Chapter 2

How Do Mineral Deposits Form

and Transform? A Systematic Approach

Abstract Formation and transformation of mineral deposits are interactions of

geospheres, one including the atmosphere, hydrosphere, biosphere, lithosphere, and
asthenosphere and the other involving the mantle and the core of the earth. Complex
chemical and thermal interactions between these two geospheres have led to distri-
bution and concentration of elements and even, later modifications, producing the
mineral or ore deposits of today. The essential processes involve magmatism,
hydrothermal, and sedimentary processes with a strong impact of tectonism and in
places, of weathering and erosion. The genetic processes vary in details. The principal
ones are outlined below with the principal products in parentheses: (1) Essentially
magmatic processes (Ni, Cu, PGE Cr, Fe–Ti); (2) Pegmatitic processes (rare metals,
ceramic, and radioactive elements); (3) Essentially magmatic hydrothermal processes
(Sn, W, U, Cu, Mo, REE); (4) Essentially amagmatic hydrothermal processes (Cu,
Pb–Zn, Au, U); (5) Sedimentary (-diagenetic) processes (Fe, Mn, U, Sn, Ti, monazite,
phosphorite, carbonate rocks, rock salt gypsum); (6) Lateritic and non-lateritic
residual processes (Fe, Mn, Al, Ni, and clays); (7) Supergene oxidation and
enrichment (Cu, Ag, Au, U); (8) Biogeochemical degradation of biomass
(peat-lignite-coal, natural gas, and oil).

Keywords Magmatic process of ore genesis Pegmatitic process of mineral for-
mation
Hydrothermal process of ore formation

SEDEX deposits VMS





deposits MVT deposits Metamorphism and ore genesis Sedimentary-diagenetic



processes of ore formation Placerization Lateritic process of ore formation



Supergene enrichment of ores Biogeochemical degradation of biomass

2.1 Introduction

The earth’s total stock of ore metals is found in two geospheres or physicochemical
systems (Brimhall 1991): the outermost geosphere is a thin reactive shell near the
surface of the earth which includes the atmosphere, biosphere, hydrosphere,
lithosphere, and the asthenosphere on which the oceanic and continental plates

© Springer Nature Singapore Pte Ltd. 2017 29

M. Deb and S.C. Sarkar, Minerals and Allied Natural Resources
and their Sustainable Development, Springer Geology,
DOI 10.1007/978-981-10-4564-6_2
30 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

move. This complex geosphere is underlain by another, comprising the mantle and
the core (cf. Fig. 1.11). It is believed that all metals are primordial, that is, they have
neither been created nor destroyed since the beginning of the earth, except for a few
metals like lead, which is formed in part by the radioactive decay of uranium and
thorium. Complex thermal and chemical interactions between the two geospheres
have redistributed the elements from time to time through Earth history. During this
migration and redistribution, mineral concentrations have taken place in rocks of all
ages by primary igneous and metamorphic processes in deeper crust or upper
mantle or by secondary processes resulting from fluid movement and weathering on
or close to the surface. Understanding the genesis of ores through their character-
ization and obtaining the precise information of magmatic, hydrothermal, tectonic,
and sedimentary events that produce the ore-forming crustal fluids and metal
sources that form these economic mineral deposits is a basic approach in ore genetic
studies. Thus many ore deposits are produced at depth in the endogenous envi-
ronment, characterized by the earth’s internal heat and its dissipation. They are
eventually exhumed or brought close to the surface either by erosion of the cover or
by tectonic uplift or both. A large number of economically important mineral
deposits also form in the exogenous environment where weathering and sedimen-
tation are major geological processes in water-dominant systems that are driven by
the solar heat flux and where biological mediation is common. Between these two
end members, there are also processes which in various combinations contribute to
the formation of ore deposits or their transformation. The ore-forming process may
be initiated in the endogenous realm but produce the deposit at or near the surface,
or the other way round, where meteoric ± connate waters penetrate the rocks,
undergo gravity-driven flow through the strata, or get convected upwards from
depth, leach metals during passage, and deposit them in specific locales in the crust,
commonly oceanic crust, thereby having the signatures of both the environments.
Presently active ore-forming processes in marine environment produce deposits of
this type and provide a clearer perception of the geological setting and processes
responsible for the generation of the ancient analogs.
We list below (Table 2.1) the mineralizing processes of eight major types. This
list includes only those mineral deposit types which are economically important for
the particular metal and account for its major reserve. For an exhaustive list of
various mineral deposit types of the different metals, the reader may refer to the
recent publication of Dill (2010). It must have been noted that we have divided the
mineralogenetic processes into several types, eight to be precise, in Table 2.1. But
why have we put the attribute “essentially” in some of the above types? Let us try to
explain. As will be obvious from the discussion that follows, endogenous
mafic/ultramafic magmas may be important contributors to the formation of Ni–Cu,
Cr, PGE ores for attaining critical composition for ore genesis. But such potentially
ore-bearing magmas generally require magma contamination or country rock
assimilation for reaching the critical composition i.e., supersaturation for chromite
deposition or Ni–Cu–Fe sulfide melt separation. Thus, the process responsible for
ore generation is mainly magmatic, though not totally. Again intrusion-related
magmatic fluids are usually the principal contributors to the formation of
2.1 Introduction 31

hydrothermal ore deposits. But in some cases, aqueous fluid contribution from the
country rocks might have been substantial. The attribute, “essentially amagmatic” is
given to SEDEX, MVT and VHMS deposits also. Fluids from which they were
deposited were essentially hydrothermal following the basic definition of
hydrothermality. Only there is little or no magmatic contribution. Some other
deposits, such as orogenic Au, unconformity type U deposits, and some rare base
metal deposits have been included in this type. Sedimentary(-diagenetic) processes
have several subtypes, as shown under (5) in Table 2.1. Their characters are straight
forward. Residual processes may give rise to both lateritic and non-lateritic (Al-rich
clay) deposits. Biogeochemical degradation produces fossil fuels from micro- and
macro-plant remains under suitable geological environments. Salient aspects of
these processes have been discussed in this chapter, except the ones at 5 (c) and
(d) and (8), which are discussed in the chapters on nonmetallic minerals (Chap. 4)
and Energy Resources (Chap. 6) respectively.
The formation of most of the earth’s mineral resources requires the presence of a
fluid phase to extract the ore elements from their hosts by dissolution, to promote
transport (mechanical and/or chemical) and ultimately to deposit them in suitable
locales. Therefore, the knowledge and understanding of the fluid phase are critical
to the development of any model of ore genesis. These fluids, which may vary
widely in terms of composition, temperature, physical state, and flow characteris-
tics, represent a state of matter in which the molecules are able to flow past one
another without any limit or without any fracture or dislocation. Their state as gas,
vapor, or liquid exhibits a progressively closer association of molecules and is
characterized by different mechanical and thermodynamic properties. At 374 °C
and 225 kg/cm3, that is, at critical temperature and pressure, the most common
solvent, water, changes to a supercritical fluid which has both the gaseous property
of being highly mobile and the liquid property of dissolving various components
(Dill 2010). The different kinds of fluids, in this context, normally reside in, are
generated within or enter into the crust from below (hypogene) or above (super-
gene). They may be mantle-derived, crustally generated or meteoric in origin. Thus,
their flow system is either internal energy-driven (endogenous) or
solar-energy-driven (exogenous), that is, hydrologic (cf. Fig. 1.11). Both the flow
systems are local to regional in extent and under particular circumstances, are
capable of horizontal fluid movement on continental scale (Norton 1977;
Mookherjee 2000). Their movement is driven by various kinds of forces, such as,
heat, tectonic deformation, gravity, buoyancy, capillary action, osmotic pressure,
and/or surface tension along thermal/pressure/compositional/permeability/chemical
potential gradients. At shallow depths, the fluid movement takes place through
fractures, dissolution cavities, and interconnected pore spaces. At greater depths, on
the other hand, fluid movement takes place in tectonically active regions within
interstratified rocks of differing competencies, which confines the movement within
brittle layers acting as “metamorphic/tectonic” aquifers.
Several types of geological situations bring about the flow of crustal fluids either
in a near-hydrostatic fluid pressure regime or in an overpressured fluid regime (Cox
2005). Hydrothermal systems develop in both magmatically active and amagmatic
32 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Table 2.1 Major processes and products in mineral deposit formation (Authors’ unpublished
work)
Ore genetic process* Products
1. Essentially magmatic processes Ni–Cu, PGE, Cr, Fe–Ti, Fe–V deposits
2. Pegmatitic process Rare metals, ceramic, and radioactive minerals,
3. Essentially magmatic
hydrothermal processes
a. Mineralization associated with Sn, W, U, Mo
quartz-rich leucogranite
b. Mineralization associated Cu, Mo, Au
with porphyry systems
c. Skarn- and greisen-related Fe, W, Au, Cu, Pb–Zn, Mo, Sn
mineralization
d. IOCG type mineralization Cu, U, Au, REE
4. Essentially amagmatic
hydrothermal process
a. Volcanic-hosted massive Cu, Zn–Pb (including present marine metallogenesis)
sulfides
b. Sedimentary exhalative Pb–Zn, Cu
(SEDEX) deposits
c. Mississippi valley type Pb–Zn
(MVT) ores
d. Sediment-hosted stratiform Cu (Zambian Cu belt; Kupferschiefer)
ores
e. Metamorphogenic ore Au (orogenic), U (Unconformity type), rare base metals
formation (e.g., Mt. Isa, Australia)
f. Sandstone-hosted U-V Colorado plateau type
5. Sedimentary(-diagenetic)
processes
a. Placerization Au, PGE, monazite (Th, REE), Sn, Ti (rutile, ilmenite),
zircon, precious stones (diamond, ruby)
b. Sedimentary-diagenetic Fe, Mn (including present marine metallogenesis), U
c. Evaporative deposition Rock salt (NaCl), gypsum, K-salts
d. Diagenetic modification of Phosphate deposits, magnesite, dolomite rocks
organic remains, carbonates
6. Lateritic and non-lateritic Fe, Mn, Al, Ni, and clays
residual processes
7. Supergene oxidation and Cu, Ag, U, Au
enrichment
8. Biogeochemical degradation Peat–lignite–coal, natural gas, and oil.
of biomass
*Here, “ore genetic processes” may be read as “Economic mineral deposit formation processes”
2.1 Introduction 33

Fig. 2.1 Sketch of the distribution of various fluid sources and pathways in a convergent regime.
Refer to text for pathway numbers (after Cox 2005)

environments, particularly in parts of accretionary and collisional orogens. Various

fluid sources and pathways (Fig. 2.1) in this context are: (1) structurally controlled
fluid flow; (2) metamorphic devolatilization; (3) thermally driven convection;
(4) fluid exsolution from magma bodies; (5) topographically driven (gravity) flow
of meteoric fluids; (6) basinal flow; (7) devolatilization of subducting slab; (8) fluid
escape along slab interface and into slab hanging wall and (9) devolatilization of
hydrated mantle wedge.
Having formed by such right combination of processes and often being modified
later on near the surface of the earth, the ore deposits remain transitory in the
geological sense and reflect the dynamic processes within and outside the earth.
These include deep weathering over a protracted period of time eroding the ore
deposit or subduction of the plate on which the ore deposit lies. They also serve as
important geochemical sensors providing useful record and history of transport
paths and forces operative in the crust.

2.2 Essentially Magmatic Processes

It is a common geological knowledge that different igneous rocks host different

associations of ore deposits and particular metal associations are found in specific
igneous rocks, e.g., Cr, V, Ni, PGE, Cu, Zn, and Au (both siderophile and chal-
cophile) are associated with basic-ultrabasic igneous rocks in which they show the
maximum crustal abundance. Similarly, elements like Be, Li, Sn, W, U, and Th, as
well as F (all lithophile elements) are associated with acidic igneous rocks. This
implies that there is clearly a strong first-order correlation between magma com-
position and metal enrichment, and a particular metal or metal association has a
relationship to the environment of magma generation and its chemical
34 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

characteristics. Magma, as is well known, is a naturally molten rock matter, which

on cooling gives rise to igneous rock/rocks, or ore material, or both. The magmatic
history of an area may be prolonged, starting from the orthomagmatic through
pegmatitic to hydrothermal stage and as described in the famous Reaction Series of
N.L. Bowen, starts with relatively low-silica and ends up with more siliceous
magmatic rocks enriched in fluids. All three stages, however, may not be present
everywhere. “Orthomagmatic” deposits are those formed where the source material
during emplacement was in the proper magmatic state. Thus, they are represented
by ultramafic to mafic-felsic (dunite-peridotite to anorthosite-troctolite to
gabbro-norite) rocks of intrusive to effusive varieties.

2.2.1 Magmatic Ore Deposits

The geologic processes mentioned above produce “orthomagmatic” ore deposits of

various transition metals (Ti, V, Cr, Fe, Ni, Cu + PGE) in different combinations.
The three main groups associated with basic to ultrabasic magmatic rocks are:
(i) Cr + PGE (Pt, Pd, Ir, Os, Re, Rh), Fe–V
(ii) Ni, Cu, PGE
(iii) Fe–Ti.
The first group may or may not have either PGE or Fe–V ores or both in the
sequence and is represented by stratiform chromite ores in large layered intrusions,
such as, Stillwater Complex, Montana, USA; Kemi, Finland; Fiskenaesset,
Greenland; and or funnel-shaped intrusions, such as, Bushveld in South Africa;
Great Dyke, Zimbabwe; Muscox and Bird River Sill in Canada; Dore Lake,
Australia and Bacuri Complex, Amapa state, Brazil (Cawthorn 1996). The
Bushveld Complex and the Great Dyke of Zimbabwe account for more than 90% of
world resource of chromium. The rocks of these intrusions include dunite, peri-
dotite, pyroxenite and anorthosite, and less commonly, gabbroic rocks. Podiform
chromite deposits in ophiolite complexes, often dismembered, occurring mainly in
Kazakhstan, Phillipines, Turkey, Cyprus, Greece, and Albania, belong to the first
group as well. Also referred to as the “Alpine type”, their irregular shape and
limited reserve is not generally conducive to mining.
In the large intrusives, the chromite-rich layers, a few mm to several meters
thick, are laterally persistent over long distances and alternate repetitively with
silicate layers. They show regular changes in mineral compositions (e.g.,
En-variation in pyroxenes and An-variation in plagioclase) and cryptic layering. In
the enormous Bushveld Complex near the city of Pretoria in the Republic of South
Africa, 29 chromitite seams (Fig. 2.2a) occur in three segments (Fig. 2.2b), eastern,
western, and northern. The igneous stratigraphy sits over the Pretoria Group
basement separated by a Marginal zone, and followed upward by the Lower zone,
the Critical zone hosting the chromitite layers and the Merensky Reef rich in PGE
2.2 Essentially Magmatic Processes 35

with some Ni–Cu, the Main zone showing little differentiation and the upper zone
with the vanadiferous magnetite layers (Fig. 2.2c). The largest orebodies are the
LG3 and LG4 chromitite (a rock composed essentially of chromite) layers in
western Bushveld. The Merensky Reef is a thin (0.3–0.6 m) sheet of pegmatitic
pyroxenite layer in an igneous zone of the complex, traceable over 200 km. Thin
chromitite bands rich in PGE mark the top and bottom of the Reef (Fig. 2.2d). The
Great Dyke of Zimbabwe is 532 km-long and 5–9.5 km wide and hosts as many as
eleven persistent chromitite seams. As discussed below, the chromite accumulations
in such intrusives have taken place through fractional crystallization, gravitative
settling, flow differentiation, and filter pressing.
In deposits of the second group, Ni:Cu ratio may vary drastically and PGE may
also be totally absent. The sulfidic nickel ores with PGE may be concentrated in the
basal zone of mafic to ultramafic intrusions, such as, in Sudbury deposits, Ontario,
Canada (Fig. 2.3a), in the Stillwater Complex, Montana, USA or Nkomati mine,
Mpumalanga, RSA or they may be hosted by rift-related volcanic rocks, such as, in
the Duluth complex, USA; in Norilsk-Talnakh deposits in Russia; at Jinchuan,
China; at Muscox, Nunavut, and Crystal Lake, Canada. The Cu–Ni sulfide ores are
common in the early cycles of some greenstone belts where they may occur in three
different subtypes: the komatiitic subtype (e.g., Kambalda deposits in Yilgarn
craton in Western Australia; Langmuir, Ontario, Canada; Selebi-Pikwe, Botswana),
the dunitic subtype (Mt. Keith, Western Australia) or the picritic subtype
(Pechenga, Kola Peninsula, Russia).
This second group of deposits commonly forms massive, network or dissemi-
nated ores (cf. Fig. 2.4) with rather simple mineralogy of pyrrhotite, pentlandite,
and chalcopyrite. They are mostly of Archean to Proterozoic age found in
unfractionated Mg-rich basic igneous rocks in old continental setting. In all these
deposits, separation of a sulfur-rich liquid containing Fe–Ni–Cu by liquation from a
parental magma and its sinking to the bottom of the magma chamber produced the
orebodies (Fig. 2.3b).
As pointed out by Cawthorn et al. (2005), some fundamental differences exist
between the base metal-rich (Ni–Cu-rich) and PGE deposits. The former are
commonly localized and are discontinuous near the base of intrusives. Important are
the three criteria pointed out by Naldrett (1989) for the magmatic base metal ores.
These are: (1) an olivine-rich magma; (2) proximity to a major fault; (3) presence of
sulfide/sulfate-bearing country rocks. PGE deposits hardly meet these criteria.
Rather they occur in rocks that have pyroxenes with a Mg number of 0.8 (sug-
gesting that the liquid contained only about 6% MgO) when PGE were concen-
trated. Their great lateral continuity means freedom from structural control. They
also occur in the middle of intrusions, where the role of country rock assimilation is
probably not important. However, as PGE occur in very small quantity (in ppb) in
the mafic-ultramafic magmas, large volumes of the latter are needed for the
development of these ores. The role of this volume factor is obvious from the
formulation of Campbell and Naldrett (1979) which controls the grade (tenor) of a
sulfide liquid:
36 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.2 a Chromitite seams of Bushveld complex (after [Link]); b Geological map of
Bushveld Complex showing the disposition of chromite, PGE (Merensky Reef) and Fe–Ti–V
orebodies in the different sectors; symbols for different mineralization same as in (c) (after
Campbell et al. 1983); c generalized stratigraphic log showing the different zones and their
mineralization; d an enlarged view of the PGE-enriched Merensky Reef (after Naldrett 1989)

CSul ¼ ½Co D ðR þ 1Þ=ðR þ DÞ;

where CSul is the concentration of the element in the sulfide fraction; Co is the
original trace element concentration in the host magma; D is the sulfide-silicate
2.2 Essentially Magmatic Processes 37

Fig. 2.3 a Geological map of

the Sudbury complex,
Ontario, Canada; b Cross
section of the Strathcona mine
showing the concentration of
the sulfide ore at the bottom
of the Ni-eruptive (after
Barnes and Lightfoot 2005)

Fig. 2.4 The billiard ball

model of Naldrett (1989)
showing the generation of
different ore textures by liquid
immiscibility
38 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

partition coefficient and R is the “R factor” defined as the mass of silicate magma
that a segregated sulfide liquid has equilibrated with (mass ratio of silicate magma
to sulfide melt). In order to achieve ore grade, the sulfide liquid must equilibrate
with significant quantities of metal-rich silicate magma, that is, have very high
R-factors (*10,000 or higher).
Most chromitites have elevated PGE content, suggesting a correlation between
the two. An explanation of this relationship is contentious. High partition coefficient
of PGE in chromite is unexpected. Recent tendency has been to explain the asso-
ciation by mechanical adherence rather than as solid solution. Hiemstra’s (1985)
preferred suggestion was that PGE crystallized as very small grains, so small that
they could not gravitate down and thus redeposited on chromite grains and ulti-
mately became constituents of the chromitite layers. Mungall (2002) perceived
change in fO2 in magma around the chromite grains to initiate formation of plat-
inum group minerals. It may be pointed out that there are many PGE-bearing reefs
that are not associated with chromite, such as the Great Dyke, J-M Reef, Platreef
(Bushveld, South Africa). It will therefore be reasonable to conclude that PGE in
chromitites (particularly, Ru and Rh) may be related both to the sulfide accumu-
lation in the matrix and metal clusters in chromite, as suggested by Barnes and
Maier (2002).
Evidence of hydrothermal activity in the PGE ore zone has been a common
observation for a long time. It has been particularly observed in the Merensky Reef.
It is an overprint on both the ores and the associated silicates. But interestingly it
did not cause perceptible redistribution of metals. Instead modification of the ore
mineralogy with the depletion of S is a common feature (Cawthorn et al. 2005).
The third metal group represents the orthomagmatic ilmenite deposits within
anorthosite or anorthosite gabbro, such as, at Allard lake, Lac Tio, Lac du Pin
Rouge deposit, Quebec, Canada; Sanford lake, USA. The largest ilmenite body
occurs at Tellnes, Norway, at the base of a noritic anorthosite body. Other deposits
are Smalands Taberg and Ulvö deposits, Sweden. Interestingly, these anorthosite
bodies are found to occur in high-grade metamorphic terrains with gneisses,
granulites, schists and amphibolites. It is believed that residual melts after differ-
entiation from anorthosite–norite magma caused a late enrichment in Fe and Ti.

[Link] Orthomagmatic Ore Genetic Processes

These are broadly categorized into two types:

1. Crystallization-differentiation, leading to disseminations or gravitative settling
of heavy crystallites into cumulates.
2. Fluid Immiscibility or liquation, leading to segregation of melts of contrasted
composition.
2.2 Essentially Magmatic Processes 39

Crystallization-Differentiation

In a liquid multicomponent chemical system, differential crystallization may take

place within the system due to the variation of physicochemical parameters, solu-
bility limit being exceeded at a given T and P for some phases, leading to aggre-
gation of the crystals into separate cumulates, commonly in the form of layers and
lenses (Fig. 2.5). This differentiation is dominated by gravity, but can as well take
place, or rather be augmented by filter pressing or tectonic squeezing across lay-
ering, diffusion, or even fluid flow, when a part of the material is still in the fluid
state.
Monomineralic layers of chromite (chromitite) or magnetite (magnetitite) are
often found in the layered mafic intrusions, represented commonly by mafic and
felsic (gabbro-anorthosite) plutonic rocks, sometimes modified to ferrogabbro and
ferrodiorite (cf. Robb 2005). They contain a fairly large portion of Cr and Fe–Ti–V
ores in the mineralized system. The development of these layers suggest as if these
were formed in the interludes when the silicate crystallization was switched off by a
natural mechanism.
Opinions, however, vary over a wide range regarding the origin of the chromitite
layers. Some major views include:
1. Crystal sinking and sorting
2. Injection of chromite-porphyritic magma
3. Liquid immiscibility
4. Variation in oxygen fugacity (fO2) and total pressure (PT)
5. Crustal contamination
6. Magma mixing.

