Pyrite compositions from VHMS and orogenic Au deposits in the Yilgarn
Craton, Western Australia: Implications for gold and copper exploration

I. Belousov, R.R. Large, S. Meffre, L.V. Danyushevsky, J. Steadman, T.

Beardsmore

PII: S0169-1368(15)30092-5
DOI: doi: 10.1016/j.oregeorev.2016.04.020
Reference: OREGEO 1795

To appear in: Ore Geology Reviews

Received date: 1 October 2015

Revised date: 19 April 2016
Accepted date: 22 April 2016

Please cite this article as: Belousov, I., Large, R.R., Mere, S., Danyushevsky, L.V.,
Steadman, J., Beardsmore, T., Pyrite compositions from VHMS and orogenic Au deposits
in the Yilgarn Craton, Western Australia: Implications for gold and copper exploration,
Ore Geology Reviews (2016), doi: 10.1016/j.oregeorev.2016.04.020

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Pyrite compositions from VHMS and Orogenic Au Deposits in the Yilgarn

Craton, Western Australia: implications for gold and copper exploration

I. Belousov1, R.R. Large1, S. Meffre1, L.V. Danyushevsky1, J. Steadman1 and T. Beardsmore2

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1
ARC Centre for Excellence in Ore Deposits (CODES), School of Earth Sciences, University of

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Tasmania, 7001, Australia

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2
Geological Survey Division, Department of Mines and Petroleum, East Perth, Western Australia,

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6004, Australia

Abstract
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The Archaean Yilgarn Craton (Western Australia) is a world-class metallogenic province, hosting
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considerable resources of Au, Ag, Ni, Cu, Zn and Fe. Here we present trace element compositions of
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pyrite from more than 30 orogenic Au and 5 volcanic hosted massive sulphide (VHMS) deposits

across the Yilgarn. Pyrites from VHMS deposits tend to have higher Sn, Se, Cu, Pb, Bi and lower Ni
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relative to orogenic deposits. VHMS deposit pyrites commonly have Co>Ni, As>100Au, Te>Au, Se>Te.
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Orogenic gold deposits could be subdivided based on association of Au with As or Te. Pyrites from
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Au-As ores generally have Pb/Bi>5, Se/Te>5, Pb/Sb<5 and Tl/Te>100 and the majority of Au is

refractory (in pyrite structure). At the same time Au-Te association pyrites are characterised by

lower values of Pb/Bi, Se/Te and Tl/Te, higher values of Ag/Au, Pb/Sb and Au generally resides in

inclusions of different compositions. Our data can be used at the exploration stage to distinguish

between VHMS vs Orogenic Au signatures. For all studied deposits inclusion populations are

summarised with implications for Au and Ag deportment. Orogenic Au deposits from the Yilgarn

mostly have multistage formation histories reflected in the presence of multiple generations of

pyrites. However, only some deposits record multiple high Au mineralisation events.

Keywords: pyrite, gold, Au, orogenic, VHMS, Yilgarn, Western Australia, exploration
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1. Introduction

Pyrite is the most abundant sulphide phase in Earths crust and it is commonly associated with

mineralization in deposits forming in different environments (e.g. VHMS, orogenic Au, porphyry,

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epithermal, BIF, and SEDEX; Large et al., 2011; Sung et al., 2009; Reich et al., 2013; Gregory et al.,

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2013; Mumin et al., 1994). Therefore, pyrite geochemistry can provide information on differences in

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compositions of fluids and conditions of formation. Furthermore, it is potentially useful in vectoring

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for some environments as it is commonly found in zones at different distances to deposits (e.g.,

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Cassidy et al., 1998). Here we present data on pyrite (and in some cases pyrrhotite, arsenopyrite and

loellingite) compositions for 33 orogenic Au and 5 volcanic hosted massive sulphide (VHMS) deposits
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from Western Australia.

Orogenic Au deposits are usually formed as the result of interaction of host metasedimentary or
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metamafic rocks with low salinity fluids originating from metamorphic processes (Kerrich and Fryer,
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1979; Phillips et al., 1987; Cline et al., 2005; Kerrich et al., 2005) or deep seated intrusion (e.g.
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Burrows and Spooner, 1985; Spooner, 1993; Johnston and Ressel, 2004). Sources of Au and other
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metals is debatable (e.g. Tomkins et al., 2013) and could be intrusive or sedimentary rocks (e.g. black

shales; see Boyle 1979, 1986; Large et al., 2011). Volcanic hosted massive sulphide (VHMS) deposits
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are usually formed on or close to the seafloor as a result of sulphide (galena, sphalerite,

chalcopyrite, and pyrite) precipitation from a hot vent fluid. A recent review of VHMS mineralization

in the Yilgarn suggests strong temporal and spatial associations to suites of HFSE-enriched granitic

intrusions (Hollis et al., 2015). A range of VHMS deposits represented in this study is believed to

reflect different ages of formation as well as different signatures.

Western Australias (WA) gold mines account for a substantial amount of the worlds Au production.

In 20122013, WA accounted for 69% of Australias gold production and 9% globally (2nd place in

the world) production from WA mines reached 179 tonnes or 5.7 million ounces of Au. Total
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endowment of Yilgarn greenstone belts is more than 9730 t or 324 Moz of Au, with the Golden Mile

deposit at Kalgoorlie alone accounting for more than 2000 t or 67.3 Moz of Au (Witt et al., 2013).

Recent studies of gold mineralisation in Yilgarn have been primarily concentrated on: 1) the

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influence of large scale lithospheric structures on the localization of mineralisation (e.g. Weinberg et

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al., 2004, Blewett et al., 2010b); 2) deciphering sources of fluid involved in the deposit genesis (e.g.

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Brown et al., 2003, Walshe et al., 2009); and 3) recognition of multiple stages of mineralisation

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within individual deposits (e.g. Miller et al., 2010, Baker et al., 2010).

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The majority of samples reported in this study come from Orogenic Au and VHMS deposits within

greenstone belts of the Yilgarn Craton, which is divided from west to east into the Murchison,
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Southern Cross and Eastern Goldfield Provinces. The Eastern Goldfields Province is further divided

into the Kalgoorlie, Kurnalpi and Burtville Terranes and the Gindalbi Domain, which possibly
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represent remnants of different accreted island arcs (e.g. Czarnota et al., 2010), but could also
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represent different stages of volcanic evolution of the same Late Archean volcanic arc (e.g. Barley et

al., 2008). VHMS mineralisation in the Murchison (~2950 Ma) and Southern Cross Provinces is
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believed to be older than VHMS mineralisation in the Eastern Goldfields Province (~2700 Ma) (e.g.

