Mineral Resources: Geology, Exploration, Economics and Environment

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

Module – 3 : Sedimentary Processes and Resulting Deposit Types

We shall discuss another important process, which is the sedimentary process and we see
how the sedimentary process is efficient as an ore forming process.

Fig. 1 A broad classification scheme of sedimentary processes and resultant deposits.

In the classification scheme that was proposed in the beginning, we broadly divided the
sedimentary deposits into two classes, the deposits resulting from process of clastic
sedimentation as a result of erosion and transportation of fragments of rock in form of
detrital sediments, and deposition in the basins, which could be a marine basin or could be
an intracontinental basin or somewhere in the continental margin. The other class is the
deposits resulting from chemogenic sedimentation (deposition from solution in response
to change in the physicochemical parameters). We will first take up, to begin with, the
deposits which result from chemical sedimentation and within this, we have a very
important class of deposits of iron and manganese, both of them being abundant metals.
Therefore, the major source of iron and manganese ores in the present day, come from this
type of ore deposits, which result from chemogenic sedimentation, in ancient (late Archean
to early Proterozoic) sedimentary basins, distributed in many parts of the world like the
Superior province in Canada, the Quadrilatero Ferrifero in Brazil, the Transvaal super
group in South Africa, rich Iron ore bearing basins in the Singhbhum and Bastar Cratons,
the greenstone belts in Dharwar Craton and the Hamersley Basin in W.Australia. These
are the examples, in which we get prolific development of iron formations, and these
basins provide the bulk of the iron ore supply of the world. Less significant in this class
are the ironstones which form mostly in the Mesozoic time. We will not be discussing
them in details, because they are not considered as resources of iron, they are mostly used
for different other purposes. The Neogene manganese deposits, which are mostly in and
around the Black Sea region in Ukraine constitute a major land-based manganese resource
of the world with some contributions from a few greenstone belts and Iron Ore provinces.

We will first take up the Precambrian banded iron formation or the BIF, to begin with.
Banded iron formation does not represent any stratigraphic unit, but it is actually used for
denoting a type of rock with the characteristic banding (alternate Fe-oxide and silica
layers). These deposits, are often associated with occurrences of manganese along with
them such as in the Noamundi Basin in the Singhbhum craton.

The Precambrian banded iron formations are of three broad categories - the Algoma type,
the Superior type and the Rapitan type. The Algoma type are associated with the middle
to Late Archaean greenstone belts and they are the oldest, in age. The Superior type which
mostly come from the type area in the Lake Superior region in Canada and are Late
Archaean to Mid Proterozoic Basins. The Rapitan type is from the Rapitan basin
(McKenzie Mountain) in Canada and its equivalent in the Damara belt of Namibia. They
are Late Proterozoic (~ 1000 to 850 Ma) and the youngest amongst the banded iron
information in the series (refer to photographs of exposure scale BIF shown in the video
lecture). As far as the banded iron formations are concerned, they are definitely very
interesting class of deposits - iron being one of the abundant metals and also as we saw
before, they do form their deposits in huge quantity, (billions of tons). This is one of the
curiosities, so far as this deposites are concerned.

They occur as banded hematite jasper (BHJ) (jasper is basically the iron rich
cryptocrystalline silica) or in the form of BHQ (banded hematite quartzite), they could also
be as BMQ (banded magnetite quartzite). The dominant mineralogy in Algoma type
constitutes of magnetite and in the Superior type and Rapitan type, the mineralogy is
dominated by hematite. Because of the fact that with increasing oxidation state, the
Superior type and the Rapitan type, by the time they formed the partial pressure of oxygen
in the atmosphere was higher compared to the time during which the Algoma type was
formed associated with the greenstones (sequence of the volcano sedimentary rocks
starting with very mafic high MgO - rich komatiites, later giving rise to Tholeiitic basalts
and the Chemogenic sediments, Clastic sediments and the bimodal volcanism and so on).
The lower member, of these greenstones are associated with this magnetite mineralization,
in the form of banded iron formation. These deposits have generated huge interests
amongst the ore geologists. They have been extensively studied for their origin and
evolution.

There are some very intriguing issues such as the very fact that such kind of extensive
occurrences of iron ores in the form of banded iron formations with lateral extent
sometimes going to hundreds of kilometers do not have much of the younger analogs in
the later part of the geologic history. So, it is a little intriguing and tricky at the same time,
because we do not see the modern day process analogs to the old deposits. It will be
difficult to give a very detailed review about these deposits, because they are older deposits
they have been subjected to a lot of later processes in the respective cationic blocks, their
characteristics, constitutions have been modified to great extents. That is the primary
reason why many different ideas on their origin, many different hypotheses have been
proposed. We will be having a brief overview of their characteristics and what we could
infer from those characteristics and as far as their origin and the understanding the process
is concerned.

As far as the dimensions are concerned, the most extensive type are the Superior type, they
are stratiform, and they are very thick almost of the extent of 100 meters or more in
thickness traceable for 100s of kilometers. Again, the Algoma type which are mostly found
in the old greenstone belts, they occur in lenticular bodies just about a meter to tens of
meter thick and a few kilometers in lateral extent. The Rapitan type are more or less
comparable to the Superior type. but are very characteristic in their lithological
assemblages with very little volcanic component in the succession and they occur at the
base of the basin overlying the basement rocks.

The Superior-type are interpreted to be occurring in the stable shelf in the margin and
basins and the Algoma type are in the greenstone belts which are extensively deformed
metamorphosed. They have a very intimate association with volcanics with seafloor rocks
of basaltic composition. now present as amphibolitic rocks and they are associated with
the oldest of the units of the greenstones. The superior type does have volcanic component,
minor but, always present in the succession and sometimes they preserve the entire
sedimentary succession from the basement to the youngest of the formations have been
worked out in many deposits. Rapitan-type do have a glaciogenic component with them
and they are also associated with the mudstone shales and conglomerate. Looking at the
way these iron formations occur in different parts, it is observed from the constitution point
of view, that they are occurring in different compositional variations which we call them
as facies of the banded iron formation. These facies are generally chemically controlled,
because we are essentially dealing with the sedimentary process which is chemogenic in
nature. They are categorized as oxide facies which is dominated by Magnetite, hematite;
carbonate facies (siderite / ankerite), sulfide facies and the silicate facies. The silicate
facies is characterized by the different types of a ferruginous clays, minneosotite and
greenalite kind of a clay minerals. The sulfide facies is dominantly of pyrite almost like
pyritic black shales.

The facies can be interpreted in terms of the variation of the oxidation state of the aqueous
environment (represented as Eh) and pH, that is the acidity or the activity of the hydrogen
ion concentration. These two parameters are important, because they are surface operating
processes on the continental shelf region or in any intercontinental basin. Since we are
working out exercise on plotting of stability fields of Fe species on Eh-pH diagrams
from redox reactions, the details are omitted here.

Interesting thing is that these deposits, which are older are definitely subjected to
metamorphism and at different places, the metamorphic grade could be variable.
Sometimes very high-grade conditions from 700-750 degree centigrade to 10 /11 kilo bar
pressure have been interpreted in some of the Algoma type deposits, and some of the
Superior type deposits have also been worked out, but some of them retain their
unmetamorphosed characters with the lithological characteristics like the associated shales
present within the different stratigraphic horizon persisting.

