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Semiconductor-Microbial Mechanism of Selective Dissolutionof Chalcocite in Bioleaching

Biao Wu1,Xinlong Yang1,*,Jiankang Wen1,Dianzuo Wang1
1National Engineering Laboratoryof Biohydrometallurgy, GRINM Group CorporationLimited, Beijing 100088, China
*

E-mail:yxl5071@163.com. Tel:+86 10 60662775.

Received 2019 Jul 23; Accepted 2019 Aug 21; Collection date 2019 Nov 5.

Copyright © 2019 American Chemical Society

This is an open access article published under an ACS AuthorChoiceLicense, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

PMCID: PMC6844112  PMID:31720528

Abstract

graphic file with name ao9b02294_0014.jpg

Chalcocite-dominantsecondary copper ore with a high pyrite contenthad a rapidly increased iron concentration in the middle and laterperiods of bioleaching, which increased the difficulty of separatingcopper and iron ions in the leaching solution. In the two aspectsof microbial community succession and energy band theory, the selectivedissolution mechanism of chalcocite in this type of copper ore wasanalyzed and illustrated using experiments and first-principles calculations.The results showed that controlling the solution potential at a lowerlevel was beneficial to the selective leaching of chalcocite, whilebacteria promoted the leaching of pyrite and chalcocite simultaneouslyby oxidizing Fe2+ to Fe3+ in the solution. Below700 mV of solution potential, the bacterial community, mainly consistingofAcidithiobacillus andSulfobacillus, had a stronger promotion on the selective dissolution of chalcocite.The solution energy level of bioleaching was higher than ideal pyritebut lower than ideal chalcocite, which resulted in the accumulationof electrons on the surface of pyrite and the formation of holes atthe top of the chalcocite valence band. When bacteria assisted theoxidation of Fe2+ to Fe3+ and caused the raiseof the solution potential, the difference between the solution energylevel and the top of the pyrite valence band would be smaller thanthe width of the pyrite energy gap. Below 700 mV, the assistance ofAcidithiobacillus andSulfobacillus onthe oxidation of Fe2+ was weak. Chalcocite would be selectivelydissolved by oxygen and a small amount of Fe3+ in the solution.Because of the existence of Fe, Cu, and S vacancies in real minerals,the atomic activity in the Cu–S bond and the Fe–S bondenhanced, and the reaction difficulty between chalcocite, pyrite,and electron acceptors in the solution reduced. The solution potentialshould be controlled at 600 mV or less to ensure the selective dissolutionof chalcocite.

1. Introduction

Chalcocite (Cu2S) is a kind of secondary mineral formedby oxidation, reduction, dissemination, and migration of primary sulfidessuch as chalcopyrite. As an important raw material for copper extraction,chalcocite has the highest copper content in copper sulfide minerals.Bioleaching of chalcocite has the advantages of economy and environmentalprotection. Its principle is to complete the oxidation of Fe2+ and S2– by bacteria and directly or indirectlypromote the dissolution of copper sulfide minerals.1 With the gradual depletion of chalcopyrite-dominant copperores, more and more chalcocite-dominant copper ores with a high pyritecontent are treated. However, in the middle and later periods of bioleachingof copper ores, iron ions in the leaching solution tend to accumulaterapidly.2 This problem increases the difficultyof separating copper and iron ions from the leaching solution andmakes the influence of wastewater on the environment deeper. Therefore,it is necessary to selectively dissolve chalcocite from the secondarysulfide copper ores with a high pyrite content in bioleaching.

In chalcocite-dominant copper ores, Fe mainly exists as pyrite(FeS2). In bioleaching, S2– on the surfaceof pyrite participates in the single electron transfer reaction, andis oxidized to Sn2–,S0, and SO42– in turn by bacteria.3 Fe2+ is oxidized to Fe3+ by bacteria and entered the solution to promote the dissolutionof chalcocite.4 Chalcocite is transformedinto covellite by multistep oxidation. Under the action of Fe3+ and dissolved oxygen, covellite is further decomposed intoCu2+ and S0.5 Obviously,Fe2+ ions produced by pyrite dissolution are closely relatedto the dissolution of chalcocite, and are also the main source ofFe2+ ions required by bacteria.

