Metabolomics reveals the potential mechanism of La(III) promoting enrichment of Sodium hydrogen arsenate and Roxarsone in Solanum nigrum L.

The rare earth element lanthanum (La(III)) has been found to effectively enhance crop yields and improve plant growth and development. Arsenic (As), as a class of toxic metals widely found in the environment, poses a serious threat to both ecological and human health. Research on the application of La(III) in phytoremediation to enhance remediation efficiency is currently lacking. This study examined the impact of La(III) on physiological and biochemical indicators of Solanum nigrum L. (S. nigrum) exposed to Sodium hydrogen arsenate (SA) and Roxarsone (ROX) treatments under hydroponic conditions. Results indicated that La(III) treatment increased S. nigrum's aboveground As transport capacity by 58.68 %-213 % compared to no La(III) application. Additionally, foliar spraying of La(III) significantly inhibited the expression of toxic metabolites in the root system of S. nigrum, reducing Benzamide by 99.79 % under SA treatment and ZON by 87.72 % under ROX treatment. La(III) is likely to promote the transport of toxins and nutrients within and out of cells by activating ABC transporters, thereby enhancing S. nigrum's arsenic tolerance and metabolic activity. These findings provide molecular-scale insights into La(III) enhancement of the resilience of hyper-enriched plants and the remediation potential of contaminated sites.

Roxarsone reduces earthworm-mediated nutrient cycling by suppressing aggregate formation and enzymic activity in soil with manure application.

The application of manure and earthworms are frequently used in fertilization practices to improve C, N, and P cycling in soil, which may be adversely affected by roxarsone (ROX), as an organoarsenical pollutant. To effectively address this issue, in this work, the interactive impacts of ROX and earthworm Eisenia foetida on the aggregate formation, input of organic carbon (OC), and changes in the available N and P following 56-day cultivation were systematically investigated. Compared to the control, earthworms increased the mean weight diameter (MWD) of the soil aggregates from 0.6 to 1.1 mm. Thereby, they activated soil enzymes including catalase (CAT), sucrase (SC), urease (UE), and neutral phosphatase (NP), with the soil's pH decreased to 7.1. Consequently, the values of OC, soluble nitrite (NO3-N), and Olsen-P content were respectively increased by 0.78-, 1.69-, and 0.87- folds in the E treatment (14.3 vs. 25.5 g/kg, 12.8 vs. 33.3 mg/kg, and 7.8 vs. 14.6 mg/kg). Although the changes in the R treatment were slight, ROX reduced the earthworm-mediated improvements of soil fertility during the application of the RE treatment compared to the E treatment, i.e., the values of MWD, OC, NO3-N, and Olsen-P were reduced to 0.9 mm, 20.4 g/kg, 25.4 mg/kg, and 11.6 mg/kg, respectively. From the well-fitted structural equation models, it was demonstrated that earthworms enhanced the aggregate formation and nutrient cycling of OC, NO3-N, and Olsen-P, which were inhibited by ROX. Overall, these adverse effects can be offset by earthworm addition, which can play the dual role of monitor and driver for the soil properties. Our work provides insightful strategies for ROX-bearing manure management.

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.

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.

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.

A Sb(III)-specific efflux transporter from Ensifer adhaerens E-60.

Antimony is pervasive environmental toxic substance, and numerous genes encoding mechanisms to resist, transform and extrude the toxic metalloid antimony have been discovered in various microorganisms. Here we identified a major facilitator superfamily (MFS) transporter, AntB, on the chromosome of the arsenite-oxidizing bacterium Ensifer adhaerens E-60 that confers resistance to Sb(III) and Sb(V). The antB gene is adjacent to gene encoding a LysR family transcriptional regulator termed LysRars, which is an As(III)/Sb(III)-responsive transcriptional repressor that is predicted to control expression of antB. Similar antB and lysRars genes are found in related arsenic-resistant bacteria, especially strains of Ensifer adhaerens, and the lysRars gene adjacent to antB encodes a member of a divergent subgroup of putative LysR-type regulators. Closely related AntB and LysRars orthologs contain three conserved cysteine residues, which are Cys17, Cys99, and Cys350 in AntB and Cys81, Cys289 and Cys294 in LysRars, respectively. Expression of antB is induced by As(III), Sb(III), Sb(V) and Rox(III) (4-hydroxy-3-nitrophenyl arsenite). Heterologous expression of antB in E. coli AW3110 (Δars) conferred resistance to Sb(III) and Sb(V) and reduced the intracellular concentration of Sb(III). The discovery of the Sb(III) efflux transporter AntB enriches our knowledge of the role of the efflux transporter in the antimony biogeochemical cycle.

