A Review of the Reliability and

Validity of Portable X-ray Fluorescence

Spectrometry (pXRF) Data
M F Gazley1 and L A Fisher2

ABSTRACT
The increasingly widespread use of portable X-ray fluorescence (pXRF) technology by the minerals industry has promoted
the collection of large multi-element geochemical data sets. However, for this technology to truly add value to the mining and
exploration process, it is necessary to recognise some of the constraints on data quality so that best possible data can be collected.
This is of particular importance where this data, or interpretation based on it, will be publicly reported. This paper reviews some
of the key quality assurance/quality control (QA/QC) issues associated with pXRF data collection so that people collecting and
interpreting this data can assess whether it is fit for purpose. We present a summary of QA/QC issues that have been raised in
the literature, discuss the application of the Joint Ore Reserves Committee (JORC) Code (2012) to pXRF data and offer suggestions
as to how pXRF data can comply with the expectations of JORC (2012). Although guidelines for the collection of pXRF data are
available in the literature, appropriate methods for data collection must be based on factors including local geology and purpose
of data collection. For this reason a prescriptive approach to pXRF data collection is not put forward. We recommend that those
reporting pXRF data ensure that they comply with the requirements for representivity and subsampling as outlined in JORC (2012)
and that they are able to demonstrate that their pXRF data is reliable, accurate and fit for purpose by following the specific criteria
for reporting of Exploration Results, Mineral Resources and Ore Reserves given by JORC (2012). A list of considerations beyond
those provided in Table 1 of JORC (2012) is provided as guidance to assist the evaluation of pXRF data quality for public reporting.

1. GAusIMM, Project Geologist, Barrick (Australia Pacific) Limited, Locked Bag 12, Cloisters Square, Perth WA 6085 and Victoria University of Wellington, PO Box 600, Wellington, New Zealand.
Research Scientist, CSIRO Earth Science and Resource Engineering, PO Box 1130, Bentley WA 6102. Email: michael.gazley@csiro.au
2. Research Team Leader, CSIRO Earth Science and Resource Engineering, PO Box 1130, Bentley WA 6102. Email: louise.fisher@csiro.au

INTRODuCTION
Portable XRF units are the miniaturisation of larger laboratory-
based units that have formed the basis of multi-element
analyses for decades. In short, pXRF units emit X-rays that
excite atoms in the sample being analysed, resulting in the
displacement of inner shell electrons (Figure 1). Outer shell
electrons fall into the space left by the displaced electrons
and in doing so, fluoresce; that is, they emit electromagnetic
radiation with an energy that is equivalent to the difference

FIG 1 - X-rays are emitted from the unit, which excite atoms in the sample being analysed; this results in the displacement of inner shell electrons.
Outer shell electrons fall into the space left by the displaced electron and in doing so emit fluorescence that is characteristic of each element.
The intensity of the energy is proportional to the concentration of the element in the sample.

