Minerals Engineering 53 (2013) 91100

Contents lists available at ScienceDirect

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

A review of the effect of water quality on otation

Wenying Liu , C.J. Moran, Sue Vink
Centre for Water in the Minerals Industry, Sustainable Minerals Institute, The University of Queensland, Brisbane, Queensland 4072, Australia

a r t i c l e

i n f o

Article history:
Received 3 May 2013
Accepted 16 July 2013
Available online 9 August 2013
Keywords:
Water quality
Flotation
Abiotic water constituent
Biotic water constituents

a b s t r a c t
As water resources become scarcer and societys demands to reduce freshwater extraction have
increased, mine sites have been increasing water reuse and accessing multiple water sources for mineral
processing to save freshwater, particularly in froth otation. Implementation of either strategy may lead
to water quality variation that may impact otation efciency. A large number of studies have been carried out to enhance the understanding of water quality variation in otation. However, these studies tend
to be performed on a case by case basis. There is a lack of a framework to put together these existing studies, which makes it difcult to understand the topic comprehensively and therefore difcult to identify
gaps and directions for future research. This would eventually hinder the ongoing implementation of
water conservation practices and thus lead to more pressure being placed on freshwater. In this paper,
a review of the existing studies on water quality variation in otation is given in three aspects: causes
of water quality variation, consequences of water quality variation and solutions for problems caused
by water quality variation. Based on the three aspects, a framework was developed, with which these
studies were categorized and structured. Organizing literature in this way makes it possible to identify
gaps in current research and future research directions.
2013 Elsevier Ltd. All rights reserved.

Contents
1.
2.

3.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Existing research on water quality variation in flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Causes of water quality variation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.1.
Internal factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.2.
External factors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Consequences of water quality variation and associated pathways. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1.
Abiotic water constituents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2.
Biotic water constituents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.
Solutions for water quality variation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.1.
Internal solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.2.
External solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Identifying gaps and future directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction
The minerals industry is being driven to save freshwater and
minimize mine water discharge by a combination of water challenges, such as limited freshwater availability (Peters and Meybeck, 2000; Ridoutt and Pster, 2010), environmental pollution
from mine water discharge (Carlson et al., 2002; Johnson et al.,
2002), increasing competition for water among multiple users
Corresponding author. Tel.: +61 7 3346 4027; fax: +61 7 3346 4045.
E-mail address: wy.liu@uq.edu.au (W. Liu).
0892-6875/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2013.07.011

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(Boulay et al., 2011; Rijsberman, 2006), community concerns over

water security and cultural or spiritual issues regarding water (Jenkins and Yakovleva, 2006; Kapelus, 2002), and corporate sustainability policies and goals (Amezaga et al., 2010; Moran, 2006).
Two important strategies being implemented to improve water
efciency are increasing water reuse and accessing alternatives
to freshwater for mineral processing, particularly in otation.
Implementation of either strategy has been shown to increase
the tendency for water quality to change, which, in turn, may affect
otation efciency. In general, otation is most effectively undertaken with clean water. As a second preference, metallurgists seek

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W. Liu et al. / Minerals Engineering 53 (2013) 91100

Fig. 1. A conceptual view of a site water system showing the internal and external factors causing water quality variation in a otation plant.

a consistent water quality so that reagent regimes for otation can

be developed and applied consistently. Variation in water quality is
undesirable because it could complicate operating conditions and
compromise otation performance (Broman, 1980; Hoover, 1980;
Levay et al., 2001; Malysiak et al., 2003; Rao and Finch, 1989).
A signicant body of research seeks to understand issues associated with water quality in otation. These studies focus mainly
on three aspects: (1) understanding the reasons for water quality
variation in otation, (2) quantifying the effect of water quality
variation on otation efciency and investigating the underlying
mechanisms to explain the effect, and (3) testing different solutions to deal with the effect. However, one common limitation of
these studies is that they approach the multifaceted topic on a case
by case basis. Lacking of a method to organize these existing studies hinders the understanding of this topic in a holistic way and
therefore makes it difcult to identify gaps in this area and possible
directions for future research. Given the limitation stated above,
after reviewing the existing research on water quality variation
in otation, a framework was developed to organize these studies.
This framework can enhance the comprehensive understanding of
this topic by showing the emphasis of current research. This helps
identify gaps in current research and directions for future research.

2. Existing research on water quality variation in otation

Water quality for otation on a mine site can vary signicantly
over time (Levay and Schumann, 2006; Luukkanen et al., 2003;
Stn et al., 2003). The composition of otation water depends on
the ore being processed, the reagent suite, the water source and
the way the site water system is managed. The entire water system
is also affected by climate. Fig. 1 shows a conceptual view of a site
water system which puts the mineral concentrator in perspective
with the main water system components. The system consists of
raw water stores, worked water stores, tailings facilities, other site
water tasks (operational uses of water), the concentrator itself and
a blender. The blender is a virtual representation of site infrastructure used to demonstrate that worked water might need to be diluted with raw water or treated water prior to its use in a specic
water task. Raw water is water that has not been previously used
for any purpose within the site (Cote and Moran, 2009). In contrast,
worked water is water that has been used for a purpose on site and
is returned for potential future use (Cote and Moran, 2009). A detailed explanation of Fig. 1 is given in Section 2.1.

