Ore Geology Reviews 134 (2021) 104149

Contents lists available at ScienceDirect

Ore Geology Reviews

journal homepage: www.elsevier.com/locate/oregeorev

Trace-element systematics and isotopic characteristics of sphalerite-pyrite

from volcanogenic massive sulfide deposits of Betul belt, central Indian
Tectonic Zone: Insight of ore genesis to exploration
Bishnu Prasad Mishra a, Pitambar Pati a, Muduru Lachhana Dora b, *, Srinivasa Rao Baswani b,
Tushar Meshram b, Mohd. Shareef c, Ram Sankar Pattanayak d, Hemraj Suryavanshi b,
Monika Mishra e, Mohd Atif Raza e
a
Department of Earth Sciences, Indian Institute of Technology, Roorkee 247667, India
b
Geological Survey of India, Nagpur 440006, India
c
Geological Survey of India, Bengaluru 560070, India
d
Chikiti Mahavidyalaya, Chikiti 761010, India
e
Geological Survey of India, Faridabad 121001, India

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

Keywords: The Paleoproterozoic volcanogenic massive sulfide (VMS) deposits in the Betul belt (BB) (ca.1.7 Ga) in central
Sphalerite India are well-known for their low-grade Zn-Cu-Pb sulfide mineralization. The physicochemical conditions of ore
Pyrite formation, size, grade, extent, and nature of mineralization are the ongoing debates and concerns to the
LA-ICP-MS
exploration agencies for the last two decades. Field examination, drill core analysis, petrography, and scanning
Stable-isotopes
VMS
electron microscopic studies reveal the occurrence of chalcopyrite, sphalerite, pyrite, galena with minor pyr­
Betul Belt rhotite in the form of dissemination, stringers, and semi-massive sulfide veins.
We present the minor-trace element contents in sphalerite and pyrite from drill core samples of four deposits
(Banskhapa, Jangaldehri, Biskhan, and Bhuyari), analyzed by electron probe microanalyzer (EPMA) and in-situ
laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS) for determining ore-forming tem­
perature, ore genesis and exploration prospectivity. The EPMA and LA-ICP-MS studies of sphalerite display a
slightly high concentration of trace elements like Mn, In with a mean value of 3533 ppm and 33 ppm, respec­
tively. On the other hand, Ga, Ge, and Ag content are low in abundance along with a low concentration of Bi, Pb,
and Sb in all four deposits. Pyrites show low Ni and high Co/Ni (mostly > 1) ratios and variable Ti, Se, As, and
Mn. Multivariate statistical analysis, especially the principal component analysis (PCA) of these trace elements,
defines the geochemical variations among the Betul belt deposits. The ore-forming temperature is estimated
using sphalerite thermometry (374 ◦ C to 402 ◦ C) and pyrite thermometry (225 ◦ C to 484 ◦ C). The geochemical
discrepancies occur due to magmatic-hydrothermal activities caused by the sub-volcanic intrusions, followed by
recrystallization and remobilization of the sub-microscopic inclusions during subsequent metamorphism.
Additionally, sulfur isotope analysis provides insights into the sulfur source variations, metals, and mineral­
ization. Carbon and Oxygen isotopes are used to understand the physicochemical conditions of the ore-forming
environment. Sphalerite, pyrite, and chalcopyrite from Banskhapa deposit suggest a broad range of δ34S values
(7.27–7.79‰, 8.37–8.61‰, and 6.58–6.72‰ respectively, n = 7), which advocate sulfur mostly derived by
thermochemical reduction (TSR) of seawater sulfate with some input of magmatic sulfur leaching from the
igneous basement. Carbon and oxygen isotope studies of carbonates from Jangaldehri and Bhuyari deposits (δ
13
C: − 6.0 to − 13.45‰ with an average value of − 9.51‰, n = 7; δ 18O: 7.32‰ to 20.58‰ with an average value
of 15.65‰, n = 7) indicate that the carbonates formed from a hydrothermal fluid (seawater with an insignificant
magmatic input), the mixing of hydrothermal fluid with ingressing seawater, or both in the mineralized zone.
These processes collectively led to Zn-Cu and Zn-Cu-Pb mineralization in the Betul belt.
High temperature, strong isotopic and trace element geochemical variations in sphalerites (Ag-Mn, In/Cd-Mn,
In/Cd-Fe, Mn-In/Ge, Fe-In/Ge, Fe-In) and pyrite (Ni-Co, As-Cu, Ag-Au, and Se-Te) attest to the mineralization as

* Corresponding author at: Geological Survey of India, Central Region, Nagpur 440006, India.
E-mail address: dorageol@gmail.com (M.L. Dora).

https://doi.org/10.1016/j.oregeorev.2021.104149
Received 27 December 2020; Received in revised form 27 March 2021; Accepted 29 March 2021
Available online 2 April 2021
0169-1368/© 2021 Elsevier B.V. All rights reserved.
B.P. Mishra et al.
being volcanogenic massive sulfide (VMS) deposits in Betul belt and differentiated from other genetic types like
Mississippi Valley-type (MVT), sedimentary-exhalative (SEDEX), skarn, porphyry, and epithermal hydrothermal
deposits.
1. Introduction
Volcanogenic massive sulfide (VMS) deposits are desirable targets
for researchers and explorers because of their polymetallic nature as
well as the occurrence in the ancient and modern geological framework
(Franklin et al., 1981, 2005; Galley et al., 2007; Hannington et al.,
1999a, 1999b; Piercey, 2009; Lentz, 1999). More than 850 VMS deposits
are reported worldwide that supply a significant amount of metals such
as Cu, Zn, Pb, along with Mn, In, Ga, Ge, Au, Ag, Bi, Sn, Ba, and Te as
secondary products (Galley et al., 2007). The Paleoproterozoic Betul
supracrustal belt (ca.1.7 Ga), a key segment of the Central India Tectonic
Zone (CITZ), is a potential belt for polymetallic sulfide mineralization.
However, ongoing debates on the style of mineralization, low-grade, and
sub-seafloor replacement VMS-type mineralization in Betul belt (BB) is
the growing consensus among the researchers. The Geological Survey of
India (GSI), using traditional exploration techniques, has discovered a
few economically viable deposits in a cluster along a ENE-WSW trend
within a 30 km stretch together with several other potential occurrences
across the belt (Raut and Mahakud, 2004; Golani et al., 2006; Praveen
et al., 2007, 2020; Raza et al., 2020). The deposits are typically Zn-
enriched with variable Cu and Pb ratios based on the nature of the
footwall lithologies (Praveen et al., 2007, 2020). Early workers were
predominantly focused on sulfide mineralization, submarine volcanic
facies analysis, sulfur source, meta-exhalites characterization, rhyolite
classification, gahnite as a tracer for exploration strategy, and resource
estimation (Chaturvedi, 2001; Ghosh and Praveen, 2008; Golani et al.,
2006; Praveen et al., 2007; Raut and Mahakud, 2004; Raza and Naidu,
2018; Kumari and Panda, 2018; Raza et al., 2020; Roy, 2011; Yousuf
et al., 2019). However, comprehensive research has not been done on
the ore-forming environment and exploration prospectivity.
Recent developments of laser ablation -inductively coupled plasma
mass spectrometry (LA-ICP-MS) analytical techniques consensus for in-
situ measurements of trace element concentrations with sub-part per
million (ppm) /part per billion (ppb) detection limits with micrometer-
scale spatial resolution. Metal sulfides such as sphalerite and pyrite
attract the interest of researcher because typically, these minerals are
common ore minerals in many hydrothermal sulfide deposits, stable
under overall physicochemical conditions, and show refractory behav­
iors to metamorphism relative to other sulfides (Caruso et al., 2018;
Cooke et al., 2020; Bauer et al., 2019; Cook et al., 2009; Craig and Vokes,
1993; Frenzel et al., 2016; Keith et al., 2018; L’Heureux, 2000; Revan
et al., 2014; Ye et al., 2011; Bailie and Gutzmer, 2011; Chen et al., 2011,
2018; Lentz, 2002). The LA-ICP-MS technique advances the sulfide
mineral chemistry research substantially by constraining the incorpo­
ration mechanism of trace elements into the mineral structures as solid
solution substitution and micro/nano inclusions (Chowdhury et al.,
2020; Ciobanu et al., 2012; Cook et al., 2016; Dehnavi et al., 2018;
Genna and Gaboury, 2015; George et al., 2016; Keith et al., 2018;
Knorsch et al., 2020; Large et al., 2009; Maslennikov et al., 2009; Deng
et al., 2019; Wang et al., 2021). Sphalerite hosts a wide variety of trace
elements, e.g., Ga, Ge, Tl, In, Ag, Hg, Fe, Mn, Co, Cu, Se, Cd, Sn, Sb, and
Pb, whereas pyrite accommodates trace elements, like Cu, Ni, Pb, Zn, Co,
Te, Tl, Sb, As, Se, Bi, Au, Ag, and Hg. The enrichment of the trace ele­
ments in the metal sulfide structures suggests the source of the metal and
ore-genesis processes (Zhang et al., 2014) and (Steadman et al., 2020).
Sphalerite trace element geochemistry is used in diverse-type deposits to
understand the critical metallogenic aspects such as origin and distri­
bution of elements, fluid pathways, ore-forming temperature, elemental
incorporation, and metamorphic effect (Chen, 2013; Cook et al., 2009;
Frenzel et al., 2016; Lockington et al., 2014; Moller, 1987; Rose, 1967;
2
Ore Geology Reviews 134 (2021) 104149
Ye et al., 2011). Sphalerite trace element content indicates genetic types
and characterizes the distinctive geochemical signatures for each de­
posit type (Cook et al., 2009; Frenzel et al., 2016). Similarly, variations
in trace element geochemistry in pyrite are useful for inferring the ore
genesis processes at deposit scale to regional to the global level in time
and space (Dehnavi et al., 2018; Keith et al., 2018; Zhang et al., 2014;
Steadman et al., 2020; Cooke et al., 2020).
Broadly, the purpose of the research is to understand the metal­
logenic evolution and discuss an exploration prospectivity for the low-
grade nature of Zn-Cu-Pb mineralization in the Betul belt specifically.
Here, we study the trace element geochemistry of sphalerite and pyrite
along with detailed ore petrography followed by principal component
analysis (PCA) of four distinct deposits viz; Banskhapa, Jangaldehri,
Biskhan, and Bhuyari. Multivariate statistical analysis, especially the
principal component analysis (PCA) of trace elements suite from the
deposits, defines the geochemical variation in VMS-type deposits in the
Betul belt. More precisely, the PCA was done to interpret the
geochemical data and find the critical pattern among these deposits in
the Betul belt. It simplified the complex data and converted it into two
principal components retaining its original trends and pattern. The trace
elements data reveal significant geochemical variation that explains the
multiple geological processes that led to the formation of the poly­
metallic mineralization and associated physicochemical conditions in
the four deposits.
Stable isotopes viz; sulfur (δ34S), Carbon (δ13C) and Oxygen (δ18O)
helped to infer the sources, constraint physicochemical parameters, and
sulfide mineralization in Betul belt (Ohmoto, 1972; Hoefs, 2009; Bailie
et al., 2010; Essaifi et al., 2019; Caruso et al., 2019; Chen et al., 2011).
The ore-forming temperature has been estimated using sphalerite geo­
thermometers devised by Kullerud (1953) and Frenzel et al. (2016) and
pyrite thermometry developed by Keith et al. (2018). In this paper, we
present trace element geochemistry of sulfides (sphalerite, pyrite) and
stable isotope systematics viz; sulfur (δ34S), carbon (δ13C), and oxygen
(δ18O) to understand the nature of the fluid source, its origin, and
temperature of the ore-forming process in the Betul belt.
2. Regional geological outline
The Betul belt (BB) is a Precambrian inlier, one of the well-known E-
W trending lithotectonic units situated in the CITZ (Fig. 1A-B). The CITZ
has been considered a trans-continental suture between the north Bun­
delkhand craton and the south Bastar craton (Radhakrishna and Naqvi,
1986; Harris, 1993). The Betul belt covers an area of approximately
4000 square kilometers. It is bounded by the Mahakoshal belt in the
north and Sausar belt in the south and covered by Deccan basalts in the
east and younger Gondwana sediments in the west and north. The Betul
belt extends linearly for about 150 km in ENE–WSW strike from Chicholi
in the west to Chhindwara in the east, having a width varying from 20 to
30 km (Golani et al., 2006; Roy and Chakraborti, 2001) (Fig. 1. This belt
exposes three significant rock associations viz; (1) Supracrustal rocks,
(2) Mafic- ultramafic rocks, and (3) Syn- to post-kinematic granitic rocks
(Chaturvedi, 2001; Golani et al., 2006; Praveen et al., 2007, 2020; Raut
and Mahakud, 2004). The details of these assemblages are given in the
stratigraphy (Table 1).
The supracrustal rocks are mainly volcano-sedimentary sequences,
predominately exposed in the eastern and central parts. In contrast,
mafic–ultramafic bodies are nearly exposed in the western and north­
western parts of the belt. The BB contains bimodal volcanics of acid and
basic composition together with meta-exahalites, quartzites, Banded
Iron Formation (BIF), metapelites, and calc-silicates (Ghosh and
B.P. Mishra et al.
Praveen, 2008). The bimodal volcanics are non-cogenetic, consists of
metabasalt and meta-rhyolite, associated with sulfide mineralization,
belong to the Bargaon Formation of the Betul Group (Chaturvedi, 2001;
Chore et al., 2002). The metabasalt is low K-tholeiitic, while the meta-
rhyolite is transitional to alkaline in composition and interpreted to be
emplaced in an old continental arc environment (Raut and Mahakud,
2004).
Moreover, pillow and vesicular structure in metabasalt, along with
hyaloclastite and autoclastite rhyolite rocks, are attributed to an effusive
kind of sub-aqueous extrusion (Praveen and Ghosh, 2009). Rare traces of
polyphase migmatitic gneisses known as Amla gneiss are also identified
within the intrusive granites. The entire belt has undergone a variable
grade of metamorphism. Three successive phases of folding initially to
isoclinal folds with ENE-WSW striking axial planes, followed by a co-
axially refolded phase and then cross folds (Roy and Prasad, 2003).
2.1. Deposit geology
The sulfide mineralization is syngenetic with the Paleoproterozoic
age’s felsic volcanic rocks (ca.1.7 Ga, (Praveen et al., 2020) (Fig. 1C, 2 A-
D). The textural characteristics of the host volcano-clastic materials of
rhyolite vary significantly in different deposits in the Betul belt
(Fig. 2A–D). Ore zones in volcano-clastic rhyolites are hydrothermally
altered and overprinted by upper amphibolite facies of metamorphism
(Praveen et al., 2005, 2020). This led to the formation of a typical
metamorphic mineral assemblage in rhyolites, which often acts as an
exploration vector. Praveen et al. (2007) reported two types of alter­
ations; type-i is Mg-Ca, mostly of anthophyllite + actinolite + tremolite
+ phlogopite, type-II is Al-Fe, quartz + garnet + biotite + staurolite
(Fig. 3A–E).
Mineralization is observed on the surface by the presence of sulfides
as disseminations, box work structure, gossanization, and secondary
veins associated with intense wall rock alteration zones (Fig. 3 F-K).
Yellow to brownish alteration halos, typical box work structures, and
gossan are explicitly observed in the metarhyolite and metasediments
(Fig. 3D). In the core samples, the sulfides viz. chalcopyrite, pyrite,
3
Ore Geology Reviews 134 (2021) 104149
pyrrhotite are found as stringers, blebs, and disseminations parallel to
the S1 schistosity of the host rocks. Their concentrations increase to­
wards the wall rock alteration zones marked by biotitization and
chloritization (Fig. 3F-G). The intimate association of gahnite and garnet
with the rich mineralized zones is ubiquitous in the Betul belt (Fig. 3E).
Borehole data [BH. No-BBH.6 (70 m); MPBBP-8 (83.45 m); MPCJD-1(92
m), BYR-1(50 m)] suggest that the width of the mineralized zones varies
significantly, show pinching and swelling structure, and mainly consist
of sub-parallel lenses with semi-massive disseminated sulfide minerali­
zation (Fig. 3F-G, J-K). Mahakud et al. (2001) noted a distinct vertical
zonation with more zinc-rich upper ore bodies and copper-rich lower ore
bodies within sub-parallel ore bodies. Silicification, biotitization, ser­
icitization, carbonatization, saussuritization, and epidotization are
common wall rock alterations observed in the BB (Fig. 3F–K). At places,
calcite veins intrude rhyolite (3H-I). Cross-cutting and parallel quartz
veins and Zn-bearing oxide phases (Zincite-Franklinite) within the
metasediments are observed (Fig. 3 L), which points towards their hy­
drothermal remobilization due to shearing.
The principal sulfide minerals in BB deposits are sphalerite and py­
rite. Chalcopyrite, galena, and pyrrhotite occur less abundantly in the
belt (Fig. 3). Praveen et al. (2007)) classified the deposits as Zn-Cu and
Zn-Pb-Cu types and related the former to the mafic unit’s presence while
the latter as felsic dominated footwall. The significant sizeable deposits
are namely, Ghisi, Mouriya, in the western segment, Banskhapa, Tarora,
Bhawaratekra, Koparpani, in the central portion and Biskhan, Bhuyari, ,
Jangaldehri, in the eastern segment located across the BB (Fig. 1C, 2 A-
D) (Golani et al., 2006; Praveen et al., 2007, 2020; Raut and Mahakud,
2004; Raza et al., 2020). There are physical differences among the de­
posits concerning the host rocks, alteration assemblages, and metal
content. However, all deposits are identified and inclusively categorized
as a part of the VMS deposits based on a specific field and characteristic
geochemical features (Galley et al., 2007; Lydon, 1984; Franklin, 1993;
Lentz, 2002). Key characteristics of the host rock, alteration, mineral
assemblages, straigraphy and ore geology of the four deposits are
compiled in Tables 2 and 3 and (Fig. 2A–D).
Fig. 1. (A) India map shows the location of different
cratons and position of Betul belt within the CITZ
after Naqvi and Rogers (1987). (B) The regional
geological map of the central region shows macro-
scale structural features and three associated Prote­
rozoic supracrustal belts viz., Mahakoshal, Betul, and
Sausar within the CITZ after Roy and Prasad (2001).
(C) General geological map of Betul belt showing
bimodal volcanic rock’s disposition within basement
gneisses, VHMS deposits, and intrusive mafic/felsic
magmatism (Geological Survey of India compiled
map).
B.P. Mishra et al.
3. Methodology
3.1. Sampling
The present research area was mapped on a scale of 1: 12,500
(Fig. 1C). Representative carbonate and sulfide ore samples were
collected from the outcrops of mineralized veins, drill hole intercepts
from the ore bodies between 120 m and − 20 m reduced level for sulfides
geochemistry and stable isotope studies. Sphalerite- and pyrite-bearing
samples from the different ore types from four deposits (Banskhapa,
Jangaldehri, Biskhan, and Bhuyari) were methodically selected for
petrographic studies. Major and trace elements of the sulfide minerals
were analyzed by electron microprobe (EPMA) followed by LA-ICP-MS
facilities available at the Geological Survey of India.
3.2. Analytical techniques
3.2.1. Electron microprobe analyses
Detailed petrographic studies examined 25 polished thin sections
before the microprobe analysis. The mineralogical and textural varia­
tions were carefully observed to choose the appropriate polished thin
sections for microprobe analysis. The major elements in sulfides
(sphalerite and pyrite) were measured by Electron Microprobe Analyser
(EPMA) (Cameca SX-100) available at NCEGR laboratories, Geological
Survey of India, Bengaluru . The EPMA instrument is armed with five
different wave dispersive spectrometers (WDS). A total of 95 point an­
alyses were obtained, out of which 44 were sphalerite points and 51
pyrite points. The instrument was set under 15 kV accelerating voltage,
one μm beam diameter, and 20 nA beam current for the measurements.
The counting times for peak and background were the 40 s and 20 s,
respectively. The precisions of the analyses were ±0.5% element con­
centrations. The ZAF matrix corrections were carried out using the
CAMECA supplied Peak sight program (Pouchou and Pichoir, 1984).
FeO and Fe2O3 are represented as total iron in the form of FeO.
Descriptive statistics of the major elements are given in Table-3. The
details are given in supplementary file no-1.
3.2.2. In situ LA-ICP-MS analyses
Quantitative trace element compositional data for sulfides was ob­
tained using a Cetac-Teledyne 213 nm (quintupled wavelength) Nd:
YAG laser-ablation system coupled to an Agilent 7700-x –Quadrupole-
Inductively Coupled Plasma Mass Spectrometer (at NCEGR, GSI, Far­
idabad, India). The ICP-MS was run at a plasma capacity of 1350 W. The
study was conducted in pure Helium (He)-atmosphere (550 ml/min)
mixed prior to entering the ICP component with Argon flow (880 ml/
Table 1
The regional tectono-stratigraphy of Betul belt, central India after Chore et al. (2002).
Lithology
Deccan Traps Basaltic lava flows and dolerite dykes
—————————————————————Intrusive contact/Disconformity———————————————————————
Gondwana Conglomerate, sandstone, and shales
Supergroup
—————————————————————Unconformable/Tectonic Contact———————————————————————
Intrusives Basic dykes, pegmatites, quartz veins
Homophanous amphibole-mica granite, Porphyritic granite
——————————————————Intrusive/Tectonic contact————————
Padhar Mafic –Ultra Diorite, gabbro, norite, pyroxenite, hornblendite, websterite, harzburgite, Anorthosite, Diorite,
Mafic Suite talc – serpentinite rock, quartz – epidote Rock
——————————————————Intrusive/Tectonic contact————————
Betul Group Sonaghati Formation Intercalated sequence of quartzite and quartz-mica schist ± granite mineralization
————————————Conformable/Tectonic contact——————————————
Bargaon Formation Meta-sediments (mica schists) metarhyolite and felsic metatuff metabasalt and amphibole
–chlorite schist ± Cu-Pb-Zn mineralization
————————————Conformable/Tectonic contact——————————————
Ranipur Formation Phyllite, banded hematite/magnetite quartzite, BIF granulite, meta-basalt, amphibolites,
carbonaceous phyllites, calcareous quartzite, calcsilicates, marble
Amla Gneiss Basement Gneiss Banded migmatite gneiss, quartzofeldspathic mica schist /gneiss
4
Ore Geology Reviews 134 (2021) 104149
min). The ICP-MS was optimized daily for optimal sensitivity and the
molecular oxide ratio (s) (232Th16O/232Th) and the double ion ratio
(140Ce2+/140Ce+) were maintained at <1.0 per cent.
Laser beam diameter was set at a constant 30–50 µm (for all sulfides
analyzed) with a repetition rate of 10 Hz. The laser energy used is 0.735
milli Joules for pyrite and sphalerite. Each analysis’s total acquisition
time was 140–180 s, with 60 s gas background measurement followed by
60–80 s of sample ablation. Certified Reference Material (CRMs) matrix-
matched standard exclusively for sulfides analysis was carried out using
MASS-1, natural polymetallic Fe-Cu-Zn-S based natural cold-pressed
sulfide pellet (Wilson et al., 2002), USGS manufactured). The quanti­
tative calculations were performed using MASS-1, BCR-2G, and NIST
610-Microanalytical Natural Reference Materials. The internal standard
correction was done with 57 Fe and 66 Zn using EPMA value for Fe-Zn-
sulfides (pyrite and sphalerite). Data were collected using time-
resolved data acquisition (TRA mode), while calculations were per­
formed using the data reduction method described by Longerich et al.
(1996) and Lin et al. (2016); using an in-house-developed excel based
spreadsheet (at LA-ICP-MS facility, NCEGR, GSI, Faridabad). Gas blank
corrections were done while integrating the raw Data-Counts per second
(cps). Trace element and rare earth element concentration of the
following isotopes 51V, 55Mn, 59Co, 60Ni, 65Cu, 71Ga, 72Ge, 75As, 77Se,
111
Cd, 115In, 118Sn, 121Sb, 125Te, 197Au, 205Tl, 208Pb, 209Bi have been
measured.
The multielement limits of detection (LOD) were in the range of
0.001–0.041 ppm (calculated as given by Lin et al. (2016) for most of the
analyses, and a majority of values better than 0.10 ppm. The accuracy of
multi-trace element determinations with matrix-matched standards was
generally found to be better than ±0.005% with a 5 to 25% RSD pre­
cision. Most of the elements displayed a high degree of accuracy ±0.008
to 0.001%, as per Pearce et al. (1997). The details are given in table no4
and supplementary file no-2.
3.2.3. Principal component analysis
The principal component analysis (PCA) was done to interpret the
critical pattern in geochemical data of the Betul belt. Multivariate sta­
tistics, principal component analysis (PCA) are used to bring out rele­
vant patterns in the trace element dataset suite to infer the dominant
trace elements and associated geological processes. The major element
Fe and trace elements such as Mn, Cd, In, Co, Ga, Ge, Ag, and Sn in
sphalerite and Co, Ni, As, Pb, Bi, Se, Mn, and Ti for pyrite were selected
for PCA study. These elements were preferred for the PCA study because
the element suites are susceptible to change their geochemical behavior
in different ore-forming environments (Cook et al., 2009; Frenzel et al.,
2016).
Age
Late Cretaceous
Permo-Carboniferous to Early
Cretaceous
Meso-Proterozoic
Archean to Proterozoic
Archean to Proterozoic
Archean to Proterozoic
Archean
B.P. Mishra et al. Ore Geology Reviews 134 (2021) 104149

