Mobility Of Antimony Research Articles

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.

Antimony (V) Adsorption at the Hematite–Water Interface: A Macroscopic and In Situ ATR-FTIR Study

The environmental mobility of antimony (Sb) is largely unexplored in geochemical environments. Iron oxide minerals are considered major sinks for Sb. Among the different oxidation states of Sb, (+) V is found more commonly in a wide redox range. Despite many adsorption studies of Sb (V) with various iron oxide minerals, detailed research on the adsorption mechanism of Sb (V) on hematite using macroscopic, spectroscopic, and surface complexation modeling is rare. Thus, the main objective of our study is to evaluate the surface complexation mechanism of Sb (V) on hematite under a range of solution properties using macroscopic, in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopic, and surface complexation modeling. The results indicate that the Sb (V) adsorption on hematite was highest at pH 4–6. After pH 6, the adsorption decreased sharply and became negligible above pH 9. The effect of ionic strength was negligible from pH 4 to 6. The spectroscopic results confirmed the presence of inner- and outer-sphere surface complexes at lower pH values, and only outer-sphere-type surface complex at pH 8. Surface complexation models successfully predicted the Sb (V) adsorption envelope. Our research will improve the understanding of Sb (V) mobility in iron-oxide-rich environments.

Oxidation and incorporation of adsorbed antimonite during iron(II)-catalyzed recrystallization of ferrihydrite.

The toxicity and mobility of antimony (Sb) are strongly influenced by the redox transformation of widely spread 2-line ferrihydrite (Fh) in natural soils and sediments. This study investigated the transformation and redistribution of adsorbed antimonite (Sb(III)) during Fe(II)-catalyzed recrystallization of Fh under anaerobic conditions. X-ray diffraction (XRD), transmission electron microscopy (TEM), and synchrotron based X-ray absorption spectroscopy (XAS) were utilized to characterize the mineralogy and morphology of generated minerals as well as the speciation of Sb and Fe. Chemical analysis and Sb LIII-edge XANES spectra demonstrated that a great part of Sb(III) (80%-90%) was oxidized to Sb(V) by reactive oxygen species (ROS) during the Fe(II)-catalyzed transformation of Fh. Chemical extraction results showed that the mobility of Sb was significantly reduced with 50%-70% of initially adsorbed Sb(III) transformed to phosphate-unextractable phase. Antimony K-edge EXAFS analysis showed the SbO6 octahedra were incorporated into secondary minerals by substituting the Fe atoms. Our findings shed new light on the understanding of the geochemical behavior of Sb(III) under anoxic conditions.

Impact of Antimony(V) on Iron(II)-Catalyzed Ferrihydrite Transformation Pathways: A Novel Mineral Switch for Feroxyhyte Formation.

The environmental mobility of antimony (Sb) is controlled by interactions with iron (Fe) oxides, such as ferrihydrite. Under near-neutral pH conditions, Fe(II) catalyzes the transformation of ferrihydrite to more stable phases, thereby potentially altering the partitioning and speciation of associated Sb. Although largely unexplored, Sb itself may also influence ferrihydrite transformation pathways. Here, we investigated the impact of Sb on the Fe(II)-induced transformation of ferrihydrite at pH 7 across a range of Sb(V) loadings (Sb:Fe(III) molar ratios of 0, 0.003, 0.016, and 0.08). At low and medium Sb loadings, Fe(II) induced rapid transformation of ferrihydrite to goethite, with some lepidocrocite forming as an intermediate phase. In contrast, the highest Sb:Fe(III) ratio inhibited lepidocrocite formation, decreased the extent of goethite formation, and instead resulted in substantial formation of feroxyhyte, a rarely reported FeOOH polymorph. At all Sb loadings, the transformation of ferrihydrite was paralleled by a decrease in aqueous and phosphate-extractable Sb concentrations. Extended X-ray absorption fine structure spectroscopy showed that this Sb immobilization was attributable to incorporation of Sb into Fe(III) octahedral sites of the neo-formed minerals. Our results suggest that Fe oxide transformation pathways in Sb-contaminated systems may strongly differ from the well-known pathways under Sb-free conditions.

