Mineral Resources: Geology, Exploration, Economics and Environment

Prof. M. K. Panigrahi
Department of Geology and Geophysics, Indian Institute of Technology, Kharagpur

Module -4

Hydrothermal Processes and Deposits

Hydrothermal processes are the most widespread and ubiquitous in formation of ore
deposits in the crust and nearly eighty percent of ore bodies belong to the broad class of
‘hydrothermal deposits. While attempting to understand hydrothermal processes, it
should be kept in mind that the process is not independent by itself, rather operates in
association of various earth processes as discussed in the beginning.

It would be worth recalling the classification scheme of ore deposits that was proposed
before.

Fig.1 Classification scheme of ore deposits. Note the ones in blue letters.

In Fig.1 some of the deposits are written in blue letters. The intention here is to point out
the commonality between them in the sense that all of them are ‘hydrothermal’ in some
form or the other.
Fig.2 A different scheme of classification of mineral deposits (‘syngenetic’ and
‘epigenetic’). Note the ones in red again have the same commonality as in Fig.1

Similarly, in another classification scheme, categorizing the deposits to ‘syngenetic’ and

‘epigenetic’, similar idea has been depicted. Here also, all that is marked in red - the
volcanogenic massive sulphide deposit, the sediment hosted massive sulphide deposits,
the epidermal deposits in volcanic islands, the Mississippi valley type deposit,
metamorphogenic gold silver deposit and so on, all these in red have a commonality that
they owe their origin to activities of a hot aqueous fluid which we call as the
‘hydrothermal’ fluid.

The term ‘hydrothermal’ is a combination of two terms ‘hydro’ meaning water and
‘thermo’ meaning heat, in other words, it indicates a ‘hot aqueous fluid’. The fluid needs
to be sourced from somewhere and there must be a heat source – as we shall see, both
could be diverse.
Conventionally, we exclude fluid on the earth’s surface. You have already seen deposits
resulting from fluids operating on the surface giving rise to deposits driven by exogenic
processes. Here we consider fluids operating below the surface, in terms of a few
hundreds of meters to a few kilometres.

Now, why we think that these deposits as we mentioned in the previous 2 diagrams, do
owe their origin to a fluid. Consider a very common situation of occurrence a body of
common crustal rock in which we observe that there is an ore body of any particular
metal - let us say copper or gold or lead or zinc or whatever it could be. Suppose it is an
ore body containing a sulphide mineral (say galena) and suppose quartz is the gangue
mineral occurring along with galena. The two possibilities before us are as per our
knowledge of formation of minerals in nature – either solidification from a melt of
equivalent composition (galena + quartz) or precipitation from an aqueous solution
containing Pb, S, and SiO2 in whatever soluble form and the chemistry of the system.

In the olden days, when the science of ore geology or mineral deposit formation was at
its infancy, there were many views, that were proposed by many philosophers /
scientists. One view was that all deposits like this one, result from the activity of a
magma, a molten material that intruded into the common crustal rock. This is primarily
due to the fact that eruptions of volcanoes, flow of lava (from deeper sources) and
formation of rocks on solidification were spectacular features on the surface of the Earth,
that fascinated scientists and they ascribed this phenomenon to whatever unusual feature
was observed in rocks. It was actually a view, which was more popularly known as the
Plutonist view. The other opposing view which was proposed, was that it was more
commonly known as the ‘theory of lateral secretion’ means it is all the activity of water,
which scavenges the metals from the surrounding rocks, and deposits them on a suitable
location. This was popular as the ‘Neptunist’ view or the concept of lateral secretion
Now let us try to find the logic as to which of the two views fits and why.

If we have to bring quartz + galena into a molten state, the temperature has to be very
high, greater than 1000 °C at least. Now if such a material is emplaced within the
common crustal rocks what would you expect? We would expect that this melt will
cause some contact effect or we call them as a ‘baking’ effect and we would be getting
some high temperature mineral transformations around this body containing quartz +
galena. In case we do not find such high temperature signature, we have to rule out the
‘Plutonist’ hypothesis. In most of the cases all the deposits that we put them under the
category of hydrothermal, and whenever they occur in such kind of forms as veins or as
spaces occupying open spaces that are created in common rocks; we actually do observe
that instead of having such kind of a high temperature contact effect; what exactly we see
that, the rock in the immediate contact is ‘hydrolysed’ or show presence of alteration
caused by hot aqueous fluid and when we move away from the vein, we get the fresh
unaltered rock. This feature of presence of altered minerals in the immediate contact of
the ore body is called ‘hydrothermal alteration’. This hydrothermal alteration may be
occurring in zones - they are symmetrically arranged around the ore body. They may be
just about one or even multiple such zones, typically they are characterized by presence
of some hydrothermal alteration minerals, which we will discuss in details in the later
sections, where we will be looking into the process. So, this gives us first-hand
information that this particular process of mineralization or emplacement of this
particular ore body is not in the form of a molten material or a magma rather it came in
the form of fluid, and that is how it has hydrolyzed or has affected the rock immediate
surrounding rock, which we call as a country rock by hydrolyzing them or altering them
or causing some alteration are characterized by hydrothermal alteration minerals. So, this
kind of hydrothermal alterations could be hydrolysis, carbonation, silicification (addition
of silica) and any other kind of situations. The second most direct evidence come from
what I showed in the distributional peculiarities of mineral resources, by looking at the
ocean floor hydrothermal systems and equivalent land based geothermal systems, where
we see that a hot aqueous fluid is in action in giving rise to mineralization. This gives us
the most direct evidence in favour of a hydrothermal origin of any of these mineral
deposits. And the other one is that when we examine such minerals from these deposits,
we see tiny fluid filled cavities is called fluid inclusions or they are supposed to be the
remnant of the fluid from which the mineral deposit was formed.

So, we have defined temperature range of 50 to 500 °C for this ore fluid ( we call
them as ore fluid or hydrothermal fluid, synonymously you can use any of these two
terms). Such metal-bearing hydrothermal fluids can have diverse sources such as (i)
juvenile water, (ii) magmatic water, (iii) metamorphic water, (iv) connate / basinal water,
(v) seawater and (vi) meteoric water. We shall discuss the characteristics of these types
of water.
(i) Juvenile Water: As the name suggests, this type of water had never been a part of the
normal hydrological cycle, rather is sourced directly from the mantle in the process of
degassing. It certainly is the most insignificant of water-type identified in any
hydrothermal ore deposit.

(ii) Magmatic water – Felsic magma (granitic) inherently contain a few weight percent of
dissolved volatile (dominantly water) which gets exsolved at the late-stage of
crystallizataion. This water can have appreciable concentrations of metals and can form
hydrothermal deposits of specific types (to be discussed later).

(iii) Metamorphic water – Metamorphism of sediments generates copious amounts of

fluids (again dominantly water) at different grades of metamorphism, through the
process of metamorphic devolatilization (from greenschist to granulite grades). This fluid
also is capable of transporting metals and can form mineral deposits in some cases.

(iv) Connate / basinal water – In depositional basins, sediments get deposited and the
water that transports them remain locked in intergranular spaces depending on the
porosity. Such water (surface water), if resident for a long time, interacts with the matrix
minerals of sediments and gets modified in its chemistry and get expelled from the
sedimentary strata as a result of tectonic processes. Such basinal / connate water also can
dissolve metals and transport them to different locales and form mineral deposits.

(v) Seawater – As we all know, all surface water (rivers) is discharged finally to the
ocean and the world oceans have been evolving through geologic time and attain a
chemistry (in the process of continuous evaporation and interactions with rocks in the
ocean floor, often at higher temperatures) that is different from surface water. Seawater
is thus actively involved in ore forming processes, specifically operating in the ocean
floor.

(vi) Meteoric water – It is simply the rain water precipitating from clouds that fall on the
earth’s surface and drained in the form of rivers and also exists in form of lakes and
ponds. However, a substantial proportion of this water also percolates to deeper parts in
the crust, through pores and fractures in the rocks and also changes in its chemistry in
course of water-rock interaction. Such waters, in many cases give rise to mineral deposits
of variable sizes and types (recall our discussion on the ‘lateral secretion’ hypothesis).
 Fig. 3. Schematic diagram depicting different water-types and their sources.

Fig. 3 is a cartoon showing different water-types and their possible sources. In case of
magmatic and metamorphic fluids, volatiles like carbon dioxide and sulphur bearing
species are also present which influence the metal-carrying capacity of these fluids. Sea
water also has a lot of dissolved ions and sulfate that play crucial roles in their ore-
forming processes.

One important thing to bear in mind at this stage is that all the fluid types mentioned
have their specific temperature – composition characteristics that help in their
identification in any hydrothermal deposit. For example, juvenile, magmatic and
metamorphic waters are likely to have higher temperatures than basinal and meteoric
fluids. These fluids have significant differences in their stable isotopic (H, O, S, C)
signatures which we shall discuss briefly.

Fig. 4: A more elaborate idea on sources of fluids and resultant mineral deposits.
Fig. 4 is a diagram which gives a better overview of the fluid types in terms of sources
and depths and resulting deposit types. It depicts the domain of the low-temperature
meteoric fluid, the sedimentary basinal fluid. As we go deeper down. so, they will be
magmatic or the metamorphic fluid; we see some of the deposits like porphyry copper
deposit here, tin-tungsten Skarn deposits and as we go to the more surficial region, we
see the volcanogenic massive sulfide which is dominantly by the sea water, then the
stratiform copper and the Mississippi Valley type deposit coming from connate water.
The epithermal deposit like the ones which is associated with volcanic islands like one in
the Japanese island have substantial meteoric fluid involvement. The most significant
thing revealed from this figure is the fact that rarely any mineral deposit form from a
single source of fluid – rather various combinations are possible. We shall see in details
in course of our dissection of many important deposit types. Sometimes the magmatic
fluid could be could mixed with a meteoric field, a basinal fluid could mix with the
meteoric fluid, a metamorphic fluid could mix with a meteoric fluid or a basinal fluid,
and we try to retrieve the signatures of such conditions or chemistry as well as the
thermal regime of the fluid through our systematic investigation of the ore minerals and

Fig. 5 Oxygen – hydrogen isotopic fingerprints of fluids of diverse sources.

the associated silicate and carbonate minerals associated with the with the ore.

Now, since we are talking about the fluid sources, coming from the meteoric or
magmatic or metamorphic or connate and so on. The question that we posed that do we
have any identity for such fluid types? The answer is yes. We do have if we are able to
sample the remnant of the particular fluid which brought about the mineralization, and
we analyze the oxygen isotope ratio, then we would possibly be able to identify the what
kind of fluid actually gave rise to a hydrothermal deposit.

Fig. 5 is a diagram depicting the variations of different fluid types on a δD versus δ18O
space. As shown, meteoric water (sampled from all over) follows a distinct linear trend
that can be fitted with an equation (Y=mX + C). Metamorphic water occupies a large
rectangular area since the T-P conditions of metamorphism are quite varied, yet, far
away from the meteoric line indicating that the metamorphic fluid gets enriched with the
heavier isotopes as a result of fluid-rock interaction at higher temperatures. The
magmatic fluid is delineated with a narrower area and has a significant overlap with
metamorphic water (since melting is the ultimate outcome of high-T metamorphism).
Connate waters characteristically are distributed in patchy areas close to the meteoric
water line but oblique to both the axes in the plot. Examples are shown from the Alberta
basin, Michigan basin and the gulf coast - these are the areas where you get
mineralization of base metals lime Pb and Zn. This is primarily due to the fact that the
water locked in sediment pore spaces exchanges both H and O isotopes. Geothermal
waters in young volcanic islands as well as in many continental interior situations plot on
lines parallel to the X-axis, joining the meteoric water line and the field of magmatic
water, indicating interplay of these two water types in geothermal systems. The plots of
points parallel to the X-axis indicates that there is exchange of the O-isotope only since
the rocks with which the fluid interacts is essentially anhydrous. In any hydrothermal
mineral deposit, if we can directly sample the paleo ore fluid and analyse it for the
oxygen and hydrogen isotopes, we can identify the fluid source, of course, with other
supportive evidence.

As stated earlier, the identity of these fluid types lies in their thermal regime
(low, moderate or high temperatures), gross chemistry (in terms of total dissolved
electrolytes and non-electrolytes) and the isotopic ratios of oxygen and hydrogen. We
just saw the fields of different water-types on a δD versus δ18O plot. As we shall discuss
later, temperature of the paleofluid can be approximated through the study of fluid
inclusions in minerals which itself is a vast topic and will only be touched upon.
However, on favourable situations, oxygen isotope ratios of coexisting minerals and
mineral-fluid can be used to estimate temperature of the fluid (see box). We consider
only the 16 and 18 oxygen for this purpose since 17O is too negligible in abundance. The
oxygen isotopic ratios in minerals and fluid can be measured in specialized instruments
called Isotope Ratio Mass Spectrometers (IRMS).

This oxygen isotope thermometry can be considered in the context of a mineral versus
mineral, or it can be considered in case of a mineral and fluid say for example, mineral
water, it could be a quartz and a mineral like say magnetite, and it could be a situation
like a mineral quartz and water because we know that these two can always exchange the
18
isotopes. The heavy isotope O, fractionates between the different reservoirs like we
know that when water evaporates from the surface of the ocean, the water vapour
18
becomes depleted in its O concentration. Similarly, when different reservoirs or
different minerals and fluid react in those kinds of scales, they do fractionate the heavy
18
isotope the O, which can be very well utilized to determine the temperature. (see box
for schematic reactions).

The equation below is a simple expression for enrichment of water with respect to the
heavier isotope (18O) and is calculated with respect to a standard as shown. There are
many standards for water (such as VSMOW – Vienna Standard Mean Ocean Water). A
positive value indicates enrichment and negative value indicates depletion with respect to
the heavy isotope.

This is based on the fact that fractionation of isotopes of light elements is a function of
temperature. This temperature dependence is applicable to mineral-mineral and mineral-
fluid pairs. For example, we can write these reactions for the equilibrium fractionation of
isotopes of oxygen:
Si16O18O + H216O = Si16O16O + H218O (one oxygen site is involved in the ractionation
with quartz)

Si16O18O + Fe316O4 = Si16O16O + Fe316O318O4 (fractionation between quartz andmagnetite)

The fractionation in these cases is represented by a parameter α

The parameter α is related to the equilibrium constant of these reactions by a relation

One needs to determine the ΔA-B i.e. the difference in the δ value of the two minerals or
the mineral and fluid in equilibrium and have to have a relationship between temperature
and 100 ln α. This relationship is determined from experiments and empirical fits. For
example the relationship for magnetite and quartz is

And is applicable in the range of 250 to 500 deg C. There are calibrations available in the
literature for many such pairs of minerals and mineral-water pairs.

