Ore Geology Reviews 124 (2020) 103647

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Ore Geology Reviews

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Textural and geochemical analysis of chalcopyrite, galena and sphalerite T

across the Mount Isa Cu to Pb-Zn transition: Implications for a zoned Cu-Pb-
Zn system
Bradley Cave⁎, Richard Lilly, Karin Barovich
Mawson Centre for Geoscience, Department of Earth Sciences, The University of Adelaide, SA 5005, Australia

ARTICLE INFO ABSTRACT

Keywords: The genesis of the Mount Isa Cu-Pb-Zn system, northern Australia, is highly debated. Three metallogenic models
Mount Isa have previously been proposed to explain the close spatial relationship between a world-class Cu and Pb-Zn
Chalcopyrite deposit: (1) ca. 1650 Ma syngenetic Pb-Zn mineralisation that has been re-mobilised and overprinted by ca.
Sphalerite 1520 Ma epigenetic Cu mineralisation; (2) ca. 1650 Ma syn-sedimentary Cu-Pb-Zn mineralisation; (3) ca.
Sulphide Chemistry
1520 Ma epigenetic Cu-Pb-Zn mineralisation. To assess the viability of these models, detailed petrography and
Ore Genesis
Petrography
core logging was completed on numerous samples across eight sections of drill core that intersect both Cu and
Pb-Zn mineralisation. This was accompanied by the analysis of trace elements in chalcopyrite, galena and
sphalerite from various samples across the lateral transition from Cu- to Pb-Zn-rich mineralisation.
Across the Cu to Pb-Zn transition there is a primary change in host lithology from Cu-rich silica-dolomite
breccia to highly-stratiform Pb-Zn-rich, carbonaceous, carbonate-rich, and fine-grained pyrite-rich shale.
Petrography suggests that sphalerite, galena and chalcopyrite co-crystallised, consistently enveloping and/or
replacing pre-mineralisation silica-dolomite, siderite, calcite, arsenopyrite, fine- and coarse-grained pyrite. From
Cu to Pb-Zn-rich mineralisation, sphalerite and galena transition from micro-inclusions primarily located within
coarse-grained chalcopyrite to dominant fine- to coarse-grained components that infill around deformed car-
bonaceous shale and selectively replace carbonate-rich and fine-grained pyrite-rich shale. Chalcopyrite transi-
tions from a coarse-grained component that replaces silica-dolomite alteration to an uncommon medium- to fine-
grained component residing within stratabound Pb-Zn mineralisation.
Trace element trends demonstrate that as Pb-Zn mineralisation is approached, the concentrations of Bi in
chalcopyrite, Cd, Se, Te, Bi in galena, and Bi and Co in sphalerite decrease, or are relatively depleted. Conversely,
the concentrations of Pb in chalcopyrite, Sb in galena, and Pb, Sb and Ag in sphalerite increase, or are relatively
enriched. These trends are consistent with a temperature gradient between Cu and Pb-Zn mineralisation during
ore emplacement. The sphalerite GGIMFis geothermometer yields a median homogenisation temperature of
343 ± 44 °C, consistent with previous temperature estimates of Cu mineralisation, silica-dolomite formation and
chlorite alteration. An epigenetic and coeval Cu-Pb-Zn model is favoured where a slight temperature gradient
(<50 °C) resulted in the deposit scale zonation of Cu → Pb → Zn-rich mineralisation outwards from the Paroo
fault. This allowed Pb and Zn-bearing fluids to migrate further into the host shale, resulting in different styles of
mineralisation relative to Cu.

1. Introduction
Five major sedimentary hosted stratiform Pb-Zn (Ag) deposits are
known within the Proterozoic Mount Isa and McArthur Basins of
northern Australia. These include the Mount Isa, Hilton and George
Fisher deposits within the Mount Isa Basin (Fig. 1), and the Century and
McArthur River deposits within the McArthur Basin (Cooke et al., 2000;
Leach et al., 2005). The Mount Isa deposit is distinctive from these Zn-
Pb (Ag) deposits as it also contains a significant Cu orebody. The close
spatial association of a large Cu and Pb-Zn system, which display sig-
nificantly different mineralogical and physical characteristics has re-
sulted in extensive debate regarding its formation. Any metallogenic
model developed for the Mount Isa Cu-Pb-Zn deposit impacts future
exploration for both Cu and Pb-Zn mineralisation and has implications

⁎
Corresponding author.
E-mail addresses: bradley.cave@adelaide.edu.au (B. Cave), richard.lilly@adelaide.edu.au (R. Lilly).

