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In the present study, two chromogenic probes, N7R2 and N7R3, each containing two binding sites, were designed and synthesized for the selective detection of arsenite in DMSO/H 2 O (1:1, v/v). The probes exhibited stability across a pH range spanning from 5 to 12. The lower detection limits of 2.01 ppb (18.86 nM) for N7R2 and 1.79 ppb (16.75 nM) for N7R3, which are much lower than the WHO recommended permissible limit of arsenite, confirmed the superior efficiency of the probes in detecting arsenite. The detection mechanism for arsenite was proposed through UV and 1 H NMR titrations, electrochemical studies, and DFT calculations. Practical applications were demonstrated through the fabrication of test strips and molecular logic gates. The probes efficiently recognized arsenite in real water, honey, milk samples, and fruit/vegetable juices. Both N7R2 and N7R3 exhibited excellent recovery rates in the analysis of food samples, demonstrating the probes' usefulness in real sample analysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

The coastal environment is an important ecosystem connecting land and sea, and arsenite (As(III)) in coastal seawater can seriously affect human health through the food chain. However, the effects of dissolved organic matter (DOM) extracted from coastal algae and rivers on As(III) photooxidation remain unclear. Results show that coastal algal DOM (CA-DOM) is significantly more effective than Suwannee River natural organic matter (SRNOM) in photooxidation of As(III), with a rate 8.3 times higher after correcting for light screening effects. CA-DOM accelerates As(III) photooxidation mainly through the 3 DOM ⁎ pathway, contributing 78.7 % to the process, whereas 3 NOM ⁎ contributes only 37.2 % for SRNOM. CA-DOM consists primarily of low-excited tyrosine and tryptophan-like protein substances, whereas SRNOM consists of humic and fulvic acid-like substances. Thus, CA-DOM exhibits a higher steady-state concentration of 3 DOM ⁎ , and the 3 DOM ⁎ reacts much faster with As(III) than the 3 NOM ⁎ . The increase in CA-DOM concentration can significantly accelerate the photooxidation of As(III), whereas the effect of SRNOM concentration is negligible. Increased salinity can accelerate As(III) photooxidation for all types of DOM. Our results provide new insights into the role of DOM from different sources in the photooxidation of As(III) in the natural environment or engineering applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In this study, two chemosensors, N5R1 and N5R2, based on 5-(4-nitrophenyl)-2-furaldehyde, with varying electron-withdrawing groups, were synthesized and effectively employed for the colorimetric selective detection of arsenite anions in a DMSO/H 2 O solvent mixture (8 : 2, v/v). Chemosensors N5R1 and N5R2 exhibited a distinct color change upon binding with arsenite, accompanied by a spectral shift toward the near-infrared region (Δλ max exceeding 200 nm). These chemosensors established stability between a pH range 6-12. Among them, N5R2 displayed the lowest detection limit of 17.63 ppb with a high binding constant of 2.6163×10 5  M -1 for arsenite. The binding mechanism involved initial hydrogen bonding between the NH binding site and the arsenite anion, followed by deprotonation and an intramolecular charge transfer (ICT) mechanism. The mechanism was confirmed through UV and 1 H NMR titrations, cyclic voltammetric studies, and theoretical calculations. The interactions between the sensor and arsenite anions were further analyzed using global reactivity parameters (GRPs). Practical applications were demonstrated through the utilization of test strips and molecular logic gates. Real water samples, honey, and milk samples were successfully analyzed by both chemosensors for the sensing of arsenite., (© 2024 Wiley-VCH GmbH.)

ZnAlFe mixed metal oxides (ZnAlFe-MMOs) were synthesized from layered double hydroxides (LDHs) prepared by the coprecipitation method at pH 9 using an initial weight composition of Zn 2+  = 75%, Al 3+  = 15% and Fe 3+  = 10%, with or without the addition of citric or oxalic acid. The solids were calcined at 400 °C to obtain the respective MMOs, which exhibited relatively high specific surface areas (165.3-63.8 m 2  g -1 ) and semiconductor properties active in the visible region (bandgap values (E g ) of 2.42-1.77 eV). The synthesized materials were tested for the removal of trivalent arsenic by adsorption and by photocatalysis under visible light irradiation (λ ≥ 420 nm). The best removal of As(III) by adsorption (65.9%) and by photocatalysis (99.9%) was obtained with the ZnAlFe-MMOs prepared in the absence of organic acids. The XPS results indicate the coexistence of As 3+ and As 5+ over ZnAlFe-MMOs after the photocatalytic reaction and also confirm the formation of Fe 2+ sites on the hematite surface that enhances the removal of As(III). Raman measurements confirmed that, in the photocatalytic experiments, As is largely retained as As(V) on ZnAlFe-MMOs, bound to Fe. The results of fluorescence of 7-hydroxycoumarin suggest that the photocatalyst produces HO • , which can be the main species for As(III) oxidation under UV-Vis irradiation. Moreover, ZnAlFe-MMOs exhibited a good reusability after regeneration making ZnAlFe-MMOs a promising material for arsenic decontamination in polluted water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Iron-based adsorbents are commonly used to remove arsenic (As) from water for drinking water purposes. Here, we study the role of biological As(III) oxidation on iron-based adsorbents in filters and its effect on overall As uptake. A lab-scale filter with iron oxide coated sand (IOCS), a commonly used adsorbent, was operated with water containing As(III) and As(V), while water samples were taken periodically over its height. As(III) oxidation initiated after approximately 10 days and increased to a first order rate constant of 0.09 s -1 after 57 days resulting in full oxidation of As(III) in <50 s. Consequently, the filter shifted from an As(III) to an As(V) adsorbing filter. Oxidation was not observed after inhibiting the microbial activity using sodium azide confirming its biogenic nature. This implies that As(III) oxidizing biomass can grow on iron-based adsorbents in water filters without requiring inoculation. As the experimental conditions were similar to full-scale As treatment plants, we believe that biological As(III) oxidation is widely overlooked in these systems. Occurrence of biological oxidation is, however, beneficial for removal, as at pH <8 the adsorption capacity for As(V) can be up to 10-fold higher than for As(III). With these new insights, arsenic treatment using iron-based adsorbents can be further optimized. We suggest a more robust new design with a biological active As(III) oxidizing top layer and an As(V) adsorbing bottom layer., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

In this study, we proposed a moderate oxidation strategy for accelerating the oxidative dissolution of zerovalent iron (ZVI) using sulfite (S(IV)), thereby improving the removal of As(V) and As(III). Results revealed that, in the presence of 2.0 mM S(IV), both As(V) and As(III) were selectively converted into scorodite at pH 0 3.0-7.0, while As(III) oxidation and As(V) immobilization were impressed over pH 0 8.0-10.0. Batch experiments, radical quenching experiments, and electron spin resonance (ESR) measurements demonstrated that ZVI initially boosted S(IV) activation to generate SO 4 •- , • OH, and protons, and in turn, ZVI was further oxidized more intensely by these radicals than by oxygen. Concurrently, substantial protons derived from S(IV) oxidation neutralized hydroxyls produced by ZVI oxidation, maintaining an acidic environment conducive to the generation of scorodite rather than iron (hydr)oxides. Characterizations of X-ray diffraction (XRD), Raman, attenuated total reflectance-Fourier transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS), field emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscopy (HRTEM) confirmed that scorodite was formed in situ and then exfoliated from the surface of ZVI, and approximately 75% of ZVI could still be recovered, which contributed to efficient As removal in successive runs and real As-polluted wastewater. The application of S(IV) achieved a balance among ZVI reactivity improvement, As(V)/As(III) removal, and raw material consumption, making it a promising approach for addressing arsenic contamination in wastewater treatment.

