Beruflich Dokumente
Kultur Dokumente
Temperature-Time Paths
Short Course in Geology: Volume 7
Metamorphic Pressure-
Temperature-Time Paths
Frank S. Spear
and
Simon M. Peacock
QShort
Course
Presented
atthe
28th International GeologicalCongress
Washington,D. C.
Library of CongressCataloging-in-Publication
Data
Spear,Frank S.
Metamorphicpressure-temperature-timepaths.
Includesbibliographies.
1. Metamorphism(Geology) 2. Rockpressure.
3.EarthTemperature. I. Peacock,Simon Muir, 1960-
II. Title.
QE475.A2S68 1989 552'.4 89-14892
ISBN 0-87590-704-0
Preface vii
1 PetrologicDetermination of Metamorphic
Pressure-Temperature-TimePaths 1
Introduction 1
Thermodynamics of Heterogeneous Systems 2
Calculationof MetamorphicPhaseEquilibria 6
Petrogenetic Grids 8
Geothermometry and Geobarometry 9
Bibliographyof Geothermobarometers11
Applicationof Thermobarometry: Procedures and PotentialPitfalls 16
Inferringa MetamorphicP-T Path 25
Thermobarometry on InclusionSuites 25
DifferentialThermodynamics: TheroreticalConsiderations25
DifferentialThermodynamics: Applications 30
A WorkedExample:Fall Mountain,New Hampshire,USA 43
ConcludingRemarks 49
Acknowledgments50
References 50
A renaissancein the study of metamorphicrocks has reachedthoseP-T conditionsor to how they arrived back at
occurredin the past decade. For a long time (with some the surface, the thermal modeling revealed that the
notable exceptions) metamorphic rocks were studied as metamorphicP-T path could be a sensitiveindicatorof the
examplesof heterogeneoussystemsat equilibrium and the thermal and tectonic evolution of a terrane. Once this fact was
study of metamorphismwas, in effect, a phase equilibria recognized,it becameclear that the studyof metamorphic
experiment.A major goalof metamorphicpetrologywas to rocksmight reveal much aboutthe tectonicevolutionof an
pigeonholethe typesof mineralassemblages encounteredinto orogenicbeltbeyondanestimate of theP-T conditions.
the appropriate metamorphic facies. Indeed, even Within this framework, a principal objective of
geothermobarometry, in all its sophistication,
is nothingbut a metamorphic petrologyhasbecomeoneof determining theP-T
quantitativeform of pigeonholing. However, all of this has evolutionof rocksin metamorphicbeltswith the goalof using
changedrecentlyand today,metamorphicrocksare studiedin thisinformationto placeconstraints
on thethermalandtectonic
large part as a meansto unravel major tectonicproblems evolutionof the belt. The analysisof metamorphicrocksin
duringorogenesis. this way placesgreatdemandson the petrologist,who must
In part this shift in emphasisstartedwith the adventof the mastertechniquesof phasepetrologyof complexsystemsin
theoryof platetectonics.Early thermalmodelsof convergent order to extract the information desired from the rocks.
plate margins revealed a region of high pressure-low Moreover, the petrologistmust be versedin applicationsof
temperature conditionsin whichit wasthoughtthatblueschists thermalmodelingto crustalorogenesisso that the P-T paths
andeclogiteswouldevolve. Much of thepioneeringwork on derived may be interpretedcorrectly. In addition, recent
the tectonicsignificanceof blueschistswas done by W. G. advancesin structuralgeologywith respectto determinationof
Ernst and coworkers in terranes such as the Franciscan the kinematicsof a body of rock providesanotherimportant
Complexof California. Theseattemptswerebasedlargelyon piece to the puzzle, as do geochronologicstudiesof the
a few experimentally measured equilibria, some crystallization and closure ages of various radiometric
thermodynamic calculations,andestimatesof the P-T locations systems.
of metamorphic facies. The recognition of a blueschist The purposeof theseshortcoursenotesis to providean
assemblageoverprinted by a greenschistassemblagehad introductionto two aspectsof the studyof metamorphism:
(1)
implicationsfor the metamorphicP-T history, even in the the applicationof phaseequilibriato the determinationof
absenceof quantitativevaluesfor theP-T conditions. metamorphicP-T conditionsand P-T paths and (2) the
The earliest attempt at explaining the origin of a application of thermal modeling to the evolution of
metamorphic belt as resulting from the thermal effects of metamorphic terranes.Muchof thephaseequilibriarequired
continentalcollisionwas in a now classicpaperby Oxburgh to apply modern techniquesto metamorphicsystemsis
and Turcotte [1974], which was little read at the time of its straightforward,but can be quite complex in detail. A
publication.The ideasembodiedin thiswork werepickedup systematicdevelopmentis presentedin order that those
and amplified by Englandand Richardson[1977] and fully unfamiliar with the techniquescan get a start in their
developed by England and Thompson [1984]. The applicationand so that the similarityof the equationsand
fundamentalconclusionof thesepaperswas quite simpleyet approaches utilizedwill be apparent. Onefactorthatshould
quiteprofound.Tectonicprocesses operatingat plate tectonic become apparenton reading the notes is that the same
velocities would perturb the thermal structure of the thermodynamic equationscanbe appliedto the solutionof
lithospherebecausethe time scalefor thermal relaxationis manydifferentproblems.It is appropriate to mentionat this
significantly longer than that for the tectonic disturbance. pointthat the development of the thermodynamic analysis
Subsequent relaxationof the thermalperturbationwouldresult presented hereinowesa greatdebtto J. B. Thompson, Jr.,
in pressure-temperature-timepaths of metamorphism that whosewritingsandlectureshaveinspireda generation of
would be characteristic of the thermal perturbation and petrologiststo try and unravelthe mysteries recordedby
exhumationhistory. This thermalmodelingopenednew vistas rocks.
for metamorphic petrology by providing the crucial link The second section of these short course notes examines the
between crustal dynamics and metamorphic processes. basicconceptsof heat flow as appliedto the crust and the
Whereasheretoforemetamorphicrockswere looked upon as construction and solution of numerical models of heat transfer.
havinga setof P-T conditions,with little regardfor how they Because of the complexity of metamorphism,numerical
vii
viii Preface
PETROLOGIC DETERMINATION
PETROLOGIC DETERMINATION OF
OF
METAMORPHIC PRESSURE-TEMPERATURE-TIME
METAMORPHIC PRESSURETEMPERA TURE TIME PATHS
PATHS
Frank: S.
Frank S. Spear
Spear
Deparnnent of
Department of Geology,
Geology, Rensselaer
Rensselaer Polytechnic
Polytechnic Institute,
Institute, Troy,
Troy, New York 12180
New York 12180
Introduction
Introduction metamorphic rock
metamorphic rock that is the
thatis the peak
peak metamorphic
metamorphic temperature.
temperature.
A second
second consideration
consideration also
also contributes
contributes to the
the notion
notion of
peak
peak metamorphic
metamorphic conditions. Mostprograde
conditions. Most prograde metamorphic
metamorphic
The
TheConcept ofan
Conceptof Equilibrium State
an Equilibrium State in
in a Metamorphic Rock
a Metamorphic Rock reactions are
reactions dehydration reactions
are dehydration reactions (although there are
(althoughthere are some
some
notable
notable exceptions
exceptions in in very
very common
common assemblages).
assemblages). If If fluids
fluids
Metamorphic
Metamorphic rocks exhibit
rocks exhibit abundant
abundant evidence of
evidence of complex
complex escape from
escape from a rock as
a rock as devolatilization
devolatilization proceeds,
proceeds, then
then this
this
histories of
histories of temperature,
temperature, pressure
pressure andand strain. Features such
strain. Features suchas
as process is
process is irreversible
irreversible unless
unless fluids
fluids can
can reenter
reenter the
the rock.
rock.
reaction textures,
reaction textures, structural fabrics, mineral
structural fabrics, mineral inclusions
inclusions andand Under crustal
Under crustalconditions,
conditions, dehydration
dehydration reactions
reactions commonly
commonly
chemical zoning
chemical zoning in minerals all
in minerals all attest
attest to
to the changing
the changing have positive
have positive slopes
slopes soso the
the maximum
maximum dehydration
dehydration statestate
conditions
conditions that
thatare experienced by
areexperienced by metamorphic
metamorphic rocks.
rocks.One Oneof
of experienced
experienced by
by aa rock
rock will
will be where the
bewhere theP-T path is
P-T path is tangent
tangentto to
the
themost
mostimportant
importantendeavors
endeavors of the
of petrologist is
the petrologist is to
to use
usethe
the the dehydration reaction,
the dehydration reaction, as as shown
shownin Figure 1A.
in Figure lA. Note that
Note that
varied
variedinformation
information contained
contained in
in rocks
rockstoto decipher
decipher this complex
thiscomplex theseconditions
these conditions areare near
nearthethepeak temperature
peak temperature andtherefore
and therefore
history, which can
history, which can then
then be related to
be related thermal and
to thermal and tectonic
tectonic reinforce thecreation
reinforce the creationof of aa peak
peakmetamorphic
metamorphic assemblage.
assemblage.
processes that
processes thathave operated in
haveoperated in the crust.
thecrust. In the
In absenceof
the absence of multiple
multiple heating
heating events, therefore,
events, therefore,
A
A fundamental
fundamentalconcept
conceptnecessary
necessaryfor for the
the analysis
analysisof of metamorphic
metamorphic rocksshould
rocks shoulddisplay
displaymineral
mineralassemblages
assemblages and
and
metamorphic rocks
metamorphic rocks isis that
thatofof an
an equilibrium
equilibriumstate,
state,which will
which will mineral chemistriesthat
mineral chemistries that reflect the peak
reflect the peak metamorphic
metamorphic
be referred to
be referred to as
as the peak metamorphic
thepeak metamorphic condition.
condition. The
The basis
basis temperatures(i.
temperatures T max ) . It
(i.e.e. Truax). It is
is also
also worth
worth noting
noting that
that
for
for this
thisconcept
conceptcomes
comesfromfrom an examination of
an examination of the kinetics of
thekinetics of deformation events
deformation eventsmaymay notnot occur
occur atat the
the same
sametime
time that
that the
the
metamorphic processes in
metamorphicprocesses in the
the context
contextof of the
the metamorphic
metamorphic peak temperatures
peak temperatures are attained.
are attained. The maximumrate
The maximum rate of
of
pressure-temperature path.
pressure-temperature path. Kinetic processes in
Kinetic processes in general
general deformationmay
deformation may occur
occurat at conditions
conditionsfar far from
from the
the thermal
thermal
conform
conformto toananArrhenius
Arrhenius relationship
relationship of
of the
theform
form maximum.
maximum.
Theabove
The aboveconsiderations
considerations justify thepostulate
justify the postulate or hypothesis
or hypothesis
Rate
Rate= (constant)
(constant)
= x
x exp(-MJ/RT)
exp(-AH/RT) (1)
(1) of an
of anequilibrium
equilibrium statefor
state foraa metamorphic
metamorphic rock thatis
rock that isat
ator
ornear
near
the thermal maximum. This is
the is not a new idea,
not a but is inherent
idea, but inherent
where
where"Rate"
"Rate"is
isaa generalized
generalized metamorphic
metamorphic rate,
rate,which
whichmaymaybe be in the
in the metamorphic faciesconcept
metamorphic facies concept of Eskola[1915;
of Eskola [ 1915;see
seealso
also
a
a diffusion rate or
diffusion rate or aa reaction
reaction rate,rate, "constant"
"constant" is is aa Thompson, 1955]. Indeed, a major goal in the analysis of
Thompson,
1955].Indeed,
a majorgoalin theanalysis
of
preexponential
preexponential constant,
constant,AH AH isis an
an activation
activationenergy,
energy,R R isis the
the metamorphicrocks
metamorphic rocks is is the
the determination
determinationof of the
the peak
peak
gas
gasconstant
constantand
andT T isis temperature.
temperature.As As aa consequence
consequence of
of this
this metamorphic
metamorphic conditions.
conditions.
relationship,
relationship,the
the rate
rate ofof generalized
generalizedmetamorphic
metamorphicprocesses
processes Followingin
Following in this
thisvein, the analysis
vein, the analysisof of metamorphic
metamorphic P-T
P-T
increases
increases exponentially
exponentially with
withincreasing
increasing temperature.
temperature. paths will be
paths will bediscussed
discussed in two
in twoparts. Thefirst
parts. The firstsection
section of these
of these
Consider
Consider a
a rock following the
rockfollowing thegeneralized
generalized P-T
P-T path
pathshown
shown noteswill
notes will focus
focuson on procedures for the
procedures for thedetermination
determination of peak
of peak
in
in Figure
FigurelA,
1A, with
withthethegeneralized
generalized T-t
T-t history
historyshown
shownin in Figure
Figure metamorphic
metamorphicconditions.
conditions.Of necessity, this
Of necessity, will involve
this will involve a a
lB. The
IB. The Arrhenius
Arrheniusrelationship (equation1)
relationship(equation predicts a
1) predicts a rate
rate reviewthe
review the thermodynamic
thermodynamic relationsthat
relations that are
areapplicable
applicableto to aa
versus
versustemperature
temperature relationship
relationship that
thatcan
canbe be projected
projectedonto
ontothethe heterogeneous
heterogeneous systemin
system in equilibrium
equilibriumas asthese
theserelations
relationsformform
temperature-time
temperature-time curve
curveof of Figure
Figure IB lB toto give
give the
therate
rate vs
vs time
time the basis
the basisofof geothermobarometry
geothermobarometry and are
and are essential
essentialfor for the
the
curve
curve shown
shownin in Figure
Figure 11C. C. Figure
Figure 11C C shows
showsthat
that rates
rates ofof understanding
understanding of how
of how metamorphic
metamorphicmineralmineralassemblages
assemblages
metamorphic
metamorphic processes
processesare are most
most rapidrapid near
near the
the peak
peak evolve.
evolve.
metamorphic
metamorphictemperature
temperatureand and that
that the
the rate
rate approximately
approximately In the
In the second
second section,
section, thethe evolution of the the mineral
doubles
doublesover the10
overthe 10C Cnear
nearthe
themetamorphic
metamorphic peak.
peak.Therefore,
Therefore, assemblage
assemblage will be
will be used
usedas as the
the basic
basictool
tool for
for inferring
inferring
most
mostmetamorphic
metamorphic recrystallization
recrystallization will
will occur
occurnear
nearthe
the peak
peak metamorphic
metamorphic P-Tpaths.
P-T paths.The
Thefundamental
fundamental assumption
assumption thatwill
that will
metamorphic
metamorphictemperature
temperatureand and the
the mineralogy
mineralogyand and mineral
mineral be invoked
be invokedin in the
the analysis
analysisof of P-T
P-T paths
pathsinin this
thisway
way is is that
that
chemistry
chemistrywill
will reflect
reflectthese
theseconditions.
conditions.In In many
manycircumstances
circumstances metamorphic
metamorphic rocksrecord
rocks record a sequence of
a sequence ofequilibrium
equilibrium states that
states that
it
it is
is possible
possible to to envision
envision an an eqUilibrium
equilibrium statestate for
for aa can
canbebeanalyzed
analyzed using
usingequilibrium
equilibrium thermodynamics.
thermodynamics.
Spear:Petrologic
determination
of metamorphic
P-T-tpaths
Spear: Petrologicdetermination
of metamorphic
P-T-t paths 3
After performing a row reductionon the right hand side of Maximum reactions= 5 ! / (4! 1!) = 5 (15)
theseequations,we have
Equation14 givesthemaximumnumberof possiblereactions
Fo =2MgO + 0FeO + 1SiO2 (8) in a givensystem,but doesnot correctlycountthenumberof
Fa =0MgO + 2FeO + 1SiO2 (9) uniquereactionsthatmay be writtenin the completesystem
En- 0.5Fo =0MgO + 0FeO + 0.55iO2 (10) becauseof compositionaldegeneracies.To find the set of
Fs-En-0.5(Fa-Fo) =0MgO + 0FeO + 05iO2 (11) unique(i.e. different)reactions,it is first necessaryto apply
Qz+Fo-2En =0MgO + 0FeO + 05iO2 (12) equation(14) to all possibleunary subsystems, then to all
possible binary subsystems,then to all possible ternary
Note that all coefficientsbelow the diagonalon the right hand subsystemsand so on. In the above example, there are no
sidearezero as a consequence of therow reductionandthatall unary reactionsbecausequartz is the only phasecomponent
coefficientsin the last two rows on the right hand side are that containsonly one systemcomponent. There are three
zero. The last two rows are thereforeequationsamongonly binary systems,SiO2-FeO, SiO2-MgO and FeO-MgO and
the phase components Fo, Fa, En, Fs and Qz. The thereis one possiblereactionin eachof the first two binary
significanceof the two equations systems(equations12 and 13). Finally, thereis one reaction
in the ternary$iO2-FeO-MgO system(equation11) for a total
Fs - En - 0.5(Fa - Fo) = 0 (11) of 3 uniquereactions.
and
Qz + Fo- 2En = 0 (12) Thermodynamic
Relations
is that any changesin the modal mineralogy or mineral The conditions of equilibrium in a multicomponent
chemistryof the assemblageolivine + pyroxene+ quartzcan heterogeneroussystemrequirethe uniformityof pressureand
be describedby thesetwo linearlyindependent reactions.The temperatureandthatfor everystoichiometric relationthatcan
first of thesereactionsis an exchangereactiondescribingthe be written among phase componentsof minerals in the
exchangeof Fe and Mg betweenolivine and pyroxene. The equilibrium assemblage,an equivalent expressioncan be
second is a net transfer reaction that describes the creation of written among the chemical potentials of those phase
pyroxene at the expense of olivine and quartz. If the components[Gibbs, 1906]. That is, for every stoichiometric
thermodynamics of thesetwo reactionsare known, then it is relation of the form
possibleto computechanges in modalmineralogyandmineral
chemistry with changesin pressure and temperatureor,
conversely,to infer changesin pressureandtemperature(a P-
0 = Zx)j,kOj,k (16)
the relation
T path) from measuredchangesin modal mineralogyand
mineralchemistry.
It shouldbe notedthat the abovealgorithmis a methodfor 0 = Yx)j,kgj,k (17)
findinga linearlyindependentsetof reactions
amongthephase
components.Otherreactionsamongthe phasecomponents also holds (see Table 1 for symbols). Equation(17) can be
that are linear combinationsof the independentset are also expandedusingtherelation
possible.For example,in theaboveassemblage thereaction
Qz + Fa - 2Fs = 0 (13)
[.tj,k= [.tj,k
+ RTlnaj,k (18)
to give
may be formedby a linearcombination of thetwo independent
reactions. Whereas only the linearly independentset of
reactionsis necessaryto computeP-T-X relationsin mineral 0 = Ag*+ RTlnKeq (19)
assemblages (and the choice of which reactions are
independentis completelyarbitrary), for the purposesof whichcanbe furtherexpandedto give
geothermobarometry it is advantageous
to examineall possible
reactions because some may be better constrained by 0= AH- TAS + RTlnKeq (20)
thermodynamic data and somemay have P-T slopesthat are
bettersuitedfor thermometryor barometry. In these
equations
Oi k isphase
component
j inphase
k, x)jk
The set of all possiblereactionsin an assemblage may be isthestoichiometric
coefficient
ofphase
component
Oj,k'n the
found by finding all linear combinationsof the independent
reactionsthat form unique reactions.In a systemof NC reaction,
gj,kisthechemical
potential
ofphasecomponentj in
systemcomponents a total of NC + 1 phasecomponents are phase
k,g*j,kisthestandard
statechemicalpotential
ofphase
necessary to form a reaction.In an assemblage with NP total component j in phase
k andaj,k is theactivity
of phase
phasecomponents, themaximumpossiblenumberof reactions component
j inphase
k relative
tothestandard
state
of g*j,k.
in the systemwith NC systemcomponentsis (from the AH* and AS* are the standardstateenthalpyand entropyof
combinatorialformula) reaction,
andKeqistheequilibrium
constant
defined
as
Spear:Petrologic
determination
of metamorphic
P-T-t paths
R = gasconstant
T = temperature
P = pressure
TR = referencetemperature
PR = referencepressure
t = firne
Truax= maximum T
Pmax= maximum P
NC = numberof systemcomponents
P = numberof phases
np = numberof phasecomponentsin a phase
NP = totalnumberof phasecomponents in anassemblage = Y.np
NRX = numberof linearlyindependentreactions
in an assemblage
Oj,k= phase component j inphase k
)j,k= stoichiometric coefficient
of phasecomponent j in phase
k
)g= stoichiometric coefficient
of gasphase
gj,k= chemical potential ofphase component j inphase k
aj,k= activityof phase component j inphasek
aj,k(s)= activityof solidphase
otj,k= sitemultiplicityof phasecomponent j in phasek
T1= activitycoefficientfor component1
fg= fugacity
of gasspecies
fig= fugacity
of gasspecies
at standard
state
Keq= equilibriumconstant
Vg= volumeof gasphase
AHm,ASm,AVm = enthalpy,entropyandvolumeof reactionm
AHm,ASm,= enthalpyandentropyof reactionm at the standardstate
AVs = volumechangeof solids
ACp= heatcapacitychangeof reaction
Xj,k= molefraction
of phase
component j inphase
k
mi = molesof systemcomponenti in the assemblage
Mk = molesof phasek in theassemblage
ni,j,k = moles
ofsystem
component
i inonemoleofphase
component
j inphase
k
WG, WH, WS, WV = Margulesparameters
for a binarysymmetricsolution
(zi= variance
of zithmeasurement
Pzi,zj= covariance
ofmeasurements
ziandzj
Tc = closuretemperature
0i = dependent
variablein differential
thermodynamic
analysis
zi = independent
variablein differentialthermodynamic
analysis
Keq= 1-I(aj,10vJ,
k (21) stateto the standardstate. The extrapolationof AH and AS
J from the reference conditions (TR,PR) to T and PR is
accomplished
byintegration
of theheatcapacity,
ACp:
For mostthermodynamic applications
enthalpy(H), entropy
(S) and volume (V) data are tabulatedat a referencestate AH(T,PR)
= AH(TR,PR)
+ IACpdT (22)
(commonly 1 bar and 298C) that is different from the
standardstate. Therefore,it is necessaryto extrapolatethe and
valuesof AH, AS andAg for thereactionsfrom thereference AS(T,PR)
= AS(TR,PR)
+I(ACp/T)dT (23)
Spear:Petrologicdetermination
of metamorphic
P-T-t paths 5
MassBalanceEquations
with
In additionto the abovethermodynamicrelations,thereare
alsomassbalanceconstraintsthat may be appliedto a system
Keq= II(aj,k(s))
j'k(fg)g (29) in heterogeneousequilibrium. Mass balance equationsare
essentialfor calculatingmodalabundances of phasesand for
Equationssuchas20 or 28 arefundamentalthermodynamic interpretingreactiontexturesin termsof pressure-temperature
relationshipsamong T, P and phase composition(Xj,k) changes.
sometimesknownas the law of massaction. In the integn/ted To be consistentwith the above descriptionof the phase
form,equation(28) canbeusedto computephaseequilibriaas equilibriaanalysis,
themassbalanceequations
taketheform
a functionof temperatureand pressureor, conversely,to
computeP andT frommeasured mineralcompositions asin miTM
Y.MkY.ni,j,kXj,k (34)
thermobarometry. k j
Thetotaldifferentialof equation(28) maybewrittenas
wheremi is themassof systemcomponent
i in therock,Mk is
themolesof phasek in theassemblage,
ni3k is themolesof
0= [RlnKeq-
(AS(TR,PR)
+I(ACp/T)dT)]
dT+AVsdP system
component
i in onemoleof phasi:'
component
j in
phase
k andXj k isthemolefractionofphase component
j in
+ RTdlnKeq (3O) phasek. The'firstsummation is overall k phases
in the
assemblage
and the secondsummationis over all j phase
or components
in eachphase.Equation(34) saysthatthemoles
6 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
of a systemcomponentin the rock are equalto the sumof the variance (F) of the systemof equationsthat describesthe
molesof eachphasein the assemblage timestheamountof that phaseequilibriaof the rock is computedas the numberof
systemcomponentin that phase. The total differential of variables(2 + NP) minusthenumberof equations (NP - NC +
equation(34) takestheform P) or
dmi= Y.Mk.ni,j,k
dXj,k
+ Y.(Y.ni,j,k
Xj,k)dMk (35) F = 2 + NC- P (41)
k j k j
whichis the Gibbsphaserule varianceof the assemblage.In
For theexampleof the assemblage
olivine+ pyroxene+ quartz the examplediscussedabove,NC = 3, P = 3 and the variance,
in the systemSiO2 - MgO- FeO discussedabove,the mass F=2.
balanceequationstaketheform The significanceof thisresultis thatin orderto calculatethe
phase equilibria of a systemthe values of a number of
msio2= MQz.1.1 + MOI(l'XFo,OI+ l'XFa,OI)+ intensivevariables(P, T, or X), the numberof whichis equal
to the phaserule variance,mustbe specifiedin orderto solve
Mpx(l'XEn,Px+ l'XFs,Px) (36) the equations.
If mass balanceequationsare also consideredthen the
mMgO= MQz.0.1+ MOI(2'XFo,OI
+ 0'XFa,Ol)
+ variablesin thesystemof equations
areP, T, Xi,k andMk of
which there are a total of 2 + NP + P. In addition to the
Mpx(l'XEn,Px+ 0'XFs,Px) (37) equationsdiscussedabove,there are also NC massbalance
constraints,one for each systemcomponent,for a total of
mFeO= MQz.0.1+ MOI(0'XFo,OI
+ 2'XFa,OI)+ NRX + P + NC = NP - NC + P + NC = NP + P equations.
The varianceof the systemof equationsthatis generatedfrom
Mpx(0'XEn,Px
+ l'XFs,Px) (38) considerationof both the thermodynamicand massbalance
constraints is
One way in which metamorphicP-T conditionscan be This result is known as Duhem's theorem, which states:
inferredis throughthe calculationof stablemineralequilibria
that are possiblein a particularsystem. Inferencesabout
metamorphic conditionsarethenmadethroughcomparison of Whatever the number of phases, of componentsor of
the computedphase equilibria with that observedin the chemical reactions, the equilibrium state of a closedsystem,
sample. for which we know the initial massesml...mc, is completely
Calculationof phaseequilibriainvolvessolutionof setsof determinedby 2 independent variables.
equations
thatdefinetheequilibrium
conditions
of thesystem.
Beforediscussingalgorithmsfor solution,it is first necessary PrigogineandDefay [ 1954]. The implicationof thisresultis
to examinethe degreesof freedompossessed by the mineral that calculationof phaseequilibriafor systemsin whichmass
assemblage. balanceequationsmay be appliedrequiresthe specification of
As developed above, the thermodynamicvariables of only two independent variables. The choice of which
interestareP, T andXj k for eachphasecomponent
in each variablesmay be chosenis arbitrary,but not all P, T, X, and
phase.In a system
,ith NC system
components
andP M variablesare independentin all assemblages.If thephase
phases,which can be describedby a total of NP phase rule varianceis 1, thenonly 1 intensivevariableis independent
components, therearea totalof 2 + NP variables(P, T andthe and the second variable chosen must be an extensive variable
mole fractionof each phasecomponentin eachphase).The (Mk). If the phaserule varianceis 2 or greaterthenany choice
numberof linearlyindependent reactionsthatcan be written of P, T, X or M shouldbe independent. For example,in a
amongtheNP phasecomponents is divariantassemblage specification of temperature
andpressure
will permitcalculation of mineralcompositions andmodesin a
NRX = NP- NC (2) systemfor whichthe bulk compositionis known.
