Formation of passivation film during pyrrhotite bioleached by pure L. ferriphilum and mixed culture of L. ferriphilum and A. caldus

Bioleaching and electrochemical experiments were conducted to evaluate pyrrhotite dissolution in the presence of pure L.ferriphilum and mixed culture of L. ferriphilum and A. caldus. The results indicate that the pyrrhotite oxidation behavior is the preferential dissolution of iron accompanied with the massive formation of sulfur in the presence of L. ferriphilum, which significantly hinders the leaching efficiency. Comparatively, the leaching rate of pyrrhotite distinctly increases by 68% in the mixed culture of L. ferriphilum and A. caldus at the 3rd day. But, the accumulated ferric ions and high p H value produced by bioleaching process can give rise to the rapid formation of jarosite, which is the primary passivation film blocking continuous iron extraction during bioleaching by the mixed culture. The addition of A. caldus during leaching by L. ferriphilum can accelerate the oxidation rate of pyrrhotite, but not change the electrochemical oxidation mechanisms of pyrrhotite. XRD and SEM/EDS analyses as well as electrochemical study confirm the above conclusions.

Hydrometallurgical processing of chalcopyrite:A review of leaching techniques

Copper,an essential metal for the energy transition,is primarily obtained from chalcopyrite through hydrometallurgical and pyrometallurgical methods.The risks and harmful impacts of these processes pose significant concerns for environmental and human safety,highlighting the need for more efficient and eco-friendly hydrometallurgical methods.This review article emphasizes current pro-cesses such as oxidative leaching,bioleaching,and pressure leaching that have demonstrated efficiency in overcoming the complicated chalcopyrite network.Oxidative leaching operates under benign conditions within the leaching media;nevertheless,the introduction of oxidizing agents provides benefits and advantages.Bioleaching,a non-aggressive method,has shown a gradual increase in copper extrac-tion efficiency and has been explored using both primary and secondary sources.Pressure leaching,known for its effectiveness and se-lectivity in copper extraction,is becoming commercially more viable with increased research investments.This research also provides im-portant data for advancing future research in the field.

Bioleaching of vanadium from stone coal vanadium ore by Bacillus mucilaginosus:Influencing factors and mechanism

Vanadium and its derivatives are used in various industries,including steel,metallurgy,pharmaceuticals,and aerospace engineering.Although China has massive reserves of stone coal resources,these resources have low grades.Therefore,the effective extraction and recovery of metallic vanadium from stone coal is an important way to realize the efficient resource utilization of stone coal vanadium ore.Herein,Bacillus mucilaginosus was selected as the leaching strain.The vanadium leaching rate reached 35.5%after 20 d of bioleaching under optimal operating conditions.The cumulative vanadium leaching rate in the contact group reached 35.5%,which was higher than that in the noncontact group(9.3%).The metabolites of B.mucilaginosus,such as oxalic,tartaric,citric,and malic acids,dominated in bioleaching,accounting for 73.8%of the vanadium leaching rate.Interestingly,during leaching,the presence of stone coal stimulated the expression of carbonic anhydrase in bacterial cells,and enzyme activity increased by 1.335-1.905 U.Enzyme activity positively promoted the production of metabolite organic acids,and total organic acid content increased by 39.31 mg·L^(-1),resulting in a reduction of 2.51 in the pH of the leaching system with stone coal.This effect favored the leaching of vanadium from stone coal.Atomic force microscopy illustrated that bacterial leaching exacerbated corrosion on the surface of stone coal beyond 10 nm.Our study provides a clear and promising strategy for exploring the bioleaching mechanism from the perspective of microbial enzyme activity and metabolites.

Microbial Community with Potential for Metal Release Isolated from Palca Mine Tailings Pond in Peru

The improvement of microbial characterization has increased the comprehension of microbial population and their ability in the microbiological metal dissolution. Bioleaching processes have been expanded to use microorganisms for the recovery of metals from ores and wastes. This study introduces Palca mine tailings pond in Peru which turned into acid mine drainage (AMD). AMD is a source of microbial communities whose microorganisms may support the aqueous extractive metallurgy for metal recovery. Four samples of AMD were collected from different locations and the elemental characterization showed concentrations of metals, such as Cu, Zn, Al, Mn, and Fe. The pH of the samples showed variation between 1.9 - 6.8. Twenty-one microorganisms were isolated and selected according the cell morphology. 16s rRNA gene sequences identified five species of which three belong to the bacterial kingdom and two to the Fungi kingdom. Two of the bacterial species were ferrous ion oxidizing bacteria, identified as Acidithiobacillus ferriphilus and Acidithiobacillus ferridurans;and the other one a ferric ion reducing bacteria identified as Acidiphilium acidophilum. The fungi species identified were Rhodotorula sinensis and Exophiala xenobiotica, a filamentous fungus isolated for the first time from an AMD.

