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J. metamorphic Geol.

, 2008, 26, 155179

doi:10.1111/j.1525-1314.2007.00756.x

On thermobarometry
R. POWELL1 AND T. J. B. HOLLAND2
1
School of Earth Sciences, The University of Melbourne, Victoria 3010, Australia (powell@unimelb.edu.au)
2
Department of Earth Sciences, University of Cambridge, Cambridge, UK

ABSTRACT

Thermobarometry, the estimation of the pressuretemperature (PT) conditions of metamorphism, can


be undertaken by using pseudosection calculations as well as by conventional methods. Conventional
thermobarometry uses only the equilibrium thermodynamics of balanced reactions between endmembers of minerals, combined with the observed compositions of minerals. In contrast, pseudosections
involve a forward calculation of mineral equilibria for a given rock composition. When related to
observed rock data such as mineral assemblages, mineral proportions and mineral compositions,
pseudosections have the power to provide valuable additional thermobarometric information. This is
because the rock composition provides added constraints on PT, unavailable in conventional
thermobarometry, such as when minerals in the mineral assemblage are no longer stable, or when
additional minerals join the mineral assemblage. Considering both conventional and pseudosection
thermobarometry, a minimum requirement is that they use the same thermodynamic data and activity
composition models for the minerals involved. A new THERMOCALC facility is introduced that allows
pseudosection datale coding to be used for conventional thermobarometry. Guidelines are given and
pitfalls discussed relating to pseudosection modelling and conventional thermobarometry. We argue
that, commonly, pseudosection modelling provides the most powerful thermobarometric tools.
Key words: ideal analysis; pseudosection; thermobarometry;

INTRODUCTION

Twenty years ago we wrote a paper (Powell & Holland,


1988) that set out a new way of addressing thermobarometry problems, and provided a software tool,
THERMOCALC, for performing them. That paper was
based at least in part on Powell (1985), and the approach was more fully explained in Powell & Holland
(1994). Now, 20 years later, we wish to review the
status of thermobarometry and to make additional
proposals regarding improving the quality and
reporting of thermobarometric results.
Thermobarometry, the determination of the PT
conditions of formation of mineral assemblages, is
underpinned by a view of how metamorphism works.
Accepting that the approach adopted is the application
of equilibrium thermodynamics, a case must be made
that the mineral assemblage to be used in thermobarometry represents a preserved equilibrium from some
(small) part of the PT path that the rock followed
(that part of the PT path being the conditions of
formation of the mineral assemblage). Preservation
must involve not only the mineral assemblage but also
the mineral compositions. Much of the metamorphic
community has implicitly adopted an equilibrium
model of metamorphism, as summarized and discussed
in Powell et al. (2005) (based on Guiraud et al., 2001
and White & Powell, 2002) for specic aspects relating
to the preservation of metamorphic mineral assemblages). Although critical to thermobarometry, dis 2008 Blackwell Publishing Ltd

THERMOCALC.

cussion of the application of the equilibrium model of


metamorphism to rocks, and thus the selection of what
might be interpreted to be a preserved equilibrium
mineral assemblage and mineral compositions, is beyond the scope of this paper.
Experimentally determined phase equilibria lie at the
heart of nearly all thermobarometric methods. However it is not uncommon for such methods to involve
an extrapolation in P, T and/or mineral composition
from the experimental conditions to those that the
mineral assemblage experienced (e.g. see discussion of
garnet-clinopyroxene Fe-Mg exchange below). Equilibrium thermodynamics then provide equations of an
appropriate shape to t the experimental data so that
they can be extrapolated. This applies not only to
mineral end-member data (e.g. Holland & Powell,
1998), but also to activitycomposition (ax) data (e.g.
Holland & Powell, 2003). Both are aided by calorimetric data, and also heuristics that guide the sign and
magnitudes of the parameters required. For example
the value of the entropy of a mineral end-member that
has not been determined calorimetrically is likely to lie
within quite a small range, determined via volumeadjusted additivity constraints (as used in Holland &
Powell, 1998).
Although the quality of the internally consistent
thermodynamic data sets of mineral end-member
properties has improved considerably in the last
20 years (compare Holland & Powell, 1996, and Berman, 1988, with the currently available Holland &
155

156 R. POWELL & T.J.B. HOLLAND

Powell data set, upgrade 5.5, tcds55.txt, from


November 2003, based on Holland & Powell, 1998),
knowledge of the ax relationships for minerals, silicate liquid and uid has been completely transformed,
particularly in terms of our ability to handle multicomponent phases that also involve orderdisorder
(Powell & Holland, 1993; Holland & Powell, 1996;
Powell & Holland, 1999; Holland & Powell, 2003). A
signicant part of this has been driven by improvements in our ability to calculate phase equilibria, not
only in terms of calculation methods but also in the
software available to do the calculations (e.g. THERMOCALC: Powell & Holland, 1988; Powell et al., 1998;
Perplex: Connolly, 1990). These ax developments
have been made largely to allow better and more reliable petrological calculations.
In fact, conventional thermobarometry has not
been the main focus of petrological calculation in
driving recent thermodynamic development. Instead,
it has been calculated PT pseudosections (e.g.
Powell & Holland, 1990, g. 5; Powell et al., 1998).
Clearly, such thermobarometric calculations on mineral assemblages and calculated pseudosections for
rocks both require ax relationships for minerals in
geologically realistic systems. On the one hand, those
who perform thermobarometry with the average
PT (or avPT) method of Powell & Holland (1994)
use ax relationships that are based on those used for
pseudosection calculations, using the software AX
(tjbh url: http://www.esc.cam.ac.uk/astaff/holland/
index.html) to calculate activities from mineral
chemical analyses. On the other hand, many thermobarometers use ax relationships, as well as
implied end-member properties, that are less defensible as they are inconsistent with established
thermodynamic properties. It certainly makes sense
to use precisely the same and best available ax
relationships (and the same end-member properties)
in thermobarometry as are used in pseudosection
calculations. Such consistency would seem to be a
minimum requirement for petrological calculations.
In this contribution, various aspects of thermobarometry are discussed, in the light of the progress
made in the last two decades.
THERMOBAROMETRIC METHODS
Equilibration volume

With the widespread adoption of an equilibrium model


of metamorphism, it has become commonplace to refer
to the equilibrium mineral assemblage, as though this
is something we can somehow prove. However this has
always been a geological interpretation; there is no way
to prove it, although there may be an absence of features that would indicate that equilibrium was not attained. Therefore, it is more appropriate to use a form
of words like the minerals that are interpreted to have
once been in equilibrium with each other. It is in this

context that we refer to equilibration volume, the


scale on which it is plausible to suggest that the minerals in the mineral assemblage being considered for
thermobarometry were in equilibrium with each other.
In assessing an equilibration volume all the normal
caveats apply: different elements have different
mobilities; the cores of growth-zoned grains are excluded, as are replacive minerals that are intepreted to
have grown after the main mineral assemblage, and
so on. Even for a correctly established equilibration
volume, the observed mineral compositions may
not correspond to those originally present if diffusive
re-equilibration has occurred during cooling.
Effectively, all thermobarometry starts with an
interpretation of the equilibration volume. For thermobarometric methods, like avPT, that use just the
mineral compositions, the equilibration volume is used
only in the sense that minerals chosen to be in the
mineral assemblage that is used in the calculations
should be in the same equilibration volume. For
compositionally homogeneous rocks, this need not
even be the case, as compositional homogeneity also
implies homogeneity in mineral assemblage and mineral chemistry.
For thermobarometry involving pseudosections, the
equilibration volume plays a more central role in that it
is the chemical composition of the equilibration volume that is used in the calculations. This composition
may be obtained by XRF analysis, for rocks that are
homogeneous on the appropriate scale, possibly with
calculation to exclude cores of growth-zoned minerals
and adjustment if the pseudosection is in a model
system that excludes elements that are signicant in the
actual rock. Alternatively the composition of the
equilibration volume may be obtained from mineral
composition maps, that also allow straightforward
exclusion of mineral cores (Clarke et al., 2001; Marmo
et al., 2002). In addition, the equilibration volume may
depend on a geological inference, for example, to allow
for the presence of a uid or melt and its volume and
composition.
Pseudosection thermobarometry

Given the composition of an equilibration volume and


the appropriate thermodynamic data, a PT pseudosection can be calculated. For the mineral assemblage
of the equilibration volume, thermobarometric information is contained in: (i) the position in PT space of
the eld that corresponds to that mineral assemblage,
and (ii) the proportions and compositions of the minerals in that eld. This can be seen in Fig. 1, an
example for the mineral assemblage garnet + cordierite + sillimanite + plagioclase + alkali feldspar +
quartz + ilmenite, using an actual aluminous pelite
composition in the system NCKFMASHTO (RH011
from White et al., 2004, Table 1). The mineral proportion contours are shown in Fig. 1a and the mineral
composition contours in Fig. 1b.
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ON THERMOBAROMETRY 157

What can be seen on such pseudosections is that


elds corresponding to particular mineral assemblages
may be small or large. If the relevant eld is small,
thermobarometry is effectively complete, although
establishing that the calculated mineral compositions
more or less match those in the rock is clearly worthwhile. It remains to evaluate the dependence of the
position (and size) of the eld on the assumptions
made in drawing the pseudosection, primarily relating
to how well established the composition of the equilibration volume is.
For large elds and the eld of the ascribed
assemblage in Fig. 1 can be considered to be a moderately large one it is appropriate to constrain the
position of the rock in the eld via mineral proportion
and mineral composition contours (e.g. Vance &
Mahar, 1998). Not surprisingly some contours change
rapidly with PT whereas others change little. The
garnet and cordierite proportions change rapidly with
pressure, whereas the remainder changes slowly. Similarly, and correlated with the corresponding proportions, the xcd and xg contours change rapidly with
pressure, with

