Highly efficient persulfate catalyst prepared from modified electrolytic manganese residues coupled with biochar for the roxarsone removal.

The contamination of organoarsenic is becoming increasingly prominent while SR-AOPs were confirmed to be valid for their remediation. This study has found that the novel metal/carbon catalyst (Fe/C-Mn) prepared by solid waste with hierarchical pores could simultaneously degrade roxarsone (ROX) and remove As(V). A total of 95.6% of ROX (20 mg/L) could be removed at the concentration of 1.0 g/L of catalyst and 0.4 g/L of oxidant in the Fe/C-Mn/PMS system within 90 min. The scavenging experiment and electrochemical test revealed that both single-electron and two-electron pathways contributed to the ROX decomposition. Spectroscopic analysis suggested the ROX has been successfully mineralized while As(V) was fixed with the surface Fe and Mn. Density functional theory (DFT) calculation and chromatographic analysis indicated that the As7, N8, O9 and O10 sites of ROX molecule were vulnerable to being attacked by nucleophilic, electrophilic and radical, resulting in the formation of several intermediates such as phenolic compounds. Additionally, the low metal leaching concentration during recycling and high anti-interference ability in various water matrices manifested the practicability of Fe/C-Mn/PMS system.

The role of organic and inorganic substituents of roxarsone determines its binding behavior and mechanisms onto nano-ferrihydrite colloidal particles.

The retention and fate of Roxarsone (ROX) onto typical reactive soil minerals were crucial for evaluating its potential environmental risk. However, the behavior and molecular-level reaction mechanism of ROX and its substituents with iron (hydr)oxides remains unclear. Herein, the binding behavior of ROX on ferrihydrite (Fh) was investigated through batch experiments and in-situ ATR-FTIR techniques. Our results demonstrated that Fh is an effective geo-sorbent for the retention of ROX. The pseudo-second-order kinetic and the Langmuir model successfully described the sorption process. The driving force for the binding of ROX on Fh was ascribed to the chemical adsorption, and the rate-limiting step is simultaneously dominated by intraparticle and film diffusion. Isotherms results revealed that the sorption of ROX onto Fh appeared in uniformly distributed monolayer adsorption sites. The two-dimensional correlation spectroscopy and XPS results implied that the nitro, hydroxyl, and arsenate moiety of ROX molecules have participated in binding ROX onto Fh, signifying that the predominated mechanisms were attributed to the hydrogen bonding and surface complexation. Our results can help to better understand the ROX-mineral interactions at the molecular level and lay the foundation for exploring the degradation, transformation, and remediation technologies of ROX and structural analog pollutants in the environment.

Organoarsenical tolerance in Sphingobacterium wenxiniae, a bacterium isolated from activated sludge.

Organoarsenicals enter the environment from biogenic and anthropogenic sources. Trivalent inorganic arsenite (As(III)) is microbially methylated to more toxic methylarsenite (MAs(III)) and dimethylarsenite (DMAs(III)) that oxidize in air to MAs(V) and DMAs(V). Sources include the herbicide monosodium methylarsenate (MSMA or MAs(V)), which is microbially reduced to MAs(III), and the aromatic arsenical roxarsone (3-nitro-4-hydroxybenzenearsonic acid or Rox), an antimicrobial growth promoter for poultry and swine. Here we show that Sphingobacterium wenxiniae LQY-18T , isolated from activated sludge, is resistant to trivalent MAs(III) and Rox(III). Sphingobacterium wenxiniae detoxifies MAs(III) and Rox(III) by oxidation to MAs(V) and Rox(V). Sphingobacterium wenxiniae has a novel chromosomal gene, termed arsU1. Expressed in Escherichia coli arsU1 confers resistance to MAs(III) and Rox(III) but not As(III) or pentavalent organoarsenicals. Purified ArsU1 catalyses oxidation of trivalent methylarsenite and roxarsone. ArsU1 has six conserved cysteine residues. The DNA sequence for the three C-terminal cysteines was deleted, and the other three were mutated to serines. Only C45S and C122S lost activity, suggesting that Cys45 and Cys122 play a role in ArsU1 function. ArsU1 requires neither FMN nor FAD for activity. These results demonstrate that ArsU1 is a novel MAs(III) oxidase that contributes to S. wenxiniae tolerance to organoarsenicals.

