Minerals Engineering 21 (2008) 905912

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

A discussion of the occurrence and undesirable otation behaviour

of orthopyroxene and talc in the processing of mac deposits
N.O. Lotter a,*, D.J. Bradshaw b, M. Becker b, L.A.S. Parolis b, L.J. Kormos a
a
b

Process Mineralogy Group, Xstrata Process Support, Falconbridge, Ontario, Canada P0M 1S0
Centre for Minerals Research, Department of Chemical Engineering, University of Cape Town, South Africa

a r t i c l e

i n f o

Article history:
Received 28 November 2007
Accepted 26 February 2008

Keywords:
Flotation
Orthopyroxene
Activation

a b s t r a c t
In the processing of sulphide ores, there is generally a concentration step such as otation, before smelting. One of the problems arising in the smelter is the presence of MgO and one of the major challenges in
the otation step is to reduce the amount of MgO recovered to the concentrate and thus reporting to the
smelter. The reporting of MgO in concentrates is a pseudo-representation of the range of actual magnesium-bearing minerals which are present in the ore and concentrator products. However, since the total
amount of MgO present in a concentrate is what drives the smelting problem, regardless of which mineral source, the MgO content is the measurement of interest.
One of the major sources of MgO is pyroxene, and particularly orthopyroxene. The common occurrence
of talc, which also bears MgO, in association with orthopyroxene, warrants additional focus on this mineral. This paper reviews the occurrences of pyroxene and talc in sulphide ore bodies, focussing on the
Merensky ore in South Africa and the Sudbury ores in Canada. The various mechanisms by which it
reports to the concentrate and methods of reducing these mechanisms, are discussed.
Four mechanisms have been identied and each of these has a different treatment route that are quite
wide ranging in effort and cost This paper shows the importance of identifying the mechanisms involved
so that the correct treatment can be used. The incorrect treatment can prove costly but in many cases
ineffective a principle of project management that is wider than this paper alone. It also shows the valuable contribution that quantitative mineralogy/process mineralogy makes to process diagnosis and
optimisation.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
In the processing of sulphide ores, there is generally a concentration step such as otation, before smelting. One of the problems
arising in the smelter is the presence of MgO. Elevated MgO
grades of nickel concentrates cause furnace operational problems
in downstream processing. This is because of increased liquidus
temperature and slag viscosity, requiring the furnace to operate
at higher temperatures, also shortening campaign life of the furnace (Jung et al., 2004). Thus one of the major challenges in the otation step is to reduce the amount of MgO recovered to the
concentrate and thus reporting to the smelter. Since the total
amount of MgO present in a concentrate is what drives the smelting problem, regardless of which mineral source, the MgO content
is the measurement of interest. The reporting of MgO in concentrates is a pseudo-representation of the actual magnesium-bearing
minerals which are present in the ore and concentrator products.
Amongst other sources, such as talc, a major source of MgO is

* Corresponding author. Tel.: +1 705 693 2761; fax: +1 705 699 3431.
E-mail address: nlotter@xstrataprocesssupport.ca (N.O. Lotter).
0892-6875/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2008.02.023

orthopyroxene and as such, any recovery of this mineral to otation concentrate would signicantly inuence the overall MgO
content of that concentrate.
Orthopyroxene has been selected as the focus of this paper in
the context of two orebodies where its recovery has been reported
as problematic, viz Bushveld Igneous Complex (BIC) in (South Africa (OConnor et al., 2006; Becker et al., 2006)) and Sudbury Igneous
Complex (SIC) in Canada (Lotter et al., 2003). There are other factors that have not been specically addressed in this paper, such
as the reduction of paymetal recovery to concentrate resulting
from presence of pyroxene and other gangue minerals, sometimes
resulting from the effect on froth stability or other means.
2. Geology and mineralogy
2.1. Composition of orthopyroxene
Orthopyroxene is a magnesium-rich ferro-magnesian inosilicate containing approximately 2735% MgO (Deer et al., 1963)
and is the generic name given to minerals with a composition
intermediate to the Mg-rich end-member (enstatite Mg2Si2O6)

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N.O. Lotter et al. / Minerals Engineering 21 (2008) 905912

