ChemicalGeology, 108 (1993) 133-162 133

Elsevier Science Publishers B.V., Amsterdam

Titanium substitution in biotite: an empirical model with

applications to thermometry, 02 and HeO barometries, and
consequences for biotite stability

Alberto E. Patifio Douce

Department of Geology, Universityof Georgia, Athens, GA 30602, USA
(Received February 5, 1993; revised and accepted April 8, 1993 )

ABSTRACT

An empirical model for solution of Ti in biotite is developed and calibrated on the basis of various equilibria among
biotite and Ti-saturating assemblages. Sources of data used for the calibration include both experimental products and
published analyses of natural assemblages. Ti solution in biotite can be satisfactorily modelled by means of the exchange
component TiFe_ 2, whose non-ideal behavior can be approximated empirically by means of a linear function of the rela-
tive concentrations of Ti and octahedral A1 in biotite. Within assemblages which fix the chemical potential of the exchange
component TiFe_2, the concentration of this component in biotite is very sensitive to temperature and oxygen fugacity,
making it possible to use biotite + oxide assemblages to obtain reliable T andf(02 ) estimates in igneous and metamorphic
rocks. In assemblages which also contain alkali feldspar, it is possible to use breakdown equilibria of Ti additive compo-
nents in biotite to estimate H20 fugacity. Such uses are likely to find important applications in rocks in which other
assemblages sensitive to temperature, f(O2 ) a n d / o r f ( H 2 0 ) are absent (in general, rocks containing a single oxide phase
plus biotite as the only mafic silicate phase, + alkali feldspar). The empirical model for solution of Ti in biotite also allows
to calculate the loci of various terminal reactions for the assemblage titanian biotite + quartz, which, by comparison with
equivalent equilibria in Ti-free systems, provide insight into the effect of Ti on the stability of biotite. Solubility of Ti in
biotite increases with temperature in a strongly non-linear fashion. As a consequence, calculations predict that the effect
of Ti on the stability of biotite is very small up to conditions typical of the beginning of the granulite facies of metamor-
phism, but beyond those conditions Ti concentration increases markedly and biotite is rendered very refractory. At mid
to deep crustal pressures ( >t 10 kbar), the vapor-absent solidus of biotite+quartz in rocks containing Ti-saturating phases
is likely to exceed 900 ° C, even in bulk compositions with suhequal concentrations of Fe and Mg.

1. Introduction thorough understanding of these petrologic

Biotite and aluminous amphiboles are the
chief reservoirs of structurally-bound H20 at
pressure-temperature conditions exceeding
those of the mid-amphibolite facies of meta-
morphism. A significant proportion of the H20
present in the mid to deep continental crust and
in subducted oceanic lithosphere is, therefore,
likely to be contained in biotite, which also
plays major roles in petrologic processes such
as crustal anatexis, granulite formation, devo-
latilization of subducted material and crystal-
lization of hydrous magmas. In order to gain a
processes it is necessary to address two impor-
tant facets of the terminal equilibria of hy-
drous minerals. In the first place, the loci of
the terminal reactions must be m a p p e d as a
function of intensive variables and composi-
tion. Secondly, it is crucial to understand the
nature of these terminal reactions, i.e. whether
H20 is liberated as a fluid (below the solidus)
or as a component of a silicate melt (at and
somewhat above the solidus), as well as the
factors that control which of these two dehy-
dration mechanisms can be expected to take
place under a given set of conditions.

0009-2541/93/$06.00 © 1993 Elsevier Science Publishers B.V. All rights reserved.

134
In addition to its role as a source of volatile
components, the importance of biotite as a
monitor of the chemical potentials of such
components within the Earth must also be rec-
ognized. Efforts to address some of these ques-
tion were pioneered by Eugster and Wones
(1962), Wones and Eugster (1965) and Ruth-
erford (1973), all of whom studied phase
equilibria of ferruginous biotite compositions.
Phase equilibria of phlogopite was investi-
gated, among others, by Bohlen et al. (1983),
Peterson and Newton (1989), Montana and
Brearly (1989) and, most exhaustively, by
Vielzeuf and Clemens (1992). In the compo-
sition space of natural biotites, however, sig-
nificant concentrations of Ti and A1 (in excess
of that required for binary annite-phlogopite
solutions) are the norm rather than the excep-
tion. The presence of these components is likely
to have major effects on the behavior of this
phase, but we do not have a detailed under-
standing of such effects, largely because of lack
of experimental work designed specifically to
address these issues. Since the early work of
Ramberg (e.g. 1948, 1949, 1952), the effect of
Ti has been known to be particularly impor-
tant in extending the thermal stability of bio-
tite. This inference is largely drawn from the
observation that Ti concentration varies di-
rectly with metamorphic grade in natural bio-
tites coexisting with Ti-saturating phases (e.g.
Dymek, 1983; Guidotti, 1984; Schreurs, 1985;
LaGrange et al., 1992). Results of synthesis
experiments have supported this conclusion, by
showing that crystallization of titanian micas
is in general facilitated at higher temperatures
and that solubility of Ti in trioctahedral micas
increases with temperature (Forbes and
Flower, 1974; Robert, 1976; Tronnes et al.,
1985; Abrecht and Hewitt, 1988 ). Phase equi-
librium experiments (Dooley and Patifio
Douce, in prep.) show that solution of Ti in
phlogopite causes the divariant assemblage Ti-
phlogopite + quartz + enstatite + sanidine +
H20 to be stable over a temperature interval
extending to at least 50°C above the tempera-
A.E. PATIIKIO DOUCE
ture of the Ti-free univariant equilibrium at the
same pressure.
The aim of this contribution is to improve
our quantitative understanding of the behav-
ior of titanium-rich biotite, particularly with
respect to the effects of Ti on dehydration and
redox equilibria of micas. In order to accom-
plish these goals a model for the thermody-
namic behavior of titanian biotite is needed.
The paper is therefore divided into two parts.
In the first part an empirical model for solu-
tion of Ti in biotite is developed and cali-
brated. Construction of this model is based
primarily upon products of melting experi-
ments, which were discussed by Patifio Douce
and Johnston ( 1991 ) and Patifio Douce et al.
( 1993 ), and is also constrained by natural data
from several literature sources and by new ex-
perimental data. The model is applied to ther-
mometry, oxygen barometry, and H20 baro-
merry of biotite + oxide_+ alkali feldspar
assemblages, yielding results which are gener-
ally in good agreement with independent esti-
mates of the values of these intensive vari-
ables. This empirical model is only a first
approximation and no substitute for a rigorous
thermodynamic understanding of Ti in micas,
which must be built upon experimental work
specifically designed for that purpose. The
working model presented here has the merit,
nonetheless, of demonstrating the usefulness of
titanian components in biotite as a means of
estimating the values of intensive variables
(particularly oxygen fugacity) in rocks in
which other indicator assemblages might not
exist. In the second part of the paper the em-
pirical model is used to analyze the effect of Ti
on phase equilibria of biotite. Calculated phase
relationships confirm that solution of Ti in
biotite extends the thermal stability of this
phase, but also show that, because Ti solubility
in biotite increases with temperature in a
strongly non-linear fashion, the terminal be-
havior of titanian biotite is more complex than
previously thought.
Ti SUBSTITUTION IN BIOTITE: EMPIRICAL MODEL WITH APPLICATIONS TO THERMOMETRY ETC.
2. Thermodynamic modelling of Ti solution in
biotite
2.1. Initial calibration from experimental data
In a series of partial melting experiments of
a natural metapelitic rock at pressures between
7 and 13 kbar, Patifio Douce and Johnston
(1991 ) found that the assemblage biotite +
garnet + sillimanite (or kyanite) + quartz +
ilmenite and/or rutile persisted over a broad
temperature interval (at least 150°C) above
the solidus. Moreover, we found that biotite
compositions vary systematically with temper-
ature and pressure, and this enabled Patifio
Douce et al. ( 1993 ) to investigate A1 solubility
in biotite and to derive a set of interaction pa-
rameters which describe mixing in the octahe-
dral layer of trioctahedral micas. In particular,
we showed that the concentration of octahe-
dral AI in biotite (A1w ), in assemblages which
fix the chemical potential of A12SiO> is very
sensitive to pressure, and that the behavior of
A1vI can be modelled by means of vacancy-
forming dioctahedral exchange components of
the form A12R_ 3 (where R can be either Mg or
Fe ). Perhaps most importantly, given a model
for the non-ideal mixing behaviors of these ex-
change components (which we calibrated
solely on the basis of our experimental data),
net-transfer equilibria among biotite and
A12SiOs-buffering assemblages provide relia-
ble estimates of crystallization pressures of
rocks of suitable composition (metapelitic
sensu lato). This last point is important not
only because it demonstrates the soundness of
the approach taken to model A1vl solubility in
biotite but also because it suggests that, even
though our partial melting experiments were
not reversed, the experimental products most
likely represent a reasonable approach to
equilibrium.
Variations in the Ti contents of experimen-
tally-produced biotites coexisting with silli-
manite (or kyanite)+garnet+ilmenite (or
rutile)+quartz are also quite systematic,
13 5
showing a marked increase with temperature
along a trend which is not affected by whether
ilmenite or rutile is the Ti-saturating phase
(Fig. la, data from Patifio Douce et al., 1993,
their Table 3). Ti concentration varies in-
versely with Fe content, and the correlation
between both composRional variables has a
slope close to - 2 (Fig. 1b). This result is con-
sistent with Ti dissolving in biotite by means
of the vacancy-forming exchange component
TiFe_2, which is equivalent to the difference
between the additive components KTiFeAI-
Si3Olo(OH)2 (Ti-annite) and KFe3A1Si3OIo
(OH)2 (annite) (see also Dymek, 1983;
Abrecht and Hewitt, 1L988; Holdaway et al.,
1988; Zhou and Lindsley, 1992 ). This partic-
ular exchange component is not the only pos-
sible way of interpreting the observed varia-
tions in biotite compositions. For example, the
exchange component TiMg_2 could be used
but, because Ti content in biotite is buffered
by equilibria involving oxide phases and ox-
ides are strongly enriched in Fe relative to Mg,
calibration of such equilibria among Mg com-
ponents will be subjeclL to much larger uncer-
tainties than if Fe components are used. Alter-
natively, the component Ti3AI_ 4 ( cf. Labotka,
1983 ), which is a linear combination of TiFe_2
and AI2Fe_3, could be used, but this choice
would again complica~te the treatment of ox-
ide-biotite equilibria unnecessarily. Oxy-ti-
tanian components are', also possible (e.g. Dy-
mek, 1983; Zhou and Lindsley, 1992), but
their presence in the experimental products
cannot be substantiated (nor ruled out) only
from electron microprobe data. The exchange
component TiFe_2 is the simplest component
which is consistent with the data and which
lends itself to straightforward thermodynamic
calculations.
The chemical potential of TiFe_2 in biotite
in the assemblages present in the experimental
products is fixed by one of the following equi-
libria, depending on whether ilmenite or rutile
is the Ti saturating phase:
136 A.E. PATIIqlODOUCE

1 )1/3
[ A12Fe_ 3 ] bio + FeTiO3 + giG2 (4)
K 2 - aA12Fe-aTiFe-~23 aFe3A--Si3C,1212
~- [ TiFe_ 2 ] bio "{- A12SiO5 ( 1)
AG ° is the standard state Gibbs free energy
[AlaFe_3 ]bio +TiO2 + ] [Fe3A12Si3012 ]gar
change of reaction i among pure end-member
+ ~SiO2 ~ [TiFe_2 ]bio + 4A12 G i G s components at the temperature and pressure
(2) of interest and aj is the activity of component
j. Because the standard state properties of end-
The equilibrium conditions for these reactions
member Ti-annite are unknown (note that
are the following: 0 0 0
flTiFe(- 2) ~---flTi-annite --flannite ), it is n o t possible
_aa o to use these equilibrium conditions to derive
lnK1 --
RT mixing properties for Ti-biotite (as was done
_aa O by Patifio Douce et al., 1993 for the Al-diocta-
InK2 - (3) hedral exchange components, which are based
RT on muscovite, an additive component of
where: known thermodynamic: properties). Rather,
activity-composition relationships in biotite
Kl -- aTiFe_2 1 will be considered ideal and the experimental
aA12Fe_ 3 aFeTiO3 data will be used to obtain an empirical cali-

0.4 1.5
(a) (b)
0.35 0 1.3

0.3
II o 1.1
.~
t~ 6
0.25

O 0.9
[-. 0
0.2 0
D
0 7 kbar (ilmenite) 0.7
0.15 [] 10 kbar (ilmenite)
• !0 kbar (rutile)
, 13 kbar (rutile)

0.1 , t , , I , 0.5 I I i I ,
800 850 900 950 1000 0.1 0.15 0.2 0.25 0.3 0.35 0.4

T e m p e r a t u r e °C Ti per 12 anions

Fig. 1. ( a ) Ti content in biotite ( a t o m s per 12 a n i o n s ) in experimental products o f P a t i f i o Douce and J o h n s t o n ( 1991 ).

