Ore Geology Reviews 111 (2019) 103004

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Ore Geology Reviews

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Trace element substitution and grain-scale compositional heterogeneity in T

enargite
Wenyuan Liua,b, Nigel J. Cookb, , Cristiana L. Ciobanub, Sarah E. Gilbertc
⁎

a
College of Zijin Mining, Fuzhou University, 350108 Fuzhou, China
b
School of Chemical Engineering and Advanced Materials, The University of Adelaide, Adelaide, SA 5005, Australia
c
Adelaide Microscopy, The University of Adelaide, Adelaide, SA 5005, Australia

ARTICLE INFO ABSTRACT

Keywords: Enargite, Cu3AsS4, is a relatively common sulphide mineral and is considered diagnostic for deposits of inter-
Enargite mediate- to high-sulphidation type. Analysis of enargite-bearing samples from deposits in the Zijinshan porphyry
Trace elements – high-sulphidation epithermal Cu-Au orefield, southeastern China, provides evidence for the diversity of trace
Substitution mechanisms elements that may be hosted within enargite and their range of concentrations. Enargite is shown to host Sb, Te,
Oscillatory zoning
Sn, Zn and Ge at concentrations up to several thousand ppm. The mineral also incorporates measurable con-
Zijinshan
High-sulphidation
centrations of Mo, Cd, Bi, Pb, Fe, Se, Ag, Au W, Ga and In. Element mapping (electron probe microanalysis and
laser ablation inductively coupled plasma mass spectrometry) provides evidence for grain-scale heterogeneity in
enargite in the form of oscillatory, grain-scale compositional zonation with respect to Sb, Sn, Te and several
other trace elements. Element mapping also clearly shows an inverse correlation between the concentrations of
As and Te, and between As and Sn. Incorporation of Sn and Te into the enargite structure is achieved by sub-
stitution of Sn4+ and Te4+ for As5+. Charge balance is maintained by incorporation of Fe2+, Zn2+ and other
divalent cations (potentially including Cu2+) into the Cu+ site. The complex intra-grain zoning results from
evolving fluids, multiple phases of growth – in turn leading to an overprinting of primary distribution patterns.
Observed patterns are also influenced by equilibrium partitioning between enargite and co-existing minerals.
Nevertheless, trace element signatures in enargite from different parts of the Zijinshan ore system show notable
differences. Enargite from the high-sulphidation stage typically shows a marked enrichment in Te and Sn
whereas enargite from intermediate-sulphidation stage is relatively depleted in Te and Sn, and comparatively
enriched in Sb and Se. These differences represent a potential vector for exploration within porphyry – high-
sulphidation epithermal systems. Furthermore, the presence of Te-rich enargite may be a prospective guide to
high Au-grade mineralization. The notable concentrations of precious metals (Au, Ag) and critical elements
(notably Te and Ge) within enargite make this mineral of particular interest from the perspective of potential
recovery of these economically important elements. The observed grain-scale zoning and inherent variability
within any given sample emphasize that spot analysis of trace elements alone without consideration of such
heterogeneity may provide quantitative data of limited use and potentially, lead to misleading interpretations.

1. Introduction (e.g., Tongamp et al., 2009). Enargite also oxidises rapidly (Lattanzi
et al., 2008), making it a potential environmental hazard.
Enargite, Cu3AsS4, is a relatively common sulphide mineral and is Enargite is one of the four thioarsenate sulphosalts (i.e., containing
considered diagnostic for deposits of intermediate- to high-sulphidation As5+). Together with the thioantimonates, thiostannates, thiogerma-
type (e.g., Arribas, 1995). Although enargite-bearing ores can contain nates, and others, they are mostly related to ZnS archetypes (Moëlo
high copper grades, the presence of arsenic can make enargite-bearing et al., 2008). The crystal chemistry and major element compositional
ores problematic to process, and resultant copper concentrates poten- variation of enargite are well known (Springer, 1969; Adiwidjaja and
tially difficult to market (Safarzadeh et al., 2014). Various metallurgical Löhn, 1970; Henao Martinez et al., 1994; Karanović et al., 2002). The
treatments have been put forward to selectively remove enargite principal substitution observed is replacement of As5+ by Sb5+. Anti-
(Senior et al., 2006), or remove As and convert enargite to digenite mony may substitute for As in the enargite structure at concentrations

⁎
Corresponding author.
E-mail address: [email protected] (N.J. Cook).

https://doi.org/10.1016/j.oregeorev.2019.103004
Received 2 May 2019; Received in revised form 22 June 2019; Accepted 4 July 2019
Available online 06 July 2019
0169-1368/ © 2019 Elsevier B.V. All rights reserved.
W. Liu, et al. Ore Geology Reviews 111 (2019) 103004

