pH-dependent release characteristics of antimony and arsenic from typical antimony-bearing ores

The pH-dependent leaching of antimony (Sb) and arsenic (As) from three typical Sb-bearing ores (Banxi, Muli and Tongkeng Antimony Mine) in China was assessed using a pH-static leaching experiment. The pH changes of the leached solutions and pH-dependent leaching of Sb and As occurred in different ways. For the Banxi and Muli Sb ores, alkaline conditions were more favorable for the release of Sb compared to neutral and acidic conditions, but the reverse was true for the pH-dependent release of As. For the Tongkeng Sb ore, unlike the previous two Sb-bearing ores, acidic conditions were more favorable for Sb release than neutral and alkaline conditions. The ores with lower Sb and As contents released higher percentages of their Sb and As after 16 day leaching, suggesting that they are the largest potential sources of pollution. This work may provide key information on the geochemistry of Sb and As in the weathering zone.     

A review of removal technology for antimony in aqueous solution

Antimony (Sb) and its compounds, toxic metalloid, have been classified as high-priority pollutants. Increasing Sb released into the water environment by natural processes and anthropogenic activities, which exposure threatens to human health and ecosystems. Therefore, it is of unquestionable importance to remove Sb from polluted water. Keeping in view the extreme importance of this issue, we summarize the source, chemistry, speciation, distribution, toxicity, and polluted situation of Sb about aqueous solution. Then, we provide the recent and common technology to remove Sb, which are based on adsorption, coagulation/flocculation, electrochemical technology, membrane technology, ion exchange, etc. In this review, we focus in detail on the adsorption method, researchers at present have been investigating to discover more advanced, cost-effective, eco-friendly, reusable adsorbents. However, to date the Sb-containing wastewater treatment technologies are not sufficiently developed and most of research have been tested only in controlled lab conditions. Few reports are available that include field studies and applications. We critically analyzed the salient features and removal mechanisms, evaluating benefits and limitations of these technologies, hoping to provide more references for further research. Finally, we considered the Fe- or Mn-based technologies was the most promising technique to remove Sb for field application.     

Bacillus sp.处理含锑废水试验研究

利用某芽孢杆菌属微生物(Bacillus sp).对锑矿选矿废水进行了处理。研究微生物的接种量、作用时间、温度、体系pH值等对废水中Sb的去除效果的影响。结果表明:作用时间4 d、微生物接种量为5%、处理体系pH为2、最佳处理体系温度为30℃时,效果最佳,对废水中Sb的去除率达到99.75%,处理后废水中Sb的浓度由122.21 mg/L降低至0.30 mg/L,出水Sb浓度低于湖南省地方标准排放限值0.50 mg/L。     

High capacity adsorption of antimony in biomass-based composite and its consequential utilization as battery anode

Antimony is more than an emerging pollutant in water but a scare resource. In this study, we report an adsorbent with the record capacity so far from the balanced view of Sb(III) and Sb(V). The composite adsorbent was fabricated by encapsulating hollow Fe₃O₄ nanosphere with the EDTA grafted chitosan, and it has superhigh adsorption capacity of for 657.1 mg/g for Sb(III) and 467.3 mg/g for Sb(V), respectively. The mechanism study reveals that the adsorption of Sb initializes from the Fe₃O₄, propagates along the chitosan with hydrogen bond, and terminates at the inner sphere complex with the EDTA moiety in the adsorbent. In view of the ultra-high adsorption capacity of the adsorbent, the recovered adsorbent that contains abundant (>36.4%) highly dispersed antimony nanoparticles (600-FCSE-Sb) is applied to Li-ion battery anode after reduction. This article provides a new idea for connecting water treatment and electric energy storage.     

