The importance of assay method and accuracy – a scandium case study

J A Horton1

1.Consulting Geologist, ResEval Pty Ltd, Brisbane, Qld 4066 Email: jhorton@reseval.com.au

ABSTRACT
For resource evaluation, assay accuracy is critical, whereas precision can consider or be offset by
sampling density.
In quality assurance and quality control (QAQC) analysis, the assessment of the selected assaying
method and its accuracy is often overlooked. Umpire samples provide an opportunity to test
alternative assaying method outcomes and accuracy. However, often umpire sampling programs
only demonstrate reproducible results for the same assay method at a different laboratory.
If certified using a different assaying method, then certified reference materials (CRMs) can help to
verify an assay method for accuracy. However, all commercial CRMs raise questions regarding the
suitability of the CRM mineral matrix and the certification assay method.
Work performed by Platina Resources Limited (Platina) on their scandium project in New South
Wales (NSW), provides some insight into these issues with the comparison of Inductively Coupled
Plasma (ICP) and X-ray Fluorescence (XRF) analytical data. It demonstrates typical small assaying
accuracy issues for Ni and Co in nickel laterites, as well as significant inaccuracy when analysing for
Sc in scandium rich laterite deposits.
Platina refocused their QAQC work on accuracy, and this paper provides several valuable learnings:
All tested assay methods by ICP were biased low for Sc, to at least some extent, and are not
considered accurate.
Alternative method assays were hidden by the structure and implementation of the
commercial database and overlooked initially.
Lack of focus on absolute accuracy undermined an otherwise well-executed QAQC process.
A few umpire assays by alternative methods can be more valuable than all the other QAQC
samples.
CRMs are not a measure of accuracy but a measure of relative performance against a group
of laboratories using the same assay method.
Use of internally sourced matrix-matched standards can be invaluable in the QAQC process.
These learnings have relevance to all mineral projects, as it is common for QAQC programs to focus
on precision and performance without fully exploring assaying accuracy.

INTRODUCTION
The introduction of glass fused XRF analytical methods to commercial laboratories has seen oxide
and industrial miners move away from traditional ICP and atomic absorption spectroscopy (AAS)
analytical techniques applied in general exploration and by sulphide miners. It is a result of both
increased accuracy and availability of full whole rock analysis offered by XRF. In particular, XRF
provides reliable silica analysis, which is essential for metallurgical understanding and mineral
processing. These benefits outweigh the slightly higher analytical cost for XRF and narrower trace
element spread than that offered by ICP using a four-acid digest method.
Platina recently completed a Feasibility Study for their Owendale Sc-Co-Ni-Pt laterite project in NSW,
with exploration and resource definition drilling completed between 2011 and 2018. An initial phase
of exploration between 2011 and 2014 used ICP with four-acid digest as the principal assay method.
A well-structured QAQC program and independent analysis raised no significant concerns at that
stage. A subsequent second phase of exploration between 2016 and 2018, included the change to
borate glass fused XRF analysis. The re-assaying of some previous samples and an internal CRMs

Mining Geology 2019 / Perth, WA, 25-26 November 2019 43

highlighted both accuracy and precision issues. These issues persist in more recent studies and can
be attributed to assay bias with the ICP method.
The results reflect work undertaken by the author over a series of other laterite projects and are
consistent with findings from different laterite projects both in Australia and overseas. The example
from the Platina dataset provides a case study of assaying issues common to laterites.
The description of the Platina results focuses on some of the data for Ni, Co and Sc and does not
present all the QAQC program undertaken for:
platinum group metals which were a significant focus for Platina or
resampling of older exploration and analyses competed in the 1980s and 1990s.
The assessment of precision is useful to understand resource variance and to improve the sampling
sample preparation process. However, it often becomes the primary focus of QAQC sampling and
analysis. From a Mineral Resource definition perspective, reduced precision (i.e., variance) can be
address with increased sampling density. However, uncertainty concerning accuracy presents a
dilemma that can severely impact project economics and decision making. Assessing analytical
accuracy deserves greater attention in our QAQC sampling and assessments, particularly the
selection and verification of the primary analytical method.
The presentation of the following case study demonstrates the need to critically assess the selected
assaying method for accuracy. CRMs alone are not enough to confirm accuracy. Umpire or check
sampling is critical for evaluating inter-laboratory consistency and should include cross-checks on
the assaying method to support our understanding of grade accuracy.
The improvement in assaying achieved by Platina was a result of refocussing QAQC sampling away
from precision to refocus on umpire assaying and accuracy. It was achieved through a culmination
of experience from earlier projects and by bringing commercial laboratories on-board with alternative
analytical methods, namely Sc analysis by XRF. Since this method was not part of their listed
services at the time, the success of those initial XRF trial programs has resulted in some laboratories,
now list Sc as a standard optional additional element for XRF analysis.

