Minerals Engineering, Vol. 8, No. 11, pp.

1347-1357, 1995
Copyright © 1995 Elsevier Science Ltd
Pergamon Printed in Great Britain. All fights reserved
0892--6875(95)00101--8 0892-6875/95 $9.50+0.00

A STUDY OF THE REMOVAL OF OXIDATION PRODUCTS

FROM SULFIDE MINERAL SURFACES

P. CLARKE, D. FORNASIERO, J. RALSTON and R. St. C. SMART

Ian Wark Research Institute, University of South Australia, The Levels, S.A. 5095, Australia
(Received 16 June 1995; accepted 18 July 1995)

ABSTRACT

The flotation and separation of sulfide minerals can be detrimentally affected by the
oxidation of the surface of these minerals. The surface oxidation products consist mainly
of metal hydroxides and sulfur-oxy species, either adsorbed in thin layers or precipitated
from solution as colloidal particles. The amount of surface oxidation will reduce the
hydrophobicity of the mineral and make the adsorption of collectors less selective. The
interaction between these oxidation layers and the mineral is generally weak, electrostatic
and~or hydrophobic in nature.

In this study, various methods were used to remove oxidation products from the surface
of sever~l sulfide minerals. The effects of mineral treatment by mechanical (sonication or
attrition by quartz) or chemical (pH change or use of complexant) methods on mineral
flotation were investigated and correlated with the amount of oxidation product removed
from the mineral surface. It was also shown that these "cleaning" methods were selective
in removing oxidation products in mixed mineral systems.

Keyworlts
Flotation, metal sulfides, oxidation, surface analysis, sonication, EDTA.

INTRODUCTION

Although moderate oxidation of the surface of sulfide minerals has been shown to be beneficial for the
adsorption of collectors and the formation of hydrophobic sulfur species, excessive oxidation is detrimental
to the effective separation of these minerals. Oxidation arises from the dissolution of minerals and grinding
media. Dissolved metal ions hydrolyse, sulfide ions oxidize: both can readsorb on mineral surfaces or react
with each other or dissolved gas molecules before precipitation [1]. Surface analytical techniques such as
scanning Auger and electron microscopies have shown the extent of surface mineral oxidation to be a thin
layer (5-80nm) of adsorbed oxidation products (eg., metal hydroxides), precipitated colloidal particles of
metal hydroxides (1-5 microns) and fine mineral particles of a few microns in size [2]. Fine particles or
slimes appear to be more oxidized than the larger mineral particles; the causes of this behaviour have been
discussed elsewhere [3]. The interaction between the oxidation products and the mineral surface is generally
weak as sonication/decantation removes these oxidation products [2]. Electrostatic and solvation forces play
an important role in this interaction [4]. The adsorption or precipitation of these oxidation products on
mineral surfaces has been described as indiscriminate [5], preventing reagents such as collectors to reach
their targeted minerals.

Presented at Minerals Engineering '95, St. Ives, Cornwall, England, June 1995

1347
 1348 P. Clarke et al.

Several methods can be used to remove the surface oxidation products and are either chemical or
mechanical in nature. The chemical method refers to the modification of the oxidation products to a form
which is no longer attracted to the mineral surface (eg., by a change in pH), or to a form which has a high
affinity for collectors or is already hydrophobic (eg., Cu(II) addition). In the mechanical methods, energy
is used to overcome the attraction of these oxidation products to the mineral surface (eg., by sonication,
attritioning with quartz as a scavenger surface). To be effective, these methods also need to be selective.

Although the majority of the results reported in this study involves sphalerite, most of the methods used are
generic and may be used to remove surface oxidation products from other sulfide minerals.

EXPERIMENTAL SECTION

All chemicals were of analytical grade quality. Potassium ethyl xanthate, KEX, was purchased from Aldrich
and was purified as described previously [6]. High purity nitrogen gas (CIG Ltd) was scrubbed by bubbling
it through a silica dispersion prior to introduction into the reaction vessel. Conductivity water, produced by
reverse osmosis, two stages of ion exchange and two stages of activated carbon prior to f'mal filtration, was
used in all experimental work. This water was "pretreated" at the specified pH with KNO 3 (0.001 mol dm -3)
as electrolyte and by bubbling nitrogen into it. The sphalerite, chalcopyrite and galena samples were
purchased from Ward's Natural Science Establishment. The chemical analyses are reported in Table 1.

