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Geokimia

temu kesebelas
2013
Types of Metamorphic reactions
- With either progressing or retrogressing metamorphism,
various types of metamorphic reactions are proceeds e.g.:
1- Univarient reactions: reactions that plot as line or curve
on the P-T diagram and depend on temperature and
pressure only e.g:
Al2Si4O10(OH)2  Al2SiO5 + 3 SiO2 + H2O
Pyrophyllite Al-silicate + Qtz + fluid
Cont. Types of Metamorphic reactions
2- Divarient reactions: reactions
occur over wide range of P-T. This
because most minerals involved
in the reaction exhibit solid
solution (e.g garnet, mica,
plagioclase); therefore, the
reaction boundaries can changed
depend on the composition of
solid solution.

KAl2Si3AlO10(OH)2 + SiO2 = KAlSi3O8 + Al2SiO5 + H2O


Ms Qtz Kfs Sill W
Devolatilization Reactions
For example the location of the reaction line on a
P-T phase diagram of the dehydration reaction:
KAl2Si3AlO10(OH)2 + SiO2 = KAlSi3O8 + Al2SiO5 + H2O
Musc Qtz Kfld Sill Water
depends upon the partial pressure of H2O (pH2O)
Devolatilization Reactions

Here the equilibrium curve


represents equilibrium
between the reactants and
products under water-
saturated conditions
(pH2O = PLithostatic)

P-T phase diagram for the reaction Ms + Qtz


= Kfs + Al2SiO5 + H2O showing the shift in
equilibrium conditions as pH2O varies
(assuming ideal H2O-CO2 mixing). Calculated
using the program TWQ by Berman (1988,
1990, 1991). After Winter (2001) An
Introduction to Igneous and Metamorphic
Petrology. Prentice Hall.
KAl2Si3AlO10(OH)2 + SiO2 = KAlSi3O8 + Al2SiO5 + H2O
Ms Qtz Kfs Sill water
 Suppose H2O is withdrawn from the system at some point on the water-saturated
equilibrium curve: pH2O < Plithostatic
 According to Le Châtelier’s Principle, removing water at equilibrium will be
compensated by the reaction running to the right, thereby producing more water
 This has the effect of stabilizing the right side of the reaction at the expense of
the left side
 So as water is withdrawn the Kfs + Sill + H2O field expands slightly at the
expense of the Mu + Qtz field, and the reaction curve shifts toward lower
temperature

Pfluid < PLith by drying out the rock and


reducing the fluid content
Pfluid = PLith, but the water in the fluid can
become diluted by adding another fluid
component, such as CO2 or some other
volatile phase
Cont. Types of Metamorphic reactions
3- Solid-solid reaction: only
involve the solid-phases for both
reactant and products (with no
fluid phases). So reactions
involves phase transformation
e.g.

Calcite  aragonite,
andalusite  sillimanite,
Albite  jadite + quartz
graphite  diamond
Solid-Solid Net-Transfer Reactions
 Differ from polymorphic
transformations: involve solids
of differing composition
 Material must diffuse from one
site to another for the reaction
to proceed

NaAlSi2O6 + SiO2 = NaAlSi3O8 Reaction curves typically pretty straight


Jd Qtz Ab DS and DV change little

MgSiO3 + CaAl2Si2O8 = CaMgSi2O6 + Al2SiO5


En An Di And

4 (Mg,Fe)SiO3 + CaAl2Si2O8 =
Opx An Plag

(Mg,Fe)3Al2Si3O12 + Ca(Mg,Fe)Si2O6 + SiO2


Gnt Cpx Qtz
Solid-Solid Net-Transfer
Reactions
If minerals contain volatiles, but the volatiles
conserved in the reaction so that no fluid phase is
generated or consumed
For example, the reaction:
Mg3Si4O10(OH)2 + 4 MgSiO3 = Mg7Si8O22(OH)2
Talc Enstatite Anthophyllite
involves hydrous phases, but conserves H2O
It may therefore be treated as a solid-solid net-
transfer reaction
Phase Transformations
Isochemical phase transformations (the polymorphs of
SiO2 or Al2SiO5 or graphite-diamond or calcite-
aragonite
The transformations depend on temperature and
pressure only

