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Increasing soil contamination of arsenic (As) and antimony (Sb) is posing a serious concern to human health. Due to insufficient studies on Sb, the biogeochemical behaviour and plant uptake of Sb are assumed to be similar to that of As. As part of extensive research unravelling As and Sb biogeochemistry and plant uptake, the diffusive gradients in thin films (DGT) technique and sequential extraction procedure (SEP) were applied to evaluate As and Sb uptake by the white icicle radish (Raphanus sativus) cultivated in diluted cattle dip soils contaminated with As only and diluted mining soils contaminated with both As and Sb under agricultural conditions. Labile As and Sb in these soils measured by DGT (C DGT ), soil solution (C sol ), and SEP (C SEP-labile ), were compared with As and Sb bioaccumulation in R. sativus tissues. Regardless of contamination sources and measurement techniques, the results showed that As was consistently more labile than Sb although total As concentrations in two soil types were lower than total Sb. Labile As in cattle dip soils was higher than that in mining soils, although there were no significant differences in soil As concentrations. The analysis of R. sativus tissues revealed that the overall As bioaccumulation was 4.5-fold higher than for Sb, and that As translocation to shoots was limited. In contrast, considerable Sb translocation to shoots was observed. The As and Sb bioaccumulation were strongly correlated with their C SEP-labile , C DGT , and C sol (R 2  = 0.87-0.99), demonstrating the effectiveness of these techniques in predicting As and Sb in the white icicle radish. Compared with the cherry bell radish previously studied, the white icicle radish exhibited higher bioaccumulation factors (BAF) for Sb, but lower BAF for As, and lower translocation of As and Sb to shoots, providing understanding of how As and Sb are accumulated by radish cultivars., (Crown Copyright © 2019. Published by Elsevier Ltd. All rights reserved.)

Metals and metalloids are priority contaminants due to their non-degradable and bioaccumulative nature, and their ability to regulate and perturb diverse physiological processes in various species. Metal(loid)s are known to cause oxidative stress through production of reactive oxygen species (ROS), thus related endpoints like lipid peroxidation (LPO) have received considerable attention as biomarkers of exposure. However, the implications of metal(loid) toxicity including LPO on actual lipid profiles of species inhabiting contaminated systems are poorly understood. Here we applied Nuclear Magnetic Resonance (NMR) spectroscopy for untargeted lipidomics of mosquitofish (Gambusia holbrooki) collected from reference and metal(loid)-contaminated wetlands. We measured a range of trace elements in water and fish using inductively coupled plasma - mass spectrometry (ICP-MS), and interpreted site differences in the lipid profiles of mosquitofish in the context of known physiological responses to sub-lethal metal(loid) exposure. Results indicate deregulation of cellular membrane lipids (i.e., glycerophospholipids, cholesterol and sphingolipids) and increased energy storage molecules (i.e., triacylglycerols and fatty acids) in fish from the contaminated wetland. These responses are consistent with the recognised induction of oxidative stress pathways in organisms exposed to metal(loid)s and could also be symptomatic of mitochondrial dysfunction and endocrine disruption. It is difficult to attribute metal(loid)s as the sole factor causing differences between wetlands, and a more controlled experimental approach is therefore warranted to further explore mechanistic pathways. Nevertheless, our study highlights the benefits of untargeted 1 H NMR-based lipidomics as a relatively fast and simple approach for field-scale assessment and monitoring of organisms inhabiting metal(loid) contaminated environments., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Antimony (Sb) and arsenic (As) are priority environmental contaminants that often co-occur at mining-impacted sites. Despite their chemical similarities, Sb mobility in waterlogged sediments is poorly understood in comparison to As, particularly across the sediment-water interface (SWI) where changes can occur at the millimeter scale. Combined diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques provided a high resolution, in situ comparison between Sb, As, and iron (Fe) speciation and mobility across the SWI in contaminated freshwater wetland sediment mesocosms under an oxic-anoxic-oxic transition. The shift to anoxic conditions released Fe(II), As(III), and As(V) from the sediment to the water column, consistent with As release being coupled to the reductive dissolution of iron(III) (hydr)oxides. Conversely, Sb(III) and Sb(V) effluxed to the water column under oxic conditions and fluxed into the sediment under anoxic conditions. Porewater DGT-DET depth profiles showed apparent decoupling between Fe(II) and Sb release, as Sb was primarily mobilized across the SWI under oxic conditions. Solid-phase X-ray absorption spectroscopy (XAS) revealed the presence of an Sb(III)-S phase in the sediment that increased in proportion with depth and the transition from oxic to anoxic conditions. The results of this study showed that Sb mobilization was decoupled from the Fe cycle and was, therefore, more likely linked to sulfur and/or organic carbon (e.g., most likely authigenic antimony sulfide formation or Sb(III) complexation by reduced organic sulfur functional groups).

