Iron nanoparticles (Fe NPs) have often been used for in situ remediation of both groundwater and soil. However, the impact of Fe NPs on the distribution and transformation of As species in contaminated soil is still largely unknown. In this study, green iron oxide nanoparticles synthesized using a euphorbia cochinchinensis leaf extract (GION) were used to stabilize As in a contaminated soil. GION exhibited excellent As stabilization effects, where As in non-specifically-bound and specifically-bound fractions decreased by 27.1% and 67.3% after 120 days incubation. While both arsenate (As (V)) and arsenite (As (III)) decreased after GION application, As (V) remained the dominant species in soil. X-ray photoelectron spectroscopy (XPS) confirmed that As (V) was the dominant species in specifically-bound fractions, while As (III) was the dominant species in amorphous and poorly-crystalline hydrous oxides of Fe and Al. Correlation analysis showed that while highly available As fractions were negatively correlated to oxalate and DCB extractable Fe, they were positively correlated to Fe²⁺ content, which indicated that Fe cycling was the main process influencing changes in As availability. X-ray fluorescence (XRF) spectroscopy also showed that the Fe₂O₃ content increased by 47.9% following GION soil treatments. Overall, this work indicated that As would be transformed to more stable fractions during the cycling of Fe following GION application and that the application of GION, even in small doses, provides a low-cost and ecofriendly method for the stabilization of As in soil.

Previous studies have indicated that natural organic matter in the aquatic environment could affect arsenic bioaccumulation and biotransformation to aquatic organisms. However, the differences between the effects of arsenite and arsenate exposure have not been studied and compared in fish exposure models. In this study, adult zebrafish (Danio rerio) were exposed to 5 mg/L inorganic As solutions, in the presence of a range of humic acid (HA) concentrations (1, 2.5, 5, 10, 20 mg/L) in 96 h waterborne exposure. Results showed that in the presence of HA, total As bioaccumulation was significantly reduced in zebrafish following arsenite exposure, while this reduction was not observed during arsenate exposure. The reduction in total arsenic bioaccumulation for arsenite exposure can be explained by the fact that HA forming a surface coating on the cell surface, hindering transport and internalization. However, this reduction in total As was not observed due to differences in uptake pathways for arsenate exposure. Results also showed that Arsenobetaine (AsB) was the main biotransformation product in zebrafish following inorganic As exposure, accounting for 44.8%–64.7% of extracted arsenic species in all exposure groups. The addition of HA caused levels of MMA and As(III) to decrease, while the distribution of AsB significantly increased in arsenite exposure groups. The increase in AsB could be because the As(III)-HA complex was formed, affecting the methylation of As(III). In contrast, the addition of HA to arsenate exposure groups, did not affect the reduction of As(V) to As(III) and therefore, an increase in the distribution of AsB was not observed in arsenate exposure groups. This study provides useful information on the mechanisms of toxicity, for improved risk assessment of As in natural aquatic environments.

Nano-silica as an important part of soil is an ideal carrier of passivator material. In this paper, nano-silica was modified by silane coupling agent containing mercapto group and iron (II) salt to afford an organic-inorganic hybrid containing –S-Fe-S functional group (coded as RNS-SFe) on the surface of nano-silica. Results demonstrate that the RNS-SFe nanoparticle has network-like spheroidal shape and a primary particle size is about 18.0 nm. The RNS-SFe hybrid as a potential immobilization agent for heavy metal in soil shows excellent performance for the remediation of the contaminated soil. Specifically, with a dosage of 3.0% (mass ratio) in the soil, it can immobilize bioavailable Pb, Cd, and As by 97.1%, 85.0%, and 80.1%, respectively. Namely, the RNS-SFe hybrid can transform the bioavailable Pb, Cd, and As into insoluble mercapto metal compounds (–S-Pb-S- and –S-Cd-S-) and less soluble iron arsenate (Fe₃(AsO₄)₂, FeAsO₄) precipitate on the surface of nano-silica particle, thereby reducing the toxicity and mobility of the toxic contaminant fractions. In the meantime, the immobilized products of the Pb, Cd and As fractions have good resistance against acid leaching. These results are contributive to the application of RNS-SFe for the remediation of multi-heavy metal-contaminated soils in field.

