11/1/2015

ANALYSISOFASHANDMINERALS

4.AnalysisofAshandMinerals

4.1Introduction
Theashcontentisameasureofthetotalamountofmineralspresentwithinafood,whereasthemineralcontentisameasureofthe
amountofspecificinorganiccomponentspresentwithinafood,suchasCa,Na,KandCl.Determinationoftheashandmineralcontentoffoodsis
importantforanumberofreasons:
Nutritionallabeling.Theconcentrationandtypeofmineralspresentmustoftenbestipulatedonthelabelofafood.
Quality.Thequalityofmanyfoodsdependsontheconcentrationandtypeofmineralstheycontain,includingtheirtaste,appearance,textureand
stability.
Microbiologicalstability.Highmineralcontentsaresometimesusedtoretardthegrowthofcertainmicroorganisms.
Nutrition.Somemineralsareessentialtoahealthydiet(e.g.,calcium,phosphorous,potassiumandsodium)whereasotherscanbetoxic(e.g.,
lead,mercury,cadmiumandaluminum).
Processing.Itisoftenimportanttoknowthemineralcontentoffoodsduringprocessingbecausethisaffectsthephysicochemicalpropertiesof
foods.

4.2.DeterminationofAshContent
Ashistheinorganicresidueremainingafterthewaterandorganicmatterhavebeenremovedbyheatinginthepresenceofoxidizingagents,which
providesameasureofthetotalamountofmineralswithinafood.Analyticaltechniquesforprovidinginformationaboutthetotalmineralcontentare
basedonthefactthattheminerals(theanalyte)canbedistinguishedfromalltheothercomponents(thematrix)withinafoodinsome
measurableway.Themostwidelyusedmethodsarebasedonthefactthatmineralsarenotdestroyedbyheating,andthattheyhavealowvolatility
comparedtootherfoodcomponents.Thethreemaintypesofanalyticalprocedureusedtodeterminetheashcontentoffoodsarebasedonthis
principle:dryashing,wetashingandlowtemperatureplasmadryashing.Themethodchosenforaparticularanalysisdependsonthereasonfor
carryingouttheanalysis,thetypeoffoodanalyzedandtheequipmentavailable.Ashingmayalsobeusedasthefirststepinpreparingsamplesfor
analysisofspecificminerals,byatomicspectroscopyorthevarioustraditionalmethodsdescribedbelow.Ashcontentsoffreshfoodsrarelyexceed
5%,althoughsomeprocessedfoodscanhaveashcontentsashighas12%,e.g.,driedbeef.
4.2.1.SamplePreparation
Aswithallfoodanalysisproceduresitiscrucialtocarefullyselectasamplewhosecompositionrepresentsthatofthefoodbeinganalyzedandto
ensurethatitscompositiondoesnotchangesignificantlypriortoanalysis.Typically,samplesof110gareusedintheanalysisofashcontent.Solid
foodsarefinelygroundandthencarefullymixedtofacilitatethechoiceofarepresentativesample.Beforecarryingoutanashanalysis,samplesthat
arehighinmoistureareoftendriedtopreventspatteringduringashing.Highfatsamplesareusuallydefattedbysolventextraction,asthisfacilitates
thereleaseofthemoistureandpreventsspattering.Otherpossibleproblemsincludecontaminationofsamplesbymineralsingrinders,glasswareor
crucibleswhichcomeintocontactwiththesampleduringtheanalysis.Forthesamereason,itisrecommendedtousedeionizedwaterwhenpreparing
samples.
4.2.2.DryAshing
Dryashingproceduresuseahightemperaturemufflefurnacecapableofmaintainingtemperaturesofbetween500and600oC.Waterandother
volatilematerialsarevaporizedandorganicsubstancesareburnedinthepresenceoftheoxygeninairtoCO2,H2OandN2.Mostmineralsare
convertedtooxides,sulfates,phosphates,chloridesorsilicates.Althoughmostmineralshavefairlylowvolatilityatthesehightemperatures,someare
volatileandmaybepartiallylost,e.g.,iron,leadandmercury.Ifananalysisisbeingcarriedouttodeterminetheconcentrationofoneofthese
substancesthenitisadvisabletouseanalternativeashingmethodthatuseslowertemperatures.
Thefoodsampleisweighedbeforeandafterashingtodeterminetheconcentrationofashpresent.Theashcontentcanbeexpressedoneitheradry
orwetbasis:

whereMASH referstothemassoftheashedsample,andMDRYandMASHrefertotheoriginalmassesofthedriedandwetsamples.
Thereareanumberofdifferenttypesofcrucibleavailableforashingfoodsamples,includingquartz,Pyrex,porcelain,steelandplatinum.
Selectionofanappropriatecrucibledependsonthesamplebeinganalyzedandthefurnacetemperatureused.Themostwidelyusedcruciblesaremade
fromporcelainbecauseitisrelativelyinexpensivetopurchase,canbeuseduptohightemperatures(<1200oC)andareeasytoclean.Porcelain
cruciblesareresistenttoacidsbutcanbecorrodedbyalkalinesamples,andthereforedifferenttypesofcrucibleshouldbeusedtoanalyzethistypeof
sample.Inaddition,porcelaincruciblesarepronetocrackingiftheyexperiencerapidtemperaturechanges.Anumberofdryashingmethodshavebeen
officiallyrecognizedforthedeterminationoftheashcontentofvariousfoods(AOACOfficialMethodsofAnalysis).Typically,asampleisheldat
500600oCfor24hours.
Advantages:Safe,fewreagentsarerequired,manysamplescanbeanalyzedsimultaneously,notlaborintensive,andashcanbeanalyzedfor
http://people.umass.edu/~mcclemen/581Ash&Minerals.html

1/6

11/1/2015

ANALYSISOFASHANDMINERALS

specificmineralcontent.
Disadvantages:Longtimerequired(1224hours),mufflefurnacesarequitecostlytorunduetoelectricalcosts,lossofvolatilemineralsathigh
temperatures,e.g.,Cu,Fe,Pb,Hg,Ni,Zn.
Recently,analyticalinstrumentshavebeendevelopedtodryashsamplesbasedonmicrowaveheating.Thesedevicescanbeprogrammedto
initiallyremovemostofthemoisture(usingarelativelylowheat)andthenconvertthesampletoash(usingarelativelyhighheat).Microwave
instrumentsgreatlyreducethetimerequiredtocarryoutanashanalysis,withtheanalysistimeoftenbeinglessthananhour.Themajordisadvantage
isthatitisnotpossibletosimultaneouslyanalyzeasmanysamplesasinamufflefurnace.
4.2.3.WetAshing
Wetashingisprimarilyusedinthepreparationofsamplesforsubsequentanalysisofspecificminerals(seelater).Itbreaksdownandremoves
theorganicmatrixsurroundingthemineralssothattheyareleftinanaqueoussolution.Adriedgroundfoodsampleisusuallyweighedintoaflask
containingstrongacidsandoxidizingagents(e.g.,nitric,perchloricand/orsulfuricacids)andthenheated.Heatingiscontinueduntiltheorganic
matteriscompletelydigested,leavingonlythemineraloxidesinsolution.Thetemperatureandtimeuseddependsonthetypeofacidsandoxidizing
agentsused.Typically,adigestiontakesfrom10minutestoafewhoursattemperaturesofabout350oC.Theresultingsolutioncanthenbe
analyzedforspecificminerals.
Advantages:Littlelossofvolatilemineralsoccursbecauseofthelowertemperaturesused,morerapidthandryashing.
DisadvantagesLaborintensive,requiresaspecialfumecupboardifperchloricacidisusedbecauseofitshazardousnature,lowsample
throughput.
4.2.4.LowTemperaturePlasmaAshing
Asampleisplacedintoaglasschamberwhichisevacuatedusingavacuumpump.Asmallamountofoxygenispumpedintothechamberand
brokendowntonascentoxygen(O22O.)byapplicationofanelectromagneticradiofrequencyfield.Theorganicmatterinthesampleisrapidly
oxidizedbythenascentoxygenandthemoistureisevaporatedbecauseoftheelevatedtemperatures.Therelativelycooltemperatures(<150oC)used
inlowtemperatureplasmaashingcauselesslossofvolatilemineralsthanothermethods.
Advantages:Lesschanceoflosingtraceelementsbyvolatilization
Disadvantages:Relativelyexpensiveequipmentandsmallsamplethroughput.

4.2.5.DeterminationofWaterSolubleandInsolubleAsh
Aswellasthetotalashcontent,itissometimesusefultodeterminetheratioofwatersolubletowaterinsolubleashasthisgivesausefulindication
ofthequalityofcertainfoods,e.g.,thefruitcontentofpreservesandjellies.Ashisdilutedwithdistilledwaterthenheatedtonearlyboiling,andthe
resultingsolutionisfiltered.Theamountofsolubleashisdeterminedbydryingthefiltrate,andtheinsolubleashisdeterminedbyrinsing,dryingand
ashingthefilterpaper.
4.2.6.ComparisonofAshingMethods
Theconventionaldryashingprocedureissimpletocarryout,isnotlaborintensive,requiresnoexpensivechemicalsandcanbeusedtoanalyze
manysamplessimultaneously.Nevertheless,theprocedureistimeconsumingandvolatilemineralsmaybelostatthehightemperaturesused.
Microwaveinstrumentsarecapableofspeedinguptheprocessofdryashing.Wetashingandlowtemperatureplasmaashingaremorerapidandcause
lesslossofvolatilemineralsbecausesamplesareheatedtolowertemperatures.Nevertheless,thewetashingprocedurerequirestheuseofhazardous
chemicalsandislaborintensive,whiletheplasmamethodrequiresexpensiveequipmentandhasalowsamplethroughput.

