EENS2120 Prof.StephenA.

Nelson TriangularPlotsinMetamorphicPetrology
Thisdocumentlastupdatedon10Mar2011

Petrology TulaneUniversity

Likeigneousrocks,mostmetamorphicrocksarecomposedof9ormoremajorelements.Thus, initiallyitwouldappearthatwearedealingwitha9or10componentsystem.Recall,however, thatthenumberofcomponentsinanygivensystemistheminimumnumberrequiredtodefine thecompositionofallphasesinthesystem.Thus,sinceconstituentslikeNa2 OandK2 Oarenot usuallyfoundasseparatemineralphases,wecancombinethesewithotherconstituents,like Al2 O3 andSiO2 inthefeldspars,andthusreducethenumberofcomponentsrequiredtodefine oursystem. Thisisespeciallyimportantifwewishtographicallydisplaychemicalrockandmineraldataina waythatiseasilyvisualized.Infact,thebestwaytovisualizesuchdataistoattempttoreduce thenumberofcomponentsto3,sothatwecanplotthecompositionsofrocksandmineralsona triangularcompositiondiagram.Beforediscussinghowthisisdone,wefirstreviewsomeofthe principlesofthreecomponentcompositionaldiagrams. GeneralThreeComponentCompositionalDiagrams Forthemomentwewillassumethatweareinatrue3componentsystemandthemineralsthat wedisplayonatriangularcompositiondiagramisasetofmineralthatareinequilibriumovera narrowrangeoftemperatureandpressure. WefirstlookathowoneofthesediagramsmightappearinthehypotheticalsystemA,B,C. Asshownonthediagram,atthepressureand temperatureunderconsideration,thereare sevenpossiblemineralsthatcanoccurinthis system,althoughweknowfromthephaserule thatnotall7canoccurinthesamerock.In general,themostcommonsetofphaseswillbe wherethenumberofdegreesoffreedom,F,is 2,i.e.wherepressureandtemperaturecanvary bysmallamountswithoutchangingthe numberofphases.Forsuchasituation,the phaseruleis: F=C+2P andwithF=2&C=3,P=3,whichtellsus thatforthisdivariantassemblage,wewillhave threecoexistingphases. Mineralphasesthatcoexistwitheachotherat thistemperatureandpressureareconnectedby lines,calledtielines. Thetielinesdividethediagramintosmallercompositionaltriangles,thattelluswhatminerals willcoexistinarockofanycompositionunderthecurrenttemperatureandpressureconditions. Forexample,forarockwithcompositionx,thedivariantmineralassemblageisAB,A,A2 C.If therockcompositionismovedslightlysothatitnowhascompositiony,notethatthemineral

assemblagewillchangetoAB,A2 C,ABC. Withineachcompositionaltriangle,wecanusetheleverruletoestimatetheproportionsofthe phasesthatwilloccurintherock.Forexample,arockwithcompositionxwillhavethesame mineralassemblageasarockwithcompositionz,butrockzwillhaveamuchhigherproportion ofthemineralA. Inararecase,notethatitispossibleforarockcompositiontolieexactlyonatieline,for exampletherockwithcompositionw.Sucharockwouldconsistofapproximatelyequal proportionsofthemineralsABCandA2 C.Notethatifweapplythephaseruletothissituation, C=3andP=2,wefindF=3.Butinreality,becausethenumberofcomponentsisdefinedas theminimumnumberrequiredtoformallminerals,wecanseethatrockwreallyliesina2 componentsystem,ratherthana3componentsystem.So,Fisstillequalto2. SimilarlyifarockhadexactlythesamecompositionasmineralABC,thenitwouldonlyhave1 phase,ABC,presentatthistemperatureandpressureandwouldbeconsidereda1component system. Wenextillustratewhatmighthappentothemineralassemblagesifwechangethepressureand temperatureconditiontosuchthatsomeofthemineralassemblageschange.Thesame compositionaltriangleisshowninthediagrambelow,butnotetheshiftinthetielines.Insteadof mineralsABandA2 Ccoexisting,atthenewconditionsmineralsABCandAcoexist.This formsnewcompositionaltriangles. Wecandeduceformthisthatachemical reactionmusthaveoccurred,causingAB+ A2 Ctoreactandbereplacedbytheminerals A+ABC. Thechemicalreactionbreaksthetielineto formanewone,andthereactioncanbe writtenas: AB+A2 C=>2A+ABC Notethatafterthereactionhasoccurred,new mineralassemblagesdevelopintherock. RockxisnowcomposedofAB,ABCandA, rockyisnowcomposedofA,A2 C,and ABC,androckz(whichhadthesame assemblageasxinthepreviousdiagram)now hasthesameassemblageasrocky,although, again,theproportionsofthethreemineralswill bedifferentinrocksyandz.. Thenextcaseweconsiderisifoneofthemineralsreactsawaycompletelybecauseitisnolonger stableunderthenewpressureandtemperatureconditions.Thiscaseisillustratedinthediagram below,wherewenotethatthemineralA2 Chasreactedaway.