https://doi.org/10.1016/j.oregeorev.2020.103647
Received 2 February 2020; Received in revised form 16 April 2020; Accepted 8 June 2020
Available online 12 June 2020
0169-1368/ Crown Copyright © 2020 Published by Elsevier B.V. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/BY/4.0/).
B. Cave, et al.
Fig. 1. (a) The location of the Mount Isa Inlier, Australia. (b) The location of Mount Isa in the Mount Isa Inlier. (c) A simplified geological map of the Mount Isa region
following Bain et al. (1992).
for the formation of other large stratiform Pb-Zn deposits both re-
gionally and globally.
Previous research on the Mount Isa Cu-Pb-Zn deposit has resulted in
the development of three main metallogenic models: (1) Syngenetic Zn-
Pb mineralisation occurred in a sedimentary exhalative (SEDEX)-like
environment at ca. 1650 Ma before subsequent metamorphism and
remobilisation at ca. 1575 Ma (Carr et al., 2004; Gulson et al., 1983;
Large et al., 2005; Smith et al., 1978). Pb-Zn mineralisation was then
overprinted by epigenetic Cu mineralisation at ca. 1520 Ma; (2) Syn-
genetic Cu-Pb-Zn mineralisation formed in a SEDEX-like environment
at ca. 1650 Ma, and was subsequently remobilised during peak meta-
morphic conditions into their current positions (Finlow-Bates and
Stumpfl, 1980; McGoldrick and Keays, 1990); (3) Epigenetic and coeval
Cu-Pb-Zn mineralisation occurred at ca. 1520 Ma (Davis, 2004; Perkins,
1997).
The trace element compositions of chalcopyrite, galena and spha-
lerite have previously been used to assess the co-crystallisation of var-
ious base metal sulphide assemblages (Cook et al., 2016; George et al.,
2015, 2018, 2016). Recently, studies have illustrated that the compo-
sition of trace elements within these minerals can be used to decipher
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Ore Geology Reviews 124 (2020) 103647
various physicochemical conditions associated with ore formation. For
example, indium concentrations in sphalerite increase with the pre-
sence of Cu (Carvalho et al., 2018; Frenzel et al., 2016), the con-
centrations of Ga, Ge, In, Mn and Fe in sphalerite can be used to esti-
mate the formation temperature of Zn-bearing ores (Frenzel et al.,
2016), and various elemental ratios in galena (Sb/Ag & Bi/Sb) can be
used to track fluid flow patterns over a deposit scale (Amcoff, 1984;
Lueth et al., 2000).
In this contribution we conduct in-depth core logging and detailed
petrography to assess the relative timing and textural characteristics of
chalcopyrite, sphalerite and galena across the lateral transition from Cu
to Pb-Zn-rich mineralisation at the Mount Isa deposit. The trace element
compositions of sphalerite, galena and chalcopyrite are analysed across
the Cu to Pb-Zn transition to assess the influence of varying physico-
chemical factors associated with ore formation. These results are then
used to assess the viability of the three main metallogenic models.
B. Cave, et al.
Fig. 2. (a) A cross section looking west showing the distribution of silica-dolomite, Cu (1%), Pb (2.5%) and Zn (2.5%) mineralisation. (b) A cross section looking
north from A − A’. (c) A cross section looking north from B − B’. The location of drill core samples used in this study are shown as numbers corresponding to the
sample list in the key.
2. Background
2.1. Regional geology
The Mount Isa Cu-Pb-Zn deposit is located in the Western Fold Belt
of the Paleoproterozoic Mount Isa Inlier (Fig. 1). Regional stratigraphy
is divided into the Leichhardt Superbasin (1800 1750 Ma), the Calvert
Superbasin (1750 1690 Ma) and the Isa Superbasin (1670 1575 Ma),
with deposition terminated by the onset of the 1610 1500 Ma Isan
Orogeny (Neumann et al., 2006; Page et al., 2000; Scott et al., 2000). In
the vicinity of Mount Isa, locally abundant formations associated with
the Leichhardt Superbasin include the 1773 ± 16 Ma Mount Guide
Quartzite Formation, the 1779 ± 4 Ma Eastern Creek Volcanics and the
1768 ± 8 Ma Myally Subgroup, which together comprise the Ha-
slingden Group (Neumann et al., 2006). A stratigraphic break between
the Calvert Superbasin and Isa Superbasin is marked by the intrusion of
the 1670 ± 3 Ma Sybella Granite (Neumann et al., 2006; Page et al.,
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Ore Geology Reviews 124 (2020) 103647
2000). The Gun, Loretta, River, Term, Lawn, Wide and Doom Super-
sequences make up the Isa Superbasin, and are composed of various
turbidites, carbonaceous shales and stromatolitic dolostones that were
deposited in a shallow to deep marine environment (Page et al., 2000;
Southgate et al., 2013). The Gun and Loretta Supersequences are
composed of the locally dominant Mount Isa Group, which contains in
stratigraphic order the Kennnedy Siltstone, Magazine Shale, Spear
Siltstone, Urquhart Shale, Native Bee Siltstone, Breakaway Shale,
Moondarra Siltstone, Warrina Park Quartzite and the Surprise Creek
Formation (Domagala et al., 2000).
The three superbasins and underlying basement have been subject
to multiphase deformation during the Isan Orogeny, with four major
shortening events (D1 D4) from 1610 1500 Ma (Bell, 1983; Bell and
Hickey, 1998; Page and Bell, 1986; Winsor, 1986). D1 involved a N–S
directed shortening event at 1610 ± 10 Ma, producing large scale E–W
trending folds and S1 cleavages (Page and Bell, 1986; Winsor, 1986). D2
involved a major E–W shortening event, producing the dominant N–S
B. Cave, et al.
grain of the Mount Isa Inlier and a slaty-like S2 cleavage (Bell, 1983;
Winsor, 1986). Earlier estimates favoured an age of 1544 ± 12 Ma for
D2 deformation (Page and Bell, 1986), but recent studies suggest that
D2 deformation occurred at ca. 1575 Ma (Duncan et al., 2006; Hand and
Rubatto, 2002). D3 (formally D2.5; (Bell and Hickey, 1998) is restricted
to localised areas affected by D2 deformation and produced highly
asymmetric deflections in S2 fabric and bedding with top to the east
movement (Bell and Hickey, 1998). D4 produced regional steep
NNW SSE striking folds and S3 foliations from 1530 to 1500 Ma (Bell,
1983; Page and Bell, 1986; Winsor, 1986).
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Ore Geology Reviews 124 (2020) 103647
Fig. 3. A schematic diagram portraying the series
of events associated with each metallogenic model
discussed in this study. (a) Model 1 represents syn-
sedimentary Pb-Zn mineralisation remobilised by
metamorphism and overprinted by syn-D4 Cu mi-
neralisation. (b) Model 2 represents the formation
of syn-sedimentary Cu-Pb-Zn-mineralisation. *The
influx of late fluids that remobilise and remove the
stratabound nature of Cu mineralisation is pro-
posed by McGoldrick and Keays (1990). (c) Model 3
represents the formation of epigenetic syn-D4 Cu-
Pb-Zn mineralisation. (d) The series of regional and
localised deformation events experienced in the
local Mount Isa area using the terminology of Davis
(2004). Age constraints: D1 (Page and Bell, 1986);
D2 (Duncan et al., 2006); D4 (Connors and Page,
1995; Page and Bell, 1986). Timing of D3 is esti-
mated only. The Mount Isa tectonic kinematics was
obtained from Bell (1983), Bell and Hickey (1998),
Winsor (1986).
The basement and overlying supersequences experienced amphi-
bolite facies metamorphism (up to 600 °C at 3 4 kbar pressure) during
regional D2 deformation of the Isan Orogeny (Rubenach, 1992). U-Pb
monazite ages of ca. 1575 Ma recording peak-metamorphic conditions
have been obtained from a cordierite-amphibolite orthogneiss within
the Hazeldene region (Hand and Rubatto, 2002) and ages of
1573 ± 12 Ma and 1577 ± 48 Ma have been produced from syn-D2
tourmaline (Duncan et al., 2006). The ca. 1575 Ma metamorphic event
has been attributed to the burial of the radiogenic element-rich Sybella
Batholith below the thick and insulating Mount Isa Group, with
B. Cave, et al.
additional heat provided by syn-D2 intrusions (McLaren et al., 1999;
Rubenach, 1992).
2.2. Deposit geology
The Mount Isa Cu-Pb-Zn deposit is hosted in the ca. 1650 Ma
Urquhart Shale of the Mount Isa Group (Fig. 1). The Urquhart Shale is
composed of highly interlayered fine-grained carbonaceous and dolo-
mitic sediments, pyritic shales and various tuffaceous beds (Neudert
and Russell, 1981). Sedimentological and microfossil data suggest the
Urquhart Shale was deposited in a shallow lacustrine environment
(Muir, 1981; Neudert and Russell, 1981). Cu and Pb-Zn mineralisation
is located adjacent the Paroo fault, which separates the Eastern Creek
Volcanics from the Urquhart Shale (Fig. 2a-c). At depth, the Paroo fault
dips moderately to the east where it is termed the Basement fault before
progressively steepening to the west (Long, 2010). Cu and Pb-Zn mi-
neralisation is located on the western limb of a regional D2 anticline
that resulted in the local Urquhart Shale being tilted ~70° to the west
(Bell et al., 1988; Davis, 2004). Overall, mineralisation is zoned from
Cu → Pb → Zn-rich outwards from the Paroo fault (Fig. 2a-c).
The largest Cu orebody (1100 orebody) is situated along a ramp in
the Paroo fault, while smaller orebodies (500 and 650 orebodies) are
positioned closer to the surface where they interdigitate, and locally
coincide with high-grade Pb-Zn mineralisation (Fig. 2a). Cu miner-
alisation is present as chalcopyrite and is largely confined to a pre-
mineralisation silica-dolomite alteration halo. Chalcopyrite post-dates
both fine- and coarse-grained pyrite, silica-dolomite, calcite and quartz,
and is traditionally considered coeval with pyrrhotite, minor sulfosalts,
and rare cubanite (Perkins, 1984). As the highest grades of Cu miner-
alisation are located within D4 folds, a syn-D4 timing is often cited for
the emplacement of Cu mineralisation (Bell et al., 1988; Perkins, 1997;
Perkins, 1984).
At the northern end of the orebody approximately 10 relatively
stratiform Pb-Zn orebodies are located at least 100 m up dip from the
Paroo fault (Fig. 2c), with the highest grades of Pb-Zn mineralisation
coinciding with the hinges and short limbs of D4 folds (Davis, 2004).
Galena and sphalerite are the dominant Pb and Zn minerals, and occurs
as stratiform bands that replace stratabound fine-grained pyrite-rich
and/or dolomitised shale layers, and as infill around highly-deformed
carbonaceous shale (Grondijs and Schouten, 1937; Perkins, 1997). At
the periphery of the Pb-Zn system, galena and sphalerite replace dis-
cordant pre-mineralisation silica-dolomite alteration (Perkins, 1997).
Siderite, coarse-grained pyrite and K-feldspar predate Pb-Zn miner-
alisation while pyrrhotite, ferberite and tetrahedrite are considered
coeval (Blanchard and Hall, 1937; Grondijs and Schouten, 1937).
2.3. Previous genetic models
The close spatial association between significant Cu and Pb-Zn mi-
neralisation is the subject of intense debate, with various models pro-
posed to explain this relationship (Fig. 3). With specific reference to the
relative timing of mineralisation events, the three contrasting me-
tallogenic models are: (1) syn-sedimentary Pb-Zn mineralisation over-
printed by epigenetic Cu mineralisation (Gulson et al., 1983; Smith
et al., 1978); (2) syn-sedimentary Cu and Pb-Zn mineralisation (Finlow-
Bates and Stumpfl, 1980; McGoldrick and Keays, 1990); and (3) Epi-
genetic syn-D4 Cu-Pb-Zn mineralisation (Davis, 2004; Grondijs and
Schouten, 1937; Perkins, 1997).
1) The most widely accepted model suggests that Pb-Zn mineralisation
formed in a syn-sedimentary SEDEX-like environment at ca.
1650 Ma (Fig. 3a). Pb-Zn mineralisation was then significantly re-
mobilised during metamorphism and D2 deformation before being
overprinted by subsequent Cu mineralisation at ca. 1520 Ma. This
model has been favoured by numerous studies (cited above) due to
the largely stratiform nature of the Pb-Zn ore relative to the
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Ore Geology Reviews 124 (2020) 103647
discordant Cu ore, which is a key criteria in the identification of