PLATINA SCANDIUM PROJECT

Platina Resources Limited is an Australian resources company focussed on the exploration and
development of a global portfolio of precious and specialty metal projects. Platina’s core focus is its
100 percent owned Platina Scandium Project, previously known as Owendale, located in central
NSW, which has the potential to become Australia’s first scandium producer with possible cobalt,
nickel, aluminium (HPA) and platinum credits.
The Mineral Resource is in central NSW, approximately 53 km north-east of Condobolin and 11 km
south-west of Tullamore. The processing plant will be constructed about 5 km north-west of the
township of Condobolin, 70 km by public road south-west of the Mine Site.
Platina proposes to develop the project in stages, each designed to meet market capacity while
minimising technical and financial risk. The ore will be mined and hauled 70 km to the Plant Site near
Condobolin. The process plant will treat high-grade scandium ore (limonitic ore) via high-pressure
acid leaching and solvent extraction to produce high purity (min. 99.99 percent) scandium oxide
product.
The proposed stages of development are:
Stage 1: small scale scandium oxide production (20 t/y).
Stage 2: increased scandium oxide production (40 t/y) by upgrading the processing train.
Stage 3: additional expansion with a second duplicate parallel processing train.
The Mineral Resource and Ore Reserves are based on high iron limonitic laterite material that has
been enriched the scandium by residual enrichment processes. The host rocks comprise the
ultramafic complex from an Alaskan style intrusive body that includes multiphase ultramafic series.
Target mineralisation is developed from pyroxenite phases where clinopyroxene has scavenged and
enriched scandium from the differentiated source magma. Ultramafic end members such as dunite

Mining Geology 2019 / Perth, WA, 25-26 November 2019 44

are richer in nickel, whereas the less mafic pyroxenite series have higher scandium. The ultramafic
series gives rise to laterites enriched in nickel or scandium. Cobalt and platinum can occur across
both ultramafic types.

ICP ANALYSIS METHOD BACKGROUND

ICP is the most common analysis method used across the minerals industry for geochemical
assessment. The attraction of ICP is that it provides a broad elemental analysis that covers both
major and trace elements. Commercial analytical laboratories often package over 30 elements with
ICP, making it cost-effective to acquire a broad elemental spread that is well suited to green-fields
exploration through to environmental sampling.
Commercial laboratory methods usually take around 0.25 to 0.5 g of pulverised mineral sample and
a sequence of dissolution and evaporation steps to acquire a final solution suitable for measurement
in an ICP device. Detection levels can be adjusted using a dilution of the solution and using different
ICP devices.
The four-acid mix used today comprises of hydrochloric acid (HCl), nitric acid (HNO3), hydrofluoric
acid (HF) and perchloric acid (HClO4). It varies from three-acid digest methods used extensively in
the past by the addition of hydrofluoric acid that dissolves more persistent silicate minerals.
ICP devices can include:
AES - atomic emission spectrometry
OES - optical emission spectrometry
MS - mass spectrometry
The intricacies of the ICP equipment are less relevant to this assessment as the primary analytical
errors discussed occur from preparing the required solution that is read by the ICP equipment.
References to ICP data in this paper are for ICP-AES for principal analysis and to a lesser extent,
ICP-OES for umpire sample analysis. The two assessment methods are similar processes but use
different equipment suppliers.
The four-acid digest preparation method has multiple steps relying on acids of known concentration
and measured volume to dissolve the rock mass, as well as evaporation steps with moisture and
assumed elemental losses all used to adjust the final ICP assay results back to a sample dry mass
grade. Though the ICP equipment is reliable with high precision and accuracy, most of the assay
method variability and error relate to the sample solution preparation.
The method usually is referred to as a “near-total” dissolution as some oxide mineral may not
dissolve in the four-acid mix. Additionally, the evaporation process can volatise some elements.
Since the acid concentration, volumes, temperatures, and evaporation periods all differ between the
commercial laboratories. There will be subtle differences between the results and suitability of the
individual laboratory methods.
To overcome some of the known inadequacies of the general four-acid ICP analysis, the commercial
laboratories may change their standard methods over time. Usually, significant changes are reflected
in different laboratory codes.
As an example, the current SGS Laboratory website indicates that their standard four-acid method
can:
volatise As, Si, Se
precipitate or have limited solubility for Al, Mn, Ti, Ba, Nb, Ta, Cr, Pb, W, Hf, Sb, Zr, Mo and
Sn.
Despite these warnings, many of the problematic elements are still reported in the ICP suite, placing
the onus on the user to determine if the elements reported are reliable.
More recently the commercial laboratories offer fusion methods to overcome some partial mineral
dissolution or other precipitation issues. These methods use a flux, for example, lithium metaborate,
to allow the sample to fuse into a glass when heated, followed by the regular acid digestion and ICP