Thereactionthathasoccurredis:

A2 C=>2A+C Notethatnowrockw,alongwithrocksyand zareinthethreephasetriangleA,ABC,C andwillcontainthemineralsA,ABC,andC, althoughthemineralswilloccurindifferent proportions. Furthermore,rockxstillhasthesamemineral assemblageAB,ABC,A,asithadinthe previousdiagram.

Anotherpossiblecaseiswhereaphasedisappearsandnewphaseappearsastemperatureand pressurechangetonewvalues.Inthediagrambelow,anewphase,ACappearsandmineral ABCdisappears. Atsomepointmovingfromthepressureand temperatureconditionsofthediagramaboveto thoseofthisdiagram,thefollowingreaction hastakenplace: 2ABC=>AB+AC+BC Notethatnow,rocksx,y,andzallliewithin thesamecompositiontriangleandhavethe samemineralassemblageAB,AC,andA, althoughagain,eachrockhasdifferent proportionsoftheseminerals. Rockw,isnowinthe2componentsystem ABAC. Aswestressedinmineralogyandinourdiscussionofigneousrocks.Manymineralsthatoccur innaturearesolidsolutions,andthustheycanhaveavariablecomposition.Solidsolution minerals,becauseoftheirpossiblerangeinchemicalcomposition,donotplotatsinglepointon thecompositiondiagrams,butinsteadplotalongalineorwithinafieldthatrepresentsthe possiblerangeinchemicalcompositions.

Whensolidsolutionsarepresent,thetie linesbecomespreadoutoverarangeof compositionsasisseeninthediagram shownhereforthehypotheticalsystemX, Y,Z.

InthisdiagramthemineralX(Y,Z)shows limitedsolidsolutionwithvariable amountsofZsubstitutingforY.Thisis shownbyasolidlineextendingfrompure XYintotheternarydiagram. Similarly,mineralX2 (Z,Y)showslimited solidsolutionofYsubstitutingforZ. ThemineralsXYZssandZssshowa rangeofpossiblecompositionsthatare representedbyashadedfieldonthe diagram.