Insights into the fate of antimony (Sb) in contaminated soils: Ageing influence on Sb mobility, bioavailability, bioaccessibility and speciation

The effect of long-term ageing (up to 700 days) on the mobility, potential bioavailability and bioaccessibility of antimony (Sb) was investigated in two soils (S1: pH 8.2; S2: pH 4.9) spiked with two Sb concentrations (100 and 1000 mg·kg−1). The Sb mobility decreased with ageing as highlighted by sequential extraction, while its residual fraction significantly increased. The concentration of Sb (CDGT), as determined by diffusive gradients in thin films (DGT), showed a reduction in potential contaminant bioavailability during ageing. The DGT analysis also showed that Sb-CDGT after 700 days ageing was significantly higher in S1–1000 compared to S2–1000, suggesting soil pH plays a key role in Sb potential bioavailability. In-vitro tests also revealed that Sb bioaccessibility (and Hazard Quotient) decreased over time. Linear combination fitting of Sb K-edge XANES derivative spectra showed, as a general trend, an increase in Sb(V) sorption to inorganic oxides with ageing as well as Sb(V) bound to organic matter (e.g. up to 27 and 37% respectively for S2–100). The results indicated that ageing can alleviate Sb ecotoxicity in soil and that the effectiveness of such processes can be increased at acidic pH. However, substantial risks due to Sb mobility, potential bioavailability and bioaccessibility remained in contaminated soils even after 700 days ageing.

Antimony release from polyester textiles by artificial sweat solutions: A call for a standardized procedure

Polyester fibres are usually contaminated by antimony because of its use as a catalyst in the production of polyethylene terephthalate and as a flame retardant synergist in a variety of new and recycled polymers. The present study determined the release of antimony (at total concentrations ranging from about 125 to 470 μg g−1) from polyester textile samples designed to be in contact with human skin using standard artificial sweat solutions (ISO 105-E04 and EN 1811). The study also examined the role of different experimental parameters on the release of the metalloid. Overall, and using the default parameters, between about 0.05 and 2% of total antimony (or 0.1–1 μg g−1) was mobilized into artificial sweat. A reduction in time (from 24 to 12 h) and temperature (from 37 to 20 or 4 °C) and an increase in pH (from 5.5 to 7) resulted in a decline in antimony mobilization from textiles, while altering textile mass to solution volume and the presence of lactate had little impact on the results. Removal of a filtration step increased antimony mobilization but this was attributed to artefacts associated with release from microfibres during extract storage and analysis. In general, antimony mobilization was sufficiently repeatable using either EN 1811 or ISO 105-E04 but the latter is recommended for an assessment of antimony mobilization and potential exposure because its pH is closer to that of human sweat. Since the first fraction of either extractions mobilized the greatest quantity of antimony, exposure can be minimized by washing articles before use.

Study on antimony mobility in a contaminated shallow lake sediment using the diffusive gradients in thin films technique

Antimony is a priority environmental contaminant. Increasing attention is being paid to the behaviors and mobilities of the various Sb species in the environment. Sb speciation in the environment and the mobilities of Sb species at mining sites have been studied well, but Sb speciation and mobility in shallow lakes requires further study. Here, we studied Sb behavior in sediment of a shallow lake in the plain rivers network in Taihu Basin that suffers continual Sb inputs from textile plants. The diffusive gradients in thin films techniques (DGT) made of zirconium oxide based binding resin gel (ZrO-Chelex), agarose diffusive gel and polyvinylidene fluoride filter were deployed in water and sediment to obtain a high-resolution record in situ. The results indicated that (1) pollutants released by textile plants caused relatively high Sb(Ⅲ), Sb(Ⅴ) and organoantimony concentrations in the eutrophic shallow lake, (2) Sb was seldomly mobile in the oxic layer where Sb(Ⅲ) was sorbed on Fe(Ⅲ) oxides and gradually formed Fe–Sb complexes in the sediment, but in the anoxic environment (oxidation-reduction potential: 366 − −344 mv) Sb(V), Fe(Ⅱ) and P (V) were simultaneously released to resupply the porewater, (3) the release of Sb from solid phase is decided by the redox condition, and the rate of release is dependent on the labile Sb content of the sediment. The mobility of Sb should be given sufficient attention when the potential ecological risk of metal(loid)s in shallow lakes and wetlands sediment are evaluated.

