Metamorphic minerals reactions

Rule 1: Solid solution in a phase will expand the stability field of that phase (or
of its associated mineral assemblage) in P-T space.
Rule 2: In a dehydration or decarbonation reaction, a change in the composition
of the fluid will expand the stability field of the assemblage with the fluid.
• Mineral reactions can be classified with regard to the phases that are involved (solid-solid and solid-
fluid reactions) or with regard to the reaction mechanisms and equilibrium conditions (discontinuous
and continuous reactions).
• A. Solid–solid reactions
• Solid–solid reactions involve only solid phases as reactants and products without direct participation
of a volatile phase. A fluid may, be a passive or indirect catalytic participant, enhancing nucleation and
providing a medium for diffusive transport of ions redistributed during growth of the new products.
• B. Solid–fluid reactions release or consume a volatile fluid and depend not only on P and T but the
composition of the volatile as well.
• Redox reactions are driven by changes in T and fugacities of volatiles, principally oxygen, and result in
changes of oxidation states and types of variable-valence phases in assemblages.
• Metasomatic reactions occur in open metamorphic systems where exchange of components between
invasive fluids and the solid phases in a rock results in an entirely new product mineral assemblage.
• C. Discontinuous reactions occur, ideally, at a single T at a particular P. Reactant and product phases are in
equilibrium along a univariant boundary line in P–T space. Discontinuous reactions are of two types:
• 1. Polymorphic phase transitions involve transformation of one solid phase to another of identical chemical
composition but different atomic structure in a one-component system, such as calcite → aragonite.
• 2. Net-transfer (heterogeneous) reactions involve marked movement of matter among multiple phases,
consuming reactants and producing new phases. Modal proportions of the compositionally contrasting
phases change during the course of the reaction.
• D. Continuous reactions are continuously at equilibrium over a range of values of the controlling intensive
variables as a result of substantial compositional variation (solid solution) in the reactant and product
phases. Chemical compositions of participating phases and their modal proportions change during the
course of the reaction.
• A continuous reaction becomes a discontinuous one if only pure end-member phases are considered. An
exchange reaction is a special subclass in which there is no change in modal proportions of reactant and
product phases, only in the concentrations of substitutive ions, such as Fe and Mg, changing the Fe/(Fe _ Mg)
ratio in participating mafic garnet, cordierite, and so on.
• Except for polymorphic transitions, most reactions in metamorphic rocks are combinations of these ideal
end-member types.
 
• Types of Metamorphic reactions:
• On the basis of applying the phase rule, any metamorphic reaction
will belong to one of two types:
• Discontinuous reactions: are those which are univariant on P-T
diagrams in the "model" system.
• A discontinuous reaction takes place between phases of fixed
chemical composition, and will always occur at the same P-T
conditions for the compositions defined.
• A discontinuous reaction takes place between phases of fixed chemical composition,
and will always occur at the same P-T conditions for the compositions defined.
• A univariant reaction is one that plots as a line or curve on a pressure-temperature
diagram.
• If all phases in the reaction are present in the rock, then we know that the rock must
have been metamorphosed at some pressure and temperature along the reaction
boundary Consider for example the simple Al2SiO5 system with excess SiO2 and H2O.
• In low grade metamorphic in this system, the reaction:
 
• Al2Si4O10(OH)2 <=> Al2SiO5 + 3SiO2 + H2O
Ky or Andal Qtz fluid
 On mineral compatibility diagrams, univariant reactions may show up as flipping tie lines as

In the diagrams, the average pelitic rock is shown as composition x. At low grade, the stable mineral assemblage is Garnet +
Chlorite + Biotite + Muscovite + Quartz. As temperature and pressure are raised, this assemblage becomes unstable and the tie
line connecting Garnet and Chlorite is replaced by one connecting Staurolite + Biotite.
The reaction that occurred is the univariant reaction:
Garnet + Chlorite + Muscovite = Staurolite + Biotite + Quartz + H 2O
Another type of univariant reaction represents a reaction that is terminal to a mineral phase for a wide variety
of compositions. For eg. if we reach a temperature and pressure region where staurolite becomes unstable.

With increasing temperature, Staurolite becomes unstable and reacts to produce Garnet, Biotite and Kyanite. Both rock
compositions x and y have the same mineral assemblages before and after the reaction, although the proportions of the different
minerals will be different in the two rocks. The reaction that is terminal to Staurolite can be written as:
Staurolite + Quartz + Muscovite <=> Garnet + Biotite + Kyanite + H 2O

The disappearance of staurolite also coincides with the appearance of Kyanite in rocks of composition x and y. If we were to
encounter this reaction in the field, it could be used to define the Kyanite Isograd.
 
