Minerals Engineering 19 (2006) 860–869

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q
Marmatite depression in galena flotation
a,* b,1
Keith Quast , Gavin Hobart
a
Ian Wark Research Institute, University of South Australia, Mawson Lakes Campus, Mawson Lakes, SA 5095, Australia
b
Onesteel-Whyalla Steelworks, Whyalla, SA 5600, Australia

Received 13 July 2005; accepted 27 October 2005

Available online 19 December 2005

Abstract

Laboratory flotation tests were conducted to investigate the role of pH, zinc sulphate and potassium metabisulphite in the flotation of
galena and marmatite in the Broken Hill orebody. Marmatite was depressed under alkaline conditions alone, however the addition of the
two depressants, either individually or combined, resulted in the greatest selectivity. The use of zinc sulphate under alkaline conditions
resulted in good selectivity whilst maintaining a high lead recovery. The addition of potassium metabisulphite under alkaline conditions
reduced zinc recovery, but high additions reduced lead recovery. The addition of both depressants at alkaline pH produced the best
result, with a lead concentrate of 72.6% at 98% recovery with less than 4% zinc recovery. The overall aim of the study was to minimise
the flotation of marmatite into the galena rougher concentrate, which was achieved under the conditions given above.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Flotation reagents; Flotation depressants

1. Introduction Limited, has been published by Tilyard (1991) and Watters

The Broken Hill orebody was originally one of the
worldÕs largest massive sulphide deposits. A number of dis-
tinct orebodies exist in the Broken Hill deposit, each with
its own characteristic association of gangue minerals and
its own distinguishing metal ratio. Galena, PbS (86.6%
Pb) is the major lead mineral, with the zinc being present
as marmatite (Zn,Fe)S, an iron rich sphalerite containing
9–11% iron. Silver is present as argentiferous galena and
tetrahedrite, also as pyrargyrite and argentite. The major
gangue minerals present are quartz, calcite, rhodonite, gar-
net, feldspar and fluorite (Higgins and Quast, 1992). Brief
histories of the operation of the South Concentrator, previ-
ously owned by Pasminco Mining, now operated by Perilya
q
Paper originally published in Proceedings Centenary of Flotation
Symposium, Brisbane, Australia, 5–9 June, 2005 by the Australasian
Institute of Mining and Metallurgy.
*
Corresponding author. Tel.: +618 8302 3816; fax: +618 8302 3683.
E-mail addresses: Keith.Quast@unisa.edu.au (K. Quast), HobartG
@onesteel.com (G. Hobart).
1
Tel.: +618 8644 5508.
(1993).
The aim of this paper is to examine lead/zinc selectivity
by manipulating pH in the range 7.5–9.5, the addition of
zinc sulphate between 0 and 200 g/t, and the addition of
potassium metabisulphite between 0 and 1000 g/t.
2. Literature review
2.1. Effect of pH
Historically, ore flotation at the South Concentrator of
Pasminco Mining was conducted at a natural pH of 7–8,
although lime is often added to pH 8 (Burgess, 1992).
The significance of pH as a flotation variable has become
more apparent with the introduction of cemented backfill-
ing techniques. Although laboratory testing showed no sig-
nificant difference between cement and lime as a pH
modifier, lead recovery suffered at pH values of 10 or
higher (Gauci and Cusack, 1971). Wark and Cox (1934)
showed that air–mineral contact for galena in the presence
of 25 ppm ethyl xanthate was only possible for a pH less

