Hydrometallurgy 108 (2011) 109114

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Implementation of sodium hydroxide pretreatment for refractory antimonial gold and silver ores
Oktay Celep a, brahim Alp a,, Doan Paktun b, Yves Thibault b
a b

Mining Engineering Department, Karadeniz Technical University, 61080, Trabzon, Turkey CANMET Mining and Mineral Sciences Laboratories, 555 Booth Street, Ottawa, Ontario, Canada

a r t i c l e

i n f o

a b s t r a c t
Alkaline pretreatment of a refractory goldsilver ore containing antimony minerals such as stibnite, andorite (Sb3PbAgS6) and zinkenite (Pb9Sb22S42) was tested using sodium hydroxide in order to determine its effectiveness in improving the recovery of gold and silver. Mineralogical investigations show that silver was present as andorite and Au/Ag alloy. Gold particles have been observed as associated with quartz and inclusions within the antimony minerals. Increasing the sodium hydroxide concentrations from 0.5 to 5 mol/L, increasing the temperature from 20 to 80 C, and reducing the particle size from 50 to 5 m enhanced the removal of antimony from the ore. Up to about 75.5% Sb removal was achieved by alkaline pretreatment, which in turn remarkably improved the extraction of silver from levels of less than 18.7% to 90% and gold from less than 49.3% to 85.4% during subsequent cyanidation. These ndings, consistent with mineralogical results, suggest that alkaline leaching can effectively be used as chemical pretreatment method as an alternate to the alkaline sulde leaching in the processing of refractory antimonial goldsilver ores. 2011 Elsevier B.V. All rights reserved.

Article history: Received 14 January 2011 Received in revised form 11 March 2011 Accepted 13 March 2011 Available online 3 April 2011 Keywords: Gold Silver Cyanidation Antimony Refractory ore Alkaline leaching

1. Introduction The Akoluk ore deposit, hosted by volcanicsedimentary rocks of the Eastern Pontides, is situated near Ordu in northeastern Turkey. The ore deposit contains a variety of sulde and oxide minerals, as well as native gold (Tysz and Akay, 2000; Yaylal-Abanuz and Tysz, 2010). Total reserves are estimated to be about 1 million tonnes (Anon, 1993). The most signicant trace and minor minerals are associated with stibnite and zinkenite (PbSb sulfosalt), which along with sphalerite are the most widespread ore minerals in the deposit (Ciftci, 2000). According to Aslaner and Ottemann (1972), gold occurs as inclusions in zinkenite (PbSb2S4). Recently, Celep et al. (2009) reported that the ore consisted predominantly of quartz, the illite/kaolinite group of clay minerals and barite with lesser amounts of pyrite, stibnite, sphalerite, zinkenite and andorite. Gold occurs as small particles ranging from 1 to 88 m in association with sulde minerals and quartz. Cyanide leaching tests of 24-h duration showed that metal extractions were consistently low, at less than 47% for gold and less than 19.2% for silver. Diagnostic leaching tests suggested that the decomposition of the sulde could improve the extraction of gold and silver by about 29.5% and 56.7%, respectively. Detailed mineralogical characterization of the Akoluk goldsilver ore has indicated that the ore contains antimony suldes, including andorite (Sb3PbAgS6) and zinkenite (Pb9Sb22S42), as the main silver and gold

Corresponding author. Fax: + 90 4623257405. E-mail address: ialp@ktu.edu.tr (. Alp). 0304-386X/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2011.03.005

carriers (Alp et al., 2010; Celep et al., 2011). Ultrane grinding and roasting of the ore were ineffective as pretreatment for improving the recovery of gold and silver by cyanidation (Celep et al., 2010). Cyanidation tests also showed that lead nitrate addition had a limited effect on gold and silver extractions. The low gold and silver extractions from the ore indicated its refractory nature to cyanide leaching and the need for a suitable chemical pretreatment process to improve metal dissolution. Refractory gold ores do not respond to direct cyanidation; therefore, such ores have to be pretreated prior to cyanidation to liberate the contained gold and silver so that they are readily amenable to extraction (La Brooy et al., 1994). Roasting, pressure oxidation, bio-oxidation and, to a limited extent, ultrane grinding have been commercially applied to increase gold recoveries from refractory ores (Corrans and Angove, 1991; Iglesias and Carranza, 1994; Gunyanga et al., 1999). Alkaline sulde leaching is a suitable pretreatment process for antimonial ores and concentrates (Ubaldini et al., 2000; Bal and Achimoviov, 2006; Curreli et al., 2009; Awe and Sandstrm, 2010; Awe et al., 2010) by making the silver available to cyanide solutions or removing the hazardous or penalty elements such as As and Sb from the ores and concentrates. Alp et al. (2010) and Celep et al. (2011) have already shown that alkaline sulde leaching is an effective pretreatment method ahead of cyanide leaching for the extraction of gold and silver from antimonial refractory ores. Recoveries as high as 90% Ag and 82.6% Au were achieved after the removal of 95% Sb in an alkaline pre-treatment stage under the conditions of 4 mol/L Na2S and NaOH, 15 m particle size, and 80 C (Alp et al., 2010). In addition, increasing NaOH concentrations