Duuring et al., 2007, Van Kranendonk et al., 2013; Belford et al., 2015; Hollis et al., 2015).
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Our study is focused on pyrite trace element contents with implications for trace element signatures

of mineralisation and Au and Ag deportment. It was designed to cover wide range of deposits with

different trace element signatures. Variations with age, metamorphism grade and host rock

mineralogy are discussed. The data presented here could be used to distinguish between Orogenic

Au and VHMS signatures during exploration.

2. Sample description

Samples were analysed from the University of Tasmania (UTAS) rock storage collection and the

OSNACA project (Ore Samples Normalised to Average Crustal Abundance

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http://www.cet.edu.au/research-projects/projects/osnaca-ore-samples-normalised-to-average-

crustal-abundance). UTASs part of the collection contained 23 ore samples from 10 Orogenic gold

and 5 VHMS deposits, while OSNACA part contained 47 samples from 23 Orogenic gold deposits

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(Table 1). Availability of good quality whole rock (WR) analyses for the OSNACA set

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(http://www.cet.edu.au/research-projects/projects/osnaca-ore-samples-normalised-to-average-

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crustal-abundance/osnaca-data) allows for a comparison of WR and pyrite compositions. All samples

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are believed to represent mineralisation of each deposit, however exact location of sampling in

many cases is not known. More information about OSNACA samples could be found at OSNACA web

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site.
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The full list of deposits used in this study is presented in Table 1, and their approximate locations are

shown on Figure 1. A total of 70 samples from 33 orogenic Au and 5 VHMS deposits were analysed
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(Table 1). A more comprehensive description of samples used is presented in the Supplementary
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Material and could be found on OSNACA website. We analysed on average more than 15 pyrites

from each deposit and believe that such number should represent a range of pyrite generations and
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provide an estimate on trace element signature characteristic for each deposit.

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3. LA-ICPMS Analytical Method

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Measuring trace element compositions of sulphide minerals by LA ICPMS is a relatively complicated

task and requires special analytical conditions and standards (Danyushevsky et al., 2011, Gilbert et

al., 2014). The instrumentation used in this study consisted of a 213-nm New Wave Nd:YAG laser

microprobe coupled to an Agilent 7500a quadruple ICP-MS. For imaging a Resonetics RESOlution 193

nm excimer laser system coupled to an Agilent 7700 quadruple ICP-MS was used (see LA-ICP-MS

maps in Supplementary). All samples were analysed at LA-ICP-MS facility at CODES, University of

Tasmania.
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Laser ablation analyses were performed in the atmosphere of pure He flowing at a rate of 0.8 l/min;

immediately past the ablation point within the cell, He carrier gas was mixed with Ar (0.85 l/min) for

improved efficiency of aerosol transport. Analyses were performed on polished section of the rock

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mounted into 1-inch-size epoxy mount. The following isotopes were measured: 13C, 23Na, 24Mg, 27Al,

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Si, 34S, 39K, 43Ca, 49Ti, 51V, 53Cr, 55Mn, 57Fe, 59Co, 60Ni, 65Cu, 66Zn, 75As, 77Se, 85Rb, 88Sr, 90Zr, 95Mo, 107Ag,

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Cd, 118Sn, 121Sb, 125Te, 137Ba, 157Gd, 178Hf, 181Ta, 182W, 195Pt, 197Au, 202Hg, 205Tl, 206Pb, 207Pb, 208Pb, 209Bi,

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232
Th, 238U. The laser beam size used was generally 35 m with a repetition rate of 5 Hz, and a laser

energy density of ~ 3.5 J/cm2.

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Each analysis was performed in the time-resolved mode (fig.2) which involves sequential peak
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hopping through the mass spectrum. Dwell times on each mass varied between 5 and 50 msec,

depending on the count rates. The dwell times were chosen to enable detection limits at the level of
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single mg/kg for trace elements at low concentrations, and at the level of single mg/g for trace
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elements at high concentrations. The total sweep time (time required to measure all isotopes once)

was 0.76 sec. The analysis time for each sample was 90 seconds, comprising a 30 second
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measurement of the background (laser off) and a 60 second analysis with the laser on. Due to the
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low levels of molecular oxide and doubly charged ion production rates, no correction was applied for
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interfering species introduced into the analyte signal. However, possible argide, oxide, and hydroxyl

interferences on Pt and Au from Gd, Hf and Ta were monitored in each analysis.

Data reduction was undertaken according to standard methods (Longerich et al., 1996), using Fe as

the internal standard element and using an in-house-developed spreadsheet. Three primary

calibration standards were used: STDGL2b2 (Danyushevsky et al., 2011) was used for quantification

of all chalcophile and siderophile elements; GSD-1G (Guillong et al., 2005) was used for

quantification of lithophile elements; and a pure pyrite crystal was used for quantification of S.

Pyrite and pyrrhotite data was normalised to 100 wt% ppm. Fixed internal element (Fe)

concentrations were used when reducing arsenopyrite (343 000 ppm) and loellingite (270 000 ppm)
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data, since measured S contents differ from real concentration when using pyrite as a standard for

sulphur (Gilbert et al., 2014). The laser beam size for standard analyses was 105 m for STDGL2b2

and 50-80 m for GSD-1G and 35 mm for pyrite. STDGL2b2 and pyrite were analysed using the same

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laser fluence as for the unknowns, whereas the fluence for analyses of GSD-1G was ~ 6.5 J/cm2. All

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three standards were analysed twice every 1-1.5 hour to monitor drift in sensitivities. Linear drift

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corrections were applied between each set of standard analyses. As none of the calibration

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standards used contained Hg, quantification of Hg concentrations was not possible. Variations of Hg

contents between samples were assessed by comparing Hg count rates normalised to Fe count

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rates. Difference in the relative signal intensity of Hg and Fe between analytical sessions, and the

drift in these intensities within each session, were assessed and corrected for by normalising them to
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the difference between Pb and Fe intensities as measured on STDGL2b2.
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Images of elemental distribution within pyrite grains were acquired by rastering a set of parallel lines
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across the sample (Large et al., 2009). Laser beam size used for imaging varied between 10 and 20

m, depending on the size of pyrite. A repetition rate of 10 Hz was used. Rastering speed was in
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most cases equal to the laser beam size per second. Spacing between the lines was equal to the laser
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beam size, resulting in full coverage of the samples. Each line on the image was pre-ablated to
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remove surface contamination from previous ablations.

Age determinations can be done using lead isotope data (e.g. Stacey and Kramers, 1975). That

method has been shown to work for pyrite (e.g. Woodhead et al., 2009; Meffre et al., 2011). For

accurate Pb-isotope analysis special conditions should be used. Our data were acquired together

with other trace elements and could be used only for approximate and relative age determinations.