Fe 
:
xk
Fe Mgk

Fig. 1. An NCKFMASHTO pseudosection for an aluminous


metapelite composition: H2O 5.65; SiO2 65.47; Al2O3
14.49; CaO 0.49; MgO 2.55; FeO 6.66; K2O 2.8;
Na2O 1.17; TiO2 0.65, and O 0.07 (molar). In (a), contours are for mineral proportions (e.g. g14 is the 0.14 garnet
proportion contour), and, in (b), contours are composition
isopleths (e.g. xcd44 is the xcd 0.44 contour), for the target
mineral assemblage, garnet-cordierite-sillimanite-plagioclaseK-feldspar-ilmenite-quartz-melt. Mineral proportions are molar,
on a one oxide basis, as normally output by THERMOCALC (to be
similar to volume proportions). Abbreviations: mu, muscovite;
bi, biotite; sill, sillimanite; g, garnet; cd, cordierite; sp, hercynitic
spinel; pl, plagioclase; ksp, K-feldspar; q, quartz; and liq, silicate
melt; xg Fe2+ (Fe2+ + Mg)|g and xcd Fe2+ (Fe2+ +
Mg)|cd. The notation, for example -pl, means that pl (plagioclase), although in the in excess list of phases at the top of the
diagram, is not present in this part of the diagram.
 2008 Blackwell Publishing Ltd

In contrast, the remainder change slowly. Thus the


usefulness of the thermobarometric information in the
contours varies considerably. Furthermore, the contour values of compositions that may not have closed
at the conditions of formation are not useful for
thermobarometry, for example feldspar composition
(Fuhrman & Lindsley, 1988; Whitney, 1991).
What constitutes a small or a large eld? The scale
for this depends in a sense on what is considered to be
achievable with more conventional thermobarometry
(including avPT). At least in avPT the answer comes
with the uncertainties on the calculated PT, as well as
rt (i.e. the square root of MSWD as used in geochronology), used to assess whether the data should be
combined. Although potentially realistic uncertainties
are given as part of the thermobarometric calculation,
this is commonly not true of other such methods. In
the latter, PT uncertainties are routinely reported that
are unrealistically small, especially in published garnetbiotite and garnet-pyroxene thermometry. This is
unfortunate as it obscures the possibility of recognizing
the situation where there is, say, effectively no PT
information in a mineral assemblage (as discussed
below).
The authors prejudice is that quoted uncertainties in
conventional thermobarometry of less than 50 C
and 1 kbar should be treated with suspicion ( is
2r, here and below). The difculty is that the uncertainties are hard to establish, and that potentially
the most damaging source of uncertainty is bias
(see below). On this basis the greatest majority of
elds on pseudosections have as much or more

158 R. POWELL & T.J.B. HOLLAND

thermobarometric information in them (not even using


mineral proportions and compositions) than conventional thermobarometers.
Pseudosections do not merely give the conditions of
formation of a mineral assemblage. They commonly
allow sections of PT paths to be deduced from the
way mineral proportions and mineral compositions
are interpreted to have evolved during the textural
evolution of a rock, when compared with phase
relationships in the corresponding pseudosection.
Pseudosections allow the observed assemblage in a
particular rock to be placed in the context of alternative mineral assemblages, in terms of other minerals
becoming stable, as well as minerals being lost from the
assemblage. Moreover the fact that pseudosections are
not dependent on establishing original mineral compositions (as required for conventional thermobarometers) is an important added advantage, particularly in
texturally complex rocks.
Having said this, pseudosections are not without
their limitations. In particular, it is not always
straightforward to determine an appropriate equilibration volume composition to use. In the presence of
growth-zoned minerals, with some elements preferentially sequestered into mineral cores, the difference
between the whole-rock composition and the equilibration volume composition can be signicant,
although an attempt can be made to account for this
(e.g. Marmo et al., 2002; Zuluaga et al., 2005). As
sequestering takes place, the equilibration volume
changes, implying that no one pseudosection can be
expected to reect all of a rocks history. In fact it is
implicit in most uses to which pseudosections have
been put that the diagrams are to be used only for the
prograde history where uid (or melt) is present
(Guiraud et al., 2001; White & Powell, 2002). In
higher-grade rocks in which textural complexity
develops via the production of domains during
decompression/cooling, representing the equilibria in
the domains is difcult, not least because the domains
are commonly not closed systems (White et al., 2008).
In situations where the observed mineral assemblage
in an equilibration volume is not matched by a eld in
the pseudosection, this may indicate that the composition of the equilibration volume has been incorrectly
assigned, but there are other possible causes. An obvious explanation is that the thermodynamic models used
for the minerals are not good enough. Appropriate
models need to exist for all relevant phases in a system
of interest. But a silicate melt model that allows partial
melting of metabasic rocks to be considered has not
been developed yet; there is no model for stilpnomelane;
no clinopyroxene model has been developed that allows
consideration of the whole range of mineral assemblages from those formed at higher temperature, where
the Ca-Tschermak end-member is important, to those
formed at lower temperature where the jadeite substitution is important, and so on. Recently, a model for
amphibole in NCFMASHO (Diener et al., 2007) has

been developed, but this needs to be extended to the Kand Ti-bearing systems so that granulite facies mineral
assemblages can be considered properly. Mn endmembers, apart from those for garnet and ilmenite,
need to be readdressed, as the current models (based on
Mahar et al., 1997) involve ideal mixing for chlorite,
biotite, etc. in the natural assemblage calibration, and
have been superceded. The quality of models also varies, with chlorite and sapphirine in FMAS due for
reassessment in the light of Holland & Powell (2006).
Regardless of the success of the pseudosection approach so far, it is important to realize that the development of thermodynamic models is a work in
progress.
Another cause of a mismatch between mineral
assemblage and pseudosection is if the modelling is
being performed in a smaller system than that controlling the equilibria. Note that there is no general
thermodynamically consistent way of extrapolating the
equilibration volume composition to a smaller system,
although it may be possible in simple cases in practice.
If a rock needs to be represented in NCKFMASHTO,
say, it will generally not be good enough to use a
KFMASH or a NCKFMASH pseudosection (as
illustrated by White et al., 2007). What is close? How
much Zn needs to be in a rock before a pseudosection
that we draw in a Zn-free system (in the absence of
models for Zn-bearing minerals) can no longer be
expected to relate to the observed phase relationships?
The question then is whether the presence of staurolite
or spinel in the rock depends on the Zn? This is difcult to answer. In a situation where we can actually do
the calculations and compare results in full and smaller
systems, the appearance of garnet with changing PT
is certainly strongly dependent on the presence of even
a small amount of Mn (Tinkham et al., 2001).
Recognizing that pseudosections need to account for
all of the real system for thermobarometric use, conventional thermobarometry might then be considered
for calculating PT in rocks where this cannot be done.
However, in practice, the activities of end-members for
which thermodynamic data still need to be calculated,
but in the presence of components of unknown inuence. Continuing the Zn example, and considering a
spinel-bearing assemblage, to use the activities of
MgAl2O4 and FeAl2O4 in thermobarometry requires
that the effect of Zn on these activities be estimated.
Conventional thermobarometry

Here, conventional thermobarometry is considered to


include all those thermobarometric methods that are
based on balanced reactions written between the endmembers of phases in the equilibration volume. For
each such reaction, an equilibrium relationship can be
written, 0 DGo + RT ln K. Generally each equilibrium relationship provides a relationship between
pressure and temperature, the observed mineral compositions having been substituted into the equilibrium
 2008 Blackwell Publishing Ltd

ON THERMOBAROMETRY 159

constant. The equilibrium relationships may additionally be a function of the composition of a phase
interpreted to have once been present, for example
aH2O. In the following, pressure and temperature are
treated as the only unknowns, with the knowledge that
the methods can be generalized to solve for additional
unknowns.
The number of reactions that can be written between
the minerals in an assemblage depends on the endmembers for which there are thermodynamic data (for
calculation of DGo), and the phases for which there are
appropriate activitycomposition (ax) models. We
refer to this combination of end-member data and ax
models as thermodynamic descriptions of phases. For
a set of thermodynamic descriptions involving n endmembers in a chemical system of m components (e.g.
oxides), there are at most nCm+1 reactions, of which
n ) m are independent (in the sense that the remaining
reactions can be written as linear combinations of
those in an independent set). Note that nCm+1
 n ) m.
Given a set of thermodynamic descriptions and the
accompanying uncertainities, as well as the compositions of the phases and their uncertainties, the optimal
thermobarometric result is given by the minimal (in
some statistical sense) adjustment of the data, such that
the PT lines for the equilibria intersect at one PT
the optimal PT. As all the PT information is held in
an independent set of equilibria, only such an independent set needs to be considered (Powell & Holland,
1988, Appendix B). So if the data are adjusted so that
the PT lines for the equilibria in an independent set
intersect at a point, then by denition all the reactions
that can be written also intersect at that point.
There is a set of possible optimal thermobarometric
methods, depending on the approach used to adjust the
data. Average PT (Powell & Holland, 1994) is one of
these: the data are adjusted via a weighted least squares
scheme in which the sum of the squares of the adjustments of the data, normalized to their uncertainties, is
minimized. This is the form of optimal thermobarometry that is implemented in THERMOCALC [Powell & Holland, 1988; now at version 3.3 (tc330); see also Gordon,
1992]. Alternative schemes can be envisaged, involving
for example minimizing the maximum adjustment of
any of the data, weighted to their uncertainties. A more
promising development is one that involves a robust
statistical approach in which outlying data are recognized and down-weighted, allowing an optimal thermobarometric result to be calculated that is not
degraded by the presence of outliers (e.g. Powell et al.,
2002, and the references to the statistics literature
therein, particularly Hampel et al., 1986).
From a practical point of view, regardless of which
optimal method is followed, assigning uncertainties can
be a problem. For mineral compositions, analytical
uncertainties should sufce, although compositional
variability may make an additional contribution. For
end-member properties, if the Holland and Powell
 2008 Blackwell Publishing Ltd

internally consistent data set is adopted, then the


uncertainties derived from the generation of the data
set are available for use (as in the THERMOCALC implementation of avPT and other calculations). However
the uncertainties associated with ax relationships are
less easy to assess (as discussed further below). The
extant avPT implementation uses a generalized way of
introducing an uncertainty on the activity of an endmember in a mineral, taking account of the number of
sites across which mixing takes place and the size of the
activity (Powell & Holland, 1988, Appendix C). The
additional facility in the THERMOCALC implementation
of avPT for assigning uncertainties to activities introduced below gives more exibility and is an improvement on the original approach.
Other conventional thermobarometric methods are
not optimal. TWEEQU-type methods, based on
looking at all the equilibria that can be written between
the end-members of the phases in the mineral assemblage (Berman, 1991; Lieberman & Petrakakis, 1991),
do not use any uncertainties or correlations between
the equilibria. The PT result is gained by eye from the
plot of the equilibria, with no information on whether
equilibria are well constrained or quite uncertain. Yet
it is obvious that there is a huge range in these
uncertainties. Furthermore, the non-statistical nature
of the approach means that no uncertainty on the PT
result is accessible. The problems with such methods
are discussed in detail in Powell & Holland (1994).
An even less optimal method is the use of two, commonly directly calibrated equilibria to estimate PT.
The data on which such direct experimental calibrations
are based have been used in the generation of internally
consistent thermodynamic data sets, so their equilibria
are subsumed in methods like avPT. Nothing is gained
by the direct calibration approach, and information
from the other independent equilibria is lost. Moreover,
using a direct approach means that the data are not put
through a thermodynamic lter (in terms of functional
form, as well as in relation to other related experimental
data), thus potentially further decreasing the reliability
of the results produced. Combining relatively uncertain
equilibria with well-constrained ones degrades results,
but in a statistical approach (like avPT) this cannot
happen. As the directly calibrated approach is not
commonly undertaken in a statistical context, it can be
that the equilibria chosen do not have as much PT
information in them as others in an independent set (e.g.
if one is Fe-Mg exchange between garnet and biotite, or
garnet and clinopyroxene), or certainly in the independent set as a whole.
INFORMATION AND TOOLS FOR
THERMOBAROMETRY
Thermodynamic and other data

