Mineralium Deposita (2019) 54:657–670

https://doi.org/10.1007/s00126-018-0834-0

ARTICLE

Chalcophile element fertility and the formation of porphyry Cu ± Au

deposits
Jung-Woo Park 1,2 & Ian H. Campbell 2 & Sanjeewa P. K. Malaviarachchi 3 & Helen Cocker 2 & Hongda Hao 2 &
Suzanne M. Kay 4

Received: 21 February 2018 / Accepted: 5 August 2018 / Published online: 8 September 2018
# The Author(s) 2018

Abstract
Chalcophile element fertility, the chalcophile metal abundance in the source magma, is likely to be a critical factor for the
formation of porphyry Cu ± Au deposits. In this study, we provide evidence to support this hypothesis by comparing the platinum
group element (PGE) geochemistry of barren and ore-bearing Cu ± Au granitic suites. We report the PGE contents of three barren
volcanic and subvolcanic suites from Argentina and Japan and two Cu ± Au bearing suites from Indonesia and Chile. These
results are compared with those from previous studies of a porphyry Cu-only subvolcanic suite from Chile and three porphyry
Cu-Au-bearing suites from Australia and the USA. The barren suites are depleted in PGE abundances by the time of fluid
exsolution (< 0.1 ppb Pd and Pd/Pt < ~ 3), which is attributed to early sulfide saturation in a mid to lower crustal magma chamber.
In contrast, the Cu ± Au ore-bearing suites contain at least an order of magnitude higher PGE contents than the barren ones at
fluid saturation (up to ~ 10 ppb Pd and Pd/Pt of 0.1–40). They are characterized by late sulfide saturation, which allows both
chalcophile elements and sulfur to concentrate by fractional crystallization before volatile saturation. We suggest that plots of Pd/
MgO against Pd/Pt for igneous suites can be used to estimate chalcophile element fertility and distinguish between barren,
porphyry Cu, and porphyry Cu-Au granitoid systems. The positive correlation of these chalcophile element fertility indicators
and ore grades suggests that metal contents in magmas play an important role in controlling ore grade, particularly Au, in
porphyry Cu ± Au deposits.

Keywords Platinum group element . Porphyry deposit . Chalcophile element fertility . Sulfide saturation

Introduction
Editorial handling: W. D. Maier
Porphyry deposits are the primary source of the world’s Cu
Electronic supplementary material The online version of this article
and Au. The metals are interpreted to have been deposited
(https://doi.org/10.1007/s00126-018-0834-0) contains supplementary
material, which is available to authorized users. from magmatic fluids exsolved from the ore-associated
porphyries (Burnham 1967). They predominantly occur
* Jung-Woo Park above subduction zones, which has led to the suggestion
[email protected] that oxidized, water-rich subduction zone magmas may
play an essential role in ore formation. However, only a
1
School of Earth and Environmental Sciences, Seoul National limited number of porphyry suites host economic deposits.
University, Seoul 08826, South Korea Most are barren. There are several critical factors required
2
Research School of Earth Sciences, Australian National University, to form a large porphyry deposit: the metal endowment of
Canberra, ACT 2601, Australia the primary magma (McInnes et al. 1999; Mungall 2002),
3
Department of Geology, Faculty of Science, University of the metal content of the evolved magma at the time of
Peradeniya, Peradeniya, Peradeniya 20400, Sri Lanka volatile exsolution (Jenner et al. 2010; Wilkinson 2013;
4
Earth and Atmospheric Sciences, Cornell University, Park et al. 2015), the efficient transfer and precipitation
Ithaca, NY 14853, USA of the ore metals by the magmatic fluid (Richards 2003;
658 Miner Deposita (2019) 54:657–670