0892-6875/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.10.022
 K. Quast, G. Hobart / Minerals Engineering 19 (2006) 860–869
than 10.7. Cusack and Stump (1977) reported that galena
losses in deleaded tailing only reached 10% above pH 11
in mill water, however this loss was noted at pH 9 using
fresh water. Sutherland and Wark (1955) observed that
the depressant action of lime was due to the formation of
a finely dispersed hydrophilic film of lime on the surface
of the sphalerite.
Finkelstein and Allison (1976) state that galena floats
selectively from sphalerite in a slightly alkaline environ-
ment (pH 8–10), with the sphalerite having to be activated
(usually by copper ions) before it floats. Higgins and Quast
(1992) showed that the addition of lime tended to slightly
depress galena flotation, but substantially depress marma-
tite flotation.
Bulatovic and Wyslouzil (1999) examined the addition
of soda ash and lime on lead recovery from two complex
Canadian lead–zinc ores. Depending on the ore, either
soda ash or lime gave a maximum in lead recovery at about
pH 9.
2.2. Addition of zinc sulphate
Sphalerite tends to resist oxidation, thus very few zinc
ions dissolve from the mineral. To ensure zinc sulphide
activation is prevented, the activity of zinc ions should be
1000 times that of lead ions in solution. As little zinc ions
are present in solution, zinc sulphate is added. Hence, by
virtue of the equilibria involving basic lead carbonate and
zinc hydroxide, the activity of zinc ions to lead ions is
higher than the equilibrium ratio, and activity cannot
occur. Solozhenkin and Vasyukevitch (cited by Finkelstein
and Allison, 1976) concluded that the adsorption of zinc
ions by marmatite, chalcopyrite and pyrite followed much
the same path as was observed with sphalerite, except that
adsorption was generally higher.
In addition to thermodynamic considerations, there is
considerable evidence that indicates that the colloids of
zinc salts, formed under conditions where precipitation
occurs, function as depressants for sphalerite. These
include precipitates of zinc hydroxide, zinc carbonate, zinc
sulphite and zinc cyanide. The depressant role of zinc
hydroxide colloids was presented by Malinovsky in 1946
(cited by Klassen and Mokrousov, 1963). He established
that zinc sulphate alone was unable to depress sphalerite,
the depressant action of zinc sulphate only occurred in
the presence of hydroxyl ions. Test work by Malinovsky
indicated that an increase in the alkalinity of the pulp
increased the depressing action of zinc sulphate, with zinc
hydroxide first precipitating at a pH of 5.2. He proposed
that the depressing action of zinc hydroxide was due to
the zinc hydroxide being adsorbed on the surface of the
sphalerite and preventing the adsorption of xanthate.
These observations were later confirmed by Livshitz and
Idelson (also cited by Klassen and Mokrousov (1963))
who demonstrated that the extent of depression of sphaler-
ite and the concentration of colloidal zinc hydroxide occur-
ring in the pulp were directly related.
861
Finkelstein and Allison (1976) summarised the possible
explanations for the adsorption of these colloidal precipi-
tates on the sphalerite surface as:
(1) A precipitate is formed in the bulk solution and
attaches itself by physical forces to the surface (i.e.
agglomeration or coagulation).
(2) A precipitate is formed, or reprecipitates, at the sur-
face through the action of nucleating sites.
(3) A monolayer of zinc hydroxy species chemisorbs at
the sphalerite surface (e.g. through an oxygen bridge)
thus providing a suitable surface for the attachment
of or the reprecipitation of precipitates formed in
the bulk.
(4) A bulk precipitate chemisorbs at the surface.
Grano et al. (1988) used zinc sulphate as a sphalerite
depressant in the flotation of galena from the heavy med-
ium slimes stream in the Mount Isa lead–zinc concentrator.
The addition of zinc sulphate plus either soda ash or lime
for pH control resulted in the depression of the sphalerite
while not affecting the flotation of the galena. Plant flota-
tion results showed that the addition of 0.9 kg/t of zinc sul-
phate at pH 8.5 halved the zinc grade of the lead
concentrate at almost one third of the zinc recovery.
El-Shall et al. (2000) examined the role of zinc sulphate
in the depression of lead-activated sphalerite from a more
fundamental point of view. They found that the activation
of sphalerite by lead ions was due to a replacement reaction
where lead replaces zinc on the surface. Depression of lead-
activated sphalerite by zinc sulphate was thought due to a
reversal of the activation reaction.
2.3. Addition of metabisulphite
Misra et al. (1985) reported that sulphite can be used to
depress sphalerite if added to the system prior to the addi-
tion of xanthate. Generally the sulphite is added in grind-
ing or during conditioning, the amount varying from 1 to
2 kg/t of ore. These workers reported that sulphite has been
used previously at Broken Hill as a zinc depressant and
also as a cleaning reagent for oxidised galena. The conclu-
sions from this study were:
(1) Contact angle measurements and flotation experi-
ments indicated that the addition of sulphite before
xanthate resulted in effective sphalerite depression.
(2) The homogeneous phase decomposition reaction of
xanthate in the presence of sulphite was dependent
on the SO2/xanthate mole ratio, dissolved oxygen
concentration and pH. The rate of decomposition
was very rapid at near neutral pH (6–6.5).
(3) Xanthate adsorption on sphalerite was limited to an
effective monolayer coverage.
(4) The selective depression of sphalerite by sulphite was
related to the relative rates of xanthate adsorption in
comparison to xanthate decomposition.
862 K. Quast, G. Hobart / Minerals Engineering 19 (2006) 860–869