Mineral Resource and Ore Reserve Estimation 1

Chapter 2 | The Resource Database
in energy between the two electron shells. The wavelength
of the energy emitted is (largely) characteristic of each
element and the intensity of the energy is proportional to the
concentration of the element in the sample. While the physics
behind how pXRF analyses are performed remains the same
as laboratory-based methods, the entire process from sample
preparation and the conditions of the analysis to quality
assurance and quality control (QA/QC) are in the hands of
the person operating the unit.
The title of this paper is adapted from an article written by
M Steven Shackley in the Society for American Archaeology
(SAA) Archaeological Record (Shackley, 2010), as it asks an
important question: is there reliability and validity in portable
X-ray fluorescence spectrometry? In that article, Shackley
reported that at a conference, a group of archaeologists were
having a heated debate on precisely this point. In writing this
paper, we seek to raise the profile of some of the important
issues associated with this method of data collection as we
believe that the way Shackley (2010) summed up the situation
for archaeologists also applies to geologists:
... it became clear that there were many pXRF instruments
out there being used for any number of applications by a
discipline not necessarily prepared for it intellectually, and
that there is a connection between the very real and serious
issue of poor scientific training … and specifically here the
potential misuse of this emerging technology …
Portable XRF technology makes everyone an analytical
chemist, even though not everyone is trained as one.
REVIEW OF APPLICATIONS
The minerals industry has embraced the use of pXRF
technology as a method for rapid data collection; geologists
at the drill rig, in the production setting or in the field are
now able to obtain near real-time geochemical analyses.
Potential applications of pXRF technology in the minerals
industry range from grade control to lithogeochemistry and
geometallurgy to soil sampling. Despite this widespread
application, to date there have only been a couple of case
studies published in the literature (Gazley et al, 2011, 2012),
though many further studies are anticipated in the near
future (eg Fisher et al, 2014; Le Vaillant et al, 2014). Methods
for the analysis of geological samples were first presented
by Morris (2009) and expanded upon by Gazley (2011) and
Gazley et al (2011).
Researchers in fields such as soil science, archaeology and
biology have also begun to use pXRF extensively. Portable
XRF technology has been used to determine the extent of
environmental pollutants such as As, Pb and other heavy
metals in soil samples (Clark et al, 1999; Kalnicky and Singhvi,
2001; Kilbride, Poole and Hutchings, 2006; Carr et al, 2008;
Markey et al, 2008; Hürkamp, Raab and Völkel, 2009; Radu
and Diamond, 2009; Jang, 2010; Peinado et al, 2010). Recent
advances in analytical techniques and issues associated with
the analysis of soil samples by pXRF technology are discussed
by Kenna et al (2011) and Parsons et al (2012). Portable XRF
has also been used to screen air-monitoring filters for metals
(eg Bernick and Campagna, 1995). Archaeologists have
used pXRF as a non-destructive method to analyse artefacts
such as obsidian, glass and stone objects to determine their
composition and potential provenance (Craig et al, 2007;
Phillips and Speakman, 2009; Kato, Kakai and Shindo, 2009;
Jia et al, 2010; Nazaroff, Prufer and Drake, 2010; Tykot, 2010;
2 Mineral Resource and Ore Reserve Estimation
Sheppard, Trichereau and Milicich, 2010). Biologists have
used pXRF to determine P and Si concentrations in biological
samples rapidly and accurately, where digestion-based
techniques are often hazardous and time-consuming and,
particularly in the case of Si, can suffer from low accuracy
due to incomplete dissolution and potential volatilisation
(Reidinger, Ramsey and Hartley, 2012). Portable XRF
technology also has industrial applications including
determining the nature of alloys and scrap metal, as well as
quality control in manufacturing and testing for heavy metals
in paint.
Different fields that utilise pXRF technology have
approached it from different points of view; they have tested
and validated aspects of pXRF data collection dependent on
the research questions or biases of that science. All of this
information should be drawn on to ensure that all users
collect the most robust and reliable data set possible.
PORTABLE X-Ray Fluorescence DATA AND
the JORC CODE
The JORC Code provides the minimum standards for public
reporting of Exploration Results, Mineral Resources and Ore
Reserves in Australasia. JORC (2012) states that for pXRF
data ‘parameters used in determining the analysis including
instrument make and model, reading times, calibrations,
factors applied and their derivations, etc’ must be supplied
along with the analyses. This paper expands on that list and
offers further recommendations to ensure that pXRF data are
both robust and reliable. We do not aim to be prescriptive
nor definitive, and those publicly reporting pXRF data must
ensure the quality of their data through whatever processes
they deem suitable. This paper has been prepared in the
context of JORC (2012) and is expected to be consistent with
the required practices of other international reporting codes
and standards.
Portable XRF data is perhaps most useful in an exploration
setting where rapid results can be obtained on materials such
as diamond core, reverse circulation or rotary air-blast chips
and hand samples. The technique is also often applied to soil
sampling to identify geochemical anomalies. In this latter
situation, it is important to consider collecting samples of the
measured soil for follow-up analysis to show reproducibility
of the data. Sampling directly onto the soil in the field,
even with a precise grid reference, is unlikely to satisfy this
requirement, as check samples are unable to be produced later
to verify the results that have been presented. Furthermore,
sampling directly in the field presents a number of significant
analytical issues and precludes a subset of the samples being
subsequently analysed by an alternate method as a check of
data quality. In the early stages of exploration, in accordance
