Arsenic Transformation Research Articles

Arsenic Stress Mitigation Using a Novel Plant Growth-Promoting Bacterial Strain Bacillus mycoides NR5 in Spinach Plant (Spinacia oleracea L.).

Present study aimed to identify arsenic (As)-resistant bacterial strains that can be used to mitigate arsenic stress. A bacterium Bacillus mycoides NR5 having As tolerance limit of 1100 mg L-1 was isolated from Nag River, Maharashtra, India. It was also equipped with plant growth-promoting (PGP) attributes like phosphate solubilization, siderophores, ammonia, and nitrate reduction, with added antibiotic tolerance. Furthermore, scanning electron microscopy (SEM) and transmission electron micrograph (TEM) suggested biosorption as possible mechanisms of arsenic tolerance. A strong peak in FTIR spectra at 3379.0 corresponding to amine in As-treated NR5 also indicated metal interaction with cell surface protein. Amplification of arsenic reductase gene in NR5 further suggested intracellular transformation of As speciation. Moreover, As tolerance capability of NR5 was shown in spinach plants in which the bacterium effectively mitigated 25 ppm As by producing defense-related proline molecules. Evidence from SEM, TEM, and FTIR, concluded biosorption possibly the primary mechanism of As tolerance in NR5 along with the transformation of arsenic. B. mycoides NR5 with PGP attributes, high As tolerance, and antibiotic resistance mediated enhanced As tolerance in spinach plants advocated that the strain can be a better choice for As bioremediation in contaminated agricultural soil and water.

Migration mechanism of PTEs in polymetallic mines under pioneer phytoremediation: A Lanmuchang mercury-thallium mine perspective

The establishment of pioneer plants in waste slag sites not only modifies the nutrient content of the waste, but also plays a significant role in regulating the pH and potentially toxic elements (PTEs), thereby providing favorable conditions for the quick introduction of other plants. However, the mechanisms by which pioneer plants impact the migration and transformation of PTEs in polymetallic mines have rarely been studied. In this study, we investigated the effects of pioneer phytoremediation on the migration and transformation of PTEs, specifically thallium (Tl), mercury (Hg), arsenic (As), and antimony (Sb), in mercury-thallium mine waste. The results showed that pioneer phytoremediation increased esters and ethers containing C-O and P-O groups in dissolved organic matter, which subsequently formed soluble complexes with Hg, As, and Sb. Nevertheless, pioneer phytoremediation reduced the migration of Tl in the waste, this was mainly because pioneer phytoremediation reduced Fe3+ in silicate minerals and iron-containing minerals to more reactive Fe2+, thereby increasing the electronegativity (El) of the waste and enhancing its adsorption capacity for metal cations, such as Hg and Tl, thus maintaining electrical neutrality. However, the increased El of the waste was detrimental to the adsorption of negatively charged oxygen-containing anions, such as As and Sb. At the same time, the dissolution of Fe2+ resulted in the release and mobility of As and Sb that had been adsorbed onto iron oxides. The results offer significant theoretical support for guiding the ecological restoration of PTEs in polymetallic mines.

Two-dimensional distribution of arsenic species in the riparian zone regulated by As-Fe co-transformation under varying river water proportions and bicarbonate concentrations

Arsenic (As) contamination of groundwater is a major issue in global environmental health. In the riparian zone, mixing river water and groundwater with different substances is proposed to affect arsenic transformation and distribution. However, the distribution of arsenic species in the riparian zone and its co-transformation with iron under varying river water proportions and bicarbonate (HCO3–) concentrations remain unclear. The two-dimensional distributions of arsenic species, including exchangeable (Ex-As), carbonates-bounded (Carb-As), FeMn(hydr)oxide-bounded (Ox-As), organic-bounded (Om-As) and residual arsenic (Res-As), were investigated in three typical profiles of the riparian zone near the lower reaches of the Hanjiang River, China. The apparent enrichment of arsenic in the pore water, either As(III) and As(V), and in the sediment, mainly Carb-As and Ox-As, were observed in the profiles. The correlation analysis showed that the distributions of arsenic species in the riparian zone were primarily related to dissolved or total organic matter (DOC or TOC), Fe, HCO3–, dissolved oxygen (DO) and oxidation–reduction potential (Eh). Further batch experiments mixing simulated river water and groundwater with different proportions and HCO3– concentrations demonstrated that the forming of the arsenic-rich area in the riparian sediment was derived from the oxidation of Fe(II) and As(III) from groundwater, controlled by the varying DO from river water and HCO3– from organics degradation. These results provide more knowledge of the transforming process of arsenic in the riparian zone and a better understanding of the role of the riparian zone in arsenic restraint.