独山锑冶炼厂周边土壤锑砷空间分布特征、污染评价及健康风险评估

以贵州省独山县某锑矿冶炼厂周边土壤为研究对象,按照辐射布点取样的原则,布设45个采样点,共采集0~30 cm的土壤样品135件.基于GIS空间分析、内梅罗指数及人群健康风险评价等研究方法,分析了地形和风向对锑（Sb）在土壤中分布的影响,并对Sb和As在该区域土壤中的含量、空间分布、污染水平及人体健康风险进行了探究与评估.结果表明,Sb在新、老两厂周边不同深度（0~10、10~20、20~30 cm）土壤中的含量平均值分别是贵州省背景值的11.90、9.24、4.32和8.13、8.06、4.88倍,且随深度增加呈明显降低的垂直分布特征,其在20~30 cm深度土壤中的含量接近贵州省土壤背景值.而As在不同深度土壤中的含量变化不明显,总体平均值在贵州省土壤背景值的1.39~1.62倍之间.老冶炼厂周边土壤中Sb有效态含量占比均高于新厂区,且随土壤深度的增加而增加,而As在各层位土壤中均以残渣态为主,其含量占比高达80%以上.Sb在新、老冶炼厂周边土壤中的分布受到地形和主导风向影响,在烟囱周边300 m范围内土壤中Sb含量最高,随距离增加呈现缓慢降低特征;同时,土壤中Sb含量随海拔的增加而降低.从土壤污染的空间分布上看,老冶炼厂东北面土壤尚属清洁,其余区域达到轻微污染水平.人体健康风险评价结果显示,冶炼厂周边土壤中As的致癌风险不明显,As和Sb对成人与儿童的非致癌健康风险均较小.     

不同来源腐殖酸对三价锑的光氧化作用及影响因素

三价锑是有毒金属锑生物地球化学循环中的不稳定还原态,其在腐殖酸体系中的光氧化过程可能是水体环境中Sb（Ⅲ）转化的重要途径.通过室内模拟实验,探讨了光照条件下不同来源腐殖酸对Sb（Ⅲ）的光氧化反应特征,并考察腐殖酸浓度、Sb（Ⅲ）初始浓度、溶液pH值、环境中普遍存在的阴阳离子等环境因素对光氧化作用的影响.结果表明：Sb（Ⅲ）在腐殖酸溶液中的光化学反应过程符合准一级动力学规律.反应体系中腐殖酸浓度的升高有利于促进Sb（Ⅲ）的光氧化作用,而Sb（Ⅲ）初始浓度增加则抑制其光氧化作用,Sb（Ⅲ）的光氧化速率常数随溶液pH值的升高而逐渐增大,褐煤来源腐殖酸对Sb（Ⅲ）的光氧化速率常数高于土壤来源腐殖酸.水环境中NO₃^-的存在促进了腐殖酸对Sb（Ⅲ）的光氧化作用,而Cl^-、SO₄^2-和Na⁺未对Sb（Ⅲ）的光氧化作用产生显著影响.羟基和超氧自由基是Sb（Ⅲ）光氧化反应中的主要活性基团,其中在酸性条件下,羟基自由基对Sb（Ⅲ）的光氧化反应起主导作用,而在中性和碱性条件下超氧自由基起主要作用.     

Simultaneous removal of arsenic and antimony from mining wastewater using granular TiO2: Batch and field column studies

Coexisting arsenic (As) and antimony (Sb) in mining wastewater is a common and great concern. On-site simultaneous removal of As and Sb from mining wastewater was achieved by using a reusable granular TiO₂ column in this study. To evaluate the accuracy of the scale-up procedure, As and Sb adsorption from wastewater was studied in both large (600 g TiO₂) and small columns (12 g TiO₂) based on the proportional diffusivity rapid small-scale column tests (PD-RSSCTs) design. The comparable As and Sb breakthrough curves obtained from small and large columns confirmed the accuracy of the PD-RSSCT theory in the design of large-scale columns. Meanwhile, the consistent As and Sb adsorption results from batch and column experiments suggested that TiO₂ adsorption for As and Sb can be predicted from bench-scale tests. Charge distribution multi-site complexation (CD-MUSIC) and one-dimensional transport modeling integrated in the PHREEQC program were performed to study the adsorption behaviors of As and Sb on the TiO₂ surface. Coexisting ions, such as Ca^2 +, Mg^2 +, and Si^4 +, play an important role in As and Sb adsorption, and the breakthrough curves were well simulated after considering the compound ion effects. The results from this study highlight the surface reactions of As and Sb on TiO₂ and provide a practical way for on-site remediation of industrial wastewater.     