Fig. 2.5 A sketch of gravity separation of chromite cumulates (black) producing a chromitite
seam. Silicates (olivine, circle, and pyroxene, plagioclase, rectangle) are also present in the system
40 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Irvine (1977) provided a logical explanation for this feature in chromite deposits,
based on the processes of magma mixing and magma contamination. His models
are portrayed in the ternary diagrams a–d in Fig. 2.6 in which the end members are
quartz, olivine and chromite (Fig. 2.6a). Irvine’s contention has been experimen-
tally confirmed by Murck and Campbell (1986) and accepted by most. In the
normal crystallization process of a magma whose composition is represented by A
in Fig. 2.6b, the only mineral to appear on the liquidus will be olivine. Settling
down of olivine will produce the ultramafic rock dunite. The changed magma
composition will now move toward the cotectic line, meeting it at B. Here, a small
proportion of chromite (*1%) will start crystallizing along with much olivine. The
magma composition will now evolve along the cotectic toward C, where olivine
will be replaced by orthopyroxene. From C the magma composition will move
toward D where plagioclase will be a new entrant to the system. This system of
crystallization of the basic magma will not lead to formation of chromite layers and
would instead form chromite as an accessory phase.
Development of a chromite seam is an extraordinary situation which is explained
by two somewhat different models:

Fig. 2.6 a A portion of the ternary system Quartz–Olivine–Chromite; b The path of

crystallization of a mafic magma; c effects of magma mixing and d magma contamination (after
Irvine 1977)
2.2 Essentially Magmatic Processes 41

1. Magma mixing
2. Magma contamination (by country rocks).
Magma mixing is introduction of a neomagma (not as primitive as the starting
one) to the system. Let us assume (Fig. 2.6c) that a neomagma of composition E is
introduced at D. Depending on the proportion of D and E, the composition of the
mixture will lie on any point on DE. In this diagram, it is at F. In the interval F-G
chromite only will crystallize and ultimately be affected by gravitative settling and
forming a seam. On reaching G, the system will evolve along the cotectic and
accessory chromite only will form along with much olivine.
Contamination of magma by siliceous country rocks is another possible mech-
anism of producing a monomineralic cumulate layer of chromite (in the interval
H-G) (Fig. 2.6d). Here magma at the assumed point E on the cotectic becomes
contaminated by the assimilation of crustal materials on the way. The contaminated
magma will have a bulk composition anywhere on the join between E and the SiO2
apex of the ternary diagram and accordingly located on it. This composition would
transiently though lie on the chromite field and would produce a monomineralic
cumulate of chromite (between H and G).
Cawthorn et al. (2005) also discuss these models and conclude that the “magma
mixing” model is more acceptible. A mixture at M1 (Fig. 2.7) of primitive
chromite-saturated magma P with its fractional derivative D is supersaturated with
chromite and would crystallize chromite till it reaches M2. This mixing model (after
Murck and Campbell 1986) provides a mechanism to cause crystallization of
chromite in the absence of olivine and pyroxene.
Many of the debates and controversies that surround the genesis of layered
chromite deposits concern the podiform chromite deposits also. Additional problem
here is the genesis of podiform or nodular structure. Suggestion of Matveev and
Ballhaus (2002) that involve equilibrium between an olivine–chromite-saturated
basaltic melt and a H2O-rich fluid at high temperature and pressure, explains the
problem better. Postdepositional petrochemical changes in chromitite (in terms of
texture and composition) are more common than generally believed.

Fig. 2.7 A magma mixing

model in the context of
chromitite layer formation in
the absence of olivine and
pyroxene. See text for more
details (after Murck and
Campbell 1986)
42 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

V–(–Ti) bearing magnetite (-hematite) deposits in gabbro-anorthosite rocks,

found at different places of the world also formed by crystallization-differentiation
process.
Another example of crystallization-differentiation is the development of mag-
netite or hemo-ilmenite (depending on the magma composition) in association with
anorthosite ± gabbro or ferrodiorite massifs. Early crystallization of plagioclase
feldspar enriches the residual magma with Fe and Ti ultimately precipitating
titaniferous magnetite or hemo-ilmenite. The precipitates accumulate on the floor of
the magma chamber or are pressed out to a neighborhood site as slurry, should the
situation so compel.

Liquid Immiscibility

Petrogenetic processes involving magma display a common phenomenon in which

a homogeneous magma is split into two, initially by chemical disintegration and
then by physical segregation. Both the neomagmas could be silicate–silicate, sili-
cate–sulfide or even silicate–oxide. We are generally more concerned with the
silicate-sulfide immiscibilities in magmatic ore genetic processes. The evidence of
silicate–sulfide immiscibility was first noted in petrography of ores or ore-gangue
masses, followed by observations in quenched volcanic rock material (Skinner and
Peck 1969). Maclean (1969) confirmed the phenomenon with his experiment in the
simple system SiO2–FeO–FeS. From a homogeneous melt, consisting of silicates
and sulfur, a sulfide melt will appear as soon as the magma attains sulfur saturation.
Sulfide solubility in the composite material decreases with increasing O2 content.

2FeO ðmeltÞ þ S2 $ 2FeS ðmeltÞ þ O2 ;

(Naldrett 1989).
Sulfide solubility increases with the increase of temperature and fS2 and
decreases with pressure, aSiO2 and aNa2O + aK2O.
Mafic-ultramafic magmas genetically associated with Ni–Cu–(PGE) ores,
formed by partial melting of the mantle rocks and leaving behind the solid residue,
ascend through the astheno-lithosphere into the crust (Fig. 2.8) or erupt on to the
surface. Arndt et al. (2005) pose a pertinent question on behalf of students of ore
geology: is there any characteristic of mantle-derived magma that makes it par-
ticularly capable to generate an economic Ni–Cu–(PGE) deposit or does the for-
mation of a deposit depend principally or entirely on events that control the magma
behavior during the ascent toward the surface? The question is briefly addressed
below.
Solubility of sulfides in mafic-ultramafic magmas is low (1000–3000 ppm,
Naldrett 2004). Once magma escapes from its mantle source and moves upward,
both its confining pressure and temperature decrease. Cooling decreases solubility
but the reduction of pressure overcompensates it (Mavrogenes and O’Neill 1999).
2.2 Essentially Magmatic Processes 43

Fig. 2.8 Generation of a mafic magma by partial melting of a portion of the mantle and its
emplacement in the crust followed by ore deposition by liquid immiscibility, segregation, and
limited redistribution (after Naldrett 1989)

Ultimately, the mafic-ultramafic magma produced becomes more sulfide under-

saturated as it rises upward (Lesher and Groves 1986). Normally, this situation will
not lead to sulfide accumulation into an ore deposit, unless the magma is close to
sulfide saturation and it quickly enters the lithosphere and begins to cool.
Obviously, it is an uncommon process and sulfide ore [Ni–Cu–(PGE)] deposits
form under specific circumstances.
Volume of the ore is disproportionately large compared to its normal solubility in
the magmas of the intrusions/host flows in nature. The most realistic process is the
assimilation of sulfur (sulfide/sulfate) by the upcoming mantle-derived magma from
the wall rocks (sulfur addition) which makes it sulfide saturated. This is supported by
field observations as well as stable isotope studies. Inflow of large volume of magma
of comparable composition (magma mixing) is also expected to cause sulfide satu-
ration. Assimilation of upper crustal rocks, incorporating SiO2, Na2O, K2O (magma
contamination) will lead to the production of sulfide-rich melt (cf. Fig. 2.9). The
initial precipitate is a monosulfide solid solution (Fe, Ni, Cu)S, which scavenged Ni
and Cu from the magma, and which on sub-solidus breakdown produces the mineral
assemblages (pentlandite + pyrrhotite + chalcopyrite) we find in nature.
Magmas most likely to form sulfide deposits are tholeiitic picrites, because the
degree of melting that leads to their formation is sufficient to remove all of the
sulfides at the source and yet make it not too undersaturated in sulfides when they
reach the crust (Mungall 1999). Sulfide saturation will thus not need much
S-assimilation from the wall rocks.
Komatiitic magmas are less qualified to form magmatic Ni–Cu(–PGE) deposits
because they would be very much undersaturated in sulfides at crustal levels.
44 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.9 Phase equilibria at 1200 °C in the system SiO2–FeO–FeS. Addition of silica will push
the homogeneous magma composition undersaturated with sulfides from A to B, into the field of
two liquid with a silicate-rich composition at Y and a sulfide-rich composition at X (after Naldrett
and MacDonald 1980)

However, komatiitic magmas are more capable of melting wall rocks, including
sulfur, at appropriate situations (Lesher 1989). This explains the origin of a number
of komatiite–hosted Ni–Cu(–PGE) deposits around the world, including Kambalda
in Western Australia.
The Sudbury Ni–Cu deposits in Ontario, Canada (Fig. 2.3a, b) are genetically
unique in that they are believed to have little or no mantle contribution. They were
derived from remelted crustal rocks, remelting triggered by a meteorite impact. The
compressed lopolithic intrusion/structure now consists of norite to granophyres,
with hugely brecciated footwall rocks injected by sulfidic material. There is a zonal
mineral distribution of pyrrhotite + pentlandite + chalcopyrite at proximal location
and low-temperature chalcopyrite + bornite at distal. The latter contains highest
PGE grades (Barnes and Lightfoot 2005; Cawthorn et al. 2005). This is due to
hydrothermal overprinting of the magmatic ores.
Liquid immiscibility is a phenomenon that in ore geology is commonly attrib-
uted to sulfidic ores as outlined above. However, Philpotts (1967) reportedly pro-
duced two immiscible melts experimentally: one on cooling produced magnetite
and apatite (2:1) and the other, a rock of dioritic composition. Nashlund et al.
(2002) reported to have obtained such magnetite ores from El Laco volcano,
northern Chile. Sillitoe and Burrows (2002), on the other hand, believe these to
have formed hydrothermally.

2.2.2 Pegmatitic Deposits

Pegmatite commonly is a coarse grained (  3 cm) igneous rock, with extreme grain
sizes of 10 cms or more and a heterogenous texture, occurring in a variety of
geological settings. Conventionally, it is a granite analog in composition and hence
2.2 Essentially Magmatic Processes 45

Fig. 2.10 Hand specimen photograph of a common mineral assemblage in pegmatite from
Bhunas mine, Bhilwara district, Rajasthan (Photo: M. Deb)

consists essentially of quartz and feldspar, with varying amounts of mus-

covite ± biotite micas and a number of other accessory minerals (Fig. 2.10). In rare
cases they may be amphibolitic, gabbroid, calc-silicate, or even sulfidic in com-
position. The latter being very rare, hereafter, by the word “pegmatite,” we will
mean granitic pegmatite only.
The pegmatites show concentration of elements, such as, Li, F, B, Cs, Ta, Nb,
etc., which are not found in abundance in the crust. Some pegmatites are thus hosts
to the following economic and strategic minerals (both metallic and industrial
minerals) (see Appendix A for mineral compositions):

Alkali feldspars Tantalite

Muscovite and biotite micas Columbite
Quartz Cassiterite
Beryl Wolframite
Pollucite Scheelite
Bertrandite Uraninite
Corundum Zircon
Gemstones Monazite
Spodumene Allanite
Lepidolite Petalite
Amblygonite Ilmenite
46 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

[Link] General Characteristics of Pegmatites

Granitic pegmatites are commonly associated with granites and granite gneisses,
but are rarely hosted by the parent granite. If they do, they form swarms and
network of fracture-filling dykes, the fractures having been produced by cooling or
post-consolidation stresses. Granitic pegmatites, which generally cluster near the
K2O end of a CaO–Na2O–K2O compositional triangle, are commonly hosted by
schists and gneisses (Fig. 2.11). Being commonly syn- or late-orogenic in
emplacement they may be foliation-parallel, folded, faulted as well as torn-apart. In
size they may be measureable in terms of meters to kilometers, the Greenbushes
pegmatites of Western Australia providing an example of the latter (Partington et al.
1995) (Fig. 2.12). Wall rock metasomatism is absent to weak around most peg-
matites (Cerný et al. 2005).
Mineral zoning, as mentioned above, is common in pegmatites, but not invari-
ably present. The ones with zoning are termed complex pegmatites while the others
without are called simple pegmatites. The number and types of minerals seen in the
border or wall zones gradually decrease inward, referred to as “core” or “core
zones”. The wall zone typically consists of quartz–plagioclase–microcline–mus-
covite–biotite–garnet–tourmaline(–beryl-apatite). This may be followed by a zone
of microcline, ending up with coarse grained quartz at the core. Rare metal

Fig. 2.11 A view of the Bhunas pegmatite mine within Bhilwara gneisses and schists, Rajasthan
(Photo: M. Deb)
2.2 Essentially Magmatic Processes 47

Fig. 2.12 Geological map and cross section of Greenbushes pegmatite showing zonation (after
Partington et al. 1995)

concentration may take place at or off the core (Fig. 2.13). Zoning of pegmatites on
regional scales, in terms of their elemental composition and mineralogy, may be
present around almost barren/barren granite pluton (Fig. 2.14).

[Link] Classification of Pegmatites

Because of varieties of granitic pegmatites in nature it has been felt necessary to

classify or group them according to certain distinctive criteria. Cerný and Ercit
(2005) and Cerný et al. (2005) provided recent updates in this respect (Table 2.2).
Notably, rare element granitic pegmatites, host to a large proportion of rare metals
and rare earth elements (RM and REE), are subdivided into two principal families,
LCT and NYF (Table 2.3). Of these the LCT pegmatites are most important in
terms of diversity, tonnage, and relationship to the associated rocks.
48 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.13 Geological map of the Metapal zoned pegmatite, Bastar-Malkangiri pegmatite belt,
Chhattisgarh (after Ramesh Babu 1999)

Fig. 2.14 Schematic representation of the regional zonation of pegmatites around a granite
intrusion (after Trueman and Cerny’ 1982)

[Link] Origin of Pegmatites and Pegmatitic Deposits

That granitic pegmatites form from plutonic granitic intrusions is proved, inter alia,
by a number of observations, including (i) granite–pegmatite suites, intruded into
Table 2.2 Major classes of granitic pegmatites (after Cerny’ et al. 2005)
Class Typical minor elements Metamorphism of host rocks Relationship to Structural features
granites wrt host rock
foliation
Abyssal U, Th, Zr, Nb, Ti, Y, REE, Mo. Rarely Be, B. Poor Upper amphibolite to None (?) Conformable to
to moderate mineralization granulite facies (*400– (segregation of mobilized
900 MPa/*700–800 °C) anatectic cross-cutting veins
2.2 Essentially Magmatic Processes

leucosomes?)
Quartzo-feldspathic Metallic minerals absent. Micas and ceramic High pressure Barrovian None (anatectic Quasi-conformable
minerals determine value amphibolite facies (ky-sill) bodies) to to cross-cutting
(500–800 MPa/520–650 °C) marginal and
exterior
Muscovite-rare Li, Be, Y, REE, Ti, U, Th, Nb > Ta. Rarely Li, Be. Moderate to high-P, Interior to Quasi-conformable
element Poor mineralization amphibolite facies 300– exterior poorly to cross-cutting
700 MPa/520–650 °C) defined
Rare element Li, Rb, Cs, Be, Ga, Sn, Hf, Nb–Ta, B, P, F, or Be, Low-P Abukuma-type Exterior, some Quasi-conformable
Y, REE, U, Th, Nb > Ta, F. Poor to abundant amphibolites to upper interior to to cross-cutting
mineralization. Gemstones, industrial minerals greenschist facies marginal
(andalusite-sillimanite) (andalusite-sillimanite)
(200–400 MPa/500–650 °C)
Mariolitic Li, Be, B, F, Ta > Nb or Be, Y, REE, Ti, U, Th, Zn, Shallow to subvolcanic Interior to Interior pods, and
Nb > Ta, F. Poor mineralization. Gemstock (*100–200 MPa) marginal cross-cutting dikes
49
50 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Table 2.3 Subdivisions in the rare element class of granite pegmatites (after Cerný et al. 2005)
Family Geochemical Bulk granite composition Pegmatite types
signature
LCT Li, Rb, Cs, Be, Sn, Peraluminous, S, I or mixed Beryl, complex albite
Ga, Ta > Nb S + I types spodumene, albite,
(BPF) elbaite
NYF Nb > Ta, Ti, Y, Peraluminous to sub-aluminous Rare earth
Sc, REE, Zr, U, and metaaluminous; A and I
Th, F types
N.B. There is another subclass or family in this class called “Mixed Family,” which, as the name
suggests, have characteristics intermediate between LCT and NYF. As pointed out by Cerny et al.
(2005), all the granite phases are weakly to strongly peraluminous and show prominent enrichment
in LCT elements that increase in the late and more pegmatitic facies

low-P greenschist to amphibolites facies country rocks; (ii) highly evolved

peripheral pegmatite dikes, locally physically linked to the interior or marginal parts
of granitic plutons; (iii) rare element pegmatites form aureoles of marginal and
exterior dikes, surrounding the granite intrusions; (iv) continuity of geochemical
signatures in numerous cases of granite–pegmatite suites. No less important is
experimental evidence that the liquidus and solidus of pegmatite forming melts
decrease with the increasing contents of Li, Rb, Cs, F, B, and H2O (Cerný 1991).
There is also a decrease in density with depolymerization of the melt, which helps
the melt to be more mobile and rise. There is also a decrease in the number of
nucleation sites of crystals and an increase in diffusion which helps large crystals to
grow.
It was the belief of many geologists until recently that pegmatites crystallize at
temperatures of the water-rich granite solidus near 650–700 °C, that is, are products
of an intermediate stage of evolution from orthomagmatic to hydrothermal (or
pneumatolytic) stage of magmatic evolution. However, it does not agree with the
P-T estimates derived from mineral assemblages, isotopic estimates, or fluid
inclusion studies. In the latter studies, the crystallization temperatures vary in the
range of 450–250 °C, which is well below the solidus temperatures of hydrous
granite melts. The most plausible explanation of this phenomenon is the presence of
fluxing components, H2O, B, F, and P in the pegmatitic magma wherein, as a result,
the melting and crystallization temperatures are reduced (London 1997). The
fluxing component needed is small in quantity. For example, the Tanco pegmatite
in Manitoba, Canada, which may be the most fractionated igneous body on earth,
contains <2 wt% of (Be2O3 + P2O5 + F) (Cerný 1991; London 1995). The upper
thermal stability of Li-aluminosilicates in the presence of quartz, however, put the
upper crystallization temperature of Li-pegmatites at *700 °C. There was a
common belief until recently that the pegmatites cooled slowly. Recent experi-
mental studies suggest that it possibly happened otherwise. The large grain sizes are
in fact the effect of fluxes. Crystallization at conditions far below the liquidus (i.e.,
crystal-melt equilibrium) generates a sequence of crystallization that matches the
natural zoning patterns exactly (London 2005).
2.3 Hydrothermal Processes of Ore Formation 51

2.3 Hydrothermal Processes of Ore Formation

A. Introduction
Etymologically, the word “hydrothermal”, long in use in ore geology, means “hot
aqueous”. So, hydrothermal mineralization means “mineralization from a hot
aqueous solution.” But, how hot? Any temperature between a few tens of centi-
grade to below solidification of granitic magmas, or beginning of low-T granulite
metamorphism set in a volcano-sedimentary sequence. Ambient pressure may be
anywhere between a few bars to a maximum of a few kilobars (3 kb at *10 km
depth).
Lindgren (1933), Emmons (1936), Jensen and Bateman (1981), Guilbert and
Park (1986), Robb, (2005) and others have discussed about hydrothermal ore de-
posits in fair details and divided them initially into three broad divisions, namely,
hypothermal, mesothermal and epithermal. Their characteristic T-P fields, as sug-
gested, are:
Epithermal: 50–250 °C, <0.5 kb (<1500 m depth)
Mesothermal: 250–500 °C, 0.5–1.5 kb (1500–4500 m depth)
Hypothermal: 500–600 °C, >1.5 kb (>4500 m depth)
It may be pointed out that these P-T values are only suggestive rather than
prescriptive. More restricted attributes will not be realistic in geology. For example,
Hedenquist et al. (2000) from a study of the modern analog of epithermal miner-
alization at Tampo, New Zealand, suggest a temperature range of 160–270 °C and
pressure equivalents of 50–1000 m. The crustal environments of these three major
classes of hydrothermal deposits are shown in Figs. 2.15 and 2.16, with reference to
Au mineralization. Not that all the above subclasses of hydrothermal mineralization
would always be found in one deposit/ore district in such orderly disposition. It will
depend on the original P-T of the ore fluids, their migration and cooling, and of
course, later erosion and superimposition.
There was a time when most ore deposits, particularly those formed as veins or
irregular bodies and accompanied by a granitic intrusive in the neighborhood, were
thought to have formed from fluids given out by the cooling granitic magma body.
If the intrusive was not detectable, it was still imagined to be there. Today, ore
geology, like most other branches of Earth Sciences, has become more precise.
Now we know that hydrothermal fluids for ore deposition may be derived from a
cooling and depressurizing granitic magma, as well as from the fluids given out by a
volcano-sedimentary pile due to an overpressured uplifted region, rock compaction
in an orogenic belt, thermal perturbations and metamorphism (Skinner 1979; Robb
2005), or a combination of these conditions. To the latter group are included the
meteoric or connate water getting heated by geothermal heat, or the heat radiated by
52 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.15 Schematic models of three different crustal environments of gold deposits formed by
hydrothermal fluids. In the hypothermal environment, a steep shear zone transects the boundary
between seismogenic and aseismogenic crust and controls the fluid movement. For the
mesothermal environment, porphyry Cu–Mo–Au, Au skarn and distal “Carlin type” Au–As–Sb
mineralizations are shown. In the epithermal environment, the relative positions of subareal
hot-spring mineralization and the deeper epithermal veins (cf. Fig. 2.16 for more details) are
shown. In the shallow marine exhalative environment, Au-rich volcanogenic massive sulfides are
depicted (after Poulsen 1995)

Fig. 2.16 Geological model

of hot-spring low sulfidation
epithermal gold deposits of
McLaughlin mine, California,
USA, showing zones of
alteration (after Sillitoe 1995)

an igneous intrusive body. However, this external contribution need not necessarily
be overemphasized (Sillitoe 2010). Hydrothermal mineral deposits can thus be
divided into two main categories (Fig. 2.17):
1. Essentially magmatogenous, or magmatic hydrothermal
2. Essentially non-magmatogenous, or amagmatic hydrothermal.
2.3 Hydrothermal Processes of Ore Formation 53

Fig. 2.17 Conceptual models of magmatic and amagmatic fluids in hydrothermal deposits. (1)
shows surface-derived water (shallow marked 1a) descending down normal faults toward the
brittle-ductile transition zone and returning to the surface to form a deposit; (2) shows
metamorphic fluids rising along faults to form a deposit; small arrow with (3) shows possible
subordinate magmatic input to the amagmatic model; (3) shows magmatic–hydrothermal
ore-forming system related to multiple intrusions (after Seedorf and Barton 2004)

Besides, based on whether the hydrothermal fluid, whatever its source, forms a
deposit within the crust at depth or exhales on to the surface, commonly on the sea
floor, and forms a mineralized mound, hydrothermal deposits are further catego-
rized into two divisions respectively:
(i) Intracrustal deposits
(ii) Exhalative deposits.
Some aspects of the above outline will be elaborated in the following few pages.
B. Structures of hydrothermal deposits
Hydrothermal deposits may assume different forms depending on the dilatant
structures in rocks they occupy by fracture-filling and crystallization [such as, in
saddle reefs (Fig. 1.9b), fissure veins, ladder veins (Fig. 1.9c), stockwork (Figs. 1.9a
and 2.18a, b), breccias-filling (Figs. 1.13 and 2.18c), or by replacement as in shear
zones. Vein filling is by growth of new crystals from the walls to the core of the vein.
It is open space filling and hence is emplaced at shallow levels, compared to those
developed by replacement. Veins may show pinch and swell structures (Fig. 1.9c)
and temporally may be emplaced more than once. They may be intersecting or
sub-parallel (Fig. 2.19b). The veins may extend for several km along strike (such as
the Mother Lode vein system in California) and about a km down the dip. In
replacement, new mineral phases grow by reaction. One may be superimposed on
the other. In case of regional scale dislocations, second-and third-order structures are
generally better locales for ore deposition as these are sites of lower pressure. Ore
54 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.18 a Cross-cutting

stockwork veinlets with
magnetite + molybdenite in
Keystone intrusion, Mt.
Emmons, Colorado, USA
(Slab gifted to SC Sarkar by
Holly Stein; slab width
10 cm). b Silicified
stockwork with chalcopyrite
mineralization, drill core, KH
prospect, Mongolia (Photo:
M. Deb). c Breccia filling by
bornite, drill core, Oyi Tolgoi
Cu–Au porphyry deposit,
Mongolia (Photo: M. Deb)

controlling structures are either penecontemporaneous with ore mineralization, or

are older structures that reopened during mineralization.
Some spectacular examples of Sn–W-bearing greisenized sheeted vein system
are seen in parts of Cornwall, SW England (Fig. 2.19a, b, c) and of Cu in northern
Chile. The veins are normally controlled by steep to moderately dipping faults that
transect granitic intrusions and their wall rocks (Fig. 2.19c). These veins may
accompany other intrusion-related deposit types but the larger ones generally occur
alone.
2.3 Hydrothermal Processes of Ore Formation 55

Fig. 2.19 a Index map of United Kingdom showing the location of Cornwall. b Map of Cornwall
granites and their relationship with Sn–W vein system (after Inst Mining and Metall 1985).
c Outcrop of greisenised granite at Cligga Head, St. Agnes district, western Cornwall, cut by a
sheeted vein system comprising greisens-bordered veins between which the granite shows
incipient greisenisation. Close up shows tourmaline-rich margins of the veins carrying
wolframite-cassiterite mineralization associated with sulfides like stannite, sphalerite, and
chalcopyrite (Photo: M. Deb)

C. Common minerals of hydrothermal origin

Ore minerals are hardly free from gangue minerals in ores. This is particularly true
of hydrothermal ores. A list of common ore and gangue minerals in these ores is
given below.

