Chapter 5

Mechanisms of metamorphism and

metasomatism on the local mineral scale :
The role of dissolution-reprecipitation during
mineral re-equilibration
Andrew Putnis & Håkon Austrheim
 Equilibration at a crystal - fluid interface

µfluid

µcryst

crystal fluid

The fluid may be an aqueous solution (or a melt), out of

equilibrium with the crystal.
 Equilibration at a crystal - fluid interface

diffusion profile
µfluid

µcryst

crystal fluid

Equilibration by volume diffusion from the fluid into the crystal?

 Equilibration at a crystal - fluid interface

recrystallisation front

crystal fluid

Equilibration by interface-coupled dissolution-precipitation?

a b

c d

Reaction interfaces on an outcrop scale

 The core of the garnet
(granulitic) has lower Fe/Mg ratio
than the lighter (eclogitic) rim

granulite

granulite

eclogite
 The core of the garnet has lower
Fe/Mg ratio than the lighter rim

recrystallisation front

crystal fluid

Pollok et al., (2008)

Equilibration by interface-coupled dissolution-precipitation.

In all the examples we have studied, and examples
taken from the literature, equilibration involves
recrystallisation to form a more stable phase.

See: Putnis (2009) Mineral Replacement Reactions In: Reviews in

Mineralogy and Geochemistry Vol. 70 (Thermodynamics and Kinetics of
Water-rock interaction)

The free energy drive for mineral replacement reactions

can be very small:

e.g. Uptake of 133Ba by BaSO4 from a saturated solution

at 230C involves a dissolution-precipitation mechanism.
Curti et al., (2010) Geochim. Cosmochim. Acta 74, 3553-3570
 recrystallisation front

BaSO4 enriched with 133Ba Uptake of 133Ba by BaSO4 from

a saturated solution at 230C
involves a dissolution-
Fluid saturated precipitation mechanism.
with respect to
BaSO4 but Curti et al., (2010) Geochim. Cosmochim.
doped with Acta 74, 3553-3570
133Ba

BaSO4

Suggests that small free energy differences may be sufficient to

drive interface-coupled dissolution-precipitation reactions.
 What is interface-coupled dissolution-precipitation?

crystal

a b c d e
(a) Dissolution of even a few monolayers of the parent crystal may result in an
interfacial fluid layer which is supersaturated with respect to another phase

(b) This product phase may nucleate on the surface of the parent

(c) The porosity generated depends on both the solid molar volume change and the
relative solubilities of parent and product in the fluid

(d-e) A reaction/replacement interface moves through the parent crystal

Pseudomorphic Mineral Replacement

Examples
Example 1:

Experiment

Single crystal aragonite replaced by calcite

BSE of cross sections of an aragonite crystal partially
replaced by calcite in a hydrothermal experiment
The dissolution of aragonite and precipitation of calcite
results in porosity in the calcite

allowing fluid to access the dissolution-precipitation front

Even though the molar volume of calcite is greater than

that of aragonite
Raman map of the 18O
distribution when the fluid
is enriched in 18O

The calcite is enriched in

18O showing that oxygen is

also replaced in the

transformation

i.e. coupled dissolution-

precipitation
The aragonite  calcite transition can also take place
by a solid state mechanism*.

* solid state mechanism - one that involves the

reorganisation of the structure without the need for
a fluid phase (i.e. no dissolution and
reprecipitation)

The activation energy for the ‘wet’ process is about half

that of the ‘dry’ process, so that at a temperature of
200oC the transformation is faster by a factor of about
1012.
Example 2:

Experiment

Calcium carbonate (Carrara marble) replaced by apatite

Cross section of cube of Carrara marble reacted with phosphate solution at
1500C for 1 week

Calcite is
partially
replaced by
apatite
Ca5(PO4)3(OH)

BSE image: L.Jonas

 calcite is being replaced
by apatite, Ca5(PO4)3(OH)

Experiments with Carrara marble with a hydrothermal fluid containing

phosphate ions. The dissolution of the calcite results in a Ca-P bearing fluid,
from which apatite nucleates. The dissolution and precipitation are coupled so
that the parent phase is replaced by the product.
porous apatite replacing calcite
How relevant is this to metamorphism?
 The conversion of gabbro to eclogite

Image: Timm John

Gabbro Eclogite

Igneous texture of the gabbro preserved: garnet replaces plagioclase,

omphacite replaces augite

from Putnis & John, Elements 6, 2010

from Putnis & John, Elements 6, 2010
Albitisation – one of the most common
metasomatic reactions
Fluid - induced chemical
reequilibration of feldspars

Albitisation of granitoid in
the Bamble sector, Norway

Plagioclase (Na,Ca)
feldspar replaced by
albite (NaAlSi3O8)
Fluid - induced chemical
reequilibration of feldspars