Mining Geology 2019 / Perth, WA, 25-26 November 2019 45

process. The process provides for the destruction of the original mineral matrix to enhance
dissolution and is particularly suitable for freeing trace elements from mineral matrices.
Fusion methods offer potentially total dissolution but introduce issues of the flux purity and degree
of oxidation involved. These methods are usually only provided at more extensive central
laboratories.

XRF ANALYSIS METHOD BACKGROUND

XRF spectroscopy has been used for analysis for a long time. The methods have improved over the
last few decades with a glass fusion method, improved detectors, and software.
A typical laterite method by glass fusion involves mixing around 0.7 g of pulverised sample with a
fixed amount of a premixed flux agent, i.e., lithium metaborate – lithium tetraborate, before fusing
the sample at about 1000°C. It destroys the original mineralogical matrix, freeing trace elements and
removing the granularity of the original pulp material. Secondly, it provides a smooth glass surface
with minimal surface scatter of the X-ray beams.
The fusion process drives off the light volatile elements held within the mineral matrix, i.e., water and
carbon. The XRF total result can be suitably checked against the expected volatile losses if a Loss
On Ignition (LOI) analysis is available. Most good commercial laboratories now bundle LOI with XRF
analysis to provide a complete report of the major elements, i.e., near 100 percent elemental
analysis.
Early XRF analysis equipment might be less quantitative but modern use of fused discs and
improvements in the software now allow accurate measurement by applying known interelement
associations. It is further enhanced by the ability to cross-check against the whole rock mass total.
As a result, for oxide material, XRF is potentially more accurate, more direct by using solid sample
material, and has a complete whole-rock elemental range (excluding trace elements).

LATERITE INDUSTRY STANDARDS

Mineral deposits generally vary in their elemental and mineral make-up, to such an extent that an
industry analytical standard method is a dangerous concept. However, these methods do present a
reasonable starting point for a project. QAQC processes should always attempt to test and prove
the selected sampling and analytical methods for both accuracy and precision. Despite this QAQC
concept, it is not uncommon for projects to adopt a perceived standard analytical approach without
enough review or verification. Such perceived standards are perhaps fire assays for gold and PGMs
and ICP for multielement analysis.
A brief review was undertaken of the 2018 public exploration reports for nickel or scandium laterites,
where the assaying method was readily identified when reporting under Australian Joint Ore
Reserves Committee (JORC) Table 1 reporting code criteria. A total of 20 reports indicated that 12
used XRF or XRF in combination with ICP, and eight used only ICP. Some of those using ICP were
still at an initial or grass-roots assessment, where ICP might even be suitable for a first pass
assessment of exploration potential consisting of a broader element scan offered by this method.
Some of the reports appear to restate older data in their assessment studies. It leaves a few who
reported ICP for infill and even feasibility level definition drilling. In these cases, there was no
indication that the suitability of the analytical method had been evaluated. There is a high probability
that the historical selection of an ICP method was continued despite industry adoption of XRF as
standard. The review suggests geologists are working on laterites that are unaware of industry best
practice or unaware of the potential assaying issues with using ICP.
The existence of a perceived standard that deviates from the general norm is perhaps an indicator
of the industry has moved its preference, even if not widely documented.
For oxide mining industries, such as iron ore, bauxite, laterites, and phosphate whole rock analysis
are crucial, as the mineral processing by furnace or acid/caustic bulk digestion methods requires an
understanding of the total chemical make-up. Bundled fused XRF analysis will include LOI and silica
that is generally not available from the standard four-acid digest ICP analysis.