Reductive transformation of birnessite and the mobility of co-associated antimony

Manganese (Mn) oxide minerals, such as birnessite, are thought to play an important role in affecting the mobility and fate of antimony (Sb) in the environment. In this study, we investigate Sb partitioning and speciation during anoxic incubation of Sb(V)-coprecipitated birnessite in the presence and absence of Mn(II)aq at pH 5.5 and 7.5. Antimony K-edge XANES spectroscopy revealed that Sb(V) persisted as the only solid-phase Sb species for all experimental treatments. Manganese K-edge EXAFS and XRD results showed that, in the absence of Mn(II), the Sb(V)-bearing birnessite underwent no detectable mineralogical transformation during 7 days. In contrast, the addition of 10 mM Mn(II) at pH 7.5 induced relatively rapid (within 24 h) transformation of birnessite to manganite (~93%) and hausmannite (~7%). Importantly, no detectable Sb was measured in the aqueous phase for this treatment (compared with up to ∼90 μmol L−1 Sb in the corresponding Mn(II)-free treatment). At pH 5.5 , birnessite reacted with 10 mM Mn(II)aq displayed no detectable mineralogical transformation, yet had substantially increased Sb retention in the solid phase, relative to the corresponding Mn(II)-free treatment. These findings suggest that the Mn(II)-induced transformation and recrystallization of birnessite can exert an important control on the mobility of co-associated Sb.

Seasonal Temperature Oscillations Drive Contrasting Arsenic and Antimony Mobilization in a Mining‐Impacted River System

AbstractArsenic (As) and antimony (Sb) speciation and mobility in river systems can be influenced by the redox conditions of benthic and hyporheic zone sediments. However, our understanding of how temperature fluctuations influence riverine As and Sb mobility over diel and seasonal time frames, via moderation of sediment redox conditions, is poorly constrained. Here we compare diel and seasonal water quality data from a river system contaminated with As and Sb with results from sediment‐water incubations conducted at temperatures spanning 8°C to 32°C under low‐dissolved oxygen conditions. Higher incubation temperatures caused faster microbial respiration, lower redox potential, and greater Asaq concentrations, coincident with reduction of As(V), Mn (III/IV), Fe (III), and SO42−. Initial rates of As3+aq formation increased exponentially with temperature (Q10 = 3.3 ± 0.5) and were positively correlated with microbial respiration (r2 = 0.99, P < 0.01). In contrast, Sbaq displayed an initially negative and comparatively weak overall temperature dependence during incubations. In river waters, diel mobilization of reduced species (As3+aq and Fe2+aq) and contrasting attenuation of Sb was coincident with lower redox potential during nightly respiration cycles. Distinct seasonal oscillations in river water Asaq were exponentially correlated with temperature (r2 = 0.68, P < 0.01), whereas Sbaq was not. These characteristics reflect the fundamental role of anaerobic metabolism (as influenced by temperature) within benthic and hyporheic zone sediments as a key driver of contrasting riverine As and Sb mobility. The findings imply that riverine As mobility may be enhanced, while Sb mobility possibly attenuated, by eutrophication or by elevated stream temperatures due to a warming climate.

Speciation of antimony in representative sulfidic hot springs in the YST Geothermal Province (China) and its immobilization by spring sediments

As a well-known toxic element, antimony occurred in a wide range of concentrations in the geothermal waters discharging from Rehai and Daggyai, two representative hydrothermal areas in the Yunnan-Sichuan-Tibet Geothermal Province of China. Antimony speciation in different types of the hot springs in Rehai and Daggyai varied greatly as well, and tri- and tetrathioantimonate were detected in most neutral to alkaline Rehai hot springs. Neutral to alkaline pH, high sulfide concentrations, and high sulfide to antimony ratios were the critical factors promoting the formation of thioantimonates. The fact that no thioantimonates were detected in neutral to alkaline Daggyai hot springs is attributed to high concentrations of coexistent arsenic capable of inhibiting the thiolation of oxyantimony anions, because thioantimonates are kinetically more labile than thioarsenates. Upon discharge of the hot springs, both total aqueous antimony and arsenic decreased rapidly and substantially via immobilization to the sediments in the spring vents and their outflow channels. Some of the common iron-bearing minerals in the spring sediments, like pyrite and goethite, are known sinks for antimony and arsenic. Yet, an interesting difference was observed with antimony and iron contents in the sediment samples showing a significant correlation that was lacking for arsenic and iron contents. The explanation might be that for arsenic, sorption affinities are known to vary significantly with aqueous arsenic speciation and mineral phases. Typically, thiolation increases, and oxidation decreases arsenic mobility. Sorption experiments for antimony conducted in the present study, in contrast, showed that different antimony species were comparably sorbed to pyrite over a wide range of initial antimony concentrations and to goethite at relatively low initial antimony concentrations (but still covering the concentration range of antimony in common natural waters), so neither thiolation nor oxidation contributed significantly to the mobility of antimony in the hot springs investigated in this study.