2.1. Causes of water quality variation

Factors that cause water quality variation in otation can be
grouped into two categories by reference to the concentrator:
internal and external (Fig. 1). Internal factors include the ore being
processed by the concentrator, reagents added into the concentrator and water internal reuse, where water is recovered from the
concentrator with the help of different kinds of concentrate/tailings thickeners, local storage tanks, etc. and used again by the concentrator. External factors are divided into external to
concentrator and external to site. External to concentrator
factors refer to factors that are within the site boundary, which include the raw water stream and water external reuse, where water
is recovered from different site water tasks (tailings storage facilities and other site water tasks), stored in an appropriate place and
used again in the concentrator. Raw water and worked water
stores are open systems that interact with the surrounding environment and local climate. These interactions result in mass and
energy transfer processes taking place across the site boundary.
These processes are dened as external to site factors, which
are shown as inputs and outputs in Fig. 1. The possible inputs
and outputs of raw water and worked water stores are summarized in Table 1 (Cote and Moran, 2009).
Different water constituents associated with both the internal
and external factors can be introduced into otation water by
either simple mixing or complex physical and biophysicochemical
watermineral interactions during mineral processing. Further,
chemical reactions may occur among constituents from different
water streams when coexisting in otation water. The processes
of different constituents being introduced into otation water are
given below.
2.1.1. Internal factors
2.1.1.1. Ore oxidation and dissolution. The chemical composition of
the ore being processed by a mine can be very complex and usually
includes a variety of minerals. Ore oxidation and dissolution during
mineral beneciation processes can introduce various substances
into otation water, which may alter the chemistry of the system
and thereby inuence otation efciency. The exact nature of the
reaction products depends on reaction conditions, such as Eh and
pH.
There are examples in the literature showing the dissolution of
ore and its potential implications for otation. For example, surface oxidation of copper ore (chalcopyrite, enargite and tennantite) leads to the dissolution of copper (II) to different extents

W. Liu et al. / Minerals Engineering 53 (2013) 91100

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Table 1
Inputs and outputs of raw water and worked water associated with external to site factors.

Raw water

Worked
water

Inputs

Outputs

The inputs include multiple sources of raw water supplies:

The outputs can be a combination of raw water and worked water:

 Surface water rainfall/runoff reservoirs, lake and rivers)

 Ground water (aquifers, water entrained in materials to be
processed)
 Sea water (estuaries and oceans)
 Third-party water (an entity in an arrangement with site to supply
water)
No exteriia1 to site inputs for worked water

at different pH values (Sasaki et al., 2010). Thiosalts and calcium

ions are released into otation water from copper ore, which may
have benecial effects on otation by depressing pyrite (Liu et al.,
1993), and improve the selectivity of nickelcopper separation
(Kirjavainen et al., 2002a,b). At lower pH and in a stronger oxidative environment, chalcocite oxidation produces copper (II) and
soluble sulfur species (Chander and Fuerstenau, 1983), which
may affect the subsequent adsorption of polymeric dispersant
onto chalcocite particles (He et al., 2011). The rate and extent
of galena dissolution depends on pretreatment conditions, with
air treatment having the highest dissolution rate and extent, followed by oxygen and nitrogen (Fornasiero et al., 1994). The production of lead ions by dissolution leads to the subsequent
formation of lead hydroxide precipitates onto galena surfaces,
which could affect galena otation (Chernyshova, 2003). Dissolution of galena also produces dissolved sulfur species, with sulfate
and sulde being the major species with and without air, respectively (Hsieh and Huang, 1989). Another example is molybdenite
oxidation, which produces molybdate ions and sulfur (Chander
and Fuerstenau, 1983).
The ore itself contributes substances to otation water that are
normally minimal in quantity due to their low solubility and low
availability from limited oxidation of valuable and gangue minerals (Johnson, 2003). However, these constituents can build up in
otation water through water reuse, and eventually affect otation
performance, e.g., the accumulation of dissolved copper leading to
inadvertent activation of sphalerite (Slatter et al., 2009).
The grinding media employed might also affect otation water
quality if they are not inert materials (Huang and Grano, 2006;
Peng and Grano, 2010). For example, Eh and dissolved oxygen
of the slurry has been found to decrease immediately after grinding upon application of reducing steel grinding media (Grano
et al., 1990). Conversely, iron hydroxide is produced due to the
oxidation of electrochemically reactive steel media (Adam et al.,
1984; Grano, 2009). As a result, otation performance can be affected because of the strong dependence of thiol collector adsorption on Eh and the presence of iron hydroxide (Freeman et al.,
2000; Grano, 2009).

