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Status and potential of exploration for PGE in India

Conference Paper in Geochimica et Cosmochimica Acta · August 2007

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Journal of Applied Geochemistry
Vol.8 No.2A (2006) pp 441-457

EXPLORATION FOR PLATINUM GROUP ELEMENTS (PGE) IN

PENINSULAR INDIA - STATUS, PROBLEMS AND SCOPE *
V. Balaram
National Geophysical Research Institute, Hyderabad - 500 007, India
E-mail : balaramv1951@yahoo.co.in
Abstract
Discovery of new platinum group of elements (PGE) deposits/mineralized zones is of great economic importance for the
country. An account of the formation mechanisms of different PGE deposits and their reported occurrences across the
world are presented. In India till date only the Baula-Nuasahi layered Complex in Orissa, mafic-ultramafic Hanmalapura
Complex in Karnataka, and the layered Sittampundi Anorthosite Complex in Tamil Nadu, are the three known promising
PGE occurrences. Recent studies show that there is a tremendous potential for PGE-mineralisation in mafic-ultramafic
complexes, ophiolite complexes and the fine grained sediments such as sulfide bearing black shales, occurring in different
parts of our country. Determination of PGE at extremely low concentrations with the accuracy and precision and at high
throughputs required for exploration studies needs optimization of critical steps such as selection of a representative
sample and application of sensitive analytical techniques, etc. For identifying economically viable deposits and their
mining, detailed geological, petrological and geochemical studies are essential on massive potential areas. These aspects
are discussed in detail with examples.
Keywords : PGE, Exploration, Mafic-ultramafic, Ophiolite complexes, Black shales, Manganese nodules, Nickel sulphide
fire assay, Laser ablation.

1. Introduction fractionation with respect to Pd-PGE. Petrological

Platinum group elements (PGE: Ru Rh, Pd,
Os, Ir and Pt) are assuming an increasingly important
role in modern industrial society. Due to their high
melting points and relatively low reactivity, these
elements together with gold (Au) are called “noble
metals” and for many years after their discovery,
their use was essentially limited to jewelry, dentistry
and minor laboratory consumption. PGE and gold
(Au) are generally present at low concentration levels
(ng/g) in crustal rocks being siderophile elements
(Naldrett, 1981; Naldrett, 1989). Table 1 presents a
comparison of concentrations of PGE, Au and Re in
continental crust, mantle and core (Baker and Krogh-
Jensen, 2004). Metallogeny and genesis of PGE ores
and the geochemistry of PGE in magmatic systems
in Ni-Cu sulfide deposits are the subjects of on-
going active and intense research world over. The
behavior of these elements in different geological
settings is well understood. PGE is sub-divided into
two sub-groups with contrasting behavoural
characteristics: a) Ir-PGE, containing Os, Ir and Ru
and b) Pd-PGE containing Pd, Pt, Rh and Au. The
former are more siderophile and refractory in
comparison to the latter, which are more chalcophile
and volatile. During magmatic processes, they show
features like i) affinity towards sulfide phase (Pd-
PGE>Ir-PGE), ii) compatible character of Ir-PGE with
olivine fractionation with respect to Pd-PGE and iii)
compatible character of Ir-PGE and Rh with spinel
as well as geochemical studies indicate that olivine,
chrome-spinel and/or sulfides are the most
compatible mineral phases for PGE-enrichment
(Zhou, 1994; Barnes et al, 1985; Barnes and Maier,
1999). The principal types of PGE deposits around
the world are summarized in Table 2 (Naldrett, 2004).
2. PGE occurences in the world
The most important PGE metallogenetic
provinces are the Bushveld Complex of South Africa,
the Siberian flood basalt province and associated
magmatic sulfide deposit of the Noril’sk region in
Russia, the Sudbury structure with associated
sulfide deposit in Canada and the Stillwater Complex,
Montana, USA. Epithermal PGE mineraliztion in
association with gold at Coronation Hill in the
northern Territory of Australia and the alluvial
deposits of PGE along rivers in Choco Province of
north western Columbia are also important in this
context (Fig. 1). World’s proven major PGE deposits
are distributed in eight countries (Fig. 2) with South
Africa as the leading country (Vermaak, 1995).
Enormous reserves of PGE within the South African
Bushveld Complex are found in the Merensky Reef,
the Platreef and UG2 chromite layer (Davis and
Tredoux, 1985). The Great Dyke of Zimbabwe
constitutes the world’s second largest reserve of
PGE after the Bushveld Complex. However, the
economically viable PGE concentrations are
restricted to sulfide disseminations of the Main

* Keynote Address
441
 V. Balaram

Table 1. Concentrations (ng/g) of PGE, Au and Re in different phases of the Earth system (Modified
after Baker and Krogh-Jensen, 2004).
Element Continental Crust Mantle Core Corbonaceious Chrondrite (C1)@
Re 0.40 0.096 122 -
Os 0.03 2.700 1110 514
Ir 0.03 2.620 - 540
Ru 1.06 5.300 - 690
Rh - - - 200
Pt 1.50 8.420 5140 1020
Pd 2.00 4.900 - 545
Au 4.00 - - 152
@ Riddle, 1993.
Table 2. Types of PGE-mineralization in the world (Naldrett, 2004).

