2012-166

2014
research-articleThematic set: portable XRFXXX10.1144/geochem2012-166M. Le Vaillant et al.pXRF in Nickel Sulphide exploration

Use and calibration of portable X-Ray fluorescence analysers:

application to lithogeochemical exploration for komatiite-hosted
nickel sulphide deposits
Margaux Le Vaillant1*, Stephen J. Barnes2, Louise Fisher2,4, Marco L. Fiorentini1
& Stefano Caruso3
1Centre for Exploration Targeting, the University of Western Australia, ARC Centre of Excellence for Core to Crust Fluid
Systems, Crawley WA6009, Australia
2CSIRO Earth Science and Resource Engineering, ARRC, PO Box 1130, Bentley WA 6102, Australia
3Dipartimento di Scienze della Terra ‘A. Desio’, Università degli Studi di Milano, Milan, Italy
4Deep Exploration Technologies Cooperative Research Centre, Adelaide, South Australia, 5950

*Corresponding author (e-mail: levaim01@student.uwa.edu.au)

Abstract: Portable X-Ray Fluorescence (pXRF) analysers allow on-site geochem-

ical analysis of rock powders and drill core. The main advantages of pXRF analysis
over conventional laboratory analysis are the speed of data collection and the low cost
of the analyses, permitting the collection of extensive, spatially representative data-
sets. However, these factors only become useful if the quality of the data meets the
requirements needed for the purposes of the study. Here, we evaluate the possible use
of portable XRF to determine element concentrations and ratios used in exploration
for komatiite-hosted nickel sulphides.
A portable XRF analyser was used to measure a series of chalcophile and litho-
phile element concentrations (Si, S, K, Ca, Ti, Cr, Fe, Ni, Cu, Zn, As, Sr, and Zr)
of 75 samples from three komatiite units associated with nickel sulphide ores in the
Yilgarn Craton, Western Australia. Crucial steps in the study were the development
of a strict calibration process as well as numerous data quality checks. The 670 analy-
ses collected in this study were compared with conventional laboratory XRF data on
discriminant diagrams commonly utilized in exploration for komatiite-hosted nickel
sulphides (Cr vs Ni and Ni/Ti vs Ni/Cr). After comparing the results obtained with
pXRF during this study with the laboratory values, we can conclude that portable
XRF analyses can be used for rapid assessment of the nickel sulphide prospectivity of
komatiites provided that strict control protocols are followed.

Supplementary material: is available at http://www.geolsoc.org.uk/SUP18706

Keywords: portable XRF, komatiite, nickel sulphide, Ni/Ti vs Ni/Cr vector, exploration targeting

Portable XRF analysis is an emerging geochemical tool that nickel sulphide resources (Hoatson et al. 2006). The deposits
allows rapid and reliable determination of a range of major were formed by the dynamic emplacement of high tempera-
and trace elements in rocks and ores. The speed with which ture, potentially erosive komatiite lava flows and sub-volcanic
analyses can be obtained makes the technique suitable to use sills that assimilate crustal sulphur reservoirs hosted in a wide
during on-site during drilling programmes, and allows better range of environments (Lesher 1989; Barnes 2006; Bekker et al.
informed decisions on planning, positioning and progression 2009). Some of the geochemical signatures of these processes
of drill holes in real time. In this contribution, we show how are potentially detectable by pXRF analysis.
this capability may be applied in the exploration for and deline- Over the years, different geochemical tools have been
ation of komatiite-hosted nickel sulphide ore deposits. developed in order to help exploration and delineation of
The world’s most economically significant komatiite-hosted komatiite hosted nickel-sulphide deposits. One approach is to
nickel deposit province is situated in the Yilgarn Craton of look for depletion of chalcophile elements to differentiate bar-
Western Australia (Barnes & Fiorentini 2012). This is one of ren and mineralized ultramafic sequences (Duke 1979; Lesher
the world’s major nickel-sulphide provinces, with pre-mining et al. 1981; Barnes et al. 1988; Fiorentini et al. 2010; Heggie et al.
resources of c. 12.7 Mt Ni, representing 17.6 % of the world’s 2012). Loss or gain of Ni, Cu, Co and PGE relative to back-
nickel-sulphide resources (Hronsky & Schodde 2006). In ground values in unmineralized rocks can be interpreted as a
Australia, komatiite-hosted nickel-sulphide deposits, mostly sign of sulphide liquid segregation and/or accumulation, thus
concentrated within the Yilgarn Craton, represent 95% of the indicating the possible presence of a mineralized body within