2.2. Bushveld Merensky

and Fe-rich end-member (ferrosilite Fe2Si2O6) of the pyroxene

mineral group. The prex ortho is derived from its orthorhombic
crystal structure and is distinct from clinopyroxene which is a
Ca-rich end-member. Orthopyroxene is a commonly occurring
rock-forming mineral, and is one of the major silicate mineral components of mineral deposits bearing economic amounts of Ni and
Cu, and in some cases platinum-bearing minerals. This is due to
the similar geochemical characteristics of these metalliferous elements and their partitioning during the formation of these igneous
deposits. However, the composition of the orthopyroxene in the
economic zones of the abovementioned deposits generally tends
to be more Mg-rich than Fe-rich, with a characteristic Mg to Mg
plus Fe ratio (e.g., Mg2+/(Mg2+ + Fe2+) = 0.70  0.90; Scribbins
et al., 1984; Cameron, 1980; Cameron, 1982; Atkins, 1969; Naldrett
and Kullerud, 1969). Examples of these deposits are the wellknown orebodies associated with the Bushveld Igneous Complex
in South Africa and Sudbury Igneous Complex in Canada.
The geochemical denition of orthopyroxene is shown in Fig. 1.
Both the Bushveld and Sudbury Igneous Complexes are relatively ancient deposits, dated at 2.06 and 1.85 Ga respectively. It
is therefore not unexpected to nd the alteration of the anhydrous
primary orthopyroxene into hydrous alteration product minerals
such as talc (Mg6Si8O20(OH)4). This has been recognised in fundamental mineralogical studies (e.g., Viti et al., 2005; Zingg et al.,
1996; Hemley et al., 1977; Nesbitt and Bricker, 1977) as well as
the more applied studies, and may be manifested as talc forming
along rims and cleavage planes of the orthopyroxene crystals
(Becker et al., 2006; Li et al., 2004; Penberthy and Merkle, 1999).
The occurrence of talc rims on orthopyroxene in both the Bushveld
and Sudbury Igneous Complexes may be a localised phenomenon,
since zones of unaltered orthopyroxene can also occur. This provides additional motivation as to why a fundamental understanding of the otation properties of both orthopyroxene and talc is
needed if they may commonly occur as binary particles within
the otation circuit. In fact, Sudbury studies show liberated, unaltered orthopyroxene is sometimes recovered to concentrate. The
mechanisms responsible for such recovery need to be understood
(Di Feo et al., 2006). Further, the presence of liberated talc in minor
to signicant quantities in the otation process should be considered, because of the interactions this produces with that otation
system.

The Bushveld Igneous Complex is an extensive geological system, comprising various limbs in the Northwest and Limpopo
Provinces of South Africa and with some evidence of its extension
under surcial cover into Botswana. The main economic interest of
the Bushveld Complex lies within the so-called Critical Zone, one of
a series of discrete layered zones within the complex. The Critical
Zone is host to the Merensky Reef and the UG2 Chromitite, both
carrying Platinum-Group Elements (PGE) in a complex array of discrete PGM and sulphide solid solution species of PGE. The Merensky Reef is also exploited for its Ni and Cu, hosted by the sulphides
pentlandite and chalcopyrite.
Both the Merensky Reef and UG2 essentially comprise the same
major minerals although showing distinct variations in texture and
relative abundance of the minerals. The base of the Merensky Reef
comprises a pegmatoidal feldspathic pyroxenite sandwiched between two thin chromitite layers. Overlying the second of these
chromitite layers, the pyroxentite grades upward into a norite
(orthopyroxene and plagioclase rich rock) and anorthosite (plagioclase rich rock). The pegmatoidal feldspathic pyroxenite layer is
typically heterogeneous varying in thickness from mine to mine
(up to 5 m) and with euhedral to subhedral pyroxene crystals
reaching up to a few centimetres in size (Viring and Cowell,
1999; Leeb-Du Toit et al., 1986; Viljoen et al., 1986; Viljoen and
Hieber, 1982).
Orthopyroxene in Merensky ore accounts for between 50 and
60% of the overall bulk assemblage. Variable but signicant recovery
of this silicate mineral to otation concentrate occurs in the Merensky otation process (Malysiak et al., 2003; Becker et al., 2006).
2.3. Sudbury Igneous Complex
The Sudbury Structure, a unique geological feature located
within the Canadian Shield of northern Ontario, Canada, is host
to nickelcopper deposits that have been mined since 1886 (Giblin,
1984). In addition to nickel and copper, the ore bodies in the Sudbury area also contain signicant amounts of Platinum Group Minerals (PGM) as well as gold, silver and cobalt.
The Structure consists of the Sudbury Igneous Complex (SIC),
the surrounding brecciated footwall rocks as well as the White-

Ca

Diopside
CaMgSi2O6

50
45

Clinopyroxene

Hedenbergite
CaFeSi2O6

Augite
Pigeonite
5

Enstatite
Mg
Mg2Si2O6

Orthopyroxene

Fe

Ferrosilite
Fe2Si2O6

Fig. 1. Chemical composition of the various minerals comprising the pyroxene group of silicates. Adapted from Morimoto et al. (1988).