Previous studieshave shown that dissolved oxygen and Fe3+ are the two mainoxidants for pyrite dissolution. With the low pHvalue, the oxidation rate of pyrite is positively correlated withthe concentration of Fe3+.6,7 Because thechange of the concentration ratio between Fe3+ and Fe2+ determined the oxidation reduction potential (ORP), thedissolution rate of pyrite is closely related to the solution potential.Electron transfer of the oxidant from the mineral surface to the solutionis a limited step in pyrite dissolution. Therefore, the oxidationof pyrite is controlled by the chemical reaction.8 When the solution potential is greater than 546 mV in bioleaching,the bonds on the surface of pyrite break and the ore begin to dissolve.9 When the solution potential is greater than 600mV, the oxidation rate of pyrite accelerated significantly,10 and bacteria can increase the oxidation rateof Fe2+ by more than 106 times.11 Therefore, it can be considered that controlling bacterialactivity and delaying the oxidation of Fe2+ are the twoessential methods to control pyrite dissolution. Previous studieshave shown that the bioleaching of chalcocite is controlled by thediffusion of Fe3+ ions and chemical reactions. When theconcentration of Fe3+ in the solution is lower than 0.058mol/L, the leaching process is mainly controlled by the mass transferof Fe3+ ions. When the concentration of Fe3+ ions is higher than 0.058 mol/L, the leaching process is mainlycontrolled by the surface charge transfer of minerals.12 Compared with pyrite, the leaching of chalcociteis less affected by bacteria. With the increase of the Cu2+ concentration in the solution, the number of bacteria on the surfaceof chalcocite decrease, and Cu+ are mainly oxidized byFe3+ in the solution.13,14 At present,the dissolution behavior of pyrite in bioleaching has been studiedextensively. However, more theoretical analyses about the dissolutioncharacteristics of mixed minerals containing pyrite and chalcociteare needed.

The surface reaction of a metal sulfide semiconductorin an electrolytesolution is the critical factor affecting its dissolution mechanism.The difference between the ORP of the solution and the Fermi levelof the solid determines the reaction mechanism. The semiconductorband model can describe the reaction process of the sulfide ore surfacein the solution clearly. Holmes and Crundwell have explained the dissolutionmechanism of pyrite in acidic solution by energy band diagram.7 The diagram shows the energy levels of solidand liquid at the pyrite–solution interface. At the dissolutionequilibrium, the Fermi levels of solids and liquids are equal. Thestudy on the mixed bioleaching system of sphalerite, pyrite, and chalcopyriteshows that bacteria enhance copper leaching mainly by enhancing theability of oxygen to obtain electrons.15 Obviously, the model of the energy band can also be used to explainthe dissolution mechanism of chalcocite in the presence of pyritein bioleaching.

Using the first-principles method of densityfunctional theory(DFT), we can accurately obtain the crystal parameters and propertiesof various minerals. This provides great convenience for the theoreticalanalysis of the energy band in the dissolution of sulfide ores. However,there are few DFT studies and band analyses in bioleaching of chalcocite,which have significant research value. Based on the analysis of previousworks, we speculate that the dissolution of chalcocite in real mineralsis easier on the conditions of higher solution potential and the ferrousoxidation rate. In this paper, pure minerals of chalcocite and pyritewere separated from secondary copper sulfide samples. By analyzingthe change of the solution potential and the bacterial community structure,the difference of dissolution of two minerals in bioleaching was studied.Subsequently, the crystal models of chalcocite and pyrite were constructed,and the energy band distributions of the two minerals in real conditionswere investigated. Our objectives are to determine the dominant groupin the selective leaching and the leaching effect of chalcocite withthe change of the solution potential and the bacterial community structure.Furthermore, the role of pyrite in selective bioleaching of real mineralsshould also be determined to explain the mechanism of selective dissolutionof chalcocite in bioleaching.

2. Results and Discussion

2.1. Effect of Bacteria on the Leaching Processof Pure Minerals

The chemical composition analysis resultsof the secondary copper sulfide sample are shown inTable1. It shows that the sample contained0.28% of Cu, 3.03% of Fe, and 3.51% of S, respectively. The sampleconsists of quartz, muscovite, pyrite, chalcocite, and a small amountof covellite, as described in the previous work.35 It can be inferred that copper mainly exists in the formof chalcocite and covellite, and iron mainly exists in the form ofpyrite.

Table 1. Chemical Composition Analysis of Sample.

elementCuSFe2O3AsSiO2Al2O3CaOK2ONa2OMgO
content (wt %)0.283.513.030.0278.7714.170.071.480.060.05

Table2 shows thechemical composition analysis results of two pure minerals separatedand enriched from the raw ore. It shows that the purity of the twopure mineral samples is greater than 92%. The content of Fe in chalcociteand Cu in pyrite is less than 3%, which means that the influence ofthe two elements on the dissolution of respective main minerals canbe neglected.

Table 2. Chemical Composition Analysis of PureMinerals (wt %).

mineralCuFeSSiO2purity
chalcocite68.422.5323.980.1192.40
chalcocite (theoretical)80.00 20.00 100.00
pyrite0.1944.1947.941.3992.13
pyrite (theoretical) 46.6753.33 100.00

The leaching experiments of pure minerals were carriedout in conicalflasks. The effect of the inoculation ratio on the leaching efficiencyof metal ions from two pure minerals was investigated. The resultsare shown inFigure1.

Figure 1.

Figure 1

Effect of various inoculation ratios (1:20, 1:10, and 1:5) on leachingefficiency of pure minerals at 30 °C.