TABLE 1 Chemical composition (weight %) of the chalcopyrite, sphalerite and galena samples

Element
minerals Cu Fe S Pb Zn

Chalcopyrite, CuFeS 2 35.5 26.3 35.8 0.07 700 (ppm)

(Messina, Transvaal)
Sphalerite, ZnS 510 (ppm) 0.3 33.1 0.9 64.9
(Elmwood mine,Tennessee)
Galena, PbS 25 (ppm) 720 (ppm) 13.7 84.4 110
(Brushy Creek, Missouri) (ppm)

Just prior to use, minerals were ground in a small amount of "pretreated" water with a ceramic mortar and
pestle. The 38-75 ~rn fraction was deslimed by three 1 minute periods of sonication in a Soniclean 500T
300W sonic bath (Transtek Systems), each period followed by decantation of the slimes.

The mineral dispersion (1.2 gram, approximately) was then transferred into a water-jacketed, closed reaction
vessel and conditioned at 25 _+ 0.2 °C for 20 rain. in 0.6 dm 3 of a 0.001 mol dm -3 KNO 3 solution in the
presence of nitrogen and at a pH of 8.5. The pH was kept at a fixed value of interest by adding small
quantities of a concentrated solution of nitric acid or potassium hydroxide. The mineral dispersion was then
conditioned for 15 min. with cupric nitrate and for 10 min. with KEX before being transferred into a
modified Hallimond tube microflotation cell. The minerals were collected after 0.5, 2, 5 and 8 min. of
flotation. In the mixed mineral experiments, minerals were ground separately but conditioned together. The
float fractions and the tail were dissolved in acid in order to measure the percentage of each mineral by
atomic absorption spectroscopy (Varian Techtron Model AA-4 ). A first order rate equation was used to
describe the flotation process. The flotation recovery maximum and flotation rate constant, k, were
calculated from the flotation data.

XPS measurements were obtained with a Perkin Elmer Physical Electronics Division (PHI) 5100
spectrometer using an MgK~ X-ray source operated at 300 W. A pass energy of 18 eV was used for all
elemental spectral regions. The pressure in the analyser chamber was 10-7 Pa. The energy scale was
 Removal of oxidationproductsfrom sulfidemineral surfaces 1349

calibrated using the Fermi edge and the 4f7/2 line (BE=84.0 eV) for gold. An accelerated Ar+ ion beam at
3 kV was used to etch the surface to a depth of approximately 2.5 nm. At the end of the 8 min. flotation
experiment, the concentrate and tail fractions were washed with pH adjusted electrolyte solution to remove
any suspended colloidal particles and were introduced immediately in the fore-vacuum of the XPS
spectrometer as a slurry [1].

Fourier Transform Infrared (FFIR) spectra were measured with a Bio-Rad model FTS65 spectrometer at
a resolution of 4 cm -1 using a broad band mercury-cadmium-telluride liquid-nitrogen-cooled detector. The
dried mineral sample was placed in the cup of a Spectra Tech diffuse reflectance apparatus inside the
spectrometer with ]potassium bromide.

Electrophoretic m obilities were measured in a vertically mounted cell inside a Rank Brothers
Microelectrophoresis Mark II apparatus. All mineral samples were conditioned at pH 8.5. At least 10
mobility measurements at each of the two stationary planes were performed at each pH (successively
reversing the platinum electrode polarization), and the average mobility was converted to zeta potential using
the Smoluchowski equation.

