Sphalerite, pyrite and chalcopyrite.

Bayda, Oman







125m


Euhedral to poorly crystalline pyrite (light yellow-white, left) surrounds sphalerite (centre) which has suffered extensive replacement by
chalcopyrite; this is an extreme example of chalcopyrite disease. The replacement of sphalerite by very fine-grained chalcopyrite is
crystallographically controlled, following growth zones and poorly defined twinning. The differences in surface colour (orange to purple)
are due to orientation effects of the fine chalcopyrite inclusions. Under crossed polars the anisotropy effects are enormous. The outer
margin of the sphalerite (grey, top left) is chalcopyrite-free and belongs to a later generation of sphalerite. Quartz (dark grey with internal
reflections) is the gangue.


Polished block, plane polarized light, x 160, oil
Location: Lasail and Bayda, Semail Ophiolite. Oman

Lasail and Bayda formed in the short time interval between the eruption of footwall
basalts (Geotimes Unit) formed along a marginal basin spreading axis and a
hangingwall lava unit (Lasail Unit) associated with an off-axis seamount.
Major Minerals: Pyrite, chalcopyrite, magnetite, haematite
Minor Minerals: Sphalerite, marcasite
Trace Minerals: Include sphene, bornite, pyrrhotite, carrollite, cubanite, molybdenite, mackinawite,
native gold
Textures: Optical zoning of pyrite (related to the cobalt content) is common. Minor amounts of
cobaltian pyrite are associated with carrollite in chalcopyrite. Inclusions of mixed
pyrrhotite-chalcopyrite and pyrrhotite-chalcopyrite-cubanite occur within euhedral
pyrite and are due to the breakdown of iss. Both pyrite and sphalerite are extensively
replaced by chalcopyrite, pyrite along its cleavage, and sphalerite along twin planes
and grain boundaries
References: Haymon et al., 1984; Ixer et al., 1984, 1986; Haymon and Koski, 1985



Volcanogenic massive sulphide deposits




Modern ocean floor volcanogenic sulphides
There are more than a thousand volcanogenic massive sulphide deposits in the world. Collectively, they are
a major source of copper, lead and zinc, and are important producers of gold and silver. The deposits are
usually zoned and comprise massive syngenetic sulphide ores overlying an epigenetic stringer zone. They
are associated with acid to basic volcanics extruded in aqueous, usually submarine, conditions. There are
many classes and subclasses: amongst these are modem sulphide deposits including the 'black smokers',
their possible fossil equivalents in ophiolite sequences, plus Besshi and Kuroko deposits and many types of
metamorphosed massive sulphides.

Modern polymetallic sulphides were first discovered along the East Pacific Rise (21N) in 1978, followed
soon after by active hydrothermal vents associated with sulphides. Although presently none are mined, they
have some potential for copper, silver and zinc. Many such sites are known, most are associated with mid-
axis ridges but some are found close to off-axis volcanism, at seamounts. The earliest and hence best known
examples include those along the East Pacific Rise at 21N and 13N, along the Juan de Fuca and Explorer
ridges and the Galapagos Rift sulphide mounds. They are important because their formation conditions can
be measured directly and they show how little time is needed to produce appreciable tonnages of 'ore'. Similarly, their rapid oxidation and
destruction show the transitory nature of these deposits. They confirm the validity of the synsedimentary volcanogenic model and, indeed,
have become its paradigm. In this model, convecting hot water (mainly. sea water) leaches metals from the underlying volcanics and
returns to the seabed via faults, rifts or volcanic conduits. There, it mixes with normal sea water to precipitate sulphides and sulphates to
form sulphide mounds, sulphide-rich chimneys and plumes of 'black smoke' (very fine-grained pyrrhotite with minor sphalerite and pyrite)
and 'white smoke' (silica, baryte and pyrite).

The styles of mineralization and dominant sulphide mineralogy of modem seafloor sulphides are not
uniform. At 21N, copper, iron and zinc sulphides form chimneys resting on sulphide mounds; at Juan de
Fuca, zinc sulphides form mounds, whereas the massive sulphides found at the Galapagos Rift are
dominated by pyrite. (Rona, 1984)

Modern off-axis sulphides
There are few descriptions of sulphides associated with off-axis seamounts, but their mineralogy comprises major pyrite and marcasite,
plus chalcopyrite, pyrrhotite and covelline with minor zinc sulphide and cobaltian pyrite, together with baryte, quartz and opaline silica.
Limonite and manganese oxyhydroxide oxidation products are common. Many seamounts have thin cobaltian manganese oxide crusts but
little or no sulphide. (Lonsdale et al., 1982; Hekinian and Fouquet, 1985)

Massive sulphides in ophiolite sequences
Essentially these are copper-bearing massive pyrite deposits that produce by-product zinc, silver and gold.
Amongst the most discussed examples are those of the Troodos Mountains, Cyprus and this class of deposit
is often called the 'Cyprus-type'. The deposits are found within, or close to, basic pillow lava sequences; all
have massive sulphide ores overlying stringer zones and many have oxidized ochreous zones comprising
goethite, quartz and traces of maghaemite lying above the massive sulphides. The mineralogy of the massive
ores is dominated by pyrite together with variable amounts of chalcopyrite, sphalerite and pyrrhotite.
Subordinate ore types include chalcopyrite-bornite-pyrite and sphalerite-pyrite. Pyrite has euhedral and collomorphic generations and
shows extensive shattering and replacement by chalcopyrite; sphalerite also is replaced by chalcopyrite. The underlying stringer zone ores
are essentially quartz-pyrite-chlorite veinlets. The deposits are widely believed to be the fossil equivalents of the East Pacific Rise black
smoker-type of mineralization, although some authors have suggested, on mineralogical grounds, that the Galapagos sulphide mounds or
modern off-axis seamount sulphides are closer analogies. (Constantinou and Govett, 1972, 1973; Constantinou, 1976, 1980; Oudin and
Constantinou, 1984)

Sulphide deposits in the Oman ophiolite: Three massive sulphide deposits, Lasail, Bayda and Aarja, occur
within pillow lava units of the Semail ophiolite. They comprise massive pyrite with subordinate copper and
zinc-rich ores that overlie a quartz-pyrite-base metal sulphide-chlorite stringer zone in footwall basalts.
Lasail and Bayda are mineralogically similar but have significant differences from Aarja. All three deposits
have been interpreted as being ocean-floor exhalative deposits associated with seamounts lying away from
spreading axis magmatism. (Alabaster and Pearce, 1985)

Besshi deposits
The type locality is the Besshi Mine, Japan, but they are also known as kieslager. Copper, zinc and by-product silver and gold are obtained
from these deposits. They are stratabound conformable copper-rich pyrite deposits found in complex sedimentary and basic volcanic
sequences. The ores comprise pyrite, chalcopyrite and locally pyrrhotite, sphalerite and magnetite, and are found as bedded or lenticular
bodies that are often restricted to a single stratigraphical horizon. Minor amounts of bornite, haematite, sphene, ilmenite and rutile are
present. In unmetamorphosed examples, graded bedding and collomorphic textures are retained in the sulphides. Many Besshi deposits,
however, are metamorphosed, so that the ores show tectonic folding and schistose textures and the sulphides are accompanied by
muscovite, chlorite, quartz, epidote, actinolite, albite and stilpnomelane. (Kanehira and Tatsumi 1970; Kase, 1977; Yui 1983; Fox, 1984)

Kuroko deposits
These were first described from the Miocene orebodies of the Green Tuff region of Japan and are associated
with felsic volcanism. Their tectonic setting, associated volcanism and ore types are different from
spreading axes sulphides. Most deposits are unmetamorphosed. Characteristically, the deposits are zoned.
The complete sequence from hangingwall to footwall is: quartz-haematite-baryte with minor sulphides
(tetsusekiei ore) lying above baryte-sulphide ores. Beneath these ores lie the main massive sulphide zones.
The uppermost zone is black ore (kuroko) which is divided into two subzones: an upper, sphalerite, baryte,
pyrite, galena and tetrahedrite subzone and a sphalerite, baryte, pyrite, chalcopyrite and quartz subzone. The
middle zone is copper-rich (oko) and comprises chalcopyrite, pyrite and quartz ores above chalcopyrite-
pyrite, and the lowest zone is pyrite-rich, comprising pyrite, chalcopyrite and sphalerite. Beneath the
massive ores lies a stringer zone (keiko ore) of quartz-pyrite veins with chalcopyrite and minor sphalerite
and galena, that passes downwards into barren footwall rhyolites or pyroclastics. (Lambert and Sato, 1974;
Shimazaki, 1974; Ohmoto and Skinner (eds.) 1983). Recently the origin of Kuroko deposits has been reinterpreted using textural evidence
from doubly polished thin sections. In the original interpretation, the pyrite, chalcopyrite and sphalerite-galena zones were believed to
reflect the progressive cooling of ore fluids as they moved away from their source.
Although the ores were essentially co-temporal, the pyrite ore was interpreted as being the earliest and
highest temperature. This model is now accepted as being too simple. The present model (Eldridge et al.,
1983) suggests that the initial hydrothermal fluids mixed with sea water and were cooled to < 200C to precipitate a 'primitive black ore'
(fine-grained collomorphic sphalerite, galena, pyrite and baryte with only minor chalcopyrite) as a sulphide mound. Later hydrothermal
fluids were protected from the full cooling effect of the sea water by this 'primitive black ore', and as the temperature of the sulphide
mound rose, the primitive collomorphic ore recrystallized and then was replaced by chalcopyrite. This ore, in turn, was replaced by pyrite
as the maximum ore fluid temperature of approximately 350C was attained. In addition to the successive replacement of lower
temperature ores by higher temperature ores, earlier ore types were remobilized to stratigraphically higher levels.
The end result is the commonly seen sequence: pyrite-rich ores overlain by chalcopyrite-rich ores,
themselves overlain by galena-sphalerite-rich black ores. This interpretation is consistent with the re-
interpretation of the presence of crystallographically controlled chalcopyrite blebs in sphalerite, a texture
that is common in these ores and many others. Previously, this texture was explained as chalcopyrite
exsolution and taken as an indication of moderate to high temperatures of formation. The concentration of
chalcopyrite blebs along grain boundaries, fractures, twin planes and cleavage in sphalerite and the
experimental data that show the limited solubility of chalcopyrite in sphalerite (below 500C) has led to the
realization that the chalcopyrite distribution (now called chalcopyrite disease) is due to epitaxial growth of chalcopyrite on sphalerite, or is
a replacement phenomenon. (Barton, 1978; Eldridge et al., 1983)

Kuroko-style deposits
Many massive sulphide deposits share the characteristics of Kuroko deposits, especially in terms of their
tectonic setting, associated volcanism and ore types. Often, however, they have suffered the combined
effects of tectonism and metamorphism, so making their classification speculative.




Bornite and chalcocite. Gortdrum, Ireland







250m


Bornite (pink-brown) is complexly intergrown with white copper sulphide, chalcocite (centre). Anhedral quartz (dark grey, top right) and
euhedral dolomite (light grey, centre) are the main gangue phases. Dolomite rhombs show bireflectance from lighter grey (centre) to
darker grey (top centre), but have higher reflectance than quartz. Black areas are polishing pits.