As shown inFigure1, the leaching effects of metal ions from chalcocite and pyrite bybacteria are obviously different. Between 0 and 120 h, the leachingefficiency of Cu increases slowly. When the leaching time exceeded120 h, the leaching efficiency increases significantly. For pyrite,the increase of leaching efficiency of Fe is the highest from 75 to220 h. After 220 h, the leaching efficiency of Fe barely changes.At the same leaching moment, the leaching efficiency of Cu is alwayshigher than pyrite. It can be seen that the change of the inoculationratio has little effect on the leaching efficiency of metal ions fromtwo pure minerals. The results show that the leaching efficiency ofCu is higher when the inoculation ratio is 1:10.

The solutionpotential was controlled during the leaching process.The dissolution differences of the two pure minerals at solution potentialsof 640 mV and 800 mV were investigated. The results are shown inFigures2 and3.

Figure 2.

Figure 2

Leaching efficiency variety of chalcocite and pyrite with timeat 640 mV of solution potential and 30 °C (the initial pH valueis 1.8).

Figure 3.

Figure 3

Leaching efficiency variety of chalcocite andpyrite with timeat 800 mV of solution potential and 30 °C (the initial pH valueis 1.8).

As shown inFigures2 and3, with the changeof the solution potential,the leaching efficiencies of copper and iron ions are different obviously.Changes of potential have little effect on the dissolution of chalcocite.At 640 mV of solution potential, the leaching efficiency of Cu ismore than 75%, while the leaching efficiency of Fe is only about 5%on day 20. At 800 mV of solution potential, the leaching efficiencyof Cu is close to 90%, and the leaching efficiency of Fe increasedabove 40%. It can be inferred that the solution potential has a significanteffect on the selective leaching of chalcocite. A lower solution potentialis helpful for selective dissolution of chalcocite.

2.2. Effect of Bacteria on Leaching Process ofMixed Pure Minerals

Due to the existence of Fe3+/Fe2+ pairs, Fe3+ in the solution can simultaneouslypromote the oxidation of Cu+ in chalcocite and Fe2+ in pyrite, and promote the dissolution of the two minerals in theleaching system. The ratio of Fe3+/Fe2+ pairwill be affected by the release of Fe2+ from pyrite dissolution,and the potential of the solution will be affected. Therefore, itis helpful to understand the selective leaching mechanism of chalcociteby mixing pure minerals of pyrite and chalcocite and studying theleaching characteristics of the mixed ore.

The chalcocite/pyritemixed pure minerals with a mass ratio of 1:2 were leached at 30 °Cfor 14 days. The variation of metal ion leaching efficiency and solutionpotential with time is shown inFigures4 and5.

Figure 4.

Figure 4

Leaching efficiencyvariety of chalcocite and pyrite with time(the initial pH value is 1.8 and the inoculation ratio is 1:10).

Figure 5.

Figure 5

Solution potential variety of mixed pure minerals withtime.

It can be seen fromFigure4 that the presence of bacteriahas different effects on theleaching efficiency of copper and iron from mixed pure minerals. Whenthere were no bacteria in leaching, because of the higher electrostaticpotential of pyrite, the contact between pyrite and chalcocite wouldproduce a galvanic effect, which would inhibit the dissolution processof pyrite as the cathode.21 The dissolutionof pyrite and chalcocite was promoted after bacterial inoculation.With the presence of bacteria, the potential of the solution increasesfrom 260 mV to about 550 mV after 14 days of bioleaching (Figure5). This indicatesthat the oxidation of Fe2+ in the solution and mineralsurface by bacteria increases the potential of the solution, acceleratesthe mineral dissolution rate, and then increases the difference ofleaching efficiency between two sulfide ores due to the galvanic effect.

Therefore, bacteria can promote the dissolution of mixed pure minerals,and the selective dissolution of chalcocite can be achieved by controllingthe potential of the solution.

2.3. Varietiesof Microbial Community Structuresduring Selective Leaching

2.3.1. Response of MicrobialCommunity Structureson Different Sulfide Minerals

The structures of the microbialcommunity absorbed on the leached sample of different sulfide oreswere analyzed by the sequencing strategy PE300. The results are showninFigure6. Originalrepresents the starting strain. Pyrite and chalcocite represent themicrobial communities in the leaching solution of the two pure minerals,respectively.

Figure 6.

Figure 6

Frequency of genus in microbial communities from bioleachingsolutionof pure minerals after 14 days of bioleaching (original representsthe starting strain).

The results inFigure6 show that the dominantgenera in the starting strain areclassified intoLeptospirillum,Acidithiobacillus, andSulfobacillus, which have strong oxidationability toward iron and sulfur.Leptospirillum isthe dominant bacterium in pyrite leaching, whileAcidithiobacillus andSulfobacillus are the dominant bacteria inchalcocite leaching. The proportion ofSulfobacillus is higher. It canbe inferred that the dissolution of pyrite is mainly promoted by theoxidation of low-valent iron byLeptospirillum, whilethe dissolution of chalcocite is mainly promoted by the oxidationof low-valent sulfur byAcidithiobacillus andSulfobacillus.