The end-member properties of minerals that are used


in most mineral equilibria calculations are from inter-

160 R. POWELL & T.J.B. HOLLAND

nally consistent thermodynamic data sets (e.g. Holland


& Powell, 1998, and upgrades), as used by THERMOCALC
and also commonly by other software. The Holland &
Powell data set is derived from a combination of
calorimetric data and experimental data, with the key
step (giving the internal consistency) being a weighted
least squares analysis of the data to determine the
enthalpies in the data set, given the entropies, volumes,
heat capacities, etc. As new calorimetric data and
experimental data are published, they are incorporated
into the data set, with upgrades released every few
years (the current release is 5.5 of November 2003).
New releases also often coincide with improvements in
methodology relating to the formulation of the thermodynamic properties as a function of PT.
Although ideally the ax relationships to be used
would be independent of end-member properties, for
many end-members this is not possible. For example
experimental data that allow properties of Tschermak
end-members to be determined necessarily involve
solid solutions. In such cases, ax relationships have
to be in place for the end-member properties to be
determined, or the data analysis must generate both.
Inevitably the interaction energies in the ax relationships will be correlated with the enthalpies of the
end-members involved.
What are being calibrated in such an approach are
the thermodynamic descriptions of the phases, not
thermobarometers. This is appropriate because the
form of the PT dependence and to a lesser extent the
composition dependence of the thermodynamic
descriptions are rather well established. Thus thermodynamics can be used to lter the data, and the process
of generating the data set of end-member properties,
commonly with the implication of consistency with ax
relationships, provides internal consistency. Among
other things it means that the results of experimental
studies, that for whatever reason are not consistent
with the remainder of the calorimetric and experimental data, can be identied. On removal, they are
not then able to degrade the overall data set. Thus
thermobarometers are best made via internally consistent data sets, and not calibrated directly.
This overall approach, as well as covering the
interpolation of the data involved, also should allow
extrapolation from the PT conditions and compositions of the experiments to those where the data will be
applied. Even if direct calibration of thermobarometers is attempted, it is unwise not to use internally
consistent data set information. The fact that the g-cpx
Fe-Mg exchange thermometer of Krogh Ravna (2000)
involves a DV and a DS (obtained by regression of the
experimental data) that are rather different from the
data set values suggests that the PT dependence of the
equilibria has not been properly distributed between
DV, DS and the implied interaction energies in the ax
relationships, and this makes extrapolation to conditions outside the PT range of the experiments suspect.
In this case another problem arises relating to the fact

that solid solutions in the experiments involve one way


of substituting Al in cpx (Ca-Tschermak molecule),
whereas in many rocks it is substituted via the jadeite
end-member (and with the cpx having a different
structure at lower temperature, in omphacite).
It is important to realize that the overall approach is
a powerful one but that we are not yet able to do
everything we would like to do. As usual more experimental data are needed. Even at the methodological
level, problems are still being recognized. Recently, a
key simplifying (and regularizing) assumption made by
all authors has been shown not to behave as intended.
This assumption, involving site Fe/Mg ratios taken to
be the same as the Fe/Mg ratio for the whole phase
(the equipartition assumption) has bad and indefensible energetic implications (Holland & Powell, 2006).
We are in the process of revising all these models to
remove the equipartition assumption (already, cpx:
Green et al., 2007; amphibole: Diener et al., 2007).
In addition to thermodynamic data, for conventional thermobarometry (and for pseudosection thermobarometry in comparing calculated mineral
compositions with observed values), a critical step is
the recalculation of mineral analyses. The conventional
way of considering mineral formula uncertainties that
stem from analytical uncertainties is to perform an
error propagation (e.g. Powell, 1978). Whereas this can
be helpful, particularly in showing how uncertainties
can magnify in dealing with, for example, charge balance calculated Fe3+ (Cawthorn & Collerson, 1974;
Droop, 1987), or calculation of xopx
Al;M1 (Carswell, 1991),
an alternative approach can be useful in manipulating
mineral analyses for mineral equilibria applications.
This has been termed the best analysis approach
(Carson & Powell, 1997; St pska & Powell, 2005), but
will be referred to here as the ideal analysis approach.
The idea is that close (in some sense) to the mineral
analysis by the electron microprobe is an analysis that
has some desired properties, for example exact stoichiometry and a specifed amount of ferric iron. The
easiest way to perform such a calculation is for close
to be calculated in a least squares sense, with the ideal
analysis being the one that minimizes the sum of the
squares of the displacements of the analysed wt%,
weighted by their analytical uncertainties (see Appendix 1).
The ideal analysis approach is a tool with uses
across a range of calculations that start with mineral
analyses. For example, in the new form of data input
for avPT with THERMOCALC using pseudosection
datale coding, the approach allows an analysis to be
in a form that corresponds to the datale coding, for
example it can be made to be stoichiometric. The
approach is particularly useful if calculations are to be
undertaken to investigate the consequence of varying
the proportion of iron in an analysis that is considered
to be ferric (Carson & Powell, 1997; St pska & Powell,
2005). In the latter study, considering g-cpx Fe-Mg
exchange thermometry for an eclogite, the cpx analyses
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ON THERMOBAROMETRY 161

were recalculated so that they were stoichiometric at a


range of specied ferric values, to investigate the
dependence of calculated temperature on this ferrous
ferric conversion. Because the calculation is a least
squares one, the rt of the analysis allows an appraisal
of whether the ideal analysis with the specied ferric
content is consistent statistically with the original
analysis given the analytical uncertainties (via a v2
constraint, e.g. Mikhail, 1976). In both papers (Carson
& Powell, 1997; St pska & Powell, 2005), the approach
allows an appreciation of the bias (see next section)
introduced by assuming that no ferric iron is involved
in the mineral analysis (in opx and cpx, respectively).
Uncertainties

An elementary requirement of any calculation is the


assessment of uncertainties on results that arise from
uncertainties on the input information, as has been
emphasized in a mineral equilibria context by Powell
(1978, 1985) and Powell & Holland (1988, 1994). It is
rarely possible to do a thorough job of this, but this
cannot be an excuse not to try. If the uncertainties are
already large, as commonly arises in the estimation of
ferric iron in minerals in the context of Fe-Mg exchange thermometry, then it is evident that nal (but
unknown) uncertainties can only be larger. Because of
the incomplete nature of the propagation, it is important to realize that quoted uncertainties should be
thought of as minima.
There are several aspects of such minimal uncertainties that need to be borne in mind. The rst concerns whether PT results on related rocks are likely to
be different or not (see also Worley & Powell, 2000).
The second concerns the fact that minor changes in
assumptions or data will cause results to move around
within such uncertainties (in a way that can be alarming, but is understandable statistically). The third,
which is a key issue in conventional thermobarometry,
is whether a particular mineral assemblage has any
temperature and/or pressure information in it. This
question should be asked in a context: in an ultrahigh
pressure (UHP) eclogite quite possibly 800 100 C is
a good result, whereas for an amphibolite or granulite
facies metapelite such a temperature range might be
deduced directly from the hand-specimen. In a
pseudosection context, a scale is provided by the size of
the eld corresponding to the mineral assemblage.
Commonly such a size is smaller than the estimated
uncertainty. The possibility of an assemblage being
thermobarometrically non-informative (by conventional thermobarometry) can be thought of in a
pseudosection context: the eld for an assemblage may
be well constrained in PT by the presence/absence of
minerals (i.e. the size of its eld), yet within the eld the
compositions of all the minerals change very little.
Why are uncertainties not all available to be propagated through calculations? Analytical uncertainties
(related to how the electron microprobe is set up),
 2008 Blackwell Publishing Ltd

uncertainties that relate to the regression of experimental data in the generation of an internally consistent data set (e.g. Holland & Powell, 1998), or the
tting of experimental data to get interaction energies
for ax relationships are available for propagation and
should certainly be propagated. But uncertainties
related to structural assumptions cannot be sensibly
propagated. Suppose an assumption in the recalculation of a mineral is wrong, related for example to
stoichiometry. Suppose the measured entropy of a
mineral end-member, assumed to be good within its
uncertainty, is wrong. Suppose the formulation of the
ax relationships is wrong. Such things give rise to
what was called systematic uncertainty in Powell
(1985), but is better referred to as bias.
Accounting for bias is a major challenge. If we are
lucky, such bias will affect the rocks that we are interested in more or less equally, so that differences between
the calculated PT values of rocks are maintained, but
all rocks are displaced to higher or lower T, say.
Something like this might apply if the mineral equilibria
are consistent with experiment at high temperature
(where equilibration occurs in the laboratory in nite
time), but the extrapolation to rock temperatures is
inappropriate: all estimated temperatures are either too
high or too low. But such systematics may well not be as
transparent. More cogently, the problem with bias is
that generally it is unknown. Only when it becomes
apparent is it relevant to consider systematics, in the
context of evaluating previously produced results.
A situation where bias can be illustrated is where the
implementation of a thermobarometer involves regularization. Regularization arises when a simplication
is made that reduces the variability in results, apparently reducing the uncertainty on a result, but in the
process introduces bias. The rst example involves
the Al-in-orthopyroxene (opx) thermobarometer for
the assemblage opx + garnet. The calculated octahedral and tetrahedral Al site occupancies can be regularized by taking each of them to be the total
recalculated Al divided by 2 (in the Na- and Cr-free
case). In the context of the actual charge balance,
AlVI + Fe3+,VI AlIV, the regularization simply
ignores the ferric iron. Although this might be a reasonable approximation in processing the original
experimental data (if they were done at low aO2), it is
unlikely to be the case when considering rocks. The
effect of removing this regularization is considered by
Carson & Powell (1997). The thermobarometric
equation involves the product of the octahedral and
tetrahedral occupancies. Calculating the charge balance properly, the product decreases as ferric iron
increases, so the pressure increases (at constant temperature). The magnitude of the pressure bias of regularization obviously depends on the composition of
the opx, as discussed by Carson & Powell (1997).
The second example involves Fe-Mg exchange
thermometry. As is obvious, and has been spelt out
by various authors, e.g. Proyer et al. (2004), the