Waste date palm-derived biochar (DPBC) was modified with nano-zerovalent iron (BC-ZVI) and silica (BC-SiO₂) through mechanochemical treatments and evaluated for arsenate (As(V)) removal from water. The feedstock and synthesized adsorbents were characterized through proximate, ultimate, and chemical analyses for structural, surface, and mineralogical compositions. BC-ZVI demonstrated the highest surface area and contents of C, N, and H. A pH range of 2–6 was optimum for BC-ZVI (100% removal), 3–6 for DPBC (89% removal), and 4–6 for BC-SiO₂ (18% removal). Co-occurring PO₄³⁻ and SO₄²⁻ ions showed up to 100% reduction, while NO₃⁻ and Cl⁻ ions resulted in up to 26% reduction in As(V) removal. Fitness of the Langmuir, Freundlich and Redlich-Peterson isotherms to As(V) adsorption data suggested that both mono- and multi-layer adsorption processes occurred. BC-ZVI showed superior performance by demonstrating the highest Langmuir maximum adsorption capacity (26.52 mg g⁻¹), followed by DPBC, BC-SiO₂, and commercial activated carbon (AC) (7.33, 5.22, and 3.28 mg g⁻¹, respectively). Blockage of pores with silica particles in BC-SiO₂ resulted in lower As(V) removal than that of DPBC. Pseudo-second-order kinetic model fitted well with the As(V) adsorption data (R² = 0.99), while the Elovich, intraparticle diffusion, and power function models showed a moderate fitness (R² = 0.53–0.93). The dynamics of As(V) adsorption onto the tested adsorbents exhibited the highest adsorption rates for BC-ZVI. As(V) adsorption onto the tested adsorbents was confirmed through post-adsorption FTIR, SEM-EDS, and XRD analyses. Adsorption of As(V) onto DPBC, BC-SiO₂, and AC followed electrostatic interactions, surface complexation, and intraparticle diffusion, whereas, these mechanisms were further abetted by the higher surface area, nano-sized structure, and redox reactions of BC-ZVI.

The contamination of ground water with arsenic is a great public health concern. This paper discusses the possible formation mechanism of high As groundwater; identify the main influences of natural and anthropogenic factors on As occurrence in groundwater; and finally estimates As-induced potential health hazards in an intensive agricultural region, Datong Basin (Northern China). Our findings indicate that the predominant controlling factors of As in groundwater can be divided into natural factors and anthropogenic activities. Natural factors can be classified as natural potential source of As, environmental geological characteristics and hydrochemical conditions; anthropogenic activities are manifested in industrial coal mining, domestic coal burning, agricultural irrigation return flow and excessive application of fertilizers, and groundwater exploitation. Microbial and/or chemical reduction desorption of arsenate from Fe-oxide/hydroxide and/or clay minerals, As-bearing Fe-oxide/hydroxide reduction coupled with sulfate reduction, and competition with phosphorus are postulated to be the major process dominating As enrichment in the alkaline and anoxic groundwater. In addition, age-dependent human health risk assessment (HHRS) was performed, and high risk values reveal a high toxic and carcinogenic risk of As contaminate for population who is subject to the continuous and chronic exposure to elevated As.

The present study proposes a maize sprouts hydroponic growth model to evaluate the As, Cd, Cr and Pb translocation from multinutrient fertilizer and to do speciation of As and Cr in this fertilizer and As in parts of plant in order to predict their phytoavailability. X-ray absorption near edge structure (XANES) was employed to speciate As and Cr directly on fertilizer solid sample. Arsenate (Asⱽ) and a solid solution of FeCrO₃ were the major species identified in the samples. The sprouts were hydroponically cultivated in water, fertilizer slurry and fertilizer extract media. Concentrations of As, Cd and Pb measured on leaves of maize sprouts ranged from 0.061 to 0.31 mg kg⁻¹, whereas Cr was not translocated to the aerial parts of sprouts. High performance liquid chromatographic with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) analysis was used to determine As speciation in maize sprouts, as well as in the fertilizer extracts and slurries. Arsenate was the only species identified in the initial fertilizer extract and this information is in agreement with the XANES results. However, the reduction of arsenate to arsenite was observed in extracts and slurries collected after sprout growth, probably due to the action of exudates secreted by plant roots. Arsenite was the predominant species identified in sprouts, the high phosphate concentration in the medium may have contributed to reduce arsenate phytoavailability.

This study examined arsenite [As(III)], arsenate [As(V)] and fluoride (F⁻) removal potential of bone char produced from sheep (Ovis aries) bone waste. Pyrolysis conditions tested were in the 500 °C–900 °C range, for a holding time of 1 or 2 h, with or without N₂ gas purging. Previous bone char studies mainly focused on either low or high temperature range with limited information provided on As(III) removal. This study aims to address these gaps and provide insights into the effect of pyrolysis conditions on bone char sorption capacity. A range of advanced chemical analyses were employed to track the change in bone char properties. As pyrolysis temperature and holding time increased, the resulting pH, surface charge, surface roughness, crystallinity, pore size and CEC all increased, accompanied by a decrease in the acidic functional groups and surface area. Pyrolysis temperature was a key parameter, showing improvement in the removal of both As(III) and As(V) as pyrolysis temperature was increased, while As(V) removal was higher than As(III) removal overall. F⁻ removal displayed an inverse relationship with increasing pyrolysis temperature. Bone char prepared at 500 °C released significantly more dissolved organic carbon (DOC) then those prepared at a higher temperature. The bone protein is believed to be a major factor. The predominant removal mechanisms for As were surface complexation, precipitation and interaction with nitrogenous functional groups. Whereas F⁻ removal was mainly influenced by interaction with oxygen functional groups and electrostatic interaction. This study recommends that the bone char pyrolysis temperature used for As and F⁻ removal are 900 °C and 650 °C, respectively.

