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THERMOBAROMETRY CALCULATIONS:
USINGMULTI-EOUILIBRIUM
A NEW TECHNIOUE,WITH PETROLOGICAL
APPLICATIONS-
ROBERT G. BERMAN
Geological Survey of Canada, 601 Booth Street,
Ottowa, Ontario KIA 0E8
SoruNaarns INTRODUCTION
Ce travail porte sur une m6thode d compatibilit One of the primary goals of petrology is to
interne (Powell 1985)d'effectuer descalculsthermobaro- quantify accurately petrogenetic conditions and
m6triques;tous les 6quilibrespossiblesimpliqu6s par un relate them to geological processes. For metamor-
assemblagede min6raux sont calcul6sau moyen d'une phic petrologists, a great deal of attention has been
banque de donn6esthermodynamiquesd compatibilit6 focused on determination of peak conditions of
interne pour les p6les et les propri6t6s de m6lange metamorphism, and much experimental and
theoretical work has been expended on the
"Geological Survey of Canada contribution number important task of calibration of equilibria that can
19091. be used for the purpose of thermobarometry. Spear
833
834 THE CANADIAN MINERALOCIST
possible reactions that can be used as ther- to assess this assumption, support for ther-
mobarometersis given by: mobarometric results must come from intra- and
intersampleconsistencyand independentgeological
n!/l(c+l)!(r-(c+l))!l (8) evidence.
TABLE 1. TWEEQU RESIJLTS FOR CALC-SIUCATE RP13 (IIOLLAND & POWELL 1990)
Mineralogy: Chl-Bt-Ms{rt-Pt-Ep-Cc-Qtz
Assemblageusedin TWEEQU calculations:Chl-Bt-MsCrt-Pl-EpQu
kevious P-T Esults: P=7.5 t 0.5 kbar @ assumed520 oC (Powell & Holland (1988)
P=7.2 I 0.3 kbar @ assumed530 oC Stolland & Powell (190)
Avemged TWEEQU results$: P=7.2 t 0.3 kbar / T=533 * 15 oC (3 indePendentreactions)
Outliss: Equilibrria 1,9, l0 (end-mernbenin comrnon:annite' almandine)
Equilib,rium 6 controls P-T detsrmination (excluding annite)
AveragedTWEEQU resuld: k 6.8 * 0.6 kbar / T=467 t 32 oC (3 indepondentrcactions)
Outlen: Equilibrium 9 (containsreliability level 3 end-memben: annite, clinozoisite)
Equilibria plottod in Figue 3 4s 4v
1: Alm + Phl = Prp + Ann -73.7 -0.31
2:5 Prp + 24Czo + 3 Qtz = 33 An + 3 Cln + 5 Grs -842.7 -67.23
3:Prp+Ms+Gn=3An+Phl -tt9.2 -7.26
4: 3 Qtz + 5 Aln + 24 Czo + 5 Phl = 5 Grs + 3 Cln + 33 An + 5 Ann -911.1 -68.77
5:Ms+Gn+Alrn=Ann+3An -132.9 -7.57
6: 6Prp + 1l Ms + 16 Grs +3 Cln = 3 Qtz+ 24Czo + 11Phl -469.0 -12.68
7: SPhl + 24 &o+ 3 Qtz = 18 An + 3 Cln + 10 GIs + 5 Ms -%t6.5 -30.91
8:3Qv,+?ACm+5Ms+10Prp=5Prrl+3Cln+48An -1438'9 -103'55
9: llMs+16Gn+3Cln+11 Alm=3Qtz+ 1lAnn+24Czo+5Prp -619.6 -16.08
1 0 :l 1 M s + 1 6 G r s + 3 C l n + 6 A h n = 3 Q t z + 6 A n n + 2 4 C z o + 5 P h l - 5 5 1 . 1 ' 1 4 . 5 3
11:3Qtz+5Aln+24Czo+5Ms+5Prp=3Cln+48Ar+5Ann -1507'3 -105'09
1 2 : 3 Q t z + 1 0 A l m + 2 4 C z o + 5 M s + 5 P h l= 3 C l n + 4 8 A n + l 0 A n n -1575.8 -106.64
$ Resultsusing Holland & Powell (1990) themodynamic data and activities; # Resuhsusing
thermodynamicdata of Berman (1988; 1990) with ideal mixing in biotite; t for TWEEQU results
is 1o imprecisiou A$ in J.Kil 4V in J'barl: abheviuions from Kretz (1983); Ch =
Clinochlore
250
MonteCarloAnalvsis
200
# tinesequilibrium
is
150 I of 3 closest
to P,ro,
100
50
5 t0 l5 io t{ 30
Ar V/lnK'
Frc. 2. Resultsof a Monte Carlo simulationof calculationsof averagepressure
using mineral compositions perturbed from perfect case (Fig. l). Average
deviation in pressure(Ap.uu;squares)is well correlatedwith weighting factor
(eqn. 9) for each equilibrium. A less precisecorrelation is observedwith the
number of timesa given reactionis one of the threeclosestto the "true" pressure
(triangles;seetext).