Relationship and effect of redox potential,jarosites and extracellular polymeric substances in bioleaching chalcopyrite by acidithiobacillus ferrooxidans

The changes of pH,redox potential,concentrations of soluble iron ions and Cu^2＋ with the time of bioleaching chalcopyrite concentrates by acidithiobacillus ferrooxidans were investigated under the different conditions of initial total-iron amount as well as mole ratio of Fe（III） to Fe（II） in the solutions containing synthetic extracellular polymeric substances （EPS）.When the solution potential is lower than 650 mV （vs SHE）,the inhibition of jarosites to bioleaching chalcopyrite is not vital as EPS produced by bacteria can retard the contamination through flocculating jarosites even if concentration of Fe（III） ions is up to 20 g/L but increases with increasing the concentration of Fe（III） ions;jarosites formed by bio-oxidized Fe3＋ ions are more easy to adhere to outside surface of EPS space on chalcopyrite;the EPS layer with jarosites acts as a weak diffusion barrier to further rapidly create a high redox potential of more than 650 mV by bio-oxidizing Fe^2＋ ions inside and outside EPS space into Fe^3＋ ions,resulting in a rapid deterioration of ion diffusion performance of the EPS layer to inhibit bioleaching chalcopyrite severely and irreversibly.

Electrochemical oxidation behavior of pyrite bioleaching by Acidthiobacillus ferrooxidans

The electrochemical oxidation behavior of pyrite in bioleaching system of Acidthiobacillusferrooxidans was investigated by cyclic voltammetry （CV）, polarization curve and electrochemical impedance spectroscopy （EIS）. The results show that in the presence or absence of A. ferrooxidans, the oxidation reaction of pyrite is divided into two steps： the first reaction step involves the oxidation of pyrite to S, and the second reaction step is the oxidation of S to SO4^2-. The oxidation mechanism of pyrite is not changed in the presence of A. ferrooxidans, but the oxidation rate of pyrite is accelerated. With the extension of reaction time of A. ferrooxidan with pyrite, the polarization current density of pyrite increases and the breakdown potential at which the passive film dissolves decreases. The impedance in the presence ofA. ferrooxidans is obviously lower than that in the absence of A. ferrooxidans, further indicating that microorganism accelerates the corrosion process of pyrite.

Interaction mechanism of Cu^(2+),Fe^(3+) ions and extracellular polymeric substances during bioleaching chalcopyrite by Acidithiobacillus ferrooxidans ATCC2370

The extracellular polymeric substances（EPS） of Acidithiobacillus ferrooxidans ATCC 23270,and iron and copper enclosed in EPS were extracted by ultrasonication and centrifugation methods to determine the interaction mechanism of Cu2＋,Fe3＋ and EPS during bioleaching chalcopyrite.Generally,Cu2＋ ions can stimulate bacteria to produce more EPS than Fe3＋ ions.The mass ratio of Fe3＋/Cu2＋ enclosed in EPS decreased gradually from about 4：1 to about 2：1 when the concentration of Cu2＋ ions increased from 0.01 to 0.04 mol/L.The amount of iron and copper bound together by EPS in ferrous-free 9K medium containing 1% chalcopyrite was about 2 times of that in 9K medium containing 0.04 mol/L Cu2＋ ions.It was inferred that the EPS with jarosites on the surface of chalcopyrite gradually acted as a weak diffusion barrier for Cu2＋,Fe3＋ ions transference during bioleaching chalcopyrite.