It is believed that when the iron species precipitate from aqueous environment, it is very
likely that instead of they being shown as oxide species, they should actually be
represented as hydrated oxide species - something like goethite (FeOOH) in different
forms (alpha / gamma form) or other hydrous minerals. What we see them in the present
form - the oxide species, mostly Magnetite and hematite. Some believe that they are
product of metamorphism. But the way they are extensive in occurrence with persistent
lateral extension that we see them, they do not seem to be (in majority of the cases) product
of metamorphism. At the most, we can think of a very low grade of metamorphism from
the associated silicates which we interpret in terms of going from very low grade to low
grade diagenetic kind of environment where these hydrated iron minerals might get
dehydrated and we get them in the form of hematite and Magnetite.

The BIF, either BHJ or BHQ or BMQ primarily can only be labeled as proto-ore with 17
to 25 wt% Iron oxide. What is mineable as ores of Iron are more than 55 wt% iron oxide.
Therefore, it is quite obvious that they must have underwent further enrichment (in most
cases) by later processes that would have selectively removed silica from the ore. While
in most of the cases they are product of surface operated ‘residual concentration’ process,
involvement of high temperature fluid at some stages is suspected in some cases.

Since the BIFs are extensive, representing huge quantity of iron being mobilized. The
very basic question arises as to what could be the source of iron. We may recall here that,
to begin with, the atmosphere was much richer in carbon dioxide, and the seawater was
hotter and corrosive. The early Archean atmosphere was much more deficient in oxygen
than the present atmosphere with partial pressure of ~0.2.

There could be two different sources for iron, one obvious choice could be continental
erosion and transportation mainly in dissolved from common Fe-silicate minerals in
crustal rocks and subordinately in particulate form. Since, we see them in chemogenic
sediments, we can more or less rule out the detrital form of transportation - chemical form
of transportation looks to be more reasonable. But then, if we do some calculations, say
for example, take simple example of a basin like Hamersley Basin (western Australia)
where we know how much of iron has been deposited there. If we presume that they have
been derived from the continental sources, and calculate the total concentration or total
amount of iron that is present there, and the time duration in which the Hamersley Basin
formed, let us say, it is about 6 million years or so, then the rate of iron input (considering
in fact they are deposited in the ocean basin in the shallow continental shelf region where
the environment is pretty oxygenated), then the amount of input of iron that will be
required per year would far exceed the present day rate of input of the metal in dissolved
form considering any major river system of the world (let us say, Mississippi river system).
Partly, it could possibly be accommodated considering that the atmosphere was more
corrosive, more of iron was dissolved in the surface water, but still the mass balance will
always be there as a concern in accepting contribution solely from the continent.

The other possible source is marine sediments that were deposited in the marine basins. It
could be the marine sediments that were getting deposited or it could be the hot oceanic
crust from which Fe could have been leached by the corrosive seawter. Again, we can also
get down into some kind of calculation on the possible sources from the seawater, because
essentially they are marine deposits and they must have formed in some way. If we
consider that, then one of the most obvious sources of this iron that we can have is the
seafloor basalt itself, which will be able to contribute the iron by in the process of reaction
with the seawater. And we already have stated that the seawater during that time was more
carbon dioxide charged, more corrosive with low pH resulting in higher solubility of Fe.
When we calculate, we find somehow it is reasonable from the present-day value of the
seawater iron concentration, which is about 0.02 to 0.03 milligram per liter. The
concentration of Fe in the Precambrian seawater is expected to be high considering the
corrosive sea in the early Precambrain time. Although the process has not been fully
understood, we could visualize upwelling of deeper water (with high dissolved Iron in
reducing condition) towards the shelf where the condition was more oxidizing thus
promoting deposition. Such a model could explain the spatial distribution of the carbonate
and sulfide facies at deeper levels than the oxide facies.

Also, in addition, we have to give an account to the source of silica and its solubility, which
depends a lot on the chemical environment, in which the system is, and we also take it that
the silica is also derived from the continental sources as well as the marine sources, the
seafloor rocks or the sediments that are depositing there, through the interaction with the
water which has a much more dissolving capability than the present day seawater and that
is how we get them deposited in the form of alternating layers of iron and silica; the issue
which will be coming to, in a while. But let us have a brief idea about the depositional
environment.

We will briefly discuss what is interpreted from the study of so many of deposits all over
the world.

Fig.2 Depositional environment of BIF (see text)

The depositional environment in the Algoma type deposits, with their association with the
older greenstone belts, could be thought of in rift related sea floor where, there has been
volcanic activity - deposition of chemogenic sediments and lava. So, they are the domain,
where these iron deposits are supposed to have deposited during that time and later on
modified, deformed and metamorphosed in later times, as we see them in most greenstone
terranes. They can be thought of as environment very much akin to the sea - floor rifting
environment, in which we have the volcanic activity and exhalations.

The Superior- type are stable shelf, as we just discussed through the diagram, on which we
looked into the hypothesis in which the bottom water, or the column of the seawater which
had higher solubility of iron, because of the low pH and the redox condition being so low
with iron, being mostly held in plus 2 state and there could be many possible ways in which
the iron could be held in solution, either in +2 state as Fe-bihydroxide; or could be as
bicarbonate. There could be many possibilities. Even the seawater could have had lot of
iron in the form of chloride complexes, about which we are not going to get into details.
But the environment of deposition is somewhat clear - a stable, continental shelf
environment. They are associated with some volcanic members, which sometimes, have
to make some modification to the deciphered environment. The Rapitan type which are
the continental basins where, they are deposited mostly in the fresh water conditions in
continental rift basins. They are in the type of area where they are associated with
glaciogenic sedimentation, but that may not be quite genetically related to this basin. The
situation is somewhat different from that of the other two and they are not associated with
any volcanic member, representing any volcanic activity.

We could now see that, if the world ocean had a very high solubility of the metal iron, held
in huge amount in soluble +2 state, then what could be the possible mechanism of
deposition in the form of its oxides, that we see in the ores. We could think of possibilities
such as a direct photo oxidation process. Direct oxidation could be an alternate mechanism.

Direct oxidation (two different ways)

4 Fe2+(aq) + O2 + 6 H2O ⇔ 4 Fe(OOH) + 8 H+

4 Fe2+(aq) + O2 + 10 H2O ⇔ 4 Fe(OH)3 + 8 H+

In these cases there is liberation of 2 mole of H+ ion for one mole of goethite / ferric
hydroxide and normally would indicate a strong control of pH of the environment.

Photo-oxidation: Fe2+(aq) + 3H2O + hν ⇔ Fe(OH)3 + 2 H+ + 0.5 H2

This mechanism also yields Fe(OH)3 and H+ in 1:2 molar proportion and additionally
liberates hydrogen. No further analysis of this mechanism is available. Photo oxidation
mechanism may apply more to Algoma type with insignificant or no free oxygen whereas
the first mechanism may be feasible for the Superior and Rapitan type.

Precipitation of Fe(OH)3 or any other hydrated oxide of Fe through photoxidation would

have absorbed the ultraviolet radiation from the sun and enhanced the growth of organisms
in the aquatic environment, or on land during that early time and possibly that is how, the
organism would start to proliferate, but that is pretty hypothetical. It could be one of the
mechanisms by which, one can have deposition of Fe.