162 R. POWELL & T.J.B. HOLLAND

(unknown) ferric iron in a microprobe analysis of a


clinopyroxene (cpx), introduces a considerable uncertainty in the Fe2+ content of the cpx, and thus in the
Kd of the Fe-Mg exchange reaction. Regularizing the
g-cpx Fe-Mg exchange thermometer result by assuming no ferric iron, introduces a strong upward bias on
temperature (e.g. St pska & Powell, 2005). The magnitude of the bias obviously depends on the composition of the cpx, becoming progressively worse for more
magnesian cpx. Even if a charge balance calculation is
undertaken, but it is assumed that the cpx is stoichiometric, an upward bias will be introduced on
temperature if the cpx contains even a small amount of
Ca-Eskola molecule (Ca12 (12 AlSi2O6), the presence of
which causes ferric iron to be progressively underestimated (Proyer et al., 2004).
A more subtle bias is introduced in Fe-Mg exchange
thermometry by using the common assumption that
Fe2+/Mg in the sites of a mineral is equal to the bulk
Fe2+/Mg (the equipartition assumption; see above). In
the g-cpx thermometer case, this problem becomes
more acute as more Fe2+ and Mg are incorporated
into the M2 site. As for most eclogites little Fe2+ and
Mg occurs on M2, the Fe2+/Mg in M1 will be very
close to the bulk value; for more augitic cpx, Fe2+/Mg
in M1 will depart from the bulk value as Fe2+ is
relatively strongly partitioned into M2 in cpx.
Bias may also be introduced via qualitative
assumptions made in thermobarometry, and this sort
of bias may affect pseudosection thermobarometry.
Considering granulite facies rocks, and particularly
UHT rocks, it may be difcult to decide upon the peak
metamorphic mineral assemblage, let alone the equilibration volume composition. So, in a sapphirinequartz-bearing rock, is sapphirine + quartz in the
peak metamorphic mineral assemblage (e.g. Baldwin
et al., 2005)? Similar problems arise relating to
assumption of the process: was a uid (or melt) present
when the mineral assemblage of interest formed?
Further discussion of such problems is given below.
Aside from bias, in both pseudosection and conventional thermobarometry, the results obviously depend on the thermodynamic descriptions of the phases
used. Uncertainties in the internally consistent data
set and in the interaction energies used in the ax
relationships need to be propagated through all calculations. In thermobarometry by pseudosection,
uncertainties that relate to the equilibration volume
composition also need to be considered. Investigating
the dependence of the position of elds in pseudosections, and their mineral proportion and mineral composition contours, involves changing the composition
and recalculating the PT pseudosection. Alternatively
Tx (at constant pressure) or Px (at constant temperature) pseudosections can be drawn in which the x
spans the composition used for the PT pseudosection
representing the composition uncertainty. In both
cases care is needed to make the composition changes
reect the likely uncertainties. The same approach can

be followed in assessing other assumptions, for example relating to aH2O or Fe2O3/(FeO + Fe2O3) (when
not measured). In conventional thermobarometry, the
uncertainties on mineral composition must be considered. Whereas the propagation of analytical uncertainties is well known (e.g. Hodges & McKenna, 1987;
Kohn & Spear, 1991), several additional aspects are
considered in the next section.
Software for thermobarometry:

THERMOCALC

Thermobarometry now inevitably involves using software for the calculations. This has always been the case
in the construction of pseudosections, but it is also true
for the avPT approach, given that it involves combining the PT information for an independent set of
reactions between end-members (as outlined above).
Even considering individual equilibria, it is unfortunate that ax relationships for many minerals are now
sufciently complicated, particularly when order
disorder is involved, that it is impossible to make a
closed-form expression to get pressure in terms of
temperature, say. The software THERMOCALC (free
download: http://www.earthsci.unimelb.edu/tpg/thermocalc) is currently the only general software for
which the ax relationships can be coded for use in all
the types of thermobarometry being discussed here.
In pseudosection modelling with THERMOCALC, the
uncertainties in the internally consistent data set, and
in interaction energies used in the ax relationships,
can be propagated through all calculations. The
uncertainties stemming from these sources can be calculated for apices of elds in the pseudosection, the
positions of the boundaries, as well as the positions of
the various contours. But what cannot be done is to
determine the correlations between the implied displacements of different eld apices, boundaries or
contours. Hence, the pseudosection would need to be
recalculated with the relevant data manually displaced
by their uncertainties. In avPT thermobarometry and
in calculations on individual end-member reactions,
THERMOCALC propagates the uncertainties in the internally consistent data set, the interaction energies, and
the input mineral compositions, through the calculations, giving the corresponding uncertainties on the
PT result. A critical number in the results is the rt,
a measure of whether the data being combined in the
calculation are likely to be consistent with each other
(see below and Powell & Holland, 1994). Diagnostics
are also calculated that help in assessing the data in
the event that the data are not consistent (Powell &
Holland, 1994).
Calculating avPT with THERMOCALC using ax datale coding follows a recent development that allows
observed mineral compositions to be inserted where
starting guesses are required in the datale for
pseudosection calculations, to prime the nonlinear
equation solver. In addition to promoting consistency
between the different types of thermobarometry, it
 2008 Blackwell Publishing Ltd

ON THERMOBAROMETRY 163

means that THERMOCALC generates the equilibrium state


of order in minerals to be used in calculations, at the
PT corresponding to the estimated conditions of
formation suggested initially by the user. When
uncertainties on the mineral compositions are included, the minerals maintain stoichiometry. For
avPT, given datale coding for minerals, and the
mineral analyses, it remains to:
1 Recalculate the mineral analysis to put it into a
form that corresponds to the chemical system and
composition variables used in the coding of the ax
relationships. Arguably the best way of doing this
is via the ideal analysis approach introduced above.
2 Assign uncertainties to the composition variables,
arising from analytical uncertainties, and depending on how the composition variables have been
calculated. Uncertainties are available for the
thermodynamic properties of the end-members that
arise from the generation of the data set used.
Propagation of analytical uncertainties through an
ideal analysis calculation (Appendix 1) is straightforward. In the past, when the activities of the endmembers were entered into THERMOCALC directly for
avPT calculations, default uncertainties on these
activities were provided by THERMOCALC. These were
formulated to cover not only composition uncertainties but also interaction energy uncertainties (Powell &
Holland, 1988, Appendix D), with the latter involving
an uncertainty of about 2 kJ mol)1 (on a one-site
basis). Now, with datale coding of ax relationships,
the uncertainties on the compositional parameters are
entered separately. The default uncertainty on interaction energies used is 2 kJ mol)1 (on a one-site basis),
a default being necessary, as generally they are not well
constrained. This default can be easily overridden, as it
must be when the uncertainties are actually known
(e.g. for cpx in Green et al., 2007). The old default
activity uncertainties can still be specied, and are still
used if old style activity input (from AX) is used. The
new uncertainty structure is available with THERMOCALC 3.26 (tc326) and more advanced versions.
Of the statistical information and diagnostics given by
THERMOCALC (Powell & Holland, 1994), rt is central in
that it allows an assessment of whether the data being
combined should indeed be combined. For example, for
avP involving a set of 10 independent reactions, rt
should be less than 1.35 for the data to belong together at
the 95% signicance level. [The value comes from
q
v2r1;0:05 =r  1;
where r is the number of independent reactions.] Considering the analogy of a set of 10 points dening a
linear trend (no outliers), for rt to be of the order of
1.35 implies that the average of the departure of the
points from the line, each divided by its r, would be
about 1. From this it is clear that if the r on the data is
changed, then rt is changed. In fact, if all the r on the
data is increased by the same proportion, the rt is
 2008 Blackwell Publishing Ltd

decreased by the same proportion. In a situation


where the data involve uncertainties that are not well
known, in this case particularly the interaction energies,
it is usual to multiply the uncertainty on calculated PT
by rt if it fails the v2 test, as done by THERMOCALC (and
as done in geochronology in so-called York model 2:
York, 1969). This results in a more realistic assignment
of uncertainty, but implicitly makes everything more
uncertain (by the factor rt). This then hides the possibility that just one or two data items are more
uncertain than originally specied, rather than all of
them being more uncertain. Considering the diagnostics given by THERMOCALC that are used to indicate the
possibility of outlying data, data may be outlying only
because a particular input has been assigned an
uncertainty that is unrealistically small.
As the uncertainties on the interaction energies are
increased, rt decreases, until the usual v2 test is passed. But these large uncertainties are propagated to
uncertainties on PT, so at least this is not a way to
make results look better than they are. If uncertainties
on interaction energies are decreased, rt increases,
with propagated uncertainties on PT decreasing, at
least until the v2 test fails. Realistic assignment of
uncertainties on interaction energies is therefore relevant. The tuning constants in the original default
uncertainty on activities (Powell & Holland, 1988, p.
198) were chosen based on our experience of analytical
and calorimetric uncertainties. With these, avPT for
rocks that were considered to be good candidates for
giving good results (i.e. for which the v2 test would be
expected to pass) actually do pass the v2 test, with rt
around 1. Therefore the default uncertainty on interaction energies is maintained at 2 kJ mol)1 (on a onesite basis).
Regarding the PT results and their uncertainties
derived by THERMOCALC, it is relevant to note that the
results may vary of the order of the rP and rT on
varying input assumptions, for example relating to the
phases included or the input uncertainties, at the same
rt). If THERMOCALC gives 10 2 kbar ( is 2rP), it is
to be expected that a calculated pressure may be anywhere within 911 kbar, say, with minor change of
inputs.
An illustration: conventional thermobarometry in eclogites
using THERMOCALC

