Infrared microthermometry of fluid inclusion in sphalerite:A case study of the Xinqiao deposit in the Middle-Lower Yangtze metallogenic belt

Infrared microthermometry allows direct measurement of fluid inclusions hosted in opaque ore minerals and can provide direct constraints on the evolution of ore-forming fluids.This study presents infrared microthermometry of spherite-hosted fluid inclusions from the Xinqiao deposit in the Middle-Lower Yangtze Metallogenic Belt and sheds new light on the ore genesis of the deposit.Considering that infrared light may lead to non-negligible temperature deviations during microthermometry,some tests were first conducted to ensure the accuracy of the microthermometric measurements.The measurement results indicated that using the lowest light intensity of the microscope and inserting an optical filter were effective in minimizing the possible temperature deviations of infrared microthermometry.All sphalerite-hosted fluid inclusions from the Xinqiao deposit were aqueous.They show homogenization temperature ranging from~200 to 350℃,but have two separate salinity groups(1.0 wt%-10 wt%and 15.1 wt%-19.2 wt%NaCl equivalent).The low-salinity group represents sedimentary exhalative(SEDEX)-associated fluids,whereas the high-salinity group results from modification by later magmatic hydrothermal fluids.Combined with published fluid inclusion data,the four-stage fluid evolution of the Xinqiao deposit was depicted.Furthermore,our data suggest that the Xinqiao deposit was formed by twostage metallogenic events including SEDEX and magmatic-hydrothermal mineralization.

Adsorption mechanism of 2-mercaptobenzothiazole on chalcopyrite and sphalerite surfaces:Ab initio and spectroscopy studies

Interaction mechanism of the collector,2-mercaptobenzothiazole（MBT）,with chalcopyrite and sphalerite surfaces were investigated by Fourier transform infrared（FTIR） and density functional theory,Results of FTIR showed that some characteristic peaks of MBT were observed on the chalcopyrite surface,including C=N,C=N-S and C-S stretching vibration peaks,and the adsorption product was CuMBT.But there were no characteristic peaks of MBT on the sphalerite surface.The thione molecular form of MBT was the most efficient and stable,N and exocyclic S were the more favourable reactive sites for nucleophilic attacked by metal atoms.Compared with ZnS（110）,MBT is more readily adsorbed on CuFeS2（112）.Attachment of MBT occurs due to strong bonding through exocyclic S p and s orbits with Cu d orbit on CuFeS2（112） and electron transfer from Cu atom to S atom.Under the vacuum condition,MBT in the form of thione molecular cannot be adsorbed on ZnS（110） spontaneously.

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.

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.

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.

Synergistic depression mechanism of zinc sulfate and sodium dimethyl dithiocarbamate on sphalerite in Pb−Zn flotation system

The depression mechanism of zinc sulfate(ZnSO4)and sodium dimethyl dithiocarbamate(DMDC)as the combined depressant on sphalerite was investigated by micro-flotation experiments,ion complexing tests,contact angle tests and X-ray photoelectron spectroscopy(XPS)analysis.The micro-flotation tests revealed that ZnSO4+DMDC had a better selective depression effect on sphalerite than using single ZnSO4 or DMDC.Ion complexing tests confirmed that DMDC had a strong complexing capacity with lead ions or hydroxy complexes.Contact angle tests illustrated that ZnSO4+DMDC makes the sphalerite surface more hydrophilic than ZnSO4 or DMDC.XPS analysis indicated that the combined depressant could prevent collector adsorbing on the Pb-activated sphalerite surface by a competitive adsorption method,while the combined depressant and collector were co-adsorbed on galena surface.

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.

Selective depression of copper-activated sphalerite by polyaspartic acid during chalcopyrite flotation

Environmentally friendly flotation reagent,polyaspartic acid(PAPA),was tested as a potential selective depressant in the flotation separation of chalcopyrite and Cu-activated sphalerite.The depression mechanism of PAPA was revealed by contact angle measurements,Zeta potential measurements,Fourier transform infrared spectroscopy(FT-IR)analysis and inductively coupled plasma(ICP)measurement.The micro-flotation tests with single minerals showed that PAPA selectively depressed Cu-activated sphalerite,while chalcopyrite remained floatable.Moreover,a concentrate containing 31.40%Cu with a recovery of 92.43%was obtained in flotation tests of artificially mixed minerals.Results of contact angle measurements,Zeta potential measurements and FT-IR spectrum revealed that PAPA exerted a much stronger adsorption on Cu-activated sphalerite surface than on chalcopyrite surface,preventing the further adsorption of sodium diethyl dithiocarbamate(DDTC)on its surface.ICP measurements indicated that PAPA had an excellent complexing ability with Cu^(2+)in flotation pulp,weakening the activation of Cu species on sphalerite surface and producing selective depression.