Our data were filtered and only values for analyses with >20 ppm Pb and low Th, U were used.

The presence of marcasite was confirmed using Raman technique. The Raman spectra were

measured using a Renishaw inVia microscope (UK) using a 50x, 0.75 NA, objective. The excitation

wavelength was a 532 nm diode laser which emitted 0.2 mW at the sample. The spectra were
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recorded from 107 1366 cm-1 using a grating of 2400 mm/l giving a spectral resolution of about

1.2 cm-1. The spectra were recorded on a Peltier cooled CCD camera with an exposure time of 1 s

using 100 accumulations.

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4. Refractory elements vs elements in inclusions

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A large number of trace elements are measurable by LA-ICPMS in pyrite. The most common groups

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of elements in rough order of abundance are: As (100-20000 ppm); Ni (10-5000 ppm); Mn (1-3000

ppm); Pb, Co, Ti, Ba, Cu, and Zn (10-2000 ppm); Sb, Cr, V, Mo, Se, Sn, and W (0.1-1000 ppm); Ag, Bi,

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Au, and Te (0.1-100 ppm); U and Tl (0.01-100 ppm) (Large et al., 2007; 2009).
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Trace metals in pyrite may occur in several ways: a) as solid solution within the pyrite structure; b)

within invisible nano-inclusions of other minerals; c) within visible micron-sized inclusions of other
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sulfides or d) within visible micron-sized inclusions of silicate or carbonate minerals. There has been
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no attempt made in this study to remove the effects of micron-sized inclusions on the pyrite

analyses. However, inspection of the LA-ICPMS signal from each laser spot analysis enables an
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estimation of whether a particular trace element occurs within a pyrite structure or within
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homogeneously distributed nano-sized inclusions (referred to as refractory for Au); or alternatively

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as larger isolated micron-sized inclusions (Fig. 2, 4). It is not possible to determine by LA-ICPMS

whether a particular element is present as nano-particles in pyrite or as solid solution in the pyrite

structure. As with previous studies (e.g. Large et al., 2009; Large et al., 2007; Deditius et al., 2011;

Thomas et al., 2011), this study has found that the suite As, Mn, Co, Ni, Se and Mo are commonly

homogeneously distributed in the pyrite, either within the pyrite structure or as nano-inclusions; the

suite Au, Ag, Cu, Zn, Sb, Te, Tl, Pb, Bi may be present as either invisible nano-inclusions (as in the

group above) or within metallic or sulfide micro-inclusions; the suite V, Ti, Cr, Zr, Sn, Ba, W, Th and U

are mostly present in pyrite within non-sulfide micro-inclusions.

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Gold and silver are present in both refractory form and as inclusions. This information is very

important for mineral processing as the deportment of these two metals has a crucial influence on

recovery rates. Our data (Table 1, Fig.4) as well as previous studies (e.g. Deditius et al., 2011) show

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that gold and silver, if not included in pyrite structure, can be present as native Au and/or Ag

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inclusions, electrum (Au+Ag) inclusions, or be associated with various sulphide, telluride, antimonide

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and/or sulfosalt inclusions containing various amounts of Te, Pb, Sb, Bi and Hg. In the following

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sections, information obtained from the LA-ICPMS time resolved graphs (e.g.Fig.4) as well as LA-ICP-

MS maps of pyrite grains (Appendix 1) is presented for different deposit types. However, in most

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cases it is not possible to accurately determine the mineralogy of the inclusions, but only trace

element associations in inclusions.

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5. Orogenic gold deposits
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5.1. Types of Orogenic Au deposits: Au-As and Au-Te

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Our LA-ICP-MS data on pyrite indicate two end-member associations in orogenic gold deposit ores
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(Fig.5):
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1) Au-As ores (pyrite As/Te>200 or 100Te/(As+Te)<0.5). Examples are: Wiluna, Sunrise Dam,
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Kanowna Belle, Paddington, Lancefield, Meekatharra Prohibition, Minjar, Youanmi, Big Bell,

Mickey Doolan Meekatharra.

2) Au-Te ores (pyrite As/Te<10 or 100Te/(As+Te)>10). Examples are: Granny Smith, Hunt,

Porphyry, St.Ives (Mars Pit), Maybell, Darlot, Songvang and Junction.

3) Between these end-members is a group of deposits that display Au-As-Te association, e.g.

Golden Mile, Chalice, Redeemer, Wallaby, Nathans Labouchere, and Fortnum (Starlight Pit).

Some of these deposits (e.g. Golden Mile) have Au-Te ores (Fimiston or Golden Mile stage)

overprinted by the Au-As ores (Mt Charlotte stage).

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Different samples from the Mt. Magnet (Hill 50) deposits display contrasting compositions, with

more Au rich samples falling into Au-Te association and Au-poor samples into Au-As association.

There are also several deposits present that have addition of VHMS-like or other style of

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mineralisation: Big Bell (Sb, W), Plutonic (Ag, Sb, Pb, Tl), Junction (W) and possibly Lancefield (Sn).

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Tellurium and arsenic rich end members may represent magmatic vs metamorphic sources for the

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fluids, as oxidized magmatic fluids associated with magmatic systems are capable of carrying Te

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(Grundler et al., 2013). However, tellurium can also be sourced from sedimentary rocks (Large et al.,

2011).

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Most of the deposits with high Au and As contents in pyrite have the majority of their Au in the
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refractory form. However, deposits such as Kanowna Belle, Lancefield and Youanmi, as well as

deposits in the Au-As-Te association (e.g. Golden Mile and Chalice), also have a considerable amount
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of Au as inclusions. Pyrites from Au-As ores have Pb/Bi>5 (except for sample from Youanmi and one
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sample form Sunrise Dam), Se/Te>5 (except in one sample from Kanowna Belle), Pb/Sb<5, and

Tl/Te>100 (Fig.5).
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In contrast, the majority of Au-Te type deposits have the highest amount of Au as inclusions within

pyrite (Table 1). These pyrite compositions are characterised by Pb/Bi<5 (except sample from
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Junction), Se/Te<5 (except the same sample from Junction), Pb/Sb>5, Tl/Te<100 (except sample

from Junction). They also show Ag>Au in most pyrites.

In terms of Co-Ni and Au-Ag relationships, Au-As and Au-Te associations display no differences.

However, both classes differ from VHMS deposits, which tend to have Co>Ni and Ag>Au.

Furthermore, the presence of pyrrhotite with pyrite in the same sample influences the Co/Ni ratio of

pyrite by shifting the compositions of pyrite towards higher Co contents (Fig.7).