Metal-Organic Framework Functionalized Chitosan/Pectin Membranes for Solar-Driven Photo-Oxidation and Adsorption of Arsenic

The presence of arsenic as neutral arsenite and oxoanionic arsenate species are a worldwide issue that requires an effective remediation technology capable to remove both AsIII and AsV from water. In this research we propose the assembly of a membrane build up from chitosan/pectin (CHIPEC) composite biopolymer and the UiO-66-NH2 porous and photo-active metal–organic framework. CHIPEC@UiO-66-NH2 membrane integrates porosity, adsorptive capacity, and activity to photo-oxidize and adsorb AsIII and AsV species. Nanometric-sized UiO-66-NH2 was synthetized and homogeneously distributed within the CHIPEC matrix, achieving a composite membrane with optical physico-chemical and optical properties (band gap of 2.91 eV) suitable to be applied on photooxidation of AsIII and adsorption of AsV. Under optimal conditions, maximum adsorption capacities (Qmax) values of 254 and 168 mg g−1 were reached for AsIII adsorption by MOF and membrane, respectively. Notably, for AsV adsorption, Qmax values of 268 and 335 mg g−1 were reached for powdered and immobilized MOF, respectively. Moreover, the membrane keeps most of its activity for AsV adsorption when employed in surface and groundwater matrixes. Further, the efficiently of UiO-66-NH2 to photo-oxidize AsIII to AsV, subsequently adsorbing the arsenate oxyanions, is improved by a factor of five when is integrated into the polymer. A detailed multi-step mechanism for the arsenic transformation and adsorption in CHIPEC@UiO-66-NH2 has been proposed on the basis of the anionic exchange at Zr hexa-nuclear clusters and amino groups in the MOF. Overall, MOF-biopolymeric composite has been proved as a straightforward, efficient, low-cost, and environmentally friendly solution for detoxifying arsenic in surface and underground water.

Meta-omics analysis reveals the marine arsenic cycle driven by bacteria

Arsenic is a toxic element widely distributed in the Earth's crust and ranked as a class I human carcinogen. Microbial metabolism makes significant contributions to arsenic detoxification, migration and transformation. Nowadays, research on arsenic is primarily in areas affected by arsenic pollution associated with human health activities. However, the biogeochemical traits of arsenic in the global marine ecosystem remain to be explicated. In this study, we revealed that seawater environments were primarily governed by the process of arsenate reduction to arsenite, while arsenite methylation was predominant in marine sediments which may serve as significant sources of arsenic emission into the atmosphere. Significant disparities existed in the distribution patterns of the arsenic cycle between surface and deep seawaters at middle and low latitudes, whereas these situations tend to be similar in the Arctic and Antarctic oceans. Significant variations were also observed in the taxonomic diversity and core microbial community of arsenic cycling across different marine environments. Specifically, γ-proteobacteria played a pivotal role in the arsenic cycle in the whole marine environment. Temperature, dissolved oxygen and phosphate were the crucial factors that related to these differentiations in seawater environments. Overall, our study contributes to a deeper understanding of the marine arsenic cycle.

Arsenic distribution characteristics and release mechanisms in aquaculture lake sediments

It is well known that aquaculture can alter the microenvironments of lakes at sediment-water interface (SWI). However, the main mechanisms underlying the effects of aquaculture activities on arsenic (As) transformations are still unclear. In this context, the present study aims to investigate the variations in the sediment As contents in Yangcheng Lake, as well as to assess its chemical transformations, release fluxes, and release mechanisms. The results showed substantial spatial differences in the dissolved As concentrations in the sediment pore water. The As release fluxes at the SWI ranged from 1.32 to 112.09 μg/L, with an average value of 33.68 μg/L. In addition, the highest As fluxes were observed in the aquaculture areas. The transformation of crystalline hydrous Fe oxide-bound As to adsorbed-As in the aquaculture lake sediments increased the ability of As release. The Partial least squares path modeling results demonstrated the great contributions of organic matter (OM) to the As transformations by influencing the sediment microbial communities and Fe/Mn minerals. The changes in the As fractionation and competing adsorption increased the dissolved As concentrations in the 0–10 mm surface sediment. Non-specifically and specifically adsorbed As were the major sources of dissolved As in the sediments. Specifically, microbial reduction of As[V] and dissolution of Fe oxides increased the dissolved As concentrations at the SWI (20 to −20 mm). The results of the current study highlight the positive enhancement effects of aquaculture on As release from sediments.