Important ore minerals Common gangue minerals

Chalcopyrite, pyrite, pyrrhotite, molybdenite, Quartz, calcite, sericite/muscovite, biotite,
galena, sphalerite, enargite, huebnerite, epidote, chlorite, alkali feldspars, barite,
scheelite, cassiterite, gold, acanthite, uraninite, fluorite, chalcedony, carbonate, clay
cinnabar, columbite, tantalite, stibnite minerals, alunite, tourmaline

A hydrothermal mineralization is identified as such by its P-T conditions of

formation within the hydrothermal range, presence of hydrous minerals in the
56 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

assemblage and the wall rocks and presence of fluid inclusions (see Sect. 2.2e) in
some constituent minerals, such as, quartz, calcite, fluorite, barite, pyrite, sphalerite.
P-T conditions are initially estimated from the assemblage, but later confirmed by
geo-thermobarometers, wherever possible.
D. Wall rock alterations
The distribution of minerals mentioned under “gangue” may be spread into either
side of the ore zone, bringing about a petrochemical change in the wall rocks. This
constitutes what is simply known as “wall rock alterations” (cf. Fig. 2.16). Around
or alongside orebodies of hydrothermal origin, the host rocks are variously affected
in terms of color, texture, mineralogy, and bulk chemistry due to these alterations.
Well-developed variations may be present from the ore zone outwards. Such spatial
changes generally have a close temporal relationship with ore deposition. A critical
analysis of this phenomenon is an important tool in mineral exploration as well.
Hydrothermal alteration essentially means, selective leaching of certain com-
ponents from the wall rocks, adding them to the solution and depositing certain
minerals that are stable in the given conditions on the two wall zones.
Monomineralic alterations, such as silicification, carbonatization, sulfidation
(pyritization) do develop, but relatively rarely.
Transfer of fluids or its contents in a wall rock alteration process may be by fluid
flow, or diffusion of chemical species guided by disjunctive structures or shears. It
is sort of a dynamic system principally controlled by changing fluid/rock ratio
(Reed 1997). If the mass transport during alteration (and even ore mineralization)
takes place on a larger scale moving through large distances, the process is com-
monly known as infiltration. It is generally unidirectional. In virtually all cases of
ore deposition, both infiltration and diffusion are operative at the same time. Wall
rock alterations may be polychronous, being pre-, syn- and post- ore mineralization.
A good example of hydrothermal alteration can be seen in the Hutti gold mine in
Karnataka. Mineralization is confined to “laminated” quartz veins in discrete shears
hosted by metabasalts and minor meta-dacites. Wall rock alteration is characterized
by narrow but distinct proximal biotite-K-feldspar zones and distal chlorite zones
that are symmetrically distributed around the quartz veins of varying widths
(Fig. 2.20). Pal and Mishra (2002) record the alteration reactions in the ore zone as
follows:
(i) Formation of chlorite and calcite by carbonation-hydration reactions of
amphiboles in the distal chlorite zones;
(ii) Sulfidation of Fe-amphiboles to form pyrrhotite.
(iii) Formation of biotite from chlorite.
(iv) Sulfidation of biotite to form pyrite and gold in the proximal zone.
2.3 Hydrothermal Processes of Ore Formation 57

Fig. 2.20 Symmetrical zones of wall rock alteration around a thin quartz vein (Q) in Hutti gold
mine, Karnataka. Hydrothermally altered meta-basalt host rock shows biotite-rich (B) and
chlorite-rich (C) zones, which display repetition and overlap due to emplacement of successive
quartz veins (Photo: M. Deb)

E. Fluid Inclusions
Fluid inclusions (FI), tiny capsules of liquid, gas, or melt, trapped in minerals,
provide the most direct clue to the nature of fluids associated with different geo-
logical processes, including ore mineralization by hydrothermal processes.
Microthermometry is the most widespread technique of FI investigations commonly
confined to transparent gangue minerals, such as, quartz, calcite, fluorite, barite,
apatite, dolomite, topaz, beryl, etc. associated with the ore. Translucent ore minerals
like sphalerite and cassiterite can also be studied. Recent development of Infrared
microscopy allows FI studies to be carried out in opaque minerals such as, pyrite, as
well. The textural relationships amongst the mineral phases in a paragenetic
association1 must be explained as logically as possible before enough meaningful
interpretations can be drawn from FI studies. Most commonly retrieved information
from fluid inclusion microthermometry includes temperature, pressure, fluid com-
position (including salinity), and density of the fluids. Techniques other than
microthermometry involve chemical and isotopic analyses of the extracted inclu-
sion fluids. The subject is somewhat elaborated below.

1
Paragenetic association: a set of genetically related minerals.
Paragenetic sequence in a mineral association connotes sequence of mineral deposition in an
association of minerals, where the constituent phases bear evidence of being genetically related.
58 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

The inclusions may vary in size from a few microns, commonly about 0.1 mm,
to much larger ones and may be trapped during the growth of the mineral (i.e.,
primary) or during later deformation and recrystallization (i.e., secondary) in
post-crystalline fractures. Pseudo-secondary inclusions are quite similar to sec-
ondary but fracturing and healing takes place before the growth is complete
(Fig. 2.21a). The inclusions may contain different combinations of phases in them,
which when identified under the petrographic microscope, provides an important
nongenetic classification. By far the most common is a low viscosity liquid and a
gas or vapor bubble occupying a volume less than that of the liquid. The inclusions
may also contain a liquid + solid, liquid + gas, and liquid + liquid (much rarer).
CO2 is often present in inclusions as both liquid (CO2-L) and gas (CO2-G). If the
liquid phase has a soluble salt and becomes supersaturated with it, the excess salt
may crystallize out as a mineral grain, such as, halite (NaCl) or sylvite
(KCl) (Fig. 2.21b). Sometimes, some unrelated pre-existing minerals are trapped in
the inclusions which are known as “captive minerals.”
It is generally assumed that when the liquid was trapped in the solid mineral, the
volume of the liquid filled the total volume of the inclusion cavity. Later, the gas
bubble was formed as a result of differential shrinkage of the liquid and the host
mineral from the higher temperature of formation to the temperature of observation,
i.e., indicating the post-entrapment changes (Fig. 2.22). Therefore, a temperature
close to that of trapping (Tt) can be estimated by heating the mineral sample with
the inclusion to the point at which the gas bubble disappears completely, this being
the temperature of homogenization (Th). The obtained temperature marks the lower
limit for the temperature of formation of the mineral. If after homogenization the
inclusion is heated further, a temperature will be obtained when the inclusion cavity
bursts or decrepitates. This temperature of decrepitation implies that the host
mineral could not have formed at a temperature above the decrepitation condition,

Fig. 2.21 a Primary (P), secondary (S) and pseudo-secondary (PS) fluid inclusions (after
Shepherd et al. 1985). b A primary fluid inclusion in Bhukia gold ore prospect, South Rajasthan.
Note the liquid (L), vapor (V), and daughter crystal (S), probably halite, in the inclusion
2.3 Hydrothermal Processes of Ore Formation 59

Fig. 2.22 Post-entrapment changes in fluid inclusions TT = Temperature of trapping;

TH = Temperature of homogenization; TR = Room temperature. CP = Critical point (after
Mookherjee 1999)

i.e., the maximum temperature of formation. Detailed discussion on various aspects of

FI studies is available in Roedder (1984) and Shepherd et al. (1985), amongst others.

2.3.1 Essentially Magmatic Hydrothermal Processes

The formation of several hydrothermal ore deposits is dependant largely on fluids of

magmatic origin and processes that operate during the late stages of felsic mag-
matism. We discuss such processes and deposits in this present section.

[Link] Ore-Forming Fluids in the Hydrothermal Processes

The magmatic hydrothermal process leading to ore formation commences with the
generation of magmas by partial melting of subducting mafic oceanic crust or
anatexis of amphibolites and/or felsic metasedimentary rocks in the lower conti-
nental crust. Depending on the source rock composition, mafic or felsic, the partial
melting process concentrates different suites of ore elements in the melt produced,
as we shall see in somewhat more details shortly. Water plays a crucial role in all
stages of the process from putting constraints on melt generation to dissolving in the
melts of different compositions at different proportions and finally, separating from
the melt with the ore elements to form the hydrothermal ore deposit.
60 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

The partial melting is induced by the presence of H2O and the P-T regime of
melting, as shown by the different experiments on solubilities of water in magmas
(Burnham 1967, 1979, 1997). At high P, H2O is bound as hydroxyl ion in hydrous
minerals and the hydrolysis reaction involved is:

H2 OðvÞ þ O
2ðmÞ , 2ðOHÞðmÞ

Here v and m refer to aqueous fluid and melt phase, respectively (Burnham
1979). However, at higher P and water contents, H2O may be present as water
molecules as well (Stolper 1982). The principal hydrous minerals in mafic rocks are
amphiboles (with 2–3% H2O) while in felsic metasedimentary rocks the micas
(biotite with 3–5% H2O and muscovite with 8–10% H2O) predominate. Hence,
H2O-activity in melts produced by the breakdown of the above-mentioned minerals
will vary considerably and will put definite constraints on the amount of melt
produced at a particular depth and temperature (Burnham and Ohmoto 1980). If we
consider cases, with source rock containing mainly one of these three minerals and
buried under the 25 °C/km geotherm (Fig. 2.23), then the rock with muscovite will
start melting at A with the H2O-content of the neomagma being 7.4 wt% H2O, the
rock with biotite at B with the neomagma having 3.3 wt% H2O and the rock with
amphibole at C with only 2.7 wt% H2O in the neo-magma. Note that the P is higher
and the H2O content is decreasing from A to C. It is expected that these magmas
produced will rise upward in the crust until they intersect the water-saturated
granitic or basaltic solidus at A′, B′, or C′ (Fig. 2.23), respectively, when they will
get emplaced and solidify. It also follows that the amphibole-sourced melt will be

Fig. 2.23 P-T diagram

showing the approximate
conditions where dehydration
melting of amphibole-rich
(A), biotite (B), and muscovite
(C)-bearing protoliths would
occur along a 25 °C/km
geothermal gradient and the
expected levels of the earth’s
crust to which melt fractions
would rise adiabatically, as a
function of the
water-saturated solidus of
granodiorite and basalt (after
Burnham 1997)
2.3 Hydrothermal Processes of Ore Formation 61

emplaced at the shallowest level in the crust. Such magma may incidentally be
H2O-undersaturated, inviting H2O-vapor from the heated adjacent country rocks.
While tracing the role of water further, experimental studies confirmed that a
granite melt will dissolve more water than a basaltic one (Fig. 2.24). The solubility
of H2O in silicate magmas of different compositions is determined mainly by
pressure and to a lesser extent by temperature. Thus, a granitic magma at the base of
the crust (*30 km and *10 kb) should be able to dissolve around 15% H2O.
A plausible explanation of the varying solubility of H2O is found in the differential
polymerization of granitic and basaltic magmas. Granitic melts have a viscosity of
the order of 108–1010 poise at 1000 °C and 1 atm. An addition of 6.4 wt% water
would, however, lower the viscosity by about 105poise (Burnham 1967). Added
water will interact with the melt in a way that breaks oxygen bridges and
depolymerizes it. Basaltic magma, on the other hand, accommodates fewer (OH)–
group in O2– sites. That is why basic magmas on cooling produce less hydrothermal
solutions compared to the granitic magmas.
As the neo-magmas formed at different crustal levels move up to different depths
from the surface, they would exsolve the dissolved aqueous fluid due to depres-
surization. The I-type granitoid magmas are generated in the deeper parts of the
lithosphere near subduction zones at higher temperatures and low water contents
with contributions from mantle-derived mafic melts. When they move up to the
shallow levels, they will exsolve the magmatic fluid by boiling and hydrofracturing
and induce vigorous circulation of hydrothermal solutions of different derivations in
the endo- and exo-contacts. This environment will encourage the formation of
porphyry Cu deposits and epithermal Au–Ag deposits. In contrast to this scenario

Fig. 2.24 Experimentally

determined solubilities of
H2O (in wt%) in silicate melts
(of basalt, andesite, and
granite/pegmatite) as a
function of pressure (after
Burnham 1979)
62 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

(Fig. 2.25), S-type granites are generated in lower to mid-crustal levels by anatexis
of metasedimentary lithologies. They will form at lower P-T conditions but will
contain significant amount of dissolved H2O due to their source material. They will
be emplaced not too far from their source at mid-crustal levels (4–5 kb) and are
often barren. Only if fractionation occurs substantially, such magmas may produce
pegmatitic bodies, or hydrothermal Sn+/W+/U mineralization through their residual
melts (Fig. 2.25).
How about the tenure of a hydrothermal system? Mineral calculations show that
convective circulation that produce near-surface hydrothermal systems are expected
to cool their intrusive heat source in a period of time not exceeding a few tens of
thousands of years, large though the intrusion may be. Long-lived (*10 My)
hydrothermal systems are likely to be the result of repeated intrusions (Cathles et al.
1997). Petrochemical alterations and ore mineralization were confined to amag-
matic intervals between porphyry intrusions. All porphyry intrusions take place in
the temperature range of 400–800 °C. Alteration ages, however record a much
younger age corresponding to 250–400 °C, when the system cooled through the
blocking temperature of biotite, K-feldspar, and sericite (Sillitoe and Mortensen
2010).
Magmatic hydrothermal ore fluids may be brine or vapor or a combination of
both, depending on the specifics of the situation. Fluid inclusion studies indicate
that partitioning of base and precious metals between magmatic vapor and

Fig. 2.25 Schematic diagram illustrating the emplacement style and metallogenic character of
granites formed under each of the conditions (A, B, C) shown in Fig. 2.23 (after Strong 1988)
2.3 Hydrothermal Processes of Ore Formation 63

hypersaline brine may be substantial and highly element specific, apparently due to
contrasting metal complexing properties of the two phases. Cu, and by inference,
Au complexing with S partition into vapour and the other heavy metals complexing
with chloride partition into the coexisting brine (Heinrich et al. 1992;
William-Jones and Heinrich 2005). Cu in the presence of high Cl− concentration
will however behave differently. As defined, the solubility of a mineral is the upper
limit of the dissolved metal contained in the mineral that a hydrothermal fluid can
transport, assuming thermodynamic equilibrium. However, solubilities of common
ore minerals as simple ions have been known to be insignificant for a long time. To
attain solubilities necessary for ore deposit formation ore metal ions must form
complexes. A complex ion is a combination of one or more metal ions (including
protons, i.e., H+) with one or more anionic or neutral species. The latter is called
ligand. The most important ligands are Cl–, HS–, or H2S and OH– (Czamanske
1959; Barnes 1979; Wood and Sampson 1998). Several factors, such as fall of
temperature, fluid mixing (dilution), and “secondary boiling”, reaction with wall
rocks play important role in precipitation of ore minerals from hydrothermal fluids.
Pressure variation and change of oxidation have conditional effects.
Fall of temperature is generally effective in destabilizing metal ligands, partic-
ularly, the chloride complexes. Mixing of two fluids, one being the ore fluid and the
other the groundwater may precipitate ores due to two reasons: dilution of the ore
fluid will break the complex after a certain value and if the adulterant fluid is
relatively cool, which often it is, mixing will reduce the temperature of the mixed
fluid and help in ore precipitation. Reduction of fluid pressure along fractures at
depth may cause “secondary boiling” and effervescence, giving out acidic com-
ponents. This will raise the pH of the solution, cool it faster and cause ore mineral
precipitation. This is particularly effective in “crack-seal” systems. Oxidation
reduces the solubilities of metal sulfide complexes, depositing ore minerals.
Examples:
þ 
4 þ H2 S ¼ PbS ðsÞ þ 2H þ 4Cl
PbCl2 o

ZnðHSÞ þ
3 þ 4O2ðaqÞ $ ZnSðsÞ þ 3H þ 2SO4
2

The first reaction will move from left to right, i.e., precipitating PbS (galena) by
the satisfaction of one or more of the following conditions: (i) if there is a loss of
temperature (assuming the mineral has prograde solubility), (ii) there is an increase
in the activity of H2So, (iii) there is a decrease in the activity of H+ (increase in pH),
(iv) decrease in the activity of Cl–. In the second, ZnS (sphalerite) precipitates when
the complex Zn(HS)3– is oxidized. There are many more plausible reactions in
which metal complex breaks down to ore minerals. More discussion on this is
beyond the scope of this text.
64 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

[Link] Granitoids and Metal Deposits

Granitic rocks spanning a wide range of compositions in terms of silica contents,

low to high-K calc-alkaline or alkaline character and varying from metaluminous to
peraluminous compositions, are genetically related to a spectrum of precious,
chalcophile and lithophile metal deposits. The metals present are dictated by
composition, degree of fractionation, and the redox state of associated intrusions
(Fig. 2.26) (Sillitoe 1996). The granites are classified into I-type or S-type which
reflects the composition of source regions (Blevin and Chappel 1992) or as mag-
netite and ilmenite series which point to the redox state of the rocks themselves
(Ishihara 1981). All S-type intrusions, peraluminous granites formed by melting of
muscovite or (muscovite + biotite)-rich source rocks, essentially belong to the
moderately reduced ilmenite series. Sn, W, and U deposits are generally associated
with S-type granites. I-type, on the other hand, includes both magnetite ()-
ilmenite and less commonly ilmenite series granites. This comparatively oxidized
calc-alkaline granite magma is related to porphyry copper systems.
A-type granites (Collins et al. 1982) are rather abnormal or atypical in the granite
family. Typical A-type granites are the alkali granites of continental rifts. Two
different ore associations occur with A-type granitoids: (i) Na-rich granites, con-
taining concentrations of Nb, U, Th, REE, and some Sn and (ii) K-rich granites with
profuse hydrothermal silicification and tourmalinization, associated with the min-
eralization of Sn, W, Pb, Zn, and F. Volcanic equivalents of this granite type
include Sn-rich topaz rhyolites in the fields of crustal distension, as in the Tertiary
volcanics in Mexico (Pohl 2011). A-type granite-associated mineral deposits are
rarely very large.
The metals and associated elements are extracted from the magma by exsolution
of an aqueous fluid phase, with the exception of certain rare metals, such as, Ta and
Li which are concentrated by direct crystallization from evolved melts (Pollard
1995). Partitioning of metals like Cu into a vapor-rich or hypersaline magmatic
fluid from wet magmas with high Cl/H2O ratios is maximum at shallow crustal
depths of 3–4 km (Candela and Piccoli 1995). The metal-rich fluid concentrates in

Fig. 2.26 Diagram showing

the control of redox state and
degree of fractionation of
granitic rocks on some
selected metal deposits,
principal, and subsidiary
concentrations differentiated
by size of the alphabets (after
Blevin and Chappell 1992)
2.3 Hydrothermal Processes of Ore Formation 65

the upper parts of the crystallizing granitic intrusion and is channeled upward
through the magma column. It also undergoes admixture with deeply convective
groundwater. Metal precipitation takes place in the mixing zone provided by the
cylindrical cupola, in the adjacent reactive carbonate horizon and in dilatant fault
zones (Fig. 2.27) (Sillitoe 1996). Sulfides (Cu, Mo, Pb, Zn, Ag, Bi, Sb), oxides (Fe,
Sn, W), fluorcarbonate (REE) and native metals are thus deposited from the
hydrothermal fluid by destabilization of aqueous, most commonly chloride com-
plexes brought about by cooling, reaction with the wall rocks and mixing with
circulating groundwater. Sequential precipitation of metals in space (zoning) and in
time (paragenetic sequence) takes place due to the physicochemical evolution of the
ore fluid and is noted at both deposit and district scales (Evans 1997). In a mixed
system Au-mineralization follows Sn-, W-, and Mo-mineralization. Bulk of base
metal deposition takes place still later, mostly in an outer zone occupied by
metasediments, where reduced sulfur present is likely to help in sulfide precipita-
tion. If Cu is present in the system, it generally precedes deposition of Pb and Zn, as
in Cornwall, England. On a district scale Zn–Pb + Ag occur on the peripheries of
Cu, Mo, Sn, W deposits.
There are six broad types of ore deposits generated by intrusion-related mag-
matic fluids (Sillitoe 1996): the largest of these (up to several thousand million tons)
is the porphyry type, while the smallest (<10 Mt) are vein deposits. Intermediate
sizes are represented typically by skarns, carbonate-replacements, greisens and
breccia-hosted deposits. The spatial interrelationship of all these types is depicted in
Fig. 2.28.