It is of interestto note the relationshipbetweenDuhem's
for each of which a relation suchas equation(28) may be theoremand the metamorphicfaciesconcept. As definedby
written. In addition, for each phase the condition of Fyfe andTurner[ 1966]:
stoichiometrymustbe obeyed:
A metamorphicfacies is a set of metamorphicmineral
I = .Xj,k (39) assemblages, repeatedlyassociatedin spaceand time, such
J
that there is a constant and therefore predictable relation
the differential form of which is betweenmineral composition and chemicalcomposition.
Spear:Petrologicdetermination
of metamorphic
P-T-t paths ?
Activitymodels coefficients
maybefunctions
of temperature
andpressure
and
written as
One further consideration that must be addressed before
computationsof phase equilibria can proceed relates to WG = WH- T'VS+ PWv (49)
activity-composition
modelsfor phasesin the assemblage.
Whereasthe abovetheoreticaltreatmentis exact,an activity whereWH, WS and Wv are constants.The differentialof this
model, by definition, is not exact, but rather a type of expressionis
thermodynamicfudgefactorthatrelatesidealizedbehaviorto
therealbehaviorof materials.Thedefinitionof activityis otj,kRTdln
1= -2X2WGdX1- WG 2dT (5O)
T
aj = exp((gj- g*j,k)/RT) (43)
if W G is independent
of T andP (notethatonlyoneof thetwo
from whichit canbe seenthatthe activityis a functionof the
differencebetweentherealchemicalpotentialof a component
components is independentandthatdX2 = -dX1 in a binary
solution). If WG is a functionof P and T the total differential
in a phase(g) anda standardstatechemicalpotentialfor that
component(go). of RTlnycaneasilybe obtainedby differentiation
of equation
It is not the intentionof thesenotesto review all activity (49) with respectto P andT.
models that have been proposedto describe geological
materials. However, for the purposesof discussion,it is CalculationAlgorithms
useful to review severalof the most commonlyemployed
activitymodels. Calculation of metamorphicphase equilibria involves
Ideal solution models. Models for ideal solution behavior solvingthe appropriatesetof thermodynamic,
stoichiometric
are the mostcommonlyemployedin geologicalliteratureand and, if needed,massbalanceconstraints.As discussedabove,
are, in general,the simplestto use. Following Kerrick and the first item to consideris the varianceof the systemof
Darken[ 1975; seealsoWood andFraser,1977),the activity equations to be solved, because the variance dictates the
of an ideal ionic solution can be written as numberof variablesthat must be specifiedin order for a
solutionto be found. For example,if the assemblageis
univariant(F = 1) then only temperature,pressure,or the
aj,k= (Xj,k)aJ,k (44) compositionof onephaseneedbe specified;the valuesof all
othervariablesmay be computed.
whereetj,kis themultiplicityof thesiteoverwhichmixing Algorithmsfor the computationof phaseequilibria are
occurs.For example,the activityof the forsteritecomponent numerous.Ample discussionscan be found in Smith and
in olivine(Mg2SiO4)is Missen [1982; see also Wood, 1987, Ghiorso, 1985, Brown
and Skinner,1974]. A review of all availabletechniques is
aFo,Ol = (XMg,OI) 2 = (XFo,OI)2 (45) beyondthe scopeof thesenotes,but it is usefulto examinea
commonlyemployedalgorithmasanexample.
The mass balance (equations 34) and stoichiometric
where OFo,Ol = 2 if it is assumedthat Fe and Mg mix (equations
39) constraintsare linear but the thermodynamic
randomly over 2 equivalentsites. Note that in olivine the constraints(equations28) are non-linearin compositionand
relationshipXMg,OI = X Fo,OIis valid (eq. 45) because thereforemustbe solvedby iterativetechniques.A systematic
mixingoccurson nly onesite. Thisrelationis generallytrue procedurefor solving systemsof non-linear, differentiable
for singlesitecrystalsalthoughnot,in general,truefor multi- equationsis the Newton-Raphson technique.This procedure
sitecrystals.The activitymodelsusedin thesenotesare all of is a standardmathematicaltechniquefor finding the rootsof
the single site variety, so the mole fraction of the phase non-linearequationsby successively solvingfor the rootsof
component(e.g.XFo,O1)maybe usedinterchangeably with the systemof equationsformedby the derivativesof the non-
themolefraction of a cationona site(e.g.XMg,OI). linearequations.The rootsof theselinearequationsare then
The naturallog of thisactivitymodelis usedas a new approximationfor the non-linearequationsand
theprocessis repeateduntil convergence is achieved.
lnaj,k= cj,klnXj (46) The applicationof the Newton-Raphsontechniqueis as
follows. The function for which the roots are to be found is
anddifferentialof thenaturallog of thisactivitymodelis approximated
by a truncatedTaylor'sseriesexpansion:
oj,kRTln1
= WG(X2)
2 (48) A newvaluefor x (x) is thencomputed
as:
where the coefficient WG is a fit parameter [the so-called
Margules parameter; see Thompson, 1967]. These x1 = x+ Ax (53)
8 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
The procedure (equations 52, 53) is repeateduntilconvergence metamorphicproblems, largely because the necessary
is attained.For systems of simultaneous, non-linearequations thermodynamic data(AH, AS andAV as well as appropriate
Taylor'sseriesexpansions of the form: activitymodels)havebeeninadequate to producemeaningful
results. However, this situationis improving rapidly and
0 = f(xl,X2....Xn)+ Y.(}f/}xi)Axi (54) applicationsarelikely to becomecommonin thenearfuture.
i
Thermodynamic
Data Bases
may be writtenfor eachequation.Theseequationsare linear
in Ax andmay be solvedby standard matrixmethods. Calculationof phaseequilibriarequiresa thermodynamic
As an example,consideran assemblageinvolving only databaseandthevalueof theresultingcalculations is directly
solidphasesthatcanbe modeledasideal ionic solutions.The related to the accuracy of the data base. Several
Taylor's seriesexpansio_nfor the thermodynamicconstraint thermodynamic databaseshavebeenpublished in recentyears;
(equation28) takestheform: someof the morefrequentlycitedare thoseof Helgesonet al.
[1978], Robie et al. [1979], Berman et al. [1985; also see
Berman, 1988], Halbach and Chatterjee[1984] and Powell
0 = Ag+ RT'lnKeq'
+ RT'&!j,kjAXj + and Holland [1985]. It is not the goal of these notes to
x'j, evaluatetherelativemeritsof differentcompilations.Different
authorshave followed different strategiesfor deriving the
(RlnKeq'
- AS(TR,PR)
- l(acptr')dT)aT
+AVsAP (55) thermodynamicdata (e.g. linear programmingvs. least
squaresanalysis) and have utilized different data sets for
where
the
superscript
' onT,wit
andXindicates
that
these
quantitiesare to be evaluated the initial guessof T and
estimationof thermodynamic parameters(e.g. calorimetryvs.
phaseequilibria). Even when similar methodsand data sets
X . This equationcan be combinedwith the Taylor'sseries are utilized, the resulting thermodynamicdata may differ
expansionof the stoichiometric
constraints: becauseof differentweightingfactorsappliedto the dataor
differing philosophies on interpretation of experimental
0 = .Zaxj (56) results. At this point in time, the phrase "Let the buyer
J
beware" applies to potential users of thermodynamicdata
to yielda system
of equations
linearin AT, AP,andAXj with bases. The bestadvice is to compareresultsfrom different
a varianceequalto the thermodynamicvariance. Giv6n a set
of initial P, T and X conditions (P, T , and X), these
compilationsandto examinethoroughlytheconsequences of
usingonedata setversusanother.
equationscan be solved for AT, AP and AX which can be
Software that will run on personal computersfor the
addedto the initial P,T' andX' conditionsto providea new
set of conditions: calculationof phaseequilibriais alsoavailable.Two programs
designed to run on a personal computer are GE0-CALC
[Bermanet al. 1987], which hasprovisionsfor calculationof
p1= po+ AP (57) P-T, T-X(H20-CO2) and P-X(H20-CO2) diagrams, and
THERMOCALC [Powell and Holland, 1988]. As of this
T 1 = T + AT (58) writing,however,theseprogramsdo not haveprovisionsfor
and
solvingfor thecompositions of coexistingminerals,although
Xj,k1= Xj' + AXj,k (59) it is possible
to specifya fixedactivityof a phasein a reaction.
The processis repeateduntil convergence
is attained(AT, AP,
andAX-
J aresufficiently
small)
, Petrogenetic Grids
If mass balance equanons are also employed, then an
additionalsetof NC equationsof theform
A petrogeneticgrid showsthe relative stabilityof different
mineral assemblageswithin a given chemical systemor
subsystem. Numerous petrogenetic grids for various
0 = Y.M'k.nid,k Xj,k+ metamorphicsubsystems have beenpublishedand thesecan
k j
be of greatbenefitin estimatingmetamorphicconditionsfor a
YM*k .ni,j,k
AXj,k+ E (Y.ni,j,kX*j,k)AMk (60) particular mineralassemblage
significanceof metamorphic
or in theinterpretation
reactions.
of theP-T
k j k j
Anotherbenefitof a quantitativepetrogeneticgrid is thatit
provides a check on the internal consistency of the
(cf. equations34 and35) areaddedto the systemof equations thermodynamicdatabasefrom whichit was derived. Errors
wheredmi hasbeensetequalto zeroto satisfyconservation of in the data base may be revealed in the constructionof a
mass. This new set now has a variance of 2 with the variables petrogenetic grid because of constraints imposed by
AT, AP, AX, and AM and can be solved as describedabove if Schreinemakers' rules,whereaserrorsmay not be apparentin
the valuesof 2 variablesare specified. In this case,not only thecalculationof a singlereactioncurve.
the compositionsbut the moles (which can be convertedto Numerouspetrogenetic gridsfor metamorphicsystems have
modes)of phasesin therock are alsocomputed. beenpresentedin the literatureand it is not the intentionof
This type of Newton-Raphsonalgorithm has been used these notes to review all of these. Rather, some general
extensivelyin geochemicalmodelingroutinessuchas the considerations with respectto the useof petrogeneticgridsfor
EQ3/6 codeof Wolery [1979] [seealsoFrantzet al., 1981] the interpretationof metamorphicP-T conditionswill be
and to some degree in igneous petrology [Russell and discussedas well as some possible pitfalls that may be
Nicholls, 1985]. To date it has not been used to solve encountered in theseapplications.
Spear:Petrologic
determination
of metamorphic
P-T-tpaths 9
10 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
2O
18
16
Tc Ct
Bi C
14
LL!
rr
: 10
[Cd, AS, Tc]
LL!
8
q 0-7
o
350 450 550 650 750
TEMPERATURE C
Fig. 2. Petrogenetic
grid for pelitic schistsin the systemSiO2-A1203-FeO-MgO-K20-H20(KFMASH). Solid
graylinesareendmemberKFASH reactions;dashedgraylinesareendmemberKMASH reactions.Gray dots
areKFASH and KMASH invariantpoints. Solid blacklinesand blacksquaresare KFMASH reactionsand
invariantpoints. From SpearandCheney[1989].
An evaluation of which equilibria are best suited for constant.Startingwith the totalderivativeof the law of mass
thermometryand barometrycan be made by examiningthe action(equation28), thatis, equations 30 and31, the three
pressureand temperaturedependenceof the equilibrium relationscanreadilybe derived:
Spear:Petrologic
determination
of metamorphic
P-T-tpaths 11
a AI203 b c xy d e Si
st
Fe
7 BI70 MnO
FeO Ch MgO Ct Ch ct
Ga
(dP/dT)lnKeq
= (RlnKeq-
AS(TR.,.?.R)
AV
- IfACp/T)dT) dependenceand large AV is required for a large pressure
dependence.These relationsare illustratedgraphicallyin
Figure 5.
= (AH(T) + [ACpOT
+ AVs(P-lB
(65)
TAV Bibliography of Geothermobarometers
(dlnKeq/dT)p
= (RlnKeq-
AS(TR.,.P_RP
- [(ACp/T)dT) It is not the intentionof thesenotesto review critically all
RT calibrationsof metamorphicequilibria that have ever been
proposedas thermobarometers.However, as a service to
= (AH(TR.,__)
+IACpdT
+ AVs(P-
1)) (66) prospectiveusers,a shortbibliographyis presentedbelow.
RT2 The reader is also directed to Essene [1982] for additional
references.
There are two types of calibrationsin the literaturefor
(dlnKeq/dP)T
= AVs (67) thermobarometers. Experimental calibrationsarethosethatrely
RT on measurements of the equilibriumconstantasa functionof
temperatureand pressurein experimentsundercontrolled
Fromequation
(65),theslopeof anisopleth
of Keqis seento laboratoryconditions. Empiricalcalibrations arethosethatrely
be a function of the entropy and volume of a reaction. In on measurements of the equilibrium constantin naturally
general,equilibriawith a largeAS relativeto RlnKe.q
have occurringassemblages wherethetemperature andpressure of
steepslopesand equilibria with a large AV have shallow equilibrationis inferredfrom othermeans.In bothcasesthe
slopes. The pressureand temperaturedependenceof the equilibrium constantis regressedas a function of the
equilibriumconstantis equallyasimportantastheP-T slope temperature andpressure of equilibration,
fromwhichvalues
for preciseP-T determinations.As shownby equations(66) of AH, AS and in somecasesAV of reactionare derived (in
and (67) a large AH is required for a large temperature manyinstances
AV of reactionis calculated
fromtabulated
Spear:Petrologicdetermination
of metamorphic
P-T-t paths
A
A
K
Celad
T
Fig. 4. AFK diagramshowingschematicphaserelationsfor B
the assemblage chlorite(Chl) + chloritoid(Cld)+ muscovite
(Ms) + quartz. (Celad = celadonite). With increasing
dehydration this assemblage sweeps across the bulk
compositionlabeled with the X and results in chloritoid
appearing in therock. Thisreactioncausestheappearanceof a
new AFM phasein bulk compositionX but the reactiondoes
not appearon the KFMASH petrogeneticgrid of Figure 2,
which does not consider the tschermak(A1A1Mg_ISi_I)
substitution.
Spear:Petrologic
determination
of metamorphic
P-T-t paths 13
reactionsgenerallyhavea smallAV with moderateAS andAH It shouldbe notedthat many of the commentsmadeabove
sothattheKe isopleth
hasa relativelysteepslope. with respectto uncertaintiesin garnetsolutionmodelsalso
The equilrium constant for exchange reactions can apply to thermobarometersthat involve garnet discussed
generallybe simplifiedas a ratio of the exchangingcationsin below.
onephasedividedby the sameratioin the secondphase.This Garnet-Cordierite. Calibrations for the reaction
formulationis defined as the distributioncoefficient(KD). For
example,the distributioncoefficientfor the exchangeof Fe 2Fe3A12Si3012
+ 3Mg2A14Si5018=
and Mg between phases A and B is defined as KD =
(Fe/Mg)A/(Fe/Mg)B. The stoichiometriccoefficientsof the 2Mg3A12Si3012
+ 3Fe2A14Si5018 (69)
reaction(x)j,k)andthesitemultiplicities
((Xj,k)aretypically
combined and taken outside of the natural logarithm in have been presentedby Currie [1971], Hensen and Green
equation (28). Therefore, when discussingpressure and [1973], Thompson[1976], Holdaway and Lee [1977] and
temperaturedependenceof the partitioning of a pair of Perchukand Lavrent'eva[ 1981].
elementsbetweentwo phases,it is commonto refer to the Garnet-clinopyroxene.Calibrationsfor thereaction
distribution coefficient (KD) rather than the equilibrium
constant
forthereaction
(Keq),although
thelogsofthetwoare Fe3A12Si3012
+ 3CaMgSi206=
relatedby a constant.
Mg3A12Si3012+ 3CaFeSi206 (70)
Garnet-biotite. Geothermometers based on the reaction:
have been given by Raheim and Green [1974], Mori and
Fe3A12Si3012
+ KMg3A1Si3010(OH)2= Green [1978], Ellis and Green [1979], Saxena [1979],
Ganguly[1979], Dahl [1980], andPowell [1985].
Mg3A12Si3012+ KFe3A1Si3010(OH)2 (68) Garnet-hornblende. An empirical calibration for the
reaction
Spear:Petrologic
determination
of metamorphic
P-T-tpaths
Mg3A12Si302
.v3KFeA1Si400(OH)2
= with this problemby taking numerouselectronmicroprobe
analysesof a singlefeldspargrainwith a largebeamdiameter.
Fe3A12Si302+ 3KMgA1Si400(OH)2 (76) These analyseswere then averaged to give an integrated
composition for theoriginalfeldspar.With thistechnique
they
hasbeencalibratedasa geothermometerby KroghandRaheim computedplausiblemetamorphictemperaturesfor granulite
[1978], Green and Hellman [1982] and Hynes and Forest facies rocks of the Adirondack Mountains, New York.
[1988].This thermometeris mostapplicablein blueschist
and Muscovite-paragonite. A similar KNa_I solvus exists
eclogitefaciesrockswherethe phengitecomponent of the betweenthe micasmuscoviteandparagonite.This solvuswas
muscoviteis high. calibratedexperimentally
by Eugster,et al. [1972].
Garnet-ilmenite. The reaction
Net TransferEquilibria
Fe3A12Si302
+ 3MnTiO3= Mn3A12Si302
+ 3FeTiO3 (77)
Many net transferequilibriamake excellentgeobarometers
hasbeencalibratedexperimentallyas a geothermometer
by becausetheyhavereasonablylargevolumechanges.Several
have been calibrated.
Powncebyet al. [1987a,b].
Garnet-plagioclase geobarometers. One of the most
Solvus Thermometers commonlyusedgeobarometers in metamorphicrocksinvolves
the exchange of Ca between the anorthite componentof
Calibrationsof severalthermometershave beenpresented plagioclasefeldsparand the grossularcomponentof garnet.
that are based on the distribution of elements across a solvus. Anorthitehasa considerably
largervolumethandoesgrossular
In many instancesthe phrase"solvusthermometry"
is a on a per-atombasis,so that grossularis favoredat high P
whereas anorthite is favored at lower P. In order to use these
misnomerbecausethe term "solvus"is restrictedto phasesthat
are isostructural and several of the so-called "solvus equilibria it is necessaryto balance the reactionbetween
thermometers"actually involve two phasesthat are not anorthite and grossularwith additional phasecomponents.
isostructural.They shouldmorecorrectlybe referredto as Severalwaysof doingthishavebeenpresented.
exchangethermometers.However,theyareincludedunder Oneof the shortcomings of garnet-plagioclasebarometers
is
thisheadingbecause of generalusage. the estimationof activity-composition relationsin both the
Two pyroxene geothermometry. Two-pyroxene garnetandplagioclase.The substitution of Ca into garnetis
geothermometry is basedon the distribution
of Ca andMg demonstrablynon-ideal and different calibrations have
betweencoexistingclinopyroxene andorthopyroxene.
This different strategiesfor estimatingthe activity of grossular.
exchange is sometimesreferredto asthepyroxenesolvusbut Similarly,theactivityof anorthite
component in plagioclase
is
this is a misnomerbecausethe two phasesin questionhave alsonon-idealat metamorphictemperatures andactivitycor-
different structural states. rections for anorthite abound. Moreover, there are structural
Calibrations
of twopyroxenethermometershavebeengiven inversions
in theplagioclase
solidsolutionseriesandmostof
by DavidandBoyd[1966],WoodandBanno[1973],Warner the availablecalibrationsarerestrictedto intermediateplagio-
and Luth [1974], Ross and Heubner [1975], Saxena and clasecompositions (approximately An15- An60).
Nehru [1975], Saxena[1976], Nehru [1976], Lindsleyand Garnet-plagioclase-quartz-A12Si05 (GASP). Theequilib-
Dixon [1976], Wells [1977], Mori and Green [1978], rium
Sachtlebenand Seck [1981], Kretz [ 1982], Lindsley and
Anderson[1983], Nickel andBrey [1984], NickelandGreen 3CaA12Si208
= Ca3A12Si302
+2A12SIO5
+ SiO2 (78)
[1985], Nickel et al. [1985] and Davidsonand Lindsley
[1985]. The readeris referredto FinnertyandBoyd [1984, has been usedwidely as a geobarometer
in crustalrocks.
1986] and Carswelland Gibb [1987] for an evaluationof Numerous calibrations have been made of this barometer
some of these calibrations. includingGhent [1976], Ghentet al. [1979], Newtonand
Calcite-dolomite. The solvusbetweencalcite and dolomiteHaselton [1981], Hodgesand Spear [1982], Gangulyand
hasbeencalibratedasa thermometer by GoldsmithandHeard Saxena [1984], Hodges and Royden [1984], Powell and
[1961],GoldsmithandNewton[1969], AnovitzandEssene Holland [1988] and Koziol and Newton [1988]. Most of
[1982,1987]andPowellet al. [1984].Thecalibration of this thesecalibrationsgive resultsthat are consistent
with the
solvus isquiteprecise,
butapplications tohighgraderocksare A12SiO5 phasediagramof Holdaway[1971].
difficultbecauseof thepropensity of calciteanddolomiteto Garnet-plagioclase-muscovite-biotite. A secondway to
exsolveandreequilibrateuponcooling. balancea Ca net transferreactionbetweenplagioclaseand
Two-feldspar geothermometry. The compositions of garnetis with muscoviteand biotite. Two reactionsare
coexistingplagioclaseandalkalifeldsparhavebeencalibrated possible:
asa geothermometer
by Stormer[ 1975],WhitneyandStormer
[1977], Powell and Powell [1977a], Brown and Parsons Fe3A12Si3012
+ Ca3A12Si3012
+ KA13Si3010(OH)2
=
[1981, 1985], Ghiorso[1984], GreenandUdansky[1986],
and Fuhrmanand Lindsley[1988]. The last threeof these 3CaA12Si208
+ KFe3A1Si3010(OH)2 (79)
papersprovideexcellentdiscussions of the development,
applicability
andpitfallsof thevariouscalibrations. and
Application of thisthermometer is complicatedby thefact
thatalkalifeldsparscrystallized
at hightemperatureexsolveon
slow cooling. In order to use the thermometer,the Mg3A12Si3012
+ Ca3A12Si3012
+ KA13Si3010(OH)2
=
composition of thefeldspar presentat themetamorphic peak
must somehow be measured.Bohlen and Essene[1977] dealt 3CaA12Si208
+ KMg3A1Si3010(OH)2 (80)
Spear:Petrologicdetermination
of metamorphic
P-T-t paths 15
Fe3A12Si3012
+ 3A12Fe.lSi_l (in Ms) + 4SIO2 3CaMgSi206+ 3CaA12Si208=
= 4A12SIO5 (82) 2Ca3A12Si3012
+ Mg3A12Si3012
+ 3SIO2 (91)
KA13Si3010(OH)2+ Fe3A12Si3012 and
3Ca2Mg4A12Si7022(OH)2
+ 2Ca3A12Si3012
+ has been calibrated by Bohlen and Liotta [1986] as a
geobarometer.
Mg3A12Si3012+ 6SIO2 (86) Garnet-rutile-ilmenite-A12SiO5-quartz
(GRAIL). Bohlenet
al. [ 1983b] have calibrated the reaction
and
Fe3A12Si3012
+ 3TIO2 = 3FeTiO3+ A12SiO5+ 2SIO2 (94)
3Ca2FesSi8022(OH)2+ 6CaA12Si208=
as a geobarometer.
3Ca2Fe4A12Si7022(OH)2+ 2Ca3A12Si3012+ As discussed by Bohlen and Liotta [1986], linear
combinationsof reactions(93) and (94) with the equilibrium
Fe3A12Si3012+ 6SIO2 (87) 2ilmenite= ulvospinel+ ruffleresultin theadditionalequilibria
havebeencalibratedempiricallyby Kohn and Spear[1989 and Fe3A12Si3012+ 3FeTiO3 = 3Fe2TiO4+ A12SiO5+ 2SIO2 (95)
in preparation].Theseequilibriagiveresultsthatarein general
agreementwith othergamet-plagioclase geobarometers andare and
of considerable use in terranes where amphibolites are
abundantandpelitesscarce. Ca3A12Si3012+ 2Fe3A12Si3012+ 6FeTiO3 =
Garnet-plagioclase-olivine.Wood [ 1975] andBohlenet al.
[ 1983a,c] presentcalibrations
of theequilibrium 6Fe2TiO4+ 3CaA12Si208+ 3SIO2 (96)
16 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
3CaTiSiO5+ Fe3A12Si3012
= 4Fe304 + 02 = 6Fe203 (105)
3FeTiO3+ Ca3A12Si3012
+ SiO2 (98) and
6CaTiSiO5+ 4Fe3A12Si3012
= Fe2TiO4+ Fe203 = Fe304 + FeTiO3 (106)
6Fe2TiO4+ 3CaA12Si208
+ Ca3A12Si3012
+ 9SIO2 (99) The first of theseis a fluid-dependentnet transferequilibrium
Calibrations
for theseequilibriahavebeenpresented
by Ghent and the second is an Fe-Ti exchange reaction between
and Stout [ 1984; reaction97] and Esseneand Bohlen [ 1985; magnetite and ilmenite. The geothermometer/oxygen
reactions98 and99], buttheyhavenotbeentestedextensively barometerhas been calibratedby Buddingtonand Lindsley
in the field. [1964], Powell and Powell [1977b], and Spencer and
Garnet-cordierite-sillimanite-quartz. Calibrationsof the Lindsley[ 1981].
equilibria As equilibria (105) and (106) indicate, the magnetite-
ilmenite geothermometerdepends on T, P, and f(O2).
3Fe2A14Si5018
= 2Fe3A12Si3012
+ 4A12SIO5
+ 5SIO2 (100) However, the pressuredependenceis minimal and can be
ignored.This leavestwo equilibriaandtwo unknownsthatcan
and be solvedsimultaneously to obtainT andf(O2).
This geothermometer hasenjoyedconsiderablesuccess in
3Mg2A14Si5018
= 2Mg3A12Si3012
+ 4A12SIO5
+ 5SIO2 (101) igneouspetrology,but is difficult to apply in metamorphic
environments. In low grade parageneses(up to 500C)
havebeenmadeby Curfie [ 1971],HensenandGreen[ 1973], magnetitein metamorphic rocksis verynearlypureFe304and
Weisbrod[1973], Thompson[1976], Tracy et al. [1976], ilmenites are complicatedby the presenceof significant
Hensen [1977], Holdaway and Lee [1977], Newton and MnTiO3 component.High temperatureassemblages tendto
Wood [1979], MartignoleandSisi [1981],Lonker[1981]and exsolve and/or oxidize on cooling, leading to complex
Aranovich and Podlesskii[ 1983]. recrystallizationtextures.BohlenandEssene[1977]describe
Pyroxene-plagioclase-quartz.
Theequilibrium the useof microprobeintegrationtechniques similarto those
appliedto thealkalifeldspars to recoverthepeakmetamorphic
NaA1Si308= NaA1Si206+ SiO2 (102) conditions in granulite facies assemblagesfrom the
Adirondack Mountains, N.Y.
governsthe upper pressurestability of albite and is an
excellentgeobarometer.It is complicatedby order-disorder Application of Thermobarometry:
Procedures and Potential Pitfalls
phenomena in boththe feldsparandpyroxene,but generally
givesgoodresultsin blueschist andeclogitefaciesterranes.
Many calibrationsof thisreactionhavebeenmadeincluding Applicationof thermobarometers is quite simple. The
those of Johannes et al. [1971], Holland [1980] and compositions of coexisting mineralsare analyzed,generally
Hemingwayet al. [ 1981]. with theelectronmicroprobe, andthevalueof theequilibrium
The reaction constantcomputed usingtheappropriate activity-composition
model.Thentheequilibrium constantis insertedintoequation
CaA12Si208= CaA12SiO6
+ SiO2 (103) (28) anda line of constantKeqis drawnon a P-T diagram.