equilibria implied by a given mineral assemblage. contain phase componentsfor which one of the
The INTERSX program computesaveragesand th.e three basic assumptions have been most com-
amount of scatter (expressed as a standard promised. Indeed, one of the main reasons for
deviation) of the diagram variables from all computing all equilibria, as opposed to an
intersections(including indifferent ones)among all independentset, is to determineif any of the phase
equilibria, both stable and metastable. The components used in a particular calculation are
averagesare weightedtoward the best-constrained significantly at odds with thesethree assumptions
intersections by using a weighting factor, and to omit them from further calculations.unless
l6.Wr.\1, wittr reassessment of all input data is permissiveof other
A' Sl 'A' vl combinations of "equilibrium" compositions of
wr = (lo)
lnKi minerals. There are several ',ryaysthe TWEEQU
analysis fulfills this task. The first is by visual
where B is the acute angle of intersectionbetween inspection of graphical thermobarometricresuhs,
equilibriai and j, and K' is definedabove. which is the easiestway of recognizing outlying
It is important to appreciatethat equilibria that equilibria. A second way is with the INTERSX
occur furthest from the true P-T of equilibration program, which repeatsthe averagingcalculations
839
THERMOBAROMETRYUSING MULTI.EQUILIBRIUM CALCU LATIONS
tainties when uncertaintiesin standard state and Second, uncertainties in thermodynamic data,
solution properties are better defined (Engi et al. particularly activity - composition relationships,
1990). are larger than many expecteddifferencesin T.,
precludingthe generalinterpretation at the present
Assessmentof equilibrium time of thermobarometricdifferencesin terms of
T6 differences.As theseuncertaintiesare reduced,
this type of interpretation may prove feasibleand
Poorly defined uncertaintiesin thermodynamic may allow geological rates of cooling to be
data, particularly solution properties, seriously determined from detailed study of ther-
compromisethe ability to quantitatively assessthe mobarometric differences. Third, and perhaps
state of equilibration of sampleson an individual most convincing, is the empirical observationthat
basis. In addition, becauseeach equilibrium has thermobarometricresultssuggestingattainment of
different uncertainties, and different reaction- equilibrium are well correlated in a variety of
propertiesthat translate into different sensitivities
mineral systemswith textural and chemicalcriteria
to errors in input data, a single limit on pressure for equilibrium. A number of these results are
and temperature for the amount of intersection discussedin detail below.
scatter cannot be establishedas the criterion to
assessequilibration state. Ideally, equilibration
state should be determined by comparison of APPLICATIoNS
calculated scatter in the intersection with thar
stemming solely from calibration and analytical Thermobarometricresultsfor RP13, a calc-sili-
uncertainties.Until the calibration uncertaintiesare caterock consideredby Holland & Powell (1990)
better defined, the strategy recommendedhere is to be "remarkably well equilibrated", offer a good
that confidencecan be gained using the TWEEQU opportunity to illustrate the TWEEQU technique.