Several possible mechanisms have been suggested for the
depressing action of sulphite on sphalerite and also as a flo-
tation modifier during the flotation of sulphide ore. These
mechanisms include:
(1) Formation of a hydrophilic surface coating such as
zinc sulphite or calcium sulphate (when lime is used
as a pH regulator).
(2) Formation of insoluble heavy metal sulphite salts and
subsequent reduction in the heavy metal ion concen-
tration in the pulp, thus preventing unintentional
activation.
(3) Xanthate decomposition due to sulphite promoted
oxidation reaction.
(4) Limited collector adsorption by control of the redox
potential.
Yamamoto (1980) stated that the simultaneous use of
zinc ions and sulphite depressed the flotation of sphalerite,
but the use of sulphite alone did not. He concluded that
ethyl xanthate adsorbed on the surface of activated sphal-
erite was not desorbed by sulphite ion.
Yamamoto (1980) supported the findings of Misra et al.
(1985) in the fact that the presence of both oxygen and sul-
phite together results in the decomposition of xanthate to
form perxanthate. In the alkaline pH range, the xanthate
decomposition was slow, but this does not correspond to
the depression of sphalerite which is possible in the pres-
ence of sulphite in the alkaline pH range. Depression of
sphalerite at higher alkalinity is more probably due to the
competition of other anions with xanthate for surface sites.
Depression at lower pH values is probably due to the
decomposition of xanthate.
Pattison (1983) reported that for unactivated sphalerite,
the likely formation of zinc sulphite species may be
expected to result in depression, although the results of
Mitrofanov and Kusnikova (1957) revealed little difference
(in alkaline solution) in the xanthate uptake of unactivated
sphalerite whether sulphite was present or not. PattisonÕs
experiments produced only trace flotation of unactivated
sphalerite with ethyl xanthate collector regardless of
whether sulphite was used in the flotation system. He con-
cluded that the mineral tested had only a limited number
of surface sites available for collection possibly because
of some degree of unintentional activation, or because of
the iron content of the sphalerite, and that the sulphite
did not prevent this limited collection. For copper-acti-
vated sphalerite, it was demonstrated that sodium sulphite

45
45 0 ZnSO4
pH 7.5
100 ZnSO4
pH 8.5
200 ZnSO4
pH 9.5 40
40

35
35

30
30
Zinc Recovery (%)
Zinc Recovery (%)

