Mobility Of Antimony Research Articles

Effects of Dissolved Organic Matter with Different Molecular Weights on Antimony Mobilization in Shallow Groundwater at the World’s Largest Antimony Mine, China

Effects of Dissolved Organic Matter with Different Molecular Weights on Antimony Mobilization in Shallow Groundwater at the World’s Largest Antimony Mine, China

Decomposition of waterside plants greatly affects the transformation and mobility of sedimentary antimony in water–sediment systems after emergency treatment: A microcosm study

Polyferric sulfate (PFS) coagulation has proven to be effective in addressing antimony (Sb) water pollution accidents; however, the impact of waterside plant decomposition on its effectiveness has not been adequately elucidated. This study investigated the effects of Alternanthera philoxeroides (AP) and Digitaria sanguinalis (DS) decomposition on Sb cycling after PFS treatment. Without plant decomposition, the Fe(OH)3 hydrolysate-associated Sb remained stable, and the sediment continued to exhibit Sb sink properties. Plant residue decomposition facilitated sedimentary Sb release, and DS decomposition had a greater impact than AP decomposition. The strong decomposition phases triggered abiotic/biotic reduction processes, leading to Fe(OH)3 dissolution and subsequent Sb(V) release. Concurrently, sulfate reduction and dissolved organic matter (DOM) release regulated Sb mobility. In addition, Sb(V) reduction occurred, and Sb(III) was elevated in the overlying water. The Sb(III) levels gradually decreased during the later aerobic stages, however, did not completely disappear within a short timeframe. Furthermore, the role of the sediment as an Sb sink was significantly hindered, maintaining relatively high levels of dissolved Sb. Sedimentary Sb speciation analysis revealed that plant decomposition induced a shift in Fe-oxyhydroxide-bound Sb to more bioavailable and stable fractions. Our results indicate that plant residue decomposition easily deteriorates PFS efficiency and increases the risk of secondary Sb pollution in water–sediment systems.

Competitive adsorption behavior of As(V) and Sb(V) on Hematite: Facet and pH dependent coordination affinity and role of outer-sphere complexes

The environmental mobility and fate of arsenic (As) and antimony (Sb) are influenced by ubiquitous iron minerals, but little is known about whether their co-adsorption behavior is affected by the exposed facets. Herein, we used cubic and rod-shaped hematite nanocrystals (HNC and HNR) to investigate the effect of exposed facets on competitive adsorption behaviors. TEM analysis indicated that the primary exposed facets of HNC and HNR were {110} and {012}, separately. Calculations supported the predictions of our model, revealing that the competition in acidic and alkaline environments was mainly influenced by the affinity and bond stability of facet-related adsorption configurations. However, the competition in neutral conditions was jointly influenced by facet-related coordination and adsorption behavior, due to the dependence of Sb(V) on protonation sites. On HNR (pH = 3), the adsorption of Sb(V) (50.6 %) was approximately twice that of As(V) (27.8 %) for its significant advantage in bidentate coordination on the {110} facet, whereas on HNC, As(V) (65.9 %) and Sb(V) (69.3 %) exhibited similar competitiveness. Notably, As(V) and Sb(V) tend to be adsorbed through outer-sphere coordination under alkaline conditions. On the {012} facet, As(V) and Sb(V) exhibited similar competitiveness for outer-sphere sites, whereas on the {110} facet, As(V) outer-sphere coordination showed stronger affinity, giving it an edge in competing on HNR. Overall, this study elucidated the critical role of varying exposed facets in the competitive adsorption process and proposed novel strategies for the selective removal of coexisting As(V) and Sb(V) through tailored fixed-facet iron oxides.

