Ore Geology Reviews 91 (2017) 509–529

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Ore Geology Reviews

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Chemistry of magnetite-apatite from albitite and carbonate-hosted Bhukia T

Gold Deposit, Rajasthan, western India – An IOCG-IOA analogue from
Paleoproterozoic Aravalli Supergroup: Evidence from petrographic, LA-ICP-
MS and EPMA studies
⁎
Rahul Mukherjeea, A.S. Venkatesha, , Fareeduddinb
a
Department of Applied Geology, Indian Institute of Technology (Indian School of Mines), Dhanbad 826004, India
b
Geological Society of India, No. 1532, 14th Main, Kumaraswamy Layout, Bangalore 560078, India

A R T I C L E I N F O A B S T R A C T

Keywords: The Bhukia gold (+copper) deposit hosted by albitite and carbonates that occur within the Paleoproterozoic
Aravalli-Delhi Fold Belt Aravalli-Delhi Fold Belt (ADFB) in western India consists of magnetite, graphite, apatite and tourmaline along
Bhukia Gold Deposit with sulfide mineralization. Ubiquitous presence of magnetite and apatite in gold-sulfide association, alteration
Hydrothermal magnetite patterns and shear controlled mineralization suggest it to be IOCG (Iron-oxide copper gold) type deposits. The
Fluorapatite
detailed mineral chemistry of magnetite and apatite are generated and interpreted in terms of their genetic
IOCG-IOA association
significance, hydrothermal and magmatic origin vis-à-vis their affiliation with IOCG deposition. The data suggest
that the magnetite has hydrothermal affiliation. The Ni/Cr ratio is greater than 1, which is explained by dif-
ferences in solubility and mobility of Ni and Cr in hydrothermal fluids and is corroborated with other key
evidences including that of wide ranging Mg concentration further supports a strong hydrothermal input that is
envisaged for the deposition of magnetite. Concentration of vanadium in magnetite is generally < 1000 ppm in
case of barren hydrothermal occurrences while in the study area, it is relatively higher as it is attributed to the
gold-sulfide-Cu mineralization. Ti vs Ni/Cr, Ni/(Cr+Mn) vs Ti+V, Ca+Al+Mn vs Ti+V and Al+Mn vs Ti+V
variations are interpreted in terms of magnetite genesis. EPMA data suggests that apatite present in Bhukia is of
fluorapatite variety with F content > 1 wt% and F/Cl > 1. Higher concentration of F and moderate Mn along
with lower concentration of Cl attests their magmatic hydrothermal character and its derivation from meta-
volcano sedimentary source. REE patterns obtained from LA-ICP-MS analysis suggest enrichment of LREE re-
lative to MREE and HREE with negative Eu anomaly. Y/∑REE, La/Sm, Ce/Th and Eu/Eu∗ vs Ce/Ce∗ values of
apatite is indicative of their origin in a highly oxidized environment. Presence of magnetite along with apatite is
a common feature in IOCG-IOA (Iron-Oxide Apatite) association. Bhukia Gold Deposit has many similarities with
Kiruna type Iron-Oxide Apatite (IOA) deposits particularly with respect to their similar tectonic setting, al-
teration patterns, mineral assemblages such as abundance of magnetite, apatite and presence of late stage sul-
fides based on EPMA and Laser ablation ICP-MS (LA-ICP-MS) studies. Lithological, petro-mineralogical and
geochemical signatures of magnetite and apatite infer that the Bhukia is a possible IOCG-IOA type gold deposit
typically associated with sulfides and graphite which may be used as petrogenetic indicators and pathfinders for
exploration.

1. Introduction
Magnetite is commonly found in various geological environments
either as a major or an accessory mineral (Dupuis and Beaudoin, 2011;
Xiaowen et al., 2014; Chen et al., 2015b; Makvandi et al., 2016). It
forms at a lower temperature from hydrothermal fluids and concentrate
to form hydrothermal magnetite deposits (Bookstrom, 1995; Groves
et al., 2010; Nadoll et al., 2012) or it can crystallized from high tem-
perature silicate and sulfide melts (Dare et al., 2014). Magnetite is a
common ore mineral in many banded iron formations (BIF) (Nadoll
et al., 2012, 2014; Chung et al., 2015), also found in varying amounts in
a wide variety of geological environments (Philpotts, 1967; Dupuis and
Beaudoin, 2011; Dare et al., 2014; Liu et al., 2015). Its universality
could be attributed to its formation under relatively high temperature

⁎
Corresponding author.
E-mail address: asvenkatesh@hotmail.com (A.S. Venkatesh).