up to 20 mol% Cu3SbS4 (Springer, 1969). In contrast, the tetragonal dominantly represented by gold-bearing iron oxides (goethite and li-
Cu3AsS4 polytype, luzonite, shows complete solid solution with the Sb monite) with intense silicification. Hypogene copper mineralization
end-member famatinite (Pósfai and Buseck, 1998). comprises an association of digenite + covellite + enargite and is in-
Several studies have used laser-ablation inductively coupled plasma timately associated with quartz + alunite alteration.
mass spectrometry (LA-ICP-MS) to examine trace element concentra- Previous research (Liu et al., 2012, 2014, 2016) has shown that
tion ranges in enargite. These have confirmed significant incorporation mineral assemblages in Zijinshan copper ore display considerable var-
of several chalcophile elements, notably Sb, Bi, Sn, Se, Te, Zn, Pb and iation both vertically and laterally. A deep chalco-
Ag, and also variability in the trace element composition of enargite at pyrite + tennantite + pyrite assemblage in the phyllic alteration zone
the scale of individual crystals and across an orebody (Deyell and gives way upwards to covellite + digenite + enargite in the alu-
Hedenquist, 2011; Maydagán et al., 2013; Dekov et al., 2016; Sahlström nite + dickite alteration zone, and laterally, from digenite + covellite
et al., 2017). Few consistent trace element correlations in enargite have, in the centre, through bornite + enargite to chalcopyrite + tennantite
however, been documented in the literature until now, and many of the in the outer zone (Fig. 2). Several minor minerals containing Sn, W, Te,
trace element substitution mechanisms proposed remain ambiguous. Bi, Ge, V, In and Mo are also found in the copper ores. The occurrence
These studies have nevertheless recognised that the commonly complex of Sn-bearing sulphides (kiddcreekite, hemusite, colusite, vinciennite,
grain-scale compositional heterogeneity present in enargite represents a stannoidite and mawsonite) is particularly notable and allows con-
key for understanding the evolution of ore-forming fluids over space straints to be placed on the physicochemical environment of ore for-
and time. mation across the broader porphyry-epithermal system (Liu et al., 2012,
The Zijinshan Cu-Au district, southeastern China, hosts several 2014, 2016).
porphyry and epithermal deposits, notably the Zijinshan high-sulphi- The Longjiangting Cu deposit lies between the Zijinshan HS Cu-Au
dation (HS) Cu-Au deposit, which contains a typical mineral association deposit and the Yueyang low-sulphidation Ag-Cu-Au deposit (Fig. 1)
of digenite + covellite + enargite + alunite, with enargite occurring in and is interpreted as an IS-type epithermal deposit with HS-epithermal
several ore zones. The deposit also features significant enrichment in overprint at uppermost levels. At upper levels (> 250 m above sea
tin, with several relatively rare Sn-bearing minerals documented (Liu level), copper minerals are dominated by digenite, bornite, covellite
et al., 2016). These including kiddcreekite, colusite, hemusite, kësterite, and pyrite, with subordinate tetrahedrite and vinciennite, associated
mawsonite, stannoidite, and vinciennite. Tin mineralogy is observed to with alunite–dickite alteration. Below 250 m, mineral assemblages are
vary from a dominance of kësterite at upper levels, through stannoidite- dominated by bornite, chalcopyrite, enargite, tennantite and pyrite,
dominant at mid-to-upper levels of the copper orebody, to vinciennite- with minor Pb-, Zn- and Bi-minerals within dickite + sericite alteration.
and mawsonite-dominant assemblages at depth. The objectives of this The Wuziqilong Cu deposit (Fig. 1) lies between the Zijinshan HS
study are to systematically examine the trace element composition of Cu-Au deposit and the Luoboling porphyry Cu-Mo deposit and has been
enargite from different stages of ore-formation at Zijinshan using interpreted as an epithermal deposit of transitional type, in which the
electron probe microanalysis (EPMA) and laser ablation inductively upper part is overprinted by HS-style mineralization. Mineral assem-
coupled plasma mass spectrometry (LA-ICP-MS). This study emphasizes blages dominantly comprise covellite, digenite, enargite, pyrite and
trace element mapping by LA-ICP-MS, which provides a valuable vi- chalcopyrite with trace amounts of Sn-sulphides within alu-
sualization of trace element distributions within individual minerals nite + dickite alteration at shallower levels, in which chalcopyrite is
and assemblages of coexisting phases. The trace element composition of replaced by digenite, covellite and enargite. At deeper levels
enargite at the grain to orebody scales also provides constraints on ore (dickite + sericite alteration zone), ore mineral assemblages are
genesis and carries implications for mineral exploration and for ore dominated by bornite, chalcopyrite, tennantite and pyrite.
processing. Furthermore, this study is the first to correlate observed
grain-scale compositional heterogeneity in enargite with an evaluation 3. Sampling and methodology
of trace element variability and substitution mechanisms.
Enargite is a major mineral in the Zijinshan deposit but less abun-
2. Geology and ore deposits in the Zijinshan ore district dant in other deposits in the district of transitional type (dominantly IS-
style but with superposition of HS-pulses in the upper part). Nine re-
The Zijinshan orefield is located in the eastern part of the Cathaysia presentative samples were collected for detailed petrographic in-
Block of South China (Fig. 1) and hosts a number of porphyry- to epi- vestigation and trace element analysis by EPMA and LA-ICP-MS. Grains
thermal-type deposits. These include the Zijinshan HS epithermal Cu- of enargite were checked with micro-Raman analysis, which showed
Au deposit, the Luoboling porphyry Cu-Mo deposit, the Yueyang low- the typical Raman shift of enargite at wavelengths of 340 cm−1 and
sulphidation (LS) epithermal Cu-Ag-Au deposit and several less-eco- 382 cm−1, thus precluding the possibility that these are luzonite rather
nomic prospects of intermediate-sulphidation (IS) type, e.g., Wuziqi- than enargite (Supplementary Appendix 1).
long, Longjiangting and Ermiaogou. By 2013, the total proven reserves The seven ore samples from the Zijinshan deposit were collected at
of the district reached 400 t Au, 6340 t Ag, 4.1 Mt Cu and 0.11 Mt Mo different elevations to address spatial variation within HS mineraliza-
(Zhang, 2013). tion. The other two samples are from the Longjiangting Cu deposit and
Zijinshan was the first HS-type epithermal deposit to be recognized Wuziqilong Cu deposits, which both represent IS-style Cu mineraliza-
in mainland China. Ores are genetically associated with early tion. Sample details are given in Table 1. All samples were prepared as
Cretaceous dacitic magmatism and are mainly hosted by granites of the 1-inch-diameter polished blocks except for two samples (11lc-2 and zjs-
Late Jurassic Zijinshan Complex and Early Cretaceous dacitic porphyry. 35), which were prepared as polished thin-sections. All samples were
Recent deep drilling indicates that Cu mineralization within the zone of characterized by reflected light microscopy and EPMA prior to LA-ICP-
advanced argillic alteration in the deposit has a vertical extension ex- MS analysis. Only areas of enargite grains free of noticeable inclusions
ceeding 1500 m from surface. Copper-Au mineralization occurs mainly were selected for LA-ICP-MS analysis.
within hydrothermal breccia and veins emplaced within NW-striking, Wavelength dispersive spectroscopy (WDS) mapping of enargite
NE-trending extensional fractures. Orebodies are characterized by su- were obtained using a JEOL-JXA 8230 electron probe micro-analyser at
pergene gold zones at upper levels and lower hypogene copper zones Fuzhou University, China, with an accelerating voltage of 20 kV and a
bounded roughly by a paleo-watertable near 600 m elevation (Fig. 2). beam current of 100 nA.
Zonation between Au-rich and Cu-rich ores is transitional, due to the Both LA-ICP-MS element mapping and spot analysis were carried
presence of fault structures that controlled supergene leaching and out using a RESOlution-LR 193 nm excimer laser attached to an Agilent
oxidation. Gold mineralization in the upper supergene zone is 7900x Quadrupole ICP-MS (Adelaide Microscopy, The University of

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W. Liu, et al. Ore Geology Reviews 111 (2019) 103004

Fig. 1. Geological map of the Zijinshan ore district (revised from Liu et al., 2016).

Fig. 2. Vertical cross-section showing distribution of mineralization and associated alteration and ore mineral assemblages along line A-A′ marked on Fig. 1. Sample
locations are marked.

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W. Liu, et al. Ore Geology Reviews 111 (2019) 103004

Adelaide, Australia). The large format S-155 ablation cell was filled
Ore type with UHP He (0.35 L/min) and was mixed with Ar (1.06 L/min) after
leaving the cell and was introduced directly to the torch through a
HS
HS
HS
HS
HS
HS
HS
IS
IS
‘squid’ mixing device. Methodology followed establishes practices for
other sulphide minerals conducted in the same laboratory (George

Longjiangting
Wuziqilong
et al., 2017, 2018).
Locations

Zijinshan

For LA-ICP-MS spot analysis, the laser fluence was 3.5 J/cm2 using a
repetition rate of 5 Hz. Spot size varied between 29 and 43 μm de-
pending on the size of the enargite grain analysed. Each analysis
comprised a 30 s background measurement followed by 40 s of sample
Elevation (m) relative to sea level

ablation. A 20 s delay was allowed after each spot analysis to prevent

cross contamination between analyses. During spot analysis and map-
ping the following suite of isotopes were measured: 27Al, 29Si, 34S, 49Ti,
51
V, 55Mn, 57Fe, 59Co, 60Ni, 65Cu, 66Zn, 69Ga, 72Ge, 75As, 77Se, 95Mo,
107
Ag, 111Cd, 113In, 115In, 118Sn, 121Sb, 125Te, 182W, 185Re, 197Au, 205Tl,
206
Pb, 207Pb, 208Pb and 209Bi. Aluminium and Si were monitored to
ensure collateral small volumes of gangue phases were not analysed
together with enargite; these elements were not quantified. During spot
−136
−23
−86
120
760
724
688
520
520

analysis, two 74 μm-diameter analyses were made on the STDGL3

(Danyushevsky et al., 2011) and GSD-1G (USGS) reference materials
after every 20 analyses of unknowns. Copper was used as the internal
Covellite-rich ore: ore minerals are dominated by covellite, pyrite, digenite and enargite, with trace amounts of colusite, kiddcreekite, and stannoidite.
Covellite-rich ore: ore minerals are dominated by covellite, pyrite, digenite and enargite, with trace amounts of colusite, kiddcreekite, and stannoidite.

standard element assuming perfect stoichiometric enargite composition

(48.42 wt% Cu). Although we acknowledge that Sb/Te rich varieties
will have slightly lower Cu content, introducing negligible errors, this
was done for purposes of ensuring consistency in the data and because
Massive digenite-rich ore: ore minerals are dominated by digenite and enargite, with lesser covellite and goldfieldite, trace native gold.

of incompatibility in the scales of volumes analysed by EPMA and LA-

ICP-MS. Impact on results and interpretations of the differences be-
Digenite-rich ore: ore minerals are dominated by digenite and pyrite, with lesser enargite, covellite, kiddcreekite and colusite.

tween distinct types of enargite are considered minimal. Iolite data

Bornite-rich hydrothermal breccia: ore minerals are dominated by bornite, digenite, pyrite, and enargite, with lesser covellite