4.3.DeterminationofSpecificMineralContent
Knowledgeoftheconcentrationandtypeofspecificmineralspresentinfoodproductsisoftenimportantinthefoodindustry.Themajor
physicochemicalcharacteristicsofmineralsthatareusedtodistinguishthemfromthesurroundingmatrixare:theirlowvolatilitytheirabilitytoreact
withspecificchemicalreagentstogivemeasurablechangesandtheiruniqueelectromagneticspectra.Themosteffectivemeansofdeterminingthe
typeandconcentrationofspecificmineralsinfoodsistouseatomicabsorptionoremissionspectroscopy.Instrumentsbasedonthisprinciplecanbe
usedtoquantifytheentirerangeofmineralsinfoods,oftentoconcentrationsaslowasafewppm.Forthesereasonstheyhavelargelyreplaced
traditionalmethodsofmineralanalysisininstitutionsthatcanaffordtopurchaseandmaintainone,orthatroutinelyanalyzelargenumbersofsamples.
Institutionsthatdonothavetheresourcesorsamplethroughputtowarrantpurchasinganatomicspectroscopyinstrumentrelyonmoretraditional
methodsthatrequirechemicalsandequipmentcommonlyfoundinfoodlaboratories.Manyofthemineralsofimportancetofoodscientistscanbe
measuredusingoneofthesetraditionalmethods.
4.3.1.Samplepreparation
Manyoftheanalyticalmethodsusedtodeterminethespecificmineralcontentoffoodsrequirethatthemineralsbedissolvedinanaqueous
solution.Forthisreason,itisoftennecessarytoisolatethemineralsfromtheorganicmatrixsurroundingthempriortotheanalysis.Thisisusually
carriedoutbyashingasampleusingoneofthemethodsdescribedintheprevioussection.Itisimportantthattheashingproceduredoesnotalterthe
mineralconcentrationinthefoodduetovolatilization.Anotherpotentialsourceoferrorinmineralanalysisisthepresenceofcontaminantsinthe
water,reagentsorglassware.Forthisreason,ultrapurewaterorreagentsshouldbeused,and/orablankshouldberunatthesametimeasthesample
beinganalyzed.Ablankusesthesameglasswareandreagentsasthesamplebeinganalyzedandthereforeshouldcontainthesameconcentrationof
anycontaminants.Theconcentrationofmineralsintheblankisthensubtractedfromthevaluedeterminedforthesample.Somesubstancescan
interferewithanalysisofcertainminerals,andshouldthereforebeeliminatedpriortotheanalysisoraccountedforinthedatainterpretation.The
http://people.umass.edu/~mcclemen/581Ash&Minerals.html

2/6

11/1/2015

ANALYSISOFASHANDMINERALS

principlesofanumberofthemostimportanttraditionalmethodsforanalyzingmineralsaredescribedbelow.Manymoretraditionalmethodscanbe
foundintheAOACOfficialMethodsofAnalysis.
4.3.2.GravimetricAnalysis
Theelementtobeanalyzedisprecipitatedfromsolutionbyaddingareagentthatreactswithittoformaninsolublecomplexwithaknown
chemicalformula.Theprecipitateisseparatedfromthesolutionbyfiltration,rinsed,driedandweighed.Theamountofmineralpresentintheoriginal
sampleisdeterminedfromaknowledgeofthechemicalformulaoftheprecipitate.Forexample,theamountofchlorideinasolutioncanbe
determinedbyaddingexcesssilverionstoformaninsolublesilverchlorideprecipitate,becauseitisknownthatClis24.74%ofAgCl.Gravimetric
proceduresareonlysuitableforlargefoodsamples,whichhaverelativelyhighconcentrationsofthemineralbeinganalyzed.Theyarenotsuitablefor
analysisoftraceelementsbecausebalancesarenotsensitiveenoughtoaccuratelyweighthesmallamountofprecipitateformed.
4.3.3.Colorimetricmethods
Thesemethodsrelyonachangeincolorofareagentwhenitreactswithaspecificmineralinsolutionwhichcanbequantifiedbymeasuringthe
absorbanceofthesolutionataspecificwavelengthusingaspectrophotometer.Colorimetricmethodsareusedtodeterminetheconcentrationofawide
varietyofdifferentminerals.Vandateisoftenusedasacolorimetricreagentbecauseitchangescolorwhenitreactswithminerals.Forexample,the
phosphorouscontentofasamplecanbedeterminedbyaddingavandatemolybdatereagenttothesample.Thisformsacoloredcomplex(yellow
orange)withthephosphorouswhichcanbequantifiedbymeasuringtheabsorbanceofthesolutionat420nm,andcomparingwithacalibrationcurve.
Differentreagentsarealsoavailabletocolorimetricallydeterminetheconcentrationofotherminerals.
4.3.4.Titrations
EDTAcompleximetrictitration
EDTAisachemicalreagentthatformsstrongcomplexeswithmultivalentmetallicions.ThedisodiumsaltofEDTAisusuallyusedbecauseitis
availableinhighpurity:Na2H2Y.ThecomplexesformedbymetalionsandEDTAcanberepresentedbythefollowingequations:
m2+ +H2Y2mY2+2H+
m3+ +H2Y2mY+2H+
m4+ +H2Y2mY+2H+