RESULTS AND DISCUSSION

Copper addition and change in pH

Metal ions can act as activators or depressants of sulfide mineral flotation depending on the pH of the
system and the concentration of these metal ions. This dual action of metal ions is well illustrated in Figure
1. Up to a Cu(II) oancentration of 5 10-6 mol dm -3, the collectorless flotation of sphalerite at pH
8.5 increases from 30% to 80% with an increase in Cu(II) concentration in solution. For higher Cu(II)
concentrations, the flotation recovery of sphalerite decreases sharply to a level even lower than that
measured in the absence of Cu(II) [7-9]. This trend is not common to all pH values. Indeed, for pH values
lower than 7 and at a pH value of 12, the flotation recovery increases with Cu(II) concentration, reaching
a plateau around 70 to 83% but no decrease in recovery is found at high Cu(II) concentrations (Figure 2).
Large changes in th,~ zeta potential of sphalerite are observed in the presence of Cu(II). These changes have
been reported in th,~ literature but it is worth describing them again in this study in order to explain the
flotation trends [10]. On addition of Cu(II), the positive zeta potential of sphalerite below pH 6.5 becomes
suddenly negative ~Lndrather independent of Cu(II) concentration. At higher pH values, the negative zeta
potential slightly increases for a Cu(II) concentration of 2 10-5 mol dm -3 but reverses sign and becomes
more positive for Ca(II) concentrations higher than 2 10-4 mol dm -3. The decrease in flotation recovery of
sphalerite for Cu(II) concentrations higher than 10-6 mol dm "3 and the sign reversal of the zeta potential for
pH values higher than 6.5 are due to the adsorption or precipitation of cupric hydroxide on sphalerite
making the surface more hydrophilic and more positively charged (the isoelectric point, iep, of Cu(OH) 2
is at a pH around 9.4 [11]). Indeed, this decrease in flotation coincides with the precipitation of Cu(OH)2(S)
in solution as shown in the thermodynamic calculations (Figures 1 and 2) and observed on the mineral
surface by XPS [12]:. A similar sign reversal of the zeta potential of quartz in the pH region 7 to 9 has been
observed in the presence of Cu(II) [12]. In conditions where copper hydroxide is not formed, at low Cu(II)
concentrations or when the pH is lower than 6.5 (see Figures 1 and 2), the sphalerite surface becomes more
hydrophobic and negatively charged in the presence of Cu(II). It has been well established that zinc
hydroxide is present on the sphalerite surface as indicated by its low collectorless flotation and its zeta
potential (iep moving from 1.6 for a non oxidized sphalerite to 8.5 for a fully oxidised sphalerite surface
or for zinc oxide [ 10]). XPS [12] and EDTA extraction reveal that the oxidation products and in particular,
zinc hydroxide, are removed from the sphalerite surface on Cu(II) addition, therefore exposing a more
hydrophobic "virgin" surface (2.9 10-6 and 5.6 10 -7 mol of surface Zn(II) per gram of mineral have been
extracted by EDTA in the absence and the presence of 2 10-5 mol dm -3 Cu(II), respectively). Figure 1
indicates that the amount of Cu(II) adsorbed on sphalerite is matched by Zn(II) which desorbs until a
concentration of Cu(II) added of approximately 10-5 mol dm -3. Thereafter, the Zn(lI) concentration in
solution remains constant while Cu(II) keeps adsorbing, probably as copper hydroxide. Moreover, Cu(II)
 1350 P. Clarke et al.

exchanges with Zn(II) ions in the sphalerite lattice with a subsequent reduction to Cu(I) [8,13,14]. This
reduction of copper has been shown to be associated with the oxidation of sulfide to elemental sulfur or
polysulfide at the mineral surface [14-16]. Sulfur and polysulfide are negatively charged [10] as is the case
for the zeta potential of sphalerite at low Cu(II) concentrations. At high pH values, the concentration of
negatively charged cupric hydroxide species increases (Figure 2). It is likely that these species are removed
from the sphalerite surface which is also negatively charged [17]. Both the removal of zinc hydroxide and
the oxidation of sulfide to elemental sulfur or polysulfide may explain the increase in sphalerite flotation
on addition of Cu(II).

100, , , , , , .,,-/U 4

80

6o 10-6

40 =

10-8

; 0 ' I .' I ' i : '

E
"O

O o &A~,
V
E
,-., lO-S
¢-
N ,o
L.. 0
O

O
~ - 10-6 I , I i ' I

10 -7 10 "e 10 -s 104
[Cu(ll)]addecl (tool drrra)
Fig. 1 (Top) Flotation of sphalerite at pH 8.5 as a function of the concentration of added Cu(II). The dashed
line represents the concentration of Cu(OH)2(s) obtained from thermodynamic calculations. (bottom)
Concentration of Cu(II) adsorbed (o) on and Zn(II) released (,) from sphalerite at a pH of 8.5
as a function of the concentration of added Cu(II) (at this pH and without copper present,
the concentration of zinc in solution is negligible).

