Effect of content and spin state of iron on electronic properties and floatability of iron-bearing sphalerite:A DFT+U study

Iron is an impurity widely occurred in sphalerite,and its effect on sphalerite flotation is complex.In this work,the effects of iron content and spin state on electronic properties and floatability of iron-bearing sphalerite are comprehensively studied using density functional theory Hubbard U(DFT+U)calculations combined with coordination chemistry flotation.The band gap of ideal sphalerite is 3.723 eV,and thus electron transition is difficult to occur,resulting in poor floatability.The results suggest the band gap of sphalerite decreases with increasing iron content.For low iron content,the decreased band gap facilitates electron transition;at this case,Fe^(2+)in a high-spin state possesses oneπelectron pair,which can form a weakπ-backbonding with xanthate,causing increasing floatability.However,for medium and high iron-bearing sphalerite,with the further decrease of band gap,Fe^(2+)is oxidized to Fe^(3+)due to electrochemical interaction,and henceπ-backbonding is eliminated,leading to lower floatability of iron-bearing sphalerite,which is consistent with the flotation experimental results.This work could give a deeper understanding of how sphalerite flotation behaviors are affected by iron content.

Study on the occurrence state of indium in sphalerite of Dulong Sn–Zn–In polymetallic deposit,Southwest China

The Dulong deposit,located in the Laojunshan area of southeastern Yunnan,China,is an important polymetallic deposit due to its high reserves of tin,zinc,and indium.The occurrence state of indium is critical for understanding its supernormal enrichment mechanism.Previous studies investigated the occurrence state of indium(including the valence state)based on the indium content in sphalerite and the correlation between metal concentrations.However,more evidence is needed to better constrain indium occurrence at the micro-,nano-,or even atomic scale.In this study,EPMA-FIB-SEM-TEM and XPS techniques were employed to investigate the indium distribution characteristics and occurrence state in sphalerite from the Dulong Sn–Zn–In polymetallic deposit.The maximum concentration of indium in the indium-rich sphalerite samples is 0.37%,and the results of the EPMA analysis showed a relatively homogeneous distribution of indium in sphalerite.The FIB-SEM-TEM results demonstrated that the lattice stripes of sphalerite were periodically and continuously distributed at the nanoscale,confirming that sphalerite in the deposit was an excellent single crystal structure,and the peak heights of the various characteristic peaks of indium in the EDX spectra were relatively close to each other,with no distinct peaks of high indium content.In addition,the XPS results indicate that the element valence state of indium in sphalerite is In^(3+),and it combines with S^(2-)to form a bond.These results indicate that indium in sphalerite of the Dulong deposit is uniformly distributed at both the micro-and nanoscale,and there is no indium-independent mineral.In^(3+)enters the crystal lattice of sphalerite by replacing Zn2+in the form of isomorphic substitution.

Photocatalytic Reduction of Cr^Ⅵ by Natural Sphalerite Suspensions under Visible Light Irradiation

The photocatalytic reductive capability of a natural semiconducting mineral, sphalerite has been studied for the first time. The sphalerite from the Huangshaping deposit of Hunan Province performed great photoreductive capability that 91.95% of the Cr^6＋ was reduced under 9 h visible light irradiation, higher than the 70.58% under 9.5 h UV light irradiation. The highly reductive ability results from its super negative potential of electrons in the conduction band. Furthermore, Fe substitution for Zn introduces donor states, and the oxidation process of Fe^2＋ to Fe^3＋ makes it an effective hole-scavenger. Cd and Cu substitute for Zn also reduce the bandgap and help broaden the absorbing edge towards the visible light. These substituting metal ions in natural sphalerite make it a hyper-active photocatalyst and very attractive for solar energy utilization.

KINETICS OF LEACHING SPHALERITE WITH PYROLUSITE SIMULTANEOUSLY BY MICROWAVE IRRADIATION

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Semiconducting Mineralogical Characteristics of Natural Sphalerite Gestating Visible-light Photocatalysis

Natural sphalerite as a natural cost-effective photocatalyst was characterized and its visible light photocatalytic activity was investigated in terms of substituting ions, impurity phases and surface defects. The substitutions of metal ions for Zn2＋ alter the band structure and result in the visible light response. The coexistence of impurity semiconductors and nanosized particles in natural sphalerite samples help to prolong the lifetime of electron-hole pairs. The cleavage planes and fracture surfaces improve the photocatalytic activity of natural sphalerite by providing more active sites than perfect faces. Both the negative charge defects from the non-isoelectronic substitutions and surface elements with variable chemical valence suppressed the recombination of electron-hole pairs by their possible role of capturing photogenerated holes.

