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.

Roxarsone transformation and its impacts on soil enzyme activity in paddy soils: A new insight into water flooding effects.

The aromatic arsenical roxarsone (ROX) has been used as feed additive for decades worldwide. The past or present application of animal manure containing ROX in paddy fields results in arsenic (As) accumulation in rice grain. However, the degradation and transformation mechanisms of ROX in paddy soil which determine As bioavailability and uptake by rice are still unclear. The current study investigated the variation of As speciation and soil enzyme activities in ROX-treated soils under flooded and non-flooded conditions for six months. Our results showed that 70.2% of ROX persisted in non-flooded paddy soils after 180 d while ROX degraded completely within 7 d in flooded soils. The rapid degradation of ROX under flooded conditions owed to the enhanced biotic transformation that was caused by the low Eh and the predominant presence of Clostridium spp. and Bacillus spp. ROX was not only transformed to As(III) and As(V) in non-flooded soils but also to 3-amino-4-hydroxyphenylarsonic acid and methyl arsenicals in flooded soils. The degradation products significantly inhibited soil enzyme activities for 7-30 d, but the inhibition effects disappeared after 90 d due to the sorption of transformed As products to amorphous Fe oxides. This study provides new insights into the flooding effect on ROX fate in paddy fields, which is important for the management of animal waste and risk control on polluted sites.

N-Hydroxyarylamine O-Acetyltransferases Catalyze Acetylation of 3-Amino-4-Hydroxyphenylarsonic Acid in the 4-Hydroxy-3-Nitrobenzenearsonic Acid Transformation Pathway of Enterobacter sp. Strain CZ-1.

The organoarsenical feed additive 4-hydroxy-3-nitrobenzenearsonic acid (roxarsone [ROX]) is widely used and released into the environment. We previously showed a two-step pathway of ROX transformation by Enterobacter sp. strain CZ-1 involving the reduction of ROX to 3-amino-4-hydroxyphenylarsonic acid (3-AHPAA) and the acetylation of 3-AHPAA to N-acetyl-4-hydroxy-m-arsanilic acid (N-AHPAA) (K. Huang, H. Peng, F. Gao, Q. Liu, et al., Environ Pollut 247:482-487, 2019, https://doi.org/10.1016/j.envpol.2019.01.076). In this study, we identified two nhoA genes (nhoA1 and nhoA2), encoding N-hydroxyarylamine O-acetyltransferases, as responsible for 3-AHPAA acetylation in Enterobacter sp. strain CZ-1. The results of genetic disruption and complementation showed that both nhoA genes are involved in ROX biotransformation and that nhoA1 is the major 3-AHPAA acetyltransferase gene. Quantitative reverse transcription-PCR analysis showed that the relative expression level of nhoA1 was 3-fold higher than that of nhoA2 Each of the recombinant NhoAs was overexpressed in Escherichia coli BL21 and homogenously purified as a dimer by affinity chromatography. Both purified NhoAs catalyzed acetyl coenzyme A-dependent 3-AHPAA acetylation. The Km values of 3-AHPAA for NhoA1 and NhoA2 were 151.5 and 428.3 µM, respectively. Site-directed mutagenesis experiments indicated that two conserved arginine and cysteine residues of each NhoA were necessary for their enzyme activities.IMPORTANCE Roxarsone (ROX) is an organoarsenic feed additive that has been widely used in poultry industries for growth promotion, coccidiosis control, and meat pigmentation improvement for more than 70 years. Most ROX is excreted in the litter and dispersed into the environment, where it is transformed by microbes into different arsenic-containing compounds. A major product of ROX transformation is N-acetyl-4-hydroxy-m-arsanilic acid (N-AHPAA), which is also used as a clinical drug for treating refractory bacterial vaginosis. Here, we report the cloning and functional characterization of two genes encoding N-hydroxyarylamine O-acetyltransferases, NhoA1 and NhoA2, in Enterobacter sp. strain CZ-1, which catalyze the acetylation of 3-amino-4-hydroxyphenylarsonic acid (3-AHPAA) formed by the reduction of ROX to N-AHPAA. This study provides new insights into the function of N-hydroxyarylamine O-acetyltransferase in the transformation of an important organoarsenic compound.

Prevalence of Arsenic in chicken feed and its contamination pattern in different parts of chicken flesh: a market basket study.