N.O. Lotter et al. / Minerals Engineering 21 (2008) 905912

water Group of rocks which inll the interior of the Basin. Ore
deposits are hosted in breccias at the base of the SIC, in a discontinuous layer known as Sublayer Norite, and in the breccias and
gneissic rocks of the underlying footwall. The Sublayer Norite is
synonymous with another term known as Dark Norite Breccia
(DNBX). While the term Sublayer Norite is most well known, the
term DNBX has been used historically within Xstrata Nickel, formerly Falconbridge Limited. These ores are generally lower grade
and more mac than the ores hosted by the footwall rocks.
Sulphide mineralogy is dominated by pyrrhotite, pentlandite
and chalcopyrite that occur as blebs, stringers, breccia or matrix
sulphides and as massive sulphide. Gangue mineralogy is largely
dependent on the host rock. The Sublayer or DNBX, with its noritic
matrix, is dominated by plagioclase, actinolite, and pyroxene,
whereas the underlying footwall breccias and gneisses have a larger component of quartz, orthoclase and plagioclase. All ore hosting units contain some amount of augite, a clinopyroxene, but
only the Sublayer or DNBX contains both clinopyroxene and orthopyroxene. Total pyroxene content in Sublayer or DNBX ores varies
between 10 and 20%. Orthopyroxene content accounts for roughly
one half of the total pyroxene content, representing 5% to 13% of
the bulk modal assemblage.
3. Flotation recovery mechanisms
In both Sudbury and Merensky ores, valuable sulde minerals
are concentrated by otation. The rst step in this process involves
comminution and size reduction of the ore to an appropriate size. If
the ore is ne, there are associated problems of separability due to
unselective recovery by entrainment. If the grind size is too coarse,
and there are composite particles which can result in either recovery or grade losses. Speciality reagents are then added to achieve
suitable selectivity, both to enhance the oatability of the valuable
minerals and to reduce the oatability of the unwanted gangue
minerals. There are reagent and mineral interactions and there
can be inadvertent activation of the gangue minerals resulting in
their reporting to the concentrate. Four mechanisms have been
identied for orthopyroxene reporting to otation concentrates.
Each of these has a different treatment route that is quite wide
ranging in effort and cost. These are listed and then discussed in
more detail in turn.
 Entrainment identied by the presence of ne liberated material in nal concentrate.
 Composite particles normally identied by mineralogical analysis of the concentrate. Prior to the commercial availability of
mineralogical image analysis systems, it was common practice
to use paymetal grades on a size by size basis to infer the presence of these particles. Composite particles may include sulphide orthopyroxene particles and of particular interest here,
talc-orthopyroxene particles manifested as talc rims in association with orthopyroxene.
 Inadvertent ion activation by the reagent suite such as activator
copper sulphate, frother type, or the dissolution of the sulphide
minerals, and is identied by presence of mid to coarse liberated
particles with no talc present in the concentrate and conrmed
with the use of TOF SIMS.
 Naturally Floating Gangue liberated talc in particular is naturally oatable. There is new evidence to suggest orthopyroxene
in Sudbury ores may also be naturally oatable.

3.1. Entrainment
Recovery of ultra ne silicate gangue by entrainment remains a
contributing process to the overall recovery of gangue to nal con-

