Mo than meets the eye: genomic insights into molybdoenzyme diversity of Seleniivibrio woodruffii strain S4T.

Seleniivibrio woodruffii strain S4T is an obligate anaerobe belonging to the phylum Deferribacterota. It was isolated for its ability to respire selenate and was also found to respire arsenate. The high-quality draft genome of this bacterium is 2.9 Mbp, has a G+C content of 48%, 2762 predicted genes of which 2709 are protein-coding, and 53 RNA genes. An analysis of the genome focusing on the genes encoding for molybdenum-containing enzymes (molybdoenzymes) uncovered a remarkable number of genes encoding for members of the dimethylsulfoxide reductase family of proteins (DMSOR), including putative reductases for selenate and arsenate respiration, as well as genes for nitrogen fixation. Respiratory molybdoenzymes catalyze redox reactions that transfer electrons to a variety of substrates that can act as terminal electron acceptors for energy generation. Seleniivibrio woodruffii strain S4T also has essential genes for molybdate transporters and the biosynthesis of the molybdopterin guanine dinucleotide cofactors characteristic of the active centers of DMSORs. Phylogenetic analysis revealed candidate respiratory DMSORs spanning nine subfamilies encoded within the genome. Our analysis revealed the untapped potential of this interesting microorganism and expanded our knowledge of molybdoenzyme co-occurrence.

Gut microbiota deficiency aggravates arsenic-induced toxicity by affecting bioaccumulation and biotransformation in C57BL/6J mice.

Gut microbiome can influence the arsenic metabolism in mammals. Confusingly, gut microbiome was found to both mitigate and exacerbate arsenic toxicity. In this study, the role of gut microbiota in arsenic bioaccumulation, biotransformation, and organ toxicity in C57BL/6J mice was investigated. Gut microbiota deficiency model was established by antibiotics (Ab) cocktail AVNM. Conventional and gut microbiota deficiency mice were exposed to NaAsO2 for 4 weeks. Comparing with Ab-treated mice, the total arsenic (tAs) in the tissues was significantly reduced in conventional mice, which was opposed to the results of those in feces. Interestingly, dimethyl arsenite (DMA) was the most abundant metabolite in the feces of Ab-treated mice, while arsenic acid (AsV) had the highest proportion in the feces of conventional mice with approximately 16-fold than that in Ab-treated mice, indicating the critical role of gut microbiota in metabolizing arsenious acid (AsIII) to AsV. Additionally, the liver and kidney in Ab-treated mice showed more severe pathological changes and apoptosis. The significant increased level of ionized calcium-binding adapter molecule 1 (IBA-1) was also found in the brains of Ab-treated mice. Our results indicated that gut microbiota protected the host from arsenic-induced toxicity in liver, kidney, and brain by reducing the arsenic accumulation.

A novel sulfidogenic process via sulfur reduction to remove arsenate in acid mine drainage: Insights into the performance and microbial mechanisms.

Biological sulfidogenic processes based on sulfate-reducing bacteria (SRB) are not suitable for arsenic (As)-containing acid mine drainage (AMD) treatment because of the formation of the mobile thioarsenite during sulfate reduction. In contrast, biological sulfidogenic processes based on sulfur-reducing bacteria (S0RB) produce sulfide without pH increase, which could achieve more effective As removal than the SRB-based process. However, the reduction ability and toxicity tolerance of S0RB to As remains mysterious, which may substantially affect the practical applicability of this process when treating arsenate (As(V))-containing AMD. Thus, this study aims to develop a biological sulfur reduction process driven by S0RB, and explore its long-term performance on As(V) removal and microbial community evolution. Operating under moderately acidic conditions (pH=4.0), the presence of 10 mg/L As(V) significantly suppressed the activity of S0RB, leading to the failure of As(V) removal. Surprisingly, a drop in pH to 3.0 enhanced the tolerance of S0RB to As toxicity, allowing for efficient sulfide production (396±102 mg S/L) through sulfur reduction. Consequently, effective and stable removal of As(V) (99.9 %) was achieved, even though the sulfidogenic bacteria were exposed to high levels of As(V) (42 mg/L) in long-term trials. Spectral and spectroscopic analysis showed that As-bearing sulfide minerals were present in the bioreactor. Remarkably, the presence of As(V) induced notable changes in the microbial community composition, with Desulfurella and Clostridium identified as predominate sulfur reducers. The qPCR result further revealed an increase in the concentration of functional genes related to As transport (asrA and arsB) in the bioreactor sludge as the pH decreased from 4.0 to 3.0. This suggests the involvement of microorganisms carrying asrA and arsB in an As transport process. Furthermore, metagenomic binning demonstrated that Desulfurella contained essential genes associated with sulfur reduction and As transportation, indicating its genetic potential for sulfide production and As tolerance. In summary, this study underscores the effectiveness of the biological sulfur reduction process driven by S0RB in treating As(V)-contaminated AMD. It offers insights into the role of S0RB in remediating As contamination and provides valuable knowledge for practical applications.