Organoarsenic compounds are widely used in chicken feed for control of coccidial parasite, quick weight gain, and for imparting attractive color to the chicken flesh. A study was conducted to assess the level of arsenic in both chicken feed and flesh. Chicken feed was collected from 10 farm houses and total arsenic was estimated. The quantitative estimation suggests that the four levels of chicken feed contain different quantities of arsenic load. The results demonstrated that feed at stages III and IV levels contain 0.01 mg/g and 0.018 mg/g of arsenic respectively. However, at stages I and II levels, the feed contains 0.005 mg/g and 0.0052 mg/g of arsenic respectively. Proceeding similarly, chicken flesh was collected from ten vendors in the local markets of Burdwan. The experimental results revealed that deposition of arsenic in different parts of chicken body is not same. The highest accumulation was recorded in the flesh of chest followed by stomach, whereas flesh of the legs and heart showed lower levels of arsenic accumulation. A comprehensive calculation was thereafter done to assess the total amount of arsenic ingestion through consumption of chicken. If a person takes 60.0 g of chicken flesh (leg, breast, muscles, and stomach) everyday, then the person may consume 0.186-0.372 µg of arsenic per day. This study therefore clearly suggests that excessive consumption of poultry chicken may prove to be fatal. However, further research is necessary to confirm the present findings. To the best of our knowledge, this is probably the first report on the likelihood of arsenic contamination in the flesh of different body parts of poultry chicken from Eastern India.

Soil attribute regulates assimilation of roxarsone metabolites by rice (Oryza sativa L.).

Roxarsone (ROX), an organoarsenic feed additive, and its metabolites, can be present in animal manure used to fertilize rice. Rice is prone to absorb arsenic, and is subject to straighthead disorder, which reduces rice yield and is linked with organic arsenic compounds. This study aims to elucidate how soil property affect arsenic accumulation in rice plants fertilized with chicken manure containing ROX metabolites. Manures of chickens fed without or with ROX, designated as control manure and ROX treated manure (ROXCM), respectively, were applied in eight paddy soils of different origins, to investigate the assimilation of arsenic species in rice plants. The results show that inorganic arsenic (arsenate and arsenite), monomethylarsonic acid and dimethylarsinic acid (DMA) were detected in all brown rice and husk, trace tetramethylarsonium and trimethylarsine oxide were occasionally found in these both parts, whereas all these arsenic species were determined in straw, irrespective of manure type. ROXCM application specifically and significantly increased brown rice DMA (P = 0.002), which remarkably enhanced the risk of straighthead disease in rice. Although soil total As impacted grain biomass, soil free-iron oxides and pH dominated arsenic accumulation by rice plants. The significantly increased grain DMA suggests manure bearing ROX metabolites is not suitable to be used in soils with abundant free-iron oxides and/or high pH, if straighthead disorder is to be avoided in rice.

Effect of roxarsone metabolites in chicken manure on soil biological property.

Roxarsone (ROX), an organoarsenic feed additive, occurs as itself and its metabolites including As(V), As(III), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in animal manure. Animal manure improves soil biological property, whereas As compounds impact microorganisms. The integral influence of animal manure bearing ROX metabolites on soil biological quality is not clear yet. Herein, the effect of four chicken manures excreted by chickens fed with four diets containing 0, 40, 80 and 120 mg ROX kg-1, on soil biological attributes. ROX addition in chicken diets increased total As and ROX metabolites in manures, but decreased manure total N, ammonium and nitrate. The elevated ROX metabolites in manures increased soil total As, As species and total N, and increased first and then decreased soil nitrate and nitrite, but did not affect soil ammonium in manure-applied soils. The promoting role of both soil As(III) and ammonium on soil microbial biomass carbon and nitrogen, respiration and saccharase activity, were exceeded or balanced by the inhibiting effect of soil nitrate. The suppression of soil catalase activity by soil As(V) was surpassed by the enhancement caused by soil nitrate and nitrite. Soil urease, acid phosphatase and polyphenol oxidase activities were not suitable bioindicators in the four manure-amended soils. Soil DMA did not affect soil biological properties, and MMA was not detectable in all manure-amended soils. The above highlights the complexity of joint influence of soil As and N on biological attributes. Totally, when ROX is used at allowable dose in chicken diet, soil biological quality would be suppressed in manure-amended soil.

Soil Behaviour of the Veterinary Drugs Lincomycin, Monensin, and Roxarsone and Their Toxicity on Environmental Organisms.