907

centrate. The reduction of gangue recovery to concentrate by froth

washing in mechanical cells was reported by Kaya and Laplante
(1990). This study included trial data for the Strathcona Mill, where
signicant increases in paymetal grade and recovery were found
by the use of washwater at a rate of 0.040.05 cm/s. This produces
a positive bias, a mechanism reducing the nett recovery of process
water in the pulp to the concentrate. Since entrained gangue is
recovered to concentrate by hydraulic action in the process water,
the wash water replaces the process water (and the gangue). Since
the problematic ferro-magnesian silicates do show a partial recovery by entrainment, this may be worth consideration in possible
options to decrease gangue recovery. Another effective technique
is to dilute the pulp density (Finch, 2006).
3.2. Composite particles
Composite particles are found in nal concentrate. The size
range of these varies but the key feature is that part of the composite particle which consists of a positively-oating mineral, be it
naturally oating (such as talc), positively oating under collection
by, for example, xanthate, and positively oating under collection
as a result of activation mechanisms.
This case is identied by presence of composites in the concentrate using mineralogy, or paymetal grade of concentrate on a sizeby-size basis. This type of problem is addressed by additional
milling, which can be expensive, however successful and economic
if well-focussed. In the case of Raglan operations, Qubec, this
amounted to regrinding of the cleaner tailing in the cleaner circuit
before scavenger otation (Lotter et al., 2002). In the case of Lac des
Isles, Ontario, this amounted to niche milling of cleaner feed
streams (Martin et al., 2003). Generally these applications improve
the nal concentrate, and sometimes the paymetal recovery. In the
case of Leinster Nickel Operations, Western Australia, the installation of an Isamill to regrind composite particles in cleaner scavenger concentrate prior to its recycle brought about an improved
grade/recovery curve (Seaman et al., 2007). In the case of talc rimming, the composite particle otation effect dominates and imparts naturally oating characteristics to the composite particle.
In Fig. 2 a photomicrograph image shows a thin section from a
Bushveld Merensky sample. The talc rimming features are
annotated.
3.3. Inadvertent activation
Inadvertent activation can occur due to the addition of reagents,
particularly copper sulphate and also can be due to the dissolution
of the metal ions from the sulphide minerals. When soluble copper
species enter this otation system however, reactions develop
which transform the inert pyroxene into a oatable mineral. A
study was performed using TOF-SIMS and XPS to investigate copper activation, and the effect of such activation on sulphide collector adsorption (Nagaraj and Brinen, 1996, 1997). This study
investigated pure pyroxene in the absence of any sulphide minerals. The adsorption of amyl xanthate and isobutyl ethoxycarbonyl
thionocarbamate on pyroxene was studied before and after copper
activation. Conditions comparable to otation were used. Before
copper activation, no adsorption of either collector on pyroxene
was measured. With copper activation only, Cu++ was found on
the pyroxene surface. When collector was added thereafter, the
Cu++ was reduced to Cu+ and collector had been adsorbed. The
reduction of Cu++ to Cu+ is indicative of a reaction between the collector and the cemented copper. The sites of copper cementation
and collector adsorption showed sufcient correspondence to conclude that the collector had adsorbed at the copper cementation
sites.

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N.O. Lotter et al. / Minerals Engineering 21 (2008) 905912

Fig. 2. Talc rim or coating around orthopyroxene (opx) on the boundary between orthopyroxene cumulate crystals and a sulphide bleb from the Merensky Reef. Other
minerals present include lathes of biotite (bio) as well as euhedral chromite (chr) crystals. Photomicrograph is 2.5 mm across, in plane polarised light.

The use of copper sulphate activator in the otation of base metal sulphides is widely practised for sphalerite and iron sulphides.
The reaction was investigated by Perry in the context of ne particle otation (Perry, 1980). It was concluded that for the pH range
6-9 the use of copper sulphate activated the base metal sulphides
but also activated certain gangue minerals such as pyroxene. This
was explained by the predominance of the copper species CuOH+
and Cu2OH++ in this pH range which interact with the silicate particles. Two interaction pathways are a condensation reaction (splitting out of water) and H-bonding:
OCu Bonds
SiOH CuOH SiOCu H2 O

H-Bonds
SiOH CuOH SiOHOHCu

The surface becomes positively charged, which is detected by zeta

potential measurements. Under these conditions the zeta potentials
of these gangue minerals are reversed as the metal ions in solution
begin to hydrolyse to their respective hydroxy complexes. The
reversal in sign of zeta potential was attributed to the adsorption
of these metal hydroxy cations on the mineral surfaces. From Perrys analysis of the soluble forms of copper in this system, the following equilibria were suggested:
Cu H2 O CuOH H

8

K1 = 2.51  10

CuOH2 s Cu 2OH

K2 = 1.6  1019
2Cu 2H2 O Cu2 OH
2
11

K3 = 1.58  10
From the above equilibria, the role of pH in the state of equilibrium is seen. Clearly acidic pH favours the production of Cu++ in Eq.
(3). Equally, high pH favours the production of Cu(OH)2(s) in Eq.