techniquewhen the thermodynamicdata passthe This softwarefacilitatescalculationsusingdifferent
first-order test of producing results for specific thermodynamic data-bases;Table I and Figure 3
systemsand phasecomponentswith (a) little scatter show TWEEQU results for this rock using
when classic"equilibrium" textures(e.g., Vernon thermodynamic data and activities of phasecom-
7976,1977,Spear1989)are observed,and (b) good ponents from Holland & Powell (1990). The
consistencyamong different domains of single calculations are based on non-fluid-phase com-
samplesand among samplesthought to have the ponents that are also given in the TWEEQU
same metamorphic and delormational history. data-base.Immediatelyobvious from the inconsis-
Calculationsfor a set of samplesshould define the tency in the position of invariant point A with the
criteria usedto define the "equilibrium" case,and other equilibria shown in Figure 3 is that one of
TWEEQU resultsfor samplesof similar bulk-com- the three basic thermobarometricassumptionshas
position with ambiguoustexturescan be taken with been violated. The sameconclusionis reflected in
some degree of confidence. Examples discussed the largelo scatter(1.5kbar, 65oC)calculatedwith
below indicate that reasonablecriteria for satisfac- the INTERSX program when all equilibria are
tion of the equilibrium assumptioncorrespondto included. This program proceedsto calculatethat
INTERSX 1o standarddeviationsof +0-40"C and threeequilibria(#l, 9, l0 of Table 1) aremorethan
0.2-0.5kbar. l.5o outside of the averageP-T, and that these
It should be noted thar rhe expectationthat all three equilibria have almandine and annite in
equilibria intersect at a single pressure and common. The position of invariant point A is
temperature(Fig. l) is unjustified in view of the controlled by the garnet - biotite Fe-Mg exchange
different closure-temperature (T6) and resistanceto equilibrium, which givestemperaturesmuch lower
retrogression of each equilibrium (Lasaga 1983, than that (520'C) preferred by Powell & Holland
Ghent et al. 1988). For example, equilibria that (1988) on the basis of calcite - dolomite ther-
depend on the Al content of orthopyroxenemay mometry. The INTERSX program focussesatten-
record higher pressuresand temperatures than tion on annite, becauseit has a reliability level of
equilibria that involve only the Fe and Mg end three, suggestingthat the problemsmay be related
members (e.g., Aranovich & Podlesskii 1989) to this phase component. Calculations repeated
becauseof the largerkinetic barriersto re-equilibra- without this phase component give the P-T of
tion of Al distribution. Nevertheless,therearethree invariant point B, but the program warns that an
reasonswhy the kind of equilibrium test described independentP or T estimateis advisedsincethere
aboveshouldbe reasonable.First, closuretempera- is no meansof checkingthis P-T determinedfrom
tures depend on grain size and cooling rate, and the intersectionof only two independentequilibria.
thus may be operationally quite similar for many An important differencewith the THERMOCALC
samplesat common geological rates of cooling. procedures(Powell & Holland 1988) is that the
THERMOBAROMETRYUSING MULTI-EQUILIBRIUM CALCULATIONS 841
10000
Cal-Dol
9000
(t)
Lr 7000
ctt
6000
<t)
r- 5000
(A
Ea 4000
<t)
tr
tr.( 3ooo
RP-13
3 rR - H&P(1990
Temperature ('C)
Frc. 3. TWEEQU resultsfor calc-silicale RP-13 (Holland& Powell 1990)'Box in
lower left corner indicatesthere are three independentequilibria (3 lR)' and
that calculationsweremadeusing the thermodynamicdata of Holland & Powell
(1990). Arrow shows the preferred temperatureof Powell & Holland (1988)
(520"C) based on calcite-dolomite thermometry. I bar shows the 2o average
bracket associatedwith pressure(Holland & Powell 1990).Numbered curves
refer to equilibria identified in Table l. See text for discussionof invariant
pointsA and B. InsetshowsTWEEQU resultsin T-X(CO2)sectionat 7.2kbar,
omitting annite from the calculations.