Nitric oxide acts upstream of indole-3-acetic acid in ameliorating arsenate stress in tomato seedlings.

After their discovery, nitric oxide (NO) and indole-3-acetic acid (IAA) have been reported as game-changing cellular messengers for reducing abiotic stresses in plants. But, information regarding their shared signaling in regulating metal stress is still unclear. Herein, we have investigated about the joint role of NO and IAA in mitigation of arsenate [As(V)] toxicity in tomato seedlings. Arsenate being a toxic metalloid increases the NPQ level and cell death while decreasing the biomass accumulation, photosynthetic pigments, chlorophyll a fluorescence, endogenous NO content in tomato seedlings. However, application of IAA or SNP to the As(V) stressed seedlings improved growth together with less accumulation of arsenic and thus, preventing cell death. Interestingly, addition of c-PTIO, {2-(4-carboxyphenyl)-4, 4, 5, 5-tetramethylimidazoline-1-oxyl-3-oxide, a scavenger of NO} and 2, 3, 5-triidobenzoic acid (TIBA, an inhibitor of polar auxin transport) further increased cell death and inhibited activity of GST, leading to As(V) toxicity. However, addition of IAA to SNP and TIBA treated seedlings reversed the effect of TIBA resulting into decreased As(V) toxicity. These findings demonstrate that IAA plays a crucial and advantageous function in NO-mediated reduction of As(V) toxicity in seedlings of tomato. Overall, this study concluded that IAA might be acting as a downstream signal for NO-mediated reduction of As(V) toxicity in tomato seedlings.

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.

Metabolomics profiling reveals the detoxification and tolerance behavior of two bread wheat (Triticum aestivum L.) varieties under arsenate stress.

The present study conducted metabolomics profiling (targeted and untargeted) in the roots of two wheat varieties (BARANI-70 and NARC-09) under arsenate stress in a hydroponic experiment. The findings indicated a better growth response of BARANI-70 compared to the NARC-09. From amino acid profiling, a total of 26 amino acids (AAs) were quantified in roots. BARANI-70 showed higher induction of stress-responsive AAs compared to the NARC-09. From untargeted metabolomics, a total of 136 metabolites were identified: AAs, fatty acids, purines, carnitines, LysoPCs, and others. The KEGG pathway identified pathways such as linoleic acid metabolism, TCA cycle, glutathione metabolism, and aminoacyl-tRNA biosynthesis that were regulated to improve the defense of tolerant variety. BARANI-70 emerged as a tolerant variety based on the psychological response, As accumulation, and behavior of stress-responsive metabolites. This study should facilitate the breeding of low-As accumulating wheat varieties for future application to ensure sustainable production and food safety.

Short-term effects of sodium arsenite (AsIII) and sodium arsenate (AsV) on carbohydrate metabolism in the perfused rat liver.

The actions of arsenite and arsenate on carbohydrate metabolism in the once-through perfused rat liver were investigated. The compound inhibited lactate gluconeogenesis with an IC50 of 25 µM. It also increased glycolysis and fructolysis at concentrations between 10 and 100 µM. This effect was paralleled by strong inhibition of pyruvate carboxylation (IC50 = 4.25 µM) and by a relatively moderate diminution in the ATP levels. The inhibitory action of arsenate on pyruvate carboxylation and lactate gluconeogenesis was 103 times less effective than that of arsenite. For realistic doses and concentrations («1 mM), impairment of metabolism by arsenate can be expected to occur solely after its reduction to arsenite. Arsenite, on the other hand, can be regarded as a strong short-term modifier of lactate gluconeogenesis and other pathways. The main cause of the former is inhibition of pyruvate carboxylation, a hitherto unknown effect of arsenic compounds.

Static and dynamic adsorption of arsenate from water by Fe3+ complexed with 3-aminopropyltriethoxysilane-modified carboxymethyl chitosan.