Fabrication of Praseodymium Vanadate Nanoparticles on Disposable Strip for Rapid and Real-Time Amperometric Sensing of Arsenic Drug Roxarsone.

Nanomaterials have versatile properties owing to their high surface-to-volume ratio and can thus be used in a variety of applications. This work focused on applying a facile hydrothermal strategy to prepare praseodymium vanadate nanoparticles due to the importance of nanoparticles in today's society and the fact that their synthesis might be a challenging endeavor. The structural and morphological characterizations were carried out to confirm the influence of the optimizations on the reaction's outcomes, which revealed praseodymium vanadate (PrVO4) with a tetragonal crystal system. In this regard, the proposed development of electrochemical sensors based on the PrVO4 nanocatalyst for the real-time detection of arsenic drug roxarsone (RXS) is a primary concern. The detection was measured by amperometric (i-t) signals where PrVO4/SPCE, as a new electrochemical sensing medium for RXS detection, increased the sensitivity of the sensor to about ∼2.5 folds compared to the previously reported ones. In the concentration range of 0.001-551.78 µM, the suggested PrVO4/SPCE sensor has a high sensitivity for RXS, with a detection limit of 0.4 nM. Furthermore, the impact of several selected potential interferences, operational stability (2000 s), and reproducibility measurements have no discernible effect on RXS sensing, making it the ideal sensing device feasible for technical analysis. The real-time analysis reveals the excellent efficiency and reliability of the prosed sensor toward RXS detection with favorable recovery ranges between ±97.00-99.66% for chicken, egg, water, and urine samples.

A screen-printed electrode modified with tungsten disulfide nanosheets for nanomolar detection of the arsenic drug roxarsone.

A sensitive electrochemical (voltammetric; DPV) sensor has been developed for the determination of coccidiostat drug (roxarsone) based on the use of an SPCE (screen-printed carbon electrode) modified with tungsten disulfide nanosheets (WS2 NSs). The electrochemical detection of roxarsone on the WS2-modified SPCE was examined by electrochemical strategies. XPS, XRD, Raman, SEM, TEM, EDS and EIS were used to characterize the nanosheets. The effects of scan rate, pH values (phosphate buffer) and buffer concentration were optimized. A selective roxarsone sensor was developed that works best at -0.64 V (vs. Ag/AgCl) and performs much better than the bare SPCE. Features include (a) a wider linear range (0.05 to 490 µM), (b) a nanomolar detection limit (0.03 µM) and (c) high sensitivity (29 µA·µM-1·cm-2). The modified SPCEs have been successfully applied to the determination of roxarsone in spiked meat samples where they gave high accuracy and good recoveries. Graphical abstract Synthesis of WS2 nanosheets and electrochemical detection of roxarsone.

Functional organic material for roxarsone and its derivatives recognition via molecular imprinting.

Roxarsone, one of feed add drugs containing arsenic, has been most widely used in poultry and swine industry. Roxarsone discharged into the environment has caused serious pollution problem. Herein, a reusable functional material for selective recognition and adsorption of roxarsone and its derivatives were designed and synthesized. The interaction mechanism is based on acid-base interaction and surface molecular imprinting. Dual functionalized core-shell structure with silica gel as the core was prepared to use as carrier for surface molecularly imprinted polymers. Surface molecularly imprinted polymers for roxarsone was successfully designed and synthesized using 3-aminopropyltriethoxysilane and methyl acryloyloxypropyltriethoxy silane as functional monomers, Ethylene glycol dimethacrylate as crosslinker, Azobisisobutyronitrile as initiator, acetonitrile as solvent. Binding study showed that the recognition selectivity for roxarsone and its derivatives can be significantly improved (3.5-4 folds) with molecular imprinting. Moreover, the prepared functional material for selective recognition and adsorption of Roxarsone was reusable for multiple times without significant decreasing their adsorption capacities.

