FDSC4763 AnalysisofFoodProducts

Ash
Ash referstotheinorganicresiduesthatremainafter

thecompleteoxidationofalloftheorganicmatterina foodstuff.
Thisresidueconsistsofmineralsthathavegenerally

beenconvertedtooxidesandsaltsbytheashing process Phosphates,chlorides,sulfates,andsilicatesaswellas saltsofsodium,potassium,calcium,magnesium,iron, andmanganesewillbecreated.Traceelementswillalso bepresent.

Ashing
Ashing referstoprocessofoxidizingorganicmatterto

produceash.
Oxidationmaybeaccomplishedseveralways. Differentsamplepreparationtechniquesmaybe

requiredbasedonsamplemoisturecontentand/orfat content.

Highmoisturesamplessuchasfreshfruitsandvegetableswill usuallyneedtobedriedpriortoashing. Highfatsamplessuchasmeatswillusuallyneedtobedried andfatextractedpriortoashing. Drysamplessuchasgrainsanddriedvegetablesneedlittleor nosamplepreparationotherthansizereduction.

DryAshing
DryAshing referstotheuseofamufflefurnaceat

temperaturesof500to600Ctoburnofforganic matterandvolatilizewatervaporandothervolatile components.

Notethatsomeminerals,suchasFe(iron),Pb (lead),Se

(selenium),andHg(mercury)maybepartially volatilizedatthesetemperatures.Theamountlostis usuallynotconsideredsignificantforcalculatingtotal ashcontent,butmayrendertheresultsinaccuratefor specificelementalanalysis.

WetAshing
WetAshing referstoaprocesswherebysamplesare

oxidizedbystrongacidsand/orotheroxidizingagents.
Mayrequireamixtureorsequentialuseofdifferent

chemicalagents.
Mayrequirespecialequipment(somechemicalssuchas

perchloric acidmayproducehighlytoxicand/or corrosivefumes).

Ispreferredforspecificelementalanalysisbecause

mineralconstituentsarenotvolatilized.

Reasonsformeasuringashcontent
Theashcontentrepresentsthetotalmineralcontent

ofafood.

Wemaywanttoknowashcontentasapartof

proximateanalysis.

Carbohydratesareusuallydeterminedbysubtraction,

thusaccurateashdeterminationisimportant.

Wemaywanttomeasureashasapartofelemental

analysisinordertodeterminethecontentofmineral nutrientssuchascalcium,iron,etc.

Ashcontentinfoods
Foodsofanimaloriginareusuallyfairlyconstantinash

content. Foodsofplantoriginareoftensomewhatvariableinash content. Ashcontentoffreshfoodsrarelytops5%;ashcontentof driedfoodsmayexceed10%(wetweightbasis). Purefatsandoilscontainlittleornoash. Meatistypicallyaround12%ash. Cerealproductscontainfromaround0.5%toaround4% (higherbrancontentequalshigherashcontent). Fruitsandvegetables(includingnuts)rangefromlessthan 0.5tomorethan3%ash.

Generalconsiderations
Notethatrelativelysmallsamplesizes(210g)aretypically

usedforashdetermination.
Thismakesinsuringthatthesamplesarerepresentativeall

themorecritical.

Notethatmilling,grinding,etc.withmetalimplements

mayintroduceelementalmaterialsintothesamplesuchas iron.
Notlikelytoaffecttotalashcontentsignificantly,butcould

significantlyalterelementalanalyses.

Water,dirtyglassware,crucibles,etc.canintroduce

mineralcontaminantsintothesamples.
Alwaysusedistilleddeionized (dd)waterforwashing,

dilutions,etc.

Preparingplantmaterials
Plantmaterialsshouldbeabout15%moistureorless

forashing tohelpavoidspattering. Plantmaterialsaregenerallydriedbeforeashing,but previouslydriedmaterialsmaybeusedasis. Dryingtemperatureisnotcriticalifthesamplewillbe usedonlyforashing.

Ifthesamplewillhavemultipleanalyticaluses,e.g.fiber

determination,thenlowertemperatureormultistage dryingmaybeneededtoavoidbiochemicalreactions suchasligninformation.

Preparinganimalproductsand otherhighfatand/orhighsugar samples

Productshighinmoistureand/orfatwilltendto

spatterand/orswellduringashing. Productshighinsugarwilltendtofoamduring ashing. Spattering,swelling,andfoamingincreasetheriskof losingsamplefromthecrucibleduringtheashing process.

Evaporatinghighmoisturesamples
Samplessuchasfreshmeats,syrups,milk,juices,etc.

shouldbeevaporatedtodrynesspriortoashing.
Maybedoneusinganinfraredlamp(heatlamp)ora

steamorwaterbathdrier.