with continued reporting to investors, when the quantity of
data is generally not sufficient to allow an estimate of Mineral
Resources, pXRF results may form an important part of a
company’s exploration data set. It is important that pXRF
results reported as Exploration Results are collected to ensure
sample representivity and the measures taken to achieve this
can be reported; see Table 1 in JORC (2012).
When considering the reporting of Resources or Reserves,
it is unlikely that pXRF data will form the primary data set
on which a Mineral Resource or Ore Reserve is calculated.
It is more likely that pXRF data will form part of a supporting
geological or geometallurgical model when Reserves or
 A Review of the Reliability and Validity of Portable X-ray Fluorescence Spectrometry (pXRF) Data | M F Gazley and L A Fisher
Resources are being reported. If pXRF data forms a key
component to the understanding of the geology of the deposit
(Gazley et al, 2011) or is used to calculate geometallurgical
factors or assumptions (eg Gazley et al, 2012), then these data
need to be of suitable quality as both the geological model and
metallurgical data will be publicly reported to support JORC
(2012) compliant Exploration Results or Resource or Reserve
statements. This can be taken to mean being transparent as to
the significance of any such data in the model. Additionally,
in mining there are requirements for internal reporting, such
as production or grade control, where the provisions of JORC
(2012) do not apply. However, the guidance that is offered in
this paper should still be applied to these data to ensure they
are of suitable quality.
INSTRUMENTATION
There are a number of key issues with regards to
instrumentation used for pXRF analyses that need to be
considered. First, the age and model of the unit: modern
units are likely to have larger detectors and hence better
detection limits. Generally, most hardware in the past has
been optimised for heavy elements using Ta and W anodes,
but more recent advances in anode technology have enabled
the use of Rh and Ag anodes for lighter element analysis –
this is particularly important for the analysis of Mg, Al,
Si, P and S. Consequently, it may be possible to determine
element concentrations with the same degree of precision
and better counting statistics in shorter analysis times than
with older models. However, this will vary between units
and the performance of each unit needs to be tested prior to
an analytical campaign; a possible process for this is outlined
in the ‘Analytical Protocols’ section below. The analytical
protocols that are suitable for one unit should not be
presumed to be suitable for another unit, nor even the same
unit at another site or geological setting.
Second, different units are optimised for different purposes.
It is important to discuss with the manufacturer the nature of
the calibration that has been set up on a pXRF unit and the
optimisation of the unit to detect certain elements (eg rare
earth elements). Furthermore, to analyse light elements (ie Mg,
Al, Si, S or P), a thin window (eg 4 µm prolene film) should be
used. If a unit is to be used only in ultramafic rocks, it could be
appropriate to calibrate it for ultramafic rocks but it may give
erroneous measurements if it is then used to analyse felsic
FIG 2 - Strontium, Rb and Zr concentrations measured in the same trachyandesite sample from Murry Canyon utilising two different portable X-ray
fluorescence units from the same manufacturer; modified after Goodale et al (2012).
rocks. Likewise, a unit that is optimised for use on silicate
rocks will likely perform poorly on rocks that have a high
sulfide content. While it is possible and potentially desirable
to calibrate a unit to a given rock type or matrix, it could,
however, be detrimental to the quality of results if someone
who was not aware of this calibration started using it, or it
was used to analyse rocks that did not match this calibration.
Accordingly, it is probably more appropriate to use a generic
calibration and in post-processing apply a correction to each
element of interest, with the correction based on analysis
of standards that are matrix-matched to the samples being
analysed. For further discussion on the importance of this,
see the ‘Calibration and Reference Materials’ section below.
Third, different units can report different concentrations
for a given element even if they measure the same sample,
despite both instruments being the same model from
the same manufacturer. This effect is highlighted by data
published by Goodale et al (2012), which is reproduced in
Figure 2 and is consistent with the authors’ experience. This
figure highlights the stark difference in precision between
two similar units, emphasising the importance of treating
data from each pXRF unit separately. Furthermore, through
time, instrumental drift may occur and a calibration or
correction that was calculated at a specific time may no
longer be suitable the next month. This is an inherent
characteristic of analytical equipment and can readily be
corrected for if it is known to be occurring. Routine analysis
of the same standard(s) as part of a set analytical protocol
(eg one in 20 samples is a standard) allows analytical drift to
be tracked. These repeat analyses can be plotted against time
to determine whether any long-term drift is occurring within
the unit. Once drift exceeds a predetermined threshold (eg
five per cent of median value), the unit should be serviced and
a new threshold set or calibration established. An example
of this type of long-term drift is shown in Figure 3. Short-
term drift has also been recognised in repeated analyses of
the same standard; examples of the types of drift that have
been identified by the authors are identified in Figure 4.
In the ideal situation, there will be no short-term drift such
as shown in Figure 4a; however, this is rarely the case. Drift
that can be readily corrected for will be either stepwise drift
(Figure 4b), which can be corrected with frequent analysis
of standards and two sets of correction factors calculated for
the data set, or gradual drift (Figure 4c), which is harder to
correct for as an interpolation is required between standards
Mineral Resource and Ore Reserve Estimation 3
Chapter 2 | The Resource Database