This study investigated the coexistence and contamination of manganese (Mn(II)) and arsenite (As(III)) in groundwater and examined their oxidation behavior under different equilibrating parameters, including varying pH, bicarbonate (HCO 3 - ) concentrations, and sodium hypochlorite (NaClO) oxidant concentrations. Results showed that if the molar ratio of NaClO: As(III) was >1, the oxidation of As(III) could be achieved within a minute with an extremely high oxidation rate of 99.7 %. In the binary system, the removal of As(III) prevailed over Mn(II). The As(III) oxidation efficiency increased from 59.8 ± 0.6 % to 70.8 ± 1.9 % when pH rose from 5.7 to 8.0. The oxidation reaction between As(III) and NaClO releases H + ions, decreasing the pH from 6.77 to 6.19 and reducing the removal efficiency of Mn(II). The presence of HCO 3 - reduced the oxidation rate of Mn(II) from 63.2 % to 13.9 % within four hours. Instead, the final oxidation rate of Mn(II) increased from 68.1 % to 87.7 %. This increase can be attributed to HCO 3 - ions competing with the free Mn(II) for the adsorption sites on the sediments, inhibiting the formation of H + . Moreover, kinetic studies revealed that the oxidation reaction between Mn(II) and NaClO followed first-order kinetics based on their R 2 values. The significant factors affecting the Mn(II) oxidation efficiency were the initial concentration of NaClO and pH. Applying an artificial neural network (ANN) model for data analysis proved to be an effective tool for predicting Mn(II) oxidation rates under different experimental conditions. The actual Mn(II) oxidation data and the predicted values obtained from the ANN model showed significant consistency. The training and validation data sets yielded R 2 values of 0.995 and 0.992, respectively. Moreover, the ANN model highlights the importance of pH and NaClO concentrations in influencing the oxidation rate of Mn(II)., Competing Interests: Declaration of competing interest The authors declare no competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The utilization of biowastes for producing biochar to remove potentially toxic elements from water represents an important pathway for aquatic ecosystem decontamination. Here we explored the significance of thiol-functionalization on sugarcane bagasse biochar (Th/SCB-BC) and rice husk biochar (Th/RH-BC) to enhance arsenite (As(III)) removal capacity from water and compared their efficiency with both pristine biochars (SCB-BC and RH-BC). The maximum As(III) sorption was found on Th/SCB-BC and Th/RH-BC (2.88 and 2.51 mg g -1 , respectively) compared to the SCB-BC and RH-BC (1.51 and 1.40 mg g -1 ). Relatively, a greater percentage of As(III) removal was obtained with Th/SCB-BC and Th/RH-BC (92% and 83%, respectively) at a pH 7 compared to pristine SCB-BC and RH-BC (65% and 55%) at 6 mg L -1 initial As(III) concentration, 2 h contact time and 1 g L -1 sorbent dose. Langmuir (R 2  = 0.99) isotherm and pseudo-second-order kinetic (R 2  = 0.99) models provided the best fits to As(III) sorption data. Desorption experiments indicated that the regeneration ability of biochars decreased and it was in the order of Th/SCB-BC (88%) > Th/RH-BC (82%) > SCB-BC (77%) > RH-BC (69%) up to three sorption-desorption cycles. Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy results demonstrated that the thiol (-S-H) functional groups were successfully grafted on the surface of two biochars and as such contributed to enhance As(III) removal from water. Spectroscopic data indicated that the surface functional moieties, such as -S-H, - OH, - COOH, and C = O were involved to increase As(III) sorption on thiol-functionalized biochars. This study highlights that thiol-grafting on both biochars, notably on SCB-BC, enhanced their ability to remove As(III) from water, which can be used as an effective technique for the treatment of As from drinking water., (© 2024. The Author(s).)

Arsenic poisoning of groundwater is one of the most critical environmental hazards on Earth. Therefore, the practical and proper treatment of arsenic in water requires more attention to ensure safe drinking water. The World Health Organization (WHO) sets guidelines for 10 μg/L of arsenic in drinking water, and direct long-term exposure to arsenic in drinking water beyond this value causes severe health hazards to individuals. Numerous studies have confirmed the adverse effects of arsenic after long-term consumption of arsenic-contaminated water. Here, technologies for the remediation of arsenic from water are highlighted for the purpose of understanding the need for a single-point solution for the treatment of As(III)-contaminated water. As(III) species are neutral at neutral pH; the solution requires transformation technology for its complete removal. In this critical review, emphasis was placed on single-step technologies with multiple functions to remediate arsenic from water., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Dissolve organic matters (DOM) usually showed negative effect on the removal of inorganic arsenic (As) in groundwater by electrochemical approaches, yet which parts of sub-component within DOM played the role was lack of evidence. Herein, we investigated the effects of land-source humic-like acid (HA) on groundwater As(III) removal using air cathode iron electrocoagulation, based on the parallel factor analysis of three-dimensional excitation-emission matrix and statistical methods. Our results showed that the land-source HA contained five kinds of components and all components presented significantly negative correlations with the removal of both As(III) and As(V). However, the high aromatic fulvic-like acid and low aromatic humic-like acid components of land-source HA presented the opposite correlations with the concentration of As(III) during the reaction. The high aromaticity fulvic-like components of land-source HA (Sigma-Aldrich HA, SAHA) produced during the reaction facilitated the oxidation of As(III) due to its high electron transfer capacities and good solubility in wide pH range, but the low aromaticity humic-like ones worked against the oxidation of As(III). Our findings offered the novel insights for the flexible activities of DOM in electron Fenton system., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Exposure to arsenic can cause various biological effects by increasing the production of reactive oxygen species (ROS). Selenium acts as a beneficial element by regulating ROS and limiting heavy metal uptake and translocation. There are studies on the interactive effects of As and Se in plants, but the antagonistic and synergistic effects of these elements based on their binding to glutathione (GSH) molecules have not been studied yet. In this study, we aimed to investigate the antagonistic or synergistic effects of As and Se on the binding mechanism of Se and As with GSH at pH 3.0, 5.0, or 6.5. The interaction of As and Se in Se(SG) 2  + As(III) or As(SG) 3  + Se(IV) binary systems and As(III) + Se(IV) + GSH ternary system were examined depending on their ratios via liquid chromatography diode array detector/electrospray mass spectrometry (LC-DAD/MS) and liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS). The results showed that the formation of As(GS) 3 was not detected in the As(III) + Se(SG) 2 binary system, indicating that As(III) did not affect the stability of Se(SG) 2 complex antagonistically. However, in the Se(IV) + As(SG) 3 binary system, the addition of Se(IV) to As(SG) 3 affected the stability of As(SG) 3 antagonistically. Se(IV) reacted with GSH, disrupting the As(SG) 3 complex, and consequently, Se(SG) 2 formation was measured using LC-MS/DAD. In the Se(IV) + GSH + As(III) ternary system, Se(SG) 2 formation was detected upon mixing As(III), Se(IV), and GSH. The increase in the concentration of As(III) did not influence the stability of the Se(SG) 2 complex. Additionally, Se(IV) has a higher affinity than As(III) to the GSH, regardless of the pH of the solution. In both binary and ternary systems, the formation of the by-product glutathione trisulfide (GSSSG) was detected using LC-ESI-MS/MS., (© 2024 John Wiley & Sons Ltd.)