Thecalciumcontentoffoodsisoftendeterminedbythismethod.Anashedfoodsampleisdilutedinwaterandthenmadealkaline(pH12.5to13).
AnindicatorthatcanformacoloredcomplexwithEDTAisthenaddedtothesolution,andthesolutionistitratedwithEDTA.TheEDTAindicator
complexischosentobemuchweakerthantheEDTAmineralcomplex.Consequently,aslongasmultivalentionsremaininthesolutiontheEDTA
formsastrongcomplexwiththemanddoesnotreactwiththeindicator.However,onceallthemineralionshavebeencomplexed,anyadditional
EDTAreactswiththeindicatorandformsacoloredcomplexthatisusedtodeterminetheendpointofthereaction.Thecalciumcontentofafood
sampleisdeterminedbycomparingthevolumeofEDTArequiredtotitrateittotheendpointwithacalibrationcurvepreparedforaseriesofsolutions
ofknowncalciumconcentration.Ifthereisamixtureofdifferentmultivalentmetallicionspresentinafoodtherecouldbesomeproblemsin
determiningtheconcentrationofaspecifictypeofion.Itisoftenpossibletoremoveinterferingionsbypassingthesolutioncontainingthesample
throughanionexchangecolumnpriortoanalysis.
Redoxreactions
Manyanalyticalproceduresarebasedoncoupledreductionoxidation(redox)reactions.Reductionisthegainofelectronsbyatomsor
molecules,whereasoxidationistheremovalofelectronsfromatomsormolecules.Anymolecularspeciesthatgainselectronsduringthecourseofa
reactionissaidtobereduced,whereasanymolecularspeciesthatloseselectronsissaidtobeoxidized,whetherornotoxygenisinvolved.Electrons
cannotbecreatedordestroyedinordinarychemicalreactionsandsoanyoxidationreactionisaccompaniedbyareductionreaction.Thesecoupled
reactionsarecalledredoxreactions:
XnXn+1+e
(Oxidationreactionlossofelectrons)
Ym+eYm
1
(Reductionreactiongainofelectrons)
Xn+YmXn+1+Ym1(Coupledreaction
transferofelectrons)
Analystsoftendesignacoupledreactionsystemsothatoneofthehalfreactionsleadstoameasurablechangeinthesystemthatcanbe
convenientlyusedasanendpoint,e.g.,acolorchange.Thusoneofthecoupledreactionsusuallyinvolvesthemineralbeinganalyzed(e.g.,X=
analyte),whereastheotherinvolvesanindicator(e.g.,Y=indicator).
Forexample,permanganateion(MnO4)isadeeppurplecolor(oxidizedform),whilethemangenousion(Mn2+ )isapalepinkcolor(reduced
form).Thuspermanganatetitrationscanbeusedasanindicatorofmanyredoxreactions:
http://people.umass.edu/~mcclemen/581Ash&Minerals.html

3/6

11/1/2015

MnO4

ANALYSISOFASHANDMINERALS
+8H+ +5eMn2+ +4H

20

(Reductionreaction)
(DeepPurple)(PalePink)
Thecalciumorironcontentoffoodscanbedeterminedbytitrationwithasolutionofpotassiumpermanganate,theendpointcorrespondingtothe
firstchangeofthesolutionfrompalepinktopurple.Thecalciumorironcontentisdeterminedfromthevolumeofpermanganatesolutionofknown
molaritythatisrequiredtoreachtheendpoint.Forironthereactionis:
5Fe2+ 5Fe3+ +5e