12000 FuruaComplex
# c-311.1
(1980)
Coolen
I r000
U)
h
s
10000
<t)
l< 9000
(t)
(t)
ct)
h
8000
7000
2 IR - TWBBQU/Ian91
6000J-
300 350 450 550 600 650 700 750 800
Temperature('C)
Ftc. 4. TWEEQU results in the system CaO-MgO-Al2O3-SiO2 (CMAS) for
first-generationphasesin granuliteC-3 I I . I from the Furua Complex,computed
with the January, 1991TWEEQU thermodynamicdata. Two of five equilibria
shown are independent(2 IR).
THERMOBAROMETRYUSING MULTI.EQUILIBRIUM CALCULATIONS 843
3 IR - TWEEQU/Ian91
FuruaComplex
# c-3 1 1 .1
Coolen(1980)
u)
t<
6J
,a
<D
Lr
an
(a)
<L)
tsr
FuruaConplex
# c-3 1 1 .1
Coolen(1980)
9n
h
cl'
,a
<D
k
v)
aa) ^
ct)
!r
tr<
3 IR - TWEEQU/Ian91
300 400 500 600 700 800
Temperature('C)
THERMOBAROMETRYUSING MULTI-EQUILIBRIUM CALCULATIONS 845
16000
c
3 IR - TWEEQU/Jan91
r5000
14000
u) r3000
Lr
clt
,a 12000
) 11000 Moecher
et al.
Lr (1e
88 )
(t) 10000
v) (1990)
Berman
)
L 9000
tr<
8000
FuruaConplex
7000 # c- 311.1
Coolen(1980)
6000
500 550 600 650 700 750 800 850 900 950 1000
Temperature('c)
Ftc. 5. a. TWEEQU resultsin the CMFAS system(F: FeO) for first-generation
phasesin granulite C-3ll.l from the Furua Complex, computedwith the
January, 1991 TWEEQU thermodynamic data. Numbered equilibria (3
independent)are listed in Table 2. b. TWEEQU resultsin the CMFAS system
for first-generation clinopyroxene and second-generationgarnet and or-
thopyroxenein granuliteC-311.1from the Furua Complex,computedwith the
January, 1991 TWEEQU thermodynamic data. Numbered equilibria (3
independent)are listed in Table 2. Note the wide scatterin the positions of all
equilibria, indicative of the disequilibrium assemblage.c. TWEEQU resultsin
the CMFAS systemfor first-generation phasesin granuliteC-311.1 from the
Furua Complex. Curves were computed with the January, l99l TWEEQU
thermodynamicdata (including garnet model of Berman 1990)'Open polygons
show the range of intersectionsfor the same equilibria using the garnet
calibrationsof Hodges& Spear(1982)and Moecheret al. (1988).Small filled
polygon shows range of intersectionsfor mixed first- and second-generation
phasescomputed with the garnet calibration of Moecher et 4/. (comparewith
Fig. sb).
1980), the importance of this ability becomes difficult to analyze rigorously because of the
paramount in the most common situation systematicdifferencesamong the data with which
petrologists are faced with, that of ambiguous they are calibrated. The TWEEQU method has
petrographic textures. Particularly critical is the been set up to facilitate comparisonsof the effect
ability to test which mineral compositionsmight be of different solution models on all equilibria'
in equilibrium where zoned minerals are present. Figure 5c compares results for first-generation
A major problem in interpreting results like phasesin the sameFurua Complex rock, using the
those shown in Figures5a and 5b is the sensitivity garnet mixing propertiesof Moecher et ol. (1988)'
of results to thermodynamic data, particularly Hodges& Spear(1982),and Berman (1990,Fig.
alternative solution-models. This sensitivity is 5a). Results with the first two calibrations are
846 THE CANADIAN MINERALOCIST
6000
Waterville (Feny 1980)
Formation
5500
5000
a)
L
cl! 4500
,Q
4000
(l)
k
;3500
an
g)
:3ooo
2500
{ Sittinanite-bearing
( Andalusite-bearing
2000
460 480 500 520 540 560 580 600
Temperature('C)
Frc. 6. Summaryof TWEEQU resultsin the KCMFASH system(K: K2O' H: H2O)
for 18samplesof WatervilleFormation pelite, computedwith the January, 1991
TWEEQU thermodynamic data. Light and dark triangles, defined by the
intersectionsof equilibria l-3 of Table 3, showthe rangeof intersectionsamong
all six equilibria (3 independent)for andalusite-and sillimanite-zonesamples'
respectively.
