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Metamorphic Pressure-

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.

American Geophysical Union, Washington, D.C.


Maria Luisa Crawford and Elaine Padovani
Short Course Series Editors

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

Copyright1989by the AmericanGeophysical


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CONTENTS

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

2 Thermal Modeling of Metamorphic Pressure-Temperature-TimePaths 57


Introduction 57
Heat Transfer--Equations
and Solutions 59
NumericalExamples 69
Literature Review 79
RegionalMetamorphism 80
ContactMetamorphism 88
SubductionZone Metamorphism 90
Appendix 98
References 99
PREFACE

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

solutions rather than analytical solutions are generally References


required. Examplesof regional and contactmetamorphism
illustratein detail the applicationof numericalmodelsof heat England, P. C. and S. W. Richardson, The influence of
transferto problemsof metamorphism.Finally, a review of erosion upon the mineral facies of rocks from different
the literature on thermal aspectsof regional, contact and metamorphicenvironments,J. Geol. Soc. London,134,
subduction zonemetamorphism is presented. 201-213, 1977.
The interestedreadermay alsowish to examinethe excellent England,P. C. andA. B. Thompson,Pressure-temperature
set of short course notes recently published by the - timepathsof regionalmetamorphism, PartI: Heattransfer
Mineralogical Associationof Canada (Nisbet and Fowler, during the evolutionof regionsof thickenedcontinental
eds., 1988) for additional discussion and alternative crust. J. Petrol., 25, 894-928, 1984.
perspectives
on the subjectof heatflow, metamorphism
and Nisbet, E.G. and C. M. R. Fowler, eds. Short Course on
tectonics.
Heat, Metamorphismand Tectonics. Mineral. Assoc.
Canada,ShortCourseHandbook,14, 319 pp., 1988.
Oxburgh,E. R., andD. L. Turcotte, Thermalgradientsand
regionalmetamorphism in overthrustterrainswith special
reference to the eastern Alps: Schweizerische
MineralogischeandPetrographische Mitteilungen,54, 641-
662, 1974.
Metamorphic Pressure-
Temperature-Time Paths
Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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.

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

Spear:Petrologic
determination
of metamorphic
P-T-tpaths

15- I [ I I of a phaseare thosethatcan be addedto or subtractedfrom a


phasewithout destructionof the integrityof that phase. For
example,thechemicalvariabilityof garnetwill be describedin
termsof thephasecomponents almandine,pyrope,spessartine
lO and grossular,rather than the system componentsSiO2,
A1203, FeO, MgO, MnO andCaO. Let the numberof phase
componentsin each phase be designatednp and the total
5 numberof phasecomponentsin all phasesbe designatedNP
(NP= Y.np). In general,NP will be greaterthan NC, the
number of system components. It can be shown that the
numberof linearly independentreactionsthat can be written
amongthe NP phasecomponents is
200 400 600 800
TC NRX: NP- NC (2)
700 [ [ I I I I I I I I I [ [

B This relationis very importantbecauseany changesin the


modal mineralogyor mineral chemistryof the assemblage
6OO
must take place by some combinationof these linearly
independent reactions. In addition, all possible
geothermometers or geobarometersfor the assemblage
canbe
formed from combinationsof these linearly independent
5OO reactions.
A setof linearly independentreactionsmay be foundquite
5O 100
easily by applicationof an algorithmof linear algebrafirst
Time (Ma) appliedto this problemby J. B. ThompsonJr. [1982]. Each
I ] [ i , I I I I of the NP phasecomponentsis defined by an equationin
termsof the NC systemcomponentsand the equationsare
arrangedas two matrices,which will be called the phase
componentmatrix and the systemcomponentmatrix. The
phasecomponentmatrixis a NP x NP identitymatrixandthe
systemcomponent matrixis anNC x NP matrixcontaining the
definitions of the NP phase components. A Gaussian
reductionis performedon the systemcomponentmatrix with
similar operationsbeingperformedon the phasecomponent
matrix (a Gaussianreduction is a processof adding and
subtractingmultiplesof equations sothatall of thecoefficients
belowthediagonalaremadeto be zero.) After thereductionis
5O 100 complete,someof therowsin the systemcomponentmatrix
will contain non-zero coefficients. The number of non-zero
Time (Ma) rowsgivestherankof thematrix,whichindicatesthe number
of systemcomponents necessary to describethe chemical
Fig. 1. (A) Typicalpressure-temperature(P-T) pathfor crust variabilityof thephases.If therankof thematrixis NC then
thickenedby overthrusting [interpolated from Englandand thecorrectnumberof systemcomponents werechosenat the
Thompson,1984]. Also shownis a generalized dehydration outset. If the rank is less than NC then the system was
reactionA = B + H20. (B) Temperature-time pathfor theP-T overspecified.The correctnumberof systemcomponents is
pathshownin (A) [interpolatedfromThompson andEngland, equalto therank.
1984]. (C) Generalizedratevs timeplotcorresponding to the The numberof rows of the systemcomponent matrixthat
T-t path of (B). Rate scaleis arbitraryand assumesan containall zerocoefficientsspecifythedimensionof the null
activationenergyof approximately250 kJ/mole. space. If the numberof systemcomponents were chosen
correctly,thentherewill be NP-NC = NRX rowswith zero
coefficients(in any case, the numberof rows with zero
coefficientsmustbe equalto NP-rank). The corresponding
NRX rows of the phasecomponentmatrix are the set of
Thermodynamics of Heterogeneous Systems linearlyindependent
reactions amongthephasecomponents.
An examplewill demonstrate how thisprocedureworks.
LinearlyIndependentReactionsAmongPhaseComponents Considerthe assemblage olivine + pyroxene+ quartzin the
systemSiO2- MgO - FeO.Theolivinewill bedescribed by
Consider a rock with NC systemcomponents(SiO2, thephasecomponents forsterite
(Fo:Mg2SiO4)andfayalite
A1203, MgO, FeO, etc.) thatconsistsof an assemblageof P (Fa:Fe2SiO4),thepyroxeneby thephasecomponentsenstatite
mineralsat a specifiedpressureand temperature.Following (En:MgSiO3)andferrosilite
(Fs:FeSiO3)andquartzbyquartz
Gibbs [1906; seealsoThompson,1982] we will describethe (Qz: SiO2). Therearea totalof 3 systemcomponents,
5 phase
equilibrium conditionsof the assemblagein terms of components and2 linearlyindependentreactions.
independently variablecomponents of phases(mineralsor Theequations
thatdefinethephase
components
in termsof
fluids)in theassemblage.Independentlyvariablecomponents the systemcomponentsare

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

Spear: Petrologicdetermination
of metamorphic
P-T-t paths 3

Fo = 2MgO + 0FeO + 1SiO2 (3) Maximum reactions = NP! (14)


Fa =0MgO + 2FeO + 1SiO2 (4) (NC+ 1) !(NP-(NC+ 1))!
En =lMgO + 0FeO + 1SiO2 (5)
Fs =0MgO + 1FeO + 15iO2 (6) For example,in the SiO2-MgO-FeOsystemdiscussed
above,
Qz = 0MgO + 0FeO + 1SiO2 (7) the maximum number of reactions is

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

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

Spear:Petrologic
determination
of metamorphic
P-T-t paths

TABLE 1. Definitionsof Symbols

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)

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

Spear:Petrologicdetermination
of metamorphic
P-T-t paths 5

Pressurecorrectionsare made by integrationof the AV of


reactionwith respectto pressure: 0=(AH(_.R,)
+}'ACdT
+AVdP-1))dT
+AVsdP
Ag(T,P)= Ag(T,PR)+ IAVdP (24) + RTdlnKeq (31)
Equation(20) can thusbe rewrittenas whichcanbe usedto compute:hanges in mineralcomposition
as a functionof P andT or to infer P-T pathsfrom chemical
0 =AH(TR,PR)
+laCpdT- T(AS(TR,PR)
+l(aCp/T)dT) changesin mineralssuchas zonedgarnets.
It shouldbe reemphasized thatan equationsuchas (28) or
+ IAVdP + RTlnKeq (25) its differentialform (30, 31) canbe writtenfor everyreaction
thatcanbe writtenamongphasecomponents of an assemblage
Equations16-25 are perfectlygeneral,but cannotbe used in equilibrium. However, it is only necessaryto write
for calculation until a standardstateis defined, which will in equations(28) for a linearly independentset of reactionsto
turnallow a def'tnifion
for theactivities(eq. 18). describecompletelythe phaseequilibriaof the system.Any
In geologic applications,a mixed standardstate is often additionalequations areredundant.
utilized where the standard state for solids is chosen to be the As an example, considerthe two independentreactions
purephasecomponentsat P andT of interestand the standard derivedfor theassemblage olivine+ pyroxene+ quartz:
stateof gasesis chosento be thepuregasspeciesat 1 barand
T of interest.Adoptingthismixedstandardstate,thepressure Fs - En - 0.5(Fa - Fo) = 0 (11)
integral (eq. 24) may be evaluatedas follows. For solid
and
phases,
,AVsis nearlyindependent
of T andP. Thereforethe
integralJAVsdPmay be approximated
as
Qz + Fo- 2En = 0 (12)
'AVsdP
= AVs(P-PR). (26)
Equation(28) takesthe form
For fluid species
V is a strongfunctionof P andT, in which
casetheintegral
JVgdP
becomes 0= AHll+IACplldT-
T(ASll+l(ACpl
1]W)dT)
+AVll(P-1)
IVgdP
=RTln(fg/fg
)=RTln(fg) (27) aFs,Px
(aFo,Ol)
0'5
+ RTln (32)
wherefe is thefugacityof thefluid(gas)species
andfgis the
fugacit3rofthepuregasspecies at thestandard state(1'barand aEn,Px
(aFa,O1)
0'5
T of interest)and hasa valueof 1. A generalizedversionof and
equaOon(25) that employsa mixed standardstateof pure
endmembercomponentsat P and T of interestfor solidsand
the pure speciesat 1 bar and T of interest for fluids may be 0=AH12
+IACp12dT
- T(AS12
+kACpldT)+AV12(P-1)
written as:
aQz,Qz aFo,O1
+ RTlnK (33)
0 =zMH(TR,PR)
+IACpdT
- T(AS(TR,PR)
+j'(aCpfr)dT) (aEn,Px)
2
+ AVs(P-1)+ RTlnKeq (28) respectively.

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

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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

Calculation of Metamorphic Phase Equilibria. F=2 + NP + P-(NP + P)=2. (42)

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.

0: .dXj,k (40) Because of the constraintsimplied in Duhem's theorem


J (thermodynamic, stoichiometric and mass balance) the
equilibriumconfiguration
for a specificbulk composition
is a
Therefore, there are a total of NRX + P = NP - NC + P reproduciblemineralassemblage, setof mineralcompositions
equationsthat apply to the assemblage
in equilibrium. The and modes.

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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:

0 = fix) = f(x') + Of(x')/Ox) (51)


dlnaj,k= otj dXj (47)
Xj,k
Non-ideal solutionmodels. Slightly more complicatedare An initial guessis madefor xandequation(51) is solvedfor
Ax:
the symmetricand asymmetricMargules expansions. For a
binary symmetricsolutionmodel, the activity coefficientfor
component1 is ax = (52)

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)

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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.

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

Spear:Petrologic
determination
of metamorphic
P-T-tpaths 9

Oneof themostimportantconsiderations to be madein the modeledby thegrid,mustalsobeconsidered.


Forthepelitic
use of a petrogeneficgrid to interpretmetamorphicP-T grid shownin Figure2, it was assumed
that the A1203
conditionsis the relationbetweenthe chemicalsubspace contentsof the mineralsmuscovite,biotiteand chloriteremain
represented
bythegridandthechemical system representedby constantover the entire grid. That is, thereare no reactions
the rock. Grids are typically constructedfor simplified thatalterthetschermak component (A1A1Mg.lSi.1) in these
chemicalsystems whereasreal rocksmay be considerably minerals.Reactions involvingtschermakcomponent may
morecomplex. Therefore,it is criticalto ascertainwhetherthe occurin a portionof thechemical system
notrepresented by
assemblagesand reactionsthat are observedin the natural the projectedphasediagram,but give the appearance of a
sampleare sameas the equilibriain the simplifiedsystem reactionthatoccurson the grid. For example,considerthe
modeled by the grid, or are instead the result of extra possible reactions
in theKFMASHsystem in theassemblage
components in thenaturalsamplethatarenotmodeledby the chloritoid+ chlorite+ muscovite+ quartzwheretschermak
grid. exchange is permitted.In additionto theFe-Mgexchange
As an example,considerthepetrogenetic grid for pelitic reactions
schistsin the SiO2-A1203-MgO-FeO-K20-H20(KFMASH)
systempresentedby Spearand Cheney[1989] (Figure2). FeMg.l(chlorite)= FeMg_1(chloritoid) (61)
This gridis basedon thermodynamic calculationsusingthe
databaseof Bermanet al. [ 1985] andBerman[ 1988] as well FeMg_1(chlorite)
= FeMg_l(muscovite ) (62)
ason inferences basedonnaturalassemblages. Thegridwas
constructed by first derivingthe locationsof reactionsin the
theexchange
reaction
endmember KFASH and KMASH systems and then
computingthe slopesof reactionsin the KFMASH system
usingnaturalpartitioning data. A1A1Mg.
lSi.l(muscovite)
= A1A1Mg.
1Si.1(chlorite) (63)
The gridshowssomeratherunconventional phaserelations and the net transfer reaction
with respectto the stabilityof garnet+ chloriteassemblages
versuschloritoid+ biotiteassemblages. Specifically,thegrid
predicts that in the KFMASH system, the paragenesis chlorite+ quartz+ A1A1Mg.
iSi. 1= chloritoid+ H20 (64)
chloritoid+ biotiteshouldbe stablein a widevarietyof bulk
compositionsat low grades. This prediction,however,is in are alsopossible.With increasingdehydration reaction(64)
contrastto observationsbasedon natural assemblagesin will proceedto the right with the resultthat the muscovitein
which garnet+ chlorite is the commonassemblagein low this assemblageshould become enriched in celadonite
grademetapelites. component,as shownon the AKF diagramin Figure 4.
Thediscrepancy betweenthepredictions of thegridandthe Because of this,bulkcompositions thatoriginallycontainonly
chlorite+ muscovite + quartzmaybeginto growchloritoidas
observations in naturalassemblages can be reconciledby thetrianglechlorite+ chloritoid+ muscovitesweeps acrossthe
considerationof theeffectthatMnO hasonthepredicted phase bulk composition,shownas a crossin Figure4. Therefore,
relations.Figure3 is a seriesof AFM projections[Thompson, chloritoidmightappearin a rocknotasa resultof anyreaction
1957]depictingthesequence of phasediagrams predictedby thatappearson the grid,butby a reactionthatoccursoff of the
the gridat approximately 4-5 kbarfrom 350 to 550'C. As can projectedphasediagram. Additionaldiscussionof the effect
be seen,the assemblage chloritoid+ biotiteis stablerelativeto of thetschermak substitutiononreactions in peliticschists
can
garnet+ chlorite(b-e) until approximately530'C, wherethe be foundin Thompson[1979].
reactionchloritoid+ biotite= garnet+ chloriteis encountered
(topologies e to f). BeloweachAFM diagramis a plotof FeO Geothermometry and Geobarometry
- MgO - MnO in whichthemineralscoexistingwith biotite,
quartz and muscovite are plotted. As can be seen in this TheoreticalBasisof Geothermobarometry
diagram,theassemblage chloritoid+ biotite+ garnet+ chlorite
is restricted to rocks that are rich in FeO. Other bulk Geothermobarometry is the name given to applications
compositions will containtheassemblage garnet+ chlorite(+ whereby the pressureand temperaturedependenceof the
biotite)if MnO is presentasan additional component andthe equilibrium constant (equation 28) is used to infer
assemblagechloritoid+ biotite will neverbe observed. This metamorphicpressures andtemperatures. The centralnotionof
analysisis consistentwith naturaloccurrences of chloritoid+ thermobarometry is thatthe valueof theequilibriumconstant
biotiteassemblages whichare restrictedto rockswith high can be determinedby measurementof the compositionsof
Fe/Mg [e.g. Hoscheck,1967]. A similaranalysisshowsthat coexistingmineralsand applicationof appropriateactivity
the extra componentCaO, which partitionsstronglyinto models.A singleequilibriumconstantwill definea line on a P-
garnet,hasthesameeffect.In a similarfashiontheassemblage T diagram.InasmuchasdifferentequilibriahavedifferentP-T
garnet+ cordieritemay be stabilizedto temperatures lower slopes,theintersection of two equilibriacanbe usedto infer a
thanthatpredictedby the KFMASH grid by thepresenceof P-T point.
MnO andCaO in thegarnet. By definition,geothermometers arethoseequilibriathatare
Thisexampledemonstrates thatthephaserelationsdepicted best suited to calculation of geologic temperaturesand
by a petrogeneticgrid may not reflect naturaloccurrences geobarometersare those equilibria that are best suited to
because of theinfluenceof extracomponents on thestabilityof calculation of geologic pressures. In general,
mineralsin the grid. The components that havethe largest geothermometersare equilibria that have little pressure
effectin typicalpeliticschists areMnO andCaO in garnetand dependenceso that an impreciseestimateof the pressureof
ZnO in staurolite. equilibrationwill only producea smallerrorin theestimateof
A second concern is that reactions that occur in the chemical temperature.Similarly, geobarometers are equilibriathat are
systemdepictedby the grid, but that are not specifically relativelyinsensitiveto temperature.

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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:

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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//] XCh Ga/ Ch


FeO/.LMgO
/
MnO
\ MnO

Ga

FeO Ch MgO FeO St Ch MgO

Fig. 3. Sequenceof AFM diagrams[Thompson,1957] andFeO-MgO-MnO trianglesdepictingthe phase


diagramtopologiesobservedin selectedP-T regions(a-i) in Figure2. All assemblages shownin the FeO-
MgO-MnO diagramscontainbiotite+ quartz+ muscovitein additionto assemblages shown.Thesediagrams
showtheexpandedfield for garnetstabilitywhenMnO is considered asan additionalcomponent.They also
showthatthe assemblagechloritoid+ biotite+ garnet+ chloriteis restrictedto rockswith high Fe/(Fe+Mg)
andthatrocksof intermediate
bulkcomposition containthecommonlyobservedassemblage garnet+ biotite+
chlorite.

(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

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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.

valuesof molar volumes). Both typesof calibrationsmay be


subject to numerous different modifications (hybrid
calibrations) by virtue of the different formulationsof the
activity-compositionrelationsthatmaybeappliedto each.
There are advantagesand disadvantages to each type of
calibration.Experimentalcalibrationsaremoreaccuratein that
the P-T conditionsof the experimentare controlledand, as a T
consequence, the variationof the equilibriumconstantwith P
and T is generally better constrainedin an experimental
calibrationthan in an empirical calibration. However, the Fig. 5. SchematicP-T diagramsshowingrepresentative
P-T
disadvantageto most experimental calibrations that are slopesfor equilibriathatwouldmakea goodgeothermometer
availableto dateis that the experimentshavegenerallybeen (A) anda goodgeobarometer (B).
performed in idealized systems. For example, the
experimentalcalibrationof the Fe-Mg partitioningbetween
garnetand biotite by Ferry and Spear [1978] was done on
almandine-pyropeand annite-phlogopitesolid solutions. the valuesderived for AH and AV so that realisticpressures
Natural garnetstypically containMnO and CaO and natural and temperatures may often be obtainedfrom them.Hybrid
biotitescontainTiO2, Fe203, andA1A1Mg_iSi_isubstitutions. calibrations that rely on experimental determinationsof
Therefore,eventhoughtheexperimental calibrationis accurate reactionsor partitioncoefficientsin the idealizedsystemand
in the idealizedsystem,the applicationof the calibrationto empiricalcalibrationsof theeffectof extracomponents in the
natural assemblagesis less certain becausethe activity- phasesinvolvedappearat thistime to givethemostinternally
compositionrelations of the phasesinvolved are not well consistent values for P and T.
understood.
Empiricalcalibrationsare lessaccuratebecausetheyrely on ExchangeThermometers
estimates of P and T from other sources for their calibration
and these are always more poorly constrainedthan in the Therearea largenumberof geothermometers thatarebased.
experiments. However, empirical calibrations tend to on cation exchange reactions, especially involving the,
incorporatethe non-idealityof the solid solutionphasesinto exchangeof Fe andMg betweencoexisting
silicates.
Exchange

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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

have been calibrated by Thompson [1976], Goldman and 4Mg3A12Si3012+ 3NaCa2Fe4A13Si6022(OH)2


=
Albee [1977], Ferry and Spear [1978], Perchuk and
Lavrent'eva[1981], Hodgesand Spear[1982], Gangulyand 4Fe3A12Si3012
+ 3NaCa2MgnA13Si6022(OH)2 (71)
Saxena[1984] andIndaresandMartingole[1985].
The Ferry and Spear[1978] and Perchukand Lavrent'eva hasbeenpresentedby GrahamandPowell [ 1984].
[ 1981] calibrationsare experimentalwhereasthe calibrations Garnet-chlorite.An empiricalcalibration
for thereaction
of Thompson [1976] and Goldman and Albee [1977] are
empcal and useKDSderivedfrom naturalassemblages and 5Mg3A12Si3012+ 3FesA12Si3010(OH)8
=
estimatesof the temperature to obtainvaluesfor AH andAS of
reaction (Goldman and Albee used oxygen-isotope 5Fe3A12Si3012
+ 3MgsA12Si3010(OH)8 (72)
temperatures).Both of the empiricalcalibrationsgive lower
temperaturesthan the Ferry and Spear calibrationand it is
possiblethat both of theserepresentcoolingtemperatures for has been presentedby Dickensonand Hewitt [1986]. With
Fe-Mg exchangebetweengarnetandbiotiteor oxygenisotope correctionsfor Ca in garnetas suggestedby HodgesandSpear
exchange, respectively. Note that all give identical [1982], this thermometergivesresultsthat are generallyin
temperatureswithin error at approximately 500C. The agreement with thegarnet-biotitegeothermometer.
refinementof HodgesandSpear[1982], whichis basedon the Garnet-orthopyroxene. Calibrationsof thereaction
experiments of FerryandSpear[ 1978],involvesincorporation
of non-idealmixing for Ca in garnetandresultsin computed Mg3A12Si3012+ 3FeSiO3 = Fe3A12Si3012
+ 3MgSiO3 (73)
temperatures that are higher than those obtained from
applicationof the thermometerwithout the correction.The havebeenpresented
by Mori andGreen[ 1978],Harley [ 1984]
refinement of Ganguly and Saxena [1984], which is also andSenandBhattacharya[1984].
Garnet-olivine. The reaction
basedon Ferry and Spear[1978], involvesincorporationof
non-idealmixing termsfor Ca, Mn and Fe-Mg solutionin
garnet. The Ca correctionis similar to that of Hodgesand 2Mg3A12Si3012+ 3Fe2SiO4=
Spear[1982]; the Mn and Fe-Mg correctionstend to have
oppositeeffectsbecausehighMn garnetsgenerallyhavelower 2Fe3A12Si3012+ 3Mg2SiO4 (74)
Fe/Mg thando low Mn garnets.The correctionof Indaresand
Martingole
[ 1985]involveconsideration
of Ti andA1vI in the has been calibrated by Kawasaki [1979] and O'Neill and
biotitesolutionmodelandgiveslowertemperatures
thanthose Wood [1979, 1980].
obtained without these corrections. Biotite-tourmaline.
An empiricalcalibrationof thereaction
At thistime,it is impossibleto saywhichcalibrationis best.
The Ca correctionto garnetappearsto be justified basedon 2Mg3A12Si3012
+ Fe-tourmaline
=
calculationsin high-Ca, low-Mn rocks from Vermont [T.
Menard, unpublisheddata]. However, becauseof the high 2Fe3A12Si3012
+ Mg-tourmaline (75)
correlationbetweenMnO and Fe/Mg in garnetsfrom many
pelitic schists,it is impossibleto concludewhetheror not the
additional correctionsof Ganguly and Saxena [1984] are hasbeenpresented
by Colopietro andFriberg[1987]
warranted. Garnet-phengite.
The reaction

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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)

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Spear:Petrologicdetermination
of metamorphic
P-T-t paths 15

Empirical calibrationsof both equilibriahave beenpresented 3Fe2SiO4+ 3CaA12Si208=


by Ghentand Smut [ 1981] andof the Fe endmember(equation
79) by Hodgesand Crowley [1985] and the Mg endmember Ca3A12Si3012
+ 2Fe3A12Si3012 (88)
(equation80) by Powell andHolland[1988].
Garnet - plagioclase- muscovite- biotite- quartz- A12Si05. Garnet- plagioclase- orthopyroxene- quartzand Garnet-
Hodges and Crowley [1985] have presented empirical plagioclase- clinopyroxene- quartz. Calibrationshavebeen
calibrationsof severalother equilibria that apply to pelitic presentedfor the reactions
schistswith the aboveassemblageusingthe samedata set as
was usedin the calibrationof equation(79). Thesereactions 3MgSiO3 + 3CaA12Si208=
are not all independent, but some make better
thermobarometers thanothers.Only thosereactionsfor which 2Mg3A12Si3012+ Ca3A12Si3012
+ 3SIO2 (89)
calibrationsappearto be well constrainedarepresentedhere:

Fe3A12Si3012+ 2Ca3A12Si3012+ 3A12Fe_lSi_l(in Ms) + 3FeSiO3+ 3CaA12Si208=

6SIO2 = 6CaA12Si208 (81) 2Fe3A12Si3012+ Ca3A12Si3012+ 3SIO2 (90)

