Induced transformation of antimony trioxide by Mn(II) oxidation and their co-transformed mechanism

Antimony (Sb) is a toxic and carcinogenic element that often enters soil in the form of antimony trioxide (Sb₂O₃) and coexists with manganese (Mn) in weakly alkaline conditions. Mn oxides such as birnessite have been found to promote the oxidative dissolution of Sb₂O₃, but few researches concerned the co-transformations of Sb₂O₃ and Mn(II) in environment. This study investigated the mutual effect of abiotic oxidation of Mn(II) and the coupled oxidative dissolution of Sb₂O₃. The influencing factors, such as Mn(II) concentrations, pH and oxygen were also discussed. Furthermore, their co-transformed mechanism was also explored based on the analysis of Mn(II) oxidation products with or without Sb₂O₃ using XRD, SEM and XPS. The results showed that the oxidative dissolution of Sb₂O₃ was enhanced under higher pH and higher Mn(II) loadings. With a lower Mn(II) concentration such as 0.01 mmol/L Mn(II) at pH 9.0, the improved dissolution of Sb₂O₃ was attributed to the generation of dissolved intermediate Mn(III) species with strong oxidation capacity. However, under higher Mn(II) concentrations, both amorphous Mn(III) oxides and intermediate Mn(III) species were responsible for promoting the oxidative dissolution of Sb₂O₃. Most released Sb (∼72%) was immobilized by Mn oxides and Sb(V) was dominant in the adsorbed and dissolved total Sb. Meanwhile, the presence of Sb₂O₃ not only inhibited the removal of Mn(II) by reducing Mn(III) to Mn(II) but also affected the final products of Mn oxides. For example, amorphous Mn oxides were formed instead of crystalline Mn(III) oxides, such as MnOOH. Furthermore, rhodochrosite (MnCO₃) was formed with the high Mn(II)/Sb₂O₃ ratio_, but without being observed in the low Mn(II)/Sb₂O₃ ratio. The results of study could help provide more understanding about the fate of Sb in the environment and the redox transformation of Mn.     

Characterization and physicochemical aspects of novel cellulose-based layered double hydroxide nanocomposite for removal of antimony and fluoride from aqueous solution

A series of novel adsorbents composed of cellulose (CL) with Ca/Al layered double hydroxide (CC_xA; where x represent the Ca/Al molar ratio) were prepared for the adsorption of antimony (Sb(V)) and fluoride (F^?) ions from aqueous solutions. The CC_xA was characterized by Fourier-transform infrared spectroscopy (FTIR), Brunauer–Emmett–Teller (BET), elemental analysis (CHNS/O), thermogravimetric analysis (TGA-DTA), zeta potential, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) analysis. The effects of varying parameters such as dose, pH, contact time, temperature and initial concentration on the adsorption process were investigated. According to the obtained results, the adsorption processes were described by a pseudo-second-order kinetic model. Langmuir adsorption isotherm model provided the best fit for the experimental data and was used to describe isotherm constants. The maximum adsorption capacity was found to be 77.2 and 63.1 mg/g for Sb(V) and F^?, respectively by CC₃A (experimental conditions: pH 5.5, time 60 min, dose 15 mg/10 mL, temperature 298 K). The CC₃A nanocomposite was able to reduce the Sb(V) and F^? ions concentration in synthetic solution to lower than 6 μg/L and 1.5 mg/L, respectively, which are maximum contaminant levels of these elements in drinking water according to WHO guidelines.     

Immobilization of antimony in soil and groundwater using ferro-magnesium bimetallic organic frameworks

Sb(Ⅲ) is often detected in contaminated soil and groundwater. Hence, high-efficiency technology is needed. In this study, bimetallic organic frameworks were used for the first time to immobilize Sb(Ⅲ) from contaminated soil and groundwater. The materials were synthesized by the hydrothermal method. Both ends of the prepared material were hexagonal tip rods,and the length became shorter as the ratio of Fe/Mg decreased. The bimetallic organic framework with a Fe/Mg feeding ratio of 0.5 was the opt...     