2.1.1.2. Reagent addition. Reagent addition can introduce various

inorganic or organic substances into otation water in the form
of residue reagents, reaction by-products, and impurities (Schumann et al., 2009). For example, lime is added in otation of
molybdenitecopper ore to maintain an alkaline pH for pyrite
depression, which causes the release of calcium ions into solution (Raghavan and Hsu, 1984). Water for reverse otation of
iron ore contains a signicant concentration of amine otation
reagents used to remove silica particles (Batisteli and Peres,
2008; Stapelfeldt and Lima, 2001). Copper cyanide complexes
are often found in water for galenasphalerite otation because

 Seepage (water leaks through the base or sides of water stores)

 Evaporation (water loss to the atmosphere)
 Supply to third-party (water supplied to an entity in an entanglement
with site)
 Entrainment (water contained in the rock or coal after being processed)
 Discharge worked water release to the surrounding environment)
 Discharge of raw water is unlikely
 Miscellaneous loss (losses that cannot be attributed to the above
processes)

of the addition of sodium cyanide in the milling circuit (Seke

and Pistorius, 2006).
Similar to ore dissolution, otation reagents themselves may
contribute a small portion of water constituents (Slatter et al.,
2009), but these constituents can be accumulated in water in
an altered or unaltered state during water reuse and eventually
reach a concentration high enough to impact otation performance. For example, otation selectivity of copperleadzinc
ore is compromised by the accumulation of the decomposition
products of a xanthate copper collector Z-200 due to water reuse
and its subsequent non-selective adsorption (Ozkan and Acar,
2004).
2.1.1.3. Water internal reuse. Water internal reuse is a typical water
management strategy targeting a concentrator. For example, the
Rosh Pinah mine in Namibia recovers water from the lead rougher
tailings thickener and lead concentrate thickener, and uses the
recovered water for milling and lead otation (Seke and Pistorius,
2006). Water recovered from concentrate ltration/drying is used
again in the ore grinding circuit in Olympic Dam (Torris and Trotta,
2009). Water internal reuse may cause issues related with processing, e.g., ore dissolution and reagent addition, to later become
water quality issues due to the recirculation of these substances
in processing plants. However, this strategy could, to some extent,
simplify water chemistry because the water is generally re-circulated rapidly without experiencing signicant alterations (Rao
and Finch, 1989).
2.1.2. External factors
2.1.2.1. Multiple sources of raw water supplies. Water quality variation in the raw water stream is dened as one of the external to
concentrator factors that can contribute to water quality variation
in the concentrator. The reason why water quality varies in raw
water stores can be tracked down to external to site factors, because raw water stores receive water inputs from multiple sources
of different quantity and quality from outside of the site boundary.
These sources, as shown in Table 1, include surface water, groundwater, sea water and third-party water.
The use of multiple sources of raw water supplies of different
quality is very common for many mine sites. For example, primary
water supplies containing high levels of salinity including calcium,
magnesium and iron salts are being used in several remote areas
(Levay et al., 2001). Humic acids, abundant in natural waters associated with dead vegetation decomposition, have been found to exist in otation water, which could depress molybdenite otation
(Lai et al., 1984), and coal otation (Arnold and Aplan, 1986). Tannic acid, commonly found in ground water, is a potential depressant which may be introduced into otation water from raw
water streams (Levay and Schumann, 2006). Some mine sites are
using treated efuent (third-party water) as a make-up water

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W. Liu et al. / Minerals Engineering 53 (2013) 91100

supply, e.g., Mt Arthur coal mine (Brereton et al., 2007), Cadia Valley goldcopper mine (Schumann et al., 2003), and Mogalakwena
platinum mine (Slatter et al., 2009). This water source may contain
high levels of total organic carbon (TOC) and microbes, which may
affect otation performance (Levay et al., 2001). Apart from these
inputs, a variety of outputs can also contribute to water quality
variation in the raw water stream (Table 1). For example, water
constituents can be concentrated due to evaporation and diluted
due to rainfall/runoff which may vary seasonally (Rao and Finch,
1989; Vink et al., 2009).
2.1.2.2. Water external reuse. A common external reuse strategy is
that water is recovered from tailings storage facilities and other
site water tasks, stored in the worked water stores and used again
in the concentrator (Department of Resources Energy and Tourism,
2008). Besides the raw water stream, this worked water stream is
dened as the other external to concentrator factor that can
cause water quality variation in otation. Similarly, this variation
can be tracked down to external to site factors. As opposed to
the raw water stream, there are no inputs but only outputs for
the worked water stream (Table 1).
One of the outputs is associated with the local climate, which
may raise signicant issues regarding water quantity and quality.
For example, evaporation can alter concentrations of dissolved
and colloidal constituents at different times of the year (Levay
et al., 2001). Changes in temperature due to diurnal (day/night)
or seasonal (summer/winter) cycles may inuence water composition, either directly or indirectly, through chemical, physico-chemical and biological processes, e.g., mineral dissolution and
oxidation, solubility of metal precipitates, all of which are affected
by temperature (Lin, 1989). These processes may change water
constituents in concentration and form. For example, physicochemical and biological processes mainly related to degradation
of otation reagents could take place in the tailings storage facilities (Chen et al., 2011; Nedved and Jansz, 2006). Tailings particles
can contain a high proportion of ne clay and other colloidal materials, which are difcult to separate from water (Ofori et al., 2011).
These changes in the tailings storage facilities can be propagated to
the concentrator through water external reuse. Similar to water
internal reuse, water external reuse may cause initial processing issues to eventually become water quality issues.
2.2. Consequences of water quality variation and associated pathways
Water quality variation is among the factors that can inuence
otation efciency. The consequences of water quality variation in
otation can be grouped into two broad categories based on the
type of water constituents: abiotic, meaning not alive (e.g., inorganic metal ions), and biotic, meaning of or related to life (e.g.,
microorganisms). For each category, the consequences can be
either negative or positive effects on otation efciency, which
can be quantied by different variables, such as recovery, grade
and oatability of valuable minerals, and selectivity between valuable minerals and gangue.
The negative or positive effects of abiotic and biotic water constituents can occur through different pathways. Firstly, water constituents could interact with and therefore change the properties of
any of the three phases involved in otation: mineral particle, air
bubbles and aqueous solution. These changes could then affect
the efciency of the three sub-processes occurring sequentially in
a otation cell. These sub-processes include collision of mineral
particles with bubbles, attachment of mineral particles to bubbles,
and formation of stable particlebubble aggregates which then rise
to the surface of the otation cell forming the froth phase (Dai
et al., 1999). Only mineral particles with certain degrees of hydrophobicity, either naturally occurring or articially rendered by