Fe3A12Si3012
+ 3A12Fe.lSi_l (in Ms) + 4SIO2 3CaMgSi206+ 3CaA12Si208=
= 4A12SIO5 (82) 2Ca3A12Si3012
+ Mg3A12Si3012
+ 3SIO2 (91)
KA13Si3010(OH)2+ Fe3A12Si3012 and

= KFe3A1Si3010(OH)2+ 2A12SIO5+ SiO2 (83) 3CaFeSi206+ 3CaA12Si208=


Reaction (83) has also been calibrated by Holdaway et al. 2Ca3A12Si3012
+ Fe3A12Si3012
+ 3SIO2 (92)
[1988].
Garnet-plagioclase-hornblende-quartz.
Theequilibria by Wood [1975: rxn. 89], Newton and Perkins [1982: rxns.
90 and 91], Bohlen et al. [1983a: rxn. 90], Perkins and
3NaA1Si308+ 6CaA12Si208+ 3Ca2MgsSi8022(OH)2= Chipera [1985: rxns. 89 and 90], Perkins[1987: rxns. 91 and
92], Powell and Holland [1988: rxns. 89 and 91] and Moecher
3NaCa2Mg4A13Si6022(OH)2
+ 2Ca3A12Si3012
+ et al. [1988: rxns 90 and 91]. All of these are based on Ca
exchangebetweengarnetandplagioclaseandhavea strong
Mg3A12Si3012+ 18SIO2 (84) pressuredependence andonly a mild temperaturedependence
andthereforemakeexcellentgeobarometers. Theseequilibria
are principally useful in granulite facies rocks where
3NaA1Si308+ 6CaA12Si208+ 3Ca2FesSi8022(OH)2= assemblages containinggarnet+ plagioclase+ pyroxene+
quartz are common.
3NaCa2Fe4A13Si6022(OH)2
+ 2Ca3A12Si3012+ Garnet-plagioclase-rutile-ilmenite-quartz(GRIPS). The
equilibrium
Fe3A12Si3012+ 18SIO2 (85)
Ca3A12Si3012
+ 2Fe3A12Si3012
+ 6TIO2 =

3Ca2MgsSi8022(OH)2+ 6CaA12Si208= 6FeTiO3 + 3CaA12Si208+ 3SIO2 (93)

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)

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

16 Spear:Petrologic
determination
of metamorphic
P-T-tpaths

Calculationsof theP-T locationsof theseequilibriahavebeen Sphalerite-pyrrhotite-pyrite.Scott[1973; 1976] andLusk


presentedby EsseneandBohlen[ 1985].Additional equilibria and Ford [1978] havepresentedcalibrationsbasedon the Fe
involvingtitaniteas an additionalTi-bearingphasecan be contentof sphaleritecoexistingwith pyrrhotiteandpyriteasa
written,namely[seeBohlenandLiotta,1986] geobarometer.Accordingto Essene[1982], however,this
equilibriumis subjectto resettingduringcooling.
CaA12Si208+ 2CaTiSiO5 = Magnetite-ilmenite geothermometry. Two equilibriacanbe
written in systemsthat contain coexisting magnetite and
Ca3A12Si3012
+ 2TIO2+ SiO2 (97) ilmenite:

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;

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Spear:Petrologic
determination
of metamorphic
P-T-t paths 17

(2) Considerationof the effectsof reequilibrationon cooling Mg partitioningbetweengarnetand biotite is known to be a


and the notion of closure temperature as applied to functionof XCa in garnet. If sucha variationis found,andis
thermobarometry; and systematic,thenthe thermobarometric calibrationshouldtakeit
(3) Interpretationof the significanceof the resultsin light of into account.If thevariationis randomandoutsideanalytical
theprecisionandaccuracyof thecalibration. errorsthenit probablymeansdisequilibrium.
Becausethe thermobarometric resultsare only as good as The fourthtestis to detemfinewhetherthetemperatures and
the quality of these assumptions, they merit detailed pressures computedfrom the geothermometer or barometerare
discussion. consistentover a small,outcrop-sizedarea. Too oftenthisis
the first test that is applied, resulting in the erroneous
Evaluationof ChemicalEquilibrium interpretationthat the calibrationis in error when, in fact, the
rockswere not equilibrated.If the calculatedP-T valuesare all
The fundamentalassumptionin the applicationof any within analyticalerror,thenit is probablysafeto assumethat
equilibriumrelationis thatthephasesinvolvedareactuallyin therocksarewell equilibratedandtheP-T pointis meaningful
equilibrium,andthisis the greatestpitfall in theapplicationof (exactly what that meaning is will be discussedbelow). If
geothermobarometers. Whereasit is possibleto prove that thereis scatterin thevaluesoutsidetheanalyticalerrorandthe
phasesare not in equilibrium,it is impossibletoprove that an scatter appears to be random, then it probably reflects
assemblageis in equilibrium. If the measuredcompositions disequilibrium.If thevariationis systematic with, say,Fe/Mg
do not represent equilibrium compositions then the or XCa in a mineral,thenit probablyreflectsa deficiencyin the
thermobarometer will yield meaninglessresults. Therefore, calibration.
somecriteria for evaluatingwhetheror not equilibriumwas Powell and Holland [1988] have suggesteda particularly
approachedmustbe established. useful approach to the evaluation of the consistencyof
Becauseequilibriumcan be disproved,but not proved,the thermobarometers.They advocateapplicationof any and all
petrologistis forcedto build a casebasedon self consistency thermobarometriccalibrationsto a suite of samplesfrom a
by conducting a series of tests designed to prove restrictedarea to check for internal consistencyof results.
disequilibrium. If the rock fails all of thesetests,then it is This approachis greatlyfacilitatedby computerprogramsto
permissible to say that the observed phase relations are calculate and plot thermobarometficresultsand should be
consistent with therockhavingattainedchemicalequilibrium. followedwhereeverpossible.
The first test is to check for zoned minerals. If zoned The final test is to consider whether the P-T conditions
mineralsareencountered thenit mustbe decidedwhatportion obtained are reasonable in the regional context. If the
of the zoned mineral is in equilibrium with which other calibrationis very far wrong, then the P-T estimateswill be
minerals in the rock. For example, if a zoned garnet is wrong. Also, it is entirely possible,albeit not likely, that a
encountered, should it be assumed that the rim or the core or suiteof mineralscouldreequilibrateon coolingall to exactly
some point intermediate to the core and the rim is in the samedegreeso that the P-T conditionscomputedfrom
equilibriumwith a biotitethatis in the matrix of therock?Or geothermobarometry wouldreflectcoolingtemperatures rather
shouldit be assumedthattherim of thegarnetis in equilibrium thanpeaktemperatures.The mechanisms of reequilibrationof
with a biotitethatis touchingthe rim? Zonedmineralsare the metamorphicassemblagesand the significanceof closure
rule more often than the exception and interpreting the temperatures arediscussed below.
significance of zonedmineralsis difficultat best. In general,a
compositionmap of the mineral is required as is a good Mechanismsof Reequilibration
understandingof how continuousnet transferand exchange
reactionsoperatein metamorphic rocksandhow diffusioncan
modify zoningprofries. With thesetoolsthe petrologistcan Continuousreactionscan operatealong both the prograde
attemptto interpretcorrectlythezoningpatternandthendecide andthe retrogradeportionof the P-T pathresultingin changes
on whichcompositions arein equilibrium. in thecompositions of mineralsin therock andhencechanges
The secondtest, once mineral pairs or assemblages have in the temperaturesand pressurescomputed from these
been chosenfor evaluation,is to check for crossingtie-line compositions.Eventually,whenthe temperaturebecomeslow
relationsor overlappingphasevolumes. A well-equilibrated enough, the reactions cease and the geothermometeror
suite of rocks may have several mineral assemblagesor a geobarometer is "frozen"in. This freezing-intemperatureis
singlemineralassemblage thatdisplaysconsiderable chemical known as the closuretemperature(Tc), and will be discussed
variation. An example would be pairs of garnet-biotite in more detail below.
associations that spana considerablerangein Fe/Mg. For this There are two typesof continuousreactionsand therefore
testthe tie-linesmustnot cross(or the phasevolumesoverlap) two ways in which rocks can reequilibrateand thus reset
or it would be possibleto write a reactionrelationamongthe thermobarometers. An exchangemechanisminvolvesonly the
minerals. If no tie-lines cross, this is consistent with exchange of two cations between a mineral pair, as, for
equilibrium.Note thatit is not necessary for all garnet-biotite example, the exchangeof Fe and Mg betweengarnet and
pairsto havethe samecomposition. biotite. A net transfermechanisminvolvesthe operationof
The third test is to check for the consistencyof element net transferreactionsand the productionor consumptionof
partitioningbothwithin a singlethin sectionandamonga suite phasesin a rock. Eachmechanism leavesa differentsignature
of samples. This is done by determiningwhetheror not the on the chemical zoning of minerals in the rock and
consequentlyon the interpretationof the thermobarometry.
same
value
ofKtnisobtained
analyseswithin a
section forseveral
or whether setsof
systematic mineral
variations With careful work it shouldbe possibleto interpretcorrectly
of Keqasa function
of bulkcomposition
arefoundin rocks the mechanism and therefore the P-T conditions.
froma singleoutcrop.Notethatit is notessential
thatKeqbe Reequilibration by exchange mechanism. Exchange
identicalin all bulk compositions.For example,KD forFe- reactionsinvolve only the exchangeof two cationsbetween

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18 Spear:Petrologic
determination
of metamorphic
P-T-tpaths

A +Qtz

GaFr
7 iix,_
.-_
B2 , Biotite
Biotite

Fig. 6. (A) AFM diagramshowingtheeffectof theretrograde exchangeof Fe andMg betweengarnetand


biotite duringcooling. G1, G2, B1 and B2 are hypotheticalanalysispointslabeledin (B).(B) Schematic
drawingof a garnet,a biotite that is touchingthe garnetand a biotitein the matrix. Contoursshowthe
schematicdistribution of Fe/(Fe+Mg) in the garnet adjacentto biotite B2. Biotite B2 is assumedto be
unzoned,hencebothB2 analysesgive identicalFe/(Fe+Mg) values.G2 is an analysispoint on the rim of the
garnettouchingthebiotiteandG 1 is an analysispointin thecoreof thegarnet.ModifiedafterRobinsonet al.
[1982].

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

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Spear:
Petrologic
determination
ofmetamorphic
P-T-tpaths 19

A
Sillimanite

A + Qtz
+ Kfs

Garnet G2/

B2\ B1
F M
Biotite

Fig.7. (A) AFM diagram showing theeffectof continuous


retrograde
nettransferreaction
ontheassemblage
garnet+ biotite+ sillimanite+ quartz+ K-feldsparwithisobariccooling.G1, G2 andB2 arehypothetical
analysispointslabeledin (C). The composition B 1 is unattainable.ModifiedafterRobinsonet al. [1982].
(B) P-T diagramcontoured for isopleths
of Fe/(Fe+Mg)in garnetin assemblagesthatcontaingarnet+ biotite.
AFM diagrams indicate
thestableassemblagein eachP-T field.Largedotandarrowshowhypothetical peak
metamorphic conditions andisobariccoolingpath.FromSpearandCheney[1989]. (C) Contourmaps
depicting
distribution
of Fe,Mg andMn in a highgradegarnetfromcentralMassachusetts [fromTracyet al.,
1976].Gi: garnetcoreanalytical
point;G2:garnetrimanalyticalpoint;B2:matrixbiotiteanalytical
point.

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

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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

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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

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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.

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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

closuretemperaturesand it is not always obviousto what


portionof the P-T paththeclosuretemperature refers. Also, 0 700
1--
where multiple thermometersand barometersare being
applied,therelativeclosuretemperatures of differentequilibria
mustbe considered.Somethermobarometers are exchange
600

reactionswheretheratelimitingstep may be intracrystalline


diffusionin a mineral suchas garnet. Others,basedon net 500,

transferreactions,may have grain-boundarydiffusion or


surface kinetics as a rate limiting step. Still other 400
complications arecausedby retrograde reactionsthatinvolvea 0 20 40 60 80 100 120 140

fluid wherethe rate limiting stepmay be the accessibility of Time (Ma)


l'luid. Theproperapplication
of geothermobarometry
must
considerall of thesecomplications,
especiallyin highgrade lO /A,B,C ;posltlon
rockswherereequilibration
on coolingis a certainty. _

Diffusi.
onalHomogenization
of Garnet

A secondquestionto addresswith respectto the application


of thermobarometry
to thecoresof crystalssuchas garnets
from high gradeterranesis "Under what conditionsdoesthe
corecompositionof thecrystalrepresentthecomposition at the
peak of metamorphism?". An approximateanswerto this
questioncan be obtainedby application of the equations of
binarydiffusionin a spherein the contextof hypothetical
temperature-time
pathsof metamorphism.
The equationsof binarydiffusionin a spherearepresented - In,hal / t- / I-H
by Crank[ 1975,chapter6). Nondimensionalized solutionsto
this equationare plottedby Crank [1975: Fig. 6.1] for the
o
o
t C Ip t I I I I I
4 6 8 lO
Core r(cm)

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

Lettersrefer to T-t curvesof (A). O5


(C) Plot of concentrationvs r/a (normalized radius) for Imtal
diffusionresultingfrom T-t curveG (Tmax = 585 *C) for 0 Co
,mjpostlon
garnetsof differentradii. Initial andboundaryconditionsasin 0 2 4 6 8

(B). Numbersrefer to garnetradiusin cm. Core r/a

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

2tl Spear:Petrologicdetermination
of metamorphic
P-T-t paths

interpolatessome additional ones. For comparisonwith O'F


2= OF/Ozl)
oZl2+ (OF/Oz2)
Oz22+
Figure8, it shouldbe notedthatthecoolingratesindicatedby
the T-t curvesof Figure 9A begin at 0 'C/M at the thermal
maximum and reach maximum valuesof approximately5 25'.5'.Pzizj
()F/'dzi)(OF/Ozj)
Ozi0.5Ozj
0-5 (109.2)
'C/Ma. Using the values for Fe-Mg diffusion in garnet i j
estimatedby Lasagaet al. [1977] it is possibleto compute
numericallyvaluesof nondimensionalized time where
Oziistheerror
ofthezithmeasurement
and
Pzizj
isthe
covariance
of thezi andzjthmeasurements.
Assuming
that
t' = t D(T)/a2 ,AtD(T)/a2 (109.1) analyticalerrorsareon the-orderof _+3-5%andthatthereis no
covarianceof measurements, thisformulapredictsa precision
of approximately _+30-50 'C for Fe-Mg exchange
for each T-t path for a given garnet radius. The final
thermometersand -+1000-2000bars for garnet-plagioclase
diffusionalzoningprofile for specifiedT-t pathsand garnet geobarometers.The fact that this methodof computingthe
radii can thenbe plottedas functionsof the T-t path(Figure errorresultsin errorslargerthanthoseobtainedfromrepetition
9B) or asa functionof garnetradii (Figure9C). of the experiment suggeststhat a moderate amount of
Figure 9B reveals that for garnetswith a radiusof 1 cm,
covarianceexistsin themeasurement of mineralcompositions.
completehomogenization of the garnetwill occuralongT-t The accuracyof the P-T estimate is a measureof how
pathsthat have thermalmaximaof approximately775 'C or closelythe estimatereproducesthe real P-T conditions.This
greater(T-t pathsA, B andC in Fig. 9A). The composition of erroris considerably moredifficult to evaluate,butobviously
the core of the garnetis modified alongT-t pathsthat have criticalto know if metamorphicP-T estimatesareto be usedto
thermal maxima greater than approximately 725 'C. constrain the thermal evolution of orogenic belts. The
Significantalterationof the zoningprofileis notobserved in T- accuracyof a thermobarometer is a functionof three major
t pathsthat havethermalmaximaof lessthanapproximately factors:(1) the accuracyof the calibration;(2) the ability of
600 'C (T-t pathsG and H in Fig. 9A). Conversely,Figure
solution models to represent accurately the activity-
9C revealsthat alonga T-t path with a thermalmaximumof
compositionrelations;and (3) the accuracyof the electron
585 'C (path G in Fig. 9A) completehomogenization will
occur in garnets with radii of less than 0.01 cm, the microprobeanalyses.
compositions of the coresof garnetswith radii lessthat 0.05 The accuracyof a P-T estimateis very difficult to estimate
because the three sources of error cited above are not well
will be alteredandthe zoningof garnetswith radii greaterthan
approximately0.5 cm will not be seriouslyaffected. constrained andthe covarianceof errorsis evenmorepoorly
These considerationsare clearly quite importantfor the known. Hodges and McKenna [1987] and Hodges and
interpretation of garnetcorecompositions with respectto their Crowley [1985] haveaddressed the questionof accuracyof
usein thermobarometry.One mustconsidernot only the T-t thermobarometric resultswith analyticalandMonte-Carloerror
historyof the rock to ascertainwhetheror not the garnetcore propagationroutines. Accordingto Hodgesand McKenna
composition will be modifiedbut alsotheradiusof thegarnet. [1987] theaccuracyof temperature estimatesmadeemploying
As a generalruleof thumb,for largegarnets(radiigreaterthan the experimentally calibratedFe-Mg exchangebetweengarnet
and biotite [Ferry and Spear,1978] is approximately+150 'C
1 cm) thatreachedpeaktemperatures below approximately 740
at constantpressureand the accuracyof garnet-plagioclase
'C, thecoreof the garnetshouldreflectthecomposition at the geobarometers is approximately-+5kbar. The fact that these
peakof metamorphism. errors are so large is surprisingbecausethey cover most of
crustalmetamorphic conditionsandsuggests thattheremay be
major covariances of errors.
Error Analysis:PrecisionandAccuracy Anotherway to estimatethe accuracyof thermobarometric
resultsis to comparethe resultsobtainedfrom several'
The final consideration that must be made in the independent techniques. For example, pressure and
interpretationof geothermobarometric resultsis the precision temperatureestimatesfrom samplescollectednear the field
andaccuracyof the P-T determination. exposureof the A12SiO5triple point in New Hampshireby
Precisionis the abilityto reproducetheexperimental results Hodgesand Spear[1982] andin New Mexico by Grambling
by repeatingthe experimentalmeasurements.Applied to [1981] indicate that the garnet-biotite Fe-Mg exchange
geothermobarometry, precisionis reflectedin the scatterof P- thermometer and garnet-plagioclase geobarometersare
T estimatesthat arise from errors in electron microprobe consistentwith the P-T conditionsof the A12SiO5triple point
analyses.For example, a measureof the precisionmay be as determinedby Holdaway [ 1971]. This type of resultdoes
obtainedby analyzing10 garnet-biotite pairsfrom a singlethin not prove the accuracy of the P-T estimate, but rather
sectionandcomputing isopleths of Keqfor each. ff thesample demonstrates the internalconsistencyof differentmethodsof
is well equilibratedand satisfiestheriteria for equilibrium estimating P-T conditions. If the accuracy of these
outlined
above,thenthespread
of theisopleths
of Keqona P- thermobarometerswere, in fact, as poor as suggestedby
T diagramreflect the precisionof the measurement.For the Hodges and McKenna [1987], then this type of correlation
Fe-Mg exchangethermometers,the precision based on shouldnot occurexceptfortuitously. It mustbe emphasized,
repeatedanalysesis generally+_20-30Cat a givenpressure. however,thatjust becausea thermobarometer appearsto give
For geobarometersbasedon the coexistenceof garnet and accurateresultsin oneP-T rangeandin rockswith a restricted
plagioclase,
theprecisionis generally+300-500barsat a given range of bulk compositions,this does not mean that the
thermobarometer will be accurate over all P-T conditions. For
temperature.
Another way to estimate precision is to use the error example,
theincrease
in Ti andA1VIcontent
of biotites
with
propagationformula,which,for a functionF of the variables increasingtemperaturein many naturalpelitesmay seriously
Zl, z2, z3 etc., gives: affecttemperatures
estimatedusinga calibrationthatdoesnot

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

26 Spear:Petrologic
determination
of metamorphic
P-T-tpaths

thesevariables,however,are mosteasilycomputedthrough Themassbalanceconstraints(equations35) maybeusedto


application
of thedifferentialformsof theseequations. modeleitheropensystembehavioror closedsystembehavior.
The appropriateequationsfor the applicationof differential With closedsystembehavior,the changein massof each
thermodynamics arethetotaldifferentials
of theequations used systemcomponentis zero;hence,equation(35) becomes
abovefor the calculationof phaseequilibria. Theseare the
thermodynamic constraints,
the stoichiometricconstraints and
the mass balance constraints:
0 = YMk
Znij,k
dXj,k+ ( ni,j,k
Xj,k)dMk (113)
k j k j
0=(RlnKeq
- (AS(TR,PR)
+I(ACffT)dT))
dT+AVsdP
Equations(40), (112) and (113) form a systemof linear
+ RTdlnKeq (30) differential
equations
in thevariables
dT,dP,dXj,kanddMk.
or
As was discussedabove,if massbalanceequationsare not
employed (equation 113), the variance of the systemof
equationsis the same as the phaserule variance. If mass
0=(AHfT)
+ITCpdT
+AVs(P-1))dT
+AVsdP balanceconstraintsare employed,then the varianceof the
systemof equationsis 2 if closedsystembehavioris assumed
(dmi = 0), consistent with Duhem's theorem, otherwise the
+ RTdlnKeq (31) varianceis equalto 2 plusthenumberof components to which
the systemis open.
Therearetwo majoradvantages to thedifferentialformsof
thethermodynamic expressionsovertheintegratedformsfor
0: .dXj,k (40) the calculation
of P-T paths. Firstly,enthalpydataare not
J
explicitlyrequiredbecausethe enthalpyof reactioncan be
inferredfromthevalueof theequilibriumconstantat T andP.
Secondly,the equationsare linear so that direct solutionfor
dmi= ZMk Zni,j,kdXj,k+ 5(5ni,j,kXj,k)dMk (35) changesin P, T, X and M can be madewithoutiteration. The
k j k j
astutereaderwill have noticedthat the Newton-Raphson
algorithmfor the solutionof the nonlinearthermodynamic
Either form of the equilibriumconstraint,equation(30) or equationsis very similarto the differentialequationsused
equation(31) is acceptable,but use of equation(30) has a here. The majordifferenceis thatbeforewe weretryingto
major advantage:enthalpyof reactiondataare not explicitly find a set of P-T-X-M valuesthat satisfiedthe equations
requiredbecausethe compositions of the coexistingminerals simultaneously. Herewe aretryingto findchanges in P-T-X-
in theequilibriumassemblage canbeusedto infer theenthalpy M valuesawayfrom a setof referenceconditions.
of reactionthroughtherelationship An alternativeway of formulatingtheaboveproblemis by
the Gibbs method [Spear et al., 1982a]. With the Gibbs
AH(TR,PR)
=-IACpdT
+T(AS(TR,PR)
+I(/XCp/T)dT)
- method, the fundamental thermodynamic variables are
arbitrarilychosento bedP,dT anddgj,kandanadditional set
AVs(P-
1)- RTlnKeq (110) of equations are addedso that the 9ariablesdXi k may be
addedto thesystem
of equations.
In theaboveethodthe
fundamental
variables
arechosen
to bedP,dT anddXi,k. The
providedAS(TR,PR),AVs,Keq, ACp,P andT are also variable dgi k may be added if desired, but is gnerally
known. Therefore,theinputdatanededfor theapplication of unnecessary
Jtrmostapplications.
Themajoradvantage
of
differentialthermodynamics to the inferenceof metamorphic the present method over that of the Gibbs method is
P-T pathsare the entropiesandvolumesof reactionand a set computational: the system of equations to be solved is
of equilibriummineralcompositions at the temperatureand considerably smallerthanwith theGibbsmethodandsolutions
pressureof equilibrafion. may be obtainedwith fewercomputations. Bothmethodsgive
As before,the assumptionof ideal ionic activity models numericallyidenticalresults.
permitsthedifferentialof theequilibriumconstant to be written As an exampleof the equationsusedin the applicationof
as (seeequation47) differentialthermodynamics, consideragainthe assemblage
olivine+ pyroxene+ quartzin the systemSiO2-MgO-FeO. If
)j,kCZj,kdXj,k olivine and pyroxeneare both binary Fe-Mg solid solutions,
dlnKeq
= Y.( ) (111) then thereare two linearly independentreactionsamongthe
phasecomponents:
Xj,k
andthethermodynamic
constraint
(equation30) to be written Fs - En - 0.5(Fa - Fo) = 0 (11)

and

0=(RlnKeq
- (AS(TR,PR)
+I(ACp/T)dT))
dT+AVsdP Qz + Fo- 2En = 0 (12)

j,ka,kdX,k for which the two differential expressions of the


+ RTZ(, ) (112) thermodynamic
constraints
taketheform (assuming
idealionic
Xj,k solution):

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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)

dXFs,Px dXEn,Px dXFa,Ol dXFo,Ol dmFeO=


RT( - - + ,) (114)
XFs,Px XEn,Px XFa,OI XFo,OI
0 = 0 + MOI(0-dXFo,OI
+ 2'dXFa,Ol)
and
+ Mpx(0'dXEn,Px
+ l'dXFs,Px)

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)

2dXFo,Ol 2dXEn,Px Theseequationscan be combinedin matrix form as shownin


RT( - ) (115) Table 2.
XFo,Ol XEn,Px Applicationsof the systemof equations(40), (112), and
(35 or 113) (e.g.Table2) aremanyand,in general,dependon
where the varianceof the assemblage.Severalexampleswill be
discussedbelow, after a generaldiscussion
of a procedurefor
XFs,PxXFo,Ol obtainingsolutions.
Keq,ll = (116) Solutionof the Systemof Equations
XEn,PxXFa,OI
and As a generalmethodof solutionof the systemof differential
thermodynamicequations,considera systemwith a variance
of v. In such a system,there are v independentvariables,
(XFo,OI)
2 whichmay be arbitrarilychosen.The only criterionthatmust
Keq,12
TM (117) be satisfiedin the choosingof variablesis that they must be
(XEn,Px)
2 linearly independent.Linear independencecan easily be
checked,for if the variableschosenare not independent,then
The two stoichiometric constraints take the form the resultant matrix obtained by removing the columns
correspondingto these variables will be singular As an
0 = dXFs,Px
+ dXEn,Px (118) example of non-independentvariables, if the phase rule
varianceof an assemblage is 1 andmassbalanceequationsare
and used,then the systemof equationswill have a varianceof 2,
butonlyoneof theintensive
variables
(dP,dT, dXj,k)is
0 = dXFa,Ol+ dXFo,Ol (119) independent. The other variable chosenmust be a mneral
abundancevariable (dMk). If the phaserule varianceis 2 or
Assumingclosed systembehavior, the three mass balance greater,
thenanycombination
of twodP,dT, dXj,k,or dMk
constraints are variablesis independent
Once a set of independentvariablesis chosen,then all n
dmsio2TM
0 dependentvariablesmay be expressedas functionsof the v
independent variables:
0 = MQzdXQz,Qz+ MoI(dXFo,01+ dXFa,01)
+ Mpx(dXEn,Px+ dXFs,Px) O1 = Ol(Zl,Z2.....Zv) (124)

+ dMQz + dMol(XFo,Ol+ XFa,O1) 02 TM02(Zl,Z2.....Zv) (125)


+ dMpx(XEn,Px+ XFs,Px) (120)

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...