1. PGE-rich zones associated with Ni-Cu deposits-Noril’sk, Sudbury

2. Stratiform layers of PGE-rich sulfides in layered instrusions
(a) near changes in magma type-Merensky and J-M Reefs, UG-2
(b) in fractionated parts of intrusions - Skaergard, Sonju Lake
3. Strata-bound zones of PGE-rich sulfide near margins of layered intrusions - Platreef, Portimo,
River Valley.
4. Associated with chromitite zones without sulfides - Bushveld Lower Zone chromitites, Ophiolite
occurrences.
5. Associated with irregular zones of remelting within intrusions - Lac des Iles
6. Hydrothermally remobilized - Duluth, Bushveld Dunite Pipes
7. Associated with recrystallised chromite schlieren - Nizhny Tagil
8. Black Shales - Suhkoi Log.

Sulfide Zone (MSZ), which is found to be in
pyroxenitic host rocks a few meters below the
transition between the lower ultramafic and the upper
mafic sequence of the Great Dyke (Oberthur et al.,
2003). Eluvial and alluvial deposits of PGE have been
found in a number of areas around the world. They
have been mined in the erstwhile USSR, Canada,
Columbia and the USA. The metals in such deposits
occur as native alloys of varied composition. At
present 98% of the world’s PGE come from four
countries, South Africa (66%), Russia (23%), USA
(5%) and Canada (4%). Recently with promising
deposits such as Jinchuan Ni, Cu-(PGE) sulfide
deposit, China has also joined these countries in a
big way. Besides the Bushveld Complex, PGE
production comes largely as a by-product of mining
and extraction from magmatic Ni-Cu deposits, such
as from the vast PGE-rich deposits of the Noril’sk-
Talnakh camp in Siberia which is the major reserve
of this type. Canada’s Sudbury deposit is also an
important source. The only other deposits currently
being mined predominantly for PGE are the JM Reef
of the Stillwater Complex in Montana, USA
(a Bushveld-like occurrence) and the unique Lac Des
lles deposit in Ontario, Canada, which is primarily a
Pd deposit.
3. Petrogenesis of different PGE deposits
In order to form a deposit the processes of
segregation, migration and enrichment or a
combination of these process in a selective
environment must bring about the enrichment of one
or more minerals or metals. It therefore requires that
the constituent elements have to be acquired and
transported from a source region, and selectively
deposited in a location where the conditions are
physico-chemically favorable for ore formation.
These three domains, namely the source region, the

442
Exploration for Platinum Group Elements (PGE) in Peninsular India - status, problems and scope

Fig. 1. Major PGE deposits and reported occurrences around the world.

Fig. 2. Distribution of the PGE resources of world’s major deposits (Vermaak, 1995).

