Recycling process water in sulfide

flotation, Part A: Effect of calcium and

sulfate on sphalerite recovery
F. Ikumapayi and M. Makitalo

Graduate students, Mineral Processing Group, Division of Sustainable Process Engineering and Division of
Geosciences and Environmental Engineering, Department of Civil, Environmental and Natural Resources
Engineering, respectively, Lule University of Technology, Lule, Sweden
E-mails: fatai.ikumapayi@ltu.se and maria.makitalo@ltu.se

B. Johansson

Project manager, Department of Process Technology, Boliden Mineral AB, Boliden, Sweden
E-mail: bjorn.johansson@boliden.com

K. Hanumantha Rao*

Professor, Mineral Processing Group, Division of Sustainable Process Engineering Lule University of
Technology, Lule, Sweden
*E-mail: hanumantha.rao@ltu.se

Abstract

In order to predict and minimize detrimental production problems due to the recycling of process water in sulfide
ore processing, the influence of major species, calcium and sulfate in process water on sphalerite flotation was
investigated through Hallimond tube flotation, zeta potential, diffuse reflectance Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) measurements using sphalerite mineral sample.
Assessment of process water species in flotation was done using deionized water, process water and simulated
water containing calcium and sulfate ions in experiments. Hallimond flotation shows increased sphalerite floatability in process water compared to deionized water, but no significant effect on the presence of calcium and
sulfate ions in deionized water using isobutyl xanthate as a collector. The presence of calcium ions reduced the
sphalerites negative zeta potential, while at higher concentrations, a charge reversal occurred, at about pH 11.
FTIR and XPS studies revealed the presence of surface-oxidized sulfoxy and carbonate species on sphalerite at
pH 11.5 in deionized water, process water and water containing calcium and sulfate ions. These surface species
do not influence xanthate adsorption.
Minerals & Metallurgical Processing, 2012, Vol. 29, No. 4, pp. 183-191.
An official publication of the Society for Mining, Metallurgy, and Exploration, Inc.

Key words: Sphalerite, Flotation, Zeta potential, FTIR, XPS, Recycling process water, Sulfide ore

Introduction

The quest for a cleaner and safer environment with

clean surface and ground water has led to increased
recycling of process water within the production cycle
of sulfide minerals processing. Since the chemistry of
process water is entirely different from fresh water,
there is a concern about the possible effects of its
components on the efficiency of the flotation process
(Liu et al., 2011; Rao and Finch, 1989). Calcium and
sulfate ions are two common components in process
water from the flotation of sulfide minerals. The usual
procedure in the flotation stage of complex sulfide ore
processing is to float Cu and Pb minerals in the first
stage of flotation, while Zn mineral is activated with
copper ions and floated in the second stage (Woodcock

et al., 2007). Zinc mineral flotation from a complex sulfide

ore can be effective with strong depression of pyrite minerals
using sulfite ions and adequate activation of zinc using copper ions (Kartio et al., 1998; Shen et al., 2001). Other factors
that affect floatability of ZnS include electrochemical effects,
components and species present in the solution phase of the
pulp (Chandra and Gerson, 2009; Chen et al., 2009; Chen et
al., 2010; Das et al., 1997; Houot and Duhamet, 1992; Rao
and Finch, 1989; Trahar et al., 1997), grinding method (Eric
Forssberg et al., 1993; Palm et al., 2010) and control of the
grinding environment, especially the metal oxidation species
produced by other undesired components, such as pyrite (Shen
et al., 2001), galena and chalcopyrite, and by the oxidationreduction state in the pulp, which in turn influences the potential
range of subsequent flotation (Grano, 2009; Ralston, 1991).

Paper number MMP-12-030. Original manuscript submitted June 2012. Revised manuscript accepted for publication August
2012. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept.
prior to May 31, 2013. Copyright 2012, Society for Mining, Metallurgy, and Exploration, Inc.
MINERALS & METALLURGICAL PROCESSING

183

Vol. 29 No. 4 November 2012

surface characteristics and flotation; the results are presented

and discussed.

