Ore Geology Reviews xxx (xxxx) xxx–xxx

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Ore Geology Reviews

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Review

A review of Te and Se systematics in hydrothermal pyrite from precious

metal deposits: Insights into ore-forming processes
⁎
Manuel Keitha, , Daniel J. Smitha, Gawen R.T. Jenkina, David A. Holwella, Matthew D. Dyeb
a
Department of Geology, University of Leicester, Leicester LE1 7RH, UK
b
Colorado School of Mines, Golden, CO 80401, USA

A B S T R A C T

Pyrite is one of the most common minerals in many precious and base metal hydrothermal ore deposits and is an
important host to a range of trace elements including Au and Co and the semi-metals As, Se, Sb, Te and Bi. As
such, in many hydrothermal ore deposits, where pyrite is the dominant sulphide phase, it can represent a major
repository for these elements. Furthermore, the concentrations and ratios of Au, As and Co in pyrite have been
used to infer key ore-forming processes. However, the mechanisms controlling the distribution of Te and Se in
pyrite are less well understood. Here we compare the Te and Se contents of pyrite from a global dataset of Carlin-
type, orogenic Au, and porphyry-epithermal deposits to investigate: (1) the potential of pyrite to be a major
repository for these elements; and (2) whether Te and Se provide insights into key ore-forming processes. Pyrite
from Carlin-type, low-sulphidation and alkaline igneous rock-hosted epithermal systems is enriched in Te (and
Se) compared to pyrite from high-sulphidation epithermal and porphyry Cu deposits. Orogenic Au pyrite is
characterised by intermediate Te and Se contents. There is an upper solubility limit for Te as a function of As in
pyrite, similar to that established for Au by Reich et al. (2005); and this can be used to identify Te present as
telluride inclusions, which are common in some epithermal-porphyry and orogenic Au deposits. Physicochem-
ical fluid parameters, such as pH, redox and temperature, as well as crystal-chemistry control the incorporation
and concentration of Se and Te in pyrite. Neutral to alkaline fluids have the ability to effectively mobilise and
transport Te. Fluid boiling in porphyry-epithermal systems, as well as wall rock sulphidation and oxidation in
Carlin-type (and orogenic Au) deposits can effectively precipitate Te in association with pyrite and Au. In
contrast, Se concentrations in pyrite apparently vary systematically in response to changes in fluid temperature,
irrespective of pH and fO2. Hence, we propose that the Se contents of pyrite may be used as a new geo-ther-
mometer for hydrothermal ore deposits. Furthermore, the comparison of bulk ore and pyrite chemistry indicates
that pyrite represents the major host for Te and Se in Carlin-type and some epithermal systems, and thus pyrite
can be considered to be of economic interest as a potential source for these elements.

1. Introduction
Pyrite is the most abundant sulphide mineral in the Earth’s upper
crust and represents a major mineral in most hydrothermal ore deposits
(Rickard and Luther, 2007; Cook et al., 2009a; Deditius et al., 2014;
Keith et al., 2016a). Pyrite is stable under various physicochemical fluid
conditions and its refractory behaviour to post-depositional meta-
morphism compared to other sulphides (Craig and Vokes, 1993; Fleet
et al., 1993; Craig et al., 1998; Agangi et al., 2013) and its near-ubiquity
makes it suitable for micro-analytical studies to reconstruct ore-forming
processes through space and time (Agangi et al., 2013; Reich et al.,
2013; Wohlgemuth-Ueberwasser et al., 2015; Keith et al., 2016b).
Previous investigations have highlighted that pyrite represents an
important sink for many trace metals including Co, Ni, Cu, As, Se, Mo,
Ag, Sb, Te, Pb, Bi, Au and PGE (e.g., Large et al., 2009; Maslennikov
et al., 2009; King et al., 2014; Smith et al., 2014; Tanner et al., 2016).
Most of these studies have focused on As and associated trace metals,
such Ag, Sb, Au and Pb (e.g., Reich et al., 2005, 2013; Large et al.,
2009; Deditius et al., 2009a, 2014; Keith et al., 2016a), but thus far very
few investigations have included Te and Se (Huston et al., 1995;
Wohlgemuth-Ueberwasser et al., 2015; Keith et al., 2016b). Hence,
much less is known about the processes that control the incorporation
of Te and Se into pyrite – adjacent group 16 elements that might be
expected to show some similarities in geochemical behaviour..
Hydrothermal processes responsible for ore deposition vary be-
tween different deposit-types and can significantly fractionate trace

⁎
Corresponding author at: Department of Geology, University of Leicester, University Road, Leicester LE1 7RH, UK.
E-mail address: mk528@le.ac.uk (M. Keith).

http://dx.doi.org/10.1016/j.oregeorev.2017.07.023
Received 25 April 2017; Received in revised form 24 July 2017; Accepted 30 July 2017
0169-1368/ © 2017 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/BY/4.0/).

Please cite this article as: Keith, M., Ore Geology Reviews (2017), https://doi.org/10.1016/j.oregeorev.2017.07.023
M. Keith et al.
elements in hydrothermal systems between the vapour, liquid and solid
phase (Cline et al., 2005; Goldfarb et al., 2005; Seedorff et al., 2005;
Simmons et al., 2005). Different deposit-types thus have variable but
characteristic trace element enrichments (Cook et al., 2009b). Tell-
urium and Au, for example, have been identified as elements of eco-
nomic interest in Carlin-type and epithermal systems. Due to its ubi-
quity and ability to concentrate trace elements, pyrite may represent an
economically important host for these metals (Reich et al., 2005; Kesler
et al., 2007). Hence, the future supply of a range of trace elements, such
as Te and Se (essential for the manufacture of photovoltaic cells in the
solar energy industry) may be resolved by the processing of minerals
including pyrite (e.g., Hofstra and Cline, 2000; Reich et al., 2013;
Deditius et al., 2014). If not recovered, both elements have potential
eco-toxicological impacts (Lussier et al., 2003; Perkins, 2011) if sent to
tailings and waste, or volatilised during pyro-metallurgical processing,
and may require specialised treatment and handling if abundant. Both
elements can have impacts (e.g. passivation) on metallurgical proces-
sing and the recovery of more valuable elements (Spry et al., 2004;
Adams, 2005) and systems and processes need to accommodate the
concentration of trace elements in ore feeds. Thus, understanding the
behaviour of Te and Se during mineralisation processes and subsequent
deportment in ore assemblages is fundamental to assess these impacts.
This study is the first investigation into the chemistry of Te and Se in
pyrite from a range of the most economically important hydrothermal
precious metal deposits: Carlin-type, orogenic Au, and porphyry-epi-
thermal deposits. We show that pyrite is a significant host for Te and Se
in some hydrothermal deposits, and that the Te contents of pyrite reveal
information on key ore-forming parameters, such as pH, redox and
temperature. Furthermore, we demonstrate that the Se contents of
pyrite can potentially be used as a geo-thermometer in studies of hy-
drothermal ore genesis.
2. Research background
2.1. Pyrite chemistry as a proxy for ore-forming conditions
Several studies have shown that pyrite chemistry can provide a
proxy for ore-forming processes in hydrothermal systems (Large et al.,
2009; Reich et al., 2013; Deditius et al., 2014; Keith et al., 2016a). It is
important to note that the composition of pyrite has been shown to be
representative for the signature of the mineralising fluids in many hy-
drothermal systems, such as porphyry-epithermal (Deditius et al., 2014)
and volcanic-hosted massive sulphide deposits (Keith et al., 2016b).
Variations in the trace element composition of pyrite have been inter-
preted to be caused by changes in physicochemical fluid parameters,
such as temperature, pH, redox and the availability of complex-forming
ligands (Huston et al., 1995; Deditius et al., 2014; Revan et al., 2014;
Keith et al., 2016a), as well as fluid-wall rock interaction and phase
separation (Wohlgemuth-Ueberwasser et al., 2015; Keith et al.,
2016a,b). Thus, pyrite chemistry is a robust indicator of fluid compo-
sition. Furthermore, the results of Wohlgemuth-Ueberwasser et al.
(2015) suggest a systematic relationship between pyrite chemistry and
the composition of the metal source. However, when using pyrite
chemistry to reconstruct processes of ore formation it is important to
take the crystal-chemical properties of pyrite into account due to their
fundamental control on the trace element incorporation (Chouinard
et al., 2005).
2.2. Te chemistry
Tellurium occurs in various oxidation states from −II to +VI in
aqueous solutions including Te2−, Te22−, Te (s), TeO32− and TeO42−
(Koelbl, 1995; Brugger et al., 2012; Grundler et al., 2013). Despite the
low crustal abundance of Te (5 ppb, Wedepohl, 1995), it can occur in
high concentrations (ten to thousands of ppm) in association with Au in
many ore deposits, which makes it an element of geochemical and
2
Ore Geology Reviews xxx (xxxx) xxx–xxx
potential economic interest (Kelley et al., 1998; Pals and Spry, 2003;
Ciobanu et al., 2006; Sung et al., 2009). The most common Te-bearing
minerals in nature are tellurides and native Te (Cook et al., 2009b;
Ciobanu et al., 2012). However, high Te contents have also been
identified in As- and Au-rich pyrite (Chouinard et al., 2005; King et al.,
2014) that usually occurs in Carlin-type, low-sulphidation epithermal
and some orogenic Au deposits (Kesler et al., 2007; Cook et al., 2009a;
Deditius et al., 2014). Chouinard et al. (2005) explained the association
of As, Te and Au in pyrite by their preferential incorporation on the
(1 1 0) surfaces in the cubic crystal system. Experimental studies ac-
companied by mineral stability calculations indicate that Te is highly
soluble in hydrothermal fluids at neutral to alkaline pH, low salinity
and high temperature and oxygen fugacity (fO2), whereas Te solubility
significantly decreases under more reduced conditions leading to Te
deposition (Cooke and McPhail, 2001; Cook et al., 2009b; Grundler
et al., 2013; Gao et al., 2017).
2.3. Se chemistry
Selenium, like other Group 16 elements in the periodic table, such as S
and Te, also occurs in several oxidation states (−II, 0, +IV, +VI;
Yamamoto, 1976; Koelbl, 1995; Schirmer et al., 2014). Selenide minerals
are rare in nature compared to tellurides (Simon et al., 1997), despite the
significantly higher crustal abundance of Se (130 ppb; Rudnick and Gao,
2003) compared to Te (5 ppb, Wedepohl, 1995). Consequently, in hy-
pogene mineralisation most Se is hosted by other minerals, such as pyrite,
galena and chalcopyrite (Yamamoto et al., 1984; Huston et al., 1995;
Williams et al., 2015; Wohlgemuth-Ueberwasser et al., 2015). Selenium is
a common trace element analysed in hydrothermal pyrite and Se varia-
tions have been commonly attributed to changes in fluid temperature
(Auclair et al., 1987; Huston et al., 1995; Maslennikov et al., 2009; Revan
et al., 2014; Keith et al., 2016a,b). However, other studies have pointed
out that Se in pyrite may vary as a function of the pH and the redox
conditions of the ore-forming fluids (Yamamoto et al., 1984; Huston et al.,
1995). Thermodynamic modelling calculations by Huston et al. (1995)
and Layton-Matthews et al. (2008) suggest that the Se content of pyrite is
directly related to ∑Se/S ratio of the parental fluid phase. It is worth
mentioning that the incorporation of Se, compared to As, Te and Au, is
less controlled by the crystal-chemical properties of pyrite (Chouinard
et al., 2005).
3. Geological overview: deposit-types and ore mineralisation
This section summarises the key magmatic and hydrothermal data,
such as host rock and physicochemical fluid composition (Table 1) and
highlights the most important features of metal precipitation in the
different deposit-types investigated in this study (Table 2). Further
details can be found in the electronic supplementary material (Table
A1).
3.1. Carlin-type deposits
The Carlin-type deposits of Nevada have been used as the type lo-
cality for Carlin-style Au mineralisation (e.g., Cline et al., 2005).
However, similar deposits have been identified in Canada, China and
Sweden (Table 2; Garnier et al., 2007; Su et al., 2008; Large et al.,
2011). Gold mineralisation in Carlin-type systems is generally accom-
panied by pyrite precipitation, which represents the primary host for
economic Au either in solid solution or as sub-micron sized Au0 inclu-
sions (Emsbo et al., 2003; Cline et al., 2005; Reich et al., 2005). Two
principal sources for the ore-forming fluids have been suggested in-
cluding a meteoric and a magmatic fluid component with variable
proportions between different deposits (Cline and Hofstra, 2000; Cline
et al., 2005). Carlin-type ore-fluids are characterised by low fluid
temperatures (< 240 °C), low fO2, low salinities and near-neutral pH
caused by fluid neutralisation due to the interaction with the carbonate
M. Keith et al. Ore Geology Reviews xxx (xxxx) xxx–xxx