Polished block, plane polarized light, x 80, air


Location: Gortdrum, County Tipperary, Ireland

This polymetallic deposit differs from most of the Irish-type deposits as the ores are
copper-rich and lead-zinc-poor. It occurs within Dinantian limestones and shales
associated with altered basic igneous rocks and close to a major fault. The
mineralization is zoned with chalcopyrite and mercury-rich tennantite within
bioclastic limestones lying above bornite and chalcocite-rich ore within shaly
dolomitized limestones.
Major Minerals: Bornite, chalcocite, chalcopyrite, Hg-rich tennantite
Minor Minerals: Pyrite, galena, sphalerite, haematite
Trace Minerals: Include arsenopyrite, cobaltite, cinnabar, amalgam, wittichenite, stromeyerite,
gortdrumite, uraninite, coffinite, digenite, covelline, native copper
Textures: Cobaltite is euhedral and zoned. Tennantite is replaced by bornite and chalcocite.
Bornite and chalcocite form characteristic symplectite-like intergrowths (myrmekitic
or graphic intergrowths) which are probably the result of simultaneous precipitation
of the two sulphides at low temperatures. Stromeyerite and wittichenite occur as
fine-grained inclusions in chalcocite. Uraninite forms collomorphic bands and is
replaced by bornite along the banding
References: Steed, 1986; Duane, 1988



Opaque and ore minerals associated with sedimentary rocks




Unmineralized sediments
Opaque phases are minor constituents of most sediments, either as part of the elastic component and hence
related to a source area, or as authigenic phases and so indicative of the depositional environment and
diagenetic conditions. Many sediments contain both detrital and authigenic opaque minerals. To overcome
the problem of the paucity of opaques in most sediments, it is advisable either to select atypical specimens
(for example, heavy mineral bands from elastic sequences) or to upgrade the opaque content by making
grain mounts. For all sediments, grain mounts are prepared after heavy mineral separation, but, in addition,
carbonate-rich rocks can be digested in dilute acid solutions in order to upgrade their opaque mineral content. Sections of the typical (and
unprocessed) sediments also are prepared. Upgraded material is used to investigate the full range of mineral species present and to
determine their relative proportions. However, textural information is more readily obtained from representative material; this is
especially true for the authigenic opaque mineral component. Reflected light studies are potentially useful in helping to provenance clastic
grains and, because many of the opaques are iron or iron-titanium oxides, the studies also play a role in explaining geomagnetic results.
Polished sections of very fine-grained rocks, like shales and mudstones, have better surfaces than those of thin sections and this allows
better fabric analysis and more accurate modal analyses to be made. The use of polished thin sections rather than thin sections in the
archaeological study of pottery has illustrated the advantages of this technique. (Amstutz and Bubenicek, 1967; Berner, 1984).

Unmineralized clastic rocks
The opaque and accessory minerals generally belong to the heavy mineral suite of oxides and silicates.
Detrital sulphides are uncommon except in young, immature sediments or those formed under unusual
reducing conditions. In maturer sediments, primary sulphides occur only within sealed rock fragments
where they have been protected from sedimentary oxidation. Original iron-titanium oxide minerals and
mafic silicates (especially biotite) are extensively altered to haematite and TiO
2
. minerals, but from textural
evidence it is possible to determine their original mineralogy. Authigenic, often euhedral, haematite and
TiO
2
. minerals form overgrowths on detrital grains of the same mineralogy but have a different minor element chemistry. Carbonaccous
material also forms part of the detrital fraction and measurements of the reflectance of vitrinite are used to determine the thermal history
of sediments.

Sandstones and siltstones
In addition to the quartz, feldspars, phyllosilicates and rock fragments that comprise the bulk of these rocks,
they contain opaque detrital phases. These include magnetite, ilmenite, (often oxidized to haematite and
TiO
2
, minerals to give 'martite' and 'leucoxene', respectively), rutile, anatase, brookite, chromite, sphene and
heavy mineral silicates, including zircon, tourmaline, epidote, pyroxenes and amphiboles, along with
carbonaceous material. Less commonly, cassiterite, mixed oxides of the rare metals (Nb, Ta, U and Ti),
monazite, xenotime and native gold are present. Sulphides are restricted to rock clasts.
Authigenic components include quartz, calcite, dolomite, ankerite, chalcedony, zeolites and sulphate
cements, together with lesser amounts of haematite, rutile, anatase, pyrite, marcasite, pyrrhotite and base
metal sulphides. The replacement of magnetite along (111) crystallographic directions by haematite forms
the very distinctive pseudomorph known as martite.
The replacement of ilmenite oxidation-exsolution lamellae in magnetite by TiO
2
,
minerals, coupled with the dissolution of magnetite to give an open boxwork texture, is often called leucoxene.
(Golding, 1961; van Houten, 1968; Dimanche and Bartholome, 1976; Turner and 'Archer, 1977; Holmes et al.,
1983)

Shales and mudstones
The mineralogy of the opaque detrital fraction is similar to that of sandstones but has a much finer grain size and only the TiO
2
minerals,
carbonaceous material and sulphides are readily apparent without using oil immersion lenses at high magnifications. Authigenic sulphides
are common and include framboidal pyrite formed from precursor iron sulphides (greigite and mackinawite), pyrite and marcasite
associated with carbonaceous matter or authigenic carbonates and discrete grains of pyrrhotite and base metal sulphides.
Siderite nodules, which are essentially pyrite and siderite, often have base metal sulphides, especially sphalerite, within them. (Love and
Zimmerman, 1961; Raiswell, 1976; Hudson, 1982; Love et al., 1983, 1984)

Limestones
These, too, have the same opaque mineralogy as sandstones and shales, especially if the limestones are argillaceous or arenaceous.
Haematite, TiO
2
minerals and carbonaceous material are the most common detrital opaque phases, and
pyrite and marcasite are the most abundant diagenetic sulphides. Other common base metal sulphides,
including sphalerite, galena and chalcopyrite, are present in minor amounts. Framboidal and recrystallized
framboidal pyrite and the selective replacement of coarse-grained carbonates by sulphides, especially within
fossils, are characteristic textures. (Love, 1970)

Coals
All coals have a sulphur content and, in addition to pyrite and marcasite, a range of sulphides have been reported including sphalerite,
galena, chalcopyrite, millerite and bornite. The sulphides (mainly pyrite and marcasite) form framboids, recrystallized framboids or
irregular aggregates associated with nodular siderite. They replace plant remains or form veinlets along the cleat. (Bocter et al., 1976;
Laznicka, 1981; Swaine, 1984)

Mineralized sedimentary rocks

Placers
Placers are Tertiary to Recent in age, and include a number of well recognized subclasses which reflect both
the mechanism of concentration and depositional environment. Amongst the most important are alluvial and
beach (littoral) placers, although screes (deluvial) and aeolian placers are mined. Many placers can be
related to their proto-ores, although for reworked placers this is more difficult. Sulphides are unusual as
modem placer minerals, although they have been recorded. Placer minerals have a number of properties.
They need to be chemically stable in the weathering cycle, be mechanically strong, lack good cleavages, be
hard (Moh's hardness > 6) and have a high density. Historically, placers have produced much of the world's noble metals and gemstones
and still remain important sources of them.
Placers from ultramafic or mafic parents are mined for platinum group metals, gold, diamond, ilmenite,
magnetite, chromite, rutile, and leucoxene; those from alkalic ultramafic parents produce pyrochlore group
minerals, apatite and Nb-Ta-bearing minerals. Placers from acidic volcanic and plutonic rocks produce
ilmenite, rutile, cassiterite, wolframite, scheelite, columbite, thorite, zircon, monazite and gold.
Unconsolidated placer ores are usually prepared as grain mounts. Consolidated fossil placers can be
regarded as normal ores and made into polished blocks or polished thin sections. (Hails, 1976)

Fossil placers
The Witwatersrand banker gold-uranium placer of the Kaapvaal Craton is perhaps the most famous example
of a fossil placer. There has been much speculation on the origin of the deposit and two main arguments
have been proposed: either that it is a fossil placer, with detrital native gold, uraninite and pyrite grains
mechanically introduced into a basin followed by redistribution of elements (notably uranium) by
metamorphism, or that the gold, uranium-bearing minerals and pyrite are epigenetic and hydrothermal in
origin. The host rock is an oligomictic conglomerate of vein quartz, chert, jasper, banded iron formation and
quartzite pebbles in a matrix of secondary quartz and phyllosilicates. It contains detrital, abraded pyrite, chromite, zircon, uraninite, gold
and other heavy minerals. Locally, gold and uranium are found within narrow carbonaceous-rich horizons. Over seventy minerals have
been recorded.

Manganese deposits
These are common and widespread and are often associated with sedimentary iron ores. There are a number
of classes of deposit, including: deep sea manganese nodules, precipitates from stagnant water, non-
volcanogenic quartz-clay-glauconite and manganese carbonate associations, and volcanogenic sedimentary
manganese ores.
Sedimentary manganese ores mainly comprise manganese oxides and hydroxides or
manganese-bearing carbonates. Manganese sulphides are uncommon ore minerals (unlike iron sulphides) and
manganese silicates are characteristic of metamorphic or metamorphosed deposits. Individual manganese minerals, especially oxides and
hydroxides, are difficult to distinguish in reflected light, hence the terms 'wad' or 'psilomelane' are often used to denote the presence of
mixtures of unidentified soft and hard manganese minerals, respectively. X-ray powder diffraction is a more successful method for the
identification of these species. Similarly, the characterization of manganese-bearing carbonates requires a knowledge of their chemistry.
(Roy, 1968,1976, 1981; Bonatti et al., 1972; Burns and Bums, 1979). Small (up to 30 cm in diameter) manganese nodules occur in vast
numbers over large areas of the deep ocean floor. They are authigenic in origin and often nucleate on detrital grains, organic material or
earlier nodules.
They comprise mixtures of oxides and hydroxides of iron and manganese, together with clays, zeolites,
quartz, opal, baryte and feldspar. The nodules carry significant amounts of cobalt, nickel and other minor
metals sorbed onto the major phases and are regarded as having potential economic interest.
In reflected light, individual minerals cannot be identified by their optical properties.
However, within the collomorphic banding that is characteristic of the nodules,
separate bands can be distinguished by reflectance differences and by the presence or
absence of bireflection and anisotropy. Amorphous iron and manganese hydroxides have low reflectances (less
than 9%), polish poorly and are isotropic, whereas todorokite and birnessite-rich bands polish better, have
reflectances of approximately 15% and show marked bireflectance and anisotropy. X-ray powder diffraction of the
different bands is the usual method employed to identify their mineralogy.
Elsewhere, manganese crusts are associated with modem deep sea volcanogenic sulphide deposits and other
volcanic activity close to seamounts; these crusts are often cobalt enriched. (Bums and Bums, 1977a,b;
Sorem and Fewkes, 1977, 1979; Bischoff and Piper (eds), 1979; Muller, 1979; Heath, 1981)

Chemical precipitates in lakes
These are the manganese equivalent of bog iron ores, and comprise hydrated manganese oxides.

Quartz-clay-glauconite associations
These occur within shallow marine deposits in stable cratonic areas. The ores are conformable and form
lenticular or nodular horizons showing mineralogical zoning, from oxide-rich to mixed oxide-carbonate to
carbonate-rich facies. These facies types primarily are related to palaeogeography but also to subsequent
supergene enrichment processes. In the shallow water oxide zone the ore mineral assemblage comprises
manganite, pyrolusite-manganite or psilomelane associated with limonite. This zone passes into a
transitional zone of manganese-bearing carbonates and manganese oxides and hydroxides which, in turn,
passes into the deeper water carbonate zone. This zone consists of nodules and lenses of cryptocrystalline manganese-bearing carbonates,
including calcic rhodochrosite, manganocalcite and manganoan calcite.

Manganese carbonates in limestones and dolomites
These are divided into the Moroccan-type, found in stable platform environments, and the Appalachian-type, found in geosynclinal
sequences. Moroccan-type deposits comprise manganese oxides, pyrolusite and psilomelane. They occur in limestones and dolomites,
often in association with red bed sequences. Appalachian-type deposits are found in limestones, dolomites and volcanic sequences where
they form beds and lenses of manganocalcite and calcic -rhodochrosite within carbonate host rocks.

Sedimentary-volcanogenic manganese deposits
These are widespread but individual deposits are small and of little economic importance. The ores are stratiform or lensoidal, and
comprise manganese oxides interbanded with chert and jasper on a centimetre scale. Many are associated with volcanogenic sulphide
deposits. Metamorphism of these deposits produces complex silicate ores that vary in mineralogy with the degree of contact and regional
metamorphism. Braunite, hausmannite, rhodonite, bustamite, tephroite, pyroxmangite and piemontite associated with haematite,
magnetite, limonite, and iron and base metal sulphides are typical minerals of this association. (Zantop, 1981)

Sedimentary iron ores
Iron is a common constituent of sediments, and, hence, sedimentary iron ores are widespread and all classes of deposit have been
exploited from the Iron Age to the present. In order of increasing economic importance, the main classes are bog iron ores, clay
ironstones, minette-type ores, Clinton-type ores and iron formations. Only the last two are mined. (James, 1954; Murray, 1979)

Bog iron ores
These are of very localized occurrence and are found in present-day lake and marsh sediments where iron has been fixed by humic
complexes. The iron is subsequently released by bacterial action and is precipitated as ferric oxides and hydroxides associated with minor
amounts of siderite and vivianite.
Limonite is the generalized term for poorly characterized iron hydroxides which include mixtures of goethite, lepidocrocite, akaganeite
and feroxyhyte.

