P-arsanilic Acid Research Articles

Elucidating the role of double-confined effect in hollow MOFs/GO catalytic membrane for deep arsenic pollution treatment

The significance of addressing arsenic contamination is huge, given its widespread environmental impact and detrimental effects on human health. Herein, we developed a double-confined catalytic membrane capable of activating peroxymonosulfate (PMS) by integrating hollow Prussian blue analogues (H-PBA) with a unique void-confinement effect into graphene oxide (GO) laminates. This delicately designed H-PBA/GO membrane displayed 98.8 % p-arsanilic acid (p-ASA) removal with a 9.03 s retention time, surpassing most reported studies. Our experiments underscored that the dual-confined architecture not only drove mass transfer but also bolstered reactant concentration, thereby multiplying catalytic activities. Remarkably, this double-confinement conduced to a sustained dominance of surface-radicals (SO4−) and singlet oxygen (1O2), bolstering p-ASA degradation across a broad pH spectrum and numerous aqueous realms, inclusive of high salinity waters pertinent to desalination pre-treatment processes. Crucially, the H-PBA/GO membrane demonstrated over 90 % degradation of p-ASA and immobilized total As, unfaltering over 80 h of continuous operation. This signified an evolution in membrane technology, promising enhanced and steadfast performance. This innovation bore profound implications for devising double-confined efficacious and robust catalysts, poised to revolutionize advanced wastewater treatment, notably augmenting desalination systems by fortifying pre-treatment and safeguarding reverse osmosis membranes from organic and arsenic fouling.

Transformation of p-arsanilic acid by dissolved Mn(III) and enhanced arsenic removal: Mechanism, toxicity and performance in complicated water matrices

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+, NO3ˉ, SO4ˉ), halide ions (e.g., Clˉ, Brˉ) 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.

Progress of photocatalytic oxidation-adsorption synergistic removal of organic arsenic in water.

Photocatalytic oxidation-adsorption synergistic treatment of organic arsenic pollutants is a promising wastewater treatment technology, which not only degrades organic arsenic pollutants by photocatalytic degradation but also removes the generated inorganic arsenic by adsorption. This paper compares the results of photocatalytic oxidation-adsorption co-treatment of organic arsenic pollutants such as monomethylarsonic acid, dimethylarsinic acid, phenylarsonic acid, p-arsanilic acid, and 3-nitro-4-hydroxyphenylarsonic acid on titanium dioxide, goethite, zinc oxide, and copper oxide. It examines the influence of the morphology of organic arsenic molecules, pH, coexisting ions, and the role of natural organic matter. The photocatalytic oxidation-adsorption co-treatment mechanism is investigated, comparing the hydroxyl radical oxidation mechanism, the hydroxyl radical and superoxide anion radical cooxidation mechanism, and the hydroxyl radical and hole cooxidation mechanism. Finally, the future prospects of metal oxide photocatalytic materials and the development of robust and efficient technologies for removing organic arsenic are envisioned.

Iron scrap derived nano zero-valent iron/biochar activated persulfate for p-arsanilic acid decontamination with coexisting microplastics

P-arsanilic acid (AA) has received widespread attention because of its conversion to more toxic inorganic arsenic compounds (arsenate and arsenite) in the natural ecosystems. Its removal process and mechanisms with co-existence of microplastics remain unkown. In this study, biochar loaded with nano zero-valent iron (nZVI) particles (ISBC) was prepared by using iron scrap obtained from a steel works and wood chips collected from a wood processing plant. The advanced oxidation system of sodium persulfate (PDS) activated by ISBC was applied for AA degradation and inorganic arsenic control in aqueous media. More than 99% of the AA was completely degraded by the ISBC/PDS system, and the As(III) on AA was almost completely oxidized to As(V) and finally removed by ISBC. HCO3− inhibited the removal of AA by the ISBC/PDS system, while Cl− had a dual effect that showing inhibition at low concentrations yet promotion at high concentrations. The effect of microplastics on the degradation of AA by the ISBC/PDS system was further investigated due to the potential for combined microplastic and organic arsenic contamination in rural/remote areas. Microplastics were found to have little effect on AA degradation in the ISBC/PDS system, while affect the transport of inorganic arsenic generated from AA degradation. Overall, this study provides new insights and methods for efficient removal of p-arsanilic acid from water with coexisting microplastics.