Antimony mobility in sulfidic systems: Coupling with sulfide-induced iron oxide transformations

Iron (Fe) oxides are important host phases for antimony (Sb), a toxic metalloid of environmental concern. In wetland soils and sediments, poorly ordered Fe oxides such as ferrihydrite may undergo reductive dissolution and mineralogical transformation upon reaction with dissolved sulfide (S(-II)). The consequences of these processes for the mobility of associated Sb have not been investigated to date. Here, we allowed Sb(V)-bearing ferrihydrite (molar ratio of Fe:Sb = 400) to react with varying S(-II) concentrations (Fe(III):S(-II) = 0.2, 0.5, and 1) at pH 6 and 8 over 32 days. Changes in speciation and concentration of Fe, S and Sb in the aqueous, colloidal and solid phase were examined through a combination of aqueous-phase analyses, X-ray diffraction and synchrotron X-ray absorption spectroscopy. Addition of S(-II) caused rapid reduction of Fe(III), thereby producing elemental S and Fe(II). X-ray diffractometry and Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that S(-II) addition resulted in the precipitation of Fe(II) sulfides (mackinawite (FeS) and pyrite (FeS2)) and formation of secondary Fe(III) oxides (goethite (FeOOH) and hematite (Fe2O3)). The formation of mackinawite and pyrite was further confirmed by S K-edge X-ray absorption near-edge structure (XANES) spectroscopy, and was found to occur to the greatest extent in the high-sulfide treatments. The initial reductive dissolution of ferrihydrite was paralleled by a fast increase in dissolved Sb concentrations, with ∼25% of total Sb being released in the high-sulfide treatments. The Sb release was followed by Sb immobilization within ∼1–7 days. Since ion-chromatography ICP-MS revealed antimonate (Sb(OH)6-) as the primary Sb aqueous phase species throughout the experiment, with only negligible concentrations of antimonite (Sb(OH)3) and only very minor amounts (<4% of total Sb) of tri- and tetrathioantimonate (HxSbS3Ox−3/HxSbS4x−3), the decrease in Sb concentrations was attributed to surface-based sorption and structural incorporation of primarily Sb(V) by the secondary Fe oxides. In accordance with the dominance of aqueous Sb(V), Sb K-edge XANES spectroscopy showed that Sb(V) was also the dominant Sb species in the solid phase, comprising up to 90% of solid-phase Sb in the low-sulfide treatments. However, higher S(-II) addition and lower pH favored production of Sb(III) and resulted in up to 40% and 20% of solid-phase Sb(V) being reduced to Sb(III) at pH 6 and 8, respectively, with this Sb(III) comprising a mixture of O- and S-coordinated species. Around 15% of < 0.45-µm Sb occurred in the colloidal (>3 kDa) size fraction at pH 8 under medium and high S(-II) conditions, while no colloidal Sb was found in other treatments. Together, these results show that Fe oxide sulfidization can have opposing effects on Sb mobility. On the one hand, the initial sulfide-promoted Fe oxide dissolution triggers Sb release into the aqueous phase. On the other hand, Sb can subsequently be immobilized via sorption to secondary Fe oxides and newly-formed Fe sulfides during the later stages of sulfidization. Sulfidization reactions, and the complex opposing impacts on Sb mobility, should therefore be considered for the risk assessment and derivation of adequate management strategies at Sb-impacted sites which experience sulfidic conditions.

Mobility and potential bioavailability of antimony in contaminated soils: Short-term impact on microbial community and soil biochemical functioning.