443
 V. Balaram
migration path-way and the depositional site,
therefore have a definite control on ore formation,
and ore deposits as prevalent for example, in the
massive chromite deposits in Bushveld Complex,
South Africa. It is suggested that primary
magmatogenetic concentrations of metals seldom
yield economically workable deposits. Subsequent
processes such as deformation, remobilization and
metamorphism acting upon the host rocks are
responsible for the release of metals entrapped in
crystal lattices of minerals in the lava piles or plutonic
igneous rocks and for mobilizing and concentrating
them in favorable locations. Recently Mungall (2005)
presented an excellent account of the behavior of
PGE in an igneous environment. According to him, it
is important to recognize that each magmatic suite is
unique, and blind application of simple
generalizations will usually lead to incorrect
conclusions. Metallic mineral deposits may also get
concentrated through hydrothermal processes at
sea-floor spreading centers.
4. Magmatic deposits
Magmatic Nickel-Copper-Platinum group
element sulfide deposits form as a result of
segregation and concentration of droplets of liquid
sulfide from mafic or ultramafic magma and the
partitioning of chalcophile elements into these from
silicate magma (Barnes and Picard, 1993). Magmatic
PGE deposits are economically significant. It is
believed that the PGE are mainly concentrated by
primary magmatic sulfides even in cases where
actually sulfur contents are relatively low, like in many
chromitites. Recently, Maier (2005) considers that
the first requirement to form primary magmatic PGE
deposit is that the mantle derived magma is fertile in
terms of PGE. The amount of PGE required for a
parental magma to form an economical PGE deposit
is not clear due to lack of data on parental magma
compositions from most of the major PGE mineralized
intrusions, but the Bushveld parental magma appears
to have about 10-15 ppb Pt and Pd each. As the PGE
have higher partition coefficients with regard to the
sulfide melts, the PGE would largely remain in the
cumulate portion and the fractionated basaltic magma
would be PGE-poor. Large degrees of mantle melting
produce komatiites and Mg-rich basalts as well as
the most important PGE deposits (Bushveld, Great
Dyke, Stillwater) which are associated with relatively
magnesium rich magmas (Mg-basalts).
Once the magma gets emplaced in the crust,
it is normally assumed that the dense droplets of
444
sulfide melt segregate at the base of the magma
chamber to form a sulfide enriched horizon, and
during this processes the highly chalcophile PGE
gets partitioned into sulfide melt. In large intrusions
(magma chamber), the sulfide droplets can equilibrate
(sink through) a large volume of magma and thus
scavenge more PGE from the magma. The mass ratio
of sulfide to silicate melt during sulfide segregation
is referred to as R factor (Cambell and Naldrett, 1979).
5. Layered intrusions
When a large body of mafic magma is
emplaced into the Earth’s crust, slow cooling takes
place. Silicate, oxide and sulphide minerals crystallize
and sink to the bottom of the magma chamber to
form texturally distinctive layers depending upon
oxygen fugacity, temperature, viscocity and other
factors. The removal of more refractory minerals in
this way depletes or enriches the residual melt in
various elements. The magma thus changes
continuously until solidification is complete. As a
result, elements such as the PGE, nickel and copper
when in the presence of a sulphide phase can become
sufficiently enriched to form mineralized horizons at
predictable levels within the intrusion (Buchanan,
1988). A prime example of such a body of layered
igneous rock is the Bushveld Complex of South
Africa.
6. Intrusive and extrusive mafic intrusions
Sulphide mineralization can also be
associated with smaller bodies of mafic and ultramafic
intrusive and extrusive magma, provided the original
magma was enriched in PGE. These intrusions can
also host significant levels of PGE mineralisations.
The Sudbury nickel sulphide deposit in Canada is a
prime example of sulphide mineralisation associated
with a small mafic intrusion.
7. Other types
Alluvial deposits of PGE for example, along
rivers in the Choco province of northwestern
Colombia are found in association with gold. Placer
platinum deposits were discovered in central Ural
Mountains in 1819, north of Sverdlovsk. In the early
1920’s, these placer deposits represented virtually
the only source of platinum upto the discovery of
Bushveld. Today, placer PGE deposits contribute
only a small proportion of the world’s PGE production
(less than 2%). Epithermal PGE mineralisation
associated with gold is also known from Coronation
Hill in the Northern Territory of Australia. In the
Zechstein copper deposits of Poland, gold and PGE
 Exploration for Platinum Group Elements (PGE) in Peninsular India - status, problems and scope
are concentrated in a layer a few centimeters thick at
the bottom of black shale. Hydrothermal fluids
probably introduced the PGE but these deposits
represent geologically exotic environments.
Although hydrothermal processes may have
redistributed or concentrated magmatic PGE, there
appears to be little realistic potential for significant
resources of PGE of purely hydrothermal origin
(McCallum et al., 1976).
8. Manganese nodules / crust as possible
sources of PGE
Marine geochemical studies of Pt and Ir show
that both these elements are relatively enriched in
manganese nodules and in manganese crust, with
concentration upto 900 ng/g and 7 ng/g respectively,
compared to 3 ng/g Pt and 0.2 ppb Ir in pelagic clays.
Pt and Ir are incorporated into hydrogenous Fe-Mn
oxyhydroxide minerals, and these phases might
control the distribution of Pt and Ir in manganese
nodules as well as in marine sediments. It is also
observed that Ir and Pt enrichments in oceanic
sediments are accompanied by enhanced Fe, Mn,
Cu and Ni concentrations (Banerjee, 2004). Fe-Mn
(FeOOH, MnO2) crusts precipitate out of cold
ambient seawater (hydrogenetic) onto hard-rock
substrates throughout the ocean basins at water
depths of about 400 to 4000 m. They grow at
incredibly slow rates (1-6 mm/myr), have high
porosity (mean 61%), and enormous specific surface
area (mean 323 m2/g). These characteristics promote
the acquisition of large quantities of metals from
seawater most notably Co from an economic
standpoint and Te in terms of enrichment (5,000-
50,000 times) relative to its Earth’s crustal abundance
Pt, Mn, Mo, Co, Bi, Tl, As, Pb, W, and Sb and the
other elements also get enriched (50-250 times) in
Fe-Mn crusts relative to their Earth’s crustal
abundances. The concentrations of PGE obtained
in the manganese crust sample from central Indian
Ocean basin (Table 3) show that these samples are
strongly enriched especially with respect to Pt, Ru
and Ir. These high concentrations of Pt, Ru and Ir
are due to oxidative scavenging into the MnO2 and
FeOOH. Studies show that manganese crusts from
the ocean basins can be an alternative resource for
PGE (Balaram, 1999; Balaram et al., 2005; Hein et al.,
2005).
9. PGE resources in India
The most important undiscovered PGE
resources are likely to occur in those regions of vast
geographic extent like Central Asia, China, India,
445
South America, the Pacific Rim and Africa outside of
South Africa (Mungall et al., 2004) (Fig. 2). There are
limited PGE occurrences in India and undiscovered
PGE resources are likely to occur in those regions.
The layered ultramafic intrusions with chromite have
indicated high to moderately anomalous PGE values,
though no significant breakthrough was achieved
in PGE discovery during the last two decades.
At present the three promising PGE occurrences,
i) Baula-Nausahi Complex in Orissa and ii) mafic-
ultramafic Hanumalpur Complex in the Shimoga
District, Karnataka and iii) Sittampundi Anorthosite
Complex in Tamil Nadu have been identified as
potential deposits (Fig. 3). Geological Survey of India
(GSI) has carried out massive exploration survey for
PGE in the ultramafic rocks, laterites and placers in
chromiferous Sukinda ultramafic belt, but the results
are not encouraging though very high values for Ag
(20-1433 mg/g) (Table 4) were obtained (Balaram et
al., 1999). The Baula-Nausahi igneous complex
however holds great promise (Mukerjee and Patra,
2001).
Nausahi ultramafic-mafic complex occurs
within the 3.2 Ga old Archaean iron ore group made
up of metasedimentary and metavolcanic rocks. The
economic potential for PGE minerals was identified
from the brecciated zone of Baula-Nausahi complex
(Mohanty and Sahoo, 1989; Mondal and Baidya,
1997; Baidya et al., 1999; Mukherjee and Patra, 2001).
This breccia zone contains high concentration of
platinum group elements (Pt upto 9.6 mg/g; Pd upto
17.9 mg/g and Au upto 6.6. mg/g (Mondal et al., 2001).
Sittampundi Anorthosite Complex, Tamil Nadu is
another promising area with the concentration of
PGE upto 0.93 mg/g (Sundaram, 1984). GSI had
carried out reconnaissance survey for PGE in
chromitite and chromite bearing pyroxenite of
Karungalpatti area, Sittampundi Anorthosite
Complex and identified ten chromitite bands in
Karungalpatti area with concentrations of ∑PGE in
the range 30ng/g to 4.67 mg/g (Kumaraguru and
Gopalakrishnan, 1996). Recent work also shows an
unusually thick sulfide-poor mineralized zone
enriched in PGE (Pt+Pd+Au nearly 6 mg/g) in the
late Archaean Hanumalapur complex, Shimoga
District, Karnataka in Western Dharwar Craton in
the south India (Devaraju et al., 2002; 2004; 2005).
Chromites are the important hosts of PGE in
the ophiolitic complexes (OC), such as the Mayari-
Baracoa OC, Cuba; Neoproterozoic OC of Bou-Azzer,
Morocco; Mersin OC, Turkey; Ray-Iz OC, Polar Urals,
Finland; Acatlan OC, Southern Mexico; New
 V. Balaram