Arsenite-induced stress granule (SG) formation can be cleared by the ubiquitin-proteasome system aided by the ATP-dependent unfoldase p97. ZFAND1 participates in this pathway by recruiting p97 to trigger SG clearance. ZFAND1 contains two An1-type zinc finger domains (ZF1 and ZF2), followed by a ubiquitin-like domain (UBL); but their structures are not experimentally determined. To shed light on the structural basis of the ZFAND1-p97 interaction, we determined the atomic structures of the individual domains of ZFAND1 by solution-state NMR spectroscopy and X-ray crystallography. We further characterized the interaction between ZFAND1 and p97 by methyl NMR spectroscopy and cryo-EM. 15 N spin relaxation dynamics analysis indicated independent domain motions for ZF1, ZF2, and UBL. The crystal structure and NMR structure of UBL showed a conserved β-grasp fold homologous to ubiquitin and other UBLs. Nevertheless, the UBL of ZFAND1 contains an additional N-terminal helix that adopts different conformations in the crystalline and solution states. ZFAND1 uses the C-terminal UBL to bind to p97, evidenced by the pronounced line-broadening of the UBL domain during the p97 titration monitored by methyl NMR spectroscopy. ZFAND1 binding induces pronounced conformational heterogeneity in the N-terminal domain of p97, leading to a partial loss of the cryo-EM density of the N-terminal domain of p97. In conclusion, this work paved the way for a better understanding of the interplay between p97 and ZFAND1 in the context of SG clearance., Competing Interests: Conflict of interest The authors declare that they have no conflicts of interests with the contents of this article., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

The performance of combined reduction of nitrate (NO 3 - ) to dinitrogen gas (N 2 ) 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., (© 2023 The Authors. Biotechnology and Bioengineering published by Wiley Periodicals LLC.)

Phosphate is the biggest competitor for arsenic removal. Nanoscale metal oxides (NMOs) are commonly used to treat arsenic-contaminated water, yet their selective adsorption mechanisms for arsenic and phosphate are poorly understood. We quantified the selectivity of iron oxide (Fe 2 O 3 ), zinc oxide (ZnO), and titanium dioxide (TiO 2 ) nanosheets for arsenic in systems containing arsenic and phosphate, and determined the interaction of phosphate and arsenate/arsenite on metal oxide surfaces through batch experiments, spectroscopic techniques, and DFT calculations. We found that Fe 2 O 3 , TiO 2 , and ZnO nanosheets exhibit selectivity for arsenate/arsenite in the presence of phosphate, with Fe 2 O 3 the most selective, followed by TiO 2 and ZnO. The bonding mechanism on these metallic oxide surfaces dominates the selectivity. The more stable inner-sphere complexes of arsenate on the surfaces of Fe 2 O 3 (bidentate binuclear), TiO 2 (bidentate binuclear), and ZnO nanosheets (tridentate trinuclear) contribute to their preference for arsenate over phosphate. This difference in arsenate selectivity can be reflected in the difference in adsorption energy, net electron transfer number, and M - O bond length of the most stable inner sphere complexes. Overall, our study elucidated the selective adsorption mechanisms of arsenate/arsenite on Fe 2 O 3 , TiO 2 , and ZnO surfaces and highlighted the need to consider the competition between arsenate and phosphate during their removal from contaminated water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Surface complexation of arsenite (As(III)) on colloidal ferric hydroxide (CFH) plays an important role not only in the adsorptive immobilization of As(III) but also in the subsequent oxidation of As(III) to arsenate (As(V)) through light-induced ligand-to-metal charge transfer (LMCT) in water at near-neutral pH. However, the effects of natural organic matter (NOM), especially humic substances (HSs) and low molecular weight carboxylic acids (CAs), on the photochemistry of the CFH-As(III) system have not been sufficiently understood. In this work, the inhibition of photooxidation of As(III) in terms of the observed apparent rate constant (k obs ) by six HSs (below 16 mg L -1 ) and seven CAs (below 2.5 mM) has been observed in water containing 66 μM Fe(III) and 5 μM As(III) at pH 7 under simulated solar irradiation consisting of UVA (λ max 365 nm) and UVB (λ max 313 nm) lights. Total inhibition factors (T) have been determined from the combined effect of light-screening factor (S) and competitive complexation factor (C), wherein both S and C varied with NOM concentration. S was obtained by determining the absorbance of NOM, and C was obtained by fitting modified Langmuir or Freundlich models to the amount of As(III) desorbed from CFH upon the addition of NOM. Statistical analysis between the experimental T exp and the calculated one according to T cal  = S × C showed that the Freundlich model (RMSE for HS 0.1609 and for CA 0.1771) was better than the Langmuir model and was statistically robust (Q LOO 2 = 0.691 > 0.5). This work provided an estimation method for the effects of NOM on As(III) photooxidation in the presence of CFH as well as a deeper understanding of the transformation of arsenic species in sunlit water., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

A sensitive electroanalytical method for the determination of arsenite, based on a heterostructure of aminated multiwalled carbon nanotubes and gold nanoparticles, was applied in an electrocoagulation (EC) treatment for the elimination of arsenite. A sensitive quantitative response was obtained in the determination of As 3+ in a secondary effluent from a wastewater treatment plant from Santiago (Chile). The preconcentration stage was optimized through a Central Composite Face design, and the most sensitive peak current was obtained at 200 s and -600 mV of time and accumulation potential, respectively, after a differential pulse voltammetry sweep. Electroanalytical determination was possible in an interval between 42.89 and 170.00 μg L -1 with a detection limit of 0.39 μg L -1 , obtaining recoveries over 99.1%. The developed method was successfully applied in an electrocoagulation treatment to remove 250 μg L -1 of arsenite from a polluted effluent in a batch system. Complete arsenite removal was achieved using a steel EC system with a current density of 6.0 mA cm -2 in less than 3 min of treatment., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

To facilitate removing As(III) from water through an "oxidation-adsorption" process, the double-shell CuO x @MnO y hollow spheres (DCMHS) have been fabricated via a two-step co-precipitation route combined with the soft-template method. The surface characterization results showed that Mn oxides were formed without segregation and uniformly distributed on the surface of CuO x hollow spheres. DCMHS could achieve outstanding performance to remove As(III) with an As maximum adsorption capacity of 32.15 mg/g. Meanwhile, the kinetics results illustrated that the oxidative activity of DCMHS was strengthened due to its specific structure, and part of As(III) was converted to As(V) during the adsorption process. Also, air aeration could further enhance As(III) oxidation and thus improving As removal. The As(III) removal performance could be maintained under neutral and weak alkaline conditions. Phosphate, silicate, and carbonate anions could depress the removal performance, while chloride ions and sulfate anions barely influenced As removal. Moreover, DCMHS could be regenerated using NaOH and KMnO 4 solutions without breaking the hollow sphere structure. Based on the spectroscopic analysis results, As(III) molecules were converted to As(V) via two pathways, including the oxidation by Mn oxides or superoxide radicals. The Cu-Mn synergistic effect could not only enhance the oxidative activity of Mn oxides but also produce superoxide radicals via the activation of surface-adsorbed oxygen molecules. Afterwards, the newly formed As(V) could be attached to the hydroxyl groups through surface complexation. Therefore, this work has provided insights into the morphology design of Mn-oxide-containing adsorbents and supplemented the interface reaction mechanisms for enhancing As(III) removal., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Arsenic contamination is an increasing global environmental problem, especially in mining industry wastewater where both arsenite (As(III)) and arsenate (As(V)) have been routinely detected. In this paper, a novel porous metal-organic framework material (ZIF-8) was composited with iron nanoparticles (FeNPs) to form a functional material (ZIF-8@FeNPs) for the simultaneous removal of As(III)/(V) from wastewater. The material effectively removed both As(III) and As(V) with removal efficiencies of 99.9 and 71.2%, respectively. Advanced characterization techniques including X-ray photoelectron spectroscopy (XPS) and Fourier infrared (FTIR) indicated that removal of As(III) and As(V) involved complex formation. Adsorption kinetics followed a pseudo-second order kinetics indicating adsorption involved chemisorption. After four cycles of reuse the he removal rate of As species was still relatively high at > 60% When ZIF-8@FeNPs were used to remove As from real wastewater from acid mines the removal efficiency was 94.27%. Finally, a As(III) and As(V) removal mechanism was proposed., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Arsenic contamination in food and groundwater constitutes a public health concern for more than 200 million people worldwide. Individuals chronically exposed to arsenic through drinking and ingestion exhibit a higher risk of developing cancers and cardiovascular diseases. Nevertheless, the underlying mechanisms of arsenic toxicity are not fully understood. Arsenite is known to bind to and deactivate RING finger E3 ubiquitin ligases; thus, we reason that a systematic interrogation about how arsenite exposure modulates global protein ubiquitination may reveal novel molecular targets for arsenic toxicity. By employing liquid chromatography-tandem mass spectrometry, in combination with stable isotope labeling by amino acids in cell culture (SILAC) and immunoprecipitation of di-glycine-conjugated lysine-containing tryptic peptides, we assessed the alterations in protein ubiquitination in GM00637 human skin fibroblast cells upon arsenite exposure at the entire proteome level. We observed that arsenite exposure led to altered ubiquitination of many proteins, where the alterations in a large majority of ubiquitination events are negatively correlated with changes in expression of the corresponding proteins, suggesting their modulation by the ubiquitin-proteasomal pathway. Moreover, we observed that arsenite exposure confers diminished ubiquitination of a rate-limiting enzyme in cholesterol biosynthesis, HMGCR, at Lys 248 . We also revealed that TRC8 is the major E3 ubiquitin ligase for HMGCR ubiquitination in HEK293T cells, and the arsenite-induced diminution of HMGCR ubiquitination is abrogated upon genetic depletion of TRC8. In summary, we systematically characterized arsenite-induced perturbations in a ubiquitinated proteome in human cells and found that the arsenite-elicited attenuation of HMGCR ubiquitination in HEK293T cells involves TRC8.

