安徽省怀宁县桂家冲铁(铜)矿床地质特征及成因探讨

安徽省怀宁县桂家冲铁(铜)矿床位于长江中下游成矿带的月山矿田内,矿体赋存于月山岩体北枝与东枝夹持的铁铺岭向斜西翼下方的接触带或附近捕虏体中。对桂家冲铁(铜)矿床地质特征、成因及控矿因素进行探讨,认为矿床成因类型为接触交代—热液型矿床,铁(铜)矿体的形成受岩浆岩、地层、构造等因素控制。此研究对在月山矿田铁铺岭向斜两翼及周边地区寻找同类型矿床有一定的指导作用。

Effect of EPS on adhesion of Acidithiobacillus ferrooxidans on chalcopyrite and pyrite mineral surfaces

Extracellular polymeric substances （EPS） were extracted from Acidithiobacillus ferrooxidans through sonication method associated with centrifugation, which was evaluated tentatively with 2-keto-3-deoxyoctonic acid （KDO） as the indicator of EPS by spectrophotometry. Then the effect of EPS of A. ferrooxidans on the adhesion on chalcopyrite and pyrite surfaces was studied through a series of comparative experiments. The untreated cells and EPS-free cells of A. ferrooxidans were mixed with EPS suspension, Fe^2＋ or Fe^3＋, respectively. The planktonic cells were monitored in 2 h during bioleaching. The results indicate that the presence of EPS on the cell is an important factor for the adhesion to chalcopyrite and pyrite. A decrease of attachment of A. ferrooxidans to minerals was produced by the deficiency of EPS, which can recover mostly when the EPS was re-added into the EPS-free cells. The restoring extent is more obvious in pyrite than in chalcopyrite. The extent of cell adhesion to chalcopyrite increased when EPS and Fe^3＋ added, and decreased when Fe^2＋ added, which imply the electrostatic interaction plays a main role in initial adhesion between bacteria and minerals and it is a driving force for bacteria to produce EPS probably as a result of regaining their attachment ability to copper sulphides.

Surface characterization of chalcopyrite interacting with Leptospirillum ferriphilum

The alteration of surface properties of chalcopyrite after biological conditioning with Leptospirillum ferriphilum was studied by adsorption,zeta-potential,contact angle and bioleaching tests.The strains of L.ferriphilum cultured using different energy sources（either soluble ferrous ion or chalcopyrite） were used.The adhesion of bacteria to the chalcopyrite surface was a fast process.Additionally,the adsorption of substrate-grown bacteria was greater and faster than that of liquid-grown ones.The isoelectric point（IEP） of chalcopyrite moved toward that of pure L.ferriphilum after conditioning with bacteria.The chalcopyrite contact angle curves motioned diversely in the culture with or without energy source.The results of X-ray diffraction patterns（XRD）,scanning electron microscopy（SEM） and energy-dispersive X-ray spectroscopy（EDS） analysis indicate that the surface of chalcopyrite is covered with sulfur and jarosite during the bioleaching process by L.ferriphilum.Furthermore,EDS results imply that iron phase dissolves preferentially from chalcopyrite surface during bioleaching.The copper extraction is low,resulting from the formation of a passivation layer on the surface of chalcopyrite.The major component of the passivation layer that blocked continuous copper extraction is sulfur instead of jarosite.

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.

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 pH values on extracellular protein and polysaccharide secretions of Acidithiobacillus ferrooxidans during chalcopyrite bioleaching

The effect of pH values on the extracellular protein and polysaccharide secretions of Acidithiobacillus ferrooxidans was comparatively investigated in different phases of bacterial growth during chalcopyrite bioleaching. The results indicate that the extracellular protein is always more than the extracellular polysaccharide secreted by attached cells on the chalcopyrite, on the contrary, and is always less than the extracellular polysaccharide secreted by free cells in the solution at bacterial adaptive phase, logarithmic phase and stationary phase whenever pH value is at 1.0, 1.5, 2.0 or 2.5; free cells are mainly through the secretion of extracellular polysaccharide rather than the extracellular protein to fight against disadvantageous solution environment, such as high concentration of metal ions and unsuitable pH solution; both amounts of polysaccharide and protein secreted by attached cells are mainly positively related to the solution acidity rather than the total concentration of soluble metal ions. The experimental results imply that bacteria are mainly through secreting more extracellular polysaccharide to fight against disadvantageous environment and the extracellular protein perhaps plays an important role in oxidation？reduction reactions in the bioleaching system.

