Ore Geology Reviews 130 (2021) 103955

Contents lists available at ScienceDirect

Ore Geology Reviews

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

Revisiting the type area VMS deposit of Besshi, SW Japan: In-situ trace
element chemistry, isotopes and Re-Os age of sulfides
Jing-Yi Wang a, M. Santosh a, b, c, *, Cheng-Xue Yang a, M. Nakagawa d
a
School of Earth Sciences and Resources, China University of Geosciences Beijing, Beijing 100083, PR China
b
Department of Earth Sciences, University of Adelaide, Adelaide, SA, Australia
c
State Key Laboratory of Continental Dynamics, Department of Geology, Northwest University, Northern Taibai Str.229, Xi’an 710069, China
d
Faculty of Science, Kochi University, Kochi 780-8520, Japan

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

Keywords: The Besshi Cu-rich volcanogenic massive sulfide (VMS) deposit occurring in the type area of Besshi, central
Besshi-type deposit Shikoku, Southwest Japan comprises tabular orebodies closely associated with mafic schist in the Cretaceous
VMS deposit Sambagawa high P/T metamorphic belt. Pyrite, chalcopyrite, and sphalerite are the dominant sulfide minerals,
Re-Os isotope
together with minor amounts of pyrrhotite and bornite. The associated greenstone samples show geochemical
Sulfur isotope
Trace element
features between N-MORB and E-MORB. The δ34S values of sulfides from the greenstones and Cu ores are in the
range of 2.10 to 7.11‰, indicating deposition from hydrothermal fluids with a heterogeneous metal source. Re-
Os analysis of sulfides show initial (187Os/188Os)i ratio of 1.14 ± 0.86 and yield an isochron age of 147.9 ± 4.2
Ma, considered as the timing of sulfide deposition on the paleo-seafloor. The lithological association,
geochemical features of the host greenstones and isotopic data from the sulfides indicate that the Besshi-type ores
formed in a pelagic setting, and are possibly associated with hydrothermal activity related to mid ocean ridge
volcanism and can be correlated to a major oceanic anoxic event.

1. Introduction include Sturgeon Lake, Abcourt, Chisel Lake, and Kidd Creek (Franklin
et al., 2005; Badrzadeh et al., 2011; Maghfouri et al., 2016).
Volcanogenic massive sulfide (VMS) deposits form at or near the The second type of VMS deposits is the mafic-backarc type (Cyprus
seafloor and represent polymetallic mineralization formed in the sub­ type). They usually form in mature ocean-ocean backarc or obducted
marine volcanic environment (Galley et al., 2007). Major VMS type oceanic spreading ridges. The major rocks associated with these deposits
deposits occur in various parts of the world and are of diverse ages. They are MORB to LILE and LREE-enriched tholeiites, or ocean island basalts.
are important resources for copper, and also supply a substantial volume The ores are either massive sulfides or occur as prominent Cu-stringer
of the world’s zinc and silver, in addition to Ge and In. zones. Global examples are Cyprus, Oman and Lokken in Norway
The VMS deposits are broadly divided into five types (Franklin et al., (Rastad et al., 2002; Franklin et al., 2005).
2005; Galley et al., 2007). The first one is the bimodal mafic-dominated The third type of VMS deposits is the bimodal felsic-dominated type
volcanic type (Noranda type) which is usually associated with ocean- (Kuroko type). They usually form in the ocean-continent arc or nascent
ocean suprasubduction arc (Badrzadeh et al., 2011). This group has arc rifting. The ore shows bulbous to tabular massive sulfides, pyrites as
been divided into two subgroups: flow dominant deposits such as Zn-Cu well as limited Cu-stringer zones. Kuroko, Skellefte, Sturgeon Lake,
deposits on the seafloor and pyroclastic dominant deposits on the sub- Buchans and Buttle Lake are all examples of bimodal felsic-dominated
sea floor which include Zn-Cu, Cu, and Ag deposits. The flow domi­ VMS deposits (Franklin et al., 2005; Yarmohammadi, 2006).
nant deposits are correlated with ocean-ocean arc or nascent arc rifting. The fourth type of VMS deposits is the felsic siliciclastic hosted type
The global examples of this type include those of Noranda, Mattgami, (Bathursy type) which usually form in mature ocean-continent backarc.
Snow Lake, Norwegian, and Caledonides among others. In the bimodal The ores are tabular massive sulfides, pyrites and pyrrhotite as well as
mafic dominated volcaniclastic type deposits, the ores show massive minor Cu-stringer zones. Bathurst, Iberia and Kazakhstan are all exam­
sulfides tabular, pyrite and limited Cu-stringer zones, and examples ples of felsic siliciclastic hosted VMS deposits (Franklin et al., 2005;

* Corresponding author at: School of Earth Sciences and Resources, China University of Geosciences Beijing, Beijing 100083, PR China.
E-mail address: [email protected] (M. Santosh).

https://doi.org/10.1016/j.oregeorev.2020.103955
Received 25 September 2020; Received in revised form 16 December 2020; Accepted 21 December 2020
Available online 25 December 2020
0169-1368/© 2020 Elsevier B.V. All rights reserved.
J.-Y. Wang et al. Ore Geology Reviews 130 (2021) 103955

Mousivand et al., 2011; Maghfouri et al., 2016). ages of pyrite from the type area of the deposit in Besshi. The Re-Os
The last type of VMS deposits is the pelitic-mafic back arc type de­ isotope system has been shown to be a robust tool for dating sulfide
posit which is also called the Besshi-type deposit. These deposits usually minerals (e.g., Walker et al., 1994; Morelli et al., 2005; Kato et al., 2009;
form in mature ocean-ocean back arc. They are associated with pelitic to Selby et al., 2009; Tang et al., 2021). The laser-based in situ analysis of
semi-pelitic distal rocks, minor siliciclastic sediments, tholeiitic basalts, trace elements in sulfides provides another modern tool to evaluate the
MORB to LILE and LREE-enriched rocks, or ocean island basalts. The ore genesis (Tang et al., 2019). Our results provide further insights into
ores occur as tabular pyrites and pyrrhotites with the deposit showing the characteristics and timing of formation of the VMS deposits in the
minor Cu-stringer zones in association with sediments, chert and iron type area of Besshi.
formations. The global examples of this type of deposits are Besshi and
Windy Craggy. (Peter and Scott, 1999; Franklin et al., 2005; Maghfouri 2. Geological setting
et al., 2016).
The Besshi-type deposits in Japan show a close association with The Japanese islands were part of mainland Asia before the opening
mafic schist (basalt) and occur as deformed stratiform or lenticular ore of the Japan Sea or the Kurile Basin in the Miocene and the opening of
beds that were metamorphosed together with host rocks, with a domi­ the Okinawa Trough (e.g., Maruyama et al., 1997; Isozaki et al., 2010).
nant ore assemblage of pyrite with minor amounts of chalcopyrite, Japan is located at the junction of four tectonic plates: the Eurasian,
sphalerite, and pyrrhotite (Kase and Yamamoto, 1988; Nozaki et al., Pacific, North American, and Philippine. The Pacific plate is subducting
2010). The type locality is the Besshi deposit in the Sambagawa meta­ at a rate of 10 cm/yr underneath NE Japan, with its leading slab down to
morphic belt in central Shikoku island of SW Japan, where more than 660 km depth under Beijing, China, as detected seismologically (Mar­
100 deposits have been traced within the Sambagawa metamorphic belt. uyama et al., 2007). The Philippine Sea plate is subducting from SE to
Following the early report of Francheteau et al. (1979) on hydrothermal NW with 4 cm/yr under SW Japan along the Nankai trough (trench) and
massive sulfide deposits on the East Pacific Rise, several studies have Ryukyu trench off SW Japan. NE Japan collides against SW Japan along
attempted to compare the Besshi-type deposits with modern seafloor the over 2000 m-high mountains that are called Japan Alps that stretch
sulfide deposits. It has been concluded that the Besshi-type deposits across the arc in the central part of the main island (Isozaki et al., 2010).
represent the ancient counterparts of Cu-rich seafloor massive sulfide The study area in Besshi is located in the Kochi prefecture of Shikoku
deposits (e.g., Koski, 1990; Sato and Kase, 1996; Kase, 2003). island in SW Japan (Fig. 1). The Besshi-type metamorphosed massive
Precise geochronological and geochemical data are essential to gain sulfide deposits (Fig. 2), occur within the Sambagawa metamorphic belt
insights on the tectonic setting and genetic environment of the Besshi- extending from Shizuoka Prefecture (Kune, Minenosawa), through
type deposits. With this objective, in this paper we present results Wakayama (Iimori) to Ehime Prefecture (Shingu, Besshi) and are
from our studies on trace element chemistry, sulfur isotopes and Re-Os correlated with Jurassic submarine basaltic volcanism (Ishihara and

Fig. 1. Geological map of SW Japan (modified after Hada et al., 2001) showing the study area marked by a box. Inset shows the Japanese island and the area covered
in the main figure.

2
J.-Y. Wang et al. Ore Geology Reviews 130 (2021) 103955

Fig. 2. Geological map of the study area showing the Besshi mine and surrounding lithology. Sample locations are also shown.