Fig. 2. Detailed geological map of the four VHMS deposits of the Betul belt (area marked by two rectangles in Fig. 1C, showing the base metal deposits. (A) detailed
geological map of Jangalderhi showing the mineralization and associated alteration zones after Mishra et al. (Mishra et al., 2009); Kumari and Panda (Kumari and
Panda, 2018). (B) detailed geological map of Biskhan showing the mineralization and associated alteration zones after Hemraj and Nambiar (Hemraj and Nambiar,
2007), Raza and Naidu (Raza and Naidu, 2018). (C) detailed geological map of Bhuyari showing the mineralization and associated alteration zones after Dora and
Praveen (Dora and Praveen, 2007). (D) Large scale geological map of Banskhapa showing the mineralization and associated alteration zones after Mahakud et al.
(2001), Shareef et al. (Shareef et al., 2011).

Before PCA, exploratory data analysis was attained then reconciled.
Except for Sn, Sb, and Bi, the detectable amount of concentration was
measured for each element in sphalerite samples. More than eighty-five
percent of the data points for Sn, Sb, and Bi were measured in samples.
The values for the rest of the data points were below the detection limit.
Hence, they were treated with an imputation method with a constant
value to obtain individual data points (Van den Boogaart and Tolosana-
Delgado, 2013). The data points were subsequently compiled and log-
transformed (Belissont et al., 2014; Frenzel et al., 2016). For all PCA-
related computations, work was accomplished using OriginPro 2016
application packages.
3.2.4. Stable isotope studies
Sulfide ore samples were selected from Banskhapa drill cores for
sulfur isotope study. The uncontaminated metal sulfides (sphalerite,
pyrite, and chalcopyrite) were selected from the core samples using a
binocular microscope. The analytical procedures of sulfur isotope sys­
tematics were followed after De Groot (2009) and Hoefs (2009). The
isotopic analysis was undertaken with Isotope Ratio Mass Spectrometer
(IRMS) (Model: Geo 20-20), the facility available at NCEGR, GSI Ben­
galuru, India. Seven samples were processed for the purpose, and each
sample was analyzed for 550 s. Each sample was measured three times
with the international general references NBS-123 to ensure an unbiased
experiment. Measurements are expressed in the VCDT scale for all
sulfur-bearing samples (Zhang et al., 1989). The δ34S VCDT (‰) value
for NBS 123 is recorded as +17.44‰ (Beaudoin and Taylor, 1994).
Multiple analysis of NBS 123 combined an average of +17.41‰ and a
standard deviation of 0.23‰.
Carbonate veins were obtained from the Jangalderhi and Bhuyari
deposits core samples for the δ 13C and δ 18O isotopic analyses. Stable
isotopic analysis (δ 13C and δ 18O ratios) of calcite was performed in a
stable isotope laboratory at Wadia Institute of Himalayan Geology
(WIHG), Dehradun, India, using a gas source, a continuous flow-isotope
ratio mass spectrometer (CF-IRMS) of Thermo Fisher Scientific, Delta V
plus gas bench II model, using the protocol provided by Paul and
Skrzypek (2007). In order to ensure accuracy and precision, the isotopic
standards ratios were taken from two separate laboratories (WIHG and
IIT Kharagpur) along with the international carbonate standard of the
International Atomic Energy Agency, NBS-18 (carbonatite). The accu­
racy of carbon and oxygen isotope ratio measurements during the car­
bonate process is ±0.10‰ for both δ 13C and δ 18O. The value of δ 13C is
expressed in Vienna PeeDee belemnite (VPDB), and the value of δ 18O is
expressed in Vienna normal mean ocean water (VSMOW).
4. Results
4.1. Petrography of ore samples
Detailed ore petrography was carried out succeeding the SEM-EDS
studies for outcrop and drill core samples. The paragenetic sequence
of sulfide mineralization in the four deposits was subsequently ascer­
tained from the petrographic studies. Each deposit has a different ore
and gangue mineral assemblage (Fig. 4A–K). The whole range of variety
essentially fine to coarse, euhedral to anhedral, coeval, mutual

5
B.P. Mishra et al. Ore Geology Reviews 134 (2021) 104149

Fig. 3. Field and sub-surface features illustrate alteration zone, nature of mineralization, nature of host rocks, and volcano-sedimentary rocks from four VHMS
deposits of the Betul belt. (A) Field photographs showing Ca-Fe-Mg alteration (tremolite and biotite association) with carbonate at Bhuyari, (B-C) Field photographs
showing garnet and chlorite (green color) and staurolite association at Bhuyari, (D) Oxidation patches traversed by carbonate veins at Bhuyari. (E). Field photographs
showing the gahnite-garnet-biotite association at Jangaldehri (F-G) Drill core photograph show fine dissemination and sulfide stringers associated with altered
rhyolite Biskhan and Jangaldehri deposits [BH. No-BBH.6 (64 m); MPCJD-1(92 M), (H-I) Drill core photograph is showing the nature of carbonate veins associated
with rhyolite at Jangaldehri deposit (J). Drill core photograph showing nature of massive sulfides at Biskhan (BBH-6 (70 m) and Banskhapa (BBP-08 (83.45 m; L)
Field photograph showing alteration assemblages of anthophyllite, willemite, and iron oxide at Bhuyari. Abbreviations: Tr tremolite, Chl chlorite, Grt garnet, St
staurolite, Ghn gahnite, Sp sphalerite, Py-pyrite, Ccp-chalcopyrite, Cal-calcite; and Wlm willemite.

boundary, and replacement texture were observed in the sulfide min­
erals. Chalcopyrite disease is a common texture observed within sphal­
erite encompassing exsolved blebs of chalcopyrite (Fig. 4A–C), pointing
towards high Fe content and high-temperature formation of sphalerite
(Govindarao et al., 2018). Within the sphalerite, chalcopyrite’s
annealing texture is also observed at places that further support the
deformation and healing of sphalerite (Fig. 4C). The development of
triple junctions in sphalerite with other sulfides and silicates indicates
recrystallization due to metamorphism (Fig. 4H). Euhedral to subhedral
pyrite (Fig. 4E) is replaced by sphalerite and chalcopyrite. At places, two
generations of sphalerite were noticed (Fig. 4D, F). In general, sphalerite
shows a pitted appearance and creamish yellow color. Inclusions of
sphalerite and chalcopyrite are also seen in the pyrite (Fig. 4F). Frac­
turing and resorption of grain margins filled with chalcopyrite and
sphalerite are typical in pyrite (Fig. 4E & F). Galena is replaced by early
sphalerite, chalcopyrite, and pyrite (Fig. 4H). Calcite occurs as a gangue
mineral in close association with pyrite and chlorite (Fig. 4J–K).
Triangular pits are common in galena (Fig. 4I), and it also occurs as

6
B.P. Mishra et al. Ore Geology Reviews 134 (2021) 104149

Table 2
Compilation of geology, mineralogy, alteration assembles, and ore details of four significant deposits viz; Banskhapa, Jangaldehri, Biskhan, and Bhuyari of the Betul
belt.
Sl. Deposit Alteration Ore Ore details Ore controlling structures Mode of occurrence Host Rocks Alteration Min. References
No type Assemblages

1 Banskhapa chloritization, Zn, 4.37 Mt @ Remobilization along the Massive sphalerite Rhyolite and Qz + Bt + Ms + (Mahakud
21◦ 59′ 28′′ : Mg-Fe-Al Cu Avg. late fracture planes. ore with calc-silicate, Ghn + Ser-Grt et al., 2001;
78◦ 23′ 42′′ alteration 1.81% Zn chalcopyrite, pyrite Qt-mica schist + Chl Shareef et al.,
and 0.32% and pyrrhotite 2011)
Cu
2 Jangaldehri chloritization, Al- Zn, 0.98 Mt @ Mineralization is mainly disseminations, altered Qz + Ser + bt + (Mishra et al.,
21◦ 58′ 40′′ Mg-Fe alteration Pb Avg. Zn controlled by lithology stringers of rhyolite Sil + Chl ± St ± 2009; Kumari
78◦ 26′ 58′′ 1.1% remobilized through sphalerite, pyrite, Amphibolite Ghn + Grt and Panda,
fracture planes and shear chalcopyrite and 2018)
planes. pyrrhotite
3 Biskhan chloritization, Al- Zn 2.15 Mt @ Mineralization is mainly disseminations, fine Altered Qz + Ser + Bt + (Hemraj and
21◦ 56′ 26′′ Mg-Fe alteration Zn-1.14%, controlled by lithology and veinlets, stringers rhyolite, Qt- Sil + Chl ± Star Nambiar,
78◦ 28′ 06.“ Avg. width remobilized through and specks of mica schist + Ghn 2007; Raza
22.9 m fracture planes and shear sphalerite and pyrite and Naidu,
planes 2018)
4 Bhuyari Silicification Zn, 1.56 Mt @ Impersistent, multiple, sub- disseminations and Alerted Qz + Ser + Bt- (Golani et al.,
21◦ 59′ 39.“ biotitization, Pb, Avg. Zn parallel, shallow to veins and bands of rhyolite, Calc- Grt + Pl + Ghn 2006).
78◦ 35′ 41′′ chloritization, Cu 2.17% Pb moderately dipping, massive to semi- silicates + St + Chl + Tr
Mg-Fe alteration − 0.52%, lensoidal, and sheet-like massive sulfides + Tlc + Ant
Cu − bodies and sub-parallel to
0.14% the stratigraphy as well as
foliation.

Deposits from sl no 1 to 4 are from west to east in the Betul belt; Abbreviation: Qz-quartz, Bt-biotite, Ms-muscovite, Ghn-gahnite, Grt-garnet, Chl-chlorite, St-staurolite,
Ser- Sericite, Sil – sillimanite, Pl – plagioclase, Tr – tremolite, Tlc – talc; Ant -(anthophyllite).