Synergistic effects of warming and humic substances on driving arsenic reduction and methanogenesis in flooded paddy soil

Microbially-driven arsenic reduction and methane emissions in anaerobic soils are regulated by widespread humic substances (HS), while how this effect responds to climate change remains unknown. We investigated potential synergistic effects of HS in response to temperature changes in arsenic-contaminated paddy soils treated with humic acid (HA) and fulvic acid (FA) at temperatures ranging from 15 to 45 °C. Our results reveal a significant increase in arsenic reduction (5.6 times) and methane emissions (178 times) driven by HS, which can be exponentially stimulated at 45 °C. Acting as a electron shuttle, HS determines microbial arsenic reduction, further stimulated by warming. The top three sensitive genera are Geobacter, Anaeromyxobacter, and Gaiella which are responsible for enhanced arsenic reduction, as well as for the reduction of iron and HS with their functional genes; arrA and Geobacter spp. The top three sensitive methanogens are Methanosarsina, Methanocella, and Methanoculleus. Our study suggests notable synergistic effects between HS and warming in stimulating arsenic reduction and methanogenesis in paddy soils. Overall, the findings of this work highlight the high sensitivity of HS-mediated microbial arsenic transformation and methanogenesis in response to warming, which add potential value in predicting the biogeochemical cycling of arsenic and methane in soil under the context of climate change.

Influence of anti-seasonal inundation on geochemical processes of arsenic speciation in the water-level-fluctuation zone soil of the Three Gorges Reservoir, China

Since the completion of Three Gorges Dam, the water-level-fluctuation zone (WLFZ) of the Three Gorges Reservoir (TGR) experiences the periodic anti-seasonal inundation. However, knowledge for mechanisms of mobilization and transformation of arsenic (As) in WLFZ soils of the TGR remains scarce. To address this gap, a combination of field observation and simulated flooding experiments attempts to illustrate the As mobilization, the transformation between As(V) and As(III), and the factors driving these processes. The study revealed that anti-seasonal inundation (with a temperature at 13 ℃) mitigated As release from submerged soils. Interestingly, the total As and ratio of As(III) (the more toxic form of As) concentrations in porewater at 13 ℃ was lower, and the prevalence of As(III) occurred later than those at 32 °C (imitate the seasonal inundation condition). The results indicated that the As reduction and the corresponding toxic risks in submerged soils were alleviated under anti-seasonal inundation. The study proposes the reduction of As-bearing manganese (Mn) mineral assemblages and competitive adsorption of dissolved organic carbon (DOC) as primary mechanisms for As mobilization. Furthermore, microorganism-mediated detoxification/reduction processes involving DOC, nitrogen, and Mn (oxyhydr)oxides were identified as central pathways for As(III) enrichment under anti-seasonal inundation. This study enhances understandings of the biogeochemical processes and fate of As in WLFZ soils influenced by artificial regulation of the reservoir.

Solar-Driven Arsenic(V) Transformation, Speciation, and Adsorption on the Chalcopyrite Surface

Solar-Driven Arsenic(V) Transformation, Speciation, and Adsorption on the Chalcopyrite Surface

Colloidal fraction on pomelo peel-derived biochar plays a dual role as electron shuttle and adsorbent in controlling arsenic transformation in anoxic paddy soil

