International Journal of Mineral Processing 102103 (2012) 116123

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International Journal of Mineral Processing

journal homepage: www.elsevier.com/locate/ijminpro

Effects of sodium thiosulphate on chalcopyrite and tennantite: An insight for

alternative separation technique
Himawan T.B.M. Petrus b, d,, Tsuyoshi Hirajima a, Keiko Sasaki a, Hideyuki Okamoto c
a

Faculty of Engineering, Kyushu University, Japan

Graduate School of Engineering, Kyushu University, Japan
Sumitomo Metal Mining Co., Ltd., Japan
d
Department of Chemical Engineering, Gadjah Mada University, Indonesia
b
c

a r t i c l e

i n f o

Article history:
Received 16 September 2010
Received in revised form 18 October 2011
Accepted 1 November 2011
Available online 7 November 2011
Keywords:
Chalcopyrite
Tennantite
Sodium thiosulphate
Flotability

a b s t r a c t
In this study, the effects of sodium thiosulphate on chalcopyrite and tennantite at various pH values were investigated. Contact angle, otation (Hallimond tube), zeta potential and X-ray photoelectron spectroscopy were
used to observe these effects and to investigate the mechanisms involved. The addition of sodium thiosulphate
depressed both chalcopyrite and tennantite at all pH values. Further addition of diethyl dithiophosphate signicantly increased the otability of chalcopyrite at all pH values as well as tennanite in acidic conditions, but not tennantite in alkaline conditions. In light of the zeta potential measurements and due to the stability of thiosulphate
over the pH range, the coverage of sulphate resulting from the oxidation of thiosulphate was responsible for the
depression of both chalcopyrite and tennantite in acidic conditions. Adsorption of diethyl dithiophosphate species
on the mineral surface resulted in otability of tennantite which was almost as high as that of chalcopyrite.
In alkaline conditions, coverage of the copper thiosulphate complex was responsible for the depression. The copper thiosulphate complex inhibited adsorption of diethyl dithiophosphate species on the mineral surface. Higher
coverage of the copper thiosulphate complex on tennantite caused an insignicant increase in its otability in
comparison to that of chalcopyrite which allowed the separation of tennantite from chalcopyrite. The XPS spectra
supported the proposed mechanism of thiosulphate depression on these minerals.
2011 Elsevier B.V. All rights reserved.

1. Introduction
It is generally acknowledged that arsenic, an inorganic material,
poses a signicant danger to both the environment and human life
(Mandal and Suzuki, 2002). This danger is reected in the environmental legislation of a number of nations which seek a progressive reduction in the threshold concentration of arsenic (Hamilton, 2000;
Habuda-Stanic et al., 2007). In some areas, high nancial penalties
are imposed on enterprises which include arsenic in their processes
and treat it carelessly. As an example, Wilson and Chanroux (1993)
reported that in Australia a heavy penalty is applied to smelters treating copper if they are revealed to have an arsenic concentration
higher than 2000 ppm. Given this legislation, and in light of the significant impact high arsenic concentrations have on the environment, it is
unsurprising that there has been much interest in the removal of arsenic at an early stage of these processes. A method which appears to
have much promise is otation. However, the use of otation techniques has been hampered by difculties related to the removal of

Corresponding author at: Graduate School of Engineering, Kyushu University,

Japan. Tel./fax: + 81 92 802 3337.
E-mail address: hirajima@mine.kyushu-u.ac.id (H.T.B.M. Petrus).
0301-7516/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2011.11.002

arsenic-bearing minerals because of their similar otation behavior to

associated valuable copper sulde minerals.
There are two major arsenic-bearing minerals in copper ores,
enargite (Cu3AsS4) and tennantite (Cu12As4S13). These minerals are
usually found in association with chalcocite (Cu2S), covellite (CuS), or
chalcopyrite (CuFeS2). Energite has been extensively studied (Lattanzi
et al., 2008), however, only a few studies have focused on the separation
of tennantite from its associated non-arsenic copper sulde minerals,
which may be due to the scarcity of high purity tennantite.
In the otation process, the success of mineral separation is determined by controlling the mineral surface which can be achieved by
modifying variables such as pH, pulp potential, and chemical addition
(modier, collector, and or frother). A successful separation method
for tennantite from its non-arsenic copper sulde minerals was proposed by Fornasiero et al. (2001) using a selective oxidation technique
in acidic conditions, or oxidation and selective dissolution in alkaline
conditions. This success was due to the formation of different species
at different pH values, different rates of oxidation among the minerals
and the stability of the oxidation species. The formation of these species
and the different rates of oxidation were previously studied by Fullston
et al. (1999) using zeta potential. These authors stated that the rate of
oxidation at pH 11 among copper sulphide minerals was in the order
of chalcocite> tennanite > enargite> covellite > chalcopyrite. In terms