Effect of pyrite, elemental sulfur and ferrous ions on EPS production by metal sulfide bioleaching microbes

Extracellular polymeric substances （EPS） produced by acidophilic bioleaching microorganisms play an important role in the production of acid mine drainage and metal sulfide bioleaching. EPS mediate the contact between microbial cells and growth substrates, having a pivotal role in organic film formation and bacterium-substratum interactions. The production and chemical composition of EPS produced by seven bioleaching strains grown with different substrates were studied. Analysis of the EPS extracted from these strains indicated that the EPS consisted of carbohydrates, proteins and galacturonic acid. The contents of EPS, carbohydrates, proteins and galacturonic acid of EPS were largely related to the kind of strain used and culture condition. The results show that EPS productions of microbes grown with pyrite were significantly higher than those of microbes grown with sulfur or FeSO4·7H2O. The highest EPS production of the seven acidiphilic strains was （159.43±3.93） mg/g, which was produced by Leptospirillum ferriphilum CBCBSUCSU208015 when cultivated with pyrite.

Control method of chalcopyrite passivation in bioleaching

Passivation is a common phenomenon on the surface of chalcopyrite in the process of bioleaching. The ordinary leaching and strengthening leaching by adding glass beads were carried out. The results show that the passivation of chalcopyrite was greatly weakened in strengthening leaching due to the change of leaching conditions. The copper leaching efficiency was increased from 50% to 89.8% through adding beads. The SEM and X-ray diffraction （XRD） analyses illustrate that there are few jarosite precipitates and weak passivation on the surface of chalcopyrite in strengthening leaching. In contrast, there are thick and compact jarosite precipitate and obvious passivation in ordinary leaching, which hinders further dissolution of chalcopyrite.

Characterization of apparent sulfur oxidation activity of thermophilic archaea in bioleaching of chalcopyrite

The apparent sulfur oxidation activities of four pure thermophilic archaea, Acidianus brierleyi （JCM 8954）, Metallosphaera sedula （YN 23）, Acidianus manzaensis （YN 25） and Sulfolobus metallicus （YN 24） and their mixture in bioleaching chalcopyrite were compared, which were characterized indirectly by the evolution of the cells concentration, pH value and sulfate ions concentration in solution. The results show that the mixed culture contributed significantly to the raising of leaching rate, which suggests that the mixed culture had a higher sulfur oxidation activity than the pure culture. Meanwhile, the results also indicate that the changes of parameters characterizing the sulfur oxidation activity of thermophilic archaea are often influenced by many factors, so it is hard to reflect accurately the specific sulfur oxidation activities among the different sulfur-oxidizing microbes when bioleaching chalcopyrite at different conditions. Accordingly, an efficient method to characterize microbial sulfur oxidation activity appears to be desirable.

Bioleaching of Pb-Zn-Sn chalcopyrite concentrate in tank bioreactor and microbial community succession analysis

The variation of microbial community structure was investigated for the tank bioleaching process of Pb-Zn-Sn chalcopyrite concentrate in the presence of mixed moderately thermophilic bacteria. The parameters, such as pH value, solution potential and concentrations of metal ions, were determined by the method of polymerase chain reaction-restriction fragment length polymorphism （PCR-RFLP） to analyze the succession of microbial community. The results showed that a final copper extraction rate of 85.6% could be obtained after tank bioleaching for 30 d. The Acidithiobacillus caldus was the dominant population with abundance of about 73.80%in the initial stage, then Sulfobacillus thermosulfidooxidans dominated from the 18th day to the end of bioleaching, while the abundance of Leptospirillum ferriphilum changed slightly. A higher solution potential within a certain range and appropriate concentration of ferric ions were essential for this tank bioleaching of chalcopyrite.

Comparison of electrochemical dissolution of chalcopyrite and bornite in acid culture medium

The electrochemical dissolution process of chalcopyrite and bornite in acid bacteria culture medium was investigated by electrochemical measurements and X-ray photoelectron spectroscopy（XPS） analysis. Bornite was much easier to be oxidized rather than to be reduced, and chalcopyrite was difficult to be both oxidized and reduced. The relatively higher copper extraction of bornite dissolution can be attributed to its higher oxidation rate. Covellite（CuS） was detected as the intermediate species during the dissolution processes of both bornite and chalcopyrite. Bornite dissolution was preferred to be a direct oxidation pathway, in which bornite was directly oxidized to covellite（CuS） and cupric ions, and the formed covellite（CuS） may inhibit the further dissolution. Chalcopyrite dissolution was preferred to be a continuous reduction-oxidation pathway, in which chalcopyrite was initially reduced to bornite, then oxidized to covellite（CuS）, and the initial reduction reaction was the rate-limiting step.