Novel insights into antimony mobilization in different high- antimony aquifers from the molecular signatures of dissolved organic matter

The crucial role of the fluorescent components of dissolved organic matter (DOM) in controlling antimony (Sb) mobilization in groundwater has been confirmed. However, the molecular signatures contributing to Sb enrichment in DOM remain unknown. This study aims to investigate the origins and molecular compositions of DOM in different high-Sb aquifers (Sb-mining and no-Sb-mining aquifer), as well as compare different molecular signatures of DOM and mechanisms for Sb migration. The findings showed that Sb concentrations in Sb-mining aquifer exhibited a positive correlation with lignin- and tannin-like molecules characterized by high O/C and low H/C ratios, indicating an increased abundance of aromatic components with higher Humification Index and SUV-absorbance at 254 nm, compared to no-Sb-mining aquifer. Correspondingly, the complexation and competitive adsorption were considered as the predominate formation mechanisms on Sb enrichment in Sb-mining aquifer. In addition, high abundances of bioreactivity DOM may facilitated the migration of Sb via electron transfer and competitive adsorption in native no-Sb-mining aquifer. The outcomes of this investigation offer novel insights into the mechanism on Sb enrichment influenced by DOM at the molecule level.

Mobilization and transformation of antimony in stibnite by microbial induced oxidation in mining environment

Elevated concentrations of antimony (Sb) in environmental and biological systems due to mining activities are of particular global concern. Microorganisms play a crucial role in the oxidation process of metallic sulfide minerals, leading to the release of metal ions into surrounding soil or water systems. However, the mechanisms and potential environmental effects of microbial induced oxidation of stibnite (Sb2S3) in mine environment remain unclear. In this study, compared with the abiotic controls, the microbial community screened from the highly contaminated soil of the Xikuangshan antimony mine in aerobic experiments did not promote Sb mobilization as expected. However, they had a significant effect on the morphology and species of oxidation products of Sb2S3 by mediating the oxidation of Sb(III) and sulfide on surface and in solution. These naturally coexisting bacteria could partially oxidize Sb2S3 to Sb(V) and SO42− directly on the mineral surface, completely oxidize the dissolved Sb(III) to Sb(V), facilitate the oxidation of S0 to S2O32−, and form the secondary Sb(V)-bearing mineral [NaSb(OH)6]. These findings support the important role of microorganisms in the mobilization and transformation of Sb from minerals/rocks in the mining environment and provide further insight into their potential environmental impacts and effective mitigation strategies.

Antimony mobility in soil near historical waste rock at the world's largest Sb mine, Central China

Soil near waste rock often contains high concentrations of antimony (Sb), but the mechanisms that mobilize Sb in a soil closely impacted by the waste rock piles are not well understood. We investigated these mobility mechanisms in soils near historical waste rock at the world's largest Sb mine. The sequential extraction (BCR) of soil reveal that over 95 % Sb is present in the residual fraction. The leached Sb concentration is related to the surface protonation and deprotonation of soil minerals. SEM-EDS shows Sb in the soil is associated with Fe and Ca. Moreover, X-ray absorption spectroscopy (XAS) results show Sb is predominantly present as Sb(V) and is associated with Fe in the form of tripuhyite (FeSbO4) as well as edge- and corner-sharing complexes on ferrihydrite and goethite. Thus, Fe in soils is important in controlling the mobility of Sb via surface complexation and co-precipitation of Sb by Fe oxides. The initially surface-adsorbed Sb(V) or co-precipitation is likely to undergo a phase transformation as the Fe oxides age. In addition, Sb mobility may be controlled by small amounts of calcium antimonate. These results further the understanding of the effect of secondary minerals in soils on the fate of Sb from waste rock weathering and inform source treatment for Sb-contaminated soils.

Co-transport of ferrihydrite–organic matter colloids with Sb(v) in saturated porous media: implications for antimony mobility

Schematic diagram of the mechanism of Fe–NOM–Sb(v) colloids formation and transport in the natural environment.

Antimony(V) behavior during the Fe(II)-induced transformation of Sb(V)-bearing natural multicomponent secondary iron mineral under acidic conditions