To recapitulate, we have started to discuss about the hydrothermal processes and

the resultant deposits, which are broadly known as the hydrothermal deposits. These
deposits occur in wide diverse spectrum of geological environments, and of almost all
metals that we have discussed so far, barring a few exceptions and as far as these
hydrothermal deposits are concerned. When we try to study these deposits and the
hydrothermal processes, we ask ourselves some fundamental questions as to where from
the fluid came or what was the source of the fluid and also the source of the metal and
other essential constituents which are responsible in giving rise to such mineralization.
Let us have a look at the spectrum of hydrothermal mineral deposits – (i) the magmatic
hydrothermal systems (porphyry copper / molybdenum / tin as well as skarn (contact
metasomatic process that evolve in a more complex way giving rise complex
morphology and mineralogy) deposits mainly of Sn, W, Mo and often Fe and Au), (ii)
the pegmatite environment (a residual magmatic fluid dominated system with specific
parent felsic magma composition) which is more important as hosts of precious stones
and mica, often is a rich source of Sn, Nb, Ta, (iii) seafloor hydrothermal systems at both
divergent and convergent margins (VMS deposits of Cu-Pb-Zn), (iv) the volcano-
associated near-surface hydrothermal systems in the circumpacific ring of fire (mainly
copper and Au-Ag, (v) the metamorphogenic hydrothermal systems in ancient
greenstone sequences as a result of convergent tectonism (mainly gold), (vi) sediment-
hosted gold deposits in accretionary prisms with complex tectonic and magmatic
activities known as Carlin-type in western US and other parts of the world, (vii) the syn-
sedimentary exhalative hydrothermal systems in fault-controlled basins within continents
and continent margins (SMS deposits of Pb-Zn), (viii) copper (+ cobalt) mineralization
in continental scale sedimentary basins (mainly diagenetically controlled) in clastic
sediments (SSC), (ix) platformal carbonate sediments hosting Pb-Zn deposits in diverse
locales resulting from flow of basinal fluids (MVT), (x) near-surface low-temperature
fluid dominated uranium mineralization controlled by unconformities separating
basement rocks and overlying sediments and finally (xi) the near-surface groundwater
dominated uranium mineralization controlled by change of environment from oxidizing
to reducing (Roll-front). This sequence is arranged more or less with decreasing
temperature of the fluid. In addition, there are some very interesting and as yet less
understood hydrothermal systems such as the IOCG (Iron oxide copper gold) originally
proposed after the discovery of the Olympic Dam deposit in south Australia with rich
uranium mineralization. Although the Olympic Dam deposit is hosted in a Proterozoic
granitoid in cratonic interior that is apparently anorogenic (not associated with any
tectonic activity), many other deposits with variable degrees of similarity in host rocks,
tectonic evolution, constitution of ores and fluid characteristics are being described as
IOCG-type. The Bayan-Obo REE deposit associated with carbonatite occurs in inner
Mongolia and is a very special type of magmatic-hydrothermal system with complex
fluid characteristics. Besides these, there are a good number of ‘epithermal’ deposits of
base and precious metals occur in many geologic provinces of the world and are
essentially meteoric water dominated system with additional heat (+ fluid) input from
proximal magmatic bodies. They are very much controlled by existing structural
elements in rocks in shallow crust that underwent brittle deformation (mainly different
types of fracture network).
While examining the volcanic system, we may not make a distinction between the
compositional varieties; like mafic intermediate or felsic. We classify them as the
volcanogenic massive sulphide deposit or the VMS. There is a spectrum of deposits with
copper dominant to copper - zinc and lead-zinc-copper mineralizations. They occur in
the divergent plate boundaries like the present day analogs what we have seen in the
form of the sulfide chimneys and black smokers, with or without sediments as well as in
convergent plate boundaries (like the Japanese arc) associated with bimodal or felsic
volcanic rocks. These volcanogenic sulfide deposits could be broadly clustered under the
submarine category. The metal deposits which are associated with young volcanic
islands (in the Circumpacific ring of fire) are the volcano associated epithermal deposits.
They are rich sources of copper, silver and gold and are results of interaction of meteoric
fluid with residual magmatic fluid in variable proportions. So, these are the deposits that
we are going to discuss in brief in due course. We will be trying to address the processes
in terms of the source of fluid, source of metal, the dominant mechanism of the transport
deposition processes operated by the fluid in different crustal domains.

Before we examine the spectrum of hydrothermal deposits in terms of the geologic

setting in which they occur and their distinctive characteristics, let us recall that
hydrothermal fluids could be of diverse sources such as meteoric, magmatic,
metamorphic, connate, seawater and juvenile. Each fluid type has its typical thermal and
chemical characteristics which can be retrieved by study of its mineralogy (you already
know the importance of study of texture and paragenetic sequence). We will try to
characterize this fluid in two broad attributes, their temperature, their gross chemistry.
We can put it broadly as a term is salinity for the time being, and also pressure which we
will see the importance through the course of discussion. We try to broadly characterize
these different fluid sources. Meteoric fluid are the ones which are likely to be of low
temperature, and also low salinity and this fluid invariably would be oxidizing in nature.
Magmatic fluid by default would be high temperature and a variable salinity; often this
solidity could be very high - in situations which we will be discussing and salinity will
be variable broadly, from very low to intermediate salinities. Metamorphic fluids are also
likely to be high temperature and generally low salinity, but on special circumstances
they may attain high salinity. This is visualized as the fluid is likely to be of high
temperature and low salinity.
There are ways to determine the thermal state of the hydrothermal fluid, they could be
done from the mineral themselves. The ore minerals like the sulfide minerals are
characterized by non-stoichiometry, which essentially means that the composition of
these sulfides, generally are not the original compositional signature, it generally is not
preserved and the composition generally get readjusted or changed from the condition of
their formation to the later decrease in the temperature conditions of the changing
environment. There are only a very few such ore minerals which indicate the temperature
conditions of their formation. One such mineral is arsenopyrite (Fe(As, Sb) S), and this
mineral is essentially can be considered as a solid solution of As and Sb and the exact
mole percent of arsenic in this arsenopyrite mineral, under specific conditions can be
used as a thermometer which is shown here. When arsenopyrite occurs along with
sphalerite which is a (FeZn)S and the compositional variations in (FeZn)S can be
expressed as mole percent of FeS. So, this mole percent of FeS in sphalerite, as well is
this arsenic atom percent in arsenopyrite indicate the temperature condition under fixed
values of the fugacity of sulphur, and with which only we can constrain the temperature
and this temperature can be approximated as the temperature of the hydrothermal ore
fluid as the minerals are result of precipitation from fluid.

We do also have on certain circumstances on which we will be able to determine the

temperature of the hydrothermal fluid from appropriate mineral assemblages that we see
in the ore. Just taking a small example here. If we take a mineral like galena and another
mineral sphalerite, which is a (FeZn)S, and these two minerals crystallize in the cubic
system, and we can consider that these minerals coexist as mineral pair satisfying the
condition of an equilibrium assemblage from the textural criteria, and we measure the
concentration of trace element such as cadmium or manganese, which are present in
these major minerals as trace elements in their lattice. Using standard thermodynamic
considerations, it can be shown that the concentration of a trace element in the coexisting
minerals is a function of temperature and thus can be used as a mineral thermometer in
natural ore systems.

So, there are ways and means to constrain, the temperature of the ore fluid; like the two
such cases that we have considered. One is use of the stable isotopes of oxygen carbon
and sulfur, and sometimes the composition of the mineral themselves such as
arsenopyrite, or using certain methods such as the trace element concentration in major
phases and formulation of the thermometry to estimate the temperature.

We will now go into the other method of temperature estimation which is a quite an
elaborate and evolved method and only a brief, here. We study fluid inclusions in
minerals (gangue minerals like quartz, calcite, fluorite and many other that form along
with ore minerals, sometimes the ore mineral themselves like sphalerite, cassiterite) to
retrieve temperature, gross chemistry (salinity) and pressure of the hydrothermal ore
fluids. It is quite an established fact that minerals forming from fluid, invariably capture
aliquots of the mother liquor in the process of growth of the minerals, in form of tiny
fluid filled cavities (mostly observable under the microscope) called the fluid inclusions.
Since they are dominantly water with dissolved electrolytes and non-electrolytes, we can
use simple principles of depression of freezing point to measure their total dissolved
solids and also approximate the temperature at which the mineral formed by doing
heating experiments using appropriate device. On examining a large number of such
fluid inclusions in minerals sampled from an ore body in a deposit, we can get a broad
idea about the temperature and salinity characteristics of the fluid and the path of
evolution (see Fig. 6). Such information is useful to decipher the fluid sources and
mechanism of transport deposition process.

Fig. 6 Schematic diagram for evolution of hydrothermal ore fluid showing various ways
that the fluid could evolve and indicate the mechanism involved in transport-deposition
process. This fluid inclusion diagram pertains to the aqueous fluid only.
And a trend which would indicate cooling also is possible theoretically, because metal
solubility is a function of temperature. So, is the temperature is high so solubility will be
high, and when the temperature drops the metal solubility will decrease and resulting in
precipitation of the metals and different forms of minerals.

So, this fluid evoluation diagram helps in getting some first-hand information or some
preliminary idea about the gross thermal and chemical characteristics of the
hydrothermal fluids of different origin, and fluid inclusion characteristic or fluid
inclusion data also helps in pointing to the dominant process involved in the
mineralisation, involved in the deposition of the minerals.

Fig. 7 Temperature-salinity ranges usually observed in some hydrothermal deposit types.

Kuroko – VMS in Japanese Island Arc, Irish – SMS deposit, Lode-Au –
metamorphogenic hydrothermal deposit. As can be seen, the magmatic hydrothermal
systems are usually characterized by high temperature and salinity.

Fig. 7 shows a scheme on which the gross fluid characteristics of a good number of
hydrothermal deposits, the porphyry essentially is corresponding to porphyry copper
deposits, which we see them in continental arc type convergent plate boundary, the skarn
deposits occur in continental interior or maybe in some of the active continental interior
or active continental margin, associated with Felsic magnetism.
For example, our objective is that weather will be in a position to decipher unequivocally
without any doubt as to whether the data we have got or whatever information we are
getting from the fluid inclusions, is actually able to tell us, not only the characteristics of
the ore fluid, but also the important process involved in it. Because it is its very essential.
Because for example, boiling - boiling is a very important process because whenever
there is a parent fluid and it undergoes boiling means it gives rise to or it splits into a
vapour and liquid, there is a substantial change in the chemistry of the of the residual
liquid here. At least we know that many of the volatiles will be getting partitioned into
the vapour phase and the initial pH of this fluid is going to change a lot in the residual
liquid after partitioning of the many of the components which we were responsible for
imparting the acidity to this fluid.

And since metal solubility depends a lot on many parameters like temperature, oxidation
state pH of the fluid, it becomes easier for us to understand the process of formation of
this mineral deposit. Similarly, mixing sometimes is important as we see from the fluid
inclusion evidence, take for example, originally a fluid was reducing and it was
transporting a metal like Sn in it is plus two state, where it is soluble and this particular
fluid in order to deposit the metal in it is oxide form, needs to encounter a more
oxidizing condition.

So, under this situation, if this particular original fluid was a magmatic fluid and was
reducing in it is nature by virtue of the original composition of the magma from which it
exsolved, and the process or interaction and it mixes up with a fluid which is oxidizing.
Let us say it could be a meteoric fluid which is oxidizing fluid. So, then it will result in
the deposition of the tin in form of the insoluble metal oxide. So, here a fluid mixing has
been the dominant process. So, it is the fluid inclusion data which will give us conclusive
evidence about the processes such as boiling mixing and cooling and also more
importantly unmixing.

For example, there was an original fluid which was a mixture of H2O plus CO2 I would
represent carbon dioxide is carbonic, thinking that this carbon dioxide also could be
mixed with a bit of methane or other reduced species or it could be say if some such fluid
was originally having a solubility, substantial solubility of metal like gold which will be
seen in details when we will be examining such deposits. It splits up into a carbonic part
and an aqueous part and this, if the carbon dioxide present was responsible in
transporting the gold then here by the process of splitting or unmixing, it will result in
the deposition of gold either in the form of free gold or whatever is the environment
allows. So, this unmixing process is also conclusively deduced by studying the fluid
inclusions in these ores.

So, to sum up we can combine stable isotope of oxygen and sulphur isotope data,
mineral thermometer - thermometric or thermo barometric data, and fluid inclusion data
and we synthesize the information together, it gives us the idea about the fluid
characteristics in terms of it is source the dominant mechanism that is involved in
formation of the hydrothermal deposits.

One thing is that among all these diverse hydrothermal mineralization environments, one
thing is very common that these hydrothermal fluids, they do transport the metals in high
concentrations which make them deposit these metals in the form of ore deposits which
are enriched and can be recovered as ores for our use.

The basic question that arises that what makes these fluids transport these metals in
whatever form and we look at exactly in what form they are transported. Analysis of the
present day hydrothermal fluids from the ocean floor hydrothermal systems as well as
the land based geothermal systems approves or gives us conclusive evidence that these
hydrothermal fluids do transport the metals in substantial quantities in concentrations to
give rise to mineral deposits, although it always depends on how much or what is the
quantity of the fluid and what is the concentration of the particular metal - that will vary
from system to system, but the fact remains that these fluids do transport the metals.

The question that is posed in this context is that, what is the form in which these metals
will be transported in the hydrothermal fluid. A first guess would be that metals are
transported as soluble ions in appropriate pH (acidic) and we may visualize the situation
taking Pb as an example and a possible reaction as

PbS + 2 H+ → Pb2+ + H2S

Where we can either take an aqueous or gaseous H2S and with equilibrium constant of
the reaction known at a desired temperature can calculate the molality of Pb+ that could
remain dissolved. Results of such calculation indicate that the molality is too low to
actually transport Pb to give rise to ore-grade mineralization of Pb. Therefore, we suspect
that the metal must be getting transported as some complex species combining with some
ligands. This requires that we know the chemistry of hydrothermal fluids in terms of
concentration of common anions and cations so that we could work out the possible
complexing of metals for their efficient transport. The table below gives results of
analyses of hydrothermal fluids sampled from present-day hydrothermal systems.

Table-1 Concentrations of anions in diverse hydrothermal fluids.

Ligand Concentartion
range (moles/kg
H2O)
∑Cl- <0.03 to > 7
∑SO42- 10-10 to 0.3
∑S2- 10-4 to 0.1
∑NH32- 10-3.9 to 10-1.5
∑CO32- 10-3.4 to 1
∑acetate 0 to 0.17
0 to 0.059
∑propionate
0 to 0.005
∑oxalate
0 to 0.025
∑malonate

As can be seen from the table, chloride is the most dominant anion reaching as high as 7
moles per kg of water and also some other inorganic and organic anions. It indicates that
metals could possibly be transported as chloride, sulfate/sulphide, carbonates and also
organometallic complexes.

While the metals are simple ions the ligands could be simple or complex ions here. So,
without getting into the much of the theoretical details of such kind of metal ligand
complexing, we will just see whether will be we say we can rationalize or we can make
some basic understanding on the transportation of the metals as metal - ligand complexes
and essentially the question that arises is that what makes a particular metal combine
with a particular ligand to form a complex. So; that means, or in other words that is
something which will say as metal - ligand specificity or a specific affinity of a particular
metal to a particular ligand. So, studies on this in this particular field in this part of the
solution chemistry it led us to the concept of classification of the metals and the ligands
into acids and bases something similar to the Lewis acids and Lewis base. And these
acids and bases were actually divided into hard soft and intermediate. Hard intermediate
and soft, similarly the bases are also divided into hard intermediate and soft.

Table -2: Hard – Soft classification of metals (acids) and ligands (base).

Table-2 above shows a classification of the metals and the ligands into hard borderline
and soft. Metals are considered as Lewis acids and are categorized as hard acids - the
ones which have a high charge by radius ratio and are the monovalent alkaline elements
like the lithium sodium potassium or the high field strength element like scandium
yttrium tungsten; tungsten 6 plus tungsten 4 plus and so on. So, most of the metals of our
interest manganese, Fe+3, Co+3, arsenic, titanium, zirconium, hafnium, molybdenum,
antimony, platinum group of elements, uranium 6+, uranium 4+, these are all coming
under the category of hard acids. The borderline acids are obviously those which are the
bivalent ones like Fe2+, manganese, cobalt, nickel, copper 2+, zinc 2+ lead 2+, Sn2+,
As3+ - these are under the category of the borderline metals on the basis of their charge
by radius ratio and metals like gold silver mercury cadmium are the soft category of
acids.

