Arsenic shapes the microbial community structures in tungsten mine waste rocks.

Tungsten (W) is a critical material that is widely used in military applications, electronics, lighting technology, power engineering and the automotive and aerospace industries. In recent decades, overexploitation of W has generated large amounts of mine waste rocks, which generate elevated content of toxic elements and cause serious adverse effects on ecosystems and public health. Microorganisms are considered important players in toxic element migrations from waste rocks. However, the understanding of how the microbial community structure varies in W mine waste rocks and its key driving factors is still unknown. In this study, high-throughput sequencing methods were used to determine the microbial community profiles along a W content gradient in W mine waste rocks. We found that the microbial community structures showed clear differences across the different W levels in waste rocks. Notably, arsenic (As), instead of W and nutrients, was identified as the most important predictor influencing microbial diversity. Furthermore, our results also showed that As is the most important environmental factor that regulates the distribution patterns of ecological clusters and keystone ASVs. Importantly, we found that the dominant genera have been regulated by As and were widely involved in As biogeochemical cycling in waste rocks. Taken together, our results have provided useful information about the response of microbial communities to W mine waste rocks.

Occurrence and dissemination of antibiotic resistance genes in mine soil ecosystems.

Metal(loid) selection contributes to selection pressure on antibiotic resistance, but to our knowledge, evidence of the dissemination of antibiotic resistance genes (ARGs) induced by metal(loid)s in mine soil ecosystems is rare. In the current study, using a high-throughput sequencing (HTS)-based metagenomic approach, 819 ARG subtypes were identified in a mine soil ecosystem, indicating that these environmental habitats are important reservoirs of ARGs. The results showed that metal(loid)-induced coselection has an important role in the distribution of soil ARGs. Furthermore, metal(loid) selection-induced ARGs were mainly associated with resistance-nodulation-division (RND) antibiotic efflux, which is distinct from what is observed in agricultural soil ecosystems. By using independent genome binning, metal(loid)s were shown impose coselection pressure on multiple ARGs residing on mobile genetic elements (MGEs), which promotes the dissemination of the antibiotic resistome. Interestingly, the current results showed that the density of several MGEs conferring ARGs was considerably higher in organisms most closely related to the priority pathogens Pseudomonas aeruginosa and Escherichia coli. Together, the results of this study indicate that mine soil ecosystems are important reservoirs of ARGs and that metal(loid)-induced coselection plays critical roles in the dissemination of ARGs in this type of soil habitat. KEY POINTS: • Mining soil ecosystem is a reservoir of antibiotic resistance genes (ARGs). • ARGs distribute via bacterial resistance-nodulation-division efflux systems. • Metal(loid)s coselected ARGs residing on mobile genetic elements in P. aeruginosa and E. coli.

Emission and transformation behaviors of trace elements during combustion of Cd-rich coals from coal combustion related endemic fluorosis areas of Southwest, China.

Long-term combustion of low-quality coal may release hazardous elements into the environment causing serious environmental problems. This phenomenon is particularly prevalent in the Three Gorges Region of Southwest (SW), China. Cadmium (Cd), as well as other harmful elements are found to be highly enriched in coals and supergene environments in this area. In the existing literature, the behavioral issue of emission and transformation of the elevated trace elements during simulated household stove combustion from Cd-rich inferior coal remains unknown. This study investigated the emission of toxic elements, mineral assemblages, and provided technical guidance for reducing pollution by means of optimization combustion tests on inferior coals. The research may improve the understanding of geochemical characteristics from toxic elements emission in coal combustion endemic diseased areas. For this purpose, a series of simulated coal combustion experiments were conducted to reveal the release, mobility, and distribution of elevated elements in Cd-rich coal combustion products. The results showed that Cd, Mo, Cr, Cu, Zn, As, and Sb were significantly enriched in the inferior coals of the study area. Furthermore, large amounts of toxic elements were released as fly ash into the environment during the combustion process. In particular, combustion conditions played an important role in the emission and transformation of elevated elements. For example, higher temperatures promoted the release of Cd, Sb, Zn, and Tl into the environment. Oxygen-deficient combustion was found to liberate more Cd, Sb, and Tl to the atmosphere and generated complex mineral assemblages of lizardite, calcite, dolomite, forsterite, and enstatite. Moreover, toxic elements were found to be absorbed in the fine particle matter of fly ash from the endemic fluorosis area of SW, China. The findings of this work may aid to control the emission of toxic elements from inferior coals and mitigate the effect of toxic elements in the environment to protect human health.