Mining Geology 2019 / Perth, WA, 25-26 November 2019 46

Hence XRF has been used in the iron ore and bauxite sectors since the 1980s and has been adopted
as industry standard industry for some time. More recently, the laterite sector has been adopting
XRF. But despite the benefits of XRF, ICP is still often used probably because of more fragmentation
in the laterite exploration and mining industry.
An early 2019 review of major commercial laboratory mineral service guides indicated:
SGS recommended XRF for iron ore, silicate, feldspar, gypsum and limestone where
sulphide minerals are <1 percent. More specifically, laterite is only mentioned under ICP
methods.
ALS recommended XRF as the industry standard for iron ore, bauxite and the suggested
method for laterites, phosphates and Cr, Sn, W, Nb, Ta, Mn, Ba, Ti or Zr deposits.
Intertek recommended XRF as the preferred method for iron ore, bauxite, chromium, nickel
laterite, manganese, potash, industrial and refractory minerals.
Bureau Veritas recommended XRF as the preferred method for iron ore, bauxite, nickel
laterites, mineral sands plus many other ores including Mn, Ta, Sn, Cr, W and Rare Earths.
Hence, most service guides provide advice consistent with the industry, though one has not yet
updated its guidance for laterites.
Most commercial and regional laboratories have ICP and AAS equipment, whereas XRF equipment
is generally centralised to major laboratory hubs close to iron ore, bauxite or laterite clients namely
Perth, Brisbane and Jakarta. As a result, commercial laboratory staff and laboratory managers have
little experience with XRF. It would be similar to other specialised analytical methods, where
additional equipment is required. Hence sales staff or laboratory managers may not have the breadth
of experience or may provide a personal bias to analytical techniques available in their laboratory or
region. This particular bias, whether intentional or not, is an issue that geologists need to be aware
of when seeking advice on suitable analytical methods.
Previous enquires with some commercial laboratories for laterite XRF services, have been answered
by staff with only ICP experience and based in laboratories or regions with no XRF services. It
demonstrates that personal bias and experience, even at large commercial laboratories, is present
and must be considered when evaluating analytical methods.
When looking for both industry preferred and alternative assaying methods, it pays to broaden ones’
research and to seek out experienced industry advice, as well as develop working relationships with
laboratory managers with both a breadth of experience and a client focus rather than a local sales
focus.

PHASE 1 ICP QAQC

To work through the case example, the basic Sc-Ni-Co QAQC from the first Platina drilling phase is
presented as scatter plots with identical scales, a diagonal 1-to-1 reference line, and a linear
regression line. Simple statistical measures are provided that exclude below detection and low-grade
values <30 ppm Sc or <0.04 percent Ni or Co. The measures include:
For precision, the average half absolute relative difference (HARD) as defined by Shaw,
Khosrowshahi, Horton and Waltho (1998).
For accuracy, the average relative difference (RD).
The initial Phase 1 drill assaying was by four-acid digest and ICP finish at:
Initially, the analysis was at Laboratory A for most of the program with umpire samples sent
to Laboratory C
The later analysis was at Laboratory B for most of the program with umpire samples sent to
Laboratory A.
Duplicate data are presented in Figure 1 for field and internal laboratory duplicates. These suggest
a regular, rather than relative differences, hence the average paired difference provides a reasonable
measure for variance, if near detection limit values are ignored. These are between 40 and 70 ppm

Mining Geology 2019 / Perth, WA, 25-26 November 2019 47

for Ni and Co and around 10 ppm Sc, compared to the laboratory reporting limit for ICP of 10 ppm
for Ni and Co and 1 ppm for Sc.
Field duplicate data late in Phase 1 drilling in Figure 1b is similar though slightly tighter.