Sonication

Figure 3 shows the effect of sonication on the flotation of chalcopyrite and galena. The rate of flotation and
the recovery increase with an increase in the power of sonication of the mineral pulp. Complementary
 Removal of oxidation products from sulfide mineral surfaces 1351

analyses (XPS, EDTA extraction) have revealed that the amount of iron and lead hydroxide on the surface
of chalcopyrite and galena, respectively, is reduced on sonication, exposing a more hydrophobic surface
[1,18]. Indeed, 1.0 10-6, 1.4 10-6 and 3.5 10-6 mol g-I (per gram of galena) of lead hydroxide is extracted
by EDTA on the galena surface after a sonication power of 0, 80 and 300 W, respectively, is applied.
Importantly, the oxidation products dislodged by sonication from the mineral surface readsorb if they are
not removed from the solution or if flotation is not performed immediately.

o~ 100 I I " I I

~" 80

o0 60

= 40
0
~ 20
0
u_ 0 ' I , I ' I ' I '

>
30 E
v
n

0 t~
t-

-30 ¸ O

-60
I I I I I 'l I I ~ 1 N

0 - - ~ ~ 1 0 " 7 ~
10s
3 5 7 9 11 13
pH
Fig.2 (top) Collectorless flotation of sphalerite as a function of pH without (o) and with 2 10-4 mol dm -3
of added Cu(II) (-). (middle) Zeta potential of sphalerite as a function of pH and concentration of added
Cu(II): (o) 0; (A) 2 10-5; (A) 2 10-4; (.) 5 10-4 mol dm -3. (bottom) Thermodynamic calculations of the
concentration of metal copper species as a function of pH.
(o) Cu 2÷, (-) Cu(OH) +, (a) Cu(OH) 2 (aq), (=) Cu(OH)2(s), (A) Cu(OH)3-, (,) Cu(OH)42-,
(+) Cu2(OH)22+ and (x) Cu +. [CU]T=2Xl0-5 tool din-3; Eh=0.25 V.

Sonication has been used in the separation of mixed minerals (Figure 4). Without sonication, good
separation of chalcopyrite from sphalerite is achieved at a pH of 8.5 in the presence of Zn(II) (2 10--4 mol
dm -3) and ethyl xanthate (3 10-5 tool dm-3). At this pH value, zinc hydroxide is formed in solution and
adsorbs or precipitates on the sphalerite surface keeping its flotation to a very low value (2%) while

8:II-G
1352 P. Clarke et al.

affecting only slightly that of chalcopyrite (62%). When 1 minute of sonication is applied to the mineral
pulp before flotation, the recovery of chalcopyrite raises to 83% while that of sphalerite is restricted to less
than 6% with an improvement in the flotation kinetics of chalcopyrite (the flotation rate constant for
chalcopyrite increases from 0.2 to 0.9 min. -1 on sonication but remains unchanged for sphalerite). For the
galena-sphalerite mixture, the effects of sonication on the mineral separation are more pronounced with a
decrease in sphalerite recovery from 55% down to 20% and an increase in galena flotation from 71% to
81%. The larger flotation recovery of sphalerite observed before sonication when this mineral is associated
with galena than when it is associated with chalcopyrite is due to the larger dissolution of lead over copper
ions (from galena and chalcopyrite, respectively) [1,18] which activate the flotation of sphalerite [12,19,20].

100, • i I I I

Chalcopyrite
k = 2.1 min-1
8O &~ 300 W
8O W
60
OW
40
k -- 1.0 min-1

2o
>
o 0 t I i I ' I ~ I
L_
Galena
t-
O 8C
k = 1.7 min-1 - 300 W
0
,-r 60 80W

40
k" _ ,1 ow
S k = 1.3 min"
20

i I i I , I , I i

0 2 4 6 8 10
Flotation time (min.)
Fig.3 Flotation recovery of (top) chalcopyrite and (bottom) galena as a function of flotation time
and sonication power (pH=8.5; k is the flotation rate constan0.

XPS measurements of the flotation concentrate fraction reveals that sonication produces a less oxidized
surface and therefore exposes more the chalcopyrite surface (increase of the XPS signals of sulfur, iron and
copper) where the collector can adsorb (Figure 4). On the other hand, the zinc signal decreases, not because
of the reduced flotation of sphalerite but, because of the removal of the precipitated zinc hydroxide from
the chalcopyrite surface during sonication.