Antimony is a priority environmental contaminant that is relatively poorly studied compared to other trace metal(loid)s. In particular, the behaviour of antimony in wetland sediments, where anaerobic conditions often dominate, has received considerably less attention compared to well-drained terrestrial soil environments. Here we report the results of a spatial assessment of antimony in the sediments and vegetation of a freshwater wetland exposed to stibnite tailings for the past forty years. The concentration of antimony in the sediment decreased rapidly with distance from the tailings deposit, from a maximum of ∼22,000 mg kg -1 to ∼1000 mg kg -1 at a distance of ∼150 m. In contrast, arsenic was distributed more evenly across the wetland, indicating that it was more mobile under the prevailing hypoxic/anoxic conditions. Less clear trends were observed in the tissues of wetland plants, with the concentrations of antimony in waterlilies (2.5-195 mg kg -1 ) showing no clear trends with distance from the tailings deposit, and no correlation with sediment concentrations. Sedges and Melaleuca sp. trees had lower antimony concentrations (<25 mg kg -1 and 5 mg kg -1 , respectively) compared to waterlilies, but showed a non-significant trend of higher concentrations closer to the tailings. For all vegetation types sampled, antimony concentrations were consistently lower than arsenic concentrations (Sb:As = 0.27-0.31), despite higher concentrations of antimony in the sediment. Overall, the results of this study highlight clear differences in the behaviour of antimony and arsenic in freshwater wetlands, which should be considered during the management and remediation of such sites., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The enrichment of soil arsenic (As) and antimony (Sb) is putting increasing pressure on the environment and human health. The biogeochemical behaviour of Sb and its uptake mechanisms by plants are poorly understood and generally assumed to be similar to that of As. In this study, the lability of As and Sb under agricultural conditions in historically contaminated soils was assessed. Soils were prepared by mixing historically As and Sb-contaminated soil with an uncontaminated soil at different ratios. The lability of As and Sb in the soils was assessed using various approaches: the diffusive gradients in thin films technique (DGT) (as CDGT), soil solution analysis, and sequential extraction procedure (SEP). Lability was compared to the bioaccumulation of As and Sb by various compartments of radish (Raphanus sativus) grown in these soils in a pot experiment. Irrespective of the method, all of the labile fractions showed that both As and Sb were firmly bound to the solid phases, and that Sb was less mobile than As, although total soil Sb concentrations were higher than total soil As. The bioassay demonstrated low bioaccumulation of As and Sb into R. sativus due to their low lability of As and Sb in soils and that there are likely to be differences in their mechanisms of uptake. As accumulated in R. sativus roots was much higher (2.5-21 times) than that of Sb, while the Sb translocated from roots to shoots was approximately 2.5 times higher than that of As. As and Sb in R. sativus tissues were strongly correlated with their labile concentrations measured by DGT, soil solution, and SEP. These techniques are useful measures for predicting bioavailable As and Sb in the historically contaminated soil to R. sativus. This is the first study to demonstrate the suitability of DGT to measure labile Sb in soils., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Mobilization of arsenic from freshwater and estuarine sediments during the transition from oxic to anoxic conditions was investigated using recently developed diffusive sampling techniques. Arsenic speciation and Fe(II) concentrations were measured at high resolution (1-3 mm) with in situ diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques. Water column anoxia induced Fe(II) and As(III) fluxes from the sediment. A correlation between water column Fe(II) and As(III) concentrations was observed in both freshwater (r(s) = 0.896, p < 0.001) and estuarine (r(s) = 0.557, p < 0.001) mesocosms. Porewater sampling by DGT and DET techniques confirmed that arsenic mobilization was associated with the reductive dissolution of Fe(III) (hydr)oxides in the suboxic zone of the sediment; a relationship that was visible because of the ability to measure the coincident profiles of these species using combined DGT and DET samplers. The selective measurement of As(III) and total inorganic arsenic by separate DGT samplers indicated that As(III) was the primary species mobilized from the solid phase to the porewater. This measurement approach effectively ruled out substantial As(V) mobilization from the freshwater and estuarine sediments in this experiment. This study demonstrates the capabilities of the DGT and DET techniques for investigating arsenic speciation and mobilization over a range of sediment conditions.

