What happens to our PROTOLITH when acted on by AGENTS OF CHANGE??

• Agents of Change T, P, fluids, stress, strain

• Metamorphic Reactions!!!!– Solid-solid phase transformation– Solid-solid net-transfer– Dehydration– Hydration– Decarbonation– Carbonation

Solid-solid phase transformation

• Polymorphic reaction a mineral reacts to form a polymorph of that mineral

• No transfer of matter, only a rearrangment of the mineral structure

• Example:– Andalusite Sillimanite

Al2SiO5 Al2SiO5

Solid-solid net-transfer• Involve solids only• Differ from polymorphic transformations: involve

solids of differing composition, and thus material must diffuse from one site to another for the reaction to proceed

• Examples:

• NaAlSi2O6 + SiO2 = NaAlSi3O8 Jd Qtz Ab

• MgSiO3 + CaAl2Si2O8 = CaMgSi2O6 + Al2SiO5 En An Di And

Solid-Solid Net-Transfer II

• If minerals contain volatiles, the volatiles must be 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

Hydration/ Dehydration Reactions• Metamorphic reactions involving the

expulsion or incorporation of water (H2O)• Example:

– Al2Si4O10(OH)2 <=> Al2SiO5 + 3SiO2 + H2O Pyrophyllite And/Ky Quartz water

Carbonation / Decarbonation Reactions

• Reactions that involve the evolution or consumption of CO2

• CaCO3 + SiO2 = CaSiO3 + CO2 calcite quartz wollastonite

Reactions involving gas phases are also known as volatilization or devoltilization reactions

These reactions can also occur with other gases such as CH4 (methane), H2, H2S, O2, NH4

+ (ammonia) – but they are not as common

Systems• Rock made of different minerals

• Metamorphic agents of change beat on it metamorphic reactions occur

• A closed system does not gain or lose material of any kind

• An open system can lose stuff – liquids, gases especially

Hunk o’ rock

Outsideworld

Thermodynamics Primer• Thermodynamics describes IF a reaction CAN

occur at some condition (T, P, composition typically)

• Second Law of thermodynamics:

• G=H – TS– Where G, Gibb’s free energy determines IF the

REACTION will go forward (-G=spontaneous)– H is enthalpy – has to do with heat…– S is entropy – has to do with bonds and order…

Thermodynamics vs. Kinetics

• Thermodynamics – comparing the potential ENERGY of things what is more stable? Will a reaction occur at some T,P, soln, melt composition go or Not?

• Kinetics IF thermodynamics says YES, the reaction should occur (always toward lower energy!) kinetics determines how fast

• Minerals out of equilibrium pass the thermodynamic test but the kinetics of their reaction is very slow…

Phase diagrams• Tool for ‘seeing’ phase transitions

• H2Oice H2Oliquid

• Reaction (line) governed by G=H – TS

• Phase Rule:– P+F=C+2– Phases coexisting + degrees of freedom =

number of components + 2– Degree of freedom 2= either axis can change

and the phase stays the same where??

Phase diagrams• Let’s think about what

happens to water as conditions change…

• P+F=C+2

• Point A?

• Point B?

• Point C?

A B

C

Mineral Assemblages in Metamorphic Rocks

• Equilibrium Mineral Assemblages• At equilibrium, the mineralogy (and the

composition of each mineral) is determined by T, P, and X

• Relict minerals or later alteration products are thereby excluded from consideration unless specifically stated

The Phase Rule in Metamorphic Systems

• Phase rule, as applied to systems at equilibrium:

F = C - P + 2 the phase rule

P is the number of phases in the system

C is the number of components: the minimum number of chemical constituents required to specify every phase in the system

F is the number of degrees of freedom: the number of independently variable intensive parameters of state (such as temperature, pressure, the composition of each phase, etc.)

The Phase Rule in Metamorphic SystemsConsider the following three scenarios:

C = 1 (Al2SiO5) F = 1 common F = 2 rare F = 3 only at the

specific P-T conditions of the invariant point

(~ 0.37 GPa and 500oC)

Figure 21-9. The P-T phase diagram for the system Al2SiO5

calculated using the program TWQ (Berman, 1988, 1990, 1991). Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.

