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 + H2O

Chl + Qtz
0

Mg/(Mg + Fe)

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
TiO2
Al2O3
Fe2O3
FeO
MnO
MgO
CaO
Na2O
K2O
P2O5

57.9
0.87
17.0
3.27
4.04
0.14
3.33
6.97
3.48
1.62
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:
C:
F:

(Al2O3+Fe2O3)(Na2O+K2O)
CaO3.3*P2O5
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:
K:
F:

(Al2O3+Fe2O3)(Na2O+K2O+CaO)
K2O
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).

AFM Projection

Al2O 3
projected pyroph.,and, ky,sill

K 2O
B=Biotite
B'=ProjectedBiotite

projected musc
projectedKspar

Kspar

pyrophyllite

Musc
Al 2O 3

and, ky,sill

+0.5
B

MgO'

+0.5
musc

B'
FeO'

Kspar
SiO2

K2 O

+0.5

0.5

Asanexample,therightdiagramshowstheprojectedpositionofbiotitefrommuscovite.Note
thattheprojectedmuscovitefallsandnegativeAcomponents.ThatisOK.
Mathematically,theAFMcoordinatesarecalculatedasfollows:
A:
F:
Mg:

Al2O33*K2O
Al2O3K2O
FeO(+MnO)
MgO

(ifprojectedfrommuscovite)
(ifprojectedfromKfeldspar)

Figure2419showsthepositionofmostcommonAFMmineralsasprojectedfrommuscovite.
Figure2420showsanAFMphasediagramappropriatefortheloweramphibolitefacies.Note
theinvariantanddivariantfields.

0.5

ChemographyofReactions
Phaseappearance/disappearancediscontinuousreaction

als

A
F

grt

chlr

als

M
st

grt

chlr

temperature
Switchingtielinediscontinuousreaction

als

st

grt

chlr

als

M
st

bt

grt

chlr

bt

temperature

Continuousreaction

c
st + H 2O
(+ ky or chl)

a
chl + ky
0

temperature

ky

ky

st

st
grt

chl

1.0

XMgO

ky

st

grt

chl

M F

grt

chl

M F