25
25

20
20

15
15

10
10

5
5

0
0 50 60 70 80 90 100
50 60 70 80 90 100 Lead Recovery (%)
Lead Recovery (%)
Fig. 2. Effect of zinc sulphate addition (in g/t) on lead/zinc selectivity at
Fig. 1. Effect of pH on lead/zinc selectivity. pH 7.5.
 K. Quast, G. Hobart / Minerals Engineering 19 (2006) 860–869
was quite an effective depressant in alkaline solution, but
that the rate of sphalerite flotation was actually enhanced
near to neutral pH by the presence of sulphite.
Grano et al. (1997) also investigated the effect of adding
sodium metabisulphite (MBS) to the flotation of the Hilton
lead–zinc ore. Previous work on the interaction of sodium
metabisulphite and ethyl xanthate for the galena flotation
from Hilton ore had been reported by Sheldon and John-
son (1988). They identified temperature and contact time
as important parameters in the pilot scale processing of this
ore. Grano et al. (1997) found that the simultaneous addi-
tion of xanthate and MBS decreased galena recovery due
to ethyl xanthate decomposition by sulphite ion derived
from MBS. The depression increased with increasing
MBS addition and pulp temperature. Under these condi-
tions there was an increase in the concentration of metasta-
ble ethyl perxanthate in solution, an intermediate product
of xanthate decomposition by sulphite ion. Pulp chemical
measurements in the Hilton Concentrator also showed
increased ethyl perxanthate concentration when MBS was
added at the same point in the flotation circuit as ethyl xan-
thate. In contrast, the application of an aeration stage after
MBS addition, but prior to ethyl xanthate addition,
45
0 ZnSO4
100 ZnSO4
200 ZnSO4
40
35
30
Zinc Recovery (%)
25
20
15
10
0 0
50 60 70 80 90 100
Lead Recovery (%)
Fig. 3. Effect of zinc sulphate addition (in g/t) on lead/zinc selectivity at
pH 8.5.
863
decreased the concentration of unreacted sulphite ion. This
was demonstrated by a decreased ethyl perxanthate con-
centration in solution and restored galena flotation recov-
ery. Under these conditions the dependency of galena
flotation on MBS (and temperature) was less marked. Pre-
vention of the solution decomposition of ethyl xanthate by
sulphite allowed the depressant action of MBS on sphaler-
ite (and iron sulphide) flotation to be optimised.
3. Materials and equipment
The material examined was provided by the then opera-
tors of the Pasminco South concentrator. This was received
as roughly 1.1 kg moist samples of primary cyclone under-
flow. The head grade of this ore was 8.5% lead, 60 g/t silver
and 10.5% zinc. Adelaide tap water was used throughout
the test work. The reagents used were sodium ethyl xan-
thate, methyl isobutyl carbinol (MIBC), zinc sulphate
and potassium metabisulphite.
The charges of cyclone underflow were ground in a
Linatex lined laboratory rod mill charged with 12 stainless
steel rods. Flotation tests were performed in a 2.5 l capac-
ity Agitair flotation cell attached to a Galigher Agitair
10
0 ZnSO4
100 ZnSO4
200 ZnSO4
8
6
Zinc Recovery (%)
2
50 60 70 80 90 100
Lead recovery (%)
Fig. 4. Effect of zinc sulphate addition (in g/t) on lead/zinc selectivity at
pH 9.5.
864 K. Quast, G. Hobart / Minerals Engineering 19 (2006) 860–869

flotation machine model LA-500. Values of pH were mea-
sured using a TPS Auto pH meter.
4. Procedure
4.1. Grinding
The grind time required to match the rougher feed sizing
on the plant (80% passing 200 lm) was determined by
grinding the charges with 650 ml of Adelaide tap water.
4.2. Flotation
The ground ore was washed into the flotation cell and
water added to raise the level of slurry to within 25 mm
of the overflow weir. If depressants were used, they were
added as dilute solutions and the pH adjusted using lime
if required. The pulp was conditioned for 5 min prior to
adding the collector and frother, at 50 g/t and 10 g/t
respectively. The pulp was then conditioned for a further
2 min, then aerated at 3 l/min. Two concentrate products
were removed into separate containers over one minute
intervals by scraping every 15 s.
A second reagent addition of sodium ethyl xanthate and
MIBC was made, 10 g/t of each. The pulp was again con-
ditioned for 2 min, then aerated and four more concen-
trates were floated over one minute intervals by scraping
every 15 s. The six flotation concentrates and tailings from
each test were filtered and dried. A sample of rougher tail
was riffled out and this plus all concentrate products were
pulverised and analysed by the Pasminco South Mine assay
department.
5. Results
5.1. Grinding test
A 20 min grind produced a flotation feed with 80% pass-
ing 175 lm, and this was used throughout the test program.
The flotation test results are presented as a series of
graphs in Figs. 1–10 and a summary of final lead and zinc
grades and recoveries presented in Table 1.
In order to compare the effects of the reagent additions
on lead and zinc flotation behaviour, the flotation data
were subjected to analysis using the first order rate equa-
tion given below:

45
45 0 MBS
0 MBS 500 MBS
500 MBS 1000 MBS
1000 MBS 40
40

35
35

30
30
Zinc Recovery (%)

25
Zinc Recovery (%)

25

20
20

15 15

10 10

5 5

0 0
50 60 70 80 90 100 50 60 70 80 90 100
Lead Recovery (%) Lead Recovery (%)