Aluminum chloride induced ferrate activation for p-arsanilic acid removal: The significant synergism mechanism and enhanced role of reactive Fe(IV)/Fe(V)

The practical applications of potassium ferrate (K2FeO4) are limited due to self-decomposition at nearly neutral pH and low removal efficiency for electron deficient pollutants. That is, K2FeO4 was often insufficient to produce sufficient oxidative material, so the lack of oxidative reactivity remained a pressing problem. This study proposed an effective induction of K2FeO4 activation by aluminum chloride (AlCl3) in a novel highly concentrated simultaneous oxidation and coagulation (HOC) system of K2FeO4/AlCl3. It innovatively focused on the interaction between K2FeO4 and AlCl3 for the removal of p-arsanilic acid (ASA) in a HOC system. The HOC system exhibited higher ASA removal (62.6%) in a shorter period of time compared to K2FeO4 oxidation (28.0%) and pre-oxidation-coagulation (POC) system (51.6%) with the addition of 1.5 mgAl/L of AlCl3 at pH 7. AlCl3 could induce the self-decomposition of K2FeO4, and more importantly, it could facilitated the conversion of Fe(VI) into the more reactive Fe(V)/Fe(IV) species for ASA removal. Moreover, AlCl3 hydrolysis promoted the in-situ H2O2 generation from K2FeO4 decomposition, enhancing Fenton-like reaction and increasing OH and O2– for ASA removal. K2FeO4 greatly influenced AlCl3 hydrolysis and promoted rapid transformation of small polyaluminum Ala and medium polyaluminum Alb to colloidal high polyaluminum Alc. The content of Fe elements in the flocs produced by the HOC-ASA floc system was 19.27%, which was much higher than the 4.58% of the POC-ASA system, which enhanced the interfacial reaction and electron transfer and facilitated the removal of ASA.

Fe electrocoagulation technology for highly-efficient p-arsanilic acid removal from water: Feasibility and mechanisms

Conventional oxidation methods are effective for the removal of p-arsanilic acid (p-ASA) in water but are limited by complicated process. Herein, Fe electrocoagulation with Fe as anodes was used to efficiently remove p-ASA with 100% total arsenic removal within 60 min (1.75–20 A/m2). Current density significantly influenced sludge production, anode loss, and energy consumption (p-value < 0.05). Kinetic analyses showed a decline in arsenic removal rate with increasing initial pH (4.0–10.0). The changes in main elements of p-ASA (As and N) were analyzed to identify intermediate products using UPLC-Q-TOF-MS, HPLC-ICP-MS, and spectrometry. Hydroxyl radicals were confirmed as the primary reactive oxygen species. The active sites of p-ASA molecules were predicted by theoretical calculations and reaction paths were proposed. The toxicity of Fe-EC effluent was effectively reduced according to the analyses of ECOSAR and E. coli colonies method. The possible mechanisms of p-ASA removal, including oxidative degradation, electrostatic attraction, and ligand complexation, were proposed. Real water containing a p-ASA concentration of 250 μg/L was treated for 48 h using continuous-flow Fe-EC and arsenic concentrations of 2–30 μg/L in effluent were obtained. Overall, Fe-EC was a simple, cost-effective, and eco-friendly technology for the removal of p-ASA.

Regulating water decontamination and food safety by a reusable, nano-sized MOF@cotton@chitosan composite through nanomolar detection of the drug nitroxinil and organoarsenic feed additive p-arsanilic acid

MOF@cotton@chitosan composite for nanomolar fluorescence sensing of nitroxinil drug and p-arsanilic acid in real samples is presented.

Adsorption Behavior of Organoarsenicals over MnFe2O4-Graphene Hybrid Nanocomposite: The Role of Organoarsenic Chemical Structures.

As a kind of emerging contaminant, organoarsenic compounds have drawn wide concern because of their considerable solubilities in water, and the highly toxic inorganic arsenic species formed during their biotic and abiotic degradation in the natural environment. Thus, the effective removal and studying of the adsorption mechanism of organoarsenic compounds are of significant urgency. In this work, MnFe2O4 and MnFe2O4/graphene were prepared through a facile solvothermal method. From the results of the Transmission Electron Microscope (TEM) characterization, it can be found that MnFe2O4 nanoparticles were uniformly distributed on the surface of the graphene. And the specific surface area of the MnFe2O4/graphene was about 146.39 m2 g-1, much higher than that of the MnFe2O4 (86.15 m2 g-1). The interactions between organoarsenic compounds and adsorbents were conducted to study their adsorption behavior and mechanism. The maximum adsorption capacities of MnFe2O4/graphene towards p-arsanilic acid (p-ASA) and roxarsone (ROX) were calculated to be 22.75 and 30.59 mg g-1. Additionally, the ionic strength, negative ions, and humus were introduced to investigate the adsorption performance of organoarsenic compounds. Electrostatic adsorption and surface complexation are the primary adsorption mechanisms on account of X-ray photoelectron spectroscopy (XPS) and the Fourier-transform infrared spectroscopy (FT-IR) analysis. This research extends the knowledge into studying the interaction between organoarsenic species and hybrid nanomaterials in the natural environment.