a. Laboratory A ICP analysis – field duplicates

b. Laboratory B ICP analysis – field duplicates

Figure 1 - Phase 1 duplicates

Umpire pulp samples submitted during both periods of Phase 1 drilling in Figure 2 also use similar
ICP methods. The umpire assay results are mostly consistent, though the umpire laboratory in Figure
2a reports slightly lower results for Ni and Co.
CRMs for Sc, Ni and Co that were submitted blind to the laboratory are restricted to one commercial
CRM for Ni and Co and two local CRMs sourced from local material and prepared and certified by a
CRM supplier. The CRMs in Figure 3 indicate some spread which is misleading on a scatter plot as
some sets contain a considerable number of data pairs; however, the plots do demonstrate no
substantial accuracy issues. Though the laboratory also inserted their own CRMs and other
standards that provide more information, there were no commercial Sc CRMs available at the time
and no additional Sc data.
An independent QAQC specialist assessed the presented data along with the PGM assay data and
some ICP method variations and no issues were raised at the time, except for some individual
batches that required further review.
The QAQC and analysis would appear to have been done very well with the usual samples taken
and independent analysis of the results by a suitable professional. Early exploration geologists can
be commended as they identified the lack of a commercial CRMs for Sc and specifically drilled and
sampled material for in-house reference materials, with the preparation and certification of that
matrix-matched material undertaken by a well-known and respected CRM manufacturer and
supplier.

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In 2011 there were no alternative assaying methods that were readily available from a commercial
laboratory, so both the CRM certification and umpire samples were based on similar ICP methods,
though by different laboratories.

a. Laboratory A ICP analysis – umpire samples at Laboratory C

b. Laboratory B ICP analysis – umpire samples at Laboratory A

Figure 2 - Phase 1 umpire samples

Laboratory A and B ICP analysis – CRMs assays vs. expected values of the day

(scatter plots contain large datasets and presented to in this manner for comparison and to
demonstrate lack of evident bias, these are unsuitable for assessing assaying precision)
Figure 3 - Phase 1 blind CRMs

HIDDEN DATA
The exploration data was stored and maintained in a well know commercial database system that
was initially set up and supported by a specialist database service firm. Day to day data uploads and
exports were completed by company staff. The system stored both primary data and specific tables

Mining Geology 2019 / Perth, WA, 25-26 November 2019 49

to manage duplicate samples, CRMs and blanks taken for QAQC. The original independent QAQC
review involved only the QAQC data tables.
A subsequent detailed review of the database and original laboratory certificates indicated that much
of the Phase 1 drilling had additional XRF analyses undertaken primarily to report silica lacking from
the initial ICP assays. Although only a limited element list was reported by XRF, some elements
were duplicated, including Ni and Co. The resulting comparison in Figure 4 contains over 10 000
sample pairs. With such an extensive data set the apparent minor bias for ICP to under-call the XRF
Ni and Co grade is reliably identified as a trend. Since the bias appears to be proportional to grade,
the mean relative difference provides a simple measure of the potential under-call. For the data in
Figure 4, the mean relative difference (RD) is six percent for Ni and Co when excluding near
detection limit and low-grade values. The implication of this for the Mineral Resource is further
described by Platina Resources Limited (2017).
In the authors’ experience, such small biases are evident in all other nickel laterite deposits when
ICP four-acid digest and XRF fusion paired data was available. The level of under-call by ICP can
vary with those in Figure 4 at the larger end of the spectrum that is more typically in the range of two
percent to four percent under-call of Ni and Co.

Figure 4 - Phase 1 Laboratory A ICP analysis vs. XRF analysis

The field duplicates for the XRF analyses, Figure 5, can be compared with the field duplicates for
ICP in Figure 1. The mean difference measure is approximately 80 ppm for Ni and Co and is
statistically similar to ICP; however, the early XRF Ni and Co grade are only reported to 100 ppm.
The results suggest a higher intrinsic precision that was rounded when reported by the laboratory.