Experimental

Materials and reagents. The sphalerite mineral sample

(containing 39.92% Zn, 20.7% S, 4.2% Fe, 1.32% Pb and 0.17%
Cu) used in the experiments was procured from Gregory, Bottley & Lloyd Ltd., UK. The main mineral phase of the sample
is sphalerite with a lot of quartz impurity. X-ray diffraction
(XRD) analysis of the sample (Fig. 1) shows the main phases
present, and its quantification indicates 58.4% sphalerite,
39.6% quartz and 2% galena. The high peaks and some low
peaks correspond to sphalerite as the dominant mineral; most
low peaks correspond to traces of quartz and galena minerals
as impurity in the sample. The mineral sample was crushed,
ground and classified into different size fractions and stored
in sealed polyethylene bags. A size fraction of 150+38 m
was used in the Hallimond tube flotation tests and 5 m size
fraction was used in zeta potential measurement, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron
spectroscopy (XPS) studies. The latter fine-size fraction was
obtained by microsieving.
All chemicals used were obtained from Boliden company
and are technical-grade reagents being used at the company
concentrator for treating complex sulfide ores. Isobutyl xanthate (IBX) and Dowfroth 250 (polypropylene oxide methanol)
were used as collector and frother, respectively. Calcium oxide
(CaO), HCl, HNO3, KOH and NaOH solutions were used as
pH regulators and K2SO4 and CaCl2 as sources of SO42- and
Ca2+ ions, respectively. Potassium nitrate (KNO3) was used to
maintain ionic strength in zeta potential measurement. Process
water containing various Ca2+ and SO42- ion concentrations
was obtained from the Boliden concentrator during the flotation
of Renstrm and Kristineberg ores. The typical concentration
range of chemical species found in Boliden process water is
shown in Table 1.

Figure 1 XRD analysis of the sphalerite sample: (1)

sphalerite, (2) galena and (3) quartz.
Table 1 Chemical species and their concentration range
in Boliden process water (Boliden company internal
report, 2008) [not in refs].
Concentrations

Species

From

To

Unit

Sulfate

SO4

200

1,500

mg/L

Calcium

Ca

100

500

mg/L

Iron

Fe

0.1

1,300

mg/L

COD (Cr)

<30

130

mg/L

0.1

10

mg/L

Phosphorus

<0.05

0.7

mg/L

Magnesium

Mg

4.3

53

mg/L

Manganese

Mn

4.4

8,000

g/L

Zinc

Zn

12

3,900

g/L

Nitrogen

Aluminium

Al

59

59,000

g/L

Cadmium

Cd

0.12

5.2

g/L

Cobalt

Co

540

g/L

Copper

Cu

2.7

20,000

g/L

Mercury

Hg

<0.1

<0.13

g/L

96

160

ms/m

Conductivity at 25 C

Hallimond flotation tests. The tests were conducted with 1

g of mineral conditioned for 10 min after collector addition in a
100-mL standard volumetric flask and subsequently transferred
into a 100-mL Hallimond tube flotation cell; this was followed
by flotation at an air flow rate of 0.2 dm3/min under magnetic
stirring for 1 min. A collector concentration of 20 mg/L and
a frother dosage of 50 g/l were used in the results presented
in Figs. 2 to 4. When the Ca2+ and SO42- species effect was
investigated, the pulp was conditioned first with the species
for 10 min prior to collector addition. All tests were carried
out at a room temperature of approximately 22.5 C and pH
11.5, unless otherwise specified.

The origins of calcium and sulfate species in process water are

the ore and flotation reagents (Broman, 1980). A number of
studies carried out in the past dealt with the effect of calcium
and sulfate ions on environmentally important organic and
inorganic anions, and the results were interpreted as either
competitive (Lefvre and Fdoroff, 2006; Wu et al., 2002),
promotive (Jia Y, 2005; Ostergren et al., 2000; Swedlund and
Webster, 2001) or indifferent (Lefvre and Fdoroff, 2006)
adsorption, depending on the speciation of the adsorbed anion
and the formation of calcium-bearing surface coprecipitates.
However, little is known about the effects of concentrated
sulfate and calcium in solution on the recovery and grade of
zinc minerals in flotation. In particular, previous work has
shown that dry comminution (Palm et al., 2010), sulfite ions
(Shen et al., 2001), lead ions and lead hydroxide (Trahar et
al., 1997) promote the flotation of sphalerite.
The possibility of recycling process water in sulfide mineral
flotation practices was investigated in this study by examining the influence of calcium and sulfate ions on sphalerite
November 2012 Vol. 29 No. 4

