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Co in regolith at Thackaringa

WHERE HAS ALL THE COBALT GONE? REGOLITH


GEOCHEMISTRY OF COBALTIFEROUS PYRITE DEPOSITS,
BROKEN HILL, NSW, AUSTRALIA

E.J. Cohen1, D.R. Cohen1, I.T. Graham1, I.J. Pringle1,2 and W. Leyh3
1
School of Biological, Earth and Environmental Sciences, University of New South
Wales, NSW 2052, Australia.
2
Broken Hill Prospecting Ltd, Lvl 14, 52 Phillip Street, Sydney, NSW 2000, Australia.
3
Eaglehawk Geological Consulting P/L, PO Box 965, Broken Hill, NSW 2880,
Australia.

Introduction
The stratabound cobaltiferous pyrite deposits at Thackaringa, southwest of
Broken Hill in far western New South Wales, were deposited in a back-arc basin on
the eastern margin of the Palaeoproterozoic Australian continent (Barovich and
Hand, 2008; Conor and Preiss, 2008). The sulphide mineralisation is hosted in what
are now quartz-albitebiotitemuscovite gneisses, and is mainly pyrite with minor
amounts of chalcopyrite, galena and sphalerite. The deposits have been subjected to
deep weathering which may extend down to >60m in some areas, especially where
sulphides are present. Cobalt is substituted within pyrite grains at concentrations up
to 6,000 ppm (Plimer, 1977; Li, 2013), however Co concentrations <5 ppm are
present in saprolite or gossans derived from the mineralised zone (Pringle, 2013).

A geochemical and petrological study of the area surrounding the Big Hill and
Pyrite Hill prospects was completed to investigate the behaviour of ore-related
elements within the secondary environment, with a focus on Co.

Methodology
Samples of cobaltiferous pyrite mineralisation, host lithologies and in situ
regolith, were collected from drill samples, outcrop and waste piles. Soil and stream
sediment samples were collected across four traverses intersecting the Big Hill and
Pyrite Hill mineralised zones and along adjacent streams. A suite of petrological and
geochemical analyses were run on the samples, including aqua-regia extraction ICP-
OES on the soils and stream sediments. Field-portable XRF analysis was
undertaken on various materials in the field, although the high detection limits for Co
(due to Fe interference) preclude analysis of this element. Adsorption isotherms
were experimentally established for Co on representative samples of gossans, soils
and stream sediments over the pH range of 4–9 (in 0.1 M NaNO3 and ~10 g/L
slurry).

E.J. Cohen, D.R. Cohen, I.T. Graham, I.J. Pringle and W. Leyh April 2015
Co in regolith at Thackaringa

Results and Discussion


Host rock saprolite is dominated by quartz, kaolinite and minor Fe-oxides.
Mineralised units have weathered to siliceous gossans displaying boxwork and more
massive Fe-oxyhydroxides, and clay-rich void-fill (Fig. 1). Some pyrite is preserved
near surface due to armouring by quartz. At the weathering front, sulphides have
been altered to jarosite, native sulfur and a range of Fe-oxyhydroxides.

5cm 5cm

(a) (b)
5cm 5cm

(c) (d)

Figure 1. Examples of gossan and related materials from the Thackaringa


pyrite deposits. (a) Host lithology strongly weathered to clays (allophane); (b)
Hematite-goethite-quartz boxwork gossan; (c) Massive secondary Fe-
oxyhydroxide precipitates in voids and fractures; (d) boxwork gossan
collected adjacent to (c).

The saprolite has largely been stripped of Co and other chalcophile elements
all the way to the base of weathering (Fig. 2), due to the acid generated by pyrite
oxidation and the lack of neutralisation capacity in the host rocks. Only trace
amounts of Co (<5 ppm) and other sulphide-related metals have been retained in the
weathered profile. These metals are largely associated with massive Fe-
oxyhydroxide accumulations in the saprolite.

The effect of intense leaching can be seen in microprobe element mapping of


partially weathered mineralised host rock (Fig 3) with a very distinct boundary
between the weathered and fresh rock zones. No specific Co minerals were
identified by XRD or EMPA in either the in-situ or transported regolith.

E.J. Cohen, D.R. Cohen, I.T. Graham, I.J. Pringle and W. Leyh April 2015
Co in regolith at Thackaringa

Fe S Co Zn Pb As Mn Ca Ti Al / Ti
(%) (%) (ppm) (ppm) (ppm) (ppm) (ppm) (%) (%)
0 12 0 16 0 1600 0 400 0 100 0 30 0 300 0 3 0 0.4 0 150
0m

10

15

Qtz- Base of weathering


20
Alb-
Py

25

30

Figure 2. Major and trace element values from the upper part of unweathered
rock through the saprolite section of RC hole BER002 and photo-log of the
chip trays at 1m intervals.

jarosite

quartz

albite

2 Fe-oxide

Si 0 245 cps Fe 0 883 cps Al 0 344 cps

cobaltian
pyrite

Co S Al Zn
0 154 cps 0 355 cps 0 58 cps

Figure 3. EMPA element mapping of cobaltian pyrite mineralisation across a


weathering front in a sample from Pyrite Hill. The weak apparent Co signals in
the weathered materials are most likely due to interference by Fe.