+ MPx(l'dXEn,Px+ 0'dXFs,Px) ..+ (}01/}Zv)zi:v


dzv (127)

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

28 Spear:Petrologicdetermination
of metamorphic
P-T-t paths

TABLE 2. Systemof equations


for theassemblage
olivine+ pyroxene
+ quartzin thesystem
SiO2-FeO-MgO

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

A11 RlnK 11 AS1I(TR,PR)


- {(ACp,11/T)dT
A12= RlnKeq,
12 AS12(TR,PR)
J(ACp,12fr)dT

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:

AO1= (301/3Zl)zi;lAZl+ (301/3Z2)zi;2


Az2
dn= (On/Zl)zil
dzl+(On/Z2)zi2
dz2... ..+ (301/3Zv)zi;v
AZv (130)
..+ (On/Zv)zivdzv (129) AO2= (302/3Zl)zi;qAZl + (302/3Z2)zi;2
Az2
In matrix form, equations127-129 may be writtenas' ..+ (302/3Zv)zi;v
AZv (131)
,

dO1 (301/3Zl) (301/3z2)... (301/3Zv) dzl

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)

(301/)Zl) (301/3z2)... Az1.


or

A02 (302/3Zl) (302/3z2)... (302/3Zv) Az2


0 = J- z (129.2) o .

. .

where is the n x 1 vectorof differentials


of thedependent
variables,J is the n x v matrix of partial derivativesand Z is (On/OZl)
(OOn/OZ2)...
(On/OZv)
the v x 1 vectorof differentialsof the independent variables.
The matrix J is called the Jacobianmatrix and equations (132.1)
(129.1) and (129.2) are a standardmathematical transforma-
tion of variables. Additional information on the mathematics Solutionto the systemof equations(127-129.2) or (130-
of Jacobians can be found in texts on calculus [e.g. 132.1) may be obtainedby matrixmanipulationof the system
Hildebrand, 1976] or in the thermodynamictext by Callen of homogeneous lineardifferentialequationsthatincludesthe
[1960]. thermodynamic constraint(112), the stoichiometfic
constraint
Changesin the dependent
variables1, 2 ....On may be (40) and, if desired,the massbalanceconstraint(35 or 113).
approximated by calculation of the partial derivatives In matrixnotation,theseequationstaketheform:

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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

0 Mix Mix MO! 1 1 1 o -Mol

0 0 Mpx 0 0 2XFo,OI XEn,Px 0 -2MoI

0 Mpx 0 2Moi 0 2XFa,OI XFs,Px 0 0

A11= RlnKeq,11
- AS1I(TR,PR)
- {(ACp
11/T)dT
A12= RlnKeq,
12 AS12(TR,PR) J(ACpi12)dT

AX =0 (133) Az2....Azv). In practice,thesesolutions


may be foundby
eithermatrixinversion,asin equation(135) or by Gaussian
X is a (n+v) x 1 vectorthat containsthe differentialsdT, dP, elimination with back substitution. New values for the
dX; k and dMk A is an n x (n+v) matrix that containsthe dependentvariables01, 02...On may be obtainedby the
coeJBcients
of'dT,dP,dX,etc.fromthethermodynamic,
relations:
stoichiometric and mass balance constraints. These matrices
areshownin Table2 for theassemblage olivine+ pyroxene+ (new) = Oi (old) + AOi (136)
quartzin the systemSiO2- MgO - FeO.
Both A andX may be split into two parts,one part that andfor theindependent
variables
by
containsthe coefficientsfor the dependent
variablesandthe
other that containsthe coefficientsfor the independent zi (new) = zi (old) + Azi (137)
variables. Thus
The procedureoutlined above is a form of numerical
A'O =-B Z integration
(134) wherethe calculated derivatives(}01/Zl)zil,
(}01/i}Z2)zi2....(}01/i}zv)ziv,are multipliedby finite
where0 is the n x 1 vectorof dependent variablesdO1, changes in theindependent variables to findthefinitechanges
dO2...dOn, A' is the n x n matrix of coefficientsfor the in thedependent variables.It is importanttorecognize thatthe
dependentvariables,Z is the v x 1 vectorof independent derivativesare not constantoverall of P-T-X-M space,but
variables dzl, dz2...dzv and B is the n x v matrix of dependon the initial conditions(P-T-X-M). For small
coefficientsfor the independentvariables. Table 3 showsthe changesin the independent variablesthederivativesmaybe
matricesfor the assemblage olivine + pyroxene+ quartzin the consideredconstantand changesfrom one stateto another
system SiO2 - MgO - FeO partitioned such that dT and computedin one iteration. However,for largechangesin
dXFo,O
1aretheindependent
variables. independentvariables,
it is necessaryto iteratein smallsteps
Premultiplication
of eachsideof equation
(134)by A'-1 andto recomputethe derivativesaftereachiteration. Justhow
results in small a step is required dependson the specificsof the
problem and the numericalprecisiondesired. The best
0 = [A'-1 (-B)] Z (135) approach is to repeatthecalculations with increasingly
small
stepsuntil thedesiredprecisionis achieved.
The procedurerequiredto perform a seriesof iterative
Comparisonof equation (135) with equations(129.1 and calculations is:
129.2) reveals that they are equivalent. That is, the (n x v) (1) Choosea referencepressure,temperatureand set of
matrix[A '-1 (-B)] is theJacobian matrixJ andcontainsthe mineralcompositionsandmineralabundances.
desiredpartialdifferentials,OO1/i}Zl)zil, (i}01/Z2)zi2, (2) Choosethevariablesto be independent(Zl, z2...Zv).
..001/Zv)ziv ,etc..Solution
for thefinitedifferences
AO1, (3) Choosevalues for the changesof thesevariables(Azl,
A02 .... AOn (e.g. equations 130-132.1) is obtained by Az2...Azv).
multiplicationof [A '-1 (-B)] by the vectorZ (i.e. AZl, (4) Computethe valuesof the coefficientsfor the coefficient

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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

arbitrarychangein pressure. To draw a completeP-T where muscovitebreaksdown the assemblageis garnet +


contour,theequations
(141-143)aresolvedfirstat theinitial biotite + A12SiO5+ K-feldspar+ quartzand isoplethsare

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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

FeMg.1 (garnet) = FeMg.1 (staurolite) (144) staurolite


+ biotite+ quartz= garnet+ muscovite
+ H20 (146)

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

32 Spear:Petrologic
determination
of metamorphic
P-T-tpaths

TABLE 4. Initial conditions (T -- 520 C,P -- 3.5kb),partialderivatives


and
finitedifferencesfor theassemblage garnet+ biotite+ staurolite
+ muscovite+
quartz+ plagioclase+ fluid (H20) in the systemMnNCKFMASH.

AP = 100 bars AXAlm = 0


OOld (Oi/)P)XAlm (Oi/)XAlm)P /5,0 ONew
(3) (1) (2) (3) (3)

T 520 -0.13002E-01 0.37392E+04 -1.3 519


p4 3500 ...... 100 3600
XAn 0.243 -0.42806E-04 0.69734E+00 -0.0043 0.2387
XAlm4 0.682 ...... 0 0.6820
xXsps 0.161 -0.10237E-04 -0.22519E+01 -0.0010 0.1600
Grs 0.038 0.89570E-05 -0.7 4561E+00 0.0009 0.0389
XAnn 0.463 -0.14593E-04 -0.90558E+00 -0.0015 0.4615
XMnBt 0.003 -0.60124E-06 0.31526E -01 -0.0001 0.0029
XFeSt 0.793 -0.13645E-05 -0.17640E+01 -0.0001 0.7929
XMnSt 0.028 -0.39990E-05 0.62917E-01 -0.0004 0.0276
MQz 0.20 -0.16221E-04 -0.34011E+01 -0.0016 0.1984
MH20 0.0 0.40554E-05 0.85027E+00 0.0004 0.0004
MMs 0.25 0.96577E-05 0.15990E+01 0.0010 0.2510
Mp1 0.10 -0.56547E-05 0.92120E -01 -0.0006 0.0994
MGar 0.15 0.14246E-04 0.21351E+01 0.0014 0.1514
MBt 0.20 -0.96577E-05 -0.15990E+01 -0.0010 0.1990
Mst 0.10 -0.20277E-05 -0.42513E+00 -0.0002 0.0998

1) Units are C/bar,mole fraction/baror moles/bar


2) Units are C/molefraction, mole fraction/mole fraction or moles/molefraction
3) Units are C,bars, mole fraction or moles
4) Independentvariables

Note thatisoplethsof XMn,Gar(Fig. 10D) alsohavenegative distributionof an exchangecomponentbetweentwo phases,


slopesbut displaya monotonicdecrease in XMn,Garwith and someare net transferreactions[Thompson,1982], which
increasingT. Isoplethsof XCa,Gar(Fig. 10B)havemoderate affect the compositionand the amountsof phasespresentin
, to steeppositiveslopesthat form a reasonablyhigh angleof the assemblage.
intersection
withthoseof XFe,Gar
andXMn,Gar indicating
that For example,equation(68) is the Fe-Mg exchangereaction
the combinationof XCa,Garwith one of theseothermole betweengarnetand biotite and hasthe resultof affectingthe
fractionswouldyield fairly preciseP-T intersections. Fe/Mg in coexistinggarnetandbiotite. The amountof garnet
As with Figure 7B, diagrams such as those shown in or biotite in the assemblageis not affectedby this reaction
Figure 10 can be used to interpretthe chemicalzoning in except insofar that the molar volumes of the Fe and Mg
garnetandothermineralsin thisassemblage. For example,an endmember garnet and biotite components are slightly
isobaricheatingpath startingat thereferenceP-T conditions different. Equation (146) is a net transferreaction,which
(dot in Figure 10) would producea garnetcrystalwhose resultsin the productionof garnet+ muscovite+ H20 at the
almandinecontentfirst increasesand thendecreases,while the expenseof staurolite+ biotite+ quartzasthereactionproceeds
spessartine
and grossularcomponentsboth decrease.Biotite to the right. This reactionplays a dominantrole in changesin
and staurolite would both show decreases in Fe and Mn modalabundances of phasesthatareexperienced by therock.
contents. Under conditionsof equilibrium crystallization Thompsonet al. [1982] and Thompson[1982] proposed
plagioclasewouldbecomeslightlymoreanorthitic.However, plottinga linearlyindependentsetof net transferreactionsfor
if fractionalcrystallization
of garnetprevails,aswouldbe the an assemblageas a "reaction space". Changesin modal
caseif zonedgarnetsare beingproduced,then plagioclase mineralogyestimatedfrompetrographic analysiscouldthenbe
would haveto becomemore albiticas a consequence of the plotted in the reactionspaceand relative P-T pathsinferred
from the trends observed.
fractionafionof Ca intogarnetasgarnetgrows.Complications
resultingfrom fractional crystallizationof phaseswill be As an example, in the assemblagegarnet + biotite +
discussed in more detail below. stau:olite + muscovite + plagioclase + quartz in the
MnNCKFMASH systemthereare two linearly independent
P-T-X-M: ReactionSpaceandMineral Abundance
Diagrams net transferreactionsthat may be written amongthe phase
components of themineralsin theassemblage, equations
(146)
For every mineralassemblage,a linearlyindependentsetof and (79). The reactionspacefor thesereactionsis shownin
stoichiometricrelationsamongthe phasecomponentsof the Figure11 whereeachaxisis definedby progressalongoneof
mineralsmay be written,asdiscussed earlier.In general,some the two reactions.Becausestaurolite,quartzandH20 appear
of thesereactionsareexchangereactions,whichonly affectthe in reaction (146) and not in reaction (79), progressalong

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Spear:Petrologic
determination
of metamorphic
P-T-tpaths 33

10 10 X,o

8 8 XAn
Pt
o
16-___._._.

4 4 -0 24..... _

400 500 600 700 400 500 600 700

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

Fig. 10. P-T diagramsdepictingisopleths of garnet,biotite,stauroliteandplagioclasecomposition for the


assemblage garnet+ biotite+ staurolite
+ muscovite
+ quartz+ plagioclase + fluid(H20) in thesystemSiO2-
A1203- MgO - FeO- MnO - CaO- Na20 - K20 - H20 (MnNCKFMASH).Reference conditions(largedot)
aregiveninTable4. (A) Isopleths
ofXFe.,Gar
(B)Isopleths
ofXCa,Gar
andXAn,PI(C)Isopleths
ofXFein
biotiteandstaurolite(D) Isopleths
of XMntn garnet,staurolite
andbiotite

reaction(146) may be describedin termsof changesin modal differenttrajectoriesthroughreactionspaceshouldrepresent


amountsof thesephases.Similarly, progressalongreaction differentP-T paths. Thompsonet al. [1982] advocatedusing
(79) may be describedin termsof changesin modalamounts net transferreactionswith asdifferentP-T slopesaspossible
of plagioclase. for thispurpose.Applicationsby Thompsonet al. [1982] and
The origin of the reaction space is an arbitrarily chosen Thompson[1982] includeexaminationof the systematicsof
referencepoint with a given setof mineralcompositions and the metamorphismof basalticrocks, the reaction spacefor
modes. Progressalong any vector in reaction spacewill whichwascalibratedusingnaturalsamplesandexperimental
modify the amountsand compositionsof the phasesin the studies. An example from a pelitic schist is given by
assemblageuntil either one or more phasesreaches zero Chamberlain[ 1986].
abundance or an endmembercomposition.The reactionspace A methodfor calibratingreactionspacewith respectto P
is thus boundedby lines marking where a phaseor phases and T can be developedfrom differential thermodynamics
reach zero modal abundanceor the limit of its exchange because the necessary relationships among pressure,
potential. The figure formed by these lines is called the temperatureand reactionprogressare containedin the setof
"reactionpolygon" [Thompson,1982]. Note that the size, differentialequationsamongthe variablesdT, dP, dX anddM.
shapeand even the facesof the reactionpolygondependon Considerfirst thatthe varianceof the systemof equationsfor a
relativemodalabundances andcompositions of themineralsat closedsystemwheremassbalanceconstraints are employedis
the origin. 2, as specified by Duhem's theorem. Therefore, any 2
Thompsonet al. [1982] and Thompson[1982] proposed independentvariables in such a systemmay be chosenas
that reactionspacecouldbe a usefulpetrologictool because independent and the "space" described by these two
changesin modal abundancesobservedin a suiteof samples independentvariablescontouredwith any of the dependent
couldbe plottedin thereactionspaceandthe observedtrends variables.For example,it is possibleto contourreactionspace
usedto infer relative P-T paths. Becauseeach net transfer with temperature, pressure and mineral composition.
reactionhas, in general,a different slopeon a P-T diagram, Alternatively,it is possibleto contourP-T spacewith mineral

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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

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Spear:Petrologicdetermination
of metamorphic
P-T-t paths 35

10

400 500 600 700

T Deg C

Fig. 12. Mineral abundanceisopleths(in moles)of garnet(solidlines), biotite (dashedlines), staurolite(dot-


dashedlines)andplagioclase(dottedlines)for the systemdepictedin Fig. 10 andTable 4. Largedot shows
reference P-T conditions.

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.

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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

The exactreactionstoichiometry alonganyP-T vectorcan TABLE 5. Partialderivatives for theassemblage


readilybe derivedfrom the differentialequationspresented garnet+ biotite+ staurolite
+ muscovite + quartz+
above. For this applicationmass balanceequationsare plagioclase+ H20 in the systemMnNCKFMASH.
requiredand,assuming closedsystembehavior,thevariance
of the systemof equationsis 2. The independent
variablesare 0 (30/3T)p (30/3P)T
chosen to be P and T so that
() (2)

X2,A= F(P,T) (153) X^n 0.18649E-03 -0.40381E-04


XAlm 0.26744E-03 0.34772E-05
X1,B = F(P,T) (154)
XSps -0.60223E-03 -0.18067E-04
XGrs -0.19940E-03 0.63644E-05
MA = F(P,T) (55) XAnn -0.24219E-03 -0.17741E-04
XMnBt 0.84312E-05 -0.49162E-06
MB = F(P,T) (156) XFeSt -0.47175E-03 -0.74980E-05
and XMnSt 0.16826E-04 -0.37803E-05
MQz -0.90956E-03 -0.28047E-04
MH20 0.22739E-03 0.70119E-05
AX2,A= (aX2,A/c]P)T
AP+ ()X2,A/c]T)p
AT (57)
MMus 0.42762E-03 0.15218E-04
AX1,B= (ohXl,B/ohP)T
AP+ (ohXl,B/ohT)p
AT (58) Mplg 0.24636E-04 -0.53344E-05
MGar 0.57100E-03 0.21670E-04
AMA = (c]MA/'0P)T
AP+ (0MA/c]T)p
AT (159) MBt -0.42762E-03 -0.15218E-04
MSt -0.11370E-03 -0.35059E-05
AMB = (c]Mldc]P)T
AP + (c]MldOT)p
AT (160)
1) Units are mole fraction/*C or moles/C
For arbitrary changesin P and T the changein mineral 2) Units are mole fraction/bar or moles/bar
compositionand abundanceof phasescan be computed.
Therefore,for anyP-T vectorthechangein molesof anyone
phaserelative to any other can be computed.The relative This analysiscan readily be invertedand if the reaction
changesin themolesof phases computed in thiswaycanthen stoichiometry can be estimatedfrom texturalanalysisof the
be arrangedin theform of a wholerockreactionthatwill occur sample, the P-T vector associated with this reaction
alonga specifiedP-T vector. The stoichiometriccoefficients stoichiometry canbe inferred.Followingtheaboveprocedure,
of phasesin thewholerockreactiondependon thedirectionof if massbalanceconstraints are employedthe varianceof the
the P-T vector; the magnitude of the coefficients can be systemof equationsis 2 soonly 2 variablesare independent.
normalizedto anyconvenientvalue. Thismeansthatthemodalchanges of only twophases(or the
Supposeit is desiredto computethe whole rock reaction ratio of the changesof two phases)is requiredto infer a P-T
stoichiometryalonga P-T vectorwith a slopeof 30 bars/*C. vector. The independentvariablesare chosento be the two
Equations(159) and (160) can be solvedwith AP = 30 bars variables for which modal abundance data are best constrained
and AT = 1 *C (or somemultiple of thesevaluesof AP and (e.g.MA andMB) andtheequations
AT) andthe changesin molesof phasesA, B, etc. computed
(i.e. AMA, AMB, etc.). Thesechangesin mineralabundance P = F(MA,MB) (163)
can thenbe arrangedin the form of a wholerockreaction.As
an example, consider the assemblagegarnet + biotite + T = F(MA,MB) (164)

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Spear:Petrologic
determination
of metamorphic
P-T-tpaths 37

and reactionsto be overstepped


or incompletereactionsto occur.
Slow diffusionratesmay resultin chemicalheterogenities
AP = OP/i)MA)MB
AlMA+ (i)P/i)MB)MA
AMB (165) within a sample or chemical zoning within a crystal.
Metasomaticeffectswill shiftthebulkcomposition
awayfrom
AT = ()TMA)MBAMA+ ()TMB)MAAMB (166) the initial state.
The important feature to recognizeabout all of these
can be solvedfor changesin P and T consistentwith the processesis that they are path dependent. That is, the end
observedchangesin MA andMB. productof the metamorphic processdependson the specific
The estimation of whole rock reactions has been addressed pressure - temperature - time - reaction - diffusion -
in the literature and some discussion is warranted here. The metasomatism paththatis followedby therock. Equilibrium
questionis usuallyposedas "By whatreactionarethesetwo calculationscanprovidean endmembercasefor the behavior
rocks,collectedat differentmetamorphicgrades,related?". of a rock,butcannotexplainmanyphenomena because of the
The problemwith thisquestionis thattheanswerdepends on pathdependence of manyimportantmetamorphic processes.
theP-T pathtakenfromonerockto theother.The question is A complete descriptionof theevolutionof a metamorphic
rock
akinto thequestion"How muchgasolinedoesit taketo drive requiresrigorouskineticanalysisof all thesephenomena and
from pointA to pointB?". The answerdependson theroad is beyondthe currentlimit of knowledge. However,it is
takenandthe speeddriven. possible to examine some path-dependentprocesses,
Leastsquaressolutionshavebeenproposedto answerthis particularlythosethatinvolvechanges in bulk composition,
question[e.g. Greenwood,1968;Laird, 1980;Pigage,1982; withtheequations of differential
thermodynamics byinvoking
seereview by Spearet al., 1982b]. The leastsquaressolution theconceptof localequilibrium.
provides the reaction stoichiometry along the shortest Processesthateffectchanges in thebulkcomposition
of the
compositionalvector betweenthe two assemblages.The rockarepathdependent because
theendproductdepends on
methodoutlinedabovepermitssolutionfor differentreaction the amount the bulk compositionchangesand the P-T
stoichiometries alongdifferentP-T trajectories.For example, conditionswhen the bulk compositionchanges. Both
it is possibleto solvefor thereactionstoichiometry alongthe fractionalcrystallization,
suchasin theproduction
of a zoned
shortestP-T vectorbetweenthe two samples;this will not, in garnetcrystal, and metasomatism,suchas the infiltration of
general, be identical to the least squares solution. exoticfluids,areprocesseswherebythebulkcomposition of
Alternatively,one can solvefor the reactionstoichiometry the rock is changed. Both fractional crystallizationand
along any P-T path by iterative solutionof equations(159- metasomatism areexamplesof opensystembehaviorthatcan
160). be modeledusingthe differentialthermodynamics formalism
A more seriousproblemwith the leastsquaresapproachis presentedabove.
thatreactionssoderivedmay haveno geologicalsignificance Opensystembehavioris modeledby addingas additional
in that,the reactionsmay bearno resemblance
to reactionsthat variablesto the systemof equationsthe differentialsof the
actuallyoccurredin eitherrock. The methodof determininga molesof thesystemcomponents to whichthesystemis open;
wholerock reactionoutlinedabove(e.g. equations153-160), for closedsystembehaviorthedifferentialsof themolesof the
on the other hand, permits possiblereactionsin a single systemcomponentswere set equal to zero (dmi --0). For
sampleto be evaluated.The reactionssodetermined may then example,if the systemis to be modeledasopento H20, then
be comparedwith petrographicobservationsand constraints dmH20 mustbe consideredas an additionalvariableof the
placedon the P-T path. system,which increasesthe varianceof the systemof
equations by 1. Dependingon thenatureof theproblemto be
Path -DependentProcesses solved,dmi may be treatedas an independentvariableor a
All of thecalculations
presentedabovecontainanimportant dependentvariable.
assumption: equilibriumis maintainedthroughout the system Metamorphicfractionalcrystallization is a specialcaseof
for all computedchanges.Becauseof this assumptionthe opensystembehaviorwheremassis lostto the systemby the
exactpath takento get from one setof conditionsto anotheris fractionationof materialinto the coresof growingcrystals
immaterialbecauseeach set of conditionsrepresentsa state suchas garnet. It is the low diffusivityof cationsin garnet
functionand is thuspath independent.(An exceptionis the under low grade metamorphicconditions that permits
analysisof wholerock reactions,whichis a path-dependent fractionalcrystallization to occur. Thereare two waysthat
process). fractionalcrystallization
canbemodeledusingtheequations of
Metamorphicrocksdo not behaveas perfectequilibrium differentialthermodynamics.The mostgeneralway is to
systems, however.Thereis abundant evidencein themajority include as new variables the differentials of the moles of the
of rocksthatequilibriumconditions do notprevailthroughout systemcomponentsthat fractionateinto the phaseof interest.
the entire system.Observationssuchas chemicalzoningin If garnetis the fractionatingphasethenthedifferentialsof the
mineralsindicate incompleteequilibrationwithin crystals. moles of SiO2, A1203, FeO, MgO, MnO and CaO (i.e.
Chemicalheterogeneityamonglike phaseswithin a sample dmsio2,dmA1203, dmFeO, dmMgO, dmMnO anddmcao)are
indicatelack of completeequilibriumon a thin sectionscale. addedas variablesto the systemof equationsincreasingthe
Reactiontextures indicateincomplete reaction.As mentioned varianceby 6. For eachiterationof thecalculations,thevalues
at theoutset,thesefeaturesareadvantageous to thepetrologist of Amsio2,AmAI203, AmFeO, AmMgO, AmMnO andAmcao
becauseit is throughanalysisof thesefeaturesthat P-T paths are setequalto the total molesof thesecomponents that were
may be inferred. However, the perfect equilibrium incorporatedinto garnetduring the last iteration,computed
calculationspresentedabovemustbe temperedsomewhatto from theequation
accommodate thesedisequilibrium
features.
Therearemanywaysin whichdeviationsfrom equilibrium Ami= AMGar .ni,,Gar
Xj,Gar (167)
may occur. Reactionkineticsor nucleationratesmay cause J

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38 Spear:Petrologic
determination
of metamorphic
P-T-tpaths

MnO Ky
A

F M

Bio

G3
/i i
G2 / i

G1

/ I
/ I
I

FeO S1 S2 K2 K3 Chlorite MgO


Stauro.lite Kyanite

Fig.13.(A) FeO-MgO-MnOplotof computed


phase
relations
inpeliticschists
atapproximately
588C
showingthecompositional
trends
of garnets
(G1,G2,G3)fromthreebulkcompositions
(BC1,BC2,BC3)
computed
usinga fractional
crystallization
modelalonganisobaricheating
path[fromSpear,
1988c;seetext
fordiscussion].
Garnet corecompositionis shown
witha square,garnetrimcompositionwitha circle.
Coexisting
staurolite
in BC1islabeled
S1. Coexisting
staurolite
andkyanitein BC2arelabeled
S2andK2.
Coexisting
kyanite
inBC3islabeled
K3.Allassemblages
alsocontain
biotite.
Inthisprojection,
kyanite
(K2,
K3)plotswiththeFe/(Fe+Mg)
of biotite.
AFMdiagram
shown
in theupper
rightshows
theschematic
AFM
topology
forthisgrade.Notethatgarnet+ kyaniteandgarnet+ chlorite
tie linesarenotstableontheAFM
diagram,buttheyarestable
ontheFeO-MgO-MnO diagram because
ofthepresence
ofMnOingarnet. (B)
Garnetzoningprofile
(molefraction
vsdistance)
forthegarnetproduced
incalculations
forbulkcomposition
2 (BC2)(seeFig. 13A).Solidportions of curvesarefinalzoningprofile(assuming no diffusional
homogenization)
attheP-TconditionsofFigure13A.Dashed portions
ofthezoningprofile
arethetraceof
therimcompositionofthegarnet
thathasbeenremovedasa result
ofconsumption
ofgarnetbyreaction168.
(C)Plotofvolume ofphasesvstemperature
computedforbulkcomposition
2 (BC2).Sharpincreases
and/or
decreases
in theabundance
of phases
occurasa resultof reactions
168and169.

