ESS312GeochemistryWeek4

TraceElementBehaviorinIgneousSystems
Patternsoftraceelementconcentrationsinrocksandmineralsprovideapowerfulwayto
quantifymeltingandcrystallizationprocesses.Wecanobtaininformationabouttheextentof
meltingandthemineralassembleageoftheparentrock.Likewise,wecanidentifytheminerals
thatcrystallizedfromameltbeforeeruption,anddeterminetheamountsremoved.Wewill
exploregeneralprinciplesofelementpartitioningbetweencoexistingmeltandmineralphases;
thesewillturnouttobeusefulinunderstandingandmodelinggeologicprocessesbeyond
magmatismanddifferentiationinigneoussystems.
TheseexercisesdependonusingExcelspreadsheetstoperformcalculations.Ifyouhaventused
Exceltodothelabandhomeworkexercisesoverthepastfewweeks,besuretocheckwithan
instructoronhowtowritespreadsheetformulae.
Whenmagmasformorcrytallize,theliquidsandsolidsinequilibriumwithoneanotherhave
differentcompositions.
Thustheseparationofapartialmeltfromitsparentrockchangesthecompositionofthe
residue,
andremovalofthesolidscrystallizingfromamagmachangesthecompositionoftheremaining
magma.Bothareimportantprocessesofdifferentiation.Twosimplifiedconceptualmodelsare
usedtounderstandtheseprocesses:
PartialMelting
a)Batch(orequilibrium)melting,inwhichtheliquidisassumedtocometoequilibriumwiththe
residualsolidmineralsinitsparentrockasasinglebatch.
b)Fractional(orRayleigh)melting,inwhichsuccessivesmallbatchesofliquidareremoved
fromtheparentrocksequentially,eachinequilibriumwiththeparentmineralsatthetimeofits
formation.
Crystallization
a)Batch(orequilibrium)crystallization,inwhichasinglebatchofcrystalsandmeltisassumed
tocometoequilibrium.
b)Fractional(orRayleigh)crystallization,inwhichcrystalsprecipitatedinequilibriumwiththe
meltareprogressivelyremoved.Thischangesboththecompositionofthemelt,andthenext
crystalstoform,ascrystallizationproceeds.
Theobjectivesofthislabareto:1)Modelbatchmelting,2)Modelfractionalcrystallization,and
3)Applythesemodelstosolveapetrologicproblemregardingtheoriginofgranitesinthe
PeninsularRangesBatholithofsouthernCalifornia.
Throughoutthelab,wewillusethefollowingdefinitions:

F=fractionofmeltinthesystem(from1forentirelyliquidto0forentirelycrystalline)
Di=distributioncoefficientforelementi
Di=(concentrationiinmineral)/(concentrationiinmelt)
ElementswithvaluesofDi>1arecalledcompatibleelements,thosewithDi<1arecalled
incompatibleelements.RecallGoldschmidtsrulesforsubstitutionoftraceelementsinto
crystalsasyouworkwiththesedefinitionsbelow.
Ci,L=concentrationofelementiintheliquid
Ci,S=concentrationofelementiinthesolid
Ci,0=concentrationofelementiinthetotalsystem(i.e.Inproblemsdealingwithmelting,Ci,0
istheconcentrationintheinitialsolid.Inproblemsdealingwithcrystallizationofa
magma,itistheoriginalconcentrationintheliquid.)
Itisimportanttokeeptheseconsistent.
I.Batch(Equilibrium)Melting
1)Showthederivationforthebatchmeltingequation:Ci,L/Ci,0=1/(F+DiFDi)
2)UsetheBatchMeltingExceltemplateprovidedtosolvethisequationfor:
Frangingfrom0to1instepsof0.05
Divaluesof0.05,0.06,0.1,0.5,1,2and10
(PuttheFvaluesinthefirstcolumn,andthensolveforeachDinthenext7columns.Youcan
writeasingleExcelequationthatcanbecopiedtoalloftheothercellsinthetable.Askif
you'renotsurehowtowriteExcelformulaethatlockrowandcolumnreferences.)
3)Maketwographs,bothplottingCi,L/Ci,0versusF.PutcurvesforallvaluesofDioneachplot.
Settheyaxisforoneplottorangefrom0to20,toseethebehavioroftheincompatible
elements.Settheothertorangefrom0to2,tohighlightthebehaviorofthecompatible
elements.
4)Ingeneral,whatisthebehavioroftheincompatibleelementsaspartialmeltingprogresses?
Whatisthegeneralbehaviorofthecompatibleelementsaspartialmeltingprogresses?
ExplainthesebehaviorsinlightofGoldschmidtsrules.Whenmantleperidotitemeltsat
moderatedepths,themagmaformsinequilibriumwitholivine,orthopyroxene,clinopyroxene
andspinel.Suggesttwotraceelementsthatwouldbehaveascompatibleelementswhenmelt
formsinthepresenceoftheseminerals.Suggesttwotraceelementsthatwouldbehaveas
incompatibleelements.
5)Assumethattwoelements,oneincompatiblewithDi=0.1andtheothercompatiblewithDj=
2,bothhadthesameC0.Onthespreadsheet,addacolumnthatcalculatestheratioofthe
incompatibletocompatibleelementinthemelt.Describehowthisratiochangesasthemelt