Usuallythisprocedure involvesnothingmoredifficultthan
hasbeencalibratedby GasparikandLindsley[ 1980]. pluggingnumbersinto an equationthat someone elsehas
Pyroxene-olivine-quartz. Recentcalibrationsfor the provided. Theinterpretation is thenmadethat,withinerror,
equilibrium therockequilibrated at conditionsalongthatisopleth.If a
second equilibriumis availablefromthesamerockor outcrop,
2FeSiO3= Fe2SiO4+ SiO2 (104) thenanisopleth
ofKeqcanbeplotted
forthatequilibrium.
The
intersection
of thetwoisoplethsprovidesa uniqueestimateof
includethoseby Bohlen et al. [1980] and Bohlenand pressureandtemperature.
Boettcher [ 1981]. Whereasthecalculation
of a pressure
or temperaturefroma
basedon thephengite published thermobarometeris straightforward,the
Phengitebarometry.Barometers
interpretation
contentof white mica have been presentedby Powell and of thesignificance
of theresultis not. There
Evans [1983], Massoneand Schreyer[1987], and Bucher-areseveralpitfallsthatmaybeencounteredandconsiderations
Nurminen [1987]. These barometersinvolve different thatmustbe madebeforea meaningfulinterpretation
maybe
made. These include
equilibria
amongthephases
muscovite
(phengite),
chlorite,
biotite,K-feldsparandquartzandsomearea functionof the (1) Evaluationof whetheror not mineral compositions
fugacityof H20 in theassemblage. represent
anequilibrium
coexistence;
Spear:Petrologic
determination
of metamorphic
P-T-t paths 17
18 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
A +Qtz
GaFr
7 iix,_
.-_
B2 , Biotite
Biotite
two minerals. For exampleFe-Mg exchangebetweengarnet over the entire grain. This can and shouldbe checkedon the
andbiotiteis def'medby thereaction microprobe. In order to obtain an accuratemeasureof the
peak metamorphictemperature,it is necessaryto obtain the
FeMg.] (garnet)= FeMg.](biotite) (68) compositionB 1 that was in equilibriumwith the core of the
garnet(G 1). If biotite crystalsare presentin the matrix away
With cooling,thisreactionproceeds to theleft renderinggarnet from the garnet rim, it is possiblethat the compositionsof
more Fe-rich and biotite more magnesian. The result is a thesereflectthecomposition of biotiteat themetamorphic peak
rotationof the tie-linesconnectinggarnetandbiotiteas shown as suggestedin Figure 6B. However, the consistencyof
on the AFM diagramin Figure6A. In the absenceof any matrix biotite compositions should be checked before a
otherreactions,the retrogradeFe-Mg ion exchangereaction temperatureis inferred. This is especiallyimportantbecause
betweengarnetandbiotitewill resultin a zoningpatternsuch biotite crystals in the matrix may be subjected to other
as seenin Figure6B. The profile is highly asymmetricand reequilibrationmechanismssuchaschloritization. Also note
onlyFe andMg arezoned.Ca andMn, whicharenotshown, thatthe greaterthe modalproportionof biotitein therock, the
are completelyunzoned.The mechanism thatproducesthe lessthebiotitecrystalswill changecompositionowingto mass
zoning is intracrystallinediffusion within the garnet in balance restrictions. Therefore, if the biotite touching the
responseto a changingboundaryconditionat the interface garnetrim is large and the diffusionprofile in the garnet is
with biotite. The boundaryconditionchangesbecausethe small, that biotite may be a suitablecandidatefor estimating
equilibrium KD for theFe-Mgexchange reaction(68)mustbe peakmetamorphictemperatures.How largeis "largeenough"
maintained at theinterface.Temperatures obtainedfrom"rim" dependson the magnitudeof the zoningin the garnetcrystal
analyseswill alwaysbe lowerthanpeaktemperatures when andmustbe evaluatedon a caseby casebasis.
retrogradeexchangereactionsare the only mechanismof Reequilibrationby net transfermechanism.In contrast,the
reequilibration. type of zoning patternsset up when retrogradenet transfer
Now turnto the questionof how to interpretgarnet-biotite reactions are operative are quite different, as are the
temperatures obtained fromanalyses of thegarnetandbiotite ramifications of this mechanismfor geothermometryand
crystalsin Figure6B. In general,if the compositions of geobarometry.To illustrate, considera rock consistingof
mineralgrainsthat are in mutualcontactare usedin the quartz + K-feldspar + biotite + garnet + sillimanite +
exchangethermometer(e.g. points B2 and G2), the plagioclasethatexperienced peakmetamorphic conditionsin
temperature obtainedwill be theclosuretemperature, which the granulitefacies at 780 C and 5 kbar. To simplify the
forgarnet-biotite is approximately 525-580C(seebelowfor a discussion,assumethat intracrystallinediffusioncompletely
moredetaileddiscussion of theclosuretemperature). If garnet eradicated any chemical zoning in the garnet at the
and biotitecompositions G1 (garnetcore) andB2 are used, metamorphic peak. The AFM diagramfor thisassemblage is
thena temperature higherthantheclosuretemperature will be shownin Figure7A (G 1 + B 1 + sillimanite).
obtained, but not necessarily the peak metamorphic The peakmetamorphic conditions wouldbe easyto compute
temperature. Notethatcompared to garnet,Fe-Mgdiffusion in from the garnet-biotite geothermometerand the garnet-
biotiteis rapid,thereforethebiotitecrystaladjacentto garnet plagioclase-A12SiO5-quartz geobarometer if the rock were
shouldbe unzonedand the composition B2 will be obtained quenched fromthesepeakconditions, buttheslowcoolingof
Spear:
Petrologic
determination
ofmetamorphic
P-T-tpaths 19
A
Sillimanite
A + Qtz
+ Kfs
Garnet G2/
B2\ B1
F M
Biotite
typical metamorphicterraneswill result in the operationof (68) and(107), the netresultis thatgarnetandbiotitebecome
continuousreactionsin a retrogradesense. Ignoring any more Fe-fich. The resultis a shift of the 3-phasetriangle
tschermakexchangesin the minerals,there are only four garnet-biotite-sillimanite
towardsmoreFe-richcompositions
independentcontinuousreactionsthat may operate in the asshownin Figure7A (G2 + B2 + sillimanite).The changes
assemblage quartz+ K-feldspar+ biotite+ garnet+ sillimanite in Fe/(Fe+Mg) resultingfrom thesereactionsare shownon an
+ plagioclasein the SiO2-Ai203-FeO-MgO-MnO-CaO-Na20- isoplethdiagramin Figure7B, wherethe XFe of garnetand
K20-H20 (MnNCKFMASH) system: biotitefromreactions(68) and(108) areplotted. (Notethatit
is not,in general,easyto predictthecompositional changeof
FeMg.1 (garnet)= FeMg_l (biotite) (68) mineralsin an assemblage followingan assumedP-T path.
The techniques of differentialthermodynamics,discussedin a
MnFe_l (garnet)= MnFe_l (biotite) (107) latersection,areideallysuitedfor theanalysisof thistypeof
problem.)
3CaA12Si208= Ca3A12Si3012+2A12SIO5+ SiO2 (78) Considerthe effectof theretrograde pathshownin Figure
7B. GametandbiotitebothbecomemoreFe-richresultingin a
Fe3A12Si3012+ KA1Si308 + H20 = shiftof the3-phaseAFM assemblage asshownby thedashed
lines in Figure 7A. Also, the garnet-biotitetie-lines will
A12SiO5+ KFe3A1Si3010(OH)2+ 2SIO2 (108) becomeshalloweras a resultof the exchangereaction(68).
Becausereaction (108) goes to the fight, garnet will be
Note that this last reactionrequiresthe additionof H20 to consumed by thisprocessat the sametime thecomposition
of
proceed. the gametin equilibriumwith theothermineralsof therock is
How theseequilibria behaveon retrogressiondependson changing.A compositiongradientis established betweenthe
the P-T path. For mosttypicalmetamorphicretrogradepaths rim of the garnetandthegarnetinterior,whichis modifiedby
that involve decompressionand cooling,reactions(68) and diffusionof components betweentheinteriorandtherim. The
(107) will move to the left, andreaction(108) will move to the resultis a diffusion-generatedzoningprofilethatmightappear
fight. Inasmuchas reaction(108) dominatesover reactions as in Figure 7C. Notice that if all four continuousreactions
20 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
2O
GARNET
t
Fe/Fe+Mg t
t
t
18 ,,
16
B
14
t
!
!
!
LU !
!
1o !
!
!
!
!
!
n- 8
i
!
!
0
350 450 550 650 750
TEMPERATURE C
Figure 7 continued
areoperative,thenzoningwill be observedin all elements(Fe, Consider now the problem of computing the peak
Mg, Mn and Ca). Also note that the zoning is more or less metamorphicconditions. It is desiredto recover the phase
symmetricabout the rim. Biotite has an Fe-Mg diffusion compositionsrepresentedby the solid trianglein Figure 7A.
coefficientthatis considerably
largerthangarnet,sobiotiteis The garnetis zonedfrom coi'eto rim as shownin Figure7C,
commonly unzoned even though garnet may be strongly and the only biotite compositionmeasuredin the rock is the
zoned. biotitein the matrix.Geothermometrybasedon the garnetrim
Spear:Petrologic
determination
of metamorphic
P-T-tpaths 21
Garnet
Figure 7. continued
andthe matrix biotite(pointsG2 andB2) will yield a closure that the rim compositionsof all minerals reflect the P-T
temperature,which is generallyon the order of 525-580 C conditionsof a single closuretemperature. It must first be
(seenext section). Geothermometry basedon the garnetcore documented througha carefulanalysisof thechemicalzoning
(point'G1) and the matrix biotite (point B2) will yield a that all equilibria did close at the sametime. For additional
temperaturegreaterthanthe thermalmaximum(notethat this discussion seeTracy et al. [ 1976],Tracy [1982] andRobinson
tie-line is steeperthan tie line.G1-B1 representativeof the et al. [1982].
thermalmaximum). There is no way to recoverthe peak T
unlessthe biotitecomposition at themetamorphic peakcanbe ClosureTemperatureand Therrnobarometry
recovered(point B 1 on Figure 7A). In somecasesa biotite
inclusion may be located that will give the desired Rockscoolfrom their maximumtemperature conditionsand
composition. The best hope is to searchfor a rock that as theydo, geothermometers and geobarometers may be reset
containsa lot of biotite and only a small amountof garnet. by the operationof continuousreactions. Eventuallythe
Mass balance will ensure that the biotite has changed temperaturebecomeslow enoughso thatreactionscease;the
composition very little from themetamorphic peak. temperature thatis recordedby a geothermometer thathasbeen
A similarproblemariseswith reaction(78). It is possibleto resetduringcoolingis, by definition,theclosuretemperature.
usethe garnetcorecomposition, but it is noteasyto saywhat Closuretemperaturefor an Fe-Mg exchangethermometer
plagioclaseto use. Plagioclasetypicallyis zoned,however,so suchas garnet-biotitecan be viewed as follows. Considera
it may be possible to reconstruct the peak plagioclase rock that contains a garnet-biotitepair that is undergoing
compositionby carefulanalysisof the zoning. retrogradeFe-Mg exchange.The startingpointwill be thepeak
In the above discussion all of the continuous reactions of metamorphism wherethe composition profileof the garnet
operatesimultaneouslyandreachtheirclosuretemperatures at is assumedto be flat. At the peak of metamorphismthe
exactly the sameP-T conditions. Therefore,equilibrium is biotite-garnetcompositionprofile lookslike curvetOin Figure
maintainedamong the rim compositionsof all the minerals 8A. On cooling,the surfaceconditionschangebecauseof the
throughout. However, in reality, different equilibria have temperaturedependenceof the equilibrium constant. A
different closure temperaturesdependingon the reaction diffusionprofile developsin the garnetand biotitebecauseof
kinetics and the relative diffusion rates within various thischangingboundaryconditionandit steepenswith time as
minerals. Moreover, if any fluid-dependentequilibria are shownin Figure 8A. BecauseFe-Mg diffusionwithin garnet
operativethenit is necessary for the fluid to first entertherock is somuchslowerthanwithinbiotite,theprofilewill be much
for retrogression to occur. It is very unlikelythatall equilibria moreapparentin garnetandmaynotbe measurable in biotite.
will closeat the sameT. The relativeclosuretemperatures of Consider now how the Fe-Mg KD between garnet and
metamorphic equilibriaareonly poorlyunderstood at present. biotitechanges.At the peak temperature,the KD recordedby
Differential closuretemperatures are also a problemwhen the garnetand biotite is that indicatedby TO. If the garnet
retrogradeP-T pathsare beingdeterminedfrom coexistingrim compositionprofile were flat thenit wouldnot matterwhere
compositions.It is simply not reasonableto assumea priori on the garnetthe analysiswas taken but once the diffusion
22 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
profile is set up, garnetcompositionand henceKD and the towardsthe core.The advantageof definingTc in thisway is
temperature recordeddependon thedistance fromtherim that that it is the temperatureactually measuredby microprobe
the analysisis taken. The closerto the rim, the lower the analysisand geothermometry.
temperature thatwill berecorded.For a pointa givendistance Dodson [1973] presenteda theoreticaltreatmentof the
from therim of the garnet,thechangein KD with temperature closure temperatureas applied to geochronology,and his
will divergefromtheequilibriumcurveandeventually become analysiscan alsobe appliedto petrologicsystems.Dodson's
asymptoticto some value (Figure 8B). The temperature [1973] equation
correspondingto this KD may be defined as the closure
temperature or Tc. Note thatdefinedthisway Tc is a precise E/R
temperature obtainedfrom theasymptote; however,Tc is also Tc = (109)
a functionof position.Tc is lowercloseto therim andhigher ARTc2D0/a
2
ln[ ]
E(dT/dt)
t3
A predictsthatclosuretemperature, Tc, shouldbe a functionof
t2
(1) theactivationenergy,E, for thethermallyactivated process
tl thatis therate limiting stepin thereequilibration(2) DO,the
diffusioncoefficientat infiniteT; (3) thecoolingrate,dT/dt (4) .
I Mg
Fe a geometricfactor, A (A = 8.7 for an infinite plane sheet
geometry)and(5) the diffusiondistance,a. Dodsonderived
to
a2
I I
al
his equationfor thediffusionof radioactivedaughterproducts
suchas argonout of hostcrystalsin orderthat the measured
Biotite Garnet age could be relatedto the age at a specifictemperatureof
closure. It is a model of a bulk diffusiveprocesswherea is
Distance
the sizeof the crystal. In geothermometry, the microprobeis
used to obtain the compositionat a point, rather than bulk
analysesas in geochronology.However the equationcan be
used to a first order if a is taken to be the distance from the rim
that the analysesare taken.
For the garnet-biotite system, the rate of Fe-Mg
intercrystallinediffusionis cona'olledby the intracrystalline
diffusionof Fe andMg in garnet,which is muchslowerthan
that in biotite. Valuesof DOandE for garnetFe-Mg exchange
havebeenestimatedby Lasagaet al. [1977] to be D0=0.0066
cm2/sec
andE = 285kj/mol.
With the abovevaluesfor DOandE appliedto equation1,Tc
as a function of cooling rate can be computedfor various
valuesof a (seeFigure8C). Microprobeanalysestakenon the
To Tc (a1) Tc(a2)
Fig. 8. (A) Schematiccompositionvs distanceplot for a
1/T garnet(right)- biotite(left) interface. Diffusivityof Fe-Mg
exchange is assumed infinitein biotiteanda functionof T in
garnet.tois time of initial,peakmetamorphic conditionsat
800
I I I I I which time garnetis homogeneous.tl, tl andt3 represent
C successive timesat lower temperatures. Diffusionprofilesat
successively lowertemperatures arecausedby theincrease in
700 Fe/Mg at therim of thegarnetbecause of theT dependence of
the Fe-Mg distributioncoefficient (KD)and the slower
diffusivityat lower temperatures.
(B) Plotof lnKD vs 1/T showingthe equilibriumdistribution
600 coefficientas a functionof T. TOis the temperatureat to (the
TcC peakmetamorphic temperature). Lightlinesshowthechange
in the garnet-biotiteFe-Mg distributioncoefficientwith
decreasing T at pointsal anda2in (A). Tc(al) andTc(a2)are
500
theclosuretemperatures for pointsal anda2.
(C) Plot of closure temperatureTc vs cooling rate for
distancesof 2, 5, 10 and 50 gm from the rim of the gamet
400 calculated using equation (109) from Dodson [1973]
1 1 10 100 1000
(assumingan infinite plane sheetA = 8.7). Note that the
closureT for a typicalgamet"rim"analysis(2-5 gm fromthe
CoolingRate (dT/dt) in C/Ma rim) is 525-580Cfor coolingratesof 10 - 100 C/Ma.
Spear:Petrologic
determination
of metamorphic
P-T-t paths 23
"rim" of garnet are in fact taken 2-5 gm from the rim, initial conditionsof a homogeneous crystalwith constantrim
depending on thesamplepreparation andthemicroprobe beam compositionfor all times t>t0. To apply this solutionto
diameter. For a distanceof 5 gm, Tc rangesfrom 525 to 580 diffusionalhomogenizatiov of garnet,a temperature-time
Cfor typicalmetamorphiccoolingratesof 10-100 C/Ma.It historymustbe specifiedand the diffusioncoefficientof the
is no coincidence thatsocahed"rim"analyses of garnet-biotite species of interestin garnetmustbeknown.Temperature-time
pairsrecordtemperatures of 525-600 C,evenfor highgrade historiesfor crustthickenedby continentalcollisionhavebeen
terranes.Another ramificationof Figure 8C is that it will be presentedby Thompsonand England [1984]. Figure 9A
very difficult to recoverpeak temperatures in smallgarnets [from Spear, 1988c] reproducesthese T-t plots and
especiallyin slowly cooledterranesbecauseof diffusional
reequilibration.This problemwill be addressed in moredetail
in the next section. On the other hand, garnet-biotite
geothermometryshouldexperienceno problemsassociated 1000
with closuretemperatures in thegreenschistandlow to middle
amphibolitefaciesin mm sizedgarnets. 900
It is very importantto keepin mindtheconceptof closure
temperatureas it applies to geothermobarometry.By
definition,all temperatures recordedby thermobarometers are 800
Diffusi.
onalHomogenization
of Garnet
lO Ol
Fig. 9. (A) Temperature-time
plotstakenandinterpolatedfrom
Thompsonand England[1984] for typical crustalresponse
followingthickeningby overthrusting. Nominalcoolingrates
for theseT-t pathsare 0 *C/Ma at the thermalmaximumand
reachmaximumvaluesof approximately
5 *C/Ma. Tmax
valuesfor the T-t curvesare A: 976, B: 901, C: 826, D: 749,
E: 686, F: 634, G: 585, H: 518 C.
(B) A plot of concentrationvs distance(in cm) for a 1 cm
radiusgarnet crystal for diffusionresultingfrom the T-t
historiesshownin Figure9A. Initial garnetcomposition is
homogeneous at C = 0. Rim compositionis constantat C = 1. 1
2tl Spear:Petrologicdetermination
of metamorphic
P-T-t paths
Spear:Petrologicdetermination
of metamorphic
P-T-t paths 25
consider the potential nonideality generated by these calculationsof closure temperature(see above) and the
components. author'sexperiencewith naturalsamples.Therefore,if no
It is worth noting with respect to the accuracy of zoninghalosare observedbut the temperature recordedis
thermobarometric calibrationsthat for many applicationsthe greaterthan 600 *C, the temperatureshouldbe treatedwith
accuracyis of secondaryimportanceto the precision.This is suspicionandotherpossiblesourcesof compositionalchange
particularlytruein thedetermination of metamorphicP-T paths examined,for examplebreakdownof biotiteto otherphases.
becauseit is thechangein P-T conditionsthatdefinesthepath, Another factor that should be kept in mind is the mass
not the absoluteconditions.If a singlesetof equilibriais used balancebetweenthe biotite inclusionand the hostgarnet,as
to infer the P-T path, thenthe path may be constrainedwithin discussed above. Large biotiteswill changecompositiononly
the precisionof the measurements. Of course,the absolute slightly and thus an analysisof a large biotite inclusionis
locationof thepathin P-T spacemay be uncertain,but,aswill likely to reflectaccuratelythe compositionof the biotiteat the
be discussedlater, this is of lesserimportancefor tectonic time of inclusion. Small biotites must changecomposition
interpretationsthanthe shapeof thepath. considerablyto maintainmassbalance.Hence,the measured
compositionof a small biotitewill not, in general,reflect the
Inferring a Metamorphic P-T Path compositionof the biotite at the time of inclusion. Justhow
large a crystalneedsto be beforethe measuredcomposition
GeneralConcepts reflectsthecompositionat thetime of inclusiondependson the
amount of diffusion that has occurredin the garnet, which
A metamorphic P-T path is the locus of pressure- dependson the startingtemperatureand the coolingrate. If
temperatureconditionsexperiencedby a rock from the zoning in a garnet host adjacentto a biotite inclusion is
beginningof itsmetamorphichistoryto whereit is exhumedat observed and change in the compositionof the biotite is
thesurface.Any informationcontained in therockthatcanbe suspected, thenthe amountof Fe andMg exchangedbetween
usedto infer the evolutionof the rock'shistorymay be usedto the garnetand biotite shouldbe estimatedby integratingthe
infer P-T paths. Clearly,if rockswereperfectlyequilibrated diffusion halo and mass balance calculations should be made
systems, thenno informationas to the pathfollowedby the to evaluatewhetheror not the biotitehassubstantially changed
rock would be available. It is the slow kinetics of composition.
metamorphic processes relativeto thedurationof thethermal Analysisof plagioclaseinclusionsin garnethostsis less
eventthat makesthe preservationand determination of P-T ambiguousin onerespectbecauseno exchangereactionsare
pathspossible. possiblebetweenplagioclaseand garnet;reactioncan only
The typesof informationusefulfor the determination of occurby net transferreactions,which can only occurif the
metamorphic P-T pathsare geothermobarometry on mineral inclusioncancommunicatewith otherphases.In addition,the
inclusionsuites,the analysisof chemicalzoningin minerals, diffusivityof NaSi(CaA1)_iin plagioclaseis sufficientlyslow
andthe studyof reactiontextures. at most crustal temperatures [Grove et al., 1984] that
significantdiffusionis not possible.This authorknowsof no
Thermobarometry on Inclusion Suites examplesof diffusionhalosof Ca in garnetaroundplagioclase
inclusionsthat can be attributedto diffusive processes.The
Thermobarometry on mineralinclusionsuitesis relatively major difficulty in interpretingplagioclaseinclusionsis (1)
straightforward andutilizestechniques discussed in the last demonstrating that they actually represent equilibrium
section.The basicprocedure is to useinclusions of minerals compositionsand (2) determiningthe assemblage that was
within other minerals to estimate the P-T conditions as the host presentin the rock at the time the plagioclasewas included.
mineralgrew. An excellentexampleis given by St-Onge The firstproblemcanbe addressed by examininga numberof
[1987], who used inclusionsof biotite and plagioclasein a plagioclase inclusions withinthegarnetcrystal.If systematic
garnethostto infer P-T pathsof severalsamplesfrom the partitioningof Ca betweengarnetandplagioclase is observed,
Wopmay Orogenin northernCanada. Temperatureswere thisis consistent with equilibriumhavingbeenattainedduring
estimated using the garnet-biotite Fe-Mg exchange garnetgrowth. Note thatthe P-T conditionsare likely to be
thermometerandpressures were estimatedusingthe garnet- changingas the garnetcrystalgrows,so that the appropriate
plagioclase-A12SiO5-quartz barometer. criterionis the systematic changeof partitioning, notconstant
Althoughstraightforwardin application,this procedure partitioning.The secondproblemis impossibleto evaluate
suffersfrom all of the samepitfalls as thermobarometry on unequivocally, unlessinclusionsof othermineralsare also
matrix mineral assemblages.For example,in the caseof presentwithin the garnet. However, using some of the
biotiteinclusions withingarnet,it is of paramount importance modelingtechniques to be discussed below,it is possibleto
to examinewhether or not biotite inclusionshave undergone testassumptions aboutthe assemblage presentas the garnet
exchange of Fe andMg with thehostgarnet.Thisis easyto grows.
checkwithdetailedmicroprobe traversesacrossthebiotiteand
into the hostgarnet. Zoningprofilesmay be very shortso Differential Thermodynamics' Theoretical
microprobe analyses with a spacingof approximately 0.002 Considerations
mm (2 gm) arenecessary.If no zoningis observed in either
thebiotiteor adjacent hostgarnet,thenit maybeassumed that TheP-T analysis of reactiontextures andmineralzoningis
thecompositions of thebiotiteandadjacent garnetreflectthe aidedby theformalismof differentialthermodynamics. The
equilibrium compositions at thetimeof entrapment andthe termdifferentialthermodynamics simplyrefersto utilizationof
garnet-biotite pair maybe usedfor thermometry.However, the differential forms of the thermodynamicexpressions
notethattypicalmetamorphic cooling of 5-100*C/Ma presented
histories above.The integrated formsof theequations are
will almost invariably generatediffusion halos around best suitedfor the calculationof absolutevaluesof pressure,
inclusionsof biotite within garnet,basedon theoretical temperature, mineralcomposition andmodes.Changesin
26 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
and
0=(RlnKeq
- (AS(TR,PR)
+I(ACp/T)dT))
dT+AVsdP Qz + Fo- 2En = 0 (12)
Spear:Petrologic
determination
of metamorphic
P-T-tpaths 27
0= (RlnKeq,
l! - (AS
!!(TR,PR)
+$(ACp,11/T)dT))dT + 0 + dMoI(2'XFo,OI+ 0'XFa,OI)
+ AVs,lldP+ + dMpx(l'XEn,Px+ 0'XFs,Px) (122)
0 = (RlnKeq,2
- (AS
12(TR,PR)
+I(ACp,12/T)dT))
dT + 0 + dMoi(0.XFo,O
1 + 2'XFa,OI)
+ AVs,12dP+ + dMpx(0'XEn,Px
+ 1-XFs.Px) (123)
or, in simplifiedform n TM
On(Zl,Z2
.....Zv) (126)
0=MQz-0 + MOI.0 + Mpx-0
(121)
Where zl, z2....Zv are the independent variablesand 1,
+ dMQz + dMol'1 + dMpx.1 02...Onarethedependent variables.The totaldifferentials
of
t31, t32....On can be written as:
dmMgO
=
0 = 0 + MOI(2.dXFo,OI+ 0'dXFa,Ol) dO1= (01/Zl)zi:l dzl + (01/Z2)zi:2
dz2...
28 Spear:Petrologicdetermination
of metamorphic
P-T-t paths
All AVs,ll RT - RT - RT RT 0 o o
XFs,Px XEn,Px XFa,O1 XFo,O1
dP
A12 AVs,12 0 -2RT 0 2RT 0 o o
XEn,Px XFo,O1 dXFs,Px
0 1 1 0 0 0 o o dXEn,
0 0 0 0 1 1 0 o o dXFa,O1
0 0 Mpx Mpx Mol Mo1 1 1 1 dXFo,01
o o o Mpx 0 2Mo1 o 2XFo,O1 XEn,Px
o o Mpx 0 2Mo1 o o 2XFa,OI XFs,Px dMo1
dMpx
dO2= ()02/)Zl)zi;q
dzl + ()02/)Z2)zi;2
dz2... (301/3Zl)zi:l, (301/3Z2)zi:2
....(301/3Zv)zi:v,etc.andby
multiplyingby finite changesin the independentvariables'
..+ (}02/}Zv)zi:v
dzv (128) AZl, Az2....AZv. Thus:
dO2= (302/3Zl)
(302/3z2)...
(302/3Zv)
dz2
, o
On=(3On/3Zl)z,_1
AZl+(3On/3Z2)zi;2
Az2
..+ (30n/3Zv)zi;v
AZv (132)
dn (On/OZl)
(OOn/i)z2)...