(Oxidationreaction)
MnO4+8H+ +5eMn2+ +4H20
(Reductionreaction)
5Fe2+ +MnO4+8H+ 5Fe3+ +Mn2+ +4H20(Coupledreaction)
Potassiumpermanganateistitratedintotheaqueoussolutionofashedfood.WhilethereisFe2+ remaininginthefoodtheMnO4isconvertedto
Mn2+ thatleadstoapalepinksolution.OncealloftheFe2+ hasbeenconvertedtoFe3+thentheMnO4remainsinsolutionandleadstotheformation
ofapurplecolor,whichistheendpoint.
Precipitationtitrations
Whenatleastoneproductofatitrationreactionisaninsolubleprecipitate,itisreferredtoasaprecipitationtitration.Atitrimetricmethod
commonlyusedinthefoodindustryistheMohrmethodforchlorideanalysis.Silvernitrateistitratedintoanaqueoussolutioncontainingthesample
tobeanalyzedandachromateindicator.
AgNO3+NaClAgCl(s)+NaNO3
Theinteractionbetweensilverandchlorideismuchstrongerthanthatbetweensilverandchromate.Thesilverionthereforereactswiththe
chlorideiontoformAgCl,untilallofthechlorideionisexhausted.Anyfurtheradditionofsilvernitrateleadstotheformationofsilverchromate,
whichisaninsolubleorangecoloredsolid.
Ag+ +ClAgCl(colorless)untilallCliscomplexed
2Ag+ +CrO42Ag2CrO4(orange)afterallCliscomplexed
Theendpointofthereactionisthefirsthintofanorangecolor.Thevolumeofsilvernitratesolution(ofknownmolarity)requiredtoreachthe
endpointisdetermined,andthustheconcentrationofchlorideinsolutioncanbecalculated.
4.3.5.IonSelectiveElectrodes
Themineralcontentofmanyfoodscanbedeterminedusingionselectiveelectrodes(ISE).ThesedevicesworkonthesameprincipleaspHmeters,
butthecompositionoftheglasselectrodeisdifferentsothatitissensitivetospecifictypesofion(ratherthanH+ ).Specialglasselectrodesare
commerciallyavailabletodeterminetheconcentrationofK+ ,Na+ ,NH4+ ,Li+ ,Ca2+ andRb+ inaqueoussolution.Twoelectrodesaredippedintoan
aqueoussolutioncontainingthedissolvedmineral:areferenceelectrodeandaionselectiveelectrode.Thevoltageacrosstheelectrodesdependsonthe
concentrationofthemineralinsolutionandismeasuredatextremelylowcurrenttopreventalterationsinionconcentration.Theconcentrationofa
specificmineralisdeterminedfromacalibrationcurveofvoltageversusthelogarithmofconcentration.Themajoradvantagesofthismethodareits
simplicity,speedandeaseofuse.Thetechniquehasbeenusedtodeterminethesaltconcentrationofbutter,cheeseandmeat,thecalcium
concentrationofmilkandtheCO2concentrationofsoftdrinks.Inprinciple,anionselectiveelectrodeisonlysensitivetoonetypeofion,however,
thereisofteninterferencefromothertypesofions.ThisproblemcanoftenbereducedbyadjustingpH,complexingorprecipitatingtheinterfering
ions.
Finally,itshouldbenotedthattheISEtechniqueisonlysensitivetotheconcentrationoffreeionspresentinasolution.Iftheionsare
complexedwithothercomponents,suchaschelatingagentsorbiopolymers,thentheywillnotbedetected.TheISEtechniqueistherefore
particularlyusefulforquantifyingthebindingofmineralstofoodcomponents.Ifonewantstodeterminethetotalconcentrationofaspecificionina
food(ratherthanthefreeconcentration),thenoneneedstoensurethationbindingdoesnotoccur,e.g.,byashingthefood.

4.3.6AtomicSpectroscopy
Thedeterminationofmineraltypeandconcentrationbyatomicspectroscopyismoresensitive,specific,andquickerthantraditionalwetchemistry
methods.Forthisreasonithaslargelyreplacedtraditionalmethodsinlaboratoriesthatcanafforditorthatroutinelyanalyzeforminerals.