fraction,F,increasesfrom0to1(fromthefirstdropofmeltformed,tothepointwherethe
systemisentirelymolten).
6)Assumetwoincompatibleelements,onewithDi=0.05andtheotherwithDj=0.06,bothhad
thesameC0.Addanothercolumntothespreadsheetthatshowshowtheratioofthesetwo
changeaspartialmeltingprogresses(placethemoreincompatibleelementinthenumerator).
Describehowthisratiochangesasthemeltfraction,F,increasesfrom0to1.
7)ItseemsreasonabletohypothesizethatlavaseruptedfromHawaiianvolcanoesformedby
partialmeltingoftheunderlyingmantle.Butwithoutactualsamplesofthemantle,wemust
useelementconcentrationsintheeruptedbasalts(Ci,L,measuredinthebasaltafterithas
cooledandsolidified)tomakeinferencesaboutthecompositionofthemantlesource(values
ofCi,0).Usingourunderstandingofelementpartitioning,wecannowmakesomeuseful
estimatesofmantlesourceconcentrationsandplacelimitsonratiosofdifferentelements.
a)Whichelements(rangesofDi)changeleastaspartialmeltingprogresses(considermelt
fractionsupto30%(F0.3),whichisprobablythemaximumextentofmeltinginthe
mantle)?
b)Generally,wedontknowthevalueofFthatproducedaparticularmagma.Nonetheless,
wecanstillestimatethemantleconcentrationsofsomeelements.Bylookingatyour
graphs,andsubstitutingsometrialvaluesforDiifnecessary,whichrangeofDivaluesgive
magmaswhoseconcentrationsarewithin25%oftheinitialcompositionoftheparent
mantleCi,0.(Again,onlyconsidermeltingupto30%;F0.3).
c)TheratioofincompatibleelementsmeasuredinHawaiianlavascanprovideuswith
informationabouttheratiooftheseelementsinthemantlesourcethatwasmelted.Interms
ofrelativeDivalues,whichelementratiosinthemagmawouldbeveryclosetothose
elementratiosinthemantlesource?
8)ThandCehaveD=0.002.ThelastlavasthateruptedonOahuarecalledtheHonolulu
VolcanicSeries.TheserockshaveThconcentrationsof2.5to12.5ppm,andCe
concentrationsof40to200ppm.Inspiteofthisrangeofconcentration,eachrockhasa
Ce/Thratioof16.
a)Canallofthesemagmashavecomefromthesamemantlesource,orismorethanone
sourcerequired?Why?
b)Whichsamplesrepresentthegreatestdegreeofpartialmelting?Whichtheleast?Assumeno
significantcrystalfractionationinamagmachamberbeforeeachlavawaserupted.
c)Nickelcontentisveryhighinalltheselavas.Nickelisaverycompatibleelement(DNi~
10).Howdoesthisrelatetoourassumptionthattherewasnosignificantcrystal
fractionationinamagmachamber?