Effect of initial pH on chalcopyrite oxidation dissolution in the presence of extreme thermophile Acidianus manzaensis

The influence of initial pH on the chalcopyrite oxidation dissolution at 65 ℃ was investigated by bioleaching and cyclic voltammetiy experiments,and the oxidation products were investigated by XRD and Raman spectroscopy.Bioleaching results show that chalcopyrite dissolution rate increases with the decrease of the initial pH in chemical leaching,while the influence of initial pH on bioleaching is on the contrary.The presence of Acidianus manzaensis does not promote chalcopyrite dissolution under initial pH1.0,which mainly results from serious inhibition of high acidity to the growth of Acidianus manzaensis.Electrochemical experiments results show that anodic oxidation currents of electrolyte with or without Acidianus manzaensis both increase with the increase of initial pH,and covellite and sulfur are detected on the electrode surface.The results confirm that chalcopyrite dissolution in chemical leaching is under the combined action of oxidation and non-oxidation of proton,with conversion of chalcopyrite to covellite and elemental sulfur.

Optimization of copper extraction for bioleaching of complex Cu-polymetallic concentrate by moderate thermophiles

Effects of initial pH, temperature, liquid volume, rotation speed, galvanic interaction （pyrite ratio） and pulp density on bioleaching of complex Cu-polymetallic concentrate were investigated. The results indicated that the copper extraction at pH 1.5 was 1.5 and 1.4 times that at pH 1.0 and pH 2.0 respectively. The copper extraction obtained at 45 ℃ was 1236.8%higher than that at 50 ℃. With the increase of rotation speed or the decrease of liquid volume, copper extraction was improved obviously. Copper extraction was improved gradually with the increase of pyrite ratio. However, when the ratio was higher than 20.0%, no further increase in copper extraction was observed. And the statistically significant interactive effects on copper extraction were found between temperature and pH, and temperature and pyrite ratio.

High efficient mixed culture screening and selected microbial community shift for bioleaching process

To screen the high efficient mixed culture and understand the bioleaching behaviors of mixed culture for low-grade copper sulfide ore bioleaching,ten mixed cultures were collected and screened from different acid mine drainages obtained from sulfide mines of China.The leaching rate was set as criterion to screen the mixed culture and the metagenomic approach.Community genome array（CGA） was used for analyzing the mixed culture microbial community shift during the bioleaching process.The results indicate that the mixed culture obtained from Yinshan（YS） lead-zinc mine in Dexing of Jiangxi province in China reaches the maximum copper extraction（68.89%） during the one bioleaching period of 24 d.CGA results show that YS culture contains nine kinds of bacteria which are belong to six divisions,and the microbial community structure is changing during the bioleaching process.This provides a good way to accelerate the bioleaching process and reveals the microbial community shift during the bioleaching process.

Surface species of chalcopyrite during bioleaching by moderately thermophilic bacteria

X-ray diffraction （XRD） and X-ray photoelectron spectroscopy （XPS） analyses were carried out to investigate the surface species and interfacial reactions during bioleaching of chalcopyrite by different strains of moderately thermophilic bacteria （45 °C）. Results show that monosulfide （CuS）, disulfide （S22？）, polysulfide （Sn2？）, elemental sulfur （S0） and sulfate （SO42？） are the main intermediate species on the surface of chalcopyrite during bioleaching byA. caldus,S. thermosulfidooxidans andL. ferriphilum. The low kinetics of dissolution of chalcopyrite inA. caldus can be mainly attributed to the incomplete dissolution of chalcopyrite and the passivation layer of polysulfide. Polysulfide and jarosite should be mainly responsible for the passivation of chalcopyrite in bioleaching byL. ferriphilumorS. thermosulfidooxidans. However, elemental sulfur should not be the main composition of passivation layer of chalcopyrite during bioleaching.