Geochemistry: Exploration, Environment, Analysis © 2014 AAG/The Geological Society of London

http://dx.doi.org/10.1144/geochem2012-166
Published Online First
2 M. Le Vaillant et al.
the same ultramafic sequence. Another geochemical approach
relies on the detection of anomalous enrichment in incompat-
ible element concentrations, such as Zr, Th and LREE, in oth-
erwise depleted mantle-derived melts (Barnes et al. 1995, 2004)
relating to the role of crustal contamination in the genesis of
komatiite-hosted ore-forming systems. Zirconium and Ti are
immobile trace elements which are resistant to post-emplace-
ment processes such as metasomatism, sea-floor alteration and
metamorphism (Huppert & Sparks 1985). The ratio Zr/Ti is
not modified by fractional crystallization and in many komati-
ites matches the ratio in the mantle source (Sun & Nesbitt
1977). Variability in Zr/Ti ratio between komatiitic flows can
be explained by different amounts of crustal contamination
during eruption (Huppert & Sparks 1985). Furthermore,
appropriate Ni, Cr and Ti ratios can be used to identify the
presence of high-flux channelized environments and conduits
where favourable physical volcanic emplacement processes
took place and where nickel sulphide systems are likely to be
hosted (Barnes & Brand 1999; Barnes et al. 2004).
The use of Ni, Cr and Ti is based on a number of properties
of these elements in komatiites. Nickel backgrounds in unmin-
eralized komatiites are high and variable, due to the compati-
bility of Ni in olivine. High olivine content is a characteristic
feature of potential host rocks to sulphide mineralization,
formed in the feeder pathways or channels within komatiite
flow fields. This variable and high background concentration
of Ni in both mineralized and unmineralized komatiites makes
it difficult to recognise subtle positive anomalies due to the
presence of small amounts of magmatic sulphide. Conversely,
Ti is incompatible in olivine. Hence, Ni/Ti ratios correlate
strongly with original olivine content; the Ni/Ti ratio can be
used to better constrain the silicate Ni background and high-
light subtle sulphide-related Ni enrichment.
Olivine-rich cumulates can also be found in layered cumu-
lates formed from differentiated komatiite magma in layered
sills or lava lakes. The latter environment also commonly con-
tains elevated proportions of cumulus chromite, and hence
low Ni/Cr ratios, but is an unfavourable environment for eco-
nomic nickel sulphide mineralization. Furthermore, mineral-
ized olivine-rich komatiite units are in some situations
anomalously Cr-depleted (Barnes & Fiorentini 2012). Hence,
relatively high Ni/Cr ratios, coupled with high Ni/Ti ratios,
can help to delineate rocks from favourable volcanic environ-
ments as well as those with mildly anomalous sulphide-related
Ni contents. Owing to the low mobility of Ni, Cr and Ti in
most hydrothermal fluids, this approach is of benefit in set-
tings where the host rocks are intensely altered or metamor-
phosed to the point where their original mineralogy is obscured.
This is commonly the case in komatiites in Western Australia
that have undergone complete replacement by talc-carbonate
assemblages (e.g. Barnes et al. 2009), and also in high metamor-
phic-grade terranes such as the Forrestania Belt (Perring et al.
1995). There is also good evidence to suggest that Ni/Ti and
Ni/Cr ratios are preserved during moderate degrees of weath-
ering (Barnes et al. in press), making the element ratio approach
applicable to bottom-hole samples from percussion drilling in
weathered terrains without the necessity for sampling com-
pletely fresh bedrock.
The Ni/Ti vs Ni/Cr approach is particularly amenable to
the application of pXRF analysis. The portable XRF instru-
ment can reliably determine the concentrations of most
major elements heavier than Si, most of the transition metals
and some trace elements such as As, Zr and Sr (Fisher et al. in
press). Copper is a highly mobile element, and therefore the
study of the enrichment or depletion of komatiites in chalco-
phile elements, as an exploration tool, also requires platinum
group element (PGEs) data. However, PGEs are not detect-
able at useful concentrations by portable XRF, as detection
limits for all the PGEs are in the 5 to 10 ppm range at best,
similar to Au, and well above the expected concentrations in
the study samples. Moreover, PGE analyses by pXRF can
also be problematic with regard to interferences such as that
for Rh with the Rh anode/target as well as overlaps with ele-
ments like Zn, As, W and Se (Aaron Baensch, pers. comm.
2012). As for the crustal contamination approach for explo-
ration targeting, the only element that could be useful and is
detectable by pXRF is Zr. In this study, we evaluate the
potential use of pXRF to determine Ni, Ti, Cr and Zr con-
centrations in komatiites, and the use of these concentrations
for nickel sulphide exploration targeting.
Materials and Methods
Instrument and settings
The portable XRF used for this study is the Olympus-InnovX
X500 desktop XRF analyser, which has a 10 W, 50 kV tanta-
lum X-ray tube with a high precision, large-area silicon drift
detector (SDD). This instrument offers two different analyti-
cal modes. The mode chosen depends on the elements of
interest and on their expected concentrations in the analysed
samples. The ‘trace’ mode (named ‘Soil’ on the operating
menu of the instrument) is used to collect data for trace ele-
ments with concentrations less than 1 wt%, where concentra-
tions are measured in ppm. The ‘major’ mode (named ‘Mining
plus’) is used to collect data for elements with concentrations
>0.5–1 wt%. In this case, the measured concentrations are
output as weight percent. The trace or soil mode conducts a
three-beam analysis of one minute each (at 50, 35 and 15 kV),
whereas the major or mining mode conducts a two-beam
analysis (at 35 and 15 kV). The beam count time of the instru-
ment can vary from 10 s to 120 s. For the purposes of this
study, the beam count was set at 60 s per beam for the trace
mode and at 30 s for heavy elements and 60 s seconds for light
elements for the major mode.
Calibration
To define the calibration equations, we selected 28 matrix-
matched control reference materials (CRMs) of similar com-
position to the samples to be analysed. We use many CRMs in
order to cover the range of concentrations needed to obtain
good calibration curves for each element. These CRMs were
selected amongst samples collected at the Miitel deposit and
previously analysed by Ultra Trace laboratories, Perth, by
XRF, ICP-MS and ICP-AES methods; they were chosen to
represent the widest range of concentration possible for the
elements of interest. The standardization protocol was to
analyse each CRM, presented as <80-mesh pulps, multiple