host rocks (Table 1; Cline and Hofstra, 2000; Cline et al., 2005;

Seedorff et al. (2005)

Jensen and Barton
Cline et al. (2005)
Muntean et al., 2011). Metal deposition is generally attributed to sul-

Simmons et al.

Simmons et al.

Goldfarb et al.
phidation of Fe in the carbonate wall rocks causing pyrite precipitation

References
accompanied by precious metal mineralisation (Cline and Hofstra,
2000; Emsbo et al., 2003; Cline et al., 2005). Phase separation, i.e. fluid

(2005)

(2005)

(2000)

(2005)
boiling, has been observed in some Carlin-type systems but never in
association with the main stage of ore formation excluding it as a
principle process for ore mineralisation (Cline and Hofstra, 2000).

Magmatic, metamorphic, minor meteoric (?)

3.2. Orogenic Au deposits

Mainly magmatic, minor meteoric (?)

Orogenic Au deposits form during the late stage of orogeny and are
typically hosted by rocks of greenschist to amphibolite metamorphic

Magmatic, minor meteoric

Meteoric, minor magmatic

grade that may be spatially related to granitoid intrusions (Table 1).
Arsenopyrite and pyrite represent the most abundant sulphide minerals

Magmatic, meteoric

Meteoric, magmatic
that occur in association with the Au mineralisation, which formed
from low salinity, CO2-bearing, reduced and near-neutral pH fluids that

Fluid sources
show a wide range in fluid temperatures from about 200 to 500 °C
(Table 1; Goldfarb et al., 2005; Cook et al., 2009b). Fluid-wall rock
interaction accompanied by host rock sulphidation and pressure fluc-
tuation due to crack and seal causing fluid phase separation represent
the most important mechanisms for metal precipitation (Sibson et al.,

Moderate-high

Moderate-high
1988; Loucks and Mavrogenes, 1999; Goldfarb et al., 2005; Gao et al.,
2017). The chemical and isotopic composition of low temperature

Salinity
orogenic Au fluids, as well as host rock sulphidation as a common

High
Low

Low

Low
precipitation process indicate that some orogenic Au deposits, such as
Sunrise Dam (Table 2; Sung et al., 2009) and Dongping (Table 2; Hart
et al., 2002; Gao et al., 2017), probably formed under conditions similar
Near neutral

Near neutral

Near neutral
Very acidic
to Carlin-type systems (Ridley and Diamond, 2000; Cline et al., 2005;

Alkaline

Acidic
Goldfarb et al., 2005).
pH

3.3. Porphyry-epithermal deposits

Intermediate
Porphyry and epithermal mineralisation are controlled by cooling
and condensation of magmatic vapours, fluid boiling and mixing of
High

High
Low

Low

Low
fO2

magmatic and meteoric fluids (Cooke and McPhail, 2001; Seedorff

et al., 2005; Simmons et al., 2005), which is in contrast to the described
ore precipitation mechanisms in Carlin-type (Cline and Hofstra, 2000;
< 200–700

Emsbo et al., 2003; Cline et al., 2005) and orogenic Au systems (Sibson
180–240
150–300

150–300

150–300

200–500
T (°C)

et al., 1988; Loucks and Mavrogenes, 1999; Goldfarb et al., 2005).

Deditius et al. (2014) stressed that metals are fractionated between
porphyry and epithermal systems. Gold, for example, generally stays in
solution in the deeper porphyry environment and precipitates at shal-
Compilation of the key magmatic and hydrothermal data for the studied ore deposits.

lower crustal levels under epithermal conditions (< 1.5 km, < 300 °C;
Simmons et al., 2005), which explains the lower Au grades in porphyry
compared to epithermal systems (Deditius et al., 2014). The Rosia
Magmatic and sedimentary, granitoid intrusions

Poieni deposit (Table 2) represents an example where a porphyry

Alkaline volcanic and subvolcanic intrusives
Mainly volcanic and subvolcanic intrusives

Mainly volcanic and subvolcanic intrusives

system has been overprinted by a later high-sulphidation epithermal

Metamorphic rocks, granitoid intrusions

vein network highlighting the close relationship between porphyry and

Abbreviations: LS = low-sulphidation, HS = high-sulphidation.

epithermal systems (Kouzmanov et al., 2010). High temperature fluids

that reach up to 300 °C in high-sulphidation epithermal systems are
mainly of magmatic origin and therefore oxidised and more acidic
compared to shallower low temperature (< 200 °C) fluids in low-sul-
phidation epithermal systems that are reduced and near neutral in pH
Carbonate-bearing

due to host rock buffering and a higher meteoric fluid component

(Table 1; White and Hedenquist, 1990; Einaudi et al., 2003; Sillitoe and
Host rock

Hedenquist, 2003; Simmons et al., 2005). These differences lead to

systematic variations in the composition of high- and low-sulphidation
epithermal deposits, such as higher Cu contents, higher abundances of
sulphosalts and a higher Au/Ag ratio in high- compared to low-sul-
phidation systems (Einaudi et al., 2003).
Epithermal (HS)

Epithermal (LS)

A notable sub-class within the epithermal deposits are those hosted

(alkaline)

Porphyry Cu
Deposit-type

within alkaline igneous rocks. These systems are commonly described

Epithermal

Orogenic

as having alteration assemblages similar to calc-alkaline-hosted low-

Carlin
Table 1

sulphidation systems, but with a greater magmatic component in the

fluids, higher temperatures, and a notably higher Te abundance (Jensen

3
M. Keith et al. Ore Geology Reviews xxx (xxxx) xxx–xxx

Table 2
The different deposit-types, corresponding mines and analytical techniques used for pyrite analyses in the listed studies.

