Minerals Engineering xxx (2016) xxxxxx

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

The depression of copper-activated pyrite in flotation by biopolymers

with different compositions
Yufan Mu a,, Yongjun Peng a,, Rolf A. Lauten b
a
School of Chemical Engineering, The University of Queensland, St. Lucia, Brisbane, QLD 4072, Australia
b
Pionera, P.O. Box 162, NO-1701 Sarpsborg, Norway

a r t i c l e i n f o a b s t r a c t

Article history: The depression of pyrite flotation is normally difficult especially when pyrite is activated by copper ions.
Received 16 December 2015 In this study, different biopolymers, modified from lignosulfonate, were examined to depress the flota-
Revised 20 May 2016 tion of copper-activated pyrite. It was found that the biopolymers (DP-1775, DP-1777 and DP-1778), dif-
Accepted 12 June 2016
fering in composition, were able to depress the flotation of copper-activated pyrite. The depression was
Available online xxxx
associated with the copper(I)-biopolymer complex formed on pyrite surface which enhanced the oxida-
tion of copper(I) and inhibited xanthate adsorption. While the molecular weight corresponded to the
Keywords:
adsorption capacity of biopolymers on pyrite, the content of functional groups of biopolymers interfered
Pyrite
Copper activation
with xanthate adsorption.
Biopolymer 2016 Elsevier Ltd. All rights reserved.
Flotation
Depression

1. Introduction tion concentrates, diluting the concentrate grade and increasing

Pyrite (FeS2), the most abundant sulfide mineral, is undesirably
associated with minerals of economic value such as chalcopyrite,
sphalerite and galena (Wang and Forssberg, 1991; Wang, 1995;
Dimitrijevic et al., 1996; Jiang et al., 1998). To produce and utilize
the valuable components, selective depression of pyrite in differen-
tial flotation is required. One typical problem associated with the
separation of pyrite from valuable minerals is the accidental acti-
vation of pyrite by copper ions dissolved from copper minerals
such as chalcopyrite and chalcocite in ores or other contaminants
present in process water (He et al., 2005). Copper activation of pyr-
ite is an electrochemical process which involves a single fast step
of copper adsorption onto the reactive sulfur sites on pyrite surface
with no migration into the bulk phase. During the adsorption, cop-
per(II) is reduced to copper(I) accompanied by the subsequent oxi-
dation of surface sulfide (Weisener and Gerson, 2000a, 2000b). XPS
studies have shown that copper(I) sulfide is the dominant activa-
tion product with Cu(OH)2 precipitation at pH over 8.5 (Weisener
and Gerson, 2000a; Chandra et al., 2012). After copper activation,
pyrite responds strongly to xanthate collector in the pH range of
610 and the copper(I) xanthate has been proposed to be the main
product contributing to pyrite flotation (Leppinen, 1990). The
unwanted activation will lead to the misreporting of pyrite to flota-
Corresponding authors.
E-mail addresses: y.mu1@uq.edu.au (Y. Mu), yongjun.peng@uq.edu.au (Y. Peng).
the smelting cost (Wang and Forssberg, 1991; Chandra and
Gerson, 2009; Huang et al., 2013).
Most flotation plants employ a depression strategy to minimize
pyrite flotation using cyanide, sulfite, high pH, or aeration.
(Janetski et al., 1977; Prestidge et al., 1993; Boulton et al., 2001;
Shen et al., 2001; Agorhom et al., 2015). Unfortunately, these
depression strategies are associated with disadvantages such as
environmental concerns and high operational costs. As a desirable
choice to replace these hazard chemicals, some organic reagents
have been tested and have shown some potential to depress pyrite
flotation (Lpez Valdivieso et al., 2004; Huang et al., 2013;
Agorhom et al., 2014). A study conducted by Mu et al. (2014)
showed that three biopolymers (DP-1775, DP-1777 and DP-
1778), modified from lignosulfonate, depressed the flotation of
both un-activated pyrite (at pH 5) and copper-activated pyrite
(at pH 9). These biopolymers produced from renewable cellulosic
biomass are non-toxic and biodegradable. They have a high inter-
nal degree of crosslinking and contain hydrophilic groups, such as
sulfonic and carboxylic acid groups in addition to various hydroxyl
groups, all grafted to a hydrophobic carbon skeleton (Ouyang et al.,
2006). The mechanism underpinning the depression action of
biopolymers on the flotation of un-activated pyrite at acidic pH
conditions has been thoroughly studied by electrochemical studies
(Mu et al., 2016). These biopolymers passivate the pyrite surface
and inhibit the adsorption and oxidation of xanthate on the sur-
face. In other words, the adsorbed biopolymer prevent the forma-

http://dx.doi.org/10.1016/j.mineng.2016.06.011
0892-6875/ 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Mu, Y., et al. The depression of copper-activated pyrite in flotation by biopolymers with different compositions. Miner.
Eng. (2016), http://dx.doi.org/10.1016/j.mineng.2016.06.011
2 Y. Mu et al. / Minerals Engineering xxx (2016) xxxxxx

tion of dixanthogen, the main species responsible for the flotation Table 2
of un-activated pyrite (Mu et al., 2016). However, the depression The molecular weight of the biopolymers used in this work and the content of main
functional groups (provided by the supplier).
mechanism of biopolymers on the flotation of copper-activated
pyrite is still unknown. The depression mechanism of biopolymers Biopolymers Counterion Molecular Main functional groups
under these two scenarios should be different due to the change of weight

pyrite surface characteristics after copper activation. Additionally, Mw Mn Sulfonic/% Carboxylic/%