Another intriguing issue is the mechanism for the persistent and repetitive banding, called
as meso banding of alternating silica rich and iron rich layers. There can be many
possibilities. First, is that the source – it could possibly be due to alternating iron rich and
silica rich input into the ocean, because of fluctuations in the climatic conditions, or the
oxidation state at the very beginning. It might have caused the quantum of input of iron
and silica to vary. The other possibility could be a phenomenon on the depositional site.
Each individual pair of layers of iron and silica would constitute one varve. There has
been suggestion that it represents the annual, that compares well with varves, which form
in the different present-day lakes. Even it was proposed that it could also be presenting
daily varves, means, during the day time, when there is ultraviolet radiation from the sun,
the iron oxide in these layers will precipitate and during the night time, in absence of
ultraviolet light silica would precipitate in the form of the cryptocrystalline silica layer
which is called ‘jasper’.

The other possibility is that both iron and silica got deposited in the form of gel, or colloidal
precipitation. The isoelectric point for iron oxide and silica have different pH and the
alternating layers could be due to fluctuation of pH.

Fig.3 Iron and Manganese – comparison of aqueous geochemistry

Now, let us move on to a brief discussion on manganese. We all know that manganese has
a very similar geochemical affinity with iron, and manganese also forms oxides. The only
difference that manganese has with iron, is that the manganese does not form a stable
sulfide (‘alabandite’), and is not generally present in ore deposits of manganese.
Manganese exhibits a wider range of oxidation state from plus 2 to plus 7 - the mineralogy
of the manganese ore is far more complicated. But the fact is that, since iron and
manganese are both geochemically very similar, they would have also followed the similar
type of geochemical cycle from the very beginning, and they also are likely to have been
transported, remained in solution and also to have been deposited in the basins, much like
the banded iron formations and that is what exactly we see. Most of the older greenstones
have manganese deposits in close proximity with iron deposits. In Superior Province and
in the Iron Ore province of eastern India and many other basins, we get manganese in very
close association with Iron and as oxide and carbonate facies.

Manganese also does form rich deposits by residual concentration process, from many
high-grade metamorphic terrains where, there are metamorphism of the manganese rich
sediments and later enrichment process, that gave rise to very rich deposits, which we are
not discussing here

As far as this particular issue is concerned, whenever we are discussing them together, it
would be worthwhile to see the close geochemical affinities of the two metals. If iron and
manganese have got similar geochemical affinity, then it would be worthwhile to see how
their oxides, and their aqueous species plot on the Eh - pH diagram. What we see is that
they are more or less comparable. What essentially is observed is that manganese only
requires a little higher oxidation state to form its oxides and under any given situation, iron
is much less soluble than that of manganese. Manganese persists in the solution for longer
time and also till higher pH conditions. This possibly is the reason why in most of the
basins, we find that the manganese bearing horizons, generally succeed the iron bearing
horizons which occupy the lower part of the stratigraphic column. Manganese only has a
higher solubility than Fe in surface environment. In Precambrian basins, Fe and Mn
deposits occur in close proximity, while the young Mn deposits like the ones which occur
around the Black Sea are devoid of any sedimentary Iron deposits. The Black sea is a
stratified sea, because of the salinity difference, the bottom part has a low pH and acidic
euxinic conditions. The Mn-rich bottom water is upwelled periodically and encounters
higher pH oxidizing conditions, where Mn is deposited in the basin rims or the edge of the
self part of the basin, resulting in rich manganese deposits. As we see, then in the Nikopol
– Chaitura deposits, Ukraine, just around the Black sea – they are of Cenozoic age. But
these deposits are not associated with any rich iron deposits, which comes out as one of
the major point of distinction. This is possibly explainable on the basis that iron is not as
soluble as manganese in the present day prevailing physicochemical environment. Any
amount of iron, which will be there, dissolved in the stratified Black sea will be deposited
on the floor as a sulfide, where the condition is reducing and we will only be getting the
manganese deposits in the upper horizons.
Fig.4 Manganese nodules on the sea floor – general idea.

It would rather be incomplete, if we do not discuss something about a very interesting

occurrence of manganese in the form of what we call them as – ‘nodules’. They are
essentially ferromanganese nodules and they do have a latitudinal restriction on the sea
floor (Fig. 4). They are distributed in almost all the seas - the Atlantic, the Indian ocean,
the Pacific. The black filled circles in the figure are representing higher value of Mn than
the open circles. These ferromanganese nodules as they are called, are richer or are
considered as a more important resource of nickel, cobalt and sometimes even some of the
radioactive metals like - radium and uranium rather than the iron and manganese, whose
land-based resources are plenty as of now. Therefore, these manganese nodules are
definitely very intriguing, because they are observed in the open ocean and the only
precondition is that they are in areas, in the open ocean where, the rate of sedimentation
has to be low for the manganese nodules to grow.

The figure (top left) shows a picture of a cross section of a manganese nodule, in the form
of concretion, at the core of it could be any particle either an older nodule, or any kind of
a detrital particle, from the ocean floor or a hard part of any organism on which, manganese
oxide grows as concentric layers. Ferromanganese encrustations are also observed on the
flanks of the MOR, they are also observed on the sea mounds (small elevations on the
sea floor) where they are richer in cobalt and are considered as rich resources of this metal.
Right at this point of time, the technology to mine them out from the seafloor has not very
well in place although many countries including India are actively exploring them and
planning their mining. This topic will be discussed in a later part.
Origin of these manganese nodules is still not very well understood. The obvious source
for this metal like manganese, could be the seafloor basalt itself. Exhalations coming from
deeper regions at higher temperature, in which the sea water is reacting with the seafloor
rocks and getting enriched with respect to manganese and some very special situations in
which, they may be depositing because otherwise in general, the seafloor situation would
not be that very oxidizing in nature, to favor the growth of this kind of nodules. There must
be some additional factors, even some biogenic factor also cannot be ruled out. The
calculated rate of growth of these manganese nodules is pretty slow and are representative
of modern-day ore forming process. Considering the huge population of these nodules,
the total nickel resources that might come from this manganese nodules, possibly will
outweigh the resource that is available on land discovered so far. Thus, we conclude our
discussion on the chemogenic sedimentary process, giving rise to the important metals like
iron and manganese – there are other important metals such as uranium that also gets
enriched in surface-operated process explained using the same principle. We shall touch
upon them in a later section.

We move on to the process which will again be an exogenic process. But they are pretty
efficient processes of the ‘Earth’s own mechanism of beneficiation’. We first discuss the
deposits which result from the process, which we broadly call as ‘mechanical
concentration’ deposits.

Mechanical concentration essentially means they are surface operating process by agents
such as water and wind. The water could either be river - a fluvial cycle, or could be the
sea waves hitting the rocks on the shore. We will restrict ourselves to the fluvial cycle,
river being the main agent of this process, and resulting in deposits which are mechanical
concentration deposits and which are broadly known as the ‘placer’ deposits.
Fig. 5 Mechanical concentration process in a fluvial environment. It schematically shows the
juvenile stage of the river after originating from a mountain and the mature stage with meanders
during which the flow velocity (transporting power) is greatly reduced.