(i)n/i)Zv) d:v
or, in matrix form:
(129.1)
. .
Spear:Petrologic
determination
of metamorphic
P-T-tpaths 29
TABLE 3. System
of equations
for thetheassemblage
olivine+ pyroxene
+ quartzin thesystem
SiO2-FeO-MgO
modified fordT anddXFo,O
1asindependentvariables.
AVs,11 RT - RT - RT 0 0 0 dP -All - RT
XFs,Px XEn,Px XFa,OI XFo,OI
AVs,12 0 -2RT 0 0 0 0 dXFsJ'x -A12 -2RT
XEn,Px XFo,01
0 1 1 0 0 0 0 dXEn,Px o
o o o 1 o o o dXFa,Ol o -1
A11= RlnKeq,11
- AS1I(TR,PR)
- {(ACp
11/T)dT
A12= RlnKeq,
12 AS12(TR,PR) J(ACpi12)dT
30 Spear:Petrologic
determination
of metamorphic
P-T-t paths
matrix, A. This involves calculatingthe activity of each reference P-T-X-M conditions and a new set of P-T-X-M
component in eachphase
andthencomputing theAS,ACp,AV conditions is computed by multiplying the appropriate
andKeafor eachreaction. derivatives by AP. The size of AP is arbitrary, but for
matrixA andsolvefor partialderivatives adequate precision, values of 50-100 bars are usually
(5) Setipcoefficient
as described above[A"I(-B)]. appropriate.The equationsare thensolvedagainat thesenew
(6) Multiplythepartialderivatives valuesof P-T-X-M conditionsandtheprocesses
by theappropriate repeateduntiltheentire
the independentvariables (Azl, Az2...Azv) and compute contour is drawn. It should be noted that the same results
changes in thedependentvariablesA01, AO2...AOn. couldbe obtainedby choosingasindependent variablesT and
(7) Computenew valuesfor the dependent
variables01, X 1,A. In thiscasechangesin P arecomputed fromarbitrary
02...On andindependent variableszl, z2...Zv. valuesof AT. Typically,valuesof AT of 1-2 *C are required
(8) Repeatsteps(4) through(7) asneeded. to preservenumericalprecision.
Constructinga contouron a P-X or a T-X diagramis very
Differential Thermodynamics: Applica..tion.q similar. Again, assumethat the variance of the systemof
equationsis 2 andit is desiredto drawa line (contour)on a T-
Applicationsof the aboveprocedures are numerousas the X diagram showing the change in the mole fraction of
systemof equationsdescribedabove may be tailored to component1 with temperature.The T-X diagram is to be
addressmany different types of problemsencounteredin drawn at constant pressure. The independentvariables
metamorphic rocks.Examplesto be described belowinclude appropriatefor this problemare againP and X1,A andthe
the analysis of P-T-X phase equilibria in metamorphic equationsto be solvedareequations(141-143). In thiscase,
systems,the analysisof reactiontextures,reactionprogress however, the diagram is to be drawn at constantpressure,
and modal changesin mineral assemblages, whole rock hencedP = 0 andAP in equations(141-143) = 0. The change
metamorphic reactions and P-T paths from zoned in T andcompositions of all phasesare computedby solving
porphyroblasts. theseequationsat theinitial referenceconditions,multiplying
The choiceof variablesto be independentis arbitrary,the by AX1,A and computing new values of T, mineral
only stipulation being that the variables actually be compositionand mineral abundances.Equations(141-143)
independent. In general,the natureof the problemto be are solvedrepeatedlyat the new conditionsuntil the entire
solveddictatesthe choiceof variablesthat are independent,as contour is drawn. It should be noted that the same result could
will be discussed below. It is because the choice of variables is be obtainedby choosingas independentvariablesT and P.
arbitrarythatthesystem
of equations
is soflexibleandmaybe Thechange
in X1,AwithT at constant
P canthenbecomputed
appliedto somanydifferentproblems. for arbitraryvaluesof AT.
Examplesof the construction of P-T contourdiagramsare
P-T, T-X and P-X Diagrams given by Spear[1988b,d],Spearet al. [1982a], Spearand
Selverstone [ 1983],Spearet al. [in preparation]
andthereader
The first applicationto be discussed
is the construction
of is directedto thesepapersfor detaileddiscussion.In these
T-X, P-X and P-T contour (isopleth) diagrams. Diagrams paperstheGibbsmethod[Spearet al., 1982a],ratherthanthe
suchasthesecanbe very usefulfor the interpretation of both differential thermodynamicapproachoutlined above,was
progradeandretrograde mineralzoning. utilized, however, both formulations give numerically
The procedure for theconstruction of P-T isoplethdiagrams equivalent
results.A reviewof someof theseapplications
will
is asfollows. First,assumethatthe varianceof the systemof demonstrate
theutilityof suchdiagrams
in theinterpretation
of
equations is 2 andit is desiredto drawan isoplethof constant metamorphicprocesses.
molefractionof component1 in phaseA. The conditionfor Figure7B showsanexampleof a P-T diagramfromSpear
this isoplethis dX1,A = 0. The independent
variablesare andCheney[ 1989]contoured for garnetcomposition in garnet
chosen to be P andX1,A andthedependentvariablesareT, + biotitebearingassemblages in theSiO2- A1203- FeO- MgO
X2,A,X1,Betc. Thus: -K20- H20 (KFMASH) system. With progressive
metamorphism the assemblagechanges, so that several
T = F(P,X1,A) (138) differentdivariantfieldsare shown. At the lowesttemperature
displayedon thediagram,theassemblage is garnet+ chloritoid
X2,A= F(P,X1,A) (139) + biotite + muscovite+ quartz. Isoplethsof Fe/(Fe+Mg) in
garnetaresteepwith slightlynegativeslopeswith Fe/(Fe+Mg)
X 1,B= F(P,X1,A) (140) decreasingwith increasingtemperature.Similarly,isopleths
of Fe/(Fe+Mg) in theassemblage garnet+ biotite+ chlorite+
so that
muscovite+ quartzarealsosteep.At temperatures abovethe
reactionsgarnet+ chlorite= staurolite+ biotiteandchloritoid
AT = OTfOP)x
1,AAP+ 0T/0X1,A)P
AX1,A(141) = garnet + staurolite+ biotite the assemblagegarnet +
staurolite+ biotite+ muscovite+ quartzis stable. Isoplethsin
AX2,A= (/}X2,A//}P)x
1,AAP+ (}X2,A/}X
1,A)P
AX1,A(142) this divariant field have negative slopesand again show
Fe/(Fe+Mg) decreasingwith increasingT. At temperatures
AX1,B= (/}X1,B//}P)XI,A
AP+ (/}X1,B//}XI,A)P
AXI,A(143) above the breakdownof staurolitethe assemblagegarnet+
biotite + A12SiO5+ muscovite+ quartzis stable. Isopleths
Becausetheisoplethis to bedrawnat constant
X1 A (dX1,A= havenegativeslopesin thekyanitefield andarerelativelyflat
0)the
the value
ofAX1 A,is
compositions
of'i set
=phases
other0.Inthis
way
may chanes
inTand
becomputed
for
in the sillimanite and andalusite
any dependentreactionscan be written.Above the conditions
fields because no fluid
Spear:Petrologicdetermination
of metamorphic
P-T-t paths 31
nearlyverticalowingto the stronglydehydrating natureof this FeMn_l (garnet) = FeMn.1 (biotite) (07)
equilibriumwith temperature. Above the reactionbiotite +
A12SiO5 = garnet + cordieritc the assemblagegarnet + FeMn_l (garnet) = FeMn.1 (staurolite) (145)
cordieritc+ biotite showsisoplethswith negativeslopesthat
becomepositivewith decreasing P. Fe-staurolite+ annite+ quartz
A diagram such as Figure 7B is useful in severalways.
Firsfly, the diagram presentsa graphical portrayal of the = almandine+ muscovite+ H20 (146)
Fe/(Fe+Mg) to be expectedin garnet+ biotite assemblages
over rangesof P-T space.Garnetswith high Fe/(Fe+Mg) are almandine+ grossular+ muscovite= anorthite+ annite (79)
to be expectedat low temperatures at all pressuresandalsoat
hightemperatures at low pressures.
Secondly, the diagram can be used to infer how the For eachof thesereactionsan equationof the form of equation
Fe/(Fe+Mg) of garnet will change with progressive (112) may be written in addition to the stoichiometric
metamorphismfollowing different P-T paths. For example, constraints (equation 40) for the phases garnet, biotite,
isobaxicheating paths will result in garnets that become stauroliteandplagioclase.The totalnumberof equations is 10
increasingly depleted in Fe/(Fe+Mg) with increasing and the total numberof variablesis 14 (dT, dP, dXFe,Gar,
temperature,except in the sillimanite and andalusitefields dXMg,Gar,
dXMn,Gar,
dXCa,Gar,
dXFe,Bt,
dXM ,Bt,dXMnBt,
where the assemblageis garnet+ biotite + A12SiO5;in these dXFe,St,
dXMg,St,
dXMn,St,
dXAb,Pl,
dgAn,Pl).
';he
casesisoplethsare nearlyparallelto an isobaricheatingpathso varianceof this systemof equationsis thus4, consistent
with
little or no changein Fe/(Fe+Mg) is expected.For P-T paths thephaserule. The additionof massbalanceequationsof the
that involve decompression with heating (a so-called form of equation(113) for eachof the 9 systemcomponents
"clockwise" P-T path) garnet should become depleted in adds9 additionalequations and7 additionalvariables(dMGar,
Fe/(Fe+Mg) where the assemblageis garnet + biotite + dMBt,dMst,dMpl,dMgu, dMQz,dMH20)for a totalof 19
chloritoidand garnet+ biotite + chlorite,but in the P-T field equationin 21 variablesanda varianceof 2, as requiredby
wherethe assemblageis garnet+ biotite+ staurolitea heating Duhem's theorem.
with decompression pathis nearlyparallelto the isopleths,so The systemof 19 equationsin 21 unknownsconsistingof
little or no changein Fe/(Fe+Mg) would occurin the garnet thethermodynamic, stoichiometric andmassconstraintscanbe
composition.Indeed,if the path is one of nearly isothermal solvedfor the construction
of isoplethsof mineralcomposition
decompression in thefieldwheregarnet+ biotite+ staurolite is on a P-T diagram, as describedabove. To illustrate the
stable,the compositionof the garnetwouldbecomeenriched procedurewith a detailedexample,considerthecalculations
in Fe/(Fe+Mg) with progressivemetamorphism. However, necessary for theconstruction of an isoplethof XFe,Gar.The
this path would alsoresultin the consumption of garnet,as appropriatevariablesto chooseas independentare dP and
will be discussed later. Similar inferences can be made for dXFe,Gar
(seeequations
138-140),although
dT anddXFe,Gar
otherP-T pathswith otherassemblages. couldjust aseasilybe chosen.The equations
to be solvedin
Thirdly, it is possibleto infer in a qualitativeway the orderto computeanisoplethof XFe,Garare141-143.Table4
amountof garnetproduced(or consumed)for comparable lists the variables, their values at the initial (reference)
changesin pressureand temperaturein differentP-T fields conditions,
thevaluesof thederivatives
00/gP)XFe,Gar
and
with different assemblagespresent. The question of (O/XFe,Gar)P,
thevaluesof AO andthenewvaluesof 13
production andconsumption of phases will be addressedagain computedas Onew= 0old + AO. The procedure to calculate
below in a more rigorous fashion, but as a general isoplethinvolves:(1) ChoosingthereferenceP, T, X, andM
consideration,the more closely spacedthe isopleths for values (column 2, Table 4), (2) Choosingthe independent
Fe/(Fe+Mg), the largerthe amountof garnetthatis produced variables(P andXFe,Gar),
(3) Choosing
thevaluesof AP and
or consumedfor comparablechangesin P and T. Hence, AXFeGat (AP = 100bars,AXFe,Gar= 0), (4) Computing
the
considerablymore garnetis producedin assemblages that coei:icients
of the matrixof simultaneous
equations,
(5)
containgarnet+ biotite+ chloritoidand garnet+ biotite + Solvingequations 141-143for thederivatives
(columns 3 and
chloritethanin otherassemblages. This is importantto keep 4, Table4) usingtheinitialreferencevalues(column2, Table
in mind when tryingto infer the assemblage thatwas present 4), (6) calculatingthechanges in dependentvariables(column
asa portionof a garnetcrystalwasgrowing. 5, Table 4), (7) Calculating new values for P, T, X, M
As a secondexampleof a P-T diagramcontouredwith (column 6, Table 4), and (8) Using the new values of the
isopleths,thistimefromtheanalysisof a naturalpelite[Spear, variablesas referencevaluesandrepeating(4)-(7) until the
1988b],considerthe assemblage garnet+ biotite+ staurolite+ entire contour is drawn.
muscovite+ plagioclase+ quartz+ fluid in the systemSiO2- The results,takenfrom Spear[ 1988b],are shownin Figure
A1203- MgO - FeO - MnO - CaO - Na20- K20- H20 10. The startingmineralcompositions andmolarproportions
(MnNCKFMASH) system.Biotiteandstauroliteareassumed for thereferencemineralassemblage aregivenin Table4. The
to be ternaryFe-Mg-Mn solutions,garnetis assumed to be a dot on eachfigureshowsthereferenceP-T conditions for the
quarternary Fe-Mg-Mn-Casolutionandplagioclase is assumed assemblage. As canbe seenin thefigure,isoplethsof XFe,Gar
to be a binarysolutionbetweenalbiteandanorthite.All other (Fig. 10A) have negative slopes similar to those of
phasesareassumed to bepure. With theseassumptions, there Fe/(Fe+Mg)for the assemblage garnet+ biotite+ staurolite+
are four linearly independentexchangereactionsand two muscovite + quartzin theKFMASH system(Figure7B). One
independent nettransferreactions: major difference,however,is that the almandineisopleths
showa maximumasa consequence of therelativeP-T stability
FeMg.1 (garnet) = FeMg.1(biotite) (68) of theMn, Fe andMg endmember reactions
32 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
Spear:Petrologic
determination
of metamorphic
P-T-tpaths 33
10 10 X,o
8 8 XAn
Pt
o
16-___._._.
4 4 -0 24..... _
T Deg C T Deg C
I x Ix x ' ,, ',.,1 I 1
x\ xx x. 0',9 x [, e,o, -
\\ x x
6 \ '<xxxxx
-<....
400 500 600
",, ":
700
,', ,;/
T Deg C T Deg C
3q Spear:Petrologic
determination
of metamorphic
P-T-tpaths
z
x
Stau
Rxn B
I I
0.2 0.3
//%
-t3.3
1
Fig.11.Reaction
space contouredforP (dotted
lines)andT (dashedlines)forthesystemdepictedin Figs.10
andTable4. Solidlinedelimits
the"reactionpolygon",whichlimitstheaccessibleportion
of reactionspace
forthisassemblage.Reactions
A andB refertoreactions(146)and(79)in text,respectively.
modesin just thesameway thatP-T spacewascontoured with ace where the axes are defined by MB and MA is
mineralcomposition above. B/)MA)T.The isothermcanbedrawnby settingAT = 0
To contourreactionspacewith temperature,for example, andcomputingAMB corresponding to an arbitrarychangein
the appropriatevariablesto chooseas independentare T and M A using equation (152). Changes in P and mineral
MA, whereMA is the molesof thephaseusedto describeone compositionalong the isothermcan be computedusing
of the reactionspaceaxes. In the examplediscussedabove, equations(150) and (151) andthe entireisoplethconstructed
thiscouldbe stauroliteor plagioclase.MB will be takenasthe by iterative solutionof equations(150-152) with AT = 0. A
molesof the phaseusedto describethe otherreactionspace secondisothermcanbe constructed by solvingequations(150-
axis. Thus: 152) for the desiredchangein T with AMA = 0 and then
constructingthis new isotherm.For example,supposeit is
P = F(T,MA) (147) desiredto drawan isothermfor a temperature 100 Cdifferent
from the reference temperature.Equations(150-152) are
solvedwith AT = 100 C and AMA = 0 and new values of P,
X2,A = F(T,MA) (148) mineral composition and MB are computed. Note that
calculationof AMB at constantMA locatesthe new isothermin
MB = F(T,MA) (149) thereactionspacealongtheMB axis. Thesenew valuesof P,
so that T, X and M now serveas a new referencepoint and a new
isotherm can be constructed as was done before. Isobars can
be constructedin a similar fashionby substitutingP for T
AP= (OP/OT)MA
AT + (OP/OMA)T
AMA (150) above as can isoplethsof mineral compositionor mineral
abundance.
zXX2,A
= (0X2,Af0T)MA
AT + (0X2,A/)MA)
T zXM
A (151) P-T contoursare drawnon the reactionspaceof Figure 11.
Isobarsare nearlyvertical and isothermshave steeppositive
zSMB= (OMB/OT)MA
AT + (OMIdOMA)TAMA (152) slopes.Significant about this plot is the small degreeof
reactionthat occurswith fairly largechangesin P andT. For
The slope of an isotherm (defined as dT = 0) on a reaction instance,a changein the molesof plagioclasein the rock of
Spear:Petrologicdetermination
of metamorphic
P-T-t paths 35
10
T Deg C
approximately +0.03 implies a change in T and P of participatein reaction(79). Therefore,the traceof the reaction
approximately-200 Cand +3.5 kbar, respectively.This is a coordinatesfor reactions (146) and (79) must be along
consequence of the amountof garnetproducedor consumed mineral abundanceisoplethsfor plagioclaseand staurolite,
by changesin T andP by this assemblage as wasdiscussed in respectively. In other words,the P-T isoplethsdefinedby
referenceto Figure7B. dMpl = 0 and dMst = 0 are the reactionspacecoordinatesfor
The complementof contoursof P and T on reactionspace reactions(146) and (79), respectively. Along eachreaction
are contoursof mineral abundanceon P-T space. To contour space coordinate, the moles of all the minerals in the
P-T spacewith mineralabundance, the appropriate
variablesto assemblage change,whichcan be computedusingequations
chooseas independentare T andM or P andM. ChoosingT (150-152). The reactionpolygoncan be foundby locating
and MA (the moles of phase A in the assemblage)as andcontouringthe isoplethwherethe molesof a phasein the
independent variables,equations(150-152) may be solvedas assemblageis zero (i.e. MA = 0).
before for isoplethsof the abundanceof mineral A. The An example of a P-T diagram contoured for mineral
condition for an isopleth of mineral A is dMA= 0; hence abundanceis shown for the assemblagegarnet + biotite +
equations(150-152) can be solved setting AMA = 0 and staurolite+ muscovite+ plagioclase+ quartz+ H20 in Figure
computingthe changein P, mineral composition(AX) and 12. Each line shown representsan isopleth of mineral
molesof otherphases(AMB etc.) alongthe isopleth.A second abundancefor one of the 7 phases in the rock. Because
mineral abundanceisoplethfor mineral A may be found by staurolite,quartzand H20 are only involvedin reaction(146)
first solvingequations(150-152) with AT = 0 andAMA equal and not in reaction (79), isopleths of these phases are
to somedesiredincrementand thendrawinga contourfor this necessarily coincident. Isopleths for garnet, biotite and
new value of MA. Mineral abundanceisoplethsfor the other staurolite(quartz and H20) have negativeslopesthat are
phasesin the assemblagecan be constructedin the same subparallelto the endmemberKFASH reaction staurolite+
manner.
annite + quartz = almandine + muscovite + H20. The
Projectionof thereactionspaceontothe P-T diagramcanbe abundanceof garnetincreaseswith increasingT whereasthe
achievedby notingthateachlinearlyindependent reactioncan abundanceof biotite and staurolitedecrease. The isopleth
be describedby a phase that does not participate in the where the moles of stauroliteequals zero shouldbe noted.
reaction. In the examplediscussedabove, plagioclasedoes This is one faceof thereactionpolygonandindicateswherein
not participate in reaction (146) and staurolite does not P-T spacestaurolitewill reactout of the assemblage.
36 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
Figure 12 can be usedto infer P-T pathsfrom reaction staurolite+ muscovite+ plagioclase
+ quartzat thereference
texturesbecausedifferentP-T vectorswill producedistinct conditions
shownin Table4. Thederivatives (3X2,A/3P)T,
reaction stoichiometries, which should be reflected in the (3X2,AT)p,(3MA/3P)T,(3MA/3T)petc.areshownin Table5.
reactiontexture. An isobaricheatingpath will resultin the A P-T vectorof 30 bars/*Cgivesa reactionstoichiometry
of
productionof garnet,muscovite,H20 and small amountsof (normalized to 10molesof garnet)
plagioclaseand the consumptionof biotite, stauroliteand
quartz. An isothermaldecompression path will result in 1.79 St + 7.24 Bi + 1.10PI +14.34 Qz
consumption of garnet,muscovite
andH20 andproduction of
staurolite,biotite,quartzandplagioclase.Whereastheseare = 10.0 Gar + 7.24 Ms + 3.59 H20 (161)
qualitative statementsof the relative change in mineral
proportions,a methodis given in the next sectionto calculate In contrast,a decompression with heatingpathof-60 bars/*C
theexactreactionstoichiometry alonganyP-T vector. givesa reactionstoichiometry of
In summary,figures such as 10 and 12 combinedwith
carefulpetrographic analysisandchemicalanalysescan be 10.0Gar + 6.66Ms +2.65H20
very usefulin the interpretation of the paragenesisof a rock
becausethey showthe changesin mineralcomposition and = 1.33 St + 6.66 Bi + 4.72 P1+10.61 Qz (162)
abundance in P-T space.A detailedexamplewill bediscussed
in a later section.
withgarnetbeingconsumed alongtheP-T vector.
Whole Rock Reactions
Spear:Petrologic
determination
of metamorphic
P-T-tpaths 37
38 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
MnO Ky
A
F M
Bio
G3
/i i
G2 / i
G1
/ I
/ I
I
Spear:Petrologic
determination
of metamorphic
P-T-tpaths 39
1.0
I I I
B
Fe/(Fe+ Mg)'
0.8 --
t-
AIm
sPex
-
0.0
PYr,
N
I I I I
-z--
"'"
Pyr
' --'---Spies I
0.0 0.4 0.8 1.2
Distance (cm)
Fig. 13 continued
summarydiagram showingthe zoning trendsin each of the and pyrope increase whereas Fe/(Fe+Mg) decreases
threegarnetsis presentedin Figure13A. The rim composition monotonically. These calculations were all performed
of eachgarnetis indicatedby circlesasarethe compositions of assuming thefractionalcrystallization
of garnet;however,it is
coexisting staurolite, chlorite or biotite (labeled in this interestingto notethatthe samegeneraltrendsin composition
projectionas kyanite). The reversalin zoningtrendseenfor are generatedin an equilibriumcrystallizationmodel (i.e.
garnetsfrom bulk composition2 and 3 (G2 and G3) result where the garnetis homogeneous throughoutand the bulk
from the consumptionof garnet that occurs during the composition remainsconstant).Thisoccursbecause of theP-
reactions T-X behavior of the equilibria that control the mineral
compositions in the assemblage
garnet+ biotite+ chlorite+
garnet+ chlorite+ muscovite= muscovite + quartz. Of course, with equilibrium
crystallization,the garnetis unzonedso that thesetrends
staurolite+ biotite+ quartz+ H20 (168) would not be measured in the rock.
and An interestingpointemergesin Figure13B with respectto
theinterpretation
of garnetzoningprofiles.Thereactions
(168)
gamet+ chlorite+ muscovite= and (169) both have P-T-X behaviorsuchthat they resultin
the rim compositionof the garnetbecomingincreasingly
biotite+ kyanite+ H20 (169) enriched
in XSpsanddepleted
in Fe/Mgwithincreasing
T as
thesereactionsoperate.This canbe seenin Figure13A for
Figure13B showsthe chemicalzoningprofilesproducedin garnetsG2 andG3 wherethezoningtrendsreversedirection.
thegarnetfrombulk composition 2 (G2) asa functionof radial However, thesereactionsalsoconsumegarnetso that as the
distancein the garnet. This plot wasproducedby converting reactionsproceedthe core of the garnetis progressively
the molesof garnetproducedover the specifiedP-T path to exposed. In the absenceof diffusion, this resultsin a
volumeand thenplottingthe compositionas a functionof discontinuous stepin thezoningprofileobservedin thegarnet
radius assuminga spherical geometry. As can be seen, as shownin Figure13B neartherim. The curiousfeatureis
spessartine
showsa bellshaped
zoningprofiletypicalof those this: the phaseequilibria(Figure 13A) predictthat the rim
observedin low to mediumgradepelitic schists.Almandine composition of the garnetshouldbecomeenrichedin Mn as
140 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
5O I I I I I I I i i i I
BC2 c
Mus
Chl
Qtz
Qtz
Mus
Chl
Bio
Ky
Sta
Gar Gar
o
480 500 520 540 560 580 600
TC
Fig. 13 continued
staurolite+ chlorite+ muscovite+ quartz= (not shownin the figure)is capableof producingonly trivial
amountsof garnet. The implicationof thisobservation is that
kyanite+ biotite+ H20 (171) when a garnetin the assemblage garnet+ kyanite+ biotite+
stauroliteis beingexaminedit is mostprobablethatthebulk of
are encounteredat which point the proportionsof garnet, the garnetdid not grow in the assemblage thatis now present
muscoviteand chlorite decrease(chlorite ultimately falls to in the rock, but rather it is likely to have grown in the
zero)andkyaniteandbiotiteincrease.Staurolitefirst increases assemblagegarnet+ chlorite + biotite. This result is of the
in abundanceand then decreases. Finally, the continuous utmostimportancein the interpretationof P-T paths from
reaction chemicalzoningin garnet,aswill bediscussed below.
Spear:Petrologic
determination
of metamorphic
P-T-tpaths ql
/42 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
Spear:Petrologic
determination
of metamorphic
P-T-tpaths 43
garnet. The P-T conditionsof equilibrationof the rim of the processesmodifiedthegrowthzonation profileandwhateffect
garnet and the matrix of the rock were estimated to be doesthishaveonthecomputed P-T path?"Theanswerto this
approximately550 *C, 7 kbar. questionin detailis beyondourcurrentcapabilityto answer
The assemblage garnet+ hornblende+ staurolite+ kyanite and would require knowledgeof the diffusivities of all
+ biotite + chlorite + plagioclase+ quartz in the system independently variablespecies
in garnet.However,general
MnNCKFMASH is divarianttherebyrequiringthat only two inferencesmaybedrawnbyexamination of simplified
binary
variablesbe chosenas independent.Models were calculated diffusionin a sphereaswasdiscussed withrespectto Figure
withdifferentpairsof thevariables
dXA1
m,dXSvs,dXGrsand 9.
dXAn asindependentandthe resultswere found-tobe similar. Theamountof diffusional homogenizationtobeexpected in
For the purpose of this discussiononly the model using a garnetcrystaldepends on the temperature-time (T-t) path
dXA1m and dXGrs will be presented.The equationsto solve because thediffusivityis exponentially
relatedto 1/T. ForT-t
are therefore paths typical of the crustalresponseto thickeningby
overthrusting(Figure 9A), completehomogenization of
T = F(XAlm,XGrs) (182) garnetswith radiiof 1 cm will occuralongT-t pathsthathave
thermalmaximaof 775 Cor greater(T-t pathsA, B andC in
P = F (XAIm,XGrs) ( 183) Fig. 9B). Significantalterationof the zoningprofileis not
observedin T-t pathsthat havethermalmaximaof lessthan
X1,B= F(XAlm,XGrs) (184) approximately585 C (T-t pathsG and H in Fig. 9B).