Chalcopyrite-rich vein: ore minerals are dominated by chalcopyrite, pyrite and bornite, with lesser enargite and tennantite

reduction software (Paton et al., 2011) was used to carry out data
Chalcopyrite-rich vein: ore minerals are dominated by chalcopyrite, pyrite and digenite, with lesser enargite and bornite
Enargite-rich vein: ore minerals are dominated by enargite and pyrite, with lesser tennantite, tetrahedrite and covellite.

calculations. Analysis of enargite in the two thin-section samples (11lc-

2, zjs-35) resulted in shorter analysis times (10–28 s) due to ablating
through the section into the glass slide. Indium concentrations were
calculated considering measurements of 115In and subtracting the cal-
culated contribution from 115Sn. Mean errors and the minimum de-
Massive digenite-rich ore: ore minerals are dominated by digenite and enargite, with lesser covellite.

tection limits for common trace elements in each sample are provided
as Supplementary Appendix 2.
LA-ICP-MS trace element mapping was achieved using the same
instrument by ablating sets of parallel line rasters in a grid across the
sample surface. A square laser beam profile was used throughout with
spot size varying between 11 and 16 μm to provide adequate spatial
resolution for each map. The spacing between adjacent trenches was
also modified to match the spot size, so there was complete coverage of
each area samples. Similarly, the laser beam scan speed was set to
11 μm/s, where 11 μm laser spot size was used. Laser fluence used was
3.5 J/cm2 using a repetition rate of 10 Hz. A 10 s background mea-
surement was acquired before the ablation of each trench, followed by a
20 s delay after ablation. Two 74 μm-diameter spot analyses were made
on STDGL3 and GSD-1G reference materials at 10 Hz before and after
each map. All LA-ICP-MS trace element maps were processed with the
Iolite software. A linear drift correction was applied to the unknown
trench analyses based on data for STDGL3 acquired before and after a
mapping run. The average background intensity for each element was
Description and mineral assemblage

then subtracted from its corresponding trench acquisition, and the re-
Overview of samples analysed in this study.

sulting time-resolved linear intensities compiled into a two-dimensional

image for each element. Copper was used as the internal standard to
produce the quantitative maps.

4. Results

4.1. Petrography

In the Zijinshan HS deposit, enargite is mostly associated with di-

genite and covellite. In digenite-rich ores (samples 11lc-2 and zjs-35),
dzk005-4
dzk403-4

enargite occur as euhedral crystals replaced by digenite, covellite and

zk301-7
510-c-1
510-c-2
Sample

zjs-418
Table 1

11lc-2
zjs-35
zjs-21

alunite (Fig. 3a). The assemblage also includes trace goldfieldite which
replaces enargite (Fig. 3b). Rare native gold is observed as inclusions in

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W. Liu, et al. Ore Geology Reviews 111 (2019) 103004

Fig. 3. Photomicrographs in reflected light (a, c, d)

and BSE image (b) showing aspects of mineral as-
semblages containing enargite in the Zijinshan HS
Cu-Au deposit. (a) Aggregates of euhedral enargite
(En) replaced by digenite (Dg) and alunite (Alu)
(sample 11lc-2); (b) Compositionally-zoned en-
argite replaced by digenite and goldfieldite (Gf)
(sample 11lc-2); (c) Enargite associated with bor-
nite (Bn) and pyrite (Py) and occurring as early
veins replaced by digenite (sample zjs-21); (d)
Enargite intimately intergrown with fine-grained
replacing covellite (Cv), tetrahedrite (Tet) and
tennantite (Ten) in massive enargite-pyrite vein
(sample dzk005-4).

goldfieldite. Enargite from bornite-rich ores (sample zjs-21) occurs as b). Enargite from digenite-rich ores (sample dzk403-4) occurs as eu-
anhedral grains and is intimately associated with bornite and pyrite, hedral grains with surrounding pyrite which is replaced by digenite.
possibly in equilibrium, as early-stage veins replaced by late digenite In the Wuziqilong Cu deposit (sample zjs-418), enargite mostly
and djurleite (Fig. 3c). In enargite-rich ore (sample dzk005-4), enargite occurs in the dickite-sericite zone in which the ore mineral assemblage
occurs as anhedral aggregates, which are intimately intergrown with is dominated by chalcopyrite, pyrite and digenite. Rare enargite occurs
fine-grained covellite, tetrahedrite and tennantite (Fig. 3d). as euhedral grains within digenite that replaces chalcopyrite (Fig. 4c).
Enargite from covellite-rich ores (sample 510-c-1/2) occur as eu- In the Longjiangting Cu deposit (sample zk301-7), enargite mostly oc-
hedral grains with surrounding pyrite. Enargite is associated with curs as subhedral grains in chalcopyrite-rich ores, associated with
covellite, pyrite, digenite, and intimately intergrowth with some rare chalcopyrite, bornite, pyrite, and lesser tennantite and minor Pb-Bi
tin-sulphides including colusite, kiddcreekite and stannoidite (Fig. 4a, minerals. Early tennantite is replaced by enargite (Fig. 4d).

Fig. 4. Photomicrographs in reflected light

showing aspects of mineral assemblages containing
enargite. (a) Enargite intimately intergrown with
pyrite, covellite, digenite and colusite (Col) (sample
510-c-1); (b) Compositionally-zoned colusite re-
placed by enargite in the same sample (510-c-1); (c)
Trace euhedral enargite associated with digenite
within chalcopyrite (Cpy)-rich ore (IS mineraliza-
tion, Wuziqilong, sample zjs-418); (d) Enargite in-
timately intergrown with tennantite and chalco-
pyrite (IS mineralization, Longjiangting, sample
zk301-7).

5
 Table 2
Summary of LA-ICP-MS data for enargite (ppm).
W. Liu, et al.

Sample Notes Fe Zn Ga Ge Se Mo Ag Cd In

mean (n = 7) 100 166 0.17 42 3.30 1.93 18.9 12.0 0.30

range 30–200 58–428 mdl-0.26 8.8–156 mdl-3.3 0.13–8.3 5.95–26.2 3.47–34.3 0.17–0.57
11lc-2
mean (n = 6) 311 261 0.12 69 3.50 4.25 128 16.3 0.58
Au-rich
range 112–520 61.3–696 0.07–0.18 20–158 mdl-4.6 0.12–15.4 38–313 1.42–48.5 0.15–0.94
mean (n = 6) 51 164 < mdl 55 3.81 0.91 5.06 115 0.64
range 8.4–132 79–378 < mdl 4-202 mdl-5.2 mdl-2.47 mdl-8.6 13–229 0.24–1.3
zjs-35
mean (n = 12) 50 122 0.11 54 7.24 0.34 80.0 64.8 0.54
Au-rich
range 7–290 8.7–429 mdl-0.2 18–132.7 1.92–24.9 0.05–1.24 21.1–217 15.8–203 0.13–1.14
mean (n = 12) 40 402 0.21 330 8.09 7.57 26.2 69.3 0.55
range 12.1–98 114–678 mdl-0.48 22.3–1570 1.8–31.6 mdl-50 1-123 8.9–196 mdl-1.08
zjs-21
mean (n = 6) 218 524 0.23 192 4.74 1.84 62 47.2 0.81
Au-rich
range 55–580 156–1063 0.05–0.58 53.4–394 mdl-6.7 0.1–6.1 35–115 18.4–85 0.31–1.22
mean (n = 24) 16.4 386 0.47 120 7.92 3.57 6.67 66.3 1.05
range 4.4–16.7 128–1015 mdl-3.52 19–403 2.19–43.8 mdl-54.7 0.54–14.5 16.24–175 0.23–30.84
mean (n = 6) 25.4 668 20.8 2062 5.30 3.19 12.2 212 6.42
510-c-1 Ge-rich
range 19.5–32.7 279–947 0.2–98 541–3461 3.62–8.49 mdl-6.5 6.89–25 103–346.7 0.89–30.84
mean (n = 11) 29 279 0.84 173 6.55 1.69 88.2 34.0 0.84
Au-rich
range 15–64.4 103–640 mdl-6.11 33.5–356 2.76–16.8 mdl-6.7 25–228 11.7–53.5 0.25–1.36
mean (n = 7) 120 504 1.18 979 26.0 409 27.1 71.5 4.26
Ge-Mo-rich
range 40–560 314–676 0.4–2.45 284–1970 6.27–39.1 90–723 2.89–76.6 49.8–140 1.03–6.74
mean (n = 5) 53 187 1.01 195 12.4 8.35 54.4 36.7 1.00
510-c-2
range 29-67 77–267 0.14–2.89 96.4–442 2.63–23.2 mdl-21.5 13.2–139 13.4–68.2 0.7–1.44
W-rich
mean (n = 20) 103 316 0.30 110 7.46 8.11 23.6 48.0 0.93
range 17.9–840 120–1012 mdl-0.93 28.4–343 1.2–22.7 0.08–29.8 2.7–70 18–200.4 0.37–1.68