• Continuous reactions: are those which take place over a range of P
and T as a result of solid solution in one or more of the phases
involved.
• Such reactions are characterized by assemblages that are at least
divariant.
• Unlike discontinuous reactions, reactants and products can coexist
over a range of P and T, but where at least one of the phases
constantly changes its composition.
• The univariant reactions that were considered above involved reaching a point in
pressure temperature space where a reaction occurred resulting in a sudden change
in mineral assemblage.
• These reactions can be considered discontinuous reactions because they occur
along specific pressure temperature curves.
• Because many minerals are solid solutions, it is also possible to have discontinuous
reactions that result in a gradual change in composition of the minerals, but not
necessarily the formation of new minerals.
• These reactions are also considered divariant reactions because they occur over a
wide range of pressure and temperature conditions.
• Consider the hypothetical case of rocks that contain minerals like chlorite and
garnet, which are both Mg-Fe solid solutions.
• The reaction that occurs with increasing temperature (at constant pressure) is:
• Chlorite + Qtz => Garnet + Mg-richer Chlorite + H2O
This reaction begins at a temperature of T1 where an initial Mg-poor garnet is produced.
As temperature increases to T2, both the garnet and the chlorite become more Mg-rich.
The reaction continues over a range of temperature until eventually the temperature reaches T 3 at which point the
much more Mgrich chlorite disappears leaving garnet with Mg/(Mg/Fe) ratio the same as that in the initial chlorite.
This reaction is a continuous reaction because there is no change in mineral assemblage between T 1 and T3, but
there is a reaction occurring and its effect is to change the compositions of the solid solution minerals
In the diagram to the left, representing the lowest grade, a rock with composition x consists of a relatively Mg-poor biotite + Mg-
poor chlorite. As metamorphic grade increases to the middle diagram, the three phase triangle - Garnet - Biotite - Chlorite has
shifted, with all three phases becoming more Mg-rich, and now composition x lies inside this 3 phase triangle, and thus now
contains garnet.
Further increase in metamorphic grade, causes further shift to of the apices of the 3 phase triangle toward more Mg-rich
compositions and eventual disappearance of chlorite from the rock with composition x. Throughout the changes in P & T, the
proportion of the 3 phases in composition x will change, as will the composition of the Fe-Mg solid solution minerals. Although
the appearance of Garnet will be sudden, the disappearance of chlorite will be gradual as P and T change. The reaction that is
taking place in this case is:
Muscovite + Chlorite + Quartz <=> Mg-richer chlorite + Biotite +Garnet + H2O
• Homogeneous Equilibria:
• A- Solid - solid reactions:
• Characteristics:
• 1- All phases taking part in the reaction are condensed phases (i.e. solids).
• 2- For the most part, they exhibit very little curvature if any, when plotted
on P-T diagrams. (Curvature usually arising from ordering of one of the
phases).
• 3- They tend to have shallow slopes in P-T space, and are therefore more
sensitive to changes in P rather than T.
• This property makes many such reactions good geobarometers.
• (1) Polymorphic transitions: e.g. Ky Sill, Calcite Aragonite, Graphite
Diamond, -quartz -quartz.
• (2) Net transfer reactions: (Coupled reactions)
• These are reactions that involve a transfer of one or more component
from one phase to another, leading to the consumption of old phases
or the production of new ones. These are of two kinds:
• Terminal reactions: Which involve the complete disappearance of a
phase, such that it is no longer stable beyond a certain P and T.
• Examples: Termial reaction
• Jd + Qz = Ab (a)
• An = grossular + Al2SiO5 + Qz (b)
• If Ab and An are both pure (i.e. have fixed compositions), these
reactions become terminal discontinuous reactions, but if their
compositions are allowed to vary (i.e. solid solution between
continuous, and the breakdown of the “plagioclase” then takes place
over a range of T and P.
• Non-terminal reactions: Which involve the appearance or
disappearance of an assemblage. E.g
• Lw + Gln = Ab + Tr + Chl
• Di + Al2SiO5 = grossular + pyrope
 
• (3) Exsolution or solvus type reactions:
• Occur in phases exhibiting complete solid solution at high T but limited
solid solution at low T (below the critical T where a solvus is defined).
• As the phase cools, it exsolves another phase, usually along cleavage
planes,.. etc.
• Because both the exsolving and exsolved phase are solids, exsolution
reactions are considered solid - solid reactions.
• Examples: Plagioclase - K-feldspar,
• Calcite - dolomite.
• Ab and An),
• These reactions become Exsolution reactions are useful for
geothermometry and geospeedometry (quantifying the rate of a
metamorphic process).
 