The speciation and fate of arsenic (As) in soil-water systems is a topic of great interest, in part due to growing awareness of As uptake into rice as an important human exposure pathway to As. Rice paddy and other wetland soils are rich in dissolved organic matter (DOM), leading to As/DOM ratios that are typically lower than those in groundwater aquifers or that have been used in many laboratory studies of As-DOM interactions. In this contribution, we evaluate arsenite (As(III)) binding to seven different DOM samples at As/DOM ratios relevant for wetland pore waters, and explore the chemical properties of the DOM samples associated with high levels of As(III)-DOM complexation. We integrate data from wet chemical analysis of DOM chemical properties, dialysis equilibrium experiments, and two-site ligand binding models to show that in some DOM samples, 15-60% of As(III) can be bound to DOM at environmentally-relevant As/DOM ratios of 0.0032-0.016 μmol As/mmol C. Binding decreases as the As(III)/DOM ratio increases. The organic sulfur (S org ) content of the DOM samples was strongly correlated with levels of As(III)-DOM complexation and "strong" binding site densities, consistent with theories that thiols are strong binding ligands for As(III) in natural organic matter. Finally, a whole-cell E. coli biosensor assay was used to show that DOM samples most effective at complexing As(III) also led to decreased microbial As(III) uptake at low As/DOC ratios. This work demonstrates that naturally-occurring variations in the S org content of DOM has a significant impact on As(III) binding to DOM, and has implications for As(III) availability to microorganisms., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The manganese is successfully induced as a "bridge joint" to fabricate a new adsorbent (CNC-Mn-PEI) connecting cellulose nanocrystal (CNC) and polyethyleneimine (PEI) respectively. It was used to remove As (III) from waste water. It has been proved that the incompact CNC and PEI were successfully connected by Mn ions, which induced the formation of O-Mn-O bonds and the removal efficiency is maintained in the broad pH range of 4-8, even with the influence of NO 3 - and CO 3 2- . The CNC-Mn-PEI was characterized by Brunauer-Emmett-Telley (BET) method and the results showed that the nanoparticle of the specific surface area was 106.5753 m 2 /g, it has a significant improvement, compared with CNC-Mn-DW (0.1918 m 2 /g). The isotherm and kinetic parameters of arsenic removal on CNC-Mn-PEI were well-fitted by the Langmuir and pseudo-second-order models. The maximum adsorption capacities toward As (III) was 78.02 mg/g. After seven regeneration cycles, the removal of As (III) by the adsorbent decreased from 80.78% to 68.2%. Additionally, the hypothetical adsorption mechanism of "bridge joint" effect was established by FTIR and XPS, which provided the three activated sites from CNC-Mn-PEI can improve the arsenic removal efficiency, and providing a new stratagem for the arsenic pollution treatment., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Groundwater contaminated with arsenic (As) must be treated prior to drinking, as human exposure to As at toxic levels can cause various diseases including cancer. Conventional aeration-filtration applied to anaerobic arsenite (As(III)) contaminated groundwater can remove As(III) by co-oxidizing native iron (Fe(II)) and As(III) with oxygen (O 2 ). However, the As(III) removal efficiency of conventional aeration can be low, in part, because of incomplete As(III) oxidation to readily-sorbed arsenate (As(V)). In this work, we investigated a new approach to enhance As(III) co-removal with native Fe(II) by the anaerobic addition of hydrogen peroxide (H 2 O 2 ) prior to aeration. Experiments were performed to co-oxidize Fe(II) and As(III) with H 2 O 2 (anaerobically), O 2 (aerobically), and by sequentially adding of H 2 O 2 and O 2 . Aqueous As(III) and As(V) measurements after the reaction were coupled with solid-phase speciation by Fe and As K-edge X-ray absorption spectroscopy (XAS). We found that complete anaerobic oxidation of 100 µM Fe(II) with 100 µM H 2 O 2 resulted in co-removal of 95% of 7 µM As(III) compared to 44% with 8.0-9.0 mg/L dissolved O 2 . Furthermore, we found that with 100 µM Fe(II), the initial Fe(II):H 2 O 2 ratio was a critical parameter to remove 7 µM As(III) to below the 10 µg/L (0.13 µM) WHO guideline, where ratios of 1:4 (mol:mol) Fe(II):H 2 O 2 led to As(III) removal matching that of 7 µM As(V). The improved As(III) removal with H 2 O 2 was found to occur partly because of the well-established enhanced efficiency of As(III) oxidation in Fe(II)+H 2 O 2 systems relatively to Fe(II)+O 2 systems. However, the XAS results unambiguously demonstrated that a large factor in the improved As(III) removal was also due to a systematic decrease in crystallinity, and thus increase in specific surface area, of the generated Fe(III) (oxyhydr)oxides from lepidocrocite in the Fe(II)+O 2 system to poorly-ordered Fe(III) precipitates in the Fe(II)+H 2 O 2 system. The combined roles of H 2 O 2 (enhanced As(III) oxidation and structural modification) can be easily overlooked when only aqueous species are measured, but this dual impact must be considered for accurate predictions of As removal in groundwater treatment., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier Ltd.)