Clay ironstones, blackband ironstones
These deposits are widespread but low grade. They occur within marine sequences and represent the fossil equivalents of bog iron ores.
Dolomite and siderite are the main iron-bearing minerals and, historically, the ores were roasted to convert iron carbonate to iron oxide.
(Curtis et al., 1975)

Minette-type ores
This is the commonest type of unmetamorphosed ironstone, but, with an iron content of 30-35% by weight,
minette-type ores are generally uneconomic. The ironstones are found in shallow marine carbonaceous
shale, mudstone, marl, limestone and ironstone sequences. The main iron-bearing minerals are limonite,
siderite and chamosite with lesser amounts of magnetite, haematite, greenalite and pyrite. Typically, the iron
ores comprise ooids of chamosite, haematite and limonite which have nucleated about detrital grains or
fossil fragments. Quartz, calcite, cellophane and silica are the main gangue minerals. Ores of Jurassic age
were mined in Europe in the nineteenth and twentieth centuries. (Kimberley, 1979, 1981; Maynard, 1986)

Clinton ores
The class is named for the Silurian Clinton Formation of the eastern United States of America where oolitic ironstones, together with
argillaceous and carbonaceous shales, limestones and dolomites, occur within shallow marine sediments. Haematite, chamosite and
siderite are the main iron-bearing minerals and are associated with calcite and silica.

Iron formations (banded iron formations)
Iron formations are defined as thinly-bedded or finely laminated chemical/biochemical sediments
comprising chert (jasper), plus iron-bearing oxides, carbonates, silicates or sulphides. These are
characteristically enormous deposits and range from Archaean to Lower Palaeozoic in age, although most
are Proterozoic. They are subdivided, partly on their tectonic environment, into Algoma-type, found in
volcano-sedimentary sequences in greenstones belts, and into Lake Superior-type, found in continental-shelf
sequences of quartzites, cherts, black shales and dolomites. The mineralogy of the ores is variable and this
reflects primary sedimentary facies variations, later diagenetic effects, and metamorphism.

Unmetamorphosed iron formations can contain four facies types, which are believed to represent original variations in the sedimentary
conditions. These are an oxide facies formed in well oxygenated waters and comprising magnetite-chert or
haematite-chert; a carbonate facies dominated by siderite; a silicate facies containing chamosite, glauconite,
greenalite and locally minnesotaite and stilpnomelane; and a sulphide facies of pyrite and minor pyrrhotite
formed in an oxygen-poor environment often associated with black shales. Silica is the main gangue of the
oxygen-rich facies, whereas carbonates including siderite, ankerite and dolomite are important in the more
reduced facies. Many iron formations have been metamorphosed, their original sedimentary and diagenetic
features destroyed and their original mineralogies altered to complex iron silicate associations. Supergene
oxidation of magnetite to martite and primary iron minerals to limonite is widespread and economically
important. (Eichler, 1976; Kimberley, 1978; Trendall and Morris (eds), 1983)

Bauxites
These are the major ores of aluminium, but with increasing amounts of hydrated iron oxides, bauxites grade
into laterites. Bauxites, which are Cretaceous to Recent in age, can be divided into a laterite crust-type
formed by the weathering of aluminous non-calcareous rocks and a karstic-type formed from aluminous
limestones or dolomites.
In bauxites the aluminium oxide mineralogy changes with increasing metamorphic
grade from gibbsite to boehmite to diaspore and finally to corundum. These minerals are accompanied by quartz,
kaolinite, halloysite, limonite and haematite, together with a very large number of relict phases from the parent
rock, including anatase, rutile, sphene, zircon, pyrite and hogbomite. Pisolitic, oolitic or conglomeratic fabrics are
common in bauxites and many ores retain relict fabrics of their parent rocks. Individual oxide and hydroxide
minerals are very difficult to distinguish in reflected light and X-ray diffraction methods are usually employed to
characterize the mineralogy of bauxites. (Brdossy, 1982)

Lateritic nickel deposits
In unmineralized basic and ultrabasic rocks, nickel is held in olivine and to a lesser extent in other mafic silicates, magnetite and
pyrrhotite. It also forms discrete sulphides and arsenides, including pentlandite, millerite, heazlewoodite and niccolite. The nickel
contribution from olivine is the most significant, and, hence, the most productive parent rocks are peridotites and similar ultramafics
although, norites are also important. Nickel, together with magnesium and iron, is released on weathering and either reprecipitates with
iron (and cobalt) and silica close to the surface to form nickel-rich limonitic ores (called nickeliferous iron ores), or passes down through
the upper weathering zones to precipitate with magnesium and silica as nickel-bearing hydrous silicates (which are collectively known as
garnierite) to form nickel silicate ores. Beneath these ores lie altered and then fresh parent rock. (de Waal, 1971; Golightly, 1981)

Oxidation of sulphides and supergene enrichment
Many primary sulphide deposits have been subjected to secondary alteration and oxidation. Oxidation is the
major process above the water table and sulphides are oxidized to sulphates, oxides and hydrated oxides,
especially limonite or, more rarely, haematite. Pocks which mainly comprise limonite and silica and which
overlie sulphide ores are called gossans. Gossans typically show a cellular structure of goethite and silica
that have precipitated along grain boundaries, cleavages or twin planes of the primary sulphides. Brightly
coloured secondary base metal carbonates and sulphates, relict sulphides and native metals are also present.
The textures and mineralogy of gossans reflect the textures and mineralogy of the original sulphide ores, especially if the primary ores
were coarse grained. Some of the metals go into solution and migrate downwards to meet the water table. Here, conditions change from
oxidizing to reducing and the metals reprecipitate as secondary sulphides. Commonly, this dramatically increases the grade of the ore,
especially where the primary ore comprises disseminated sulphide. This zone is known as the supergene enrichment zone. Supergene
enrichment occurs as a series of oxidation and hydration reactions acting upon the original sulphide species. The degree of oxidation of
the more susceptible minerals often controls the subsequent oxidation and alteration of the less susceptible ones. The generalized sequence
of susceptibility is: pyrrhotite > chalcopyrite > fine-grained pyrite > sphalerite > galena > coarse-grained pyrite. (Sillitoe and Clark, 1969;
Blain and Andrew, 1977; Andrew 1980; Sangameshwar and Barnes, 1983; Nickel and Daniels, 1985)

Sedimentary-hosted base metal deposits
These deposits range from Proterozoic to Tertiary in age and are hosted by shales, siliciclastics and carbonates. They are important ores of
copper, lead, zinc, uranium and silver, and can be syngenetic, syndiagenetic or epigenetic in origin. Older
deposits are often metamorphosed. (Sangster (ed.), 1983)

Black carbonaceous shale-hosted copper deposits
These stratiform deposits account for a significant proportion of the world's copper reserves. Two main copper provinces: the Upper
Proterozoic Zambian Copper Belt and the Lower Permian Kupferschiefer of central and northwest Europe have been studied intensively.
Both provinces have huge, essentially syngenetic/diagenetic ores found in shallow marine sediments associated with major transgressions.
Anoxic conditions and bacterial reduction of sea water sulphate were important controls on mineralization. The ores have both lateral and
vertical mineralogical zonation related to palaeogeographical conditions. In the Kupferschiefer, this zoning is copper- and silver-rich
passing upward into lead- and zinc-rich ores, whereas in the Zambian Copper Belt, it is chalcocite passing basinwards into bornite, then
chalcopyrite and finally pyrite. In unmetamorphosed examples the sulphides are fine-grained and their distribution reflects primary
sedimentary features of the host sediments. Associated volcanicity is minor in extent or absent.

The main sulphides of the unmetamorphosed Kupferschiefer are fine-grained pyrite, chalcocite, galena, sphalerite, digenite, djurleite,
bornite, chalcopyrite and covelline. Minor minerals include anilite, tennantite, luzonite, mooihoekite, haycockite together with trace
amounts of cobaltite-gersdorffite, smaltite-chloanthite, clausthalite, molybdenite, native gold, native silver and platinum group minerals.

Stratiform copper-silver ores in green siliciclastics
Some shallow marine clastics contain minor green-grey siltstone, light-coloured sandstone or carbonate-rich
horizons within a dominantly purple-red sequence. The subordinate horizons are hosts to low grade copper-
silver ores which are believed to be diagenetic in origin. Copper, iron and silver stripped from the main
oxidized reddened sequence are reprecipitated as pyrite, followed by copper-iron and copper sulphides.
Although discrete silver minerals are present in trace amounts most of the silver occurs within copper
sulphides ('chalcocite'), including digenite, anilite, djurleite and chalcocite. Typically, the sulphides are
finely disseminated or form veinlets parallel with the bedding of the host rocks. (Hayes and Einaudi, 1986; Lange et al., 1986, 1987)

Sandstone-hosted uranium-vanadium and base metal deposits
There are two main classes of deposit: uranium deposits and red bed copper (lead and zinc) deposits. The ores are mined for uranium,
copper, vanadium and minor silver, lead and zinc. Both classes are hosted by continental to very shallow marine sediments laid down
under and conditions. The sequences are characteristically reddened by fine-grained haematite coatings (called 'pigment') around the
clastic grains. The mineralization is conformable, often associated with primary sedimentary features and is concentrated in bleached or
grey-green organic and pyrite-rich beds. The ores are diagenetic to epigenetic and, because of the porosity of the host sediments, are often
characterized by a large number of brightly coloured secondary oxidation zone minerals.

Uranium deposits in sandstones. (Colorado Plateau, Wyoming rollfront deposits)

Large scale deposits are found in the western states of the USA, mainly within Mesozoic fluviatile sandstones and siltstones. The deposits
form flats, pods or the characteristic roll-fronts at the junctions between oxidized and reduced clastics. Uranium, in association with
pyrite, is initially fixed in the clastics by organic material; on oxidation of these sediments (reddening), the uranium is oxidized and moves
in solution until it encounters reducing conditions when it reprecipitates (often replacing plant material). Uraninite (as pitchblende),
coffinite, uranium-rich organic material, carnotite and tyuyamunite, together with many secondary uranium and vanadium phases, are the
main ore minerals. These are associated with lesser amounts of pyrite, marcasite, galena, sphalerite, chalcopyrite, bornite and chalcocite.
(Fischer, 1968; Harshman, 1968; Kelley et al., 1968; Young, 1984)

Red bed copper deposits
Although some are lead-zinc-rich and economic, the majority are copper-rich, small and sub-economic. The
ores are concentrated into bleached horizons within reddened sequences, where they form syndiagenetic
cements around elastic silicate grains. The main sulphides include the blue copper sulphides (chalcocite),
bornite, pyrite, galena, sphalerite and covlline, together with many secondary copper, lead and zinc
carbonates and sulphates. The primary (and secondary) mineralization is controlled by the local porosity and
permeability of the host rocks. (Holmes et al., 1983; Zielinski et al., 1983)

Carbonate-hosted Irish-type deposits
This class has similarities with the older exhalative shale-hosted lead-zinc deposits (Mount Isa type) and
those of the Mississippi Valley type. The type examples are found in Lower Carboniferous shelf carbonate
sequences of the Central Irish Plain. The carbonates lie transgressively over Devonian siliciclastics and
mineralization is localized close to Caledonian-trending faults. The deposits occur in argillaceous to
dolomitic carbonates and most have simple mineralogies but complex synsedimentary textures. The main
sulphides are pyrite, sphalerite, galena and marcasite, and locally chalcocite and bornite accompanied by
minor amounts of tetrahedrite-tennantite, boulangerite, bournonite and other sulphosalts. Mineralization is believed to be the result of
fluid exhalations onto the seafloor, accompanied by replacement and void infilling of the underlying sediments. (Hitzman and Large,
1986; Russell, 1986)

Mississippi Valley-type
This class of deposit is mined for lead, zinc, fluorite and baryte. These epigenetic deposits usually occur
within Phanerozoic limestones and dolomites in sequences that are often associated with evaporates.
Individual deposits may be small, but, collectively, they occur within large ore fields. Mineralization is
concentrated along erosional surfaces, karstic surfaces or in faulted and brecciated carbonate, and comprises
void infilling and metasomatic replacement ores. Associated wallrock alteration is restricted to
dolomitization, silicification and the introduction of pyrite. Mineralization is polyphase. Three mineralogical
subclasses are recognized, the most common is the zinc-rich, but lead-rich and fluorite-rich subclasses are also important. (Heyl, 1983;
Kisvarsanyi et al. (eds), 1983; Hagni, 1986; Kyle and Price, 1986)

South Pennines and Mendip Hills, Britain
Both void infilling and metasomatic replacement deposits occur within Lower Carboniferous limestones, or
more rarely dolomites, and have many of the characteristics of the fluorite-rich subclass of the Mississippi
Valley deposits. Galena and sphalerite are accompanied by bravoite, pyrite, marcasite and chalcopyrite
within a fluorite, baryte and calcite 'gangue'. (Dunham, 1983, Ixer, 1986).