We can see the diagram (Fig.5), a cartoon drawn just for your understanding. Let us take
an example, here is an exposed rock present in a hill somewhere in the continent, let it be
a granite. Associated with common silicate minerals, the granite contains an ore mineral
of much higher specific gravity represented as black dots (exaggerated). Let us say it could
be a cassiterite (tin oxide) or could be a uraninite (UO2) or could be native metal like gold.
This particular mass of hill is being subjected to active weathering, maybe it could be just
mechanical weathering which could be just depositing some sediments on the foot hill,
where we call them the eluvial sediments in close proximity to the foothill. The area is
also being dissected by a river. In the juvenile stage of the river evolves with high flow
velocity and bulk transport without any deposition. At the mature stage the river is
meandering with gradual decrease in flow velocity. Further, in the meander, there is a
significant velocity contrast between the outer and inner curvatures – the latter being less.
This favors deposition of the minerals of higher specific gravity selectively. Since
minerals like cassiterite, or uraninite or could be gold which are at least 3 or 4 times more
in specific gravity compared to silicate minerals, they get enriched with the deposit formed
as ‘point bars’ on the inside bend of the meander. These are called the ‘alluvial placers’
and there are many examples of such deposits of U, Au, Sn, Th and so on. It may be noted
that the placer deposit does not constitute purely of the mineral of interest, but mixed with
detrital grains of other minerals and thus needs a better understanding of what exactly
happens – in other words, to look into the mechanism of this. The hydrodynamic condition
in which the detrital particle will be transported in a river channel and what the conditions
would be, that will result in deposition of these particles needs to be understood.

Fig. 6 General idea about transport of sediments in a fluid channel (river).

Here there are some very fundamental illustrations of flow conditions in a channel (Fig.6).
The flow velocity increases as we move up in the z direction and the flow could either be
a laminar flow or turbulent flow depending on a parameter which is the Reynold number,
that depends on very fundamental parameter like fluid velocity, the height of the channel,
the fluid density and the viscosity of the fluid. The situation could be anything between
turbulent and laminar, where, if we look at this section of the river channel, we see that the
bed of the river and the immediate layer which is adjoining the bed is the viscous sublayer,
where there is a drag that is experienced by the water and there is a threshold shear stress.
In the region above, the flow will be different. In the viscous sublayer, the flow is basically
the turbulence generation layer and as we move up, the turbulence decreases and
approaches towards something like laminar, but much less of the turbulence. And this is
the outer core region. So, most of the transportation of the river system will be taking
place, where as we go up in the river section. In the upper regions where flow velocity is
higher (pressure is lower), particle sizes will be finer and finer, they will be in suspension.
Fig.7 A close view of mode of transport of detrital particles on a river bed and the fluid
flowing above.

Closest to the river bed, detrital particles are transported by a series of jumps or saltation
where they could be sliding or rolling (Fig. 7). We have different minerals of different
sizes, shapes, specific gravity and we shall see how, and what conditions we can get them
deposited.

Fig. 8 Hjulström diagram showing how sedimentary processes can be assessed in terms
of hydrodynamic (flow velocity) and physical (grain size) parameters. Critical
conditions for deposition are shown, as well as those for erosion and transportation for
two situations in which cohesive and non-cohesive channel beds apply
This is a very fundamental diagram - the Hjulstrom curve (Fig. 8). It basically shows how
sedimentary processes can be assessed in terms of hydrodynamic flow. On the X-axis, you
have the sediment size going from clay to bolder size as, you know the size ranges of them
about less than 0.001 of a millimeter (clay size) going to 1,000 millimeters to the boulder
size with all possible intermediate sizes. So, we are seeing 3 regions dominantly - the
region which is marked in pink, is the dominant domain of deposition and deposition
actually depends on the increasing particle size. So, even higher the particle size, here they
can even be deposited even if the velocity is high. The diagram is self-explanatory with
the critical erosion velocity, settling velocity and domains of transportation as bed load
and suspension.

What essentially we will be looking at is the sorting mechanism. Sometimes we see that
in a placer deposit of say gold, we see quartz, gold and maybe some other mineral together
constituting the placer deposit, and we know that they vary in their specific gravity and
their sizes. We will see how and under what conditions we get them deposited.

So, essentially there are 4 such mechanisms for the deposition or the hydraulic sorting
mechanisms. They are relevant to placer formation. It could be a (i) free or hindered
settling of the grains, (ii) entertainment of grains, when the grain will be moved from its
rest position, it will start moving from the granular bed load, by flowing water, (iii)
shearing of grains in a moving fluidized bed, or (iv) differential transport.

Fig.9 Illustration of hydraulic equivalence – particles of different specific gravity, diameter

settling together at one place.
Velocity of settling is given by

𝑔𝑔𝑑𝑑2 �𝛿𝛿𝑝𝑝 − 𝛿𝛿𝑓𝑓 �

𝑉𝑉 =
18η

where δp and δf are the densities of the particle and the fluid respectively, η is the dynamic
viscosity. This is simple Stokesian settling in laminar flow conditions. So, this illustration;
here what it is actually showing is something which is called the hydraulic equivalence;
where quartz of a larger diameter (16 mm), pyrite of an intermediate diameter (1 mm) and
gold of the smallest diameter (0.5 mm), with their densities being 2 g/cc, 5 g/cc and 17
g/cc respectively. We see that they have the same settling velocity. (VQ = VP = VG). Here,
we see that the settling velocity is being the expressed as the square relationship with the
diameter. A square relationship fails in many situations. There are three inadequacies in
Stokesian settling to explain complex placer forming processes: (i) flow is not necessarily
laminar always, (ii) particles deviate from spherical shape and sizes may be too small or
large with significant frictional drag (e.g. biotite and quartz) and (iii) in case of high
particle population, the interparticle collision causes retardation of settling velocity.
Therefore, a more realistic settling velocity is given by

1/2
𝑉𝑉 = �4�𝛿𝛿𝑝𝑝 − 𝛿𝛿𝑓𝑓 �𝑔𝑔𝑔𝑔/3𝛿𝛿𝑓𝑓 𝐶𝐶𝑑𝑑 �

Where Cd is the coefficient of drag and is equal to 24/Reynold number

So, looking at this, more realistic relationship has been deduced. Instead of having a square
relationship with ‘d’, a square root relationship has better predictability. The square root
relationship involves another parameter Cd, which is the coefficient of drag and is equal
to 24 upon the Reynolds number.

Entrainment is the other sorting mechanism that give rise to deposition following the
relationship given below. The process depends on a dimensionless parameter known as
the Shield parameter (θ) that depends on the critical shear stress required to initiate
movement (τc).

𝜃𝜃 = 𝜏𝜏𝑐𝑐 /��𝛿𝛿𝑝𝑝 − 𝛿𝛿𝑓𝑓 �𝑔𝑔𝑔𝑔�

Fig. 10 See captions below the figures

If we look at this the diagram (Fig. 10), the left explains us what exactly happens. If we
take the shield parameter (on a logarithmic scale in the figure) and plot with Reynold
number, we can define zones of ‘entrainment’ and ‘no movement’. If the shield parameter
is low, there will be no movement even at high Reynold numbers. In this context, the
parameter ‘p’ and ‘D’ are of some significance. If we consider a smaller grain along with
large grains of diameter d, whether the grain will be entrained or not will depend upon the
value of p, the height to which it protrudes. If p=0, the particle will not move. The more
the p, the greater the chances of its entrainment. The shear stress that is required for the
entrainment depends on the density of the particle. So, when gold is around 19 and ilmenite
is 5, quartz is 2.5, we see that the critical shear stresses is more. The more is the diameter,
more is the shear stress and more is the density, more is the shear stress required to get the
particle entrained in any flow condition.

Fig.11 In case of transport in a fluidized column (see captions and discussion in text).
Shear sorting: Shear sorting is important in case of concentrated flow of suspended
particles in a fluidized medium (Fig. 11).