A diffusive gradients in thin films (DGT) technique for selectively measuring As(III) utilizes commercially available 3-mercaptopropyl-functionalized silica gel. Deployment of the new technique alongside the Metsorb-DGT for total inorganic arsenic allows the calculation of As(III) directly and As(V) by difference. Uptake of As(III) by mercapto-silica was quantitative and elution with a mixture of 1 mol L(-1) HNO(3) and 0.01 mol L(-1) KIO(3) gave a recovery of 85.6 ± 1.7%. DGT validation experiments showed linear accumulation of As(III) over time (R(2) > 0.998). Accumulation was unaffected by varying ionic strength (0.0001-0.75 mol L(-1) NaNO(3)) and pH (3.5-8.5). Deployment of mercapto-silica DGT and Metsorb DGT in seawater spiked with As(III) and As(V) demonstrated the ability of the combined approach to accurately quantify both species in the presence of potential competing ions. Ferrihydrite DGT, which has been previously reported for the measurement of total inorganic arsenic, was evaluated in seawater and shown to underestimate both As(III) and As(V) at longer deployment times (72 h). Reproducibility of the new mercapto-silica DGT technique was good (relative standard deviations < 9%), and the average method detection limit was sufficiently low to allow quantification of ultratrace concentrations of As(III) (0.03 μg L(-1); 72 h deployment).

A new diffusive gradients in a thin film (DGT) technique, using a titanium dioxide based adsorbent (Metsorb), has been developed and evaluated for the determination of dissolved inorganic arsenic and selenium. As(III), As(V), and Se(IV) were found to be quantitatively accumulated by the adsorbent (uptake efficiencies of 96.5-100%) and eluted in 1 M NaOH (elution efficiencies of 81.2%, 75.2%, and 88.7%). Se(VI) was not quantitatively accumulated by the adsorbent (<20%). Laboratory DGT validation experiments gave linear mass uptake over time (R(2) >or= 0.998) for As(III), As(V), and Se(IV). Consistent uptake occurred over pH (3.5-8.5) and ionic strength (0.0001-0.75 mol L(-1) NaNO(3)) ranges typical of natural waters, including seawater. Field deployments of DGT probes with various diffusive layer thicknesses confirmed the use of the technique in situ, allowing calculation of the diffusive boundary layers and an accurate measurement of inorganic arsenic. Reproducibility of the technique in field deployments was good (relative standard deviation <8%). Limits of detection (4 day deployments) were 0.01 microg L(-1) for inorganic arsenic and 0.05 microg L(-1) for Se(IV). The results of this study confirmed that DGT with Metsorb was a reliable and robust method for the measurement of inorganic arsenic and the selective measurement of Se(IV) within useful limits of accuracy.

Background and Aims: Bioremediation of soils contaminated with metal(loid)s is an attractive research area due to its sustainability and economic benefits. In the Slovak Republic, there are several abandoned mines containing high concentrations of arsenic (As) and antimony (Sb). This calls for new options for removing these hazardous metalloids from contaminated substrates. Studies on bioleaching of soils co-contaminated with both metalloids are very rare. This study aimed to test the effectiveness of bioleaching of soils heavily co-contaminated with As and Sb (up to 1463 mg.kg–1 and 5825 mg.kg–1, respectively) at a former stibnite mining site (Poproč, eastern Slovakia) through biostimulation and bioaugmentation. Methods: Bioleaching of As and Sb from four soils was induced by biostimulation of autochthonous microflora with Sabouraud medium (SAB) and SAB+glucose, and bioaugmentation of the soil with bacterial strains Cupriavidus oxalaticus and Cupriavidus metallidurans. Soil samples were subjected to determination of physico-chemical properties, microbiological parameters, and additional mineralogical analysis. Results: An inverse relationship between the total metalloid concentration and the microbial diversity was confirmed. In experiments with Cupriavidus metallidurans and Cupriavidus oxalaticus, mean bioleached As fractions were 37.6% and 41.3%, while Sb bioleaching was significantly lower, ranging between 17.0–26.2%. The mean bioleached fraction of As and Sb using SAB was 40.7% and 14.4%, respectively. The addition of glucose to SAB increased As bioleaching (50.7%) but not that of Sb. Conclusion: Collectively, the results highlighted a role of microorganisms in the mobility of metalloids in soils with their prospective applications in remediation of contaminated sites. [ABSTRACT FROM AUTHOR]