Note:afewdripsofoliveoilcanhelppreventsample spatter/lossasthesampledries.

Hotplatesmaybeused,butextremecaremustbetaken

toavoidburningthematerialorlosingmaterialthrough bubblingover.

Laboratorysteamdriers

Preparinghighfatsamples
Samplesthatarehighinfatmayspatter,butmayalso

canemitacombustiblemixtureoffumesinthemuffle furnacewhenbeingashed. Twooptionsfordealingwithhighfatcontent:

1.

Fatmaybeextractedpriortoashing usingabasicfat extractionprocedure.

Etherextractioniscommonlyused becarefulnottoplace sampleinfurnaceuntiletheriscompletelyevaporated.

2.

Fatmaybeburnedoffinthepresenceofoxygenby keepingthedoorofthemufflefurnaceopenduring preliminaryheating,beforebeginningthenormal ashing procedure.

Dryashing istypicallydoneusinga mufflefurnace

Amufflefurnace isdefinedasafurnaceorkilnin

whichthematerialbeingheatedisisolatedfromdirect contactwiththeheatingfuelandanyproductscreated byfuelcombustion,includinggasesandash.

Modernmufflefurnacesgenerallyuseelectricheating

elementstoreachtemperaturesof500Corhigher.

MuffleFurnaces

Crucibleselection
Acrucible isavesselusedtoholdasamplesubjected

tohightemperatures.
Manytypesandsizesofcruciblesexist;somearebetter

suitedfortestingdifferenttypesofproducts.

Quartzcrucibles
Can withstand high temperatures (~1100 to 1500C), are resistant to acids and halogens, but not alkali.

Ceramic (porcelain) Crucibles

Similar physical properties to quartz crucibles, but much more susceptible to cracking with temperature changes.

SteelCrucibles

Resistant to acids and alkalines, but can contribute metal contaminants to samples. Maximum temperature range is from about 500 to 800 C.

PlatinumCrucibles

Resistant to almost all chemicals. Maximum temperature range is from about 1000 to 1600 C. Very expensive.

Specialtysilica(glass)Crucibles
Inert and non-porous, clear, but susceptible to cracking.

Vycor
Good to about 900C

Pyrex
Good to about 500C

Quartzfiber crucibles
Disposable, unbreakable, allow better air circulation during ashing, cool very quickly. Not readily reusable.

Advantagesanddisadvantagesof dryashing
Advantages: relativelysafe;fewifanyreagentsare

required;manysamplescanbeanalyzedatonetime; procedureisnotlaborintensiveanddoesnotrequireclose supervision;andashcanbeusedforotheranalysessuchas specificelementcontents,watersolubleash,etc. Disadvantages: requiresarelativelylongtime(1224 hours);mufflefurnacesareexpensivetopurchaseandcan becostlytooperate;volatilemineralswillbelostathigh temperatures,e.g.,As,B,Cd,Cr,Cu,Fe,Pb,Hg,Ni,P,V, andZn.

Basicdryashing procedure
1. 2. 3. 4.

5. 6. 7. 8.

Wash,dry,andprefirecruciblesasneeded.Storein dessicator priortouse. Weighpreparedcruciblestogettareweigh. Weigh510gsampleintotared crucible(pretreat samplesasnecessary). Placecruciblesintocoolmufflefurnace.Usepersonal protectiveequipment(PPE)asrequired,e.g.gloves, goggles,etc.Usetongstomovecruciblesiffurnaceis warm. Ignitefurnaceandashsamples,e.g.at550Cfor1218 hours. Turnofffurnaceandallowittocooltoatleast250C. Usetongstotransfercruciblesquicklyintodessicator. Allowcruciblestocooltoroomtemperature. Weighcooledcruciblestocalculate%ash.

Considerationswhendryashing
Aircurrentsmaydisruptsamplesifthedoorofthe

mufflefurnaceisopenedsuddenlyafterashing.Tryto placesamplesatleast1.5inchesfromthefrontofthe furnaceand1inchfromtherearwallofthefurnace.

Bewarethatavacuummayforminthedessicator as

samplescoolafterashing.Slidethecoverofftothe sidetograduallyreleasethevacuumifthisoccurs.

Ashcontentonawetweightbasis
Formulaforcalculatingashcontentonawetweight

basis:
(wt of ashed sample tare wt of crucible) % ash = original sample wt x 100

Miniquiz:Assumeforasampleofapple
wt of ashed sample = 56.381 g tare wt of crucible = 56.359 g original sample weight = 9.398 g

Whatisthe%ash?
0.234 %

Ashcontentonadryweightbasis
Formulaforcalculatingashcontentonadryweight

basis:
(wt of ashed sample tare wt of crucible) % ash = (original sample wt x dry matter coefficient) x 100

where:dry matter coefficient equals (% solids/100) Miniquiz:Ifasampleofappleis80%moisture(dry

basis),whatisthedrymattercoefficient? 0.2

Usesofwetashing
Sometimescalledwetoxidation orwetdigestion. Isprimarilyusedtopreparesamplesforfurther

mineralanalysis.
Hence,notoftenusedforbasicproximateanalysis.

