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Research article Geochemistry: Exploration, Environment, Analysis

Published Online First https://doi.org/10.1144/geochem2018-077

Assessing copper fertility of intrusive rocks using field portable

X-ray fluorescence ( pXRF) data
Ayesha Ahmed1*, Anthony J. Crawford2, Christopher Leslie2, Joshua Phillips1,
Tristan Wells2, Amos Garay1, Shawn B. Hood1 & David R. Cooke1
1
Transforming the Mining Value Chain, An ARC Industrial Transformation Research Hub, CODES, University of Tasmania,
Hobart, Tasmania, Australia
2
Centre for Ore Deposit and Earth Sciences (CODES), University of Tasmania, Hobart, Tasmania, Australia
C.L., 0000-0002-2867-1020; T.W., 0000-0001-5229-4619; S.B.H., 0000-0002-5680-7597; D.R.C., 0000-0003-3096-5658
* Correspondence: [email protected]

Abstract: Based on a global compilation of whole-rock geochemical data, Sr/Y and Sr/MnO are identified as effective
discriminators between ore-forming and unprospective intrusions in the porphyry Cu setting. Intrusive rocks are classified into
three fertility groups – prospective, unprospective and mixed-signal – designed to assist explorers as a discrimination tool,
narrowing the exploration search space in porphyry Cu districts.
Portable X-ray fluorescence ( pXRF) data of Sr, Y and MnO were collected on pulp powders and rock slabs from six
porphyry Cu (±Mo ± Au) districts. Pre- and post-mineralization intrusions from porphyry Cu districts have lower Sr/Y and Sr/
MnO values than syn-mineralization intrusions from the same districts, although absolute values are variable between districts.
pXRF data were compared to conventional whole-rock data to determine if pXRF data were appropriate substitutes for
conventional whole-rock methods of evaluating the ore-forming potential of intrusive rocks. pXRF data collected on pulp
material were found to be more accurate (within 16% of conventional methods) and more precise (<5% relative standard
deviation (RSD)) than those collected on intact rock slabs (within 37% of conventional methods and <24% RSD). These
differences are attributed to the grain size and mineral homogeneity of samples. Despite the low precision of pXRF analyses on
individual rock slabs (mean RSD of 24% Sr/Y and 32% Sr/MnO), the mean values for each sample plot in the expected fertility
field on the Sr/Y and Sr/MnO diagram. Our results demonstrate that in situ pXRF data collection provides an effective
discriminator of Cu fertility, and represents a powerful field exploration tool.
Supplementary material: Tabulated pXRF data for all samples including standards are available at https://doi.org/10.6084/
m9.figshare.c.4447769
Received 16 November 2018; revised 23 March 2019; accepted 25 March 2019

The ore-forming potential of intrusive rocks in the porphyry Cu Copper prospectivity diagrams can illustrate the potential of
environment can be assessed using bulk-rock compositions, intrusive rock suites to form porphyry and high-sulphidation ore
particularly variations in SiO2, Sr, Y, Mn, La and Yb contents deposits (Baldwin & Pearce 1982; Ballard et al. 2002; Richards &
(e.g. Baldwin & Pearce 1982; Lang & Titley 1998; Richards & Kerrich 2007; Loucks 2014). These diagrams use rock samples
Kerrich 2007; Loucks 2014). Magmas associated with porphyry Cu from known areas of mineralization to produce thresholds that
mineralization are typically oxidized and hydrous (Ballard et al. correspond to prospective or unprospective compositions. Global
2002; Mungall 2002; Cooke et al. 2005; Sillitoe 2010; Sun et al. compilations of whole-rock geochemical data independently show
2013) and are associated with arc rocks that have characteristically that, relative to unmineralized magmatic rocks, ore-forming
high La/Ybn and Sr/Y values, and low Mn contents (Baldwin & intrusions in subduction-related tectonic environments are char-
Pearce 1982; Thiéblemont et al. 1997; Lang & Titley 1998; acterized by elevated Sr, low Y and low MnO (Baldwin & Pearce
Richards & Kerrich 2007; Richards et al. 2012 ; Loucks 2014). 1982; Richards & Kerrich 2007; Loucks 2014). Existing studies
Amphibole can accommodate significant amounts of Mn and Y into using data for these elements have proposed fertility discrimination
its structure (Greenland et al. 1968; Sisson 1994). High magmatic diagrams using Sr/Y v. Y, Sr/Y v. SiO2 and Y v. MnO (Baldwin &
water contents (≥4 wt%) promote amphibole formation and early Pearce 1982; Loucks 2014). In this study, we combine the indices
amphibole fractionation (or garnet during high-pressure fraction- from several studies into a single bivariate plot of Sr/Y v. Sr/MnO.
ation), resulting in progressively lower Mn and Y contents as Traditional Cu prospectivity diagrams use geochemical data
hydrous magmas evolve (Baldwin & Pearce 1982; Richards & collected by conventional methods such as inductively coupled
Kerrich 2007). Under the same hydrous conditions, plagioclase plasma mass spectrometry (ICP-MS), inductively coupled plasma
crystallization is supressed, resulting in evolved magmas with high emission spectrometry (ICP-ES) or X-ray fluorescence (XRF; e.g.
Sr contents (Richards & Kerrich 2007; Richards 2011). Under Baldwin & Pearce 1982; Richards & Kerrich 2007; Loucks 2014).
oxidized conditions, titanite and/or magnetite are stable (Richards The cost and time of conventional laboratory analyses may limit the
2003; Costa et al. 2004; Loader et al. 2017). Progressive number of samples analysed. These conventional whole-rock datasets
fractionation of hornblende and titanite ± magnetite ± garnet are typically interpreted after field exploration has been conducted
increases the La/Ybn and Sr/Y ratios of magmas (Sisson 1994; and analytical results have been returned from the laboratory. As
Castillo et al. 1999; Bachmann et al. 2005; Rooney et al. 2011; such, the results do not necessarily provide real-time insight or inform
Loucks 2014). decision making during field sampling or drilling programmes.

© 2019 The Author(s). Published by The Geological Society of London for GSL and AAG. All rights reserved. For permissions: http://www.geolsoc.org.uk/
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A. Ahmed et al.

Fig. 1. World map showing the locations of the

case-study districts discussed in this paper:
(1) Yerington porphyry Cu (±Mo-Au) district,
USA; (2) Resolution porphyry Cu-Mo deposit,
USA; (3) Las Bambas, Cu-Fe skarn district,
Peru; (4) Cadia Cu-Au district, Australia;
(5) Northparkes Cu-Au district, Australia; and
(6) Cowal Cu-Au district, Australia. Map URL:
https://eoimages.gsfc.nasa.gov/images/
imagerecords/74000/74167/world.200410.
3x5400x2700.jpg. Photo credit: Stöckli (2004).

