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Int r oduct ion t o Or e Micr oscopy II


Erich U. Petersen
MINERAL PARAGENESIS
The term 'paragenesis' refers to the time-successive order of formation of a group
of associated minerals within a particular deposit. Since the great majority of ore mineral
occurrences have been formed by several distinct periods of mineralization, the complete
description of the paragenesis of a deposit involves establishing the order in which the
constituent minerals have been formed and the sequence of resorptions and replacements
that have occurred. In order to establish the paragenetic sequence in a deposit, two broad
approaches are useful:
1. the study of open-space fillings
2. the study of alteration reactions - replacement relations among the ore minerals
In near-surface regimes, rocks yield by fracturing rather than by flowage; open
channel ways develop and layers or crusts of minerals may be deposited from successive
pulses of fluid that pass through the fractures. By searching for variations in mineral grain
size, symmetrical banding, and certain diagnostic structures (comb, cockade), one can
recognize open-space filling and by studying the composition of sequential crusts along the
walls of the vein, one can determine the paragenetic sequence. Three kinds of ore mineral
deposition may be considered:
a) simultaneous deposition (in which two or more minerals are formed from the
beginning to the end of the process) e.g., galena-sphalerite, tetrahedrite-
tennantite-pyrite
b) overlapping deposition (in which two or more minerals have formation periods
that overlap in part) e.g., sphalerite-pyrite
c) successive deposition (in which the formation periods of two or more minerals
succeed each other with practically no overlap) e.g., sulfide-carbonates
In this review we shall concentrate on the second approach - - the study of alteration
reactions - replacement relations of ore minerals - - in determining the paragenetic sequence
of minerals present in polished sections. During the deposition of minerals, the physico-
chemical conditions may change and this leads to the replacement of mineral phases which
become unstable by phases that are more stable in the new environment. After the final
changes, the minerals which remain have survived together and will, to some extent,
provide evidence of these last changes; one must not, however, conclude that all of them
were stable phases, even during these last changes, nor that they are really stable under the
conditions in which they are now found. All textures that show evidence that the 'primary'
mineral content resulting from deposition has been changed may be classed under the
heading 'replacement-alteration textures'. On the basis of Schneiderhons (1935) work,
three broad categories are distinguished: (i) deposition textures, (ii) exsolution textures,
and (iii) replacement textures. The last two types will be considered next.
1. Exsolution Textures
A solid solution in which two different elements A and B are completely
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interreplaceable at high temperatures (in disordered mineral structures) but not at lower
temperatures (in ordered mineral structures) will tend to break down on cooling into two
separate phase, one rich in A and the other in B. This breakdown of a homogeneous solid
solution is known as exsolution. The extraneous materials which are forced out of the
mineral structure upon cooling tend to accumulate along cleavage surfaces or
crystallographically controlled directions, in small blebs and blades. Lamellar textures are
especially diagnostic of exsolution. Slow cooling, anomalous mixtures, small foreign
inclusions, and tectonic stresses are some factors that facilitate exsolution. Silicates and
some oxides which have stable and compact lattices exsolve with much greater difficulty
than do the sulfide minerals.
Some exsolutions are chemically 'closed', that is, the previously simple solid
solution is chemically equivalent to the composition of the disintegration products. An
example is perthite of 70 percent orthoclase and 30 percent albite lamellae that was earlier a
homogeneous high temperature feldspar with 70 percent Or and 30 percent Ab
composition. An ore example is hematite-ilmenite.
Other exsolutions are chemically 'open' in that a change in the stoichiometric
relationships is observed. For example, if a feldspar exsolves to yield orthoclase and small
hematite plates, then either the solid solution could not have been expressible by the
feldspar formula or some elements were added or removed. Another example is the
ilmenite-magnetite pair. No solid solution exists between the endmembers, but blebs of
magnetite are found in ilmenite and vice versa - - a phenomenon attributed to the expulsion
of iron from ilmenite and titanium from magnetite. This exsolution is not due to a solvus
separation. Note that a high-temperature solid solution may form disintegration
(exsolution) products that are quite different in their chemistry and crystallography from the
initial solid solution. Such a complete re-mineralization is quite similar to the exsolution
phenomenon. Examples of re-mineralization are: decomposition of a hematite-ilmenite into
rutile and magnetite ('tie line switch') and the decomposition of bornite into chalcocite or
chalcopyrite.