Table 3. Comparative data (in ng/g) of PGE in a few manganese nodule samples from central Indian
Ocean by NiS-FA and ICP-MS from two different laboratories (Balaram et al., 2006).

Au Ir Pd Pt Rh Ru
Sample
USGS NGRI USGS NGRI USGS NGRI USGS NGRI USGS NGRI USGS NGRI
CC2/ADR12 18 21 11 7 13 13 636 580 40 35 17 11
CC2/ADR10 7 16 6 2 5 13 149 65 13 6 1 6
CC2/ADR11 11 277 6 2 6 13 166 88 13 17 1 8
CC2/ADR18 10 9 10 7 10 13 610 523 33 30 30 25
CC2/ADR19 13 9 9 7 8 11 568 512 38 35 20 18
CC2/ADR20 14 26 8 5 11 13 673 623 31 28 12 8
CC2/ADR24A 19 13 4 2 4 15 101 80 7 6 12 10
CC2/ADR24B 29 16 5 3 11 11 110 89 9 8 15 12
CC2/ADR26 15 7 3 2 6 12 102 79 6 6 12 8
CC2/ADR27 18 10 10 6 20 11 286 229 23 21 31 20
CC2/ADR4 13 3 5 1 8 9 111 36 10 5 15 5
CC2/LDR5B 11 8 5 4 7 11 148 150 13 13 12 10
CC2/LDR5A 22 22 10 6 13 11 292 223 25 21 17 14

NGRI : NiS fire-assay (11000C) - Te coprecipitation - ICP-MS estimation

USGS : NiS fire-assay (12000C) - ICP-MS estimation

Table 4. Concentration (μg/g) of precious elements in some chromite ore samples from the Sukinda valley,
Orissa, (Balaram et al., 1999).

Element Su-1 Ti-1 Ka-1 K1-1 Kt-1

Ru 0.12+0.01 0.10+0.01 0.08+0.01 0.05+0.01 0.03+0.01
Rh 0.06+0.01 0.05+0.01 0.05+0.01 0.04+0.01 0.03+0.01
Pd 0.24+0.02 0.19+0.02 0.17+0.01 0.21+0.01 0.21+0.02
Ag 570.83+17.11 35.65+0.01 19.78+1.20 64.37+1.95 1452.68+43.5
Os 0.03+0.01 0.04+0.01 0.08+0.01 0.05+0.01 0.07+0.01
Ir 0.08+0.01 0.11+0.01 0.12+0.01 0.11+0.01 0.03+0.01
Pt 0.12+0.01 0.08+0.01 0.07+0.01 0.09+0.01 0.14+0.01
Au 0.07+0.01 0.08+0.01 0.05+0.01 0.09+0.01 0.13+0.01

