Accepted Manuscript

The adsorption of gold(I) on minerals and activated carbon (preg-

robbing) in non-ammoniacal thiosulfate solutions - effect of
calcium thiosulfate, silver(I), copper(I) and polythionate ions

O. Sitando, G. Senanayake, X. Dai, P. Breuer

PII: S0304-386X(18)30442-0
DOI: doi:10.1016/j.hydromet.2018.10.016
Reference: HYDROM 4926
To appear in: Hydrometallurgy
Received date: 16 June 2018
Revised date: 9 October 2018
Accepted date: 21 October 2018

Please cite this article as: O. Sitando, G. Senanayake, X. Dai, P. Breuer , The adsorption
of gold(I) on minerals and activated carbon (preg-robbing) in non-ammoniacal thiosulfate
solutions - effect of calcium thiosulfate, silver(I), copper(I) and polythionate ions. Hydrom
(2018), doi:10.1016/j.hydromet.2018.10.016

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 ACCEPTED MANUSCRIPT

The adsorption of gold(I) on minerals and activated carbon (preg-

robbing) in non-ammoniacal thiosulfate solutions - Effect of calcium

thiosulfate, silver(I), copper(I) and polythionate ions

O. Sitandoa,b, G. Senanayakea*, X. Daib, P. Breuerb

a
Chemical & Metallurgical Engineering, Environmental Engineering & Chemistry, Murdoch University, 90 South Street,

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Murdoch, Perth WA6150, Australia
b
CSIRO Mineral Resources Flagship, Australian Minerals Research Centre, 7 Conlon Street, Waterford, Perth WA6152,

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Australia

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Abstract

The ability of some typical gangue minerals and activated carbon to adsorb gold(I) (preg-

robbing) in non-ammoniacal thiosulfate solutions was examined at different calcium

thiosulfate concentrations. In the absence of calcium thiosulfate, sulfide minerals such as

pyrite and chalcopyrite, and carbon were highly preg-robbing with 100% gold being adsorbed

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within half an hour. The oxide minerals examined including kaolinite, goethite and hematite

were significantly less preg-robbing under the same conditions. The presence of free

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thiosulfate can significantly reduce or eliminate the preg-robbing of gold on mineral surfaces.

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With an initial thiosulfate concentration of 0.1 M, gold adsorption by oxide minerals was

completely eliminated, while that of sulfide minerals and carbon was insignificant at 0.2 M
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free thiosulfate.
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Copper(I) was found to enhance the preg-robbing of gold by oxide minerals but to reduce

the preg-robbing of gold by sulfide minerals and by carbon. Similar effect of silver(I) was

observed except for chalcopyrite. Trithionate, a by-product of thiosulfate degradation, has no

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significant effect on the preg-robbing of gold(I). Tetrathionate, another by-product of

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thiosulfate degradation, significantly increases the preg-robbing of gold(I) onto pyrite.

Activated carbon enhances the degradation of tetrathionate to trithionate and thiosulfate, the
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latter helps stabilise the gold(I) in solution.

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Keywords: Thiosulfate; Gangue minerals; Carbon; Gold; Adsorption

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1. Introduction

Thiosulfate has received much attention as an alternative non-cyanide lixiviant for gold

extraction over the last three decades. Thiosulfate leaching of gold can be classified under

ammoniacal or non-ammoniacal systems (Aylmore, 2016a,b; Ji et al., 2003). The status of

understanding of these two leaching systems has been recently reviewed (Aylmore, 2016;

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Zhang and Senanayake, 2016; Sitando et al., 2018). The non-ammoniacal process has shown

to be one of the most promising as evident from the thiosulfate gold processing plant

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commissioned in November 2014 at Barrick’s Goldstrike operation in the USA for treating

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double refractory ore (Choi et al., 2013). In both ammoniacal and non-ammoniacal systems,

the gangue minerals can have significant impact on gold leaching efficiency, gold stability
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and thiosulfate consumption. Sulfide minerals such as pyrite, chalcopyrite and chalcocite
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have a beneficial effect on gold leaching efficiency in an ammonia free system through

galvanic interaction with gold (Breuer et al., 2012; Sitando et al., 2015; Zhang et al., 2013).

However, the same minerals have a detrimental effect in ammoniacal systems due to the
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enhanced consumption of the oxidant (Xu et al., 2017; Feng and van Deventer, 2002; Xia,
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2008; Liu et al., 2017). Moreover, during thiosulfate leaching of gold, under certain

conditions, the leached gold concentration decreases over time (preg-robbing) indicating
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instability of dissolved gold(I) due to: (i) adsorption of gold(I) by certain gangue minerals
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and/or carboneacous material; and (ii) re-precipitation of gold(I) in a different form of solid

caused by the change in leach conditions (Muir and Aylmore, 2002; 2004; Xia and Yen,

2005).

Preg-robbing behaviour of different gold ores and common gangue minerals in

ammoniacal thiosulfate solutions has been extensively studied (Aylmore et al., 2014; Feng

and van Deventer, 2001); however, little information is available for non-ammoniacal

thiosulfate solutions. Although there have been some studies on the effect of polythionate
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ions, such as tetrathionate and trithionate ions produced by the reaction of copper(II) and/or

oxygen with thiosulfate, on the stability of gold in the presence of pyrite in calcium

thiosulfate solutions (Daenzer et al., 2016), no information is available on the effects of

silver(I), copper ions, and other common gangue minerals on the loss of gold from non-

ammoniacal thiosulfate leach solutions to the solid phase. In thiosulfate-oxygen system low

concentrations of copper ions are required to significantly increase the rate of gold leaching

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(Zhang and Nicol, 2005; Zhang et al., 2013). The beneficial effect of silver in gold leaching

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has been reported (Oraby et al., 2014; Sitando, 2017; Webster, 1986; Zhang et al., 2008).

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Recently, researchers at Barrick Gold Corporation claimed that pre-treating certain oxide ores

with activated carbon in oxygenated water followed by leaching with calcium thiosulfate,
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significantly improved gold recovery from oxide ores (Choi and Gharelar., 2014)

highlighting the need to study the effect of carbon on the adsorption of gold.
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In this article, the preg-robbing behaviour of six common minerals and activated carbon

in calcium thiosulfate solutions are investigated and discussed. The effect of temperature and
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addition of CaS2O3, silver(I), copper(II) and polythionate ions on the adsorption of gold(I)-
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thiosulfate is also examined. Special emphasis is given to the adsorption of gold(I) on pyrite
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and activated carbon.

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2. Experimental
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Common sulfide and gangue minerals found in gold ores, namely pyrite, chalcopyrite,

goethite, hematite, quartz and kaolinite, were used as potential preg-robbers. The

mineralogical composition of the ores was determined by X-ray diffraction (XRD) and

quantitative XRD techniques at the CSIRO laboratories in Waterford, Western Australia.

