Release characteristics and stabilization of heavy metals in antimony tailings in Yunnan Province,China

The pollution caused by the mining and smelting of heavy metals is becoming an increasingly severe environmental problem.In this study,the environmental risks of mine tailings were explored using typical antimony tailings(the depth of the sample taken from the ground to the deepest position of 120 cm)from the Zuoxiguo mine in Yunnan Province,Southwest China.The tailings were examined to explore the geological background,distribution characteristics,and release characteristics of heavy metals.Additionally,stabilizer treatments for heavy metals were investigated in consideration of waste treatment.The results showed that the contents of Sb and As(8.93×103 and 425 mg/kg,respectively)in the tailings were considerably higher than the local soil background values,suggesting that these metals pose a considerable threat to the surrounding environment.The geological background values of Cr,Cd,Pb,Cu,and Zn were relatively low.The results of static release showed that Sb,As,Cd,and Cr leached from the tailings more easily than Cu,Zn,and Pb under acidic conditions(pH=2.98).Geo-accumulation indices and potential ecological risk indices showed that Sb,As,Cd,and Pb were highly enriched in the tailings,whereas Cu,Cr,and Zn contents were relatively low.The single factor ecological risk index of the mining area showed that Sb and As are high ecological risk factors,whereas Cr,Cu,Zn,Cd,and Pb are not.The results of the orthogonal test results showed that by adding 15.0%(m/m)fly ash and 15.0%(m/m)zeolite powder to the quicklime and curing for 28 d,a significant stabilization effect was observed for Sb,As,and Pb.This study helps determine the priority control components for characteristic heavy metals in antimony tailings,and provides valuable insights regarding the formulation of appropriate mitigation strategies.

Trace element compositions of pyrite and stibnite:implications for the genesis of antimony mineralization in the Yangla Cu skarn deposit,Northwestern Yunnan,China

The Yangla Cu skarn deposit is located in the central part of the Jinshajiang Suture Zone,southwest China,with a total reserve of 150 Mt Cu@1.03%.The newly discovered antimony orebodies at the depth of Yangla are strictly controlled by the stratum,structure,and lithology,which are lenticular and vein-like within the marble fracture zone,which can provide a window into multistage miner-alization and ore genesis at Yangla.Mineralization can be divided into three types,Cu–Pb–Zn(skarn)pyrite,galena,and sphalerite,Cu(porphyry)chalcopyrite and pyrite,and Sb(hydrothermal)stibnite and pyrite.The mineral assem-blages were stibnite+pyrite+calcite+quartz±minor scheelite in antimony ores.This study presents quantitative measurements of the trace element compositions of pyrite and stibnite from the Yangla antimony ores.Analysis of pyrite with electron probe microanalysis(EPMA)showed enrichment in Co,Ni,Sb,As,and Mo,and deficit in its S and Fe contents when compared to the stoichiometric con-centrations of S and Fe in pyrite.The Sb-related pyrite may belong to sedimentary-reworked genesis and may be modi-fied by hydrothermalfluids,thereby presenting a certain dif-ference(i.e.,crystal morphology,texture,and chemical com-position)compared to the skarn and porphyry Cu-related pyrite in the Yangla Cu skarn deposit.Analysis of stibnite with EPMA and inductively coupled plasma-mass spectrom-etry showed enrichment in As,Pb,Sn,Pb,Cu,and Zn,and presented much higher Sb contents and slightly lower S con-tents when compared to the stoichiometric concentrations of Sb and S in stibnite.Statistical analysis of the stibnite trace elements showed correlations for the elemental pairs Cu–Pb,As–Sb,and Sn–Pb,and the coupled substitution equations Sb^(3+)↔Cu^(+)+Pb^(2+),Sb^(3+)↔As^(3+),and Sn^(2+)↔Pb^(2+)may be the major factors governed the incorporating Cu,Pb,As and Sn within the stibnite.Moreover,this study preliminary shows that the antimony mineralization may belong to a car-bonate replacement hydrothermal genesis at Yangla.