Fig. 5. Effect of metabisulphite addition (in g/t) on lead/zinc selectivity at Fig. 6. Effect of metabisulphite addition (in g/t) on lead/zinc selectivity at
pH 7.5. pH 8.5.
 K. Quast, G. Hobart / Minerals Engineering 19 (2006) 860–869
10
0 MBS
500 MBS
1000 MBS
8 8
6
Zinc Recovery (%)
4
2
0
50 60 70 80
Lead Recovery (%)
Fig. 7. Effect of metabisulphite addition on lead/zinc selectivity at pH 9.5.
RðtÞ ¼ Rmax ð1  expðktÞ
where R(t) is the recovery of mineral at time t, Rmax is the
theoretical maximum recovery (at infinite time by curve fit-
ting the experimental data) and k is the rate constant in
units of time1. The data were fitted to the equation using
a least squares fit program, giving the data listed in Table 2.
The rate data were only reported to 1 decimal place and the
Rmax data to the nearest integer in keeping with the accu-
racy of the experimental data.
6. Discussion
The laboratory grinding size comparison to the plant
flotation feed sizing, although not presented here, showed
a slightly reduced amount of material coarser than
300 lm compared to the plant feed, possibly as a conse-
quence of using a laboratory rod mill rather than a labora-
tory ball mill. The 80% passing size of the laboratory
20 min grind was 175 lm compared to the plant value of
200 lm. Under these conditions, liberation should be
almost complete, as Cusack and Stump (1977) reported
that grinding this ore to 92.5% passing 300 lm achieved
96% liberation of the lead and zinc sulphides.
865
10
100/500 g/t
200/500 g/t
100/1000 g/t
200/1000 g/t
6
Zinc Recovery (%)
4
2
90 100 0
70 80 90 100
Lead Recovery (%)
Fig. 8. Effect of combined depressant addition (ZnSO4/MBS in g/t) on
lead/zinc selectivity at pH 7.5.
ð1Þ
Fig. 1 shows that lime depresses zinc, particularly at pH
9.5, where zinc recovery was only 6.6% compared to 30–
40% for pH 7.5 and 8.5. The selectivity fell away after
the second and third stages of flotation at pH 7.5 and
8.5, possibly due to the fact that most of the fast floating
galena had already been floated, so zinc began to float.
Similar results were also reported by Higgins and Quast
(1992) for ore from the same mine, who found that pH
9.5 resulted in the greatest lead/zinc selectivity. The flota-
tion of the marmatite at the lower pH values could be
greater in the laboratory than at the concentrator due to
the use of Adelaide tap water that would not have the same
concentration of zinc ions present in the circuit water used
at Broken Hill.
Figs. 2 and 3 show that the addition of small amounts of
zinc sulphate greatly increased the lead/zinc selectivity at
pH 7.5 and 8.5. At pH 9.5 the effect was not as pronounced
(Fig. 3). From Table 1, at pH 7.5 and 100 g/t zinc sulphate,
the zinc recovery was 6.3%, whereas at pH 9.5 and 200 g/t
zinc sulphate addition, the zinc recovery was 4.7%. The
addition of zinc sulphate had no effect on lead recov-
ery, with higher lead grades corresponding to higher zinc
866 K. Quast, G. Hobart / Minerals Engineering 19 (2006) 860–869
10
100/500 g/t
200/500 g/t
100/1000 g/t
200/1000 g/t
8 8
6 6
Zinc Recovery (%)
4
2
0 70
70 80
Lead Recovery (%)
Fig. 9. Effect of combined depressant addition (ZnSO4/MBS in g/t) on
lead/zinc selectivity at pH 8.5.
sulphate additions at pH 9.5 (see Table 1). Similar results
were also reported by Higgins and Quast (1992). The best
results using pH and zinc sulphate additions corresponded
to the addition of 200 g/t at pH 9.5, where a lead recovery
of 98.7% at a grade of 70.1%, with a zinc recovery of only
4.7% (see Table 1).
This result supports the work of both Malinovsky and
Livshitz and Idelson (both cited by Klassen and Mokrou-
sov, 1963) in that more alkaline conditions provided an
increase in hydroxyl ions, and, along with the greater pres-
ence of zinc ions, more colloidal zinc hydroxide will be
formed. This would precipitate on the surface of the mar-
matite and prevents the adsorption of the xanthate, and
Livshitz and Idelson demonstrated that the extent of sphal-
erite depression was related to the concentration of colloi-
dal zinc hydroxide in the pulp.
The results in Figs. 5–7 show that the use of metab-
isulphite alone depressed marmatite, although Yamamoto
(1980), Mitrofanov and Kusnikova (1957) and Pattison
(1983) suggested that sulphite had little depressant activity
on sphalerite in the absence of zinc ions. The addition of
MBS was very effective in depressing the marmatite, espe-
10
100/500 g/t
200/500 g/t
100/1000 g/t
200/1000 g/t
Zinc Recovery (%)
4
2
0
80 90 100
90 100 Lead Recovery (%)
Fig. 10. Effect of combined depressant addition (ZnSO4/MBS in g/t) on
lead/zinc selectivity at pH 9.5.
cially at the higher addition (1000 g/t). The lower additions
of MBS were not as effective as marmatite depressants as
the zinc sulphate, however lead recovery remained very
high at 98% (see Table 1). The higher addition resulted in
very low zinc recoveries, but lead recovery was slightly
reduced. The decision as to the optimum additions and
conditions rest with the plant operation philosophy i.e. is
a higher lead grade or higher recovery the most desirable.
It must be remembered that these are roughing tests, so
some of the marmatite that floats here could possibly drop
out in the lead cleaning stages.
The fact that this test work was performed in the alka-
line region would appear to reject the proposals of Misra
et al. (1985). Their concept of the depressant action of sul-
phites was due to xanthate decomposition at neutral pH,
with very little decomposition of xanthate to perxanthate
at pH 9.5. Pattison (1983) also reported that sulphite was
a successful depressant for copper-activated sphalerite,
but the presence of sulphite had little effect on unactivated
sphalerite. This was not the case in the present study. By
adding and conditioning the MBS ahead of xanthate addi-
tion seemed to avoid the xanthate decomposition by MBS
noted by Grano et al. (1997).
 K. Quast, G. Hobart / Minerals Engineering 19 (2006) 860–869 867