Arsenic release and reduction in anoxic environments can be mitigated or facilitated by biochar amendment. However, the key fractions in biochars and how they control arsenic transformation remain poorly understood. In this study, a biochar produced from pomelo peel was rich in colloids and was used to evaluate the roles of the colloidal and residual fractions of biochar in arsenic transformation in anoxic paddy soil. Bulk biochar showed a markedly higher maximum adsorption capacity for As(III) at 1732 mg/kg than for As(V) at 75.7 mg/kg, mainly because of the colloidal fraction on the surface. When compared with the control and treatments with the colloidal/residual fraction, the addition of bulk biochar facilitated As(V) reduction and release in the soil during days 0–12, but decreased the dissolved As(III) concentration during days 12–20. The colloidal fraction revealed significantly higher electron donating capacity (8.26 μmole−/g) than that of bulk biochar (0.88 μmole−/g) and residual fraction (0.65 μmole−/g), acting as electron shuttle to promote As(V) reduction. Because the colloidal fraction was rich in aliphatic carbon, fulvic acid-like compounds, potassium, and calcium, it favored As(III) adsorption when more As(III) was released, probably via organic-cation-As(III) complexation. These findings provide deeper insight into the role of the colloidal fraction of biochar in controlling anaerobic arsenic transformation, which will be helpful for the practical application of biochar in arsenic-contaminated environments.

Vertical distribution of arsenic and bacterial communities in calcareous farmland amending by organic fertilizer and iron-oxidizing bacteria: Field experiment on concomitant remediation

The migration and transformation mechanisms of arsenic (As) in soil environments necessitate an understanding of its influencing processes. Here, we investigate the subsurface biogeochemical transformation of As and iron (Fe) through amended in the top 20 cm with iron oxidizing bacteria (FeOB) and organic fertilizer (OF). Our comprehensive 400-day field study, conducted in a calcareous soil profile sectioned into 20 cm increments, involved analysis by sequential extraction and assessment of microbial properties. The results reveal that the introduction of additional OF increased the release ratio of As/Fe from the non-specific adsorption fraction (136.47 %) at the subsoil depth (40–60 cm), underscoring the importance of sampling at various depths and time points to accurately elucidate the form, instability, and migration of As within the profile. Examination of bacterial interaction networks indicated a disrupted initial niche in the bottom layer, resulting in a novel cooperative symbiosis. While the addition of FeOB did not lead to the dominance of specific bacterial species, it did enhance the relative abundance of As-tolerant Acidobacteria and Gemmatimonadetes in both surface (39.2 % and 38.76 %) and deeper soils (44.29 % and 23.73 %) compared to the control. Consequently, the amendment of FeOB in conjunction with OF facilitated the formation of poorly amorphous Fe (hydr)oxides in the soil, achieved through abiotic and biotic sequestration processes. Throughout the long-term remediation process, the migration coefficient of bioavailable As within the soil profile decreased, indicating that these practices did not exacerbate As mobilization. This study carries significant implications for enhancing biogeochemical cycling in As-contaminated Sierozem soils and exploring potential bioremediation strategies. Environmental implicationThe long-term exposure of sewage irrigation has potential adverse effects on the local ecosystem, causing serious environmental problems. Microorganisms play a vital role in the migration and transformation of arsenic in calcareous soil in arid areas, which highlights the necessity of understanding its dynamics. The vertical distribution, microbial community and fate of arsenic in calcareous farmland soil profile in northwest China were studied through field experiments. The results of this work have certain significance for the remediation of arsenic-contaminated soil in arid areas, and provide new insights for the migration, transformation and remediation of arsenic in this kind of soil.

Toxic Effects of Arsenic on Four Freshwater Aquatic Species and Its Transformation Metabolism in Crucian Carp (Carassius auratus).

Inorganic arsenic is a well-known carcinogen that is much more toxic than its organic counterpart. While much is known about the accumulation and transformation of arsenic in marine organisms, little is known regarding these processes in freshwater aquatic species. In this study, the acute toxicity and toxicological effects of inorganic arsenic on four freshwater organisms (Cyprinus carpio, Misgurnus anguillicaudatus, Pseudorasbora parva, Eriocheir sinensis) commonly found in rice-fish farming systems were investigated. The organisms exhibited different levels of sensitivity to inorganic arsenic, with crustaceans being more sensitive than fish. Fish were found to be more tolerant to As(V) than As(III). The study also investigated the accumulation, transformation, and release of inorganic arsenic in crucian carp, an omnivorous species with high environmental tolerance. The fish accumulated As(III) rapidly in various tissues, and were able to transport it to other tissues through gills, intestines, and skin. The accumulated As(III) was converted into less toxic forms, such as monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA), via methylation. The fish also converted As(III) into arsenate (AsV) via enzymatic and oxidative reactions. After the transferal to clean water, the forms of arsenic in the various tissues decreased rapidly, but the rates of excretion of the four forms of arsenic were not the same among the different tissues. Our results suggest that crucian carp can reduce the environmental toxicity of As(III) at certain concentrations by transforming it into less toxic forms within their bodies.