Fe(II)-induced phase transformations of secondary iron minerals have attracted considerable attention due to their influence on antimony (Sb) mobility. However, Fe(II)-induced natural multicomponent secondary iron mineral (nmSIM) transformations and the corresponding repartitioning of Sb on nmSIM under acidic conditions upon Fe(II) exposure have not been systematically examined. Herein, we investigated the effect of Fe(II) on nmSIM mineralogy and Sb mobility in Sb(V)-bearing nmSIM at pH 3.8 and 5.6 at various Fe(II) concentrations over 15 d. The Sb(V)-bearing nmSIM phase transformation occurred under both strongly and weakly acidic conditions without Fe(II) exposure, while the presence of Fe(II) significantly intensified the transformation, and substantial amounts of intermediary minerals, including jarosite, ferrihydrite, lepidocrocite and fougerite, formed during the initial reaction stage, especially at pH 5.6. X-ray diffraction (XRD) analyses confirmed that goethite and hematite were the primary final-stage transformation products of Sb(V)-bearing nmSIM, regardless of Fe(II) exposure. Throughout the Sb(V)-bearing nmSIM transformation at pH 3.8, Sb release was inversely related to the Fe(II) concentration in the initial stage, and after maximum release was achieved, Sb was gradually repartitioned onto the nmSIM. No Sb repartitioning occurred in the absence of Fe(II) at pH 5.6, but the introduction of Fe(II) suppressed Sb release and improved Sb repartitioning on nmSIM. This transformation was conducive to Sb reimmobilization on Sb(V)-bearing nmSIM due to the structural incorporation of Sb into the highly crystalline goethite and hematite generated by the Sb(V)-bearing nmSIM transformation, and no reduction of Sb(V) occurred. These results imply that Fe(II) can trigger mineralogical changes in Sb(V)-bearing nmSIM and have important impacts on Sb partitioning under acidic conditions. These new insights are essential for assessing the mobility and availability of Sb in acid mine drainage areas.

Contrasting optical properties of dissolved organic matter in rivers around an antimony mine, Hunan Province, China: implications for antimony mobility

Contrasting optical properties of dissolved organic matter in rivers around an antimony mine, Hunan Province, China: implications for antimony mobility

Mobility of antimony in contrasting surface environments of a mine site: influence of redox conditions and microbial communities.

Microbial processes can influence the complex geochemical behaviour of the toxic metalloid antimony (Sb) in mining environments. The present study is aimed to evaluate the influence of microbial communities on the mobility of Sb from solid phases to water in different compartments and redox conditions of a mining site in southwest (SW) Spain. Samples of surface materials presenting high Sb concentrations, from two weathered mining waste dumps, and an aquatic sediment were incubated in slurries comparing oxic and anoxic conditions. The initial microbial communities of the three materials strongly differed. Incubations induced an increase of microbial biomass and an evolution of the microbial communities' structures and compositions, which diverged in different redox conditions. The presence of active bacteria always influenced the mobility of Sb, except in the neutral pH waste incubated in oxic conditions. The effect of active microbial activities in oxic conditions was dependent on the material: Sb oxic release was biologically amplified with the acidic waste, but attenuated with the sediment. Different bacterial genera involved in Sb, Fe and S oxidation or reduction were present and/or grew during incubation of each material. The results highlighted the wide diversity of microbial communities and metabolisms at the small geographic scale of a mining site and their strong implication in Sb mobility.

Antimony immobilization mechanism on schwertmannite: Insights from the microstructure of schwertmannite

Schwertmannite affects the mobility of antimony (Sb) in acid mine drainage, yet the Sb sorption mechanism remains elusive. In this study, the molecular-level mechanism and the driving force of Sb(V) immobilized on schwertmannite were investigated by a combination of wet chemistry, extended X-ray absorption fine structure (EXAFS) analysis, density functional theory (DFT) calculations, and a surface complexation model (SCM). The observed sorption capacity for Sb(V) was as high as 235.63 mg/g. Such remarkable sorption capacity is primarily achieved by the anion exchange reaction and surface complexation reaction of Sb(V) with sulfate and surface/tunnel inner-surface hydroxyl groups, respectively, and the contribution of the anion exchange reaction to Sb(V) immobilization decreases markedly with increasing Sb(V) loading or pH. The loading of Sb(V) appears to be the key parameter controlling its immobilization mechanism on schwertmannite. Low-loaded Sb(V) primarily generates bidentate-mononuclear and bidentate-binuclear surface complexes (adsorption products) and is concurrently partly incorporated into the Fe-O framework of schwertmannite to form a hexadentate-hexanuclear complex (incorporation product). With increasing Sb(V) loading, Sb is primarily adsorbed on the surface and in the tunnel of schwertmannite with the formation of bidentate-mononuclear (dominant) and bidentate-binuclear complexes without incorporation. The inconsistency of the immobilization mechanism is controlled by the amount of released sulfate induced by Sb(V). The substantial system energy reduction caused by the formation of Sb(V) adsorption and incorporation products on the surface and in the tunnel of schwertmannite is the driving force for the stable immobilization of Sb(V) by schwertmannite, and the energy reduction caused by tunnel complexes is far more obvious than that caused by surface complexes. A charge distribution multisite complexation model was established based on bidentate-mononuclear and bidentate-binuclear surface complexes with fitted Log K values of 21.99 ± 0.18 and 12.84 ± 0.92, respectively, which consistently predicted Sb(V) sorption across pH 3.0–9.0 for all involved Sb(V) loadings. In addition, Sb(V) has a strong stabilizing effect on the schwertmannite structure and broadens its pH stability window (pH 3.0–9.0). This study facilitates elucidation of the fate and geochemical cycling of Sb in the mining environment and helps to promote the application of the microstructure of schwertmannite in other studies of microscopic interface chemistry.