Urban soils contaminated with heavy metals and pesticide residues are of great concern because of their adverse impact on human health. A total of 66 agricultural topsoil samples (15 cm) were collected to represent the study area and determine how anthropogenic activities adversely affect soil quality and human health. Sampling was conducted in the summer, when it was dry and hot, and in the winter, after atmospheric deposition. Seventeen potentially hazardous metals/metalloids (Ag, As, Al, B, Ba, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Mo, Pb, Se, Zn, and V) were measured in the soils. The mean concentrations of metals ranged between 0.05 and 8080 mg/kg, and their distribution was site-specific, with high pollution at the sampling sites owing to proximity to human activities. In agricultural areas, the greatest arsenic concentration was recorded at 48 mg/kg. The potential ecological risk index (PERI) and health hazard index (HI) were calculated, as well as metal contamination indices including contamination factor (Cf), geo-accumulation index (Igeo), and pollution load index (PLI). The mean PLI was calculated to be 4.89, indicating that the area is highly polluted. The potential ecological risk index showed remarkably high risks for As, Cd, and Hg, and moderate risks for Ni and Pb. The arsenic hazard index (HI) was greater than one (2.41) in children, indicating a risk of exposure through ingestion. Pesticide residue analyses were performed in areas where the metal intensity was high. Banned or restricted organochlorine pesticide (OCPs) residues, including, dieldrin, endrin ketone, endosulfan I, II, heptachlor, heptachlor epoxide, lindane (γ-HCH), PP-DDD, and methoxychlor, were detected between 0.002 and 1.45 mg/kg in the soil samples. [ABSTRACT FROM AUTHOR]

Antimony (Sb) and arsenic (As) co-contamination occurs in Sb smelting areas and is harmful to the surrounding ecological environment. The purpose of this study is to explore the spatial distribution characteristics of Sb and As in abandoned Sb smelting area and carry out risk assessments. Soil samples were collected from the smelting area profile and background points, and groundwater samples were also collected. Samples from two geological background sections were collected to understand the geological background characteristics of Sb and As. The spatial distribution was drawn via the inverse distance weighted interpolation method. The hazard assessment was carried out by the geo-accumulation index and potential ecological hazard methods. The results showed that special high geological background value of Sb and As in study area. Sb and As co-contamination is one of the characters in soil. And the contents of Sb and As decrease as depth increases, reflecting the weak migration capacity. The spatial distribution of Sb and As is affected by slag distribution and rainfall leaching. The Sb content in groundwater was higher in the wet and normal seasons than in the dry season, slag leaching may be one of the elements. The potential ecological hazards of Sb and As are high and considerable, respectively. In abandoned smelting area with high geological background values, it is necessary to focus on the pollution abatement and protection of ecological health. [ABSTRACT FROM AUTHOR]

The impact of water and bottom sediment pollution of a river subjected to a strong industrial anthropogenic pressure of metal(loid) (including arsenic and its species) accumulation in riverbank plants such as Solidago virgaurea L., Phragmites L. and Urtica dioica L. was investigated. The high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) technique was used to study organic and inorganic arsenic species in selected plants and their response to heavy metal and arsenic contamination. The modified BCR extraction results showed that arsenic was mainly bound to the mobile reducible and organic-sulfide fractions in the Kłodnica River bottom sediments. Research has shown that the bottom sediments of the Kłodnica River are contaminated with metals, including Pb, Zn, Ni, As, and among arsenic species, the As(V) form dominated quantitatively, with its highest concentration being 49.3 mg kg−1 and the organic species occurred extremely rarely. The highest concentration of arsenic, among the tested plants, occurred in Phragmites communis L. The evaluation of the bottom sediment pollution was performed using Sb/As factor, geoaccumulation index (Igeo), enrichment factor (EF) and pollution load index (PLI). The ability of the plant to assimilate metals from the substrate was studied by calculation of the bioaccumulation factor (BAF). Values of the Igeo change in a wide range from class 1 (uncontaminated to moderately polluted for Cu and Zn) at the first sampling point, to 5 (highly to extremely polluted for Ba and Fe) at the K4 sampling point. The Igeo results show an increase in the contamination with elements toward the runoff of the Kłodnica River. [ABSTRACT FROM AUTHOR]