Determining Pressure with Daughter Minerals in Fluid Inclusion by Raman Spectroscopy:Sphalerite as an Example

Raman frequency of some materials, including minerals, molecules and ions, shifts systematically with changing pressure and temperature. This property is often used as a pressure gauge in high pressure experiments with the hydrothermal diamond anvil cell （HDAC）. Since the system of fluid inclusion is similar to that of HDAC, it can also be used to determine the internal pressure of fluid inclusions. Sphalerite is a common daughter mineral. In this study, the frequency shift of the 350 cm-1 peak of sphalerite has been studied from 296 to 523 K and from 0.07 to 2.00 GPa using the HDAC. The global slope of the isotherms （V350/p）T is 0.0048 in the studied pressure range. No significant variation of the slopes with temperature has been observed. The correlation between the frequency shift of the 350 cm-1 peak of sphalerite and pressure and temperature is constrained as P=208.33（△ Vp）350＋3.13T-943.75. This relationship may be used to estimate the internal pressure of the sphalerite-bearing fluid inclusions.

Quantum-mechanical study of effect of lattice defects on surface properties and copper activation of sphalerite surface

The electronic properties of sphalerite(110)surface bearing Fe,Mn and Cd impurities were calculated using density-functional theory,and the effects of impurities on the copper activation of sphalerite were investigated.Calculated results indicate that both Fe and Mn impurities narrow the band gap of sphalerite surface and lead to the Fermi level shifting to conduction band.Impurity levels composed of Fe 3d and Mn 3d orbital appearing in band gap are beneficial to electrons transfer from the valence band to the conduction band and promote the surface conductivity and the electrochemical activity.The results show that Fe and Mn impurities cannot be replaced by Cu atom,which reduces the exchange sites(Zn)for Cu atom,hence Fe-and Mn-bearing sphalerites are hard to be activated by copper.Cd impurity has little effect on electronic structure of sphalerite surface;however,Cd atom is easily replaced by Cu atom,and this is the reason why the Cd-bearing sphalerite can be easily floated.

Zn release from fluid inclusions in a natural sphalerite

The type, size, and compositions of fluid inclusions in a natural sphalerite were investigated and the total concentration of Zn released from the fluid inclusions was measured. To compare the total concentration of Zn released from the fluid inclusions with that dissolved from the sphalerite itself, dissolution experiments and theoretical calculations for the dissolution equilibrium of the sphalerite were also performed. The results indicate that large numbers of fluid inclusions with various sizes exist in the sphalerite, which can be divided into four types, i.e., pure gaseous inclusions, pure liquid inclusions, gas-liquid inclusions, and gas-liquid inclusions containing solid minerals. These inclusions were broken open during the grinding process, and their compositions were released to the solution. The total concentration of Zn released from these inclusions reaches 18.35×10^-6 mol/L, which is much higher than that of Zn dissolved from the sphalerite itself （1.93×10^-6 mol/L） and the theoretical calculation value （2.73×10^-8 mol/L）.

An electrochemical investigation on collectorless flotation of sphalerite in presence of Cu^(2+) ions

The collectorless flotation behaviors of sphalerite in the presence of Cu 2+ ions have been established. The effects of pH, potential and Cu 2+ concentration on the flotation have been studied using a micro flotation cell specially designed, where the potential can be controlled by a potentiostat. The flotation results have shown that the Cu activated sphalerite displays a good collectorless floatability in a pH range of 0～13. The higher potentials can improve the flotation recovery. The surface species formed during the Cu ion activation have been examined using a special electrochemical technique—a composite sphalerite electrode. Zinc deficient sulfide (Zn 1- x Cu x S) and Cu poly sulfide (Cu y+z S y ) species have been determined. They are responsible for the collectorless flotation of sphalerite. In additional, they can improve the conductivity of the sphalerite surface.