Fe3+ complexed with 3-aminopropyltriethoxysilane (APTES)-modified carboxymethyl chitosan (CMC) named Fe-ACMC was synthesized by a one-step method at room temperature and pressure. The surface morphology and chemical structure of Fe-ACMC were characterized by SEM-EDS, XRD, BET, FT-IR, XPS, and ζ-potential. In batch adsorption, the optimum pH for arsenate [As(V)] adsorption onto Fe-ACMC was 3-9 with removal efficiency > 99%. The adsorption of As(V) could reach equilibrium within 25 min and the maximum adsorption capacity was 84.18 mg g-1. The pseudo-second-order model fitted well the kinetic data (R2 = 0.995), while the Freundlich model well described the adsorption isotherm of As(V) on Fe-ACMC (R2 = 0.979). The co-existing anions (NO3-, CO32-, and SO42-) exhibited a slight impact on the As(V) adsorption efficiency, whereas PO43- inhibited As(V) adsorption on Fe-ACMC. The real applicability of Fe-ACMC was achieved to remove ca. 10.0 mg L-1 of As(V) from natural waters to below 0.05 mg L-1. The regeneration and reuse of Fe-ACMC for As(V) adsorption were achieved by adding 0.2 mol L-1 HCl. The main adsorption mechanism of As(V) on Fe-ACMC was attributed to electrostatic attraction and inner-sphere complexation between -NH2···Fe3+ and As(V). In fixed-bed column adsorption, the Thomas model was the most suitable model to elucidate the dynamic adsorption behavior of As(V). The loading capacity of the Fe-ACMC packed column for As(V) was 47.04 mg g-1 at pH 7 with an initial concentration of 60 mg L-1, flow rate of 3 mL min-1, and bed height of 0.6 cm.

Innovative methodology for comprehensive utilization of arsenic-bearing neutralization sludge.

Arsenic-bearing neutralization (ABN) sludge is a classical hazardous waste commonly found in nonferrous metallurgy. However, the current storage of these hazardous wastes not only has to pay costly hazardous waste taxes but also poses significant risks to both the environment and human health. To address these issues and achieve the comprehensive utilization and minimization of ABN sludge, this study proposes a new combined process. The process involves selective reduction roasting, leaching, and carbonation, through which, the arsenate and gypsum in the ABN sludge were recovered in the form of As(s), high-purity CaCO3, and H2S. The selective reduction behaviors of arsenate and gypsum were investigated through thermodynamic analysis and roasting experiments. The results indicated that the 95.35 % arsenate and 96.55 % gypsum in the sludge were selectively reduced to As4(g) and CaS at 950 °C by carbothermic reduction. The As4(g) was condensed to As(s) and enriched in the dust (As, 96.78 wt %). In the leaching process, H2S gas was adopted to promote the leaching of CaS, and resulted in 97.41 % of CaS in the roasted product was selectively leached in the form of Ca(HS)2, leading to a 74.11 % reduction in the weight of the ABN sludge. Then, the Ca(HS)2 was subjected to capture CO2 for the separation of Ca2+ and S2-. The result depicted that 99.69 % of Ca2+ and 99.12 % of S2- were separated as high-purity (99.12 wt %) CaCO3 and H2S (24.89 vol %) by controlling the terminal carbonation pH to below 6.55. The generated H2S can be economically converted to sulfur by the Clause process. The whole process realized the comprehensive resource recovery and the minimization of the sludge, which provides an alternative solution for the clean treatment of hazardous ABN waste.

Isolation and characterization of PGPR obtained from different arsenic-contaminated soil samples and their effect on photosynthetic characters of maize grown under arsenic stress.