times (5 to 10) using both the trace and the major modes of
the pXRF analyser (Gazley et al. 2011a, b). The main oxide
concentrations of the CRMs were obtained at the Ultra Trace
laboratory by X-Ray fluorescence spectrometry on samples
cast using 12:22 flux to form a glass bead. The elements deter-
mined were Fe, Ti, Cr, Cu, Ni, Zn and Mn. The samples were
then digested and refluxed with a mixture of acids including
hydrofluoric, nitric, hydrochloric and perochloric acids. This
extended digest approaches a total digest for many elements:
a few refractory minerals such as zircon and chromite are still
not completely attacked, although recoveries of better than
90 % are indicated for most samples (Barnes et al. 2004). The
samples obtained were then analysed by inductively coupled
plasma mass spectrometry (ICP-MS) to obtain Zr, Sr and As
 pXRF in Nickel Sulphide exploration
#12
#14
#13
#15
#83
2.5 cm #84
#95
#96
#101 #103
#151
#102 #104
#106
Fig. 1. Komatiite sample from the Miitel deposit, used to evaluate sample precision. The numbers represent the location of the pXRF analyses
made on the sample.
concentrations. Chromium, Cu, Fe, Ni and Ti were also deter-
mined after this total digestion by ICP atomic emission spec-
trometry (ICP-AES).
By plotting the average values of the concentration of each
element obtained by portable XRF for the different CRMs
against the values obtained by Ultra Trace laboratories, it was
possible to calculate linear calibration equations. These calcu-
lated factors and offsets were applied as part of the data reduc-
tion process. Even though it is customary in geoanalysis to
assign the lab value to the y-axis and the test value (pXRF) to
the x-axis, we inverted the axes to then be able to use the
regression equations to calculate the corrected pXRF value, y.
The control reference material pulps were analysed through
a thin plastic bag. Prior to the definition of the calibration
equations, the impact of the plastic bag on the results had to be
evaluated and any attenuation effect assessed. Four hand spec-
imens with various concentrations were analysed multiple
times, with and without the plastic bag at the contact. The
attenuation due to the presence of the plastic bag varies with
the atomic number of the element and is relative to the amount
present in the sample; the plastic bag has a greatest impact on
the concentration of light elements (atomic number between
12 and 25). Using these repeated analyses, correction factors
specific to each element were calculated by plotting against
each other the values obtained with and without the plastic bag
for various concentrations. These correction factors were then
applied to the values obtained with pXRF on the standards
before evaluating the calibration.
Precision, detection limits and QA/QC
Precision can be divided into two types: instrumental and sam-
ple precision, where instrumental precision is defined by the
reproducibility of multiple analyses on the same point or pulp,
and sample precision by the reproducibility of multiple analy-
ses on different points (in the case of analyses on core sur-
faces) or different aliquots from the same sample. Variability in
precision arises from counting statistics on the instrument for
the former, and sample heterogeneity and representativeness
of sampling for the latter. In this study, both precisions were
determined. The instrument precision on both pulps and half
cores was obtained by multiple determination using three
3
#18 #20
#16
#19 #21
#17
#01 pXRF analysis - Trace mode
#97 #02 pXRF analyses - Major mode
#98
#99
#100
#107 #115
#109 #111 #113 #116
#108
#110 #112 #114
standards containing different concentrations of the various
elements of interest: DRD102-238, MID024-628 and MID046-
310.3. For each sample, the 10 repeated analyses were carried
out exactly at the same point on the sample. For every element,
the sample containing the median concentration was used to
calculate the instrumental precision for this element. The pre-
cision was evaluated by calculating the relative standard devia-
tion of the concentrations obtained for the 10 replicates for
both the trace and the major mode of the instrument. The
precision ‘P’ of the element ‘x’ was then calculated as being
twice the relative standard deviation (RSD) (Thompson &
Howarth 1973); P=200*σ/μ, where μ is the mean and σ is the
standard deviation. Four different instrumental precision val-
ues for each element were measured: on pulps using the trace
mode, on pulps using the major mode, on half core using the
trace mode and on half core using the major mode.
The sample precision varies considerably between samples
since it depends on both the composition heterogeneity of the
sample and on the grain size relative to the size of the analysis
window, which is only 1.5 cm2. We determined the sample pre-
cision for a talc carbonate komatiite from the Miitel deposit
(Fig. 1) by carrying multiple analyses (17) at different locations
on the sample. We calculated the relative standard deviation
between the concentrations obtained for these different loca-
tions, which gave us the sample precision, P=2*RSD. The same
exercise was carried out on a fine-grained basalt sample in order
to demonstrate the variability of the sample precision as a func-
tion of the sample heterogeneity and grain size.
With pXRF analysers, detection limits are difficult to deter-
mine precisely. They depend on numerous factors such as the
abundance of the element, matrix effects, peak overlaps and
instrument count times. A useful empirical estimate of detec-
tion limit is the lowest concentration where the relative stand-
ard deviation (RSD) between replicate analyses is less than half
of the median replicate analysis. Detection limits were deter-
mined for the most significant elements: Ni, S, Cr, Cu, Co, Fe,
Ti and Zr. The detection limits for the purpose of this study
were calculated as being three times the standard deviation.
They were obtained using replicates of the same analysis on
standards which contain relatively small amounts of the vari-
ous elements of interest. Finally, periodic replicates, SiO2 blank
analyses and repeats of one of the CRMs were used to monitor
4 M. Le Vaillant et al.
drift and ensure that the linear corrections applied to the sam-
ples were robust.
Samples
The samples used for the study are hand specimens of sawn
half-cores. Analyses were carried out directly on the samples,
on the flat surface to avoid the diffraction of X-ray from the
detector (e.g. Morris 2009). The samples were polished prior to
analysis to minimise errors due to the relief of the sample and
to avoid contamination from the saw and from oxidized mate-
rial (Morris 2009). The average grain size of the samples used
for this study is 200 to 500 μm, and the surface of the measure-