adding certain otation reagents, can attach to bubble surfaces.

The efciency of the three sub-process are dened as the fraction
of particles colliding with a bubble, the fraction of colliding particles which actually attach to the bubble surface, and the fraction
of attached particles which are successfully transported across
the pulpfroth interface, respectively (Dai et al., 1999; Seaman
et al., 2006). Finally, these changes are reected in the change of
the nal otation efciency. In addition, water constituents can
also react with reagents added to otation circuits, thus changing
reagent properties.
The pathways by which a particular water constituent affects
otation performance may be different for each mineral and reagent combination. These possible pathways to explain the negative and positive effects of different abiotic and biotic water
constituents are given below.
2.2.1. Abiotic water constituents
2.2.1.1. Negative effects.
2.2.1.1.1. Reduction in particle surface hydrophobicity by metal ions.
Metal ions are important abiotic water constituents which can impact otation performance. Metal ions hydrolyze in alkaline pH
solutions and precipitate as hydrophilic metal hydroxides, sulfates
or carbonates if their concentrations are above their respective solubility limits (Fuerstenau et al., 1985). Formation of metal hydroxides is inuenced by aqueous pH (Font et al., 1999). Precipitation of
these hydrophilic metal hydroxides on mineral surfaces has been
generally described as indiscriminate (Kitchener, 1984), resulting
in formation of a hydrophilic barrier to collector adsorption on
mineral surfaces (Fornasiero and Ralston, 2006; Senior and Trahar,
1991).
Calcium, iron and aluminum ions are the cations most cited in
the literature as precipitated species with a detrimental effect on
mineral recovery and grade (Hoover, 1980). The effect of these
multivalent ions on coal otation has been investigated, the result
of which shows that multivalent electrolytes depress coal otation
in the pH region of metal hydroxide precipitation (Celik and
Somasundaran, 1986; Rao and Finch, 1989; Somasundaran et al.,
2000). Sphalerite recovery has been found to be reduced by the
presence of zinc ions (200 ppm) due to the formation of colloidal
hydroxide on the mineral surface (Williams and Phelan, 1985).
Copper (II) acts as the activator at a threshhold concentration but
a depressant for sphalerite at high concentrations (Fornasiero
and Ralston, 2006). A critical concentration of copper sulfate exists
where sphalerite gains the maximum recovery. Above that critical
concentration, sphalerite recovery decreases as a result of excess
copper hydroxide on the sphalerite surfaces (Boulton et al.,
2005). Coarse particles are the rst particles to be affected by a reduced surface hydrophobicity as they are more easily detached
from bubbles in the high turbulent regions of a otation cell (Ralston et al., 2007).
The reduction in mineral surface hydrophobicity due to the precipitation of hydrophilic metal hydroxides could compromise the
efciency of the particlebubble attachment sub-process (Koh
et al., 2009; Schwarz and Grano, 2005). It can also cause lower contents of mineral particles entering the froth, which might compromise the efciency of the sub-process of formation of stable
particlebubble aggregates (Ali et al., 2000; Ata, 2012; Johansson
and Pugh, 1992; Moolman et al., 1996). The presence of dissolved
ions in water can also change the stability of particlebubble
aggregates in the froth phase (Bak et al., 2012; Farrokhpay and
Zanin, 2012).
2.2.1.1.2. Change in particle surface charge by metal ions. Metal
ions in otation water can alter the surface charge of particles
and consequently affect interactions between particles and waste
gangue or between particles and collectors. This could affect particlebubble attachment and also formation of stable particlebub-