Audétat and Simon 2012; Wilkinson 2013), and the vol- Geological settings and samples
ume of magma and the duration of magmatic activity
(Chelle-Michou et al. 2017; Chiaradia and Caricchi Barren suites
2017). Metal transfer by degassing from a deep to shallow
magma chamber (Halter et al. 2005; Chiaradia et al. 2012) The Rachaite complex is a small calc-alkaline suite of ba-
and destabilization of magmatic sulfide (Nadeau et al. saltic andesite to dacite flows in northwest Argentina that
2010; Mungall et al. 2015) have also been suggested as erupted between 7.2 and 8.4 Ma (Kay et al. 2010). It in-
contributing factors in ore formation. cludes some of the least evolved lavas in the northern Puna
The chalcophile metal contents in a magma, the Volcanic Complex. Whole-rock major and trace element
chalcophile element fertility, at the point of fluid exsolu- geochemistry and Sr, Nd, Pb, and O isotopic data suggest
tion have been considered to be one of the key factors in that these northern Puna volcanic rocks crystallized from
the formation of porphyry Cu ± Au deposits (e.g., hybrid magmas that formed by mixing of mantle-derived
Wilkinson 2013), but there is no empirical evidence magmas with pelitic crustal melts in a 50 to 75 km,
supporting this hypothesis. This is mainly due to the dif- contractionally thickened crust (Kay et al. 2010). During as-
ficulties in measuring the metal contents of the magma cent, the magma ponded at a depth of 20–25 km and
from which the ore-forming fluid exsolved. The Cu and underwent further assimilation-fractional crystallization
Au contents of igneous rocks, particularly those associated (AFC). The Rachaite suite is associated with Pb, Zn, and Ag
with porphyry Cu ± Au deposits, are often remobilized by mineralization, but not with Cu or Au mineralization (Coira
hydrothermal alteration and do not reflect magmatic and de Brodtkorb 1995). Ten samples from Kay et al. (2010),
composition. which range from olivine-bearing basalt to glassy dacite, were
Recent studies on platinum group element (PGE) geo- analyzed for PGE and selected trace elements.
chemistry of subvolcanic rocks associated with porphyry The Cretaceous-Paleogene granitoids in the Japan arc are
Cu ± Au deposits (Cocker et al. 2015; Hao et al. 2017; classified into two groups, the reduced Ryoke and Sanyo
Lowczak et al. 2018) have suggested that the relative ilmenite-series and the oxidized Sanin magnetite-series, based
timing of fluid and sulfide saturation plays an important on their magnetic susceptibility (Kanaya and Ishihara 1973).
role in the formation of porphyry Cu ± Au deposits. The Ryoke and Sanyo suites are dominant in the southern parts
These studies used PGEs to indicate chalcophile element of the Japan arc where the basement is mainly a Jurassic accre-
fertility at fluid saturation. The PGEs are used in prefer- tionary complex. In contrast, the Sanin magnetite-series gra-
ence to Cu and Au for two reasons. First, their partition nitic rocks are mainly distributed over the northern part of
coefficients in immiscible sulfide melts are one to two or- the arc (Takagi 2004). There are no porphyry deposits as-
ders of magnitude higher than those of Cu and Au respec- sociated with the Cretaceous-Paleogene Japanese granit-
tively (Mungall and Brenan 2014). Second, because they oids (Ishihara 2007), whereas the Sanin magnetite-series
are appreciably less affected by alteration than Cu and Au, host Mo vein and Pb-Zn skarn deposits and the Sanyo-
they are more likely to preserve original igneous geochem- Ryoke granitoids are associated with W deposits and local-
istry (e.g., Crocket 2000; Park et al. 2016). ly a few minor Cu skarn deposits (Ishihara 2007). Nine
In this paper, we evaluate the role of chalcophile ele- granitic samples from the Sanin suite and 11 samples from
ment fertility in determining the ore-forming potential of the Sanyo-Ryoke suite were analyzed in this study. Sample
porphyry systems by comparing the PGE geochemistry of locations are reported in Electronic Supplementary
barren suites with that of economic Cu and Cu-Au suites. Material (ESM) Fig. 1 and ESM Table 1.
We measured PGE contents of three barren volcanic and
intrusive suites, the Rachaite suite from Argentina, and the Porphyry Cu ± Au suites
Ryoke and Sanyo ilmenite-series and Sanin magnetite-
series granitoids from Japan (Fig. 1). We also determined The Chuquicamata porphyries, which host one of the largest
PGE contents of subvolcanic rocks associated with the porphyry Cu deposits in the Andes, are located at the southern
Chuquicamata porphyry Cu (Chile) and the Grasberg por- end of the Chuquicamata Intrusive Complex. They intrude a
phyry Cu-Au deposits (Indonesia) for comparison (Fig. 1). pre-Cenozoic igneous, sedimentary, and metamorphic basement
These results will be discussed together with literature data along the late Eocene to Oligocene West Fissure strike-slip fault
from the El Abra porphyry Cu system in Chile, the zone (Ballard et al. 2001). The mineralized intrusive suite con-
Northparkes and Cadia Au-Cu porphyry systems in sists of the East, West, and Bench porphyries, which are
Australia (Cocker et al. 2015; Hao et al. 2017; Lowczak composed of granodiorite, monzogranite, and monzodiorite.
et al. 2018), and the Bingham porphyry Cu-Au system in Six of the least altered samples from Ballard et al. (2001) were
the USA (Maughan et al. 2002). selected for this study.
Miner Deposita (2019) 54:657–670 659

Fig. 1 Locations of volcanic and

subvolcanic rock suites included
in this study. The red circles
represent the locations of active
porphyry copper mines (Singer et
al. 2005). Thick light blue solid
lines represent subduction zone

The Grasberg Cu-Au porphyry is the world’s largest Au NIST 612 were ± 1 to 4% (1σ) depending on the elements.
producer (Cooke et al. 2005). The deposit is situated within Analytical accuracy is better than 10% for all elements,
the Grasberg-Ertsberg porphyry-skarn mineralized district in except for Cu (25%) and Cr (18%). The results are shown
the highlands of Papua, Indonesia. The Grasberg deposit is in ESM Table 3 where our measured values for NIST 612
associated with a group of brecciated diorites to quartz mon- are compared with the reference values from GeoReM da-
zonites intrusive units that form a pipe-shaped body, which tabase (Jochum et al. 2005).
intrudes the siliciclastic and carbonate units of the New
Guinea Limestone Group (MacDonald and Arnold 1994; PGE and Re
Leys et al. 2012). Five of the least altered samples from the
Main Grasberg Intrusions, which are most closely associated The whole-rock PGE and Re contents of the samples were de-
with the Grasberg porphyry mineralization, and Kali intru- termined by the Ni-sulfide fire assay-isotope dilution ICP-MS
sions were included in this study. method described by Park et al. (2012b). The results are reported
in Table 1. The sensitivities during analysis were ~ 3 × 105 cps/
ppb for mass 89, 140, and 205 using Agilent 7700x quadrupole
Analytical methods ICP-MS at ANU. The Ir, Ru, Pt, Pd, and Re contents were
measured by isotope dilution using the 99Ru/101Ru, 191Ir/193Ir,
195
Major and trace elements Pt/194Pt, 105Pd/108Pd, and 185Re/187Re ratios, respectively.
Rhodium contents were determined by the method described
Major and trace elements of some Rachaite samples were mea- in Meisel et al. (2003), which used the count rate of 103Rh and
106
sured by EPMA and LA-ICP-MS at ANU using the method of Pd assuming that the recovery rates of Rh and Pd were similar
Campbell (2003) and the results are reported in Electronic to each other during the analytical procedure. Molecular inter-
Supplementary Material (ESM Table 2). Synthetic glass beads ferences on PGEs by Ni, Cu, Zn, Co, Hf, Mo, Zr, and Ta argides
were prepared using 0.375 g of sample powder and 0.75 g of or oxides were monitored, and the effects of the interferences
lithium borate flux (12:22 Li2B4O7/LiBO2 mass ratio). The were corrected using measured oxide (0.3–0.4%) and argide
EPMA was performed by a CAMECA SX100 electron micro- production rate (0.003–0.006%). The interference on Ir, Pt,
probe in WDS mode with the beam conditions of 15 kV and and Re by the metal oxide and argide is negligible. The interfer-
20 nA. The LA-ICP-MS analysis was carried out at a laser ences on 105Pd and 108Pd by 65Cu40Ar, 68Zn40Ar, 102Zr16O,
repetition rate of 5 Hz with a spot size of 105 μm. Each spot 102
Mo16O, and 108Cd are corrected. The differences between
analysis consisted of 30 s of background measurement follow- data before and after the correction are < 2%. There is significant
ed by 40 s of sample ablation. The BCR-2g (USGS) standard interference on 101Ru by 61Ni40Ar. The differences for Ru ranges
was analyzed before and after analyses of 10 unknown sam- from 9 to > 100% due to low contents of Ru in samples.
ples. The NIST 612 was used to monitor quality control. Ca Procedural blanks were measured from the sample-free analysis.
concentrations measured by XRF (Kay et al. 2010) or The average procedural blanks and the method detection limits
EPMA (this study) were used as an internal standard to that are taken as three standard deviations of the procedural
determine the absolute concentrations of the elements. blanks are reported in ESM Table 4. The accuracy and precision
Analytical uncertainties obtained by multiple analyses of of the analyses were assessed by multiple measurements (n = 7)
660 Miner Deposita (2019) 54:657–670