ment window of pXRF is 1.5 cm2. Approximately 2000 grains
are analysed by the instrument for each measurement.
Heterogeneity due to coarse grain size relative to the size of the
sample spot is a problem to take into account when choosing
the type of samples used for a study, and results from samples
with grain sizes in the mm range are unlikely to be representa-
tive (Fisher et al. in press).
Case study
This study presents results from pXRF analysis of samples
from three different komatiite-hosted nickel sulphide
deposits situated in the Yilgarn Craton of Western Australia:
the Perseverance, the Miitel and the Wannaway deposits
(Fig. 2). The samples analysed during this study contain no
or very little sulphides and were collected in diamond drill
holes from centimetres to hundreds of metres away from
the ore bodies. All the samples are half cut cores obtained
by diamond drilling.
The three nickel sulphide ore deposits are situated at the
basal contact between the host komatiites and the underlying
unit. They are classified as Type 1 systems, defined as sulphide-
rich contact deposits containing massive and net-textured ores
(Lesher & Keays 2002). The Perseverance deposit also con-
tains a large tonnage of Type 2 disseminated mineralization,
which overlies the massive, and matrix ore.
The Perseverance deposit is situated in the Agnew Wiluna
Greenstone Belt, where a series of cumulate-rich komatiite
units can be mapped over a continuous strike length in excess
of 100 km (Naldrett & Turner 1977; Groves et al. 1982; Marston
1984; Barnes et al. 1988b, 2012; Fiorentini et al. 2007). The
Agnew-Wiluna Greenstone Belt in Western Australia is the
most highly nickel-endowed komatiite belt in the world and
contains two world-class nickel deposits, Mount Keith and
Perseverance, as well as numerous economic deposits, such as
Yakabindie, Waterloo, Cosmos-Alec Mairs, Sinclair, Tapinos,
Prospero, Cliffs, Rocky’s Reward-Harmony, and 11 Mile Well
(Beresford et al. 2004; Barnes et al. 2011). The Agnew-Wiluna
Greenstone Belt is better endowed than the next richest
Ni-bearing komatiite belt by a factor of 5 (Hoatson et al. 2006;
Mamuse et al. 2010). The Perseverance deposit (called the
Agnew deposit prior to 1989) is the largest Type 1, Archaean
komatiite-hosted nickel deposit in the world, with reserves of
c. 45 million tonnes at 2.05 % Ni. This deposit is highly deformed
and metamorphosed at low to mid amphibolite facies, 550°C
and 3 Kb (Barnes et al. 1988a; Gole et al. 1987). In the immediate
vicinity of the ore body, primary igneous minerals and textures
are entirely overprinted by metamorphic minerals and fabrics.
This overprinting renders geochemical interpretation of pri-
mary lithology and depositional environment, accessible using
Ni, Ti and Cr ratios, most useful.
The Miitel and the Wannaway deposits are respectively situ-
ated on the eastern and the western flank of the Widgiemooltha
Dome, in the southern Kalgoorlie Terrane (McQueen 1981; Seat
et al. 2004). Both deposits are Type 1 komatiite-hosted nickel sul-
phide deposits. Miitel comprises numerous small ore bodies
organized along a shallow plunging, boomerang-shaped channel
c. 150 m wide × 3.5 km long. The Wannaway ore is distributed as
pods rather than ribbons of sulphides. Both the Miitel and the
Wannaway mineralization is hosted by talc carbonate altered
ultramafic rocks resting either directly on a tholeiitic unit or on a
thin veneer of sulphidic sediments that was deposited during a
hiatus between tholeiitic volcanism and the emplacement of
komatiite flows (Marston 1984). The ore distribution for both
deposits is partly controlled by the presence of embayments or
troughs in the upper surface of the footwall meta-basalt (Stone
et al. 2004). The metamorphic grades observed around the
Widgiemooltha Dome range from low green-schist facies (Miitel)
to mid-amphibolite facies (Wannaway) (Goscombe et al. 2009).
Results
Precision and accuracy
During this study, we evaluated both the instrument and the
sample precision. The instrument precision of the Olympus-
InnovX X500 desktop pXRF analyser was determined for
each element of interest on two sample types (drill core and
pulps). The results of this study show that the instrument pre-
cision does not depend on the sample type, but differs from
one element to the other, varies with the mode used (major or
trace) and is partly dependent on elemental abundance (Table
1, Supplementary material 1 and 2). For the elements deter-
mined with pXRF, the precision on drill core varies from 0.9 %
for Si using the major mode, to 7.8 % for Sr using the trace
mode. For the purposes of the study, the precision obtained
for Ni (2.4 % - trace mode), Ti (1.5 % - trace mode) and Cr
(3.9 % – trace mode) was amply sufficient, especially when
compared to the sample precision. The values of instrument
precision obtained for the ratios Ni/Ti and Ni/Cr are respec-
tively 4.3 % and 2.7 %. The instrument precision improves
with the concentration until it reaches a plateau (Supplementary
material 3).The sample precision obtained for the talc carbon-
ate komatiite from the Miitel deposit is considerably lower
(worse) than the instrument precision, which was expected
considering the grain size and the heterogeneity of the sample.
For Ni, Ti, Cr and Zr the sample precision results are, respec-
tively, 35 %, 63 %, 65 % and 66 % and for the Ni/Ti and Ni/Cr
ratios sample precision is 51 % and 66 % (Table 2). In com-
parison to the komatiite sample, the results obtained for sam-
ple precision on the fine grained basalt are significantly better.
Table 3 lists the comparison between sample precision on a
komatiite, sample precision on the basalt and instrument preci-
sion for all the elements used in this project. The detection
limits obtained for the various elements used in this study vary
between the elements and the analytical mode, ranging from
300 ppm for Ca (major mode) to 2 ppm for Zr and As (trace
mode) (Table 4). For Ni, Cr and Ti, the respective detection
limits obtained are 15 ppm, 30 ppm and 70 ppm.
The accuracy of the analyses obtained with pXRF is con-
strained by the quality of the calibration applied to the instru-
ment. In order to determine a calibration of the instrument
adequate for the purposes of our study, we had to evaluate the
effect of plastic attenuation when analysing the standards used
for the calibration. The attenuation correction factors obtained
and applied to the pXRF values for the standards (pulps in plastic
bags) are listed in Table 5. They differ for each element and
depend on the mode of analysis (trace or major). For Ni, Cr, Ti
and Zr, the correction factors respectively are 1.2, 1.3, 1.3 and 0
(Fig. 3). Once the plastic attenuation correction was applied, the
pXRF values obtained with the CRMs were used to determine
 pXRF in Nickel Sulphide exploration 5