Deposit-type Mine Location Analytical techniques Reference

Carlin Screamer Nevada EPMA Reich et al. (2005), Deditius et al. (2011), Muntean et al. (2011)
Deep Star Nevada EPMA Reich et al. (2005), Deditius et al. (2011), Muntean et al. (2011)
Meikle Nevada EPMA, LA-ICP-MS Emsbo et al. (2003), Reich et al. (2005), Muntean et al. (2011)
Lone Tree Nevada EPMA Deditius et al. (2011)
Northern Carlin Nevada LA-ICP-MS Large et al. (2009), Muntean et al. (2011)
Getchell district Nevada EPMA Cline and Hofstra (2000), Cline (2001), Barker et al. (2009), Muntean
et al. (2011)
West Banshee Nevada EPMA Barker et al. (2009), Muntean et al. (2011)
Saint-André-de- Canada EPMA Garnier et al. (2007)
Ristigouche
Shuiyindong China EPMA Su et al. (2008, 2009, 2012)
Alum Shale Sweden LA-ICP-MS Large et al. (2011)
Epithermal high-sulphidation Pueblo Viejo Dominican Republic EPMA Muntean et al. (1990), Deditius et al. (2009, 2011)
Palai-Islica Spain EPMA Ruano et al. (2000), Rosua et al. (2003)
Bawone and Binebase Indonesia EPMA, LA-ICP-MS King et al. (2014)
Mount Kasi Fiji EPMA Naden and Henney (1995)
Kawah Ijen Indonesia LA-ICP-MS Scher et al. (2013)
Yanacocha Peru EPMA Hayba et al. (1986), Bell et al. (2004), Harvey et al. (2004), Simmons
et al. (2005), Deditius et al. (2009)
Wilhelmine mine Germany EPMA Okrusch et al. (2007)
Rosia Poieni Romania LA-ICP-MS Kouzmanov et al. (2010)
El Indio Peru LA-ICP-MS Tanner et al. (2016)
Epithermal El Valle Spain EPMA Cepedal et al. (2000, 2008)
low-sulphidation North Arm Australia Proton microprobe Griffin et al. (1991)
Epithermal alkaline Porgera (alkaline) Papua New Guinea EPMA Reich et al. (2005)
Emperor (alkaline) Fiji EPMA, SIMS Naden and Henney (1995), Pals et al. (2003)
Tuvatu (alkaline) Fiji EPMA Naden and Henney (1995), Spry and Scherbarth (2006), Scherbarth
and Spry (2006)
Cripple Creek (alkaline) Colorado EPMA Jensen (2003), Dye (2015)
Orogenic Au Baogutu China EPMA An and Zhu (2010)
Dongping China LA-ICP-MS Mao et al. (2003), Cook et al. (2009a), Gao et al. (2017)
Hougou China LA-ICP-MS Cook et al. (2009a)
Huangtuliang China LA-ICP-MS Cook et al. (2009a)
Bhukia-Jagpura India EPMA, LA-ICP-MS Deol et al. (2012)
Bogosu-Prestea Ghana EPMA Mumin et al. (1994, 1996)
Dargue's Reef Australia ICP-MS, ICP-OES Ho et al. (1995)
Cowarra Australia ICP-MS, ICP-OES Ho et al. (1995)
Bendigo Australia LA-ICP-MS Jia et al. (2000), Wood and Large (2007), Large et al. (2009, 2011),
Thomas et al. (2011)
Golden Ridge Australia LA-ICP-MS Morey et al. (2008)
Sunrise Dam Australia LA-ICP-MS Brown et al. (2003), Sung et al. (2009)
Mother Load California EPMA Savage et al. (2000)
Spanish Mountain British Colombia LA-ICP-MS Large et al. (2009)
Roudny deposit Czech Republic EPMA, LA-ICP-MS Zachariáš et al., (2004)
Colombia Mine Venezuela LA-ICP-MS Velásquez et al. (2014)
Sukhoi Log Russia LA-ICP-MS Distler et al. (2004), Large et al. (2007, 2009, 2011)
Porphyry Cu Dexing China EPMA, SIMS Reich et al. (2013), Li and Sasaki (2007)

and Barton, 2000; Kelley and Spry, 2016). This sub-class includes some
of the world’s largest epithermal Au-Te deposits, such as Porgera
(Papua New Guinea), Cripple Creek (USA) and Emperor (Fiji). Previous
studies have suggested that these deposits may be useful as sources of
by-product Te in the future (Green, 2009).
4. Methods
The results presented in this study are based on previously pub-
lished data of pyrite and arsenian pyrite (n = 3283) and arsenopyrite
(n = 61), to complete the range in As contents, from different hydro-
thermal precious metal deposits (Table 2). Analyses were carried out by
electron microprobe analysis (EPMA), Laser Ablation ICP-MS (LA-ICP-
MS) and to a lesser extent by secondary-ion mass spectrometry (SIMS)
and proton microprobe analysis. In addition, pyrite crystal separates
were analysed by ICP-MS and ICP-OES (Table 2). Elements investigated
in this study include: Fe, S, V, Cr, Ni, Cu, Zn, As, Se, Mo, Te and Au
(Table 3). Details of other trace elements, such as Co, Cd, Sb, Pb and Bi
in pyrite can be found in the electronic supplementary material (A2).
The data set includes pyrite analyses of both Te and Se but also some
analyses where only Se or Te were reported (e.g., low-sulphidation
epithermal deposits, Table 3). The minimum detection limit for each
element with respect to the analytical technique can be found in
Table 4. For detailed information about the analytical techniques we
refer to the source references as listed in Table 2.
The data set was supplemented by bulk ore data from the OSNACA
data base (http://www.cet.edu.au/) and previously published and un-
published Te and Se bulk ore data from Carlin-type (Emsbo et al.,
2003), orogenic Au (Koneev et al., 2005), epithermal (Kwak, 1990;
Mueller et al., 2002; Dye, 2015) and porphyry Cu deposits (Cioacă
et al., 2014).
5. Results
5.1. As-Fe-S in pyrite
Iron and S are major elements in pyrite and arsenopyrite and vary
from 32.0 to 48.9 wt.% and 18.4 to 56.0 wt.%, respectively (Table 3).
However, As shows an even wider variation including trace (< 0.1 wt.
%) and major element concentrations (up to 47.6 wt.%, Table 3). Based

4
M. Keith et al. Ore Geology Reviews xxx (xxxx) xxx–xxx

Table 3
Compilation of the pyrite, arsenian pyrite and arsenopyrite investigated in this study.

Deposit-type Fe S (wt.%) V (ppm) Cr (ppm) Ni (ppm) Cu (ppm) Zn (ppm) As (ppm) Se (ppm) Mo (ppm) Te (ppm) Au (ppm) Se/Te Au/As
(wt.
%)

Carlin Min. 32.0 21.3 0.14 4.63 7.12 20.0 0.43 100 4.62 1.97 1.00 0.04 0.05 < 0.01
n = 479 Max. 48.6 54.6 4543 1185 30400 12590 3410 472200 4248 2657 6600 8400 337 0.74
SD 2.85 6.10 1396 449 4347 2944 551 85516 1237 714 1190 1479 127 0.05
Mean 43.1 47.8 983 408 2594 2037 327 72246 998 597 573 1519 92.3 0.03

Epithermal (HS) Min. 33.5 35.4 0.02 0.15 < 0.01 0.53 0.00 0.71 0.4 0.00 0.11 < 0.01 0.07 < 0.01
n = 789 Max. 48.4 56.0 11.7 3.22 2500 60010 7400 37600 2150 512 1820 1200 1581 2.00
SD 2.19 1.03 1.08 0.64 347 13838 649 4939 629 89.0 429 176 139 0.37
Mean 44.6 53.1 0.20 0.42 304 11317 153 2086 535 31.7 343 50.9 37.5 0.16

Epithermal (LS) Min. 33.0 18.4 n.a. n.a. 100 23.0 0.00 149 8.00 6.00 100 400 n.a. < 0.01
n = 35 Max. 45.9 52.6 n.a. n.a. 1400 7800 600 475600 1900 143 1200 4600 n.a. 0.02
SD 5.09 15.2 n.a. n.a. 554 1581 207 142489 491 54.3 535 1661 n.a. 0.01
Mean 40.8 40.4 n.a. n.a. 420 708 161 68236 198 57.3 600 1533 n.a. 0.01

Epithermal Min. 40.5 40.9 n.a. n.a. 300 10 400 10.0 600 n.a. 0.24 0.19 n.a. < 0.01
(alkaline) Max. 48.8 55.2 n.a. n.a. 2900 6500 2100 166020 1200 n.a. 7940 11057 n.a. 3.50
n = 777 SD 1.4 1.6 n.a. n.a. 585 972 571 16230 234 n.a. 1047 1084 n.a. 0.30
Mean 46.2 52.4 n.a. n.a. 595 546 700 14143 867 n.a. 546 421 n.a. 0.08

Orogenic Min. 30.8 19.3 0.01 0.26 0.28 0.06 0.14 0.94 1.80 0.01 0.05 < 0.01 0.19 < 0.01
n = 933 Max. 47.5 54.6 68.8 3924 25699 46633 2946 474000 199 111 20823 11506 445 1988
SD 6.12 13.5 15.1 276 1607 3167 262 118656 33.8 13.9 1736 699 61.3 118
Mean 38.8 37.4 8.99 48.8 716 758 59.2 44598 34.3 5.00 306 126 37.4 10.9