Unlocking the potential of ultra-thin two-dimensional antimony materials:Selective growth and carbon coating for efficient potassium-ion storage

Antimony-based anodes have attracted wide attention in potassium-ion batteries due to their high theoretical specific capacities(∼660 mA h g^(-1))and suitable voltage platforms.However,severe capacity fading caused by huge volume change and limited ion transportation hinders their practical applications.Recently,strategies for controlling the morphologies of Sb-based materials to improve the electrochemical performances have been proposed.Among these,the two-dimensional Sb(2D-Sb)materials present excellent properties due to shorted ion immigration paths and enhanced ion diffusion.Nevertheless,the synthetic methods are usually tedious,and even the mechanism of these strategies remains elusive,especially how to obtain large-scale 2D-Sb materials.Herein,a novel strategy to synthesize 2D-Sb material using a straightforward solvothermal method without the requirement of a complex nanostructure design is provided.This method leverages the selective adsorption of aldehyde groups in furfural to induce crystal growth,while concurrently reducing and coating a nitrogen-doped carbon layer.Compared to the reported methods,it is simpler,more efficient,and conducive to the production of composite nanosheets with uniform thickness(3–4 nm).The 2D-Sb@NC nanosheet anode delivers an extremely high capacity of 504.5 mA h g^(-1) at current densities of 100 mA g^(-1) and remains stable for more than 200 cycles.Through characterizations and molecular dynamic simulations,how potassium storage kinetics between 2D Sb-based materials and bulk Sb-based materials are explored,and detailed explanations are provided.These findings offer novel insights into the development of durable 2D alloy-based anodes for next-generation potassium-ion batteries.

Soil Profile Concentration Distributions of Antimony and Bismuth across Southeastern Missouri (USA)

Recent research has suggested that increased industrial and technological utilization of antimony and bismuth necessitates greater research to determine the soil and water chemistry and the environmental risks associated with these elements. The near-total soil profile concentrations of antimony and bismuth were determined for key soil series across southeastern Missouri. The antimony concentrations ranged from 0.65 to 0.08 mg kg−1, whereas the bismuth soil profile concentrations ranged from 0.92 to 0.03 mg kg−1. Most pedons showed antimony concentrations ranging from 20 to 30 mg kg−1, whereas bismuth concentrations were commonly 10 to 20 mg kg−1. For soils having argillic horizons, antimony and bismuth concentrations were greater for the illuvial horizons than the eluvial horizons, whereas Entisols, Inceptisols, and one Vertisol showed rather uniform antimony and bismuth concentrations, features paralleling the soil texture distribution. Both antimony and bismuth showed significant correlations with iron.

Growth and Antimony Bioconcentration Characteristics of Wild Ramie(Boehmeria nivea)under Sb Stress in Different Valence States