Goethite, hematite, quartz and kaolinite had a particle size range (P80) of 75 μm. Pyrite and
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chalcopyrite samples were also milled to the same size using a ball mill. Activated carbon of

average particle size ~ 2 mm supplied by Jacobi Carbons was used. The surface area of the

minerals and carbon was measured using a surface area and porosity analyser, Micrometrics

Tristar II. The specific surface area (m2/g) of partciles was determined by physical

adsorption of N2 gas on the surface of the solid and by calculating the amount of adsorbed

gas corresponding to a monomolecular layer on the surface (Lowell et al., 2004).

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Reproducibility of the results were tested by running the analysis in triplicate and reported

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values are the average of the three with errors below 3%.

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A 100 mg L-1 gold stock solution as Na3Au(S2O3)2·2H2O, 1 M copper stock solution of
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CuSO4·5H2O and 100 mg L-1 silver stock solution of AgNO3 were prepared using milli-Q

water. The stock solutions were prepared about 20 to 30 minutes before the start of the
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experiment. The calcium thiosulfate stock solution from Tessendero Kerley, USA had a

concentration of 1.86 M. Unless otherwise specified, the synthetic solution consisted of 0.05
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M calcium thiosulfate and 10 mg L-1 Au(I) at pH 10. Solutions were prepared by adding
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calculated amounts of 1.86 M calcium thiosulfate stock solution, gold, copper, silver salts of
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interest or polythionate salts (Na2S3O6 / Na2S4O6) to give the desired target concentrations.
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The reagent concentrations were based on literature data (Aylmore et al., 2014) and the recent

work on fundamental studies of gold leaching in calcium thiosulfate (Sitando, 2017). The
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solutions were adjusted to pH 10 using 0.1 M NaOH.

Experiments were performed by bottle rolling 65 mL of the synthetic solutions

containing 5 g of the mineral or 1.5 g activated carbon at 25 °C, unless otherwise specified.

The bottle roll speed was 60 rpm. The pulp density was chosen based on literature data (Feng

and van Deventer, 2001; Sitando, 2017). Bottles were tightly closed during the adsorption
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process. Before the addition of mineral or carbon, a sample was taken and analysed for gold,

copper, silver ions or polythionates (Na2S3O6 / Na2S4O6). Subsequent samples of 2 mL were

taken from the bottle at predetermined time intervals and analysed for the metal ions using

AAS, Agilent model 240FS AA or polythionate and thiosulfate ions using High Pressure

Liquid Chromatography (HPLC), Waters Alliance model 2695. To ensure reproducibility of

results, AAS and HPLC measurements were conducted in triplicate and reported values are

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the average of the three. The relative standard deviations were below 2.5%.

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In order to determine the gold, copper and polythionate adsorption isotherms, a fixed

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amount of mineral was added to the bottles containing increasing initial concentrations of

metal ions or polythionate in 0.05 M calcium thiosulfate solutions. Adsorption was quantified
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in this work as the decrease in concentration of gold(I), silver(I), copper or polythionate ions

when the synthetic solution was equilibrated with minerals in sealed, air-tight bottles. The
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calcualations were made using Eq. 1, where, C0 represents the concentrations of metal or

polythionate ion at the start (t=0) and Ct represents the residual concentration after t hours. In
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order to ensure that no adsorption of gold(I)-thiosulfate by the bottle took place, a blank
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experiment was carried out in the absence of minerals or activated carbon. The blank test
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was run for 24 hours without the addition of mineral or carbon at pH 10 and 25 °C. The test
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was carried out by bottle rolling 10 mg L-1 Au(I) added as Na3Au(S2O3)2·2H2O in the

absence of a background thiosulfate salt in a sealed bottle.

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% Adsorption = ×100 (1)

3 Results and discussion

3.1 Minerallogical assays and blank test

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The mineralogical composition of the solids based on qualitative and quantitative XRD is

listed in Table 1. The surface area and porosity are listed in Table 2. In the blank test in the

absence of other solid additives the gold concentration remained unchanged with time,

indicating that the adsorption of gold(I) on the glass surface of the bottle surface was

negligible.

INSERT TABLE 1

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INSERT TABLE 2

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3.2 Adsorption of gold(I)

3.2.1 Adsorption of gold in the absence of free thiosulfate

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The residual gold(I) concentration in solutions in the presence of different oxide/silicate

minerals: (i) quartz, (ii) kaolinite, (iii) hematite and (iv) goethite, in the absence of free
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thiosulfate and the adsorption of gold(I) on minerals as a function of time is shown in Fig.1a.

Likewise, the results in the presence of sulfide minerals and activated carbon: (i) pyrite, (ii)
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chalcopyrite and (iii) carbon are shown in Fig. 1b. For all the minerals, the adsorption process
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was very fast and equilibrium reached within 0.5 – 4 hours. It is also clear from Fig.1a that
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oxide/silicate minerals show less preg-robbing effect in thiosulfate deficient solutions i.e.
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solution of zero background thiosulfate concentration. Quartz adsorbed only 1.7% of gold

while goethite, kaolinite and hematite adsorbed around 18%. However, at zero background
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thiosulfate concentration, sulfide minerals and carbon are highly preg-robbing with 100%

gold adsorbed within half an hour (Fig. 1b). A similar observation was made in ammoniacal

thiosulfate systems where sulfide minerals and carbon were found to highly preg-robbing in

the absence of free thiosulfate compared to oxide minerals (Aylmore et al., 2014).

INSERT FIG. 1
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3.2.2 Effect of thiosulfate

The effect of thiosulfate concentration on the residual gold(I) concentration and

adsorption of gold on oxide/silicate minerals after bottle rolling for 4 hours is shown in Fig.

2. A thiosulfate concentration of 0.05 M was found to be sufficient to eliminate adsorption of

gold on oxide/silicate minerals (Fig. 2a). Free thiosulfate helps to stabilise Au(I) in two ways:

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(i) by stabilising Au(I) as Au(S2O3)23− in solution (Senanayake, 2005), or (ii) compete with

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gold(I)-thiosulfate for adsorption sites, as discussed further in later sections. The adsorption

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of gold on chalcopyrite, pyrite and carbon is also significantly lower in the presence of free

thiosulfate (Fig. 2b). Only 10, 21 and 39% of gold was adsorbed in the presence of
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chalcopyrite, pyrite and carbon, respectively, in 0.05 M calcium thiosulfate compared to

100% adsorption in solutions free of background thiosulfate. An increase in background

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thiosulfate from 0.05 to 0.2 M calcium thiosulfate almost eliminated the adsorption of gold

on sulfide minerals and carbon (Fig. 2b). The results thus highlight the importance of
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maintaining a high level background thiosulfate concentration throughout the leaching to

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achieve good gold stability. However, a further increase in thiosulfate concentration can
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result in an increase in sulphur species in the system which has a detrimental effect on gold
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leaching process (Baron et al., 2013; Watling, 2007).