Two grains of different densities (δ) coming to rest in the same horizon would have
relative sizes (d) given by

𝑑𝑑ℎ = 𝑑𝑑𝑙𝑙 (𝛿𝛿𝑙𝑙 /𝛿𝛿ℎ )1/2

Where dh and dl are the diameters of the heavy and light particles respectively.

It is essentially a function of the 2 different densities – of the lighter (l) and the heavier
(h). So, the shear sorting is always in terms of the relative values of the densities of the
particles. So, here is the lighter and the heavier grains of different densities coming to rest
in the same horizon would have the relative sizes of the heavy particle and the lighter
particle as indicated by the expression where the dh and dl are the diameters of the heavy
and the light particles and the other two parameters as defined before.

What is interesting to see here is that, suppose we start with a material constituted of quartz
and magnetite. Quartz and magnetite are of different densities and suppose we have started
with a material where, quartz and magnetite are in a proportion of 90 is to 10. Here the
relative height of any bed where they have been transported there will be a particular zone
within this column, in which, there will be an increase in the magnetite proportion. The
figure shows the proportion of magnetite being doubled compared to the starting value.

Fig.11 Transport sorting (see captions and discussion in text).

Transport sorting is a hydraulic sorting mechanism that arise due to differential transport
rates that existed in movement of particles in a flowing fluid medium - suspension sorting
and bed load movement being the two dominant mechanism. Here again, the heavy and
the light particles are taken into consideration and they are coexisting at any point in the
channel flow. Here, Ca is the reference concentration ‘h’ is for the heavy and the ‘l’ is for
the light particle and the ‘v’ is for the velocity of the heavy particle and velocity of the
light particle.

The governing equation for transport sorting is:

(𝐶𝐶/𝐶𝐶𝑎𝑎 )ℎ = (𝐶𝐶/𝐶𝐶𝑎𝑎 )𝑣𝑣𝑙𝑙 ℎ/𝑣𝑣𝑙𝑙

So, this predicts that particles in a turbulent flowing channel, will be sorted vertically
according to the settling velocities which in turn, according to the Stokes law are
determined by the relative sizes and densities. Stokes law only talks about the relative
sizes, it is also according to this transport sorting, the velocities at which these particles
are moving, is also a parameter which decides whether there will be deposition and there
will be sorting.

Now, you can see how we can correlate the process of placer formation with the flow
conditions and particle characteristics. It requires a little bit of a finer details on the exact
process of sedimentation, that is taking place when a cross bedding is forming with the
foreset laminae in a flowing water system. The details of the sedimentation process will
not be discussed in detail here.

Fig. 12 Geological map of the Witwatersrand paleoplacer gold deposit.

But the fact is that these processes are manifest in, starting from very small to very large
dimensions. If we are examining a particular sedimentary horizon we observe many types
of sedimentary structures. Sedimentary features that we see, especially the cross beddings,
we know that they form because of the velocity differences in small length scales and the
transporting characteristics. So, you should be able to see situations in which the particle
entrainment and the sorting of these particles took place and fraction of the heavier
particles that will be there, in any particular domain can be correlated and we see that it
comes out clear. So, whenever you look at a paleoplacer deposit, you should be able to
dissect it through, to look how such small domains or the local scale enrichments have
given rise to such huge accumulations in the form of a big placer deposit, and what we see
here (Fig. 12) is, the famous Witwatersrand paleoplacer gold deposit in South Africa of
Archaean age. The Witwatersrand Basin is about 60,000 square kilometers in area, has the
central Witwatersrand group. Possibly, it is difficult to find any present day analog of such
kind of huge fluvial system in operation. There are about 6 – 7 gold fields in the basin as
shown in the figure.

Fig. 13 shows vertical cross sections at the 7 gold fields and we see that the Au-U bearing
conglomerates (termed as reefs) are correlatable across the whole basin. The Vredeford
dome which is essentially a meteoritic impact crater is located in the center of the basin.

Fig. 13 Vertical sections of the 6 gold fields of the Witwatersrand deposit with correlation
of the reefs.

Most of the gold comes from the stratigraphically lowest reefs (Fig.13). They are not just
pure gold, they contain gold and uranium with pyrite and quartz and the conglomerate
horizons essentially formed from auriferous quartz (veins / lodes), which might have been
exposed anywhere in the nearby areas.

Fig. 14 Cross section of auriferous reefs formed in multiple successive stages and the
intervening sandstone and scour structure as a result of the fluvial sorting process.

So, while discussing about the manifestations of the mechanisms that we discussed in all
possible scales, Fig. 14 shows the scours, where we get dominantly the sand deposits and
the intervening conglomerates are essentially the gold bearing reefs and we see, that there
are series of such gold bearing conglomerate reefs. They occupy exactly the position just
above an unconformity, which indicates that there have been many series of such of
reworking, several stages of such erosion and deposition in this basin, that has gone in and
that might have possibly worked in getting the gold further and further enriched to give
rise to this rich gold occurrences, with thickness ranging a few cm to 2 m.

It is observed here that thinner the bands are, the richer they are in gold. Fig. 15 gives an
idea about the relative uranium and gold concentrations in these reefs. The grey part shown
is for uranium and the lighter part for gold.
Fig. 15 Spatial variation of gold and uranium in the Witwatersrand deposit.

The uranium and gold proportions vary which is shown in the figure. The anastomosing
braided pattern of the basin is the feature to be noted, representing local scale controls of
enrichment. The slope is actually from north to south and is very well correlated with the
uranium and uranium by gold ratio. A simple explanation for this is the higher specific
gravity of gold (~ 19) compared to uraninite (~10), due to which gold deposited early in
the upslope regions and uraninite was carried and deposited downslope.

Fig. 16 A synoptic 3-D view of the Witwatersrand basin

Fig. 16 is a synoptic 3-D view of the Witwatersrand belt basin which is interpreted to be a
result of some 5 or 6 major rivers with the sequence of the sedimentation almost goes to 6
to 7 kilometers in thickness and one would wonder, that how such thick sedimentation
took place. It is visualized that there has been progressive uplift on the provenance area,
during the formation of the basin. The provenance could be as distant as the Limpopo belt
which is about 250-300 kilometers from the basin. We still do not see any such present
day comparable situations in which such large river systems are at work and whether any
such kind of representative deposit forming process is actually operating or not.
It is a case of a classic placer deposit which was developed by 5 to 6 major rivers, and the
provenance was the gold bearing quartz load deposits in the nearby cationic area. It is also
unique in the sense that it is also a major resource of uranium, where there is significant
enrichment of the metal in the form of detrital uraninite along with gold.

As it happens with all the gold deposits, the ideas about the origin of these deposits will
always be debated. There are features, which will be indicating origin in a mechanism
which would otherwise look different from the well accepted mechanical concentration
model. The gold grains here retain their detrital characteristics, indicating long distance
transportation, along with the detrital quartz grains constituting the conglomerate bed, and
the localization of enriched mineralization at the contacts whenever there is an older
unconformity erosion surface. The evidence of the glacier model also comes from the fact
that gold has been transported dominantly as detrital, rather than being dissolved in some
fluid and getting enriched in the deposit, because of the believed reducing condition of the
Archaean atmosphere, where gold was not soluble, in the crustal fluid. An oxidizing fluid
can transport gold. And so is uranium, uraniumnite which also cannot get transported in
the fluid in a soluble form under reducing condition and that is how we believe the detrital
model, and there is little indications of this deposit being metamorphosed to any higher
grade rather than simple very low grade greenschist facies metamorphism, and which
possibly would not be efficient enough to mobilize other fluid.