THE KINETICS OF FERRIC CHLORIDE LEACHING OF SPHALERITE IN THE MICROWAVE FIELD

The kinetics of ferric chloride leaching of sphalerite in the microwave field has being studied in this paper.According to the experimental data,the rate of dissolution of sphalerite microwave irradiation heating is faster than that with conventional heating.The dissolution of sphalerite in the microwave field was investigated in different condition of temperature,concentration of FeCl,and particle size and a nonisothermal kinetic equation has being obtained.

Trace Elements in Sphalerite from the Dadongla Zn-Pb Deposit, Western Hunan-Eastern Guizhou Zn-Pb Metallogenic Belt, South China

The western Hunan-eastern Guizhou Zn-Pb metallogenic belt is one of the important Zn-Pb mineralization regions in China.The Dadongla deposit,located in the northeast of Guizhou Province,is one of the typical Zn-Pb deposits in the region and has estimated resources more than 12 million metric tons(Mt)with an average grade of 4.11 wt%Zn+Pb.Its orebodies are hosted in the lower Cambrian Aoxi Formation dolomite,occurring as bedded,para-bedded in shape,and in conformity with the wall rock.The ore mineral assemblage is simple,dominated by sphalerite with minor pyrite and galena,and the gangue minerals are composed of dolomite,calcite with minor bitumen and barite.In view of the lack of geological and geochemical researches,the genesis of Zn-Pb ore is still unclear.Laser ablation-inductively coupled plasma mass spectrometry(LA-ICPMS)spot and mapping analyses were used to obtain sphalerite trace element chemistry in the Dadongla Zn-Pb deposit in Guizhou,China,aiming to constrain its ore genesis.The results show that sphalerite is characterized by the enrichment of Cd,Fe,Ge and Hg,corresponding with that of typical MVT deposits.Four zones were identified in the sphalerite crystal from Dadongla from the center to margin according to the color bands.in which the zone in the center,representing the early ore-stage sphalerite,is characterized by enrichment of Cd relatively,while the zone forming at late ore-stage is enriched in Ge and Hg relatively.The finding was controlled by differential leached metals content in ore-forming fluid from its source rock.Notably,critical element Ge trends to be enriched at the late ore-stage and follows a substitution of 2 Zn^2+(?)Ge^4++□(vacancy).Moreover,the calculated ore-forming temperature ranges from 79.9℃to 177.6℃by the empirical formula,which is similar to that of typical Mississippi Valley-type(MVT)deposits.Compared with the features of trace elements in sphalerite from different types of deposits,together with the geology,the Dadongla deposit belongs to an MVT Zn-Pb deposit.

Sphalerite Chemistry, Niujiaotang Cd-Rich Zinc Deposit, Guizhou, Southwest China

Sphalerite in the Niujiaotang Cd rich zinc deposit, Duyun, Guizhou is characteristically light yellow in color with significant enrichment of cadmium which ranges from 0.83% to 1.97% (averaging 1.38%) in concentration in the mineral, corresponding to an enrichment coefficient as high as 30.47 to 72.96. In comparison with other major Pb Zn deposits in the world (the Mississippi Valley deposits, and the Fankou and Jinding deposits in China) the Niujiaotang deposit is n-n×10 times richer in cadmium. Sphalerite in the deposit is also rich in Ga and Ge, but poor in In, Mn and Fe, suggesting some special mechanisms that govern the geochemical behavior of these trace elements. Except for a minor amount of independent minerals like greenockite, cadmium occurs mainly as isomorphous impurity in the crystal lattice of sphalerite. During weathering and leaching under supergene condition, cadmium was separated from Zn, resulting in some secondary minerals of Cd, including oxides and otavite.

Effect of vacancy defects on electronic properties and activation of sphalerite(110) surface by first-principles

The electronic properties of sphalerite(110) surface with Zn-vacancy and S-vacancy were calculated by using density-functional theory,and the effects of vacancy defect on the copper activation of sphalerite were investigated.The calculated results indicate that surface state occurs in the band gap of Zn-vacancy sphalerite,which is from the contribution of S 3p orbital at the first layer of the surface.The presence of S-vacancy results in surface state appearing near the Fermi level and the bottom of conductor band,which are composed of S 3p and Zn 4s orbital,respectively.The surface structure of Zn-vacancy sphalerite is more stable than S-vacancy surface due to the occupation of Zn-vacancy by Cu atoms;hence,the substitution reaction of Cu for Zn vacancy is easier than the substitution of Cu for Zn atoms with S-vacancy surface.