Similarly, the bases – fluoride, hydroxide, oxide, bisulfate, and sulfate are the complex
anions. It is not an exhaustive list of the anions and cations, there could be other ligand
such as organic ligands also could be incorporated here according to their characteristics,
but then we are seeing the most common ones and we see that chloride ion is the most
soluble of these species in hydrothermal fluid occurring in maximum concentration in
almost all types of hydrothermal fluids. Chloride ion belongs to the borderline category
and forms chloride complexes with the intermediate metals. Bisulfide, sulphide, H2S,
cyanide bromide kind of anions are the soft acids and have affinity for soft metals for
complexing.

What does it tell us - without getting into much of the theoretical details it gives us a
broad framework to understand that hard acids are likely to combine with hard bases to
form there complexes, borderline acids will combine with the borderline ligand to form
their complexes that is how we could correlate that Pb2+ , Zn2+ , Cu, to form their
chloride complexes and soft metals like gold silver mercury will readily form there bi
sulfides sulfide kind of complexes.

So, this gives us a broad outline although the exact mode in which the metal is
transported depends on which of these species are more dominant and there is always a
competition for the metals to combine with the particular ligand, also are very much
dependent on the stability of such kind of ligands. For example, the sulfurous species
will be strongly dependent on the pH. So, depending on the pH of the environment if
there is the dominance of the bi sulfide or the sulfide species then only the gold or the
silver or the mercury will get the opportunity to get complexed as bi sulfide; sulfide
otherwise if there is a dominance in the chloride and also these kind of complexes are a
function of the dominance of the type of complex which forms as a function of the
temperature, but within those limitations these give us a good guideline to understand
which of the metals are being transported in what form.

So, it helps us also to understand the process during the deposition of metals as to what
kind of physicochemical change we would expect for the metals to be deposited.
Because this mineralization process involves the substantial solubility of these metals in
the hydrothermal fluid under a given physicochemical condition, we need to have a
change to be brought about in the environment, the chemical environment. so, that the
metals will be deposited when the solubility decreases.
So, here we can represent the mechanism of complex formation. So, the complex can be
represented if it dominantly happens to be chloride complexing because the chloride
complexing is the one which has been very extensively studied through experiments. So,
this gives a schematic relation. The metal ion with q + charge and n number of the
ligand with - p charge will form a complex which is MLn q minus np.

The net charge on the complex will depend on the value of n and here we can represent
the equilibrium constants and formation constants of such kind of complexes through
generally represented equilibrium constant as βn which will be K 1, K 2, K 3 or K 4
which will be explained as follows.

Suppose the bivalent metal with +2 charge and n number of chloride and forms a metal
chloride complex then this will be forming a complex which will be MCl2-n and the
equilibrium constant is expressed as the concentration or the activity of the this complex
which has got a charge of 2 - n and this is how the concentration can be expressed.
So, here if we take a sulfide like galena which is MS that reacts with 2H+ is giving rise to
a bivalent and M2+ and H2S aqueous. So, here the equilibrium constant is given by this
expression which is M 2 plus into these. So, here these are essentially representing the
terms which are the thermodynamic concentration or the activity and in case, it happens
to be a gaseous species, we can represent it as fugacity or the corrected partial pressure
and if we take ideal conditions then they all be representing a simple concentration terms
for example, for a metal it will be representing a term concentration term as molal or in
case of a species like H2S, we can always represent it in terms of atmosphere.

And now if we try to find out the what exactly is the total amount of the metal M which
is there in the solution then we have to consider the metal to be present in the form of
M2+ and the total concentration of the metals which is complexed in different
stoichiometry because this is summation term so, that means, if happens to be a MCl or
MCl2 or MCl3 and so on, then the total concentration will be coming out of all the
possible complex stoichiometry responsible for a bivalent metal like say for example,
lead.

So, here for the time being, even you can ignore this activity coefficient term because we
we are taking them to be ideal and activity coefficient taken as one. So, this becomes this
the total solubility become the activity of the metal ion plus all the activities of the
chloride ion or in terms of their concentration. Now here we can replace since since the
equilibrium constant through this reaction is coming out in the form of the H2S gas
partial pressure here we can replace M2+ from this equation as the equilibrium constant
into the hydrogen ion concentration square divided by the fugacity of H2S and these
keeps as an expression.

So, this is a total concentration of the metal. So, as we stated before that if we consider
the metal to be transported only as metallic 2 plus ion and the because of the equilibrium
constant very low equilibrium constant of this kind of reactions, but in actual what is
happening is that this metal like M with availability of the ligand which is chloride is
able to form complexes and the total solubility of the metal is contributed by formation
of the complexes of the metal.
Here is the example that take a metal like lead. So, here this is the solubility product
which is activity of the concentration of the led 2 plus and the fugacity of H2S by the
activity of hydrogen ion square and the total concentration of the lead expressed is molal
is given by an expression where it is the solubility product of this reaction into the pH
divided by the fugacity of the partial pressure of H2S.

So, what is coming out from here it gives us a clear-cut idea that the solubility of the
metal is dependent on one of the important parameters that comes here is the pH. So,
when the activity of H+ ion will be directly responsible to what the concentration of the
total metal is and other variables are also contributing to it.

Now, coming to the actual mechanism taking the example of lead here, if we consider
that lead is a bivalent metal and the in a hydrothermal fluid we have abundant chloride
ion as the ligand, then Pb can possibly form a series of such complexes as shown in the
box above. So, these are these are the correct species which form as the complexes are
for Pb.
So, then here the total concentration of Pb here is being shown as the total concentration
coming from the molality of lead in the form of Pb+, PbCl+, PbCl2, PbCl3-, PbCl42-. Each
of these complexes can be related to the concentration of the total chloride and the
concentration of the sulfur-species responsible for causing deposition.

So, the amount of the metal, taking example for a metal like lead here in this situation
would be similar for other bivalent metals like zinc.

So, likewise there have been several experimental studies on the solubility behavior of
gold as different complexes as chloride and bi sulfide, solubility of many of these base
metals copper led zinc in hydrothermal fluids in different wide range of temperature and
a composition mainly affected by the pH.

So, there is a good amount of information that is available to us that under diverse type
of ore forming hydrothermal environments that we have discussed. The metals are
dominantly transported in the form of metal complexes - likes chloride complex is one as
dominant metal, there could be bicarbonate complex, bisulfide or sulfate and other type
of complexing depending on the gross chemistry of the fluid.

So, in order to get the hydrothermal fluid deposit in the form of a mineral deposit or in an
ore body we need to have a change in the physicochemical environment from a
dominantly transporting regime to a depositional regime. So, this is brought about, as we
have already discussed before in the context of fluid inclusion that the basically brought
about by processes like boiling of the fluid, mixing of fluid, fluid unmixing or phase
separation and interaction with the wall rock with simple cooling as one possibility.

So, these processes operate in combination and then, as we stated in the very beginning
regarding the ore deposits, these process have to operate at a particular scale and then in
an optimum intensity and in optimum environment which will give rise to a
hydrothermal deposit, deposit of a size in terms of the quantity of the metal that will be
deposited in a particular locale to give rise to a deposit sometimes they do give rise to
deposits which are fairly large in size giving a good amount of the metal in terms of the
total tonnage that is available and sometimes, if the conditions are not that very
favorable they result in what we call as a lean or uneconomic ores. So, then if we are
going from a transporting to the depositional regime, then we see the what exactly we
would expect.
When the hydrothermal fluid flows through rocks and deposit metals in suitable locales,
it leaves its imprint in the host and country rocks which we broadly identify as the
hydrothermal alteration which invariably has a zonal pattern in most cases. For example,
a metal which is being transported as a chloride complex, and that is now coming in
contact with or that is now coming to a situation where the partial pressure of H2S is
increased to the extent, the metal sulphide (MS) forms and in that process, it liberates H+
ions. So, as a direct consequence of deposition of this metal complex to a sulfide there
will be release of this H+ in the fluid. So, in order for the particular reaction to advance or
to go on to completion, there must be something which will absorb this H+ (ion) or which
will act as a sink for this H+ ion to be accommodated. This H+ ion is eventually
consumed by the wall-rock of appropriate mineralogy (silicate / carbonate) causing
alteration to the mineralogy. The whole spectrum of hydrothermal mineral deposits that
we have listed out in the beginning are very characteristically associated with their
typical hydrothermal alteration zones.

We will look at them individually when we look at these deposits, but these
hydrothermal alteration zones are very prominent in deposits like porphyry copper
deposit, skarn deposits, VMS, the lode type gold deposits, the epithermal deposits and
there are some nomenclature which are proposed for such kind of hydrothermal
alterations like potassic alteration, phyllic alterations, argillic alteration, propylitic
alteration, advanced argillic alteration (as observed in porphyry copper systems),
silicification, carbonate alterations often quite common in many hydrothermal deposits.

To, recapitulate we have been discussing about the attributes of hydrothermal fluids, and
made a brief attempt to understand the role of temperature and the retrieval of
temperature through different techniques such as fluid inclusions, mineral
thermobarometry that provides us a background in understanding the role of fluid, the
characteristic of the fluid. Further we would again see some of the other important aspect
or attribute of hydrothermal fluid which is pressure. Pressure is also an important
parameter, although in many of the low temperature conditions pertaining to surface
operated process which are governed by solubilities of different elemental metallic
species, anionic and cationic species in the fluid, is rather insensitive to variation of
pressure. But when we deal with a fluid at deeper conditions in the crust, pressure also
becomes an important attribute which we will try to explain diagrammatically as shown
in Fig. .

In the near surface conditions, the fluid flows in interconnected pores and fractures in the
rocks, where the movement of the fluid is generally in response to a hydrostatic head and
fluid, such as groundwater move through the porous medium of the rock abiding by
certain simple physical principles which we will not be discussing in details here. Our
concern mainly will be in relation to solubility of different species in the hydrothermal
fluid and the consequences of variation of pressure. At depth, and in case of non-porous
and impermeable rocks, fluid will be generated within the deeper parts of the rock layers
in the crust and the fluids will get accumulated in the rocks. Dissolution of electrolytes in
crustal fluids, which you know is less dependent on pressure. However, solubility of
some important gaseous species like carbon dioxide and the halogen species (chlorine
fluorine), sulphurous species like sulphur dioxide and H2S, which play a very important
role in controlling the solubility metal transporting deposition phenomena, is controlled
by pressure. Some simple examples will explain the consequences on the variation of
pressure within the fluid.
Fig. 8 Schematic sketches depicting possible situations of fracturing and fluid activity in
the crust.

If you look at the diagram (Fig. 8), case one, where the hydrothermal mineralization is in
response to fracturing in a shallow crust. Let us take for example a mass of rock which is
porous and there are pore spaces inside this rock which is filled up by water. And take
any arbitrary depth variation within - from surface to any deeper part of the earth within
the rock layers, the pressure should vary as per the lithostatic pressure which we know
how to calculate it from the rock density, and the height of the rock column at any
particular point. Now, let us think of a situation where there is a discontinuity in the form
of a fracture which is created in the rock which is possible if there is some kind of an
extensional deformation as shown by the thick red line representing the width of the
fracture. So, the moment there is a fracturing if the fracture is opened to the surface, then
this fractured zone essentially becomes a zone of reduction of pressure. And fluid from
the surrounding will flow to the fracture in response to this pressure gradient. And any of
the chemical species which are there in the fluid, the most common which you can
consider is silica. The solubility of silica which is commonly very low in the crustal
water dominated fluids in terms of millimole per kg will undergo deposition because
with the response to the reduction of pressure and the pressure difference will always be
a function of depth. If the fractures the fracture is open to the surface pressure anywhere
within the fracture will be the hydrostatic pressure which will be at least roughly about 1
by 2.5 of the pressure any point here the lithostatic pressure. So, this will create a
pressure gradient and the fluid will converge into the fracture zone. And in response to
that will start depositing the materials especially for example, silica and that is how we
get lots of quartz veins in the crustal rocks under diverse types of rock composition. So,
here we could also have some of the important metallic species also getting deposited in
the form of their ore minerals.

There could be a situation which could be that the fracture which has been created in this
rock mass does not open to the surface. So, the pressure of the fluid on any of the point
within the fracture space would be something which will be intermediate between
lithostatic and hydrostatic pressure. So, we see such kind of situations where this kind of
brittle deformation within the earth’s crust gives rise to formation of the mineralized
veins, and such kind of situation sometimes lead to an interesting phenomenon which we
discussed previously. And that can be also understood with the help of a simple diagram
here.

L
Pressur Cp

Temperature

Fig. 9: Unary phase diagram showing the stability of liquid and vapor fields. The upper
arrow indicates the initial PT condition in which the water-rich fluid originates in the
crust and the line represents the path of reduction of pressure (say due to upward flow of
the fluid along a fracture). The lower arrow indicates the point in P-T space
corresponding to boiling (coexistence of liquid and vapor). If the condition in the
fracture reaches that point, the fluid will boil (exsolving a vapor to which volatiles get
partitioned).

If the fluid was present within the rock in unconnected or impermeable region where the
fluid was at lithostatic pressure. When the fracture is created in response to the pressure
difference, if this pressure difference happens to be exactly in quantity similar to the
pressure that is required for the fluid to intersect the boiling curve, then the fluid boils.

And we have already discussed about the importance of boiling in as a process in the
hydro thermal transport deposition phenomena. And because this boiling results in a lot
of difference in the change in the chemistry of the fluid, which ultimately deposits these
metals. And we see many such cases in hydrothermal systems where the deposition is
due to boiling and which is preserved as imprint in the fluid inclusion evidence in
minerals which deposit along with the ore minerals.

Fig. 10 Schematic sketches showing the situation in which fluid from deeper sources
could be released and trigger hydrothermal mineralization.

There are situations corresponding to as a shown above (Fig. 10). If you look at the first
sketch here, the situation here is that, the surface represents something (in the deeper part
of the crust) where the rocks are undergoing metamorphism under high pressure and
temperature conditions. And this metamorphism is resulting in extensive devolatilization
( fluid which was initially bound to the hydrous mineral phases), and liberation of water
charged with significant CO2 as well as S-species. This is happening at a much deeper
part of the earth where the fluid is not able to escape or not able to move out because it is
bounded by some kind of a ductile layer which is acting like a lid below which fluid keep
accumulating and exerting pressure. And if it also happens to be a zone where there is
active deformation going on then this fluid within here will be experiencing a pressure
which is over what is expected to be lithostatic pressure here which we call it as a ‘supra
lithostatic pressure here. And just about in this region, if we bring about a crustal scale
deformation something like shearing, then it creates a channel way for the fluid to escape
through such kind of crustal scale zone. And this fluid will escape through this fracture
zone through which it will experience a sudden change in pressure and deposition of
whatever is dissolved under high pressure. We know that very high-pressure temperature
condition materials like silica remains dissolved in substantial amount and if the fluid is
channelized through such kind of crustal scale shear zone then it gives rise to what we
observe in many of the situations as large quartz veins which sometimes bear
mineralization especially with respect to gold. So, this process essentially shows how
pressure is important in hydrothermal fluid and when we are talking about the fluid
which is of a deeper source, this also could this process which is shown in a simplified
form. Now, this crustal scale shear zone which will experience deposition of the
materials will get filled up or will get sealed. After the fluid is deposited and again the
pressure builds up here and this fluid itself will either cause a hydro fracturing or as has
been proposed in many of the cases. it may be in response to a tectonic activity like an
earthquake in which this shear zone again can be reactivated or reopened. And there
could be subsequent batches of fluid released from this region where it is accumulating
in response to the increasing pressure temperature condition and the devolatilization and
accumulation of the volatiles in this region. So, this is how we could visualize the
spectrum from surficial low temperature pressure conditions to much deeper conditions.