Albitisation of granitoid in
the Bamble sector, Norway

Plagioclase (Na,Ca)
feldspar replaced by
albite (NaAlSi3O8)
Feldspar replacement microstructure
Note the
porosity
developed
An22Ab77
in the
product
phase

The crystal
An2Ab95 structure
is
preserved
across the
sharp
interface
Engvik et al. (2008) Can. Mineral
What happens to the ’charged’ fluid which has albitised the
country rock? - Ore deposits

after Korneliussen et al., 2000

In Australia, < 100 kms south west of Broken Hill

Albitisation in the Curnamona Province, South Australia

Albitisation in the Curnamona Province, South Australia
How much saline fluid is needed to albitise such large volumes?
How does the fluid move through the rock?

Albitisation in the Curnamona Province, South Australia

Ultimately albitisation can replace the whole rock

David Ettner

Albite quarry in Turkey

Albite (dark) growing within phlogopite (pale)during albitisation

Ab

Image: Håkon Austrheim

Albite (dark) growing within phlogopite (pale) during albitisation

How is this “extra volume” created?

Ab

Image: Håkon Austrheim

Metasomatism and Metamorphism

Both involve dissolution-transport-precipitation

Is it just a question of the spatial scale?

Can we define any equilibrium reactions?

 Metasomatic rocks often are not recognised as such......
but how do we recognise a “metamorphic event”?

Vernon RH, White RW, Clarke GL (2008) False metamorphic events

inferred from misinterpretation of microstructural evidence and P-T
data. Journal of Metamorphic Geology, 26, 437-449.

In Vernon’s context a “metamorphic event” constitutes a

series of reactions through P,T space, and he addresses
the problem of recognising textures which indicate crossing
a particular P,T reaction line., i.e. recognising phases which
define an equilibrium assemblage at some point in time.
Vernon identifies two reliable microstructural
criteria for recognising a metamorphic event:

• partial replacement textures

• reaction coronas at grain boundaries
between two reacting phases
Metasomatic rocks often are not recognised as such......
but how do we recognise a “metamorphic event”?

Two typical partial replacement textures:

An22

An2

Apatite-OH replacing Apatite-Cl Albite (An2) replacing plagioclase (An22)

Metasomatic rocks often are not recognised as such......
but how do we recognise a “metamorphic event”?

Two typical partial replacement textures:

In these examples the equilibrium (if any)

An
is
22
between the product phase and the
interfacial fluid
and
not between the parent and the product
An 2

solid phases

Apatite-OH replacing Apatite-Cl Albite (An2) replacing plagioclase (An22)

A sharp interface between two “apparently co-
existing’ phases does not mean they are in
equilibrium.

Partial replacement textures cannot be used

as a criterion for a ‘metamorphic event’ in the
sense of crossing a reaction line in P,T space.
Vernon identifies two reliable microstructural
criteria for recognising a metamorphic event:

• partial replacement textures

• reaction coronas at grain boundaries
between two reacting phases
 Corona textures

• A concentric
arrangement of one
or several rims of
minerals around a
core mineral

• Dimensions: µm to
dm across

• ”Easy” to interpret
and frequently used
to unravel the history
of rocks
Granulite from the Bergen Arcs, Norway
 Interpretation

A reaction texture
formed due to
changing P and T.

B
Assumptions:
C
Core is older than D
the rim E

The system is A
closed
Solid-solid reaction Reaction deduced:
A+ B= C +D + E
Converting a gabbro
to a granulite facies rock
 Application in
• P-T diagram
petrology

• Provided we know
the stability fields

Pressure (P)
of the mineral
assemblages, we
can infer the P - T
path.

Temperature (T)
 Mechanism of Corona formation

1. Nucleation at the
contact between the
reacting minerals
2. Diffusion of material
through the product
mineral
3. The growth must slow
down with time Ol
4. New rims may Opx
nucleate as P and T Cpx
continue to change
Grt
5. Regarded as solid –
solid reaction Plag
Corona formation
and fracturing

Double opx rims

around olivine

Discontinuous rims. oliv

How can we explain
this?
plag
 Are coronas a reliable indicator of a “metamorphic event”?
A typical reaction corona:

spr + plag
Straume and
Austrheim, 1999

Reaction between garnet + kyanite to plagioclase + sapphirine

along grain boundaries (but not all grain boundaries)
Are coronas a reliable indicator of a metamorphic event?

