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.

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.

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.

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.

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）.

Cu^2+-catalyzed mechanism in oxygen-pressure acid leaching of artificial sphalerite

The potential autoclave was used to study the catalytic mechanism of Cu^2+during the oxygen pressure leaching process of artificial sphalerite.By studying the potential change of the system at different temperatures and the SEM–EDS difference of the leaching residues,it was found that in the temperature range of 363–423 K,the internal Cu^2+formed a Cu S deposit on the surface of sphalerite,which hindered the leaching reaction,resulting in a zinc leaching rate of only 51.04%.When the temperature exceeds 463 K,the system potential increases steadily.The increase in temperature leads to the dissolution of the CuS,which is beneficial to the circulation catalysis of Cu^2+.At this time,the leaching rate of Zn exceeds 95%.In addition,the leaching kinetics equations at 363–423 and 423–483 K were established.The activation energy of zinc leaching at 363–423 and 423–483 K is 38.66 and 36.25 kJ/mol,respectively,and the leaching process is controlled by surface chemical reactions.

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.

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.

An Experimental Calibration on the Sphalerite-Galena Sulfur Isotope Geothermometer

A new experimental calibration was undertaken in this study to get a more reliable sphalerite-galena sulfur isotope geothermometer. The experimental conditions selected in study were very similar to those of natural hydrothermal solution. The high-precision SF6 method was used in sulfur isotope analyses. The obtained calibration curve for sulfur isotope fractionation between sphalerite and galena can be expressed with the equation 10001nαSp-Gn= 0.74×106T-2+0.08.

Investigation of a New Exsolved Cu-Fe-S Phase in“Abnormal Sphalerite”

A new exsolved copper-iron-sulfur phase in sphalerite has been found in the Dajing cassiterite- sulfidecopper-silver-tin deposit, Inner Mongolia, China. After investigating the optical properties, chemical composi-tion, crystal structure and exsolved Characters of the exsolved phase, the authors present important evidencefor its being a new exsolved copper-iron-sulfur phase mineral. Its formation mechenism is discussed in consider-ing heating experiments, phase equilibrium data and the geology of the deposit.

First-principle study on the surface atomic relaxation properties of sphalerite

The surface properties of sphalerite （ZnS） were theoretically investigated using first principle calculations based on the density functional theory （DFT）. DFT results indicate that both the （110） and the （220） surfaces of sphalerite undergo surface atom relaxation after geometry optimization, which results in a considerable distortion of the surface region. In the normal direction, i.e., perpendicular to the sur- face, S atoms in the first surface layer move outward from the bulk （dl）, whereas Zn atoms move toward the bulk （d2）, forming an S-enriched surface. The values of these displacements are 0.003 nm for dl and 0.021 nm for d2 on the （110） surface, and 0.002 nm for dl and 0.011 nm for d2 on the （220） surface. Such a relaxation process is visually interpreted through the qualitative analysis of molecular mechanics. X-ray photoelectron spectroscopic （XPS） analysis provides the evidence for the S-enriched surface. A polysulphide （S n^2- ） surface layer with a bind- ing energy of 163.21 eV is formed on the surface of sphalerite after its grinding under ambient atmosphere. This S-enriched surface and the S 2- surface layer have important influence on the flotation properties ofsphalerite. Keywords：

Fractal Modeling of Sphalerite Banding in Jinding Pb-Zn Deposit, Yunnan, Southwestern China

Sphalerite banding is a common texture in Jinding （金顶） Pb-Zn deposit, Yunnan （云南）, southwestern China. The frequency distribution and irregularity of sphalerite grains observed in the bandings are characterized quantitatively by fractal models. Fractal dimensions calculated by several fractal models including box-counting model, perimeter-area （P-A） model, and number-area （N-A） model show the gradual change from outer banding to inner banding, indicating a decrease in area percentage, in irregularity, in shape and in grain size, and an increase in the numbers of grains. These results may imply an inward growth of sphalerite during mineralization, and self-organization properties are involved in the nonlinear process of mineralization.

Influence of mechanical excitation on adsorption of sodium diethylamino dithio-formate on galena and sphalerite

The adsorption of SDD on galena, pyrite and sphalerite in the process of agitating and in the process of grinding using different mediums is studied by ultraviolet spectrophotometer. It has been found that the grinding process can cause more adsorption of SDD on these sulfides than the agitating process do and the environments of grinding with metal mediums do the best. The reason for these phenomena is because of the action of the mechanical activation and mechanical excitation. The ulteriorly principles of these theories are discussed in this paper.

Electrogenerative leaching for sphalerite-MnO_2 in the presence of Acidithiobacillus thiooxidans

A dual cell system was used to study the electrogenerative leaching sphalerite-MnO2 in the presence and absence of Acidithiobacillus thiooxidans (A. thiooxidans). The polarization of anode and cathode, and the relationship between the electric quantity (Q) and some factors, such as the dissolved rate of Zn2+ and Fe2+, and the time in the bio-electro-generating simultaneous leaching (BEGL) and electro-generating simultaneous leaching (EGL) were studied. A three-electrode system was applied to studying anodic and cathodic self-corrosion current, which was inappreciable compared with the galvanic current between sphalerite and MnO2. The results show that the dissolved Zn2+ in the presence of A. thiooxidans is nearly 43% higher than that in the absence of A. thiooxidans; the electrogenerative quantity in the former is about 150% more than that in the latter. The accumulated sulfur on the surface of sulfides produced in the electrogenerative leaching process can be oxidized in the presence of A. thiooxidans, and the ratio of biologic electric quantity reaches 27.9% in 72 h.

POTENTIAL-CONTROLLED FLOTATION OF SPHALERITE

The collector and collectorless notation of sphalerite by potential control,called potential-controlled flotation(PCF),have been investigated in this paper.The results have shown that the oxidative environment of flotation pulp or higher pulp potential could improve and activate the PCF of sphalerite,which was depressed under reducing conditions or lower pulp potential.The mechanisms of PCF have been simply discussed.

Spectroscopic Features and Formation Conditions of Sphalerite in the Lead-Zinc Deposit, Guangdong,China

Electron paramagnetic resonance spectra, absorption spectra, cathodoluminescence spectra and infrared spectra of sphalerite from the Lechang remoulded sedimentary lead-zinc deposit have been studied so as to provide microscopic evidence for the formation conditions and mineralization stages of the deposit as well as the geochemical processes of mineralization. On the basis of thermodynamic calculations, the stable fields of sphalerite from different mineralization stages were determined and are shown in logfs_2-logfo_2 diagrams; furthermore. the physico-chemical conditions of mineralization and the properties of mineralization solutions are discussed so that reliability of the genetic information provided by the spectroscopy of sphalerite may also be verified. It is suggested that the temperature and pH value of the mineralization system decrease, and so do the fugacities of O_2, S_2, H_2. and H_2S and the activities of HS^- and SO_4^(2-) from the early to late stages of minerahzation.