Letter

Geochemical Perspectives Letters

aerospace and automotive industries. In solid oxide fuel cells, the addition of Sc
to the electrolyte improves conductivity and lowers the operating temperature,
extending fuel cell life.
© 2017 European Association of Geochemistry
Despite a crustal abundance of ca. 22 ppm (Rudnick and Gao, 2014),
comparable to common elements such as copper or lead, current Sc production
Scandium speciation in a world-class is limited to 10 t to 15 t per year (U.S. Geological Survey, 2016). The large ratio of
lateritic deposit ionic radius to charge of Sc3+ hinders the concentration of scandium during most
geochemical processes (Samson and Chassé, 2016). A notable exception concerns
lateritic deposits developed over ultramafic–mafic rocks where Sc concentrations
M. Chassé1,2*, W.L. Griffin2, S.Y. O’Reilly2, G. Calas1
up to 100 ppm make it a potential by-product (Aiglsperger et al., 2016; Maulana et
al., 2016). Recently, lateritic deposits with Sc concentrations high enough to mine
as a primary product have been reported in Eastern Australia (Jaireth et al., 2014).
Among these, the Syerston–Flemington deposit contains about 1350 t of Sc at an
Abstract doi: 10.7185/geochemlet.1711 average concentration of 434 ppm Sc (Pursell, 2016), providing a century-long
Scandium (Sc) has unique properties, highly valued for many applications. Future supply resource at the present levels of world consumption.
is expected to rely on unusually high-grade (up to 1000 ppm) lateritic Sc ores discovered in
Eastern Australia. To understand the origin of such exceptional concentrations, we investi- We present the first data on Sc speciation in lateritic deposits by combining
gated Sc speciation in one of these deposits. The major factors are unusually high concentra- quantitative mineralogy, geochemical analysis and X-ray absorption near-edge
tions in the parent rock together with lateritic weathering over long time scales in a stable structure (XANES) spectroscopy on drill-core samples from the lateritic profile of
tectonic context. At microscopic and atomic scales, by combining X-ray absorption near-edge the Syerston–Flemington deposit. The results explain the geochemical conditions
structure spectroscopy, X-ray diffraction and microscopic and chemical analyses, we show
that Sc-rich volumes are associated with iron oxides. In particular, Sc adsorbed on goethite
required to form such exceptional Sc concentrations and improve our under-
accounts for ca. 80 % of the Sc budget in our samples. The remaining Sc is incorporated in standing of the geochemical behaviour of this under-explored element.
the crystal structure of haematite, substituting for Fe3+. Scandium grades reflect the high
capacity of goethite to adsorb this element. In contrast, the influence of haematite is limited
by the low levels of Sc that its structure can incorporate. These crystal-chemical controls play
a major role in lateritic Sc deposits developed over ultramafic–mafic rocks.
Geological Context

In Eastern Australia, lateritic profiles developed under seasonally dry humid

Received 6 August 2016 | Accepted 31 October 2016 | Published 23 November 2016
tropical climatic conditions that resulted in intensive weathering during the
Tertiary; the present occurrences are often erosional remnants of fossil laterite
(Milnes et al., 1987). The Syerston–Flemington deposit (Fig. 1a and Table S-1) is
Introduction
part of the lateritic cover developed over the Tout complex, an ultramafic–mafic
Scandium is embedded in the very fabric of modern society, making it one of the ‘Alaskan-type’ intrusive complex in the Lachlan Fold Belt (Johan et al., 1989).
most valuable elements. End-uses range from biomedical research to electronics, Scandium anomalies have been found over a body of nearly pure clinopyroxenite
lasers and ceramics but the demand is driven by energy issues (Emsley, 2014). (Fig. S-1), with Sc concentrations (ca. 80 ppm; Table S-3) twice as high as those in
Scandium finds applications in Al–Sc superalloys, increasing tensile strength and typical mantle clinopyroxenites (Samson and Chassé, 2016). Similar concentra-
improving weldability while maintaining light weight, an energy-saving factor in tions (60 ppm to 80 ppm) occur in other ‘Alaskan-type’ clinopyroxenites (Burg
et al., 2009) and in clinopyroxenes from ocean-island basalts (Dorais, 2015). This
suggests the accumulation of clinopyroxene in subvolcanic feeder conduits during
fractional crystallisation of a mantle-derived melt. Anomalies of Sc concentration
1. Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie (IMPMC), Sorbonne Universités, in the parent rock result from specific conditions of formation and are not shared
UPMC Université Paris 06, UMR CNRS 7590, UMR IRD 206, Muséum National d’Histoire ­Naturelle, 4 by all ultramafic–mafic bedrocks.
Place Jussieu, 75005 Paris, France
2. Australian Research Council Centre of Excellence for Core to Crust Fluid Systems (CCFS) and GEMOC,
Department of Earth & Planetary Sciences, Macquarie University, NSW 2109, Australia
* Corresponding author (email: [email protected])