Experiments at 950°C, 7 kbar, a n d 900°C, 10 k b a r contain b o t h ilmenite a n d rutile. Ti-saturating phase in other experi-
m e n t s as shown in the figure. Full analyses given in Patifio Douce et al. (1993). U n c e r t a i n t i e s in Ti contents (2 s t a n d a r d
deviations o f m e a n of 10 to 15 probe analyses of different crystals) shown in ( b ) . ( b ) Correlation between Ti a n d Fe
(total Fe calculated as Fe 2÷ ) contents in the same experimental biotites shown in (a). Slope of line = - 2 .
Ti SUBSTITUTION IN BIOTITE: EMPIRICAL MODEL WITH APPLICATIONS TO THERMOMETRY ETC. | 37

id
bration of l n K 1 a s a function of temperature aTi_an n
and pressure, of the form:
1024 3 2
"~ff "SFe M2S T i M2X D MI XAI IVX s i S K S o i l -
AhT PArT AsT
InK1 = - ~---- (5)
RT RT R
id = 2 5 6 X 2
amos 27 AI
M2X mX
[]
3
-AIIvXsiXKXoH-
2 (8)
where Ah~', As~' and Av~' are constants that
proxy for the enthalpy, entropy and volume
changes (respectively) of equilibrium (1) at with mole fractions as defined in Table 1. The
the temperature and pressure of interest. Both activity of the exchange components is given
ilmenite-bearing and rutile-bearing assem- by the ratio between the activities of the cor-
blages can be used to calibrate the empirical responding additive components (e.g.
expression for equilibrium ( 1 ), by combining Thompson, 1982; Patifio Douce et al., 1993),
the standard state Gibbs free energy change so that:
( AG ° ) of the equilibrium:
id id
a Ti-ann 4 X T i M2X D MI
TiO2 + ~Fe3A12Si3012
aTiFe_2- id
a ann
-- XFeM2XFeMI
~FeTiO3 + ~A12SiO5 + 2SIO2 (6)
id a mido S X 2 I M2.Xw] MI
with that of equilibrium (2), in order to obtain: aAl2Fe_3-- id - - 2 (9)
a ann g F e M2.XFe MI
, aG o
lnK2 t ~ - = InK1 Note that these exchange components involve
(7)
only octahedral substitutions, so that all the
AhT PArT AsT
=-RT RT ~ R
TABLE 1
An analogous transformation allows one to
convert kyanite-bearing assemblages to silli- Mole fractions for activity-composition expressions (biotite
stoichiometry on 12 anion basis )
manite-bearing equilibria.
Calculation of the equilibrium constants re- Tetrahedral sites
quires explicit activity-composition relation-
Xs, = S i / 4
ships. Patifio Douce et al. ( 1993 ) discussed the
calculation of ideal activities in trioctahedral -¥Al'V= Al~V/4
micas containing vacancy-forming substitu-
Octahedral M1 site
tions. They proposed a model for mixing in the
octahedral layer which assumes that all vacan- Fe 2+
cies are formed in the M 1 site whereas A1 and XF. . . . M g + Fe2 + • ( X - 6 )
Ti order into the two M2 sites. Given these
X~,,,, = 7 - 2
premises, and assuming also that Si and A1 mix
randomly over 4 sites in the tetrahedral layer, Octahedral M2 sites
the following expressions for the ideal activi-
Fe 2+ 2 _ A l V l _ T i _ F e 3+
ties (a id ) of annite (ann), Ti-annite (Ti-ann)
XveM2 = M g + Fe 2+ 2
and muscovite (mus, the Al-dioctahedral ad-
ditive c o m p o n e n t ) are derived: A~m2 =AlVa/2

XTiM2=Ti/2
a~, - 2 5 6 X 2 e M~XFe M, XAIIvX3siXKX2H -

27
Note: L'= total sum of octahedral plus tetrahedral cations.
138 A.E. PATIIqO DOUCE

contributions to their ideal activities from the ments the calculated activity coefficients (after
tetrahedral layer, from interlayer sites and from Ghiorso, 1990) are close to 1. Garnets in the
anionic sites cancel out. This simplifies the experimental products (Table 2 ), in contrast,
expressions considerably and avoids uncer- contain concentrations of Mg, Ca and Mn
tainties about partial dehydroxylation and te- which result in non-negligible calculated activ-
trahedral ordering in the calibration of the em- ity coefficients (Patifio Douce et al., 1993, their
pirical expression for lnK~. It must be kept in Table 2 ) which will be included in this analy-
mind, however, that cancellation of tetrahed- sis. Table 2 also shows the calculated values of
ral contributions to the activity expressions lnK~ (for ilmenite-bearing assemblages), and
would not be correct if significant cross-site lnK2 and lnK2+AG°/RT ( = l n K i ) for rutile-
mixing effects existed between tetrahedral and bearing assemblages (standard state proper-
octahedral sites. The data available do not al- ties for equilibrium (6) from Berman, 1988 ).
low this topic to be pursued further. Note that two experiments (those at 950°C, 7
The calculated values of the ideal activities kbar and 900 ° C, 10 kbar) contain both ilmen-
of the exchange components TiFe_2 and ite and rutile and that in both cases there is
A12Fe_3 in the experimental products are good agreement between the values of lnKl
shown in Table 2 (compositional data from calculated directly (i.e. from ilmenite compo-
Patifio Douce et al., 1993, their Table 3 ). For sitions ) and those calculated from
the remaining activity terms in Eqs. (4) I have InK2+AG°/RT (i.e. from garnet composi-
chosen to consider the behavior of ilmenite as tions). This agreement provides further confi-
ideal (a (FeTiO3) = X(FeTiO3 ) ) and to model dence in the approach to equilibrium during
non-ideality in garnet after Berman (1990). the experiments and in the soundness of in-
Oxide compositions in the experimental prod- cluding both ilmenite-bearing and rutile-bear-
ucts are in general close to end-member ilmen- ing assemblages in the analysis.
ite (cE Table 2), and for these compositions A plot of lnK~ vs. 1/IF for the experimental
and the temperature conditions of the experi- products (Fig. 2) shows a well-defined nega-

TABLE 2

Experimental data for calibration of e q u i l i b r i u m ( 1 )

1' T Ti-phase a(TiFe_2) a(Al2Fe 3) X(FeTiO3) lnKi X(alm) InK2 AG~,~/RTAG°/RT

I kbar) (C) (ideal) (ideal) (ilm) (gar) +INK2

7 825 il 0.506 0.1481 0,938 1.2931 - - -

7 850 il 0.582 0.1126 0.909 1.7386 . . . .
7 875 il 0.809 0.1224 0.900 1.9947 . . . .
7 900 il 0,856 0.1141 0.884 2.1384 - - -
7 950 il 2.331 0.1374 0.854 2.9887 - - -
7 950 ru 2.331 0.1374 - 0,555 3.3901 -0.3491 3.0410
10 825 il 0.524 0.2326 0.922 0.8933 - - -
10 850 il 0.734 0.2685 0.915 1.0942 - - -
10 875 il 0.944 0.2267 0.896 1.5368 - - -
10 900 il 1.254 0.3173 0,871 1.5123 - - -
10 900 ru 1.254 0.3173 - 0.680 1.7508 -0.1063 1.6445
10 925 ru 1.369 0.2878 - 0.671 1.9416 -0.1259 1.8156
10 950 ru 2.022 0.3013 - 0.614 2.5~652 -0.1449 2.2203
13 900 ru 1.684 0.5002 - 0.674 1.'i911 -0.0216 1.5696
13 950 ru 2.725 0.5085 - 0.644 2.0985 0.0058 2.1043

N o t e : Full c o m p o s i t i o n a l d a t a g i v e n in Patifio D o u c e et al., 1993.

Ti S U B S T I T U T I O N IN BIOTITE: EMPIRICAL MODEL W I T H APPLICATIONS TO T H E R M O M E T R Y ETC.
3 •
2.5
~- 2 A1), whereas pressure will act in the opposite
].q
m
• m
1 synthesis experiments of titanian phlogopites.
11.5
8 8.5
104/Y ( K e l v i n -x)
Fig. 2. Variation of lnK~ (cf. Eq. 5 ) with temperature and
pressure. For rutile-bearing assemblages InKt calculated
from InK2and standard state Gibbs free energy change of
reaction (6) (see text, Eq. 7). Uncertainties in experi-
mental temperature and lnK~ (the latter propagated from
mineral compositions) shown by cross.
tive correlation and also demonstrates that
there is a non-negligible effect of pressure on
the position of equilibrium ( 1 ). Regression of
these data with the linear model given by Eqs.
( 5 ) and (7) results in the following values and
standard errors for the regression parameters
(with r 2 = 0 . 9 7 ) :
AhT = 125.8 _+ 12.4 k J / m o l e
AsT = 134.9 + 10.8 J / K e l v i n - m o l e
ArT = 1.49 + 0.23 J / b a r - m o l e
These values are based on sillimanite as the
aluminosilicate polymorph in equilibrium ( 1 ).
Standard state changes for the equilibria silli-
manite ~ kyanite or sillimanite ~ andalusite
can be added to Ah~', As~' and Av]' in order to
obtain a corresponding set of empirical coeffi-
cients for equilibrium ( 1 ) with kyanite or an-
dalusite, respectively.
F r o m the values of Ah~', As~' and Av~" and
the stoichiometry of reaction ( 1 ) it is possible
to draw some conclusions about the effects of
Ti on the t h e r m o d y n a m i c properties of biotite.
Thus, comparison of the values of As]' and
Av~' with those of S°l - Silm o - Sqtz
0 (=-56.91
J/Kelvin- mole ) and Vs°~- - V O m - - V q ° z
( = - 0.56 J/bar- mole), respectively, suggests
that solution of Ti in mica at the expense of A1
139
is accompanied by considerable increases in the
• 7 kbar molar entropy and volume of this phase. We
• 10 kbar can thus expect that, in general, temperature
, 13 kbar
will favor solution of Ti in biotite (relative to
direction. This is the behavior observed by
Robert (1976) and Tronnes et al. (1985) in
Although the empirical model for equilib-
9 9.5
rium ( 1 ) appears to be well behaved in the ex-
perimental products used to calibrate it, the
fact that this model is based upon the explicit
assumption that Ti and AI c o m p o n e n t s mix
ideally in trioctahedral micas must be kept in
mind. As shown ( a m o n g others) by McMullin
et al. ( 1991 ) and Patifio Douce et al. (1993),
this is far from being 'the case, and the differ-
ence between the (non negligible) excess
chemical potentials of TiFe_ 2 and AI2Fe_ 3 in
the experimental biotites is in reality being in-
cluded in the regression parameters and being
"averaged out" over the temperature-pres-
sure-composition range covered by the melt-
ing experiments used to calibrate the model. It
is not possible to estimate excess mixing terms
from these experimental data alone, because
most of the observed variability a m o n g these
data is explained by the three parameters Ah ~',
As]", and Av~' and additional regression pa-
rameters will result in an ill-conditioned linear
model. An appraisal of the effect of non-ideal
mixing in biotite on the position of equilib-
rium ( 1 ) must, at this point, be based predom-
inantly on data from natural assemblages. This
issue is discussed in the following sections, in
connection with applications of Ti-biotite
equilibria to the estimation of intensive vari-
ables in metamorphic and igneous assemblages.
2.2. Temperature estimation from biotite-
oxide equilibria
Because equilibrium (1) has a relatively
steep Clapeyron slope (As~'/Av~'~90 b a r /
Kelvin) it should be possible to use it to esti-
mate crystallization temperatures of bio-
140 A.E. PATI/qO DOUCE

TABLE 3

Samples used for biotite-ilmenite-aluminosilicate-quartzthermometry

Sample T (°C) P (bar) T (°C) Ah ex Ti/ T (°C)

No. ( 1) (2) (3) kJ/mole (Ti+A1) (4)

Holdawayetal.(198~
79 542 2400 702 -21.21 0.144 536
4a 603 3550 735 - 17.20 0.225 621
47 621 2800 705 - 11.14 0.157 549
19 609 3150 750 -17.99 0.227 635
112 619 3650 707 - 11.83 (3.162 556
50 635 4650 778 - 18.02 0.258 680
63 635 3500 767 -16.66 0.242 660
30 637 3750 753 -14.83 0.225 636
8 677 5050 800 -15.30 0.297 724
140 657 3500 770 - 14.24 0.260 674
77-3 662 5070 780 -14.96 0.258 683
77-2 668 4310 777 - 13.76 (3.260 681
90 664 5020 807 - 17.60 0.306 735
76 667 5120 816 -18.21 0.323 753
56 676 4980 812 -16.70 0.312 744

Pigage(198~
p367 619 5250 751 - 17.23 0.199 621
p223 607 4695 738 - 17.23 0.185 599
p74 640 5030 798 -19.72 0.280 713
p40 598 5085 755 -20.37 0.211 632

Williams and Grambling (1990)

77-46d 547 3970 722 -23.19 0.152 562
77-45 541 3950 781 -29.95 0.158 615
84-1622 515 3530 757 -30.75 0.142 582
80-218 561 2100 740 -22.76 0.124 552
c81-148 629 2300 720 - 11.87 0.173 572
81-213 559 2830 795 -28.74 0.203 657
82-62 572 2850 749 -22.54 0.081 528
c81-244 502 1800 721 -28.33 0.079 501
82-12 536 1960 727 -24.55 0.085 511

( 1 ) T from garnet-biotite, with the model ofPatifio Douce et al., 1993.