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.

Influence of dissolved organic matter on the anaerobic biotransformation of roxarsone accompanying microbial community response.

Roxarsone (ROX), commonly employed as a livestock feed additive, largely remains unmetabolized and is subsequently excreted via feces. ROX could cause serious environmental risks due to its rapid transformation and high mobility in the anaerobic subsurface environment. Dissolved organic matter (DOM) is an important constituent of fecal organics in livestock waste and could affect the ROX biotransformation. Nonetheless, the underlying mechanisms governing the interaction between DOM and ROX biotransformation have not yet been elucidated in the anaerobic environment. In this study, the changes of ROX, metabolites, and microbial biomass in the solutions with varying DOM concentrations (0, 50, 100, 200, and 400 mg/L) under anaerobic environments were investigated during the ROX (200 mg/L) degradation. EEM-PARAFAC and metagenomic sequencing were combined to identify the dynamic shifts of DOM components and the functional microbial populations responsible for ROX degradation. Results indicated that DOM facilitated the anaerobic biotransformation of ROX and 200 mg/L ROX could be degraded completely in 28 h. The tryptophan-like within DOM functioned as a carbon source to promote the growth of microorganisms, thus accelerating the degradation of ROX. The mixed microflora involved in ROX anaerobic degrading contained genes associated with arsenic metabolism (arsR, arsC, acr3, arsA, nfnB, and arsB), and arsR, arsC, acr3 exhibited high microbial diversity. Variations in DOM concentrations significantly impacted the population dynamics of microorganisms involved in arsenic metabolism (Proteiniclasticum, Exiguobacterium, Clostridium, Proteiniphilum, Alkaliphilus, and Corynebacterium spp.), which in turn affected the transformation of ROX and its derivatives. This study reveals the mechanism of ROX degradation influenced by the varying concentrations of DOM under anaerobic environments, which is important for the prevention of arsenic contamination with elevated levels of organic matter.

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.

Arsenic behavior in soil-plant system under the manure application with the combination of antibiotic and roxarsone.

Limited attention has been given to the interaction between antibiotics and arsenic in the soil-plant system. In this investigation, Medicago sativa seedlings were grown in soil treated with cow manure containing oxytetracycline (OTC) or sulfadiazine (SD), as well as arsenic (introduced through roxarsone, referred to as ROX treatment). The study revealed a notable increase in As(III) and dimethylarsinic acid (DMA(V)) levels in rhizosphere soils and plant root tissues as arsenic contamination intensified in the presence of antibiotics, while concentrations of As(V) and monomethylarsonic acid (MMA(V)) decreased. Conversely, elevated antibiotic presence resulted in higher levels of As(V) but reduced DMA concentrations in both rhizosphere soils and plant root tissues in the presence of arsenic. The arsenic biotransformation gene aioA was inhibited by arsenic contamination when antibiotics were present, and suppressed by antibiotic contamination in the presence of arsenic, especially in SD treatments, resulting in reduced expression levels at higher SD concentrations. Conversely, the arsM gene exhibited consistent upregulation under all conditions. However, its expression was found to increase with higher concentrations of ROX in the presence of antibiotics, decrease with increasing SD concentrations, and initially rise before declining with higher levels of OTC in the presence of arsenic. Bacterial genera within the Proteobacteria phylum, such as Geobacter, Lusitaniella, Mesorhizobium, and Methylovirgula, showed significant co-occurrence with both aioA and arsM genes. Correlation analysis demonstrated associations between the four arsenic species and the two arsenic biotransformation genes, emphasizing pH as a critical factor influencing the transformation and uptake of different arsenic species in the soil-plant system. The combined stress of antibiotics and arsenic has the potential to modify arsenic behavior and associated risks in soil-plant systems, highlighting the necessity of considering this interaction in future research endeavors.