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5.2. The Au-As relationship in pyrite

Reich et al. (2005) showed that the maximum possible amount of gold in solid solution in

pyrite depends on the As content of pyrite. The As-Au relationships in pyrite have proved to be

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useful for distinguishing between the refractory and free gold ores (e.g., Large et al; 2007, 2009,

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2011, 2013; Thomas et al; 2011). In Fig.6, pyrite LA-ICPMS analyses which plot above the maximum

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solubility line (pink field) contain free gold inclusions, whereas analyses which plot below the line

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contain solid solution (refractory) gold in pyrite. Our data from Yilgarn orogenic gold deposits (Fig. 6)

suggest that the maximum Au solubility line might be lower for pyrites from WA than previously

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determined by Reich et al. (2005), meaning that more Au goes into inclusions rather than stays in
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pyrite structure. This is possibly one of the factors enhancing the productivity of Yilgarn gold

deposits.
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Our data also show that even for the Au-As type deposits, there is a positive correlation
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between Au and Te (Fig.5). This can be explained by either a coupled Au-Te transfer in fluids or

enhancement of Au partitioning into pyrite with increasing Te concentrations (besides As). Tellurium
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in As-Au association pyrites also tends to be refractrory.

Arsenopyrite (Aspy) coexists with pyrite in samples from Minjar, Youanmi, Meekatharra
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Prohibition, Paddington, Lancefield, and Sunrise Dam. The Jaguar VHMS deposit also contains Aspy,

whereas at Griffins Find and Three Mile Hill arsenopyrite occurs together with pyrrhotite, implying a

higher degree of metamorphism for the latter deposits (e.g. Tomkins et al., 2009). High Au

arsenopyrite was analysed in some samples from Sunrise Dam and Lancefield and intermediate gold

(up to 50 ppm) in Meekatharra Prohibition. Others have quite low Au in arsenopyrite (Fig.7C).

Arsenopyrites can contain quite high Sb and in some cases Te and Se contents (Fig.7). The highest Te

contents in arsenopyrites from Sunrise Dam deposit are coupled with highest Au contents, while in

arsenopyrites from Paddington Au and Te contents display negative correlation. The highest Sb

contents were analysed in arsenopyrite from Lancefield. In general, average Sb and Au contents of
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arsenopyrites are higher than their contents in pyrites from the same deposit (except for

Paddington) (Fig.7C); however individual analyses reveal negative correlation between Au and Sb in

arsenopyrites from Meekatharra Prohibition and Youanmi. Analysed sample from the Griffins Find

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deposit also contains loellingite (FeAs2) together with arsenopyrite and pyrrhotite. Loellingite

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contains 190-300 ppm Au and had higher Ni and slightly higher Co contents compared to

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arsenopyrite from the same sample (Fig.7).

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5.3. Distribution of other metals

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Most deposits of the Au-Te type, such as Granny Smith, Hill 50, Hunt, and Porphyry have the

highest amount of Au in inclusions. In most cases Au is present as AuAgTe inclusions (Table 1), but
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populations of PbBiTe inclusions containing gold exist in Kanowna Belle, Hill 50, Hunt and Maybell.

Ag in most cases is related to Pb+BiTeSb inclusions. The highest Ag (>50 ppm) is found in pyrites
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from Plutonic (Fig. 4B), Songvang (Fig. 4C) and Chalice (Fig. 4A). The latter has relatively low Pb
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contents, and the high Ag in pyrites from this deposit is not related to Pb-rich inclusions, but to

electrum (Ag+AuTe) (Fig.4A) and As+Cu+Sb+Ag+Hg inclusions. Some pyrite grains from Golden Mile,
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Sunrise Dam and Big Bell also contain high Ag.

Pyrites with >1 wt% Ni were found at Wallaby, Mickey Doolan, and Minjar, while grains with
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>1wt% Co exist in the Fortnum and Mickey Doolan deposits. Copper and Zn are usually associated

with inclusions of chalcopyrite and sphalerite. The highest Cu contents are in pyrites from Minjar and

Chalice, while some pyrites from Golden Mile, Kanowna Belle and Plutonic have high Zn contents.

The highest Pb analyses come from the Plutonic deposit. They are also characterised by high

Au, Ag, Sb, Te, Se, Bi (Fig. 4B) and most likely represent mixtures of pyrite with micro- or nano-

inclusions of galena (Fig. 3B). The highest Bi contents are in pyrite from Plutonic (Fig. 4B) and

Redeemer deposits (Fig. 4D). Some Bi is also present in pyrites from Sunrise Dam, Songvang (Fig.4C),
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Maybell, Granny Smith and Porphyry. It mostly occurs together with Pb, apart from in Songvang and

Junction deposits (Fig. 4).

Apart from Plutonic (Fig. 4B), very high Sb contents are characteristic for pyrites/marcasites

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from Big Bell and pyrites from Youanmi, however in Big Bell Sb is present in as refractory or

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SbWAg inclusions (Appendix 1), whereas in Youanmi it is usually present as Sb+Cu+Zn+Ag

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inclusions (Fig.4E). Other deposits with high Sb contents in some pyrites include Sunrise Dam,

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Kanowna Belle, Minjar, Lancefield, Paddington, Golden Mile and Micky Doolan, where it is mostly

occurring together with Pb, Cu or Bi (Table 1).

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The highest Se contents are in pyrites from Plutonic (Fig. 4B) and Fortnum, while some
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pyrites from Redeemer (Fig. 4D), Porphyry, Junction (Fig. 4F), Hunt, Songvang (Fig. 4C), Mars and

Sunrise Dam also have high Se contents. Elevated Tl contents are in some pyrites from Golden Mile
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and Plutonic. Selenium is present mostly in refractory form, while Tl resides in Pb-rich inclusions.
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Both of those elements are known to be highly volatile and their elevated concentrations may

indicate low temperatures of formation.

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High-Sn pyrites from Lancefield also contain high Cu, Au and Sb contents, however the

highest contents of Au and Sb are in arsenopyrite from this deposit. Trace element mapping reveals
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that Sn in this deposit comes together with Cu (Appendix 1). Tungsten is mostly found in Ti+W or

silicate matrix inclusions, except for Big Bell and Junction deposits, where it is mostly associated with

marcasite or ilmenite/rutile (Appendix 1, Appendix 2).

