargedevice(GD)servesasaversatilesource,asitcansimultaneouslyintroduceandatomize
thesample.Theglowdischargeoccursinalowpressureargongasatmospherebetween1and10torr.In
thisatmosphereliesapairofelectrodesapplyingaDCvoltageof250to1000Vtobreakdowntheargon
gasintopositivelychargedionsandelectrons.Theseions,undertheinfluenceoftheelectricfield,are
acceleratedintothecathodesurfacecontainingthesample,bombardingthesampleandcausingneutral
sampleatomejectionthroughtheprocessknownassputtering.Theatomicvaporproducedbythis
dischargeiscomposedofions,groundstateatoms,andfractionofexcitedatoms.Whentheexcitedatoms
relaxbackintotheirgroundstate,alowintensityglowisemitted,givingthetechniqueitsname.
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Therequirementforsamplesofglowdischargeatomizersisthattheyareelectricalconductors.
Consequently,atomizersaremostcommonlyusedintheanalysisofmetalsandotherconductingsamples.
However,withpropermodifications,itcanbeutilizedtoanalyzeliquidsamplesaswellasnonconducting
materialsbymixingthemwithaconductor(e.g.graphite).
Hydrideatomization

Hydridegenerationtechniquesarespecializedinsolutionsofspecificelements.Thetechniqueprovidesa
meansofintroducingsamplescontainingarsenic,antimony,tin,selenium,bismuth,andleadintoan
atomizerinthegasphase.Withtheseelements,hydrideatomizationenhancesdetectionlimitsbyafactorof
10to100comparedtoalternativemethods.Hydridegenerationoccursbyaddinganacidifiedaqueous
solutionofthesampletoa1%aqueoussolutionofsodiumborohydride,allofwhichiscontainedinaglass
vessel.Thevolatilehydridegeneratedbythereactionthatoccursissweptintotheatomizationchamberby
aninertgas,whereitundergoesdecomposition.Thisprocessformsanatomizedformoftheanalyte,which
canthenbemeasuredbyabsorptionoremissionspectrometry.
Coldvaporatomization

Thecoldvaportechniqueanatomizationmethodlimitedtoonlythedeterminationofmercury,duetoit
beingtheonlymetallicelementtohavealargeenoughvaporpressureatambienttemperature.Becauseof
this,ithasanimportantuseindeterminingorganicmercurycompoundsinsamplesandtheirdistributionin
theenvironment.ThemethodinitiatesbyconvertingmercuryintoHg2+byoxidationfromnitricand
sulfuricacids,followedbyareductionofHg2+withtin(II)chloride.Themercury,isthensweptintoalong
passabsorptiontubebybubblingastreamofinertgasthroughthereactionmixture.Theconcentrationis
determinedbymeasuringtheabsorbanceofthisgasat253.7nm.Detectionlimitsforthistechniquearein
thepartsperbillionrangemakingitanexcellentmercurydetectionatomizationmethod.