exhalative ore types (Leach et al., 2005). Smith et al. (1978) showed
that a large range in 34S/32S isotope values were given by samples
containing Pb-Zn mineralisation, contrary to a relatively small range
in 34S/32S isotopes from Cu-bearing samples. This study suggested
that samples containing sulphides from Pb-Zn mineralisation were
in isotopic equilibrium, while sulphide-bearing samples from Cu
mineralisation were in disequilibrium (Smith et al., 1978). This
evidence was used to suggest that Pb-Zn was deposited before re-
gional metamorphism and epigenetic Cu mineralisation formed after
regional metamorphism (Smith et al., 1978). Carr et al. (2004) used
an Pb isotope growth curve controlled by the Pb-isotope composi-
tion of feldspars from independently dated granites to differentiate
the sources of Cu and Pb-Zn mineralisation. As Pb isotopes from Pb-
Zn mineralisation plotted close to ca. 1650 Ma reference line, syn-
sedimentary Pb-Zn mineralisation was favoured. Differences in the
Pb isotope composition from Cu-bearing samples was used to imply
a second, separate Cu mineralising event.
2) The second model suggests that both Cu and Pb-Zn mineralisation
formed in a SEDEX-like environment at ca. 1650 Ma (Fig. 3b). A
geometric model produced by Finlow-Bates and Stumpfl (1980)
argued that the ore-bearing solution boiled its way up through the
stratigraphy, resulting in the brecciation of the pre-mineralisation
silica-dolomite lithology. Cooling of the ore solution resulted in the
precipitation of chalcopyrite within the stockwork, and fluids con-
taining Pb and Zn were expelled across the ocean floor, precipitating
galena, then sphalerite. The temperature drop associated with the
seawater mixing was used to explain the deposit scale-zonation of
Cu → Pb → Zn, consistent with the temperature-dependent solubi-
lity of the metals (Finlow-Bates and Stumpfl, 1980). Based on var-
ious volatile and whole rock trace-element data, McGoldrick and
Keays (1990) proposed a direct genetic link between Cu and Pb-Zn
mineralisation. The source of S was proposed as sedimentary with a
relatively cool (<200 °C) oxidized brine responsible for Cu and Pb-
Zn mineralisation. The Cu → Pb → Zn zonation was attributed to the
relative solubility of these metals (McGoldrick and Keays, 1990). It
was argued that the stratabound nature of the Cu ore was subse-
quently destroyed by post-ore fluids that channelled up through the
Paroo fault and re-distributed the Cu to higher levels to form the
smaller 500 and 650 Cu-orebodies (Fig. 3b; (McGoldrick and Keays,
1990).
3) The third model suggests that Cu and Pb-Zn mineralisation is both
epigenetic and coeval (Fig. 3c). Based on petrology completed on
250 polished blocks, Grondijs and Schouten (1937) suggested that
Cu and Pb-Zn ores replace carbonate, while stratiform Pb-Zn mi-
neralisation replaced bedding-parallel carbonate, deformed shale,
and fine-grained pyrite-rich shale. Analysis of the microstructural
and textural evidence of Pb-Zn ore by Perkins (1997) favoured a
coeval and epigenetic Cu-Pb-Zn model. It was suggested that an
evolving alteration system occurred alongside the formation of
layer-parallel and cross-cutting steep cleavages on the carbonaceous
Urquhart Shale during D4 deformation (Perkins, 1997). This was
subsequently overprinted by a short-lived Cu-Pb-Zn mineralisation
event (Perkins, 1997). Davis (2004) focused on the structural con-
trols on Pb-Zn mineralisation, favouring a syn-D4 Pb-Zn miner-
alisation event. This study showed that the Pb-Zn orebodies corre-
late with the presence of D4 folds, with the highest Pb-Zn grades
centred on the short limbs and hinges of D4 folds. By reconstructing
the pre-deformation architecture of the deposit, it was shown that a
syn-sedimentary model could not account for the geometry of the
Pb-Zn orebodies (Davis, 2004).
B. Cave, et al.
3. Methods
3.1. Core logging and sampling procedure
Using the dataset available from the Mount Isa Copper Operations, a
model defining the 1% shell of Cu, and 2.5% shell of Pb and Zn was
produced. This model was used to assess the availability of drill core
that intersected both Cu and Pb-Zn mineralisation. Resin blocks con-
taining each sample were produced following standard procedures and
used for Mineral Liberation Analysis (MLA) mapping and subsequent
LA-ICP-MS analyses. The lithology and mineralogy of the 8 drill cores
selected for this study were logged and sampled at least 8 times across
the transition from Cu to Pb-Zn-rich mineralisation. Attention was
given to the abundance and distribution of sulphides, and any corre-
sponding lithological changes. A combination of petrology and MLA
mapping was used to examine textural relationships and determine
mineral paragenesis. For comparison between trace element abun-
dances, chalcopyrite, sphalerite and galena-bearing samples from high-
grade Cu and Pb-Zn zones were also analysed. Samples representing
high-grade Pb-Zn mineralisation were selected from historic samples
available at The University of Adelaide and are representative of the
open cut Black Star Mine, and the No. 5 and No. 9 Pb-Zn orebodies
(Fig. 2c). Samples were also collected from a recently drilled explora-
tion hole (R25ED1) that intersected high-grade Pb-Zn mineralisation
above the 1100 Cu orebody (Fig. 2a). Samples representative of high-
grade Cu mineralisation were collected from the 650 and 3000 or-
ebodies (Fig. 2a, c). A sample from the silicified basalt-derived chlorite
schist from beneath the Paroo fault (also known as the basement) was
also analysed to represent the composition of coarse-grained galena and
chalcopyrite proximal to the Paroo fault (Fig. 2a).
3.2. SEM and MLA analysis
Electron Backscatter imaging and Mineral Liberation Analyses
(MLA) maps of the samples were completed using the Quanta 600 SEM
at Adelaide Microscopy. MLA maps were acquired using the raster
mode with an X-ray spectra collected every 4 µm. Attention was given
to sulphide textures, mineral inclusions, and the recognition of various
stages of mineralisation.
3.3. LA-ICP-MS analyses
LA-ICP-MS spot analyses of chalcopyrite, sphalerite and galena were
completed using a NWR213 solid state 213 nm laser ablation system
coupled with an Agilent 7900 quadrupole ICP-MS at Adelaide
Microscopy. Ablation was conducted in an atmosphere of He (0.6 L/
min) that was mixed with Ar (0.88 L/min) upon leaving the ablation
cell. The material then passes through a pulse-homogenisation device
before being introduced to the ICP torch.
To reduce the amount of cross-contamination from Pb within the
cell, sulphides were analysed in the order of chalcopyrite, sphalerite
then galena. Ablation spot size ranged from 12 70 µm in diameter
depending on the size of the mineral analysed. To overcome the het-
erogeneous nature of sulphide minerals (as documented by (Cook et al.,
2016), a minimum of 20 spots was analysed across each coarse-grained
mineral. Fine-grained minerals were characterised by analysing as
many spots as possible over the area of the grain.
The repetition rate of the laser was 5 Hz with a consistent fluence of
~4 J/cm2. Pre-ablation consisted of 5 pulses, followed by a 20 s delay
to allow adequate cell wash out before the proceeding analyses. Data
collection consisted of 30 s background collection, followed by 40 s of
ablation. The isotopes monitored include: 27Al, 29Si, 55Mn, 57Fe, 59Co,
60
Ni, 65Cu, 66Zn, 69Ga, 71Ga, 75As, 77Se, 95Mo, 109Ag, 111Cd, 113In, 115In,
118
Sn, 121Sb, 125Te, 182W, 197Au, 201Hg, 205Tl, 206Pb, 207Pb, 208Pb, and
209
Bi. The dwell time of each isotope was 0.02 s, except for 27Al, 29Si,
34
S, and 55Mn with dwell times of 0.005 s and 59Co, 60Ni, 65Cu, 66Zn
6
Ore Geology Reviews 124 (2020) 103647
206
Pb, 207Pb, and 208Pb with dwell times of 0.01 s. The GSD-1G (USGS)
and STDGL3 standards (CODES, University of Tasmania;
(Danyushevsky et al., 2011)) were analysed using a 70 µm diameter
spot size with a 25:2 standard sample bracketing approach (2 standard
samples analysed twice every 25 unknowns).
Each analysis was individually checked for mineral inclusions by
inspecting the time-resolved depth profile of each isotope during data
processing. Data with obvious inclusions were disregarded, and inclu-
sion-free portions of the time-resolved depth profile were selected. This
resulted in a total of 677, 381, and 249 successful analyses of chalco-
pyrite, sphalerite and galena, respectively.
LA-ICP-MS analyses were processed using Iolite (Paton et al., 2011),
with instrumental drift and mass bias corrected for using the Trace_E-
lement_IS DRS (Woodhead et al., 2007). The STDGL3 standard was used
as the primary standard, with GSD-1G used as a secondary standard to
perform accuracy checks. An exception to this was Ga, where the GSD-
1G standard was used as the primary standard. Due to isobaric inter-
ference between 113In and 113Cd using the ICP-MS, 115In was primarily
used to estimate the concentration of In. Likewise, the concentration of
69
Ga and 72Ge were used to estimate the concentrations of Ga and Ge
respectfully. The Sn content in these sulphides was sufficiently low so
the interference of 115Sn on 115In was insignificant. Chalcopyrite was
assumed to be stoichiometric and processed using an internal standard
of 34.63 wt% Cu. Galena was processed using an internal standard of
86.60 wt% 208Pb. Sphalerite was processed using an assumed internal
standard of 5% Fe, with resulting concentrations normalized to assume
a stoichiometric composition of 100% (Zn,Fe)S. To check the validity of
this method, the concentration of Zn, Fe and S was measured on various
sphalerite samples using a Cameca SXFive Electron Microprobe at
Adelaide Microscopy. A comparison between the normalised LA-ICP-MS
data and the microprobe show good agreement (typically < 10%) and
were always within error of the normalised LA-ICP-MS data
(Supplementary Table 1).
4. Results
4.1. Petrography
High-grade Cu mineralisation is primarily hosted by discordant pre-
mineralisation silica-dolomite alteration (Fig. 4a–j). Silica-dolomite is
the term used to describe coarse-grained crystalline dolomite that has
undergone subsequent silicification. Stratiform fine-grained pyrite is
largely absent in areas containing abundant Cu mineralisation and only
occurs in variable-sized shale fragments brecciated by silica-dolomite
(Fig. 4c). The formation of silica-dolomite predates minor calcite
veining and the precipitation of siderite (Fig. 4c–d). Coarse-grained
pyrite forms in the calcite veins (Fig. 4c), silica-dolomite (Fig. 4e–f, i)
and siderite dominant lithologies. Arsenopyrite often rims and forms
around coarse-grained pyrite, suggesting later growth. Coarse-grained
chalcopyrite and pyrrhotite often replace silica-dolomite, while also
enveloping and replacing calcite and siderite (Fig. 4a–j). Chalcopyrite
and pyrrhotite envelope and infill cracks in coarse-grained pyrite and
arsenopyrite, implying they are paragenetically later (Fig. 4h–i). Fine-
to medium-grained gangue minerals associated with Cu-mineralisation
include biotite, chlorite, K-feldspar, apatite and cobaltite. Sphalerite
and galena are commonly found in areas of high-grade Cu mineralisa-
tion as 20 200 µm sized inclusions located primarily within chalco-
pyrite (Fig. 4g–j). Larger (>2 mm) sphalerite and galena grains are
uncommon (Fig. 4h). Additionally, sphalerite and galena occur repla-
cing silica-dolomite and calcite (Fig. 4g–i), as inclusions within pyr-
rhotite (Fig. 4j), and as infill in fractured coarse-grained pyrite and
arsenopyrite (Fig. 4c, h i).
Through the transition from Cu to Pb-Zn mineralisation, highly-
stratiform carbonaceous shale and fine-grained pyrite-rich shale be-
come more abundant and often occur as clasts brecciated by silica-do-
lomite (Fig. 5a). Fine-grained pyrite is primarily stratiform (Fig. 5a),
B. Cave, et al. Ore Geology Reviews 124 (2020) 103647