Sulfur enhances iron plaque formation and stress resistance to reduce the transfer of Cd and As in the soil-rice system

Sulfur plays an essential role in agricultural production, but few studies have been reported on how sulfur simultaneously impacts the transformation of cadmium (Cd) and arsenic (As) in the soil-rice system. This research selected two soils co-contaminated with both Cd and As, varying in acidity and alkalinity levels, to study the impacts of elemental sulfur (S) and calcium sulfate (CaSO4) on the migration and accumulation of Cd and As by rice. Results indicated that two types of sulfur had a substantial (P < 0.05) impact on decreasing the contents of Cd (28.3–50.4 %) and As (20.1–38.6 %) in brown rice in acidic and alkaline soils. They also increased rice biomass (29.3–112.8 %) and reduced Cd transport coefficient (27.2–45.6 %) significantly (P < 0.05). Notably, sulfur augmented the generation of iron plaque on rice root surfaces, which increased the fixation of Cd (17.6–61.0 %) and As (14.0–45.9 %). SEM-EDS results also indicated that the rice root surface exhibited significant enrichment of Fe, Cd, and As. The mechanism of simultaneous Cd and As immobilization by sulfur application was mainly ascribed to the contribution of iron plaque. Additionally, sulfur reduced the contents of Cd and As in soil porewater and promoted the transformation of As(III) to As(V) to reduce the toxicity of As. The K-edge XAFS of As in iron plaque also confirmed that sulfur application significantly promoted As(III) oxidation. Sulfur also promoted the activities of antioxidant enzymes and the contents of NPT, GSH, and PCs in rice plants. In general, this study establishes a foundation for sulfur to lower As and Cd bioavailability in paddy soils, enhance iron plaque and rice resistance, and reduce heavy metal accumulation.

Effects of biodegradable microplastics on arsenic migration and transformation in paddy soils: a comparative analysis with conventional microplastics

The combined pollution of microplastics (MPs) and arsenic (As) in paddy soils has attracted more attention worldwide. However, there are few comparative studies on the effects of biodegradable and conventional MPs on As migration and transformation. Therefore, conventional (polystyrene, polyethylene, polyvinyl chloride) and biodegradable (polybutadiene styrene, polylactic acid, polybutylene adipate terephthalate) MPs were selected to explore and demonstrate their influences and mechanism on As migration from paddy soils to overlying water and As speciation transformation through microcosmic experiment with measuring the changes of As chemical distribution, physicochemical indexes and microbial community in paddy soils. The results showed that biodegradable MPs enhanced As migration and transformation more effective than conventional MPs during 60 d. Biodegradable MPs indirectly increased the content of As(Ⅲ) and bioavailable As by changing the microbial community structure and affecting the biogeochemical cycles of carbon, nitrogen, sulfur and iron in soils, and promoted the As migration and transformation. PBS showed the strongest promoting effect, transforming to more As(Ⅲ) (11.43%) and bioavailable As (4.28%) than control. This helps to a better understanding of the effects of MPs on As biogeochemical cycle and to clarify the ecological and food safety risks of their combined pollution in soils.

Enhancing the bioreduction and interaction of arsenic and iron by thiosulfate in groundwater