Thetielinesthatconnecttherangesforthesolidsolutioncompositionsarejustsomeofan infinitearrayofpossibletielines.But,notethatarockwithacompositionshownas"a"inthe diagram,willconsistoftwophasesanX2 (Z,Y)solidsolutionandanXYZsolidsolution.The compositionsofthesecoexistingsolidsolutionsareindicatedbytheshadedcircleattheendof thetielinethatrunsthroughpointa. Forrockswithcompositionsthatplotinthe3phasetriangles,likebandcinthediagram,the mineralassemblagewouldconsistofthethreephasesatthecornerofthetriangles.Ifsolid solutionmineralsoccuratoneormoreoftheapicesofthecompositionaltriangle,thenthe compositionofthesolidsolutionmineralwillbethatfoundattheapexofthetriangle.These solidsolutioncompositionsareshownaswhitefilledcircles. Forexample,arockwithcompositioncatthepressureandtemperatureofthediagramwillbe madeupofY,Zss,andXYZss.ArockwithcompositionbwillbemadeupofX(Y,Z), X2 (Z,Y),andX. CommonTriangularPlotsUsedinMetamorphicRocks Asstatedabove,commonmetamorphicrockscontainmanymorethanthe3componentswe wouldliketohaveforeasygraphicaldescriptionofcompositionandmineralassemblage.The 13majorelements(expressedasoxides)inmost(notall)metamorphicrocksareSiO2 ,Al2 O3 , TiO2 ,FeO,Fe2 O3 ,MnO,CaO,MgO,K2 O,Na2 O,P2 O5 ,H2 O,andCO2 .Obviouslyifarock consistsonlyofoneortwooftheseconstituents,theproblemiseasy.Forexample,apure QuartzsandstonewouldcontainonlySiO2 ,orapurecalcitelimestonewouldcontainonlyCaO andCO2 .But,themorecommonrockslikeshales,basalts,siliceousdolomites,orgranites,are notsosimple. Therearevariousmethodsavailabletoreducethenumberofcomponentstoaworkablenumber. Amongtheseare: 1. Ignoresomecomponents.ThisisprobablyOKifthecomponentoccursinsmallamounts orisalwayspresentinatherocks.Also,aconstituentmaybeignoredifitoccursinavery mobilephase,thatcouldalwaysbepresent,suchasH2 OandCO2 .Or,asmentioned above,wecouldignoreacomponentifitsoccurrencewasalwayswithinaparticular phase,forexampleNa2 Oisusuallyonlyfoundinalbite,orK2 Oisusuallyonlyfoundin Kspar.

2. Combinesomecomponentsthatareknowntofreelysubstituteforoneanother.For exampleFeandMgorFeandMncouldbecombinedas(Mg,Fe,Mn)Obecausethey readilysubstituteforoneanotherintheferromagnesiansilicates. 3. Limittherangeofcompositionthatadiagramwouldapplyto.Inotherwordsconstruct diagramsthatonlydealwithasubsetofrocks,limitedbycomposition,andspecifically statethatthediagramsonlyapplytothissubset. 4. Useprojection.Thatisassumethataconstituentwillalwaysbepresentandproject compositionsfromthatconstituentinafourorfivecomponentsystemtothe3component system.Wehaveseenthisdonetoalimitedextentinourstudyofphasediagramsin igneousrocksandwewillseemoredetailonthisinthediscussionsthatfollow. ACFDiagrams OneofthefirstusesofthesetypesofdiagramswasbyEskola(1915)whoemployedadiagram knownastheACFdiagraminhisstudyofmetamorphicrocks.ToplotarockontheACF diagram,thechemicalanalysisoftherockisfirstrecalculatedtomolecularproportionsby dividingthemolecularweightofeachoxideconstituentbythemolecularweightofthatoxide. Nominally,theACFdiagramplotsthefollowingcomponents: A=Al2 O3 C=CaO,and F=FeO+MgO However,theAvaluewewantisthevalueofexcessAl2 O3 leftafterallottingNa2 OandK2 Oto formalkalifeldspar.TheCaOvaluewewantistheexcessCaOafterallottingP2 O5 toform apatite,assumingthatanyP2 O5 intherockwillsuckupCaOtoformapatite.Wewillassume thenthatallmineralassemblagesplottedmayalsocontainalkalifeldsparandquartz(and apatite). So,toobtaintheplottingparameters,wecalculatethefollowing,wherethebracketsymbols[] indicatethemolecularproportionsoftheoxides. a=[Al2 O3 +Fe2 O3 ][Na2 O+K2 O] c=[CaO]3.33[P2 O5 ] f=[FeO+MgO+MnO] Sinceweareonlyplottingthese3components,theyhavetobenormalizedsothattheyaddupto 1(or100ifweareplotting%). ift=a+c+f,thentheplottingparametersare: A=100*a/t C=100*c/t F=100*f/t