Mercury is the highest in Golden Mile and Chalice pyrites, where it is present in the pyrite

structure as well as in inclusions with or without Au, Ag, Te, Sb. Some Hg is also present in pyrites

from Big Bell, Sunrise Dam, Kanowna Belle, Minjar, Hunt, Lancefield, Nathans Labouchere, Darlot

and Meekatharra Prohibition (Appendix 1), where it is mostly present in the refractory form.
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5.4. Effects of Metamorphism and redox conditions

During low to medium grade metamorphism, many trace elements that might originally be

present in the structure of pyrite (e.g. Pb, Zn, Cu, Bi, Te, Ag, Au) tend to leave the pyrite structure

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and form inclusions of other sulphides and tellurides within pyrite (e.g., inclusions of galena,

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sphalerite, chalcopyrite, Bi-tellurides, and Pb-Bi-Au-Ag tellurides). Gold and Ag are commonly

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associated with such inclusions. Identification of whether Au and Ag are in the refractory form or are

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associated with inclusions is very important for Au and Ag recovery. The higher the As content of the

ores, the more likely gold will be refractory in either arsenian pyrite or arsenopyrite. For example,

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low metamorphic grade arsenic-rich ores will have >90% gold refractory, whereas As-poor, medium
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to high metamorphic ores will have >90% gold as free gold grains or gold telluride grains.

Most gold deposits in the greenstone belts of Yilgarn have experienced greenschist facies
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metamorphism, except for Wiluna, which is sub to low greenschist facies, and deposits from the SW
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Yilgarn and Norseman Provinces as well as the Big Bell deposit (e.g. Qiu et al., 99; Barnicoat et al.,

91), which have undergone amphibolite to granulite facies metamorphism. The increasing grade of
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metamorphism in these deposits is reflected in the change in sulphide mineralogy.

Pyrrhotite was found together with pyrite in Hill 50, Maybell and Plutonic samples, but only
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pyrrhotite was analysed in samples from Randalls, Karonie, Griffins Find, Three Mile Hill, and some

samples from Plutonic. In all samples pyrrhotite has very low Au (Fig.7C), with only 2 analyses with

Au> 1 ppm in Karonie pyrrhotites are associated with Pb+Au+Ag+Te and electrum (Ag+Au)

inclusions. Overall, pyrrhotite has a small number of trace elements included into its structure (Co,

Ni, and Se), whereas all other elements are present in inclusions (e.g. Ag, Te, Sb, Pb). In pyrrhotites

from Griffins Find, Hill 50 and Maybell, Ni contents are much higher than Co, while pyrrhotites from

Three Mile Hill deposit have much higher Co (Fig.7). Pyrrhotites from Plutonic, Karonie, and Randalls

have Co/Ni values close to 1. Lowest Se contents are characteristic for pyrrhotites from Griffins Find,

Hill50 and Maybell, while Plutonic pyrrhotites have the highest Se contents. At the same time
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pyrrhotites from Griffins Find, Hill 50 and Maybell have Se/Co>1, while the others have Se/Co<1.

Generally pyrrhotites have lower much lower Co compared to pyrite from the same deposits;

therefore they have much lower Co/Ni ratios (Fig.7). The presence of pyrrhotite in a sample

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influences Co/Ni ratio in pyrite shifting it towards higher Co contents (Fig.7). Such an effect has been

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described for pyrite that has crystallized at the expense of pyrrhotite during retrograde cooling

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(Craig and Vokes, 1993; Steadman, 2015).

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The presence of metastable arsenian pyrite (As>1Wt%) in samples from Sunrise Dam,

Wiluna, Kanowna Belle, Chalice, Meekatharra Prohibition, Paddington, and Mickey Doolan may be

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due to their lowest metamorphic grades. In contrast, the presence of arsenopyrite in samples is an
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indication that these deposits either formed from slightly hotter fluids or were metamorphosed to a

higher degree. Arsenian pyrite coexists with arsenopyrites in samples from Sunrise Dam,
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Meekatharra Prohibition and Paddington, while low As pyrite coexists with arsenopyrites in samples
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from Lancefield and Youanmi. Loellingite is present together with arsenopyrite in Griffins Find, which

suggests even higher grades of metamorphism (e.g. Tomkins et al., 2001). In this deposit Au is being
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redistributed into loellingite, however it was shown that at higher degrees of metamorphism Au
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starts to form inclusions on the arsenopyrite/loellingite boundary (Tomkins et al., 2009).

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Marcasite (orthorhombic FeS2) is known to form at lower pH (i.e. more acidic fluid) relative

to pyrite and its formation is favoured at higher temperatures (e.g., Qian et al., 2010). Marcasite and

mixes of marcasite with pyrite were analysed for Big Bell and Junction deposits. Their presence was

confirmed using Raman. Raman spectra for pyrites and marcasites from both samples are given in

Supplementary (Appendix 2). Marcasites from both Big Bell and Junction deposits contain high W

contents.

High grades of metamorphism force most of trace elements to leave the pyrite mineral

structure, whereby they end up in the matrix. Analysis of host rocks by LA-ICPMS also revealed

presence of Au-containing inclusions in the rock matrix for Karonie, Hunt and Golden Mile and on
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edges of pyrite at Big Bell. Free gold occurrence in the matrix on the margins of arsenopyrite crystals

was also described for Randalls (Steadman et al., 2014), where arsenopyrite was shown to coexist

with pyrrhotite. For Griffin Find it was shown during prograde metamorphism initially present gold

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most likely partitions from pyrite into arsenopyrite, then into loellingite and inclusion formation

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takes place during retrograde metamorphism (Tomkins et al., 2009; 2001).

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5.5. Is pyrite composition of orogenic gold deposit ores dependant on geographic location?

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The lowest Au contents are found in pyrites from Junction, Mickey Doolan Meekatharra, Minjar and

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Nathans Labouchere, whereas the highest are in Kanowna Belle and Sunrise Dam. Pyrites with over

10 ppm Au were also analysed in Chalice, Golden Mile, Granny Smith, Lancefield, Paddington,
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Porphyry, Hill 50 and Wiluna.

We have subdivided orogenic Au deposits based on their location to assess possible province related
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characteristics:
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Murchison Province: Big Bell, Mt.Magnet (Hill 50), Minjar, Meekatharra Prohibition, Micky Doolan
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Meekatharra, and Youanmi (Fig.1).

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Deposits are subdivided into groups based on As and Te contents (Fig.8a):

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- Au-As association: Meekatharra Prohibition, Youanmi, Micky Doolan Meekatharra, Minjar,

Big Bell

- Au-Te association: Mt. Magnet (Hill 50)

Meekhatharra Prohibition pyrite is characterised by highest Au and As contents (Fig.8a), but lowest

Te, Co and Ni. Some Au is also locked in arsenopyrite. Highest Ag contents are in pyrites from Minjar

and Big Bell. Mixture of pyrite and marcasite from Big Bell deposit are most enriched in Sb, Tl, W, but

depleted in Au and Bi (VHMS signature?) (see Appendix 1). Lowest As and highest Te contents are in

pyrites from Mt. Magnet (Hill 50). They also have quite low Co and Ni contents, but not as low as

pyrites from Meekatharra Prohibition.