H.T.B.M. Petrus et al. / International Journal of Mineral Processing 102103 (2012) 116123

of the interaction of tennantite with a collector, a comprehensive study

using amyl xanthate as the collector and surface characterization analytical instruments (FTIR and XPS) was conducted by Mielczarski et al.
Sasaki et al. (2010) reported further surface characterization (XPS and
Raman) of tennantite at various pH values during oxidative dissolution
and explained the different species over the pH range used. In their
study, the oxidation rate of tennantite, in comparison with energite
and chalcopyrite, was found to resemble the order stated by Fullston
et al. (1999). Further observations on tennanite in acidic conditions
were also studied by Asbjornsson et al. (2004) using an electrochemical
technique.
From the studies found in the literature, use of a depressant to
separate tennanite from its non-arsenic copper sulphide minerals
has not yet been explored. On the other hand, the effect of a depressant on non-arsenic copper sulde minerals has been investigated
and reported in some publications. One of the studies was conducted
by Eliseev and Kirbitova (1984), where sodium thiosulphate was used
to depress chalcopyrite. The depression was affected by the coverage
of the copper thiosulphate complex which was very stable in alkaline
conditions. The study included a otation study and titration to distinguish the otability and the formation as well as the stability of
the copper thiosulphate complex.
In the present study, the effect of sodium thiosulphate on tennantite
and the possible separation of tennantite from chalcopyrite were determined. The change in hydrophobicity of each mineral was monitored by
contact angle measurement, while the Hallimond tube method was
used to observe the otability of both chalcopyrite and tennantite. By
modifying the mineral surface using sodium thiosulphate with and
without the collector (diethyl dithiophosphate/DTP) and observing
the effect on both chalcopyrite and tennantite we aimed to investigate
the possibility of separation. The zeta potential was also determined
to distinguish the surface charge of both tennantite and chalcopyrite before and after treatment which enabled investigation of the mechanism
involved. Knowing the effect of these chemicals on the otability of
each mineral and the mechanism involved, it is hoped that the separation of tennanite from chalcopyrite using this treatment can be conducted in a more complex system and may be implemented on an
industrial scale.
2. Materials and methods
2.1. Mineral samples
In order to eliminate the effect of impurities in this study, handpicked natural samples of both chalcopyrite and tennantite were
used. Chalcopyrite of 95% purity was obtained from Sayama Mines,
Akita Pref., Japan. While natural tennantite sample of 92% purity was
obtained from Magma Mines Superior, Pinal, Arizona, USA. Determination of the chemical composition of tennantite and chalcopyrite was
conducted using ICP-AES as shown in Table 1.
The samples, which were kept in the freezer ( 25 C) in order
to minimize oxidation, were crushed using a porcelain mortar
and sieved in a nitrogen atmosphere glove box to obtain particles
of 105 m to + 78 m in size for the otation experiments and
particles of 38 m in size for the zeta potential and X-ray photoelectron
spectroscopy experiments. For contact angle measurements, samples of
both chalcopyrite and tennantite with a minimum surface size of
5 5 mm were selected and treated as described in. 2.2. Mineral
conditioning.
Table 1
Chemical compositions of chalcopyrite and tennantite (mg/g).
Minerals