In other words, at each iteration a certain number of moles of compositions


in theMnKFMASHsystemwereinvestigated
garnetof a knowncomposition
is produced,which is then alongisobaricheatingpathsfrom 440 to 588 C. In these
removed from the mass of the system by fractional calculations,
massbalanceconstraints
wereemployed sothe
crystallization. systemof equations
hada varianceof 2. Theindependent
An alternativeway of achievingthe sameresult,whichis variables
werechosen
to beP andT sothatchanges
in mineral
computationallymuchsimpler,is to setthemolesof garnetin chemistryandmineralabundancecouldbemonitored along
theassemblage equalto zeroateachiteration
(MGar= 0). This any P-T path by solutionof equations(153-160). Natural
ensuresthat the bulk composition changesby exactlythe assemblages and partitioningdata were usedto infer the
correct amount for the amount of garnet that has been temperaturesof assemblagechanges andthecompositions of
produced. newmineralsin theassemblage.
An example
of a fractional
crystallization
modelforgarnetis Each bulk compositionnucleatesgarnetat a different
presented by Spear [1988c]. Three different bulk temperatureandexperiences a differentreactionhistory. A

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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

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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

thereactionproceeds,but becausethe interiorof the garnetthat staurolite+ muscovite+quartz=


is exposedis richerin Mn thantherim, thenetresultis thatthe
Mn profile is steepened, as shown in Figure 13B for garnet+ biotite+kyanite+ H20 (172)
spessartine. This result only applies to reaction (168),
however.Reaction(169) involvesa sufficientlylargeincrease results in decreases in the abundances of the reactants and
of Mn towardsthe rim so that the net resultis an upturnin the increasesin the abundances of theproducts.
spessartinezoning at the rim [see Spear, 1988c for more An importantfeatureof the metamorphism of rocksto be
details). seenin diagramssuchasFigure13C is therelativeproportions
Figure13C showsthechangesin themodalproportions of of minerals produced over different P-T intervals. In
phaseswith progressivemetamorphismalong the isobaric particular,it shouldbe notedthatreaction(170) is capableof
heating path. As can be seen, the proportion of garnet producing significantly greater amounts of garnet for a
increases at theexpenseof chloriteas thereaction specified change in temperaturethan is reaction (172).
Similarly,thereaction
chlorite+ muscovite+ quartz= garnet+ biotite+ H20 (170)

proceedsuntil reactions(168) and kyanite+ biotite+ quartz= garnet+ muscovite (173)

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.

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Spear:Petrologic
determination
of metamorphic
P-T-tpaths ql

Garnet-plagioclasephase relations. Anotherinteresting (o3P/o3XAlm)XSps,XGrs,XAn


AXAIm
resultemergeswith respectto the growthrelationsof garnet
and plagioclasein systemsin which garnetis undergoing + (o3P/o3XSps)XAlm,XGrs,XAn
AXSps
fractionalcrystallization. If garnetis undergoingfractional
crystallization,thenthe effectivebulk compositionof the rock + (o3P/o3XGrs)XAlm,XSps,XAn
AXGrs
is continuouslybeing depletedin the componentsthat are
enrichedin garnet,notablyCa andMn. If theonly Ca-bearing + (3P/3XAn)XAIm,XSps,XGrs
AXAn (179)
phasesin therockaregarnetandplagioclase thenmassbalance
requires that plagioclase coexisting with garnet becomes
increasinglyalbitic as the garnetgrows,regardlessof the P-T
AX1,B (o3X
1,B/o3XAlm)XSps,XGrs,XAn
AXAlm
path. Therefore,underclosedsystembehavior,garnetshould + (o3Xl,B/o3Xsps)XAlm,XGrs,XAn
AXSps
zone towardslower Ca contentson the rim and plagioclase
inclusionsin garnetandthecoresof zonedplagioclasecrystals
shouldbe more anorthiticthantherims of plagioclasecrystals + (o3X1,B/o3XGrs)XAim,XSps,XA
n AXGr
s
in the matrix. Note, however, if other Ca-rich phasesare
present such as epidote, margarite or carbonate, then the + (o3Xl,B/o3XAn)XAlm,XSps,XGrs
fiXAn (180)
breakdown of one or more of these phases may release
sufficientCa to permit bothgarnetandcoexistingplagioclase AX2,B ()X2,B/)XAlm)XSps,XGrs,XAn
AXAIm
to becomeincreasinglyCa-rich.
+ OX2,B/i)XSps)XAlm,XGrs,XAn
AXSps
P-T Pathsfrom ZonedPorphyroblasts
+ ()X2,B/)XGrs)XAIm,XSps,XAn
AXGrs
Spearand Selverstone[ 1983]presenteda methodwhereby
thechemicalzoningpreserved in zonedgarnetsandplagioclase + 0X2,B//)XAn )XA!m,XSps,XGrs AXAn(181)
could be used to infer metamorphic P-T paths. The
fundamentalassumptions of this methodare that the zoning etc...
observedin the garnetis theproductof growthby continuous
reaction and that the zoning has not been modified by Additionalequationsarerequiredfor eachadditionaldependent
diffusionalprocesses
sincethegrowthof thecrystal.In other variable.
words,the zoningobservedin garnetis assumedto reflect the The P-T conditionsestimatedfor the rim of the garnetin
equilibrium rim composition of the crystal as the crystal equilibriumwith thematrixmineralassemblage areusedasthe
grows. reference (initial) conditions. The entropies,volumes and
With these assumptions,the change in pressure and activities of all phase components are computed at the
tempei'ature
(P-T path)consistent
withtheobserved
zoningin referenceP-T conditions
andthe AS, AV andKeqof each
garnet and plagioclasecan be computedby choosingas reactioncomputed. The matrix A (equn. 133) is set up and
independentvariables the compositionalparametersXAlrn, solvedas describedaboveand valuesof AT, AP, AX1,B,
XSps,,,XGrs
andXAn. If thevariance
is 4 thenall four AX2,B etc. are computedusingvaluesof AXAIm,AXSps,
vanames are chosenas independent. If the varianceis 3 or AXGrs and AXAn corresponding to the first measured
lessthenonly the molefractionsof components in the garnet incrementof zoningin the garnet.From thesevaluesof AT,
are chosenas independent. In the procedureof Spear and AP, I,B, AX2,Betc., new valuesof T, P, X1,B, X2,B etc.
Selverstone[ 1983], only intensivevariablesare usedto infer are computedand the processrepeateduntil the core of the
P-T paths(that is, no massbalanceconstraintsare employed). garnetis reached. The computedvaluesof T andP at each
Therefore,phaserule variancesof 3 or 4 arequitecommonin stepare the P-T path.
the assemblages investigated. Although straightforwardin concept,applicationof this
Assuming that the variance is 4, then the appropriate techniquerequiresconsideration of thefollowingpoints:
equationsare (1) It is imperativethat the assemblage presentin the rock
over the interval of garnetgrowth be known; otherwisethe
T = F(XAIm,XSps,XGrs,XAn)(174) correctthermodynamicconstraintswill not be employedand
the resultswill be wrong.Moreover,it is critical to note that
P = F(XAim,XSps,XGrs,XAn)(175) the assemblage presentas the garnetgrew is not alwaysthe
sameas the assemblagethat is presentin the matrix of the
X 1,B= F(XAlrn,XSps,XGrs,XAn)(176) rock. In the examplepresentedby Selverstoneet al. [1984]
argumentswere presentedsupportingthe hypothesis that the
X2,B= F(XAlm,XSps,XGrs,XAn)(177) matrix assemblage waspresentthroughoutgarnetgrowth,but
etc .... so that
in severalexamplesexaminedby SpearandRumble[ 1986]it
was demonstrated that the matrix assemblage was not present
overmuchof thegarnetgrowthhistory.In thislattercase,the
AT =
(}T/JXAIm)XSps,XGrs,XAn
Z(Alm matrixassemblage wasgarnet+ biotite+ staurolite+ kyanite+
muscovite+ plagioclase+ quartz but most of the garnet
+ (}T/JXSps)XAIm,XGrs,XAn
AXSps growthwasinterpretedto haveoccurredwith theassemblage
garnet+ biotite+ chlorite+ muscovite+ plagioclase + quartz.
+ (}T/JXGrs)XAIm,XSps,XAn
AXGrs Determinationof the assemblagepresentduring garnet
growthis notofteneasyandrequires
a considerableamountof
+ (}T/JXAn)XAlrn,XSps,XGrs
l(An (178) petrologicdetectivework. Especiallyusefulis the careful

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

/42 Spear:Petrologic
determination
of metamorphic
P-T-tpaths

examinationof any inclusionspresentin the garnet.In some


samples,
unequivocal proofis impossible
andthebestthat
maybeachieved
is aninternal
consistency
argumentbasedon ?o-
a combination of both inverse and forward modeling. A
forwardmodeling
technique
usingdifferential
thermodynamics._t
=65-
is describedin the sectionentitledPath dependentprocesses <
andby Spear[1988c]. GROSS
(2) For many assemblages that producegarnet with 6o-
increasingtemperature,it is the changein almandineand -15
spessartine
(aswell asFe/(Fe+Mg))thatprovidethelargest
constrainton temperaturechangesand it is changesin
grossular
andanorthitethatprovidetheconstraints
onpressure 40- -10 u
changes.For example,in theassemblage garnet+ biotite+
chlorite+ muscovite
+ plagioclase
+ quartz,thedominant
garnetproducing
reaction
is s
-15

chlorite+ muscovite+ quartz= garnet+ biotite+ H20 (170)


-10
Progressalong this reaction controls the Fe, Mg and Mn
contents of garnet and coexisting Fe-Mg-Mn silicates.
Inasmuch as this reaction has a steep P-T slope, these A FH-1M
components largelyreflectchangesin temperature.
I
I I I
0 I 2 3 4
In contrast,the grossularcomponent in garnetandanorthite DISTANCE, mm
componentin plagioclaseare largelycontrolledby equilibria
with considerably flatterP-T slopes,thereforechangesin these
componentslargely reflect changesin pressure. (This last
statementis not exactly true, becausemassbalancemustalso
be considered). In rocksof varianceof 4 it is thereforecritical
thatan accuratecorrelationbetweenthe zoningin plagioclase i i i i i

and the zoningin garnetbe madein orderto obtaina precise


estimateof changesin pressure.The mostideal situationis B
where plagioclaseinclusionsare found within the garnet
crystaland anorthitecontentcan be correlateddirectly with
Sample FH-1M
grossularcontent.
These considerations are extremely important in the
applicationof theprocedureof SpearandSelverstone [ 1983]
to the inferenceof P-T pathsof crystallizationfrom growth CORE
zonationin garnet. If resolutionof changesin P andT is to be
made with certainty,then it is imperativethat the variables
chosenas independentin the assemblage have P-T isopleths
that intersect at a reasonably high angle. In an exactly
analogousway, if absolutevalues of P and T are to be
estimatedfrom thermobarometry, thenit is necessarythat the
two equilibriahavea relativelyhighangleof intersection.The
mostcertainway to ascertainwhetheror not the isoplethsin
questionhave a high angle of intersectionis to construct
isoplethmapsasdescribedabove. As a generalconsideration,
however, isoplethsof almandineand spessartineare often
I Xalm&&Xgross
Xspess Xgross] T
subparalleland therefore,do not providegoodresolutionof
AP and AT simultaneously.Generally,isoplethsof grossular o Xalm& Xgross - 'IT
areat a fairly highangleto thoseof almandineandspessartine,
soa combination
of XGrswithXAlmorXSpsprovides
a good RIM
combinationof independent
variables.
An example.An exampleof thesecalculations
will be given
from thepaperby Selverstone et al. [ 1984] from the Tauern
Window, Austria. This wasthe first garnetthatwasanalyzed i
530
I i I
540
I
550
I

in detailusingthetechniquesof SpearandSelverstone [1983] T, C


andit illustratessomeinterestingfeatures.The rockmodeled
was a coarse-grainedgarbenschieferthat contains the Fig. 14. (A) Zoningprofileacross
a garnetfromthewestern
assemblage garnet+ hornblende+ staurolite
+ kyanite+ biotite Tauern Window from Selverstoneet al. [ 1984; sampleFH-
+ chlorite+ plagioclase+ quartz.The chemicalzoning 1M] usedin thequantitative
modeling
of P-T paths.(B) P-T
measuredin the garnetis shownin Figure 14A. Numerous pathscomputed
fromgarnetprofilesin (A) usingdifferent
plagioclases were analyzedand were foundto rangein combinations
of independent
variables.FromSelverstone
et
composition fromAn16in thematrixto An32in thecoreof the al. [ 1984].

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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

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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

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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

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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.

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Spear: Petrologicdetermination
of metamorphic
P-T-t paths q7

BF-86B

Fe/(Fe + Mg) Almandine

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].

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

Spear:Petrologic
determination
of metamorphic
P-T-t paths t9

discussedin the next section,P-T paths can be useful for


constraining tectonic transport rates as well as rates of
BF-86B' Model II exhumation or denudation.

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.

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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

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supportedby National Science Foundation grant EAR- Aranovich, L. Ya. and K.K. Podlesskii, The cordierite -
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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

Spear:Petrologicdetermination
of metamorphic
P-T-t paths

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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P-T-tpaths 53

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Mineral. Petrol., 66, 75-80, 1978. Fe-Mg partitioning between garnet and olivine and its
Laird, J., Phaseequilibriain mafic schistfrom Vermont.J_ calibrationsas a geothermometer. Contrib.Mineral. Petrol,,
Petrol., 21, 1-38, 1980. 70, 59-70, 1979.
Lasaga,A. C., Richardson,
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sillimanite equilibrium. Am. J. Sci., 281, 1056-1090, plagioclase-quartz
barometry:
Refinement andapplication
to
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sphaleritegeobarometer
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519, 1978. formingreactions.
Can.Mineral.,20, 349-378,1982.

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

5tl Spear:Petrologicdetermination
of metamorphic
P-T-t paths

Powell, R., Regressiondiagnosticsandrobustregressionin geothermometry.Contrib. Mineral. Petrol.,7_8,157-165,


geothermometer/geobarometercalibration: the garnet- 1981.
clinopyroxenegeothermometer revisited. J. Metamorph. Saxena,S. K., Two-pyroxenegeothermometer:A modelwith
Geol., 3, 231-243, 1.985. an approximate solution. Am. Mineral., 61, 643-652,
Powell, R., Condliffe, D. M. and E. Condliffe, Calcite- 1976.
dolmotitegeothermometryin the systemCaCO3-MgCO3- Saxena, S. K., Garnet-clinopyroxene geothermometer.
FeCO3:An experimentalcalibration.J. Metamorph.Geol., Contrib. Mineral. Petrol., 70, 229-235, 1979.
2, 33-42, 1984. Saxena, S. K. and C. E. Nehru, Enstatite-diopsidesolvus
Powell, R. and J. A. Evans, A new geobarometerfor the and geothermometry.Contrib. Mineral. Petrol.,49, 259-
assemblagebiotite - muscovite- chlorite- quartz. J_. 267, 1975.
Metamorph.Geol., 1, 331-336, 1983. Scott, S. D., Experimental calibration of the sphalerite
Powell, R. and T. J. B. Holland, An internally consistent geobarometer.Econ. Geol., 68,466-474, 1973.
thermodynamic datasetwith uncertainties
andcorrelations: Scott, S. D., Applicationof the sphaleritegeobarometerto
1. Methodsand a worked example. J. Metamorph.Geol., regionally metamorphosedterrains. Am. Mineral., 61,
3, 327-342, 1985. 661-670, 1976.
Powell, R. and T. J. B. Holland, An internally consistent Selverstone,J., Spear, F. S., Franz, G., and G. Morteani,
thermodynamic datasetwith uncertainties
andcorrelations: High pressuremetamorphismin the SW Tauernwindow,
3. Applicationsto geobarometry,worked examplesand a Austria: P-T paths from hornblende-kyanite-staurolite
computerprogram. J. Metamorph.Geol., 6, 173-204, schists. J. Petrol., 25, 501-531, 1984.
1988.
Sen,S. K. andA. Bhattacharya,An orthopyroxene - garnet
Powell, R. and M. Powell, Plagioclase-alkali feldspar thermometerandits applicationto theMadrascharnockites.
thermometryrevisited. Mineral. Mag., 4._1,
253-256, Contrib. Mineral Petrol., 88, 64-71, 1984.
1977a. Smith, W. R. and R. W. Missen, Chemical reaction
Powell, R. and M. Powell, Geothermometryand oxygen equilibriumanalysis:Theory_
and algorithms.JohnWiley
barometry using iron-titanium oxides: A reappraisal. and Sons,New York, 364 pp., 1982.
Mineral. Mag., 4__!_1,257-263,
1977b. Spear,F. S., Thermodynamicprojectionandextrapolation
of
Pownceby,M. I., Wall, V. J. and H. St. C. O'Neill, Fe-Mn high-variancemineral assemblages. Contrib. Mineral.
partitioning between garnet and ilmenite: experimental Petrol., 98, 346-351, 1988a.
calibrationand applications.Contrib.Mineral. Petrol.,97, Spear,F. S., The Gibbs methodand Duhem'stheorem:The
116-126, 1987a. quantitativerelationships
amongP, T, chemicalpotential,
Pownceby,M. I., Wall, V. J. and H. St. C. O'Neill, Fe-Mn phasecompositionand reactionprogressin igneousand
partitioning between garnet and ilmenite: experimental metamorphicsystems. Contrib. Mineral. Petrol.,99, 249-
calibrationand applications(correction).Contrib.Mineral. 256, 1988b.
Petrol., 9_2.7,
539, 1987b. Spear, F. S., Metamorphic fractional crystallizationand
Prigogine, I. and R. Defay, Chemical Thermodynamics. internal metasomatismby diffusional homogenizationof
Longmans,Green and Co., London,1954. zoned garnets. Contrib. Mineral. Petrol., 99, 507-517,
1988c.
Raheim,A. andD. H. Green, Experimentaldeterminationof
the temperatureand pressuredependenceof the Fe-Mg Spear,F. S., Relativethermobarometry andmetamorphic P-T
partition coefficient for coexisting garnet and paths.In Daly, J. S., Cliff, R. A. and B. W. D. Yardley,
clinopyroxene. Contrib. Mineral. Petrol., 48, 179-203, eds., Evolutionof MetamorphicBelts,GeologicalSociety
1974. SpecialPublicationNo. XX, in press,1988d.
Robie, R. A., Hemingway, B. S., and J. R. Fisher, Spear, F. S. and C. P. Chamberlain, Metamorphicand
Thermodynamic properties of minerals and related tectonicevolutionof the Fall Mountainnappecomplexand
substances at 298.15K and 1 bar(105pascals) pressure adjacent Merrimack synclinorium. In P. Robinson,ed.,
and at higher temperatures.U.S. Geol. Surv. Bull. 1452, Regionalmetamorphism andmetamorphic phaserelationsin
456 pp., 1979 northwestern and central New England. Field trip
Robinson,P. R., Hollocher, K. T., Tracy, R. J. and C. W. guidebook for the 14thgeneral meeting of theInter.
Dietsch, High gradeAcadianregionalmetamorphismin Mineral. Assoc., University of Massachusetts, Amherst,
south-central Massachusetts(R. Joesten and S. Quarrier, Massachusetts,121-143, 1986.
eds.) NEIGC 74th Ann. Meet., Storrs, CT, 289-340, Spear,F. S. andJ. T. Cheney, A petrogenetic grid for pelitic
1982. schistsin the systemSiO2 - A1203 - FeO- MgO- K20 -
Ross, M. and J. S. Heubner, A pyroxene geothermometer H20. Contrib. Mineral. Petrol., in press,1989.
basedon composition-temperature of naturally Spear, F. S., Ferry, J. M. and D. Rumble, Analytical
relationships
occurringorthopyroxene,pigeoniteand augite,Extended formulationof phaseequilibria: The Gibbs method.In J.
Abstracts,Int. Conf. Geothermometryand Geobarometry. M. Ferry, ed. Characterizationof Metamorphismthrough
The Pennsylvania State University, University Park, Mineral Equilibria. Mineral. Soc. Am. Rev. Mineral., 10,
Pennsylvania,1975. 105-152, 1982a.
Russell, J. K. and J. Nicholls, Application of Duhem's Spear, F. S., Hickmott, D. D., J. Selverstone, The
theorem to the estimation of extensive and intensive metamorphicconsequences of thrust emplacement,Fall
propertiesof basalticmagmas.Can. Mineral., 23, 479-488, Mountain,New Hampshire,in preparation.
1985. Spear,F. S., Rumble,D., and J. M. Ferry, Linear algebraic
Sachtleben, Th. and H. A. Seck, Chemical control on the A1- manipulationof n-dimensionalcompositionspace.In: J.
solubilityin orthopyroxeneandits implications
onpyroxene M. Ferry, ed., Characterizationof Metamorphismthrough

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

Spear:Petrologicdetermination
of metamorphic
P-T-t paths 55

Mineral Equilibria, Mineral. Soc. Am. Rev. Mineral, 1._Q0, Thompson, J. B. Jr., and J. L. R. Rosenfeld,
53-104, 1982b. Reinterpretationof nappesin the Bellows Falls-Brattleboro
Spear, F.S. and D. Rumble, Pressure, temperature and area, New Hampshire- Vermont. in J. W. Skelanand P.
structural evolution of the Orfordville Belt, west-central H. Osberg, eds., The Caladonides in the USA - Geol.
New Hampshire.J. Petrol.,27, 1071-1093, 1986. Excursions in the Northeast Appalachians, Weston
Spear,F. S. and J. Selverstone,QuantitativeP-T pathsfrom Observatory_, Weston,MA, 117-121, 1979.
zonedminerals:Theory and tectonicapplications.Contrib. Tracy, R. J., Compositional zoing and inclusions in
Mineral. Petrol., 83, 348-357, 1983. metamorphicminerals.In J. M. Ferry, ed. Characterization
Spencer,K. J. and D. H. Lindsley, A solutionmodel for of MetamorphismthroughMineral Equilibria.Mineral. Soc.
coexistingiron-titaniumoxides. Am. Mineral., 66, 1189- Am. Rev. Mineral, 10, 355-397, 1982.
1201, 1981. Tracy, R. J., Robinson, P. and A. B. Thompson, Garnet
St-Onge,M. R., Zonedpoikiloblasticgarnets:P-T pathsand compositionandzoningin thedetermination of temperature
syn-metamorphic uplift through30 km of structuraldepth, andpressureof metamorphism, centralMassachusetts. Am.
Wopmay Orogen,Canada. J. Petrol.,28, 1-22, 1987. Mineral., 61,762-775, 1976.
Stormer, J. C., A practical two-feldspar geothermometer. Warner, R. D. and W. C. Luth, The diopside-orthopyroxene
Am. Mineral., 6._Q0, 667-674, 1975. and orthopyroxene-clinopyroxene relationshipsin simple
Thompson, A. B., Mineral reactions in pelitic rocks: II. and complexsystems.Contrib. Mineral. Petrol.,42, 109-
Calculationof someP-T-X(Fe-Mg) phaserelations.Am. J. 124, 1974.
Sci., 276, 425-454, 1976. Weisbrod, A., Refinementsof the equilibrium conditionsof
Thompson,A. B. and P. C. England, Pressure- temperature the reactionFe-cordierite- almandine- quartz- sillimanite
- time pathsof regionalmetamorphismII: Their inference (+H20). CarnegieInstitutionof WashingtonYearbook,
and interpretation using mineral assemblages in 72, 518-521, 1973.
metamorphicrocks. J. Petrol., 2_5, 929-954, 1984.
Wells, P. R. A., Pyroxene thermometry in simple and
Thompson,J. B., Jr., The thermodynamicbasis for the
mineralfaciesconcept. Am. J. Sci., 253, 65-103, 1955. complexsystems.Contrib.Mineral. Petrol.,62, 129-139,
1977.
Thompson, J. B., Jr., The graphical analysis of mineral
assemblages in pelitic schists.Am. Mineral., 4_2,
842-858, Whitney, J. A. and J. C. Stormer, The distribution of
1957. NaA1Si308betweencoexistingmicroclineandplagioclase
Thompson,J. B., Jr., Thermodynamicpropertiesof simple and its effect on geothermometriccalculations. Am.
solutions,(P.H. Abelson, ed.), Res. in Geochem.,2, 340- Mineral., 62, 687-691, 1977.
361 Wiley, New York, 1967. Wolery, T. J., Calculation of chemical equilibria between
Thompson, J. B., Jr., The tschermak substitution and aqueous solutions and minerals: the EQ3/6 software
reactionsin pelitic schists(in Russian). In: Zharikov, V. package.Lawrence Livermore National Lab. Livermore,
A., Fonorev, V. I. and J.P. Korikovskii, eds., Problems CA URCL-52658, 191 pp., 1979
in physicochemicalpetrology,1, 146-159, Academy of Wood, B. J., The influenceof pressure,temperatureandbulk
Sciences,Moscow, (The original Englishmanuscriptwas compositionon the appearance of garnetin orthogneisses
an
privatelycirculated),1979. examplefrom SouthHarris, Scotland. Earth Planet. Sci.
Thompson, J. B., Jr., Reaction space: an algebraic and Let., 26, 299-311, 1975.
geometricapproach.In J. M. Ferry, ed. Characterization of Wood, B. J., Thermodynamicsof multicomponentsystems
metamorphismthroughMineral Equilibria. Mineral. Soc. containingseveralsolid solutions. In Carmichael,I. S. E.
Am. Rev. Mineral., 1._Q0, 33-51, 1982. and H. P. Eugster, eds., Thermodynamic Modeling of
Thompson, J. B., Jr., Laird, J. and A. B. Thompson, GeologicalMaterials:Minerals,FluidsandMelts. Mineral.
Reactionsin amphibolite, greenschistand blueschist.J_ Soc. Amer. Rev. in Mineral., 17, 71-95, 1987.
Petrol.,23, 1-17, 1982. Wood, B. J. and S. Banno, Garnet-orthopyroxeneand
Thompson,J. B. Jr., Robinson,P., Clifford, T. N., and N. garnet-clinopyroxene relationshipsin simpleandcomplex
J. Trask, Nappes and gneissdomesin west-centralNew systems.Contrib.Mineral. Petrol.,42, 109-124, 1973.
England.In E-an Zen et al., Eds., Studiesof Appalachian Wood, B. J. and D. G. Fraser, Elementary thermodynamics
Geol., Northernand Maritime, 203-218, JohnWiley, New for geologists.Oxford UniversityPress,Oxford, 303 pp.,
York, 1968. 1977.