6
mean (n = 5) 37 930 0.53 173 4.43 0.11 8.35 63.1 1.14
range 8.4–89 255–1478 0.25–0.77 96–236 3.4–6.1 mdl-0.11 3.94–15 29.1–91.8 0.31–1.68
Au-rich mean (n = 11) 111 842 0.51 169 5.90 0.05 25.9 54.7 1.34
dzk403-4
range 22.5–355 329–2120 0.1–1.58 66.4–344 3.76–9.6 mdl-0.11 15.6–36.7 33.8–84.2 mdl-3.08
W-rich mean (n = 4) 50 425 0.50 261 6.61 0.08 26.7 35.1 0.58
range 18.7–62 236–797 0.19–0.75 85–480 5.2–8.2 mdl-0.08 18.46–36 26.5–49.6 0.24–1.13
mean (n = 9) 397 730 0.39 363 52 0.05 30.9 26.5 2.18
dzk005-4
range 11–950 50–1525 0.11–1.45 78.3–660 22.6–77.8 mdl-0.07 9.4-56 4.4–45.1 0.16–7.7
Mo-rich mean (n = 5) 463 38 0.06 316 13.7 206 8.88 3.89 0.18
range 151–634 32–44.4 mdl-0.06 51.3–512 8.7–19 60.4–274 1.4-15 1.9-7 0.07–0.28
Sn-poor mean (n = 15) 50 4.49 0.06 263 15.1 31.5 0.84 0.49 0.04
zjs-418
range 5.1–281 1.8–12.5 mdl-0.15 133.4–511 6.1–30 10.1–102 0.43–2.02 0.11–1.27 0.02–0.14
Sn-rich mean (n = 4) 18 1318 0.24 313 < mdl 1.43 18.1 80.3 1.52
range 10.1–28 1005–1488 0.07–0.45 169–700 < mdl mdl-2.8 mdl-34 61.5–88.6 1.26–1.78
mean (n = 8) 143 65 0.10 427 244 55.9 15.8 1.86 0.27
zk301-7
range 30.3–322 17.5–172 mdl-0.2 162–1030 186–284 5.3–191 2.41–47 0.85–4.44 0.04–0.8

Sample Sn Sb Te W Au Tl Pb Bi Ti V

1321 10,667 2523 10.4 1.13 0.09 58 49 1.95 1.02

380–3040 5670–14920 363–4950 1.8–29.9 0.33–2.01 0.03–0.24 15.93–171 13.1–88.4 1.5–2.6 0.1–5.72
11lc-2
2091 7890 7022 43.2 28.5 0.18 271 296 1.91 1.65
774–4250 4180–16140 3560–13160 11.3–108 7.6–69 0.06–0.3 48–802 115–570 1.16–2.7 0.33–3.82
2778 4839 1148 22.6 2.44 0.06 41 18 2.20 2.74
760–4400 1459–8320 46.7–2272 0.65–107 mdl-5.3 mdl-0.09 0.88–127 0.08–42.9 mdl-2.47 mdl-9.53
zjs-35
1866 6574 3262 7.39 61.3 0.17 63 93 2.07 1.08
523–4510 3070–11540 729–9520 0.18–30.8 21.2–239.5 mdl-0.78 0.79–373 13.4–239.1 1.85–2.59 mdl-5.56
(continued on next page)
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 W. Liu, et al.

Table 2 (continued)

Sample Sn Sb Te W Au Tl Pb Bi Ti V

2406 6238 1931 11.5 1.34 0.10 20 26 3.28 1.11

439–6120 3800–9530 301–5240 0.18–44 mdl-4.21 mdl-0.49 2.77–76.1 0.59–75.2 1.2–3.5 0.16–2.53
zjs-21
2994 7713 4750 15.3 11.0 0.30 82 132 1.82 2.96
1049–5190 5340–9490 3140–8430 2.78–51.8 6.2–19 0.1–0.8 21–217 56–209 1.12–2.16 0.38–11.6
3305 10,174 942 3.84 1.32 0.04 12.0 19.2 2.33 0.38
900–7100 3559–15400 87–2120 0.7–11.4 0.02–3.77 mdl-0.3 0.77–30 1.66–53 1.82–2.82 0.03–0.89
2814 12,995 1399 7.66 2.17 0.05 32.3 44.2 2.28 1.81
510-c-1
1530–4860 10390–16150 916–1750 1.81–26.5 0.86–4.64 0.02–0.07 13.3–51 18.3–73.2 2.02–2.66 0.09–7.54
2900 8936 3450 3.87 29.6 0.08 28 87 2.46 0.80
1330–4310 5140–12790 1760–8250 1.07–11.5 8.1–83.5 0.02–0.26 7.56–76.6 33.4–165.3 2.2–2.46 0.23–2
1057 1789 759 23.8 2.38 2.26 95 58 2.35 4.22
28–3460 134.4–4140 110–2677 2.3–70 0.19–6 0.61–4.66 17–272 15–131 1.82–3.05 0.85–9.8
1815 6268 2312 138 8.10 0.20 23 95 2.46 13.61
510-c-2
514–3050 3590–8770 470–4550 56–229 1.6–20.1 mdl-0.66 9.2-41 13.4–141 1.83–3.11 3-49
2381 3678 1429 9.04 3.71 0.21 23 31 2.38 1.16
810–6080 1650–6360 325–2958 1.24–32 0.68–13.6 0.01–1 2.45–64.4 0.52–91.4 1.95–2.88 0.08–9.6
3939 8108 439 11.29 1.49 0.11 61 15 2.61 1.30

7
987–6820 5580–11450 121–920 4.25–18 0.42–3.87 mdl-0.19 17.7–136 5.23–27.9 2.01–3.2 0.23–2.77
3714 6829 1821 21.79 9.86 0.16 153 50 2.32 2.07
dzk403-4
1560–7710 4740–9640 960–3850 5.11–48.2 5.46–48 0.06–0.42 93–221 34.7–77.9 1.22–3.3 0.45–5.6
2185 5340 2023 169 11.1 0.11 196 50 2.13 12.00
960–3990 3720–7610 1540–2620 104–261 7.25–15.8 0.05–0.17 110–272 26-72 1.91–2.51 6.9–17.6
1359 23,144 102 36 0.17 0.09 25 120 2.16 3.24
dzk005-4
80–4870 15040–31280 26–408 2.51–176 0.06–0.37 0.02–0.19 7.39–48 17.80–266 1.82–2.63 0.06–13.38
2.58 9184 1.99 0.03 0.28 5.31 97 16 1.98 10.73
mdl-3.5 3960–14970 0.76–4 mdl-0.04 mdl-0.44 1.97–9.45 34–171 43,395 1.42–2.4 0.78–15.5
0.36 8933 1.51 0.02 0.02 0.31 7 23 2.05 1.34
zjs-418
mdl-0.86 712–23220 0.66–2.71 mdl-0.03 mdl-0.03 0.04–1.17 mdl-24.4 0.78–66.7 0.99–2.92 0.11–6.2
4028 5008 1070 58.3 3.61 0.05 46 16 2.08 8.20
2510–5010 4090–7060 63–2030 1.94–137 mdl-5.28 mdl-0.10 2.54–81 1.2–45 1.65–2.76 0.32–16.4
207 6076 65.41 1.92 0.53 0.08 5 14 3.96 0.61
zk301-7
15.3–950 4610–9430 14.7–179 0.05–5.8 mdl-2.01 0.01–0.21 1.46–8.5 3.31–46 1.74–2.65 0.06–2.14