Figure 5 - Phase 1 Laboratory A XRF analysis – field duplicates

The oversight in assessing the XRF data in the original QAQC program raises an issue that can
happen on sites where multiple assay methods are used for a primary sample. The databases are
typically constructed to extract the “best” assayed grade for each element using a complicated
database query that accepts the assays by different methods. It is often established during the
construction of the initial database, and the extraction query must be updated each time a new

Mining Geology 2019 / Perth, WA, 25-26 November 2019 50

primary assay method is added for those results to be able to flow through to the final data export of
“preferred” assays.
Outside of regular QAQC data, duplicate primary assays may exist for various reasons, including:
Any instruction or procedure for the laboratory to re-assay a sample, e.g. for a different ore
grade method above a threshold.
Alternative assaying for additional elements as in our case study.
Alternative re-assaying for metallurgical or environmental purposes.
Automatic laboratory re-assays due to upper detection limits or for re-assaying using ore
grade analysis methods.
None of these will be considered QAQC samples as far as database storage, but they can provide
valuable QAQC information.
For the case study, the duplicate data using an alternative assay method was never identified and
never included in any data export. Hence the valuable comparative data and the most extensive
QAQC data set was not assessed at the time. The commercial database systems typically provide
no method to extract or even find potential duplicate primary analyses without reviewing a dump of
the entire raw assay table.
This example and the structure of many of the available commercial database systems raises several
points for project geologists:
The need to know all the assaying methods used (both current and past) and what should
be available for QAQC review.
The need to know, document, and review the preferred assay derivation process, i.e., the
desired precedence of assaying methods used by the database queries for data exports.

PHASE 2 XRF ASSESSMENT

Phase two of the exploration program commenced with a review of the assaying methods, QAQC
data, and resubmission of previous samples to test alternative assay methods. A preferred primary
assay method using XRF borate glass fusion was adopted as it could report all significant whole
elements as well as all potentially valuable minor elements (excluding PGMs) that included Ni, Co,
Sc, Cu, Zn, and V.
The field and laboratory duplicates in Figure 6, indicates a tighter spread with a mean difference of
20 to 60 ppm for Ni and Co and around 10 ppm for Sc. Ni, Co and Sc are reported at a level of 10
ppm, hence the low spread in Sc suggests there is more precision available to XRF which is limited
by the level of reporting by the laboratory.
The reanalysis of Phase 1 samples by fused XRF in Figure 7 suggest a consistent under-call of Sc
grade by ICP with the degree of bias correlating with some whole-rock mineral trends, i.e. mineralogy
affects the degree of bias. The bias is then different again at each laboratory, indicating that the
specific laboratory sample digestion and solution preparation process plays a significant role in the
level of bias. Hence the assaying issue is related to the preparation of the particulate samples into a
solution and not related to the ICP equipment.
Three sample preparation processes could contribute to the loss of Sc from the final solution in ICP
analysis:
incomplete digestion of the Sc bearing minerals
reprecipitation of Sc with mineral phases or nanoparticles
volatilisation of Sc during solution evaporation steps.