Cu

Fe

As

Si

Al

Na

Others

Chalcopyrite
Tennantite

346.2
475.2

289.8
32.4

336.5
293.7

n.d.
186.3

7.9
3.8

0.12
0.09

0.05
0.06

19.43
8.45

117

In this study, sodium thiosulphate (Na2S2O3. 5H2O), which functioned as the surface modier, was of analytical grade and bought
from Wako Pure Chemical Industries. Ltd. Diethyl dithiophosphate
(DTP), which was the chosen collector, was a commercial product
under the name of AEROFLOAT 208 by Cytec Technology Co. Diethyl
dithiophosphate (DTP) was the preferred collector rather than xanthate
due to its better selectivity for pyrite rejection in complex sulde ores
(Fuerstenau et al., 1971; Nagaraj and Brinen, 2001).
2.2. Mineral conditioning
All samples in each analytical instrument were treated with the same
conditioning sequence of chemicals and time periods. Firstly, ensuring a
fresh surface in each sample before treatment is crucial to eliminate variability of the initial mineral surface. In the contact angle measurements,
a fresh mineral surface was produced by the gradual polishing method
up to 1 m of diamond paste (Struers, Germany) as described in
Section 2.3. Contact angle measurement. Crushing the hand-picked mineral prior to each experiment was carried out in the otation, zeta potential, and X-ray photoelectron spectroscopy measurements.
After providing a fresh surface for each sample, the samples were
then treated in solution at the desired pH (either pH 4, 6, or 9) for
2 min. Adjustment of the desired pH was conducted using HCl or
KOH solution. Conditioning with sodium thiosulphate was then performed for 10 min, followed by 10 min of conditioning with DTP
(6 10 5 M). Adjustment of pH was also carried out after each chemical
conditioning due to pH change. The otability (Hallimond tube), contact
angle, and zeta potential were measured after each step of the conditioning process in order to distinguish the effect of sodium thiosulphate and
DTP.
2.3. Contact angle measurement
The contact angles were measured using a Goniometer (Dropmaster
300, Kyowa Interface Science Co., Ltd.). To measure contact angles, a
mineral sample of the appropriate size was chosen, epoxied and cut
using a diamond cutter to provide a rough at surface. The rough at
surface was then wet ground under a stream of deionized distilled
water on grit papers of #500 to #2400. Further polishing was carried
out using an MD pan cloth mounted on a plate using 3 m and 1 m
of the diamond paste. After careful polishing, the polished samples
were cleaned with jets of distilled water to remove any particles left
on the surface. In the nal stage of polishing, 1 m of diamond paste
and an MD pan cloth were used to atten the sample surface followed
by ultra pure nitrogen (N2) gas jet blowing. The contact angle of the
mineral samples was measured before and after treatment as described
in Section 2.2. Mineral conditioning. Contact angles were measured
using the sessile drop method. The average value of three readings
was used for all measurements.
2.4. Flotation
2.4.1. Single mineral
The otability test on each mineral was carried out using the Hallimond tube method (Fuerston Fuerstenau et al., 1957). For the otation
test, 0.5 g of each mineral was suspended in 150 ml of pure water and
conditioned with sodium thiosulphate and DTP. The size fraction of
the mineral particles in this experiment was 105 m to +78 m.
The solution was transferred into a Hallimond tube, and otation was
initiated by passing nitrogen (N2) through at a ow rate of 20 ml/min
for 1 min. The oated and tailing fractions were collected separately
and weighed after lyophilization.
2.4.2. Arsenic copper concentrate
One hundred gram (0.05 g) of arsenic copper concentrate A was
wet ground for preliminary determined time in ceramic laboratory

H.T.B.M. Petrus et al. / International Journal of Mineral Processing 102103 (2012) 116123

ball mill to the size of about 20 m in P80. The product was poured
into a 0.8-liter cell of Fahrenwald otation test machine. Staged conditioning was applied with modiers (pH and sodium thiosulphate)
for 8 min. During this conditioning certain amount of KOH or HCl was
added to maintain the operating pH. After that diethyl dithiophosphate
(DTP) as collector (Cytec AP208) and methyl isobuthyl carbinol (MIBC)
as the frother were added and conditioned for 2 min. Rougher otation
was then performed for 8 min. All products were dried at 90 C then
submitted to XRF analysis for copper and arsenic assay. The composition of the arsenic copper concentrate A can be seen in Table 2.

80

70

Contact angle (o)

118

2.5. Zeta potential measurement

60

50

2.6. X-ray photoelectron spectroscopy (XPS)

Solid residues of single mineral samples treated by pH conditioning
(pH 4 and 9) and thiosulphate at those pHs in the concentration of
100 kg/ton were freeze-dried overnight for analysis with X-ray photoelectron spectroscopy (PHI 5800 ESCA). The collected data were analyzed with Casa XPS software (Ver, 2.3.12). Background corrections
were made using the Shirley method (Shirley, 1972). Peak shapes
were dened using a GaussianLorentzian function. CC bond has a
well-dened position at EB [C1s] = 284.6 eV, which was used as a reference peak to correct for charging effects.
3. Results and discussion
3.1. Contact angle and recovery (otability study)
To investigate the hydrophobicity and otability of chalcopyrite
and tennantite before and after sodium thiosulphate treatment with
and without DTP, contact angle measurement and otation using
the Hallimond tube were determined. The results of the contact
angle measurements for chalcopyrite are depicted in Fig. 1, while
the results of the contact angle measurements for tennantite are
shown in Fig. 2. Measurements of the contact angle of fresh samples
with pH treatment only, sodium thiosulphate, DTP, and the combination of sodium thiosulphate and DTP were conducted. It can be seen
in Fig. 1 that the contact angle of the fresh sample of chalcopyrite decreased with increasing pH and was about 73 in acidic conditions
and decreased to about 68 in alkaline conditions. When chalcopyrite

Table 2
Mineral compositions of arsenic copper concentrate A.

a
40

10

pH
Fig. 1. Contact angle of chalcopyrite; a) fresh sample; after conditioning using b)
diethyl dithiophosphate (DTP), c) sodium thiosulphate, and d) both chemicals, at certain concentration (100 kg/ton of Na2S2O3; 6 10 5 M of DTP).