Table 1 Platinum group element and Re concentrations in volcanic and subvolcanic rocks

Sample MgO Cu Ir Ru Rh Pt Pd Re Pd/MgO × 109 Pd/Pt

(wt.%) (ppm) (ppb) (ppb) (ppb) (ppb) (ppb) (ppb)

Volcanic rocks from the Rachaite suite, Argentina

P17-2A 1.80 10 0.0015 < 0.0014 0.0016 0.039 0.080 0.019 0.044 2.0
P17-2B 1.89 15 0.0007 < 0.0014 < 0.0003 0.019 0.047 0.071 0.025 2.4
P17-3 0.77 11 < 0.0003 < 0.0014 < 0.0003 < 0.005 < 0.009 < 0.012 0.012 1.8
P17-5 1.54 4 < 0.0003 < 0.0014 < 0.0003 < 0.005 0.014 0.050 0.009 2.7
P17-7 1.50 7 < 0.0003 < 0.0014 < 0.0003 < 0.005 0.016 < 0.012 0.010 3.1
RA95-1 2.20 11 0.0055 0.0086 0.0029 0.030 < 0.009 0.079 0.004 0.3
RA95-2 3.54 17 0.0007 0.0066 < 0.0003 0.015 0.032 < 0.012 0.009 2.1
RA95-3 3.66 9 0.0014 0.0047 0.0012 0.033 0.017 0.012 0.005 0.52
P17-4 4.42 30 0.0098 0.0020 0.0011 0.071 0.046 0.066 0.010 0.65
P17-6 5.83 4 0.0281 0.0179 0.0183 0.344 0.214 0.038 0.037 0.62
Granitoids from the Sanyo-Ryoke-Sanin magmatic belt, Japan
Sanyo-Ryoke magnetite-series
SJ3 0.42 n.d. 0.0009 0.005 0.002 < 0.018 0.035 0.064 0.082
SJ5 0.15 n.d. < 0.0002 0.006 0.001 < 0.018 0.004 0.116 0.024
SJ5 duplicate 0.15 n.d. 0.0003 0.004 < 0.0001 < 0.018 0.004 0.147 0.023
SJ6 0.96 n.d. 0.0004 0.003 0.0003 0.035 0.012 0.907 0.012 0.33
SJ6 duplicate 0.96 n.d. < 0.0002 < 0.003 0.0003 0.070 0.010 0.838 0.010 0.14
SJ8 0.50 n.d. 0.0006 0.006 0.002 0.019 0.009 0.120 0.019 0.49
SJ9 0.60 n.d. < 0.0002 < 0.003 0.0003 0.037 0.009 0.253 0.016 0.25
SJ10 3.10 n.d. 0.0006 0.008 0.005 0.025 0.020 0.234 0.007 0.80
SJ10 duplicate 3.10 n.d. 0.0004 0.030 0.008 0.023 0.020 0.402 0.007 0.89
SJ27 0.79 n.d. 0.0006 < 0.003 0.001 0.023 0.008 0.107 0.010 0.33
SJ39 1.32 n.d. 0.0008 < 0.003 0.003 < 0.018 0.015 0.033 0.012
SJ42-1 0.34 n.d. 0.0003 < 0.003 0.002 0.019 0.008 0.347 0.024 0.41
Sanin ilmenite-series
SJ11 5.98 n.d. 0.0002 0.004 < 0.0001 < 0.018 0.008 0.878 0.001
SJ11 duplicate 5.98 n.d. < 0.0002 0.007 0.0003 < 0.018 0.009 1.059 0.002
SJ17 1.00 n.d. 0.0004 0.008 0.008 < 0.018 0.014 0.256 0.014
SJ17 duplicate 1.00 n.d. 0.0003 < 0.003 0.003 < 0.018 0.011 0.263 0.011
SJ18 0.12 n.d. 0.0044 < 0.003 0.0003 0.037 0.006 0.118 0.048 0.16
SJ18 duplicate 0.12 n.d. 0.0005 0.005 0.001 0.025 0.006 0.148 0.052 0.25
SJ22 0.13 n.d. < 0.0002 < 0.003 0.000 0.148 0.008 0.098 0.060 0.05
SJ45 0.34 n.d. 0.0007 0.007 < 0.0001 0.080 0.002 0.441 0.005 0.02
SJ50 1.45 n.d. < 0.0002 0.011 0.002 < 0.018 0.004 0.021 0.003
SJ50 duplicate 1.45 n.d. < 0.0002 < 0.003 < 0.0001 < 0.018 < 0.001 0.015 0.0007
SJ51 5.91 n.d. 0.0003 < 0.003 0.001 0.042 0.019 0.319 0.003 0.45
SJ54 1.93 n.d. 0.0028 0.004 0.003 0.091 0.231 0.338 0.120 2.5
SJ60 0.18 n.d. < 0.0002 0.006 0.033 < 0.018 0.015 0.067 0.084
SJ60 duplicate 0.18 n.d. 0.0003 < 0.003 0.033 < 0.018 0.013 0.059 0.069
SJ61 1.05 n.d. < 0.0002 0.003 0.0005 0.037 0.005 0.513 0.005 0.15
SJ61 duplicate 1.05 n.d. 0.0005 < 0.003 0.0003 0.020 0.011 0.438 0.011 0.56
SJ64-1 0.37 n.d. 0.0004 0.010 0.0002 < 0.018 0.016 0.209 0.043
SJ64-1 duplicate 0.37 n.d. 0.0004 < 0.003 0.001 < 0.018 0.018 0.237 0.049
Subvolcanic rocks from the Chuquicamata porphyry Cu deposit, Chile
98-508 0.56 397 < 0.0003 < 0.0014 < 0.0003 0.019 0.057 1.00 0.102 3.0
98-511 0.63 2615 0.0030 0.0040 < 0.0003 0.036 0.071 1.62 0.113 2.0
98-503 0.64 11,213 < 0.0003 < 0.0014 0.0015 0.031 0.031 6.28 0.048 1.0
Miner Deposita (2019) 54:657–670 661