Comparative study of Fe(II)/sulfite, Fe(II)/PDS and Fe(II)/PMS for p-arsanilic acid treatment: Efficient organic arsenic degradation and contrasting total arsenic removal

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.

Facet-dependent adsorption of aromatic organoarsenicals on hematite: The mechanism and environmental impact

Aromatic organoarsenic feed additives have been extensively used in poultry and livestock farming; however, a risk of releasing toxic inorganic arsenic exists when they are exposed to the environment. An in-depth understanding of the adsorption -migration behavior of aromatic organoarsenicals on environmental media is limited. In this study, p-arsanilic acid (p-ASA) and roxarsone (ROX) were considered as examples to systematically study their adsorption behaviors on the surface of hematite, a representative iron oxide in soil. By comparing the adsorption abilities and adsorption kinetics of hematite exposed with different facets (hexagonal nanoplates, HNPs, mainly exposed with {001} facets and hexagonal nanocubes, HNCs, exposed with {012} facets), combined with in situ shell-isolated nanoparticle enhanced Raman spectroscopy characterization and density functional theory simulation, the facet-dependent adsorption performance was observed and the mechanism revealed. The results showed that p-ASA formed a bidentate binuclear complex on HNCs and HNPs, whereas ROX formed monodentate mononuclear and bidentate binuclear configurations on the {001} and {012} facets, respectively. These differences not only lead to facet-dependent adsorption capacities but also affect their stability, as verified by sequential extraction experiments, affecting the environmental behavior and fate of aromatic organoarsenicals. This study not only provides insights into the environmental behavior of aromatic organoarsenicals but also offers theoretical support for the development of functional adsorbents and remediation strategies.

3D-Printed MOFs/Polymer Composite as a Separatable Adsorbent for the Removal of Phenylarsenic Acid in the Aqueous Solution.

Metal-organic frameworks (MOFs) are emerging as advanced nanoporous materials to remove phenylarsenic acid, p-arsanilic acid (p-ASA), and roxarsone (ROX) in the aqueous solution, while MOFs are often present as powder state and encounter difficulties in recovery after adsorption, which greatly limit their practical application in the aqueous environments. Herein, MIL-101 (Fe), a typical MOF, was mixed with sodium alginate and gelatin to prepare MIL-101@CAGE by three-dimensional (3D) printing technology, which was then used as a separatable adsorbent to remove phenylarsenic acid in the aqueous solution. The structure of 3D-printed MIL-101@CAGE was first characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), and thermogravimetry and differential thermogravimetry (TG-DTG). The octahedral morphology of MIL-101 (Fe) was found unchanged during the 3D printing process. Then, the adsorption process of MIL-101@CAGE on phenylarsenic acids was systematically investigated by adsorption kinetics, adsorption isotherms, adsorption thermodynamics, condition experiments, and cyclic regeneration experiments. Finally, the adsorption mechanism between MIL-101@CAGE and phenylarsenic acid was further investigated. The results showed that the Langmuir, Freundlich, and Temkin isotherms were well fit, and according to the Langmuir fitting results, the maximum adsorption amounts of MIL-101@CAGE on p-ASA and ROX at 25 °C were 106.98 and 120.28 mg/g, respectively. The removal of p-ASA and ROX by MIL-101@CAGE remained stable over a wide pH range and in the presence of various coexisting ions. The regeneration experiments showed that the 3D-printed MIL-101@CAGE could still maintain a more than 90% removal rate after five cycles. The adsorption mechanism of this system might include π-π stacking interactions between the benzene ring on the phenylarsenic acids and the organic ligands in MIL-101@CAGE, hydrogen-bonding, and ligand-bonding interactions (Fe-O-As). This study provides a new idea for the scale preparation of a separatable and recyclable adsorbent based on MOF material for the efficient removal of phenylarsenic acid in the aqueous solution.