Porphyry Min. 43.7 51.5 n.a. n.a. 100 0.10 100 0.08 0.02 n.a. 0.02 0.01 < 0.01 < 0.01
n = 331 Max. 47.6 54.5 n.a. n.a. 7000 15980 300 25800 100 n.a. 542 10.8 542 4.75
SD 0.54 0.60 n.a. n.a. 893 1708 51.8 6476 12.5 n.a. 71.6 1.13 71.6 0.65
Mean 46.3 53.5 n.a. n.a. 483 447 159 3230 5.46 n.a. 26.3 0.38 26.3 0.18

The mean concentrations, the standard deviation (SD) and the minimum and maximum values of the presented elements are due to the variation between analyses of the studied deposit-
types. Note that this table includes paired and unpaired Te and Se data, as indicated by the Se/Te ratio. References to the data set as listed in Table 2. (n = number of analyses, n.a. = not
analysed).

on these chemical variations two compositional end-members can be
defined in the As-Fe-S system, namely pyrite (FeS2) and arsenopyrite
(FeAsS, Fig. 1). Arsenic-rich pyrite with As contents between the two
specified end-members is usually called arsenian pyrite (Fe(As, S)2 or
(Fe,As)S2) and characteristically shows ppm to wt.% levels of As (Reich
et al., 2005; Deditius et al., 2008). Compositional variations in As-poor
pyrite along the Fe-S join in the As-Fe-S system are most likely related
to the incorporation of trace elements substituting for Fe and S
(Deditius et al., 2014).
Arsenic occurs in several oxidation states (−I, +II, +III, +V) and
can therefore substitute into the pyrite lattice as either a cation or anion
(Reich et al., 2005; Qian et al., 2013; Deditius et al., 2014). Alter-
natively, As may be concentrated into liquid nano-inclusions hosted in
pyrite (Deditius et al., 2009b). Deditius et al. (2014) presented a
method to distinguish between different types of As substitution into
pyrite, based on the composition of pyrite and arsenopyrite in the
ternary As-Fe-S system (Fig. 1). Pyrite that plots on a line parallel to the
As-S join mainly incorporates As− due to isovalent S substitution in
tetrahedral sites (Fig. 1). Hence, As-S substitution apparently occurs in
pyrite and arsenopyrite from Carlin-type, low-sulphidation epithermal,
alkaline rock-hosted epithermal and orogenic Au ores and a distinct Fe-
deficiency was observed for pyrite from the Bhukia-Jagpura orogenic
Au deposit (Fig. 1, Table 2). In contrast, As2+/3+ substitutes for Fe in
pyrite in octahedral sites, such pyrite plots parallel to the Fe-As join in
the As-Fe-S ternary system (Fig. 1; Deditius et al., 2008, 2014; Qian
et al., 2013; Tardani et al., 2017). Consequently, As2+/3+ -pyrite occurs
in high-sulphidation epithermal systems, as described by Deditius et al.
(2008) for the Yanacocha deposit (Fig. 1, Table 2).

5.2. Te and Se in pyrite

Across all deposit-types Te and Se concentrations in pyrite vary from

Fig. 1. Composition of pyrite and arsenopyrite (bold symbols) from orogenic Au, Carlin-
type, high- (HS) and low-sulphidation (LS) epithermal and porphyry Cu deposits in the
As-S-Fe system, concentrations in at. %. Pyrite that plots parallel to the As-S join in-
corporates As− due to As-S substitution. Concentrations parallel to the As-Fe join re-
present As2+/3+ pyrite, which is related to the substitution of cationic As for Fe. (Figures
in colour can be found in the web version of this article.)
0.02 ppm (the minimum detection limit for both elements) to
20,800 ppm and 4250 ppm, respectively (Fig. 2, Table 3). Carlin-type
pyrite generally shows the highest average concentrations of Se
(1000 ppm, Table 3) and Te (570 ppm, Table 3). In contrast, the lowest
average concentrations of Se (6 ppm, Table 3) and Te (26 ppm, Table 3)
were observed in porphyry Cu pyrite. Epithermal pyrite is characterised

5
M. Keith et al. Ore Geology Reviews xxx (xxxx) xxx–xxx

Table 4
Minimum detection limits of the studied elements with respect to the analytical techniques used for pyrite analysis.

Analytical techniques Fe (wt.%) S (wt.%) V (ppm) Cr (ppm) Ni (ppm) Cu (ppm) Zn (ppm) As (ppm) Se (ppm) Mo (ppm) Te (ppm) Au (ppm)

EPMA 0.02 0.02 10.0 20.0 50 89.0 128 91.0

LA-ICP-MS 0.01 0.15 0.01 0.06 0.14 0.10 0.10 0.01 0.01 0.002
SIMS 0.10 0.08 0.02 0.02 0.01
Proton microprobe 23.0 17.0 8.00 6.00 10.0
ICP-MS 5.00 0.20 0.20
ICP-OES 5.0 5.0 24.0 5.00

References to the analytical techniques as listed in Table 2.

by highly variable Te and Se concentrations ranging from 0.1 to

7940 ppm and 0.4 to 2150 ppm, respectively (Table 3). Hence, epi- 100000
thermal pyrite overlaps with Carlin-type and porphyry Cu pyrite in A 39PY53
terms of its Te and Se content (Fig. 2). It is worth noting that pyrite 10000
from alkaline rock-hosted epithermal systems shows the highest Te
concentrations (up to 7940 ppm) compared to high- and low-sulphi- 1000
dation epithermal pyrite (Table 3). Orogenic Au pyrite has intermediate

Te (ppm)
Te and Se contents but characteristically shows a significant Te varia- 100
tion over a small range of Se (Fig. 2). Unpaired data for Te reaches
major element levels of up to 20,800 ppm (Table 3) in a few pyrite 10
crystals from the Chinese Huangtuliang and Dongping Au deposits,
which has been explained by the occurrence of telluride inclusions 1
(Cook et al., 2009a; Ciobanu et al., 2012). In contrast, Se in orogenic Au
pyrite generally occurs in trace amounts with concentrations below 0.1
200 ppm (Fig. 2, Table 3).
0.01
0.01 1 100 10000 1000000
6. Discussion
As (ppm)
6.1. Te and Se incorporation into hydrothermal pyrite 10000
B
Previous studies have suggested that Te and Se in pyrite can be
1000
either structurally bound in the lattice due to S substitution (Huston
et al., 1995; Chouinard et al., 2005; Kesler et al., 2007) or hosted as
micron to sub-micron sized inclusions (Emsbo et al., 2003; Pals et al., 100
Se (ppm)

2003; Cook et al., 2009a; Tanner et al., 2016).

10

100000
1
Orogenic
10000 Carlin
0.1
Epithermal
1000
Porphyry 0.01
Te (ppm)

100 0.01 1 100 10000 1000000

As (ppm)
10
Orogenic Epithermal (LS)
1 Carlin Epithermal (alkaline)
Epithermal (HS) Porphyry
0.1
Fig. 3. Concentrations of (A) Te and (B) Se vs. As in pyrite and arsenopyrite (bold
0.01 symbols) from orogenic Au, Carlin-type, high-sulphidation (HS) epithermal, low-sulphi-
dation (LS) epithermal, alkaline rock-hosted epithermal and porphyry Cu deposits. Note
0.01 0.1 1 10 100 1000 10000 the wedge-shaped zone between Te and As (grey dashed line). The black dashed line
Se (ppm) defines the solubility limit for Te solid solution in pyrite as a function of As, which is
based on the equation presented by Reich et al. (2005) for the Au-As system. Tellurium
Fig. 2. Concentrations of Te vs. Se in pyrite from orogenic Au, Carlin-type, epithermal concentrations above the solubility line indicate telluride inclusions in pyrite. The light
and porphyry Cu deposits. The black arrow represents the continental crust reference line grey and dark grey fields represent the Dongping-Huangtuliang and the Bawone-Binebase
based on the average continental crust Se/Te ratio (26/1; Wedepohl, 1995; Rudnick and data, respectively. Note that analysis 39PY53 is a typical example for Au-telluride-bearing
Gao, 2003). The different fields represent the bulk ore composition of the investigated pyrite in alkaline-hosted epithermal systems (Pals et al., 2003). Consequently, analysis
deposits-type with the same colour coding as the corresponding pyrite data. References to 39PY53, as well as the light and dark grey fields include analyses of telluride-bearing
the bulk ore data as listed in the text (cf. Section 4). Note that there is no paired Te and Se pyrite from the different deposit-types. (Figures in colour can be found in the web version
data available for arsenopyrite. (Figures in colour can be found in the web version of this of this article.)
article.)