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Eastern Goldfields

Eastern Terranes: Sunrise Dam, Granny Smith, Lancefield, Wallaby, and Porphyry (Fig.1)

Deposits can be subdivided into groups based on As and Te (Fig.8b):

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- Au-As association: Lancefield and Sunrise Dam

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- Au-Te association: Granny Smith, Porphyry and Sunrise Dam

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- low As, Te: Wallaby

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Highest Au contents are in pyrites from Sunrise Dam, Granny Smith and Lancefield (Fig.8b).

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Arsenopyrites from Lancefield and Sunrise Dam also have high Au contents (Fig.7). Lowest Au

contents are in pyrites from Porphyry and Wallaby, which are accompanied with low As. Granny
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Smith pyrites also have low As contents, but high Te, Ag and W. Lancefield pyrites spread to highest

contents of Sn, Zn, Tl and Sb, and lowest Co, Ni, W and Bi. Pyrites from Porphyry have highest Se and
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Bi and lowest Sb, Cu and Zn contents (Fig.8b).

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Four samples from Sunrise Dam have different pyrite compositions reflecting complex geological
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structure of the deposit and several stages of mineralisation present (e.g. Baker et al., 2010, Sung et
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al, 2009). Pyrites from the BIF sample from Sunrise Dam have lower Te, Se, Tl and Bi contents

compared to other samples.

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Western Terranes, south: Paddington, Kanowna Belle, Golden Mile, Hunt, St Ives (Mars), Chalice,

Junction, and Maybell (Norseman) (Fig.1)

Deposits could be subdivided into groups based on As and Te (Fig.8c):

- Au-As association: Kanowna Belle, Paddington

- Au-Te association: Hunt, St Ives (Mars)

- Au-As-Te association: Chalice, Golden Mile

- low As, Te: Maybell, Junction

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Highest Au, As, Sb and Pb contents are in Kanowna Belle sample from OSNACA collection. Kanowna

Belle sample from UTAS collection has lower contents of most metals except Co, Ni, Se (Fig.8c) and

might represent unmineralised part of the deposit. Au and As in Junction pyrites and marcasites are

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below detection limits (Appendix 1). They also have low Te and Sb, but high Se, Cu, Bi and highest W

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contents. Pyrites from Paddington have lowest Co, Ni and W contents and low Ag and Te contents.

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Pyrites from Maybell have low Au, As, Co, Sb, Zn, Tl and Sn, but highest Bi contents. Golden Mile

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samples have highest Tl and lowest Bi contents and together with pyrites from Chalice spread to

high Au, Ag, As, Te and Sb contents (Fig.8c). Different samples from Golden Mile deposit have quite

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different Co/Ni, Se/Te, Se/Tl and Se/Au ratios (Fig.5). Sample from Mars Pit is likely to be

unmineralised since its pyrites have low contents of most metals.

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Western Terranes, north: Darlot, Redeemer, Songvang and Wiluna (Fig.1)

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- Au-As association: Wiluna

- Au-Te association: Darlot, Songvang

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- Au-As-Te association: Redeemer

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Grains with more than 10 ppm Au were analysed only in Wiluna samples (Fig.8d), which has the
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highest Au, As, Sb, Tl, W, but lowest Co, Se and Bi contents. Pyrites from Redeemer have the second

highest Au contents and are characterised by high As, Se and Te contents and low W contents.

Pyrites from Songvang have the largest spread of Te and spread to lowest Bi, Zn, Pb contents, but

have high Ag and W contents. Pyrites from Darlot are characterised by the lowest Ni contents.

Summary: Although variations inside each group are large due to differences in composition of

mineralizing fluids, pyrites from orogenic Au deposits from Murchison generally show lower Ag, Te,

Se and Bi contents (Fig.9). Pyrites from deposits from SW Eastern Goldfields have lowest mean As,

Sb and Tl contents. Kalgoorlie deposit pyrites are the most enriched in Au, As, Te, Ag, Sb and Tl

contents. However, pyrites from Plutonic deposit are even more enriched in Ag, Sb and Tl. Orogenic
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Au deposits from Capricorn Orogen are much more depleted in Au, Ag, Sb, Tl and enriched in Se

compared to Yilgarn deposits (Fig.8e, 9). VHMS as well as Orogenic Au deposits located to the north

of the Murchison Province (DeGrussa, Horseshoe Lights, Plutonic, Nathans Labouchere, Fortnum)

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have much younger ages relative to deposits from Yilgarn (Fig.11).

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6. Multi-stage mineralisation history

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Multistage formation history is common for orogenic Au deposits. For Yilgarn deposits it was

shown for Golden Mile (Bateman et al., 2004; Mueller et al., 2013; Steadman et al., 2015), Sunrise

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Dam (Baker et al., 2010, Brown et al., 2002, Brown et al., 2003, Sung et al, 2009), Chalice (Bucci et

al., 2002, 2004), Kanowna Belle (Ross et al., 2004), Big Bell (Mueller et al., 1996), Wiluna (Hagemann
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et al., 2003), Junction (Polito et al., 2001). Usually multiple mineralisation stages could be seen in

multiple pyrite generations present (e.g. Large et al., 2009, 2011, Steadman et al., 2015, Velasquez
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et al., 2014). Our data show the presence of several stages in most deposits from this study.
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Different generations of pyrite could be distinguished based on Co/Ni ratios and contents of Au, As,
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Co, Ni, Te, Sb, Bi. We havent found any pyrite generation with Au>10 ppm that also have Co/Ni>10.
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Some of different pyrite generations from our dataset were found to have different Pb
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isotope ratios (Fig.11). In some cases, like for Plutonic deposit, age differences between different

generations could be real. However, for most other cases (e.g. Golden Mile) such difference in Pb-

isotopic composition is likely not due to different ages of mineralisation, but due to different sources

of metals. Multiple high Au stages are present in Golden Mile, Sunrise Dam, Kanowna Belle and

possibly Chalice and Paddington.

In some orogenic Au deposits deposits, addition of VHMS-like, or other style of fluid is

apparent at certain stages in their geological history: Big Bell (Sb, W), Plutonic (Ag, Sb, Pb, Tl),

Junction (W) and possibly Lancefield (Cu, Sn). The most Au-rich analysis from Plutonic mine come

from a mixture of pyrite+galena+Sb+Ag+Tl (Fig.3), which are possibly much older (by ~600 My)
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(Fig.11) than the rest of pyrites that have much lower Au contents, but still high Ag. Big Bell and

Junction deposits also contain marcasite (Appendix 1, 2), which are characterised by high Sb and W

for Big Bell and high W for Junction. Elevated Sn was found in pyrites from Lancefield, which comes

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together with Cu indicating possible interaction with a VHMS fluid.