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%.

Biotransformation of roxarsone by earthworms and subsequent risk of soil arsenic release: The role of gut bacteria.

The organoarsenical feed additive roxarsone (ROX) is a ubiquitous threat due to the unpredictable levels of arsenic (As) released by soil bacteria. The earthworms representing soil fauna communities provide hotspots for As biotransformation genes (ABGs). Nonetheless, the role of gut bacteria in this regard is unclear. In this study, the changes in As speciation, bacterial ABGs, and communities were analyzed in a ROX-contaminated soil (50 mg/kg As in ROX form) containing the earthworm Eisenia feotida. (RE vs. R treatment). After 56 d, earthworms reduced the levels of both ROX and total As by 59 % and 17 %, respectively. The available As content was 10 % lower in the RE than in R treatment. Under ROX stress, the total ABG abundance was upregulated in both earthworm gut and soil, with synergistic effects observed following RE treatment. Besides, the enrichment of arsM and arsB genes in earthworm gut suggested that gut bacteria may facilitate As removal by enhancing As methylation and transport function in soil. However, the bacteria carrying ABGs were not associated with the ABG abundance in earthworm gut indicating the unique strategies of earthworm gut bacteria compared with soil bacteria due to different microenvironments. Based on a well-fit structural equation model (P = 0.120), we concluded that gut bacteria indirectly contribute to ROX transformation and As detoxification by modifying soil ABGs. The positive findings of earthworm-induced ROX transformation shed light on the role of As biomonitoring and bioremediation in organoarsenical-contaminated environments.

Multifunctional Eu(III)-modified HOFs: roxarsone and aristolochic acid carcinogen monitoring and latent fingerprint identification based on artificial intelligence.

The exploration of multifunctional materials and intelligent technologies used for fluorescence sensing and latent fingerprint (LFP) identification is a research hotspot of material science. In this study, an emerging crystalline luminescent material, Eu3+-functionalized hydrogen-bonded organic framework (Eu@HOF-BTB, Eu@1), is fabricated successfully. Eu@1 can emit purple red fluorescence with a high photoluminescence quantum yield of 36.82%. Combined with artificial intelligence (AI) algorithms including support vector machine, principal component analysis, and hierarchical clustering analysis, Eu@1 as a sensor can concurrently distinguish two carcinogens, roxarsone and aristolochic acid, based on different mechanisms. The sensing process exhibits high selectivity, high efficiency, and excellent anti-interference. Meanwhile, Eu@1 is also an excellent eikonogen for LFP identification with high-resolution and high-contrast. Based on an automatic fingerprint identification system, the simultaneous differentiation of two fingerprint images is achieved. Moreover, a simulation experiment of criminal arrest is conducted. By virtue of the Alexnet-based fingerprint analysis platform of AI, unknown LFPs can be compared with a database to identify the criminal within one second with over 90% recognition accuracy. With AI technology, HOFs are applied for the first time in the LFP identification field, which provides a new material and solution for investigators to track criminal clues and handle cases efficiently.

Roxarsone biotransformation by a nitroreductase and an acetyltransferase in Pseudomonas chlororaphis, a bacterium isolated from soil.