Aragonite is the stable


CaCO3 polymorph
commonly found in
blueschist facies
terranes
Phase Transformations
Independent of other
minerals present, fluids,
etc.
Andalusite -> Sill as T and P
increase
regardless of other phases
Stau, Mus, Qtz
Phase Transformations
Small DS for most polymorphic transformations
 small DG between two alternative polymorphs, even
several tens of degrees from the equilibrium boundary
 little driving force for the reaction to proceed 
common metastable relics in the stability field of other
Coexisting polymorphs may therefore represent non-
equilibrium states (overstepped equilibrium curves)

Staurolite poikiloblast
Cont. Types of Metamorphic reactions
4- Dehydration reactions: reactions
that liberate H2O. This always occur in
the prograde reaction, i.e. with
increasing temperature e.g

chlorite + muscovite 
orthoclase + andalusite +
H2O

5- Decarbonation reaction : reactions

that liberate CO2 e.g

Calcite + quartz  Wollstonite + CO2 


Decarbonization Reactions
CaCO3 + SiO2 = CaSiO3 + CO2 (26-6)
Cal Qtz Wollastonite

Figure 26-5. T-XCO2 phase diagram for the reaction Cal + Qtz
= Wo + CO2 at 0.5 GPa assuming ideal H2O-CO2 mixing,
Figure 26-1. A portion of the equilibrium boundary for the calcite- calculated using the program TWQ by Berman (1988, 1990,
aragonite phase transformation in the CaCO3 system. After 1991). Winter (2001) An Introduction to Igneous and
Johannes and Puhan (1971), Contrib. Mineral. Petrol., 31, 28-38. Metamorphic Petrology. Prentice Hall.
Winter (2001) An Introduction to Igneous and Metamorphic
Petrology. Prentice Hall.
Cont. Types of Metamorphic reactions

6- Oxidation-reduction reaction: reactions that involve change the


valence state of Fe-Ti oxide phases (Fe+2 and Fe+3) e.g: the
breakdown of biotite to K-feldspars and magnetite at high P-T
conditions
biotite + O2  K-feldspars + Magnetite + H2O

7- Cation exchange reaction: reaction involves ionic substitution


of two or more phases in the system e.g:
Fe-garnet + Mg-biotite  Mg-biotite + Fe-garnet

8- Ionic reactions: reaction that balanced by inferring involvement


of ionic species derived from the fluid phase
Ion Exchange Reactions
• Reciprocal exchange of components between 2 or
more minerals
– MgSiO3 + CaFeSi2O6 = FeSiO3 + CaMgSi2O6
Enstatite + Hedenbergite = Ferrosilite + Diopside

• Expressed as pure end-members, but really involves


Mg-Fe (or other) exchange between intermediate
solutions
• Basis for many geothermobarometers
Protoliths of metamorphic rocks
As we discuss, The yielded metamorphic rocks is function
of:
- Protolith (original rock) nature  bulk-rock chemistry
- P (pressure)-T (temperature)-X (active fluids) conditions
- Time

At specific P-T-X conditions, reactions in solid state toke place in


the rock and new equilibrated mineral assemblage and
corresponding textures are arise, which equivalent to the
influence metamorphic conditions.
Protoliths of metamorphic rocks
The protoliths of the metamorphic rocks could be:

-Sedimentary rocks
- Shales (Pelitic rocks)
- Sandstones (Arenaceous rocks and semipelitic rocks)
- Carbonate (Calcareous rocks)
- Marl rocks
- Igneous rocks
- Basic igneous rocks (metabasites)
- Ultramafic rocks
- Granitoid rocks
- Prior metamorphic rocks
Metamorphic Reactions
 Isograds are reaction
 lines
Exsolution
Some solid solutions
are unstable at lower
T, and exsolve as T
falls.

Classic example K-spar


and Ab form a solid
solution at 1000oC but
separate into
Microcline + Albite ->
Perthitic Texture
Figure 6-16. T-X phase diagram of the system
albite-orthoclase at 0.2 GPa H2O pressure. After
Bowen and Tuttle (1950). J. Geology, 58, 489-511.
Winter (2001) An Introduction to Igneous and
Metamorphic Petrology. Prentice Hall.
exsolution, in mineralogy, process through
which an initially homogeneous solid solution
separates into at least two different
crystalline minerals without the addition or
removal of any materials. In most cases, it
occurs upon cooling below the temperature of
mutual solubility or stability of the solution.
The sodium-rich feldspar albite (NaAlSi3O8)
and the potassium-rich feldspar orthoclase
(KAlSi3O8), for example, may exist in a
homogeneous solid solution above 650° C
(1,200° F), but below that temperature
exsolution will occur.
See you soon.......coz