FIG 3 - Long-term drift of a single portable X-ray fluorescence unit over 12 months analysing the same standard each time. 5 × analyses were collected at the start of
each analysis session. Note low analyses, which will result when the sample is not sitting well against the unit; low and high outlier analyses suggest using a median
rather than an average concentration to calculate a correction factor is likely to yield better results. Dashed lines indicate rapid changes in measured concentration at
the same date on each panel. (A) Ca; (B) Mn; and (C) Cu concentrations of metabasalt standard PLU-1 (expected concentrations presented in Fisher et al, 2014).

or multiple correction factors calculated. Such drift patterns
are potentially the result of an increase in machine internal
temperature (and consequently air pressure), which could
result in peak positions migrating, so some elements
would increasingly over-report and others under-report.
Manufacturers are working on building these corrections
into the software and hardware (eg by installation of
barometers and thermometers), so drift may be less likely
to occur in new models. Apparently, random fluctuation
between two values has been observed in a number of pXRF
units and presents itself in a manner such as Figure 4d. This
is virtually impossible to correct for and to detect during
an analysis run and needs to be identified during routine
analysis of standards. If this is identified in standard data,
it should be noted when the battery is switched in the unit
and whenever the unit is restandardised, but if this fails to
fix the issue the unit should be sent for servicing.
Fourth, analytical and sample interferences need to also be
considered. While the energy emission lines of the emitted
energy are (largely) characteristic of a given element, this is
not always the case and there are certain pairs of elements that
have peaks that overlap each other. This can be problematic
for elements such as W, As, Pb, Zn and Au, Ba and V, Fe and
Co and rare-earth elements. An example of the similarities
between two elemental lines is shown in Figure 5 for Au
and W. If the detector in the pXRF unit does not have sufficient

4 Mineral Resource and Ore Reserve Estimation

 A Review of the Reliability and Validity of Portable X-ray Fluorescence Spectrometry (pXRF) Data | M F Gazley and L A Fisher

FIG 4 - Four type-examples of short-term analytical drift from real portable X-ray fluorescence (pXRF) data. Data collected in a single analysis session with repeated
analyses of the same standard at a constant temperature. These data show the types of analytical drift that can occur in pXRF data and need to be corrected for by
frequent, and appropriate, standards and calculation of correction factors. (A) Ideal data; (B) a step change during analysis, potentially caused by the sample moving
or a step change in the internal calibration of the unit; (C) gradual drift, potentially occurs soon after start-up of the unit before it is warmed up; and (D) random
fluctuation between two values.

resolution to determine the difference between these lines, or
the software within the unit is unable to deconvolve the peaks
successfully, a false concentration for Au will be determined
when W is present. This process can be aided by the use of
other lines to identify elements such as using both the Mα1
and Mα2 lines, as well as the L lines to identify Au instead of
the Lα1 line (9.71 keV) of Au, which can be interfered with by
the Lβ1 line of W (9.67 keV) (see Figure 5). While historically
users have had no choice in which peak(s) the pXRF unit uses
to identify elements, they needed to be aware of elements that
can potentially cause interference effects so that they could
determine when concentrations were real or may be the
result of interference. It is now possible to have an advanced
user configuration installed on some units that enable the
user to change which emission lines are used to identify
which elements; however, this type of configuration should
only be carried out following discussion with manufacturers
regarding the specific project requirements.
SAMPLE CONSIDERATIONS
Nature of the material to be analysed
For any kind of geochemical analysis, sample heterogeneity
needs to be addressed. For elements such as gold, which can
have a high nugget effect, it would be unwise to assume that
a 20 cm long piece of core represents a 1 m interval. The same
applies to pXRF data, where a single spot-analysis that is
approximately 10 mm in diameter (the size of the analysis
window of a pXRF unit) cannot be assumed to represent 1 m
of diamond drill core. Many trace elements are present in
single-phase minerals (eg As in arsenopyrite), thus a sample
that is to be analysed by pXRF may need to be homogenised
to be representative. The same is true of a coarse-grained rock
‘sample’; with only a small surface area available to the pXRF
unit to analyse, it is possible to end up analysing single phases
(Figure 6). Furthermore, the depth that the X-rays from the
unit penetrate into the sample is limited, while varying by
atomic weight of the element, it is typically submillimetre.
Multiple analyses that are then averaged within a defined
interval may help to improve representivity (Le Vaillant et al,
2014) if it may be assumed that the material being sampled is
consistent (eg the material at the surface of core is the same as
that beneath the penetration depth of the X-rays).
If a sample contains moisture, this attenuates X-rays and
results in low concentrations being recorded. Figure 7 is
reproduced from Parsons et al (2012) and shows the effect of
analysing samples that are not completely dry. For example,
a moisture content of ~30 per cent will result in attenuation of
measured Fe, Mn and As concentrations to be 40 - 60 per cent
of their true values. This suggests that soil sampling or in situ
analyses of samples needs to be carried out with the utmost
care, or concentrations that are significantly lower than the
true values will be determined by pXRF analysis in the field.
In light of the data presented in Parsons et al (2012), consider
the effect of a shower of rain or sampling in the vicinity of
a watercourse on a soil-sampling campaign. It may also be
possible to monitor moisture contents in the field using a