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enhanced the dissolution of Sb-bearing minerals. This nding was consistent with reports on leaching of antimonial suldes such as stibnite (Anderson and Krys, 1993; Ubaldini et al., 2000; Sminckov and Komorov, 2005; Sminckov, 2009). Sminckov (2009) showed that the leaching of stibnite by sodium hydroxide was possible. Bal (2000) showed that proustite (Ag3AsS3) and pyrargrite (Ag3SbS3) decompose during the alkaline leach, which makes high silver recovery possible during subsequent cyanidation. No such studies on alkaline pretreatment of antimonial ores containing andorite (Sb3PbAgS6) and zinkenite as the main gold/silver bearing minerals have been reported in the literature. Recent studies (Alp et al., 2010, Celep et al., 2011) indicated that gold losses (up to 13%) occur during the alkaline sulde leaching and the losses increase at high temperatures and high concentrations of sulde. Furthermore, considering the problematic health issues associated with the sulde leaching, this study was designed to evaluate alkaline leaching using sodium hydroxide as a potential pretreatment process alternative to alkaline sulde leaching. 2. Experimental 2.1. Materials The ore used in this study is an antimony-rich refractory gold silver ore from Akoluk (Ordu-Turkey). The ore samples were reduced in size by crushing and grinding. A laboratory-scale stirred media mill was used for ne grinding (80% passing size, d80 = 50, 15 and 5 m) prior to the leaching tests. Particle size analysis of the ore samples was performed by a Malvern Mastersizer 2000 model laser analyzer. The earlier chemical and mineralogical studies (Celep et al., 2009) indicated that it is a high grade gold and silver ore assaying at 220 g/t Ag and 20 g/t Au. In addition, the ore contained 52.2% SiO2, 17.1% Ba, 4.7% Al2O3, 6.9% S, 1.6% Sb, 1.5% Zn, 1.3% Fe2O3, 0.4% Pb, 0.02% As and 0.04% Cu (all in weight percent). Quartz, the illite/kaolinite group clay minerals and barite are the predominant phases in the ore. Pyrite, stibnite, sphalerite, zinkenite and andorite are the main sulde minerals identied in the ore (Celep et al., 2011). 2.2. Mineralogical characterization of the ore Mineralogical analysis of the ore sample was performed to determine gold and silver bearing phases. Characterization studies were carried out using a FEI Quanta 400MK2 Scanning electron microscopy (SEM) equipped with EDAX Genesis 4XMI at the Mineral Research and Exploration Institute of Turkey and a HITACHI variable-pressure SEM with a Link microanalysis system at CANMET. Microanalysis of the mineral grains was performed by a JEOL JXA 8900 electron probe X-ray microanalyzer (EPMA) at CANMET utilizing ve wavelength dispersive spectrometers (WDS) operated at 20 kV with a probe current of 20 to 30 nA. 2.3. Experimental work Tests were designed to evaluate the effects of sodium hydroxide concentrations, temperature and particle size (d80: 550 m). The ground samples (d80: 50 m) were leached in a 1-L glass reactor immersed in a water bath to control the leaching temperature (20 80 C) within 2 C. The vessel with 200-mL leach solution (NaOH) and 70 g ore sample (solids 35% w/vol) was continuously stirred at 750 rpm. Sodium hydroxide (NaOH, assay 99.9% Merck) in the range of 0.55 mol/L NaOH was used to maintain the alkalinity. The leach solution was sampled (10 mL) at regular time intervals for the analysis of antimony. At the end of leaching after 120 min, solid and liquid phases were separated by ltration and the ltrates were analyzed for Sb, Au, Ag, Pb, Zn, Cu and Fe. The residues were airdried, and sampled for analysis to determine the metal recoveries.