Response of soil microbial communities to roxarsone pollution along a concentration gradient.

The extensive use of roxarsone (3-nitro-4-hydroxyphenylarsonic acid) as a feed additive in the broiler poultry industry can lead to environmental arsenic contamination. This study was conducted to reveal the response of soil microbial communities to roxarsone pollution along a concentration gradient. To explore the degradation process and degradation kinetics of roxarsone concentration gradients in soil, the concentration shift of roxarsone at initial concentrations of 0, 50, 100, and 200 mg/kg, as well as that of the arsenic derivatives, was detected. The soil microbial community composition and structure accompanying roxarsone degradation were investigated by high-throughput sequencing. The results showed that roxarsone degradation was inhibited by a biological inhibitor, confirming that soil microbes were absolutely essential to its degradation. Moreover, soil microbes had considerable potential to degrade roxarsone, as a high initial concentration of roxarsone resulted in a substantially increased degradation rate. The concentrations of the degradation products HAPA (3-amino-4-hydroxyphenylarsonic acid), AS(III), and AS(V) in soils were significantly positively correlated. The soil microbial community composition and structure changed significantly across the roxarsone contamination gradient, and the addition of roxarsone decreased the microbial diversity. Some bacteria tended to be inhibited by roxarsone, while Bacillus, Paenibacillus, Arthrobacter, Lysobacter, and Alkaliphilus played important roles in roxarsone degradation. Moreover, HAPA, AS(III), and AS(V) were significantly positively correlated with Symbiobacterium, which dominated soils containing roxarsone, and their abundance increased with increasing initial roxarsone concentration. Accordingly, Symbiobacterium could serve as indicator of arsenic derivatives released by roxarsone as well as the initial roxarsone concentration. This is the first investigation of microbes closely related to roxarsone degradation.

ArsP: a methylarsenite efflux permease.

Trivalent organoarsenic compounds are far more toxic than either pentavalent organoarsenicals or inorganic arsenite. Many microbes methylate inorganic arsenite (As(III)) to more toxic and carcinogenic methylarsenite (MAs(III)). Additionally, monosodium methylarsenate (MSMA or MAs(V)) has been used widely as an herbicide and is reduced by microbial communities to MAs(III). Roxarsone (3-nitro-4-hydroxybenzenearsonic acid) is a pentavalent aromatic arsenical that is used as antimicrobial growth promoter for poultry and swine, and its active form is the trivalent species Rox(III). A bacterial permease, ArsP, from Campylobacter jejuni, was recently shown to confer resistance to roxarsone. In this study, C. jejuni arsP was expressed in Escherichia coli and shown to confer resistance to MAs(III) and Rox(III) but not to inorganic As(III) or pentavalent organoarsenicals. Cells of E. coli expressing arsP did not accumulate trivalent organoarsenicals. Everted membrane vesicles from those cells accumulated MAs(III) > Rox(III) with energy supplied by NADH oxidation, reflecting efflux from cells. The vesicles did not transport As(III), MAs(V) or pentavalent roxarsone. Mutation or modification of the two conserved cysteine residues resulted in loss of transport activity, suggesting that they play a role in ArsP function. Thus, ArsP is the first identified efflux system specific for trivalent organoarsenicals.

Organoarsenical Biotransformations by Shewanella putrefaciens.