Often two or more generations of exsolutions can be observed in a mineral, for
example, sphalerite will disintegrate to form chalcopyrite which in turn will contain
exsolutions of FeS (mackinawite). An exsolution bleb which is separated at high
temperatures is often itself still a complex and non-stoichiometric solution with which a
further decrease in temperature will tend to exsolve new compounds by exsolution in
several stages. A different situation is observed in the FeTiO
3
-Fe
2
O
3
system in which the
strong supersaturation of one component in the mineral leads to the formation of second
generation exsolution discs.
The forms of exsolution bodies are often quite similar to those of replacement
textures or to those of the simultaneous oriented crystallization. In a rigorous sense, one
could view exsolution as a type of replacement phenomenon, for in the regions in which
new exsolved minerals formed, the parent mineral must have diffused outwards and the
exsolved mineral inwards. This latter diffusive movement is, therefore, a type of
replacement. Many oxide exsolutions will maintain their geometry (i.e. outline) after their
formation. However, in the case of sulfides, and especially soft sulfides, the surface
tension and velocity of migration of species is sufficiently large even at moderate
temperatures that sharp-cornered exsolution bodies will be rounded off, lamellae will flow
into rows of dots, and fine exsolution bodies will coalesce into larger globs. The resulting
forms are quite similar to typical replacement textures and thus may not always be
interpreted correctly as primary exsolutions. Relicts of exsolution textures not destroyed in
such 'collectivization' may still be present in 'armored' inclusions, for example, quartz.
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Some forms of exsolution blebs are outlined below:
1. Variable in size and form, not uniformly distributed. If the high temperature
mineral was compositionally zoned with the highest concentration of the extraneous
element in the center of the grain, one might see a greater concentration of
inclusions in the core of the grain as opposed to the periphery.
2. Number and size different along different directions in the parent mineral. Cracks,
twin lamellae, inclusions, lattice distortions often cause preferred orientation of
blebs.
3. Irregular forms - - spontaneous vs. coalesce. (147, 148, 167)
4. Dispersions of regular shaped particles, for example, cubic minerals show stars or
octahedra development. (151, 152).
5. Lamellar texture well developed among cubic and hexagonal minerals, (147,156,
157, 158, 159, 160, 169).
6. Myrmekitic - - often thought to be exsolution products where lattice structure of
components is similar. (171)
7. Flame structure of pentlandite in pyrrhotite. (166)
8. Multiple exsolution. (172)
9. Some complications messing up the picture - - first exsolved mineral may
subsequently become transformed; first exsolution mineral may disintegrate into
several later components.
The following table lists some exsolution textures. The source of the data is Ramdohr
(1969).
Characteristic type Relative amount of
Parent Mineral Exsolved Phase of intergrowth parent exsolved
1 bornite chalcopyrite individual lamellae 1:3
2 chromite hematite platelets 1:5
3 chromite ilmenite platelets 1:10
4 chalcocite bornite network 1:2
5 chalcocite chalcopyrite - -
6 chalcopyrite bornite - -
7 chalcopyrite pyrrhotite - -
8 enargite chalcopyrite - 1:10
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9 galena argentite dispersion 1:10
10 hematite ilmenite discs (0001) all
11 ilmenite magnetite thin plate-like bodies (111) 1:5
12 ilmenite hematite discs (0001) all
13 ilmenite rutile plates 1:10
14 magnetite ulvspinel network (100) 1:3
15 magnetite ilmenite platelets 1:1
16 pentlandite pyrrhotite dispersion 1:4
17 pentlandite chalcopyrite cellular-net shaped 1:10
(similar and more common
as replacement)
18 pyrrhotite pentlandite myrmekitic (flames) 1:5
19 pyrrhotite chalcopyrite - 1:4
20 pyrrhotite magnetite platelets (v. characteristic) 1:10
21 sphalerite pyrrhotite - -
22 sphalerite chalcopyrite emulsion 1:4
23 sphalerite cpy-po-cub emulsion 1:4
2. Replacement Textures
When a mineral which formed early in the paragenetic sequence is chemically
altered to form a new phase, the parent mineral is said to have undergone 'replacement'.