Photooxidation of Fe(II) to schwertmannite promotes As(III) oxidation and immobilization on pyrite under acidic conditions.

Pollution of arsenic (As) in acid mine drainage (AMD) is a universal environmental problem. The weathering of pyrite (FeS2) and other sulfide minerals leads to the generation of AMD and accelerates the leaching of As from sulfide minerals. Pyrite can undergo adsorption and redox reactions with As, affecting the existing form and biotoxicity of As. However, the interaction process between As and pyrite in AMD under sunlight radiation remains unclear. Here, we found that the oxidation and immobilization of arsenite (As(III)) on pyrite can be obviously promoted by the reactive oxygen species (ROS) in sunlit AMD, particularly by OH. The reactions between hole-electron pairs and water/oxygen adsorbed on excited pyrite resulted in the production of H2O2, OH and O2-, and OH was also generated through the photo-Fenton reaction of Fe2+/FeOH2+. Weakly crystalline schwertmannite formed from the oxidation of Fe2+ ions by OH contributed much to the adsorption and immobilization of As. In the mixed system of pyrite (0.75 g L-1), Fe2+ (56.08 mg L-1) and As(III) (1.0 mg L-1) at initial pH 3.0, the decrease ratio of dissolved total As concentration was 1.6% under dark conditions, while it significantly increased to 69.0% under sunlight radiation. The existence of oxygen or increase in initial pH from 2.0 to 4.0 accelerated As(III) oxidation and immobilization due to the oxidation of more Fe2+ and production of more ROS. The present work shows that sunlight significantly affects the transformation and migration of As in AMD, and provides new insights into the environmental behaviors of As.

Field aging declines the regulatory effects of biochar on cadmium uptake by pepper in the soil.

Biochar application is not only being widely promoted as an ideal strategy to mitigate global climate warming, but it also has the advantage of reducing heavy metal bioavailability and migration in the soil. However, studies on the effects of field aging on biochar to reduce heavy metals from the soil are still limited. The present study aimed to explore the effects and mechanisms of aged biochar added to the soil planted with pepper plants on cadmium (Cd) uptake. To achieve this, un-amended soil (control), soil amended with fresh biochar, and aged biochar (biochar recovered from a long-term field trial after 9 years) were used to investigate the effects of field aging on biochar adsorption efficiency. The results revealed that the amount of Cd in the plant planted in control soil, amended with fresh and aged biochar, accounted for 40 ± 6.10, 17.18 ± 1.19, and 18.68 ± 0.79, respectively. There was a significant difference (P < 0.05) in the amount of Cd that was uptaken by plants among all treatments. However, soil amended with fresh biochar significantly (P < 0.05) decreased the amount of Cd in plants compared with soil amended with aged biochar. This indicates that field aging declines the potential of biochar to lower heavy metal bioavailability and retention in the soil. This study demonstrates that long-term burial lessens the ability of biochar to interact with Cd and suggests that biochar amendment can lower Cd in the soil, depending on the freshness and aging of biochar.

Root microbiome assembly of As-hyperaccumulator Pteris vittata and its efficacy in arsenic requisition.

The assemblage of root-associated microorganisms plays important roles in improving their capability to adapt to environmental stress. Metal(loid) hyperaccumulators exhibit disparate adaptive capability compared to that of non-hyperaccumulators when faced with elevated contents of metal(loid)s. However, knowledge of the assemblage of root microbes of hyperaccumulators and their ecological roles in plant growth is still scarce. The present study used Pteris vittata as a model plant to study the microbial assemblage and its beneficial role in plant growth. We demonstrated that the assemblage of microbes from the associated bulk soil to the root compartment was based on their lifestyles. We used metagenomic analysis and identified that the assembled microbes were primarily involved in root-microbe interactions in P. vittata root. Notably, we identified that the assembled root microbiome played an important role in As requisition, which promoted the fitness and growth of P. vittata. This study provides new insights into the root microbiome and potential valuable knowledge to understand how the root microbiome contributes to the fitness of its host.

