Minerals Engineering, Vol. !1, No. 2, pp.

171-187, 1998
Pergamon © 1998 Elsevier Science lad
All rights reserved. Printed in Great Britain
0892--6875(97)00149-0 0892-6875/98 $19.00+0.00

INCREASING FINE COPPER RECOVERY AT THE

OK TEDI CONCENTRATOR, PAPUA NEW GUINEA

D. ORWE ~, S.R. GRANO t, and D.W. LAUDER ~

§ Ok Tedi Mining Limited, P.O. Box 1, Tabubil, Western Province, Papua New Guinea
I" Ian Wark Research Institute, University of South Australia,
Adelaide 5095, Australia. E-mail: Stephen.Grano@levels.unisa.edu.au
(Received 29 July 1997; accepted 13 October 1997)

ABSTRACT

This paper describes laboratory and plant based investigations on methods to increase
fine copper recovery during flotation treatment of Ok Tedi porphyry sulphide ores.
Currently the Ok Tedi concentrator treats a mixed porphyry/skarn ore blend, which is
ground to a dso of 180 lzm with flotation carried out using a dithiophosphate
/monothiophosphate collector mixture, at pH 11.5. Plant survey data showed that recovery
of fine copper minerals in the Ok Tedi concentrator was at moderate levels, with only
81% of the -10 pm copper in the feed recovered in roughing and scavenging stages.
Pulp and surface chemical measurements during the survey period suggested that
oxidation of copper minerals occurred during processing.

Attention then focused on characterising the size-by-size laboratory flotation response of

two porp~yry sulphide ore samples, as an initial step towards developing methods to
increase fine copper recovei'y. These tests showed that for an ore sample in which the
predominant copper mineral was digenite, - 1 0 / a n copper recovery was only 40%. By
contrast, .for an ore sample in which the predominant copper mineral was chalcopyrite,
- 1 0 pm copper recovery was 80%. Low recovery of fine (-10 tzrn) copper in the digenite
ore sample was linked to the degree of oxidation of this mineral during laboratory
grinding and conditioning.

Controlled potential sulphidisation experiments were undertaken to counter the adverse

effects of digenite oxidation. The electrochemical potential of sulphidisation was
optimised. These experiments showed clear increases in fine copper recovery for the
digenite ore sample and, to a lesser extent, the chalcopyrite ore sample. Results from
plant trials of sulphidisation on a variety of porphyry sulphide ore blends are discussed.
The size-by-size copper recovery in the Ok Tedi concentrator with and without
sulphidisation treatment during two plant surveys are discussed. © 1998 Elsevier Science
Ltd. All rights reserved

Keywords
Sulphide ores; fine particle processing; flotation reagents

Presented at Minerals Engineering '97, Santiago, Chile, July-August 1997

171
172 D. Orwe et al.

~TRODUCTION

Ok Tedi Mining Limited (OTML) operates a large porphyry copper-gold mine at Mt. Fubilan in the Star
Mountains of the Western Province, Papua New Guinea. The concentrator treats a mixed porphyry/skarn
ore blend, with the porphyry zone consisting of both sulphide and non-sulphide copper minerals. Broadly,
the porphyry sulphide ore can be classified as either monzonite, in which the predominant copper minerals
are digenite and chalcopyrite, and monzodiorite, in which the predominant copper mineral is chalcopyrite
only. The flotation behaviour of monzonite and monzodiorite porphyry sulphide ores in both laboratory and
plant based investigations is the focus of the current study.

The OTML concentrator consists of two parallel and independent grinding and flotation circuits, each
operating at 40kTPD. The concentrator flowsheet and equipment list have recently been described [1]. The
flotation feed has a dso of 180 pro, while flotation is carried out using a dithiophosphate/monothiophosphate
collector mixture (Cytec Collector 7249), at pH 11.5. For the fiscal year 1997, the copper head grade was
0.86% copper, resulting in a final concentrate grade of 34.2% copper at 83.2% copper recovery [2]. Size-by-
size analysis of a typical concentrator monthly composite sample (March, 1995) showed that copper in the
+20-75 prn size range exhibited above average recovery of 93%, while copper in the -20 pm size fraction
had a substantially lower recovery of only 62%. Laboratory roughing flotation studies on the monzonite ore
suggested that this particular sample exhibited low copper recovery (72%), compared with the monzodiorite
ore (88%), although monzonite ores generally perform better than monzodiorite ores. Hence, attention
focused on the oxidation behaviour of chalcocite, and how oxidation may adversely affect copper recovery
from monzonite ores. This has been reported in a separate publication [3]. This latter study also investigated
the oxidation behaviour of single minerals of chalcocite and covellite [3]. In this current study particular
attention is paid to the size-by-size flotation rate behaviour of the monzonite and monzodiorite ore samples
and defining the size-by-size copper recovery in the Ok Tedi concentrator itself.

REVIEW

Attention will now turn to a brief literature review of chalcocite oxidation. It is well established that
chalcocite may undergo rapid oxidation at alkaline pH and moderately oxidising potentials, with the
oxidation products being copper hydroxide and the concomitant sublayer of copper-depleted chalcocite
(CU2_xS) [3,4,5]. Chalcocite oxidation may significantly modify interaction mechanisms of ehalcocite with
thiol collectors. The presence of copper hydroxide on the chalcocite surface may increase collector uptake
and therefore consumption, but adsorption may result in a significantly less hydrophobic surface [6,7]. The
disparity between collector uptake and flotation recovery for oxidised chalcocite prompted further studies
on the structure of the adsorbed collector layer on oxidised chalcocite by both infrared and XPS techniques
[8,9].

The adverse effect of surface oxidation in practice is most commonly countered by the application of
sulphidisation [10]. Sulphidisation is commonly applied in the flotation of tenorite [11], malachite and
chrysocolla [12] by common thiol collectors. An essential feature of sulphidisation is to maintain an
optimum sulphide ion concentration in solution during the sulphidisation step, while ensuring removal of
excess sulphide ion during subsequent collector adsorption and flotation steps. Early studies focused on
minimising the adverse effect of excessively high sulphide ion concentration by aeration and/or solution
replacement after the initial sulphidisation step [13]. Interaction of the sulphide ion with oxidised surfaces
may also, through a catalytic reaction involving the surface, cause the adsorbed sulphide ion to be oxidised
to a range of sulphur--oxy species, most notably thiosulphate [12]. The presence of high concentrations of
thiosulphate after sulphidisation may also cause unintentional depression of value mineral [12].