[Objectives] To explore the effects of antimony(Sb) in different valence states on the growth and Sb bioconcentration and transfer of wild ramie(Boehmeria nivea). [Methods] A pot experiment was conducted to study the effects of Sb(Ⅲ) and Sb(Ⅴ) stress on plant height, biomass, leaf SPAD value, Sb contents in various organs, Sb bioconcentration and transfer factors, and other indexes. [Results] Both kinds of Sb treatments showed a trend of "first increasing and then decreasing" in plant height as Sb concentration increased. The plant heights in Sb(Ⅲ) treatments with a concentration lower than 1 000 mg/kg and Sb(Ⅴ) treatments with concentrations lower than 4 000 mg/kg were significantly higher than that of the control check(CK);and the Sb(Ⅲ) treatment of the high concentration(4 000 mg/kg) resulted in a significant decrease in plant height, while the 8 000 mg/kg Sb(Ⅴ) treatment still showed an increase in plant height, indicating that the toxicity of Sb(Ⅴ) to wild ramie was significantly lower than that of Sb(Ⅲ). The Sb(Ⅲ) treatments with a concentration lower than 2 000 mg/kg had little effect on the dry weight of the aboveground part, while the treatment with a higher concentration showed a significant decrease;and the dry weights in various concentrations of Sb(Ⅴ) treatments showed no significant differences, but they were significantly higher than the CK and corresponding concentration of Sb(Ⅲ) treatment. Both types of Sb stress could promote the increase of SPAD value in wild ramie leaves, and the performance was significantly higher than the CK. As the concentration of Sb treatment increased, the Sb content in both the aboveground and underground parts showed a significant increase;and the comparison of Sb content under corresponding concentrations of the two types of Sb treatments showed that in the aboveground part, Sb(Ⅲ) was higher than Sb(Ⅴ), while in the underground part, the opposite was true. The bioconcentration factor(BF) of Sb decreased with the increase of Sb treatment concentration overall, and the value of Sb(Ⅴ) was smaller than that of Sb(Ⅲ), but both kinds of Sb stress were significantly smaller than the CK. The transfer factor(TF) of Sb in wild ramie showed a trend of "increasing first and then decreasing" with the concentration of Sb treatment, and various treatments of Sb(Ⅲ) were higher than the CK, with significant differences, while among various treatments of Sb(Ⅴ), except treatment B3, the reduction of which was not significant, other Sb(Ⅴ) treatments showed significant decreases. Comparing the two types of Sb treatments, the BF and TF values of Sb in wild ramie under Sb(Ⅲ) treatments were higher than those under Sb(Ⅴ) treatments, and the TF reached a significant level, indicating that the Sb transport ability of wild ramie under Sb(Ⅲ) treatments was stronger. [Conclusions] This study provides a theoretical basis for the mining of wild ramie Sb restoration genes and the application of large-scale cultivation in ecological restoration.

Unraveling the influence of interface defects on antimony trisulfide solar cells

Antimony trisulfide(Sb_(2)S_(3)) solar cells suffer from large open circuit voltage deficits due to their intrinsic defects which limit the power conversion efficiency.Thus,it is important to elucidate these defects’ origin and defects at the interface.Here,we discover that sulfide radical defects have a significant impact on the performance of Sb_(2)S_(3)solar cells.Moreover,it has been illustrated that these defects at the CdS/Sb_(2)S_(3)interface can be reduced by optimizing the deposition process.A trap distribution model is used to quantify the defect density at the CdS/Sb_(2)S_(3)interface.It shows that the interface defects can be reduced by24% by improving the deposition process.This work reveals the importance of interface defects and guides the future optimization of Sb_(2)S_(3)solar cells.

Effect of thickness of antimony selenide film on its photoelectric properties and microstructure

Antimony selenide(Sb2Se3) films are widely used in phase change memory and solar cells due to their stable switching effect and excellent photovoltaic properties. These properties of the films are affected by the film thickness. A method combining the advantages of Levenberg–Marquardt method and spectral fitting method(LM–SFM) is presented to study the dependence of refractive index(RI), absorption coefficient, optical band gap, Wemple–Di Domenico parameters, dielectric constant and optical electronegativity of the Sb2Se3films on their thickness. The results show that the RI and absorption coefficient of the Sb2Se3films increase with the increase of film thickness, while the optical band gap decreases with the increase of film thickness. Finally, the reasons why the optical and electrical properties of the film change with its thickness are explained by x-ray diffractometer(XRD), energy dispersive x-ray spectrometer(EDS), Mott–Davis state density model and Raman microstructure analysis.

Effects of Antimony Stress on Root Growth,Antimony Accumulation and Physiological Characteristics of Ramie(Boehmeria nivea(L.) Gaudich.)

