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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
INTRODUCTION
THERMOCALC.
ON THERMOBAROMETRY 157
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have been superceded.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
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
ON THERMOBAROMETRY 161
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
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
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
24
26
28
30
32
34
36
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
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
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
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
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)
ON THERMOBAROMETRY 171
Vp AT pA
AVp AT
pideal pT V1
p pideal p
m
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
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
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.
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
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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