A simple spectrophotometric method for determination of gold (III) in aqueous samples

A simple method for rapid determination of trace Au in natural water was presented by using UV–vis spectrophotometry after reaction of gold (III) with 3,3′, 5,5′-tetramethylbenzidine hydrochloride (TMBH) in acidic solution. Under the optimum conditions, in a concentration range of 100–2000 μg L^?1 of Au (III) a good linear calibration graph was obtained (r = 0.9969, n = 7). The percent relative standard deviation (RSD) for determination of 1000 μg L^?1 Au was 10% (n = 3) and limit of detection based on a signal-to-noise ratio (S/N) of 3 (3S_bl) was 50 μg L^?1. The proposed method has been successfully applied to the determination of gold spiked and real aqueous samples.     

Ionic liquid-based modified cold-induced aggregation microextraction (M-CIAME) as a novel solvent extraction method for determination of gold in saline solutions

Modified-cold-induced aggregation microextraction (M-CIAME) was used for determination of gold in saline solutions. It is robust against the much higher concentration of salt (up to 40%). In this method sodium hexafluorophosphate (NaPF₆) was added to the sample solution containing Au-TMK complex and a very small amount of 1-hexyl-3-methylimidazolium tetrafluoroborate [Hmim][BF₄]. Afterward the solution was cooled in an ice bath and a cloudy solution was formed. After centrifuging, the extractant phase was analyzed using a spectrophotometric detection method. Under the optimum conditions, the limit of detection (LOD) was 0.7 ng mL^?1 and the relative standard deviation (RSD) was 1.65% for 50 ng mL^?1 gold. The method was applied for the determination of trace amount of Au in mineral and seawater with satisfactory results.     

Simultaneous determination of Au(III) and Cu(II) with 1-phenyl-1,2-propanedione-2-oximethiosemicarbazone (PPDOT) on solid phase

A new method for the simultaneous determination of copper and gold was developed by derivative spectrophotometry using a previous preconcentration on solid phase. The method is based on the formation of Cu(II)-PPDOT and Au(III)-PPDOT complexes that are extracted from aqueous solution in only 20 min on cationic exchange SP Sephadex C25. In this simultaneous determination, the second derivative and the zero crossing method were used. The copper and gold determinations were carried out at 278.0 nm and 282.0 nm, respectively. The determination range for both analytes was 1.6 × 10⁻⁸–141 × 10⁻⁸ mol L⁻¹. Good levels of repeatability (RSD) of 1.3% and 1.4% were observed for copper and gold, respectively. The method was applied successfully for the copper and gold determination in mineral residuals, minerals and natural water samples. The results were consistent with those provided by ICP-mass spectrometry.     

Multicolumn solid phase extraction with hybrid adsorbent and rapid determination of Au,Pd and Pt in geological samples by GF-AAS

A novel hybrid adsorbent (HA) composed of cellulose fiber, activated carbon, and anion exchange resin Dowex 1 × 8 was prepared for the preconcentration and separation of noble metals, namely, gold (Au), palladium (Pd) and platinum (Pt), in geological samples. The optimal experimental parameters, such as flow rate, sample volume and interfering ions, were investigated. The accuracy of the method was confirmed by added/found method for tap and sea water, and evaluated by analyzing certified reference materials with good agreement. Under the optimal experimental conditions, the detection limits (3σ criteria) of the developed technique were 0.008 ng mL⁻¹ (Au), 0.017 ng mL⁻¹ (Pd) and 0.014 ng mL⁻¹ (Pt) and the sample throughput reach to 30 samples every eight hours. Moreover, the adsorption capacity of HA for Au, Pd and Pt was determined to be 48.2, 35.9 and 29.8 mg g⁻¹, respectively.     

Simultaneous determination of iron and copper in pregnant liquid solutions

A new method for the determination of Fe_Total and Cu is proposed. The method is based on the formation of the iron and copper complexes with 5-sulfosalicylic acid (SSA), the optimal conditions were found, using SSA 5.1 g L⁻¹ in the presence of ammonia 7.5 g L⁻¹ (pH = 10). Under these conditions the selected analytical wavelengths were 488.5 and 423.5 nm for the determination of iron and copper, respectively, by using the zero crossing approach. The detection and quantification limits were 0.02 mg L⁻¹ and 0.07 mg L⁻¹ for iron and 1.14 mg L⁻¹ and 3.80 mg L⁻¹ for copper. The proposed method was applied to the determination of both analytes in pregnant liquid solutions and the recovery was between 98% and 100% and in all cases the relative standard deviation was minor to 2%.     