Multiple effects of nitrate amendment on the transport, transformation and bioavailability of antimony in a paddy soil-rice plant system

Nitrate (NO₃^?) is known to be actively involved in the processes of mineralization and heavy metal transformation; however, it is unclear whether and how it affects the bioavailability of antimony (Sb) in paddy soils and subsequent Sb accumulation in rice. Here, the effects of NO₃^? on Sb transformation in soil-rice system were investigated with pot experiments over the entire growth period. Results demonstrated that NO₃^? reduced Sb accumulation in brown rice by 15.6% compared to that in the control. After amendment with NO₃^?, the Sb content in rice plants increased initially and then gradually decreased (in roots by 46.1%). During the first 15 days, the soil pH increased, the oxidation of Sb(III) and sulfides was promoted, but the reduction of iron oxide minerals was inhibited, resulting in the release of adsorbed and organic-bound Sb from soil. The microbial arsenite-oxidizing marker gene aoxB played an important role in Sb(III) oxidation. From days 15 to 45, after NO₃^? was partially consumed, the soil pH decreased, and the reductive dissolution of Fe(III)-bearing minerals was enhanced; consequently, iron oxide-bound Sb was transformed into adsorbed and dissolved Sb species. After day 45, NO₃^? was completely reduced, Sb(V) was evidently reduced to Sb(III), and green rust was generated gradually. Thus, the available Sb decreased due to its enhanced affinity for iron oxides. Moreover, NO₃^? inhibited the reductive dissolution of iron minerals, which ultimately caused low Sb availability. Therefore, NO₃^? can chemically and biologically reduce the Sb availability in paddy soils and alleviate Sb accumulation in rice. This study provides a potential strategy for decreasing Sb accumulation in rice in the Sb-contaminated sites.     

Chlorine promotes antimony volatilization in municipal waste incineration

Antimony volatilization in municipal waste incineration was studied. Two municipal waste samples and antimony(III) oxide (Sb₄O₆) were heated to 500°C and 700°C in an air stream in a quartz furnace. The volatilization of Sb₄O₆ occurred more at 700°C that at 500°C. Conversely, antimony volatilization form municipal waste was stronger at 500°C than at 700°C. This implies that antimony from municipal waste is volatilized as chloride instead of oxide. The chlorine sources for antimony chlorination, a gas-phase reaction involving hydrochloric acid and a solid-phase reaction of inorganic chlorine, e.g., CaCl₂, were compared. Only the solid-phase reaction could offer enough active chlorine to induce chlorination of antimony oxide. Received: July 2, 1998 / Accepted: January 28, 1999     

环境敏感地区纺织染整工业锑污染物排放限值探究

在对纺织染整企业集聚、环境位置敏感的两个典型区域调研的基础上,通过类似重金属标准和毒性类比、排污治理情况及水体底泥中锑含量的分析、水环境承载力和允许排放浓度计算等技术论证,提出环境敏感地区纺织染整工业锑的排放限值按不同排放情形可分别设定为0.1 mg/L和0.05 mg/L。工程实例表明,采用基于聚合硫酸铁混凝沉淀法的高低浓度废水分质处理技术可满足排放限值要求,且经济成本可接受。     