Enrichment of ferric iron on mineral surface during bioleaching of chalcopyrite

In order to investigate the enrichment of ferric iron bound by extracellular polymeric substance （EPS） on the mineral surface during bioleaching of chalcopyrite, several methods including sonication, heating and vortexing were used and sonication at 48℃ was shown as a good way to extract ferric iron. Scanning electron microscope （SEM） and energy dispersive X-ray spectrometer （EDX） analysis showed that lots of cracks and pits can be found on the chalcopyrite surface after bioleaching and that iron oxide was filled in these cracks and pits. The variations of contents of ferric iron and EPS on the chalcopyrite surface were investigated. The results indicated that the content of EPS increased rapidly in the first 10 d and then maintained at a stable level, while ferric iron content increased all the time, especially in the later stage of bioleaching.

Mechanism of sodium sulfide on flotation of cyanide-depressed pyrite

The mechanism of sodium sulfide(Na2S)on the flotation of cyanide-depressed pyrite using potassium amyl xanthate(PAX)as collector was investigated by flotation test and electrochemical measurements.The flotation results show that both PAX and Na2S can promote the flotation recovery of cyanide-depressed pyrite and their combination can further improve the pyrite flotation recovery.Electrochemical measurements show that PAX and Na2S interacted with cyanide-depressed pyrite through different mechanisms.PAX competed with cyanide and was adsorbed on the pyrite surface in the form of dixanthogen,thus enhancing the hydrophobicity and flotation of cyanide-depressed pyrite.Unlike PAX,Na2S rendered the pyrite surface hydrophobic through the reduction of ferricyanide species and the formation of elemental sulfur S0 and polysulfide Sn2-.The combined application of PAX and Na2S induced superior pyrite flotation recovery because of a synergistic effect between PAX and Na2S.

Bioleaching and dissolution kinetics of pyrite,chalcocite and covellite

In this work,the bioleaching process of pyrite,chalcocite and covellite which were the main phase compositions for Zijin copper mineral was comprehensively studied.The influence parameters,such as leaching temperature,Fe^(3+)concentration,pH of solution and bacteria concentration were investigated.The leaching kinetics of the pyrite,chalcocite and covellite under the studied conditions was successfully modeled by an empirical diffusion-like equation,respectively.The apparent activity energy of pyrite leaching,chalcocite leaching(stage Ⅱ)and covellite leaching was calculated to be 69.29,65.02 and 84.97 kJ/mol,respectively.

Influences of collector DLZ on chalcopyrite and pyrite flotation

The interaction mechanism of collector DLZ in the flotation process of chalcopyrite and pyrite was investigated through flotation experiments,zeta potential measurements and infrared spectrum analysis.Flotation test results indicate that DLZ is the selective collector of chalcopyrite.Especially,the recovery of chalcopyrite is higher than 90% in neutral and weak alkaline systems,while the recovery of pyrite is less than 10%.When using CaO as pH regulator,at pH=7-11,the floatability of pyrite is depressed and the recovery is less than 5%.Zeta potential analysis shows that the zeta potential of chalcopyrite decreases more obviously than that of pyrite after interaction with DLZ,confirming that collector DLZ shows selectivity to chalcopyrite and pyrite.And FTIR results reveal that the flotation selectivity of collector DLZ is due to chemical absorption onto chalcopyrite surface and only physical absorption onto pyrite surface.

Xanthate interaction and flotation separation of H2O2-treated chalcopyrite and pyrite

This study investigated the effects of H2O2 treatment on xanthate interaction and flotation separation of chalcopyrite and pyrite by making use of a series of laboratory flotation experiments and surface analysis techniques.Flotation test results showed that H2O2 treatment influenced the flotation behaviors of the two minerals;however,flotation of pyrite was depressed more significantly than that of the chalcopyrite.Under well-controlled H2O2 concentration,the selective separation of chalcopyrite from pyrite was realized at pH 9.0,at which the recovery of chalcopyrite was over 84%and that of pyrite was less than 24%.Zeta potential,UV-visible and IR spectrum measurements revealed that the collector interacted differently with the two minerals after H2O2 treatment,and the surface of chalcopyrite adsorbed much greater amount of xanthate than that of the pyrite.IR and XPS analyses showed that the H2O2 treatment significantly changed the surface properties of pyrite to very hydrophilic species that inhibited the adsorption of collector and thus depressed the floatability of pyrite.While,the surface of chalcopyrite remained mildly inert to H2O2,as a result,the adsorption of xanthate and its oxidation to dixanthogen were very effective,which enhanced the flotation of chalcopyrite.