6
M. Keith et al. Ore Geology Reviews xxx (xxxx) xxx–xxx

6.1.1. Te incorporation 100000

It has been shown that As-rich pyrite is usually enriched in trace A y = 1.05x + 23.24
elements compared to As-poor pyrite. For example, Ag, Cd, Sb, Au, Hg, 10000 R² = 0.55
Tl and Pb in pyrite form a triangular wedge-shaped zone with As in a
log–log diagram. Concentrations of these elements that plot outside the
1000
wedge-shaped zone with respect to their As content are interpreted to
39PY53

Te (ppm)
reflect micro- or nano-particle inclusions in pyrite (Reich et al., 2005,
100
2013; Deditius et al., 2014; Keith et al., 2016a). Interestingly, most of
the Te data also form a triangular wedge-shaped zone (Fig. 3A) with As
in a log–log plot similar to the elements listed above. Chouinard et al. 10
(2005) proposed that the association of Te and As is controlled by the
crystal-chemical properties of pyrite due to their preferential in- 1
corporation on the (1 1 0) surfaces in the cubic crystal system. How-
ever, some orogenic Au (Dongping and Huangtuliang, Table 2) and a 0.1
few high-sulphidation epithermal (Bawone and Binebase, Table 2) As-
poor pyrites show elevated Te concentrations and therefore plot outside 0.01
the wedge-shaped zone (Fig. 3A) suggesting that those pyrites host 0.001 0.1 10 1000 100000
telluride inclusions. Au (ppm)
According to Reich et al. (2005) high Au/As ratios (> 0.02, Table 3)
in pyrite imply that Au is hosted as Au0 sub-micron inclusions. Those 10000
pyrites plot above the Au solubility line, which defines the upper con- B
centration limit for Au solid solution in pyrite as function of the As 1000
content (Fig. 4). Hence, Au- and Te-rich but As-poor pyrite from the
Dongping and Huangtuliang orogenic Au deposits (Figs. 3A and 4) most
likely hosts Au-telluride inclusions. Cook et al. (2009a) confirm that the 100
Se (ppm)
high Te and Au concentrations identified in As-poor pyrite from
Dongping and Huangtuliang are related to Au-telluride inclusions, 10
namely calaverite (AuTe2). Deditius and Reich (2016) pointed out that
the Au solubility line can also be used to identify Hg and Tl inclusions in
1
pyrite in a log (Hg, Tl)-log (As) diagram due to the similar covalent
radii of Hg (132 pm), Tl (145 pm) and Au (136 pm). Importantly, the
covalent radius of Te (138 pm) is very similar to that of Au (136 pm) 0.1
indicating that the Au solubility line may also be used for Te in the same
0.01
100000 0.001 0.1 10 1000 100000
39PY53 Au (ppm)
10000
Orogenic Epithermal (LS)
1000
Carlin Epithermal (alkaline)
100
Au (ppm)

Au0 Epithermal (HS) Porphyry

10 Fig. 5. Concentrations of (A) Te and (B) Se vs. Au in pyrite and arsenopyrite (bold
symbols) from orogenic Au, Carlin-type, high-sulphidation (HS) epithermal, low-sulphi-
1 dation (LS) epithermal, alkaline rock-hosted epithermal and porphyry Cu deposits. Note
Au+1
the positive correlation between Au and Te with a Te/Au ratio close to one. The light grey
0.1 and dark grey field represents the Dongping-Huangtuliang and the Bawone-Binebase
data, respectively. The dark grey dashed line displays the linear regression line for Te vs.
0.01 Au (R2 = 0.55). The black solid lines represent the compositional range of common Au-
tellurides based on their Te/Au ratio: petzite (∼0.8), calaverite (∼1.4), krennerite
0.001 (∼1.7) and sylvanite (∼1.3). Note that analysis 39PY53 is a typical example for Au-
0.01 1 100 10000 1000000 telluride-bearing pyrite in alkaline-hosted epithermal systems (Pals et al., 2003). (Figures
in colour can be found in the web version of this article.)
As (ppm)
Orogenic Epithermal (LS) way as for Hg and Tl. The positive correlation of Te and Au in pyrite
Carlin Epithermal (alkaline) (R2 = 0.55, Fig. 5A) supports this conclusion and suggests that the
incorporation of these elements is controlled by a similar process and
Epithermal (HS) Porphyry that they are closely associated in the pyrite structure (Pals and Spry,
Fig. 4. Concentrations of Au vs. As in pyrite and arsenopyrite (bold symbols) from oro- 2003; Pals et al., 2003; Kesler et al., 2007). Pals et al. (2003) identified
genic Au, Carlin-type, high-sulphidation (HS) epithermal, low-sulphidation (LS) epi- Au-telluride inclusions (calaverite, krennerite, sylvanite and petzite) by
thermal, alkaline rock-hosted epithermal and porphyry Cu deposits. Note the wedge- LA-ICP-MS time-resolved depth profiles in pyrite (39PY53) from the
shaped zone between Au and As (grey dashed line). The black dashed line defines the alkaline rock-hosted Emperor epithermal deposit, which also plots
solubility limit for Au solid solution in pyrite as a function of As after Reich et al. (2005).
above the Au solubility line in the Te-As (Fig. 3A) and Au-As system
Gold concentrations above the solubility line indicate Au0 inclusions in pyrite. The light
(Fig. 4). Similarly, it has been shown that Au-telluride inclusions in low-
grey and dark grey fields represent the Dongping Huangtuliang and the Bawone-Binebase
data, respectively. Note that analysis 39PY53 is a typical example for Au-telluride-bearing sulphidation epithermal pyrite are common (Pals and Spry, 2003; Pals
pyrite in alkaline-hosted epithermal systems (Pals et al., 2003). (Figures in colour can be et al., 2003; Kesler et al., 2007), which correlates with the position of
found in the web version of this article.) many alkaline-hosted epithermal pyrites above the solubility line in the

7
M. Keith et al.
log (Au, Te)-log (As) diagrams (Figs. 3A and 4). Hence, it is reasonable
to propose that Au-telluride inclusions in pyrite may be identified based
on the combined use of the Au solubility line by Reich et al. (2005) in
the Te-As (Fig. 3A) and Au-As (Fig. 4) systems, as previously reported
for Hg and Tl by Deditius and Reich (2016). This conclusion is sup-
ported by the positive correlation of Au and Te in pyrite (R2 = 0.55)
and in particular by the Te/Au ratio of the regression line, which is
close to one (Fig. 5A). In addition, pyrite (39PY53) from Emperor that
hosts Au-telluride inclusions plots into the compositional range of cal-
verite (AuTe2), krennerite (Au3AgTe8), sylvanite (AgAuTe4) and petzite
(Ag3AuTe2, Fig. 5A), which also intersects the data set of the Dongping
and Huantuliang orogenic Au deposits (Fig. 5A) where calaverite in-
clusions have been identified in pyrite (Cook et al., 2009a). However,
future SIMS depth profiles, LA-ICP-MS time-resolved spectra and high-
resolution transmission electron microscopy (HRTEM) on pyrite crys-
tals with variable Te and As contents are necessary to prove the validity
of the newly presented Te solubility line (Duran et al., 2015; Reich
et al., 2005; Deditius et al., 2011; Tardani et al., 2017).
Some high-sulphidation epithermal pyrites from the Binebase and
Bawone deposits show Te concentrations above (Fig. 3A) but Au con-
centrations below the Au solubility line (Fig. 4). Hence, potential tell-
uride inclusions may be characterised by high Te/Au ratios either due
to high Te contents or high abundances of other elements, such as Cu,
Ag, Pb and Bi. Tellurium in pyrite from Binebase and Bawone correlates
with Au (R2 = 0.45, Fig. 6A) but also with Cu (R2 = 0.59, Fig. 6B),
10000
A As, Au and other trace elements in solid solution due to extra vacancies
1000
100
Te (ppm)
10 R² = 0.45
1
0.1
0.01
0.001 0.01 0.1 1 10 100
Au (ppm)
10000
B trace elements (Fig. 7) including V (R2 = 0.69), Cr (R2 = 0.85), Ni
1000
Te (ppm)
100
10
1 R² = 0.59
0.1
0.1 10 1000 100000
Cu (ppm)
Fig. 6. Concentrations of Te vs. (A) Au and (B) Cu in pyrite from the Bawone and
Binebase high-sulphidation epithermal deposits. Note the positive correlation between Te
and the other trace elements possibly indicating Au-Cu telluride inclusions. The dark grey
line represents the best fit regression line for the presented data set. The black solid lines
represent the compositional range of common Cu-Au-tellurides based on their Te/Au and
Te/Cu ratio: bogdanovite (∼0.2 and ∼0.9), bezsmertnovite (∼0.1 and ∼1.1), bili-
binskite (∼0.4 and ∼2.2) and kostovite (∼2.5 and ∼9.7). Further diagrams and cor-
relation coefficients (R2) between Te and other trace elements in the different deposits
can be found in the electronic supplementary material A2. (Figures in colour can be found
in the web version of this article.)
8
Ore Geology Reviews xxx (xxxx) xxx–xxx
which might be related to the occurrence of Au-Cu telluride inclusions.
Similarly, Naden and Henney (1995) identified Au-Cu tellurides, such
as kostovite (AuCuTe4) in the high-sulphidation system of Mount Kasi
(Fiji). High-sulphidation epithermal systems are generally enriched in
Cu compared to their low-sulphidation counterparts (Einaudi et al.,
2003). However, pyrite from Binebase and Bawone differs from the
compositional range defined by Au-Cu tellurides, such as kostovite
(AuCuTe4), bezsmertnovite ((Au,Ag)4Cu(Te,Pb)), bilibinskite
(Au3Cu2PbTe2) and bogdanovite ((Au, Te, Pb)3(Cu, Fe)) indicating that
the high Te/Au ratios and the positive Cu-Te correlation (Fig. 6B)
cannot be explained by Cu-rich telluride inclusions. Hence, Te is hosted
in pyrite as a telluride phase not considered here or in its native form,
which is reasonable to conclude because native Te is stable in asso-
ciation with pyrite in acidic and oxidised high-sulphidation epithermal
fluids (Naden and Henney, 1995; Cook et al., 2009b). Alternatively, Te
may be hosted by complex Cu-bearing sulfosalts, such as goldfieldite
(Cu10Te3S13), that typically occur in high-sulphidation epithermal sys-
tems (Naden and Henney, 1995; Berger et al., 2014).
In contrast, As-rich Carlin-type pyrite mainly plots inside the wedge-
shaped zone and below the Te solubility line in the Te-As system
(Fig. 3A) implying that Te most likely occurs in solid solution. The
different covalent radii of As (119 pm) and S (105 pm) suggest that the
high amounts of As incorporated into Carlin-type pyrite by substituting
the smaller S atom (Fig. 1) expand the unit cell causing structural dis-
tortion, which facilitates the incorporation of heavier and larger ele-
ments, such as Te (138 pm) in solid solution. Furthermore, Reich et al.
(2005) pointed out that Carlin-type pyrite incorporates high amounts of
and lattice defects caused by rapid crystal growth under non-equili-
brium conditions at low temperatures (< 250 °C). Due to the close as-
sociation of Te with As and Au in pyrite (Figs. 3A and 5A), we propose
that the incorporation of Te in solid solution into Carlin-type pyrite
(Fig. 3A) is also facilitated by non-equilibrium conditions.
6.1.2. Se incorporation
No systematic correlation exists between Au and Se in pyrite
(Fig. 5B; Kesler et al., 2007) indicating that Au-Se inclusions in pyrite
are absent, rare or of minor importance for the Se distribution in hy-
drothermal pyrite on a larger scale. However, more detailed observa-
tions on distinct deposit-types (e.g., Carlin) or on an individual deposit
revealed that Se systematically varies with other trace elements on a
smaller scale (electronic supplementary material A2). For example,
Carlin-type pyrite displays a positive correlation between Se and other
(R2 = 0.59), Cu (R2 = 0.55), Zn (R2 = 0.75) and Mo (R2 = 0.85) and
characteristically shows elevated Se concentrations reaching 4250 ppm
(Table 3) probably indicating selenide inclusions of Ni, Cu, Zn and Mo
with a composition similar to mäkinenite (NiSe), bellidoite (Cu2Se),
tyrrellite (Cu(Co, Ni)2Se4), stilleite (ZnSe) and drysdallite (MoSe2,
Fig. 7C–F). In contrast, there are no known minerals that contain Se and
V or Cr. Alternatively, the presence of these elements in pyrite may
distort the lattice facilitating the incorporation of Se in solid solution.
However, another possibility to take into account is an inverse me-
chanism where the incorporation of Se facilitates the incorporation of
other trace elements such as those listed above. Similar correlations
between Se and other trace elements have been observed for high-
(electronic supplementary material, Table A2.2) and low-sulphidation
(Table A2.3) epithermal pyrites also reaching Se concentrations of up to
1900 and 2150 ppm, respectively. Kouzmanov et al. (2010) identified
Au-Ag selenide inclusions in pyrite from the Rosia Poieni high-sulphi-
dation epithermal system. In contrast, orogenic Au and porphyry Cu
pyrites are depleted in Se compared to the other deposit-types (Fig. 2,
Table 3) and Se generally lacks any systematic variation with other
trace elements (Tables A2.4–A2.5). Hence, selenides seem to be of
minor importance in these deposits and Se most likely occurs in solid
solution in the corresponding pyrites due to isovalent S substitution.
M. Keith et al. Ore Geology Reviews xxx (xxxx) xxx–xxx