Radiationsources
WehavetodistinguishbetweenlinesourceAAS(LSAAS)andcontinuumsourceAAS(CSAAS).In
classicalLSAAS,asithasbeenproposedbyAlanWalsh,thehighspectralresolutionrequiredforAAS
measurementsisprovidedbytheradiationsourceitselfthatemitsthespectrumoftheanalyteintheformof
linesthatarenarrowerthantheabsorptionlines.Continuumsources,suchasdeuteriumlamps,areonly
usedforbackgroundcorrectionpurposes.Theadvantageofthistechniqueisthatonlyamediumresolution
monochromatorisnecessaryformeasuringAAShowever,ithasthedisadvantagethatusuallyaseparate
lampisrequiredforeachelementthathastobedetermined.InCSAAS,incontrast,asinglelamp,emitting
acontinuumspectrumovertheentirespectralrangeofinterestisusedforallelements.Obviously,ahigh
resolutionmonochromatorisrequiredforthistechnique,aswillbediscussedlater.
Hollowcathodelamps
Hollowcathodelamps(HCL)arethemostcommonradiation
sourceinLSAAS.Insidethesealedlamp,filledwithargonor
neongasatlowpressure,isacylindricalmetalcathode
Hollowcathodelamp(HCL)
containingtheelementofinterestandananode.Ahighvoltage
isappliedacrosstheanodeandcathode,resultinginan
ionizationofthefillgas.Thegasionsareacceleratedtowardsthecathodeand,uponimpactonthecathode,
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sputtercathodematerialthatisexcitedintheglowdischargetoemittheradiationofthesputteredmaterial,
i.e.,theelementofinterest.Mostlampswillhandleahandfulofelements,i.e.58.Atypicalmachinewill
havetwolamps,onewilltakecareoffiveelementsandtheotherwillhandlefourelementsforatotalof
nineelementsanalyzed.
Electrodelessdischargelamps
Electrodelessdischargelamps(EDL)containasmallquantityoftheanalyteasametalorasaltinaquartz
bulbtogetherwithaninertgas,typicallyargon,atlowpressure.Thebulbisinsertedintoacoilthatis
generatinganelectromagneticradiofrequencyfield,resultinginalowpressureinductivelycoupled
dischargeinthelamp.TheemissionfromanEDLishigherthanthatfromanHCL,andthelinewidthis
generallynarrower,butEDLsneedaseparatepowersupplyandmightneedalongertimetostabilize.
Deuteriumlamps
DeuteriumHCLorevenhydrogenHCLanddeuteriumdischargelampsareusedinLSAASfor
backgroundcorrectionpurposes.Theradiationintensityemittedbytheselampsdecreasessignificantlywith
increasingwavelength,sothattheycanbeonlyusedinthewavelengthrangebetween190andabout
320nm.
Continuumsources
WhenacontinuumradiationsourceisusedforAAS,itis
necessarytouseahighresolutionmonochromator,aswillbe
discussedlater.Inaddition,itisnecessarythatthelampemits
radiationofintensityatleastanorderofmagnitudeabovethat
ofatypicalHCLovertheentirewavelengthrangefrom190nm
to900nm.Aspecialhighpressurexenonshortarclamp,
operatinginahotspotmodehasbeendevelopedtofulfillthese
requirements.

Spectrometer
Asalreadypointedoutabove,thereisadifferencebetween
mediumresolutionspectrometersthatareusedforLSAASand
highresolutionspectrometersthataredesignedforCSAAS.
Thespectrometerincludesthespectralsortingdevice
(monochromator)andthedetector.
SpectrometersforLSAAS