(2) P from biotite-garnet-aluminosilicate-quartz,with the model of Patifio Douce et al., 1993.
( 3 ) T from biotite-ilmenite-aluminosilicate-quartzwith Eq. ( 5 ) (this paper).
( 4 ) T from biotite-ilmenite-aluminosilicate-quartzwith compositional term, Eq. ( 21 ) (this paper).

tite + sillimanite + ilmenite + quartz assem- to temperatures from garnet-biotite Fe-Mg

blages. Analyses of coexisting biotites and
ilmenites from medium-grade metapelitic
rocks published by Pigage ( 1982 ), Holdaway
et al. (1988) and Williams and Grambling
(1990) are well-suited to test this application.
Figure 3 (see also Table 3) shows tempera-
tures for these rocks calculated from equilib-
rium (1), with the values of Ah~', As~" and
Av]' given in the previous section, compared
exchange calculated with the biotite mixing
model of Patifio Douce et al. ( 1993 ). Temper-
atures from equilibrium ( 1 ) are always higher
than garnet-biotite temperatures, in most cases
by about 100 to 150°C. The difference be-
tween both sets of temperatures is quite sys-
tematic (cf. Fig. 3 ), suggesting that the cause
of the discrepancy might lie in factors which
are not accounted for in the empirical model,
Ti S U B S T I T U T I O N IN BIOTITE: EMPIRICAL MODEL WITH APPLICATIONS TO T H E R M O M E T R Y ETC. 141

950 0.4
IOPatino Dcuce et al., 1993
• Holdaway et al., 1988
I
900 , 0.35 mPigage, 1982
* Williamsand Grambling, 1990
A P ~ o Douee and Beard, n prep.
850 0.3
C 800 • 0.25 O

00::'/
6o t
600/
X
0.2

0.15

0.1
**** ~I** 0

0
~ o
0
o
0
o

i •
550 0.05

500 ' : ' ' 0

500 550 600 650 700 750 800 850 900 950 0 0.05 0.1 0.15 0.2

Expected T ( ' C ) X
Tim

Fig. 3. Temperatures calculated from biotite-ilmenite- Fig. 4. Variations in Ti and A1vl contents of biotites dis-
aluminosilicate-quartz equilibrium, plotted against gar- cussed in the text and shown in Figs. 1 and 3 (mole frac-
net-biotite temperatures ( = "expected"), the latter cal- tions calculated as in Table 1).
culated with the model of Patifio Douce et al. (1993).
Sources of data for natural samples given in Table 3. For Ti-rich and Al-poor biotites are present in the
experimental products of Patifio Douce and Beard, tem-
peratures calculated from biotite-ilmenite-almandine-
products of melting experiments of two Fe-rich
quartz plotted against nominal run temperatures. Diago- greywacke-like protoliths (Patifio Douce and
nal line shows 1:1 correlation. Estimated uncertainties Beard, in preparation; biotite, ilmenite and
shown by cross. garnet compositions from these experimental
products are summarized in Table 4). Alumi-
rather than in uncertainties in pressures or
nosilicate is not present in these experimental
mineral compositions or in retrograde equili-
products, but it is possible to calculate temper-
bration of Fe-Mg partitioning between garnet
atures from the assemblage garnet + biotite +
and biotite.
ilmenite + quartz by considering the
Biotites in the natural assemblages de-
equilibrium:
scribed by Pigage (1982), Holdaway et al.
(1988) and Williams and Grambling (1990) ½[ A12Fe_ 3] bio + FeTiO3 + 3 SiO2
have lower concentrations of Ti relative to A1
than the higher-temperature biotites present in [TiFe_2 ] b i o -~- ½Fe3AI2Si3 O12 (10)
the experimental products of Patifio Douce et for which:
al. ( 1993 ), cf. Fig. 4. Although this composi-
tional trend is qualitatively consistent with the AG°2 AhT PAvT AsT
lnK, o 4 - - - lnK1 . . . . ÷ --
behavior predicted by equilibrium ( 1 ), the fact RT RT RT R
that temperatures calculated with this equilib- ,.i ~1/2
rium are consistently too high suggests that a -- t~TiFe_2 "/'/aim ( 1 1 )
1x10--~1/2 .,.,
compositional term involving Ti and A1 con- t~ A I 2 F e - 3 ~ F e T i O 3

centrations is needed in order to extrapolate the
calibration of equilibrium ( 1 ) beyond the
compositional range of the experimental prod-
ucts of Patifio Douce et al. ( 1993 ). As a test of
this hypothesis we can examine the behavior
of equilibrium ( 1 ) in biotites richer in Ti (rel-
ative to A1) than those used to calibrate the
empirical model (see Fig. 4).
and where AG o2 is the standard state Gibbs
free energy change of the reaction:
½KFe3 A1Si3O,0 (OH)2 + AI2 SiOs + ½SiO:
~ ½KAlaA1Si3Olo(OH)2 + ½Fe3AI2Si3012
(12)
Temperatures calculated in this way for the
142 A.E. PATIlqO DOUCE

TABLE 4 pected values. Before exploring this topic fur-

Biotite, ilmenite and garnet from new melting experiments ther it is convenient to discuss the application
of biotite-oxide assemblages to the estimation
P (kbar) 10 10 10 of oxygen fugacities.
T(C) 900 850 900

Biotite 2.3. Calculation of oxygen fugacities from

-¥AI~M2~ 0.069 0.067 0.070 biotite-oxide equilibria
'gri(M2) 0.157 0.159 0.170
XF~ M 2 ~ 0.722 0.443 0.404
XV,IM1 i 0.699 0.443 0.395 Equilibrium among titanian biotite and il-
X~Mt ~ 0.251 0.225 0.258 menite can be used to calculate the thermody-
T i / ( T i + AI ) 0.695 0.704 0.708 namic effective pressure', of oxygen by means
lhnenite
of the following reaction:
XF~T,O3 0.909 0.905 0.883
FeTiO3 + 302 ~- [TiFe_:~ ]bio+ ~Fe203
3 (13)
Garnet
In order to utilize the empirical calibration of
XA~m 0.805 0.705 0.702
7AL,, 0.954 0.940 0.944 equilibrium ( 1 ) to this end, the reaction:

T ( ° C ) (Eq. 5) 809 810 824 KFe3A1Si3Olo(OH)2 + A12SiOs + 302

Ah ~ (k J / m o l e ) 9.98 4.38 8.22
T ( ° C ) (Eq. 21 ) 868 870 885 ~-KA12A1Si3Oto(OH) 2 +SiO2 + 3Fe203

Melting experiments of two non-peraluminous greywacke-like

(14)
compositions (Patifio Douce and Beard, in preparation). 7" is added to reaction ( 1 ). The following expres-
and P in heading are nominal experimental conditions. Ac-
tivity coefficient for almandine after Berman, 1990.
sion for oxygen fugacity as a function of tem-
perature, pressure and c'ompositions of coex-
isting biotite and ilmenite solid solutions can
three new experimental products are shown in
then be derived:
Fig. 3 and Table 4, and are systematically lower
than the nominal temperatures of the experi- 4
lnfo 2 -- rz~t/T,l +PAVe] lids
ments (standard state properties for equilib- 3RT t 14
rium ( 12 ) and garnet non-idealities calculated TASk4] - ~lnKl -_t_
-- - ~41
, n , ~k-solids
13 (15)
after Berman, 1988 and 1990). Figure 4 shows
that these biotites are considerably richer in Ti in which fugacity of O2 is calculated relative to
relative to A1 than those in the experiments of a standard state of pure 02 at the temperature
Patifio Douce et al. (1993). Comparison of of interest and 1 bar, A/t ~4,1 and AS r are the
Figs. 3 and 4 suggests that there is a systematic standard state enthalpy and entropy changes,
relationship between the Ti/A1 ratio of biotite respectively, of reaction (14) at the tempera-
and the misfit between biotite-ilmenite tem- ture of interest and 1 bar, AV, sol~d~ is the vol-
•..~v14
peratures and "expected" temperatures (i.e. ume change among the solid phases in equilib-
garnet-biotite temperatures or nominal exper- rium ( 14 ), lnKi is calculated with equation ( 5 )
imental temperatures). Biotites with the low- at the temperature and pressure of interest, and
est Ti/A1 ratios (e.g. those described by Wil- KSO~,d~
~3 is calculated from mineral composi-
liams and Grambling, 1990) display the tions as follows:
greatest departures from the expected temper- id . t,,~ '13/2
]{Tsolids a T i F e - 2 kt'tFe2037
atures. Adding a Ti-A1 compositional term to •",3 - (16)
the empirical calibration of equilibrium (1) avcTiO3

could therefore be capable of displacing bio- The usefulness of titanian biotite as a moni-
tite-ilmenite temperatures towards the ex- tor of oxygen fugacity can be tested by apply-
Ti SUBSTITUTION IN BIOTITE: EMPIRICAL MODEL WITH APPLICATIONS TO THERMOMETRY ETC.
ing Eq. (15) to rocks which contain both il-
menite and magnetite solid solutions, and then
comparing f(O2) values calculated from bio-
tite-ilmenite with those obtained from ilmen-
ite-magnetite at the same temperature.
Ghiorso and Sack ( 1991 ) presented tempera-
ture andf(O2) estimates for a large number of
volcanic rocks which contain two oxides.
Among these, the rocks described by Hildreth
( 1977 ), Whitney and Stormer ( 1985 ), Grun-
der and Mahood (1988), Flood et al. (1989)
and Carmichael (1967) also contain biotite.
Oxygen fugacities for these biotite-phyric vol-
canic rocks calculated with Eq. ( 15 ) are com-
pared to Ghiorso and Sack's f(O2) values in
Fig. 5 (see also Table 5 ). Biotite-ilmenite cal-
culations were performed at the temperatures
given by Ghiorso and Sack ( 1991 ) and pres-
sures fixed at 3 kbar for the Bishop Tuff (Hil-
dreth, 1977 ), 7 kbar for the Fish Canyon Tuff
(Whitney and Stormer, 1985) and 5 kbar for
all the other cases. Standard state properties for
equilibrium (14) were taken from Berman
-9
Biotite-ph~ric volcanic r o c k s ~
-11
5 13
~L
G~. -15
-17
-19
-19 -17 -15 -13 -11 -9
log f(O) (Ghiorso and Sack, 1991)
Fig. 5. Oxygen fugacities for biotite-phyric volcanic rocks
calculated from biotite-ilmenite equilibrium (Eq. 15),
plotted against oxygen fugacities calculated from magne-
tite-ilmenite, given by Ghiorso and Sack (1991 ). Both
sets of oxygen fugacities calculated at the same tempera-
tures. Details of samples and original sources given in Ta-
ble 5. Diagonal line shows 1 : 1 correlation. Uncertainties
in biotite-ilmenite f(O2) values propagated from stan-
dard errors of the regression parameters Ah ~', As~', and
Av~' (see text).
143
(1988 and 1990). Activities of ilmenite and
hematite were considered ideal, because for the
temperatures and oxide compositions of most
of these examples the ratio among the non-ide-
alities of ilmenite and haematite predicted by
the model of Ghiorso ( 1990 ) are much smaller
than the uncertainties associated with the em-
pirical model for equilibrium ( 1 ).
Figure 5 shows that there is a clear correla-
tion between oxygen fugacity values estimated
from biotite-ilmenite and those obtained from
two-oxide equilibria. There is, however, a sys-
tematic displacement of the biotite-ilmenite
values towards conditions more reducing than
those indicated by two-oxide equilibria, com-
monly by a factor of 1 to 1.5 orders of magni-
tude. This misfit is quite systematic over a
range of oxygen fugacities of almost 8 orders
of magnitude, suggesting that it might reflect a
deficiency in the empirical model for titanian
biotite, as discussed in the previous section,
rather than more haphazard causes such as
disequilibrium among phenocryst phases or
post-eruptive oxidation of oxide phases pref-
erentially to biotite. With few exceptions, al-
most all of the biotites used for this compari-
son lack A1vl (cf. Table 5, Fig. 4 ), again hinting
that a Ti-A1 compositional term might be re-
quired in the empirical expression for lnKI.
2.4. Improvement of the empirical model for
Ti-biotite equilibria
The observed discrepancies in calculated
temperatures and oxygen fugacities can be used
to derive the compositional term which ap-
pears to be required by the empirical model for
equilibrium ( 1 ). In order to accomplish this
task, Eq. (5) is modified in the following
manner:
AhT+Ah~ PAvT AsT
lnKl -- -- + ( 17 )
RT RT R
where Ah eXis an enthalpy term which accounts
for the change in the difference between the
excess chemical potentials of TiFe_2 and
144 A.E. PATII~O DOUCE