Table 3
Descriptive statistics of concentrations of major elements Zn, Fe, and S in bulk sphalerite (n = 44) from Banskhapa, Jangaldehri, Biskhan, and Bhuyari, in Betul belt,
obtained from electron microprobe analysis.
Deposits Banskhapa Jangaldehri Bhuyari Combined

Mineral Name Sphalerite* Sphalerite*

Sample No BP/DC-4, BP/DC-2, BP/DC-6 JD/DC-7 BY/DC-1 –
Boreholes and depth BP-8/55.9; BP-17/145.2 JD-1/90 m BH.3-B/61.3 m –
Coordinates 21◦ 56′ 26′′ ::78◦ 28′ 06′′ and 21◦ 58′ 40′′ :: 78◦ 26′ 58′′ 21◦ 59′ 39′′ 78◦ 35′ 41 –
21◦ 59′ 45.5′′ ::78◦ 24′ 0.5′′
No of analyses done (n = 44) n = 29 n=9 n=6 n = 44
Statistical Parameters Zn (wt%) Fe(wt%) S(wt%) Zn (wt%) Fe(wt%) S(wt%) Zn (wt%) Fe(wt%) S(wt%) Zn (wt%) Fe(wt%) S(wt%)
Mean 59.67 6.41 32.80 57.16 8.01 35.56 55.76 10.28 34.00 58.62 7.27 33.53
Standard Error 0.29 0.20 0.21 0.17 0.05 0.37 0.37 0.19 0.57 0.30 0.24 0.24
Median 60.03 6.53 32.64 57.15 7.97 36.22 55.93 10.18 34.22 58.79 6.77 33.13
Mode N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A
Standard Deviation 1.54 1.06 1.11 0.50 0.14 1.12 0.90 0.48 1.41 2 1.62 1.59
Sample Variance 2.39 1.13 1.23 0.25 0.02 1.25 0.81 0.23 1.98 4.02 2.64 2.52
Kurtosis 0.54 0.89 1.71 − 0.01 1.20 − 1.43 0.01 1.60 1.19 − 1.05 − 0.12 − 0.60
Skewness − 0.83 0.31 0.66 − 0.42 1.15 − 0.89 0.06 1.12 − 0.72 − 0.15 0.51 0.45
Range 6.55 4.62 5.51 1.62 0.45 2.70 2.57 1.37 4.16 7.59 6.56 6.29
Minimum 55.57 4.55 30.18 56.30 7.85 33.77 54.53 9.74 31.65 54.53 4.55 30.18
Maximum 62.12 9.17 35.69 57.91 8.30 36.47 57.10 11.11 35.81 62.12 11.11 36.47
Sum 1730.31 185.95 951.23 514.44 72.08 320.05 334.57 61.65 203.99 2579.32 319.68 1475.26
Count 29 29 29 9 9 9 6 6 6
Total 44 44 44

*N/A: Not applicable, which signifies the mathematical operation does not apply to the specific parameter.* combined analysis from Banskhapa, Jangaldehri, and
Bhuyari deposit, Betul Belt.

triangular inclusions within the sphalerite in places (Fig. 4I). Secondary sulfide minerals are formed due to oxidation along the grain
Based on field examination (Fig. 3A–L), ore-gangue mineral associ­ margins of early sulfides. Malachite and limonite are two secondary
ations, and crosscutting mutual relationships from petrographic studies minerals identified in these deposits.
combined with published textural interpretations (Ghosh and Praveen,
2008; Shareef et al., 2011; Raza et al., 2020; Praveen et al., 2020) , the
4.2. Sphalerite elemental composition
entire mineralization sequence for the four deposits are classified into
four distinct stages. a) Stage-I; formation of sphalerite, chalcopyrite,
The EPMA measurements of sphalerite in the Betul belt shows mean
pyrrhotite, b) Stage-II; formation of pyrite, and sphalerite, c) Stage-III;
major element concentrations of Zn, Fe, and S as 58.62 wt%, 7.27 wt%,
Sphalerite, chalcopyrite, and galena; d) Stage-IV; formation of galena
and 33.53 wt%, respectively (n = 44). The maximum, minimum, mean,
during cooling of hydrothermal solution. Chalcopyrite disease is pref­
and corresponding standard deviation of the major elements of sphal­
erentially found in Stage-I sphalerite, while stage- II minerals show
erite, along with other statistical parameters appraised using electron
dominant mutual boundary texture with sphalerite (Fig. 4D). Evidence
microprobe analysis, are summarized in Table 3 and supplementary file
of metamorphism and deformation is recognized in Stage-I sphalerite.
no-1. The maximum and minimum value of Zn acquired in the research

7
B.P. Mishra et al. Ore Geology Reviews 134 (2021) 104149

Fig. 4. Transmitted and reflected light photomicrographs and backscattered images showing different relationships of ore samples. (A-C) Fine chalcopyrite blebs
(chalcopyrite disease, dusting) within sphalerite (Sp-I), associated with galena and pyrite (D) BSE image showing recrystallized sphalerite with pyrite and LA-pits. (E)
Partly fragmented pyrite cube with LA- pits. (F) remobilized ductile galena and chalcopyrite along with partially recrystallized pyrite in the sphalerite matrix, (G) BSE
image showing partially recrystallized pyrite grains with chalcopyrite inclusion. (H) remobilized ductile galena and chalcopyrite showing triple junction in the
sphalerite matrix. (I) a large patch of recrystallized sphalerite (Sp-II) with sub-rounded galena inclusions with la-pits. (J-K). Photomicrograph showing large calcite
grains in close association with chlorite and pyrite under transmitted light. Abbreviations: Py -pyrite, Ccp- chalcopyrite, Cal-calcite, Chl-chlorite, Sp sphalerite, Gn
galena abbreviated after Whitney and Evans (2010).

is 62.12 wt% (Banskhapa deposit) and 54.53 wt% (Bhuyari deposit), and
Jangaldehri shows 57.91 wt% of Zn. Fe concentration in sphalerite
varies from 4.55 wt% (Banskhapa) to 11.11 wt% (Bhuyari) with a mean
and standard deviation of 7.27 and 1.62 wt%, respectively. Ranges in
concentration for major elements are presented in box plots (Fig. 5).
Trace element content was measured with in situ LA-ICP-MS,
expressed in parts per million (ppm), and shown in Table 4 and Fig. 4
D, I. The trace element concentration ranges are presented in box plots
(Fig. 5). The samples with chalcopyrite disease have purposefully been
left out from LA-ICP-MS spot analysis after thorough microscopic ob­
servations. Nonetheless, at least in a few samples, there may be profound
inhomogeneity due to the presence of sub-microscopic spatial variability
of these features. The inhomogeneity in a particular element can also be
inferred if the standard deviation of the same element’s concentrations
is more than its mean value. A few elements, notably Pb, Co, Cu, and Bi,
have higher variation than their corresponding mean concentration
values. On the other hand, Cd, In, and Sn show comparatively lower
mean values. Their occupancy in bulk sphalerite specimens as micro-
inclusion is not well documented.
Sphalerite shows significant variations in concentrations, differences
in trace element patterns among the four deposits, shown in box and
whisker plots. Sphalerite is slightly enriched in Mn, moderately In, and
characterized by low Ga, Co, Ge, Ag, Bi, and Pb. Concentrations of some
informative elements are similar to the global VMS sphalerite data
(Fig. 6A–I) in Frenzel et al. (2016).
4.3. Pyrite elemental composition
The EPMA and LA-ICP-MS measurements of pyrites display variable
results (Fig. 4E), given in Tables 5, 6, and details are given in supple­
mentary file no-2. Pyrites show a restricted concentration range of major
elements. The average Fe and S values are 46.43 wt% and 52.43 wt% in
Banskhapa; 46.19 wt% and 53.45 wt% in Jangaldehri; 46.69 wt% and
52.06 wt% in Bhuyari.
Pyrite trace element data show significant variations in Co, Ni, Se,
Te, Bi, and As, presented in the Box and whisker plot (Fig. 7A-E). The
statistical parameters of the trace elements in pyrite are given in Table 5.
Pyrites from the four deposits plotted in the submarine hydrothermal
field of Ni vs. Co discrimination plot, except few analyses (Fig. 8A)
(Bajwah et al., 1987; Xu, 1998) and showed high Co and low Ni con­
centrations (Fig. 7A, B). Moreover, it supports the submarine hydro­
thermal affinity and unrelated to SEDEX, copper porphyry, or skarn
(Fig. 8A–E). The binary plot of As vs. Se/Ti and As vs. Cu reveals high
and low temperature and differentiates orogenic and VMS type (Fig. 8 B-
D). Though the enrichment of gold in pyrite samples is not clearly un­
derstood, gold-rich VMS deposits are commonly associated with tran­
sitional to calc-alkaline felsic volcanic rocks (Langevin et al., 2011).

8
B.P. Mishra et al. Ore Geology Reviews 134 (2021) 104149

Fig. 5. (A) Box plots showing the variations of all important trace elements (EPAM (n = 44, and LA-ICPMS, n = 26) in sphalerites from the Betul Belt. (B-E) Box plots
showing the variations of Fe, In, Cd, and Mn in Banskhapa, Jangaldehri, Biskhan and Bhuyari deposits in Betul belt (deposits are from left to right); Fe concentrations
are taken from EPMA, while In, Cd and Mn are obtained from LA-ICP-MS.

9
 B.P. Mishra et al.
Table 4
Elemental composition of sphalerite (n = 26) determined with LA-ICP-MS and the ore-forming temperature of the four deposit of the Betul belt, calculated by the GGIMFis geothermometer of Frenzel et al. (2016) and by
Kullerud (1953) (Fe concentrations are obtained from EPMA, whereas Mn and Cd concentrations are taken from the LA-ICP-MS dataset for corresponding samples).
Sl. Deposit Name Sample no and Mineral Name Thermometry
No. Coordinates
No Analyses performed Sphalerite: LA-ICP MS (ppm) Frenzel et al., Kullerud, 1953 Temperature
2016 (◦ C)
Temperature
(◦ C)

Analysis Zn (wt Fe (wt Pb Mn Co Cu Ga Ge Ag Cd In Sn Bi PC1 Tmin Tmax Fe Mn Cd Temp

No %) %) mol% mol% mol (◦ C)
%

n ¼ 26 LOD 0.02 0.05 0.01 0.029 0.001 0.037 0.001 0.005 0.001 0.041 0.005
1 Banskhapa n = 5 BP/DC-4 BA/1 61.31 5.12 0.08 1920.13 0.01 39.49 0.46 0.15 0.37 1569.36 26.6 0.9 0.07 − 3.06 362 386 7.78 0.46 0.09 319
2 ————————————————Jangaldehri 21◦ 56′ BA/2 62.12 4.72 0.33 1752.37 0.01 196.9 0.48 0.23 0.31 1524.76 24.72 1.16 0.32 − 2.9 354 377 7.82 0.42 0.08 319
3 n = 10 26′′ :78◦ 28′ 06′′ BA/3 60.9 4.73 0.27 1716.15 0.23 36.64 0.42 0.04 0.52 1524.9 26.5 0.41 0.24 − 3.32 374 402 8 0.49 0.09 331
4 BA/4 60.75 4.55 1.21 1636.05 0.02 428.26 0.44 0.21 0.81 1531.77 29.16 0.57 1.21 − 2.94 356 379 7.77 1.54 0.1 319
5 BA/5 60.24 4.65 0.09 1643.49 0.02 53.85 0.41 0.09 0.38 1518.24 26.87 0.52 0.1 − 3.12 365 390 9.69 1.43 0.1 380
6 JD/DC-1 JA/1 57.914 7.854 1.02 643.67 1.65 40.42 0.08 0.58 1.25 378.19 7.65 1.23 0.01 − 2.97 357 381 15.85 1.45 0.11 543
7 21◦ 58′ 40′′ : 78◦ JA/2 57.116 7.91 0.74 2171.4 19.32 30.65 0.74 0.49 1.14 1132.4 26.22 0.02 0.1 − 2.91 354 377 15.48 1.4 0.12 536
8 26′ 58′′ JA/3 57.245 7.972 0.97 2201.82 20.37 79.35 0.76 1.82 1.75 1216.68 32.42 0.61 2.14 − 2.62 341 359 12.33 0.36 0.1 522
9 JA/4 57.455 8.007 0.71 1736.65 11.56 29.13 0.12 2.33 1.64 1157.07 22.32 2.51 0.26 2.88 353 375 12.29 0.29 0.09 527
10

−
10 JA/5 57.153 8.094 2.69 1496.64 14.89 389.18 0.12 1.32 1.74 1039.76 23.87 1.2 2.07 − 2.98 358 381 12.15 0.25 0.08 451
11 JA/6 57.099 7.945 0.26 1695.77 15.33 23.59 0.27 0.3 0.61 1105.14 26.88 0.84 0.15 − 3.16 366. 392 11.85 0.28 0.09 453
12 JA/7 56.535 7.886 0.82 1555.52 19.62 30.1 0.16 0.47 1.14 801.35 18.16 0.86 0.42 − 3.13 365 390 12.45 0.26 0.06 456
13 JA/8 57.621 8.302 0.59 1872.8 16.1 42.84 0.29 0.39 0.8 1002.5 20.87 0.96 0.33 − 3.09 363 388 12.02 0.31 0.08 450
14 JA/9 56.299 8.113 8.69 1629.06 13.71 263.91 0.19 2.13 2.37 835.76 22.64 0.98 11.99 − 2.79 349 370 12.83 0.27 0.07 457
15 JA/10 54.50 7.95 95.56 1448.7 13.9 28.08 0.43 1.25 1.13 958.85 19.63 0.87 2.81 − 2.68 344 363 12.78 0.24 0.08 510
16 Biskhan n = 5 BK/DC BI/1 55.57** 5.62** 1.61 2836.87 0.06 80.27 0.44 0.19 0.43 1163.42 100.39 0.21 2.18 − 3.28 372 400 11.29 0.49 0.1 423
17 188 BI/2 55.77** 5.59** 0.09 2902.27 0.07 74.19 0.69 0.1 0.4 1168.98 99.58 0.14 0.04 − 3.32 374 402 10.94 0.28 0.1 413
18 21 56 26 : 78 BI/3
◦ ′ ′′ ◦
56.73** 5.47** 0.31 2727.48 0.09 67.59 0.52 0.3 0.31 1109.11 97.55 0.15 0.03 − 3.12 365 390 10.66 0.27 0.09 408
19 28′ 06.“ BI/4 57.51** 5.16** 0.02 2625.67 0.06 63.97 0.49 0.25 0.28 1070.09 94.88 0.02 0.01 − 3.14 365 391 10.33 1.58 0.09 398
20 BI/5 57.64** 5.66** 0.12 2866.63 0.07 69.18 0.52 0.19 0.51 1179.31 98.39 0.07 0.17 − 3.24 370 398 10.89 1.48 0.1 411
21 Bhuyari n = 6 BY/DC-1 BH/1 57.1 11.11 0.61 9954.13 0.17 138.78 0.81 0.44 2.23 1213.89 5.37 0.29 0.01 − 3.14 366 392 12.17 0.51 0.13 452
22 21◦ 59′ 39′′ 78◦ BH/2 56.02 10.14 2259.86 8899.97 0.09 2431.39 0.94 0.85 3.34 1082.17 4.75 0.2 0.02 − 2.9 354 376 12.02 0.34 0.13 450
23 35′ 41 BH/3 56.07 10.47 520.21 8828.89 0.02 884.73 0.56 0.42 1.63 1113.17 5.21 0.12 0.01 − 3.19 368 394 15.82 0.31 0.13 543
24 BH/4 55.01 9.97 11.25 8204.55 0.3 1176.06 0.76 0.99 1.31 1187.18 5.34 0.03 0.03 − 2.9 354 376 16.45 0.29 0.13 556
25 BH/5 55.84 9.74 2.07 8246.71 0.26 135.79 0.64 0.85 0.61 1036.36 4.96 0.05 0.08 − 2.96 357 380 16.3 0.06 0.39 550
26 BH/6 54.53 10.22 1.22 8652.54 0.35 134.1 1 0.49 0.7 1172.58 5.93 0.11 0.01 − 3.03 360 384 16.02 0.05 0.37 548

Ore Geology Reviews 134 (2021) 104149

Total 26 Average
Min 55 5 0.02 644 0.01 24 0.08 0.04 0.28 378 5 0.02 0.01 Min 342 360 319
Avg 57 7 112 3533 6 268 0.49 0.7 1.0 1146 34 0.58 0.95 Avg 361 385 451
Max 62 11 2260 9954 20 2431 1 2 3 1569 100 3 12 Max 374 403 556

Major elements Zn and Fe reported in wt%. **-Fe and Zn values of Raza et al. (2020) used as internal standard for LA-ICPMS (present study). All trace elements concentrations reported in part per million (ppm).*Deposits
names- BK- Biskhan: BP: Banskhapa: BY-Bhuyari; JD- Jangeldehri, *Avg. –Average, DC-Drill core samples, LOD: Limit of detection.
B.P. Mishra et al. Ore Geology Reviews 134 (2021) 104149

Fig. 6. (A-I) Boxplots of the log-transformed concentration of major and trace elements with different deposit types compiled from Frenzel et al. (2016) and Ye et al.
(2011) (MVT, HTMR, SHMS, SEDEX) and comparison with the concentration obtained from Banskhapa, Jangaldehri, Biskhan, and Bhuyari deposits sphalerite in the
Betul belt. The values show a typical range for individual deposit types with a small degree of overlap in between. Fe concentrations are obtained from EPMA and
expressed in weight percentage (wt%).