Table 1 (continued)

Sample MgO Cu Ir Ru Rh Pt Pd Re Pd/MgO × 109 Pd/Pt

(wt.%) (ppm) (ppb) (ppb) (ppb) (ppb) (ppb) (ppb)

98-601 0.42 1221 < 0.0003 < 0.0014 < 0.0003 0.094 1.88 4.79 4.485 20.1
98-505 0.59 600 < 0.0003 < 0.0014 < 0.0003 0.009 0.106 0.65 0.178 11.9
98-506 0.44 155 0.0025 < 0.0014 < 0.0003 0.015 0.080 0.79 0.182 5.2
Subvolcanic rocks from the Grasberg porphyry Cu-Au deposit, Indonesia
Gras11 1.36 0.310 1.8
Gras2 1.45 0.426 1.8
Gras12 1.69 0.548 2.7
Gras13 2.27 1.852 2.0
Gras14 1.77 3.147 8.9

Numbers in italics are calculated using the limit of detection values

n.d. not determined

of reference material TDB-1. The results are shown in ESM and thermodynamic studies (Wood 1987; Sassani and
Table 5. Reproducibility represented as the relative standard Shock 1990; Fleet and Wu 1993, 1995; Taran et al. 1995;
deviation (1σ) is < 10% for Pt, Rh, Ru, and Re for 14% for Pd Hanley et al. 2005; Simon and Pettke 2009), show that the
and 23% for Ir. The measured values are consistent with previ- PGEs are normally appreciably less mobile than Cu and Re
ously reported values within 2σ. in magmatic-hydrothermal fluids.
The relative mobilities of Cu and Pd in the felsic suites
considered in this study can be assessed from Fig. 2, which
Results and discussion shows a plot of Cu against Pd for the porphyries associated
with the Cu and Au-Cu deposits discussed in this paper.
The major and trace element and PGE contents of the Copper varies by × 100 in samples from the Chuquicamata
Chuquicamata Cu porphyry and Grasberg Cu-Au porphyry, Cu porphyry and by almost × 10,000 in El Abra samples with
obtained for this study, are presented in Table 1 and ESM no evidence of a correlated increase in Pd as might be expect-
Table 2. These results will be discussed and compared with ed if Pd was an important component in the hydrothermal
those of previous studies on the El Abra Cu porphyry in
Chile (Cocker et al. 2015), the Northparkes and Cadia Au-Cu
porphyries in Australia (Hao et al. 2017; Lowczak et al. 2018),
and the Bingham porphyry Cu-Au in the USA (Maughan et al.
2002).

Effect of alternation and mineralization

Because the emphasis of this study is on primary magmatic

processes, the samples analyzed were the freshest possible.
Nevertheless, some of the porphyry-related rocks used in
this and previous studies contain some hydrothermal sul-
fides, including hydrothermal Cu. Furthermore, some min-
eralized porphyry systems are known to contain hydrother-
mal Pd and Pt (Economou-Eliopoulos 2005 and references
therein), showing that hydrothermal fluids can mobilize Pd
and Pt and, in rare cases, porphyry Cu deposits can contain
up to 2400 ppb Pd (e.g., Skouries Cu porphyries, Greece;
Economou-Eliopoulos and Eliopoulos 2000). However,
Fig. 2 Plot of Pd against Cu for the ore-bearing and barren suites
empirical geochemical investigations (Yudovskaya et al. included in this study. The Cadia, Northparkes, and El Abra data are
2008; Tagirov et al. 2013; Zelenski et al. 2013, 2015; from Lowczak et al. (2018), Hao et al. (2017), and Cocker et al. (2015)
Park et al. 2016), supported by the results of experimental respectively
662 Miner Deposita (2019) 54:657–670

fluid. For example, the least mineralized sample from a

Chuquicamata (98–506), with 155 ppm Cu, and the most
mineralized sample (98–503) with 11,213 ppm Cu, have sim-
ilar PGE contents (Table 1). The Cu content of the samples
from the Au-Cu deposits vary by only × 10, so the influence of
increasing Cu on Pd is less clear. What is clear is that there is
no correlation between these elements and that samples from
the Cu-rich Northparkes deposit contain less Pd than those
from Cu-poor Cadia.