PrinciplesofAtomicSpectroscopy
http://people.umass.edu/~mcclemen/581Ash&Minerals.html

4/6

11/1/2015

ANALYSISOFASHANDMINERALS

Theprimarycauseofabsorptionandemissionofradiationinatomicspectroscopyiselectronictransitionsofoutershellelectrons.Photonswiththe
energyassociatedwiththistypeoftransitionarefoundintheUVvisiblepartoftheelectromagneticspectrum.Inthisrespectatomicspectroscopyis
similartoUVvisiblespectroscopy,however,thesamplesusedinatomicspectroscopyareindividualatomsinagaseousstate,whereasthoseusedin
UVvisiblespectroscopyaremoleculesdissolvedinliquids.Thishasimportantconsequencesforthenatureofthespectraproduced.Inatomic
spectroscopythepeaksarenarrowandwelldefined,butinUVvisiblespectroscopytheyarebroadandoverlapwithoneanother.Thearetwomajor
reasonsforthis.Firstly,becauseabsorptionoremissionisfromatoms,ratherthanmolecules,therearenovibrationalorrotationaltransitions
superimposedontheelectronictransitions.Secondly,becausetheatomsareinagaseousstatetheyarewellseparatedfromeachotheranddonot
interactwithneighboringmolecules.
Theenergychangeassociatedwithatransitionbetweentwoenergylevelsisrelatedtothewavelengthoftheabsorbedradiation:E=hc/,where,
h=Planksconstant,c=thespeedoflightandthewavelength.Thusforagiventransitionbetweentwoenergystatesradiationofadiscrete
wavelengthiseitherabsorbedoremitted.Eachelementhasauniqueelectronicstructureandthereforeithasauniquesetofenergylevels.
Consequently,itabsorbsoremitsradiationatspecificwavelengths.Eachspectrumisthereforelikea"fingerprint"thatcanbeusedtoidentifya
particularelement.Inaddition,becausetheabsorptionandemissionofradiationoccursatdifferentwavelengthsfordifferenttypesofatom,one
elementcanbedistinguishedfromothersbymakingmeasurementsatawavelengthwhereitabsorbsoremitsradiation,buttheotherelementsdonot.
Absorptionoccursprimarilywhenelectronsinthegroundstatearepromotedtovariousexcitedstates.Emissionoccurswhenelectronsinan
excitedstatefallbacktoalowerenergylevel.Atomscanexistinanumberofdifferentexcitedstates,andcanfallbacktooneofmanydifferentlower
energystates(notnecessarilythegroundstate).Thustherearemanymorelinesinanemissionspectrathanthereareinanabsorptionspectra.
Atomicspectroscopyisusedtoprovideinformationaboutthetypeandconcentrationofmineralsinfoods.Thetypeofmineralsisdeterminedby
measuringthepositionofthepeaksintheemissionorabsorptionspectra.Theconcentrationofmineralcomponentsisdeterminedbymeasuringthe
intensityofaspectrallineknowntocorrespondtotheparticularelementofinterest.Thereductioninintensityofanelectromagneticwavethattravels
throughasampleisusedtodeterminetheabsorbance:A=log(I/Io).TheBeerLambertlawcanthenbeusedtorelatetheabsorbancetothe
concentrationofatomsinthesample:A=a.b.c,whereAisabsorbance,aisextinctioncofficient,bissamplepathlengthandcisconcentrationof
absorbingspecies.Inpractice,thereareoftendeviationsfromtheaboveequationandsoitisoftennecessarytoprepareacalibrationcurveusinga
seriesofstandardsofknownconcentrationpreparedusingthesamereagentsasusedtopreparethesample.Itisalsoimportanttorunablanktotake
intoaccountanyimpuritiesinthereagentsthatmightinterferewiththeanalysis.
AtomicAbsorptionSpectroscopy
Atomicabsorptionspectroscopy(AAS)isananalyticalmethodthatisbasedontheabsorptionofUVvisibleradiationbyfreeatomsinthegaseous
state.Thefoodsampletobeanalyzedisnormallyashedandthendissolvedinanaqueoussolution.Thissolutionisplacedintheinstrumentwhereitis
heatedtovaporizeandatomizetheminerals.Abeamofradiationispassedthroughtheatomizedsample,andtheabsorptionofradiationismeasuredat
specificwavelengthscorrespondingtothemineralofinterest.Informationaboutthetypeandconcentrationofmineralspresentisobtainedby
measuringthelocationandintensityofthepeaksintheabsorptionspectra.
Instrumentation