Microbes play a critical role in the global arsenic biogeocycle. Most studies have focused on redox cycling of inorganic arsenic in bacteria and archaea. The parallel cycles of organoarsenical biotransformations are less well characterized. Here we describe organoarsenical biotransformations in the environmental microbe Shewanella putrefaciens. Under aerobic growth conditions, S. putrefaciens reduced the herbicide MSMA (methylarsenate or MAs(V)) to methylarsenite (MAs(III)). Even though it does not contain an arsI gene, which encodes the ArsI C-As lyase, S. putrefaciens demethylated MAs(III) to As(III). It cleaved the C-As bond in aromatic arsenicals such as the trivalent forms of the antimicrobial agents roxarsone (Rox(III)), nitarsone (Nit(III)) and phenylarsenite (PhAs(III)), which have been used as growth promoters for poultry and swine. S. putrefaciens thiolated methylated arsenicals, converting MAs(V) into the more toxic metabolite monomethyl monothioarsenate (MMMTAs(V)), and transformed dimethylarsenate (DMAs(V)) into dimethylmonothioarsenate (DMMTAs(V)). It also reduced the nitro groups of Nit(V), forming p-aminophenyl arsenate (p-arsanilic acid or p-AsA(V)), and Rox(III), forming 3-amino-4-hydroxybenzylarsonate (3A4HBzAs(V)). Elucidation of organoarsenical biotransformations by S. putrefaciens provides a holistic appreciation of how these environmental pollutants are degraded.

Fenton process-affected transformation of roxarsone in paddy rice soils: Effects on plant growth and arsenic accumulation in rice grain.

Batch and greenhouse experiments were conducted to examine the effects of Fenton process on transformation of roxarsone in soils and its resulting impacts on the growth of and As uptake by a rice plant cultivar. The results show that addition of Fenton reagent markedly accelerated the degradation of roxarsone and produced arsenite, which was otherwise absent in the soil without added Fenton reagent. Methylation of arsenate was also enhanced by Fenton process in the earlier part of the experiment due to abundant supply of arsenate from Roxarsone degradation. Overall, addition of Fenton reagent resulted in the predominant presence of arsenate in the soils. Fenton process significantly improved the growth of rice in the maturity stage of the first crop, The concentration of methylated As species in the rice plant tissues among the different growth stages was highly variable. Addition of Fenton reagent into the soils led to reduced uptake of soil-borne As by the rice plants and this had a significant effect on reducing the accumulation of As in rice grains. The findings have implications for understanding As biogeochemistry in paddy rice field receiving rainwater-borne H2O2 and for development of mitigation strategies to reduce accumulation of As in rice grains.

Effect of central metal ions of analogous metal-organic frameworks on adsorption of organoarsenic compounds from water: plausible mechanism of adsorption and water purification.

The adsorptive removal of organoarsenic compounds such as p-arsanilic acid (ASA) and roxarsone (ROX) from water using metal-organic frameworks (MOFs) has been investigated for the first time. A MOF, iron benzenetricarboxylate (also called MIL-100-Fe) exhibits a much higher adsorption capacity for ASA and ROX than activated carbon, zeolite (HY), goethite, and other MOFs. The adsorption of ASA and ROX over MIL-100-Fe is also much more rapid than that over activated carbon. Moreover, the used MIL-100-Fe can be recycled by simply washing with acidic ethanol. Therefore, it is determined that a MOF such as MIL-100-Fe can be used to remove organoarsenic compounds from contaminated water because of its high adsorption capacity, rapid adsorption, and ready regeneration. Moreover, only one of three analogous MIL-100 species (MIL-100-Fe, rather than MIL-100-Al or MIL-100-Cr) can effectively remove the organoarsenic compounds. This selective and high adsorption over MIL-100-Fe, different from other analogous MIL-100 species, can be explained (through calculations) by the facile desorption of water from MIL-100-Fe as well as the large (absolute value) replacement energy (difference between the adsorption energies of the organoarsenic compounds and water) exhibited by MIL-100-Fe. A plausible adsorption/desorption mechanism is proposed based on the surface charge of the MOFs, FTIR results, calculations, and the reactivation results with respect to the solvents used in the experiments.

Electrochemical stimulation of microbial roxarsone degradation under anaerobic conditions.