W. Liu et al. / Minerals Engineering 53 (2013) 91100

ble aggregates (Ali et al., 2000; Ata, 2012; Johansson and Pugh,
1992; Moolman et al., 1996).
Investigations have been carried out on the role of calcium ions
in modulating the surface properties of molybdenite and in controlling the interaction between molybdenite and the most predominant gangue mineral, namely quartz, in copper porphyries.
The results show that the oatability of ne molybdenite particles
is signicantly reduced when calcium ions and silica coexist in the
otation pulp. This is because the adsorption of calcium ions on
molybdenite and quartz reduces the magnitude of negative surface
charges and thus causes heterocoagulation of molybdenite and
quartz (Raghavan and Hsu, 1984). The adsorption of calcium and
other metal ions that exist in otation water leads to a reduction
in the negative surface charges and xanthate adsorption on galena,
which may have detrimental effects on galena otation (Ikumapayi
et al., 2012). Experimental results suggest that generally, metallic
cations present in electrolytes hinder the otation of pyrochlore,
an oxide mineral. This is because the negative surface charge on
pyrochlore is reduced by the adsorption of cationic species, which
hinders the adsorption of cationic amine collector on pyrochlore
surfaces (Espinosa-Gomez et al., 1987; Rao et al., 1988).
2.2.1.1.3. Inadvertent activation of unwanted minerals by metal
ions. Some metal ions can also inadvertently activate unwanted
minerals, thus affecting otation selectivity in varying degrees.
For example, metal ions such as lead, silver and iron are present
in otation water as impurities and can inadvertently activate
sphalerite surfaces (Chandra and Gerson, 2009; Finkelstein,
1997). The undesirable activation by metal ions, copper (II), iron
(II) and calcium (II), causes pyrite to oat together with sphalerite
in sphalerite otation circuits, leading to poor selectivity (Boulton
et al., 2003; Zhang et al., 1997). Inadvertent activation of sphalerite
and pyrite by copper ions in water leads to a low copper grade in
copper otation circuits (Broman, 1980; Rao and Finch, 1989). Copper (I) cyanide could activate sphalerite in otation of leadzinc
sulde ore reducing lead grade (Seke and Pistorius, 2006).
2.2.1.1.4. Slime coatings on mineral surfaces. The formation of a
slime coating on valuable mineral surfaces can lead to depression
of otation of valuable minerals. For example, positively charged
serpentine gangue minerals, such as chrysotile and lizardite, has
been found to severely reduce the otation of negatively charged
(unoxidized) pentlandite by forming a hydrophilic slime coating
on pentlandite surfaces (Edwards et al., 1980). The coverage of colloidal iron oxide (hematite) slimes originating from the steel grinding media, iron sulde minerals and non-sulde gangue, on galena
surfaces can reduce the mineral surface hydrophobicity and therefore have a signicant depressing effect on the otation of galena
particles (Bandini et al., 2001). The slime coating of montmorillonite clay on coal is detrimental to coal otation (Xu et al., 2003).
2.2.1.1.5. Interactions with otation reagents. Like metal cations,
anions may also have a negative effect on otation performance by
interacting with otation reagents. For example, anions in treated
efuent have been identied as having a negative effects on copper
and molybdenum recoveries (Fisher and Rudy, 1976). Sulde ions
have been found to decompose xanthate collector in the presence
of oxygen (Shen et al., 2001). Under solution conditions which favor rapid xanthate decomposition by sulte, xanthate adsorption
onto galena is signicantly reduced and galena otation strongly
depressed (Grano et al., 1997a,b). Salts in water are particularly liable to react with fatty acid reagents and form insoluble complexes
(Ozkan and Acar, 2004). Calcium ions react with the collector used
in apatite otation, thus reducing its concentration for otation,
leading to a decline in apatite recovery (dos Santos et al., 2010).
Variations in pH and Eh usually affect the chemistry of otation
reagents and species present in otation water. For example, pulp
pH can alter the form of some frothers and thus inuence their
effectiveness. Cresol, with the optimum performance in the molec-

95

ular form, has been found to be converted into ionized form at high
pH, which then does not act as a frother. Quinoline exists in ionized
form in acid pH, andconsequently has poor frothing properties
(Bulatovic, 2007). Dissolved oxygen is also important in controlling
the composition of the mineral surface of some minerals and the
effect of the reagents on the minerals in otation systems (Gaudin,
1974).
2.2.1.2. Positive effects.
2.2.1.2.1. Compression of electrical double layer. The presence of
electrolytes can improve particlebubble attachment efciency
through compressing the electrical double layer and thus reducing
the electrostatic repulsion between particles and bubbles (Kurniawan et al., 2011). Investigation of oil agglomeration of coal in inorganic salt solutions shows that coal recovery increases markedly as
salt concentration (NaCl) is raised (Yang et al., 1988). Coal recovery
is improved by using saline water (Ofori et al., 2005; Wang and
Peng, 2013). Flotation of methylated quartz is improved with
increasing KCl concentration (Laskowski and Kitchener, 1970).
The efciency of the attachment of methylated quartz particles
to nitrogen bubbles has been found to increase with the increase
in KCl electrolyte concentration (Dai et al., 1999). Flotation
improvement in the presence of electrolytes is explained by the
compression of the electrical double layer by electrolytes, thus
reducing electrical repulsion and subsequently facilitating the particlebubble attachment process. The reduction in electrostatic
repulsion between particles or between particle and bubbles may
in turn decrease the adsorption of positively charged hydrophilic
slimes such as magnesium silicates and thus increase bubbleparticle attachment (Bremmell et al., 2005; Hewitt et al., 1994; Morris
et al., 1995).
2.2.1.2.2. Formation of smaller bubbles. Electrolytes are favorable to the formation of smaller stable bubbles due to the inuence
of the electrolytes on surface tension and gas solubility (Pugh et al.,
1997). Smaller bubbles increase the particlebubble collision probability (Bournival et al., 2012; Pugh et al., 1997), and also improve
particlebubble attachment efciencies (Hewitt et al., 1994). Finer
gas bubbles in high salt concentrations may result in reduced reagent consumption (Quinn et al., 2007). However, it is noteworthy
to mention that along with the benets discussed above, an increase in ionic strength can cause a negative effect by enhancing
frothability and therefore increasing gangue recovery (Manono
et al., 2012, 2013).
2.2.2. Biotic water constituents
2.2.2.1. Negative effects. Biotic water constituents in otation
water, including organics and microorganisms, may be surface active, or act as dispersants or occulants, which can interfere with
otation process (Levay et al., 2001; Rao and Finch, 1989). Residue
reagents such as xanthate and their decomposition products in otation water could absorb non-selectively on most suldes and reduce otation selectivity (Seke and Pistorius, 2006).
There are cases in literature showing the effect of organic species on otation efciency through different pathways. For example, humic acids, abundant in some natural waters, have been
found to readily adsorb on molybdenite surfaces and result in decreased hydrophobicity and oatability of molybdenite (Lai et al.,
1984). The presence of a small amount of strongly hydrophilic
lignosulfonates is sufcient to render molybdenite surfaces hydrophilic, which hinders the attachment and spreading of an oily collector over the molybdenite surface (Ansari and Pawlik, 2007a,b).
The presence of organic species, the exact composition of which
is not known, has a negative effect on pyrochlore otation selectivity by promoting the otation of silicate minerals along with
pyrochlore (Espinosa-Gomez et al., 1987; Rao et al., 1988). The
accidental incorporation of oils and lubricants into the mill feed