Whenthesecalculationsaredoneforawide varietyofrockcompositionsandgroupedas pelitic,quartzofeldspathic,basic,and calcareous,thefieldsareasshownhere. MostshaleswillplotinthefieldofPelitic Rocks.Quartzofeldspathicrockslike feldspathicsandstones,granites,andrhyolites willplotintheQuartzoFeldspathicfield. Basicigneousrocks,likebasaltsandgabbros willplotinthefieldofBasicRocks,and siliceouslimestonesanddolomiteswillplotin thefieldofCalcareousRocks. Thisdiagramandthefieldsshownwill becomeanimportantpartoflaterdiscussions, soitiswisetoknowapproximatelywherethe fieldsofthesedifferentchemicaltypesoccur ontheACFdiagram. PlottingmineralsontheACFdiagramissomewhateasierifyouknowthechemicalformulaof themineral,sincemineralformulaearealreadyintheformofmolecularproportions.Thusfora minerallikehypersthene,(Mg,Fe)SiO3 ,wehave1moleculeof(FeO+MgO)forevery1 moleculeofSiO2 .Thus: a=0 c=0 f=1 t=1 so,theplottingparametersbecome A=100*0/1=0 C=100*0/1=0 F=100*1/1=100% andweseethathypersthenewouldplotattheFcorneroftheACFdiagram. Asasecondexample,lookattheformulafortremoliteCa2 (Mg,Fe)5 Si8 O22 (OH)2 Wecanrewritethisformulaas2CaO5(Mg,Fe)O8SiO2 H2 O then: a=0 c=2 f=5 t=7

sotheplottingparametersbecome: A=100*0/7=0 C=100*2/7=28.57% F=100*5/7=71.43% Othermineralsaremorecomplicated.Forexample,theformulaforchloriteis (Mg,Al,Fe)12 (Si,Al)8 O20 (OH)16 .Thuswehaveseveralpossibilitiesforwritingtheformulafor chlorite,anddependingonwhichformulaweuse,chloritewillplotatdifferentlocationsonthe diagrams.Youwillexplorethepossiblesolidsolutionrangesinalabonthistopic.

Althoughyouwillcalculatetheplottingpositionsofsomerocksandawidevarietyofmineralsin lab,thediagramaboveshowstheplottingpositionsofsomeofthemorecommonmineralsthat occurinmetamorphicrocks.Notethatthisdiagramisforreferenceonly,itdoesnotshow mineralassemblagesinrocks(therearenotielines).Notethatalkalifeldsparsdonotplotinthis diagram,butareassumedtobepresentbecauseofthewaywecalculatetheAcomponent.

AKFDiagrams InAKFdiagramsweassumethatbothalkalifeldsparandplagioclasefeldsparcanbepresent, thustheamountofAl2 O3 thatweuseistheexcessAl2 O3 leftafterallottingittoallofthe feldspars.ToobtaintheplottingparametersforACFdiagrams,calculatethefollowing: a=[Al2 O3 +Fe2 O3 ][Na2 O+K2 O+CaO] k=[K2 O] f=[FeO+MgO+MnO] Lett=a+k+f,thentheplottingparametersin%are: A=100*a/t K=100*k/t

F=100*f/t MineralsareplottedinthesamewayaswasdonefortheACFdiagrams,andanexampleAKF diagramshowingthepottingpositionsofcommonmetamorphicmineralsisshownbelow.