Roxarsone (3-nitro-4-hydroxyphenylarsonic acid, Rox), a widely used organoarsenical feed additive, can enter soils and be further biotransformed into various arsenic species that pose human health and ecological risks. However, the pathway and molecular mechanism of Rox biotransformation by soil microbes are not well studied. Therefore, in this study, we isolated a Rox-transforming bacterium from manure-fertilized soil and identified it as Pseudomonas chlororaphis through morphological analysis and 16S rRNA gene sequencing. Pseudomonas chlororaphis was able to biotransform Rox to 3-amino-4-hydroxyphenylarsonic acid (3-AHPAA), N-acetyl-4-hydroxy-m-arsanilic acid (N-AHPAA), arsenate [As(V)], arsenite [As(III)], and dimethylarsenate [DMAs(V)]. The complete genome of Pseudomonas chlororaphis was sequenced. PcmdaB, encoding a nitroreductase, and PcnhoA, encoding an acetyltransferase, were identified in the genome of Pseudomonas chlororaphis. Expression of PcmdaB and PcnhoA in E. coli Rosetta was shown to confer Rox(III) and 3-AHPAA(III) resistance through Rox nitroreduction and 3-AHPAA acetylation, respectively. The PcMdaB and PcNhoA enzymes were further purified and functionally characterized in vitro. The kinetic data of both PcMdaB and PcNhoA were well fit to the Michaelis-Menten equation, and nitroreduction catalyzed by PcMdaB is the rate-limiting step for Rox transformation. Our results provide new insights into the environmental risk assessment and bioremediation of Rox(V)-contaminated soils.

Interaction between roxarsone, an organic arsenic compound, with humic substances in the soil simulating environmental conditions.

In environmental systems, the soil is a principal route of contamination by various potentially toxic species. Roxarsone (RX) is an arsenic (V) organic compound used to treat parasitic diseases and as an additive for animal fattening. When the animal excretes RX, the residues may lead to environmental contamination. Due to their physicochemical properties, the soil's humic substances (HS) are important in species distribution in the environment and are involved in various specific interaction/adsorption processes. Since RX, an arsenic (V) compound, is considered an emerging contaminant, its interaction with HS was evaluated in simulated environmental conditions. The HS-RX interaction was analyzed by monitoring intrinsic HS fluorescence intensity variations caused by complexation with RX, forming non-fluorescent supramolecular complexes that yielded a binding constant Kb (on the order of 103). The HS-RX interaction occurred through static quenching due to complex formation in the ground state, which was confirmed by spectrophotometry. The process was spontaneous (ΔG < 0), and the predominant interaction forces were van der Waals and hydrogen bonding (ΔH < 0 and ΔS < 0), with an electrostatic component evidenced by the influence of ionic strength in the interaction process. Structural changes in the HS were verified by synchronized and 3D fluorescence, with higher variation in the region referring to the protein-like fraction. In addition, metal ions (except ions Cu(II)) favored HS-RX interaction. When interacting with HS, the RX epitope was suggested by 1H NMR, which indicated that the entire molecule interacts with the superstructure. An enzyme inhibition assay verified the ability to reduce the alkaline phosphatase activity of free and complexed RX (RX-HS). Finally, this work revealed the main parameters associated with HS and RX interaction in simulated environmental conditions, thus, providing data that may help our understanding of the dynamics of organic arsenic-influenced soils.

Bifunctional protein ArsRM contributes to arsenite methylation and resistance in Brevundimonas sp. M20.