Fig. 2. Map of the Kalgoorlie Terrane, Yilgarn Craton, locating the three case studies used for this project: the Miitel, the Wannaway and the
Perseverance deposits.
6 M. Le Vaillant et al.

Table 1. Instrumental precision obtained for the various elements used in the study on both pulps and drill core samples, n = 10. Concentrations and standard deviations (‘SD’) in % in the
major mode and in ppm in the trace mode. RSD, relative standard deviation; P, precision (2*RSD)

Precision on drill core Precision on pulps

Element sample concentration SD RSD P (%) Element sample concentration SD RSD P (%)

Major Si DRD102 27.8 0.12 0.4 0.9 Si DRD102 18.6 0.4 2.2 4.4
mode S MID024 0.4 0.01 3.1 6.3 S MID024 2.8 0.1 2.1 4.3
Ca MID024 3.9 0.04 1.1 2.3 Ca MID024 4.7 0.0 0.9 1.8
Fe DRD102 5.6 0.05 0.9 1.7 Fe MID024 8.9 0.1 0.9 1.9
Trace Cr DRD102 346 7 2.0 3.9 Cr DRD102 286 6 2.1 4.2
mode Ti MID046 3119 23 0.7 1.5 Ti MID046 3152 37 1.2 2.3
Cu MID046 126 2 1.8 3.6 Cu MID024 523 15 2.8 5.7
Zn MID024 97 4 3.7 7.4 Zn UMI-07-054 134 2 1.7 3.4
As DRD102 37 1 3.3 6.7 As DRD738 47 1 2.5 5.0
Sr MID046 27 1 3.9 7.8 Sr UMI-08-028 28 1 3.0 6.0
Zr DRD102 41 1 3.1 6.2 Zr UMI-07-054 73 2 3.0 6.0
Ni MID024 3665 44 1.2 2.4 Ni DRD738 870 40 4.6 9.1
Ni/Ti MID024 2.4 0.05 2.1 4.3
Ni/Cr MID024 1.5 0.02 1.4 2.7

Table 2. Sample precision obtained for the various elements used in this study for a komatiite sample (UMI-02-064-158.8) from the Miitel nickel sulphide deposit (Fig. 1). N = 17; MM,
major mode; TM, trace mode; SD, standard deviation; RSD, relative standard deviation; P, precision (2*RSD)

Ca_pct Fe_pct S_ppm Ti_ppm Cr_ppm Ni_ppm Cu_ppm Zn_ppm As_ppm Zr_ppm Sr_ppm Ni/Ti Ni/Cr
MM MM TM TM TM TM TM TM TM TM TM

Average concentration 5.3 8.4 1825 1586 2138 1174 29 109 3 11 16 0.8 0.6
SD 2.6 0.7 483 503 699 207 25 23 1 4 18 0.2 0.2
RSD 48.9 8.5 26.4 31.7 32.7 17.6 86.6 21.5 42.5 33.1 109.2 25.5 33.2
P (%) 97.7 16.9 52.9 63.5 65.3 35.2 173.2 42.9 84.9 66.2 218.3 51.1 66.5