Attrition with quartz

The action of quartz present in an ore on the flotation of the other minerals is well known. Chander [21]
found that when the proportion of quartz particles contained in a chalcopyrite or pyrite quartz mixture is
 Removalof oxidationproductsfromsulfidemineralsurfaces 1353

increased, the flotal!ion of chalcopyrite and pyrite is improved. They have attributed this behaviour to the
preferential adsorption or precipitation, on the quartz surface rather than on the sulfide surface, of the metal
hydroxides formed in solution following their dissolution from the corresponding metal sulfide mineral.
Apart from this increase in flotation recovery, a corresponding decrease of the zeta potential of quartz was
observed, implying that some positively charged species, probably metal hydroxides, have adsorbed on the
quartz surface [21]. We have found that a similar trend is observed in the flotation recovery of sphalerite
in the presence of quartz with also a decrease of the quartz zeta potential (Figure 5). The magnitude of this
zeta potential decrease (10 mV) is rather small but comparable to that observed by Chander [21]. We add
that, to be able to raeasure the zeta potential, quartz particles of smaller size (and therefore larger surface
area) than in the flotation experiment have to be used, and this may explain the rather small decrease in
quartz zeta potential measured. The removal by quartz of oxidation products from a mineral surface already
oxidized seems to indicate that attritioning is the mode of surface cleaning by quartz [12].

1O0

"0 o

0 10 20 30 40 50 60
Sphalerite recovery (%)
40

30
¢-
(1)
t-
;!0
O

E
~

10
0
<
t3
0 S Zn Fe Cu 0 S Zn Fe Cu
Element
Fig.4 (top) Flotatio]a recovery of chalcopyrite versus flotation recovery of sphalerite without (.) and with
sonication (o). Flot~,tion recovery of galena versus flotation recovery of sphalerite without (A) and with
sonication (A) (pH= 8.5; 80 W sonication power for 1 min.; float fractions have been collected at 0.5, 2,
5 and 8 min.; the straight line represents the conditions of no selectivity). (bottom) XPS atomic
concentration of surface elements in the chalcopyrite-sphalerite flotation concentrate fraction
(the empty areas refer to the sample whose surface has been etched 2.5 nm).
1354 P. Clarke et al.

100 I I " | I

7
V

~, 80

8
,~ 60

iT" q
I i I i I i I

2o o 10 20 30 40 50
Quartz (%)
-40, , , '

~E,~"50
~ -60

~ -70

~4 -80
, I i I i I ,

"903 5 7 9
pH

Fig.5 (top) Flotation recovery of sphalerite as a function of the percentage of quartz in the mineral
mixture (pH=8.5). (bottom) Zeta potential of quartz as a function of pH and percentage of quartz
in the mineral mixture: (o) 100 %, (A) 43 %, (.) 25 % and (A) 11%.

EDTA extraction

EDTA, a strong complexant, has been used in mineral processing in two ways: first, to give information
about the amount of oxidation products covering the surface of minerals [22,23] and secondly, to remove
these surface oxidation products [24-27]. In this study, EDTA has already provided some information on
the level of oxidation on the sphalerite and galena surfaces. Figure 6 shows an increase in flotation recovery
of sphalerite and galena at intermediate concentrations of EDTA added and a decrease in flotation for higher
EDTA concentrations. Adsorption of EDTA on the mineral surface occurs at high EDTA concentrations as
indicated by the presence of characteristic peaks in the infrared spectra of sphalerite and galena [12]. EDTA,
with its carboxyl and amine groups, is a hydrophilic molecule which, when adsorbed on sphalerite and
galena, is likely to be responsible for the observed decrease in flotation of these minerals [24,26]. The
flotation maximum for galena and sphalerite occurs at different concentrations of added EDTA. These
EDTA concentrations for optimum flotation should reflect the affinity of EDTA for the various metal
species at the mineral surface and the concentration of these species. For example, the stability constant of
 Removal of oxidation products from sulfide mineral surfaces 1355

EDTA-Pb(II) (1018.0) is higher than that of EDTA-Zn(II) (1016.5) [28]. These values are much less than
the stability constant of PbS (1028.8) or ZnS (1025.1) [1,29] assuring that EDTA does not dissolve the metal
in the mineral lattice. This was verified experimentally by measuring the concentration of lead and zinc
dissolved from galena and sphalerite, respectively and it was found that with an increase in EDTA
concentration, the concentration of metal species dissolved reached a plateau [12].