10000 10000 Fig. 7. Concentrations of Se vs. (A) V, (B) Cr,

A B (C) Ni, (D) Cu, (E) Zn and (F) Mo in pyrite from
Carlin-type deposits. Note the positive correla-
1000 R² = 0.69 1000 tion between Se and the other trace elements
R² = 0.85 possibly indicating selenide inclusions in
Se (ppm)

Se (ppm)
Carlin-type pyrite. The dark grey line represents
100 100 the best fit regression line for the presented data
set. The black solid lines define the composi-
tional range of Ni, Cu, Zn and Mo selenides
10 10 including for example maekinenite, bellidoite,
tyrrelite, stilleite and drysdallite. Further dia-
grams and correlation coefficients (R2) between
1 1 Se and other trace elements in the different
0.1 1 10 100 1000 10000 1 10 100 1000 10000 deposits can be found in the electronic supple-
mentary material A2. (Figures in colour can be
V (ppm) Cr (ppm) found in the web version of this article.)

10000 10000
C D
1000 1000 R² = 0.55
Se (ppm)

Se (ppm)

100 100
R² = 0.59
10 10

1 1
0.1 10 1000 100000 10 100 1000 10000 100000
Ni (ppm) Cu (ppm)

10000 10000
E F
1000
R² = 0.75 1000 R² = 0.85
Se (ppm)

Se (ppm)

100
100
10
10
1

0.1 1
0.1 1 10 100 1000 10000 1 10 100 1000 10000
Zn (ppm) Mo (ppm)

(Chouinard et al., 2005; Reich et al., 2013). Moreover, Se forms no
wedge-shaped zone with As in a log (Se)-log (As) diagram (Fig. 3B)
opposed to Te (Fig. 3A) suggesting an As independent incorporation of
Se into pyrite.
6.2. Effect of coexisting phases: bulk ore vs. pyrite chemistry
The combined use of bulk ore and pyrite chemistry (Fig. 2) provides
important information on the control of bulk ore Te and Se by pyrite
and coexisting phases. Carlin-type pyrite is generally enriched in Te and
Se compared to the bulk ores implying that pyrite is the main host for
these elements in Carlin-type ores (Fig. 2; Kesler et al., 2007). In con-
trast, a compositional overlap exists between orogenic Au pyrite and
the corresponding bulk ores indicating that Te and Se in pyrite may
represent the bulk ore composition. Orogenic Au deposits also host
pyrite that is depleted in Te but similar in Se compared to the bulk ore
implying that Te is incorporated into another mineral phase that occurs
in association with pyrite. Some epithermal pyrites show Te and Se
contents higher than the bulk ore, as characteristically shown for
Carlin-type systems, or are enriched in Se but depleted in Te compared
to the bulk ore. This suggests that epithermal pyrites represent the main
hosts for both elements or only for Se, whereas most Te is hosted by
mineral phases other than pyrite. Porphyry Cu pyrite shows a much
larger range in Te and Se than the corresponding bulk ores suggesting a
complex history of pyrite precipitation (Reich et al., 2013), where
pyrite can either represent the main host for these elements or is de-
pleted in them due to the competitive incorporation by other mineral
phases.
Pyrite from low-sulphidation and alkaline-rock hosted epithermal
systems is generally enriched in As and tends to show higher Te con-
tents compared to pyrite from high-sulphidation deposits (Fig. 3A,
Table 3). The lower As contents of pyrite in high-sulphidation epi-
thermal and porphyry Cu systems correlate with the occurrence of other
common As-rich phases, such as realgar (AsS), and sulphosalts in-
cluding enargite (Cu3AsS4), luzonite (Cu3AsS4) and tennantite ((Cu, Ag,
Zn, Fe)12As4S13; Einaudi et al., 2003), which probably host most of the
As in the bulk ores. However, As seems to be an essential component in
pyrite to incorporate high amounts of Te, and hence it is likely that Te is
hosted in another mineral phase in high-sulphidation epithermal and
porphyry Cu systems (cf. Section 6.1.1) or is depleted in the ore-
forming fluids. Selenides are very rare in contrast to telluride minerals
(Simon et al., 1997), which makes them less important for the Se dis-
tribution in the bulk ores. Only porphyry Cu pyrite shows Se con-
centrations lower than the bulk ores (Fig. 2) indicating that most of the

9
M. Keith et al. Ore Geology Reviews xxx (xxxx) xxx–xxx

Se is hosted by a mineral phase other than pyrite or occurs as free se-

lenides. For example, it has been shown that chalcopyrite and galena
can potentially incorporate Se in high concentrations reaching 1500
(Wohlgemuth-Ueberwasser et al., 2015) and 1900 ppm (Williams et al.,
2015), respectively.