Co-leaching of brominated compounds and antimony from bottled water

A fast-growing bottled water market is occasionally challenged by reports calling for contaminant leaching from water-contact materials (plastics). Our focus was on leaching of antimony (Sb) and brominated compounds expressed by total soluble bromine (Br) measurements, including those of polybrominated diphenyl ethers (PBDE). Studies are lacking on concomitant leaching of two or more inorganic plastic constituents from the same bottle. A market-representative basket survey of bottled water was initiated in Boston, USA supermarkets. Bottled water classes sampled were: i) non-carbonated (NCR), ii) carbonated (CR), and iii) non-carbonated and enriched (NCRE). Plastic bottle materials sampled were: polyethylene terephthalate (PET), high-density polyethylene (HDPE), polystyrene (PS), and polycarbonate (PC). Storage conditions for the 31 bottled water samples were: 23 °C temperature, no-shaking and 12 h/12 h light/dark for 60 days of equilibration. Average Br and Sb concentrations after 60-days of storage followed the order of NCR < CR = NCRE, and NCR < CR < NCRE, respectively, suggesting that the presence of dissolved carbon dioxide in CR samples coupled to additions of flavors and color to NCRE could explain the elevated leaching of Br and Sb. Combining all bottled water classes and plastic material types, a highly significant (p < 0.001) correlation was observed between log-transformed soluble Br and Sb concentrations, suggesting similar leaching behavior. Among samples with the highest soluble Br concentrations, BDE-209 congener was qualitatively confirmed in three out of four bottled water samples. The PC, HDPE, and PS samples exhibited significantly (p < 0.05) lower Sb and Br leaching than PET. Upon quantitative validation of PBDE leaching from certain plastic bottles into water, a revisit to existing PBDE exposure assessment reports will be deemed necessary.     

Temporal and spatial distribution of atmospheric antimony emission inventories from coal combustion in China

A multiple-year inventory of atmospheric antimony (Sb) emissions from coal combustion in China for the period of 1980-2007 has been calculated for the first time. Specifically, the emission inventories of Sb from 30 provinces and 4 economic sectors (thermal power, industry, residential use, and others) are evaluated and analyzed in detail. It shows that the total Sb emissions released from coal combustion in China have increased from 133.19 t in 1980 to 546.67 t in 2007, at an annually average growth rate of 5.4%. The antimony emissions are largely emitted by industrial sector and thermal power generation sector, contributing 53.6% and 26.9% of the totals, respectively. At provincial level, the distribution of Sb emissions shows significant variation. Between 2005 and 2007, provinces always rank at the top five largest Sb emissions are: Guizhou, Hunan, Hebei, Shandong, and Anhui.     

贵州某锑冶炼厂周边农田土壤锑、砷污染与人体健康风险评估

本研究以贵州省独山县某锑冶炼厂周边农田土壤为研究对象,系统采集17个土壤样品,测定了土壤中Sb、As总含量,并采用生理提取试验(PBET)和简化生物可给性提取试验(SBET)两种体外胃肠模拟实验方法分析了土壤中Sb、As的生物可给态含量,基于土壤Sb、As总量和生物可给性(PBET和SBET)评估了研究区锑、砷污染土壤...     

Distribution and phytoavailability of antimony at an antimony mining and smelting area,Hunan, China

An investigation of the distribution, fractionation and phytoavailability of antimony (Sb) and other heavy metals in soil sampled at various locations in the vicinity of a Sb mine revealed elevated levels of Sb, most certainly due to the mining activities. The concentration of Sb in the soil samples was 100.6–5045 mg kg⁻¹; in comparison, the maximum permissible concentration for Sb in soil in The Netherlands is 3.5 mg kg⁻¹, and the maximum permissible concentration of pollutant Sb in receiving soils recommended by the World Health Organization is 36 mg kg⁻¹. The soil sampled near the Sb mine areas had also contained high concentrations of As and Hg. Root and leaf samples from plants growing in the Sb mine area contained high concentrations of Sb, with the concentration of Sb in the leaves of radish positively correlating with Sb concentrations in soil. The distribution of Sb in the soil showed the following order: strongly bound to the crystalline matrix > adsorbed on Fe/Mn hydrous oxides, complexed to organic/sulfides, bound to carbonates > weakly bound and soluble. Solvents showed varying levels of effectiveness in extracting Sb (based on concentration) from the soil, with , in decreasing order. The concentration of easily phytoavailable Sb was high and varied from 2.5 to 13.2 mg kg⁻¹, the percentage of moderately phytoavailable Sb ranged from 1.62 to 8.26%, and the not phytoavailable fraction represented 88.2–97.9% of total Sb in soils.