Endo, 2007). belt. The Sambagawa belt is considered to be part of an accretionary

The Besshi copper mine in the Niihama City of central Shikoku complex derived from oceanic crust with pelagic sediments and trench
(Fig. 1), operated by the Sumitomo Group produced 700,000 tons of turbidites (Isozaki et al., 2010). The Besshi deposit is the largest
copper from 1691 to 1973 (Nakagawa, 2013). Total mine output from cupriferous deposit in Japan, and the tabular ore body of the massive
1691 to 1973 in Besshi mine was approximately 30 million tons with sulfide ore ranging in thickness from a few tens of cm to meters occurs
total copper of around 7.6 million tons, with an average grade of ca. between mafic schist and quartz schist (Fig. 3a; Nakagawa, 2013). The
2.5% (Nakagawa, 2013). foot wall and hanging wall are dominantly quartz schist (Kase and
The Sambagawa metamorphic belt that hosts the Besshi-type de­ Yamamoto, 1988). The ore mainly consists of pyrite and chalcopyrite
posits occurs within the Cretaceous orogenic core and has been the topic with sphalerite and bornite as accessory minerals. The Besshi sulfide
of several previous investigations including metamorphic history (e.g., deposit is considered to be of hydrothermal origin, formed by the mid-
Banno and Sakai, 1989; Otsuki and Banno, 1990) and the emplacement oceanic ridge volcanism and later been accreted onto the proto­
mechanism of high pressure rocks (Okamoto et al., 2000; Terabayashi –Japanese Island by underplating (Nakagawa, 2013). Thin slivers of
et al., 2005), although the tectonic setting of the Sambagawa Belt is still greenstone, mafic schist, calcareous schist and banded ore are associated
unsure and controversial (Nozaki et al., 2006; Isozaki et al., 2010). with the ore body and were co-folded (Fig. 3a). Conformable massive
Many bedded cupriferous iron sulfide deposits are associated with sulfide deposit occurs within pelitic and mafic schists of the Sambagawa
the mafic schists in the Cretaceous Sambagawa high P/T metamorphic metamorphic belt, with thin beds of siliceous schists at the footwall and

Fig. 3. (a) Occurrence of the cupriferous iron sulfide ore in the Besshi deposit (after Doi, 1961; Nakagawa, 2013), (b) Geologic cross section of the massive sulfide
deposit of the Besshi mine (modified from Kase, 1988).

3
J.-Y. Wang et al. Ore Geology Reviews 130 (2021) 103955

hanging wall (Fig. 3b; Kase, 1988). In the type area around Besshi, the of the sulfide from representative samples. A summary of the analytical
deposit was estimated to extend for around 1800 m along the strike techniques employed is given below.
(N40◦ W-N70◦ W) and over 2500 m down the dip (45◦ -70◦ N). Two layers
of massive sulfide ores and a layer of banded ores in between were
3.1. Geochemistry
identified. The banded ores consist of thin alternation of quartz-chlorite
rich and sulfide-rich layers with the body showing the thickness of 2 to 3
Two representative greenstone samples including BSH-1-1 and BSH-
m (Kase, 1988).
2-1B were analyzed for major and trace elements.
Samples in this study were gathered from the abandoned mines and
Major elements were analyzed at the Wuhan Sample solution
surrounding areas in the type area Besshi in Niihama Prefecture, within
Analytical Technology Co., Ltd., Wuhan on whole rock powders using an
the Sambagawa Belt in the Shikoku Island (Figs. 1 and 2), with the
XRF (Primus II, Rigaku, Japan). The sample powder (200 mesh) was
objective to constrain the timing of ore mineralization and to evaluate
placed in an oven at 105 ◦ C and dried for 12 h. And ~1.0 g of the dried
the genesis and source of pyrite. The Sambagawa Belt in Shikoku is
sample was placed in a ceramic crucible and then heated in a muffle
composed of the Kawaguchi, Koboke, Minawa and Ojoin Formations in
furnace at 1000 ◦ C for 2 h. After cooling to 400 ◦ C, the sample was
ascending order (Nozaki et al., 2006).
placed in the drying vessel and weighed again to estimate the loss on
Our samples were collected from a stream bed exposure near an old
ignition (LOI). 0.6 g sample powder was mixed with 6.0 g cosolvent
mine adit (Fig. 4a). The dominant rock type is fine grained, thinly lu­
(Li2B4O7 : LiBO2 : LiF = 9:2:1) and 0.3 g oxidant (NH4NO3) in a Pt
minous schistose greenstone. The rock is dominantly composed of
crucible, which was placed in the furnace at 1150 ◦ C for 14 min. The
greenish chlorite, hornblende, plagioclase and epidote. The greenstone
melted sample was quenched with air for 1 min to produce flat discs on
carries thin bands and intercalations of black schist as well as quartz
the fire brick for the XRF analyses.
mica schist. Several blocks of cupriferous ore bearing rocks occur in this
An Agilent 7700e ICP-MS housed at the Wuhan Sample Solution
locality. These ores are medium to fine grained and show layered
Analytical Technology Co., Ltd., Wuhan, China was used for element
structures. Abundant sulfide minerals are present (Fig. 4b). Sulfide ore
analysis. The sample powder (200 mesh) was placed in an oven at 105 ◦ C
occurs as lenticular bodies within the layers of quartz schist sandwiched
for drying 12 h, following which 50 gm was weighed into a Teflon bomb.
between thick layers of greenschist and black schist.
And 1 ml HNO3 and 1 ml HF were added into the Teflon bomb. The
The cupriferous greenstone is medium to fine grained showing thin
Teflon bomb was placed in a stainless steel pressure jacket and heated to
banding and associated with abundant euhedral to subhedral medium to
190 ◦ C in an oven for >24 h. After cooling, the Teflon bomb was opened
fine grained fresh sulfide minerals (Fig. 4c and d). The cupriferous
and placed on a hotplate at 140 ◦ C and evaporated to incipient dryness,
greenstones probably represent the original or primary ore association.
and then 1 ml HNO3 was added and evaporated to dryness again. Then 1
ml of HNO3, 1 ml of MQ water and 1 ml internal standard solution of 1
3. Analytical techniques
ppm In were added, and the Teflon bomb was resealed and placed in the
oven at 190 ◦ C for >12 h. The final solution was transferred to a poly­
In this study, we obtained data from petrography, host rock
ethylene bottle and diluted to 100 g by the addition of 2% HNO3.
geochemistry, trace elements and S isotope of pyrite, and Re-Os isotopes
The analytical data are given in Supplementary Table 1.

Fig. 4. Representative field photographs. (a) Steam bed exposures of Besshi type greenstone assemblage. The bridge on the top leads to mine entrance. (b) Cu-ore
sample showing abundant pyrite (BSH-1-3), (c) Cu-ore sample showing abundant pyrite (BSH-1-5), (d) greenstone sample showing pyrite (BSH-2-3).