PGE geochemistry of ore-bearing suites

Figure 3 shows the Pd concentrations of the barren, Cu

porphyry and Cu-Au porphyry suites plotted against
MgO. The Pd contents of the volcanic and subvolcanic rocks b
associated with the Cadia and Northparkes Au-Cu suites are
generally > 3 ppb and remain enriched until late in magma
differentiation (< 1 wt.% MgO). The PGE contents of the
highest MgO samples are comparable to those of primitive
arc picrites and basalts (Fig. 3a), suggesting that they experi-
enced little (Cadia) or no (Northparkes) sulfide segregation
while fractionating in crustal magma chambers until a late
stage of magma differentiation (Hao et al. 2017; Lowczak et
al. 2018). Once the magma became sulfide-saturated PGE
concentrations dropped rapidly due to their strong affinity
for immiscible sulfide melts (D sul-sil PGEs > ~ 1 × 10 6 ;
Mungall and Brenan 2014). The Pd of the melt follows Cu
and Au because all of these elements are incompatible with
silicate and oxide minerals but strongly compatible with sul-
fide melts (e.g., Park et al. 2013, 2015). Therefore, the Cadia Fig. 3 a Plot of Pd against MgO for the ore-bearing and barren suites
and Northparkes magmas, which reached sulfide saturation included in this study. The colored lines are references, which show
late in their history, had sufficient Cu and Au at the time of variations in Pd during magma differentiation for each suite. The kinks
fluid exsolution to form Au-Cu ore deposits (Hao et al. 2017; in the reference lines show the point of sulfide saturation. Black dotted
arrows represent data below the detection limit. Black circles with letters
Lowczak et al. 2018).
are average Pd contents for arc basalts and picrites with MgO contents
The Pd contents of intrusive rocks associated with the between 8 and 14 from different localities. P = Pual Ridge basalt (sample
Chilean El Abra porphyry Cu deposit are seen to be con- MD3; Park et al. 2013), N = Niuatahi-Motutahi basalts (average of
sistently lower than those associated with the Australian samples DG26-2 and DG26-3; Park et al. 2015), A = Ambae picrite
(sample 68638; Park et al. 2012a), T = Tonga picrites (average of
porphyry Au-Cu deposits at the same MgO content (Fig. samples ND03-01 and 04-01; Dale et al. 2012). b Plot of Pd against
3a). The decrease in the abundance of Pd seen in the El MgO for the barren Wombin and Goonumbla suites from Northparkes.
Abra samples with < 2.5 wt.% MgO suggests that sulfide Reference lines for three of the ore-bearing suites in a are shown for
segregation was taking place before the onset of volatile comparison
saturation which was placed at 1.1–1.5 wt.% MgO by
Cocker et al. (2015). Cocker et al. (2015) further suggested
that the El Abra magma formed a BCu-only^ porphyry of magnitude higher than those in barren suites at a similar
deposit because small amounts of sulfide segregation dur- wt.% MgO. This implies that the Chuquicamata magma had a
ing fractional crystallization before fluid saturation deplet- chalcophile element budget similar to that of the El Abra mag-
ed the magma in the more chalcophile Au and not the less ma at fluid saturation, which can explain why Chuquicamata
chalcophile Cu (Dsul-silAu = ~ 1 × 104 and Dsul-silCu = ~ 1 × is also a Cu-only deposit.
103; Ripley et al. 2002; Mungall and Brenan 2014 and
references therein). PGE geochemistry of barren suites
The intrusive rocks associated with the Chuquicamata por-
phyry Cu deposit have similar Pd contents to the El Abra The PGE contents of barren rocks from the Rachaite suite,
porphyries with the contents in both being at least an order Argentina, and the Sanyo-Ryoke-Sanin suites, Japan, are
Miner Deposita (2019) 54:657–670 663

systematically depleted compared with the Cu ± Au ore- Rachaite case provides an example of how a chalcophile
bearing igneous suites at the same MgO content (Fig. 3a and element-rich mantle-derived magma became barren during
ESM Fig. 2). This suggests that either they have lost most of crustal evolution.
their chalcophile element budget by sulfide segregation at The Sanin-Sanyo-Ryoke granitoids, Japan, are charac-
depth or that they originated from a chalcophile element- terized by marked depletion in all PGEs, including the
poor source. The Pd and Pt contents of the Rachaite volcanic mafic samples with > 3 MgO wt.% (Fig. 3a), which sug-
rocks gradually decrease with decreasing MgO from 5.8 to gests that the Sanin-Sanyo-Ryoke magma may have either
0.8 wt.% (Fig. 3a and ESM Fig. 2). These trends are different undergone extensive sulfide segregation in a mid-lower
from those typically observed in sulfide-saturated magmatic crustal magma chamber or that the primary magma was
systems in which Pd and Pt drop rapidly after sulfide satura- chalcophile element-poor. There have been several sugges-
tion (Fig. 3 and ESM Fig. 2). As already noted, the Rachaite tions as to why there are no porphyry Cu deposits associ-
suite magmas were produced by mixing between mantle- ated with the Cretaceous-Paleogene intrusive rocks of
derived basaltic and pelitic crustal melts (Kay et al. 2010). southeastern Japan, including shallow erosion depth and
We performed mixing and AFC model following methods lack of thick continental crust (Qin and Ishihara 1998).
reported in Kay et al. (2010). The detailed conditions and However, our results show that the low chalcophile ele-
parameters for the AFC model are in ESM Appendix I. The ment fertility can be an important factor.
results show that the major and trace element geochemistry The Sanyo-Ryoke ilmenite-series granitoids are repre-
of the Rachaite suite is best explained by mixing between sented by high initial 87Sr/86Sr ratios between 0.7050 and
the mafic and the felsic end-members (Fig. 4 and ESM Fig. 0.7106 and high δ18O (> 8 ‰), suggesting the extensive
3). The Pd variations for most samples can also be as- involvement of crustal materials during their magma gen-
cribed to mixing between the two end-members, although eration (Ishihara 2007 and references therein). The primary
some show depletion in Pd/Nd and fall below the mixing magma of the Sanyo-Ryoke ilmenite-series granitoids is
curve, suggesting sulfide segregation may have occurred interpreted to have formed by mixing between mantle-
locally during mixing (Fig. 4). If magmas become locally derived basaltic magma and partial melts of carbonaceous
equilibrated with sulfide melt, Pd will decrease markedly meta-sedimentary rocks (Ishihara 2007). Assimilation of
with no corresponding change in Nd or Rb due to the high sedimentary carbon into the magma will lower its oxygen
Dsul-silPd > ~ 1 × 105 (Mungall and Brenan 2014), resulting fugacity and therefore its sulfur solubility. As a conse-
in low Pd/Nd and Pd/Rb ratios. quence, the Sanyo-Ryoke magmas are expected to leave
The Pd content of the mafic end-member, which is an order sulfide in their source region following partial melting
of magnitude lower than that of primitive arc magmas (Fig. and to reach sulfide saturation early in their evolution.
3a), suggests that the mafic magma has lost some chalcophile They are not prospects for Cu and Au mineralization.
elements before mixing with the felsic crustal magma. We The Sanin magnetite-series granitoids are interpreted to
suggest that the Rachaite primary magma lost its fertility have originated from mantle-derived basaltic melt that assim-
through a combination of early sulfide segregation in the low- ilated carbon-poor meta-igneous basement rocks (Ishihara
er crust and mixing with sulfide-saturated, a chalcophile 2007). Their relatively low δ18O (~ 5.5–8‰; Ishihara 2007),
element-poor felsic magma in a mid-crustal chamber. This compared to those of the ilmenite-series, imply lesser amounts
process may have depleted the Rachaite magma in Au and of crustal input during their genesis. The Sanin magnetite-
Cu, but not in Pb and Zn as it hosts Cu-poor, Pb-Zn series granitoids are oxidized relative to the ilmenite-series
polymetallic deposits (Coira and de Brodtkorb 1995). The because they had little interaction with carbon-rich materials