Mu et al. (2014) found that the three biopolymers differing in DP-1775 Na+ 39,000 2400 6.1 8.7
molecular weight and polymer chemistry exhibited different effi- DP-1777 Na+ 13,700 2000 8.5 9.5
ciencies in depressing the flotation of copper-activated pyrite at DP-1778 Ca2+ 6000 800 4.8 14.5

basic pH. Studies on the adsorption behavior of lignosulfonate have

shown that the molecular weight and bivalent cation may influ-
ence the adsorbed amount of polymers on mineral surface, while
the functional group may determine their affinity to the mineral
surface (Nanthakumar et al., 2010). However, how the structural
characteristics of lignosulfonate-based biopolymers affect their
depression on the flotation of copper-activated pyrite is unclear.
In this study, three lignosulfonate-based biopolymers (DP-1775,
DP-1777 and DP-1778) were examined as depressants in the flota-
tion of copper-activated pyrite at basic pH. Electrochemical tech-
niques were employed to investigate how they modified the
surface of copper-activated pyrite. Adsorption isotherms were also
measured to compare their adsorption capability. A combination of
these results allowed to speculate how lignosulfonate-based
biopolymers depress the flotation of copper-activated pyrite with
different molecular compositions.
2. Materials and methods
2.1. Materials and reagents
Pyrite was purchased from GEO discoveries, Australia. The
chemical composition of this material, analyzed by Inductively
Coupled Plasma Mass Spectroscopy (ICP-MS), is shown in Table 1.
The elemental content of iron and sulfur is 45.4 wt% and 50.5 wt%,
respectively. The analysis of the sample reveals the composition of
96 wt% pyrite with minor quartz, galena and copper minerals. The
sample was crushed using a roll crusher and then screened to col-
lect the +0.63.2 mm particle size fraction which was split, sealed
in polyethylene bags and stored in a fridge to avoid further oxida-
tion. The working electrode used in electrochemical studies was
prepared by cutting the pyrite sample to rectangular dimensions
of approximately 5  5  10 mm. It was connected by a copper
wire to one of the 5  5 mm faces and then mounted in a glass tube
with an electrochemically inert epoxy resin leaving one face of the
pyrite exposed.
The collector, potassium amyl xanthate (PAX) was provided by
Orica Australia Pty Ltd. The NASCOL 442 was used as frother. The
lignosulfonate-based biopolymers were supplied from Pionera,
Norway. The detailed physiochemical properties of these biopoly-
mers which were provided by the supplier are listed in Table 2.
DP-1775 has the highest molecular weight and lowest content of
anionic functional groups. DP-1777 has a lower molecular weight
grade CuSO4
5H2O was used for activating pyrite. Calcium ions
were reported to enhance adsorption or depression function of
polymer depressants by a bridging effect (Liu et al., 2000;
Bulatovic, 2007). Here, CaCl2 was used to introduce Ca2+ to under-
stand the role of counterion (Ca2+) of biopolymer DP-1778. The pH
was adjusted by the addition of AR grade NaOH or HCl solutions.
All solutions used in the experiment were prepared with analytical
grade reagents in deionized water just prior to the experiment.
2.2. Methods
2.2.1. Flotation procedure
The flotation procedure was detailed elsewhere (Mu et al.,
2014). Crushed pyrite (100 g) was combined with 100 mL water
and ground with 3.6 kg of grinding media in a laboratory stainless
steel rod mill for 6.5 min so that 80 wt% of the particles were less
than 106 lm. The pulp was then transferred to a 1.5 L JK flotation
cell at 900 rpm. NaOH solution was added to adjust the pH to 9.0.
Collector (PAX, 120 g t 1) and frother (NASCOL 442, 120 g t 1)
were added and conditioned for 2 min, respectively. Four flotation
concentrates were collected after cumulative times of 1, 3, 6 and
10 min at an air flow rate of 6 L min 1. The flotation froth was
scraped every 10 s. When biopolymers were used, they were added
after the pH adjustment, prior to collector addition. Copper sulfate
(500 g t 1) was added between pH adjustment and biopolymer
addition. A 2 min conditioning period was used for both biopoly-
mer and copper sulfate additions to allow sufficient time for the
adsorption of biopolymer and copper activation to occur.
2.2.2. Adsorption isotherms
1 g pyrite was pulverized to 38 lm just prior to the test. The
particle size distribution of the pulverized sample was measured
by a Malvern sizer 2000 (Malvern, UK) and the results are shown
in Fig. 1. To measure the size distribution, 1 g pulverized pyrite
was added into 50 mL deionized water, followed by 20 min stirring.
8 100
Volume
Cumulative volume
80
Cumulative volume/%

6
and higher content of functional groups than DP-1775. DP-1778
has the lowest molecular weight among the three biopolymers 60
Volume/%

with special counterion Ca2+, and a large proportion of carboxylic

4
group (14.5%).
Sodium borate (Na2B4O7
10H2O) and hydrochloric acid (HCl) 40
were used to prepare pH 9 buffer solution (0.01 M). Analytical
2
20
Table 1
Chemical compositions of the pyrite sample.
0 0
Mineral Species present (wt.%) 0.1 1 10 100 1000
Fe S Cu Bi Pb Al2O3 SiO2 Ti Zn Particle size/ m
Pyrite 45.40 50.50 0.10 0.02 0.13 0.03 0.35 0.04 0.05
Fig. 1. Particle size distribution of the pulverized sample for adsorption test.

