Minerals Engineering 18 (2005) 849–854

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Beneficiation of a gold bearing enargite ore by flotation

and As leaching with Na-hypochlorite
L. Curreli *, M. Ghiani, M. Surracco, G. Orrù
Department of Geoengineering and Environmental Technologies (DIGITA), University of Cagliari, 09123 Cagliari, Italy

Received 30 November 2004; accepted 14 January 2005

Available online 31 May 2005

Abstract

The deep mineralized bodies of the Italian Serrenti-Furtei gold-bearing deposit, located in southern Sardinia, contain substantial
amounts of enargite-luzonite and pyrite with subordinate tennantite, covellite, chalcopyrite and arsenopirite. The gold, which occurs
as grains of between a few tens of micrometres and submicron size, is not amenable to direct cyanidation. These ores are beneficiated
by bulk flotation using sulphydryl collectors and the resulting concentrates are then pyrometallurgically processed to produce gold
and copper. However, the concentrates contain significant amounts of arsenic, severely reducing their market value; the abatement
of this highly toxic metal in the flue gas to comply with stringent emission limits, increases processing costs significantly.
In order to reduce the arsenic content in the concentrates and hence the penalties incurred, we carried out an investigation on
enargite leaching using sodium hypochlorite to selectively dissolve the arsenic.
By suitably adjusting the main influencing variables, leaching was found to be effective, achieving 96% arsenic removal without
significant Au and Cu losses, increasing the commercial value per tonne of concentrate.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Gold ores; Sulphide ores; Froth flotation; Leaching; Environmental

1. Introduction
The mineralogic and petrographic characteristics of
the epithermal gold mineralisations in the Serrenti-Fur-
tei mining district in southern Sardinia vary consider-
ably with depth (Garbarino et al., 1991; Fadda et al.,
2004). The upper part of the deposit, where the rock is
moderately porous due to intense oxidation and con-
tains lower gold grades, has been open-pit mined and
the gold recovered by direct cyanidation using either
heap or vat leaching. The deeper parts host mainly
sulphide mineralisations which have a more compact
*
Corresponding author. Tel.: +39 70 675 5525; fax: +39 70 675 5523.
E-mail address: curreli@unica.it (L. Curreli).
structure and are composed for the most part of enarg-
ite-luzonite, to which chiefly gold is associated, and pyr-
ite. These minerals are not amenable to direct
cyanidation but contain economically interesting con-
centrations of enargite. A conventional flotation process
was devised to recover the gold and copper in a bulk
concentrate to be subjected to further processing via
pyrometallurgical techniques (Ghiani et al., 2000).
The process was designed using ethylxanthate as col-
lector and lime as pyrite depressant. Commercial appli-
cation to the ores in question proved to be fairly
efficient, achieving high Cu and Au recoveries in the
bulk concentrate (Di Giovanni et al., 2003).
Unfortunately, the prevalence of enargite among the
copper-bearing minerals and as a result the relatively
high As content in the concentrates severely reduces
their economic value, owing to the hazardous emissions

0892-6875/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.01.023
850 L. Curreli et al. / Minerals Engineering 18 (2005) 849–854

generated from pyrometallurgical processing. Thus, in

unfavourable metal market conditions, direct roasting
may well prove to be an uneconomical option.
In an attempt to solve this problem, we explored the
possibility of dissolving the arsenic from the concen-
trates prior to pyrometallurgical processing.
Two techniques for arsenic removal from enargite are
proposed in the literature, namely:

(a) alkaline leaching of enargite concentrates using

sodium sulphide solutions after mechanical activa-
tion via fine grinding (Baláž et al., 2000);
(b) leaching of natural enargite crystals with sodium
hypochlorite under alkaline oxidizing conditions
whereby the enargite is converted into crystalline
CuO and the arsenic solubilises forming AsO34
(Viñals et al., 2003).
The second method was judged to be especially
attractive in terms of its potential application at the
commercial scale. Thus we decided to focus our atten-
tion on this particular leaching technique.
The investigation described here aimed at exploring
the possibility of applying this method to the marketable
Au–Cu concentrates obtained by flotation of the sul-
phide ores from the Serrenti-Furtei deposit described
above. We experimentally determined the influence of
the most important process variables, such as grain size
of the solid material, solids concentration in the solu-
tion, temperature, pH and hypochlorite concentration
in the leachant as well as contact time.
2. Experimental procedure
The bulk Au–Cu concentrate used in the experiments
was obtained in a laboratory flotation cell from drill
cores made in the deep zones of the deposit during
Fig. 1. XRD patterns of a representative sample of the flotation
concentrate.
Leach tests were conducted in a 1-litre thermostated
Pyrex glass reactor containing NaClO solutions mechan-
ically stirred at 500 rpm, as shown in the schematic of
Fig. 2.
As mentioned in the introduction, the effect of the
main influencing parameters, namely solids concentra-
tion (0.004, 0.01, 0.04 w/w), initial hypochlorite concen-
tration (0.05, 0.13, 0.20, 0.28 M), pH (10.5, 11.5, 12.5),
temperature (20, 30, 40, 45 °C), leach time (up to
120 min) was experimentally evaluated on both grain
size fractions. All experiments were carried out using
0.5 kg of leachant.
The influence of the single variables was then deter-
mined following the classic procedure of varying the
value of one variable while keeping the other variables
constant.
Leach results were evaluated through As, Cu and Au
determinations on the leachate and solid residue ob-
tained after filtration. Sodium hypochlorite consump-
7

prospecting.
The as received material was first dry crushed to
100% passing 2 mm and then wet ground to below
0.150 mm operating in closed circuit in a porcelain ball
8
mill.
1
The ground product was subjected to flotation with
ethylxanthate after pyrite depression with lime. The
cleaned concentrate obtained, assaying 90.25 g/103 kg 2 3 4

Au, 33.15% Cu, 12.55% As and 9.16% Fe, was suitable

for the pyrometallurgical production of gold and 6 Chemical
analysis
copper. Leach residue

Diffractometric analysis (XRD) (Fig. 1) shows the

concentrate to contain significant concentrations of Leach solution
Chemical
analysis
enargite. 9 5

This concentrate 0.150 mm and samples of the same

Fig. 2. Schematic of the experimental set-up and procedure: (1)
wet ground to less than 0.050 mm, were experimentally thermostated reactor, (2–3) heated circulating bath, (4) pH-meter, (5)
investigated to evaluate the potential of sodium hypo- filtering flask, (6) Bückner funnel, (7) mechanical stirrer, (8) electrode,
chlorite leaching to remove the arsenic. (9) vacuum pump.
 L. Curreli et al. / Minerals Engineering 18 (2005) 849–854 851

tion was determined using the iodide titration method

(Clesceri et al., 1998).
For a certain number of tests we also analysed the
leach residues using diffractometric (XRD) and, for
mineral-petrographic observations, scanning electron
microscope (SEM) techniques to determine the chemi-
cal-mineralogical changes undergone during hypochlo-
rite leaching. The results of some of the XRD analyses
are shown, by way of example, for the two different
grain sizes 0.150 and 0.050 mm, in Figs. 3 and 4
respectively.
The concentrations of elements such as S, As, Sb, Cu
and Fe were determined in different points of specially
prepared polished sections by means of electronic micro-
probe analysis. Mean data were found to agree with re-
ports in the literature (Viñals et al., 2002 ; Viñals et al.,
2003) concerning the formation of tenorite (CuO) on the
surface of leached particles as the oxidation product of
enargite. The photos of Fig. 5 show the tenorite in the
form of a multilayered microporous structure enclosing
the enargite nucleus, which has remained intact.

Fig. 3. XRD patterns of a sample of solid leach residue. Grain size

0.150 mm.

Fig. 5. SEM (BSE) images of leached enargite grains. Grain size

0.150 mm.

3. Results and comments

3.1. Influence of solids concentration and grain size

Fig. 6 illustrates the effect of solids concentration on

Fig. 4. XRD patterns of a sample of solid leach residue. Grain size
0.050 mm.
the leaching process for both grain size fractions
examined.
As can be seen, arsenic leaching efficiency deteriorates
rapidly with increasing solids concentration but im-
proves for the smaller grain size, because of the higher
specific surface area available. The gradual diminishing
of the differences in arsenic removal efficiencies between
852 L. Curreli et al. / Minerals Engineering 18 (2005) 849–854

100 100

10 minutes
-0.150 mm
80 30 minutes
-0.050 mm 80
60 minutes
As removed [%]

As removed [%]
120 minutes
60 60

40 40

20 20

0
0
0 0.01 0.02 0.03 0.04 0.05
10 10.5 11 11.5 12 12.5 13
Solid concentration (weight %) pH