The adsorption of inorganic arsenic (As) plays an important role in the mobility and transport of As in the river environment. In this work, the adsorption and desorption of arsenite [As(III)] and arsenate [As(V)] on river sediment were conducted under different pH, initial As concentrations, river water and sediment composition to assess As adsorption behavior and mechanism. Both adsorption kinetics and equilibrium results showed higher adsorption capacity of sediment for As(V) than As(III). Adsorption of As(III) and As(V) on river sediment was favored in acidic to neutral conditions and on finer sediment particles, while sediment organic matter marginally reduced adsorption capacity. In addition, higher adsorption affinity of As(III) and As(V) in river sediment was observed in deionised water than in river water. For the release process, the desorption of both As(III) and As(V) followed nonlinear kinetic models well, showing higher amount of As(III) release from sediment than As(V). Adsorption isotherm was well described by both Langmuir and Freundlich models, demonstrating higher maximum adsorption capacity of As(V) at 298.7 mg/kg than As(III) at 263.3 mg/kg in deionised water, and higher maximum adsorption capacity of As(III) of 234.3 mg/kg than As(V) of 206.2 mg/kg in river water. The XRD showed the changes in the peaks of mineral groups of sediment whilst FTIR results revealed the changes related to surface functional groups before and after adsorption, indicating that Fe-O/Fe-OH, Si(Al)-O, hydroxyl and carboxyl functional groups were predominantly involved in As(III) and As(V) adsorption on sediment surface. XPS analysis evidenced the transformation between these As species in river sediment after adsorption, whilst SEM-EDS revealed higher amount of As(V) in river sediment than As(III) due to the lower signal of Al., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Photooxidation of As(III) by TiO 2 is a complicated process in which the oxidation mechanisms are always controversial. In this study, the enhanced photooxidation rates of As(III) with increasing pH values from 8.0 to 11.0 indicate the high photocatalytic reactivity of TiO 2 under alkaline conditions. Moreover, As(III) improves the production of H 2 O 2 , indicating H-abstraction from As(III) (soluble or adsorbed) for H 2 O 2 production. Although O 2 ˙ - , h + , ˙OH and -OOH are always regarded as the reactive oxygen species in the UV-TiO 2 system, the superoxo and peroxo species formed on the surface of TiO 2 also contribute to As(III) oxidation. The As(III)-O-Ti(IV) surface complexes formed on TiO 2 , as well as the decreased bandgaps of TiO 2 with increasing concentrations of As(III) indicate that the ligand-to-metal charge transfer (LMCT) pathway also contributes to the oxidation of As(III) under alkaline conditions. Electrochemical analyses further reveal that As(III) enhances the electron density on the surface of TiO 2 , thereby improving the catalytic reactivity of TiO 2 . We therefore suggest that H-abstraction from As(III) or H 2 O to the formed superoxo and peroxo species results in the formation of H 2 O 2 , accompanied by the oxidation of As(III). This enriches our knowledge on the oxidation of As(III), as well as other contaminants rich in -OH groups during the photocatalytic oxidation processes.

Hypothesis: The easy aggregation of superparamagnetic iron oxide nanoparticles (SPION) greatly reduces their adsorption performance for removing arsenic (As) from polluted water. We propose to exploit the porosity and good diffusion properties of a cube-shaped cellulose sponge for loading SPION to reduce the aggregation and to develop a composite adsorbent in the cm-scale that could be used for industrial applications., Experiments: SPION were in-situ synthesized by co-precipitation using a commercial cube-shaped sponge (MetalZorb®) as support. The morphology, iron-oxide phase, adsorption performance and thermodynamic parameters of the composite adsorbent were determined to better understand the adsorption process. X-ray absorption spectroscopy (XAS) was used to investigate the chemical state of the adsorbed As(III)., Findings: The adsorption of the supported SPION outperforms the unsupported SPION (ca. 14 times higher adsorption capacity). The modelling of the adsorption isotherms and the kinetic curves indicated that chemisorption is controlling the adsorption process. The thermodynamic analysis shows that the adsorption retains the spontaneous and endothermic character of the unsupported SPION. The XAS results revealed an adsorption-oxidation mechanism in which the adsorbed As(III) was partially oxidized to less toxic As(V) by the hydroxyl free radical (•OH) generated from Fe(III) species and by the hydroxyl groups., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

Whole-cell sensors for arsenite detection have been developed exclusively based on the natural arsenite (As(III)) sensory protein ArsR for arsenic metabolism. This study reports that the quorum-sensing LuxR/Plux system from Vibrio fischeri, which is completely unrelated to arsenic metabolism, responds to As(III) in a dose-dependent manner. Due to as many as 9 cysteine residues, which has a high binding affinity with As(III), LuxR underwent As(III)-induced insoluble form, thereby reducing its effective cellular concentration. Accordingly, the expression level of green fluorescent protein under the control of Plux gradually decreased with increasing As(III) concentration in the medium. This is a novel As(III)-detection system that has never been proposed before, with a unique ON-to-OFF transfer function., (Copyright © 2021 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.)

Nanoscale zerovalent iron (nZVI) is considered as a highly efficient material for sequestrating arsenite, but the origin of its high efficacy as well as the chemical transformations of arsenite during reaction is not well understood. Here, we report an in situ X-ray absorption spectroscopy (XAS) study to investigate the complex mechanism of nZVI reaction with arsenite under anaerobic conditions at the time scale from seconds to days. The time-resolved XAS analysis revealed a gradual oxidation of As III to As V in the course of minutes to hours in both the solid and liquid phase for the high (above 0.5 g/L) nZVI dose system. When the reaction time increased up to 60 days, As V became the dominant species. The quick-scanning extended X-ray absorption fine structure (QEAXFS) was introduced to discover the transient intermediate at the highly reactive stage, and a small red-shift in As K-edge absorption edge was observed. The QEAXFS combined with density functional theory (DFT) calculation suggested that the red-shift is likely due to the electron donation in a Fe-O-As complex and possible active sites of As sequestrations include Fe(OH) 4 and 4-Fe cluster. This is the first time that the transient reaction intermediate was identified in the As-nZVI sequestration system at the fast-reacting early stage. This study also demonstrated usefulness of in situ monitoring techniques in environmental water research.

The blood-brain barrier (BBB) is the most critical obstacle in the treatment of central nervous system disorders, such as glioma, the most typical type of brain tumor. To overcome the BBB and enhance drug-penetration abilities, we used angiopep-2-modified liposomes to deliver arsenic trioxide (ATO) across the BBB, targeting the glioma. Angiopep-2-modified calcium arsenite-loaded liposomes (A2-PEG-LP@CaAs), with uniformly distributed hydrodynamic diameter (96.75 ± 0.57 nm), were prepared using the acetate gradient method with high drug-loading capacity (7.13 ± 0.72%) and entrapment efficiency (54.30 ± 9.81%). In the acid tumor microenvironment, arsenic was responsively released, thereby exerting an anti-glioma effect. The anti-glioma effect of A2-PEG-LP@CaAs was investigated both in vitro and in vivo. As a result, A2-PEG-LP@CaAs exhibited a potent, targeted anti-glioma effect mediated by the lipoprotein receptor-related (LRP) receptor, which is overexpressed in both the BBB and glioma. Therefore, A2-PEG-LP@CaAs could dramatically promote the anti-glioma effect of ATO, as a promising strategy for glioma therapy., Competing Interests: Declaration of competing interest There are no conflicts to declare., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Arsenosugars are a group of arsenic-containing ribosides that are found predominantly in marine algae but also in terrestrial organisms. It has been proposed that arsenosugar biosynthesis involves a key intermediate 5'-deoxy-5'-dimethylarsinoyl-adenosine (DDMAA), but how DDMAA is produced remains elusive. Now, we report characterization of ArsS as a DDMAA synthase, which catalyzes a radical S-adenosylmethionine (SAM)-mediated alkylation (adenosylation) of dimethylarsenite (DMAs III ) to produce DDMAA. This radical-mediated reaction is redox neutral, and multiple turnover can be achieved without external reductant. Phylogenomic and biochemical analyses revealed that DDMAA synthases are widespread in distinct bacterial phyla with similar catalytic efficiencies; these enzymes likely originated from cyanobacteria. This study reveals a key step in arsenosugar biosynthesis and also a new paradigm in radical SAM chemistry, highlighting the catalytic diversity of this superfamily of enzymes., (© 2021 Wiley-VCH GmbH.)