Please cite this article in press as: Mu, Y., et al. The depression of copper-activated pyrite in flotation by biopolymers with different compositions. Miner.
Eng. (2016), http://dx.doi.org/10.1016/j.mineng.2016.06.011
 Y. Mu et al. / Minerals Engineering xxx (2016) xxxxxx
The prepared sample was transferred to the measurement cell. The
measurement was repeated three times. The experimental results
were interpreted by volume-based average particle size. The
pulverized particle size exhibited a standard normal distribution
with a peak at around 13 lm and the maximum particle size being
less than 38 lm.
The pulverized sample was first conditioned in 50 mL deionized
water with pre-adjusted pH 9 and 5  10 4 M CuSO4
5H2O in a
beaker agitated by a magnetic stirrer for 10 min. Then, biopolymer
solution of known concentration was added to the suspension and
the mixture was conditioned for a further 15 min in the beaker.
Afterwards, the suspension was centrifuged for 3 min at 450 rpm
and filtered by 0.45 lm syringe-driven filter to collect the super-
natant. The ultraviolet spectra of biopolymer samples were col-
lected by a Cary-50 UVvis spectrophotometer using the
absorption cell (Hellma Analytics) with 10 mm light path and
3500 lL volume in absorbance mode. The scan was conducted
between 200 nm and 400 nm wavelength. The UV spectra of the
three biopolymers are shown in Fig. 2 displaying the typical
adsorption peaks near 280 nm (owing to phenolic groups), shoul-
ders at 230 nm and the maximum adsorption at 200208 nm
(assigned to conjugated C@C) (Ge et al., 2013). In this study, the
biopolymer concentration in the transparent supernatant was
determined by the UV spectra at a wavelength of 280 nm. Blank
corrections were taken for all samples by using 1 g pyrite in the
background solution (50 mL deionized water with preset pH) as a
baseline. Biopolymers dissolved in the background solution were
used to establish calibration curves. The adsorbed amount was
then calculated from the difference between the initial (known)
concentration and the equilibrium (measured) concentration
(Nanthakumar et al., 2010).
2.2.3. Electrochemical studies
The electrochemical investigations were conducted using the
CHI 920D Scanning Electrochemical Microscope (SECM) with a
conventional three electrode electrochemical cell. A double layer
wall glass reactor was used as the electrochemical cell with an
effective volume of 200 mL. A 3 M KCl Ag/AgCl electrode, a plat-
inum plate electrode with a surface area of 1 cm2 and a pyrite elec-
trode were used as reference, counter and working electrodes,
respectively. All the measured potentials were converted to and
expressed in standard hydrogen electrode (SHE) scale.
The pyrite electrode surface was renewed by wet polishing
using 1200 grit silicon carbide paper and rinsed with deionized
water several times and then immediately inserted into the solu-
DP-1775
DP-1777
DP-1778
Absorbance
Phenolic groups
200 250 300 350
Wavelength / nm
Fig. 2. Ultraviolet spectra of the three biopolymers.
Please cite this article in press as: Mu, Y., et al. The depression of copper-activated pyrite in flotation by biopolymers with different compositions. Miner.
Eng. (2016), http://dx.doi.org/10.1016/j.mineng.2016.06.011
3
tion following the procedure published in the literature
(Hicyilmaz et al., 2004; Guo et al., 2015). Then the reference and
counter electrodes were attached to the electrochemical cell. One
open circuit potential (OCP) sweep was conducted before each type
of electrochemical experiments. The cyclic voltammetry of pyrite
was conducted starting from the OCP up to 520 mV, then to
280 mV and went back to the OCP with a scan rate of 20 mV s 1.
The voltammograms were circled five times for each measure-
ment. The impedance spectra were obtained at the OCP by apply-
ing a sinusoidal excitation signal of 10 mV in the frequency range
of 10 kHz to 10 MHz. Similar conditions were applied to all
experiments.
Pyrite activation was studied by adding 5  10 4 M CuSO4
5H2O
and conditioning the pyrite electrode at Eh of 80 mV maintained
by the Amperometric i-t Curve technique in buffer solution for
10 min since the reducing condition favors the copper activation
of pyrite. The activated pyrite electrode was then conditioned
with biopolymers and PAX individually or in combination to
investigate the influence of biopolymers on copper activation
and PAX adsorption. 15 min was allowed for pyrite electrode to
react after the addition of each chemical. The pyrite electrode
was then taken out and inserted into a fresh buffer solution for
analyses.
3. Results and discussion
3.1. Review of the flotation results
Results from the flotation of copper-activated pyrite in the pres-
ence of biopolymers at pH 9 are shown in Fig. 3. In all flotation
tests, 1  10 4 M CuSO4
5H2O was used to activate pyrite. Pyrite
exhibited a high flotation performance in alkaline condition after
copper activation with 85.4% recovery obtained in the absence of
biopolymers. All three biopolymers depressed the flotation of
copper-activated pyrite and pyrite recovery decreased with
biopolymer concentration. The three biopolymers displayed differ-
ent depression abilities. At a concentration of 33 mg L 1, DP-1775
and DP-1778 decreased pyrite recovery to 21.4% and 23.4%, respec-
tively, while only a slight decrease in pyrite recovery was observed
with DP-1777. However, at a concentration of 50 mg L 1, all three
biopolymers depressed the flotation of copper-activated pyrite sig-
nificantly with recoveries around 67%. Therefore, DP-1775 and
DP-1778 were more powerful in depressing the flotation of
copper-activated pyrite than DP-1777.
DP-1775
80 DP-1777
DP-1778
62.5%
Pyrite recovery / %
60
40
23.4%
20
21.4%
0
0 10 20 30 40 50
-1
400 Biopolymer concentration / mg L
Fig. 3. Flotation of copper-activated pyrite in the presence of DP-1775, DP-1777
and DP-1778 at pH 9 reproduced from Mu et al. (2014).
4 Y. Mu et al. / Minerals Engineering xxx (2016) xxxxxx
3.2. Adsorption tests
The flotation results show that pyrite recovery decreased with
biopolymer concentration. It appears that the depression effect of
biopolymers was associated with the adsorbed amount of biopoly-
mers on the surface of copper-activated pyrite. The measured
adsorption isotherms of the three biopolymers on copper-
activated pyrite at pH 9 are shown in Fig. 4. The adsorption of
the three biopolymers on un-activated pyrite at pH 9 were also
conducted and it was found that insignificant amounts of
