Dissolved Mn(III), as a potent one-electron transfer oxidant, is ubiquitous in natural waters and sediments and actively involved in the transformation of organics in biogeochemical processes and water treatment. However, the important role of Mn(III) has long been overlooked because of its short life. This study was the first to investigate the performance of Mn(III) in organoarsenic transformation and to highlight the environmental implications. Both homogeneous and heterogeneous Mn(III)-based systems were effective to remove p-arsanilic acid (p-ASA, 15 μM) with degradation efficiency approaching 40.4 %-98.3 %. Two degradation pathways of p-ASA were proposed, in which As-C bond and amino group were vulnerable sites to Mn(III) attack, leading to the formation of more toxic arsenate (As(V)) and nitarsone. Through transforming organoarsenic to inorganic arsenic species, the removal efficiency of total arsenic and dissolved organics were enhanced to 65.1 %-95.5 % and 16.6 %-36.6 %, respectively, by post-treatment of coagulation or adsorption, accompanied with significant reduction of cytotoxicity and environmental risks. Particularly, polymeric ferric sulfate and granular activated alumina showed superior performance in the total As removal. Moreover, oxidation efficiency of Mn(III) was hardly affected by common cations and anions (e.g., Ca2+, Mg2+, NH4+, NO3-, SO4-), halide ions (e.g., Cl-, Br-) and natural organic matter, showing high robustness for organoarsenic removal under complicated water matrices. Overall, this study shed light on the significance of Mn(III) to the fate of organoarsenics in manganese-rich environments, and demonstrated the promising potential of Mn(III)-based strategies to achieve targeted decontamination in water/wastewater purification.

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

Arsanilic acid (p-AsA), a prevalently used feed additive, is frequently detected in environment posing a great threat to humans. Potassium ferrate (Fe(VI)) was an efficient way to tackle arsenic contamination under acid and neutral conditions. However, Fe(VI) showed a noneffective removal of p-AsA under alkaline conditions due to its oxidation capacity attenuation. Herein, a magnetic iron-doped carbon nanotubes (F-CNT) was successfully prepared and further catalyzed Fe(VI) to remove p-AsA and total As species. The Fe(VI)/F-CNT system showed an excellent capability to oxidize p-AsA and adsorb total As species over an environment-related pH range of 6-9. The high-valent iron intermediates Fe(V)/Fe(IV) and the mediated electron-transfer played a significant part in the degradation of p-AsA according to the probes/scavengers experiments and galvanic oxidation process. Moreover, the situ formed iron hydroxide oxide and F-CNT significantly improved the adsorption capacity for total As species. The electron-donating groups (semiquinone and hydroquinone) and high graphitization of F-CNT were responsible for activating Fe(VI) based on the analysis of X-ray photoelectron spectroscopy (XPS). Density functional theory calculations and the detected degradation products both indicated that the amino group and the C-As bond of p-AsA were main reactive sites. Notably, Fe(VI)/F-CNT system was resistant to the interference from Cl-, SO42-, and HCO3-, and could effectively remove p-AsA and total As species even in the presence of complex water matrix. In summary, this work proposed an efficient method to use Fe(VI) for degrading pollutants under alkaline conditions and explore a new technology for livestock wastewater advanced treatment.

The widespread used organoarsenicals have drawn attention for decades due to their potential environment risks. In this study, a heterogeneous system of goethite/oxalate irradiated using UVA light (λ = 365 nm) was applied for the removal of ASA, a kind of organoarsenicals used in animal feeding operations as additives, from the aqueous phase through photodegradation. Results showed that the presence of 5 mM of oxalate significantly enhanced the photodegradation efficiency of ASA in the 0.1 g/L of goethite suspended system from 28 to ~100% within 180 min reaction at pH 5. Acid conditions favored the photoreaction rate, compared with neutral and basic conditions. This reaction process was also influenced by the initial concentration of oxalate and ASA. Furthermore, the mechanism study was conducted by quenching experiments and revealed the important roles of ·OH in the degradation of ASA in the goethite/oxalate/UVA system. By analyzing the reaction products, both inorganic arsenic (As(III) and As(V)) and ammonia were detected during the photodegradation of ASA. These findings help to gain a better understanding of the geochemical behavior of ASA in surface water and can also provide a potential treatment method for the organoarsenicals contaminated water.