Arsenoplatin-1 (AP-1) is an innovative dual-action anticancer agent that contains a platinum(ii) center coordinated to an arsenous acid moiety. We found that AP-1 spontaneously aggregates in aqueous solutions generating oligomeric species of increasing length. Afterward, we succeeded in solving the crystal structure of the adduct formed between the model protein lysozyme and an early AP-1 oligomer that turned out to be a trimer. Remarkably, this crystal structure traps an early stage of AP-1 aggregation offering detailed insight into the molecular process of the oligomer's growth.

Up to now, complicated organoarsenicals were mainly identified in marine organisms, suggesting that these organisms play a critical role in arsenic biogeochemical cycling because of low phosphate and relatively high arsenic concentration in the marine environment. However, the response of marine macroalgae to inorganic arsenic remains unknown. In this study, Pyropia haitanensis were exposed to arsenate [As(V)] (0.1, 1, 10, 100 μM) or arsenite [As(III)] (0.1, 1, 10 μM) under laboratory conditions for 3 d. The species of water-soluble arsenic, the total concentration of lipid-soluble and cell residue arsenic of the algae cells was analyzed. As(V) was mainly transformed into oxo-arsenosugar-phosphate, with other arsenic compounds such as monomethylated, As(III), demethylated arsenic and oxo-arsenosugar-glycerol being likely the intermediates of arsenosugar synthesis. When high concentration of As(III) was toxic to P. haitanensis, As(III) entered into the cells and was transformed into less toxic organoarsenicals and As(V). Transcriptome results showed genes involved in DNA replication, mismatch repair, base excision repair, and nucleotide excision repair were up-regulated in the algae cells exposed to 10 μM As(V), and multiple genes involved in glutathione metabolism and photosynthetic were up-regulated by 1 μM As(III). A large number of ABC transporters were down-regulated by As(V) while ten genes related to ABC transporters were up-regulated by As(III), indicating that ABC transporters were involved in transporting As(III) to vacuoles in algae cells. These results indicated that P. haitanensis detoxifies inorganic arsenic via transforming them into organoarsenicals and enhancing the isolation of highly toxic As(III) in vacuoles., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

As (III) is widely distributed in groundwater which is relatively harder to be removed comparing to As (V). Co-grinding Ca(OH) 2 with Al(OH) 3 was conducted to manufacture katoite (Ca 3 Al 2 (OH) 12 ) for the complete removal of As(III) (concentration below drinking water standard of WHO (<10 ppb)) during one-step agitation operation. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TG), and X-ray photoelectron spectroscopy (XPS) were applied for the illustration of adsorption mechanism. Katoite could intercalate As(III) into the layered space forming arsenite pillared Ca-Al layered double hydroxide (LDH). The coexisting anions such as Cl - , SO 4 2- , and NO 3 - had minor effects on As (III) removal performance using katoite. Techno-economic analysis demonstrated the feasibility of large-scale katoite production and its practical application for As(III) polluted groundwater purification, especially in the undeveloped areas where groundwater was used as irrigation and drinking water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Fe-Mn nodules affect the speciation, transformation and migration of arsenic (As) via redox and adsorption reactions. However, few studies have been concerned with their interaction in the presence of dissolved oxygen. In this work, the interaction mechanism of As(III) and Fe-Mn nodules was studied in different atmospheres. The influence of pH, dissolved oxygen concentration and chemical composition of nodules on the reaction was also investigated. The results indicated that manganese oxides and iron oxides in nodules respectively contribute to As(III) oxidation and As(III,V) adsorption. Under oxic conditions, Fe-Mn nodules acted as a catalyst to accelerate the oxidation of Mn(II) to Mn(III,V) oxides, which significantly enhanced As(III) oxidation. In the system containing 10 mg L -1 As(III) and 1.0 g L -1 Fe-Mn nodules, the maximum oxidation capacity of As(III) reached 3.22, 3.48 and 3.71 mg g -1 , and the corresponding As(III,V) adsorption capacity reached 2.49, 2.40, and 2.39 mg g -1 in nitrogen, air and oxygen atmosphere, respectively. The oxidation capacity of As(III) increased and decreased with increasing dissolved oxygen concentration and pH, respectively. This work clarifies the mechanism of As(III) oxidation by soil Fe-Mn nodules in various systems and contributes to a better understanding of the behaviors and fate of As in environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Commercially available drug-eluting embolization beads (100-500 μm) reduced the occurrence of adverse events related to an anticancer drug, but were unascertained to remarkably benefit the transcatheter arterial chemoembolization (TACE) treatment of intermediate-stage liver cancer. Dextran-coated arsenite nanoparticles with the size ranging from 400 to 600 nm were developed as a nanosized drug-eluting bead (NDEB) for chemoembolization therapy of the rabbit VX2 liver tumor. We fully characterized their relevant physicochemistry and drug release properties. Their hemolysis was investigated before vessel embolization. The introduction of the NDEB allowed continuous embolization of tumor feeding vessels and sustained release of arsenic trioxide, thereby causing severe tumor necrosis and reduced vascularity. Sonography including B mode ultrasound, color Doppler flow imaging (CDFI) and dynamic contrast-enhanced ultrasound (CEUS) were performed to evaluate the tumor vascularity and viability. Additionally, its hepatotoxicity was tolerable at a medium dose. NDEB-TACE might be an effective therapeutic strategy for interventional therapy.

Deoxynucleotides can be good monomers for arsenite ion-imprinted polymers (IIPs) due to the successful obtainment of aptamers which can specifically recognize arsenite. However, the recognition and interaction mechanism between arsenite and deoxynucleotides is still not clear. In this work, the binding interactions between arsenite and deoxynucleotides (dAMP, dTMP, dGMP, dCMP) as pH changing from 1 to 14 were investigated using density functional theory calculations as well as spectroscopy analysis. dGMP was calculated to have the largest affinity towards arsenite. H 3 AsO 3 0 -dGMP 0 binding at phosphate group, H 3 AsO 3 0 -dAMP 2- , H 3 AsO 3 0 -dCMP 0 and H 3 AsO 3 0 -dTMP 2- binding around nucleobase were found to be the most stable complexes. This suggests the optimal pH ranges for binding interactions of dAMP, dCMP, dGMP and dTMP towards arsenite might be 6.10-9.23, 1.00-4.50, 1.00-2.40 and 6.40-9.23, respectively, which agree with UV/VIS experimental results. Reduced Density Gradient method indicated that the binding interactions of arsenite with deoxynucleotides are mainly attributed to hydrogen bonds (H-bond). The strengths of these H-bonds are affected by pH. FT-IR and NMR spectroscopy analysis also provided essential H-bonding information, giving direct evidence to support the computational conclusions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The application of conventional electrocoagulation (EC) process for removal of As(III) from groundwater suffers from the need of external oxidation agent for oxidation of As(III) to As(V). To tackle this limitation, an aerated EC reactor for the removal of As(III) from groundwater was evaluated in this study. The effect of initial pH i , air flow rate, applied current, and electrode height in the EC reactor was examined. The experimental results showed that removal of arsenic mostly dependent on the applied current, electrode height in EC reactor, and air flow rate. The As(III) removal efficiency (99.2%) was maximum at pH i of 7.5, air flow rate of 6 L min -1 , applied current of 0.30 A, and electrode height in EC reactor of 5 cm, with an total operating cost of 0.583 $ m -3 . Furthermore, the carcinogenic risk (CR) and non-carcinogenic risk of arsenic (As) was in the range of tolerable limits at all operating conditions except applied current of 0.075 A at the end of the aerated EC process to remove As from groundwater. The present EC reactor process is able to remove As(III) from groundwater to below 10 μg L -1 , which is maximum contaminant level of arsenic in drinking water according to the World Health Organization (WHO)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The threat of arsenic contamination to public health, particularly in developing countries, has become a serious problem. Millions of people in their daily lives are still highly dependent on groundwater containing high levels of arsenic, which causes excessive exposure to this toxic element, due to the high cost and lack of water-treatment infrastructures. Therefore, a technique for large-scale treatment of water in rural areas to remove arsenic is needed and should be low-cost, be easily customized, and not rely on electrical power. In this study, in an effort to fulfill those requirements, we introduce a three-dimensional (3D), printed water-filtration system for arsenic removal. Three-dimensional printing can provide a compact, customized filtration system that can fulfill the above-mentioned requirements and that can be made from plastic materials, which are abundant. Armed with the versatility of 3D printing, we were able to design the internal surface areas of filters, after which we modified the surfaces of the 3D, printed filters by using iron (III) oxide as an adsorbent for arsenite. We investigated the effects of the controlled surface area on the flow rate and the deposition of the adsorbent, which are directly related to the adsorption of arsenic. We conducted isotherm studies to quantify the adsorption of arsenic on our 3D, printed filtration system., Competing Interests: The authors have declared that no competing interests exist.