However,note that evenfor T-t pathswith thermalmaxima
X2,B= F(XAlm,XGrs) (185) below 585 'C (e.g. G and H), a largepercentage of the
originalzoningprofileof the garnetmay be modifiedif the
etc .... and garnetis sufficiently
small. Forexample,asshownin Figure
9C, a garnetwitha radiusof 0.01cm(100gm)is completely
AT = (T/XAlm)XGrs
AXAlm homogenized alongT-t pathG. The reasonfor thisbehavior
is that the lengthscalefor diffusionalongany T-t path is
+ (}T/)XGrs)XA1
m ZSGrs (186) relativelyconstant,but a largerportionof smallgarnetsare
affectedfor anygivenlengthscaleof diffusion.
AP = (i}P/iXAlm)XGrs
AXAlm These considerationssuggestthat garnets of radii of
approximately1 mm or greaterthat havegrownalongP-T
+ (P/XGrs)XAlmGrs (187) pathsthathavethermalmaximaof lessthanapproximately 550
Cshouldpreserve therecordof theirP-T-X growthhistory.
(}X1,B/}XAlm)XGrs
AXAlm
A Worked Example' Fall Mountain,
+ (}X1,B/}XGrs)XAlm
Grs (188) New Hampshire, USA
AX2,B = ()X2,B/)XAlm)XGrs
AXAlm The rocksfrom Fall Mountain,New Hampshirewill serve
as an exampleof the applicationof thesetechniques.At Fall
+ (}X2,B/XGrs)XAIm
AXGrs (189) Mountain, two different structural levels, the Fall Mountain
nappeandthe Skitchewaugnappe,are exposedacrossa thrust
fault or decollement surface [Thompsonet al., 1968;
etc. ThompsonandRosenfeld,1979;Spearet al., in preparation].
Rocksof theupperplate(theFall Mountainnappe)consistof
Usingthe composition of mineralsandthermodynamic data high gradeschistsand gneisses that havebeenextensively
presentedby Selverstone et al. [1984]theP-T pathshownin retrogradedandrehydratedin the amphibolitefacies. Lower
Figure14Bwascalculated.Thiswasdoneby firstcomputing plate rocks show a completelydifferentparagenesiswith
the derivativesin equations186-189and multiplyingthese metamorphic conditions never exceeding the middle
derivativesby the first incrementof zoningmeasuredin the amphibolite facies.Thisdiscussion
will focusontheP-T paths
garnet (AXAlm and AXGrs) to obtain the changesin the inferredfor rocksof boththe upperandlowerplatesandthe
dependent variables associated with these changes in inferencesthatcanbe drawnfrom theseP-T pathsaboutthe
independent variables.A newpressure, temperature
andsetof tectonicevolutionof the nappecomplexin west-centralNew
mineral compositionswere then computedby adding these Hampshire.This discussion is basedon work by Spearand
changesto the old valuesand the processrepeateduntil the Chamberlain[1986], Spear [1988d] and Spear et al. [in
coreof the garnetwas reached. preparation].
The resultingP-T path(Fig. 14B) showsapproximately 3-4
kbarof decompression with minorheating(approximately 20 UpperPlate P-T Paths
C)from the coreto the rim. This path is consistentwith the
thermalbehaviorof tectonicallythickenedcrustasmodeledby Schistsfrom the upper plate at Fall Mountain (the Fall
thethermalcalculations of EnglandandRichardson[ 1977] and Mountain nappe) containlarge pseudomorphs (up to 4 cm
EnglandandThompson[ 1984]andwasthefirstverificationin long) of sillimaniteafter andalusite,which suggestthat the
naturalsamplesthatthesetypesof P-T pathswouldindeedbe early P-T pathpassedthroughthe andalusitefield. The peak
encountered in an orogenicbelt. metamorphicmineral assemblageis inferred to be garnet+
Diffusional reequilibrationof garnet. One questionthat biotite + sillimanite + quartz + plagioclase+ K-feldspar +
naturallyariseswith respectto the interpretationof growth rutile + ilmenite. Peak metamorphicconditionshave been
zonation in garnet is "To what extent have diffusional estimatedto be 700-750 C at pressuresof 3-4.5 kbar based
Spear:Petrologic
determination
of metamorphic
P-T-t paths
on garnet-biotitethermometryon garnetcoresand biotite garnetsare zonedin Fe, Mn, Ca and Mn (see Figure 15A)
inclusionswithin sillimaniteandwithinquartzcrystalsthatare with almandine,grossular andFe/(Fe+Mg)increasing towards
themselvesincluded in garnet, and garnet- plagioclase the rim, pyropedecreasingtowardsthe rim and spessartine
geobarometryon garnetcoresand plagioclaseinclusions increasinginitiallyandthendecreasingtowardstherim.
within garnet. Representative analysesof garnetand biotite Secondgeneration garnetsaresmall(0.2-0.5mm diameter),
from the peakmetamorphic mineralassemblage are givenin euhedral and occur in muscovite-rich reaction zones. As
Table 6. shownin Figure 15B thesegarnetsare zonedwith almandine
and Fe/(Fe+Mg) increasingand spessartineand pyrope
decreasingtowards the rim. Grossularcontent is nearly
constant.
TABLE 6. Representative garnetand
biotiteanalysesfor thepeakmetamorphic The chemicalzoningin theprimarygarnetsfromtheupper
assemblage garnet+ biotite+ sillimanite+ plate schistsis clearly not related to garnet growth, but to
K-feldspar+ quartz+ plagioclase(An;o) diffusionalprocesses thathaveoccurredduringretrogression.
Therefore, the techniqueof Spear and Selverstone[ 1983] is
not appropriatefor thesegarnets.However,constraints on the
Garnet Biotite
retrogradeP-T pathmay be obtainedby examinationof theP-
SiO2 37.21 34.11 T-X-M phaserelationsof the upper plate assemblages as
A1203 20.92 19.60 described abovethroughtheconstruction of contourdiagrams.
TiO2 nd 2.65 The assumptionthat is inherentin the use of contour(or
MgO 3.12 7.89 isopleth) diagrams for the interpretation of retrograde,
FeO 36.01 21.83
diffusioncontrolledzoningin garnetsis that the diffusionis
MnO 1.60 0.07
drivenby changesin the compositionof therim of thegarnet.
CaO 1.16 0.05
At leasttwo processes areactiveduringretrogression. Firstly,
Na20 nd 0.29 the P-T conditionsarechangingsothatthecomposition of the
Total 100.01 94.98
garnetin equilibriumwith the matrix mineral assemblage is
changingbecauseof the P-T-X behaviorof the equilibriathat
Cations are operativein the assemblage. If the mineral assemblage
12 Oxygens 22 Oxygens changesduring retrogression,then the equilibriachangebut
the rim conditionsof the garnet are assumedto be in local
Si 3.001 Si 5.260
equilibriumwith the matrix mineral assemblageat all times.
A1 1.989 Aliv 2.740 Secondly,retrogression may causeconsumption or production
Mg 0.375 of garnet,so the rim of the garnetmay be movingduringthe
Fe2+ 2.429 A1vi 0.824 retrogradeprocess(a moving boundaryproblem).If growth
Mn 0.109 Ti 0.307 occursthenthe zoningmay be locally a growthzonation,but
Ca 0.100 Mg 1.813 the relatively rapid diffusion rates at or near the peak
Fe2+ 2.816 metamorphicconditionswill ensurethat mostof the zonation
Mn 0.009 observedis diffusion,ratherthangrowth,controlled.The net
Sum Oct 5.769 result as the boundarycompositionat the rim of the garnet
changeswith time is that a diffusion profile is established
Prp 0.124 Ca 0.009 between the rim and the interior, initially homogeneous,
Aim 0.806 Na 0.088 crystal. By carefulexaminationof the zoningat therim of the
Sps 0.036 K 1.659 garnet,thechangein the garnetrim composition with timecan
Grs 0.033 Sum A 1.756 be inferred.Thischangein composition canbecompared with
theoreticalP-T-X-M isoplethdiagramsto constrainthe P-T
Fe paththatcouldproducesuchcompositional changes.
Fe+Mg 0.866 0.608 Isoplethdiagramsfor the peak metamorphicassemblage
garnet + biotite + sillimanite + K-feldspar + quartz +
plagioclaseare shownin Figure 16 [from Spear, 1988d].
Because K-feldspar is replaced during retrogressionby
Retrogradetexturesaboundin the upperplateschists.The muscovite,isoplethsare shownin both the K-feldsparand
porphyroblasticsillimaniteshave selvagesof fine grained muscovite fields. In the K-feldspar field isopleths of
muscovite+ staurolite;garnetporphyroblastshave resorbed almandine,spessartine andanorthitearesteepbuttheybecome
rims with muscovite, biotite, and locally staurolite and relativelyflat with slightlypositiveslopesin the muscovite
fibrolitic sillimanite in reaction zones; and late chlorite is field. Almandinedisplaysmaximain boththeK-feldsparand
abundant.Thesetexturessuggestextensivehydrationof these muscovitefields with valuesfalling off to eithersideof the
rocks at conditionsof the amphibolitefacies following the maxima. Spessartine increaseswith decreasingT in the K-
metamorphic peak. feldsparfield and decreasing P in the muscovitefield and
Two generations of garnetarepresentin theserocks. Large anorthiteshowsthe oppositebehavior.Grossularisopleths
garnetswith diametersup to 1 cm are interpretedasprimary havepositiveslopes withgrossular increasingwithdecreasing
garnetsthat were presentat the metamorphic peak. These T. Isopleths of mineralabundance areshownin Figure16D.
garnetsare generallyanhedraland displaycomplexreaction In thisdiagram, onlytheisopleth representingnochange in the
zonesaroundtheir margins.Primarygarnetsare unzonedin molesof the indicatedphaseis drawn (i.e. dMk = 0). This
theirinteriorsexceptin thevicinityof biotiteinclusions
where diagramdemonstrates thatwith decreasingT in theK-feldspar
theyarezonedin Fe andMg only. At theirmargins,primary field sillimanite,biotite,plagioclaseand quartzgrow at the
Spear:Petrologic
determination
of metamorphic
P-T-tpaths 45
0.5 1.0
i i 1 i
L i
A
Fe/(Fe + Mg)-
Fe/(Fe
+Mg)
,,
0.4 0.9
aim
alrn
_
0.8 +
.,
0.2
o.7 E
x
prp, sps
0.1 0.6
_
sps%....
0.0 grs
-
_
I 0.5
0.0 1.0 2.0 0.0 0.5
Core
mm Rim Coremm Rim
Fig. 15.Chemicalzoningprofilesin primary(A) andsecondary
(B) garnets
fromthegrayschistof theupper
plateof theFall Mountainnappe,west-central
New Hampshire.
FromSpear[1988d].
expenseof garnet,K-feldsparand H20. In the muscovite An additionalconstrainton the retrogradeP-T path for
field, however, an isobaric cooling path would resul in upper plate schistsmay be obtainedfrom analysisof the
growthof garnetandmuscoviteat the expenseof sillimanite, zoningobservedin the secondary garnets.The zoningin these
biotite,plagioclase andquartz. garnetsis interpretedasgrowthzoningbecauseof the euhedral
In order to utilize the isoplethdiagramsin Figure 16 to shapeof the garnets,the much shorterlength scale of the
constraintheretrogradeP-T pathsof the upperplateschiststhe zonationin thesegarnetsas comparedto the primarygarnets
change in the garnet rim compositionwith time must be and the fact that the muscovite-bearing assemblagein which
inferredfrom the zoningprofilespresentedin Figure 15. A thesegarnetsare found will produce,rather than consume,
detailedanalysisis presented in Spear[ 1988d]andSpearet al. garnetwith cooling(seeFigure 16D). With the assumption of
[in preparation],and the following conclusionsdrawn. The growthzonationthe methodof Spearand Selverstone[ 1983]
garnetwas unzonedat the metamorphicpeak and the initial can be used to infer the P-T history of these garnets. The
change in garnet rim compositioninvolved a decreasein assemblage presentduringgarnetgrowthwas assumedto be
almandine,an increasein spessartineand no changein the garnet + biotite + sillimanite + plagioclase+ muscovite+
grossularcontent. As shownin Figure 16C, the absenceof quartzwhich, in the MnNCKFMASH systemhas a variance
change in grossularconstrainsthe retrograde P-T path to of 4. Changesin thecomposition of plagioclasewereusedin
initially follow the zeroisoplethof grossular(pathA). Along additionto thezoningof almandine,spessartine andgrossular
this path in the K-feldspar field almandine decreases, as independentvariables. No plagioclaseinclusionswere
spessartine increasesand garnetis consumedas is consistent observedin thesecondary garnetsto helpconstrainthechange
with the observations. Following these initial changes, in plagioclase
composition,
but zoningof plagioclasein the
almandineand grossularincreasetowardsthe rim whereas matrix invariably showscoresmore anorthiticthan rims
spessartinedecreases. These changesare consistentwith suggestingthatplagioclase
becameincreasinglyalbiticwith
cooling paths in assemblageswhere K-feldspar has been garnetgrowth. This trendis alsoconsistent
with massbalance
replaced by muscovite. Two paths consistentwith these considerations
discussedabove.Becauseof the uncertaintyin
inferencesarethe low temperature continuationof pathA and AXAn, three different models were run with fiXAn = 0, +0.1
pathB shownin Figure16C. An additionalpointof reference and +0.2 from the rim to the core of the garnet. StartingP-T
for the upperplate schistsare the P-T conditionsrecordedby conditionsfor therim were takento be thosecomputedfor the
the matrix mineral assemblage,which are 430-510 C at 2 to matrixmineralassemblage (500 *C, 5 kbar).
6.5 kbar with a preferredvalue at approximately500 C, 5 The P-T path computedfor the model assumingthat AXAn
kbar. Therefore, the retrogradepath must intersectthese = +0.1 is shownin Figure 16C and labeled as path C. All
conditions. threecomputedpathsshowcoolingwith minordecompression
Spear:Petrologic
determination
of metamorphic
P-T-t paths
7 aimandyne
06
0,.. 0411,.
02
400 500 600 700 800 900 400 500 600 700 800 900
Ternp C Temp C
//anorthte /
_
06 -06
C 13.
Kfs Bt H20 / / \ J
_
+Kfs
04 HO 04
02
I 1 1
400 500 600 7OO 800 900 400 500 6C0 700 800 900
Temp oC Temp oC
Fig. 16. (A,B,C)Isoplethdiagramsfor the assemblage garnet+ biotite+ A12SiO5+ quartz+ K-feldsparor
muscovitein the systemMnNCKFMASH. Reference(peak metamorphic)conditionsindicatedby the dot;
compositionsof phasesat the referenceconditionsfrom Table 6. Box in (C) showspreferredretrogradeP-T
conditionsfrom the matrix. Arrows labeled A, B and C in (C) are three P-T paths discussedin the text.
Modified from Spear[1988d]. (D) P-T diagramwith isoplethsof zero changein the molesof the phases
garnet,biotite, sillimanite,quartz,H20, muscoviteand K-feldspar. Each isoplethdividesthe P-T diagram
into two regions,one where the phaseis producedand one where the phaseis consumed.From Spear
[1988d].
from the coreto the rim. The pathlabeledC is similarto path evidence in the lower plate assemblagesfor the high
B, which was inferred from the secondstageof retrograde temperaturemetamorphism observedin the upperplaterocks.
zoningobservedon the primarygarnets.Taken together,the Constraintson the P-T path of the lower plate rockshave
chemical zoning observedin upper plate garnetsis best been inferred by analysis of growth zonation in garnets
modeled by initial cooling from the metamorphic peak following the method of Spear and Selverstone[1983; see
followed by nearly isothermalcompressionwhich was then Spearet al., in preparation]. A zoningmap and traversesfor
followedby nearlyisobariccooling. one of the garnetsanalyzedin detail is shownin Figure 17.
Plagioclasein thesesamplesis irregularlyzoned with more
Lower Plate P-T Paths anorthiticcompositionsin the cores(An30-34)thanat the rims
(An20-24). The assemblageused to model the rim of this
Lower plate rocks at Fall Mountain display a distinctly samplewas garnet+ biotite+ chlorite+ quartz+ plagioclase+
differentparagenesis from upperplaterocks. Many locations muscovite,which is the assemblage in the matrix of the rock.
havepseudomorphs thatareinterpretedto be afterandalusite, Severaldifferent modelswere attemptedfor the coreof these
but thesepseudomorphs now consistof muscovitelocallywith garnets,but the preferredmodel was with the assemblage
late stagestaurolite,kyaniteandfibrolite. P-T conditionsof garnet + biotite + andalusite+ plagioclase+ muscovite+
equilibrationof thematrixmineralassemblages for lowerplate quartz. This assemblage is consistentwith the existenceof
rocksrangefrom 2.5 to 7 kbar and 470-560 Cwith higher andalusitepseudomorphs in the sampleand the fact that the
pressures derived from samples that display better- matrix chlorite is late stage.The variance of these mineral
equilibratedtextures.It is believedthatthe observedspreadin assemblagesin the MnNCKFMASH systemis 4 and the
P-T valuesreflectsthe variabledegreesof equilibrationof variables XA1m, XSps, XGrs andXAn were chosenas
samplesalong complex and varied P-T paths. There is no independent in themodeling.
Spear: Petrologicdetermination
of metamorphic
P-T-t paths q7
BF-86B
Fig.17.(A)Chemical
zoning
mapofagarnetfromthelower
plateoftheFallMountainnappe,west-central
NewHampshire.(B)Chemical
zoning
profile
ofgarnet
along
thetraverse
labeled
A in(A). FromSpear
etal.
[in preparation].
48 Spear:Petrologic
determination
of metamorphic
P-T-tpaths
0.5 1.0
BF-86B' Garnet 2 B
0.4 0.9
0.3 0.8
0.2 0.7
E
Prp
0.1 0.6
Sps
Grs
0.0 0.5
0 o.1 o.2
Core Rim
rnrn
Fig. 17 continued
The results of P-T path calculationson three traverses separatedin the field by the BellowsFalls pluton. The heat
throughgarnetcrystalsfrom this sampleare shownin Figure sourcefor the early high T, low P metamorphismis therefore
18. The P-T pathsall showa periodof nearlyisobaricheating most reasonablyassociatedwith the intrusionof this pluton.
in the corefollowedby nearlyisothermalcompression towards However, becausethe peak metamorphicconditionsof the
the rim. upperplaterocksare somuchhigherthanthe andalusite-zone
conditionsof the lower plate rocks(700-750 Cas compared
ThermalandTectonicInterpretation with 480-520 *C), it is requiredthatthe upperandlower plate
rocks were in different thermal regimes prior to their
The P-T paths computed for upper and lower plate juxtaposition.
assemblages may be usedto constraina thermo-tectonic model The P-T pathsfrom both the upperand lower plate rocks
for the evolutionof the nappecomplex. Pathsfrom boththe haveportionsthatdisplaynearlyisothermalcompression of 2-
upperplateandlowerplatesamplesindicateanearlyperiodof 3 kbar. This compressionis associatedwith a period of
high temperature,low pressuremetamorphism culminatingin thrusting(thenappestageof deformation)thatbroughtthetwo
andalusite-bearing assemblagesin the lower plate and platestogether.Note that the isothermalcompression inferred
sillimanite + K-feldspar bearing assemblagesin the upper for the upperplate rocksrequiresthat an additionalthrustlies
plate. Thesepathsare consistentwith early metamorphism in above the current erosion surfacein order to producethe
a contactmetamorphicenvironmentand in this regardit is crustal thickening responsible for the pressure change
significant to note that the upper and lower plate rocks are observed in these samples. The maximum pressure
Spear:Petrologic
determination
of metamorphic
P-T-t paths t9
Concluding Remarks
6
Traverse
2A,i
Rim
_
It is worthemphasizing thatnot all rock samplescollectedin
the field readily reveal the secretsof their P-T histories. In
Traverse
2B'"'% many samplesno amountof petrologicdetectivework will
resultin a satisfactoryanswer. The reasonssomesamplesare
so recalcitrantare many but may arise becauseeither the
geologichistoryis exceedinglycomplex,the sampleis of an
inappropriate bulk compositionto haveproducedmineralsthat
record events in their historiesor becauseof the quirks of
kinetic factors. In this author'sexperience,only 1-5% of the
samples collected and examined in thin section contain
adequateinformationfor the type of detailedpetrologicwork
2 I I i describedabove.This meansthat a minimum of 20 samples
should be collected in an area from which it is desired to infer
4OO 500 600
a P-T path.
TC Most of the applicationsof the methodspresentedabove
involve the metamorphismof pelitic schists. In many ways
pelitic schiststhat contain quartz + muscovite+ garnet +
plagioclase+ additionalFe-Mg silicatesare the simplestto
Fig. 18. P-T pathscomputedfrom zonedgarnetshownin understandand this is the reasonthey havereceivedso much
Figure17. FromSpearet al. [in preparation]. attention here. However, it is probable that more detailed
information will be forthcoming from more calcic bulk
compositions.The reasonis that in pelitesin which the only
calcicphasesare plagioclaseandgarnet,in orderfor garnetto
experienced
by the lower plate(P = 5-6 kbar)rocksimplies grow andpreserveits growthrecordin its zoningrecord(i.e.
thattheoverburdenimmediatelyfollowingthenappestagewas to fractionate), plagioclase must be consumed. As a
18 to 22 km. consequence, plagioclaseinclusionsare not overly common
The upper plate P-T path showsnearly isobariccooling within garnet crystals and there is a tendencyfor matrix
following the compression(nappe stage) event. This is plagioclase crystalsto recrystallize.Only very carefulwork
consistentwith the hot rocksof the upperplate havingbeen and a bit of luck enablesthe correlationof plagioclaseand
emplacedupon cooler rocks of the lower plate. The lower garnetzoningto be madewith certainty.However,in a rock
plateP-T pathlocally alsoshowsminorcoolingimmediately that contains additional calcic phases such as epidote,
following the thickening(nappe stage)event (see Fig. 18). margarite,calcite,or calcicamphibole, plagioclaseandgarnet
This implies that the lower plate was itself emplacedon yet maygrowsimultaneously thusincreasing thelikelihoodthat
cooler rocks and as a result experiencedcooling following the zoningrecordof both phaseswill be preserved.The
emplacement. drawbackto usingcalcicrockscontaining thesephasesis that
A tectoniccartoonillustrating thesefeaturesis shownin thesolutionproperties
arenotat all well understood,especially
Figure19. Prior to nappeemplacement the upperandlower for phasessuchas amphibole,and the phaserelationsare
platerockswerelocatedin a basinto theeastof theirpresent considerablymore complexand thereforeless tractable.
location. Intrusion of the Bellows Falls pluton (BFP) However,thesetwo problemsshouldberectifiedin thefuture
immediatelybeforeor duringthrustingheatedthe rocksof astheneedto usethesetypesof rocksbecomes increasingly
bothplatesto differenttemperatures because of theirdifferent apparent.
ambientconditions. The depthof the lower and upperplate Finally, it should be reiterated that the pursuit of
samplesprior to thrusting,basedon the thermobarometric metamorphic P-T pathshasopenedan entirenew vistafor
constraints,
wasapproximately 10 km. Thrusting(1) loaded metamorphic petrology.No longercanmetamorphic mineral
rocksof theupperplate,(2) juxtaposedrocksof thelowerand assemblagesbe cubbyholed as natural examples of
upperplates,and(3) emplacedtheentirepackageuponcooler heterogeneous systems in equilibrium. Indeed, the
rocks to the west. The overburden thickness immediately fundamental objectiveof metamorphicpetrologyhasshiftedin
followingthrustingwas on the orderof 20 km. Additional recentyearsfromtheanalysis of metamorphicphaseequilibria
details of this model are discussedin Spear et al. [in for its own saketo the studyof metamorphicrocksascluesto
preparation]. the tectonicand thermal evolutionof the lithosphere. This
The aboveexampleillustratesthetypesof informationthat endeavorbrings the fields of metamorphicpetrology,
may be derived from detailedpetrologicanalysisand the structural
geology,geochronology andgeodynamics closely
constraintson the thermaland tectonicevolutionthat may be togetheranduniteseffortsin thesedisciplines
intoa single
obtained from such data. Of particular use for tectonic goal. Greatstrideshavebeenmadein therecentpastandit is
reconstructions are the estimates of crustal overburden that the predictionof this authorthatthe nextdecadewill see
follow from the inferredchangesin pressure.Moreover,when tremendous newinsightsintothebehaviorof thecrustduring
combined with inferences from thermal modeling to be orogenesis.
50 Spear:Petrologic
determination
of metamorphic
P-T-t paths
LP 5
BFP
P
l0
15
l0
P 15
,BFP
2O
25
3O
w E
Fig. 19. Cartoonshowingthetectonicevolutionof theFall Mountainnappe.(A) Conditionsimmediatelyprior
to thrusting.(B) Conditionsimmediatelyfollowing thrusting.LP - lower plate sample,UP - upperplate
sample,BFP = BellowsFallspluton. From Spearet al. [in preparation].
Acknowledgments References
The author would like to acknowledgethe careful and Anovitz, L. M. and E. J. Essene, Phase relations in the
thoughtfulreviews by J. Cheney,R. Haugerud,F. Florence, system CaCO3-MgCO3-FeCO3. Eos Trans. AGU, 63.
M. Kohn, T. Menard and S. Peacock. Discussions with J. 464, 1982.
Cheneyover the yearshavecontributedgreatlyto the content Anovitz, L. M. and E. J. Essene, Phaseequilibria in the
of these notes. N. Rivers is thanked for her assistance in systemCaCO3-MgCO3-FeCO3. J. Petrol.,28, 389-414,
preparationof the manuscript. This work was partially 1987.
supportedby National Science Foundation grant EAR- Aranovich, L. Ya. and K.K. Podlesskii, The cordierite -
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and
Spear:Petrologicdetermination
of metamorphic
P-T-t paths
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internallyconsistent
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Report, 377, 62 pp., 1985. Mg distributionsbetweencoexistinggarnetand pyroxene:
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CALC: Softwarefor calculationanddisplayof P-T-X phase 866, 1980.