Fig. 4. Photographs and MLA images of samples representative of Cu mineralisation. (a) Chalcopyrite dominant mineralisation with minor pyrrhotite replacing
discordant silica-dolomite alteration. (b) Coarse-grained chalcopyrite and pyrrhotite replacing silica-dolomite alteration. (c) MLA map showing a calcite vein cutting
through the silica-dolomite containing pyrite, arsenopyrite and sphalerite. Note the presence of fine-grained pyrite within the shale clast. (d) MLA map showing
siderite and quartz surrounding dolomite. Minor chalcopyrite, pyrrhotite and apatite are also present. (e) MLA map showing a fragmented piece of shale infilled by
silica-dolomite, coarse-grained pyrite and chalcopyrite. (f) MLA map of silica-dolomite alteration that has undergone subsequent silicification. Pyrrhotite with minor
chalcopyrite are present between the contact of silica-dolomite and quartz. (g) MLA map of chalcopyrite and pyrrhotite replacing dolomite. Galena and sphalerite are
present as inclusions within chalcopyrite. (h) MLA map of coeval sphalerite and chalcopyrite replacing coarse-grained pyrite and dolomite. (i) MLA map of chal-
copyrite with minor sphalerite and galena replacing silica-dolomite and enveloping coarse-grained pyrite. (j) MLA map of pyrrhotite replacing silica-dolomite with
minor chlorite and K-feldspar. Sphalerite and galena are present as inclusions within pyrrhotite. Abbreviations: Cpy = Chalcopyrite, Gal = Galena, Sph = Sphalerite,
Asp = Arsenopyrite, Cgpy = Coarse-grained Pyrite, Fgpy = Fine-grained Pyrite, Pyrr = Pyrrhotite, Sid = Siderite, Dol = Dolomite, Sil-dol = Silica-dolomite,
Chl = Chlorite, Ap = Apatite, Kfs = K-feldspar, Bt = Biotite.