Eclogites present particular challenges for thermobarometry. When they contain hydrous minerals in
addition to phengite, for example amphibole(s), a
pseudosection approach has the capacity to be the most
effective (e.g. Carson et al., 1999; Wei et al., 2003). But
when they are not involved, because temperatures are
higher, or because aH2O is lower, the garnet-omphacitephengite kyanite quartz/coesite mineral assemblage is stable over a huge range of temperature and
pressure. Given that such rocks occur most commonly
in subduction settings, estimating the PT of formation

164 R. POWELL & T.J.B. HOLLAND

of such mineral assemblages has important geodynamic


implications (e.g. Hacker, 2006).
Using conventional thermobarometry to consider
the mineral assemblage, garnet-omphacite-phengitekyanite-quartz/coesite, it is now widely recognized that
equilibria that involve Fe end-members of minerals, in
particular in garnet-omphacite Fe2+-Mg exchange
thermometry, will be unreliable unless Fe3+ can be
measured in the minerals (Galazka-Friedman et al.,
1998; Sobolev et al., 1999; Schmid et al., 2003; Li
et al., 2005). Thus Krogh Ravna & Terry (2004)
advocated using the intersection of reactions among
the mineral end-members: grossular, pyrope, diopside,
muscovite, celadonite, kyanite and quartz (or coesite).
Here we look at these equilibria, and others involving
end-members of these phases, using THERMOCALC and
the ax datale codings in Appendix 2, with the aim of
undertaking thermobarometry in this mineral assemblage.
The example chosen to illustrate the ideas involved
is sample SM93, a Dabie Shan eclogite studied by
Proyer et al. (2004). Critically, they used Mossbauer
to determine ferric iron in their omphacite (and
garnet). The mineral asemblage involves garnet-omphacite-phengite-kyanite-coesite, and additionally
talc, and in their avPT calculations it was assumed
that the mineral assemblage was water-saturated.
They showed that the calculations are much more
consistent once the relatively large conversion of FeO
to Fe2O3 is made (0.54 0.1) (also see Appendix 1
below). As an aside, a subtly different conclusion can
be drawn in favour of the avPT approach: the effect
of using all Fe-as-FeO in the omphacite degrades the
statistics (compare rt 1.38, Table 3, with 0.48,
Table 6) but in fact does not signicantly change the
result (compare 589 C and 29.9 kbar with 585 C
and 30.8 kbar; PT results are quoted here and below to 0.1 kbar and 1 C, for comparative purposes;
for reporting thermobarometric results commonly
quoting to 0.5 kbar and 5 or 10 C is usually
appropriate). This is because the default activity
uncertainty used by THERMOCALC in their calculations
(Proyer et al.) sufciently downweighted the inherently more sensitive Fe2+ end-member-bearing equilibria (particularly the garnet-omphacite Fe-Mg
exchange reaction) such that their initial results were
effectively unaffected by using the wrong clinopyroxene composition.
In the following, the presence of talc in the assemblage (and the inferred original presence of a H2O
uid) will be ignored so that focus can be on the
mineral assemblage of interest: garnet-omphacitephengite-kyanite-coesite. The calculations are made
with THERMOCALC 3.26 (Powell et al., 1998; most recent
upgrade), using the thermodynamic data set 5.5
(Powell et al., 1998; most recent upgrade), and the ax
coding in the datale in Appendix 2. The composition
variables for the minerals are given in the datale in
the Appendix. First, some equilibria for this assem-

blage are considered, including the Krogh Ravna &


Terry (2004) ones, with particular reference to the
uncertainties that are involved, in the light of the new
facilities available in THERMOCALC. The following are
the results for this rock using the Mossbauer-determined ferrousferric compositions for omphacite and
garnet:
T (C)/P (kbar)

24

26

28

30

32

34

36

py + gr + 2coe 3di + 2ky


3cel + 4ky py + 3mu + 4coe
gr + 3cel + 2ky 3di + 3mu + 2coe
alm + gr + 2coe 3hed + 2ky
3fcel + 4ky alm + 3mu + 4coe
gr + 3fcel + 2ky 3hed + 3mu + 2coe
3hed + py 3di + alm
py + 3fcel alm + 3cel
di +vfcel hed + cel

779
558
448
461
)
404
617
614
601

730
589
517
525
459
501
627
618
575

685
620
586
588
611
596
636
622
549

642
649
653
651
759
688
646
625
524

601
678
719
715
899
778
656
629
500

562
706
784
778
+
864
666
633
476

525
732
848
842
+
948
676
637
452

and, for the intersection involving the rst three reactions (as used by Krogh Ravna & Terry, 2004),
29.8 kbar and 646 C. The second set of three reactions are for the equivalent Fe2+ equilibria, with an
intersection at 27.5 kbar and 571 C. The third set is
for the corresponding Fe-Mg exchange reactions.
If the calculation is performed with all Fe-as-FeO in
the omphacite (and garnet), the rst intersection moves
little, to 31.2 kbar and 666 C, well within the uncertainties on the above result (see next). This supports
the assumption made by Krogh Ravna & Terry (2004)
and Hacker (2006) that just using the Fe-free equilibria
minimizes the problems stemming from ferric iron not
being known for microprobe analyses of minerals.
Looking at the Fe-Mg garnet-omphacite exchange
reaction, the temperature at 30 kbar moves from 646
to 952 C, if it is assumed that the omphacite is ferricfree (as would be deduced from a simple charge-balance calculation, Appendix 1). The second intersection
moves to very high temperatures and pressures if no
ferric iron is used.
The uncertainties involved in the equilibria stem
from the mineral analyses and from thermodynamics.
However if several eclogites are considered, and their
relative positions in PT are the main issue, then
uncertainties on the mineral analyses (random
uncertainties) can be considered alone, giving rise to
relative uncertainties on results (see also Worley &
Powell, 2000). However if one eclogite needs to be
placed in PT, then all uncertainties need to be combined, giving absolute uncertainties on PT (that in
general are much larger).
To start to evaluate the random uncertainty contributions to the uncertainties on PT, the likely main
contributor is omphacite. Using only the Monte Carloderived uncertainties on the datale coding variables
x Fe2+/(Fe2+ + Mg), j Na/(Na + Ca) and f
Fe3+/(Fe3+ + Al) (Fig. 3 in Appendix 1) gives
29.8 3.2 kbar and 646 52 C (with a strong positive correlation between them), stemming just from
the resulting uncertainty on the activity of the diopside
 2008 Blackwell Publishing Ltd

ON THERMOBAROMETRY 165

end-member, the only omphacite end-member involved. Including additional uncertainties from the
compositions of garnet and muscovite increase these
uncertainties by <10%.
Such relative uncertainties on PT are of a sufciently small magnitude to be useful. What are the
absolute uncertainties? Just considering the data
set-derived uncertainties alone contributes 29.8
0.7 kbar and 646 11 C. But considering additionally the likely uncertainties on the interaction energies
(Coggon & Holland, 2002; Green et al., 2007), as well
as the composition uncertainties, gives 29.8
9.2 kbar and 646 164 C. At face value, this means
that we have no real idea of the PT for such eclogites
(continuing to ignore the presence of talc in this particular eclogite), except that the positive correlation
between pressure and temperature (around 0.75), and
the fact that the rock contains coesite (not quartz),
means that the lower PT end of the implied PT
range is not supported.
Why are the uncertainties so large? The main
reason is that we are dealing with solidsolid equilibria and that they tend to be relatively uncertain,
coupled with the large and uncertain ferric content
of omphacite (even with the Mossbauer data). If the
uncertainties are large for these equilibria, they are
huge for the omphacite-garnet Fe-Mg exchange.
Even just considering the random uncertainty associated with the omphacite analysis, the temperature
at 30 kbar is 646 198 C (suggesting that the
similarity of this temperature to the Krogh Ravna &
Terry temperature is quite fortuitous).
Given that the omphacite-garnet Fe-Mg exchange
is not a useful thermometer, it is unlikely to be useful
to invest further effort in rening a calibration. Just
using the current Holland & Powell data set and
current ax models gives similar results to recent
published thermometers. For example, using the
Krogh Ravna (2000) calibration, with a Monte Carlo
estimate of Fe2+/Mg 0.128 0.074 (using the
same approach as in Appendix 1), gives 610 65 C,
before a calibration uncertainty is included. In using
tted entropy and volume of the exchange reaction
that are larger than better established data set values,
the calibration is, to an extent, not only regularized
(by making uncertainties smaller), but it also makes it
likely that the extrapolation in PT from the conditions of the experimental data to those of rocks will
not be correct. But in fact a much bigger problem is
that the core clinopyroxene system in the high PT
experiments is diopside-hedenbergite-cats-enstatite,
whereas the core for applications is diopside-hedenbergite-jadeite-acmite. Thus much of the activity
coefcient information needed to t the experiments
becomes irrelevant, and separately established information (regarding jadeite and acmite) needs to be
included for applications. Using the Holland &
Powell internally consistent data set with the ax
coding in Appendix 2 does just this.
 2008 Blackwell Publishing Ltd

We nish this section by giving the results of a forward pseudosection-type calculation with the coding in
Appendix 2 for the Sun & McDonough (1989) average
MORB composition, including their ferric content. At
30 kbar and 650 C, this gives, for the mineral
assemblage of interest (see Appendix 2 for the meaning
of the composition variables):
x(o)
0.08732
x(g)
0.5391
v(mu)
0.06560
mode

j(o)
0.4055
z(g)
0.2754
na(mu)
0.01798
o
0.4787

f(o)
0.1661
f(g)
0.01004
x(mu)
0.1205
g
0.3936

Q(o)
0.2300

Qaf(o)
0.02139

Qfm(o)
)0.01675

s(mu)
0.8759
mu
0.03226

f(mu)
0.01039
ky
0.01937

coe
0.07604

This involves an apparently relatively oxidized


omphacite, with Fe3+ f j 0.067 and Fe2+
x(1 ) j) 0.052, similar to that in the Proyer sample
discussed earlier, yet the corresponding lO2
)445.0 kJ. This is just one log unit above the quartzfayalite-magnetite buffer (QFM) at these conditions.
DISCUSSION
Strategies for thermobarometry