Mineral Resource and Ore Reserve Estimation 5

Chapter 2 | The Resource Database
FIG 5 - Spectra for Au and W showing the similarities between the two and
how the Lβ1 peak (9.67 keV) of W can interfere on the Lα1 peak (9.71 keV) of Au.
If the detector in the portable X-ray fluorescence unit does not have sufficient
resolution to determine the difference between these peaks, or the software in
the unit is unable to deconvolve them successfully, then a false concentration
for Au may be determined when W is present.
A
B approximately 30 cm long on both the curved and flat surfaces
FIG 6 - Sampling precision will be reduced in samples with coarse grain size;
for this reason it is recommended that samples are pulverised prior to analysis
as this ensures the representivity of the analysis.
6 Mineral Resource and Ore Reserve Estimation
FIG 7 - Normalised attenuation of measured concentrations of As, Fe and Mn due
to the presence of soil moisture (normalised as a percentage concentration loss);
after Parsons et al (2012). Error bars = standard deviation from five replicates.
moisture probe and apply a post-processing correction to
account for this, or to at least highlight the potential need for
further verification sampling.
Pulverising a sample allows an opportunity for the issues
of representivity and moisture content outlined above to be
addressed. During this process, the sample can be dried to
ensure that when it is analysed it is free of moisture and the
resulting analyses are not falsely low. Pulverising a sample
also increases the homogeneity of a sample, increasing
the precision of a single analysis of the pulverised sample.
Figure 8 shows the uncorrected results of analysing a single
piece of fine-grained dolerite (grain size <1 mm) core that is
20 times using an Innov-X Omega pXRF unit. The same sample
was then crushed to 97 per cent passing 2.8 mm and analysed
while contained in a plastic bag. This same material was then
pulverised to 90 per cent passing 70 µm and again analysed
 A Review of the Reliability and Validity of Portable X-ray Fluorescence Spectrometry (pXRF) Data | M F Gazley and L A Fisher

FIG 8 - Box and whisker plots for K, Zr, Ca and Sr showing variation in concentrations for the same interval of dolerite core with decreasing particle size; solid
curved core, solid flat core, crushed core (97 per cent passing 2.8 mm) and pulverised core (90 per cent passing 70 µm). Note how the interquartile range and
outliers decrease significantly when the flat side of the core is used instead of the curved surface and it decreases further when particle size is also reduced.
The central box is the middle 50 per cent of the data, the mean is the circle and the median the line.

in the same plastic bag. Attenuation by the plastic bag was
found to be insignificant and no elements were added by
the presence of the plastic, as verified by analysis of the core
and a SiO2 blank both with and without the plastic between
the pXRF unit and the blank. It should, however, be noted
that pulverisation in steel and tungsten carbide mills can
introduce contamination from the mill material (Hickson and
Juras, 1986). Pulverising the sample also allows for a suitable
powdered standard to be analysed during an analysis session
to allow correction of the data (see ‘Calibration and Reference
Material’); this is important as it is difficult to find a suitable
standard material for solid-rock analysis. However, if solid-
rock standards are not available, pulverised material may be
used instead (eg Le Vaillant et al, 2014).
the raw data. It is important to know the effect of the sample
container as paper and plastic can contain elements such as
Ca, Cu, Zn, As and Zr.
Care must be taken to ensure that the thickness of the
sample in the container is sufficient to ensure that the X-rays
emitted by the pXRF unit do not penetrate through the
entire sample as this will result in falsely low concentrations.
Figure 10, after Parsons et al (2012), quantifies this effect
using increasingly small volumes of a pulverised sample in a
Mylar® XRF cup for analysis. As sample thickness decreases,
the measured concentrations decrease as well. The intensity
of this effect is largely dependent on the atomic weight of the
element being measured, with heavier elements less affected.