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Simon M. Peacock
Abstract
principles.In metamorphicpetrology,the forwardapproach
combinesthe basic equationsof heat transfertheory with
Numerical models of heat transferduring metamorphism modelsof platetectonicsandmetamorphic reactionsin orderto
permit constructionof theoretical metamorphicpressure- simulatemetamorphicevents. Forwardmodelingprovides
temperature-timepaths. Numerical modelsplace important insightintotheimportantvariablesthatcontrolmetamorphism.
constraintson metamorphicprocesses,particularlyregarding In particular, forward modeling provides information
the time scales involved in metamorphic events. In this regardingthe time scale(duration)of metamorphic eventsthat
contribution,numericalfinite differenceapproximationsare is verydifficultto extractusingradiometric datingtechniques.
developed for the time-dependentheat transfer equation. The combination of both forward and inverse methods
Explicit, implicit, and Crank-Nicolson finite difference resultsin a much greaterunderstanding of metamorphism.
approximations to partialdifferentialequationsaredeveloped. Field andlaboratorystudiesof metamorphicrocksprovidethe
The finite differencemethodis appliedto examplesof regional necessaryconstraintsneededto constructforward models. In
and contact metamorphism in order to illustrate the return, forward modelsplace constraintson the important
fundamental principles involved in constructing finite processesthat control metamorphism. The two methods
difference models in general, and metamorphicpressure- complementeach other; feedbackbetweenthe two methods
temperature-time paths of interest here. In addition, this has substantially advanced our understanding of
contributioncontains a summary of the scientific literature metamorphismandtectonics.
pertaining to numerical and analytical models of regional, Recently, the Mineralogical Association of Canada
contact,and subductionzonemetamorphism. (M.A.C.) held a shortcourseon 'Heat, Metamorphismand
Tectonics'[Nisbet and Fowler, 1988]. Many of the topics
discussed in these short course notes are also covered in the
M.A.C. notes, althoughour emphasisand treatmentdiffer
Introduction from theirs. The two sets of short course notes document the
mostrecentforwardandinversemodelingtechniquesusedto
"Metamorphictemperatureandpressureconditionsrecord deteminemetamorphic pressure-temperature-time
paths.
transientthermalconditions perturbedby tectonics..." The mineral assemblage of a metamorphicrock generally
reflectsthe maximumtemperature thattherockwassubjected
EnglandandBickle [1984] to duringthe metamorphicevent. The heatrequiredto raise
the temperatureof a rock duringmetamorphismcomesfrom
three general mechanisms: (1) conduction of heat down
Metamorphic petrology has traditionally been concerned thermal gradients (heat flows from hot rocks to cold rocks;
with the extraction of information, such as pressureand e.g., heatflows from the hot mantleinto the baseof the cooler
temperature,from metamorphicrocks. As we haveseenin the crust); (2) advectionof heat(e.g., hot fluids movingthrough
first part of this short course,petrologistshave developed therock); and (3) internalheatsources(e.g.,radioactiveheat
increasinglysophisticatedgeothermobarometric techniques production).
suchthat we can now extractportionsof pressure-temperature Thermal gradientsin the crust vary through time. Plate
paths by analyzing zoned minerals from rocks containing tectonicprocessesalterthe thermalstructureof the continental
suitable mineral assemblages. The Gibbs method, crustat convergentplate margins. Pairedmetamorphicbelts
geothermometry,and geobarometryare examplesof inverse [Miyashiro, 1961; Zwart, 1967] resultfrom dramaticchanges
techniques.Much geologicresearchis concerned with inverse in the thermal structureof continentalmarginsinducedby
techniquesby which we attemptto "read"the rock recordin tectonics. In this setting,oceanicrocksare rapidly buriedin
order to understand how the rocks formed. the subduction zone and undergo high-pressure/low-
More recently,forward techniques havebeendevelopedthat temperature metamorphism. In the magmatic arc, the
attempt to model geologic processesusing a set of basic emplacementof abundantplutonic bodiesat shallowcrustal
57
58
58 MODELING OF METAMORPHIC
TIIERMAL MODELING
THERMAL METAMORPIUC P-T-t
P-T-t PATHS
PATHS
levels results
levels results in
in low-pressure/high-temperature
low-pressure/high-temperature meta- meta
morphism.
morphism.
burial and
The burial and uplift
uplift history
history of
of a rock
rock profoundly
profoundly affects
affeets the
the
A
pressure-temperature-time path
pressure-temperature-time path followed
followed byby aa metamorphic
metamorphic
"
rock. Rocks
rock. Rocks are
are poor
poor conductors
conductors ofof heat;
heat; they
they heat
heat up
up and
and "- .
-- 200C
200C ',,1-
(C)
'HRUST
cool down
down slowly.
slowly. Rates ofof burial
burial and
and uplift
uplift may
may be be 20 km
---
MANTLE
MANTLE
processes, such
processes, such as
as in a subduction
subduction zone
zone or beneath thrust
beneatha thrust
nappe, or
nappe, or by
by sedimentary
sedimentary processes.
processes. Similarly, rocks may
Similarly,rocks may bebe
uplifted by
uplifted by tectonic
tectonic processes,
processes, such
such as
as along
along low-angle
low-angle normal
normal
faults, or
faults, or by
by erosion
erosion of
of the
the overlying
overlying crust.
crust.
Oxburgh and
Oxburgh and Turcotte
Turcotte [1974]
[1974] used
used the
the Peclet
Peelet number
number toto
demonstrate that
demonstrate that thrusting can cause
thrustingcan cause a
a major
major perturbation
perturbation of
of
the steady-state
the steady-state geotherm.
geotherm. The Peclet
The Peelet number
number is is aa
dimensionless ratio
dimensionless ratio between the rate
betweenthe rate of
of advective
adveetive heat
heat transport
transport
(e.g., heat
(e.g., heat emplacement
emplacement during
during thrusting)
thrusting) and the rate
andthe rate of
of heat
heat
conduction. The
conduction. The Peclet
Peelet number
number (Pe
(pe #) is defined
#) is defined as:
as:
vL
vL
Pel
=
Pe# =
lC (1)
(1)
JST
where v
where v== velocity of heat emplacement [mls],
velocityof heatemplacement [m/s], MANTLE
L characteristic length
lengthscale [m], and
=
seconds), calculated
Peelet
Peclet number
numberis is approximately
approximately10. 10. The The thrust
thrustsheet sheetis is The
The absolute
absolutetemperatures
temperatures in
in stable crust are
stablecrust primarily a
are primarily a
emplaced
emplacedrapidly
rapidlyas as compared
compared to
to thethe rate
rate at at which
whichheat heat function
functionof of the
thethermal
thermalproperties
properties of
of the
therock
rockpile,
pile,the
theamount
amount
conducts
conducts into
into or
or out
out of
of the
the thrust
thrust sheet.
sheet. As As will
will bebe discussed
discussed of
of radioactive
radioactive heating,
heating,andandthetheheat
heatflux
flux into
intothe
thebase
baseofof the
the
later,
later,models
modelsof of regional
regional(crustal
(crustalthickening)
thickening) metamorphism
metamorphism crust
crustfrom
from the
themantle.
mantle. InIn stable
stablecratonic
cratonicareas,
areas,thethetemperature
temperature
commonly
commonlystart startwithwith anan 'instantaneously'
'instantaneously' emplaced
emplacedthrust thrust at
ataagiven
givendepth
depthis isessentially
essentially constant
constant over
overtime,
time,that
thatis,
is,there
there
sheet.
sheet. is
isaasteady-state
steady-state geotherm.
geotherm. The
Theslope
slopeof of the
thegeotherm
geotherm is
iscalled
called
The
Theposition
positionof of aa metamorphic
metamorphic rock
rockwithwithrespect
respect to
tofaults
faults the
thegeothermal
geothermal gradient.
gradient.In In tectonically
tectonically active
activeareas,
areas,such
suchasas
and magmatic intrusions strongly influences
and magmaticintrusionsstronglyinfluencesthe pressure- the pressure subduction
subduction zones,
zones,temperatures
temperatures vary
varyover
overtime
timeand
andin ingeneral
general aa
temperature-time
temperature-time path.
path. Rocks
Rocksin in the
thelower
lowerplateplateof of aa thrust
thrust steady-state
steady-state geotherm
geotherm is
isnever
neverachieved.
achieved.
fault
faultwill
will be
beheated
heatedby by the
theoverriding,
overriding,hotter
hotterupper
upperplate.plate. In In Consider
Consider the
thepressure-temperature-time
pressure-temperature-time paths
pathsof of regionally
regionally
contrast,
contrast,rocks
rocksin in the
theupper
upperplate
platewillwill bebe cooled
cooledas asheat
heatis is metamorphosed
metamorphosed rocks
rocksshown
shown in
in Figure
Figure2. 2. Several
Severalgeotherms
geotherms
conducted
conducted downward
downwardinto intothethecooler,
cooler,lowerlowerplate.
plate. Frictional
Frictional are
are shown
shownforfor different
different times.
times. The The shape
shapeof of the
the geotherm
geotherm
heating
heatingmaymaylocally
locallyincrease
increase temperatures
temperatures in
in the
thethrust
thrustzone.
zone. varies
variesover
overtime
timereflecting
reflecting different
differenttectonic
tectonic processes
processes such
suchasas
The
The intrusion
intrusion of of magma
magma into into the the crust
crust willwill increase
increase burial
burialand
anderosion.
erosion.During
Duringburial,
burial,the thegeotherm
geothermis is depressed
depressed
temperatures
temperatures in
in the
thenearby
nearbyadjacent
adjacentcountry
countryrock. rock. Heat Heatis is and
andtemperatures
temperatures are
arerelatively
relativelycool coolat atdepth.
depth.During
Duringuplift,
uplift,
adveeted
advected with
withthe therising
risingmagma,
magma, and
andis isconducted
conducted into
intothethewall
wall the
thegeotherm
geotherm is
iselevated
elevated and
andtemperatures
temperatures are
arerelatively
relatively warm
warm
rocks
rocksduring
duringand andafter
afteremplacement.
emplacement. Hydrothermal
Hydrothermal circulation
circulation for
foraagiven
givendepth.
depth.At At any
anygiven
giventime,time,the
themetamorphic
metamorphic rock,
rock,
can
canredistribute
redistribute significant
significant amounts
amounts of
of heat
heataround
aroundplutons.
plutons. by
bydefinition,
definition, is
isat
atthe
thetemperature
temperature dictated
dictated by
bythe
thegeothermfor
geothermfor
PEACOCK 59
Tmax q = -kdT
dz
(2)
wherep = density
[kg/m3],
and
C = specificheatper unitmass[J/(kgK)].
This relationis importantbecauseit pointsout that three,and
that time. Most metamorphicreactionsare temperature only three,of the variablesc,k, p, andC needto be specified
sensitive,thusthe mineralassemblage of a metamorphic rock in a numerical model.
generallyreflectsthe highesttemperature(Tmax)experienced
by therock. In general,themineralassemblagewill reflectthe Heat TransferEquation
confining pressure(PTmax)at the maximum temperature.
PTmaxis often substantiallylessthanthe maximumpressure Time-dependent
heattransferis described
by thedifferential
experiencedby the rock. The locusof Tmax-PTmaxpoints equation:
determinedfor a suiteof metamorphicrocksmay be called a
metamorphicP-T array(= metamorphicgeothermof England
andRichardson[ 1977]) (Figure2). EachrockreachesTmaxat iT 2 A
=cV T-vVT+
a different time, thusthe metamorphicP-T array represents t pC
P-T conditions achieved at different times and does not (4)
representa crustalgeothermthat existedat any one specific
time [England and Richardson,1977]. The slope of the [Carslaw and Jaeger, 1959] which in one-dimension,with
metamorphic P-T arrayis calledthemetamorphicfield gradient z = depth, reducesto:
which can be calculated from the observed variation in P-T
2
conditionswithin a metamorphic
terrane[Spearet al., 1984].
3T 3 T 3T A
TheoreticalmetamorphicP-T arrayscanbe calculated using =f-V z +
a forward modeling approach and compared to observed 3t 2 3z pC
metamorphicP-T arraysobservedin the field. 3z
(5)
2OO 2OO
t
t
4OO 400
6OO 600
8OO 8OO
to
lOOO lOOO
PEACOCK
time. The straightline labeled t o in Figure 3 representsa importantheat sourceis the radioactivedecayof K, U, and
constantgeothermalgradient and is called the steady-state Th. Whereastheradioactive heatproduction of a typicalrock
solution; steady state refers to a thermal structure that is is small (e.g., 2 x 10-6 W/m3 for granite),its effectis
constantover time (/)T/i}t = 0). In the exampledepictedin importanton thetime scaleof millionsof years. Indeed,most
Figure 3, the steady-stategeothermis approachedover a of the earth's present surface heat flow is a result of
periodof thousands of years. radioactiveheatproduction.
It is important to point out that heat may be conducted Metamorphicreactionscanconsumeor releasesignificant
througha rockevenff therockremainsat constanttemperature amountsof heat. Progrademetamorphicreactionsthatoccur
with time, as is the casefor the steady-statesolution. From with increasingtemperaturearegenerallyendothermic, thatis,
Fourier'slaw (eqn. 2), we see that the amountof conductive they consumeheat. In contrast,retrogradereactionsare
heat flux is proportionalto the thermal gradient, which is exothermicandreleaseheat. Consider1 kg of shalethat is
constant,but non-zero,in the steady-statesolution. Heat is metamorphosed from 0 to 600 C. Given a specificheat,
beingconductedupwardthroughthe slab;the heatflux into the C = 1000 J/(kg K), 600 kJ of heat are requiredto raisethe
baseof the slab is the sameas the heat flux out of the top. temperatureof the rock from 0 to 600 C. Metamorphic
Becauseno heat is consumedor producedwithin the slab, reactions that release 5 wt % volatiles consume about
temperaturesin the slab remain constantover time and dT/dt 160 kJ/kg rock [Walther and Orville, 1982]; thus the heat
equalszero. consumedby metamorphicreactionscan be significant.
Equation(6) providesa very usefulgeneralapproximation Similarly,in magmaticsystems,theheatof crystallization
and
for pureheatconduction problems' heat of fusion are importantheat sourcesand heat sinks,
respectively.
(6) AnalyticalSolutions
where L = characteristic
lengthscale[m],
c= thermaldiffusivity[m2/s],and Analyticalsolutionsexistfor certaintypesof heattransfer
t = characteristictime scale[s]. problems [e.g., Carslaw and Jaeger, 1959]. Considerthe
Equation(6) approximates the distancea thermalpulsewill instantaneousheatingof a 1-kin-thickslab as illustratedin
travelgiventhe thermaldiffusivityof the mediumandlength Figure 3. The slab has a constantthermal diffusivity,
of time overwhichconduction operates.Usingthe example c= l mm2/s,
andisinitiallyat0C.Thetemperature
atthe
depictedin Figure3, we cancalculatethatin 1000yr theheat baseof theslabis raisedinstantaneously
to 1000Cresulting
in
pulsewill travel 178 m. Approximately200 m of rock has thegradualheatingof the slab.
beensignificantlyaffectedby theheatpulse.Alternatively,we The time-dependent,analyticalsolutionto this problem,
can rearrangeequation(6), solvingfor time as a functionof modifiedfromCarslawandJaeger[1959,p. 310,eqn.6], is:
lengthscale,andcalculatethat~30,000yr arerequiredfor the
heatpulseto travelthroughthe 1000 m slab. Keep in mind
that equation (6) is only a "back-of-the-envelope"
oo
FrfF.(2n+x)+x.
efff(2n+l)L-x.l
approximation andhasan uncertainty of perhaps
a factorof 2. (7)
Heat advection.Heatcardedalongby a movingmediumis
a form of heat transfer called advection. In mathematics and where erf is the error function (defined below),
physics,thisform of heattransferis calledconvection,but the T = temperature[K],
term advection is used herein to avoid confusion with the Tb = basaltemperature[ 1000 K],
geologicalmeaningof convectionwhichimpliesa circulation L = thicknessof the slab [ 1000 m],
system(a specialkind of advection). Several forms of heat x = position[m],
advection
occurin geologicalsystems.The burialandupliftof c= thermal
diffusivity
[1 mm2/s],
and
a rock involves movement of material, and thus is a form of t = time [s].
heatadvection.The diapiricriseof a magmaadvectsheatfrom Temperatureprofiles representingthe thermal structureas a
the sourceregionto theemplacement region. Fluidsflowing function of time are depictedin Figure 3A. Over tens of
throughrocksmay cool or warm infiltratedrocks. thousands of years, the thermal structure of the slab
Heat advectionis proportionalto the velocityof the moving approachesa steadystate.
medium and the thermal gradient as shown by the second The error function (erf) is definedas:
fight-handterm in equations(4) and (5). In the caseof burial
xe-2d
or uplift, thevelocityof themovingmediumis simplytherate
of burial or the rate of uplift. In the caseof fluid flow the erf(x)= 2
velocityis bestexpressed asa volumetricfluid flux, thatis, the
volume
offluidmovinthrough
a givencross-sectional
area, (8)
perunittime[units= mfluid/ (m2 s)]. Notethatthisreduces
to units of velocity [m/s]. The important point for heat Values for the error function of x may be found in most
advectionis thatheatis transported
from 'upstream'
regionsto standardmathematicaltablesor may be storedas an implicit
'downstream'regions. For example,fluids flowing from hot functionin a computer.
rocks into cold'rocks will warm up the infiltrated rocks. Analytical solutionsfor simple casesprovidea necessary
Conversely,fluidsflowingfrom coldrocksintohot rockswill check on the accuracyof the numericalsolutionsdiscussed
cool the infiltrated rocks. In essence,heat advectiontranslates below. However, analytical solutionsare not known for
the thermalstructurefrom upstreamto downstream
areas. complex geometriesor modelsthat containheterogeneities,
Heat sources and sinks. Heat can be producedor such as variable thermal diffusivity during metamorphic
consumedwithin a rock by heatsourcesandsinks. The most reaction. Most models of metamorphismuse numerical
NumericalSolutions- Finite-DifferenceMethod
2
AT A T AT A
--K-Vz+
At 2 Az pC
Az
(5B)
PEACOCK 63
replacedby an approximation in termsof dependent variableat Let us apply the finite-difference equation (15) to the
nearbygrid points.The followingfourequations arecommon probleminvolvingthe instantaneous heatingof a slab(Figure
finite differenceapproximationsfor first- and second-order 3) thatwassolvedanalyticallyabove.We startby definingan
derivativesat pointi: arrayof pointsevery 100 m alongthe z-axis(Figure3B). At
eachpointwe definean initial temperature condition:T(z,t=0)
)T Ti+-Ti = 0 C, and we will use the same constanttemperature
+ O{Ax} boundary conditions: T(z=0,t) = 0 C and T(z=l km,t) =
3-= Ax (10) 1000 C. Note thatthe initial temperature profile (labeledto)
is an approximation to theinitial temperatureprofileshownin
Figure3A. Numericalsolutions to differentialequations only
3-= Ax
}T Ti-Ti'l+O{Ax} approximate the analyticalsolutions. However, in principle,
a
(11) numericalsolutioncanbe madeasaccurateasrequiredsimply
by increasingthe numberof arraypointsanddecreasingthe
)T Ti+l_ Ti4 2 sizeof the time step(i.e. At andAz approachzero).
+ O{(ax) } Oncewe havedefinedtheinitial temperature at eacharray
}x- 2Ax (12) point, we simplyneedto calculatethe slopeandcurvatureof
the temperatureprofile at eachpoint in the arrayin orderto
define the first and second finite differences, AT/Az and
)2r Ti+_2Ti+ Ti4 2 A2T/Az
2, respectively.
Equation
(15)canbesolvedat each
- + O{(ax) }
OX 2 2 interiorpointin thearray. Thereis no needto solveequation
(ax) (13) (15) for the two boundarypoints(z = 0 andz = 1 km) because
the temperatureat thesepointsis constantovertime.
Equations (10) and (11) are forward and backward Explicit vs. implicitfinite differencemethods. Equation
differenceequations,respectively,for first orderderivatives. (15) is consideredanexplicitfinitedifferenceequationbecause
Equation(12) is a centraldifferenceequationfor first order the temperaturesat time n+l depend explicitly on the
derivatives;equation(13) is a centraldifferenceequationfor temperatures
at time n. In eachequationthereis oneunknown
secondorderderivatives. In equations(10) through(13) the temperature,Ti at time n+ 1, that dependsexplicifiyon three
term O{---} refers to the 'order'of the truncationerror which known temperatures - Ti+l, Ti, and Ti-1 at time n. This
is relatedto the orderof the first term truncatedin a Taylor relationship
is shownschematically
in Figure5A. The point
seriesexpansion.A FDE witha truncation errorof O{ (Ax)2} Tin is considered
theexpansion
pointaboutwhichthefinite
hassecond-order accuracyandis thereforemoreaccuratethan differenceapproximation
wasconsreacted.
a FDE with a truncationerrorof O{Ax}. The majoradvantageof theexplicitfinite-difference
method
In the explicit finite differencemethod,discussedin detail is that it is relatively easy to implement. Figure 6 is a
below,thetimederivativein equation(9) is approximated by a flowchartof thealgorithmusedto generatethefinite-difference
forwarddifferenceequation(10) andthesecond-order spatial solutionsdepicted in Figure 3B. The actual FORTRAN
derivativeis approximated with a centraldifferenceequation programis listedin Appendix1. Mostof theprogramis just
(13), resultingin thefollowingequation: bookkeeping;only two lines of code are neededto calculate
A2T/Az 2 and AT!
Tn+l n The majordrawbackof theexplicitfinite-difference method
i -Ti n 2Tq- n 2
At
Ti+- Ti4+O{At,(Ax)
2
} is the constrainton the sizeof the time step(At). In orderfor
the calculationto be mathematically stable,the time stepis
(ax) subjectedto the constraint:
(14)
t
Tn+l n
_.n+l.....n+lTn+l 2
i - Ti
=1 'fi+l- Z'fi + i-1 +O{At,(Ax)
,
2
}
At
Difference
/
molecule
Expansion point- T(i,n) (17)
n-1
Lettings= r,At/(Ax)
2 andrearranging,
wecanwrite
i-2 i-1 i i+1 i+2
B.Implicit
method We canwrite an equation(18) for eachinteriorgrid pointat a
giventime level in the solutiondomainresultingin a setof I-2
equationswith I unknowns.The two boundaryconditions,at
n+2
x = 0 and x = 1, provide the two necessaryadditional
equations.For the case of constanttemperatureboundary
conditions,the resultingsystemof equationscanbe writtenin
n+l
matrixform as shownin Table 1A. Becausethe temperatures
at the two boundariesare actuallyknownfor time n+ 1, we can
reducethe systemof equationsby two as shownin Table lB.
Expansionpoint - T(i,n+l )
The systemof equationsin Table lB is of the form:
n
Difference molecule
Tn=A Tn+l (19)
n-1
Expansion
point-
equations by matrixinversiontechniques.Seetextfor detailed
T(i,n+l/2) discussion of the threefinite differencemethods.(A) Explicit
n
finite differencemethod. The temperaturefor grid point i at
thenexttimelevel(Tin+1)depends
explicitly
ontemperatures
Difference molecule
at the currenttime level: Ti_l n, Ti n, Ti+ 1,n. (B) Implicit
finite differencemethod. The temperaturefor grid point i at
n-1
thenexttimelevel(Tin+1)depends
implicitly
ontemperatures
at thenexttimelevel:Ti_ln+t, Tin+l, Ti+l, n+l - and
explicitlyon Tin. (C) Crank-Nicolson implicitfinite differ-
encemethod. The temperature for gridpointi at the nexttime
level(Tin+1)depen,ds
implicitly
ontemperatures
atthenext
timelevel:Ti-1n+t, Tin+1, Ti+1,n+1, andexplicitly
on
temperatures
at thecurrenttimelevel:Ti-1n, Ti n, Ti+ 1,n.
PEACOCK 65
At =- (Ax)
2
Calculatetemperatureat boundaries K n1- 2T+T ni-1
ti+ 2 2
usingboundaryconditions +-- , + O{(At) ,(Ax) }
,
2 (ax)
2 (21)
EXIT
es whereu = velocityof the movingmediumin the x-direction.
In the explicitmethod,the time stepis constrained
theadvecting mediumdoesnotmovemorethanonegridspace
suchthat
in a singletime step. As was the casefor diffusion,the
Fig. 6. Flowchart of one-dimensional,explicit finite- presence of an advectivetermin theheattransferequation does
differencealgorithmusedto solveheatconductionproblem notimposeanystabilityconstraints on implicitfinitedifference
presentedin Figure3B. A FORTRAN programbasedon this methods. For detailed discussions of finite difference
algorithmis listedin Appendix1. solutionsto partialdifferentialequationsinvolvingadvective
and non-linear terms, the reader is referred to Carnahan et al.
[1969], Noye [1982], andPresset al. [1986].
The temperatures at time n+1 may be calculatedby finding Finite difference methods are not limited to one-dimensional
theinverseof matrixA andmultiplyingthroughby the vector problems.Explicitandimplicitfinitedifference
equations
can
Tn: be constructed for 2- and 3-dimensional problems. A
1 o o o o o o o
-s (1+2s) -s 0 0 0 0 0
0 -s (1+2s) -s 0 0 0 0
0 0 . . . 0 0 0
0 0 0
0 0 0 0 -s (1+2s) -s 0
0 0 0 0 0 -s (1+2s) -s
0 0 0 0 o o o 1
2
where s = rat / (Ax)
,114 1
(1+2s) -s 0 0 0 0 0 0
-s (1+2s) -s 0 0 0 0 0
0 -s (1+2s) -s 0 0 0 0
0 0 . . . 0 0 0
0 0 0 0 -s (1+2s) -s 0
0 0 0 0 0 -s (1+2s) -s
0 0 0 0 0 0 -s (1+2s)
2
where s = rat / (Ax)
n n+l
d2= T2+ sT1
d3= T 3
d4= T 4
dI_3= Ti_3
dI_2= Ti_2
n n+l
dI_1= Ti_1- sTI
PEACOCK 67
d2 (l+s) -s 0 0 0 0 0 0
-s (l+s) -s 0 0 0 0
0 -s (l+s) -s 0 0 0
0 0 . . . 0 0 0
2
where s = rat / (Ax)
n 1 n
d2=sT1+(1-s)T
+5-sT
3
1 n 1 n
d3=-sT
2+(1-s)T
+-sT
4
1 n 1 n
d4=-sT
3+(1-s)T
+-sT
5
1 n
dI_3= n+
sTt4
= sTn
di_2 I-3+ + sTn
1 n n
di_
1=-sTi_
2+(1-s)T_
1+sTI
x=l Ax
-
T(x+Ax)
=T(x)
+ -+ 2 3x
2 (28)
(25)
Solvingfor 3T/3x, we find:
Solvingfor Ti n+1,
Tn+l _n+l 3T T(x+Ax)-T(x) Ax021
'
1 = T2 -C2Ax (26)
Ax 2 3X2 (29)
In the explicit method, equation (26) is solved at the
boundariesafter the temperatures at the interiorgrid points The fundamental basis of differential calculus is that 3T/3x
havebeencalculatedat t = n+1. In implicitmethods,thefinite equalsthe first term on the right sideof equation(29) in the
differenceequation(26) is incorporatedinto the systemof limit where Ax approaches 0. The higherordertermson the
equationsthataresolvedat eachtime stepby matrixinversion. fight sideof equation(29) representthe truncationerrorof the
Note that the truncationerror given in equation(25) is not finite difference equation which tends toward 0 as Ax
of the same order as the truncation error for the central approaches 0. Equation(29) is identicalto the forwardfinite
differenceequationusedfor the spatialderivativeat interior differenceequation(10); thus equation(10) is a consistent
grid points(eqn.13). This problemcanbe overcomeby using finite difference equation. In a similar fashion, it can be
a more accuratepolynomialapproximationat the boundary shownthat thefinite differenceequationspresentedaboveare
such as: consistent with theirrespectivepartialdifferentialequations.
A stablenumericalschemeis one in which errorsfrom any
__n+l n+l _n+l 2 source(e.g., truncationerrors,round-offerrors)do not grow
3(,_)
-3'1'1
+4T2
-'1'3
+O{(Ax)
}
_...
as the calculationproceedsfrom one time level to the next
x=l 2Ax [Noye, 1982]. Stability is commonly demonstratedusing
(27) either discrete perturbation stability analysis or yon
Neumann'smethod[Noye, 1982]. In discreteperturbation
The third type of boundaryconditionis a combinationof stability
analysis,
anerrorisintroduced
atanarbitrary
Tinand
DirichletandNeumannboundaryconditions. the error'seffect on the calculationof subsequent
valuesis
It is importantto checkthe sensitivityof the finite difference examined.The constrainton the time stepin theexplicitfinite
modelto the chosenboundaryconditions.For example,what differencemethoddiscussedaboveis necessaryso thaterrors
is theeffectof varyingthevalueof themantleheatflux into the do not becomegreaterover time. In contrast,implicit finite
baseof the crust?Different computerrunsshouldbe madein differencemethodsaregenerallyunconditionally stablefor any
orderto evaluatethe effectof varyingtheboundaryconditions. sizetime step.
Convergence, consistency,and stability. In order to be The finite difference methods discussed above can be
usefula finite differencesolutionmustaccuratelyapproximate shown to be both consistent and stable, and therefore the
the solution to the original partial differential equation. solution to a finite difference equation convergeson the
Rigorousmathematicalderivationshave shownthat the finite solution to the partial differential equation as At and Ax
difference methods discussed above are valid, accurate approachzero.