Microaerophilic Oxidation of Fe(II) Coupled with Simultaneous Carbon Fixation and As(III) Oxidation and Sequestration in Karstic Paddy Soil.

Microaerophilic Fe(II)-oxidizing bacteria are often chemolithoautotrophs, and the Fe(III) (oxyhydr)oxides they form could immobilize arsenic (As). If such microbes are active in karstic paddy soils, their activity would help increase soil organic carbon and mitigate As contamination. We therefore used gel-stabilized gradient systems to cultivate microaerophilic Fe(II)-oxidizing bacteria from karstic paddy soil to investigate their capacity for Fe(II) oxidation, carbon fixation, and As sequestration. Stable isotope probing demonstrated the assimilation of inorganic carbon at a maximum rate of 8.02 mmol C m-2 d-1. Sequencing revealed that Bradyrhizobium, Cupriavidus, Hyphomicrobium, Kaistobacter, Mesorhizobium, Rhizobium, unclassified Phycisphaerales, and unclassified Opitutaceas were fixing carbon. Fe(II) oxidation produced Fe(III) (oxyhydr)oxides, which can absorb and/or coprecipitate As. Adding As(III) decreased the diversity of functional bacteria involved in carbon fixation, the relative abundance of predicted carbon fixation genes, and the amount of carbon fixed. Although the rate of Fe(II) oxidation was also lower in the presence of As(III), over 90% of the As(III) was sequestered after oxidation. The potential for microbially mediated As(III) oxidation was revealed by the presence of arsenite oxidase gene (aioA), denoting the potential of the Fe(II)-oxidizing and autotrophic microbial community to also oxidize As(III). Thisstudy demonstrates that carbon fixation coupled to Fe(II) oxidation can increase the carbon content in soils by microaerophilic Fe(II)-oxidizing bacteria, as well as accelerate As(III) oxidation and sequester it in association with Fe(III) (oxyhydr)oxides.

Occurrence and mobility of toxic elements in coals from endemic fluorosis areas in the Three Gorges Region, SW China.

Fluorine (F) is a topic of great interest in coal-combustion related endemic fluorosis areas. However, little extent research exists regarding the environmental geochemistry of toxic elements that are enriched in coals and coal wastes in traditional endemic fluorosis areas, particularly focusing on their occurrences and mobilities during the weathering-leaching processes of coals and coal wastes in the surface environment. This paper addressed the issue of toxic elements in coals and coal wastes in the Three Gorges Region, Southwest (SW) China, where endemic fluorosis has historically prevailed, and investigated the distribution, occurrence, mobility features, and associated potential health risks. For this purpose, a modified experiment combined with long-term humidity cell test and column leaching trial was applied to elucidate the mobility of toxic elements in coals and coal wastes. In addition, sequential chemical extraction (SCE) was used to ascertain the modes of occurrence of toxic elements. The results demonstrated that the contents of toxic elements in the study area followed the order: stone coals > gangues > coal balls > coals. Furthermore, modes of occurrence of toxic elements were obviously different in coals and coal wastes. For example, cadmium (Cd) was mainly associated with monosulfide fraction in coals, molybdenum (Mo) and arsenic (As) were mainly associated with carbonate and silicate in coal gangues and stone coals, chromium (Cr) mainly existed in silicate and insoluble matter in coal gangues and coal balls, thallium (Tl) mainly occurred in organic matter in stone coals and sulfide in coals, and the occurrence of antimony (Sb) varied with different kinds of samples. Moreover, a large amount of toxic elements released to the leachates during the weathering and leaching process, which might pollute the environment and threaten human health. Based on the geo-accumulation index (Igeo), single factor index (Pi) and Nemerow index (PN), soils in the study area were mainly polluted by Cd, which constituted a potential risk to locally planted crops.

Characterization of the microbial community composition and the distribution of Fe-metabolizing bacteria in a creek contaminated by acid mine drainage.