NotethatKfeldsparplotsinthelowerrighthandcorner.Toseewhy,wefirsttakethechemical formulaofKfeldsparKAlSi3 O8 andrewriteitinoxideformas1/2K2 O1/2Al2 O3 3SiO2 .Then: a==0 k= f=0 t= So, A=100*0/=0% K=100*/=100% F=100*0/=0% AnotherexampleismuscoviteKAl3 Si3 O10 (OH)2 or1/2K2 O3/2Al2 O3 3SiO2 H2 O.For muscovite: a=3/21/2=1 k=1/2 f=0 t=1=1.5 So, A=100*1/1.5=66.7%

K=100*0.5/1.5=33.33% F=100*0=0% NotethatAKFdiagramsareusedforCaOpoor,K2 Orichrocks,whereasACFdiagramsshould beusedforAl2 O3 andCaOrichrocks. AKFMProjectionontoAFM TheACFandAKFdiagramsdiscussedsofar,arefairlysimple,butuseful.Oneoftheproblems associatedwithACFandAKFdiagramsisthatFeandMgareassumedtosubstituteforone anotherandactasasinglecomponent.Weknow,however,thatinnaturalmineralsthe compositionofFeMgsolidsolutionsisverymuchdependentontemperatureandpressure. Thus,intreatingFeandMgasasinglecomponent,welosesomeinformation.Realizingthis, J.B.Thompsondevelopedaprojecteddiagramthattakesintoaccountpossiblevariationinthe Mg/(Mg+Fe)ratiosinferromagnesiumminerals,andhasprovenveryusefulinunderstanding metamorphosedpeliticsediments. Thompsonstartswiththe5componentsystemSiO2 Al2 O3 K2 OFeOMgOandignores minorcomponentsinpeliticrockslikeCaOandNa2 O.Becausequartzisaubiquitousphasein metamorphosedpeliticrocks,thefivecomponentsystemisprojectedintothefourcomponent systemAl2 O3 K2 OFeOMgOasshownbelow. Next,becausemuscoviteisalsoacommonmineralintheserocks,allcompositionsareprojected frommuscoviteontothefrontfaceofthediagram.(Al2 O3 FeOMgO).Thefrontfaceofthe diagrambecomestheAFMdiagram. MineralsthatcontainnoK2 Olikeandalusite,kyaniteandsillimaniteplotattheAcornerofthe diagram,andmineralslikestaurolite,chloritoid(Ctd),chlorite,andgarnetplotonthefrontfaceof thediagram. Biotite,however,doescontainK2 OandhasvaryingamountsofAl2 O3 andthusisasolidsolution thatliesinthefourcomponentsystem.BecausemuscoviteisrelativelyKpoor,thisresultsin biotitebeingprojectedtonegativevaluesofAl2 O3 . Anyrockcomposition,likecompositiona,showninthediagram,willalsoprojecttothefront face,andmayormaynotplotatnegativevaluesofAl2 O3 .

TocalculatetheplottingparametersfortheAFMdiagramthefollowingformulaeareused: A=[Al2 O3 3K2 O] F=[FeO] M=[MgO] Usingtheseparameters,onecangridofftheAFMdiagramwiththeverticalscalerepresentedby thenormalizedvaluesfortheAparameter [Al2 O3 3K2 O]/[Al2 O3 3K2 O+FeO+MgO] andthehorizontalpositionbasedontheratioofMgO/(FeO+Mg).asseembelow.Ofcourse thesevaluesareobtainedafterconvertingthechemicalanalysisoftherocktomolecular proportions.