Usuallyemploysacombinationofacids/oxidizersto

getcompletesampledigestion.
Nitricacid+sulfuricacidand/orhydrochloricacid

and/orhydrogenperoxideiscommonlyused.Variesby sampletype. Nitricacid+perchloric acidisveryeffectiveformany typesofsamples,but

Perchloric acidfumesandsomeperchlorates arehighly explosive.

Advantagesanddisadvantagesof wetashing
Advantages: volatilemineralsarenotlostbecauseof

thelowertemperaturesused;requiressignificantlyless timethandryashing;may notrequirespecial equipmentaboveandbeyondlaboratoryglassware,a hotplate,andafumehood. Disadvantages: requiresnearconstantattention duringdigestion;requiresaspecialfumehoodif perchloric acidisused;lowsamplethroughput.

Basicwetashing procedure
1. 2. 3. 4. 5. 6.

7.

AcidwashanddrysuitablePyrexflasks(e.g.125ml Erlenmeyer). Weighabout1gofsampleintothepreparedflasks. Prepareasuitableblankcontainingthedigestionmixtureina separateflask. Addthedigestionmixturetothesamplesintheflasks(e.g.3 mlofsulfuricacidfollowedby5mlofnitricacid). Heatthesamplesinafumehoodtoaround200C(boiling), untilbrownyellowfumesceaseandwhitefumesareobserved. Removeflaskfromheat,slowlyadd35mlofnitricacidand reheat.Repeatasneededuntilthesolutioniscleartostraw yellow. Reducesamplewithheatasneeded,transfercooledsampleto volumetricflask,andmaketovolumewithultrapurewater.

Microwavewetashing
Principle: usemicrowaveradiationtoheatacid

digestionmixtures. Advantages: ashing procedurescanbemoreorless automatedintermsofdispensingreagents,heating samples,etc.;digestionsmaybeaccelerated;multiple samplesmayberunatthesametimedependingon theequipment. Disadvantages: equipmentisrelativelycostlyto purchaseandmaintain.

Typesofmicrowavewetashing equipment
Closedvessel: samplesareheldinsealedvesselsthatare

usuallydesignedtowithstandpressuresupto1500psi.
Thisallowsdigestionmixturestobeheatedbeyondtheir

boilingpointatatmoshperic pressures,thuscuttingdigestion timessignificantly.

Openvessel:samplesareheldinvesselsthatarenot

sealed.Unitsaredesignedtocontainfumes,willoften recirculate acidviaarefluxsystem.

Usedwithsamplesthatwillgeneratesignificantvolumesof

fumesduringdigestionorwhenlargersamplesizesare needed.

Microwavewetashing units

Closed Vessel Systems

Open Vessel System

Microwavedryashing
Principle: usemicrowaveradiation s0metimesin

combinationwithconventionalelectricalresistance heating toheatsamplesuptoashing temperatures, ashighas1200C. Advantages: ashing procedurescanbemoreorless automatedintermsofheatingprofiles;ashing time maybecuttounderhalfanhourasopposedtoseveral hoursinaconventionalmufflefurnace. Disadvantages: equipmentisrelativelycostlyto purchaseandmaintain.

Microwavedryashing units

LowTemperaturePlasmaAshing
Principle: samplesareplacedintoasealedchamber

whichisevacuatedusingavacuumpump.Gaseous oxygenisintroducedintothechamberandbroken downtoionizedoxygenusinganelectromagnetic field.Theorganicmatterinthesampleisrapidly oxidizedandthemoistureisevaporated. Advantages: Lowerashing temperatures(<150oC) resultinlessvolatilizationthanothermethods. Disadvantages: Relativelyexpensiveequipment; smallsamplethroughput.

Lowtemperatureplasmaashing unit

Comparisonsofmajorashing techniques
Dryashing: Usefulforavarietyofsamples. Relativelyeasy. Relativelyhighsamplethroughput. Usuallyusedfortotalmineralcontent,butashmaybeused forsubsequentanalysissuchaswatersolubleash,acid solubleash,etc. Wetashing: Methodusuallymoretailoredtospecificsampletypes. Typicallylesssamplethroughput,morelabor. Usuallyusedasawaytopreparesampleforsubsequent elementalanalyses.