Xenonlampasacontinuousradiation
source

InLSAASthehighresolutionthatisrequiredforthemeasurementofatomicabsorptionisprovidedbythe
narrowlineemissionoftheradiationsource,andthemonochromatorsimplyhastoresolvetheanalytical
linefromotherradiationemittedbythelamp.Thiscanusuallybeaccomplishedwithabandpassbetween
0.2and2nm,i.e.,amediumresolutionmonochromator.AnotherfeaturetomakeLSAASelementspecific
ismodulationoftheprimaryradiationandtheuseofaselectiveamplifierthatistunedtothesame
modulationfrequency,asalreadypostulatedbyAlanWalsh.Thiswayany(unmodulated)radiationemitted
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forexamplebytheatomizercanbeexcluded,whichisimperativeforLSAAS.Simplemonochromatorsof
theLittrowor(better)theCzernyTurnerdesignaretypicallyusedforLSAAS.Photomultipliertubesare
themostfrequentlyuseddetectorsinLSAAS,althoughsolidstatedetectorsmightbepreferredbecauseof
theirbettersignaltonoiseratio.
SpectrometersforCSAAS
WhenacontinuumradiationsourceisusedforAASmeasurementitisindispensabletoworkwithahigh
resolutionmonochromator.Theresolutionhastobeequaltoorbetterthanthehalfwidthofanatomic
absorptionline(about2pm)inordertoavoidlossesofsensitivityandlinearityofthecalibrationgraph.The
researchwithhighresolution(HR)CSAASwaspioneeredbythegroupsofOHaverandHarnlyinthe
USA,whoalsodevelopedthe(upuntilnow)onlysimultaneousmultielementspectrometerforthis
technique.Thebreakthrough,however,camewhenthegroupofBeckerRossinBerlin,Germany,builta
spectrometerentirelydesignedforHRCSAAS.ThefirstcommercialequipmentforHRCSAASwas
introducedbyAnalytikJena(Jena,Germany)atthebeginningofthe21stcentury,basedonthedesign
proposedbyBeckerRossandFlorek.Thesespectrometersuseacompactdoublemonochromatorwitha
prismpremonochromatorandanechellegratingmonochromatorforhighresolution.Alinearcharge
coupleddevice(CCD)arraywith200pixelsisusedasthedetector.Thesecondmonochromatordoesnot
haveanexitslithencethespectralenvironmentatbothsidesoftheanalyticallinebecomesvisibleathigh
resolution.Astypicallyonly35pixelsareusedtomeasuretheatomicabsorption,theotherpixelsare
availableforcorrectionpurposes.Oneofthesecorrectionsisthatforlampflickernoise,whichis
independentofwavelength,resultinginmeasurementswithverylownoiselevelothercorrectionsarethose
forbackgroundabsorption,aswillbediscussedlater.

Backgroundabsorptionandbackgroundcorrection
Therelativelysmallnumberofatomicabsorptionlines(comparedtoatomicemissionlines)andtheir
narrowwidth(afewpm)makespectraloverlaprarethereareonlyveryfewexamplesknownthatan
absorptionlinefromoneelementwilloverlapwithanother.Molecularabsorption,incontrast,ismuch
broader,sothatitismorelikelythatsomemolecularabsorptionbandwilloverlapwithanatomicline.This
kindofabsorptionmightbecausedbyundissociatedmoleculesofconcomitantelementsofthesampleor
byflamegases.Wehavetodistinguishbetweenthespectraofdiatomicmolecules,whichexhibita
pronouncedfinestructure,andthoseoflarger(usuallytriatomic)moleculesthatdontshowsuchfine
structure.Anothersourceofbackgroundabsorption,particularlyinETAAS,isscatteringoftheprimary
radiationatparticlesthataregeneratedintheatomizationstage,whenthematrixcouldnotberemoved
sufficientlyinthepyrolysisstage.
Allthesephenomena,molecularabsorptionandradiationscattering,canresultinartificiallyhigh
absorptionandanimproperlyhigh(erroneous)calculationfortheconcentrationormassoftheanalytein
thesample.Thereareseveraltechniquesavailabletocorrectforbackgroundabsorption,andtheyare
significantlydifferentforLSAASandHRCSAAS.