So, with these kinds of simple explanations we give a bit of a background understanding
to the hydrothermal fluids. And we demonstrate or we at least make an understanding
that when we say that a mineral deposit formation is earth’s own mechanism of
beneficiation, then we have come to a stage to realize that yes this hydrothermal fluid is
one of the most efficient and effective agent to do that beneficiation which gives us a
wide range of mineral deposits as we have seen when we classified them under the broad
category of hydrothermal deposits. In addition to that, there are many other chemical
parameters that control the transport deposition phenomena which we have seen - the pH
the acidity of the fluid is a very important parameter where the normal variation of the
hydrothermal fluid the pH could be anything two or three units positive or negative from
the neutrality. The redox state the fugacity of oxygen and on the surficial process we use
parameters such as the redox potential Eh and pH to explain formation of many different
types of ore deposits of the surficial conditions.
Then with the activities of the dominant cationic species the dominant like potassium,
sodium, which are in abundant calcium, magnesium and the anionic species like sulphate
and chloride.

And now we will make a brief survey of the different types of hydrothermal systems.
And in terms of the origin, we discussed that magmatic hydrothermal system is one
important class of the hydrothermal fluid based on the origin that the fluid is essentially
having a magmatic origin. So, under this category, we have the porphyry type deposits,
copper, molybdenum, tin and we have the skarn and greisens, the pegmatites. And there
are many other deposits which are of uncertain affiliation where magmatic source is
sometimes suspected like some of the uranium deposits, some special circumstances
where a magmatic affiliation is only suspected through retrieval of temperature and fluid
sources from stable isotopies. So, we will be considering them of some special cases.

We will take the porphyry type deposits as our type example which are the most studied
magmatic hydrothermal process and then briefly touch upon others. So, once we make an
understanding as to how this magmatic hydrothermal system works we will be able to
understand the other variations giving different types of other metals. This porphyry
deposits an important source for copper molybdenum and tin, and also gold.

Now, what we discussed about the magmatic deposits when we discussed about the
chromite and other deposits which are essentially ortho magmatic in nature. So, this is a
domain in which we have primarily been dealing with felsic magma. Whenever we say
magmatic hydrothermal system by default we mean it is a felsic magma, which is
responsible in giving rise to the mineralization. So, we must understand what is so
special about this felsic magma as compared to the mafic magma which is dry. We can
call them as wet magma or the magma which is charged with lots of volatiles, water
being the dominant species. The halogen species, chlorine, fluorine and sulphur bearing
species sulphur dioxide and H2S depending on what is the oxidation state of the magma
is. Therefore, we must first understand the basic difference, so that is why when we
consider the ortho magmatic deposits associated with mafic magmatism we only looked
into the mechanism of a crystallization of the melt. Here we have to take into
consideration in addition to the crystallization of a felsic magma, we do also have to look
into more critically on the melt fluid regime where a fluid phase evolves from a
crystallizing felsic magma and what are the different possibilities that we see.

Number one is that it depends on the source from which the magma is generated. In most
of the cases we know that the magma is generated in the lower crust region, the magma
which is generated in the continental arc subduction zone situations. Melting from the
subducting slab often involving the mantle wedge. so, they give rise to the calc alkaline
magma. And the magma is derived from a source where there is plenty of availability of
the volatiles mainly water and other halogen plus S-bearing species. In case of the
porphyry copper deposits which are coming from the active continental margin like the
Andean margin we know that this type of magma is coming out due to melting of the
slab which was generatedin the mid oceanic ridges, and it has a long history of
interaction of the seawater. So, it essentially is a modified or a changed material along
with the ocean floor sediments and it is getting subducted in the subduction zone
undergoing high temperature pressure metamorphism and melting partially where it is
giving rise to the magma. And this magma with which the porphyry copper deposits are
associated are generally classified as I - type magma or the magma from an original
igneous source even though we know that it is the seafloor basalt which is
metamorphosed to almost like an amphibolite and undergoing partial melting as and
when it goes down into the asthenosphere and encounters higher and higher temperature.

The initial water content and the volatile content is a very critical parameter that dictates
what the hydrothermal activity will be. The oxidation state is also related - what exactly
we are labelling this I- type magma is supposed to be or is observed to have a higher
oxidation state which is indicated by the dominance of the oxidized sulphurous species
which has an important bearing on the evolution of the hydrothermal fluid.
Another important parameter with this system is the water saturation of the melt which
undergoes crystallization. Initially there is a dominance of the nominally hydrous
minerals like amphibole or other anhydrous minerals which crystallize and after a
substantial proportion of crystallization the residual melt gets enriched with respect to
the volatile and reach a value of saturation. When the magma which are generated in the
condition that we have just discussed can have water content of 2.7 to 2.8 weight percent
to as high as 6 to 7 percent depending on the availability of the water. The water-rich
fluid at volatile saturation is already rich in halogens and other cations and is invariably a
high-salinity fluid and by virtue of high concentration of complexing ligands, have high
concentrations of metals (Cu, Mo, Au) at the time of exsolution from melt (melt-fluid
interaction domain). The evolves in different ways (the common process of evolution
described in the following section) in different conditions and give rise to generally large
deposits with very high tonnage going to almost like 700, 800, even 1000 million tons
and are generally of low grade of metal (copper percent is going to just about a little over
1 percent). And they are dominantly the copper dominated which are the porphyry
copper deposits though although many of the porphyry copper deposits will have
insignificant molybdenum concentration also. There are gold only, there are
molybdenum only (example – Climax Deposit, Colorado, USA) porphyry deposits which
will see them and they have a very interesting specificity on the type of rocks that they
are associated with. The porphyry type deposits can be present in diverse composition
felsic rocks like quartz diorite, granodiorite, quartz monzogranite diorite even up going
up to the syenite monzonite type of composition.
Fi. 11: A generalized geologic section depicting the porphyry-copper model.

Let us take a look at this figure (Fig. 11) which is a model for the occurrence of the
porphyry copper deposits. What we see here is, generally that, the porphyry copper
deposit is associated with a small plug like magmatic body of felsic composition, the
range which we have already seen and this small stock gives rise to a deposit, the
quantity of the metals which we get in terms of several million tonnes. So, if we go by a
mass balance, this granite being the sole contributor of the metal of course, there is no
other possible source. Here, it is the granite, which is the source for the metal, then it
does look like that, such huge mineralization is very unlikely to be resulted by a small
magmatic body like this with our understanding on the felsic system, in general and
looking into the porphyry system in particular. This particular model was proposed long
back, where it is proposed and what we see is a small stock in the mineralized area,
which ever porphyry deposit we visit, it is actually a result of a larger, much larger felsic
magmatic system at deeper levels and this small body is the one, which actually gets
separated out of the larger granitic pluton, which was emplaced at a particular depth
condition, in the earth’s crust. The figure is a generalized model for the porphyry copper
deposits. These deposits are essentially characterized by the alteration zones, which
surround the mineralized plug like body and has a very characteristic porphyritic texture
from which the name of the deposit is derived as porphyry type deposit. They do have a
porphyritic texture in having some early formed phenocryst with ground mass type of
texture and they are associated with many other features.

Fig. 12 : Schematic diagram depicting evolution of the magmatic hydrothermal system

in a porphyry copper deposit.

Fig. 12 has schematic diagrams proposed, based on the understanding of the felsic
system and the way they evolve and the mineralization is resulted. First of all as we
know from the very source, from which the granitic magma has generated. They are
generated from some kind of a basaltic amphibolite type of source, which contain water
in their structure and the water content could be anything like 2 to 5 weight percent and
what is more important is, when the rocks partially melt the amount of water that is
contributed by the partial melt which can be also be calculated by taking some mass
balance calculations. And if we take this particular body which is emplaced in any part
of a crust, then during the progress of crystallization this represents a hypothetical 1000
degree solidus for the system and what is shown here is, there are some smaller
injections of this felsic materials in the form of dykes here. S1 is representing the water
saturated solidus surface. This solidus is actually suppressed here, because of the water
content and this particular crystallizing body, with crystallization of substantial
crystallization of the early crystallizing phases. The residual melt is is concentrated with
respect to water, which keeps on in increasing and is accumulating on the top part, which
can be called as a water saturated carapace.

Now, here at a later stage of solidification, volatile water along with all the chlorine
fluorine and sulphurous vapour, all are accumulating in the carapace. They are exerting
pressure on the overlying rock and if the yield strength of the overlying rock is exceeded,
then this results in a network of fracture and through which the crystal melt mush along
with the residual fluid is emplaced within the shallow part of the system and which is
exemplified by the dense network of fractures, which basically called as the stockwork
and resulted by the hydro fracturing. The pressure that is exerted with the percentage of
fluid that is accumulated or exerting the pressure can be very well calculated from
thermodynamic consideration by the change in volume of the fluid with decrease in
pressure. The separation of the volatile phase from crystallizing magma with initial
crystallization of anhydrous minerals is something called as a ‘retrograde boiling’ or
‘second boiling’ and accumulation of the fluid within the carapace region of the
crystallizing pluton and building of pressure, which results in brecciation in the overlying
country rock. So, this gives us a very dense network of fracture and a complicated
pattern, but this is actually the region in which the fluid deposits metals and give rise to
alteration zones.

Fig. 13 Waning stage of the porphyry system and cross section of a typical porphyry
copper deposit with zonal pattern of alteration.

So, in a later waning stage of the hydrothermal system (Fig. 13), there we see lots of
such dykes and the brecciated regions. With this general picture of evolution of a
magmatic hydrothermal system, which should actually apply to almost all the porphyry
system associated to felsic magmatism. The initial water content and the value of water
concentration at saturation that means, the point at which the fluid phase gets saturated,
getting separated or exsolved out of the crystallizing melt, they are the critical parameter,
the ratio, the value that we get by dividing the original water content, which we can
represent as a parameter, which is as a concentration, which we call as a concentration of
water, of the say, of the melt, initially when it is initially Cl 0.

So, this is the initial concentration of water, in terms of weight percent. The parameter
CwS is the concentration of water at saturation is also quite critical. The ratio Cw, l 0 by C
s
wl is usually high, if the original water content is high and is low and there has been
good amount of crystallization of the melt and then it is attaining to water saturation, it
also is very sensitive to the depth at which it is emplaced and in the context of the
porphyry copper deposits. they are generally emplaced at depths corresponding to
pressure of almost 500 bars to 2 kilo bars, not more than that. That means, almost about
6 / 7 kilometres to 2 kilometres to 3 kilometres in the below the earth’s surface.

So, what results by this process can be schematically shown on right sketch of the figure.
It is taken from the San Manuel, Kalamazoo deposit in Arizona and if we look at these
two diagrams here, then this is the core representing the small plug like body, which is
emplaced and then, surrounding that is essentially a zone where there is a low-grade
mineralization. - chalcopyrite pyrite molybdenite and then there is a rich ore cell part,
which contains the maximum concentration of copper and the richest part of the ore body
and is surrounded by again a cell, where it is pyrite rich, but chalcopyrite is poor and the
mineralization dies out in space. So, here this has a very good correspondence with the
alteration, which we will be discussing here. The core part which has the highest
temperature and the fluid has got all the signatures of a directly magmatically derived
fluid, with high salinity and very high temperature and this zone is characterized by the
kind of mineral alteration, which we call them as potassic, which we will see the
reactions. It is followed in space by the phyllic alteration, which is dominated by
assemblage of quartz and sericite and the ore shell is essentially on the richest part of the
mineralization coincides with the boundary of the potassic and the phyllic alteration
zones and then there is the argillic alteration zone and then this surrounded by a
propylitic alteration zone and sometimes we do also have an advance argillic zone which
as mentioned later. So, this is kind of a generalized picture, which can be obtained and is
observed in deposits all over the world. There may be some minor variations, here and
there sometimes all the alteration zones may not be developed or one later alteration
zone, might mask or might overprint. The earlier alteration zone and many variations are
possible depending on the local geological conditions, but porphyry copper deposits, all
over the world do conform to such kind of a general morphology.

Basically, the hydrothermal alteration zones represent an evolving system of the fluid.
The early formed mineral assemblages are out of equilibrium with the changed chemistry
of the fluid and this example is the potassic alteration in the core of the porphyry copper
deposits, where early hornblende gets altered to biotite and plagioclase to K-feldspar,
can be written by a very simple reaction of addition of potash - like Albite + K+ giving
rise to potash feldspar and Na+. So, it is very much controlled by the concentration ratios
of these two important elements, which is sodium and potassium or we can even write
such reactions for calcium. So, this reaction which is hypothetically, this is an edenitic
hornblende which is acted upon by the potash rich fluid, which is there in the core of the
system, with the evolution of the hydrothermal fluid and this fluid the pH of the fluid is
such that we have there in the sulphate stability field. So, this reaction is proposed for
conversion of hornblende to biotite in a potassic alteration zone typically seen in the
core of the porphyry copper deposit, what is to be observed here, this also gives rise to
calcium sulphate, which is anhydride, which is a very ubiquitous in occurrence, in the
core zone of the porphyry copper deposits very widely and this is taken one of the
important criteria, for identification of porphyry copper deposits.

When it is understood that sulphur is in sulphate or in the higher oxidation state, it has
also got important bearing in the sense that the metals which were initially dissolved in
the melt will not be getting precipitated in the form of sulphides or disseminated
sulphide, in that case the result in getting a highly enriched deposit, would not be
possible. So, the fluid essentially has to have a higher oxidation state at the beginning.
so, that the metals, most of this important metals; like copper, molybdenum, or gold will
get partitioned into the vapor phase efficiently. So, that the deposit will result.

Then when we have the Phyllic and Argillic alteration zones, where the Phyllic alteration
zone can be represented by the reactions as potash feldspars, acted upon by H+ ion to
give rise to muscovite, which is essentially in the alteration zone. It is sericite the white
mica plus silica and liberate potassium ion. This reaction also depends on the activity of
K+ ion. So, it is understandable that it is essentially the pH of the fluid, which is coming
to be the controlling factor and one interesting thing here, is that with the waning stage of
the magmatic hydro system, like porphyry copper here. Now, once the system is the
hydrothermal or the magmatic stage is ending, that time. It has enough of opportunity for
low temperature fluids like the meteoric fluid essentially, to come, to actually is get
infiltrated into the system and interact with the materials to give rise to different types of
alterations and the Phyllic and then when we see the Argillic alterations, where mineral,
which is produced here in the say Phyllic zone is muscovite, which is getting again
attacked by H+ ion to give rise to kaolinite, which is the index mineral which
characterizes the Argillic alteration zone, around the porphyry copper deposit, following
or immediately enveloping the Phyllic alteration zone.
Reactions for Advanced Argillic Alteration in porphyry copper system. See the alunite
forming reactions in particular

Sometimes, we do get the advanced Argillic alteration, giving rise to minerals like
alunite, where the kaolinite which is produced in the Argillic alteration zone is again
acted upon by potash and we have very high acidic, when the pH has gone to much
lower value with the abundance of hydrogen ion, this gives rise to alumnite and alumnite
is one of the very characteristic minerals associated with the advanced Argillic alteration
zone, in porphyry copper deposits. There are several such reactions which can be written.
Muscovite can be acted upon by sulphate at a very low pH conditions to give alumnite or
even potash feldspar, also at very low ph conditions can give rise to alumnite.

Reactions for propylitic alteration in porphyry system representing lower fluid/rock ratio
than argillic alteration and greenschist grade mineralogy.
And the alteration zone, which is basically labelled as a Propylitic alteration zone, which
is characterized by the presence of epidote and chlorite, that is a little bit of a difference
here, because it is a zone which rather indicates rock dominated or low fluid by rock
ratio and kind of the original greenschist facies assemblages persistence in the rock.

So, what essentially we are getting in a system here? The porphyry copper deposits are
very much characterized by multiple phases of such intrusions in one particular deposit,
particular mineralization zone and sometimes it is observed that the latest phase is
essentially the productive stage, which is a product of the crystallization evolution of a
larger granitic magmatic melted depth.