TABLE 5

Samples used for biotite-ilmenite oxygen barometry

Sample T ( °C ) l o g f ( Oz ) logf(02 ) A h ex Ti / log/( 02 )

No. (1) (2) (3) kJ/mole (Ti+AI) (4)

Hildreth(197~
20 726 - 15.58 -17.06 21.23 1.000 -15.36
48 736 - 15.29 -17.01 24.92 1.000 - 15.33
52 782 - 13.89 -15.46 23.78 1.000 -13.84
69 773 -14.22 - 15.74 22.83 1.000 -14.11
70 782 -13.87 - 15.53 25.15 1.000 -13.92
71 790 -13.58 - 15.18 24.42 1,000 -13.58
72 789 -13.61 -15.14 23.33 1.000 -13.53
73 796 - 13.42 - 15.24 27.94 1.000 -13.65
74 778 -13.96 -15.55 23.99 1.000 -13.93
75 695 -16.70 -17.68 13.62 1.000 -15.92
77 812 -13.10 -14.98 29.29 1.000 - 13.41
78 813 - 12.90 - 14.81 29.78 1.000 -13.25
79 785 - 13.76 - 15.43 25.37 1.000 -13.82
80 704 -16.37 - 17.51 15.99 1.000 -15.77
81 698 -16.55 -17.43 12.27 1.000 -15.68
89 691 - 16.80 -17.71 12.60 1.000 -15.95
95 699 -16.55 -17.60 14.65 1000 -15.85
105 706 - 16.27 - 17.53 17.71 1,000 -15.80
107 768 -14.36 - 16.08 25.71 1.000 -14.44
108 756 -14.64 -16.04 20.68 1000 -14.39
109 700 - 16.46 - 17.72 17.60 1.000 -15.97
110 705 - 16.28 - 17.91 22.89 1.000 -18.44
111 677 -17.34 -18.00 9,00 1.000 -16.21
128 719 - 16.11 -17.00 12,68 1.000 -15.28
133 778 - 14.02 - 15.78 26,56 1.000 - 14.16
135 780 - 13.92 - 15.66 26,31 1.000 -14.04
136 758 -14.57 - 16.20 24,13 1.000 - 14.55
137 799 -13.55 -15.49 29,86 1.000 -13.90
139 808 -13.24 -14.96 26.70 1.000 -13.39
140 710 - 16.16 - 17.51 19.05 1.000 -15.78
141 705 -16.32 - 17.62 18.26 1.000 -15.88

Whitney and Stormer (1985)

$42 705 - 13.92 - 15.3 19.38 0.920 - 13.89
S3a 796 - 12.31 - 13.78 22.56 1.000 - 12.19
S3b 729 - 13.36 - 14.72 19.57 1.000 - 13.02
$46 775 - 12.87 - 13.76 13.39 0.650 - 13.43
$48 745 - 12.91 - 14.40 21.78 1.000 - 12.73

Flood et al. (1989) (5)

T rhy 839 - 11.95 - 13.32 21.87 1.000 - 11.79
Pah 829 - 11.89 - 13.50 25.48 0.898 - 12.32

Grunder and Mahood (1988)

! 19 803 - 12.42 - 15.22 43.26 1,000 - 13.64
144 866 - 11.47 - 13.74 37.12 1.000 - 12.24

Carmichael (1967)
cam86 975 - 10.25 - 11.60 24.19 1.000 - 10.24
cam93 990 - 10.10 - 11.77 30.29 1.,300 - 10.42
call9 818 - 11.60 - 12.93 20.83 1.,300 - 11.37
1118 838 - 11.21 - 12.81 25.52 1.000 - 11.28

( 1) T e m p e r a t u r e f r o m G h i o r s o a n d S a c k ( 1 9 9 1 , T a b l e 1 ).
(2) l o g f ( O 2 ) f r o m G h i o r s o a n d S a c k ( 1 9 9 1 , T a b l e 1 ).
(3) logf(02 ) from biotite-ilmenite without Ti-A1 compositional term (this paper).
(4 ) logfl 02 ) from biotite-ilmenite with Ti-Al compositional term (this paper).
(5) F l o o d et al. ( 1 9 8 9 ) s a m p l e s a r e : T i v a C a n y o n r h y o l i t e ( T r h y ) a n d P a h C a n y o n ( P a h ) .
Ti S U B S T I T U T I O N IN BIOTITE: E M P I R I C A L M O D E L W I T H A P P L I C A T I O N S T O T H E R M O M E T R Y ETC.
A12Fe_ 3 of a given biotite composition relative
to the biotite compositions used to calibrate the
model. In other words, Ah ex has been (arbi-
trarily) averaged out to 0 when the experimen-
tal data were fitted to Eq. (5), and by includ-
ing this term now we are measuring how much
the excess chemical potential of TiFe_2
changes relative to that ofAl2Fe_ 3 with biotite
composition, referred to the average differ-
ence between these excess chemical potentials
in the experimental products of Patifio Douce
etal. (1993).
The value ofAh ex is derived from the differ-
ence between the value of an intensive variable
calculated from a Ti-biotite equilibrium and
the value of that variable used as reference, as
follows. For temperatures calculated from bio-
tite-ilmenite-aluminosilicate-quartz equilib-
rium, Ah ex is given by:
Ah ex= ( TR _ To) (AsT - RInKI )
where TR is the expected or reference temper-
ature (e.g. from garnet-biotite) and Tc is the
temperature calculated from equilibrium ( 1 ).
For temperatures calculated from aluminosil-
icate-absent assemblages with equilibrium
( 10 ) the expression for Ah ex is:
Ah ex= ( TR - - Tc) (AsT + ASlr~ - R l n K l 0 ) (19)
where TR and Tc are as above and AS ~R is the
standard state entropy change of equilibrium
( 12 ) at the expected temperature. Finally, dis-
crepancies in oxygen fugacities lead to the fol-
lowing expression for Ahex:
3RT
Ah~x= ~- (lnfo2,R--lnfo2,c)
wherefo2,R is the expected oxygen fugacity (in
this case, the values given by Ghiorso and Sack,
1991 ) and fo2,c is the oxygen fugacity calcu-
lated at the same temperature from biotite-il-
menite equilibrium, with Eq. ( 15 ).
Figure 6 shows that the values of Ah ex are
fairly well correlated with the ratio T i /
(Ti+A1). This correlation is far from being
perfect but it is remarkable because it is ob-
145
50
Ah e~ - 3 1 , 1 + 55.5 [ T i / ( T i + A I ) ] kJ/mole
=
25 ©
-25 l *
O]OIqoldaway et al., 1988
• Pigage , 1982
• Williams a n d Gratabling. 1990
• Patino D o u c e and Beard, in p r e p
iotite-phyr:~c volcanic rocks
-50 ' ~--
0.2 0.4 0.6 0.8
T i / ( T i + A1 )
Fig. 6. Correlation between Ahex (see text) and Ti/
(Ti + A1) in biotite. Regressionline fitted by least squares,
with regressionparameters shownat the top of the figure.
Double arrow showsrange in Ti / (Ti + AI) in experimen-
tal biotitesof Patifio Douceand Johnston ( 1991), see text
for explanation.
( 18 ) tained from three different equilibria operat-
ing on different bulk compositions, and cov-
ering wide ranges of temperatures, pressures
and oxygen fugacities. Linear regression of the
data in Fig. 6 yields:
Ah ex( k J / m o l e ) = - 3 1 . 1 ( _+ 1.8)
+55.5(_+2.2) [ T i / ( T i + A1) ]
with r2=0.88 and standard errors of regres-
sion coefficients shown in parentheses.
The double arrow in Fig. 6 indicates the
range in T i / ( T i + A 1 ) covered by the experi-
mental products of Patifio Douce et al. ( 1993 ).
If the discrepancies in calculated temperatures
and oxygen fugacities discussed earlier were
(20) entirely accounted for by this additional com-
positional term then the regression line should
intersect the Ahex=0 ordinate somewhere
within the range indicated by the arrow, and
this is not the case. This denotes a limitation
of the empirical model which is not possible to
address further with the nature and quality of
the database used to develop it. One possible
cause of this limitation could be the fact that
varying M g / F e ratios have not been consid-
ered. Although Patifio Douce et al. (1993)
146 A.E. PATII~IODOUCE

found that the differences between MgA1 and 950 . . . . . . . . . . .

FeA1 and MgTi and FeTi interactions in bio- 900 ~ ,

tite are small compared to the absolute values 850
of these interactions, these differences are not
entirely negligible (see also Zhou and Lin-
dsley, 1992), and varying Mg/Fe ratios will
have some effect on the excess chemical poten-
C 800
E-
750
700 '~Y
=*
_% ./ l

tials of biotite components. Another possibil- d 650

ity is that there might exist important cross-site • # • Holdawayet al, 1988
(tetrahedral-octahedral) contributions to non- 550
##
• •
• Pigage, 1982
rambling,1990
~, PatinoDouce~nd Beard, in prepI
,
ideal mixing in biotite, and changes in tetra- 500/'" j. ~,.oo.... . I
hedral AI content are ignored in the activity 500 550 600 650 700 V50 800 850 000 950
Expected T (°C)
expression for the TiFe_2 exchange compo-
nent. In spite of these uncertainties, I argue that Fig. 7. Same as Fig. 3, except that biotite-ilmenite tem-
the main purposes of this empirical model, peratures were calculated including the empirical Ti-AI
which are demonstrating the potential of Ti compositional term.
components in biotite as a thermodynamic tool
and stressing the need to obtain rigorous ther- -9
modynamic data for such components, are ~" -11 Biotite-phyric volcanic rock s[ ~ / v ~ / ~~_ ]

clearly fulfilled.

2.5. Application of the expanded empirical -13

model E
0 -15

Combining the expression for Ahex with the

regression coefficients Ah]', As~' and Av7 -17
yields the following empirical expression for
lnKl, which can be used to calculate tempera- -19
-19 -17 -15 -13 -ll -9
tures from biotite-ilmenite-sillimanite-quartz
log f(O2) (Ghiorso and Sack, 1991)
assemblages (cf. Eq. 17 ):
Fig. 8. Same as Fig, 5, except that biotite-ilmenite oxygen
fugacities were calculated including the empirical Ti-AI
l n K l = - - 1 ( 1 1 3 9 3 + 6 6 7 5 [ TTi@A1]+I80P ) compositional term.