A small watershed heavily contaminated by long-term acid mine drainage (AMD) from an upstream abandoned coal mine was selected to study the microbial community developed in such extreme system. The watershed consists of AMD-contaminated creek, adjacent contaminated soils, and a small cascade aeration unit constructed downstream, which provide an excellent contaminated site to study the microbial response in diverse extreme AMD-polluted environments. The results showed that the innate microbial communities were dominated by acidophilic bacteria, especially acidophilic Fe-metabolizing bacteria, suggesting that Fe and pH are the primary environmental factors in governing the indigenous microbial communities. The distribution of Fe-metabolizing bacteria showed distinct site-specific patterns. A pronounced shift from diverse communities in the upstream to Proteobacteria-dominated communities in the downstream was observed in the ecosystem. This location-specific trend was more apparent at genus level. In the upstream samples (sampling sites just below the coal mining adit), a number of Fe(II)-oxidizing bacteria such as Alicyclobacillus spp., Metallibacterium spp., and Acidithrix spp. were dominant, while Halomonas spp. were the major Fe(II)-oxidizing bacteria observed in downstream samples. Additionally, Acidiphilium, an Fe(III)-reducing bacterium, was enriched in the upstream samples, while Shewanella spp. were the dominant Fe(III)-reducing bacteria in downstream samples. Further investigation using linear discriminant analysis (LDA) effect size (LEfSe), principal coordinate analysis (PCoA), and unweighted pair group method with arithmetic mean (UPGMA) clustering confirmed the difference of microbial communities between upstream and downstream samples. Canonical correspondence analysis (CCA) and Spearman's rank correlation indicate that total organic carbon (TOC) content is the primary environmental parameter in structuring the indigenous microbial communities, suggesting that the microbial communities are shaped by three major environmental parameters (i.e., Fe, pH, and TOC). These findings were beneficial to a better understanding of natural attenuation of AMD.

Microbial diversity and community structure in an antimony-rich tailings dump.

To assess the impact of antimony (Sb) on microbial community structure, 12 samples were taken from an Sb tailings pile in Guizhou Province, Southwest China. All 12 samples exhibited elevated Sb concentrations, but the mobile and bioaccessible fractions were small in comparison to total Sb concentrations. Besides the geochemical analyses, microbial communities inhabiting the tailing samples were characterized to investigate the interplay between the microorganisms and environmental factors in mine tailings. In all samples, Proteobacteria and Actinobacteria were the most dominant phyla. At the genus level, Thiobacillus, Limnobacter, Nocardioides, Lysobacter, Phormidium, and Kaistobacter demonstrated relatively high abundances. The two most abundant genera, Thiobacillus and Limnobacter, are characterized as sulfur-oxidizing bacteria and thiosulfate-oxidizing bacteria, respectively, while the genus Lysobacter contains arsenic (As)-resistant bacteria. Canonical correspondence analysis (CCA) indicates that TOC and the sulfate to sulfide ratio strongly shaped the microbial communities, suggesting the influence of the environmental factors in the indigenous microbial communities.

Diversity of the Sediment Microbial Community in the Aha Watershed (Southwest China) in Response to Acid Mine Drainage Pollution Gradients.

Located in southwest China, the Aha watershed is continually contaminated by acid mine drainage (AMD) produced from upstream abandoned coal mines. The watershed is fed by creeks with elevated concentrations of aqueous Fe (total Fe > 1 g/liter) and SO4 (2-) (>6 g/liter). AMD contamination gradually decreases throughout downstream rivers and reservoirs, creating an AMD pollution gradient which has led to a suite of biogeochemical processes along the watershed. In this study, sediment samples were collected along the AMD pollution sites for geochemical and microbial community analyses. High-throughput sequencing found various bacteria associated with microbial Fe and S cycling within the watershed and AMD-impacted creek. A large proportion of Fe- and S-metabolizing bacteria were detected in this watershed. The dominant Fe- and S-metabolizing bacteria were identified as microorganisms belonging to the genera Metallibacterium, Aciditerrimonas, Halomonas, Shewanella, Ferrovum, Alicyclobacillus, and Syntrophobacter. Among them, Halomonas, Aciditerrimonas, Metallibacterium, and Shewanella have previously only rarely been detected in AMD-contaminated environments. In addition, the microbial community structures changed along the watershed with different magnitudes of AMD pollution. Moreover, the canonical correspondence analysis suggested that temperature, pH, total Fe, sulfate, and redox potentials (Eh) were significant factors that structured the microbial community compositions along the Aha watershed.