In this paper, we show that: (1) based on a global compilation of Wright 1988) and Bear quartz monzonite; syn-mineralization units
data, whole-rock values of Sr/Y and Sr/MnO can effectively include the Luhr Hill granite and associated granite porphyry dykes
discriminate between ore-forming and unprospective intrusions in (168.5 ± 0.4 Ma; Dilles & Wright 1988). The Shamrock monzonite
the porphyry Cu environment and (2) portable X-ray fluorescence post-dates Cu mineralization in the district (165.8 ± 0.4 Ma; Dilles &
( pXRF) data, calibrated to conventional whole-rock data, can be Wright 1988).
used in place of conventional whole-rock analytical data to inform
the Sr/Y v. Sr/MnO Cu prospectivity discrimination diagram. We Resolution, USA
present comparisons of conventional ICP-MS/ICP-ES and pXRF
results from six mineralized districts: (1) the Yerington porphyry Cu The Resolution porphyry Cu deposit is in the Superior district, which
(±Mo-Au) district, USA; (2) the Resolution porphyry Cu-Mo occurs along a prominent ENE-trending, 50 km long belt of porphyry
deposit, USA; (3) the Las Bambas Cu-Fe skarn district, Peru; (4) the Cu deposits in Arizona, USA (Fig. 1; Ballantyne et al. 2003). In
Cadia Cu-Au district, Australia; (5) the Northparkes Cu-Au district, 2012, Resolution had an inferred resource of 1787 Mt at 1.54% Cu
Australia; and (6) the Cowal Cu-Au district, Australia. To and 0.035% Mo (Hehnke et al. 2012). The deposit is concealed
demonstrate that pXRF data can be acquired directly from beneath 1.5 km of post-mineralization cover and only minor volumes
unprocessed rocks in the field, we evaluated the accuracy and of felsic intrusive rocks are exposed at the surface. The pre-
precision of pXRF data collected from both pulp material mineralization intrusion is a 2 by 3 km quartz diorite stock that
(120 mesh) and intact rock slabs (up to 0.5 cm grain size) to those intruded Proterozoic and Paleozoic rocks 6 km NW of Resolution, at
of conventional ICP-MS/ICP-ES whole-rock data. the Silver King prospect. The quartz diorite stock is intruded by a
smaller porphyritic intrusion of dacitic composition. Throughout the
district, the pre-mineral sequence of Proterozoic to Paleozoic rocks
Geology of pXRF sample locations has been crosscut by narrow dacitic dykes and sills, which are
Figure 1 shows the geographical location of each ore deposit district particularly well-developed in the Magma mine (Hammer & Peterson
from which samples were analysed using pXRF. The deposit type 1968) and at Resolution (Manske & Paul 2002; Hehnke et al. 2012).
and igneous geochronology of the samples used in this study are About 12 km to the NE of Resolution is the polyphase Schultze
described in Table 1. Where absolute (radiometric) ages of Granite. The Schultze Granite is composed of up to 15 texturally
intrusions were unavailable, the relative age of each intrusion distinct, but chemically indistinguishable, intrusive phases (Creasey
( pre-, syn- or post-mineralization) was determined based on cross- 1980, Stavast 2006). The Schultze granite is widely interpreted as the
cutting relationships identified by field mapping or in drill cores. causative pluton for mineralization in the local Globe–Miami and
Superior districts (Creasey 1980; Stavast 2006; Maher 2008).

Yerington district, USA Las Bambas, Peru

The Yerington mining district (Yerington) in western Nevada, USA The Las Bambas Cu skarn district in southern Peru is within the
(Fig. 1), is a well-mapped, well-studied area that contains porphyry Andahuaylas–Yauri belt (Fig. 1) and consists of three deposit
Cu and skarn deposits (Fig. 1; Einaudi 1977; Harris & Einaudi centres: Chalcobamba, Ferrobamba and Sulfabamba. The total Cu
1982; Proffett & Dilles 1984; Dilles 1987; Dilles & Einaudi 1992). resource for the Las Bambas district is 1873 Mt at 0.85% Cu (2017;
The combined geological resource and production of the district is www.mmg.com). Copper skarn mineralization is associated with
in excess of 6 Mt Cu in sulphide ores and >100 Mt Fe in oxide ores late Eocene quartz diorite plutons, including the Jahuapaylla
(Dilles & Proffett 1995). The Ann Mason deposit in the Yerington monzodiorite, Ferrobamba monzodiorite and La Cresta monzodior-
district has a combined measured and indicated mineral resource of ite (Perelló et al. 2003; Cannell et al. 2017). Copper skarn ore from
4.49 Mt Cu, 84.8 kt Mo and 37.7 t Au (Kulla et al. 2015). Ann the main mineralization event is crosscut by post-mineralization
Mason, and other porphyry and skarn Cu deposits in the district quartz monzodiorite porphyry stocks and swarms of monzogranite
(e.g. Casting Copper and Ludwig), are associated with the Luhr Hill and monzodiorite dykes. The Pioneros quartz diorite stock and the
granite and granite porphyry dykes, part of the Yerington batholith Rayusco diorite, to the north of Ferrobamba, are unmineralized and
(Proffett & Dilles 1984; Dilles 1987; Dilles & Wright 1988). The pre-date mineralization at Las Bambas (Cannell et al. 2017).
Yerington batholith is a medium- to high-K calc-alkaline polyphase
intrusive complex (Dilles 1987). The batholith intruded a sequence of
Cadia, New South Wales, Australia
sedimentary and volcanic rocks over a span of 1 myr (Dilles &
Wright 1988). Intrusive phases include the pre-mineralization The Cadia Valley district, central New South Wales, Australia, is
McLeod Hill quartz monzodiorite (169.4 ± 0.4 Ma; Dilles & one of the largest and most metal-endowed alkalic porphyry camps
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Table 1. Summary of the intrusive geological history from the deposit locations used in this study showing pre-, syn- and post-mineralization intrusions in each district

Pre-mineralization rocks Syn-mineralization rocks Post-mineralization rocks

Assessing porphyry copper fertility with pXRF

Geological site Deposit type Country Unit Age (Ma) Unit Age (Ma) Unit Age (Ma) Reference
Yerington Porphyry Cu-Mo (±Au) USA McLeod Hill 169.4 ± 0.4 Luhr Hill granite and 168.5 ± 0.4 Shamrock monzonite 165.8 ± 0.4 Dilles (1987) and Dilles & Wright (1988)
monzodiorite granite porphyry
Bear monzonite Banik et al. (2017)
Resolution Porphyry Cu (±Mo) USA Silver King quartz diorite 74 Schultze granite 67–61 - - Creasey (1980)
Las Bambas Skarn Cu-Fe Peru Pioneros diorite 38.1 Jauapaylla monzodiorite 33.8 - Cannell et al. (2017)
Rayusco diorite Ferrobamba quartz monzodiorite -
La Cresta quartz monzodiorite -
Cowal Porphyry-epithermal Cu-Au Australia E43 diorite Marsden granodiorite Muddy Lake diorite Zukowski (2010) and Rush (2013)
E43 quartz diorite E43 quartz feldspar porphyry E42 monzonite
E43 granodiorite Lake monzonite
Marsden quartz diorite Lake diorite
Marsden granodiorite
E41 monzonite
Dewars diorite
Northparkes Porphyry Cu-Au Australia - - Porphyry 1 444–439 Trachyte - Lickfold et al. (2003)
- - Porphyry 2 Monzonite -
- - Biotite quartz monzonite
Cadia Porphyry Au-Cu Australia Turnbridge Wells diorite - Cadia Far East monzonite - - - Wilson (2003)
Cadia Hill monzonite - - - -
Cadia Quarry monzonite - - - -
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A. Ahmed et al.