2.3.2. Response of the CommunitySuccession onSolution Potential

The leaching experiments of secondarycopper sulfide samples were carried out in a stirred tank reactor.The effect of the solution potential on the leaching efficiency ofCu from copper sulfide ore samples was investigated. The results areshown inFigure7.

Figure 7.

Figure 7

Leachingefficiency variety of Cu and Fe ions with solution potentialafter 14 days (the initial pH value is 1.8 and the inoculation ratiois 1:10).

The initial solution potentialis 370 mV.Figure7 shows that the Cu in the sample has obviousselective dissolution characteristics when the solution potentialis controlled. When the solution potential is greater than 700 mV,the Cu leaching efficiency is greater than 75%, while the Fe leachingefficiency is only about 6%. Although the Cu leaching efficiency reachedabout 80% above 700 mV, the Fe leaching efficiency rapidly increasedto more than 30%. Therefore, the selective leaching of chalcociteis effective when the solution potential is controlled below 700 mV.

The structure of the microbial community absorbed on the leachedsample at different solution potentials was analyzed by the sequencingstrategy PE300. The results are shown inFigure8. Samples are represented by numbers 1–6.The potential of sample 1 is not controlled during leaching, and thepotential is higher than 840 mV. The solution potential of samples2–6 are controlled to be 800, 760, 700, 640, and 600 mV, respectively.

Figure 8.

Figure 8

Frequencyof genus in microbial communities of copper sulfide oresat different potentials after 14 days of bioleaching (1–6 representthe samples from different potential control conditions).

As shown inFigure8, the structures of microbial communities change greatly atdifferentpotentials. At 840 mV, the dominant bacteria is mainlyLeptospirillum, whose proportion decreases rapidly at lower potential. It was reportedthatLeptospirillum ferriphilum wasthe dominant iron(II)-oxidizer in later stages of leaching.22,23 At 700 mV or a lower potential, the proportion ofLeptospirillum decreases to almost 0, and is mainly replaced byAcidithiobacillus andSulfobacillus.

It can be inferred thatthe iron oxidizing ability of the communitydominated byLeptospirillum at high potential isstronger. The increased dissolution rate of pyrite leads to more ironions and is not conducive to the extraction and separation of copperfrom the leaching solution. Conversely, the sulfur oxidation abilityof the community dominated byAcidithiobacillus andSulfobacillus at low potential is stronger. The two bacteriaare conducive to the selective dissolution of chalcocite. It was reportedthat in pyrite bioleaching ofAcidithiobacillus,the thiosulfate leads to sulfate without S formation.24 Obviously, the presence of sulfur-oxidizing bacteria alsoeliminates the effect of sulfur in leaching.

2.4. Semiconductor Band Theory Analysis of SelectiveLeaching of Chalcocite

Based on the density functional theory,the crystal models of chalcocite and pyrite were constructed usingthe program CASTEP. Structural optimizations and electronic propertycalculations were also performed. The crystal structures is showninFigure9. Thereare Fe–S bonds and S–S bonds in the pyrite cell, andonly Cu–S bonds and Cu–Cu bonds in the chalcocite cell.

Figure 9.

Figure 9

Coordinationof Fe and Cu atoms in chalcocite and pyrite. (A) chalcocite;(B) pyrite.

2.4.1. Analysis of MullikenPopulation

Mulliken population is a method proposed to showthe distributionand bonding of electric charges between constituent atoms, which characterizesthe distribution, transfer, and bonding properties of electrons betweenatoms. When the population is greater, the covalent bonds formed betweenthe atoms are stronger. Conversely, for a smaller population, electronclouds have a small degree of overlap and the bond exhibits ionicity.The atomic coordination of the two minerals are shown inFigure9. Mulliken populationanalysis focuses on bonds formed by atoms around vacancies. The populationsof ideal and defective pyrite and chalcocite are listed inTables3 and4.

Table 3. Mulliken Population of Ideal and DefectivePyrite.
 bondlength (Å)population
idealcrystalFe–S2.2410.48
S–S2.1780.31
Fe vacancyFe–S12.2460.47
 Fe–S22.2400.48
Fe–S32.2680.43
Fe–S42.2540.47
Fe–S52.2030.50
Fe–S62.2350.48
S–S2.1880.32
S vacancyFe–S12.2420.48
 Fe–S22.2330.48
Fe–S32.2390.47
Fe–S42.2410.47
Fe–S52.2420.48
Fe–S62.2480.48
S–S2.1750.35
Table 4. Mulliken Population of Ideal and DefectiveChalcocite.
 bondlength (Å)population
ideal crystalCu1–Cu22.6870.05
 Cu1–S12.2880.40
Cu1–S22.3400.40
Cu1–Cu32.6830.70
Cu1–S32.4060.30
Cu1–Cu42.6090.16
Cu vacancyCu1–Cu22.7420.05
 Cu1–S12.5220.18
Cu1–S22.6840.09
Cu1–Cu32.2440.45
Cu1–S32.6490.12
Cu1–Cu42.3180.39
S vacancyCu1–Cu22.7230.04
 Cu1–S12.4480.24
Cu1–S22.6390.12
Cu1–Cu32.2270.52
Cu1–S32.6720.12
Cu1–Cu42.3520.33