Since the sulfide minerals and carbon were found to be more preg-robbing than
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oxide/silicate ores in solutions free of background thiosulfate, these minerals and carbon

might possess active sites for adsorption and/or reduction of gold(I)-thiosulfate (Rees and van

Deventer, 2000). Gold(I)-thiosulfate complex ion may be adsorbed and reduced on defected

sulfide surface according to Eq. 2 (Xia and Yen, 2005). Moreover, the gold(I)-thiosulfate

adsorbed at zero background thiosulfate concentration could be reduced to metallic gold on

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the surface of the sulfide minerals according to Eq. 3 in the presence of iron(II) (Xia and Yen,

2005):

Au(S2O3)23− + defected sulfide surface + e- = Au + 2S2O32− (2)

Au(S2O3)23− + Fe2+ + 3OH− = Au + 2S2O32− + Fe(OH)3 (3)

INSERT FIG 2

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3.3 Adsorption of copper(I) ions

Copper is commonly added as copper(II) to a non-ammoniacal thiosulfate leaching

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system as a catalyst to enhance the gold leach rate. However, in the absence of ammonia,

copper(II) is readily reduced by thiosulfate to copper(I) to form copper(I) thiosulfate

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complexes and tetrathionate (Zhang and Nicol, 2005; Senanayake, 2005).Therefore,

maintaining a certain level of copper in the leach solution is important to achieve a good
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leach efficiency. The deportment of copper during leaching is thus of interest. In the presence
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of free thiosulfate, copper(I) is the species adsorbed on the mineral surface, if it occurs. The
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plots for the adsorption of copper(I) thiosulfate on oxide/silicate minerals as a function of

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time are shown in Fig. 3a. Among oxide minerals, iron oxides such as goethite and hematite

have preference for the adsorption of copper. A similar trend was reported for goethite and
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kaolinite in ammoniacal thiosulfate solutions (Aylmore et al., 2014). Pyrite, which is an iron

containing sulfide mineral, was also found to strongly adsorb copper ions (Fig. 3b). More

than 60% copper was removed from solution in the presence of pyrite. Thus, the presence of

pyrite would significantly reduce the amount of copper available for the gold leaching

process and impact on the gold leach efficiency. In all cases the precipitation of copper

sulfide cannot be ruled out, as CuS and Cu2S are shown as stable species associated with
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thiosulfate solutions of pH 10, in the presence (Aylmore and Muir, 2001) or absence of

ammonia (Sitando et al., 2018). Carbon does not readily adsorb copper, as indicated in Fig.

3b where less than 10% of copper being adsorbed even after 24 hours.

INSERT FIG. 3

3.4 Adsorption of silver(I)

Naturally occurring gold ores commonly contain different levels of silver. The

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dissolved silver causes instability of gold particularly in the presence of polythionates due to

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precipitation (Aylmore et al., 2014). Therefore, its deportment during leaching is also of

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interest. Fig. 4a shows the adsorption of silver(I) on oxide/silicate minerals as a function of

time in copper-free 0.05 M calcium thiosulfate solutions. The equilibrium for the adsorption
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of silver(I) was reached after approximately four hours for all the minerals. The preg-robbing

behaviour of oxide/silicate ores is almost similar with 10-15% of silver adsorbed after 24
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hours (Fig. 5a). However, adsorption of silver(I) in Fig. 4a was significantly greater than that

of gold(I) in Fig. 2 in the presence of 0.05 M calcium thiosulfate. This can be attributed to the
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large size of Au(S2O3)23− which makes it difficult to coordinate with oxides containing
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hydroxyl groups (Aylmore et al., 2014).

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The results for the adsorption tests of sliver(I) on the pyrite, chalcopyrite and carbon

samples are presented in Fig. 4b. The pyrite sample was found to be a stronger absorbent of
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silver(I) compared to chalcopyrite and carbon. Almost 100% silver(I) was

adsorbed/precipitated on pyrite in four hours compared to 64 and 27% on chalcopyrite and

carbon, respectively. Again, the precipitation cannot be ruled out.

INSERT FIG. 4

3.5 Adsorption of thiosulfate

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The adsorption of thiosulfate on pyrite and carbon in the absence of metal ions is shown

in Fig. 5. For pyrite, the concentration of thiosulfate decreased more than 78% after 24 hours.

This could be attributed to a combined effect of adsorption and pyrite catalysed degradation

of thiosulfate (Zhang and Jeffrey, 2008). By comparison, the adsorption or degradation of

thiosulfate on carbon increased slowly with time, with only 14% adsorbed after 24 hours. The

amount of thiosulfate adsorbed / degraded increases with an increase in the amount of carbon

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(Fig. 6). The effect of pyrite and carbon on the adsorption of thiosulfate is further discussed

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later.

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INSERT FIG. 5
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INSERT FIG. 6

3.6 Equilibrium adsorption isotherms

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3.6.1 Gold(I) ions

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The adsorption isotherms of metal ions or polythionates are reported as the variation of ions
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adsorbed as a function of equilibrium concentration of ions in solution (Aylmore et al., 2014;

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Jeffrey and Brunt, 2007). Fig. 7 shows the adsorption isotherms for gold(I) on carbon, pyrite

and chalcopyrite in 0.05 M calcium thiosulfate solutions in the absence of copper ions. The
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equilibrium adsorption of gold by the minerals is shown as mg gold per kg of dry mineral

which is the adsorption capacity of the mineral (q), calculated using Eq. 4 (Omri and

Benzina, 2012); where, Co and Ce are the initial and equilibrium concentration of ions in (mg

L-1), respectively; V is the volume of solution (L); and m is the mass of the dry mineral (kg).
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(4)

With an initial concentration of 10 mg L-1 Au(I), carbon loads around 150 mg gold per kg

which is higher compared to 40 and 12 mg per kg for pyrite and chalcopyrite, respectively.

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However, the adsorption of gold per unit surface area is very small for carbon (Table 3).

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INSERT FIG. 7

INSERT TABLE 3
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Adsorption data at equilibrium for carbon and pyrite (Fig. 7) were fitted to the Langmuir

and Freundlich isotherms. The Langmuir isotherm is based on the monolayer adsorption of
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gold(I)-thiosulfate ions on the surface of the mineral and is expressed in linear form
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according to Eq. 5 (Langmuir, 1918):

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(5)

where, Ce is the equilibrium concentration (mg L-1); qe is the amount adsorbed at equilibrium
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(mg kg-1); Qo is the monolayer adsorption capacity (mg kg-1); and KL is constant related to

the heat of adsorption (L mg-1). A plot of Ce/qe as a function of Ce should give a straight line.

The Freundlich isotherm is based on the assumption that cations and anions are adsorbed on

the same surface simultaneously and is also expressed in a linear form according to Eq. 6

(Freundlich, 1906),
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( ) (6)

where, KF (mg/kg (L/mg)1/n) and 1/n represent the relative adsorption capacity of the

adsorbent and the intensity of adsorption, respectively.

The isotherm models for carbon and pyrite are presented in Fig. 8 and 9, respectively.