Investigation into the electrochemical advanced oxidation of p-arsanilic acid: Peculiar role of electrolytes and unexpected formation of coupling byproducts

Although banned in some countries, p-arsanilic acid (ASA) is still widely used as feed additive in poultry production. As a result, ASA is usually released into the aquatic environment without any treatments. Although ASA exhibits low toxicity, it can be transformed into highly toxic aromatic amines and inorganic arsenic species (As (V) as H2AsO4− and HAsO42−) under natural environmental conditions. Hence, it is necessary to develop efficient technologies for its removal or degradation. In this contribution, electrochemical advanced oxidation technology with boron-doped diamond (BDD) had been initially used to degrade ASA pollutants. A five-level central composite rotatable design (CCRD) was implemented to optimize the various influencing factors involved, among applied current density, NaCl concentration, Na2SO4 concentration and NaHCO3 concentration on the oxidation efficiency; the latter was assessed in terms of ASA degradation percentage. The results obtained highlighted the unique and important roles of electrolytes during the electrolytic oxidations. Meanwhile, the major degradation byproducts detected were also strongly dependent on the electrolyte adopted. In particular, several oligomer byproducts with novel structures were initially identified in BDD-treated ASA solutions. Two different electrochemical transformation pathways of ASA on BDD anode were thus proposed. This study demonstrated the effectiveness of BDD technology in the degradation of ASA, as well as the potential minor risk of its application in actual ASA wastewater treatment.

Enhanced removal of organic arsenic by using potassium ferrate coupled with metal coagulants: Role of iron species and effect of AlCl3 and FeCl3

This study investigated the removal performance and synergistic mechanism of p-arsanilic acid (p-ASA) using a pre-oxidative coagulation system of potassium permanganate (K2FeO4) with aluminum chloride (AlCl3) or ferric chloride (FeCl3). The arsenic removal efficiencies of K2FeO4-AlCl3 and K2FeO4-FeCl3 reached 93.46% and 98.58%, respectively. K2FeO4 could alter the distribution of hydrolysis products of the coagulants and the addition of the coagulants directly or indirectly influenced the generation of intermediate valence iron (Fe(IV) and Fe(V)), interestingly, the mechanisms of aluminum and iron salts enhancing the removal of p-ASA by potassium ferrate were different. During the coupling process, AlCl3 and FeCl3 enhanced the self-decomposition rate of K2FeO4 with △kAl = 3.0530 and △kFe = 0.0912, respectively, resulting in difference on the generation of Fe(IV) and Fe(V). FeCl3 facilitated more effective Fe(IV) and Fe(V) production (FeCl3eff/AlCl3eff＞1), and multiple active iron species degraded p-ASA into inorganic arsenic, p-aminophenol (p-AP), nitarsone (NIA), and other products. Additionally, in the presence of K2FeO4, the hydrolytic dominant species of AlCl3 and FeCl3 were influenced under near-neutral conditions (pH 6–8), and Al13 and polynuclear Fe-hydroxides (PnFe-H) effectively improved the removal efficiency of inorganic arsenic and other organic products. The in-situ generation of nanoiron particles by K2FeO4 altered the original floc structure of the coagulants, with the specific surface areas of the flocs being 8733.176 cm2/cm3 for K2FeO4-AlCl3 and 7232.856 cm2/cm3 for K2FeO4-FeCl3. The coupling of K2FeO4 with metal salt coagulants not only enhanced p-ASA removal but also effectively improved the floc structure.

Enhanced photodegradation of p-arsanilic acid by oxalate in goethite heterogeneous system under UVA irradiation.

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.

Biomass-derived foams with three-dimensional hierarchical structure for efficient p-arsanilic acid removal

As an emerging micro-pollutant, p-arsanilic acid (p-ASA) exist widely in the environment, and it can form highly toxic arsenate and arsenite during the migration and transformation process, which greatly increases the risk of arsenic pollution in the ecosystem. Additionally, three-dimensional (3D) porous block materials have the advantage of stronger adsorption performance, faster adsorption rate and easy recovery, showing broad application prospects in water pollution control. Hence, the aminozed collagen fibers foam (ACFF) with 3D porous block structure was synthesized. The maximum adsorption capacity of ACFF for p-ASA was 476.19 mg·g−1 due to the rich honeycomb porous structure and the synergistic effect of electrostatic attraction, hydrogen bonding effect and amphiphilicity. Moreover, ACFF is not only easy to recycle, but also has good elastic recovery and regeneration performance. The pore size of ACFF was concentrated in the range of 25–5000 nm, and the porosity was 71.66%. ACFF may be an adsorbent with great potential for the removal of organoarsenic contaminants in water.

Efficient removal of p-arsanilic acid and arsenite by Fe(II)/peracetic acid (Fe(II)/PAA) and PAA processes

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.

The adsorption of arsenate and p-arsanilic acid onto ferrihydrite and subsequent desorption by sulfate and artificial seawater: Future implications of sea level rise

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.