biopolymers (less than 1 mg/g) were adsorbed on pyrite. This is
because at pH 9 pyrite surface is negatively charged and the sul-
fonic and carboxylic groups are dissociated making the biopolymer
molecules more anionic; therefore, the electrostatic repulsion
between the biopolymers and the surface inhibits the adsorption
of biopolymers. However, a small amount of biopolymers was
still adsorbed on the un-activated pyrite surface. This indicates
that except the electrostatic interaction, specific interactions like
hydrogen/chemical bonding may also contribute to the overall
adsorption process.
It can be seen from Fig. 4 that after copper activation significant
amounts of the three biopolymers were adsorbed on pyrite surface
to different extents. This implies that copper ions played a vital
role in aiding biopolymers adsorption. On the one hand, copper
ions on pyrite surface may reverse the surface from negative to
positive and promote biopolymers adsorption through chemical
bonding. On the other hand, the aqueous copper ions may screen
the functional groups making biopolymers less anionic. The
reduced electrostatic repulsion between the biopolymers and
copper-activated pyrite surface can facilitate the dense adsorption
of biopolymer molecules. In Fig. 4, the adsorption isotherms show
the regularity that with increasing biopolymer concentration, the
adsorption amount increased until reaching a plateau. The rapid
attainment of a single plateau suggests the high-affinity adsorption
in which virtually all of the available biopolymers bind to the
copper-activated pyrite surface until monolayer coverage is
attained. The adsorption isotherms appear to be of Langmuir form
(Ratinac et al., 2004; Pang et al., 2008). The Langmuir adsorption
model was developed to explain adsorption by assuming that an
adsorbate behaves as an ideal gas at isothermal conditions. It is
often used to describe and understand the physical mechanism
of polymer adsorption by assuming the Langmuir model to be valid
(Grigg and Bai, 2004; Ratinac et al., 2004; Li et al., 2012; Ge et al.,
2013).
5 DP-1775
DP-1777
DP-1778
-1
Adsorbed amount / mg g
4
3 and Barany, 2011). The great amount of carboxylic groups may also
2 sulfonic groups in DP-1778 also facilitates its adsorption.
1
0
0 50 100 150 200 250
-1
Biopolymer concentration / mg L
Fig. 4. Adsorption isotherms of DP-1775, DP-1777 and DP-1778 on copper-
activated pyrite at pH 9.
Please cite this article in press as: Mu, Y., et al. The depression of copper-activated pyrite in flotation by biopolymers with different compositions. Miner.
Eng. (2016), http://dx.doi.org/10.1016/j.mineng.2016.06.011
The plateau level corresponding to monolayer coverage of DP-
1778 (4.71 mg g 1) estimated from Fig. 4 was significantly larger
than that of DP-1775 (2.72 mg g 1), followed by DP-1777
(1.41 mg g 1). Meanwhile, at a similar biopolymer concentration,
the adsorbed amount of DP-1775 was almost doubled that of DP-
1777. Therefore, the adsorption capability of the three biopolymers
is in the order of DP-1778 > DP-1775 > DP-1777. This coincides
with the flotation results showing that DP-1775 and DP-1778 are
stronger depressants than DP-1777. The adsorption inversely cor-
relates with the content of sulfonic groups. DP-1778 with the low-
est amount of sulfonic groups (4.8%) gave the highest adsorption
density on copper-activated pyrite surface, while DP-1777 with
the highest amount of sulfonic groups (8.5%) displayed the lowest
adsorption capability. This is consistent with the study conducted
by Nanthakumar et al. (2010). A study by Yan et al. (2010) has
shown that sulfonic groups mainly distribute on the surface of lig-
nosulfonate molecules. A lower content of sulfonic groups may
provide less electrostatic repulsion between biopolymers and pyr-
ite surfaces thereby enhancing polymer adsorption. DP-1775 and
DP-1778 had different adsorption behavior but their depression
was similar. Obviously, besides the adsorption amount, other fac-
tors also played a role in depressing the flotation of copper-
activated pyrite.
Based on the physiochemical properties of biopolymers in
Table 2, DP-1775 and DP-1777 have similar chemical properties
but different molecular weights. The higher molecular weight of
DP-1775 than DP-1777 may contribute to the higher adsorption
capacity of DP-1775. It has been widely reported that with the
increase of lignosulfonate molecular weight, the adsorbed amount
increases (Ouyang et al., 2006; Yang et al., 2007; Pang et al., 2014).
This is because the proportion of negatively charged functional
groups decreases with an increase in biopolymer molecular
weight, which may in turn reduce the electrostatic repulsive force
between pyrite surface or the hydrophilic functional groups
already adsorbed on the pyrite surface and the approaching
biopolymer molecules. DP-1775 with the higher molecular weight
(39,000) and less sulfonic groups (6.1%) presented a higher adsorp-
tion capability than DP-1777. Furthermore, DP-1775 with the
highest molecular weight has long branched chains which may
also reinforce its adsorption (Shortridge et al., 2000; Gregory and
Barany, 2011).
It is interesting that DP-1778 with a low molecular weight
(6000) exhibited a high adsorption capacity. This is probably due
to its special counterion, Ca2+, and the large amount of carboxylic
groups. The calcium ions may function similar as copper ions in
reversing surface charge from negative to positive and neutralizing
the negative charges of functional groups of biopolymers already
adsorbed or in solution enhancing subsequent adsorption. The car-
boxylic groups in DP-1778 present a high chelating ability with
metallic ions, which may enhance the adsorption of DP-1778
through complexing with copper ions on copper-activated pyrite
(Gonalves and Benar, 2001; Nanthakumar et al., 2010; Gregory
strengthen the ability of hydrogen bonds forming between DP-
1778 and pyrite surfaces. As discussed earlier, the low content of
3.3. Electrochemical studies
3.3.1. Cyclic voltammetry
Cyclic voltammetry was conducted to investigate the electro-
300 chemical reactions occurring on pyrite surface exposed to various
solutions. Fig. 5 shows the voltammograms of pyrite electrode in
the absence and presence of 5  10 4 M CuSO4 in buffer solution
at pH 9 and it displays the surface oxidation and reduction of
un-activated pyrite and copper-activated pyrite. In the absence of
 Y. Mu et al. / Minerals Engineering xxx (2016) xxxxxx 5