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The constants calculated from Fig. 8 and 9 as well as the correlation coefficients are

presented in Table 4. It can be observed that the experimental data for the adsorption of

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gold(I)-thiosulfate on carbon adequately fit both the Langmuir and Freundlich isotherm

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models. The adsorption of gold on pyrite obeys the Freundlich isotherm model. Adsorption is

favourable in the range 0.1 < 1/n < 1 (Raji and Anirudhan, 1998); thus, the adsorption of gold
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is more favourable on carbon than on pyrite.
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INSERT FIG. 8
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INSERT FIG. 9
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INSERT TABLE 4
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The Langmuir equilibrium constant (KL) can be used to calculate the standard Gibbs free
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energy change (ΔG°) for dilute solution of charged adsorbate (Liu, 2009). The Langmuir

equilibrium constant in L mol-1 can be converted to dimensionless constant by multiplying it

with 55.5 mol water per litre (Liu, 2009), and ΔG° is calculated according to Eq. 7, where, T

is the temperature in Kelvin and R is the ideal gas constant with a value of 8.314 J mol-1

K-1.
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ΔG° = -RT ln(55.5KL) (7)

The standard Gibbs free energy for the adsorption of gold(I) on activated carbon was

calculated at 25 °C as -34.5 kJ mol-1 using KL in Table 3. The negative value of ΔG°

confirms the feasibility of the adsorption process.

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3.6.2 Copper(I) ions

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Fig. 10 depicts the adsorption isotherm of copper(I) in 0.05 M calcium thiosulfate

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solutions. The isotherms indicate that pyrite and goethite have a higher loading capacity for

copper compared to the capacity of carbon. The adsorption of copper per unit area of pyrite is
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higher compared to that on goethite and carbon (Table 5). However, the reduction of

copper(I) or precipitation on the surface of the minerals is also possible, as noted in Section
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3.3.

INSERT FIG. 10
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INSERT TABLE 5
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3.6.3 Polythionate ions

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The adsorption isotherms for trithionate and tetrathionate from a thiosulfate synthetic
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solution onto pyrite and carbon were also investigated. In the presence of pyrite, there was no

significant adsorption of trithionate. The tetrathionate concentration was found to increase

with time as a result of catalysed degradation of thiosulfate adsorbed on the surface of pyrite

(Feng and van Deventer, 2005; Xu and Schoonen, 1995; Zhang and Jeffrey, 2008). The

equilibrium concentration of polythionate ions after five hours is shown in Table 6 with their

corresponding isotherms shown in Fig. 11. The amount of trithionate adsorbed on carbon was
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low compared to that of tetrathionate ions (Fig. 11). A similar trend was reported for carbon

in ammoniacal thiosulfate solutions (Aylmore et al., 2014). In a leach solution containing

5 mM of polythionate ions, 4 g kg-1 and 30 g kg-1 of trithionate and tetrathionate,

respectively, would be adsorbed by carbon, indicating a higher affinity for tetrathionate. The

removal of tetrathionate from the leach solution during the leaching process is beneficial as

this can help reduce passivation of the gold surface (Zelinsky, 2014). The role of carbon in

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the removal of tetrathionate is explained further below.

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INSERT TABLE 6

INSERT FIG. 11
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3.7 Effect of Cu(I), Ag(I) and polythionate on adsorption of gold(I)

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3.7.1 Effect of copper(I) ions

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The detrimental effect of copper due to the enhanced adsorption of gold(I) from
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ammoniacal thiosulfate solutions, where copper exists as both copper(II) ammine and
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copper(I) thiosulfate complexes, in the presence of kaolinite and goethite have been reported

(Aylmore et al., 2014). The effect of copper ions on the adsorption of gold(I)-thiosulfate on
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minerals and carbon from non-ammoniacal thiosulfate solutions in the present study is shown

in Fig. 12. It is clear that an increase in copper concentration results in an increased preg-

robbing of gold causing a higher loss of gold to the selected oxide/silcate minerals. Lower

gold losses can be achieved by maintaining the concentration of copper ions below 1.5 mM.

However, copper concentrations less than 1 mM may not be sufficient to achieve the catalytic

effect of copper on the gold dissolution process. The increase in Cu(II) addition may also
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reduce the free thiosulfate concentration due to its oxidation of thiosulfate to tetrathionate and

its complexation with thiosulfate to form copper(I) thiosulfate complexes (Senanayake,

2005).

INSERT FIG. 12

Contrary to the results for selected oxide/silicate minerals, the presence of copper(I)

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thiosulfate decreased the adsorption of gold(I) ions on pyrite and carbon. As shown in Fig.

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12(c, d), 4 mM copper(I) significantly decreased gold adsorption on pyrite from 40 mg kg-1 to

7.5 mg kg-1. It also decreased the adsorption of gold on carbon from 48 mg kg-1 to 39 mg kg-

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1
. The significant decrease in the adsorption of gold on pyrite in the presence of copper ions
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could be attributed to one or more of the following: (i) the formation of copper(I)-thiosulfate

species (Smith and Mertell, 1976; Senanayake, 2005) that would compete with Au(S2O3)23−
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to adsorb on the mineral surface and reduce the adsorption of gold (as demonstrated in Fig. 3,

pyrite has a high affinity for copper(I)); (ii) copper(I) maintains potentials near the mineral
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surfaces sufficiently high to prevent reduction of Au(I) to Au(0) (Aylmore et al., 2014) and;
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(iii) in alkaline solutions, at high concentration, copper precipitation as Cu2S and or CuO is
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possible (Zhang, 2007) which can passivate the adsorbing surface for gold.
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3.7.2 Effect of silver(I) ions

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The effect of silver(I) ions on the adsorption of gold(I)-thiosulfate on pyrite and

chalcopyrite from copper free thiosulfate solution has been studied. The results are presented

in Fig. 13. The adsorption of gold(I) on pyrite decreases with the increase in silver(I)

concentration. With the addition of 0.46 mM silver(I), gold adsorbed on pyrite decreased

significantly from 27 mg kg-1 to 3 mg kg-1 whilst the adsorption of gold on chalcopyrite

increased from around 8 mg kg-1 to 16 mg kg-1. The addition of silver(I) ions to thiosulfate
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solutions results in the formation of silver(I)-thiosulfate species (Smith and Mertell, 1976;

Hogfeldt, 1982) which would compete with gold(I) for adsorption sites on the pyrite mineral.

However, in the case of chalcopyrite, the presence of high concentration of silver(I) and

copper(I) induces the precipitation of gold and the process is accelerated when there is no

sufficient oxidant (Zhang et al., 2013) and in the presence of tetrathionate (Aylmore et al.,

2014). In an oxygen deficient thiosulfate system, gold precipitates mainly as gold sulfide

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according to Eq. 8 (Gudkov et al., 2010; Zhang et al., 2013).

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2Au(S2O3)23- + S2- = Au2S + 4S2O32-; ∆Go298K = -63.3 kJ mol-1

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(8)
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INSERT FIG. 13
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3.7.3 Effect of polythionate ions

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(a) Gold adsorption on carbon in the presence of trithionate

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The results for the adsorption of gold(I) on carbon from 0.05 M calcium thiosulfate

solutions without and with 10 mM sodium trithionate are presented in Fig. 14. Initially, the
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rate of gold adsorption was high in the first four hours after which there was little change in

the amount of gold adsorbed. It is interesting to note that the addition of trithionate had a

negligible effect on gold adsorbed on carbon. For example, with an initial concentration of 10

mg L-1, gold adsorbed on carbon was 153 mg kg-1 and 147 mg kg-1 in the absence and

presence of 10 mM trithionate, respectively. The minor changes in concentration of sulfur

species as a function of time in the presence of trithionate is shown Fig.15. The adsorption of
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trithionate from solution was low and the results are consistent with Fig.11. The formation of

tetrathionate (Fig.15b) and decrease in thiosulfate and trithionate (Fig. 15a, b) in solution may

be due to the degradation of trithionate and thiosulfate according to Eq. 9.