Arsenite is a highly toxic compound present in many water sources around the world. The removal of arsenite from water requires its oxidation to arsenate which is much more amenable to treatment using well attested technologies. Prior research has shown that the oxidation of arsenite by hydroxyl radicals is significantly accelerated in the presence of carbonate ions but the intrinsic mechanisms of the acceleration have not yet been established. The main goal of the present work was to examine the oxidation of arsenite in the framework of the density functional theory, to establish a detailed microscopic level mechanism of interactions between arsenite and hydroxyl radicals and to elucidate the nature of the catalytic effect of carbonate ions. Results of this study demonstrate that the [As(OH) 2 CO 3 ] - complex is the thermodynamically most stable species formed in the system H 3 AsO 3 -CO 3 2- /HCO 3 - -H 2 O. Interactions of the hydroxyl radical with the [As(OH) 2 CO 3 ] - complex yield the pre-reaction complex [As(OH) 3 CO 3 ] -∗ in the reaction of subsequent oxidation of arsenite. The structures of the reactants, products and transition states, as well as pre- and post-reaction complexes corresponding to several possible mechanisms of the first stage of As(III) oxidation to As(IV) intermediate using hydroxyl radicals in the absence and in the presence of [As(OH) 2 CO 3 ] - , were determined in this study. The data demonstrate that the arsenite-carbonate complexes [As(OH) 2 CO 3 ] - are characterized by a significantly lower activation energy of the first oxidation stage under the action of a hydroxyl radical (2.8 kcal/mol) compared to that for the free arsenite H 3 AsO 3 (13.6 kcal/mol)., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Several studies have demonstrated that gypsum (CaSO 4 ·2H 2 O) and calcite (CaCO 3 ) can be important hosts of arsenic in contaminated hydrogeological systems. However, the extent to which microbial reducing processes contribute to the dissolution and transformation of carbonate and sulfate minerals and, thereby, to arsenic mobilization is poorly understood. These processes are likely to have a strong impact on arsenic mobility in iron-poor environments and in reducing aquifers where iron oxyhydroxides become unstable. Anoxic batch bioassays with arsenate (As(V)) coprecipitated with calcite, gypsum, or ferrihydrite (Fe(OH) 3 ) were conducted in the presence of sulfate or molybdate to examine the impact of bioprocesses (i.e. As(V), sulfate, and Fe(III)-reduction) on arsenic dissolution, speciation, and eventual remineralization. Microbial reduction of As(V)-bearing calcite caused an important dissolution of arsenite, As(III), which remained in solution up to the end of the experiment (30 days). The reduction of As(V) from gypsum-As(V) also led to the release of As(III), which was subsequently remineralized, possibly as arsenic sulfides. The presence of sulfate triggered arsenic dissolution in the bioassays with ferrihydrite-As(V). This study showed that although gypsum and calcite have a lower capacity to bind arsenic, compared to iron oxides, they can play a critical role in the biogeochemical cycle of arsenic in natural calcareous and gypsiferous systems depleted of iron since they can be a source of electron acceptors for reducing bioprocesses., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Ligands may increase the yields of reactive oxygen species (ROS) in zero-valent iron (ZVI)/O 2 systems. To clarify the relationship between the properties of ligands and their effects on the oxidative removal of contaminants, five common ligands (formate, acetate, oxalate, ethylenediaminetetraacetic acid (EDTA), and phosphate) as well as acetylacetone (AA) were investigated with arsenite (As(III)) as the target contaminant at three initial pH values (3.0, 5.0, and 7.0). The addition of these ligands to the ZVI/O 2 system resulted in quite different effects on As(III) removal. EDTA enhanced the oxidation of As(III) to arsenate (As(V)) but inhibited the removal of As(V). Oxalate was the only ligand in this work that accelerated both the removal of As(III) and As(V). By analyzing the ligand effects from the four aspects: dissolution of surface iron (hydr)oxides, corrosion of ZVI, reaction with ROS, and interference with precipitation, the following properties of ligands were believed to be important: ability to provide dissociable protons, complexation ability with iron, and reactivity with ROS. The complexation ability is a double-edged sword. It could enhance the generation of ROS by reducing the reduction potential of the Fe(III)/Fe(II) redox couple, but also could inhibit the removal of arsenic by coprecipitation. The elucidated relationship between the key property parameters of ligands and their effects on the ZVI/O 2 system is helpful for the rational design of effective ZVI/ligand/O 2 systems., (Copyright © 2019. Published by Elsevier B.V.)

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 H 2 O 2 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 H 2 O 2 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., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

We investigated the impact of aging-induced structural modifications of carbonate green rust (GR), a mixed valent Fe(ii,iii) (hydr)oxide with a high oxyanion sorption affinity, on the partitioning and binding mode of arsenic (As). Suspensions of carbonate GR were produced in the presence of As(v) or As(iii) (i.e. co-precipitated with As(iii) or As(v)) and aged in anoxic and oxic conditions for up to a year. We tracked aqueous As over time and characterized the solid phase by X-ray absorption spectroscopy (XAS). In experiments with initial As(v) (4500 μg L-1, As/Fe = 2 mol%), the fresh GR suspension sorbed >99% of the initial As, resulting in approximately 14 ± 8 μg L-1 residual dissolved As. Anoxic aging of the As(v)-laden GR for a month increased aqueous As to >60 μg L-1, which was coupled to an increase in GR structural order revealed by Fe K-edge XAS. Further anoxic aging up to a year transformed As(v)-laden GR into magnetite and decreased significantly the aqueous As to <2 μg L-1. The As binding mode was also modified during GR transformation to magnetite from sorption to GR particle edges to As substitution for tetrahedral Fe in the magnetite structure. These GR structural modifications altered the ratio of As partitioning to the solid (μg As/mg Fe) and liquid (μg As per L) phase from 2.0 to 0.4 to 14 L mg-1 for the fresh, month, and year aged suspensions, respectively. Similar trends in GR transformation and As partitioning during anoxic aging were observed for As(iii)-laden suspensions, but occurred on more rapid timescales: As(iii)-laden GR transformed to magnetite after a day of anoxic aging. In oxic aging experiments, rapid GR oxidation by dissolved oxygen to Fe(iii) precipitates required only an hour for both As(v) and As(iii) experiments, with lepidocrocite favored in As(v) experiments and hydrous ferric oxide favored in As(iii) experiments. Aqueous As during GR oxidation decreased to <10 μg L-1 for both As(v) and As(iii) series. Knowledge of this interdependence between GR aging products and oxyanion fate improves biogeochemical models of contaminant and nutrient dynamics during Fe cycling and can be used to design more effective arsenic remediation strategies that rely on arsenic sorption to GR.