in the world (Fig. 1; Wilson 2003; Cooke et al. 2007; Harris et al. Yandera deposits); (2) Cu-Au (Panguna, Waisoi, Grasberg,
2014; Fox et al. 2015). The Cadia province has a mineral resource of Skouries and Bajo de la Alumbrera); (3) Cu-Mo (Bagdad, Ray-
8.7 Mt Cu and 43 Moz Au (2016; www.newcrest.com.au) and Christmas, Safford, El-Teniente; Fujiawu, Tongchang, Tuwu-
includes four porphyry Au-Cu deposits, Cadia Hill, Cadia Quarry, Yangdong, Baogotu, Zhanaga, Yulong, Malasongduo,
Ridgeway and Cadia East, and two related skarn deposits, Big Cadia Duoxiasongduo, Mongzong, Yerington, Los Pelambres, El Abra,
and Little Cadia. This Ordovician alkalic porphyry mineralization Qulong, Riduo and El Salvador); (4) Cu-Mo-Au (Chikang,
(c. 440 Ma; Wilson et al. 2007) is associated with composite Cevizlidere, and Altar); and (5) Au (Shuteen). The comparator
monzonite to diorite dykes and plugs and stocks, and some barren sample suite is a compilation of data from the Sunda and
mineralization also occurs locally in the host Forest Reef volcanic Surigao arcs and the Collahuasi deposit. The Sunda Arc dataset was
rocks. The Cadia Intrusive Complex hosts the Cadia Hill and Cadia selected because it represents a typical mid-crustal thickness arc
Quarry deposits and varies from diorite to quartz monzodiorite, but magma not associated with any known porphyry Cu (or other)
is dominantly composed of porphyritic monzonite stocks (e.g. the mineralization (Soller et al. 1982; Wölbern & Rümpker 2016).
Cadia Hill stock). The Ridgeway deposit, 2.5 km NW of Cadia Hill,
is hosted in monzonites of the Ridgeway Intrusive Complex, and in
ICP-MS/ICP-ES
the Forest Reef volcanics and underlying Weemalla Formation.
Conventional whole-rock geochemical data from 82 rock chip and
Cowal District, Australia drill core samples were evaluated from the six case-study areas
(Yerington, Resolution, Las Bambas, Cowal, Cadia and
The Cowal Gold mine is located c. 40 km NE of West Wyalong, Northparkes). These rock samples were analysed by ICP-MS/ICP-
central New South Wales, Australia (Fig. 1). Here, the Cowal ES for their major and trace element compositions. Samples from
Igneous Complex hosts several Au deposits and prospects, with two each case-study area were analysed separately, as part of larger
dominant mineralization styles: (1) structurally controlled, epither- analytical batches; however, analytical methods were consistent
mal-related Au ± Ag mineralization; and (2) bulk-tonnage porphyry between sample batches. Whole-rock geochemical analyses were
Au-Cu (Zukowski 2010). One of the best-known porphyry deposits completed at either Bureau Veritas Mineral Laboratories in
is Marsden with an indicated and inferred mineral resource of Vancouver, Canada, or ALS Laboratories in Perth, Australia. The
180 Mt at 0.38% Cu with 0.20 g t-1 Au (www.evolutionmining. methods followed at each lab were similar. Bureau Veritas
com.au). The Cowal Igneous Complex is cut by a poorly defined analytical methods are described here. Samples were jaw-crushed,
WNW-trending structure, the Marsden lineament, which juxtaposes split and pulverized. The pulverized samples were dried and loss on
the volcanic and sedimentary epithermal host rocks to the north with ignition was determined from changes in sample weight before and
plutonic rocks that host the porphyry Cu-Au deposits to the south. after heating. A total of 43 major and trace elements were analysed
using the lithium borate fusion package LF200. A 0.2 g powdered
Northparkes, Australia sample was fused in a graphite crucible with 1.5 g of LiBO2/LiB4O7
flux at 980°C for 30 min and then dissolved in 5% HNO3. Major
The Northparkes district in central western New South Wales
elements, including MnO, were determined using a Jarrel Ash
(Fig. 1) has current reserves at 107.5 Mt at 0.81% Cu-equivalent
AtomComp Model 975/Spectro Ciros Vision ICP-ES. Trace
grade containing 667 kt Cu (http://www.chinamoly.com).
elements, including Sr and Y, were analysed using a Perkin-Elmer
Economic Cu-Au mineralization is associated with discrete alkalic
Elan 6000 or 9000 ICP-MS. Laboratory quality assurance and
pencil porphyries emplaced in the late Ordovician (c. 444–439 Ma;
quality control procedures were employed with digested standards
Lickfold et al. 2003, 2007; Crawford et al. 2007). Host rocks to
run every 68 samples and a digestion duplicate run every
porphyry Cu deposits include the 445–436 Ma Wombin volcanics,
15 samples, with recalibration of the instrument every 68 samples.
a series of high-K calc-alkaline to shoshonitic volcaniclastic
Carbon and sulphur contents were measured by Leco analysis.
sedimentary rocks and interbedded lavas that, along with the
Nelungaloo and Goonumbla Volcanics, comprise the Goonumbla
Volcanic Complex (Heithersay & Walshe 1995; Lickfold et al. pXRF workflow
2003, 2007). The Nelungaloo Volcanics were intruded by
The pXRF data collection workflow used in the current study was
monzodiorite porphyries with sub-economic mineralization at
modified from Fisher et al. (2014) and Gazley & Fisher (2014) and
481 ± 4 Ma (early Ordovician; Simpson et al. 2005; Glen et al.
follows a two-part process: (1) data collection and (2) data
2007). The Nelungaloo Volcanics are overlain by the Goonumbla
calibration. An Olympus Vanta M series pXRF instrument was
Volcanic Complex on a low-angle unconformity (Krynen et al.
used, with a 50 kV Rh tube (instrument number 801231). All the
1990; Lickfold et al. 2007). A series of basaltic trachyandesite and
pXRF data were collected in Geochem mode. At the beginning of
augite monzonite porphyry dykes post-date mineralization in the
each analytical session, the pXRF unit was initialized to a
Northparkes district (Lickfold et al. 2003).
calibration disc provided by the unit manufacturer. A series of in-
house matrix-matched standards were used for quality assurance
Methods and quality control: the Priory monzonite (TAS-MONZ), diorite
(TAS-DIOR), Grant Point granite (TAS-GRAN) and dolerite (TAS-
Sources of data for Sr/MnO v. Sr/Y diagram
BAS). Standards and/or a silica blank were run at a minimum of
Conventional whole-rock geochemical data of intrusive rocks (ICP- every 20 analyses, and at the beginning and end of each analytical
MS/ICP-ES and XRF) from a wide variety of porphyry settings session. Standard materials were collected from the St Helens region
were compiled from both published work and PhD theses. Samples of Tasmania by Cocker (1971) and prepared at the University of
included in this dataset were visibly unaltered based on petrographic Tasmania. To make the pressed powder standard mounts used in the
and field observations made by the respective authors. Following current study, standard samples were jaw-crushed to <6 mesh
the methodology of Loucks (2014), fertile sample suites were diameter. Material was then split and lots of 200 g were pulverized
selected from representative syn-mineralization intrusive rocks from in a tungsten carbide mill to 120 mesh and pressed into 30 cm
porphyry and high-sulphidation ore deposits. Districts and diameter round mounts.
associated data were divided into groups based on economic pXRF data were collected on both loose pulp material (120 mesh)
metal content: (1) Cu (the Koloula, Luzon, Frieda River and in press cups through propylene film and intact rock slabs. To
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Assessing porphyry copper fertility with pXRF

Fig. 2. Whole-rock geochemical data compilation of samples from barren ( pre- or post-mineralization intrusions) and syn-mineralization intrusions from
porphyry Cu (±Mo-Au) deposits. Three prospectivity fields are shown: prospective (associated with porphyry Cu, skarn or epithermal mineralization),
unprospective ( pre- or post-mineralization intrusions, or not associated with any known porphyry Cu, skarn or epithermal mineralization) and mixed signal
(overlap between prospective and unprospective fields). Fields were calculated based on the 95th percentile of data for the fertile and barren datasets
respectively. Altar: Maydagán et al. (2014); Bagdad: Lang & Titley (1998); Bajo de la Alumbrera: Ulrich & Heinrich (2001); Baogutu: Shen et al. (2009);
Batu Hijau: Garwin (2000); Bayugo: Braxton (2007); Luzon: Imai (2002); Hedenquist et al. (1998); Boyongan: Braxton (unpublished data); Cevizlidere:
̇
Imer (2015); Imer et al. (2015); Chikang: Jiang et al. (2015); Collahuasi: Sellés et al. (2009); Copper Basin: Lang & Titley (1998); Copper Creek: Lang &
Titley (1998); Duoxiasongduo: Zengqian et al. (2003); El Abra: Cocker et al. (2015); El Salvador: Lee (2008); El Teniente: Cannell et al. (2005); Vry et al.
(2010); Ertsberg: McMahon (1994); Frieda River: Mason & McDonald (1978); Whalen et al. (1982); Fujiawu: Wang et al. (2005); Grasberg: McMahon
(1994); Koloula: Chivas (1978); Los Pelambres: Reich et al. (2003); Malasongduo: Zengqian et al. (2003); Panguna: Ford (1976); Qulong: Yang et al.
(2009), Hu et al. (2015); Ray and Christmas: Lang & Titley (1998); Riduo: Zengqian et al. (2003); Safford: Lang & Titley (1998); Sanbujiala: Jiang et al.
(2015); Shuteen: Batkhishig et al. (2010); Sierrita: Anthony & Titley (1988); Skouries: Frei (1995); Sunda Arc: Whitford (1975); Whitford et al. (1981);
Wheller (1986); Wheller & Varne (1986); Wheller et al. (1987); Stolz et al. (1990); Tongchang: Wang et al. (2005); Tuwu-Yandong: Zhang et al. (2006);
Waisoi: Imai et al. (2007); Yandera: Watmuff (1978); Yulong: Jiang et al. (2008); Zengqian et al. (2003); Zhanaga: Zengqian et al. (2003).

overcome the natural grain-size heterogeneity inherent to rock slabs, of the same sample. This process is referred to herein as niche
three separate analyses were collected on each rock slab sample and sampling. Spot locations were selected to avoid visible alteration,
averaged. Two to three analyses were collected on pulp material veins and weathering where present.
(Supplementary material B). Averaging of multiple pXRF analyses Calibrations curves for Sr, Y and MnO were created using
is routinely applied to overcome the low sampling precision of regressions of the pXRF results on the four matrix-matched
pXRF data on heterogeneous material (e.g. Potts et al. 1997; standards v. conventional whole-rock data for the standards to
Holding 2014; Le Vaillant et al. 2014; Simandl et al. 2014). provide correction factors for the pXRF data. Two sets of calibration
Standard deviation values from the mean (1σ) were calculated to curves were devised to calibrate data collected on different sample
evaluate the sampling precision of multiple analyses from the same media. The pXRF data collected directly on rock slabs were
sample. On rock slabs, the X-ray beam was placed on different parts calibrated to standards placed directly on the pXRF detector,
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A. Ahmed et al.