Fig. 2.27 Sketch showing the generation, accumulation and focused release of magmatic fluid
along the cylindrical cupola during the crystallization of a granitic intrusion. Note the mixing
zones with deeply convecting groundwater, the reactive carbonate horizon and the dilatants fault
zone (after Sillitoe 1996)
66 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.28 Sketch showing the spatial interrelationship between porphyry Cu, skarn, carbonate
replacement, breccias, and vein deposits in and around a porphyry cupola above a granitic intrusion.
Note that not all the six deposit types occur in a single granitic system (after Sillitoe 1996)

The porphyry deposits, several being giant in size (Fig. 2.29a), contain mainly
Cu, Mo + Au. Their regional distribution is mostly along Mesozoic and Cenozoic
orogenic belts (Fig. 2.29b), along island arcs and continental margins. They are
centered in and around cupolas (<100 m to several km in diameter) on top parts of
granitic plutons which are commonly multiphase high level (<6 km) intrusions
overlain by co-magmatic, calc-alkaline, or less commonly, alkaline volcanic rocks
forming a stratovolcano (Fig. 2.30). The highest ore grades are generally associated
with the early phases. Major part of the metals in porphyry deposits commonly
occur in anastomosing stockwork veinlets of sulfides + quartz (Fig. 2.18a, b) that
accompany K-silicate or potassic (K-feldspar) alteration. The stockwork is the
result of brecciation and shattering of the endo- and exo-contacts of the pluton due
to volume increase during resurgent boiling when P(fluid) > P(confining). At an early
high temperature stage, a single phase low- to moderately saline liquid exits the
magma and undergoes phase separation during ascent, due to P-dependence of H2O
solubility, to generate an immiscible hypersaline liquid and vapor which produce
potassic alteration (*500 °C) along with the contained low (or high?) sulfidation
2.3 Hydrothermal Processes of Ore Formation 67

Fig. 2.29 a View of the giant porphyry Cu deposit at Bingham, Utah, SW USA (Photo: M. Deb).
b Global distribution of porphyry deposits worldwide

Fig. 2.30 Spatial relationship between porphyry Cu stocks, underlying pluton, overlying
co-magmatic volcanic sequence and the lithocap. The precursor pluton is multiphase whereas
the parental pluton is a single body undergoing inward consolidation shown by concentric dotted
lines (after Sillitoe 2010)

state porphyry Cu + Au mineralization (Fig. 2.31) (Sillitoe 2010). The character-

istic mineral in the potassic alteration zone is new-formed K- feldspar and/or biotite,
brought about by K+ metasomatism and hydrolysis. Sericite, chlorite, quartz, and
iron oxides may be present in small to minor proportions. In a few cases (for
example, Yerrington porphyry copper deposit, Nevada, U.S.A.) the position of K
may be partly taken up by Na and Ca. Phyllic or sericitic alteration is a very
common type of alteration in hydrothermal mineralization, where white potassic
mica develops from K-feldspar by reaction with water:
68 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.31 A schematic model of evolution of a porphyry Cu system with time. Generation of
different alteration zones and HS and LS epithermal deposits are also shown. See text for more
details (after Sillitoe 2010)

3KAlSi3 O8 þ 2H þ $ KAl3 Si3 O10 ðOHÞ2 þ 6 SiO2 þ 2 K þ

ðK-feldsparÞ ðmuscovite=sericiteÞ ðquartzÞ

The reactant phase may be plagioclase or mafic minerals instead. Because

temperature controls are less stringent, this type of alteration is more common than
the potassic alteration. Propylitic alteration, characterized by the development of
chlorite, epidote, zoisite, albite, and calcite is common as an outer envelope to the
porphyry system. Unless set in the geological context, the petrographic character of
this zone may be distinguished from greenschist metamorphism only with difficulty.
The zone is characterized by low temperature (200–350 °C) minerals and a low
fluid/rock ratio. Besides, base leaching related to epizonal precious metal miner-
alization in porphyry systems often gives rise to intense argillic alteration in the
near-surface zone (cf. Fig. 2.16). The involved fluid is acidic and is of low tem-
perature (<250 °C). It may be noted that these alterations are interpreted as a
temporal sequence, either from early propylitic to late silicic and argillic, or as
spatial progression from a potassic zone outward to a propylitic halo (Henry et al.
1997).
2.3 Hydrothermal Processes of Ore Formation 69

Skarn deposits develop where carbonate rocks are converted to Ca–Mg–Fe–Mn

silicate assemblages by reactive fluids in the vicinity of intermediate to granitic
intrusions. Their development is controlled by a combination of favorable lithology
and structures, and therefore are mostly stratabound and vein and fracture-filled.
They may be closely associated with porphyry deposits (Fig. 2.28) or may remain
largely unmineralized. Early prograde silicate assemblages of garnet and pyroxenes
in calcic systems are deficient in ore metals but the later retrograde stage brings
most of the metals in association with hydrous phases such as, actinolite, biotite,
muscovite, chlorite, talc, quartz, and carbonates. Skarn deposits can be classified
based on the dominant economic metal as Fe, W, Cu, Zn–Pb, Mo, and Sn skarns
(Einaudi et al. 1981). Skarn deposit formed at or close to the inner contact zone of
an intrusive is called endoskarn, and that formed at the outer contact is called
exoskarn. Examples of some well-known skarn deposits are Memé mine, northern
Haiti (Cu), Sarbai, Kazakstan (Fe), King Island, Tasmania (W), MacMillan Pass,
Canada (W), Pine Creek, California (W), Cantung, NWT, Canada (W), Atamina,
Peru (Zn, Cu).
It may be noted that the economic metal concentration in skarns has some
general relationship with the composition of the associated intrusive body, oxida-
tion state, tectonic setting, or country rocks: Fe and Au skarn deposits, as a general
rule appear to be associated with intrusions of mafic to intermediate compositions;
Cu, Pb, Zn, and W skarns to calc-alkaline I-type intrusions and Mo and Sn to
S-type, i.e., ilmenite series granitoid. Further, interesting is the case of Bingham
Canyon, Utah, USA, which is not only the host to a very large porphyry Cu deposit
but also the largest Cu skarn deposit of the world.
Carbonate replacement deposits are formed where magmatic hydrothermal
fluids interact with carbonate rocks beyond the skarn front and produce
semi-massive to massive sulfides (Fig. 2.28). These deposits, commonly of Sn or
Zn–Pb–Ag, have stratabound manto or steep chimney configuration and may occur
alone or as distal extension to skarn deposits (Einaudi et al. 1981). Several
examples of this type are found in Rocky Mountains, Colorado.
Greisens are a secondary mineral assemblage formed by alteration of either the
granitic, or the country rocks by the addition of elements, such as, Si, Li, Be, B, F,
and H2O. The resultant mineral assemblage commonly consists of white mica
(generally Li-rich), quartz, topaz, tourmaline, and fluorite. The greisenized area may
show some kind of zoning. There is often evidence of feldspathization before
greisenization, and kaolinization following it, the effect being reflective of varying
fluid–rock equilibria with falling temperatures (Strong 1988). Greisen deposits are
related to shallow level felsic granites (<6–8 km) to subvolcanic setting and are
represented by various metals such as Sn, W (as wolframite) and sometimes Mo,
Bi, or Be accompanied by base metals which are paragenetically late in the
sequence and occur as disseminated mineralization in pervasively altered cupolas
and their wall rocks (Fig. 2.32) (Sillitoe 1996). They commonly show a close
relationship to quartz-dominated sheeted or stockwork vein system, where pressure
permits fractures to dilate. A continuum in mineralization is noted from pegmatites
to veins/greisens in many places.
70 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.32 A sketch of a Sn-dominated system centered on a granitic cupola, showing the relationship
between pegmatite, greisen, skarn, carbonate replacement, and sheeted veins (after Sillitoe 1996)

The Breccia deposits comprise vertically extensive pipes that develop either
within the granitic intrusions or in overlying wall rocks. Cu-bearing breccias occur
within or around porphyry Cu deposits (Fig. 2.28) but the breccias may contain one
or more of the other magmatically concentrated metals (Sillitoe 1985).

[Link] Iron Oxide–Copper–Gold (IOCG) Deposits

This is a recently perceived ore-type, characterized above all by the presence of iron
oxide, Cu, and Au, along with U and REE. The nomenclature relates to mineralization
in the Olympic Dam deposit, discovered in 1975 (with production starting in 1988),
about 560 km north of Adelaide in South Australia. This was the end result of a
concept-oriented exploration work based on a Ph.D thesis in Australian National
University, Canberra (Haynes, 1972 in Haynes 2006) which conjectured that conti-
nental tholeiite basalts, when altered to albite-hematite-phyllosilicate-epidote-carbonate
assemblages, become potent copper source rocks dependant on their Fe3+/Fe2+ ratios
and total Na (as albite) content. The Cu–Au–Ag–U–REE mineralization at Olympic
Dam occurs in a hematite-rich granite breccia complex within the Mesoproterozoic
(1600–1585 Ma) Roxby Downs Granite with A-type affinities in the Gwaler craton
(Solomon and Groves 2000). The complex is overlain by the flat-lying sedimentary
2.3 Hydrothermal Processes of Ore Formation 71

sequence of the Stuart shelf geological province. The ore mineralization is structurally
controlled and is of hydrothermal origin. Owned totally by BHP-Billiton, the Olympic
Dam deposit with its polymetallic ore composition is the world’s fourth largest
remaining copper deposit, fifth largest gold deposit, and the largest uranium deposit. It
also contains significant quantities of silver. The REE minerals won as a by-product of
the ore in this deposit are monazite, bastnaesite, fluocerite, and florencite.
Since the discovery of Olympic Dam deposit, exploration has been spearheaded
worldwide on deposits that varyingly resemble it, as the Olympic Dam deposit still
stands unique. Some deposits having varying resemblance to this type are Salobo,
Cristalino in Carajas region of Brazil (2.6 Ga), Ernest Henry in Cloncurry district,
Australia (1.7 Ga), Wernecke breccias, Yukon (1.3 Ga), Michelin and Sue-Dianne
in Canada, Candelaria (115 Ma) and El Laco deposits in Coastal Cordillera, Chile
and some deposits surrounding the Kaapvaal craton in South Africa. A somewhat
similar apatite-magnetite deposit in Sweden is known as the Kiruna-type. It is now
understood that IOCG represents a diverse variety of ore systems, formed in a
variety of tectonic settings, geological environments, and with differing ore com-
ponents but with a sort of commonality that binds them together. IOCG ore bodies
range from around 10 million tons to 4000 million tons or more of contained ore,
and have a grade of between 0.2 and 5% copper, with gold contents ranging from
0.1 to 3+ grams per ton. The large size, relatively simple metallurgy and relatively
high-grade IOCG deposits can produce extremely profitable mines.
A few years ago Groves et al (2010) made a critical review of the deposits
commonly referred to as IOCG in modern geological literature. They believe the
earlier definition of IOCG deposits has been a little too liberal. Many of the smaller
deposits ascribed to this group and in which Cu and/Au grades are much higher, i.e.,
typical of skarns, should be left out of the domain of IOCG deposits. The deposits
which have been included through this liberal definition of IOCG group are:
1. Fe-oxide Cu–Au deposits (IOCG deposits sensu stricto)
2. P-rich iron oxide deposits
3. F- and REE-rich iron oxide deposits
4. Carbonatite-hosted (Cu, F, REE)-rich deposits
5. Cu–Au and Fe-skarns deposits
6. High-grade Fe-oxide-hosted Au(± Cu)-magnetite deposits
We may exclude subgroup 5 from this list as they constitute well-defined deposit
types themselves. Precambrian deposits are better qualified for inclusion in the IOCG
group. These authors hold and have recently reiterated (Groves et al. 2016) that
IOCG (sensu stricto) deposits are magmatic-hydrothermal in origin. A recent
approach in this context (Richards 2016) is to differentiate between intrusion-related
IOCG from non-intrusion-related IOCG deposits, because in several deposits the
association of a granitic intrusive remains elusive. This also reduces difficulties in
developing a robust exploration model for the mineral deposit type.
72 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

The complex character of the IOCG deposits may be outlined as follows

(Hitzman et al 1992; Papers in Porter 2000, 2002; Williams et al. 2005; Groves
et al. 2010, 2016; Sarkar and Gupta 2012):
1. Cu and Au are the principal economic metals in this type of ore. The Cu-grade
in >60% of Cu–Au deposits range between 0.5 and 1.5 wt%, averaging about
1 wt%. Chalcopyrite is the principal Cu mineral. Au commonly is <1 ppm.
U content variable, not large except in bulk.
2. Iron oxides (magnetite, hematite) present are intimately associated with Fe–Cu
sulfides (Fig. 2.33) and are of low-Ti variety. Fe silicates (grunerite, Fe acti-
nolite, and fayalite) may be present instead. Magnetite may be accompanied by
a phosphate (apatite).
3. Sulfides are low-S variety (pyrrhotite, chalcopyrite, bornite, chalcocite). Sulfur
isotope data (d34 S) are typically, but not invariably, close to 0 ± 5 per mil.
4. Ores are generally enriched (0.5–10 wt%) in LREE.
5. Structurally controlled, commonly with breccias; pervasive alkali
(Na ± K ± Ca) metasomatism is commonly present in the ore zone. IOCG
mineralization and alkali metasomatism is co-itinerant but not isochronous,
metasomatism preceding by 10–20 Ma.
6. IOCG mineralization is not time specific, the major ones however, being
Proterozoic in age.
7. Ore zone minerals show high temperature (>250 °C), hypersaline, and CO2-
rich fluid inclusions.

Fig. 2.33 Drill core from Olympic Dam deposit, Australia showing brecciated ore with magnetite
(M) and chalcopyrite (C) in a hematitic (H) groundmass (Photo courtesy Indrani Mukherjee)
2.3 Hydrothermal Processes of Ore Formation 73

8. The deposits show clear temporal but not necessarily spatial association with
causative intrusions which formed from hybrid mantle-crustal magmas sourced
from metasomatized SCLM. Thus, there are felsic intrusions, commonly A-type
granites with alkaline to sub-alkaline affinity in the IOCG districts.
9. The ore zone is characterized by low silicification, in contrast to many
admittedly hydrothermal ore deposits.
10. The deposits are located in areas that are cratonic or of continental margin
environment, characterized by extensional tectonics (Fig. 2.34).
A review of the descriptions of this type of deposits leads to the following
definition: IOCG deposits have Cu and Au as the principal economic metals, are
structurally controlled, and surrounded by wall rock alteration and/or brecciation,
both regional in scale. The ore zone is depleted in SiO2 content and pyrite,
notwithstanding the mineralization is hydrothermal. The Cu mineral is chalcopy-
rite + bornite + chalcocite. The IOCG deposits differ from typical hydrothermal
deposits in the magmatism involved. (Partington and Williams 2000). Moreover,
there is enough evidence for the involvement of ultrabasic to basic mantle-derived
magmas, some with alkaline affinity, participating in the regional magmatic event.
IOCG deposits generally occur inboard of lithospheric boundaries. Kerrich et al.
(2005, 2010) explained the intra-continental occurrence of the IOCG system as due
to focusing of lithospheric extension and accompanying melting of metasomatized
subcontinental lithospheric mantle (SCLM) at necked transition between thick
Archean and thinner Proterozoic SCLM that guided mantle underplating. This
process produced basic and ultrabasic melts probably of alkaline affinity and
enriched in volatiles, Cu and Au. The melt ponds at the crust-lithosphere boundary,

Fig. 2.34 Tectonic and lithospheric setting of IOCG deposits (after Groves et al. 2010)
74 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

causes partial melting and production of felsic melts. Deep volatile exsolutions
produce giant breccias pipes of silicate rocks replaced by iron oxides followed by
Cu, Au and other enriched elements (Hart et al. 2004).
Origin of IOCG deposits has been controversial right from the beginning (Refs.
above). Earlier, two models held the sway. One held that the hydrothermal fluids
causing wall rock alterations, or producing the mineralization exsolved from
cooling granitic intrusives below, though, as indicated earlier, such granitic bodies
remain elusive in some cases. The other major model held that the hypersaline
fluids owe their origin to (an invisible) evaporate unit in the sequence. The most
logical explanation, based on petrologic and isotopic evidence, the LREE and
volatile enrichment, the giant size of the host breccia – bodies in some deposits and
the intense SiO2-depletion in the alteration halos put forward by Groves et al.
(2010) suggest devolatilization of deep, volatile-rich, mantle-derived magmas as the
primary energy- and fluid driving source for the IOCG ore systems, which produced
wall-rock alteration and metal deposition at greater depths than normal porphyry
Cu–Au producing dioritic to granodioritic magmas. Presence of Ni and Co in
economic/subeconomic proportions further bear evidence of the possible involve-
ment of mafic-ultramafic magmatism in the process. Uranium could be leached
from the crustal rocks the fluids passed through. On the other hand, evaporative and
mixed magmatic and non-magmatic brines are only responsible for pre-ore regional
scale alteration and have nothing to do with the mineralization itself. Majority belief
at the present moment is that the IOCG systems are produced not only by
deep-seated fluid-rich sources but also by fluid circulations controlled by crustal
scale dislocations. Further, Groves et al (2010) emphasize that size of the associated
alteration is a defining characteristic of the IOCG deposits.
Richards and coworkers (Richards 2013; Richards and Mumin 2013; Richards
2016) have more recently compared and generalized the conditions of formation of
intrusion-related IOCG (IR-IOCG) and Porphyry Copper Deposits (PCDs).
Similarities highlighted between the two types include generation from fluids
exsolved from moderately oxidized, calc-alkaline to moderately alkaline arc or
orogenic magmas while dissimilarities rest on lower S-content and larger
feldspar-stable alteration zones in the former compared to the latter. Sulfur-poor arc
related magmas in the Precambrian, ascribed to S-poor, reduced deep ocean waters
in the subduction zones at these times, produced IR-IOCG deposits whereas S-rich
magmas in similar setting in the Phanerozoic produced the sulfidic PCDs when
deep ocean water sulfate levels rose sharply after the Neoproterozoic oxygenation
event. Low fS2 and High fO2 conditions were favorable for the formation of low-S
(Sn-W) porphyry and some IOCG deposits (such as, in Chile) in post-subduction
tensional regimes of the back arc in the mid-Cretaceous (Fig. 2.35).
Giant Precambrian IOCG provinces formed about 100–200 My after super-
continent assembly. While majority of the IOCG deposits formed in anorogenic
domains, the phosphate-rich iron oxide deposits formed late, during convergent
orogenies.
2.3 Hydrothermal Processes of Ore Formation 75

Fig. 2.35 Sketch showing the development of IR-IOCG deposits in transtensional back arc
settings in the mid-Cretaceous (after Richards 2016)

Summing up, it may be concluded that there is no straight jacket view about the
IOCG deposits, although they share amongst them many things in common.
Similarly, there is similarity and difference in their genetic history. It is possible that
in future the IOCG deposits will be considered to have formed by interplay of
several processes. Some of the persisting unresolved questions about IOCG
deposits include: (a) the source of the large amount of Fe in the deposits; (b) role
and type of magmatism; (c) presence of a large variety of elements (U, P, REE, Cu,
Au, Mo, F, Ba, etc.). Do they indicate multiple source and mixing of reservoirs?
(d) Deficiency of sulfides in some deposits; (e) presence of low-Ti–magnetite.
Could it be from a non-mafic magma, formed by low-T solutions? High salinity of
fluid inclusions in the ore zones is rather suggestive of this.

[Link] Rare Hydrothermal Nickel Deposits

The Avebury nickel deposit, Tasmania, which contains a resource of 2,60,000 tons
of Ni at a grade of 0.9% and associated with an ophiolite sequence is an uncon-
ventional deposit of nickel. The ophiolite consists of cumulate peridotite and dunite
of Middle Cambrian age. The principal nickel mineral is pentlandite. Modest to
strong correlation between Au, Pd, REE, Sn, Mo, W with Ni suggests that the
nickel mineralization was caused by the hydrothermal solutions given out by a
Devonian granite intrusion at the site (Keays and Jowitt 2013). This should be an
eye-opener for other explorers.
76 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

2.3.2 Essentially Amagmatic Hydrothermal Processes

Sources of hydrothermal fluids and the mineral deposits formed there from are
shown schematically in Fig. 2.36. Water in rocks is genetically classified into four
types: juvenile, derived from magmas; metamorphic, produced by devolatilization
during metamorphism; meteoric, contributed by the atmosphere; and connate,
contained within sediments. Metamorphogenic hydrothermal solutions are formed
from sedimentary(-volcanic) rocks undergoing metamorphism, with greenschist
facies conditions producing more ore fluids than other grades. The ore mineral-
ization from such fluids is not much different from that produced from juvenile
fluids. Deposits formed during burial and diagenesis of sediments are also
hydrothermal deposits and have many things common with epithermal deposits.

[Link] Volcanic-Hosted Massive Sulfide (VHMS) Deposits

Volcanic-hosted massive sulfide deposits (VHMS: Large et al. 2001; Huston et al.
2010), volcanic-associated massive sulfide deposits (VAMS: Franklin et al. 2005)
and volcanogenic massive sulfide deposits (VMS: Franklin et al. 2005) mean the
same. Only in the last, the connotation is to genesis and in the other two, it is rather
descriptive.

Fig. 2.36 Different fluid sources and different types of hydrothermal ore deposits with examples
2.3 Hydrothermal Processes of Ore Formation 77

These are deposits formed at or near the sea floor in a submarine volcanic
setting, either in ocean spreading ridge or in the back arc of an island arc
(Fig. 2.37). They are characterized by massive sulfides, that is,  60% of sulfides
of Fe–Cu–Zn–Pb (Fig. 2.38) with additional quantities of Au, Ag, Cd, In, Sn, Ge,
etc. The mineralogy is generally simple: sphalerite, galena, chalcopyrite. Fe is
present mostly as sulfides (pyrite, pyrrhotite, arsenopyrite) and less often as mag-
netite. Morphologically, most of these deposits can be divided into two parts: the
concordant sulfidic upper part, underlain by a stockwork of ore minerals and sili-
cates (Fig. 2.39). The upper part is generally stratiform and in fair measures,
stratified and composed of the massive ores. They generally occur as member(s) of
a dominantly volcanic sequence. There is also the presence of thin, but aerially
extensive units of ferruginous chemical sediments formed from exhalations in the
topmost part of these deposits. This picture is mainly based on the deposits in the
Kuroko district of Japan where the role of felsic centere, explosive activity at the
vent, brecciation, stringer zone, exhalites and metal zonation are conspicuous. In
Canada, based on the Archean deposits of the Noranda camp, an upward stratig-
raphy has been traced (Lydon 1984) (Fig. 2.40) which involved alteration zone in
the footwall with veins and stockwork, and layering, breccias, massive sulfides,
and exhalites in the hanging wall. These zones vary in shape and size depending on
the host rocks, geologic setting, water depth, etc.
Temporal distribution of VHMS is wide, starting from Archean until the present,
interrupted by some breaks or lean periods. These periods are between 2500–2000,

Fig. 2.37 Tectonic settings of volcanic-hosted massive sulfide deposits in convergent margins
(after Huston et al. 2010)
78 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.38 Banded massive sphalerite-pyrite ore; drill core from Deri mine, Southern Rajasthan
(Photo: M. Deb)

Fig. 2.39 A model of VMS ore formation (after Franklin et al. 2005)
2.3 Hydrothermal Processes of Ore Formation 79

Fig. 2.40 A schematic section across a Noranda type VMS deposit (after Franklin 1995)

1700–1400, and 1000–750 Ma. They are believed to correspond to periods of

supercontinent stability or breakup (Huston et al. 2010). Rodinia is however, an
exception. There are about 800 deposits of this class worldwide. Some are forming
on the ocean floor at present. The average size of a VMS deposit is *10 Mt, with
the modern sea floor deposits being *0.2 Mt. Any deposit >50 Mt is considered to
be a giant deposit of the kind.
VHMS deposits do not occur in any unique geological situation. Rather, they
occur in a couple of different settings, represented by varying lithotectonic asso-
ciations. The following five lithostratigraphic associations of VHMS are recognized
(Barrie and Hannington 1999; Franklin et al. 2005):
1. Bimodal mafic
2. Mafic
3. Pelitic-mafic
4. Bimodal-felsic/alkaline
5. Siliciclastic felsic.
The first three types are related to ocean–ocean subduction and represent nascent
arc rifting (Type 1) to mature back arc development (Types 2 and 3). In Archean
greenstone terrains, environments of Type 1 also include a mantle plume
(komatiite) association. Bimodal-felsic and siliciclastic felsic types (Type 4 and 5)
formed in ocean-continent margins to continental back arcs. Bimodal alkaline
lithofacies have Pb  Zn > Cu and its geodynamic setting involves paleo-plume
producing sea mount and submarine epicontinental rift. Characters of these types
are discussed somewhat elaborately in Table 2.4. As we shall see later, these
petrologic associations have genetic significance also.
These lithostratigraphic associations are represented by a number of rock types
in different proportions, having formed in varied tectonic settings (Table 2.4). To
facilitate discussion of the criteria for classification of VHMS deposit and introduce
80 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Table 2.4 Lithotectonic types of VHMS deposits and their metal contents (geometric mean).
(Based on Barrie and Hannington, 1999 and Franklin et al., 2005)
Petrogenetic types Petrologic Geodynamic Ore metals
associations settings Cu Pb Zn Au Ag
% % % ppm ppm
1. Bimodal mafic Basalt-dominated Incipient-rifted 1.24 0.30 2.32 0.81 21.14
(but with up to bimodal volcanic
25% felsic arcs above
volcanic rocks); intra-oceanic
pillowed and subduction
massive basaltic
flows; subordinate
volcaniclastic
rocks; immature
wacke; sandstone
and argillite;
hydrothermal
chert in immediate
hanging walls in
some deposits
2. Mafic Ophiolite and Mature 1.82 0.02 0.84 1.40 10.62
ophiolite-like intra-oceanic
assemblages, back arc, some
dominated by transform fault
pillowed and related (oceanic
massive basaltic mature back arc)
flows, minor felsic
volcanics; minor
ultramafic flows;
synvolcanic mafic
dykes and/or sills
up to 50%;
sedimentary rocks
minor
3. Pelitic-mafic Basalt and pelite Oceanic mature 1.23 0.68 1.58 0.75 19.29
subequal, or pelite back arc. Co may
dominant; mafic be present in the
sills up to 25%; ore metal
felsic volcanic association
rocks
absent/negligible.
Sediments:
carbonates,
argillite,
subordinate
siltstone and
wacke; mafic
ultramafic sills
and flows in
sedimented
(continued)
2.3 Hydrothermal Processes of Ore Formation 81