Thiosulfate influences the bioreduction and migration transformation of arsenic (As) and iron (Fe) in groundwater environments. The aim of this study was to investigate the impact of microbially-mediated sulfur cycling on the bioreduction and interaction of As and Fe. Microcosm experiments were conducted, including bioreduction of thiosulfate, As(V), and Fe(III) by Citrobacter sp. JH012–1, as well as the influence of thiosulfate input at different initial arsenate concentrations on the bioreduction of As(V) and Fe(III). The results demonstrate that Citrobacter sp. JH012–1 exhibited strong reduction capabilities for thiosulfate, As(V), and Fe(III). Improving thiosulfate level promoted the bioreduction of Fe(III) and As(V). When 0, 0.1, 0.5, and 1 mM thiosulfate were added, Fe(III) was completely reduced within 9 days, 3 days, 1 day, and 0.5 days, simultaneously, 72.8%, 82.2%, 85.5%, and 90.0% of As(V) were reduced, respectively. The products of As(III) binding with sulfide are controlled by the ratio of As-S. When the initial arsenate concentration was 0.025 mM, the addition of thiosulfate resulted in the accumulation of soluble thioarsenite. However, when the initial arsenate level increased to 1 mM, precipitates of orpiment or realgar were formed. In the presence of both arsenic and iron, As(V) significantly inhibits the bioreduction of Fe(III). Under the concentrations of 0, 0.025, and 1 mM As(V), the reduction rates of Fe(III) were 100%, 91%, and 83%, respectively. In this scenario, the sulfide produced by thiosulfate reduction tends to bind with Fe(II) rather than As(III). Therefore, the competition of arsenic-iron and thiosulfate concentration should be considered to study the impact of thiosulfate on arsenic and iron migration and transformation in groundwater.

Arsenic-methylating microbial community in sediment along the water flow is correlated with the distance to a low-temperature hot spring

Abstract Microbially mediated arsenic methylation, remains understudied in subgeothermal environments. This study aimed to investigate the activity and diversity of arsM-carrying microorganisms in sediment samples (termed YC1, YC2, and YC5) from a low-temperature hot spring. Microcosm assays revealed that only YC1 and YC2 exhibited limited As-methylating activities, generating a maximum of 2.3–3.5 μg/L methylarsenate (MMA) and 2.2–2.8 μg/L dimethylarsenate (DMA). The addition of lactate and arsenite significantly promoted these activities, increasing the concentrations to 26.1–184.0 μg/L MMA and 38.1–204.0 μg/L DMA. The arsM gene abundance also increased by 46–276%, indicating that lactate can activate arsenite methylation. YC1 and YC2, which were closer to the hot spring hole than YC5 was, had similar patterns, and shared a similar arsM community structure, dominated by Actinobacteriota, Firmicutes, and Proteobacteriota on days 7 and 21. In contrast, at YC5, the sampling site far from the spring hole, representatives of Acidobacteriota were dominant on day 7, whereas those of Actinobacteriota were prevalent on day 21. Acidobacteriota co-occurred with dimethylarsenate production, and Mycobacterium co-occurred with DMA demethylation. These findings suggested that the low-temperature arsenic hot spring possessed diverse arsenic-methylating species, whereas demethylating bacteria preferred to inhabit niches farther from the hot spring.

Soil Microbiomes and their Arsenic Functional Genes in Chronically High-Arsenic Contaminated Soils.

Microbial arsenic transformations play essential roles in controlling pollution and ameliorating risk. This study combined high-throughput sequencing and PCR-based approaches targeting both the 16S rRNA and arsenic functional genes to investigate the temporal and spatial dynamics of the soil microbiomes impacted by high arsenic contamination (9.13 to 911.88mg/kg) and to investigate the diversity and abundance of arsenic functional genes in soils influenced by an arsenic gradient. The results showed that the soil microbiomes were relatively consistent and mainly composed of Actinobacteria (uncultured Gaiellales and an unknown_67 - 14 bacterium), Proteobacteria, Firmicutes (particularly, Bacillus), Chloroflexi, and Acidobacteria (unknown_Subgroup_6). Although a range of arsenic functional genes (e.g., arsM, arsC, arrA, and aioA) were identified by shotgun metagenomics, only the arsM gene was detected by the PCR-based method. The relative abundance of the arsM gene accounted for 0.20%-1.57% of the total microbial abundance. Combining all analyses, arsenic methylation mediated by the arsM gene was proposed to be a key process involved in the arsenic biogeochemical cycle and mitigation of arsenic toxicity. This study advances our knowledge about arsenic mechanisms over the long-term in highly contaminated soils.