Cyanide leaching of the residues was then carried out to determine the effects of alkaline leaching pretreatment on the extraction of gold and silver. Glass reactors (1 L) were used for cyanide leaching of the residues. The reactors were mechanically agitated with pitched-blade turbine impellers and aerated at a ow rate of 0.3 L/ min (Alp et al., 2010; Celep et al., 2011). NaCN (Merck) and NaOH were used to adjust the pH at 10.5 during cyanidation. In all tests, 10-mL samples were taken from the leach pulp at pre-determined time intervals and then centrifuged to obtain clear aliquots for the determination of Au, Ag and free cyanide in solution. Silver nitrate titration in the presence of p-dimethylamino-benzal-rhodanine (0.02% w/w in acetone) as the indicator was used to determine the concentration of free CN in samples (Celep et al., 2011). If required, concentrated cyanide solution (5% NaCN) was added to maintain free CN concentration at the initial level of 1.5 g/L NaCN, and consumption of NaCN was recorded (Celep et al., 2011). On the termination of cyanide leaching tests, the residues were digested in acid (HCl, HNO3, HClO4 and HF) to determine the undissolved metal content. Analysis of gold, silver and antimony from the solutions was carried out using an atomic absorption spectrometer (AASPerkin Elmer AAnalyst 400). The extraction of metals was calculated based on the metal content of leaching residues. 3. Results and discussion 3.1. Alkali pretreatment Alkaline leaching has a signicant advantage over the alkaline sulde leaching due to lower reagent costs. In addition, a small amount of gold can be dissolved in alkaline sulde solutions (Anderson, 2001; Jeffrey and Anderson, 2003; Alp et al., 2010; Celep et al., 2011). This situation will bring additional costs in the course of gold recovery from solution. The alkaline sulde leaching has also potential environmental issues related to the formation of H2S gasses. 3.1.1. Dissolution of metals during pretreatment Alkali pretreatment of the ore at 15 m (d80 particle size) using 3 mol/L NaOH at 80 C in sodium hydroxide solution caused the dissolution of elements in the following proportions: 64.4% Sb, 0.5% Ag, 0.06% Fe, 1.5% Cu, 0.05% Zn and 0.03% Pb. The pretreatment had no effect on the dissolution of gold. The results indicate that sodium hydroxide leaching is highly selective for the removal of antimony from the ore. Although alkaline leaching using alkali metal hydroxides is potentially applicable to elements that form anionic complexes such as Al, Sb, As, Cu, Fe and Pb, the higher metal extractions would require high pressure or temperatures under oxidizing conditions (Gupta and Mukherjee, 1990; Filippou et al., 2007). The alkaline leaching (3 mol/L NaOH, 80 C, d80: 15 m) had no important effect on the dissolution of metals with the exception of antimony. For this reason, the effects on the removal of antimony of NaOH concentration, temperature and particle size were investigated. 3.1.2. Effect of NaOH concentration The effect of leaching time on antimony removal from the ore was investigated at different reagent concentrations (0.55 mol/L NaOH) at the xed slurry temperature of 80 C. The experimental results are presented in Fig. 1. Antimony dissolution varies between 10.4 and 70.1%. Increasing leaching time resulted in the increase of antimony extraction. Most of antimony dissolution had occurred within the rst 5 min at high reagent concentrations. When the leaching time was increased to 2 h, antimony removal was improved only slightly, even at 5 mol/L NaOH. Fig. 1 shows the effect of NaOH concentration (0.55 mol/L) on the removal of Sb from the ore (d80 = 15 m) at 35% w/v solids and 80 C. The dissolution of Sb improved with increasing the

O. Celep et al. / Hydrometallurgy 108 (2011) 109114

111

100

100

80

0.5 M NaOH 1 M NaOH 3 M NaOH 5 M NaOH

80

20C 40C 60C 80C

Sb removal, %

Sb removal, %

60

60

40

40

20 20 0 0 0 20 40 60 80 100 120 0 20 40 60 80 100 120

Leach time, min.

Fig. 3. Effect of leaching time and temperature on the removal of antimony from the ore (3 mol/L NaOH, d80: 15 m).

Leach time, min.

Fig. 1. Effect of leaching time and NaOH concentrations on the removal of antimony from the ore (d80: 15 m, 80 C).

concentration of NaOH. The highest removal of Sb at 70.1% was achieved at the highest reagent concentration of 5 mol/L NaOH. The benecial effect of sodium hydroxide pretreatment is attributed to the decomposition of antimonial phases such as andorite, stibnite and zinkenite present in the ore. Based on the speciation of Sb (Fig. 2), decomposition of these phases by hydroxide would release antimony in the form of species such as SbO 2 , Sb(OH)4 , Sb(OH)6 , SbOS , and SbS (Bal , 2000; Anon, 2005). Sminckov (2009) reported that 2 stibnite was dissolved as SbOS and SbS 2 species (Eq. (1)) in the leaching by sodium hydroxide (at 0.54 wt.% NaOH). In the case of the arsenical silver-bearing sulde minerals such as proustite (Ag3AsS3) in alkaline leaching, it was indicated that silver could remain in Ag2S

(Eq. (2)) phase which is highly soluble within cyanide solutions (Bal, 2000). It is afrmed that the antimonial minerals such as andorite and zinkenite as well as stibnite can be decomposed with similar mechanism.