2005年中国燃煤大气锑排放清单

采用基于燃料消耗的排放因子法,按照经济部门(电力、工业、生活消费及其他)、燃料类型(原煤、洗煤、焦炭、型煤)、燃烧方式(层燃炉、煤粉炉、流化床锅炉等)和除尘脱硫设施(机械式除尘器、湿式除尘器、电除尘器、袋式除尘器等)等将燃煤排放源进行分类,根据各省、市、自治区不同排放源类型的煤炭消耗量及平均锑含量,建立了2005年中国燃煤大气锑排放清单.结果表明,2005年中国燃煤导致的大气锑排放总量约为530.86t,排放量超过30t的省份依次为贵州(49.28t)、湖南(45.96t)、河北(37.36t)、山东(35.12t)、安徽(30.92t),表明中国燃煤大气锑排放主要集中在中东部地区.大部分排放来自工业和电力部门,分别占排放总量的47.2%和39.9%.     

Molecular diversity of arbuscular mycorrhizal fungi at a large-scale antimony mining area in southern China

Arbuscular mycorrhizal fungi(AMF) have great potential for assisting heavy metal hyperaccumulators in the remediation of contaminated soils. However, little information is available about the community composition of AMF under natural conditions in soils contaminated by antimony(Sb). The objective of this study was to investigate the characteristics of AMF molecular diversity, and to explore the effects of Sb content and soil properties on the AMF community structure in an Sb mining area. Four Sb mine spoils and one adjacent reference area were selected from around the Xikuangshan mine in southern China. The association of AMF molecular diversity and community composition with the rhizosphere soils of the dominant plant species was studied by Polymerase Chain Reaction-Denaturing Gradient Gel Electrophoresis(PCR-DGGE). Results from all five studied sites showed that the diversity of AMF decreased with increasing Sb concentration. Principal component analysis(PCA) indicated that the AMF community structure was markedly different among these groups. Further redundancy analysis(RDA) showed that Sb contamination was the dominating factor influencing the AMF community structure in the Sb mine area. However, the multivariate analysis showed that, apart from the soil Sb content, extractable nitrogen content and organic matter content also attributed to AMF sequence distribution type. Some AMF sequences were only found in the highly contaminated area and these might be ideal candidates for improving phytoremediation efficiency in Sb mining regions. Gene sequencing analysis revealed that most species were affiliated with Glomus, suggesting that Glomus was the dominant AMF genus in the studied Sb mining area.     

Molecular diversity of arbuscular mycorrhizal fungi at a large-scale antimony mining area in southern China

Arbuscular mycorrhizal fungi (AMF) have great potential for assisting heavy metal hyperaccumulators in the remediation of contaminated soils. However, little information is available about the community composition of AMF under natural conditions in soils contaminated by antimony (Sb). The objective of this study was to investigate the characteristics of AMF molecular diversity, and to explore the effects of Sb content and soil properties on the AMF community structure in an Sb mining area. Four Sb mine spoils and one adjacent reference area were selected from around the Xikuangshan mine in southern China. The association of AMF molecular diversity and community composition with the rhizosphere soils of the dominant plant species was studied by Polymerase Chain Reaction-Denaturing Gradient Gel Electrophoresis (PCR-DGGE). Results from all five studied sites showed that the diversity of AMF decreased with increasing Sb concentration. Principal component analysis (PCA) indicated that the AMF community structure was markedly different among these groups. Further redundancy analysis (RDA) showed that Sb contamination was the dominating factor influencing the AMF community structure in the Sb mine area. However, the multivariate analysis showed that, apart from the soil Sb content, extractable nitrogen content and organic matter content also attributed to AMF sequence distribution type. Some AMF sequences were only found in the highly contaminated area and these might be ideal candidates for improving phytoremediation efficiency in Sb mining regions. Gene sequencing analysis revealed that most species were affiliated with Glomus, suggesting that Glomus was the dominant AMF genus in the studied Sb mining area.     

Molecular diversity of arbuscular mycorrhizal fungi at a large-scale antimony mining area in southern China