Microbial community analysis in rice paddy soils irrigated by acid mine drainage contaminated water.

Five rice paddy soils located in southwest China were selected for geochemical and microbial community analysis. These rice fields were irrigated with river water which was contaminated by Fe-S-rich acid mine drainage. Microbial communities were characterized by high-throughput sequencing, which showed 39 different phyla/groups in these samples. Among these phyla/groups, Proteobacteria was the most abundant phylum in all samples. Chloroflexi, Acidobacteria, Nitrospirae, and Bacteroidetes exhibited higher relative abundances than other phyla. A number of rare and candidate phyla were also detected. Moreover, canonical correspondence analysis suggested that pH, sulfate, and nitrate were significant factors that shaped the microbial community structure. In addition, a wide diversity of Fe- and S-related bacteria, such as GOUTA19, Shewanella, Geobacter, Desulfobacca, Thiobacillus, Desulfobacterium, and Anaeromyxobacter, might be responsible for biogeochemical Fe and S cycles in the tested rice paddy soils. Among the dominant genera, GOUTA19 and Shewanella were seldom detected in rice paddy soils.

Potential health risk in areas with high naturally-occurring cadmium background in southwestern China.

In various parts of the world, high cadmium (Cd) concentrations in environment are not related to anthropogenic contamination but have natural origins. Less is known about health risks that arise under these conditions. This study aimed to discuss the pollution of Cd with natural sources, and to investigate the concentration of Cd in food crops and the urine of inhabitants in an area of southwestern China. The results showed that the arable soils are moderately contaminated by Cd (I(geo)=1.51) relative to the local background, with a high ecological risk (Er=218). The chemical fractions of Cd in soils with natural sources are probably controlled by parent materials and mostly in residual phase. The average Cd concentrations were 0.68 mg kg(-1) (fresh weight) in local vegetables, 0.04 mg kg(-1) in rice, and 0.14 µg L(-1) in water. Leafy vegetable tends to accumulate more Cd than the other crops. The calculated Target Hazard Quotient (THQ) had a much higher value (4.33) for Cd, suggesting that Cd represents a significant potential risk to the local population. The urinary Cd concentrations (mean at 3.92 µg L(-1) for male and 4.85 µg L(-1) for female) of inhabitants in the study area were significantly higher (p<0.05) than those from the control area (mean at 0.8 µg L(-1) for male and 0.42 µg L(-1) for female). Male and female test subjects had similar urinary Cd levels (p>0.05), but age seemed to lead to an increase in Cd in the urine. These findings show that naturally-occurring Cd in local soils is taken up appreciably by local food crops, and that dietary exposure of Cd through vegetable ingestion is a major exposure pathway for local populations, and a potential risk to public health in the study area.

Antimony in the Soil-Plant System in an Sb Mining/Smelting Area of Southwest China.

The distribution, bioavailability, and accumulation of antimony (Sb) at the interface of rhizospheric soils and indigenous plants from a large Sb mining/smelting area in Southwest China were explored. Results showed that the local soil was severely polluted by Sb, and the aluminum magnesium silicate minerals and the carbonate fraction may mainly contribute to bound Sb. The sequential extraction results of soil samples revealed that the portion of bioavailable Sb was low, but the bioavailable Sb concentration was up to 67.2 mg/kg, due to high total Sb concentrations in the soil. The Sb content in local plants showed a wide range, from 21 to 21148 mg/kg. The species of Chenopodium album Linn., Sedum emarginatum Migo, and Sedum lineare Thunb showed high accumulation of Sb at levels of above 1000 mg/kg. The Sb contents in the tissues for most plants decreased with the order of root > leaf > stem. The bioaccumulation coefficients and/or the biological transfer factors for most plants were less than 1. All of the studied plant species were not identified as Sb-hyperaccumulators, but the species of Chenopodium album Linn., Sedum emarginatum Migo, and Sedum lineare Thunb could be applied as alternative plants for phytoremediating Sb-polluted soils.

High Accumulation and Subcellular Distribution of Thallium in Green Cabbage (Brassica Oleracea L. Var. Capitata L.).