Fig. 3. Standard values for selected elements, Sr (a), MnO (b) and Y (c), ( y-axis) and pXRF values (x-axis). Equations for each regression line are shown in
Table 2. Calibration curves (regression lines) for the pressed-powder standard placed directly onto the pXRF detector were used to calibrate the pXRF data
collected on intact rocks slabs. Calibration curves for the pressed-powder standards with a thin (4 µm) propylene film placed between the standard and the
pXRF detector were used to calibrate the loose pulp material prepared in press cups.

whereas pXRF data collected on loose pulp material (measured (Table 2). Differences between all the pXRF and conventional
through 4 µm thick propylene film) were calibrated to standards also laboratory datasets are consistently offset, as shown by the R 2 values
analysed through 4 µm thick propylene film. in each diagram (R 2 = 0.97–1; Table 2). High positive correlation
values between the XRF and pXRF results for Mn and Sr from this
Results study compare favourably with similar results from Piercey &
Devine (2014) (R 2 > 0.8).
Global compilation of conventional whole-rock data
A compilation of conventional whole-rock data is presented on a Precision and accuracy of pXRF data
diagram of Sr/Y v. Sr/MnO in Figure 2. Samples from the barren All the instrument precision data (instrument error) are tabulated in
Sunda Arc, Surigao and Collahuasi reference suite have low Sr/Y Supplementary material B. Mean values for the analytical errors
(<50) and low Sr/MnO (<13 250) values. Samples of syn- associated with pXRF measurements of Sr, Y and Mn are presented
mineralization intrusive rocks have overall higher Sr/Y and Sr/ in Table 3. Analytical errors for Sr and Mn are below 2.1% of the
MnO values than samples from intrusions not associated with average values for these elements in samples analysed in the current
mineralization (Fig. 2). Correlation between the Sr/Y and Sr/MnO study (Table 3). Yttrium has the highest analytical error (7.6%;
values, and the empirical prospectivity of intrusions, defines Table 3) due to the low concentrations of Y in some samples, which
three fields on the Sr/Y v. Sr/MnO diagram shown in Figure 2: approach the analytical detection limit of the pXRF (near 1 ppm).
(1) prospective, (2) unprospective and (3) mixed signal. These fields Analytical precision was also evaluated by analysing the same spot
were calculated from the 95th percentile of data associated with ore- on a rock slab ten times (Fig. 4; Table 4). This exercise resulted in a
forming intrusions ( prospective field) and those not associated with RSD value of 0.9% Mn, 0.4% Sr and 5.9% Y (Table 4).
known mineralization (unprospective field). Samples from Bajo de The sampling precisions of the pXRF data on rock slabs and pulp
la Alumbrera and some samples from Bayugo, Malasongduo, material were evaluated by calculating the 1σ error (standard
Mongzong, Baogutu, Koloula and Batu Hijau plot in the mixed deviation from the mean value of all the analyses collected on a
signal field. Two samples of intrusions associated with known sample). These values are listed in Tables 5 and 6. RSD values were
porphyry Cu deposits, Resolution and Duoxiasongduo, plot near calculated to assess the magnitude of variation between multiple
the upper Sr/MnO boundary of the unprospective field (Fig. 2). All analyses on the same sample relative to the mean and are included in
the other samples associated with porphyry Cu mineralization plot
in the prospective field with high Sr/Y (>50) and high Sr/MnO
Table 2. Calibration factors and correlation coefficients applied to pXRF
(>13 250). data

Olympus Vanta
pXRF
Element Factor R2
Calibration of pXRF data to ICP values
Direct measurement
Calibration curves and associated calibration factors for MnO, Sr
Sr 1.00 1.00
and Y based on the conventional XRF data and pXRF data collected
MnO 1.01 0.99
on the same standards are presented in Figure 3 and Table 2. The
Y 0.97 0.98
associated XRF and pXRF data for standards are tabulated in
Through propylene film
Supplementary material A. The concentrations of MnO, Sr and Y
Sr 1.02 1.00
analysed by pXRF are within 15% of the values for both standards MnO 1.11 1.00
sampled by direct measurement and through propylene film. These Y 0.87 0.98
values correspond to calibration factors between 0.85 and 1.15
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Assessing porphyry copper fertility with pXRF

Table 3. Analytical precision of Sr, Y and Mn measured by pXRF (>100), consistent with its classification as a syn-mineralization
instruments compared to average values of samples analysed in this study intrusion. Samples of the post-mineralization Shamrock monzonite
Olympus Vanta (n = 271) plot in the ‘mixed’ prospectivity field; however, these samples
returned lower Sr/MnO (<11 000) and Sr/Y (<100) values
Mean value* (ppm) Error (ppm) Error (%) compared to those of pre- and syn-mineralization rocks (Fig. 6a).
Sr 760 ±3.0 0.4 Two samples of the syn-mineralization Schultze granite from
Y 13 ±0.99 7.6 Resolution plot in the prospective field (Sr/MnO >10 000), and one
Mn 550 ±12 2.1 syn-mineralization intrusive sample plots in the unprospective field
(Fig. 6b). Two samples of pre-mineralization intrusions plot in the
Standards and blanks are excluded from average value calculations due to the absence unprospective field. At Las Bambas, syn-mineralization intrusions
or low concentrations of some elements. have higher Sr/MnO (>10 000) and Sr/Y values (90–120), than
*Calculated mean value of all pXRF data of intrusive rocks analysed in the current
study. pre-mineralization samples (Sr/MnO = 2000–10 000, Sr/Y <50;
Fig. 6c). For the Cadia area, syn-mineralization samples plot wholly
within the prospective field (Fig. 6d). Most pre-mineralization
samples also plot within the prospective field, but at overall lower
Tables 5 and 6. Sampling precision was also evaluated by analysing Sr/MnO values (<10 500; Fig. 6d). Unlike the Yerington and Las
ten different spots on a single sample (Fig. 4) and calculating the Bambas districts, Sr/Y values of syn-mineralization intrusions are
RSD for each element (Table 4). RSD values for Sr, Y and Mn are variable (Fig. 6a–d). Syn-mineralization samples from Cadia have
between 5.5 and 16% (Table 4). Sr/Y values between 50 and 80, whereas pre-mineralization
The accuracy of the pXRF data was evaluated by calculating the intrusions have Sr/Y values ranging from 10 to 100 (Fig. 6d).
relative difference (RD) between the pXRF data (the mean value of Samples from the Cowal district show a similar relationship to
multiple analyses) and conventional laboratory data for the same other districts (Fig. 6e). Samples of syn-mineralization intrusions
samples. Results are illustrated graphically in Figure 5 and included plot within the prospective field and pre- and post-mineralization
in Tables 5 and 6. At low values of Sr/Y (<100), there is a good intrusions plot close to or within the unprospective field. Syn-
correlation between pXRF data from rock slabs and ICP-MS data, mineralization intrusions from the Cowal district have both elevated
whereas at higher Sr/Y values (>100) the pXRF overestimates Sr/MnO (>10 000) and Sr/Y (>80) compared to the pre-, and post-
values by up to 54% (Fig. 5c). For both pulp powders and rock mineralization intrusions. Similarly, syn-mineralization intrusions
slabs, there is excellent correlation between the Sr/MnO values from Northparkes have a high Sr/MnO (>7000) and Sr/Y (>40)
reported by pXRF and ICP-MS/ICP-ES (R 2 = 0.73–0.94; Fig. 5). relative to the pre-mineralization intrusions. There is no overlap
However, in both cases, the pXRF underestimates Sr/MnO values between the pre-, syn- and post-mineralization datasets from Las
relative to conventional whole-rock analytical methods (Fig. 5). Bambas, Cadia, Cowal or Northparkes (Fig. 6).
Overall, RD values are lower for pXRF data collected on pulp
powders compared to intact rock slabs (Fig. 5; Tables 5 and 6). Altered rocks
Many samples analysed by pXRF in the current study have
Relative prospectivity of pre-, syn- and post-mineralization been weakly altered to epidote ± albite or contain thin epidote veins
(e.g. Fig. 4). To evaluate the potential effects of alteration minerals
intrusions
that commonly occur in the porphyry–distal environment, such as
The Sr/Y and Sr/MnO values of pre-, syn- and post-mineralization epidote and albite on Sr, Y and Mn values, pXRF data were
intrusions from each case-study area are illustrated in Figure 6. At collected directly on veins and altered rock in two spots on a single
Yerington, samples of pre- and syn-mineralization igneous rocks sample (Fig. 4; Table 4). Results from these two analyses were
plot within the prospective fields on the Sr/MnO v. Sr/Y Cu- significantly different (i.e. the standard deviation for Sr = 573 ppm);
prospectivity diagram (Fig. 6a). Samples from the Luhr Hill granite however, mean values for Sr and Y in altered spots were within 17%
return the overall highest Sr/MnO (>10 000) and Sr/Y values of the mean values for the least-altered spots (Table 4).