Other studies have focused on the stabilising effect of the sulphidised surface on dixanthogen attachment
to the mineral surface in the ease of malachite [14] and chrysocolla [15]. The latter study found that in spite
of marked adsorption of xanthate onto the oxide mineral in the absence of sulphidisation, no floatability was
conferred. This was in contrast to the same mineral after sulphidisation for which flotation recoveries were
very high, without appreciable changes in xanthate uptake [15]. The findings in the absence of sulphidisation
 Increasing fine copper recovery 173

are in accord with those of Barzyk et al. [7] for heavily oxidised chalcocite. In the case of chrysocolla, it
has been considered that increased hydrophobicity of the sulphidised surface increased physical adsorption
of dixanthogen, stabilising dixanthogen attachment and increasing flotation recovery [15].

However in the ca~e of chalcocite, sulphidisation apparently does not make its surface hydrophobic in the
absence of collector [16]. Walker et al. [16] have studied the sulphidisation of chalcocite surfaces by
hydrogen sulphide ion. Sulphidisation does not induce hydrophobicity on chalcocite in the absence of
collector, in contrast to gold and pyrite for which minerals evidence for deposition of a sulphur film has
been demonstrated [16]. In the case of chalcocite, Walker et al. [16] concluded that sulphidisation forms
a copper sulphide phase with a higher sulphur to copper ratio than the underlying chalcocite surface. This
conclusion is in agTeement with the findings of McCarron et al. [17] in the case of chalcopyrite at high
sulphide concentrations and also recent studies on chalcocite sulphidisation [3]. In the particular case of
chalcopyrite, sulph:idisation extends the metal-deficiency of the sulphide lattice, as well as reducing the iron
oxy hydroxide phase [17].

It seems likely that sulphidisation minimises collector consumption during the flotation of oxidised sulphide
minerals by precipitating metal hydroxides, present both at the surface and in solution, as the insoluble metal
sulphide. Direct collector attachment to the unoxidised mineral surface is then possible by an
electrochemical me~:hanism, provided the electrochemical potential is restored to a region where electron
transfer may proceed (usually by aeration). Sulphidisation is likely to result in a strongly hydrophobic
surface in the presence of collector, provided further mineral oxidation is avoided prior to flotation. It is
probable that fine particles of chalcocite (-10 ~rn) may suffer more significantly the adverse effects of
oxidation (in comparison to intermediate size particles) for a variety of reasons and, hence, sulphidisation
may show promise for increasing their recovery in flotation. It is significant to note that Raghavan et al.
[ 18] found greater and more rapid uptake of sulphide ion on both chrysocolla and brochantite for fine (-74
lam) size fractions ~aan on coarser size fractions.

The advent of ion :selective electrodes has allowed the development of controlled potential sulphidisation
(CPS), in which excess sulphide concentrations are avoided by strict control of the sulphide electrode
potential [19,20]. ".['his technique has advantages when considering ore feeds of varying oxidation and
composition, and hence different sulphide ion requirements. Jones and Woodcock [20] found that the
optimum potential (as measured by a platinum electrode) during the sulphidisation step of an oxide copper
ore, containing malachite, azurite and chalcopyrite, was approximately -100 mV (SHE). CPS has recently
been successfully applied to the laboratory treatment of Ok Tedi porphyry sulphide ores [21].

More recent investigations have highlighted mechanisms of chalcocite depression by hydrogen sulphide [22].
These studies have suggested that chalcocite may be depressed by ion exchange of collector in the adsorbed
copper-collector complex by hydrogen sulphide ion, in addition to a reductive mechanism at potentials
below -50 mV (SHE) [22]. In the current study, an aeration stage is provided after the sulphidisation stage
significantly reducing sulphide ion activity prior to collector adsorption. Hence, depression by either
mechanism becomes unlikely. Other studies have shown that the optimum sulphide electrode potential for
conditioning and flotation of a mixed copper oxide/sulphide ore occurs in the region of -150 to -350 mV
(SHE) [23,24]. In these particular studies, the potential was controlled to a set value throughout conditioning
by controlling hydrogen sulphide addition, with nitrogen used as the flotation gas [24]. In the current study,
the potential of the sulphidisation stage only was optimised, with all tests incorporating an aeration stage
(air purging) to inc:rease the potential to its equilibrium value prior to collector adsorption and flotation.

It is the purpose of this current study to define the size-by-size copper recovery in the Ok Tedi concentrator,
with and without sulphidisation treatment during two plant surveys. Pulp chemical measurements and
samples for surface analysis by X-ray photoelectron spectroscopy (XPS) were taken during these particular
plant surveys. Results of laboratory studies of two porphyry sulphide ores, monzonite and monzodiorite, are
also discussed. These studies aimed to characterise the ore types in terms of mineralogy and their propensity
to form copper hydroxide on mineral surfaces. Other laboratory tests investigated the effect of sulphidisation
on the size-by-size flotation behaviour of both monzonite and monzodiorite porphyry sulphide ore samples.
174 D. Orweet al.

EXPERIMENTAL

Plant surveys

Two plant surveys are described. In Survey 1, the plant was operating under standard conditions, without
sodium hydrogen sulphide (NariS) addition. In Survey 2, the potential of a platinum electrode was
controlled by NaI-IS addition to flotation feed to maintain a constant potential of -50 mV (SHE). A
combination platinum electrode was placed in a continuous slurry stream bleed from flotation feed, passing
through a box and overflow weir. The combination platinum electrode was placed in the rising zone of
slurry in the box [25]. Slurry pH was also measured, and used to compensate for changes in desired
electrode potential due to pH changes [2]. This control strategy avoided problems associated with pH
fluctuations which may cause fluctuations in required electrode potential. During the survey period, samples
for XPS analysis were collected and measurements of pH, Eh, and metal ions extractable by ethylene
diaminetetraacetic acid (EDTA) di-sodium salt undertaken at various points in the circuit. Experimental
procedures are described more fully below.

As previously stated, the Ok Tedi concentrator consists of two independent grinding and flotation circuits.
Due to significant variations in plant feed characteristics with time, the preferred method of plant evaluation
is to alter one circuit only, on an on--off basis, comparing metallurgical performance of the two flotation
circuits over an extended period. However, for the sake of collection of surface and pulp chemical samples
in the surveys described in this particular study, Survey 1 was conducted prior to Survey 2 on the same
circuit. Other on-off trials are also discussed in which plant metallurgical data were collected using the
preferred evaluation method. This method allowed collection of statistically meaningful data, largely
compensating for variations in feed characteristics between the two circuits.

Laboratory studies on ore types

The copper mineralogy of the monzonite and monzodiorite ore samples are shown in Table 1, on a size-by-
size basis [26]. Both ehalcopyrite and digenite (closely related to chalcocite) dominate in the monzonite ore,
while only chalcopyrite is dominant in the monzodiorite ore. The head grades were 0.77% Cu and 0.37%
Cu for the monzonite and monzodiorite ore samples respectively.