TABLE 3. TWEEQU RES(r'LTSFOR WATERVILLE FORMATION with the other mineral phasesin theserocks. This
PELITES GERRY I98O)
may be the resultof retrogression of biotite caused
Minonlo$/: Bt+Qtz t Cln, Cn, Pl, St, Crd" And, Sil, Mc, Cc, Ep, Cm, Ap,
Gr, Ilm, Po
by interaction with late fluids introduced through
Assmblage usedin TWEEQU calculadons:Ms-Bt-Gn-Pl-Qtz-Aod/Sil aicess along the MonasheeD6collement.Alterna-
Original P-T csdmate: P= 3.5 * 0.2 kbr / T= 46G550 oC (Ferry I 980) tively, the disequilibrium assemblagemay have
Avemge TWEEQU rcsults (l 8 mples): P= 2.6 - 4.2 kbu /'f = 490-575oC
(3 independentMclions) beenproducedby mechanicalrepositioningduring
post-metamorPhicshearing.
Equilibda ploued in Figms 6, 7, l0 ArS drV
1:2Sil+Qtz+Gn=3An -lll.1 -5.45 Pigage (1976) eavedetailed compositional data
2: Prp + Ms = Phl + Qtz + 2 Sil -8.2 -1.81 for St-Sit zone pelitesof the Settler Schist,British
-t3.7
3: Phl + Alm = Ann + Prp
-132.9
-0.31
Columbia, that contain the assemblageGrt-Ms-
4:Ms+Gn+Alm=Ann+3An
5: Alm + Ms = 2 Sil + Qtz + Ann "21.8 Bt-Pl-Qtz-Rt-Ilm + St * KvlSil. Pigage(1976)
6:PrD+Ms+Cs=3An+Phl -119.2 -7.26 reported that syn- to post-tectonic metamorphic
from Krctz (1983)
A"Sin J.K't; d"V in J.brl; abbrcviations reirystallization produced sharp crystal margins
with little alteration,but that "textural evidencefor
equilibrium is inconclusive". Chemicalhomogene-
with the occurrence of these kyanite-bearing ity on a thin-sectionscaleand uniform distribution-
samplesjust downgradeof the sillimanitezone.The coefficientsbetweensamplesare suggestive,how-
likely explanation for the discrepant SGAM ever, of attainment of equilibrium. TWEEQU
pressures and the extreme spread in Grt-Bt calculationsbasedon 2l equilibria (4 independent)
temperaturesis that biotite is out of equilibrium support this conclusion(Fig. 8, Table 4). For each
848 THE CANADIAN MINERALOGIST
14000
Monashee
Mountains
Pelites
tr GASPpre$sure
12000
o SGAMpressurc
at)
t<
10000
@
cl!
8000
<D
t<
6000
at)
(t)
q)
t<
4000
2000
10000
9000
8000
ut2
L
cll 7000
,Q
6000
J
,<
2000
300 350 400 450 500 550 600 650 700 750 800
re ('c)
Temperatu
Frc. 8. TWEEQU resultsin the KCMFASTH system(T: TiO2)for sample5 of the
SettlerSchist,computedwith the January,1991TwEEQU thermodynamic data.
All equilibria(4 independent)are listed in Table 3. Inset showsthe rangeof
intersectionsfor all six samplesthat contain Ky-Sil.