Solvent extraction and separation of palladium(II) and platinum(IV) from hydrochloric acid medium with dibutyl sulfoxide

The solvent extraction and separation performances of Pd(II) and Pt(IV) from hydrochloric acid solutions were investigated using dibutyl sulfoxide (DBSO) diluted in kerosene. Pd(II) was strongly extracted by a lower concentration DBSO in a lower concentration hydrochloric acid solution while the reverse was obtained for Pt(IV) extraction. Based on independent extraction and separation experiments of Pd(II) and Pt(IV), the separation parameters of Pd(II) and Pt(IV), including dibutyl sulfoxide concentration, contact time of aqueous and organic phases, organic/aqueous (O/A) phase ratio and H⁺ concentration of aqueous phase, were studied in detail, and the optimal separation parameters were obtained and summarized as the following: dibutyl sulfoxide concentration 0.6–1.2 mol dm^?3, organic/aqueous (O/A) phase ratio 0.6–1.0, H⁺ concentration of aqueous phase 1.0–1.5 mol dm^?3 and contact time of two phases 5 min. The as-prepared separation parameters were corroborated by the extraction and separation from a synthetic stock solution containing Pd(II), Pt(IV) as well as several common impurities like Fe(II), Cu(II) and Ni(II). The results revealed that Pd(II) could be separated efficiently from Pt(IV) with a high separation coefficient of Pd(II) an Pt(IV) (2.7 × 10⁴) by predominantly controlling dibutyl sulfoxide and hydrochloric acid concentrations. The extraction saturation capacity of Pd(II) was determined from 1.0 mol dm^?3 HCl solution with 3 mol dm^?3 dibutyl sulfoxide and its experimental value exceeded 14 g dm^?3 under the experimental conditions.Stripping of Pd(II) from loaded organic phase was performed using a mixed aqueous solution containing NH₄Cl and ammonia solutes. Pd(II) (99.2%) was stripped using the stripping solution containing 3% (m/v) NH₄Cl and 5 mol dm^?3 ammonia, respectively.     

Solubilization of heavy metals from gold ore by adjuvants used during gold phytomining

Adjuvants such as cyanide, thiocyanate, and thiosulfate are applied to gold-bearing ores to increase gold solubility and plant uptake of gold during phytomining. The influence of these three adjuvants, added at rates comparable to field application (1 g kg DW^?1 ore), on the leaching of heavy metals from gold ore from the Davis stockpile at the Stawell Gold Mines was examined in batch and column studies. The overall goal was to provide data that specifically addressed the possible collateral impacts that could occur during adjuvant-assisted phytomining in terms of heavy metal solubilization and leaching. Leachate from the cyanide-amended ore had the highest concentrations of Au, Co, Cu, and Ni, with the Au concentration representing ～22% of the total gold present. Thiosulfate-amended ore leached the highest Fe concentration while thiocyanate-amended ore leached the highest Al and Zn concentrations. The results suggest that for this ore, while these adjuvants are present, there is the potential for the mobilization of undesirable elements and Au out of the ore and potentially into groundwater unless adequate hydraulic controls are implemented following adjuvant addition.     

Extraction of titanium (IV) from acidic media by tri-n-butyl phosphate in kerosene

The extraction of titanium (IV) from sulfate, and nitrate solutions has been studied using tri-n-butyl phosphate (TBP) in kerosene. Extraction of titanium was affected by acid concentration over the range of 0.5–4 mol L^?1. The titanium distribution coefficient reached a minimum between 1 and 2 mol L^?1 acid for both sulfate and nitrate solutions. Third phase formation was observed in the extraction of titanium from acidic media at all condition tested. At the next stage, the stripping of titanium was studied using H₂SO₄, H₂SO₄ + H₂O₂ and Na₂CO₃. The kinetics of the stripping were very slow for H₂SO₄. The use of complex forming stripping agents (H₂SO₄ + H₂O₂) and Na₂CO₃ significantly improved the kinetics of stripping. About 98% recovery was achieved by extracting titanium from an aqueous nitrate solution using TBP and stripping with sodium carbonate.     