4
J.-Y. Wang et al. Ore Geology Reviews 130 (2021) 103955

3.2. Trace elements in pyrite at –50 to –80 ◦ C in an ethanol-liquid nitrogen slush; the top is sealed
using an oxygen-propane torch. The tube was then placed in a stainless-
Pyrite grains separated from representative Cu-ore and greenstones steel jacket and heated for 10 h at 230 ◦ C. Upon cooling, the bottom part
from Besshi (samples BSH-1-2A, BSH-1-3, BSH-1-5, BSH-2-1A, BSH-2-2) of the tube was frozen, the neck of the tube is broken, and the contents of
were analyzed for trace elements. the tube were transferred into a distillation flask and the residue was
The samples were mounted in 25 mm diameter epoxy discs together washed out with 40 ml of water.
with standard Sierra for analyses. Standard blocks (cast separately to be For the distillation of Os: Os, in the first step, OsO4 was distilled at
reused) were made by mounting 1 to 2 grain fragments of pyrite. Two 105–110 ◦ C for 50 min and was trapped in 10 ml of water. The residual
sample mounts were polished to set the surfaces of the standard and Re-bearing solution was retained in a 50 ml beaker for Re separation.
sample blocks at the same level in the sample holder and then coated The water trapped solution plus 40 ml of water was distilled a second
with 30 nm of high purity gold. time. The OsO4 was distilled for 1 h and trapped in 10 ml of water which
Pyrite trace elements were analyzed with a Resonetics S-155-LR 193 was then analyzed by ICPMS (USA TJA POEMES) for the Os isotope
nm excimer laser ablation system coupled to an Agilent 7700x quad­ ratios. The Re-bearing solution was then evaporated to dryness, 1 ml of
rupole ICPMS, housed in the GeoHistory Facility (GHF), John de Laeter water was added, and heated to near-dryness twice. 10 ml of 20% NaOH
Centre, Curtin University, Perth, Australia. The methodology and were added to the residue followed by Re extraction with 10 ml of
analytical conditions were the as with those described in by Wang et al. acetone in a 120 ml Teflon separation funnel. The acetone phase was
(2018). Following 30 s background analysis, the samples were ablated washed with 2 ml of 20% NaOH, and transferred into 100 ml beaker that
for 50 s at a repetition rate of 7 Hz, using a 50 and 75 μm beam and laser contains 2 ml of water. The acetone phase and water were evaporated to
energy of 1.6 to 2.5 J cm− 2. The flow rates were tuned for a ThO/Th of dryness, and separated in 2% HNO3 for ICP-MS analysis of Re isotope
<0.5% in order to minimize the oxide polyatomic interferences. Ultra­ ratio. Cation-exchange resin was used to remove Na if the salt of the Re-
high purity He (0.68 L min− 1) and N2 (2.8 ml min− 1) were used to flush bearing solution is more than 1 mg/ml. Average blanks for the total
the sample cell, and high purity Ar was employed as the plasma carrier Carius tube procedure as described above are ca. 10 pg Re and ca. 1 pg
gas. The primary reference material was international glass standard Os.
GSD-1G for the computation of elemental concentrations and to correct
the instrument drift on all elements except Au. Laflamme Po726, which 4. Results
is the synthetic pyrrhotite doped with platinum group elements and Au,
which is a certified sulfide standard, was utilized as the primary stan­ 4.1. Petrography
dard for Au calculation. Stoichiometric 57Fe was used as the internal
standard element to correct the instrument drift. Standard blocks were The greenstone samples are highly schistose and thinly layered. The
run every 10 unknowns. The precision is better than 5% for most ele­ sulfide ores from the Besshi deposit are mostly fine-grained with pyrite
ments based on repeated analyses of secondary internal standards BCR- as the dominant sulfide (Fig. 5a). Chalcopyrite, and sphalerite together
2G (GeoReM: http://georem.mpch-mainz.gwdg.de/). Data were with minor amounts of pyrrhotite and bornite also occur.
collected on a total of 22 trace elements, including Ti, V, Mn, Ni, Cu, Zn, Polished sections under reflected microscope reveal euhedral to
Ga, Ge, As, Se, Mo, Ag, Cd, In, Sn, Sb, Te, W, Au, Hg, Pb, and Bi. subhedral pyrite grains (up to 1 mm) which are infilled with chalcopy­
rite, sphalerite, bornite, and pyrrhotite (Fig. 5b and c). Sample BSH-1–5
3.3. S isotopic analyses has more chalcopyrite/pyrrhotite (Fig. 5b) whereas sample BSH-1–6
shows a markedly smaller grain size of the sulfide minerals (0.01–0.4
Pyrite grains separated from representative Cu-ore and greenstones mm) (Fig. 5c). Sample BSH-2–3 is composed of pyrite and silicate
(BSH-1-2A, BSH-1-3, BSH-1-5, BSH-2-1A) were analyzed for S isotopes. minerals with very minor chalcopyrite infilling in the pyrite grains
A CAMECA IMS1280 large-geometry ion microprobe housed at the (Fig. 5d). Silicate minerals are contained in all sulfide ore samples
Centre for Microscopy, Characterization and Analysis, The University of (Fig. 5).
Western Australia was employed for the measurement of sulfur isotopic
compositions. The nuclear magnetic resonance regulation and sulfur 4.2. Host rock geochemistry
isotopes (32S, 33S and 34S) were measured by using a multicollector
Faraday cup detector. Following a 30 s pre-sputter by a ~2 nA Cs + Major and trace element data on the two representative greenstone
primary ion beam, secondary sulfur ions from the target samples were samples from Besshi are given in Table 1. The SiO2 contents are in the
extracted at − 10 kV and admitted to the mass spectrometer, with range of 44.70–44.81 wt%, and mostly comparable to the typical
automated centering of the secondary ion beam in the field aperture and basaltic SiO2 contents (SiO2 = 45–52 wt%) in spite of the metamorphic
entrance slit. The detailed analytical conditions were same with those overprint. The concentration of TiO2 which is one of the highly immo­
described in LaFlamme et al. (2016). Measurements of unknowns were bile elements is 0.68–0.93 wt%, and is similar to that of typical tholeiitic
interspersed with matrix-matched reference material Sierra pyrite (δ33S basalt (e.g., Winchester and Floyd, 1976). The rocks show relatively
= 1.09‰ and δ34S = 2.17‰; LaFlamme et al., (2016) to calibrate isotope moderate MgO (1.34–2.21 wt%), Na2O (2.99–4.10 wt%), CaO
ratios and monitor internal precision. (2.50–3.63 wt%) and Fe2OT3 (4.10–4.94 wt%), but low K2O (2.99–4.10
wt%) and P2O5 (0.13–0.23 wt%).
3.4. Re-Os isotopic analyses On the chondrite-normalized rare earth element (REE) plots (Fig. 6a)
(normalization after Sun and McDonough, 1989), the greenstone sam­
A total of 7 representative pyrite samples from Cu-ores (BSH-1-2A, ples show a relatively flat REE trend, comparing with the features be­
BSH-1-3, BSH-1-5) and greenstone (BSH-2-1, BSH-2-2, BSH-2-1A, BSH- tween N-MORB and E-MORB. In the primitive mantle normalized
2-1B) were selected for Re-Os isotopic analyses. spidergram (Fig. 6b), the rocks display a generally flat trend with partly
The Re-Os isotope analyses were conducted at the Re-Os Lab, Na­ serrated pattern which is also comparable to the features of N-MORB or
tional Center of Geoanalysis, Chinese Academy of Geological Sciences, E-MORB.
Beijing. The weighed sample was loaded in a Carius tube composed of
thick-walled borosilicate glass ampoule for sample digestion, following 4.3. Trace elements in pyrite
techniques described in Shirey and Walker (1995) and Du et al. (2001).
The mixed 190Os and 185Re spike solutions and 2 ml of 12 M HCl and 6 A total of 173 pyrite LA-ICPMS spot analyses were performed on
ml of 15 M HNO3 were loaded while the bottom part of the tube is frozen pyrite separates from five samples of the Besshi deposit, including 45

5
J.-Y. Wang et al. Ore Geology Reviews 130 (2021) 103955

Fig. 5. Representative reflected light photomicrographs illustrating the textural features of the sulfide ores. (a) Cu-ore sample dominated by pyrite grains (sample
BSH-1-3). (b) Cu-ore sample composed of rich sulfide with minor bornite, chalcopyrite and silicate minerals (sample BSH-1-5). (c) Cu-ore sample composed of
subhedral pyrite with minor pyrrhotite, sphalerite and silicate minerals (sample BSH-1-6). (d) Greenstone sample composed exclusively of pyrite with minor
chalcopyrite and infilled with silicate minerals (sample BSH-2-3). Mineral abbreviations: Py-pyrite; Ccp-chalcopyrite; Po-pyrrhotite; Brn-bornite; Sp-sphalerite.

Among the analyzed elements, Ag, Pb, Te and Bi show moderate

Table 1
levels in pyrite from sample BSH-1-2A with highly variable concentra­
Sample numbers, rock types, localities, GPS reading of samples collected for this
tions ranging from 0.02 to 9.55 ppm, 0.007 to 179 ppm, 288–12300 ppm
study.
and 0.0079 to 17.16 ppm, respectively (Table 1). Among all the samples,
Serial Sample Locality Rock type Coordinates pyrite from sample BSH-1-2A has the highest concentrations of Ti
No. No.
(1.67–3610 ppm, average 153 ppm), Ga (0.01–0.71 ppm, average 0.16
1 BSH-1-1 Besshi Greenstone N 33◦ 51′ 04.54′′ , E ppm), Se (1.93–313 ppm, average 26.88 ppm), Sn (0.01–1.61 ppm,
mine 133◦ 21′ 05.39′′
average 0.17 ppm) and W (0.002–2.91 ppm, average 0.19 ppm), and
2 BSH-1-2A Besshi Cu-ore N 33◦ 51′ 04.54′′ , E
mine 133◦ 21′ 05.39′′ lowest concentrations of Mo (0.005–49.6 ppm, average 3.93 ppm). Py­
3 BSH-1-3 Besshi Cu-ore N 33◦ 51′ 04.54′′ , E rite from sample BSH-1–3 has the highest concentration of Mn
mine 133◦ 21′ 05.39′′ (0.55–54.2 ppm, average 15.84 ppm), Sb (0.08–7.23 ppm, average 1.95
4 BSH-1-5 Besshi Cu-ore N 33◦ 51′ 04.54′′ , E ppm) and Te (30–2160 ppm, average 432 ppm), and lowest concentra­
mine 133◦ 21′ 05.39′′
5 BSH-1-6 Besshi Cu-ore N 33◦ 51′ 04.54′′ , E
tions of Ti (1.75–3.03 ppm, average 2.24 ppm), Ni (0.60–47.5 ppm,
mine 133◦ 21′ 05.39′′ average 18.47 ppm), Cu (5.07–8590 ppm, average 1152 ppm), In
6 BSH-1-7 Besshi Cu-ore N 33◦ 51′ 04.54′′ , E (0.0007–0.51 ppm, averaging 0.61 ppm), Sn (0.005–0.24 ppm, average
mine 133◦ 21′ 05.39′′ 0.04 ppm), Te (30–2160 ppm, averagi3 432 ppm) and Bi (0.02–8.83
7 BSH-1-8 Besshi Cu-ore N 33◦ 51′ 04.54′′ , E
ppm, average 1.32 ppm). Pyrite from sample BSH-1-5 has the highest
mine 133◦ 21′ 05.39′′
8 BSH-2-1A Besshi Greenstone N 33◦ 50′ 53.86′′ , E concentrations of V (0.03–27.79 ppm, average 3.12 ppm), Ni (5.82–286
mine 133◦ 23′ 05.75′′ ppm, average 76.74 ppm), Hg (105–6960 ppm, average 667.76 ppm)
9 BSH-2-1B Besshi Greenstone N 33◦ 50′ 53.86′′ , E and Bi (0.07–1201 ppm, average 11.64 ppm). Pyrite from sample BSH-2-
mine 133◦ 23′ 05.75′′ 2 has the highest concentrations of Zn (1.06–93900 ppm, average 3309
10 BSH-2-2 Besshi Greenstone N 33◦ 50′ 53.86′′ , E
mine 133◦ 23′ 05.75′′
ppm), As (1.53–0.33 ppm, average 72 ppm), Mo (0.01–653 ppm,
11 BSH-2-3 Besshi Greenstone N 33◦ 50′ 53.86′′ , E average 57.37 ppm), Ag (0.09–69 ppm, average 3.72 ppm), Cd
mine 133◦ 23′ 05.75′′ (0.01–190.9 ppm, average 7.23 ppm), In (0.002–7.54 ppm, average
0.42 ppm), Au (0.011–0.49 ppm, average 0.12 ppm) and Pb (2.05–5420
ppm, average 260 ppm), and lowest concentrations of V (0.02–1.13
analyses of pyrite from Cu-ore sample BSH-1-2A, 36 analyses of pyrite
ppm, average 0.20 ppm). Pyrite from sample BSH-2-1A has the highest
from Cu-ore sample BSH-1-3, 29 analyses of pyrite from Cu-ore sample
concentrations of Cu (23.2–122600 ppm, average 2599 ppm) and lowest
BSH-1-5, 33 analyses of pyrite from greenstone sample BSH-2-2, and 30
concentrations of Mn (0.40–18.7 ppm, average 1.29 ppm), Zn
analyses of pyrite from greenstone sample BSH-2-1A. The detailed data
(0.17–830 ppm, average 36.80 ppm), Ga (0.01–0.71 ppm, average 0.09
are presented in Supplementary Table 2.
ppm), As (1.18–227.6 ppm, average 40.17 ppm), Se (1.02–11.52 ppm,