Characterization and kinetic study on ammonia leaching of complex copper ore

Ammonia leaching kinetics of a complex Cu-ore assaying 8.8% Cu and 36.1% Fe was examined. Mineralogical characterization indicated that the major phase of the ore was siderite with chalcopyrite as the major sulfide mineral. The effects of parameters such as agitation, temperature, NH3 concentration, particle size and oxygen partial pressure （Po2） were investigated. Under the standard leaching conditions of 125-212 μm particle size, 120 ℃, 1.29 mol/L NH3 and 202 kPa ofpo2, about 83% Cu could be selectively extracted in 2.5 h. However, when using higher NH3 concentration and lower particle size, more than 95% extraction was achieved. The leaching process was found to be surface reaction controlling. The estimated activation energy was （37.6±1.9） kJ/mol and empirical orders of reaction with respect topos and [NH3] were about 0.2 and 1, respectively.

Synthesis and characterization of Cu-Cr-O nanocomposites

Cu-Cr-O nanocomposites that can be used as additives for the catalytic combustion of AP(ammonium perchlorate)-based solid-state propellants were synthesized via a citric acid(CA) complexing approach. Techniques of TG-DTA, XRD as well as TEM were employed to characterize the thermal decomposition procedure, crystal phase, micro-structural morphologies and grain size of the as-synthesized materials respectively. The results show that well-crystallized Cu-Cr-O nanocomposites can be produced after the CA-Cu-Cr precursors are calcined at 500 ℃ for 3 h. Phase composition of the as-obtained Cu-Cr-O nanocomposites depends on the molar ratio of Cu to Cr in the starting reactants. Addition of the as-synthesized Cu-Cr-O nanocomposites as catalysts enhances the burning rate as well as lowers the pressure exponent of the AP-based solid-state propellants considerably. Noticeably, catalyst with a CuCr molar ratio of 0.7 exhibits promising catalytic activity with high burning rate and low pressure exponent at all pressures, due to the effective phase interaction between the spinel CuCr2O4 and delafossite CuCrO2 contained in the as-synthesized Cu-Cr-O nanocomposites.

Effects of copper ions on dissolution mechanism of marmatite

The dissolution mechanism of marmatite in the presence of Cu^(2+)was intensively studied by experiments and density functional theory(DFT) calculations. Leaching experiments showed that Cu^(2+)accelerated marmatite dissolution at high temperatures(above 55 ℃), but the trend was reversed at low temperatures(below 45 ℃), which may be because the reaction mechanism between Cu^(2+)and marmatite changed from surface adsorption to bulk substitution with increasing temperature. The substitution reaction caused more zinc atoms in the marmatite crystal lattice to be released and enhanced the electrochemical reactivity, while the adsorption of copper ions at low temperatures would passivate marmatite, thus inhibiting the reaction process. DFT calculations showed that the energy of the substitution reaction was more negative than that of the adsorption reaction at high temperatures, which further verified the proposed mechanism.

Ultrasonic-enhanced selective sulfide precipitation of copper ions from copper smelting dust using monoclinic pyrrhotite

The sulfide passivation film produced on the surface seriously prevents further reaction in the process of using monoclinic pyrrhotite(MPr)to treat heavy metal ions in wastewater.Ultrasonic technology was introduced to assist MPr to recover the copper ions.XPS result proves that CuS products exist on the surface of MPr.XRD and SEM results show that the CuS on the particles’surface is stripped under ultrasonic condition.The kinetics results indicate that the reaction under both conventional and ultrasonic conditions conform to the Avrami model.The reaction process changes from diffusion control to chemical reaction control under the ultrasonic condition as the solid layer is stripped off.The presence of ultrasonic significantly reduces the acidity and temperature required for the reaction and enhances the utilization efficiency of MPr;by controlling the amount of MPr,the removal rates of copper and arsenic in copper smelting dust leachate exceed 99%and 95%,respectively.

Biodissolution of pyrite and bornite by moderate thermophiles

Acid mine drainage(AMD)has become a widespread environmental issue and its toxicity can cause permanent damage to the ecosystem.However,there are few studies focusing on the formation of AMD under moderately thermophilic conditions,hence we employed X-ray diffraction(XRD),scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS)and 16S rRNA sequencing to study the dissolution of pyrite and bornite by a moderate thermophilic consortium,and explored the role of free and attached microorganisms in the formation of AMD.The consortium mainly comprised Acidithiobacillus caldus,Leptospirillum ferriphilum and Sulfobacillus thermosulfidooxidans.The results indicated that total iron in pyrite solution system reached 33.45 g/L on the 12th day,and the copper dissolution rate of bornite dissolution reached 91.8%on the 24th day.SEM results indicated that the surfaces of pyrite and bornite were significantly corroded by microorganisms.XRD and XPS results showed that ore residues contained jarosite,and the dissolving residue of bornite contained elemental sulfur.The dominant bacterial genus in pyrite dissolution was A.caldus,and L.ferriphilum in bornite dissolution.To sum up,microbes significantly accelerated the mineral dissolution process and promoted the formation of AMD.