II.FractionalCrystallization(RayleighCrystallization)
Wewillnowsimulatethepartitioningofelementsbetweencrytsalsandresidualmeltina
magmachamberthatisundergoingcoolingandfractionalcrystallizationinthecrust.Itwillhelp
considerablyifyouhaveinmindagoodphysicalpictureoftheprocess.Fractional(orRayleigh)
crystallizationdescribestheidealizedprocessinwhichinfinitesimalamountsofsolidareformed
andimmediatelyremovedfromamagma.Aseachincrementofcrystalsisremoved,the
compositionoftheresidualliquidchanges,andthecompositionofthenextcrystalstoformmust
changealso.Wheneveraprocessoccursbysmallincrements,itshouldbeanalyzedby
differentiation,andthecumulativeeffectsoftheprocesscalculatedbyintegration.Inthis
exercisewe'llsimulatetheinfinitesimalchangesbymakingaspreadsheetthatbreaksupthe
processintosmallsteps.Inasimplecaselikethis,wecancomparetheresultstoananalytical
solution,whichisgivenbelow.
Remember,thatinafractionallycrystallizingmagmachamber,Fdecreasesfrom1to0.Thisis
theoppositeofthecaseofmelting,inwhichFincreasesfrom0to1(whichwedealtwithinPart
1ofthislab).Wewillbuildastepbystepmodelofthecrystallizationprocess.Eachtimea
smallamountofcrystalsform,wewillcalculatetheconcentrationofsomeelement(i)inthat
crystalbasedonitsDvalue.Wethenremovethissolidfromthesystem,andcrystallizesome
more.
Thereisanexactsolutionthatdescribesthisprocess.Althoughalittletrickytoderive,youcould
integratetoobtainananalyticalformulafortheconcentrationofiinthecrystallizingliquid:

Ci,L/Ci,0=F(D1)
Aftersettinguptheincrementalmodel,wewillcomparetheresultstothisexactformula.
__________________________________________________
1)WorkonthesecondsheetoftheExceltemplate(itislabeledFractionalCrystallization).
2)Thevariablesandtheirinitialvaluesare:
Divalue(Ci,S/Ci,L)

0.1

startingconcentrationintheliquid(Ci,0)

0.01

startingliquidweight

100

amountcrystallizedeachstep

Youwillwanttowriteequationsthatrefertothesevalues(i.e.putcellreferencesratherthan
numericalvaluesintoyourequations).Bydoingsoyou'llbeabletochangethenumbers

abovetoanswerquestionsaboutthebehaviorofelementswithdifferentDivaluesand
differentstartingconcentrations.
3)Thefirstthingtokeeptrackofishowmanygramsofliquidareinthesystem.Dothisin
columnA.InA13startwiththeinitialliquidweight(D7)andhaveitdecreasebythe
crystallizationincrement(D8).(Numbersshouldextendfromrow13torow113).
4)IncolumnBkeeptrackofthegramsofsolidformedandremovedateachstep(startingwith
step2).Thisisalreadyenteredinthetemplateforyou.Becauseourcrystallization
incrementisconstant,youhavethesamenumberallthewaydown.Westartintherowthat
has99gramsofliquid,sincetherecan'tbeanysolidifthereis100gramsliquid.
5)Nowwerereadytostartfillinginthemodelcalculations.Todoso,observethatateachstep,
wedividethetotalamountoftheelementthatwaspresentintheliquidatthepreviousstep
betweennewlyformedsolidandthenew(smaller)amountofliquid.Wecanconnectthe
twostepsbywritinganequationforconservationoftheelementsmassbetweenthepresent
step(subscriptedn)andthepreviousstep(subscriptedn1):