Zeta potential measurements. The measurements were

carried out with the aid of a ZetaCompact instrument equipped
with a charge-couple device (CCD) video camera and Zeta4
software. The software allows the direct reading of zeta potential calculated from the electrophoretic mobilities using
Smoluchowski equation. The result is a particle distribution
histogram, from which the mean mobilities are recalculated to
zeta potential values. In each measurement, 10 mg of a 5 m
fraction of the mineral sample at a concentration of 10 mg/100
mL of solution was used. The ionic strength was maintained
with KNO3 at a concentration of 0.01M and the pH was adjusted
with solutions of HNO3 and KOH accordingly. The required
concentration of each solution was prepared, usually followed
by the addition of the mineral, conditioning for 10 minutes and
addition of other required reagents and species. The pH of the
184

MINERALS & METALLURGICAL PROCESSING

suspension after conditioning prior to

zeta potential measurement is always
regarded as the pH of the measurement.
All zeta potential measurements were
performed at a flotation pH of 11.5,
unless stated otherwise.
Diffuse reflectance FTIR spectroscopy measurements. The FTIR
measurement was done using a Bruker
FTIR spectrometer model IFS 66v/s instrument. The samples were prepared as
for the zeta potential measurement, and
the pulp was subsequently filtered. Pulp
solids were left to dry overnight on the
filter paper at room temperature. The pH
of the suspension after conditioning and
prior to filtration was always regarded as
the pH of the measurement. The diffuse
reflectance infrared Fourier transform
(DRIFT) method was used in the measurement, with 2.8 wt% concentration of
the sample in potassium bromide (KBr)
mixture. Each spectrum was recorded
after 256 scans.

Figure 2 Recovery of sphalerite at different pH values in deionized and

process water.

XPS measurements. The samples

subjected to XPS measurement were
prepared exactly as those used in FTIR
measurement. The instrument used was a
Kratos Axis Ultra electron spectrometer
using mono AlK operated at a 150W
X-ray source and a low-energy electron
flood gun for charge compensation. The
spectrometer was equipped with a nitrogen precooling chamber to prevent the
evaporation of volatile components of
the sample. The measurement procedure
and data acquisition was as described by
Sandstrm et al. (2005).

Results and discussion

Hallimond flotation studies. All

experiments are repeated three times and
the mean of three data are recorded. The
comments and conclusions drawn from
the results are specific to the sphalerite
sample used in this study and are relative
to an impure sample containing a high
amount of silica compounds. The recovery of sphalerite at different pH levels
in both deionized and process water is
shown in Fig. 2. The recovery decreases
sharply when pH increases from pH 3
to pH 4, then keeps constant in process
water. In the case of deionized water,
the same trend in recovery decrease
when pH increases from pH 3 to pH 5
is seen. However, the recovery decrease
is more significant in process water. It is
clear that the collector is not adsorbed
even in process water containing various
metal ions, such as Cu2+ (Chandra and
Gerson, 2009), Fe2+ (Zhang et al., 1992)
and Cd2+ (Ralston and Healy, 1980), that
MINERALS & METALLURGICAL PROCESSING

Figure 3 Effect of added calcium ions on sphalerite flotation in both deionized

and process water at pH 11.5.

Figure 4 Effect of added sulfate ions on sphalerite flotation in both deionized

and process water at pH 11.5.

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Vol. 29 No. 4 November 2012

could function as a zinc mineral activator.