It is of interest to use UV-sulfite based processes to degrade pollutants in wastewater treatment process. In this work, arsenic (As(III)) has been selected as a target pollutant to verify the efficacy of such a hypothesized process. The results showed that As(III) was quickly oxidized by a UV-sulfite system at neutral or alkaline pH and especially at pH 9.5, which can be mainly attributed to the generated oxysulfur radicals. In laser flash photolysis (LFP) experiments (λ ex = 266 nm), the signals of SO 3 •- and e aq - generated by photolysis of sulfite at 266 nm were discerned. Quantum yields for photoionization of HSO 3 - (0.01) and SO 3 2- (0.06) were also measured. It has been established that e aq - does not react with SO 3 2- , but reacts with HSO 3 - with a rate constant 8 × 10 7 M -1 s -1 .

Gold nanoparticles (AuNPs) have been extensively used for detecting arsenite, As(III). Many methods rely on a DNA aptamer that claimed to bind specifically to inorganic arsenic. In these cases, the focus was on arsenic binding to the aptamer, while the potential interactions between As(III) and the AuNP surface were ignored. Herein, a set of spectroscopic and isothermal titration calorimetry (ITC) experiments were conducted to measure the adsorption of As(III) by AuNPs and its competition with DNA adsorption. With 10 mM As(III), 18% of adsorbed DNA was displaced from AuNPs, while preadsorption of only 20 μM As(III) inhibited DNA adsorption by around 50%. The affinity of As(III) on AuNPs is comparable to Br - and guanosine. ITC and Raman spectroscopy both indicated that only As(III) can be adsorbed, while As(V) had no measurable interactions with the AuNPs. Based on this understanding, a random DNA sequence was used and a similar colorimetric response in the presence of As(III) was observed. This study confirmed the affinity between As(III) and the gold surface. The As(III)/gold interaction is strong enough to affect DNA adsorption, and care should be taken to interpret the observations based on the color change of AuNPs for the detection of As(III).

Arsenic mobility in soils, sediments and groundwater systems is strongly controlled by adsorption occurring at iron oxide/water interfaces, and the extent of this adsorption may be influenced by the presence of natural organic matter (NOM). This study aims to investigate the adsorption of As(III) and As(V) onto coprecipitates made with ferrihydrite (Fh) and humic acid (HA) with two organic carbon (OC) loadings of 5 and 15 wt% OC. We show that the coprecipitation of HA with Fh can significantly reduce the retention of both As(III) and As(V) over a wide pH range (4-11), and with increased OC loading, there is reduced arsenic adsorption. On pure Fh, As(III) is adsorbed to a greater extent than As(V) at pH > 6.5 (the crossover pH), whereas the crossover pH shifts to more acidic pH in the presence of HA, implying that the binding of As(III) is more favorable than As(V) in the presence of NOM. Both As(III) and As(V) are complexed with the ferric hydroxyl functional groups, and no ternary Fh-HA-As complexes are detected. We observe that ∼40% of the adsorbed As(III) is oxidized to As(V) on pure Fh, compared to only ∼29% of As(III) oxidation on the Fh-HA coprecipitate, indicating that NOM hinders As(III) oxidation on iron (hydr)oxide. The results of this study suggest that NOM interacts with arsenic in ways that promote arsenic mobility and especially promote the mobility of arsenate relative to arsenite, which is of great significance for evaluating the migration and bioavailability of arsenic in both natural and contaminated environments., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

TiO 2 is one of the most cheap materials which can both adsorb arsenic and oxidize arsenite [As(III)] to arsenate [As(V)]. In this study, anatase TiO 2 crystals with different main facets such as {101}, {001} and {100} are synthesized and used to investigate arsenic adsorption kinetics, adsorption isotherms, photocatalytic oxidation (PCO) process and the pH effects. The adsorption kinetics of arsenic on TiO 2 crystals can be described by the pseudo second-order kinetic model. For the adsorption isotherms, the Langmuir model is better than the Freundlich model for arsenic on these TiO 2 crystals. For the PCO process, the rate of As(III) oxidation can be denoted by the pseudo first-order kinetic model. It should be noted that at neutral condition the adsorption and PCO rates of the three kinds of TiO 2 crystals follow the order of {101} > {001} > {100}. The pH effect is above all important for both the arsenic adsorption and its PCO. The highest PCO speed appears at high pH values such as at pH 11 or 12., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Arsenic, a common contaminant in groundwater environments, usually coexists with other contaminants, for example, ammonium, iron, and manganese. In our previous studies, an iron-manganese (Fe-Mn) oxides filter media was developed for catalytic oxidation removal of ammonium, iron, and manganese. In this study, batch oxidation/adsorption kinetic experiments revealed that the filter media could easily oxidize arsenite (As(III)) to arsenate (As(V)). And the sorption kinetics was found to follow the pseudo-second-order kinetic model. X-ray powder diffraction (XRD) and Fourier transform infrared spectra (FTIR) along with X-ray photoelectron spectroscopy (XPS) were used to analyze the surface change in the Fe-Mn oxides. Based on sorption and spectroscopic measurements, the mechanism of As(III) removal by the Fe-Mn oxides filter media was found to be an oxidation coupled with sorption approach. As(III) in the aqueous solution was firstly oxidized to As(V) on the surfaces of the Fe-Mn oxides filter media. Then the converted As(V) was attracted to the Fe-Mn oxides filter media surfaces and bounded with the active sites (-OH groups), through weak intermolecular H-bondings. Our results indicated that the novel Fe-Mn oxides filter media could be applied for the simultaneous removal of ammonium, iron, manganese, and As(III) in drinking water treatment and environmental remediation. PRACTITIONER POINTS: A novel iron-manganese oxides filter for efficient As(III) removal was established. The exhausted filter media could be easily regenerated by NaHCO 3 solution. Mn(III) related to surface lattice oxygen species was responsible for As(III) oxidation. The oxidation and adsorption processes were involved in As(III) removal. The filter media could be successfully applied to simultaneous removal of ammonium, manganese, iron, and arsenic., (© 2019 Water Environment Federation.)

Arsenic trioxide (ATO), an FDA-approved drug for acute promyelocytic leukemia, also has great potential for treatment of solid tumors. Drug delivery powered by recent advances in nanotechnology has boosted the efficacy of many drugs, which is enlightening for applications of ATO in treating solid tumors. Herein, we reported arsenite-loaded multifunctional nanoparticles that are capable of pH-responsive ATO release for treating hepatocellular carcinoma (HCC) and real-time monitoring via magnetic resonance imaging. We fabricated these nanoparticles (designated as magnetic large-pore mesoporous silica nanoparticle (M-LPMSN)-NiAsO x ) by loading nanoparticulate ATO prodrugs (NiAsO x ) into the pores of large-pore mesoporous silica nanoparticles (LPMSNs) that contain magnetic iron oxide nanoparticles in the center. The surface of these nanodrugs was modified with a targeting ligand folic acid (FA) to further enhance the drug efficacy. Releasing profiles manifest the responsive discharging of arsenite in acidic environment. In vitro experiments with SMMC-7721 cells reveal that M-LPMSN-NiAsO x -FA nanodrugs have significantly higher cytotoxicity than traditional free ATO and induce more cell apoptosis. In vivo experiments with mice bearing H22 tumors further confirm the superior antitumor efficacy of M-LPMSN-NiAsO x -FA over traditional free ATO and demonstrate the outstanding imaging ability of M-LPMSN-NiAsO x -FA for real-time tumor monitoring. These targeted arsenite-loaded magnetic mesoporous silica nanoparticles integrating imaging and therapy hold great promise for treatment of HCC, indicating the auspicious potential of LPMSN-based nanoplatforms.