Antimony (Sb) and its compounds are emerging priority pollutants which pose a serious threat to the environment. The aim of this study was to evaluate the short-term fate of antimonate added to different soils (S1 and S2) with respect to its mobility and impact on soil microbial communities and soil biochemical functioning. To this end, S1 (sandy clay loam, pH 8.2) and S2 (loamy coarse sand, pH 4.9) soils were spiked with 100 and 1000mg Sb(V) kg-1 soil and left in contact for three months. Sequential extractions carried out after this contact time indicated a higher percentage of labile antimony in the Sb-spiked S1 soils than S2 (e.g. ~13 and 4% in S1 and S2 treated with 1000mg Sb(V) kg-1 respectively), while the opposite was found for residual (hardly bioavailable) Sb. Also, a reduced number of culturable heterotrophic bacteria was recorded in Sb-spiked S1 soil (compared to the unpolluted S1), while an increased one was found in S2. Heterotrophic fungi followed the opposite trend. Actinomycetes and heat-resistant aerobic bacterial spores showed a variable trend depending on the soil type and Sb(V) treatment. The Biolog community level physiological profile indicated a reduced metabolic activity potential of microbial communities from the Sb-spiked S1 soils (e.g. <50% for Sb-1000 compared to the unpolluted S1), while an increase was recorded for those extracted from the Sb-spiked S2 soils (e.g. >2-fold for Sb-1000). The soil dehydrogenase activity followed the same trend. High-throughput 16S rRNA amplicon sequencing analysis revealed that Sb did not influence the bacterial α-diversity in both soils, while significantly affected the composition of the respective soil bacterial communities. Several phyla (e.g. Nitrosospira Nitrososphaeraceae, Adheribacter) were found positively correlated with the concentration of water-soluble Sb in soil. Overall, the results obtained suggest that the risk assessment in soils polluted with antimony should be a priority especially for alkaline soils where the high mobility of the anionic Sb(OH)6- species can pose, at least in the short-term, a serious threat for soil microbial abundance, diversity and functionality, soil fertility and eventually human health.

Antimony Sorption to Goethite: Effects of Fe(II)-Catalyzed Recrystallization

The environmental mobility and bioavailability of antimony (Sb) are strongly influenced by sorption to Fe(III) oxide minerals, such as goethite (αFeOOH). Exposure to aqueous Fe(II), as occurs, for ...

Antimony mobility during the early stages of stibnite weathering in tailings at the Beaver Brook Sb deposit, Newfoundland

The aqueous speciation and mineralogy of antimony (Sb) in waters and tailings at Beaver Brook antimony deposit have been analyzed to understand Sb mobility during the initial stages of stibnite (Sb2S3) weathering in a near-surface environment. Dissolution of stibnite in oxidizing conditions releases Sb in drainage water and Sb is incorporated into the mineral structures of several secondary minerals. The most abundant Sb host in Beaver Brook tailings is primary stibnite, which dissolves, releasing Sb(III) to the pore water which rapidly oxidizes to Sb(V). The maximum concentration of Sb in tailings pore water is 26.4 mg/L and only 0.9% is in the form of Sb(III). In all surface water, Sb concentration ranges from 0.01 to 26.1 mg/L (average 9.4 mg/L) and is mostly present in its Sb(V) form (98.9–99.2% of total Sb). The secondary minerals containing Sb formed in tailings impoundment include tripuhyite-like Sb–Fe oxides (FeSbO4) where Sb is an important part of their structure, with variable Fe/Sb ratios and Sb concentrations of up to 37.8% by weight (average of 21.7%). These are important Sb host phases in the top 30 cm of tailings. Iron oxides enriched in Sb, such as goethite (FeOOH), where Sb (average of 3.9% by weight) is adsorbed or incorporated in the structure are common but represent less than 1.3% of the total mass of Sb. The elevated Mg concentrations in tailing ponds and pore water promote the precipitation of brandholzite (Mg[Sb(OH)6]2·6H2O) (in association with gypsum) during dry periods, which is easily dissolved during rainy periods. Brandholzite dissolution may significantly contribute to the concentration of dissolved Sb, together with stibnite dissolution, whereas Sb–Fe oxides are stable in the neutral pH, oxidized surface environment. Arsenic (As) accompanies Sb in all media but its behavior differs from that of Sb. The source of As is arsenopyrite, which decomposes more slowly than stibnite. This may be due to the formation of oxidation rims on arsenopyrite grains composed of Fe, As, S, Sb, and Ca which slow the dissolution, whereas no rims are seen on stibnite. Also, despite similar As and Sb concentration in bulk tailings, the concentration of Sb in drainage water is higher than that of As. In pore water, As(III) is the dominant oxidation state of As suggesting that the oxidation of dissolved As is slower than that of Sb.

