Depression mechanism of sulfite ions on sphalerite and Pb^(2+)activated sphalerite in the flotation separation of galena from sphalerite

The depression mechanism of sulfite ions on sphalerite and Pb^(2+)activated sphalerite in the flotation separation of galena from sphalerite still lacked in-depth insight.Therefore,the depression mechanism of sulfite ions on sphalerite and Pb^(2+)activated sphalerite in the flotation separation of galena from sphalerite was further systematically investigated with experiments and density functional theory(DFT)calculations.The X-ray photoelectric spectroscopy(XPS)results,DFT calculation results,and frontier molecular orbital analysis indicated that sulfite ions were difficult to be adsorbed on sphalerite surface,suggesting that sulfite ions achieved depression effects on sphalerite through other non-adsorption mechanisms.First,the oxygen content in the surface of sphalerite treated with sulfite ions in creased,which enhanced the hydrophilicity of the sphalerite and further increased the difference in hydrophilicity between sphalerite and galena.Then,sulfite ions were chelated with lead ions to form PbSO_(3)in solution.The hydrophilic PbSO_(3)was more easily adsorbed on sphalerite than galena.The interaction between sulfite ions and lead ions could effectively inhibit the activation of sphalerite.In addition the UV spectrum showed that after adding sulfite ions,the peak of perxanthate in the sphalerite treated xanthate solution was significantly stronger than that in the galena with xanthate solution,indicating that xanthate interacted more readily with sulfite ions and oxygen mo lecules within the sphalerite system,leading to the formation of perxanthate.However,sulfite ions hardly depressed the flotation of ga lena and could promote the flotation of galena to some extent.This study deepened the understanding of the depression mechanism o sulfite ions on sphalerite and Pb^(2+)activated sphalerite.

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.

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.

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.

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.

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.

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 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.

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.

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.

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.

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.

Influence of high concentration Zn^(2+) on floatability of sphalerite in acidic system

The influence of high concentration Zn^(2+) on the floatability of sphalerite in an acidic system was investigated via flotation experiments,zeta potential measurements,contact angle measurements,and X-ray photoelectron spectroscopy.The results indicated that Zn^(2+) was adsorbed on the sphalerite surface and a Zn-hydroxyl complex was formed at a pH of 4 and a Zn^(2+) concentration of 4×10^(-2) mol/L.The zeta potential increased and the contact angle decreased from 84.80°to 36.48°,strongly inhibiting the floatability of sphalerite.When S^(2−) or Cu^(2+) activator was used alone,sphalerite was not activated after Zn^(2+) was adsorbed,and its contact angle did not change significantly.However,by using a combination of S^(2−) and Cu^(2+) activators,its floatability was realized after Zn^(2+) adsorption.This result was attributed to the removal of the Zn-hydroxyl complex on the surface of sphalerite by S^(2-).After this removal,Cu^(2+) was adsorbed on the sphalerite surface to form a Cu_(2)S·S^(0) hydrophobic film.

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.