with minor fine-grained pyrite occurring in veins. Despite the common
occurrence of shale clasts within the silica-dolomite breccia containing
fine-grained pyrite, there are no examples of stratabound sphalerite and
galena being brecciated and overprinted by silica-dolomite. Sphalerite
and galena occur primarily as medium- to coarse-grained components
that replace the silica-dolomite breccia surrounding the shale clasts
(Fig. 5a). Across the Cu to Pb-Zn transition, chalcopyrite is pre-
dominantly located in zones containing variable amounts of Pb-Zn
mineralisation (Fig. 5b–c), with minor chalcopyrite also occurring in
pyrrhotite-dominated lithologies. Galena and sphalerite replace silica-
dolomite breccias (Fig. 5a, c), siderite, carbonate-rich shale layers, fine-
grained pyrite-rich shale, and occur as infill around deformed carbo-
naceous shale (Fig. 5b–c). Consistent with high-grade Cu-mineralisa-
tion, chalcopyrite, sphalerite and galena envelope coarse-grained
pyrite, arsenopyrite, siderite and calcite (Fig. 5d–i). Gangue minerals
associated with the ore-stage mineralisation are often fine-grained and
include biotite, chlorite, K-feldspar and apatite (Fig. 5f–i). SEM imaging
reveals that chalcopyrite, galena and pyrrhotite appear coeval, and
slightly postdate the precipitation of sphalerite (Fig. 5e). When chal-
copyrite, sphalerite and galena are present together in stratabound or
deformed layers, galena, chalcopyrite and pyrrhotite are often dis-
tributed between sphalerite and the enclosing host rock (Fig. 5b–c). In
some instances, there is a zonation from sphalerite to galena to chal-
copyrite and pyrrhotite, with chalcopyrite and pyrrhotite located clo-
sest to the carbonaceous shale and sphalerite the most distal. Chalco-
pyrite often occurs in discordant veins that stem from stratabound Pb-
Zn mineralisation (Fig. 5f). Although texturally chalcopyrite and galena
appear coeval, the observation that chalcopyrite often occupies the
paragenetically last sites supports a slightly later precipitation.
Towards high-grade Pb-Zn mineralisation, the presence of silica-
dolomite significantly decreases (Fig. 6a–d). Deformed carbonaceous
shale, fine-grained pyrite-rich shale and shale with carbonate-rich
layers become the dominant mineralised lithologies (Fig. 6a–e). Spha-
lerite is common in lithologies consisting of stratabound fine-grained
pyrite where it exhibits infill and replacement textures (Fig. 6a–c).
While sphalerite is still regularly abundant, galena is primarily localised

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Fig. 5. Photographs, BS and MLA images of samples representative of mineralisation across the Cu to Pb-Zn transition. (a) Fragments of shale and fine-grained pyrite-
rich shale brecciated by silica-dolomite alteration. Minor sphalerite is present as infill within the silica-dolomite. (b c) Highly deformed carbonaceous shale infilled
by sphalerite, galena, pyrrhotite and chalcopyrite. Chalcopyrite occupies areas around highly deformed fold hinges. (d) BS image of deformed arsenopyrite infilled by
subsequent sphalerite and galena. (e) BS image of chalcopyrite, sphalerite and galena replacing coarse-grained pyrite. Chalcopyrite is seen replacing sphalerite. (f)
MLA map of a siderite-rich lithology partially replaced by coarse-grained pyrite, sphalerite, galena and chalcopyrite. Chalcopyrite appears in a discordant vein that
extends outward from stratabound Pb-Zn mineralisation. (g) MLA map showing clasts of shale brecciated by quartz with minor dolomite and siderite. Chalcopyrite,
sphalerite and galena are co-genetic and infill/replace the quartz dominant lithology. (h) MLA map of coeval sphalerite, galena and chalcopyrite replacing and
enveloping a quartz-dominated lithology. (i) MLA map showing sphalerite and galena replacing coarse-grained pyrite, quartz and dolomite with minor apatite,
biotite, chlorite and K-feldspar. Abbreviations: Cpy = Chalcopyrite, Gal = Galena, Sph = Sphalerite, Cgpy = Coarse-grained Pyrite, Pyrr = Pyrrhotite,
Sid = Siderite, Dol = Dolomite, Sil-dol = Silica-dolomite, Chl = Chlorite, Bt = Biotite, Asp = Arsenopyrite, Ap = apatite, Kfs = K-feldspar.

to carbonate-rich layers, discordant silica-dolomite, and in deformed
carbonaceous shale (Fig. 6d–e). On a macroscopic scale, Pb-Zn miner-
alisation regularly crosscuts the shale stratigraphy. BS imaging and
MLA mapping show that in regions of high-grade stratiform Pb-Zn
mineralisation, galena, sphalerite and pyrrhotite infill and replace a
previous assemblage consisting of at least in part fine- and coarse-
grained pyrite, dolomite, quartz (Fig. 6f), and siderite. Other minerals
associated with Pb-Zn mineralisation include fine-grained apatite,
chlorite, K-feldspar, freibergite and tetrahedrite. In every instance, ga-
lena appears to have crystallised after sphalerite (Fig. 6g–h). Chalco-
pyrite is uncommon in areas of high-grade Pb-Zn mineralisation and is
documented as very fine- to medium-grains occurring alongside spha-
lerite, galena and pyrrhotite (Fig. 6a, d, g), and as micro-inclusions
within fractured coarse-grained pyrite.
4.2. Assay data and core logging
Assay data across the Cu to Pb-Zn transition reveals a range of
trends (Fig. 7). Pb and Zn concentrations often show a positive corre-
lation, and occasionally a negative correlation with Cu. The trends
between Cu and Pb and/or Zn are less obvious. However, peaks and
troughs in Pb and Zn concentrations regularly coincide with Cu. Ex-
amples of this are found from 230 250 m in drill core 201003232
(Fig. 7a), 470 490 m and 502 510 m in drill core 201208592 (Fig. 7d),
300 320 m and 350 370 m in drill core 200209312 (Fig. 7e). Assay
data often emphasises the preferred host lithology of Cu and Pb-Zn
mineralisation. Higher Cu assays often correlate with the presence of
silica-dolomite alteration, a relationship that is demonstrated from
90 100 m and 120 125 m in drill core 201008392 (Fig. 7f),
100 140 m in drill core 201502192 (Fig. 7g) and 130 140 m in drill
core 200501422 (Fig. 7h). The occurrence of fine-grained stratiform
pyrite occasionally correlates with an increase in Pb and Zn assay

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Fig. 6. Photographs, BS and MLA images of samples representative of high-grade Pb-Zn mineralisation. (a) Carbonaceous shale with multiple layers of fine-grained
pyrite and crystalline dolomite. Sphalerite replaces the dolomite and fine-grained pyrite. Minor chalcopyrite is present. (b) Carbonaceous and fine-grained pyrite-rich
shale brecciated by silica-dolomite alteration. Sphalerite is present in fractures around the fine-grained pyrite, and as infill in the silica-dolomite lithology. (c) BS
image of Fig. 6a showing the replacement of fine-grained pyrite by sphalerite. (d) Highly stratabound Pb-Zn mineralisation. Sphalerite replaces fine-grained pyrite,
galena replaces a crystalline dolomite layer and chalcopyrite is present as infill within a discordant vein. (e) High-grade Pb mineralisation replacing nearly stra-
tabound silica-dolomite alteration with minor pyrrhotite. (f) MLA map of high grade Zn-mineralisation replacing a previous assemblage of coarse-grained pyrite,
quartz and dolomite. (g) BS image showing sphalerite, galena and chalcopyrite replacing dolomite around shale clasts. It is shown that galena forms around sphalerite
and occasionally chalcopyrite. (h) BS image showing high-grade Pb mineralisation. Galena envelopes sphalerite, pyrrhotite and dolomite. Abbreviations:
Cpy = Chalcopyrite, Gal = Galena, Sph = Sphalerite, Cgpy = Coarse-grained Pyrite, Pyrr = Pyrrhotite, Sid = Siderite, Dol = Dolomite, Sil-dol = Silica-dolomite,
Ap = Apatite.

