Dissolution Of Chalcopyrite Research Articles

The Dissolution Behavior of Pyrite and Chalcopyrite During Low-Temperature Pressure Oxidation: Chalcopyrite Influence on Pyrite Oxidation

The research of this paper was carried out on the low-temperature (100 ± 2 °C) pressure (0.2–0.8 MPa) leaching of pyrite, chalcopyrite and their mixture. According to experiments on chalcopyrite dissolution, increasing the oxygen pressure from 0.2 up to 0.8 MPa had a slight effect on chalcopyrite dissolution. Oxygen pressure and initial sulfuric acid concentration in the range of 10–50 g/L had the greatest positive effect on the pyrite oxidation. The SEM and EDX mappings indicate the chalcopyrite and pyrite surfaces to be passivated by elemental sulfur. The oxidation degree of pyrite in its mixture with chalcopyrite increased significantly from 54.5 up to 80.3% in 0–240 min. The reaction time is relative to the dissolution of the individual mineral, while the dissolution of chalcopyrite remained virtually unchanged. The addition of Cu (II) and Fe (III) ions does not influence pyrite dissolution when chalcopyrite is added in a leaching process, which can be explained by the formation of an electrochemical link between the minerals. The positive effect of chalcopyrite addition is associated with a decreased formation of elemental sulfur on the surface of pyrite. The described method can be used for the hydrometallurgical processing of copper raw materials with increased pyrite content, as well as for the pretreatment of copper concentrates with gold-rich pyrite concentrates to increase the recovery of gold and silver.

Kinetic characteristics of bornite and chalcopyrite dissolution in nitric acid

The kinetic characteristics of dissolution of copper-bearing sulfides – chalcopyrite (CuFeS₂) and bornite (Cu₅FeS₄) – in nitric acid were studied. The kinetics of the dissolution process was described using a compressible nucleus model. Chalcopyrite of the Vorontsovskoye deposit and bornite of the Karabash deposit were used as research objects. Solution and cake samples were analyzed by optical emission spectrometry and X-ray fluorescence analysis, respectively. The results obtained were processed in the MS Excel software package. The influence of various factors, including temperature, solvent concentration, particle size, and process duration on the dissolution degree of minerals was studied. The process parameters were varied as follows: temperature – from 35 to 95°C; HNO₃ concentration – from 1 to 9 mol/dm³; particle size – from +0.1 to 0.056 mm; duration – from 0 to 60 min. It was established that an increase in temperature and acid concentration leads to a significant increase in the degree of dissolution of both chalcopyrite and bornite. A decrease in particle size also contributes to a more efficient dissolution of both minerals in nitric acid. The calculated activation energy values were 55 kJ/mol for chalcopyrite and 43 kJ/mol for bornite, which is characteristic of the kinetic region of the process. The reaction orders in terms of reactant were determined: 1.62 for chalcopyrite and 1.57 for bornite. In terms of particle size, these were -1.16 for chalcopyrite and -2.53 for bornite. On this basis, generalized equations of dissolution kinetics for both minerals were derived. The results obtained allow an assumption about the kinetic nature of dissolution of chalcopyrite and bornite under the studied conditions.

The combined leaching of copper, gold and uranium in chloride solutions. I. Chalcopyrite

In a study (Part II) aimed at the simultaneous heap leaching of copper (predominantly chalcopyrite), gold and uranium from an ore, it was found that this could be achieved using chlorate as the oxidant in chloride solutions. As a result, a more detailed study has been made using electrochemical and batch leach tests on pure chalcopyrite electrodes under typical heap leach conditions.The use of chlorate at moderately low concentrations has shown that enhanced rates of dissolution of chalcopyrite can be maintained over periods up to 4 days at ambient temperatures in acidic chloride solutions. The rate of dissolution is enhanced at higher acid concentrations. The rate in the presence of chlorate does not appear to depend on the iron(III) (and presumably the copper(II)) concentration.The observed rates are significantly greater than those predicted for oxidative dissolution from the electrochemistry and the mixed potential model. An alternative non-oxidative mechanism has been revisited to account for this difference.A preliminary measurement has been made of the kinetics of the oxidation of hydrogen sufide and iron(III) by low concentrations of chlorine produced by reaction of chlorate with chloride ions. These reactions are rapid, and theory shows that they would support the proposed non-oxidative mechanism.