901% o '
t/\
~ 70(~~ Galena . ..-----.-~

50

g 30
17"
100 1 n
2 I n

3
[EDTA]aaaed (10 .4 mol drrr3)

Fig.6 Flotation recovery of sphalerite and galena as a function of EDTA concentration (pH=8.5).

CONCLUSIONS

The results presentexl in this paper have indicated that several methods can be used to remove oxidation
products and in particular, metal hydroxides, from sulfide mineral surfaces. Both chemical (dissolution by
pH alteration, Cu(II) activation and EDTA extraction) and mechanical (sonication and attritioning with
quartz) means of removal have been tested. Their effectiveness in removing surface oxidation products has
been measured by flotation recovery and surface analytical techniques such as zeta potential and XPS
measurements.

The adjustment of the conditioning pH outside the pH range where metal hydroxides are formed leads to
an increase in mineral flotation recovery. It has been found that this method is more efficient in preventing
the formation and the precipitation of metal hydroxides rather than in removing them from the mineral
surface.

Cu(II), due to its high affinity for sulfide ions, displaces zinc hydroxide from the sphalerite surface and
exchanges with zinc ions in the sphalerite lattice. Its subsequent reduction to Cu(I) is associated with the
formation of elemental sulfur or polysulfide which, with the removal of zinc hydroxide, increase the overall
surface hydrophobicity and hence sphalerite flotation.

EDTA has also a strong affinity for mineral surfaces and more particularly with metal ions. Only weakly
attached metal species such as hydroxides can be dissolved by EDTA. However, an excess of either Cu(II)
or EDTA has a detrimental effect on the mineral flotation.
1356 P. Clarke et al.

Of the mechanical methods, sonication appears to be a method with a lot of potential to remove, selectively,
oxidation products from mineral surfaces.

The preferential adsorption onto the quartz surface of metal ions either dissolved or removed by attrition
from mineral surfaces leads to large improvements in flotation recovery, up to 50% in the case of sphalerite.

ACKNOWLEDGMENTS

Financial support for this work from the Australian Mineral Industries Research Association and the
Australian Research Council is gratefully acknowledged.

REFERENCES

. Fomasiero, D., Li, F., Ralston, J. & Smart, R. St., Oxidation of Galena Surfaces: I. X-
Ray Photoelectron Spectroscopic and Dissolution Kinetics Studies, J. of Colloid Interf.
Sci., 164, 333-344 (1994).
. Smart, R. St., Surface Analysis, AMIRA P260 report N ° 8, (Sep. 1990).
3. Fuerstenau, D.W., Fine Particle Flotation: Fine Particle Processing (ed., P. Somasundaran), Proc.
Int. Symp. Fine Particles Processing, Las Vegas, 1,669-705 (1980).
4. James, R.O. & Healy, T.W, Adsorption of hydrolysable metal ions at the oxide-water interface,
I-III, J. Colloid and Interface Sci., 40, 42-81 (1972).
5. Healy, T.W., Pulp chemistry, surface chemistry and flotation, Principles of Mineral Flotation,
Wark Symposium (eds., M.H. Jones and J.T. Woodcock) 43-56 (1984).
6. Montalti, M., Fornasiero, D. & Ralston, J., UV-visible spectroscopic study of the kinetics of
adsorption of ethyl xanthate on pyrite, J. of Colloid Interf. Sci., 143, 440--450 (1991).
7. Trahar, W.J. & Dunkin, M.H., The Effects of an excessive addition of copper sulphate on the
flotation of sphalerite, Proc. AUSIMM, 173, 13-29 (1954).
8. Finkelstein, N.P. & Allison, S.A., Flotation, A.M. Gaudin Memorial Volume, (ed., M.C.
Fuerstenau) Am. Inst. Min. Metall. Pet. Eng. Inc., New York, N.Y., 1, 414--457 (1976).
9. Baldwin, D.A., Manton, M.R., Pratt, J.M. & Storey, M.J., Studies on the flotation of sulphides. I.
The effect of Cu(lI) ions on the flotation of zinc sulphide, Int. J. Miner.Process., 6, 173-192
(1979).
10. Moignard, M.S., Dixon, D.R. & Healy, T.W., Electrokinetic Properties of the Zinc Sulphide-Water
and Nickel Sulphide-Water Interfaces, Proc. Aus. Inst. Min. Metall., 263, 31-38 (1977).
11. Parks, G.A., The Isoelectric Points of Oxides, Solid Hydroxides, and Aqueous Hydroxo Complexes
Systems, Chem. Reviews, 65, 177-198 (1965).
12. Clarke, P., The Interaction of Metal Ions and their Hydrolysis Products with Sulphide Mineral
Surfaces, Ph.D. Thesis, University of South Australia (1995).
13. Fuerstenau, D.W., The Principles of Flotation, South African Inst. Min. MetaU., Johannesburg,
183-198 (1982).
14. Wang, X., Forssberg, K.S.E. & Bolin, N.J., The Aqueous and Surface Chemistry of Activation in
the Flotation of Sulphide Minerals---A Review. Part I: An Electrochemical Model, Miner. Process.
Extract. MetaIl. Review, 4, 135-165 (1989).
15. Ralston, J. & Healy, T.W., Activation of zinc sulphide with Cu(II), Cd(II), Pb(II): I-II., Int. J. of
Miner. Process., , 7, 175-201 and 203-217 (1980).
16. Ralston, J., Alabaster, P. & Healy, T.W., Activation of zinc sulphide with Cu(II), Cd(lI), Pb(II):
IlL The mass-spectrometric determination of elemental sulphur, Int. J. Miner. Process., 7, 279-310
(1981).
17. Kristall, Z., Grano, S.R., Reynolds, K., Smart, R.St. & Ralston, J., An Investigation of Sphalerite
Flotation in the Murchison Zinc Concentrator, Fifth Mill Operators' Conference, Roxby Downs,
South Australia, 171-179 (1994).
18. Fairthorne, G., The Interaction Of Thionocarbamate Collectors with Sulphide Mineral Surfaces,
Ph.D. Thesis, University of South Australia (1995).
 Removalof oxidationproductsfrom sulfidemineral surfaces 1357

