The document discusses mineral paragenesis, which refers to the time-successive order that minerals form in an ore deposit. There are two main approaches to establishing the paragenetic sequence: 1) studying how minerals fill open spaces, and 2) studying alteration reactions and replacement relations between minerals. The document focuses on the second approach and describes different types of replacement textures that can occur as physico-chemical conditions change and earlier mineral phases become unstable and are replaced by more stable phases. Exsolution textures, where a solid solution separates into two phases upon cooling, and replacement textures, where one mineral is chemically altered to form a new phase, are discussed in detail.
The document discusses mineral paragenesis, which refers to the time-successive order that minerals form in an ore deposit. There are two main approaches to establishing the paragenetic sequence: 1) studying how minerals fill open spaces, and 2) studying alteration reactions and replacement relations between minerals. The document focuses on the second approach and describes different types of replacement textures that can occur as physico-chemical conditions change and earlier mineral phases become unstable and are replaced by more stable phases. Exsolution textures, where a solid solution separates into two phases upon cooling, and replacement textures, where one mineral is chemically altered to form a new phase, are discussed in detail.
The document discusses mineral paragenesis, which refers to the time-successive order that minerals form in an ore deposit. There are two main approaches to establishing the paragenetic sequence: 1) studying how minerals fill open spaces, and 2) studying alteration reactions and replacement relations between minerals. The document focuses on the second approach and describes different types of replacement textures that can occur as physico-chemical conditions change and earlier mineral phases become unstable and are replaced by more stable phases. Exsolution textures, where a solid solution separates into two phases upon cooling, and replacement textures, where one mineral is chemically altered to form a new phase, are discussed in detail.
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 1996 2 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. 1996 3 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 1996 4 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 1996 5 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 1996 6 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. 1996 7 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. 1996 8 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.