values, and a corresponding decrease in Cu values. This occurs from
520 550 m in drill core 200206252 (Fig. 7b) and 380 400 m in drill
core 200209162 (Fig. 7c). Assay data shows the transition from dom-
inantly Cu to Pb-Zn mineralisation varies from abrupt to gradual as
demonstrated from 360 400 m in drill core 200209162 (Fig. 7c),
480 530 m in drill core 201208592 (Fig. 7d), 320 350 m in drill core
200209312 (Fig. 7e) and 50 100 m in drill core 201008392 (Fig. 7f).
4.3. Sulphide trace element compositions
Trace element data collected in this study is presented in
Supplementary Table 2 and Figs. 8 to 11. For consistency, the Cu to Pb-
Zn transition is documented as the first time Cu > Pb + Zn in assay
data, or vice versa. Samples were arranged and plotted in the relative
order of their distance across the Cu to Pb-Zn transition (Figs. 9 to 11).
The median concentration (excluding samples from high-grade Cu and
Pb-Zn ore used for comparison) was calculated for each element using
samples from either side of the interpreted Cu to Pb-Zn transition
(Fig. 7). Where a consistent trend in the data is present, a locally
weighted scatter-plot smoother (LOESS) curve was fitted, which also
does not include the samples from high grade Cu and Pb-Zn ore used for
comparison (Figs. 9 to 11).
In the chalcopyrite, sphalerite and galena mineral assemblages
analysed, chalcopyrite is the preferred host of Ni, Ge and Sn, galena is
the preferred host of Ga, Se, Ag, Sb, Te, Tl and Bi, and sphalerite is the
preferred host of Mn, Co, Cd and In (Fig. 8; Supplementary Table 2).
Chalcopyrite and galena possess similar Mn concentrations, and chal-
copyrite and sphalerite possess similar concentrations of Se, Te and Tl
(Fig. 8). The As and Al concentration in chalcopyrite, sphalerite and
galena are relatively subequal (Fig. 8). For the mineral assemblage
analysed, the concentration of W, Mo and Au were consistently below
the detection limit of the ICP-MS.

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Fig. 7. Assay data, corresponding lithologies and mineral abundances from the drill core sections used in this study. The transition is defined as the first time Cu
assays > Pb + Zn (or vice-versa). Note the correlation in peaks and dips between Pb, Zn and Cu assay data. Abbreviations: Cpy = Chalcopyrite, Gal = Galena,
Sph = Sphalerite, Asp = Arsenopyrite, Cgpy = Coarse-grained pyrite, Pyrr = Pyrrhotite, Sid = Siderite, Cob = Cobaltite, Ksp = K-feldspar.

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B. Cave, et al. Ore Geology Reviews 124 (2020) 103647

Fig. 7. (continued)

11
B. Cave, et al.
Fig. 8. Box and whisker plots displaying the concentration of Al, Mn, Co, Ni, Ga, Ge, As, Se, Ag, Cd, In, Sn, Sb, Te, Tl and Bi in chalcopyrite, galena and sphalerite.
4.3.1. Chalcopyrite
Chalcopyrite hosts measurable concentrations of Al, Mn, Co, Ni, Zn,
Ga, Ge, As, Se, Ag, Cd, In, Te, Sn, Sb, Tl, Pb and Bi. The median con-
centration of Bi in chalcopyrite decreases from 2.54 ppm in samples
associated with Cu mineralisation to 0.25 ppm in samples associated
with Pb-Zn mineralisation (Fig. 9a). An overall trend is also present,
showing a decrease in Bi concentrations in chalcopyrite from Cu to Pb-
Zn-rich mineralisation. The concentration of Pb in chalcopyrite is
highly variable and often varies over an order of magnitude within a
single grain (Fig. 9b). The median concentration of Pb in chalcopyrite
increases across the Cu to Pb-Zn transition from 5.69 ppm in Cu
dominant samples to 18.9 ppm in Pb-Zn dominant samples (Fig. 9b).
Chalcopyrite from the historic Black Star Pb-Zn mine, and the nearby
high-grade Pb-Zn prospect (R25ED1) are consistent with the trends
above and possess relatively low concentrations of Bi (0.02 0.22 ppm)
and relatively high concentrations of Pb (4.34 480 ppm). Comparably,
chalcopyrite from high-grade Cu mineralisation in the 1100 and the
650 Cu orebodies possesses relatively high concentrations of Bi
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Ore Geology Reviews 124 (2020) 103647
(0.51 38.8 ppm) and relatively low concentrations of Pb
(2.72 173 ppm), also conforming to the trends above (Fig. 9a–b). In
contrast, a chalcopyrite bearing sample from the basement possesses
low to moderate concentrations of Bi (0.01 0.41 ppm), which is in-
consistent with the trends presented above, and a low to moderate
concentration of Pb (1.69 480 ppm).
4.3.2. Galena
Galena hosts measurable concentrations of Al, Mn, Ni, Co, Cu, Fe,
Zn, Se, Ag, As, Cd, Ga, Ge, In, Sn, Sb, Te, Tl and Bi. The median con-
centration of Se and Te in galena is relatively enriched in samples as-
sociated with Cu mineralisation (Se = 133 ppm, Te = 17.5 ppm)
compared to galena from samples associated with Pb-Zn mineralisation
(Se = 5.9 ppm, Te = 1.04 ppm; Fig. 10a–b). The Cd concentration of
galena shows a decreasing trend across the transition from Cu to Pb-Zn
mineralisation (Fig. 10c). The concentration of Bi in galena decreases in
orders of magnitude from Cu mineralisation to Pb-Zn mineralisation
(Fig. 10d). In contrast, the median concentration of Sb in galena
B. Cave, et al. Ore Geology Reviews 124 (2020) 103647

Fig. 9. The concentration of (a) Bi and (b) Pb in chalcopyrite as a function of the distance across the Cu to Pb-Zn transition. Box plot colours reflect the drill core
sampled. The solid vertical line represents the interface between Cu and Pb-Zn mineralisation where Pb + Zn > Cu in assay data. Horizontal dotted lines represent
the median values of samples associated with Cu and Pb-Zn mineralisation. The solid blue line represents the LOESS regression while shaded regions represent the
95% confidence interval. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

increases by orders of magnitude from Cu to Pb-Zn-rich mineralisation
(Fig. 10e). Comparable samples from high-grade Pb-Zn mineralisation
conform to the trends above and have comparably low concentrations
of Se (0.61 31.4 ppm), Cd (3.86 110 ppm), Te (0.16 3.05 ppm) and
Bi (3.53 13.16 ppm), and high concentrations of Sb (5910 420 ppm;
Fig. 10). Analysis of a galena-bearing sample from the basement (re-
presentative of mineralisation close to the Paroo fault) mostly agrees
with the trends above, containing elevated concentrations of Se
(82.5 93.6 ppm), Cd (150.1 282.2 ppm), Te (15.1 21.9 ppm) and Bi
(756.8 1169 ppm; Fig. 10). In contrast, this sample is relatively en-
riched in Sb (325 879 ppm), inconsistent with the trend displayed in
Fig. 10d.
4.3.3. Sphalerite
Sphalerite hosts measurable concentrations of Al, Mn, Cu, Co, Ni,
Ga, Ge, As, Se, Ag, Cd, In, Sn, Sb, Te, Tl, Bi and Pb. Note that no
sphalerite was observed in samples obtained from drill core
201003232, and therefore no corresponding analysis was made.
Although there is large variation in the data, sphalerite associated with
Cu mineralisation is generally enriched in Co (median = 117.3 ppm)
and Bi (median = 1.45 ppm) compared to sphalerite associated with
Pb-Zn mineralisation (median Co = 5.37 ppm, median Bi = 0.22 ppm;
Fig. 11a–b). Even with large variations in the concentration of in-
dividual grains, the LOESS trends show an increase in the concentration
Sb, Pb and Ag in sphalerite across the transition from Cu to Pb-Zn
mineralisation (Fig. 11c–e). Samples from high-grade Pb-Zn miner-
alisation largely conform to the trends described above, possessing
highly variable concentrations of Co (0.03 52.7 ppm), Ag
(1.2 329.7 ppm), Sb (0.5 348.1 ppm) and Pb (2.4 7425 ppm) and
relatively low concentrations of Bi (0.01 0.11 ppm; Fig. 11b). A
sphalerite bearing sample representative of high-grade Cu mineralisa-
tion (2003061422) possesses relatively high Co (46.9 54.4 ppm) and
moderate concentrations of Ag (11.5 52.4 ppm), Sb (1.22 3.45 ppm)
and Pb (11.92 52.2 ppm; Fig. 11a, c–e). In contrast, this sample has a
relatively low concentration of Bi (0.05 0.11 ppm), inconsistent with
the trend shown in Fig. 11b.