446
 Exploration for Platinum Group Elements (PGE) in Peninsular India - status, problems and scope
Caledonia OC, France; Veria OC, Northern Greece,
etc. In India, ophiolite sequences occur in i) Dras
ophiolite in the Himalayas, ii) Naga Hills Ophiolite
(NHO) belt, and iii) the Andaman-Nicobar Islands,
though economic deposits of PGE are not reported.
The Nagaland ophiolite belt is favourable for PGE
and the Pt, Pd and Rh concentrations in the mafic
and ultramafic rocks particularly from the chromite
bearing horizons of the belt in which PGE range from
33.8 to 209 ng/g (Tables 5 and 6) are encouraging
(Subba Rao et al., 2004b; Balaram et al., 2004; Balaram
et al., 2006). The Indus Suture Zone (ISZ) ophiolites
contain a sequence of chromite, PGE and Ni-sulfides
minerals. The Nidar ophiolite, one of the largest
ophiolite complexes of the ISZ in the eastern part of
the Ladakh, chromites and sulfides (chalcopyrite,
pyrrhotite, pyrite and arsenopyrite) occur within the
serpentinised ultramafic rocks. The massive
chromitites contain 1-2.5 μg/g of PGE (Siva Siddaiah
and Masuda, 2001). Unlike the Siberian traps of
Russia which host the Norilsk-Talnakh Ni-Cu-PGE
deposit, the continental flood basalt (CFB) provinces
of India were not studied in detail for PGE-
mineralization. Recently, Crocket and Paul (2004)
studied PGE-mineralization in a suite of mafic rocks
(basalts and dolerite dykes) from Maharashtra region
in the Western Deccan volcanic province. But, the
PGE concentrations reported are of no economic
significance. Subba Rao et al. (2004a) identified
promising PGE concentrations (Σ PGE ranging from
19-165 ng/g) in the Archaean layered mafic-ultramafic
rocks from Nuggihalli greenstone belt, South India.
In addition to this, the chromite bearing ultramafic
rocks from Bababudan Nallur shear zone in Karnataka
contain significant concentrations of PGE (Hussain
and Sunder Raju, 2005).
10. PGE-Exploration studies
Metallogenic investigations of PGE rely on a
synthesis of geochemical, tectonic and structural
information coupled with deposit models to define
characteristics of terrains favorable for deposit
formation. PGE-exploration techniques have radically
changed our outlook and approach to PGE-
resources. These include analytical techniques and
experimental methods, the role of fluids in layered
igneous complexes, ophiolites, the discovery of
economically viable PGE deposits in non-traditional
rocks such as, metaliferous black shales and PGE
concentrations in other marine sediments and
porphyry copper deposits. (Martin, 2002). Not only
“orthomagmatic” environments in layered igneous
complexes (or in ophiolites) are relevant for
447
exploration, but pegmatoids, breccias, alteration
zones and veins should also be considered. The
structurally controlled “offset” deposits in the
footwall of Sudbury Complex, Ontario, often have
high levels of PGE. On the regional scale, features
such as the irregular distribution of PGE, at only
moderately varying PGE contents, as in the Merensky
Reef of the Bushveld Complex point towards fluid
controlled distribution, or redistribution of PGE.
These irregular patterns cannot be easily explained
by sulfide scavenging PGE from turbulently mixed
magmas in the hanging wall of a reef. On the local
(km) scale, the recognition of oxides represented a
breakthrough. This was followed by the discovery
of minable quantities of oxidic PGE ores in the Great
Dyke of Zimbabewe (Stumpfl, 2004).
11. Chondrite-Normalized PGE and Au
distribution patterns
Ir and its geochemical analogue, Os form high-
temperature alloys and behave as compatible
elements being retained in refractory mantle residues.
Pt and Pd are incompatible elements and partition
into the silicate melt, but are also strongly partitioned
into sulfides relative to silicate minerals and melts
(Naldrett and Duke, 1980) and hence their behavior
is largely considered exclusively chalcophilic in
sulfide bearing systems. The sulfide component and
sulfur abundance are, therefore, central to any study
of PGE signatures in the upper mantle and to an
understanding of the genesis of magmatic PGE-rich
sulfide ore bodies associated with basaltic
magmatism (Lorand, 1989; Baidya et al., 1999). The
concentrations of PGE and Au, normalized on the
basis of elemental abundance in Type 1
carbonaceous chondrite (C1), are plotted against
these elements in the order of their melting points,
which provide patterns that are much more regular
than those that would be obtained if the unnormalized
data were directly plotted. The elemental abundances
in C1 chondrites (Table 1) are the best available
indication of cosmic abundances (Naldrett and Duke,
1980). These chondrite-normalised PGE and Au
distribution patterns provide information on the
source and redistribution of elements within a
deposit after emplacement of the metal bearing
sulfide liquid by fractional crystallization, diffusion
of elements in response to thermal gradient and
hydrothermal activity. These chondrite-normalized
plots also help in the assessment of the accuracy of
PGE and Au data. Fig. 4 presents chrondrite-
normalised PGE patterns for a few selected samples
from Baula Complex (Auge et al., 2002).
 V. Balaram

Fig. 3. Reported occurrences of PGE in India.