Post-regrind selective depression of pyrite in pyritic copper–gold flotation using aeration and diethylenetriamine

The present study investigates the effect of aeration and diethylenetriamine (DETA) on the selective depression of pyrite in a porphyry copper–gold ore, after regrinding (at grind sizes, d₈₀ = 38 and 8 μm) with respect to Au recovery and grade using oxygen demand tests, flotation, QEMSCAN, X-ray spectroscopy (XPS) and EDTA extraction analysis. It was found that pyrite depression increases after aeration and with decreasing grind size. This was observed to be due to the markedly higher oxygen consumption rate of pyrite at the 8 μm (kla = 0.10 min⁻¹) than at the 38 μm grind size (kla = 0.02 min⁻¹). The addition of DETA improved pyrite depression (9% with aeration only versus 39% with aeration + DETA) at the 38 μm grind size. Gold and copper flotation recovery followed pyrite recovery for the two grind sizes using XD5002 in the presence of air and DETA.The surface analysis (XPS and EDTA extraction) revealed that the significant pyrite depression at the 8 μm grind size was due to increased amount of surface iron oxides, oxy-hydroxides (FeO/OH), sulphate species and increased liberation of mineral phases (QEMSCAN analysis), whilst the poorer pyrite depression at the 38 μm grind size was due to insufficient liberation of mineral phases and the persistence of activating Cu on the pyrite surface. The addition of DETA increased pyrite depression at the coarser grind size due to a significant reduction in Cu(I)S and increased Cu(II)O species, correlating with the flotation results of pyrite under this test condition. Two-stage copper and pyrite flotation, followed by Au cleaning after regrinding to 38 μm grind size, under high pH or aerated condition is proposed as the recommended route to optimise Au flotation.     

Evaluation of leaching parameters for a refractory gold ore containing aurostibite and antimony minerals: Part I – Central zone

A cyanidation study was conducted on a mild refractory gold ore sample from the Central zone of Clarence Stream Property, owned by Freewest Resources Canada, to develop a leaching strategy to extract gold. Gold, at a grade of 8.00 g/t, is present as native gold, electrum and aurostibite. The ore also contains 2.8% pyrrhotite, together with several antimony minerals (0.8% berthierite and gudmundite, 0.18% native antimony and stibnite). It also exhibits weak preg-robbing properties with 0.16% organic carbon. Aurostibite, a gold antimony compound, is particularly known to be insoluble in cyanide solution. The antimony dissolves in cyanide solution to form antimonates, which retards gold dissolution. Industrial practice of extracting gold from aurostibite generally consists of producing a flotation concentrate, which is leached in a pipe reactor at low alkalinity and high oxygen pressure with about 20 g/L cyanide.The proposed new approach is efficient and allows the extraction of gold directly from an ore at atmospheric pressure and a low cyanide concentration at pH 10.5. The effects of grinding, pre-treatment, lead nitrate, kerosene and cyanide concentrations have been investigated. The maximum gold extraction obtained on the ore was 87.9% using 800 ppm NaCN, 500 g/t lead nitrate, 30 g/t kerosene, DO (dissolved oxygen) 10 ppm and pH 10.5 in 168 h. The associated cyanide consumption was 1.3 kg/t. The additions of lead nitrate and kerosene increased gold extraction. In comparison to a P₈₀ of 74 μm, a P₈₀ of 30 μm significantly increased gold extraction. Gold in solid solution in gudmundite and arsenopyrite was believed to be responsible for the un-leached fraction until mineralogical analysis of hydroseparation concentrates of leach residues showed that most of the un-leached gold occurs as aurostibite, either as locked grains in sulphides/sulpharsenides or as grains with passivation rims of an Au–Sb–O phase. Coarse gold was also found. Gold extraction was not sensitive to cyanide concentration from 250 to 1200 ppm NaCN and high pH was detrimental. Decreasing the cyanide concentration reduced the cyanide consumption from 1.39 to 0.85 kg/t. The removal of coarse gold using a Knelson concentrator and a Mosley table prior to leaching increased the gold extraction to 90.4% (leach residue at 0.77 g/t).     