was treated with sodium thiosulphate, this resulted in a lower contact

angle at all pH values tested. A signicant decrease in contact angle
was seen after the addition of 10 kg/ton of sodium thiosulphate.
The contact angle was similar for all pH treatments and was about
65. After conditioning using both sodium thiosulphate and DTP
(6 10 5 M), an increase in contact angle was observed and was a little
bit higher than that of the fresh sample of chalcopyrite at all pH values.
However, this value was lower than that of chalcopyrite conditioned
using DTP only, and was about 76 in acidic conditions and about 71
in alkaline conditions. Hence, the depressive effect of thiosulphate on
chalcopyrite remained even after addition of the collector.
A similar trend was observed for treated tennantite at all pH
values and chemical treatments, as seen in Fig. 2. However, it was
noted that the reduced contact angle was more severe in comparison
with chalcopyrite treated with the same concentration of sodium
thiosulphate (100 kg/ton). The fresh sample of tennantite had a contact angle of about 70 in acidic conditions (pH 4), which decreased to
about 45, and the contact angle of chalcopyrite increased only by
about 10. In alkaline conditions, the decrease in contact angle was
also severe for tennantite and was 10 higher than that of chalcopyrite

80

70

Contact angle (o)

The zeta potential of chalcopyrite and tennantite was measured

using the ZEECOM ZC-2000 system (Kyowa Interface Science Co., Ltd.)
equipped with a video recorder. All measurements were conducted at
the same ionic strength using KCl at a concentration of 10 3 M. Chemical conditioning was conducted using sodium thiosulphate and diethyl
dithiophosphate at certain pH values as detailed in Section 2.2. Mineral
conditioning and the zeta potential was then measured. Each zeta potential reading represented an average of 50 measured particles. In this
study, the average of three readings at each data point (pH) was used
in all the experiments.

60
a

50
Minerals

Percentage (%)

Chalcopyrite; CuFeS2
Bornite; Cu5FeS2
Chalcocite; Cu2S
Tennantite; (CuFe)12As4S13
Molybdenite; MoS2
Pyrite; FeS
Sphalerite; ZnS
None sulde gangues
Total

59.6
0.8
4.3
1.4
0.5
18.9
0.4
14.1
100

40

10

pH
Fig. 2. Contact angle of tennantite; a) fresh sample; after conditioning using b) diethyl
dithiophosphate (DTP), c) sodium thiosulphate, and d) both chemicals, at certain concentration (100 kg/ton of Na2S2O3; 6 10 5 M of DTP).

H.T.B.M. Petrus et al. / International Journal of Mineral Processing 102103 (2012) 116123

100
a

80

Recovery (%)

which was about 2. After addition of the collector (DTP), there was a
signicant increase in contact angle at all pH values, similar to that for
chalcopyrite. However, in alkaline conditions (pH 9), the contact angle
of tennantite was about 50 lower than that of the fresh sample which
was 53. This decrease in contact angle suggests a reduction in the hydrophobicity of both chalcopyrite and tennantite with a higher reduction
in tennantite than chalcopyrite, especially in alkaline conditions.
Further investigations on the otability of each treated mineral
using the Hallimond tube resembled the ndings obtained from the
contact angle measurements. The results of the otation experiment
are depicted in Figs. 3 and 4. From Fig. 3, it can be seen that the recovery
of the fresh sample of chalcopyrite decreased with increasing pH. In
acidic conditions, recovery was 90% which declined to about 70% in alkaline conditions. Similarly, recovery was reduced with increasing pH in
the fresh sample of tennantite as shown in Fig. 4. The recovery of this
sample was about 80% in acidic conditions which decreased to about
40% in alkaline conditions. The depressive effect of sodium thiosulphate
on chalcopyrite, shown by the reduction in contact angle measurement,
was also noted in the recovery of treated chalcopyrite, which was about
60% in acidic conditions and about 50% in alkaline conditions. For tennantite, recovery increased to about 30% in acidic conditions and was
about 20% in alkaline conditions. Further treatment of chalcopyrite
with DTP resulted in an increase in recovery up to the value of the
fresh sample at all pH values. For tennantite, a similar trend in recovery
was found at pH 4 and pH 6, while at pH 9 (alkaline conditions) the increase was insignicant showing that the depressive effect of sodium
thiosulphate was highest in this condition. The recovery of tennantite
after the addition of sodium thiosulphate and DTP in alkaline conditions
was about 20%, as depicted in Fig. 4.
It was observed that the otability of the fresh samples of chalcopyrite
and tennantite as a function of pH was in accordance with previously
reported studies (Fornasiero et al., 2001; Sasaki et al., 2010) with regard
to the oxidation of both minerals during dissolution. In acidic conditions,
the otability was higher due to the coverage of elemental sulfur on both
minerals (Gardner and Woods, 1979; Asbjornsson et al., 2004), while in
alkaline conditions the coverage species were either metal oxide and/or
hydroxide which have hydrophilic characteristics (Fullston et al., 1999;
Guler and Hicyilmaz, 2004). Moreover, as seen from Figs. 3 and 4, the recovery of tennanite in alkaline conditions was about 40 for the fresh
sample which was lower than that for chalcopyrite at about 70%. This
may be due to the faster rate of oxidation of tennantite compared with
chalcopyrite (Fullston et al., 1999; Sasaki et al., 2010). In addition, this
study also conrmed that selective oxidation can be conducted in