Note: concentration data for some samples has been split to represent compositionally-distinct domains.
Ore Geology Reviews 111 (2019) 103004
W. Liu, et al. Ore Geology Reviews 111 (2019) 103004

4.2. LA-ICP-MS spot analyses analyses, showing both smooth and irregular profiles are given as
Fig. 6.
A summary of enargite LA-ICP-MS data for each sample is given in The trace element distributions in enargite which has replaced by
Table 2 and shown in Fig. 5. The complete LA-ICP-MS spot analysis digenite and goldfieldite from HS mineralization at upper levels
dataset is deposited as Supplementary Appendix 3. There is significant (sample 11lc-2, 760 m) clearly show two stages of growth. The grain
incorporation of Sb (up to 33,120 ppm) and Te (up to 13,160 ppm) in core is distinctly Sb-rich (average 10,667 ppm) whereas grain rims
enargite, both elements locally exceeding 1 wt%. Other enriched trace feature enrichment in Te (7022 ppm), as well as higher concentrations
elements include Sn (up to 7710 ppm), Zn (up to 2120 ppm), and Ge (up of Au (24.5 ppm), Ag (128 ppm), Bi (296 ppm), Pb (271 ppm), Sn
to 3461 ppm), all at concentrations exceeding 0.1 wt%, as well as Mo (2,091 ppm), Zn (261 ppm), Fe (311 ppm), Ge (69 ppm), W (43.2 ppm),
(up to 723 ppm), Cd (up to 347 ppm), Bi (up to 819 ppm), Pb (up to Mo (4.25 ppm), Se (3.5 ppm), V (1.65 ppm), In (0.58 ppm) and Tl
802 ppm), Fe (up to 950 ppm), Se (up to 284 ppm), Ag (up to 323 ppm), (0.18 ppm).
Au (up to 240 ppm) and W (up to 261 ppm). Less abundant trace ele- Patterns of trace elements in enargite from simple digenite + en-
ments include Ga (up to 98 ppm), In (up to 30 ppm), V (up to 49 ppm), argite assemblages in HS mineralization (sample zjs-35) are similar to
and Tl (up to 9 ppm). Mean concentrations of Co, Ni, Mn and Re those in sample 11lc-2 and feature a rim characterised by elevated Au
are < 1 ppm in all samples analysed. (61.3 ppm), Te (3262 ppm), Ag (80 ppm), Sb (6574 ppm), Sn
The concentrations of most of the elements analysed in this study (1866 ppm), Zn (122 ppm), Bi (93 ppm), Pb (63 ppm), Fe (50 ppm), Ge
show great variation within individual grains, within single samples (54 ppm), W (7.4 ppm) and traces of Mo, Ga, In, V and Tl.
and across the dataset. Variation may reach up three orders of magni- The enargite associated with bornite and pyrite within HS miner-
tude in some cases, notably for Sn, Te, and Zn. One important exception alization from upper levels (sample zjs-21, 688 m) features a Au-Te rich
is Sb, which is present at concentrations of 0.1–1 wt% in almost all zone containing Au (mean 11 ppm), Te (4750 ppm), Ag (62 ppm), Sb
analyses. Representative time-resolved depth spectra for single spot (7713 ppm), Sn (2994 ppm), Zn (524 ppm), Bi (132 ppm), Pb (82 ppm),

Fig. 5. Schematic representation of the variation of trace elements contained in enargite from each sample analysed (ppm). Each line represents an individual spot
analysis.

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W. Liu, et al. Ore Geology Reviews 111 (2019) 103004

Fig. 6. Time-resolved LA-ICP-MS depth profiles for selected spots of analysed enargite.

Fig. 7. Top – EPMA element maps of zoned enargite grains associated with digenite from HS mineralization at upper levels (sample 11lc-2, 760 m above sea level);
Bottom – zoned enargite grains associated with covellite from lower levels (sample 510-c-1, 520 m above sea level).

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W. Liu, et al. Ore Geology Reviews 111 (2019) 103004

Fe (218 ppm), Ge (192 ppm) and W (15.3 ppm). (5008 ppm), Zn (1318 ppm), Cd (80.3 ppm), W (58.3 ppm), Ag
Enargite associated with tin minerals (colusite and kiddcreekite) in (18 ppm), and Au (3.6 ppm), a Mo-rich mantle with higher Fe
covellite-rich veins, represented here by sample 510-c-1, shows three (463 ppm), Mo (206 ppm), Ge (316 ppm), Pb (97 ppm), V (10.7 ppm)
distinct compositional groups: a Sn-rich core containing up to and Tl (5.3 ppm), and a Sn-poor rim with higher Sb (8933 ppm) and Bi
7000 ppm Sn and lesser Te (average 942 ppm); a Ge-rich mantle con- (23 ppm).
taining up to 3461 ppm Ge together with higher Zn and Cd (average Lastly, enargite associated with chalcopyrite and tennantite in IS-
668 ppm and 212 ppm, respectively); and a Au-rich rim with higher Te type mineralization from Longjiangting (sample zk301-7) contains
(3450 ppm), Au (29.6 ppm), Ag (88.2 ppm), and Bi (87 ppm). In a lower Sn (207 ppm), Te (65 ppm), Zn (65 ppm), Au (0.5 ppm) but, no-
second sample (510-c-2) containing the same assemblage, there are also tably, also higher Se (244 ppm) and Ge (4 2 7) compared to the other
three distinct groups of enargite compositions: a Sn-rich core (up to samples.
6080 ppm), a Ge-Mo-rich zone with higher Ge (979 ppm), Mo
(409 ppm), Cd (72 ppm), as well as the highest Tl (2.3 ppm), and a W-
4.3. EPMA and LA-ICP-MS element mapping
rich zone with higher W (138 ppm), Te (2312 ppm), and moderate Au
(8.1 ppm).
Complex compositional zoning patterns are readily observable on
Enargite in a massive enargite + pyrite vein from lower levels
BSE images of enargite (Fig. 3b). Oscillatory zoning with respect to As,
(sample dzk403-4, −84 m) displays two groups of compositions: a Sn-
Sb, Te and Sn is revealed by EPMA X-ray mapping (Fig. 7). Grain-scale
rich core with up to 11,450 ppm Sn, as well as up to 1478 ppm Zn, is
zoning patterns clearly show an inverse correlation between the con-
surrounded by a Te-rich rim that also features higher Au (9.9 ppm) and
centrations of As and those of Te, Sb and Sn. There are, however, no-
Pb (153 ppm). There is also a W-rich zone with higher W (169 ppm).
tably differences in zoning patterns within individual enargite grains.
Enargite from a enargite-pyrite-(tennantite)-(tetrahedrite) vein assem-
Enargite associated with digenite from HS mineralization at upper le-
blage also at lower levels in the system (sample dzk005-4) contains the
vels (sample 11lc-2, 760 m) displays oscillatory core-to-rim zoning with
highest concentrations of Sb (23,144 ppm), Zn (730 ppm), and Fe
respect to Sb and Te, in which Sb decreases and Te increases outwards
(397 ppm) but with lower Te (102 ppm) and apparent depletion in Mo
from the core. Comparable oscillatory zoning is seen in enargite asso-
(< 0.1 ppm).
ciated with covellite from lower levels in the system (sample 510-c,
Enargite associated with chalcopyrite and digenite from IS-style
520 m). The zoning (Fig. 7) is particularly marked with respect to Sn, in
mineralization (Wuziqilong, sample zjs-418) displays three different
which the element decreases from core to rim.
stages of overgrowth: a Sn-rich core with higher Te (1070 ppm), Sn
Trace element mapping by LA-ICP-MS is an extremely valuable

Fig. 8. Reflected light image (top left) and LA-ICP-MS element maps of zoned enargite (En) in a digenite-rich sample (sample 11lc-2, upper level, 760 m above sea
level, Zijinshan deposit). Scales in counts-per-second. Dg-digenite, Cv-covellite.