Pollution assessment of antimony in shooting range soils

Soil samples collected from the berm at Thebephatshwa (TAB) shooting range found in Botswana showed variable total concentrations of antimony in the range 38±1 to 283±12 mg/kg. Total antimony concentrations found in the soils were higher than the set regulatory levels by the World Health Organization (36 mg/kg) and the United States Protection Agency (31 mg/kg). The upper berm showed elevated levels of antimony (283±12 mg/kg) due, in part, to the highest density of spent projectiles found in this part of the berm. Sequential extraction studies established that antimony was partitioned mostly in the organic and residual fractions of the soil. Environmental pollution risk assessment based on geoaccumulation index (Igeo), contamination factor (CF) and enrichment factor (EF) indicated all four sections of the berm posed high risk to the environment. The upper berm exhibited extreme pollution from antimony (Igeo ~9), very high contamination (CF ~744) and extreme antimony enrichment (EF ~506) compared to the other three sections studied. Elevated levels of antimony at TAB shooting range call for best shooting range management practices, soil remediation and reclamation methods to be carried out at this shooting range to minimize the mobility and bioavailability of antimony.

Geochemical impact of dissolved organic matter on antimony mobilization in shallow groundwater of the Xikuangshan antimony mine, Hunan Province, China

Dissolved organic matter (DOM) is widely used in aquatic systems to control the environmental fate of As. However, similar to the behavior of As, Sb mobilization driven by DOM is poorly understood. A total of 25 samples were collected from shallow groundwater in the Xikuangshan mine to compare the spectroscopic characteristics and chemical properties of DOM between high- and low-Sb groundwater and to determine the roles of DOM in Sb mobility. The concentrations of Sb and DOM varied from 0.003 to 18.402 mg/L (mean: 3.407 mg/L) and 0.38 to 9.90 mg/L (mean: 2.49 mg/L), respectively. The DOM of the D3x4 water was primarily dominated by terrestrial and microbial humic-like and fulvic acid substances, with a relatively small contribution of tryptophan-like components. Complexing agents, competitive adsorption, and photopromoted oxidation under sunlight were considered as the formation mechanisms for DOM-controlled Sb(V)-dominated Sb species in D3x4 water. The weakly alkaline and oxidizing conditions, and the presence of Fe hydroxides facilitated the promotion of Sb(V) concentration. The findings of this study further enhance our understanding of the Sb migration mechanism in oxic groundwater.

Geochemical Impact of Dissolved Organic Matter on Antimony Mobilization in Shallow Groundwater of the Xikuangshan Antimony Mine, Hunan Province, China

Geochemical Impact of Dissolved Organic Matter on Antimony Mobilization in Shallow Groundwater of the Xikuangshan Antimony Mine, Hunan Province, China

New Mobilization Pathway of Antimonite: Thiolation and Oxidation by Dissimilatory Metal-Reducing Bacteria via Elemental Sulfur Respiration.

