METAMORPHICREACTIONS

Thewordmetamorphismmeanstransformation.Metamorphismofrocksinnatureinvolves
reactionsamongminerals.Becausemineralsarechemicalcompounds,metamorphisminvolves
chemicalreactions.

Typeofmetamorphicreactions

Polymorphicphasetransformation

ThesimplestmetamorphicreactioninvolvespolymorphictransformationofmineralsasPorT
changes.ThemostimportantmetamorphicpolymorphsareintheAl2SiO5system,theminerals
andalusite,kyanite,andsillimanite.Thetransformationofcalcitetoaragonitewithpressurein
subductionzonesisalsoanimportantmetamorphictransformation.

Solidsolidnettransferreactions

Thesereactionsinvolvetheformationofanewmineralassemblagefromanoldmineral
assemblage,withouttheinvolvementofavolatilephase.Anexampleisthereaction:

NaAlSi3O8(albite)NaAlSi2O6(jadeite)+SiO2(quartz),

thatoccursinsubductionzoneswithincreaseinpressure.

Anotherexampleisthereaction

Mg3Si4O10(OH)2(talc)+4MgSiO3(enstatite)Mg7Si8O22(OH)2(anthophyllite)

Thisreactionhashydrousminerals,butnovolatilephaseisproducedorconsumed.

Devolatilizationreactions

Mostmetamorphicreactioninvolvetheproductionorconsumptionofavolatilephase.Because
theyalsoinvolveachangeinmodalproportionofminerals,theyarealsonettransferreactions.
Anexampleis:

KAl2AlSi3O10(OH)2+SiO2KAlSi3O8+Al2SiO5+H2O.

Becausedevolatilizationreactionsinvolveproductionofahighvolumevolatilephase(the
reactionshavehighpositiveV),thetemperaturesthatthesereactionsoccuratarehighly
dependentonpressureandtheproportionoftherelevantvolatilecomponentinthefluidphase,
becausethefluidphasemaycontainadditionalcomponent,suchasCO2.


Figs.262and264fromWinter,2001

Continuousreactions

Rocksthatcontainmineralsthataresolidsolutionsusuallyundergocontinuousreactionsovera
broadtemperaturerange.Continuousreactionsareparticularlyimportantinpeliticrocksinthat
mineralshavevariableFe/Mgratios.Considerthereaction

Chl+QtzGrt+H2O.

Chlorite,garnetandbiotiteareallsolidsolutionscontainingFeandMgendmembers.This
impliesthatthereactionwilloccuroveragiventemperaturerange,dependingontheFe/Mgratio
oftherock.Thisreactioncanbeillustratedusingthefollowingschematicphasediagram,that
looksjustliketheolivinemeltorplagioclasemeltbinarydiagramsthatwecoveredinigneous
petrology:
 Grt + H 2O

Chl + Qtz

0 Mg/(Mg + Fe) 1
Duringthereaction,thefirstgarnetthatwillformwillbemoreFerichthanchlorite.With
increasingT,moregarnetwillformattheexpenseofchloriteasbothwillbecomemoreMgrich.
Thereactionwillbecompletedwhenallchloritedisappears.

Ionexchangereactions

Ionexchangereactionsinvolvetheexchangeoftwoionsbetweentwomineralsasafunctionof
temperatureand/orpressure.Anionexchangemayormaynotinvolveacontinuousreactionas
above.Anexampleofanionexchangereactioninwhichnomineralisconsumedorproducedis
theFeMgexchangebetweenbiotiteandgarnet.Theexchangereactioniswritteninthe
followingforms:

annite+pyrope=phlogopite+almandine

or

Ionexchangereactionsformthebasisforgeothermometryandgeobarometrytobecoveredlater.

Oxidation/reduction(redox)reactions

Thesereactioninvolvetheadditionorremovalofoxygenfromtherocks.Theyprimarilyinvolve
oxideminerals.Twoexamplesare:

4Fe3O4+O26Fe2O3(MH)

or

3Fe2SiO4+O22Fe3O4+3SiO2(FMQ)
(Thesereactionsalsooccurinigneousrocks).Atagivenpressure,thesereactionsareunivariant.
Therefore,whenmineralsonbothsidesofthereactionarepresent,atagiventemperaturethey
fix(buffer)thepartialpressureofoxygen(fugacity)intherockormagma.