The accumulation of thallium (Tl) in brassicaceous crops is widely known, but both the uptake extents of Tl by the individual cultivars of green cabbage and the distribution of Tl in the tissues of green cabbage are not well understood. Five commonly available cultivars of green cabbage grown in the Tl-spiked pot-culture trials were studied for the uptake extent and subcellular distribution of Tl. The results showed that all the trial cultivars mainly concentrated Tl in the leaves (101∼192 mg/kg, DW) rather than in the roots or stems, with no significant differences among cultivars (p = 0.455). Tl accumulation in the leaves revealed obvious subcellular fractionation: cell cytosol and vacuole >> cell wall > cell organelles. The majority (∼ 88%) of leaf-Tl was found to be in the fraction of cytosol and vacuole, which also served as the major storage site for other major elements such as Ca and Mg. This specific subcellular fractionation of Tl appeared to enable green cabbage to avoid Tl damage to its vital organelles and to help green cabbage tolerate and detoxify Tl. This study demonstrated that all the five green cabbage cultivars show a good application potential in the phytoremediation of Tl-contaminated soils.

Spatio-seasonal patterns and sources of major ions in the Longjiang River catchment, Southern China.

River water quality is closely related to the major ion sources and hydrological conditions. However, there is a limited cognition about the geochemical sources and the seasonal variations of major ions. Thus, in this study, a total of 90 water samples were collected from the Longjiang River and its three tributaries in the dry and wet seasons. The samples were analyzed, including major ion concentrations and physicochemical parameters. Statistical analysis, such as correlation analysis and principal component analysis (PCA), was employed to investigate the spatial and seasonal variations in major ion composition and their respective sources. Our study revealed that the predominant major ions in the studied samples are Ca2+, Mg2+, HCO - 3, and SO2 - 4. Most of ions exhibited notable spatial disparities attributable to variations in geological settings and human activities. Regions characterized by igneous rock outcrops tend to exhibit higher levels of K+ and Na+, while areas with higher population densities in the middle and downstream segments show elevated concentrations of Cl-, NO - 3, SO2 - 4, Na+, and K+. The observed peak SO2 - 4 levels may be attributed to active mining operations. Most parameters displayed higher values in flood season than those in dry season due to dilution effects. Stoichiometric analysis indicated that carbonate weathering inputs contribute to over 85% of the mean total cation concentrations in the water, followed by contributions from silicates, atmospheric deposition, and anthropogenic inputs. On the whole, although the water quality remains non-polluted and is suitable for drinking and irrigation purposes, the enrichment of SO2 - 4 and NO - 3 may contribute to water eutrophication. Caution is warranted during the dry season due to reduced water flow resulting from dam interceptions and limited dilution capacity, potentially leading to elevated pollutant concentrations. Taken together, our results provided a scientific basis for water quality managements of monsoon rivers.

The rhizosphere microbiome reduces the uptake of arsenic and tungsten by Blechnum orientale by increasing nutrient cycling in historical tungsten mining area soils.

The growth of pioneer plants in metal mining area soil is closely related to their minimal uptake of toxic elements. Pioneer plants can inhibit the uptake of toxic elements by increasing nutrient uptake. However, few studies have focused on the mechanisms by which the rhizosphere microbiome affect nutrient cycling and their impact on the uptake of toxic elements by pioneer plants. In this study, we selected Blechnum orientale to investigate the potential roles of the rhizosphere microbiome in nutrient cycling and plant growth in a historical tungsten (W) mining area. Our results showed that while the arsenic (As) and W contents in the soil were relatively high, the enrichment levels of As and W in the B. orientale were relatively low. Furthermore, we found that the As and W contents in plants were significantly negatively correlated with soil nutrients (S, P and Mo), suggesting that elevated levels of these soil nutrients could inhibit As and W uptake by B. orientale. Importantly, we found that these nutrients were also identified as the most important factors shaping rhizosphere microbial attributes, including microbial diversity, ecological clusters, and keystone OTUs. Moreover, the genera, keystone taxa and microbial functional genes enriched in the rhizosphere soils from mining areas played a key role in nutrient (S, P and Mo) bioavailability, which could further increase the nutrient uptake by B. orientale. Taken together, our results suggest that rhizosphere microorganisms can improve pioneer plant growth by inhibiting toxic element accumulation via the increase in nutrient cycling in former W mining areas.