http://dx.doi.org/10.1016/j.oregeorev.2017.09.005
Received 22 November 2016; Received in revised form 6 September 2017; Accepted 11 September 2017
Available online 13 September 2017
0169-1368/ © 2017 Elsevier B.V. All rights reserved.
R. Mukherjee et al.
Fig. 1. (A) Log fO2–T diagram representing relevant fields for the Fe–Si–O system where HM: hematite–magnetite, FMQ: fayalite–magnetite–quartz, MW: magnetite–wüstite, IW:
iron–wüstite, IM: iron-magnetite, and QIF: quartz–iron–fayalite. (B) Schematic fO2–fS2 phase diagram for the Fe–O–S system. The geometry of the diagram remains same, though fO2 and
fS2 values significantly vary with temperature. (A) is after Frost et al. (1988), Frost (1991a) and Nadoll et al. (2014). (B) is after Hall (1986) and Nadoll et al. (2014).
conditions and appropriate fO2 regimes. At lower temperature it con-
centrates to form hydrothermal magnetite deposits and at high tem-
perature it crystallizes together with silicate-sulfide minerals from pri-
mary magmatic melts. It could be clearly demonstrated from log fO2-T
diagram with the barriers of Fe-O-S system and a schematic fO2-fS2
phase diagram for Fe-O-S system (Fig. 1A and B respectively) (Frost
et al., 1988; Frost, 1991a; Nadoll et al., 2014). The lower limit of
magnetite stability at minimum oxygen fugacity for any given tem-
perature is the iron-magnetite (IM) or magnetite-wüstite (MW) barrier
line (Buddington and Lindsley, 1964; Frost, 1991a). Incorporation of Fe
into magnetite and silicates is marked by the fayalite–magnetite–quartz
(FMQ) barrier line. Above the FMQ line, iron is mainly present within
magnetite, while the inclusion of Fe within silicates is present below the
FMQ line. Most of the Fe occurs in native state below the quartz–ir-
on–fayalite (QIF) line. Hematite-magnetite (HM) barrier line marks the
upper limit for magnetite stability, above which hematite is the prin-
cipal Fe-oxide mineral (Buddington and Lindsley, 1964; Frost, 1991a).
Magnetite compositions can reveal the physicochemical conditions
under which it was formed. Trace elements commonly present within
the magnetite structure include Mg, Al, Sc, Ti, V, Cr, Mn, Co, Ni, Zn, Ga,
Ge, Y, Hf, Nb, Mo, Ta and Zr in addition to Fe (Klemm et al., 1985;
Nadoll and Koenig, 2011; Nadoll et al., 2012; Dare et al., 2012, 2014).
These trace elements are useful petrogenetic indicators and pathfinder
minerals for exploration (Carew et al., 2006; Reguir et al., 2008;
Beaudoin and Dupuis, 2009; Dupuis and Beaudoin, 2011; Galicki et al.,
2012; Angerer et al., 2013; Dare et al., 2012, 2014; Nadoll et al., 2012,
2014; Boutroy et al., 2014; Huang et al., 2014; Chen et al., 2015a).
Incorporation of trace elements within the magnetite depends on many
factors including similarities of the ionic radius and cation valences,
oxygen fugacity (fO2), magma/fluid composition and temperature
(Buddington and Lindsley, 1964; Lindsley, 1991; Toplis and Carroll,
1995; Dare et al., 2014; Nadoll et al., 2014; Chen et al., 2015b). Dare
et al. (2012) used distribution of trace elements to differentiate between
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Ore Geology Reviews 91 (2017) 509–529
magnetite crystallized from silicate melts, those crystallized from sul-
fide melts and hydrothermal fluids. In view of the above assumptions,
the magnetite compositions vary in different ore forming environments
such as Iron Oxide–Copper–Gold (IOCG), Kiruna apatite-magnetite,
banded iron formation (BIF), porphyry Cu, Fe–Cu skarn, Magmatic Fe-
Ti-V-Cr, Ni–Cu–PGE, Cu–Zn–Pb volcanogenic massive sulfide (VMS)
and Archean porphyry Cu–Au (Dupuis and Beaudoin, 2011; Nadoll
et al., 2014; Makvandi et al., 2016).
In addition to magnetite, apatite is also useful as an indicator mi-
neral from IOCG deposits to record the host rock composition and the
volatiles present within the crystal structure of apatite which in turn
reflects the content of volatiles within the parental magmas (Patiño
Douce and Roden, 2006; Boyce and Hervig, 2009; Filiberto and
Treiman, 2009; Boyce et al., 2010; Greenwood et al., 2011; Gross et al.,
2013; Tartèse et al., 2014; Treiman et al., 2014; McCubbin et al., 2015).
Besides magnetite, apatite is often most common and important ac-
cessory mineral present in a wide range of igneous, metamorphic and
sedimentary environments, along with rare bio-mineralization process
(Sha and Chappell, 1999; Seifert et al., 2000; Elliott, 2002; Hughes and
Rakovan, 2002; Piccoli and Candela, 2002; Spear and Pyle, 2002;
Liferovich and Mitchell, 2006; Mason et al., 2009; Marks et al., 2012;
Teiber et al., 2015; Pan et al., 2016). Due to low solubility of P2O5 in
silicates and limited quantity of phosphorus accepted by common rock-
forming minerals, apatite occurs in low concentration in most igneous
rocks, albeit some exception such as nelsonite (Piccoli and Candela,
2002; Spear and Pyle, 2002; Patiño Douce and Roden, 2006; Webster
and Piccoli, 2015). Based on F, Cl and OH concentrations, apatite can
be classified as fluorapatite, chlorapatite and hydroxyl-apatite. As an
important constituent of many mineral deposits, the apatite has also
been effectively used as metallogenic indicator (Roegge et al., 1974;
Williams and Cesbron, 1977; Treloar and Colley, 1996; Belousova et al.,
2002; Imai, 2004) including recently reported IOCG systems. Major,
minor and trace elements along with REE concentrations of apatite are
R. Mukherjee et al.
controlled by various factors such as temperature, pressure, oxygen
fugacity and composition of parent magma (Watson and Green, 1981;
Sha and Chappell, 1999; Belousova et al., 2001; Parat et al., 2002; Chu
et al., 2009; Miles et al., 2014).
In this contribution, detailed mineral chemistry of both magnetite
and apatite is determined using EPMA and LA-ICP-MS from
Paleoproterozoic Bhukia Gold Deposit within the Aravalli-Delhi Fold
Belt, western India with an aim to decipher the genetic significance of
these minerals in a possible IOCG-IOA association. Presence of apatite
along with magnetite is a typical signature of IOCG-IOA association
reported from various deposits viz. Kiruna type deposits of Northern
and Central Sweden (Talab et al., 2015; Mao et al., 2016), Ningwu
Basin of China (Yu et al., 2011), El laco deposit of Chile (Talab et al.,
2015), Kiruna type Los Colorados IOA deposit (Mao et al., 2016), Mt.
Isa deposit in Conclurry district of Australia (Belousova et al., 2001),
Khanlogh deposit of NE Iran (Zarei et al., 2016), Chador-Malu, Chogart
and Esfordi deposit in Bafq district of Central Iran (Torab and Lehmann,
2007; Taghipour et al., 2015; Talab et al., 2015; Heidarian et al., 2016).
Paleoproterozoic Bhukia Gold Deposit is unique in terms of its mineral
assemblages such as Cu-sulfides, graphite, tourmaline, carbonates and
albite which markedly differ from the known gold deposits of India
(Mukherjee et al., 2016). Magnetite and apatite are present in sub-
stantial amounts along with other sulfides and at many places magne-
tite is associated with gold and thus the chemistry of magnetite played
an important role in the origin and evolution of Bhukia Gold Deposit.
An attempt has been made to i) understand the significance of trace and
REE systematics with respect to the nature of apatite as to whether it is
fluorapatite/chlorapatite variety; ii) integrated chemical behavior of
magnetite and apatite in a possible IOCG-IOA association akin to the
well-established deposits. In this paper, we present detailed LA-ICP-MS
trace element/REE chemistry of magnetite and apatite to decipher the
evolution of magnetite and apatite in magmatic-hydrothermal condi-
tions vis-a-vis gold mineralization that has a definite bearing on me-
tallogenetic significance and may throw light on exploration in allied
prospects.
2. Geological overview
The geological set up of the Aravalli-Delhi Fold Belt (ADFB) in
western India (Fig. 2A) includes a 3.3–2.5 Ga Archean basement com-
plex, known as Banded Gneissic Complex (BGC) marked by granitic
gneisses with meta-volcano-sedimentary rocks and intrusives (Roy and
Kröner, 1996; Golani et al., 2002). They are overlain by 2.2–1.85 Ga
Paleoproterozoic cover sequences of the Aravalli and Delhi Supergroups
[(Fig. 2B), (Kaur et al., 2009, 2011)]. Yadav et al., 2016 also suggested
that the Sm-Nd model age of davidite from the Paleoproterozoic rocks
within BGC varies from 1851 to 2200 Ma. The Aravalli sequence ap-
pears to have formed as part of the continental rift basins (Singh, 1988;
Bhattacharya and Bull, 2010). The interface of BGC and Aravalli Su-
pergroup between Delwara and Ghatol in southeastern Rajasthan is
mineralized (Cu-Au-iron oxide-graphite). The focus of the current study
area, Bhukia Gold Deposit belongs to the Aravalli Supergroup which
occupies the south central part of the Banswara District comprising of
meta-volcano-sedimentary supracrustal rocks. Gupta et al. (1997) sug-
gested that staurolite schist is a part of the basement rock (BGC). The
contact between staurolite schist and the Aravalli Supergroup is sheared
and referred to as Ghatol Shear Zone (Fareeduddin et al., 2012).
2.1. Deposit-scale geology
The Bhukia gold (+copper) deposit is the largest deposit reported
from Paleoproterozoic Aravalli Supergroup. The Geological Survey of
India (GSI) has carried out subsurface exploration (42942 m drilling in
155 boreholes) and reported a total resource of 105.81 mt with average
grades of 1.97 g/t gold and 0.15% of copper (GSI Bulletin Series, 2014).
The mineralized lodes distributed in about 11 parallel to sub-parallel
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zones are highly variable in thickness (1–56 m) and average metal
content (0.5 g/t to 20.13 g/t Au and 0.1–1.14% Cu).
Major lithotypes in the Bhukia area are quartzite, marble, albitite,
tourmalinite, calc-silicate rocks, mica-schist and a small unit of am-
phibolite (Fig. 3A). These lithounits have been affected by upper
greenschist to lower amphibolite facies metamorphism. Generalized
structural trend of the lithounits of Bhukia deposit is NNW-SSE with
moderate to steep dips towards WSW. Ore minerals present in Bhukia
area in the order of abundance are pyrrhotite, arsenopyrite, chalco-
pyrite, pyrite, loellingite along with magnetite, graphite, goethite and
native gold. Invisible gold has been reported within arsenopyrite, pyr-
rhotite and pyrite (Mukherjee et al., 2016). The mineralization is both
structurally and lithologically controlled. Auriferous mineralization
with or without sulfides is hosted by albitite, dolomitic marble, am-
phibolite and quartzite in order of decreasing abundance. Gold miner-
alization occurs as disseminations, en-echelon patterns within S2 shear
fractures, along deformed dilatant zones, especially in the hinge por-
tions of F2 folds forming part of NNW-SSE regional shear system as Au-
sulfide-carbonate association.
2.2. Structural aspects and controls of mineralization
The rocks of Aravalli Supergroup are affected by three phases of
deformation events (Sengupta, 1976; Deol et al., 2012). The first phase
of deformation D1 has generated steeply plunging (65°–70°), isoclinal or
reclined F1 folds towards northwest and southeast (Fig. 3B). Mineral
lineation, parallel to F1 folds axes, is a common feature of this area. Due
to the isoclinal nature of F1 folds, S1 schistosity is parallel to the bed-
ding plane schistosity (S0) except at the hinges of the F1 folds, where it
shows perpendicular relationship (Deol et al., 2014). The super-
imposition of later phases of folding has caused strong curvature both at
the hinge and axial planes of first generation folds. The second gen-
eration folds (F2) are different from that of the F1 folds by their style
and geometry. The second phase of deformation generated open to
tight, symmetrical and asymmetrical, normal to overturned, moderately
plunging folds (Fig. 3C). However, the third deformation D3 has re-
sulted broad, open warp, F3 folds. Mineralization in the study area
mainly occurs along the hinges of F2 folds and shear fractures (Fig. 2A).
The auriferous sulfides show crisscrossing relationships with two dis-
tinct loci- i) along the axial trace of F2 folds and ii) numerous lenses of
varying dimensions along the NNW-SSE trending shear zones. Petro-
graphic studies confirm the localization of mineralization along S2
planes. Predominant shear fractures present within the albite grains
contain mineralization (Fig. 4A). Magnetite and apatite occurs within
albitite, mica-schist and tourmaline-rich albitite. Magnetite is aligned
parallel to S1 as rotated grains within these lithounits. Apatite occurs as
disseminated form and is associated with magnetite at many places. In
the study area, magnetite is closely associated with gold-sulfide and
graphite (Mukherjee et al., 2016).
2.3. Major alteration zones surrounding mineralization
The close association of signatures of hydrothermal alterations with
mineralization is present in and around the area viz. albitization,
tourmalinization and graphitization (Garhia et al., 2001; Mukherjee
et al., 2016). Albitization and tourmalinization are the major types of
alteration recorded in close proximity of the mineralized lodes along
with graphite. Extensive Na-Al and Na-B-Ca-Fe-Ti alteration is present
in early and late phases and is represented by the development of al-
bitite, tourmaline, calcite/dolomite, martite and titanite. Albitite con-
stitutes the bulk of the alteration zones in Bhukia. Albitites contain in
excess of 80% albites which are largely untwined with diffused grain
margins. Tourmaline occurs as three different types viz. i) very fine
crystals of tourmaline thinly laminated with albitites exhibiting color
zoning in the form of dark brown cores and pale brown rims (Fig. 4B),
ii) Euhedral, zoned, green color tourmaline with pale yellow core
R. Mukherjee et al.
associated with fine grained albitites (Fig. 4C) and iii) highly corroded
grains of zoned, prismatic green tourmaline with pale yellow core as-
sociated with both albitites and carbonate rocks (Fig. 4D). Zones with
more than 80% of tourmaline in albitites are termed as tourmalinite
(Fareeduddin et al., 2010; Mukherjee et al., 2016). Mineralized veins
are recorded within tourmaline rich albitite (Fig. 4E). Graphitic al-
teration patterns within the study area are also represented by the
presence of graphite along with magnetite, sulfides and silicates
(Fig. 4F and G). Morphologically graphite occurs in two forms viz. flaky
sheets and lath shaped crystals. Association of graphite with albitite
suggests graphitization and is linked with extensive Na-metasomatism.
δ13C ‰ (PDB) values of around −18‰ suggest organic nature of
carbon in graphite (Fareeduddin et al., 2014). Later on, due to mixing
of hydrothermal carbon and organic carbon resulted in precipitation of
carbonates. Formation of graphite from the precursor organic carbon
enhanced by further hydrothermal influx led to gold precipitation
(Sahoo and Venkatesh, 2014). Late phase of alteration is marked by the
presence of martite formed due to martitization process. Magnetite is
replaced by hematite in oxidizing environment, which later replaced by
goethite in highly oxidized gossan zone. Occurrence of native gold in
the weak zones of goethite can be seen in gossan zone from the study
area (Fig. 4H).
3. Stages of mineralization vis-à-vis magnetite-apatite-gold
Gold-copper association of Paleoproterozoic Bhukia Gold Deposit is
unique in terms of its host lithologies such as albitite and carbonate
which differs from the Archean greenstone-hosted gold deposits of
Dharwar Craton in southern India (Sahoo and Venkatesh, 2014;
Mukherjee et al., 2016). The Au-Cu mineralized zone occurs within
albitite-graphitic rocks with substantial amounts of apatite. Fluid in-
clusion studies from the ore zones of Bhukia support evolution of fluid
from high temperature magmatic hydrothermal to low temperature
brines. The temperature of mineralizing fluid ranges from low (110 °C)
to high (560 °C) with the presence of contrasting salinity ranges from 5
to 30 wt%, recommend mixing of low saline and high saline fluids
(Garhia et al., 2001; Guha, 2004; Deol et al., 2010; Fareeduddin et al.,
Fig. 2. (A) Simplified geological map of Rajasthan showing the location of Aravalli-Delhi Fold Belt (Modified after Kilaru et al., 2013). (B) Regional map of Aravalli Craton showing
location of Paleoproterozoic Aravalli Supergroup, the basement (Banded Gneissic Complex) BGC and the study area (Bhukia) (Modified after Shekhawat et al., 2007 and Pandit et al.,
2003).
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2012). Involvement of magmatic hydrothermal fluids in the miner-
alizing events of Bhukia is confirmed on the basis of fluid inclusion data
(mostly high saline fluids) along with other key features viz. i) presence
of the syntectonic granitic intrusive bodies in the vicinity of this de-
posits; ii) presence of sulfide assemblages of pyrrhotite-arsenopyrite-
pyrite-loellingite-chalcopyrite along with gold; iii) existence of ex-
tensive Na-B-Si metasomatism and iv) depleted δ13C and δ18O values
(Deol et al., 2012; Fareeduddin et al., 2012). There is good evidence of
ultra-saline mineralizing conditions in the Bhukia area such as i) pre-
sence of pervasive ultrasodic proximal and distal alteration zones along
with exsolved phases of Na-rich feldspar (albite) (Fig. 4A–E); ii) pre-
sence of high magnesian dravites with povondraite component;
(Fig. 4B–D) and iii) presence of high saline fluids in the mineralized
zones and low salinity fluids in the barren zones (Fareeduddin et al.,
2012). δ18O values from the carbonates of Bhukia are much depleted
compared to the much enriched values of carbonates from the non-
magmatic evaporitic environments. Deol et al. (2010) shown that the
fluid inclusion data of quartz from the granitic plutons from this region
possess high salinity fluids, which recommend the role of granite in
contributing these high saline mineralizing fluids. Dilatant zones act as
major pathways to supply high Na+Mg mineralizing brines and pre-
cipitate povondraitic tourmaline in the study area (Fareeduddin et al.,
2012).
In the study area, magnetite and apatite occurs in two different
styles viz. i) as disseminated grains and ii) as quartz-carbonate-apatite
veins. It is suggested that the magnetite and apatite are precipitated
from initial high temperature hydrothermal fluids in the first stage of
mineralization in relatively oxidized state suggestive of high fugacity of
oxygen. In the second stage, remaining Fe-P rich hydrothermal fluids
mixed with relatively low temperature and high saline hydrothermal
brines which promoted further precipitation of magnetite-apatite.
Magnetite in this stage is associated with shear zones where the grains
are rotated and deformed. Later, the Fe-rich fluids are mixed with lower
temperature hydrothermal fluids and associated ligands promoted sui-
table reducing conditions for precipitation of sulfides such as pyr-
rhotite, arsenopyrite and pyrite along with albite and tourmaline. As
the temperature decreased further, graphite was precipitated in the
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Fig. 2. (continued)