[Objectives]This study was conducted to investigate the toxicity of heavy metal antimony(Sb) to ramie(Boehmeria nivea(L.) Gaudich.) and the tolerance response in ramie. [Methods] A pot experiment was conducted to study the effects of Sb stress on root growth and Sb accumulation and transport of the root system of cultivated ramie Zhongzhu No.1, as well as on the physiological characteristics of ramie leaves. [Results] The plant height and root dry weight and volume of Zhongzhu No.1 showed an effect of "promoting at low concentrations and inhibiting at high concentrations" with the increase of Sb concentration, and decreased significantly at the concentration of 4 000 mg/kg, but no obvious toxic growth symptoms were observed. The content of Sb in roots(289.7-508.6 mg/kg) and the root-shoot transfer factor(0.09-0.57) of Zhongzhu No.1 increased with the increase of soil Sb concentration, but the change of Sb bioconcentration factor in roots was opposite, indicating that high concentrations of Sb in soil could promote the absorption of Sb in roots and the transport of Sb to the aboveground part, but the Sb enrichment capacity of roots was relatively reduced with the increase of soil Sb. Sb stress had a certain impact on the physiological characteristics of ramie leaves. With the increase of Sb treatment concentration, MDA, POD and SOD showed a change trend of "first increasing and then decreasing", while CAT gradually increased, indicating that Sb stress caused changes in the physiological characteristics of ramie leaves, thereby affecting plant growth and development. [Conclusions] This study provides a theoretical basis for ecological restoration of ramie in mining areas.

Recovery of antimony from antimony-bearing dusts through reduction roasting process under CO–CO_2 mixture gas atmosphere after firstly oxidation roasted

This paper mainly investigated the antimony recovery from antimony-bearing dusts through reduction roasting process after the dust firstly oxidation roasted.CO–CO2 mixture gas was used as reducing agent,and the antimony-containing phase was reduced into Sb4O6,volatilized into smoke,and finally recovered through the cooling cylinder.The antimony recovery rate increased from 66.00 wt%to 73.81 wt%in temperature range of 650 to 800°C,and decreased with temperature increased further to 900°C due to the reduction of Sb4O6 to the nonvolatile Sb.Similarly,the CO partial pressure also played a double role in this test.Under optimized conditions of roasting temperature of 800°C,CO partial pressure of 7.5 vol%and roasting time of 120 min,98.40 wt%of arsenic removal rate and 80.40 wt%antimony recovery rate could be obtained.In addition,the“As2O3”product could be used for preparing ferric arsenate which realized the harmless treatment of it.

Effects of Antimony Stress on Photosynthetic Characteristics of Vegetable Leaves

[Objective] This study aimed to investigate the effects of different concen- trations of antimony and modifier calcium magnesium phosphate on photosynthetic characteristics of edible amaranth, flowering Chinese cabbage, spinach and flowering Chinese cabbage. [Method] By outdoor potting simulation experiment, soil matrixes containing 10.00, 20.00, 50.00, 70.00 and 100.00 mg/kg antimony （Sb3＋） were pre- pared; soil without antimony was used as control （CK）. Each pot was loaded with 0.10 kg/kg vegetable special fertilizer, mixed evenly, and divided into two shares： one share was supplemented with 1.75 g/kg modifier calcium magnesium phosphate and mixed evenly; the other share contained no calcium magnesium phosphate. Af- ter the generation of three true leaves, seedlings with uniform growth were trans- planted into the prepared soil matrixes, eights seedlings per pot. Vegetable seedlings were watered regularly to maintain 70% of field capacity. After 45 d, veg- etable plants were harvested and washed clean with distilled water for measurement of indicators of photosynthetic characteristics. [Result] With the increase of antimony concentration, relative chlorophyll content （SPAD value） and net photosynthetic rate of four vegetable species increased first and then declined, while stomatal conduc- tance of vegetable leaves was linearly reduced. [Conclusion] Appropriately adding modifier calcium magnesium phosphate can effectively improve the photosynthetic characteristics of four vegetable species and reduce the toxic effects of heavy metal antimony on vegetables.