Mining Geology 2019 / Perth, WA, 25-26 November 2019 51

 a. Laboratory B XRF analysis – field duplicates

b. Laboratory B XRF analysis – laboratory duplicates

Figure 1 - Phase 2 duplicates

a. Laboratory A XRF reanalysis of Phase 1 Laboratory A ICP

b. Phase 2 Laboratory B XRF reanalysis of Phase 1 Laboratory B ICP

Figure 2 - Phase 1 reassays by XRF

Mining Geology 2019 / Perth, WA, 25-26 November 2019 52

A final potential analytical error is in the management of the sample pulp moisture content. Since
laterites are generally hydroscopic, they can both retain and absorb free moisture at the laboratory.
The fused XRF disc is free of moisture and corrected for the LOI analysis. In contrast, the ICP sample
preparation may not be dehydrated at the commencement of the analysis It could be one of the
underlying reasons why ICP commonly displays minor Ni and Co biases, although it is not anticipated
to be the main contributor to the Sc bias.
Sc distribution in laterite ore is diffuse with limited mineral dissolution issues that could result in the
significant biases noted for Sc.
In contrast where Cr occurs as chromite partial dissolution often result in low Cr assays for laterites.
Internal laboratory tests suggest that reprecipitation is the likely issue with four acid digest ICP. This
is addressed with borate fusion ICP, which only requires more straightforward acid digestion. The
subsequent elimination of fluorine in solution may resolve precipitation issues. The smaller remaining
Sc under call by fusion ICP is similar to the small biases noted for Ni ad Co and suggest the remaining
problems are moisture related.
XRF umpire samples, for the Phase 2 drilling, at another laboratory correspond well, indicating
similar accuracy and precision, Figure 8a.
Umpire samples sent to ANSTO for Neutron Activation Analysis (NAA) using extended irradiation,
display similar accuracy and high precision for Sc and Co (Ni was not reported for NAA), Figure 8b.
Since NAA is considered both a quantitative and accurate method for analysing solid materials, the
results confirm the accuracy of the XRF method and the consistent bias by ICP.
In parallel to work completed by Platina, Jervois Mining Limited (2014a) at a nearby laterite project,
identified Sc mineralisation and determined issues with four-acid ICP analysis results for Sc when
compared to a handful of initial NAA results. Working with their laboratory, they applied an improved
ICP assaying method, developed using a lithium metaborate initial fusion. The NAA re-assay results
were never reported, and the enhanced ICP fusion results only summarised above a cut-off with a
significant increase in Sc grade and drill intercept length by Jervois Mining Limited (2014b).
Scandium International (2016) at another nearby project also noted significantly higher grades using
ICP fusion over conventional ICP four-acid-digest methods.
Figure 8c indicates that the comparison for the case study between XRF and the improved fusion
ICP method. It displays a marked improvement over the four-acid digest ICP method. However, a
small bias persists when comparing ICP fusion method from another laboratory.
Work by Platina has indicated that all ICP assay methods tested displayed under-call of Sc against
XRF and NAA. Though newer fusion ICP methods are improved, they still under-call Sc slightly.
Most laboratories do not currently offer extensive multi-element reports from the ICP fusion methods.
Undertaking both four acid and fusion ICP analysis to obtain the required elements also increases
the total assay cost over a single XRF and LOI analysis.

INTERNAL CRM ASSESSMENT

Through foresight and planning by Platina exploration geologists, two internal CRMs were
established, since no commercial CRMs for Sc were available at the commencement of Platina’s
exploration in 2011. An independent CRM manufacturer ten analyses for each CRM. Five of the
laboratories used a four-acid digest ICP method, and one used a three-acid digest ICP method. At
the time, commercial laboratories did not offer off-the-shelf XRF analysis or tailored fusion ICP
methods for Sc.
Because Platina contracted the CRM preparation and certification, the full certification analysis set
was available for review. Figure 9 summarises the data for each laboratory and method for the
certification results and the subsequent analysis over the last two exploration phases.

Mining Geology 2019 / Perth, WA, 25-26 November 2019 53

 a. Laboratory B XRF analysis – umpire samples at Laboratory D XRF

b. Laboratory B XRF analysis – umpire samples at ANSTO by NAA

c. Laboratory B XRF analysis – umpire samples at Laboratory B by borate fusion ICP

Figure 8 - Phase 2 umpire samples

For the low-grade CRM, all the laboratories are mostly within a 5 ppm tolerance of the expected
value of 75 ppm Sc. The possible accuracy of the XRF method is lost in the rounding of the results
by the laboratories to 10 ppm. Overall, at this low-grade range, ICP appears to perform adequately
for the low iron saprolitic clay matrix.
For the high-grade limonite CRM, the mineral matrix is very different and dominated by Fe and Al
clays and a substantially higher Sc grade. The original certified grade of 555 ppm Sc was reviewed
and adjusted to 595 ppm Sc; it was based on the consistent and tightly arranged results for NAA and
XRF.

Mining Geology 2019 / Perth, WA, 25-26 November 2019 54

 Figure 9 - Box plots of Platina CRM analysis for Sc

Phase 1 drilling results by laboratory A, underperformed against the original CRM expected value
and raised no concerns at the time in the independent specialist review. The even lower grade
performance of laboratory B, late in Phase 1 was only recognised well afterward and was part of the
review of the preferred assaying method at the start of Phase 2. The subsequent evaluation of the
certification results raised concerns over the reliability of ICP with both the full spread of the
certification assays and that a disproportionate number of “outlier” high-grades were excluded from
the original certification. A more critical review of the certification assay results for the internal CRM
and addition of an alternative assay method such as NAA, that was available at the time, may have
uncovered the assaying issues with standard ICP methods at the start of the exploration program.
Instead, considerable investigation and re-assaying have been required to understand and re-
evaluate the deposit eight years later.
The seven percent under-call of the CRM Sc grade is significant, and the umpire samples indicate
this bias is higher at other grade ranges. Overall the results indicate four acid ICP analysis at Lab A
was biased ten percent low, and Lab B bias 21 percent low. These accuracy issues had and still
have a significant impact on the Mineral Resource grade and tonnage.