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W. Liu, et al. Ore Geology Reviews 111 (2019) 103004

Fig. 9. Reflected light image (top left) and LA-ICP-MS element maps of zoned enargite (En) from a covellite-rich sample (sample 510-c-1, medium depth, 520 m
above sea level, Zijinshan HS Cu-Au deposit). Scales in counts-per-second. Py-pyrite, Dg-digenite.

technique to provide a visualization of trace element distributions rim enriched in Au, Ag, and Te, and a Bi-Se-rich zone that is depleted in
within individual minerals and is well suited to minerals in which zo- Sn and Sb. A latest overprinting of pre-existing patterns is recorded by
nation is subtle and expressed by variation of trace elements at ppm elevated Zn, Ge, Cd and Mo along fractures. Interestingly, the maps also
levels. Zonation patterns, in terms of inter-element correlations within reveal trace amounts of Tl and sub-ppm levels of Re along the grain
zoned enargite are highlighted on four selected element maps shows as margins.
Figs. 8–11. A fourth series of quantitative maps (Fig. 11) show trace element
Qualitative trace element maps of euhedral enargite from a di- distributions in euhedral enargite within IS-type chalcopyrite-pyrite-
genite-rich sample from the upper part of the Zijinshan deposit (sample (digenite-enargite-bornite) mineralization from the Wuziqilong deposit.
11lc-2) are shown as Fig. 8. This grain, contained within digenite, The maps reveal multi-stage growth with core-mantle-rim structure.
displays two growth stages with increasing Te, Ge, Bi, Au, Ag and Pb The core zone is characteristically rich in Te, Sn, Au, Ag and W, the
from core to rim, and, inversely, a decrease in Sb concentration from mantle zone is characterised by enrichment in Zn, Cd, Ge, Mo, V, Ga,
core to rim. Enrichment in Au and Ag displays a strong correlation with Fe, Pb and Tl, and the outer rim is rich in Sb, Bi, Ge and Se. The maps
that of Te. The distributions of Fe and Cd correlate with Zn in the show that Au and Ag correlate positively with Te whereas the con-
margin and in some patchy zoning along the c axis of the crystal. The centrations of Cd and Ge are positively correlated with those of Zn.
enclosing digenite contains similar concentrations of Ag but lesser Au Core-to-rim zonation trends in a single euhedral enargite grain
when compared to the enargite. hosted within digenite from the same sample are addressed in Fig. 12.
Qualitative trace element maps of a euhedral enargite grain in a These EPMA maps feature a Te-Sn-rich core and Ge-Mo-Sb-rich rim. LA-
covellite-rich sample from the middle part of the Zijinshan HS Cu-Au ICP-MS spot data for the same grain show a decrease in Te, Sn, Au, Ag,
deposit (sample 510-c-1) are shown in Fig. 9. This grain shows a later Zn, Cd and In from core to rim, whereas Sb, Ge, Mo, Se and Fe increase.
overprinting of early enargite in the margin or in the inner zone of the
grain which features replacement by covellite and relict inclusions of 5. Discussion
colusite (recognizable by higher W and V). The overprinting zone of the
grain is characteristically rich in Au, Ag, Bi and Te, which is followed by The quantitative data and EPMA and LA-ICP-MS mapping presented
Zn, Cd, Ge and Ga-enrichment. Enclosing pyrite contains lesser Ag and in this contribution demonstrate that enargite, like many other sul-
Au than the enargite. phides, is a highly complex mineral with respect to trace element
Qualitative trace element maps of another euhedral enargite grain chemistry, and grain-scale zonation. There is clearly extensive variation
in a comparable assemblage are shown in Fig. 10. This grain features from grain to grain within a single sample, between samples, and be-
replacement of early W-V-rich colusite by enargite, which in turn dis- tween different deposits within a zoned orefield. Identification of the
plays multiple growth stages. The maps show an early Sn-rich core, a fundamental reasons for the observed heterogeneity lies beyond the

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W. Liu, et al. Ore Geology Reviews 111 (2019) 103004

Fig. 10. Reflected light image (top left) and LA-ICP-MS element maps of zoned enargite (En) from a covellite-pyrite-(digenite)-(enargite) vein assemblage (sample
510-c-2, medium depth, 520 m above sea level, Zijinshan HS deposit). Scales in counts-per-second. Col-colusite, Cv-covellite, Dg-digenite, Py-pyrite.

scope of the present study and would require the systematic study of a The presence of measurable concentrations of precious metals, Au and
substantially larger suite of samples, and independent empirical evi- Ag, as well as so-called ‘critical’ elements, notably Te and Ge, within
dence for the evolution of fluid conditions. We therefore focus on enargite is sure to attract interest from the perspective of potential re-
evaluating patterns and mechanisms for trace element substitution, the covery of these elements from enargite-bearing ores.
origin of grain-scale zoning, partitioning between co-existing minerals, Models for the crystal structure of enargite (Karanović et al., 2002)
the potential constraints on ore genesis, and not least, for the value of show an orthorhombic structure derived from wurtzite by ordered ca-
enargite compositions as a vectoring tool in exploration. tion substitution in which each cation is tetrahedrally coordinated to
four sulphur atoms, and each sulphur atom is tetrahedrally coordinated
5.1. Enargite as a carrier of trace elements and substitution mechanisms by one arsenic and three copper atoms. The different size of the tetra-
hedral (CuS4) and (AsS4) polyhedra may cause a significant distortion
The dominant minor element in enargite is Sb, but the mineral also in the enargite structure (Karanović et al., 2002). Hexagonal packing of
contains measurable amounts of several other elements, including Te, the anions can compensate for such distortion much better than cubic
Sn, Zn, Ge, Cd, Mo, Fe, Ag, Bi, Pb, Au, and Se. These elements display packing (Pfitzner and Reiser, 2002).
uniformly flat spectra during analysis (Fig. 5), and commonly occur at The nominal ionic states of Cu, As, and S ions in enargite have been
concentrations several orders of magnitude above minimum detection confirmed as Cu+, As5+ and S2-, respectively (Di Benedetto et al.,
limits of the LA-ICP-MS method. The uniform spectra of these elements 2011). Evidence has been put forward suggesting the presence of Cu2+
suggest that they are structurally bound within the crystal lattice of in enargite (Frost et al., 2006) but this is thought to be an oxidation-
enargite. Rare irregular signals for Fe, Sb, Bi, Sn, W, Ag, Au, Pb, and Mo related phenomenon. Substitution of Sb is readily achieved by re-
may, however, suggest the presence of micron- to nanoscale inclusions placement of As5+ by Sb5+. In this study, the LA-ICP-MS dataset shows
of discrete minerals, as was also noted by Deyell and Hedenquist significantly incorporation of chalcophile elements in enargite, espe-
(2011). The Au content in these enargites varies from below detection cially Te, Sn, Zn and Ge. The grain-scale zoning patterns clearly show
limit to tens of ppm, and one analysis records 240 ppm, confirming that an inverse correlation between the concentrations of (As, Sb) and Te
enargite can, potentially be a significant Au carrier in HS ore systems. (Fig. 7), and the spot data show a positive correlation between Te and

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Fig. 11. Reflected light image (top left) and LA-ICP-MS element maps of zoned enargite (En) from IS-type chalcopyrite-pyrite-(digenite-enargite-bornite) miner-
alization, Wuziqilong deposit (sample zjs-418). Scales in parts-per-million. Note, only the elements within the enargite are quantifiable and the yellow regions for Ag
are Fe are artefacts from data processing. Dg-digenite. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of
this article.)