6
J.-Y. Wang et al. Ore Geology Reviews 130 (2021) 103955

Fig. 6. (a) Chondrite normalized (Sun and McDonough, 1989) plots of greenstone samples. (b) Primitive normalized (Sun and McDonough, 1989) plots of green­
stone samples.

average 3.16 ppm), Ag (0.01–2.69 ppm, average 0.65 ppm), Sb means their Bi contents are more than 1 ppm and are probably influ­
(0.03–3.757 ppm, average 0.81 ppm), W (0.002–0.147 ppm, average enced by sediments. Most of the data plots are consistent with hydro­
0.03 ppm), Au (0.004–0.105 ppm, average 0.27 ppm), Hg (86–800 ppm, thermal pyrites (Fig. 9e and f).
average 190 ppm) and Pb (0.03–147.2 ppm, average 18.34 ppm). Mo,
Cd and W are generally lower than the detection limit (Supplementary 4.4. S isotopes in pyrite
Table 1), and some samples show low abundance, with maximum con­
centrations of a few tens of ppm. Meteoritic sulfide is considered to represent the primordial Earth’s
Silver shows a strong association with Pb, Sb and Cu (Fig. 7a, b and sulfur isotopic composition (Nielsen et al. 1991). Variations in the iso­
c). Telluride is the most abundant trace element with concentrations topic composition of terrestrial sulfur relative to VCDT (Vienna Canyon
ranging from 30 ppm to 58100 ppm among all the samples and shows a Diablo Troilite) are used to understand the origin of sulfur (Seal, 2006).
positive correlation with Au (Fig. 7d). Copper shows good correlation The complete data on sulfur isotopic analysis in the present study (n =
with Ag, Pb and Zn (Figs. 7c, 8a and b), furthermore, As vs Au, As vs Se, 54) is provided in Supplementary Table 2. The pyrite grains from Besshi
Zn vs Cd and In vs Sn plots show positive correlations (Fig. 8c,8d, e and show δ34SV-CDT values ranging from 2.10‰ to 7.11‰, with a mean of
f). The spots are scattered in Fig. 9a and b, which shows there is no 4.10‰ (Fig. 10). The δ33S values display a narrow range from 1.02‰ to
correspondence between Mn and Se as well as Cu and Se. In Fig. 9c, Ag 3.81‰ with corresponding δ34S values between 2.10‰ and 7.11‰,
shows prominent correlation with Au for all the samples except one Cu- which shows a distinct linear relation (δ33S = 0.5286δ34S-0.1068, R2 =
ore sample BSH-1-2A, and it’s the same in Fig. 7a, b and c. In Fig. 9d, 0.988) (Fig. 11).
most of the spots fall in the field in the upper part of the figure, which The pyrites have a narrow variation in Δ33S values between − 0.32

Fig. 7. Binary plots of (a) Ag versus Pb, (b) Ag versus Sb, (c) Ag versus Cu, (d) Te versus Au in pyrite. The measurements below the minimum detection limit are
not shown.

7
J.-Y. Wang et al. Ore Geology Reviews 130 (2021) 103955

Fig. 8. Binary plots of (a) Zn versus Cu, (b) Cu versus Pb, (c) As versus Au, (d) As versus Se, (e) Zn versus Cd, (f) In versus Sn in pyrite. The measurements below the
minimum detection limit are not shown.

and 0.16 (Table 2) and the results are plotted in the δ34S versus Δ33S determined as 1.14 ± 0.86. This isochron yields an age of 147.9 ± 4.2
diagram (Fig. 12) to evaluate the source of sulfur and the formation Ma (MSWD = 18, n = 7). As shown in Fig. 13b, the pyrites in this study
process. yielded Re–Os model ages ranging from 149.1 to 173.6 Ma. Three py­
rites from the Cu-ore samples yielded similar model ages from 169.8 to
4.5. Re-Os data and age of mineralization 173.6 Ma, with a mean value of 171.9 Ma and a peak age of 172 Ma
(Fig. 13b). Four pyrites from the greenstone samples yielded model ages
Whole-rock Re-Os isotope analytical results for 7 samples are listed with a narrow range from 149.1 Ma to 152.9 Ma and a mean value of
in Table 3. The Re concentrations range from 17.99 ppb to 188.7 ppb 150.7 Ma as well as a peak age of 150 Ma (Fig. 13b).
and Os concentrations vary from 0.11 to 0.36 ppb (Table 3). Re content
(17.99–188.7 ppb), and Os content (0.11–0.36 ppb) are significantly 5. Discussion
lower than the primitive mantle values (Re = 0.32 ppb, Os = 3.4 ppb;
Palme and O’Neill, 2014). The 187Os/188Os values for all samples range 5.1. Source of sulfur and ore genesis
from 3.79 to 87.04, which are much higher than depleted mantle
(0.1246) (Meisel et al., 1996) and primitive mantle (0.1296). The Pyrite is a major constituent of hydrothermal mineralization in a
187
Re/188Os values vary from 1310 to 34800. wide variety of ore systems such as porphyry copper deposits, volca­
All the samples plot on a liner array in the isochron diagram nogenic massive sulfide deposits, and Carlin-type gold deposits, among
(Fig. 13a). The isochron was calculated by means of the 187Re decay others (Reich et al., 2013). Although pyrite has an ideal composition of
constant of 1.666 × 10− 11a− 1 (Smoliar et al., 1996) using the ISOPLOT FeS2 (Abraitis et al., 2004), the mineral often carries high contents of
software (Model 3, Ludwig, 1999). According to the best-fit calculation trace elements hosted by substitution within the crystal lattice, as micro-
(Ludwig, 1999), a precise slope and initial 187Os/188Os value can be inclusions, or as nanoparticles (Huston et al., 1995; Deditius et al.,

8
J.-Y. Wang et al. Ore Geology Reviews 130 (2021) 103955

Fig. 9. Binary plots of (a) Mn versus Se, (b) Cu versus Se, (c) Ag versus Au, (d) Cd versus Bi, (e) Ni versus Au, (f) Zn versus Pb in pyrite. The measurements below the
minimum detection limit are not shown. The fields and lines in (c)–(f) were modified after Large et al. (2009) and Liu et al. (2018b).