mineralizing system due to mixing of low temperature hydrothermal
fluids with precursor organic carbon.
Gold precipitation is promoted by interaction of fluids with organic
carbon (Neall and Phillips, 1987). Sulfides and graphite provided fa-
vorable conditions for precipitation of gold. In this stage, gold is co-
precipitated with sulfides and locked into the crystal lattices of
pyrrhotite, arsenopyrite and pyrite. With increase in shearing aided by
fluid-rock interaction with organic carbon, lattice bound gold is been
expelled and remobilized due to destabilization of gold-sulfide complex
and restored in first generation sulfides (Jha et al., 2015; Sahoo and
Venkatesh, 2015). In the final stage, further increase in shearing results
in the expulsion of gold grains from the sulfides and precipitation along

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Fig. 3. (A) Geological map of Bhukia gold (+copper) deposit showing different litho-units (chronologically) and structural patterns (modified after Mukherjee et al., 2016). (B) Field
photograph showing both isoclinal F1 and tight F2 fold in calc-silicates. (C) Calc-silicate rocks are folded and these F2 folds are the main structural features present in the study area.

the grain boundaries of sulfide in a native state (5–35 μm in size) events from Bhukia Gold Deposit are presented in Fig. 5.
(Mukherjee et al., 2016). Mineralization is located in shear fractures,
multiple quartz-carbonate veins. Mineral paragenetic sequence of dif-
ferent mineral phases identified from the relationships between host 4. Mineralogical characterization of magnetite and apatite in
rocks and ore, textural features, ore assemblages, mineralization asso- Bhukia
ciated with alteration zones and mineralization related to structural
Detailed field, optical microscopy and EPMA studies indicate that

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Fig. 4. Photomicrographs and EPMA-BSE images of mineral assemblages related to alteration zones and shear systems. (A) Photomicrograph showing the nature of mineralized shear
system showing shear fractures that cross cut the albite grains. (B) Fine grained, thinly laminated, zoned, brown tourmaline grains present within the albitites. (C) Euhedral, rounded,
zoned, green tourmalines along with biotite associated with albitites. (D) Elongated, prismatic, zoned, green tourmaline grains occurrences within the albitites. (E) Mineralization is
associated with extensive hydrothermal alterations viz. albitization and tourmalinization. (F) Photomicrograph showing the relationship between graphite with magnetite and silicates.
(G) EPMA-BSE image of graphite associated with mineralized sulfides in the study area. (H) Native gold along with goethite within the gossan zone.

magnetite occurs in the form of typical euhedral grains aligned parallel associated with sulfides along with gold and graphite at many places
to the shear fractures as rotated grains within mica-schist, albitite and (Fig. 6B and C). Martitization is the most conspicuous feature where
tourmaline-rich albitite rocks (Fig. 6A). Magnetite is intimately hematite occurs along the cracks, fractures, grain boundaries and

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Fig. 5. Evolution of gold mineralization with respect to various oxide, sulfide and altered minerals are shown in a paragenetic order based on relationships between host rock mineral
assemblages-ore, textural and micro-structural relationships/controls and mineralization surrounding alteration zones.
sometimes along octahedral planes of magnetite (Fig. 6D) along with
goethite (Fig. 6E). Magnetite grains are deformed and show preferred
orientation along with the silicates in the shear zone to form pressure
shadows and as rotated grains (Fig. 6F and G). Titano-magnetite present
in the Bhukia area infers higher oxygen fugacity conditions (Fig. 6H).
Apatite is an important accessory mineral present within the albitite
and carbonate rocks in Bhukia area (Fig. 7A and B). At many places
apatite is associated with magnetite grains (Fig. 7C). Inclusions of
sphene can also be seen within apatite grains (Fig. 7D–F).
5. Materials and methods
Detailed mineral chemical analysis has been carried out for major,
minor and trace elements of magnetite (Zn, Cu, Ni, Mn, Mg, Cr, V, K, Sn,
Ca, Ti, Al, Si) and apatite (Na, Mg, Al, Si, Zn, Fe, Ca, Cr, B, F, P, K, Ti
and V) with a CAMECA SX-5 Electron Probe Micro-Analyzer (EPMA)
equipped with five wavelength dispersive spectrometers at Central
Research Facility (CRF), Indian Institute of Technology (Indian School
of Mines), Dhanbad, India. Both magnetite and apatite grains are ex-
amined microscopically as well as through BSE (back-scattered elec-
tron) images for mineralogical and chemical variations if any and the
conspicuous absence of any prominent zoning is also observed in both
the mineral assemblages. A minimum of two spots are taken on each
magnetite and apatite grains that are analyzed to check the presence of
any elemental variations. The EPMA has been carried out using the
wavelength dispersion mode with a beam current of 15 nA, excitation
voltage of 15 kV with a beam size of 5 μm. Peak and background time
are 10 s and 5 s respectively. Data reduction has been carried out using
X-Phi method. The standards, X-ray lines and crystals that are used to
analyze magnetite and apatite samples are: MgO, Mg-Kα, TAP; TiO2, Ti-
Kα, PET; V, V-Kα, LIF; Cr2O3, Cr-Kα, PET, Rhodonite, Mn-Kα, LIF; Fe,
Fe-Kα, LIF; Co, Co-Kα, LIF; Ni, Ni-Kα, LIF; ZrSiO4, Zr-Lα, PET; SnO2, Sn-
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Lα, PET; W, W-Lα, LIF; Kyanite, Al-Kα, TAP; Albite, Si-Kα, TAP;
Apatite, P-Kα, PET; Apatite, Ca-Kα, PET; B, B-Kα, PC2; CaF2, F-Kα, TAP;
Pyromorphite, Cl-Kα, PET; Sphalerite, Zn-Kα, LIF; Orthoclase, K-Kα,
PET and Albite, Na-Kα, TAP. Analytical conditions were similar to that
of Hazarika et al., 2016a for the analysis of magnetite and apatite. X-ray
mapping of magnetite and apatite using EPMA has been carried out to
get idea about elemental distribution as well as presence of zoning.
Colorized X-ray mapping of magnetite shows maximum concentration
of uniformly distributed Fe and scattered distribution of Al and Si. Ni
and V are uniformly distributed throughout the magnetite grain
(Fig. 8a). X-ray mapping reveals uniform distribution of major elements
such as Ca and P in case of apatite besides F, Ce and Y (Fig. 8b).
Trace element and REE characterization of magnetite and apatite
has been carried out using Laser Ablation-Inductively Coupled Plasma
Mass Spectrometry (LA-ICP-MS) at the Department of Geology and
Geophysics, Indian Institute of Technology, Kharagpur, India. The
analyses were conducted using Cetac 213 nm Nd YAG laser ablation
system that is connected to a Varian 820 quadrupole ICP-MS (Hazarika
et al., 2016b). The ablation was performed at 10 Hz pulse frequency,
30–60 μm spot size and 730 V energy. The samples were analyzed in
peak hopping mode with each analysis consisting of a 20 s background
measurement with the laser turned off and 40 s peak signal measure-
ment with the laser turned on conditions. The NIST 612 glass was used
for calibration purposes and the data is synthesized using the Glitter©
software (Griffin et al., 2008) with Fe as an internal standard for
magnetite and Ca for fluorapatite. Within sequence, reproducibility 2σ
is estimated from repeated analyses of the NIST 610 glass are as: V, Co,
Rb, Mo, Ag, < 3%; Ni, Sr, Ba, La, Pr, Nd, < 5%; Sc, Ti, Zn, Y, Zr, Nb, La,
Ce, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, < 10%; W, < 12%; and
Fe, < 21%. Time-resolved LA-ICP-MS signals for La/Ce and Zr were
carefully monitored for any effects of inclusions of monazite and zircon
respectively. The trace elements were normalized after Boynton (1984).
R. Mukherjee et al. Ore Geology Reviews 91 (2017) 509–529

Fig. 6. Photomicrographs of various generations of mineral assemblages such as magnetite-martite-goethite-sulfides-graphite-gold and their linkages to the shear zone characteristics and
deformation patterns. Rotated deformed fabric of magnetite grains within the mica-schist are aligned parallel to the S1 schistosity planes exhibiting sigmoidal forms; Second generation
euhedral magnetite associate with first generation pyrite grains; BSE image of euhedral magnetite associated along the grain boundaries of hydrothermal laths of graphite; Martitization
process suggesting low temperature evolution and high oxidation conditions; Fine laminated gold precipitated along the weak growth zones and selectively replaced colloidal goethite
within the gossan zone; Intense shear features of deformed muscovite exhibiting kink banding, pressure solution of minute laminae of quartz grains, pinch and swell features, deformed
and rotated magnetite grains along the foliation planes of quartz-mica schist. Development of magnetite pressure shadow zone; Coarse grained titanomagnetite exhibiting octahedral
cleavage which in turn occupied by hematite.

