Bacteria play crucial roles in the biogeochemical cycle of arsenic (As) and selenium (Se) as these elements are metabolized via detoxification, energy generation (anaerobic respiration) and biosynthesis (e.g. selenocysteine) strategies. To date, arsenic and selenium biomineralization in bacteria were studied separately. In this study, the anaerobic metabolism of As and Se in Shewanella sp. O23S was investigated separately and mixed, with an emphasis put on the biomineralization products of this process. Multiple analytical techniques including ICP-MS, TEM-EDS, XRD, Micro-Raman, spectrophotometry and surface charge (zeta potential) were employed. Shewanella sp. O23S is capable of reducing selenate (SeO₄²⁻) and selenite (SeO₃²⁻) to red Se(-S)⁰, and arsenate (AsO₄³⁻) to arsenite (AsO₃³⁻). The release of H₂S from cysteine led to the precipitation of AsS minerals: nanorod AsS and granular As₂S₃. When As and Se oxyanions were mixed, both As–S and Se(-S)⁰ biominerals were synthesized. All biominerals were extracellular, amorphous and presented a negative surface charge (−24 to −38 mV). Kinetic analysis indicated the following reduction yields: SeO₃²⁻ (90%), AsO₄³⁻ (60%), and SeO₄²⁻ (<10%). The mix of SeO₃²⁻ with AsO₄³⁻ led to a decrease in As removal to 30%, while Se reduction yield was unaffected (88%). Interestingly, SeO₄²⁻ incubated with AsO₄³⁻ boosted the Se removal (71%). The exclusive extracellular formation of As and Se biominerals might indicate an extracellular respiratory process characteristic of various Shewanella species and strains. This is the first study documenting a complex interplay between As and Se oxyanions: selenite decreased arsenate reduction, whereas arsenate stimulated selenate reduction. Further investigation needs to clarify whether Shewanella sp. O23S employs multi-substrate respiratory enzymes or separate, high affinity enzymes for As and Se oxyanion respiration.

Arsenic is a potent toxicant, and long-term exposure to inorganic arsenic causes lung damage. M2 macrophages play an important role in the pathogenesis of pulmonary fibrosis. However, the potential connections between arsenic and M2 macrophages in the development of pulmonary fibrosis are elusive. C57BL/6 mice were fed with drinking water containing 0, 10 and 20 ppm arsenite for 12 months. We have found that, in lung tissues of mice, arsenite, a biologically active form of arsenic, elevated H19, c-Myc, and Arg1; decreased let-7a; and caused pulmonary fibrosis. For THP-1 macrophages (THP-M) and bone-marrow-derived macrophages (BMDMs), 8 μM arsenite increased H19, c-Myc, and Arg1; decreased let-7a; and induced M2 polarization of macrophages, which caused secretion of the fibrogenic cytokine, TGF-β1. Down-regulation of H19 or up-regulation of let-7a reversed the arsenite-induced M2 polarization of macrophages. Arsenite-treated THP-M and BMDMs co-cultured with MRC-5 cells or primary lung fibroblasts (PLFs) elevated levels of p-SMAD2/3, SMAD4, α-SMA, and collagen I in lung fibroblasts and resulted in the activation of lung fibroblasts. Knockout of H19 or up-regulation of let-7a in macrophages reversed the effects. The results indicated that H19 functioned as an miRNA sponge for let-7a, which was involved in arsenite-induced M2 polarization of macrophages and induced the myofibroblast differentiation phenotype by regulation of c-Myc. In the sera of arseniasis patients, levels of hydroxyproline and H19 were higher, and levels of let-7a were lower than levels in the controls. These observations elucidate a possible mechanism for arsenic exposure-induced pulmonary fibrosis.