200 Buffer solution 200 CuSO4

-4 A2
5 10 M CuSO4 CuSO4 + DP-1775 A2
CuSO4 + DP-1777 *
A1
100 A1
*
100 CuSO4 + DP-1778

Current/A
Current/A

A1
A1
0 0

C1
*
C1
-100 -100 *
C2 C2 C1

-300 -150 0 150 300 450 -300 -150 0 150 300 450
E vs SHE/mV E vs SHE/mV
Fig. 5. CVs of pyrite electrode in the absence and presence of 5  10 4 M CuSO4 at Fig. 6. CVs of copper-activated pyrite electrode in the presence of 50 mg L 1
pH 9 in 0.01 M Na2B4O7 buffer solution (third cycle; sweep rate, 20 mV s 1). biopolymers (DP-1775, DP-1777 and DP-1778) at pH 9 in 0.01 M Na2B4O7 buffer
solution (third cycle; sweep rate, 20 mV s 1; 5  10 4 M CuSO4).

copper ions, the voltammogram was characterized by two anodic

copper-activated pyrite surface is not an electrochemical process.
peaks (A1 and A2), one cathodic shoulder (C1) and one cathodic
All three biopolymers reduced the current intensity of peak A2
peak (C2). The current in the potential range from 100 mV to
attributed to the oxidation of pyrite surface. Thus, the adsorption
520 mV at A2 was produced by the oxidation of pyrite surface
of the three biopolymers passivated pyrite surface. However, the
resulting in the formation of ferric hydroxide, and a sulfur-rich
current intensities of the anodic peak A1 and the cathodic peak
sub layer which may be elemental sulfur (S0), polysulfides (FeSn)
C1 due to the electrochemical activity of copper(I) sulfide were
or metal deficient sulfide (Fe1 xS2) (Tao et al., 2003). Aggressive
all enhanced by the three biopolymers. The anodic peak area
oxidation of pyrite may occur when the upper potential increases
reflects the amount of oxidized products formed on electrode sur-
to 520 mV leading to the formation of SO24 (Miller et al., 2002;
face (You et al., 2013). Both the enhanced peak intensity and
Tao et al., 2003). The cathodic peaks were attributed to the reduc-
broadened peak area of peak A1 suggest that more copper(I) spe-
tion of the oxidation species formed during the anodic process. The
cies were oxidized in the presence of biopolymers leading to the
shoulder C1 commencing at 100 mV was due to the reduction of
extension of the cathodic peak C1. Therefore, biopolymers reacted
ferric hydroxide to ferrous hydroxide, while the peak C2 starting
with copper(I) sulfide sites on the copper-activated pyrite surface.
at 100 mV was related to the formation of HS by the reduction
Apparently, the adsorption of biopolymers on pyrite surface
of elemental sulfur (Hicyilmaz et al., 2004). The reversal of the
formed a copper(I)-biopolymer complex which was easily oxi-
potential from cathodic to anodic evidenced the commencement
dized. The current intensity of peak A1 in the presence of DP-
of the broad anodic wave (A1) attributed to the reformation of S0
1777 and DP-1778 was higher than that of DP-1775 indicating that
(Tao et al., 2003; Hicyilmaz et al., 2004). Since the pyrite electrode
more copper(I) species were oxidized in the presence of the former
was prepared by polishing in air and the voltammogram displayed
two biopolymers.
in Fig. 5 was the third sweep, the oxidation of ferrous to ferric
The voltammograms of copper-activated pyrite electrode in the
hydroxide might also contribute to the wave A1 (Tao et al., 1994).
absence and presence of 1  10 3 M PAX in buffer solution of pH 9
The voltammogram of pyrite electrode in the presence of cop-
are shown in Fig. 7. The addition of PAX did not bring in any new
per ions was different from that in the absence of copper ions. As
peaks. Therefore, the interaction between copper-activated pyrite
shown in Fig. 5, a new anodic peak (A1) starting from 300 mV
and correspondingly a new cathodic peak (C1) starting from the
similar potential appeared after the addition of copper ions. Stud-
-4
ies on copper activation of pyrite have confirmed that copper ions 200 5 10 M CuSO4
exist mainly in the form of copper(I) sulfide (Cu2S or CuS) on pyrite -4 -3
A2
5 10 M CuSO4 + 1 10 M PAX
surface. At basic pH conditions a small amount of Cu(OH)2 may
also precipitate on the surface (Leppinen, 1990; Laajalehto et al.,
100
1999; Weisener and Gerson, 2000a). Therefore, the anodic peak
Current/A

*
A1
A1 was due to the oxidation of surface copper(I) sulfide to copper
hydroxide. Accordingly, the cathodic peak C1 was due to the reduc- A1
tion of copper hydroxide. This is in accordance with the results 0
obtained by Hicyilmaz et al. (2004). Copper(I) sulfide is very stable
and not easily oxidized. Therefore, the anodic peak A1 was rather
weak. *
C1
Fig. 6 shows the voltammograms of copper-activated pyrite -100 C2
electrode in the presence of 50 mg L 1 biopolymers (DP-1775,
DP-1777 and DP-1778). The voltammogram obtained with the
-300 -150 0 150 300 450
copper-activated pyrite electrode in the absence of biopolymers
is included for a comparison. No new peaks appeared on the E vs SHE/mV
voltammogram upon the addition of biopolymers and the occur- Fig. 7. CVs of copper-activated pyrite electrode in the presence of 1  10 3 M PAX
rence potentials of the oxidation and reduction peaks remained at pH 9 in 0.01 M Na2B4O7 buffer solution (third cycle; sweep rate, 20 mV s 1;
unchanged. This indicates that the adsorption of biopolymers on 5  10 4 M CuSO4).