TABLE 1 Deportment of copper minerals in the monzonite and monzodiorite ore samples for
different particle size ranges, as determined by QEM*SEM. Other copper minerals
includes copper contained in goethite and copper oxides.

Monzonite (size range / ~ ) Monzodiorite (size range / ~m)

+150 +31 +13 +150 +31 +13

Digenite 49.0 47.1 40.4 28.0 0 0 0.2 0.3
Covellite 1.0 1.2 2.6 7.0 0 0.3 0.2 0.5
Bornite 18.3 19.2 24.9 31.0 0.1 0.2 0.9 1.1
Chalcopyrite 23.9 23.9 25.0 21.2 90.7 91.9 92.7 84.6
Other Copper Minerals 7.8 8.6 7.1 12.8 9.2 7.6 6.0 13.5

In the flotation studies, 2.15 kg samples of ore were ground separately to a alsoof 150 ~ml, and transferred
to a laboratory Denver D12 flotation cell. The natural pH after milling was 5.6 for both ores. The pH is
increased with lime to a set value (the standard is pH 11.5), followed by conditioning with 15 g/t of Cytec
7249 collector and a frother. Flotation was carried out for a total of 10 minutes, with incremental
concentrates collected. The products are then assayed, sized and the size fractions assayed in a standard
manner.

When sulphidisation was applied, a freshly prepared 1% (w/v) solution of sodium hydrogen sulphide
(NariS) was added after pH adjustment. The sulphidisation step was undertaken for 1 minute to a set Eh
value. The Eh was measured using a combination platinum electrode and was calibrated using a Fe3÷/Fe2÷
 Increasingfinecopperrecovery 175

solution [27]. The smooth platinum electrode was maintained in bright condition by frequent cleaning in
chromic acid solution. This was important due to the possibility of poisoning of the platinum electrode by
the sulphide ion [2;8]. Eh values are expressed relative to the standard hydrogen electrode.

Size-by-size flotation data has been analysed, assuming first order kinetic behavior, using the following
equation [29]:

Recovery (t) = Rm,~ (1 - exp -kt)

where Rm~ is the maximum recovery at infinite time and k is the first order rate constant (rain,-1). This
analysis assumes that only one floatable species, with a rate constant k, is present. A linear least-squares
fitting program was used to fit the above expression to the experimental data and obtain values for the
parameters, Rm~ and k.

Other studies investigated the dissolution and oxidation behaviour of the two porphyry sulphide ore samples
after grinding. In rite dissolution studies, the concentration of soluble copper was determined after filtration
of the pulps at 0.22 gm and acidification of the liquor. The concentration of copper in solution was
measured by inductively coupled plasma atomic emission spectrometry (ICP-AES). These experiments were
carried out as a function of pulp pH. In the oxidation studies, dissolution of copper hydrolysis products in
solutions of EDTA was determined. In these experiments, a 0.01 dm3 aliquot of slurry was conditioned with
0.190 dm 3 of 3% (w/v) solution of EDTA for 5 minutes. The final EDTA concentration is approximately
10-2 mol dm -3. The concentration of copper soluble in EDTA is determined, and the total EDTA-extractable
copper in the leached solution expressed as a percentage of the total copper in the dry solids [30]. The same
procedures were eraployed for studies on plant pulps.

RESULTS

Plant survey under standard conditions---no NariS---Survey 1

In Survey 1 the final concentrate copper grade and recovery were 33.3% and 87.8% respectively (feed head
grade=0.80% copper) (Figure 1). Size-by-size analysis suggested that there was a significant decrease in
copper recovery for particle sizes less than 20 ~ n (Figure 2). However, copper recovery for this fine size
fraction was not as low, relative to intermediate size fractions, as had previously been suggested from
monthly composite samples. Reasons for this disparity are linked to the ore type treated during these
particular plant surveys. The effect of feed copper mineralogy on fine copper recovery is discussed in detail
further below. Approximately 15% of the total copper in the feed is in the -20 lam size range. The acid
soluble copper in the feed was at a moderate level of 0.12%, of which 22% was in the -20 lxrn fraction.
The contribution to the low overall copper recovery in the fine size fraction (-20 lma) was only partly due
to low recovery of acid soluble copper minerals (i.e. malachite, azurite etc.) (Figure 2b). Clearly, low
recovery of sulphide minerals themselves was the major contributor to the low overall recovery of fine (-20
~trn) copper in Survey 1.

The experimental Eh/pH data points for Survey 1 suggests that chalcocite oxidation may occur during
milling in the concentrator (Figure 3). Both the ball mill cyclone overflow and the ninth cell of flotation are
within the stability region of cupric oxide and copper-depleted chalcocite. Practically, the cupric oxide phase
may also include cupric hydroxide. The stability diagram (Figure 3) is calculated assuming metastable
copper sulphides (Cu2_xS) and SOas the only oxidation product of S(-II) [31]. EDTA-extractable copper
measurements confirmed that copper oxidation had indeed occurred, and that recovery of EDTA extractable
forms of copper was low at 9.5% (Figure 1). New flotation feed EDTA-extractable copper was 1.39% in
Survey 1 (Figure 1), a value suggestive of only low quantities of oxidised digenite, a point which is
discussed further below. This may explain the relatively high fine copper recovery noted for this particular
survey in the absence of NariS (Figure 2a). Of interest is the fact that the combined EDTA-extractable
copper flow in the final concentrate (0.019 TPH) and scavenger tail (0.183 TPH) is significantly greater than
EDTA-extractable copper flow in new flotation feed (0.112 TPH) for Survey 1 (Figure 1). This suggests
176 D, O r w e et al.

not only that flotation is selective against EDTA extractable forms of copper, but that oxidation also occurs
during flotation and/or regrind in the plant. Further work should be undertaken investigating copper
oxidation after regrind and in cleaning flotation.