Theradiationsource.ThemostcommonlyusedsourceofradiationinAASisthehollowcathodelamp.Thisisahollowtubefilledwithargonor
neon,andacathodefilamentmadeofthemetallicformoftheelementtobeanalyzed.Whenavoltageisappliedacrosstheelectrodes,thelampemits
radiationcharacteristicofthemetalinthecathodei.e.,ifthecathodeismadeofsodium,asodiumemissionspectrumisproduced.Whenthisradiation
passesthroughasamplecontainingsodiumatomsitwillbeabsorbedbecauseitcontainsradiationofexactlytherightwavelengthtopromotetransition
fromoneenergyleveltoanother.Thusadifferentlampisneededforeachtypeofelementanalyzed.
Chopper.Theradiationarrivingatthedetectorcomesfromtwodifferentsources:(i)radiationemittedbythefilamentofthelamp(whichis
partiallyabsorbedbythesample)(ii)radiationthatisemittedbytheatomsinthesamplethathavebeenexcitedtohigherenergylevelsbyabsorption
ofenergyfromtheatomizer.ToquantifytheconcentrationofmineralsinasampleusingAASitisnecessarytomeasurethereductioninamplitudeof
thebeamofradiationthathaspassedthroughthesample,ratherthantheradiationemittedbytheexcitedsample.Thiscanbedoneusingamechanical
device,calledachopper,inconjunctionwithanelectronicdevicethatdistinguishesbetweendirectandalternatingcurrents.Thechopperisaspinning
diskwithaseriesofslitswhichisplacedbetweentheradiationsourceandthesample.Theradiationfromthelightsourceisthereforecontinuously
beingswitchedonandoffataspecificfrequency,i.e.,itisanalternatingcurrent.Ontheotherhand,theradiationemittedfromtheexcitedatomsinthe
sampleisconstanti.e.,itisdirectcurrent.Theoveralldetectedradiationisthereforethesumofavaryingcomponentandaconstantcomponent.
Electronicdevicesareavailablewhichcanseparatealternatingandconstantcurrent.ThesedevicesareusedinAASinstrumentstoisolatethesignal
generatedbythelightfromthatemittedbytheatomsinthesample.
Atomizer.Atomizersareusedtoconvertthesampletobeanalyzedintoindividualatoms.Theatomizationprocessisachievedbyexposingthe
sampletohightemperatures,andinvolvesthreestages:(i)removalofwaterassociatedwithmolecules,(ii)conversionofmoleculesintoagas,and(iii)
atomizationofmolecules.Athighertemperaturestheatomsmaybecomeionized,whichisundesirablebecausetheatomicspectraofionizedatomsis
differentfromthatofnonionizedones.Consequently,itisimportanttouseahighenoughtemperaturetoatomizethemolecules,butnotsohighthat
theatomsareionized.Twotypesofatomizerarecommonlyusedinatomicabsorptioninstruments:flameandelectrothermalatomization.
Flameatomizersconsistofanebulizerandaburner.Thenebulizerconvertsthesolutionintoafinemistoraerosol.Thesampleisforcedthrough
atinyholeintoachamberthroughwhichtheoxidantandfuelareflowing.Theoxidantandfuelcarrythesampleintotheflame.Theburneris
usually510centimeterslongsoastogivealongpathlengthfortheradiationtotravelalong.Thecharacteristicsoftheflamecanbealteredby
varyingtherelativeproportionsandtypesofoxidantandfuelusedintheflame.AiracetelyneandNitrogenoxideacetylenearethemost
commonlyusedmixturesofoxidantandfuel.Thusflameswithdifferenttemperaturescanbeproduced.Thisisimportantbecausetheenergy
requiredtocauseatomization,butnotionization,variesfromsubstancetosubstance.Instrumentmanufacturesprovideguidelineswiththeir
instrumentsaboutthetypeofflametouseforspecificelements.
InelectrothermalAASthesampleisplacedinasmallgraphitecupwhichiselectricallyheatedtoatemperature(typically2,0003,000oC)high
enoughtoproducevolatilizationandatomization.Thecupispositionedsothattheradiationbeampassesthroughtheatomizedsample.The
advantageofelectrothermalatomizersisthatsmallersamplesarerequiredanddetectionlimitsarelower.Majordisadvantagesarethattheyare
moreexpensivetopurchase,havealowersamplethroughput,aremoredifficulttooperateandhavealowerprecisionthanflameatomizers.
http://people.umass.edu/~mcclemen/581Ash&Minerals.html