Please cite this article in press as: Mu, Y., et al. The depression of copper-activated pyrite in flotation by biopolymers with different compositions. Miner.
Eng. (2016), http://dx.doi.org/10.1016/j.mineng.2016.06.011
6 Y. Mu et al. / Minerals Engineering xxx (2016) xxxxxx
and xanthate ions is primarily chemical in nature. This is in accor-
dance with the findings by Hicyilmaz et al. (2004). Similar to the
case with biopolymers, the current intensity of peak A2 due to pyr-
ite surface oxidation was significantly reduced in the presence of
PAX, suggesting that PAX also passivated the pyrite surface.
Another important observation was that the addition of PAX elim-
inated the anodic peak A1 and cathodic peak C1 related to the elec-
trochemical reactions of copper(I) sulfide. This is probably due to
the preferential interaction of copper(I) on pyrite surface with xan-
thate forming the copper(I)-xanthate complex. The color of buffer
solution also demonstrates the corresponding change. It was
observed that during the experiment, the color of buffer solution
changed from weakly blue due to the presence of copper ions to
yellow with a significant amount of precipitates formed in solution
as soon as PAX was added. The yellow precipitates in solution were
believed to be copper xanthate formed through the interaction of
aqueous copper ions and xanthate ions. Copper xanthate is unsta-
ble and may easily decompose to copper(I) xanthate and dixan-
thogen which may precipitate on pyrite surface (Chandra et al.,
2012). Copper(I) xanthate is a very stable complex and its presence
may explain the lack of traces of copper(I) oxidation in the
voltammogram.
The influence of biopolymers on PAX adsorption on copper-
activated pyrite surface was studied by adding 50 mg L 1 biopoly-
mers prior to the addition of 1  10 3 M PAX and the voltammo-
grams are shown in Fig. 8. The voltammogram in the presence of
PAX only is also included. In the presence of biopolymers, the
peaks (A1 and C1) re-appeared and the peak area was broadened
when biopolymers were added before PAX. This suggests that the
copper(I) was oxidized and a significant amount of species possibly
copper-biopolymer/Cu(OH)2/CuSO4 formed during the anodic scan
in the presence of biopolymers. It can be inferred that pre-added
biopolymers interacted with copper(I) sulfide present on the
copper-activated pyrite surface and formed copper(I)-biopolymer
complex which inhibited the adsorption of xanthate ions. Due to
the larger magnitude of A1 and C1 peaks, the copper(I)-
biopolymer complex formed was more electrochemically active,
facilitating the oxidation of copper(I). Also in this case color
changes in the buffer solution were observed during the experi-
ment. The color of buffer solution changed from weakly blue due
to the copper ions to light brown when biopolymers were added
and the solution remained transparent after conditioning for
15 min. Further addition of PAX into the buffer solution changed
150
CuSO4 + PAX A2
CuSO4 + DP-1775 + PAX
100
CuSO4 + DP-1777 + PAX A1
*
CuSO4 + DP-1778 + PAX
50
Current/A
A1
0 0
-50
*
C2 C1
-100
-300 -150 0 150 300 450
E vs SHE/mV
Fig. 8. CVs of copper-activated pyrite electrode in the presence of 50 mg L 1
biopolymers (DP-1775, DP-1777 and DP-1778) and 1  10 3 M PAX at pH 9 in
0.01 M Na2B4O7 buffer solution (third cycle; sweep rate, 20 mV s 1; Biopolymer
added before PAX; 5  10 4 M CuSO4).
Please cite this article in press as: Mu, Y., et al. The depression of copper-activated pyrite in flotation by biopolymers with different compositions. Miner.
Eng. (2016), http://dx.doi.org/10.1016/j.mineng.2016.06.011
the color from light brown to dark brown. However, no visible yel-
low precipitates (copper xanthate) were observed and the solution
was still transparent after conditioning for another 15 min. The
current intensity of peak A1 in the presence of DP-1778 was the
highest, followed by DP-1777 and DP-1775.
The special counterion of DP-1778, Ca2+, was found to enhance
the biopolymers ability to inhibit xanthate adsorption in the un-
activated pyrite system at pH 5 (Mu et al., 2016). Ca2+ can neutral-
ize the negatively charged pyrite surface enhancing biopolymers
adsorption. To confirm if Ca2+ enhanced the ability of DP-1778 in
inhibiting xanthate adsorption in copper-activated pyrite system,
the cyclic voltammetry of copper-activated pyrite electrode in
the presence of 50 mg L 1 DP-1777 and 0.01 M Ca2+ at constant
PAX concentration (1  10 3 M) in buffer solution of pH 9 was con-
ducted and the voltammogram is shown in Fig. 9. The voltammo-
grams of copper-activated pyrite electrode in the absence and
presence of DP-1777 at a constant PAX concentration are included
for a comparison. When Ca2+ was present, the peaks A1 and C1
identified as the oxidation and reduction of surface copper(I) spe-
cies did not appear on the voltammogram. The shape of voltammo-
gram in the potential range of 200 mV to 400 mV remained similar
as that in the presence of PAX only. This indicates that the presence
of Ca2+ did not enhance the ability of DP-1777 to inhibit xanthate
adsorption. This may be because in copper-activated pyrite system,
the surface copper ions played the leading role in neutralizing pyr-
ite surface and enhancing biopolymers adsorption. The function of
Ca2+ in this aspect was overlooked. It was also observed that the
current intensity of peak A2 due to pyrite surface oxidation was
suppressed in the presence of Ca2+, indicating that Ca2+ caused sur-
face passivation probably due to the precipitation of Ca(OH)+/Ca
(OH)2 and calcium-biopolymer complex on pyrite surface limiting
the transfer of oxidant.
3.3.2. Electrical impedance spectroscopy
Electrical impedance spectroscopy (EIS) was conducted in situ
to detect the modification of pyrite surface chemistry in the pres-
ence of different reagents. The measured EIS data are shown in
Fig. 10(a and b) in the form of Nyquist plots. The Nyquist plots
compose of the imaginary impedance (Y-axis) and the real impe-
dance (X-axis) (Bayoudh et al., 2008).
The Nyquist plot of pyrite electrode in buffer solution displays
an incomplete semicircle, which is ascribed to capacitance at the
electrode/electrolyte interface and the charge transfer resistance
150
CuSO4 + PAX
A2
CuSO4 + DP-1777 + PAX
100
CuSO4 + DP-1777 + CaCl2 + PAX *
A1
50
Current/A
A1
-50
*
C1
C2
-100
-300 -150 0 150 300 450
E vs SHE/mV
Fig. 9. CVs of copper-activated pyrite electrode in the presence of 50 mg L 1 DP-
1777, 1  10 3 M PAX and 1  10 2 M CaCl2 individually or in combination at pH
9.0 in 0.01 M Na2B4O7 buffer solution (third cycle; sweep rate, 20 mV s 1;
5  10 4 M CuSO4).
 Y. Mu et al. / Minerals Engineering xxx (2016) xxxxxx 7

(a) 4 (b) 4

CPE
3 Rs 3
Rct

Zi/K cm
Zi/K cm

2 2
Buffer solution
CuSO4 CuSO4+ PAX
1 CuSO4 + DP-1775 1 CuSO4 + DP-1775 + PAX
CPE
Rs CuSO4 + DP-1777 CuSO4 + DP-1777 + PAX
Rct W CuSO4 + DP-1778 CuSO4 + DP-1778 + PAX
0 0
0 2 4 6 8 10 0 2 4 6 8 10
Zr/K cm Zr/K cm

4 1
Fig. 10. EIS of pyrite electrode exposed to various solutions at pH 9 in 0.01 M Na2B4O7 buffer solution: 5  10 M CuSO4 + 50 mg L biopolymers (DP-1775, DP-1777 and
DP-1778) (a) and 5  10 4 M CuSO4 + 50 mg L 1 biopolymers + 1  10 3 M PAX (b).