+ 16.23
with P in kbar and T in Kelvin. In a similar
fashion, calculation of oxygen fugacities in-
cluding the Ti-A1 compositional term is ac-
complished by calculating lnKl in Eq. (15 )
with Eq. (21 ) rather than with Eq. ( 5 ).
The results of applying the expanded empir-
ical model to the same data discussed previ-
ously are shown in Figs. 7 and 8 (see also Ta-
bles 3 and 5). Temperatures recovered from
equilibria ( 1 ) and (10) are now much closer
to the expected values, in most cases within
(21)
+_50°C. The differences between calculated
and expected temperatures are still not en-
tirely random but, given the uncertainties in the
garnet-biotite geotherrnometer used as refer-
ence for the natural assemblages, the signifi-
cance of this observation is not clear. Equilib-
rium (1) nevertheless appears capable of
yielding reasonable estimates of crystallization
temperatures of biotite+ aluminosilicate +
quartz+ilmenite assemblages, which will be
particularly valuable in rocks lacking other
temperature-sensitive assemblages (e.g. gar-
Ti SUBSTITUTION IN BIOTITE: EMPIRICAL MODEL WITH APPLICATIONS TO THERMOMETRY ETC. 147

net-free mica schists and peraluminous
granitoids).
The agreement between calculated and ex-
pected oxygen fugacities is also fairly good
(Fig. 8), in most cases within a factor of 2.
Discrepancies also show a somewhat system-
atic trend, with calculated f ( O 2 ) values tend-
ing to be more oxidized than the expected ones
in the more reduced samples and viceversa in
the more oxidized samples. In this case the dis-
crepancies m a y arise from neglecting Fe 3+
contents in biotite. Figure 9 shows the differ-
ences between biotite-ilmenite and magne-
tite-ilmenite f ( O 2 ) values plotted against
A1ogf(O2) (---- 1ogf(O2)--logf(O2) QFM at the
temperature of interest, e.g. Frost et al., 1988 ).
Moving from more reducing towards more ox-
idizing conditions will cause greater propor-
tions o f F e 2+ in biotite to be oxidized to Fe 3+,
thus causing the activity of TiFe_2 calculated
under the assumption that all Fe is Fe z+ to be
lower than the real activity of the exchange
c o m p o n e n t (cf. Eq. 9). The effect will be that
the calculated oxygen fugacity will also be lower
than the actual f(O2 ), generating a trend such
as that observed in Fig. 9. In spite of this short-
coming, the biotite-ilmenite redox equilib-
rium is demonstrably capable of providing
reasonable estimates of oxygen fugacity and
this should prove usefial in metamorphic and
intrusive rocks which lack two-oxide (or other
f(O2 )-sensitive ) assemblages.
2.6. Application of Ti-biotite to H20
barometry
Breakdown of Ti-annite to ilmen-
ite + sanidine + H20 takes place according to
the following reaction:
KTiFeAISi3010(OH)2
~-KA1Si3Os+FeTiO3+H20 (22)
This equilibrium can b,e used to estimate H20
fugacity from the assemblage biotite+alkali
feldspar+ ilmenite, which is very c o m m o n in
granitic and rhyolitic rocks and in m a n y gran-
ulites and migmatites. An empirical approxi-
mation to the equilibrium constant for reac-
tion (22) can be obtained by combining the
expression for lnKl (Eq. 21 ) with the change
in standard-state properties for the muscovite
breakdown equilibrium:

Biotite-phyric volcanic rocks

KA12A1Si3O1o(OH) 2 + SiO2
~KA1Si308 +AlzSiO5 + H 2 0 (23)
o
The resulting equation for fugacity of H20
o ~
o2~, o o ° (relative to a standard state of pure H20 at the
c 0,% 0% temperature of interest and 1 bar) is then the
~
0~_1
o (' c following:
o

1
-21 A ggl,T D A IZ solids
o lnfH20 = ~ [ -- ,--~• 23 ----~--23 + TASk31
-3
1 0 1 2 3 4 - lnK~ - lnK~°lidS.2 ( 24 )
Alog f ( O ) (QFM)
where bat/J3 ,1 and ASiI~ are the standard state
Fig. 9. Misfit between calculated (biotite-ilmenite) and enthalpy and entropy changes, respectively, of
expected (magnetite-ilmenite) oxygen fugacities of bio- reaction (23) at the temperature of interest and
tite-phyric volcanic rocks, plotted as a function of
Alogf(02 )QVM( = log)C(02 )--loDr(02) of QFM at the same 1 bar, '~--23Av~°lidsis the volume change of the
T and P). The negative correlation can be a result of ig- crystalline phases in reaction (23), and K ~ ~ids
noring Fe3+ contents in biotite (see text). is given by:
148 A.E. PATI/qO DOUCE

the temperature and pressure of interest) cal-

Kso|ids
22 --
ailm "aksp
aTi-annite
The activity of Ti-annite for this empirical for-
mulation is taken to be ideal, as given by Eq.
(8). It is important to note that, in contrast to
the empirical expressions for temperature and
oxygen fugacity, which involve a Ti exchange
component in biotite, estimation of H20 fu-
gacity must rely on an additive component.
The activity of the Ti-annite additive compo-
nent is subject to greater uncertainties than the
activities of the exchange components, chiefly
because of the (unknown) tetrahedral and/or
cross-site contributions to the excess Gibbs free
energy of mica. In spite of these uncertainties,
application of Eq. (24) to natural examples
yields H20 fugacity values which are in most
cases reasonable.
Table 6 shows fugacities and activities of
H20 (relative to the fugacity of pure H20 at
(25) culated for several examples taken from the lit-
erature. The first three examples correspond to
silicic volcanic rocks which were also included
in the discussion of Ti-biotite as an oxygen ba-
rometer. Estimated activities of H 2 0 for the
Bishop Tuff define two distinct populations
(Fig. 10 (a) and Table 6 ). In the early-erupted
pumices, thought to represent the shallower
and more HzO-rich portions of the magma
chamber, calculated a (H20) are more or less
evenly distributed over the range 0.4 to 1.0,
with some samples yielding values greater than
1.0 (up to 1.7). For welded-tuffsamples, rep-
resenting deeper and drier levels in the magma
chamber, calculated a (H20) cluster in the in-
terval 0.4 to 0.8. These values are consistent
with the concept that the Bishop magma-
chamber was rich in H 2 0 , probably approach-
ing H20-saturation in its upper levels (e.g. An-
derson et al., 1989). The samples which yield

TABLE 6

Application of Ti-biotite to H20 barometry

Data set Range in calculated Corresponding

f ( H 2 0 ) (bar) a(H20)

Hildreth (1977) (Bishop Tuff)

Pumices 1100 to 4000 0.4 to 1.7
Welded Tufts 500to 1900 0.2 to 0.8
Whitney and Stormer ( 1985 ) (Fish Canyon Tuff ) 1200 to 2500 0.16 to 0.34
Flood et al. (1989) (Paintbrush Tuff) 750 to 2000 0.16 to 0.42
Hansen et al. ( 1987 ) (Granulites from S India and Sri Lanka)
Kabbal-type gneisses 1000 to 2000 0.16 to 0.32
Kabbal-type charnockites 700 to 1600 0.11 to 0.25
Ponmudi-type gneisses 400 to 1100 0.07 to 0.17
Ponmudi-type charnockites 200to 800 0.03 to 0.13
Srikantappa et al. ( 1985 ) (Kerala Charnockites) 200 to 5000 0.04 to 0.88
Janardhan et al. (1982) (Karnataka Charnockites)
Lowland localities 250 to 1850 0.05 to 0.35
Highland localities 350 to 800 0.04 to 0.08
Bhattacharya and Sen ( 1986 ) (Madras Granulites)
Charnockites 950 to 2400 0.07 to 0.20
Metapelites 200 to 400 0.02 to 0.04
Grant and Frost (1990) (Morton Pass aureole)
Opx-bearing rocks 500 to 1500 0.18 to 0.50
Opx-free rocks 2 0 t o 100 <<0.1
Tracy ( 1978 ) (Pelitic migmatites, Massachusetts) 2 0 t o 100 <<0.1

Temperatures and pressures for the first three examples as in Table 5.

Temperatures and pressures for all the other examples from the original references.
Ti S U B S T I T U T I O N IN BIOTITE: E M P I R I C A L M O D E L W I T H A P P L I C A T I O N S T O T H E R M O M E T R Y ETC.
(a)
~ 0.4 g 04
r,
.~ 0.2 .o 0.2
0
0 0.2 0.4 0.6 0.8 1
0
a (He0)
(b) : processes (named Kabbal-type and Ponmudi-
Kabbal-type
0.8
0.6
0.4 g under lower H20 activity than Kabbal-type
: 0.2
;.a.,
0 that a (H20) calculated from equilibrium ( 22 )
o 0.I 0.2 0.3 0.4 0.5
a (H O)
Fig 10. (a) (Top) H 2 0 activities in different units of the
Bishop Tuff, calculated from breakdown of Ti-annite to
ilmenite + sanidine + H20 , Eq. 24 (mineral compositions
from Hildreth, 1977). Some pumice samples yield (erro-
neous) H 2 0 activities greater than 1 (see Table 6). (b)
(Bottom) H20 activities (calculated with Eq. 24) in the
two types of charnockites from southern India and Sri
Lanka, described by Hansen et al., 1987 (mineral com-
positions from these authors).
values greater than 1 are clearly in error, per-
haps arising from a large Fe 3+ content in bio-
tite or, alternatively, reflecting the uncertain-
ties in the activity of the Ti-annite additive
component discussed above. In contrast to the
H20-rich Bishop Tuff, the Fish Canyon Tuff
appears to have been strongly undersaturated
in H20 (Whitney and Stormer, 1985 ). Fugac-
ities of H20 estimated from Ti-biotite (1200
to 2500 bars, cf. Table 6) are in excellent
agreement with the fugacities proposed by
Whitney and Stormer (2000 ___1000 bars). Fi-
nally, although independent estimates of H20
fugacity for the Paintbrush Tuff are not avail-
able, a (H20) values estimated from Ti-biotite
(0.16 to 0.42 ) seem reasonable for a rather hot
silicic magma (cf. Flood et al., 1989).
The next four examples included in Table 6
correspond to granulitic rocks from the high-
grade terranes of Southern India and Sri Lanka.
149
The rocks discussed by Hansen et al. (1987)
constitute particularly good test-cases. These
authors studied "close-pairs" of rocks of the
same bulk composition straddling the amphi-
bolite-to-granulite transition and differing in
whether orthopyroxene was present (char-
0 0.2 0.4 0.6 0.8 nockites) or absent (gneisses). They con-
a (H20) cluded that two distinct charnockite-forming
type, after the respective localities) can be
identified in these high-grade terranes and that
Ponmudi-type charnockites were generated
charnockites. Figure 10(b) and Table 6 show
0 0.1 0.2 0.3 0.4 0.5
a (H20) is distinctly lower in the Ponmudi-type char-
nockites than in the Kabbal-type ones. Fur-
thermore, charnockites tend to record lower
H20 activities than isochemical orthopyrox-
ene-free gneisses. These trends are in good
agreement with the conclusions of Hansen et
al. (1987). Estimated H20 activities from
other charnockitic localities are also generally
low (cf. Table 6 ), but in the Madras granulites
(Bhattacharya and Sen, 1986) metapelites
yield much lower H20 fugacities than adjacent
charnockites. This difference is opposite to that
inferred by Bhattacharya and Sen, and is likely
to reflect a shortcoming of the empirical Eq.
(24), as will become more clearly apparent by
reference to the last two examples in Table 6.
Metamorphic conditions in the contact au-
reole of the Laramie anorthosite complex have
been discussed in detail by Grant and Frost
(1990). Many of the rocks affected by contact
metamorphism are of broadly pelitic compo-
sition, but there is enough variability in bulk
compositions that some rocks contain ortho-
pyroxene + cordierite whereas other, more al-
uminous ones, lack orthopyroxene in favor of
cordierite + garnet _+sillimanite. There is a no-
ticeable difference in the AI content of biotite
from both kinds of rocks, with the more alu-
minous ones containing 2 to 3 times more oc-
tahedral A1 than the less aluminous ones. Cal-
culated H20 fugacities are much lower in the
150
more aluminous assemblages (cf. Table 6 ). In
fact, H20 fugacities calculated for the latter as-
semblages are almost certainly erroneous, be-
cause it is unlikely that biotite could be stable
at the P - T conditions of the Morton Pass au-
reole at such low H20 pressures. H20 fugaci-
ties estimated from orthopyroxene-bearing
rocks, on the other hand, appear reasonable
even though it remains unknown whether or
not these are the true values. The last example
in Table 6 is taken from a package of pelitic,
aluminosilicate-bearing migmatites described
by Tracy (1978). In this case estimated H20
fugacities are uniformly very low and almost
certainly erroneous.
It is apparent that Eq. (24) does not yield
reasonable estimates of H20 fugacity in pelitic
rocks, in which biotite is very rich in A1, but
that results obtained from less aluminous bio-
tites are in general plausible. In order to ra-
tionalize this conclusion it must be recalled that
the compositional term in the empirical equa-
tion for lnK1 accounts for relative changes in
the magnitudes of the excess chemical poten-
tials of the exchange components TiFe_2 and
AleFe_ 3, but that this empirical correction fac-
tor cannot address the absolute magnitudes of
the excess chemical potentials of the additive
components. The results summarized in Table
6 suggest that the empirical model for lnK~ (Eq.
21 ) provides a good approximation to the be-
havior of the Ti-annite additive component as
long as the ratio T i / ( T i + A1) remains close to
1, but that if biotite contains a non-negligible
concentration of A1w this approximation
quickly diverges from the real behavior of the
mica. This inference is consistent with the sug-
gestion of Patifio Douce at al. (1993), in the
sense that there appears to be a large Ti-A1 ex-
cess free energy of mixing in biotite. Note that
if this is the case then the activity of Ti-annite
in pelitic rocks would increase (perhaps very
significantly) relative to the ideal activities
considered in Eq. (25), thus generating higher
calculated H20 fugacity values. Until these is-
sues are resolved, Eq. (24) should be applied
A.E. PATIIqODOUCE
with caution. It is nevertheless clear from the
examples discussed here that the locus of equi-
librium (22) is very sensitive to the prevailing
chemical potential of H20, so that the widely
distributed assemblage biotite + ilmenite + al-
kali feldspar should constitute a reliable H20
barometer once a rigorous thermodynamic
model for biotite is available.
3. Dehydration and melting equilibria of biotite
in Ti-bearing bulk compositions
Although there is gene,ral agreement on the
fact that Ti saturation extends the thermal sta-
bility of biotite, the actual magnitude of this
effect remains unknown owing to the lack of
thermodynamic data for titanian components
in biotite. The empirical model discussed here
can be used to calculate phase relationships of
assemblages containing 'biotite and a Ti-satu-
rating phase. A preliminary analysis is pre-
sented below, focused on the effects of Ti sat-
uration on the loci and nature of the terminal
reactions of biotite in the non-peraluminous
system: MgO-FeO-Fe203-TiO2-SiO2-
KA102-H20 ( M F F ' T K S H ) . Comparison with
the equivalent Ti-free system M g O - F e O -
Fe203-SiO2-KA102-H20 ( M F F ' K S H ) will
serve to visualize the extent to which solution
of Ti modifies the behavior of biotite. The re-
suits will improve our understanding of the
ability of biotite to transport H20 to the deep
crust and of the conditions under which titan-
ian biotite will break down and induce melting
in the continental crust.
3.1. Topological relationships of biotite
devolatilization reactions in Ti-saturated and
Ti-free systems
The first steps in this analysis are to estab-
lish the topological relationships among the
Ti SUBSTITUTION IN BIOTITE: EMPIRICALMODELWITH APPLICATIONSTO THERMOMETRY ETC. 151