Fig. 4 Mixing, AFC and FC

modeling for plots of a Rb/Nd a b
and b Pd/Nd against Rb for the
Rachaite suite. Labeled markings
on AFC and FC curves represent
the percentage of melt (F)
remaining in a system. Numbers
on the mixing curves indicate the
percentage of the mafic end-
member in a system
664 Miner Deposita (2019) 54:657–670

during melting. This has led to the suggestion that they may have experienced the extensive fluid exsolution required to
have the potential for porphyry Cu deposits (Qin and Ishihara form a porphyry Cu deposit despite their chalcophile ele-
1998). However, our results show that their chalcophile ment budgets being comparable to those of some other
element depletion is similar to that of the ilmenite-series porphyry Cu ± Au suites. The Northparkes barren suites
granitoids, which suggests that either the primary Sanin show that although the chalcophile element fertility is a
magma was deficient in chalcophile elements or that it critical factor, it is not the only factor required to form a
was not sufficiently oxidized to exhaust all the sulfide porphyry Cu ± Au deposits.
phases in the source during melting.
Chalcophile element fertility indicator
Northparkes barren suites
This study shows that the PGE can be used as a tracer for Cu
The igneous rocks exposed around the Northparkes Au-Cu and Au and their geochemistry reflects changes in chalcophile
suites in Australia include two barren suites, the Goonumbla element fertility during magma evolution, confirming the re-
and Wombin Volcanics (Lickfold et al. 2003). These Middle to sults of recent studies on the PGE geochemistry of felsic-
Upper Ordovician lavas occur associated with monzodioritic intermediate igneous rock suites (Cocker et al. 2015; Park et
intrusions with a zircon U-Pb age of ~ 450 and 439 Ma, re- al. 2015; Hao et al. 2017; Lowczak et al. 2018).
spectively (Butera et al. 2001). These ages coincide with the We suggest that plots of Pd/MgO against Pd/Pt are indica-
main Au-Cu mineralization period of the Northparkes deposit, tors of chalcophile element fertility and can be used to test its
which is between 445 and 437 Ma (Lickfold et al. 2003). role in the formation of porphyry Cu ± Au deposits (Fig. 5).
Figure 3b compares Pd variations in the Goonumbla and Palladium contents are normalized by MgO to correct for
Wombin Volcanics with those of the Northparkes Au-Cu variations in Pd abundance caused by differences in fractional
suites. The progressive depletion in Pd with decreasing crystallization. The Pd/Pt ratio is used as a measure of the
MgO indicates that they have undergone early sulfide satura- amount of fractional crystallization before sulfide saturation.
tion and lost some Cu and Au to cumulus sulfide phases in a This is because prior to sulfide saturation, Pd behaves incom-
deep parental magma chamber (Hao et al. 2017). However, patibly whereas Pt typically is sequestered by Pt-Fe alloys
their Pd contents are still comparable to those of Cu- and Au- during fractionation of arc magma systems so that the Pd/Pt
Cu suites at < 3 wt.% MgO, implying some potential for ratio increases with fractionation (Fig. 6a; e.g., Park et al.
forming a porphyry Cu ± Au deposit. 2013, 2016). Once the magma becomes sulfide saturated, its
The evolution of the Goonumbla and Wombin suites are Pd/Pt ratio begins to fall because Pd is more chalcophile than
characterized by plagioclase-pyroxene fractionation whereas Pt (Fig. 6a; Park et al. 2016; Hao et al. 2017). The Northparkes
the Northparkes Au-Cu suites are dominated by plagioclase- and El Abra suites exhibit an abrupt decrease in Pd/Pt ratio
amphibole fractionation (Hao et al. 2017). They are also not after the onset of sulfide segregation (Fig. 6b). The seemingly
associated with porphyries or magmatic-hydrothermal alter- opposite trend for the Cadia suite may be ascribed to their
ation (Crawford et al. 2007). These observations suggest that open system evolution (e.g., magma replenishment,
Goonumbla and Wombin magmas were dry and may not Lowczak et al. 2018).

Fig. 5 Chalcophile element

fertility diagram showing the
difference between barren, Cu-
only, and Cu-Au suites. Samples
with < 2.5 wt.% MgO were
plotted except for the Cadia and
Bingham suites, for which
samples with < 3.2 wt.% MgO
and 1.4–4.6 wt.% MgO
respectively were used. The
barren, porphyry Cu, and
porphyry Cu-Au bearing suites
can be divided by dotted lines.
The gray field represents a range
of Pd/Pt values of primitive arc
magmas (Dale et al. 2012; Park et
al. 2012a, 2013, 2015)
Miner Deposita (2019) 54:657–670 665

a associated with andesitic intrusions (Lowczak et al. 2018;

Maughan et al. 2002).
Low Pd/MgO and Pd/Pt ratios distinguish most barren suites
from the ore-bearing suites (Fig. 5) and porphyry Cu from
porphyry Cu-Au suites. Most of the Cu-Au suites have Pd/Pt
ratios higher than those of primitive arc magmas, suggesting
they have experienced prolonged sulfide-undersaturated frac-
tionation or limited sulfide melt segregation (e.g., Cadia),
which increased their chalcophile element fertility. The
Goonumbla and Wombin barren suites have chalcophile ele-
ment fertility similar to those of porphyry Cu suites but do not
have Cu mineralization due to the low water content of their
magmas.