Fig. 4. Rock slab from the Yerington district (YE16AA144) divided into 12 areas that were analysed by pXRF to assess the instrument precision, sampling
precision and the effect of epidote and albite alteration on the Sr, Mn and Y values. The associated pXRF data are listed in Table 4.
 Downloaded from http://geea.lyellcollection.org/ by guest on August 6, 2019

A. Ahmed et al.

Table 4. Measurements of analytical and sampling precision for the Olympus Vanta pXRF

Olympus Vanta pXRF

Sample ID Spot Mn Sr Y Spot Mn Sr Y Spot Mn Sr Y

YE16AA144 4 396 803 6 5 499 1236 8 1 423 1252 9
YE16AA144 9 446 1613 8 5 501 1244 7 2 464 1151 9
YE16AA144 - - - - 5 496 1239 8 3 478 1105 12
YE16AA144 - - - - 5 503 1232 8 5 533 1157 13
YE16AA144 - - - - 5 499 1240 8 6 525 1050 10
YE16AA144 - - - - 5 509 1241 8 7 476 1149 10
YE16AA144 - - - - 5 502 1234 8 8 548 1174 8
YE16AA144 - - - - 5 508 1241 9 10 457 1178 9
YE16AA144 - - - - 5 502 1250 8 11 583 1039 12
YE16AA144 - - - - 5 510 1238 8 12 489 1170 10
Mean 421 1208 7 503 1240 8 498 1143 10
Standard deviation 35 573 1.4 4.7 5.1 0.5 48.6 63.2 1.6
RSD 8.4 47.4 20.2 0.9 0.4 5.9 9.8 5.5 15.9

All element concentrations are in ppm. Spot locations are shown on Figure 4.

Discussion In addition to being more precise, pXRF data of pulp material

are also more accurate than data of rock slabs relative to
In situ pXRF analysis of coarse-grained rocks conventional ICP-MS and ICP-ES data (Fig. 5; Tables 5 and 6).
Sampling precision and accuracy The mean RDs between values of Sr/Y and Sr/MnO are lower for
pulp material (16% Sr/Y and 19% Sr/MnO; Table 6) than for
The analytical spot size of the pXRF is c. 1 cm diameter, and the intact rock slabs (78% Sr/Y and 32% Sr/MnO; Table 5). There are
penetration depth of X-rays into the sample is variable depending on two explanations for this. First, samples collected in the field
the elements analysed (up to 1.1 cm; Potts et al. 1997). Potts et al. were split by hand. One half of the sample was sent for
(1997) described sampling precision as variations in the mineral conventional whole-rock analysis and the other half was used for
assemblage (typically due to grain size) within the volume of rock pXRF analysis. Although split from a single rock mass, the two
analysed by pXRF when replicate measurements are made on rock halves are not duplicates. It is therefore not surprising that
different parts of a particular sample. To minimize the variability the whole-rock and pXRF values are not identical given an
due to sampling precision, we used the average values from three expected degree of natural heterogeneity between the two sample
measurements on rock slabs (2–3 for pulp powders), following the halves. Another difference between the two methods is that
methods outlined in previous studies (e.g. Le Vaillant et al. 2014; conventional whole-rock sampling analyses the sample in its
Simandl et al. 2014). entirety, whereas the pXRF data acquisition on rock slabs targeted
Mean RSD values of the Sr/Y and Sr/MnO pXRF data on pulp the least-altered parts of the sample. The pXRF data of rock slabs
samples were lower (<7%) than the pXRF data collected on intact may therefore represent the most pristine or unaltered values for a
rock slabs (24–32%; Tables 5 and 6). These results indicate that given rock sample, whereas conventional data may include some
repeat measurements of pulp material return more consistent veins and/or weak alteration.
values than those on rock slabs. The higher sampling precision of The RD between the pXRF data of rock slabs and conventional
pulp powders is not surprising given the homogeneity of the laboratory data is greater for Sr/Y values (78%) than for Sr/MnO
sample volume, both with respect to grain size and mineralogy. values (32%; Table 5). This difference is likely due to the low
Conversely, intact rock slabs have a variable grain size and the concentration of Y in some samples, particularly where ferromag-
distribution of minerals is not uniform across the sample (Fig. 4). nesian minerals, such as hornblende and biotite, are absent or were
Despite the significant differences between repeat measurements not analysed by the pXRF. Overall, syn-mineralization intrusions
of rock slabs (Table 5), the mean values for each sample plot have lower Y values than pre- or post-mineralization intrusions from
within the expected fields on the Sr/Y v. Sr/MnO prospectivity the same district (Fig. 6), and Y values can approach 1 ppm, which
diagram (Fig. 6). Furthermore, the variability between repeat is near the detection limit of the pXRF instrument (Supplementary
measurements of the same sample, as measured by 1σ standard material B). Manganese and Sr occur in much higher concentrations
deviation values, is less than the differences in Sr/Y and Sr/MnO in all the rocks (hundreds of ppm; Supplementary material B) and
between syn-mineralization intrusions and other intrusions from are therefore not affected by analytical detection-limit issues. In this
the same district (Fig. 6). Where there is overlap between datasets way, pXRF values of Sr/MnO may be a more robust approximation
from different groups, such as at Yerington (Fig. 6a), the mean of whole-rock fertility signatures. Despite the challenges of the
values of each dataset are sufficiently different from one another to analytical detection limit, Sr/Y values of syn-mineralization
assess the relative fertility of each group. Figure 7 illustrates that intrusions were still higher overall than pre- or post-mineralization
there is no overlap between the 1σ error bars for the mean values of intrusions from the same district.
pre- and syn-mineralization intrusive rocks at Yerington and post-
mineralization intrusive rocks, unprospective for porphyry Cu
mineralization. There is overlap between the Sr/Y and Sr/MnO The potential effects of alteration on prospectivity
values of pre- and syn-mineralization intrusions, which can be assessment
attributed to the genetic relationship between different phases of Loucks (2014) highlighted the importance of selecting least-
the Yerington batholith, which formed by progressive fractional altered rocks for Cu-prospectivity analysis due to the mobility of
crystallization (Dilles 1987). elements such as Sr (and Mn) during alteration associated with
Table 5. ICP and pXRF data for intact rock slabs

pXRF – rock RD (pXRF

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ICP-MS/ICP- slabs: standard pXRF - rock v. ICP-MS/
ES pXRF – rock slabs: mean deviation slab: RSD ICP-ES)

District Sample ID Unit name/rock type Relative timing Sr/Y Sr/MnO MnO Sr Y Sr/MnO Sr/Y Sr/MnO Sr/Y Sr/MnO Sr/Y Sr/Y Sr/MnO
wt% ppm ppm
Cowal CD17CL005 Lake diorite Syn-mineralization 69 15 160 0.048 707.3 9.7 14 971 73 2799 2 19 3 6 1
CD17CL064 E43 diorite Pre-mineralization 34 2668 0.222 696.0 15.2 3152 46 349 4 11 10 35 18
CD17CL069 E43 quartz diorite Pre-mineralization 13 3300 0.072 273.3 15.2 3781 18 456 1 12 6 39 15
CD17CL111 E42 monzonite Post-mineralization 18 2719 0.187 593.3 27.7 3177 21 207 1 7 3 19 17
CD17CL137 Dewars diorite Post-mineralization 24 2877 0.090 339.0 12.9 3772 26 308 2 8 7 10 31
CL17CD001 Lake monzonite Syn-mineralization 55 16 100 0.018 278.0 3.9 15 520 72 1725 2 11 3 31 4
Las Bambas LB15DC027 Ferrobamba monzodiorite Syn-mineralization 85 16 740 0.040 999.7 7.8 27 509 138 12 602 38 46 27 63 64
LB15DC035 Jahuapaylla monzodiorite Syn-mineralization 65 10 986 0.044 965.9 10.9 22 416 91 2947 18 13 20 40 104