The bioaccessibility of arsenic and its speciation are two important factors in assessing human health risks exposure to contaminated soils. However, the effects of human gut microbiota on arsenic bioaccessibility and its speciation are not well characterized. In this study, an improved in vitro model was utilized to investigate the bioaccessibility of arsenic in the digestive tract and the role of human gut microbiota in the regulation of arsenic speciation. For all soils, arsenic bioaccessibility from the combined in vitro model showed that it was <40% in the gastric, small intestinal and colon phases. This finding demonstrated that the common bioaccessibility approach assuming 100% bioaccessibility would overestimate the human health risks posed by contaminated soils. Further to this, the study showed that arsenic bioaccessibility was 22% higher in the active colon phase than that in the sterile colon phase indicating that human colon microorganisms could induce arsenic release from the solid phase. Only inorganic arsenic was detected in the gastric and small intestinal phases, with arsenate [As(V)] being the dominant arsenic species (74%–87% of total arsenic). Arsenic speciation was significantly altered by the active colon microbiota, which resulted in the formation of methylated arsenic species, including monomethylarsonic acid [MMA(V)] and dimethylarsinic acid [DMA(V)] with low toxicity, and a highly toxic arsenic species monomethylarsonous acid [MMA(III)]. Additionally, a high level of monomethylmonothioarsonic acid [MMMTA(V)] (up to 17% of total arsenic in the extraction solution) with unknown toxicological properties was also detected in the active colon phase. The formation of various organic arsenic species demonstrated that human colon microorganisms could actively metabolize inorganic arsenic into methylated arsenicals and methylated thioarsenicals. Such transformation should be considered when assessing the human health risks associated with oral exposure to soil.

Microbial assemblages such as biofilms around aquatic plants play a major role in arsenic (As) cycling, which has often been overlooked in previous studies. In this study, arsenite (As(III))-oxidizing, arsenate (As(V))-reducing and As(III)-methylating bacteria were found to coexist in the phyllosphere of Hydrilla verticillata, and their relative activities were shown to determine As speciation, accumulation and efflux. When exposed to As(III), As(III) oxidation was not observed in treatment H(III)-B, whereas treatment H(III)+B showed a significant As(III) oxidation ability, thereby indicating that epiphytic bacteria displayed a substantial As(III) oxidation ability. When exposed to As(V), the medium only contained 5.89% As(III) after 48 h of treatment H(V)-B, while an As(III) content of 86.72% was observed after treatment H(V)+B, thereby indicating that the elevated As(III) in the medium probably originated from As(V) reduction by epiphytic bacteria. Our data also indicated that oxidizing bacteria decreased the As accumulation (by approximately 64.44% compared with that of treatment H(III)-B) in plants, while reducing bacteria played a critical role in increasing As accumulation (by approximately 3.31-fold compared with that of treatment H(V)-B) in plants. Regardless of whether As(III) or As(V) was supplied, As(III) was dominant in the plant tissue (over 75%). Furthermore, the presence of epiphytic bacteria enhanced As efflux by approximately 9-fold. Metagenomic analysis revealed highly diverse As metabolism genes in epiphytic bacterial community, particularly those related to energetic metabolism (aioAB), and As resistance (arsABCR, acr3, arsM). Phylogenetic analysis of As metabolism genes revealed evidence of both vertical inheritance and horizontal gene transfer, which might have contributed to the evolution of the As metabolism genes. Taken together, our research suggested that the diversity of As metabolism genes in epiphytic bacterial community is associated with aquatic submerged macrophytes which may play an important role in As biogeochemistry in aquatic environments.

The microbe-driven iron cycle plays an important role in speciation transformation and migration of arsenic (As) in soil-rice systems. In this study, pot experiments were used to investigate the effect of bacterial iron (Fe) reduction processes in soils on As speciation and migration, as well as on As uptake in soil-rice system. During the rice growth period, pH and electrical conductivity (EC) in soil solutions initially increased and then decreased, with the ranges of 7.4–8.8 and 116.3–820 mS cm⁻¹, respectively. The concentrations of Fe, total As and As(III) showed an increasing trend in the rhizosphere and non-rhizosphere soil solutions with the increasing time. Fe concentrations were significantly positively correlated with total As and As(III) concentrations (***p < 0.001) in the soil solutions. The abundances of the arsenate reductase gene (arsC) and the As(III) S-adenosylmethionine methyltransferase gene (arsM) in rhizosphere soils were higher than those in non-rhizosphere soils, while the abundance of the Fe-reducing bacteria (Geo) showed an opposite trend. Moreover, it showed that the Geo abundance was significantly positively correlated with that of the arsC (***p < 0.001) and arsM (**p < 0.01) genes, respectively. The abundances of Geo, arsC and arsM genes were significantly positively correlated with the concentrations of Fe, total As and As(III) in the soil solutions (*p < 0.05). Moreover, the abundances of arsC and arsM genes were significantly negatively correlated with total As and As(III) in rice grains (*P < 0.05). These results showed that the interaction of bacterial Fe reduction process and radial oxygen loss from roots promoted the reduction and methylation of As, and then decreased As uptake by rice, which provided a theoretical basis for alleviating As pollution in paddy soils.