(Au + Ag) (Fig. 13a). Tellurium-rich members of the tetrahedrite group has been observed among chalcophile elements. Furthermore, con-
have been widely described, in which Te occupies the (As,Sb) site via centrations of Cd and Ge correlate positively with those of Zn, as seen in
the coupled substitution: (Cu,Fe,Zn)2+ + (As,Sb)3+ → Cu+ + Te4+ the plot of (Zn + Cd) vs. (Sn + Ge + Mo) presented as Fig. 13b. Liu
(Kase, 1986; Shimizu and Stanley, 1991). et al. (2014, 2016) note that in the Zijinshan ore district, enargite is
In many sulphide-bearing refractory gold ores, “invisible gold” ac- intimately associated with Sn-minerals (colusite, vincennite, kiddcree-
counts for an important proportion of the gold present (Cook and kite, hemusite and stannoidite). Enargite is notably closely intergrown
Chryssoulis, 1990). “Invisible gold” may be structurally-bound or occur with colusite, which features the complex coupled substitution invol-
as Au-bearing nanoparticles (< 1000 Å in size) of native gold and/or ving (As, Sb) and (Sn, Ge), according to either (As,Sb)5+ ↔
Au-(Ag)-tellurides (Simon et al., 1999; Palenik et al., 2004; Ciobanu (Sn,Ge)4+ + Cu+ (Spry et al., 1994), or (As,Sb)5+ + Cu+ ↔
et al., 2012). Numerous studies have pointed out that arsenian pyrite (Sn,Ge)4+ + (Fe,Zn,Cu)2+ (Frank-Kamenetskaya et al., 2002). It is also
and arsenopyrite are particularly good hosts for invisible gold (e.g., inferred that incorporation of Sn, Te, Ge and Mo substitution may take
Simon et al., 1999; Reich et al., 2005), prompting the question of place via incorporation of Sn4+, Te4+, Ge4+ and Mo4+, creating a
whether other As-bearing minerals might also carry significant amounts charge imbalance that is met by substitution of Zn2+, Fe2+ and other
of gold. Whereas the oxidation state of invisible gold in common sul- divalent cations (Cd2+ and Pb2+) into the Cu+ site. Although no sup-
phides is still debated, most researchers agree that Au+ is the dominant porting evidence exists, the charge imbalance could plausibly also be
form of Au in sulphide (Simon et al., 1999). Incorporation of Au3+, or met by oxidation of Cu+ to Cu2+. The existence of related Ge-rich
even Au-, has however been hypothesized (e.g., Arehart et al., 1993; Li colusite might suggest that Ge is, in part, incorporated via the coupled
et al., 1995) but remains unproven by spectroscopic evidence. As- substitution As5+ + Cu+ ↔ Ge4+ + Zn2+, as proposed by Bernstein
suming that Cu and Au are monovalent and that As is pentavalent, it (1985).
can be inferred that Te substitution may take place via incorporation of Based on the correlations observed, several possible substitutions
Te4+ creating a charge imbalance that is met by a coupled substitution can be invoked. These can be summarised generically as:
of the type: 2(Ag,Au)+ + Te4+ ↔ (As,Sb)5+ + Cu+, although this
would necessitate occupancy of interstitial positions. M12 + + M24 + As5 + + Cu+ (1)
The enargite trace element dataset also reveals an inverse correla-
tion between As and Sn in many cases, whereas a positive correlation Te4 + + 2M3+ As5 + + 2Cu+ (2)

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Fig. 12. (a) BSE image and EPMA maps and (b) core-to-rim profiles of LA-ICP-MS spot analyses within a relatively coarse euhedral enargite grain, IS-type miner-
alization (Wuziqilong deposit, sample zjs-418), showing compositional variation in trace element concentrations. En-enargite, Dg-digenite.

where M1 = Zn, Fe, Cd and Pb; M2 = Sn, Te and Ge; and M3 = Ag, Au zoning with respect to As, Sb, Sn and Te. The LA-ICP-MS maps
and Tl. Minor components Bi and In are almost certainly trivalent and (Figs. 8–11), offering levels of sensitivity better suited to trace elements
Se almost certainly substitutes, as Se2-, into the sulphur site. Although present at low concentration, also reveal a marked zonation with re-
the charge imbalance caused by incorporation of Sn4+, Te4+, Ge4+ and spect to Au, Ag, Bi, Ge, Zn, Cd, Pb, W, Mo and Tl. The similar patterns
Mo4+ appears to be achieved by substitution of Zn2+, Fe2+ and other shown by Au, Ag, Bi and Te could indicate that substitution of As by Te
divalent cations (Cd2+ and Pb2+) into the Cu+ site. enhances incorporation of Au and Ag in enargite. Although additional
studies would be required, grain-scale compositional zoning in enargite
may be widespread, even ubiquitous.
5.2. Grain-scale compositional zoning

Previous studies show that single enargite grains contain variable 5.3. Chemical and textural relationships between enargite and co-existing
concentrations of trace elements which may be caused by the presence minerals
of complex growth zones (Deyell and Hedenquist, 2011). Borgheresi
et al. (2013) show a single luzonite crystal exhibiting concentric (os- The studied enargite is intimately associated with pyrite, colusite,
cillatory) and sectorial zoning with respect to Sb and Sn. EPMA maps digenite and covellite. Most of the colusite and pyrite belongs to an
presented in the present study (Figs. 7 and 12) show marked oscillatory earlier stage of mineralization that is replaced by enargite and latter

Fig. 13. Plots illustrating the correlation between (a) Te and (Au + Ag), and (b) (Zn + Cd) and (Sn + Ge + Mo) in enargite.