Assessing porphyry copper fertility with pXRF

LB16AG048 La Cresta monzodiorite Syn-mineralization 68 28 750 0.041 1114.9 13.1 27 012 85 1102 5 4 6 25 6
LB16AG009 Pioneros quartz diorite Post-mineralization 149 6342 0.072 216.8 2.7 2642 75 1061 45 40 60 50 58
LB16AG162 Rayusco diorite Post-mineralization 16 2480 0.042 443.1 18.6 10 615 24 369 4 3 16 51 328
Resolution RE16JP022 Schultz granite Syn-mineralization 46 29 000 0.016 609.7 4.4 43 405 517 14 760 728 34 141 1025 50
RE15JP023 Schultz granite Syn-mineralization 49 21 533 0.025 637.7 12.9 26 886 51 6819 12 25 23 5 25
RE15JP061 Schultz granite Syn-mineralization 13 9375 0.022 215.3 12.9 10 086 17 3344 6 33 35 34 8
RE16JP077 Quartz diorite Pre-mineralization 48 5927 0.098 721.7 12.3 7413 59 816 6 11 10 23 25
RE16JP075 Quartz diorite Pre-mineralization 42 3700 0.097 803.0 10.3 8727 83 2486 26 28 31 97 136
Yerington YE16AA082 Shamrock monzonite Post-mineralization 88 14 702 0.103 585.0 17.1 6046 39 2426 21 40 54 56 59
YE16AA097 Shamrock monzonite Post-mineralization 41 7689 0.077 628.3 9.7 8187 66 671 10 8 15 62 6
YE16AA112 Shamrock monzonite Post-mineralization 38 6052 0.116 454.0 15.8 4526 29 2509 4 55 14 24 25
Mean 6253 45
Standard deviation 1839 19
YE16AA237 McLeod Hill quartz monzodiorite Pre-mineralization 47 10 403 0.047 617.0 8.1 13 128 81 1223 26 9 32 72 26
YE16AA200 McLeod Hill quartz monzodiorite Pre-mineralization 85 96 880 0.020 1035.7 11.6 54 461 98 16 265 36 30 36 16 44
YE16AA226 McLeod Hill quartz monzodiorite Pre-mineralization 109 36 263 0.027 1007.3 4.2 37 852 243 2306 35 6 14 123 4
YE16AA012 Bear quartz monzonite Pre-mineralization 85 43 770 0.014 769.0 8.1 55 981 121 16 516 62 30 51 42 28
YE16AA013 Bear quartz monzonite Pre-mineralization 94 44 330 0.020 1035.3 3.9 51 634 285 11 453 141 22 50 204 16
YE16AA014 Bear quartz monzonite Pre-mineralization 87 45 385 0.032 996.0 2.0 8961 125 8961 125 100 100 44 80
YE16AA060 McLeod Hill quartz monzodiorite Pre-mineralization 47 7572 0.049 362.0 4.5 7384 82 839 20 11 24 74 2
YE16AA066 McLeod Hill quartz monzodiorite Pre-mineralization 111 38 030 0.039 1012.7 7.4 26 692 150 6645 53 25 35 35 30
YE16AA069 McLeod Hill quartz monzodiorite Pre-mineralization 127 25 543 0.053 1406.0 9.9 30 050 144 13 045 19 43 13 13 18
YE16AA131 McLeod Hill quartz monzodiorite Pre-mineralization 75 15 748 0.080 1372.7 16.1 17 270 96 1312 48 8 50 28 10
YE16AA144 McLeod Hill quartz monzodiorite Pre-mineralization 122 14 588 0.062 1191.3 7.1 19 466 169 2296 17 12 10 38 33
YE16AA169 McLeod Hill quartz monzodiorite Pre-mineralization 85 11 424 0.096 1273.3 15.5 13 322 82 1126 2 8 3 3 17
YE16AA192 Bear quartz monzonite Pre-mineralization 99 27 055 0.033 1097.7 4.5 33 693 265 3293 105 10 40 168 25
Mean 28 453 149
Standard deviation 17 288 72
YE16AA238 Luhr Hill granite Syn-mineralization 141 25 807 0.021 607.0 6.8 30 280 96 8653 33 29 35 32 17
YE16AA215 Luhr Hill granite Syn-mineralization 160 137 570 0.013 1282.3 7.7 100 057 169 36 273 31 36 18 6 27
(continued)
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A. Ahmed et al.

porphyry Cu mineralization. However, most porphyry Cu

5
Sr/MnO

38
56

24
36
26

18
37
v. ICP-MS/
RD (pXRF
deposits typically have large alteration footprints that can

ICP-ES)
extend kilometres from the deposit centre (Lowell & Guilbert
1970; Gustafson & Hunt 1975; Seedorff et al. 2005; Sillitoe

46

69
28
74
39
48

78
Sr/Y

256

130
2010; Cooke et al. 2014), which can make least-altered samples
difficult to find. Baldwin & Pearce (1982) used both unaltered

Mean
and weakly altered samples in their discrimination of productive
21 and unproductive intrusions using MnO and Y. They concluded
56
47
18
41
82
69
28
32
Sr/Y

that the replacement of hornblende by biotite ± ilmenite ± titanite

pXRF - rock
slab: RSD

did not affect the classification of a sample as either productive

or unproductive.
17
25
65
22
28

39
18
Sr/MnO

24
6
Some samples from the six porphyry districts presented in the
current study were weakly altered to epidote ± albite ± chlorite ±
actinolite, common alteration minerals in the porphyry–distal

Mean
environment (Cooke et al. 2014; Fig. 4). Epidote and albite can
incorporate significant amounts of Sr into their crystal structures
26

45

94
Sr/Y

235
146

122
223
226
slabs: standard

(Frei et al. 2004). The presence of these minerals (likely in

pXRF – rock

deviation

significant quantities) may therefore result in a false positive

6073

1295
15 369
48 192
14 584
11 308

23 655
13 134
Sr/MnO

fertility signature on the Sr/Y v. Sr/MnO fertility diagram if they

are analysed in the sample volume excited by the pXRF. This
kind of false positive is highlighted in the current study (Table 4),
Sr/Y

127
416
313
260
295
271
327
333
261
101

in which one analysis that included an epidote vein yielded

nearly 400 ppm more Sr than the least-altered parts of the same
sample. False positives can be mitigated, at least in part, by
Sr/MnO

36 029
62 695
74 547
67 097
40 974
22 143
60 638
71 541
56 600
23 909

selecting the least-altered part of a rock sample for pXRF

analyses (Fig. 4).
4.8
3.5
4.6
3.5
2.9
2.6
4.8
3.9
ppm
Y
pXRF – rock slabs: mean

Standard deviation

Calibration curves
598.3

909.0
790.3
485.7
833.3
1181.0
1277.5

1229.7

The calibration curves applied in this study used data collected on

ppm
Sr

Mean

pulverized standard material prepared in press cups. The pXRF

RSD values are shown for multiple analyses collected on individual samples. The RDs between the pXRF and ICP data are also shown.

analysis of press cup material presents a smooth uniform surface to

0.017
0.020
0.023
0.014
0.021
0.022
0.015
0.018

the pXRF, enabling complete contact between the instrument and the
MnO
wt%

sample surface. Furthermore, the rock material was homogenized into

a very fine-grained powder (120 mesh), decreasing the effects of
Sr/MnO

26 180
40 313
69 480
53 915
30 057
29 953
57 570
60 820

mineral and grain size heterogeneity. Ideally, all the samples would
ICP-MS/ICP-

be presented to the pXRF in this way, as it is demonstrated in the

ES

current study that pXRF data on pulp powders return more accurate
results than those on rock slabs (Fig. 5; Tables 5 and 6). However,
87
Sr/Y

117
185
203
170
195
221
145

field applications present less ideal and more variable sample

surface geometries and coarser grain sizes, making sample
Syn-mineralization
Syn-mineralization
Syn-mineralization
Syn-mineralization
Syn-mineralization
Syn-mineralization
Syn-mineralization
Syn-mineralization

presentation an issue that can affect data quality (Young et al.