PEUTES(PIGACE 1976)
TABLB 4. TWEEQURESUL]SFORSrrrl-m' SCHTST the calculationsleads to much less scatter in the
MireElogJrM&BtCn-PlQtr-R![m (! Ky, Sil, Sr Chl)
As@blsee usedi! TmEQU @lculdioN: M!-BtCd-Pl-Ky/Sil{bRlIln
resultsbasedon threeindependentequilibria (Table
Previo$ P-TqdmE: P - G8 kbu I T = 550-7moCeigage, 1t6) 3) for eachsample(Fig. 9, bold triangles).Much
A@ge TWIEQU Bula (6 mpls)i P = 5.7-7.I kbs / T = 554-6180C
(4 indepetrdetrt
improved consistency among all equilibria is
@ti@)
obtained with a reducedactivity of rutile (inset in
Equilibris ploaed itr Fig@ 8 4s Fig. 9), which might be attributed to dilution by a
1: Als + Ihl s Itp + Am -13.7 -0.31
2:6Rt+2Prp+Cn+2Am=3Anr6llnr2Phlr3Qu "119.4 ,8.89 smallamount of nonstoichiometriccomponents(no
3 : 6 R r i P r p + 2 A d = 6 [ m + M s + P h+
l 3 Qtz 0.1
4:3 Rt+P!p+Am= 3 lln iPhl t2 QtrrSil 5.5 -1J7 analytical data are given for rutile by Tracy 1978).
5:6RraGni2Alr!-3A!+6ILn+3Qu lK.1
-n.5
-9.5l Similar improvement is obtained with increased
6:2Aln+ltrlr6Rt=3QtriPrp+Ms+6116
7:Aln+Am+6Rt-3Qtr+Ms+6[rn -13.8 -1.93 activity of ilmenite, possibly reflecting continued
-,9.2 -2.08
8:Ala+3Rr=Sir2Qtrr3nn
-119.2 -7.26
retrograde exchange of ilmenite with sulfide
9i Prp+ Ms + GN - 3 An + Phl
10:cc+6nm12Msr3Qtr=6Rtr3An+2Am -119.1 -5.& minerals.
1l:3Silr3Rt+Iip+2Gs+Am=6Anr3llniPhl -2n,2 "t2.47
l2:2 Sil+Qu+GE = 3 A! "108.3 ').JJ
Tracy(1978)
a)
t<
6
'Q
LogActivityRutile
e)
t<
q)
(t)
(D
Lr
-
Temperature('C)
Ftc. 9. Summaryof TWEEQU resultsin the KCMFASTH systemfor four pelitic
samples with the assemblageGrt-Ms-Bt-Pl-Qtz-Rt-Ilm-Sil (Tracy 1978),
computed with the January, 1991TWEEQU thermodynamicdata. Thin-ruled
polygons show the range of intersectionsamong 2l equilibria (4 independent)
listed in Table 4. Bold triangles show the range of intersectionsamong six
equilibria (3 independent)listed in Table 3 that do not involve ilmenite and
rutile. Inset shows P-Activity(rutile) diagram computed at 500"C for sample
534r (seetext for discussion).
in this paper lends itself to this problem becauseit equilibria listed in Table 3 is significantly greater
offers a general way to test this assumption of than obtained for other "well-equilibrated" suites
equilibrium. In addition, given confidencein the of samples(e.g., Figs. 6 and 8), TWEEQU results
thermodynamic data used, one can look for (nig. lb) appear to indicate that many of their
textural signsof disequilibriumto try to reconstruct samples did re-equilibrate fully at temperatures
P-T paths from samplesor portions of samples between 475 and 600'C. Although it may be
that have locally re-equilibratedat different times tempting to conclude that the distribution of
along a prograde or retrogradepath. samples parallel to the slope of the GASP
St-Onge(1987)deriveda P-T path from analysis equilibrium is an artifact of Fe-Mg exchangeto
of mineral inclusionsin a zonedgarnet, but the full lower temperaturewithout GASP re-equilibration'
advantageof the TWEEQU technique cannot be considerationof the effects of Fe-Mg exchangeon
gained in this example because only two inde- the SGAM equilibrium in the manner describedby
pendent equilibria can be written for the Grt-Bt- Frost & Chacko (1989)showsthat this conclusion
Ky-Pl-Qtz assemblagepresent in these rocks. is unjustified. The extent of Fe-Mg exchange
Hodges & Royden (1984) have calculated a P-T necessaryto reducethe temperatureof the 725'C
path for a portion of the northern Scandinavian sampleof Hodges& Royden(1984)by the observed
Caledonidesfrom pelitic samplesthat apparently 250;C (increasingXp" in Grt or decreasingXo" in
underwent different histories of retrogression. Bt by about 0.14) producesa shift in the SGAM
Although the scatter for three rocks using the barometer between4 and 8 kbar' The magnitude
13m
3 IR - TWEEQU/Ian9I
umO
(1984)
& Royden
Hodges
llm
a lmo
t-
GI
'a 9m
<u 8m0
t-r
7t) 7m0
(t>
)
r{ m00
-
5m0
4m0
30m
4m 450 5m 550 6m 650 7m ?50 8m 850 9m
Temperature('c)
Frc. 10. TWEEQU resultsin the KCMFASH svstemfor pelitesfrom th1l9I49T
Scandinaviari Caledonides, computed with the January, 1991 TWEEQU
thermodynamicdata. Triangles, defined by the intersectionsof equilibria 1-3
of Table 3, show the rangeof intersectionsof all equilibria (3 independent)'See
text for discussion.