Contamination of the environment due to speedup of anthropogenic activities has become a serious threat to modern humanity. Among the contaminants, the new emerging concern is the heavy metal (HM) contamination in the environment. Because the persistence and harmfulness of heavy metals affect the ecosystem and the health of plants, animals, and humans, they are the most toxic substances in the environment. Among them, Arsenic (As) emerged as major environmental constraint leading to enormous negative effects on the plant, animal, and human health. Even in minute quantity, As is known to cause various critical diseases in humans and toxicity in plants. Research was performed to observe the capability of plant growth-promoting strains of bacteria in enhancing Zea mays (L.) growth in arsenic polluted soil. Total 30 bacterial strains were isolated from the polluted soils, screened for plant growth promotion potential and arsenic tolerance. Eighteen isolates showed resistance to different levels of sodium arsenate (ranging from 0 to 50 mM) in agar plate using LB media. Of 18 isolates, 83.3% produced IAA, methyl red, and hydrogen cyanide; 55.5% exhibited catalase activity; 61.1% showed siderophore production; 88.8% showed phosphate solubilization; and 44.4% showed oxidase, Voges proskauer activity, and KOH solubility. The most efficient isolates SR3, SD5, and MD3 with significant arsenic tolerance and plant growth-promoting (PGP) activity were examined via sequencing of amplified 16S rRNA gene. Isolates of bacteria, i.e., SR3, SD5, and MD3, showing multiple PGP-traits were identified as Bacillus pumilus (NCBI accession number: OR459628), Paenibacillus faecalis (NCBI accession number: OR461560), and Pseudochrobactrum asaccharolyticum (NCBI accession number: OR458922), respectively. Maize seeds treated with these PGPR strains were grown in pots contaminated with 50 ppm and 100 ppm sodium arsenate. Compared to untreated arsenic stressed plants, bacterial inoculation P. asaccharolyticum (MD3) resulted 20.54%, 18.55%, 33.45%, 45.08%, and 48.55% improvement of photosynthetic pigments (carotenoid content, chlorophyll content, stomatal conductance (gs), substomatal CO2, and photosynthetic rate), respectively. Principal component analysis explained that first two components were more than 96% of the variability for each tested parameter. The results indicate that in comparison to other isolates, P. asaccharolyticum isolate can be used as efficient agent for improving maize growth under arsenic polluted soil.

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 mobilization was driven by the formation of arsenite-S(-II) colloids and formation of methylthiolated arsenates (up to 59% of the sum of As species) and to a minor extent also of inorganic thioarsenates (6%-30%) and oxymethylated arsenates (5%-24%). Sorption experiments using a purified model peat, the Lehstenbach peat, natural (to mimic winter conditions) and reacted with S(-II) (to mimic late summer conditions) at acidic and neutral pH confirmed low sorption of methylthiolated arsenates. At acidic pH and in the presence of S(-II), oxymethylated arsenates were completely thiolated. This methylthiolation decreased As sorption up to 10 and 20 times compared with oxymethylated arsenates and arsenite, respectively. At neutral pH, thiolation of monomethylated arsenates was incomplete, and As could be partially retained as oxymethylated arsenates. Dimethylated arsenate was still fully thiolated and highly mobile. Misidentification of methylthiolated arsenates as oxymethylated arsenates might explain previous contradictory reports of methylation decreasing or increasing As mobility.

Exploring the interference mechanisms of surface and aqueous complexes with groundwater arsenate and arsenite adsorption.

Ca2+, Mg2+, and HCO3- are extremely common coexisting ions with arsenic (As) in geogenic As-polluted groundwaters. Although extensive research has improved our knowledge of groundwater As removal techniques and mechanisms, there is still a lack of a definite explanation of the distinct influences of Ca2+ and Mg2+ on As immobilization. Furthermore, the question of whether the occurrence of metal-As aqueous complexes has positive or detrimental effects on As adsorption is still open, which hinders our ability to predict the effectiveness of groundwater As removal. The goal of our present work was to investigate the molecular-level interference mechanisms of Ca2+, Mg2+, and HCO3- on arsenic adsorption with batch/column filtration experiments and spectroscopic techniques. The results showed that the co-presence of Ca2+ and As significantly increased As(V) and As(III) adsorption by 22.1 and 12.2% in batch studies and by 20.1 and 16.7% in column adsorptive filtrations, which could be explained by forming a ternary Ca-As-TiO2 complex. Without the surface complex, Mg2+ only had a slightly positive effect on As removal. Co-existence of Ca2+ and HCO3- prevented the generation this surface complex, which significantly decreased the elimination of As(III). Inversely, the As(V) ternary complex and adsorption were not interfered by HCO3-. Moreover, an aqueous Ca-As(V) complex was detected without surface, which facilitated generation of the surface complex and As(V) adsorption. The results of this work clarified the distinct effects of Ca2+ and Mg2+ and As(V) and As(III) adsorption, which was critical in predicting the As adsorption efficiency in column filtration processes.

Soil Humic Acid Stimulates Potentially Active Dissimilatory Arsenate-Reducing Bacteria in Flooded Paddy Soil as Revealed by Metagenomic Stable Isotope Probing.