Leaching and CIL processes in gold recovery from refractory ore with thiourea solutions

In this study, the applicability of leaching and CIL processes in gold recovery with thiourea method, alternative to the cyanidation from the refractory Gümüşhane-Kaletaş/Eastern Black Sea Region (Turkey) ore was investigated.The experiments were conducted at laboratory conditions using ore samples of which approximately 80% were ground to −0.038 mm. The grade of the ore samples was 6.8 g Au/ton. At the first part of the experimental studies, assuming that the gold could be recovered with CIC and CIP processes, the effects of pH, thiourea, oxidizing agent consumption, and leaching time on leaching were investigated. Then, on the basis of the optimum pH and reagent consumption values obtained in the first part (pH = 1.5, 15.2 kg thiourea/ton ore, 140.9 kg iron(III) sulfate/ton ore and 46.2 kg sulfuric acid consumption/ton ore) and adding 50 kg activated carbon/ton ore at the beginning of experiments, the gold leaching extents were obtained for the same leaching times. At this part, the applicability of CIL process in gold recovery with thiourea was investigated for the first time. As a result of the experiments, although higher gold leaching extents were obtained in CIL process, the increase in extent was about maximum 8% and the highest gold leaching extent was obtained as 75% at the end of the 5th hour.     

The interaction of sodium mercaptobenzothiazole with gold electrode and nanorod surfaces

Attenuated total reflectance Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy have been applied to characterise and investigate the interaction of sodium mercaptobenzothiazole (MBT) with gold surfaces and gold nanorods. Gold nanorods (Au NRs) with average aspect ratio of 4.04 ± 0.08 were synthesised and reacted with MBT. Gold(I) mercaptobenzothiazole and the dithiolate, 2,2′-dithiobisbenzothiazole ((MBT)₂) were synthesised and characterised to provide a basis for compound identification. It was concluded that MBT could link two Au NRs by adsorption through the exocyclic S atom on one NR and the endocyclic S atom on the other NR, thereby leading to the formation of Au nanochains in the suspension. The MBT flotation of 100 μm gold particles was also investigated utilising controlled potential techniques. The gold metal particles floated in the cell when the potential reached 0.5 V. At that potential, (MBT)₂ was observed on the gold particles, and their floatability was attributed to the adsorption of that dithiolate species.     

Study on separation of heavy rare earth elements by solvent extraction with organophosphorus acids and amine reagents

The present work describes a study of the separation of rare earth elements (REE) from heavy REE concentrate through solvent extraction. Seven extractants were investigated: three organophosphorus acids (DEHPA, IONQUEST^®801 and CYANEX^®272), a mixture of DEHPA/TOPO (neutral ester) and three amines (ALAMINE^®336, ALIQUAT^®336 and PRIMENE^®JM-T). The organophosphorus extractants were investigated in hydrochloric and sulphuric media whereas the amines performance was assessed in a sulphuric medium. The variables investigated were: concentration of the extractant agent, aqueous phase acidity, aqueous/organic volumetric ratio, contact time, stripping agent concentration (hydrochloric acid solution) and the selective stripping step. In the extraction step, the best separation factors for the adjacent elements were obtained with DEHPA and IONQUEST 801. For 1.0 mol L⁻¹ DEHPA in an initial acidity of 0.3 mol L⁻¹ H⁺, the separation factor was 2.5 Tb/Dy, 2.1 Dy/Ho, 1.9 Ho/Er, 2.0 Ho/Y and 1.1 Y/Er; for 1 mol L⁻¹ IONQUEST 801 in 0.3 mol L⁻¹ of H⁺ it was 2.7 Tb/Dy, 2.4 Dy/Ho, 2.1 Ho/Er, 2.1 Ho/Y e 1.5 Y/Er. The study concluded that for the extractants investigated, IONQUEST 801 is the most indicated for the separation of heavy REE because it has lower affinity with the REE compared to the affinity of DEPHA/REE, which makes the strip of the REE from Ionquest 801 easier than from DEHPA. Moreover, the number of stages necessary for the stripping of the REE from IONQUEST 801 is much lower than that observed when DEPHA is employed.     