8s2 THE CANADIAN MINERALOGIST
of this effect should clearly be discerniblewithin cheque form, payable to "Receiver General of
reasonableexpectationsof uncertaintiesin calibra- Canada", in order to coverhandlingcosts.
tion. The TWEEQU results,therefore,support the
notion that thesesampleshave frozen in a record ACKNOWLEDGEMENTS
of a portion of the retrogradeP-T path, although
the exact P-T trajectory derived here is somewhat I am grateful for the efforts of L. Aranovich,
lesssteepthan that derived by Hodges & Royden B.R. Frost, J. Lieberman,J.A. Percival,M.R. St.
(1e84). Onge,and M.L. Williams, who offerred perceptive
and very useful reviewsof this paper. I would also
like to use the opportunity of this specialvolume
CONCLUSIoNS
honoring H.J. Greenwoodto thank Hugh for the
years of generous guidance and suppofi, and
The thermobarometrictechniqueproposed in oftentimesinspiration he has given me.
this paper offers a test of the critical assumption
that all minerals used in a calculation lasr REFERENCES
equilibratedat the samepressureand temperature.
The correlation of convergentTWEEQU results Arlovrrz,L.M. & EssENE, E.J. (1987):Compatibility
with independent indications of equilibrium in of geobarometersin the systemCaO-FeO-Al2O3-
SiO2-TiO2 (CFAST): implications for garnet
someof the examplesdiscussedabovesuggeststhat mixing models.J. Geol. 95, 633-645.
this techniquemakesit possibleto reasonablyassess
the stateof equilibration of samplesfor systemsin & _ (re90):Thermobarometry and
which the thermodynamicpropertiesappear to be pressure - temperature paths in the Grenville
well described.The number of situationsin which Province of Ontario. ,I. Petrol. 31. 197-241.
independentevidencefor equilibrium is ambiguous
underscoresthe importance of being able to apply AnaNovrcu, L.Ye.. & Poolrssrrr, K.K. (1989):
this thermobarometric test in a general way. In Geothermobarometry of high-grade metapelites:
addition, the technique offers the means to simultaneously operating reactions. .|le Evolution
of Metamorphic Belts (J.S. Daly, R.A. Cliff &
reconstructportions of P-T pathsfrom appropriate
B.W. Yardley, eds.). Geol. Soc. London, Spec.
samples. Publ. 43,45-61.
Although this analysis is hindered by poorly
describeduncertaintiesin thermodynamicdata, as Brnuer, R.G. (1988): Internally-consistent ther-
theseuncertaintiesbecomebetter known, they can modynamic data for minerals in the system
be incorporated into the analysisin the sameway Na2O-K2O-CaO-MgO-FeO-Fq03 -Al2O3-Si02*
as Lieberman & Petrakakis (1991) describefor TiO2-H2O-CO2. J. Petrol. 29, M5-522.
compositionalerrors.At present,this techniquewill
(1990): Mixing properties of Ca-Mg-Fe-Mn
prove most useful in systemsthat involve minerals
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with the smallestuncertaintiesin calibration. but
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