Table 1
Final grades and recoveries for lead and zinc
Test no. pH Zinc sulph. (g/t) Pot. meta. (g/t) Lead (%) Zinc (%)
Gde. Rec. Gde. Rec.
1 7.5 – – 49.2 93.6 18.4 27.6
2 8.5 – – 41.5 96.2 23.5 40.2
3 9.5 – – 67.0 97.4 5.7 6.6
4 7.5 100 – 61.1 98.7 5.5 6.3
5 8.5 100 – 66.2 97.4 5.3 5.8
6 9.5 100 – 68.8 98.6 5.1 5.4
7 7.5 200 – 68.1 97.5 4.5 5.0
8 8.5 200 – 67.1 97.9 4.7 4.9
9 9.5 200 – 70.1 98.7 3.8 4.7
10 7.5 – 500 56.8 97.6 11.2 13.8
11 8.5 – 500 66.8 98.4 6.8 8.0
12 9.5 – 500 69.5 97.9 5.1 8.3
13 7.5 – 1000 67.8 96.4 4.9 6.5
14 8.5 – 1000 72.4 95.4 3.5 3.3
15 9.5 – 1000 69.9 95.4 4.6 4.0
16 7.5 100 500 63.9 98.1 5.1 6.1
17 8.5 100 500 68.7 97.7 4.2 4.7
18 9.5 100 500 72.6 98.0 3.3 3.7
19 7.5 200 500 64.7 97.2 4.9 5.4
20 8.5 200 500 68.5 97.5 4.2 4.5
21 9.5 200 500 62.7 97.2 5.7 6.7
22 7.5 100 1000 71.2 97.4 3.6 3.9
23 8.5 100 1000 72.7 97.5 3.7 4.0
24 9.5 100 1000 65.1 96.9 5.3 5.5
25 7.5 200 1000 67.7 96.5 4.5 4.7
26 8.5 200 1000 66.3 97.0 4.8 5.2
27 9.5 200 1000 66.1 96.3 4.9 5.1