Table 5
Descriptive statistics of concentrations of major elements Fe, and S in bulk pyrite (n = 51) from Banskhapa, Jangaldehri, and Bhuyari, in Betul belt, obtained from
electron microprobe analysis.
Deposits Banskhapa Jangaldehri Bhuyari Combined

Mineral Name Pyrite Pyrite

Sample No BP/DC-6 JD/DC-7 BY/DC-2 –
Boreholes and depth BP-8/55.9; BP-17/145.2 JD-1/9s m BH.3-B/61.3 m –
Coordinates 21◦ 56′ 26′′ : 78◦ 28′ 06′′ 21◦ 59′ 45.5′′ : 78◦ 24′ 0.5′′ 21◦ 58′ 40′′ : 78◦ 26′ 58′′ 21◦ 59′ 39′′ 78◦ 35′ 41 –
analysis done (n = 51) n ¼ 33 n¼7 n ¼ 11 n ¼ 51
Statistical Parameters Fe(wt%) S(wt%) Fe(wt%) S(wt%) Fe(wt%) S(wt%) Fe (wt%) S (wt%)
Mean 46.43 52.43 46.19 53.45 46.69 52.06 46.45 52.49
Standard Error 0.07 0.09 0.13 0.44 0.17 0.12 0.06 0.10
Median 46.37 52.40 46.23 53.65 46.63 52.07 46.42 52.39
Mode 46.23 53.07 N/A N/A N/A N/A 46.23 53.07
Standard Deviation 0.40 0.53 0.36 1.17 0.56 0.40 0.45 0.74
Sample Variance 0.16 0.28 0.13 1.37 0.32 0.16 0.21 0.55
Kurtosis 1.15 − 0.83 − 0.15 − 2.12 0.54 − 1.52 0.10 1.89
Skewness 0.70 − 0.09 0.38 − 0.18 − 0.71 − 0.11 0.40 1.21
Range 1.84 1.73 1.01 2.87 1.84 1.07 1.84 3.30
Minimum 45.51 51.52 45.77 51.96 45.51 51.52 45.51 51.52
Maximum 47.35 53.25 46.78 54.82 47.35 52.59 47.35 54.82
Sum 1531.87 1730.27 323.32 374.15 513.61 572.69 2368.80 2677.11
Count 33 33 7 7 11 11
Total 51 51

4.4. Thermometry in hydrothermal pyrite (Auclair et al., 1987; Huston et al., 1995; Mas­
lennikov et al., 2009; Revan et al., 2014). LA-ICP-MS analysis of pyrite
4.4.1. Pyrite thermometry samples (n = 41) of all four deposits shows the variable content of Se and
Selenium (Se) is a temperature-sensitive trace element often studied Te (Table 6), shown in box and whisker plot (Fig. 7A, E). Te

11
 B.P. Mishra et al. Ore Geology Reviews 134 (2021) 104149

concentration is deficient (0.1–0.8, except one value 2.3 ppm); however,

Se shows good variation among all four deposits. Jangaldehri shows the
Temp highest concentration of Se ranges from 64 to 721 ppm and a mean of
Pyrite Thermometry

(◦ C)

324

225

484
423 ppm; Bhuyari shows extremely low values varying from 0.1 to 0.4

–
ppm, with an average of 0.2 ppm. Banskhapa displays moderate Se
varies from 33 to 55 with an average of 39 ppm, and Biskhan shows a
Average

39.69

5.86

0.26
302.16
low concentration of Se varies from 3.7 to 7.9 ppm with an average of
Se

5.8 ppm (Fig. 7E).

Based on Se content in pyrite, the ore-forming temperature (T) from
26.32
16.01
13.96
21.26

18.61
20.40
23.25
7.17

3.90
6.00
5.03
3.16

1.96
1.92
1.79
0.28
all four Betul belt deposits has been estimated using the equation pro­
Co/
Ni
Trace element concentrations of pyrite (n = 41) obtained from LA-ICP-MS analysis for the four different VMS deposits along with pyrite thermometry from the Betul Belt, central India.

vided by Keith et al. (2018).

Se pyrite = 5*1013 *T− 4.83 (1)
4.71

5.75

6.81

6.61
5.20

3.64
132.33
437.56

165.89
10.30
10.40
36.37

71.18

24.49
49.78

21.91
0.01

Based on the geothermometers of Keith et al. (2018); Jangalderhi

Mn

show temperature between 177 ◦ C to 292 ◦ C and an average of 225 ◦ C;

Banskhapa from 301 ◦ C to 334 ◦ C; and Biskhan ranges from 452 ◦ C to
6.43

5.86
1.38
7.90
3.77

0.26
0.13
0.47
0.15
302.16
193.91
423.63
39.69

55.90
33.94

64.88
0.05

527 ◦ C with an average of 484 ◦ C. These temperature ranges also plotted

Se

against Se values shows a strong negative correlation (Fig. 8 F). They are
also compared with the Porphyry, Carlin, Epithermal, and Orogenic
7.87
9.25

0.70

3.53
5.28

0.01

0.16
0.25
0.68
0.01
24.99

11.04
14.34
44.39

15.33
0.01

0.3

deposit’s thermal regime, field adopted after Keith et al. (2018) (Fig. 8F,
Bi

G).
0.005

41.13
30.18
90.74

10.88

10.63
15.82
45.50
2.53
3.16
9.84
0.01

3.26

2.19
3.77

0.01

0.05
Pb

4.4.2. Sphalerite geothermometry

Various sphalerite geothermometers have been devised in the liter­
19.72
0.02
0.01
0.04
0.02

0.02
0.01
0.05
0.02

9.55
6.58

0.02

0.10
0.13
0.30
0.02
0.02

ature over time by different authors. Each geothermometer devised has a

Au

distinct degree of potential to reflect accurate results and has also been
associated with particular inadequacies. The two key geothermometers
0.01

0.88
0.76
2.39
0.07

0.26
0.21
0.52
0.03

0.07
0.05
0.16
0.01

0.03
0.04
0.10
0.02

Abbreviation: BP-Banskhapa-Pipariya; JD: Jangaldehri; BK: Banskhapa, BY-Bhuyari, DC-Drill core samples, LOD: Limit of detection.
Te

applied for the sphalerite of the BB are FeS-ZnS geothermometry pro­

posed by Kullerud (1953) and the latest GGIMFis geothermometry
0.003

0.004

0.003

proposed by Frenzel et al. (2016). Kullerud (1953) studied the phase

0.06
0.07
0.22

0.43
0.32
0.84

0.12
0.16
0.38
0.03

0.44
0.66
1.71
0.04
Sb

equilibrium in the system FeS-ZnS and confirmed that the solubility of

FeS in sphalerite increases with an increase in fluid temperature. The
0.012

0.15
0.08
0.24
0.01

1.85
2.33
7.55
0.04

0.04
0.03
0.08
0.02

0.04
0.04
0.12
0.01

ore-formation temperatures of sphalerite have been inferred using Kul­

Sn

lerud (1953) phase diagram from the same samples used for the LA-ICP-
MS study. Inclusion-free grains were selected for this purpose (Fig. 9).
0.041

0.20
0.24
0.72
0.04

3.00
2.91
9.07
0.34

0.16
0.18
0.45
0.01

0.22
0.36
1.00
0.00
Ag

The total FeS mol% obtained from the EPMA study is given in Table 3
with the corresponding temperature.
136.16

288.56

111.43
177.39
454.83

119.70
173.96
552.97
73.17

10.93
5.25

2.52
3.68

0.15

1.29

1.72

Frenzel et al. (2016) verified that ore-fluid temperature controls Ga,

0.001
As

Ge, In, Mn, and Fe concentrations within the sphalerite structure. Then,
the elements were validated with relevant thermometric data using
117.53
265.48
868.75
2.75
2.25
5.52
0.31

0.80

2.22
1.08
4.69
1.15

1.82
1.98
5.56
0.23

statistical measures, mainly PCA. The results obtained from the PCA
0.01
Cu

shows a strong correlation between the primary principal component

(PC1)
LA-ICPMS (values in ppm)

0.029

12.57
1.40
1.78
6.17
0.21

4.39
4.09
9.98
0.22

0.25
0.11
0.41
0.06

4.03
3.58

1.06

The relationship is as follows,

Ni

( )
C0.22 .C0.22
PC1 = ln 0.37Ga 0.20Ge 0.11 (2)
232.12
36.74
28.56
86.10

81.73
83.40

22.55
4.38

1.58

0.97
0.65
2.05
0.20

7.88
6.88

0.30
0.01

CFe .CMn .CIn

Co

where Ga, Ge, Mn, and In concentrations in parts per million, Fe con­
0.01

0.01
0.01
0.02
0.01

0.07
0.12
0.39
0.01

0.02
0.01
0.04
0.01

0.02
0.02
0.06
0.00

centrations are in weight percent (Table 3). The relation between PC1
V

and temperature of homogenization, T, is expressed asT(◦ C) = -(54.4 ±

7.3) * PC1 + (208 ± 10) (3)
21◦ 56′ 26′′ : 78◦ 28′ 06.“

21◦ 59′ 39.“ 78◦ 35′ 41′′

21◦ 58′ 40′′ : 78◦ 26′ 58′′

This is known as the GGIMFis geothermometer. The maximum,

minimum, and average values of both ore-formation temperatures are
Sample no and

presented in Table 4 and Fig. 9. The GGIMFis geothermometer and

coordinates

Kullerud (1953) yielded ore-forming temperature of sphalerite that

21◦ 59′ 42′′
78◦ 23′ 52′′

BK/DC-8

BY/DC-2
BP/DC-6

JD/DC-7

range from 374.37 ◦ C to 402.84 ◦ C and 319 ◦ C to 556 ◦ C, respectively

Pyrite

(Fig. 9). FeS-ZnS geothermometer shows the lower temperature for

Banskhapa deposit (319 ◦ C to 380 ◦ C), moderate temperature for Bis­
khan (398 ◦ C to 423 ◦ C), higher temperature for Bhuyari (452 ◦ C to
Total analyses n =

556 ◦ C) and Jangalderhi deposits (450 ◦ C to 543 ◦ C) (Table 4, Fig. 9).

Deposits name

Jangaldehri
Banskhapa

Biskhan

Bhuyari

4.5. Principal component analysis of elements

Mean

Mean

Mean

Mean
LOD

Max

Max

Max

Max
Min

Min

Min

Min
SD

SD

SD

SD
41

Multivariate data analysis is a statistical method in which multidi­

Table 6

mensional variables are concisely represented by emphasizing variables

No
Sl

relationships, especially in ore minerals (Yuan et al., 2018). Principal

12
B.P. Mishra et al. Ore Geology Reviews 134 (2021) 104149

Fig. 7. Trace element content (LA-ICPMS) in pyrite (n = 41) from four deposits (Banskhapa, Jangaldehri, Biskhan, and Bhuyari) in the Betul Belt. (A) Box plots
showing the variations of all important trace elements in pyrites. (B-E) Box plots showing the comparison of Co, Ni, As, Se Te, and Au concentrations in pyrite among
four deposits in the Betul belt.

13
B.P. Mishra et al. Ore Geology Reviews 134 (2021) 104149

Fig. 8. (A) Pyrite geochemistry plots of Co vs. Ni showing magmatic-hydrothermal signature after Bajwah et al. (1987) and distinctly different from Porphyry,
Epithermal, orogenic and Carlin-type, fields were obtained after Keith et al. (2018). Pyrite field for submarine hydrothermal vent taken from Keith et al. (2016),
Porphyry Copper from Deditius et al. (2014), Zhang et al. (2014), SEDEX from Mukherjee and Large (2017), VMS deposits from Revan et al. (2014), Dehnavi et al.
(2018) and Sedimentary pyrite from Large et al. (2014). (B) Se/Ti - As showing high- and low-temperature division after Maslennikov et al. (2009); C-D) Cu-As and
Au-Ag discriminatory scatter plot from Large et al. (2009), Belousov et al. (2016). “n” signifies the number of data points. (E) Se- Te shows the scattered nature of
Betul belt pyrites (F) Se concentrations in pyrite versus the ore deposition temperature from Betul, showing a strong negative correlation. (G) Average Se con­
centrations in pyrite vs. the ore deposition temperature from orogenic Au, Carlin-type, high-sulphidation (HS) epithermal, low-sulphidation (LS) epithermal, alkaline
rock-hosted epithermal and porphyry Cu systems. Field .
adopted from Keith et al. (2018)

component analysis, a standard tool, is used in the present study for the
suites of trace elements variables of metal sulfides (sphalerite and py­
rite) to reduce to principal components (PCs) with minimal data loss
(Belissont et al., 2014; Frenzel et al., 2016; Winderbaum et al., 2012;
Yuan et al., 2018). The results obtained from the Betul belt, after the
PCA of the LA-ICP-MS dataset of sphalerite (n = 26) and pyrite (n = 41),
are presented in Figs. 10 and 11. The trace elements such as Fe, Mn, Cd,
In, Co, Ga, Ge, Ag, and Sn in sphalerite as well as Co, Ni, As, Pb, Bi, Se,
Mn, and Ti for pyrite were selected for PCA study in connection with
deposit characterization of all four deposits in the Betul belt (Abraitis
et al., 2004; Belissont et al., 2014; Cook et al., 2009; Pasava et al., 2013).
Two PCs are selected to represent the variables and their charac­
terized correlation coefficients, and two PCs, F1 and F2, are plotted in a
2-D graph. The two PCs, F1 and F2, explained the total elemental
dataset’s cumulative variability for sphalerite and pyrite. For sphalerite,
the horizontal axis is the first principal component; F1 includes Fe, Co,
Ge, Ag, Cd, and In accounts for 41.59% variability, characterized by two
sub-sets. The first set consists of Fe, Co, Ge, and Ag, whereas the second
set is Cd and In (Fig. 10 C-E). The second principal component, F2,
represents 31.69% variability in the vertical axis, includes Mn, Ga, and
Sn. The variables (elements) are represented by the red vector line
within the correlation circle (Fig. 10 C). The interpretations are based on
the angle between the variable vectors or between variables and PCA
dimensions, i.e., F1 and F2. The acute angle reflects a positive correla­
tion of the variables, whereas the obtuse angle a negative correlation.
Moreover, the right-angle implies that the variables are uncorrelated.
The closeness between the vectors indicates the strength of the
correlation.
In the same fashion, element concentrations in pyrite (Co, Ni, As, Pb,
Bi, Se, Mn, and Ti) were studied and shown in Fig. 11 A-E. The first
principal component, F1, comprises Co, As, Pb, Bi, and Se, representing
36.61% data variability, while the second principal component F2
comprises Ni, Mn, and Ti, representing 22.44% data variability.
4.6. Stable isotope analyses
Seven sulfur isotopic measurements were performed on sphalerite (n
= 3), chalcopyrite (n = 2), and pyrite (n = 2) from Banskhapa drill core
samples (B.H-MPBBP-8 (83.45 m); Sample no-BP/DC-1 to 7). The
measured δ34S values in metal sulfides (sphalerite, chalcopyrite, and

14
B.P. Mishra et al.
Fig. 9. Figure showing the sphalerite and pyrite’s geochemical characteristics based on petrography, major and trace element geochemistry, and thermometry
studies using EPMA and LA-ICPMS analyses, a mirror bar chart showing the temperature range of sphalerite formation in the four deposits (Biskhan, Banskhapa,
Bhuyari, and Jangaldehri) of the Betul belt as per the geothermometers of Kullerud (1953) and Frenzel et al. (2016). For the GGIMFis geothermometer, Tmax values
have been taken into account. Pyrite thermometry is also shown based on Se content using the equation of Keith et al. (2018).
pyrite) indicate variability in δ34S and show a small range of + 6.58 to +
8.61‰ (n = 7) (Fig. 12). Sphalerite show a narrow δ34S values ranging
from + 7.27 to + 7.89‰ (n = 3), pyrite δ34S values exhibit + 8.36 to +
8.61‰ (n = 2), chalcopyrite δ34S values display + 6.58 to + 6.72‰ (n =
2). The essence of analytical data is listed in Table 7 and compared with
other deposits and illustrated in Fig. 12.
Carbonate veins are associated with the massive to semi-massive
mineralized zones. The veins cross-cut the mineralized zones and par­
allel to the alteration zones and, at places, subparallel to host foliation.
Six carbon isotopic measurements were performed on calcite (n = 4)
from drill core samples (BY/DC-1 to 3) and dolomite (BY/BR:4–5; n = 2)
at Bhuyari and one sample from Jangaldehri (JD/DC-7, n = 1). The δ13C
(PDB) ranges from − 6.00 to − 13.45‰ while δ18O (PDB) ranges from
− 9.96‰ to –22.83‰. Majority of δ18O (PDB) values (− 14 to − 8‰) plot
near those reported for the marine carbonates of Paleoproterozoic age.
One sample has δ18O (PDB) (–22.23) and δ13C (PDB) (− 6‰) values
similar to primary carbonates (Fig. 13). All these indicate the involve­
ment of marine and hydrothermal fluids in the formation of these calcite
veins. The details of isotope data are listed in Table 6 and compared with
other deposits and illustrated in Fig. 13.
5. Discussion
5.1. Significance of sphalerite geochemistry in deposit characterization
Mainly, host lithologies, ore-fluid chemistry, and prevailing physi­
cochemical conditions control the elemental makeup of metal sulfides
precipitated from the fluid. Trace elements of sphalerite deliver infor­
mation about ore-forming processes, ore-forming environments, and
deposit characterization (Abraitis et al., 2004; Belissont et al., 2014;
Cook et al., 2009; Pasava et al., 2013; Ye et al., 2011; Lentz, 2002).
From a regional perspective viewpoint, Betul sphalerite is charac­
terized by high Fe, In, and Mn, resembling massive sulfides (syngenetic)
and magmatic-hydrothermal type deposits (In > 50 ppm and Mn >
15
Ore Geology Reviews 134 (2021) 104149
1000 ppm) (Frenzel et al., 2016). The low Co concentration in sphalerite
differs from skarn (Ye et al., 2011) and MVT deposits (Frenzel et al.,
2016). The samples from all the four deposits of the BB show strong
geochemical signature matching with typical global VMS deposits
except in terms of Ga, Ge, and Ag (Frenzel et al., 2016) (Fig. 6A-I). These
deposits have been further characterized using discrimination diagram
of Ag vs. Mn, In/Cd vs. Mn, Mn vs. In/Ge, In + Sn vs. Mn, Fe vs. In/Ge, Fe
vs. In, Mn vs. Fe, In/Cd vs. Fe and Mn/Fe vs. In (Fig. 14 A-I). The
sphalerite in BB is characterized by the enrichment of Fe (4.55 wt% to
11.11 wt% with mean = 7. 27 wt%). A range of 5.16 to 9.91 wt% of Fe
was reported from the Zinkgruvan VMS deposit (Axelsson and
Rodushkin, 2001). An average of 5.6 wt% range was reported in the
VMS deposit literature (Cook et al., 1990).
The principal component, F1, divides BB sphalerite into Fe-rich and
Fe-poor categories (Fig. 10D). Fe-rich samples are basically from
Bhuyari and Jangaldehri deposits, whereas Fe-poor samples from Bis­
khan and Banskhapa deposits (Fig. 5B, 10). Fe-rich sphalerites have
relatively high concentrations (not necessarily always) of Mn (±Ag ±
Co) in these sphalerites (Fig. 10). Similarly, Fe-poor sphalerites are
depleted in these elements except Mn. Moreover, based on PCA
(Fig. 10C-E) and comparison diagrams of the trace elements (Fig. 5B–E),
Bhuyari and Jangaldehri sphalerite are characterized by high Fe, high
Mn, and appreciable In content suggest high-temperature ore formation
and mixing of the magmatic fluid (Chon and Shimazaki, 1986; Frenzel
et al., 2016). Sphalerite from Biskhan and Banskhapa are characterized
as low Fe with enriched Mn suggests relatively low-to-moderate tem­
perature VMS deposits. Sphalerite from Banskhapa is low in In content;
however, the enriched In found in Biskhan is enigmatic. Cd content is
similar in all four deposits, indicates deposits were evolved with a
relatively thick sediment sequence in the center of the Betul basin (e.g.,
(Quin, 1987). The two sphalerite geothermometers do not show the
same results but agree with a high sphalerite formations temperature.
FeS-ZnS geothermometry (Kullerud, 1953) suggests a relatively high
mineralization temperature in Jangaldehri and Bhuyari compared to
B.P. Mishra et al. Ore Geology Reviews 134 (2021) 104149

Fig. 10. Graphical representation of the results obtained from the Principal Component Analysis (PCA) of the LA-ICP-MS dataset (n = 26) from the four deposits viz;
Biskhan, Banskhapa, Bhuyari, and Jangaldehri. Concentrations of trace elements in sphalerite are log-transformed and then analyzed for PCA. (A) Scree plot showing
the line plot of eigenvalues (largest to smallest) of principal components determines the number of significant components retained in the analysis. The first two
principal components explain 73.29% cumulative variability of the whole dataset. (B) Component loadings in the principal component analysis show correlations
coefficient between elements (variables) and two principal components. (C) The plotting of elements in the plane is defined by two principal components (F1 vs. F2),
which explains 73.29% of the total variability. (D-E) Individual sample points (spot analysis) plotted on F1 vs. F2 plane and with active variables (elements),
explaining 73.29% data variability.