Sb2 S3s + 2NaOH NaSbOSaq + NaSbS2aq + H2 O

2Ag3 AsS3s + 6NaOH 3Ag2 Ss + Na3 AsO3aq + Na3 AsS3aq + 3H2 O

2 3.1.3. Effect of temperature The inuence of temperature (2080 C) on the release of antimony during the NaOH alkaline pretreatment (3 mol/L NaOH, d80: 15 m and 120 min.) is shown in Fig. 3. An increase of temperature from 20 to 80 C improved the antimony extraction. At 20 C, only 23.1% of the antimony was solubilized from the ore. The extraction of Sb was substantially improved to 64.4% with an increase in the temperature

100

80

Sb removal, %

60

40 50 m 20 15 m 5 m 0 0 20 40 60 80 100 120

Leach time; min.

Fig. 2. EhpH diagrams of the system SbOH (Sb = 10 10 mol/L, 25.15 C, 105 Pa.) (JNC-TDB/GWB) (Anon, 2005). Fig. 4. Effect of particle size on the removal of antimony from the ore (3 mol/L NaOH, 80 C).

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a 100
80

Ag extraction, %

60 as-received ore after alkaline leach

40

20

0 0
Fig. 5. Au particle in quartz matrix with framboidal pyrite.

12

16

20

24

Leach time, hours

b 100
to 80 C. These ndings suggest that temperature is the most inuential factor in the alkaline treatment process. 3.1.4. Effect of particle size The effect of particle size of the ore (d80: 51550 m) on the alkaline leaching process was studied at a xed reagent concentration of 3 mol/L NaOH, and a slurry temperature of 80 C. Decreasing the particle size (d80) from 50 to 5 m produced a positive effect on the solubilization of Sb, which improved from 54 to 72.5% Sb removal (Fig. 4). In addition to increased surface area and liberation of antimony suldes, the benecial effect of reducing particle size can be also attributed to mechanical activation phenomena as reported by Bal (2000). It appears that not all the antimony is responding to alkaline leaching. Approximately ~25% antimony remained in the residue. It appears that the framboidal pyrite with concentric enrichments of antimony and silver is probably responsible for this behavior (Fig. 5, Table 1). In this case, unrecovered antimony would represent the amount tied to framboidal pyrite. 3.2. Cyanidation after treatment The inuence of the sodium hydroxide alkaline pretreatment prior to cyanidation was shown to be effective for the decomposition of the most of antimony minerals. All cyanidation tests indicated that silver and gold recoveries improved after antimony removal by alkaline leach. While less than 18.7% Ag was extracted from the untreated ore, 90% of the silver was recovered following 75.5% antimony removal by alkaline leaching (Fig. 6). The highest silver recovery (90% Ag) was obtained with 3 mol/L NaOH at 80 C and 5 m particle size. Similarly, gold extraction was shown to improve from 49.3% to 55.885.4% following the pretreatment (Fig. 7). The high overall Au and Ag extractions with pretreatment conrm that a large proportion of the gold and silver was refractory in nature because of their occurrence in the structures or as unliberated (i.e. locked) inclusions in the antimony minerals that are apparently insoluble in cyanide solutions. The occurrence and association of gold and silver are illustrated in Fig. 8 where sections of the feed sample were analyzed under SEM-WDS. Table 2 shows the results of microprobe analyses of the phases within the numbered spots in Fig. 8. Andorite is the main gold and silver-bearing mineral in the ore (Fig. 8). Gold particles containing silver also occurred associated with quartz and as inclusions within the minerals such as andorite (Table 2). Andorite were identied to be the most important Ag bearing sulde phase. These ndings indicate andorite (Sb3PbAgS6) and zinkenite (Pb9Sb22S42) as the main gold and silver bearing and hosting minerals (Celep et al. 2011) are not amenable to cyanide leaching without NaOH pretreatment process.

80

R = 0.9775

Ag recovery, %

60

40

20

0 0 20 40 60 80 100

Sb removal, %
Fig. 6. (a) Effect of pretreatment on the silver extraction by cyanidation (3 mol/L NaOH, 80 C, d80: 5 m) and (b) dependence of the cyanide extraction of silver on the removal of antimony by the alkaline pretreatment (d80: 15 m, 80 C).