105 Geochem. Persp. Let. (2017) 3, 105–114 | doi: 10.7185/geochemlet.1711 Geochem. Persp. Let. (2017) 3, 105–114 | doi: 10.7185/geochemlet.1711 106
Geochemical Perspectives Letters Letter Letter Geochemical Perspectives Letters

micro-X-ray fluorescence (µ-XRF). Scandium speciation was determined by

synchrotron-based micro-X-ray absorption near-edge structure (µ-XANES) spec-
troscopy at Sc and Fe K-edges. Detailed descriptions are given in the Supple-
mentary Information.

Characteristics of the Lateritic Deposit

The lateritic profile shows five levels (Fig. 1b; see also Supplementary Infor-
mation, Section 2 and Table S-2); from bottom to top: saprolite, with smectite
from the weathering of clinopyroxene, which is still visible in the deepest parts;
transitional laterite where smectite is progressively replaced by Fe oxides and
kaolinite; limonitic laterite dominated by goethite with haematite, kaolinite and
gibbsite; haematitic laterite dominated by haematite with goethite, kaolinite and
gibbsite; and transported laterite of similar composition but containing clasts
and evidence of former alluvial channels. Similar lateritic profiles are developed
over other ultramafic–mafic rocks in Australia (Anand and Paine, 2002), with
most of the weathering profile directly inherited from the parent rock except
for the transported level. The depth of the profile indicates that the weathering
occurred over long time scales, possibly starting as early as 430 million years
ago (Fergusson, 2010), in a stable tectonic context. Bulk assays show that Sc
concentration increases upward, from ca. 100 ppm in the transitional laterite to
ca. 500 ppm in the limonitic laterite (Fig. 1b,c and Table S-3). The concentration
then decreases in the haematitic laterite and drops to ca. 250 ppm in the trans-
ported laterite.

Figure 1 (a) Geographical location of the Syerston–Flemington deposit. (b) Schematic cross
section of the lateritic cover forming the Syerston–Flemington deposit, constructed from Identification of Iron Oxides as Main Scandium Hosts
petrographic analysis of drill-cores. Average Sc concentrations ([Sc]avg) are calculated for each
layer from ICP-MS analyses of samples collected every metre on each core. (c) Distribution of The mineralogy is typical of lateritic profiles developed over ultramafic rocks
Sc with depth along the different levels of a typical profile (Tran.: transitional laterite). (Freyssinet et al. (2005); Fig. 2a,b and Table S-4). The ore is dominated by haema-
tite and Al-bearing goethite, associated with kaolinite and gibbsite. Minor phases
include anatase, quartz and an Fe oxide with an inverse spinel structure, either
maghemite or magnetite. The broad X-ray diffraction lines (Fig. 2a) reflect the
Core Sampling and Analytical Methods
poor crystallinity or small particle size (<100 nm) of the Fe oxides. The bulk Sc
Each metre of 26 vertical aircore holes has been analysed for Sc and two diamond content is correlated with the proportion of Al-bearing goethite, indicating its
drill-cores of about 30 m length have been sampled to collect rock chips from the potential role as a Sc host in the ore (Fig. 2c).
limonitic part of the lateritic cover. Quantitative mineralogical compositions were Systematic SEM–EDXS mapping confirms the absence of discrete Sc
determined by X-ray diffraction (XRD) and Rietveld refinement. Major and trace phases, as expected from the scarcity of such phases in nature (Samson and
elements were determined by X-ray fluorescence (XRF) analysis and inductively Chassé, 2016). The EMP analyses of Si, Ti, Al, Fe and Sc have been averaged
coupled plasma mass spectrometry (ICP-MS), respectively. Mapping of major on each grain type, as identified by combining SEM images, major elements
elements was done using scanning electron microscopy–energy dispersive X-ray and Sc contents and applying statistical clustering (Supplementary Information,
spectroscopy (SEM–EDXS) on polished sections of samples embedded in epoxy Section 6 and Table S-6). Scandium contents are low to extremely low in Al-rich
resin. The electron microprobe (EMP) gave point analyses for major and minor grains (ca. 300 ppm), Ti-rich oxides (ca. 100 ppm) and quartz (below detection
elements along with Sc. The distribution of Sc was mapped by synchrotron limit, ca. 30 ppm). The highest Sc contents (ca. 1300 ppm) are encountered in Fe