North Pennine Orefield, Britain
Lower Carboniferous limestones and sandstones, that have been mineralized, lie unconformably upon
granitic basement. The mineralization within the orefield is zoned: an inner higher temperature zone is
characterized by a pyrrhotite, chalcopyrite and quartz association with minor lead and zinc, and is
surrounded by galena-rich and sphalerite-rich outer zones. The minor ore mineralogy within all of the zones
is complex, with nickel-cobalt-iron arsenides and sulpharsenides, bismuth, silver and antimony minerals and
rare earth phosphates and fluorocarbonates. This mineralogy suggests a geochemical contribution from the
underlying granite. (Dunham, 1948, 1983; Brown et al., 1987)

Syngenetic exhalative lead-zinc deposits in shales and carbonates (Mount Isa type)
There are few examples of this class of deposit, but they are large and produce significant by-product silver. The deposits are Middle
Proterozoic to Palaeozoic in age and are found in shallow water black shales, siltstones, cherts and evaporates or their metamorphosed
equivalents. Basalts and tuffs form part of these sequences but do not appear to be related genetically to mineralization. In
unmetamorphosed deposits the sulphides are very fine-grained and often contain much framboidal pyrite; with metamorphism the
sulphides coarsen in grain size. Pyrite, sphalerite, galena, pyrrhotite and freibergite are the main ore minerals and, amongst the silver-
carriers, freibergite, stephanite, pyrargyrite, argentopyrite and native silver are important. Basinal compaction with the expulsion of
interstitial saline brines along faults is the most widely accepted model for the genesis of these deposits. (Love and Zimmerman, 1961;
Stanton, 1963; Mathias and Clark, 1975; Finlow-Bates and Stumpfl, 1979; Perkins, 1984)
Molybdenite. Jersey, Channel Islands, Britain







500m


Coarse blades and laths of molybdenite show strong bireflectance and reflection pleochroism. The strong basal cleavage of molybdenite
(left) parallel to (0001) is clearly seen, as are deformation effects similar to kink banding (centre). The dark grey area (bottom) is quartz.
Four trigonal carbonate crystals showing bireflectance are lighter grey (bottom left). Black areas are polishing pits.


Polished block, plane polarized light, x 40, air
Location: Quartz-sulphide veins associated with granites. Jersey,Channel Islands, Britain

The three granite outcrops on Jersey contain minor crosscutting quartz-sulphide
veining.
Major Minerals: Molybdenite, sphalerite, chalcopyrite, pyrite
Minor Minerals: Galena, pyrrhotite, arsenopyrite
Trace Minerals: Include stannite group minerals, tetrahedrite group minerals, bournonite, native
antimony
Textures: Sphalerite stars have exsolved from chalcopyrite. Sphalerite has suffered from
chalcopyrite disease. Oriented tetrahedrite and stannite group minerals are present in
sphalerite; the latter is due to exsolution. Alteration of pyrrhotite to bird's-eye
intergrowths of pyrite and marcasite is extensive
Reference: Ixer, 1980



Opaque and ore minerals associated with intermediate and acid igneous rocks




Opaque minerals in unmineralized intermediate rocks
The primary iron-titanium oxide minerals (magnetite ulvspinel, ilmenite-haematite and rutile), together
with their secondary oxidation products (maghaemite, haematite, pseudobrookite, TiO
2
minerals and
sphene), are similar to those found in basic rocks. Chromite, however, is less common but other metal
oxides, namely cassiterite, columbite and bixbyite, are more abundant. Early sulphides include pyrrhotite,
pyrite, chalcopyrite and marcasite. (Haggerty, 1976b).

Opaque minerals in unmineralized to lightly mineralized granites
Although the mineralogy of granites is variable, they are essentially quartz and feldspar rocks that carry
micas, amphiboles and pyroxenes, together with a wide variety of accessory minerals. Accurate
characterization of the minor and accessory phases within granites should complement geochemical studies,
especially if mass-balance calculations are to be performed. Reflected light investigation of the opaque and
accessory phases has an important role in helping to discriminate fertile from infertile granites, in terms of
their potential for economic metalliferous deposits or for geothermal energy (the so-called high heat
producing granites). Accessory minerals are found as 10-100m diameter grains between quartz and feldspars, or commonly within mafic
and especially altered mafic minerals. Pleochroic halos in mafic minerals usually suggest the presence of one or more accessory minerals
and repay careful study. Amongst the more common primary opaque and accessory minerals are zircon, allanite, sphene, tourmaline,
epidote; ilmenite-haematite, magnetite-ulvspinel, cassiterite, columbite-tantalite, uraninite, thorite, TiO
2
minerals, pyrochlore group
minerals, wolframite; apatite, monazite, xenotime; pyrite, pyrrhotite, chalcopyrite, sphalerite, arsenopyrite and molybdenite. In addition,
numerous rare earth element-bearing carbonates and fluorocarbonates and U-Nb-Ti-bearing oxide minerals have been recorded. The
accessory minerals occur as loose aggregates, often with symplectite-like intergrowths, at crystal boundaries of the silicates, or lie along
the cleavage planes and grain boundaries of mafic minerals.
Few granites have escaped post-magmatic alteration by hydrothermal fluids and so show alteration and
localized migration of their primary phases. Alteration includes the replacement of ilmenite by sphene and
TiO
2
minerals, and titanomagnetite by leucoxene. The crystallization of TiO
2
, minerals, ilmenite and
haematite along the cleavages of altered mafics, especially biotite, suggest local redistribution of elements
from silicates into oxides. Haematite and sulphides, notably pyrite, marcasite and chalcopyrite, are
introduced during hydrothermal alteration. Many of the accessory minerals are translucent to semiopaque
and so polished thin sections are more useful than polished blocks. Accessory minerals are often irregular in
their distribution, complexly intergrown with each other and, because of their low and similar reflectances and strong internal reflections,
are difficult to characterize in reflected light. Oil immersion and high magnification are required for the discrimination of fine-scale
properties like zoning. Transmitted light petrography and chemical characterization by SEM or electron microprobe are also needed.
Autoradiographs and Lexan overlays are used for locating the sites of uranium- and thorium-bearing phases. (Ishihara, 1977; Basham et
al., 1982; Mackenzie et al., 1984; Chatterjee and Strong, 1985)

Mineralization associated with granites
The classical sequence of late-stage magmatic to post-magmatic alteration and mineralization involves pegmatite formation followed by
greisenization, albitization and, finally, hydrothermal quartz-sulphide veining. (Eugster, 1985; Plant, 1986)

Pegmatites
Granite pegmatites are economically important sources of quartz, feldspar and micas. In addition, they are
major producers of Li, Be, Cs, Pb, W, Sn, Th, Nb-Ta, rare earth element (REE) minerals and gemstones.
Minerals in pegmatites are often coarse-grained. Simple pegmatites are essentially quartz, potash feldspar,
sodic plagioclase and biotite, together with muscovite, tourmaline and garnet. Complex pegmatites are
zoned and have the same essential mineralogy as simple pegmatites, together with more exotic silicates.
Opaque and semi-opaque minerals include Th-bearing phases, thorianite and thorite; U-bearing phases
including uraninite and uranothorite; Nb- and Ta-bearing phases, columbite, tantalite, pyrochlore group minerals and ilmenorutile; Sn-
bearing phases, primarily cassiterite; W bearing phases, wolframite and scheelite; and a wide variety of REE-phases, including monazite,
xenotime, allanite, samarskite, bstnasite and parisite group minerals. Native bismuth, bismuthinite, molybdenite, stannite group minerals
and many base metal sulphides are found in minor amounts. (Cerny (ed.), 1982; Brown and Ewing (eds.), 1986)

Post-pegmatite alteration
Late stage fluids metasomatically alter acidic and alkaline plutonic rocks and the resulting metasomatites are
found in apical areas of the parent pluton. Albitization, microclinization and greisenization are amongst the
most important alteration processes to be associated with mineralization. The alteration sequence is not
uniform; in Nigeria, albitization is followed by microclinization and then by greisenization, whereas in
Comwall albitization is later than microclinization. (Jackson, 1986)

Albitization
In Nigeria, sodium-rich fluids have altered a variety of granites into quartz-albite rocks containing minor
amounts of Li-rich mica. Accompanying the alteration is an enrichment of Nb (Ta), Zr, Hf, Th, U, PEE, Fe,
and Mn. Different compositions of the primary granites are reflected in different mineralogies in their
secondary albitites; for example, niobium mineralization in peraluminous granite is present as columbite, in
peralkaline granites as pyrochlore, and in metaluminous granites as fergusonite.

Microclinization
At Ririwai, potassic metasomatism has converted a biotite granite into a quartz, microcline and white mica
rock with subordinate amounts of topaz and sericite. Minor amounts of tin and tungsten were introduced.

Greisenization
This is a widespread and important ore forming process produced by hot acidic fluids. Greisen is a quartz
and white mica (muscovite, sericite, zinnwaldite) rock, forming irregular masses, veins or stockworks
cutting apical regions in granites. Topaz, tourmaline, fluorite, biotite and albite can be present in significant
amounts in addition to ore minerals. Greisens can carry an extensive opaque mineralogy, including
cassiterite, wolframite, scheelite, columbite, haematite, magnetite, brannerite, molybdenite, pyrrhotite,
pyrite, marcasite, arsenopyrite, chalcopyrite, sphalerite, galena, stannite, tetrahedrite group minerals, native
bismuth and bismuthinite. Cassiterite, wolframite and scheelite-bearing greisens, and wolframite, molybdenite and native bismuth-bearing
greisens are economically the most important. (temprok, 1985; Taylor and Strong, 1985)

Mineralized quartz veins within granite
Cross-cutting quartz veins in granites are common and carry metal oxides, base metal sulphides and
arsenides. Associated wallrock alteration includes greisenization and tourmalinization. These are the
classical tin-tungsten-molybdenum-bismuth-arsenic-bearing hydrothermal veins associated with apical areas
of granites. The ore mineralogy of the veins is similar to that of greisens except that sulphides become
volumetrically the more abundant and oxide minerals less so. The mineralogy of granite-associated quartz
veins is extensive. Common minerals include cassiterite, wolframite, molybdenite, stannite group minerals,
bismuthinite, chalcopyrite, sphalerite, galena, pyrrhotite, pyrite, marcasite, arsenopyrite, lollingite and tetrahedrite group minerals. These
are accompanied by minor amounts of sulphosalts and native metals.

Porphyry deposits
Much of the world's copper and molybdenum are produced from very large tonnage low grade sulphide ores
associated with high level, acid to intermediate, porphyritic intrusions of Tertiary to Quaternary age; these
are the porphyry deposits. Three main types are recognized: porphyry copper, porphyry molybdenum and
smaller porphyry-style tin-tungsten stockwork deposits. By-product gold, silver and base metals are
produced.