Copper and zinc sulfides bioleaching by an extremely thermophilic archaeon in high NaCl concentration

Chloride bioleaching has received attention of several mineral processing industries, particularly in countries where there is scarcity of freshwater and only chloride-containing waters can be used. Therefore, the present work investigated the effect of NaCl (1.0 mol L−1) on the bioleaching of three sulfide minerals: chalcopyrite, bornite, and sphalerite by the thermophilic archaea Sulfolobus acidocaldarius. Chalcopyrite dissolution was only 25 % in the biotic experiment in the absence of chloride, but reached 90 % in the presence of both microorganisms and chloride, while less than 60 % extraction was observed in the abiotic experiment with chloride. In the experiments of bornite bioleaching, 86 % and 77 % of copper were extracted in the biotic and abiotic tests with chloride, respectively. In the absence of NaCl, the biotic and abiotic experiments presented similar copper dissolution (∼35 %). Finally, bioleaching experiments carried out with sphalerite showed zinc extractions below 35 % in all conditions tested. The main contribution from the archaea was its ability to produce low concentrations of ferric ion, which was partially precipitated as jarosite, resulting in low redox potential values (< 450 mV vs. Ag/AgCl), and efficiently bioleached bornite and chalcopyrite. Furthermore, XRD and SEM-EDS analyses demonstrated that sphalerite was practically not leached while bornite was transformed into new copper sulfide phases (CuS and Cu3FeS4). Jarosite and elemental sulfur were products of chalcopyrite and bornite bioleaching in the presence of chloride.

Source Apportionment and Human Health Risks of Potentially Toxic Elements in the Surface Water of Coal Mining Areas.

Contamination with potentially toxic elements (PTEs) frequently occurs in surface water in coal mining areas. This study analyzed 34 surface water samples collected from the Yunnan-Guizhou Plateau for their hydrochemical characteristics, spatial distribution, source apportionment, and human health risks. Our statistical analysis showed that the average concentrations of PTEs in the surface water ranked as follows: Fe > Al > Zn > Mn > Ba > B> Ni > Li > Cd > Mo > Cu > Co > Hg > Se > As > Pb > Sb. The spatial analysis revealed that samples with high concentrations of Fe, Al, and Mn were predominantly distributed in the main stream, Xichong River, and Yangchang River. Positive matrix factorization (PMF) identified four sources of PTEs in the surface water. Hg, As, and Se originated from wastewater discharged by coal preparation plants and coal mines. Mo, Li, and B originated from the dissolution of clay minerals in coal seams. Elevated concentrations of Cu, Fe, Al, Mn, Co, and Ni were attributed to the dissolution of kaolinite, illite, chalcopyrite, pyrite, and minerals associated with Co and Ni in coal seams. Cd, Zn, and Pb were derived from coal melting and traffic release. The deterministic health risks assessment showed that 94.12% of the surface water samples presented non-carcinogenic risks below the health limit of 1. Meanwhile, 73.56% of the surface water samples with elevated As posed level III carcinogenic risk to the local populations. Special attention to drinking water safety for children is warranted due to their lower metabolic capacity for detoxifying PTEs. This study provides insight for PTE management in sustainable water environments.

Study on Chalcopyrite Dissolution Mechanism and Bioleaching Community Behavior Based on Pulp Concentration Gradient at 6 °C

Low-temperature bioleaching is relevant to the recovery of metals in alpine mines, but its development has been constrained by low bioleaching rates at high pulp concentrations. To this end, the bioleaching effect of the microbial community after the domestication of pulp concentration at 6 °C was studied. Domestication improved the bioleaching rate of copper. Environmental scanning electron microscopy (ESEM), X-ray diffraction (XRD), and electrochemical measurements revealed that the domestication process aggravated the corrosion of the chalcopyrite surface by accelerating its dissolution reaction. High-throughput sequencing technology indicated that Acidithiobacillus spp., Leptospirillum spp., and Acidiphilium spp. were the major lineages of the domesticated microbial community. The analysis of the microbial community revealed that domestication changed the microbial structure, enhancing the adaptability of the microbial community to pulp concentrations and acidic conditions. This study uncovered the mechanism by which domestication enhanced the bioleaching efficiency of the microbial community at low temperatures.