Dissimilatory arsenate reduction contributes a large proportion of arsenic flux from flooded paddy soil, which is closely linked to soil organic carbon input and efflux. Humic acid (HA) represents a natural ingredient in soil and is shown to enhance microbial arsenate respiration to promote arsenic mobility. However, the community and function profiles of metabolically active arsenate-respiring bacteria and their interactions with HA in paddy soil remain unclear. To probe this linkage, we performed a genome-centric comparison of potentially active arsenate-respiring bacteria in anaerobic microcosms amended with 13C-lactate and HA by combining stable-isotope probing with genome-resolved metagenomics. Indeed, HA greatly accelerated the microbial reduction of arsenate to arsenite. Enrichment of bacteria that harbor arsenate-respiring reductase genes (arrA) in HA-enriched 13C-DNA was confirmed by metagenomic binning, which are affiliated with Firmicutes (mainly Desulfitobacterium, Bacillus, Brevibacillus, and Clostridia) and Acidobacteria. Characterization of reference extracellular electron transfer (EET)-related genes in these arrA-harboring bacteria supports the presence of EET-like genes, with partial electron-transport chain genes identified. This suggests that Gram-positive Firmicutes- and Acidobacteria-related members may harbor unspecified EET-associated genes involved in metal reduction. Our findings highlight the link between soil HA and potentially active arsenate-respiring bacteria, which can be considered when using HA for arsenic removal.

Multifaceted response mechanisms of Oryza sativa L. 'KDML105' to high arsenite and arsenate stress levels.

Toxicity resulting from high levels of inorganic arsenic (iAs), specifically arsenite (AsIII) and arsenate (AsV), significantly induces oxidative stress and inhibits the growth of rice plants in various ways. Despite its economic importance and significance as a potent elite trait donor in rice breeding programmes, Khao Dawk Mali 105 (KDML105) has received limited attention regarding its responses to As stress. Therefore, this study aimed to comprehensively investigate how KDML105 responds to elevated AsIII and AsV stress levels. In this study, the growth, physiology, biochemical attributes and levels of As stress-associated transcripts were analysed in 45-day-old rice plants after exposing them to media containing 0, 75, 150, 300 and 600 µM AsIII or AsV for 1 and 7 days, respectively. The results revealed that AsIII had a more pronounced impact on the growth and physiological responses of KDML105 compared to AsV at equivalent concentrations. Under elevated AsIII treatment, there was a reduction in growth and photosynthetic efficiency, accompanied by increased levels of hydrogen peroxide (H2O2) and malondialdehyde (MDA). Notably, the total contents of antioxidants, such as proline, phenolics and flavonoids in the shoot, increased by 8.1-fold, 1.4-fold and 1.6-fold, respectively. Additionally, the expression of the OsABCC1 gene in the roots increased by 9.5-fold after exposure to 150 µM AsIII for 1 day. These findings suggest that KDML105's prominent responses to As stress involve sequestering AsIII in vacuoles through the up-regulation of the OsABCC1 gene in the roots, along with detoxifying excessive stress in the leaves through proline accumulation. These responses could serve as valuable traits for selecting As-tolerant rice varieties.

Determination and speciation of arsenic in drinking water samples by X-ray spectrometry technique.

Arsenic is ranked as the first compound in the Substance Priority List 2023 by the Agency for Toxic Substances and Disease Registry (ATSDR). The most prominent entrance to the human body is through drinking water wherein the predominant species are arsenite and arsenate. The more toxic As(III) has rigorously threatened human health worldwide; hence, speciation and separation are the need of the hour. In this article, we have reported a simple method of arsenic speciation by wavelength dispersive X-ray fluorescence (WD-XRF) spectrometer. Valence to core (VtC) electronic transitions, i.e., AsKß2,5 fluorescence lines were used for arsenic speciation. This speciation study by WD-XRF entails direct measurement of activated alumina pellets containing arsenate and arsenite species adsorbed from water sample without separation of the trivalent and pentavalent species. This is the first report wherein the X-ray technique has been explored for speciation analysis of arsenic and the biggest advantage of the method lies in its applicability to direct analysis of synthesized nanotubes or other solid-phase extraction sorbents entrapping both the arsenic species. For determination of total arsenic using activated alumina as adsorbent, the most intense AsKα1,2 analytical lines were used and the instrumental limit of detection and the lower limit of quantification were 0.23 µg/L and 0.89 µg/L, respectively. For speciation, these limits were calculated to be 50 µg/L and 200 µg/L, respectively.