InTable3, withthe presence of Fe vacancy in the pyrite crystal, the length of mostFe–S bonds increases slightly, the population decreases from0.48 to 0.43, and the bonds covalency are stronger. The length ofthe S–S bond increases slightly with a little change of thepopulation. In the pyrite crystal with S vacancy, the lengths of mostFe–S bonds increase slightly and the populations remain unchanged.The length of the S–S bond decreases slightly, while the populationincreases from 0.31 to 0.35, and the bond covalency is also stronger.The above results show that the surface of pyrite with Fe vacancyhas stronger hydrophilicity than ideal pyrite.18 The presence of vacancy enhances the atomic activity inthe Fe–S bond, and reduce the reaction difficulty between pyriteand electron acceptors such as O2 and Fe3+ inthe solution. The presence of S vacancy mainly weakens the activityof S atoms in S–S bonds and increases the reaction difficultybetween pyrite and electron acceptors in the solution.

InTable4, withthe presence of Cu vacancy in the chalcocite crystal, the lengthsof Cu–S bonds decrease significantly, the populations decreasefrom 0.30–0.40 to 0.09–0.18, and the bond ionicity becomesstronger. In the chalcocite crystal with S vacancy, the populationsof Cu–S bonds decrease to 0.12, with a stronger bond ionicity.The length and population of Cu–Cu bonds in chalcocite withvacancy have no directional variation trend. The above results showthat the surface of chalcocite with Cu or S vacancy has stronger hydrophilicitythan ideal chalcocite. The presence of vacancies enhances the atomicactivity in Cu–S bonds and reduces the reaction difficultybetween chalcocite and electron acceptors in the solution. It is difficultto bond between S atoms in chalcocite.

2.4.2. Analysisof Density of States (DOS)

The band structure and atomicdensity of states (DOS) of two mineralcells are shown inFigures10 and11. The value of the Fermi levelis set at 0 eV.

Figure 10.

Figure 10

DOS of atoms on different types of pyrite. (A) ideal crystal;(B)Fe vacancy crystal; (C) S vacancy crystal.

Figure 11.

Figure 11

DOSof atoms on different types of chalcocite. (A) ideal crystal;(B) Fe vacancy crystal; (C) S vacancy crystal.

InFigures10 and11, the DOS at the Fermi level is close to 0. Therefore,the crystals mainly exhibit semiconductor properties. As shown inFigure10, the valence bandof pyrite from −17 to −10 eV is mainly contributed bythe S 3s orbital, followed by the Fe 3d, Fe 4s, and S 3p orbitals,and the Fe 4p orbit has the least contribution. The energy range from−8.0 to −1.5 eV below the top of the valence band ismainly contributed by Fe 4s and S 3p orbitals. Among them, S 3p orbitalcontributes more, followed by the Fe 4s orbital. The Fe 3d orbitalin the valence band near the Fermi level contributes more and theactivity of Fe atoms are stronger. With the presence of Fe and S vacancies,the DOS of pyrite from 0.4 to 3.5 eV is less than ideal pyrite, andthe atomic activity of Fe increases, which is consistent with theresults of Mulliken population analysis. S vacancy also leads to anincrease of DOS at the Fermi level and a decrease of the energy gap,which enhances the metallicity of pyrite.

As shown inFigure11, the valence bandof chalcocite from −15 to −13 eVis mainly contributed by the S 3s orbital, followed by the S 3p orbital.The energy range from −7.0 to 0 eV below the top of the valenceband is mainly contributed by Cu 3d and S 3p orbitals. The Cu 3d orbitalin the valence band near the Fermi level contributes more and theactivity of the Cu atoms are stronger. With the presence of Cu andS vacancies, the DOS of chalcocite from −7.5 to 0.5 eV is lessthan ideal chalcocite, and the atomic activity of Cu and S increases.The Cu and S vacancies in chalcocite lead to a decrease of the bondenergy of copper and S from −7.5 to 0.5 eV, and an increaseof the activity of copper and S atoms. The S vacancy also leads toan increase of DOS and a decrease of the energy gap at the Fermi level.S vacancy also leads to an increase of DOS at the Fermi level anda decrease of the energy gap.

2.4.3. Analysisof Band Theory in Selective Dissolutionof Chalcocite

Previous studies showed that at the higherFermi level than the ORP of the solution, the electrons would migratefrom the semiconductor to the solution and the electron-deficientregion would be formed on the semiconductor surface.25,26 The Fermi levels of chalcocite and pyrite were calculated by Dmol3. The results are shown inTable5.