Legacy arsenic (As) contamination from past mining operations remains an environmental concern in lakes of the Yellowknife area (Northwest Territories, Canada) due to its post-depositional mobility in sediment and potential for continued remobilization to surface waters. Warmer temperatures associated with climate change in this subarctic region may impact As internal loading from lake sediments either by a direct effect on sediment porewater diffusion rate or indirect effects on microbial metabolism and sediment redox conditions. This study assessed the influence of warmer temperatures on As diffusion from contaminated sediment of two lakes with contrasting sediment characteristics using an experimental incubation approach. Sediments from Yellowknife Bay (on Great Slave Lake) contained predominately clay and silt with low organic matter (10%) and high As content (1675 μg/g) while sediments of Lower Martin Lake had high organic matter content (~70%) and approximately half the As (822 μg/g). Duplicate sediment batches from each lake were incubated in a temperature-controlled chamber, and overlying water was kept well-oxygenated while As flux from sediment was measured during four weekly temperature treatments (7°C to 21°C, at ~5°C intervals). During the experiment, As diffused from sediment to overlying water in all cores and temperature treatments, with As fluxes ranging from 48–956 μg/m2/day. Arsenic fluxes were greater from Yellowknife Bay sediments, which had higher solid-phase As concentrations, compared to those of Lower Martin Lake. Short-term warming did not stimulate As flux from duplicate cores of either sediment type, in contrast with reported temperature enhancement in other published studies. We conclude that warmer temperatures were insufficient to strongly enhance sediment As diffusion into overlying oxic waters. These observations are relevant for evaluating climate-warming effects on sediment As mobility in subarctic lakes with little or no thermal stratification and a well-oxygenated water column. [ABSTRACT FROM AUTHOR]

Arsenic (As) is commonly sequestered at the sediment–water interface (SWI) in mining-impacted lakes through adsorption and/or co-precipitation with authigenic iron (Fe)-(oxy)hydroxides or sulfides. The results of this study demonstrate that the accumulation of organic matter (OM) in near-surface sediments also influences the mobility and fate of As in sub-Arctic lakes. Sediment gravity cores, sediment grab samples, and porewaters were collected from three lakes downstream of the former Tundra gold mine, Northwest Territories, Canada. Analysis of sediment using combined micro-X-ray fluorescence/diffraction, K-edge X-ray Absorption Near-Edge Structure (XANES), and organic petrography shows that As is associated with both aquatic (benthic and planktonic alginate) and terrestrially derived OM (e.g., cutinite, funginite). Most As is hosted by fine-grained Fe-(oxy)hydroxides or sulfide minerals (e.g., goethite, orpiment, lepidocrocite, and mackinawite); however, grain-scale synchrotron-based analysis shows that As is also associated with amorphous OM. Mixed As oxidation states in porewater (median = 62% As (V), 18% As (III); n = 20) and sediment (median = 80% As (-I) and (III), 20% As (V); n = 9) indicate the presence of variable redox conditions in the near-surface sediment and suggest that post-depositional remobilization of As has occurred. Detailed characterization of As-bearing OM at and below the SWI suggests that OM plays an important role in stabilizing redox-sensitive authigenic minerals and associated As. Based on these findings, it is expected that increased concentrations of labile OM will drive post-depositional surface enrichment of As in mining-impacted lakes and may increase or decrease As flux from sediments to overlying surface waters. [ABSTRACT FROM AUTHOR]

Aims: The biogeochemical cycles of elements from soils to plants are mainly governed by their rhizosphere processes. Understanding these processes is challenging and remains largely unresolved due to the complex interrelationships among different elements and due to a lack of appropriate techniques for simultaneous spatiotemporal monitoring. Methods: This study employed an updated In-situ Porewater Iterative (IPI) sampler to collect porewater across the rice rhizosphere at a spatial resolution of 1.7 mm and a time interval of 3–10 days. An IPI sampler array (0–22 mm measurement distance every 1.7 mm) was adopted to capture the in situ spatiotemporal dynamics of ten elements (Fe, Mn, As, P, S, Cr, Co, Zn, Sb and Cd) in the paddy rhizosphere to examine their covarying changes in time and space dimensions, with an emphasis on As and Cd. Results: The findings revealed that the solute-phase concentration of most elements, other than Sb and Cd, increased to a peak after 30 days of paddy soil flooding and then decreased. Additionally, Sb and Cd continuously decreased during flooding. Fe (−52%), Mn (−17%), P (−43%), Co (−11%), and As species (−74%) were substantially immobilized within a 10 mm zone around the roots, while Zn (28%) and Cd (41%) increased. Almost all arsenite-oxidizing genes were significantly promoted in the rhizosphere. Conclusions: Our study showed most sampled elements covaried with Fe both in time and space in the rhizosphere, but the elements are temporally and spatially determined by multiple biogeochemical processes in soils as well as exudates from plant roots. [ABSTRACT FROM AUTHOR]