CONCLUSION
In this case study, the need to critically assess the laboratory analysis method is presented. It
includes the evaluation of the certification data for the CRMs used to determine assaying accuracy.
The study indicates that ICP methods suffer from varying degrees of bias for Sc. This could not be
adequately identified and assessed without using alternative assaying methods such as XRF and
NAA.
A laboratory manager or chemist will be focussed on laboratory precision and performance of their
laboratory against its’ peers for the same assaying method. Though performance monitoring is
required to catch and address batch by batch issues, ultimately a geologist should be more
concerned with absolute accuracy than routine performance.

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CRMs can offer some measure of accuracy. However that might only be relative to other laboratories
using the same method. Ultimately, umpire samples are the main armoury to assessing accuracy by
using alternative and potentially more reliable methods than the conventional approach. In such
cases, it may be more valuable to send fewer samples to a more expensive boutique laboratory or
specialist method to verify the accuracy of the primary or regular assay method.
Some commercial CRMs now carry results from alternative methods, such as NAA that are not used
as part of the certification process but provide additional information. It can help corroborate the
accuracy of the CRM, but such data is often overlooked during QAQC reviews.
It should be noted that internal laboratory CRMs are generally not selected to prove assay accuracy,
but to determine that the for each batch of analysis, results are within the specification for the
assaying method. Hence much of the consumption for CRMs is driven by laboratory chemists to
monitor performance.
Because it is often not possible to purchase CRMs with a suitable mineral matrix to match a project,
development of internal CRMs can be extremely valuable.
The Platina case example demonstrates the significant assay bias that can occur with assays and
the importance of using alternative assay methods for either or both umpire samples and CRMs.
The study is an example of the significant assay accuracy issues for scandium using ICP. As well
as small ICP biases for nickel and cobalt that are common for nickel laterite projects. The study also
demonstrates the problems of relying on CRM’s that are certified using only the one assay method
and no other corroboration.
The implications of assaying accuracy affect not only the Mineral Resource and Ore Reserve grades
but also tonnage and ultimately economic development decisions. Often metallurgical test work has
little QAQC process and the understanding of assaying accuracy; hence, geological QAQC
programs are also crucial to interpret the real metallurgical recovery and mass balance issues.

ACKNOWLEDGMENTS
The Author thanks Platina for allowing publication of the case study and the scandium test work as
well to Robert Mosig for the early support to investigate and address the assaying issues identified
early in Phase 2. The author also acknowledges the input to the test work and paper by Gideon
Steyl, Corey Nolan and Boyd Willis from the Platina project team and Andrew Richmond for his
comments. Finally, the author thanks Shaun Kenny from ALS Brisbane for his support in assessing
the analytical issues with Sc for initially trialing scandium analysis by XRF.

REFERENCES
Jervois Mining Limited, 2014a. EL 7805 Syerston Scandium Project, Re-Assayed and Amended Results from May 2014
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30 May 2019].
Jervois Mining Limited, 2014b. Re-Assayed and Amended Results from August 2013 and May 2014 Drilling Program.
Available at <www.asx.com.au> (ASX:JRV announcement dated 30 June 2014) [Accessed: 30 May 2019].
Platina Resources Limited, 2017. Cobalt and Scandium Mineral Resource increases at Owendale. Available at
<www.asx.com.au> (ASX:PGM announcement dated 14 Aug 2017) [Accessed: 30 May 2019].
Scandium International, 2016. Feasibility Study - Nyngan Scandium Project Bogan Shire, NSW, Australia, NI 43-101
Technical Report dated 15 April 2016. Available at <www.sedar.com> [Accessed: 30 May 2019].
Shaw, W J, Khosrowshahi, S, Horton, J and Waltho, A, 1998. Predicting and monitoring variability in sampling, sample
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