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7. VHMS deposits

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Pyrites from the VHMS deposits tend to have higher Cu, Pb, Bi, Sn, Se and lower Ni relative

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to the orogenic gold deposits (Fig.5). The VHMS deposits mostly have Co>Ni, As>100Au, Te>Au, and

Se>Te. They have much more abundant inclusions of galena, chalcopyrite and sphalerite. Commonly

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inclusions of tellurides or complex sulfosalts were apparent (Pb+Bi+Ag+Te+Sb) from the laser data.
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Au is mostly low and refractory with rare inclusions of free Au or telluride complexes. Generally

pyrites from the VHMS deposits could be distinguished from the orogenic Au deposits by having

Sb/Au>8.
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Pyrites from Golden Grove, Scuddles and Jaguar are characterised by low Te contents and

fall into the field of the Au-As association, whereas pyrites from the DeGrussa and Horseshoe Lights
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deposits fall into the As-Te association (Fig.5). Golden Grove pyrites are the poorest in As, Te, Se, Tl

and Pb, whereas those from DeGrussa are the richest in Au, As, Se, Te, and Pb (Fig.10). Some pyrites
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from Horseshoe Lights also have elevated Au, As, Te, Ag and Se, but lowest Tl, W and Sn (the only

VHMS deposit analysed that contains <1 ppm Sn). The sample from the Jaguar Mine has pyrite with

lowest Cu, but high Ag, Tl, Pb, Sb and Se. The Pb-isotope data suggest older mineralisation for the

Murchison Province VHMS deposits (Golden Grove and Scuddles) and Jaguar deposit relative to

DeGrussa and Horseshoe Lights (Fig.11).

8. Chemical Discrimination between Orogenic Au deposit pyrite and VHMS pyrite

Based on five VHMS deposits and 33 orogenic Au deposits from Western Australia, our data

indicate in general terms that VHMS pyrites have higher levels of Cu, Co, Pb, Se, Zn, Sn and Bi, whereas
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orogenic gold pyrites have higher levels of Ni, As, Au, W and V (Fig.5). These differences may partly relate to

the source of the ore fluids (i.e. sedimentary, mafic volcanic or felsic volcanic), but are also affected by the

temperature and salinity of the fluids. Orogenic gold deposits in some cases have wide salinity ranges of

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associated fluid inclusions (e.g., Hagemann et al., 2003). Different models exist for formation of VHMS

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deposits from variable salinity fluids (e.g. Large, 1992) and temporal variations of sea water salinities were

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also shown (Huston et al., 2010). However, Orogenic gold deposit ore fluids are generally believed to have

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lower salinity compared to VHMS fluids (e.g., Ho et al., 1992; Groves et al., 1998; Large et al., 2001). Low

salinity and neutral pH favours transport of Au and As in the more soluble bi-sulfide complexes (e.g.,

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Goldfarb et al., 2003; Hagemann et al., 2003; Kendrick et al., 2011). Copper, Pb, Zn, Co and Sn are all

transported as chloride complexes in saline and weakly acidic hydrothermal fluids. Co and Se tend to
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concentrate in high temperature pyrites, usually found in the copper-rich parts or footwall alteration zone

of VHMS systems (Huston et al., 1995).

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Most (>90%) of VHMS pyrites have Co/Ni > 1, and 61% have Co/Ni > 10. In contrast, 65% of orogenic

Au deposit pyrites have Co/Ni < 1 and 94% have Co/Ni < 10 (Fig. 5, 12). This relates to the fact that Co is
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more soluble than Ni in moderate to high temperature saline fluids, similar to VHMS fluids. The presence of
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pyrrhotite also influences Co/Ni ratios (Fig.7). Therefore, metamorphism of rocks from Orogenic Au deposits
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may shift pyrite compositions into the VHMS field (Co/Ni>1). However, samples may also contain different

generations of pyrite that have different Co/Ni ratios that could also be influenced by host rock

composition.

VHMS pyrites generally have higher Cu and Sn contents, and the Cu-Sn plot (Fig. 5) is very

useful for discrimination of VHMS from Orogenic Au deposit pyrite. The higher copper content of

VHMS pyrite is likely a function of mafic volcanic source rocks and higher salinity and temperature of

fluids. Orogenic Au deposit pyrites are commonly W-bearing (0.1 to 3000 ppm) and Sn-poor (< 1

ppm Sn), whereas VHMS pyrites have variable Sn (0.1 to 20,000 ppm) and low W (< 10 ppm). In

deposits from this study, tungsten is mostly seen in Ti+W (rutile) or matrix inclusions in pyrite, but

refractory in marcasites from Big Bell and Junction deposits. High Sn contents in pyrites from
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Lancefield are associated with elevated Cu and most probably reflect an additional VHMS signature.

Sn and W are generally thought to be sourced from granites (e.g. Groves et al., 2003), but tungsten

(W) could also be sourced from the metamorphic breakdown of ilmenite in sedimentary rocks (Cave

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et al., 2015). Tin (Sn) could be derived from breakdown of silicate phases in volcanic rocks which are

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most probable source of Sn in VHMS deposits. It is most likely present in inclusions of cassiterite in

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pyrites from VHMS deposits, but is in refractory form in pyrites from Lancefield.

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9. Conclusions

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Trace element compositions of pyrites can be used to effectively discriminate orogenic gold and

VHMS deposit signatures during exploration. VHMS pyrites generally have higher levels of Cu, Co,
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Pb, Se, Zn, Sn and Bi, whereas orogenic gold deposit pyrites have higher levels of Ni, As, Au, W, V and

Cr. These differences relate to source rocks and differences in salinity, temperature and pH of the
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ore fluids. Vectoring scores have been developed for both VHMS and orogenic gold deposit pyrites
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and enable a pyrite from drill intersection to be classified as background, distal, proximal or a high
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priority target.
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Orogenic Au deposits can be subdivided into Au-As and Au-Te associations based upon pyrite
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geochemistry. Pyrites from Au-As ores have the most amount of Au in refractory form, Pb/Bi>5,

Se/Te>5, Pb/Sb<5, and Tl/Te>100. In contrast, the majority of Au-Te type deposits have the highest

number of Au inclusions. The location of deposits with highest Au contents in pyrites is not restricted

to any particular area or host rock type, but is most probably associated with the fertility of the

series of enrichment events and the degree of their focussing. Most of deposits studied here are

characterized by multistage formation history, however only a few of them (Golden Mile, Sunrise

Dam, Kanowna Belle) have multiple high Au events.