Relative timing

2016; Duée et al. 2019). Given that we calibrated pXRF data of

coarse-grained rock slabs using calibration factors derived from
standards in pressed powder mounts, there is the potential for these
data to be affected by unforeseen mineral matrix effects due to
differences in the relative proportions of minerals present in the rock
slab and standard material. Unfortunately, the heterogeneity of
medium- to coarse-grained rock slabs makes developing a matrix-
matched standard nearly impossible.
Unit name/rock type

Luhr Hill granite

Luhr Hill granite
Luhr Hill granite
Luhr Hill granite
Luhr Hill granite
Luhr Hill granite
Luhr Hill granite
Luhr Hill granite

Implications for exploration

The whole-rock geochemical compilation (ICP-MS/ICP-ES; XRF)
of nearly 30 porphyry Cu districts from the current study shows that
Sr/Y and Sr/MnO values can be used to discriminate between
prospective and unprospective intrusions (Fig. 2). However, there is
YE16AA044
YE16AA065
YE16AA070
YE16AA135
YE16AA157
YE16AA163
YE16AA166
YE16AA181

overlap between the prospective and unprospective datasets. This

Sample ID

overlap is consistent with other published studies that also assessed

Table 5. (Continued)

the ore-forming potential of intrusions, which show a significant

overlap in the values of key element fertility indicators between
unmineralized and mineralized suites (Fig. 2; Baldwin & Pearce
1982; Loucks 2014; Dilles et al. 2015; Lu et al. 2016), especially
District

for porphyry Cu and porphyry Cu-Mo suites generated in thick crust

Andean-type environments.
Table 6. ICP and pXRF data for pulp powders

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pXRF – pulp
powders: RD (pXRF
ICP-MS/ICP- standard pXRF - Pulp v. ICP-MS/ICP-
ES pXRF – pulp powders: mean deviation powders: RSD ES)

MnO Sr Y Sr/MnO Sr/Y Sr/MnO Sr/Y

District Sample ID Unit name/rock type Relative timing Sr/Y Sr/MnO wt.% ppm ppm Sr/MnO Sr/Y Sr/MnO Sr/Y % % % %
Cadia 151 708 Diorite Pre-mineralization 61 5781 0.198 1483 17.3 7481 86 300 6 4 7 29 41
151 709 Diorite Pre-mineralization 65 6522 0.131 1451 10.7 11 098 138 687 21 6 15 70 112
151 790 Monzonite Syn-mineralization 25 25 950 0.034 627 17.6 18 251 36 430 6 2 16 30 45
152 862 Monzonite Syn-mineralization 50 26 567 0.036 912 20.7 25 032 44 684 2 3 4 6 12
152 863 Monzonite Syn-mineralization 36 47 300 0.020 507 15.5 25 875 33 1335 1 5 3 45 9

Assessing porphyry copper fertility with pXRF

152 865 Monzonite Pre-mineralization 41 10 071 0.080 773 21.2 9619 36 9 1 0 3 4 11
152 866 Monzonite Pre-mineralization 38 13 760 0.057 740 20.2 13 086 37 340 1 3 4 5 4
152 867 Monzonite Pre-mineralization 39 10 317 0.073 671 18.8 9161 36 114 0 1 0 11 9
152 868 Diorite Pre-mineralization 79 7375 0.167 1244 16.0 7467 78 26 0 0 0 1 2
152 869 Diorite Pre-mineralization 12 2510 0.200 534 41.4 2667 13 51 0 2 0 6 7
152 871 Diorite Pre-mineralization 70 7013 0.106 842 14.8 13 670 25 261 2 2 6 95 65
Cowal 168 147 E41 diorite Pre-mineralization 23 2260 0.215 564 16.0 2645 35 414 3 16 10 17 53
168 163 E41 diorite Pre-mineralization 15 1844 0.225 474 14.4 2149 33 450 5 21 14 17 120
168 172 E41 diorite Pre-mineralization 30 2798 0.175 681 16.6 3946 42 843 10 21 24 41 40
168 630 E41 monzonite Pre-mineralization 31 9703 0.048 46 19.8 989 2 110 0 11 5 90 92
168 674 E41 monzonite Pre-mineralization 31 4781 0.126 301 20.4 2401 16 4 5 0 31 50 50
177 113 Marsden quartz diorite Pre-mineralization 4 898 0.103 92 25.4 901 4 99 0 11 12 0 9
177 118 Marsden quartz diorite Pre-mineralization 17 4396 0.078 388 19.1 5069 20 1216 4 24 18 15 20
177 126 Marsden quartz diorite Pre-mineralization 37 6871 0.093 691 16.3 7604 46 1969 17 26 37 11 24
177 127 Marsden quartz monzodiorite Pre-mineralization 8 4288 0.029 122 15.7 4291 8 327 1 8 12 0 2
177 134 Marsden granodiorite Syn-mineralization 69 19 303 0.032 607 7.3 18 837 84 1834 11 10 13 2 22
Yerington YE16AA013 Bear quartz monzonite Pre-mineralization 94 44 330 0.025 924 10.4 36 766 89 0 0 0 0 17 5
YE16AA014 Bear quartz monzonite Pre-mineralization 87 45 385 0.021 947 10.8 46 021 88 2312 5 5 6 1 1
YE16AA065 Luhr Hill granite Syn-mineralization 117 40 313 0.034 1190 10.8 35 430 110 42 8 0 7 12 6
YE16AA069 McLeod Hill quartz monzodiorite Pre-mineralization 127 25 543 0.065 1439 11.8 22 302 122 748 7 3 5 13 4
YE16AA082 Shamrock monzonite Post-mineralization 88 14 702 0.098 1257 16.5 12 810 76 415 3 3 4 13 13
YE16AA088 Shamrock monzonite Post-mineralization 47 31 357 0.032 875 19.3 27 643 45 838 1 3 3 12 4
YE16AA097 Shamrock monzonite Post-mineralization 41 7689 0.097 635 17.0 6580 37 22 0 0 0 14 9
YE16AA112 Shamrock monzonite Post-mineralization 38 6052 0.122 674 19.8 5505 34 84 0 2 0 9 10
YE16AA144 McLeod Hill quartz monzodiorite Pre-mineralization 122 14 588 0.082 1182 11.6 14 464 102 321 5 2 5 1 16
YE16AA157 Luhr Hill granite Syn-mineralization 170 30 057 0.031 892 6.1 28 605 146 787 15 3 10 5 14
YE16AA163 Luhr Hill granite Syn-mineralization 195 29 953 0.039 885 5.2 22 988 172 618 22 3 13 23 12
YE16AA169 McLeod Hill quartz monzodiorite Pre-mineralization 85 11 424 0.106 1228 14.6 11 582 84 236 4 2 5 1 1
YE16AA181 Luhr Hill granite Syn-mineralization 145 60 820 0.023 1216 7.5 53 816 161 1791 0 3 0 12 11
YE16AA192 Bear quartz monzonite Pre-mineralization 99 27 055 0.041 1072 9.4 26 332 114 0 0 0 0 3 15
YE17AA237 McLeod Hill quartz monzodiorite Pre-mineralization 47 10 403 0.064 677 14.6 10 513 46 60 3 1 6 1 1
(continued)
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Table 6. (Continued)

pXRF – pulp
powders: RD (pXRF
ICP-MS/ICP- standard pXRF - Pulp v. ICP-MS/ICP-
ES pXRF – pulp powders: mean deviation powders: RSD ES)

MnO Sr Y Sr/MnO Sr/Y Sr/MnO Sr/Y

District Sample ID Unit name/rock type Relative timing Sr/Y Sr/MnO wt.% ppm ppm Sr/MnO Sr/Y Sr/MnO Sr/Y % % % %
Northparkes NP17TW001 BQM Syn-mineralization 62 8000 0.154 1275 22.0 8255 58 43 3 1 5 3 6
NP17TW007 BQM Syn-mineralization 57 6767 0.141 872 15.7 6190 55 84 2 1 4 9 3
NP17TW016 BQM Syn-mineralization 89 12 318 0.051 573 11.0 10 606 90 219 7 2 7 14 1