Bioleaching of heavy metals from contaminated alkaline sediment by auto- and heterotrophic bacteria in stirred tank reactor

Bioleaching Xiangjiang River alkaline sediment contaminated by multiple heavy metals was investigated. Multiple metals in alkaline sediment possess significant toxicity to aquatic organisms or humans and will greatly inhibit bioleaching. The bioleaching method using autotrophic bacteria mixed with heterotrophic bacteria can solve this problem successfully. The experiment results showed that bioleaching efficiencies of Zn, Mn, Cu, and Cd were 95.2 %, 94.2 %, 90.1 %, and 84.4 %, respectively. Moreover, the changes of heavy metal concentrations in different fractions in contaminated sediment before and after bioleaching were analyzed by selective sequential extraction, and it was discovered that the main fractions of Zn, Mn, Cu and Cd after bioleaching are Fe-Mn oxide, organic associated form and a residual form. Its biotoxicity decreased greatly. The bioleaching heavy metals from sediment using autotrophic bacteria combined with heterotrophic bacteria can effectively improve the bioleaching efficiency and reduce toxicity.

Effect of moderately thermophilic bacteria on metal extraction and electrochemical characteristics for zinc smelting slag in bioleaching system

The effects of moderately thermophilic bacteria on the extraction of metals from zinc smelting slag and electrochemical characteristics of zinc smelting slag carbon paste electrode in bioleaching process were studied. The results show that the extraction rates of Fe, Cu and Zn from the slag reach 86.7%, 90.3% and 66.7% after adsorbed bacteria sterilize, while those with adsorbed bacteria are 91.9%, 96.0% and 84.5% in conditions of pulp density 2%, pH 1.0, temperature 65 °C and stirring rate 120 r/min, respectively. Some stretching peaks of functional groups from bacterial secretes on the bioleached residue surface, such as 1007 cm-1 and 1193 cm-1, turn up through FI-IR analysis and indirectly reveal the presence of the adsorbed bacteria on the slag particles surface. Besides, the corrosion of zinc smelting slag is enhanced by bacteria according to the characteristics of cyclic voltametry and Tafel curves in bioleaching system.

Formation and evolution of secondary minerals during bioleaching of chalcopyrite by thermoacidophilic Archaea Acidianus manzaensis

The formation and evolution of secondary minerals during bioleaching of chalcopyrite by thermoacidophilic Archaea Acidianus manzaensis were analyzed by combining synchrotron radiation X-ray diffraction（SR-XRD） and S, Fe and Cu Kα X-ray absorption near edge structure（XANES） spectroscopy. Leaching experiment showed that 82.4% of Cu2＋ was dissolved by A. manzaensis after 10 d. The surface of chalcopyrite was corroded apparently and covered with leaching products. During bioleaching, the formation and evolution of secondary minerals were as follows： 1） little elemental sulfur, jarosite, bornite and chalcocite were found at days 2 and 4; and 2） bornite and chalcocite disappeared, covellite formed, and jarosite gradually became the main component at days 6 and 10. These results indicated that metal-deficiency sulfides chalcocite and bornite were first formed with a low redox potential value（360-461 m V）, and then gradually transformed to covellite with a high redox potential value（461-531 m V）.

Decomposition mechanism of pentlandite during electrochemical bio-oxidation process

Electrochemical measurements were carried out to elucidate decomposition mechanism of pentlandite using modified powder microelectrode with Acidithiobacillus ferrooxidans attached or without on the mineral powder surface.Cyclic voltammetry（CV） results show that at a low potential of about-0.2 V（vs SCE）,the pentlandite was transformed to an intermediated phase like Fe4.5-yNi4.5-xS8-z when Fe and Ni ions were evacuated from mineral lattice;when the potential was changed from-0.2 V to 0.2 V,the unstable violarite（Fe3Ni3S4） and FeNi2S4 were formed which was accompanied by element sulfur formed on the mineral surface;when the potential increased over 0.2 V,the unstable intermediated phase decomposed entirely;at a higher potential of 0.7 V,the evacuated ferrous ion was oxidized to ferric ion.The presence of Acidithiobacillus ferrooxidans made the oxidation peak current increase with initial peak potential negatively moving,and the bacteria also contributed to the sulfur removing from mineral surface,which was demonstrated by the reduction characteristic at potential ranging from-0.75 to-0.5 V.Leaching experiments and electrochemical results show that the solution acidity increasing when pH2 may impede the oxidation process slightly.