The alternate model which have been proposed by many workers is the hydrothermal
model for this origin of the deposit. We will defer the discussion till the time that, we
discuss about the nature of hydrothermal fluid, and what hydrothermal fluids are, but for
the time being we finish off the discussion of this particular deposit with the fact, that there
has been alternate model of hydrothermal origin for mineralization of gold, and uranium
in this deposit.

So, with this let us move over to the situations where, we could see some of the very recent
placer deposits which are of mechanical concentration origin.
Fig. 17 The Orange River diamond placer system, S. Africa – mixed alluvial and beach
placer system with the provenance area containing diamondiferous kimberlites shown.

There are Cenozoic placer systems, one is the Otago region in South Island New Zealand,
which is the area where with the sediments are derived from the Otago schist belt, where
there are gold deposits. The Ballarat gold field Victoria, Australia is also a gold only
deposit of mechanical concentration origin. Fig. 17 shows the Orange River diamond
placer system in South Africa. All those which is shown with diamond symbol are
generally the areas having diamond deposits in the form of the kimberlite diamond.

This is also essentially fluvial although the deposition has taken place unlike in the case of
Witwatersrand where the deposition has been more on the fluviodeltaic part of the system,
here some of the deposition has also has been taken place in the near shore / offshore
region where it is also driven by the eddy currents. And this is one example where we can
see a mechanical concentration process, which has been operating in giving rise to
diamond deposits of placer origin.
As we know that placer deposits could also originate by sea waves, by the tidal waves that
we see in the littoral region of the sea. Mechanism wise, it is difficult that the beach placers
should be having any kind of a settling type of sorting here, because of the very narrow
and a very turbulent, very energetic conditions prevailing there, and in the swath region.
Entrainment also looks to be unlikely, but all depends on the local conditions of the tide
and it is energy, where in some of the beaches it is believed that there is some amount of
entrainment mechanism which also works. With this kind of situation we mostly would be
explaining, the sorting, and entrainment of this high density material in the form of placer
by shear, and by transportation sorting kind of mechanism.

Examples of beach placers - we get a huge accumulation of a minerals like monazite,

which is essentially the primary source of the metal thorium, which is very essential for
generation of nuclear energy. The eastern coast of India, where we get lots of such
occurrences / enrichments which, we call them as the beach placers. Some ilmenite bearing
sand deposits at some localities in the east coast are also of placer origin. Availability of
such kind of placers is very much dependent on provenance characteristics

Now we will be switching over to another important process which is also an exogenic
process driven the energy being provided by sun.
Fig. 18 Cartoon representing Residual Concentration process.

The process is essentially a process of enrichment called ‘residual concentration’ process.

Essentially it is a process which arises out of the differential leaching of constituents from
the rocks leaving behind constituents, which are economically important. Fig. 18 is a
cartoon which shows the original rock, say a rock of granitic composition, which contains
silica alumina, sodium, calcium, potassium magnesium, and other major oxides. And this
particular rock is subjected to a weathering condition on the surface, and the
physicochemical conditions will be such that other than aluminum and a little bit of iron,
most other constituents - silica the alkali and alkaline earth oxides are leached out from
the rock leaving a residue which is enriched with respect to aluminium. Such kind of
residual concentration process have been in operation, and they are all results of recent
phenomena (Quaternary deposits), which are being exploited in many different parts of
the world. The necessary precondition is that the rock should be aluminum rich and also
the concentrations of silica should be low. The situation is favored by proper topographic,
and climatic parameters. Generally, we observe that this kind of weathering processes are
more facilitated in humid tropical kind of climate, where weathering and the dissolution
of many of the elemental oxide species is favored, and is efficiently done by the fluid,
which essentially is the meteoric fluid, which precipitates on surface. Obviously, such kind
of residual concentration process will be very much dependent on the nature of the surface
of the rock. It should have enough of surface area available for the interaction of the fluid
with the rock. The rock with a good fracture density in the surficial region will allow
efficient percolation of the meteoric fluid, and will always be a better host to give rise to
such deposit, than a rock which is massive not providing any porosity / permeability for
the meteoric fluid to percolate.
Fig. 19 Eh-pH diagram showing the relative solubility of Al and Si that is a fundamental
aspect controlling the operation of residual concentration process for giving rise to bauxite
deposits.

Now, if you want to understand the process, then we have to get into a little bit of
fundamentals on the behavior of elemental oxide like silica, and alumina (Fig. 19). Here
we are considering silica and alumina, because the constituent silica is the one which we
essentially would like to be removed from the rock so that the rock becomes richer in
alumina, and we get the deposits. A very familiar process that we see in case of rocks
getting converted to laterites is essentially the lateralization process by which a rock gets
converted into a rock rich richer in iron, giving it a very typical pisolitic texture similar to
what we see in bauxite. So, here we see the antipathic relationship between the two
important species like, silica, and alumina. Alumina is amphoteric and its solubility
increases both in the alkaline and the acidic conditions, and passes through minima at
around a pH of just about 6. So, it would indicate that anywhere, we get such kind of a
fluid where the alumina will be insoluble, and silica will be soluble, and that will be a
situation where it will be the most favorable condition for getting a rock enriched with
respect to alumina. And one more important thing is that the topographic factor is also an
important one, since we need the components like the alkali, magnesium silicon, all to be
dissolved in the meteoric water, and to be out of the system or to leave the system, not to
be reprecipitated in any form, that means, we need to have a favorable topography for this
process to operate efficiently.

Fig.20 : Optimum conditions for formation of bauxite. Fields 1 and 2 – leaching of both Fe and Al
and no laterite will form and Si-rich soil will form; Fields 3 and 4 are characterized by restricted
solubility of Fe and Al and laterites and bauxites will only form if the bedrock composition itself
has high iron or aluminum contents. In field 3 bauxites are unlikely to form because of preferential
leaching of Al from the soil, although over a protracted time period and given the right climatic
conditions, high Fe laterites will form under these conditions. Groundwater solutions forming in
field 5 will contain more Fe than Al and laterites will form in this environment. The optimum
conditions for bauxite formation are provided in field 6 where groundwater solutions will
preferentially remove Fe. In this field Al hydrolysates are stable, especially at pH between 5 and
7, and gibbsite will accumulate.

Let us look at this diagram (Fig. 20) which is an Eh - pH is diagram, which we discussed
in the context of iron deposits in the previous section. On this diagram the thick line curve
is for ISO or equal solubility of both aluminum, and iron.
Note: The ore which is called ‘bauxite’ is an aggregate of hydrous Al-oxides such as
bohemite and diaspore (different form of AlO(OH)) and gibbsite (Al(OH)3).

So, the outcome of for this process of residual concentration is the formation of the bauxite
ore. It just needs the appropriate combination of the physical, and the chemical
environment, even in a rock like basalt which contains very less amount of silica compared
to rocks which are granitic, can also be lateritized. Any rock which is aluminum-rich for
example, the sillimanite and garnet bearing quartzofeldspathic gneiss, and garnet bearing
granulites in the Eastern Ghats which are known as the khondalites. They have been the
important major source rock from which the massive East Coast bauxite ores formed and
constitute the bulk of Al resource of India.