A. Ahmed et al.
NP17TW017 Porphyry 2 Syn-mineralization 58 14 175 0.051 573 11.0 11 156 52 47 2 0 5 21 10
NP17TW022 Porphyry 1 Syn-mineralization 70 4200 0.043 169 3.8 3969 45 113 1 3 1 5 36
NP17TW023 BQM Syn-mineralization 59 31 633 0.034 918 16.0 26 758 57 1683 0 6 0 15 3
NP17TW025 Porphyry 2 Syn-mineralization 122 64 750 0.025 1270 11.3 51 007 112 2055 1 4 1 21 8
NP17TW026 Porphyry 2 Syn-mineralization 261 46 950 0.022 889 4.1 40 183 220 2045 27 5 12 14 16
NP17TW028 Porphyry 2 Syn-mineralization 70 16 075 0.043 611 9.9 14 105 62 170 4 1 7 12 12
NP17TW030 Porphyry 1 Syn-mineralization 36 12 800 0.026 262 8.2 9897 32 236 2 2 6 23 12
NP17TW032 Porphyry 2 Syn-mineralization 33 17 000 0.019 327 9.4 17 048 35 669 3 4 10 0 6
NP17TW037 BQM Syn-mineralization 39 17 475 0.043 669 17.7 15 475 38 502 2 3 5 11 3
NP17TW046 Porphyry 1 Syn-mineralization 69 19 200 0.033 576 8.5 17 644 68 262 0 1 0 8 1
NP17TW050 BQM Syn-mineralization 22 4245 0.121 459 21.7 3793 21 106 1 3 4 11 4
NP17TW058 Porphyry 1 Syn-mineralization 132 5077 0.134 640 5.7 4782 113 37 0 1 0 6 14
Np17TW047 Porphyry 1 Syn-mineralization 58 8280 0.052 419 8.2 8109 52 297 3 4 7 2 11
NP17TW087 Trachyte Pre-mineralization 6 925 0.262 229 34.8 874 7 16 0 2 3 6 9
NP17TW088 Monzonite Pre-mineralization 8 592 0.279 158 19.1 566 8 4 0 1 3 4 3
Mean 5 7 Mean 16 19

RSD values are shown for multiple analyses collected on individual samples. The RDs between pXRF and ICP data are also shown.
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Assessing porphyry copper fertility with pXRF

Fig. 5. Comparisons between the pXRF data (mean values for a given sample) and conventional laboratory data for different sample media. (a) Sr/Y: pXRF
data from pulp material in press cups and ICP-MS/ICP-ES data. (b) Sr/MnO: pXRF data from pulp material in press cups and ICP-MS/ICP-ES data.
(c) Sr/Y: pXRF data from intact rock slabs and ICP-MS/ICP-ES data. (d) Sr/MnO: pXRF data from intact rocks slabs and ICP-MS/ICP-ES data. All the
data are included in Tables 5 and 6.

The overlap between the prospective and unprospective datasets methods. The first is cost; although the purchase of a pXRF instrument
from the conventional whole-rock prospectivity diagram (Fig. 2) is requires an initial cost, there is no limit to the number of analyses
consistent with the pXRF results of intrusive rocks from the six collected after the purchase within the lifespan of the instrument. This
case-study areas (Fig. 6). Overall, the relative prospectivity of each makes the cost of a single pXRF analysis one or two orders of
intrusion from the six case-study areas correlates with its temporal magnitude lower than that of whole-rock geochemical analyses from a
relationship to mineralization (Fig. 6). Samples of pre- and post- commercial laboratory. Second is time; a single pXRF analysis can be
mineralization intrusions, unprospective for porphyry Cu forma- collected in around 90 s. Third is the volume of data; the speed with
tion, return lower Sr/Y and Sr/MnO values than syn-mineralization which pXRF data can be obtained permits multiple analyses to be
intrusions. However, the absolute values of Sr/Y and Sr/MnO that collected for a single sample and many samples to be analysed from a
separate prospective and unprospective intrusions vary between single lithological unit. Larger sample populations allow for better
districts (Fig. 6). Here we propose that, while global reference suites statistics to be performed on the dataset and for increased confidence in
should continue to be used to understand the general relationship an individual intrusion plotting as either prospective or unprospective.
between mineralized and unmineralized intrusions, as has been The fourth and final benefit of pXRF data acquisition, in this context, is
done in the current study, they should not be used to develop hard niche sampling. Data collection using pXRF permits the user to target
numerical boundaries that define the ore-forming potential of an the least-altered parts of an outcrop or hand sample (Fig. 4). Together,
intrusion – this needs to be treated on a district-by-district basis. The the four benefits of pXRF data collection support rapid, low-cost data
use of a global set of numerical prospectivity boundaries may lead collection in the field that can result in real-time decision making about
to false positive classifications of unprospective intrusions or, the prospectivity of intermediate to felsic rocks in a given exploration
conversely, misclassification of fertile intrusions as unprospective. search space.
The method outlined in the current study is therefore best applied in
regional exploration where there is some pre-existing knowledge of
the background Sr/Y and Sr/MnO values. Conclusions
A global compilation of conventional whole-rock geochemical data
The benefits of pXRF data acquisition from a wide variety of porphyry Cu settings shows that ore-forming
We have identified four benefits of using pXRF data to inform Cu intrusive rocks have higher Sr/Y and Sr/MnO values than an
prospectivity diagrams rather than the conventional ICP-MS or XRF unprospective suite of rocks (Fig. 2). Higher Sr/Y and Sr/MnO
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A. Ahmed et al.

Fig. 6. The pXRF data of the pre-, syn- and post-mineralization intrusive rocks from six porphyry Cu and skarn districts plotted on Sr/MnO v. Sr/Y
diagrams using the fertility fields outlined in Figure 2. The sample medium analysed for each district is listed here. (a) Yerington district, USA; rock slabs.
For clarity, pulp powder analyses from Yerington are not included on this diagram. (b) Resolution deposit, USA; rock slabs. (c) Las Bambas district, Peru;
rock slabs. (d) Cadia district, Australia; pulp powders. (e) Cowal district, Australia; pulp powders and rock slabs. (f ) Northparkes district, Australia; pulp
powders. Error bars (1σ) are shown for each datapoint and were calculated as one standard deviation from the mean of multiple analyses on each sample.
Where error bars are not visible, they are smaller than the symbol size. Mean Sr/Y and Sr/MnO values for each sample in each dataset are included in
Tables 5 and 6. Data from individual analyses are tabulated in Supplementary material B.

proportions are interpreted to reflect the combined processes of Calibrated pXRF data collected on both pulp powders and intact
hornblende fractionation and plagioclase suppression in hydrous rock slabs from six globally significant porphyry districts highlight
melts, characteristic of ore-forming intrusions (Baldwin & Pearce how the binary plot of Sr/Y v. Sr/MnO can be applied to rapidly
1982; Richards & Kerrich 2007; Richards 2011; Loucks 2014). identify the ore-forming potential of an intrusive rock in the field
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Assessing porphyry copper fertility with pXRF

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Acknowledgments Many thanks to Jay Thompson, manager of the 08120090601146771
pXRF laboratory facilities at the University of Tasmania. All samples analysed by Cooke, D.R., Hollings, P., Wilkinson, J.J. & Tosdal, R.M. 2014. Geochemistry of
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permission of the owners of the samples. Thanks to Tim Ireland (Collahuasi) and Costa, F., Scaillet, B. & Pichanvant, M. 2004. Petrological and experimental
Alan Wilson (Cadia) for providing their samples and associated whole-rock constraints on the pre-eruption conditions of Holocene dacite from Volcan San
geochemical data for this study. Sincere thanks to Matt Cunningham of Hudbay Pedro (36° S, Chilean Andes) and the importance of sulphur in silicic
Minerals (formerly Mason Resources), George Eliopolous and Todd Bonsall subduction-related magmas. Journal of Petrology, 45, 855–881, https://doi.
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anonymous reviewer for their comments and suggestions, all of which greatly complexes in the Ordovician Macquarie Arc, New South Wales. Australian
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Funding This research is part of a PhD project funded by the AMIRA doi.org/10.2113/gsecongeo.75.6.830
International P1153 project ‘Applying the explorer’s toolbox to discover Cu, Au, Dilles, J.H. 1987. Petrology of the Yerington Batholith, Nevada; evidence for
and Mo deposits’, an Australian Postgraduate Award and an AusIMM Education evolution of porphyry copper ore fluids. Economic Geology, 82, 1750–1789,
Endowment Fund scholarship. It was also supported by the ARC Research Hub https://doi.org/10.2113/gsecongeo.82.7.1750
for Transforming the Mining Value Chain. Dilles, J.H., Kent, A. J., Wooden, J.L., Tosdal, R.M., Koleszar, A., Lee, R.G. &
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