Implications for the porphyry ore-forming process

b
The seminal study of Cline and Bodnar (1991) and recent
numerical modeling studies (Chelle-Michou et al. 2017;
Chiaradia and Caricchi 2017) argued that intrusion volume
and duration of magma activity are the first-order factors con-
trolling metal endowments, and particularly metal-enriched
magmas are not essential for the genesis of economic porphy-
ry Cu deposits. Chelle-Michou et al. (2017) suggested that any
Bnormal^ hydrous arc magmas have potential to produce
fluids capable of forming porphyry Cu deposits and can form
large porphyry deposits (> 20 Mt Cu) if they have long-lasting
activity (> 1 Ma) and large volume (> 1000 km3) regardless of
metal contents in a magma.
Two of the critical factors that control the economics of a
porphyry system are its size and grade. The former is logically
controlled by the size of the magma event associated with the
Fig. 6 Plot of Pd/Pt against MgO for a the Niuatahi-Motutahi lavas,
Tonga rear arc (Park et al. 2015), and the Pual Ridge lavas, Eastern hydrothermal mineralization and the latter by a combination
Manus Basin (Park et al. 2013) and b the Northparkes, El Abra, and of chalcophile element fertility and efficient transfer of metals
Cadia suites. The Pd/Pt ratios of some Niuatahi-Motutahi lavas from the melt to the fluid. Therefore, the higher the Cu and Au
(diamonds with dotted line) are minimum estimation values obtained contents of the ore-associated magma at the time of volatile
using Pd data of each sample and Pt data of DG26-3 in Park et al.
(2015). Upward trending arrows result from Pt-rich alloy crystallization, saturation, the higher tenor of the ore for a given fluid/melt
downward trend lines sulfide melt segregation, and flat trend the absence partition coefficient for Cu and Au. The ore grade and tonnage
of both alloy and sulfide precipitation. The primitive upper mantle (PUM) data for the porphyry deposits considered in this study are
and primitive mantle (PM) values are from Becker et al. (2006) and presented in Table 2. The Northparkes and Grasberg magmas,
McDonough and Sun (1995) respectively. P = Pual Ridge basalt
(sample MD3; Park et al. 2013), N = Niuatahi-Motutahi basalts which have the highest chalcophile element fertility at fluid
(average of samples DG26-2 and DG26-3; Park et al. 2015), A = saturation (Fig. 5; Table 2), are associated with the highest Cu
Ambae picrite (sample 68638: Park et al. 2012a), T = Tonga picrites ore grades of > 1 wt.% among studied suites. Given the ton-
(average of samples ND03-01 and 04-01; Dale et al. 2012) nage of the Northparkes deposit is ~ 0.15 Gt, which is at least
an order of magnitude smaller than those of other porphyry
deposits in this study (Table 2), the magma volume involved
Bearing in mind that most porphyry Cu ± Au deposits in the formation of the Northparkes deposit may have been at
are hosted by highly evolved andesitic to rhyolitic rocks, least an order of magnitude smaller than other deposits.
only samples with < 2.5 wt.% MgO are plotted on Fig. 5, However, the Northparkes magma formed an economically
which assumes that these low MgO samples are the most significant porphyry Au-Cu deposit (1.6 Mt Cu and 70 t Au;
representative of the magma composition at the time of Cooke et al. 2007) due to high chalcophile element fertility.
fluid saturation. Relatively mafic samples were included Magma composition appears to be particularly controlling the
for the Cadia (< 3.2 wt.% MgO) and Bingham suites Au grade of a porphyry deposit. Figure 7 shows that the Au
(1.4–4.6 wt.% MgO), as their Cu ± Au mineralization is grades of porphyry ores are positively correlated with the Pd
666 Miner Deposita (2019) 54:657–670

Table 2 Tonnage, metal endowment, and grade of the porphyry Cu ± Au deposits included in this study and chalcophile element fertility indicators of
the associated suites

Deposit Tonnage (Gt) Cu (Mt) Au (t) Cu (wt.%) Au (g/t) Au/Cu grade Pd/Pt Pd/MgO References for t
he ore deposit data

Cu-only
El Abra 1.8 8.8 18 0.49 0.01a 0.02 1.2 0.2 1
Chuquicamata 7.5 66.4 301 0.55 0.04 0.07 7.2 0.9 2
Au-Cu
Northparkes 0.15 1.6 70 1.03 0.46 0.45 22 2.5 3
Grasberg 2.5 30.5 2604 1.13 1.05 0.93 3.4 1.3 2
Cadia 1.3 4.4 1050 0.31 0.74 2.39 4.5 0.9 3
Binghamb 3.2 28.5 1227 0.88 0.38 0.43 3.2 0.7 2, 4

References: 1 = Singer et al. (2008), 2 = Cooke et al. (2005), 3 = Cooke et al. (2007), 4 = Maughan et al. (2002)
a
Assumed value, no information due to Au is not present in detectable concentrations (Singer et al. 2008)
b
Pd/Pt and Pd/MgO values were calculated by average of Tick-52A, 59A, and 69A from Maughan et al. (2002)

content of the magma at fluid saturation, as determined from chalcophile than Cu, sulfide saturation leads to marked chang-
the Pd content of the ore-associated porphyries. This observa- es in the Au/Cu ratio of the melt. Figure 8 shows a theoretical
tion suggests that the Au grade of the studied deposits is con- model of the effect of sulfide saturation relative to fluid satu-
trolled by the Au contents of the magma at fluid saturation. ration using the Rayleigh fractionation equation after Cocker
Mantle-derived arc magmas can be expected to undergo et al. (2015). Models 1 and 2 assume sulfide saturation at 30
assimilation and fractional crystallization as they ascend and 70% fractionation, respectively, with an assumed sulfide
through the crust and this will modify their compositions. melt fraction of 0.2 wt.% (e.g., Hao et al. 2017; Park et al.
The principal processes that control the Cu and Au contents 2013, 2015) and gradual linear increase in the rate of sulfide
in magmas at volatile exsolution are the relative timing of fluid segregation over a 10% fractionation interval (e.g., Keays and
and sulfide saturation. Furthermore, because Au is more Tegner 2015). The sulfide melt and silicate melt partition co-
efficients (Dsul-silMetal) used for these models are 2 × 105 for
Pd, 1 × 104 for Au, and 1.3 × 103 for Cu (Mungall and Brenan
2014 and references therein). Model 1 represents the Rachaite
and Sanin-Sanyo-Ryoke cases (Fig. 8a). The magmas experi-
enced early sulfide saturation due to the assimilation of re-
duced C-rich crustal materials and lost most of their
chalcophile element and sulfur budget in cumulates within a
deep crustal magma chamber. Their chalcophile element fer-
tility was therefore low at the time of fluid saturation, which is
assumed to occur long after sulfide saturation. Magmas from
these suites are expected to be barren.
Model 2 represents suites associated with porphyry Cu ± Au
deposits, such as those included in this study. If fluid saturation
occurs at, or slightly after, 70% fractionation, the melts are
enriched in both Cu and Au and therefore have the potential
to form an Au-rich porphyry Cu deposit (Fig. 8b). It should be
noted that 70% fractionation of a sulfide-undersaturated magma
differentiation increases not only Cu and Au but also volatile
elements such as S and Cl in the melt by more than a factor of
Fig. 7 Plot of Au grade in the ore against Pd concentration in the melt at three times the initial values, which will significantly improve
fluid saturation. The large symbols represent the average of each suite. the ore grade and reduce the duration and volume of
References for the Au grades are given in Table 2. MgO contents of the magmatism required for economic porphyry Cu ± Au deposits.
samples used to constrain the Pd concentrations in the melt at fluid saturation
are 0.5–1.5 wt.% for the Northparkes (Hao et al. 2017), 1.0–1.5 wt.% for the
The PGE geochemistry of the Northparkes suite is consistent
El Abra (Cocker et al. 2015), 2.5–3.5 wt.% for the Cadia (Lowczak et al. with this model (Fig. 3; Hao et al. 2017) and the high Pd/MgO
2018), and 0.4–0.7 wt.% for the Chuquicamata suite (this study) and Pd/Pt ratios of the Grasberg samples (~ 1.5 wt.% MgO; Fig.
Miner Deposita (2019) 54:657–670 667