Synthesis and Crystal Structure of t he Complex of Antimony Trichloride and Dioxane

New solid complex of the antimony trichloride and dioxane was obtained th rough a reaction of the dioxane and the absolute methanol solution of the antimony trichloride.The formula of the complex is[SbCl_(3)·{(CH_(2))_(4)O_(2)}_(1.5)].The crystal structure of the comple x belongs to cubic system,space group I-43d,a=17.1417(5)?,Z=16.The trivalent antimony ion not only bonds directly to three chlorine anions,but also is co ordinated by three oxygen atoms of th e dioxane molecules.Two oxygen atoms in a dioxane molecule wi ll coordinate to different antimony ions,respectively.

Separation of arsenic from arsenic-antimony-bearing dust through selective oxidation-sulfidation roasting with CuS

The feasibility of a new method for separating arsenic from arsenic-antimony-bearing dusts using Cu S was put forward,in which Sb was transformed into Sb2O4 and Sb2S3 that stayed in the roasted calcine while As was volatilized in the form of As4O6.The factors such as roasting temperature and Cu S addition amount were studied using XRD,EPMA and SEM-EDS.Cu S has an active effect on the separation of arsenic due to the destruction of(Sb,As)2 O3 structures in the original dust and the simultaneous release of As in the form of As4O6.At a roasting temperature of 400°C and Cu S addition amount of 130%,the volatilization rates of arsenic and antimony reach 97.80 wt.%and 8.29 wt.%,respectively.Further,the high As volatile matter can be used to prepare ferric arsenate after it is oxidized,with this treatment rendering the vapor harmlessness.

Mineralogical characterization and pretreatment for antimony extraction by ozone of antimony-bearing refractory gold concentrates

The mineralogical characterization of antimony-bearing refractory gold concentrates and the antimony extraction by ozonein HCl solution were investigated.The mineralogical study shows that there exist stibnite(Sb2S3),arsenopyrite(FeAsS),pyrite(FeS2)and quartz in the concentrates,and the gold is mainly(67.42%)encapsulated in sulfides.The antimony extraction by ozone inhydrochloric acid was employed and the influences of temperature,liquid/solid ratio,HCl concentration and stirring speed on theextraction of antimony were investigated.High antimony extraction(93.75%)is achieved under the optimized conditions.After thepretreatment by ozone,the antimony is recovered efficiently and the gold is enriched in the leaching residue.

POLYMORPH CONTROL OF ANTIMONY WHITE(Sb_2O_3)PREPARED BY HYDROMETALLURGY METHOD

The effects of reaction solvent, the properties of Sb 4O 5Cl 2 material and the ligand additives on the reaction rate and polymorph of antimony white(Sb 2O 3) in the reaction of Sb 4O 5Cl 2 transforming into Sb 2O 3 have been investigated by XRD and IR method. It is revealed that the reaction solvent and the properties of Sb 4O 5Cl 2 are the key factors affecting the reaction rate. The polymorph of antimony trioxides is determined by the reaction mechanism, i.e. the coordination state of the antimony activated complex. Adding a little ligand such as EDTA is the most economical and effective method of synthesizing cubic antimony white(Sb 2O 3)in hydrometallurgical transformation process.

Determination of trace amount of antimony (Ⅲ) by adsorption voltammetry on carbon paste electrode

A sensitive method is described for the determination of trace antimony based on the antimony-bromopyrogallol red (BPR) adsorption at a carbon paste electrode (CPE). Three steps were involved in the overall analysis: preconcentration,reduction and stripping. Optimal conditions were found to be an electrode containing 25% paraffin oil and 75% high purity graphite powder as working electrode;a 0.10 mol/L HCl solution containing 40 μmol/L BPR as accumulation medium;a 0.20 mol/L HCl solution as reduction and stripping electrolyte;accumulation time,150 s;reduction potential and time,-0.50 V,60 s;scan range from -0.50 to 0.20 V. Interferences by other ions were studied as well. The detection limit was found to be 0.5 nmol/L for 150 s preconcentration. The linear range was from 1.0 nmol/L to 0.50 μmol/L. Application of the proposed method to the determination of antimony in water and human hair samples gave good results.