against pyrite oxidation (Liu et al., 2011). This indicates that pyrite
oxidation was mainly controlled by a charge transfer process (Liu
et al., 2011). The equivalent circuit Rs(Rct CPE) shown in Fig. 10
was proposed to fit the spectra in buffer solution. The equivalent
circuit Rs(Rct CPE) consists of a resistor Rs representing solution
resistance in series with a parallel circuit containing a capacitor
CPE (interfacial capacitance) and a resistor (charge transfer resis-
tance). Here, the so-called constant phase element (CPE) is used
to represent the capacitance due to double layer charging and/or
possible surface layers. According to Ekmeki et al. (2010), the
CPE can provide better fitting results to an electrochemical system
when the electrode surface is rough and inhomogeneous. The sur-
face roughness of the electrode is indicated by a factor n, which
usually varies between 0.5 and 1. When n = 1, the CPE is equivalent
to an ideal capacitor (Ekmeki et al., 2010; Guo et al., 2015). The
CPE and Rct depend on the dielectric and conducting features at
the electrode/electrolyte interfaces.
For the pyrite electrode exposed to various reagents, the shape
of the impedance spectra for pyrite electrode was changed, with an
incomplete semicircle in the high frequency region followed by a
45 oblique line at low frequency. These impedance spectra were
mainly associated with oxygen reduction and copper(I)/iron sul-
fide oxidation on pyrite surface. The linear part of the impedance
spectra in the low frequency region is the typical feature of War-
burg impedance representing the mass transfer resistance caused
by the diffusion of oxidizing agents (e.g., O2 and Cu2+) or products
(e.g., OH and Cu+) across the interface of electrode (Liu et al.,
2011). This indicates that the reactions occurring at pyrite elec-
trode was controlled by charge transfer process at high frequency
(semicircular) and diffusion controlled at lower frequency (linear).
Therefore, the equivalent circuit Rs(CPE (Rct W)) in Fig. 10 can be
used to fit the impedance data of pyrite electrode in the presence
of reagents. The Rs, Rct and CPE have the same meaning as
described above. W represents the diffusion impedance compo-
nent. The change in the equivalent circuit is accompanied by a
decrease in Rct value along with an increase in W value (Liu
et al., 2011). The fitting values of the impedance data in Fig. 10
using the corresponding equivalent circuit are summarized in
Table 3. v2 represents the sum of quadratic deviations between
experimental and calculated data (Liu et al., 2011). As shown in
Table 3, the low v2 values suggest that the proposed circuits are
appropriate for interpreting the impedance data.
The results in Table 3 show that the OCP of pyrite electrode in
the background solution was 259.5 mV. The addition of oxidant
copper ions increased the OCP, while the addition of PAX to
copper-activated pyrite caused the decrease of the OCP. Therefore,
the oxidation of xanthate ions also occurred on the copper-
activated pyrite surface. However, when biopolymers were pre-
sent, the OCP of copper-activated pyrite electrode remained similar
whether PAX was present or not. Obviously, the effect of xanthate
was masked by the presence of biopolymers. The solution resis-
tance Rs varied only slightly in different electrolytes. The Rct and
CPE values of pyrite electrode in bare buffer solution (Table 3-1)
were 9614 X cm2 and 197 lF cm 2, respectively. When copper
ions were present individually (Table 3-2) or in combination with
biopolymers (Table 3, 35), the Rct values significantly decreased
with a rise of W value. This is also obvious in the Nyquist plot
(Fig. 10a) where the radii of the semicircles (representing Rct) for
pyrite electrode in the presence of copper ions alone or together
with the three biopolymers in the high frequency region were sig-
nificantly smaller compared with pyrite electrode in bare solution.
The Rct is inversely proportional to the net rate of electrochemical
reactions on the surface (De Wet et al., 1997). Therefore, the
decrease of Rct in the presence of biopolymers indicates that
copper-activated pyrite surface became more active. This is in
accordance with the results from cyclic voltammetry studies.

Table 3
4 1 3
The fitting values of the resistances and capacitances using the corresponding equivalent circuits (5  10 M CuSO4, 50 mg L biopolymers, 1  10 M PAX).

No. Electrode OCP vs SHE/mV Rs/X cm 2

Rct/X cm 2
CPE/lF cm 2
n W/X cm2 v2/10 3

1 Py 259.5 214.9 9614 197.0 0.90 4.71

2 Py-Cu2+ 292.4 223.1 2940 284.8 0.82 2709 2.09
3 Py-Cu2+-DP-1775 285.7 254.3 2932 331.6 0.75 2741 2.79
4 Py-Cu2+-DP-1777 283.9 236.6 2841 438.8 0.75 2973 1.78
5 Py-Cu2+-DP-1778 283.9 224.2 2906 458.7 0.74 2939 3.54
6 Py-Cu2+-PAX 269.9 183.4 7842 146.0 0.86 2138 1.70
7 Py-Cu2+-DP-1775-PAX 286.9 220.0 4717 254.9 0.78 2893 2.38
8 Py-Cu2+-DP-1777-PAX 284.9 226.8 2954 339.6 0.77 2842 1.74
9 Py-Cu2+-DP-1778-PAX 283.9 195.9 2282 405.3 0.76 2448 2.96