Table 2.4 (continued)

Petrogenetic types Petrologic Geodynamic Ore metals
associations settings Cu Pb Zn Au Ag
% % % ppm ppm
mid-oceanic ridge
and back arc
basins
4. Bimodal-felsic Felsic volcanic Continental 1.04 1.14 4.36 1.06 56.35
rocks constitute margin arcs and
35–70% of related nascent or
volcanic strata and primitive
basalt 20–50%; epicontinental
terriginous back arcs,
sediments *10%. including
Some portions submarine
may be subaerial continental rift
settings
5. Siliciclastic-felsic Siliciclastic rocks Mature 0.62 1.09 2.70 0.59 38.54
dominant epicontinental
(*80%); felsic back arc
volcaniclastic
rocks (with minor
flow domes, etc.)
constitute about
*25%. Mafic
(tholeiitic to
alkaline) flows,
volcaniclastic
rocks and sills in
the hanging wall
succession
(*10%) Fe-, Mn-,
Ca-, Ba-rich rocks
in the hanging
wall

the influence of the form and composition of volcanism on the development of

VHMS deposits, the five lithostratigraphic types are further subdivided on the basis
of their occurrence in successions dominated by one of the three end member
lithofacies: flow, volcaniclastic, and sedimentary (Franklin et al. 2005).
Based on metal association (Cu:Pb:Zn) in the VHMS deposits (Fig. 2.41), and
considering their type area of occurrence, they are classified into following four types:
(1) Cu (mafic-dominated) (Cyprus type)
(2) Cu–Zn (Archean greenstone terranes) (Noranda type)
(3) Zn–Cu–Pb (Phanerozoic terranes) (Kuroko type)
(4) Pb–Zn–Cu (sediment-dominated settings) (Besshi type)
82 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.41 Triangular

classification of VMS
deposits based on the metal
content (after Franklin 1995)

Deposits of felsic-dominated associations have significantly lower 100 Zn/

(Zn + Pb) and these associations become important as the age of the deposit
decreases.
Origin of VHMS Deposits.
Geological features, results of laboratory experiments and direct observations on
ore formation on sections of sea floor (see a later section for more details) con-
vincingly established that these deposits have close relationships in space, time, and
genesis with the volcanic rocks with which they are associated. Geological
observations further suggest that they are products of volcanically generated
hydrothermal systems. Sawkins (1990) argue that the genesis and distribution of
VMS deposits should be viewed as integral parts of the spectrum of magmatic-
hydrothermal ores related to subduction-related magmatism in arc environments.
He suggests that the variations in both metal composition of such ores, as men-
tioned above and the petrochemistry of coeval intrusions relate in a fundamental
way to the siting of their emplacement in arc and back arc systems and the duration
of the subduction process.
Sources of Ore Fluids, Metals, and Sulfur
Close association of VHMS with volcanic rocks has been generally taken to suggest
that the fluids that produced the deposits were evolved seawater (Franklin et al.
1981), formed by downward penetration of cold oxidized seawater into fractured
oceanic crust ± magmatic hydrothermal fluids. It is also generally accepted that
these systems have important subvolcanic intrusions that actually work as heat
engines causing/enhancing hydrothermal fluid flow (Fig. 2.39). The data from
Kuroko deposits in Hokuroku district of Japan including the range of dD values
(–10 to –40‰) obtained from fluid inclusions in these ores, however, lend support
to a major involvement of magmatic hydrothermal fluids in their genesis (Urabe
1987). The released magmatic fluids merge with modified seawater convection
system after breaching through the silicified impermeable barrier which acts as a
2.3 Hydrothermal Processes of Ore Formation 83

reservoir cap. Metal enrichment in the magmatic fluid may also supplement the
metal content of the seawater convection system. This flow system has two-way
movements: the hot lighter fluid moves upward and draws down the cold seawater.
Up flow of vent fluids that react with the wall rocks form distinct alteration zones in
the footwall with strong depletion of Si, Na, and Ca and enrichment of Mg, K, and
SO4. Thus, a sericite zone forms outwards and Fe/Mg-chlorite inwards, depending
on the host rocks being altered. A number of studies of the deeper parts of the
semi-conformable regional alteration zones, produced by large-scale fluid flow in
VHMS districts, showed that these are leached of metals and at places sulfur,
with/without input from below. Host rock contribution is indicated by some data in
Table 2.4. The ore-bearing hot fluids ultimately vent out on to the sea floor along
dislocation zones (Fig. 2.39), producing the sulfide mound. The stages of evolution
of the mound and its zone refining are presented in Fig. 2.42 (Huston and Large
1989). These include: (1) Low T, Zn-rich mound formation at *200 °C with
sericitic alteration of wall rocks by acid fluid. (2) At *250 °C the mound has
grown and sericite zone is broader. (3) Higher T fluids (300–350 °C) move up and
get Cu-rich solutions encroaching and formation of chlorite alteration in the pipe

Fig. 2.42 A model for stage-wise evolution of a VMS mound on the sea floor (after Eldridge et al.
1983; Huston and Large 1989)
84 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

zone (Fe from fluid reacts with wall rock); (4) Large mound has formed, zone refining
occurs; late Fe-rich solutions invade and replace chalcopyrite formed above.
Ore Deposition
Deposition of VHMS is due to mainly two reasons:
1. Mixing between upwelling hot ore-bearing fluids and the cold down-moving
water.
2. Cooling of the upflowing hot hydrothermal solution.
Both will destabilize the ore-bearing complexes and precipitate ore.
Sulfur isotope values of VHMS varied with time, in both sulfide and sulfate
minerals. Sulfide minerals from Archean and Proterozoic VHMS deposits are
characterized by d34S values ’0 per mil, with little variation between the deposits.
The picture changed completely during the Phanerozoic when d 34S became highly
variable (Franklin et al. 1981; Huston 1999).
It is obvious from the above discussion that the VHMS deposits are at least
penecontemporaneous with host rocks, if not exactly syngenetic in all cases. Most
of the geological environments in which they are deposited are, in due course of
time, subjected to thermo-tectonic modifications in different degrees. As a result,
they are deformed and petrologically modified, along with the host rocks, i.e.,
metamorphosed. The mineral compositions of the wall rocks consequently undergo
change. Thus, development of Fe-poor mica and amphiboles as well as Ca-poor
plagioclase in the wall rocks are common. These probable changes may be kept in
mind while studying and exploring for a VHMS deposit.

[Link] Present-Day Marine Metallogenesis

Studies on recent marine metallogenesis have provided deep insight to our

understanding of ore-forming processes in such environment, in both present and
past. Many chemical processes operate in the oceans, proto-oceans, and shallow
seas producing hydrothermal and sedimentary deposits of certain metals in sub-
stantial amounts. The former is discussed in the following paragraphs and the latter
finds mention under Sect. 2.4.3.
The oceanic setting has two environments: (i) pelagic areas and (ii) continental
margins where phosphorite deposits form by upwelling in water depths <1000 m,
such as, in the offshore of SW Africa and Peru-Chile. Hydrothermal deposits form
in pelagic areas of divergent as well as convergent plate margins. Intra-plate regions
generally have sedimentary deposits. The divergent margins could be fast/medium
spreading such as in East Pacific Rise (EPR) and Gorda-Juan de Fuca ridge where
Fe, Zn, Cu-rich sulfide chimneys are forming. The active chimneys are classified
into black smokers if the precipitates are dark in color (high temperature), or white
smokers if the precipitates are light colored (low temperature). The inactive
chimneys are physically and chemically unstable and are reduced to rubble, forming
2.3 Hydrothermal Processes of Ore Formation 85

part of the basal mounds (Zierenberg et al. 1984). Petroleum reserves may also be
generated in thick sedimentary pile of such setting, such as, in Guayamas basin on
EPR at 72oN. Slow spreading divergent margins are characterized by Mn and Fe
oxide crusts and Fe–Zn−Cu chimneys as in Mid-Atlantic Ridge (MAR), Snake pit
at 23oN, TAG field at 26oN, Broken Hill spur at 29oN and Lucky strike at 37oN.
The relatively scarce sediment-filled troughs on MOR host large deposits of mas-
sive sulfides (Fe, Zn, Pb, rarely with As, Sb) formed by reactions of hydrothermal
solutions with the sediments, such as, in Escanaba trough, Gorda ridge; Middle
valley, Juan de Fuca ridge (Zierenberg et al. 1993; Goodfellow and Franklin 1993).
Hydrothermal processes in convergent margins produce Mn-rich crusts such as in
Tonga-Karmadec ridge in SW Pacific and Fe, Cu, Zn, Pb, + Au accumulations in
extensional regimes of back arc basins related to subduction zones. Both
intra-oceanic (e.g., Lau basin, Manas basin in SW Pacific) and intra-continental
(e.g., Okinawa trough and Izu-Ogasawara trough in the Japan Sea) settings produce
sea floor deposits (Roy 1999).
The Red Sea, which represents an early stage of opening of an ocean
(proto-ocean), is a large repository of massive sulfide deposits. In this slow
spreading center, seawater penetrates into basic volcanic and Miocene
(halite-bearing) evaporites, thereby gaining extreme salinity (9–10x seawater).
Dissolved metals as chloride complexes in hot (*200 °C), circulating modified
seawater are discharged as solutions into isolated troughs (deeps) rather than on
ridge crests (as in MAR). The density-stratified hydrothermal fluid ponds into the
deeps at low temperatures (*65 °C) due to slow rate of discharge in a stagnant
basin (Fig. 2.43a). The well studied “Atlantis II” deep is 7 km in diameter at a
water depth of 2000 m, hosts polymetallic sulfides (Fe, Zn, Cu, Pb, Ag, Au)
estimated at 100 Mt (Shanks and Bischoff 1980). Mn in the hydrothermal solution
diffuses upward into the oxidizing zone without precipitating in the sulfidic zone,
around which it forms a geochemical halo, just like the plume-driven Mn haloes
around black smoker fields in EPR and MAR.
Examples of shallow seas are the Baltic and Black seas. The former has oxic sea
floor with Fe–Mn nodules and sub-oxic to anoxic deeps with Fe–Mn carbonates
and sulfides. The latter has an oxygen stratified water column which hosts Fe
sulfides on deep sea floor and Fe–Mn oxides in the shallow margins (Roy 1999).
The ore-forming process in all the oceanic situations mentioned above begins
with the seawater penetrating the permeable oceanic crust for several kms down-
wards, getting heated by the prevailing geothermal gradient and probably by the heat
from a subvolcanic magma chamber (Hutchinson et al. 1980). Geophysical studies
have confirmed this last conjecture in the superfast-spreading EPR by identifying
relatively shallow (1.2–2.4 km below sea floor) axial magma chamber (Detrick et al.
1987). Magmatic contribution to the ore-forming fluid, besides supplying heat, has
also been identified based on the high ratios of volatile (3He, CH4, H2S) to
non-volatile (Mn, Fe) in the plumes of EPR (Urabe et al. 1995) just like in the
eastern Manus back arc basin, W. Pacific. The circulating seawater is reduced by
reaction with Fe2+-silicates with its sulfate forming pyrite and magnetite. As it
penetrates deeper, reaction between the modified seawater and basalts at
86 2 How Do Mineral Deposits Form and Transform? A Systematic Approach
 2.3 Hydrothermal Processes of Ore Formation 87

JFig. 2.43 Development of massive sulfide deposits on the sea floor. a A density-stratified pond of
hydrothermal solution giving rise to a bowl-shaped deposit; b Hydrothermal fluid, less dense than
seawater, forms a sulfide mound and rises buoyantly to form an exhalative plume that settles on the
sea floor to produce ferromanganese oxide crust and other exhalites (after Rona 1988);
c Formation of chimney and sulfide mound on the sea floor (after Barnes 1988)

temperatures in the range of 350–400 °C lowers the pH further and the water-rock
interactions leach metals like Fe, Mn, Cu, Zn, Si, etc. in substantial amounts. At still
deeper levels of penetration, H2O and CO2 get reduced to H2 and C2, respectively in
the presence of magnetite. The heated water is buoyant at temperatures around 400 °C
and starts convecting upward along fractures and dislocation zones when the reduced
carbon and hydrogen combine to produce CH4 and C2H6 in the enriched seawater. In
the vent, as pressure is released, it induces boiling, steam generation, phreatic
explosions, brecciation, etc. and the hydrothermal fluid starts mixing with shallow
circulating SO4-rich brine. Finally, it exhales on to the sea floor near the ridge crest
through black or white smokers (depending on the temperature) at a wide range of
temperature (*10–400 °C) and flow rate (1–2 cm to 1–2 m s−1) and mixes with
cold, alkaline, and oxygenated ambient seawater. The sulfides precipitate from the
turbulent waters to form a mound which holds chimneys, both upright and collapsed,
(Fig. 2.43b, c). The picture is very similar to that described for ancient VMS deposits
in Fig. 2.39. However, it must be pointed out that information on black smokers at
present-day active spreading (as opposed to back arc) ridges cannot be directly applied
to the genesis of VMS deposits even though the mechanism of final sulfide deposition
in both may be essentially similar (Lydon 1988). This is because subduction-related
magmatism is an essential attribute in all major deposits of this type (cf. Sawkins
1990).

[Link] SEDEX Deposits

SEDEX deposits are defined as sediment-hosted sulfide deposits that form from the
discharge of metal-rich hydrothermal fluids on the sea floor, commonly by venting
of fluids into reduced sedimentary basins on continental margins or in
intra-continental rift settings. They have been referred to by a variety of terms
including shale-hosted, stratiform sediment-hosted Zn-Pb and sedimentary exhala-
tive (SEDEX), the last being the most popular general descriptor of this economi-
cally important class of deposits. SEDEX deposits are an important resource type
and comprise more than 50% of the world’s Zn and Pb reserves and more than 25%
of the world’s Zn and Pb production. The grades and tonnage of Pb and Zn in this
class of deposits (Fig. 2.44) are an order of magnitude greater than VHMS deposits.
Pb + Zn grades vary between 5 and 20% commonly. Some of the large (+100 Mt)
deposits of this type are Broken Hill, H.Y.C., Mt. Isa, and Century in Australia,
Gamsberg, and Big Syn in South Africa, Fuenteheridos in Spain, Sullivan (now
closed) and Howards Pass in Canada and Red Dog in Alaska. SEDEX deposits are
noted first in the early Proterozoic, at about 1800 Ma and are somewhat rare after
88 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.44 Grade vs tonnage plot for well-known SEDEX deposits worldwide. Note the position
of Rampura-Agucha and Rajpura-Dariba deposits

the end of the Mississippian Epoch, except for minor deposits in Jurassic and
Cretaceous Periods. They show two major peaks of ore formation – one in the later
part of Paleoproterozoic (1800–1600 Ma) and another in the Phanerozoic, between
Cambrian and Carboniferous (Fig. 2.45). The major characteristics of SEDEX
deposits are treated at length by Goodfellow (2004), Lydon (2004) and Leach et al.
(2005), and summarized below.
Most SEDEX deposits are hosted by basinal sediments deposited within
intra-continental rifts or fault-bounded grabens of reactivated rifted continental
margins. They occur commonly in second or third order basins, spatially associated
with syn-sedimentary faulting. The extent of rifting can vary; while some failed to
develop an oceanic crust, others terminated after forming an oceanic lithosphere.
This gave rise to highly variable hydrothermal reaction zones and composition of
the hydrothermal fluids which are commonly saline and show a temperature range
between >200–250 °C.
The ambient sedimentary rocks consist of autochthonous carbonaceous chert,
shale, siltstone and coarser clastics, sedimentary breccias and carbonate rocks, and
allogenic clastic sediments. Highly carbonaceous non-bioturbated laminated sedi-
ments, absence of benthic fauna, anomalously high sulfur-carbon ratio and upward
increasing positive d34S trends in pyrite in host sedimentary rocks in many deposits
suggest that they formed during periods when the oceans were stratified with
reduced H2S-rich bottom waters. Many SEDEX deposits are composed of two
major hydrothermal facies, a sedimentary hydrothermal facies and a vent facies
(Fig. 2.46). However, the vent complexes in some deposits are absent, which is
probably due to poor preservation or accumulation of sulfidic products in the vent.
The sedimentary hydrothermal facies generally comprise sphalerite, galena, pyrite,
2.3 Hydrothermal Processes of Ore Formation 89

Fig. 2.45 Age distribution of SEDEX deposits worldwide (after Lydon 2004)

barite, and carbonate, and are interbedded with allogenic and autochthonous sedi-
ments. The ores are interbedded with Fe sulfides (pyrite, pyrrhotite) and basinal
sedimentary rocks which points toward a syn-sedimentary origin. In the vent facies,
the underlying sediments are veined, brecciated, infilled, and variably replaced by
quartz, carbonate, micaceous minerals, and some sulfides. The hydrothermal
alteration generally consists of silicification, carbonatization, sercitization, and
chloritization along with various sulfide formation. The hydrothermal facies
deposited above the vent complex are typically replaced at a later stage by higher
temperature sulfide–silicate–carbonate assemblages. The deposits are often strongly
zoned with Pb:Zn ratios decreasing away from the upflow zone. Sedimentary
textures such as graded and cross-laminated beds, sulfide sedimentary breccias,
slump structures, all indicate that most of the sulfides were deposited as sediments
on the sea floor. They were then subjected to local redistribution and
90 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.46 Cross section through an idealized SEDEX deposit, showing the different facies of
ores/sediments (after Lydon 2004)

recrystallization of mineral matter through subsequent diagenesis and metamor-

phism. Where the ore deposit has been metamorphosed and tectonized, the above
picture will obviously be distorted and may have varying degrees of aberration.
The proximity of the sulfides to the fluid discharge sites defines whether an ore
body is to be characterized as proximal or distal. The former has an alteration zone
in the footwall along with fragmental (brecciated) sedimentary rocks. The distal
ores form commonly in a brine pool depression away from the vent and are
characterized by well-laminated sulfides interbedded with sediments that have a
conspicuous absence of any wall rock alteration.
In summary, most SEDEX deposits form during post-rift reactivation of
extensional structures accompanying the thermal subsidence or “sag” phase of a
long-lived (100–200 My) basin (Fig. 2.47). They occur mostly within third-order
basins near their down faulted margins. There is also a close spatiotemporal rela-
tionship between SEDEX deposits and sills, dykes, and related magmatic rocks in
some instances. Magma injection into the lithosphere seems to have played an
essential role in generating the heat source necessary for convection of metallif-
erous hydrothermal fluids and formation of SEDEX deposits. The nature of the
sediment-fill in the basin plays a crucial role in SEDEX deposit formation. The
syn-rift clastic sequence in the lower part of the basin acts as an aquifer while the
reduced black shale and chert facies acts as an aquitard. The aquifer allows the
fluids to carry metals and convect and slowly gets geopressured. Finally, the cap
rock is ruptured and the mineralizing fluid is focused along active faults. As it
2.3 Hydrothermal Processes of Ore Formation 91

Fig. 2.47 SEDEX deposit model, based on the Bathurst Mining Camp, Canada. All the critical
factors mentioned in the text are seen in this model (after Goodfellow 2004)

exhales on the sea floor, it mixes with the H2S in the ocean water column. Based on
available fluid inclusion data, morphology of stratiform sulfide bodies and vent
textures, the hydrothermal fluids that vented into seawaters behaved either as
buoyant plumes or bottom hugging brines, eventually producing vent proximal and
distal deposits. Mineral assemblages, fluid inclusions, and stable isotope data
indicate that many of the SEDEX deposits formed from Zn−Pb(± Cu, Fe, Ag, Au,
Ba)-rich, low to moderate temperature, weakly to highly saline basinal fluids
(Fig. 2.48) that were generated by reaction with sediments derived from continental
crust and leached the metals from the Fe-oxide/-hydroxide coatings of grains in
sandstones, lithic clasts, etc.

Fig. 2.48 Model for the

generation of metalliferous
brine and SEDEX deposit
(after Lydon 2004)
92 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

[Link] Mississippi Valley Type (MVT) Deposits

This deposit type refers to Zn–Pb mineralization hosted by dolomitized carbonate

rocks and rarely sandstone and takes the name from the type area of Mississippi in
USA. Other well-known deposits are Pine Point and Polaris in Canada and several
deposits in maritime Canada and in Ireland. The ores generally have a simple
mineralogy of coarse galena ± sphalerite and colloform sphalerite at times.
Zn  Pb in these deposits. The ores also contain the association of Ba–F–Cu–Ag–
Ge–Co–V. The ores show evidence of low temperature cavity filling and replace-
ment. The age of the MVT deposits range from Precambrian to Tertiary with the
majority of deposits aged <1 Ga. Mineralization postdates the host rocks, even by
several hundred million years.
Deposits in Ireland have significant reserves and grades (e.g., Navan deposit
+120 Mt, 12% Zn–Pb) and have enough shared characteristics and differences from
other carbonate-hosted zinc-lead deposits worldwide to be given the name of
“Irish-type” (Hitzman 1999). The stratabound mineralization occurs in this field in a
transgressive sequence of Lower Carboniferous marine carbonate rocks lying above
a wedge of Upper Devonian continental red beds, similar to those seen in maritime
Canada. The orebodies follow dislocation structures, such as, normal faults. Besides
sphalerite and galena, Fe sulfides, and barite may be locally important. Textures of
the ores are complex and variable; some indicate early diagenetic origin. The
tectonic setting of these deposits indicates the extensional regime of a riftogenic
basin margin and reactivation of basement faults. The Pb isotopes in the ores are
radiogenic.
The MVT deposits are hosted by platform carbonates on stable cratons that
postdate clastic wedge deposition. The dolomitization produces the necessary
porosity-permeability in the host rocks for the movement of basinal fluids. Fluids
are metal rich, saline Na–K–Ca–Cl rich brines and are commonly <150 °C, but may
be hotter (<250 °C) in some cases, as in the Irish deposits. They are similar to
basinal brines found in oil and gas districts. Mineralization is considered to have
formed by basin dewatering, the reasons for which are often debated. Three distinct
models are available for the explanation of the generation and movement of basinal
fluids associated with MVT deposits. These are: (i) Topographic or gravity-driven
fluid flow model; (ii) Sedimentary and tectonic compaction model; and
(iii) Hydrothermal convection model. The first involves flushing of subsurface
brines out of a sedimentary basin by groundwater flow from recharge areas in
elevated regions of a foreland basin to discharge areas in regions of lower elevation
(Garven et al. 1993) (Fig. 2.49). In the second, expulsion of basinal fluids through
diagenesis and compaction and episodic fluid release from overpressured aquifers is
envisaged (Fig. 2.50). The last invokes deep convection of hydrothermal brines due
to buoyancy forces related to temperatures and salinity variations and producing
long-lived flow systems that recycles solutions through the rock mass and brings
about regional dolomitization.
There is a general consensus among many geologists that a continuum exists
between VHMS and SEDEX deposits on one hand and between SEDEX and MVT
2.3 Hydrothermal Processes of Ore Formation 93

Fig. 2.49 Topography or gravity-driven fluid flow model for MVT deposits. Fluid flow initiated
by the elevated thrust-faulted landmass which provides the hydraulic head (after Garven et al.
1993)

Fig. 2.50 Model for the formation of MVT deposits by expulsion of basinal fluids through
diagenesis and compaction and episodic fluid release from overpressured aquifers (after Evans
1997)

(cf. Sangster 1990) on the other. Compared to most VHMS deposits, hydrothermal
systems that generate SEDEX deposits are commonly long-lived, produce a tem-
perature maximum quickly and decay slowly over millions of years. SEDEX and
94 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

VHMS deposits form from hydrothermal fluids vented onto the sea floor, so that the
age difference between the ores and the immediate host rocks is always small. MVT
deposits formed in the subsurface by precipitation in open spaces within carbonate
platformal sequences; thus the age difference between ores and host rocks can be
much larger than for SEDEX deposits. The model for SEDEX deposits is similar to
VHMS deposits. The difference lies just in the heat source and lower T in the
SEDEX formation, as discussed above. The metal association and alteration types
are also different in the two deposit types. Besides, formation of VMS deposits may
be less dependent on an ambient anoxic water column, compared to the SEDEX
deposits. Distinction between the three deposit types is based not only on their
geological features and geological environments, but also on their genetic models.
Some workers believe (cf. Goodfellow 2004) in the cogenetic formation of some
SEDEX and MVT deposits involving the mixing of basinal metalliferous fluids
with ambient anoxic waters at the sea floor and within permeable reef carbonates, as
shown in Fig. 2.51.