Bioleaching of sphalerite by Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans cultured in 9K medium modified with pyrrhotite

Elective culture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans in 9K medium modified with pyrrhotite was studied.Bioleaching of flotation concentrate of sphalerite by the selected bacteria was carried out.The results show that the microorganisms cultured by pyrrhotite are a mixture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans,of which the capability to oxidize ferrous to ferric irons is enhanced by the high mass ratio of Fe to S in pyrrhotite.Three pyrrhotite samples were separated into various parts with corresponding S/Fe ratios by magnetic separation and were used to culture the elective bacteria as the substrate.The association of the cultures could provide a more rapid and complete oxidation of sphalerite than that of bacteria cultivated by conventional methods.

Chalcopyrite Intergrowths in Sphalerite in the Meixian Lead-Zinc Deposit, Fujian Province and Their Metallogenic Significance

Ore textures and electron microprobe analyses show that in addition to highly scattered blebs in sphalerite grains, intergrown chalcopyrite also occurs as reds, myrrmekites andlamellae aligned along cleavages and twin boundaries of the host sphalerite. The majority of theintergrowths could have been formed by replacement of sphalerite by chalcopyrite, albeit part ofthem may have resulted from exsolution. Not only copper, but also iron were introduced intothe sphalerite by replacive fluids.While the front of the replacing fluid was moving forward through a sulphide orebody, Znand Pb were dissolved and Cu was precipitated, resulting in zonal refining of the sulphide ores.The remobilized zinc and lead were precipitated at favourable sites with changed physiccrchemical conditions. This is a Possible mechanism for the formation of copper-poor zinc and lead oresabove or lateral to the copper orebodies in some of the massive sulphide deceits reworked andoverprinted by late-stage granites and their hydrothermal fluids.

Flotation and surface modification characteristics of galena,sphalerite and pyrite in collecting-depressing-reactivating system

The flotation tests and XPS analyses on galena,sphalerite and pyrite have been carried out in a collecting-depressing-reactivating system(hereafter referred as the CDR system).In this system,sulfide minerals were first collected and activated by the collector,and then depressed strongly by Ca(OH)2 in the strong alkaline solution,and finally reactivated by H2SO4.The flotation tests of pure minerals show that in this system the flotation behaviors of sphalerite and pyrite present irreversible characteristics along with the change of pulp potential.Furthermore,through the CDR system,considerable differences in the flotabilities between galena and sphalerite/pyrite are also observed.The XPS analysis results for galena,sphalerite and pyrite in a CDR system show that in the strong alkaline solution,some of the collectors,that have been already adsorbed on the mineral surface in the collecting process,are desorbed by Ca(OH)2.The XPS analysis results also show that in H2SO4 reactivating process,the surface hydroxides of galena are desorbed again by H2SO4 and replaced by diethyl dithiocarbamate,but those of sphalerite and pyrite are not desorbed.This flotation system may be applied to the bulk-differential flotation process of sulfur-bearing low-grade lead-zinc ores.

Timing of formation of the Hongdonggou Pb-Zn polymetallic ore deposit,Henan Province,China:Evidence from Rb-Sr isotopic dating of sphalerites