Roxarsone (4-hydroxy-3-nitrophenylarsonic acid) has been commonly used in animal feed as an organoarsenic additive, most of which is excreted in manure. Roxarsone is easily biodegraded to 4-hydroxy-3-aminophenylarsonic acid (HAPA) under anaerobic conditions, but HAPA persists for long periods in the environment, increasing the risk of arsenic contamination through diffusion. We investigated the electrochemical stimulation of the microbial degradation of roxarsone under anaerobic conditions. After the carbon sources in the substrate were depleted, HAPA was slowly degraded to form arsenite under anaerobic conditions. The degradation rate of HAPA was significantly increased when 0.5 V was applied without adding a carbon source. The two-cell membrane reactor assays reveal that the HAPA was degraded in the anode chambers, confirming that the anode enhanced the electron transfer process by acting as an electron acceptor. The degradation product formed with electrochemical stimulation was arsenate, which facilitates the removal of arsenic from wastewater. Based on the high performance liquid chromatography-ultraviolet-hydride generation-atomic fluorescence spectrometry (HPLC-UV-HG-AFS) and gas chromatography-mass spectrometry (GC-MS) data, the pathway for the biodegradation of roxarsone and the mechanisms for the electrochemically stimulated degradation are proposed. This method provides a potential solution for the removal of arsenic from organoarsenic-contaminated wastewater.

Medium entropy FeCoNi nanoalloy supported on reduced graphene oxide for efficient electrochemical detection of roxarsone in food samples.

Herein, a novel FeCoNi(b)-800 ternary metal nanoalloy was uniformly mixed with reduced graphene oxide (RGO) to synthesize the FeCoNi(b)-800@RGO(2:1) composite. The addition of RGO not only stopped the accumulation of FeCoNi(b)-800 alloy, but also heightened the electrocatalytic activity of composite. Particularly, the FeCoNi(b)-800@RGO(2:1) composite displayed the significantly strong electrocatalytic capacity for the reduction of roxarsone (ROX). Furthermore, the FeCoNi(b)-800@RGO(2:1) composite possessed enough porosity and metal catalytic sites, facilitating the transport and electrochemical reduction of the ROX. Thus, the FeCoNi(b)-800@RGO(2:1) composite modified glassy carbon electrode (FeCoNi(b)-800@RGO(2:1)/GCE) showed the superb electrochemical detection effect for ROX with relatively wide working range (0.1-1500 µM) and low detection limit (0.013 µM). Importantly, the FeCoNi(b)-800@RGO(2:1)/GCE sensor could accurately determine the contents of ROX in actual pork, chicken, duck and egg samples, indicating that it had good suitability in food safety monitoring.

3D/2D-Bismuth Oxybromide Spheres with Selenium-Doped Graphitic Carbon Nitride Sheets: An Efficient Electrocatalyst for the Detection of Arsenic Drug Roxarsone.

Heavy metals are crucial carcinogenic agents threatening the environment and living habituates. Among them, arsenic (As) is an important metalloid that is categorized as a group I toxic carcinogen. Roxarsone (RX) is an organoarsenic antibiotic compound primarily used as a veterinarian drug and growth promoter for poultry animals. The extensive usage of RX increased the accumulation of As in living beings and the ecosystem. Therefore, we have prepared an electrochemical sensor based on 3D bismuth oxybromide with 2D selenium-doped graphitic carbon nitride (BOB/SCN) electrocatalyst for the rapid detection of RX. The elemental and structural details were thoroughly investigated with several spectroscopic techniques. The electrochemical properties were measured by impedance and voltammetric measurements. The electrocatalytic behavior toward the RX was estimated with different voltammetric methods. Therefore, our BOB/SCN-based electrochemical sensor demonstrated a low detection limit (2.3 nM), low quantification value (7.7 nM), optimal sensitivity (0.675 µA µM-1 cm-2), and good linear ranges (0.01-77 and 77-857 µM). Additionally, this sensor showed good electrochemical performance and was applied to monitor the RX in various real samples with remarkable recoveries. Based on these results, our BOB/SCN sensor is a promising electrochemical platform for determining RX.

Reusable MOF-Coated Chitosan@Paper Strip Composite for Real-Time Monitoring of Pesticide Pendimethalin and Organoarsenic Feed Additive Roxarsone Levels in Environmental Water, Food, and Vegetable Samples.