[Link] Sediment-Hosted Stratiform Copper (SSC) Deposits

This deposit type constitutes some of the world’s largest copper deposits and
contributes about 25% of the world production of the red metal, being only second

Fig. 2.51 Model for cogenetic formation of SEDEX and MVT deposits (after Goodfellow et al.
1993)
2.3 Hydrothermal Processes of Ore Formation 95

to porphyry copper deposits. Some deposits also produce large amount of Ag and a
few are sources of Co, U, and other metals. The deposits are widespread, occurring
in almost all geological eras from Early Proterozoic, postdating the first occurrence
of undisputed red beds and cyanophytes (ca. 2.3–2.4 Ga), to Recent (Kirkham
1989). The most important and large deposits occur in Late Proterozoic and Late
Paleozoic rocks which correlate closely with widespread desert sedimentary envi-
ronment. Major part of the production comes from a few very large deposits and
districts of the Central African Copper belt of Zambia and Zaire, Dzhezkazgan, and
Udokan in erstwhile Soviet Union, and Lubin in Poland. White Pine, Michigan and
Spar Lake, Montana are the significant producers in North America.
These deposits have several distinguishing features (Kirkham 1989). They
contain disseminated, commonly zonally distributed sulfides that occur in reduced
rocks near oxidation-reduction boundaries. The sequence of minerals from the
oxidized to the reduced side comprises all or some of the following: hematite,
native copper, chalcocite, bornite, chalcopyrite, galena, sphalerite, and pyrite.
Mineral zones overlap upward and outward. In most localities, typical associated
rock types are red beds and evaporites. Major deposits (“Kupferschiefer type”) are
located in anoxic sedimentary rocks immediately overlying typically red, conti-
nental clastic sedimentary rocks. The host rocks were characteristically deposited in
arid to semi-arid areas within 20o–30o of the paleo-equator and in most areas are
interbedded with evaporites.
Theories on the origin of sediment-hosted stratiform copper deposits revolve
around two main issues: the source of their contained metal, sulfur, and other
constituents and the manner of migration to and precipitation of these constituents
in their depositional sites. The large stratiform Cu deposits appear to have formed in
basins with unique conditions that allowed accumulation of large amounts of
metal-bearing fluids, sufficient reduced sulfur, large amounts of reductants, and
focusing of fluid movement into relatively small areas (Hitzman et al. 2010).
General stratigraphic sequence in productive basins (Fig. 2.52) comprises a basal
horizon of syn-rift red beds, often with mafic or bimodal volcanic rocks that serve
as a source for rock-buffered oxidized fluids as well as a source of metals, partic-
ularly copper. This oxidized sedimentary package is overlain by marine to lacus-
trine sediments of sandstone, siltstone and shale, which may locally be organic-rich.
This siliciclastic sequence grades upward to marine carbonates that contain a thick
evaporite sequence. The upper portion of the basin contains shallow marine to
continental siliciclastic sediments. The evaporate beds provide an effective top seal
to the hydrologic system, whereas the basin edges themselves provide lateral
containment. The total thickness of the sediments in the basin may range from
several to >10 km. The stratiform Cu orebodies owe their origin to residual brines
or brines from evaporate dissolution that undergo diagenetic infiltration and move
downward into the basal oxidized red bed sequence. Geothermal heat and heat from
igneous activity initiate convection of these highly saline fluids which leach metals
from both the red beds and the basement. The oxidized metal-rich brines on their
upward flow encounter organic-rich sediments which work as reductants and help
to precipitate the copper sulfides. Fluids may also move up the faults in the basin
96 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.52 Sketch of an intracratonic, hydrologically closed basin where stratiform copper deposits
form (after Hitzman et al. 2010)

and precipitate sulfides where they encounter reductants, such as natural gas, pet-
roleum, etc. However, the roles played by evaporites, red beds and anoxic host
rocks demonstrate the importance of the environment of sedimentation and of
diagenetic oxidation–reduction processes in the formation of this deposit type,
which therefore, may also be classified under “Mineralization under
sedimentary-diagenetic processes” (see below).

[Link] Metamorphism of Massive Sulfide Deposits

The relationship of ore deposits with metamorphism in a metamorphic belt may be

casual or causal giving rise to metamorphosed or metamorphogenic deposits,
respectively (Mookherjee 1976). It is generally noted by most ore geologists that
the majority of stratabound VMS, SEDEX, SSC and MVT deposits, particularly in
Precambrian terrains and/or in orogenic belts, are co-deformed and isofacially
metamorphosed with their host rocks. The metamorphic record is better preserved
in the associated rocks and the silicate gangue minerals, as the sulfides are less
reactive and their thermal stability is generally inferior to the accompanying oxides
and silicates. Ores show metamorphism in grades varying from greenschist to the
granulite facies in the broad temperature range of 400–800 °C and at about 4–7 kb
pressure. Some ores are also known to display evidence of polymetamorphism with
the signatures of regional metamorphic event overprinted by a thermal imprint. In
most situations, the orebodies may display morphological changes from their
original, textural, and mineralogical changes and evidence of translocation if
remobilized. Massive sulfide deposits of all kinds may retain textural features of
deformation or get partially or wholly recrystallized while undergoing deformation
2.3 Hydrothermal Processes of Ore Formation 97

and may turn into a metamorphic tectonite. Thus, distinguishing between primary,
diagenetic, and subsequent deformation-recrystallization textures in such ores can
be critical in defining the time of ore emplacement and developing appropriate
genetic models. Metamorphism in middle to high grade does not generally obsure
the original mineralogy of these deposits, even though some significant miner-
alogical changes may be produced. Pyrite may be converted to pyrrhotite by
reaction with ferrous silicate minerals or by degassing of sulfur from the sulfide
orebodies during metamorphism. During metamorphic retrogression, pyrrhotite
may react to form pyrite and magnetite in minor quantities.
Metamorphosed deposits of these types are known in all continents (vide Spry
et al. 2000), the best studied ones being in the Scandinavian Caledonides, Mt. Isa
belt and Broken Hill deposit as well as Mt. Lyell and Roseberry, Tasmania, in
Australia and deposits in the Cape province in South Africa–Namibia. In India,
some of the best example of ore-host rock metamorphism is noted in the
Paleoproterozoic sediment-hosted Pb–Zn sulfide deposits, and Neoproterozoic
VMS deposits of Rajasthan, India (Deb 1979, 1990). Ore metamorphic features are
also reported from Paleoproterozoic Khetri copper belt, Rajasthan (Sarkar and
Dasgupta 1980) and Singhbhum copper belt, Jharkhand (Sarkar and Deb 1974).
While field studies, including detailed structural mapping help to identify the
phases of deformation, petrographic criteria of crystallization–deformation relations
in minerals in the host rocks and ores, along with conspicuous textural and min-
eralogical changes, and their compositional characteristics help to trace the
tectono-thermal evolution of the mineralized belts (cf. Tiwary et al. 1998).
Deformational structures in ores and ore bodies vary from folds (Fig. 2.53a), faults
(including ductile shears) to compressional (flattening) and extensional stretching
(with or without tearing). A fold structure in ores may be syn-deformational or
post-deformational. In the first case, one will expect crestal thickening (in the base
metal sulfide ores in particular) and may be, also axial cleavage in competent layers
(Fig. 2.53b). These features will be absent if the fold-form is inherited through
hydrothermal replacement of a compositionally suitable rock layer. Of course,
deformational features may be recorded in a single grain to an entire ore body.
Microfabrics indicating ductile deformation are slip bands, kinks, and translation
twin lamellae in softer sulfides. The brittle vs ductile character of a mineral, ore or
otherwise, is controlled by the mineral structure, ambient temperature and the rate
of strain. Strong deformation in conjunction with enhanced temperature during
dynamothermal metamorphism eventually leads grain growth and annealing. While
softer sulfides are annealed and developed annealing twin lamellae and foam
structure (Fig. 2.53c, d), the harder sulfides and some oxides underwent metablastic
growth with flowage of sulfide–silicate schistosity and rare pressure shadows, and
in some cases, intense fracturing during brittle deformation. Grain size generally
increases with the rise in grade of metamorphism. But if the deformation outlasts
recrystallization, then the deformational fabric with the grain size reduction may be
conspicuous. The above two broad textural varieties may coexist in neighboring
domains due to uneven strain-distribution. In extreme cases, a durchbewegung
structure may develop in an ore which includes rootless fragments and rounded
98 2 How Do Mineral Deposits Form and Transform? A Systematic Approach
 2.3 Hydrothermal Processes of Ore Formation 99

JFig. 2.53 a Intricate folding in carbonaceous chert and interlayered recrystallized pyrite bands in a
sample from Balaria, Zawar ore deposit, Rajasthan (Photo: M. Deb). b Crenulated bands in
pyrite-sphalerite-black chert rhythmite from Rajpura-Dariba deposit, Rajasthan. Note the
transposed schistosity at high angles to the pyrite laminae and the subparallel orientation of
pyrite boudins along it (after Deb and Bhattacharya 1980). c SEM photograph of foam structure in
galena mass in Deri deposit, Rajasthan. Note the deformed twin lamellae in adjacent sphalerite
(after Deb 1979). d Mosaic of recrystallized chalcopyrite grains in Ambaji deposit, Gujarat. Note
relict translation gliding in patches of chalcopyrite (after Deb 1979)

clasts of competent components (silicate rocks and hard ore minerals) studded
throughout an incompetent (sulfide) matrix. Such ores equate with high-strain
domains of partitioned, non-coaxial rotational deformation arising through extreme
heterogenous flow during a single event or separate overprinting events (Marshall
and Gilligan 1989). Large-scale chemical mass-transfer from an ore deposit during
metamorphism is not established.

[Link] Orogenic Gold Deposits

Gold mineralization in metamorphic tectonites, until recently, was generally

referred to as “Lode gold” (Poulsen 1995), “Mesothermal gold” (Nesbitt et al.
1986), “Shear gold” (Laznicka 1993) or “Gold–quartz–carbonate lodes” (Kerrich
and Fyfe 1981). It is clear that the nomenclature varies depending on which aspect
of the mineralization is emphasized. Also it is now known that several deposits
belonging to this broad group formed in P-T conditions surpassing the classical
conditions of mesothermal regime. A term widely accepted now is “orogenic gold
deposits” (Groves et al. 1998) which is defined as quartz-dominant lode gold
systems formed in the compressional regimes of crustal accretion along convergent
margins of continents (Fig. 2.54).
Giant orogenic gold deposits (>500 t Au) have been mined throughout the 20th
century. These include Homestake, McIntyre-Hollinger, Kirkland-lake,
Berezovkoe, Grass valley-Nevada City, Bendigo, and Kolar. Some continue to be
important resource still, such as, Ashanti, Golden Mile/Superpit, Campbell-Red
Lake, Morro Velho, Linglong, etc. Gold grades in this deposit type of ores are
highly variable – ranging from as low as 1 g/t to often as much as 20–30 g/t.
Figure 2.55 shows relative abundance of Au, Ag, and base metals in orogenic gold
deposits in greenstone belts along with other common types of hydrothermal ore
deposits for comparison (Poulsen et al. 2000).
Orogenic gold deposits share the following common features (Groves et al.
1998):
1. Orogenic gold deposits are quartz-dominant vein systems in which sulfides
(mostly Fe sulfides) generally constitute  3–5% and carbonates  5–15%,
with high Au: Ag ratio (*10:1 to 5:1)(Goldfarb et al. 2005). In the more
common greenschist facies environment albite, white mica, chlorite, scheelite,
and tourmaline are present as gangue in small but variable proportions. In the
100 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.54 Tectonic setting of different types of gold deposits, including orogenic gold deposits
(after Groves et al. 1998)

Fig. 2.55 Triangular plot of the relative abundance of Au (ppm), Ag (ppm), and base metals (%)
in orogenic gold deposits in greenstone belts and other common types of hydrothermal ore
deposits (after Poulsen et al. 2000)
2.3 Hydrothermal Processes of Ore Formation 101

amphibolites-granulite facies environment, hornblende, biotite, diopside, and

even augite may be present in addition.
2. Orogenic gold deposits are mostly hosted in deformed metamorphic belts of all
ages. They are most common in greenstone belts in Precambrian shield areas
and in late Neoproterozoic-Phanerozoic sedimentary rock dominant fold belts.
Syn-gold intrusions generally occur at, or within a few km of the deposits, but
there are some notable exceptions (e.g., Golden Mile, Bendigo).
3. Metamorphic grade of host rocks is typically greenschist facies, but higher (e.g.
Kolar) and lower (e.g., Donlin Creek) grades are also observed. Peak P-T
conditions in the country rocks have been reached within a few million to tens
of million years prior to ore formation for almost all deposits. Orogenic gold
deposits in eastern Asia, in very high-grade metamorphic rocks, provide a
globally unique example, where important deposits postdate metamorphism of
their host rocks by billions of years; these are the only large Phanerozoic gold
deposits known to be hosted in Precambrian cratons (Goldfarb et al. 2007).
4. The ore is epigenetic, hydrothermal in nature with characteristic albitization,
sericitization, carbonatization, sulfidation, and tourmalinization of the wall
rocks. Gold occurs mostly in veins but may also be present in the wall rocks.
5. Two major controls of gold mineralization of this type are structures and
petrochemistry of the source and host rocks. First-order controlling structures
are regional fault/shear zones in which the vein systems may extend for kms
along strike, 1–2 km along dip with little change in mineralogy or even gold
grade. A diversity of second-and third-order structures, from shear zones to fold
hinges, is recognized as controlling the gold mineralization. Brittle-ductile
structures locally host the ores. Hodgson (1989) proposed four types of
structures for shear-related vein-type gold: shear fracture, extension fracture,
hybrid (shear + extension) fracture, and fold-related structures. Robert and
Poulsen (2001), on the other hand, identified four major vein types: fault-fill
veins (mostly shear veins), extensional veins, stockworks , and breccias. The
first is most common in these gold deposits, characterized by laminated quartz,
slickenlines, and slip surfaces. Most fault-fill veins form lenticular mineralized
structures in the central part of ductile or brittle-ductile shear zones, either
parallel to or at a low angle with the shear zone boundary (Chattopadhyay
2010) (Fig. 2.56).
6. From a geochemical angle rocks rich in carbon or Fe2+ occurring along the path
of hydrothermal fluid flow are conducive to gold deposition through redox
reactions. Precambrian sulfide facies BIFs are often good hosts of gold
mineralization.
7. The ores are interpreted to have formed from low salinity, near neutral H2O–
CO2 + CH4 fluids.
8. Emplacement of orebodies vis-à-vis the stage of metamorphism and the source
of ore fluids and ore elements are other relevant issues in this context.
Ore-forming fluids may be introduced during pre-peak/syn-peak stages of
prograde metamorphism or during retrograde metamorphism.
102 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.56 Different types of shear and extension (or hybrid) veins associated with orogenic gold
deposits (after Chattopadhyay 2010)

9. The general consensus regarding the potential ore sources for such deposits are
metamorphic dehydration in a subducted slab, mantle devolatilization, magma
crystallizing at depths, deep basinal fluids, or even the surface-derived fluids
that penetrated deep into the crust (Goldfarb et al. 2005). Some deposits have
been suggested to be multisourced and to have a multistage history of formation
(cf. Deb 2014 and Chap. 5).
10. The gold resources in orogenic gold deposits show a secular concentration
between 2.8–2.55, 2.1–1.75, 750–35 Ma (Fig. 2.57) which correlates well with
continental growth, corresponding to the formation of Kenorland, Columbia,
Gondwana/Pangea and perhaps a new super-continent, respectively. The gold
deposits formed during growth of Rodinia appear to have been lost from
geologic record due to erosion of Meso-Neoproterozoic blocks to their deep
crustal levels that are below gold-favorable zones (Goldfarb et al. 2001; Groves
et al. 2005).

[Link] Unconformity-Related Vein Complexes of Uranium

These deposits constitute approximately 33% of the world uranium resources and
form due to geological and chemical changes in the hydrothermal solutions close to
major unconformities. Uranium deposits that occur close to the early-middle
Proterozoic unconformity or paleo-weathering surface and may be located above,
below, or along it, are assigned to this group. Unlike the QPC deposits they are not
hosted by pebbly rocks but are located at the base of a Proterozoic sandstone
2.3 Hydrothermal Processes of Ore Formation 103

Fig. 2.57 Global resource versus age of orogenic gold deposits. Crustal growth through time and
supercontinent assembly also shown (after Groves et al. 2005)

sequence, where they unconformably overlie pre-Middle Proterozoic metamorphic

basement rocks which generally include graphitic pelitic units and underwent
complex post-depositional transformation. The mineralization may be monotonous
uranium-only or polymetallic, with Ni, Co, and As accompanying uranium min-
eralization in fair proportions along with some minor elements. The most
well-known examples of this deposit type are in the Athabasca and Thelon basins of
Canada and in the Pine Creek region of the Northern Territory, Australia. The most
important deposits in the Athabasca basin in Saskatchewan, Canada are Cigar lake,
Key lake, Rabbit lake, McArthur River, and Eagle Point while notable Australian
deposits are Ranger I and III and Jabiluka I and II. The average grade range from
0.17% U in Ranger III to as high as 12.2% U in the main pod of the Cigar Lake
deposit. The Australian deposits are lower grade but exhibit a larger ore tonnage.
Three conceptual genetic models have been proposed for the Canadian deposits
of this type (Ruzicka 1995):
104 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

(i) Near-surface supergene derivation of ore constituents from basement rocks,

transport by surface and groundwaters and deposition under reducing
conditions.
(ii) Magmatic or metamorphic hydrothermal origin with derivation of ore con-
stituents from deep-seated source and transport and deposition from
ascending solutions.

Fig. 2.58 A conceptual

genetic model of
unconformity-hosted uranium
deposits. Arrows indicate
flow paths of reduced and
oxidized convective waters.
Various styles of
mineralization are: (1)
High-grade polymetallic
mineralization below the
unconformity; (2)
Medium-grade monometallic
mineralization below the
unconformity; (3) low grade
monometallic mineralization
above the unconformity (after
Ruzicka 1995)
2.3 Hydrothermal Processes of Ore Formation 105

(iii) Diagenetic-hydrothermal origin with precipitation of uranium from local

reductants (Fig. 2.58). Uranium was introduced in the geochemical cycle of
granitic magmatism in the Late Archean or Early Proterozoic and was
concentrated subsequently in sedimentary rocks and as
pitchblende-brannerite deposits. Principal concentration of the ore elements
took place during the pedogenesis of these basement rocks and diagenesis of
the basinal sediments produced the metal reservoir. Subsequent
tectono-thermal events involving the basin activated the hydrological system
and caused convective cycling of fluids with mobilization/remobilization of
the metals from the reservoir.

[Link] Sandstone-Hosted Uranium Deposits

This deposit type is also known as Colorado Plateau type or “roll-front” uranium
deposit and takes its name from the type area of Colorado Plateau (Northrop and
Goldhaber 1990) in Utah and New Mexico. They are also found in Wyoming,
South Dakota and South Texas in U.S.A. Most deposits are Devonian or younger.
Secondary roll-front deposits are mainly Tertiary. The deposits may be associated
with sediment-hosted deposits of V and Cu in similar environment. These strata-
bound deposits are characterized by microcrystalline uranium oxides, coffinite,
pyrite deposited during diagenesis in localized organic-rich reducing environments
within fine to medium-grained sandstone (feldspathic or tuffaceous) beds in the
interstices of detrital quartz and feldspar grains. Mudstone or shale occurs above
and/or below the host sandstone. The ore bodies are tabular, lensoid, or roll-like,
i.e., sinuous in both plan and section, with the crescentic lens cutting across bed-
ding. Replacement of wood or other carbonaceous material by ore constituents is
observed. The ore is sometimes dispersed throughout the host rock. Ore grades vary
from 0.1 to 1% U3O8. Oxidation of primary uraniferous minerals produces a variety
of minerals, notably yellow carnotite in V-rich ores. The depositional environments
are commonly continental-basin margins, fluvial channels, and braided stream
deposits. Adjacent major uplifts provide favorable topographic conditions.
A common genetic model of roll-type uranium hinges on the paleohydrology of
meteoric waters and the two valence states of uranium, U6+, U4+: U+6 being strongly
soluble in oxidizing conditions while U+4 being relatively insoluble in reducing
conditions. Three stages of U-collection to subsequent deposition in geological sit-
uations are recognized (Fig. 2.59): (1) Oxidative leaching of uranium from slightly
enriched felsic rocks (in basement or clasts in host sequence). (2) Transportation by
oxidizing surface and groundwaters through porous and permeable rocks.
(3) Precipitation on reaching a redox boundary (Goldhaber et al. 1978). Roll-type
deposits thus form when oxidized meteoric fluids containing uranyl carbonate com-
plexes flow down a reduced aquifer which is highly permeable during mineralization,
but is subsequently restricted by cementation and alteration. Redox reactions involved
produce the uranium ores. Oxidized iron minerals characterize the rocks up dip while
106 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.59 A schematic model for the origin of roll-type uranium deposit (after Goldhaber et al.
1978)

reduced iron minerals are found in rocks down dip from the redox interface. Some
uranium oxides may be redistributed by groundwater at the interface between reduced
and oxidized ground. Felsic volcanic and plutonic rocks in the district are the common
sources of uranium. In tabular ores, the source rocks for ore-related fluids are
commonly in overlying or underlying mud flat facies sediments. Tabular ores form by
fluid mixing at the interface between two low temperature meteoric fluids. The lower
one, relatively stagnant, is a brine containing Na+, Mg2+, Ca2+ and Cl−, and SO42−.
Another low-density flow containing such complexes as, UO2(CO3)2− +
2 and VO move
along the upper surficial zone of the lower unit, interact, and precipitate the ore
(Northrop and Goldhaber 1990). Uranium oxide is produced by the breakdown of the
uranyl complex, while the uranous ion and silica combine to form none too uncommon
silicate U-ore mineral, coffinite.

2.4 Sedimentary(-Diagenetic) Processes

The ore deposits that form in the exogenous environment may have been trans-
ported from varying distances as terrigenous clastics into the basin or zone of
deposition, and are termed allochthonous deposits. In contrast, there are other
deposits of ore metals which form in the environment in which they are deposited
and are termed autochthonous deposits (Evans 1997). The first group belong to the
mechanically concentrated placer deposits (alluvial, beach, and eluvial) and their
ancient counterparts, the quartz pebble conglomerate-type, paleo-placer deposits.
The second group on the other hand, includes the various chemical (+biochemical)
precipitates, such as the banded iron formations (BIFs), the sedimentary manganese
deposits, stratiform/sedimentary copper deposits, to name the most important ones
2.4 Sedimentary(-Diagenetic) Processes 107

in economic terms. The sedimentary(-diagenetic) processes which mainly produce

the second group of deposits may also have their imprint on some of the first group,
such as the paleo-placer deposits, as discussed below. The residual deposits of Fe,
Al, Ni, Mn, and Au and supergene deposits of Cu and Ag also develop in the
exogenous environment but will be dealt with separately.

