4/23/2011 "Classical" Thermobarometry

Teaching Phase Equilibria

Inte gra ting R e se arch a nd Education > Te a ching P hase Equilibria > "Classical" The rm obarom e try

"Classical" Thermobarometry
Donna W hitne y, Unive rsity of Minne sota

Thermobarometry is the quantitative determination of the temperature and pressure at which

a metamorphic or igneous rock reached chemical equilibrium. The term "classical"
thermobarometry refers to methods for calculating the P-T conditions of a specific chemical
reaction.

Why do we need to know pressures and temperatures of petrologic

events?

If you know the pressure (P) and temperature (T) at

which an igneous or metamorphic rock equilibrated, you
can determine a lot about where in the Earth the rock
formed and how the rock formed. For example, some
tectonic processes are associated w ith characteristic
pressures and temperatures: e.g., low temperatures at
high pressure occur only in subduction zones.

How do we determine (paleo) pressures

and temperatures?
Figure 1 . P hotomic rograph of a blues c his t from
Mineral assemblages and textures may provide
Sivrihis ar, T urkey, c ontaining glauc ophane
information about the conditions at w hich a rock
(blue), garnet (pink), and laws onite (white).
Field of view = 4 mm. equilibrated. In metamorphic rocks, w e use qualitative
terms such as low -grade, medium-grade, and high-grade (and even 'medium-low ' or 'very high
grade') to describe the approximate temperature conditions of metamorphism. These
designations do not provide information about pressure, and are therefore not useful for
describing subduction zone rocks.

Other methods for characterizing metamorphic conditions include:

(1) index minerals : characteristic minerals that provide an indication of the temperature (and, in
some cases, pressure) conditions at which a rock formed (e.g., kyanite in metamorphosed
shale; magmatic epidote in plutons and volcanic rocks). Not all rocks have a suitable bulk
composition to produce index minerals.

(2) metamorphic facies : assemblages of minerals, each characteristic for a particular bulk
composition and indicating the range of pressure-temperature conditions at which the rock
equilibrated (Figure 2). For example, high-pressure - low -temperature conditions characterize
the blueschist facies.

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Some igneous assemblages are also

characteristic of crystallization w ithin
particular ranges of temperature/pressure
conditions.

Are qualitative methods for

determining P-T conditions 'good
enough'?

Qualitative methods don't necessarily

provide information about both pressure
and temperature. In addition, qualitative
techniques in some cases give only a
Figure 2 . P res s ure- temperature diagram s howing the loc ations
minimum pressure or temperature: e.g.,
of the metamorphic fac ies . M odified from Spear (1 9 9 3 ). T he
the presence of a high-T index mineral may
A l 2SiO 5 phas e diagram is als o s hown for referenc e. A nd =
not tell you w hether the rock formed at
andalus ite; Ky = kyanite; S il = s illimanite. 700 °C or 1000°C, and the occurrence of
eclogite facies minerals may not tell you w hether the rock formed at a depth of 40 km or 75 km.
This degree of uncertainty makes the interpretation of metamorphic and tectonic processes
difficult.

Thermobarometry

Conceptual basis: The compositions of coexisting minerals in equilibrium are related by the
thermodynamic properties of the minerals to the pressure and temperature conditions of
equilibration. Thermometers are assemblages that form by reactions that are sensitive to
temperature but not (much) to pressure. Barometers are assemblages that are sensitive to
pressure but not (much) to temperatures. Not all rocks contain assemblages that make suitable
thermometers or barometers.

To apply a thermometer or barometer (H T M L File 7 kB M ar3 1 0 7 ) to an equilibrium mineral

assemblage, you need to know :
1. The compositions of all minerals that can have variable composition (e.g., solid
solutions).
2. Thermodynamic data for the phases of interest.
3. A 'calibration' that allows you to relate mineral composition to pressure or
temperature.

Thermometry

Exchange reactions. Exchange reactions involve the exchange of cations with similar sizes and
charges betw een tw o minerals. These reactions are typically very temperature-sensitive, but
are not pressure-sensitive because no major change in volume is involved in the exchange.
Temperature-sensitive reactions have steep slopes on P-T diagrams (Figure 3a). The most
common exchange thermometers involve exchange of Fe 2+ and Mg between two minerals, e.g.,
between garnet and biotite.

Solvus thermometry involves phases that form a solid solution at high-T but that 'unmix' into
separate phases during cooling. The composition of coexisting minerals that have a solvus
relationship is an indicator of temperature (Figure 3b), although in some cases this may be a
temperature representing part of the cooling path of a rock. Examples: muscovite-paragonite;
calcite-dolomite; orthopyroxene-clinopyroxene; feldspars.

Figure 3 .

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4/23/2011 "Classical" Thermobarometry
Sc hematic P - T
(a) and T -X
(s olvus ) (b)
diagrams
illus trating
general
c harac teris tic s
of
thermometers
and
barometers .
T hermometers
have s teep
s lopes and
barometers
have s hallow s lopes on a P - T diagram.