LA-ICP-MS technique is very effective in determining trace element contents of sulphide minerals,

mapping trace element distributions between different phases and metal deportment studies. The
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data obtained by this method could be used to distinguish between Orogenic Au and VHMS

signatures during exploration and estimate proximity to the deposit. That approach was tested on

several drill holes from Western Australia and proved to be successful.

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Acknowledgements

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The analyses from this study have been done as a part of collaborative project between CODES and

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GSWA. The authors would like to thank Margaret Ellis and Rick Rogerson at the GSWA for their

assistance in developing this project and to GSWA core library staff for providing access and valuable

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assistance in the collection of core samples from the Perth and Kalgoorlie core libraries. Also thanks

to Margy Hawke for providing samples from DeGrussa and surrounding deposits and to Carl
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Brauhart, Stephen Hagemann, Tim Mueller, Brent Simpson and Mike Doepel for providing samples

from the OSNACA collection. The authors are very grateful to two anonymous reviewers for efficient
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editorial handling that improved considerably the early version of the manuscript.
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Appendix 1.
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LA-ICP-MS images of pyrite grains from deposits of Western Australia

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(in counts per second)

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Chalice

Big Bell
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Meekatharra Prohibition
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PTE
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Junction
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Hunt
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Granny Smith
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Lancefield
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Appendix 2.
Raman spectra of pyrite and marcasite from Big Bell and Junction deposits

Positions of pyrite (black) and marcasite (red) Raman bands from White, 2009
and scatter for pyrite from RRUFF database (grey field) are given for
comparison.

Junction
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Big Bell
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Fig.1. Schematic map of Yilgarn Craton (modified from Pawley et al., 2012) with inserts given to show

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deposit locations. All deposits are shown with studied deposits marked with larger symbols and text.

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Fig.2. Time-resolved record of the signal recorded on the ICPMS (in counts per second) during a

single analysis. First, background levels are recorded, then, at 32 seconds laser is turned on and

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ICPMS collects data from the sample for each element. As long as Fe signal doesnt change much, we

are analysing pyrite. Some elements are incorporated into pyrite structure and show no or gradual
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change (zonation), others are concentrated in inclusions (spikes). Note that evenly distributed micro

inclusions may also show no or gradual change in the signal. At the data reduction stage signal from
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the whole interval gets averaged and standard analyses are used to recalculate counts per second
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data into concentrations.

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Fig.3. Photographs of pyrite grains from a) Chalice, b) Plutonic, c) Songvang, d) Redeemer, e)

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Youanmi, f) Junction deposits. Abbreviations: Py pyrite, Aspy arsenopyrite, Mt magnetite, Po

pyrrhotite, Ga galena. Round holes represent Laser Ablation spots.

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Fig.4. Examples of time-resolved graphs during analysis of pyrites from respective deposits from

Fig.3. It is not possible to determine mineralogy of inclusions from LA signal, therefore only trace

element associations are discussed and shown on the graphs. a) Chalice Ag+Au+Te and Hg-bearing

inclusions of; b) Plutonic mixture of pyrite and galena with high evenly distributed contents of Sb,

Bi, Ag and Au; c) Songvang low Au, but Ag+Te, Pb, Bi-bearing inclusions; d) Redeemer high

contents of Bi, Pb, Co, As and some Sb, Cu, Tl, Te, Ag and Au, all present in refractory form; e)

Youanmi free Au, Sb+Cu+Zn+Ag-bearing inclusions and some refractory Pb and Bi; f) Junction

pyrite/marcasite high refractory Co, W, Cu, some Ni and Bi, the latter partly associated with

inclusions.
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Fig.5. Average trace element compositions of pyrite from Yilgarn deposits. Different generations are

shown only for Golden Mile, Sunrise Dam, Plutonic, DeGrussa and Horseshoe Lights deposits. Table

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S1 also contains data for different generations in Wiluna, Hill50, Minjar, Fortnum and pyrite as well

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as marcasite data from Big Bell. Lines on some of the graphs indicate certain ratios and are given for

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reference.

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Fig.6. a) Position of Au-As solubility line for pyrites from Yilgarn deposits relative to described in

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Reich et al., 2005, symbols are marked based on deposit type and presence of Au in refractory form

or as inclusions; b) Same solubility Au-As solubility plot, but symbols are marked based on
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association of Au with As and Te. All analysed pyrites are plotted. Information on form of Au

occurrence is based on time resolved graphs of LA-ICP-MS analyses (e.g. Fig.4).

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Fig.7. Comparison of coexisting pyrite, pyrrhotite and arsenopyrite compositions from Yilgarn
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deposits. Data for Randalls deposit is shown from Steadman et al., 2014. Coexisting minerals are
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connected with lines.

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Fig.8. Comparison of trace element contents for pyrites from orogenic Au deposits a) Murchison
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Province; b) Eastern Terranes of Eastern Goldfields Province; c) southern part of Western Terranes of

Eastern Goldfields Province; d) northern part of Western Terranes of Eastern Goldfields Province; e)

Capricorn Orogen and Marymia Inlier

Fig.9. Comparison of trace element contents for pyrites from orogenic Au deposits from different

locations.

Fig.10. Comparison of trace element contents for pyrites from VHMS deposits from different

locations
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Fig.11. Average lead isotope ratios diagram for different pyrite generations from a) orogenic Au

deposits, b) VHMS deposits. The model Pb curve is from Stacey and Kramers (1975), =10.5

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Graphical Abstract
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Highlights

Pyrites from VHMS deposits tend to have higher Sn, Se, Cu, Pb, Bi and lower Ni relative to
Orogenic Au deposits.
Orogenic Au deposits could be subdivided based on association of Au with As or Te. Pyrites

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from Au-As ores generally have Pb/Bi>5, Se/Te>5, Pb/Sb<5 and Tl/Te>100 and the majority

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of Au is refractory (in pyrite structure). At the same time Au-Te association pyrites are
characterised by lower values of Pb/Bi, Se/Te and Tl/Te, higher values of Ag/Au, Pb/Sb and

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Au generally resides in inclusions of different compositions.
Our data can be used at the exploration stage to distinguish between VHMS vs Orogenic Au

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signatures.
For all studied deposits inclusion populations are summarised with implications for Au and
Ag deportment.

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Orogenic Au deposits from the Yilgarn mostly have multistage formation histories reflected
in the presence of multiple generations of pyrites.
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