These bauxites could possibly be classified or could be distinguished on the basis of the
kind of source rock from where they are derived, and also they exhibit different type of
structure, and texture. Most situations where we get this bauxite is at the surface blanket -
we can call them the highland laterite, or highland lateritic bauxite, which forms from
common rocks.

And one thing with respect to this diagram also you should remember, that it is virtually
not quite possible to get a bauxite which will be absolutely or free of iron, invariably the
bauxite will have some amount of iron in it. So, the hydrated oxide of iron which is a
limonite (hydrated Fe-oxide) are also there in the bauxite. So, the surface blanket we find
is more gibbsitic (Al(OH)3) resting directly on the parent rock, with the parent rock texture
preserved, and it is controlled by the joint pattern in the rock. We can also get bauxite in
interlayered beds, lenses, in strartigraphic sequence. In volcanic domes, the bauxite is
pisolitic and is bohemitic (AlO(OH)).

There are pocket deposits in limestone which essentially are the karst type of bauxite,
which form in the solution cavities that are formed in the limestone, because of dissolution
phenomena, later on deposited by aluminous clay and later converted to pockets of bauxite.
Bauxite formed from igneous rocks are structureless, more gibbsitic and pisolitic.

We also sometimes get detrital bauxite which have been transported from the previously
formed bauxite which are basically sedimentary or the reworked deposits. There are also
possibilities, that in many of the areas where there is rich bauxite, they actually result from
the continentally derived wind-blown dust which get converted to bauxite. We cannot
discuss much on their exact mechanism because it is not known.

Fig. 21: Different types of bauxite ores.

Here are some of the pictures of the typical look of a bauxite, they are made up of small
hemispherical masses called the pisolites, and they range from a few millimeters to
centimeters in diameter. The first is a typical bauxite ore, which is a highland bauxite with
pisolitic texture. The second one is more iron bearing, and the third is a typical karst
bauxite in Ural in Russia.
Fig.22 Enriched Iron ore in the form of blanket from proto-ore.

While discussing the Iron deposits, it was mentioned that the rich high grade mineable ores
are actually results of enrichment from the BIF proto-ores. Fig.22 is an example that results
from a residual enrichment process. So, iron deposits also can get enriched to high grade
from the low grade parent material, and in this process where we have to have a situation
where, there will be enhanced solubility of the silica which is present in the
cryptocrystalline a form called jasper, they have to be selectively leached out of the
material giving rise to the high grade ore.

The other important metal which also is enriched in the process of residual concentration
is nickel, and the source rock are the ultramafic rocks. In fact, these resources of nickel in
the residual concentration is even higher than what are available in the form of the
nickelliferous sulfide deposits in the ultramafic rocks. So, essentially the minerals in the
ultramafic rocks mainly olivine and pyroxene contain nickel in their structure, and when
they are exposed and are acted upon by the surface processes, they get serpentinezed. And
this serpentine after a further process of enrichment gives rise to horizons, where the nickel
is trapped.
 Iron Crust
Ni
Pisolite Cr, Al and Fe
Pedolith
decrease; Si and Mg
Red Limonite
increase in this zone
Yellow Limonite

Ore within Boulders

Saprolith Garnierite

Rocky Ore

Bed Rock

Fig. 23: A typical Ni-enrichment profile.

Fig. 23 is a typical profile of nickeliferous lateritic zone which will be having a iron crust,
followed by a psiolitic lateritic kind of zone, then will be followed by a red limonite, and
yellow limonite. And then will have the ore within boulders, and this is the zone which is
labeled as ‘garnierite’ (garnierite is essentially a generic name given to the nickeliferous
clay minerals), which are derived through the process of alteration and hydration of the
primary ferromagnetism minerals like olivine, and finally in the deeper part there is fresh
rock. And if you take the nickel concentration, then the nickel concentration is low within
this top part which is defined by the pedolith (essentially pedolith is the term that denotes
the soil top soil layer), and the saprolith is the layers which actually indicates, the more
rock like characteristics, where this saprolith zone which is the one which is more enriched,
and the zone in which you get the concentration of nickel trapped in the nickeliferous clay
minerals, which are the garnierite. And if you look at this profile a nickel concentration
has a high in these zones where, we have the ore within the boulders - the garnierite, and
again falls back to normal background value, when it is the basement rock or the host rock.
And in this situation we see that chromium, aluminum and iron will always decrease, in
this particular region they will have the minimum value, because this region is the ore.
Nickel can be extracted where Ni can attain concentration of the order of even 1 to 2
percent, and silicon, and magnesium will also be increasing in this zone, because they are
leached out from the surface and deposited here, within this region and so, where we get
the clay which are essentially alumino silicates. - hydrated aluminum silicate. So, that is
how we get the zone here.

So, these are the examples of surface operated process, or exogenic process, which gives
rise to rich ore deposits of important metals like aluminium, and sometimes with a nickel,
and gold. And also if we consider that enrichment of the primary iron ore to give rise to
the high grade ores by selective leaching of silica that also, can be included in this process.

Next, we will discuss another such important enrichment process, where actually it is
essentially a process by which a primary ore gets enriched or gets concentrated in a definite
part of the existing ore body.

Fig. 24: Cartoon representing the supergene oxidation and secondary sulfide enrichment.
The figures can be visualized as representing the sequence of the process that operates on
any multimetal sulfide ore body.
We call this process essentially as the supergene oxidation and secondary sulphide
enrichment process. If you look at it (Fig. 24), this is a cartoon that depicts the scenario
here. What is shown here. for example, say it is a tabular ore body which extends to depths
of several hundreds of meters from the surface. This deposit definitely formed at a deeper
condition in the crust when it formed primarily and now this deposit has been exposed to
the surface and this has been a primary ore body of a metal sulphide and has abundant
pyrite (FeS2), as the dominant mineralogy along with other sulphide minerals like
chalcopyrite or it could be galena and sphalerite as well.

And suppose this particular body is now exposed to the surface. What is shown here as
WT is the water table. We all know the water table is the surface at which we will get
water, that is a surface which is essentially in an unconfined condition is the water table.
So, above the water table the condition here is actually known as the zone of aeration,
where the pore spaces in the rocks or the fractures are either partly filled up with water or
are filled up with air and that is why we call it as a zone of aeration or zone of oxidation,
and below the water table, where the pore spaces are fully filled up with water it is the
zone of reduction. The significance of this with respect to this ore body which is exposed
at the surface is like this - we have the primary sulphides essentially dominantly pyrite on
the surface. So, one of the necessary conditions for this process to operate is that the ore
body has to have a certain abundance of the mineral pyrite. why is it so, we will just see
in a while.

So, what happens here is that the primary pyrite gets oxidized in the presence of water and
oxygen and generates huge amount of sulphuric acid (H2SO4) and this H2SO4 which is
generated here in this zone, actually dissolves the other metals like lead or zinc or copper,
which are there in minerals like chalcopyrite or sphalerite or galena and then they are
soluble then they are converted to their soluble sulphate form and descend to deeper
regions because, this zone is essentially the zone where the permeability is essentially high
through which this dissolved form of the metals like copper zinc and lead they go down.
When they cross this water table and encounter reducing environment, all the sulphates
get again reduced to form their secondary sulphides.

So, in terms of the process the results are that, below the water table, we get some zone
which we call as the secondary sulphide enrichment zone; in which the primary
sulphides of the ore like chalcopyrite / galena / sphalerite are replaced by the secondary
sulphides.