6.3. Redox- and pH-controlled Te and Se incorporation into pyrite

The speciation of As in pyrite has been used to compare the redox

conditions of ore-forming fluids between different deposit-types, which
is based on the redox sensitivity of As indicated by its occurrence in
several oxidation states (−I, +II, +III, +V; Reich et al., 2005; Qian
et al., 2013; Deditius et al., 2014). Carlin-type, low-sulphidation epi-
thermal and orogenic Au systems are all characterised by reduced ore
fluids (Table 1; Cline et al., 2005; Goldfarb et al., 2005; Simmons et al.,
2005; Deditius et al., 2008), which coincides with the formation of As−
-pyrite in these systems (Fig. 1). According to Einaudi et al. (2003),
high-sulphidation epithermal fluids characteristically show higher fO2
compared to their low-sulphidation counterparts, which explains the
occurrence of As2+/3+ -pyrite in these systems (Fig. 1).
Importantly, Te is typically enriched in As−- pyrite from Carlin-type
and low-sulphidation epithermal systems, including those hosted in
alkaline igneous rocks (Fig. 3A; Kesler et al., 2007). Previous studies
pointed out that Te is less soluble in reduced hydrothermal fluids and
that the reduction of Te4+ results in the precipitation of Te (Cooke and
McPhail, 2001; Grundler et al., 2013). Surprisingly, As-poor pyrite from
the Dongping and Huangtuliang orogenic Au deposits also shows high
Te contents (Fig. 3A; Cook et al., 2009a) probably reflecting an As-poor
but Te-rich ore-forming fluid. Gao et al. (2017) stressed that the pyrite
and telluride precipitation in the Dongping orogenic Au deposit was
caused by a decrease in fO2 similar to the deposit-types described
above. Hence, we conclude that the incorporation of Te in pyrite is
highly sensitive to redox changes in the parental fluids and high Te
contents in pyrite are related to low fluid fO2.
Grundler et al. (2013) pointed out that Te is highly soluble in
neutral to alkaline fluids that typically exist in Carlin-type, low-sul-
phidation epithermal and alkaline rock-hosted epithermal systems (e.g.,
Cripple Creek, Emperor, Table 2) and some orogenic Au deposits
(Table 1; Goldfarb et al., 2005; Seedorff et al., 2005; Simmons et al.,
2005). However, the high Te contents in pyrite from these systems re-
quire an efficient precipitation process, which is therefore mainly pH
independent. Consequently, high pH fluids may effectively mobilise Te
Fig. 8. Average (A) Se and (B) Te concentrations in pyrite vs. the temperature of ore
from the source rocks and transport it to the site of deposition but the deposition from orogenic Au, Carlin-type, high-sulphidation (HS) epithermal, low-sul-
precipitation of Te is mainly controlled by redox changes in the par- phidation (LS) epithermal, alkaline rock-hosted epithermal and porphyry Cu systems.
ental fluid phase. In contrast, Se shows no systematic variation between Average Se concentrations and the corresponding fluid temperatures as listed in Table A1
As− -pyrite from Carlin-type, low-sulphidation epithermal and alkaline- (electronic supplementary material). The error bars specify the 1σ standard deviation.
hosted epithermal systems compared to As2+/3+ -pyrite from high- Note the negative correlation (R2 = 0.40) as indicated by the solid regression line be-
tween Se in pyrite and the temperature of ore precipitation. (Figures in colour can be
sulphidation epithermal deposits (Fig. 3B) suggesting that Se in pyrite is
found in the web version of this article.)
not primarily controlled by fO2 and fluid pH (Maslennikov et al., 2009;
Revan et al., 2014; Keith et al., 2016a,b).
(electronic supplementary material, Table A1). The regression line be-
6.4. Effects of fluid temperature on Te and Se in pyrite tween Se in pyrite and the ore-forming fluid temperature (T) of the
investigated deposits yield the following equation:
Tellurium shows no systematic variation in pyrite with the tem- Sepyrite = 5∗1013∗T −4.82 (1)
perature of ore deposition (Fig. 8A). Hence, the incorporation of Te into
pyrite seems to be temperature independent but highly sensitive to Early pyrite from the El Indio deposit shows average Se contents
changes in fO2 (cf. Section 6.3). It has been shown that Se in pyrite can (100 ppm) similar to other high-sulphidation epithermal systems
be used as a proxy for relative temperature estimations in ore-forming (Fig. 8B), but the suggested fluid temperature for early precipitated
fluids and most studies have suggested that the Se content of pyrite pyrite (∼700 °C, 650–1150 m depth; Tanner et al., 2016) significantly
increases with increasing fluid temperature (Auclair et al., 1987; exceeds typical ore-forming temperatures of high-sulphidation epi-
Maslennikov et al., 2009; Revan et al., 2014). In contrast, the numerical thermal systems (< 300 °C; Simmons et al., 2005). Sulphur isotope geo-
simulations by Huston et al. (1995) imply that Se-rich pyrite usually thermometry on alunite-pyrite pairs from El Indio revealed similar
forms from low temperature fluids. The results presented in this study depositional temperatures of ∼700 °C (Jannas et al., 1999). Tanner
are in agreement with Huston et al. (1995) and display a negative et al. (2016) explained these high temperatures by the direct pre-
correlation (R2 = 0.40, Fig. 8B) between average Se in pyrite from the cipitation of pyrite from a hot magmatic vapour phase. However, Deyell
different deposits and the mean temperature of ore deposition et al. (2004) argued that these temperatures are unreasonably high and