Table 5. Calculated Valueof Fermi Levels ofChalcocite and Pyrite.
mineralsthe calculatedvalue (eV)
pyrite (ideal)–5.690
pyrite (Fe vacancy)–5.638
pyrite (S vacancy)–5.621
chalcocite (ideal)–4.555
chalcocite (Cu vacancy)–4.539
chalcocite (S vacancy)–4.446

As shown inTable5, the Fermi levels of ideal chalcocite and ideal pyriteare −4.56eV and −5.69 eV, respectively. Fe, Cu, and S vacancies raisethe Fermi level of chalcocite and pyrite. The increase of the Fermilevel is beneficial to the transfer of electrons from the mineralsurface to the solution, and to the adsorption of dissolved oxygenon the surface. With the increase of the hole on the surface, S2– and S are more easily oxidized to SO42–. This causes the formation of more hydrophilic groupson the surface of the two sulfide ores and the acceleration of mineraldissolution. No matter what vacancy exists, there are significantdifferences between the Fermi levels of the two minerals. The bandgap width of pyrite is about 0.95 eV, while that of chalcocite isabout 1.1 eV.27,28 Based on the Fermi level datainTable5, the schematicdiagrams of the energy band structure of chalcocite and pyrite aredrawn inFigure12.

Figure 12.

Figure 12

Energy band structure of chalcocite and pyrite including the solutionenergy level.EF,Ec, andEv represent Fermi energy,valence band maximum, and conduction band minimum, respectively. Thesubscripts Fe, S, and i represent Fe vacancy, S vacancy, and idealcrystal, respectively.

In semiconductor physics,the energy level of the standard hydrogenelectrode (SHE) can be determined to be −4.5 eV. The relationshipbetween energy levelE and solution potentialEh can be expressed byeq1.29

2.4.3.1

In bioleaching, the solution potentialfluctuatesin the range of 250–850 mV (vs SHE). The energy level correspondingto the potential is between the Fermi level of chalcocite and pyrite.According to the Nernst equation, when the ratio of Fe3+/Fe2+ changes from 10–3 to 103, the corresponding energy levels of potential change from −5.45to −5.09 eV. The energy levels of the solution and Fe3+/Fe2+ pairs are also shown inFigure12.

Figure12 showsthat the Fermi level of ideal pyrite (−5.69 eV) is lower thanthe energy level of the solution (−4.75 to −5.35 eV)without adding bacteria. Electrons can migrate from the solution tothe pyrite surface and form an electron accumulation zone. At a lowersolution potential (Figure5, about 330 mV), the energy difference between the top ofthe pyrite valence band and the solution (about 1.04 eV) is greaterthan the width of the pyrite gap (0.95 eV). Therefore, it is difficultto form electron holes at the top of the valence band, and the apparentdissolution rate of pyrite is relatively low (Figure4). The Fermi level (−4.56 eV) of idealchalcocite is greater than the energy level of the solution. Electronscan easily migrate from the chalcocite surface to the solution. Theformation of more holes on the surface of chalcocite promotes thefracture of the Cu–S bond, which shows a higher apparent dissolutionrate (Figure4).

Fermi levels of pyrite and chalcocite increase with the presenceof vacancies in both crystals. For pyrite, it is easier to form holeson the Fe–S bond and the dissolution rate of pyrite increases.For chalcocite, the rate of electron migration from the Cu–Sbond to the solution accelerates. Chalcocite tends to further transforminto covellite and dissolve.

With the presence of bacteria,Acidithiobacillus andSulfobacillus oxidizelow-valent sulfur toS0, S2O32–, andSO42– and assist the oxidation of Fe2+, which increases the ratio of Fe3+/Fe2+ and the solution potential. When the energy level of the solutioncrosses the bottom energy level of the ideal pyrite conduction band(−4.92 eV) and approaches the top energy level of the valenceband (−5.87 eV), the electron holes at the top of the valenceband increase, and the dissolution rate of pyrite also increases.At the same time, the loss of electrons at the top of the ideal chalcocitevalence band brings a large number of holes. Cu+, whichmoves to the solid–liquid interface continuously is oxidizedto Cu2+ by dissolved oxygen and Fe3+ of thesolution. When the potential is not controlled, the concentrationof Fe3+ and the potential of the solution will continueto increase. Above 800 mV,Leptospirillum becomesa dominant group, rapidly oxidizing Fe2+ and leads to theincrease of the Fe3+/Fe2+ ratio continuously.It is difficult to inhibit the dissolution of pyrite.

If vacanciesexist in pyrite and chalcocite crystals,Leptospirillum will replaceAcidithiobacillus andSulfobacillus as the dominant group earlier because of the higher Fe2+ concentration in the solution.