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Fig. 10. The concentration of (a) Se, (b) Te, (c) Cd, (d) Bi and (e) Sb in galena as a function of distance across the Cu to Pb-Zn transition. Box plot colours reflect the
drill core sampled. The solid vertical line represents the interface between Cu and Pb-Zn mineralisation where Pb + Zn > Cu in assay data. Horizontal dotted lines
represent the median values of samples associated with Cu and Pb-Zn mineralisation. The solid blue line represents the LOESS regression while shaded regions
represent the 95% confidence interval. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

4.4. Sphalerite geothermometry
Using the concentration of Ga, Ge, In, Mn and Fe in sphalerite from
all samples, the GGIMFis geothermometer (Frenzel et al., 2016) yields a
median homogenisation temperature of 343 ± 44 °C (Fig. 12a;
Supplementary Table 3). Of the 221 calculations, temperature estimates
(using the 2σ error of each analyses) ranged from a minimum of
267 ± 25 °C to a maximum of 397 ± 82 °C. Due to: (1) the relatively
small number of samples that possessed reliable Mn, Ga, and Ge con-
centrations (n = 221/384); (2) large errors associated with each esti-
mate (averaging 46.6 °C); and (3) occasionally large variations from
analyses within single grains (up to 103.3 °C), portraying temperature-
related patterns across the Cu to Pb-Zn transition using this method is
considered speculative, and therefore has not been attempted in this
study.
5. Discussion
5.1. Trace element substitution mechanisms and correlations with
physicochemical factors
The concentrations of trace elements in chalcopyrite, sphalerite and
galena are the result of lattice-bound solid solution or mineral inclu-
sions (Cook et al., 2009; George et al., 2015, 2018, 2016). As this study
is focused on defining physicochemical conditions across the Cu to Pb-
Zn transition, only the trace elements that exhibit a change in con-
centration across this transition are discussed below.
5.1.1. Chalcopyrite
It has been shown by George et al. (2016) that chalcopyrite is often
the least preferred host of trace elements when co-crystallised with
other base metal sulphides such as sphalerite and galena, resulting in
comparably lower concentrations of Co, Se, Ag and Bi. This conclusion
is consistent with our results (Fig. 8) where chalcopyrite is not the
primary host of any of the elements mentioned above but is also not the
least preferred host to any of these elements.
This study shows that the concentration of Bi decreases over the
transition from Cu to Pb-Zn mineralisation (Fig. 9a). As galena is the
primary host of Bi (Fig. 8), the decrease in Bi concentrations from Cu to
Pb-Zn mineralisation likely reflects either the presence and/or absence
of co-crystallising galena, or the availability of Bi during chalcopyrite
crystallisation. As Bi is also relatively depleted in both galena and
sphalerite across the Cu to Pb-Zn transition, it is suggested that the
increased concentration of Bi in chalcopyrite reflects the distribution of

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Fig. 11. The concentration of (a) Co, (b) Bi, (c) Ag, (d) Sb, and (e) Pb in sphalerite as a function of distance across the Cu to Pb-Zn transition. Box plot colours reflect
the drill core sampled. The solid vertical line represents the interface between Cu and Pb-Zn mineralisation where Pb + Zn > Cu in assay data. Horizontal dotted
lines represent the median values of samples associated with Cu and Pb-Zn mineralisation. The solid blue line represents the LOESS regression while shaded regions
represent the 95% confidence interval. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Bi within the primary ore-bearing fluid during chalcopyrite crystal-
lisation.
The concentration of Pb in chalcopyrite increases across the Cu to
Pb-Zn transition (Fig. 9b). Pb can be incorporated into chalcopyrite as a
lattice bound constituent, or as micro-inclusions of galena. Due to the
large variation in Pb concentrations within a single grain, it is suggested
that Pb likely exists within chalcopyrite as micro-inclusions of galena.
This is consistent with the petrographic observations that show galena
as inclusions within chalcopyrite in areas of high-grade Cu miner-
alisation. The increase in Pb towards Pb-Zn mineralisation is consistent
with the zonation of the ore-deposit, reflecting the relative solubility of
Pb in comparison to Cu.
5.1.2. Galena
The concentrations of Se and Te in galena are enriched in samples
associated with Cu-mineralisation compared to samples associated with
Pb-Zn mineralisation (Fig. 10a–b). Selenium is likely incorporated into
galena through the involvement of solid solution with clausthalite
(PbSe) via the substitution Se2− ↔ S2− (Liu and Chang, 1994). Sele-
nium has previously been suggested as a temperature-sensitive trace
element and has been documented to increase in pyrite as the direct
result of an increasing crystallisation temperature (Grant et al., 2018;
Keith et al., 2018). High concentrations of Se in galena have also been
recorded in Cu-rich ore compared to Cu-poor ore in the Neves-Corvo
VHMS deposit (Carvalho et al., 2018), which was attributed to its
proximity to the mineralising fluid source. Galena does not form a
continuous solid solution with altatide (PbTe), resulting in inclusions of
altatide within galena (Darrow et al., 1966; Liu and Chang, 1994).
Tellurium is mobile in fluids that have a neutral to alkaline pH, are of
low salinity, and possess a high fO2 (Grundler et al., 2013; Keith et al.,
2018). Keith et al. (2016) concluded that the Te concentration of pyrite
varied with stratigraphic depth in the Skouriotissa volcanic-hosted
massive sulphide deposit, being enriched in the hotter stockwork zones
compared to pyrite formed in the shallower massive sulphide mounds.
Conversely, a recent study by Keith et al. (2018) concluded that the
concentration of Te in pyrite is largely temperature independent.
Grundler et al. (2013) suggested that processes such as fluid-rock in-
teraction and fluid-mixing results in a dramatic decrease in Te solubi-
lity, leading to its precipitation.
Cadmium is typically incorporated into the galena via the sub-
stitution Cd2+ ↔ Pb2+ (George et al., 2015). Galena is the secondary
host of Cd behind sphalerite, consistent with previous studies regarding
co-crystallised galena and sphalerite (George et al., 2015, 2016). As the
Cd concentration of sphalerite does not show any systematic variation