Broussonetia papyrifera, Cryptomeria fortunei, Arundo donax, and Robinia pseudoacacia were planted on a zinc smelting slag site. The habitat conditions and spatial distribution of arsenic (As) and antimony (Sb) in slag were analyzed after seven years of restoration. The results showed that the pH, conductivity (EC), and moisture content of phytoremediated slag were lower than those of the control slag. The redox potential (Eh) and EC decreased with increasing slag depth. Phytostabilization significantly increased the contents of total nitrogen (TN), total phosphorus (TP), available nitrogen (AN), available phosphorus (AP), and dissolved organic carbon (DOC) in slag. TN, AN, AP, and DOC in slag showed obvious surface polymerization. Phytostabilization increased the content of calcite and gypsum in the slag. As and Sb concentrations were significantly lower than control slag, with an average decrease of 651–844 and 422–693 mg·kg −1, respectively. Residual As and Sb in phytoremediated slag was the most present form, the proportion of which was higher than that in the control slag. The proportions of calcium-bound and aluminum-bound As and Sb were lower. The contents of arsenic and antimony in plants had lower levels and followed the order of roots > leaves > stems. As and Sb showed a strong positive correlation with pH, EC, moisture content, and a negative correlation with TN, TP, AN, AP, and DOC. In summary, phytostabilization significantly improved slag site conditions and reduce As and Sb available concentrations. Novelty statement Co-contamination of As and Sb is common in mining areas because of similar chemical properties. There are only few reports on the effects of matrix modification and phytoremediation (without additional soil cover) on the soil physicochemical properties, the spatial distribution, and the bioavailability of As and Sb in zinc slag with an alkaline pH. The research determined that phytostabilization significantly improved slag site conditions and reduce As and Sb available concentrations. The results obtained can be used as necessary information for the large-scale ecological restoration or vegetation reconstruction of zinc smelting slag yards. [ABSTRACT FROM AUTHOR]

We studied the speciation of arsenic and antimony in the rhizosphere of 6 pioneer plants grown in zinc smelting slag to understand the main affecting factors of phytoremediation. Compared with the control slag, the pH of rhizosphere decreased significantly (p < 0.05) and the DOC content increased significantly (p < 0.05). Overall, the contents of arsenic (except Photinia serrulata and Lolium perenne) and antimony in the rhizosphere were lower than those of control slag. The proportions of residual arsenic and antimony in the rhizosphere were the highest and significantly higher than control slag. Exchangeable state, aluminum-bound state and calcium-bound state were lower than control slag. The contents of arsenic and antimony in plants were normal and followed the order of roots > leaves > stems. Arsenic and antimony were significantly positively correlated with Free iron and aluminum oxides and negatively correlated with DOC. After 7 years of phytoremediation, the content and bioavailability of arsenic and antimony in the rhizosphere were significantly reduced and have a normal contents in plants. It is speculated that phytoremediation increases the migration of arsenic and antimony to the surrounding area, and Photinia serrulata and Lolium perenne exhibited the best performance on stabilise arsenic in slag. [ABSTRACT FROM AUTHOR]

Environmental context: Toxicity and mobility of antimony and arsenic in aqueous systems are largely determined by their speciation and redox chemistry. In a highly contaminated freshwater system, one antimony species (dissolved SbV) dominated, while dissolved arsenic was more responsive to environmental conditions. Arsenic (as AsV) increased significantly during a drought period; this increase in As mobility presents a threat for first flush events and water contamination in a changing climate. Aqueous and solid-state antimony (Sb) and arsenic (As) speciation is assessed in an Australian freshwater system contaminated by mining of primary sulfide minerals. The study aims to understand metalloid transformation and mobilisation in the system, and coincides with a severe drought providing the opportunity to examine the influence of extreme low-flow conditions. X-ray absorption spectra identified only SbV in <2 mm sediments, despite boulder size stibnite evident in the creek. Roméite-group minerals were detected by X-ray diffraction in oxidation rims of creek-bed stibnite, which potentially limit the contribution of dissolved SbIII to the waterway. Arsenic in <2 mm sediments was dominated by AsV (17–91 %) and orpiment (16–93 %), while the co-occurrence of AsIII (11–36 %) with orpiment suggests that primary As minerals are an important ongoing source of AsIII to the system. Dissolved metalloids (<45 µm filtered) dominated total water column concentrations and comprised mainly pentavalent species. Arsenic(III) was however identified in most water samples (up to 6.6 µg L−1), while dissolved SbIII was only detected in one sample (3.4 µg L−1) collected during the drought period. Dissolved AsV increased significantly in samples collected in low-flow conditions, considered a result of reductive dissolution of sediment Fe-oxyhydroxide host phases, but a similar increase in dissolved Sb was not observed. This study highlights a greater risk from As in this system, and the likelihood of increased As mobility under the warmer and drier environmental conditions predicted with climate change, especially during first-flush events. Environmental context. Toxicity and mobility of antimony and arsenic in aqueous systems are largely determined by their speciation and redox chemistry. In a highly contaminated freshwater system, one antimony species (dissolved SbV) dominated, while dissolved arsenic was more responsive to environmental conditions. Arsenic (as AsV) increased significantly during a drought period; this increase in As mobility presents a threat for first flush events and water contamination in a changing climate. [ABSTRACT FROM AUTHOR]