(4). Also, Eq. (3) has the highest equilibrium constant, inferring
that the monohydroxide might be the predominant form. Copper
activation is described in its simplest form as a cementation reaction of the type
MS Cu CuS M

where MS = metal sulphide and M = divalent metal.

The free availability of Cu++ to drive Eq. (5) to the right-hand
side is therefore a factor in determining the degree of cementation
of copper on the metal sulphide surface. This in turn is, for copper
sulphate, dependent on lower rather than higher pH. The increased
metallic copper surface on the metal sulphide improves the amenability of collector adsorption, rendering that metal sulphide particle hydrophobic, or oatable.
Perry, 1980 concluded that:
1. In acid pH regimes with 3 < pH < 4, and in the absence of copper
sulphate, use of collectors yielded optimum recoveries for chalcopyrite, pentlandite and pyrrhotite.
2. In higher pH regimes with 8 < pH < 9, and in the absence of copper sulphate, the recovery of these sulphides was much lower,
and in particular for pyrrhotite.
3. When copper sulphate was used ahead of collector dosage, the
recovery of all three minerals improved at the higher pH values,
in particular pentlandite.
For the cementation reaction described in Eq. (6), this is denitely the case with sphalerite (and iron grinding media). However,
the above two reactions (Eqs. (3) and (4)) occur with many other
sulphides, based on the observation that EDTA extraction removes
Cu in these cases, but not from sphalerite (Finch, 2006).
In other sulphide work, Weisener and Gerson, 2000 showed
that, for copper activation of pyrite at pH 8.5, the adsorption of
copper on pyrite followed a two-step mechanism. First, Cu++ rapidly adsorbs onto reactive sulphur sites, where it is reduced to
Cu+ via sulphur oxidation. As the copper activation process pro-

N.O. Lotter et al. / Minerals Engineering 21 (2008) 905912

ceeded (after ve minutes of reaction time), a second step starts

whereby an overlayer of Cu(OH)2 develops on the pyrite surface.
Malysiak et al. (2004) and OConnor et al. (2006) characterised
the oatability of the pentlandite-pyroxenite system. Using ToFSIMS to measure any cementation reactions, they showed that
inadvertent activation of pyroxene by both Cu++ and Ni++ occurred
at pH 9. The copper was present as CuSO4  5H2O at a strength of
5  105 M. Micro-otation tests were used to produce concentrates. The pyroxene demonstrated positive (true) otation by xanthate adsorption. They proposed that the nickel species were
sourced in the pentlandite present, which demonstrated chemisorption of xanthate, releasing Ni++ in exchange. This theory was
proposed because comparative measurements of adsorbed nickel
on orthopyroxene on its own as against in the presence of pentlandite showed that there was a higher degree of nickel adsorption
on the orthopyroxene when in the presence of pentlandite. In the
same study, Malysiak et al. showed that for pure orthopyroxene
on its own, the addition of copper sulphate increased the zeta potential of that orthopyroxene. On the basis of the following discussion, it is probable that the species involved with this activation
mechanism are the monohydroxides of copper and nickel.
This work concluded that the metal monohydroxide species is
generally more surface active. It also explained why the charge reverses, i.e., because the interaction is chemical and not entirely
electrostatic. The free energy release for the chemical interaction
is higher than for the electrostatic mechanism. The metal monohydroxide continues to interact with the mineral surface, resulting in
a surface species M+ which can now interact with xanthate.
Malysiak et al. (2002) showed that an equivalent cementation
reaction occurred between Cu++ and feldspar. The effect was more
marked at pH 9 than pH 6. This pH effect implies that it is the
monohydroxy species and not the Cu++ which is adsorbing (Finch,
2006).
Comparative microotation tests using hand-selected specimens of talc, chromite, feldspar, orthopyroxene and quartz, and
supported by zeta-potential measurements, showed that in that
alkaline pH range, the addition of copper sulphate at a concentration of 104 M caused marked changes in the zeta potential (Martinovic et al., 2005). In particular, at pH 7 the zeta potential
becomes positive for all minerals tested. This corresponds to the
pH at which the maximum concentration of the species CuOH+ occurs. Table 1 shows the results of microotation tests of 10 minutes duration, using copper sulphate and isobutyl xanthate. Both
reagents were dosed and conditioned ahead of that otation at
strengths of 104 M. These results show that the addition of copper
sulphate to the otation system increases the 10-minute recovery
of orthopyroxene from 3 to 65%.
The reactions between copper sulphate and xanthate proposed
by Fornasiero and Ralston, 1992, were proposed by Martinovic
et al. to be active in the microotation system. These were
CuOH2 2X CuX2 2OH