amount of element i L,n1 amount of element i L,n amount of element i S,n

g liquid n1 Ci,L,n1 g liquid n Ci,L,n g solid n Ci,S,n
RearrangethisbyrewritingCi,S,nintermsofCi,L,n.Thengrouptermstogetanexpressionfor
Ci,L,n,whichyoucanusetofillinline14,columnFofthespreadsheet.YourExcelformula
willrefertotheconstantsatthetopofthesheet,valuesonthepreviousline,andvaluesin
columnsAandB.
6)IncolumnCkeeptrackoftheconcentrationofiinthesolid(Ci,S).(Youhavetofigureout
howtocalculatethisusingtheknownDivalue.)
7)IncolumnD,keeptrackofthetotalgramsofelementithatgointothesolidineachstep.The
columnislabeledas"gramselementiinsolid".(Hint:thetotalnumberofgramsofthe
elementinthesolidiscalculatedfromthetotalweightofthesolid(1gramineachstep)and
theelementconcentrationwhichyouaretrackingincolumnC.)
8)IncolumnE,keeptrackoftotalgramsofelementithatremainintheliquidafterthesolidhas
formedineachstep.Thecolumnislabeledas"gramselementiinliquid".(Asabove,you
cancalculatethisfromthetotalweightoftheliquidremainingandtheelement
concentrationintheliquid(fromcolumnF.)
IfyouvewrittentheformulaeforcellsC,D,EandFwithclevercellreferences,youshould
nowbeabletocopythemdownthespreadsheettothefinalline,inwhichthelastgramof
liquidcrystallizes.CheckwithaTAorinstructorifyouneedhelponthis.
YoucancheckwhetheryourequationsarecorrectbyaddingupthevaluesincolumnD.The
totalforthiscolumnshouldequalthestartingconcentrationintheliquidCi,0xtheinitial
massoftheliquid.Fortheinitialvaluesof100gliquidandCi,0=0.01,theinitialamountof
elementiis1g.

NowcompareyourincrementalmodeltotheexactRayleighequation.Theresultsshouldbe
closeuntilthelastfewsteps,wheretheincrementalmodelwillbegintobreakdownbecause
oftheinabilityofthecoarsemodelstepstohandlethelargeconcentrationchanges.

9)IncolumnGkeeptrackofF,thefractionofliquidinthesystem.(RememberthatFshouldgo
from1to0.)
10)IncolumnH,labeled"ExactRayleighEqnCi,L",entertheRayleighformula(Ci,Lasa
functionthatreferstoCi,0,DiandF.BesuretoreferencecellsD5andD6,soyoucan
changethosevalueslater).RememberthattheRayleighequationisgivenasCi,L/Ci,0,soyou
willhavetorearrangeitslightly.

CheckthatthestepbystepcalculationandtheexactequationagreecloselyforFvalues
greaterthanabout0.10.2.Youcantabulatethepercentagedifferencebetweenthetwoin
columnI.

11)NowusetheexactvaluesincolumnHtomakeonelastcolumnofCi,L/Ci,0values(columnJ).
UsethestartingvalueofCi,0incellD6asthedenominator,sothatyou'llbeabletochange
thistoanswerthelastfewquestions.MakeaplotofCi,L/Ci,0vsF.AsyouchangeDfrom
0.05to10,howdoesCi,L/Ci,0varywithF?(RecallthatinthiscasetheprocessstartsatF=1
andproceedstoF=0asthemeltcrystallizes).
12)Inbasalticmagma,NihasaDofabout10.IntheHonoluluvolcanicrockstheNi
concentrationrangesfromabout300to250ppm.Assumethesamplewiththehighest
concentrationisamagmathathasundergonenofractionalcrystallization.Whatistherange
offractionalcrystallizationrequiredtolowertheNicontentto250ppm?Doesthissupport
orargueagainsttheassumptionmadeinPartI,questions8band8c?
13)Inabasalticmagma,theREEshaveDvaluesthatchangeinaregularwayfrom0.10forLa
(thelightestREE)to0.15forLu(theheaviestREE).Considerabasalticmagmachamber
thatisgraduallycrystallizing.DescribehowyouwouldexpecttheREEpatterntochangein
aseriesoflavaseruptedfromthechamberasthemagmacrystallizes.Asastarting
composition,assume(chondritenormalizedvalues)La=30andLu=5,andastraightREE
pattern.(UseF=1toF=0.5instepsof0.1;CalculateLuandLaateachstep.Theinitial
La/Luratio=30/5=6.Howdoesthisratiochangeasthemagmacrystallizes?