448
 Table 5. PGE concentrations (ng/g) in the ultramafic suite of NHO belt (Subba Rao et al., 2004b).

0 7.3 8.6 6.4 0 16.5 8.5 2.7 7.4 12.4 11.9 7.3 12.8 4.5
0.7 1.1 2.4 0.8 0 3.4 1.7 1.1 2.4 2.9 3.2 1.2 2.3 1.4
12.4 60.8 0 0 0 44.0 0 15.2 44.8 134.4 0 0 24 14.8
0.1 3.1 6.2 3.3 0.4 9.6 4.3 2.3 4.5 6.9 6.8 2.9 7.0 3.1
3.3 6.1 13.6 11.4 2.4 14.8 7.5 3.9 95.0 24.4 27.7 6.2 22.3 9.2
12.6 8.7 12.1 55.7 0 22.7 8.8 7.2 12.0 28.3 16.4 6.6 10.1 7.3
4.7 0 0 0 0 18.0 15.8 69.4 5.7 0 0 1.7 20.3 0
34.0 87.0 42.9 78.0 2.8 129.0 47.0 102.0 172.0 209.0 66.0 25.9 99.0 40.0

449
449
Table 6. PGE and gold concentrations (ng/g) in the gabbros of the NHO belt (Subba Rao et al., 2004b).

NOB-94 NOB-95 NOB-99 NOB-100 NOB-121 NOB-122

Ir 1.2 0.01 1.30 1.5 0.3 0.01
Ru 2.9 0.70 0.70 1.5 0.8 0.50
Rh 236.0 0.01 60.40 170.0 28.4 18.80
Pt 0.2 0.10 0.01 0.6 0.2 0.01
Pd 1.3 0.50 0.30 1.0 0.4 0.30
Os 12.1 1.80 3.80 9.9 14.9 6.50
Au 22.2 12.90 9.90 18.3 26.5 37.40
Exploration for Platinum Group Elements (PGE) in Peninsular India - status, problems and scope

ΣPGE + Au 275.9 16.02 92.40 202.8 71.5 63.50

 V. Balaram
Rock/Chondrite
Fig. 4. Chondrite-normalised PGE patterns for a few selected samples from Baula Complex (Auge et al.,
2002).
PGE mineralization in the Baula Complex
occurs in two environments both associated with
the Bangur Gabbro. The first type of mineralization
is Pt-dominant and restricted to the basal part of the
Bangur Gabbro, where chromitite has been
incorporated into the gabbro as nodules (magmatic
origin). The second type is Pt-dominant and occurs
in gabbro matrix of the breccia zone in
hydrothermally altered rock, where it is usually
associated with basemetal sulfides and ferrian
chromite (hydrothermal origin). PGE, Au and Re
content of a few selected samples from two
mineralized environments from Baula complex, India
are provided in Table 7 (Auge et al., 2002). A zircon
age of 3122+5 Ma was obtained on PGE mineralized
gabbro intrusion of the Baula Complex (Auge et al.,
2003). Fig. 5 presents the chrondrite - normalized
PGE patterns of rocks from the NHO belt. The
patterns in gabbro show negative slopes towards
the Ir-PGE indicating their more fractionated nature,
while the ultramafic cumulates have relatively flat
patterns with a slight enrichment of Pd over Pt except
in a few samples suggesting only a limited
fractionation of PGE in them (Subba Rao, 2004).
450
12. PGE analysis - general principles
Exploration for precious metal deposits is
typically characterized by large-scale integrated
surveys comprising of remote sensing, geophysical
survey, geological mapping, petrological and
geochemical studies, exploration geochemistry,
sampling and analysis leading to the establishment
of iso-concentration contour maps, describing the
distribution and occurrence of economically
important deposits. Consequently, analytical
methods developed for the determination of precious
metals in geological samples must have sufficient
sensitivity to quantify individual PGE at ng/g level
and sufficient rapidity to make sampling and analysis
in exploration studies economically feasible. The first
challenge in this process is to obtain a representative
sample for analysis. The PGE are not evenly
distributed between the mineral phases in most of
the rocks and often segregate in PGE minerals, as
inclusions in phases such as spinel, or in solid
solution within sulfides (Barnes et al., 1985). Hence,
PGE are generally found to be heterogeneously
distributed within an ore body and tend to be
 Exploration for Platinum Group Elements (PGE) in Peninsular India - status, problems and scope

Table 7. PGE, Au and Re content (ng/g) of selected samples from the two mineralized environments,
Baula Complex, India (Auge et al., 2002).

ppb Os Ir Ru Rh Pt Pd Au Re
Type 1 Magmatic
OBG1 226 636 1670 2210 5240 770 15 20
OBG1R 143 485 1220 1800 1100 173 2 13
BN40 355 1250 3550 3830 9700 1720 20 32
Type 2A Hydrothermal, sulfide-bearing
BLR96 30 113 188 1170 1650 25800 3250 28
FGH4 2 7 53.6 249 280 4350 3070 149 <1
FGH4 59 6 16.4 128 37 516 2300 70 <1
Type 2B Hydrothermal, sulfide-free
FGH5 91 16 33.8 207 85 1000 1210 92 2
FGH5 92 30 78.7 429 203 2460 2200 46 4
FSH1 42 15 39.5 201 161 1230 1450 55 2