Lincomycin, monensin, and roxarsone are commonly used veterinary drugs. This study investigated their behaviours in different soils and their toxic effects on environmental organisms. Sorption and mobility analyses were performed to detect the migration capacity of drugs in soils. Toxic effects were evaluated by inhibition or acute toxicity tests on six organism species: algae, plants, daphnia, fish, earthworms and quails. The log Kd values (Freundlich model) of drugs were: lincomycin in laterite soil was 1.82; monensin in laterite soil was 2.76; and roxarsone in black soil was 1.29. The Rf value of lincomycin, roxarsone, monensin were 0.4995, 0.4493 and 0.8348 in laterite soil, and 0.5258, 0.5835 and 0.8033 in black soil, respectively. The EC50 for Scenedesmus obliquus, Arabidopsis thaliana, Daphnia magna and LC50/LD50 for Eisenia fetida, Danio rerio, and Coturnix coturnix were: 13.15 mg/L,32.18 mg/kg dry soil,292.6 mg/L,452.7 mg/L,5.74 g/kg dry soil and 103.9 mg/kg (roxarsone); 1.085 mg/L, 25 mg/kg dry soil, 21.1 mg/L, 4.76 mg/L, 0.346 g/kg dry soil and 672.8 mg/kg (monensin); 0.813 mg/L, 35.40 mg/kg dry soil, >400 mg/L, >2800 mg/L, >15 g/kg dry soil, >2000 mg/kg (lincomycin). These results showed that the environmental effects of veterinary drug residues should not be neglected, due to their mobility in environmental media and potential toxic effects on environmental organisms.

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.

Limited carbon source retards inorganic arsenic release during roxarsone degradation in Shewanella oneidensis microbial fuel cells.

Directly relevant to the toxicity, mobility, and fate of arsenic, the biotransformation of inorganic and organic arsenicals has been extensively concerned, including roxarsone, a widely applied organoarsenical feed additive in poultry industry. Yet, little is known about the transformation details of roxarsone in microbial fuel cells (MFC). In this study, a two-chambered Shewanella oneidensis MR-1 microbial fuel cell was employed to investigate the transformation processes of roxarsone at various carbon source levels. Results show that limited carbon source remarkably inhibited inorganic arsenic release along roxarsone transformation, whereas numerous arsenical species were detected to be released into systems with sufficient carbon source supply, including trivalent and pentavalent inorganic arsenics, monomethylarsonous acid (MMA), and 4-hydroxy-3-aminobenzene arsonic acid (HAPA). Shewanella oneidensis MR-1 was able to cleave the C-As bond of trivalent HAPA yielding inorganic arsenics and MMA, even in the absence of the arsI gene encoding ArsI C-As lyase. We proposed a two-step nitro- and pentavalent-arsenate group reduction pathway for the roxarsone bioelectrochemical transformation. In addition, results indicated that the attached cells onto the electrode surface played a key function in the two-step reduction of roxarsone to trivalent HAPA, whereas planktonic cells were most likely responsible for the C-As bond breakage and the following dearylation. With these qualitative and quantitative estimations, it provides new insights into the mechanistic understanding of the roxarsone biotransformation process in microbial fuel cells, which is important for the biogeochemical cycling of arsenic.

Roxarsone exposure jeopardizes nitrogen removal and regulates bacterial community in biological sequential batch reactors.

Roxarsone is widely present in wastewaters of many animal farms in China. However, little is known about how long-term roxarsone exposure influences the nitrogen removal of biological wastewater treatment in agricultural settings. Here we investigated the nitrogen removal performance of a biological sequential batch reactor (SBR) and the changes of bacterial community, upon long-term roxarsone exposure. The long-term roxarsone dosing decreased the SBR nitrogen removal by 52.4%, with an immediate inhibition on denitrification and a delayed inhibition on nitrification. The analyses of bacterial enzymatic activities and 16 S rRNA sequencing revealed that bacterial activities generally decreased, and the nitrogen-cycling bacterial community was changed, particularly by the decrease (Acinetobacter and Methylophilaceae), persistence (Flavobacterium and Methylotenera), and emergence (Aeromonas) of certain bacterial genera. Overall, chronic roxarsone exposure could suppress nitrification and denitrification, which may even have broad implications on the use efficiency and cycling of nitrogen in agroecosystems.

Quantitative and qualitative assessment of additives present in broiler chicken feed and meat and their implications for human health.