a melt to precipitate from the silicate melt (0.023 wt.%) be-

ing about a factor of ten less than other arc-related magmas
(~ 0.2 wt.%; Hao et al. 2017; Park et al. 2013, 2015) and
the R factor being less than DAu (R = silicate melt/sulfide
melt ratio = 14,000; Lowczak et al. 2018). The small frac-
tion of sulfide melt segregation may be due to destabiliza-
tion of the sulfide melt by interaction with volatile phases
(e.g. Mungall et al. 2015).
The Cu and Au grades of the 37 largest known porphy-
ry Cu and Au-Cu deposits (Cooke et al. 2005), including
those investigated in this study, are presented in Fig. 9.
For the giant porphyry Cu deposits (> 10 Mt Cu and Au/
Cu grade < 0.1 × 10−3), the Cu and Au grades are positive-
ly correlated regardless of the tonnage of each deposit,
suggesting that the duration and volume of magma activ-
b ity are not the primary controls on the ore grade. Note that
as the Cu grade decreases from 1.2 to 0.3 wt.%, the Au
grade shows almost two orders of magnitude depletion
from ~ 0.4 to ~ 0.002 g/t. Fluid composition and emplace-
ment depth have been considered to be significant factors
controlling the ore grade and Au/Cu ratio (Murakami et al.
2010). However, we suggest that this trend can also be
explained by variations in chalcophile element fertility
due to differences in the interval between sulfide and fluid
saturation in each deposit. To test this hypothesis, we cal-
culated the Cu and Au grades of the ores precipitated from
the fluid in equilibrium with the melt compositions pre-
dicted by model 2 assuming initial Cu and Au contents of
50 ppm and 4 ppb respectively (Lee et al. 2012; Park et al.

Fig. 8 Models simulating the Pd, Au, and Cu contents in the silicate melt
as a function of fractionation with sulfide saturation at a 30%
fractionation and b 70% fractionation. The single-headed arrow repre-
sents the assumed timing of sulfide saturation. The double-headed arrows
represent the assumed timing of fluid exsolution and the expected ore
types formed from the fluid

5) suggest that they also remained sulfide undersaturated until

the final stages of magma differentiation.
If fluid saturation occurs after sulfide saturation at ~ 80%
fractionation, the 10% fractionation interval between sulfide
and fluid saturation can deplete the melt in Au without remov-
ing a significant amount of Cu because the partition coeffi-
cient of Au into an immiscible sulfide melt is about ten times
higher than that of Cu (Mungall and Brenan 2014 and
references therein; Fig. 8b). The result is a BCu-only^ deposit
as seen in the El Abra (Cocker et al. 2015) and Chuquicamata
suites (this study). Fig. 9 Plot of Cu and Au grades in ores for giant porphyry deposits,
An apparent exception is Cadia, which reached sulfide sat- including those investigated in this study. Names of ore deposits with
uration at 6.8 wt.% MgO (Fig. 3a), well before fluid saturation tonnages of > 5 Gt are also shown. Data are from Cooke et al. (2005,
2007). The solid lines represent the Cu and Au grades of the ore formed
at ~ 3 wt.% MgO (Lowczak et al. 2018). Nevertheless, the from the fluid in equilibrium with the melt for model 2 in Fig. 7, assuming
Cadia magma retained enough Cu and Au to form a porphyry Dfluid-meltCu and Dfluid-meltAu of 50–120 and precipitation efficiency of
Au-Cu deposit due to a combination of the fraction of sulfide 50%. The dashed lines are fractionation (%) from model 2 in Fig. 7
668 Miner Deposita (2019) 54:657–670

2015). The trends of the ore grades of the giant porphyry supported by the Australian Research Council Discovery Grants to Ian
Campbell. We also acknowledge the support from the Korea Government
Cu deposits can be best explained if fluid saturation oc-
Ministry of Science, ICP and Future Planning (NRF-
curs between 70 and 82% fractionation in model 2, with 2015R1C1A1A01054101 and NRF-2017K1A1A2013180). Ryoji
Dfluid-meltCu and Dfluid-meltAu of 50–120 and precipitation Tanaka is thanked for his assistance for field trips in Japan.
efficiency of 50% (e.g., Chiaradia and Caricchi 2017). These
D values compare well with experimentally determined values Open Access This article is distributed under the terms of the Creative
(Simon et al. 2006; Simon et al. 2007). The results show that Commons Attribution 4.0 International License (http://
as the interval between sulfide and fluid saturation increases, creativecommons.org/licenses/by/4.0/), which permits unrestricted use,
the Au grade abruptly decreases with the slight decrease of the distribution, and reproduction in any medium, provided you give
appropriate credit to the original author(s) and the source, provide a link
Cu grade, supporting for the role of chalcophile element fer- to the Creative Commons license, and indicate if changes were made.
tility in controlling the ore grade of the giant porphyry Cu
deposits. Although this calculation has considerable uncer-
tainty introduced by the assumptions, which include the initial References
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