Ecotoxicity characterization assisted performance assessment of electro-bioremediation reactors for nitrate and arsenite elimination.

The performance of combined reduction of nitrate (NO3 - ) to dinitrogen gas (N2 ) and oxidation of arsenite (As[III]) to arsenate (As[V]) by a bioelectrochemical system was assessed, supported by ecotoxicity characterization. For the comprehensive toxicity characterization of the untreated model groundwater and the treated reactor effluents, a problem-specific ecotoxicity test battery was established. The performance of the applied technology in terms of toxicity and target pollutant elimination was compared and analyzed. The highest toxicity attenuation was achieved under continuous flow mode with hydraulic retention time (HRT) = 7.5 h, with 95%, nitrate removal rate and complete oxidation of arsenite to arsenate. Daphnia magna proved to be the most sensitive test organism. The results of the D. magna lethality test supported the choice of the ideal operational conditions based on chemical data analysis. The outcomes of the study demonstrated that the applied technology was able to improve the groundwater quality in terms of both chemical and ecotoxicological characteristics. The importance of ecotoxicity evaluation was also highlighted, given that significant target contaminant elimination did not necessarily lower the environmental impact of the initial, untreated medium, in addition, anomalies might occur during the technology operational process which in some instances, could result in elevated toxicity levels.

Comparative study of Fe(II)/sulfite, Fe(II)/PDS and Fe(II)/PMS for p-arsanilic acid treatment: Efficient organic arsenic degradation and contrasting total arsenic removal.

As a widely used feed additives, p-arsanilic acid (p-AsA) frequently detected in the environment poses serious threats to aquatic ecology and water security due to its potential in releasing more toxic inorganic arsenic. In this work, the efficiency of Fe(II)/sulfite, Fe(II)/PDS and Fe(II)/PMS systems in p-AsA degradation and simultaneous arsenic removal was comparatively investigated for the first time. Efficient p-AsA abatement was achieved in theses Fe-based systems, while notable discrepancy in total arsenic removal was observed under identical acidic condition. By using chemical probing method, quenching experiments, isotopically labeled water experiments, p-AsA degradation was ascribed to the combined contribution of high-valent Fe(IV) and SO4•-in these Fe(II)-based system. In particular, the relative contribution of Fe(IV) and SO4•- in the Fe(II)/sulfite system was highly dependent on the molar ratio of [Fe(II)] and [sulfite]. Negligible arsenic removal was observed in the Fe(II)/sulfite and Fe(II)/PDS systems, while ∼80% arsenic was removed in the Fe(II)/PMS system under identical acidic condition. This interesting phenomenon was due to that ferric precipitation only occurred in the Fe(II)/PMS system. As(V) was further removed via adsorption onto the iron precipitate or the formation of ferric arsenate-sulfate compounds, which was confirmed by particle diameter measurements, fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Through tuning solution pH, complete removal of total arsenic could achieve in all three systems. Among these three Fe-based technologies, the hybrid oxidation-coagulation Fe(II)/PMS system demonstrated potential superiority for arsenic immobilization by not requiring pH adjustment for coagulation and facilitating the in-situ generation of ferric arsenate-sulfate compounds with comparably low solubility levels like scorodite. These findings would deepen the understanding of these three Fe-based Fenton-like technologies for decontamination in water treatment.

Regulation and mechanism of pyrite and humic acid on the toxicity of arsenate in lettuce.

Pyrite and humic acid are common substances in nature, and the combined effects of pyrite and humic acid on arsenic phytotoxicity are more widespread in the actual environments than that of a single substance, but have received less attention. In this study, the interaction between pyrite and humic acid in arsenate solution was studied, and the effects of pyrite and humic acid on plant toxicity of arsenate were evaluated. The results showed that arsenate + pyrite + fulvic acid (V-PF) treatment immobilized more arsenic by forming chemical bonds such as AsS and Fe-As-O and reduced the migration of arsenic to plants. Compared to the arsenate + fulvic acid (VF), arsenate + pyrite (VP) and arsenate (V) group, the inorganic arsenic content of lettuce leaves in the V- PF group was reduced by 19.8 %, 13.4 % and 13.4 %, respectively. In addition, the V-PF group increased the absorption of Ca, Fe and Cu in plant roots, and improved the activity of superoxide dismutase (SOD) in plant leaves. Compared to the VF group, SOD and MDA in the V-PF group increased by 34.1 % in 30 days and decreased by 47.3 % in 40 days, respectively. The biomass of lettuce in V-PF group was increased by 29.3 % compared with that in VF group on day 50. The protein content of the V-PF group was 58.3 % higher than that of the VF group and 23.1 % higher than that of the VP group. Furthermore, metabolomics analysis showed that the V-PF group promoted glycolysis by up-regulating glyoxylic acid and dicarboxylic acid metabolism, thus reducing carbohydrate accumulation. Phosphocreatine metabolism was also up-regulated, which decreased the oxidative damage in lettuce induced by arsenic. This study will provide new ideas for scientifically and rationally assessing the ecological environmental risks of arsenic and regulating its toxicity.