Fig. 6. Influence of solids concentration on arsenic removal efficiency. Fig. 7. Influence of pH on arsenic removal efficiency for various contact
NaClO concentration = 0.20 M, pH = 12.5, temperature = 30 °C, con- times. Grain size = 0.050 mm, solids concentration = 0.004 w/w,
tact time = 60 min. NaClO concentration = 0.20 M, temperature = 30 °C.

the two size classes examined can be clearly attributed to

the insufficient availability of the leachant vis-à-vis the
amount of arsenic to be removed, as confirmed by the
100
results subsequently obtained for the influence of molar
45 °C
concentration of the leaching agent.
40 °C
The above findings suggest that, for suitable solids 80
30 °C
concentration, the efficiency of arsenic removal can be
As removed [%]

20 °C
enhanced by finer grinding and point to the importance 60

of grain size in process optimization, also in economic

terms as well. 40

3.2. Influence of pH and contact time

20

The influence of these two parameters, as well as of

0
temperature and hypochlorite concentration discussed 0 20 40 60 80 100 120
below, was assessed for solids concentrations of Time [min]
0.004 w/w and 0.050 mm grain size, that is for the condi-
tions yielding optimum arsenic removal efficiency in the Fig. 8. Influence of temperature on arsenic removal efficiency versus
contact time. Grain size = 0.050 mm, solids concentration = 0.004
above tests, keeping the other variables constant. The w/w, NaClO concentration = 0.20 M, pH = 12.5.
results obtained, summarised in Fig. 7, show that:

– optimum pH of the leachant solution was found to be

around 12.5, as at higher values the hypochlorite was
observed to rapidly decompose, in agreement with
Viñals et al. (2002);
– arsenic removal efficiency increases with contact time.
In this regard, the removal rate was found to be rel-
atively rapid in the first 20–30 min, after which it grad-
ually slowed down, evidently because of the competing
effect of the surface formation of tenorite, which im-
pedes further oxidation of the underlying enargite, and
of the reduction in ClO concentration.
3.3. Influence of temperature
The influence of leachant temperature, is shown in
the diagram of Fig. 8 where arsenic removal efficiency
is plotted versus time for varying solution temperatures.
Generally speaking, leaching efficiency was found to
increase with temperature up to a certain point, beyond
which the trend is reversed. This ‘‘inversion tempera-
ture’’, observed at between 40° and 45 °C for contact
times of less than one hour, decreases when contact time
is prolonged.
This behaviour may be explained by the fact that at
temperatures higher than the inversion temperature
some copper passes into the solution causing a shift in
pH to values of below 12.5 due to precipitation of
hydroxides, thereby reducing arsenic removal efficiency.
This is confirmed by the bluish colour of the leachates
observed in these conditions and the difficulty in main-
taining pH at close to 12.5. The higher copper solubilisa-
tion rate observed for longer leachant/mineral contact
times is likely the cause of the decrease in inversion
temperature.
 L. Curreli et al. / Minerals Engineering 18 (2005) 849–854 853

3.4. Influence of hypochlorite concentration temperature at 30 °C and pH at 12.5, arsenic removal

efficiency of 92.5% was obtained in 60 min, compared
The diagrams of Fig. 9 clearly show the major role to 74.6% in 120 min with no hypochlorite solution
played by this parameter which already emerged to top-up.
some extent in the tests for evaluating the effect of solids
concentration.
Over the concentration range tested (0.05–0.28 M), 4. Conclusions
both removal efficiency and leaching rate gradually in-
crease with molar concentration of the leachant, in keep- Hydrometallurgical processing using sodium hypo-
ing with the hypochlorite consumption determined by chlorite solutions has proven to be an effective technique
the dissolution of arsenic (Fig. 10). for removing the arsenic contained in the enargite-rich
The results of this series of tests showed that the ar- gold concentrates obtained by flotation of the ores
senic can be practically completely removed (As up to hosted in the deeper sulphide portions of the Italian
0.71%) by suitably adjusting the molar concentration Serrenti-Furtei mine. The presence of arsenic in these
of the leachant solution. From an applicative stand- concentrates, which are further beneficiated by pyromet-
point, the findings suggest keeping hypochlorite concen- allurgical processing, severely reduces their market
tration constant by topping up the solution, also to value.
enhance arsenic dissolution rate. Additional experiments The leaching process does not produce any adverse
performed to corrobate this finding confirmed expecta- effects on the gold which concentrates in the leach resi-
tions. By maintaining constant NaClO concentrations at due. Only at temperatures higher than 40 °C does the
0.20 M, solids concentration in solution at 0.004 w/w, copper solubilise to a minor extent, most of which is
converted to CuO.
Thus the environmental impact of pyrometallurgical
100
0.28 M processing is substantially mitigated, increasing the
0.20 M
0.13M value of the copper–gold concentrates.
80 0.05 M
Process efficiency depends to a large extent on opti-
mum adjustment of a number of variables. The experi-
As removed [%]