Perspectives for Photochemical Leaching Processes of Chalcopyrite: A Solar Radical-Leaching Process

This paper review presents a comparison between conventional leaching and advanced photochemical leaching processes and their potential for use in chalcopyrite leaching. Likewise, it presents an analysis of the differences between the advanced leaching processes, photoleaching and radical-leaching, indicating that the photochemical mechanisms (photooxidation/photoreduction and generation of radical oxygen species (ROS) and radical sulfur species (RSS)) would improve the oxidative dissolution of chalcopyrite, taking advantage of the high oxidizing power of free radicals. Initial experimental results of solar-assisted radical-leaching on chalcopyrite are presented, demonstrating that sulfate radicals (SO4−) allow copper to be leached at a rate 4.7 times higher than in the absence of radicals and sunlight. With these results, a radical-leaching process is presented for the first time, with a perspective toward the future development of a new hydrometallurgical route: solar-assisted radical-leaching.

In-situ and ex-situ experimental investigation on the chalcopyrite replacement in saline solution at 310-365°C and 15-25 MPa

Abstract The replacement of chalcopyrite in NaCl solutions was investigated from 310 to 365° and 15 to 25 MPa with ex-situ surface characterization techniques and in-situ electrochemical methods. The replacement products and reactions were analyzed ex-situ using Raman spectroscopy, scanning electron microscope (SEM) and energy dispersive X-ray spectrometer (EDS). Chalcopyrite dissolution was monitored by open circuit potential (OCP), polarization curves and electrochemical impedance spectroscopy (EIS). The ex-situ and in-situ measurements show that: (i) elevated temperature and pressure promote the oxidative dissolution of chalcopyrite by different pathways; (ii) the altered chalcopyrite surface consists of an outer layer of hematite and an inner layer of covellite; (iii) at elevated temperature, removal of more copper from chalcopyrite surface enhances chalcopyrite dissolution, and favors hematite formation over covellite in the alteration rind; and (iv) at elevated pressure, more iron ions diffuse through the passive covellite layer by point defects, promoting chalcopyrite replacement by covellite over hematite. This study provides experimental evidence on the replacement of chalcopyrite by covellite, the precipitation of hematite and the exchange of Fe/Cu ions between chalcopyrite and hydrothermal brine.

Influencing mechanism of visible light and silver ions on p- and n-type chalcopyrite bioleaching

Different effects and mechanisms of visible light and silver ions (Ag+) on the bioleaching of p- and n-type chalcopyrite (Cpy A and Cpy B, respectively) in the presence of Acidithiobacillus ferrooxidans were investigated. The semiconductor characteristics, bioleaching behaviors, surface morphologies, main phases and surface species of chalcopyrite were evaluated by Hall effect test, bioleaching tests, X-ray diffraction, scanning electron microscope and X-ray photoelectron spectroscopy. According to the results, Cpy A had a higher carrier concentration and greater carrier mobility than Cpy B, resulting in a faster dissolution rate. After 24 d of bioleaching, the copper extraction rate of Cpy A was 91.05%, which was 17.86% higher than that of Cpy B (73.19%) when light illumination and Ag+ existed together. Obviously, visible light and Ag+ promoted the bio-dissolution process of Cpy A more strongly than Cpy B, which was mainly attributed to the higher carrier mobility in Cpy A. Furthermore, charge transfer occurred more rapidly on the chalcopyrite surface when illuminated, and more Ag2S was accumulated, especially for Cpy A. As a result, the dense structure of the passivation layer was destroyed, reducing the passivation effect and promoting chalcopyrite dissolution.