119

60

40

20

pH
Fig. 4. Recovery of tennantite; a) fresh sample; after conditioning using b) diethyl
dithiophosphate (DTP), c) sodium thiosulphate, and d) both chemicals, at certain concentration (100 kg/ton of Na2S2O3; 6 10 5 M of DTP).

collector-based otation to separate tennantite from chalcopyrite. Following the addition of DT only, at a concentration of 610 5 M at pH
9, it was found that the recovery of chalcopyrite was about 80%, while
that of tennantite was about 60%.
Although selective oxidation allows the separation of tennantite
from non-arsenic copper sulde minerals as conrmed in this study
both with and without collector, the recovery after sodium thiosulphate treatment with collector was found to be higher in alkaline
conditions (pH 9). For chalcopyrite, the recovery after treatment
with sodium thiosulphate and DTP was about 70% which differed by
50% from that of tennantite which had a recovery of about 20%. This difference might allow higher separation of tennantite from chalcopyrite
in a more complex system in comparison to the applied selective oxidation process.
Eliseev and Kirbitova (1984) suggested that the depression of
chalcopyrite was caused by the coverage of the copper thiosulphate
complex which occurred when thiosulphate ions were added to the
system. This is in accordance with Eq. (1) as follows:

2Cu

6S2 O3


3
2
2 CuS2 O3 2
S4 O6

100
a

Recovery (%)

80

60

40

20

In this study, the depressive effect of sodium thiosulphate was conrmed in both chalcopyrite and tennantite in term of otability. Severe
depression which was insignicantly affected by the addition of further
collector was obtained with tennanite in alkaline conditions. However,
from the contact angle as well as the otation experiments, the existence and coverage of the copper thiosulphate complex, which is responsible for the depression as suggeted by Eliseev and Kirbitova, has
not yet been proved. In order to study the mechanism of depression
caused by sodium thiosulphate, zeta potential measurements was
then conducted.
3.2. Zeta potential measurements

pH
Fig. 3. Recovery of chalcopyrite; a) fresh sample; after conditioning using b) diethyl
dithiophosphate (DTP), c) sodium thiosulphate, and d) both chemicals, at certain concentration (100 kg/ton of Na2S2O3; 6 10 5 M of DTP).

By measuring the zeta potential of the mineral, the species on the

mineral surface can be predicted. However, in sulphide minerals, the
zeta potential, representing the electrokinetic behavior, is more difcult
to determine compared with that of oxide minerals. This is due to the
surface reactivity of sulphide minerals to environmental conditions
which determines the species, which in turn, determines the zeta potential (Fullston et al., 1999).

H.T.B.M. Petrus et al. / International Journal of Mineral Processing 102103 (2012) 116123