The Ca2+ and SO42- ions have no significant effect on the
sphalerite floatability, since the sample is not responding to
flotation (Figs. 3 and 4). However, Ca2+ ions in deionized
water relatively decrease the flotation of sphalerite up to 200
mg/L, after which the recovery remains constant. A gradual
decrease can also be seen in process water up to 600 mg/L
calcium concentration, above which the recovery is restored
to the initial level. In general, the recoveries are a little higher
in process water than in deionized water, which could be due
to the presence of cationic species in the process water that
activate sphalerite, such as copper ions (Chandra and Gerson,
2009; Laskowski et al., 1997), lead ions (Trahar et al., 1997)
and rest reagents (Chen et al., 2009). Similar results can also be
seen with SO42- ions (Fig. 4). The flotation results show only
partial recovery of sphalerite; for its flotation, the necessity
of copper ion activation prior to xanthate collector addition is
well documented.

point (iep) of sphalerite is in the range of pH 2 to 7 (Healy and

Moignard, 1976; Vergouw et al., 1998), due to different levels
of surface oxidation and other impurities. The results of the
present sphalerite sample show that it is negatively charged in
the entire pH range studied, and an iep at pH 2 can be noticed
while extending the curve.
In deionized water, the zeta potential becomes more negative
from pH 3 to 4, remains constant until pH 10 and significantly
reduces from pH 10.5 to 11.5. It is higher (less negative) in
process water than in deionized water, due to the presence of
positively charged metal ions in process water, which adsorb
on the surfaces of the mineral particles. This is an indication
that adsorption of negatively charged collectors on sphalerite
particles may be enhanced (Fuerstenau and Pradip, 2005; Zhang
et al., 1997), a behavior that results in the small increase in
floatability in process water under Hallimond flotation. The
zeta potential is also higher in the presence of Ca ions, and
the zeta potential curve at 500 ppm Ca ion concentration is
very close to the process water curve, due to the same level
Zeta potential studies. The zeta potential of sphalerite as a
of calcium ion concentration in process water. At pH 11.5 and
function of pH in deionized water, process water and deionized
500 ppm Ca ion concentration, a charge reversal to positive
water containing different Ca2+ ion concentrations is shown
can be observed. At pH 11.5, calcium ions exist as divalent
in Fig. 5. Studies in the literature indicate that the isoelectric
cations and calcium hydroxyl (CaOH+) ions as predominant
species, and their adsorption is seen to decrease
the magnitude of negative surface charge and is
responsible for the charge reversal.
The zeta potential of sphalerite at pH 11.5
with increasing concentrations of calcium and
in combination with sulfate is shown in Fig.
6. The zeta potential increases with calcium
ion concentration, while sulfate ions have no
significant effect. Since sphalerite is highly
negative at pH 11.5, anionic sulfate ions could
hardly influence its surface charge.
The significant effect of calcium ions over
sulfate ions on the zeta potential of sphalerite in
solution can be clearly seen in Fig. 7. There are
no great effects of NaHSO3 and xanthate in solution (Figs. 8 and 9). Generally, all zeta potentials
measured in the presence of calcium ions are
identical, and also identical to those measured
Figure 5 Zeta potential response of sphalerite at different pH values
in process water. The higher zeta potential in
in the presence of deionized water, process water and deionized water
process water and in the presence of calcium
containing 200, 500 and 1,000 ppm Ca.
ions compared to in deionized water is due to

Figure 6 Zeta potential of sphalerite at different added calcium ion concentrations and with a fixed
700 mg/L concentration of sulfate ions at pH 11.5.

November 2012 Vol. 29 No. 4

186

MINERALS & METALLURGICAL PROCESSING

Figure 7 Zeta potential of sphalerite at different added sulfate ions concentration and with a fixed 300 mg/L
concentration of calcium ions at pH 11.5.