Soil organic matter affects arsenic and antimony sorption in anaerobic soils

Soil organic matter (SOM) affects arsenic (As) and antimony (Sb) mobility in soils under waterlogged conditions by acting as an electron donor, by catalyzing redox–cycling through electron shuttling and by acting as a competing ligand. This study was set up to disentangle these different effects of SOM towards As and Sb sorption in anaerobic soils. Nine samples were taken at different depths in an agricultural soil profile to collect samples with a natural SOM gradient (<1–40 g soil organic carbon kg−1). The samples were incubated either or not under waterlogged conditions in an anaerobic chamber for 63–70 days, and glucose (5 g C kg−1) was either or not added to the anaerobic incubated samples as an electron donor that neither acts as an electron shuttle nor as a competing ligand. The solid-liquid distribution coefficients (KD) of As and Sb were measured at trace levels. The KD values of As decreased ∼2 orders of magnitude upon waterlogging the SOM rich topsoil, while no additional changes were observed when glucose was added. In contrast, smaller changes in the As KD values were found in the low SOM containing subsoil samples, unless glucose was added that mobilised As. The Sb KD values increased upon reducing conditions up to factor 20, but again only in the high SOM topsoil samples. Surprisingly, the Sb immobilisation during waterlogging only occurred in Sb amended soils whereas the geogenic Sb was mobilised upon reducing conditions, although total dissolved Sb concentrations remained low (<10 nM). The change in As and Sb sorption upon waterlogging was similar in the SOM rich topsoil as in the low SOM subsoil amended with glucose. This suggests that the SOM dependent changes in As and Sb mobility in response to soil waterlogging are primarily determined by the role of SOM as electron donor.

Mechanism of microbial dissolution and oxidation of antimony in stibnite under ambient conditions

In this study, we demonstrate that a bacterial isolate Paraccocus versutus XT0.6 from the Xikuangshan antimony mine, the world largest antimony deposit, is capable of stibnite dissolution, oxidation of Sb(III), and formation of secondary Sb(V) bearing mineral. The isolate could oxidize dissolved Sb(III) aerobically and anaerobically. It was able to dissolve Sb(III) in solid minerals, which was subsequently oxidized to Sb(V) completely. Part of Sb(V) was scavenged by the formation of secondary Sb(V)-bearing mineral mopungite [NaSb(OH)6] in the biotic experiments. In contrast, Sb(III) released from mineral/rocks was only partially oxidized to Sb(V) and no secondary Sb-bearing mineral was formed in abiotic controls. These results demonstrated that microbial processes involved in the mobilization, oxidation, and transformation of antimony in minerals/rocks under ambient environmental conditions and offer new insights in biogeochemistry of Sb at mining areas.

Antimony mobility from E-waste plastic in simulated municipal solid waste landfills

The fate of antimony (Sb) leached from electronic and electrical equipment plastic when disposed of in a municipal solid waste (MSW) landfill was assessed using simulated anaerobic landfill lysimeters and three different batch leaching tests: toxicity characteristic leaching procedure (TCLP), EPA method 1313, and MSW leachate extractions. Plastic from cathode ray tube televisions sets was noted to have the highest Sb concentrations, and was thus the focus of the study. Sb leachability from EPA 1313 stat and TCLP were similar at approximately 0.1% by weight at the same pH (4.93), while MSW landfill leachates extracted less Sb at approximately 0.02% by weight. Solution pH was not the controlling factor, and other conditions resulting from the landfill leachate resulted in lower concentrations of leached Sb. In simulated landfill experiments, Sb leached at approximately 0.01% by weight after a liquid-to-solid ratio of 3. Sb behaves differently in the landfill environment than arsenic leaching from a similar study, most likely from the reducing conditions brought on by the decomposing waste.

Effect of Water Chemistry on Antimony Removal by Chemical Coagulation: Implications of ζ-Potential and Size of Precipitates.