Porphyry copper deposits
These are mined for copper with by-product molybdenum, gold and silver; some contain tungsten as
wolframite. A central, small, porphyritic stock is surrounded by a series of genetically related alteration
zones and ore shells that carry hypogene sulphide (and minor oxide) mineralization in disseminated quartz
veinlets and healed microveinlets. In some deposits, larger veins carrying gold and silver mineralization are
found in the outermost alteration zone.
Moving from the porphyritic stock outwards, the hydrothermal wallrock alteration zones are: potassic,
phyllic, argillic and propylitic. Each carries a distinctive hypogene sulphide-oxide assemblage. The inner
potassic zone, characterized by the development of secondary orthoclase and biotite together with quartz,
albite, sericite,. anhydrite and apatite, is roughly coincident with an innermost low-grade chalcopyrite,
pyrite, molybdenite, magnetite and bornite zone. Molybdenite, then chalcopyrite and finally pyrite increase
in amounts towards the phyllic zone, but generally chalcopyrite is more abundant than pyrite.
Rocks in the phyllic zone comprise quartz, sericite and pyrite (with up to 10% by volume pyrite). The main
economic ore shell occurs within this zone, often at its junction with the potassic zone. Pyrite is
accompanied by chalcopyrite, molybdenite, bornite, chalcocite, magnetite, enargite and sphalerite within
abundant quartz veinlets. The argillic zone comprises montmorillonite, illite, chlorite and kaolinite and
carries pyrite with chalcopyrite and bornite with trace amounts of chalcocite, enargite, molybdenite,
tennantite, sphalerite, galena and wolframite. The propylitic alteration zone comprises chlorite, epidote, calcite and pyrite. Pyrite is the
main sulphide and trace amounts of bornite, molybdenite, sphalerite, galena, magnetite, specularite, rhodochrosite and rhodonite are also
present.
The outermost part of this zone carries chalcopyrite, galena and sphalerite veins with gold and silver
mineralization. Superimposed upon this primary mineralization can develop an extensive supergene
'chalcocite lanket'. This comprises chalcocite, djurleite, digenite with minor blaubleibender covelline,
cuprite and native copper. Often overlying the chalcocite blanket and primary zones is a 'limonite' gossan
containing jarosite, copper carbonates- copper oxides, native copper and haematite. (Titley and Hicks (eds.),
1966; Drummond and Godwin, 1976; Ney et al., 1976; Hollister, 1979; Beane and Titley, 1981; Titley (ed.),
1982)

Porphyry molybdenum deposits
These are rarer than porphyry copper deposits and produce byproduct tungsten. They are Mesozoic to Tertiary in age and have been
divided into 'Climax-type' (stockwork type), associated with multiple porphyritic granitic intrusions with
molybdenite and pyrite as major sulphides, accompanied by wolframite, cassiterite, stannite and bismuth
sulphosalts; and the ,quartz-monzonite' type, associated with granites, granodiorites and quartz
monzodiorites. In addition to molybdenite and pyrite, these carry minor amounts of scheelite, bismuth
sulphosalts and chalcopyrite. Both types of porphyry molybdenum deposits are accompanied by potassic,
phyllic, argillic and propylitic alteration but also by more minor silicification, quartz vein, greisenization
and garnet-rich zones. The majority of the molybdenite occurs as stockwork quartz-molybdenite veins. The
potassic zone contains K-feldspar, quartz, magnetite and biotite, and the phyllic zone abundant sericite and
pyrite. Both zones carry minor molybdenite. In the argillic zone, kaolinite, montmorillonite and sericite replace feldspar, and biotite is
altered to muscovite, sericite plus minor rutile, leucoxene, pyrite, carbonates and fluorite. The propylitic zone carries chlorite, epidote and
pyrite accompanied by calcite, clays and sericite. Greisen veins comprise quartz, molybdenite, topaz, pyrite, magnetite and muscovite,
whereas in the garnet zones spessartine is accompanied by galena, sphalerite and rhodochrosite. Supergene mineralization in porphyry
molybdenum deposits is weak to absent. (Wallace et al., 1978; Sillitoe, 1980; White et al., 1981)

Other porphyry-style deposits
Other deposits, notably tin- and tungsten-bearing, show many similarities to porphyry copper and
molybdenum deposits. They are associated with high level porphyritic stocks that are accompanied by
broadly concentric alteration and mineralization zones. Potassic alteration is rarer, although greisenization is
more common than for porphyry copper deposits. (Sillitoe et al. 1975, Grant et al. 1980; Noble et al. 1984)


Sphalerite, bournonite and galena. Navan, Ireland







125m


Sphalerite crystals display abundant light yellow to brown internal reflections and are cemented by bournonite, which shows its
characteristic polysynthetic twinning on (110) 'parquet-twinning' (centre). Minor amounts of galena (lilac-white, bottom centre,) are
intergrown with bournonite. The lilac-white colour of galena is due to the partial crossing of the polars.


Polished block, plane polarized light, x 160, oil
Location: Navan, County Meath, Ireland

The deposit has the characteristic mineralogy of Irish-type deposits. Stratiform
galena-sphalerite lenses are hosted by Middle to Upper Courceyan shallow-water
carbonates, with minor pyritic mineralization in the overlying boulder
conglomerates.
Major Minerals: Iron-poor sphalerite, galena, marcasite, pyrite
Minor Minerals: Semseyite, bournonite, freibergite, pyrargyrite, boulangerite, cylindrite
Trace Minerals: Include franckeite, argyrodite and jordanite
Textures: Sphalerite, galena and baryte show rhythmical lamination (bedding parallel), graded
bedding and soft sediment disruption. Pyrite/marcasite, sphalerite and galena show
stalactitic forms. Crustiform. sphalerite, galena, pyrite, marcasite, calcite, dolomite
and baryte are associated with void-infilling of breccia zones or cross-cut the
rhythmical ore. Galena carries fine-grained sulphosalt inclusions along grain
boundaries. Locally, pyrite and marcasite form framboid-rich layers.
References: Andrew and Ashton, 1982, 1985; Ashton et al., 1986; Fontbote and Amstutz, 1986



Opaque and ore minerals associated with sedimentary rocks




Unmineralized sediments
Opaque phases are minor constituents of most sediments, either as part of the elastic component and hence
related to a source area, or as authigenic phases and so indicative of the depositional environment and
diagenetic conditions. Many sediments contain both detrital and authigenic opaque minerals. To overcome
the problem of the paucity of opaques in most sediments, it is advisable either to select atypical specimens
(for example, heavy mineral bands from elastic sequences) or to upgrade the opaque content by making
grain mounts. For all sediments, grain mounts are prepared after heavy mineral separation, but, in addition,
carbonate-rich rocks can be digested in dilute acid solutions in order to upgrade their opaque mineral content. Sections of the typical (and
unprocessed) sediments also are prepared. Upgraded material is used to investigate the full range of mineral species present and to
determine their relative proportions. However, textural information is more readily obtained from representative material; this is
especially true for the authigenic opaque mineral component. Reflected light studies are potentially useful in helping to provenance clastic
grains and, because many of the opaques are iron or iron-titanium oxides, the studies also play a role in explaining geomagnetic results.
Polished sections of very fine-grained rocks, like shales and mudstones, have better surfaces than those of thin sections and this allows
better fabric analysis and more accurate modal analyses to be made. The use of polished thin sections rather than thin sections in the
archaeological study of pottery has illustrated the advantages of this technique. (Amstutz and Bubenicek, 1967; Berner, 1984).

Unmineralized clastic rocks
The opaque and accessory minerals generally belong to the heavy mineral suite of oxides and silicates. Detrital sulphides are uncommon
except in young, immature sediments or those formed under unusual reducing conditions. In maturer
sediments, primary sulphides occur only within sealed rock fragments where they have been protected from
sedimentary oxidation. Original iron-titanium oxide minerals and mafic silicates (especially biotite) are
extensively altered to haematite and TiO
2
. minerals, but from textural evidence it is possible to determine
their original mineralogy. Authigenic, often euhedral, haematite and TiO
2
. minerals form overgrowths on
detrital grains of the same mineralogy but have a different minor element chemistry. Carbonaccous material
also forms part of the detrital fraction and measurements of the reflectance of vitrinite are used to determine
the thermal history of sediments.

Sandstones and siltstones
In addition to the quartz, feldspars, phyllosilicates and rock fragments that comprise the bulk of these rocks,
they contain opaque detrital phases. These include magnetite, ilmenite, (often oxidized to haematite and
TiO
2
, minerals to give 'martite' and 'leucoxene', respectively), rutile, anatase, brookite, chromite, sphene and
heavy mineral silicates, including zircon, tourmaline, epidote, pyroxenes and amphiboles, along with
carbonaceous material. Less commonly, cassiterite, mixed oxides of the rare metals (Nb, Ta, U and Ti),
monazite, xenotime and native gold are present. Sulphides are restricted to rock clasts.
Authigenic components include quartz, calcite, dolomite, ankerite, chalcedony, zeolites and sulphate
cements, together with lesser amounts of haematite, rutile, anatase, pyrite, marcasite, pyrrhotite and base
metal sulphides. The replacement of magnetite along (111) crystallographic directions by haematite forms
the very distinctive pseudomorph known as martite.
The replacement of ilmenite oxidation-exsolution lamellae in magnetite by TiO
2
,
minerals, coupled with the dissolution of magnetite to give an open boxwork texture,
is often called leucoxene. (Golding, 1961; van Houten, 1968; Dimanche and Bartholome, 1976; Turner and
'Archer, 1977; Holmes et al., 1983)

Shales and mudstones
The mineralogy of the opaque detrital fraction is similar to that of sandstones but has a much finer grain size and only the TiO
2
minerals,
carbonaceous material and sulphides are readily apparent without using oil immersion lenses at high magnifications. Authigenic sulphides
are common and include framboidal pyrite formed from precursor iron sulphides (greigite and mackinawite), pyrite and marcasite
associated with carbonaceous matter or authigenic carbonates and discrete grains of pyrrhotite and base metal sulphides.
Siderite nodules, which are essentially pyrite and siderite, often have base metal sulphides, especially sphalerite, within them. (Love and
Zimmerman, 1961; Raiswell, 1976; Hudson, 1982; Love et al., 1983, 1984)

Limestones
These, too, have the same opaque mineralogy as sandstones and shales, especially if the limestones are
argillaceous or arenaceous. Haematite, TiO
2
minerals and carbonaceous material are the most common
detrital opaque phases, and pyrite and marcasite are the most abundant diagenetic sulphides. Other common
base metal sulphides, including sphalerite, galena and chalcopyrite, are present in minor amounts.
Framboidal and recrystallized framboidal pyrite and the selective replacement of coarse-grained carbonates
by sulphides, especially within fossils, are characteristic textures. (Love, 1970)

Coals
All coals have a sulphur content and, in addition to pyrite and marcasite, a range of sulphides have been reported including sphalerite,
galena, chalcopyrite, millerite and bornite. The sulphides (mainly pyrite and marcasite) form framboids, recrystallized framboids or
irregular aggregates associated with nodular siderite. They replace plant remains or form veinlets along the cleat. (Bocter et al., 1976;
Laznicka, 1981; Swaine, 1984)

Mineralized sedimentary rocks

Placers
Placers are Tertiary to Recent in age, and include a number of well recognized subclasses which reflect both
the mechanism of concentration and depositional environment. Amongst the most important are alluvial and
beach (littoral) placers, although screes (deluvial) and aeolian placers are mined. Many placers can be
related to their proto-ores, although for reworked placers this is more difficult. Sulphides are unusual as
modem placer minerals, although they have been recorded. Placer minerals have a number of properties.
They need to be chemically stable in the weathering cycle, be mechanically strong, lack good cleavages, be
hard (Moh's hardness > 6) and have a high density. Historically, placers have produced much of the world's noble metals and gemstones
and still remain important sources of them.
Placers from ultramafic or mafic parents are mined for platinum group metals, gold, diamond, ilmenite,
magnetite, chromite, rutile, and leucoxene; those from alkalic ultramafic parents produce pyrochlore group
minerals, apatite and Nb-Ta-bearing minerals. Placers from acidic volcanic and plutonic rocks produce
ilmenite, rutile, cassiterite, wolframite, scheelite, columbite, thorite, zircon, monazite and gold.
Unconsolidated placer ores are usually prepared as grain mounts. Consolidated fossil placers can be
regarded as normal ores and made into polished blocks or polished thin sections. (Hails, 1976)

Fossil placers
The Witwatersrand banker gold-uranium placer of the Kaapvaal Craton is perhaps the most famous example
of a fossil placer. There has been much speculation on the origin of the deposit and two main arguments
have been proposed: either that it is a fossil placer, with detrital native gold, uraninite and pyrite grains
mechanically introduced into a basin followed by redistribution of elements (notably uranium) by
metamorphism, or that the gold, uranium-bearing minerals and pyrite are epigenetic and hydrothermal in
origin. The host rock is an oligomictic conglomerate of vein quartz, chert, jasper, banded iron formation and
quartzite pebbles in a matrix of secondary quartz and phyllosilicates. It contains detrital, abraded pyrite, chromite, zircon, uraninite, gold
and other heavy minerals. Locally, gold and uranium are found within narrow carbonaceous-rich horizons. Over seventy minerals have
been recorded.