S2O32- + S3O62- = SO32- + S4O62- (K = 7.9 × 108 at 25 °C) (9)

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INSERT FIG. 14

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INSERT FIG. 15
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(b) Gold adsorption on carbon in the presence of tetrathionate
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Fig. 16 illustrates gold adsorption from copper free thiosulfate solutions on carbon in

the absence and presence of tetrathionate . The adsorption of gold from tetrathionate solution,
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unlike in the presence of trithionate (Fig.14), was found to increase continuously with time. It
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is of interest to note that the presence of tetrathionate significantly decreased gold adsorbed
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indicating the competition between S4O62- and Au(I) for the adsorption sites on carbon. The
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gold adsorbed on carbon was reduced significantly from 153 mg kg-1 to 78 mg kg-1 after a

contact time of 24 hours without reaching equilibrium (Fig. 16). This could be attributed to
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the increase in thiosulfate concentration as a result of tetrathionate degradation (Fig. 17a, b);

thus, more thiosulfate is available to stabilise Au(S2O3)23- in the slurries or to compete with

gold(I)-thiosulfate for adsorption on carbon. The rapid decrease in tetrathionate and

corresponding increase in thiosulfate and trithionate in the presence of carbon also indicates

that carbon is possibly catalysing the degradation of adsorbed tetrathionate to thiosulfate (Eq.

10):
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2S4O62− + 3OH− = 2.5S2O32− + S3O62− + 1.5H2O (K = 1.1 × 1010) (10)

INSERT FIG. 16

INSERT FIG. 17

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(c) Gold adsorption on pyrite in the presence of trithionate

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The adsorption of gold on the pyrite mineral in the absence and presence of trithionate
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is illustrated in Fig. 18. Gold adsorption on pyrite is also not influenced to any appreciable

extent by the presence of sodium trithionate. The change in thiosulfate, trithionate and
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tetrathionate species as a function of time in the presence of trithionate is shown in Fig. 19.

The increase in trithionate and formation of tetrathionate in solution may be attributed to the
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catalytic activity of pyrite on thiosulfate degradation (Feng and Deventer, 2005; Xia and Yen,
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2005; Zhang and Jeffrey, 2008). Thus, the degradation of thiosulfate can be represented by
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Eqs. 9 and 11 as suggested by Zhang and Jeffrey (2008):

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3S2O32- + 6OH- = 2S3O62- + 3H2O + 8e- (11a)

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2O2 + 4H2O + 8e- = 8OH- (11b)

3S2O32- + 2O2 + H2O = 2S3O62- + 2OH- (K = 8.6 × 1077) (11)

INSERT FIG. 18
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INSERT FIG. 19

(d) Gold adsorption on pyrite in the presence of tetrathionate

It was observed that preg-robbing on pyrite mineral increases significantly with time in

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the presence of tetrathionate (Fig. 20), with more than 96% of the initial gold adsorbed after

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24 hours. Thus, in the presence of pyrite, the concentration of tetrathionate should be kept

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low during the leaching process to prevent excessive loss of gold. The change in

concentration of sulfur species in the presence of tetrathionate is shown in Fig. 21. The
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concentration of thiosulfate decreases with time due to the catalytic degradation of thiosulfate

on the surface of pyrite as indicated earlier in Eq. 9. Tetrathionate formed from the
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degradation of thiosulfate also decompose (Eq. 12), forming thiosulfate and trithionate, the

latter is quite stable in alkaline solutions (Zhang and Dreisinger, 2002):

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2S4O62− + 3OH− = 2.5S2O32− + S3O62− + 1.5H2O (K = 1.1 × 1010) (12)

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INSERT FIG. 20

INSERT FIG. 21
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4. Conclusions

The preg-robbing behaviour of minerals i.e. the adsorption of gold(I) ions from the

pregnant liquor, depends mainly on the concentration of thiosulfate. In the absence of free

thiosulfate, pyrite, chalcopyrite and carbon are highly preg-robbing with 100% gold being

adsorbed within half an hour. The preg-robbing ability of the oxide minerals to adsorb gold(I)
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in the absence of free thiosulfate is less compared to that of sulfide minerals and follows the

descending order: goethite > hematite > kaolinite > quartz. Adsorption of gold(I) onto the

minerals is significantly lower in the presence of free thiosulfate. An initial thiosulfate

concentration of 0.1 M completely eliminates the adsorption of gold by oxide minerals. In

comparison, a higher free thiosulfate concentration of 0.2 M is required to lower the

adsorption of gold by sulfide minerals and carbon to insignificant values.

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The preferential adsorption of gold(I) ions on minerals follow the descending order:

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carbon > pyrite > chalcopyrite. The adsorption of copper(I) ions on minerals followed a

different sequence: pyrite > goethite > carbon. However, the decrease in total copper in
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solution may also be attributed to the formation of copper precipitates. Adsorption of gold(I)-

thiosulfate on carbon obeys both Langmuir and Freundlich isotherm, while that of gold(I)-
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thiosulfate on pyrite follows only the Freundlich isotherm. Copper(I) adsorption on carbon

and pyrite decreases the gold adsorption by these adsorbents, whilst the presence of copper(I)
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increases the adsorption of gold by hematite and kaolinite. Silver(I) has a similar effect as
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copper(I) in the presence of pyrite, hematite and kaolinite.

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Carbon catalyses the degradation of tetrathionate to form trithionate and thiosulfate

which stabilise gold in solution and compete with gold(I)-thiosulfate for adsorption sites.
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Tetrathionate leads to significant loss of gold in the presence of pyrite. Trithionate is

relatively stable in aqueous alkaline solutions and had no significant effect on the adsorption

of gold by pyrite and carbon.

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References

Aylmore, M.G., Muir, D.M., 2001. Thiosulfate leaching of gold – a review. Minerals

Engineering 14, 135-174.

Aylmore, M.G., Muir, D.M., Staunton, W.P., 2014. Effect of minerals on the stability of gold

PT
in copper ammoniacal thiosulfate solutions - The role of copper, silver and

RI
polythionates. Hydrometallurgy, 143, 12-22.

SC
Baron, J.Y., Mirza, J., Nicol, E.A., Smith, S.R., Leitch, J.J., Choi, Y., Lipkowski, J., 2013.
NU
SERS and electrochemical studies of the gold-electrolyte interface under thiosulfate

based leaching conditions. Electrochimica Acta, 111, 390-399. Breuer, P.L., Dai, X.,
MA

Zhang, H., Hewitt, D., 2012. The increased activity in the development of thiosulfate

based process for gold recovery. Refractory gold ore symposium. Proceedings of the
D

ALTA 2012 Gold Sessions, Perth, Western Australia, 21 May-1 June 2012, pp. 1-13.
E
PT

Choi, Y., Baron, J.Y., Wang., Q., Langhans, J., Kondos, P., 2013. Thiosulfate Processing -
CE

From Lab Curiosity to Commercial Application. Proceedings of the World Gold

Conference, Bribane, Australia, 26-29 September 2013. AusIMM. pp. 45-50.