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Fig. 7. EPMA BSE images and photomicrographs of apatite mineral phases; (A) Rounded to sub-rounded aligned apatite grains surrounded by elongated and stretched sphene grains both
participated in the shearing activity within the host albititic lithounits; (B) Coarse grained deformed apatite grain; (C) Lath of second generation magnetite in association with apatite
within carbonates; (D) Rounded sphene enclosed by apatite within albitite. (E) Photomicrograph of apatite-sphene association within albitite. (F) Photomicrograph showing occurrence of
lenticular apatite grain along with gold-bearing sulfide mineralization.

The Eu-anomaly (Eu/Eu∗)N is calculated as [EuN/SQR(SmN ∗ GdN)],
and Ce anomaly is calculated as [CeN/SQR(LaN ∗ PrN)]. All the mineral
abbreviations are used after Kretz (1983).
6. Results and discussion
6.1. Source characterization
In addition to Fe, magnetite from the Bhukia gold (+copper) de-
posit contains important major, minor and trace elements such as Mg,
Al, Si, Ca, Ti, Mn, V, Co, Ni, Cr, Sn, Li, Na, Ga, Rb, Sr, Y, Zr, Nb, Mo, Ba,
Ta, Hf, W, Pb, Bi, Th and U along with REE which are analyzed using
Electron Probe Micro Analyzer and Laser ablation ICP-MS (Table 1).
These elements in magnetite are very useful to understand the type of
the ore deposit as well as the environment and genesis of magnetite
which has a bearing on the overall magnetite-apatite-tourmaline-
copper-graphite-gold metallogeny in the study area (Dupuis and
Beaudoin, 2011; Carranza et al., 2012; Dare et al., 2012, 2014; Gao
et al., 2013; Huang et al., 2013; Nadoll et al., 2014; Chen et al., 2015a;
Makvandi et al., 2016). Detailed mineral chemistry of the magnetite
grains show wide ranging concentration of Al (200–2600 ppm), Ti
(100–600 ppm), Mg (100–2900 ppm), Co (356–4064 ppm), Ni

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Fig. 8. Colored X-ray maps generated from EPMA depicting elemental variation of magnetite and apatite grains: (A) Fe, Al, Ni, Si and V distribution in magnetite without any conspicuous
zoning as is common in typical IOCG deposits; (B) Ca, Y, Ce, F and P distribution within apatite grain showing substantial values of F and lower Cl values suggesting its typical fluorapatite
character.
(865–11125 ppm), Si (100–900 ppm), Ca (100–3200 ppm), Mn
(617–3943 ppm), Cr (373–7679 ppm) and V (up to 12000 ppm).
Crystallization of magnetite from silicate melt commonly enriches
lithophile elements viz., Ti, Cr, V, Al, Mn, Ca, Nb, Ga, Ta, Hf and Zr
whereas, concentration of chalcophile elements such as Ni, Co, Sn, Pb is
more in magnetite precipitated from sulfide-rich fluid (Cygan and
Candela, 1995; Toplis and Corgne, 2002; Simon et al., 2008; Dare et al.,
2012). Hydrothermal magnetite has lower concentration of Ti, Al, V
and Cr, moderate to lower concentration of Si and Ca, and wide ranging
Mg content (Hu et al., 2014; Nadoll et al., 2014; Heidarian et al., 2016).
Magnetite also can be formed by metamorphism of sulfides and has low
concentration of Ti, Cr, V, Ni and Mn (Boutroy et al., 2014). Constraints
on the chemical constituent variations of trace elements are shown in
Fig. 9 based on LA-ICP-MS data to understand their inter-relationships.
The relation between the minor and trace elements of magnetite from
the study area reflect strong influence on the host rock geochemistry. It
has been noted that Mg, Al, Ti, V, Cr, Mn, Ni and Ca, hold significant
genetic connotation from IOCG deposits based on their variations
within magnetite.
6.2. Magmatic vs. hydrothermal magnetite
Trace elemental concentrations in magnetite depend on the com-
position of fluid or water and magnetite concentration processes
(Nystrom and Henriquez, 1994; Frietsch and Perdahl, 1995; Toplis and
Corgne, 2002; Dare et al., 2014; Nadoll et al., 2014). Trace elements
present in the magnetite have been used elsewhere to differentiate
between magmatic and hydrothermal deposit types including iron
oxide–copper–gold (IOCG), Kiruna apatite–magnetite, banded iron
formation (BIF), porphyry Cu, Fe–Cu skarn, magmatic Fe–Ti–V–Cr or
Ni–Cu–PGE, Cu–Zn–Pb volcanogenic massive sulfide (VMS) and Ar-
chean Au–Cu porphyry deposits (Dupuis and Beaudoin, 2011; Dare
et al., 2014; Nadoll et al., 2014). Magmatic and hydrothermal magne-
tite show differing chemical and textural signatures (Singoyi et al.,
2006). The main factors which control the concentrations of trace
elements present within magmatic magnetite comprise composition of
the magma, coexisting minerals, oxygen fugacity (fO2), temperature,
pressure, cooling rate, sulfur fugacity (fS2) and silica activity
(Buddington and Lindsley, 1964; Ghiorso and Sack, 1991; Toplis and
Corgne, 2002; Dare et al., 2012). Temperature, composition of fluid,
oxygen and sulfur fugacity, silicate and sulfide activity, host rock buf-
fering, re-equilibration processes, ionic radius and charge balance are
the factors responsible for variable concentrations of trace elements in
hydrothermal magnetite found in various settings (Lemarchand et al.,
1987; Frost et al., 1988; Cygan and Candela, 1995; Simon et al., 2008).
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Ore Geology Reviews 91 (2017) 509–529
Mg, Ti, V, Cr, Ni and Co are the useful trace elements obtained from
LA-ICP-MS that can differentiate between igneous and hydrothermal
origin of magnetite from Bhukia. Wide ranging concentration of Mg
within magnetite (100–2900 ppm) infers its hydrothermal origin
(Nadoll et al., 2014). The Co/Ni ratio of magnetite from the Bhukia area
is lower than 1 (0.05–0.48) which suggests its hydrothermal origin.
Lower concentrations of Ti, Al, Zr, Hf, Nb and Ta with higher con-
centration of Ni, V, Co, Zn and Mn in magnetite from the study area also
confirm the hydrothermal origin. Most of the hydrothermal magnetites
contain Ti less than < 2 wt% and Al < 1 wt% (Hu et al., 2015). Mean
concentration of Ti and Al in magnetite is ∼350 ppm and ∼890 ppm
respectively, which support the magmatic hydrothermal origin in the
study area. Low concentration of these elements in hydrothermal
magnetite is justified in terms of their immobility during hydrothermal
alteration (Van Baalen, 1993).
Ti is generally compatible in magnetite, but low concentration of Ti
in magnetite from Bhukia suggests that the fluid that precipitated
magnetite was poor in Ti. Higher concentration of Co in excess of
100 ppm (895 ppm mean) in Bhukia magnetite is also indicative of its
magmatic hydrothermal source. Mg concentrations are also important
to distinguish between igneous and hydrothermal magnetite. According
to Nadoll et al., 2014, Mg concentration ranges from 100 to 1000 ppm
for igneous magnetite whereas hydrothermal magnetite has wide range
of Mg concentration from 100 ppm to above 1000 ppm. Magnetite in
Bhukia favors hydrothermal origin with Mg concentration ranging from
100 to 2900 ppm i.e., well above 1000 ppm. These may be the result of
evolution of fluid from initial high temperature magmatic hydro-
thermal fluid to low temperature brines. In general, hydrothermal
magnetite has lower concentration of V (below 1000 ppm) in barren
zones (Rusk et al., 2009). However, in Bhukia, it is relatively higher
(700–1400 ppm) due to the association of other sulfide-hosted gold
mineralization.
Concentrations of Cu and Pb are less in magnetite despite their
common occurrences in hydrothermal fluids which can be justified by
the competition of Cu with magnetite for sulfide precipitation and the
incompatible nature of Pb into magnetite (Dare et al., 2014). Trace
element concentrations (Ti vs Ni/Cr) of magnetite in Bhukia indicate
hydrothermal magnetite characteristics (Fig. 10A). Ni/Cr ratio is ≤1
for magmatic magnetite, as both are compatible in silicate magmas at
the time of fractionation, while in many high temperature magmatic
hydrothermal settings, such as skarn, IOCG, iron-oxide-apatite (IOA)
and porphyry, Ni/Cr ratio of magnetite is ≥1 (Dare et al., 2012). This
can be explained by differences in solubility and mobility of Ni and Cr
in hydrothermal fluids. In the Bhukia area, both LA-ICP-MS and EPMA
data shows Ni/Cr ratio of magnetite is > 1, attesting further its
R. Mukherjee et al. Ore Geology Reviews 91 (2017) 509–529

Table 1
EPMA and LA-ICP-MS data showing major, minor and trace element concentration of magnetite from Bhukia gold (+copper) deposit, western India.

Elements/Lithology L-5 L-5 L-5 L-5 L-5 CS-14 CS-14 L-1 L-1 L-1 L-1 L-1

Albitite Mica-schist

EPMA (wt%)
Mg 0.02 0.01 0.13 0.25 0.29 0.01 0.04 0.02 0.01 0.01 0.01 0.02
Ti 0.06 0.03 0.04 0.02 0.04 0.04 0.03 0.05 0.02 0.01 0.04 0.03
Fe 69.63 68.80 69.78 68.95 68.17 70.55 70 70.14 70.31 70.95 70.36 68.05
Al 0.11 0.26 0.02 0.05 0.05 0.09 0.04 0.10 0.07 0.04 0.06 0.09
Si 0.01 0.01 0.09 0.06 0.03 0.01 0 0 0 0.01 0.01 0.09
P 0 0 0.02 0 0.01 0 0 0 0 0 0 0
S 0.01 0 0.05 0.02 0.05 0 0.01 0 0.02 0.01 0 0
Ca 0.01 0.03 0.32 0.32 0.32 0.04 0.02 0.01 0.01 0.02 0.01 0.04
O 20.25 20.31 19.99 19.38 19.95 20.42 20.23 20.29 20.86 20.51 20.32 19.83