5/6

11/1/2015

ANALYSISOFASHANDMINERALS

Wavelengthselector.Awavelengthselectorispositionedintheopticalpathbetweentheflame(orfurnace)andthedetector.It'spurposeisto
isolatethespectrallineofinterestfromtherestoftheradiationcomingfromthesample,sothatonlytheradiationofthedesiredwavelengthreaches
thedetector.Wavelengthselectorsaretypically,monochromaticgratingsorfilters.
Detector/Readout.Thedetectorisaphotomultipliertubethatconvertselectromagneticenergyreachingitintoanelectricalsignal.Mostmodern
instrumentshaveacomputertodisplaythesignaloutputandstorethespectra.
AtomicEmissionSpectroscopy
Atomicemissionspectroscopy(AES)isdifferentfromAAS,becauseitutilizestheemissionofradiationbyasample,ratherthantheabsorption.
Forthisreasonsamplesusuallyhavetobeheatedtoahighertemperaturesothatagreaterproportionoftheatomsareinanexcitedstate(althoughcare
mustbetakentoensurethationizationdoesnotoccurbecausethespectrafromionizedatomsisdifferentfromthatofnonionizedatoms).Therearea
numberofwaysthattheenergycanbesuppliedtoasample,includingheat,light,electricityandradiowaves.
Instrumentation
InAESthesampleitselfactsasthesourceofthedetectedradiation,andthereforethereisnoneedtohaveaseparateradiationsourceorachopper.
Thesampleisheatedtoatemperaturewhereitisatomizedandasignificantproportionoftheatomsisinanexcitedstate.Atomicemissionsare
producedwhentheelectronsinanexcitedstatefallbacktolowerenergylevels.Sincetheallowedenergylevelsforeachatomaredifferent,theyeach
havecharacteristicemissionspectrumfromwhichtheycanbeidentified.Sinceafoodusuallycontainsawidevarietyofdifferentminerals,eachwitha
characteristicsemissionspectrum,theoverallspectrumproducedcontainsmanyabsorptionpeaks.Theemittedradiationisthereforepassedthrougha
wavelengthselectortoisolatespecificpeaksinthespectracorrespondingtotheatomofinterest,andtheintensityofthepeakismeasuredusinga
detectoranddisplayedonareadoutdevice.
AtomizationExcitationSource.Thepurposeoftheatomizationexcitationsourceistoatomizethesample,andtoexcitetheatomssothattheyemit
asignificantamountofdetectableradiation.ThetwomostcommonlyusedformsofatomizationexcitationsourcesinfoodanalysisareFlameand
InductivelyCoupledPlasma(ICP)devices.
InflameAESanebulizerburnersystemisusedtoatomizethemineralsinthesampleandexcitealargeproportionofthemtohigherenergy
levels.
InICPAESaspecialdeviceisusedthatheatsthesampletoveryhightemperatures(6,000to10,000K)inthepresenceofargonions.The
mineralsinthesamplearenotionizedatthesetemperaturesbecauseofthehighconcentrationofargonions(ArAr+ +e)leadstotherelease
ofelectronsthatpushtheequilibriumtowardsthenonionizedformofthemineral(M+ +eM).
Wavelengthselectors.Wavelengthselectorsareusedtoisolateparticularspectrallines,whicharecharacteristicofthematerialbeingstudied,from
alltheotherspectrallines.Anumberofdifferenttypesofwavelengthselectorareavailableincludingfiltersandgratings.Afiltercanonlybeusedto
measuretheintensityataparticularfixedwavelength,whereasagratingcanbeusedtomeasuretheintensityatmanydifferentwavelengths.Afilter
canthereforeonlybeusedtoanalyzeforonetypeofmineral,whereasagratingcanbeusedtomeasuremanydifferenttypesofminerals.
Practicalconsiderations
Priortomakingatomicspectroscopymeasurementsafoodsampleisusuallyashed.Theresultingashisdissolvedinasuitablesolvent,suchas
waterordiluteHCl,beforeinjectingitintotheinstrument.Sometimesitispossibletoanalyzeasamplewithoutashingitfirst.Forexample,vegetables
oilscanbeanalyzedbydissolvingtheminacetoneorethanolandinjectingthemdirectlyintotheinstrument.
Concentrationsofmineralelementsinfoodsareoftenatthetracelevelandsoitisimportanttouseverypurereagentswhenpreparingsamplesfor
analysis.Similarly,oneshouldensurethatglasswareinverycleananddry,sothatitcontainsnocontaminatingelements.Itisalsoimportanttoensure
therearenointerferingsubstancesinthesamplewhosepresencewouldleadtoerroneousresults.Aninterferingsubstancecouldbesomethingthat
absorbsatthesamewavelengthasthemineralbeinganalyzed,orsomethingthatbindstothemineralandpreventsitfrombeingefficientlyatomized.
Therearevarioustechniquesavailableforremovingtheeffectsoftheseinterferingsubstances.

BacktoMcClementsHomePage
BacktoFDSCI581Page
ToPreviousLecture(Moisture)
ToNextLecture(Lipids)

http://people.umass.edu/~mcclemen/581Ash&Minerals.html

6/6