Review of rate constants for thiosulphate leaching of gold from ores,concentrates and flat surfaces: Effect of host minerals and pH

A review of literature data for different types of sulphide concentrates and gold ores has been carried out to examine the impact of host minerals and pH upon gold leaching. Analysis of initial rate data over the first 30–60 min of gold leaching from sulphide concentrates or silicate ores over a range of ammonia, thiosulphate, and copper(II) concentrations, pH (9–10.5) and temperatures up to 70 °C shows the applicability of a shrinking sphere kinetic model with an apparent rate constant of the order k_ss = 10⁻⁶–10⁻³ s⁻¹. The dependence of apparent rate constant on pH and initial concentrations of copper(II) and thiosulphate is used to determine a rate constant k_Au(ρr)⁻¹ of the order 1.0 × 10⁻⁴–7.4 × 10⁻⁴ s⁻¹ for the leaching of gold over the temperature range 25–50 °C (ρ = molar density of gold, r = particle radius). These values are in reasonable agreement with rate constants based on electrochemical and chemical dissolution of flat gold surfaces: k_Au = 1.7 × 10⁻⁴–4.2 × 10⁻⁴ mol m⁻² s⁻¹ over the temperature range 25–30 °C. The discrepancies reflect differences in surface roughness, particle size and the effect of host minerals.     

Adsorptive removal of arsenic from river waters using pisolite

This work presents the experimental results for arsenic removal from aqueous solutions using pisolite as a natural inorganic sorbent, a waste mineral product from Brazilian manganese ore mines. A pisolite sample was submitted to physical and chemical characterization; particle size analysis by screening, X-ray diffractometry, X-ray fluorescence, surface area determination by the Brunauer–Emmett–Teller (BET) method and atomic absorption spectrophotometry (AA) for the determination of the species concentration in the pisolite and in the aqueous solution samples from the experiments.Column and batch tests to contact pisolite and aqueous feed solutions were carried out for evaluation of the pisolite’s performance as a natural sorbent for arsenic removal. Experiments using activated pisolite and aqueous feed solutions prepared with Velhas River water were also performed. In the column system, 1.0 g of pisolite removed 1.41 mg of As (4.05% As extraction) from 630 ml of the aqueous feed solution and 1.0 g of activated pisolite extracted 3.51 mg of As (11.6% As extraction). Results for the batch tests with 100 ml of aqueous feed solution and 1.0 g of pisolite removed 1.29 mg of As (24.7% As extraction) and 1.0 g of activated pisolite extracted 3.17 mg (58.2% As extraction).     

Selective elution of the gold cyanide complex from anion exchange resin using mixed solvents

This study is concerned with the use of mixed solvents for the elution of the cyanide complexes of copper and gold from Purolite A500, a strong-base anion exchange resin. The mixed solvents investigated include acetone + water, dimethylsulfoxide + water and N-methyl-2-pyrrolidone + water. Three types of counterions are employed in each of the mixed solvents: CN⁻, Cl⁻ and OH⁻. The effects of counterion concentration and mixed solvent composition on the elution of the complexes are examined. High recoveries of the gold cyanide complex are achieved in the mixed solvents at relatively low counterion concentrations. In contrast, the recoveries of the copper cyanide complexes are 1–3 orders of magnitude lower for the given initial loading of the metals on the resin. The selectivity of the elution process for gold is discussed in terms of the degree of solvation of the various anions in the mixed solvents. The results of this study point to the possibility of using mixed solvents to develop an elution process that is selective for gold over multivalent cyanide complexes.     

