Salinity stress affects aquatic microalgal growth and their physiological responses have been studied extensively. However, arsenic (As) accumulation and biotransformation by freshwater phytoplankton under a salinity gradient have never been addressed. This study reports a distinctive pattern of As uptake, accumulation, and biotransformation by four axenic freshwater phytoplankton species, i.e., Scenedesmus acutus, Closterium aciculare, Staurastrum paradoxum, and Pediastrum duplex. Phytoplankton cells were incubated in sterilised C medium modified with varying salinity levels (0–5‰) in association with arsenate and phosphate concentrations. The biotransformation of arsenate (i.e., As(V)) to arsenite (As(III)) and to further methylated species decreased with increasing salinity in the culture medium whereas As accumulation increased. Among the four strains, only S. acutus and S. paradoxum converted As(V) to As(III), with no detected methylated species. In contrast, C. aciculare and P. duplex biotransformed As(V) to As(III) and further to methyl arsenic species, such as DMAA. S. acutus and S. paradoxum exhibited higher accumulation tendency than the other two species. S. paradoxum showed the lowest As reduction rate (i.e., As(V) to As(III)) compared to other species, although, without significant variations. The morphological changes were observed in phytoplankton cells in response to increased salinity stress. Moreover, As(V) concentrations in the culture medium significantly decreased by day 7–14. Thus, this study presents a conceptual model of the As biotransformation pattern by axenic freshwater phytoplankton.

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.

Water management such as drainage for creating aerobic conditions is considered to be an adequate method for reducing the accumulation of arsenic (As) in rice grains; however, it is difficult to conduct drainage operations in some areas that experience a lengthy rainy season as well as in soils with poor drainage. In this regard, application of oxygen-releasing compounds (ORCs) may be an alternative method for maintaining aerobic conditions even under flooding in paddy soils. Therefore, a pot experiment was conducted to investigate the effects of application of an ORC, calcium peroxide (CaO₂), on the growth and accumulation of As in rice plants grown in As-contaminated paddy soils. The rice plants were grown in two soils with different characteristics and As levels, and all of the tested soils were treated with 0, 5, 10, and 20 g CaO₂ kg⁻¹. Results revealed that the concentration of As and the distribution of arsenite in the pore water of all tested soils was reduced by CaO₂ application. In addition, the grain yields increased and the concentration of inorganic As in brown rice decreased by 25–45% upon CaO₂ treatment of low-As-level soils (<16 mg kg⁻¹). However, the effect of CaO₂ application on the accumulation of inorganic As in brown rice in As-enriched soils (>78 mg kg⁻¹) could not found in this study, due to the rice plant suffered from serious As phytotoxicity. It suggests that CaO₂ amendment may be suitable for reducing the As concentration of rice grains grown in low-As-level paddy soils, but for As-enriched soils, the proposed CaO₂ application method is not feasible.

Ubiquitous contamination of microplastics and arsenic in soil ecosystems can induce many health issues to nontarget soil organisms, and will also cause many potential threats to the gut bacterial communities of soil fauna. However, the changes in the gut bacterial communities of soil fauna after exposure to both microplastics and arsenic remain unknown. In this study, the toxicity and effects on the gut microbiota of earthworm Metaphire californica caused by the combined exposure of microplastics and arsenic were examined by using arsenic species analysis and high throughput sequencing of gut microbiota. Results showed that total arsenic and arsenic species in the earthworm gut and body tissues after exposure to combination of microplastics with arsenate (As(V)) were significantly different from that treated with As(V) alone. Microplastics lessened the accumulation of total arsenic and the transformation rate of As(V) to arsenite (As(III)). Microplastics alleviated the effect of arsenic on the gut microbiota possibly via adsorbing/binding As(V) and lowering arsenic bioavailability, thus prevented the reduction of As(V) and accumulation of total arsenic in the gut which resulted in a lower toxicity on the earthworm. The study broadens our understanding of the ecotoxicity of microplastics with other pollutants on the soil animals and on their gut microbiota.

