Thioarsenate sorbs to natural organic matter through ferric iron-bridged ternary complexation to a lower extent than arsenite.

Understanding processes regulating thioarsenate (HAsSO; n = 1 - 3; x = 1 - 3) mobility is essential to predicting the fate of arsenic (As) in aquatic environments under anoxic conditions. Under such conditions, natural organic matter (NOM) is known to effectively sorb arsenite and arsenate due to metal cation-bridged ternary complexation with the NOM. However, the extent and mechanism of thioarsenate sorption onto NOM via similar complexation has not been investigated.

Long-Term Paddy Soil Development Buffers the Increase in Arsenic Methylation and Thiolation after Sulfate Fertilization.

Sulfate fertilization has been proposed to limit arsenic (As) mobility in paddy soils and accumulation in rice grains. However, As and sulfur (S) have complex biogeochemical interactions. Besides the desired precipitation of sulfides that sorb or incorporate As, S can enhance As biotic methylation and abiotic thiolation.

Arsenic immobilization and greenhouse gas emission depend on quantity and frequency of nitrogen fertilization in paddy soil.

Nitrogen (N) fertilization in paddy soils decreases arsenic mobility and methane emissions. However, it is unknown how quantity and frequency of N fertilization affects the interlinked redox reactions of iron(II)-driven denitrification, iron mineral (trans-)formation with subsequent arsenic (im-)mobilization, methane and nitrous oxide emissions, and how this links to microbiome composition. Thus, we incubated paddy soil from Vercelli, Italy, over 129 days and applied nitrate fertilizer at different concentrations (control: 0, low: ∼35, medium: ∼100, high: ∼200 mg N kg soil) once at the beginning and after 49 days.

Quantitative proteomics reveals the Sox system's role in sulphur and arsenic metabolism of phototroph Halorhodospira halophila.

The metabolic process of purple sulphur bacteria's anoxygenic photosynthesis has been primarily studied in Allochromatium vinosum, a member of the Chromatiaceae family. However, the metabolic processes of purple sulphur bacteria from the Ectothiorhodospiraceae and Halorhodospiraceae families remain unexplored. We have analysed the proteome of Halorhodospira halophila, a member of the Halorhodospiraceae family, which was cultivated with various sulphur compounds.

Long-term paddy use influences response of methane production, arsenic mobility and speciation to future higher temperatures.

Anaerobic microbial metabolisms make flooded paddy soils a major source of the greenhouse gas methane (CH) and mobilize toxic arsenic (As), threatening rice production and consumption. Increasing temperatures due to climate change enhance these microbially mediated processes, increasing their related threats. Chronosequence studies show that long-term paddy use ("age") changes soil properties and redox biogeochemistry through soil organic carbon (SOC) accumulation, its association to amorphous iron (Fe) phases, and increased microbial activity.

Simultaneously decreasing arsenic and cadmium in rice by soil sulfate and limestone amendment under intermittent flooding.

Water management in paddy soils can effectively reduce the soil-to-rice grain transfer of either As or Cd, but not of both elements simultaneously due to the higher mobility of As under reducing and Cd under oxidizing soil conditions. Limestone amendment, the common form of liming, is well known for decreasing Cd accumulation in rice grown on acidic soils. Sulfate amendment was suggested to effectively decrease As accumulation in rice, especially under intermittent soil flooding.

Seasonal Formation of Low-Sorbing Methylthiolated Arsenates Induces Arsenic Mobilization in a Minerotrophic Peatland.

Peatlands are known sinks for arsenic (As). In the present study, seasonal As mobilization was observed in an acidic, minerotrophic peatland (called Lehstenbach) in late summer, accompanied by a peak in dissolved sulfide (S(-II)). Arsenic speciation revealed the lowest seasonal porewater concentrations of arsenite and arsenate, likely due to As(III)-S-bridging to natural organic matter.

Arsenic Thiolation in Rice and .