Phase transformation of schwertmannite in paddy soil under different water management regimes and its impact on the migration of arsenic in soil.

Schwertmannite (Sch) holds a great promise as an iron material for remediating Arsenic (As)-contaminated paddy soils, due to its extremely high immobilization capacities for both arsenate [As(V)] and arsenite [As(III)]. However, there is still limited knowledge on the mineral phase transformation of this metastable iron-oxyhydroxysulfate mineral in paddy soils, particularly under different water management regimes including aerobic, intermittent flooding, and continuous flooding, and how its phase transformation impacts the migration of As in paddy soils. In this study, a membrane coated with schwertmannite was first developed to directly reflect the phase transformation of bulk schwertmannite applied to paddy soils. A soil incubation experiment was then conducted to investigate the mineral phase transformation of schwertmannite in paddy soils under different water management regimes and its impact on the migration of As in paddy soil. Our findings revealed that schwertmannite can persist in the paddy soil for 90 days in the aerobic group, whereas in the continuous flooding and intermittent flooding groups, schwertmannite transformed into goethite, with the degree or rate of mineral phase transformation being 5% Sch >1% Sch > control. These results indicated that water management practices and the amount of schwertmannite applied were the primary factors determining the occurrence and degree of mineral transformation of schwertmannite in paddy soil. Moreover, despite undergoing phase transformation, schwertmannite still significantly reduced the porewater As (As(III) and As(V)), and facilitated the transfer of non-specifically adsorbed As (F1) and specifically adsorbed As (F2) to amorphous iron oxide-bound As (F3), effectively reducing the bioavailability of soil As. These findings contribute to a better understanding of the mineralogical transformation of schwertmannite in paddy soils and the impact of mineral phase transformation on the retention of As in soil, which carry important implications for the application of schwertmannite in remediating As-contaminated paddy soils.

Antimony and arsenic migration in a heterogeneous subsurface at an abandoned antimony smelter under rainfall.

While antimony (Sb) and arsenic (As) co-contamination in subsurface soil systems due to the legacy of Sb smelting wastes has been documented, the role of inherent heterogeneity on pollutant migration is largely overlooked. Herein this study investigated Sb and As migration in a slag impacted, vertically stratified subsurface at an abandoned Sb smelter. A 2-dimensional flume was assembled as a lab-scale analogue of the site and subject to rainfall and stop-rain events. Reactive transport modeling was then performed by matching the experimental observations to verify the key factors and processes controlling pollutant migration. Results showed that rainfall caused Sb and As release from the shallow slag layer and promoted their downward movement. Nevertheless, the less permeable deeper layers limited physical flow and transport, which led to Sb and As accumulation at the interface. The re-adsorption of Sb and As onto iron oxides in the deeper, more acidic layers further retarded their migration. Because of the large difference between Sb and As concentrations, Sb re-adsorption was much less effective, which led to higher mobility. Our findings overall highlight the necessity of understanding the degree and impacts of physicochemical heterogeneity for risk exposure assessment and remediation of abandoned Sb smelting sites.

Antimony isotope fractionation and the key controls in the soil profiles of an antimony smelting area.

The controlling factors of antimony migration and transformation in soil profiles are still unclear. Antimony isotopes might be a useful tool to trace it. In this paper, antimony isotopic compositions of plant and smelter-derived samples, and two soil profiles were measured for the first time. The δ123Sb values of the surface and bottom layers of the two soil profiles varied in 0.23‰-1.19‰ and 0.58‰-0.66‰, respectively, while δ123Sb of the smelter-derived samples varied in 0.29‰-0.38‰. The results show that the antimony isotopic compositions in the soil profiles are affected by post-depositional biogeochemical processes. The enrichment and loss of light isotopes at 0-10 cm and 10-40 cm layers of the contrasted soil profile may be controlled by plant uptake process. The loss and enrichment of heavy isotopes in the 0-10 cm and 10-25 cm layers of the antimony from smelting source in the polluted soil profile may be controlled by the adsorption process, while the enrichment of light isotopes in the 25-80 cm layer may be related to the reductive dissolution process. The conclusion emphasizes that the promotion of the Sb isotope fractionation mechanism will play a crucial role in understanding the migration and transformation behaviors of Sb in soil systems.