Fig.2610fromWinter,2001
Metasomaticionexchangereactions

Thesereactionsinvolvetheexchangeofionsbetweenfluidsandminerals.Thereforethese
reactionscanbethoughtofasdiageneticreactions.Someexamplesinclude:

NaAlSi3O8+K+Cl(influid)KAlSi3O8+Na+Cl(influid)[occursathighT]

or

2KAlSi3O8+2H+(acid)+H2OAl2Si2O5(OH)4(kaolinite)+SiO2+2K+[truediagenesis].

APPLICATIONOFTHEPHASERULETOMETAMORPHICROCKS

InigneouspetrologywecoveredtheGibbsphaserule:

F=C +2.
Inmagmaticsystems,bothpressureandtemperaturecanchangeduringevolutionofamagma,
hencethe2attheendofthephaseruleequation.Consider,however,arockthatequilibratedat
agivenmetamorphicfaciesatfixedPTconditions.Inthatcase,thephaserulereducesto:

F=C
Thismeansthatforamineralassemblagetobeinchemicalequilibrium,thenumberofphases
(minerals)mustbeequaltoorislessthanthenumberofcomponents.Theaboveformofphase
ruleiscalledtheGoldschmidtsmineralogicphaseruleorsimplymineralogicphaserule.

Howmanypossiblemineralscantherebeinametamorphicrockthatisinastateofequilibrium?
Letusconsidercompositionofanandesitethatmayhaveundergonemetamorphism:
SiO2 57.9
TiO2 0.87
Al2O3 17.0
Fe2O3 3.27
FeO 4.04
MnO 0.14
MgO 3.33
CaO 6.97
Na2O 3.48
K2O 1.62
P2O5 0.05

Thereareelevenoftheseoxides,whichatfirstviewmaysuggestthatwecouldhave11minerals
intherock.Remember,however,thatmineralsaremadeofmultipleoxidesandwehaveto
reducethenumberofcomponentstoaminimumforthephaseruletowork.Inanandesite,we
knowthat

1) AllsilicateshaveSiO2plusthereisquartz,sowedonotneedtoconsiderit.
2) Na2OandK2Ooccuressentiallyonlyinfeldsparwheretheyarealwaystiedupwith
aluminum.SoweonlyhavetoadjustAl2O3forthesetwocomponentsandeliminatethem
fromconsideration.
3) FeO,MgO,andMnOusuallysubstituteforeachotherinferromagnesianminerals,sowe
cancombinethemintoonecomponent.
4) Fe2O3canbelow,butifitishigh,itusuallybehavesasAl2O3,sowetreatisthesameas
alumina.
5) P2O5occursmostlyinapatite,sowecorrectCaOforitspresence.
6) WeignoreTiO2,becausethereisonlylittleofit.However,itcancausethepresenceof
ilmeniteorrutile,whichareoxides.

Soweendupwiththesethreecomponentsonmolarbasis:

A: (Al2O3+Fe2O3)(Na2O+K2O)
C: CaO3.3*P2O5
F: FeO+MgO+MnO

Thus,fromthemanycomponentsystemthatwestartedwith,wehavereducedittothethree
componentsystem,whichwecandepictonaflatpieceofpaper.Thismeansthatinadditionto
quartz,alkalifeldspar,andapatite,wecanhavethreeadditionalmineralsatafixedpressureand
temperature,oragivenfacies.Becauseinthereductionoftherockcompositiontothethree
componentsweimplicitlyconsideredquartz,alk.feldspar,andapatite,wesaythatthe
compositionnoftherockorincludemineralsareprojectedfromthesemineralsortheir
componentsNa2O,K2O,SiO2,P2O5,SiO2.

CHEMOGRAPHICREPRESENTATIONOFMETAMORPHICFACIES
Mineralassemblagesinprojectedmetamorphicsystemscanbedepictedonternarydiagrams.
ThebasicACFandAKFdiagramsweredevisedbyEskolain1915.