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

THERMAL MODELING OF METAMORPHIC


PRESSURE-TEMPERATURE-TIME PATHS: A FORWARD APPROACH

Simon M. Peacock

Departmentof Geology,ArizonaStateUniversity,Tempe,AZ 85287-1404

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

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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
---

cool Rates 35km


35 km HRUST
sufficently rapid
sufficently rapid such
such that
that the
the thermal
thermal structure
structure of
of the
the crust
crust is
is
4000C
._
--- ___ 400oC
strongly affected
strongly affected byby these
these processes.
processes. BothBoth tectonic
tectonic and
and
sedimentary processes
sedimentary processes may
may contribute
contribute to
to the
the burial
burial and
and uplift
uplift C R U ST
CRUST
history of
of the
the rock. Rocks may
rock. Rocks may bebe buried
buried byby tectonic
tectonic ----'--6 000C
600C ;;.;"";;.;;;.;;.....-
history
_____ ___

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
=

L = characteristic scale[m], and


lC thermal diffusivity
c= thermal
= diffusivity [m-/s].
[m2/s].
Peelet numbers
Peclet much greater
numbersmuch than one
greaterthan one indicate
indicatethat
thatheat
heatis
is
emplaced
emplacedfaster
fasterthan
than heat
heat is conducted away;
is conducted away; the
the thermal
thermal
structure
structureof of the
the crust
crust will
will bebe affected
affected by by the emplacement
the emplacement Fig. 1.
Fig. 1. Schematic
Schematic illustration
illustrationof crustal thickening
of crustal event
thickeningevent
process. Peelet numbers
process.Peclet numbers much
muchlesslessthan
thanoneone indicate
indicatethat heat
thatheat resulting in
resulting regional metamorphism.
in regional metamorphism. The emplacement of
The emplacement of a
a
is conducted
IS conducted away faster than
awayfaster thanheat
heatis emplaced; the
is emplaced; the thermal
thermal 20 km thick thrust sheet results
thrust sheet results in thickening
thickening of the the
structure
structureofof the crust will
the crust not be
will not be affected
affectedby by the
the emplacement
emplacement continental crust
continental crustto
to 55 km. Point A, initially
km. Point initially at
at the
the surface,
surface,is
is
process.
process. buried
buried2020 km
km by
by the
the overriding
overridingthrust
thrustsheet.
sheet. Subsequent
Subsequent
Consider
Consider thethe tectonic
tectonic burial
burial of
of aa rock
rock beneath
beneath aa 20 20 km-thick
km-thick thermal
thermalrelaxation
relaxationin creases the
increases thetemperature
temperature at
atpoint
pointA,A, causing
causing
thrust
thrustsheet
sheetasasillustrated
illustrated in Figure 1.
in Figure 1. Will
Will the
theemplacement
emplacement of
of regional metamorphism.
regional metamorphism.
the
the thrust sheet affeet
thrust sheet affect the
the thermal
thermal structure
structure of of the
the continental
continental
crust?
crust? WeWe can
can calculate
calculate the Peelet number
the Peclet number for for this
this situation
situationin in
order
order to to answer
answerthis this question.
question. The relevant characteristic
The relevant characteristic
length
lengthscale (L) in
scale(L) in this
thisproblem
problemis is 20
20 km,
km,thethethickness
thickness of
of the
the
overriding
overridingthrust
thrustsheet.
sheet.Typical
Typicalthermal
thermaldiffusivities
diffusivities (lC)
0c)ofof Before
Beforeexamining
examining the
thedifferent
differentformsformsof of heat
heattransfer,
transfer, let
letus
us
crustal
crustal rocks
rocksare areapproximately
approximately 11 mm2/s.
mm2/s.Let Letus usassume
assume that
that discuss
discussthe the relationship
relationshipbetween
betweenaa crustalcrustalgeotherm
geothermand and
the
the thrust
thrust sheet
sheet was was emplaced
emplaced at at plate
plate tectonic
tectonic rates rates metamorphic
metamorphic gradients
gradients observed
observed in
in the
thefield.
field. InIn stable
stablecratons,
cratons,
(v = 33 cm/yr).
(v =
cm/yr). Using Using these these values
values and and appropriate
appropriate temperature
temperature increases
increases monotonically
monotonically with
withdepth.
depth.The Thevariation
variation
conversions
conversions (1 year
(l year- 3.156
3.156xx 107 107seconds), the
thecalculated of
of temperature
temperature as
asaa function
functionof of depth
depthis is called
calledthethegeotherm.
geotherm.
=

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

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

PEACOCK 59

Temperature Heat Transfer- Equations and Solutions


Fourier's Law

The amountof heat passingthrougha surfaceper time is


given by Fourier'sLaw:

Tmax q = -kdT
dz
(2)

Metamorphic where q = conductiveheatflux [J/(m2 s) = W/m2],


P-T array k = thermalconductivity[W/(m K)],
T = temperature[K], and
P-T-t paths z = distanceor depth [m].
Higher thermalgradients(dT/dz) resultin higherconductive
heat fluxes.
20 m.y. 40 m.y. 60 m.y. Measured conductive, surfaceheat fluxes in stable cratonic
regionsaverageapproximately
40 mW/m2 (0.04 W/m2).
Geotherms [Note: In someliterature,heat flow is reportedin heat flow
units (HFU), where 1 HFU = 0.042 W/m2.] Using an
averagerock thermalconductivityof 2.25 W/(m K), we can
Fig. 2. Schematictemperature-pressure
diagramillustrating useequation(2) to calculatean averagethermalgradientof
the relationship between the geotherm, the pressure- 18 C/km. Measuredsurfaceheatfluxesabovemagmaticarcs
temperature-time path followed by a rock, and the lie between
60 and150mW/m2 implyingsteeper
thermal
metamorphic P-T array. A geotherm represents
temperatureas gradientsin the underlyingcrust[vandenBeukelandWortel.
a functionof depthat afixed time. Platetectonicprocesses, 1986]. In contrast,
surface
heatfluxeslessthan40 mW/m:
arecommonabovearc-trench
such as burial and uplift, perturb the geotherm. Different gapsat convergent platemargins
geothermsare shown with thin lines, labeled with time in [vandenBeukelandWortel, 1986]indicatingthatrocksabove
millions of years. During a crustal thickening event, a subducting slabsarerelativelycool.
metamorphicrock will generallyfollow a counter-clockwise The minus sign in equation(2) reflects the fact that heat
loopin pressure-temperature
space(withpressure increasing flows downthermal gradients.If temperatureincreaseswith
downward). The mineralassemblage generallyreflectsthe depth(z), thatis dT/dz is positive,thenheatflows upwardin
maximumtemperature (Tmax)andthe concomitant pressure the negativez direction. Note that z (depth)increasesdown-
(PTmax)achievedby the rock. The locusof Tmax-PTmax ward.
points preserved in a metamorphic terrane is called the Thermalconductivity,k, is relatedto thermaldiffusivity,c
metamorphic P-T array(= metamorphic geotherm of England [m2/s], bythefollowing relation:
andRichardson
[ 1977]= metamorphic
fieldgradientof Spear
et al. [1984]). Different rocks will reach Tmax at different
times; thus, the metamorphicP-T array does not reflect a pC
geotherm thatexistedat anysingletime. (3)

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)

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

60 THERMAL MODELING OF 1VIETOC P-T-t PATHS

(A) Temperature(C) (B) Temperature(C)


0 200 400 600 800 1000 o 200 400 600 800 lOOO

2OO 2OO

t
t
4OO 400

6OO 600

8OO 8OO

to
lOOO lOOO

Fig. 3. (A) Analyticalsolution


(eqn.7) to theinstantaneous
heatingof a 1 km-thickslab. Theslabhasa
constantthermal diffusivity,
c= 1mm2/s,andisinitiallyat0 C. Att = 0,thetemperature atthebase
ofthe
slabisinstantaneouslyraisedto1000Cresulting ingradualheating oftheslab.Theupper boundaryofthe
slabremains ata fixedtemperature
of0 C.Thicklinelabeled 'to'represents
theinitialtemperaturecondition.
Curves labeledwithtimeinthousands ofyearsillustrate
thethermal evolution
oftheslab; therateofheating
is
initially
rapid,butslows downovertime.Linelabeled 'too'
represents thesteady-state solutionapproached
aftertensofthousands ofyears.(B) Finitedifference
solution (eqn.14)tothesame instantaneous
heating
problem asFigure 3A. Curves arelabeled
withtimeinthousands ofyears.Finite-difference equations
are
solvedateachpointasdescribed
in thetext. Thecoarse
array-spacing
illustrates
thefinitenatureof thefinite-
difference
method.
Moreclosely spaced
points
wouldmoreaccurately
reproduce
theanalytical
solution.
In
general,
theaccuracy
ofthefinite-element
technique
islimited
onlybythetimestep
andthearrayspacing.
See
text for discussion.

where T = temperature[K], derivativeof temperature


is equalto /)T//)z,thegeothermal
t = time [s], .gradient.
Thesecond spatial
derivative
isequaltothechange
c= thermaldiffusivity[m2/s], n the geothermalgradientwith depth, or )2T/z2. A
z = depth[m], .geothermal
gradient
thatchanges
rapidly
withdepth
willresult
v = velocityof the medium [m/s], nrapidratesof heating
orcooling.A geothermalgradient
that
Vz= velocityof themediumin thez-direction[m/s], is constant
with depthis in steady-state
equilibrium
andthe
A = volumetric
heatproduction [W/m3], temperature
will not changeovertime.
C = specific
heat[.J/(kg
K)], and Aspects of heatconduction canbestbeillustrated
bymeans
p = density[kg/ma]. of an example.Considerthecaseof a rockslab,1 km thick
Equations(4) and(5) definethechangein temperature over and initially at 0 C, that is suddenlyexposedto 1000C
timeasa functionof threedifferenttypesof heattransfer:
heat temperatureat its base(Figure3). This modelis notmeantto
conduction, heat advection, and heat sources and sinks simulate
a particular
geologic
environment,
although
it crudely
representedby the threetermson therightsideof equations, approximatescontactmetamorphismabovea basalticsill.
respectively. Heat will conductrapidlyinto the baseof the slabbecause
of
Heat conduction. Heat is conducted down thermal the increasein temperaturefrom 0 Cto 1000Cat thebase.
gradientsfrom hot regionstowardcoldregions.As canbe Duringthefirstthousand years,temperatures nearthebaseof
seenfromthefirsttermontheright-hand sideof equations(4) theslabincrease
rapidlybecause
of thesharpchanges
in the
and(5), therateat whicha rockwarmsor coolsby conduction geothermalgradientnearthebase. Over time,heatconduction
dependson the thermaldiffusivity of the rock 0c) and the actsto smoothoutchanges in the geothermal gradientuntila
secondspatialderivativeof temperature.A higherthermal constantgeothermalgradientis establishedconsistentwith the
diffusivityresultsin a morerapidrateof heatingor cooling. boundaryconditions.Becausechangesin the geothermal
In a one-dimensional modelwith z = depth,thefirst spatial gradientdiminishovertime,therateof heatingdecreases
over

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

62 THERMAL MODELING OF METAMORPHIC P-T-t PATHS

techniquesto solveequation(4), thuswe shahconcentrateon


numericalmethods. For extensivediscussions of analytical
solutions,the readeris referredto Carslawand Jaeger[ 1959]
and Turcotte and Schubert [ 1982].

NumericalSolutions- Finite-DifferenceMethod

With the advent of computers,the numerical solution of Boundary


differential equationshas become commonplace. Large condition' cBonUila
7
numbers of differential equationsthat can not be solved T(0,t)=g(t)
analytically,canbereadilysolvedusingnumericaltechniques.
Perhapsthe most commonnumericaltechniquesfor solving
differentialequationsarefinite differencemethods.Complex
problemsinvolvingirregulargeometriesmay be solvedusing
finite-elementtechniques. x
Constructing a finite difference model. In the finite- 0 Initial
condition:
T(x,0)
= f(x) 1
differencemethod,the infinitesimalderivativesin equations
(4) and (5) are replacedby finite differences.Let us compare
equation (5) in both its infinitesimal differential and finite
difference forms.
Infinitesimal differential form: BI t
2 1
dT i3 T i3T A
d-=c--- Vz--+--
}Z
2 }Z pC (5A)

Finite difference form:

2
AT A T AT A
--K-Vz+
At 2 Az pC
Az
(5B)

The 'A' refers to a discrete, finite difference between two


0 1
points. Note that as At and Az approachzero, equation(5B) Ax
reducesto equation(5A), a propertycalledconsistency.
In order to illustrate how to construct a finite difference
Fig. 4. Relation betweenthe solutiondomain of a partial
model, let us considerthe partial differential equationthat differentialequationandthe finitedifferencegridcoveringthe
describesone-dimensional,
time-dependent heatconduction: solution domain. (A) Graphical representation of the
temperature solutiondomainfor thepartialdifferentialequation
oT o governingone-dimensional,time-dependentheat conduction
(eqn. 9). Temperatureis the dependentvariable;time (t) and
i3t )x2 (9) position (x) are the independentvariables. The initial and
boundary conditions define the borders of the solution
Equation (9) is also known as the diffusionequation,as it domain. The spatialdomain(x) hasbeennon-dimensionalized
applies to chemical diffusion in addition to heat diffusion suchthat 0 _<x _<1.(B) Graphicalrepresentation of the finite
(conduction). In order to solve equation (9) using a finite difference grid covering the solutiondomain. In the finite
differencemethod,the followingstepsarefollowed: differencemethod,approximationsto the partial differential
Step 1 - Define a grid whichcoversthe solutiondomain. At equation are calculatedat each grid point separatedby an
eachgrid pointin the solutiondomainan approximatesolution spatialgrid spacing(Ax), anda temporalgrid spacing,or time
will be found by algebraic means. In equation (9), step(At). In the finite differencemethod,calculations'march'
temperatureis the dependentvariableand time and space(x) throughtime,startingwith theinitialtemperature conditionand
are independent variables: T = f(x,t). The temperature subsequently calculating the temperature distribution at
solution domain therefore has two dimensions - time and successive time levels.
space. Figure 4 illustratesthe geometricrelationbetweenthe
solutiondomainandthe grid coveringthe solutiondomain.
Step 2 - Initialize all dependent variables. Because As canbe seenin Figure4, the initial andboundaryconditions
metamorphismis a time-dependentheat transferprocess,we definetemperatureat the bordersof our solutiondomain.
needto specifythe initial valuesfor temperatureat t = 0 (initial Step 3 - Constructa finite differenceequation(FDE) that
conditions)and the values for temperature as a function of approximatesthe continuouspartial differential equation
time at the boundariesof our model (boundaryconditions). (PDE). At each grid point, the continuousderivative is

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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)

where the subscriptsrefer to spatial grid points and the 1 (Az)


At _<
superscripts
referto timegridpointsasillustratedin Figure5.
Rearrangingequation(14) and droppingthe truncationerror (16A)
yields:
for a one-dimensional model. In the one-dimensional
numerical solutiondepictedin Figure 3B, where Az = 100 m
_.n+l n n - 2Tq-Ti-1
Ti+l n andc= 1 mm2/s,At mustbe lessthan158yr; therefore,
I
T i = T i + cAt choseAt = 100 yr. For a two-dimensionalmodel, the time
2
stepconstraintis:
(ax) (15) 2
1 (Az)
At <
whichexpresses
the temperatureat point i afteronetime step 4 c (16B)
(Tn+')asa function of temperatures
atneighboring
pointsat
thebeginningof thetimestep(Tn). In problemsinvolvingmetamorphic reactions,it is generally
Step4 - Use theFDE consreacted in step3 (i.e., eqn. 15) to undesirableto use large time stepsbecauseof the dangerof
calculateapproximatevaluesof thedependentvariableat grid overstepping reactionboundaries.In suchcases,the time step
pointsin the solutiondomain. For time-dependent problems, constraintis easily satisfiedand the explicit finite difference
we start at t = 0 and 'march' through time until a methodis computational straightforwardandefficient.
predeterminedtime is reached (e.g., once the pluton has Implicit finite differencemethodsdo not suffer from the
cooledbelow 500 C). time stepconstraintof theexplicitfinite differencemethod,but

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

6t THE MODELING OF METAMORPHIC P-T-t PATHS

implicit methodsare slightlymorecomplexin that a set of


A. Explicit
method equations must be solved simultaneouslyusing matrix
methods. In a simple implicit scheme finite differenc
n+2
equations
areconstructed
aboutan expansion
pointTin+
(Figure 5B). The time derivative is approximatedby a
backwarddifferenceequation(11) andthe second-order spatial
derivativeis approximated by a centraldifferenceequation(13)
n+l resultingin the followingFDE:

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

n .,,n+l ,..,n+l n+l


T i = -sii+ 1 + (1 +ZS)l i - sTi_1 (18)

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

i-2 i-1 i i+1 i+2


Fig. 5. Graphicalrepresentation of the grid pointsusedto
calculatetemperatures at eachsuccesive time ]eve] (t = n+1).
The differencemoleculeoutlinesthegridpointsinvolvedin the
calculationand the expansionpoint represents the grid point
aboutwhich finite differenceapproximationsare expanded
C. Crank-Nicolson
method (derived). The explicit andimplicit methodshavefirst-order
temporalaccuracywhereasthe Crank-Nicolsonmethodhas
n+2
second-ordertemporalaccuracy. All three methodshave
second order spatial accuracy. Explicit methods are
computationally straightforward,butthesizeof thetime step
in the explicit methodis constrained.Implicit and Crank-
Nicolson methods have no constraints on the size of the time
n+l
step, but require the solutionof a systemof simultaneous

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.

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

PEACOCK 65

Tn+l= A4Tn (20)


Initialize thermal parameters
Initialize model parameters Fortunately,matrix A is a tridiagonalmatrix (Table lB)
meaningthat coefficientsonly occuralongthe diagonaland
one position before and after the diagional; all other
coefficientsare zero. Tridiagonal matricescan be inverted
rapidly usingsimple algorithmssuchas thosepresentedin
Carnahan et al. [1969] and Anderson et al. [1984]. Because
matrixA is tridiagonal,only the threediagonalbandsneedto
Calculate second derivative at be storedin computermemory;there is no need to storethe
entire matrix.
each point:
The major advantageof the implicit methodis that it is
unconditionallystablefor any size time step. The implicit
AT Ti+l' 2Ti+ Ti-1 methodhasthe sameaccuracy(truncationerror)asthe explicit
method,thatis O{At, (Ax)2}. AsAt increases,
theaccuracy
Az
2 (Az)
2 of the implicit finite differencesolutiondecreases
so that,in
practice,very large time stepsare not desirable. The user
shouldtesttheaccuracyof thenumericalsolutionby rerunning
theprogramusinga smallertime step.
A common finite difference method that has second-order

Calculate T at each point: temporal accuracyis the Crank-Nicolsonimplicit method


[Crank and Nicolson, 1947]. In the Crank-Nicolson method
theexpansion
pointischosen
tobeTin+l/2asshown
in Figure
5C. Centraldifferenceequationsare usedfor both time and
Tnew,
i _-Told,
i + c At space,resultingin a systemof equationsof theform:
Az2
Tn+l
i _Tin c Ti+l
_n+l'---i
9.Tn+l+ Ti-1
n+l

At =- (Ax)
2
Calculatetemperatureat boundaries K n1- 2T+T ni-1
ti+ 2 2
usingboundaryconditions +-- , + O{(At) ,(Ax) }
,

2 (ax)
2 (21)

The systemof equationswritten in matrix form is given in


Table 1C. Equation(21) hasa higherordertruncationerror,
Print out temperatures O{ (At)2, (Ax)2), andis therefore
thepreferred
methodfor
manyone-dimensional, time-dependentdiffusionproblems.
Finite difference methodscan be used to solve partial
differentialequationsinvolvinga variety of termsincluding
advectionand non-linearterms. Advectiontermsare usually
approximated using backward, or upwind, difference
No equations.The occurrenceof an advectionterm imposesan
Finished? additionalstabilityconstraint
on theexplicitmethodof:

At < Ax/u (22)

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

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66 THERMAL MODELING OF METAMORPHIC P-T-t PATHS

TABLE 1A. Systemof equationsfor theimplicitfinite differencemethod


with constanttemperature boundaryconditions.

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)

TABLE lB. Compactsystemof equations


for theimplicitfinite differencemethod
with constanttemperatureboundaryconditions.

,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 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

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PEACOCK 67

TABLE 1C. Systemof equationsfor Crank-Nicolsonmethod


with constant
temperatureboundaryconditions.

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

0 0 0 ' . ' . ' . 0 0


n+l
0 0 0 0 -s (l+s) -s 0 I-3
n+l
0 0 0 0 0 -s (l+s) I-2
a+l
0 0 0 0 0 0 -s (l+s) [-1

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

particularlyusefulmethodfor 2- and3-dimensional problems equationis replacedby its equivalentintegralform and the


is the alternating-direction
implicit (ADI) method[Peaceman resultingsystemof equationsis minimizedusingthe calculus
and Rachford, 1955]. The ADI methodis a time-splitting of variations. Examplesof finite elementtechniques
applied
methodthathasthefollowingadvantages: (1) the ADI method to geologicalproblemsincludeShi andWang [ 1987] andBird
is unconditionallystablefor any size time step;(2) the ADI [1988].
methodhas second-order temporalaccuracy, that is, the Boundary Conditions. Boundary conditions must be
truncationerror is O{(At)2, (Ax)2, (Ay)Z} for a two- specifiedin orderto solveany differentialequation,whether
dimensional problem;and(3) theresultingsystemof equations using analytical or numerical methods. The steady-state
is tridiagonalandthereforecanbereadilyinverted.Accessible solutionof a partialdifferentialequationdependssolelyon the
descriptions of the ADI methodmay be foundin Carnahanet boundaryconditionsand not on the initial conditions.Up to
al. [1969], Smith [ 1985], and Presset al. [ 1986]. now we haveconsideredonly one specifictypeof boundary
Finiteelementtechniques arecommonlyemployedto solve condition- constanttemperature.Therearethreegeneraltypes
problemsin a variety of engineeringapplicationsand are of boundary conditions, two of which are commonly
particularlyusefulfor problemsinvolvinghighly irregular encountered in geologicproblems.
geometries. Finite element methods differ from finite A Dirichlet boundaryconditionspecifiestemperature at the
differencemethodsin two ways: (1) In the finite difference boundaryas functionof time [Noye, 1982]. Many geologic
method,grid pointsaredefinedat theintersection of parallel problems involve boundary conditions that are periodic
lines. In the finite elementmethod,theregionis dividedup functionsof time (e.g., daily surfacetemperature).Because
into irregularly-shapedelements,the cornersof which are we marchthroughtime in the finite differencemethod,we can
connectedto discretepointson the boundary. Many finite easilycalculatethe temperatureat a Direchletboundaryat each
elementschemesusea triangularelementandthe differential time level. The constanttemperatureboundaryconditions
equationis approximated at the centroidof eachtriangle. usedin the exampleaboveare the simplestform of Dirichlet
(2) In the finite element method, the partial differential boundarycondition.