Antimony (Sb) mobilization is widely explored with dissimilatory metal-reducing bacteria (DMRB) via microbial iron(III)-reduction. Here, our study found a previously unknown pathway whereby DMRB release adsorbed antimonite (SbIII-O) from goethite via elemental sulfur (S0) respiratory reduction under mild alkaline conditions. We incubated SbIII-O-loaded goethite with Shewanella oneidensis MR-1 in the presence of S0 at pH 8.5. The incubation results showed that MR-1 reduced S0 instead of goethite, and biogenic sulfide induced the formation of thioantimonite (SbIII-S). SbIII-S was then oxidized by S0 to mobile thioantimonate (SbV-S), resulting in over fourfold greater Sb release to water compared with the abiotic control. SbIV-S was identified as the intermediate during the oxidation process by Fourier transform ion cyclotron resonance mass spectrometry and electron spin resonance analysis. The existence of SbIV-S reveals that the oxidation of SbIII-S to SbV-S follows a two-step consecutive one-electron transfer from Sb to S atoms. SbV-S then links with SbIII-S by sharing S atoms and inhibits SbIII-S polymerization and SbIII2S3 precipitation like a "capping agent". This study clarifies the thiolation and oxidation pathway of SbIII-O to SbV-S by S0 respiration and expands the role of DMRB in the fate of Sb.

Potentially Mobilizable Geogenic As and Sb in an Agricultural Wetland Soil

The mobility of arsenic (As) and antimony (Sb) in soils is controlled by several processes (adsorption/desorption, (co)precipitation/dissolution and oxidation/reduction), depending on various environmental factors that are often convoluted and site-dependent. This study investigated: (i) the content and solid-phase distribution of geogenic As and Sb in a vertical soil profile (0–130 cm) of an agricultural wetland subject into alternating oxic and anoxic conditions induced by periodic waterlogging and (ii) identifies the stability of the As and Sb host phases during soil reduction (laboratory incubation) using a sequential extraction procedure (fractions: loosely and strongly adsorbed, carbonates, easily reducible, reducible, oxidable and residual). The field results showed that, in the deeper, permanently water-saturated soil layers (<60 cm), the amounts of As and Sb were relatively low (As: 8 ± 2 µg·g−1 and Sb: 0.9 ± 0.2 µg·g−1) and related to the Fe content. In the periodically flooded upper soil layers (0–40 cm), the amounts of As and Sb were higher compared to the deeper layers (As: 36 ± 3 µg·g−1 and Sb: 1.14 ± 0.05 µg·g−1). The observed enrichment towards the surface was attributed to the higher content of organic matter (for Sb) and metalloids distribution among the easily reducible fraction (for As). The anoxic laboratory incubation of periodically waterlogged soil showed that, during soil reduction, As is largely mobilized from the easily reducible fraction and undergoes partial readsorption. Unlike As, Sb displayed a higher affinity for more stable soil components (e.g., reducible and residual fractions), which highlights its limited mobility in periodically waterlogged soil compared to As. The potentially mobilizable As and Sb estimated as the sum of the acetate-exchangeable, P-exchangeable, easily reducible and H2O2-organic fractions represent up to 83%, 69% and 53% of the total As and up to 53%, 44% and 54% of the total Sb at 0–20-cm, 40–60-cm and 90–110-cm depths, respectively. Thus, unpolluted soils may act as sources of As and Sb to aquatic environments and therefore have negative consequence on the downstream water quality.

Effect of Municipal Solid Waste Compost on Antimony Mobility, Phytotoxicity and Bioavailability in Polluted Soils

The effect of a municipal solid waste compost (MSWC), added at 1 and 2% rates, on the mobility, phytotoxicity, and bioavailability of antimony (Sb) was investigated in two soils (SA: acidic soil; SB: alkaline soil), spiked with two Sb concentrations (100 and 1000 mg kg−1). The impact of MSWC on microbial activity and biochemical functioning within the Sb-polluted soils was also considered. MSWC addition reduced water-soluble Sb and favored an increase in residual Sb (e.g., by 1.45- and 1.14-fold in SA-100 and SA-1000 treated with 2% MSWC, respectively). Significant increases in dehydrogenase activity were recorded in both the amended soils, as well as a clear positive effect of MSWC on the metabolic activity and catabolic diversity of respective microbial communities. MSWC alleviated Sb phytotoxicity in triticale plants and decreased Sb uptake by roots. However, increased Sb translocation from roots to shoots was recorded in the amended soils, according to the compost rate. Overall, the results obtained indicated that MSWC, particularly at a 2% rate, can be used for the recovery of Sb-polluted soils. It also emerged that using MSWC in combination with triticale plants can be an option for the remediation of Sb-polluted soils, by means of assisted phytoextraction.