Combined Feed - Total C o p p e r R o u g h e r Tail - Total C o p p e r Scavenger Tail - Total C o p p e r

is~lo~ 117.314671
Is' 0.16128.9 1428 ISl IO.lO 112.2 1978.91
New Feed - Total C o p p e r
0.10114.6 1064 I $2 10.08 110.4 1981.51

ISl 1o.8ol loo 11000 I Roughers Scavengers t ~

[ s210.741 lOO ,11ooo1 I '
S c a v e n g e r Tail
- EDTA-F_zttractable C o p p e r
New Feed - E D T A - E x t r a e t a b l e Copper
__ I is, 1,83 ]
I
$1 ] 1.39 II00 10.1121
$2 ]2.33 1100 ]0.1721
Scavenger Cone. - Total C o p p e r

S110.30 116.7 1449 I

113.0 10.1021

s21o.38 I 4.2 I 82 I

Rougher Cone. - Total C o p p e r

Isll 180188.41 39.41

Cleaner Tail - Total C o p p e r
IS21 40195.21177.2 I
SI 10.25 10.6 ] 18.31 Cleaners/ [
$210.26 15.6 1158.61 includes regdnd]

FinalConcentrate.TotalCopper FIM! Cone. - E D T A . E x t r a e t a b l e C o p p e r

I sll 33.3187.8 121.1 I Is1 10.27 I 9.5 10.0191

$2 35.7189.6 18.5 ]s2 ]0.31 116.7 10.0201

K E Y - Total K E Y - E D T A . E x t r n c t a b l e Co
Survey CoGrade Cu Rex. Solids Survey l EDTA-Cu EDTA'-Cu EDTA-Cu
/% /% /TPH /% Rex/% : Flow/TPH
Survey2 Cu Grade Cu Rex. Solids S u r v e y 2 EDTA-Cu EDTA-Cu EDTA-Cu
I% /% /TPH /% Rex/% F l o w / T P H
whereCu C_mmdeis thetotalCugradeof stream, w e percentage ol is extractable
CuReciscopperrecoverywithrespecttonewfeed in EDTA solution, EDTA-Cu R ~ is the reonvery of copper extractable
andSolidsis thetotaldrysolidsmassflowfI'PH). in EDTA solution with respect m recalculated New Feed and EDTA-Cu Flow
is the mass flow crPI-D of copper extractable in EDTA solution.

Fig.1 OTML simplified flotation circuit, showing copper, solids and EDTA-extractable copper balance
for Surveys 1 (without NariS) and 2 (with NariS) (22/8/96). Note: Cleaners include two stages of
cleaning.

Attention will now turn to XPS analysis of the plant samples from Survey 1. The rougher feed surface was
dominated by oxygen containing species (Table 2), almost certainly indicative of the various gangue oxides
in the feed (silica, aluminosilicates, magnetite). Silicon occurs in the expected form of silica and occurs to
a high concentration on feed samples from both surveys (Table 2). The nonsulphide gangue assemblage
gives rise to a highly insulating surface. Referencing to uncharged, adventitious hydrocarbon at 284.6 eV
showed that the feed sample surface was charge shifted by 4.6 eV (not shown), indicating this surface to
be highly insulating. A 5 min. argon ion etch (Ar÷ at 4 kV) removed greater than 90% of the carbon signal
(Table 2, etched surface), suggesting that adsorbed collector present on sulphide minerals was only on a
small part of the total feed surface.

A noteworthy feature of the feed sample in both Surveys 1 and 2 was the occurrence of iron which occurred
only in the form of iron oxy hydroxides. A broad band between 711 and 712 eV (Figure 4a and b, charge
corrected) can be assigned to Fe(OH)3, FeOOH, Fe203 or Fe304 [32], and is referred to here collectively
as iron 'oxy hydroxide'. The Fe (2p) signal of pyrite lies at a binding energy near 707.4 eV [33], whilst iron
 Increasingfinecopper recovery 177

in chalcopyrite occurs at 708 eV [34]. There was no exposure of an Fe (2p) signal from either pyrite or
chalcopyrite on the feed sample surface without sulphidisation. The S (2p) emission for the rougher
concentrate in the absence of sulphidisation is characteristic of sulphur in adsorbed collector on chalcocite
near 162 eV [3511 and metal deficient sulphide near 163.4 eV (not shown in figures). A 5 rain. argon ion
etch largely removed the metal-deficient sulphide component, but increased overall atomic concentration
of sulphur derived from the underlying sulphide mineral in the rougher concentrate (Table 2). There was
no detectable S (2p) emission on the surface of the feed samples (Table 2), owing to the low concentration
of sulphide minerals in the feed.

100
(a) Total Copper
80

60

40

20

o . . . . . . . . I • . • • • = . , )

(b) Acid Soluble Copper

80

60

40

20

0 • i • • | • | l

1 lO 100 1000
Size / M i c r o n s

Fig.2 (a) Total copper recovery as a function of particle size over the plant copper rougher/scavengers
for Survey 1 cells 1-3 (O) and cells 1-15 (zx) without NariS, and Survey 2 cells 1-3 (o) and cells
1-15 (*) with NariS.
(b) Acid soluble copper recovery as a function of particle size over the plant copper
rougher/scavengers for Survey 1 cells 1-3 (O) and cells 1-15 (a) without NariS, and Survey 2
cells 1-3 (Q) and cells 1-15 (A) with Nal-IS.

In the case of the Cu (2p) spectrum, and in the absence of sulphidisation, there was clear evidence for
oxidised copper in the higher binding energy component near 936 eV (Figure 5a) on the rougher concentrate
surface. A 5 rain. argon ion etch substantially reduces the occurrence of oxidised copper (Figure 5b),
suggesting that the oxidation products were at the surface only. It should be noted that low concentrations
of copper appearing on the surface of the rougher food (Table 2), as well as significant charge shifting for
this samples surface, made reliable assignment of copper speciation impossible. There was exposure of an
Fe (2t)) emission from pyrite near 707.4 eV on the rougher concentrate sample surface in Survey 1 (Figure
4c).
178 D. Orwe et al.

- -- -...o,/ I
.2o -~Z-.~-. I cuo + s °
cus + cu2.S ~...
q--..f"---L- - . ~ . . .

0 .Cu2.S + cuo
J= -... ~a2o . • .
-400 i
Cu°+ H ~ .Cu+ S2"
-800
0 2 4 6 8 10 12 14
pI-I
Fig.3 Eh-pH predominance diagram for the Cu-S-H20 system showing experimental Eh/pH points for
the plant surveys, ball mill cyclone overflow for Surveys 1 and 2 (O), feed distribution box for
Survey 2 with NariS (,), and rougher cell 9 for Surveys 1 and 2 (I).

Fe 2p

W
e-
!

(c)

I I 1 I I
735 730 725 720 715 710 705 700
Binding Energy, eV

Fig.4 Iron (2p) spectra for (a) rougher feed Naris off (Survey 1), (b) rougher feed NaI-IS on (Survey 2),
(c) rougher concentrate Naris off (Survey 1) and (d) rougher concentrate Naris on (Survey 2). All
spectra for unetched surfaces.
 Increasing fine copper recovery 179

TABLE 2 Surface atomic concentration of plant samples during surveys determined by XPS
analysis, for the initial surface and after argon ion etching (5 nm). ND=Not Detected.
Feed is new rougher feed and Conc. is rougher concentrate (cells 1-3).