Table 2
Calculated values of rate constants (min1) and Rmax (%) for tests
Test no. pH Zinc sulph. (g/t) Pot. meta. (g/t) Lead Zinc
k Rmax k Rmax
1 7.5 – – 0.9 100 0.4 31
2 8.5 – – 1.0 96 0.1 100
3 9.5 – – 1.0 98 0.5 7
4 7.5 100 – 1.6 97 0.5 6
5 8.5 100 – 1.6 97 0.5 6
6 9.5 100 – 1.6 98 0.6 5
7 7.5 200 – 2.0 96 0.8 5
8 8.5 200 – 1.6 97 0.5 5
9 9.5 200 – 1.4 99 0.4 5
10 7.5 – 500 1.1 99 0.2 20
11 8.5 – 500 1.8 97 0.5 6
12 9.5 – 500 2.0 96 0.6 7
13 7.5 – 1000 1.7 95 0.4 7
14 8.5 – 1000 2.0 94 0.8 3
15 9.5 – 1000 1.9 94 0.6 4
16 7.5 100 500 2.1 97 0.4 7
17 8.5 100 500 1.5 96 0.4 5
18 9.5 100 500 1.8 97 0.7 3
19 7.5 200 500 1.9 95 0.5 4
20 8.5 200 500 1.9 96 0.3 6
21 9.5 200 500 2.1 95 0.6 6
22 7.5 100 1000 2.0 96 0.5 4
23 8.5 100 1000 1.6 96 0.5 4
24 9.5 100 1000 2.0 95 0.5 5
25 7.5 200 1000 1.5 94 0.4 5
26 8.5 200 1000 2.0 96 0.4 6
27 9.5 200 1000 2.0 95 0.6 4
868 K. Quast, G. Hobart / Minerals Engineering 19 (2006) 860–869
The effects of adding various combinations of zinc sul-
phate and MBS on lead/zinc selectivity are shown in Figs.
8–10. Comparing these figures reveals similar trends to
those observed previously for the reagents added individu-
ally. It is obvious that pH plays a significant role in the
effects of different concentrations of reagents. For the lower
pH ranges, results indicate that the best selectivity occurred
with the addition of 100 g/t zinc sulphate and 1000 g/t
MBS, where at pH 8.5, lead recovery was 97.5% and zinc
recovery 4.0%. The best overall result was pH 9.5, 100 g/t
zinc sulphate and 500 g/t MBS, giving 98% lead recovery
and 3.7% zinc recovery (see Table 1). The overall aim of
this test program was to minimise the misreporting of zinc
to the lead concentrate.
The depression of the marmatite when both depressants
are added is expected to be due to the formation of zinc sul-
phite. When this forms, it is adsorbed onto the surface of
the marmatite, resulting in competition for surface sites
between those anions and xanthate as proposed by Misra
et al. (1985) under alkaline conditions. The result of the
depressive action of zinc sulphate and MBS together is also
supported by Yamamoto (1980) who observed that sphal-
erite flotation was depressed by the simultaneous use of
zinc ions and sulphite.
The kinetic data reported in Table 2 generally support
the experimental data listed in Table 1. Values of the flota-
tion rate constant for the galena are always greater than for
the marmatite as would be expected. The high zinc recov-
eries reported for Tests 1, 2 and 10 in Table 1 are also evi-
dent in Table 2. Ignoring these zinc data, the comparative
flotation rate data corresponding to the various conditions
can be compared. From Table 1, the ‘‘best’’ test was Test
18, and the kinetic analysis showed a very low Rmax for zinc
(3%), even though the rate constant for the zinc was rela-
tively high. The corresponding rate constant for the lead
was moderate and Rmax high, all supporting the values
reported in Table 1 for this test. Unfortunately no replica-
tion testing was conducted at the time of this test program.
The laboratory results were only to be used as a guide to
possible improvements in plant performance, with the main
aim of minimising the recovery of marmatite into the
galena rougher concentrate.
7. Conclusions
The addition of lime to increase the pH to 9.5 in the
absence of the addition of any other zinc depressants was
effective in reducing marmatite flotation. This was thought
to be due to the formation of a thin film of lime on the sur-
face of the marmatite. The addition of zinc sulphate
resulted in marmatite depression and increased lead/zinc
selectivity at higher pH and zinc sulphate additions. This
was believed due to the formation of a zinc hydroxide pre-
cipitate on the marmatite surface, thus hindering xanthate
adsorption. The addition of MBS also increased lead/zinc
selectivity, but galena recoveries can be reduced at higher
MBS additions. The best results observed in this laboratory
test program was the addition of 100 g/t zinc sulphate and
500 g/t MBS at pH 9.5. Under these conditions, lead recov-
ery was 98% at 72.6% grade and zinc recovery into the lead
concentrate was only 3.7% at 3.3% zinc grade. Kinetic
analysis supported the experimental data, with the minimi-
sation in zinc recovery to the overall lead concentrate being
the main driver for the test program.
Acknowledgements
The authors are very grateful to the staff of the Metal-
lurgy and Assay departments of the then Pasminco South
Concentrator at Broken Hill at the time this study was
undertaken. The authors also wish to thank the manage-
ment of Perilya Limited, the current operator of this mine
and concentrator, for permission to publish this paper.
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