LA-ICP-MS (ppm)
Li 93.58 44.86 < 143.03 12.33 < 7.56 < 10.25 < 7.54 9.20 < 8.20 < 14.29 < 8.80 < 6.14
Be < 0.00 101.03 < 0.00 4.22 < 5.99 < 0.00 1.65 10.69 < 0.00 < 11.14 < 0.00 < 0.00
Na 11313.36 12232.80 < 6332.85 < 308.29 432.49 < 408.56 < 323.56 255.61 < 325.41 < 610.84 < 318.07 < 245.29
V 52227.30 275.46 155475.50 10885.93 9991.46 10716.08 10491.57 12289.60 10810.25 9589.96 10715.05 10571.91
Cr 1198.61 455.82 7679.40 1046.14 1016.18 878.81 952.98 605.56 667.15 712.46 372.57 998.93
Mn 2932.07 3942.72 8971.29 822.53 616.57 2039.28 1296.82 2450.62 1901.13 1611.36 1820.09 2106.96
Co 1548.85 1328.97 4064.36 358.21 355.56 420.51 423.17 505.95 433.54 371.72 451.50 478.33
Ni 4101.27 6843.25 11125.01 6589.72 5840.43 1259.74 1815.39 1111.91 1018.25 865.15 1019.09 988.32
Cu 66.89 807.05 < 155.47 6.9 < 4.37 < 10.47 < 7.32 < 3.63 < 7.73 < 12.23 < 7.84 < 5.57
Zn 3061.96 83.43 6397 74.63 21.20 59.99 71.35 46.41 82.62 < 32.14 94.85 46.51
Ga 2027.93 19.97 6737.52 337.89 280.93 361.95 412.12 424.05 383.72 315.08 335.78 388.07
Rb 165.92 84.39 50.31 2.52 7.35 < 3.71 2.47 < 1.57 5.45 < 4.19 < 2.84 2.52
Sr 55.43 824.18 56.50 21.22 4.28 0.57 4.57 7.21 3.12 0.68 0.92 1.01
Y 88.19 138.47 178.02 1.40 0.21 2.26 32.64 1.71 2.49 < 0.00 0.11 0.084
Zr 2010.56 1854.24 < 0.00 164.26 11.50 67.22 4125.59 72.42 329.54 0.43 < 0.78 14.38
Nb 13.85 2.11 < 15.22 12.23 0.53 < 0.00 14.62 5.41 11.82 13.48 0.83 8.74
Mo 8.90 452.56 < 118.47 < 3.93 2.59 < 6.12 < 4.78 < 2.59 < 5.38 6.38 2.02 < 2.63
Cd < 42.71 < 2.07 < 0.00 < 4.69 < 0.00 < 5.65 < 4.93 0.87 1.46 < 0.00 < 4.95 1.03
Sn 132.66 < 146.99 9.69 < 6.77 < 43.59 78.91 < 119.86 < 5.86 7.11 18.42 103.41 38.07
Cs 7.50 4.07 11.08 1.33 0.37 < 0.273 < 0.24 < 0.21 0.56 0.39 < 0.24 0.10
Ba 649.18 1000.77 123.51 13.17 29.70 < 0.00 3.89 2.81 11.26 1.73 0.89 4.29
La < 0.00 595.02 < 0.00 1.26 0.36 < 0.261 0.062 0.56 < 0.00 0.12 < 0.00 < 0.00
Ce 0.67 1019.12 1.41 2.42 0.55 < 0.00 0.50 0.40 < 0.00 < 0.00 < 0.00 < 0.00
Pr < 0.00 123.43 < 0.00 0.69 0.08 < 0.00 < 0.00 0.03 < 0.00 < 0.00 < 0.00 < 0.12
Nd 2.78 540.52 5.82 2.06 0.23 < 0.00 < 0.00 0.15 < 0.00 < 0.00 < 0.00 < 0.00
Sm < 0.00 77.42 < 25.16 0.34 < 0.00 0.44 0.79 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00
Eu < 0.00 12.03 < 0.00 < 0.00 < 0.00 < 0.00 0.063 < 0.00 0.068 < 0.00 < 0.00 < 0.00
Gd 3.06 47.04 12.83 < 0.00 0.23 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00
Tb 1.20 6.90 2.50 0.04 0.06 < 0.00 0.10 0.04 0.04 < 0.00 < 0.00 < 0.00
Dy 11.36 36.18 27.57 0.18 0.14 < 0.00 1.82 0.09 0.15 < 0.00 < 0.00 < 0.00
Ho 2.39 5.63 8.34 0.04 < 0.00 0.06 1.36 0.08 0.14 < 0.00 < 0.00 < 0.00
Er 16.04 13.10 11.99 0.12 < 0.00 0.32 6.81 0.25 0.72 0.19 < 0.35 < 0.00
Tm 3.31 2.18 3.85 0.12 < 0.00 < 0.13 1.61 0.16 0.20 < 0.21 < 0.00 < 0.00
Yb 17.58 23.70 36.80 < 0.00 0.13 0.23 15.78 0.27 1.92 < 0.00 < 0.00 < 0.00
Lu 3.75 2.62 6.41 0.08 < 0.00 0.10 3.65 0.04 0.35 < 0.00 0.03 < 0.00
Hf 64.49 40.74 < 0.00 4.7 0.17 2.24 130.22 1.61 11.12 < 0.00 < 0.00 0.27
Ta 2.47 0.25 0.74 0.93 < 0.11 < 0.12 1.53 0.21 0.75 0.99 0.06 0.51
W 4.11 1.66 2.86 0.16 0.25 < 0.00 0.25 0.08 0.27 0.25 < 0.00 < 0.00
Pb 22.20 – 64.25 60.33 8.23 < 2.45 33.70 5.70 < 1.86 < 3.08 < 1.75 < 1.45
Bi 5.87 133.11 15.2 0.46 < 0.19 < 0.17 0.91 0.17 0.15 < 0.39 < 0.11 < 0.14
Th 6.19 410.06 23.2 0.06 0.05 0.21 6.75 0.53 0.11 0.25 < 0.00 0.02
U 26.62 1014.91 20.81 3.89 0.44 0.66 37.82 0.65 5.14 0.16 0.06 0.06
Co/Ni 0.38 0.19 0.37 0.05 0.06 0.33 0.23 0.46 0.43 0.43 0.44 0.48
Ni/Cr 3.42 15.01 1.45 6.30 5.75 1.43 1.90 1.84 1.53 1.21 2.74 0.99

hydrothermal origin. Co, Ni, Cr, Ti and V concentrations have been
used to differentiate hydrothermal and magmatic magnetite as the
concentrations of these elements in magnetite are considered to reflect
nature of the parent magma and the resultant fluids.
6.3. Magnetite in an IOCG deposit
Many trace elements are very useful indicators of provenance and
facilitate the identification of various ore deposit types and their origin
(Basu and Molinaroli, 1991; Belousova et al., 2002; Dupuis and
Beaudoin, 2011; Dare et al., 2012, 2014; Carranza et al., 2012; Nadoll
et al., 2014). Dupuis and Beaudoin (2011) suggested from the sig-
natures of Ni/(Cr+Mn) vs Ti+V and Ca+Al+Mn vs Ti+V, to
differentiate amongst a broad variety of mineral deposits which include
IOCG, BIF, porphyry Cu, skarn, Ni–Cu–PGE, VMS and Kiruna types.
Trace element concentrations in magnetite from Bhukia show their
typical IOCG association (Fig. 10B and C) and Al+Mn vs Ti+V sig-
natures (Nadoll et al., 2014) also suggest that magnetite is linked to
IOCG deposit type (Fig. 10D). Some of the important trace element
variations for magnetite (Mt) were normalized to bulk continental crust
to identify the possible source (Dare et al., 2014). Multi-element dis-
tribution within magentite from the Bhukia Gold Deposit are akin to the
IOCG fields as outlined in Fig. 11. Multi-element distribution with re-
spect to their compatibility into magnetite is comparable with Mt from
hydrothermal deposits, such as IOCG.
The role of oxygen fugacity (fO2) is very crucial on the composition

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Fig. 9. Mineral chemistry variations using LA-ICP-MS and

EPMA within magnetite depicting relationships between
important major and trace constituents: i.e., higher Ni, V, Co
values and Ni/Cr ratio ideally depicting the IOCG environ-
ment.

of magnetite. Presence of V and Ti in the magnetite is strongly influ- Ti and V. Cr and Mn are also linked with oxygen fugacity (Reguir et al.,
enced by oxygen fugacity, whereas elements like Ca, Ni, Co and Mg 2008). Due to the occurrence of Cr and V in multiple valence states,
have no role on oxygen fugacity (Toplis and Corgne, 2002). Under same their presence is affected by oxygen fugacity (Nielsen et al., 1994;
magmatic conditions, oxygen fugacity decreases with the enrichment of Ryabchikov and Kogarko, 2006; Righter et al., 2006) and presence of

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Fig. 10. Evolution of magnetite from Bhukia gold (+copper) deposit as depicted in several plots: (A) Magmatic and hydrothermal magnetites are distinguished based on Ti vs Ni/Cr
(Bhukia deposit magnetite grain analytical data is depicted in Dare et al., 2012). (B) Ni/(Cr+Mn) vs Ti+V (Dupuis and Beaudoin, 2011) suggesting IOCG deposit style. (C) Ca+Al+Mn
vs Ti+V of Dupuis and Beaudoin (2011) and (D) Al+Mn vs Ti+V (Nadoll et al., 2014) also corroborate the IOCG affiliation based on magnetite EPMA data.

titano-magnetite also controls the oxygen fugacity (Buddington and
Lindsley, 1964; Andersen and Lindsley, 1985; Ghiorso and Sack, 1991;
Toplis and Carroll, 1995). Incorporation of elements such as Al and Ti
in magnetite is considered to be temperature controlled as temperature
of formation is an important criteria for compositional variations in
magmatic and hydrothermal magnetite. Trace element data from study
area suggest that the magnetite forms under high temperature
hydrothermal conditions and in turn favors the IOCG type of deposits
(200–650 °C). Compositional variations in hydrothermal magnetite are
controlled by host rock buffering, mainly in case of large scale meta-
somatic processes. Hydrothermal fluids are enriched in Mg and Mn due
to extensive fluid-rock interactions (Meinert, 1987). Extensive martiti-
zation is seen in the study area which generally depends on the oxygen
fugacity and pH conditions and represent significant changes in the

Fig. 11. Multi-element variation diagram of Dare et al.

(2014) for magnetite normalized to bulk continental crust
(normalized value from Rudnick and Gao, 2003) in in-
creasing order of compatibility into magnetite that shows
close similarity with IOCG deposits.

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Table 2
EPMA and LA-ICP-MS data showing major, minor and trace elements along with REE concentrations within apatite from Bhukia gold (+copper) deposit, western India.