Biskhan and Banskhapa. This result is consistent with trace element
enrichment in the sphalerite from other VMS deposits of the world.
5.2. Pyrite geochemistry in deposit characterization
Compositional variations in pyrite are due to variations in physico­
chemical parameters viz, temperature, redox, pH, and ligands types
(Huston et al., 1995; Keith et al., 2016; Caruso et al., 2018; Zhang et al.,
2014; Dora et al., 2020), as well as fluid-rock interaction (Keith et al.,
2018, 2016). The pyrite trace element content plays a crucial role in
deposit characterization (Bajwah et al., 1987).
The Co/Ni ratio of pyrite is sensitive to the mode of formation
(Bajwah et al., 1987; Campbell and Ethier, 1984) and primarily
controlled by temperature and fS2 in ore-fluids (Maslennikov et al.,
2009). The Co/Ni ratio > 1 endorses VMS deposits in the Betul belt, as
reported elsewhere by Barrie et al. (Barrie et al., 2005) and Huston et al.
(Huston et al., 1995). The Co/Ni ratio (which is highly variable and
more than one) confirms that most of the BB pyrites are of hydrothermal
origin (Bralia et al., 1979; Campbell and Ethier, 1984; Craig et al., 1998;
Caruso et al., 2018) (Fig. 8A). However, pyrites from Banskhapa and
Jangaldehri deposits show high Co, low Ni concentrations, and Co/Ni >
10, which are likely to be precipitated from volcanogenic-hydrothermal
fluids. Se vs. Te indicates that Betul belt pyrites are different from Por­
phyry, Orogenic, and Carlin-type deposits but more or less similar to the
pyrite compositions of worldwide VMS deposits (Fig. 8E). The discrim­
inatory scatter plot of Cu vs. As and Au vs. Ag helps differentiate the
pyrites of VMS deposits from the orogenic gold (Belousov et al., 2016;
Large et al., 2009) (Fig. 8C-D). Pyrites plots in VMS space in the Au-Ag
plot except for the pyrites from the Biskhan deposit. The high Au con­
centration in the pyrites from Biskhan deposits may be related to a small
amount of mafic rock encounters in few boreholes (Fig. 3J). In contrast,
in the Cu-As plot, all the data points are plotted towards orogenic gold
space except Jangaldehri and some data points of Biskhan because of
deficient Cu in the samples. It is interpreted that Cu occurs as submi­
croscopic inclusions and is remobilized during the peak stage of meta­
morphism. The low Ni concentration in the pyrites from all four deposits
indicates low concentration in the ore-fluid, a distinctive feature of
felsic-hosted VMS deposits (Bajwah et al., 1987). The average pyrite
geochemistry in the Betul belt are similar to pyrites from several VMS
deposits of the world, e.g., the Kidd Creek deposit, the eastern Australia
VMS, Mobron VMS deposit, Boliden deposit, and Yaman-Kasy deposit
reported by Cabri et al. (1985), Huston et al. (1995), Larocque et al.
(1995), Wagner et al. (2007) and Maslennikov et al. (2009) respectively.
In deposit scale, the principal component analysis (Fig. 11) and the
trace element comparison (Fig. 7A-E) studies confirm that Jangaldehri
pyrites are dominant in Se (64–423 ppm, average 302 ppm) and highly
variable Co (1–232 ppm, average 81 ppm) may indicate magmatic
contribution (Hannington et al., 1999a, 1999b; Huston et al., 1995).

16
B.P. Mishra et al. Ore Geology Reviews 134 (2021) 104149

Fig. 11. Graphical representation of the results obtained from the Principal Component Analysis (PCA) of the LA-ICP-MS dataset from the four deposits viz; Biskhan,
Banskhapa, Bhuyari, and Jangaldehri. Concentrations of trace elements in pyrite are log-transformed and then analyzed for PCA. (A) Scree plot showing the line plot
of eigenvalues (largest to smallest) of principal components determines the number of significant components retained in the analysis. The first two principal
components explain 59.06% cumulative variability of the whole dataset. (B) Component loadings in the principal component analysis show correlations coefficient
between elements (variables) and two principal components. (C) Plotting of elements in the plane defined by two principal components (F1 vs. F2), which explain
59.06% of the total variability. (D-E) Individual sample points (spot analysis) plotted on F1 vs. F2 plane and with active variables (elements), explaining 59.06% data
variability.

High Co and Se content in pyrite is a characteristic feature of Cu-rich,
high-temperature VMS deposits (Hannington et al., 1999a, 1999b;
Huston et al., 1995; Raymond, 1996; Walshe and Solomon, 1981). High-
temperature mineralization at Jangaldehri is too interpreted in this
work from sphalerite geothermometry (Table. 3) Bhuyari shows
extremely low Se in association with Cu-rich zone. The Mn content is
almost constant in all four deposits except for a few high values (5–438
ppm) at Jangaldehri, formed in sub-alkaline seawater with oxygen
during sulfide growth (Eremin, 1983). In contrast, low Mn(3–22 ppm)
content in pyrites confirms high temperature reduced fluids at Bhuyari
(Maslennikov et al., 2009). The higher As contents are seen from
Bhuyari, Biskhan, and Banskhapa, the result of rapid precipitation
(Huston et al., 1995) during the mixing of sulfides with seawater
(McClenaghan et al., 2009). Pyrites from the Jangaldehri deposit are
distinct and relatively abundant in Co and low As concentrations
compare to other deposits. This suggests a characteristics feature of low
to moderate temperature ore fluid responsible for pyrite mineralization
at Jangaldehri. PCA studies indicate that trace element-wise pyrites
from the four deposits can be classified into four distinct types Ti-
bearing, As-bearing, Se-bearing, and Co-bearing pyrites (Fig. 11D).
The principal component F1 suggests that pyrites from Jangaldehri are
compositionally different from pyrites from Biskhan and Bhuyari de­
posits. Banskhapa deposits have fairly similarities with Jangaldehri. This
interpretation is consistent with the sphalerite trace element
geochemistry.
5.3. Isotopic characteristics and constraints on the ore-forming
environment
The VMS deposits are formed due to seawater’s complex interactions
(±magmatic fluid) with adjacent volcanics and sediments (Lydon, 1984;
Franklin, 1993; Galley et al., 2007; Bailie and Gutzmer., J, 2011; Caruso
et al., 2019). The seawater sulfate, upon reduction by various
geochemical processes, including bacterial reduction, and igneous
leaching, precipitates as sulfide (Essaifi et al., 2019). Raza et al. (Raza
et al., 2020) investigated δ34S from three VMS deposits, i.e., Ghisi,
Jangaldehri, and Biskhan, in the western and eastern parts of the Betul
belt. They interpreted multiple sulfur sources that led to Cu-Zn-Pb
mineralization. The present study of δ34S values for sphalerite, pyrite,
and chalcopyrite in Banskhapa deposit in the central sector show very
restricted ranges, i.e., 7.27–7.59‰ (n = 3), 8.37–8.61‰ (n = 2) and
6.58–6.72‰ (n = 2) respectively. This indicates the origin of sulfur
primarily from seawater sulfate and little contribution from hydro­
thermal sulfur as recorded from several VMS deposits (Solomon et al.,
2004). Thermochemical sulfate reduction is likely to be the process
responsible for seawater sulfate reduction at the Banskhapa deposit. The

17
B.P. Mishra et al. Ore Geology Reviews 134 (2021) 104149

Fig. 12. Sulfur isotope (δ34S) composition of metal sulfide (pyrite and sphalerite) Banskhapa, in the Betul belt compared with the field of other three deposits after
Raza et al. (2020). Range of δ34S for magmatic and marine-evaporite systems obtained after Hoefs (2009) and Chen and Zhou (2012).

hydrothermal sulfur may be due to igneous leaching by a magmatic- Shields and Veizer (2002). Bhuyari deposit shows a distinct field that
hydrothermal fluid with an insignificant magmatic contribution. This overlaps the Afterthought carbonate fields, Archean deposit of Lake
result is consistent with sphalerite trace element chemistry, which shows Sturgeon, Canada (Herrmann and Hill, 2001). They are mostly inter­
the igneous elements Mn > 1500 ppm, In > 20 ppm in Banskhapa preted to have formed due to hydrothermal carbonate alteration of
(Table 3). The small variability in ranges of δ34S values suggests that the volcanic rocks. Thus, the δ13C and δ18O isotopic signatures in the
seawater chemical reduction of sulfate is observed in several other VMS chlorite-carbonate alteration zones at Bhuyari indicate that the fluids
deposits elsewhere on the globe (Sakaki and Kajiwara, 1971; Seal, were predominantly formed from a hydrothermal fluid (seawater with
2006). As the hydrothermal system continues to evolve and heat up to an insignificant magmatic input), the mixing of hydrothermal fluid with
300 ◦ C and above, either the fluids begin to dissolved rock S or a direct ingressing seawater, or both in the mineralized zone. The source of this
magmatic injection introduces S, Se, Cu, and other high-temperature hydrothermal fluid is seawater.
metals into the evolving system. This produces the Cu-rich zone pre­
sent at Banskhapa and is inferred as a product of the hydrothermal
5.4. Ore genesis and metamorphism
system, which underwent regional metamorphism, a common phe­
nomenon among ancient VMS deposits (Galley et al., 2007). In general,
The genetic relation between metallic mineralization, alteration, and
the effect of later metamorphism after ore deposition on the isotopic
metamorphism on sulfide minerals has been explained by Craig and
composition of sulfide did not change much of its original composition
Vokes (1993). A dearth of information is available on the metamorphism
(Hoefs, 2009).
effect on VMS deposits (Cook, 1996; Vokes, 1971). Like VMS deposits
Several authors have investigated δ13C and δ18O isotope to under­
elsewhere globally, Betul belt VMS deposits were modified by regional
stand the physicochemical conditions of the ore-forming environment of
metamorphism and deformation (Vokes, 1966; Spry et al., 2000; Cor­
various mineral deposits, including VMS deposits (Davidson, 1993;
riveau and Spry, 2014).
Huston, 1997; Zaw and Large, 1992; Zheng and Hoeffs, 1993; Mondillo
The sphalerite and pyrite in the Betul belt have undergone upper
et al., 2017; Wang et al., 2021). Moreover, Huston (Huston, 1999) found
amphibolite facies metamorphism and are affected by the syn-meta­
δ13C shows a limited range (− 5 to 0‰) where δ18O relatively large
morphic recrystallization. The textural studies confirm that the bulk of
variations for typical VMS deposits. The present study confirms two
sphalerite and pyrite grains have undergone both deformations and
distinct isotopic populations at Bhuyari deposit, for calcite veins (δ13C
recrystallization. The detailed textural and mineralogical changes due to
values − 7.92 to − 9.74‰ (n = 4) and δ18O values 17.72 to 20.58‰ (n =
metamorphism are described in Section 4.1. Pyrite crystals are deformed
4) whereas the surface dolomite samples show − 6 to − 13‰ (n = 2) and
into a wide range of shapes. Sphalerite grains are remobilized and
7.32 to 15.23‰, (n = 2) respectively (Fig. 13) (Table 6). The increased
recrystallized. Metamorphism added new phases (gangue minerals) into
oxygen isotope values from the surface to the subsurface were possibly
the sulfide assemblage (Fig. 4 H). The essential gangue minerals asso­
influenced by changes in temperature and fluid interaction with the
ciated with sulfide assemblages are gahnite, garnet, anthophyllite,
wall-rocks (Huston, 1997; Zaw and Large, 1992). The surface alteration
sillimanite, staurolite, ilmenite, biotite, chlorite, and quartz. Gahnite,
zone has oxygen isotopic values that indicate a magmatic component,
garnet, staurolite, and biotite show high Zn concentration (~2% Zn). Zn
reported by Praveen et al. (Praveen et al., 2020). The sub-surface values
inclusions are present in the silicate minerals (Fig. 4A). Metamorphism
suggest marine and hydrothermal fluids’ involvement in forming these
partially redistributed the trace elements content in sulfide minerals.
calcite veins, nearly matching Palaeoproterozoic marine carbonate
The low concentration of the elements like Bi and Pb in sphalerite

18
 B.P. Mishra et al.
Table 7
Sulfur isotopic compositions (n = 7) of minerals from the Banskhapa deposits and Carbon and Oxygen isotope from Bhuyari (n = 6) and Jangalderhi (n = 1) deposits of the Betul belt.
Deposit No of analysis Sample Name/ Coordinates Host Drillcore Mineralogical Types of Mineral δ34 S Stand Nature of Samples
name performed (n = type (Bed rock/ rock and depth composition analysis Dev.
14) Drill core) performed
Sp Py Ccp Cal

Banskhapa 7 BP/DC-1 21◦ 59′ 29.6′′ GGMS BP-12/ Sp-Py Sulfur Isotope 7.79 – – – 0.22 Massive lumps of sphalerite
78◦ 23′ 45′′ 44.00 (δ34 S)
BP/DC-2 21◦ 59′ 45.5′′ GMS BP-17/ Sp-Py 7.59 – – – 0.03 Stringers of sphalerite along the
78◦ 24′ 0.5′′ 145.2 foliation plane
BP/DC-3 22◦ 00′ 20′′ QMS BP-17/ Sp-Py 7.27 – – – 0.58 Disseminated and veins of
78◦ 24′ 05′′ 218.00 sphalerite along the foliation
plane
BP/DC-4 21◦ 56′ 26′′ QSS BP-8/55.9 Py-Sp – – 6.72 – 0.39 Chalcopyrite stringers along the
78◦ 28′ 06′′ foliation plane
BP/DC-5 21◦ 59′ 41′′ GMS BP-15/ Py-Ccp-Sp – 6.58 – 0.22 Chalcopyrite veins
78◦ 23′ 51′′ 84.25
BP/DC-6 21◦ 59′ 42′′ QSS BP-3/85.5 Py-Ccp – 8.61 – – 0.56 Disseminated Pyrite
78◦ 23′ 52′′
BP/DC-7 21◦ 59′ 45.5′′ QSS BP-17/ Py-Ccp-Sp – 8.37 – – 0.1 Coarse dissemination of pyrite
78◦ 24′ 0.5′′ 145.2
19

Bhuyari Carbon and oxygen isotope Calcite Nature of Samples

13
C/12C 18
O/16O SMOW
(VPDB) (VPDB)

6 BY/DC-1 21◦ 59′ 39′′ 78◦ BH 3-A Cal-Py-Chl – – – − 9.74 − 9.96 20.58 Fine to coarse-grained carbonate
35′ 41 − 61 m with sulfide disseminations
(pyrite + sphalerite)
BY/DC-2 21◦ 59′ 39′′ 78◦ BH3-B/ Cal-Py-Sp C and O – – − 9.47 − 11.06 19.45
35′ 41 61.3 m Isotope
BY/DC-3 21◦ 59′ 39 78
′′ ◦
BH 3-C- Cal-Sp-Ccp-Chl – – − 7.92 − 13.24 17.20
35′ 41 61.5 m
BY/DC-4 21◦ 59′ 39′′ 78◦ BH-1–86.7 Cal-Chl – – − 8.87 − 12.73 17.72 Fine to coarse-grained carbonate
35′ 42 m
BY/BR-5 21◦ 59′ 45′′ 78◦ BT29S/5 Tr-Act-Dol – – – − 13.45 − 15.16 15.23 Fine-grained carbonate with large
35′ 42′′ tremolite-actinolite laths.
BY/BR-6 21◦ 59′ 45 78
′′ ◦
BT29S/6 – – – − 6 − 22.83 7.32 Mostly white, fine-grained
35′ 43′′ carbonate segregations in
tremolite-talc rock

Ore Geology Reviews 134 (2021) 104149

Jangaldehri 1 JD/DC-7 21◦ 58′ 40′′ 78◦ JD-1/90 m Cal-Chl-Sp-Py-Qt – – – − 11.12 − 18.20 12.09 Fine to coarse-grained carbonate
26′ 58′′ with sulfide disseminations

Abbreviation: BP-Banskhapa-Pipariya; BY-Bhuyari, JD: Jangaldehri; DC-Drill core samples; BR-Bed rock; GGMS: Garnet-gahnite-mica schist; QMS: quartz-mica schist; GMS: Garnet-mica schist; QSS: quartz sericite schist;
Tr: tremolite, Act-actinolite; Dol-Dolomite, Cal-calcite; Sp- sphalerite, Py-Pyrite, Ccp-Chalcopyrite, Qt- quartz.
B.P. Mishra et al. Ore Geology Reviews 134 (2021) 104149

Fig.13. Stable isotope (C and O) data of carbonate rocks from Bhuyari deposit. The fields for magmatic carbonate are from Herrmann and Hill (2001), Mantle
carbonate from Taylor (1987), other VMS deposits from Huston (1999), Praveen et al. (2020) and Paleoproterozoic marine carbonate from Shields and Veizer (2002)
and Ophicarbonate (Perkins et al., 2006). Bhuyari carbonates show an overlapping field with Afterthought VHMS deposit (Huston, 1999).