E.J. Cohen, D.R. Cohen, I.T. Graham, I.J. Pringle and W. Leyh April 2015
Co in regolith at Thackaringa

A conceptual model of the terrain around the Thackaringa deposits is shown


in Figure 4. While broadly similar to other profiles in the deeply weathered terrain of
the Curnamona region (Hill, 2004), there is a lack of the classic pallid, mottled or
duricrust zones. This may be attributed to erosion as most of the mineralisation
occurs along ridges. The areas of low relief are covered with varying depths (to ~5m)
of transported cover dominated by quartz, secondary Fe-oxides, kaolinitic clays and
some partially weathered materials, along with variable amounts of calcrete.

Outcrop Sub-crop
Colluvium + Deeper colluvium
coarse lag + overbank deposits

Finer-grain Recent
colluvium alluvium
Saprolite

Base of weathered
profile Palaeo-gravel lenses

Palaeo-colluvium
Unweathered bedrock + sheetwash

Former stream beds

Figure 4. Conceptual regolith model for the Thackaringa area and examples of
the main terrain components.

Across Pyrite Hill, Co concentration in soils decreases progressively towards


the drainages areas, whereas elevated As and Pb concentrations are largely
restricted to the areas above and immediately adjacent to the outcropping
mineralisation (Fig. 5). Carbonate accumulations in drainage areas appear to have
had little effect on the mobility of elements such as Co, Ni, and Pb, and (along with
quartz) only act as a dilutant.

Adsorption of Co onto gossan follows typical patterns for Fe-oxyhydroxides


such as goethite (McLaren et al., 1986), with little retention below pH 4.5 (Fig. 6). In
the soils and stream sediments, however, the isotherms are more complicated with
significant adsorption below pH 4.5 which may be onto clays, Mn oxides and
possibly some Fe-oxyhydroxides.

E.J. Cohen, D.R. Cohen, I.T. Graham, I.J. Pringle and W. Leyh April 2015
Co in regolith at Thackaringa

1000 100k

100 75k

10 50k

1 As 100 Ca 25k
100
0.1 75 0

10 50 Cu
2000 Pb 25
600
1 0
1500 450

1000 300

S 80 250
500
40
Mn
0 60
Zn 0

30 40

20 20
40
10 0
6.0
Co 0
30

4.5
Fe 28
20

3.0
21 Cr 10

1.5 0

0
14
Ni
7

A A’ Quartz-albite
gneiss with
305m 305m Horizons containing sporadic low
disseminated conc Co-py
pyrite in quartz-
albite gneiss
275 275

0 250 500 750 1000 1250 1500m 0 250 500 750 1000 1250 1500m

Figure 5. Stacked element profile for aqua-regia extractable metal contents in


soils for a traverse across Pyrite Hill.

100

80
Pyrite Hill gossan
60 sample THK1020

40

20 10 ppm
100 ppm
0

100

80
% of Co(II) Composite soil (<30 μm
60 fraction)
adsorbed or
precipitated 40

20 10 ppm
100 ppm
0

100

80
Composite stream
60 sediment (<30 μm
fraction)
40

20 10 ppm
100 ppm
0
3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5
pH

Figure 6. Adsorption isotherms (vs pH) for Co at 10 and 100 ppm on gossan
sample THK1020, and the <200μm fraction of a composite soil and a composite
stream sediment sample from Big Hill.

E.J. Cohen, D.R. Cohen, I.T. Graham, I.J. Pringle and W. Leyh April 2015
Co in regolith at Thackaringa

Conclusions
Despite high Co concentrations in the primary sulphides, in situ regolith
materials derived from the mineralized zones are largely stripped of Co and other
mobile chalcophile elements. In adjacent soils, the Co is retained to a greater extent
than other transition metals, even at pH below 4.5, on clays and minerals other than
goethite. This study has shown that during oxidation of the Co-bearing sulphides, the
Co has been rapidly removed from the system.

References
BAROVICH, K. & HAND, M., 2008. Tectonic setting and provenance of the
Paleoproterozoic Willyama Supergroup, Curnamona Province, Australia:
Geochemical and Nd isotopic constraints on contrasting source terrain components.
Precambrian Research, 166, 318–337.

COHEN, E.J., 2014. Cobalt dispersion in the secondary environment at the


Thackaringa cobaltiferous pyrite deposits, Broken Hill, NSW. Honours thesis,
University of New South Wales.

HILL, S.M., 2004, Broken Hill 1:100,000 regolith-landform map. CRC LEME and
Geoscience Australia.

LI, R.L., 2013. Geochemistry of the sulphide mineralisation at the Railway Prospect,
Broken Hill, Australia. Honours Thesis, University of New South Wales.

MCLAREN, R.G., LAWSON, D.M. & SWIFT, R.S., 1986. Sorption and desorption of cobalt
by soils and soil components. Journal of Soil Science, 37, 413.

PLIMER, I.R., 1977. The origin of the albite-rich rocks enclosing the cobaltian pyrite
deposit at Thackaringa, N.S.W., Australia. Mineralium Deposita, 12, 175-187.

PRINGLE, I.J., 2012. Thackaringa cobalt deposits: Sulphide formation by microbial


activity in a Paleoproterozoic anoxic brine basin. Report to Broken Hill Prospecting
Ltd.

E.J. Cohen, D.R. Cohen, I.T. Graham, I.J. Pringle and W. Leyh April 2015