So, the alteration that we get is essentially within this granitic or the felsic country rock
which are there or sometimes could be the sediments. So, this propylitic alteration zone
is characterized by presence of biotite and epidote, which is a product of alteration of
hornblende and gets altered to phlogopite. Biotite can be hydrolyzed to give rise to
chlorite. So, maybe the combination of such kind of reactions will be giving rise to a
situation, where we would have epidote and chlorite to be dominant in this alteration
zone, which is characteristic of the propylitic alteration zone and it is understood that
from potassic zone to the advanced argillic zone, in the propylitic zone, the temperature
of the fluid is decreasing it is gradually from an original magmatic fluid, which is getting
cooled with mixing of meteoric fluid. In terms of salinity, the fluid is the most saline in
the potassic alteration zone. Isotopic studies and many other kind of studies done on the
porphyry copper deposits, very clearly shows the involvement of magmatic fluid.
So, with that in mind if we just try to see what the porphyry molybdenum deposits
generally do have an antipathetic relationship with copper in terms of the distribution the
areas like the Chilean Andes or the regions in the West American cordillera where there
are there is dominance of porphyry copper deposit, we do not see much of molybdenum
deposits there. The Henderson and Climax deposits in Colorado and the there are some
such rich deposit of molybdenum which are not associated with or not in very close
special association with the porphyry copper deposits. Although, many of the porphyry
copper deposits do have concentrations of molybdenum in insignificant quantity, here
the differences which have been found out in such cases are that the parent magma is
more enriched with fluorine and other volatiles. So, apparently, it looks like that the
source, the magmatic rock, which gives rise to porphyry molybdenum deposit, is more
felsic in its composition and have a very high concentration of the volatile components
like, fluorine and other volatile species. It is indicated by presence of topaz and
abundance of fluorite in the alteration zones and mineralized domains in the porphyry
molybdenum deposit and one of the important differences is the critical parameter, which
is the ratio of the Cw,l 0 by Cwl,s that is the initial water content divided by the water
content at saturation is generally very high in case of molybdenum deposits and is low in
case of copper deposit. Because of the very inherent, difference between these two
elements molybdenum and copper, copper is more compatible than molybdenum in its
nature although, porphyry copper deposits are abundant in the other parts, say Circum
pacific region.

So, this is what exactly we have been seeing, that in the Circum pacific region, Iran,
China, and many other in the Chilean Andes, these porphyry molybdenum deposits are
rather rare and mostly confined to the Western American cordillera. The rich
molybdenum deposits appear to be associated with a rift phase, which is actually not
very conclusively known in case of the porphyry copper deposits. Molybdenum deposits
are associated with the magmatic bodies, which are product during the convergent type
tectonics settings, where the richest part of the porphyry molybdenum deposit are
associated with a situation, which more corresponds to a rifting phase where you have
highly evolved rhyolitic and alkaline kind of magma which gives rise to porphyry
molybdenum deposit, which is not known in the porphyry copper deposit situation;
whereas; the alteration characteristics are more or less similar in the two types of
deposits.
Fig. 14: Geologic cross section of a typical porphyry tin deposit.

We do have the other type of porphyry deposit, which are the porphyry tin deposits (Fig.
14). They are mostly spatially, if we look at the Chilean Andes margin, a little to the east
of the porphyry-copper belt, typified by the Bolivian tin belt, which are observed to be
occurring to the continental side from the Andean margin. And, so, more or less
conforming to the similar kind of architecture, the porphyry tin deposits. The only
difference is that, the way we saw the stock, in case of the porphyry copper deposits,
which is more cylindrical and is emplaced in the form of a porphyritic stock, with a small
plug like body, maximum occurring within just about a 1 square kilometre or so. In the
porphyry tin deposit, the magmatic body is characteristically inverted cone shaped kind
of body, and the potassic alteration zone generally misses from this porphyry tin
deposits, and here, it is also observed that the fundamental difference between a
porphyry copper and a porphyry tin deposit is that, the parent magma, which gives rise to
the porphyry tin deposits do have a much lower oxidation state, corresponding to the
porphyry copper deposit. In fact, in the context of the tin and the copper deposit there is a
classification scheme that was proposed for the granitoids which is basically the I type
which is basically derived from igneous protolith or igneous precursor compared to that
the granitoids which are named as S - type (S standing for sedimentary), and these S type
granites represent reduced magma that can have higher concentration of Sn.

So, even though these deposits like the Bolivian tin are being labelled as porphyry type,
but there are many variations in their characteristics and sometimes there are some
amount of debate, as to whether they truly represent porphyry type or not, but as of the
present state of the art knowledge we do call them as a porphyry tin deposit.
We will discuss another class of deposits that are associated with felsic magma, but a
little different type of a situation here resulting from the interaction of the felsic magma
within the crust where there are some pre-existing sedimentary sequences and here we
broadly categorize them into the contact metamorphic or contact metasomatic
deposits. The mostly dominant ones are generally the Skarn deposits. In the literature,
the skarn deposits have been divided into 2 as the reaction skarns and replacements
skarns, but we shall not be going by this kind of classification. In general, this skarn
deposits result when a felsic intrusive body comes in contact with the rocks through
which it intrudes and is emplaced in that in the surrounding of them and then here these
deposits are observed to be confined to specific lithologic horizon. So, that is why you
can call them broadly as strata bound and they are the class of deposit are the important
sources of tin and tungsten mainly. They do also result in formation of iron skarn, iron
gold tin tungsten and molybdenum gold etcetera sometimes some rare earth mineral also.

Fig. 15 : A conceptual model of origin and evolution of the skarn system.

Let us first have a look at what has been the popular model for the formation of this
skarn deposits, or this skarn process. This skarn process could be visualized by looking
at these 3 diagrams in Fig. 15, the number 1 the first one which was existing in any
particular domain in the crust, which has been intruded by a felsic magma, which are far
more evolved compared to the kind of magma which give rise to porphyry deposits, quite
enriched with many of the volatiles for example, boron lithium and many other volatiles
including the ore forming elements.
So, when this particular intrusive body is emplaced within a sequence of these rocks then
first thing it does is that it drives out the pore fluid and then gives rise to the skarn
formation which forms something we can call as a ‘metamorphic aureole’. In this
metamorphic aureole this argillaceous units are converted to the hornfelse with typical
skarn minerals such as garnet the other minerals – this hornfelse, containing some
ferromagnesian minerals, wollastonite and diopside type of mineral which also form
along the carbonate rock contact. The dotted boundary in the figure shows that it is
converted into a metamorphic aureole thereby creating some change, basically they
make the conditions very conducive for the fluid to be further acted upon. The host the
magmatic body has caught up a fragment of the sediment as a xenolith here.

Now, in the second stage the magma when it crystallizes, it eventually expels or evolves
or exhales a magmatic volatile phase as exactly happens in the porphyry system. So, this
fluid is now channelized through the metamorphic aureole and then the horizons mainly
the calcareous horizons which were converted into the skarn, to the contact aureole are
acted upon by the fluid which are evolving from this magmatic body that is crystallized
and the fluid evolves and escapes through because this contact are providing the suitable
channel way for the fluid to flow through the country rock.

The zone which is shown as hatched here are basically the mineralization zone which
forms at this skarn, mineralization in the form of the tin tungsten oxides and scheelite
which is a Ca-tungstate. So, these mineralized zones which occur on the other side of the
intrusive contact contoured into the country rock – are labelled as exoskarn.

Deposition of minerals also take place within the intrusive granite side of the contact
which is called endoskarn, and this gives rise to we can say that this coincides with the
very, very initial phase or the phase in which a magmatic volatile is actually playing a
dominant role in the mineralization. The early phase mineralization is supposed to be the
condition as also supposed to be manifested in them and then now after the pluton has
cooled down and the system has retrograded, it is a stage in which there will be
retrograde cooling and that retrograde cooling will allow meteoric water to infiltrate and
then alter the originally formed skarns and then the skarm minerals can get altered, the
hornfels and the other part of the system and we also do see some later stage of
mineralization in the form of metal sulfides which actually overlaps or later overprint the
earlier mineralization episode and still preserve. So, the source of the fluid in this kind of
skarn is of course, a dominantly a magmatic source is always identifiable with
temperature even going well above 600 degree centigrade and is of high salinity. So, as
far as this skarn deposits are concerned, although all over the world they are observed to
be occurring in different tectonic regimes. A high angle subduction oceanic type of
tectonic setting is observed to be giving rise to iron copper and gold skarns. We do have
a kind of subduction against the continental lithosphere with moderate angle moderate
dip which gives rise to tungsten molybdenum and sometimes zinc and lead also.

So, this possibly will explain why we do sometimes have a bit of a problem in
categorizing the deposits as to whether it is a porphyry tin or a skarn, but they can very
well be distinguished on the basis of the exact morphology of the type of the intrusive
and the exact mode of occurrence of the mineralization which is stratabound in case of
the skarn deposits. The magma of skarn deposits are mostly very evolved and alkali
type of felsic magma, which give rise to the tin deposits, the tin skarns and they are more
richer, say you could see here some of them also do have uranium, beryllium and
lithium and the ones which have the maximum concentration of the elements like
lithium and beryllium and these also do have sometimes development of tourmaline in
the country rock because of this boron metasomatism.

Pegmatites are generally rich source of tin, tantalum, niobium, cesium and sometimes
uranium. The salient features here that they are they occur from near surface to as deep
as 11 kilometer depths. There is a classification scheme followed for the different type of
depth range. But essentially the pegmatites represent extreme situation of a fluid
saturated felsic magma, that evolves in such a way, that the last stage the residual melt
almost get changed to a to almost like a fluid like mass and get separated out of the
parent crystallizing granitic pluton and they form veins along weak planes (foliation /
fracture). So, pegmatites are essentially seen as veins in different types of rocks and in
some situations, they do have been labelled as metamorphic the only example of it being
one of the deeper pigmented body occurring at the Rossing pegmatite in Namibia which
uranium-bearing. Pegmatites represent the extreme case of fractionation of water -rich
melt from parent granitic melt and they are rich in the volatiles the large ion lithophile
elements, the high field strength elements and they occur as veins traverse into fractures -
weak planes. They are often zoned depending on the kind of a country rock and
depending on the compositional characteristics and the rate at which these pegmatites are
crystallizing. They give rise to zoned pegmatites. So, essentially since the pegmatites are
essentially characterized by very, very coarse-grained nature and then the constituent
minerals like quartz K-feldspar and mica. So, pegmatites are actually in fact, the most
important and rich sources of industrial mineral like mica. and they are also rich sources
of graphite. They occur as extremely coarse grained and sometimes these are the
pegmatites which give rise to the gem variety of many of the minerals like beryl,
tourmaline which are much sought after and they are the most and the richest sources of
this kind of gemstones in many parts of the world including India.

So, with the pegmatites, many of the others, features of uncertain affiliation we now we
now closed we now complete the discussion of the hydrothermal systems or the
hydrothermal mineralization associated with felsic megmatism and we will switch over
to a situation which is another class of deposits, where the situation is a little bit
different.
Fig. 16: A conceptual model of origin of the lode-type gold deposits in granite-
greenstone rocks – generation, flow of fluid and formation of lode-type deposits in
shallow to intermediate crust.

So, we will be switching over to this particular class, a very important class of
hydrothermal deposits which are the lode- type gold deposits in many older cationic
blocks in the world like the Abitibi province in Canada, Dharwar Cotrona in India
Yilgarn block in western Australia, Barberton mountain range in South Africa and so
on. So, these are the deposits which are the lode- type gold deposits in granite greenstone
terrains, these are widely believed to be a metamorphic hydrothermal system. So, we
will see these deposits and see the role of metamorphism in giving rise to or in giving
rise to such kind of a hydrothermal system.

So, these are the deposits which are extensively studied all across the continents and are
the rich sources of gold all over the world including the richest gold deposit in India,
which is the Kolar gold (now closed) deposit from where the substantial amount of gold
was produced in the country. Right at this moment also there are other occurrences
where gold is being produced. So, let us see these deposits through the model depicted in
the figure above. In this model what we see here is that there is granitic body which is
basically a syn-kinematic granite (contemporaneous with metamorphism and tectonism).

What is shown here in Fig. 16 is amphibolite facies metamorphism partial melting Now
what exactly is happening here is that it is being shown that this mass of rock, they are
undergoing high temperature low pressure metamorphism and during this metamorphic
process there is devolatilization of the sediments undergoing metamorphism and there is
generation of copious amount of volatiles which are essentially dominantly water and
charged with variable concentration of carbon dioxide and S-species in this fluid. It is
different from the ore fluid exsolving from felsic magma of porphyry systems. What gets
metamorphosed is thick volcanosedimentary pile that actually formed on the sea floor
(greenstones) and acquired its chemistry through interaction with seawater. Now recall
the diagram which we discussed previously while discussing the role of pressure. The
fluid which is being generated here are experiencing high pressure, in excess of what is
actually expected a lithostatic pressure here, because this fluid is somehow not being
able to escape because of the low permeability of the rocks which are lying above. Now,
what is represented as these vertical structures are the ones which are the crustal scale
shear zones or the faults, which are created through the process of deformation of the
crust of the lithosphere. They are deep seated fracture or the shear zones and now they
become the channels through which this fluid could escape, because once this crustal
scale weak zones are created they are the zones in which the pressure is reduced. And so,
this fluid which is present in much high pressure will always be channelled through these
kinds of crustal scale structures.

Now this fluid on it upward migration is likely to, encounter diverse the host rock type
for the occurrence of these gold deposits as observed in many different parts of the
continents, for example, here we have a mafic body which is a unmineralized iron rich
tholeiite, and this fluid could possibly may be passing through such kind of rock and this
this horizon is a chemogenic sediment which is a BIF the fluid could also encounter a
horizon like this, there could be some carbonaceous sediments which will be having a
environment which will be reducing and also the fluid might get ponded within that kind
of a horizon here and deposit gold in response to reduction in pressure, interaction with
different rock types. These crustal scale shear zone themselves will be the locales of
deposition of this huge amount of silica that is dissolved in this fluid which is generated
as a very high-pressure temperature conditions and will be present as what we call as
mega veins or lodes and the way we see them in different parts that they constitute the
host of gold deposition.

So, number one is, that they might occur as lodes means whatever is present in a shear
zone which could be running for several kilometers in it is strike length and is of
substantial crustal depth extension and will be characterized by complicated intense
deformation signatures - mostly they are shear zones and we see them that they are
present as gold quartz lodes. So, here we get free gold deposited along with the quartz.
The second other possibility is we get them as lodes with quartz gold also sometimes
some amount of sulphide minerals like pyrite arsesnopyrite also associated with them.
We get them within the BIF where Fe of the BIF reacts with gold-bisulfide complex. the
iron oxide phases in the banded iron formation and formation of the sulfides as host of
the gold which is liberated within this from the fluid which traverses through this and
encounters the banded iron formation. A mafic body may also act as a trap as per the
same mechanism as BIF (Fe in mafic rock gets sulfidized releasing the god).
Carbonaceous a sediment also act as trap by inducing reducing condition at which the
gold is deposited. The lode-type gold deposits associated with metamorphosed
greenstones are typically late-Archean to lower-Proterozoic and are also known as the
‘orogenic gold deposits’ occurring in almost all cratons. These greenstones, specifically
the ones which start from very high MgO bearing basalt, which are the komatiites and
give rise to sequence of tholeitic basalt evolving with bimodal volcanism chemogenic
sediments such as the BIFs, clastics and Felsic volcanic units.

But the model of course, proposes that there is no need to have litho units with a higher
concentration of gold, because the capability of this fluid, which is liberated during the
process of metamorphic devolatilization is efficient enough to carry gold, in substantial
concentration and the popularly held belief is that, the maximum amount of gold is
deposited, at the amphibolite-greenschist transition and this is how the rich deposits are
observed with the shallower lithologies, although mineralization saw with a continuum
up to higher amphibolite or granulaite grade is also observed in some of the deposits.