BackgroundcorrectiontechniquesinLSAAS
InLSAASbackgroundabsorptioncanonlybecorrectedusinginstrumentaltechniques,andallofthemare
basedontwosequentialmeasurements,firstly,totalabsorption(atomicplusbackground),secondly,
backgroundabsorptiononly,andthedifferenceofthetwomeasurementsgivesthenetatomicabsorption.
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Becauseofthis,andbecauseoftheuseofadditionaldevicesinthespectrometer,thesignaltonoiseratioof
backgroundcorrectedsignalsisalwayssignificantlyinferiorcomparedtouncorrectedsignals.Itshould
alsobepointedoutthatinLSAASthereisnowaytocorrectfor(therarecaseof)adirectoverlapoftwo
atomiclines.InessencetherearethreetechniquesusedforbackgroundcorrectioninLSAAS:
Deuteriumbackgroundcorrection
Thisistheoldestandstillmostcommonlyusedtechnique,particularlyforflameAAS.Inthiscase,a
separatesource(adeuteriumlamp)withbroademissionisusedtomeasurethebackgroundabsorptionover
theentirewidthoftheexitslitofthespectrometer.Theuseofaseparatelampmakesthistechniquethe
leastaccurateone,asitcannotcorrectforanystructuredbackground.Italsocannotbeusedatwavelengths
aboveabout320nm,astheemissionintensityofthedeuteriumlampbecomesveryweak.Theuseof
deuteriumHCLispreferablecomparedtoanarclampduetothebetterfitoftheimageoftheformerlamp
withthatoftheanalyteHCL.
SmithHieftjebackgroundcorrection
Thistechnique(namedaftertheirinventors)isbasedonthelinebroadeningandselfreversalofemission
linesfromHCLwhenhighcurrentisapplied.Totalabsorptionismeasuredwithnormallampcurrent,i.e.,
withanarrowemissionline,andbackgroundabsorptionafterapplicationofahighcurrentpulsewiththe
profileoftheselfreversedline,whichhaslittleemissionattheoriginalwavelength,butstrongemissionon
bothsidesoftheanalyticalline.Theadvantageofthistechniqueisthatonlyoneradiationsourceisused
amongthedisadvantagesarethatthehighcurrentpulsesreducelamplifetime,andthatthetechniquecan
onlybeusedforrelativelyvolatileelements,asonlythoseexhibitsufficientselfreversaltoavoiddramatic
lossofsensitivity.Anotherproblemisthatbackgroundisnotmeasuredatthesamewavelengthastotal
absorption,makingthetechniqueunsuitableforcorrectingstructuredbackground.
Zeemaneffectbackgroundcorrection
Analternatingmagneticfieldisappliedattheatomizer(graphitefurnace)tosplittheabsorptionlineinto
threecomponents,thecomponent,whichremainsatthesamepositionastheoriginalabsorptionline,and
twocomponents,whicharemovedtohigherandlowerwavelengths,respectively(seeZeemanEffect).
Totalabsorptionismeasuredwithoutmagneticfieldandbackgroundabsorptionwiththemagneticfieldon.
Thecomponenthastoberemovedinthiscase,e.g.usingapolarizer,andthecomponentsdonot
overlapwiththeemissionprofileofthelamp,sothatonlythebackgroundabsorptionismeasured.The
advantagesofthistechniqueare
1. thattotalandbackgroundabsorptionaremeasuredwiththesameemissionprofileofthesamelamp,
sothatanykindofbackground,includingbackgroundwithfinestructurecanbecorrectedaccurately,
unlessthemoleculeresponsibleforthebackgroundisalsoaffectedbythemagneticfield
2. usingachopperasapolariserreducesthesignaltonoiseratio.Whilethedisadvantagesarethe
increasedcomplexityofthespectrometerandpowersupplyneededforrunningthepowerfulmagnet
neededtosplittheabsorptionline.