Fabrication of magnetic bifunctional composite via anchoring CoY on waste heating pad as a cycling material for peroxymonosulfate activation to degrade p-arsanilic acid and simultaneously eliminate secondary As(V)

Herein, waste heating pad, which mainly contains iron and vermiculite components after calcination in air, was used to support cobalt-yttrium bimetallic oxide for the first time. The magnetic material (IV@CoY) was applied for the activation of peroxymonosulfate (PMS) to simultaneously realize the removal of p-arsanilic acid (p-ASA) and the secondary inorganic arsenic (As(V)). 50 µM p-ASA was completely degraded in the system of IV@CoY (0.2 g/L) and PMS (0.5 mM) within 7 min, and about 99 % of the produced As(V) was adsorbed within 150 min. Electrochemical experiments illustrated that IV@CoY possessed the superior conductivity as compared to CoY, which greatly boosted PMS activation. The pseudo-first-order rate constant (kIV@CoY) was high up to 0.873 min−1, which was 7.6 times larger than kCoY (0.115 min−1). Catalytic mechanism analyses revealed that the produced SO4•−, •OH and 1O2 participated in the oxidation of p-ASA and As(III). The adsorption of the produced As(V) was achieved by ion exchange with −OH/CO32− on the surface of IV@CoY. The degradation pathways of p-ASA were further proposed on the basis of the detection of its intermediate products. Initial pH exerted a significant effect on the degradation-adsorption reaction and weak acidic or neutral condition was beneficial to the removal of p-ASA and As(V). To evaluate the practical application potential of IV@CoY, the disposal of p-ASA and secondary As(V) were also carried out in real water samples. Furthermore, IV@CoY was consecutively used for 5 times, and almost 100% degradation of p-ASA and over 97% adsorption of inorganic arsenic were still achieved even in the fifth round, which prove its high stability and reusability. Our results fully demonstrate that the magnetic IV@CoY is a promising catalyst to activate PMS for eliminating organoarsenic from water.

Magnetic Fe3O4/MIL-101 composite as a robust adsorbent for removal of p-arsanilic acid and roxarsenic in the aqueous solution

The p-arsanilic acid (p-ASA) and roxarsenic (ROX) are typical organic arsenic compounds (OACs), which can be evolved into highly poisonous inorganic arsenic species in the aqueous solution. Herein, a magnetic MOFs-based composite of Fe3O4/MIL-101 was successfully obtained by a stepwise solvothermal method and further used in the adsorption of p-ASA and ROX. The structural and physicochemical characteristics of Fe3O4/MIL-101 were firstly investigated in detail. It was found that Fe3O4 microspheres were evenly embedded on the polyhedral MIL-101 surface after the solvothermal process and exhibited a strong superparamagnetic property. After adsorption, a simple external magnetic field can be used to quickly separate the composite from the aqueous solution. The adsorption experiments indicated that the composite is an excellent adsorbent with maximum adsorption capacities of 683.44 and 946.57 mg·g−1 for p-ASA and ROX, respectively. In addition, the effects of composite dosage, initial pH and co-existing anions on the adsorption efficiency were investigated. The main adsorption mechanism consists of the existence of hydrogen bonding, π-π stacking and As-O-Fe coordination between Fe3O4/MIL-101 composite and OACs. We believe that this study would be very meaningful to promote the application of magnetic MOFs based composites for effective adsorption for OACs in the environmental remediation.

The interfacial behaviors of different arsenic species on polyethylene mulching film microplastics: Roles of the plastic additives.

Plastic additives widely existed in plastic mulching films, but their roles in microplastics (MPs) derived from these plastics as vectors of pollutants were not clear. This work clarified the role of plastic additives on the sorption-desorption behaviors of four arsenic species (arsenite (As(Ⅲ)), arsenate (As(Ⅴ)), roxarsone (ROX), and p-arsanilic acid (p-ASA)) on/from virgin polyethylene (V-PE), white PE mulching film (W-PE, with Si-containing additives), and black PE mulching film (B-PE, with CaCO3 and TiO2 additives) MPs. The maximum sorption amounts of arsenic species on V-PE (3.33-20.10mg/kg) and W-PE MPs (4.78-21.93mg/kg) had no significant difference, while those on B-PE (43.02-252.19mg/kg) facilitated by its additives were up to one order of magnitude greater than V-PE or W-PE (p<0.05). Desorption hysteresis index (HI) indicated the irreversible arsenic sorption on three PE MPs, especially for B-PE containing additives that can co-precipitate and complex with arsenicals. The effects of pH, humic substances, and coexisting anions on arsenic sorption by B-PE were more obvious than that by V-PE or W-PE MPs, attributing to electrostatic interaction enhanced by CaCO3 and TiO2 additives. This work provides theoretical basis for migration of arsenic species on MPs containing plastic additives and their potential environmental risk assessment.