Fig. 17: Location of Carlin-type gold deposits in western USA.

So now we will switch over to a new class of deposit, which are also a very important
source of gold, these are the Carlin type gold deposit and here (Fig. 17) is a map of the
Western United States of the state of Nevada, which has been magnified here.

So, these deposits we could see is a classic gold belt in the Western American Cordillera
and these deposits are essentially associated with a sedimentary sequence. Although the
fluid that caused in the mineralization, is not necessarily a sedimentary or a connate
fluid, but it is one of the most complicated, most intricate, one of the most complicated
deposit types, but they are very rich gold occurrences, which are very much sought after.
Very active exploration goes on in this region for discovery of new deposits. Some of the
localities like Carlin and all these areas in Nevada constitute the major occurrences of
Carlin type of gold deposits. They occur in Paleozoic marine sedimentary sequences,
formed in accretionary zone and during and after the deposition of this Paleozoic
sedimentary sequences, they were subjected to compressive regime and they were
intricately thrusted during the Mesozoic tectonic activity and they acquired a very
intricate Mesozoic tectonic fabric. Essentially the sequence consists of argillaceous and
calcareous rocks and then in the post Mesozoic this terrain experienced magmatic
activity, in the form of intrusion of some of felsic rocks in form of stocks, as well as
dykes broadly granitic in composition and here the speciality of these deposits is that
gold occurs extremely fine grained nature, associated is with silicification and quartz
veining.

The mineralization essentially is by replacement of the calcareous rocks by silica which

is termed as jasporoid in this particular type of deposits, and gold occurs as thin coatings
on pyrite on surface of amorphous carbon and also dispersed in auriferous pyrite and
realgar, here the ore fluid is essentially, a low saline carbon dioxide containing and H2S
containing fluid which resembles sometimes to, some of the epithermal mineral deposits.
But they are being classed as their individual type, which are named after in the most of
these deposits were studied and their distinctiveness were brought out, clearly there is a
role played by the late granitic intrusive. Gold and the fluid in terms of sulfur and the
complexing species, were contributed by these felsic magma and these mineralization
resulted and this is tentatively or this is a very simplistic way, of presenting the origin of
this kind of very important class for deposits, they are not only confined to the Carlin
trend the in the in the Western United States, there are similar type of deposits which are
also reported elsewhere.
Fig. 18: The Olympic Dam deposit – a plan view of the mineralized zone in a granite
body.

We would now go over to discuss another very special type of hydrothermal system
which is the iron oxide copper gold (IOCG)system, and actually this particular class of
deposits came into limelight after the discovery of the Olympic Dam deposit in South
Australia, which can be told as one of the major discoveries of the recent past, in the
history of mineral exploration, where a huge concentration of copper gold and uranium
was found in a body of a brecciated granite. The ore zone is a brecciated zone with
hematite that led to categorization as Iron Oxide Copper Gold deposits. The deposit has
huge tonnage of copper with gold of 0.5 g/tonne. The breccia complex within granitic
rocks is in the Gawler craton in South Australia. Occurrence of such kind of
mineralization in a in a granitite in a continental interior was not known till that time.
Fig. 18 above is the plan view of the deposits and figure below is a cross section. The
Roxby Downs granite, within which the breccia complex occurs is almost 4 to 6
kilometers of area, and is essentially covered by later sediments, and the majority of the
ore body is a lenticular subhorizontal within the interior of the breccia complex. Figure
shows the disposition of the ore in the subsurface section.
Fig. 19: Geologic cross section of the Olympic Dam deposit – an IOCG type deposit.

As you can see here (Fig. 19), this is a cross section of the Olympic dam deposit, where
the breccia complex and the mineralization is shown. The lithology is a mid Proterozoic
sequence, of the granite and the mafic and felsic dykes and the breccia zone, which
contains the mineralization. If we look at one of the ore body in it is subsurface section,
we get a clearer idea as to what the mineralization is like. There is clearly a richer
mineralization of copper in form of bornite, it straddles the lower grade or the
chalcopyrite zone, and the uranium mineralization is pretty distinct, and occurs as an ore
body in the upper part. This deposit led to a lot of speculation about, the origin. The fluid
characteristics does not indicate a very clear-cut magmatic source, but from the
temperature and salinity value of this fluid that gave rise to this Olympic Dam deposit,
does indicate that there has been involvement of more than one type of fluid in giving
rise to this mineralization. The popularly held view is that it evolved by mixing of 2
fluids - one, an oxidized fluid with sulphate and a reduced fluid. And the deposition of
metals was brought about by inorganic reduction of sulfate. While the oxidized fluid is
speculated to be an evolved mamatic fluid, the reduced fluid could be a connate fluid.
The deposit in itself is a distinct type which is different from the porphyry type deposits
or any of this skarn type of mineralization. In the most simple term possibly, it could be
thought of is some kind of an epithermal system, but it does not have any such kind of
alteration zones as we see in the porphyry copper or epithermal deposits.
They were discovered in many other areas in the world although with a lot of differences
in characteristics

Epithermal Deposits in Young Volcanic Islands (Cu, AU AG)

Fig. 20: Distribution of Volcano Associated Epithermal Deposits in the circum Pacific
ring of fire.

Now, we would like to go over to a very interesting class of deposits, which are
essentially known as Epithermal deposits, in young volcanic islands. We have been
seeing through such kind of maps of the pacific ring of fire (Fig. 20) and the deposits
which we are going to discuss now, are distributed all around is of the Pacific plate or
what is basically known as the circumpacific ring of fire. The important ones we could
see in the figure, just about near the Papua New Guinea island there is one small island
which is the Lihir island which holds a very rich important gold deposit, the Ladolam
deposit. If we see the Japanese island arc, there are some deposits like in the Kyushu
province - there is the Hishikari deposit - one of the very rich gold deposit. In the
Western Margin of this South American continent and the Western American Cordillera.
we get series of such deposits, which also are essentially epithermal essentially meaning
that, they are confined to the top 5 kilometer within the earth’s crust - means the active
ore forming process is within that kind of a depth range as compared to many of the
deep-seated hydrothermal systems, which we have discussed so far are dee seated. These
are the near surface operating hydrothermal systems. So, here as you can expect that, the
young volcanic islands are definitely responsible for formation of such kind of deposits.
So, as far as this particular class of deposits in the young volcanic islands are concerned,
these deposits are broadly classified into 2 types, the low-sulfidation type and the high-
sulfidation type.

On the diagram the ones with open circles or open square are the high sulfidation ones,
on the filled circles and filled squares as the low sulfudation ones and ones as you could
see in the figure, the high sulfidation ones, are occurring in the Chilean Andes in the
South in the Western Margin of South American continent are very closely, specially
associated with porphyry copper deposits. So, that means, they must be having some
common parentage as far as the mineralization process is concerned, and in most such
deposits it is observed that they do have a very close time relationship, they are mostly
synchronous or at the same time as formation of this porphyry copper deposits, which
themselves are very young. Deposits such as Ladolam, which is almost about 400000
years over this 0.4 million years old.

So, these deposits give us ample scope to understand the hydrothermal ore farming
process, we can call them almost as present day ore forming systems. So, the distinction
based on the classification is the low sulfudation and high sulfudation is essentially based
on the oxidation state of sulfur - sulfur is mostly in the +6 state here, and actually the
classification based on the ratio of sulfur to chalcophile metals, it is not exactly that they
do contain a lot of sulfur, but the deposits essentially they have a high sulfur versus
chalcoohile metals and the sulphidation state is higher means, as expected the high
sulfidational deposits are likely to be dominated by mineralogy which are pyrite or
bornite, whereas, the low sulfidation ones will be pyrrhotite arsenopyrite dominated
mineralogy. Characteristically the high sulfidation deposits, have very low, going to the
low pH and their alteration characteristics are accordingly reflected in the in the
alteration zones compared to the low sulfidation deposits. High sulfidation deposits are
as dominantly of base metals like copper, and the low sulfidation deposits dominantly
are for the precious metals like gold and silver, although they will have some trace of the
each in the other.

What is more interesting is that, the low sulfidation in similar geological terrain like the
Japanese island arc, can have, as you can see from the from the legends here, both can
have the low sulfidation and high sulfidation deposits. So, as would be expected
occurrence of the low sulfidation or high sulfidation has some local controls, although
broadly the kind of volcanism of the composition of the host rocks, would look to be
more or less similar.

Fig. 21 : A geologic cross section of a high-sulfidation epithermal deposit.

Here is a cross section of a typical high-sulfidation epithermal deposit (Fig, 21). So, we
shall just briefly look into the characteristics of these high sulfidation and the low
sulfidation deposits, to the left is a cross section of a high sulfidation deposit, where it is
observed that the deposits occur very close to the volcanic center. This is an example of
one high sufidation deposit in Philippines where the porphyry deposit in the close
vicinity is also shown, and the way the migration path of the fluid and the decreasing
trend of the temperature is shown. So, they are less than about a kilometre within the
volcanic center, and their depth range is about within 1.5 to 2 kilometers from the
surface, this is a classic example and they are sometimes associated with breccias, and
interestingly, these ore bodies do have an inverted teardrop type of shape, and they are
essentially associated with something which is a very interesting feature, which a
residual and vuggy silica, which indicates that before the mineralization episode the fluid
which interacted within this particular zones was extremely acidic in nature and it
almost dissolved out the rest of the component just leaving behind the vuggy silica zone.
Later on, the metals were deposited as metal sulphide in this vuggy silica zone, that is
basically the mineralized zone and they are they are surrounded by the alteration, which
is advanced argilic alteration, which is alunite bearing and kaolinite bearing advanced
argillic alteration and with peripheral argillic and propylitic kind of unaltered situation
also is observed. Hydrothermal brecccia coincide with the ore zone and here, this kind of
brecciation within the mineralized zone does indicate that there must have been some
boiling of the fluid, which caused the hydro fracturing and formation of the breccia and
this is kind of a thing which is a model for the origin of the high sulfidation deposits,
setting of an acid alteration and high sulfidation ore formation and ore forms.

Fig. 22: Cross section of a high-sulfidation epithermal deposit showing the fluid flow
and alteration characteristic.

So, here (Fig. 22) this zone is the formation of ore with the temperature (of ore fluid)
contours shown, and as you could see here the ore fluid generally is of high salinity,
below this there is a zone which defines the fluid characteristics to be of higher
concentration brines, compared to the ones which is causing the mineralization by
effectively by dilution with meteoric water during the process of mineralization. So, the
deposition is in response to mixing of meteoric fluid with acid gas rich fluid, rising from
underlying magma chamber, the magma chamber is responsible in providing the very
acidic sulfurous vapour, that condenses into the meteoric fluid and becomes very acidic
in it is nature, sulfate rich and cause the alteration value right type of alteration and they
are very typical of the high sulfidation deposit.

The low sulfidation deposits as against the high sulfidation ones,

Fig. 23: Geologic cross section of a typical low-sulfidation epithermal deposit.

have an overall is higher pH than the fluid which is involved in the formation of the high
sulfidation deposits. They generally do have different types of ores - disseminated, vein
type, and as well as the hot - spring type are deposits. In fact, these are the deposits
which were earlier classed as the as the geothermal type or the hot spring type, because
of their close resemblance to the geothermal systems. They are associated with the hot
spring or the sinter type of ore deposits where we get sometimes good concentrations of
arsenic and antimony sulfide in form of realgar and orpiment and also mercury deposits,
which resemble very much like the sinters on the hot spring, vent of the hot springs in
different parts.

One major distinction of these deposits is that, they do occur distal to the volcanic center,
they can be away from the volcanic center by even 5, 10 kilometers from the active
volcanic center. A shown in the figure, the disseminated ore, this gold silver vein ore,
and a magnified view of these veins shows the alteration to chlorite - calcite - epidote
type of alteration, smectite mixed layer alteration,. sericite type of alteration, and and
more typically adularia which is a low temperature polymorph of K- feldspar which also
is stable is also associated with the sericiting alteration zone around this kind of veins.

And since these assemblages are stable at pH higher compared to the assemblages which
have the alunite type of alteration minerals. So, in general they indicate that this system
was operating with the fluid, which was near-neutral in the stability field of K-feldspar.
Fig. 24: Process operating in a low-sulfidation epithermal deposits.

Fig. 24 is a schematic diagram on the origin of such kind of deposits. In the low
sulfidation, they are generally gold silver type of deposits. The deposit which occurs in
the Kyushu province of Japan, the famous Hishikari deposit belongs to this category,
where we get these deposits in forms of discrete veins, and which has the alteration
zones dominated by sericite and adularia.

So, what is basically inferred from these deposits is that, they are more akin to the
geothermal systems where we see a much broader scale of fluid circulation, where the
mineralization is generally confined to the fluid up flow zones. The fluid generally is in a
hydro thermal convection cell set up because of the heat that is produced by the
intrusives at depth, and such fluids flow to the subsurface they get richer in silica, and
they scavenge the metallic components and then in the up-flow zone they undergo
boiling, and which comes out as a very efficient mechanism for deposition of the sulfide
minerals from them. They do sometimes also have this fluid which are essentially within
200 to 250-degree centigrade temperature, and have a very significant meteoric water
component. The pH of the fluid is within the stability field or K feldspar, and also
sometimes we get calcite in the mineralogy. And the minerals are deposited in fissures
veins in such systems.

The present-day hydrothermal systems operating on the young volcanic islands are
interesting as far as the present-day ore forming processes are concerned giving us direct,
proof of involvement of such kind of fluid in mineralization.
Volanogenic Massive Sulfide (VMS) Deposits

Fig. 25: Location of major present-day seafloor hydrothermal sites.

Let us move on to discussing a very, very important class of deposits. So, from the
continental, we will now go towards the oceanic or the seafloor hydrothermal systems.
Here, the purpose of showing this diagram is again we could see the Pacific ring of fire.
And I would like to draw your attention to the areas which are indicated by these solid
circles. And as you have seen them before, they are the mid oceanic ridge system of the
lithosphere measuring about 55,000 kilometers in total length. The MOR system have
been investigated by submersibles, and seeing the processes that is taking place. In one
of the previous classes, some of the features such as black smokers which are observed
on these this kind of ridge ocean ridge system.So, the hydrothermal activity associated
with the ocean ridge system. We saw their photographs as so many such features can be
seen. Some of the important localities which are marked here is the TAG (the
transatlantic geo traverse), Snake Pit, then the 21 degree east pacific rise (EPR) and so
many others such as the Guaymas basin geothermal system, and there are many like
associated with back arcs for example, the Lau basin. The entire ridge system either on
active rifting or on the back arc, such locales are active sites of hydrothermal activity,
and they result in hydrothermal mineralization. They are observed in black smokers, and
sulfide chimneys which form on this kind of hydrothermal vents and are so very similar
to the mineralogy of the deposits, which we are going to discuss right now which go
under the class of VMS deposits, which are an important class of deposits contributing
Fig. 26: An idealized cross section of VMS deposit.

the base metals - copper led and zinc. Some of them also do give metals like gold as by
product. The VMS deposits in fact have been variously classified. They are classified
based on composition like copper dominant, copper zinc, or lead, zinc, copper. These
deposits are essentially ocean floor hydrothermal systems and are associated with 2
broadly different kind of tectonic regime. The rift related regimes, they present in
addition to what we see on the presentday ocean floor. There are some of the deposits
like one occurring in the in the Cyprus and the Troodos ophiolite belt – the Cyprus-type
deposit (deposits similar in nature and in older cratons are labeled as Cyprus-type).