10.00000 1.00000

1.00000
0.10000
Rock/Chondrite
Rock/Chondrite

0.10000
0.01000
0.01000
0.00100
0.00100

0.00010
0.00010

0.00001 0.00001
Os Ir Ru Rh Pt Pd Os Ir Ru Rh Pt Pd
Fig. 5. Chondrite-normalized PGE patterns of ultramafic cumulates (a) and mafic cumulates (gabbros) (b) of
Naga Hills Ophiolite belt, India (Subba Rao et al., 2004).

451
 V. Balaram

agglomerated in discrete particles or phases. These
characteristics should be taken into consideration
when sampling strategies are formulated. Sample
preparation protocols must incorporate sufficient
grinding and mixing to homogenize the collected
sample. The extent to which this can be minimized
and representative PGE concentrations obtained
from any individual sample aliquot depends on:
i) the initial distribution of individual PGE between
different PGE-rich phases; ii) the average particle
size (many PGE minerals are <5 nm size across) in the
crushed sample; and iii) the mass of sample analyzed
(larger test portions contain greater number of PGE
rich particles and thus average out statistical
variations (McDonald, 1998). Some workers have
concluded that it may be impossible to entirely
homogenize Au and PGE in many geological materials
(e.g., Potts, 1987). Hence, usually relatively high
amounts (5-50 g) of sample masses are typically used
in the chemical analysis of PGE. Regardless of how
precise the actual analysis procedure is, there will
always be a degree of uncertainty over how
representative any selected aliquot is relative to the
whole sample. Moreover, the analysis of a single
aliquot does not allow measurements of all possible
uncertainties involved, particularly those caused by
sampling. Therefore, replicate analyses are the best
means by which one can assess the reproducibility
of data from rocks, that are heterogeneous with
respect to Au and PGE.
Following the selection of a representative
sample of the ore, one should look for an appropriate
Table 8. Comparative detection limits of PGE and Au by atomic, nuclear and mass spectroscopic techniques.
analytical method for the precise determination of
PGE. Analytical techniques such as flame atomic
absorption spectrometry (F-AAS) and inductively
coupled plasma atomic emission spectrometry (ICP-
AES) cannot achieve the sensitivities required for
the precise estimation of PGE in different rocks and
ore samples. Table 8 presents a comparison of the
detection limits offered by different analytical
techniques for PGE and Au. Obviously, it requires a
high sensitive analytical technique such as
inductively coupled plasma mass spectrometry (ICP-
MS) for their precise estimation. In addition, the low
abundances of PGE in geological minerals require
the use of separation and preconcentration
processes. The most common procedure is the well-
known fire assay technique. Here the ore sample is
fused with a known amount of flux and the Au and
PGE are selectively extracted and collected either in
a lead or nickel sulfide phase. In the case of lead
collection, the button is cupelled in a furnace to give
a noble metal prill, which will be typically dissolved
using aqua regia, and the PGE and Au are determined
by ICP-MS. In the case of nickel sulfide pre-
concentration, NiS beads or buttons are generally
dissolved in HCl, and PGE and Au remain as the
residue. The residue is dissolved in aqua regia and
analyzed by ICP-MS or instrumental neutron
activation analysis (INAA) (Stone and Crocket, 1993;
Balaram, 2001; Balaram et al., 2006). With the advent
of these sensitive mass spectrometer techniques,
especially, ICP-MS and more innovative chemical
procedures, the capability to analyse PGE and gold

Limit of determination (ng/g)

Element GF-AAS Flame-AAS INAA ICP-AES AMS ICP-MS
(ng/g) (μg/g) (ng/g) (ng/g) (ng/g) (ng/g)
Ru 3.0 0.50 10.0 125 3.90 0.016
Rh 0.5 0.10 1.0 25 0.45 0.010
Pd 0.2 0.10 4.0 30 4.40 0.010
Ir 2.5 0.75 0.1 160 0.26 0.005
Pt 1.6 1.00 10.0 40 0.11 0.004
Au 0.1 0.20 1.0 10 0.01 0.010
GF-AAS : Graphite Furnace Atomic Absorption Spectrometry
Flame-AAS : Conventional atomic absorption spectrometry
INAA : Instrumental neutron activation analysis
ICP-AES : Inductively coupled plasma atomic emission spectrometry.
ICP-MS : Inductively coupled plasma mass spectrometry
AMS : Accelerator mass spectrometry (Wilson et al., 1995)