BACKGROUND: Arsenic (As) with various chemical forms, including inorganic arsenic and organic arsenic, is the most prevalent water and environmental toxin. This metalloid occurs worldwide and many of its forms, especially arsenite [As(III)], cause various diseases including cancer. Organification of arsenite is an effective way for organisms to cope with arsenic toxicity. Microbial communities are vital contributors to the global arsenic biocycle and represent a promising way to reduce arsenite toxicity. METHODS: Brevundimonas sp. M20 with arsenite and roxarsone resistance was isolated from aquaculture sewage. The arsHRNBC cluster and the metRFHH operon of M20 were identified by sequencing. The gene encoding ArsR/methyltransferase fusion protein, arsRM, was amplified and expressed in Escherichia coli BL21 (DE3), and this strain showed resistance to arsenic in the present of 0.25-6 mM As(III), aresenate, or pentavalent roxarsone. The methylation activity and regulatory action of ArsRM were analyzed using Discovery Studio 2.0, and its functions were confirmed by methyltransferase activity analysis and electrophoretic mobility shift assays. RESULTS: The minimum inhibitory concentration of the roxarsone resistant strain Brevundimonas sp. M20 to arsenite was 4.5 mM. A 3,011-bp arsenite resistance ars cluster arsHRNBC and a 5649-bp methionine biosynthesis met operon were found on the 3.315-Mb chromosome. Functional prediction analyses suggested that ArsRM is a difunctional protein with transcriptional regulation and methyltransferase activities. Expression of ArsRM in E. coli increased its arsenite resistance to 1.5 mM. The arsenite methylation activity of ArsRM and its ability to bind to its own gene promoter were confirmed. The As(III)-binding site (ABS) and S-adenosylmethionine-binding motif are responsible for the difunctional characteristic of ArsRM. CONCLUSIONS: We conclude that ArsRM promotes arsenite methylation and is able to bind to its own promoter region to regulate transcription. This difunctional characteristic directly connects methionine and arsenic metabolism. Our findings contribute important new knowledge about microbial arsenic resistance and detoxification. Future work should further explore how ArsRM regulates the met operon and the ars cluster.

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.

Simultaneous oxidation of roxarsone and adsorption of released arsenic by FeS-activated sulfite.

The conventional oxidation-adsorption methods are effective for the removal of roxarsone (ROX) but are limited by complicated operation, toxic residual oxidant and leaching of toxic metal ions. Herein, we proposed a new approach to improve ROX removal, i.e., using the FeS/sulfite system. Experimental results showed that approximately 100% of ROX (20 mg/L) was removed and more than 90% of the released inorganic arsenic (As(V) dominated) was adsorbed on FeS within 40 min. This FeS/sulfite system was a non-homogeneous activation process, and SO4·-, ·OH and 1O2 were identified as reactive oxidizing species with their contributions to ROX degradation being 48.36%, 27.97% and 2.64%, respectively. Based on density functional theory calculations and HPLC-MS results, the degradation of ROX was achieved by C-As breaking, electrophilic addition, hydroxylation and denitrification. It was also found that the released inorganic arsenic was adsorbed through a combination of outer-sphere complexation and surface co-precipitation, and the generated arsenopyrite (FeAsS), a precursor to ecologically secure scorodite (FeAsO4·2H2O), was served as the foundation for further inorganic arsenic mineralization. This is the first attempt to use the FeS/sulfite system for organic heavy metal removal, which proposes a prospective technique for the removal of ROX.

Roxarsone Delivery Nanocomposite Based on Nitrite-Functionalized Mesoporous Polydopamine for Multidrug-Resistant Bacterial Infections via Enhanced Chemo-Photothermal Therapy.

Current treatments for infections caused by multidrug-resistant bacteria still remain challenging and therapeutic materials with high efficacy are of demand. Herein, a bactericidal nanocomposite was constructed by loading Roxarsone (ROX) onto nitrosylated mesoporous polydopamine (named mPDA@NO-ROX). The designed nanocomposite exhibited considerable photothermal effect and controlled NO and ROX co-delivery under the irradiation of near-infrared laser (NIR) to achieve enhanced chemo-photothermal antibacterial therapy. The in vitro antibacterial evaluation of the mPDA@NO-ROX demonstrated the effective elimination of the Gram-negative tetracycline-resistant Escherichia coil and Gram-positive methicillin-resistant Staphylococcus aureus under mild NIR irradiation compared to merely ROX loaded unmodified mPDA, indicating the NO enhanced chemo-photothermal therapy. In addition, the cytotoxicity experiments indicated that mPDA@NO-ROX exhibited only 5 % of hemolysis rate and high cell viability at 1 mg mL-1 against mammalian fibroblasts, suggesting the excellent biocompatibility. In conclusion, the mPDA@NO-ROX could be a promising candidate for anti-infection therapy of multidrug-resistant bacteria.

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.