OBJECTIVE: To determine the various constituents of commercial, broiler chicken feed and the presence of these constituents in their meat. METHODS: The experimental study was conducted at the Pakistan Council of Scientific and Industrial Research laboratory, Karachi. Samples of commercial broiler chicken feed and meat were collected in 2015 from a large poultry farm that supplies chicken meat to various suburban areas of the city. Another set of organic chickens were bred in an animal house. The samples of feed, meat and droppings were then analysed for the estimation of basic constituents and additives in the laboratory. Data was analysed using SPSS 20.0. RESULTS: The constituents were measured in 26 samples of chicken meat from each group. Calories (p<0.01), amount of protein (p<0.01), total fats (p<0.05), cholesterol (p<0.01), saturated fats (p<0.01), monounsaturated (p<0.05) and polyunsaturated fats (p<0.01) were significantly increased in commercial broiler chicken compared to that of organic chicken meat. The commercial chicken feed was found to contain crude carbohydrate, crude protein, crude fat, crude fibre, vitamins, amino acids, premixes of vitamins and toxicities of roxarsone, melamine and pesticides. Additive constituents were also present in the commercial chicken meat. These components were absent in organic chicken meat and droppings which suggests that they were absent in their feeding contents. CONCLUSIONS: Organic chickens were found to be safer for consumption than commercial chickens.

Response of microbial communities to roxarsone under different culture conditions.

Roxarsone is a feed additive widely used in the broiler and swine industries that has the potential to contaminate the environment, mainly via the use of poultry manure as fertilizer, which results in release of inorganic arsenic to the soil and water. This study was conducted to investigate roxarsone degradation and the response of the microbial community under different culture conditions using high-throughput sequencing technology. Poultry litter was incubated for 288 h in the presence of roxarsone under light aerobic, dark aerobic, or dark anaerobic conditions. The results showed that roxarsone was completely degraded after 48 h of dark anaerobic incubation, while 79.9% and 94.5% of roxarsone was degraded after 288 h of dark aerobic and light aerobic incubation, respectively. Under dark aerobic conditions with microbial inhibitor sodium azide, roxarsone was rarely degraded during the 288 h of incubation, illustrating that microorganisms play an important role in roxarsone degradation. Microbial community structure was significantly different among various culture conditions. Olivibacter, Sphingobacterium, and Proteiniphilum were the top 3 genera in the control samples. Sphingobacterium and Alishewanella dominated the light aerobic samples, while the dominant microflora of the dark aerobic samples were Acinetobacter spp. Pseudomonas and Advenella were the predominant genera of dark anaerobic samples. This study emphasizes the potential importance of microbes in roxarsone degradation and expands our current understanding of microbial ecology during roxarsone degradation under different environmental conditions.

Methylated Phenylarsenical Metabolites Discovered in Chicken Liver.

We report the discovery of three toxicologically relevant methylated phenylarsenical metabolites in the liver of chickens fed 3-nitro-4-hydroxyphenylarsonic acid (ROX), a feed additive in poultry production that is still in use in several countries. Methyl-3-nitro-4-hydroxyphenylarsonic acid (methyl-ROX), methyl-3-amino-4-hydroxyphenylarsonic acid (methyl-3-AHPAA), and methyl-3-acetamido-4-hydroxyphenylarsonic acid (or methyl-N-acetyl-ROX, methyl-N-AHPAA) were identified in such chicken livers, and the concentration of methyl-ROX was as high as 90 µg kg-1 , even after a five-day clearance period. The formation of these newly discovered methylated metabolites from reactions involving trivalent phenylarsonous acid substrates, S-adenosylmethionine, and the arsenic (+3 oxidation state) methyltransferase enzyme As3MT suggests that these compounds are formed by addition of a methyl group to a trivalent phenylarsenical substrate in an enzymatic process. The IC50 values of the trivalent phenylarsenical compounds were 300-30 000 times lower than those of the pentavalent phenylarsenicals.

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.

A disulfide-bond cascade mechanism for arsenic(III) S-adenosylmethionine methyltransferase.