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W. Liu et al. / Minerals Engineering 53 (2013) 91100

at a coppergold concentrator has been shown to promote librated

gangue particles, leading to uncontrollable frothing associated
with a drop in selectivity (Bos and Quast, 2000). Copper and gold
otation has been found to be negatively affected by total organic
carbon (TOC) in otation water (Schumann et al., 2003).
A variety of microorganisms at meaningful concentrations can
be introduced into otation water due to the use of alternative
water sources that contain microorganisms, such as treated efuent. Furthermore, otation circuits can provide conditions conducive to microbial growth, given that there is potential nutrition
from reagent addition, appropriate oxygen levels and suitable temperature. For example, the total bacterial count in the plant otation pulp on a mine site can be as high as 109 cfu/mL (Levay
et al., 2001), where cfu stands for colony-forming units. Unlike
direct microscopic counts (cell/ml) where all cells (dead and viable) are counted, cfu only estimates viable cells. Thus the concentration of dead plus viable bacterial cells in the otation pulp may
be higher than 108 cell/ml. For comparison, E. coli concentration in
typical raw sewage (i.e., untreated municipal wastewater) is at a
magnitude of 105 cell/mL (Carr et al., 2004). The presence of bacteria in otation water could pose potential risks to otation performance (Levay et al., 2001; Slatter et al., 2009). For example,
bacteria (c-Proteobacteria) have been shown to reduce the oatability of apatite due to their interactions with calcium-containing
minerals and strong occulation (Evdokimova et al., 2012). E. coli
has been found to have a negative effect on copper otation mainly
due to its attachment onto chalcopyrite surfaces and the resulting
reduction in chalcopyrite surface hydrophobicity (Liu et al., 2013a;
Liu et al., 2013c).
2.2.2.2.. Positive effects. In some cases, biotic water constituents
may bring positive effects on otation efciency. Two types of biotic water constituents can exemplify the positive effects: residue
reagents and bacteria. Residue reagents brought to otation circuits through water external reuse allows retention of some reagents and therefore lowers reagent consumption. For example,
the dosage of amine collector in the reverse otation of iron ores
can be reduced by up to 50% through water external reuse (Batisteli and Peres, 2008; Stapelfeldt and Lima, 2001). Bacteria could be
used to reduce the recovery of one mineral over that of another
in situations where a selective otation is required (Elmahdy
et al., 2011; Evdokimova et al., 2012; Pecina-Trevino et al., 2012).
Further research will advance and rene the search for suitable
solutions to take advantage of the positive effects of biotic water
constituents.
2.3. Solutions for water quality variation
As otation efciency can be affected by water quality change,
different strategies are required to manage water quality change
to avoid compromising otation efciency. Solutions that can be
applied to deal with otation problems caused by water quality
can be divided into two categories by reference to the concentrator: internal and external (external to concentrator and external
to site).
2.3.1. Internal solutions
Generally, otation problems from water quality are dealt with
by internal solutions, which focus on the otation operation itself.
One conventional internal solution to deal with the problems is to
adjust the reagent regime.
There are examples of reagents added to control otation problems caused by water quality in literature. Zinc hydroxide precipitates can be dissolved by acids, thus improving sphaleritegalena
separation (Levay et al., 2001). Removal of calcium ions by oxalic
acid improves pyrochlore recovery (Rao et al., 1988). The addition