2011). The geochemical and textural features of pyrite can be used to

trace changes in fluid chemistry during the evolution of the hydrother­
mal system from which it was precipitated (e.g., large et al., 2007;
Agangi et al., 2013; Reich et al., 2013). The subtle variations in chem­
istry can be detected from in situ analysis, and the results can be
employed to trace pyrite growth history and physicochemical environ­
ment (e.g., Zhao et al., 2011; Ward et al., 2017). The trace element
systematics of pyrite are sensitive to subtle changes in hydrothermal
fluid composition and temperature, and are useful in ore deposit
exploration as well as in evaluating the ore genesis (Steadman et al.,
2020).
Figs. 7, 8 and 9 illustrate the trace element chemistry of pyrite from
Besshi, where the plots show a correlation with the inclusions of
sphalerite and chalcopyrite. The correlation table for each pyrite sample
is presented in Supplementary Table 2. The almost perfect positive
correlation between Zn and Cd (Fig. 8e) indicates that almost in all
cases, the Cd measured in pyrite is hosted in sphalerite inclusions
(Genna and Gaboury, 2015). In Fig. 8, Cu is associated, to varying de­
grees, with Ag and Zn, indicating that these elements in pyrite are
Fig. 10. Histogram of the sulfur isotopic compositions (δ34S) of the pyrite.
influenced by chalcopyrite inclusions (Genna and Gaboury, 2015).
As one of the stable isotopes, sulfur has been commonly used to trace
the sources of ore fluids (Du et al., 2017; Liu et al., 2018a). The sulfur

9
J.-Y. Wang et al. Ore Geology Reviews 130 (2021) 103955

Table 2
Sulfur isotopic composition of the pyrite from Besshi, central Shikoku, South­
west Japan.
Analysis δ34S δ33S Δ33S

BSH-1-2A-01 2.79 1.47 0.03

BSH-1-2A-02 3.59 1.85 0.00
BSH-1-2A-03 2.88 1.53 0.04
BSH-1-2A-04 2.56 1.29 − 0.02
BSH-1-2A-05 2.89 1.56 0.07
BSH-1-2A-06 2.13 1.08 − 0.02
BSH-1-2A-07 2.81 1.47 0.03
BSH-1-2A-08 2.99 1.53 − 0.01
BSH-1-2A-09 3.25 1.76 0.09
BSH-1-2A-10 2.10 1.13 0.05
BSH-1-2A-11 3.01 1.52 − 0.02
BSH-1-2A-12 4.41 2.27 0.00
BSH-1-2A-13 4.17 2.11 − 0.04
BSH-1-2A-14 2.96 1.52 0.00
BSH-1-2A-15 3.16 1.51 − 0.12
BSH-1-3-01 3.90 1.97 − 0.04
BSH-1-3-02 3.88 1.93 − 0.06
BSH-1-3-03 4.16 2.09 − 0.05
BSH-1-3-04 3.98 2.05 0.00
BSH-1-3-05 3.58 1.73 − 0.11
BSH-1-3-06 3.58 1.75 − 0.09
Fig. 11. Plot of δ34S versus δ33S from the pyrite of the samples in the Bes­ BSH-1-3-07 2.62 1.30 − 0.05
shi deposit. BSH-1-3-08 3.90 1.90 − 0.10
BSH-1-3-09 3.54 1.71 − 0.11
BSH-1-3-10 3.84 1.80 0.17
isotope compositions (2.10‰ to 7.11‰) of sulfides from the Besshi de­ −
BSH-1-3-11 4.05 2.03 0.05
posit in this study is within the general range of δ34S isotope composi­
−
BSH-1-3-12 4.20 2.13 − 0.03
tions of sulfide from typical VMS-type deposit (about 0‰-10‰, Huston, BSH-1-5-01 3.51 1.66 − 0.14
1999). The δ34S isotope composition of pyrites is also a function of the BSH-1-5-02 2.33 1.09 − 0.11
oxidation state of fluids (Ohmoto, 1979; Neumayr et al., 2008), which BSH-1-5-03 3.06 1.26 − 0.32
BSH-1-5-04 2.95 1.41 0.11
plays a major role in mineralization. The pyrite as the dominant sulfide
−
BSH-1-5-05 2.35 1.11 − 0.10
phase in the Besshi deposit shows positive δ34S values (mean 4.10‰). BSH-1-5-06 2.15 0.99 − 0.12
Since redox-indicative mineral assemblages such as magnetite and BSH-1-5-07 3.21 1.57 − 0.09
limonite are absent, relatively reducing fluids are indicated (Neumayr BSH-1-5-08 2.29 1.02 − 0.15
BSH-1-5-09 3.44 1.64 0.13
et al., 2008). In general, VMS deposits are formed on or immediately −
BSH-1-5-10 3.57 1.65 − 0.19
below the seafloor through high temperature and evolved, seawater- BSH-1-5-11 3.67 1.79 − 0.10
dominated hydrothermal fluid (Franklin et al., 2005; Gibson and Galley, BSH-1-5-12 2.50 1.16 − 0.12
2007). Heated and compositionally modified seawater under a steep BSH-2-1A-01 5.70 3.09 0.16
geothermal gradient is considered to leach out metals without any BSH-2-1A-02 6.49 3.34 0.01
BSH-2-1A-03 5.99 3.09 0.01
distinct magmatic contribution (Galley, 1993; Franklin et al., 2005). The
BSH-2-1A-04 5.71 2.89 − 0.05
probable sources of sulfur in the case of VMS deposits might include: BSH-2-1A-05 6.08 3.03 − 0.09
seawater sulfate (δ34S = 17‰; Strauss, 1999) and/or sulfur leached from BSH-2-1A-06 5.79 2.90 − 0.08
the underlying basalts (δ34S = 0–1‰; Kusakabe et al., 1990; Alt et al., BSH-2-1A-07 6.04 3.03 − 0.08
BSH-2-1A-08 6.22 3.19 0.01
1993) and silty sandstone sediments (Maghfouri et al., 2016). The −
BSH-2-1A-09 6.17 3.03 0.14
relatively narrow range of δ34S isotope compositions of pyrites in this
−
BSH-2-1A-10 5.58 2.85 − 0.02
study (2.10 to 7.11‰) can be compared with those of sulfides in MORB, BSH-2-1A-11 6.54 3.35 − 0.01
OIB, or from oceanic crust rather than from seawater (Fig. 14). BSH-2-1A-12 5.91 3.12 0.08
BSH-2-1A-13 5.84 2.90 − 0.10
BSH-2-1A-14 5.93 2.98 − 0.07
5.2. Age of mineralization BSH-2-1A-15 7.11 3.81 0.16

Constraining the timing of ore mineralization is important to eval­ Jurassic (Fig. 13a), which agrees well with previously constrained ages
uate the genesis, tectonic history as well as the source of metals. The ore (147.0–160.4 Ma) for ore formation in this region (Nozaki et al., 2010,
age is generally constrained by dating host volcanic rocks or by fossil 2013). The good linear distribution of the Re-Os isochron given by the
strata in the case of volcanogenic massive sulfide (VMS) deposits. massive ores from the deposit suggests an equilibrium state of Re and Os
However, if host rocks experienced varying degree of alteration and isotopes at the beginning of crystallization and closed system behavior
metamorphism, the age obtained from ores in the ancient seafloor VMS during crystallization (Yang et al., 2005). The large range of 187Re/188Os
deposits could be debated (Hou et al., 2003). Traditional dating methods ratios from 1310 to 34,800 may be due to different partition coefficients
(i.e., Rb-Sr and K-Ar) often yield younger age for the host volcanic rocks. of Re and Os between monosulfide solid solution (Mss) and sulfide liquid
In this case, the Re-Os isotopic system has been employed to pre­ (Yang et al., 2005). The distinction between crust and mantle sources for
cisely obtain the ore-forming ages (Stein et al., 1998). Both Os and Re ore metals could be inhibited due to the relative incompatibility of Re to
are siderophile/chalcophile elements tending to be concentrated into Os during mantle melting events (Allegre and Luck, 1980; Luck and
sulfide minerals, and Re-Os ages can therefore be used to date the timing Allegre, 1983) and also because of the large difference in 187Re/188Os
of sulfide mineralization (Walker et al., 1994; Stein et al., 2001). and 187Os/188Os ratios between crust and mantle (Morgen et al., 1981;
The large ranges of 187Re/187Os ratios and high Re concentrations in Lambert et al., 1998).
pyrite from Besshi deposit are favorable for Re-Os dating (Table 3). In The Re-Os isochron ages of the sulfide ores can be considered
this study, the isochron yields an age of 147.9 ± 4.2 Ma within the Late

10
J.-Y. Wang et al. Ore Geology Reviews 130 (2021) 103955

that of voluminous CO2 input into the atmosphere through seafloor

volcanism. The concentration of atmospheric CO2 in the Late Jurassic is
considered to be the highest of the past 300 Myr, as well as an order of
magnitude higher than that of the present day (Berner and Kothavala,
2001; Fig. 15). Thus, Nozaki et al. (2013) proposed that intense seafloor
hydrothermal activity at a mid-ocean ridge was the primary trigger for
the formation of Besshi-type deposits and their preservation occurred
under stagnant anoxic conditions through gradually covering by pelagic
chert (metamorphosed to quartz schist). These packages were then
subsequently accreted onto the paleo-Japanese Islands. Nozaki et al.
(2013) thus correlated the Sambagawa Besshi-type VMS deposit to be a
consequence of the Late Jurassic ocean anoxic events affecting the
Panthalassa Ocean as well as the Tethys Ocean (Fig. 15), following
Pearce et al. (2010).
The geological framework, lithologic association and published S
and Re isotopic data of Besshi VMS deposit confirm its pelagic setting
(Sato and Sasaki, 1980; Sato and Kase, 1996; Kase, 2003; Nozaki et al.,
2010). The geochemical data from host greenstones presented in this
study, and those of the mafic schist reported by Nozaki et al. (2006)
Fig. 12. Diagram showing the sulfur isotope (δ34S and Δ33S) as determined by suggest N-MORB features. These features suggest that the Besshi massive
in situ SIMS analysis in pyrite. hydrothermal sulfides formed through volcanism from a mid ocean
ridge.
equivalent to the timing of sulfide deposition on a paleo-seafloor
(Nozaki et al., 2013). For the Besshi-type deposits, all the Re-Os ages 6. Conclusions
are much older than the estimated age of peak metamorphism in the
Sambagawa metamorphic belt (110–120 Ma - Okamoto et al., 2004; 90 (1) The orebodies in the VMS-type deposits in the type area of Besshi
Ma - Wallis et al., 2009). in SW Japan are tabular and closely associated with mafic schist
Nozaki et al. (2013) evaluated the correlation between the formation of the Cretaceous Sambagawa metamorphic belt. The dominant
of Besshi-type deposits with major global environmental changes and sulfide minerals are pyrite, chalcopyrite, and sphalerite together
noted that the timing of sulfide deposition in these ores coincides with with minor amounts of pyrrhotite and bornite.