¢x/
0
~ (op,qz)

mt+qz "~ .

~ z " ~ o j (op.qz)

1÷ z tbi,sa~

~ opx
Constant P, T, PFeSi03

(il)

,/2, He 0
Fig. 11. Topological relationships among various terminal reactions for titanian biotite in the system MgO-FeO-Fe203-
TiO2-KAIO2-SiO2-H20, at constant temperature, pressure and orthopyroxene composition. The stability of bio-
tite + quartz assemblages is limited by the series of reactions shown with thick solid lines. Abbreviations are as follows, bi:
biotite solid solution (an nite-phlogopite-Ti-annite ); qz: quartz; op: orthopyroxene solid solution ( enstatite-ferrosilite );
sa: sanidine; ru: rutile; il: ilmenite solid solution (ilmenite-haematite); mr: magnetite solid solution (magnetite-ulvos-
pinel ); hm: haematite solid solution (haematite-ilmenite).

equilibria that will be discussed, and the inten-
sive variables relative to which these phase re-
lationships will be examined. In Ti-saturated
bulk compositions equilibria among biotite and
oxide phases must be considered. Because of
this fact, an isothermal and isobaric analysis of
phase relationships as a function o f the chem-
ical potentials (or fugacities) o f O2 and H 2 0 is
most useful in visualizing the effect of Ti on
biotite stability (cf. Figs. 11 and 12). The dis-
cussion can be simplified by treating these fu-
gacities independently of any considerations of
fluid compositions, or, indeed, o f the actual
presence of a free fluid phase (cf. Spear et al.,
1982). Thus, " H 2 0 " in these phase diagrams
can indicate either a c o m p o n e n t in a fluid
phase, or a c o m p o n e n t dissolved in a silicate
melt, or a situation in which no fluid phase nor
melt are present but the chemical potential of
H20 is defined by the mineral assemblage (e.g.
Thompson, 1983 ).
In the system M F F ' T K S H the crystalline
phases of interest are: biotite solid solution
(ss.), orthopyroxene ss., magnetite ss., ilmen-
ite ss., hematite ss. *, rutile, sanidine and
quartz. Subsets of six phases from this list con-
stitute trivariant assemblages (with H 2 0 and
02 fugacities treated as discussed a b o v e ) ,
which will become pseudoinvariant if three in-
tensive variables are fixed. Therefore, if pres-
*The distinction between ilmenite ss. and hematite ss. is
made on the basis of whether FeTiO3 or Fe203 is the ma-
jor component of the solution; however, as long as only
the topological relationships are considered, the actual
compositional span of each of these phases remains
undefined.
152
(mt)
Fig. 12. Same as Fig. 11, but for the Ti-free system MgO-FeO-Fe203-KA102-SiO2-H20. The stability of the assemblage
biotite+quartz is in this case limited by the oxygen-independent reaction shown with a thick solid line. Abbreviations as
in Fig. 11, except that mt in this case is pure end-member magnetite and bi does not include Ti-annite.
sure, temperature, and the chemical potential
of a component in one of the crystalline phases
are fixed, a six-phase assemblage can only exist
at a pseudoinvariant point on the f ( O 2 ) -
f ( H 2 0 ) plane, around which there will be ar-
ranged 6 pseudounivariant equilibria. For
computational simplicity it is often conve-
nient to use orthopyroxene composition as a
fixed parameter, so that the isothermal and
isobaric phase diagrams are shown at constant
chemical potential of FeSiO3 (this choice is
purely arbitrary, however). The topology of the
phase relationships (at constant T, P and or-
thopyroxene composition) in the Ti-saturated
system MFF' TKSH are shown in Fig. 11.
The ultimate stability of the assemblage Ti-
biotite + quartz is given by the sequence of de-
volatilization reactions (shown by the thick
solid lines in Fig. 11 ) which produce orthopy-
roxene, sanidine and a Ti-saturating oxide
A.E. PATIiqO DOUCE
(op,qz)
op+O 2
(bi.sa)
~z o p x
Constant P, T, FeSi03
/t£ H2 0
phase (rutile, ilmenite ss., or magnetite ss., in
order of increasing f(O2 ) ). The intervals over
which these devolatilization reactions are sta-
ble are defined by successive, H20-indepen-
dent, biotite- and sanidine-absent, orthopy-
roxene oxidation reactions. Each of these H20-
independent reactions limits the stability of a
particular oxide phase in the presence of or-
thopyroxene of fixed composition; the ulti-
mate stability of orthopyroxene of this com-
position is given by the most oxidizing of these
reactions. All of the orthopyroxene-oxide re-
actions move towards more oxidizing condi-
tions as the bulk composition becomes more
magnesian.
The effect of oxygen fugacity on the stability
of the assemblage Ti-biotite + quartz varies de-
pending on which is the Ti-saturating oxide
phase. For conditions reducing enough to sta-
bilize rutile (at the P, T and Mg# of interest),
Ti SUBSTITUTION IN BIOTITE: EMPIRICAL MODEL WITH APPLICATIONS TO THERMOMETRY ETC.
the stability of biotite + quartz is independent
of oxygen fugacity, but as the Ti-saturating ox-
ide phase becomes enriched in Fe 3+ the stabil-
ity of the assemblage biotite + quartz becomes
more sensitive to oxygen fugacity (cf. Fig. 11 ).
The actual magnitude of this effect is not large,
however, and will be discussed in more detail
below.
Phase relationships in the Ti-free system
M F F ' K S H are shown in Fig. 12. In this case
magnetite is the only oxide phase that needs to
be considered, because, for fixed orthopyrox-
ene composition, the oxidation of orthopyrox-
ene to Ti-bearing magnetite solid solution (cf.
Fig. 11 ) must take place at anf(O2 ) lower than
that at which orthopyroxene is oxidized to pure
magnetite. Hence, the entire phase diagram for
Ti-saturated bulk compositions (Fig. 11 ) must
lie at oxygen fugacities more reducing than the
ultimate stability of orthopyroxene in Ti-free
bulk compositions (the H20-independent
equilibrium in Fig. 12). This relationship
makes it unnecessary to consider hematite-
bearing assemblages in Ti-free bulk
compositions.
In the Ti-free system only five phases can co-
exist at fixed pressure, temperature and ortho-
pyroxene composition, so that the assemblage
orthopyroxene ss. + biotite ss. + magnetite +
sanidine+ quartz defines a pseudoinvariant
point in t h e f ( O 2 ) - f ( H 2 0 ) plane (Fig. 12).
At conditions more oxidizing than those of this
pseudoinvariant point, biotite oxidizes to
magnetite+sanidine regardless of the pres-
ence of quartz in the assemblage. Orthopyrox-
ene is only stable at oxygen fugacities below
that of the pseudoinvariant point, and under
these conditions the stability of the assemblage
biotite + quartz is limited by the magnetite-ab-
sent OffO2 )-independent) devolatilization re-
action which produces orthopyrox-
e n e + sanidine. A comparison of the calculated
locus of this reaction with the loci of the equiv-
alent reactions in Ti-saturated bulk composi-
tions will provide insight regarding the effect
of Ti on the stability of the assemblage bio-
15 3
tite+quartz. However, the stability of all of
these subsolidus equilibria relative to melting
reactions must be discussed first.
3.2. Melting relationships in Ti-saturated,
biotite-bearing assemblages
Because biotite breakdown occurs at P-T
conditions which overlap those at which an
H20-bearing felsic silicic melt can exist, por-
tions of the phase diagrams in Figs. 11 and 12
can be metastable relative to melting reac-
tions. The biotite+quartz dehydration equi-
libria determine the lower values of the chem-
ical potential of H20 at which this assemblage
is stable (cf. Figs. 11 and 12). Whether or not
such subsolidus dehydration equilibria are sta-
ble relative to melt-present assemblages de-
pends on the fugacity of H20 required to sta-
bilize a silicate melt at the temperature,
pressure and bulk composition of interest. The
relative stabilities of subsolidus dehydration
relative to melting reactions can be addressed
by comparing the topology of an isothermal
and isobaric/z (O2)-/~ (H20) diagram with that
of a P-T diagram at fixed chemical potentials
of fluids, cf. Fig. 13. Only one vapor-saturated
melting curve is shown in the P-T diagrams,
corresponding to the haplogranitic vapor-sat-
urated solidus: quartz+ sanidine+ vapor=
melt. As discussed by Vielzeuf and Clemens
(1992), this reaction is close enough to the
equivalent phlogopite-bearing reaction (phlo-
gopite+ quartz+ sanidine+ vapor= melt)
that it can serve as an effective model for the
latter equilibrium. This conclusion is based on
the fact that the solubility of MgO in low-tem-
perature silicic melts is very low, so that its ef-
fect on the chemical potentials of the essential
components of such melts (quartz, feldspar
and H20) is almost negligible. Because the sol-
ubilities of FeO and TiO2in such melts are also
very low (e.g. Puziewicz and Johannes, 1988;
Patifio Douce and Johnston, 1991 ), the hap-
logranitic, vapor-saturated solidus is a good
analogue, in general, for the biotite-present re-
154
(a)
o"
[]
H-HzO
(b
t
~ [ ] z~,I
* '[ N
] ,
+ ~,
i C) or vapor saturated melting (if the fugacity
/~Hzo
Fig. 13. Possible topological relationships among the va-
por-saturated solidus (see text for more details) and the
subsolidus dehydration reaction of biotite + quartz. (a)
Melting occurs at a fugacity of H20 higher than that at
which biotite dehydrates (in quartz-bearing assem-
blages). Within region (A) the solid assemblage bio-
rite+quartz is stable. An isothermal and isobaric de-
crease in /~(H20) leads to subsolidus dehydration, i,e.
conditions move into region (C); this can be seen directly
in the/L(O2)-l~(H20) diagram, and can also be deduced
from the P- Tdiagram by noting that a decrease in/t( H20 )
will displace the melt-absent curve towards lower temper-
atures (see also Vielzeufand Clemens, 1992). An isother-
mal and isobaric increase in lt(H20) will cause vapor-sat-
urated melting of the assemblage biotite + quartz (region
B ). (b) Melting occurs at a fugacity of H20 below that at
which the assemblage biotite + quartz dehydrates. An an-
hydrous subsolidus assemblage is the only stable assem-
blage in region (D). Melt is stable everywhere above the
vapor-present solidus (region E); note that only the
metastable extension of the biotite + quartz devolatiliza-
lion reaction can be crossed in this case. Because the va-
por-absent solidus (V in the figure) is fixed on the P - T
plane (see Vielzeuf and Clemens, 1992), it can only be
seen on the fl(O2)-fl(H20 ) plane if this plane is con-
strucled for a P - T point on the vapor absent solidus. In
such case (not shown in the figure) the vapor-absent so-
lidus on the f l ( O 2 ) - ~ / ( H 2 0 ) plane will be only a point,
corresponding to the conditions at which the vapor-satu-
rated solidus and the subsolidus dehydration equilibrium
intcrsect. In every other case (the general case shown in
the figure) the vapor-absent solidus does not exist on the
~ ( O 2 ) - ~ ( H 2 0 ) plane.
A.E. PATIIqO DOUCE
(v) action (both in Ti-saturated and in Ti-free bulk
compositions):biotite + quartz + sanidine +
vapor = melt, and also for the low-pressure
biotite-absent reaction: orthopyroxene + san-
idine + quartz + vapor = melt.
If the fugacity of HzO required to stabilize a
melt at the given P-Tconditions is higher than
that at which biotite+quartz dehydrate (Fig.
13a), the topological relationship between the
T subsolidus-dehydration and melting equilibria
(v) corresponds to that between the stable por-
tions of these curves in the P - T diagram. For
H20 fugacities within region (A) an entirely
solid, biotite+quartz-bearing assemblage is
stable. Such assemblage can undergo either
subsolidus dehydration (e.g. by an isothermal
and isobaric decrease in H20 fugacity, region
of HzO increases at constant P and T, region
T
B). These relationships can be seen directly on
the ~t(Oz)-fl(H20 ) diagram, and can also be
inferred from the P - T diagram by noting that
an increase in f l ( U 2 0 ) will lower the tempera-
ture of the vapor-saturated solidus, whereas a
decrease in # (H20) will lower the temperature
of the subsolidus dehydration reaction.
In contrast to the case discussed in the pre-
vious paragraph, if a melt is stabilized at a fu-
gacity of H 2 0 lower than that at which bio-
rite+quartz dehydrate ,(Fig. 13b), then the
topology corresponds to that observed in the
P - T diagram between the vapor-saturated so-
lidus and the metastable extension of the sub-
solidus dehydration reaction. Under these
conditions the assemblage biotite + quartz, and
hence the biotite+quartz terminal reactions
shown in Figs. 11 and 12, are never stable. If
the fugacity of H20 is lower than that at the
vapor-saturated solidus (region D) the stable
condensed assemblage consists only of anhy-
drous crystalline phases. For fugacities of H20
above this solidus a melt is always stable (re-
gion E).
Because widespread melting of metamor-
phic assemblages is believed to take place in
many cases under vapor-absent conditions, it
Ti S U B S T I T U T I O N IN BIOTITE: E M P I R I C A L M O D E L W I T H A P P L I C A T I O N S TO T H E R M O M E T R Y ETC. 1 55