III.OriginofgranitesinthePeninsularRangesBatholith
InsouthernCaliforniaandnorthernBajaMexicoalong,narrow,northwesttrendingseriesof
granitesareexposedthatmakeupthePeninsularRangesBatholith.Althoughthecompositionof
thebatholithdoesnotchangemuchasonesamplesfromsoutheasttonorthwestalong600km,

therearedramaticchangesincompositionfromwesttoeastoveronly100km.Inthisproblem
wewilllookattherareearthelement(REE)compositionofthewesternandeasterngranites,
andtrytodeterminewhattheimplicationsarefortheirorigins.
InthefinalsheetofyourExcellabtemplate(labeledPeninsularRangesBatholith)youhave
thedatayouneedforthislab:REEconcentrationsfortwogranites(#2and#56;columnsB&
C),thechondriteconcentrations(columnD)touseinmakingtheREEchondritenormalized
plot,andthedistributioncoefficientsforseveralminerals(columnsAthroughE,rows16
through24).
AlthoughtonalitesfromthewesternandeasternpartsofthePRBhaveverydifferentREE
patterns(seequestion1below),theyhaveverysimilarmajorelementcompositions.This
suggeststhattheywerederivedbypartialmeltingofsourceswithsimilarmajorelement
compositions.Itislikelythatmuchofthecrustattheedgeofthecontinentismadeofbasalt
eruptedinoldervolcanicarcs.WewilltestthehypothesisthatthePRBgranitesformedby
partialmeltingofolderbasalticcrust.UsethefollowingastheREEconcentrationtypicalof
basalticcrust(alreadydividedbychondriticvalues):
Assumedbasalticcrustcomposition(chondritenormalized;incellsG5thruG12)
Ce
15.0
Gd
10.5
Nd
13.0
Dy
10.0
Sm
12.0
Er
9.5
Eu
10.6
Yb
9.0
Themineralogyofthebasaltthatweproposetomeltdependsonitsdepthinthecrust.At
pressureslessthan15kbweexpect:
60%clinopyroxeneand40%plagioclase.
Atpressuresgreaterthan15kbthebasaltwillhaveadifferentmineralogy:
60%clinopyroxene+30%garnet+10%hornblende
Thequestionwewilltrytoansweris:couldwesternand/oreasterngraniteshavebeen
formedbypartialmeltingofdeeporshallowbasalticcrust?
1) IncellsE5throughF12,calculatethechondritenormalizedvaluesforsample#2andsample
#56.PlottheREEpatternforthesesamplesandthemodelbasalticcrustonthesameREE
plot.Sample#2istypicalofthewesterngranitesandsample#56istypicaloftheeastern
granites.BrieflydescribethedifferencesinREEpatternsbetweenwesternandeastern
granites.(Fromnowon,alwaysusethechondritenormalizedvaluesinyourcalculations
nottheppmvalues).
2) Ifyouaremeltingarockcontainingmorethanonemineral(e.g.,cpxandplag)providethe
generalformulaforhowyouwouldcalculateanoverallorbulkDvalueforthatrock.
StartingincellsG17andH17,calculatethebulkDfortheshallowbasaltandthedeepbasalt,

usingmineralproportionsgivenaboveandthedistributioncoefficientsprovidedinyour
template.
3) Inrows26through48,calculatetheREEcompositionofBatchEquilibriumpartialmeltsof
thedeepandshallowbasalticcrust.Youwillhavetotryavarietyofvaluesforthedegreeof
partialmelting(i.e.,forF).Canyouproduceareasonablemodelthatyieldstheobserved
REEpatternsforthewesternandeasterngranites?ShowyourresultsonappropriateREE
plots.
4) BasedonyourREEmodeling,whatcanyouinferaboutthedepth(s)ofthesourceregion(s)
forthePRB?Drawacrosssectionthatschematicallydepictsyourmodel.
Relateittoasubductionzonesetting;drawthediagramwithadepthscaleandsketchin
featuresatappropriatedepthsandthicknesses;considertheBenioffzonedepth