Elements/Lithology CS-14 CS-14 CS-14 CS-14 CS-14 CS-14 B-1 B-1 B-1 B-1 B-1 CS-17 CS-17 CS-17 CS-17

Albitites Tourmaline-rich albitites

EPMA (wt%)
Ca 40.10 39.38 38.64 39.39 39.40 39.02 39.40 39.92 39.30 39.95 39.78 39.88 39.65 39.40 39.20
P 17.70 18.13 18.49 18.41 17.50 18.21 17.70 17.87 17.43 17.78 18.09 18.29 18.22 18.10 18.10
F 2.14 4.23 3.92 3.45 2.93 4.85 2.17 2.26 1.89 2.56 1.87 1.74 4.75 2.93 3.09
O 39.60 39.47 39.02 39.23 38 38.90 38.50 38.95 39.02 39.68 39.46 39.65 38.86 39.10 38.80
Mg 0 0 0.01 0.01 0.01 0.01 0.01 0 0.01 0 0.01 0 0 0.01 0
Al 0 0 0 0 0 0 0.01 0 0 0 0 0 0 0 0
Si 0.03 0.03 0.03 0.02 0.03 0.04 0.04 0.02 0.05 0 0.02 0.02 0.03 0.02 0.04
Fe 0 0 0.04 0.03 0.05 0 0.05 0.07 0 0.03 0 0.02 0 0.04 0.05
Cl 0.09 0.05 0.05 0.07 0.09 0.03 0.09 0.08 0.10 0.07 0.11 0.10 0.04 0.07 0.07
K 0 0.01 0.02 0 0 0 0 0 0 0.01 0 0 0 0 0
Ti 0 0.02 0 0 0 0 0 0 0 0 0 0 0 0 0

LA-ICP-MS (ppm)
Li 0.44 < 0.44 < 0.59 0.50 < 0.37 0.73 < 0.71 < 0.63 0.91 0.40 < 0.54 0.46 0.87 1.11 < 0.62
Be < 0.00 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00 < 0.00
B < 6.24 < 6.55 < 7.62 < 5.23 < 5.64 < 5.81 < 5.89 < 7.27 < 6.57 < 5.77 < 6.65 6.26 13.88 8.32 17.63
Na 137.86 300.34 855.21 116.4 261.47 63.24 244.44 62.58 103.65 659.06 292.94 555.56 318.26 151.79 734.19
V < 0.38 0.81 1.88 1.06 1.66 2.27 9.66 7.40 1.50 6.40 4.12 8.57 1.45 3.39 1.13
Cr < 2.02 3.49 4.82 129.04 2.91 < 1.98 < 2.12 19.79 < 2.30 < 1.97 3.23 < 1.66 91.21 2.49 < 2.73
Mn 498.61 566.39 526.83 441.90 485.55 444.67 394.51 310.57 364.72 612.16 522.78 529.2 358.97 383.37 544.02
Co 0.56 < 0.26 0.51 0.63 0.56 0.44 0.25 0.44 0.32 0.64 0.66 0.36 < 0.16 0.50 0.30
Ni 1.14 2.24 < 0.88 1.90 0.84 2.66 0.95 1.28 1.20 1.59 1.66 0.91 < 1.24 1.80 < 0.82
Cu < 0.32 0.44 0.66 0.45 < 0.25 < 0.37 < 0.76 < 0.69 < 0.47 0.35 < 0.54 < 0.26 < 0.57 < 0.30 2.47
Zn 0.84 < 1.05 2.42 < 0.79 1.16 < 1.00 < 1.23 < 1.30 < 1.17 2.06 5.33 < 0.93 1.93 < 0.93 2.57
Ga 1.34 1.68 1.53 0.86 1.70 1.29 0.79 0.36 1.20 3.20 1.67 2.52 2.61 1.19 1.70
Rb < 0.16 < 0.13 < 0.16 0.11 0.16 < 0.13 < 0.23 < 0.22 < 0.16 < 0.14 < 0.14 < 0.20 < 0.24 0.2 < 0.20
Sr 74.33 79.34 76.96 67.43 66.06 67.69 44.24 60.02 64.47 77.66 74.74 77.33 57.32 68.43 66.41
Y 306.04 159.67 129.94 316.13 253.88 491.75 231.48 65.21 297.44 303.86 220.03 244.68 332.22 644.42 152.68
Zr 0.10 0.09 38.76 0.11 0.03 1.04 0.15 0.26 0.19 0.53 0.24 495.55 0.32 0.37 0.98
Nb 0.02 0.01 0.02 0.01 < 0.00 < 0.00 0.01 0.01 0.04 < 0.00 < 0.00 < 0.00 < 0.00 0.01 < 0.00
Mo < 0.27 < 0.25 < 0.44 < 0.14 < 0.23 < 0.23 < 0.49 < 0.33 < 0.20 < 0.16 < 0.53 < 0.21 < 0.79 < 0.18 0.32
Cd < 0.46 < 0.26 < 0.29 0.25 < 0.47 0.36 < 0.00 < 0.39 < 0.29 < 0.23 < 0.30 < 0.38 < 0.39 < 0.00 0.12
Sn < 0.49 < 0.51 < 0.59 0.75 < 0.47 0.48 < 0.54 < 0.43 < 0.48 0.47 0.53 0.50 < 0.77 0.52 < 0.64
Cs < 0.00 0.01 < 0.02 < 0.01 0.06 0.01 < 0.03 < 0.02 < 0.00 < 0.00 < 0.030 < 0.01 0.07 0.02 < 0.02
Ba 0.16 0.06 0.45 0.18 0.15 0.12 0.19 0.14 0.18 0.37 0.36 0.72 0.64 0.11 0.73
La 418.33 469.14 455.96 193.73 489.26 324.37 280.28 206.11 263.34 995.72 624.12 1058 869.7 279.95 832.11
Ce 538.42 527.61 490.23 296.86 584.52 449.91 380.69 224.76 414.43 1198.08 699.46 1192.78 970.06 381.96 794.42
Pr 40.80 34.98 33.86 26.45 46.86 36.97 34.70 16.63 40.48 111.18 52.11 96.81 73.65 34.87 60.76
Nd 134.98 114.60 100.13 96.57 146.30 137.80 129.49 56.29 178.96 391.36 167.15 323.05 233.71 154.28 192.77
Sm 28.79 17.57 14.41 23.25 24.21 32.61 29.31 8.09 41.73 61.01 28.33 49.93 40.83 45.97 26.27
Eu 7.25 5.93 5.50 13.46 9.35 17.22 8.03 3.11 17.65 10.53 9.65 11.63 12.38 17.74 7
Gd 40.87 25.43 21.51 38.35 37.67 55.73 40.90 10.41 49.6 67.21 35.79 54.23 52.97 71.26 32.26
Tb 6.62 3.29 2.54 6.26 5.21 9.02 5.40 1.261 6.63 7.73 4.49 6.03 7.18 11.53 3.64
Dy 46.14 23.96 17.84 46.28 34.45 68.18 36.97 8.80 42.92 47.78 29.79 36.65 48.94 89.88 23.73
Ho 10.44 5.22 4.37 10.65 8.04 14.89 8.56 1.99 9.73 10.06 6.89 7.97 10.41 21.36 4.60
Er 33.26 16.33 12.83 30.61 24.01 42.80 24.28 5.91 28.81 27.16 20.37 23.82 31.79 63.61 14.24
Tm 4.67 2.23 1.697 4.30 3.34 6.06 3.24 0.861 3.86 3.77 2.66 3.40 4.62 9.05 1.96
Yb 34.06 17.07 12.43 29.95 22.90 41.49 19.96 5.85 26.60 22.98 17.25 22.62 29.24 58.81 14.43
Lu 7 3.21 2.16 5.09 4.13 7.87 3.56 1.217 4.52 4.06 2.93 4.14 5.23 9.11 2.51
Hf 0.06 0.02 1.33 0.02 0.03 0.05 0.03 0.01 0.02 0.02 0.03 12.66 0.02 0.08 0.01
Ta 0.02 0.01 0.01 0.02 0.01 0.02 0.02 < 0.00 0.02 0.02 0.01 0.01 0.01 0.01 0.03
W 4.14 4.25 10.94 10.06 3.96 16.16 4.89 7.06 7.47 5.44 2.71 2.77 1.09 8.19 2.92
Pb 5.68 4.08 2.23 2.24 3.91 3.30 1.93 0.73 3.32 8.35 4.85 10.50 6.90 5.21 6.84
Bi 0.64 0.34 0.20 0.78 0.38 0.81 0.31 0.34 0.77 0.58 0.50 0.46 0.56 0.68 0.27
Th 42.86 18.09 9.42 13.23 21.69 25.24 10.57 2.52 25.32 44.26 26.88 63.14 43.55 46.56 27.04
U 29.68 23.50 15.66 27.37 40.91 41.97 12.61 2.29 31.78 53.09 47.44 62.57 60.82 54.78 39.55
Eu/Eu* 0.65 0.86 0.96 1.38 0.95 1.24 0.71 1.04 1.19 0.50 0.93 0.68 0.81 0.95 0.74
Ce/Ce* 0.93 0.93 0.89 0.94 0.87 0.93 0.87 0.87 0.91 0.82 0.88 0.84 0.87 0.88 0.80
∑LREE 1132.53 1146.33 1080.18 613.61 1266.94 949.05 825.16 503.79 897.21 2696.34 1542.84 2670.64 2147.12 851.06 1880.06
∑MREE 76.91 48.93 41.42 75.06 71.23 105.56 78.24 21.61 108.98 138.75 73.77 115.79 106.18 134.97 65.53
∑HREE 142.19 71.31 53.87 133.14 102.08 190.31 101.97 25.89 123.07 123.54 84.38 104.63 137.41 263.35 65.11
∑REE 1351.63 1266.57 1175.47 821.21 1440.25 1244.92 1005.37 551.29 1129.26 2958.63 1700.99 2891.06 2390.71 1249.38 2010.7
Y/∑REE 0.23 0.13 0.11 0.38 0.18 0.4 0.23 0.12 0.26 0.1 0.13 0.08 0.14 0.52 0.08
(La/Sm)N 14.51 26.7 31.64 8.33 20.21 9.95 9.56 25.46 6.31 16.32 22.03 21.19 21.32 6.09 31.67
(Ce/Th)N 12.54 29.17 52.04 22.44 26.96 17.82 35.94 13.77 16.37 27.07 26.32 18.89 22.25 8.2 29.38
Th/U 1.44 0.77 0.6 0.48 0.53 0.6 0.84 1.1 0.8 0.83 0.56 1.01 0.72 0.85 0.68

volume of the rocks (Mücke and Raphael Cabral, 2005). Martitization 6.4. IOCG-IOA affiliation based on magnetite-apatite in a Proterozoic gold
supports high oxidation and low-temperature conditions for most of the regime
IOCG, Kiruna and porphyry Cu deposits.
Apatite from Bhukia gold (+copper) deposit consists of major,