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

THERMAL MODELING OF METAMORPHIC P-T-t PATHS

A Neumannboundaryconditionspecifiesthefirstderivative methodsin that they satisify the criteria of convergence,


of temperatureat the boundaryas a functionof time [Noye, consistency,andstability[e.g.,Noye, 1982].
1982]. Thederivativemaybenormalto theboundary (3T/3x) A solutionto a finite difference equation(FDE) which
or tangentialto the boundary(3T/3t). Normal derivative approximates a partialdifferentialequation(PDE) is saidto be
boundaryconditionsare encounteredin geologicproblems convergentif at every point in the solutiondomain,the FDE
wheretheheatflux is specified(e.g., mantleheatflux into the solutionapproaches thePDE solutionasthegridspacings (At,
baseof thecrust).Note thatspecifying 3T/3x at theboundary Ax, Ay) approachzero [Noye, 1982]. Convergencecan be
fixestheslopeof thetemperatureprofileat theboundary. rigorously demonstratedfor a few simple cases (e.g.,
Neumann boundary conditions are approximated as 1-dimensionaldiffusion),but analyticalsolutionsdo not exist
polynomial expressions of nearby interior grid points. for manycommonly encountered partialdifferentialequations.
Considerthe caseof a constantheatflux boundarycondition Fortunately, convergencecan be demonstratedfor linear
definedby Fourier'slaw: problemsby usingLax's equivalencetheoremwhich states
"Given a properlyposedinitial value problemand a finite
q=C=-k3-T difference approximation to it that satisfiesthe consistency
(23) condition,stabilityis thenecessary andsufficientconditionfor
convergence"[Noye, 1982]. In other words, in order to
where q = heat flux and k = thermal conductivity. demonstrate the convergence of a finite differenceequation,
Rearranging, we needonlydemonstrate consistency andstability.
A FDE is said to be consistent with a PDE if in the limit as
3T -C 1 the grid spacingstendtowardzero,theFDE becomesthe same
)x- k -C2 asthePDE at eachpointin thesolutiondomain[Noye,1982].
(24) Consistencyof finite differenceequations
can be shownby
consideringthe relationbetweenT(x+Ax) andT(x) usinga
and using a forward difference equation for T1 at the Taylor seriesexpansion:
boundary:
2
n+l _n+l
Ax3T(Ax)32T
C2=
) T2-T1O{Ax} =

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.

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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:

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70 THERMAL MODELING OF METAMORPHIC P-T-t PATHS

(1) the amountand distributionof radioactiveheat-producing


elementsin the crust,and (2) the amountof heatflowing into Temperature(C)
the base of the crust from the mantle.
It is generallyacceptedthat the uppercrustis enrichedin 0 100 200 300 400 500 600
radioactiveheat-producingelementswith respectto the lower 0
crust, but the precise distribution of such elements is not
known. One commonmodelis to assumethatheat-producing
elements decrease exponentially with depth over a 5
characteristiclength scale (1/e dropoff length), L [e.g.,
Lachenbruch, 1970]. Other models assume that heat-
producing elements are uniformly distributed in the
uppermost,say 10 km, of the continentalcrust. 10
If an exponential relationshipis adopted,a steady-state
continentalgeothermmay be calculatedfrom the following j:= 15
equation[modifiedfrom eqn. (4-30) of Turcotteand Schubert,
1982]:
20
qm z -(1
T=T s+----+ AL - e-%
(30)
25
whereTs= surface
temperature
[K],,
qm = mantle heatflux [W/mZ],
z = depthIra], 3O
k = thermalconductivity[W/(m K)],
A = volumetric
heatproduction
rate[W/m3],and
L = characteristiclengthscale[m]. 35 ' ' ' ' ' ' '
Figure7 is a plot of the steady-state
continentalgeotherm
calculatedusing equation(30) where Ts %0 C,qm= Fig. 7. Initial pre-thickening
crustalgeothermcalculatedusing
-0.03 W/m2, k = 2.25 W/(m K), A = 2 x 10-0 W/m, and equation (30) and the following parameters: Ts = 0 C;
L = 10 km. Note that the concentration of heat-producing qm= -0.03W/m2;k = 2.25W/(mK); p = 2700kg/m3;
elementsin the upper crust resultsin the geothermbeing C = 1000 J/(kg K); radioactiveheat production,A = 2 x 10-
curvedratherthan a straightline. The heatflux throughthe W/m 3 at the surfacedecreasing exponentially over a
surface(z = 0 km) is -0.05 W/m2; thus,heat-producing characteristiclength scale of 10 km. The concentrationof
elements
resultin anadditional tothe heat-producingelements in the upper crust result in the
-0.02W/m2 beingadded
mantle heat flux of-0.03 W/m 2. geotherm being curved, rather than a straight line. The
Models of crustal thickening. In order to model regional temperatureat the baseof the 35 km-thick continentalcrustis
metamorphismresultingfrom crustalthickeningwe need to 553 C and the surfaceheat flux is -0.05 W/m 3.
considerthe geometry of crustal thickening. England and
Thompson [1984] describe three different end-member
geometries,two of which will be discussedhere. Note that
England and Thompson[ 1984] do not use the exponential exponentiallywith depthover a characteristiclengthscaleof
distributionof heat-producing elementsadoptedhere. 20 km, insteadof 10 km (Figure 8D).
In the first model, the crust is thickenedinstantaneously Neither model is intendedto accuratelyrepresenta specific
along a single thrustfault. The thrustsheetis 35 km thick; orogenic event, but rather the two models representend-
after emplacementthe crustis 70 km thick, twice the normal member casesof crustal thickening. The sawtooth model
thickness. The resulting geotherm, shown in Figure 8A, more closely approximatescontinent-continentcollision
resemblesa "sawtooth",thusthis model is commonlyreferred characterizedby rapid convergencealong a discretethrust
to asthe sawtoothmodel. The thrustingeventredistributes the system whereas the homogeneousmodel more closely
heat-producing elementsinto two layers,the topsof which lie approximatesslow convergencedistributedamongnumerous
at 0 and 35 km depth (Figure 8B). In both layers the thrust faults or crust thickened in a ductile manner.
concentration of heat-producing elements decreases Initial and boundary conditions. Figure 8 representsthe
exponentiallywith depthover a characteristiclengthscaleof initial conditionsrequired for our finite-differencemodels.
10 km. Figures8A and8C definetemperatureasa functionof depthat
In the second model, the crust is thickened to 70 km in a time = 0, T(z, t = 0), for the sawtooth and homogeneous
ductile fashion, rather than along a discrete thrust fault. models, respectively. Figures 8B and 8D define the heat
Becausethis modelapproximateshomogeneous shorteningof productionfrom radioactivedecay as a function of depth,
the crust(or homogeneous thickening)it is referredto as the A(z). Strictly, radioactiveheat productionis a functionof
homogeneousmodel. The resulting geotherm, shown in time, but we can ignore this because: (1) the temporal
Figure 8C, is achieved by "stretching"the pre-thickening variation is minor over the tensof m.y. consideredin these
geothermparallel to the depth axis. The temperatureat the models;and(2) the temporalvariationis muchsmallerthanthe
base of the crust is still 553C, but the base of the crust now uncertaintyin the absoluteconcentrationand distributionof
lies at 70 km depth. The distributionof heat-producing heat-producing elements.
elements is stretchedin a similar fashion. In this case, the The boundaryconditionsfor the two modelsare the same.
concentration of heat-producing elements decreases At the top of each model the surfacetemperatureis held

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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

PEACOCK

(A) Temperature (C) (B) Heat production(W/m**3)


o 100 200 300 400 500 600 0e+0 1 e-6 2e-6
o 0

lO 10

2o 2O

E 30 E 30

_ 40 - 40

50 50

6O 6O

7O 7O

(c) Temperature(C) (D) Heat production(W/m**3)


o 100 200 300 400 500 600 0e+0 1 e-6 2e-6
o 0

lO 10

2o 2O

3o E 30

4o _ 40

5o 50

6o 6O

7o
I . I . I I . I
7O

Fig.8. Initialgeotherms anddistributionsof heat-producing elementsusedin thecrustal thickening models.


(A) Initialsawtooth geotherm representingtheinstantaneous thrusting
of a 35 km-thickthrustsheetontopof
thecrustthatresultsin a doublingof thecrustalthicknessto 70 km. Thegeotherm is derivedby stacking two
initialgeotherms (Figure7), oneontopof theother. Theindividual datapointsillustrate thefinitearray
spacing usedin themodels.(B) Distribution of heat-producingelementsin thesawtooth model.Radioactive
heatproducting elements occurin twolayers,thetopsof whichlie at 0 and35 km depth.In bothlayersthe
concentrationof heat-producingelements decreases downward exponentiallyovera characteristic
lengthscale
of 10km. (C) Initialhomogeneous geotherm representingthehomogeneous thickeningof thecrustto 70km.
Thegeotherm isderivedbystretching theoriginalgeotherm (Figure7) bya factorof two,parallelto thedepth
axis. (D) Distribution of heat-producingelements in thehomogeneous model.Theconcentration of heat-
producing elements decreasesdownward exponentiallyovera characteristic
lengthscaleof 20km.

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

72 THERMAL MODELING OF METAMORPHIC P-T-t PATHS

Temperature (C) Temperature(C)


0 200 400 600 800 1000 0 200 400 600 800 1000
0

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

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

PEACOCK 73

(A) Temperature(C) (B)


0 200 400 600 800 1000
0 ..... 600

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 . , , . ,

10 . 500 40kl '


20
o.

400. _
- 300
m
;o 200
40
oo[
o; , 1'0 ' ' 3'0 ' 40
o Time (m.y.)

Fig. 10. Derivationof temperature-timepathsfor sawtooth andhomogeneous modelswith no erosion.


Geotherms labeledwithtimein m.y. (A) Thermalevolution of sawtoothmodelshowing temperature
increasesfora rocklocatedat40kmdepthin thethickened crust.Thispointwasinitiallyat5 kmdepthand
wassubsequently buriedbytheinstantaneousemplacement of a 35km-thick
thrustsheet.(B) Temperature-
timepaths forrockslocatedat30km(upper plate)and40km(lowerplate)in thethickenedcrust.Duringthe
firstseveralm.y.,thedecreasein temperature
at 30 kmdepthis mirroredbytheincrease in temperature
at
40kmdepth.Thisreflects therapidconductionof heatfromtheupperplatedownward intothelowerplate.
Subsequently, bothrocksundergo heating
asthegeotherm relaxestowardthesteady-stategeotherm.(C)
Thermal evolutionofhomogeneous modelshowing temperature
increases
fora rocklocatedat40kmdepthin
thethickened
crust.Thispointwasinitiallyat 20 kmdepthandwassubsequently
buriedto 40 kmdepth
duringinstantaneous
homogeneous
crustal
thickening.
(D) Temperature-time
pathsforrockslocatedat30km
and40kminthehomogeneously
thickened
crust.Bothrocks
heatupatapproximately
thesame ratereflecting
thedecayof radioactive
elementsandtheconduction
of heatintothebaseof thecrustfromthemanfie.

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

7/4 THERMAL MODELING OF 1VIETOC P-T-t PATHS

evolutionof a rock locatedat 30 km depth,5 km above the


thrust fault. This rock initially cools as heat is conducted Temperature(C)
downward;after 6 m.y. temperaturesbeginto increaseas the
geothermrelaxestoward the steady-stategeotherm. During 200 400 600 800 1000
thefirst severalmillionyears,thedecrease in temperature at 30
km depthis mirroredby the increasein temperatureat 40 km
depth. This reflects the rapid conductionof heat from the
upperplatedownwardinto thelowerplate. At latertimes,heat 10
flux from the mantle and radioactive decay increases
temperatures at thesedepths.
Similar diagramsare shownfor the homogeneous modelin
Figures10C and 10D. The rock at 40 km depthwasinitially 2O
at 20 km depthprior to homogeneous thickening;similarlythe
rock at 30 km depth was initially at 15 km depth.
Temperatures at both30 km and40 km depthincreaseslowly
over time as the geotherm approachesthe steady-state
geotherm.
The incorporationof uplift into thefinite differencemodels a) 40
allowsus to calculatepressure-temperature-time paths. (Note
I am usingthe term uplift in a broadsensethat includesboth
tectonicunroofingand sedimentaryerosion.) Uplift can be 5O
thoughtof as the upwardtransportof materialthroughthe
surface(z = 0), that is, rocks are broughtup from deeper
crustal levels to shallower levels as material is removed
6O
(eroded) from the surface. Uplift implies advectiveheat
transfer.As a rockmovestowardthesurface,it carriesalong
its associated "heat". If there is no heat conduction or heat
7O
production,the temperatureof a rock would stay the same
during the uplift process. Uplift, like all advective heat
transfermechanisms,translatesthe thermalstructurealong Fig. 11. Illustrationof theeffectof uplift anderosionon the
with the movingmedium. sawtoothgeothermin modelwith no heatconductionand no
Figure 11 illustratessomeimportantaspectsregardingthe heatproduction.Diagionalstripingdelineates baseof thecrust
incorporationof erosioninto a finite-differencemethod. Once thathasmovedup20 km over20 m.y.(upliftrate= 1 mm/yr).
a finite differencearrayhasbeendefined,it is generallyfixed Uplift, like all advectiveheattransfermechanisms,translates
for the durationof the program. Uplift can be modeledby the thermal structure.along with the moving medium.
eitherhavingthe surfacemigratedownwardover time, or by Temperatures in theuppercrustincreasesubstantially
because
havingthebaseof thecrustmigrateupwardovertime. In my uplift anderosionexposesdeeper,hotterrocks. The lack of
models,I havechosento havethe baseof the crustmigrate heatconduction in the modelis for demonstration
purposes
upwardwith time. Figure 11 showsthe (unrealistic)effectof only;conduction wouldresultin therapidsmoothing outof
eroding20 km of crust(20 m.y. of erosionat 1 mm/yr), but the sharpkinksin thegeotherm.
not permittingany heat conductionor heat production. The
thermal structureof the crust is simply translated20 km
upwardasillustratedby the arrows. The baseof the crusthas
movedup 20 km from a 70 km depthto 50 km depth. Note
thatthe surfacetemperatureis still 0 Cin orderto satisfythe
upperboundarycondition. instantaneous thickening(the startof the model). In Figure
Several different erosion (uplift) models have been 12C, a 20 m.y. time lag occursbetweenthe thickeningevent
proposedin the literature,but, in general,complexmodelsdo and the onsetof erosion. On bothdiagramsthe dashedline
not appearto be justified given the currentuncertaintyabout with arrows showsthe depth (pressure)- temperaturepath
the drivingforcesfor uplift andlongterm uplift rates. I have followedby a rock initially at 40 km depthafterinstantaneous
chosento modelerosionas takingplaceat a constantrate. I thrusting. In the model depictedin Figure 12A, the rock
have also followed the modelsof Englandand Thompson reachesa maximumtemperature of 399 Cat a depthof 23 km,
[ 1984] in allowinga possibletime lag to occurbetweencrustal 17 m.y. after crustal thickening. In the model depictedin
thickeningandthe onsetof uplift. While thereappearsto be Figure 12C, the rock experiences a periodof isobaricheating
little geologicaljustificationfor a timelag beforethebeginning for 20 m.y. prior to the onsetof erosion. Subsequentlythe
of uplift, a time lag may be necessaryin order to achieve rock reachesa maximumtemperatureof 511C at a depthof
temperatures necessaryfor high-grademetamorphism.It is 26 km, 34 m.y. after thickening. The time lag before the
possible that the uplift time lag makes the instantaneous onset of erosion resulted in a 110 C difference in the
thickeningmodelmorerealisticbecause continentcollisionis a maximumtemperatureachievedby therock becausethe rock
processthattakesplaceovertensof millionsof years. wasallowedto heatup at depthbeforebeingforcedup toward
Two different thermal evolutiondiagramsare shownin the cooler surface.
Figure 12 for the sawtoothmodel. In Figure 12A, erosion Metamorphic pressurescan be calculated from crustal
takes place at 1 mm/yr and starts immediately after depthsusingtherelation:

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

PEACOCK 75

P = pgz (31) Figure 13 shows the thermal evolution and pressure-


temperature-timepaths for two homogeneousthickening
where P = pressure
[Pa], models. In the first modelerosionbeginsimmediatelyafter
p = density[kg/m], thickening (Figures 13A and 13B), whereasin the second
g = gravitational
constant
[9.8m/s2],and model erosionbegins20 m.y. after thickening(Figures13C
z = depth[mi. and 13D). Erosionof homogeneously thickenedcrustresults
In our modelswe have useda constantcrustaldensityof in elevatedthermalgradientsin the upperpart of the crustas
2700kg/m3, suchthatP (MPa)= 0.02646z(m). Usingthis comparedto the casewithouterosion(compareFigures 13A
relation,we cangeneratepressure-temperature-time
pathsfor and 13C with Figure 10C).
differentrocksfrom the diagramspresentedin Figures12A Pressure-temperature-time paths in the homogeneous
and 12C. modelsare qualitativelysimilarfor rockslocatedat 30 and 40
Figure 12B showsthe pressure-temperature-time pathfor km depth in the thickened crust because there is no
two rocks in the sawtooth model where erosion begins discontinuityat 35 km depthas thereis in the sawtoothmodel.
immediatelyafterinstantaneous thickening.The curvelabeled In Figure 13B, both rocks experience approximately
'40 km' in Figure12Brepresents a rockinitiallyat 5 km depth isothermaldecompressionfor over one-half of their uplift
that was buried to a depth of 40 km by instantaneous history. The '40 kin' rock reachesTmax= 388 C at PTmax=
overthrustingof a 35 km-thick thrustsheet. Subsequently, 662 MPa, at t = 15 m.y. after thickening. The '30 kin' rock
pressuredecreases aserosiontakesplaceandtherockheatsup reachesTmax- 295 C at PTmax= 556 MPa, at t = 9 m.y.
asthe geothermrelaxestowardthe steady-state geotherm.The after thickening. It is importantto note that the two rocks
rock reachesa maximum temperature,Tmax= 399 C, at a achievedTmaxat different times. In a metamorphicterrane,
pressure PTmax = 609 MPa. PTmax-Tmax are the P-T rocksof differentmetamorphicgradegenerallyrepresentP-T
conditionsthat are thoughtto be recordedby the mineral conditions achieved at different times.
assemblage in a metamorphicrock [Spear,thisvolume]. The In Figure 13D, both the '30 km' and '40 km' rocks
pressure-temperature-timepathhasthreeimportantfeatures: experience 20 m.y. of isobaric heating that increases
(1) The pressureat Tmax is only ~60% of the maximum temperatures-95 C followed by a periodof approximately
pressureexperiencedby the rock (Pmax= 1058 MPa). (2) isothermal decompression. The '40 km' rock reaches
The rock spends50% of its uplift history(from 34 to 13 km, Tmax = 479 C at PTmax= 741 MPa, at t = 32 m.y. after
900 to 344 MPa) within50 Cof themaximumtemperature. thickening.The '30 kin' rockreachesTmax= 374 C at PTmax
Thus,a majorpartof the rock'shistoryis spentundergoing = 609 MPa, at t = 27 m.y. after thickening.Onceagain,peak
approximately isothermal decompression. (3) The pressure- metamorphicconditionsare achievedat differenttimes.
temperature-time pathdefinesa counter-clockwise loopon a After severalm.y., the P-T-t pathsin Figures12D and 13D
P-T diagramwithP increasing downward.On a P-T diagram areremarkablysimilar. The slightdifferencesresultprimarily
drawnwithP increasing upward(asis thecasein mostphase from the different distributionsof heat-producingelements
equilibriadiagrams) thepressure-temperature-time pathdefines betweenthe two models. The long-termthermalevolutionof
a clockwiseloop. thecrustis insensitive to thethickeningmechanism.
The curve labeled '30 km' in Figure 12B representsthe
pressure-temperature-time pathfollowedby a rock locatedin ContactMetamorphism
the upperplate, 5 km abovethe thrustfault. The rock cools
quickly,from 485 Cto 328 C,in 2 m.y. in response to the Thermal modeling of contact metamorphicaureolesis
rapidconduction of heatdownward intothecoollowerplate. particularlywell-suitedto numericaltechniques.In contrastto
Temperatures continue to declinethroughout theuplifthistory mostanalyticalmethods,numericalmethodspermit variable
of the rock;thus,any metamorphism recordedby thisrock thermal parametersas a functionof time and space. Thus,
will be retrograde. heatsof crystallization andheatsof metamorphic reactionscan
Figure12D illustrates pressure-temperature-time pathsfor be incorporated into models of contact metamorphism.
two different rocks in the sawtooth model where erosion Explicit finite differencemethodsmay be moreefficient than
begins20 m.y. afterthethickening event. The twopathsare implicitmethodsfor modelsof contactmetamorphism because
qualitativelysimilarto thepathsshownin Figure12Bwiththe small time steps must be taken in order not-to overstep
followingexceptions. crystallizationandreactionintervals.
The first 20 m.y. of the '40 km' path consistsof isobaric Figure 14 illustratesa simple one-dimensionalnumerical
heatingfrom102Cto 453 C. Onceerosion begins,therock modelof contactmetamorphism.The finite-difference arrayis
undergoes approximate isothermal decompression. Therock orientedperpendicularto the intrusivecontact. The intrusion
reachesa maximumtemperature, Tmax= 511 C at PTmax= is assumedto be emplacedinstantaneously alongthe left side
688 MPa, at t = 34 m.y. afterthickening. of the model. Becausethis is a one-dimensionalmodel, the
The '30 km' curvein Figure12D definesa slighfiymore intrusionis consideredto extend infinitely in the directions
complexpressure-temperature-time path. For thefirst6 m.y. perpendicular to the finite-differencearray.
the rock coolsisobaricallyfrom 485 C to 311 C. For the At t = 0, the initial temperatureprofile is a step-function
next 14 m.y., the rock undergoes minorisobaricheatingto with temperaturesat points in the intrusion initialized to
349 Casthegeothermrelaxes(Figure12C). With theonset Tmagmaand temperaturesat points in the countryrock
of erosionand decompression, temperaturescontinueto initia-lized to Trock. In considering possible boundary
increase slightly, reaching Tmax = 371 C at PTmax= conditions,we can take advantageof the symmetryof the
582 MPa, at t = 28 m.y..after thickening. However, the problem. The left-sideboundary(at x = 0) coincideswith the
maximumtemperature is lessthantheinitial temperature of center of the intrusion, a plane of symmetry (Figure 14).
485 C,sonoprogrademetamorphism will occur. Becausethe temperatureat the centralplaneis at a maximum,

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

76 PEACOCK THERMAL MODELING OF METAMORPHIC P-T-t PATHS

(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 ' ' ' ', ' , ,

(C) Temperature(C) (D) Temperature(C)


0 200 400 600 800 1000 0 100 200 300 400 500 600
0

10 2OO

20
400

30
600
40

800
50 3o km

1000
60
4O km
70 1200

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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.

Fig. 12. Thermalevolutionandpressure-temperature-time pathsfor thesawtoothmodelwith two different


upliftmodels.Geotherms labeledwith timein m.y. Diagonalstripingmarksbaseof crust. (A) Thermal
evolutionof sawtoothmodelwith an uplift rate of 1 mm/yrstartingimmediatelyafterthickening.Points
connectP-T pointsfor a rock locatedinitially at 40 km depthin the thickenedcrust. (B) Pressure-
temperature-time pathsfor rockslocatedat depthsof 30 km (upperplate)and 40 km (lowerplate) in the
sawtooth model.Dashedline,with arrows,represents theportionof thepressure-temperaturepathimpliedby
the instantaneous thickeningmodel. The 40 km rock definesa counter-clockwise loop in P-T space.Over
50% of its uplift historyoccursunderapproximately isothermalconditions.The 30 km rockundergoes
coolingthroughout its thermalhistory. (C) Thermalevolutionof sawtoothmodelwith an uplift rate of
1 mm/yrstarting20 m.y. afterthickening.PointsconnectP-T pointsfor a rocklocatedinitially at 40 km
depthin thethickened crust.(D) Pressure-temperature-time pathsfor rockslocatedat 30 and40 km depthin
the sawtoothmodelwith delayeduplift. Duringthe first 20 m.y. prior to the onsetof regionaluplift, the
40 km rock heatsup ~360 C isobarically.The 30 km rock coolsisobaricallyover the first 6 m.y. after
whichtime the rockstartsto heatup. After 20 m.y., therocksare upliftedapproximatelyisothermallyuntil
they approachthe surface. The maximumtemperature achievedby the 30 km rock is lessthanits initial
temperature,suchthatanymetamorphism will beretrograde.