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digenite and covellite. LA-ICP-MS mapping shows that digenite repla- enriched in Au and Te, enargite from the centre of the Lepanto HS
cing enargite contains higher amounts of Ag and Fe and comparable deposit is enriched in Ag, Fe and Pb, and enargite from the most distal
amounts of Bi, Pb, and Au (Figs. 8, 9 and 11). Enclosing pyrite contains ores is enriched in Zn ( ± Cd). The ores containing Au-Te-bearing en-
comparable amount of Ag, Pb, and Bi (Figs. 9 and 10). In contrast, argite that were sampled from the HS-style orebodies in Lepanto close
covellite seems a poor host for most of trace elements except Se to the volcanic pipe should represent the HS hydrothermal centre, and
(Fig. 10). Trace element distributions in Cu-(Fe)- sulphides are identical thus be a guide to high-grade Au mineralization. Deyell and Hedenquist
to the preliminary spot analyses given by Liu et al. (2017), which (2011) considered that the observed trace element patterns may re-
showed digenite and djurleite to contain measurable concentrations of present a potentially valuable vectoring tool in exploration of porphyry-
Au, whereas pyrite contains < 1 ppm Au. Previous studies state that epithermal environments.
digenite and chalcocite have the potential to be major carriers of Ag Data given by Sahlström et al. (2017) would suggest that enargite
(and possibly Au) in epithermal deposits (Reich et al., 2010; Cook et al., associated with chalcopyrite-tennantite–pyrite assemblages formed in
2011). LA-ICP-MS results in the present study show that enargite gen- the IS-stage are depleted in Sn, Te, Au, and Zn. Collectively, these data
erally contains higher concentrations of Ag, Au, Te and Sn than the indicate that changes in trace element signature may be inconsistent or
surrounding minerals. In the extreme HS stage (characterized by an non-systematic from deposit to deposit. However, published data are
association of covellite-digenite, Einaudi et al., 2003), enargite contains relatively few, and without details of mineral associations or a careful
the highest amount of Au, Ag, Bi, and Te, also implying that enargite assessment of grain-scale heterogeneity in some of the published stu-
may scavenge Au, Ag, Bi and Te from surrounding minerals. Enargite dies, a clear evaluation of the implications for ore genesis or application
may also act as an important carrier of Sn in HS-type systems, in which as an exploration vector must await future work.
the Sn may be inherited from early Sn-sulphides (colusite and kidd- In the present study, enargite from the HS stage typically shows a
creekite) and provide a source of Sn for late-stage Sn-sulphides such as marked enrichment in Te and Sn whereas enargite from the IS-stage is
colusite and stannoidite. Te-Sn-depleted and relatively enriched in Sb and Se. If validated by
According to previous work on the Zijinshan deposit (Liu et al., comparative studies elsewhere (see below), such differences represent a
2016), gold mostly occurs as electrum and calaverite in digenite-(cov- potential vector for exploration within porphyry – HS-epithermal sys-
ellite) ore that also contains Te-rich tennantite (or goldfieldite). Elec- tems. Furthermore, the presence of Te-rich enargite may be a pro-
trum and calaverite occur as elongate or irregular grains (~10 μm in spective guide to high Au-grade mineralization.
size) included within digenite, Te-rich tennantite or goldfieldite. It is
plausible that early Au-Te-rich enargite was replaced by Te-rich ten- 5.5. Implications and future work
nantite and goldfieldite with associated release of Au and Te.
Additional evidence should be sought for systematic variation of
5.4. Interpretation of trends across the dataset: constraints on ore genesis enargite composition from other high- to intermediate sulphidation ore
systems worldwide to validate the findings outlined here. Such work
Enargite grains from the Zijinshan HS deposit show at least four might assess whether the trace element distributions we have docu-
stages of growth: from core to rim, the trace element signature varies mented are widely applicable across systems that differ in terms of age,
from Sn-Sb-bearing, through Te-Au-Ag-bearing, and Zn-Cd-Ge-Mo- geological setting, and/or commodities within the deposits. Successful
bearing, to rims that are relatively enriched in Se and Bi (Fig. 11). affirmation that these trends are systematic would underpin the inter-
Enargite associated with pyrite and bornite represents the earlier stage pretations of ore genesis and application of enargite as an exploration
of HS mineralization and contains the highest concentrations of Sb and vector.
Sn. Enargite associated with digenite and covellite represents the ex- Future study should also address aspects of compositionally-zoned
tremely high-sulphidation mineralization and is conspicuous by ele- enargite at the nanoscale. Research questions would include whether
vated Te, Au, Ag and Bi. Enargite formed in the late HS stage contains the scale of compositional zoning extends below the micron-scale,
higher Zn, Cd, Mo and Ge, whereas higher amounts of Se and Bi whether modifications to crystal structure facilitate trace element in-
characterize the (waning) IS-stage. Notably, enargite associated with corporation, or whether selective trace element incorporation is asso-
chalcopyrite, bornite, and tennantite from the Longjiangting IS deposit ciated with particular crystal axes. Careful observation at the nanoscale
shows depletion in Sn, Te and Zn, but also higher Se and Ge compared observation might also allow a check on whether there are lattice-scale
to the other samples. Trace element patterns recorded in enargite from intergrowths of enargite and its polymorph, luzonite, in zoned enargite,
the Wuziqilong Cu deposit clearly record two growth stages. The HS analogous to that observed among ZnS polymorphs (e.g., Ciobanu et al.,
stage core displays enrichment in Sn, Te, Zn and Au, whereas the IS- 2011). Pósfai and Sundberg (1998) indicate that both polytypes may
stage rim shows a marked enrichment in Se, Sb, Mo and Fe, and relative occur in highly disordered structures, whereby luzonite-type and en-
depletion in Sn, Te, Au and Zn. There is thus a remarkable and sys- argite-type structures are intergrown at the atomic scale.
tematic variation in the composition of enargite from the HS- to IS- The presence of measurable concentrations of the precious metals,
stage, which reflects fluid evolution during its transition. Au and Ag, as well as key so-called ‘critical’ elements, notably Te and
Other trace elements, notably W, V, Tl, In and Ga, are also re- Ge, within enargite are sure to attract interest from the perspective of
mobilized at HS conditions. Trace mineral assemblages containing W, potential recovery of these elements from enargite-bearing ores.
Sn, Bi, Te, Se, Ga, V, In and Ge are reported in many HS-style epi-
thermal deposits worldwide (e.g., Bogdanov et al., 2004), hinting that 6. Conclusions
these chalcophile elements are easily remobilized during the most HS
conditions, a finding of potential significance for ore genesis and ex- 1. Enargite is shown to host Sb, Te, Sn, Zn and Ge at concentrations up
ploitation. to several thousand ppm. The mineral also appears to contain Mo,
Previous studies (Deyell and Hedenquist, 2011; Maydagán et al., Cd, Bi, Pb, Fe, Se, Ag, Au W, Ga and In.
2013; Dekov et al., 2016; Sahlström et al., 2017) have demonstrated 2. This study provides the first example of oscillatory, grain-scale
that enargite (or luzonite) can incorporate chalcophile elements (Sb, Bi, compositional zoning in enargite with respect to Sb, Sn, Te and
Sn, Se, Te, Zn, Pb, and Ag), and that significant variability in the trace several other trace elements. Although zonation patterns differ
element signature of enargite may be expected across an orebody. The somewhat from grain to grain, they reveal an evolution of ore-
spatial distribution of trace elements in enargite from the Mankayan forming fluids, with two elements of particular interest (Au and Te)
District, Philippines, documented by Deyell and Hedenquist (2011) largely concentrated in rim overgrowths formed during the HS stage
show that enargite from close to the Far Southeast porphyry deposit is of mineralization. Although the sample suite was carefully selected,

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it is nevertheless small relative to the scale of the orefield. Borgheresi, M., Buccianti, A., Di Benedetto, F., Vaughan, D.J., 2013. Application of
3. Aside from the well-known substitution of As5+ by Sb5+, in- compositional techniques in the field of crystal chemistry: a case study of luzonite, a
Sn-bearing mineral. Math. Geosci. 45, 183–206.
corporation of Sn and Te into the enargite structure is achieved by Ciobanu, C.L., Cook, N.J., Utsunomiya, S., Pring, A., Green, L., 2011. Focussed ion beam –
substitution of Sn4+, Ge4+ and Te4+ for As5+. Charge balance is transmission electron microscopy applications in ore mineralogy: bridging micron-
maintained by incorporation of Fe2+, Zn2+, Cd2+, Pb2+, (and, po- and nanoscale observations. Ore Geol. Rev. 42, 6–31.
Ciobanu, C.L., Cook, N.J., Utsunomiya, S., Kogagwa, M., Green, L., Gilbert, S., Wade, B.,
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This research was undertaken while W.L. was a visiting scholar at Kase, K., 1986. Tellurian tennantite from the Besshi type deposits in the Sambagawa
The University of Adelaide. This research was funded by the National metamorphic belt, Japan. Canadian Mineral. 24, 399–404.
Lane, D.J., Cook, N.J., Grano, S.R., Ehrig, K., 2016. Selective leaching of penalty elements
Natural Science Foundation of China (No. 41672035, 41002016) with
from copper concentrates: a review. Miner. Eng. 98, 110–121.
additional funding from Education Department of Fujian Province Lattanzi, P., Da Pelo, S., Musu, E., Atzei, D., Elsener, B., Fantauzzi, M., Rossi, A., 2008.
gratefully acknowledged. N.J.C. acknowledges additional support from Enargite oxidation: a review. Earth Sci. Rev. 86, 62–88.
Li, J.L., Feng, D.M., Qi, F., Zhang, G.L., 1995. The existence of the negative valence state
the ARC Research Hub for Australian Copper-Uranium (Grant
of gold in sulfide minerals and its formation mechanism. Acta Geol. Sin. 69, 67–77 (in
IH130200033). We extend our appreciation to two anonymous re- Chinese with English abstract).
viewers for their constructive comments and thank Editor-in-Chief Liu, W.Y., Liu, Y., Qiu, X.P., 2012. The first discovery of hemusite in China and its mi-
Franco Pirajno for his handling of the manuscript. neralogical features. Acta Mineral. Sinica 32, 493–497 (in Chinese with English ab-
stract).
Liu, W.Y., Dong, C., Gu, X.P., Liu, Y., Qiu, X.P., Chen, Y.C., 2014. The crystal structure of
Appendix A. Supplementary data kiddcreekite solved using micro X-ray diffraction and the EPCryst program. Mineral.
Mag. 78, 1517–1525.
Liu, W.Y., Cook, N.J., Ciobanu, C.L., Liu, Y., Qiu, X.P., Chen, Y.C., 2016. Mineralogy of
Supplementary data to this article can be found online at https:// tin-sulfides in the Zijinshan porphyry–epithermal system, Fujian Province, China. Ore
doi.org/10.1016/j.oregeorev.2019.103004. Geol. Rev. 72, 682–698.
Liu, W.Y., Chen, Y.C., Liu, Y., 2017. EPAM and LA-ICP-MS micro-analysis of Cu-Fe-S
minerals in Zijinshan orefield: implications for ore genesis. Earth Sci. Front. 24,
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