Arbuscular mycorrhizal fungi (AMF) have great potential for assisting heavy metal hyperaccumulators in the remediation of contaminated soils. However, little information is available about the community composition of AMF under natural conditions in soils contaminated by antimony (Sb). The objective of this study was to investigate the characteristics of AMF molecular diversity, and to explore the effects of Sb content and soil properties on the AMF community structure in an Sb mining area. Four Sb mine spoils and one adjacent reference area were selected from around the Xikuangshan mine in southern China. The association of AMF molecular diversity and community composition with the rhizosphere soils of the dominant plant species was studied by Polymerase Chain Reaction-Denaturing Gradient Gel Electrophoresis (PCR-DGGE). Results from all five studied sites showed that the diversity of AMF decreased with increasing Sb concentration. Principal component analysis (PCA) indicated that the AMF community structure was markedly different among these groups. Further redundancy analysis (RDA) showed that Sb contaminationwas the dominating factor influencing the AMF community structure in the Sb mine area. However, the multivariate analysis showed that, apart from the soil Sb content, extractable nitrogen content and organic matter content also attributed to AMF sequence distribution type. Some AMF sequences were only found in the highly contaminated area and these might be ideal candidates for improving phytoremediation efficiency in Sb mining regions. Gene sequencing analysis revealed that most species were affiliated with Glomus, suggesting that Glomus was the dominant AMF genus in the studied Sb mining area.     

广西大厂矿区土壤-植物系统中Sb、As的迁移转化特征

以广西大厂多金属矿区为例,选择了3个典型矿渣堆,对其中的土壤和植物进行样品采集,分析了土壤与植物样品中Sb、As含量的分布特征,并对土壤样品进行水溶态浸提实验.结果表明,矿山活动作为环境中Sb、As的一个重要来源,已经对矿区及其周边环境形成威胁.土壤pH值对Sb、As的活动性具有很大影响,pH值越高,土壤中Sb、As的活动性越高.相比之下,Sb比As的活动性更强.Sb、As在矿区土壤-植物体系的分布特征表明,蜈蚣草对Sb、As均具有一定的吸收能力,其吸收能力均表现为:根叶茎,但Sb从植物地下部向地上部转运的能力较As弱.     

微囊藻对锑(V)生物吸附作用研究

以富营养化湖泊水华暴发的主要藻种-微囊藻干物质作为生物吸附剂,考察不同生物量、初始pH值、吸附时间等因素对废水中锑（V）生物去除作用的影响,探讨微囊藻对Sb（V）的生物吸附性能;通过zeta电位和红外光谱技术揭示其吸附机理,并推断其反应方程式.结果表明：在室温条件下,吸附剂用量为0.5g：20mL,pH值为2.0,时间为1h时,Sb（V）的生物吸附达到最大容量为5.84mg/g（以干重计）,吸附等温线符合Langmuir等温方程（R²=0.993）,生物吸附动力学过程遵循假二级动力学模型（R²=0.994）.在pH值2.0~9.0范围内,其生物吸附效率随pH值增加逐渐下降.Zeta电位和ATR-IR光谱结果表明微囊藻细胞壁表面的氨基、羧基和羟基为Sb（V）的主要吸附位点,其中质子化的氨基通过静电吸引作用结合Sb（V）,羧基和羟基则通过表面络合作用与Sb（V）结合形成内源络合物.     

次生铁矿物及其与环境中锑的相互作用研究进展

我国锑矿资源丰富,锑矿资源开发利用过程导致锑进入表生环境并富集。锑作为人体非必需重金属,具有高化学毒性,是国际公认优先控制金属污染物。次生铁矿物在形成过程中和成矿后能以共沉淀、吸附等方式固定有害金属,但又易受环境因子变化的影响,重新释放被固定的有害金属,对有害金属的环境行为和归宿有着重要影响。本文面向我国锑污染现状,立足于常见次生铁矿物的基本结构和表面过程,以次生铁矿物相转变为切入点,论述了次生铁矿物与锑的相互作用机理,总结了环境pH、溶解性有机物、Fe(II)、微生物及环境温度等外界因素作用下次生铁矿物对锑环境行为的作用规律,以期从矿物学角度厘清环境因素-次生铁矿物-锑之间的微观作用机制,为表生环境锑污染的环境风险评价和修复治理提供理论指导。     

Antimony transformation and mobilization from stibnite by an antimonite oxidizing bacterium Bosea sp. AS-1

Soils and waters are heavily contaminated by antimony in Xikuangshan（XKS） mine area.It is widely accepted that oxidative dissolution of sulfide minerals and aqueous dissolution are the most prevalent geochemical mechanisms for the release of Sb to the environment.Bosea sp. AS-1 is an antimonite-oxidizer isolated from the mine slag in Xikuangshan Sb mine. Whole genome sequencing revealed the presence of multiple sulfur-oxidizing genes,antimony（Sb） metabolism genes and carbon fixation genes in AS-...     