2.4.1 Placer and Paleo-Placer Formation

Mechanically concentrated placer deposits may contain many economically

important resources, such as, gold, diamond, ilmenite, monazite, tin which are all of
high-specific gravity and mostly of high hardness (barring gold), and are therefore
resistant to attrition during winnowing and transportation by an aqueous medium.
They are chemically stable as well. The source rocks which contain these economic
minerals undergo weathering and the minerals are dislodged and subsequently
transported over varying distances by water. The amount and distance of trans-
portation are dependent on the quantum and velocity of the flow. Any physical
feature which can bring about a drop in the rate of flow, such as, where the gradient
flattens or at the inside of river meanders, a dike across the river, natural riffles on
the floor of the river or stream, below rapids and falls, beneath boulders, in veg-
etation mats or where a tributary produces a confluence, can be responsible for the
concentration of the economic heavy minerals by its separation from the lighter
detritus, mainly silica sand. Such placer concentrations can get buried by later
sediments and can occur along buried paleochannels. The most common aqueous
environments for accumulation of placers are stream channels or beach and shelf
regions. Stable coastal regions receive sediments from deeply weathered high-grade
metamorphic terrains. The winnowing action of the surf brings about heavy mineral
concentration, including that of gold and diamond (Sutherland 1982) if present in
the source rocks, in raised, present and submerged beaches (Fig. 2.60). Both these
environments are well represented in India, as detailed in a subsequent chapter.
Well-known alluvial placer deposits of gold are recorded in Subarnarekha river in
Jharkhand, Nilambur valley in Kerala, some tin deposits are found in Thailand and
Malaysia whereas well-known beach placers are the ilmenite and monazite beach
sands of the Malabar coast of India (Sarkar et al. 1995) and diamond deposits of
Namibian coast. Russia produces about 200 t of placer gold per year.

[Link] Quartz Pebble Conglomerate (QPC) Deposits

Quartz pebble conglomerate (QPC) deposits, found in the Archean and Proterozoic
sequences, are economically very important, being a major source of gold and a
significant source of uranium. The world class example is the Witwatersrand gold
fields in South Africa, which has a gold reserve of 52  103 t Au, accompanied by
533  103 t U, >3  103 t Ag, *30 t PGE, and *1000 t Hg. Other QPC deposits
108 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.60 An idealized section of a continental shelf showing the probable location of limestone,
sand and gravel, phosphates (in outer portion of the shelf) and placer gold, Ti-minerals, monazite
etc. (in the inner shelf). Salt domes may develop locally where previously deposited salt beds are
deeply buried. This environment is conducive to oil and gas migration and entrapment (after Craig
et al. 2001)

include Serra de Jacobina in Bahia state of Brazil, Dominion Reef, RSA, Tarkwa in
Ghana. In the Blind River-Elliot Lake in Canada (with resource about 432  103 t U,
350  103 t Th and 72 t REE+Y), Witwatersrand and Jacobina deposits, uranium is
extracted as a by-product of gold.
The Witwatersrand Goldfields in South Africa are located in the central portion
of the Archean Kaapvaal craton within low-grade metamorphosed siliciclastic
sediments of a Mesoarchean (2.9 Ga old) intracratonic basin. Seven major gold-
fields and a few smaller occurrences located around the northern and western
margin of the 350 km-long Witwatersrand basin (Fig. 2.61) have so far yielded
one-third of all gold ever produced on Earth and still remains the largest repository
of gold resource (*30,000 tons still remaining) in the world. Each goldfield
comprises one major and several minor reef horizons. The ore bodies are essentially
stratiform, 1 cm to several meters in thickness, within fluvial to fluvio-deltaic,
predominantly pyrite-rich (locally also uraninite-rich) quartz pebble conglomerates
(“reefs”), polymictic conglomerate, carbon seam and pyritic quartzites, which
overlie regional unconformity surfaces (Phillips and Law 2000; Frimmel 2005;
Tucker et al. 2016).
Stratigraphically, the host Witwatersrand Supergroup overlies the +3.0 Ga
basalts, volcaniclastics, and minor quartzites of the Dominion Group which rep-
resents the rifting phase of the granites and greenstones of the basement. The
Witwatersrand Supergroup comprises a lower, dominantly marine West Rand
Group (base fixed at 2.970 Ga) overlain by the mineralized fluvial sands, con-
glomerates and minor shales of the Central Rand Group. Subrounded pebble shapes
(Fig. 2.62) suggest textural maturity and the oligomictic conglomerates are inter-
preted as channel-filled deposits (paleoplacers). A downstream decrease in grain
size along with differentiation of heavy minerals indicates fluvial transport of ore
minerals. The mineralized zone occurs at/close to the base of the host sequence. The
2.4 Sedimentary(-Diagenetic) Processes 109

Fig. 2.61 Simplified geological map of the Witwatersrand basin, showing the location of the
goldfields (after Frimmel 2005)

Fig. 2.62 A polished slab of a drill core from Witwatersrand deposit comprising subrounded to
elliptical quartz and pyrite pebbles (Photo: M. Deb; sample from the collection of Late Prof.
M. Schidlowski, MPI, Mainz, Germany)
110 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

ore zone successions are succeeded upward by volcanics of the Ventersdorp

Supergroup (commencement age fixed at 2.714 Ga) (cf. Tucker et al. 2016) and the
Transvaal sequence (Fig. 2.63).
The mineralogy of the reefs is dominated by pyrite with lesser pyrrhotite and
arsenopyrite, widespread nickel, and cobalt sulfarsenides, and low quantity of base
metal sulfides. The main elemental association with gold is Fe, C, and U. Beside
uraninite and pitchblende, brannerite, thucholite (U-Kerogen), and pyrite are pre-
sent in the ore zone. Carbon isotope studies (Hoefs and Schidlowski 1967) showed
that this kerogen has a biogenic derivation possibly from prokaryotic life forms.
Further, Schidlowski (1981) suggested that mobile hydrocarbon-bearing fluids
permeated through the conglomeratic horizons and were radiolitically polymerized
by intense alpha-radiation from accumulations of preexisting uraninites. Uraninite
grains in QPC contain high (1–12 wt%) ThO2, characteristic of high temperature
(magmatic) origin (Cuney, 2010). A distinctive mineral assemblage of pyrophyl-
lite–chloritoid–muscovite–chlorite–quartz–rutile–pyrite is found to occur around

Fig. 2.63 Distribution of gold(-uranium) in a the basal sequence in Witwatersrand, RSA (Inset
field photo by M. Deb) and b Elliot Lake, Canada (after Laznicka 1993)
2.4 Sedimentary(-Diagenetic) Processes 111

the reefs in all the goldfields. This is considered as an alteration halo by some
(Phillips and Law 2000) and denotes a metamorphic temperature between 300 and
400 °C.
The enormous, high-grade gold deposits of Witwatersrand clearly required three
essential elements for their formation: source of the gold, concentrating mechanism,
and preservation potential. While the primary source of gold is generally considered
to be the greenstone belts and hydrothermally altered granites of the Archean
Kaapvaal craton (Robb and Meyer 1990; Tucker et al. 2016), the gold mineral-
ization at Witwatersrand has had its share of controversies revolving around the
concentrating mechanism of gold, whether it was introduced as detrital particles
during sedimentation (a placer theory), and underwent enhancement of concen-
tration during burial, diagenesis, and subsequent metamorphism (a modified placer
theory) or precipitated by epigenetic hydrothermal solutions moving along the
sedimentary facies at a later stage of basin evolution (hydrothermal model). This
spectrum of opinions is discussed briefly below.
In the early part of the history of Witwatersrand geology, since its discovery in
the later part of ninteenth century, the unmodified placer model was popular. It
envisaged that gold was transported from a source region into the basin in detrital
form and deposited through sedimentary sorting processes (Fig. 2.64). It of course
underwent burial but retained the original features of the depositional setting. This
model however, lost favor by the beginning of twentieth century and saw a revival
in the 1970s and 80s. Several studies, in more recent years (Minter et al. 1993;
Minter 1999) inferred that the shape and/or composition of the gold grains reflect
the source terrain. The accompanying rounded “buckshot” auriferous pyrite
(Fig. 2.62) and uraninite grains were thought to be detrital, and presented strong
evidence for primary sedimentary origin of gold in the anoxic atmospheric con-
ditions presumably prevailing at about 2.85 Ga ago.
The modified placer model is based on the presence of secondary textures and
typical hydrothermal minerals, silicates and sulfides, in the Witwatersrand reefs. In
this model, gold and its associated minerals are considered as primarily detrital,
partitioned into the coarse sedimentary fraction during transport and deposition and
then remobilized after burial in scales of centimeters. Geochemical studies show an
excellent correlation between carbon, gold, and uranium which is explained by
trapping of the metals in algal mats (carbon seams). The placer models however,
suffer from several weaknesses. A major problem is the difference between
Witwatersrand reefs and modern placers. The reefs are planar whereas the modern
placers are linear. A viable source area and large-scale alteration are the other
controversial issues in this regard (Philips and Law 2000).
In the hydrothermal replacement model, stages of early basin formation, early
diagenesis and generation of hydrocarbons, compression, migration of meteoric,
and basin-derived fluids and gold mineralization are envisaged (Philips and Law
1997). A reduced, low salinity fluid is considered to have been introduced into the
Witwatersrand Supergroup during metamorphism and tectonic evolution of the
basin, resulting in widespread alteration. The fluid was channelized along struc-
tures, unconformity surfaces and primary stratification and the gold precipitation
112 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.64 Illustration of the placer modelplacer showing processes operating within a single fan
and zones of gold concentration, being maximum in the mid-fan region. The distal portion of the
fan is asymmetrical reflecting the effect of the long shore current. The algal mat is the inferred
precursor of the carbon seams (after Pretorius 1976)

was controlled by reactions with carbon- or iron-bearing rocks above the uncon-
formity surfaces. One hydrothermal model infers a separate origin for gold, ura-
ninite, and hydrocarbons (Phillips and Law 2000), whereas another invokes a
cogenetic origin (Barnicoat et al. 1997).
Agreement exists between the two viewpoints that the gold-bearing reefs of
Witwatersrand show evidence of interaction with hydrothermal fluids, at least some
of which brought about the precipitation of gold together with sulfide phases and
bitumen. The basic difference between the two rests on whether the mineralization
took place essentially during sediment deposition or it postdates sediment deposi-
tion. Recently, Large et al. (2013), based on a LA-ICP-MS study of pyrites, have
concluded that both the competing models for the genesis of Witwatersrand gold
are likely to be correct. They suggest that the hydrothermal event was widespread in
the kilometer scale and involved basinal fluids that scavenged gold, arsenic, tel-
lurium, and other trace elements from the gold-bearing sedimentary units in the
Central Rand Group. Thus, the source of the gold in Witwatersrand deposits was
both intra- and extra-basinal and involved multiple concentration processes. Some
recent observations on the PGE content of gold in Witwatersrand deposits and
identification of gold and uraninite grains which predate the commencement of
Witwatersrand sedimentation are important in this context. The Re–Os ages of the
2.4 Sedimentary(-Diagenetic) Processes 113

gold are more than the sedimentation age (Kirk et al. 2002). Moreover, this gold has
considerably higher Os-concentration and near mantle initial 187Os/186Os ratio
(Frimmel et al. 2005). Minter (2006) determined U–Pb ages of 3.05 Ga for ura-
ninite grains and a Re–Os isochron age of 2.99 Ga from pyrite grains in the
Dominion and Witwatersrand conglomerate, having a depositional age of 2.97 Ga.
These justify the belief that at least a part of the gold was detrital, while another part
hydrothermal, derived by modification of the sediments during diagenesis-
metamorphism or the hydrothermal fluids ingressed from below along structural
discontinuities.

2.4.2 Banded Iron Formations and Related Ores

Within the broad group of chemically precipitated iron-rich sediments, banded iron
formations are internally laminated stratigraphic units with at least 15% Fe. Band
thickness varies from meters (macroband) through centimeters (mesobands) to
millimeters (microbands). The interlayers are made principally of iron oxides and
quartz/chert/jasper (cf. Figs. 3.1, 3.2 and 3.3), followed by carbonates. The oolitic
chamosite–siderite–goethite–clay-rich rocks, commonly referred to as ironstones,
are recognized as a distinctly separate type of iron-rich sediments. They formed in
different environments than the cherty iron sediments and probably have a different
origin and source of iron.
The banded iron formations are classified based on their general characteristics,
depositional environments and the kinds of sedimentary rocks associated with them.
Accordingly, there are two main types, the Algoman type and the Lake Superior
type (Gross 1966). The former has limited resource of iron being relatively thin and
discontinuous, traceable along strike for only a few tens of kilometers, shows
intimate association with tholeiitic to calc-alkaline volcanic rocks and
greywacke-type volcanoclastic sediments in deeper parts of basins or “eugeosyn-
clinal” belts (Cloud 1973). Soft sediment slump and deformation structures are
common, indicating their initial deposition as water-saturated chemical sediments in
unstable, subsiding basins accompanied by extensive mafic volcanism. The min-
eralogy of the banded ores varies depending on the type of sedimentary facies
(James 1954). The oxide facies are composed of magnetite  haematite and their
mixtures, deposited mostly as primary iron oxides. In general, these iron formations
reflect highly reduced conditions of deposition from seawater-hydrothermal effu-
sive systems. Silicate minerals in the silicate facies range from greenalite and
minnesotaite to stilpnomelane, cummingtonite, and grunerite. Carbonate facies
generally comprise siderite associated with magnetite or iron silicates but ankerite
or ferroan dolomites are prevalent where carbonates are associated with
hematite-rich facies. The sulfide facies of iron formations usually consist of fine
grained pyritic carbonaceous mudstone with interlayered chert or siliceous shales.
They exhibit rapid changes among the different facies. These iron formations often
have a close spatial and genetic affiliation with other important metalliferous ores,
114 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

notably with certain Ni sulfide deposits, auriferous lodes, and massive base metal
(Cu, Zn) sulfide deposits (Hutchison 1981). They are widespread in Archean
(>2.5 Ga) greenstone belts in the world’s ancient cratons and reappear with lesser
intensity in later ages. Examples are in the Superior province in northeastern
Ontario, in the Yilgarn block of Western Australia, in the Kaapvaal craton of South
Africa, and in the Baltic shield of northern Norway. In India, this type of BIF is
mainly found in western Dharwar and in all the auriferous greenstone belts of
eastern Dharwar craton.
Lake Superior type iron formations are, on the other hand, the main repository of
iron resource in the world with the association of quartzites, dolomites, and black
slates developed in shallow continental shelf environment. Epiclastic sediments are
present but basic volcanic rocks in the ore districts are not as closely associated as
in the Algoma type. These iron formations are commonly fine grained and oolitic,
show lateral extent up to few hundred kilometers with great continuity. The
thickness of these BIFs could measure in hundreds of meters. The conspicuous
banding of the BIFs is due to alternation of cryptocrystalline silica/jaspilite and iron
oxide bands, if the BIF is not metamorphosed above sub-greenschist facies.
Otherwise, silica bands are quartzites. Oxide facies are predominant with
hematite > magnetite, with the other facies rarely developed. They occur in a
remarkably narrow time-stratigraphic interval of 2.0–2.5 billion years in age in
virtually all of the earth’s Precambrian shields. They do not reappear significantly in
younger rocks. Examples of this BIF type (with synonyms, such as, taconite, jas-
pilite, itabirite) are numerous: Lake Superior and Labrador iron ranges of North
America, deposits of the Hamersley basin in Western Australia, of the Transvaal
Supergroup in South Africa, of Cerro Bolivar in Venezuela, of Quadrilátero
Ferífero of Minas Gerais in Brazil, of Krivoi Rog in Ukraine. Deposits of this BIF-
type are considered to have formed by deposition of iron and silica in colloidal size
particles by chemical and biological processes in the oxygenated waters of a
generally clastic-free shelf after upwelling currents brought reduced iron from
iron-rich clastics from the continental slope (Drever 1974).
The two-fold classification scheme mentioned above is not applicable in every
geological situation. For example, the BIFs with significant resource of iron in India
are 3.1 or 2.6–2.7 Ga old and therefore not of Paleoproterozoic age. They generally
do not have pillow lavas in close spatial relation as in case of the Algoma type, but
mafic volcanic units, especially hydrovolcanics occur in the host sequence. Their
mineralogy often is dominated by martite, secondary after magnetite. Thus, the
Indian BIFs in many places have the characteristics of both the Algoman and
Superior types of ores.
A third type of iron ores, the Rapitan type, has been described from the
McKenzie Mountains of NW Canada from Neoproterozoic glaciogenic sediments
(Klein and Buekes 1993). The host banded chert-hematite facies occurs in grabens
and along fault scarps. The tectonic environments for the deposition of different
iron formations mentioned above are illustrated in Fig. 2.65 (after Gross 1993).
The importance of iron being what it is today, the iron formations and the related
ores have been in serious investigation during the last 100 years or so. Yet many of
2.4 Sedimentary(-Diagenetic) Processes 115

Fig. 2.65 Tectonic environments for the deposition of different iron formations (after Gross 1993)

the questions regarding these iron formations remain controversial. The moot
questions concern:
(a) Ore petrography, including structure and textures.
(b) Sources of Fe and Si in the iron formations.
(c) Deposition of primary iron formation.
(d) Formation of ores.
Ore Petrography
BIFs and GIFs (Granular Iron Formations) are two petrogenetic varieties. BIFs were
precipitated as chemical muds and the GIFs formed well-sorted chemical sands.
The original mineral phases in the BIFs and GIFs are not yet incontrovertibly
established, although some have reported the nano-spheric primary granules (120–
200 nm) and microplaty hematite (Ahn and Busek 1990; Han 1988). Some inter-
preted magnetite to be early diagenetic (Johnson et al. 2008), while some others
(Ayres 1972) held that most magnetite and hematite postdate burial stylolitization
and even regional metamorphism (e.g., Morey 1999; Taylor et al. 2001). Both
magnetite and hematite can form during diagenesis, but much of it is linked with Fe
enrichment leading to Fe ore genesis (Bekker et al. 2010).
Much, but not all of banding and lamination in BIFs and GIFs is sedimentary.
The mineralogy is generally not original. Layering in banded Fe-ores, on close
inspection, is found not strictly parallel. Further, Fe-hydroxide particles, which
believably were the initial Fe-components in these rocks, are highly reactive to
dissolved silica in the system. This may be taken to imply that the silica component
in the BIF was scavenged from seawater and later released during diagenesis when
Fe(III)-hydroxides were transformed into stable Fe oxides. A part of the silica was
possibly bound in clay. A reasonable implication of this view is that chert was not a
direct chemical precipitate, as was generally believed until recently. Also laminated
116 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

magnetite, whether layer concordant or discordant, may not be typically

sedimentary.
Source of Fe and Si
Where did the Fe in the iron formations come from? An earlier view, persistent over
a considerable period of time, was that iron was of continental derivation (Cloud
1973; Holland 1973, 1984). Holland concluded that the annual contribution of
particulate iron to the oceans was of the order of 1015 gms. <1% of this Fe,
mobilized and precipitated in appropriate sedimentary environment is enough to
satisfy this need. But that will require a large volume of organic matter for the
mobilization of Fe (Isley 1995). Rather, the Eu/SmCN > 1 in iron formations relates
them best to volcanic hydrothermal systems (Bau and Moller 1993; Kato et al.
2002). Earlier to this, Jacobsen and Pimental-Klose (1988) obtained Fe/Nd ratio in
the Archean/Early Proterozoic BIFs in the order of 105, like what is obtained in the
modern hydrothermal systems. Some researchers are of the view that the deposition
of large iron formations correspond closely in time with major mantle plume events.
The Precambrian sea must have been saturated with volcanic silica [Si(OH)4] in the
absence of silica-mediating organisms. So there should not have been any difficulty
for the supply of silica for the initial iron formations.
Primary Iron Deposition
Here also opinion varies. The principal views comprise the following:
(a) Oxidation of Fe(II) by cynobacterial O2
(b) Metabolic Fe-oxidation
(c) UV photooxidation of Fe(II).
Cynobacterial Oxidation
This model invokes oxidation of dissolved Fe(II) with cyanobacteria-produced
photosynthetic oxygen. These prokaryotic microbes likely flourished in the photic
zones of near-coastal waters where Fe(II) and nutrients were rather easily available
by upwelling of deep water, carrying hydrothermal inputs, with or without conti-
nental contributions.

CO2 þ H2 O ð þ lightÞ ) CH2 O ðorganic moleculeÞ þ O2

Oxygen thus produced, was lethal to the biota that produced it until the latter did
not have the O2-mediating enzymes. In order to maintain the ecological balance, the
oxygen produced had to be immediately removed from the system. This was done
by oxidizing Fe(II) in solution. The process, Cloud (1973) suggested, was effective
during the Early Proterozoic (2500–1900 Ma) time.
Metabolic Iron Oxidation
Metabolic ferrous iron oxidation is another interesting mechanism of iron formation
deposition, a conclusion backed up by laboratory experiments with iron bacteria, as
2.4 Sedimentary(-Diagenetic) Processes 117

well as by modeling. This phototropic bacteria would have been capable of oxi-
dizing enough Fe (II) to fully account for all the primary ferric iron deposited as
BIF precursor sediment (Konhauser et al. 2002; Kappler et al. 2005).
U–V Photo-oxidation
This is an alternative to the biological models for Fe(II) oxidation, though suggested
earlier (Cairns-Smith 1978). It proposes that the ferrous iron could have been
photo-oxidized by the high flux of ultraviolet photons that would have reached
Earth’s surface prior to the rise of atmospheric oxygen and a protective ozone layer.
þ
2 Fe2ðaqÞ þ 2 H þ þ hv ) 2 Fe3ðaqÞ
þ
þ 2H2 O

The dissolved Fe(III) formed is substantially hydrolised as ferric oxy-hydroxide.

There are new suggestions too. Bekker et al (2010) emphasized the need for a
view in which enhanced hydrothermal processes in Deep Ocean determined the
ocean redox state independently of, or complementary to, atmospheric oxidation
state (Fig. 2.66).
Origin of BIF (+GIF)-Related Fe Ores
Iron ores containing  55% Fe, and associated with banded iron formations, par-
ticularly Lake Superior type, are commonly believed to have been secondarily
derived from the latter with the help of oxidizing aqueous solutions. There are
convincing field and laboratory evidence for it. There are however, a set of ques-
tions related to this. Did the process involve mainly the removal of silica or the
addition of Fe? Was the aqueous fluid descending (supergene) or ascending
(hypogene)? If ascending, was the aqueous fluid hot (hydrothermal) or cold? If
ascending, was the water juvenile or modified meteoric? When did it take place in
the history of the evolution of the iron formation? Researches to find the answers
are still on. However, the present-day status of answers is as follows: the alteration
process could be wholly supergene, wholly hypogene, hypogene with a supergene
over-printing (Fig. 2.67) and supergene with a hydrothermal overprinting (Beukes
2002; Sarkar and Gupta 2005). A more recent study by Rasmussen et al. (2007)
shows that hydrothermal iron ore formation from the BIF could be a long-lived,
multistage process, spanning more than one billion years.