Nanoconfinement boosts affinity of hydrated zirconium oxides to arsenate: Surface complexation modeling study.

Nanoscale hydrated zirconium oxide (HZO) holds great potential in groundwater purification due to its ability to form inner-sphere coordination with arsenate. Despite being frequently used, especially as encapsulations in host materials for practical application in water treatment, the adsorption mechanisms of solutes on HZO are not appropriately explored, in particular for arsenate adsorption. In this study, we investigated the Zr-As coordination configuration and identified the most credible Zr-As configuration using surface complexation modeling (SCM), XPS and FT-IR analysis. The corresponding intrinsic coordination constants (Kintr) values was calculated by SCM, and the nanoconfinement effects were distinguished by comparing bare HZO with the HZO nanoparticles (NPs) encapsulated inside the strongly basic anion exchanger D201. Potentiometric titration suggests that the surface Zirconium hydroxyl groups (≡ZrOH) mainly exist in protonated form (≡ZrOH2+). Batch adsorption experiments demonstrate that the D201 hosts could adsorb As(V) through ion exchange by the quaternary ammonium groups under the low ionic strength (≤0.01 M NaNO3) and at pH > 6. The nanocomposite (HZO@D201) exhibits a higher adsorption capacity in a wide range of pH (3-10) and ionic strength (0.001-0.1 M NaNO3) than bare HZO. SCM simulations reveal that the coordination configuration of diprotonated monodentate mononuclear (MM-H2) dominates at pH 3-6, while deprotonated bidentate binuclear (BB-H0) dominates at pH > 7. For each configuration, the intrinsic coordination constants (Kintr) of HZO@D201 (10-0.66 and 10-16.10, respectively) are significantly higher than those of bare HZO (10-12.24 and 10-44.42, respectively), indicating a superior chemical bonding affinity caused by nanoconfinement. The obtained Kintr values are used to predict arsenate adsorption isotherms in pH 3 and 9, and the results align with the SCM simulation outcomes. This study may offer a feasible method for investigating the nanoconfinement effect of emerging nanocomposite adsorbents from a thermodynamic perspective, and provide reference coordination equilibrium constants of HZO for research and practical application.

Geochemical fractionation and potential release behaviour of heavy metals in lead‒zinc smelting soils.

The lack of understanding of heavy metal speciation and solubility control mechanisms in smelting soils limits the effective pollution control. In this study smelting soils were investigated by an advanced mineralogical analysis (AMICS), leaching tests and thermodynamic modelling. The aims were to identify the partitioning and release behaviour of Pb, Zn, Cd and As. The integration of multiple techniques was necessary and displayed coherent results. In addition to the residual fraction, Pb and Zn were predominantly associated with reducible fractions, and As primarily existed as the crystalline iron oxide-bound fractions. AMICS quantitative analysis further confirmed that Fe oxyhydroxides were the common dominant phase for As, Cd, Pb and Zn. In addition, a metal arsenate (paulmooreite) was an important mineral host for Pb and As. The pH-stat leaching indicted that the release of Pb, Zn and Cd increased towards low pH values while release of As increased towards high pH values. The separate leaching schemes were associated with the geochemical behaviour under the control of minerals and were confirmed by thermodynamic modelling. PHREEQC calculations suggested that the formation of arsenate minerals (schultenite, mimetite and koritnigite) and the binding to Fe oxyhydroxides synchronously controlled the release of Pb, Zn, Cd and As. Our results emphasized the governing role of Fe oxyhydroxides and secondary insoluble minerals in natural attenuation of heavy metals, which provides a novelty strategy for the stabilization of multi-metals in smelting sites.