Metamorphic facies• P-T conditions, presence of fluids induces

different metamorphic mineral assemblages (governed by thermodynamics/ kinetics)

• These assemblages are lumped into metamorphic facies (or grades)

Aluminosilicate Minerals

Andalusite Kyanite Sillimanite

• SILLIMANITE: Orthorhombic: Octahedral Al chains (6-fold) are crosslinked by both Si and Al tetrahedra (4-fold).

• ANDALUSITE: Orthorhombic: 5-coordinated Al; Same octahedral (6-fold) chains.

• KYANITE: Triclinic: All the Al is octahedrally coordinated (6- and 6-fold).

•Clearly, changes in structure are in response to changing P and T. Result is changes in Al coordination. •Phase transformations require rebonding of Al. Reconstructive polymorphism requires more energy than do displacive transformations. Metastability of these 3 are therefore important (Kinetic factors limit equilibrium attainment).•All 3 are VERY important metamorphic index minerals.

Aluminosilicate Minerals

• 3 polymorphs of Al2SiO5 are important metamorphic minerals

Andalusite Kyanite Sillimanite

Topaz• Aluminosilicate mineral as well, one oxygen

substituted with OH, F

• Al2SiO4(F,OH)2

• Where do you think Topaz forms??

Serpentine Minerals

• Mg3Si2O5(OH)4 minerals (principally as antigorite, lizardite, chrysotile polymorphs)

• Forms from hydration reaction of magnesium silicates– Mg2SiO4 + 3 H2O Mg3Si2O5(OH)4 + Mg(OH)2

forsterite serpentinebrucite

• Asbestosform variety is chrysotile (accounts for 95% of world’s asbestos production MUCH LESS DANGEROUS than crocidolite)

Phyllosilicates

Serpentine:Serpentine: Mg Mg33 [Si [Si22OO55] (OH)] (OH)44

T-layers and T-layers and tritriocathedral (Mgocathedral (Mg2+2+) layers ) layers

(OH) at center of T-rings and fill base of VI layer (OH) at center of T-rings and fill base of VI layer

Yellow = (OH)Yellow = (OH)

T T O O -- T T O O -- T T OO

vdwvdw

vdwvdw

weak van der Waals bonds between T-O groups weak van der Waals bonds between T-O groups

Serpentine

Octahedra are a bit larger than tetrahedral Octahedra are a bit larger than tetrahedral match, so they cause bending of the T-O match, so they cause bending of the T-O layers (after Klein and Hurlbut, 1999).layers (after Klein and Hurlbut, 1999).

Antigorite maintains a Antigorite maintains a sheet-like form by sheet-like form by

alternating segments of alternating segments of opposite curvatureopposite curvature

Chrysotile does not do this Chrysotile does not do this and tends to roll into tubesand tends to roll into tubes

Serpentine

The rolled tubes in chrysotile resolves the apparent The rolled tubes in chrysotile resolves the apparent paradox of asbestosform sheet silicatesparadox of asbestosform sheet silicates

S = serpentine T = talcS = serpentine T = talcNagby and Faust (1956) Am. Mineralogist 41, 817-836.

Veblen and Busek, 1979, Science 206, 1398-1400.

Chlorite• Another phyllosilicate, a group of

difficult to distinguish minerals

• Typically green, and the dominant and characteristic mineral of greenschist facies rocks

• Forms from the alteration of Mg-Fe silicates (pyroxenes, amphiboles, biotite, garnets)

Prehnite-Pumpellyite

• Minerals related to chlorite, form at slightly lower P-T conditions

• Prehnite is also green, pumpellyite

Micas• Biotite and Muscovite are also important

metamorphic minerals (muscovite often the principle component of schists)

• Phlogopite – similar to biotite, but has little iron, forms from Mg-rich carbonate deposits and a common mineral in kimberlites (diamond-bearing material)