Table 3
Re-Os isotopic composition of the pyrite from Besshi, central Shikoku, Southwest Japan.
187 187 187
Sample Rock type Weight (g) Re (ng/g) Common Os (ng/ Re (ng/g) Os (ng/g) Re/188Os 187
Os/188Os Model age
g) (Ma)

Data 2σ Data 2σ Data 2σ Data 2σ Data 2σ Data 2σ Data 2σ

BSH-1-2A Cu-Ore 0.20087 19.69 0.16 0.0250 0.0002 12.38 0.10 0.0356 0.0003 3798 40 10.92 0.02 172.2 1.8
BSH-1-3 Cu-Ore 0.20167 17.99 0.13 0.0663 0.0005 11.31 0.08 0.0327 0.0002 1310 13 3.793 0.007 173.6 1.8
BSH-1-5 Cu-Ore 0.20088 59.30 0.67 0.0559 0.0005 37.27 0.42 0.1056 0.0008 5125 70 14.51 0.06 169.8 2.3
BSH-2-1 Greenstone 0.20110 72.48 0.54 0.0296 0.0002 45.55 0.34 0.1146 0.0009 11,841 128 29.73 0.13 150.9 1.6
BSH-2-2 Greenstone 0.30069 78.65 0.59 0.0301 0.0003 49.42 0.37 0.1261 0.0010 12,636 140 32.14 0.14 152.9 1.6
BSH-2-1A Greenstone 0.20060 173.2 1.3 0.0240 0.0002 108.9 0.80 0.2724 0.0021 34,800 392 87.04 0.35 149.9 1.6
BSH-2-1B Greenstone 0.05000 188.7 1.4 0.0340 0.0003 118.6 0.90 0.2949 0.0022 27,304 289 68.80 0.36 149.1 1.5

Fig. 13. (a) Re-Os isochron diagram of Cu-ores from the Besshi deposit. The isochron ages are calculated using the ISOPLOT software. (b) Pyrite Re depleted model
(TRD) age data using the kernel density distribution approach (Spencer et al., 2017).

11
J.-Y. Wang et al. Ore Geology Reviews 130 (2021) 103955

Fig. 14. Results from sulfur isotope analyses conducted in this study compared with sulfur isotopic compositions of seafloor and subduction-related materials and
those in other settings. Width of bars relate to the distribution of samples in a specific group (modified after Marschall et al., 2011).

Fig. 15. Timing of Besshi-type VMS deposition with Os-isotope and atmospheric CO2 curves (modified after Nozaki et al., 2013). Secular change of 187Os/188Os ratio
and mass ratio of atmospheric CO2 compared to (RCO2) (Berner and Kothavala, 2001) are shown from the Permian to the present together with major ocean anoxic
events (OAEs).

(2) Geochemically, the greenstone samples show N-MORB and E- Acknowledgments

MORB features.
(3) The δ34S values and trace elements of pyrites from the ore deposit We thank Editor-in-Chief Prof. Franco Pirajno for handling our paper
suggest origin from high temperature hydrothermal fluids. and an anonymous referee for providing us with constructive comments
(4) The Re-Os isotope geochronology of pyrite suggests the timing of that helped in improving this paper. We sincerely thank Dr. Christopher
sulfide deposition at 147.9 Ma. Spencer at Curtin University, Australia for the kind help in arranging the
(5) The geological setting, lithological association and geochemical trace element and sulfur isotope analyses. M. Santosh acknowledges
as well as isotopic features suggest ore formation in a pelagic China University of Geosciences Beijing, China as Foreign Expert and
setting, associated with mid ocean ridge volcanism. Professorial position at the University of Adelaide, Australia for sup­
porting this work. This work forms part of the PhD project of Jingyi
Declaration of Competing Interest Wang at CUGB, supported by Fundamental Research Fund of Central
Universities (Grant No. 2652019185).
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence Appendix A. Supplementary data
the work reported in this paper.
Supplementary data to this article can be found online at https://doi.