AC

Choi, Y., Gharelar, A.G., 2014. Method for the pre-treatment of gold bearing oxide ores.

Patent WO 2014/191832 A1.

Daenzer, R., Dreisinger, D., Choi, Y., 2016. Role of polythionates on the stability of gold in

thiosulfate leaching of refractory ores in the calcium thiosulfate-air leaching system.

 ACCEPTED MANUSCRIPT

Refractory gold ore symposium. Proceedings of the ALTA 2016 Gold Sessions, Perth,

Western Australia, 21-26 May 2016, pp. 282-298.

Jeffrey, M.I., Brunt, S.D., 2007. The quantification of thiosulfate and polythionates in gold

leach solutions and on anion exchange resins. Hydrometallurgy, 89, 52-60.

PT
Feng, D., van Deventer, J.S.J., 2001. Preg-robbing phenomena in thiosulfate leaching of gold

RI
ores. Minerals Engineering, 14(1), 1387-1402.

SC
Feng, D., van Deventer, J.S.J., 2002. Leaching behaviour of sulphides in ammoniacal
NU
thiosulfate systems. Hydrometallurgy, 63(2), 189-200.
MA

Feng, D., van Deventer, J.S.J., 2005. Thiosulfate decomposition in the presence of sulfides.

In: Deschenes, G., Hodouin, D., Lerenzen, L. (Eds.), Treatment of gold ores, Canadian
D

Institute of Mining, Metallurgy and Petroleum, pp. 129-143.

E
PT

Freundlich, H.M.F., 1906. Over the adsorption in solution. Journal of Physical Chemistry, 57,
CE

385-470.
AC

Gudkov, A., Zhuchkov, I., Mineev, G., 2010. Mechanism and kinetics of sulfite-thiosulfate

dissolution of gold. Russian Journal of Non-Ferrous Metals, 51(5), 393-397.

Hogfeldt, E., 1982. Stability constants of metal-ion complexes, 2nd supplement, IUPAC

Chemical data series no. 21, part A, Inorganic ligands, Pergamon: Oxford, UK.
 ACCEPTED MANUSCRIPT

Langmuir, I., 1918. The adsorption of gas on the plane surfaces of glass, mica and platinum.

Journal of American Chemical Society, 40, 1361-1403.

Liu, Y., 2009. Is the free energy change of adsorption correctly calculated? Journal of

Chemical and Engineering Data, 54, 1981-1985.

PT
Liu, X., Xu, B., Min, X., Li, Q., Yang, Y., Jiang, T., He, Y., Zhang, X., 2017. Effect of pyrite

RI
on thiosulfate leaching of gold and the role of ammonium alcohol polyvinyl phosphate

SC
(AAPP). Metals, 2017, 7(7), 278-294.

Lowell, S., Shields, J.E., Thomas, M.A., Thommes, M., 2004. Characterization of porous
NU
solids and powders: Surface area, pore size and density. Particle Technology Series,
MA

Vol. 16. Springer Netherlands. pp. 58-81.

D

Muir, D.M., Aylmore, M.G., 2004. Thiosulfate as an alternative to cyanide for gold
E

processing issues and impedients. Mineral Processing and Extractive Metallurgy

PT

Review, 113(1), 2-12.

CE

Muir, D.M., Aylmore, M.G., 2004. Thiosulfate as an alternative to cyanide for gold
AC

processing-issues and impediments. Proceedings of the Green Processing 2002

Conference 29-31 May AusIMM, Melbourne.

Omri, A., Benzina, M., 2012. Removal of manganese(II) ions from aqueous solutions by

adsorption on activated carbon derived a new precursor: Ziziphus spina-christi seeds.

Alexandria Engineering Journal, 51, 343-350.

 ACCEPTED MANUSCRIPT

Oraby, E.A., Browner, R.E., Nikraz, H.R., 2014. Effect of silver in thiosulfate leaching of

gold-silver alloys in the presence of copper and ammonia relative to pure gold and

silver. Mineral Processing and Extractive Metallurgy Review, 35(2), 136-147.

Raji, C., Anirudhan, T.S., 1998. Batch Cr(VI) removal by polyacrylamide-grafted sawdust:

kinetics and thermodynamics. Water Resources, 32, 3772-3780.

PT
RI
Rees, K.L., van Deventer, J.S.J., 2000. Preg-robbing phenomena in the cyanidation of sulfide

SC
gold ores. Hydrometallurgy, 58, 61-80.
NU
Senanayake, G., 2005. Kinetic model for anodic oxidation of gold in thiosulfate media based

on the adsorption of MS2O3− ion-pair. Hydrometallurgy, 76(3-4), 233-238.

MA

Senanayake, G., 2005. Role of copper(II), carbonate and sulphite in gold leaching and
D

thiosulphate degradation by oxygenated alkaline non-ammoniacal solutions. Miner.

E

Eng. 18(4), 409-426.

PT
CE

Sitando, O., 2017. Gold leaching in thiosulfate-oxygen solutions. Ph.D. Thesis. Murdoch

University, Perth, Australia.

AC

Sitando, O., Dai, X., Senanayake, G., Zhang, H., Nikoloski, A.N., Breuer, P., 2015. Gold

dissolution in non-ammoniacal thiosulfate solutions. Comparison of fundamentals and

leaching studies. In the Proceedings of the World Gold Conference, Gauteng, South

Africa, 29 September - 1 October 2015. SAIMM. pp. 273-288.

 ACCEPTED MANUSCRIPT

Sitando, O., Senanayake, G., Dai, X., Nikoloski, A.N., Breuer, P., 2018. A review of factors

affecting gold leaching in non-ammoniacal thiosulfate solutions including degradation

and in-situ generation of thiosulfate. Hydrometallurgy 178, 151-175.

Smith, R.M., Martell, A.E., 1976. Critical Stability Constants. Inorganic complexes, vol. 3.

Plenum Press, New York.

PT
RI
Webster, J.G., 1986. The solubility of gold and silver in the system gold-silver-sulfur-

SC
oxygen-water at 25 ºC and 1atm. Geochimica Cosmochimica Acta. 51(9), 1837-1845.
NU
Watling, K.M., 2007. Spectroelectrochemical studies of surface species in the

gold/thiosulfate system. Ph.D. Thesis. Griffith University, Queensland, Australia.

MA

Xia, C., Yen, W.T., 2005. Iron sulfide minerals in thiosulfate-gold leaching: some problems

and solutions. In: Deschenes, G., Hodouin, D., Lerenzen, L. (Eds.), Treatment of gold
D

ores, Canadian Institute of Mining, Metallurgy and Petroleum, pp. 259-278.

E
PT

Xia, C., 2008. Associated sulfide minerals in thiosulfate leaching of gold: problems and
CE

solutions. Ph.D Thesis. Queens’s University, Ontario, Canada.