Please cite this article in press as: Mu, Y., et al. The depression of copper-activated pyrite in flotation by biopolymers with different compositions. Miner.
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8 Y. Mu et al. / Minerals Engineering xxx (2016) xxxxxx
In the presence of xanthate the Rct of copper-activated pyrite
electrode (Table 3-6) increased substantially from 2940 X m2 in
the presence of only copper (Table 3-2) to 7842 X cm2. This is also
reflected by the radii of the semicircles in the high frequency
region in Nyquist plots (Fig. 10b). This was due to the passivation
of both the pyrite surface and copper(I) sulfide-covered sites as
proposed previously using cyclic voltammetry technique. Also
shown in Table 3 is the substantial decrease of Rct when biopoly-
mers were added prior to xanthate. At the same time, CPE value
was raised from 146.0 lF cm 2 for the copper-activated pyrite
with xanthate alone to different extents by the three biopolymers.
The impedance spectra obtained in solution containing both
biopolymers and PAX in Fig. 10b are similar to those recorded in
the absence of PAX (Fig. 10a). Thus, the species formed after
biopolymer adsorption inhibited the adsorption of xanthate and
formation of the copper(I) xanthate surface layer, which is in line
with the cyclic voltammetry study. The fitting values in Table 3
(79) show that the Rct value in the presence of DP-1778 was the
lowest, followed by DP-1777 and DP-1775. Therefore, the ability
of the three biopolymers in inhibiting xanthate adsorption fol-
lowed the order of DP-1778 > DP-1777 > DP-1775. According to
the biopolymer chemistry shown in Table 2, DP-1778 has the high-
est content of functional groups and it exhibited the strongest abil-
ity to inhibit xanthate adsorption. While the DP-1775 has the
lowest content of functional groups and displayed the weakest
ability to inhibit xanthate adsorption. Therefore, the functional
group played a significant role in inhibiting xanthate adsorption.
The electrochemical results also show that the chemical state of
surface copper(I) species on copper-activated pyrite surface sites
underwent a significant change in the presence of biopolymers
and/or xanthate as shown in Fig. 11. This can be explained by the
chelating ability of biopolymer molecules. When copper(I) inter-
acts with pyrite-S or xanthate-S, the copper(I) which has a fully
occupied 3d shell (3d10) readily accepts an electron pair and S acts
in part as an electron donor. Thus, a coordinate, covalent bond
between copper(I) and S forms, leading to the formation of
hydrophobic copper(I) sulfide/xanthate responsible for pyrite
flotation. The covalent bond may partially delocalize the S electron
cloud towards copper, giving it more character typical of copper(I)
with a fully occupied 3d shell (3d10) (Chandra et al., 2012). The
outer-shell electron of copper(I) nucleus is not easy to lose thereby
preventing the oxidation of copper(I) to copper(II) (3d9) as indi-
cated in Fig. 7. In the presence of biopolymers, copper(I) on pyrite
surface interacts with the two oxygen atoms in carboxylic and
hydroxyl groups forming a multiple six-member-ring complex.
The chelate compound is more stable than the single coordination
complex. Thus, the copper(I)-biopolymer complex is more stable
than the copper(I)-sulfide complex, favoring the interaction
- -
O O
O S
+ -
Cu S (Pyrite-S)
Biopolymer
PAX O CH3
- HO
S -
+ O OH
H11C5 O Cu + +
- Cu Cu
S
Fig. 11. Possible changes of the chemical state of copper species on copper-activated pyrite surface.
Please cite this article in press as: Mu, Y., et al. The depression of copper-activated pyrite in flotation by biopolymers with different compositions. Miner.
Eng. (2016), http://dx.doi.org/10.1016/j.mineng.2016.06.011
between biopolymer and copper(I). Due to the high electronegativ-
ity of O in the coordination ligands, the bond formed between cop-
per(I) and biopolymer is ionic in nature and its formation draws
the electron in the outer shell of copper(I) nucleus towards oxygen.
As a result, the copper(I) can be easily oxidized to copper(II) when
the potential is over the equilibrium value of copper(I)/copper(II)
couple as shown in Figs. 6 and 8. In the presence of biopolymers,
the copper(I) bound in a biopolymer chelate also reduces the pos-
sibility of interacting with xanthate. The solution copper ions may
also bind with biopolymers and precipitate on pyrite surface,
which restricts the further activation of pyrite. The hydrophilic,
negatively charged functional groups of adsorbed copper-
biopolymer complexes and the oxidation product, Cu(OH)2/Fe
(OH)3, accumulating on pyrite surface inhibit the approach and
adsorption of xanthate. Thus, the flotation of copper-activated pyr-
ite is depressed.
The results show that DP-1778 has the highest adsorption capa-
bility onto copper-activated pyrite and highest ability to inhibit
xanthate adsorption. However, its depression effect is similar to
DP-1775 as shown in Fig. 3. This may be caused by the larger
molecular size of DP-1775 due to its highest molecular weight. In
general, the floatability of pyrite depends on the balance between
hydrophobic and hydrophilic species on the surface (He et al.,
2005; Lpez Valdivieso et al., 2005). DP-1775 molecules may cover
a significantly large surface area leaving small active sites available
for xanthate adsorption. Besides, the longer branched chains of the
adsorbed DP-1775 molecules may better encapsulate copper(I)
inside the proposed chelate. Both mechanisms can inhibit the
interaction between xanthate and pyrite surface. Thus, the depres-
sion effect of DP-1775 is also strong. DP-1777 with a low molecular
weight and low surface coverage, presents the lowest depression
effect although it exhibits a little higher ability than DP-1775 in
inhibiting xanthate adsorption.
The biopolymers acted differently in the depression of copper-
activated pyrite at pH 9.0 and un-activated pyrite at pH 5.0 in flota-
tion. In the un-activated pyrite flotation, pyrite surface was passi-
vated by the adsorption of biopolymers, which inhibited the
oxidation of xanthate and the formation of dixanthogen, the main
entity responsible for pyrite flotation (Mu et al., 2016). While in
copper-activated pyrite flotation, biopolymers functioned through
chelating with the activating ion, copper(I), on activated pyrite sur-
face, inhibiting the combination of copper(I) with xanthate. Simi-
larities were also observed in these two systems regarding the
influence of biopolymer structure. For example, a higher molecular
weight and the counterion Ca2+ corresponded to a higher biopoly-
mer adsorption amount, while the content of functional groups
corresponded to biopolymers ability to inhibit xanthate adsorp-
tion (Mu et al., 2016).
Chelating effect
CH3
O -
O Lignin S O
O O
CH3 CH3 S Lignin
O
O
O O
OH HO
- -
O O
+ + + + + + +
Cu Cu Cu Cu Cu Cu Cu
Pyrite surface
 Y. Mu et al. / Minerals Engineering xxx (2016) xxxxxx
4. Conclusion
In this study, three lignosulfonate-based biopolymers (DP-1775,
DP-1777 and DP-1778) were tested as depressants for the flotation
of copper-activated pyrite and the modification of surface proper-
ties were studied by electrochemical techniques. Cyclic voltamme-
try suggests that copper(I) sulfide occurred on the copper-
activated pyrite surface and was responsible for the flotation in
the presence of xanthate. In the presence of biopolymers, a
copper(I)-biopolymer complex formed and then accelerated the
oxidation of copper(I) and inhibited xanthate adsorption. Biopoly-
mers might also combine with solution copper ions precipitating
on pyrite surface, which restricted the further activation of pyrite
surface. The impedance spectra confirm that copper-activated pyr-
ite surface became diffusion controlled in the presence of biopoly-
mers due to the formation of metallic hydroxides species and the
pre-adsorbed biopolymers restricted xanthate adsorption on pyrite
surface.
The physiochemical properties of biopolymers played a vital
role in their depression behavior. The depression of copper-
activated pyrite in flotation in the presence of biopolymers was
related to the adsorption amount of biopolymers on pyrite surface.
The correlation between biopolymer structures and adsorption iso-
therms reveals that the high depression effect of DP-1775 might be
due to its high molecular weight leading to a high adsorption
amount. The special counterion Ca2+, the large amount of car-
boxylic group and the small amount of sulfonic group of DP-
1778 molecules might enhance DP-1778 adsorption on copper-
activated pyrite surface. Electrochemical studies show that DP-
1778 effectively inhibited xanthate adsorption probably due to
its large content of functional groups.
Acknowledgements
The authors gratefully acknowledge financial support from the
Australian Research Council and Pionera, Norway with a grant
number of LP120200162. The first author also thanks the scholar-
ship provided by the University of Queensland and China Scholar-
ship Council.
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Please cite this article in press as: Mu, Y., et al. The depression of copper-activated pyrite in flotation by biopolymers with different compositions. Miner.
Eng. (2016), http://dx.doi.org/10.1016/j.mineng.2016.06.011