Manganese deposits
These are common and widespread and are often associated with sedimentary iron ores. There are a number
of classes of deposit, including: deep sea manganese nodules, precipitates from stagnant water, non-
volcanogenic quartz-clay-glauconite and manganese carbonate associations, and volcanogenic sedimentary
manganese ores.
Sedimentary manganese ores mainly comprise manganese oxides and hydroxides or
manganese-bearing carbonates. Manganese sulphides are uncommon ore minerals (unlike iron sulphides) and
manganese silicates are characteristic of metamorphic or metamorphosed deposits. Individual manganese minerals,
especially oxides and hydroxides, are difficult to distinguish in reflected light, hence the terms 'wad' or
'psilomelane' are often used to denote the presence of mixtures of unidentified soft and hard manganese minerals,
respectively. X-ray powder diffraction is a more successful method for the identification of these species.
Similarly, the characterization of manganese-bearing carbonates requires a knowledge of their chemistry. (Roy,
1968,1976, 1981; Bonatti et al., 1972; Burns and Bums, 1979). Small (up to 30 cm in diameter) manganese nodules occur in vast numbers
over large areas of the deep ocean floor. They are authigenic in origin and often nucleate on detrital grains, organic material or earlier
nodules.
They comprise mixtures of oxides and hydroxides of iron and manganese, together with clays, zeolites,
quartz, opal, baryte and feldspar. The nodules carry significant amounts of cobalt, nickel and other minor
metals sorbed onto the major phases and are regarded as having potential economic interest.
In reflected light, individual minerals cannot be identified by their optical properties. However, within the
collomorphic banding that is characteristic of the nodules, separate bands can be distinguished by
reflectance differences and by the presence or absence of bireflection and anisotropy. Amorphous iron and
manganese hydroxides have low reflectances (less than 9%), polish poorly and are isotropic, whereas
todorokite and birnessite-rich bands polish better, have reflectances of approximately 15% and show marked
bireflectance and anisotropy. X-ray powder diffraction of the different bands is the usual method employed
to identify their mineralogy.
Elsewhere, manganese crusts are associated with modem deep sea volcanogenic sulphide deposits and other
volcanic activity close to seamounts; these crusts are often cobalt enriched. (Bums and Bums, 1977a,b;
Sorem and Fewkes, 1977, 1979; Bischoff and Piper (eds), 1979; Muller, 1979; Heath, 1981)

Chemical precipitates in lakes
These are the manganese equivalent of bog iron ores, and comprise hydrated manganese oxides.

Quartz-clay-glauconite associations
These occur within shallow marine deposits in stable cratonic areas. The ores are conformable and form
lenticular or nodular horizons showing mineralogical zoning, from oxide-rich to mixed oxide-carbonate to
carbonate-rich facies. These facies types primarily are related to palaeogeography but also to subsequent
supergene enrichment processes. In the shallow water oxide zone the ore mineral assemblage comprises
manganite, pyrolusite-manganite or psilomelane associated with limonite. This zone passes into a
transitional zone of manganese-bearing carbonates and manganese oxides and hydroxides which, in turn,
passes into the deeper water carbonate zone. This zone consists of nodules and lenses of cryptocrystalline manganese-bearing carbonates,
including calcic rhodochrosite, manganocalcite and manganoan calcite.

Manganese carbonates in limestones and dolomites
These are divided into the Moroccan-type, found in stable platform environments, and the Appalachian-type, found in geosynclinal
sequences. Moroccan-type deposits comprise manganese oxides, pyrolusite and psilomelane. They occur in limestones and dolomites,
often in association with red bed sequences. Appalachian-type deposits are found in limestones, dolomites and volcanic sequences where
they form beds and lenses of manganocalcite and calcic -rhodochrosite within carbonate host rocks.

Sedimentary-volcanogenic manganese deposits
These are widespread but individual deposits are small and of little economic importance. The ores are stratiform or lensoidal, and
comprise manganese oxides interbanded with chert and jasper on a centimetre scale. Many are associated with volcanogenic sulphide
deposits. Metamorphism of these deposits produces complex silicate ores that vary in mineralogy with the degree of contact and regional
metamorphism. Braunite, hausmannite, rhodonite, bustamite, tephroite, pyroxmangite and piemontite associated with haematite,
magnetite, limonite, and iron and base metal sulphides are typical minerals of this association. (Zantop, 1981)

Sedimentary iron ores
Iron is a common constituent of sediments, and, hence, sedimentary iron ores are widespread and all classes of deposit have been
exploited from the Iron Age to the present. In order of increasing economic importance, the main classes are bog iron ores, clay
ironstones, minette-type ores, Clinton-type ores and iron formations. Only the last two are mined. (James, 1954; Murray, 1979)

Bog iron ores
These are of very localized occurrence and are found in present-day lake and marsh sediments where iron has been fixed by humic
complexes. The iron is subsequently released by bacterial action and is precipitated as ferric oxides and hydroxides associated with minor
amounts of siderite and vivianite.
Limonite is the generalized term for poorly characterized iron hydroxides which include mixtures of goethite, lepidocrocite, akaganeite
and feroxyhyte.

Clay ironstones, blackband ironstones
These deposits are widespread but low grade. They occur within marine sequences and represent the fossil equivalents of bog iron ores.
Dolomite and siderite are the main iron-bearing minerals and, historically, the ores were roasted to convert iron carbonate to iron oxide.
(Curtis et al., 1975)

Minette-type ores
This is the commonest type of unmetamorphosed ironstone, but, with an iron content of 30-35% by weight,
minette-type ores are generally uneconomic. The ironstones are found in shallow marine carbonaceous
shale, mudstone, marl, limestone and ironstone sequences. The main iron-bearing minerals are limonite,
siderite and chamosite with lesser amounts of magnetite, haematite, greenalite and pyrite. Typically, the iron
ores comprise ooids of chamosite, haematite and limonite which have nucleated about detrital grains or
fossil fragments. Quartz, calcite, cellophane and silica are the main gangue minerals. Ores of Jurassic age
were mined in Europe in the nineteenth and twentieth centuries. (Kimberley, 1979, 1981; Maynard, 1986)

Clinton ores
The class is named for the Silurian Clinton Formation of the eastern United States of America where oolitic ironstones, together with
argillaceous and carbonaceous shales, limestones and dolomites, occur within shallow marine sediments. Haematite, chamosite and
siderite are the main iron-bearing minerals and are associated with calcite and silica.

Iron formations (banded iron formations)
Iron formations are defined as thinly-bedded or finely laminated chemical/biochemical sediments
comprising chert (jasper), plus iron-bearing oxides, carbonates, silicates or sulphides. These are
characteristically enormous deposits and range from Archaean to Lower Palaeozoic in age, although most
are Proterozoic. They are subdivided, partly on their tectonic environment, into Algoma-type, found in
volcano-sedimentary sequences in greenstones belts, and into Lake Superior-type, found in continental-shelf
sequences of quartzites, cherts, black shales and dolomites. The mineralogy of the ores is variable and this
reflects primary sedimentary facies variations, later diagenetic effects, and metamorphism.

Unmetamorphosed iron formations can contain four facies types, which are believed to represent original
variations in the sedimentary conditions. These are an oxide facies formed in well oxygenated waters and
comprising magnetite-chert or haematite-chert; a carbonate facies dominated by siderite; a silicate facies
containing chamosite, glauconite, greenalite and locally minnesotaite and stilpnomelane; and a sulphide
facies of pyrite and minor pyrrhotite formed in an oxygen-poor environment often associated with black
shales. Silica is the main gangue of the oxygen-rich facies, whereas carbonates including siderite, ankerite
and dolomite are important in the more reduced facies. Many iron formations have been metamorphosed, their original sedimentary and
diagenetic features destroyed and their original mineralogies altered to complex iron silicate associations. Supergene oxidation of
magnetite to martite and primary iron minerals to limonite is widespread and economically important. (Eichler, 1976; Kimberley, 1978;
Trendall and Morris (eds), 1983)

Bauxites
These are the major ores of aluminium, but with increasing amounts of hydrated iron oxides, bauxites grade
into laterites. Bauxites, which are Cretaceous to Recent in age, can be divided into a laterite crust-type
formed by the weathering of aluminous non-calcareous rocks and a karstic-type formed from aluminous
limestones or dolomites.
In bauxites the aluminium oxide mineralogy changes with increasing metamorphic
grade from gibbsite to boehmite to diaspore and finally to corundum. These minerals are accompanied by quartz,
kaolinite, halloysite, limonite and haematite, together with a very large number of relict phases from the parent
rock, including anatase, rutile, sphene, zircon, pyrite and hogbomite. Pisolitic, oolitic or conglomeratic fabrics are
common in bauxites and many ores retain relict fabrics of their parent rocks. Individual oxide and hydroxide
minerals are very difficult to distinguish in reflected light and X-ray diffraction methods are usually employed to
characterize the mineralogy of bauxites. (Brdossy, 1982)

Lateritic nickel deposits
In unmineralized basic and ultrabasic rocks, nickel is held in olivine and to a lesser extent in other mafic silicates, magnetite and
pyrrhotite. It also forms discrete sulphides and arsenides, including pentlandite, millerite, heazlewoodite and niccolite. The nickel
contribution from olivine is the most significant, and, hence, the most productive parent rocks are peridotites and similar ultramafics
although, norites are also important. Nickel, together with magnesium and iron, is released on weathering and either reprecipitates with
iron (and cobalt) and silica close to the surface to form nickel-rich limonitic ores (called nickeliferous iron ores), or passes down through
the upper weathering zones to precipitate with magnesium and silica as nickel-bearing hydrous silicates (which are collectively known as
garnierite) to form nickel silicate ores. Beneath these ores lie altered and then fresh parent rock. (de Waal, 1971; Golightly, 1981)

Oxidation of sulphides and supergene enrichment
Many primary sulphide deposits have been subjected to secondary alteration and oxidation. Oxidation is the
major process above the water table and sulphides are oxidized to sulphates, oxides and hydrated oxides,
especially limonite or, more rarely, haematite. Pocks which mainly comprise limonite and silica and which
overlie sulphide ores are called gossans. Gossans typically show a cellular structure of goethite and silica
that have precipitated along grain boundaries, cleavages or twin planes of the primary sulphides. Brightly
coloured secondary base metal carbonates and sulphates, relict sulphides and native metals are also present.
The textures and mineralogy of gossans reflect the textures and mineralogy of the original sulphide ores, especially if the primary ores
were coarse grained. Some of the metals go into solution and migrate downwards to meet the water table. Here, conditions change from
oxidizing to reducing and the metals reprecipitate as secondary sulphides. Commonly, this dramatically increases the grade of the ore,
especially where the primary ore comprises disseminated sulphide. This zone is known as the supergene enrichment zone. Supergene
enrichment occurs as a series of oxidation and hydration reactions acting upon the original sulphide species. The degree of oxidation of
the more susceptible minerals often controls the subsequent oxidation and alteration of the less susceptible ones. The generalized sequence
of susceptibility is: pyrrhotite > chalcopyrite > fine-grained pyrite > sphalerite > galena > coarse-grained pyrite. (Sillitoe and Clark, 1969;
Blain and Andrew, 1977; Andrew 1980; Sangameshwar and Barnes, 1983; Nickel and Daniels, 1985)

Sedimentary-hosted base metal deposits
These deposits range from Proterozoic to Tertiary in age and are hosted by shales, siliciclastics and
carbonates. They are important ores of copper, lead, zinc, uranium and silver, and can be syngenetic,
syndiagenetic or epigenetic in origin. Older deposits are often metamorphosed. (Sangster (ed.), 1983)

Black carbonaceous shale-hosted copper deposits
These stratiform deposits account for a significant proportion of the world's copper reserves. Two main copper provinces: the Upper
Proterozoic Zambian Copper Belt and the Lower Permian Kupferschiefer of central and northwest Europe have been studied intensively.
Both provinces have huge, essentially syngenetic/diagenetic ores found in shallow marine sediments associated with major transgressions.
Anoxic conditions and bacterial reduction of sea water sulphate were important controls on mineralization. The ores have both lateral and
vertical mineralogical zonation related to palaeogeographical conditions. In the Kupferschiefer, this zoning is copper- and silver-rich
passing upward into lead- and zinc-rich ores, whereas in the Zambian Copper Belt, it is chalcocite passing basinwards into bornite, then
chalcopyrite and finally pyrite. In unmetamorphosed examples the sulphides are fine-grained and their distribution reflects primary
sedimentary features of the host sediments. Associated volcanicity is minor in extent or absent.