is important to discuss how these topological 10

relationships lead to the demarcation of the 8/~' /~/ /

vapor-absent solidus of Ti-bearing biotite. The
vapor-absent solidus is shown with (V) in the
P - T diagrams in Fig. 13, but is not shown in "2"
the ] I ( O 2 ) - I I ( H 2 0 ) diagrams. This is so be- / / /
e~
cause the vapor-absent solidus does not neces-
sarily exist on the/~(O2)-/z(H20) plane. As // '
discussed by Clemens and Vielzeuf ( 1987 ) and
Vielzeuf and Clemens (1992), the vapor-ab- ~'* M g # = 0.51l
sent solidus is fixed in P - T space, and inde- 0
pendent of/1(H20). Thus, the vapor-absent 750 800 850 900
T ('C)
solidus will only intersect the # (O2)-/z (H20)
plane if the latter is constructed for a P - T p o i n t
which lies on this solidus. In such case the pro-
Fig. 14. Calculated loci of the dehydration-melting solidi
jection of the vapor-absent solidus on the of biotite ( M g = = 0 . 5 ) + q u a r t z assemblages in Ti-free
# ( O 2 ) - # ( H 2 0 ) plane will be a single point, (broken line) and Ti-saturated (solid lines) bulk com-
defined by the intersection of the vapor-satu- positions. Ti-saturated solidi calculated at QFM and
rated solidus with the subsolidus devolatiliza- QFM-3; Ti-free solidus is independent off(O2), see text.
In Ti-bearing bulk compositions not rich enough to con-
tion reaction (i.e., this point will correspond tain ilmenite, melting will begin within the interval be-
to the invariant point shown in the P - T dia- tween both solidi, and biotite will persist (becoming pro-
grams, cf. Clemens and Vielzeuf, 1987). This gressively enriched in Ti) up to the conditions of the Ti-
line of reasoning can be used to calculate the saturated solidus, at which point ilmenite will crystallize.
The experimental phlogopite + quartz solidus (after Viel-
dehydration-melting solidus of Ti-saturated
zeufand Clemens, 1992) shown for comparative purposes.
biotite + quartz assemblages, by using the em-
pirical model for Ti solution in biotite to cal-
culate the loci of devolatilization equilibria because the empirical model for Ti-solubility
(e.g. b i o t i t e + q u a r t z + O 2 ~ orthopyroxene is likely to yield more reliable results at such
+ sanidine + ilmenite + H20) and matching intermediate compositions, but this ratio is also
fugacities of H20 on such equilibria with fu- a reasonable approximation to "average" crus-
gacities of H20 on the vapor-saturated solidus tal bulk compositions. Two dehydration-melt-
(see discussion of this procedure in Vielzeuf ing solidi, calculated at riO2) conditions of
and Clemens, 1992 ). QFM and QFM-3, are :shown together with the
Examples of solidi calculated in this fashion, equivalent 0c(O2)-independent) dehydration-
for Ti-saturated biotite of M g # = 0 . 5 ( + melting solidus calculated for Ti-free biotite
quartz), are shown in Fig. 14. The empirical with the same Mg/Fe ratio, plus quartz. The
model for Ti solution in biotite (plus stan- calculated loci of the Ti-saturated solidi are in
dard-state thermodynamic properties from good agreement with ,experimental results of
Berman, 1988 and 1990) were used to calcu- Patifio Douce and Beard (in preparation), who
late H20 fugacities along the three (Ti-satu- observed the onset of biotite dehydration-
rated ) biotite + quartz subsolidus dehydration melting at 10 kbar, in a somewhat more
reactions shown in Fig. 11. Intersections were magnesian (Mg# = 0.57 ), plagioclase-bearing
sought (at fixed oxygen fugacity conditions) and Ti-saturated bulk composition, at approx-
with H20 fugacities at the vapor-saturated so- imately 900°C (see also Skjerlie and John-
lidus given by Vielzeuf and Clemens (1992, ston, 1992).
their Fig. 7). An Mg/Fe ratio of 1 was chosen Calculations suggest (cf. Fig. 14 ) that the ef-
156
fect of Ti saturation on biotite stability is con-
siderable, arresting the beginning of melting of
biotite + quartz assemblages (at 10 kbar) by
70°C (or more, depending on redox condi-
tions) relative to otherwise equivalent Ti-free
bulk compositions. The solidus for Ti-bearing
bulk compositions in which the Ti content is
not sufficient to saturate biotite will be located
between the Ti-free and Ti-saturated solidi. In
such case biotite will react-out over a more or
less wide temperature range, becoming pro-
gressively enriched in Ti until ilmenite satura-
tion is attained at the locus of the Ti-saturated
solidus. It is clear that the abundance of Ti in
metamorphic rocks is likely to have a major ef-
fect on the readiness with which they can gen-
erate granitoid melts by dehydration-melting of
biotite+ quartz. The magnitude of this effect
may be even stronger than that of Fe-Mg solid
solution in biotite, as can be seen by the fact
that the solidus for Ti-free phlogopite + quartz
(shown in Fig. 14 after Vielzeuf and Clemens,
1992 ) occurs for the most part at temperatures
lower than those of the Ti-saturated solidi cal-
culated here for biotite of intermediate Mg#.
The prevailing oxygen fugacity at the site of
melting can also be expected to have some ef-
fect on the solidus temperature. The assem-
blage Ti-biotite + quartz becomes more refrac-
tory as conditions become more reducing, but
the effect is not strong, on the order of 20°C
for a change in f(O2) of three orders of mag-
nitude, from QFM to QFM-3 (cf. Fig. 14). A
stronger effect is predicted for more Fe-rich
bulk compositions and for changes in f(O2)
towards more oxidizing conditions, but nei-
ther of these instances is likely to be very sig-
nificant within the context of large-scale crus-
tal processes. It is important to note at this
point that the effect of excess A1 appears to act
in a direction opposite to that of Ti, lowering
the vapor-absent solidus temperature of bio-
tite + quartz assemblages. This conclusion can
be derived from the experimental results of
Vielzeufand Holloway ( 1988 ), Le Breton and
Thompson (1988) and Patifio Douce and
A.E. PATI/~IODOUCE
Johnston (1991 ), all of whom observed that
biotite dehydration-melting in aluminosili-
cate-bearing assemblages (which also con-
tained Ti-saturating phases) starts well below
850°C at 10 kbar. The effect of excess A1 mer-
its further study, but a detailed discussion of it
is beyond the scope of this paper.
3.3. Effect of Ti on subsolidus dehydration of
biotite
Devolatilization of biotite at temperatures
which are too low to stabilize silicate melts can
take place (even at relatively high pressure) if
the fugacity of H20 is reduced by addition of
"inert" fluid components such as CO2 (e.g.
Newton et al., 1980). Because Ti solution in
biotite has the effect of rendering this phase
more refractory, it could be expected that Ti-
saturated biotite will be more resistant to sub-
solidus dehydration than Ti-free biotite. The
actual stabilizing effect of Ti at subsolidus con-
ditions is quite small, however, as revealed by
Figs. 15 and 16. These figures show the calcu-
lated loci, on the f ( O 2 ) - f ( H 2 0 ) plane, of the
subsolidus devolatilization reactions of Ti-sat-
urated biotite (solid lines, compare Fig. 11 )
and Ti-free biotite (broken lines, compare Fig.
12), assuming in both cases stoichiometric
A1Si3 tetrahedral occupancy in the mica. Also
shown are some of the biotite-absent reactions
which limit the stabilities of different oxide
phases. For the Ti-bearing system, the portion
of the phase diagram above the oxidation of
ilmenite ss. ( + orthopyroxene) to magnetite
ss. (cf. Fig. 11 ) is not shown so as not to clut-
ter the figure, but the ultimate stability of or-
thopyroxene in Ti-saturated compositions is in
every case within a tenth of a logf(O2 ) unit of
the breakdown of orthopyroxene in Ti-free
compositions (shown in Figs. 15 and 16 with
broken lines). All the diagrams were calcu-
lated for orthopyroxene of M g # = 0 . 5 , at 700
and 800°C and 5, 10, and 15 kbar pressure (see
Appendix for details of the calculations).
Comparison with Fig. 14 shows that these P - T
Ti S U B S T I T U T I O N IN BIOTITE: EMPIRICAL M O D E L W I T H APPLICATIONS TO T H E R M O M E T R Y ETC. 157

2_5
5 kbar
2
t~
1-5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ~ .............................. m!+qz
nat + qz I op + 02
op + il + 02 op + sa + il + ~] op + , s a + H20
~ o_5
"1 , I ,
0
311 3.2 33
log f(l'120 ) - b a r s

2.5
10 kbar
2
mt + qz
1-5 ................................... .....7•r . . . . . . . . . . . . . . . . . . . . . . . mT~-~; ......... o~'~;
1 --- op + s a + il + t120 ] op + s a + H20 op + il + 02
- -x.~/ %1_
0-5
bi + q z l + 02 i bi + qz
%', 3'.6 317 3.8
log ( f ( H 2 0 ) - bars

2.5
rnt+ qz 15 kbar
op + 0 2
m t + qz
v 1_5
op + i l + 02 '; il + qz
O op ~- s a + H20 op + ru + 02
1
m op + s a + ru + H20 "%l~X.
0-5
"~'L , b +qz
bij+ qz~
0
4.1 4.2 43
log f(H20 ) - bars

Fig. 15. Subsolidus dehydration equilibria of biotite + quartz in Ti-saturated (solid lines) and Ti-free (broken lines) bulk
compositions, calculated at 700°C (compare Figs. 11 and 12; abbreviations as in these figures). For the Ti-saturated
system reactions above the oxidation of op + il to mt + qz are not shown. Oxygen fugacities plotted relative to Q F M at the
temperature and pressure of interest. H20 fugacities plotted in log units, note that coordinates shift with pressure.