CuOH 2X CuX2 OH

CuX2 CuX 1=2X2

Table 1
Flotation recovery by microotation at pH 9 (Martinovic et al., 2005)
Mineral

10 min recovery
xanthate only

10 min recovery copper

sulphate and xanthate

Quartz
Feldpar
Talc
Chromite
Orthopyroxene

13
3
61
21
3

62
75
42
66
65

909

The stoichiometry of these reactions imply that one molecule of

copper reacts with two molecules of xanthate to form a Cu(II) xanthate, which rapidly decomposes to form Cu(I) xanthate and 50% in
the form of Cu(OH)2. However, this assumes that the presence of
species such as Cu(OH)X at the surface is very small.
When orthopyroxene (Opx) enters the otation system, further
difculties develop. In cases where Opx is present in signicant
quantities in the ore treated by a concentrator, problems can develop by way of a reactive and interactive system that causes the Opx
to oat and to interfere with sulphide otation. There are two main
types of response.
The rst type of effect includes the destabilisation of the rst
rougher otation froth, reducing pentlandite recovery to that product. It was shown that the choice of frother type may either enhance selectivity against Opx, or enhance Opx otation by
adsorption of frother on that Opx. Dowfroth 250, a polyglycol ether
frother, was shown to be present on magnesium-enriched sites of
the Opx surface in otation concentrate. Substitution of this frother
by MIBC, an alcohol, reduced this interference considerably. This
work also showed that the addition of CMC to the otation system
restored much of the desired metallurgical performance by
depressing the Opx from otation (Lotter et al., 2003).
The second type of effect is an activation mechanism brought
about by metal ions in he process water, be they from the addition
of copper sulphate as an activator for sulphides, or the release of
nickel from pentlandite as a result of chemisorption of xanthate
(Malysiak et al., 2004).
3.3.1. Use of chelating agents to reverse activation
A detailed study to improve the selectivity of separation of
pentlandite from pyroxene using zeta-potential and TOF-SIMS
measurements of otation test products from dened conditions
was reported by Shackleton et al. (2003). This work was performed
as a mixed mineral system, i.e., the pyroxene and pentlandite were
together in the microotation test setup. It was found that copper
adsorption was non-selective. Both pentlandite and pyroxene become copper-activated in the presence of copper sulphate and subsequently, in the presence of xanthate, adsorption of this collector
on both minerals occurs on the copper-activated sites. This leads to
otation of both minerals to different extents. This work went on
to investigate the effects on selectivity of introducing polyphosphate and DETA to the system. Zeta potential measurements
showed that the polyphosphate altered the surface charge of the
pentlandite, thus limiting the development of slime coatings.
Introduction of DETA reduced the overall degree of copper coating
on both minerals, but predominantly on the pyroxene. Subsequent
otation tests demonstrated that signicant advances in selectivity
of pentlandite over pyroxene could be gained by using these two
reagents.
Shackleton et al. (2003a, b) showed that copper-activated and
nickel-activated pyroxene reacted to ethylenediamine (EDA) at
pH 9, producing soluble EDA-Cu and EDA-Ni complexes. This signicantly reduced the amount of adsorbed copper and nickel on
the pyroxene. This suggests not cementation (as in the case of
sphalerite) but more the monohydroxy species discussed earlier
(Finch, 2006). OConnor et al. (2006) discussed these mechanisms
of the reduction of the effect of metal ions and attributed them
to complexes formed.
It was shown by Malysiak et al. (2003) that, for a pyroxenepentlandite system, the presence and quantity of calcium ions affected the otation properties of both minerals. For pH settings
of 6 and 9, increasing concentrations of calcium ions in the pyroxene-pentlandite system progressively reduced the recovery of both
minerals by otation. This effect was more marked at pH 9, and affected the pyroxene to a greater extent than the pentlandite. It was
determined from TOF-SIMS measurements that the calcium

