Limitations of PT estimations

The successful application of geothermometric and geobarometric techniques to rocks,

regardless whether conventional geotermobarometers or internally-consistent
thermodynamic data-sets are used, requires that the mineral assemblage under consideration
is in equilibrium. Unfortunately, equilibrium cannot be proven irrefutably, but it is feasible to
use some criterio to recognise a disequilibrium situaion. The concept of local equilibrium or
equilibration volumen is important in this context. Local equilibrium impkies that parts of a
rock may have reached equilibrium, where as other parts are still in disequilibrium. The
recognition of such local equilibrium domains, to which equilibrium thermodynamics can be
applied, is important, especially at low temperatures, as the size of the equilibration volume
decreases rapidly with falling temperature. The application of conventional
geothermobarometry to determine PT paths is potentially dangerous as the reconstruction of
a path depends on the various local equilibria and disequilibria preserved in the rock. For
kinetic reasons, it is usually the metamorphic (thermal) peak assemblage that is preserved in
rocks. If this assemblage is not re-equilibrated after the termal peak, for example because of
the lack of a suitable fluid phase to revolatilise dehydrated and/or decarbonated mineral sor
because of uplift associated with rapid erosion, etc., the mineral compositions of the preserved
peak assemblage are likely to reflect the equilibrium conditions of the thermal peak.

Obviously, geothermobarometric investigations on this assemblage will yield the maximum

temperature Tmax experienced by the rock and the pressure at the temperature PTmax, which
may not correspond to the maximum pressure that was attained, if the equilibration of a rock
reamined “frozen-in” during the subsequent evolution of the rock, the PT path experienced by
the rock cannot be determined, but only a point on the PT trajectory. Apart from this problem
there are other factors which can influence the results of geothermobarometric methods.

The experimental calibration of ion-exchange reactions as thermometers and mass-transfer

reactions as barometers must, for kinetic reasons, be carried out at temperatures high enough
to allow equilibrium between reactants and products to be attained in the short time span
available in a laboratory. Thus, the phase equilibria are frequently investigated at geologically
unrealistic high temperatures and must be extrapolated over a large temperature and/or
pressure range, which may lead to large uncertainties in the obtained results. For example, the
grossular-kyanite-quartz-anorthite geobarometer was essentially calibrated at pressures and
temperatures well in excess of 17kbar and 950°C (FIG 5) but is frequently applied to
assemblages that formed at much lower pressures and temperatures.

The quality or precisión of the thermodynamic data is of importance for any PT estimation.
Obviously, different values for the enthalpy of formation, entropy, heat capacity etc. Influence
the AG0 term in the fundamental thermodynamic equation O=AG0 + RTlnK and, hence will lead
to different results in PT estimations. It is reassuring, however, that the thermodynamic data of
the mineral end-members that are common to the widely used internally-consistent
thermodynamic data sets of HOLLAND AND POWELL (1990) and BERMAN (1991) coincide
reasonably well with each other.

Some cristal chemical and/or physical parameters can influence PT estimations considerably.
Many minerals, for example mica, amphibolite, chlorite, staurolite, etc., contain ferrous and
ferric iron whose proportions in the minerals cannot be determined through micropobe
análisis. There are various computational schemes to estimate the Fe2O3 contents in minerals.
Generally, each maethod will give a different Fe2+/Fe3+ ratio, which, of course, affects the
equilibrium constant K. Consequently, PT estimates that are base don mineral equilibria
involving such minerals can be strongly influenced by the method use to estimate Fe2+/Fe3+
ratio. As pointed out by WILL (1998), the Fe2O3 contents of a particular mineral should always
be estimated using the same method as this allows at least a calculation scheme-independent
comparison of the PT estimates.