conditions are below the solidus of both Ti-free stabilizing effect of Ti increases notably from
and Ti-saturated assemblages with this Mg/Fe 700 °C to 800 ° C, and at the latter temperature
ratio. it is on the order of a few hundred b a r s f ( H 2 0 )
The magnitude of the effect of Ti on the sub- at 5 kbar, to about 3,000 bars f ( H 2 0 ) at 15
solidus stability of biotite + quartz can be as- kbar. Secondly, the displacement of the devo-
sessed by the displacement of the devolatiliza- latilization reaction for Ti-saturated biotite
tion curves in Ti-saturated bulk compositions relative to that for Ti-free biotite tends to de-
towards lower f ( H 2 0 ) values, relative to the crease slightly with increasing pressure, re-
corresponding curves for Ti-free assemblages. flecting the (small) negative effect of pressure
Some important observations can be made on on Ti solubility in biotite. Finally, the effect of
these diagrams. In the first place, the predicted oxygen fugacity on the breakdown of bio-
enhancement of the subsolidus stability of bio- tite + quartz to orthopyroxene + sanidine + il-
tite by solution of Ti is surprisingly small. The menite is almost negligible within the f(O2)
158 A.E. PATIIqO DOUCE

2.5
5 kbar
2
g.
~--
..-,. 1.s mt + qz
g -Y ..... mt'7:~i ........ , op + O2
op + il + 02 O/¢~L._~ op + sa + nzo '~l'x~"
05 op + sa + il + H 2 ~,
"~/ bi + qz + O2 bi + ~q Z

0;2 33 3'.4 I 3.5

log f(H20 ) - bars

2.5
10 kbar
2
mt + qz
1.5 op + 0 z
I nat + qz
1

0.5
op + sa + il + H e
"'~/bi
o/_ + qz + 02
op + sa +

"~! bi + qz
op + il + Oz

/ I
o3'. 318 3'.9
log (f(H20) - bars

2.5
15 kbar
2 ........................................................................... _mr_+ . ~ t z
1.5 mt + qz I op + 0 z
0 op + il + 02 /~ t il + qz

1 V~.~.. op + sa + H20 I~--% op + ru + 02

05 op + sa + ru + H:O
"~i--bi+qz
"~.~l bi + qz
.i I
0;-
.1 4.2 4.3 4.4
log f(HzO ) - bars

Fig. 16. S a m e as Fig. 15, f o r a t e m p e r a t u r e o f 8 0 0 ° C . N o t e t h a t t h e s t a b i l i z i n g e f f e c t o f T i is c o n s i d e r a b l y s t r o n g e r t h a n a t

7 0 0 C.

range of the diagrams, and becomes even less lution of Ti in biotite increases the molar en-
important for more reducing conditions. tropy of this phase, as noted previously. Be-
The results shown in Figs. 15 and 16 suggest cause the entropy increase of dehydration
that Ti saturation is not likely to affect very reactions is much larger than that of melting
notably the ability of biotite to resist subsoli- reactions, the increase in the entropy of biotite
dus dehydration caused by an isothermal de- will have a stronger effect on the entropy
crease in the chemical potential of H20, even change, and hence on the equilibrium posi-
at upper amphibolite facies conditions. This tion, of melting reactions than on those of de-
suggestion appears to be at odds with the con- hydration reactions. In the second place, the
clusion derived in the previous section regard- solubility of Ti in biotite is a very strong (al-
ing the major stabilizing effect of Ti on the most exponential) function of temperature.
vapor-absent solidus of biotite-I-quartz assem- This can be seen in Fig. 17, which shows the
blages. Both observations can be reconciled, calculated mole fraction of Ti (on 2 M2 sites,
however, upon the basis of two different (but cf. Table 1 ) in biotite coexisting with ortho-
complementary) effects. In the first place, so- pyroxene ( M g # = 0 . 5 ) , ilmenite ss. (or futile
Ti SUBSTITUTION IN BIOTITE: EMPIRICAL MODEL WITH APPLICATIONS TO THERMOMETRY ETC. 159

0,25 acteristic of the granulite facies can enough Ti

M g # = 0.5 be dissolved in biotite to cause important dis-
f ( O ) = QFM
0.2 placements of the terminal equilibria of this
--5 kbar / phase.
-10 kbar / "
0.15 --15 kbar /// The behavior illustrated by Fig. 17 has im-
portant implications bearing on the role of bio-
X
(}.1 /;/
j
tite as an H20 reservoir. Thus, Ti saturation is
not likely to inhibit subsolidus dehydration of
0.05 /, " / , / "
biotite (in response to a decrease in the fugac-
ity of H20) up to conditions in the neighbor-
hood of the amphibolite-to-granulite transi-
6S0 700 750 800 850 900
tion. However, if the P-T-f(HzO) path of a
T ('C)
rock containing Ti-saturating phases is such
that biotite persists to temperatures of about
Fig. 17. Calculated Ti mole fractions in biotite
750 to 800°C, then this phase can become very
( Mg~ = 0.5 ) in equilibrium with ilmenite ss. (rutile at 15
kbar), sanidine, orthopyroxene ss. and quartz at the QFM refractory by a marked increase in its Ti con-
buffer. Note the strongly non-linear increase of Ti solubil- tent. The following orthopyroxene-producing
ity in biotite with temperature. Calculated Ti concentra- net-transfer reaction can serve as a model for
tions are somewhat lower than observed Ti concentra-
this Ti enrichment:
tions (e.g. compare Fig. 4). See footnote below for a
possible explanation. FeTiO3 + 3SIO2 ~ [ TiFe_ 2 ] bio q" 3FeSiO3
Note that this reaction does not liberate H20.
at 15 kbar), sanidine, quartz and vapor at the
Ti-biotite can fix a large amount of H20 well
oxygen fugacity of the QFM buffer *. Ti con-
into the granulite facies, and widespread va-
tent is predicted to rise in a strongly non-linear
por-absent melting may not be possible unless
fashion, in agreement with the observation that
the temperature exceeds 900°C or so.
natural biotites undergo an abrupt enrichment
in Ti in granulite-facies rocks relative to am-
4. Conclusions
phibolite-facies rocks of equivalent bulk com-
position (e.g. Dymek, 1983; Guidotti, 1984;
Although we are still far from having a rig-
Schreurs, 1985 ). Figure 17 also shows the rel-
orous thermodynamic understanding of mi-
atively small magnitude of the inverse effect of
cas, the empirical model for solution of Ti in
pressure on Ti solubility in biotite. The chief
biotite presented here generates new insights
conclusion to be derived from Fig. 17, how-
into the behavior of this phase. In the first
ever, is that up to P-T conditions characteris-
place, it demonstrates what are some of the key
tic of the amphibolite-to-granulite transition,
phase equilibria determining the Ti content of
the solubility of Ti in biotite is too small to have
biotite and how these equilibria may prove very
a major effect on the stability of this phase.
useful in estimating intensive variables within
Only at temperatures well within those char-
the Earth. In particular, it is evident that Ti
*Calculated Ti concentrations are somewhat lower than content in biotite coexisting with an iron-tita-
Ti concentrations observed in biotite present in rocks nium oxide phase is sensitive to oxygen fugac-
which crystallized at the same P-T
conditions. This dis- ity. This makes it possible to estimate reliable
crepancy arises in part from the assumption of stoichio- oxygen fugacity values from biotite-oxide as-
metric AISi3 tetrahedral site occupancy, full interlayer
cation occupancy and full O H - anion occupancy in the
semblages, which are widespread in metamor-
modelled compositions. None of these conditions are phic and plutonic igneous rocks. The break-
common in natural biotite. down reaction of Ti-annite to potassium
160
f e l d s p a r + i l m e n i t e + H 2 0 is also capable of
serving as a sensitive H20 barometer. The fact
that in many rocks no other assemblages sen-
sitive tof(O2) o r f ( H 2 0 ) exist emphasizes the
need to improve upon the empirical model
presented here, by developing an accurate
thermodynamic model for titanian biotite (re-
lying on rigorous phase equilibrium
experiments ).
Some potentially important aspects of the
thermodynamics of biotite, such as the effects
of Fe 3+ and oxy-titanium substitutions, have
not been addressed here because the data used
did not make it possible. It may be safe to ig-
nore such effects as long as treatment is re-
stricted to exchange components, because un-
certainties in the O H - or Fe 3+ contents of
additive components will cancel out, at least
partially (cf. eqs. 8 and 9 ), but even in this case
such simplification could lead to significant
errors, for example if there are strong cross-site
interactions between anions and octahedral
cations. The latter consideration could be im-
portant in the case of oxy-titanium substitu-
tion, because local charge-balance can be ex-
pected to favor T i - O over T i - O H bonds.
Despite all of the uncertainties associated
with the empirical model for Ti solution in
biotite, I argue that this model is capable of
reasonably predicting the behavior of titanian
biotite in the mid to deep continental crust. In
this context, the effect of Ti on biotite phase
equilibria is revealed to be more complex than
previously thought, because the stabilizing ef-
fect of Ti only becomes significant at temper-
atures characteristic of the granulite facies of
metamorphism. As a consequence, biotite-
bearing rocks which also contain Ti-saturating
phases will be quite refractory as sources of
granitoid magmas but will not be particularly
refractory to subsolidus dehydration up to at
least upper amphibolite facies conditions. Far
from contributing to resolve the debate on
whether subsolidus dehydration or dehydra-
tion melting is the primary granulite-forming
process, the predicted behavior of biotite high-
A.E. PATIIqO DOUCE
lights the fact that operation of one or the other
of these processes will be very sensitive to the
specific details of the P-T-f(H20) path of a
rock.
Acknowledgements
The manuscript benefitted considerably
from reviews by Jacques Touret and Jack Rice,
and from discussions with Debra Dooley. Work
supported by NSF grant number EAR-9118418
to A.E. Patifio Douce.
Appendix. Calculation of phase diagrams
The phase diagrams in Figs. 15 and 16, the
solidi in Fig. 14 and the mole fractions of Ti in
biotite in Fig. 17 were all calculated by resolv-
ing each equilibrium of interest into a number
of linearly-independent heterogeneous equi-
librium conditions. For example, the reaction:
biotite + quartz + 02 v--~ orthopyroxene+ il-
m e n i t e + sanidine+ H20 is resolved into the
following four heterogeneous equilibria:
KFe3 A1Si30 lo (OH) 2 4" 3 SiO2
3FeSiO3 + KAISi3 O8 + H2 O
KFe3A1Si3Olo (OH)2 4 302
~3
~ ~Fe203 ÷ KAISi308 ÷ H 2 0
[TiFe_2 ]bin + 3Fe203 zeFeTiO~ + 302
KFe3AISi3OIo(OH)2 + 3MgSiO3
~KMg3AISi3 Cqo (OH)2 + 3FeSiO3
These four heterogeneous equilibrium condi-
tions are solved simultaneously with homoge-
neous equilibrium conditions for orthopyrox-
ene, ilmenite and biotite. Mixing in
orthopyroxene and ilmenite is modelled by
means of parametrizations of the activity-
composition relationships for the respective
binaries given by Sack and Ghiorso (1989,
their Fig. 18a) and Ghiorso (1990, his Fig.
12). Geikielite content of ilmenite was ig-
nored. Biotite was constrained to a ternary
Ti SUBSTITUTION 1N BIOTITE: EMPIRICAL MODEL WITH APPLICATIONS TO THERMOMETRY ETC.
phlogopite-annite-Ti-annite solution in which
Fe-Mg mixing was modelled after Patifio
Douce et al. ( 1993 ). All standard state prop-
erties (and lambda transition properties for the
oxides) are from Berman (1988 and 1990).
Magnetite-bearing equilibria were calculated in
a similar fashion, except that magnetite-ulvos-
pinel mixing behavior was parametrized after
Sack and Ghiorso ( 1991, their Fig. 1 lc).
A program was written to carry out these
calculations, requiring as input parameters:
temperature, pressure, orthopyroxene or bio-
tite Fe/Mg ratio, and oxygen fugacity. The
program returns H20 fugacity and composi-
tions of the phases not specified as input. Phase
diagrams (Figs. 15 and 16 ) and Ti mole frac-
tions (Fig. 17 ) are obtained directly from this
output. In order to calculate the vapor-absent
solidi, isobaric T-f(H20 ) contours are plotted
for the vapor-saturated solidus shown by Viel-
zeuf and Clemens ( 1992, their Fig. 7 ) and for
the biotite devolatilization reaction (at con-
stant orthopyroxene composition and
AlogflO2) ). An isobaric intersection of both
contours generates a P-T point on the solidus.
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