523
R. Mukherjee et al.
Fig. 12. Mineral chemistry variations based on EPMA and LA-ICP-MS data from key trace
elements and REE systematic within apatite grains; Cl exhibiting negative trending with
respect to higher F values indicating its typical flourapatite nature. (B) LA-ICP-MS ana-
lytical results of chondrite normalized REE from apatite of Bhukia gold (+copper) deposit
showing marked enrichment of LREE relative to MREE and HREE, with negative Eu
anomaly akin to apatite associated with IOCG-IOA deposits (normalized value from
Boynton, 1984); (C) Evolutionary patterns of apatite ranging from moderate to high
oxidizing environments as evidenced from Eu/Eu* vs Ce/Ce*.
524
Ore Geology Reviews 91 (2017) 509–529
minor and trace elements like Na, Mg, Al, Si, Zn, Fe, Ca, Cr, B, F, P, K,
Ti, V, Mn, Sr, Y, Th, U along with REE which are analyzed using
Electron Probe Micro Analyzer and Laser ablation ICP-MS (Table 2).
Detailed analysis of apatite shows wide range of concentrations for Na
(63–855 ppm), Si (200–500 ppm), Zn (100–1000 ppm), Fe (200–700
ppm), Mn (310–612 ppm), Cr (100–300 ppm), K (100–200 ppm), V
(100–300 ppm). Calcium and phosphorus are the most abundant ele-
ments present within apatite and their concentration ranges from
39.02-40.08 wt% and 17.43–18.49 wt% respectively. Apatite is of
fluorapatite variety as fluorine content is significantly high
(1.87–4.85 wt%). F and Cl exhibit a negative trend (Fig. 12a). Depletion
of Cl (0.03–0.11 wt%) with enrichment of F from the Bhukia area
suggests remelting of pre-existing meta-volcano-sedimentary source
rocks that had enrichment of F and subsequent loss of Cl owing to its
higher solubility nature in aqueous solution (Brehler and Fuge, 1974;
Sha and Chappell, 1999; Cao et al., 2012).
Apatite is commonly Ca-rich, while Y, Mn, Sr, Th, U and REE are
depleted as these elements are assumed to partition the Ca site of
apatite (Roeder et al., 1987; Coulson and Chambers, 1996; Mao et al.,
2016). The F is enriched in Fe-rich melt due to its higher partition
coefficients (Hou et al., 2011), mixed with hydrothermal fluid and
precipitate as F-rich apatite (Fluorapatite). Hence relatively high con-
centration of F in apatite could be attributed to the involvement of
magmatic hydrothermal activity in the study area (Zhu and Sverjensky,
1991). Mg concentration in apatite is up to 100 ppm as is common in
IOCG-IOA. Y concentration varies from 65-644 ppm with lower Sr
concentration (44–79 ppm) reflecting the contrasting behavior of these
elements during the fractionation process (Belousova et al., 2002).
Lower concentration of Sr in apatite indicates partitioning of Sr in
plagioclase (Belousova et al., 2001, 2002).
Apatite from Bhukia contains 551–2959 ppm REE. The REE patterns
of apatite samples show enrichment of LREE (∑LREE = 504–2696 ppm)
and flat to depleted MREE and HREE (∑MREE = 22–139 ppm and
∑HREE = 26–263 ppm) exhibiting negative Eu anomaly (Eu/
Eu∗ = 0.5–1.38) (Fig. 12b). Lower values of Mn and Y/∑REE along with
higher values of (La/Sm) and (Ce/Th) indicate that the apatite is
crystallized from highly oxidized environment (Belousova et al., 2001,
2002). Cao et al. (2012) and Mao et al. (2016) suggested that variation
in As and V contents within apatite from 400-800 ppm and 100–300
ppm respectively indicates oxidizing environment. Eu/Eu∗ vs. Ce/Ce∗
(Cao et al., 2012) suggests oxidized source of apatite (Fig. 12c). Lower
concentration of Cd and Na along with variable Th/U suggest meta-
volcano-sedimentary source for apatite (Rajabzadeh et al., 2014).
EPMA and Laser ablation ICP-MS data suggest that the Paleoproterozoic
Bhukia gold deposit is akin to Kiruna-type IOA (Iron-Oxide Apatite)
deposits (Yu et al., 2011; Talab et al., 2015; Mao et al., 2016; Zarei
et al., 2016) which is considered as end-member of hydrothermal IOCG
deposits (Hitzman et al., 1992; Hitzman, 2000; Williams et al., 2005;
Groves et al., 2010). Based on the host rock geochemical signatures, the
study area has extensional tectonic setup related to intracontinental rift
system (Singh, 1988; Ray, 1990; Shekhawat et al., 2007; Bhattacharya
and Bull, 2010; Fareeduddin et al., 2010) which is similar to the tec-
tonic setting of most of the IOCG-IOA deposits. Presence of extensive
hydrothermal alterations, abundance of magnetite over hematite, pre-
sence of Cu+Au+REE, occurrence of late stage pyrite and presence of
apatite further corroborates IOCG-IOA association (Yu et al., 2011).
Comparison between Paleoproterozoic Bhukia Gold Deposit and other
key Proterozoic IOCG deposits is shown in Table 3.
6.5. Gold-Magnetite-Apatite association
Gold is associated with magnetite in Bhukia and the latter holds a
key role in the precipitation of gold in Bhukia Gold Deposit. Magnetite
is ubiquitously present in many magmatic hydrothermal deposits (more
so in IOCG deposits) and has certain bearing on the hydrothermal
system that led to gold sulfide mineralization in Bhukia area (Gammons
 Table 3
Comparison between Paleoproterozoic Bhukia gold (+copper) deposit vis-a-vis key IOCG deposits.

Deposit Age Host rocks Structural setting Ore minerals Alterations Tonnage and grade Elemental References
association
R. Mukherjee et al.

Olympic Dam, Gawler 1590 Ma, A-type granite, Meta- Fault controlled breccia Bornite, chalcopyrite, Quartz, hematite, sericite, 9576 Mt at 1.2% Cu, Fe, Cu, Au, F, Porter (2010), Hayward
Craton, Australia Mesoproterozoic volcanic rock complex at intersection of chalcocite, native copper, chlorite and carbonate 0.5 g/t Ba, LREE, U, and Skirrow (2010),
major lineaments formed gold, magnetite, hematite, Au, 6 g/t Ag, 0.04% Ag, Co, P Ehrig et al. (2012) and
at shallow crustal levels pyrite, uraninite U3O8, Zhu (2016)
0.05% REE
Ernest Henry, Mount Isa 1514–1504 Ma, Intermediate Hydrothermal breccias in Chalcopyrite, gold, Albite, feldspar, quartz, 226 Mt at 1.1% Cu and Fe, Cu, Au, Mn, Williams et al. (1999),
Inlier, Northern Mesoproterozoic metamorphosed felsic ductile–brittle shear zone, hematite, magnetite, Biotite, garnet, chlorite, 0.5 g/t Au Mo, As, Mark et al. (2000),
Australia volcanic rock, diorite, some stratabound in pyrite, pyrrhotite muscovite, magnetite, Co, Ba, F, U, W, Oliver et al. (2004),
psammite, calc-silicate carbonaceous host rocks diopside and hornblende LREE Porter (2010), Duncan
rock et al. (2014)
Starra, Mount Isa Inlier, > 1505 Ma, Ironstones, mica-schist, Ductile-brittle shear zone, Magnetite, hematite, Albite, quartz, calcite, 253 Mt at 0.34% Cu and Fe, Cu, Au, Co, Rotherham et al.
Northern Australia Mesoproterozoic calc-silicates, breccia chalcopyrite, pyrite, gold, sericite, chlorite, Biotite, 0.48% Au W, Sn, F, Mo, (1998), Williams et al.
amphibolites chalcocite, bornite muscovite, hematite and LREE (2001), Oliver et al.
magnetite (2004), Zhu (2016)
Mt Elliott, Cloncurry 1510 Ma, Carbonaceous schist, Breccia and veins in Magnetite, pyrite, Albite, actinolite, diopside, 570 Mt at 3.6% Cu and Fe, Cu, Au, Co, Mark et al. (2001),
district, Mount Isa Mesoproterozoic phyllite, Amphibolite, dilational jog in shear pyrrhotite, chalcopyrite tourmaline, apatite and 1.8 g/t Au Ni, F, P, Wang and Williams
Inlier, Northern trachyandesite zone controlled by brittle magnetite LREE, Mo, Se, (2001) Oliver et al.
Australia faults Te, U (2004), Zhu (2016)
Alemao, Carajas district, Paleoproterozoic Metavolcanic rocks, Steeply dipping tabular Magnetite, chalcopyrite, Albite, K-Ca-feldspar, 219 Mt at 1.40% Cu and Au, Cu, Zn, Co, Requia and Fontboté
Southern Amazon dioritic dikes, siderite- breccias bodies bornite, hematite, gold calcite, epidote, sericite, 0.86 g/t Au Mo, U, LREE (2000), Requia et al.
Craton, Brazil chlorite breccia biotite (2003), Xavier et al.
(2012), Zhu (2016)
NICO, Great Bear 1850 Ma, Sub-arkosic wacke, Diatreme and fracture Magnetite, hematite, K-feldspar, magnetite, 42 Mt at 0.1% Co, 0.5 g/t Fe, Au, Co, As, Goad et al. (2000)
Magmatic Zone, Paleoproterozoic rhyolite, siltstone breccias at intersection of arsenopyrite, cobalt, carbonates, chlorite, Au and 0.1% Bi Bi, W, Te, Ba, B,