PEACOCK 69
Testingof the numericalmodel. "A conceptualmodel and stratesomeof the basicconceptsinvolvedin constructing
the computercode derived from it are validated when it is numericalmodelsof heattransferduringmetamorphism.
confumedthat the conceptualmodel and the computercode
providea goodrepresentation of theactualprocesses occurring RegionalMetamorpln'sm
in a real system.Validationis thuscarriedout by comparison Most regional metamorphismis believed to result from
of calculationswith field observationsand experimental crustalthickeningassociatedwith continentcollision [e.g.,
measurements [InternationalAtomicEnergyAgency,1982]." EnglandandThompson,1984]. Regionalmetamorphic rocks
The conceptualmodel consistsof a model structureor exposedin orogenicbelts commonlyrecord pressuresin
geometry, together with necessaryinitial and boundary excessof 5 kb (500 MPa) corresponding to burialdepthsin
conditions. The computer code simulates the physical excessof 18 kin. Today, theseregionalmetamorphicrocks
processes that occurin the Conceptual model. For example, are underlain by crust of normal thickness (~35 km),
the computer code written for models of metamorphism suggesting that during metamorphism the crust was
reproducesthe variousheattransferprocesses that takeplace abnormallythick. Regional metamorphicbelts, suchas the
in a metamorphic terrane. In order to be a good Appalachians, Caledonides, Alps, and Urals appear to
representation, the modelmustbe simplerthanthereal world, representsites of past continent collision. The continental
but the model must be accurateenough for the specified crustbeneaththeHimalayasandtheTibetanplateau,theactive
objective.Field andexperimental observations
arerequiredto: collision zone betweenthe Indian and Eurasianplates, is
(1) identify the parametersof interest and the range of between55 and70 km thick[Molnar,1986]. Youngregional
conditionsto be investigated;(2) constrainthe model;and (3) metamorphicrocks exposedin the Himalayassupportthe
test the model.
concept thatcontinent
collisionresultsin crustalthickening
and
Before embarkingon the constructionof any model, we regional metamorphism. In the following section we
need to specify the observableparameters,the accuracy investigate pressure-temperature-time paths of regional
required,and the rangeof conditionsto which the modelwill metamorphismthat result from several different models of
be applied.In theforwardmodelingof metamorphism, we are crustalthickening.
primarilyconcerned with thepressure-temperature-timehistory Despite the complexity of continent-continentcollisions,
of a metamorphicterrane. We may also be concernedwith one-dimensional modelsof crustalthickeninghaveprovided
otherphenomenonsuchas the amountof fluid that infiltrates importantinsightinto the fundamental parameters governing
the rock as a functionof time. With the developmentof regionalmetamorphism[e.g., Oxburghand Turcotte, 1974;
computers, the accuracyof modelsolutionsis generallylimited England and Richardson,1977; England and Thompson,
by uncertainties in thermal parameters(such as thermal 1984; Thompsonand England, 1984]. In England and
diffusivity)andcrustalgeometries, andis not limited by the Thompson'sone-dimensionalmodels,the crustis assumedto
accuracy of thenumericaltechniques.As a roughestimate,we be instantaneouslythickened;this assumptionis justified
may want to predicttemperatures to within approximately becauseratesof heatemplacementare fasterthanratesof heat
10 C. Our modelsshouldbe sufficienfiyflexibleto allow us conduction, as discussed above. After instantaneous
to varydifferentparameters, suchasthethermalproperties of thickening,the thermalstructureof the crustis permittedto
therocks,andtheburialandupliftrates. relax, and the crust is uplifted and denudedover tens of
Ideally,a goodmodelgenerates specificpredictionsthatcan millionsof yearsuntil it reattainsnormalthickness.
be tested. Modelsof regionalmetamorphism makespecific Modeling regional metamorphismin only one dimension
predictions withrespectto themaximumtemperature achieved requiresthreesubstantial simplifications:
by a givenrock and the durationof metamorphism.These (1) The pre-collisionthermal structureof the continental
predictions canbetestedby comparison withmetamorphic P-T marginsis neglected.Prior to collision,one or bothmargins
estimates andradiometricdatingof metamorphic terranes. will be the site of ocean-continentconvergenceand will
In additionto the convergence, consistency,
andstability containsubductionzone(s) and magmaticarc(s). Thus, the
criteriadiscussed above,the accuracyof a numericalsolution thermal structureof the continentalmargins will be very
canandshouldbe testedin two ways: complex. At present,no modelshave been developedthat
(1) Whenever possiblethe numericalsolutionshouldbe incorporate thiscomplexity.
compared to an analyticalsolutionto theproblem.Analytical (2) The burialportionof thepressure-temperature-time path
solutions existfor manysimpleheattransferproblems[e.g., is neglectedbecausethe crustis thickened"instantaneously".
Carslaw and Jaeger, 1959], but most realistic geologic The model beginswith rocks at their maximumdepth. As
problemsdonothaveanalytical solutions.It is generally
only shownby EnglandandThompson[ 1984],metamorphic rocks
possible to check simplified versions of the numerical achievetheir maximum temperatureduring uplift, thus this
solution.
simplification is notcritical.Recently,theburialportionof the
(2) Additionalcomputerrunsshouldbe madeusinga pressure-temperature-timepath has been examined by
smallertime stepanda smallergrid spacing.I generallytest 'marrying'closelyspacedone-dimensional models[Karabinos
my numericalsolutionsusing0.5 Az and0.25 At. Thesetests andKetcham,1988] andby truetwo-dimensional models[Shi
are particularlyimportantfor the implicit finite-difference andWang, 1987].
methodbecause of thelackof a stabilityconstraint
on thesize (3) Only verticalheattransferis permitted.As shownby
of thetime step. Shi and Wang [1987], substantialamountsof lateral heat
transfercanoccurduringthethrusting(thickening)eventif the
Numerical Examples fault planedipsconsiderably (30 in Shi andWang'smodel).
Indeed, a true 'sawtooth'geothermis not achievedexceptat
In this section, we examine examples of pressure- unrealistically highconvergence rateson theorderof 2 m/yr.
temperature-timepathsdeterminedfrom numericalmodelsof Initial geotherrnprior to thickening. In stablecontinental
regional and contactmetamorphism.The examplesdemon- crust, the steady-stategeothermis primarily a functionof:
PEACOCK
lO 10
2o 2O
E 30 E 30
_ 40 - 40
50 50
6O 6O
7O 7O
lO 10
2o 2O
3o E 30
4o _ 40
5o 50
6o 6O
7o
I . I . I I . I
7O
10 10
20 20
E
30
m 40 (o 40
50 50
/
60 60 5
10
20
70 70
Fig. 9. (A) Thermalevolutionof thesawtooth
model.Curveslabeledwithtimein millionsof yearsafter
instantaneousthickening.
Duringthefirstseveral
millionyears,heatisconducted
rapidlyfromtheupperplate
downwardintothe lowerplate. Subsequently, temperatures increase
slowlyas a resultof the decayof
radioactive elements and the conduction of heat into the base of the thickened crust from the mantle. Curve
labeledtoorepresents
steady-statesolution.(B) Thermalevolution
of thehomogeneous
model.Temperatures
increaseslowlyasa resultof thedecayof radioactive
elementsandtheconduction
of heatintothebaseof the
thickened crust from the mantle.
constantover time at 0C; T(z = 0, t) = 0. At the bottomof the directedupward(alongthe thermalgradient). The geotherm
models, the heat flux into the baseof the crust from the mantle evolvestowardthe steady-stategeotherm(labeledtoo)overtens
is fixedat-0.03 W/m2;qm(z = 70, t) = -0.03. Themantle of millionsof years. The thickenedcrustis slowlyheatedby
heat flux is a negativequantitybecauseheat flows upward the simultaneous conduction of heat into the base of the crust
from the crustin the negativez direction. Given a uniform from the mantle and radioactivedecay of heat-producing
thermalconductivityanda constantmantleheatflux, Fourier's elementswithin the crust. The steady-stategeothermis
Law (eqn.2) fixes the slopeof thegeothermat the baseof the determinedby the boundaryconditionsandthe distributionof
crust.Fork = 2.25W/(mK) andqm= -0.03W/m2,theslope heat-producing elements; it is independent of the initial
of the geothermat 70 km, (dT/dz)70km= 13.3 K/km. temperature profile.
Finally, as discussedearlier, we needto define threeof the In the homogeneous model(Figure9B), thethickenedcrust
four parameters:k, ,c, p, and C. In thesemodels,I have evolvesslowlytowardthe steady-state geothermovera period
chosen
to definek = 2.25 W/(m K), p = 2700kg/m3, and of tens of millions of years. Note that the homogeneous
C = 1000 J/(kg K). Thermal diffusivity, ,c, is then defined steady-stategeothermis slightlydifferentfrom the sawtooth
by equation
(3) to equal8.33x 10-7m2/s. steady-stategeothermbecauseof the different distributionof
Thermal evolutionof thickenedcontinentalcrust. Now that heat-producing elementsbetweenthetwo models(seeFigures
we have defined the initial conditions, the boundary 8B and 8D).
conditions,and the necessarythermalparameters,we can Pressure-temperature-time paths. Temperature-timepaths
calculate the thermal evolution of the thickened crust as a for selectedrockscanbe calculatedfrom Figure9. Pressureis
functionof time usingthe finite-differencemethod.Figures constantfor thesetemperature-time pathsbecausewe havenot
9A and 9B show the thermal evolution of the sawtooth and yet incorporated erosionintoour models.
homogeneous models,respectively. Figure 10A showsgraphicallythe thermalevolutionof a
In the sawtoothmodel (Figure9A), the abruptchangesin rock locatedat 10km depthin the thickenedcrust. This rock
thethermalgradientnearthethrustat 35 km depthresultin the wasinitially at 5 km depthandwassubsequently buriedby the
rapidconduction of heatdownwardfrom the hot upperplate instantaneous emplacementof a 35 km-thickthrustsheet. As
intothecoollowerplate. Downwardheatconduction persists shown in Figure 10B, the rock initially heats up rapidly
for ~3.5 m.y.,duringwhichtime theinvertedthermalgradient because of the conduction of heat downward from the
is progressivelyerased. After ~3.5 m.y., temperature overlying thrust sheet. The rate of heating subsequently
increasesmonotonic ally with depth and all heat flow is decreasesovertime. Also shownin Figure 10B is the thermal
PEACOCK 73
10 - 500 40km _
400
;)0 300 m"'"oaaaaac
0km
30 200
40 F- 100
50 00 -'
10 --'-'-
20' '--" '-
30 40
60 Time (m.y.)
70
(C) Temperature
(C) (D)
0 200 400 600 800 1000
0 600 . , , . ,
PEACOCK 75
(A) Temperature
(C) (B) Temperature
(C)
0 200 400 600 800 1000 0 100 200 300 400 500 600
0 0
10
2OO
20
n 400 ,.
30
a) 600
40
,- 800 I
50
n 30km
60 1000 I
40 km
70 1200 ' ' ' ', ' , ,
10 2OO
20
400
30
600
40
800
50 3o km
1000
60
4O km
70 1200
PEACOCK 77
dT/dx = 0 andno heatwill flow acrossthisplane. Therefore, effective specificheat of the rock and decreasethe effective
the heat flux, q, is set equal to 0 at the left-side boundary. thermaldiffusivityof therock. As a first approximation, we
(Note thatat x > 0, the heatflux will be non-zero.) The right- considermetamorphic reactionsto consume100kJ/kgovera
side boundaryis placed far away from the intrusivecontact 400 Cinterval.Theeffectiveheatcapacityof thecounlxy
rock
such that it does not influence the thermal evolution of the is therefore1250J/(kgK) andtheeffectivethermaldiffusivity
contact aureole. This is called a "far-field" boundary is 7.2 x 10-7 m2/s.
condition. The temperatureat the fight-hand boundary Figures15A and 15C showthe thermalevolutionof contact
remainsconstantat Trock. aureoles adjacent to a basaltic intrusion and a granitic
In this example, we consider the thermal effects of intrusion,respectively. The basalticmagmais emplacedat
crystallizationandmetamorphic reactions.The crystallization 1150 C andreleases400 kJ/kg of heatduringcrystallization.
of a magmareleasessignificantquantitiesof heat. A basaltic The granitic magma is emplacedat 825 C and releases
magmamayrelease400 kJ/kgduringcrystallization whereasa 100 kJ/kg of heat during crystallization. Both magmas
graniticmagmamay release200 kJ/kg. The amountof heat crystallizeovera 100 Ctemperature interval. In bothmodels
releasedalsodependson the amountof crystallizationthathas theinitial temperature
of thecountryrockis 100 C.
taken place in the magma prior to intrusion. The heat of Over time, a heatpulsetravelsoutwardfrom the intrusion
crystallizationcan be modeled by calculatingan effective into thecounlryrock. The approximatedistancetheheatpulse
thermaldiffusivity,,c*, definedas: travelsas a functionof time onceagaincan be estimatedfrom
the "back-of-the-envelope" approximationgiven in _equation
,c* = k/(p C*) (32) (6). For a thermaldiffusivity,,c = 7.2 x 10-7 m2/s,and
t = 1 m.y., the heat pulse will travel approximately4.8 km
whereC* is an effectivespecificheatdefinedas: into the country rock. As can be seenin Figures 15A and
15C, at t = 1 m.y. approximately5 km of countryrock have
C* = C + (AH/AT) (33) beenheatedup to one-halfof theinitial temperature difference
betweenthe intrusionandcounu'yrock.
where AH = heatof crystallization[J/kg],and The effect of the heatof crystallizationcan be observedby
AT = temperature intervalof crystallization[K]. examining the area boundedby the t = 0 and t = 0.1 m.y.
The heatof crystallization
increases theeffectivespecificheat curvesin Figure 15A. The areaboundedby the curveswithin
of therock anddecreases the effectivethermaldiffusivityof the plutonis a factorof 4 timessmallerthanthe areabounded
the rock. In other words,a crystallizingmagmathat cools by the samecurvesin the countryrock (comparethe shaded
1 C releases more heat than a rock that cools 1 C. regionsin Figure 15A). This differencereflectsthe large
In thenumericalmodel,the thermaldiffusivityat pointsin amount of heat released during the crystallization of the
the intrusionreflectwhetheror not crystallizationis taking magma. Duringcrystallization,1 kg of magmathatcools1 C
place. After eachtime step,the temperature at eachpointis releasesenoughheatto warmup 4 kg of countryrock 1 C.
comparedto the solidustemperature of the intrudingmagma Figures 15B and 15D illustratethe maximumtemperature
composition. If the temperature is below the solidus achievedduringthecontactmetamorphic eventasa functionof
temperature,
thethermaldiffusivityis setto 9.0 x 10-7m2/s. distancefrom theintrusivecontact.Selectedpointsarelabeled
If crystallization
is takingplace,thenthethermaldiffusivityis with the time after intrusion at which Truax was achieved.
definedby equations (32) and(33). For a basalticmagmathat Basaltic magmasare emplacedat higher temperaturesthan
releases400 kJ/kgovera 100 Cinterval,theeffectivethermal graniticmagmas,and thereforeresultin highertemperature
diffusivity
is 1.8x 10-7m2/s.A granitic
magma
intruded
with contact aureoles. The curves illustrate that maximum
50% crystalsthatreleases100kJ/kgovera 100Cintervalhas temperaturesdecreasewith distancefrom the contactand that
aneffective
thermal
diffusivity
of 4.5x 10-7m2/s. thetimingof peakmetamorphism increaseswith distancefrom
Progrademetamorphicreactionsoccuringin the country the contact. Thus,the metamorphicP-T conditionspreserved
rock consumesignificantamountsof heat. As is the casewith in a contactaureole do not record a thermal gradientthat
magmaticcrystallization,metamorphicreactionsincreasethe existedat anyonespecifictime.
lO
2OO
2o
4OO
30
6OO
g- 40
8OO
50 3O km
lOOO
60
4O km
7O 1200 ! ! I . I . I
10 2OO
20
4OO
30
6OO
g- 40
8OO 3O km
50
lOOO
60 4O km
1200
70
PEACOCK 79
+ +
COUNTRY ROCK INTRUSION COUNTRY ROCK
+ +
20 km
+ i_+ 80 km
T = Trock
x
symmetry
plane
Fig. 14. Schematic illustration of the one-dimensionalnumerical model used to simulate contact
metamorphism. Thefinite-difference
arrayis oriented
perpendicular
to theintrusive
contact.Temperatures
at
pointswithintheintrusionareinitiallysetto Tmagma;temperatures
outside theintrusion
aresetto Trock--
100 C. The left-sideboundaryis locatedin the centerof the intrusion. Symmetryrequiresthat the
temperaturein thecenterof theintrusionis alwaysa localmaximum;thereforedT/dx -- 0 andno heatflows
acrosstheboundary, q: 0 (seeFourier'slaw, equation2). The right-sideboundary is locatedsignificantly
far away, 80 km from the centerof the intrusion,suchthat the constanttemperatureboundarycondition
(T - 100 C) will not effect the thermalevolutionof the contactaureole. The thermal diffusivitiesof the
intrusionand countryrock are adjustedfor the effectsof crystallizationand metamorphicreactions,
respectively;
seetextfor furtherexplanation.
600 x
E
400 I- 400
200
o
O I I I 200 ........... , , , ,
0 10 20 30 40 0 5 10 15
Distance(km) Distance(km)
a) 800 ,
o
o
600
1.3 m.y.
x
co 600
E
400
E
!- 400 a' 4.3
/
m.y. 9.8m.y.
!- 200 3. , x 10 ,
0 10 20 30 40 0 5 10 15
Distance(km) Distance(km)
Fig. 1:5.Results
of numerical
models
of contact
aureoles
adjacent
to basaltic
andgranitic
intrusion.
The
basaltic
magma
isintruded
at1150Candreleases
400kJ/kduring
crystallization.
Thegranitic
magma
contains$0%crystals,is intruded
at 825C,andreleases 100lcl/kgduring crystallization.
Bothmagmas
crystallize
overa 100Ctemperature interval.(A) Thermalevolutionof contact
aureoleadjacent
tobasaltic
intrusion.Curveslabeledwithtimein m.y. Notethatright-hand boundary of thenumericalmodelis at
80kin. (B) Truaxasa functionof distance
fromintrusivecontactforbasalticmodel.Selected pointsare
labeled
withtimeinm.y.illustrating
theoutward migration
of theheatpulsefromtheintrusion.(C) Thermal
evolutionof contact
aureoleadjacenttogranitic
intrusion.
Curveslabeled withtimein m.y.(D) Truaxasa
function
of distance
fromintrusive
contact
forgranitic
model.
PEACOCK
, DISTANCE
DISTANCE " DISTANCE
CRUST
SHORTENED
INE
-THICKENIN
CRUST 54' TENEO PRE - THRUSTING LITHId4EI 10ilITFNF. J) IqE-fHICJNledG
BY THRUSTIM OR UNOISTURO NOiOMEOUSL Oil STD lOOStv
CRUST CST CRUST
zF'
'',
' -- ---,
t_' .... i
; :<;';':";'"''"1 -- --
-- ...... I
- -'c- - x / . -
....
....
c
b ','-- -7 io'yo
TEMPERATURE C
d 7%.
PEACOCK 83
CrustalThinningafterCrustalThickening
c0
coo
Crustalthinningresultingfromextension of thecrustoccurs
in several different geologicsettings. Following crustal
PEACOCK 85
AND IL
lO 4
(Intrusion)
6
2O
B
3O
4
40
A KY 16
18
5O
0 200 400 600 800 1000
Temperature (C)
Fig. 19. Pressure-temperaturepathsfollowedby upperandlowerplaterocksin thickened crusttakinginto
account possiblemeltingof thelowercrustandsubsequent intrusionat highercrustallevels[modifiedfrom
DeYoreoet al., in press]. TO representsinitial sawtoothgeothermafter instantaneous thickening;
o1representsequilibrium(steady-state)geotherm in theabsence of erosion.PathA represents P-T path
owedby lowerplaterockinitiallyat 50 km depth.PathB represents P-T pathfollowedby upperplate
rockinitiallyat30 km depth.Duringuplifta 2-km-thick intrusionisemplaced withitsuppersurface at 12km
causingP-T pathB to crosstheandalusite to sillimanite
reactionin theprogradedirection.AND - andalusite,
KY - kyanitc,SIL - sillimanitc.SeeDeYoreoct al. [inpress]forthermalparameters usedin one-dimensional
model.
thickening,isostaticforcesresultin uplift of the continental deep crustal mctamorphismmay result from continental
crust and the developmentof extensionalstresses. Active extension. Deep crustalP-T-t pathsresultingfrom crustal
extensionis occurringtodayat convergent platemarginssuch extensiondiffer from pathsresultingfrom crustalthickening.
astheHimalayasandthe Andes[e.g.,Molnar, 1986]. Crustal CrustalextensionP-T-t pathsare characterizedby heatinginto
extension also occurs above zones of asthenospheric the granulitefaciesat constantor decreasing
pressurefollowed
upwellingsuchasmay existtodaybeneathEastAfrica andthe by coolingat constantor increasingpressureafter extension
BasinandRangeprovinceof the westernUnited States. ceases[SandifordandPowell, 1986]. Lithosphericextension
Crustalthinningmayresultin eitherheatingor coolingof a may alsoresultin the meltingof upwellingasthenosphere or
metamorphicrock. Lithospheric thinning results in the lower crust.
upwardmovementof the asthenosphere/lithosphere boundary, In contrast to lower crustal rocks, shallow crustal rocks
therebyincreasingthermalgradientswithinthelithosphere and may cool during extensionas they are broughtcloserto the
enhancingheatflow from themantleinto the baseof thecrust. earth'ssurface. Crustal extensionmay be accomodatedby
As discussedabove, crustal extension and increased mantle brittle (e.g., low-angle normal faults) or ductile processes.
heat flow has been proposedas the causeof low-pressure Rocksin the lower plate of a normalfault will cool as a result
regionalmetamorphism in thePyrenees[WickhamandTaylor, of moving closerto the earth'ssurfacewhereasrocks in the
1985; 1987]. Sandifordand Powell [1986] proposedthat upper plate may be heatedas they are juxtaposedagainst
0 5
DeformationandPressure-Temperature-Time
Paths AA SA
4.0
We have already discussedthe importanceof large-scale
advectiveheat transfermechanisms, suchasburial anduplift,
on metamorphicP-T-t paths. Advective heat transferalso
occurson smallerscales,suchasduringthe formationof folds
in a metamorphicterranes. In general,the effect of smaller- 500 600 700
scale advectivemechanismsis proportionalto the distance T
betweenthe rock andparticulardeformationstructure.A rock
closerto a thrustfault will be affectedmoreby advectiveheat
transfer than a rock further from the thrust.
Fig. 20. Pressure-temperaturepathsfollowedby metamorphic
In a studybasedon a complexlydeformedmetamorphic rocksin a multiple-foldedregionin southernNew Hampshire,
terrane in southern New Hampshire, Chamberlain and U.S.A. [Chamberlainand Karibinos,1987]. Two generations
Karabinos[ 1987] demonstrated that differentP-T pathsresult of non-coaxialfolding (F2 andF3) resultedin intersections
of
from the folding, and subsequentthermal relaxation, of anticlines(A) and synclines(S). AA repre-sentsP-T path at
isothermsduring deformation. The formationof an anticline F2 andF3 anticlineintersection.SS represents P-T pathat F2
resultsin coolingof rocksin the coreof the anticline,whereas and F3 synclineintersection. AS representsP-T path at F2
the formationof a synclineresultsin the warmingof rocksin anticlineandF3 synclineintersection.SA represents P-T path
thecoreof the syncline.In a polydeformed terraneaffectedby at F2 syncline and F3 anticline intersection. Inset shows
multiplefoldingevents,complicated P-T trajectoriescanresult isograds(first appearanceof K-feldsparanddisappearance of
(Figure20). muscovite)and fold axes where P-T path were observed.
Chamberlain and Karabinos [1987] also demonstratedthat
[Reproduced by permissionof GeologicalSocietyof America
complicatedP-T pathscan resultin thrustbelts. During and from C.P. Chamberlain and P. Karabinos, Influence of
shortly after thrusting, rocks in the lower plate undergo deformationon pressure-temperature
pathsof metamorphism,
heatingwhereasrocksin the upperplate undergocooling. In Geology, 15, 42-44, 1987.]
terraneswith multiplethrustsheets,a rockinitiallyin thelower
plate of an early thrust may be in the upperplate of a later
thrust. A variety of complexP-T pathsresultdependingon
the location of a rock relative to thrust faults and the relative
sequenceof thrusting.
The relative timing of metamorphicmineral growth vs.
deformation (foliation formation) has been the subject of DEFORMATION
PEACOCK 87
Metamorphic Fluids and Heat Transfer During Regional duringregionalmetamorphism do not significantlyperturbthe
Metarnorphism thermal structureof the crust, assumingthat fluid flow is
pervasivealonggrainboundaries or closely-spacedfractures.
Duringprogrademetamorphism, fluidsare evolvedby the Focusing of fluid flow into channelscan significantly
breakdownof volatile-bearing mineralspecies.Ferry [1986a, elevate fluid fluxes and enhance the thermal effects of fluid
b] summarizeda number of petrologic investigationsfrom advection [e.g., Peacock, 1987b, c; Brady, in press]. As
different metamorphic terranes which suggestthat large shownby Peacock[ 1987b], the thermalperturbationthat is
volumes of fluid infiltrate rocks during metamorphism. causedby channelizedflow will differ from thatof pervasive
Volumetric fluid/rock ratios greater than one have been flow only if the channels are widely spaced. During
calculatedusing the measuredprogressof devolatilization channelizedfluid flow, heatis simultaneouslyadvectedalong
reactions and stable isotopic systematicsfor a variety of the channel and conductedlaterally away from the channel.
lithologies
andfor areasgreaterthan100km2. Thereis a The approximatedistancethatthe lateralconductiveheatpulse
growingbody of evidencethat large amountsof fluid pass will travelis givenby:
throughrocksduringregionalmetamorphism.
The potentialimportanceof advectiveheattransferby L = t-rt (6)
metamorphic fluid flow hasbeenrecentlyinvestigated several
workers including Bickle and McKenzie [1987], Peacock
[1987b, c, in press],and Brady [in press]. One-dimensional whereL is the characteristic distance,cis thermaldiffusivity,
advectiveheattransferis governedby theequation: and t is the characteristictime scale. For c= 1 mm2/s and
t= 1 m.y., the characteristic distance is 5.6 km. For
3T 3T
t = 10 m.y., L = 17.8 km. In orderfor the thermaleffectsof
3t = -v 3z (34) neighboring channels not to impinge on one another, the
channelsmustbe spacedgreaterthan 11 km apartfor a 1 m.y.
wherev is the velocityof the advectingmedium. In the case characteristictime scaleof fluid flow and greaterthan 35 km
of fluid flow, v is proportionalto the Darcy velocity, or apartfor a 10 m.y. time scale.
volumetric fluid flux (the volume of fluid passingthrougha Given sufficientspacingbetweenchannels,the magnitude
cross-sectionalarea per unit time). In addition, the Darcy of the temperatureperturbationcausedby channelizedfluid
velocitymustbe multipliedby a factorcrepresenting theratio flow dependsprimarily on the vertical thermalgradient,the
of the volumetricheatcapacityof the fluid to the volumetric total amountof fluid that passesthroughthe channel,and the
heat capacity of the rock [Peacock, 1987c]. For crustal durationof flow. Fluids that are producedover a large region
conditions, thevolumetricheatcapacityof H20 variesbetween in the crust may be focused into a narrow channel or
2 and4 J/(cm3oK); thevolumetric heatcapacity of common metamorphicaquifer;focusingresultsin greaterfluid fluxes.
minerals varies between 2.6 and 4.2 J/(cm3oK) for A focusingratio may be defined as the ratio of the horizontal
temperatures
between200 and800 C [dataof Helgesonet al., cross-sectionalarea of the sourceregion to the horizontal
1978]. Thus, the factorc is closeto one for crustalconditions cross-sectionalareaof the channel. Large focusingratioslead
[Peacock,1987c]. to largetemperatureperturbations.