• Sericite – white mica (similar to muscovite) – common product of plagioclase feldspar alteration at low grades

Zeolites• Diverse group of minerals forming at lower

metamorphic grades• Framework silicas, but characteristically

containing large voids and highly variable amounts of H2O

– Name is from the greek – meaning to boil stone as the water can de driven off with heat

– Voids can acts as molecular sieves and traps for many molecules

– Diversity of minerals in this group makes a for a wide variety of sieve and trapping properties selective for different molecules

Epidote Group

• Sorosilicates (paired silicate tetrahedra)

• Include the mineral Epidote Ca2FeAl2Si3O12(OH), Zoisite (Ca2Al3Si3O12(OH) and clinozoisite (polymorph)

Garnets

Garnet (001) view blue = Si purple = A turquoise = BGarnet (001) view blue = Si purple = A turquoise = B

Garnet: AGarnet: A2+2+33 B B3+3+

22 [SiO [SiO44]]3 3

““Pyralspites”Pyralspites” - B = Al - B = AlPyPyrope: Mgrope: Mg33 Al Al22 [SiO [SiO44]]3 3

AlAlmandine: Femandine: Fe33 Al Al22 [SiO [SiO44]]33

SpSpessartine: Mnessartine: Mn33 Al Al22 [SiO [SiO44]]33

““Ugrandites”Ugrandites” - A = Ca - A = CaUUvarovite: Cavarovite: Ca33 Cr Cr22 [SiO [SiO44]]33

GrGrossularite: Caossularite: Ca33 Al Al22 [SiO [SiO44]]33

AndAndradite: Caradite: Ca33 Fe Fe22 [SiO [SiO44]]33

Occurrence:Occurrence:Mostly metamorphicMostly metamorphicSome high-Al igneousSome high-Al igneousAlso in some mantle peridotitesAlso in some mantle peridotites

Staurolite• Aluminosilicate - Fe2Al9Si4O22(OH)2

• Similar structure to kyanite with tetrahedrally coordinated Fe2+ easily replaced by Zn2+ and Mg2+

• Medium-grade metamorphic mineral, typically forms around 400-500 C– chloritoid + quartz = staurolite + garnet– chloritoid + chlorite + muscovite = staurolite + biotite +

quartz + water

• Degrades to almandine (garnet at higher T)– staurolite + muscovite + quartz = almandine +

aluminosilicate + biotite + water

Actinolite

Metamorphic Facies• Where do we find

these regimes of P-T ‘off’ of the typical continental isotherms??

• How is the environment that forms a blueschist facies rock different from one forming a hornfels?

• Table 25-1. The definitive mineral assemblages that characterize each facies (for mafic rocks).

Metamorphic Facies

• Miyashiro (1961) initially proposed five facies series, most of them named for a specific representative “type locality” The series were:

1. Contact Facies Series (very low-P)

2. Buchan or Abukuma Facies Series (low-P regional)

3. Barrovian Facies Series (medium-P regional)

4. Sanbagawa Facies Series (high-P, moderate-T)

5. Franciscan Facies Series (high-P, low T)

Facies Series

Fig. 25-3.Fig. 25-3. Temperature-Temperature-pressure diagram pressure diagram showing the three showing the three major types of major types of metamorphic metamorphic facies series facies series proposed by proposed by Miyashiro (1973, Miyashiro (1973, 1994). 1994). Winter Winter (2001) An (2001) An Introduction to Introduction to Igneous and Igneous and Metamorphic Metamorphic Petrology. Petrology. Prentice Hall.Prentice Hall.

Isograds

• Lines (on a map) or Surfaces (in the 3D world) marking the appearance or disappearance of the Index minerals in rocks of appropriate compositione.g. the ‘garnet-in isograd’; the ‘staurolite-out isograd’Complicated by the fact that most of these minerals are solid solutions

• Isograds for a single shale unit in southern Vermont

• Which side reflects a higher grade, or higher P/T environment?