BackgroundcorrectiontechniquesinHRCSAAS

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InHRCSAASbackgroundcorrectioniscarriedoutmathematicallyinthesoftwareusinginformationfrom
detectorpixelsthatarenotusedformeasuringatomicabsorptionhence,incontrasttoLSAAS,no
additionalcomponentsarerequiredforbackgroundcorrection.
Backgroundcorrectionusingcorrectionpixels
IthasalreadybeenmentionedthatinHRCSAASlampflickernoiseiseliminatedusingcorrectionpixels.
Infact,anyincreaseordecreaseinradiationintensitythatisobservedtothesameextentatallpixelschosen
forcorrectioniseliminatedbythecorrectionalgorithm.Thisobviouslyalsoincludesareductionofthe
measuredintensityduetoradiationscatteringormolecularabsorption,whichiscorrectedinthesameway.
Asmeasurementoftotalandbackgroundabsorption,andcorrectionforthelatter,arestrictlysimultaneous
(incontrasttoLSAAS),eventhefastestchangesofbackgroundabsorption,astheymaybeobservedinET
AAS,donotcauseanyproblem.Inaddition,asthesamealgorithmisusedforbackgroundcorrectionand
eliminationoflampnoise,thebackgroundcorrectedsignalsshowamuchbettersignaltonoiseratio
comparedtotheuncorrectedsignals,whichisalsoincontrasttoLSAAS.
Backgroundcorrectionusingaleastsquaresalgorithm
Theabovetechniquecanobviouslynotcorrectforabackgroundwithfinestructure,asinthiscasethe
absorbancewillbedifferentateachofthecorrectionpixels.InthiscaseHRCSAASisofferingthe
possibilitytomeasurecorrectionspectraofthemolecule(s)thatis(are)responsibleforthebackgroundand
storetheminthecomputer.Thesespectraarethenmultipliedwithafactortomatchtheintensityofthe
samplespectrumandsubtractedpixelbypixelandspectrumbyspectrumfromthesamplespectrumusinga
leastsquaresalgorithm.Thismightsoundcomplex,butfirstofallthenumberofdiatomicmoleculesthat
canexistatthetemperaturesoftheatomizersusedinAASisrelativelysmall,andsecond,thecorrectionis
performedbythecomputerwithinafewseconds.Thesamealgorithmcanactuallyalsobeusedtocorrect
fordirectlineoverlapoftwoatomicabsorptionlines,makingHRCSAAStheonlyAAStechniquethat
cancorrectforthiskindofspectralinterference.

Seealso
Absorptionspectroscopy
BeerLambertlaw
Inductivelycoupledplasmamassspectrometry
JAASJournalofAnalyticalAtomicSpectrometry
Laserabsorptionspectrometry

References
1. "RobertBunsenandGustavKirchhoff".ChemicalHeritageFoundation.Retrieved20140729.
2. McCarthy,G.J."Walsh,AlanBiographicalentry".EncyclopediaofAustralianScience.Retrieved22May
2012.
3. Koirtyohann,S.R.(1991)."AHISTORYOFATOMICABSORPTIONSPECTROMETRY".Analytical
Chemistry63(21):1024A1031A.doi:10.1021/ac00021a716.ISSN00032700.
4. L'vov,Boris(1990).Recentadvancesinabsoluteanalysisbygraphitefurnaceatomicabsorptionspectrometry.
SpectrochimicaActaPartB:AtomicSpectroscopy45.pp.633655.doi:10.1016/05848547(90)80046L.
5. "AnalyticalMethodsforGraphiteTubeAtomizers"(PDF).http://www.agilent.com.AgilentTechnologies.
Externallinkin|website=(help)
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Furtherreading
B.Welz,M.Sperling(1999),AtomicAbsorptionSpectrometry,WileyVCH,Weinheim,Germany,
ISBN3527285717.
A.Walsh(1955),Theapplicationofatomicabsorptionspectratochemicalanalysis,Spectrochim.
Acta7:108117.
J.A.C.Broekaert(1998),AnalyticalAtomicSpectrometrywithFlamesandPlasmas,3rdEdition,
WileyVCH,Weinheim,Germany.
B.V.Lvov(1984),Twentyfiveyearsoffurnaceatomicabsorptionspectroscopy,Spectrochim.Acta
PartB,39:149157.
B.V.Lvov(2005),FiftyyearsofatomicabsorptionspectrometryJ.Anal.Chem.,60:382392.
H.Massmann(1968),VergleichvonAtomabsorptionundAtomfluoreszenzinderGraphitkvette,
Spectrochim.ActaPartB,23:215226.
W.Slavin,D.C.Manning,G.R.Carnrick(1981),Thestabilizedtemperatureplatformfurnace,At.
Spectrosc.2:137145.
B.Welz,H.BeckerRoss,S.Florek,U.Heitmann(2005),HighresolutionContinuumSourceAAS,
WileyVCH,Weinheim,Germany,ISBN3527307362.
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