Peacock[in press]constructedone-dimensional modelsof As an example of the thermal effect of channelizedfluid
regionalmetamorphismin order to constrainratesof fluid flow, let us assumean averagefluid flux out of the lower 40
productionandfluid flux asa functionof time andpositionin km of thethickened
crustof 0.05kg/(m2oyr),
equivalent
to
thickened crust. I presentedfour end-membernumerical 5.6x 10-5m3(fluid)/(m2oyr)
fora fluiddensity
of 900kg/m.
experimentsresultingfrom combinationsof sawtoothrs. If the modelsof Peacock[1987b] and Brady [in press]are
homogeneousthickening geometries and continuousrs. used,focusingratios that exceed~60 would result in thermal
discontinuousmetamorphicreactionsthatreleaseup to 5 wt % anomaliesgreaterthan 100 C in the channels. Higher fluid
H20. In the sawtoothmodels, maximum fluid fluxes out of fluxesrequirelower focusingratiosto achievethe sameeffect.
Given the fluid fluxes calculated from the one-dimensional
the 40-km-thicklowerplateare ~0.2 kg (fluid)/(m2oyr).
Maximum fluid fluxesin the homogeneous
thickeningmodels numericalexperiments,(i) the thermal effectsof fluid flow
aresubstantially
lower,<0.06kg(fluid)/(m2oyr). duringregionalmetamorphismwill only be significantif fluid
Brady [in press] determined that significant regional flow is stronglyfocused,and (ii) fluid flow that is strongly
temperatureincreaseswould resultfrom situationswherethe focused into widely spacedchannelscould possibly cause
productof volumefluid f) and distance significantthermalperturbations,suchas thosereportedfrom
flux
s(.V transport(L)is
greaterthan3.6 x 10-7 m2/ He defineda dimensionlessNew Englandby ChamberlainandRumble[ 1986,in press].
parameter,B, analogousto a thermalPecletnumber,as: My calculationssuggestthat the majority of fluid flow
infiltratesrocksprior to the peakof metamorphism[Peacock,
in press]. High fluid/rock ratios that suggestmetamorphism
g _.
vfL pf Cp,f may be driven by fluid infiltration are difficult to explain in
k (35) terms of a pervasive, single-passflow system. Strongly-
focussedor multi-passfluid circulationsystemsappearto be
where vf = volumefluid flux, L = transportdistance,pf = required.
density
of thefluid,Cpf = volumetric
heatcapacity
of the
fluid,andk = thermal
c'nductivity
of therock. Valuesof B AdditionalReferences
greaterthan0.5 resultin noticeable
thermaleffects.Usingthe
fluid fluxes calculated by Peacock [in press] above, we Additionalanalyticaland numericalsmodelsof regional
calculate B = 0.4 for the sawtooth models and B < 0.1 for the metamorphism havebeenconstructed by: Birdet al. [ 1975],
homogeneousmodels. Therefore fluid fluxes generated GrahamandEngland[ 1976],England[1978, 1987], Sleep
1.00
0.90
0.60 = 0 + --
Oxt 20 [ l(2h
Z-x) +I 2hVT)]
0.40
h'eT= 33331/3
0.30
5OO0
2 hY= lOOOO
0.10
OF DIKE DIKE
WALL ROCK
0.0
[1979], Oxburgh and England [1980], Brewer [1981], simplegeometry[e.g., Lovering, 1935; Jaeger,1957; 1959;
Walther and Orville [ 1982], Fowler andNisbet [1982], Nisbet 1964; Carslaw and Jaeger, 1959]. For example,Figure 22
andFowler [1982], Rubie [1984], EnglandandBickle [1984], showsthe thermalevolutionof a dike and adjacentwall-rock
JaupartandProvost[ 1985],Chamberlain andEngland[ 1985], as a functionof time as calculatedby Lovering [ 1935], well
Selverstone[1985], Davy and Gillet [1986], England and beforetheintroduction of computers.The curvesin Figure22
Thompson[1986], and Harte and Dempster[1987], among representsolutionsto the equation[modifiedfrom Lovering,
others. 1935]:
T=T0+
T m- T O
2
erf/L-x' erflL+
Contact (Intrusion-Related) Metamorphism
(36)
Thecrystallization andcoolingof a magmaintrudedintothe
crustreleasesheat that metamorphoses surroundingcountry where T = temperature[K],
rock. The extentand degreeof metamorphism dependson TO= countryrock temperature[K],
manyparameters includingthetemperature of themagmaand Tm = magmatemperature[K],
countryrock,thecomposition anddegreeof crystallization
of L = one-half the thicknessof the dike [m],
the magma,the size and geometryof the intrusion,and the x = distance [m],
thermalproperties of themagmaandcountryrock. At shallow c= thermal
diffusivity
[m2/s],
crustallevels, a multi-passhydrothermalcirculationsystem t = time [s], and
may developthat redistributesthe heat releasedfrom the err = errorfunction[definedin equation(8)].
cooling intrusion. Dependingon the scaleof the problem As demonstrated,a rock locatedcloseto the dike will reach
underconsideration,contactmetamorphicprocessesmay be its maximumtemperature at an earliertime thana rocklocated
considered a heat conduction, a heat advection, or a heat further from the dike; the time at which Truax (peak
sourceproblem. For example,the calculationof temperature metamorphism)occursincreaseswith distancefrom the
profiles adjacentto a basalticdike primarily concernsheat contact.One of the shortcomings of analyticalsolutionsis the
conductionandthe heatreleasedduringcrystallization(a heat treatmentof the heat of crystallizationwhich is generally
source).On the crustalscale,thegenerationof a lower crustal approximatedby increasingthe initial temperatureof the
melt resulting from crustal thickening and subsequent magmaor by increasingthewidthof theintrusion.
emplacementat highercrustallevelscanbe considered a heat In a classic contribution, Norton and Knight [1977]
advection problem; the generation, migration, and constructed numericalmodelsof hydrothermalsystemscaused
emplacement of the magmasimplyredistributes heatfrom the by the intrusionof magmabodiesat shallowcrustallevels
lower crustto highercrustallevels. (<10 km). In this paper, Norton and Knight solve coupled,
Analytical solutionsexist that approximatethe thermal two-dimensional heat andmasstransferequationsin orderto
evolution of country rock adjacentto intrusionshaving a calculate the thermal evolution of magmatic/hydrothermal
PEACOCK 89
COMIJCTIVE t NO FLQM ,
! i
+ + + + +
+ + + + +
o6 Tz80.
+ + + + +
+ + + + + Cool,
more dense
+ + + + + T.
porefluid
+ + + + +
k I0 -17 4 = 4QO
+ + + + +
+ + + + + To 20C/km
low density
+ + + + +
porefluid
+ + + + +
+ + + + + Tp = 870C
Intrusion Country rock
I .I__m_RTINO t NO FI. ON
Fig. 23. Schematicillustrationof convection of an aqueous
fluid in a porousmediumadjacentto an igneousintrusion. o YEARS 20,000 YEARS
Lateral thermalgradientscauselateral variationsin fluid A.
density. Heatedporefluidsadjacentto the intrusionhavea
relativelylow densityandtendto rise. Cooler,higher-density
fluids move towardthe intrusionto replacethe rising fluid,
thuscreatinga circulationsystem.
CONOUCI'IVE , NO FLOM
i
Fig.24. Thermalevolution
of a coolingplutonviaconductive
coolingalone [Norton and Knight, 1977]. The thermal
'1_
structure is shown for a two-dimensional cross section of a
pluton(rectangle)and surrounding
countryrock. In the
model,an 870 Ci_mpermeable
plutonis emplacedintolow
permeability
(10-17cm2) country
rock. Thecountry
rock
permeability is toolow to permitconvectionof porefluids,
thusall coolingtakesplaceby conduction.A constant linear
initial geothermalgradientof 20 C/km is assumed with a
surfacetemperature of 20 C. Temperature
distributionsare
shownfor t = 0.02, 0.05, 0.1, 0.16, and 1 Ma after intrusion
(A, B, andC). [Reproduced
by permissionof the American IIlJIlIl t NO FLOM
Journalof Sciencefrom D. Norton and J. Knight, Transport 160,000 YEARS 1,000,000 YEARS
phenomena
in hydrothermal
systems:
coolingplutons,Am.J.
Sci., 277, 937-981, 1977.] C.
IIULRTINO NO AdditionalReferences
100000 YERRS
PEACOCK 91
employed[e.g.,TurcotteandSchubert,1973]. In addition,as
CAL
!C
M
aSECM _
1.0--,
characteristic
lengthscaleof 50 km (one-halfthe thicknessof
/CAL/CM;SEC
--
1.0-
0.5-
theoceanic
lithosphere),
anda thermal
diffusivity
of 1 mm2/s, ..,zo... o,..
4OO
-
tooo
' .
--.....-
16o0-_
tooo
_
subductingslab.
Oceanic crust, consistingof mafic igneousrocks and 2.0- HIeAT FLOW t 10.8 MY -
oceaniclithosphere.Meltingof basaltandsedimentary
rock I.O
-
0.5- ,Z
CAL/CM
HORIZONTAL
DISTANCE,
KM -
occursat lower temperatures thanperidotite(mantle),thusthe 0
600-
/////////////' ,.r,,,
', '"
-
-
-
of these early thermal models require frictional heating 00- -
(A) (B)
DISTANCE, KM DISTANCE, KM
400 300 200 I00 0 400 300 200 mOO
0 '
, _ ;?
,/ / , , , ,
,
.
1oo
200J
STREAM FUNCTION STREAM FUNCTION
0.87 M Y I0 MY
DISTANCE, KM DISTANCE,KM
400 3OO 200 I00 0 400 300 200 I00 0
_
ioo /I Ioo
300 /
5oo
700
, '
oo"--Y.'
'"
900
/' ioo
200 - - - 200 i i
TEMPERATURE , DEG C TEMPERATURE,DEG C
0.87 MY I0 MY
rheologyinto their numericalmodels. Their modelpredicts Graham and England [1976] proposedthat shearheating
that "low-angle subduction can extend several hundred alongtheVincentthrustsystemresultedin theformationof the
kilometersinlandonly in casesof highconvergentvelocities PelonaSchistinvertedmetamorphicgradient.In Grahamand
(>15 cm/yr) and old (>120 Ma) lithosphere." Honda and England's one-dimensionalmodel, shear heating elevates
Uyeda[ 1983]reviewedexistingthermalmodelsandpresented temperaturesin the thrust zone and createsan inverted
models of the thermal structure of numerous subduction zones metamorphicgradientin the top portion of the lower plate.
based on combined heat transfer/comer flow solutions. Van Post-thrustingthermalrelaxationleads to lower thrustzone
der Beukel and Wortel [1986, 1987] used surface heat flow temperatures andthepreservationof aninvertedmetamorphic
measurements to constrain shear stresses in the shallow gradient. In orderto generateinvertedthermalgradientsin
portionsof subduction zones.They concludethatat depthsof excess
of-50 C/km,shearheating
mustexceed
0.25W/m2
25-75 km, shearstresses between20 and60 MPa arerequired for a periodof 1 m.y. or more [GrahamandEngland,1976;
to satisfyheatflow constraintsand achievethe temperatures Peacock, 1987d]. Greater amounts of shear heating are
necessary for blueschist
faciesmetamorphism. requiredto generatethe -100 to -250 C/km metamorphic
gradientsrecordedin severalCordilleranpaleo-subduction
Frictional(Strain)Heating zones. Invertedmetamorphicgradientsarediscussed
in detail
in a later section.
The importanceof strainheatinghasbeendebatedin both The amountof frictionalheatingon a slip surfaceis given
subduction
andregionalmetamorphic settings. by theexpression
[TurcotteandSchubert,1982,p. 189]:
PEACOCK 93
invertedmetamorphic gradient.
The importanceof shear heating during metamorphism 0
remains uncertain. The long-term theological behavior of
rocks (consistingof several different minerals) at elevated
pressureand temperatureis difficult to extrapolatefrom
laboratoryexperimentsof relatively short duration. In my
opinion, many cited field examplesof frictional heatingat
depthsgreaterthan 10 km [e.g., Scholtz, 1980] can be also
interpretedas resultingfrom otherheat transfermechanisms.
At shallow crustallevels, glass-bearingpseudotachylites in 35O
constructed,
they superimposed
the petrogenefic
grid on the Temperature B Temperature
subduction zone thermal structure of Hasebe et al. [1970].
One of their conclusionsis that 14A-chlorite (a relatively
hydrousphase)may persistto depthsin excessof 200 km.
Althoughheattransferandmetamorphicreactionsare strictly
coupled,Delaney and Helgeson'scontributionprovidesa
goodfirstapproximation
to dehydration
reactions
occurringin
subduction zones.
Inaddition
todehydration
reactions
inthe
subducting
slab,
thermal models should consider the effect of hydration // HW ! HW
reactions
(e.g.,serpentinization)
in theoverlying
mantle SS SS
wedge
[Peacock,
1987a,
c].Extensive
hydration
ofthe
hangingwall of paleo-subduction zoneshasbeendocumented
by Bebout[ 1986] andPeacock[ 1987a]. Hydrationreactions
are exothermic,releasingsignificantamountsof heat, and
thereforedelay cooling of the hangingwall. The combined
effect of prograde reactions in the subducting slab and
retrogradereactionsin thehangingwall is to retardthethermal
evolution of the subduction zone and to preserve the
temperaturecontrastbetween the subductingslab and the
overlyingmantle. This effect will be partly counteractedby Fig. 29. Schematicverticalgeothermsthrougha subduction
the increaseddownward heat conductionresultingfrom the zone showingthermaleffectsof (A) pervasiveupwardfluid
preservedtemperature contrast. flow and (B) channelizedfluid flow [after Peacock, 1987c].
Horizontal dotted line representshanging wall (HW) -
subducting slab(SS) interface.Solidcurvesrepresent vertical
Fluids in Subduction Zones
geothermafter a periodof subduction,neglectingeffectsof
fluids. Dashed curves representqualitative effects of (A)
Fluidsreleasedin subductionzonesmay sufferoneof three pervasiveupwardfluid flow and(B) channelized fluid flow up
possiblefates: (1) fluidsmay migrateupwardandescapeto alongthe subduction shearzone. Seetext for discussion.
the surface; (2) fluids may cause retrograde (hydration,
carbonation)reactionsand be reincorporatedinto overlying
rock; or (3) fluids may participatein meltingreactionsand
becomeincorporated into a magma. Channelizedfluid flow resultsin higher fluid fluxes and
As discussed above, the thermal effect of fluid flow is thereforea greaterlocalizedthermaleffectthanpervasivefluid
proportionalto volumetricfluid flux, that is, the volumeof flow (Figure29B). Fluidsderivedfrom a largeareamay be
fluid passingthrougha cross-sectional areaper time. Because concentratedin the subductionshearzone becauseof higher
the volumetricheatcapacities of rockandfluid aresimilar,the permeabilities andthedevelopment of metamorphic foliation
thermaleffectsof fluid infiltrationand uplift are similar. The parallelto the shearzone. Conductionof heatawayfrom the
amountof fluid releasedby progrademetamorphicreactions zoneof concentrated fluid flow limits the temperatureincrease
duringsubductionis surprisinglysmall. resulting from advective heat transport. As a first
Considerthe following simplifiedcalculation,takenfrom approximation, we canconsidertheeffectivewidthof thefluid
Peacock[1987b], in whichoceaniccrustcontainingan average flow channelto equaltwice the characteristic diffusivelength
of 2 wt % H20 is subducted at 5 cm/yr. In orderto maximize scale(L) givenbyL = (,c.t)0.5(eqn.6). For,c= 1 mm2/sec
the thermal effects of released fluid, let us assumethat all of and t = 1 to 10 m.y., the effective width of the fluid flow
the subductedH20 is releasedin dehydrationreactions;no channel is ~20 km. If we use the same geometry and
volatilesarerecycledinto themantle. For eachkm of trench, parameters discussedabove,the effectivefluid flux along[the
2.4 x 107kg of H20 is subducted
peryear. Usinga fluid subduction
shear zonewilldecrease
linearlyfrom~1x 10- m3
densityof 1200kg/m3,eachyear~2x 104m3 ofH20 willbe H20/(m2.yr)at thesurfaceto zeroat 150km depth.The
releasedper km of trench. thermaleffectof fluid flow at 75 km depthis equivalentto the
Considerthe caseof pervasiveupwardfluid flow. For a shearzonethermalstructuremovingup-dipat 0.5 to 1 mm/yr
45 subduction zone, the released fluid will infiltrate rocks (Figure 29B). Clearly subductionof cool lithosphereat
located between the trench and 150 km arcward. The 5 cm/yr will swampthe fluid advectionterm. Preliminary
pervasiveDarcy fluid flux is therefore1.3 x 10-4 two-dimensionalnumericalcalculationssuggestthat 10 m.y.
m3H20/(m2-yr).Because thevolumetric
heatcapacities
of of channelized fluid flow at 75 km depth will only elevate
rock and fluid are within a factor of 2, the thermal effect of shearzonetemperatures ~10 C.
pervasivefluid flow is comparableto the thermaleffect of Fluid flow may play a more importantrole in the thermal
regionaluplift at a rate of 0.13 to 0.26 mm/yr. Ten million evolutionof accretionary wedgeswheresubstantial amountsof
yearsof subductionwill translatethe thermalstructureof the porefluids are releasedduringthe compactionof sediments.
hanging wall only ~2 km towards the surface. Thermal Reck [1987] noted an apparentparadoxbetweenmeasured
modelsof subductionzoneshave shownthat the top part of near-surface thermal gradients of 24-36 C/km and
the subductingslab is cooler than underlyingrocks and the temperaturesof 150 C at depths>15 km predictedfrom
overlying hanging wall [e.g., Minear and Toksoz, 1970; conductivemodelsfor the northeastJapanaccretionaryprism.
Oxburgh, 1974]. Thus, fluids released from dehydration Reck [1987] was able to resolve this apparentparadox by
reactionsin thedowngoingslabthatmigrateupwardwill tend
to coolthe lowerpartof the hangingwall (Figure29A). considering
advective
heat
transfer
_y
3m3/(m2oyr)].
vertical
fluidflow
ratesontheorderof 10'10m/s[3 x 1at
Despite
PEACOCK 95
Sierra Pelona
Vincent N]
Thrust
mylonites /
San Andreas
Fault
Pelona
Schist
0 I 2 3 4 5km
Subduction-Related
InvertedMetamorphicGradients heatdownwardfromthe hangingwall into theupperportion
of the subductingslab. As the slab is subducted,inverted
Peak metamorphic temperatures and recrystallization thermalgradients in excessof- 100 C/kmformat thetopof
increasestructurallyupwardin severalpaleosubduction zones theslabasshownin Figure32. In orderto bepreserved in the
in the western United States [Peacock, 1987d]. These geologicrecord,the invertedmetamorphic gradientmustbe
invertedmetamorphic gradientsincludethePelona-Orocopia accretedto the baseof the hangingwall. Accretionof the
Schist (southern California), the Catalina Schist (southern upperportionof the subductingslab may occurbecauseof
Californiaborderland),theCentralMetamorphic Belt (Klamath decliningtemperatures thatcausedownwardmigrationof the
province), the South Fork Mountain Schist (northern viscousslip zone and/or greenschistfacies devolatilization
California Coast Ranges),and possiblythe ShuksanSuite reactionsthat weaken the descendingslab. Model 1 best
(northernWashington).With theexceptionof the SouthFork explainsthe invertedmetamorphic gradientpreservedin the
Mountain Schist,peak metamorphictemperaturesincrease CentralMetamorphicBeltwhichappears to representa discrete
structurallyupward from ~400 C to ~650 C over 1-2 km, slice of oceaniccrust accretedto the baseof the Trinity
indicating metamorphicgradientsin excessof-100 C/km peridotite(mantle).
(Figure 31). The tectonicsettingsand high metamorphic Model 2. Alternatively,invertedmetamorphicgradients
pressures (~800 MPa) suggestthatthe invertedmetamorphic may representthe continuousaccretionof materialat ratesof
gradientsformedin paleosubduction zones. 1-10 mm/yr under conditionsof declining temperature.
Peacock[ 1987d]constructed two separatetwo-dimensional Continuously-accreted invertedmetamorphic gradientscould
numerical models in order to constrain the thermal conditions form beneathoceaniclithosphere asold as 30 Ma. Model 2 is
underwhich invertedmetamorphicgradientsare createdand probably more applicable to sediment-rich inverted
preserved.Two possiblescenariosexist: metamorphic gradientssuchasthePelona-Orocopia Schist.
Model 1. Rapid subduction(~10 cm/yr) beneathyoung In both models, continued subduction of ~1000 km of
oceaniclithosphere(<10 Ma) resultsin therapidconduction of oceaniclithosphereis requiredto effectivelyrefrigeratethe
PEACOCK 97
4
Fig. 32. Developmentof an invertedthermalgradientat the
top of a subductingslab calculatedusinga 2-dimensional
=e- t= 0 finite-differencemodel [Peacock,1987d]. Thermal evolution
-*' t = 0.1 m.y. of the uppermost10 km of a subductingslab showingthe
effect of downwardheatconductionduringdescentbeneatha
t = 0.2 m.y. hot hanging wall. The thermal profile is oriented
t = 0.3 m.y. perpendicularto the surfaceof the descendingplate. The
t = 0.424 m.y. initial temperatureprofile, labeledt = 0, is a 10 Ma oceanic
geothermof TurcotteandSchubert'[ 1982]. In thismodelthe
convergence rateis 10 cm/yr. Thermalprofilesare shownfor
0.1, 0.2, 0.3, and 0.424 m.y. after the initiation of
subduction. The 0.424 thermal profile represents the
temperature distributionin thesubducting slabwhenthetopof
the slab has reacheda depth of 30 km. Thermal gradients
exceed-100 C/kmat thetopof theslab. This invertedthermal
gradientwould be preservedas an invertedmetamorphic
gradientif thetopportionof thesubducting slabis accretedto
10 the baseof the hangingwall.
C
C PROGRAMTSLAB - This program approximates the thermal evolution
C of an instantaneously heated, 1-kin-thick slab using an
C explicit finite difference method.
C
C Initial conditions' T (z, t=0) = 0C
C
C Boundary conditions: T(z=0,t) = 0 C
C T(z=l,t) = 1000 C
C
C-
PROGRAM TSLAB
IMPLICIT REAL*8 (A-H,O-Z)
REAL* 8 KAPPA
DIMENSION TEMP (11) , DERIV2 (11)
100 CONTINUE
C
C *** End of time step loop ***
C
CLOSE (UNIT=11)
STOP
END
PEACOCK 99
Adch'tio
nal References Carslaw, H.S. and Jaeger, J.C., Conduction of Heat in
Solids. Oxford University Press,New York, 510 pp,
Additionreferencesregardingmodelingof subductionzone 1959.
metamorphisminclude: Andersonet al. [ 1976, 1980],Derore Carnahan, B., Luther, H.A., and Wilkes, J.O., Armlied
[1983], Closs [1985], Platt [1987], Ernst [1988], Dahlen and NumericalMethods. J. Wiley and Sons,New York, 1969.
Bart [in press],andBart andDahlen [in press]. Chamberlain,C.P., and England,P.C., The Acadian thermal
historyof theMerrimackSynclinoriumin New Hampshire.
Acknowledgements. I am extremelygratefulfor the helpful J. Geol., 93, 593-602, 1985.
reviewsprovidedby thefollowingpeople:Paul Barbera,John Chamberlain, C.P., and Karabinos, P., Influence of
Goodge, Brooks Hanson, Ralph Haugerud, Emmerich
Knoebl, David Palais, Frank Spear, and David Williams.
deformation on pressure-temperature paths of
metamorphism.Geology, 15.42-44, 1987.
Their careful reviews of earlier forms of this manuscript Chamberlain, C.P., and Rumble, D. III, Thermal anomaliesin
resultedin a greatlyimprovedpaper. Any omissionsor errors
a regionalmetamorphicterrane:evidencefor convectiveheat
remainmy responsibility.This work was partially supported
transportduring metamorphism. Geol. Soc. Am. Abstr.
by NationalScienceFoundationgrantEAR-8720343. Programs,1_ 561, 1986.
Chamberlain, C.P., and Rumble, D. III, Thermal anomaliesin
References Cited a regionalmetamorphic terrane:an isotopicstudyof therole
of fluids. J. Petrol., 29. in press.
Anderson, D.A., Tannehill, J.C., and Pletcher, R.H., Cloos,M., Flow melanges:Numericalmodelingand geologic
Computational Fluid Mechanics and Heat Transfer. constraintson their origin in the Franciscansubduction
HemispherePubl.Co., New York, 600 pp., 1984 complex,California. Geol. Soc. Am. Bull., 93. 330-345,
Anderson, R.N., DeLong, S.E., and Schwarz, W.M., 1982.
Thermal model for subductionwith dehydrationin the Cloos, M., Flow melangesand the structuralevolution of
downgoingslab. J. Geol., 731-739, 1978. accretionarywedges. Geol. Soc. Am. Special Paper,No.
Anderson, R.N., DeLong, S.E., and Schwarz, W.M., 198, 71-79, 1984.
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subductionzones. J. Geol., 88. 445-451, 1980.
Thermalmodelingandreevaluationof isotopicAr-agesfor
Anderson,R.N., Uyeda, S., and Miyashiro, A., Geophysical blueschists in the Franciscan complex of California.
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plateboundaries Tectonics, 4, 421-433, 1985.
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R, Astr0n, Soc., 4_44
333-357, 1976. Crank, J., and Nicolson,P., A practicalmethodfor numerical
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Soc., 38, 237-251, 1974. 50-67, 1947.
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press. Geophys.Res., in press.
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metamorphism:Catalina Schist terrane, Santa Catalina collisionzonesandits thermalconsequences. Tectonics,5,
Island, CA. Geol. Soc. Am. Abstr. Programs,18,538, 913-929, 1986.
1986. Day, H.W., Controls on the apparent thermal and baric
Bickle, M.J., Hawkesworth,C.J., England,P.C., and Athey, structureof mountain belts. J. Geol., 95, 807-824, 1987.
D., A preliminary thermal model for regional Delany, J.M., and Helgeson, H.C., Calculation of the
metamorphismin the EasternAlps. EarthPlanet.Sci. Let., thermodynamic consequences
of dehydrationin subducting
2_.6,13-28, 1975. oceanic crust to 100 kb and > 800C. Am. J. Sci., 278,
Bickle, M.J., and McKenzie, D., The transportof heat and 638-686, 1978.
matterby fluids duringmetamorphism.Contrib.Mineral, DeVore, G.W., Relationsbetweensubduction,slab heating,
Petrol., 95. 384-392, 1987. slab dehydration and continental growth. Lithos, 16,
Bird, P., Stressand temperaturein subductionshearzones: 255-263, 1983.
Tonga and Mariana. Geophys. J. R. Astron. Soc., 55, De Yoreo, J.J., Lux, D.R., and Guidotti, C.V., The role of
411-434, 1978. crustal anatexis and magma migration in the thermal
Bird, P., Formationof the RockyMountains,WesternUnited evolution of regionsof thickenedcontinentalcrust. In
States:A continuumcomputermodel. Science,239, 1501- Evolutionof Mountain Belts,J. Geol. Soc.LondonSpecial
1507, 1988. Publ., in press.
Bird, P., Toksoz, M.N., and Sleep, N.H., Thermal and Draper, G.R., and Bone, R., Denudation rates, thermal
mechanical models of continent-continentconvergence evolution,andpreservationof blueschistterrains.J. Geol.,
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