spectrum of the sample are

due to oxidized species on
the surface, since the samples
were prepared open to the
atmosphere. The oxidized
surface state of sphalerite
mainly consists of zinc
sulfate and thiosulfate, and
zinc carbonate. In Fig. 10,
the bands at 1,055, 1,100,
and 1,160 cm-1 can be assigned to SO vibrations in
zinc sulfate (Godockov et
al., 2002). Absorption bands
characteristic of CO vibrations in zinc carbonate are
seen at about 871 and 1,441
cm-1 (de Donato et al., 1999;
Godockov et al., 2002). The
Figure 8 Zeta potential of sphalerite at different added NaHSO3 concentrations in
extent of surface oxidation
deionized and process waters and with a fixed 9 x 10-5 M IBX concentration at pH 11.5.
is also dependent on pH. In
deionized water, the sulfate
the adsorption of calcium and other metal ions that are present
and carbonate band intensities are low at pH 3, increased at pH
in the water on the surfaces of the mineral particles. Negative
7 and then marginally decreased at pH 11.5. In both types of
surface charge arises due to the sulfide anions, copper and
water, zinc carbonate bands (around 871 and 1,441 cm-1) are
iron cations interacting with the oxygen of hydroxyl species.
observed to have higher intensity in deionized water compared
The adsorption of Ca2+ ion species on sphalerite is reported
to their intensity in process water; it is possible that the presence
by Moignard et al. (1977) through a shift in the iep. An increase
of anionic sulfate and/or carbonate species inhibits xanthate
in zeta potential to positive above pH 10 in the presence of 500
adsorption. This may also explain the increased recovery using
ppm Ca can be attributed to the presence of CaOH+ species
process water in the Hallimond tube flotation.
and their adsorption on the surface (Fig. 5). These species were
The spectra of sphalerite treated with xanthate in deionalso proven to be good depressants for pyrite and sphalerite
ized and process waters and in the presence of calcium and
minerals during sulfide mineral flotation (Hu et al., 2009). Their
sulfate ions, after subtracting the pure mineral spectrum and
effects are also part of low floatability observed in the presence
conditioned in respective waters at the same experimental
of calcium ions under Hallimond tube flotation.
pH 11.5 without xanthate, are shown in Fig. 11. The xanthate
concentrations of 5 x 10-4 and 5 x 10-5 M used in deionized
Diffuse reflectance FTIR studies. Although sphalerite is
water show prominent weak vibration bands associated with
a nonconductive solid in which superficial oxidation is limited
xanthate species on sphalerite at 1,050, 1,078 and 1,175 cm-1
in the absence of surface activation (de Donato et al., 1999;
(Leppinen, 1990; Larsson et al., 2000; Termes and Richardson,
Persson and Persson, 1991), the several bands seen in the
1986) and at 1,078 and 1,177 cm-1 in process water.
MINERALS & METALLURGICAL PROCESSING

187

Vol. 29 No. 4 November 2012

Figure 9 Zeta potential of sphalerite at different concentrations of added IBX in both deionized
and process waters and in the presence of calcium and sulfate ions at pH 11.5.

Figure 10 Spectra of sphalerite conditioned at pH 3, 7 and 11.5 in deionized water (left) and process
water (right) .

The surface-oxidized species of sphalerite are expected to

be removed during the abstraction of xanthate as seen in the
spectrum for 5 x 10-4 M xanthate in deionized water and in
the presence of calcium and sulfate in both waters. The presence of oxidation species in other spectra indicates that the
maximum initial xanthate concentration is not adequate to
form monolayer coverage. The reduced xanthate bands could
be a result of xanthate formation of soluble complex with the
metal ions in process water.
In process water, the carbonate bands (1,450 and 877 cm1) dominate over sulfate and xanthate species bands, weak
November 2012 Vol. 29 No. 4

intensity bands compared to deionized water, inferring lower

adsorption of xanthate. In addition, the presence of both calcium
or sulfate ions and xanthate show a minute carbonate band at
877 and 1,450 cm-1, indicating that the surface carbonate layer
is more concentrated when treated in process water than in
the presence of xanthate. This could be due to ion exchange
between carbonate anions and xanthate, or to surface metal ion
carbonation/calcium carbonate precipitation being impeded in
the presence of xanthate.
The intensity of C-O bands was seen to increase with increasing calcium concentration in water; hence, these represent
188

MINERALS & METALLURGICAL PROCESSING

Table 2 XPS binding energies and atomic concentrations on sphalerite surfaces at different conditions (DW and PW - deionized
and process water).
Atomic concentration in % on ZnS surfaces from XPS measurement
DW