of citric acid has been found to eliminate the detrimental effects of

calcium ions and to restore the selectivity of chalcopyritegalena
separation with dextrin (Liu and Zhang, 2000). Chemical dispersants, e.g., polyphosphate, can be used to disperse precipitated colloidal species from mineral surfaces (Levay et al., 2001). Addition
of complexing agents, such as amine complexes, can help to revert
inadvertent activation effects of metal ions on the selective otation of pentlanditepyroxene (Shackleton et al., 2003). The selectivity of sphalerite and pyrite can be increased by the use of
sulfoxy depressants against pyrite that has been inadvertently activated by metal ions (Chandra and Gerson, 2009). Dithionite has
been used as a reducing reagent to control electrochemical reactions in otation, notably to prevent oxidation of sulde minerals
(Sui et al., 2000). Activation of sphalerite by copper species during
the selective otation of galena and sphalerite can be eliminated by
removing copper with sodium cyanide (Seke and Pistorius, 2006).
Soda ash is added to precipitate calcium and other interfering cations from the pulp for otation of phosphate ore (Nanthakumar
et al., 2009). Changing the slime surface charge by chemical additives, such as carboxy methyl cellulose, has been shown to be
effective in reducing the adverse effect of the slime on pentlandite
otation (Edwards et al., 1980). Coal otation recovery increases
signicantly by removing the ne fraction from the feed using a
hydrocyclone (Oats et al., 2010).
In some cases, the internal solution of adjusting reagent regime
is an efcient way to deal with otation problems associated with
both internal and external factors. However, this solution requires
much time, energy and attention to be spent on the selection of reagents and control of reagent additions to ensure proper concentrations and the most effective separation. In addition,
operational efciency cannot be guaranteed. For example, despite
continuous process improvement, the problem of pyrite activation
by metal ions and its misreporting to sphalerite concentrates still
remains (Boulton et al., 2003; Zhang et al., 1997). Chemical sidereactions between the reagents added and otation water constituents, metal ions for example, may also affect mineral surface
properties and thus their oatability (Sui et al., 2000).
Water treatment by conventional technologies and operational
techniques to meet otation requirements is also considered as an
internal solution. A wide variety of technologies and techniques
are available for the minerals industry. The main types of water
treatment and their application domains in mining operations
can be found in The Water Management Handbook (Department
of Resources Energy and Tourism, 2008). A few examples of water
treatments employed to meet mineral processing requirements are
given here. Metal ions can be removed using ion exchange and
membrane technologies. For example, the adverse effect of zinc
ions on sphalerite otation is eliminated by treating otation water
to remove zinc ions before the water enters the mill (Williams and
Phelan, 1985). The use of low-cost natural iron ore has been shown
to be effective in removing arsenic from water (Aredes et al., 2012).
Laboratory experimental results show that a combination of activated carbon and ion exchange to remove Ca2+, Mg2+ and organic
species appears to be an effective means for improving selective
otation of pyrochlore (Espinosa-Gomez et al., 1987; Rao et al.,
1988). Pretreatment of water with aeration or with activated carbon has been found to signicantly improve molybdenite recovery
in the presence of humic acid (Lai et al., 1984). Removal of organic
species from otation water by activated carbon can produce a statistically signicant improvement in nickel grade and recovery (Levay et al., 2001).
Each water treatment technique has its own advantages and
limitations. Therefore, the optimum treatment approach should
be selected according to the water quality requirements for a specic water task. For example, treatments for most mineral processing applications would not require potable grade water. A

W. Liu et al. / Minerals Engineering 53 (2013) 91100

97

combination of different approaches may be used to deal with difcult or complex water quality issues. The selection of water treatment approaches, which match the water quality requirement for
specic water tasks, can be challenging. The cost of water treatment and the undesirable additional energy incurred may pose a
challenge for maintaining an environmentally and economically
sustainable mining operation.

2.3.2. External solutions

Although they may efciently deal with otation problems from
water quality, the technologies and processes implemented by
internal solutions have not considered the connectivity of the site
water system, leading to a constrained view of opportunities to
deal with the problems. In contrast, external solutions attempt to
consider opportunities across the entire water system to deal with
otation problems caused by water quality. External solutions
have generally received less attention compared to internal solutions. Therefore, there is a lack of literature on external solutions
that could be applied to manage water quality problems.
Flotation water quality is dynamic because of the inuence by
the internal and external factors discussed in Section 2.1. The
water system on a mine site acts as a complex system with feedbacks and interactions between the local climate and the engineered reticulation (Vink et al., 2009). Therefore, solving otation
problems caused by water quality requires an understanding of
the properties of different water streams and their connectivity.
If this information is known, in some cases relatively simple external water management practices can be applied to help stabilize
plant operations without overreliance on chemical additions. For
example, taking water from a location in the water store that provided water of consistent quality was proposed as a possible
external to concentrator solution to control the risk posed by
water salinity variation to a coal washing plant (Liu et al., 2011).
Using tailings as a potential adsorbent to bacteria was considered
as a possible external to concentrator solution to mitigate the
risk posed by water-borne bacteria to copper and gold otation
(Liu et al., 2013b). In this case study, one possible external to site
solution might be to treat the bacteria-containing water stream before it enters the mine.
It is understandable that more attention has been paid to internal solutions simply because it is simpler to do so. It takes more effort to think about external factors and interconnectivities of the
system. Looking at external solutions may require a change in paradigm or change in the way of thinking.

Fig. 2. Framework for organizing the literature on water quality management in

otation.

Fig. 3. Emphasis of current research on water quality management in otation

(darker color equals more work).