The widespread occurrence of p-arsanilic acid (p-ASA) in natural environments poses big threats to the biosphere due to the generation of toxic inorganic arsenic (i.e., As(III) and As(V), especially As(III) with higher toxicity and mobility). Oxidation of p-ASA or As(III) to As(V) followed by precipitation of total arsenic using Fe-based advanced oxidation processes demonstrated to be a promising approach for the treatment of arsenic contamination. This study for the first time investigated the efficiency and inherent mechanism of p-ASA and As(III) oxidation by Fe(II)/peracetic acid (Fe(II)/PAA) and PAA processes. p-ASA was rapidly degraded by the Fe(II)/PAA process within 20 s at neutral to acidic pHs under different conditions, while it was insignificantly degraded by PAA oxidation alone. Lines of evidence suggested that hydroxyl radicals and organic radicals generated from the homolytic OO bond cleavage of PAA contributed to the degradation of p-ASA in the Fe(II)/PAA process. p-ASA was mainly oxidized to As (V), NH4+, and p-aminophenol by the Fe(II)/PAA process, wherein the aniline group and its para position were the most vulnerable sites. As(III) of concern was likely generated as an intermediate during p-ASA oxidation and it could be readily oxidized to As(V) by the Fe(II)/PAA process as well as PAA alone. The in-depth investigation demonstrated that PAA alone was effective in the oxidation of As(III) under varied conditions with a stoichiometric molar ratio of 1:1. Efficient removal (> 80%) of total arsenic during p-ASA oxidation by Fe(II)/PAA process or during As(III) oxidation by PAA process with additional Fe(III) in synthetic or real waters were observed, mainly due to the adsorptive interactions of amorphous ferric (oxy)hydroxide precipitates. This study systematically investigates the oxidation of p-ASA and As(III) by the Fe(II)/PAA and PAA processes, which is instructive for the future development of arsenic remediation technology.

Sea level rise (SLR) is estimated to impact 25% of the world\'s population along coastal areas leading to an increase in saltwater intrusion. Consequently, changes in the soil biogeochemistry of currently non-saline and/or well-drained soils due to saltwater intrusion are of major concern. Saltwater intrusion is expected to affect farmland across large broiler producer regions, where large amounts of manure containing organic arsenicals were applied over the past decades. To determine how SLR may impact the speciation and mobility of adsorbed inorganic and organic As, we used in situ real-time attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) to determine the adsorption and desorption mechanisms of As(V) and 4-aminophenylarsonic (p-ASA, a poultry feed additive) on ferrihydrite (Fh) in the presence of sulfate at varying pH. The adsorption of As(V) and p-ASA increased at lower pH, with As(V) showing IR features consistent with the formation of inner-sphere of As-Fh surface complexes, while p-ASA also formed others structures as H-bonded As-surface complexes, likely mediated by outer-sphere complexes, based on our FTIR and batch experiments data. No observable As(V) or p-ASA desorption from the Fh surface was promoted by sulfate, however sulfate adsorption on the Fh surface was remarkably larger for p-ASA than for As(V). Complimentary, we carried out batch studies of As(V) and p-ASA desorption by Fh, using artificial seawater (ASW) at varying concentrations. The 1% ASW desorbed ∼10% of initially sorbed p-ASA, while at 100% ASW desorbed ∼40%. However, <1% of As(V) was desorbed by 1% ASW solution and only ∼7.9% were desorbed at 100% ASW. The spectroscopic data support the more extensive desorption of p-ASA compared to As(V) observed in batch experiments, suggesting that organoarsenicals may be easily desorbed and, after conversion to inorganic forms, pose a risk to water supplies.

As a typical wide band gap photocatalyst, titania (TiO2) cannot use the visible light and has fast recombination rate of photogenerated electron-hole pairs. Simultaneous introduction of erbium ion (Er3+) and graphene oxide (rGO) into TiO2 might overcome these two drawbacks. In this study, Er3+ and rGO were co-doped on TiO2 to synthesize Er3+-rGO/TiO2 photocatalyst through a two-step sol-gel method. Based on the UV-visible diffuse reflectance spectra and photoluminescence spectrum, the introduction of Er3+ and rGO increased the visible light absorption efficiency and enhanced the migration of photogenerated electron. Pure TiO2 has almost no photocatalytic activity for arsanilic acid (p-ASA) degradation under visible light irradiation. However, while doping with 2.0 mol% Er3+ and 10.0 mol% rGO, the p-ASA could be completely degraded within 50 min by the Er3+-rGO/TiO2 photocatalyst under visible light irradiation, and most of produced inorganic arsenic was in situ removed by adsorption from the solution. The reactive oxygen species (ROS) reacting with p-ASA was determined and superoxide radical (O2•-) and singlet oxygen (1O2) were the dominant ROS for the oxidation of p-ASA and arsenite. This work provides an approach of introducing Er3+ and rGO to enhance the visible light photocatalytic efficiency of TiO2.