NotethatifweprojectKsparfrommuscovite,thatthearrowpointstowardtheKcornerofthe4 componenttetrahedron,andthusKsparwouldprojectawayfromthefrontfaceofthediagram. Thus,asseenontheAFMface,Ksparwouldplotatnegativeinfinity. Theprojectionfrommuscoviteworkswellformetamorphicrocksthatcontainmuscovite.But,at highergradesofmetamorphism,intheupperamphibolitefaciesandthegranulitefacies, muscovitebecomesunstableandisreplacedbyKfeldspar+quartz+anAl2 SiO5 mineral.In ordertoshowrocksandmineralassemblagesatthesehighergradesofmetamorphism,anew projectionismadefromKspar,asshownbelow. Forthisdiagramtheplotting parametersaremuchmorestraight forward,with A=[Al2 O3 ] F=[FeO] M=[MgO] Allonamolecularbasisandthen renormalizedtosumto100%. Notetheabsenceofallhydrous phases(staurolite,chloritoid, muscovite)exceptbiotiteinthis projection. ResolvingProblems Assoonaswestartignoringcomponentsorprojectingintothreecomponentcomposition diagramsthereisapotentialtoloseinformation.Sometimesthelossofinformationcreatesa

dilemmathatmustberesolvedinordertounderstandthemineralassemblage. Forexample,acommonmediumgradeassemblageinapeliticrockisstaurolite,garnet, muscovite,biotite,quartz,andplagioclase.PlottingthesemineralsonACF,AKF,andAMF diagrams,asshownbelowcreatesaproblem.Fordivariantequilibriumweexpectthenumberof componentstoequalthenumberofphases(c=3,sop=3)atleastfortheternarypartofour system. Thus,intheACFdiagram,arocklikecompositionxwouldhaveplagioclase,garnet,staurolite (+quartz+muscovite),butbiotitecannotberesolvedfromgarnetbecausetheyplotnearthesame point(s).Still,intheACFdiagram,xplotswithina3phasetriangle.

IntheAFMdiagramthesamerockofcompositionxisseentohavegarnet,staurolite,andbiotite (+quartz+muscovite).Plagioclaseisignoredbythediagram(becauseCaOisnotplotted),but wecanresolvebiotiteandgarnetbecausetheyclearlyhavedifferentcompositionsintheAFM plot. IntheAKFplotthereisanambiguity.Compositionxplotsinthecorrect4phasefieldof muscovite,garnet,staurolite,andBiotite,butdivariantequilibriumrequiresthatitplotina3 phasetriangle. TheproblemintheAKFdiagramimpliesoneofthefollowing: 1. Theassemblagerepresentsonewhereequilibriumhasnotbeenachievedintherock.

2. Theassemblageisreallyaunivariantassemblage,ratherthanadivariantassemblage. 3. TheAKFdiagramisnottrulybehavingasathreecomponentsystembecauseof informationlosttocreatetheprojection. Becausethemineralassemblageisverycommoninmediumgradepeliticrocks,itisunlikelythat equilibriumhasnotbeenachieved,anditisunlikelythatitrepresentsaunivariantassemblage (univariantassemblagesarerarecomparedtodivariantassemblages. NotethattheAFMplotdoesshowtheproperassemblage,whichsuggeststhattheFeandMg componentsbehaveasseparatecomponents.IncalculatingtheAKFandACFdiagramswe havecombinedFeandMg.Thus,neithertheAKFnortheACFdiagramstrulyrepresentathree componentsystem,andthisresultsintheambiguity. Whileallofthesediagramsareuseful,wemustalwaysrememberthatthediagramsare simplificationsofamorecomplexsystem,andthus,whenambiguitiesappear,onemustapply reasontofigureoutwhythediagramsdonotexplainwhatisobservedintherock. Examplesofquestionsonthismaterialthatcouldbeaskedonanexam 1. BeabletoplotthecommonmineralsonAFCandAFKdiagramsbyusingthechemical formulaeoftheminerals. 2. BeabletoplotthecompositionfieldsforPetlitic,QuartzoFeldspathic,Calcareous,Basic, andUltraBasicsrocksonbothACFandAKFDiagrams. 3. Inasequenceoftriangulardiagramsrepresentingincreasingpressureandtemperature,be abletodeducethechemicalreactionsthatoccurtocausethebreakingoftielines.Note thattielinescanbebrokenin3differentways. 4. Whydon'tthesetriangulardiagramsalwaysgiveusresultsthatreproducenature? ReturntoEENS2120HomePage