ACFdiagram

ThemineralswhichfallintheACFsystemcanberepresentedinaternarydiagram.Their
positioninthediagramiscalculatedwiththeequationsshownabove(seeFig.244).Atagiven
facies,arockofagivencompositionwillhaveasetofthree(ortwo)ACFminerals,inaddition
toquartz,alk.feldspar,andapatite.(Fig.245).Atanotherfacies(PT)conditions,thesetof
mineralswillbedifferent.TheACFdiagramismostusefulforillustratingmineralassemblages
inmafic,calcareous,andcalcsilicaterocks.

Figs.244and245fromWinter,2001

AKFdiagram

TheAKFdiagramismostusefulforillustratingreactionsinpeliticandmaficrocks.Itis
aprojectionfromplagioclase,alkalifeldsparandquartz.Thethreecomponentsarecalculatedas
follows:

A: (Al2O3+Fe2O3)(Na2O+K2O+CaO)
K: K2O
F: FeO+MgO+MnO

NotethatincalculationoftheAcomponent,weareinterestedinAl2O3thatoccursinexcessof
theamounttiedupinplagioclaseandalkalifeldspar.ThepositionsofthemostcommonAKF
mineralsandexampleofassemblagesinthelowPamphibolitefaciesareshowninFigures246
and247.


Figs.244and245fromWinter,2001
AFM(AKFM)diagram

In1957,JamesB.ThompsonrecognizedthatthereisadeficiencyintheACFandAKF
diagrams,inthattheydonotconsidertheimportantsolidsolutionpropertiesofFeandMg.The
problemoflumpingFeandMgtogetherisespeciallycriticalforpeliticrocks,becauseminerals
canhavevariableFe/Mgratios.
Thompsonrecognizedthatvirtuallyallpeliteshavemuscovite(orKfeldsparatgranulite
facies),quartz.Anotherassumptionhemadeisnotusuallytrue,isthatPH2O=Ptotal,whichimplies
thatallhydrousmineralscontainonlyOHontheirhydroxylsites.(Thisisnotalwaystrue,
however.)Thederivethediagram,firsthereducedthecomponentsK2O,Al2O3,andSiO2into
twocomponents,byprojectingallappropriatemineralsfromSiO2(leftdiagrambelow).Thenhe
projectedrestofthemineralsfromeithermuscoviteorKfeldsparuntotheAl2O3FeOMgO
plane(rightdiagrambelow).

Al2O 3
AFM Projection
K 2O
projected pyroph.,and, ky,sill

B=Biotite
B'=ProjectedBiotite
Kspar
pyrophyllite
projected musc
Musc
projectedKspar and, ky,sill Al 2O 3 +0.5 MgO'
B 0.5
+0.5
musc B'
FeO'
+0.5
Kspar

SiO2 0.5
K2 O

Asanexample,therightdiagramshowstheprojectedpositionofbiotitefrommuscovite.Note
thattheprojectedmuscovitefallsandnegativeAcomponents.ThatisOK.

Mathematically,theAFMcoordinatesarecalculatedasfollows:

A: Al2O33*K2O (ifprojectedfrommuscovite)
Al2O3K2O (ifprojectedfromKfeldspar)
F: FeO(+MnO)
Mg: MgO

Figure2419showsthepositionofmostcommonAFMmineralsasprojectedfrommuscovite.
Figure2420showsanAFMphasediagramappropriatefortheloweramphibolitefacies.Note
theinvariantanddivariantfields.
 ChemographyofReactions

Phaseappearance/disappearancediscontinuousreaction

A
als

A
als

grt
F chlr
M
st

grt
F chlr
M

temperature

Switchingtielinediscontinuousreaction

A
als

st

A
grt als
F chlr
M

st
bt

grt
F chlr
M

bt
temperature
Continuousreaction

c
st + H2O
(+ ky or chl) b

a
chl + ky

0 XMgO 1.0
temperature

A A A
ky ky ky

st st st

grt grt grt

F chl M F chl M F chl M

a b c