12
J.-Y. Wang et al. Ore Geology Reviews 130 (2021) 103955

org/10.1016/j.oregeorev.2020.103955. Kato, Y., Suzuki, K., Nakamura, K., Hickman, A.H., Nedachi, M., Kusakabe, M.,
Bevacqua, D.C., Ohmoto, H., 2009. Hematite formation by oxygenated groundwater
more than 2.76 billion years ago. Earth Planet. Sci. Lett. 278, 40–49.
References Koski, R.A., 1990. A comparison of sulfide deposits from modern sediment-covered
spreading axes with Besshi-type deposits of Japan. In: McMurray, G.R. (Ed.), Gorda
Abraitis, P.K., Pattrick, R.A.D., Vaughan, D.J., 2004. Variations in the compositional, Ridge: A Seafloor Spreading Center in the United States Exclusive Economic Zone.
textural and electrical properties of natural pyrite: a review. Int. J. Miner. Process. Springer-Verlag, New York, pp. 117–130.
74 (1-4), 41–59. https://doi.org/10.1016/j.minpro.2003.09.002. Kusakabe, M., Mayeda, S., Nakamura, E., 1990. S, O and Sr isotope systematics of active
Agangi, A., Hofmann, A., Wohlgemuth-Ueberwasser, C.C., 2013. Pyrite Zoning as a vent materials from the Mariana backarc basin spreading axis at 18◦ N.Earth Planet.
Record of Mineralization in the Ventersdorp Contact Reef, Witwatersrand Basin, Sci. Lett. 100, 275–282.
South Africa. Econ. Geol. 108 (6), 1243–1272. https://doi.org/10.2113/ LaFlamme, C., Martin, L., Jeon, H., Reddy, S.M., Selvaraja, V., Caruso, S., Bui, T.H.,
econgeo.108.6.1243. Roberts, M.P., Voute, F., Hagemann, S., Wacey, D., 2016. In situ multiple sulfur
Alt, J.C., Shanks, W.C., Jackson, M.C., 1993. Sources and cycling of sulfur in subduction isotope analysis by SIMS of pyrite, chalcopyrite, pyrrhotite, and pentlandite to refine
zones: the Mariana island arc and back arc trough. Earth Planet. Sci. Lett. 119, magmatic ore genetic models. Chem. Geol. 444, 1–15.
477–494. Lambert, D.D., Foster, J.G., Frick, L.R., Ripley, E.M., Zientek, M.L., 1998. Geodynamics of
Badrzadeh, Z., Barrett, T.J., Peter, J.M., Gimeno, D., Sabzehei, M., Aghazadeh, M., 2011. magmatic Cu-Ni- PGE sulfide deposits: new insights from the Re-Os isotope system.
Geology, mineralogy, and sulfur isotope geochemistry of the Sargaz Cu–Zn Econ. Geol. 93, 121–137.
volcanogenic massive sulfide deposit, Sanandaj–Sirjan Zone, Iran. Miner Deposita 46 Large, R.R., Maslennikov, V.V., Robert, F., Danyushevsky, L.V., Chang, Z., 2007.
(8), 905–923. https://doi.org/10.1007/s00126-011-0357-4. Multistage sedimentary and metamorphic origin of pyrite and gold in the giant
Berner, R.A., Kothavala, Z., 2001. GEOCARB III: a revised model of atmospheric CO2 Sukhoi Log deposit, Lena gold province, Russia. Econ. Geol. 102, 1233–1267.
over Phanerozoic time. Am. J. Sci. 301 (2), 182–204. Large, R.R., Danyushevsky, L., Hollit, C., Maslennikov, V., Meffre, S., Gilbert, S., et al.,
Banno, S., Sakai, C., 1989. Geology and metamorphic evolution of the Sanbagawa 2009. Gold and trace element zonation in pyrite using a laser imaging technique:
metamorphic belt, Japan. Geol. Soc. Lond. Spec. Publ. 43 (1), 519–532. https://doi. implications for the timing of gold in orogenic and carlin-style sediment-hosted
org/10.1144/GSL.SP.1989.043.01.50. deposits. Econ. Geol.
Deditius, A.P., Utsunomiya, S., Reich, M., Kesler, S.E., Ewing, R.C., Hough, R., Walshe, J., Liu, L., Zhou, T., Zhang, D., Yuan, F., Liu, G., Zhao, Z., Sun, J., White, N., 2018a.
2011. Trace metal nanoparticles in pyrite. Ore Geol. Rev. 42 (1), 32–46. https://doi. S isotopic geochemistry, zircon and cassiterite U-Pb geochronology of the Haobugao
org/10.1016/j.oregeorev.2011.03.003. Sn polymetallic deposit, southern Great Xing’an Range, NE China. Ore Geol. Rev. 93,
DOI, M., 1961. Geology and Cupriferous Pyrite Deposits (Besshi Type) of the Sanbagawa 168–180.
Metamorphic Zone including the Besshi and the Sazare Mines in Central Shikoku (I). Liu, Z., Shao, Y., Zhou, H., Liu, N., Huang, K., Liu, Q., Zhang, J., Wang, C., 2018b. Major
Mining Geology. 11 (50), 610–626. and trace element geochemistry of pyrite and pyrrhotite from stratiform and
Du, A.-D., Wang, S.-X., Sun, D.-Z., Zhao, D.-M., Liu, D.-Y., 2001. Precise Re-Os dating of lamellar orebodies: implications for the ore genesis of the Dongguashan copper
molybdenite using Carius tube, NTIMS and ICPMS. In: in Piestrzynski and others (gold) deposit, eastern China. Minerals. 8 (9), 380.
(eds.) Mineral Deposits at the 21st Century, pp. 405–407. Ludwig, K.R., 1999. ISOPLOT/Ex—a geochronological toolkit for Microsoft Excel,
Du, L.J., Li, B., Huang, Z.L., Zhou, J.X., Zou, G.F., Yan, Z.F., 2017. Carbon-oxygen Version 2.05. Berkeley Geochronology Center Special Publication, vol. 1, p.49.
isotopic geochemistry of the Yangla Cu skarn deposit, SW China: Implications for the Luck, J.M., Allegre, C.J., 1983. 187Re-187Os systematics in meteorites and
source and evolution of hydrothermal fluids. Ore Geol. Rev. 88, 809–821. cosmochemical consequence. Nature 302, 130–132.
Francheteau, J., Needham, H.D., Choukroune, P., Seguret, M., Ballard, R.D., Fox, P.J., Maghfouri, S., Rastad, E., Mousivand, F., Lin, Y., Zaw, K., 2016. Geology, ore facies and
Normark, W., Carranza, A., Cordoba, D., Guerrero, J., Rangin, C., Bougault, H., sulfur isotopes geochemistry of the Nudeh Besshi-type volcanogenic massive sulfide
Cambon, P., Heikinian, R., 1979. Massive deep-sea sulfide deposits discovered on the deposit, southwest Sabzevar basin, Iran. J. Asian Earth Sci. 125, 1–21.
East Pacific Rise. Nature 277, 523–528. Marschall, H.R., Shimizu, N., Hacker, B.R., Kylander-Clark, A.R.C., 2011. Sulfur isotopes
Franklin, J.M., Gibson, H.L., Jonasson, I.R., Galley, A.G., 2005. Volcanogenic Massive in high pressure rocks. In: The 9th International Eclogite Conference Abstracts,
Sulphide Deposits. 100th Anniversary Volume. The Economic Geology Publishing pp. 43–44.
Company. 523–560. Maruyama, S., Isozaki, Y., Kimura, G., Terabayashi, M., 1997. Paleogeographic Maps of
Galley, A.G., 1993. Characteristics of semi-conformable alteration zones associated with the Japanese Islands: plate tectonic synthesis from 750 Ma to the present. The Island
volcanogenic massive sulphide districts. J. Geochem. Explor. 48, 175–200. Arc. 6, 121–142.
Galley, A.G., Hannington, M.D., Jonasson, I.R., 2007. Volcanogenic massive sulphide Maruyama, S., Santosh, M., Zhao, D.P., 2007. Superplume, supercontinent, and
deposits. Mineral deposits of Canada: A synthesis of major deposit-types, district postperovskite: mantle dynamics and anti-plate tectonics on the core-mantle
metallogeny, the evolution of geological provinces, and exploration methods: boundary. Gondwana Res. 11, 7–37.
Geological Association of Canada, Mineral Deposits Division, Special Publication. 5, Meisel, T., Walker, R.J., Morgau, J.M., 1996. The Osmium isotopic composi-tion of
141–161. primitive upper mantle. Nature 383, 517–520.
Genna, D., Gaboury, D., 2015. Deciphering the hydrothermal evolution of a VMS system Morelli, R.M., Creaser, R.A., Selby, D., Kontak, D.J., Horne, R.J., 2005. Rhenium–osmium
by LA-ICP-MS using trace elements in pyrite: an example from the Bracemac-McLeod geochronology of arsenopyrite in Meguma Group gold deposits, Meguma Terrane,
deposits, Abitibi, Canada, and implications for exploration. Econ. Geol. 110 (8), Nova Scotia, Canada: evidence for multiple gold-mineralizing events. Econ. Geol.
2087–2108. 100, 1229–1242.
Gibson, H.L., Galley, A.G., 2007. Volcanogenic massive sulphide deposits of the Archean, Morgen, J.W., Wandless, G.A., Petriev, R.K., Irving, A.J., 1981. Composition of the
Noranda district, Quebec. In: Goodfellow, W.D. (Ed.), Mineral Deposits of Earth’s upper mantle I: Siderophile trace elements in upper mantle nodules.
Canada—A Synthesis of Major Deposit-types, District Metallogeny, the Evolution of Tectonophys. 75, 47–67.
Geological Provinces, and Exploration Methods. Geological Association of Canada, Mousivand, F., Rastad, E., Meffre, S., Solomon, M., Peter, J.M., Zaw, K., 2011. U-Pb
Mineral Deposits Division, Special Publication 5. pp. 533–552. geochronology and Pb isotope characteristics of the Chahgaz volcanogenic massive
Hada, S., Ishii, K.I., Landis, C.A., Aitchison, J., Yoshikura, S., 2001. Kurosegawa terrane sulfide deposit, southern Iran. Int. Geol. Rev. 53, 1239–1262.
in southwest Japan: disrupted remnants of a Gondwana-derived terrane. Gondwana Nakagawa, M., 2013. Industrial Heritage of the Besshi Copper Mine and the Sanbagawa
Res. 4 (1), 27–38. Metamorphic Rocks in the Besshi Area, Central Shikoku, Japan : Field Guide for the
Hou, Z., Wang, S., Du, A., Qu, X., Sun, W., 2003. Re-Os Dating of Sulfides from the 57th Annual Meeting of the Clay Science Society of Japan. The Clay Science Society
Volcanogenic Massive Sulfide Deposit at Gacun, Southwestern China. Resour. Geol. of Japan. 52 (1), 23–31.
53 (4), 305–310. Neumayr, P., Walshe, J., Hagemann, S., Petersen, K., Roache, A., Frikken, P., Horn, L.,
Huston, D.L., Sie, S.H., Suter, G.F., Cooke, D.R., Both, R.A., 1995. Trace elements in Halley, S., 2008. Oxidized and reduced mineral assemblages in greenstone belt rocks
sulfide minerals from eastern Australian volcanic-hosted massive sulfide deposits; of the St. Ives gold camp, Western Australia: vectors to high-grade ore bodies in
Part I, Proton microprobe analyses of pyrite, chalcopyrite, and sphalerite, and Part II, Archaean gold deposits? Miner. Deposita 43 (3), 363–371.
Selenium levels in pyrite; comparison with δ34S values and implications for the Nielsen, H., Pilot, J., Grinenko, L.N., Grinenko, V.A., Lein, A.Y., Smith, J.W. and Pankina,
source of sulfur in volcanogenic hydrothermal systems. Econ. Geol. 90, 1167–1196. R.G., 1991. Lithospheric sources of sulphur. In Stable isotopes: natural and
Huston, D., 1999. Stable isotopes and their significance for understanding the genesis of anthropogenic sulphur in the environment. Krouse HR, Grinenko VA (eds) SCOPE
volcanic-associated massive sulfide deposits: a review. In Barrie, C., Hannington, M. 43, J Wiley and Sons, pp. 65–132.
(Eds.) Volcanic-associated massive sulfide deposits: processes and examples in Nozaki, T., Nakamura, K., Awaji, S., Kato, Y., 2006. Whole rock geochemistry of basic
modern and ancient settings. Soc. Econ. Geol., vol. 8, pp. 157–179. schists from the Besshi area, central Shikoku: implications for the tectonic setting of
Ishihara, S., Endo, Y., 2007. Indium and other trace elements in volcanogenic massive the Besshi sulfide deposit. Resour. Geol. 56, 423–432.
sulfide ores from the Kuroko, Besshi and other types in Japan. Bull. Geol. Surv. Nozaki, T., Kato, Y., Suzuki, K., 2010. Re–Os geochronology of the Iimori Besshi-type
Japan. 58, 7–22. massive sulfide deposit in the Sanbagawa metamorphic belt, Japan. Geochim.
Isozaki, Y., Aoki, K., Nakama, T., Yanai, S., 2010. New insight into a subduction-related Cosmochim. Acta 74 (15), 4322–4331.
orogen: A reappraisal of the geotectonic framework and evolution of the Japanese Nozaki, T., Kato, Y., Suzuki, K., 2013. Late Jurassic ocean anoxic event: Evidence from
Islands. Gondwana Res. 18 (1), 82–105. voluminous sulphide deposition and preservation in the Panthalassa. Sci. Rep. 3,
Kase, K., 1988. Tin, Arsenic, Zinc and Silver vein mineralization in the Besshi mine, 1889.
central Shikoku. Mining Geology. 38 (211), 407–418. Ohmoto, H., 1979. Isotopes of sulfur and carbon. Geochemistry of hydrothermal ore
Kase, K., 2003. Genesis and classification of Besshi-type Cu deposits. In Resource and deposits 509–567.
Environmental Geology (ed. Society of Resource Geology). pp. 87–94. Okamoto, K., Maruyama, S., Isozaki, Y., 2000. Accretionary complex origin of the
Kase, K., Yamamoto, M., 1988. Minerals and geochemical characteristics of ores from the Sanbagawa, high P/T metamorphic rocks, Central Shikoku, Japan –Layer-parallel
Besshi-type deposits in the Sambagawa Belt, Japan. Min. Geol. 38, 203–214. shortening structure and greenstone geochemistry–. J. Geol. Soc. Jpn. 106, 70–86.