Preservation of Hydrothermal Fluid Copper Isotope Signatures in Chalcopyrite‐Rich Chimneys: A Case Study From the PACMANUS Vent Field, Manus Basin

AbstractCopper isotopes (δ65Cu) in hydrothermal fluids have the potential to provide information on ore‐forming processes occurring below the seafloor, but Cu isotope data from high‐temperature fluids are scarce. Here, we examine the extent to which coexisting sulfide minerals in a hydrothermal chimney can preserve fluid Cu isotope ratios using a fluid‐solid pair of a black smoker (333°C) from the Roman Ruins vent area (PACMANUS) in the Manus Basin. Two ca. 3 cm long transects through the chalcopyrite‐rich chimney wall show an increase in δ65Cu from 0.48 to 2.28‰ from the interior to the exterior, coupled with limited variation in sulfide δ34S (1.52–4.72‰). The Cu isotopic composition of chalcopyrite from the innermost wall closely resembles the δ65Cu value of the paired hydrothermal fluid, indicating that chalcopyrite in the inner ∼5 mm of the chimney records the Cu isotope ratio of the venting fluid. Beyond this, an increase in sulfide δ65Cu toward the exterior correlates with an increase in the relative abundance of secondary Cu sulfides. The appearance of bornite coincides with the presence of small barite crystals, suggesting this represents a redox gradient between reduced hydrothermal fluids and oxidized seawater admixing inwards. Elevated δ65Cu in this zone can be explained by the precipitation of secondary Cu sulfides from 65Cu‐enriched fluids formed during oxidative chalcopyrite dissolution. Our findings indicate that interactions with oxidizing seawater shift chalcopyrite δ65Cu values over small spatial scales, and that caution must be applied if chimney sulfides are used to reconstruct δ65Cu values of high‐temperature hydrothermal fluids.

Enhanced Chalcopyrite Dissolution in Acidic Culture Medium: The Impact of Arsenopyrite Presence

Nowadays, research on promoting the dissolution of chalcopyrite is important. As a natural symbiotic mineral of chalcopyrite, arsenopyrite will have an impact on the dissolution of chalcopyrite. This paper shows the influence of arsenopyrite on the dissolution of chalcopyrite in an acidic culture medium. The leaching results showed that adding arsenopyrite increased the leaching concentration of copper by 332 mg/L. The residues showed a decrease in sulfur through X-ray diffraction analysis (XRD) and an increase in dissolution degree through scanning electron microscope (SEM). Electrochemical experiments have shown that the rest potential of arsenopyrite is higher than that of chalcopyrite, so there is a galvanic interaction, and the impact on chalcopyrite is greater than that of arsenopyrite. The polarization curve also proves this. Under the interaction of galvanic couples, the reduction of S0 production and the enhancement of Cu2+ release can promote the dissolution of chalcopyrite. In addition, X-ray photoelectron spectrometer (XPS) analysis under the action of galvanic coupling indicates that more SO42− is generated on the surface of chalcopyrite, replacing Sn2−/S0, and SEM shows a stronger corrosion morphology. All results confirm that the electrochemical effect between arsenopyrite and chalcopyrite promotes the dissolution of chalcopyrite in the acidic culture medium.

Comparison of bioleaching of a sulfidic copper ore (chalcopyrite) in column percolators and in stirred-tank bioreactors including microbial community analysis

Chalcopyrite is the most abundant Cu-sulfide and economically the most important copper mineral in the world. It is known to be recalcitrant in hydrometallurgical processing and therefore chalcopyrite bioleaching has been thoroughly studied for improvement of processing. In this study, the microbial diversity in 22 samples from the Sarcheshmeh copper mine in Iran was investigated via 16S rRNA gene sequencing. In total, 1063 species were recognized after metagenomic analysis including the ferrous iron- and sulfur-oxidizing acidophilic genera Acidithiobacillus, Leptospirillum, Sulfobacillus and Ferroplasma. Mesophilic as well as moderately thermophilic acidophilic ferrous iron- and sulfur-oxidizing microorganisms were enriched from these samples and bioleaching was studied in shake flask experiments using a chalcopyrite-containing ore sample from the same mine. These enrichment cultures were further used as inoculum for bioleaching experiments in percolation columns for simulating heap bioleaching. Addition of 100 mM NaCl to the bioleaching medium was assessed to improve the dissolution rate of chalcopyrite. For comparison, bioleaching in stirred tank reactors with a defined microbial consortium was carried out as well. While just maximal 32% copper could be extracted in the flask bioleaching experiments, 73% and 76% of copper recovery was recorded after 30 and 10 days bioleaching in columns and bioreactors, respectively. Based on the results, both, the application of moderately thermophilic acidophilic bacteria in stirred tank bioreactors, and natural enrichment cultures of mesoacidophiles, with addition of 100 mM NaCl in column percolators with agglomerated ore allowed for a robust chalcopyrite dissolution and copper recovery from Sarcheshmeh copper ore via bioleaching.