Such replacement of one mineral by another can be partial, in which case some remnants of
the parent grains are preserved, or complete, wherein no trace of the original mineral can be
observed. The associated replacement textures show a considerable variety of form owing
to the mobility and frequent transformations of the minerals involved. The genetic
significance of some replacement textures will be outlined below, but first, a few general
remarks on the replacement phenomena are in order:
Time of replacement :
1) Immediate during precipitation of coexisting minerals. cf. analogy of crystallization
in a simple binary system in which the crystals that have been precipitated first are
altered by the remaining solution (melt) and are replaced by solid solutions
(crystals) of different composition, or by another type of crystal with resultant
excellent replacement textures. Complete or partial resorption of phases that are
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initially precipitated.
2) Later hydrothermal - - minerals not in equilibrium with bypassing solutions.
3) Metamorphic attack and re-equilibration.
4) Weathering (oxidation and supergene enrichment).
Mechanism of Replacement :
Early minerals undergo replacement when altering solutions circulate and penetrate
along fissures and cracks between individual mineral grains or along cleavage planes,
twin planes and crystal defects in individual crystals. A front of alteration can often be
observed as solutions penetrate through a given rock. The later mineral may replace
the earlier around the periphery of the latter without penetrating it, or it may penetrate
and then attack from the core outwards. Successive minerals may be deposited from
single evolving solutions with complete or partial resorption of phases that were
initially precipitated.
Textures of repl acement :
The relative amounts of the later and the earlier mineral produce textures to which
different names have been given - - cataclastic, pseudo-eutectic, dendritic, etc.
Unfortunately, most replacement texture classifications have genetic connotations
associated with them and are not based on an objective, descriptive approach. Such
genetic classifications are dangerous and ought to be avoided for many textures can
form in a variety of ways.
Form of replacements related to: hardness, cleavages, degree of cataclasis, chemical
stability of the lattice structure, T, pH, Eh, composition of altering fluids (are they
saturated with respect to components in the mineral that is being altered?)
The following capsule descriptions of textures are based on Rahmdor's proposed
classification (1969):
1. Filigree network -- (209) favors ore minerals lacking definite cleavage or showing
cataclastic texture.
2. Inclusions -- Inclusions are small particles of one mineral included in the material of
another, and they represent a kind of texture. Inclusions can be either the relicts of a
mineral that is being replaced, or else the early signs of a new mineral that is
replacing the old; otherwise they can consist of a phase that has been unmixed from
the host crystal. Schneiderhon (1943) has established four types of relations
between an inclusion and a host crystal:
a) Older foreign crystal inclusions engulfed by a growing new mineral (e.g.,
chromite in Pt) - No Reaction Relation.
b) Inclusions unmixed from the material of the host mineral after the primary
crystallization of this (e.g., sphalerite in galena) - Exsolution.
c) Transformed inclusions that have been altered (e.g., 'exploded bombs' of
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pyrite) - Replacement.
d) Inclusions which are later than the host (e.g., zones of cementation and
oxidation).
Inclusions are often quite irregular in shape, but in other cases they show regular
orientation in the host crystal, as was observed in the discussion of exsolution
phenomena. The relation of the inclusion to the host mineral is often of great
importance in determining the paragenetic sequence in a section. A few examples
of inclusions and their host mineral are given below:
Inclusion Enclosing Mineral
argentite galena
bornite chalcopyrite
bornite chalcocite
breithauptite niccolite
cubanite cuprite
chalcopyrite sphalerite
chalcopyrite enargite
gold pyrite
hematite magnetite
ilmenite magnetite
ilmenite chromite
pyrrhotite sphalerite
pyrrhotite chalcopyrite
pentlandite pyrrhotite
(211-217)
3. Shredded Texture -- resembles island form structures, typical concave replacement
relicts. (213)
4. Skeleton shaped textures -- rapid growth of corners and edges of crystals leads to
incorporation of inclusions. (218)
5. Lattice forms -- develop in minerals with well-developed cleavage cf. pyrite
replaced by sphalerite. (221)
6. Zonal replacements -- cf. chromite replaced by niccolite along fractures and
preferentially along its marginal zones. (218)
7. Dendritic textures -- replaced along cleavage directions and along lines of
intersection of these. Invasion of solutions along twin lamellae. (219, 221)
8. Real frontal Replacements -- mineral lacks cleavage, fractures, grain boundaries
and inclusions and no zones of apparent inclusions. Thus, replacement 'fronts' set
in as irregular, blob-like forms often developing uniformly rounded and smooth
boundaries.
A rule of thumb that be helpful is that harder minerals are replaced by softer ones. For
example, the sequence pyrite < sphalerite < chalcopyrite < galena < argentite is quite
commonly observed.