Biotransformation of Pb and As from sewage sludge and food waste by black soldier fly larvae: Migration mechanism of bacterial community and metalloregulatory protein scales

The accumulation and transformation of lead (Pb) and arsenic (As) during the digestion of sewage sludge (SS) by black soldier fly larvae (BSFL) remain unclear. In this study, we used 16 s rRNA and metagenomic sequencing techniques to investigate the correlation between the microbial community, metalloregulatory proteins (MRPs), and Pb and As migration and transformation. During the 15-day test period, BSFL were able to absorb 34–48 % of Pb and 32–45 % of As into their body. Changes in bacterial community abundance, upregulation of MRPs, and redundancy analysis (RDA) results confirmed that ZntA, EfeO, CadC, ArsR, ArsB, ArsD, and ArsA play major roles in the adsorption and stabilization of Pb and As, which is mainly due to the high contribution rates of Lactobacillus (48–59 %) and Enterococcus (21–23 %). Owing to the redox reaction, the regulation of the MRPs, and the change in pH, the Pb and As in the BSFL residue were mainly the residual fraction (F4). The RDA results showed that Lactobacillus and L.koreensis could significantly (P < 0.01) reduce the reducible fraction (F2) and F4 of Pb, whereas Firmicutes and L.fermentum can significantly (P < 0.05) promote the transformation of As to F4, thus realizing the passivation Pb and As. This study contributes to the understanding of Pb and As in SS adsorbed by BSFL and provides important insights into the factors that arise during the BSFL-mediated migration of Pb and As.

Mineralogical transformation of arsenic at different copper smelting workshops: The impact on arsenic bioaccessibility

Soil arsenic (As) contamination associated with the demolition of smelting plants has received increasing attention. Soil As can source from different industrial processes, and also participate in soil weathering, making its speciation rather complex. This study combined the usage of chemical sequential extraction and advanced spectroscopic techniques, e.g., time of flight secondary ion mass spectrometry (ToF-SIMS), to investigate the mineralogical transformation of soil As at different processing sites from a typical copper smelting plant in China. Results showed that the stability of arsenic species decreased following the processes of storage, smelting, and flue gas treatment. Arsenic in the warehouse area was incorporated into pyrite (FeS2) as well as its secondary minerals such as jarosite (KFe3(SO4)2(OH)6). At the smelting area, a large proportion of As was adsorbed by iron oxides from smelting slags, while some As existed in stable forms like orpiment (As2S3). At the acid-making area, more than half of As was adsorbed on amorphous iron oxides, and some were adsorbed on the flue gas desulfurization gypsum. More importantly, over 86% of the As belonged to non-specifically and specifically adsorbed fractions was found to be bioaccessible, highlighting the gypsum-adsorbed As one of the most hazardous species in smelting plant soils. Our findings indicated the importance of iron oxides in As retention and suggested the potential health risk of gypsum-adsorbed As. Such detailed knowledge of As speciation and bioaccessibility is vital for the management and remediation of As-contaminated soils in smelting plants.

Effects of citric acid on arsenic transformation and microbial communities in different paddy soils

Root exudate is a major source of soil organic matter and can significantly affect arsenic (As) migration and transformation in paddy soils. Citric acid is the main component of rice root exudate, however, the impacts and rules of citric acid on As bioavailability and rhizobacteria in different soils remains unclear. This study investigated the effects of citric acid on As transformation and microbial community in ten different paddy soils by flooded soil culture experiments. The results showed that citric acid addition increased total As and arsenate (As(V)) in the soil porewater by up to 41-fold and 65-fold, respectively, after 2-h incubation. As(V) was the main As species in soil porewater within 10 days with the addition of citric acid. Non-specifically sorbed As of soils, total Fe and total As were the main environmental factors affecting the soil microbial communities. High-throughput sequencing analysis demonstrated that citric acid addition significantly altered the soil microbial community structure, shifting the Proteobacteria-related reducing bacteria to Firmicutes-related reducing bacteria in different paddy soils. The relative abundance of Firmicutes was promoted by 174–196%. Clostridium-related bacteria belonging to Firmicutes became the dominant genera, which is believed to regulate As release through the reductive dissolution of iron oxides or the direct reduction of As(V) to arsenite (As(III)). However, citric acid addition significantly decreased the relative abundance of Geobacter and Anaeromyxobacter, which are also typical active As(V)- and ferric-reducing bacteria. Real-time quantitative polymerase chain reaction (qPCR) also revealed that the addition of citric acid significantly decreased the relative abundances of Geobacter in the different soils by 8–28 times while the relative abundances of Clostridium increased by 2–5 times. These results provide significant insight on As transformation in different types of rice rhizospheric soils and guidance for the application of rice varieties with low citric acid exuding to restrict As accumulation.