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

78 THE MODELING OF 1VIETOC P-T-t PATHS

(A) Temperature(C) (B) Temperature (C)


0 200 400 600 800 1000 o 100 200 300 400 500 600
o o

lO
2OO

2o
4OO

30
6OO

g- 40
8OO
50 3O km

lOOO
60
4O km
7O 1200 ! ! I . I . I

(c) Temperature(C) (D) Temperature(C)


0 200 400 600 800 1000 o 100 200 300 400 500 600
0 o

10 2OO

20
4OO

30
6OO

g- 40
8OO 3O km
50

lOOO
60 4O km

1200
70

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

PEACOCK 79

Fig. 13. Thermalevolutionandpressure-temperature-time pathsfor the homogeneous modelwith two


differentuplift models. Geothermslabeledwith time in m.y. Diagonalstripingmarksbaseof crust.
(A) Thermalevolutionof homogeneous modelwith an uplift rateof 1 mm/yrstartingimmediately after
thickening.PointsconnectP-T pointsfor a rocklocatedinitiallyat 40 km depthin the thickenedcrust.
(B) Prossure-temperature-time pathsfor rockslocatedat 30 and40 km depthin thehomogeneous model.
Dashedlines,witharrows,rapresent theportionof therespective pressure-temperaturepathsimpliedby the
instantaneous homogeneous thickening model.Over50% of theuplifthistoryoccursunderapproximately
isothermalconditions.(C) Thermalevolution of homogeneous modelwithupliftat 1 mm/yrstarting 20 m.y.
afterthickening.Pointsconnect P-T pointsfor a rocklocatedinitiallyat 40 km depthin thethickened
crust.
(D) Pressure-temperature-time pathsfor rockslocatedat 30 and40 km depthin thehomogeneous modelwith
delayeduplift. Duringthefirst20 m.y.priorto theonsetof uplift,therocksheatup ~ 95 C isobarically.
After20 m.y.,therocksareupliftedapproximately isothermally untiltheyapproach thesurface.Notethe
similaruplifttrajectories
for thesawtooth andhomogeneous models(compare Figures12D and13D). The
longtermthermalevolution of thickened crustisrelatively
insensitive
to thegeometryof thickening.

Literature Review havechosento discussthosearticlesthatI considerimportant


'landmark'papersandarticlesthatareparticularlyilluminating
or innovative. The followingdiscussion is admittedlybiased
The purposeof this sectionis to providethe readerwith an toward my researchinterests,but I have tried to achieve a
overview of analyticaland numericalmodelsof heat transfer masonablybalancedpresentation.The readeris encouraged to
andmetamorphic pressure-temperature-time pathspresentedin searchthe past literatureusingthe referencescited in these
thegeologicalliterature.It is beyondthescopeof thiswork to papersand to searchthe future literatureusing the Science
discussall of themodelspresented in theliterature.Instead,I Citation Index.

+ +
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.

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

THERMAL MODELING OF METAMORPHIC P-T-t PATHS

(A) 1200 (B) 8oo


lOOO BASALT .'
800
o 600 4.8m.y.

o

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)

(C) 1200 (D) 8oo..... , ..... , .....


1000
o
I ' I I ' GRANITE

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 ' , ' , ' , 200 I . , I .

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.

Thediscussion belowis dividedupintothreepartscoveting stronglysuggeststhat regionalmetamorphism resultsfrom


regional,contact,and subduction zonemetamorphism.In crustalthickening.The Alpine,Appalachian,andCaledonide
somecasesthereis overlapbetweenthedifferentsections.A mountainbeltsrepresentthedeeplevelsof continent-continent
list of additionalreferences,
not discussedin detail,may be collisionzones.Regionalmetamorphism ispresumablytaking
found at the end of each section. placetodaybeneaththe HimalayanMountainsandTibetan
Plateau(India-Asiacollisionzone). Indeed,youngregional
Regional Metamorphism
metamorphicrocks have already been exposedin the
Himalayas.
Regional metamorphismis intimately associatedwith
mountainbuildingprocesses
that occurat convergent
plate Fundamental
ControlsonRegionalMetamorphism
margins. The commonobservationthat metamorphic
rocks
subjectedto pressuresin excessof 500 MPa (5 kb) are now Richardson[ 1970]establishedthe relationshipbetweena
exposedat the surfaceof crustof averagethickness
(~35 km) petrogenetic
grid,thefaciesseriesconcept,andthegeothermal

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

PEACOCK

gradient during metamorphism. He recognized that the


geothermduringmetamorphism mustdiffer from the "normal" -- P-T plthfealolwrock &

geotherm,that is, metamorphismmustreflecttransientthermal _L MlmOrlh:


geothirm.t
a reck faacJmstim surgacl
conditions in the crust. Furthermore, Richardson [1970]
demonstratedthat rapid burial followed by rapid uplift is
requiredto createandpreserveblueschistfaciesconditions.
As shown earlier, the thermal relaxation of thickened
continental crust results in regional metamorphismof the
middle and lower crust. Oxburgh and Turcotte [ 1974] used
argumentsbasedon the Peclet number to demonstratethat
overthrustingcausesa major perturbationof the regional
conductivegeotherm. They constructeda "sawtooth"model
representinginstantaneousthickeningof the crust along a
thrustfault, in orderto simulateregionalmetamorphism
in the
Alps. The sawtoothgeothermrelaxestowardthe steady-state
geothermovera periodof tensof millionsof years.;blueschist
faciesconditionsare achievedin the first severalmillion years
after instantaneousthickening. The resultsof Oxburghand o 2oo ,too 6oo ,oo
Turcotte [ 1974] suggestedthat time constraintson Alpine
Temperature
C
metamorphism requirean anomalously high mantleheatflow
of 75 mW/m2 intothebaseof thecrustin orderto explain
hightemperature metamorphism. Fig. 16. Pressure-temperature diagramshowingrelationship
At approximatelythe same time, Bickle et al. [1975] betweenmetamorphicgeotherm(= metamorphicP-T array),
presenteda similarcrustalthickeningmodelfor the Eastern P-T-t path, and crustalgeotherms[Englandand Richardson,
Alps. Using a slightlymorecomplexsawtoothmodel,Bickle 1977]. Dashedlines representcontinentalgeotherms20, 40,
et al. [ 1975] demonstratedthat the time lag of ~30 m.y. 60, and 80 Ma after crustal thickening by overthrusting.
between overthrusting and the peak of metamorphismis Arrows representP-T-t path followed by rock A, labeledwith
consistent with the time scale of thermal relaxation of time in Ma. Thin solid line representsthe metamorphic
thickened crust. Their model indicates that greenschist- geotherm,the locusof Tmax-PTmax pointsachievedby rocks
amphibolitefaciesmetamorphism observedin theEasternAlps whichsubsequently reachthe surface,labeledwith the time at
requireda heat flow contributionfrom the lower crust and which the rocks reach the surface. See England and
mantleof only25-42mW/m2 (0.6-1.0HFU),consistent
with Richardson[ 1977] for detailsof theparticularone-dimensional
other estimates. model. [Reproducedby permissionof the GeologicalSociety
England and Richardson [1977] demonstrated that from P.C. England and S.W. Richardson,The influence of
uplift/erosionplaysa veryimportantrolein thedevelopment of erosion upon the mineral facies of rocks from different
different metamorphicfacies. Becausethermal relaxation metamorphicenvironments,J. Geol. Soc.London,134, 201-
(heating)anderosion(decompression) of thickenedcontinental 213, 1977.]
crust take place simultaneously,the pressureduring peak
metamorphism is significantlylessthanthe maximumpressure
experiencedby themetamorphic rock. Their modelrigorously
demonstratedthe relation betweenthe pressure-temperature- EnglandandThompson[ 1984]andThompsonandEngland
time path followedby a metamorphicrock, the metamorphic [ 1984] presenteda setof one-dimensionalthermalmodelsin
geotherm(= metamorphicP-T array),andthe crustalgeotherm order to evaluate the fundamentalparametersthat control
which varies over time (Figure 16). The incorporationof regional metamorphismresulting from crustal thickening.
erosion into the heat transfer model explains the relative England and Thompson [1984] consideredthree different
scarcity of Precambrianblueschistfacies rocks; blueschist geometriesof crustalthickeningresultingin a doublingof the
terranesrequirerelativelyrapiduplift to be preservedandare crustal thickness from 35 to 70 km (Figure 17): (a)
followedto the surfaceby highertemperaturegreenschist and instantaneous thrusting of the crust; (b) homogeneous
amphibolitefacies rocks. During thermal relaxationof the thickeningof the crust;and (c) homogeneousthickeningof the
thickenedcontinentalcrust,uplift and erosionwill transport lithosphere.They concludethat the major factorscontrolling
hot deeprockstowardthe surfacetherebypromotingmelting the thermal structure of the thickened crust are the distribution
of the lower crust. of heat-producingelements,the basalheat flux, the thermal
England and Richardson [1977] also proposed a test conductivity of the crust, and the length and time scalesof
wherebythe shapeof the metamorphicP-T arraymay be used erosion. Rocks involved in crustal thickening follow a
to distinguishbetweencrustthickenedby tectonicprocesses counter-clockwisepath in P-T spacewith pressureincreasing
andcrustthickenedby magmaaddition. Tectonicthickening downward(Figure 17). After thickening,rocksheatup as the
results in a metamorphic P-T array concave toward the geothermrelaxestowardthe steady-stategeothermsupported
temperatureaxis whereasmagmaticthickeningresultsin a by the thickenedcrust. Subsequently,the rockscool as they
metamorphicP-T array convextoward the temperatureaxis. approachthe cold Earth'ssurface.Most pressure-temperature-
In practice, this test is difficult to apply becauseof the time paths for rocks lie within 50 C of the maximum
uncertaintiesin geothermobarometry and the spatialvariation temperature for one-thirdor moreof thetotaluplift history.
of thermal parameters. A more powerful approachto the All three metamorphicfacies series are encounteredin
unravelingof tectonicsettingof metamorphicrocks is the England and Thompson's[1984] thermal models. Kyanite-
construction of pressure-temperature-time paths from sillimanitefaciesseriesmetamorphismoccurswhen the crust
individualrocksasdiscussed by Spear[thisvolume]. is thickened by a factor of two or more provided the

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

82 TI-RMAL MODELING OF METAMORPHIC P-T-t PATHS

THICKENING OF THE CONTINENTAL CRUST AND LITHOSPHERE

BY THRUSTING CRUSTONLY HOMOGENEOUSLY


(CRUST ONLY) HOMOGENEOUSLY
(WHOLE LITHOSPHERE)

, 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%.

Fig. 17. Threeone-dimensional modelsof crustalthickeningconstructed by EnglandandThompson[ 1984]


showinggeometryof thickening(A, B, andC), subsequent evolutionof geotherms andP-T paths(D, E, and
F), andtherelationof P-T pathsto metamorphic facies(G, H, andI). (A) Model 1: Instantaneous thickening
of thecontinental crustalonga singlethrust.Uppercrustis shownby diagonalhatching; lowercrustby cross
hatching. Schematicisothermslabeledwith temperaturein C. The one-dimensional modelsimulatesthe
thermalevolutionof the thickenedcrustin the middleof the diagram.No lateralheattransferis permitted.
(B) Model 2: Homogeneous thickeningof thecrustequivalentto ductileshortening or numerous distributed
thrustfaults. (C) Model 3: Homogeneous thickeningof the entirelithosphere(includingthe crust).
(D) Thermalevolutionof Model 1. Geothermsare labeledwith time in Ma after instantaneous thickening.
Geothermslabeled'0' and 'vo'representinitial andsteady-state geotherms, respectively.P-T-t pathsare
shownfor rocksinitiallyat 20, 40, and60 km depth.Dotson P-T-t pathsrepresent10 Ma intervals.In the
model there is a 20 Ma time lag prior to the onsetof erosion. See Englandand Thompson(1984) for
particularthermalparameters anddetailsof the models. (E) Thermalevolutionof model2. (F) Thermal
evolutionof model3. (G) Relationof P-T-t pathsto metamorphicfaciesfor Model 1. Ve represents
equilibriumgeothermpriorto instantaneous thickening.Gla-Jad,galucophane jadeitefaciesseries;Kya-Sil,
kyanite-sillimanitefaciesseries;And-Sil,andalusite-sillimanitefaciesseries.(H) Relationof P-T-t pathsto
metamorphic faciesfor Model2. (I) Relationof P-T-t pathsto metamorphic faciesforModel3. [Reproduced
by permission of Oxford UniversityPressfrom P.C. EnglandandA.B. Thompson,Pressure-temperature-
timepathsof regionalmetamorphism I. Heattransferduringtheevolutionof regionsof thickened continental
crust,J. Petrol., 25, 894-928, 1984.]

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

PEACOCK 83

lithosphereis not thickened. Andalusite-sillimanite facies conclusions regardingtheearly thermalevolutionof thickened


series metamorphism commonly occurs, but is always crustdrawnsolelyfrom one-dimensional models.
accompaniedby melting of the lower crust which is not Karabinos and Ketcham [1988] created a pseudo-two-
explicitlyincorporated intotheirmodels.Glaucophane-jadeite dimensional model of the thermal evolution of active thrust
faciesseriesmetamorphism requiresa low mantleheatflux as beltsby 'marrying'a seriesof closely-spaced one-dimensional
resultsfrom homogeneous thickeningof theentirelithosphere. models. Their results,which agreewith the resultsof Shi and
Becauseregional crustalglaucophane-jadeite facies series Wang [ 1987],indicatethatsignificantamountsof heattransfer
metamorphismis not commonlyobserved,this geometryof occursduring the thrustingprocess.Relativelycomplicated
crustalthickeningis probablynot correct. pressure-temperature-time pathsmay be followed by rocks
In additionto thegeologicimplicationsof theirmodels,the located between two thrust faults. Karabinos and Ketcham's
mannerin which Englandand Thompson[ 1984] presentthe modelis strictlyapplicableonly to low-anglethrusts(dipping
resultsof differentcomputerrunsevaluatingtheimportanceof < 10) becausethe 'marrying' of one-dimensionalmodels
different parametersis particularly instructive. For each precludeslateralheattransfer.
variable parameter,England and Thompson[1984] choose Two-dimensional models are also needed to address the
three valuesrepresentingminimum, average,and maximum importanceand consequences of lateralvariationsin thermal
reasonable values.The resultsof all possiblecombinations are parameters(e.g., thermaldiffusivityor heatproduction)and
illustratedfor importantvariablessuchasthermalconductivity, uplift rates. Day [1987] noted that the map intersectionof
radioactive heat production, and geometry of thickening, apparentisothermsand isobarsof peak metamorphismis
whereasfor lessimportantparameters, suchaserosionaltime difficult to explainunlessuplift ratesor thermalparameters
scales,the full rangeof erosionalmodelsis illustratedonly for vary laterally. Lateralvariationsin thermalparameters leadto
averagethermalparameters.It wouldbe almostimpossibleto lateral variationsin peak metamorphictemperatures.Lateral
displayall possiblecombinations of variableparameters. variations in uplift rates exert a major control on recorded
Haugerud[ 1986] designedan interactive,screen-oriented pressuresof metamorphism. Furlong and Chapman[1987]
microcomputer program that simulates one-dimensional demonstratethat compositionalheterogeneitiesin the crust
thermal histories. The Pascal program (called 1DT) can complicatethe observedlinear relationshipbetweensurface
simulatea varietyof geologicphenomenaincludingthrusting, heat flow and heat productionof near surfacerocks; their
uplift, homogeneousstrain (thickening or thinning), and resultssuggestthat mostestimatesof mantleheat flux are too
radioactive heat production. Two of the more important large.
featuresof theprogramare:(1) theprogramis interactive,and
(2) the program producesa variety of graphic displays Regional,Low-PressureMetamorphism
includinga depthvs. temperature plot thatis displayedduring
programexecution. The programsourceand objectcode is Over thepastseveralyears,theformationof regional,low-
available from Haugerud (U.S.G.S., 959 National Center, pressure metamorphic belts has been the subject of
Reston, VA 22092). The programmingpackagemakes an considerableinvestigation.TheseBuchanmetamorphicbelts
excellentteachingandresearchtool [e.g.,Zen, 1988]. are characterized by prograde andalusite to sillimanite
metamorphism in contrast to the kyanite to sillimanite
Two-Dimensional Models metamorphism characteristic of Barrovian regional
metamorphicterranes[e.g., Miyashiro, 1961; Zwart, 1967].
Most numerical models of crustal thickening are one- Richardson [1970] considered low-pressure/high-
dimensional,consideringonly verticalheattransfer. Lateral temperaturemetamorphismto be the productof long-term
(horizontal)heat transferis assumedto be less important. radioactiveheating. England and Thompson's[1984] one-
Peclet numberargumentspresentedOxburghand Turcotte dimensional, conductive heat transfer models of crustal
[ 1974] suggestthatduringcrustalthickeningheattransferis thickeningpredict that andalusite-sillimaniteP-T conditions
dominatedby the emplacementprocessand relativelylittle canbe achievedgivenhighcrustalradioactiveheatproduction,
conductiveheattransferoccurs;thus,the thickeningepisodeis high mantle heat flux, or low crustal thermal conductivity.
"commonly modeled asoccurring instantaneously. [It should However, progradepressure-temperature pathsdo not cross
be pointedout thatthePecletnumbercalculated by Oxburgh the andalusite-sillimanite phase boundary; retrograde
and Turcotte [1974, p. 644] is for an emplacementrate of transformationof sillimanite to andalusiteupon cooling is
10 cm/yr rather than 3 cm/yr as stated in their text. predicted by crustal thickening models. England and
Nevertheless,the correctPecletnumberof 10 for v = 3 cm/yr Thompson [1984] also point out that under the conditions
still suggeststhat heat advection(emplacement)dominates necessaryto produceandalusite-sillimanitemetamorphism
overheatconduction duringcrustalthickening.] extensive melting of the lower crust should occur. The
Recently,heattransferduringthe emplacement processhas subsequent rise andemplacementof thesemagmasat shallow
beenexaminedby severalgroupsof investigators.Shi and crustallevelswill stronglymodify the thermalstructureof the
Wang [1987] developeda two-dimensionaltime-dependent uppercrust. In casesof extensivemeltingof the lower crust,
finite-element model of the thermal evolution of overthrust purelyconductiveheattransfermodelsbecomeinapplicable.
terrains. Their results,shownin Figure 18, show that for a Wickham and Taylor [1985] and Wickham and Oxburgh
thrust sheet emplaced along a 34 thrust plane at cm/yr [1987] proposed that the high-temperature/low-pressure
convergentrates,a temperatureinversiondoesnot occurin Hercynian metamorphism in the Pyrenees resulted from
contrast to the inversion assumedby the one-dimensional continentalrifting. Accordingto their model,the upwellingof
instantaneous thrustmodel. Sawtooth-shaped geothermsonly hot asthenosphereduring rifting causesan increasein the
occurat unreasonable plateconvergence rateson theorderof mantle heat flux and the intrusion of mantle-derived basaltic
2 m/yr. The results of Shi and Wang's [1987] two- magmasinto the crust. In their model, large-scalecrustal
dimensional models suggest we should be skeptical of anatexis occured at depths of 10-12 km and granodiorite

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

THERMAL MODELING OF METAMORPHIC P-T-t PATHS

0.8 m.y. magmasformedin the lowercrust. Oxygenandhydrogen


isotopic
datasuggest thatthemetamorphismwasaccompanied
by the infiltration of seawaterprior to or during peak
c0
coo
metamorphism.
wd Lux et al. [ 1986]presented
an alternative
modelby which
high-temperature/low-pressure
metamorphism iscaused
bythe
intrusionof sill-like granitic bodiesat intermediatecrustal
depths. In the caseof the northernNew Englandhigh-
0.0 20.0 40.0 60.0 60.0 100.0
temperature/low-pressure metamorphic belt,Lux et al. [1986]
DISTANCE (KM) proposed thatthegraniticmagmas resultedfrommeltingof the
lower crust causedby crustalthickening. An important
observation is that whereasthe highest-grade metamorphic
rocksgenerallyoccuradjacentto theplutons,distinctcontact
aureolesarelacking. The abundance of graniticintusionsand
the sill-like geometryof the intrusionscausewidespread
150
(regional) hightemperature/lowpressure metamorphism.
Zen [1988] investigatedanatexis(partial melting) in
thickenedcontinentalcrustusingthe one-dimensional heat
transferprogramof Haugerud[1986]. Zen'sresultssuggest
0.0 20.0 40.0 60.0 60.0 100.0
thattheupliftrateandthetimelagbeforetheonsetof upliftare
DISTANCE (KM) thedominantcontrolson the amountof crustalmelting. In
agreementwith earliermodels,Zen demonstrated
that anatexis
occursseveraltensof millionsof yearsafterthickening,
a fact
1.8 m.y. that must be consideredin interpretingtectonomagmatic
histories.
De Yoreo et al. [in press] present one-dimensional
md
Z"
-" -'
numerical models of thickened crust that take into account
o crustalmeltingand the upwardmigrationof the resulting
magmas. Extensivemeltingof the lower crustresultsin the
ascentof magmasthatstronglyaffectthe thermalevolutionof
o
o

0.0 20.0 4.0 8).0 8).0 100.0 theuppercrust. Figure19 showsthepressure-temperature-


DISTANCE (KM) timepathfollowedby a rockinitiallyat 30 km depththatis
intrudedby a graniticmagmaduringits uplift path. The
intrusionof magmaat shallowlevels causesprograde
andalusite
to sillimanitemetamorphism.
Hanson and Barton [in press]constructed2-dimensional
numericalmodelsof regionallow-pressurefacies series
metamorphicbelts. Their models suggestthat the most
importantfactor in the developmentof thesebelts is the
distribution
of magmatism overtime. Becausemagmatism
occursover an extendedperiod of time, the final distribution
0.0 20.0 40.0 60.0 8).0 100.0
of metamorphicisogradsmay bearlittle resemblance
to the
DISTANCE (KM)
distribution
of isotherms
at anyonetime.
o

CrustalThinningafterCrustalThickening

c0
coo
Crustalthinningresultingfromextension of thecrustoccurs
in several different geologicsettings. Following crustal

0.0 2).0 4).0 8).0 8).0 100.0


Fig. 18. Two-dimensionalkinematicsand thermal structures
DISTANCE (KM) of continentalcrust during overthrusting[Shi and Wang,
1987]. Diagrams are for 0.8, 1.8, and 2.8 Ma after the
initiationof thrustingat 2 cm/yr. Dashedline represents the
fault plane. For this particular geometry and cm/yr
convergencerates,no invertedthermalgradientdevelops,in
COo contrastto one-dimensional instantaneousthickeningmodels.
Z"
v
Only at unreasonable convergence ratesof theorderof 2 m/yr
c.)o. do inverted thermal gradientsdevelop. [Reproducedby
o
I-.. o ----- 300 -------- permissionof GeologicalSocietyof Americafrom Y. Shi and
C.-Y. Wang,Two-dimensional modelingof theP-T-t pathsof
0.0 2).0 4.0 0).0 8).0 100.0 regional metamorphism in simple overthrust terrains,
DISTANCE (KM) Geology, 15, 1048-1051, 1987.]

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

86 TI-IE MODELING OF METAMORPHIC P-T-t PATHS

warmerdeeperrocks. Ductile thinningof the crustresultsin F2


all rocksbeingmovedcloserto the earth'ssurface;all rocksin
the uppercrustwill undergocooling.
Ruppelet at. [ 1988] constructedone- andtwo-dimensional 6.0
finite differencemodelsof crustalextension. Rocks uplifted AS
by simpleshearand pure shearmechanisms exhibit similar
pressure-temperature-time paths. Given the currentaccuracy
of geothermobarometry,the two P-T-t paths can not be
resolved.

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

continuingdebate. Porphyroblastsare commonlyclassifiedas


being pre-, syn-, or post-deformation[e.g., Spry, 1969]. In pre- post-
principle,numericalmodelsshouldaid in theunderstanding of
the relationship between metamorphismand deformation. - reactionscatalysedby deformation
However, one-dimensional numerical models of crustal
- shear
heating
thickeninggenerally assumeinstaneousthickening,thus all
metamorphismis constrainedto occurafter deformation(the
a - deformation
givingrisetoburial
thickeningevent). Furthermore,mineralgrowthreflectsshort-
term (e.g., local folding) as well as long-termdeformation < - rockscooledbyjuxtaposition
events,so the applicationof numericalmodelsis difficult. of hot aainst cooler

Thompsonand Ridley [1987] proposeddifferentrelationhips - rocksabovea zoneof


betweenmineral growth and deformationdependingon the extensional deformation

fundamental causes of deformation and metamorphism


(Figure 21).
Perhapsthe best conclusionthat can be drawn from this
discussionregardingthe influenceof local deformationon Fig. 21. Relativetimingof deformationandmineralgrowth
metamorphic P-T paths is that care must be taken in for different geometriesof deformationand for different
determiningthe fundamentalcausesof regionalmetamorphism settingsof metamorphicrocks[ThompsonandRidley, 1987].
basedon a P-T path from a single rock. P-T paths from [Reproduced by permissionof the Royal Societyfrom A.B.
numerousrocks must be combinedwith careful geologic ThompsonandJ.R.Ridley,Pressure-temperature-time (P-T-t)
mappingandgeochronological datain orderto unravelthe P-T historiesof orogenicbelts. Philos. Trans. R.Soc. London,
historyof complexly-deformed metamorphic terranes. A321, 27-45, 1987.]

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

BB TI-tERMAL MODELING OF METAMORPHIC P-T-t PATHS

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

Fig.22. Thermalevolution of a dikeandadjacentcontactaureolederivedfromananalytical model[modified


fromLovering,1935]. Temperatures aregivenasfractionsof 190,theinitialtemperature
differencebewteen
the dike and the countryrock. The dike is 20 metersthick. Curvesare shownfor differenttimes after
instantaneous
intrusion,
in unitsof 2h.(t)1/2whichis related
to c,thermal
diffusivity,
t, time,andL, dike
half-width.SeeLovering[ 1935]for details.