AC

Xu, Y., Schoonen, M.A.A., 1995. The stability of thiosulfate in the presence of pyrite in low-

temperature aqueous solutions. Geochim. Cosmochim. Acta. 59(22), 4605-4622.

Xu, B., Kong, W., Li, Q., Yang, Y., Jiang, T., Li, X., 2017a. A review of thiosulfate leaching

of gold: Focus on thiosulfate consumption and gold recovery from pregnant solution.

Metals, 7(6), 222-237.

 ACCEPTED MANUSCRIPT

Xu, B., Yang, Y., Li, Q., Jiang, T., Zhang, X., Li, G., 2017b. Effect of common associated

sulfide minerals on thiosulfate leaching of gold and the role of humic acid additive.

Hydrometallurgy, 171, 44-52.

Zelinsky, A.G., 2014. RDE study of thiosulfate oxidation on gold. Electroanalytical

PT
Chemistry, 735, 111-114.

RI
Zhang, H., Dai, X., Breuer, P., 2013. Factors affecting gold leaching in thiosulfate-O2

SC
solutions. Cyanide alleviation forum, Proceedings of the ALTA 2012 Gold Sessions,

Perth, Western Australia, 25 May-1 June 2013, pp. 214-222.

NU
Zhang, H., Dreisinger, D.B., 2002. The kinetics for the decomposition of tetrathionate in
MA

alkaline solutions. Hydrometallurgy, 66(1), 59-65.

D

Zhang, H., Jeffrey, M., 2008. A study of pyrite catalysed oxidation of thiosulfate. In: Young,
E

C.A., Taylor, P.R., Anderson, C.G., Choi, J. (Eds.), Hydrometallurgy 2008, 6th
PT

International Symposium. SME, Littleton, pp. 769-778.

CE

Zhang, S., 2004. Oxidation of refractory gold concentrate and simultaneous dissolution of
AC

gold in aerated alkaline solutions. Ph.D. Thesis. Murdoch University, Murdoch,

Western Australia, Australia.

Zhang, S., Nicol, M. J., 2005. An electrochemical study of the dissolution of gold in

thiosulfate solutions. part II. effect of copper. Journal of Applied Electrochemistry,

35(3), 339-345.
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Zhang, X.M., Senanayake, G., 2016. A review of ammoniacal thiosulfate leaching of gold-an

update useful for further research in non-cyanide gold lixiviants. Minerals Processing

and Extractive Metallurgy Review, 37(6), 385-411.

Zhang, X.M., Senanayake, G., Nicol, M.J., 2008. The beneficial effect of silver in thiosulfate

PT
leaching of gold. In: Young, C.A, Talor, P.R, Anderson, C.G., Choi, Y. (Eds),

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Hydrometallurgy 2008, SME, Colorado, pp. 801-810.

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Table 1. Quantitative XRD analysis of minerals

Component in % (w/w) Mineral

Goethite Hematite Kaolinite Quartz Pyrite Chalcopyrite

CaCO3a 0.3 0.3

FeO(OH)b 99.1 3.9

Fe2O3c 0.6 92.1

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Al(OH)3d 1.1

Al2Si2O5(OH)4e 1.7 98.5

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SiO2f 1.1 1.5 99.7 1.5 1.4

FeS2g

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99.5

CuFeS2h 90.2

Ca5(PO4)3Fi 7.2
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Mg3Si4O10(OH)2j 1.2

a
calcium carbonate, b goethite, c hematite, d aluminium hydroxide, e kaolinite, f quartz, g pyrite,
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h
chalcopyrite, i apatite, j talc.
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Table 2. Brunauer-Emmett-Teller (BET) surface area of minerals

Mineral BET surface area / (m2 g-1)

Goethite 14.4
Kaolinite 16.2
Quartz 1.3

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Pyrite 0.33
Chalcopyrite 0.31

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Activated carbon 890

Goethite, kaolinite, quartz, pyrite and kaolinite had a particle size range

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of 80% passing 75 μm; carbon average particle size was ~ 2 mm.
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Table 3 Comparison of gold adsorption per unit mas and unit surface area of carbon, pyrite and

chalcopyrite at equilibrium

Adsorbent Surface area Adsorption

(m2 g-1) (mg kg-1) (mg m-2)
Carbon 890 153 0.00017

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Pyrite 0.33 40 0.121
Chalcopyrite 0.31 12 0.039

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Conditions: Initial [Au(I)] = 10 mg L-1, 0.05 M CaS2O3 at initial pH 10 and 25 ºC.

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Table 4. Fitting parameters of Langmuir and Freundlich isotherms for the adsorption of gold on carbon and

pyrite

Adsorbent Isotherm model Constants (at 25 °C) Value

Carbon Langmuir Qo 435

KL 0.1
R2 0.99

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Freundlich KF 43.7

1/n 0.7

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R2 0.99

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Pyrite Freundlich KF 1.5
1/n 1.6
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R 0.99
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Table 5. Comparison of copper adsorption per unit mass and unit surface area of carbon, goethite and

pyrite

Adsorbent Surface area Adsorption

(m2 g-1) (mg kg-1) (mg m-2)
Carbon 890 104 0.00012
Goethite 14.4 377 0.039

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Pyrite 0.33 775 2.35

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Conditions: initial [Cu(I)] = 100 mg L-1, 0.05 M CaS2O3 at initial pH 10 and 25 ºC.

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Table 6. Equilibrium concentration of sodium trithionate and sodium tetrathionate in solution after contact

with carbon

Initial concentration After 5 hours

2- 2-
of polythionates / mM S3O6 / mM S4O6 / mM
5.0 4.6 3.3
7.0 6.5 4.3

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10.0 9.0 5.2

Conditions: Initial pH 10 at 25 ºC, 5 hours contact time. 2.3% (w / v) carbon

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Fig. 1

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Fig.1. Change in residual concentration of gold(I) (solid lines and open symbols) and % gold adsorbed

(dashed lines and solid symbols) on (a) oxide/silicate minerals, (b) sulfide minerals and carbon from

solutions free of background thiosulfate. Conditions: 10 mg L-1 Au(I) as Na3Au(S2O3)2·2H2O, 0 M free

thiosulfate,7.7% (w / v) minerals, 2.3% (w / v) carbon at pH 0 and 25 ºC.

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Fig. 2

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Fig. 2. Effect of calcium thiosulfate concentration on residual concentration of gold(I) (solid Lines and

open symbols) and % gold adsorbed (dashed lines and solid symbols) on (a) oxide/silicate minerals, (b)

sulfide minerals and carbon. Conditions: 10 mg L-1 Au(I) as Na3Au(S2O3)2·2H2O, 7.7% (w / v) minerals,

2.3% (w / v) carbon, 4 hours contact time at pH 10 and 25 ºC.

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Fig. 3

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Fig. 3. Change in residual concentration of total copper (solid lines and open symbols) and % copper
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Adsorbed (dashed lines and solid symbols) on (a) oxide/silicate minerals, (b) pyrite and carbon as a

function of time. Conditions: 100 mg L-1 copper(II), 0.05 M CaS2O3, 7.7% (w / v) minerals, 2.3% (w / v)
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carbon, at pH 10 and 25 ºC.