If the potential of the solutionis controlled at a lower level(<700 mV or −5.2 eV), the oxidation extent of Fe2+ byLeptospirillum is limited, and the concentrationof Fe3+ in the solution is relatively low. Chalcocite isselectively dissolved by oxygen and a small amount of Fe3+ in the solution. Because of the presence of Fe, Cu, and S vacancies,the Fermi level of real minerals is higher than ideal. Therefore,the solution potential should be controlled at 600 mV or less to ensurethe selective dissolution of chalcocite.

Accordingly, we canconsider the feasibility of treating the secondarysulfide ore by two-stage bioleaching. In the first stage of bioleaching,ORP is maintained below 600 mV, so that chalcocite is completely convertedto covellite and some copper ions, and the iron leaching amount iscontrolled at a low level. In the second stage, the separation ofcovellite and pyrite is considered to realize the effective controlof the iron ion concentration in the leaching solution. The kineticinvestigation of the two-stage dissolution process of chalcocite alsosupports this view indirectly.30

3. Conclusions

Through bioleaching and first-principlesmethod analysis of secondarycopper ores and pure minerals, the mechanism of selective dissolutionof chalcocite in bioleaching was explained.

For pure minerals,the leaching efficiency of copper from chalcocitewas higher than pyrite at the same leaching time. Controlling thesolution potential at a lower level was beneficial to the selectiveleaching of chalcocite. For mixed pure mineral, bacteria increasedthe leaching efficiency of metal ions from pyrite and chalcocite simultaneouslyby oxidizing Fe2+ to Fe3+ in the solution.

Acidithiobacillus andSulfobacillus were the dominant group in theleaching of chalcocite, and the proportion ofSulfobacillus was higher.Leptospirillum was the dominant bacteriumin the leaching of pyrite. Below 700 mV of solution potential, thebacterial community, mainly consisted ofAcidithiobacillus andSulfobacillus, had a stronger promotion onthe selective dissolution of chalcocite.

In bioleaching, thesolution energy level was higher than idealpyrite but lower than ideal chalcocite, which resulted in the accumulationof electrons on the surface of pyrite and the formation of holes atthe top of the chalcocite valence band. When bacteria assisted theoxidation of Fe2+ to Fe3+ and caused the raiseof the solution potential, the difference between the solution energylevel and the top of the pyrite valence band would be smaller thanthe width of the pyrite energy gap. Then, the holes at the top ofthe pyrite valence band increased. The acceleration of pyrite dissolutionprovided more Fe2+ forLeptospirillum.Below 700 mV, the assistances ofAcidithiobacillus andSulfobacillus on the oxidation of Fe2+ were weak, and the concentration of Fe3+ was relativelylow. Chalcocite was selectively dissolved by oxygen and a small amountof Fe3+ in the solution.

Because of the presenceof Fe, Cu, and S vacancies in real minerals,the surface of chalcocite and pyrite had stronger hydrophilicity thanideal minerals. The atomic activity in the Cu–S bond and theFe–S bond enhanced, and the reaction difficulty between mineralsand electron acceptors in the solution reduced. Real minerals hadsmaller energy gaps and higher Fermi levels.Leptospirillum could replaceAcidithiobacillus andSulfobacillus as the dominant group at 600 mV or more. Therefore, the solutionpotential should be controlled at a lower level to ensure the selectivedissolution of chalcocite.

4. Materials and Methods

4.1. Samples

The secondary copper sulfidesample was obtained from the Zijinshan Copper Mine of Fujian Provinceof China. The particle size of the sample was less than 2 mm. Pureminerals of pyrite and chalcocite were obtained by separating andenriching from raw ore through hand sorting, gravity separation, andflotation. Pure minerals were all ground and sieved to minus 0.074mm.

The bacteria used in the experiment were collected fromthe sump pit of ore heap of Zijinshan Copper Mine. After 4 to 5 days’breeding and domestication in the laboratory, the bacteria with goodtolerance on copper and iron ions were obtained. Bacteria were culturedon 9 K medium. The optimum growth temperature of the bacteria is 30–45°C, and the optimum pH value is about 1.2–2.5.

4.2. Leaching Experiments

The copper sulfidesample and pure minerals were ground and sieved to minus 0.074 mm,respectively. The leaching experiments of pure minerals were carriedout in conical flasks. A certain amount of samples and 9 K mediumwere added into the conical flask. The pH of the solution was adjustedto a certain value between 1.8 and 2.0 with 20% (v/v) sulfuric acidand ensured that the initial pH of the solution in the conical flaskswas the same so that the initial solution potential was roughly thesame. The initial inoculated cell density was 2 × 107 cells/mL. The inoculation ratio (volume ratio of bacterial liquidto pulp) in conical flasks were 1:20, 1:10, and 1:5, respectively.In the process of leaching, the pH and potential of the solution weremeasured every day, and the concentration of copper and iron ionsin the supernatant were measured every 3 days. After leaching, residueswere filtered and dried. The leaching experiments of copper sulfidesamples were carried out in a stirred tank reactor, as shown inFigure13. The reactor coulddetect the solution pH value and ORP online and control the potentialby filling different gases during the leaching process. Before everyleaching, the pulp concentration was adjusted to 5%. In the leachingprocess, the stirring speed was 120 rpm, and the temperature was controlledin the range of 30–35 °C. The pH range of the solutionwas the same as that of pure mineral leaching experiment. After leaching,residues were filtered and dried.