2.4.3 Sedimentary Manganese Deposits

Manganese deposits of diverse genetic types occur in the terrestrial geologic record.
These deposits are of three lithologic associations: sedimentary rock-hosted, vol-
canic rock-hosted and karst-hosted, in order of predominance. Two genetic types of
sedimentary rock-hosted deposits can also be identified: those with Mn derived via
upwelling from oxygen-minimum zones and those formed on the margins of
118 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.66 Idealized models for the generation of Archean and Proterozoic iron formations (after
Bekker et al. 2010)

euxinic basins. Most of the large tonnage deposits appear to form by the euxinic
mechanism (Maynard 2010). The sedimentary rock-hosted manganese deposits
easily outclass the other types with regard to size, spatial, and temporal distribution
(Roy 1997). These ores occur in a variety of host rocks, mostly sedimentary, and
2.4 Sedimentary(-Diagenetic) Processes 119

Fig. 2.67 Formation of Fe-ores from Banded Iron Formation by hypogene and supergene
processes (after Sarkar and Gupta 2005)

rarely where volcanic rocks coexist. Some of these host rocks share a common
genetic link with these deposits which form through a sequence of stages involving
supply of the metal from a source or multiple sources, transport to a basin followed
by direct deposition or concentration aided by early diagenesis. The geologic setting
of most of these ancient manganese deposits indicates formation in shallow water
basin-margin regimes. Manganese may be brought into the basin by endogenic
hydrothermal solutions and by exogenic processes on the continent and coastal areas.
Eh-pH of inorganic aqueous systems exert major controls on the solution and
deposition of Mn as different species (Fig. 2.68). Further, presence of HCO3−, SO42−,
HPO42−, and organic matter may affect the behavior of Mn in exogenic conditions.
Experimental studies have also indicated a much greater solubility of Mn compared
to Fe at room T-P. Microbially mediated changes in the oxidation states of Mn
leading to its dissolution and precipitation is also a distinct possibility.
Manganese deposits that form in the sedimentary environment can also be cat-
egorized as under:
1. Shallow marine manganese deposits with/without remobilization in subareal
conditions
a. Clastic-hosted deposits, e.g., Nikopol, Ukraine (Early Oligocene); Molango,
Mexico (Late Jurassic); Groote Eylandt, Australia (Cretaceous), etc.
120 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.68 Eh-pH diagram

showing the stability of Mn
oxides and Mn carbonates in
natural waters. Dotted lines
demarcate the boundary of
natural waters. The dashed
and the bold lines represent
10−4 and 10−6 M Mn2+,
respectively, (after Roy 2006)

b. Carbonate-hosted deposits, e.g., Úrkút, Hungary (Early Jurassic); Taojiang,

China (Middle Ordovician); Imini-Tasdremt, Morocco (Cretaceous).
c. Banded iron formation (BIF)-hosted, e.g., *2.2 Ga giant Kalahari Mn field
and *2.4 Ga Rooinekke deposit in South Africa (Paleoproterozoic),
*0.74 Ga Otjosondu deposit in Namibia.
2. Manganese deposits in black shales, e.g., Ulukent and Dodu, Turkey; large
Early Proterozoic deposits in Francevillian succession in Gabon and in Birimian
succession in West Africa, and the Kisenge district of DRC.
3. Manganese nodules and crust in deep marine environment.
Manganese deposits of the first two categories appeared in the Late Archean
corresponding to development of oxygen oases in the otherwise reducing hydro-
sphere (Roy 1997). Examples in India are found in Chitradurga Group of western
Dharwar, in the Eastern Ghat sequence in Kodur and Garbham and in the Iron Ore
Group in Joda in Odisha. In the last occurrence, the Mn orebodies are constituted by
pyrolusite, manganite, cryptomelane, braunite, interbedded with shale, and surfi-
cially modified by weathering. For all these Archean deposits there is no direct
evidence of volcanic/hydrothermal input of manganese.
2.4 Sedimentary(-Diagenetic) Processes 121

Large-scale deposition of manganese started from Early Proterozoic due to

oxygenation of the atmosphere and development of stratified ocean, as explained
below. The Kalahari Mn field with a potential resource of 13,600 million metric
tons of ore (or 4200 Mt manganese metal), with Mn content between 20 and 48%,
is the largest, representing 77% of the world’s known land-based Mn resources.
Here Mn oxide and Mn carbonate ores are interbedded with BIF in a cratonic shelf,
constituting the 2.2 Ga old Hotazel Iron Formation in the Transvaal Supergroup
(Beukes 1983). The Paleoproterozoic Sausar Group (*2.0 Ga) of central India
hosts sedimentary manganese orebodies at Mansar, Chikla, Tirodi, etc. enclosed in
metamorphic equivalents of limestone–shale–orthoquartzite assemblage indicating
a shelf environment (Roy 1966, 1981). Presence of dolomite at the top (Bichua Fm)
indicates further shallowing of the basin. Interbanded Mn oxide orebodies (repre-
sented by braunite, bixbyite, hollandite, jacobsite, hausmannite) and Mn
silicate-oxide rocks (gondite) are hosted by metapelites and orthoquartzites (Mansar
Fm) and less commonly occur as conformable lenses in carbonate rocks of older
Lohangi Fm. The host sequence is complexly deformed and metamorphosed to
grades ranging from low greenschist to upper amphibolite facies (Roy 1997).
There is a conspicuous gap in sedimentary rock-hosted Mn deposits between
1800 and 800 Ma (the “Boring Billion” period in Earth history, Mukherjee and
Large 2015) that may correspond to a monotonous, low-oxygen ocean, but one
without sulfidic deep water. Alternatively, Mn may have been precipitated entirely
in the deep ocean, beneath a sulfidic oxygen minimum layer (Maynard 2010). Late
Proterozoic Mn deposits are known in Jacadigo Group in Urucum, Brazil, in
Damara sequence of Namibia, in the interglacial transgressive-regressive Datangpo
sequence in China where Mn carbonates are hosted by black shales. The best Indian
example is in the Penganga Group in the Godavari valley in Andhra Pradesh (Roy
1997). Sedimentary manganese deposits are more widespread, some examples of
which are mentioned above. Very large deposits of unmetamorphosed Mn oxide
and carbonate ores of Early Oligocene age occur at Chiatura (Georgia), and Nikopol
and Bol’shoi Tokmak (Ukraine) in shallow marine intracratonic setting overlying
the basement rocks of the Ukrainian shield. The Phanerozoic deposits are tempo-
rally coeval with stratified oceans, events of transgression and ocean anoxia (Force
and Cannon 1988).
The geological–geochemical conditions of sedimentary manganese deposition
through earth history demonstrates a primary redox control brought about by
interplay of a variety of processes, mainly tectonic, along with the resultant climatic
conditions prevailing in different periods (Roy 2006). Concentration of dissolved
Mn in O2-deficient seawater and/or sediment pore water through hydrothermal or
terrigenous supply in stratified oceans and transfer of the dissolved metal to toxic
continental shelves across the Mn2+/Mn4+ redoxcline during transgression was
responsible for deposition of Mn oxyhydroxide on shallow continental shelves
(Fig. 2.69). When this initially precipitated Mn complex in oxic environment of
stratified ocean got buried below the oxic-anoxic boundary of the water column, the
metal was redissolved and when Mn2+ reached an optimum concentration level it
reacted with organically derived bicarbonates in sediment pore water to produce
122 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

Fig. 2.69 Model representing sedimentary Mn deposition related to sea level changes (after Roy
2006)

Mn carbonates (Roy 2006). As noted in the earlier discussion, there is a strong

concentration of Mn deposits in the Paleoproterozoic and a lesser occurrence in the
Neoproterozoic, but, unlike Fe, there is an additional strong peak in the Oligocene.
Therefore, it can be deduced that Mn is not controlled entirely by the level of
2.4 Sedimentary(-Diagenetic) Processes 123

oxygen in the earth’s atmosphere. At each peak of Mn deposition, the associated

ore deposits are concentrated in a few districts, suggesting a more local than global
control on manganese metallogenesis (Maynard 2010).
Two major mineral deposit types occur commonly on present-day sea floor and
ocean beds. These are the manganese nodules and crust, and metalliferous sedi-
ments, crusts, and mounds. They have been explored and studied extensively since
they were discovered by the expedition of HMS Challenger between 1873 and
1876. Several useful reviews are available on the subject. The following summary
is based on the publications of Cronan (1980); Roonwal (1986); Gross and Mcleod
(1987). The manganese nodules and crust are widely distributed in deep ocean
basins within 30o of the equator in the Pacific and Indian oceans, and in the south
and southeastern Pacific, mainly at depths greater than 2000 m, below the carbonate
compensation depth, where there is minimal detrital sedimentation and high bio-
logical productivity. Manganese nodules are commonly spheroidal to ellipsoidal,
botroidal, discoidal, tabular, or faceted in shape, commonly 2–5 cm in their greatest
dimension, and range from micronodules <1 mm in size to ones 1 m in diameter
weighing a ton. Their growth rates average about 5 mm in a million years.
Todorokite, birnessite, psilomelane, and hollandite are the most common of the
large number of complex hydrous manganese oxide mineral phases present in the
nodules. Iron in the nodule occurs as goethite, lepidocrocite, hematite, maghemite,
and amorphous hydrated ferric iron oxide gel. The manganese nodules contain 1.7–
3.5% combined Cu and Ni in minimum abundance of 10 kg/m2 and with high Mn:
Fe ratio. Estimates of potential resources of nodules in the world’s oceans based on
this minimum abundance and grade range from 14 to 99 billion tons.
Ferromanganese crusts containing 0.3–1% Co and occasionally platinum and
deficient in Cu and Ni (in contrast to the nodules) are common at depths of 800–
2500 m on seamounts older than 25 Ma in the Central Pacific. They also spread
over thousands of square km on plateaus, rise and the eastern flank of the
Mid-Atlantic ridge. Mineral occurrences in the Indian Ocean consist mainly of
metalliferous sediments and sulfidic stockwork. These crusts were hydrogenetically
deposited in areas of Oxygen Minimum Zone (OMZ) either from dissolved metals
and/or oxide flocs suspended in the water column (Roy 1999).
The origin of the ferromanganese nodules involves the source of the metals and
the mode of accretion of the oxyhydroxide phases. The source of metals in the
nodules is attributed to a variety of processes and their combinations. These include
discharge of hydrothermal fluids along active tectonic regimes, related to deep sea
volcanism, or terrestrial weathering and transport by rivers into the sea. Secondary
processes can also play significant role, e.g., leaching of metals from bottom sed-
iments and volcanic rocks during diagenesis and lithification followed by transport
and deposition by interstitial waters or by seawater and deposition at favorable sites.
Two major mechanisms of nodule formation include precipitation, from enriched
seawater around solid nuclei, of dMnO2 with roughly equal Mn and Fe and
124 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

relatively high content of Ce, Co, Pb, and Ti. The other mechanism is of diagenetic
precipitation of todorokite with Mn > Fe and high content of Cu, Ni, Mo, and Zn.
The role of microorganisms in the precipitation of Mn and Fe on the sea floor has
also been emphasized by some workers.

2.5 Lateritic and Non-lateritic Residual Processes

Chemical weathering aided by water action and percolation leaves behind a host of
economically important mineral resources as residual deposits near the surface.
These include deposits of aluminum, iron, nickel, gold, and manganese. Chemical
weathering proceeds in three distinct stages (Robb 2005): Dissolution, oxidation,
and hydrolysis of the weathered rock material and removal of the soluble ions from
the rock mass by percolating water; formation of new secondary minerals such as,
clays, oxides, hydroxide, and carbonates; further breakdown of these secondary
minerals and accumulation of hydroxides of iron and alumina in particular in the
weathered zone.

2.5.1 Bauxites

Most common among the residual products is bauxite, a porous to pisolitic rock
which could also be massive, nodular or earthy, comprising varying amounts of
gibbsite, boehmite, diaspore, and kaolinite with subordinate amounts of silica, Fe
oxides, and hydroxides and Ti oxides. Some bauxite ores are the source of gallium.
Deposits typically occur on plateaus in tectonically stable areas. A large amount of
scientific literature is available on this main economic resource for the Al metal,
among which a mention may be made of Valeton (1972), Goudie (1973), Norton
(1973), Maynard (1983) and Bardossy and Aleva (1990). Two major types of
bauxites are distinguished in industry as well as in scientific literature. These are:
1. Lateritic bauxite
2. Karst bauxite.
Lateritic bauxite develops on or near the surficial parts of Al-silicate-rich rocks,
such as granites, granite gneisses, basalts, arkoses, alkaline rocks, etc. as 85% of
world’s bauxite reserves belong to this type. The bauxite deposits on
alumino-silicate rocks are commonly of the blanket type (Fig. 2.70) while the karst
bauxites in impure carbonate rocks are irregular or sack formed. The most
important stage in bauxite formation is Al-silicate breakdown in a weathering
profile (Fig. 2.69):
2.5 Lateritic and Non-lateritic Residual Processes 125

Fig. 2.70 A simplified section of a weathering profile on Alumino-silicate rocks, showing the
formation of bauxite (after Craig et al. 2001)

þ þ
2KAlSi3 O8 þ 2Haq þ 7 H2 O ) Al2 Si2 O5 ðOHÞ4 þ 2 Kaq þ 4H4 SiO4aq
ðK-FeldsparÞ ðKaoliniteÞ
Al2 Si2 O5 ðOHÞ4 þ 5 H2 O ) Al2 O3 :3H2 O þ 2H4 SiO4aq
ðKaoliniteÞ ðGibbsiteÞ

Plagioclase feldspar and even muscovite mica may be involved in such a

reaction if present in the protolith of the original rock (vide Sarkar and Gupta 2012).
In karstic bauxite formation carbonate minerals dissolve out and the residue,
dominated by clay minerals alter to bauxite mineral.
Bauxite accumulation can also be transported or detrital. Most deposits are
Cenozoic in age. Largest resources are found in Australia, Brazil, Guinea, and
India.
Several variables control the origin and quality of the residual product. These
include: (1) climate (tropical with a mean temperature of 23–26 °C and annual
rainfall of 1200–4000 mm); (2) topography (ancient planation surface dissected by
valleys); (3) groundwater movement above the groundwater table; (4) relative rates
of chemical and mechanical erosion; (5) type and amount of vegetation (tropical to
savannah forest cover); (6) character of the bed rock; (7) lastly but most impor-
tantly, groundwater quality with respect to Eh, pH, and organic solutes.
Ni-rich in situ lateritic products are often found to develop on dunites and
peridotites which have been uplifted and exposed to chemical weathering in warm,
humid climates but protected by low rates of physical erosion. They are often
associated with podiform chromite or serpentine-hosted asbestos deposits. The
source rocks could be Precambrian to Tertiary in age, but the deposits form com-
monly by Cenozoic weathering. The weathered sequence from the top comprises:
red, yellow, and brown limonitic and pisolitic soil; saprolites – continuous transi-
tion from soft saprolite below limonite zone, hard saprolite, and saprolitized peri-
dotite to fresh peridotite. Boxwork of chalcedony and garnierite occurs near bed
rock – weathered rock contact. Within such laterites, Ni-rich iron oxides are most
common. Some deposits have a predominance of Ni silicates, such as, garnierite
over quartz and goethite. The oxide and silicate ores are end members and most
126 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

mineralization contains some of both. The upper limonite zone contains 0.5–2% Ni
in iron oxides; lower saprolite and boxwork zone typically contains 2–4% Ni in
hydrous silicates (Singer 1986). Well-known deposits of this kind are known in
New Caledonia, Australia, USA (Oregon).
Humid tropical climate with abundant rainfall and vegetation, in concert with
suitable topography, e.g., plateaus, drainage system, and parent rock composition
can produce a manganese deposit with commercial yield within the zone of
weathering. The chemical weathering process is dependent on the role of humic and
fluvic organic acids formed by the decay of vegetation in releasing the manganese
from the source rocks (Nicholson, 1992). In a Al–Fe–Mn triad, the solubility of Mn
is maximum, as is its mobility. Thus during downward movement of Fe and Mn in
supergene solutions, a change in Eh-pH may lead to precipitation of Fe in prefer-
ence to Mn thereby bringing about a separation between the two elements. Where
the weathered profile is of sufficient thickness, the upper zone is depleted in Mn
which travels deeper and is reprecipitated in the lower zone (Roy 1981).

2.5.2 Lateritic Gold

Secondary gold enrichment in laterites is common in sulfidic deposits, though

development of a fresh deposit of this type is not very common. Some important
amongst them comprise Boddington-Hedges, (16.8 t/2.1 gm t−1), and Gibson
(8.5 t/1.6 gm t−1) in Western Australia, Omai, Guiana (17 t/1.44 gm t−1) and at a
number of places in South America. Such deposit type prospects are also known in
Nilambur region of northern Kerala (vide Sect. 3.5.5). These deposits occur in
lateritic profile developed over greenstone-type mineralizations. Although gold in
this situation could be largely secondary, primary gold may locally be present in
considerable proportions. The secondary gold is generally of greater fineness
(990) and may have forms varying from euhedral crystals through dendrites to
irregular particles. The complexes that are believed to be capable of dissolving gold
in such a situation and relocate it are chloride and thiosulfate ions, humic acid and
may also be cyanide ions (Butt 1989).
Dissolution of gold from veins and lodes in near-surface environment are
envisaged to take place by such reactions (Mann 1984):

4 Auo þ 16 Cl þ 3 O2 þ 12 H þ ! 4 AuCl

4 þ 6H2 O
AuCl
4 þ 3 Fe
þ2
þ 6 H2 O ! Auo þ 3 FeOOH þ 4 Cl þ 9 H þ

Auo precipitation from a solution in which gold exists as AuCl4−complex may

take place as a result of (1) lowering of Cl− ion concentration; (2) by raising the pH,
or (3) reduction of AuCl4− ion by ferrous ion, as shown above. The last suggestion
appears to be more realistic in view of the common association of gold with ferric
hydroxide.
2.5 Lateritic and Non-lateritic Residual Processes 127

Mention of other enrichments, sometimes even reaching ore grades, are relevant
in this context. These include gold contained in various surficial deposits and their
cements, such as red brown hard pans, pedogenic calcrete, and secondary alumi-
nosilicates. In some cases, gold is present in recently precipitated carbonates as well
as in early formed pisolites (Butt 1989). Someone seeking explanations of gold
nuggets, which have fascinated so many people for so long, may get an idea of the
mechanism from the discussion made above. The accompanying diagram
(Fig. 2.71) illustrates the enrichment and depletion of gold at Boddington-Hedges,
Western Australia (Butt 1989).

Fig. 2.71 Formation of supergene gold in deeply weathered lateritic profile in Western Australia
(after Butt 1989)
128 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

2.5.3 Supergene Oxidation and Enrichment

(including “Exotic Ores”)

When a sulfidic ore body is brought close to the earth’s surface through erosion, it
will also get easily affected by the agents of chemical weathering. The sulfur is
expected to get oxidized to sulfate ion, SO=4 . The oxidation may go through the
intermediate stages of SO2 and free sulfur, but these products are rarely detected in
the oxidized zone. The metals may be converted into insoluble compounds stable
under surface conditions (e.g. oxides, carbonates, sulfates, silicates) or may be
taken into solution. The dissolved metal will be slowly removed by the ground-
water. Part of it may get deposited above the regional water table to form oxidized
ores but the major part will get carried to the unoxidized portion of the sulfide
deposit, where it will be precipitated by reaction with the primary sulfide minerals
to form the supergene enriched sulfide ore (Fig. 2.72).
The weathering of sulfides, a complex natural process, thus results in: (a) metal
ions getting into solution or into the form of an insoluble compound stable under
surface condition; (b) conversion of the sulfur into sulfate ion and (c) production of
relatively acid solution. We are particularly referring to the Cu-sulfide ores, as they
are most susceptible to the above phenomena within the sulfide kingdom. This is
because Cu has very low solubility of its sulfides and relatively high solubility of
compounds it forms with the common anions in the oxidized zone. The stability of
these phases is not only affected by higher redox potential (Eh), but also by lower
pH or higher acidity. Some common reactions for acid production in geochemical
environments are as follows:

Fig. 2.72 A sketch of a

near-surface section showing
the formation of gossan,
leached zone, oxidized ores,
and supergene enriched ore,
with special reference to a
primary lean vein ore of
copper. The dashed vertical
line gives the Cu-content of
the protore
2.5 Lateritic and Non-lateritic Residual Processes 129

4CuFeS2 þ 17 O2 þ 10 H2 O ! 4 FeðOHÞ3 þ Cu2 þ þ 8 SO2

4 þ8 H
þ

ðChalcopyriteÞ ðGoethiteÞ
2FeS2 þ 15=2 O2 þ 4H2 O ! Fe2 O3 þ 4SO¼4 þ8 H
þ

ðPyriteÞ ðHematiteÞ

The reactions mean that the oxidation of chalcopyrite liberates Cu2+ into the
aquous medium and leaves behind Fe oxide/hydroxide (regolith). Dissolution of
pyrite often leaves behind polyhedral vacuoles, produced by the removal of Fe
oxide/hydroxide. The material now obtained is a pock-marked goethitic/limonitic
mass with some clay in most cases. It is called gossan.
Cu2+ leached from the top zone, i.e., gossan zone, percolates downward toward
the groundwater surface, unless arrested by some specific reactions. Reactants
available, the percolating fluids produce a complex mineralogy of Cu-carbonates,
-silicates, -phosphates, -sulfates, -arsenates, as well as Cu oxide/hydroxide. A few
partially altered grains of pyrite and chalcopyrite may still be there. The zone
between the gossan and groundwater surface is called the zone of oxidation.
Below the groundwater table (surface) the environment is supposed to be
reducing. The reactions there are like:

CuFeS2 þ 3 Cu2 þ ! 2 Cu2 S þ Fe2 þ

ðchalcopyriteÞ ðchalcociteÞ
CuFeS2 þ Cu2 þ ! 2 CuS þ Fe2 þ
ðchalcopyriteÞ ðcovelliteÞ
14Cu þ þ þ 5FeS2 þ 12H2 O ! 7Cu2 S þ 5Fe þ þ þ 3SO¼
4 þ 24H
þ

Whether chalcocite or covellite will get preferentially deposited would depend

on the Eh and pH at any particular location. Fe, Zn, and other metals displaced by
Cu are carried away in solution and deposited later as limonite or smithsonite, etc. if
the solution reaches an oxidizing or less acid environment. As the neo-formed
phases, i.e., chalcocite and covellite are richer in Cu than chalcopyrite, which earlier
dominated the ores below the groundwater surface, the metal-content, particularly
of Cu increased and it is therefore called the zone of secondary or supergene
enrichment. This zone gradually merges with the original ore or the protore
(Fig. 2.72).
Silver also has necessary properties to show supergene enrichment whereas Pb,
Zn, Ni, Co and Hg do not undergo such enrichment. Ag may be stuck in the
oxidized zone as a chloride or may be reduced to the native metal if Eh remains
low. However, solutions in the oxidized zone generally have low enough chloride
ion and high enough Eh to permit considerable downward migration of Ag+ to
levels where very insoluble sulfide can precipitate. The simple sulfide argentite
(Ag2S) and the more complex sulfo-salt, proustite (Ag3AsS3) and pyrargyrite
130 2 How Do Mineral Deposits Form and Transform? A Systematic Approach

(Ag3SbS3), are the common secondary minerals of silver in the zone of supergene
enrichment.
Leaching, supergene enrichment and “exotic” deposit developments are inter-
related, but not that if one of these phenomena developed well in one deposit, the
other two will develop equally well there, or that all three will develop at all
together. The “exotic deposits” of copper are rather less well known, although the
mining of oxidic ore at Chuquicamata in northern Chile by the Incas and Spanish
explorers took place hundreds of years ago. With breaks it was continuing until the
middle of the last century when, however, the exotic deposit (now South Mine) was
discovered beneath oxide tailing dumps, followed by systematic exploration and
development. As Mote et al. (2001) defined, “generally exotic mineralization”
occurs in paleo-drainage networks, leading away from principal porphyry deposits
that have undergone supergene enrichment. Acidic, oxidizing copper-bearing fluids
escaped the supergene enrichment system into the headwaters of the surrounding
drainage network and flowed downhill to sites, where the precipitation of copper
ore bodies occurred. More than 12 exotic copper deposits were reported from
northern Chile. But what is not clear as yet is what caused the lateral escape of
copper from the supergene system. Further, paleo-channel that may contain such a
mineralization may be gravel covered and elude successful exploration.
Metals present, other than Cu in the exotic ores, are Mn, K, and Co. These are
apparently contributed by the leached capping. When Mn is present in substantial
proportions, the ore is referred to as copper-wad.

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