Table 3. Comparison between instrument precision and sample precision on both a talc carbonated komatiite and a fine-grained basalt from the Miitel nickel sulphide deposit

Element Ti Cr Ni Cu As Zr Sr Si S Ca Fe

Instrument precision 1.5 3.9 2.4 3.6 6.7 6.2 7.8 0.9 6.3 2.3 1.7
Sample precision komatiite (UMI-02-064) 63 65 35 173 84 66 218 <DL 53 98 17
Sample precision basalt (DRD901-522) 28 12 26 153 29 5 29 11 137 24 21

Table 4. Results obtained when evaluating the detection limits with pXRF for the elements used in this study. DL, detection limit (3*SD)

Major mode - % Trace mode - ppm

Sample DRD102 MID024 DDB6 DRD737 MID024 DRD1352 DDB6

Element Si S Fe Ca Ti Cu Zr As Zn Cr Ni
Median concentration 3.5 34 0.19 0.31 482 71 6.5 21.5 93 127 109
SD 0.11 0.05 0.006 0.01 23 4.4 0.53 0.6 2.8 9.4 5
DL 0.33% 0.15% 200 ppm 300 ppm 69 ppm 13 ppm 2 ppm 2 ppm 8 ppm 28 ppm 15 ppm

calibration equations for the following elements: Si, S, K, Ca, Ti, Table 5. Attenuation coefficients, due to the presence of a plastic bag around the pulp
samples, evaluated for the elements used in this study
Cr, Fe, Ni, Cu, Zn, As, Sr, and Zr. Elements lighter than Si failed
to yield acceptable results and some elements such as Co, V, Rb Element Attenuation coefficient Attenuation coefficient
or Th with interferences or low concentrations could not be reli- Major mode Trace mode
ably calibrated. The calibration curves and the data points fit par-
Si 5.4 NA
ticularly well for Ni, Zn, S, Fe and Zr. For these elements, the
Si 3.2 2.6
correlation coefficient between the expected values and the K 2.9 1.6
pXRF values are 1.00 for Ni and Zn and 0.99 for S, Fe and Zr. Ca 1.6 1.3
(Fig. 4, Supplementary material 4). Ti 1.5 1.3
Cr 1.4 1.1
Case study results Fe 1.3 1.1
Barnes et al. (2004) proposed the use of a plot that combines Ni 1.2 1.3
Ni/Ti and Ni/Cr ratios to assist in the discrimination between Cu 1 1
different komatiite flow environments (Hill et al. 1995): layered Zn 1.5 1.5
As NA 1.1
lava lakes and/or sills (LLLS), dunitic compound sheet flows
Sr NA 1
(DCSF), thin differentiated flows (TDF) and compound sheet Zr NA NA
flows with internal pathways (CSF) (Table 6), CSF and DCSF
 pXRF in Nickel Sulphide exploration 7

A Si - % - plastic attenuation B S - % - plastic attenuation

40 4.0

without plastic
without plastic y = 5.4x y = 3.2x
30 3.0

20 2.0

10 1.0

0 0.0
0 2 4 6 8 0.0 0.4 0.8 1.2
with plastic with plastic
C 9
Ca- % - plastic attenuation D Ti - ppm - plastic attenuation
5000
without plastic

y = 1.6x y = 1.3x

without plastic
7 4000

5 3000

3 2000
1000
1
0 0
0 1 2 3 4 5 6 0 1000 2000 3000
with plastic with plastic

E Cr - % - plastic attenuation F Fe - ppm - plastic attenuation

0.25 180000
0.20
without plastic
without plastic

140000 y = 1.1x
0.15
y = 1.3x
100000
0.10
60000
0.05
20000
0.00 0
0.00 0.05 0.10 0.15 0.20 0 20000 60000 100000
with plastic with plastic
Fig. 3. Plots illustrating the effect of the presence of a thin plastic bag between the sample and the pXRF analyser. The correlation coefficient
of these plots represents the attenuation due to the plastic bag; it is greater for light elements. This correlation coefficient is to be applied to the
results when analysing a sample through this same plastic bag.