A strategy for source control of acid mine drainage by intelligent management of mine wastes

For mine site management, the release of acid and heavy metal ions from sulfur-containing waste rock or tailings (principally chalcopyrite and pyrite) under natural deposit conditions is a major environmental problem. In this study, the interaction between chalcopyrite and pyrite at different mass ratios under a simulated acid mine drainage environment was investigated. The dissolution experiments showed that a low proportion of pyrite promotes chalcopyrite dissolution, while a high proportion inhibits dissolution. However, this phenomenon is weakened by the presence of microorganisms. In addition, the combined characterization by X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy indicated that a high ratio of pyrite incorporation facilitated the formation of passivation layers on the chalcopyrite surface. Scanning electron microscopy results show that many oxidation etching pits are found on the surface of the chalcopyrite residues surface in a low ratio of pyrite addition, whereas numerous islands are observed and tightly wrapped around the surface of the chalcopyrite residues surface in a high ratio of pyrite addition. The current work presents a viable, practical approach to tailings stacking that reduces the release of the heavy metal ions copper and acid through the appropriate proportioning of ores.

Potential of single and designed mixed cultures to enhance the bioleaching of chalcopyrite by oxidation-reduction potential control

Biomining is the extraction of target metals from ores or wastes such as the dissolution of chalcopyrite for copper recovery. A key outstanding topic of study is to improve the rate and total copper released from chalcopyrite that can become ‘passivated’ by surface layers, which hinders oxidative attack on the metal sulfide bond. One strategy to increase chalcopyrite bioleaching is to control of the oxidation-reduction potential in the desired range by using ‘weak’ iron oxidizers. In this study, 15 acidophilic species were evaluated for their ability to catalyze chalcopyrite dissolution that resulted in the addition of Acidithiobacillus ferrianus, Sulfobacillus thermotolerans, and Metallosphaera sedula to the known ‘weak’ iron oxidizing species. Based upon these data, four microbial consortia were designed including mesophiles (25° and 37 °C), moderate thermophiles (49 °C), and thermophiles (70 °C) that increased copper recoveries by up to 32% compared to abiotic controls. The best performing consortium was the moderate thermophiles Sulfobacillus thermotolerans, Sulfobacillus acidophilus, and Ferroplasma acidiphilum that maintained the oxidation-reduction potential in the desired range. However, the consortia also showed evidence of synergistic interactions between ‘weak’ iron oxidizers that increased the efficiency of ferrous iron oxidation that resulted in oxidation-reduction potentials above the desired range and lower copper release. Therefore, while designing microbial consortia is a promising strategy to improve the performance of chalcopyrite bioleaching, care must be taken to ensure synergistic effects do not result in high oxidation-reduction potentials.

Kinetics of nitric acid leaching of bornite and chalcopyrite

The paper presents a study of the process of nitric acid dissolution of the natural minerals chalcopyrite and bornite. The influence of various parameters, including temperature, nitric acid concentration and particle sizes, on this process was examined. Based on the data obtained, the values of apparent activation energy (57.41 and 42.98 kJ/mol for chalcopyrite and bornite, respectively), empirical orders with respect to nitric acid (1.62 and 1.57 for chalcopyrite and bornite, respectively) and with respect to particle size (–1.16 and –2.53 for chalcopyrite and bornite, respectively) were calculated using the shrinking core model. Generalized kinetic equations for the dissolution process of both minerals were derived. Based on the calculations performed, it was suggested that the dissolution processes of chalcopyrite and bornite under these conditions are limited by internal diffusion.