Reduction of antimony mobility from Sb-rich smelting slag by Shewanella oneidensis: Integrated biosorption and precipitation

The dissimilatory Fe(III)-reducing bacteria play a significant role in the mobility of antimony (Sb) under reducing environment. Sb-rich smelting slag is iron (Fe)-containing antimonic mine waste, which is one of the main sources of antimony pollution. In this study, the soluble antimony reacted with Fe(III) by S. oneidensis (Shewanella oneidensis strain MR-1) was performed in reduction condition, then the dissolution behavior of the Sb-rich smelting slag with S. oneidensis was investigated. The results showed that the released Sb was immobilized by S. oneidensis and the strain adsorbed Sb(III) preferentially. Sb(V) can be reduced by S. oneidensis without aqueous Fe. In the presence of Fe(III), S. oneidensis mediated Sb bio-adsorption and the chemical redox of Sb-Fe occurred simultaneously. Sb was co-precipitated with Fe to form the Sb(V)-O-Fe(III) secondary mineral, which was identified as the bidentate mononuclear edge-sharing structure by extended X-ray absorption fine structure (EXAFS) analysis. These results suggest that S. oneidensis has a positive effect on the immobilization and minimizing toxicity of antimony in anoxic soil and groundwater, which provides a theoretical basis for the treatment of antimony contamination.

Antimonite oxidation and adsorption onto two tunnel-structured manganese oxides: Implications for antimony mobility

Manganese (Mn) oxides have high oxidation and sorption capacities, which enables them to play important roles in antimony (Sb) migration and transformation. In this study, the oxidation and adsorption behaviors of antimonite (Sb(III)) on two tunnel-structured Mn oxides, pyrolusite (β-MnO2) and manganite (γ-MnOOH), were investigated and compared using batch kinetic techniques; the adsorption isotherms, edges and spectroscopic characteristics of Sb(III) and Sb(V) on the two minerals were also compared and modeled. The adsorption isotherms and edges indicated that the affinity of Sb(III) and Sb(V) toward the two Mn oxides depended on the Sb species, the pH of the solution and the characteristics of the two minerals. Acidic pH favored the sorption of both Sb(III) and Sb(V) onto the two minerals, with the rate of sorption decreasing subsequently with the increase in pH. The sorption capacity of β-MnO2 for both Sb(III) and Sb(V) was much lower than that of the γ-MnOOH. Sb(V) was the main species after Sb(III) and Sb(V), which adsorbed onto the surface of both β-MnO2 and γ-MnOOH. Furthermore, Sb(V) combined with γ-MnOOH through inner-sphere complexation and with β-MnO2 through outer-sphere complexation. These results therefore provide new insights into the mechanism of Sb(III) oxidation and adsorption on the surfaces of two tunnel-structured Mn oxides and indicates that γ-MnOOH would exhibit a huge capacity in Sb oxidation and sorption.

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-1′s genome. We therefore hypothesized that under oxic conditions, AS-1 could mediate the oxidation of sulfide and Sb(III) in stibnite (Sb2S3) and lead to the release of Sb. Indeed, strain AS-1 was discovered as an autotrophic Sb(III)-oxidizer. Antimony mobilization studies conducted with strain AS-1 showed significantly enhanced mobilization of Sb, and complete oxidation of released Sb and sulfur to Sb(V) and sulfate. In addition, AS-1 induced a faster release of Sb under heterotrophic condition, and new acicular minerals might form. These findings support the hypothesis that microorganisms play an important role in the mobilization and transformation of Sb in XKS mine area and may contribute to our further understanding of the Sb biogeochemical redox cycle in natural environment.