The bioavailability of the metalloid arsenic (As) in paddy soil is controlled by microbial cycling of As and other elements such as iron (Fe) and sulfur (S), which are strongly influenced by water management in paddy fields. In this study, we evaluated how water management affects As bioavailability by growing rice plants in a geogenic As-contaminated soil. We determined As speciation in soil porewater and the diversity of the associated microbial community. Continuous flooding enhanced the release of Fe and As and increased arsenite (As(III)) and methylated As species concentrations in the rice grain compared with aerobic treatment. Total inorganic and organic As in the grain was 84% and 81% lower, respectively, in the aerobic treatment compared with the continuous flooding treatment. The amounts of Fe(III)-reducing bacteria (FeRB) increased in the flooded rhizosphere soil. The abundance of FeRB in the soil correlated with the dissolution of Fe and As. Among the As-transformation genes quantified, the aioA gene for As(III) oxidation and arsM gene for As(III) methylation were most abundant. The arsM copy number correlated positively with the levels of dsrB (dissimilatory (bi) sulfite reductase β-subunit), suggesting that dissimilatory sulfate-reducing bacteria (SRB) may play an important role in dimethylarsenate (DMAs(V)) production in soil. Our results show that decreased populations of rhizosphere FeRB and SRB contributed to a lower bioavailability of As, and decreased production of methylated arsenicals under oxic conditions.

Arsenic (As) is a metalloid element that is ubiquitous in the marine environment and its contamination has received worldwide attention due to its potential toxicity. Arsenic can induce multiple adverse effects, such as lipid metabolism disorder, immune system dysfunction, oxidative stress and carcinogenesis, in animals. Inorganic arsenic includes two chemical forms, arsenite (As (III)) and arsenate (As (V)), in natural environment. As (V) is the dominant form in natural waters. In the present study, metabolomic and proteomic alterations were investigated in juvenile rockfish Sebastes schlegelii exposed to environmentally relevant concentrations of As (V) for 14 d. The analysis of iTRAQ-based proteomics combined with untargeted NMR-based metabolomics indicated apparent toxicological effects induced by As (V) in juvenile rockfish. In details, the metabolites, including lactate, alanine, ATP, inosine and phosphocholine were significantly altered in As-treated groups. Proteomic responses suggested that As (V) could not only affected energy and primary metabolisms and signal transduction, but also influenced cytoskeleton structure in juvenile rockfish. This work suggested that the combined proteomic and metabolomic approach could shed light on the toxicological effects of pollutants in rockfish S. schlegelii.

The effects of arsenic (As), cadmium (Cd) and zinc (Zn) on each other's uptake and oxidative stress in As-hyperaccumulator Pteris vittata were investigated. P. vittata plants were exposed to 50 μM As, Cd and/or Zn for 15 d in 0.2-strength Hoagland solution. When applied alone, P. vittata accumulated 185 mg kg⁻¹ As, 164 mg kg⁻¹ Cd and 327 mg kg⁻¹ Zn in the fronds. While Cd and Zn did not impact each other's uptake, As affected Cd and Zn uptake. Whereas As decreased Zn uptake, Zn affected As speciation in P. vittata fronds, with more arsenate (AsV) than arsenite (AsIII) being present. At 50 μM As, 75 μM Zn increased As accumulation in P. vittata fronds by 10 folds to 2363 mg kg⁻¹ compared to 50 μM Zn. Although AsV was the predominant As species in all tissues, Cd enhanced AsIII levels in the fronds but increased AsV in the roots. Co-exposure of Cd + Zn elevated oxidative stress basing on thiobarbituric acid reactive substances, H₂O₂ content, Evans blue dye uptake, membrane injury index and reactive oxygen species (ROS) relative to single metal. By lowering Cd and Zn concentrations in P. vittata fronds, As reduced the associated stress comparative to Cd or Zn treatment. The results enhance our understanding of the mechanisms underlying the interactions between As, Cd and Zn in As-hyperaccumulator P. vittata.