To observe the effect of sodium thiosulphate and propose the mechanism involved, a study was conducted using several concentrations of
sodium thiosulphate (10 kg/ton, 50 kg/ton, and 100 kg/ton). The effect
of DTP addition at a concentration of 6 10 5 M was also determined
at 100 kg/ton of sodium thiosulphate, where the difference in recovery
for both minerals obtained was higher than the conrmed recovery by
selective oxidation conducted in this study with and without DTP.
3.2.1. Effect of sodium thiosulphate
Fig. 5 depicts the zeta potential measurement of treated chalcopyrite
without DTP, and the zeta potential measurement of tennanite is shown
in Fig. 6. It can be seen that the fresh samples of chalcopyrite and tennantite had negative zeta potential values in the pH range 3 to 12. These results show that the fresh sample was not yet oxidized or had been
oxidized in a very low state (Fullston et al., 1999; Fairthorne et al.,
1997). In addition, Kelebek and Smith (1989) have also indicated that
the zeta potential of non-oxidized sulde minerals are negative. In the
case of chalcopyrite, the zeta potential was similar to that of elemental
sulfur and was found at pH values between 1 and 2. The zeta potential
of fresh samples of chalcopyrite and tennantite supported the method
used to produce fresh samples for all the experiments of both chalcopyrite and tennantite which aimed to eliminate any disturbance during the
study due to oxidation of chalcopyrite and tennantite.
When sodium thiosulphate was introduced into the solution, the
zeta potential value was negative at all pH values tested. The higher
the concentration of sodium thiosulphate added to the mineral solution, the more negative the zeta potential value of both chalcopyrite
and tennanite were. In acidic conditions, the zeta potential tended
to be more negative and was about the same for both minerals. The
tendency in alkaline conditions was different. It was found that the
zeta potential of tennantite was more negative than that of chalcopyrite
when the same concentration of sodium thisulphate was added.
This difference in acidic and alkaline conditions may be caused by
instability of thiosulphate in acidic conditions, where thiosulphate
has a tendency to oxidize and form sulphate (Gonzalez-Lara et al.,
2009). Sulphate species resulting from thiosulphate oxidation were
responsible for the negative zeta potential in acidic conditions
which affected both chalcopyrite and tennantite in a similar manner
based on specic adsorption.
In alkaline conditions, thiosulphate was more stable enabling the
formation of the copper thiosulphate complex. As seen in Eq. (1), formation of the copper thiosulphate complex is not only a function of
thiosulphate concentration but also the availability of Cu 2+ in the solution. Tennantite, which has a higher oxidation rate than chalcopyrite,

0
a

-20

Zeta potential (mV)

120

-40

-60

-80

-100

10

12

14

pH
Fig. 6. Zeta potential of tennantite at varied sodium thiosulphate concentration; a) no
addition or fresh sample, b) 10 kg/ton, c) 50 kg/ton, and d) 100 kg/ton.

may result in a higher amount of Cu 2+ once the mineral is conditioned

in the solution system. Thus, the more negative zeta potential of tennantite was due to higher formation and coverage of the copper thiosulphate complex on the tennantite surface. However, the surface reaction
on the mineral surface was much more complicated. The formation of
oxide and hydroxide also occurred during conditioning. This competitive reaction may be responsible for the change in orientation of the
zeta potential which was clearly seen in tennantite in alkaline conditions (especially at about pH 10), where after 100 kg/ton, the zeta potential in this pH region shifted to a more negative value than that in
acidic conditions. For chalcopyrite, the zeta potential in alkaline conditions was higher than that in acidic conditions.
It is possible that the shifting zeta potential shown for tennantite
in alkaline conditions (especially around pH 10) may be seen with
chalcopyrite, where the zeta potential will be shifted in the same
manner to that of tennantite at higher concentrations of added sodium
thiosulphate due to coverage of the copper thiosulphate complex. Consequently, providing an appropriate concentration at which the coverage
of the copper thiosulphate complex on the mineral surface is optimal is
the most crucial part in distinguishing the degree of separation of tennantite in the complex otation unit.

0
0
a

-20

Zeta potential (mV)

Zeta potential (mV)

-20

-40

-60

-40

-60

-80
-80

-100

-100
0

10

12

14

10

12

14

pH

pH
Fig. 5. Zeta potential of chalcopyrite at varied sodium thiosulphate concentration; a) no
addition or fresh sample, b) 10 kg/ton, c) 50 kg/ton, and d) 100 kg/ton.

Fig. 7. Zeta potential of chalcopyrite; a) fresh sample; after conditioning using b) sodium thiosulphate, and c) diethyl dithiophosphate (DTP) and sodium thiosulphate, at
certain concentration (100 kg/ton of Na2S2O3; 6 10 5 M of DTP).

H.T.B.M. Petrus et al. / International Journal of Mineral Processing 102103 (2012) 116123

0
a

conditions was found to be similar to that for chalcopyrite, while in alkaline conditions the increase in zeta potential was insignicant.
This increase in zeta potential to a more positive value following
the addition of DTP was a result of the formation and attachment of
dithiophosphate species on the surface of both chalcopyrite and tennantite. The attachment competitiveness of DTP species decreased
the propensity of copper thiosulphate complex to occur on the mineral surface. The possible species involved were: CuDTP, Cu(DTP)2, and
(DTP)2 which would be attached on the mineral surface as shown in
Eqs. (2) and (3) (Guler and Hicyilmaz, 2004).

Zeta potential (mV)

-20

-40

-60

2CuDTP2 2CuDTP DTP2

2Cu

-80

-100

10

121

12

14

pH
Fig. 8. Zeta potential of tennantite; a) fresh sample; after conditioning using b) sodium
thiosulphate, and c) diethyl dithiophosphate (DTP) and sodium thiosulphate, at certain
concentration (100 kg/ton of Na2S2O3; 6 10 5 M of DTP).