Mining activities are acknowledged to introduce contaminants into localised environments and cause wider spread diffuse pollution. The concentration, distribution and fate of arsenic (As) and antimony (Sb) were studied at the former metalliferous Louisa Mine at Glendinning, Scotland. Soils and surface water were sampled and subsequently analysed to map the distribution of contamination and identify pollution sources. The maximum concentrations of As and Sb of 15,490 and 1504.2 mg kg−1, respectively, were determined in soils associated with the ore processing area and spoil heaps. The fractions of dissolved As and Sb in soils were < 1 and < 5% of total soil content, respectively, confirming findings of previous studies that As and Sb are relatively immobile. Yet, the concentrations of As and Sb released by soils exceeded regulatory limits. Concentrations of As and Sb in surface water in the immediate vicinity of the mine were impacted by a gully discharge, but rapidly diluted. While the concentrations affected by the run-off waters did not exceed EU environmental standards for freshwater, the concentrations of both, As and Sb, sharply increased above the said environmental standards approximately 100 m downstream of the mine site. The unaltered As-to-Sb ratio in water samples suggests a geogenic source. While there is a justifiable concern about the soil pollution caused by the historic mining in the area, the Glenshanna Burn is affected more by indigenous geochemical processes than the derelict mine. [ABSTRACT FROM AUTHOR]

This study aimed to investigate the Sb and As co-accumulating processes of Pteris vittata under soil culture condition, including the transformation of Sb and As, and the difference in co-accumulating ability among different plant species/populations. Two populations of P. vittata and one population of As-tolerant species Holcus lanatus L. were grown on soil co-contaminated by Sb and As. Sb and As speciation in plants was assessed by X-ray absorption near-edge structure (XANES) spectroscopy. P. vittata displayed strong As- but limited Sb-accumulating ability, with the highest shoot concentrations of As and Sb reaching 455 and 26 mg kg−1, respectively. After 28 days culture, the concentrations of Sb and As in the soil solution were reduced by up to 22% and 36% in the P. vittata treatments, respectively. Holcus lanatus showed limited uptake for both metalloids. In P. vittata, the reduction of arsenate to arsenite occurred (with As in shoots all existing as arsenite), but limited reduction of antimonate to antimonite (with more than 90% of Sb in shoots existing as antimonate) was observed. In terms of the differences in metalloid uptake between the two P. vittata populations, the population from the habitat with higher soil As concentration showed 35% higher As uptake than the population from the habitat with lower As concentration. This populational difference may partly result from varying As transformation efficiencies. However, no significant difference was observed in Sb accumulation between the two populations. [ABSTRACT FROM AUTHOR]

Diffusive gradients in thin films technique (DGT) is a dynamically passive sampling technique which has been applied increasingly to the environmental monitoring field. In the preliminary period, the DGT with zirconium hydroxide-silver iodide as the binding phase (ZrO-AgI DGT) has been developed for the determination of sulfide (S(II)). On this basis, this paper developed its determination method for inorganic arsenite (As(III)) to further realize the simultaneous and high-resolution measurements of labile inorganic As and S(II) in sediments. ZrO-AgI binding gel had a strong ability in adsorbing and fixing As(III), showing a linear increase in the initial 12.5 min. After saturation of S(II) on ZrO-AgI binding gel, the adsorption rate and adsorption capacity of As(III) reduced by 8 and 14%, respectively. A stable elution rate (89.1 ± 2.2%) was obtained by extraction of As(III) on the binding gel using a mixture solution of 1.0 M NaOH and 1.0 M H2O2 (1:1). The DGT capacity of As(III) determined by the ZrO-AgI DGT was 23.6 μg cm−2. DGT uptakes of As(III) were independent of pH (4.0-9.0) and ionic strength (0.01-100 mM), and they did not interfere with each other during the uptake process. Simultaneous measurements of labile As and S(II) in four sediment cores of Taihu Lake (China) with ZrO-AgI DGT showed that they had similarly vertical distributions in the top 16-mm layer in one core and in the whole profile up to the 35 mm depth in two cores. It likely reflected a simultaneous release of As and S(II) in sediments by synchronous reduction of As-hosted oxidized iron and sulfate, respectively. The simultaneous decreases of labile As and S(II) from their co-precipitation (e.g., As2S3) were not obvious in deeper sediment layer through the measurement with ZrO-AgI DGT. [ABSTRACT FROM AUTHOR]