Presentation of the sample to the unit Calibration and reference materialS

While it is advantageous to pulverise a sample before analysis,
pulverising means that the sample has to be presented to the
pXRF unit in a sample container. It is possible to analyse
powder directly, but this would introduce high potential for
cross-contamination of samples, with powder from previous
samples adhering to the unit’s analysis window. Paper
and plastic bags have been used in a number of studies
(eg Morris, 2009; Gazley et al, 2011; 2012; Fisher et al, 2004)
and can be effective depending on required data quality. For
optimum data quality, pressed powder in Mylar® cups is the
preferred way to present samples to a pXRF unit (Figure 9).
However, this is not always practicable, and the effect of
the sample container is best corrected for by ensuring that
the calibration standard is also in a similar container. Any
contaminants within this material can be monitored through
the analysis of a SiO2 blank (in the sample container) and
corrected for by subtracting any added concentrations from
Each pXRF unit will be slightly different so a series of basic
tests and checks should be run when setting up a new unit
to establish appropriate settings for the planned analytical
work. An initial check of the instrument calibration should
be run by analysing standards with a range of compositions
to ensure that there are no major discrepancies between the
expected and measured concentrations for each standard.
To minimise matrix effects during analysis, the standards
used for calibrating a pXRF unit should be of comparable
composition to the samples to be analysed; ie they should
be matrix-matched. This may include standards that are
created in-house and sourced from local material or those
that are commercially available. In an environment where
two or more disparate lithological groupings are likely to
be analysed, it may be advisable to set up two separate
calibrations that can be applied retroactively as part of a
lithogeochemical schema and data management workflow.

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Chapter 2 | The Resource Database

FIG 9 - Effect of the nature of the material between standard and unit; after Fisher et al (2014). Ac = analysis in container and A = analysis with no container,
such that the analysis of the sample with no container plots along the line at 1. Thicker material, such as paper or plastic bags cause greater attenuation and
may also contain elements that cause additions to the analysis. Attenuation is typically greater for lighter elements.

FIG 10 - Thickness of sample (by weight in Mylar® cup) after Parsons et al (2012); showing decreasing analysed value with decreasing sample thickness.

The importance of matrix matching is demonstrated by
comparing calibration factors and offsets: calculated using
a suite of standards that represent a broad suite of rock
types and calibration factors, against those calculated using
a set of pulverised rock samples from an ultramafic-hosted
nickel-sulfide deposit (Fisher et al, 2014), shown in Figure 11.
When the different calibrations are plotted against each
other, they show that for some elements the slope of the
line is similar with some differences in offset, whereas for
other elements there is a significant difference in the slope
of the calibration line. In cases where calibrations diverge
at high or low concentrations, a correction that was not
matrix-matched could result in large errors when applied
to data that fell above or below this threshold. If data from
samples with ultramafic compositions were corrected using a
calibration determined from analysis of standards with felsic
to ultramafic compositions, this could result in under- or
over-estimation of elements such as Cr and Ti, particularly at
higher concentrations. Therefore, a suite of matrix-matched
standards should be selected prior to collecting pXRF data as
part of an orientation sampling trial.

8 Mineral Resource and Ore Reserve Estimation

 A Review of the Reliability and Validity of Portable X-ray Fluorescence Spectrometry (pXRF) Data | M F Gazley and L A Fisher

Ti

Actual concentration (ppm)
Measured concentration (ppm)

Cr
Actual concentration (ppm)

Measured concentration (ppm)

FIG 11 - Variations in calculated corrections (linear fit) based on the matrix of standards used; after Fisher et al (2014). Note there can be a significant difference
between the correction factors calculated based on multiple rock types (all rock – standards with felsic to ultramafic composition) and ultramafic rocks only.