Survey Sample c I o C u ] F e [ S Na [ K I Si I " g l C,

1 Feed 14.2 61.0 0.46 1.16 ND 0.5 0.8 17.3 1.4 2.9
Initial 19.8 53.O 2.44 2.68 3.3 0.5 0.5 13.8 2.5 1.5
2 Feed 21.2 55.1 0.36 1.18 ND 0.9 0.7 16.9 1.0 2.7
Initial Cone 19.1 51.5 2.46 2.43 4.0 0.4 0.4 14.0 4.2 1.5
1 Feed 2.3 66.9 0.34 1.74 ND 0.5 1.1 21.7 1.8 3.4
Etched " Cone 2.5 54.2 5.17 6.40 6.9 0.7 0.7 17.7 4.3 1.6
2 Feed 2.0 67.9 0.20 1.68 ND 0.5 0.9 21.5 2.2 3.1
Etched " Conc 3.4 49.4 4.99 7.62 7.8 ND 0.5 15.9 8.7 1.7

i Cu 2p

_g

! I I I I !
975 965 955 945 935 925
Binding Energy, eV

Fig.5 Copper (2p) spectra for (a) rougher Concentrate NariS off (Survey 1) - - unetched surface, (b)
rougher concentrate Naris o f f (Survey 1) - - etched surface, (c) rougher concentrate NaI-IS on
(Survey 2) - - unetched surface and (d) rougher concentrate NariS on (Survey 2) m etched
surface.

Laboratory studies of porphyry sulphide ores

Copper is readily dissolved from the monzonite ore but not the monzodiorite ore, for pH values less than
6 (Figure 6a). Copper dissolution from digenite contained in the monzonite ore (Table 1) cannot be
explained by simple dissociation of Cu2S, owing to the low solubility of this sulphide. Rather, only oxidation
180 D. Orwe et al.

of digenite to form soluble copper hydrolysis products may explain this high copper concentration. Copper
(II) hydroxide has its lowest solubility at pH 8, with its dissolution increasing towards lower pH values,
forming predominantly copper (II) ion (Figure 7). Evidently, digenite in the monzonite ore readily oxidises
under these conditions, by contrast to chalcopyrite in the monzodiorite ore.

10 -2

I (a)
"~... 10"3I

~o '~ 10"4I

1o-,r
(b)

r~ 10
o

u A . . . A . .'1~.

o
0 2 4 6 8 10 12
pH
Fig.6 (a): Dissolution of copper from the monzonite (O) and monzodiorite (@) ores, as a function of pH.
(b): EDTA extractable copper, expressed as a percentage of the total copper, for the monzonite (O)
and monzodiorite (0) ores, as function of pH.

._9 c u ^. ~ O H v + C u 2 . ,-,..,~.,-, ,4-

3

•Cu(CO 3)2-
o=

i .Cu(OH)2"
2 4 6 8 10 12
pH
Fig.7 Solubility diagram for the Cu (II)-H20-CO 2 system. [CO2]to~= 10-3 mol dm-3 [39].
 Increasingfinecopperrecovery 181

Digenite oxidation in the monzonite ore at alkaline pH values was confirmed by its significant extraction
in EDTA solutions (Figure 6b). Approximately 9% of the total copper in the monzonite sample was
extractable by EDTA at pH 6, increasing to 13% at pH 12. By contrast, only approximately 0.8% of the
copper in the monzodiorite sample was extractable by EDTA (Figure 6b). In the case of the monzonite ore,
the concentration of copper extractable by EDTA in the undiluted pulps (prior to EDTA addition) is
equivalent to approximately 10-2 mol dm -3, suggesting its likely precipitation in a range of copper
hydroxides and carbonates at alkaline pH values (Figure 7). This was confirmed by low dissolution of
copper from the monzonite ore at alkaline pH and in the absence of EDTA (Figure 6a). These EDTA-
extractable copper values suggests that the new flotation feed in both plant surveys contained only low
concentrations of oxidised chalcocite (1.39% EDTA-extractable copper in Survey 1, Figure I).

It appears likely that digenite in the monzonite ore may undergo rapid oxidation after grinding and
conditioning at alkaline pH and mildly oxidising potentials, as encountered in both laboratory [3] and plant
pulp chemical environments (Figure 3). Investigations focused on the effect of controlled potential
sulphidisation (CPS) for the recovery of fine oxidised copper minerals. Initially, the optimum Eh and pH
of sulphidisation was determined for each ore type. At pH 11.5, the optimum Eh of sulphidisation was -100
mV for both ore samples (Figure 8), for which NariS consumption was 240 g/t in the case of the monzonite
ore sample and 65 g/t in the case of the monzodiorite ore sample. At pH 9.0, the optimum Eh of
sulphidisation was also -100 mV though, in this case, greater copper recovery was achieved for the
monzodiorite ore sample (Figure 8b). Increased Naris consumption of the monzonite ore sample may be
attributed to higher levels of EDTA-extractable copper as surface oxidation products on digenite. Other tests,
not discussed here, showed promise for increased copper recovery from a monzodiorite ore by NariS
addition to the labo:ratory grinding mill.

100

90

80

70
NaturalEh
60

50

90

80
0 70

60
Natural Eh
50

40 • . . i . , . | . . . | . • . | . . . | . • .

-200 -100 0 100 200 300 400

Eh / m V

Fig.8 (a): Copper recovery as a function of conditioning Eh adjusted by sodium hydrogen sulphide for
flotation tests on the monzonite ore at pH 11.5 (O) and pH 9.0 (O). Natural Eh values, in the
absence of NaI-IS also shown.
(b): Copper recovery as a function of conditioning Eh adjusted by sodium hydrogen sulphide for
flotation tests on the monzodiorite ore at pH 11.5 (O) and pH 9.0 (O). Natural Eh values, in the
absence of NariS also shown.
182 D. Orwe et al.

Attention will now turn to the size-by-size flotation behaviour of both ores in the absence of NariS. Under
standard processing conditions, the monzonite ore exhibits a marked decrease in maximum copper recovery
for particle sizes less than 30 pm (Figure 9a). The relatively coarse particle size at which the maximum
recovery decreases in this current study and the method of analysis of the kinetic data, suggests that a
genuine difference exists in the surface properties of the copper minerals in the floating and non-floating
components of copper in particle size less than 30 tun. The origin of this difference is linked to digenite
oxidation in the monzonite ore sample. By contrast to maximum recovery, the rate constant of copper
flotation decreases for particle sizes less than 50 larn for the monzonite ore (Figure 9b). The decrease in
rate constant over the particle size range of 50 ~rn to 15 Inn may be expected from particle size effects
alone, decreasing bubble-particle collision rates [36], though a decrease in surface hydrophobicity may also
contribute to the decrease in rate constant within this particle size range. In the case of the monzodiorite
ore (Figure 10a), maximum recovery of both fine (-30 vrn) and coarse (+106 lain) copper was markedly
higher than copper in the same size fractions of the monzonite ore sample. The rate constant of copper
flotation from the monzodiorite ore sample is also dependent on particle size (Figure 10b). The highest rate
constant is obtained near a particle size of 50 ~rn for both ore types•

100
(a)
80

60

4o

"i 20 Monzonite Ore

. . . . . . . t . . . . . . . .