525
Canada structural lineaments bismuth, pyrite, pyrrhotite, tourmaline P, F, LREE
chalcopyrite
Sue-Dianne, Great Bear 1850 Ma, Rhyodacite ignimbrite, Diatreme breccia at Hematite, magnetite, K-feldspar, hematite, 17.3 Mt at 0.72% Cu, 2.7 Fe, Cu, Ag, U, Goad et al. (2000), Zhu
Magmatic Zone, Paleoproterozoic marginal to rapakivi intersection of structural chalcopyrite, bornite, magnetite, quartz, garnet, Ag and 0.06 g/t Au Mo, Ba, P, Bi, (2016)
Canada pluton lineaments chalcocite, covellite, epidote, fluorite Co, F, REE
molybdenite
Tjårrojåkka, Sweden Paleoproterozoic Andesitic metavolcanic Shear/fault next to chalcopyrite, bornite, Albite, biotite, magnetite, 3.2 Mt at 0.9% Cu Cu, Fe, P, F, Ba, Edfelt and Martinsson
rock, dolerites intersection of two major magnetite, pyrite, apatite, carbonates Au, Ag, Te, Mo, (2003), Edfelt et al.
shear zones chalcocite, covellite, Th, REE (2005)
molybdenite
Nautanen, Sweden Paleoproterozoic Intermediate Shear zone chalcopyrite, magnetite, Albite, K-feldspar, biotite, 0.63 Mt at 2.4% Cu, 1.3 g/ Cu, Fe, Au, Ag, Martinson and Aaltonen
metavolcanic rocks(?) pyrite, Sphalerite, galena, magnetite, garnet, t Au and 11 g/t Ag Ba, B, Co, Zn, W (2004)
molybdenite bornite, tourmaline
chalcocite
Laurinoja, Finland 1800 Ma, Mafi c metavolcanic rock, Bend in reverse thrust/ Magnetite, pyrite, Albite, K-feldspar, biotite, 33 Mt at 43% Fe, < 0.1 Fe, Cu, Au, Ag, Hiltunen (1982),
Paleoproterozoic diorite, mica gneiss, fault zone pyrrhotite, chalcopyrite, magnetite 11.0% Cu, < 0.1–6.6 g/t Bi, Ba, Co, Mo, Niiranen et al. (2007)
quartzite, marble (?) gold, molybdenite Au and < 0.1–17.7 Ag Sb, Te, LREE and Billström et al.
(2010)
Rautuvaara, Finland 1800 Ma, Mafi c metavolcanic rock, Next to reverse thrust/ Magnetite, pyrite, Albite, biotite, K-feldspar, 4 Mt at < 0.1–1.5% Fe, Cu, Au, Ag, Hiltunen (1982),
Paleoproterozoic diorite fault pyrrhotite, chalcopyrite, Titanite, chlorite, magnetite Cu, < 0.1–2.6 g/t Au Ba, Bi, Mo, Se, Niiranen et al. (2007),
uraninite and < 0.1–1.2 g/t Ag Te, Th, U, LREE Billström et al. (2010)
and Zhu (2016)
Boss-Bixby, St Francois Mesoproterozoic Syenite, rhyolite Breccia, vein and magnetite, ilmenite, K-feldspar, garnet, calcite, 40 Mt at 0.8% Cu Fe, Cu, Au, Ag, Porter (2010)
Terrain, replacement hematite, pyrite, fluorite, gypsum, chlorite Mo, Co, REE
midcontinent, mineralization at contact molybdenite, cobaltite, and quartz, epidote
Missouri, USA of central intrusive cuprite, chalcopyrite,
complex bornite, sphalerite, galena,
chalcocite
Warrego, Tennant Creek Paleoproterozoic Quartz-muscovite schist, Metasomatic ironstone, chalcopyrite, native gold, Albite, chlorite, biotite, 6.750 Mt at 6.6 g/t Au Fe, Cu, Au, Bi Porter (2010)
(continued on next page)
Ore Geology Reviews 91 (2017) 509–529
R. Mukherjee et al. Ore Geology Reviews 91 (2017) 509–529

Mukherjee et al. (2016)

and Williams-Jones, 1997; Larocque et al., 2000; Groves and Santosh,

Zhao and Zhou (2011),

(2014), Fareeduddin
2015). Initial high oxygen fugacity conditions are attributed to mag-

Knight et al. (2002)

et al. (2012, 2014),

GSI Bulletin Series
Frost-Killian et al.
Zhu (2014, 2016)
netite precipitation (Fig. 5). The relation between magnetite, apatite
and gold in Bhukia suggests that all were resulted from hydrothermal

Zhu (2016)
References

fluid activity. The enrichment of Fe-P could be attributed to the silicate

(2016)
liquid immiscibility at the late magmatic stage promotes the direct
precipitation of magnetite from the hydrothermal fluid with increase in
the fluid influx (Dare et al., 2014). Phosphorous is added in magma due

Ag, U, Th, LREE

Fe, Cu, REE, Au

Fe, Cu, Au, As,

Cu, Fe, Au, As,

Cu, Fe, Zn, As,
to contamination from the upper crust. Later, the concentration of vo-
Fe, Cu, Mo,

Mo, Co, Ni,

association

Co, Ag, Bi
Elemental

latile like F is enriched in Fe-rich melt due to its higher partition

REE, Au

coefficients (Hou et al., 2011), mixed with hydrothermal media and

precipitated as F-rich apatite (Fluorapatite). This suggests that magne-
tite and apatite from Bhukia Gold Deposit could have co-precipitated
33.4 Mt at 1.12% Cu and

105.18 Mt at 1.97 g/t Au

106 Mt at 0.92% Cu and

192 Mt at 0.90% Cu and

phase-wise from the similar fluids nevertheless in different bouts. Fer-

140 Mt at 1.1–1.7% Cu rous iron and gold can be carried by relatively low temperature hy-
Tonnage and grade

and 0.5 g/t Au

drothermal fluids and aqueous vapor from a possible granitic intrusive

and 0.15% Cu
and 1.9% Cu

source (Gammons and Williams-Jones, 1997; Simon et al., 2004; Jowitt

0.19 g/t Au

0.18 g/t Au

1.41 g/t Au

et al., 2014; Mukherjee et al., 2016). Liang et al. (2009) shows that
precipitation of magnetite could supply reduced sulfur to hydrothermal
systems, promoting sulfide mineralization along with gold.
carbonate, sericite, chlorite

calcite, dolomite, ankerite,

magnetite, apatite, Biotite,

Albitite, Biotite, grunerite,

Albite, K-feldspar, quartz,

7. Concluding remarks
Chlorite, Biotite, sericite
K-feldspar, carbonates,
muscovite, magnetite

magnetite, graphite

1) Sulfide-oxide mineralization with variable concentration of mag-

tourmalinization,
carbonatization,
graphitization

netite, apatite, arsenopyrite, pyrrhotite, pyrite, chalcopyrite, gra-

Albitization,
Alterations

muscovite

phite and gold is hosted in albitites, metapelites and carbonates

from the Paleoproterozoic Bhukia Gold Deposit.
2) Detailed LA-ICP-MS and EPMA mineralogical/chemical character-
ization of magnetite and apatite provided important clues regarding
magnetite, graphite, native
arsenopyrite, molybdenite

the genetic environment in which Bhukia Gold Deposit has formed.

Chalcopyrite, pyrrhotite,
Chalcopyrite, magnetite,

Pyrrhotite, arsenopyrite,
cobaltite, bismuth, gold,
arsenides, arsenopyrite,
cobaltite, bismuthinite,

chalcopyrite, Fe-Co-Ni
Magnetite, pyrrhotite,

This study suggests that the magnetite together with apatite plays
chalcopyrite, bornite
Magnetite, hematite,

cubanite, Sphalerite,

pyrite, chalcopyrite,
magnetite, hematite

pyrite, magnetite,

key role in precipitation of gold-sulfide mineralization in hydro-

thermal IOCG setup.
Ore minerals

3) Mineral chemical data suggest that the apatite associated with mag-
netite is of fluorapatite variety with low Cl and its close association with
silver
gold

gold

the gold (+Cu) is suggested to have evolved in an IOCG-IOA setup.

4) Elemental concentration in apatite from Bhukia is indicative of
coalescing lenses in shear

parental fluid oxidizing conditions. Presence of fluorapatite, de-

Stratiform-stratabound,
Hydrothermal breccia

Deformed superposed
folds, in shear system
Breccia and multiple
possibly in fold limb

pleted Cd and Na with variable Th/U suggests meta-volcano-sedi-

Replacement within

dissemination and
Structural setting

mentary source of apatite.

breccias pipes,

5) Paragenetic relationships of mineral phases suggest that magnetite

and apatite are precipitated from initial Fe-P rich high temperature
veinlets

folding

magmatic hydrothermal fluids in higher oxygen fugacity environ-

zones

ment. Further dilution of these magmatic hydrothermal fluids led to

form low temperature hydrothermal brines and promoted further
Marble and meta-volcanic

Meta-carbonate rocks and

Albitites, quartzite, mica-

quartzites, tourmalinite,

precipitation of magnetite and apatite in the second stage of mi-

amphibolite quartzite
garnetiferous chlorite

Albitite, carbonates,

neralization. Magnetite and apatite in this stage are associated with

rocks, amphibolite,

schist and banded

staurolite schist,

shear zones where the grains are rotated and deformed. Later due to
quartzite, slate

schist, marble

further influx of hydrothermal fluids in the mineralizing system,

amphibolite
metabasalt
Host rocks

cessation of oxidation condition has prevailed. Low temperature

Albitite

hydrothermal fluids with associated ligands promote suitable re-

ducing conditions for precipitation of sulfides. As the temperature
decreased further, graphite was precipitated due to the mixing of
low temperature hydrothermal fluids with precursor organic carbon.
Paleoproterozoic
Mesoproterozoic

Mesoproterozoic

Neoproterozoic

Neoproterozoic

Precipitation of gold is aided by interaction of fluids with organic

1850 Ma,

carbon. Gold evolved in three phases, beginning with invisible/re-

fractory, as substrates and latter remobilized to form as main lodes/
Age

nuggets.
6) Occurrence of magnetite along with apatite is a common feature in
Dahongshan, Kangdian
basement, Yangtze

basement, Yangtze

Guelb Moghrein, West

Bhukia Gold Prospect,

Supergroup, India

Supergroup, India
Craton, SW China

IOCG-IOA association. This typogenic association together with

Inlier, northern

African Craton,
Craton, China
Table 3 (continued)

characteristic mineral chemistry suggests that the Bhukia Gold

Khetri, Aravalli
Mauritania
Lala, Kangdian

Deposit is much similar to IOCG-IOA deposits. The above features

Australia

Aravalli

together with similar tectonic setting, extensive albitite alteration,

Deposit

presence of Cu-Au-REE association, enrichment of magnetite over

hematite, presence of sulfides and apatite further attest IOCG-IOA
association of Bhukia gold deposit.

526
R. Mukherjee et al.
Conflict of interest
The authors state that they have no conflict of interest.
Acknowledgement
The authors are thankful to the Director, Indian Institute of
Technology (Indian School of Mines), Dhanbad for the facilities; IIT
(ISM) Central Research Facility, for Electron Probe Analysis; Dr.
Dewashish Upadhyay, Department of Geology and Geophysics, IIT
Kharagpur for LA-ICP-MS analysis; Geological Survey of India (GSI),
Western Region, Jaipur for support in the field areas. Mr. I. R. Kirmani
(Additional Director General, GSI, WR, Jaipur, India), Mr. Amit
Shrivastava (Senior Geologist, GSI, NER, Shillong, India) and Mr. R. L.
Jat (Senior Geologist, WR, Jaipur, India) helped RM in the field studies
and we thankfully acknowledge the same. The authors thank
Department of Science and Technology, Govt of India for the support
through DST-FIST grants to Department of Applied Geology, IIT(ISM).
We thank Dr P R Sahoo for some important discussions related to this
work. Thanks are also due to Prof Franco Pirajno for the editorial
handling and for his useful suggestions. We are grateful for the con-
structive comments of Prof. Qun-Ke Xia, Dr. Hassan Heidarian and an
anonymous reviewer which helped to improve the manuscript. R.M.
acknowledges the financial support received from IIT (ISM), Dhanbad
for his research fellowship.
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