Fig. 14. (A-I) Binary plots Ag-Mn, In/Cd-Mn, Mn-In/Ge, In + Sn-Mn, Fe-In/Ge, Fe-In, Mn-Fe, In/Cd-Fe and Mn + Fe-In in sphalerite from the Betul belt (Biskhan,
Banskhapa, Bhuyari, and Jangaldehri deposits only). Each plot distinctly indicates VMS type mineralization and different from Mississippi Valley-type (MVT),
epithermal, distal skarn, magmatic-hydrothermal, vein-type Pb-Zn, and SEDEX. Plotting fields were obtained from Cook et al. (2009), Ye et al. (2011), and Wei
et al. (2018).

20
B.P. Mishra et al.
(Table 3) is likely to be the consequence of the complete recrystallization
and remobilization of the sub-microscopic inclusion during meta­
morphism. The effect of metamorphism on lattice-bound elements like
Zn and Fe is relatively well documented and expected to increase with
an increase in temperature (Kullerud, 1953; Hutchison and Scott, 1981;
Lusk et al., 1993). However, Betul belt sulfide minerals exhibit a low
abundance of such elements. The syn-metamorphic ore remobilisation
likely led to a redistribution of Zn in associated silicates and redeposition
of base metal sulfides. It is reasonable to interpret that metamorphism
eventuated at the time of post-depositional maturation of the ore bodies.
Thus, zinc grade has significantly decreased in the Betul belt deposits
that affect its economic significance. The archetypical low zinc grade in
BB and not very high trace elements’ suite values are interpreted due to
metamorphism.
Moreover, the characteristic chalcopyrite disease is evident in the
sphalerite from Bhuyari, Biskhan, and Jangaldehri (Fig. 4C). Chalco­
pyrite disease is a prevalent texture observed in metamorphosed vol­
canogenic massive sulfides deposits (Barton and Skinner, 1967;
Govindarao et al., 2018; Large, 1992; Ohmoto, 1996. Despite the origin
debate, diffusion-controlled replacement, partial melting, and co-
precipitation are presumptive mechanisms for forming chalcopyrite
disease in sphalerite (Barton and Bethke, 1987; Govindarao et al., 2018;
Sugaki et al., 1987. Metamorphism homogenized the trace element
distribution in the sphalerite, evidenced by the absence of compositional
zoning in the specimens. We have interpreted the lack of compositional
zoning due to the post-depositional diffusion process agreeing with
Toshio (1988). Cook et al. (1994) suggested that recrystallization during
Fig. 15. Schematic model of ore-fluid evolution and mineralization (occur as a stringer and massive bands shown in stratigraphic columns, represented by M and S)
in the Betul belt VMS system, depicted from metal sulfide (sphalerite and pyrite) geochemistry and sulfur isotope systematics. Data were collected from Biskhan,
Banskhapa, Bhuyari, and Jangaldehri VMS deposits belonging to Bargaon Formation from the Betul belt’s eastern segment, central India.
21
Ore Geology Reviews 134 (2021) 104149
metamorphism can obliterate compositional zoning in sphalerite
crystals.
6. Exploration significance
In India, the VMS deposits are known from Ambaji and Deri, the
South Delhi fold Belt (SDFB) in Rajasthan (Deb et al., 2001). Like the
SDFB, it took considerable time to realize VMS style mineralization in
the Betul Belt in central India (Golani and Dora, 2003). However, there
is no comprehensive geological model for exploration. This field and
laboratory research work brought out a broad understanding of the ore-
forming environment and ore deposit type. Together with the earlier
work, this study categorized Betul belt sulfide mineralization as a typical
VMS deposit with high-temperature ore formation.
It is best known that VMS deposits are formed from metal-rich ore
fluid associated with seawater convection within-host lithologies
(Franklin et al., 1981; Barrie and Hannington, 1999; Hannington et al.,
1999a, 1999b). The lithologies are either volcano-sedimentary or vol­
canic rocks (Galley et al., 2007). A heat source triggers the convection
process either by a magma chamber at depth or by subvolcanic in­
trusions (Franklin et al., 1981; Barrie and Hannington, 1999). Thus
targeting high heat sources and permeable host rock across the Betul belt
is critical in locating mineralization (Barrie and Hannington, 1999).
Hence deciphering the thermal corridor across the Betul belt may help to
understand regional metallogenesis. Advanced suitable geophysical
tools can locate shallow subvolcanic intrusions that are understandably
the primary heat source across the Betul belt. The PCA studies confirmed
B.P. Mishra et al.
that Jangaldehri sphalerites are dominated by magmatic elements such
as Mn and In, which are likely added by magmatic fluid from sub­
volcanic intrusions (Fig. 10E). It also confirms that Cd’s high variability
in samples from all four deposits suggests sedimentary, high permeable
host rock during the mineralization in the eastern segment of the Betul
belt (Quin, 1987). Hence eastern segment of the Betul belt was likely to
be a region of a high heat source and permeable host rock, which in­
dicates an ideal geological setup for VMS style mineralization. Thus a
further deep level exploration is warranted in this belt.
Litho-geochemistry and petrochemical assemblages are useful
exploration tools for discovering the VMS style mineralization (Lesher
et al., 1986; Piercey, 2011). The VMS bearing rhyolites are formed by
high temperature melting at a shallow level (Lentz, 1998; Lesher et al.,
1986). Thus, FII and FIII type rhyolites based on Lesher et al. (1986)
classification can be applied in the Betul belt to narrow down the search
area for exploration interest. Similarly, the high-temperature alteration
assemblage can be used for vectoring toward the mineralisation center
(Fig. 3). Metal sulfide chemistry and sulfur isotopes indicate that the
Betul belt is a promising target for VMS-related mineralisation for the
future. For a detailed understanding of the four deposits, a conceptual
model is given in Fig. 15 based on multiple geological parameters.
Despite primary sulfide and stable isotope geochemistry studies,
further reasonable research is needed to understand the VMS system’s
ore-forming conditions (pH, redox, fluid composition, etc.) and its
spatio-temporal distribution in the Betul belt within the CITZ.
7. Concluding remarks
The integrated study by combining field observations, drill core
analysis, petrography, and in situ LA-ICP-MS analysis of metal sulfide
(sphalerite and pyrite) geochemistry along with stable isotope system­
atics, brought out the following conclusions in the archetypal felsic-
hosted low zinc grade metamorphosed deposits of the Betul belt:
1. Sphalerite trace elements are characterized by enriched Fe, In, and
Mn, and depleted Ga, Ge, Ag, and Pb in all four deposits, similar to
VMS deposit, distinct from Skarns, MVT, SEDEX, or Copper Por­
phyry. Ore forming temperature (375 ◦ C to 402 ◦ C) has been deter­
mined with the GGIMF method. This suggests that temperature may
be one of the primary parameters that play a crucial role from fluid
circulations to metal deposition in a VMS mineral system in the Betul
belt.
2. Pyrite trace elements show high Co/Ni (>1), and δ34SCDT (5.01‰ to
8.54‰) values indicate that pyrites in the Betul belt were derived
from the same magmatic-hydrothermal origin, resemble VMS type.
Thus, Zn-Cu-Pb mineralization is genetically linked to high-
temperature magmatic-hydrothermal fluids. Se content in pyrite is
used as a proxy for estimating relative temperature (225 to 484 ◦ C) in
ore-forming fluids of VMS deposits in the Betul belt. Thus, pyrite
geochemistry aids in understanding the genesis of a VMS mineral
system.
3. Ore petrography and sulfur isotope geochemistry confirm high
temperature hydrothermal ore-fluid mineralization were from mul­
tiple sulfur sources. Their reduction at different depths led to varied
mineralization assemblages from Zn-Cu-Pb to Zn-Cu.
4. The δ 13C and δ 18O isotopic characteristics suggest that the fluids
were predominantly formed from upwelling hydrothermal fluid
(modified seawater with a minor magmatic input) and/or mixing the
hydrothermal fluid with infiltrating seawater in the mineralized
zone. The original hydrothermal fluid is derived from the seawater.
5. Statistical methods, such as PCA on pyrite and sphalerite, established
a geological framework and revealed the hydrothermal evolution of
Bhuyari, Banskhapa, Biskhan, and Jangaldehri VMS deposits. It
concludes that geochemical variations exist within a sizeable VMS
system of the Betul belt. Thus, a suitable integrated strategy can be
adopted for deeper level exploration for these small deposits in
22
Ore Geology Reviews 134 (2021) 104149
central India’s lesser-known VMS deposits to classical global VMS
deposits.
Funding
No particular funding was received for this work. This is GSI regular
investigation program in Betul Belt, Central India.
CRediT authorship contribution statement
Bishnu Prasad Mishra: Writing - original draft, Methodology,
Visualization. Pitamber Pati: Conceptualization, Writing - review &
editing, Supervision. Muduru Lachhana Dora: Conceptualization, Su­
pervision, Project administration, Writing - review & editing. Srinivasa
Rao Baswani: Resources, Investigation. Tushar Meshram: Resources,
Investigation. Mohd. Shareef: Resources, Formal analysis. Ram Sankar
Pattanayak: Resources, Formal analysis. Hemraj Suryavanshi: Re­
sources, Investigation. Monika Mishra: Resources, Formal analysis.
Mohd Atif Raza: Resources, Formal analysis.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
MLD extends sincere thanks to Dr. Ranjit Rath, Director General, and
Shri G. Vidyasagar, Head of Department and Addl. Director-General,
Geological Survey of India, Nagpur, for their kind inspiration and
permission to publish this research article. MLD, thank Shri. Sanjeev
Raghav, DDG, and RMH-III, Nagpur, for his continuous encouragement
to write this quality manuscript. The Geological Survey of India entirely
supported this research work under different Field Season Programme.
Acknowledge the Wadia Institute of Himalaya Geology (WIHG), India,
for providing a facility for carbon isotope study. The authors extend
their sincere thanks, gratitude, and are enormously grateful to Prof.
Huayong Chen, the Editor-in-Chief, Ore Geology Reviews, Guangzhou
Institute of Geochemistry, Guangzhou, China for his kind guidance and
valuable suggestions from time to time during the entire review process.
Authors extend their sincere thanks to Prof. David Lentz, Canada Asso­
ciate Editor, Ore Geology Reviews, University of New Brunswick,
Fredericton, New Brunswick, Canada, for his encouragement and kind
submissions for improving the quality of the manuscript. The author also
thankful to Dr. Stefano Caruso, Associate Editor, Ore Geology Reviews,
for his critical suggestions in the previous version. Prof. Xiao-Hua Deng,
Beijing Institute of Geology, China; Dr. Russell Bailie, University of the
Western Cape, South Africa, and one anonymous reviewer for their
thorough and critical reviews and excellent suggestions are instrumental
in improving the quality and finalization of a revised manuscript.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.oregeorev.2021.104149.
References
Abraitis, P.K., Pattrick, R.A.D., Vaughan, D.J., 2004. Variations in the compositional,
textural, and electrical properties of natural pyrite: a review. Int. J. Miner. Process.
74, 41–59. https://doi.org/10.1016/j.minpro.2003.09.002.
Auclair, G., Fouquet, Y., Bohn, M., 1987. Distribution of selenium in high-temperature
hydrothermal sulfide deposits at 13 Degree North, East Pacific Rise. Can. Mineral.
25, 577–587.
Axelsson, M.D., Rodushkin, I., 2001. Determination of major and trace elements in
sphalerite using laser ablation double-focusing sector field ICP-MS. J. Geochem.
Explor. 72, 81–89. https://doi.org/10.1016/S0375-6742(00)00166-7.
B.P. Mishra et al.
Bailie, R., Gutzmer, J., Strauss, H., Stucken, E., McClung, C., 2010. Sulfur isotope
characteristics of metamorphosed Zn-Cu volcanogenic massive sulfides in the
Areachap Group, Northern Cape Province, South Africa. Miner. Depos. 45, 481–496.
Bailie, R., Gutzmer, J., 2011. Age and primary architecture of the Copperton Zn-Cu VMS
deposit, Northern Cape Province, South Africa. Ore Geol. Rev. 39–3, 164–179.
https://doi.org/10.1016/j.oregeorev.2011.02.001.
Bajwah, Z.U., Seccombe, P.K., Offler, R., 1987. Trace element distribution Co: Ni ratios
and genesis of the Big Cadia iron-copper deposit, New South Wales, Australia. Miner.
Depos. 22, 292–300.
Barrie, C.T., Hannington, M.D., 1999. Classification of volcanic-associated massive
sulfide deposits based on host rock composition, in Barrie, C.T., and Hannington, M.
D., eds, Volcanic-associated massive sulfide deposits: processes and examples in
modern and ancient settings: Society of Economic Geologists. Econ. Geol. 8, 1–11.
Barrie, C.T., Taylor, C., Ames, D.E., 2005. Geology and metal contents of the Ruttan
volcanogenic massive sulfide deposit, northern Manitoba. Canada. Miner. Depos. 39,
795–812. https://doi.org/10.1007/s00126-004-0455-7.
Barton, P.B., Bethke, P.M., 1987. Chalcopyrite disease in sphalerite: pathology and
epidemiology. Am. Mineral. 72, 451–467.
Barton, P.B., Jr., Skinner, B.J., 1967. Sulfide mineral stabilities. In: Barnes, H. L., ed.,
Geochemistry of hydrothermal ore deposits: New York, Holt, Rinehart, and Winston.
pp. 236–333.
Bauer, M.E., Burisch, M., Ostendorf, J., Krause, J., Frenzel, M., Seifert, T., Gutzmer, J.,
2019. Trace element geochemistry of sphalerite in contrasting hydrothermal fluid
systems of the Freiberg district, Germany: insights from LA-ICP-MS analysis, near-
infrared light microthermometry sphalerite-hosted fluid inclusions, and sulfur
isotope geochemistry. Miner. Depos. 54, 237–262. https://doi.org/10.1007/s00126-
018-0850-0.
Beaudoin, G., Taylor, B.E., 1994. High precision and spatial resolution sulfur isotope
analysis using MILES laser microprobe. Geochim. Cosmochim. Acta. 58, 5055–5063.
https://doi.org/10.1016/0016-7037(94)90231-3.
Belissont, R., Boiron, M.C., Luais, B., Cathelineau, M., 2014. LA-ICP-MS analyses of
minor and trace elements and bulk Ge isotopes in zoned Ge-rich sphalerites from the
Noailhac – Saint-Salvy deposit (France): insights into incorporation mechanisms and
ore deposition processes. Geochim. Cosmochim. Acta. 126, 518–540. https://doi.
org/10.1016/j.gca.2013.10.052.
Belousov, I., Large, R.R., Meffre, S., Danyushevsky, L.V., Steadman, J., Beardsmore, T.,
2016. Pyrite compositions from VHMS and orogenic Au deposits in the Yilgarn
Craton, Western Australia: implications for gold and copper exploration. Ore Geol.
Rev. 79, 474–499. https://doi.org/10.1016/j.oregeorev.2016.04.020.
Bralia, A., Sabatini, G., Troja, F., 1979. A revaluation of the Co/Ni ratio in pyrite as
geochemical tool in ore genesis problems – evidences from southern tuscany pyritic
deposits. Miner. Depos. 14, 353–374. https://doi.org/10.1007/BF00206365.
Cabri, L.J., Campbell, J.L., Leigh, R.G., Maxwell, J.A., Scott, J.D., 1985. Proton
microbeam analysis of trace elements in sulfides from some massive-sulfide deposits.
Can. Mineral. 23, 133–148.
Campbell, F.A., Ethier, V.G., 1984. Nickel and cobalt in pyrrhotite and pyrite from the