Purpose: Understanding the status and dynamics of labile arsenic (As), iron (Fe), and manganese (Mn) across the sediment/water interface (SWI) is essential for As cycling in eutrophic lakes. This study conducted systematic monitoring of labile As, Fe, and Mn in water and sediments in regions of varying eutrophic levels in Lake Taihu to investigate Fe- or Mn-coupled cycling of As in sediments.Materials and methods: We arranged high-resolution combined ZrO-Chelex diffusive gradients in thin films (DGT) probes in intact sediment cores to measure labile As, Fe, and Mn (i.e., DGT-labile As, Fe, and Mn) under static condition for 24 h. After retrieval, we rinsed each probe first with lake water and then with deionized water to remove any visible sediment particles for analysis.Results and discussion: Results showed that DGT-labile As in overlying water and sediments was relatively higher in the middle or hyper-eutrophic regions compared to the mesotrophic region. Diffusive flux across the SWI further demonstrated that the internal dissolution of As in the middle or hyper-eutrophic region was stronger than the mesotrophic region, indicating that eutrophic environments may facilitate As release in sediments. We observed a positive correlation between DGT-labile As and Fe or Mn, which indicated that the reductive dissolution of As binding Fe/Mn oxyhydroxides in sediments was responsible for the internal release of As, which strengthens under eutrophic environments. Furthermore, the DGT-labile molar ratio of Fe/As or Mn/As had a significant positive relation with Fd, further confirming that labile Fe or Mn is much more relevant for sediment As cycling.Conclusions: Eutrophic environments facilitated reductive dissolution of As binding Fe/Mn oxyhydroxides in sediments, resulting in the release of more labile As in the middle or hyper-eutrophic region. [ABSTRACT FROM AUTHOR]

The in situ stabilization has been widely used to remediate metal-contaminated soil. However, the long-term retaining performance of heavy metals and the associated risk after in situ stabilization remains unclear and has evoked amounting concerns. Here, Pb- or As-contaminated soil was stabilized by a commercial amendment. The availability of Pb and As after in situ stabilization were estimated by ten different in vitro chemical extractions and DGT technique. After amendment application, a significant decline in extractable Pb or As was observed in treatments of Milli-Q water, 0.01 M CaCl, 0.1 M NaNO, 0.05 M (NH)SO, and 0.43 M HOAc. Potential available metal(loid)s determined by DGT also showed remarkable reduction. Meanwhile, the results of in vivo uptake assays demonstrated that Pb concentrations in shoots of ryegrass Lolium perenne L. declined to 12% of the control samples, comparable to the extraction ratio of 0.1 M NaNO (15.8%) and 0.05 M (NH)SO (17.3%). For As-contaminated soil, 0.43 M HOAC provided a better estimation of relative phytoavailability (64.6 vs. 65.4% in ryegrass) compared to other extraction methods. We propose that 0.1 M NaNO or 0.05 M (NH)SO for Pb and 0.43 M HOAc for As may serve as surrogate measures to estimate the lability of metal(loid)s after soil remediation of the tested contaminated soils. Further studies over a wider range of soil types and amendments are necessary to validate extraction methods. [ABSTRACT FROM AUTHOR]

The rapid redox transformation of arsenic (As) species in waters presents a great environmental challenge in the accurate determination of its concentration and toxicity. The motivation of the present study was therefore to develop a method for rapid on-site separation of As(V) and As(III) in various aqueous matrices. The authors synthesized a thiol-modified sand (T-sand) that selectively removed As(III) but did not adsorb As(V). The novel application of this T-sand in a disposable cartridge was able to successfully separate As(V) (37-970 µg L−1) and As(III) (not detected to 488 µg L−1) in 23 groundwater samples collected in areas with naturally occurring As. The As speciation results determined with T-sand separation in the field were consistent with those obtained using high-performance liquid chromatography-atomic fluorescence spectrometry. Furthermore, the T-sand cartridge was applicable in a wide variety of matrices, including groundwater, leachants of the toxicity-characteristic leaching procedure, and extracts from the California waste extraction test; sequential extraction test; and in vitro gastrointestinal extraction. This easy-to-use separation method is especially suitable for routine field monitoring of As speciation. Environ Toxicol Chem 2014;33:1692-1696. © 2014 SETAC [ABSTRACT FROM AUTHOR]