Although calculated mineral equilibria have come a


long way in the past two decades, there is no magic
bullet for thermobarometry. However, regardless of
the limitations described above, the pseudosection
approach, when carefully applied, is commonly an
easy-to-use and powerful way of gaining thermobarometric information on rocks. Our prejudice is that, in
most circumstances, much more can be revealed by this
approach than by conventional thermobarometry, not
only giving the peak metamorphic conditions, but also
PT path information, as well as allowing investigation of metamorphic processes (like partial melting and
melt loss).
The essential precursor to pseudosection modelling
is detailed petrography, and the selection of rocks to
model. These rocks need to be the ones that are likely
to reveal the information of interest, while being representable in a model system as close to the real
chemical system as allowed by the available thermodynamic models for the minerals involved. Commonly
this model system is, NCKFMASHTO, though in
certain circumstances Mn can be added to this (noting
the stricture given above about the quality of data for
Mn-bearing end-members). The O in NCKFMASHTO represents Fe2O3. In much pseudosection modelling omission of ferric iron has been a common, but
unjustied, simplication. Omitting Fe2O3 (and TiO2)
not only means that the Fe-Ti oxides cannot be considered, but also that FeO/(FeO + MgO) is wrongly
assigned if all analysed Fe is taken to be FeO. Using an
inappropriate system for modelling amounts to introducing bias into the estimation of conditions. Given

166 R. POWELL & T.J.B. HOLLAND

the current state of knowledge of thermodynamic


models of phases, there are certainly rocks that cannot
be modelled reliably.
Pseudosection modelling has to be undertaken in
the context of the processes envisaged to have been
involved in the formation of the rocks. The more
complex the metamorphic history, the more the
pseudosections that are likely to be needed to understand each rock. Separate pseudosections might be
needed to understand different parts of the prograde
and retrograde history as the equilibration volume
composition changes; separate pseudosections to consider assumptions relating to loss/gain of uid/melt,
with Px and Tx pseudosections being particularly
relevant, and so on. Modelling is not restricted to PT,
Px and Tx pseudosections. Variables to use as axes
on pseudosections come in conjugate pairs of intensive
and extensive variables (e.g. P or V, T or S, and lk or
xk, for each component, k), Powell et al. (2005).
Depending on the processes envisaged to be involved
in the formation of a mineral assemblage, it may well
be that P, T and x are not the most informative choice
of axes for a pseudosection. Even when knowledge of
PTx is sufcient to understand rocks, bearing in
mind that rocks do not form at a point on a PT path,
but are a more or less encoded record of a larger or
smaller section of the path, pseudosections can be used
to try and understand the preservation of the observed
mineral assemblage and the compositions and zoning
of the minerals.
In terms of interpreting the results of pseudosection
modelling, assessment of uncertainties is important,
and insufcient attention has been paid to this up to
now. As noted earlier, pseudosection calculations can
be devised to help, for example Tx and Px pseudosections spanning the estimated equilibration volume
composition. Such diagrams are particularly important
if in fact the observed mineral assemblage is not found
on the pseudosection, allowing an assessment of whether it is a misassignment of composition (but within
likely uncertainty) that is responsible. A subtle consequence of slightly inappropriate equilibration volume
composition (or thermodynamic models) can be that a
mineral that would be present only in a minor amount
is either present when it should not be, or absent when
it should be. Such a problem is common with hydrous
eclogites in which garnet, omphacite and quartz make
up a substantial proportion of the rock, the remainder
of the composition varying widely for small changes in
the equilibration volume composition. As a consequence these small changes can result in marked
changes in the remaining phases that nevertheless are
present in small proportions.
Is there a role for conventional thermobarometry?
Yes, in certain circumstances, if carefully applied. It is
interesting to look at the literature for the last decade
and see that in the majority of studies that have
adopted pseudosection modelling, conventional thermobarometry is not used (but see St pska & Powell,

2005, for an exception). It is tempting to suggest that


once metamorphic geologists adopt the pseudosection
approach, conventional thermobarometry is seen as
less useful. In fact we are not aware of any study where
the two approaches have been used in competition with
each other (but see Coggon & Holland, 2002, for calculations on the Parigi garnet quartzite). It would be
interesting to know if there were examples where the
pseudosection approach produced less useful results
than conventional thermobarometry. Such a case
would need to be made using a realistic assignment of
uncertainties (as above, in this paper), as well as by
using the same thermodynamic models for the minerals. It does not seem appropriate now, in 2008 to
use just conventional thermobarometry in the absence
of reasons not to use the pseudosection approach.
A potentially important use for conventional thermobarometry is when the pseudosection approach is
ineffective. It might be useful for rocks in which there
are signicant additional phases and/or elements such
that pseudosections cannot be calculated, but such
rocks are commonly accompanied by rocks that are
amenable to pseudosection modelling. A situation
where avPT might be valuable is where the rocks involve sufcient unconstrained factors, for example
relating to presence/absence of uid and to unknown
activities of H2O and CO2, in which a pseudosection
approach would be difcult to apply usefully. In fact
Powell & Holland (1994) have an example where avPT
has been used, omitting the end-members H2O and
CO2 in the generation of the independent set of reactions for a carbonate-bearing rock (RP13), so that the
results are independent of uid and its end-members.
But corresponding pseudosections have not been
calculated for this example.
Conventional thermobarometry may also have a
role to play where the eld of interest on a pseudosection is large and the mineral proportions and
compositions are slowly varying in PT, for example in
essentially anhydrous eclogites (e.g. Krogh Ravna &
Terry, 2004; Hacker, 2006). However this is precisely
the situation where conventional thermobarometry
fails, given that the spacing of isopleth (and mineral
proportion) contours is intimately related to the PT
dependence in thermobarometers. Faced with such a
situation, St pska & Powell (2005) used g-cpx Fe-Mg
exchange thermometry to get a temperature of 760 C
at 18 kbar with an uncertainty of the order of 100C,
for a quarter-space pseudosection eld that opens to
higher pressure and temperature from 17 kbar and
700 C. In this circumstance, against suggestions of
much higher temperature, this is a useful result for this
Bohemian Massif eclogite. With a better thermodynamic model for clinopyroxene (see above), PT could
most likely be better constrained by contours of calcium Tschermak molecule, calcium Eskola molecule,
etc., rather than us having to resort to exchange
thermometry. In the context of such conventional
thermobarometry
complementing
pseudosection
 2008 Blackwell Publishing Ltd

ON THERMOBAROMETRY 167

thermobarometry it is appropriate to consider the approaches being integrated, and the possibility of doing
that is discussed below (as hybrid methods).
Another circumstance in which conventional thermobarometry has the capacity to complement
pseudosection modelling is via chemical systems which
are effectively orthogonal to the systems that have
been used for pseudosection modelling. The recent
experimental calibration of various trace element
thermometers provides methods that, for example,
involve the solubility of Ti in zircon (in equilibrium
with rutile and quartz), Zr in rutile (in equilibrium with
zircon and quartz), and Ti in quartz (in equilibrium
with rutile) (Wark & Watson, 2006; Watson et al.,
2006; Tomkins et al., 2007). These methods need not
be standalone: there is no reason why the equilibria
involved cannot be incorporated into pseudosection
modelling.
Considering standalone conventional thermobarometry, it is crucial that uncertainties are handled
realistically. This is because they constrain the estimated PT, whereas commonly in pseudosection
thermobarometry it is the existence of the elds of
alternative mineral assemblages that constrains PT.
As shown in the illustration above the situation is
particularly serious with Fe-Mg exchange thermometry. In our experience, in the absence of constraints
from H2O-bearing reactions, temperature is not well
constrained by thermobarometry, such that avP using
geological prejudice for temperature is more useful (as
suggested in Powell & Holland, 1994). With the
exception of uncertainties arising from estimating
ferric iron, uncertainties on ax relationships are
commonly the most important uncertainties in avP
(and avPT).
Conventional thermobarometry tends to have large
or relatively large uncertainties on individual PT
estimates (absolute uncertainties). However if relative
thermobarometry is the purpose of studying a sequence of rocks, and if they have the same mineral
assemblage, the uncertainties on the PT differences
tend to be much smaller (i.e. the delPT approach of
Worley & Powell, 2000). This is because the uncertainties deriving from the internally consistent data set
and the ax relationships tend to cancel, leaving just
the uncertainties stemming from the analysis of the
minerals.
Thermobarometry of granulite facies and UHT rocks

As this is a Special Issue on Granulites and Granulites,


this section considers some specic aspects of thermobarometry on such rocks. Thermobarometry of granulite facies rocks and, even more so, UHT rocks, presents
particular difculties. They stem partly from the role
that partial melting commonly plays, but mainly from
the fact that diffusion, being strongly temperaturedependent, becomes notably faster into the granulite
facies and, even more so, into UHT conditions.
 2008 Blackwell Publishing Ltd

Partial melting plays a critical role in granulite facies


metamorphism in creating structural complexity via
leucosome development, and in controlling the preservation of mineral assemblages via melt loss (e.g.
White & Powell, 2002). Both are relevant in the context
of thermobarometry, the former in making it more
difcult to determine equilibration volumes, the latter
in relation to the PT conditions that are represented
in the preserved mineral assemblage.
Partial melting and melt loss also play a more subtle
role in changing rock composition and in lowering
aH2O. If the prograde history of a rock that has involved melt loss is to be modelled using pseudosections, then the addition of melt back into the observed
rock composition needs to be attempted (e.g. White
et al., 2004). In thermobarometry of mineral assemblages formed at subsolidus conditions, assuming
uid-present conditions, i.e aH2O 1, is commonly
justiable (at least when CO2 or CH4 is not implicated). In thermobarometry of mineral assemblages
formed above the solidus, aH2O is treated as an additional unknown, along with PT, in conventional
thermobarometry. In pseudosection modelling it is
reasonable to assume that the rocks were just H2Osaturated at the solidus, for rst-cycle metasediments
that were H2O-saturated throughout their prograde
history. However this is unlikely to be a good
assumption for subsequent cycle metasediments (i.e.
ones being reworked), if they were substantially dried
out in a previous metamorphism, and not then rehydrated. Such concerns may apply to any orthogneiss
that may never have been H2O-saturated.
Faster diffusion at higher temperatures introduces a
different set of problems. At lower temperature, the
preservation of a mineral assemblage when a rock uses
up its uid starting to retrogress (e.g. Guiraud et al.,
2001) also appears to coincide with the preservation of
mineral compositions. Particularly in the absence of a
metamorphic uid, temperature is effectively below the
closure temperature of the various exchange reactions
that might continue to change the mineral compositions during cooling. Into the granulite facies this is no
longer true. Feldspar and Fe-Ti oxides do not record
their peak metamorphic compositions. Continued FeMg exchange between minerals occurs during cooling.
In such circumstances, in which the mineral compositions cannot be used reliably, conventional thermobarometry is of little use, unless original mineral
compositions can be reconstructed (e.g. Pattison &
Begin, 1994; Pattison et al., 2003).
Pseudosection thermobarometry, which does not
rely on observed mineral compositions, can be used if
the composition of an equilibration volume can be
established. Even in texturally complex rocks, for
example when high-grade mineral assemblages have
been affected by retrogression, such pseudosection
modelling can be successful. However the retrograde
partitioning of coarse-grained rocks into domains by
diffusion in the earlier stages of decompression/cooling