The main sulphides of the unmetamorphosed Kupferschiefer are fine-grained pyrite, chalcocite, galena, sphalerite, digenite, djurleite,
bornite, chalcopyrite and covelline. Minor minerals include anilite, tennantite, luzonite, mooihoekite, haycockite together with trace
amounts of cobaltite-gersdorffite, smaltite-chloanthite, clausthalite, molybdenite, native gold, native silver and platinum group minerals.

Stratiform copper-silver ores in green siliciclastics
Some shallow marine clastics contain minor green-grey siltstone, light-coloured sandstone or carbonate-rich
horizons within a dominantly purple-red sequence. The subordinate horizons are hosts to low grade copper-
silver ores which are believed to be diagenetic in origin. Copper, iron and silver stripped from the main
oxidized reddened sequence are reprecipitated as pyrite, followed by copper-iron and copper sulphides.
Although discrete silver minerals are present in trace amounts most of the silver occurs within copper
sulphides ('chalcocite'), including digenite, anilite, djurleite and chalcocite. Typically, the sulphides are
finely disseminated or form veinlets parallel with the bedding of the host rocks. (Hayes and Einaudi, 1986; Lange et al., 1986, 1987)

Sandstone-hosted uranium-vanadium and base metal deposits
There are two main classes of deposit: uranium deposits and red bed copper (lead and zinc) deposits. The ores are mined for uranium,
copper, vanadium and minor silver, lead and zinc. Both classes are hosted by continental to very shallow marine sediments laid down
under and conditions. The sequences are characteristically reddened by fine-grained haematite coatings (called 'pigment') around the
clastic grains. The mineralization is conformable, often associated with primary sedimentary features and is concentrated in bleached or
grey-green organic and pyrite-rich beds. The ores are diagenetic to epigenetic and, because of the porosity of the host sediments, are often
characterized by a large number of brightly coloured secondary oxidation zone minerals.

Uranium deposits in sandstones. (Colorado Plateau, Wyoming rollfront deposits)

Large scale deposits are found in the western states of the USA, mainly within Mesozoic fluviatile sandstones and siltstones. The deposits
form flats, pods or the characteristic roll-fronts at the junctions between oxidized and reduced clastics. Uranium, in association with
pyrite, is initially fixed in the clastics by organic material; on oxidation of these sediments (reddening), the uranium is oxidized and moves
in solution until it encounters reducing conditions when it reprecipitates (often replacing plant material). Uraninite (as pitchblende),
coffinite, uranium-rich organic material, carnotite and tyuyamunite, together with many secondary uranium and vanadium phases, are the
main ore minerals. These are associated with lesser amounts of pyrite, marcasite, galena, sphalerite, chalcopyrite, bornite and chalcocite.
(Fischer, 1968; Harshman, 1968; Kelley et al., 1968; Young, 1984)

Red bed copper deposits
Although some are lead-zinc-rich and economic, the majority are copper-rich, small and sub-economic. The
ores are concentrated into bleached horizons within reddened sequences, where they form syndiagenetic
cements around elastic silicate grains. The main sulphides include the blue copper sulphides (chalcocite),
bornite, pyrite, galena, sphalerite and covlline, together with many secondary copper, lead and zinc
carbonates and sulphates. The primary (and secondary) mineralization is controlled by the local porosity and
permeability of the host rocks. (Holmes et al., 1983; Zielinski et al., 1983)

Carbonate-hosted Irish-type deposits
This class has similarities with the older exhalative shale-hosted lead-zinc deposits (Mount Isa type) and
those of the Mississippi Valley type. The type examples are found in Lower Carboniferous shelf carbonate
sequences of the Central Irish Plain. The carbonates lie transgressively over Devonian siliciclastics and
mineralization is localized close to Caledonian-trending faults. The deposits occur in argillaceous to
dolomitic carbonates and most have simple mineralogies but complex synsedimentary textures. The main
sulphides are pyrite, sphalerite, galena and marcasite, and locally chalcocite and bornite accompanied by
minor amounts of tetrahedrite-tennantite, boulangerite, bournonite and other sulphosalts. Mineralization is believed to be the result of
fluid exhalations onto the seafloor, accompanied by replacement and void infilling of the underlying sediments. (Hitzman and Large,
1986; Russell, 1986)

Mississippi Valley-type
This class of deposit is mined for lead, zinc, fluorite and baryte. These epigenetic deposits usually occur
within Phanerozoic limestones and dolomites in sequences that are often associated with evaporates.
Individual deposits may be small, but, collectively, they occur within large ore fields. Mineralization is
concentrated along erosional surfaces, karstic surfaces or in faulted and brecciated carbonate, and comprises
void infilling and metasomatic replacement ores. Associated wallrock alteration is restricted to
dolomitization, silicification and the introduction of pyrite. Mineralization is polyphase. Three mineralogical
subclasses are recognized, the most common is the zinc-rich, but lead-rich and fluorite-rich subclasses are also important. (Heyl, 1983;
Kisvarsanyi et al. (eds), 1983; Hagni, 1986; Kyle and Price, 1986)

South Pennines and Mendip Hills, Britain
Both void infilling and metasomatic replacement deposits occur within Lower Carboniferous limestones, or
more rarely dolomites, and have many of the characteristics of the fluorite-rich subclass of the Mississippi
Valley deposits. Galena and sphalerite are accompanied by bravoite, pyrite, marcasite and chalcopyrite
within a fluorite, baryte and calcite 'gangue'. (Dunham, 1983, Ixer, 1986).

North Pennine Orefield, Britain
Lower Carboniferous limestones and sandstones, that have been mineralized, lie unconformably upon
granitic basement. The mineralization within the orefield is zoned: an inner higher temperature zone is
characterized by a pyrrhotite, chalcopyrite and quartz association with minor lead and zinc, and is
surrounded by galena-rich and sphalerite-rich outer zones. The minor ore mineralogy within all of the zones
is complex, with nickel-cobalt-iron arsenides and sulpharsenides, bismuth, silver and antimony minerals and
rare earth phosphates and fluorocarbonates. This mineralogy suggests a geochemical contribution from the
underlying granite. (Dunham, 1948, 1983; Brown et al., 1987)

Syngenetic exhalative lead-zinc deposits in shales and carbonates (Mount Isa type)
There are few examples of this class of deposit, but they are large and produce significant by-product silver. The deposits are Middle
Proterozoic to Palaeozoic in age and are found in shallow water black shales, siltstones, cherts and evaporates or their metamorphosed
equivalents. Basalts and tuffs form part of these sequences but do not appear to be related genetically to mineralization. In
unmetamorphosed deposits the sulphides are very fine-grained and often contain much framboidal pyrite; with metamorphism the
sulphides coarsen in grain size. Pyrite, sphalerite, galena, pyrrhotite and freibergite are the main ore minerals and, amongst the silver-
carriers, freibergite, stephanite, pyrargyrite, argentopyrite and native silver are important. Basinal compaction with the expulsion of
interstitial saline brines along faults is the most widely accepted model for the genesis of these deposits. (Love and Zimmerman, 1961;
Stanton, 1963; Mathias and Clark, 1975; Finlow-Bates and Stumpfl, 1979; Perkins, 1984)




Pyrite, marcasite, wolframite, arsenopyrite, molybdenite, rutile and cassiterite. Mount Pleasant, New Brunswick, Canada







125m


Pyrite (light yellow-white, centre top left) forms small euhedral crystals within marcasite (blue-green white, higher reflectance, centre
bottom right). This is typical of pyrrhotite replacement/alteration by iron disulphides. Rhombic arsenopyrite (white, high reflectance,
bottom centre) is present. Prismatic wolframite (brown-grey, centre and left centre) is enclosed within a pseudomorph after pyrrhotite (left
centre) but mainly occurs within the gangue (black). Rutile (light grey, centre) is rimmed by cassiterite (dark grey, lower reflectance than
wolframite, centre). Curved laths of molybdenite (light to dark grey, bottom centre, centre right) show strong bireflectance and reflection
pleochroism.




Polished block, plane polarized light, x 160, oil
Location: Porphyry-style wolframite-molybdenite-arsenopyrite-sphalerite. Mount
Pleasant, New Brunswick, Canad

Two quartz-feldspar porphyritic stocks have intruded Carboniferous acid volcanics
and both the mineralization and wallrock alteration are zoned about them. Potassic
alteration of the porphyry stocks has produced numerous orthoclase, quartz, fluorite
and molybdenite veinlets and passes out into a zone of phyllic-style alteration
comprising quartz, muscovite and chlorite with minor topaz and fluorite. Within this
zone, silicification accompanied by topaz and fluorite is intense and passes outwards
to a chlorite zone with lesser amounts of silica and fluorite. Early tungsten,
molybdenum and bismuth minerals with arsenopyrite and minor cassiterite occur
along joint planes or are disseminated within the stock a5 an inner zone. Cassiterite,
arsenopyrite, sphalerite and chalcopyrite are disseminated within breccia pipes and
dykes as a middle zone, and sphalerite, arsenopyrite, cassiterite, chalcopyrite, galena,
and bismuthinite occur as a replacement deposit at the margins of the stocks.
Major Minerals: Arsenopyrite, sphalerite, wolframite (ferberite), molybdenite, native bismuth,
cassiterite, lollingite chalcopyrite, galena
Minor Minerals: Scheelite, rutile, bismuthinite, stannite, kesterite, stannoidite, pyrite, tennantite,
marcasite
Trace Minerals: Include wittichenite, galenobismutite, aikinite, cosalite, covelline, blaubleibender
covelline, bornite, pyrrhotite, pyrargyrite
Textures: Rutile is prismatic or acicular. Tabular wolframite is associated with scheelite.
Euhedral, simply twinned cassiterite is replaced by chalcopyrite and sphalerite.
Molybdenite encloses the oxide minerals. Arsenopyrite/lollingite carry native
bismuth inclusions and are fractured. A number of sphalerite generations are present
and enclose pyrrhotite and stannite group minerals. Chalcopyrite disease in sphalerite
is widespread. Chalcopyrite carries stannite inclusions as does galena. Pyrrhotite is
altered to, and pseudomorphed by, pyrite and marcasite to give bird's-eye and lath-
shaped textures
References: Dagger, 1972; Petruk, 1973; Parrish, 1977; Davis and Williams-Jones, 1985;
Kooiman et al., 1986



Opaque and ore minerals associated with intermediate and acid igneous rocks




Opaque minerals in unmineralized intermediate rocks
The primary iron-titanium oxide minerals (magnetite ulvspinel, ilmenite-haematite and rutile), together
with their secondary oxidation products (maghaemite, haematite, pseudobrookite, TiO
2
minerals and
sphene), are similar to those found in basic rocks. Chromite, however, is less common but other metal
oxides, namely cassiterite, columbite and bixbyite, are more abundant. Early sulphides include pyrrhotite,
pyrite, chalcopyrite and marcasite. (Haggerty, 1976b).