Immobilization and transformation of co-existing arsenic and antimony in highly contaminated sediment by nano zero-valent iron

Arsenic(As) and antimony(Sb) are usually coexistent in mine wastes and pose a great threat to human health. The As immobilization by nano zero-valent iron(n ZVI) is promising, however, the stabilization for co-occurring As and Sb is not known. Herein, the immobilization and transformation of As and Sb in n ZVI-treated sediments were evaluated using complementary leaching experiments and characterization techniques. Raw sediment samples from a gold-antimony deposit revealed the co-existence of ul...     

基于文献计量的锑对农作物影响研究趋势

为了明确锑对农作物影响领域的研究现状和发展趋势,基于Web of Science数据库,检索了1991~2021年该领域的文献,利用文献计量学软件CiteSpace对年发文量、发文国家/地区、研究机构以及关键词共现网络、突显关键词、文献共被引网络和关键文献进行了可视化分析,并总结了未来研究发展趋势.结果显示：1991~2021年,本研究领域发文量整体呈快速增长模式,中国、美国、巴西、印度、意大利、西班牙等发文量较多,是推动该领域发展的主要国家.中国科学院和中国农业科学院是全球发文数量排名前10的中国研究机构,占总发文量的10.5%.基于关键词共现网络及突显词分析,锑对农作物的影响研究从主要考虑农作物生长、产量和品质的影响研究发展到考虑土壤、作物、水体、沉积物等环境中锑的迁移转化机制研究,土壤微生物群落活性的响应机理以及锑对人类健康的风险评价研究成为近年来的研究热点.     

Kinetics of antimony biogeochemical processes under pre-definite anaerobic and aerobic conditions in a paddy soil

While the transformation of antimony(Sb) in paddy soil has been previously investigated, the biogeochemical processes of highly chemical active Sb in the soil remain poorly understood. In addition, there is a lack of quantitative understanding of Sb transformation in soil. Therefore, in this study, the kinetics of exogenous Sb in paddy soils were investigated under anaerobic and aerobic incubation conditions. The dissolved Sb(V) and the Sb(V) extracted by diffusive gradient technique decreased u...     

3种耐锑土壤细菌的筛选及对锑的吸附研究

从湖南省冷水江锡矿山尾渣土壤中筛选分离出3株具有较高锑耐性的细菌,通过宏观吸附结合X射线光电子能谱（XPS）,阐明3株细菌对Sb（Ⅲ）和Sb（Ⅴ）的吸附机制.根据生理生化指标和16S rDNA序列同源性对比,鉴定出1株革兰氏阴性菌和2株革兰氏阳性菌,分别为人苍白杆菌（Ochrobactrum anthropi）、芽孢杆菌（Bacillus sp.）及蜡状芽孢杆菌（Bacillus cereus）.3株细菌都呈杆状,且都能在高锑含量营养液中良好生长.3株细菌对锑的等温吸附符合Langmuir模型,对锑的最大吸附量约为11.0~14.3 mg·g^-1,其中,蜡状芽孢杆菌对锑的吸附能力高于其它两株细菌,3株细菌对Sb（Ⅲ）的吸附量略高于Sb（Ⅴ）.XPS结果表明,细菌表面的羧基和氨基在锑吸附过程中发挥主导作用.本研究结果对于理解土壤微生物吸附固定锑机制及其在土壤修复中的应用有重要意义.     

Antimony smelting process generating solid wastes and dust：Characterization and leaching behaviors

A large amount of solid waste has been produced by the antimony smelting process in the＂World Capital of Antimony＂, Xikuangshan area in China. This study comprehensively investigated the physical and chemical characteristics of the various solid wastes, as well as the leaching behavior of the solid wastes, which included water-quenched slag,arsenic-alkali residue, desulfurized slag and blast furnace dust. These four types of waste were enriched in a variety of heavy metals and metalloids and more specifically with As and Sb levels up to 8.6 × 104 and 3.16 × 105mg/kg, respectively, in arsenic-alkali residue. For desulfurized slag and water-quenched slag, the leaching concentration of Sb significantly exceeded the acceptable limits during the leaching tests using the toxicity characteristic leaching procedure and the synthetic precipitation leaching procedure. In addition, As leaching in arsenic-alkali residue was extraordinarily hazardous, being three orders of magnitude higher than the regulatory level of As. According to the results of the extraction tests, all the tested wastes were classified as hazardous waste.