168 R. POWELL & T.J.B. HOLLAND

can make it difcult to establish an appropriate composition for pseudosection modelling to consider peak
metamorphic conditions. Modelling the textural complexity itself is also possible but is likely to require the
use of chemical potential-chemical potential diagrams
(e.g. White et al., 2008). This is because the domains
commonly cannot be considered as closed systems as
some elements are mobile on a scale larger than the
domains, being available as needed in various domains
(complex textures of White et al., 2008).
Extreme melting and melt loss mean that consideration of a rocks prograde history may be effectively
impossible. Even if an equilibration volume composition can be established, recognition of the peak metamorphic mineral assemblage itself can be difcult. For
example, a pseudosection may have elds with the
diagnostic sapphirine + quartz mineral assemblage,
but it may not be clear whether the two minerals ever
coexisted in the rock, with for example the sapphirine
occurring in domains that have become SiO2-undersaturated early in the cooling history. Particular
problems may occur in orthogneisses in which igneous
precursor minerals are preserved, presenting the danger of combining minerals with a quite different history
for thermobarometry, generating misleading results
(e.g. Racek et al., 2008).
In summary, pseudosections are likely to be the most
effective form of thermobarometry for granulite facies
and UHT rocks, on taking into account the provisos
and difculties discussed above, and with the adoption
of the strategies for pseudosection modelling outlined
in the previous section.
Towards the future: hybrid methods

Thermobarometry using pseudosections has been


essentially qualitative, once the composition of the
equilibration volume is chosen, and the diagram drawn
(the forward part of the modelling). The inverse part
of the modelling involves a qualitative comparison of
the observed mineral compositions and proportions
with the calculated equilibria. On the other hand,
conventional thermobarometry is pure inverse modelling, but only using the observed mineral compositions, not the composition of the equilibration volume
nor the mineral proportions.
Hybrid methods can be envisaged that use more (or
all) of the observations. The prerequisite for this is that
the modelling can be done with a chemical system that
is sufciently close to that in which the equilibration
volume occurs (e.g. NCKFMASHTO). Then it is
straightforward to set up a weighted least squares
problem in which the mineral compositions are to be
matched with the calculated values, the mineral proportions with the calculated ones, and the equilibration
volume composition with the calculated one (via the
calculated mineral proportions and compositions).
Similar to avPT, this could involve minimizing in a
least squares sense the adjustments of the mineral

proportions, mineral compositions and the equilibration volume composition to give the (optimal) PT
result.
Such a complete hybrid method has not yet been
implemented. Compared with the qualitative use of
pseudosections, it would have the merit of bringing into
play the uncertainty in the equilibration volume composition, the effect of which can be difcult to assess
currently (see below). It is worth noting that the variance of the mineral assemblage in the model system is
relevant in considering the control of the equilibration
volume composition on phase relationships, as well as
the dependence of mineral compositions on this composition. For a divariant mineral assemblage, all the
mineral compositions are xed by PT. The equilibration volume composition controls only the position
of the PT eld where the divariant assemblage occurs,
not the mineral compositions. For progressively higher
variance elds, the mineral compositions tend to
become progressively more dependent on the equilibration volume composition, as well as on PT. In such
higher variance elds, thermobarometry, via calculated
mineral composition or mineral proportion isopleths,
actually requires an input rock composition for determining PT. In a hybrid method, the imposed rock
composition becomes a critical constraint, allowing
PT estimation in rocks where conventional thermobarometry cannot be applied at all.
Regardless of the dependence of calculated mineral
compositions on the equilibration volume composition
(as well as on PT), the advantage of pseudosections is
that calculated mineral compositions can be looked at
directly. In contrast, in conventional thermobarometry
the mineral compositions are present only in the
encoded form of the equilibrium constant for the
equilibria being considered. It is the nature of this
encoding that gives rise to the more or less strong correlations between the reaction lines in PT. Because of
this it is usually difcult to see what the consequence is
of varying mineral compositions, or conversely what the
implied compositions are, having performed an avPT
calculation. It is possible to calculate the adjusted
activities implied by the avPT result, but generally not
what are the implied mineral compositions.
An added strength of hybrid methods relates to
handling unknowns in thermobarometry in addition to
PT, like aH2O or aO2. The dependence of results on a
superimposed value of say aO2 can be established in
conventional thermobarometry, but only in the context
of observed (or estimated) ferric iron in the minerals.
In hybrid methods that involve a model chemical system that approaches the rock one, there are more
interesting possibilities that involve superimposing say
aO2 and then calculating the ferric iron contents of the
minerals using it. These contents can then be compared
with the observed or estimated values, or can be used
per se if these values are not known (as is commonly
the case). This then amounts to a generalization of the
above complete hybrid approach in which, addition 2008 Blackwell Publishing Ltd

ON THERMOBAROMETRY 169

ally, some compositional variables of the minerals are


calculated as part of the solution, at specied values of
intensive variables.
ACKNOWLEDGEMENTS

We thank the convenors of the Granulites and


Granulites meeting in Brasilia in 2006 for the
opportunity to talk about thermobarometry there,
and to contribute here. We would like to acknowledge discussions concerning most aspects of mineral
equilibria over the last several years with R. White.
J. Diener, R. White and E. Green are thanked for
reading earlier versions of the manuscript. D. Tinkham, C. Warren and Z. Page are thanked for helpful
reviews, and M. Brown for valuable editorial guidance in how to improve the manuscript.
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APPENDIX 1: IDEAL ANALYSIS APPROACH

the variations from the original analysis, weighted by the corresponding uncertainties, is minimized subject to the specied constraints.
The ideal analysis approach complements a consideration of the
propagation of analytical uncertainties (stemming primarily from
the Poisson counting statistics in electron probe microanalysis) (e.g.
Hodges & McKenna, 1987; Kohn & Spear, 1991). For visual power
in considering the propagation of uncertainties, the best approach is
a Monte Carlo one in which many virtual analyses (produced from
the real one by varying the oxide wt% within their uncertainties)

The ideal analysis approach is a tool for handling mineral


chemical analyses, rst suggested by Carson & Powell (1997) and
also used by St pska & Powell (2005). It involves calculating an
analysis which is closest (in some sense) to the real analysed one
but which has specied stoichiometric or other constraints. This
calculated analysis can be thought of as the ideal analysis that
matches these constraints. The simplest way of doing this calculation is to use weighted least squares: the sum of the squares of

Received 06 May 2007; revision accepted 06 November 2007.

 2008 Blackwell Publishing Ltd

ON THERMOBAROMETRY 171

are recalculated and presented for example in histogram form. It is


easy in such an approach to exclude virtual analyses that conict
with given stoichiometric constraints, particularly inequalities, for
example, Si > 2 in omphacite (recalculated on 6 oxygen). In fact,
in combination with the ideal analysis approach, Monte Carlo can
be used to propagate analytical uncertainties with stoichiometric
equalities obeyed identically.
The power of the ideal analysis approach comes when there are
unknowns in the mineral analysis, for example the proportion of allFe-as-FeO to be converted to Fe2O3, and the standard approach is to
use a stoichiometric constraint to estimate it. Such so-called ferric
ddles are notoriously senstive to the quality of the mineral analysis.
Sometimes there are several things that are unconstrained in an
analysis, for example in a clinopyroxene analysis the Fe3+ content
and M2-site vacancy (associated with the Ca-Eskola end-member
Ca12 (12 AlSi2O6). Then there must be as many independent stoichiometric constraints as there are things to be estimated. In the clinopyroxene case these could be Si 2 and charge balance, but this is
very restrictive, although it might be appropriate for lower temperature eclogitic clinopyroxene.
A better approach is to accept that unknowns in an analysis
cannot be estimated from the analysis alone, and to use the ideal
analysis approach to investigate the consequences of a variety of
values for the unknowns, either in terms of the recalculated analysis
itself or in a thermobarometric context. This can be aided by the use
of a calculated rt (in relation to a chi-squared test) to ascertain
whether the implied modication of the analysis is appropriate or
not. The technique may bracket an acceptable range in an unknown,
or conversely show that the unknown is unconstrained by the analysis.
In the context of using THERMOCALC for conventional thermobarometry, an additional use of the ideal analysis approach is to modify
an analysis so that it has the stoichiometry of the ax datale coding,
bearing in mind that the rt should be acceptable.

Fe2O3. The proportional conversion, x, may either be specied in


the calculation or solved for (with sufcient constraints). The
conversion can be formulated by pre-multiplying p by a matrix F,
starting with an identity matrix (a square matrix with ones on the
diagonal, and zeroes elsewhere). If there are no unknowns (no
conversion) then F remains as the identity matrix in the following.
With x, F is modied as follows: (i) the diagonal element at the
Fe2O3 position is made zero; (ii) the diagonal element at the FeO
position is set to 1 ) x [so that the corresponding p value becomes
(1 ) x)pFeO]; and (iii) the off-diagonal element in the Fe2O3 row
and FeO column is set to x/2 (so that the Fe2O3 p value becomes
(x/2)pFeO).
The general constraint form can then be written as
hT Fp bo  nMaT Fp 0

hT Fp pSiO2 pTiO2  pFeO 1  x  pMgO  pMnO


 pCaO  4pNa2 O  4pK2 O 0
Using Mikhail (1976, p. 138), an ideal analysis, pideal, is given by
pideal p 

For cation, ck, in recalculation on an n-oxygen basis


wk
n
n
mk P wi pk mk P
ck
o i ri
oi pi
rk
in which wk is the wt% of oxide k, rk is the molecular weight of k,
pk wi/ri is the (unnormalized) mole proportion of k, and ok and mk
are the number of oxygen and cations in the formula unit of k,
respectively. In vector form, this is
n
1
c Mp T
o p
in which p is the vector of mole proportions, o is the vector of
number of oxygens in the oxide formulae, and M is a diagonal matrix
with diagonal elements that are the number of cations in the oxide
formulae.
Formulating a constraint on the cations, for example that the
cation sum in a pyroxene is 4, involves specifying a linear combination of the cations, a, to be a value b:
aT c b
In this example, a is a vector of ones, and b 4. Substituting for c
using Eq. (1) gives
n
b aT c aT Mp T
o p
Rearranging gives a general constraint form
hT p  bo  nMaT p 0

with h bo ) nMa being the vector that represents the constraint.