3. Identifying gaps and future directions

A review of the literature shows that a signicant amount of research has been carried out on each of the three aspects of water
quality variation in otation (reasons, effects and solutions). The
reasons why water quality varies are explained by internal and
external factors. The consequences of water quality variation are
either negative or positive effects on otation efciency, which
can be quantied by different variables, such as recovery, grade
and oatability of valuable minerals, and selectivity between valuable minerals and gangue. Solutions to deal with the effect are divided into internal and external solutions.
Given the absence of a method to organize these case-by-case
studies, we developed a three-component framework to classify
the existing literature. This three-component framework consists
of causes of water quality variation, consequences of water quality
variation and solutions for problems caused by water quality variation (Fig. 2). The framework structures the literature in such a
way that makes it possible to identify gaps in each component
and associated research directions. Fig. 3 shows the emphasis of
current research on each of the three components by different levels of color. Darker color equals more research work. Accordingly,
research gaps were identied in three broad areas.
The rst gap lies in the focus of current research on the two
types of water constituents. Compared to abiotic water constituents, there is a lack of an understanding on the impacts, processes
and solutions associated with biotic water constituents (Rao et al.,
2010). This could be a barrier for mine sites sourcing alternative
water sources that contain biotic water constituents of concentrations sufciently high to affect otation efciency, such as treated
efuent, when attempting to reduce freshwater withdrawal. Consequently, more pressure would be put on the limited freshwater
resources and the people and ecosystems that rely upon it. Therefore, further research is needed to understand how biotic water
constituents affect otation and the optimal solutions that can be
adopted to deal with the effect. It is important for mine sites to
be aware that the effect of biotic water constituents may be sitespecic. Different mine sites may have different external water
sources with different biotic constituents. Some mines are located
near populated areas with an option of treated efuent and may
need to study the impact of fecal bacteria, etc. Other mines are in
forested areas, which may have a water source containing different
types of bacteria, algae or tannic acids (from plant decomposition)
that may affect otation.

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W. Liu et al. / Minerals Engineering 53 (2013) 91100

The second gap is about the solutions applied to deal with water
quality problems in otation. Currently, water quality problems in
otation are generally dealt with by internal solutions that focus
on the otation operation itself more or less haphazardly, that is,
without a diagnostic and proactive understanding of the causes
for water quality variation. This may lead to a constrained view
of opportunities to deal with the problems and thus hinders the
ongoing implementation of good water management practices that
conserve freshwater. Therefore, further research work is required
to explore multiple external solutions that consider opportunities
across the entire water system as opposed to the otation operation itself. The ultimate solution might be the best combination
of internal and external solutions. Finding such a solution requires
mine sites to have a good understanding of the connectivity of the
site water system and the properties of different water streams.
This leads to the third gap.
The third gap is associated with understanding the reasons
why water quality varies. This relies on water quality monitoring
information and an understanding of the connectivity of the site
water system. Even though water quality monitoring is conducted
on mine sites, in some cases, the monitoring tends to be performed without clear objectives and consideration of the connectivity of different water streams, and not at the desired locations
or at the desired frequency. This poses a potential challenge for
subsequent utilization of these data to analyze water quality variation. Therefore, there is an essential need to develop a method
which could help set up clear objectives and therefore target
the monitoring at the desired water streams. The way the information on water quality variation in otation is organized, i.e.,
from the perspective of internal and external factors, could be a
starting point for developing such a method. After understanding
the internal and external factors that cause water quality variations, mine sites can design a monitoring program that measures
the chosen components at the right locations and for a suitable
long time period.
The applicability of this three-component framework may not
be limited to organizing research on water quality problems in otation but extended to broader external to concentrator and
external to site areas involving water quality change, such as
the impact of water quality variation on heap leaching within the
site boundary and on the local ecosystem outside mine sites. Further research is required to test the applicability of this framework.
From the perspective of water management, integrated water
management requires water issues be treated as a risk management exercise. This is because water is one of the risk factors that
increase the likelihood of mining operations having accidents
which could injure or kill people, damage the environment and
cause serious loss of production and prots (Byrne et al., 2012; Catalan et al., 2000; Cote and Moran, 2008; Saleh and Cummings,
2011). As for water quality management in otation, a previously
published risk-based approach was suggested as a tool to assist
mine sites in managing the risk of water quality variation in otation in a consistent and structured manner (Liu et al., 2011). This
approach integrates the three components stated above to quantify
the risk posed by water quality variation to otation and evaluate
different scenarios for risk mitigation. The potential of the approach as such a management tool that can be put in place has
been tested using two otation case studies. The rst is to manage
the risk of saline water to coal otation (Liu et al., 2011). The second deals with the risk posed by water-borne bacteria to copper
and gold otation (Liu et al., 2013a). The two case studies demonstrate the potential of the risk-based approach to deal with complexity and allow specic situations to be considered in a generic
manner. They also show that water quality problems can be dealt
with more effectively by considering opportunities from the entire

water system rather than only focusing on the local area where the
problems occur.
Acknowledgements
Funding for this study was provided by Australian Research
Council linkage project (LP0883872) Impact of recycled and low
quality process water on sustainable mineral beneciation practices, which is part of AMIRA project P260E.
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