107 Geochem. Persp. Let. (2017) 3, 105–114 | doi: 10.7185/geochemlet.1711 Geochem. Persp. Let. (2017) 3, 105–114 | doi: 10.7185/geochemlet.1711 108
Geochemical Perspectives Letters Letter Letter Geochemical Perspectives Letters

oxide grains that contain Al (ca. 7 wt. %) and have low EMP analytical totals (ca. higher goethite component. A third type of matrix is slightly enriched in both Al
85 wt. %). These grains appear to correspond to the Al-bearing goethite identi- and Si, which is consistent with the presence of minor kaolinite mixed with Fe
fied by XRD. Another type of Fe oxide grains, with a lower concentration of Sc oxides. The Sc content of this matrix is ca. 400 ppm, which suggests that kaolinite
(ca. 200 ppm) and high Fe could correspond to the haematite phase identified is only a minor Sc host.
using XRD. To distinguish between goethite and haematite, we also used Fe K-edge
Much of each sample consists of a fine-grained matrix with three distinct XANES spectra. Using the relative normalised intensity of the absorption maxima
compositions. Two correspond to mixtures of Fe oxides with different Sc contents, of goethite and haematite, at 7133.8 eV and 7136.9 eV, respectively (Combes et al.,
ca. 650 ppm for one and ca. 400 ppm for the other. The former contains slightly 1989), we obtained Fe-speciation maps (Fig. 3a). Comparison with µ-XRF maps
less Fe but more Al and has a lower analytical sum than the latter, reflecting a of Sc (Fig. 3b) indicate that Sc-poor and Sc-rich grains mostly contain haematite
and goethite, respectively. Iron K-edge XANES spectra in the complete range
of energy confirm these observation (Fig. 4a), showing a good match between
spectra of goethite and Sc-rich zones and between spectra of haematite and
Sc-poor zones.

Figure 3 (a) Map of Fe speciation obtained by subtracting normalised synchrotron µ-XRF maps
at 7133.9 eV, the energy characteristic of goethite and 7136.7 eV, the energy characteristic of
haematite. (b) Synchrotron µ-XRF mapping of Sc.
Figure 2 (a) X-ray diffraction pattern of ore sample JSD-1 – 15.4 m and associated multiphase
Rietveld refinement (Al-gt: Al-bearing goethite, hem: haematite, kln: kaolinite, gbs: gibbsite,
mgh: maghemite, ant: anatase). (b) Average phase proportions in the samples calculated
from Rietveld refinement. (c) Bulk Sc concentration versus proportion of Al-bearing goethite
estimated from Rietveld refinement.

109 Geochem. Persp. Let. (2017) 3, 105–114 | doi: 10.7185/geochemlet.1711 Geochem. Persp. Let. (2017) 3, 105–114 | doi: 10.7185/geochemlet.1711 110
Geochemical Perspectives Letters Letter Letter Geochemical Perspectives Letters

in haematite are about 200 ppm Sc. As haematite accounts for about 30 % of the
mineral phases, Sc in haematite may represent ca. 50 ppm, corresponding to most
of the remaining 20 % of total Sc.