An alarming increase in the use of pesticides and organoarsenic compounds and their toxic impacts on the environment have inspired us to develop a selective and highly sensitive sensor for the detection of these pollutants. Herein, a bio-friendly, low-cost Al-based luminescent metal-organic framework (1')-based fluorescent material is demonstrated that helps in sustaining water quality by rapid monitoring and quantification of a long-established pesticide (pendimethalin) and a widely employed organoarsenic feed additive (roxarsone). A pyridine-functionalized porous aluminum-based metal-organic framework (Al-MOF) was solvothermally synthesized. After activation, it was used for fast (<10 s) and selective turn-off detection of roxarsone and pendimethalin over other competitive analytes. This is the first MOF-based recyclable sensor for pendimethalin with a remarkably low limit of detection (LOD, 14.4 nM). Real-time effectiveness in detection of pendimethalin in various vegetable and food extracts was successfully verified. Moreover, the aqueous-phase recyclable detection of roxarsone with an ultralow detection limit (13.1 nM) makes it a potential candidate for real-time application. The detection limits for roxarsone and pendimethalin are lower than the existing luminescent material based sensors. Furthermore, the detection of roxarsone in different environmental water and a wide pH range with a good recovery percentage was demonstrated. In addition, a cheap and bio-friendly 1'@chitosan@paper strip composite was prepared and successfully employed for the hands-on detection of pendimethalin and roxarsone. The turn-off behavior of 1' in the presence of pendimethalin and roxarsone was examined systematically, and plausible mechanistic pathways were proposed with the help of multiple experimental evidences.

2D sheet structure of zinc molybdate decorated on MXene for highly selective and sensitive electrochemical detection of the arsenic drug Roxarsone in water samples.

Water contamination is a serious environmental issue posing a significant global challenge. Roxarsone (ROX), a widely used anticoccidial drug is excreted in urine and feces, potentially disrupting natural habitats. Therefore, rapid and cost-effective ROX detection is essential. In this study, we developed a 2D sheet structure of zinc molybdate decorated on MXene (ZnMoO4/MXene) for detecting ROX using electrochemical methods. The materials were characterized using appropriate spectrophotometric and voltammetric techniques. The ZnMoO4/MXene hybrid exhibited excellent electrocatalytic performance due to its rapid electron transfer rate and higher electrical conductivity. The ZnMoO4/MXene-modified GCE (ZnMoO4/MXene/GCE) showed a broad linear range with high sensitivity (10.413 µA µÐœ-1 cm-2) and appreciable limit of detection (LOD) as low as 0.0081 µM. It also demonstrated significant anti-interference capabilities, excellent storage stability, and remarkable reproducibility. Furthermore, the feasibility of utilizing ZnMoO4/MXene/GCE for monitoring ROX in water samples was confirmed, achieving satisfactory recoveries.

Design and fabrication of La-based perovskites incorporated with functionalized carbon nanofibers for the electrochemical detection of roxarsone in water and food samples.

The pentavalent arsenic compound roxarsone (RSN) is used as a feed additive in poultry for rapid growth, eventually ending up in poultry litter. Poultry litter contains chicken manure, which plays a vital role as an affordable fertilizer by providing rich nutrients to agricultural land. Consequently, the extensive use of poultry droppings serves as a conduit for the spread of toxic forms of arsenic in the soil and surface water. RSN can be easily oxidized to release highly carcinogenic As(III) and As(IV) species. Thus, investigations were conducted for the sensitive detection of RSN electrochemically by developing a sensor material based on lanthanum manganese oxide (LMO) and functionalized carbon nanofibers (f-CNFs). The successfully synthesised LMO/f-CNF composite was confirmed by chemical, compositional, and morphological studies. The electrochemical activity of the prepared composite material was examined using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The obtained results confirmed that LMO/f-CNF showed enhanced electrocatalytic activity and improved current response with a good linear range (0.01-0.78 µM and 2.08-497 µM, respectively), exhibiting a low limit of detection (LOD) of 0.004 µM with a high sensitivity of 13.24 µA µM-1 cm-2 towards the detection of RSN. The noteworthy features of LMO/f-CNF composite with its superior electrochemical performance enabled reliable reproducibility, exceptional stability and reliable practical application in the analysis of tap water and food sample, affording a recovery range of 86.1-98.87%.