[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

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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

' 2KII ' ' '


systemsand the geometryof the inducedhydrothermal ,

system.In rocksof sufficientpermeability,


theexistence of T.
steephorizontalthermalgradientswill causeconvection of
porefluids(Figure23). Porefluidsadjacentto an intrusion
will becomelessdense(morebouyant)astheyare heatedand
the fluid will tend to rise; cooler, more dense fluids from
furtherawaywill flow towardtheintrusionto taketheplaceof
therisingporefluid. Thus,a hydrothermal systemis setup
by the intrusion of a pluton into rocks of sufficient
permeability.Hydrothermalsystemsplay a very important
rolein theformationof oredeposits
abovegraniticplutonsand
in thecoolingof oceaniccrustformedat mid-ocean ridges.
Figure 24 [Norton and Knight, 1977] showsthe time- IH,SULRTI 10 FL01,6
dependent thermalstructureadjacentto an 870 C shallow- 50,000 YEARS IOO,OOO YEARS
level pluton intruded into country rock having a low
permeability
of 10-17cm2/s.Suchlowpermeabilities
resultin B.
fluidfluxes<10-9 g/(cm2os)
andinsignificant
advective
heat
transfer. Figure 24, therefore,illustratesthe coolingof a
plutonby purelyconductive heattransfer.
Figure 25 [Norton and Knight, 1977] showsthe time-
dependent thermalstructureadjacent to a 920 Cshallow-level

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.

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

90 THERMAL MODELING OF METAMORPHIC P-T-t PATHS

NortonandTaylor [ 1979]constmctea numericalmodelof


the hydrothermalsystemassociatedwith the Skaergaard
Intrusionusingthegeometryof theplutonandstableisotopic
k I0 -II dataasconstraints.Their modelsuggests thattheSkaergaard
To2('C/km systemwas characterized by extensivefluid circulationin the
permeablebasaltsandportionsof thegabbroicpluton.Two of
their more importantconclusionsare: (1) whereasconvective
coolingdidnot affecttherateof crystallization of themagma,
the solidifiedplutoncooledapproximately twiceasfastin the
presenceof thehydrothermalsystem;and(2) 75% of thefluid
infiltrated the intrusionat temperatures>480 C, consistent
with the observationthat significantoxygenisotopicshifts
occurin rocksexhibitingonly minor hydrothermalalteration
products.
Harrison and Clarke [1979] constructeda two-dimensional
numericalmodelof thecoolingof theQuottoonpluton,British
Columbia. As a constraint on their model, Harrison and
Clarke [1979] used a cooling curve determinedfrom the
differentclosuretemperaturesof a varietyof isotopicsystems
IIRTINO NO F'I..I:
(e.g., Rb-Sr hornblendeage,K-Ar biotiteage). Their results
5(1000 YEP
suggestthatafterseveralmillionyears,the dominantcooling
CONOUCTIV z NO mechanism wastheupwardtransport of crustalmaterial(uplift
' 11 ' . ' '"'s';m--r='t
---.d ' ' and erosion).
Wells [1980] presented
one-dimensionalconductionmodels
of crust thickened by magmatic intrusion. Wells [1980]
demonstratedthat the accretion mechanism,that is, whether
c. - new magmaticmaterialwasaddedaboveor belowpreviously
accretedmaterial,stronglyaffectsthe pressure-temperature-
time historyof rocksin thecrust.

IIULRTINO NO AdditionalReferences
100000 YERRS

Additionalthermalmodelsof contactmetamorphism have


been presentedby Irving [1970], DeYoreo et al. [in press],
andHansonand Barton[in press];the last two referencesare
partially discussedin the Regional Metamorphismsection
above.

Subduction Zone Metamorphism

The adventof plate tectonictheoryin the late 1960sand


early 1970swas accompaniedby a comprehensive effort to
understand the thermalprocesses andevolutionof subduction
zones. Geoscientistsusedanalyticalandnumericalsolutions
Fig. 25. Thermalevolutionof a coolingplutonvia conductive to heat transfer models in order to explain fundamental
and advective cooling [Norton and Knight, 1977]. In this observations regarding subduction zones such as the
model,a 920 Cplutonis emplacedintorelativelypermeable generationof arc magmasand the distributionof heat flow
(10-11cm2) country rock. Streamfunctions andthethermal above subductingslabs (low heat flow above trenchesand
structureare shown for t = 0.02, 0.05, 0.1, and 0.16 Ma after
high heatflow abovevolcanicarcs).
intrusion (A, B, C, and D). Stream functionsrepresent
instantaneous averagepathlinesfollowedby pore fluid; fluid Thermal Effectof SubductingLithosphere
circulationis counter-clockwise.[Reproducedby permission
of the American Journal of Science from D. Norton and
Upon first consideration,the subductionof cool oceanic
J. Knight, Transportphenomenain hydrothermalsystems' lithosphereinto the asthenosphere shoulddepressisotherms
coolingplutons,Am. J. Sci., 277, 937-981, 1977.] creatingP-T conditionsunfavorablefor magmageneration.
Observations,however,suchas the circum-Pacific"ring of
fire", clearly demonstrate that subduction of oceanic
lithosphereresults in the generationof magmas. In the
pluton intrudedinto countryrock having a permeabilityof discussionbelow,possiblesolutionsto this apparentparadox
10-11cm2/s.A vigorous hydrothermal circulation system are discussed,including the subductionof oceanic crust,
developsin thecountryrockthattransports heatfromthesides frictionalheating,inducedasthenospheric convection,therole
of the plutonto a regionlocatedabovethepluton. The system of volatiles,andmetamorphicreactions.
coolsprimarily by advectiveheat transfervia the convecting In general,thermalmodelingof subductionzonesrequires
fluid. the numerical solutionof the heat transferequationin two

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

PEACOCK 91

dimensions,although analytical approximationshave been 1.5


HEAT FLOW I )24 MY -

employed[e.g.,TurcotteandSchubert,1973]. In addition,as
CAL
!C
M
aSECM _
1.0--,

discussedbelow, it is commonly necessaryto include the 0.5-


HORIZONTAL DISTANCE. K
_

rheologicalbehavior of the asthenosphere and subducting


4OO
0-1

lithospherein thenumericalmodels. eoo-

Figure26 showsthe thermalstructureof a subductionzone


12oo

predictedby the'two-dimensional numericalmodelof Toksoz


et al. [1971]. The subductionof cool oceaniclithosphere
clearlyresultsin the depression
of isotherms.We canusethe $00-
A ie _
Peclet number discussed above to demonstrate this 2.0-
HEAT FLOW I '648 MY
phenomenon. Using a subductionrate of 5 cm/yr, a 1.5-

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,..

we calculateusingequation(1): 40O " 400'


.eoo

Pc = (v- L)/c I00- ,- Il:P


....._
= (0.05rn/yr/ 3.16x 107s/yr)-(50000
m)/(1x 10-6m2/s)
= 79 200-

The Pecletnumberfor this situationis muchgreaterthan


one,thustheadvectionof heatalongwith thesubductingslab
occurs at a faster rate than the conduction of heat into the
300 -

4OO
-
tooo
' .
--.....-
16o0-_
tooo
_

subductingslab.
Oceanic crust, consistingof mafic igneousrocks and 2.0- HIeAT FLOW t 10.8 MY -

sedimentaryrocks, comprisesthe uppermost7-10 km of


1.5

oceaniclithosphere.Meltingof basaltandsedimentary
rock I.O
-
0.5- ,Z
CAL/CM
HORIZONTAL
DISTANCE,
KM -
occursat lower temperatures thanperidotite(mantle),thusthe 0

meltingof oceaniccrustcould explainthe generationof arc


.............
_
Ioo -

magmasin subductionzones. Indeed, there is a body of


geochemicalevidenceindicatinga significantoceaniccrustal
componentin arc magmas[e.g., Gill, 1981]. :)o- -

Early thermal models of subduction zones focused on


producingthe temperaturesnecessaryfor the melting of
oceaniccrustat the top of the subductingslab [Hasebeet al.,
1970;OxburghandTurcotte,1970;Minear andToksoz,1970;
Toksoz et al., 1971, 1973; Turcotteand Schubert,1973]. All
400- .-"/'/'/
500-

600-
/////////////' ,.r,,,
', '"
-
-

-
of these early thermal models require frictional heating 00- -

(viscousdissipation) at thetopof thesubducting slabin order


to generatethetemperatures necessaryfor meltingat depthsof 800 C
100-150 kin.
McKenzie[ 1969]recognized thata slabsubducting
beneath Fig. 26. Thermalevolutionof a subductionzoneshowingthe
an islandarcmustsetup stresses in themantlethroughwhich depressionof isothermscausedby the subductionof cool
it moves. Using an analytical model, McKenzie calculated oceaniclithosphereat 8 cm/yr [Toksozet al., 1971]. Adiabatic
steady-statesteam lines for mantle flow driven by the compression, phasechanges, andstrain(frictional)heatingare
subductingslab. Viscousdragat the top of the subducting incorporatedin thenumericalmodel. Shadingindicateszones
slabinducesconvectiveflow in theoverlyingasthenospheric of phasechanges.Also shownis the heatflow patternabove
wedge. the subductionzone, which is constantover time. (A) t = 3.24
In an importantcontribution,Andrewsand Sleep[1974] Ma after initiation of subduction. (B) t = 6.48 Ma after
superimposed analyticalsolutions
for flow in a wedge-shaped initiation of subduction. (C) t = 10.8 Ma after initiation of
region with numerical heat transfer solutions in order to subduction. [Reproducedby permissionof the American
calculate the two-dimensional, time-dependentthermal GeophysicalUnion from M.N. Toksoz, J.W. Minear, and
structureof a subductionzone. Figure 27, taken from B.R. Julian,Temperaturefield and geophysicaleffectsof a
Andrews and Sleep [1974], shows the streamlinesand downgoingslab,J. Geophys.Res., 76, 1113-1138, 1971.]
isotherms in a subduction zone 0.87 and 10 Ma after the
initiation of subduction. The subductingslab inducesa
clockwiseflow in the overlyingasthenospheric wedgethat
elevatesisothermsin the arc andback-arcregions. Induced Schubertet al. [ 1975] investigatedthe role of phasechanges
asthenospheric flow increasesmantle temperatures in the [olivine-> spinel,spinel-> oxide)on thethermalstructureand
regionoverlyingthe subductingslab,resultingin increased body forces within subductionzones. Bird [1978] used a
heatflow andpossibleextensionin backarc regions. Note force balance model to calculate the distribution of stress and
thattemperatures in thesubducting
slabaretoolow to permit temperature within the Tonga and Mariana subduction
melting of the slab itself; if this model is realistic, then arc systems. Hsui and Toksoz [1979] investigatedthe thermal
magmasmustbe generated
in theoverlyingasthenosphere. structureof the mantle on both sidesof the subductingslab.
Subsequentwork has refined and expanded our Furlong et al. [1982] investigated the variable dip of
understandingof the thermal structureof subductionzones. subductingslabs by incorporatinga temperature-dependent

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

92 THERMAL MODELING OF METAMORPHIC P-T-t PATHS

(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

Fig. 27. Isotherms andstreamlinesin subduction


modelthatincorporates inducedasthenosphericflow above
thesubducting slab[AndrewsandSleep,1974]. Streamlines arelinesthataretangentto thevelocityvectorat
everypointin theflow field. Theycanbeconsidered averageinstantaneous pathlines
followedby particlesin
the asthenosphere. The inducedasthenosphericflow is clockwisein bothdiagramsandresultsin elevated
temperatures in the mantleoverlyingthe subductingslab. The top of the subducting
slabis markedby the
dashedline. Taken from Andrewsand Sleep (1974). (A) Isothermsand streamlinesafter 0.87 Ma of
subduction at 10 cm/yr. (B) Isothermsand streamlines after 10 Ma of subductionat 10 cm/yr. Induced
asthenospheric flow elevatesmantletemperatures
200-300km fromthetrench.[Reproduced bypermissionof
the RoyalAstronomical SocietyfromD.J. AndrewsandN.H. Sleep,Numericalmodelingof tectonicflow
behind island arcs,Geophys.J. R. Astron.Soc.,38, 237-251, 1974.]

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]:

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

PEACOCK 93

q = ux (37) Distance .L Trench(km)

whereq = rateof heatproduction


perunitarea[W/m2], o 35o o 35O
u = rateof movementalongthe surface[m/s], and
x = shearstressacrossthe surface[Pa].
For a convergence rateof 5 cm/yr,a constantshearstressof
160MPa (1.6 kbar)is requiredto generate
a 0.25W/m2 heat
source. All of the early thermalmodelsof subducfionzones
required shear stressesin excessof 100 MPa (1 kbar) to
generatetemperatures sufficientto meltthesubducting oceanic
crust. Suchshearstresses are 1-2 ordersof magnitudegreater 35O
than estimatesof rock strengthsat elevatedpressuresand
temperatures[e.g., Brune, 1970; Sleep, 1975; Bird, 1978;
Yuen et al., 1978]. It is unlikely that shearstressesin excess o

of 100 MPa could be maintained in rocks undergoing


dehydrationreactions[RaleighandPaterson,1965; Heard and
Rubey,1966]or in rocksat temperatures closeto theirmelting
point [e.g., Yuen et al., 1978].
Shearheatingmay be importantduringthe early stagesof
thrustingprior to the arrival of wet rocks at depth [Pavlis,
1986]. Early shearbetween 'dry' lithologiesmay preheat
rocks in the thrust zone and could result in the creation of an 35O

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

fault zonesdocumentthe importanceof frictionalheatingon


the local,centimeterscale. In my opinion,at thepresenttime,
Fig. 28. Thermal evolution of a subduction zone with
the body of evidence suggeststhat frictional heating is
frictionalheatingand dehydrationreactions[Andersonet al.,
probablynot a significan*factor during metamorphism,but
1978]. Thin lines represent 200, 400, 600, 800, and
this questionis far from resolved.
1000C isotherms. Filled region at 30 m.y. is "cold spot"
definedby closed400C isotherm(Note - I believethis is an
Effectof MetamorphicReactions artifact of the calculation scheme and would not occur in
nature.) At 40 and 50 m.y., upper and lower boundariesof
The importanceof metamorphicreactionsin the subducting filled regionare definedby 400 C isothermfor friction-only
slabhavebeeninvestigatedby severalworkers[e.g.,Oxburgh andfriction+ dehydrationmodels,respectively.[Reproduced
andTurcotte,1976;Andersonet al., 1976, 1978;Delaneyand by permissionof the University of ChicagoPressfrom R.N.
Helgeson,1978;Peacock,1987a,c]. Progrademetamorphic Anderson,S.E. DeLong, and W.M. Schwarz,Thermal model
reactions, particularly devolatilization reactions, consume for subductionwith dehydrationin the downgoing slab,
significantamountsof heatandthereforesignificantlyperturb J. Geol., 86, 731-739, 1978.]
the thermalstructureof thedowngoingslab.
Anderson et al. [1978] used a finite-difference model,
combinedwith an estimateof hydrousmineralsin subducted
oceaniccrust,to evaluatethe thermaleffectsof dehydration mineralogyresultsin an averageH20 contentfor the oceanic
reactions. Anderson et al. [1978] calculated that the crust of 6 wt %. Estimatesof the H20 contentof the oceanic
dehydrationof oceaniccrust[consistingof 25% amphibole, crustare poorly constrainedand tendto be biasedby dredge
20% serpentine, 25% chlorite, and 5% talc], consumes haul samplesfrom fracturezoneswhere permeabilities,and
~ 130 kJ of heatper kg of rock. Furthermore,theyconsidered therefore H20 contents, are anomalouslyhigh. Peacock
that the advection of released water would remove an [ 1987c]proposedthat2 wt % H20 maybe a morereasonable
equivalentamountof heat, thus they modeleddehydration estimatefor averageoceaniccrust. Secondly,Andersonet al.
reactionsas a 260 kJ/kgheatsink. The heatsinkresultsin the [ 1978] modeledthe advectionof releasedwater as a heat sink,
furtherdepression of isothermsin a subducfionzoneas shown whereasit is actuallyan advectiveheat transfermechanism.
in Figure 28. Dehydration reactions occurring in the Peacock [ 1987c] has demonstratedthat the advectionof heat
subductingslab substantiallydelay the warming up of the by fluidsin subduction
zoneshasonly a minorthermaleffect
subductingslab. (see discussionbelow).
Two considerationssuggestthat the thermal retardation DelaneyandHelgeson[ 1978] calculatedtheP-T locations
effect of dehydrationreactionsmay havebeenoverestimated of invariantandunivariantdehydration
reactionsin the system
by Andersonet al. [1978]. First, their assumedhydrous CaO-MgO-Na20-K20-A1203-SiO2-H20 to 100 kbar. Once

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

914 THERMAL MODELING OF METAMORPHIC P-T-t PATHS

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

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

PEACOCK 95

the largeamountof fluid releasedin accretionary


prisms(up to (A) TEMPERATURE (C)
50% of the subduetedsedimentvolume), fluid flow must still
be focussedinto a zone lessthan 10 km wide (parallel to the 0 200 400 600
X i 0
trench) in order to reproduce the thermal gradients. ee "ee
e
Alternatively,lessfocusingis requiredif thetemperature
at the ... ...
base of the accrefionaryprism is greateror if the prism is Z 3. '2 1
thinner and a subductionchannel separatesthe accreted
sedimentsfrom the descendingslab [e.g., Shreveand Cloos, '1o
1986].
-4::)
CreationandPreservationof Blueschists - 03
Q 20 UJ
A 6 rr
The preceding discussionhas focused on the thermal
evolutionof subductionzonesand the importantparameters
that affect the thermal structure of subduction zones.
Blueschists, rocks that record the high pressure-low 30 -8
temperatureconditionsof subductionzones,have yet to be 0 0 20 26 m..
discussed.The creationand preservationof blueschistsis a
complex problem involving structural,as well as thermal,
considerations.
Whereasthe generalthermalrequirements for
the creationand preservationof blueschistfacies rocks have
beenworkedout [e.g.,EnglandandRichardson,1977;Draper
and Bone, 1981], the coupled thermal/structuralproblem (B) TEMPERATURE
(C)
remainsto be completelysolved. 0 200 400 600
In a seriesof classicpapers,Ernst [1970, 1971a, 1971b, 0 i,_ ., ' ,'. , '. , 0
1973] established the connection between blueschist facies
I\N ". ".. "..
metamorphism and the low-temperature/high-pressure 'x '.. '
conditions encountered in subduction zones.
section of a subductionzone, Ernst [1973] superimposed
On a cross-
10L
NX...,'l'"'
z
isotherms and metamorphicfacies boundariesin order to
demonstrate that blueschist facies conditions are achieved at
' 4
convergentplateboundaries.
In the two-dimensional thermal models discussedabove,
blueschistfaciesconditionsare encountered by the subdueting
slab. However, no provision is made for getting these
blueschistsback to the surface;continuedsubducfionsimply
20- ..........
"'4 X
transportstheserocks further into the mantle. The return of
30 .... 8
blueschists to the surfaceinvolvescomplicatedprocesses that
occur in accretionary wedges including offscraping,
underplating, imbricate faulting, duplex formation, and
melange formation. For detailed discussionsof material Fig. 30. Geothermsand P-T pathsillustratingdifficulty of
transportwithin accretionarywedges,the readeris referedto preservingblueschistterranes[modifiedslightlyfrom Draper
Cloos [1982, 1984], Shreve and Cloos [1986], and Moore andBone, 1981]. A- amphibolitefacies;B - blueschist facies;
and Silver [1987]. G - greenschistfacies;P - prehnite-pumpellyitefacies;Z -
Englandand Richardson[ 1977] demonstratedthat erosion zeolitefacies. (A) Geothermsin the accretionaryprism as a
plays a very importantrole in the preservationof blueschist function of time resultingfrom thermal relaxation and self-
faciesrocks. Blueschistfaciesconditionsrecordabnormally heatingfollowing cessationof subductionand assumingno
low temperaturesfor a given depth. Upon cessationof the erosion. Note that after 26 m.y., the geothermno longer
tectonic burial process that created the blueschist facies passesthroughthe blueschistfacies. (B) P-T paths(dashed
conditions(subduction),rockswill heat up as the geotherm lines) followed by a rock initially at 30 km depth assuming
relaxestowardthe highertemperaturesteady-state geotherm. different erosionrates (labeled in cm/yr). Draper and Bone
In orderto preservethe blueschistfaciesconditions,the rocks (1981) estimateerosionratesin excessof 0.04 to 0.14 cm/yr
mustbe upliftedrapidlyor elsethe blueschistconditionswill are requiredto prevent thermal erasureof blueschistfacies
be thermallyerased. assemblages. Solidlinesrepresentsinitial geotherm.
Draper and Bone [ 1981] constructeda one-dimensional
modelof an accretionary prismoverlyingoceaniclithosphere
in order to constraindenudationrates necessaryfor the
preservationof blueschistterranes. Figure 30A showsthe 0.1 cm/yr result in maximum temperaturesoccurringin the
progressivethermalerasureof a subductiongeotherm.After highertemperaturegreenschist or amphibolitefacies. Draper
cessationof subducfion, temperaturesincreasedueto thermal and Bone [1981] conclude that minimum denudation rates
relaxation and radioactive heating. After 26 m.y., the between 0.04 and 0.14 cm/yr are required to preserve
geothermno longerintersects theblueschist
field. Figure30B blueschistterranes.Suchdenudationratesare morerapidthan
shows,for differentdenudationrates,the P-T path followed normal fiuvio-glacial erosionrates suggestingthat tectonic
by a rock initially at 30 km depth. Erosionrates less than unloading/upliftis required.

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

96 THERMAL MODELING OF METAMORPHIC P-T-t PATHS

Sierra Pelona
Vincent N]
Thrust
mylonites /
San Andreas
Fault

Pelona
Schist

0 I 2 3 4 5km

Fig.31. Schematicgeologic cross


sectionthroughtheinverted
metamorphic gradientpreservedin thePelona
Schistin theSierraPelonaarea,SanGabrielMountains, California[modifiedafterGraham andEngland,
1976].Thedashed linesbelowtheVincent thrust
markthelocationsof metamorphic isograds;
theoligoclase
isogradoccurs closest
to thethrustandthelowertemperaturegarnetisogradliesatdeeperstructurallevels.
Metamorphic gradein thelowerplateof theVincentthrustsystem decreasesstructurally
downward from
amphibolite facies(amph)throughalbite-epidote amphibolitefacies(alb-epiamph)to high-pressure
greenschist
facies(gsch).Not to scale;maximumverticalrelief is ~750 m.

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

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

PEACOCK 97

Temperature(C) earlyaccretedinvertedmetamorphicgradient Syn-subduction


uplift and/or moderately fast post-subductionuplift of
lOO 2OO 3OO 4OO 500 6OO ~1 mm/yr is requiredto preservethe invertedmetamorphic
gradient.
The numerical models predict that (1) the high-grade
metamorphicrocksin invertedmetamorphicgradientsform
earlyin the subduction
processandthereforeeffectivelydate
the initiation of subduction,and (2) inverted metamorphic
gradientsmark sitesof majorplateconvergencein excessof
1000 km [Peacock,1987d]. Thesepredictionsexemplifyhow
numericalmodelscan placeconstraintson geologicprocesses
and vica versa.

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.

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

98 TttERMAL MODELING OF METAMORPHIC P-T-t PATHS

Appendix. An explicit finite difference program.

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)

Initialize thermal parameters

KAPPA=i. 0D-6 !Thermal diffusivity (m**2/s)


DO 10 I=l, ll
TEMP (I)=0.0D00 !Initialize temperature array
DERIV2 (I) =0.0D00 !Zero out second derivative array
10 CONTINUE
TEMP (11) =1000 .D00 !Lower boundary condition

Initialize model parameters

SECYR=3 . 156D+ 7 !Number of seconds in one year


TIMYR=100 .D00 !Time step (yr)
TIMSE C=T IMYR * SE CYR !Time step (s)
ISTEPS=200 !Number of time steps
TIME=0.0D00 !Running time (yr)
SLAB=i. 0D+3 !Thickness of slab (m)
DELTAZ=100 .D00 !Array spacing (m)

Open output file and write out thermal parameters

OPEN (UNIT=11, FILE=' TSLAB. OUT ' )


WRITE (11, 9000) KAPPA
90OO FORMAT ( 'KAPPA = ', El2.4)
WRITE (11, 9100) TIME, (TEMP (JJ) , JJ=l, 11)
9100 FORMAT('T=',F6.0,' YR',l!F6.1)
C
C *** Start of time step loop ***
C

DO 100 I=i, ISTEPS


TIME=TIME+TIMYR !Increment time counter
DO 110 J=2,10 !Calculate second derivative
DERIV2(J)=(TEMP(J-1)-2.D00*TEMP(J)+TEMP(J+l))/DELTAZ**2.D00
11o CONTINUE
DO 120 J=2,10 !Calculate new temperatures
TEMP(J)=TEMP(J)+KAPPA*DERIV2(J)*TIMSEC
120 CONTINUE
WRITE(ll,9100)TIME, (TEMP(JJ),JJ=l,11)

100 CONTINUE
C
C *** End of time step loop ***
C

CLOSE (UNIT=11)
STOP
END

Copyright American Geophysical Union


Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

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.
Dehydration,asthenosphericconvectionand seismicityin Cloos, M., Thermal evolutionof convergentplate margins'
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.
andgeochemical constraints at converging
plateboundaries Tectonics, 4, 421-433, 1985.
- Part I: Dehydrationin the downgoingslab. Geophys.J.
R, Astr0n, Soc., 4_44
333-357, 1976. Crank, J., and Nicolson,P., A practicalmethodfor numerical
Andrews, D.J., and Sleep, N.H., Numerical modeling of evaluationof solutionsof partialdifferentialequationsof the
tectonic flow behind island arcs. Geor>hvs. J. R. Astron. heat-conductiontype. Proc. Cambridge Phil. Soc., 43,
Soc., 38, 237-251, 1974. 50-67, 1947.
Barr, T.D., andDahlen, F.A., Steady-statemountainbuilding Dahlen, F.A., and Barr, T.D., Steady-statemountainbuilding
2. Thermal structureand heatbudget. J. Geophys.Res., in 1. Deformation and mechanical energy balance. J.
press. Geophys.Res., in press.
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Short Courses in Geology Metamorphic Pressure-Temperature-Time Paths Vol. 7

0 THERMAL MODELING OF METAMORPHIC P-T-t PATHS

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