Faro and Sullivan orebodies. Can. Min. 22, 503–506.
Caruso, S., Fiorentini, M.L., Hollis, S.P., LaFlamme, C., Baumgartner, R.J., Steadman, J.
A., Savard, D., 2018. The fluid evolution of the Nimbus Ag-Zn-(Au) deposit: An
interplay between mantle plume and microbial activity. Precambrian Res. 317,
211–229. https://doi.org/10.1016/j.precamres.2018.08.012.
Caruso, S., Fiorentini, M.L., Barnes, S.J., LaFlamme, C.K., Martin, L.A.J., 2019.
Microchemical and sulfur isotope constraints on the magmatic and hydrothermal
evolution of the Black Swan Succession, Western Australia. Miner. Depos. 55,
535–553. https://doi.org/10.1007/s00126-019-00891-7.
Chaturvedi, R.K., 2001. A review of the geology, tectonic features, and tectono
lithostratigraphy of Betul belt. Geol. Surv. Ind. Spl. 1, 299–315.
Chen, H., 2013. External sulfur in IOCG mineralization: Implications on the definition
and classification of the IOCG clan. Ore Geol. Rev. 51, 74–78. https://doi.org/
10.1016/j.oregeorev.2012.12.002.
Chen, H., Tian, W., Falloon, T.J., Chen, M., 2011. Pyrite trace element geochemistry of
mafic granulite xenoliths from Xikeer: Implications for the source of Cu in the
sediment-hosted mineralization in the northwestern Tarim Basin (Northwest China).
Miner. Depos. 46, 1001–1006. https://doi.org/10.1007/s00126-011-0387-y.
Chen, H., Wan, B., Pirajno, F., Chen, Y., Xiao, B., 2018. Metallogenesis of the Xinjiang
Orogens, NW China – New discoveries and ore genesis. Ore Geol. Rev. 100, 1–11.
https://doi.org/10.1016/j.oregeorev.2018.02.035.
Chon, H.T., Shimazaki, H., 1986. Iron, manganese, and cadmium contents of sphalerites
and their genetical implications to hydrothermal metallic ore deposits in Korea.
J. Korean Inst. Min. Geol. 19, 139–149.
Chen, W.T., Zhou, M.F., 2012. Paragenesis, stable isotopes, and molybdenite Re-Os
isotope age of the Lala iron-copper deposit, Southwest China. Econ. Geol. 107,
459–480.
Chore, S.A., Chakraborty, S., Vishwakarma, L.L., Thaplial, A.P., 2002. Petrology of base
metal- bearing volcano sedimentary litho assemblages of the Betul Belt of Central
India and its possible significance in the evolutionary history of the Central Indian
Tectonic Zone. Geol. Surv. Ind. Rec. 135 (6), 16–17.
Chowdhury, S., Pal, D.C., Papineau, D., Lentz, D.R., 2020. Major and trace element and
multiple sulfur isotope composition of sulfides from the Paleoproterozoic Surda
copper deposit, Singhbhum shear Zone, India: Implications for the mineralization
processes. Ore Geol. Rev. 120, 103396 https://doi.org/10.1016/j.
oregeorev.2020.103396.
Ciobanu, C.L., Cook, N.J., Utsunomiya, S., Kogagwa, M., Green, L., Gilbert, S., Wade, B.,
2012. Gold-telluride nanoparticles revealed in arsenic-free pyrite. Am. Min. 97,
1515–1518. https://doi.org/10.2138/am.2012.4207.
23
Ore Geology Reviews 134 (2021) 104149
Corriveau, L., Spry, P.G., 2014. Metamorphosed hydrothermal ore deposits. In: Scott, S.
D. (Ed.), Geochemistry of Mineral Resources, second ed. Treatise on Geochem.
Elsevier, New York, 13, pp. 175–194.
Cooke, D.R., Wilkinson, J.J., Baker, M., Agnew, P., Phillips, J., Chang, Z., Chen, H.,
Wilkinson, C.C., Inglis, S., Hollings, P., Zhang, L., Gemmell, J.B., White, N.C.,
Danyushevsky, L., Martin, H., 2020. Using mineral chemistry to aid exploration: a
case study from the resolution porphyry Cu-Mo deposit, Arizona. Econ. Geol. 115,
813–840. https://doi.org/10.5382/ECONGEO.4735.
Cook, N.J., 1996. Mineralogy of the sulphide deposits at Sulitjelma, northern Norway.
Ore Geol. Rev. 11, 303–338.
Cook, N.J., Ciobanu, C.L., George, L., Zhu, Z.Y., Wade, B., Ehrig, K., 2016. Trace element
analysis of minerals in magmatic-hydrothermal ores by laser ablation inductively-
coupled plasma mass spectrometry: approaches and opportunities. Minerals 6.
https://doi.org/10.3390/min6040111.
Cook, N.J., Ciobanu, C.L., Pring, A., Skinner, W., Shimizu, M., Danyushevsky, L., Saini-
Eidukat, B., Melcher, F., 2009. Trace and minor elements in sphalerite: a LA-ICPMS
study. Geochim. Cosmochim. Acta. 73, 4761–4791. https://doi.org/10.1016/j.
gca.2009.05.045.
Cook, N.J., Halls, C., Kaspersen, P.O., 1990. The geology of the Sulitjelma ore field,
northern Norway – some new interpretations. Econ. Geol. 85, 1720–1737. https://
doi.org/10.2113/gsecongeo.85.8.1720.
Cook, N.J., Klemd, R., Okrusch, M., 1994. Sulfide mineralogy, metamorphism, and
deformation in the Matchless massive sulfide deposit. Namibia. Miner. Depos. 29,
1–15. https://doi.org/10.1007/BF03326392.
Craig, J.R., Vokes, F.M., 1993. The metamorphism of pyrite and pyritic ores: an
overview. Mineral. Mag. 57, 3–18. https://doi.org/10.1180/
minmag.1993.057.386.02.
Craig, J.R., Vokes, F.M., Solberg, T.N., 1998. Pyrite: physical and chemical textures.
Miner. Depos. 34, 82–101. https://doi.org/10.1007/s001260050187.
Davidson, G.J., 1993. Carbon/oxygen isotopes-their principles and uses in the
exploration and understanding of fossil hydrothermal systems. Exploration
Geochemistry and Hydrothermal Geochemistry, Part 2- Master of Econ. Geol. Course
Work Manual 12.
Deb, M., Thorpe, R.I., Kristic, D., Corfu, F., Devis, D.W., 2001. Zircon U-Pb and galena
isotope evidence for an approximate 1.0 Ga terrain constituting the western margin
of the Aravalli-Delhi orogenic belt, northwestern India. Precamb. Res. 108, 195–213.
Deditius, A.P., Reich, M., Kesler, S.E., Utsunomiya, S., Chryssoulis, S.L., Walshe, J.,
Ewing, R.C., 2014. The coupled geochemistry of Au and As in pyrite from
hydrothermal ore deposits. Geochim. Cosmochim. Acta. 140, 644–670.
De Groot, P.A., 2009. Handbook of Stable Isotope Analytical Techniques. Elsevier,
Amsterdam, p. 1372, 2.
Dehnavi, A.S., McFarlane, C.R.M., Lentz, D.R., Walker, J.A., 2018. Assessment of pyrite
composition by LA-ICP-MS techniques from massive sulfide deposits of the Bathurst
Mining Camp, Canada: from textural and chemical evolution to its application as a
vectoring tool for the exploration of VMS deposits. Ore Geol. Rev. 92, 656–671.
https://doi.org/10.1016/j.oregeorev.2017.10.010.
Deng, X.H., Mathur, R., Li, Y., Mao, Q.G., Wu, Y.S., Yang, L.Y., Chen, X., Xu, J., 2019.
Copper and zinc isotope variation of the VMS mineralization in the Kalatag district,
eastern Tianshan, NW China. J. Geoch. Expl. 196, 8–19.
Dora, M.L., Praveen, M.N., 2007. Prospecting for base metal mineralization in Bhuyari
Block, Chhindwara district, M.P, E-I stage. GSI report for the Field Season. 2003-04.
Dora, M.L., Upadhyay, D., Randive, K.R., Shareef, M., Baswani, S.R., Ranjan, S., 2020.
Trace element geochemistry of magnetite and pyrite and sulfur isotope geochemistry
of pyrite and barite from the Thanewasna Cu-(Au) deposit, western Bastar Craton,
central India: implication for ore genesis. Ore Geol. Rev. 117 https://doi.org/
10.1016/j.oregeorev.2019.103262.
Eremin, N.I., 1983. Differentiation of Volcanogenic Sulfide Deposits. Moscow State Uni.
Press, Moscow, p. 256.
Essaifi, A., Goodenough, K., Tornos, F., Outigua, A., Ouadjou, A., Maacha, L., 2019. The
Moroccan massive sulfide deposits: evidence for polyphase mineralization. Minerals
9, 1–31. https://doi.org/10.3390/min9030156.
Franklin, J.M., Gibson, H.L., Jonasson, I.R., Galley, A.G., 2005. Volcanogenic Massive
Sulphide Deposits. 100th Anniversary Volume. The Economic Geology Publishing
Company. 523–560.
Franklin, J.M., Sangster, D.M., Lydon, J.W., 1981. Volcanic-associated massive sulfide
deposits: Econ. Geol. 75th Ann. Vol. pp. 485–627.
Franklin, J.M., 1993. Volcanic-associated massive sulfide deposits, in Kirkham. R.V.,
Sinclair, W.D., Thorpe, R.I., and Duke, J.M., eds., Mineral deposit modeling, Geol.
Ass. Can. Sp. Paper 40, 315–334.
Frenzel, M., Hirsch, T., Gutzmer, J., 2016. Gallium, Germanium, Indium, and other trace
and minor elements in sphalerite as a function of deposit type – a meta-analysis. Ore
Geol. Rev. 76, 52–78. https://doi.org/10.1016/j.oregeorev.2015.12.017.
Galley, A.G., Hannington, M.D., Jonasson, I.R., 2007. Volcanogenic massive sulfide
deposits, in Goodfellow, W.D., ed., Mineral Deposits of Canada: A Synthesis of Major
Deposit-Types, District Metallogeny, the Evolution of Geological Provinces, and
Exploration Methods: Geological Association of Canada, Mineral Deposits Division,
Sp. Pub. 5, 141–161.
Genna, D., Gaboury, D., 2015. Deciphering the hydrothermal evolution of a VMS System
by LA-ICP-MS using trace elements in pyrite: an example from the Bracemac-McLeod
deposits, Abitibi, Canada implications for exploration. Econ. Geol. 110, 2087–2108.
https://doi.org/10.2113/econgeo.110.8.2087.
George, L.L., Cook, N.J., Ciobanu, C.L., 2016. Partitioning of trace elements in co-
crystallized sphalerite-galena-chalcopyrite hydrothermal ores. Ore Geol. Rev. 77,
97–116. https://doi.org/10.1016/j.oregeorev.2016.02.009.
B.P. Mishra et al.
Ghosh, B., Praveen, M.N., 2008. Indicator minerals as guides to base metal sulfide
mineralization in Betul Belt, central India. J. Earth Syst. Sci. 117, 521–536. https://
doi.org/10.1007/s12040-008-0050-x.
Golani, P.R., Dora, M.L., 2003. A report of polymetallic sulfide mineralization and
associated hydrothermal alteration in Bhuyari area, Chhindwara district, Geol. Surv.
Ind., www.gsi.gov.in.
Golani, P.R., Dora, M.L., Bandyopadhyay, B.K., 2006. Base metal mineralization
associated with hydrothermal alteration in felsic volcanic rocks in Proterozoic Betul
Belt at Bhuyari, Chhindwara district, Madhya Pradesh. J. Geol. Soc. Ind. 68,
797–808.
Govindarao, B., Pruseth, K.L., Mishra, B., 2018. Sulfide partial melting and chalcopyrite
disease: An experimental study. Am. Mineral. 103, 1200–1207. https://doi.org/
10.2138/am-2018-6477.
Hannington, M.D., Bleeker, W., Kjarsgaard, I., Huston, D.L., Sie, S.H., Suter, G.F.,
Cooke, D.R., Both, R.A., 1999a. Trace elements in sulfide minerals from eastern
Australian volcanic-hosted massive sulfide deposits; Part I, Proton microprobe
analyses of pyrite, chalcopyrite, and sphalerite, and Part II, Selenium levels in pyrite;
comparison with delta 34S values and Giant Kidd Creek Volcanogenic Massive
Sulfide Deposit. West. Abitibi Subprov. Canada 10. https://doi.org/10.5382/
Mono.10.08.
Hannington, M.D., Poulsen, K.H., Thompson, J.F.H., Sillitoe, R.H., 1999b. Volcanogenic
gold in the massive sulfide environment, in Barrie, C.T., and Hannington, M.D.,
Volcanic-Associated Massive Sulfide Deposits: Processes and Examples in Modern
and Ancient Settings: Reviews in Econ. Geol. 8, pp. 319–350.
Harris, L.B., 1993. Correlations of tectonothermal events between the Central Indian
Tectonic Zone and the Albany Mobile Belt of Western Australia. Gondwana
assembly, evolution, and dispersal, 165-180.
Hemraj, S., Nambiar, K.V., 2007. Final report on prospecting for base metals in Biskhan
Block of Betul district, Madhya Pradesh. Geol. Surv. Ind. www.gsi.gov.in.
Herrmann, W., Hill, A.P., 2001. The Origin of Chlorite-Tremolite-carbonate rocks
associated with the thalanga volcanic-hosted massive sulfide deposit, North
Queensland, Australia. Econ. Geol. 96, 1149–1173.
Hoefs, J., 2009. Stable Isotope Geochemistry, sixth ed. Springer-Verlag, Berlin,
Heidelberg.
Huston, D.L., 1997. Stable isotopes and their significance for understanding the genesis
of volcanic-hosted massive sulphide deposits: A Review. In Volcanic Associated
Massive Sulfide Deposits: Processes and Examples in Modern and Ancient Settings.
(A volume to accompany a GAC-MDD-SEG co-sponsored short course).
Huston, D.L., 1999. Stable isotopes and their significance for understanding the genesis
of volcanic-hosted massive sulfide deposits: a review. Rev. in Econ. Geol. 8,
157–180.
Huston, D.L., Sie, S.H., Suter, G.F., Cooke, D.R., Both, R.A., 1995. Trace elements in
sulfide minerals from eastern Australian volcanic-hosted massive sulfide deposits:
part I. Proton microprobe analyses of pyrite, chalcopyrite, and sphalerite, and part II.
Selenium levels in pyrite: comparison with δ34S values and implications for the
source of sulfur in volcanogenic hydrothermal systems. Econ. Geol. 90, 1167–1196.
https://doi.org/10.2113/gsecongeo.90.5.1167.
Hutchison, M.N., Scott, S.D., 1981. Sphalerite geobarometry in the Cu–Fe–Zn–S system.
Econ. Geol. 76, 143–153.
Keith, M., Häckel, F., Haase, K.M., Schwarz-Schampera, U., Klemd, R., 2016. Trace
element systematics of pyrite from submarine hydrothermal vents. Ore Geol. Rev.
72, 728–745. https://doi.org/10.1016/j.oregeorev.2015.07.012.
Keith, M., Smith, D.J., Jenkin, G.R.T., Holwell, D.A., Dye, M.D., 2018. A review of Te and
Se systematics in hydrothermal pyrite from precious metal deposits: insights into
ore-forming processes. Ore Geol. Rev. 96, 269–282. https://doi.org/10.1016/j.
oregeorev.2017.07.023.
Knorsch, M., Nadoll, P., Klemd, R., 2020. Trace elements and textures of hydrothermal
sphalerite and pyrite in Upper Permian carbonates of the North German Basin.
J. Geoch Expl. 209, 93.
Kullerud, G., 1953. The FeS-ZnS System, a geological thermometer. Nor. Geol. Tidsskr.
32, 61–147.
Kumari, S., Panda, B., 2018. Exploration for base-metal mineralization in Jangaldehri
block, Betul Belt, Chhindwara district, M.P. Geol. Surv. Ind. Rec. 151–6, 160–161.
L’Heureux, I., 2000. Origin of banded patterns in natural sphalerite. Phys. Rev. E - Stat.
Physics, Plasmas, Fluids. Relat. Interdiscip. Top. 62, 3234–3245. https://doi.org/
10.1103/PhysRevE.62.3234.
Langevin, P.M., Hannington, M.D., Valerie Becu, B.D., 2011. The gold content of
volcanogenic massive sulfide deposits. Miner. Depos. 46, 509–539. https://doi.org/
10.1007/s00126-010-0300-0.
Large, R.R., 1992. Australian massive sulfide deposits: features, styles, and genetic
model. Econ. Geol. 87, 471–510.
Large, R.R., Danyushevsky, L., Hollit, C., Maslennikov, V., Meffre, S., Gilbert, S., Bull, S.,
Scott, R., Emsbo, P., Thomas, H., Singh, B., Foster, J., 2009. Gold and trace element
zonation in pyrite using a laser imaging technique: Implications for the timing of
gold in orogenic and Carlin-style sediment-hosted deposits. Econ. Geol. 104,
635–668. https://doi.org/10.2113/gsecongeo.104.5.635.
Large, R.R., Halpin, J.A., Danyushevsky, L.V., Maslennikov, V.V., Bull, S.W., Long, J.A.,
Gregory, D.D., Lounejeva, E., Lyons, T.W., Sack, P.J., McGoldrick, P.J., Calver, C.R.,
2014. The trace element content of sedimentary pyrite as a new proxy for deep-time
ocean-atmosphere evolution. Earth Planet. Sci. Lett. 389, 209–220. https://doi.org/
10.1016/j.epsl.2013.12.020.
Larocque, A.C.L., Hodgson, C.J., Cabri, L.J., Jackman, J.A., 1995. Ion-microprobe
analysis of pyrite, chalcopyrite and pyrrhotite from the Mobrun VMS deposit in
northwestern Quebec; evidence for metamorphic remobilization of gold. Can. Min.
33, 373–388.
24
Ore Geology Reviews 134 (2021) 104149
Lentz, D.R., 1998. Petrogenetic evolution of felsic volcanic sequences associated with
Phanerozoic volcanic-hosted massive sulfide systems: the role of extensional
geodynamics. Ore Geol. Rev. 12, 289–327. https://doi.org/10.1016/S0169-1368
(98)00005-5.
Lentz, D.R., 1999. Petrogenetic evolution of felsic volcanic sequences associated with
Phanerozoic volcanic-hosted massive sulphide systems: the role of extensional
geodynamics. Ore Geol. Rev. 12–5, 289–327.
Lentz, D.R., 2002. Sphalerite and arsenopyrite at the Brunswick No. 12 massive-sulfide