Inorganic and methylated thioarsenates have recently been reported to form in paddy soil pore waters and accumulate in rice grains. Among them, dimethylmonothioarsenate (DMMTA) is particularly relevant because of its high cytotoxicity and potential misidentification as nonregulated dimethylarsenate (DMA). Studying DMMTA uptake and flag leaf, grain, and husk accumulation in rice plants during grain filling, substantial dethiolation to DMA was observed with only 8.

Changes in arsenic mobility and speciation across a 2000-year-old paddy soil chronosequence.

Rice accumulates arsenic (As) when cultivated under flooded conditions in paddy soils threatening rice yield or its safety for human consumption, depending on As speciation. During long-term paddy use, repeated redox cycles systematically alter soil biogeochemistry and microbiology. In the present study, incubation experiments from a 2000-year-old paddy soil chronosequence revealed that As mobilization and speciation also change with paddy soil age.

Widespread occurrence of dimethylmonothioarsenate (DMMTA) in rice cakes: Effects of puffing and storage.

Thioarsenates have recently been detected in rice and rice-based products, with particularly high contents in puffed rice cakes. Here, we show that puffing rice can cause almost complete transformation of dimethylarsenate (DMA) to dimethyldithioarsenate (DMDTA) and dimethylmonothioarsenate (DMMTA). Analysis of puffed rice cakes after 3 months of non-sealed storage at room temperature showed transformation of DMDTA mainly into DMMTA.

Immobilizing arsenic in contaminated anoxic aquifer sediment using sulfidated and uncoated zero-valent iron (ZVI).

Arsenic (As) is carcinogenic and of major concern in groundwater. We collected sediment material from a contaminated anoxic aquifer in Sweden and investigated the immobilization of As by four commercial zero-valent iron (ZVI) particles. Solid-phase As and Fe speciation was assessed using X-ray absorption spectroscopy (XAS) and solution-phase As speciation using chromatographic separation.

Microbial communities in paddy soils: differences in abundance and functionality between rhizosphere and pore water, the influence of different soil organic carbon, sulfate fertilization and cultivation time, and contribution to arsenic mobility and speciation.

Abiotic factors and rhizosphere microbial populations influence arsenic accumulation in rice grains. Although mineral and organic surfaces are keystones in element cycling, localization of specific microbial reactions in the root/soil/pore water system is still unclear. Here, we tested if original unplanted soil, rhizosphere soil and pore water represented distinct ecological microniches for arsenic-, sulfur- and iron-cycling microorganisms and compared the influence of relevant factors such as soil type, sulfate fertilization and cultivation time.

Mobilization of Colloid- and Nanoparticle-Bound Arsenic in Contaminated Paddy Soils during Reduction and Reoxidation.

The association of arsenic (As) with colloidal particles could facilitate its transport to adjacent water systems or alter its availability in soil-rice systems. However, little is known about the size distribution and composition of particle-bound As in paddy soils, particularly under changing redox conditions. Here, we incubated four As-contaminated paddy soils with distinctive geochemical properties to study the mobilization of particle-bound As during soil reduction and subsequent reoxidation.

Methanogens-Driven Arsenic Methylation Preceding Formation of Methylated Thioarsenates in Sulfide-Rich Hot Springs.

Hot springs represent a major source of arsenic release into the environment. Speciation is typically reported to be dominated by arsenite, arsenate, and inorganic thiolated arsenates. Much less is known about the relevance and formation of methylated thioarsenates, a group with species of high mobility and toxicity.

Consequences of sea level rise for high metal(loid) loads in the Ría of Huelva estuary sediments.

Ría of Huelva, located in southwestern Spain, is a highly metal(loid)-contaminated estuary system where sediments are exceeding action limits in an increasing order for Cd, Zn, Pb, Cu, and As. With a predicted sea level rise over the next 50 years, the estuary will be subject to flooding with brackish water or seawater. To evaluate the risk of metal(loid) mobilization under future climate scenarios, different locations along the estuary were sampled at different depths.

Decreasing arsenic in rice: Interactions of soil sulfate amendment and water management.