13
J.-Y. Wang et al. Ore Geology Reviews 130 (2021) 103955

Okamoto, K., Shinjoe, H., Katayama, I., Terada, K., Sano, Y., Johnson, S., 2004. SHRIMP Strauss, H., 1999. Geological evolution from isotope proxy signals—sulfur. Chem. Geol.
U-Pb zircon dating of quartz-bearing eclogite from the Sanbagawa Belt, south-west 161 (1–3), 89–101.
Japan: implications for metamorphic evolution of subducted protolith. Terra Nova Sun, S.-S., McDonough, W.F., 1989. Chemical and isotopic systematics of oceanic basalts:
16 (2), 81–89. implications for mantle composition and processes. Geol. Soc. Lond. Spec. Publ. 42,
Otsuki, M., Banno, S., 1990. Prograde and retrograde metamorphism of hematite bearing 313–345.
basic schists in the Sanbagawa belt in central Shikoku. J. Metamorph. Geol. 8 (4), Tang, L., Hu, X., Santosh, M., Zhang, S., Spencer, C., Jeon, H., Zhao, Y., Cao, H., 2019.
425–439. Multistage processes linked to tectonic transition in the genesis of orogenic gold
Palme, H., O’Neill, H.S.C., 2014. Cosmochemical estimates of mantle composition. Treat. deposit: A case study from the Shanggong lode deposit, East Qinling, China. Ore
Geochem. (Second Ed.) 3, 1–39. Geol. Rev. 111, 102998.
Pearce, C.R., Coe, A.L., Cohen, A.S., 2010. Seawater redox variations during the Tang, L., Zhao, Y., Zhang, S.T., Sun, L., Hu, X.K., Sheng, Y.M., Zeng, T., 2021. Origin and
deposition of the Kimmeridge Clay Formation, United Kingdom (Upper Jurassic): evolution of a porphyry-breccia system: evidence from zircon U-Pb, molybdenite Re-
evidence from molybdenum isotopes and trace metal ratios. Paleoceanography 25 Os geochronology, in situ sulfur isotope and trace elements of the Qiyugou deposit,
(4). China. Gondwana Res. 89, 88–104.
Peter, J.M., Scott, S.D., 1999. Windy Craggy, northwestern British Columbia: the world’s Terabayashi, M., Okamoto, K., Yamamoto, H., Kaneko, Y., Ota, T., Maruyama, S.,
largest Besshi deposit. Rev. Econ. Geol. 8, 261–295. Katayama, I., Komiya, T., Ishikawa, A., Anma, R., Ozawa, H., Windley, B.F., Liou, J.
Rastad, E., Miralipour, A., Momenzadeh, M., 2002. Sheikh-Ali copper deposit, a Cyprus- G., 2005. Accretionary complex origin of the mafic-ultramafic bodies of the
type VMS deposit in Southeast Iran. J. Sci. Islamic Republic Iran 13 (1), 51–63. Sanbagawa belt, central Shikoku, Japan. Int. Geol. Rev. 47, 1058–1073.
Reich, M., Deditius, A., Chryssoulis, S., Li, J.-W., Ma, C.-Q., Parada, M.A., Barra, F., Walker, R.J., Morgan, J.W., Horan, M.F., Czamanske, G.K., Krogstad, E.J., Fedorenko, V.
Mittermayr, F., 2013. Pyrite as a record of hydrothermal fluid evolution in a A., Kunilov, V.E., 1994. Re– Os isotopic evidence for an enriched-mantle source for
porphyry copper system: A SIMS/EMPA trace element study. Geochim. Cosmochim. the Norilsk-type,
́ ore-bearing intrusions, Siberia. Geochim. Cosmochim. Acta. 58,
Acta v. 104, 42–62. 4179–4197.
Sato, K., Kase, K., 1996. Pre-accretionary mineralization of Japan. Isl. Arc 5, 216–228. Wallis, S.R., Anczkiewicz, R., Endo, S., Aoya, M., Platt, J.P., Thirlwall, M., Hirata, T.,
Sato, K., Sasaki, A., 1980. Lead isotopic feature of the Besshi-type deposits and its bearing 2009. Plate movements, ductile deformation and geochronology of the Sanbagawa
on the ore lead evolution. Geochem. J. 14 (6), 303–315. belt, SW Japan: tectonic significance of 89–88 Ma Lu–Hf eclogite ages.
Seal, R.R., 2006. Sulfur isotope geochemistry of sulfide minerals. Rev. Mineral. Geochem. J. Metamorph. Geol. 27 (2), 93–105.
61 (1), 633–677. Wang, C., Yang, L., Bagas, L., Evans, N.J., Chen, J., Du, B., 2018. Mineralization
Selby, D., Kelley, K.D., Hitzman, M.W., Zieg, J., 2009. Re–Os sulfide (bornite, processes at the giant Jinding Zn–Pb deposit, Lanping Basin, Sanjiang Tethys
chalcopyrite, and pyrite) systematics of the carbonate-hosted copper deposits at Orogen: Evidence from in situ trace element analysis of pyrite and marcasite. Geol. J.
Ruby Creek, southern Brooks Range, Alaska. Econ. Geol. 104, 437–444. 53 (4), 1279–1294.
Shirey, S.B., Walker, R.J., 1995. Carius tube digestion for low-blank rhenium- osmium Ward, J., Mavrogenes, J., Murray, A., Holden, P., 2017. Trace element and sulfur isotopic
analysis. Anal. Chem. 67, 2136–2141. evidence for redox changes during formation of the Wallaby gold deposit, Western
Smoliar, M.I., Walker, R.J., Morgan, J.W., 1996. Re-Os ages of group IIA, IIIA, IVA, and Australia. Ore Geol. Rev. 82, 31–48.
IVB iron meteorites. Science 271 (5252), 1099–1102. Winchester, J.A., Floyd, P.A., 1976. Geochemical magma type discrimination:
Spencer, C.J., Yakymchuk, C., Ghaznavi, M., 2017. Visualising data distributions with application to altered and metamorphosed basic igneous rocks. Earth Planet. Sci.
kernel density estimation and reduced chi-squared statistic. Geosci. Front. 8, 1–6. Lett. 28 (3), 459–469.
Steadman, J.A., Large, R.R., Olin, P.H., Danyushevsky, L.V., Meffre, S., Huston, D., Yarmohammadi, A., 2006. Mineralogy, Geochemistry and Genesis of the Barika Gold
Wells, T., 2020. Pyrite trace element behavior in magmatic-hydrothermal (and Barite and Base Metal) Mineralization, East of Sardasht, Northwestern Iran
environments: An LA-ICPMS imaging study. Ore Geol. Rev. 103878. Unpublished M.Sc. Thesis. Tarbiat Modares University, NY, pp. 260 (in Persian with
Stein, H.J., Sundblad, K., Markey, R.J., Morgan, J.W., Motuza, G., 1998. Re-Os ages for English abstract).
Archean molybdenite and pyrite, Kuittila-Kivisuo, Finland and Proterozoic Yang, G., Du, A., Lu, J., Qu, W., Chen, J., 2005. Re-Os (ICP-MS) dating of the massive
molybdenite, Kabeliai, Lithuania: Testing the chronometer in a metamorphic and sulfide ores from the Jinchuan Ni-Cu-PGE deposit. Sci. China, Ser. D Earth Sci. 48
metasomatic setting. Miner. Deposita 33 (4), 329–345. (10), 1672–1677.
Stein, H.J., Markey, R.J., Morgan, J.W., Selby, D., Creaser, R.A., McCuaig, T.C., Behn, M., Zhao, H.X., Frimmel, H.E., Jiang, S.Y., Dai, B.Z., 2011. LA-ICP-MS trace element analysis
2001. Re–Os dating of Boddington molybdenite, SW Yilgarn: two Au mineralization of pyrite from the Xiaoqinling gold district, China: implications for ore genesis. Ore
events. AGSO-Geosci Australia, Record. 37, 469–471. Geol. Rev. 43, 142–153.

14