Fine debismuthizing with calcium,magnesium and antimony

In order to achieve fine debismuthizing of lead bullion,the effects of temperature,adding amount of calcium and magnesium and antimony on the bismuth removal from lead bullion were investigated.The mechanism of debismuthizing was also discussed.The results show that when adding amounts of calcium and magnesium reach 0.112% and 0.395%,respectively,bismuth level of 0.001%（mass fraction） in the final lead is achieved at 330 ℃,without the need for antimony addition.Maintaining addition amount of magnesium at 0.155%,when calcium addition amount is less than 0.09%,the concentration of peritectic reaction point,the bismuth concentration can be easily decreased to 0.001% by the following antimony treatment.But the effect of antimony treatment on debismuthizing gets bad if the calcium addition exceeds 0.09%.

Bacillus sp. Treatment of Wastewater Containing Antimony

Antimony ore dressing wastewater was treated by using Bacillus sp. and the influences of treatment time, temperature, inoculation size, and pH value on Sb removal effect were explored. The results showed that the best removal efficiency of Sb in mineral processing wastewater could reach 99.75% in 4 d under the optimum conditions of 30 ℃, microbial inoculated quantity 5%, and pH value at 2.0. After the treatment, the concentration of Sb in wastewater was reduced from 122.21 to 0.30mg/L, which was lower than the local industrial wastewater discharge standard of0.50 mg/L.

Experiment Study of Optimization of Antimony Ore-processed Wastewater Treatment by Bacillus sp.

Antimony ore-rocessed wastewater was treated with the optimized bacterium Bacillus sp.The effects of the evaluation indices,including the amount of inoculation,pH value,processing time,and temperature,on the treatment of antimony ore-rocessed wastewater were studied through orthogonal experiments.The results show that the degrees of effects of the indices on the removal of antimony from wastewater by Bacillus sp.are in the following descending order：the amount of inoculation,pH value,processing time,and temperature.The optimal treatment conditions were attained when the amount of inoculation was 5％,the pH value was 2.5,the processing time was three days,and the temperature was 30 ℃.

Synthesis and application of antimony pent(isooctyl thioglycollate)

A new type of thermal stabilizer, antimony pent（isooctyl thioglycollate）(Sb(SCH2COOC8H17)5), was synthesized by using antimony trioxide, isooctanol and thioglycolic acid in 2 steps. Firstly, antimony trioxide was oxidized into colloidal antimony peroxide. Then antimony peroxide and isooctyl thioglycollate reacted stoichiometrically for 2 h with the yield of 87%. This compound was used as thermal stabilizer for polyvinyl chloride（PVC）. The results show that the thermal stability time is 52min at 200℃ by heat-ageing oven test when adding 2.5% thermal stabilizer to PVC resin. Compared with antimony tris（isooctyl thiolycollate）, the initial thermal stability of antimony pent（isooctyl thioglycollate） is better than that of antimony tris（isooctyl thioglycollate）, while the long-term thermal stability time is shorter than that of antimony tris（isooctyl thioglycollate）. Meanwhile, the synergism of antimony pent（isooctyl thioglycollate） with calcium stearate was studied, indicating that when the mass ratio of antimony pent（isooctyl thioglycollate） to calcium stearate is （2∶1,） the thermal stability time of PVC is 58min.

SYNTHESIS AND CHARACTERIZATION OF DI(2,4,6-TRIBROMOPHENOXY)TRIPHENYL-ANTIMONY

The synthetic method and characterization of di(2,4,6-tribromophenoxy)triphenyl antinony are reporledin this paper.This compound is prepared by reacting dihalotripheny-antimony with tribromophenol under defi-nite conditions and its yield is 70-80%.Relow 250℃,the product has good lhernal stability.It makes alavorable flame resisting effect on polyethylene.while the addition is ouly l0 Phr without using animeny1rioxide,the oxygen index of the polymer increases from 18.51o 26.5,and there are no adverse effects on themechanical properties of polyelhylene.