Rainwater-borne H2O2 accelerates roxarsone degradation and reduces bioavailability of arsenic in paddy rice soils.

Contamination of rice by arsenic represents a significant human health risk. Roxarsone -bearing poultry manure is a major pollution source of arsenic to paddy soils. A mesocosm experiment plus a laboratory experiment was conducted to reveal the role of rainwater-borne H2O2 in the degradation of roxarsone in paddy rice soils. While roxarsone could be degraded via chemical oxidation by Fenton reaction-derived hydroxyl radical, microbially mediated decomposition was the major mechanism. The input of H2O2 into the paddy soils created a higher redox potential, which favored certain roxarsone-degrading and As(III)-oxidizing bacterial strains and disfavored certain As(V)-reducing bacterial strains. This was likely to be responsible for the enhanced roxarsone degradation and transformation of As(III) to As(V). Fenton-like reaction also tended to enhance the formation of Fe plaque on the root surface, which acted as a filter to retain As. The dominance of As(V) in porewater, combined with the filtering effect of Fe plaque significantly reduced the uptake of inorganic As by the rice plants and consequently its accumulation in the rice grains. The findings have implications for developing management strategies to minimize the negative impacts from the application of roxarsone-containing manure for fertilization of paddy rice soils.

Inhibitory effect of polyethylene microplastics on roxarsone degradation in soils.

Roxarsone (3-nitro-4-hydroxyphenylarsonic acid, Rox(V)), an extensively used organoarsenical feed additive, enters soils through the application of Rox(V)-containing manure and further degrades to highly toxic arsenicals. Microplastics, as emerging contaminants, are also frequently detected in soils. However, the effects of microplastics on soil Rox(V) degradation are unknown. A microcosm experiment was conducted to investigate soil Rox(V) degradation responses to polyethylene (PE) microplastics and the underlying mechanisms. PE microplastics inhibited soil Rox(V) degradation, with the main products being 3-amino-4-hydroxyphenylarsonic acid [3-AHPAA(V)], N-acetyl-4-hydroxy-m-arsanilic acid [N-AHPAA(V)], arsenate [As(V)], and arsenite [As(III)]. This inhibition was likely driven by the decline in soil pH by PE microplastic addition, which may directly enhance Rox(V) sorption in soils. The decreased soil pH further suppressed the nfnB gene related to nitroreduction of Rox(V) to 3-AHPAA(V) and nhoA gene associated with acetylation of 3-AHPAA(V) to N-AHPAA(V), accompanied by a decrease in the relative abundance of possible Rox(V)-degrading bacteria (e.g., Pseudomonadales), although the diversity, composition, network complexity, and assembly of soil bacterial communities were largely influenced by Rox(V) rather than PE microplastics. Our study emphasizes microplastic-induced inhibition of Rox(V) degradation in soils and the need to consider the role of microplastics in better risk assessment and remediation of Rox(V)-contaminated soils.

Insights into the influence of Fe(III) on the interaction between roxarsone and humic acid using multi-spectroscopic techniques.

The influence of Fe(III) on the interaction between roxarsone (ROX) and humic acid (HA) was investigated by multi-spectroscopic techniques. The fluorescence quenching experiment indicated that the fluorescence intensity of HA-ROX was quenched by Fe(III) through a static quenching process. Synchronous fluorescence spectra provided further information concerning the competitive combination between ROX and Fe(III) for HA. The results of the dialysis equilibrium experiment confirmed the existence of Fe(III) (0.05-0.1 mmol/L) promotes the combination of HA and ROX. Binding mechanisms were further characterized by FTIR spectroscopy, and the carboxyl functional group is involved in the binding process of HA/Fe/ROX. In addition, acidic and neutral conditions are more conducive to the combination of ROX and HA/Fe than alkaline conditions. The above discussion is of great significance in understanding the environmental fate of ROX under the coexistence of Fe(III) and HA.