Insights into the effect of ethyl xanthate on the adhesion and biofilm formation by Acidianus manzaensis on chalcopyrite

Adhesion and biofilm formation play important roles in the bio-dissolution of metal sulfides, which can initiate dissolution and enhance bioleaching. Ethyl xanthate, a commonly used flotation reagent, remained in flotation concentrates of metal sulfides and may have an impact on the bioleaching of metal sulfides. Therefore, it is important to analyze the effect of ethyl xanthate on microbial initial adhesion and biofilm formation. The results showed that the adhesion percentage of Acidianus manzaensis on chalcopyrite decreased with increasing ethyl xanthate concentration after adsorption equilibrium, due to the toxicity of ethyl xanthate to A. manzaensis. However, a low concentration (0.01 mg/L) of ethyl xanthate had little effect on the growth of A. manzaensis. The hydrophobicity of chalcopyrite increased after the addition of ethyl xanthate, leading to an increase in total interaction energy and adhesion force. The presence of ethyl xanthate inhibited the early growth of biofilm and delayed the formation of microcolonies on chalcopyrite. While biofilm coverage was larger with the addition of ethyl xanthate than that of the control when biofilm was mature. Furthermore, in the presence of ethyl xanthate, more and larger microcolonies were observed on the chalcopyrite surface when biofilm was matured, resulting in an increased corrosion degree and more jarosite produced on the chalcopyrite surface. This study suggested that a low concentration (0.01 mg/L) of ethyl xanthate could promote the dissolution of chalcopyrite, which could be significant for bioleaching of flotation reagent-bearing flotation concentrates.

Exploring chalcopyrite (bio)leaching mechanisms under thermophilic conditions

Chalcopyrite is highly recalcitrant to bioleaching and its dissolution mechanisms are still debatable. In this study, both concentrated and low-grade chalcopyrite were subjected to bioleaching using three microbial consortia under thermophilic conditions. Copper extraction efficiency from concentrated chalcopyrite was assessed in Erlenmeyer flasks and reached nearly 90 % in all consortia, whereas it was limited to 30 % in the abiotic control. Results indicate the prevalence of the chalcocite mechanism, in which chalcopyrite is initially reduced to chalcocite followed by its dissolution. This mechanism was enabled by maintaining the solution potential (ES) lower than the Nernst potential (E1), with microbial activity playing an essential role in lowering ES. The most abundant microorganisms were affiliated with primary producers (such as Cyanobacteria) and chemoorganotrophs (such as Bradyrhizobium), contributing to chalcopyrite dissolution indirectly. Microorganisms kept pH within 1.9–2.1, which led to higher Fe3+ precipitation and lower ES. Copper extraction in low-grade ore reactors was assessed in batch system with closed circulation between a five-liter jacketed packed bed reactor and a five-liter buffer vessel, simulating a (bio)leaching heap. Differently from the observed in concentrated ore, copper extraction efficiency from low-grade chalcopyrite was higher in the abiotic control (60 % compared to 40–47 % under biotic conditions). Based on thermodynamic calculations, a new two-step model for ferrous-promoted chalcopyrite leaching was proposed, whereby chalcopyrite is reduced to bornite followed by its fast oxidation. Understanding copper extraction through different routes is crucial for achieving efficient (bio)leaching of chalcopyrite.