3.2.2. Effect of diethyl dithiophosphate (collector)

In this study, the effect on zeta potential of the addition of collector
(100 kg/ton of sodium thiosulphate) to depressed chalcopyrite and tennantite was determined. A similar concentration of diethyl dithiophosphate to that added in the otability study (6 10 5 M) was used.
The results for chalcopyrite are depicted in Fig. 7, while Fig. 8 depicts
the results for tennantite. As a comparison, the zeta potential of the
fresh sample and the sodium thiosulphate-treated minerals are included
in both gures.
From these gures, it can be seen that addition of DTP increased
the zeta potential to a more positive value at all pH values tested
compared with the zeta potential after treatment with 100 kg/ton of
sodium thiosulphate added to chalcopyrite. However, this increase
was observed to be lower in alkaline conditions compared with acidic
conditions. For tennantite, the increase in zeta potential in acidic

4DTP 2CuDTP2

The insignicant increase observed for tennanite in alkaline conditions, as seen in Fig. 8, showed lower coverage of the dithiophosphate
species on the surface of tennantite which might be due to the saturated surface coverage of the copper thiosulphate complex which
inhibited the attachment of dithiophosphate species.
The results from the measurement of zeta potential describe the
mechanism of the depression of sodium thiosulphate based on the
surface charge of both chalcopyrite and tennantite, which are in accordance with the results of the contact angle and otation. It was
found that the signicant difference in otability between tennantite
and chalcopyrite in alkaline conditions was caused by the coverage of
the copper thiosulphate complex which inhibited the attachment of
DTP species onto the mineral surface. With this particular treatment,
the rendered attachment of DTP was lowest for tennantite suggesting
more coverage of the copper thiosulphate complex than for chalcopyrite due to the higher rate of oxidation.
3.3. X-ray photoelectron spectroscopy (XPS)
In order to prove the existence of thiosulphate species on the mineral surface, X-ray photoelectron spectroscopy was conducted on
treated single mineral samples. Figs. 9 and 10 show the S 2p spectra
for chalcopyrite and tennantite before and after conditioning using

b
S 2p

Intensity (cps)

Intensity (cps)

S 2p

pH 9

157

Thiosulphate + pH 9
Thiosulphate + pH 4

500 cps

500 cps

pH 4

163

Binding energy (eV)

169

157

163

169

Binding energy (eV)

Fig. 9. XPS-spectra of S 2p region for; a) original chalcopyrite, and b) after being treated using sodium thiosulphate, at pH 4 and pH 9. Binding energy was corrected by EB[C1sA] from
hydrocarbon = 286.4 eV. Vertical bars indicate 500 cps.

122

H.T.B.M. Petrus et al. / International Journal of Mineral Processing 102103 (2012) 116123

b
S 2p

pH 9

157

Thiosulphate + pH 9
Thiosulphate + pH 4

500 cps

500 cps

pH 4

Intensity (cps)

Intensity (cps)

S 2p

163

169

157

163

Binding energy (eV)

169

Binding energy (eV)

Fig. 10. XPS-spectra of S 2p region for tennantite after being treated using sodium thiosulphate at pH 4 and pH 9. Binding energy was corrected by EB[C1sA] from hydrocarbon = 286.4 eV. Vertical bars indicate 500 cps.

3.4. Copper concentrate otation

Sodium thiosulphate was applied in the otation test of fresh sample of arsenic copper concentrate A. As it can be seen in Fig. 11 (80% of
copper recovery), the arsenic recovery of copper concentrate A at
both pHs was found relatively high before thiosulphate conditioning
at about 78.5% for pH 4 and at about 75.3% for pH 9. After thiosulphate
conditioning in the concentration of 100 kg/ton, the arsenic recovery
decreased signicantly at pH 9 to the value of 65.1%. The result acquired in arsenic copper concentrate A otation test was in similar
tendency as that in the single mineral study.
Furthermore the relationship between copper recovery and arsenic grade was shown in Fig. 12. It shows that there was no signicant

decrease of arsenic grade when pH 4 conditioning applied. The lowest

arsenic grade obtained was about 3200 ppm. At 80% of copper recovery, the arsenic grade was 3300 ppm. The arsenic grade slightly decreased in pH 9 conditioning to the value of 3275 ppm at the same
copper recovery, while the most reduction of arsenic grade was
gained when thiosulphate conditioning applied at pH 9. The value
of 2650 ppm was reached in this conditioning.
4. Conclusions
From the ndings specied in this paper, it can be concluded that
the prospective separation of tennantite from chalcopyrite using the
otation technique can be conducted using the addition of sodium
thiosulphate in alkaline conditions. Flotation recovery and contact