Other : The composition of coexisting plagioclase and calcic amphibole (e.g., hornblende) can be
used to estimate temperature. Other thermometers involve trace element concentrations of
phases. For example, the concentrations of Ti in quartz and zircon in equilibrium with rutile
(TiO 2 ), and the concentration of Zr in rutile are very sensitive to temperature. These
thermometers can be applied to igneous and metamorphic rocks, but require an ion microprobe
for analysis of trace concentrations (ppm) of Ti and Zr. Another trace element thermometer w ith
applications to metamorphic rocks involves the yttrium concentration of coexisting monazite and
garnet (or monazite and xenotime).

The concentration of stable isotopes of oxygen and carbon in coexisting minerals can also be
used to determine the temperature at w hich the system became closed to exchange of these
isotopes. For example, the O 18 /O 16 ratio in coexisting quartz and magnetite is a thermometer,
as is the C 13 /C 12 ratio in coexisting quartz and calcite or calcite and graphite.

Barometry

Pressure-sensitive reactions (barometers) involve a significant volume change, such as the

transformation of anorthite (Ca-plagioclase) to grossular (Ca-garnet) + kyanite + quartz. Many
barometers are net transfer reactions, and have shallow slopes on P-T diagrams (Figure 3a).
Other barometers involve the concentration of an element in a certain mineral in equilibrium
with a particular assemblage (e.g., Al in hornblende, Si in phengite).

Uncertainties

Uncertainties in thermobarometric calculations can be determined by propagating errors from all

stages of the P-T determinations: the mineral composition analyses, the thermodynamic data,
and the calibration method. Typical uncertainties are ± 50 °C, ± 1 kbar.

Sources of error in thermobarometry

Common sources of error in thermobarometric calculations include:

The assumption that the minerals record equilibrium conditions may not be valid.
The choice of mineral compositions to use in thermobarometric calculations is easy if
all phases are homogeneous, but if minerals are zoned, the selection of compositions
to use can be more uncertain.
The stability of minerals may be affected by the presence of elements that are difficult
to analyze w ith standard techniques. For example, electron microprobe analyses do
not distinguish betw een Fe 2+ and Fe 3+, but the difference is important. A
thermobarometric calculation may be substantially in error if all Fe is assumed to be
Fe 2+ for minerals that contain substantial Fe 3+.

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Thermobarometric calculations rely on thermodynamic data and a 'calibration' that
allow s mineral composition to be related to temperature or pressure. The mineral
compositions and crystal structures in the rock being analyzed should not be too
different from the compositions and structures on w hich the calibrations are based.
Temperature calculations require an estimation of pressure, and pressure calculations
require an estimation of pressure. You therefore either need to know one variable, or
use a thermometer or barometer that is very insensitive to the other variable. Hence,
the best thermometers have nearly vertical slopes on a P-T diagram and the best
barometers have nearly horizontal slopes.

What do calculated P-T conditions mean?

For igneous rocks, calculated pressures and temperatures likely represent the conditions at
crystallization, particularly for rapidly cooled rocks. Metamorphic rocks have more complex
thermal and pressure histories, but the most typical interpretation of thermobarometric results
is that the calculated P and T represent the conditions at the thermal maximum (peak of
metamorphism) (Figure 4). It is important to recognize that the thermal maximum may not
represent the pressure maximum (Figure 4). Furthermore, it is important to examine the
textures of a metamorphic rock and determine if the mineral assemblages/textures are
consistent w ith the interpretation that peak metamorphic conditions are preserved and have
not been overprinted during later events.

Figure 4 . A c ommon pres s ure- temperature path for

regional metamorphis m. T he firs t s tages of
metamorphis m involve burial and heating. Following the
attainment of maximum pres s ure (depth), roc ks - -
whic h are poor c onduc tors of heat and therefore are
s low to heat relative to tec tonic rates of burial -- may
reac h their maximum temperature c onditions during the
initial s tages of dec ompres s ion. T herefore, the peak of
metamorphis m (thermal maximum) may not c oinc ide
with the depth maximum.

Resources

Thermobarometry (more info)

Dave Waters' on-line tutorial on Practical

Thermobarometry
Problem Set: Calculating Pressures and
Temperatures of Petrologic Events:
Geothermobarometry - Donna Whitney, University of Minnesota
Thermobarometry Problem Set - Jane Selverstone, University of New Mexico
Thermodynamic Calculation of Mineral Reactions II Lab (M ic ros oft Word 4 8 kB M ar2 9 0 7 ) -
This Excel-based one w eek exercise, provided by Dave Pattison at the University of
Calgary, includes problems sets involving equilibrium constants, activities and
calculation of thermodynamic equilibria involving impure phases, and 'conventional'
thermobarometry using the GTB program.
Multi-equilibrium Thermobarometry Lab (M ic ros oft Word 5 3 kB M ar2 9 0 7 ) - This Excel-based
one week exercise, provided by Dave Pattison at the University of Calgary, includes
problems sets involving multi-equilibrium thermobarometry using TWQ and
ThermoCalc's 'AvePT' module ('Optimal thermobarometry').

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