Modelling the scale-up of the iodine-assisted chalcopyrite leaching in ferric sulfate media from reactors to columns and simulating heap operations

The iodine-assisted heap leaching of chalcopyrite involves the addition of iodide in ferric sulfate media to accelerate the dissolution of chalcopyrite at ambient temperature. The previous studies using reactor leaching tests identified the solution potential, the amount of iodide added, and temperature as the factors controlling the process performance. In the present study, the iodine-assisted chalcopyrite leaching process was scaled up from reactors to 1-m and 6-m columns to further understand how these parameters control the process performance at a larger scale. This is essential to optimize the process in industrial-scale heap leach pads. The HeapSim-2D model was calibrated with the 1-m and 6-m column leach tests together with the kinetic parameter values obtained in the previous reactor leaching tests. When the iodine-assisted chalcopyrite leaching was scaled up from reactors to 1-m and 6-m columns, the leaching became slower because the ore used in the column leaching tests had larger particle sizes with partially-liberated chalcopyrite particles. The calibrated model was then used to carry out the sensitivity analyses to assess the response of the process performance to key design and operating variables, including irrigation rate, ferric concentration, total iodide concentration, temperature, and heap height. The analyses show that the copper extraction could be optimized by adjusting these key design and operating parameters.

The importance of reaction mechanisms and coupled dissolution with reprecipitation (CDR) reactions when modelling copper leaching in heap systems

Chalcopyrite is an abundant source of copper, which can be extracted from low-grade ores in heaps. The dissolution of chalcopyrite is relatively slow partly because of the formation of secondary minerals at the chalcopyrite surface also referred to as surface ‘passivation’. Although the passivation mechanism has been extensively studied, present models do not adequately account for it. Hence, a surface-passivate model (SPM) was used in a reaction path model (RPM) to examine and illustrate how passivation limits copper recovery from chalcopyrite. In addition, the role of different gangue minerals and different chalcopyrite dissolution mechanisms were assessed by incorporating rate equations from Kimball et al. (2010) and Rimstidt et al. (1994) into the RPM, and the state of saturation was determined for various minerals to constrain limiting conditions for copper recovery. RPM with different rate laws describing proton-promoted, ferric-iron promoted, and combined ferric-iron-proton promoted chalcopyrite dissolution in the presence of gangue minerals in chloride system were used. Ferric-iron promoted chalcopyrite dissolution was the fastest reaction mechanism leading to the highest copper mobilization. However, copper mobilization was limited by the formation of iron-hydroxy sulphates (e.g., jarosite), and iron oxide (e.g., hematite) and different gangue minerals, pointing to the importance of accurate representation of primary and secondary reactions, their co-location, and their reaction kinetics. The SPM was capable to simulate surface coverage of the chalcopyrite surface by jarosite, thereby lowering the reactive surface area and consequently suppressing chalcopyrite dissolution. Conversely, the SPM failed to model the incongruent dissolution of chalcopyrite leading to a copper sulfide layer deficient in iron in the form of covellite because covellite was continuously undersaturated in trial models. Further, the presence of gangue minerals like hematite and gypsum may have a positive effect on chalcopyrite dissolution, whereas the presence of silicates (e.g., feldspar and muscovite) have a negative influence. The findings of this study are important as it provides new insights into concurrent reactions controlling the recovery of copper in heaps and how these reactions can be best modelled.

Effect of pine oil on the adhesion and biofilm formation of Acidianus manzaensis on chalcopyrite

Pine oil, commonly used as a flotation frother, could affect the bioleaching process. The attachment and biofilm development of acidophiles on metal sulfides were essential for bioleaching. This study focused on the role of pine oil in the early adhesion and biofilm development by Acidianus manzaensis YN-25 on the chalcopyrite surface. It was revealed that pine oil had a negative effect on the adhesion amount of A. manzaensis on the chalcopyrite surface. After having reached adhesion equilibrium, the percentage of attached cells decreased as the concentration of pine oil increased. The addition of pine oil was found to decrease the negative charge of chalcopyrite and cells, resulting in a higher attraction of acid-base interaction energy and total interaction force. This ultimately led to a stronger adhesion force between chalcopyrite and A. manzaensis. While the addition of pine oil initially delayed the formation of cell microcolonies during the first stage of biofilm formation, which ultimately resulted in larger biofilm coverage compared with the control group. The microcolonies on the mineral surface were also larger and the corrosion pits were bigger with the addition of pine oil. Furthermore, the addition of pine oil weakened the passivation effect and promoted the biological dissolution of chalcopyrite. This study offers a better understanding of the effect of pine oil on the bioleaching of chalcopyrite.