100

Arsenic Recovery (%)

sodium thiosulphate at pH 4 and pH 9. As for chalcopyrite, the S 2p

spectrum before treatment using sodium thiosulphate was composed
of three peaks for both treated pHs. When the chalcopyrite was treated at pH 4, the peaks were at around 161.0, 162.2 and 163.8 eV.
About the same peaks at around 160.9, 162.3, and 163.9 eV were observed at pH 9 (Fig. 9a). After conditioning using sodium thiosulphate, there was additional peak at around 168.1 eV observed only
at pH 9 (Fig. 9b). Similarly, when tennantite was treated using sodium thiosulphate, the additional peak at around 168.4 eV was only observed at pH 9 (Fig. 10).
The peak at around 161.0 eV is originated from the S 2 in chalcopyrite (Mielczarski et al., 1996), while the other two peaks at around
162.2 and 163.8 eV are assigned to monosulde and elemental sulfur
(Sasaki et al., 2010) . In tennantite, the originated peak from the S 2
was obtained at around 161.7 eV which is in agreement with the previous report by Mielczarski et al. (1996). The peak at around 168.1 eV
of chalcopyrite and 168.4 eV of tennantite that was obtained after sodium thiosulphate conditioning was attributed to intermediate sulfur
species which is thiosulphate (Grano et al., 1990). The presence of the
thiosulphate species at both chalcopyrite and tennantite surface was
possibly resulted by the interaction between the adsorbed thiosulphate and either chalcopyrite or tennantite surface. From the relative
intensity, it can be noticed that tennantite possesses higher coverage
of thiosulphate of 0.08, while in chalcopyrite it is 0.04.

80

60

40
0

100
pH 4

100
pH 9

Thiosulphate concentration (kg/ton)

Fig. 11. Effect of sodium thiosulphate addition on arsenic recovery of copper concentrate (75 g/t-AP208/collector and 50 g/t-MIBC/frother).

H.T.B.M. Petrus et al. / International Journal of Mineral Processing 102103 (2012) 116123

Arsenic grade (ppm)

4,000

123

species. The existence of sulphate coverage with specic adsorption

was demonstrated by the negative zeta potential measured in this
study. Similarly, in otation of arsenic copper concentrate, it was
found that the thiosulphate depression provided better result when
it was conducted in alkaline condition (pH 9) providing a possibility
to separate tennantite from the arsenic copper concentrate.

3,000

2,000

Acknowledgement

1,000

The authors express appreciation for support of this research by

Sumitomo Metal Mining, Co., Ltd., and Global COE program Novel
Carbon Resources Sciences, Kyushu University. The authors also acknowledge the support of the Hitachi Scholarship Foundation in providing a scholarship grant to Himawan T.B.M. Petrus.

pH 4
0

20

pH 9
40

Thiosulphate + pH 9
60

80

100

Copper recovery (%)

Fig. 12. Effect of pH and sodium thiosulphate addition on arsenic grade in concentrates
(75 g/t-AP208/collector and 50 g/t-MIBC/frother).

angle measurement showed a signicant difference between tennantite and chalcopyrite. At pH 9 (alkaline conditions), tennantite recovery was only about 20%, much lower than that of chalcopyrite at
about 70%. In terms of contact angle which represented the hydrophobicity of each mineral, the contact angle of tennantite was about
45, approximately 25 lower than that of chalcopyrite. This difference was a result of the depressive effect of sodium thiosulphate addition. The coverage of the copper dithiosulphate complex on the
mineral surface induced separation by inhibiting the attachment of
diethyl dithiophosphate species (either CuDTP, Cu(DTP)2 or (DTP)2).
This inhibitory effect is a function of the degree of coverage of the
copper thiosulphate complex which was different for tennantite and
chalcopyrite. For tennantite, the coverage of the copper thiosulphate
complex was greater than that for chalcopyrite at a similar concentration of added sodium thiosulphate, due to a higher rate of oxidation
than chalcopyrite. This resulted in a more pronounced resistance to
the attachment of diethyl dithiophosphate which reduced the otability of tennantite to a lower value than that of chalcopyrite. Zeta
potential measurements of both tennantite and chalcopyrite showed
evidence of the copper thiosulphate complex coverage which was indicated by the more negative zeta potential value following the addition of sodium thiosulphate. In addition to that, XPS spectra showed
qualitatively and quantitatively the existence of thiosulphate on
both mineral surfaces resembling the proposed mechanism of thiosulphate depression.
Although the depression of both tennantite and chalcopyrite was
detected in acidic conditions, the otability of both tennantite and
chalcopyrite increased signicantly after ditheyl dithiophosphate addition. The recovery of tennantite was found to be about 90% which
was similar to the recovery of chalcopyrite at about 95%. This may
be due to the coverage of sulphate on the mineral surface as a result
of the instability of thiosulphate in acidic conditions forming sulphate
ions which did not inhibit the attachment of diethyl dithiophosphate

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