Methylation of the toxic metalloid arsenic is widespread in nature. Members of every kingdom have arsenic(III) S-adenosylmethionine (SAM) methyltransferase enzymes, which are termed ArsM in microbes and AS3MT in animals, including humans. Trivalent arsenic(III) is methylated up to three times to form methylarsenite [MAs(III)], dimethylarsenite [DMAs(III)] and the volatile trimethylarsine [TMAs(III)]. In microbes, arsenic methylation is a detoxification process. In humans, MAs(III) and DMAs(III) are more toxic and carcinogenic than either inorganic arsenate or arsenite. Here, new crystal structures are reported of ArsM from the thermophilic eukaryotic alga Cyanidioschyzon sp. 5508 (CmArsM) with the bound aromatic arsenicals phenylarsenite [PhAs(III)] at 1.80 Šresolution and reduced roxarsone [Rox(III)] at 2.25 Šresolution. These organoarsenicals are bound to two of four conserved cysteine residues: Cys174 and Cys224. The electron density extends the structure to include a newly identified conserved cysteine residue, Cys44, which is disulfide-bonded to the fourth conserved cysteine residue, Cys72. A second disulfide bond between Cys72 and Cys174 had been observed previously in a structure with bound SAM. The loop containing Cys44 and Cys72 shifts by nearly 6.5 Šin the arsenic(III)-bound structures compared with the SAM-bound structure, which suggests that this movement leads to formation of the Cys72-Cys174 disulfide bond. A model is proposed for the catalytic mechanism of arsenic(III) SAM methyltransferases in which a disulfide-bond cascade maintains the products in the trivalent state.

Earth Abides Arsenic Biotransformations.

Arsenic is the most prevalent environmental toxic element and causes health problems throughout the world. The toxicity, mobility, and fate of arsenic in the environment are largely determined by its speciation, and arsenic speciation changes are driven, at least to some extent, by biological processes. In this article, biotransformation of arsenic is reviewed from the perspective of the formation of Earth and the evolution of life, and the connection between arsenic geochemistry and biology is described. The article provides a comprehensive overview of molecular mechanisms of arsenic redox and methylation cycles as well as other arsenic biotransformations. It also discusses the implications of arsenic biotransformation in environmental remediation and food safety, with particular emphasis on groundwater arsenic contamination and arsenic accumulation in rice.

Efficient roxarsone degradation by low-dose peroxymonosulfate with the activation of recycling iron-base composite material: Critical role of electron transfer.

Pollutant degradation via electron transfer based on advanced oxidation processes (AOPs) provides an economical and energy-efficient method for pollution control. In this study, an iron-rich waste, heating pad waste (HPW), was recycled as a raw material, and a strong magnetic catalyst (Fe-HPW) was synthesized at high temperature (900 °C). Results showed that in the constructed Fe-HPW/PMS system, effective roxarsone (ROX) degradation and TOC removal (72.54%) were achieved at a low-dose of oxidant (PMS, 0.05 mM) and catalyst (Fe-HPW, 0.05 g L-1), the ratio of PMS to ROX was only 2.5:1. In addition, the released inorganic arsenic was effectively removed from the solution. The analysis of the experimental results showed that ROX was effectively degraded by forming PMS/catalyst surface complexes (Fe-HPW-PMS*) to mediate electron transfer in the Fe-HPW/PMS system. Besides, this system performed effective ROX degradation over a wide pH range (pH=3-9) and showed high resistance to different water parameters. Overall, this study not only provides a new direction for the recycling application of HPW but also re-emphasizes the neglected nonradical pathway in advanced oxidation processes.

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.

Mo-doped Co LDHs as Raman enhanced substrate for detection of roxarsine.

BACKGROUND: Roxarsone (ROX) is widely used as a feed additive, which is indigestible after ingestion by poultry, and most of it can only be excreted into the natural environment and degraded into highly toxic and carcinogenic inorganic arsenic compounds, which pose a hazard to the ecosystem and human health. However, for roxarsone, traditional detection methods require complex and time-consuming procedures, so it is urgent to find a new fast detection method for detection of ROX. RESULTS: In this work, we developed a novel Raman enhancement material and utilized the Surface-enhanced Raman scattering (SERS) technique to achieve rapid and sensitive detection of roxarsone. Specifically, Mo-doped cobalt layered double hydroxides (Co-LDHs) semiconductor material (abbreviated as CMM-100) was prepared by a simple method of using ion-assisted MOF etching. Under laser excitation at a wavelength of 532 nm, the CMM-100 showed excellent SERS property to various organic dye molecules such as methylene blue (MB), Toluidine Blue(TB), and Crystal Violet (CV). Especially, an enhancement factor (EF) of 1.4 × 106 was achieved for MB. Compared with the traditional method, this work utilized the fast and non-destructive SERS technology, which achieved a rapid detection of ROX. The detection limit was as low as 9.73 × 10-10 M, and the detection range was from 10-9 M to 10-3 M. SIGNIFICANCE: In this work, SERS technology was adopted for the rapid and sensitive detection of ROX. This study provides a Raman-enhanced substrate named CMMs for detection of food additives, pesticides, biomolecules, etc., which also broadens the application areas of SERS materials.