(b)

1.5

1.0

O
0.5

0.0 • . . . . . . ~ . . . . . . . . . . . . i i i

10 100 1000
Size / Microns

Fig.9 (a): Copper maximum recovery as a function of particle size for the monzonite ore for tests without
(O) and with sulphidisation ( S ) (-100 mV at pH 11.5 corresponds to approximately 250 g/t of
NariS for 1 minute conditioning).
(b): Copper rate constant as function of particle size for the monzonite ore for tests with (O) and
without sulphidisation (0).

Attention will now turn to the effect of sulphidisation on the size-by-size flotation rate behaviour of the
monzonite (Figure 9) and monzodiorite (Figure 10) porphyry sulphide ore samples. Sulphidisation clearly
increases maximum recovery of both fine (-30 pin) and coarse copper (+106 pln) from the monzonite ore
(Figure 9a). It is now apparent that the low maximum recovery of both fine and coarse copper from this
ore sample, in the absence of sulphidisation, was due to digenite oxidation. This has clearly been countered
by sulphidisation. By contrast to maximum recovery, sulphidisation only marginally increased the rate
 Increasing fine copperrecovery 183

constant of copper flotation for coarse size fractions only (Figure 9b). In the case of fine copper, it is clear
that effects not related to digenite oxidation dominate the rate constant/particle size relationship over the
size interval of 15 to 50 lain. This shows the value of kinetically analysing size-by-size flotation data, to
extract rate constant and maximum recovery information.

100
(a)
~, 8o

o 6o

4o

"I 20 Monzodiorite Ore

o . . . . . . . . | . . ,

(b)

~
,IIM 1.5

1.0

0.5

o.o
lO 100 1000
Size / Microns

Fig.10 (a): Copper maximum recovery as a function of particle size for the monzodiorite ore for tests
without (C}) and with sulphidisation ( 0 ) (-100 mV at pH 11.5 corresponds to approximately 65
g/t of NariS for 1 minute conditioning).
(b): Copper rate constant as function of particle size for the monzodiorite ore for tests with (O) and
without sulphidisation (0).

Sulphidisation also increases the maximum recovery of fine and coarse copper from the monzodiorite ore
sample, though the increases are not as marked (Figure 10a). It is clear, however, that the high maximum
recovery of fine and coarse copper in the absence of sulphidisation limits potential increases in copper
recovery with sulphidisation for this ore sample. The high recovery of copper from this ore in the absence
of sulphidisation is almost certainly due to its high chalcopyrite content (Table 1), a mineral known not to
rapidly oxidise [37]. This highlights the importance of knowing the copper mineralogical makeup of ores
in laboratory testing, as well as the ore composition during plant trials of sulphidisation on a widely varying
feed mineralogical composition.

Plant survey under nonstandard conditions--with NariS--Survey 2

Controlled potential sulphidisation was applied in the plant with the addition of NariS to the flotation feed
stream to maintain a constant potential of -50 mV in Survey 2. This showed clear increases in copper
recovery for the ore blend being treated during these surveys. With sulphidisation, both final concentrate
copper grade and recovery were increased to 89.6% and 35.7% copper respectively (Figure 1). Other plant
on-off trials on a variety of ore blends, suggested that sulphidisation may increase copper recovery by 3.4%
(on average), with an 80% probability of increasing copper recovery by at least 1.8% [2].
184 D, Orwe et al.

Size-by-size data also showed that a substantial contribution to the increase in copper recovery in Survey
2 occurred as increases in fine copper recovery (Figure 2). While the increase in fine copper recovery is not
as marked as that observed in laboratory studies, it is probable that the lower digenite composition of the
ore blend treated during these particular surveys limited the observed increase in overall fine copper
recovery. The EDTA-extractable copper of the new flotation feed during these surveys most closely
resembles that of the monzodiorite ore, suggesting that chalcopyrite was the predominant copper mineral.
This is also borne out by the relatively high fine copper recovery in the absence of sulphidisation (Survey
1, Figure 2) and the relatively unoxidised state of the rougher concentrate, as determined by XPS (Figure
5a). Other studies also suggest that sulphidised chalcocite may reoxidise after attainment of an appropriate
Eh value necessary for flotation [3]. This may have also partly contributed to the less than expected increase
in fine copper recovery in this particular plant study.

There is also a modest increase in acid soluble copper recovery in fine size fractions in Survey 2. It should
be noted that while acid soluble copper may indicate the content of the oxide copper mineral phases, it is
suggested that the superficial surface oxidation of copper sulphide minerals themselves gives rise to the low
flotation recovery of fine copper. Thus, acid soluble copper measurements may not adequately reflect
alterations in the surface properties of sulphide minerals, either during oxidation or sulphidisation, and how
these alterations may affect flotation recovery.

The application of sulphidisation in Survey 2 reduced the Eh of flotation feed into the stability region of
chalcocite (Figure 3). However, by the ninth cell of flotation the Eh had increased to a similar value to that
obtained for Survey 1 in the absence of sulphidisation. It is of course recoguised that an appropriate Eh for
chalcocite flotation (-50 to +200 mV at pH 11 in [38]) must be attained after sulphidisation. However, this
may give rise to reoxidation of the sulphidised surfaces [3], especially for fine copper minerals for which
residence time in the plant flotation cells may be significantly greater. Other studies have shown that
sulphidised chalcocite may reoxidise after 10 minutes oxygen purging [3]. Further studies should determine
the optimum Eh of collector adsorption and flotation after sulphidisation at a fixed Eh, as the first step
towards determining if reoxidation is occurring.

Sulphidisation treatment decreased the recalculated EDTA-extractable copper in the feed by 40%, while
recovery of EDTA-extractable copper remained low (Figure 1). Sulphidisation could be viewed as a surface
treatment prior to flotation, with flotation still being selective against oxidised mineral surfaces. By contrast
to Survey 1, the recalculated feed flow of EDTA-extractable copper for the final concentrate (0.020 TPH)
and scavenger tailing (0.102 TPH) is now less than the new feed flow (0.172 TPH) (Figure 1), suggesting
that oxidation of copper minerals during flotation is arrested by sulphidisation.