PW

DW 300

PW 300

DW 5.10-5

PW 5.10-5

DW 300

PW 300

DW 1,000

PW 1,000

pH 10.5

pH 10.5

ppm Ca

ppm Ca

M KAX

M KAX

Ca KAX

Ca KAX

SO4 KAX

SO4 KAX

Line

BE, eV

C 1s

285.0

8.81

12.18

10.61

6.59

15.15

13.18

11.47

16.27

15.11

14.14

286.7

3.75

4.3

4.06

2.1

5.41

2.73

4.98

4.53

3.07

3.4

C-O

288.7

1.65

1.43

1.96

1.25

2.45

1.57

2.27

1.93

2.48

1.93

COOH

290.0

1.14

2.59

1.33

8.62

1.2

6.99

1.8

1.88

0.89

1.39

carbonate

530.3

6.23

4.87

4.42

2.97

3.99

3.84

4.29

3.62

4.72

3.96

O 1s

Species

C-(C,H)

Zn-O ?
Zn-OH,

531.5

11.51

7.22

8.56

5.53

9.2

8.45

5.48

8.56

10.85

9.47

carbonate
SO4, etc

532.6

36.36

39.7

38.78

41.04

35.01

39.56

40.02

35.97

34.23

37.28

Si 2p

103.3

K 2p 3/2

293.8

0.88

0.66

0.71

0.39

0.7

0.57

0.72

0.65

0.84

0.89

Zn 2p 3/2

1,022

13.65

11.19

12.34

7.11

10.91

7.59

11.67

9.99

11.63

10.86

S 2p 3/2

161.8

14.81

13

13.91

7.57

13.9

8.71

14.63

13.19

13.25

13.31

SiO2

8.55

163.1
168.6

Organic,

0.94

0.92

1.4

0.54

0.81

1.01

1.09

1.19

1.52

0.85

0.8

0.67

0.55

0.96

0.66

1.02

0.98

1.08

1.1

1.11

7.06

0.72

5.38

1.01

1.3

0.76

0.77

100.01

99.99

99.99

100

99.53

100.01

100

100

100

ZnS
S22-?
poly-S ?
KAX ?
SO42-

Ca 2p 3/2

348.1
99.73

calcium carbonate precipitation on the sphalerite surface or

in bulk solution, as seen in XPS results (Table 2). Since the
solubility of calcium sulfate is much higher than calcium
carbonate, the formation of calcium carbonate coating on the
surface is understandable.
XPS studies. The binding energies at which the spectra
of sphalerite surface components were recorded in this study
corroborate the common binding energies found in databases
and in previous works (Kartio et al., 1998). The most important
results are shown in Figs. 12 and 13, while the detailed results
are summarized in Table 2.
The XPS results of sphalerite treated in both deionized and
process water show that the surface contains the equivalent of
oxidized (Zn-O; Zn-OH) and sulfide (Zn-S) species, but with
a little more intensity of oxidized species in deionized water.
In process water, the surface also contains Ca species, and
relatively more CO32- species. Adsorption of xanthate species
in process water is high, in addition to a significant amount of
Ca2+ and CO32- species, while xanthate adsorption is relatively
reduced in deionized water. Thus, the surface calcium carbonate
in process water is not inhibiting xanthate adsorption.
In process water, the significant reduction of carbonate species bands seen with FTIR (Fig. 11) is also observed in XPS
results, with a decrease in carbonate species when sphalerite
is treated with xanthate in the presence of calcium and sulfate
independently. The marginally higher recoveries of sphalerite
in process water than in deionized water in Hallimond flotation
correlate directly with the surface species.
The C 1s level of sphalerite treated in deionized and process
water solution of xanthate shows peaks of four chemically
different carbon atoms on the sphalerite surface (Fig. 12). The
peaks are observed at BEs 285, 286.8, 288.7 and 290 eV. The
atoms have been identified by different authors as originating
MINERALS & METALLURGICAL PROCESSING

189

Figure 11 Different DRIFT spectra of sphalerite treated

with 5 x 10-4 M, 5 x 10-5 M xanthate and calcium and sulfate
ions in the presence of 5 x 10-5 M xanthate, after subtracting
the mineral spectrum treated in deionized water (left) and
similar spectrum in process water (right) at pH 11.5.