A highly efficient, eco-friendly and relatively low-cost catalyst is necessary to tackle bottlenecks in the treatment of industrial wastewater laden with heavy metals and antibiotic such as livestock farm and biogas liquids. This study investigated co-oxidative removal of arsenite (As(III)) and tetracycline (TC) by iron nanoparticles (Fe NP)-impregnated carbons based on heterogeneous Fenton-like reactions. The composites included Fe NP@biochar (BC), Fe NP@hydrochar (HC), and Fe NP@HC-derived pyrolysis char (HDPC). The functions of N and S atoms and the loading mass of the Fe NP in the Fe NP@BC in heterogeneous Fenton-like reactions were studied. To sustain its cost-effectiveness, the spent Fe NP@BC was regenerated using NaOH. Among the composites, the Fe NP@BC achieved an almost complete removal of As(III) and TC under optimized conditions (1.0 g/L of dose; 10 mM H₂O₂; pH 6; 4 h of reaction; As(III): 50 μM; TC: 50 μM). The co-oxidative removal of As(III) and TC by the Fe NP@ BC was controlled by the synergistic interactions between the Fe NPs and the active N and S sites of the BC for generating reactive oxygen species (ROS). After four consecutive regeneration cycles, about 61 and 95% of As(III) and TC removal were attained. This implies that the spent carbocatalyst still has reasonable catalytic activities for reuse. Overall, this suggests that adding technological values to unused biochar as a carbocatalyst like Fe NP@BC was promising for co-oxidative removal of As(III) and TC from contaminated water.

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.

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.

N⁶-methyladenosine (m⁶A), the most abundant and reversible RNA modification, plays critical a role in tumorigenesis. However, whether m⁶A can regulate p53, a leading antitumor protein remains poorly understood. In this study, we explored the regulatory role of m⁶A on p53 activation using an arsenite-transformed keratinocyte model, the HaCaT-T cell line. We created the cell line by exposing human keratinocyte HaCaT cells to 1 μM arsenite for 5 months. We found that the cells exhibited an increased m⁶A level along with an aberrant expression of the methyltransferases, demethylase, and readers of m⁶A. Moreover, the cells exhibited decreased p53 activity and reduced p53 phosphorylation, acetylation, and transactivation with a high nucleus export rate of p53. Knockdown of the m⁶A methyltransferase, METTL3 significantly decreased m⁶A level, restoring p53 activation and inhibiting cellular transformation phenotypes in the arsenite-transformed cells. Further, using both a bioinformatics analysis and experimental approaches, we demonstrated that m⁶A downregulated the expression of the positive p53 regulator, PRDM2, through the YTHDF2-promoted decay of PRDM2 mRNAs. We showed that m⁶A upregulated the expression of the negative p53 regulator, YY1 and MDM2 through YTHDF1-stimulated translation of YY1 and MDM2 mRNA. Taken together, our study revealed the novel role of m⁶A in mediating arsenite-induced human keratinocyte transformation by suppressing p53 activation. This study further sheds light on the mechanisms of arsenic carcinogenesis via RNA epigenetics.

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.

Dietary arsenic (As) intake from food is of great concern, and developing a reliable model capable of predicting As concentrations in plant edible parts is desirable. In this study, pot experiments were performed with 16 Chinese upland soils spiked with arsenate [As(V)] to develop a predictive model for As concentrations in pepper fruits (Capsicum annum L.). Our results showed that after three months’ aging, concentrations of bioavailable As (extracted by 0.05 M NH₄H₂PO₄) in various soils varied widely, depending on soil total As concentrations and soil properties such as soil pH and amorphous iron (Fe) contents. Furthermore, both the bioconcentration factor (BCF, denoted as the ratio of fruit As to soil As) and total As concentrations in pepper fruits were largely determined by concentrations of bioavailable As, which explained 27% and 69% variations in the BCF and fruit As concentrations, respectively. Apart from bioavailable As, soil pH and Fe contents were another two important factors influencing As accumulation in pepper fruits. Taking the three factors into account, concentrations of fruit As can be well predicted using a stepwise multiple linear regression (SMLR) analysis (R² = 0.80, RMSE = 0.17). Arsenic species in soils and edible parts were also analyzed. Although As(V) predominated in soils (>96%), As in pepper fruits presented as As(V) (46%) and arsenite [As(III)] (39%) with small amount of methylated As (<15%). Aggregated boosted tree (ABT) analysis revealed that inorganic As concentrations in pepper fruits were determined by concentrations of bioavailable As, phosphorus (P) and Fe in soils. In contrast to inorganic As, methylated As concentrations were not correlated with those factors in soils. Taken together, this study established an empirical model for predicting As concentrations in pepper fruits. The predictive model can be used for establishing the As threshold in fruit vegetable farming soils.

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.

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.