Opaque minerals in unmineralized to lightly mineralized granites
Although the mineralogy of granites is variable, they are essentially quartz and feldspar rocks that carry
micas, amphiboles and pyroxenes, together with a wide variety of accessory minerals. Accurate
characterization of the minor and accessory phases within granites should complement geochemical studies,
especially if mass-balance calculations are to be performed. Reflected light investigation of the opaque and
accessory phases has an important role in helping to discriminate fertile from infertile granites, in terms of
their potential for economic metalliferous deposits or for geothermal energy (the so-called high heat
producing granites). Accessory minerals are found as 10-100m diameter grains between quartz and feldspars, or commonly within mafic
and especially altered mafic minerals. Pleochroic halos in mafic minerals usually suggest the presence of one or more accessory minerals
and repay careful study. Amongst the more common primary opaque and accessory minerals are zircon, allanite, sphene, tourmaline,
epidote; ilmenite-haematite, magnetite-ulvspinel, cassiterite, columbite-tantalite, uraninite, thorite, TiO
2
minerals, pyrochlore group
minerals, wolframite; apatite, monazite, xenotime; pyrite, pyrrhotite, chalcopyrite, sphalerite, arsenopyrite and molybdenite. In addition,
numerous rare earth element-bearing carbonates and fluorocarbonates and U-Nb-Ti-bearing oxide minerals have been recorded. The
accessory minerals occur as loose aggregates, often with symplectite-like intergrowths, at crystal boundaries of the silicates, or lie along
the cleavage planes and grain boundaries of mafic minerals.
Few granites have escaped post-magmatic alteration by hydrothermal fluids and so show alteration and
localized migration of their primary phases. Alteration includes the replacement of ilmenite by sphene and
TiO
2
minerals, and titanomagnetite by leucoxene. The crystallization of TiO
2
, minerals, ilmenite and
haematite along the cleavages of altered mafics, especially biotite, suggest local redistribution of elements
from silicates into oxides. Haematite and sulphides, notably pyrite, marcasite and chalcopyrite, are
introduced during hydrothermal alteration. Many of the accessory minerals are translucent to semiopaque
and so polished thin sections are more useful than polished blocks. Accessory minerals are often irregular in
their distribution, complexly intergrown with each other and, because of their low and similar reflectances and strong internal reflections,
are difficult to characterize in reflected light. Oil immersion and high magnification are required for the discrimination of fine-scale
properties like zoning. Transmitted light petrography and chemical characterization by SEM or electron microprobe are also needed.
Autoradiographs and Lexan overlays are used for locating the sites of uranium- and thorium-bearing phases. (Ishihara, 1977; Basham et
al., 1982; Mackenzie et al., 1984; Chatterjee and Strong, 1985)

Mineralization associated with granites
The classical sequence of late-stage magmatic to post-magmatic alteration and mineralization involves
pegmatite formation followed by greisenization, albitization and, finally, hydrothermal quartz-sulphide
veining. (Eugster, 1985; Plant, 1986)

Pegmatites
Granite pegmatites are economically important sources of quartz, feldspar and micas. In addition, they are
major producers of Li, Be, Cs, Pb, W, Sn, Th, Nb-Ta, rare earth element (REE) minerals and gemstones.
Minerals in pegmatites are often coarse-grained. Simple pegmatites are essentially quartz, potash feldspar,
sodic plagioclase and biotite, together with muscovite, tourmaline and garnet. Complex pegmatites are
zoned and have the same essential mineralogy as simple pegmatites, together with more exotic silicates.
Opaque and semi-opaque minerals include Th-bearing phases, thorianite and thorite; U-bearing phases
including uraninite and uranothorite; Nb- and Ta-bearing phases, columbite, tantalite, pyrochlore group minerals and ilmenorutile; Sn-
bearing phases, primarily cassiterite; W bearing phases, wolframite and scheelite; and a wide variety of REE-phases, including monazite,
xenotime, allanite, samarskite, bstnasite and parisite group minerals. Native bismuth, bismuthinite, molybdenite, stannite group minerals
and many base metal sulphides are found in minor amounts. (Cerny (ed.), 1982; Brown and Ewing (eds.), 1986)

Post-pegmatite alteration
Late stage fluids metasomatically alter acidic and alkaline plutonic rocks and the resulting metasomatites are
found in apical areas of the parent pluton. Albitization, microclinization and greisenization are amongst the
most important alteration processes to be associated with mineralization. The alteration sequence is not
uniform; in Nigeria, albitization is followed by microclinization and then by greisenization, whereas in
Comwall albitization is later than microclinization. (Jackson, 1986)

Albitization
In Nigeria, sodium-rich fluids have altered a variety of granites into quartz-albite rocks containing minor
amounts of Li-rich mica. Accompanying the alteration is an enrichment of Nb (Ta), Zr, Hf, Th, U, PEE, Fe,
and Mn. Different compositions of the primary granites are reflected in different mineralogies in their
secondary albitites; for example, niobium mineralization in peraluminous granite is present as columbite, in
peralkaline granites as pyrochlore, and in metaluminous granites as fergusonite.

Microclinization
At Ririwai, potassic metasomatism has converted a biotite granite into a quartz, microcline and white mica rock with subordinate amounts
of topaz and sericite. Minor amounts of tin and tungsten were introduced.

Greisenization
This is a widespread and important ore forming process produced by hot acidic fluids. Greisen is a quartz
and white mica (muscovite, sericite, zinnwaldite) rock, forming irregular masses, veins or stockworks
cutting apical regions in granites. Topaz, tourmaline, fluorite, biotite and albite can be present in significant
amounts in addition to ore minerals. Greisens can carry an extensive opaque mineralogy, including
cassiterite, wolframite, scheelite, columbite, haematite, magnetite, brannerite, molybdenite, pyrrhotite,
pyrite, marcasite, arsenopyrite, chalcopyrite, sphalerite, galena, stannite, tetrahedrite group minerals, native
bismuth and bismuthinite. Cassiterite, wolframite and scheelite-bearing greisens, and wolframite, molybdenite and native bismuth-bearing
greisens are economically the most important. (temprok, 1985; Taylor and Strong, 1985)

Mineralized quartz veins within granite
Cross-cutting quartz veins in granites are common and carry metal oxides, base metal sulphides and
arsenides. Associated wallrock alteration includes greisenization and tourmalinization. These are the
classical tin-tungsten-molybdenum-bismuth-arsenic-bearing hydrothermal veins associated with apical areas
of granites. The ore mineralogy of the veins is similar to that of greisens except that sulphides become
volumetrically the more abundant and oxide minerals less so. The mineralogy of granite-associated quartz
veins is extensive. Common minerals include cassiterite, wolframite, molybdenite, stannite group minerals,
bismuthinite, chalcopyrite, sphalerite, galena, pyrrhotite, pyrite, marcasite, arsenopyrite, lollingite and tetrahedrite group minerals. These
are accompanied by minor amounts of sulphosalts and native metals.

Porphyry deposits
Much of the world's copper and molybdenum are produced from very large tonnage low grade sulphide ores
associated with high level, acid to intermediate, porphyritic intrusions of Tertiary to Quaternary age; these
are the porphyry deposits. Three main types are recognized: porphyry copper, porphyry molybdenum and
smaller porphyry-style tin-tungsten stockwork deposits. By-product gold, silver and base metals are
produced.

Porphyry copper deposits
These are mined for copper with by-product molybdenum, gold and silver; some contain tungsten as
wolframite. A central, small, porphyritic stock is surrounded by a series of genetically related alteration
zones and ore shells that carry hypogene sulphide (and minor oxide) mineralization in disseminated quartz
veinlets and healed microveinlets. In some deposits, larger veins carrying gold and silver mineralization are
found in the outermost alteration zone.
Moving from the porphyritic stock outwards, the hydrothermal wallrock alteration zones are: potassic,
phyllic, argillic and propylitic. Each carries a distinctive hypogene sulphide-oxide assemblage. The inner
potassic zone, characterized by the development of secondary orthoclase and biotite together with quartz,
albite, sericite,. anhydrite and apatite, is roughly coincident with an innermost low-grade chalcopyrite,
pyrite, molybdenite, magnetite and bornite zone. Molybdenite, then chalcopyrite and finally pyrite increase
in amounts towards the phyllic zone, but generally chalcopyrite is more abundant than pyrite.
Rocks in the phyllic zone comprise quartz, sericite and pyrite (with up to 10% by volume pyrite). The main
economic ore shell occurs within this zone, often at its junction with the potassic zone. Pyrite is
accompanied by chalcopyrite, molybdenite, bornite, chalcocite, magnetite, enargite and sphalerite within
abundant quartz veinlets. The argillic zone comprises montmorillonite, illite, chlorite and kaolinite and
carries pyrite with chalcopyrite and bornite with trace amounts of chalcocite, enargite, molybdenite,
tennantite, sphalerite, galena and wolframite. The propylitic alteration zone comprises chlorite, epidote,
calcite and pyrite. Pyrite is the main sulphide and trace amounts of bornite, molybdenite, sphalerite, galena,
magnetite, specularite, rhodochrosite and rhodonite are also present.
The outermost part of this zone carries chalcopyrite, galena and sphalerite veins with gold and silver
mineralization. Superimposed upon this primary mineralization can develop an extensive supergene
'chalcocite lanket'. This comprises chalcocite, djurleite, digenite with minor blaubleibender covelline,
cuprite and native copper. Often overlying the chalcocite blanket and primary zones is a 'limonite' gossan
containing jarosite, copper carbonates- copper oxides, native copper and haematite. (Titley and Hicks (eds.),
1966; Drummond and Godwin, 1976; Ney et al., 1976; Hollister, 1979; Beane and Titley, 1981; Titley (ed.),
1982)

Porphyry molybdenum deposits
These are rarer than porphyry copper deposits and produce byproduct tungsten. They are Mesozoic to
Tertiary in age and have been divided into 'Climax-type' (stockwork type), associated with multiple
porphyritic granitic intrusions with molybdenite and pyrite as major sulphides, accompanied by wolframite,
cassiterite, stannite and bismuth sulphosalts; and the ,quartz-monzonite' type, associated with granites,
granodiorites and quartz monzodiorites. In addition to molybdenite and pyrite, these carry minor amounts of
scheelite, bismuth sulphosalts and chalcopyrite. Both types of porphyry molybdenum deposits are
accompanied by potassic, phyllic, argillic and propylitic alteration but also by more minor silicification, quartz vein, greisenization and
garnet-rich zones. The majority of the molybdenite occurs as stockwork quartz-molybdenite veins. The potassic zone contains K-feldspar,
quartz, magnetite and biotite, and the phyllic zone abundant sericite and pyrite. Both zones carry minor molybdenite. In the argillic zone,
kaolinite, montmorillonite and sericite replace feldspar, and biotite is altered to muscovite, sericite plus minor rutile, leucoxene, pyrite,
carbonates and fluorite. The propylitic zone carries chlorite, epidote and pyrite accompanied by calcite, clays and sericite. Greisen veins
comprise quartz, molybdenite, topaz, pyrite, magnetite and muscovite, whereas in the garnet zones spessartine is accompanied by galena,
sphalerite and rhodochrosite. Supergene mineralization in porphyry molybdenum deposits is weak to absent. (Wallace et al., 1978;
Sillitoe, 1980; White et al., 1981)

Other porphyry-style deposits
Other deposits, notably tin- and tungsten-bearing, show many similarities to porphyry copper and
molybdenum deposits. They are associated with high level porphyritic stocks that are accompanied by
broadly concentric alteration and mineralization zones. Potassic alteration is rarer, although greisenization is
more common than for porphyry copper deposits. (Sillitoe et al. 1975, Grant et al. 1980; Noble et al. 1984)