As a feed additive, p-arsanilic acid (p-ASA) is hardly metabolized in animal bodies and is excreted chemically unchanged via feces and urine, which can be transformed into more toxic inorganic arsenic species and other organic by-products upon degradation in the aquatic environment. In this study, UV-LED/persulfate (PS)/Fe(Ⅲ) and UV-LED/peroxymonosulfate (PMS)/Fe(Ⅲ) processes were developed to remove p-ASA and immobilize the formed inorganic arsenic via tuning solution pH. UV-LED/PMS/Fe(Ⅲ) (90.8%) presented the best performance for p-ASA degradation at pH 3.0, and the p-ASA degradation in these processes both followed the pseudo-first-order kinetics. The ∙OH played the major role in UV-LED/PS/Fe(Ⅲ) and UV-LED/PMS/Fe(Ⅲ) systems. Solution pH greatly affected the p-ASA degradation and the maximum removal can be achieved at pH 3.0 due to the presence of more Fe(OH)(H2O)52+. The dosages of Fe(III) and PMS (PS), SO42- and HCO3- significantly influenced the performance of p-ASA oxidation, while HA, Cl- and NO3- slightly affected the p-ASA degradation. According to quantum chemical calculation, radical addition on the C atom in the C-As bond of p-ASA was corroborated to be the dominant reaction pathway by SO4∙- and ∙OH. Additionally, the reactive sites and reasonable degradation pathways of p-ASA were proposed based on DFT calculation and HPLC/MS analysis. The release of inorganic arsenic in both processes can be effectively immobilized and the toxicity of the reaction solution dramatically reduced by adjusting solution pH to 6.0. UV-LED/PMS/Fe(Ⅲ) process was found to be more cost-effective than UV-LED/PS/Fe(Ⅲ) process at the low oxidant dosages.

A sensitive electrochemical immunosensor was prepared for rapid detection of ASA based on arsanilic acid (ASA) monoclonal antibody with high affinity. In the preparation of nanomaterials, polyethyleneimine (PEI) improved the stability of the solution and acted as a reducing agent to generate reduced graphene oxide (rGO) with relatively strong conductivity, thereby promoting the transfer of electrons. The dual conductivity of rGO and silver nanoparticles (AgNPs) improved the sensitivity of the sensor. The synthesis of nanomaterials were confirmed by UV-Vis spectroscopy, X-ray diffraction, transmission electron microscopy and scanning electron microscopy. In the optimal experiment conditions, the sensor could achieve the detection range of 0.50-500 ng mL-1 and the limit of detection (LOD) of 0.38 ng mL-1 (S/N = 3). Moreover, the sensor exhibited excellent specificity and acceptable stability, suggesting that the proposed sensor possessed a good potential in ASA detection. Thus, the as-prepared biosensor may be a potential way for detecting other antibiotics in meat and animal-derived foods.

Efficient and rapid removal of p-arsanilic acid (p-ASA) in water is very important in environmental protection and human health, however it is still a severe challenge in actual engineering. Herein, a novel sorbent (CF-PEI) was successfully fabricated by simply modifying the amphiphilic skin collagen fiber (CF) substrate with Polyethylenimine (PEI). The as-prepared CF-PEI exhibits high-efficiency adsorption for negatively charged p-ASA with aromatic rings due to the introduction of amino groups and the existence of hydrophobic bands, and the maximum adsorption capacity of CF-PEI for p-ASA was high up to 285.71 mg g-1. In addition, the adsorption mechanism of CF-PEI on p-ASA mainly includes electrostatic interaction, hydrogen bond and amphiphilicity. The multi-level all-fiber structure of CF makes it mainly focus on surface mass transfer with short mass transfer distance, and its capillary drainage effect can realize large flow and rapid separation. CF-PEI based on CF can realize the ability to separate low-concentration p-ASA with high flow rate and high efficiency. The effective processing volume was 12.5 L g-1 when the separation flux reached as high as 9931.27 L m-2 h-1. Notably, the p-ASA adsorbed on CF-PEI was almost completely eluted by NaOH (0.5 mol L-1). The adsorbent is convenient to prepare, recyclable, high in efficiency, and has a great application prospect in removing organic micro-pollutants.