On the nanobubbles interfacial properties and future applications in flotation

Nanobubbles, generations forms, basic studies and applications constitute a growing research area, included their usage in advanced mineral flotation. Yet, there are investigation needs for sustainable generation procedures, stability and understanding the nanobubbles interfacial properties and structures. Results proved that a reduction in pressure makes the super-saturated liquid suffers cavitation and nanobubbles were generated. Medium pH and solutions tested were adjusted, in the air saturation vessel, before the nanobubbles were formed, and this allowed to control (in situ) the surface charge/zeta potential-size of the forming nanobubbles. Measurements obtained with a ZetaSizer Nano equipment showed zeta potential values, in the presence of 10⁻² mol L⁻¹ NaCl, displaying sigmoidal pH behaviour between pH 2 (+26 mV) and 8.5 (−28 mV); an isoelectric point was attained at pH 4.5 and were positively charged (up to 23 mV) in acidic medium, a phenomenon which has not been previously observed. In alkaline medium, bubbles were highly negative zeta potential (−59 mV) at pH 10. The double layers appear to play a role in the formation of stable nanobubbles providing a repulsive force, which prevents inter-bubble aggregation and coalescence. Accordingly, the sizes of the nanobubbles depended on their charge and increased with pH, reaching a maximum (720 nm) around the isoelectric point (±5 mV). Highly charged and small nanobubbles (approximately 150–180 nm) were obtained in the presence of surfactants (10⁻⁴ mol L⁻¹ of alkyl methyl ether monoamine or sodium dodecyl sulphate); the zeta potential values in these experiments followed a similar trend of other reported values, validating the technique used with the nanobubbles sizes varying with pH from 150 to 400 nm. Thus, charged and uncharged stable nanobubbles can be tailor-made with or without surfactants and it is expected that their use will broaden options in mineral flotation especially if collectors coated nanobubbles (“bubble-collectors”) were employed. A detailed and updated review on factors involving stability, longevity and coalescence of nanobubbles was made. It is believed that future trend will be on sustainable formation and application of nanobubbles at industrial scale contributing to widen applied research in mineral, materials processing and liquid effluent treatment by advanced flotation.     

Zinc precipitation by heavy-metal tolerant sulfate-reducing bacteria enriched on phosphogypsum as a sulfate source

In the present study, heavy-metal tolerance and precipitation by a mixed culture of sulfate-reducing bacteria (SRB) were evaluated. These bacteria have been enriched during a previous study from a sewage sludge using phosphogypsum as sulfate source. Taking into account that both sulfate and zinc are naturally occurring in phosphogypsum, zinc tolerance of SRB was tested in synthetic media containing 20 mM sulfate and zinc chloride at concentrations ranging from 0 to 200 mg L⁻¹. Zinc tolerance was determined by bacterial growth susceptibility and zinc removal monitoring. Bacterial growth and sulfate reduction were possible between 10 and 150 mg L⁻¹ of initial zinc concentration. Zinc concentrations more than 150 mg L⁻¹ were lethal to SRB. Zinc was removed effectively by SRB to less than 5% from medium containing 150 mg L⁻¹ initial zinc concentrations or less. Energy-dispersive X-ray analysis showed that precipitation of zinc occurred in the form of sulfide. The results presented in this paper have shown that this mixed culture might be of use for bioremediation of sulfate and heavy-metals containing wastewaters.     

Impact of organic carbon on the leachability of vanadium,manganese, iron and molybdenum from shale residues

From 1942 to the 1966, oil was produced by pyrolysis of shale, in Kvarntorp, Sweden. This generated some 40 million m³ of metal rich pyrolyzed shale and discarded fines that were piled on site with its original metal content almost intact. The present study focuses on the leaching of vanadium, manganese, iron and molybdenum from fines after addition of wood chips and steel slag, in outdoor 1 m³ reactor systems at low liquid to solid ratio, in order to evaluate the potential environmental impact and recovery of the elements from the leachates. Seasonal variations were observed, with increased leaching during peak summer. For vanadium and molybdenum, high addition of wood chips decreased the leaching, probably due to adsorption. Manganese showed the opposite behavior while leaching of iron was almost independent of the amount of wood chips. Depending on the systems, up to 2200 μg L⁻¹ vanadium, 90 μg L⁻¹ molybdenum, 25 mg L⁻¹ manganese and 500 mg L⁻¹ iron was found in the aqueous phase. Applied to the 40 million m³ pile, the annual leaching of those elements may reach 14 ton, 0.6 ton, 200 ton and 2400 ton, respectively.     

Effects of quartz addition on chalcopyrite bioleaching in shaking flasks

This paper studies the effects of quartz on bioleaching of chalcopyrite by Acidithiobacillus ferrooxidans, LD-1 through shaking flask experiments. The results showed that quartz concentration can affect the copper extraction. After 32 days, copper extraction of the leaching system at 50 g L⁻¹ quartz concentration increased by about 20%, compared with that of the leaching system without quartz. XRD analysis showed that the amounts of jarosite on the chalcopyrite surface may reduce by the mechanical friction action between fine particles of quartz and chalcopyrite. The analysis of SEM indicated that the surfaces of chalcopyrite particles were eroded by different degrees and the degrees of change were the same as the effects of quartz concentration on copper extraction.