452
 Exploration for Platinum Group Elements (PGE) in Peninsular India - status, problems and scope
in rock samples has increased to parts per billion
(ppb) and even parts per trillion (ppt) range. Analysis
of PGE and Au is subjected to a number of significant
oxide-based interferences in ICP-MS. Their removal
would therefore constitute a significant improvement
in analytical accuracy. A dynamic reaction cell (DRC)
based ICP-MS can be utilized with oxygen as the
reaction gas to promote oxidation of interfering
species to higher oxides, with a resulting separation
of analytes from the interfering oxides (Simpson et
al., 2001). Of particular concern is the possible
contamination of samples during sample preparation,
sample grinding and powdering. Minimizing cross
contamination between samples is more important.
Laboratory reagents and laboratory environment are
also important factors that affect the accuracy of
determination. At low concentrations, the reagent
blank becomes a limiting factor for the accurate
determination of PGE. Although every reagent used
in the procedure contributes, the PGE content in
nickel powder is very important. High pure nickel
powder (99.999%, - 100 mesh) with extremely low
blank values only is suitable for such estimations
(Balaram et al., 2006). Other sources of laboratory
contamination can be minimized by using ultra-pure
reagents, clean laboratory atmosphere for sample
preparation, and good laboratory practices (e.g. no
jewelry worn and use of gloves).
13. In-situ analysis of PGE
The distribution of PGE in sulfide minerals
will provide important information for researchers in
studying, mantle processes, magma generation,
magmatic ores and crustal contamination. In order
to establish the first order link between PGE and
sulfides in magmatic systems, it is necessary to
determine PGE concentrations in different sulfides,
by identifying the different PGE bearing minerals.
For industrial metallurgical extraction studies, in
addition to the information on the bulk values of
PGE, it is also necessary to identify and characterize
different PGE minerals with which these elements
are associated. Laser ablation inductively coupled
plasma mass spectrometry (LA-ICP-MS) is highly
suitable for such studies (Schonberg and McMurtry,
1994). However, interferences caused by metal-
argide molecules are problematic especially when
considering in-situ analysis of Ni, Cu, Co and Zn
sulfides. Two slightly different external correction
methods are commonly applied. The first involves
the analysis of several reference materials (pure PGE,
Ni-bearing PGE etc.) during each analytical session
453
and directly measuring argide interferences
(Sylvester, 2001). Alternatively, a pure metal such as
copper can be analyzed during each session and
ratio of metal / metal-argide determined (Allard et al.,
2000). Cox and Barnes (2005) successfully reduced
the effects of argide interferences using high-
resolution ICP-MS (HR-ICP-MS) or by the use of
reductant gases in a hexapole collusion cell ICP-QMS
instrument (HEX-ICP-QMS). The method was
applied to natural samples in the study of
compositionally zoned sulfide droplets from
Medvezhy Creek mine, Norilsk, Russia. This study
also demonstrated that PGE compositional variations
could now be studied effectively at the 40-80 mm
scale.
14. Constraints in exploration studies in
India and future directions
The Indian subcontinent is bestowed with
good mineral wealth and there may be many mineral
deposits, which are yet to be discovered. There is
also a great need to develope intensive and extensive
integrated methods of exploration in conjunction
with geological, geophysical and geochemical
techniques for discovering world-class concealed
PGE deposits which might have remained undetected
so far by conventional methods of exploration.
Metallogenic investigations of metallogeny of PGE
rely on a synthesis of geochemical, tectonic and
structural information with deposit-scale ore deposit
models to define the characteristics of terranes
favourable for deposit formation. The results of
metallogenetic models can be used to assess the
potential for undiscovered PGE deposits of different
types on a regional scale. Such studies are extremely
important, especially in view of the increasing
demand for PGE. In our country, the efforts made so
far for PGE exploration studies appear to be
inadequate despite the presence of several favorable
locales. It is high time that a comprehensive action
plan for the exploration of PGE is initiated. It is also
necessary to assess and consolidate our national
PGE resources including known and potential
reserves, update the knowledge and techniques of
PGE exploration, and improve our understanding of
PGE as tracers of geochemical processes and of the
mechanisms of formation of major deposits of the
PGE. Detailed geological, petrological and
geochemical studies have to be carried out on a
massive scale in different potential areas across
Peninsular India and the data should be evaluated
for the purpose of potentiality of PGE mineralization
 V. Balaram
and identifying economically viable deposits and
their mining. By combining on-going research on
the regional and deposit-scale controls on PGE
mineralization with the knowledge available in the
regional and global database, we will be able not
only to define metallogenetic provinces based upon
known mineral occurrences, but also to define
regions of high potential based upon general
principles of PGE deposit formation. It is also
necessary to strengthen chemical laboratories of
earth science R & D organizations across the country
by setting up several fire-assay laboratories with
ICP-MS, LA-ICP-MS, SEM-EDS and other related
state-of-the-art analytical instrumentation. The staff
should be properly trained with latest advancements
in PGE exploration.
Acknowledgements
The author is grateful to Dr. V.P. Dimri,
Director, National Geophysical Research Institute,
Hyderabad for permission to publish this paper.
Dr. R. Gopalakrishnan (Sr. Geologist) AMSE Wing,
Geological Survey of India, Bangalore and
Dr. S.N. Charan (NGRI) are thanked for their valuable
comments on the earlier version of the manuscript.
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Received on 31-03-06; Revised Ms accepted on 15-06-06