19. Yelloji Rao, M.K. & Natarajan, K.A., Effect of electrochemical interactions among sulfide minerals
and grinding medium on the flotation of sphalerite and chalcopyrite., Int. J. Miner. Process., 29,
175-194 (1990).
20. Rey, M. & Formanek, V., Some factors affecting the selectivity in the differential flotation of
lead-zinc ores, particularly in the presence of Oxidised Lead Minerals, Trans. Inst. Min. Metall,
London, 343-353 (1960).
21. Chander, S., Electrochemistry of sulphide flotation: Growth characteristics of surface coatings and
their properties, with special reference to chalcopyrite and pyrite, Int. J. Miner. Process., 33,
121-134 (1991).
22. Kant, C., Rao, S.R. & Finch, J.A., Distribution of Surface Metal Ions among the Products of
Chalcopyrite Flotation, Minerals Engineering, 7, 905-916 (1994).
23. Rumball, J.A. & Richmond, G.D., Measurement of Oxidation in a Base Metal Flotation Circuit.
Personal Communication (1994).
24. Wang, X. & Forssberg, E., A study of the natural and induced hydrophobicity of some sulphide
minerals by collectorless flotation, Processing of Complex Ores (eds. G.S. Dobby and S.R. Rao)
Pergamon, Elmsford, NY, 3-19 (1989).
25. Senior, G.D. & Trahar, W.J., The influence of metal hydroxides and collector on the flotation of
chalcopyrite, Int. J. of Miner. Process., 33, 321-341 (1991).
26. Pang, J. & Chander, S., The Effect of EDTA on Collectorless Flotation of Pyrite, Electrochemistry
in Mineral and Metal Processing--Ill, (eds., P.E. Richardson and R. Woods) TheElectrochemistry
Society, 92-17, 221-231 (1992).
27. Trahar, W.J., Senior, G.D & Shannon, L.K., Interactions between Sulphide Minerals--The
CoUectorless flotation of Pyrite, Int. J. of Miner. Process., 40, 287-321 (1994).
28. Martell, A.E. & Smith, R.M., Critical Stability Constants, Vol.1, Amino Acids, Plenum Press, New
York (1974).
29. Wang, X., The Chemistry of Flotation, Activation and Depression of Iron-containing Sulfide
Minerals, Ph.D. Thesis, Lulea University of Technology, Lulea, Sweden (1989).