The Hongdonggou Pb-Zn polymetallic ore deposit, located in the southwestern part of the Luanchuan Mo-W-Pb-Zn-Ag polymetallic ore mineralization in Henan Province, China, is an important part of the East Qinling metallogenic belt. The orebodies in the deposit, which are vein, bedded and lenticular, are mainly hosted in the syenite porphyry, and formed within the carbonate and clastic rocks of the Yuku and Qiumugou formations partially. The genesis of the deposit has previously been argued to be of hydrothermal-vein type or of skarn-hydrothermal type. In this study, we report the results of Rb-Sr isotopic dating based on sphalerites from the main orebody of the Hongdonggou Pb-Zn polymetallic ore deposit, which yield an isochron age of 135.7 ± 3.2 Ma, constraining the timing of mineralization as early Cretaceous. The age is close to those reported for the Pb-Zn deposits in the Luanchuan ore belt. The （87Sr/86Sr）i values of the sphalerites （0.71127± 0.00010） are lower than that of terrigenous silicates （0.720） and higher than the mantle （0.707）, suggesting that the metallogenic components were mainly derived through crust-mantle mixing. Combining the results from this study with those from previous work, we propose that the Hongdonggou Pb-Zn polymetallic ore deposit is a hydrothermal-vein deposit associated with the early Cretaceous tectonothermal event, and the mineralization is controlled by NW- and near EW-trending faults in the Luanchuan Mo-W-Pb-Zn-Ag polymetallic ore concentration belt.

Kinetics and Modeling of Chemical Leaching of Sphalerite Concentrate Using Ferric Iron in a Redox-controlled Reactor

This work presents a study for chemical leaching of sphalerite concentrate under various constant Fe3+ concentrations and redox potential conditions. The effects of Fe3+ concentration and redox potential on chemical leaching of sphalerite were investigated. The shrinking core model was applied to analyze the experimental results. It was found that both the Fe3+ concentration and the redox potential controlled the chemical leaching rate of sphalerite. A new kinetic model was developed, in which the chemical leaching rate of sphalerite was proportional to Fe3+ concentration and Fe3+ /Fe2+ ratio. All the model parameters were evaluated from the experimental data. The model predictions fit well with the experimental observed values.

Single and cooperative bioleaching of sphalerite by two kinds of bacteria——Acidithiobacillus ferriooxidans and Acidithiobacillus thiooxidans

A cooperative bioleaching(Acidithiobacillus ferriooxidans and Acidithiobacillus thiooxidans)and single bioleaching(Acidithiobacillus ferriooxidans or Acidithiobacillus thiooxidans)of sphalerite were investigated by X-ray diffractometry,energy dispersive spectrography and scanning electron microscopy.The experimental results show that the leaching rate of zinc in the mixed culture is higher than that in pure culture and the sterile control.In these processes,two kinds of bacteria perform different functions and play a cooperative role during leaching of sphalerite.The bioleaching action carried out by Acidithiobacillus ferriooxidans(A.ferriooxidans)is not directly performed through Fe2+ but Fe3+,and its role is to oxidize Fe2+ to Fe 3+ and maintain a high redox potential.Moreover,the addition of an appropriate concentration of ferric iron to the leaching systems is beneficial to zinc dissolution.In the leaching systems without Acidithiobacillus thiooxidans(A.thiooxidans),elemental sulfur layers are formed on mineral surface during the dissolution of zinc and block continuous leaching.Acidithiobacillus thiooxidans,however,eliminate the passivation and cause the bioleaching process to continue in the leaching systems.At the same time,protons from the bacterial oxidization of the elemental sulfur layers also accelerate the leaching of zinc.

Kinetic study on pressure leaching of high iron sphalerite concentrate

The kinetics of pressure leaching high iron sphalerite concentrate was studied.The effects of agitation rate,temperature, oxygen partial pressure,initial acid concentration,particle size,iron content in the concentrate and concentration of Fe2 +added into the solution on the leaching rate of zinc were examined.The experiment results indicate that if the agitation rate is greater than 600 r/min,its influence on Zn leaching rate is not substantial.A suitable rise in temperature can facilitate the leaching reaction,and the temperature should be controlled at 140-150℃.The increase trend of Zn leaching rate becomes slow when pressure is greater than 1.2 MPa,so the pressure is controlled at 1.2-1.4 MPa.Under the conditions of this study,Zn leaching rate decreases with a rise in the initial sulfuric acid concentration;and Zn leaching rate increases with a rise of iron content in the concentrate and Fe 2+ concentration in the solution.Moreover,the experiment demonstrates that the leaching process follows the surface chemical reaction control kinetic law of“shrinking of unreacted core”.The activation energy for pressure leaching high iron sphalerite concentrate is calculated,and a mathematical model for this pressure leaching is obtained.The model is promising to guide the practical operation of pressure leaching high iron sphalerite concentrate.