(i) The grt + ky

reaction only takes
place on some
interfaces
spr + plag
(ii) The plag contains
>10% albite
component

Straume and Austrheim, 1999

Conclusion: Reaction has only taken place where an Na-

bearing fluid has infiltrated
Partial reactions on some grain boundaries and not others is
typical of such corona reaction textures and is more
consistent with a metasomatic reaction limited by fluid
availability than with a solid state volume diffusion controlled
reaction.

Both of the Vernon et al. “reliable criteria” for a metamorphic

event are indicators of metasomatism.

The equilibrium (if any) is not likely to be that between the parent
and product phases but between the fluid and the product.
The Journal of Geology, 26, 542-554 (1918)

“Metamorphic reactions should be balanced on volume”

 The conversion of gabbro to eclogite

Image: Timm John

Gabbro Eclogite

Igneous texture of the gabbro preserved: garnet replaces plagioclase,

omphacite replaces augite
The problem of identifying metasomatism when there is no
chemical or physical reference frame.

Small zircon crystals are

often associated with ilmenite
grain boundaries in a wide
range of rock types.

During metasomatism where

the ilmenite and hornblende
are replaced by phlogopite,
the zircon may remain
unreacted and outlines the
position of the former ilmenite
grain boundary.

Note: no deformation has

been involved in this
replacement.
Austrheim et al., 2008
Serpentinisation of olivine : Volume increase?
 Molar volumes:

Olivine ~ 46.5 ccs

Antigorite ~ 110 ccs

2Mg2SiO4 + 2H+ + 2H2O  Mg3[Si2O5](OH)4 + Mg2+

3Mg2SiO4 + H4SiO4 (aq) + 2H2O  2Mg3[Si2O5](OH)4

5Mg2SiO4 + 2H2O +8H+  2Mg3[Si2O5](OH)4 + 4Mg2+ + H4SiO4(aq)

 2
0

Pressure (kbars)
Jadeite + Quartz
1
5

1 Albite
0

200 400 600 800

0
Temperature C

NaAlSi3O8  NaAlSi2O6 + SiO2

Does this reaction represent the actual mechanism?

 Albite being replaced
isovolumetrically by jadeite
Albite

NaAlSi3O8  NaAlSi2O6 + SiO2(aq)

???
Jadeite
Molar volumes:
Albite~ 100.1 ccs
a 0.2 mm
Jadeite~ 60.4 ccs

To balance the reaction on

volume:
Albite
0.6 Albite + Fluid  1.0 Albite

To mass balance the reaction the

Fluid phase must add 0.4 moles
Jadeite of Na and Al, and 0.2 moles of Si

b Image: R. Rysza
 Jadeite being replaced
isovolumetrically by albite

NaAlSi2O6 + SiO2(aq) NaAlSi3O8

???

Molar volumes:
a Albite~ 100.1 ccs
Jadeite~ 60.4 ccs

To balance the reaction on

volume:

1.6 Jadeite  1.0 Albite + Fluid

To mass balance the reaction the

Fluid must remove 0.6 moles of
Na and Al, and 0.2 moles of Si

b Image: M.Shigeno
Some problems this raises

How do we determine the thermodynamics of these open

system reactions?

The textures imply a very significant element exchange in

……… the fluid phase?

How does the fluid pass through the minerals?

Partial transformation of single crystal coesite (cubic,
isotropic) to polycrystalline low quartz (trigonal, anisotropic)

0.2 mm 0.5 mm
Image: J.R.Smyth Image: J.R.Smyth
Element maps of metasomatic tournaline. The Ca and Ti distribution preserve
chemical features of the precursor phases.

Bast R. MSc 2010

Pervasive metamorphism requires pervasive fluid
infiltration and diffusion of elements through the fluid.

How do fluids move through low permeability rocks?

1….Reaction generated porosity.

Plenty of experimental evidence for interface-coupled

dissolution-precipitation, which involves fluids accessing
internal reaction interfaces within crystals.

Fluid infiltration through nanopores which are generated

within the product phase due to differences in the relative
molar volumes and solubilities of parent and product
phases.
Pervasive metamorphism requires pervasive fluid
infiltration and diffusion of elements through the fluid.

How do fluids move through low permeability rocks?

2. Reaction generated fractures …….. or dissolution

pathways? The product phase nucleates within these
fractures.
Implications of interface-coupled dissolution-precipitation as a
mechanism of mineral replacement

Fluid control of metamorphic reactions

Austrheim et al., (1987), Pollok et al., (2008)

 Implications of interface-coupled dissolution-precipitation as a
mechanism of mineral replacement

Is the fluid more than just a catalyst in a metamorphic reaction?

A + B + F1  C + D + F2 ?
or
Pressure

C+D

A+ B

Temperature
Acknowledgements

This work is supported by:

The EU ITN Network Delta-Min

(Mechanisms of Mineral Replacement
Reactions)

The Humboldt Foundation