Roxarsone (3-nitro-4-hydroxyphenylarsonic acid, ROX) is an arsenic-containing compound widely used as a feed additive in poultry industries. ROX excreted in chicken manure can be transformed by microbes to different arsenic species in the environment. To date, most of the studies on microbial transformation of ROX have focused on anaerobic microorganisms. Here, we isolated a pure cultured aerobic ROX-transforming bacterial strain, CZ-1, from an arsenic-contaminated paddy soil. On the basis of 16S rRNA gene sequence, strain CZ-1 was classified as a member of the genus Enterobacter. During ROX biotransformation by strain CZ-1, five metabolites including arsenate (As[V]), arsenite (As[III]), N-acetyl-4-hydroxy-m-arsanilic acid (N-AHPAA), 3-amino-4-hydroxyphenylarsonic acid (3-AHPAA) and a novel sulfur-containing arsenic species (AsC₉H₁₃N₂O₆S) were detected and identified based on high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS), HPLC-ICP-MS/electrospray ionization mass spectrometry (ESI-MS) and HPLC-electrospray ionization hybrid quadrupole time-of-flight mass spectrometry (ESI-qTOF-MS) analyses. N-AHPAA and 3-AHPAA were the main products, and 3-AHPAA could also be transformed to N-AHPAA. Based on the results, we propose a novel ROX biotransformation pathway by Enterobacter. sp CZ-1, in which the nitro group of ROX is first reduced to amino group (3-AHPAA) and then acetylated to N-AHPAA.

Preoxidation of As(III) to As(V) is required for the efficient removal of total arsenic in the treatment of wastewater. In this work, the electro-Fenton oxidation of As(III) with a high efficiency was successfully achieved by using the system of the stainless steel net (SSN) coating with reduced graphene oxide (RGO@SSN) as the cathode and stainless steel net (SSN) as the sacrificial anode. The RGO@SSN was synthesized by electrophoretic deposition-annealing method. The carbon disorder and defects of RGO resulted from the remained oxygen-containing functional groups facilitated the electrocatalytically active sites for two-electron oxygen reduction reaction (ORR). A high concentration (up to 1000 μmol/L) of H₂O₂ was in-situ produced through two-electron oxygen reduction reaction of electro-catalysis, and then served as the electro-Fenton reagent for the oxidation of As(III). HO generated by H₂O₂ participating the electro-Fenton reaction or decomposed at the surface of RGO@SSN cathode at acid condition endowed the strong oxidizing ability for As(III). The electro-Fenton equipped with RGO@SSN cathode has a promising application in the oxidation and removal of organic or inorganic pollutants in wastewater.

Inhibition of reductive transformation of arsenic (As) in flooded paddy soils is of fundamental importance for mitigating As transfer into food chain. Anaerobic arsenite (As(III)) oxidizers maintain As in less mobile fraction under nitrate-reducing conditions. In this study, we explored the dynamic profile of As speciation in porewater and As distribution among the pools of differential bioavailability in soil solid phase with and without nitrate treatment. In parallel, the abundance and diversity of As(III) oxidase gene (aioA) in flooded paddy soil with nitrate amendment was examined by quantitative PCR and aioA gene clone library. Furthermore, the impact of nitrate on As accumulation and speciation in rice seedlings was unraveled. With nitrate addition (25 mmol NO₃⁻ kg⁻¹ soil), porewater As(III) was maintained at a consistently negligible concentration in the flooded paddy soil and the reductive dissolution of As-bearing Fe oxides/hydroxides was significantly restrained. Specifically, nitrate amendment kept 81% of total soil As in the nonlabile fraction with arsenate (As(V)) dominating after 30 days of flooding, compared to only 61% in the unamended control. Nitrate treatment induced 4-fold higher abundance of aioA gene, which belonged to domains of bacteria and archaea under the classes α-Proteobacteria (6%), ß-Proteobacteria (90%), ɣ-Proteobacteria (2%), and Thermoprotei (2%). By nitrate addition, As accumulation in rice seedlings was decreased by 85% with simultaneously elevated As(V) ratio in rice plant relative to control after 22 days of growth under flooded conditions. These results highlight that nitrate application can serve an efficient method to inhibit reductive dissolution of As in flooded paddy soils, and hence diminish As uptake by rice under anaerobic growing conditions.