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Fig. 4

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Fig. 4. Change in residual concentration of silver(I) (solid lines and open symbols) and % silver adsorbed
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(dashed lines and solid symbols) on (a) oxide/silicate minerals, (b) sulfide minerals and carbon.

Conditions: 100 mg L-1 silver(I), 0.05 M CaS2O3, 7.7% (w / v) minerals, 2.3% (w / v) carbon at initial pH
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10 and 25 °C.
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Fig. 5

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Fig. 5. Change in residual concentration of thiosulfate in solution (solid lines and open symbols) and %

thiosulfate adsorbed (dashed lines and solid symbols) on carbon and pyrite as a function of time.
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Conditions: Initial [CaS2O3] = 0.05 M, 7.7% (w / v) pyrite, 2.3% (w / v) carbon at initial pH 10 and 25 ºC.
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Fig. 6

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Fig. 6. Effect of amount of carbon on the residual concentration of thiosulfate (solid line and open

symbols) and % thiosulfate adsorbed (dashed line and solid symbols) on carbon (Initial [CaS2O3] = 0.05

M, 2.3% (w / v) carbon, contact time 4 hours at initial pH 10 and 25 ºC).

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Fig. 7

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Fig. 7. Equilibrium adsorption of Au(I) on solids as a function of Au(I) in solution. Conditions: 0.05 M

CaS2O3, 4 hours contact time, roll speed 60 rpm at pH 10 and 25 °C, 7.7% (w / v) minerals, 2.3% (w / v)

carbon, initial Au(I) concentration of 2.5, 5, 10 and 12.5 mg L-1.

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Fig. 8

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Fig. 8. Isotherm models for gold(I) adsorption on carbon from calcium thiosulfate solutions: (a) Langmuir

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model, (b) Freundlich model. Conditions: 0.05 M CaS2O3, pH 10 at 25 °C, 2.3% (w / v) carbon.
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Fig. 9

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Fig. 9. Isotherm models for gold(I) adsorption on pyrite from calcium thiosulfate solutions, (a) Langmuir

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model, (b) Freundlich model. Conditions: 0.05 M CaS2O3, pH 10 at 25 °C, 7.7% (w / v) pyrite.
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Fig. 10

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Fig. 10. Equilibrium adsorption of copper(I) thiosulfate on solids as a function of copper ions in solution.
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Conditions: 0.05 M CaS2O3, 4 hours contact time, 7.7% (w / v) minerals, 2.3% (w / v) carbon at initial pH

10 and 25 °C.
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Fig. 11

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Fig. 11. Equilibrium adsorption of polythionate on carbon as a function on polythionate ion in solution.

Conditions: 50 mM free CaS2O3, 5 hours contact time at initial pH 10 and 25 ºC, 2.3% (w / v) carbon, no
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Fig. 12

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Fig. 12. Effect of copper(II) on the adsorption of gold on (a) hematite, (b) kaolinite, (c) pyrite, (d) carbon
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from calcium thiosulfate solutions. Conditions: 10 mg L-1 Au(I) as Na3Au(S2O3)2·2H2O, 0.05 M CaS2O3, 4
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hours contact time, 2.3% (w / v) carbon, 7% (w / v) minerals at initial pH 10 and 25 ºC.

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Fig. 13

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Fig. 13. Effect of silver(I) on the adsorption of gold on pyrite (a) and chalcopyrite (b). Conditions: 10 mg

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L-1 Au(I) as Na3Au(S2O3)2.·2H2O, 0.05 M CaS2O3, 7.7% (w / v) minerals, without copper at initial pH 10

and 25 ºC.
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Fig. 14

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Fig. 14. Effect of trithionate on the adsorption of gold on carbon. Conditions: 50 mM initial CaS2O3, 10
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mg L-1 Au(I) added as Na3Au(S2O3)2·2H2O, 2.3% (w / v) carbon, without copper at initial pH 10 and 25

ºC.
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Fig. 15

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Fig. 15. Variation of concentration of sulfur species in the presence of 10 mM sodium trithionate and
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carbon. (a) thiosulfate, (b) trithionate and tetrathionate. Conditions: 50 mM intial CaS2O3, 10 mg L-1 Au(I)

as Na3Au(S2O3)2·2H2O, 2.3% (w / v) carbon, without copper at initial pH 10 and 25 ºC.

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Fig. 16

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Fig. 16 – Effect of tetrathionate on the adsorption of gold on carbon. Conditions: 50 mM initial CaS2O3, 10

mg L-1 Au(I) added as Na3Au(S2O3)2·2H2O, 2.3% (w / v) carbon, without copper at initial pH 10 and 25
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Fig. 17

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Fig. 17 – Variation of concentration of sulfur species in the presence of 10 mM sodium tetrathionate and

carbon. (a) thiosulfate, (b) tetrathionate and trithionate. Conditions: 50 mM CaS2O3, 10 mg L-1 Au(I) as
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Na3Au(S2O3)2·2H2O, 2.3% (w / v) carbon, without copper at initial pH 10 and 25 ºC.

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Fig. 18

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Fig. 18. Effect of trithonate on the adsorption of gold on pyrite. Conditions: 50 mM initial CaS2O3, 10 mg
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L-1 Au(I) added as Na3Au(S2O3)2·2H2O, 7.7% (w / v) pyrite, without copper at initial pH 10 and 25 ºC.
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Fig. 19

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Fig. 19. Variation of concentration of sulfur species in the presence of 10 mM sodium trithionate and

pyrite. (a) thiosulfate, (b) trithionate and tetrathionate. Conditions: 50 mM CaS2O3, 10 mg L-1 Au(I) as
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Na3Au(S2O3)2·2H2O, 7.7% (w / v) pyrite, without copper at initial pH 10 and 25 ºC.

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Fig. 20

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Fig. 20 – Effect of tetrathionate on the adsorption of gold on pyrite. Conditions: 50 mM initial CaS2O3, 10

mg L-1 Au(I) added as Na3Au(S2O3)2·2H2O, 7.7% (w / v) pyrite, without copper at initial pH 10 and 25 ºC.
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Fig. 21

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Fig. 21. Variation of concentration of sulfur species in the presence of 10 mM sodium tetrathionate and

pyrite. (a) thiosulfate, (b) tetrathionate and trithionate. Conditions: 50 mM CaS2O3, 10 mg L-1 Au(I) as
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Na3Au(S2O3)2·2H2O, 7.7% (w / v) pyrite, without copper at initial pH 10 and 25 ºC.

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Highlights

 Higher preg-robbing of Au(I) by pyrite, chalcopyrite and carbon compared to that

by oxide/silicate minerals

 Au(I) adsorption eliminated by free thiosulfate at 0.1 M (oxides or silicates) or

0.2 M (sulfides or carbon)

 Cu(I) enhances preg-robbing of Au(I) by oxide/silicate but the opposite effect

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observed for sulfide/carbon.

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 Effect of Ag(I) similar to that of Cu(I), except for chalcopyrite.

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 In the presence of pyrite or carbon degradation products of tetrathionate lowers

Au(I) adsorption
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