60
mental results show in fact that temperature and pH
of the leachant should be maintained at around 30 °C
40 and 12.5 respectively, and fine grain sizes, low solids
concentration and high hypochlorite concentrations in
20 the leachant solution are also required.
In practice, however, the optimum adjustment of
0 these last three variables is dictated essentially by con-
0 20 40 60 80 100 120 siderations of an economic nature. For example, finer
Time [min]
grinding may well yield the same arsenic removal effi-
Fig. 9. Influence of NaClO molar concentration on arsenic removal ciency at higher solid/liquid ratios or using lower con-
efficiency versus contact time. Grain size = 0.050 mm, solids concen- centrations of hypochlorite in the leachant solution.
tration = 0.004 w/w, pH = 12.5, temperature = 30 °C.

Acknowledgements
100
0.28 M
0.20 M Research funded by MIUR (Italian Ministry for Edu-
80 0.13 M cation, Universities and Research) and CNR (Italian
0.05 M
National Research Council).
NaClO residue [%]

60 The authors would like to thank Prof. C. Garbarino

for his assistance in performing the mineralogic and
40 petrographic analyses.

20
References
0 Baláž, P., Achmovičová, M., Bastl, Z., Ohtani, T., Sánchez, M., 2000.
0 20 40 60 80 100 120
Time [min] Influence of mechanical activation on the alkaline leaching of
enargite concentrate. Hydrometallurgy 54, 205–216.
Fig. 10. NaClO consumption for different molar concentrations versus Clesceri, L.S., Greenberg, A.E., Eaton, A.D., 1998. Standard Methods
contact time. Grain size = 0.050 mm, solids concentration = 0.004 for the Examination of Water and Wastewater, 20th ed. APHA,
w/w, pH = 12.5, temperature = 30 °C. AWWA, WEF, Washington, pp. 453–458.
854 L. Curreli et al. / Minerals Engineering 18 (2005) 849–854
Di Giovanni, S., Ghiani, M., Peretti, R., Serci, A., Zonnedda, G.,
Zucca, A., 2003. Beneficiation of gold bearing ores associated with
the Tertiary volcanism in south Sardinia (Italy). In: Proceedings of
22nd International Mineral Processing Congress (IMPC), Cape
Town, pp. 493–500.
Fadda, S., Fiori, M., Grillo, S.M., Matzuzzi, C., 2004. Vertical zoning
of mineralization in some drill-holes of the M.S. Miali sector at the
Furtei epithermal gold deposit, Sardinia, Italy. In: Proceedings of
the interim IAGOD conference, Vladivostok (Russia), pp. 423–426.
Garbarino, C., Grillo, S.M., Marcello, A., Pretti, S., Uras, I., Fiori,
M., 1991. First data on epithermal occurrences in Sardinia, Italy.
In: Brazil Gold Õ91. Balkema, pp. 143–150.
Ghiani, M., Serci, A., Peretti, R., Zucca, A., 2000. Beneficiation of
gold sulphide ores from south Sardinia, Italy. In: Ozbayoglu, et al.
(Eds.), Mineral Processing on the Verge of the 21st Century.
Balkema, pp. 305–308.
Viñals, J., Roca, A., Benavente, O., Hernandez, M.C., Herreros, O.,
2002. Removal of arsenic, selenium and tellurium from base metal
concentrate. In: Palfy, P., Vircikova, E. (Eds.), Proceedings of the
5th International Conference on Metallurgy, Refractories and
Environment, Kosice, Slovakia, pp. 481–486.
Viñals, J., Roca, A., Hernandez, M.C., Benavente, O., 2003. Topo-
chemical transformation of copper oxide by hypochlorite leaching.
Hydrometallurgy 68, 183–193.