ANALYtical PROTOCOLS as determined through multiple analyses of different spots on

The required rate of sample throughput should be considered
when establishing an analytical workflow. This will require
consideration of any sample preparation required as well
as the need to balance the speed of analysis with required
accuracy and precision.
The analysis time that is used for each unit is specific to
that unit and will vary from site-to-site depending on
the purpose of the data (Bédard and Barnes, 2010). Test
work on counting times (Fisher et al, 2014; Figure 12) has
demonstrated that improvements in analytical precision may
be minimal after counting times exceeding 20 s per filter. A
filter (also referred to as ‘beam’) is a combination of voltage
and amperage that allows different elements to be detected;
a pXRF unit may use two or three filters in a single analysis.
However, a consistent improvement in the counting statistics
is observed with increased counting times. Therefore, the
count times selected must fit the purpose for which the data
is collected. For instance, if Ti concentrations are being used
to track lithogeochemistry within a mafic unit (eg to suggest
or verify correlations of subunits), the counting times should
be sufficient that the standard deviation of Ti analyses
within a unit is appropriately low for statistically significant
determination of the variation in Ti between the units.
Other issues that should be considered include sampling
precision versus analytical precision (Le Vaillant et al, 2014).
When measuring a coarse-grained rock, sampling precision
the rock will be poorer than the analytical precision associated
with repeat analyses of a single spot on that rock. As noted
above, such issues can be largely resolved by analysing
pulverised material. However, high count times may result in
a high analytical precision that greatly exceeds the sampling
precision and this should be clarified in reporting the results
(Le Vaillant et al, 2014). Of course, this situation is also true if
rock or core is not appropriately subsampled before analysis
in a laboratory.
Best-practice protocols for pXRF analysis have been
proposed (Gazley, 2011; Gazley et al, 2011; Parsons et al, 2012;
Fisher et al, 2014) and form a good basis for development
of project-specific guidelines for data collection and
management. These are not reproduced here.
VALIDATION AND PRESENTATION OF DATA
It is the role of the person reporting the pXRF data to ensure that
the data being presented is robust. There are two ways that the
authors believe this should be done: first, by presenting a table
such as Figure 13 (from Gazley et al, 2012) that shows elements
reported, expected value of the standard, median value,
standard deviation, calculated lower limit of determination
and the interquartile range concentrations from the data set
being analysed, which can be calculated by following the
methods of MacDougall and Crummett (1980). Alternatively,
a graph or similar plot showing paired conventional and pXRF

Mineral Resource and Ore Reserve Estimation 9

Chapter 2 | The Resource Database

B
A

C D

FIG 12 - Test work should be conducted to determine optimum analysis time balancing sample throughput, analytical precision, analytical accuracy and analytical
error. (A) Changes in analytical accuracy and precision with increased count time for analysis of Mn in NIST2702 (n = 10). (B) Average counting statistics associated
with analyses in (A) show improvement in analytical error with increased count time. (C) Changes in analytical accuracy and precision with increased count time for
analysis of Zn in NIST2702 (n = 10). (D) Average counting statistics associated with analyses in (C) show improvement in analytical error with increased count time
(modified after Fisher et al, 2014).

FIG 13 - An annotated example of Table 1 in Gazley et al (2012) showing elements reported, expected value of the standard, median value, standard deviation,
calculated lower limit of determination (after MacDougall and Crummett, 1980) for 21 repeated analyses of an appropriate concentration standard; and the
interquartile range concentrations from the data set being analysed.

10 Mineral Resource and Ore Reserve Estimation

 A Review of the Reliability and Validity of Portable X-ray Fluorescence Spectrometry (pXRF) Data | M F Gazley and L A Fisher

analyses (with associated error bars) for the same sample could model, reading times, calibrations, factors applied and their
be presented to demonstrate accuracy. derivations, etc’ must be supplied along with the analyses.
Second, a proportion of the samples that have been analysed The authors would suggest that a more complete list should
by pXRF should be subjected to conventional analysis. A rate include:
of approximately five per cent of total samples (one in 20) •• instrument/unit make and model(s)
is generally considered to be industry standard for Mineral
•• mode of operation
Resource reporting and is suggested to be appropriate (eg
•• analysis time
Abzalov, 2011); these can be presented in two ways, either
as a table (eg Figure 13; Gazley et al, 2012) or graphically •• calibration used
(ie regression analysis). If an unacceptable number of the •• name of the standards used to determine the calibration
samples reanalysed by conventional techniques do not fall (if not factory calibration)
within an acceptable tolerance (say ±10 per cent), the entire •• nature of standard reference material
data set should be repeated by conventional techniques or •• nature of sample analysed (eg solid rock or pulverised)
else not relied upon. •• nature of blank material used
In order for others to evaluate the validity of pXRF data •• sample preparation procedures
sets, it is imperative than any database also stores meta- •• method to ensure samples were dry
data including, but not limited to, unit number, mode of
•• material used to contain the sample
operation, calibration used, blanks, standards, the name of
•• type of correction used
the operator and whether analyses were collected on core,
chips, pulp, hand specimens, etc. Both raw and corrected data •• correction factor for each element reported
should be stored so that calibrations and other QA/QC data •• duplicate/replicate data
can be independently verified as robust and fit for purpose. •• conventional analysis data for samples.
It is critical the pXRF data is not mixed up with conventional An example of an appropriate summary is presented in
assaying data within a database and that a hierarchy of data Table 1 for the data set published in Gazley et al (2011) and
quality is maintained. Figure 13.