Attention will now turn to the effect of sulphidisation in Survey 2 on the XPS analysis of the mineral
surfaces. Sulphidisation causes a significant decrease in surface atomic concentration of oxygen on the feed
sample surface (Table 2). The decrease in oxygen probably occurs as a reduction in hydroxides on both
sulphide and possibly nonsulphide minerals, as discussed further below. Sulphidisation did not increase
surface exposure of sulphur on the feed sample to levels greater than the detection limit (Table 2), and did
not decrease charge shifting of the feed sample surface (4.6 eV). This may be expected given the low
concentration of sulphide minerals in the feed and the dominance of nonsulphide gangue minerals. The most
significant alterations with sulphidisation occur in the Cu (2p) and Fe (2p) spectra of the rougher
concentrates. By contrast to Survey 1, sulphidisation substantially reduced the high binding energy shoulder
in the Cu (2p) spectrum near 936 eV (Figure 5c). In this case, a 5 rain. argon ion etch did not reduce this
shoulder (Figure 5d), suggesting that this shoulder may be a feature of the unoxidised mineral in this
particular matrix, resulting from differential charging. This was evidenced by the C (Is) spectrum for this
samples surface (not shown). In concert with the decreased state of copper oxidation on the rougher
concentrate surface for Survey 2, there was also a relative increase in exposure of iron in pyrite near 707.4
eV (Figure 4d).
 Increasing fine copperrecovery 185

DISCUSSION

Sulphidisation is commonly applied for the surface treatment of oxide copper minerals prior to their flotation
with standard thiol collectors. However, this study has demonstrated that digenite contained in porphyry
sulphide ores at Ok Tedi may oxidise during treatment, both in plant and laboratory pulp chemical
environments. Significant digenite oxidation may also occur in the open pit, owing to the prevailing climatic
conditions and stockpiling. Oxidation adversely affects maximum recovery of fine digenite from the
monzonite ore sample. By contrast, chalcopyrite in the monzodiorite ore sample was significantly less
oxidised and exhibited higher maximum recovery of fine copper. It is significant to note that while a large
difference in the maximum recovery of fine copper was apparent between these ore types, both ores
exhibited similar flotation rate constant/particle size relationships. This suggests that factors apart from
surface hydrophobicity may be responsible for the decrease in flotation rate constant in the particle size
range from 50 to It5 lam.

Sulphidisation mmkedly increased maximum recovery of fine copper from the monzonite ore sample, and
to a lesser extent from the monzodiorite ore sample. This is in accord with the relative levels of EDTA-
extractable copper for these ore samples after grinding and conditioning. Sulphidisation in the particular
plant survey described in the current study did not increase fine copper recovery as significantly as
laboratory testing on monzonite ore. The level of EDTA-extractable copper in the plant new feed was low,
suggesting that unoxidised copper minerals were present. This also explained the relatively high fine copper
recovery in the absence of sulphidisation for these particular plant surveys. Other on--off plant trials on a
variety of porphyry sulphide ore blends showed significant increases in overall copper recovery with
sulphidisation.

CONCLUSIONS

A particular plant survey showed that the recovery of fine copper minerals in the Ok Tedi concentrator was
at moderate levels, with 81% of -10 pm copper in the feed being recovered in the roughing and scavenging
stages. While this fine copper recovery was high relative to monthly composite size-by-size data, it was still
lower than that of intermediate sized (+20-75 prn) copper in the same plant survey. Pulp and surface
chemical measurements during the survey suggested that significant oxidation of the copper minerals was
occurring during processing. However, the extent of oxidation was not as significant as during laboratory
treatment of the monzonite ore, owing to the large digenite content of this ore sample.

Attention then focused on characterising the size-by-size laboratory flotation response of two porphyry
sulphide ore sample, s, as an initial step towards developing methods to increase fine copper recovery. These
tests showed that for the monzonite ore sample, in which the major copper minerals are digenite and
chalcopyrite, that --20 ~un copper recovery was only 60%. By contrast, for an ore type in which the
predominant copper mineral was chalcopyrite only (monzodiorite), -20 ~ n copper recovery was 85%. The
low recovery of fine copper in the monzonite ore sample was linked to the degree of oxidation of digenite
during laboratory grinding and conditioning.

Controlled potential sulphidisation experiments were undertaken to counter the adverse effects of surface
oxidation. The electrochemical potential of sulphidisation was optimised. These experiments showed clear
increases in fine copper recovery for the monzonite ore sample and, to a lesser extent, the monzodiorite ore
sample. Plant trials of controlled potential sulphidisation increased copper recovery by 3.4% (average) on
a variety of porphyry sulphide ore blends, substantially increasing fine copper recovery. The extent of
increase in copper recovery was linked to the ore type treated.

ACKNOWLEDGMENTS

Financial support for this work from Ok Tedi Mining Limited and the Australian Mineral Industry Research
Association is gratefully acknowledged. Discussions with Daniel Fornasiero are warmly acknowledged. The
support of Pawittar Arora in the XPS analysis is gratefully acknowledged.
186 D. Orweet aL