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N.O. Lotter et al. / Minerals Engineering 21 (2008) 905912

depression mechanism was by adsorption of calcium on these mineral surfaces. This effect is quite common. Some suggest a blocking action which prevents copper adsorption and or xanthate
uptake (Finch, 2006; OConnor et al., 2006).
3.4. Naturally oating gangue
3.4.1. Problem statement and generic treatment
There are two aspects to talc otation in these systems. One is
talc rimming of other silicate particles such as orthopyroxene. This
has been discussed in the section on composite particle effects. The
other is the behaviour of liberated talc.
Talcaceous minerals are naturally oatable and enhance froth
stability. This increases entrainment of non-oatable gangue minerals. Talc has two types of surface due to its phylosilicate, or thin
sheet-like, structure. One surface is an uncharged plane, the other
a charged edge. The plane is hydrophobic and causes talc to have
natural otation properties. The traditional approach to depressing
magnesium-bearing gangue minerals is to add either carboxymethyl cellulose (CMC) or a guar gum to the otation system. This
depresses the otation properties of the magnesium-bearing minerals and modies the froth. As a result, kinetics and selectivity are enhanced. The proposed mechanism for this depression is by
adsorption on the mildly hydrophobic surface of the silicate and creating a hydrophilic surface. This prevents particle-bubble attachment and therefore depresses otation (Bradshaw et al., 2005).
3.4.2. Choice of depressant
Comparative adsorption studies of CMC, guar and starch
depressants on talc were reported by Steenberg and Harris, 1984.
The measurements made of these reagents individually adsorbed
on talc showed that the starch and guar produced a much higher
level of adsorption on talc than did the CMC for any equilibrium
concentration of that reagent. Zeta potential measurements made
showed that the talc was negatively charged for all three pH values
tested (4, 7 and 11). Furthermore, the depressants were all negatively charged to some degree. Electrostatic attraction was therefore ruled out as a possible mechanism for the adsorption
process. The authors concluded that the adsorption was taking
place on two different sites of the talc surface. These were the basal
cleavage planes, and the edges. This was supported by the depressant adsorption demonstrating between one and three plateaux in
responding to the increasing equilibrium concentration.
Comparative adsorption studies of dextrin and guar gum onto
talc were also carried out by Rath et al. (1997). Adsorption, otation and electrokinetic measurements indicated that the adsorption process is governed by hydrogen bonding as well as
chemical interaction between the polysaccharides and metal
hydroxide groups on the surface of talc. The superior depressant
activity of guar gum was attributed to its more favourable conguration of cis-hydroxyl groups.
Polyacrylamides have been investigated as talc depressants by
Gong et al. (1999), Morris et al. (1999). Microotation studies
showed that both functional group substitution and molecular
weight played important roles in the ability of these polymers to
depress talc. The effect of ionic strength and pH on the adsorption
of CMC and synthetic polyacrylamides was investigated by Morris
et al. (2002). They found that at high pH and low ionic strength,
adsorption density of anionic polymers was low, while at either
high ionic strength or low pH, adsorption density increased. The
adsorption of non-ionic polymers on talc was not inuenced by
changes in pH or ionic strength.
3.4.3. Effect of molecular weight and degree of substitution
The effect of molecular weight of CMCs and guars on talc
adsorption was studied by Shortridge et al., 2000. This work found