Leaching of chromite ore in concentrated KOH by catalytic oxidation using CuO as catalyst

CuO was used as a catalyst in the concentrated KOH solution to enhance the leaching of chromium from the chromite ore.The impacts of temperature,KOH-to-chromite ore mass ratio,CuO-to-chromite ore mass ratio,and gas flow rate on the chromiumleaching rate were investigated.The results indicated that CuO played an important role in improving the chromium leaching rate.The leaching rate reached98%after leaching for6h when CuO was applied,whereas it was only60.8%without CuO under thesame reaction conditions:temperature230°C,KOH-to-ore mass ratio6:1,stirring speed700r/min,gas flow rate1L/min.Accordingto the kinetics study,the catalytic oxidation was controlled by surface chemical reaction and the activation energy was calculated tobe15.79kJ/mol when the temperature was above230°C.In contrast,without CuO,the rate-determining step was external diffusionand the apparent activation energy was38.01kJ/mol.

Formation of arsenic−copper-containing particles and their sulfation decomposition mechanism in copper smelting flue gas

The heat recovery steam generator(HRSG)of copper smelting generates a large number of arsenic−coppercontaining particles,and the in-situ separation of arsenic and copper is of importance for cutting off environmental risk and realizing resource recovery.The formation of arsenic−copper-containing particles was simulated,the method of in-situ decomposition of arsenic−copper-containing particles by pyrite was proposed,and the decomposition mechanism was confirmed.It was found that particles with high arsenic content were formed in the simulated HRSG,and copper arsenate was liable for the high arsenic content.Pyrite promoted the sulfation of copper,leading to the in-situ decomposition of copper arsenate.In this process,gaseous arsenic was released,and thus the separation of arsenic and copper was realized.

Flotation and electrochemical behaviors of chalcopyrite and pyrite in the presence of N-propyl-N′-ethoxycarbonyl thiourea

The characteristics of N-propyl-N′-ethoxycarbonyl thiourea（PECTU） were studied in the flotation experiments of chalcopyrite and pyrite compared with butyl xanthate（BX）. The interaction mechanism between mineral and PECTU was investigated according to zeta potential and electrochemistry measurements in the presence of PECTU. The results proved that PECTU performed a stronger ability to capture chalcopyrite and a better selectivity against pyrite. The zeta potential of chalcopyrite was positively shifted after interacting with PECTU, which indicated that the collector PECTU was obviously adsorbed on chalcopyrite surface. The cyclic voltammetry and Tafel curves results indicated that the oxidation and corrosion rates of chalcopyrite surface were limited in the presence of PECTU, while the effect of PECTU on pyrite in weak alkaline solution can be neglected basically according to the results of zeta potential and electrochemical tests.

Relationships among bioleaching performance, additional elemental sulfur, microbial population dynamics and its energy metabolism in bioleaching of chalcopyrite

To estimate the relationships among bioleaching performance, additional elemental sulfur （S0）, microbial population dynamics and its energy metabolism, bioleaching of chalcopyrite by three typical sulfur- and/or iron-oxidizing bacteria, Acidithiobacillus ferrooxidans, Leptospirillum ferriphilum and Acidithiobacillus thiooxidans with different levels of sulfur were studied in batch shake flask cultures incubated at 30 °C. Copper dissolution capability （71%） was increased with the addition of 3.193 g/L S0, compared to that （67%） without S0. However, lower copper extraction was obtained in bioleaching with excessive sulfur. Microbial population dynamics during chalcopyrite bioleaching process was monitored by using PCR-restriction fragment length polymorphism （PCR-RFLP）. Additional S0 accelerated the growth of sulfur-oxidizing bacteria, inhibited the iron-oxidizing metabolism and led to the decrease of iron-oxidizing microorganisms, finally affected iron concentration, redox potential and bioleaching performance. It is suggested that mixed iron and sulfur-oxidizing microorganisms with further optimized additional S0 concentration could improve copper recovery from chalcopyrite.