from both hydrocarbon contaminants on the sphalerite surface

and species from the xanthate. The peak at BE 285 eV is symmetric (FWHM = 1.2 eV), with high intensity in deionized
water, and broad (FWHM = 1.3 eV), with lower intensity in
process water. In contrast, the peak at BE 290 eV is broad
in both deionized and process waters (FWHM = 1.1 and 1.2
eV, respectively), but with higher intensity in process water.
The peak at 286.8 eV is also broad, with higher intensity in
Vol. 29 No. 4 November 2012

Figure 12 C 1s XPS spectra of sphalerite treated in

solution containing 5 x 10-5 M IBX in deionized water (top)
and process water (bottom) at pH 11.5.

Figure 13 S 2p XPS spectra of sphalerite treated in

solution containing 5 x 10-5 M IBX in deionized water (top)
and process water (bottom) at pH 11.5.

deionized water than in process water (FWHM = 1.6 and 1.4

eV, respectively), while the one at 288.7 eV is similarly broad,
with higher intensity in deionized water than process water.
The most intense C 1s peak observed on all samples is at 285
eV and it can be associated with C-(C,H) species. The peak at
286.8 eV can be associated with C-O, 288.7 eV with COOH
species, while the peak at 290 eV is associated with carbonate species (CO32-), suggesting the presence of ZnCO3 on the
sample treated in both waters (Nowak and Laajalehto, 2000)
and CaCO3 in process water. It has long been established that
the peaks 285, 286.8 and 288.7 eV are due to hydrocarbon
contamination and substantial adsorption of xanthate or a
component derived from xanthate in an oxidative environment,
with the intensity of 286.8 eV peaks increasing while that of
285 and 288.7 eV decreases in the presence of xanthate (Pillai
et al., 1983). Therefore, it is suggested here that the observed
low intensity of 285 and 288.7 eV peaks in process water and
high 286.8 eV peak in deionized water were due to the adsorption of xanthate on the samples. In case of the peak at 290 eV,
the increased intensity in samples treated with process water
could also be due to precipitation of CaCO3 resulting from the
presence of calcium in the process water.
The two S 2p peaks at 161.7 and 163 eV can be assigned
to S 2p levels of the ZnS substrate (Fig. 13). A low-intensity
peak around 163 eV was suggested to be due to the presence of
xanthate, while the peak around 169 eV indicates the presence
of a surface sulfoxy species such as SO42-, due to the oxidation
of surface sulfur, as well as the presence of SO42- in solution
(Pillai et al., 1983). The xanthate-associated peaks are low,
with no significant difference in samples treated in deionized
water and process water, while the sulfoxy peak is somewhat
higher for samples treated in process water. Therefore, these
suggest that process water components do not affect xanthate
adsorption on sphalerite.

Conclusions

November 2012 Vol. 29 No. 4

Calcium and sulfate ions hardly have any effect on Hallimond flotation recovery of sphalerite. However, recoveries
are relatively better in process water than deionized water.
Sphalerite is negatively charged in the entire pH region in
deionized water, except at pH 11.5 in the presence of 500 ppm
calcium. The magnitude of negative charge is significantly
higher in deionized water compared to process water, illustrating the adsorption of positively charged ions that exist in
process water. A significant effect from calcium ions, but not
sulfate ions, is observed on the zeta potentials of sphalerite.
DRIFT spectra of a pure sample of sphalerite showed that
the surface is partially oxidized, depicting surface sulfoxy
and carbonate species bands. XPS studies revealed a similar
observation with sulfide surfaces. Process water, sulfate and
calcium ions do not suppress xanthate adsorption. On the addition of calcium and sulfate to process water in the presence
of xanthate, the surface carbonate species bands are seen to
diminish, thereby indicating ionic exchange/replacement of
the carbonate anions by xanthate anions.

Acknowledgments

Financial support from the Swedish VINNOVA foundation

and Boliden and Lundin Mining is gratefully acknowledged.
Prof. K.H. Rao would also like to acknowledge the support
from the Centre for Advanced Mining and Metallurgy (CAMM)
at the Lule University of Technology, Sweden.

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