10
M. Keith et al.
that the alunite-pyrite pairs probably indicate a S isotope dis-
equilibrium. Magmatic vapour inclusions displayed average homo-
genisation temperatures of ∼270 °C (Jannas, 1995), which are similar
to the temperature estimations (200–300 °C) presented by Deyell et al.
(2004). Eq. (1) can be used to estimate the average precipitation tem-
perature of pyrite yielding a temperature of 268 °C ± 49 °C for the
deposition of early pyrite at El Indio, which is well in the range of ty-
pical high-sulphidation epithermal precipitation temperatures
(< 300 °C; Simmons et al., 2005). Importantly, the Binebase and Ba-
wone high-sulphidation epithermal deposits are genetically similar to El
Indio and pyrite deposition occurred due to magmatic vapour con-
densation under epithermal conditions at 900–1300 m paleo-depth and
temperatures between 250 and 340 °C (King et al., 2014). These in-
dependent results confirm that the estimated fluid temperatures of
268 °C ± 49 °C for the deposition of early pyrite at El Indio are in a
reasonable range.
Therefore, we conclude that Eq. (1) represents a potential geo-
thermometer to estimate the average precipitation temperature of
pyrite in various deposit-types. The presented results further imply that
Se in pyrite is apparently related to the temperature of ore deposition
(Fig. 8B) irrespective of the fO2 and the pH of the ore-forming fluids (cf.
Section 6.3). Alternatively, Se in pyrite may vary due changes in the
∑Se/S ratio of the ore-forming fluids (Huston et al., 1995). Hence, in
high temperature magmatic-hydrothermal systems (e.g., high-sulphi-
dation epithermal-porphyry deposits) the fluids are either depleted in
Se compared to their low temperature counterparts (e.g., low-sulphi-
dation epithermal and Carlin-type deposits) or Se is competitively in-
corporated by other minerals or forms selenides (e.g., Rosia Poieni,
Kouzmanov et al., 2010) that precipitate in association with pyrite.
6.5. Fluid-rock interaction vs. fluid boiling: Effects of ore precipitation
processes on Te and Se in pyrite
The different deposit-types investigated in this study are char-
acterised by distinct ore precipitation mechanisms. Carlin-type miner-
alisation is generally attributed to carbonate-hosted Fe2+ sulphidation
and oxidation in the surrounding wall rocks causing pyrite precipitation
accompanied by precious metal mineralisation (Cline and Hofstra,
2000; Emsbo et al., 2003; Cline et al., 2005). Loss of S from the ore
fluids due to wall rock sulphidation destabilises the Au-bisulphide
complexes causing Au deposition (Cline and Hofstra, 2000; Embso
et al., 2003; Cline et al., 2005; Muntean et al., 2011). The oxidation of
Fe2+ in the wall rocks to Fe3+ due to the interaction with the ore-
forming fluids results in a fO2 decrease in the fluid phase causing effi-
cient Te precipitation (cf. Section 6.3), which can therefore explain the
Au-Te association in As− -pyrite from Carlin-type systems (Figs. 3–5).
Fluid boiling is one of the most important processes for ore de-
position in porphyry-epithermal systems (Cooke and McPhail, 2001;
Seedorff et al., 2005; Simmons et al., 2005). Deditius et al. (2009a) and
Tardani et al. (2017) pointed out that processes such as fluid boiling can
fractionate trace elements in hydrothermal fluids causing systematic
compositional differences and chemical zonation in precipitated pyrite.
Low-sulphidation epithermal and alkaline-hosted epithermal pyrite is
enriched in Te compared to high-sulphidation and porphyry Cu pyrite
(Figs. 3A and 5A) suggesting different Te concentrations in the parental
fluid phase, variable degrees of Te precipitation during fluid boiling or
the competitive incorporation of Te in mineral phases other than pyrite
(cf. Section 6.2). Thermodynamic modelling calculations by Grundler
et al. (2013) revealed that Te can partition into the vapour phase during
fluid boiling, which is most efficient from acidic fluids prevalent in
high-sulphidation epithermal and porphyry Cu systems (Table 1;
Seedorff et al., 2005; Simmons et al., 2005). Similarly, Cooke and
McPhail (2001) pointed out that fluid boiling causes metal sulphide
precipitation in epithermal-porphyry systems; however, under acidic
(high-sulphidation) conditions Te fractionates into the vapour phase
and precipitates at shallower crustal levels in Au-rich zones (Cooke and
11
Ore Geology Reviews xxx (xxxx) xxx–xxx
McPhail, 2001) yielding low Te and Au grades in the deeper high-sul-
phidation epithermal and porphyry environment. In contrast, under
neutral to alkaline fluid conditions Te partitions into the liquid phase
during fluid boiling (Grundler et al., 2013); the strong affinity of H2S to
the vapour phase significantly reduces the S content of the corre-
sponding liquids, which destabilises the Au-bisulphide complexes
causing Au deposition (Cooke and McPhail, 2001; Simmons et al.,
2005). Importantly, As-rich pyrite associated with Au and Te miner-
alisation usually forms from hydrothermal fluids with low S contents
(Reich et al., 2005) that typically occur in low-sulphidation and alka-
line-rock hosted epithermal systems, as well as in Carlin-type deposits
(Figs. 3–5).
Tellurium in pyrite from orogenic Au deposits shows a wide varia-
tion overlapping with porphyry Cu, epithermal and Carlin-type systems
(Fig. 2, Table 3). The high chemical variability of orogenic Au ores has
previously been described and assigned to complex variations in fluid
composition and metal precipitation through time (Goldfarb et al.,
2005). It has been shown that some orogenic Au districts formed by
reduced fluids with near-neutral pH and isotopic signatures similar to
Carlin-type systems (Ridley and Diamond, 2000; Cline et al., 2005;
Goldfarb et al., 2005; Cook et al., 2009; Gao et al., 2017). Goldfarb et al.
(2005) pointed out that fluid-rock interaction accompanied by sulphi-
dation of Fe-rich wall rock represent the most important processes for
metal sulphide precipitation in orogenic Au systems. The composition
of the ore-forming fluids in combination with the precipitation process
may explain the high Te and Au contents of some orogenic Au pyrites
that are similar to those from low-sulphidation epithermal, alkaline-
rock hosted epithermal and Carlin-type deposits (Fig. 5A). However, the
low Au and Te contents in other orogenic Au pyrites that overlap with
those of high-sulphidation epithermal and porphyry Cu deposits
(Fig. 5A) indicate that the precipitation mechanisms in these systems
prevent extensive Te deposition associated with pyrite precipitation or
that Te is hosted by mineral phase other than pyrite (Fig. 2, Section
6.2).
No systematic variation has been observed for Se in pyrite between
the different deposit-types in relation to the mineralisation process
(Fig. 3B and 5B). Hence, Se most likely does not fractionate during fluid
boiling or wall rock sulphidation in contrast to Te. This suggests that
the precipitation of Se and its distribution in pyrite is mainly controlled
by fluid temperature (cf. Section 6.3).
6.6. Source rock control on Te and Se in pyrite
The Te and Se contents in the source rocks of hydrothermal systems
are still largely unknown. However, it has been shown that alkaline
rock-hosted low-sulphidation epithermal deposits, such as Cripple
Creek (Colorado) and Emperor (Fiji), are Au- and Te-rich (Naden and
Henney, 1995; Jensen and Barton, 2000). Oceanic sediments are Te-
rich and melting of these sediments in subduction zones represents a
potential source for Te in alkaline magmas and associated low-sulphi-
dation epithermal systems (Jensen and Barton, 2000). Similarly, the
results of Loftus-Hill and Solomon (1967) and Schirmer et al. (2014)
highlight that oceanic sediments and carbonate-bearing rocks are en-
riched in Te and Se compared to other rock-types associated with hy-
drothermal systems. Importantly, pyrite from Carlin-type and alkaline-
hosted epithermal systems typically shows the highest average Te
contents (Table 3) suggesting a potential source rock control for Te in
pyrite. In contrast, Se is not particularly enriched in these pyrites pos-
sibly indicating that the distribution of Se in pyrite is less controlled by
the source composition, as observed for other trace metals in pyrite
(Keith et al., 2016a). We conclude that Te (but not Se) in pyrite is
potentially controlled by its concentration in the source rocks. Hence,
the high Te contents in Carlin-type and alkaline rock-hosted epithermal
pyrite are probably related to a combination of host rock enrichment
(Naden and Henney, 1995; Jensen and Barton, 2000; Schirmer et al.,
2014) and neutral to alkaline fluid conditions, which are necessary for
M. Keith et al.
the efficient mobilisation and transportation of Te from the source re-
gion to the depth of deposition (Grundler et al., 2013; Gao et al., 2017).
6.7. Economic relevance
The bulk ores and significant amounts of the pyrite data show Te/Se
ratios (> 0.038) above the average continental crust reference line
(Fig. 2, Wedepohl, 1995; Rudnick and Gao, 2003), and therefore re-
present an important reservoir for Te in the continental crust. It has
been shown that As-rich pyrite represents the primary host for Au in
Carlin-type deposits, which highlights that trace metals can be enriched
in pyrite in economic amounts (Palenik et al., 2004; Large et al., 2009;
Deditius et al., 2014). Gold and Te, for example, reach concentrations of
up to 8400 and 6600 ppm, respectively, in Carlin-type pyrite (Table 3).
Bulk ore analyses from the Northern Carlin Trend (Nevada) display Au
and Te contents of up to 390 and 75 ppm, respectively (Emsbo et al.,
2003). Even higher Au and Te concentrations of up to 550 and
690 ppm, respectively, were observed in mineralised ores from the al-
kaline rock-hosted Cripple Creek (USA) epithermal deposit and pyrite
associated with these ores shows Au and Te concentrations reaching
8710 and 7940 ppm, respectively (Dye, 2015). Consequently, Carlin-
type and alkaline rock-hosted epithermal pyrite displays similar Te
concentrations (Fig. 3A, Table 3) but variable concentrations in the
bulk ores. Tellurium is enriched in the Cripple Creek ores compared to
those from the Northern Carlin Trend, which can be explained by the
common occurrence of free telluride minerals that are associated with
Te-rich pyrite (Jensen, 2003; Dye and Smyth, 2012; Dye, 2015). Hence,
in Carlin-type systems most Te is hosted by pyrite (Fig. 2, Section 6.2),
as is Au (Palenik et al., 2004; Large et al., 2009; Deditius et al., 2014),
free-telluride minerals are absent or rare (Emsbo et al., 2003). How-
ever, Emsbo et al. (2003) present no paired Se-Te data and hence, pyrite
that occurs in association with free-telluride minerals is not shown in
the Se-Te diagram (Fig. 2). This suggests that alkaline igneous rock-
hosted epithermal fluids reach the Te saturation limit during their
evolution opposed to many Carlin-type fluids that are Te under-
saturated indicated by the lack of telluride minerals in their precipitates
(Fig. 3A, Sections 6.1 and 6.2). Pyrite is the most important sink for As
in these systems and the positive correlation of Au and Te with As
(Fig. 3A and 4) suggests that bulk ore As can possibly be used as a tracer
to target Te in Carlin-type and alkaline rock-hosted epithermal systems.
Furthermore, the high Te concentrations in pyrite imply that Te is of
potential economic interest in these deposits. However, processing of
“invisible” structurally bound or nanoparticle Te and Au in pyrite is
difficult because Au cannot be recovered by direct cyanidation The ore
therefore requires a pre-treatment step including either chemical oxi-
dation, roasting, pressure oxidation or bio-oxidation prior to cyanida-
tion (Spry et al., 2004) and the behaviour of Te in the pre-treatment is
not well understood.
7. Summary and conclusions
The results of this study highlight that the observed systematics of
Te and Se in pyrite reflect the different source rock compositions and
precipitation processes in relation to the physicochemical composition
of the ore-forming fluids. Tellurium forms a triangular wedge-shaped
zone with As in pyrite in a log (Te)-log (As) diagram, which indicates
that As significantly affects the incorporation of Te into pyrite due to
structural distortion. The new application of the Au solubility line in the
Te-As system presents a method to distinguish between Te solid solu-
tion and an inclusion related appearance in pyrite. Future HRTEM
studies, as well as SIMS depth profiles and LA ICP-MS time-resolved
spectra on pyrites with variable As and Te contents can be used to verify
the newly proposed solubility line for Te. In contrast, Se varies less
systematically with other trace elements, including As, suggesting that
different physicochemical fluid parameters control the incorporation of
Te and Se in pyrite between different deposit-types. Carbonate-rich
12
Ore Geology Reviews xxx (xxxx) xxx–xxx
sediments or alkaline magmatic rocks usually show high Te con-
centrations and neutral to alkaline fluids can effectively mobilise Te
from these rocks and transport it to the depth of deposition. Tellurium
fractionation during fluid boiling between the vapour and liquid phase
as a function of fluid pH results in significant Te variations in pyrite
between different epithermal and porphyry systems. Carlin-type (and
orogenic Au) pyrite forms due to wall rock sulphidation and char-
acteristically shows high Te contents. Fluid boiling and fluid-rock in-
teraction affect the redox conditions of the ore-forming fluids and the
results of this study imply that Te-rich pyrite precipitates from reduced
fluids. In contrast, Se in pyrite seems to be mainly a function of the fluid
temperature irrespective of the fO2 and the pH of the fluids. It has been
shown that such processes can cause chemically zoned pyrite crystals,
which emphasizes that studies of Te and Se on the crystal scale are
important to improve our understanding ore-forming processes.
The high Te concentrations in pyrite from Carlin-type and some
epithermal deposits in relation to the corresponding bulk ores suggest
that these systems possibly represent a valuable Te resource with pyrite
as the main Te host. This highlights the importance of improving cur-
rent leaching methods in order to recover Au, Te and other potentially
valuable metals from pyrite in an economic and environmentally sus-
tainable way.
Acknowledgements
The authors would like to thank the reviewers Martin Reich and
Artur Deditius for their comments that improved the quality of the
manuscript. This study was funded by the UK Natural Environment
Research Council (NERC); Minerals Security of Supply (SoS) grant NE/
M010848/1, Tellurium and Selenium Cycling and Supply (TeaSe).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.oregeorev.2017.07.023.
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