An ancient copper deposit occurring in the Abitibi belt, in the Quebec province in
Canada which is the Noranda deposit. So, this type of deposits do have something in
common they are essentially copper rich deposits, and they are associated with mid
oceanic ridge type of extensional regime or rift kind of setting. And they are broadly
known by the term as Cyprus type. Essentially this type of deposits are in the open ocean
mid oceanic ridges, where we could only expect the volcanic components. So, these
deposits are essentially devoid of any clastic sedimentary units, because they do not get
any sedimentation on the site where the rifting is taking place. But they can have
chemogenic sediments, and the ones which are observed in the present - these deposits as
was also shown in the temporal spectrum, range in age from Precambrian to recent. For
example, the Cyprus type deposits which are associated with the Oman ophiolite, are
very young deposits. We do not get much of felsic counterpart there. Kuroko-type
deposits are essentially associated with the island arc and are mostly associated with
felsic volcanic units. and they are essentially Pb-Zn deposits. They do occur much later
in the geological history. The third type of deposit the Besshi-type of deposit are also.
associated the rift settings. But because of their proximity to continents, this type of
deposits which are also copper or copper-zinc deposit. There by virtue of their proximity
to the continent, they do have a significant member of clastic sediments in them.

Fig. 26 is a generalized section of the VMS deposit where we see is typical morphology.
The footwall volcanics have the feeder dyke with stockwork of mineralized veins
indicating that there must have been the zone through which the fluid has been
channelized. The major part of the mineralization is in the form of bulbuous lens, which
is the massive sulfide lens. The name massive sulfide is derived from the fact, that these
deposits are essentially rich deposit with high grade of the metals like copper or lead or
zinc and can be substantially higher with low tonnage. The feeder zones will be
characteristically surrounded by an alteration zone or alteration pipe which is essentially
a chloritic and sericitic alteration, because alteration of the ferromagnesian minerals in
the basalt will essentially give rise to chlorite. And this massive sulfide deposit, once it is
formed it also could be later on covered by the hanging wall volcanics, because it is a
zone where constant volcanic activity is going on with sometimes maybe a chemeogenic
precipitation of siliceous or ferruginous component could also be there.

Fig. 27: Cross section of two classic Cyprus-type VMS – the Noranda Deposit, Quebec,
Canada (Precambrian) and the Cyprus deposit.

Now, on that backdrop, let us see a cross section of the deposit that, I just mentioned is
Noranda in Quebec Canada. And this is the cross section of the cyprus deposit, where we
would roughly identify this footwall and the hanging wall units. And they do have some
kind of a zoning and here is the in case of the Noranda deposit the stock work zone is
here with the alteration pipe. There is vertical zoning of metals copper-rich at depth
giving rise to zinc-rich upper part.

Fig. 28: Cross section of the young Pb-Zn Kuroko-type VMS in the Japanese Island.

And this one (Fig. 28) is from the is a typical cross section of a Kuroko deposit, where
we see that the rock is felsic rhyolitc dome. And there is also this late stage sulfide veins,
then the top and this is the feeder dyke. And in the Kuroko terminology, the ore is known
as the ‘black ore’ which is shown here as this blanket of the black ore. And this is the
yellow ore which is chalcopyrite- pyrite, and the black ore is essentially lead-rich ore.
The mineralization is also associated with some barite. In the assemblage - barite as well
as gypsum, indicating that the fluid is essentially the seawater.

As regards to the geology of these deposits, they are present in quite diverse situations
like the Japanese arc is essentially a zone of convergent plate tectonics setting, the
difference with the ones in divergent zones lies in the composition of the volcanics,
which is dominated by the seafloor basalt. The convergent type setting has bimodal
volcanism and sometimes is more of a felsic component which dominates here like
Andesitic type of bodies. Situations in back arc like this Lau basin is essentially
sometimes the tectonic settings is of a mixed type or a composite type, where a
convergent setting is also associated with a back arc spreading center where, we get the
bimodal type of volcanism and the desired conditions or the conducive conditions for the
formation of such kind of a mineralizing system. Mineralization is resulted by the setting
up of huge hydrothermal convection cells through the heat that is generated from below
that percolates through the dense fracture network in the seafloor basalt and interacts
with the seafloor with the seafloor basalt and gets enriched with respect to the ore
constituents the metals. And then deposits them in the form of sulfides on the vents of
this hydrothermal fluid when they get discharged on the way up after they become
buoyant which will have a look

Fig. 29: Mechanism of formation of a typical VMS on the ocean ridge.

The model for this kind of the formation of the volcanogenic massive sulfide deposits
have been worked out (Fig. 29). The essential components of this model is that it should
have a sub volcanic intrusion to provide a sustainable source of heat. For the for the
process to operate in these zones and initially this zone is an impermeable barrier, which
is dominantly constituted of quartz (silica). It could either be a result of a very low pH in
which most constituents could have been leached out from this particular area and only
been converted to a silica rich zone, impermeable barrier or it could be any kind of a
process of actually deposition, through some tuffaceous kind of material which could
have formed this impermeable barrier. So, by that process in this zone, where the fluid
by rock ratio is low and the pH of the fluid is very low as well. And it builds up the
pressure and then there are channel ways which are created in the form of these faults,
which is shown here, and the fluid rises and on this particular zone which is above this
barrier. The sea floor is the hydrothermal circulation cell as I was talking about is shown
here with this arrow and the fluid.
The sea water percolates through this fracture network gets heated up, interacts with the
rock here, here the water wave rock ratio is high much more than one and also pH is
higher compared to the fluid over here which carries the metals and also the metal which
is leached from the sea floor basalt. And here they this is essentially the site where the
hydrothermal fluid vents out and the deposition takes place in the form, what we have
just seen the form of the sulfide chimneys or the dominant sulfide minerals they formed.

This is the situation where we are essentially looking at the process which is giving rise
to the massive sulfide lens, exactly on the site where this kind of a hydrothermal venting
is taking place. So, such kind of a sub volcanic intrusives which is required for this
process to be carried agree agrees well with most many of the fossil hydrothermal or the
VMS deposits, which is which we see in older cratonic blocks and deposits on it varying
edges that they are is. In fact, associated with such kind of a felsic intrusive body in the
subsurface and the volume that is calculated for the generation of the heat agrees well.

Sediment-hosted Massive Sulfide Deposits (SMS)

The sediment hosted massive sulfide deposits or which are abbreviated as the SMS is
kind of analogous to the volcano genic massive sulfide is VMS. They have been
variously named; they were they were the deposits which we know as SEDEX type of
deposit or synsedimentary exhalative type of deposits meaning that the process involves
interplay of fluids (with or without metals) from deeper sources that were debouched to
the basin during deposition of sediments where we observe the SMS deposits. We shall
prefer to call them as the SMS the way we have been naming the hydrothermal systems.

Fig. 30: Typical style of SMS deposits.

They are in fact, distributed in all almost all the continents and are quite rich in terms of
their quantity in tonnage contributing most of lead and zinc. The Sullivan deposit in
Canada is one which is worth mentioning. Mount Isa mineralizing system in Queensland
in Australia and also the MacArthur river basin in Australia, Rammelsberg in Germany,
the Irish deposits and some important occurrence in NW India (Zawar, Rajpura Dariba
in the northwestern India the Aravalli fold belt). Mineralization is dominantly in marine
or continental sediments, pyritic carbonaceous shale or platform carbonates, sometimes
the presence of a tuffacious horizon. They are essentially Stratiform in nature as could be
seen from the diagram and have an idealized morphology like the one shown in the
figure, where we can we see that there are synsedimentary basinal fault which is
invariably present and there is a brecciated zone which is also present and there are
proximal sulfide mineralization in the form of the sedimentary hydrothermal facies,
where sphalerite, galena, pyrite, pyrrhotite chalcopyrite mineralization is associated and
also a distal sedimentary facies with barite, carbonate. In terms of the grade, they are
rather lean type of mineralization or low grade whereas, the proximal one is the rich
mineralization and there are some post or sedimentary rocks. What exactly is observed is
that the sulfide body is pretty much conformable with the sedimentary strata, like what
we get in the VMS deposits - the pre ore sedimentary rocks and constituting of different
facies, the feeder pipe and the vent complex. In the figure, the crosshatched part is the
vent complex and this is how is the general morphology of the SMS deposit. They can be
called stratiform mineralization. The lateral zoning is prominent, but not the vertical and
they are always associated with synsedimentary fault. They are not associated with any
significant or prominent magmatic component.

Fig. 31: Conceptual exhalative model for the SMS deposits.

Fig. 31 is a conceptual model for the exhalative conceptual model for SMS deposit,
where the hydrothermal fluid could be squeezed from the reservoir rock which is the
reaction zone could be are arenaceous / argillaceous rock. The hydrothermal fluid rises
through a feeder zone with a moderate or subtle hydrothermal. But one can always
imagine analogous to a situation what happens in case of a volcanogenic massive sulfide
that there could be some magmatic / volcanic activity which could be there in the
subsurface providing the heat and because this fluid has to be buoyant and has to be
compressed and move upward and mix with basinal water. So, it also depends on the
volume of the rock that is involved it would require if it, if the metal has to be only be
derived from this sedimentary pile then it definitely would require a far greater amount
of the rock to be involved and the fluid to be squeezed out from this sedimentary horizon
and to be channelized to such kind of system as it as shown here.

Fig. 32: Temporal distribution of VMS and SMS deposits.

Here (Fig. 32) is a brief comparison of the temporal spectrum of these deposits, they
range from early proterozoic to end of the paleozoic. So, the frequency of occurrence is
far more within the Proterozoic as compared to, the volcanogenic massive sulfide
deposits which range in age from Archean to Cenozoic, . these deposits are not found to
occur in rocks which are younger than Paleozoic, the Mesozoic and Cenozoic
sedimentary basins seem to be devoid of these deposits which is the reason why it is not
very well known, why is it so, but there is an observational fact
Copper in Stratiform Sediments (SSC)

Fig. 33: Cross section of the Kupferschiefer – a typical copper deposit in stratiform
sediments (SSC).

The sediment hosted stratiform copper deposit or the SSC deposits are a major
contributor of copper. They possibly are next to the porphyry copper deposits accounting
for 20 to 25 percent of the world’s copper production and more importantly they are also
a resource of cobalt. Two important occurrences can be quoted as far as this important
deposit type is concerned the one is the Zambian copper belt in Africa which is a huge
copper bearing black shale horizon wherein a reducing condition likely prevailed that
caused deposition of copper sourced from continental red beds. The other one which is
shown in Fig. 33 above is known as the Kupferschiefer which is essentially a copper
bearing black shale horizon. The Kupferschiefer is a very unusual situation where this
particular horizon has a total area of coverage about more than 600000 square kilometer
distributed over about 7 countries in central Europe - Germany, Poland and the UK.
They are definitely some very selected areas especially where it is exposed in Poland and
some other areas where they are being very actively exploited for the metal copper and
cobalt. The ore is in reduced black shale horizon with associated continental red beds and
evaporites. The association with continental red bed is very prominent and very critical
to the situation of the SSC deposits as well as evaporites. Because the evaporites bear a
bit of significance as far as the hydrothermal system in general are concerned, most of
our ideas coming from the situation which prevails in the Red Sea where the fluid is
essentially a very concentrated briny fluid much more in salinity than average seawater.
Because these fluids are supposed to be derived by dissolution of these evaporite beds
which are the beds of the salt which result because of the evaporation of seawater in
landlocked basins. And they are predominantly stratiform even more stratiform
characteristics than the SMS and much larger lateral extent. They are fine grained
disseminated copper sulphides - chalcocite, bornite, chalcopyrite some amount of
significant lead zinc and silver.

This mineralogy is very characteristic in this sense that the minerals like chalcocite or
diginite and copper rich type of minerals which are generally observed in low
temperature environments or in this supergene sulfide enrichment kind of zone in
existing deposits. These are the kind of mineralogy which dominates the sedimentary
stratiform copper deposits like what we see in the Kupferschiefer or the Zambian copper
belt and there is no associated volcanic and there is prominent lateral and vertical zoning
that is also observed in the source.

So, mineralogically it is a copper rich system with average copper grade varying from 1
to 5 percent. The proposed genetic model is synsedimentary or syndiagenetic because the
synsedimentary process (which we just have just seen in case of the SMS deposit) is a
very efficient mechanism and that during the process of sedimentation there is some
extra input in terms of fluid or the metal from another source which can cause the
minerals deposit along with the sedimentary strata. Syndiagenetic in the sense that the
deposit formation follows the stage of compaction at very low temperature situation in
which the mineral start to reconstitute. The synsedimentary process is akin to anoxic
water column that is currently prevailing in the Black Sea which is a stratified water
column where we see that the lowermost part is very reducing giving rise to euxinic kind
of environment in which the the metal sulfides can precipitate as layers. So, the ore fluid
is always a low temperature fluid less than 100 degree celsius, but still we can put them
in the category of hydrothermal. There the association with red bed is important because
the fluid must have been at some point of time in equilibrium with hematite and must
have been oxidizing to transport metals. The overlying evaporite bed contributed to the
high salinity of this hydrothermal fluid and for the efficient transport of metals. The ore
accumulation is in response to decreasing oxidation state of the fluid on encountering the
reduced zone which is the Black Shales with carbonaceous particles which created a
reducing zone where the sulfides could favorably be deposited. Sometimes these
sedimentary strata are also associated or overly thick mafic volcanic which could
possibly provide the metals then the marine sediments. So, red beds with mafic detritus
are the possible source of metal.

As regards to the paleotectonic setting, these deposits are much expected to be in

continental rift settings, that resulted in the elongated sediment filled depressions
bounded by normal fault and the SSC deposits are absent in archaean much like the
SMS seems to be controlled by the first appearance of red beds. That is one of the very
significant aspect of these deposits that they never formed in the Archaean in which we
know that the condition was reducing.

The Mississippi Valley Type Deposits (MVT)

Another important class is the Mississippi valley type of deposits which are also the
major contributor of lead and zinc in the world and Fig. 34 is a composite diagram which
shows all the possible conditions in which we can see this MVT type of ores forming.
Situation 1- it could be a solution collapse breccia related to karstification (dissolution of
limestones), that means, they these are essentially the cavities in the limestone which we
call them as karst and there could be deposition of these sulfides metal sulfates of lead
and zinc.
Fig. 34: Various possible modes of occurrence of MVT deposits (conceptually shown on
one sketch – different deposits have specifically different modes of occurrence)

The situation 2 could be a collapse structure resulting from thinning of underlying beds
and subsurface drainage and here it could be a facies change with / without reef at
boundary relation to unconformities. It is not exactly known whether they are related to
unconformities, but there is a facies change in the sedimentary horizon and they seem to
have been controlled by this process They could be on a basement high which is shown,
the mud bank or the talus or pinch out kind of structure, drape kind of structure and the
reef in the limestone.

So, essentially this Mississippi valley type deposits are characteristically hosted in
carbonate rocks and there could be many different possible locales in which the ores
could be localized or the deposition of the ores could be controlled.
So, main attributes of the Mississippi valley type deposits is they are hosted by
unmetamorphosed platformal carbonate this sequence is just not they do not show any
indication of bit getting metamorphosed and the most preferred horizon is basically the
dolostones, the carbonate rocks they startabound. So, startabound generally indicates that
need not have to be seen sedimentary or they need not have to be seen genetic, they
rather more likely to be epigenetic; that means, the mineralization being temporally away
temporarily different or younger to the formation of the host carbonate rocks.

Mineralogy is simple - low iron sphalerite galena fluoride barite. In fact, these are the
deposits from which the most of the fluid inclusion data on these sphalerites have come
because the low irons sphalerite are far more amenable to fluid inclusion studies because
of their transparent characteristics and they provide important inputs to the fluid
characteristics. The mineralization is prominently cavity filling type as we have seen
whether it is a karst or it is a facies change or the situation to be created for the
deposition of the sulfides. They range in age from proterozoic cretaceous widely
distributed in north America, but dominantly Paleozoic there are some Australian
occurrences as well.