Accumulation of inorganic arsenic (iAs) and dimethylarsenate (DMA) in rice threatens human health and rice yield, respectively. We studied the yet unclear interactions of soil sulfate amendment and water management for decreasing As accumulation in rice grain in a pot experiment. We show that soil sulfate amendment (+200 mg S/kg soil) decreased grain iAs by 44% without clearly increasing grain DMA under intermittent flooding from booting stage to maturation.

Low levels of arsenic and cadmium in rice grown in southern Florida Histosols - Impacts of water management and soil thickness.

Rice is planted as a rotation crop in the sugarcane-dominant Everglades Agricultural Area (EAA) in southern Florida. The Histosols in this area are unlike other mineral soils used to grow rice due to the high organic content and land subsidence caused by rapid oxidation of organic matter upon drainage. It remains unknown if such soils pose a risk of arsenic (As) or cadmium (Cd) mobilization and uptake into rice grain.

Different sulfide to arsenic ratios driving arsenic speciation and microbial community interactions in two alkaline hot springs.

Arsenic (As) is ubiquitous in geothermal fluids, which threatens both water supply safety and local ecology. The co-occurrence of sulfur (S) and As increases the complexity of As migration and transformation in hot springs. Microorganisms play important roles in As-S transformation processes.

Mechanism of Arsenic Partitioning During Sulfidation of As-Sorbed Ferrihydrite Nanoparticles.

Knowledge of how arsenic (As) partitions among various phases in Fe-rich sulfidic environments is critical for understanding the fate and mobility of As in such environments. We studied the reaction of arsenite and arsenate sorbed on ferrihydrite nanoparticle surfaces with dissolved sulfide at varying S/Fe ratios (0.1-2.

Dimethylated Thioarsenates: A Potentially Dangerous Blind Spot in Current Worldwide Regulatory Limits for Arsenic in Rice.

Arsenic (As) occurrence in rice is a serious human health threat. Worldwide, regulations typically limit only carcinogenic inorganic As, but not possibly carcinogenic dimethylated oxyarsenate (DMA). However, there is emerging evidence that "DMA", determined by routine acid-based extraction and analysis, hides a substantial share of dimethylated thioarsenates that have similar or higher cytotoxicities than arsenite.

Dimethylmonothioarsenate Is Highly Toxic for Plants and Readily Translocated to Shoots.

Arsenic is one of the most relevant environmental pollutants and human health threats. Several arsenic species occur in soil pore waters. Recently, it was discovered that these include inorganic and organic thioarsenates.

Microbial communities contribute to the elimination of As, Fe, Mn, and NH from groundwater in household sand filters.

Household sand filters (SFs) are widely applied to remove iron (Fe), manganese (Mn), arsenic (As), and ammonium (NH) from groundwater in the Red River delta, Vietnam. Processes in the filters probably include a combination of biotic and abiotic reactions. However, there is limited information on the microbial communities treating varied groundwater compositions and on whether biological oxidation of Fe(II), Mn(II), As(III), and NH contributes to the overall performance of SFs.

Widespread Occurrence of the Highly Toxic Dimethylated Monothioarsenate (DMMTA) in Rice Globally.

Arsenic (As) accumulation in rice is of global concern for human health and international trade. Rice is typically reported to contain inorganic As (iAs) and dimethylated arsenate (DMA), with current food guidelines limiting toxic iAs but not less-toxic DMA. Here, we show that the highly toxic dimethylated monothioarsenate (DMMTA) is also found in rice worldwide and has been unknowingly determined as less-toxic DMA by previous routine analytical methods.

Alternating Wet-Dry Cycles Rather than Sulfate Fertilization Control Pathways of Methanogenesis and Methane Turnover in Rice Straw-Amended Paddy Soil.

Alternate wet-drying (AWD) and sulfate fertilization have been considered as effective methods for lowering CH emissions from paddy soils. However, there is a clear knowledge gap between field studies that focus on the quantification of emissions and laboratory studies that investigate mechanisms. To elucidate mechanisms of CH production and oxidation under field conditions, rice was planted in straw-amended mesocosms with or without sulfate fertilization under continuously flooded conditions (FL) or two wet-dry cycles.