TABLE 1
PUBLIC REPORTING RECOMMENDATIONS An example of a table to present analysis conditions of portable X-ray
The integrity of any geochemical data set is highly reliant on fluorescence data (data are after Gazley et al, 2011).
the quality of sampling and analytical procedures that were
used to analyse it. This is particularly important with pXRF Instrument Model: Innov-X Omega
data as the entire analysis process from sample collection to Tube current: 10 - 50 µA
analysis to reporting of the data is potentially in the hands of Tube voltage: 10 - 40 kV
one person, who may not be fully aware of all the factors that Mode of operation Soil
can impact the reliability of a data collection. These factors
Analysis time (per filter) 90 s
include:
•• unit set-up (anode type, window material type) Calibration used Factory
•• homogeneity/representivity of the sample Reference material utilised JB-1
•• nature of the sample when presented to the unit (eg Nature of reference material Powder
curved surface of core) Nature of blank Pressed powder SiO2
•• nature of material containing the sample
Nature of sample Powder (90% passing 75 µm)
•• moisture content of the sample
•• inter-unit variation Moisture content Dried for >2 hours at 110°C
•• short- and long-term drift Sample container Paper bag
•• thickness of the sample Type of correction Single point
•• selection of suitable calibration and standards Ti 0.58
•• appropriate counting statistics and analysis times.
Zr 1.00
It is recommended that where pXRF data is to be publicly Correction factors
reported, it should be supported by documented, rigorous Cr 0.70
standardisation and calibration procedures and with K 1.18
chemical analyses by conventional laboratory techniques
suited to the element(s) of interest on a subset of samples
(eg five per cent). The lower limit of determination (or a conclusions
similar value) should be reported along with the expected This paper has reviewed some of the currently recognised
range (or interquartile ranges) of the elements of interest. issues that can have significant effects on elemental
This data could be presented in a format such as that shown concentrations determined by pXRF and framed them in a
in Figure 13 to make them accessible to the reader and to manner to make it easier for those collecting this type of data
ensure confidence in the results. Neither of these suggestions to ensure that it is robust and fit for purpose. This is in no
is particularly onerous and will result in robust and reliable way intended to be an exhaustive list, nor should this paper
pXRF data being collected and reported. be regarded as the definitive guide to producing pXRF data
JORC (2012) states that for pXRF data, ‘parameters used that is of suitable quality for public reporting to support
in determining the analysis including instrument make and JORC (2012) compliant Exploration Results or Resource

Mineral Resource and Ore Reserve Estimation 11

Chapter 2 | The Resource Database
or Reserve statements. By raising these issues and making
some suggestions about possible solutions, our aim is to
enable those who are collecting, interpreting and reporting
pXRF data to make informed judgements about the quality
of their data and whether the results are fit for purpose.
Above all, it must be remembered that regardless of how
precise and accurate an analytical method is, if the material
presented to the unit is not a representative sample, or the
correction, standards or data processing post-collection are
inappropriate, the results may not be reliable or verifiable.
ACKNOWLEDGEMENTS
Funding for the authors’ research in the field of pXRF
technology comes jointly from Barrick (Australia Pacific)
Limited, the CSIRO Minerals Down Under Flagship and the
Deep Exploration Technologies Cooperative Research Centre
(DETCRC). Cathylee McCauley is acknowledged for her
assistance for collecting both the long- and short-term drift
data and the size-fraction data. Aaron Latham and Chelsea
Tutt are also thanked for the ongoing assistance with all
things pXRF at Plutonic Gold Mine. The authors are grateful
for discussions with, and a review from, Bill Shaw that
greatly improved this manuscript. We also thank Mark Berry
and Steve Barnes for their comments and Alistair White and
Aaron Baensch for their thoughtful reviews of an early draft
of this manuscript.
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14 Mineral Resource and Ore Reserve Estimation