In general such constraints are not met without p being modied.
If all elements are analysed, there are no unknowns and the
analysis is modied to match the constraints using the approach
below. For ferromagnesian minerals, some of the analysed FeO
(the microprobe giving all Fe as FeO) needs to be converted to

 2008 Blackwell Publishing Ltd

Vp AT pA
AVp AT

in which A is derived from the constraint (3), with A hTF, and Vp


being the covariance matrix of p. Using a relative error of 1% on the
wt% of the oxides, then Vp is a diagonal matrix with the kth diagonal
element being (0.01 pk)2. The form of Eq. (4) is that of a single
iteration step: only one step is needed as long as A and Vp are constants. Moreover, using a standard result
r2fit

Setting up a general stoichiometric constraint

By substituting into this, and dividing through by two, the constraint


for the above clinopyroxene example is

pideal  pT V1
p pideal  p
m

where m is the number of oxides in p. This measure of goodness of t


(which is referred to as the MSWD in geochronology, the mean of
the sum of the weighted deviates, McIntyre et al., 1966) is distributed as v2, so for example for a 11-element analysis rt < 1.34 for
95% condence that the resulting ideal analysis is consistent with the
original analysis.

Example
The following example uses the omphacite analysis from Proyer et al.
(2004), Table 2, column 5), used by them for their thermobarometry
and also used in the thermobarometry example in the main text. In
the following table, the rst column in each pair is in wt%, the
second column is cations on 6 oxygen. The rst two columns are for
the analysis with all Fe-as-FeO, the second two columns with the
Mossbauer FeO:Fe2O3, the conversion of FeO to Fe2O3 being x
0.54 0.1(2r) (labelled moss). The last two columns are for an ideal
analysis with x 0.54, with Si 2, and with a specied proportion
of Ca-Eskola molecule of 0.035. The rt associated with this ideal
analysis is only 0.19.
No Fe3+
SiO2
TiO2
Cr2O3
Al2O3
Fe2O3
FeO
MnO
MgO
CaO
Na2O
K2O

Moss

56.97
0.05
0.06
11.72

2.0155
0.0013
0.0017
0.4888

3.82
0.04
7.79
11.69
7.63
0.03

0.1130
0.0012
0.4107
0.4432
0.5234
0.0014

56.97
0.05
0.06
11.72
2.29
1.76
0.04
7.79
11.69
7.63
0.03

Ideal
2.0053
0.0013
0.0017
0.4864
0.0607
0.0517
0.0012
0.4087
0.4409
0.5208
0.0013

56.76
0.05
0.06
11.78
2.30
1.76
0.04
7.82
11.74
7.66
0.03

2.0000
0.0013
0.0017
0.4893
0.0610
0.0519
0.0012
0.4108
0.4432
0.5233
0.0014

172 R. POWELL & T.J.B. HOLLAND

The A matrix used for this ideal analysis calculation is


0 1
Si
1
Ti B
B 2
Cr B
B 3
Al B
B 3
Fe3 B
B 0
AT Fe2 B
B 1 x2
Mn B
B 1
Mg B
B 1
B
Ca B 1
@
Na
1
K
1

2
1
4  2e
C
4  2e
C
C
3e
C
C
3e
C
C
0
C
4x  1  e1 x2 C
C
C
e  4
C
C
e  4
C
C
e  4
C
A
e  16
e  16

APPENDIX 2: DATAFILE CODING FOR

THERMO-

CALC

with the rst row of A (the rst column of AT) forcing Si 2 and the
second forcing the specied proportion of Ca-Eskola molecule.
Figure 2 shows the dependence of rt on proportion of Ca-Eskola
molecule, for a range of FeO to Fe2O3 conversion of 0.54 0.1
(Proyer et al., 2004).
As noted by Proyer et al. (2004), a simple charge-balance ferric
calculation for this omphacite gives no ferric iron, for a cation sum of
4 (i.e. for no Ca-Eskola molecule). But even a small proportion of
Ca-Eskola molecule allows signicant ferric by such a calculation.
Whereas it appears that in HP eclogites this molecule is not signicant, so that charge balance calculations may work (even if they have
large attendant uncertainties), for UHP eclogites charge balance
calculations are unhelpful.
Propagation of uncertainties for a clinopyroxene analysis such as
this one can be undertaken using Monte Carlo combined with the
ideal analysis approach. Here this is done to investigate the uncertainties on the variables used in the THERMOCALC ax datale coding
(Appendix 2) as used in the main text. The uncertainties are shown in
Fig. 3, resulting from the input uncertainties of 1% relative on the
wt% oxides, FeO to Fe2O3 conversion of 0.54 0.1, and an allowed
Ca-Eskola molecule proportion of 0 to 0.06. Ideal analyses were
excluded that involved rt > 1.34. Using the same propagation approach on Fe2+/Mg gave r 0.037, translating to r 65 C on T
with the thermometer of Krogh Ravna (2000). Note that this large
value comes just from the analytical uncertainties, even given the
Mossbauer result.

In this appendix the ax relationships for omphacite (Green et al.,


2007), garnet (based on White et al., 2007) and muscovite (based on
Coggon & Holland, 2002) for use in THERMOCALC are given. These
allow the same ax relationships to be used for calculations on
individual reactions, and in avPT, as in pseudosection calculations.
In the former cases, THERMOCALC calculates the individual activities
from the overall coding for the phase involved, including calculating
the equilibrium state of orderdisorder.
We face a particular problem in this new use of ax coding in that
there is a requirement of more complete models in order to handle
real mineral compositions. The program, AX (http://www.esc.
cam.ac.uk/astaff/holland/index.html), in calculating activities of
mineral end-members from mineral analyses, handles the necessary

300

x(o)

250
200
150
100
50
0.05

0.1

0.15

300

0.2
j(o)

250
200
150
100
50
0.51

0.52

0.54

0.56

300

0.58
f(o)

250
200
150
100
50
0.05
Fig. 2. Using the ideal analysis approach on the Proyer et al.
(2004) omphacite analysis. The x-axis is the specied proportion
of the Ca-Eskola molecule in the omphacite, e, and the y-axis is
the rt for the modication of the analysis for it to have the
specied ferric, as well as the specied stoichiometry. The band is
for the analysed ferric iron, x 0.54 0.1. See text for details.

0.1

0.15

0.2

Fig. 3. The result of a Monte Carlo analysis for the Proyer et al.
(2004) omphacite with x 0.54 0.1, e in the range 0 to 0.1,
using the ideal analysis approach, discarding resulting analyses
which fail the chi-squared test. The individual histograms are
for the composition variables in the THERMOCALC datale coding.
See text for details.
 2008 Blackwell Publishing Ltd

ON THERMOBAROMETRY 173

contraction/extrapolation from real chemical systems into model


systems, as described in axnotes.pdf at the same website. This is not
necessarily a straightforward step, as can be illustrated by considering muscovite.
For muscovite, AX returns activities of the end-members, mu, pa,
cel and fcel, from its recalculation of a mineral analysis. Site allocations may include A-site vacancy (pyrophyllite substitution),
Fe2+ + Mg onto the M1 site (trioctahedral substitutions), as well as
Fe3+ onto M2A (ferric substitution), based on Coggon & Holland
(2002). Whereas the ideal-mixing activities are made with these site
fractions, the non-ideality is expressed without specic consideration
of the additional end-members, thus implicitly taking the corresponding interaction energies to be zero. As these are minor constituents of muscovite, the error introduced by this is minimal, and
indeed such an assumption is necessary for any calculation to be
made using muscovite.
In using the datale coding, the recalculated mineral analysis needs
to be formulated with the composition variables used in the coding.

This means that the necessary assumptions in writing the thermodynamics should be explicitly a part of the coding: the coding needs
to include the pyrophyllite, trioctahedral and ferric substitutions.
This is in contrast to the standard Coggon & Holland-based datale
coding for pseudosections that assumes muscovite is a stoichiometric
strictly dioctahedral mica. Although such an approach is possible
with real muscovite analyses, it is not clear how the observed mineral
composition can be projected into the simple system, and the
composition variables assigned, except by an explicitly thermodynamic procedure. However, in the following, the substitution of CaEskola molecule in omphacite has not been explicitly coded, nor is
the trioctahedral substitutions in muscovite.
In situations where observed mineral compositions are slightly
non-stoichiometric, but are within analytical uncertainty of being
stoichiometric, and/or where there is no reason to suspect signicant
non-stoichiometry (unlike in the case of both the pyrophyllite and
trioctahedral substitutions in muscovite), the ideal analysis approach
provides the tool for handling mineral analyses.

In the following ax coding, the position of the starting guess compositions (that prime the nonlinear equation solver for pseudosection
calculations) is used for the observed mineral compositions in the context of single-reaction calculations and avPT. End-members that are
not to be used for single reaction or avPT calculations have the keyword exclude, in the block where the ideal activity expression for the
end-member is specied. Uncertainties on composition variables and interaction energies are provided using the keyword sd followed by
the value (all are set to zero below, allowing uncertainties stemming just from the thermodynamic dataset to be identied).

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174 R. POWELL & T.J.B. HOLLAND

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ON THERMOBAROMETRY 175

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176 R. POWELL & T.J.B. HOLLAND

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ON THERMOBAROMETRY 177

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178 R. POWELL & T.J.B. HOLLAND

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ON THERMOBAROMETRY 179

 2008 Blackwell Publishing Ltd

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