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Examples of Important Ore Mineral Parageneses
Often one has the problem of identifying an unknown mineral in a polished section
(an understatement?). Sometimes certain textures or the nature of certain inclusion can give
indications which are useful in the determination of the unknown. One can generally
reduce the number of possibilities of what the unknown is by considering the assemblage
of minerals with which it occurs, i.e. the paragenesis can help. Certain minerals typically
occur in association with other minerals of a particular class or paragenesis; for example,
the assemblage py-po-sl-cpy-mt is common. Unfortunately, there are some minerals which
occur very widely in various ore bodies, and thus are not especially indicative of a
particular assemblage or environment of formation. Hence, neither can use be made of the
presence of other minerals to identify these, nor can use be made of their presence to
identify other minerals accompanying them. It is apparent that paragenesis can be useful in
determination only when one is concerned with minerals of relatively uncommon
occurrence or with those that are associated with relatively rare minerals. Several examples
of important parageneses are presented below.
1. Titanomagnetite-ilmenite paragenesis
Derivative of simatic magma
Titanomagnetite or ilmenite are early crystallization products from basaltic or gabbroic
rocks. Exsolution phenomena common: in gabbroic rocks at high solidification
temperatures. Titanomagnetites in which segregation lamellae of ilmenite occur are first
formed. At lower temperature, ilmenite or ilmenite borders to previously separated
magnetite grains form. Both phenomena may be seen in the same rock.
Ilmenite - shows twin lamellae commonly and hematite exsolution blebs.
2. Nickel-pyrrhotite paragenesis
Sudbury, Canada
Associated with gabbroic to quartz dioritic rocks, often rich in Pt. Deposit occurs both
intramagmatically as segregations and as hydrothermal formations; deposits associated
with parent rock as impregnations occurring in alien rocks (e.g. granites) as fissure
infillings.
Association: main minerals:
pyrrhotite, pentlandite
chalcopyrite always present
magnetite, ilmenite frequently as magmatic segregations from the rocks
which were impregnated by the hydrothermal sequences.
Bulk of paragenesis is always formed from pyrrhotite. Pentlandite, which usually
appears later, occurs: as (1) an intragranular film, from which it replaces the pyrrhotite,
(2) a migration into the pyrrhotite from clusters; thus, pentlandite intrudes outward
from cluster in flame-shaped aggregates (3) may have the pentlandite forming primary
flame-shaped segregations. These are aggregates of irregular lens shape parallel to the
base of the intruded segregation particles of pyrrhotite.
Silicates are chlorite, actinolite.
Later alteration of sulfides: pyrrhotite to pyrite and pentlandite to bravoite into limonite.
At pH less than 7, possible to form marcasite from pyrrhotite and at higher Eh, possible
to form magnetite from pyrrhotite, starting as a rule from grain boundaries. Note that
this magnetite could not display exsolutions of ilmenite.
Paragenesis fairly uniform except that rarely see late-stage hydrothermal solutions
depositing other sulfides, cf. stibnite.
The initial parageneses were formed at relatively high temperature, so that it was
possible for cubanite to form.
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3. Chrome-spinel paragenesis
Segregation products of magma rich in Cr, and as a rule, peridotitic type.
Paragenesis highly uniform, consisting essentially of chrome-spinels c.f. chromite (Fe,
Mg) (Cr,Al,Fe)
2
O
4
and FeAl
2
O
4
-MgAl
2
O
4
spinels.
Sulfides are rare with chromite -- pyrrhotite or arsenides. Due to affinity of As for Ni,
and due to high Ni content of peridotite.
Host rock of chromite deposits - olivine and pyroxene rich; serpentine.
One can use paragenetic reasoning to distinguish between two similar looking
minerals in a section. As an example, consider the minerals ilmenite and manganite
(MnO(OH)). Both minerals are of generally similar properties and can easily be
distinguished in large grains. In very small grains, however, the paragenetic reasoning can
be useful, as they have two radically different modes of occurrence.
Ilmenite Manganite
Found especially in basic Characteristic of superficial and
igneous rocks low temperature formations - cement
Typical paragenesis: Typical paragenesis:
ilmenite manganite
magnetite goethite
chromite psilomelane
platinum limonite
pyrrhotite siderite
rutile
niccolite
pyrite
Clearly, just by observing the minerals in the section with which the 'unknown' mineral
occurs, one can without hesitation rule out several possibilities.

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