Scandium Speciation in the Ore

Scandium K-edge XANES spectra of synthetic reference materials show that Sc
incorporation in goethite or in haematite can be distinguished using the posi-
tion of the edge crest at 4508.2 eV and 4511.8 eV, respectively (Fig. 4b), while Sc
adsorbed on goethite is identified by a broad, featureless edge crest extending
from 4508 eV to 4511.5 eV. On the low energy side, a pre-edge feature bears
additional information (e.g., Galoisy et al., 2001). There is a noteworthy enhance-
ment of the intensity of this feature in the substituted samples due to the distor-
tion of the Sc site. The Sc K-edge XANES spectra on lateritic goethite grains
show a broad edge crest and a low-intensity pre-edge feature, consistent with Sc
adsorbed on goethite. In contrast, lateritic haematite grains show an edge crest at
4512 eV and a more intense pre-edge feature, corresponding to Sc incorporated
in haematite. The same distinction holds when investigating the matrix: the high
Sc concentrations are associated with Sc-adsorbed goethite. However, lateritic
samples give less resolved spectra than the crystalline references. Comparison
is limited because Sc K-edge XANES spectra are scarce in the literature, but this
may reflect a poor crystallinity in fine-grained natural phases, or some minor
contribution of other Sc species.

A Mechanism for Scandium Enrichment

Due to the high concentration of Sc in clinopyroxenes, weathering leads to Sc-rich
waters circulating in the regolith below the water table. Seasonal precipitation of
goethite allows the adsorption of Sc3+. During dry periods, haematite develops
from goethite, and may incorporate part of the adsorbed Sc in its crystal structure.
However, this process is limited by the size difference between six-fold coordi-
nated Sc3+ and Fe3+ but such size differences will not influence the adsorption
capacity of goethite under near-neutral pH conditions.
Scandium is often associated with the rare earth elements (REE). The
ionic radius of Sc3+ is slightly smaller than those of heavy REE for the same
Figure 4 XANES spectra at the (a) Fe K-edge. (b) Sc K-edge (gt: goethite and hem: haematite).
coordination number. During lateritic weathering of ultramafic–mafic rocks, Sc
The numbers in brackets refer to the position given in Figure 3.
behaves like the heavy REE. The enrichment factor of Sc between the ore and
Using the EMP-derived Sc concentration in goethite, around 1300 ppm, fresh saprolite is ca. 5 (Table S-5, Fig. S-2). For the REE, it increases continuously
and the proportion of goethite obtained from Rietveld refinement, about 30 %, with decreasing ionic radii, from ca. 2 for the light REE to ca. 3.5 for the heavy
we calculate that goethite hosts about 400 ppm Sc out of the average ca. 500 ppm REE. The low prospectivity of the lateritic deposits for REE reflects the low REE
of Sc in the samples, i.e. ca. 80 % of total Sc. Average EMP-derived concentrations content in the parent rock compared to average crustal concentrations (two to
ten times lower, Rudnick and Gao, 2014).

111 Geochem. Persp. Let. (2017) 3, 105–114 | doi: 10.7185/geochemlet.1711 Geochem. Persp. Let. (2017) 3, 105–114 | doi: 10.7185/geochemlet.1711 112
Geochemical Perspectives Letters Letter Letter Geochemical Perspectives Letters

Lateritic profiles over ultramafic–mafic rocks usually show Sc concentra- Cite this letter as: Chassé, M., Griffin, W.L., O’Reilly, S.Y., Calas, G. (2017)
tions lower than 100 ppm, corresponding to enrichment by a factor of ten during ­Scandium speciation in a world-class lateritic deposit. Geochem. Persp. Let. 3,
lateritic weathering (Aiglsperger et al., 2016; Maulana et al., 2016). This is similar 105–114.
to the maximum factor of enrichment found in the Syerston–Flemington deposit
where the limonitic laterite reaches 800 ppm Sc compared to ca. 80 ppm in the
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