that as the molecular weight of guars increases, so did their

depressing ability on talc. Increasing the molecular weight of
CMC did not have a decisive effect on the depression. At the conditions tested (0.001 M KNO3), guar gums were far more effective
depressants of talc than CMC.
The effect of charge, molecular weight and the presence of cations Ca++, Mg++ and K+ on the adsorption of CMC on talc were investigated by Parolis et al. (2005). Adsorption of CMC was more
enhanced by the presence of Ca++ and Mg++ than K+. Higher ionic
solution strengths further improved the rate of adsorption. By
varying the degree of substitution of the CMC molecule, it was
shown that higher degrees of substitution were associated with
lower adsorption density on talc. Changing the molecular weight
had no inuence on the adsorption density. Intrinsic viscosity
and light scattering experiments by Parolis et al. (submitted for
publication) showed that Ca++ ions interact with the CMC molecule
to change the conformation and cause greater coiling than K+ ions
at an equivalent ionic strength. At high ionic strength when the
coiling of the CMC molecules is the same Ca++ ions still cause greater adsorption densities than K+ ions indicating that there is a specic interaction between Ca++ ions, the CMC and the talc surface.
3.4.4. Case studies
Earlier, Pietrobon et al. (1997) reported that, for nickel ores
sampled from the Australian nickel belt, which contained altered
magnesium silicates, the use of CMC to depress the otation of
MgO minerals was signicantly enhanced by the addition of soda
ash. This was explained in terms of improved dispersion in the
pulp.
Muinonen (2006) reported successful application of the use of
CMC at the Thompson Mill, Manitoba. In this case, the increase
in ore coming from the Birch Tree Mine had introduced critical levels of magnesium-bearing minerals to the otation system (mostly
talc), and caused a sharp increase in the assayed MgO grade of the
nickel concentrate from the traditional <2.5% MgO to 58% MgO. In
this case, however, an expanded cleaner circuit had also to be
added to the ability of the concentrator to handle the extra cleaning requirements. The owsheet change and use of CMC resulted in
a reduction of assayed MgO in nickel concentrate to an average of
3%.
In Sudbury, orthopyroxene dilution into the Strathcona nickel
concentrate became problematic in 20052006. Mineralogical
work, including QemSCAN and ToF SIMS, was undertaken. Results
show liberated orthopyroxene in both ultrane and ne-mid size
fractions in the nickel concentrate. This indicated that both
entrainment and otation were occurring. ToF-SIMS analysis did
not detect the presence of either Cu or Ni ions on the surface of
the orthopyroxene. While talc rims on orthopyroxene grains have
been identied on occasion, the majority of orthopyroxene appears
unaltered. This work leaves open the possibility that orthopyroxene in the Sudbury Sublayer or DNBX ores may have natural otation properties. The use of CMC in this otation system, together
with a owsheet change, signicantly reduced the recovery of
orthopyroxene to the nickel concentrate. The results of this work
will be separately reported (Di Di Feo et al., 2006).

4. Conclusions
This review has attempted to elucidate and summarise the
occurrences, otation and depression of orthopyroxene in ultramac deposits. At this stage, the following conclusions may be
drawn:
1. For the two igneous geological systems reviewed, orthopyroxene occurs in quantities sufcient to be considered as signi-

N.O. Lotter et al. / Minerals Engineering 21 (2008) 905912

2.

3.

4.

5.

cant to the mineral processes treating these ores and its presence has been shown to be problematic.
There are two major effects on the base metal sulphide otation
performance arising from acquired otation properties of orthopyroxene. These are:
a. Dilution of the otation concentrate, reducing the paymetal
grade and increasing the magnesium grade,
b. Reduction in paymetal recovery to that concentrate.
Four mechanisms have been identied and each of these has a
different treatment route these routes are quite wide ranging
in effort and cost, vis
a. Entrainment identied by presence of ne liberated material and addressed quite simply by froth washing.
b. Composite particles identied by presence of composites
using mineralogy or grade of size by size of concentrate,
and addressed by additional milling which can be expensive. Talc rimming causing natural otation is a part of the
composite particle theory. This is identied by presence of
talc rims on the particles in the concentrate, using carefully
analysed quantitative mineralogy and addressed with the
use of polymeric depressants (otherwise used for talc).
c. Inadvertent ion activation identied by presence of coarse
liberated particles without the presence of talc in the concentrate and conrmed with the use of TOF-SIMS and
addressed by chelating agents and changing reagent suites.
d. Naturally oating silicate gangue specically liberated talc
demonstrates positive collectorless otation and needs to be
depressed by the dosage of either CMC or guar depressants.
A secondary interference with sulphide otation was noted, in
which frother type, was shown to have a signicant effect on
otation performance.
Further work should be done to evaluate whether there are
other mechanisms for pyroxene to report to the concentrate
and to understand the differences between clinopyroxene and
orthopyroxene as well as to test the treatment methods.

Acknowledgements
The authors would like to thank the management of Xstrata for
permission to publish this review. The Centre for Minerals Research University of Cape Town; Professor Jim Finch McGill
University; Mr. Phil Thwaites, Manager of Process Control, Falconbridge, and Mr Jim Schmitt Akzo Nobel, contributed signicantly
to this review and to the Falconbridge Milling School, Sudbury, in
May 2006, entitled Flotation and Depression of Ferro-Magnesian Silicates, kindly sponsored by Dr Michael King, Director of Technology, and Mr. Allen Hayward, Vice-President of Nickel Operations,
Falconbridge.
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