Figure 13.

Figure 13

Stirred tank reactor with the functionof detecting and controllingthe pH and potential of the solution.

4.3. Model of Crystal Structures of Minerals

Based on the density functional theory, the calculations were performedusing the programs CASTEP and DMol3. Structural optimizationsand electronic property calculations were performed using CASTEP andGGA-PW91.16,17 The valence electrons (Fe 3d64s2, S 3s23p4, and Cu 3d104s2) were considered using ultra-soft pseudopotentials.18 A plane wave basis set with an energy cutoffof 270 eV was employed for the geometry optimization. A Monkhorst–Packk-point sampling density of 2 × 2 × 2 mesh was used.19,20 The convergence tolerances forgeometry optimization calculations were set to the maximum displacementof 0.002 Å, the maximum force of 0.08 eV Å–1, the maximum energy change of 2.0 × 10–5 eV/atomand the maximum stress of 0.1 GPa, and the self-consistent field (SCF)convergence tolerance was set to 2.0 × 10–6 eV/atom. The spin-polarization was used for all calculations. Propertieswere calculated with the same parameters as geometry optimization.The Fermi levels of crystals were calculated by Dmol3,with the GGA-PW91 method, DNP basis set, effective core potentials,a fine quality, and SCF convergence threshold of 1.0 × 10–6 eV/atom.

4.4. Analytical Techniques

The chemicalcompositions were confirmed by X-ray fluorescence spectroscopy (XRF,XRF-1700, Shimadzu, Kyoto, Japan) using a standardless quantitativeanalysis method and chemical analyses. Microscopic observation andanalysis of element distribution in leaching residues were conductedusing a mineral liberation analyzer, which included a scanning electronmicroscope (JSM-7001F, Japan Electron Optics Laboratory, Tokyo, Japan)and an energy-dispersive X-ray fluorescence spectrometer (INCA X-Max,Oxford Instruments, Oxford, U.K.). Potential and pH of the leachingsolution were determined by the pH/ORP meter (Seven Excellence S400,Mettler Toledo, Zurich, Switzerland) and a Pt electrode with referenceto a Ag/AgCl electrode. All of the potential values mentioned werenormalized to the hydrogen scale in this work. The concentrationsof Cu2+ and total iron were determined by inductively coupledplasma optical emission spectrometry (725-Agilent Technologies, California).

The leaching efficiencyE of metal ions were calculatedbyeq2. In the equation,C is the concentration of metal ions,V is the volume of the solution, α is the grade of the metal,m is the mass of ore samples, andM isthe molecular weight

4.4.2

Microorganisms were harvestedfrom 5.0 mL representative leachingsolutions. The cells were centrifuged at 12000g for10 min for cell collection. Total DNA was extracted using the PowerWaterDNA Isolation Kit (QIAGEN China Co. Ltd., Beijing, China). DNA qualityassessment and quantification were conducted using a NanoDrop ND-1000Spectrophotometer (NanoDrop Technologies Inc., Wilmington, DE). PCRwas conducted on Applied Biosystems (ABI) Veriti 96-well Fast ThermalCyclers with bacterial primer pair (341 F of the forward primer and805 R of the reverse primer) for the V3-V4 region of the 16 S rRNAgene.31,32 Each sample was amplified under the followingconditions: 94 °C for 5 min, 28 cycles at 94 °C for 45 s,62 °C for 45 s, and 72 °C for 1 min, then 10 min at 72 °C.PCR products were purified using the EZNA Gel Extraction Kit (OmegaBio-tek). The library quality was assessed on the QuantiFluor-ST (Promega).Then, the library was sequenced on an Illumina Miseq platform (Majorbio,Shanghai) with the sequencing strategy PE300. The sequencing datasetsof bacteria and fungi have been deposited in the National Center forBiotechnology Information (NCBI) Sequence Read Archive (SRA) (accessionNo. PRJNA555796).

4.5. Data Analysis

All sequence processingand diversity estimates were performed using the QIIME. To obtainclean tags, low-quality sequences and chimeras were filtered, trimmed,and removed.33 Most of the sequence lengthsafter quality control were between 450 bp and 460 bp. High-qualitynonchimeric sequences were clustered into operational taxonomic units(OTUs) using a 97% similarity threshold and the uclust algorithm withoptimal uclust settings. The taxonomy of OTU representative sequenceswas phylogenetically assigned to taxonomic classifications by theRDP Classifier with a confidence threshold of 0.8.34 All experiments were performed at least three times. Eachdata point and error bar represented the mean and standard deviation,respectively.

Acknowledgments

This project wasfinancially supported by the National NaturalScience Foundation of China (No. 51574036).

The authors declare nocompeting financial interest.

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