In case of copper, they are Cu 2 S (chalcocite) and Cu S (covellite), these 2 minerals rarely
form in primary sulphide ore bodies, So, the zone which is shown here essentially at the
zone in which there will be enrichment on the metal in the form of the secondary sulphide
which are the chalcocite and covellite. So, this is how the process goes on, and what
happens here is all as we know that iron cannot remain in the soluble Fe 2+ form for long
on the surface, it immediately gets oxidized to form it is respective insoluble oxide or the
hydrated oxide. So, what is shown here with this orange colour material is essentially this
material is actually called, it is like a oxide cap or oxide reach iron cap or this also in
mining geology term it is also called as ‘iron hat’ - also very popularly known by the term
‘gossan’. So, this part we can call as the supergene oxidation zone, and the immediately
following zone just below the area is essentially the zone from which most of the metals
copper lead at zinc depending on what the deposit is or leached and this is the enriched
zone.

Above the WT

2 FeS2 + 7 O2 + 2 H2O = 2 FeSO4 (aq) + 2 H2SO4 (aq)

2 FeSO4 (aq) + H2SO4 (aq) + 0.5 O2 = Fe2(SO4)3 + H2O

Fe2(SO4)3 + 6 H2O = 2 Fe(OH)3 + 4 H2SO4

CuFeS2 + 8 Fe2(SO4)3 + 8 H2O = CuSO4(aq) + 17 FeSO4 + 8 H2SO4

Below the WT

2 Cu2+ + HSO4- + 7 H+ + 10 e- = Cu2S (s) + 4 H2O

2 Cu2+ + SO42- + 8 H+ + 10 e- = Cu2S (s) + 4 H2O

Cu2S (s) + HSO4- + 7 H+ + 6 e- = 2 CuS (s) + 4 H2O

Cu2S (s) + SO42- + 8 H+ + 6 e- = 2 CuS (s) + 4 H2O

Schematic reactions taking place in the oxidation and reduction zones in a ‘supergene
oxidation and secondary sulfide enrichment’ process are given above. Let us look at the
mechanism - the way it works in form of the reaction. So, here we could see what exactly
we discussed the reaction is pyrite, plus oxygen, plus water giving rise to a ferrous sulphate
which is soluble aqueous and generation of H2SO4 this sets up a chain reaction where the
FeSO4 is again acted upon by sulphuric acid to form ferric sulphate. This ferric sulphate
gets oxidized - the iron getting oxidized to form the Fe(OH)3 which actually is the part of
that iron hat or the gossan which was just mentioned, again releasing H2SO4. So, that is
how the amount of H+ released is high and the system becomes far more acidic, and if you
look at it, acts upon the mineral like chalcopyrite, then it forms the soluble copper sulphate
and similar reactions also could be written if we have sphalerite or it would have been a
galena. So, it dissolves the metal in the form of copper sulphate and these are the reactions
which take place above the water table and below the water table, the reactions that take
place is that this copper ion which is being transported through the fluid gets reduced to
Cu2S, that is the chalcocite or even CuS. So, these 2 sets of reactions they operate above
the water table and below the water table and explains the formation of the supergene
sulfide enrichment.

Fig. 26: Eh-pH diagram showing stabilities of Cu-species in a supergene process.

The situation also can be explained with the help of Eh - pH diagram (Fig. 26), where the
appropriate reactions could be written. If the conditions are such the appropriate pH and
the Eh conditions are such, we also can have formation of native

Gossan

Secondary
Enrichment Zone

Fig. 27: Example of a copper deposit with an oxidation zone with red Fe-oxide with a
secondary sulfide enrichment zone (black) dominanted by chalcocite.

copper as we see them and the oxides and they generally are within the oxidation zone,
because we could see the pH stability of these oxide minerals like tenorite or native copper
or cuprite, generally will happen when the pH is much higher. So, the situation where the
country rock is able to neutralize the acid that is generated by the process of a pyrite
oxidation, then the copper of the primary ore and oxidized zones may not be able to be
dissolved that efficiently, some amount of copper will be left behind in the oxidation zone
to form the minerals like tenorite and cuprite and some native copper as well.
 Fig. 27 is an example from the Malanjkhand copper mine in central India, details of which
we will discuss when we will be discussing Indian mineral deposits. Just to show as an
example, the altered / weathered granite at the top and ore body which is exposed on the
surface and is converted to a entire mass enriched with limonite or this is exactly where
the Gossan looks like. Just below the gossan here we see that this is the zone, which is
secondary enrichment zone and the chalcocite and covellite impart a very typical black
colour and they give such kind of an appearance and sometimes these zones are also called
as the ‘sooty ore body’ in the mining geological terms, and if one goes further down then
the primary ore body is encountered. So, in such kind of an ore body almost like for a
vertical height of almost 20 - 30 meters, and for 30 - 40 meters, such kind of zone generally
is observed - the supergene sulfide zone below the supergene oxidation zone, which is
characterized by the presence of this gossan.

Thick black lines – quartz Quadrangular pattern: b – Average type

veins; b – cell walls of cross structure, c, d – thin
limonite; c, e – interstitial angular web work
limonite (Porphyry copper
Deposit)

Fig. 28: Types of limonitic boxwork as product of the supergene process.

These gossans actually as we will be discussing sometime later when we take up

exploration topics, they are very interesting. First of all, when such an ore body has
undergone supergene oxidation on the surface, and is a clear cut indication that there must
 be a secondary enrichment zone down below and more importantly the presence of an ore
body in the subsurface and that is what exactly we look for.

So, this serves as very good geological indicator for exploration; that means, the process
of finding out new ore bodies in areas where they are not known to be occurring and these
limonitic cap or the gossan zone, usually is there in the area of the ore body has a
considerably fractured that is how the fluid could percolate to the fracture zone and they
do display various types of forms which are known as the ‘limonite box work’, Fig. 28
shows 3 examples which is shown here the first one is the typical box work which is
produced from a chalcopyrite ore. The thick lines are the veins of quartz because they are
essentially present in the mineralized quartz veins. So, these are the original quartz veins
in which the minerals, the primary sulphide minerals has been leached out and have been
left behind by the interstitial limonite. So, this c, e and b are all the interestitial limonite
and has come from typical type of copper deposit, which are known as the porphyry copper
deposit, which we will be discussing later. The ‘A’ pattern has come up from a
quadrangular pattern where there is some cross structure and triangular boxwork. These
are actually the indications that what kind of an ore body could be expected below, whether
it is a chalcopyrite rich ore body ore similarly we see that this is the kind of box work
which is created (‘B’), if there are sphalerite rich ore body.

Coarse Cellular
Galena Boxwork: A- Regular Pattern; B – Diamond
Boxwork of
Mess type
Sphalerite
Fig. 29: Limonitic boxwork formed due to supergene oxidation of sphalerite and galena
ores.

Because, sphalerite by virtue of it is morphology, it’s crystal habit and the way it forms in
the fractured spaces in the deposit results in gossan of a different morphology and so is
galena (Fig. 29). Sphalerite gives rise to a course cellular box work. Galena rich ore gives
rise to a diamond mess type pattern.

So, these processes which we have discussed, the surface operating processes - the
mechanical concentration, the residual concentration, and the supergene sulfide
enrichment are essentially very efficient processes in giving rise to ore deposits, as well as
getting the already existing deposit enriched to high grade values. So, they are even as
important as the primary or forming processes,