Table 1 Microprobe phase analyses from spots in Fig. 5. Spot wt.% Au Ag Cu Fe Sb Pb As Zn S Si O Total 1 Gold 85.57 13.79 2 Pyrite 3.63 0.32 33.77 8.32 5.38 0.62 0.08 44.5 0.09 2.91 99.62 3 Pyrite 0.18 0.36 42.23 1.76 0.58 0.69 0.31 49.09 0.06 2.07 97.33 4 Pyrite 0.78 0.41 41.16 1.67 1.21 0.57 0.14 48.85 0.26 2.16 97.21 5 Pyrite 0.25 0.34 42.01 1.77 0.78 0.58 0.55 48.81 0.05 2.94 98.06

99.36

O. Celep et al. / Hydrometallurgy 108 (2011) 109114

113

100

80

Au extraction, %

60

40

20

as-received ore after alkaline leach

0 0 4 8 12 16 20 24

Leach time, hours

b 100
80

Au recovery, %

R = 0.9457
60

40

20

0 0 20 40 60 80 100

Sb removal, %
Fig. 7. (a) Effect of pretreatment on the gold extraction by cyanidation (3 mol/L NaOH, 80 C, d80: 5 m) and (b) dependence of the cyanide extraction of gold on the removal of antimony by the alkaline pretreatment (d80: 15 m, 80 C). Fig. 8. Backscattered electron images showing the locations of microprobe analyses listed in Table 2. (a) Disseminated gold grains (white) and SbPbAg sulde (whitish gray) in andorite grains (light gray) (b) SbAg sulde grains (white) in quartz (gray).

The consumption of cyanide was determined to be 4.85 kg NaCN per ton of the ore. In comparison with the consumption of 9.1 kg/t for the untreated ore (Celep et al., 2009), this gure represents a signicant reduction in cyanide consumption with important cost and environmental implications, including the treatment costs of residual cyanide in the tailings pond water. Thus, the alkaline pretreatment process is considered to be an appropriate method for processing of the antimonial refractory goldsilver ores.

4. Conclusion Sodium hydroxide pretreatment of the refractory goldsilver ore from the Akoluk deposit showed that up to 75.5% of the antimony can be removed by adjusting the molar concentration of the leaching solution. Temperature, particle size and NaOH concentrations were identied to be the most important factors affecting the extraction of antimony and subsequent cyanide extraction of silver and gold. Whereas the direct cyanidation resulted in gold recoveries of about 49.3%, the alkaline pretreatment process signicantly improved the gold recovery to 85.4%. With the removal of about 75.5% Sb during pretreatment, Ag

recoveries reached 90% from very low levels of 510%. A signicant increment in gold and silver extractions corresponded to the removal of antimony from the ore during the alkaline pretreatment. Based on mineralogical investigation, silver was present as andorite and Au/Ag alloy. Gold particles containing silver have been observed as associated with quartz and inclusions within the antimony minerals such as andorite. These ndings were consistent with the alkali pretreatment results. Experimental results demonstrated that sodium hydroxide pretreatment is a viable extractive metallurgy technique for the processing of refractory antimonial gold and silver ores. Mineralogical characterization of materials resulting from alkaline pre-treatments could shed further light on mechanisms of Au and Ag liberation and will be discussed in details at another paper.

Acknowledgements Sincere thanks and appreciation go to the General Directorate of the Mineral Research and Exploration of Turkey (MTA) for SEM-EDX analysis and to Anatolia Minerals Development Ltd. for kindly providing the ore samples.

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Table 2 Microprobe analyses (wt.%) of andorite, an unknown SbAg sulde, gold and quartz grains shown in Fig. 8. Spot wt.% Au Ag Cu Sb Pb S Si O Total 1 SbPbAg sulde 6.7 0.3 32.9 38.3 20.2 2 Andorite 10.1 1.3 40.3 26.0 21.8 3 Andorite 11.4 1.5 42.8 22.0 22.4 4 Andorite 9.9 1.4 40.8 25.9 21.9 5 Gold 84.8 14.6 0 6 Gold 88.2 11.9 b 0.1 7 Gold 85.5 12.7 b 0.1 8 SbAg sulde 12.7 51.7 34.2 9 SbAg sulde 13.1 52.2 34.3 45.4 52.7 98.1 10 Quartz

98.4

99.5

100.1

99.9

99.4

100.2

98.3

98.6

99.6

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