REFERENCES

. England, J.K., Copper concentrator practice at Ok Tedi Mining Limited, Papua New Guinea. The
Sir Maurice Mawby Memorial Volume, Second Edition, Australasian Institute of Mining and
Metallurgy, Parkville, Vict., 661-665 (1993).
. Orwe, D., Increasing fine copper recovery from the porphyry sulphide ores of Ok Tedi Mining
Limited, Papua New Guinea, M. Appl. Sci. Thesis, University of South Australia (1997).
3. Orwe, D., Grano S.R. & Lauder, D.W., Chalcocite oxidation and its influence on fine copper
recovery at the Ok Tedi concentrator, Papua New Guinea, Accepted for publication, Fifth Mill
Operators Conference, Madang, PNG (1997).
. Mielczarski, J. & Suoninen, E., XPS study of the oxidation of cuprous sulphide in aerated aqueous
solutions, Coll. Surf., 33, 231-237 (1988).
5. Walker, G.W., Stout, J.V., HI & Richardson, P.E., Electro--chemical flotation of sulfides: reactions
of chalcocite in aqueous solution, Int. J. Miner. Process., 12, 55-72 (1984).
6. Adamczyk, Z., Barzyk, W., Czarnecki, J. & Pomianowski, A., Kinetic study of abstraction of ethyl
xanthate ions by oxidised chalcocite surface, Int. J. Miner. Process., 7, 57-77 (1980).
7. Barzyk, W., Malysa, K. & Pomianowski, A., The influence of surface oxidation of chalcocite on
its floatability and ethyl xanthate sorption, Int. J. Miner. Process., 8, 17-29 (1981).
8. Mielczarski, J., XPS study of ethyl xanthate adsorption on oxidised surface of cuprous sulfide, J.
Coll. Interfi. Sci., 120(1), 201-209 (1987).
9. Mielczarski, J. & Minni, E., The adsorption of diethyldithiophosphates on cuprous sulphide,
Surface Interface Anal., 6, 221-226 (1984).
10. Malghan, S.G., Role of sodium sulphide in the flotation of oxidised copper, lead and zinc ores,
Miner. Met. Process., 3, 158-163 (1986).
11. Castro, S., Goldfarb, J. & Laskowski, J., Sulphidising reactions in the flotation of oxidised copper
minerals, I. Chemical factors in the sulphidisation of copper oxide, Int. J. Min. Process., 1,
141-149 (1974).
12. Castro, S., Soto, H., Goldfarb, J. & Laskowski, J., Sulphidising reactions in the flotation of
oxidised copper minerals, II. Role of adsorption and oxidation of sodium sulphide in the flotation
of chrysocolla and malachite, Int. J. Min. Process., 1, 151-161 (1974).
13. Soto, M. & Laskowski, J., Redox conditions in the flotation of malachite with a sulphidizing agent,
Trans. Inst. Min. Metall., C153-157 (1973).
14. Bustamante, H. & Castro, S., Hydrophobic effects of sodium sulphide on malachite flotation,
Trans. Inst. Min. Met., 84, C167-171 (1975).
15. Castro, S.H., Gaytan, H. & Goldfarb, J., The stabilising effect of Na2S on the collector coating of
chrysocoUa, Int. J. Miner. Process., 3, 71-82 (1976).
16. Walker, G.W., Waiters, C.P. & Richardson, P.E., Hydrophobic effects of sulfur and xanthate on
metal and mineral surfaces, Int. J. Miner. Process., 18, 119-137 (1986).
17. McCarron, J.J., Walker, G.W. & Buckley, A.N., An X-ray photoelectron spectroscopic investigation
of chalcopyrite and pyrite surfaces after conditioning in sodium sulfide solutions, Int. J. Miner.
Process., 30, 1-16 (1990).
18. Ragahavan, S., Adamec, E. & Lee, L., Sulfidization and flotation of chrysocolla and brochantite,
Int. J. Miner. Process., 12, 173-191 (1984).
19. Jones, M.H. & Woodcock, J.T., Evaluation of an ion-selective electrode for control of sodium
sulphide additions during laboratory flotation of oxidised ores, Trans. Inst. Min. Metall., 87,
C99-106 (1978).
20. Jones, M.H. & Woodcock, J.T., Optimisation and control of laboratory sulphidisation of oxidised
copper ores with an ion selective electrode, Proc. Australas. Inst. Min. Metall., 266, 11-19 (1978).
21. Glen, R.M., Heyes, G.W. & Senior, G.D., A laboratory investigation of some techniques for
increasing copper recovery from Ok Tedi ore, CSIRO Minerals Report DM-R130, (1995).
22. Gebhardt, J.E. & Kotlyar, D.G., Hydrosulphide depression of copper-sulphide minerals floated by
xanthate and thionocarbamate collectors, In: Copper 91 (G.S. Dobby, S.A. Argyropoulos and S.R.
Rao, Eds.), Pergamon Press, Vol. II, 201-215 (1991).
 Increasingfinecopperrecovery 187

23. Nagaraj, D.R. & Gorken, A., Potential controlled flotation and depression of copper sulphides and
oxides using hydrosulphides in non-xanthate systems, In: Processing of Complex Ores, (G.S.
Dobby and S.R. Rao, Eds.), Pergamon, Elmsford, NY, 203-214 (1989).
24. Nagaraj, D.R. & Gorken, A., Potential-controlled flotation and depression of copper sulfides and
oxides using hydrosulfide in non-xanthate systems, Can. Met. Q., 30(2), 79-86 (1991).
25. Senior, G.D. & Heyes, G.W., Plant testing of a new sulphidisation strategy at Ok Tedi Mining
Limited, CSIRO Minerals Report DM-R336 (1996).
26. Adair, B.J. & Wilkie, G.J., The characterisation of two porphyry ores from the Ok Tedi mine using
QEM*SEM, CSIRO Division of Minerals, Report No. DM-R264 (1996).
27. Light, T.S., Standard solution for redox potential measurement, Anal Chem., 44(6), 1038-1039
(1972).
28. Natarajan, K.A. & Iwasaki, I., Effect of poisoning of platinum electrodes on Eh measurements,
Trans. Am. Inst. Min. Engrs., 254, 22-28 (1973).
29. Lynch, A.J., Johnson, N.W., Manlapig, E.V. & Thorne, C.G., In: Mineral and Coal Flotation
Circuits their Simulation and Control, Developments in Mineral Processing, Elsevier, Amsterdam,
57-96 (1981).
30. Kant, C., Rao, S.R. & Finch, J.A., Distribution of surface metal ions among the products of
chalcopyrite flotation, Min. Eng., 7(7), 905-916 (1994).
31. Woods, R., Yoon, R.H. & Young, C.A., Eh-pH Diagrams for stable and metastable phases in the
copper-suttfur-water system, Int. J. Miner Process., 20, 109-120 (1987).
32. Pratt, A.R., Nesbitt, H.W. & Muir, I.J., Generation of acids from mine wastes: Oxidative leaching
of pyrrhotite in dilute H2SO4 solutions at pH 3.0. Geochimica et Cosmochimica Acta, 58(23),
5147-5159 (1994).
33. Buckley, A.N. & Woods, R., The surface oxidation of pyrite, Applied Surface Science, 2/, 437--452
(1987).
34. Buckley, A.N. & Woods, R., An X-ray photoelectron spectroscopic study of the oxidation of
chalcopyrite, Aust. J. Chem., 37, 2403-2413 (1984).
35. Laajalehto, K., Johansson, L.S., Mielczarski, J., Anderson, S. & Suoninen, E., Electron
spectroscopic studies of interaction of xanthate collectors with different substrates, In: K.S.E.
Forssberg (Ed.), Proc. XVI Int. Min. Process. Congr., Stockholm, Sweden, 691-702 (1988).
36. Ralston, J., A unified approach to flotation, In: Fifth Mill Operators Conference (Aust. Inst. Min.
Metall. PubI.), Roxby Downs, 15-27 (1994).
37. Fairthorne, G., Fornasiero, D. & Ralston, J., The effect of oxidation on the collectorless flotation
of chalcopyrite, Int. J. Miner. Process., 49, 31--48 (1997).
38. Heyes, G.W. & Trahar, W.J., Oxidation-reduction effects in the flotation of chalcocite and cuprite,
Int. J. Miner Process., 6, 229-252 (1979).
39. Attia, Y.A., Surface chemistry of copper minerals in water, Trans. Inst. Min. Metall., 84, C221-230
(1975).

C o r r e s p o n d e n c e on papers published in Minerals Engineering is invited, preferably by e-

mail to bw@minerals.avel.co.uk, or by Fax to +44-(0)1326-318352