The process of coagulation and precipitation affect the fate and mobility of antimony (Sb) species in drinking water. Moreover, the solubility and physico-chemical properties of the precipitates may be affected by the media chemistry. Accordingly, the present study aimed to investigate the removal of Sb(III, V) species by ferric chloride coagulation under various water chemistry influences with a particular focus on the role of the properties of the precipitates. The results indicated that the amount of Sb(III) removed increased with increasing solution pH, showing the insignificant effects of the hydrodynamic diameter (HDD) and ζ-potential of the precipitates. However, no Sb(V) removal occurred at alkaline pH values, while a highly negative ζ-potential and the complete dissolution of precipitates were observed in the aqueous solution. The solution pH was also useful in determining the dominant coagulation mechanisms, such as co-precipitation and adsorption. The Fe solubility substantially affects the Sb removal at a certain pH range, while the HDD of the precipitates plays an insignificant role in Sb removal. The presence of divalent cations brings the ζ-potential of the precipitates close to point of zero charge (pzc), thus enhancing the Sb(V) removal at alkaline pH conditions. Pronounced adverse effects of humic acid were observed on Sb removal, ζ-potential and HDD of the precipitates. In general, this study may provide critical information to a wide group of researchers dealing with environmental protection from heavy metal pollution.

Low-Molecular-Weight Organic Acid Complexation Affects Antimony(III) Adsorption by Granular Ferric Hydroxide.

Antimony(III) mobility in natural aquatic environments is generally enhanced by dissolved organic matter. Tartaric acid is often used to form complexes with and stabilize dissolved Sb(III) in adsorption studies. However, competition between such low-molecular-weight organic acid complexation and adsorption of Sb(III) has received little attention, which prompted us to measure Sb(III) adsorption by iron oxyhydroxide adsorbents commonly used in water treatment plants. Sb K-edge X-ray absorption fine structure (EXAFS) spectra gave Sb-O and Sb-Fe distances and coordinations compatible with a bidentate binuclear inner-sphere complex with trigonal Sb(O,OH)3 polyhedra sharing corners with Fe(O,OH)6 octahedra and a bidentate mononuclear inner-sphere complex but with Sb(O,OH)4 tetrahedra at alkaline pH. Experimental batch titration data were fitted using the charge-distribution multisite surface complexation (CD-MUSIC) model, constrained by the EXAFS molecular level information and taking competitive effects by the organic ligand into consideration. The proportion adsorbed at acid to neutral pH decreased as the Sb(III) concentration increased. The CD-MUSIC adsorption model indicates that this was solely caused by strong competition from tartrate complexation in solution, which leads to adsorption constants higher than those derived without taking this competition into account. The adsorption model results allow for calculating a pe-pH predominance diagram using the USGS PhreePlot code. The study provides consistent surface complexation stability constants, allowing the new database to be used also to reliably model adsorption of toxic oxyanions in anoxic aqueous environments: for example, to accurately simulate competition between Sb(III) and As(III).

Enhanced removal of antimony by acid birnessite with doped iron ions: Companied by the structural transformation

In the environment, antimony as a priority control pollutant is mainly associated with Fe- or Mn- related minerals. In this work, acid birnessite (AB) doped with iron was synthesized as the artificial mineral to study the adsorption and oxidation of antimony. As compared to the pristine birnessite, Fe-doping birnessites show a markedly enhanced removal efficiency for both Sb(III) and Sb(V), where 10% Fe exhibited an excellent adsorption capacity of 759 mg/g Sb(III). The removal of Sb(III) clearly underwent a novel kinetic process of adsorption-desorption- (re-adsorption). By monitoring the kinetics with XRD, XPS, and IR, it is demonstrated that the three-stage kinetics were attributed to the strong interaction between Sb(III) and birnessite, including Sb(III) oxidation, followed by destruction of birnessite and then phase transformation into vernadite. Furthermore, the increase of iron content doped into birnessite enhanced the rate of its phase transition, which led to an increased adsorption of the oxidized antimony on the surface of vernadite by substituting iron and manganese associated with hydroxyl group. This work suggested that the strong interactions between heavy metal ions and mineral particles, more than adsorption, are critical to the transformation, mobility and biotoxicity of antimony in nature.