being the most prospective environments for komatiite-hosted
nickel sulphide deposits. The results provided by the pXRF
analyses on all the komatiite samples are used to test the pos-
sible use of selected komatiite nickel sulphide exploration
plots. The variations and differences observed between the
different types of komatiite samples are greater than the instru-
ment and the sample precision represented by the error bars
on the various graphs.
In order to test the use of pXRF to generate Ni, Ti and Cr
ratio plots, we analysed 75 komatiite samples collected from
the Miitel, Perseverance and Wannaway deposits, generating
c. 670 single analyses which represent c. 9 analyses per sample.
Figure 5 shows the three different types of komatiites analysed
for this project.
Samples from the Wannaway and Perseverance deposits
plot within the mineralized field on a Cr versus Ni plot (Fig. 6),
with a noticeable enrichment in Ni and low Cr concentrations.
This enrichment in Ni is to be expected from samples collected
not farther than 10 m away from the ore body. The size of
anomalous geochemical signatures around magmatic nickel sul-
phide deposits is an important question for exploration target-
ing, and has been addressed by Heggie et al. (2012) at Maggie
Hays, and by Barnes et al (in press) and Lesher et al (2001) at
Kambalda. The samples from the Miitel deposit have been col-
lected farther away from the ore body (50 m to >230 m) and
show low Cr values and background Ni contents.
Most samples from the Perseverance deposit were collected
close to the ore body and contain disseminated sulphides. In
the Ni/Ti vs Ni/Cr diagram (Fig. 7) they plot in the field rep-
resenting samples with >1 % sulphides. In this same diagram,
the samples from the Miitel and Wannaway deposits mainly
plot in the CSF and DCSF fields, or in the intersection between
DCSF and above the 1 % S fields for samples containing small
amounts of sulphides. Some komatiite samples from the Miitel
deposits were also analysed by Ultra Trace laboratories in
Perth. These samples plot closely together with the Miitel
komatiite samples analysed by pXRF in Figures 6 and 7.
Figure 8 shows the results obtained with the data collected
with pXRF for the Zr vs Ti diagram used to evaluate crustal
contamination of komatiite flows. Most of the samples plot
8 M. Le Vaillant et al.

A Calibration curve S - Major mode B Calibration curve Cr - Trace mode

25 2500

Lab values_ppm
Lab values_pct
20 2000
y=2.6x+1.6 y=1.1x-161
15 1500

10 1000

5 500

0 0
0 1 2 3 4 5 6 7 8 0 500 1000 1500 2000
pXRF values_pct pXRF values_ppm

C Calibration curve Ti - Trace mode D Calibration curve Fe - Major mode

14000 25
Lab values_ppm

Lab values_pct
12000
10000 y=1.1x-618 20
y=1.4x-4.3
8000 15
6000
10
4000
2000 5
0
0 2000 4000 6000 8000 10000 12000 14000 0
0 5 10 15 20
pXRF values_ppm pXRF values_pct

E Calibration curve Ni - Trace mode F Calibration curve Zr - Trace mode

300
14000
Lab values_ppm

250
Lab values_ppm

10000
y = 1.5x + 300 200 y=1.2x+1.8
150
6000
100

2000 50

0 0
0 2000 4000 6000 8000 10000 0 20 40 60 80 100 120 140 160
pXRF values_ppm pXRF values_ppm
Fig. 4. Calibration curves for S, Cr, Ti, Fe, Ni and Zr. These calibration curves were obtained using mafic and ultramafic standards from the Miitel
komatiite-hosted nickel sulphide deposit. The calibration equations are to be applied for matrix-matched samples only.

Table 6. Definition of the komatiite volcanic facies described in Barnes et al. (2004) and used in this study

Facies Description Type example

Thin Differentiated Flows Multiple compound spinifex-textured flows; generally less than 10 m thick, Munro Township (Pyke et al. 1973)
(TDF) with internal differentiation into spinifex and cumulate zones.
Compound Sheet Flows Compound thick cumulate-rich flows with central olivine-rich lava pathways Silver Lake Member at Kambalda (Lesher et al. 1984)
with internal pathways flanked by multiple thin differentiated units, from tens of metres to about
(CSF) 200 m maximum thickness.
Dunitic Compound Sheet Thick olivine-rich sheeted units with central lenticular bodies of olivine Perseverance and Mt. Keith (Hill et al. 1995)
Flows (DCSF) adcumulates, up to several hundred metres thick and 2 km wide, flanked by
laterally extensive thinner orthocumulate-dominated sequences with minor
spinifex. CSF and DCSF correspond to “Flood Flow Facies” of Hill et al.
(1995).
Dunite Sheet Flow (DSF) Thick, laterally extensive, unfractionated sheet like bodies of olivine Sounthern section of Walter Williams Formation
adcumulates and mesocumulates, in some cases laterally equivalent to (Gole & Hill 1990; Hill et al. 1995)
layered lava lake bodies.
Layered Lava Lakes and / Thick, sheeted bodies of olivine mesocumulates and adcumulates with Kurrajong section of the Walter Williams Formation
or Sills (LLLS) lateral extents of tens of kilometres, with fractionated upper zones (Gole & Hill 1990; Hill et al. 1995)
including pyroxenites and gabbros, up to several hundred metres in total
thickness.
 pXRF in Nickel Sulphide exploration 9

A B C

1 cm
1 cm 1 cm

Fig. 5. Three different types of komatiite samples analysed during this project. The samples come from (A) the Miitel deposit, (B) the Persever-
ance deposits and (C) the Wannaway deposit.