Fluid inclusion studies indicate a very high density, but low temperature fluid of 80 to
220 degrees centigrade and the ore fluid is very characteristic in the sense that they do
have appreciable hydrocarbon concentration. The fluid inclusions contain a significant
component of methane and other heavier hydrocarbons and they almost look like oilfield
brines and the temperature is low from 80 to 200 degree, the fluid is inferred to be
basinal that migrated for long distance and no clear indication with rift type.

So, here corresponding to the penultimate point it is very interesting. In fact, these are
the deposits from which the concept of the long distance migration of connate fluid was
proposed because of the fact that the fluid characteristics did not quite match with any
fluid that could possibly be generated from the host carbonate rocks So, good degree of
replacement in during the mineralization and then there are many ideas that were
proposed, like whether the metal and the sulfur were carried together or the metal and the
sulfur were derived from different types of fluid and those detailed discussion is out of
score for this discussion, but they are a very interesting case and this hypothesis is still
being held at the Mississippi valley type deposits a result of long distance migration of
fluid
So, this would actually mean that there must have been some kind of tectonic activity
that could have driven the fluid out of the sedimentary horizons from one particular local
and then migration of the fluid either a through a gravity type of flow or because
compaction driven flow. But, since they are basinal connate fluid, salinity will be high
and they are potential metal contributor - lots of metal like zinc and lead could be
complexed in such kind of chloride rich fluid and these deposits also, the possibility of
metals getting complex in organic complexes like some organic ligands being more
prominent in the fluid for the dip for the transportation of lead is also being proposed .

So, with this we conclude the discussion of a range of hydrothermal deposits - the
volcanogenic massive sulfide deposit, the sediment hosted massive sulfide deposit, the
sedimentary stratiform copper deposit and the Mississippi valley type deposits. They
exhibit many different types of situations, but somehow, they do have some features
which can be compared like for example, a distal type VMS and an SMS deposit could
possibly be having the similar type of morphology and attributes and so, that is how they
make a good case of comparing them in terms of the ore fluid involvement of connate
fluid for the mineral for transportation and deposition of the sulfides. So, these four
constitute a very interesting and important class of deposits which have generated
enough of academic interest in addition to the fact that they have been major contributor
of metals base metals like copper lead and zinc.

Uranium Deposits

We shall now discuss about an important metal, the deposits of an important metal; that
is uranium. We all know that it is one of the important sources of generation of energy;
nuclear energy - and it is a most sought-after metal. And we all know that the Indian
scenario is not that very good as far as the resources of this particular metal is concerned
and let us have a brief look on the important types of deposits of uranium in the global
scenario.

Unconformity Associated Uranium Deposits (Example – Athabasca Basin, Canada)

We do have many genetic types of deposits of uranium as seen before. We discussed

about the Paleo placer taking the Witwatersrand example which has been a major source
of uranium, the Olympic dam deposit which is belonging to the IOCG class and is a one
of the major contributors of uranium.
We shall discuss on 3 important types of uranium deposit contributing rich sources of
uranium and contribute a major proportion of the total uranium production of the world.
The first important category is the uranium mineralization associated with the
unconformity. So, that is how these deposits are included in this spectrum of
hydrothermal mineralization. They are essentially hydrothermal; their deposition is
resulted from hydrothermal fluid and we will see of what nature whether it is possible to
ascertain the fluid characteristics.

Fig. 35: Cross section of a typical unconformity associated Uranium deposit (e.g.
Athabasca Basin, Canada)

So, this uranium mineralization associated with unconformity constitute a very important
and rich class of ore deposits; two important locations - the richest ones are the (i)
Athabasca basin in Saskatchewan, Canada, is the most prolific and (ii) the Alligator river
basin in Australia. The famous Cigar Lake deposit in Athabasca basin which is the one
of the richest in the world and where uranium (U3 O8) can go up to 20 percent (
compared to the kind of deposits that we work out in India, where the value can go to 0.4
percent).

As shown in Fig. 35, the ore bodies are generally sited just below straddling a major
unconformity at the base of the intracratonic sedimentary basin. So, they could be
broadly classified as structurally controlled because unconformity we all know provides
the suitable structure; where they could act as a trap for the fluid to encounter the change
in environment in which the deposit could take place.

The diagram here is an idealized morphology of the deposit, where the black part is
actually the enriched part of the ore constituting of the minerals mostly uraninite,
pitchblende, coffinnite type of mineralization associated with a friable zone. It is also
characterized by some alteration dominantly of sericitic alteration which is observed and
the immediate rock surrounding the ore body seems to be desilicified (leached of silica)
and the silica is deposited in the form of friable quartz cemented zone above the ore
body.

And in this situation; it could be granitic gneiss basement overlain by sandstone with a
prominent unconformity.

Fig. 36 – A sketch of the genetic model of a typical unconformity associated uranium

deposit depicting the process and domains of dissolution and deposition of Uranium.

As far as the origin of such deposit is concerned, let us recall that uranium is a metal,
where it is soluble in the oxidized plus 6 state and insoluble in the plus 4 state. So, the
general idea is that wherever in whatever the situation, if it has to be fluid assisted or the
fluid operated, then the fluid needs to be an oxidizing fluid which will be able to dissolve
substantial amount of uranium in any different kind of complexing. And then it has to
encounter an environment, where it should be a zone of reduction where the fluid will be
able to deposit the uranium in the plus 4 state is UO2. So, if that is the general
framework; the situation that generally believed to be prevailing in a unconformity
related uranium mineralization. The sketch (Fig. 36) shows the depositional regime in a
magnified form showing the overlying sandstone layer as the source where there is a
hydrothermal convection cell being generated and the condition is oxidizing and U was
+2
probably carried as UO2 or chloride kind of complex. And this convection, in
whichever way it is driven and, in its way, down it encounters a graphitic material as
shown, that induces a reducing condition. So, here the fluid temperature could be
anything between 120 to 200 degree centigrade and pressure corresponding to a depth of
about 2 to 4 kilometers. The unconformity associated mineralization exemplified by the
Athabasca basin is generally Paleo to Meso proterozoic in age and the mineralization is
at least about 100 million years after the sedimentation; and this is what is kind of a
model, which is proposed for the origin of this kind of deposits.

Sandstone-hosted Tabular Uranium Deposits

Fig 37 - Generalized scenario of Sandstone-hosted tabular Uranium deposits. The map

is a plan view covering large area (small-scale map).
The other important and interesting class of deposits are the sandstone hosted tabular
uranium deposits and are known as the Colorado Plateau type. The ore body is
essentially tabular and flat lying (Fig. 37) generally with relatively low-grade ores, where
fine grained coffinite, uraninite and uranium complexed in amorphous organic matter
have been precipitated in the pore spaces of fluvial sandstone. This is a general idea
about the occurrence, where this is kind of a basin which could be exemplified by a
saline lake kind of basin. The region shown is actually the sandstone - it is kind of a
mudstone, a with locations are for the mineralization in the Colorado Plateau. this
represent it as a huge area in which the uranium ore bodies are shown. The associated
lithology could be mudstone and alluvial plane sandstone. The margin is essentially the
saline lake which is known as Playa lake. A cross section (Fig. 38 shown below) would
make it clear here - so, this is the alluvial plane and this is the Playa, which is the saline
lake, and the region of mineralization is the mudflat. The basin characterized by presence
of felsic to tuffaceous material as flow that are probable source of uranium.

Fig. 38 – Cross section of a typical tabular Uranium ore body at the interface of
groundwater and reducing reflux brine of the Playa lake.
What is important here is that we do have more than one flow path of the fluid; the one
part which is there in the more oxidizing zone in the regional groundwater is shown here;
a transitional brine this is the base of the aquifer and the deposition takes place when
there is an interaction of the reflux brine from the Playa lake, which is reducing in nature
and the fluid which circulating as groundwater in the basin here in this region is
oxidizing and is supposed to have carried the uranium. And the uranium coming from the
two-process material which is present in this as shown here, in this horizon and the
uranium is precipitated.

So, abiding by the simple mechanism that if the fluid that is oxidizing here carrying the
uranium and it has to encounter a region, where it should be reducing and then the
uranium will be deposited and that is how exactly it is visualized. So, it is an interface
between the saline reflux brine and the low salinity shallow regional groundwater, which
is oxidizing and is the potential uranium carrier. Although these deposits are not as rich
as the unconformity related type, but they do contribute some proportion of the metal.

Roll-front type Uranium Deposits, Colorado Plateau

Fig. 39 – A schematic diagram on Roll-front type Uranium deposits.

The last type of uranium deposit which are a interesting class would deposit are the roll
front type uranium deposit. The name actually derives from the very way the ore body
occurs - the U shape type of the ore body is very characteristic (Fig. 39).

They are essentially Mesozoic and Cenozoic - such kind of deposits are not known in the
Archaean. Even during the time of the Paleozoic and Mesozoic are also not known to be
existing till so far and they are also observed in the Colorado Plateau and the Gulf of
Mexico. Here also the general framework of the chemistry of uranium is abided - the
solubility of the uranium species. Strictly speaking, this particular type of uranium
deposit does not qualify to be called as a hydrothermal deposit. Because this fluid is
essentially a low-temperature shallow circulating oxidizing groundwater. So, they do not
fall in the temperature range that we have defined for hydrothermal deposit. So, this is an
exception to the general class, but just for the sake of continuity this deposit is included
in this discussion. And as you could see in the figure (a large-scale map on plan view),
the general morphology shows the oxidized and reduced sandstone with uraninite (black)
deposited in the interface. Deposition of uraninite seems to be controlled by presence of
carbonaceous material sometimes some wood fragments, some plant material or some
carbonaceous material which are present which provide the desired reducing
environment for reduction of U+6 to U+4 and sometimes the ore even mimic the shape of
such kind of fossil wood or materials which are present in this particular horizon.

So, a cross section which is shown here is the shale and the oxidized sandstone uranium
6+ in groundwater; this is high Eh, fugacity of oxygen, oxidation of pyrite to goethite
and sulfate in solution. So, this particular solution is carrying the uranium in 6 plus state
and is moving through the aquifer (gravity driven) along a hydraulic head or by some
kind of process there. But these are essentially low temperature situation - it is not driven
by any kind of a thermal related any convection or any kind of a flow. And then there is
facies change from this oxidized sandstone to reduced sandstone. And the interface of
the oxidized sandstone - reduced sandstone is the domain of deposition and this
deposition takes a very characteristic U shape or the shape of a roll. So, that is how; and
this particular zone is also by virtue of its carbonaceous content is methane and H2S
bearing.
Fig 4 (repeated) - Conceptual summary showing involvement of different types of
fluids in formation of selected hydrothermal deposits.

So, what we essentially have been going through it is kind of a journey through a whole
spectrum of mineral deposits that result from the activity of a fluid and in almost all, but
one case it is a hot aqueous fluid, water rich fluid and the fluid could have any source;
could have a very high temperature, magmatic sources as we saw in case of the porphyry
type deposits, this skarn deposit and the metamorphogenic deposit.

So, let us have another look on this particular diagram from which where we started and
we see whether we have; now with this kind of discussion, we could possibly review this
diagram and see the different types of deposits that we have discussed. And keeping in
mind that the hydrothermal systems; even though we classify them as magmatic,
metamorphic or basinal or meteoric. They do the actual mineralization process is brought
about in most of the cases by mixing of fluid of different sources; very common are the
magmatic deposits which are the porphyry type deposit, where the mineralization is
brought about by at; least by some component by the cooling of the magmatic fluid by
meteoric fluid and the alteration like the propylytic zone and the phyllic zone are
generated with involvement of fluids of meteoric source.

So, mixing of magmatic fluid with meteoric fluid, metamorphic fluid with meteoric fluid
are very commonly observed in many such deposits. We have seen some special type of
deposits; the iron oxide copper gold deposit, IOCG, epithermal deposits in young
volcanic island (both high sulfidation and low sulfidation deposits). The Stratiform
diagenetic deposit which are essentially coming from very low temperature connate
water, Stratiform copper deposits, Mississippi valley type deposits also are result of
activity of very low temperature connate water. So, if we summarize - the important
attributes of the hydrothermal fluid is basically the source which can be identified or can
be traced only when we characterize the fluid completely in terms of temperature and
also pressure which sometimes is significant. And then we have to characterize the fluid
in terms of the salinity - concentration of all the dissolve species; not only just the metal,
but the other constituents which are essential for transportation of the metal in different
types of - in forms of complexes. We realized that it is important to understand the
mechanism of transport of metals in the hydrothermal fluid. Temperature can be
measured from fluid inclusions in minerals. These fluid inclusions in minerals could be
studied in the ore minerals or the associated gangue minerals like quartz. And quite
often, we do the fluid inclusion studies in calcite, fluorite. And even the ore minerals
themselves like we have seen this sphalerite and ore minerals like cassiterite, these ore
minerals also can be studied for fluid inclusions; can also be studied in these ore minerals
and the characteristic of the fluid can be very well constrained.

But majority of the fluid inclusion work is carried out in gangue like quartz; where we
generally find that the quartz is very intimately associated with the mineralization, with
the sulfides. And they do represent the characteristics of the original hydrothermal fluid
from which the mineralization has taken place.

Fluid inclusions data comprise results of freezing and heating experiments that constrain
the thermal and chemical characteristics. Temperature can also be constrained from
stable isotopes, which is mainly oxygen and deuterium and also equally possible is also
the isotopes of carbon and sulfur We can combine the study of fluid inclusion and stable
isotope to arrive at the data on the temperature of the fluid; which will be far more
dependable than getting this temperature, only depending only on one source such as
fluid inclusions or stable isotope.

And the other one which we saw as the source of hydrothermal fluid as meteoric,
magmatic, metamorphic and connate - these four being the most important ones and the
juvenile being very insignificant and sea water in some cases is a distinct fluid
component because it is nothing, but a modified meteoric water.
And we know that this source could be identified on the basis of the del 18 O; versus del
D plot; which we saw the different fields on this particular diagram then the areas or the
fields or could be very well delineated and so, if we have the oxygen and deuterium
isotope data, we could conclusively talk about the source of the fluid.

The mechanism or the process which operated during the hydrothermal mineralization
could be very well constrained from fluid inclusion data and combined with isotope data,
that boiling of the fluid, mixing of the fluid, these two being the most important; other
being cooling, at times could be a good mechanism. So, these processes also could be
identified through a systematic and thorough study of the fluid inclusion characteristics
in the ore minerals and the associated silicate gangue minerals. So, whenever we are
talking about a hydrothermal deposit then we have to answer essentially to the basic
question as source of metal and source of sulfur when the deposit is dominantly a sulfide
deposit like the deposits we have been discussing; may it be a porphyry copper deposit or
a skarn deposit or a VMS, SMS or SSC or MVT deposit. So, the source of sulfur is also
important and we know that in most cases whenever the deposits are at least Paleozoic,
post Paleozoic or so, we generally get a very significant sea water signature; the sea
34 34
water evolved in terms of its delta S. As far as the delta delta S signature is
concerned; it is generally identifiable on the basis of the analysis of the ore minerals for
their delta 34S values. These are the aspects which can be collated, combined to build up
the hypothesis on genesis of any of the hydrothermal deposit. But through our journey or
through the overview that we have made of the entire spectrum of hydrothermal deposits,
covering most of them possibly; we see that it has not been possible to get very definitive
answers to these basic queries about the source of metal and source of sulfur in all these
deposits. And also one of the aspects which also remain conjectural in many of these
situations are the tectonic setting of the older deposits. Although we see that the modern-
day hydrothermal systems, we can understand the process very well, but there are always
some number of gaps that remain here and there.