Determination of Fe and Zn contents and distributions in natural sphalerite/marmatite by various analysis methods

The contents of Fe and Zn in natural sphalerite samples were determined by chemical titration and spectroscopic techniques(portable X-ray fluorescence(P-XRF) spectrometry, electron probe microanalysis with energy dispersive spectroscopy(EPMA-EDS), electron probe microanalysis with wavelength dispersive spectroscopy(EPMA-WDS), and time-of-flight secondary ion mass spectrometry(To F-SIMS)). Besides, the distribution of Fe and Zn in sphalerite samples was analyzed by imaging EPMA-WDS and imaging To F-SIMS. The results show that Fe and Zn contents determined by each spectroscopic technique have good linearity with those determined by chemical titration(R^2>0.77), and the R^2 values of Fe are generally greater than those of Zn. The imaging analysis results revealed that Fe and Zn are not uniformly distributed in the sphalerite.

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.

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.

KINETICS OF LEACHING SPHALERITE WITH PYROLUSITE SIMULTANEOUSLY BY MICROWAVE IRRADIATION

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Bioleaching of sphalerite sample from Kooshk lead-zinc tailing dam

The zinc extraction from Kooshk lead-zinc tailing dam’s sample was investigated by bioleaching method. The Kooshk lead-zinc deposit/mine is located in Yazd province, Iran, and its tailing dam contains about 3.64%zinc, 0.97%lead and 24.18%iron. Experiments were designed and carried out by a mixed culture of mesophile bacteria as well as a mixed culture of moderate thermophile strain in the shake flasks. The results indicated that, more than 90% of sphalerite was dissolved during 14 d, while without bacteria, 44% of Zn was merely extracted. In addition, some experiments were performed in the absence of the bacterial medium （9K）. The results of these experiments indicated significant difference in Zn extraction with and without 9K until the 10th day of bioleaching, but after that the Zn extraction was improved and the same extraction was achieved at the end of bioleaching tests. This improvement can be attributed to the increase of the number of bacteria or Fe3＋concentration at the last days of leaching. Zn extraction kinetics of moderate thermophile bacteria was significantly higher than that of the mesophile, therefore sphalerite was successfully dissolved in preference to the pyrite using moderate thermophile bacteria in a lower redox potential.

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.

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.

Oxygen pressure acid leaching of artificial sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation

The mechanism of oxygen pressure acid leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation was investigated in this study.Artificial sphalerite was fabricated with varying amounts of iron content via the sintering of ZnS and FeS and used for the pressure acid leaching experiment.The variations in the potential of the pressure leaching system were investigated by using a self-designed potential autoclave.The results showed that compared to the non-iron sphalerite,there was a violent redox reaction between the 25.70%Fe-artificial sphalerite and dissolved oxygen during the process of pressure leaching;and the catalytic mechanism was attributed to the redox couple Fe^3+/Fe^2+,where Fe3+oxidizes the H2S gas film and the reduced Fe2+state is subsequently oxidized by the dissolved oxygen.Furthermore,the effect of temperature,H2SO4 concentration,and oxygen partial pressure on the artificial sphalerite with different iron contents was studied.The sphalerite samples with iron content were observed to dissolve more easily in sulfuric acid compared to the non-iron samples.Moreover,the activation energy of artificial sphalerite was observed to be lower in the sample with 25.70%iron content(22.26 kJ/mol)compared to that with no iron(32.31 kJ/mol);and the apparent reaction orders were obtained with respect to H2SO4 concentration(1.10 and 1.36)and oxygen partial pressure(1.29 and 1.41),respectively.A comprehensive kinetic model was developed on the basis of the experimental data and the fitted leaching ratio plot;and the kinetic equations for the leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation were determined.

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.

Sulfur speciation transformation during bioleaching of pyrite-containing sphalerite concentrate by thermophile Sulfolobus metallicus at 65 °C

Sulfur speciation transformation during bioleaching of pyrite-containing sphalerite concentrate by thermophile Sulfolobus metallicus （S. metallicus） at 65 ℃ was investigated by X-ray diffraction （XRD）, diffuse reflectance Fourier transform infrared spectroscopy （FT-IR） and sulfur K-edge X-ray absorption near edge structure spectroscopy （XANES）. The results show that the presence of S. metallicus effectively enhances the dissolution of the mineral. The yield of zinc increases from 0.5 g/L in sterile control to 2.7 g/L in bioleaching. The pyrite in the concentrate facilitates zinc dissolution in the early stage, but has hindrance role in the late stage for the formation of jarosite. Sulfur speciation analyses show that jarosite and elemental sulfur are main products in bioleaching process, and the accumulation ofjarosite is mainly responsible for the decline of leaching efficiency.

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.