• (4) Exchange reactions:
• These are reactions involving element exchange between two phases that
exhibit solid solution.
• Such as the exchange of Fe and Mg between any two ferromagnesian
phases, e.g. Biotite and garnet, clinopyroxene and garnet, ...etc..
• Such an exchange may be represented by the notation:
• FeMg-1 (Gt) = FeMg-1 (Cpx) in the case of the Gt - Cpx pair. The balanced
reaction in this case is:
• Mg3Al2Si3O12 + 3 CaFeSi2O6 Fe3Al2Si3O12 + 3 CaMgSi2O6
• py hd alm di
• II- Heterogeneous Equilibria
• B- Reactions involving a fluid phase:
• All of these reactions can be considered of the net transfer type, since
they involve the appearance or disappearance of new phases.
 
• Types:
• (1) Dehydration reactions:
• These are reactions that have H2O (usually) among their higher T
products. They are characterized by
• (1) a "stepwise" nature, where H2O may be released in increments as T
increases,
• (2) steep P-T slopes and endothermic nature (usually, but not always), and
• (3) the slopes and P-T locations vary with variations in the fluid
compositions (i.e. amounts of components other than H2O in the fluid
phase).
 
• Examples:
• A good example is a typical dehydration reaction:
• Muscovite + Qz = Sillimanite + K-spar + H2O
• On 25 Gln + 6 Cz + 7 Qz + 14 H2O = 6 Tr + 9 Chl + 50 Ab
• A third type of dehydration reaction is exothermic, releasing heat and H2O, such as:
• Jadeite + H2O = Analcime
 
• (2) Decarbonation reactions:
• These are reactions that release CO2.
• They are important in the metamorphism of calcareous rocks.
• They have positive steep slopes on P-T diagrams and positive convex upward curves on
T-XCO2 diagrams (reaction 2; Fig. 4).
• Example: CaCO3 + SiO2 = CaSiO3 + CO2.
 
• (3) Mixed volatile reactions:
• These are reactions that involve two fluid phases, such as H2O and CO2.
• There are two types:
• A reactions in which H2O and CO2 are on the same side (i.e. either reactants or products);
• Example, which on T-XCO2 diagrams would plot as convex upward curves with maxima the
locations of which depend on the stoichiometric reaction coefficients of CO2 and H2O, is:
• Tr + Cc + Qz = Di + 3 CO2 + H2O
• (where the "maximum" will occur at XCO2 = 3/(3+1) = 0.75) (reaction 4 on Fig. 4).
• B reactions in which H2O and CO2 are on different sides of the reaction (one reactant,
the other a product).
• Examples of the second type, which is characterized by a sigmoidal shaped curve with an
inflection point on a T-XCO2 diagram include:
• Zo + CO2 = An + Cc + H2O, and
• Do + Qz + H2O = Tc + Cc + CO2
 
• (4) Oxidation-reduction reactions:
• These are reactions that involve a change in the oxidation state of one or more of the
elements involved.
 
• Examples:
• Fe - O2, containing the phases hematite, magnetite and O2.
• 2 Fe3O4 + 1/2 O2 = 3 Fe2O3
• From the phase rule, f = 2-3+2=1. This means that only one parameter is allowed to vary
independently in the system without bringing about an appearance or disappearance of a
phase.
• At constant P, possible sources of system variance are T and the composition of fluid and
solid phases.
• Assuming that hematite and magnetite are both pure (generally a reasonable the other
hand, a few reactions may have H2O among their low T reactants, such as:
assumption), they will have unit activities. Therefore, at a given T, fO2 is immediately fixed at a
unique value. A rock containing both hematite and magnetite is therefore considered
“buffered” for fO2.
• Other buffers of fO2:
• 3 Fayalite + O2 = 2 Mgt + 3 Qz (FQM buffer, lower fO2 than Hm-
Mgt).
• Fe + 1/2 O2 = FeO (Wustite) (Fe-Wustite buffer) (Figs. 5 & 6).
• C (graphite) + O2 = CO2
• Because CO2 is a common constituent of metamorphic fluids, the
occurrence of graphite in a metamorphic rock indicates that it was
metamorphosed under reducing conditions in which the fO2 values
were below those defined by this buffer.
• Common metamorphic reactions affected by changes in fO2:
• Other reactions that involve a change in the oxidation state of one or
more elements include the reaction between lawsonite and epidote.
• In the literature, you will commonly find it mentioned that an increase
in T is needed to form Ep at the expense of Lw. However, in the
presence of Mgt, an increase in fO2 is also needed, as demonstrated
by the reaction:
• Lw + Mgt + O2 = Ep + H2O
• which, unlike the Hm - Mgt reaction does not have sufficient buffering
capabilities. However at fO2 values higher than those defined by the
Mgt - Hm buffer, the breakdown of Lw to Ep is indeed driven solely by
a change in T according to the reaction: Lw + Hm = Ep (Fig. 7)