deposit, Bathurst Camp, New Brunswick: constraints on P-T evolution. Can. Mineral.
40–1, 19–31.
Lesher, C.M., Goodwin, A.M., Campbell, I.H., Gorton, M.P., 1986. Trace-element
geochemistry of ore-associated and barren, felsic metavolcanic rocks in the Superior
Province, Canada. Can. J. Earth Sci. 23, 222–237. https://doi.org/10.1139/e86-025.
Lin, J., Liu, Y., Yang, Y., Hu, Z., 2016. Calibration and correction of LA-ICP-MS and LA-
MC-ICP-MS analyses for element contents and isotopic ratios. Solid Earth Sci. 1,
5–27. https://doi.org/10.1016/j.sesci.2016.04.002.
Lockington, J.A., Cook, N.J., Ciobanu, C.L., 2014. Trace and minor elements in sphalerite
from metamorphosed sulfide deposits. Mineral. Petrol. 108, 873–890. https://doi.
org/10.1007/s00710-014-0346-2.
Longerich, H.P., Jackson, S.E., Günther, D., 1996. Laser ablation inductively coupled
plasma mass spectrometric transient signal data acquisition and analyte
concentration calculation. J. Anal. At. Spectrom. 11, 899–904. https://doi.org/
10.1039/JA9961100899.
Lusk, J., Scott, S.D., Ford, C.E., 1993. Phase relations in the Fe–Zn–S system to 5 kbars
and temperatures between 325◦ and 150 ◦ C. Econ. Geol. 88, 1880–1903.
Lydon, J.W., 1984. Ore deposit models #14, Volcanogenic massive sulfide deposits. Part
I: A descriptive model. Geosci. Can. 11, 195–202.
Mahakud, S.P., Raut, P.K., Hansda, C., Ramteke, P.F., Chakraborty, U., Praveen, M.N.,
Sisodiya, D.S., 2001. Sulfide mineralization in the central part of Betul Belt around
Ghisi-Mouriya-Koparpani area, Betul district, Madhya Pradesh. Geol. Surv. Ind. Spl.
Pub. 64, 377–385.
Maslennikov, V.V., Maslennikova, S.P., Large, R.R., Danyushevsky, L.V., 2009. Study of
Trace Element Zonation in Vent Chimneys from the Silurian Yaman-Kasy Volcanic-
Hosted Massive Sulfide Deposit (Southern Urals, Russia) Using Laser Ablation-
Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS). Econ. Geol. 104,
1111–1141. https://doi.org/10.2113/gsecongeo.104.8.1111.
McClenaghan, S.H., Lentz, D.R., Martin, J., Diegor, W.G., 2009. Gold in the Brunswick
No. 12 volcanogenic massive sulfide deposit, Bathurst Mining Camp, Canada:
Evidence from bulk ore analysis and laser ablation ICP-MS data on sulfide phases.
Miner. Depos. 44, 523–557. https://doi.org/10.1007/s00126-009-0233-7.
Mishra, M.N., Vishwakarma, L.L., Ghosh, B., 2009. Report on the investigation in the
unexplored parts of the Betul Belt with emphasis on demarcating the host rock units
of base metal mineralization in Betul and Chhindwara districts, Madhya Pradesh.
Geol. Surv. Ind. www.gsi.gov.in.
Moller, P., 1987. Correlation of homogenization temperatures of accessory minerals from
sphalerite-bearing deposits and Ga/Ge model temperatures. Chem. Geol. 61,
153–159. https://doi.org/10.1016/0009-2541(87)90035-0.
Mondillo, N., Boni, M., Joachimski, M., Santoro, L., 2017. C-O stable isotope
geochemistry of carbonate minerals in the nonsulfide zinc deposits of the middle
east: a review. Minerals 7, 1–13. https://doi.org/10.3390/min7110217.
Mukherjee, I., Large, R., 2017. Application of pyrite trace element chemistry to
exploration for SEDEX style Zn-Pb deposits: McArthur Basin, Northern Territory,
Australia. Ore Geol. Rev. 81, 1249–1270. https://doi.org/10.1016/j.
oregeorev.2016.08.004.
Naqvi, S.M., Rogers, J.W., 1987. Precambrian Geology of India, viii + 223 pp. Clarendon
Press; Oxford Uni. Pr, New York, Oxford. ISBN 0 19 503653 0.
Ohmoto, H., 1972. Systematics of sulfur and carbon isotopes in hydrothermal ore
deposits. Econ. Geol. 67, 551–578.
Ohmoto, H., 1996. Formation of volcanogenic massive sulfide deposits: the Kuroko
perspective. Ore Geol. Rev. 10, 135–177. https://doi.org/10.1016/0169-1368(95)
00021-6.
Pasava, J., Frimmel, H., Vymazalová, A., Dobes, P., Jukov, A.V., Koneev, R.I., 2013.
A two-stage evolution model for the Amantaytau orogenic-type gold deposit in
Uzbekistan. Miner. Depos. 48, 825–840. https://doi.org/10.1007/s00126-013-0461-
8.
Paul, D., Skrzypek, G., 2007. Assessment of carbonate-phosphoric acid analytical
technique performed using GasBench II in continuous flow isotope ratio mass
spectrometry. Int. J. Mass Spect. 262, 180–186. https://doi.org/10.1016/j.
ijms.2006.11.006.
Pearce, N.J.G., Perkins, W.T., Westgate, J.A., Gorton, M.P., Jackson, S.E., Neal, C.R.,
Chenery, S.P., 1997. A compilation of new and published major and trace element
data for NIST SRM 610 and NIST SRM 612 glass reference materials. Geostand.
Geoanalyt. Res. 21–1, 115–144. https://doi.org/10.1111/j.1751-908x.1997.
tb00538.x.
Perkins, G.B., Sharp, Z.D., Selverstone, J., 2006. Oxygen isotope evidence for subduction
and rift-related mantle metasomatism beneath the Colorado Plateau-Rio Grande rift
transition. Cont. Min. Petr. 151, 633–650. https://doi.org/10.1007/s00410-006-
0075-6.
Piercey, S.J., 2011. The setting, style, and role of magmatism in the formation of
volcanogenic massive sulfide deposits. Miner. Depos. 46, 449–471. https://doi.org/
10.1007/s00126-011-0341-z.
Piercey, S.J., 2009. An overview of petrochemistry in the regional exploration for
volcanogenic massive sulfide (VMS) deposits. Geoch Explor. Environ. Anal. 10, 1–18.
https://doi.org/10.1144/1467-7873/09-221.
Pouchou, L., Pichoir, F., 1984. A new model for quantitative X-ray microanalysis. Rech.
Aerospatiale 3, 167–192.
B.P. Mishra et al.
Praveen, M.N., Ghosh, B., 2009. Submarine volcanic facies and its implication as a
possible tracker of sulfide mineralization - a study from Jilharidev area, Betul belt,
central India. Curr. Sci. 97, 670–679.
Praveen, M.N., Ghosh, B., Shrivastava, H.S., Dora, M.L., Gaikwad, L.D., 2007. Sulfide
mineralisation in Betul Belt: classification and general characteristics. J. Geol. Soc.
India 69, 85–91.
Praveen, M.N., Ghosh, B., Shrivastava, H.S., Kumaran, G.S., Roy, S., Sisodiya, D.S., 2005.
Metamorphic mineral assemblages associated with sulfide mineralization in Betul
belt: a possible hydrothermal origin. Proceeding Vol. 1st Indian Miner. Congr.
Showcasing Indian Miner. Ind. 21st Century (eds Sinha, A. Singh, S. K.), ISM,
Dhanbad, India, Allied Publ. New Delhi. 193–218.
Praveen, M.N., Nambiar, C.G., Huston, D.L., 2020. Geochemistry and petrogenesis of
rhyolite hosted zinc-rich metamorphosed volcanogenic massive sulfide deposits in
the eastern Betul Belt, central India, Ore Geol. Rev. doi: https://doi.org/10.1016/j.
oregeorev.2020. 103918.
Quin, Z., 1987. Trace element in galena and sphalerite and their geochemical
significance in distinguishing the genetic types of Pb-Zn ore deposits. Chi. J. Geoch.
6, 177–190.
Radhakrishna, B.P., Naqvi, S.M., 1986. Precambrian continental crust of India and its
evolution. J. Geol. 94, 145–166.
Raut, P.K., Mahakud, S.P., 2004. Geology, geochemistry, and tectonic setting of the
volcano-sedimentary sequence of Betul belt, Madhya Pradesh, and genesis of zinc
and copper sulfide mineralisation. Geol. Surv. Ind. Sp. 133–146.
Raymond, O.L., 1996. Pyrite composition and ore genesis in the Prince Lyell copper
deposit, Mt Lyell mineral field, western Tasmania, Australia. Ore Geol. Rev. 10,
231–250. https://doi.org/10.1016/0169-1368(95)00025-9.
Raza, M.A., Naidu, V.S.S.A., 2018. Exploration for the base metal in Biskhan block, Betul
Belt, Betul District, M.P. Geol. Surv. Ind. Rec. 151–6, 155–156.
Raza, M.A., Shareef, M., Naidu, B.V.S.S.A., Suryavanshi, H., Baswani, S.R., Dora, M.L.,
Meshram, T., Akhter, P., Raghuram, Kumari, S., Panda, B., Saha, S.K., Maura, L.M.S.,
Sarkar, S.S., John, M.M., Sarala Bai, S.R., 2020. Multiple sulfur sources for the
volcanic-hosted massive sulfides in Betul Belt, Central India: evidence from the
sulfide ore chemistry and sulfur isotope geochemistry. Geochem. 80–4, 125632
https://doi.org/10.1016/j.chemer.2020.125632.
Revan, M.K., Genç, Y., Maslennikov, V.V., Maslennikova, S.P., Large, R.R.,
Danyushevsky, L.V., 2014. Mineralogy and trace-element geochemistry of sulfide
minerals in hydrothermal chimneys from the Upper-Cretaceous VMS deposits of the
eastern Pontide orogenic belt (NE Turkey). Ore Geol. Rev. 63, 129–149. https://doi.
org/10.1016/j.oregeorev.2014.05.006.
Rose, A.W., 1967. Trace elements in sulfide minerals from the Central district, New
Mexico, and the Bingham district. Utah. Geochim. Cosmochim. Acta 31, 547–585.
https://doi.org/10.1016/0016-7037(67)90034-8.
Roy, A., Chakraborti, K., 2001. Precambrian mafic-ultramafic magmatism in Central
Indian suture zone. J. Geol. Soc. of Ind. 72–1, 123–140.
Roy, A., Prasad, M.H., 2001. Precambrian of central India: a possible tectonic mode.
Geol. Surv. Ind. Sp. Pub. 64, I77–197.
Roy, A., Prasad, H.M., 2003. Tectonothermal events in Central Indian Tectonic Zone
(CITZ) and its implications in the Rodinia crustal assembly. J. Asian Earth Sci. 22,
115–129. https://doi.org/10.1016/S1367-9120(02)00180-3.
Roy, S.K., 2011. Possible VMS-Type Base Metal Mineralization at Pastalaimal and
associated alteration features: Implication for Identification of future targets in Betul
Belt, Central India. 17th Conv. Ind. Geol. Cong. Int. Confe. NPESMD 10–12.
Sakaki, A., Kajiwara, Y., 1971. Evidence of isotopic exchange between seawater sulfate
and some syngenetic ores. Soc. Mining Geol. Japan Spec. Is. 3, 289–294.
Seal, R.R., 2006. Sulfur isotope geochemistry of sulfide minerals. Rev. Min. Geochem. 61,
633–677. https://doi.org/10.2138/rmg.2006.61.12.
Shareef, M., Mahajan, M., Suryavanshi, H., 2011. Detailed petrographic studies of
mineralized zones, alteration zones, and associated rock types of Banskhapa,
Pipariya block in Betul belt, Madhya Pradesh. Geol. Surv. Ind. 142–144, 154–155.
Shields, G., Veizer, J., 2002. Precambrian marine carbonate isotope database: Version
1.1. Geochem. Geophys. Geosyst. 3–6 https://doi.org/10.1029/2001GC000266.
Solomon, M., Gemmell, J.B., Zaw, K., 2004. Nature and origin of the fluids responsible
for forming the Hellyer Zn-Pb-Cu, volcanic-hosted massive sulfide deposit,
Tasmania, using fluid inclusions and stable and radiogenic isotopes. Ore Geol. Rev.
25, 89–124. https://doi.org/10.1016/j.oregeorev.2003.11.001.
Spry, P.G., Marshall, B., Vokes, F.M., 2000. Metamorphosed and metamorphogenic
deposits. Rev. Econ. Geol. Eds. 11.
Steadman, J.A., Large, R.R., Olin, P.H., Danyushevsky, L.V., Meffre, S., Huston, D.,
Fabris, A., Lisitsin, V., Wells, T., 2020. Pyrite trace element behavior in magmatic-
25
Ore Geology Reviews 134 (2021) 104149
hydrothermal environments: An LA-ICPMS imaging study. Ore Geol. Rev. 10.1016/j.
oregeorev.2020.103878.
Sugaki, A., Kitakaze, A., Kojima, S., 1987. Bulk compositions of intimate intergrowths of
chalcopyrite and sphalerite and their genetic implications. Miner. Depos. 22, 26–32.
Taylor, B., 1987. Stable isotope geochemistry of ore forming fluids in Mineralogical
association of Canada, Short Course in Stable isotope geochemistry of low
temperature fluids, Mineralog. Asso. of Can. (Ed. T.K. Kyser).
Toshio, M., 1988. Compositional homogenization of sphalerite in hydrothermal ore
deposits of Japan by post-depositional diffusion processes: with particular reference
to metamorphosed Besshi-type deposits. Min. Geol. 38, 263–278.
Van den Boogaart, K.G., Tolosana-Delgado, R., 2013. Analyzing Compositional Data with
R. Springer, London, UK. 10.1007/978-3-642-36809-7.
Vokes, F.M., 1971. Some aspects of the regional metamorphic mobilization of preexisting
sulfide deposits. Min. Dep. 6, 122–129.
Vokes, F.M., 1966. On the possible models of origin of the Caledonian sulfide ore deposit
at Bleikvassli, Nordland. Norway. Econ. Geol. 61, 1130–1139.
Wagner, T., Klemd, R., Wenzel, T., Mattsson, B., 2007. Gold upgrading in
metamorphosed massive sulfide ore deposits: direct evidence from laser-ablation-
inductively coupled plasma-mass spectrometry analysis of invisible gold. Geol. 35,
775–778. https://doi.org/10.1130/G23739A.1.
Walshe, J.L., Solomon, M., 1981. An investigation into the environment of formation of
the volcanic-hosted Mt Lyell copper deposits using geology, mineralogy, stable
isotopes, and a six-component chlorite solid solution model. Econ. Geol. 76,
246–284. https://doi.org/10.2113/gsecongeo.76.2.246.
Wang, Jing-Yi, Santosh, M., Cheng-Xue, Yang, Nakagawa, M., 2021. Revisiting the type
area VMS deposit of Besshi, SW Japan: In-situ trace element chemistry, isotopes and
Re-Os age of sulfides. Ore Geol. Rev. 130 https://doi.org/10.1016/j.
oregeorev.2020.103955.
Wei, C., Huang, Z., Yan, Z., Hu, Y., Ye, L., 2018. Trace element contents in sphalerite
from the Nayongzhi Zn-Pb deposit, northwestern Guizhou, China: insights into
incorporation mechanisms, metallogenic temperature, and ore genesis. Minerals 8.
https://doi.org/10.3390/min8110490.
Whitney, D.L., Evans, B.W., 2010. Abbreviations for names of rock-forming minerals.
Am. Min. 95, 185–187.
Wilson, S.A., Ridley, W.I., Koenig, A.E., 2002. Development of sulfide calibration
standards for the laser ablation inductively-coupled plasma mass spectrometry
technique. J. Anal. At. Spectrom. 17, 406–409. https://doi.org/10.1039/b108787h.
Winderbaum, L., Ciobanu, C.L., Cook, N.J., Paul, M., Metcalfe, A., Gilbert, S., 2012.
Multivariate Analysis of an LA-ICP-MS Trace Element Dataset for Pyrite. Math.
Geosci. 44, 823–842. https://doi.org/10.1007/s11004-012-9418-1.
Xu, G., 1998. Geochemistry of sulfide minerals at Dugald River, NW Queensland, with
reference to ore genesis. Mineral. Petrol. 63, 119–139. https://doi.org/10.1007/
BF01162771.
Ye, L., Cook, N.J., Ciobanu, C.L., Yuping, L., Qian, Z., Tiegeng, L., Wei, G., Yulong, Y.,
Danyushevskiy, L., 2011. Trace and minor elements in sphalerite from base metal
deposits in South China: A LA-ICPMS study. Ore Geol. Rev. 39, 188–217. https://doi.
org/10.1016/j.oregeorev.2011.03.001.
Yousuf, I., Subba Rao, D.V., Balakrishnan, S., Ahmad, T., 2019. Geochemistry and
petrogenesis of acidic volcanics from Betul-Chhindwara Belt, Central Indian Tectonic
Zone (CITZ), central India. J. Earth Syst. Sci. 128 https://doi.org/10.1007/s12040-
019-1255-x.
Yuan, B., Zhang, C., Yu, H., Yang, Y., Zhao, Y., Zhu, C., Ding, Q., Zhou, Y., Yang, J.,
Xu, Y., 2018. Element enrichment characteristics: Insights from element
geochemistry of sphalerite in Daliangzi Pb–Zn deposit, Sichuan, Southwest China.
Jour. Geoch. Expl. 186, 187–201. https://doi.org/10.1016/j.gexplo.2017.12.014.
Zaw, K., Large, R.R., 1992. The precious metal-rich South Hercules mineralization,
western Tasmania: a possible subsea-floor replacement volcanic-hosted massive
sulfide deposit. Econ. Geol. 87, 931–952. https://doi.org/10.2113/
gsecongeo.87.3.931.
Zhang, J., Deng, J., Yong, H., Yang, Qiang, L., Cooke, D., Danyushevsky, L., Gong, Jie, Q.,
2014. LA-ICP-MS trace element analysis of pyrite from the Chang’an gold deposit,
Sanjiang region, China: implication for ore-forming process. Gond. Res. 26,
557–575. https://doi.org/10.1016/j.gr.2013.11.003.
Zheng, Y.F., Hoeffs, J., 1993. Carbon and oxygen isotopic variations in hydrothermal
calcites. Theoretical modelling on mixing processes and application to Pb-Zn
deposits in the Harz Mountains, Germany. Min. Dep. 28, 79–89.
Zhang, Q.L., Chang, T.L., Ding, T., 1989. Analysis of the reference material NBS-123 and
the atomic weight of sulfur. Chi. Sci. Bull. 34, 10.