9000
Komatiite from Miitel - pXRF
8000 Komatiite from Wannaway - pXRF
Cr ppm Komatiite from Miitel - Ultratrace
7000 laboratories
Komatiite from Perseverance - pXRF
6000
U90 Ni/Cr =1 Unmineralised
Mineralised
5000 Instrument precision

4000
M90
3000 U50 Sample precision

2000
M50
1000
Ni ppm
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 22000

Fig. 6. Cr vs Ni plot adapted from Barnes et al. (2004). Contours represent 50th and 90th percentiles of both mineralized and unmineralized
komatiite flows of any type. Within the diagrams, the data obtained for Ni and Cr concentrations of komatiites from the Miitel, the Wannaway
and the Perseverance nickel sulphide deposits are plotted. The error bars represented on the diagram have been calculated as 2 times the RSD
(respectively representing the instrumental and the sample precision), for values of Ni and Cr of 2000 ppm.

along the mantle Zr/Ti ratio, but have slightly and consistently
higher Zr values consistent with a Zr blank of c. 5 ppm.
Notwithstanding this, the correspondence of the measured
slope in the Zr/Ti plot with the expected mantle value is
remarkable, and testifies to the reliability of the method. A
small proportion of samples have increased values of Zr, plot-
ting well above the mantle ratio, implying a component of
crustal contamination in the host flows.
Recommended Protocol
This investigation of the application of pXRF to komatiite-
hosted nickel sulphide exploration allowed us to develop a
simple recommended protocol for the analysis of drill core
samples from komatiite-hosted nickel sulphide systems,
essentially similar to that recommended by Fisher et al. (in
press). Drill core samples should be sawn in order to allow
analysis on a flat surface (Morris 2009). Samples can also be
quickly polished in order to reduce relief and contamination
problems. The instrument set-up recommended depends on
the types of samples analysed, and as the results of this study
show, sample precision in particular will change significantly
as a function of grain size and heterogeneity of the samples.
Instrumental precision improves at longer counting times,
but there is no advantage in having instrumental precision
greatly better than sample precision, so the value of increased
counting times diminishes rapidly; in most cases, we would
recommend a minimum of 20 seconds count time per beam,
and maxima of 60 s per beam times for the trace mode and
30 s for heavy elements and 60 s for light elements using the
major mode. To obtain appropriate calibration equations, the
standards need to be chosen carefully to match the composi-
tion of the samples to be analysed, and we counsel the user
to regularly analyse blanks, standards and produce replicates
to control and assure the quality of the data. Finally, it is
important to archive the data with detailed information about
its quality (instrument, count times, record of CRM and
detection limits; Fisher et al. in press).
10 M. Le Vaillant et al.

Komatiite from Miitel - pXRF

1000
Komatiite from Wannaway - pXRF
Komatiite from Miitel - Ultratrace
laboratories
Komatiite from Perseverance - pXRF
100 samples > 1%
DCSF
LLLS
10

Ni/Ti
CSF
1

TDF
0.1
instrument precision
sample precision
Ni/Cr
0 0.1 1 10 100
Fig. 7. Ni/Ti vs Ni/Cr adapted from Barnes et al. (2004) used as a tool for the assessment of komatiite prospecitivity in exploration targeting. The
contours represent the 50th percentile of different komatiite volcanic facies (Table 6). In the diagram the data obtained on the komatiite samples
from the Miitel, the Wannaway and the Perseverance nickel sulphide deposits are plotted. The error bars represented on the diagram have been
calculated as 2 times the RSD (respectively representing the instrumental and the sample precision), for values of Ni/Ti and Ni/Cr of 1.

Komatiite from Miitel - Ultratrace Komatiite from Wannaway - pXRF

laboratories
Komatiite from Miitel - pXRF Komatiite from Perseverance - pXRF
80
instrument precision

50 Zr ppm
tle ratio
Man

Ti ppm

0 1000 2000 3000 4000 5000 6000 7000 8000

Fig. 8. Ti vs Zr diagram for all the samples analysed from the Miitel, the Wannaway and the Perseverance nickel sulphide deposits.

Conclusion
The results obtained by pXRF on the samples from the Miitel,
Wannaway and Perseverance deposits match well with labora-
tory data, and plot in the appropriate areas of discriminant
plots involving the elements Ni, Cr, Ti and Zr. Therefore, we
conclude that the use of pXRF analysis, in conjunction with
thorough calibration and QA/QC, produces meaningful data-
sets allowing a rapid assessment of the nickel sulphide pro-
spectivity of komatiites. For the typical abundances of Ni, Cr,
Ti and Zr in komatiites, pXRF data on drill core or pulps can
be used as an effective guide.
Nickel and Cu concentration results can be successfully col-
lected during exploration campaigns and interpreted to evalu-
ate sulphide segregation and define the nickel sulphide
prospectivity of komatiitic units. The quality of analytical data
for Ti, Cr and Zr enables discriminant element ratios (e.g. Ni/
Ti, Ni/Cr, Zr vs Ti diagrams) to be used to gain information
on the volcanic environment and on the extent of crustal con-
tamination of host komatiite flows.
Portable XRF is a powerful instrument, which permits
rapid testing of working hypotheses made in the field, and
which enables rapid decisions to be made on-site in real time
during drilling programmes. This study demonstrated that for
komatiite-hosted nickel sulphide exploration, pXRF repre-
sents a robust tool that complements other common field
analyses. Laboratory XRF analysis on pulps can subsequently
be used to confirm and refine results and to obtain research
quality applications.
 pXRF in Nickel Sulphide exploration
Support for this research and permission to publish comes from
MERIWA and jointly from BHP Billiton, Mincor Resources NL and
First Quantum Minerals Ltd. Peter Mucilli, Than Doan, Caroline Per-
ring, Michael Verrall and John Miller are thanked for their help and
comments on a draft of this manuscript. This is an output from the
CSIRO Minerals Down Under National Research Flagship, and this
is contribution 249 from the ARC Centre of Excellence for Core to
Crust Fluid Systems.
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