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B. Cave, et al.
Fig. 12. (a) A histogram of the calculated homogenisation temperature of sphalerite using the GGIMFis geothermometer (Frenzel et al., 2016) with a normal
distribution overlay. (b) Previous temperature estimates of ore-forming processes and alteration stages from within the deposit. The S-isotope equilibrium between
sphalerite and galena and sphalerite and pyrrhotite are from 1Painter et al. (1999). The estimated temperature of Cu mineralisation and silica-dolomite alteration are
given by 2Heinrich et al, (1989), the formation of chlorite-alteration is given by 3Waring (1990) and temperature estimates using δ18O thermometry are from 4Mering
et al. (2018).
Fig. 13. The correlation between Bi + Sb vs Ag in galena. Red dots were not
used in the calculation of the slope or R2. Shade of each data point is re-
presentative of their bismuth concentration. As Bi concentrations increase, the
slope of the Bi + Sb vs Ag line decreases. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this
article.)
over the Cu to Pb-Zn transition, it is suggested that the decrease in Cd
concentrations in galena associated with Cu-mineralisation reflects the
absence of co-crystallising sphalerite, resulting in an increase of Cd
partitioning into galena.
Bismuth shows a significant decrease in concentration across the Cu
to Pb-Zn transition (Fig. 10d), while Sb shows a significant increase
(Fig. 10e). The exception to this trend is the concentration of Sb from
the basement sample, which possesses relatively high Sb. This could
reflect early crystallisation of this sample during the infiltration of the
ore-bearing fluids, crystallising while the availability of Sb, Ag and Bi
were elevated, and therefore possessing a relatively high concentration
of all three elements. Bi and Sb can be incorporated into galena via the
solid solution Ag+ + (Bi, Sb)3+ ↔ 2Pb2+ (Sharp and Buseck, 1993), or
(Ag, Tl, Cu)+ + (Bi, Sb)3+ ↔ 2Pb2+ (George et al., 2015). Due to the
positive correlation between Ag vs Bi + Sb (Fig. 13) the former sub-
stitution mechanism is expected to be dominant. When Bi
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Ore Geology Reviews 124 (2020) 103647
is < 100 ppm, there is a strong positive correlation (R2 = 0.99) be-
tween Ag vs Bi + Sb with a slope of 0.789. When Bi increases to
100 5000 ppm, R2 = 0.96 with a decreased slope of 0.718. When Bi is
high (>5000 ppm), R2 = 0.98 and the slope further decreases to 0.563
(Fig. 13). Ideally, the Ag vs (Bi + Sb) line should have a slope of 1.
However, it has been suggested by George et al. (2015) that if there is
significantly more Bi and Sb available to galena than Ag, Tl and Cu
during formation, then Bi and Sb can undergo solid solution through
2(Bi,Sb)3+ + □↔ 3Pb2+ (vacancy denoted by □). The results above
indicate that when Bi is <100 ppm, Sb is the dominant element un-
dergoing solid solution with Ag via Ag+ + (Sb)3+ ↔ 2Pb2+. Here, the
slope of the Ag + (Bi + Sb) line is already 0.789, suggesting that Sb is
significantly more abundant than the combined concentration of Ag, Cu
and Tl available to galena during crystallisation. As shown above, when
Bi increases > 5000 ppm, the slope of Bi + Sb vs Ag line decreases,
suggesting that the additional Bi results in significantly more solid so-
lution. Previous studies have demonstrated that the concentration of Sb
in galena typically increases from source to sink in porphyry, skarn and
polymetallic replacement deposits (Amcoff, 1984; George et al., 2015;
Lueth et al., 2000). Lueth et al. (2000) showed that a decrease in Sb in
galena correlated with increasing S-isotope values, tracing previously
established flow paths over a deposit scale. It has also been shown that
the Bi/Sb ratio in galena will often increase down stratigraphy towards
galena-rich ore due to a larger solubility of Ag-Bi compared to Ag-Sb
(Amcoff, 1984). Both Bi and Sb exist as hydroxide complexes (Bi
(OH)3(aq)/Bi(OH)2+ (aq) and Sb(OH)3(aq)) in neutral pH, low to medium
salinity hydrothermal fluids, a mixture of hydroxide and chloride
complexes (Bi(OH)3/BICl3 and Sb(OH)3/SbClnn−3) in acidic fluids with
moderate Cl concentrations, and predominantly as chloride complexes
in highly acidic, Cl-rich fluids (Brugger et al., 2016; Etschmann et al.,
2016; Pavlova et al., 2006; Tooth et al., 2013). While there are many
similarities in the behaviours exhibited by Bi and Sb in geofluids, there
is a substantial difference in the temperature-dependent solubilities of
Bi and Sb (Tooth et al., 2013). High temperature (>400 °C) fluids are
required for any significant transport of Bi, while Sb is highly mobile at
lower temperatures, resulting in the formation of low-temperature
(<200 °C) Sb deposits (Bailly et al., 2000; Guillemette and Williams-
Jones, 1993; Tooth et al., 2013). Therefore, it is suggested that the
correlations shown in Fig. 10d–e are the result of a decreasing fluid
temperature, resulting in Bi being concentrated closer to the source of
the fluids and Sb being concentrated further away from the source.
B. Cave, et al.
5.1.3. Sphalerite
Sphalerite from Cu-rich mineralisation are enriched in Co relative to
sphalerite from Pb-Zn-rich mineralisation (Fig. 11a). Due to the similar
size of the Co2+ ion compared to the Fe2+ ion, Co directly replaces Fe
via Co2+↔ Fe2+ (Cook et al., 2009). As sphalerite is the preferred host
of Co within the chalcopyrite, galena and sphalerite assemblage, the Co
concentration likely reflects its original distribution within the ore-
bearing fluid during sphalerite precipitation. A recent study by Lee
et al. (2019) demonstrated that within the Taebaeksan metallogenic
province, Korea, higher Co concentrations in sphalerite were associated
with higher temperature deposits compared to lower temperature de-
posits. Moreover, a recent study by Wang et al. (2018) also highlighted
a positive relationship between increased Co concentrations in spha-
lerite and crystallisation temperature.
The concentration of Bi in sphalerite decreases across the Cu to Pb-
Zn transition (Fig. 11b). This behaviour is consistent with the con-
centration of Bi in galena and chalcopyrite, which show the same trend.
As discussed previously, this reflects the solubility and mobility of Bi in
the ore-bearing fluid, both of which decreased significantly across the
Cu to Pb-Zn transition, consistent with a small decreasing temperature
gradient across the Cu to Pb-Zn transition. Alternatively, the distribu-
tion of Bi could reflect the composition of the source fluid or the po-
sitioning of the samples relative to the fluid input. The progressive
crystallisation of sulphides containing Bi would gradually decrease the
concentration of Bi in the fluid. This would result in samples proximal
to the fluid source being enriched in Bi relative to samples more distal
from the source.
Despite the concentration in individual grains being highly variable,
the overall concentration of Pb, Sb and Ag in sphalerite all increase
across the Cu to Pb-Zn transition (Fig. 11c–e). The large range in con-
centrations from individual minerals indicates the presence of micron-
scale Ag-Sb-Pb sulfosalt inclusions, consistent with observations in
previous studies (Cook et al., 2009; Lockington et al., 2014; Wang et al.,
2018). Recent studies have shown that Sb in sphalerite is enriched in
lower temperature deposits compared to higher temperature Zn-Pb
deposits (Lee et al., 2019). It has been shown that Ag, Sb and Pb are all
enriched in pyrite distal to the trans-Atlantic Geotraverse (TAG) hy-
drothermal mound source, compared with pyrite proximal to the source
(Grant et al., 2018). Their study also demonstrated that the abundance
of micro-scale inclusions of minerals (sphalerite, chalcopyrite, galena
and sulfosalts) within pyrite was also strongly temperature dependent.
As the presence of mineral-inclusions is likely controlled by the solu-
bility of the elements they are composed of (Grant et al., 2018), this
scenario is applicable to mineral inclusions within sphalerite and other
sulphide minerals. Therefore, the increased abundance of Ag-Sb-Pb
sulfosalt inclusions in sphalerite likely represent a change in conditions
promoting the precipitation of such minerals. This is consistent with a
decrease in temperature, consequently decreasing the solubility of Ag,
Sb and Pb and leading to the formation of the mineral inclusions.
5.2. Temperature of ore formation
Out of 221 measurements, the GGIMFis geothermometer produced
an estimated median homogenisation temperature of 343 ± 44 °C
(Fig. 12a). This is consistent with a previous study that utilised the
GGIMFis geothermometer on two sphalerite-bearing samples from
Mount Isa, producing a temperature estimate of 305 ± 110 °C (Frenzel
et al., 2016). This estimate is within error of the estimated formation
temperature of 220–350 °C derived from the isotopic equilibrium of
sulphur between sphalerite and pyrrhotite mineral pairs, but is incon-
sistent with an estimated Pb-Zn formation temperature of 120–240 °C
derived from the deposit scale isotopic equilibrium of sulphur from
sphalerite and galena (Fig. 12b; (Painter et al., 1999)). This estimate is
also within error of the modelled temperature of 300 °C for Cu miner-
alisation from the 650 orebody, the 1100 orebody at 323 °C, and pre-
mineralisation dolomitic alteration from 270 to 350 °C (Fig. 12b;
17
Ore Geology Reviews 124 (2020) 103647
(Heinrich et al., 1989)). The results are also within the estimated
327 ± 25 °C temperature of chlorite alteration below the deposit
(Fig. 12b; (Hannan et al., 1993)) and the estimated ore-formation
18
25 °C and 397 40 °C using dolomite δ O thermometry
temperature of 297+29 +48
(Fig. 12b; (Mering et al., 2018)). Therefore, the sphalerite GGIMFis
geothermometer provides evidence to suggest that Zn mineralisation
was relatively hot (>300 °C) upon placement, in line with previous
estimates regarding Cu mineralisation.
5.3. Implications for a deposit model
Fine-grained pyrite represents the earliest hydrothermal event and
could either be diagenetic (Painter et al., 1999) or replacive (Perkins,
1998) in origin. Formation of the silica-dolomite breccia post-dates
fine-grained pyrite, as shown by the brecciation of shale clasts con-
taining stratabound fine-grained pyrite (Fig. 5a). This was followed by
the formation of calcite veins and siderite precipitation (Fig. 4c–e).
Coarse-grained pyrite then precipitated, followed by arsenopyrite and
the main mineralisation stage dominated by the sulphides chalcopyrite,
pyrrhotite, sphalerite and galena. There is no textural evidence sug-
gesting that Pb-Zn mineralisation has been brecciated by subsequent
silica-dolomite alteration. Instead, across the Cu to Pb-Zn transition,
sphalerite and galena preferentially replace the discordant silica-dolo-
mite breccia coeval with chalcopyrite and pyrrhotite (Fig. 4g–j; Fig. 5
b–d, f). It is also shown that across the Cu to Pb-Zn transition, chalco-
pyrite is only documented in areas containing galena and sphalerite,
and occasionally pyrrhotite. This observation is consistent with assay
data showing comparable peaks and dips in Cu, Pb and Zn concentra-
tions across the Cu to Pb-Zn transition (Section 4.2; Fig. 7) and could be
used as evidence to suggest a single common depositional fluid. Pet-
rography indicates that sphalerite precipitated out first, followed by the
co-crystallisation of chalcopyrite, galena and pyrrhotite (Fig. 5f). The
textural setting of chalcopyrite is suggestive of crystallisation slightly
later than sphalerite and galena, an observation that is consistent with
Perkins (1997). As Zn is significantly more soluble than Cu and Pb in
fluids with the same characteristics (Reed and Palandri, 2006; Zhong
et al., 2015), the ore-bearing fluid may have become saturated in Zn
relatively early compared to Cu and Pb. This would favour the pre-
cipitation of sphalerite before galena and chalcopyrite. As Pb is com-
parably more soluble than Cu in similar fluids (Reed and Palandri,
2006; Zhong et al., 2015), this interpretation could also be used to
explain the observation that chalcopyrite is often located in late tex-
tural settings, suggestive of slightly later precipitation. The petro-
graphic observations presented here are consistent with previous stu-
dies (Grondijs and Schouten, 1937; Perkins, 1997) and suggest that Pb-
Zn mineralisation was not a primary constituent of the Urquhart Shale,
but was introduced subsequent to silica-dolomite alteration, calcite
veining, siderite formation and the crystallisation of arsenopyrite and
coarse-grained pyrite. Based on the observation of co-genetic chalco-
pyrite, sphalerite and galena across the Cu to Pb-Zn transition, and the
lack of brecciated shale clasts containing syngenetic sphalerite and
galena mineralisation, the likelihood that a ~150 Ma time gap exists
between Cu and Pb-Zn mineralisation can be largely discounted. This
interpretation disagrees with the published S- and Pb-isotope data in
favour of separate Cu and Pb-Zn mineralisation events (Carr et al.,
2004; Smith et al., 1978). The claim made by Smith et al. (1978) sug-
gesting that sulphides from the Pb-Zn ore are in isotopic equilibrium,
while sulphides from Cu-ore are in disequilibrium has been disputed by
Andrew et al (1989) and Gulson et al (1983). These studies suggest that
chalcopyrite, pyrrhotite and coarse-grained pyrite are in isotopic
equilibrium. Andrew et al. (1989) also showed a large variation in δ34S
values in samples from Cu mineralisation, which is explained by the
interaction of the ore-bearing fluid with the pyrite-bearing sediments.
Therefore, different ranges in δ34S values of sulphide-bearing samples
from Cu and Pb-Zn mineralisation from Smith et al. (1978) likely reflect
the sample position and host rock lithology, not separate mineralisation
B. Cave, et al.
events. Pb-isotope data presented by Carr et al. (2004) showed sig-
nificant differences in samples collected from Cu and Pb-Zn ore. Al-
though Gulson et al. (1983) favoured separate Cu and Pb-Zn miner-
alisation events, it was shown that the isotopic arrays of Cu bearing
samples always pass through the average Pb-isotope value of the Pb-Zn
ore. Cu-bearing samples that were contaminated by the presence of the
Urquhart Shale reported substantially different Pb-isotope signatures
(Gulson et al., 1983). The low number of analysis (Cu samples = 7; Pb-
Zn samples = 2) reported by Carr et al. (2004) and the lack of clarity
regarding the samples and techniques used in the study make it possible
that differences in the Pb-isotope composition from different Cu and Pb-
Zn bearing samples could reflect contamination by the Urquhart Shale,
not separate mineralisation events. As the bulk of Cu mineralisation
occurs within a pre-mineralisation silica-dolomite halo, which clearly
brecciates the host lithology (Fig. 4a; Fig. 5a), it is logical to assume
that the Urquhart Shale was at least semi-consolidated, or completely
consolidated before subsequent Cu and Pb-Zn mineralisation. These
observations can discount a sedimentary exhalative model where Cu
and Pb-Zn mineralisation sprawled across the ocean floor, but cannot
discriminate between an epigenetic subsurface model that formed at ca.
1650 Ma (e.g. Finlow-Bates and Stumpfl, 1980; McGoldrick and Keays,
1990) or an epigenetic syn-D4 model (Davis, 2004; Perkins, 1997).
Detailed structural studies on the Cu and Pb-Zn orebodies favour a syn-
D4 timing for mineralisation and associated silica-dolomite alteration
(Bell et al., 1988; Bell and Hickey, 1998; Davis, 2004; Perkins, 1984).
Bell et al. (1988) suggested that the combined effects of D1–D3 de-
formation resulted in the easterly-dipping (40–50°) Eastern Creek Vol-
canic abutting a steeply (60–70°) west-dipping Urquhart Shale. During
D4 deformation, the sub-horizontal ramp in the Paroo fault (Fig. 2) was
at a high angle to the maximum extensional direction (Bell et al., 1988;
Perkins, 1984). The development of asymmetric folds during D4 de-
formation generated differential movement and dilation across the fault
plane and within D4 fold hinges and short limbs (Bell et al., 1988). This
caused a large drop in fluid pressure which resulted in explosive frac-
turing and local brecciation, providing access for syn- to late-D4 hy-
drothermal fluid to form the silica-dolomite alteration and Cu miner-
alisation (Bell et al., 1988; Perkins, 1984). This sequence of events
explains why the position of Cu orebodies is controlled by the presence
of D4 fold hinges and their associated short limbs (Bell et al., 1988;
Davis, 2004). A detailed study by Davis (2004) found that high-grade
Pb-Zn-mineralisation has a close spatial association with the hinges and
short limbs of D4 folds, with the highest grades of Pb-Zn coinciding with
the D4 folds closest to Cu mineralisation (Davis, 2004). This is con-
sistent with the grade contours of Pb-Zn ore being parallel to D4 fold
hinges and silica-dolomite alteration (Davis, 2004). Furthermore, by
rotating the bedding and orebodies to their horizontal pre-Isan Orogeny
positions, it was shown that the geometries of the Pb-Zn orebodies were
inconsistent with the formerly proposed syn-sedimentary style of mi-
neralisation (Davis, 2004). Based on evidence from this study combined
with detailed structural evidence from previous studies, an epigenetic
(syn-D4) and coeval Cu-Pb-Zn model is favoured.
5.4. Separation of the Cu and Pb-Zn ore
Two major contributors to metal zonation are pH and temperature
(e.g. Reed and Palandri, 2006), with both possibilities for the Cu-Pb-Zn
zonation at Mount Isa discussed below.
It is well established that changes in pH contribute to the zonation
and precipitation of metals in many ore deposits (e.g. Reed and
Palandri, 2006). Changes in pH associated with the prograde dissolu-
tion of silica-dolomite during the infiltration of Cu-Pb-Zn bearing fluids
could have played a key role in the overall distribution and separation
of Cu and Pb-Zn-rich mineralisation. The dissolution of silica-dolomite
would result in an increased pH towards neutral (Heinrich et al., 1989),
precipitating chalcopyrite first, followed by galena and sphalerite (Reed
and Palandri, 2006). This phenomenon has previously been suggested
18
Ore Geology Reviews 124 (2020) 103647
as a contributor to the precipitation of Cu mineralisation at Mount Isa
(Heinrich et al., 1989; Waring, 1990). The pH change would result in
chalcopyrite being largely confined to the silica-dolomite alteration
halo, allowing the Pb and Zn bearing fluids to migrate outwards further
into the adjacent shale. While the solubility of Cu, Pb and Zn must be
considered (Section 5.3), changes in pH alone are inconsistent with
sphalerite precipitating first, followed by galena then chalcopyrite.
Geochemical modelling by Wilde et al. (2006) supports this inter-
pretation, suggesting that the changes in pH associated with dolomite
dissolution were unlikely to precipitate major amounts of Cu in the
Mount Isa deposit. Therefore, it is suggested that while changes in pH
are an important factor in the zonation of metals in many ore deposits,
its contribution to the zonation of metals in the Mount Isa Cu-Pb-Zn
deposit is considered minimal.
The deposit scale zonation could also reflect the temperature-de-
pendent solubility of Cu, Pb and Zn in hydrothermal fluids, which de-
crease in that order (e.g. Hemley et al., 1992; Hemley and Hunt, 1992;
Zhong et al., 2015). The temperature dependent solubility of Cu, Pb and
Zn has been used previously by authors to explain the occurrence of
metal zonation at Mount Isa (Finlow-Bates and Stumpfl, 1980;
McGoldrick and Keays, 1990; Perkins, 1997). Similarly, we suggest that
as the ore-bearing fluid migrated through the silica-dolomite breccia
and adjacent shale, the high solubility of Zn allowed it to be transported
further from the fluid source relative to Pb and Cu. Sphalerite pre-
cipitated out first due to early saturation of Zn in the ore-bearing fluid
relative to Pb and Cu, which was assisted by a decreasing fluid tem-
perature away from the source. Petrography and trace element patterns
in chalcopyrite, galena and sphalerite across the Cu to Pb-Zn transition
are consistent with this interpretation and are directly comparable with
previous studies that discuss the effect temperature and fluid-rock in-
teraction has on the trace element composition of various sulphide
minerals (e.g. Carvalho et al., 2018; Grant et al., 2018; Lueth et al.,
2000). We suggest the variation in concentrations of Bi and Pb in
chalcopyrite, Se, Bi and Sb in galena and Pb, Sb, Ag, Bi and Co in
sphalerite over the Cu to Pb-Zn transition are due to the presence of a
temperature gradient between Cu and Pb-Zn mineralisation upon ore
emplacement. However, it is important to consider the effect sulphide
crystallisation has on the concentration of these elements within the
ore-bearing fluid. The progressive crystallisation of sulphides con-
taining the elements (Bi, Se, Tl, Sb and Co) would gradually decrease
the concentration of these elements in the fluid. This could result in
samples proximal to the source being enriched in these elements re-
lative to samples that are more distal to the source. Alternatively, this
could explain the decrease of the various trace elements in the sul-
phides away from the Paroo fault. Decreased Te concentrations in ga-
lena associated with Pb-Zn mineralisation could reflect a combination
of temperature effects and increased fluid-rock interaction. As the
GGIMFis geothermometer (Fig. 12; Supplementary Table 3) suggests
that sphalerite was relatively hot upon placement (>300 °C), to be in
line with previous estimates regarding Cu mineralisation
(also > 300 °C; Fig. 12b), the temperature gradient from Cu → Pb →
Zn-rich mineralisation must be relatively small (<50 °C). This small
temperature gradient allowed Pb and Zn to be transported further away
from the fluid source relative to Cu, consequently resulted in different
host lithologies and styles of mineralisation.
6. Conclusions
1) In-depth petrography of multiple samples across the Cu to Pb-Zn
transition at Mount Isa reveals co-genetic chalcopyrite, sphalerite
and galena that post-date the formation of fine-grained pyrite, silica-
dolomite, quartz, calcite, siderite, as well as the formation of coarse-
grained pyrite and arsenopyrite.
2) Variations in the concentrations of Bi and Pb in chalcopyrite, Se, Te,
Bi and Sb in galena, and Co, Bi and Pb-Ag-Sb sulfosalts in sphalerite
are consistent with temperature changes having a key role in the
B. Cave, et al.
separation of Cu and Pb-Zn mineralisation.
3) The GGIMFis geothermometer yields an estimated formation tem-
perature of 343 ± 44 °C, consistent with previous estimations of
silica-dolomite formation, chlorite alteration and Cu mineralisation.
4) A coeval and epigenetic Cu-Pb-Zn model is favoured where a slight
temperature gradient (<50 °C) resulted in Pb and Zn being trans-
ported further from the fluid source relative to Cu. This resulted in
Cu mineralisation being deposited within the silica-dolomite close to
the Paroo fault. Conversely, Pb-Zn mineralisation was deposited
further from the fluid source and within selective carbonate- and
fine-grained pyrite-rich units of the adjacent Urquhart Shale.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
We would like to thank Daniel Taylor, James Hewitt, Daniel
Travers, Diana Bastin and all the other geologists from the Mount Isa
Copper Operations for their hospitality and assistance during sampling
and core logging. The Mount Isa Core Shed team is thanked for their
assistance during core sampling. We would also like to thank Trevor
Shaw, Peter Rea and the Mount Isa Resource Development team for
their insightful comments regarding the discussion and logistical as-
sistance. I would also like to thank Bill Perkins for the many en-
lightening chats on the Mount Isa deposit, and Thomas Blenkinsop for
structural discussions. Furthermore, Dave Kelsey, Sarah Gilbert and
Benjamin Wade are thanked for their support and guidance with ana-
lytical procedures. The authors would also like to thank the anonymous
reviewers for their comments and feedback, of which improved the
quality of the manuscript. This study was funded by Mount Isa Mines - a
Glencore Company and forms part of the Mount Isa Research for
Geology and Exploration (MIRGE) project. The funding source played
no role in the writing of the manuscript, study design, analysis or in-
terpretation of the data. B.C is supported by the Australian Government
Research Training Program.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.oregeorev.2020.103647.
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